Biogenic Manganese Oxide Generation and

Environmental
Science
and
Technology
(2014)
Volume 1
Edited by
George A. Sorial
Jihua Hong
ISBN 978-0976885368
Library of Congress Cataloging-in-Publication Data
Environmental Science and Technology 2014 Vol. 1
Proceedings from the 7th International Conference on Environmental Science and Technology, held on
June 9-13, 2014 in Houston, Texas, USA
Includes bibliographical references

ISBN: 978-0976885368
I. Sorial, George A.
II. Hong, Jihua
III. International Conference on Environmental Science and Technology
(7th : 2014 : Houston : Texas)
Printed in the United States of America
Copyright © 2014 American Science Press. All rights reserved. This document, or parts thereof, may not
be reproduced in any form without the written permission of the American Science Press. Requests for
permission or further information should be addressed to the American Science Press, 9720 Town Park
Dr. Ste. 18, Houston, TX 77036, USA
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Website: www.AASci.org/conference/env
ISBN 978-0976885368
© 2014 American Science Press
Environmental Science
and Technology
(2014)
Volume 1
Edited by
George A. Sorial
Jihua Hong
American Science Press, Houston, USA

Environmental Science & Technology 2014 Vol. 1
TABLE OF CONTENTS
INTRODUCTION
George A. Sorial and Jihua Hong ………………………………………………………….... 1
PLENARY SESSION
Aerobic Sludge Granulation: Current Perspectives, Advances and the Way Forward. Kuan-Yeow
Show, Duu-Jong Lee, Yan Yuegen, and Joo-Hwa Tay ……………………..………….…..………… 4
Hydraulic Fracturing, Water Conservation and Environmental Protection. Davis L. Ford ……..…. 10
Global Climate Change -The Quantifiable Sustainability Challenge. Frank Princiotta …………… 11
Development of a PV-Powered Electrochemical Wastewater Treatment System. Michael R.
Hoffmann, Kangwoo Cho, Clement Cid, and Qu Yan ………………………….…………....… 12
Evolving Conceptual Model of Natural Attenuation of Groundwater Plumes. Charles J. Newell and
David T. Adamson ………………………………………………………………………………….. 13
WATER POLLUTION AND WATER QUALITY
Rivers, Lakes and Estuary Systems
New Findings on Sources of Orthophosphate in Upper Malibu Creek Watershed: A Geologic Source
Primarily? Barry Hibbs, Kathleen Kuepper, and Yola Wong K …………………………….……… 15
Evaluation on Eco-security of Water Resources and Regulating & Control Mode of Environmental
Planning for Lake Basin --- A Case of Taping Lake, Anhui Province, China. Xiangrong Wang… 16
Key Issues for River Regulation: An Illustration from Dianchi Inflowing Rivers in China. Baoxue
Zhou, Ke Huang, JinHua Li, Jing Bai, ZhuJing Jin, FengLe Yang. …………………………….. 17
Watershed Management
Trace Element Mobilization by Oxidation via Anthropogenic Nitrate in Southern California

Watershed. Yola Wong K, Barry J. Hibbs ………………………………………………………. 18
Sustainable or Green Water Management Practices by South African Mining Companies. Mbofho
Stanley Liphadzi & Andre Vermaak …………………………………………………………………… 19
Water Resources and Assessment
Crude Palm Oil Production: Environmental Impacts Assessment of Freshwater Consumption Using
LCA Approach. Zainura Zainon Noor, Noor Salehan M. Sabli, Che Hafizan Che Ahmad ……. 20
The ART In-Well Technologies, Re-Engineering Existing Remedies to Reduce Time, Costs & Risks.
Mohamed Odah …………………………………………………………………………………..………. 21
Environmental Risk Assessment of Caffeine in Parana’s Rivers (Brazil). Maiara C. Perussolo,
Isadora Terumi Saruhashi, Pauline Lais Nasatto, Andréa Fernandes, Eliane Carvalho de
Vasconcelos, and Cíntia Mara Ribas de Oliveira. …………………………………………………… 22
Progress on the Research of Flood Routing under the Effect of Seepage in Seasonal Streams. Wu
Guizhi , Li ningning and Wu Zhouhu ………………………………………………………………….. 23
i
Mass Fluxes of Urban Micropollutants and Integrated Modelling of the River – Groundwater –
Interaction in the City of Halle/Germany. Frido Reinstorf, Sebastian Leschik, Andreas Musolff2,
Gerhard Strauch, Karsten Osenbrueck and Mario Schirmer....................................................... 24
Improving Implementation Capacities of Cities by sharing best practices in Urban Water Cycle
Services. Kees van Leeuwen ......................................................................................................... 25
Sustainability of Water Resources of Ho Chi Minh City, Vietnam. N.C. Woo, Minh T. Ngo, Jae M.
Lee ............................................................................................................................................... 26
Assessment of Groundwater Recharge Using Water-Table Fluctuation Method and Water Balance
Model. Sasmita Sahoo, Madan K. Jha .......................................................................................... 27
Evaporation Reduction Based Design of Water Ponds surface Areas Using Palm Frond. Ibrahim
Elsebaie ........................................................................................................................................ 35
Hydraulic Fracturing: A Look at Efficiency and the Environmental Effects of Fracking. Emily C
Jackson and David E Dismukes. .................................................................................................. 42
Groundwater
Correlations between Chlorinated Aliphatic Hydrocarbons and Environmental Variables in a

Contaminated Groundwater in Shanghai, China. Lu Qiang, Li Hui, Lin Kuang Fei, and Liu Yong
Di .................................................................................................................................................. 47
Remediation of Acidic Groundwater Using a Sodium Bicarbonate Injection System, Christina
Brown, Paul Marotta, David Wall, Teresa Jordan, and Christina DeJarlais …………………….. 48
A Comparative Study of Enhanced Bioremediation Techniques for a BTEX Compound (Toluene) in
Contaminated Groundwater. B.K Yadav, Shreejita Basu, Anuj Mathur and Shashi Mathur……. 49
Interactions of Arsenic Desorption and Indigenous Bacterial Activity in Shallow Groundwater
System. Zuoming Xie, Guangming Ouyang, Xiaoyan Sun, Dong Yang, Yanxin Wang …………. 55
Optimization of Fluoride Removal from Aluminium Smelter Contaminated Ground Water. Scott
Sleap, Brett Turner, Kristian. KrabbenhØft and Scott Sloan ……………………………………….. 56
A Pilot Scale Permeable Reactive Barrier for the Treatment of Spent Potliner Contaminated Ground
Water. Brett Turner, Scott Sleap, Kristian. KrabbenhØft and Scott Sloan ………………………… 57
Residues of Veterinary Antibiotics in Environmental Waters in Central Jianghan Plain, China. Tong
Lei, Wang Yanxin, Liu Hui, Li Minjing ........................................................................................ 58
Prediction of County-level Contamination Exceeding Rate from Groundwater Sampling Data
through Intelligent Data Dependent Modeling. Qing Li, Fengxiang Qiao, Lei Yu …………….. 59
Exploring the Influence of Dissolved Organic Matter on Phosphorus Mobility in Groundwater.
Christine A. Rumsey, Darwin L. Sorensen, David K. Stevens, Joan E. McLean ……………….. 65
An Analysis of Groundwater Chemistry of Hot Springs in the Soutpansberg Basin in South Africa.
Ayanda Shabalala, A.P.K. Nyabeze and Zuko Mankayi. ……………………………………………. 66
Non-point Sources
Atmospheric Reactive Nitrogen Deposition onto Coastal Regions of China. Xiaosheng Luo and
Xuejun Liu ……………………........................................................................................................ 67
Nutrient Load Predictions in Streams using LS-SVM and Wavelet-ANN. Raj Mohan Singh …….. 68
Wastewater Discharge Management
The Study of Destructive Effects of Wastewater Caused by the Activities of leather Manufacturing
Factories in Tehran. Shobeiri Seyed Mohammad, Kavei Behrouz, Shotorbani Azarmir Marjan,
Alireza Bassiri, Nazari Batoul ...................................................................................................... 77
ii
Theoretical Analysis of Pollutant-Mixing Zone for Rivers with Variant Lateral Diffusion Coefficient.
Zhou-hu Wu, Wen Wu ............................................................................................................... 78
Effect of Textile Effluent on Germination and Growth of Gram. Monika Chandel, Tank Shantilal K.. 83
In-Situ Measurement and Monitoring
Monitoring of Cyanotoxin and T&O Compound Producing Cyanobacteria in Drinking Water

Reservoirs using qPCR Method. Tsair-Fuh Lin, Yi-Ting Chiu, Hung-Kai Yen 88
A Novel Flow-cell for in situ Spectrophotometric Detection of Contaminants in Water Samples.
Emanuele Reggiani, Richard Bellerby, Kai Sørensen 89
A Microfluidic Colorimetric Analyser for pH in Water. John Cleary, Deirdre Cogan, Thomas
Phelan, Kamil Jankowski, Dermot Diamond 90
Drinking Water
Sustaining Safe Drinking Water Supply in Developing Countries: Lebanon Case Study. Mey Jurdi.. 91
Biological Desalination of Seawater Using Marin Microalga Scenedesmus sp. and Chlorella
vulgaris. E. Sahle-Demessie, Ashraf Aly Hassan, Amy Zhao……………………………………….. 92
Analysis for Atmospheric Water for Drinking. Qing XIA and Shu GENG ……………………………. 93
Source Water Protection for Drinking Water Production: A European River Memorandum. Peter G
Stoks and Ina Brüning .................................................................................................................. 94
Community Water Supply and Treatment Project in Cameroon: Chlorinator Design and
Development. Kristen Chorney and Sam Miller........................................................................... 95
Vulnerability Assessment of Small Community Water Systems in Puerto Rico. Adaíl Alicea-
Martínez, Rafael A. Rios ............................................................................................................... 96
Water Quality Assessment/Management
An Independent Investigation into the Physico-Chemical Purification Capacity of Gravity Fed Home
Water Treatment Devices Supplied in South Africa. Cherie Ann Kruger, Tobias George
Barnard, Natasha Hodgkinson and Cathleen Bartie ................................................................... 97
Improving Surface Water Quality of Agricultural Watershed using Planned Intervention
Microwatershed Approach. Durga D. Poudel. ............................................................................ 98
An Analytical Model for Pollutant Transport in the Rosetta Branch of the Nile River, Egypt.
Mohamed Mostafa and Robert W. Peters. ................................................................................... 99
Polychlorinated Biphenyls (PCBs) in Industrial and Municipal Effluents: Concentrations, Congener
Profiles, and Partitioning onto Particulates. Aparna Balasubramani, Hanadi S. Rifai, and Nathan
L. Howell. .................................................................................................................................... 100
Characteristics of Optimization Problems for Coastal Ground Water Management. Karen Ricciardi 106
Quantifying E. coli Discharge from Onsite Sewage Facilities in the Dickinson Bayou Watershed,
Texas. Derek Morrison, Clyde Munster, R. Karthikeyan, John Jacob……………………………. 107
Impact of Soil Type on the Salt Accumulation Due To Recycled Water Irrigation. Muhammad
Muhitur Rahman, Dharma Hagare, Basant Maheshwari and Peter Dillon……………………….. 108
Diversity of Aquatic Flora in Relation to Water Quality in Kolleru Lake, Andhra Pradesh, India. P.
Brahmaji Rao ............................................................................................................................... 109
Heavy Metal Analysis in Catchment and Fish Communities of Mista-Ali Tin Mine Lake, Middle-
Belt Nigeria. Jatau-Emeagha, G. L, Wade, J.W.W and Ufodike, E.B.C …………………………… 110
Study on Water Quality Variation during Rainfall Runoff Evolution Process in a City Residential
District. Huaien Li, Jiake Li and Zengchao Liu. ......................................................................... 119
iii
Low Cost Autonomous Sensing Platforms for the Direct Determination of Nutrients in Water.
Deirdre Cogan B, John Cleary, Kamil Jankowski, Dermot Diamond, Mark Bowkett ………….. 120
QUAL2K Water Quality Analysis and Source Locations Identification: A Case Study of North
Buffalo Stream. Jenberu Feyyisa, Shoou-Yuh Chang ………………………………………………. 127
Technical, Financial and Administrative Capacity Evaluations and Improvement of Small
Community Water Systems in Puerto Rico. Adaíl Alicea-Martínez, Rafael A. Rios …………….. 128
Nitrogen-Phosphorus Wastewater Treatment / Sludge Treatment
Simultaneous Removal of Ammonia and Nitrate by Electrolytic Decomposition as Tertiary

Wastewater Treatment. Jing Ding, Qingliang Zhao, Wei Li, and Kun Wang. …………………… 134
Enhancement of Anammox Biomass Activity with External Electric Field Application. Sen Qiao,
Xin Yin, Jiti Zhou, Yingjun Cheng ................................................................................................ 140
Anaerobic Oxidation of Ammonium Coupled to Electricity Production in a Microbial Electrolysis
Cell. Bo Qu and Bin Fan. ............................................................................................................ 146
Effect of Bamboo Biochar on Fertility and Nutrient Leaching of a Sandy Pear Orchard Soil in
Southeast China. Lou Liping, George A.Sorial ........................................................................... 147
Sludge Treatment
Changes of Bacterial Community Diversity in Oxic-Settling-Anaerobic (OSA) Activated Sludge

Process. Lianpeng Sun, Jinxin Tan, Xiaoyu Yu, and Lili Chen…………………………………….. 148
Identification and Characterization of Dye Degrader Microbes in Microbial Granular Sludge
Treating Synthetic Textile Wastewater. K. Muda, A. Aris, M.R.Salim, Z. Ibrahim, M.Z Nawahwi. 155
Compost Bioremediation of Oil Sludge by Using Different Manures under Laboratory Conditions.
Ubani O., Atagana H. I. and Thantsha M. S. …………………………………………………………. 156
Identification and Characterization of Oil Sludge Degrading Bacteria Isolated from Compost Ubani
O., Atagana H. I. and Thantsha M. S. and Adeleke R. ............................................................... 157
Effect of Acid Treatment on Sewage Sludge Derived Carbons for Catalytic Wet Peroxide Oxidation.
Yang Yu, Huangzhao Wei, Yamin Wang, Li Yu, Wentian Jiang, Songbo He, Chenglin Sun…….. 158
Appraisal of Certain Anaerobic Digestion Studies. Ram Pal Singh and P. Pal ……………………… 159
Municipal Wastewater Biotreatment
Applying Static Magnetic Field on Physical Properties of Activated Sludge: Optimization through
Response Surface Methodology. Nur Syamimi Zaidi, Khalida Muda and Johan Sohaili……….. 167
Life Cycle Assessment of a Municipal Wastewater Treatment Plant- A Case Study in Kinmen,
Taiwan. Huan-Yu Shiu and Pei-Te Chiueh. ................................................................................ 173
Evaluation of Bacteria and Metals in Sewage Dump Site in Jos-Nigeria. Yakubu, Juliet M, Agarry,
Olaitan O ..................................................................................................................................... 174
The Effect of EPS on Mixed Liquor Characteristics and Membrane Fouling in UCT¬MBR Process.
Qiongyuan Dong, Xiaonan Feng, Tao Tao, Lin Chen, Junhong Zhou and Guohong Yang…… 175
An Approach for Selection of Wastewater Treatment Units using Analytical Hierarchy Process.
Nekram Rawal, A.K.Sachan ......................................................................................................... 181
Structure and Function of Dominant Microbial Community in Enhanced Aerobic Granular Sludge
Process. Liang Zhu, Xiangyang Xu, Xin Dai, Jiaheng Zhou ………………………………………… 187
Industrial Wastewater Biotreatment
iv
Biogenic Manganese Oxide Generation and Mn(II) Removal by Manganese Oxidizing Bacteria
using Response Surface Methodology. Narsi R. Bishnoi and Shalu. ……………………………… 188
Reduction of Vinasse Soybean Pollution Using Different Strains of the Genus Cupriavidus Necator.
Elizabeth dos Santos Costa Alexandre, Luiz Gustavo Lacerda, Marco Aurélio da Silva Carvalho
Filho ............................................................................................................................................. 194
The Application of Nitrification-Denitrification Process to Enhance Treatment Efficiency in
Livestock Wastewater. B. S. Lee, S. S. Ton ................................................................................ 195
Refinery Wastewater Treatment: A Challenge towards Zero Liquid Discharge. Farid Benyahia…… 200
Examining Process Wastewater Treatment and Grey Water Footprint of Biofuel Produced via Fast
Pyrolysis and Hydrotreating. May Wu .......................................................................................... 201
Isolation of a Lysinibacillus Strain B1-CDA Showing Potentials for Arsenic Bioremediation. Aminur
Rahman, Noor Nahar, Jana Jass, and Abul Mandal………………………………………………… 202
Effects of Zinc on Germination, Seedling Growth and Nutrient Contact of Rauvolfia Serpentine.
Milvee K. Vyas, Kailash Patel, Parimal Patel ………………………………………………………… 203
Adsorption/Desorption for Wastewater Treatment
Synthesis and Characterization of Cu(II) Imprinted Nanoparticles Based on Polyethyleneimine for

Selective Recognition of Copper. Jin jia，Shengji Luan, and Aihua Wu. ……………………… 206
Adsorption of Pb(II) on Nanoscale Iron-Oxide Doped Granular Activated Carbon. Zhihua Xu,
Daofang Zhang and Weifang Chen …………………………………………………………………… 207
Synthesis and Characterization of High Ordered Mesoporous Carbon (OMC) Using Polyacrylamide
for Resorcinol Removal. Wan Shou, Hanlong Ren, Zhong Ren and Dianel Dianchen Gang…. 213
Adsorption of Phenol onto Low Cost Adsorbent: Optimization of Adsorption Process Parameters
Ramakant S. Ingole and Dilip H. Lataye …………………………………………………………….. 219
Removal of Diclofenac Sodium and Carbamazepine from Water by Regenerable Granular Carbon
Nanotubes/Alumina Adsorbents. Shubo Deng, Haoran Wei, Bin Wang, Jun Huang, Gang Yu … 225
Fluoride Biosorption with Modified Eichhornia crassipes and Typha Elephantina. Suvendu Manna,
Prosenjit Saha, Debasis Roy, Basudam Adhikari, Ramkrishna Sen……………………………… 226
Removal of Chromium (VI) by Ethyl Cellulose Treated with Polyaniline. Bin Qiu, Zhanhu Guo,
Cuixia Xu, Suying Wei ………………………………………………………………………………….. 227
Synthesis and Structure Characterization of Modified Ordered Mesoporous Carbons for Total
Organic Carbon (TOC) Model Compound (Resorcinol) Removal. Hanlong Ren, Wan Shou,
Chong Ren and Dianel Dianchen Gang ………………………………………………………………. 228
Characterization and Absorption Behavior of Ammonia and Methylene Blue by Biochar Derived
from Common Reed. Lun Lu, Fengmin Li, and Zhi Liang. ………………………………………… 233
Adsorption of Nicotine on Magnetically Separable Ordered Mesoporous Carbons in Aqueous
Solution. Hsin-Yu Lin, Ya-hsuan Liou, and Pei-Te Chiueh. ……………………………………… 234
Cleaning Metal Contaminated Water Using Pyrolyzed Banana Peels. Bluyé Demessie, E. Sahle-
Demessie, George A. Sorial ……………………………………………………………………………. 235
Ion Exchange/Adsorption/Desorption To Recover Nutrients from Conventional and Segregated
Streams of Domestic Wastewater for Further Use as Fertilizer. Bilsen Beler Baykal …………… 236
Elucidating the Role of Phenolics in the Effectiveness of DOM Adsorption on Activated Carbon.
Liang Yan and George. A. Sorial ………………………………………………………………………. 242
Removal of Fluoride from Water Using Chemically Modified Jute. Basudam Adhikari, Suvendu
Manna, Prosenjit Saha, Debasis Roy…………………………………………………………………… 243
Effect of Effluent Organic Matter on Organic Micropollutants Sorption onto Activated Carbon.
Caroline Soares-Pereira, Romain Mailler, Adèle Bressy, Emilie Caupos, Lila Boudahmane,
Mohamed Saad, Jonhy Gasperi, Vincent Rocher, Gilles Varrault …………………………… 249
v
Removal of Emerging Micropollutants from WWTP Discharges: Is Activated Carbon Adsorption

Suitable for Wastewater Application? Romain Mailler, Johnny Gasperi, Yves Coquet, Cécile
Cren-Olivé, Nathalie Cartiser, Sifax Zedek, Steven Deshayes, Adèle Bressy, Emilie Caupos,
Régis Moilleron, Ghassan Chebbo and Vincent Rocher. ………………………………………… 250
Biosorption of Heavy Metals from Aqueous Solution by Bacteria Staphylococcus aureus & Bacillus
spp. Patel Ritixa, Tank Shantilal……………………………………………………………………….. 251
Adsorption of Uranium, Strontium and Cesium in Radioactive Waste by Modified Attapulgite. Jie
Yang, Na Guo, Jingsheng Wang, Haiyang Chen……………………………………………………… 255
Physico-chemical Wastewater Treatment
Bioinspired Gradient-structure Fibers for Water Collection at Micro- and Nano-level. Yongmei
Zheng………………………………………………………………………………………………………... 260
Advanced Oxidation Methods-Fenton Process for Dye Removal in Textile Wastewater. Macid
Nurbas and Burak Dindas ……………………………………………………………………………… 261
Unconventional Oil Contaminated Industrial Effluent Treatment by Catalyzed Hydrogen Peroxide
and Sodium Persulfate. Niina Dulova, Eneliis Kattel, Marika Viisimaa, Anna Goi, Deniss
Klauson, Marina Trapido, Alar Saluste, and Taavo Tenno. ……………………………………… 262
Efficient Dechlorination of 2,4-Dichlorophenol in An Aqueous Media Using a Pd/TiO2NTs/Ti
Cathode. Jiangkun Du and Jianguo Bao……………………………………………………………… 269
Treatability of Aqueous Alcohol Ethoxylates Solution by Electrocoagulation and Coagulation.
Çisem Ecer, Işık Kabdaşlı, Olcay Tünay, Tuğba Ölmez Hancı. …………………………………… 279
Removal of Chromium Cr(VI) From Wastewater Using Saudi Activated Bentonite. Saad Al-
Shahrani ………………………………………………………………………………………………….. 280
Chromium(VI) Removal by a Fe-Mn Binary Oxide with and without H2O2. Si-Hyun Do and Yong-
Jae Kwon………………………………………………………………………………………………… 281
Electrochemical Advanced Oxidation Process for Optimal Decontamination of Phenolic
Wastewater Containing Inorganic Species. Nuhu Dalhat Muazu, Gulraiz Khan1 and Nabil
Jarrah ………………………………………………………………………………………………………. 282
Reactions and Degradation of Wastewater Contaminants
Continuous Treatments of Estrogens through Polymerization and Regeneration of Electrolytic Cells.

Vo Huu Cong, Sota Iwaya and Yutaka Sakakibara ………………………………………………….. 283
Assessment of Cometabolic Biodegradation Potential of Diclofenac in The Presence of Acetate
under Anaerobic Conditions. Sevgi Sari, Emel Topuz, Egemen Aydin, Didem Okutman Tas….. 290
Nanotechnology Applications
Graphene-Hapten-Based Nanosensor for Ultrasensitive Detection of Bisphenol A with an

Optofluidic Biosensing Platform. Feng Long, Hanchang Shi. ………………..…………………… 291
Effect of Freshwater Relevant Conditions on the Agglomeration of Titanium Dioxide Nanoparticles,
Emel TOPUZ, Laura SIGG and Ilhan TALINLI……………………………………………………… 292
Using Persulfate Activated by an Emplaced Zone of Iron Nanoparticles to Treat a Trichloroethylene
Source Zone. Mohammed A. Al-Shamsi, Neil R. Thomson………………………………………… 293
Mathematical Simulation of Nano Sized Aluminum Phages to Purify Water. V.K. Katiyar and Rohit
Agarwal………………………………………………………………………………………………….. 294
Interaction of Bacterial Biofilms with Engineered Nanoparticles, Hengye Jing, George Sorial, Ashraf
Aly Hassan, E. Sahle Demessie, and Christina Bennett-Stamper. ………………………………… 295
vi
Evaluating Stability and Structural Changes of Nanocomposites and Developing Methods to

Evaluate the Release of Nanoparticles. Amy Zhao, E. Sahle-Demessie, Heidi Grecsek ………… 296
Preparation of a Novel Magnetic Nanoparticle Adsorbent and Its Adsorption Behavior of Arsenic in
Groundwater. Shuqiong Kong, Yanxin Wang, Qinhong Hu and Abass K. Olusegun…………….. 297
Surface Chemistry of Iron-Impregnated Mineral Oxides and Catalytic Activity for Oxidation of
Aqueous Contaminants. Yue Li , Weile Yan. ………………………………………………………….. 298
Electrocatalytic Characteristics of Hybrid MWCNTs and GNPs with Different Surface Morphology.
Yanping Cui, Yu Zhu, Yaohui Wang, Yanyan Qin…………………………………………………….. 299
Visible-Light Responsive Photocatalytic Fuel Cell Based for Simultaneous Wastewater Treatment
and Electricity Generation. Baoxue Zhou, Jing Bai, JInhua Li and Suqin Jiang……………….. 303
Water Purification Technologies
Low Grade Heat: An Underused Energy Source for Desalination Using Membrane Distillation.
Farid Benyahia. ……………………………………………………………………………………….…. 304
AIR POLLUTION AND AIR QUALITY CONTROL
Aerosol
Performance of Aerosol Sampling Inlet from Aircraft Platform. Baoqing Wang, Shu Yao, Zebei
Wang, Ronghui Chen, and Yangyang Li, Zhuoru Wang. ………………………………………… 306
Air Quality Assessment
Application of Factal Analysis to Assess of Air Pollutant Emission Rates in Opencast Coal Mines-
An Innovative Approach. Mrinal K.Ghose…………………………………………………………… 312
PLS-Path Model Analysis for Understanding the Cause-Effect Relationship of Ground Level Ozone
Concentration. A. K. Gorai, F. Tuluri, and P. B. Tchounwou…………………………………….. 313
Intra-urban Spatial and Temporal Comparison of Fine and Quasi-Ultrafine Particles in Houston TX.
Yuncan Guo, Masoud Afshar, and Inkyu Han………………………………………………………. 314
Non-Parametric Regionalized Model Performance Evaluation of PM2.5 Chemical Transport
Models. Jeanette Reyes and Marc Serre. ……………………………………………………………. 315
On-line Measurement of Aerosol from Desulfurization Flue Gas Based on Aerosol Mass
Spectrometry. Pan Danping, Guo Yanpeng, Bao Jingjing, Yang Linjun………………………. 316
Metabolic Characteristics and Community Diversities of Airborne Microbes at Different Functional
Regions in Qingdao in Winter. WU Dengdeng, and SONG Zhiwe. ……………………………. 317
Source Identification of Atmospheric Particulate Matter Using Radiocarbon and Molecular Source
Markers. Hyun-Min Hwang, Bruce Buchholz, Thomas Young …………………………………… 318
Air Pollutant Watch List of Texas – Port Arthur Example. Tara Capobianco, Ross Jones, and Darrell
McCant……………………………………………………………………………………………………. 319
Atmospheric Pollution in a North African City: The Ceuta Paradigma. S. Garcia Dos Santos, R.
Fernández Patier, M.A. Sintes Puertas, A. Aguirre Alfaro, J. Alonso Herreros and S. Guevara
Hernández, R. Benarroch Benarroch and J.M. Cantón Gálvez, Saul García ………………… 320
Occupational Exposure to Chemicals in Nail Salons. Tasneem Islam, Margaret Back, Katherine
Chin, Morgan Dashko, Alisa Feinswog, Aliza Heeren, Ben Krause, Molly Pearlman, Maia
Rodriguez-Semp, Madeline Rosenberg, Emily Scharf, Shanlai Shangguan, Emily Weisfeld, Brett
Aronson, Joseph Allen, Matt Fragala, Theodore Myatt, James Stewart, Laura Goldin………. 321
Source Apportionment of Indoor PM2.5 at Santiago, Chile. Héctor Jorquera and Francisco Barraza. 322
vii
Atmospheric Carcinogenic Polycyclic Aromatic Hydrocarbons in Houston, TX, USA: Pine Needles
as Passive Samplers. Sharmila Bhandari, Hyun-Min Hwang……………………………………… 323
Effectiveness of Low Emission Zones: Analysis of the Changes in Fine Dust Concentrations (PM10)
in 19 German Cities. Peter Morfeld, David.A. Groneberg, and Michael Spallek…………………. 324
A Comparative Study of Economic Evaluation Methods on PM2.5 Health Impact. Hao Yin, Linyu
Xu………………………………………………………………………………………………………….. 325
Impacts of Vehicle to Infrastructure Communication Technologies on Vehicle Emissions. Qing Li,
Fengxiang Qiao, Lei Yu ………………………………………………………………………………… 326
A GIS-Based Spatial Analysis of Air Pollution in Nanning. Bo Wei, Fengxiang Qiao, Zhihu Huang,
Juan Ma, Lei Yu …………………………………………………………………………………………. 333
Vehicle Emission Analysis at Restaurant Drive-Through Facilities with Different Configurations.
Keziah Hill, Mehdi Azimi, Fengxiang Qiao, and Lei Yu. …………………………………………… 339
Prediction of Pollutant Concentration through the Consolidation of Multiple. Air Dispersion Models
Using a Superensemble. Shoou-Yuh Chang and Frank Gronwald ………………………………. 345
Effects of Quarry Operation Processes to Air Quality in Istanbul Cebeci Zone According to PM10
Emissions, Kadir Alp, İsmail TORÖZ , Edip Avşar, Ezgi Erdoğan, Banu Özlem, İlker Akmırza… 346
Scenario Modeling as A Tool for Multi-Pollutant Policy Development in California. Joshua
Cunningham, Nicole Dolney…………………………………………………………………………… 353
The Use of Locally Manufactured Activated Carbon Filters for Indoor Air Quality Improvement.
Abdullah M. Al-Qahtani, Waleed H. Al- Rwaily, Jamal Al-Radaideh ………………………… 354
Transport of Pollutants
Source Apportionment of Selected Heavy Metals in Aerosol Samples Collected from Sebele,
Botswana. Alfred S. Likuku, Gilbert K. Gaboutloeloe and Khumoetsile B. Mmolawa………….. 355
Study on an Ozone Episode over the Pearl River Delta, China. Jin SHEN, Hao CHEN, XueSong
WANG, JinFeng LI, Wei LV, YuanHang ZHANG, Luan Yuan, Liuju ZHONG ………………….. 356
Waste Gas Control Techniques
Styrene Degradation by Biotrickling Filters with Single and Mixed Packings. Ailing Ren, Huanhuan
He, Bin Guo and Xi Lv…………………………………………………………………………………… 373
Treatment of Mixture of n-Hexane, Benzene, and Methanol in an Integrated Scheme of Cyclic
Adsorption/ Desorption Beds and Trickle Bed Air Biofilter. Abderrahman Zehraoui and George
A. Sorial…………………………………………………………………………………………………… 380
Removal of Chloroform as a Model Trihalomethane in the Presence of Co Metabolite and / or
Surfactant by Using Anaerobic Biotrickling Filter, Bineyam Mezgebe, George Sorial, E. Sahle
Demessie and Ashraf Aly Hassan. ……………………………………………………………………. 381
Air Pollutant Monitoring
Wrestling with Fenceline Fugitives: Nuisance Air Monitoring. Ben Bolton, John Siler, and Rick
Bolton……………………………………………………………………………………………………. 382
Characterization of PM2.5-bound Nitrated and Oxygenated PAHs in Diesel Exhaust Particles.
Meiling Hou, Jianjun LI, Wanglai Cen, Huaqiang Yin, Yangjun Wang ………………………… 383
Daily and Seasonal Variations of Volatile Organic Compounds and Carbonyls in the Atmosphere of
Monterrey, Mexico. H. Lizette Menchaca and Alberto Mendoza………………………………… 384
Characteristics of Greenhouse Gas Emission in the Yellow River Delta Wetland. Qingfeng Chen,
Junjian Ma, Hongyan Yang and Wenguo Dong…………………………………………………….. 385
viii
A Monitoring Study on Fine and Coarse Particulate Matter at Construction Sites. Harmonie A.
Hawley, James Miller, and Brian O’Dell. ………………………………………………………….. 386
2012 Air Quality in Alberta Oil Sands Community of Fort McKay versus Canadian Urban Locations.
Warren Kindzierski and Md. Aynul Bari. …………………………………………………………….. 392
Development of Vehicle Emission Database for Air Quality Analyses. Po-Hsien Kuo, Fengxiang
Qiao, Lei Yu ………………………………………………………………………………………………. 393
Vehicle Emission Estimation while Picking up Passengers at Airport Terminals. Larry Hill,
Fengxiang Qiao, Keziah Hill, Lei Yu …………………………………………………………………... 398
Effective Approaches for Public Communication of Air Quality Results from Two Environmental
Dredging Projects. Scott Manchester and Matt Traister …………………………………………….. 403
Hazardous Gas Biofiltration /

Catalysts for Reducing Emission
Methane Slip Emission Treatment by Pt/Pd/Al2O3 Washcoated Monolith with Spatial Concentration
Measurements. Gregory Bugosh, Vencon Easterling, and Michael Harold………………………. 404
Predicting SO2 Oxidation over a Pt/Al2O3 Diesel Oxidation Catalyst. Tayebeh Hamzehlouyan,
Chaitanya S. Sampara, and William S. Epling ……………………………………………………….. 405
Why Silver/Mesoporous Silica Catalyst is Unique for CO and HCHO Catalytic Oxidation
Elimination? Zhenping Qu, Dan Chen and Xiaodong Zhang…………………………………….. 406
Fuel Gas DeSOx, DeNOx, and Metal Removal
The SO2 Removal Method of a Sulfuric Acid Process Exhausts Gas. Jianjun LI, Huaqiang YIN, Xin
LI…………………………………………………………………………………………………………… 407
Air Pollution Prevention and Management
Charactering Air Pollutant Effects Caused by Extra Commuting Time due to Housing Price Factor.
Ling Liu, Fengxiang Qiao, Lei Yu ……………………………………………………………………… 408
Noise
Modelling of Road Traffic Noise during Journeys in Mumbai Metropolitan Region, India. Vishal
Konbattulwar, Saurav Jain, and Nagendra R. Velaga* …………………………………………….. 413
GLOBAL WARMING AND CLIMATE CHANGE
Global Warming and Its Impacts
Adaptation of Agricultural Sector to the Impacts of Climate Change in Saudi Arabia: Reallocation
of Irrigation Water among the Comparative Advantage Crops. Ahmed M. Alabdulkader; Fawzi
S. Awad; and Ahmed I. Al-Amoud …………………………………..………………………………….. 415
Adaptation of Field Crops to Climate Changes Impact. Tawfik M.M., Thalooth A.T., E. M. Abd El
Lateef, B. B. Mekki, Amany , A. Bahr and Magda , H. Mohamed ………………………………….. 424
Influence of ENSO on Rainfall, Streamflow and Vegetation in Pranhita Catchment, India. Rajashree
Vinod Bothale, Yashwant B. Katpatal …………………………………..…………………………… 425
Performance Comparison of Methods for Temporal Precipitation Downscaling in Urban Area: the
Kunming Case. Hua Bai, Siyu Zeng, Xin Dong, and Jining Chen ………………………………… 432
ix
Better To Save A MW Rather To Generate A MW. Mehboob Alam Khan, Asif Hussain Siddiqui,
Abdul Fawad …………………………………..…………………………………………………………. 438
Carbon Discharge Reduction
The Interactions of Rock with CO2 and Brine under CO2 Sequestration Conditions. Y. Soong, L.
Zhang, B. H. Howard, S. W. Hedges, R. Warzinski, R. Dilmore, D. J. Soeder, R. T. McClendon,
M. L. Gray, I. Haljasmaa and D. Crandall ………………………………………………………….. 439
Bioremediation and Biotransformation of CO2 Using Biocatalyst. Bhagat Chintan, Tank Shantilal K,
Bhasar Sunilkumar, Dudhagara Pravin ………………………………………………………………. 440
Space Distribution of Carbon Emissions in China. Mi Hong, Zhang Tiantian, Zhou Wei …………. 445
x
INTRODUCTION
The Seventh International Conference on Environmental Science and Technology 2014 was held in
Houston, Texas, USA, June 9-13, 2014. The Program included 16 sections, containing 60 sessions with
approximately 600 platform and poster presentations. This conference series strives to provide a platform
for an extremely diverse group of environmental topics for engineers and scientists from around the world.
Authors of the presentations accepted for the program were invited to submit their papers to the
Conference Organizing Committee. More than 120 papers were received and then reviewed by the editors,
session chairs, and the members of the Scientific/Technical Committee of the conference. Those papers and
abstracts accepted for publication were assembled into two volumes.
Sections are arranged basically according to their order listed in the original program except the
sessions entitled Land (Soil, Waste Solid) Pollution and Remediation. This exception was made to balance
the length of the two volumes. The conference also consisted of having a plenary session with four speakers
from different universities at the United States and other countries.
Environmental Science and Technology 2014 (Volome 1) contains the following sections:
• Plenary Presentation
• Water Pollution and Water Quality Control
• Air Pollution and Air Quality Control
• Global Warming and Climate Change
Sections included in Environmental Science and Technology 2014 (Volume 2) are as follows:
• Land (Soil, Waste Solid) Pollution and Remediation
• Ecosystem Assessment and Restoration
• Bio-Assessment and Toxicology
• Wetlands and Sediments
• Metals (Distribution, Removal, Remediation, Speciation, and Phytoremediation)
• Chlorinated and Other Persistent Organic Compounds
• Modeling
• GIS for Environmental Assessment, Database, and Remote Sensing Applications
• Environmental Analysis and Measurements
• Society and the Environment
• Environmental Planning and Management
1
• Renewable Energy Development

We would like to especially thank the session chairs who were instrumental in the success of
the conference. The Conference was sponsored and organized by the American Academy of
Sciences, with financial contributions from the co-sponsors and supporting organizations.
The papers in these proceedings represent the authors’ results and opinions. No sponsors,
cosponsors, participating organizations or editors should be construed as endorsing any specific
contents or conclusions in the proceedings.
George A. Sorial, Ph.D.
University of Cincinnati
Jihua Hong, Ph. D.
American Academy of Sciences
2
PLENARY PRESENTATION
3
AEROBIC SLUDGE GRANULATION:

CURRENT PERSPECTIVES, ADVANCES AND THE WAY FORWARD
Kuan-Yeow Show1, Duu-Jong Lee2, Yan Yuegen3, and Joo-Hwa Tay4

1
Puritek Environmental Technology Institute, Nanjing, China
2
National Taiwan University, Taipei, Taiwan
3
Puritek (Nanjing) Co., Ltd, Nanjing, China
4
University of Calgary, Calgary, Alberta, Canada
ABSTRACT: Aerobic granulation was developed as a novel approach to agglomerating loose biomass into
dense and compact biogranules. Compared with conventional biological flocs, aerobic granules are
characterized by well defined shape and compact build up, superior biomass retention, enhanced microbial
functions, and resilient to toxicity and shock loading. Their unique features lead to a promising prospect in
overcoming the problem of biomass washout often encountered in activated sludge processes, thus offering
a new dimension for wastewater treatment. This paper provides a review of current development in aerobic
granulation. Factors affecting granulation such as seed sludge, type of substrate and organic loading, and
mode of reactor operation are delineated. Maintaining granule structural stability is a major challenge of
aerobic granulation. This paper also outlines approaches to addressing granule disintegration and stability
for practical applications of aerobic granulation. Challenges and future work of aerobic granulation are also
discussed.
INTRODUCTION
Granulation is a self-immobilization phenomenon in which fluffy biological solids agglomerate as
dense and compact granular sludge under controlled conditions. Aerobic granules possess superior
characteristics such as distinct shape and structure, high settling velocities and biomass accumulation, and
its ability to withstand high organic loadings (Tay et al., 2001). Because of its unique features, application
of aerobic granulation is perceived as one of the promising technologies since it was developed in the 90s.
Aerobic granulation has been investigated in various laboratory-scale bioreactors (Ho et al., 2010).
Extensive work on granule characterization, factors affecting granulation, response of granules to various
environmental and operating conditions, and granulation mechanisms has been documented. There is,
however, limited study of pilot- or full-scale aerobic granular sludge systems. For practical industrial
applications, continuous-flow reactors are preferred over sequential batch reactors (SBRs) for lower
installation cost as well as simpler reactor operation, maintenance and control. However, it appears that
maintaining granule of adequate structural stability poses a major challenge for full-scale operation. A study
had revealed that aerobic granules developed in a continuous-flow reactor would disintegrate faster than
those in a sequencing batch reactor (SBR) (Chen et al., 2009). On the other hand, it appeared that stable
granule structure can only be sustained for a limited time in an SBR (Li et al., 2007).
This paper presents a review on recent development in aerobic granulation. Factors affecting
granulation and approaches to addressing granule stability are discussed. Challenges and future work of
aerobic granulation are also outlined.
FACTORS AFFECTING GRANULATION
4
Seed Sludge. Activated sludge has been used as seed in most aerobic granulation studies. Aerobic granules
can also be cultivated by seeding completely autotrophic nitrifying microorganisms in SBR (Zhang et al.,
2010). Different microbial community in seed sludge exhibited different agglomeration abilities arising
from variation of physico-chemical characteristics (Bos et al., 1999) which can be associated with microbial
strain, hydrophilic or hydrophobic nature, or it can be a result of certain extracellular polymeric substances
(EPS) activities (Martienssen et al., 2001). The greater number of hydrophobic microbial community in the
seed could result in faster aerobic granulation with excellent settleability (Wilen et al., 2007).
Single culture aerobic granules using separate isolates from a phenol-fed aerobic granule had been
successfully cultivated (Adav et al., 2008a). The isolates presented high phenol-degrading and high auto-
aggregation capabilities. Conversely, isolates with low auto-aggregation capability failed to develop into
single-culture granules. Aerobic granules were cultivated using single culture Corynebacerium sp. DJ1 with
high auto-flocculating and high phenol-degrading capabilities (Ho et al., 2010). The cultivated granules
were subsequently used to degrade phenol at concentrations greater than 2500 mgl-1 with good efficiency.
Substrate and Loading. Various types of substrate were used to cultivate aerobic granules. These included
glucose, acetate, phenol, starch, ethanol, molasses, sucrose and other synthetic wastewaters (Adav and Lee,
2008). Inorganic carbon source dominated by nitrifying bacteria was used to cultivate aerobic granules (Tay
et al., 2002; Tsuneda et al., 2003). Granules were cultivated from activated sludge using nitrobenzene as
sole carbon and nitrogen sources (Wang and Zhou, 2010). The type of substrate dictates the diversity and
dominancy of the bacterial species, granule surface, and structure (Liu and Tay, 2004). Aerobic granules
have been cultivated with OLRs ranging from 2.5 to 15.0 kg chemical oxygen demand (COD) m-3d-1 (Moy
et al., 2002; Liu et al., 2003). High organic loading enhanced biogas production causing higher upflow
liquid velocity serving as a selection pressure for granulation (Hulshoff Pol et al., 1988). It was reported
that optimal OLR for granulation was 2.52 kg COD m-3d-1 (Kim et al., 2008). While it had been found that
granulation cannot be accomplished at OLRs less than 2 kg m-3d-1 (Tay et al., 2004), granules were
successfully cultivated at OLRs of 1.05–1.68 kg COD m-3d-1 (Wang et al., 2009) over a cultivation period
of a year. A long granule cultivation time of over 400 days using SBR fed with municipal wastewater with
low OLR was recorded (Liu et al., 2010).
Mode of Operation. It appears that aerobic granules had been successfully cultivated only in sequencing
batch reactor (SBR). Settling time and exchange ratio of liquid volumes at the end of each SBR cycle serve
as a selection pressure to remove non-granular biomass. Short cycle time results in short hydraulic retention
time (HRT) favoring rapid granulation (Liu et al., 2007). Granules cultivated at 1.5 h cycle time showed
the largest size, while those cultivated at 4h cycle exhibited the densest structure. Short settling time washes
away poorly settling solids and retains only well settling granules (Hu et al., 2005). A shift in microbial
community for granules cultivated at different settling times was noted (Adav et al., 2009). Short settling
time leads to washout of non-flocculated strains, and the flocculated strains can be enriched in granules
without competition from non-flocculated strains being washout. It had been hypothesized that periodic
starvation in SBR increases cell surface hydrophobicity, which in turn facilitates aerobic granulation (Liu
et al., 2004). Conversely, starvation may be detrimental to surface hydrophobicity (Castellanos et al., 2000)
while starvation cycle is not a prerequisite for aerobic granulation (Liu et al., 2007; Liu and Tay, 2008).
Environmental Factors. It appears that dissolved oxygen (DO) in the liquid is not a dictating factor for
aerobic granulation, as granules can be developed at DO levels as low as 0.7-1.0 mgl-1 (Peng et al., 1999)
to as high as 2–6 mgl−1 (Tsuneda et al., 2003). While most aerobic granulation work was carried out at 20–
25 ºC, granulation was reported in a SBR operated at 8ºC. The granules cultivated were in irregular shape
with excessive growth of filamentous microbes, causing severe biomass washout and unstable operation
(de Kreuk et al., 2005). The pH of reactor liquid has a profound impact on the microbial growth. Fungi
would become prolific at low pH and may play a role in the initial granulation (Williams and Reyes, 2006).
5
It has been observed that granulation at a pH of 4.0 was dominated by fungus with granule size approaching
as large as 7 mm. At a higher pH of 8.0, granulation was dominated by bacteria with granule size reduced
to 4.8 mm (Yang et al., 2008).
GRANULE STABILITY
Deterioration in granule stability over time is a common issue of aerobic granulation for full-scale
operation. Studies have shown that aerobic granules would disintegrate after prolonged operation (Lee et
al., 2010). Overgrowth of filamentous bacteria can lead to fluffy and loose granules that are unstable and
can be easily washed out of the reactor. Liu and Liu (2006) showed that overgrowth of filamentous
microorganisms can lead to reactor failure when the DO was low. It has been shown that strong shear force
caused by intense aeration would also provide sufficient oxygen to suppress filament growth (Adav et al.,
2007).
Zheng et al. (2006) noted that at a high OLR of 6.0 kg COD m−3 d−1, granules grew larger with
remarkable filamentous growth but gradually deteriorate in stability. Granules became unstable at high
OLRs of up to 8 kg/m3-d (Tay et al., 2004). When granules grow oversize to such an extent that its radius
is larger than the oxygen transfer limit, anaerobic conditions could develop within the granule. Inherent
anaerobic metabolites such as fatty acids and biogas can weaken the granule internal structure resulting in
disintegration of granules (Zheng et al., 2006). It was reported that rupture of mature granules is attributable
to clogging of pores and channels in granules, hence hindering nutrients intake by the microbes (Lemaire
et al., 2008). Moreover, mineral complexes associated to granule EPS matrix would dissolved at low pHs
causing damages to the granule. It was observed that granule became unstable during an extended idling
period under high storage temperature (Tay et al., 2004). A high storage temperature in the absence of
substrate supply can lead to endogenous respiration and a rapid disintegration of the granules.
It has been reported that EPS constituting proteins, polysaccharides, humic acids, and lipids
secreted by bacteria help to initiate aerobic granulation process (Liu et al., 2004). It was hypothesized that
EPS bridge bacterial cells and other particulates into an aggregate forming the precursor of a granule (Liu
et al., 2004). Non-soluble beta-polysaccharides form the outer shell of aerobic granules to withstand shear
(Wang et al., 2005). On the contrary, a non-cellular protein core in aerobic granules provides mechanical
stability to the granule (Zhang et al., 2007). Granule structure is supported by a network composed
principally of β-polysaccharides as the backbone for embedment of proteins, lipids, α-polysaccharides, and
cells, and hydrolysis of β-polysaccharides caused disintegration (Zhang et al., 2007). In essence,
enrichment of certain EPS enhanced microbial granulation and granule stability.
CHALLENGES AND FUTURE WORK

Maintaining granule with adequate structural integrity is one major challenge that hinders practical
application of aerobic granulation. Current bottleneck of aerobic granulation development highlights the
need for further research in granule stability for full-scale operation. There is a need to explore ways or
techniques in developing granules with sustainable integrity.
A few strategies were proposed to enhance granule stability for practical operation. It has been
established that applying an appropriate OLR is essential to control granule stability (Li et al., 2010). Li et
al. (2010) proposed that operating at high OLRs (>2.0 kg COD m-3d-1) is an effective strategy to control
fungal bloom and maintain granule stability. Conversely, granules subject to high OLRs may disintegrate
(Moy et al., 2002; Zheng et al., 2006; Liu and Liu, 2006; Adav et al., 2008b).
Overgrowth of filamentous microorganisms could result in granule disintegration when the DO is
inadequate especially operating at high OLRs (Liu and Liu, 2006). Granules may grow oversize at high
OLRs, and DO may not be diffused into the internal matrix due to limitation of mass transfer. This would
create an anaerobic environment beyond the DO diffusion limit extending into the granule core (Zheng et
al., 2006). The subsequent anaerobic metabolites such as volatile fatty acids and biogas including the toxic
hydrogen sulfide may damage the granule structure leading to disintegration. Instead of allowing fast-
6
growing filamentous microbes to thrive in the culture, promoting slow-growing organisms such as
phosphate or glycogen accumulating bacteria could enhance granule stability at low oxygen saturation
(20%) (de Kreuk et al., 2004). Other slow-growing microbes such as the denitrifiers would thrive with
nitrate or nitrite supplement, which could penetrate into the granule core. In essence, granule structure can
be strengthened by promoting heterotrophic growth within the granule.
Studies revealed that addition of Ca2+ ions accelerated aerobic granulation (Jiang et al., 2003), and
bacterial alginate reacted with calcium ions principally contributed to stability of aerobic granules (Lin et
al., 2008). Accelerated formation of granules with larger size and denser interior was reported in reactor
dosed with 10 mgl-1 Mg2+ (Li et al., 2009) and 100 mg Ca2+ l-1 in the feed (Jiang et al., 2003).
A technological know-how for cultivating granules of adequate structural stability for storage has
been described for the first time (Lee et al., (2010). It appears that the drying did not cause notable impact
on the granules in terms of morphology and functionality. The granules were recuperated after being dried
for 21 days. It was reported that COD removal of the dried granules upon recuperation was not affected by
the drying. The removal efficiency was comparable with active fresh granules without subjecting to drying.
The finding may suggest the use of drying as a novel treatment of granule for storage purpose. The novel
drying technique of aerobic granules would allow convenient storage and handling of granules for use as
inoculums for rapid startup and as granule supplement to enhance treatment. Further research is needed to
ascertain other impact of the drying such as settleability, density, surface hydrophobicity, specific oxygen
uptake, strength and ECP content of granule.
To further explore the potential of aerobic granulation, the following studies are proposed:
(1) Enrichment and distribution of certain EPS components in promoting granulation and maintaining
granule stability. Using CLSM coupled with specific florochromes, spatial distribution of proteins, α-,
β-polysaccharides, and lipids within the granule can be examined for a better understanding on granule
internal structure and stability.
(2) As most research work on aerobic granulation has been based on SBR sequencing operating mode,
aerobic granulation in continuous operating mode need to be established. Continuous operation of
reactor is advantageous over batch or sequencing mode for efficient full scale operation.
(3) Coupling granulation technology with other treatment systems, for example MBR to complement
benefits from both processes. Cultivation of aerobic granules with genetically engineered microbial
species with multiple targeted genes for removing multiple toxicants by single transformed bacterium.
Treatment capacities of aerobic granulation system can be easily adjusted to accommodate varying
loading rates, wastewater composition, and treatment goals by bioaugmentation with genetically
engineered granules.
(4) Use of drying as a treatment of granule needs to be explored to ascertain stability of aerobic granules
and other impact of the treatment. Novel treatment of granules would allow convenient storage and
handling for use as inoculums and as granule supplement to enhance treatment of existing systems.
CONCLUSIONS
Aerobic granulation evolves as a promising technique for high strength and/or toxic wastewater
treatment. Stability of aerobic granules for practical applications remains a major challenge that has yet to
be resolved. There is a need to explore ways or techniques in developing granules with sustainable integrity.
Strategies for generating a more stable granule including selection of slow-growing microorganisms,
inhibiting the activity of anaerobic bacteria, along with strengthening the core of the granule were
heartening, while findings of granule cultivated with durable stability in a continuous-flow reactor, and
granule storage with drying technique are encouraging. The novel drying technique of aerobic granules
would allow convenient storage and handling of granules for use as inoculums and as granule supplement.
Further research is needed to ascertain other impact of the drying, and to ascertain stability of granules in
pilot- and full-scale long-term operation and storage.
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under different feeding alkalinity and pH conditions.” Process Biochem 43:8–14.
Zhang, L. L., X. X. Feng, N. W. Zhu and J. M. Chen. 2007. “Role of extracellular protein in the formation
and stability of aerobic granules.” Enzymes Microb Technol 41:551–557.
Zhang, Z. J., W. W. Wu and J. L. Wang. 2010. “Granulation of completely autotrophic nitrifying sludge in
sequencing batch reactor.” Huanjing Kexue 31:140–146.
Zheng, Y. M., H. Q. Yu, S. J. Liu and X. Z. Liu. 2006. “Formation and instability of aerobic granules under
high organic loading conditions.” Chemosphere 63:1791-1800.
9
HYDRAULIC FRACTURING, WATER CONSERVATION AND ENVIRONMENTAL

PROTECTION
Davis L. Ford
(University of Texas Austin, Davis L. Ford & Associates, Austin, Texas 78746, USA)
The discovery of enormous amounts of energy reserves, mostly proven, which are in “tight” shale and
sandstone formations, both oil and gas, is transforming the United States to be totally independent of foreign
fossil energy. Our import energy has dropped from over 60% to less than 30% in the past few years,
dramatically enhancing our GDP. Recently, the United States has passed Russia and Saudi Arabia in fossil
fuel production. Currently, over 90% of U.S. energy demand depends on fossil fuel. Subsidies for “green
energy” are now under review. While wind and solar energy are increasing in selected areas, biofuels and
particularly ethanol, because of their huge water demand, are becoming less popular and cost effective.
Natural gas is the least cost option for new power generation in most areas, and has a minimal
greenhouse gas footprint.
The fundamentals of this enhanced oil and gas extraction will be outlined in this presentation, with
major emphasis on the associated water issues. It is imperative that the use of fresh water in the fracking
process be reduced or eliminated through conservation and cost effective reuse of flowback and produced
water generated in this process. The reuse technologies such as reverse osmosis, electrocoagulation, and
related desal technologies generally are in place, but reduced costs per volume is essential in the overall
enhanced oil and gas economics as well as the preservation of fresh water sources for human and crop
irrigation uses. Although the fracking process normally occurs in depths of 8,000 feet or more below the
surface, drinking water quality can be adversely affected by poor surface casing and/or imperfect
cementing, as well as surface contamination from tank storage of fuel and trucking activities (spills and
leaks)
10
GLOBAL CLIMATE CHANGE -THE QUANTIFIABLE SUSTAINABILITY CHALLENGE
Frank Princiotta
(USEPA-National Risk Management Research Laboratory, Durham, NC 27711, USA)
Humanity is on an unsustainable trajectory; developmental pressures, spawned by an increasing demand

for resource intensive goods, foods and services, are altering the planet in ways that threaten the long-term
well being of humans and other species. The presentation provides an updated analysis of the emission
reductions needed to constrain this warming, and the energy technologies needed to achieve these emission
reductions. Transparent modeling tools and the most recent literature are used, to quantify the challenge
posed by climate change and potential technological remedies. The presentation examines forces driving
CO2 emissions, how different emission trajectories could affect warming this century, a summary of
mitigation options, and R&D priorities. Major focus is on the power generation and mobile source sectors
both globally & for the United States, assuming a target of 50% Carbon Dioxide (CO2) emission reductions
(from 2007) by 2050. The current generation of energy generation and end use technologies are capable of
achieving less than half of the emission reduction needed for a serious CO2 mitigation program. New
technologies will have to be developed and deployed at a rapid rate, especially for the power generation
and transportation sectors. A discussion of the adequacy of the current global efforts to develop &
demonstrate such technologies is also discussed.
11
Development of a PV-Powered Electrochemical Wastewater Treatment System
Michael R. Hoffmann, Kangwoo Cho, Clement Cid, and Qu Yan

(Environmental Science & Engineering, California Institute of Technology,
Pasadena, California 91125, USA)
We have developed a transportable prototype wastewater treatment system designed for the treatment of
raw domestic wastewater, human urine, human feces, and synthetic human waste analogues. After several
hours of PV-powered electrochemical treatment, the turbid, black-water influent can be clarified with the
elimination of the suspended particles along with the reduction or total elimination of the chemical oxygen
demand (COD), total enteric coliform disinfection via in situ reactive chlorine species generation, and the
elimination of measurable protein after 3 to 4 hours of PV-powered treatment. Our advanced prototype
incorporates additional features such as a residual sludge handling unit, a hydrogen purification and filter
system, a closed water reuse system, and microbial fuels cells. We have packaged our second-generation
prototypes into modified shipping containers that are ready for field-testing in remote locations that lack
traditional urban infrastructure. The electrochemical treatment units employ bismuth oxide doped titanium
dioxide (BiOx/TiO2) electrode arrays with underlying layers of sequential nano-particulate coatings of IrO2,
Ta2O5, SnO2, and Bi2O3. A robust kinetic model, which assumes a chemical reaction limited regime, is
used to investigate the role of various redox reactions mediated by Cl- ion oxidation to chlorine and by
hydroxyl radical generated at the electrode surfaces. Under current densities (J) higher than 200 A m–2, the
oxidative elimination of the chemical oxygen demand (COD) and ammonium ion can be modeled using
experimentally-determined pseudo first-order rate constants and current efficiencies In combination with a
microbial fuel cell pretreatment step, the human urine and feces is processed. The COD, protein, and color
are eliminated within 4 hours of continuous treatment. The treated water is then recycled for reuse.
In the laboratory, we investigated the electrochemical treatment of real domestic wastewater
coupled with simultaneous production of molecular H2 as useful by-product. The electrolysis cells employ
multi-layer semiconductor anodes with electro-active bismuth-doped TiO2 functionalities and stainless steel
cathodes. DC-powered Laboratory-scale electrolysis experiments were performed under static anodic
potentials (+2.2 or +3.0 V NHE) using domestic wastewater samples, with added chloride ion in variable
concentrations. A 95% reduction in chemical oxygen demand (COD) and ammonium ion were achieved
within 6 hours. In addition, we experimentally determined a decreasing overall reactivity of reactive
chlorine species towards COD with an increasing chloride ion concentration under chlorine radicals (Cl∙,
Cl2–∙) generation at +3.0 V NHE. The current efficiency for COD removal was 12% with the lowest specific
energy consumption of 96 kWh kgCOD–1 at the cell voltage of near 4 V in 50 mM chloride. The current
efficiency and energy efficiency for H2 generation were calculated to range from 34 to 84% and 14 to 26%,
respectively. The hydrogen comprised 35 to 60% by volume of evolved gases. The efficacy of our
electrolysis cell was further demonstrated by a 20 L prototype reactor totally powered by a photovoltaic
(PV) panel, which was shown to eliminate COD and total coliform bacteria in less than 4 hours of treatment.
12
EVOLVING CONCEPTUAL MODEL OF NATURAL ATTENUATION

OF GROUNDWATER PLUMES
Charles Newell and David T. Adamson

(GSI Environmental Inc., Houston, Texas, USA)
Natural attenuation of contaminants that comprise groundwater plumes has evolved considerably since its
origin in the 1980s. Up to 1994, there natural attenuation was described using terms such as “natural
assimilation,” “natural biodegradation,” “intrinsic remediation,” and largely focused on aerobic
biodegradation of hydrocarbon compounds such as benzene and other petroleum-related aromatics. Then
in 1994 the U.S. Air Force issued a ground-breaking Draft Protocol for evaluating natural attenuation of
fuel hydrocarbons, and in 1998 a Technical Protocol for Evaluating Natural Attenuation of Chlorinated
Solvents in Ground Water was issued by the US Environmental Protection Agency. Both of these high-
utilized, highly-cited technical protocols had two things in common:
• Recommended use of up to three lines of evidence: i) Documented loss of contaminants at the
field scale, ii) Contaminant and geochemical analytical data, and ii) Direct microbiological evidence;
• Emphasis on a few key naturally occurring biodegradation reactions in the plume downgradient of
the source (direct oxidation reaction with naturally occurring electron receptors for fuel hydrocarbons,
reductive dechlorination with naturally occurring electron donors for chlorinated solvents.
By the mid-2000s these protocols had been applied extensively around the world, and formed the basis for
managing contaminated groundwater plumes at hundreds of sites. In the past 10 years, however, there has
been important new thinking about why, how, and where MNA is applied. Key new developments include:
• Application to new contaminants such as fuel oxygenates, metals, radionuclides, dioxane and other
emerging contaminants, and to new settings such as LNAPL and chlorinated solvent source zones;
• Better appreciation of new attenuation processes including biogeochemical transformation of
chlorinated solvents, natural source zone depletion;
• Revisions to our understanding and reliance on mechanical dispersion, and a new understanding of
when DNAPL is present in chlorinated solvent source zones and when matrix diffusion alone may be
sustaining plumes;
• New measurement tools such as more powerful compound specific isotope analyses and molecular
biological tools;
• New tools for evaluating MNA, including new analytical models such as U.S. EPA’s REMChlor
model, mass flux based dilution calculations, and matrix diffusion models;
• A growing recognition that long term and lengthy restoration processes may be inevitable (Leeson
et al., 2013; ITRC, 2011) and that “Transition Assessments” may be needed to determine when to transition
from active treatment to long-term, more passive treatment such as MNA (National Research Council,
2012).
These developments paint a picture where the useful, but narrow original conceptual model of
MNA (a single biodegradation reaction in the groundwater plume is evaluated) is being replaced by a
broader, more powerful MNA conceptual model that includes dilution at exposure points, long-term storage
in low permeability zones, and a diverse assortment of degradation reactions that is applied to a wide variety
of contaminants, problems, and management roles.
13
WATER POLLUTION
AND
WATER QUALITY CONTROL
14
NEW FINDINGS ON SOURCES OF ORTHOPHOSPHATE IN UPPER MALIBU CREEK

WATERSHED: A GEOLOGIC SOURCE PRIMARILY?
Barry J. Hibbs, Kathleen Kuepper, and Yola Wong K

(California State University, Los Angeles, CA, USA)
Recent studies have suggested dissolution of geologic strata by percolating groundwater is the most
important source of orthophosphate during dry weather flow conditions (2 weeks after any rain event) in
Upper Malibu Creek Watershed of Southern California. The earliest concepts on nutrient levels in the
watershed, which were somewhat anecdotal, pointed to urban runoff as the principal source of
orthophosphate in residential and commercially developed parts of the watershed. More recently, it has
been established that baseflow is a principal source of dry weather stream flow in many parts of the
watershed. The observation that creeks are fed to a significant extent by groundwater, and that
orthophosphate is elevated in the creeks along the upper watershed corridor (where Monterey/Modelo
Miocene marine strata are the main source rocks feeding baseflow into the creeks and streams) led some
investigators to conclude that the phospatic member of Monterey/Modelo strata is the source of elevated
orthophosphate. Concentrations in surface water in Upper Malibu Creek Watershed are typically in the
range of 0.4 to 1.0 mg/L dissolved orthophosphate. To test the hypothesis of geologic origins of phosphate
in the upper watershed, we undertook extensive studies to evaluate geologic and other sources. Our studies
included extensive sampling of stream water, shallow groundwater, dry weather urban runoff, and
hyporheic zone water. Water samples were analyzed for nutrients, standard inorganic constituents, and
stables isotopes of oxygen, hydrogen, sulfur, and nitrogen. Our findings indicate that groundwater sourced
directly from Monterey/Modelo strata contains less than 0.3 mg/L dissolved orthophosphate in more than
95% of groundwater samples, while urban runoff sourced from both tap and reclaimed water sources
contains 0.2 to 9 mg/L dissolved orthophosphate. Mass balance analysis demonstrably points to the fraction
of urban runoff (10 to 40%) to be an additive source of orthophosphate that at least doubles the
concentration in the developed parts of the watershed. Orthophosphate loading from dry weather urban
runoff blends with baseflow and undergoes complex processes in stream riffles and pools, and especially
within the hyporheic zone, to both remove and release orthophosphate into pore water and stream water.
The hyporheic zone processes seem to favor release of sorbed orthophosphate due to abundant organic
matter that creates semi-oxic redox conditions and reactions in interstitial spaces to mobilize
orthophosphate while competing for clay sorption sites. Our studies indicate that hyporheic zone processes
and urban runoff are more important source of orthophosphate than loading from baseflow from the
Monterey/Modelo strata proper.
15
EVALUATION ON ECO-SECURITY OF WATER RESOURCES AND REGULATING &

CONTROL MODE OF ENVIRONMENTAL PLANNING FOR LAKE BASIN --- A CASE OF
TAPING LAKE, ANHUI PROVINCE, CHINA
Xiangrong Wang
(Fudan University, Shanghai 200433, China)
Under the guidance of 'source-flow-sink' of ecological theory, the eco-security evaluation and regulating &
control mode for environmental planning of water resource in Lake basin were carried out in this paper
from the research of water system, wetland and vegetation system, farmland system, point and non-point
source pollution, geological disaster and ecological sensitivity using the coupling evaluation methodology
of EF-ES model and 3S (RS, GIS and GPS) techniques within 1770 km2 of Taiping Lake Basin, Anhui
Province, China.
The SWOT conditions of main resource and eco-environmental issues were identified for the study
of environmental capacity, eco-vulnerability and carrying capacity as well as ecosystem service function in
both lake body and lakeshore area. The environmental planning and management strategies of regulating
and control mode for water resource were put forward. This paper aims to study the methodology of eco-
security evolution and regulating & control mode of environmental protection planning for water resources
of whole lake basin, and explore for a benign circulation mechanism of economico- socio development and
environmental protection by taking Taiping Lake Basin as an example.
16
KEY ISSUES FOR RIVER REGULATION: AN ILLUSTRATION FROM DIANCHI

INFLOWING RIVERS IN CHINA
Ke Huang, JinHua Li, ZhuJing Jin, FengLe Yang, BaoXue Zhou

(School of Environmental Science and Engineering, Shanghai Jiao Tong University, No. 800 Dongchuan
Rd, Shanghai, China)
An effective approach for river regulation (RR) should be seen as a chance for development and
improvement of social and environmental conditions in surrounding areas. However, there
is currently no good way to control severe polluted rivers, especially to those in developing areas with large
population and low technological level. This paper tried to provide a useful guideline for other polluted
rivers regulation. In the context, three key issues for RR based on the regulation work of eutrophicated
Dianchi inflowing rivers (DIRs) were illustrated. The first key issue is execution of river management,
which was the most important for the area with low productivity. An effective responsibility system for the
leaders in charge of the DIRs is necessary to improve inefficient execution. Furthermore, another key issue
is to raise sufficient funds by strengthening market operation, thus introducing many financing channels for
engineering-based treatment. As the third key issue, comprehensive engineering including ecological
engineering also plays a very important role in pollution reduction and ecological remediation. After more
than six years of practicing in DIRs, related regulation work gets better results. Ecology environment of
DIRs has been improved obviously; the amount of pollutants from the DIRs to the DL decreased by 10%,
and the comprehensive pollution index of major DIRs decreased by 56%.
17
TRACE ELEMENT MOBILIZATION BY OXIDATION VIA ANTHROPOGENIC NITRATE IN

SOUTHERN CALIFORNIA WATERSHED
Yola Wong K and Dr. Barry Hibbs

(California State University, Los Angeles, CA, USA)
A comparative study of two creeks (having similar land use practices and geology) in Malibu Creek
Watershed in Southern California investigated the variability of nitrate (NO3--N) and toxic trace element
(selenium, Se) concentrations. The study area’s geological framework is unique, containing selenium
enriched strata facilitating geochemical reactions resulting in possible selenium oxidation and
mobilization in shallow groundwater that feeds into the creeks as baseflow. Previous studies demonstrated
a positive correlation of nitrate to selenium in the shallow groundwater and surface water of the creeks,
creating toxicity concerns to terrestrial aquatic species. One major tributary, Las Virgenes Creek, has nitrate
concentrations of 2 to 8 mg/L NO3--N and 10 to 50 ug/L dissolved Se, exceeding the MCLs for freshwater
species. The neighboring tributary, Medea Creek, has generally low nitrate concentrations < 1 mg/L NO3--
N, and does not have high oxidizing potential for selenium, resulting in less than 5 to 10 ug/L dissolved Se
in surface water and groundwater. These conditions apply during normal and dry years. Wet weather and
dry weather impacts the Malibu Creek watershed water quality concentrations. In very wet years, the
groundwater baseflow is so much higher that there appears to be temporarily very high selenium due
to recent recharge waters having very high dissolved oxygen leading to rapid oxidation of selenium in
rocks. In addition, water tables rise during extremely wet years into strata that are normally not saturated,
facilitating leaching of selenium directly into groundwater. In dry weather, dissolved oxygen is consumed
quickly because of the more sluggish groundwater flow regime that exists. There is limited oxidation
potential, except where anthropogenic nitrate is high in particular creeks. We hypothesize that selenium is
oxidized by elevated nitrate in shallow groundwater flowing through Monterey/Modelo formation adjacent
to Las Virgenes Creek, the only creek in Malibu Creek Watershed that is known for relatively high
nitrate. Shallow groundwater sampling of springs and seeps that flow into Medea Creek and Las Virgenes
Creek feasibly confirms our hypothesis through water quality testing. Analysis of hydrogen and oxygen
stable isotopes, nitrate isotopes, selenium, and other redox-sensitive species in surface water and
groundwater demonstrate creek characteristics, sources of water feeding into the
creeks, anthropogenic source(s) of nitrate and selenium concentrations in the watershed. Laboratory batch
studies are underway to determine the efficacy of nitrate oxidizing selenium contained in Monterey/Modelo
strata. These hydrogeological investigations in can assist water agencies improve water quality and the
Malibu Creek Watershed habitat for aquatic species.
18
SUSTAINABLE OR GREEN WATER MANAGEMENT PRACTICES BY SOUTH AFRICAN

MINING COMPANIES
Mbofho Stanley Liphadzi1 & Andre Vermaak2

(1. Water Research Commission, Private Bag X03, Gezina, 0031, South Africa; 2. School of Business and
Leadership, University of South Africa, Midrand, Johannesburg, South Africa)
Sustainable and green water management practices are aimed at facilitating environmental, social and
economic performance of the company. The assumption is that there is no business or company that can
attain long term growth and sustainability if it degrades the environment, violate human rights, or fails to
make profit. However, green practices are mostly focused on promoting environmental sustainability as a
platform for use to enhance social and economic sustainable performances. Sustainable or green water
management practices adopted by the mining industry includes those prescribed by the Global Reporting
Initiatives (GRI) and the International Council on Mining and Metals (ICMM) geared towards addressing
Water Use (reduce use, recycle &reuse), Pollution Reduction and Prevention, Reclamation &
Rehabilitation, and Planning. The objectives of the study were to investigate which sustainable or green
water management practices are used by the selected mining companies; to identify factors (or main drivers)
that determine the kind of water management practices that the selected mining companies use in mining
operations; to determine if currently used water management practices of the mining company are
sustainable / green, and to identify gaps or areas that mining companies can improve on to enhance their
environmental sustainability. Mining companies with activities associated with toxic mine water production
were identified and included in the study. While the study showed that a suit of sustainable water
management initiatives are used by the mines, there are still more strategic action needed for the mining
sector to be sustainable.
19
CRUDE PALM OIL PRODUCTION: ENVIRONMENTAL IMPACTS ASSESSMENT OF

FRESHWATER CONSUMPTION USING LCA APPROACH
Zainura Zainon Noor, Noor Salehan M. Sabli and Che Hafizan Che Ahmad
(Universiti Teknologi Malaysia, Skudai, Johor, MALAYSIA)
Freshwater use and its consumption have emerged as areas of high environmental concern. The problems
surrounding the management of this vital resource have stimulated public awareness, especially in the last
decade. However, water use and related impacts are still widely excluded from Life Cycle Assessment
(LCA) methodologies, which aim at measuring and assessing the environmentally relevant emissions and
resources consumed, over the entire life cycle of a product or service: the supply chain, the product
assembly, the use and disposal phase or recycling (ISO 14044). LCA is increasingly applied and required
by industry, authorities and consumers to make sustainability decisions. One main reason of neglecting
water has been the absence of comprehensive impact assessment methods associated with freshwater use.
The Malaysian oil palm industry is a very important industry since it contributes immensely to the nation’s
economy. The industry is asked again and again to prove the sustainability of their products. Sustainability
is no longer an option because it will be the primary driver of economic development in the long-term.
Sustainability has to be part of the oil palm industry’s business strategy. Just as how carbon footprint or
GHG emissions are playing such an important role in the oil palm industry, the next thing the world is
moving into is water footprint. In view of the imminent need for the oil palm industry to be accountable for
its water consumption, it is very crucial to first quantify the water footprint of the industry and identify
areas of high water intensity despite the fact that Malaysia is n. The next step will be to reduce the water
consumption as much as possible. In this manner, the oil palm industry will remain competitive and
sustainable in the global market. The main objectives of the study are to identify the areas of high water
consumption and the potential environmental impacts associated with them. This study embarked on a
cradle-to-gate water footprint of the production of crude palm oil (CPO). It was found that milling process
consumed the highest amount of water and the production of significant amount of palm oil mill effluent
(POME) from the milling process and may lead to environmental degradations. Nonetheless, certain
measures can be taken up to minimize the water consumption as well as mitigate the potential environmental
impacts. Even though the study for now covers up to the palm oil mill, in the near future, it will be further
expanded to also cover right up till the production of palm biodiesel and other downstream products.
20
THE ART IN-WELL TECHNOLOGIES, RE-ENGINEERING EXISTING REMEDIES TO

REDUCE TIME, COSTS & RISKS
Mohamed Odah
(Accelerated Remediation Technologies, Inc Overland Park, Kansas 66212, USA)
Building on the multiple remediation concepts combined within the ART Technologies, ART has
engineered an alternative to traditional air sparging and soil vapor extraction (AS/SVE) remedial systems.
This patent-pending alternative utilizes similar processes as traditional AS/SVE, but is applied differently.
The ART AS/SVE well consists of two screens separated by a solid section. The lower screen is
positioned near the bottom of contamination. The upper screen intersects the water table. An innovative,
specially designed packer will be strategically positioned in the solid riser portion, between the two screen
zones, to force injected air to exit the well via the lower screen. The vapors are captured through the upper
screen along with additional vapors captured from the vadose zone, thus reducing or eliminating vapor
intrusions issues. In addition to reduced drilling cost, savings also include reduced trenching and piping
installations and maintenance activities.
Traditional AS/SVE methods may cause uncontrolled air sparging into the formation that is
difficult to recapture allowing possible expansion of plume boundaries and vapor intrusion into nearby
structures. However, the ART AS/SVE well utilizes one below grade structure to achieve greater control
of component processes as well as decreased costs due to initial construction and long term operation and
maintenance. The ART AS/SVE design allows for a more controlled recapture of the sparged air as the
vapor extraction component is included within the same sub-grade structure. Furthermore, the ART
Innovative AS/SVE allows for the addition of amendments to the subsurface through the sparging screen
if it becomes necessary.
21
ENVIRONMENTAL RISK ASSESSMENT OF CAFFEINE IN PARANA’S RIVERS (BRAZIL)
Maiara C. Perussolo, Pauline Lais Nasatto, Isadora Terumi Saruhashi*, Andréa Fernandes, Eliane
Carvalho de Vasconcelos, Cíntia Mara Ribas de Oliveira
(Universidade Positivo, Curitiba, PR, Brazil)
The presence of pharmaceuticals in the environment has been intensively researched, and the risk posed by
these substances has been still considered as an important issue to assess the aquatic organisms exposure.
Caffeine can be found in pharmaceuticals and foods and it has been reported as a continuous pollution tracer
in the aquatic environment. Environmental risk assessment of caffeine shows interesting scenarios
concerning anthropogenic inputs to the aquatic environment, mainly in developing countries, in which
many people have no basic sanitation. The herein study analyzed the environmental risk of caffeine in some
rivers in Alto Iguaçu Basin (Paraná State – Brazil). The risk quotient (RQ) was calculated using the ratio
between the measured environmental concentrations (MEC) of some stations in the basin and the aquatic
organisms measured low effect concentrations (LEC). The average concentrations ranged from 6.8 ng/L to
608 µg/L. High environmental risk situations were identified for most of the stations (RQ ≥ 1). The highest
quotients were found to the stations into the Barigui river, which may be related to the anthropogenic
activities in the area. The presence of caffeine in Paraná’s rivers from the Alto Iguaçu Basin showed the
significant impacts from irregular domestic wastewater discharges.
22
PROGRESS ON THE RESEARCH OF FLOOD ROUTING UNDER THE EFFECT OF

SEEPAGE IN SEASONAL STREAMS
Wu Guizhi *, Li ningning and Wu Zhouhu

(Qingdao Technological University ,Qingdao, Shandong Province, China)
Flood is one of the major natural disasters in the world. The simulation on stream flood routing has realistic
significance in order for flood control and prevention. Seasonal seepage in streams causes obvious damages
in arid or semiarid areas, which affects the flood flow and process.The study on the effect of seepage on
seasonal flood routing can provide scientific methods and basis for flood forecast, prevention and control,
and comprehensive utilization of water resources of seasonal rivers.It describes the main results of domestic
and foreign researchers about the effect of seasonal seepage on flooding routing. Moreover, it analyzes the
progress of domestic studies in China and discusses the trend of development.
23
MASS FLUXES OF URBAN MICROPOLLUTANTS AND INTEGRATED MODELLING OF

THE RIVER – GROUNDWATER – INTERACTION IN THE CITY OF HALLE/GERMANY
FRIDO REINSTORF1, Sebastian Leschik2, Andreas Musolff2, Gerhard Strauch2, Karsten Osenbrueck3 and
Mario Schirmer4
1
( University of Applied Sciences Magdeburg-Stendal, Department of Water and Waste Management,
Breitscheidstrasse 2, 39114 Magdeburg, Germany; 2,3Helmholtz Centre for Environmental Research –
UFZ, Permoserstrasse 15, 04318 Leipzig, Germany; 4EAWAG, Swiss Federal Institute of Aquatic
Science and Technology, Department Environmental Toxicology, Ueberlandstrasse 133, 8600
Duebendorf, Switzerland)
The urban aquatic environment is increasingly polluted by low concentrated but high eco-toxic compounds
as pharmaceuticals, fragrances and endocrine disruptors. These so-called xenobiotics are emitted into the
surface and subsurface waters by outlets of waste water treatment plants and/or by seeping processes of
waste water. This contamination could have a long-time impact on the urban ecosystem and on human
health.
Within an interdisciplinary project on risk assessment of water pollution, we work on the
identification of water and substance fluxes in urban areas. The objective is an integrated modelling tool
for the description of transport of substances in the urban environment. Transport processes of interest are
related to surface water, groundwater and the groundwater – surface water interaction zone.
In a first attempt we used a flow model concept with in- and output and surface water transport represented
by the city of Halle, Germany, and the river Saale. The river Saale acts as surface water system collecting
lateral inputs along the city traverse. Using indicators for xenobiotic impacts on water resources such as
Bisphenol A and t-Nonylphenol, Carbamacepine, Galaxolide and Tonalide investigations of the pathways
and the behaviour of the substances in the environment have been carried out. In the city of Halle,
concentrations of the indicators at a magnitude of ng/L to g/L were found in rivers and in groundwater.
A balance of water and substance fluxes in the rivers was built up for the city as a whole. The calculation
of the loads shows increasing values of the investigated indicators over the distance of the city passage.
The understanding of the interaction between groundwater and surface water is important to
quantify the exchange of substances between the two hydrological compartments. In order to investigate
this, a transient hydrodynamic river reach model of the Saale River and a groundwater flow model of the
area connected to the reach were built up and coupled. Using this model, the inter-compartmental transport
of the indicator Carbamacepine that exfiltrated from the Saale River into the groundwater was simulated
over a time period of one year.
24
IMPROVING IMPLEMENTATION CAPACITIES OF CITIES BY SHARING BEST

PRACTICES IN URBAN WATER CYCLE SERVICES
C.J. Van Leeuwen

(KWR Watercycle Research Institute, P.O. Box 1072, 3430 BB Nieuwegein, The Netherlands)
The European Innovation Partnership on Water (EIP Water) is one of five European Innovation
Partnerships which aim is to promote innovation that contributes to solving social challenges, enhances
Europe's competitiveness and creates employment and economic growth. EIPs help to pool expertise and
resources by bringing together public and private actors at EU, national and regional levels. The overall
objective of the EIP Water is to support and facilitate the development and implementation of innovative
solutions to deal with the many water related challenges Europe and the World are facing, as well as to
promote economic growth by bringing such solutions to the market in Europe and further afield.
“City Blueprints” is one of nine initial EIP Water AG’s which have been selected from a total of 64
proposals submitted in 2013 (http://www.eip-water.eu/working-groups/city-blueprints-improving-
implementation-capacities-cities-and-regions). The “City Blueprints” for Water is a baseline assessment of
the sustainability of water management in a city (or other dominantly urban region). The result allows a
city to quickly understand how advanced it is in sustainable management of its urban water cycle services
(UWCS) and to compare its status with other leading cities. City Blueprints” is also an opportunity to take
part in a new and innovative programme to improve city-level water steward-ship, in the spirit of smart and
sustainable cities. The basic output is a simple radar chart.
The paper highlights the assessments done in 25 cities in the world. The advantages and limitations of
the approach will be discussed, as well as the next steps that are needed to solve the challenges in (1) water
safety, (2) water scarcity and (3) water governance in cities around the world.
25
SUSTAINABILITY OF WATER RESOURCES OF HO CHI MINH CITY, VIETNAM
Minh T. Ngo, Jae M. Lee, Nam C. Woo

(Yonsei University, Seoul, Korea)
As a fresh-water source, groundwater is a critical element of sustainable development of coastal areas. This
study identifies the causes of saline-water intrusion into the main water-supplying aquifer, the Upper
Pliocene aquifer (n22), of the Ho Chi Minh City. Hydrogeochemistry, isotope signatures and water-level
data indicated that saline-water intrusion be induced by groundwater over-exploitation from the aquifer to
meet the increased water demand from population growth and expansion of industrial complexes. During
the period of 2004–2009, the saline boundary had moved inland with the farthest distance being about 3.2
km. The ratios of Br:Cl and δ2H and δ18O values of the samples indicated that the salinization of
groundwater resulted mainly from mixing with seawater over a long period. Calculation results of the
groundwater sustainability indicators (GWSIs) show that groundwater resources of the study area face a
significant risk for its sustainable development, and thus, management strategies for the coastal aquifer
should be implemented urgently.
26
ASSESSMENT OF GROUNDWATER RECHARGE USING WATER-TABLE FLUCTUATION

METHOD AND WATER-BALANCE MODEL
Sasmita Sahoo and Madan K. Jha

(Indian Institute of Technology Kharagpur, Kharagpur, West Bengal, India)
ABSTRACT: Accurate quantification of groundwater recharge is essential for sustainable management

and protection of valuable groundwater resources. The main objective of this study is to determine and
compare the spatial distribution of groundwater recharge using two methods: (a) water-table fluctuation
(WTF) method and (b) water-balance method using Visual HELP model. In water-table fluctuation method,
the site-specific recharge was computed at 13 observation wells using specific yield and water-level data.
In water-balance approach, the Visual HELP model was used to estimate site-specific groundwater recharge
at 8 selected sites considering soil characteristics, land cover and weather data as inputs to the model. The
point estimates of recharge obtained by both the methods were then subjected to geostatistical modeling to
determine the spatial distribution of groundwater recharge in the study area. Comparison of results from the
above two methods indicated that the mean annual recharge for the 11-year period range from 55.1 to 348
mm/year and from 196.6 to 326.1 mm/year for WTF method and Visual HELP model, respectively. Thus,
the WTF method shows a high range of spatial variability as compared to Visual HELP model. However,
the most of the groundwater recharge in the study area was found to occur during the monsoon season. Based
on the findings of this study, it can be inferred that comparison of multiple methods is imperative for
determining the range of pragmatic recharge in a study area. Moreover, the results presented in this paper
is useful for future studies of groundwater recharge and water management planning as well as construction
and calibration of groundwater flow simulation models.
INTRODUCTION
In order to meet demand for freshwater, there has been indiscriminate exploitation of groundwater
resources. If pumping exceeds the total amount of recharge, groundwater mining occurs and the aquifer
becomes no longer sustainable (Sophocleous, 2005). Since recharge is a key parameter in groundwater
resources, a reliable estimate of recharge is essential in order to develop a sustainable management scheme
for protection of this vital resource. The key to the successful estimation of groundwater recharge lies in
the utilization of a variety of independent methods. It is difficult to estimate groundwater recharge reliably
by one method because of uncertainties and assumptions associated with different methods, which could
eventually have detrimental impacts on resource management decisions. For this reason, it is strongly
recommended that recharge should be estimated using multiple methods to increase reliability of recharge
estimates (Healy and Cook, 2002; Misstear et al., 2009). They have demonstrated that recharge estimates
can widely vary depending on the estimation technique employed.
The different methods available for recharge estimation include lysimeters, chemical tracing,
Darcian approach, water-balance method, water-table fluctuation method, numerical modeling with
groundwater flow models, infiltration models, hydrograph separation method, isotopes method. The choice
of methods will depend on the spatial and temporal scale of investigation, the characteristics of the aquifer,
the mechanism sought for understanding, the availability of data of adequate quantity and quality, and the
spatial and temporal resolution of the results (Flint et al., 2002; Heppner et al., 2007). Water- balance
methods used for recharge estimation are based on the fact that water entry should be equal to the amount
discharged plus or minus the variation in the volume of water that is stored. Water-balance methods
have several advantages like availability of data, their straightforward implementation and relatively low
cost, and their applicability to all types of recharge and aquifer media (Sophocleous, 1991; Rivard et al.,
2008). On the other hand, the water-table fluctuation method (WTF) method assumes groundwater rises in
27
an unconfined aquifer as a result of recharge reaching the groundwater level and it is one of the most widely
used techniques for estimating net recharge rates (Healy and Cook, 2002).
The main objectives of this paper are to present the application of two important methods, namely
water-table fluctuation (WTF) method and water-balance model using Visual HELP to estimate site-
specific groundwater recharge and then to determine its spatial distribution by interpolating the point
estimates of recharge using geostatistical modeling and GIS.
MATERIALS AND METHODS
Study Area Description. The Kushabhadra-Bhargavi Interbasin of Mahanadi delta, Odisha, India (Figure
1) was selected as a study area for quantifying groundwater recharge. It is located between 19° 49' 04'' N
to 20° 18' 45'' N latitude and 85° 54' 47'' E to 86° 03' 26'' E longitude. The two major rivers, namely
Kushabhadra and Bhargavi River form the eastern and western boundaries of the study area, respectively.
The topography of the area is almost flat with the elevation varying from 0 to 26 m MSL and it encompasses
an area of 620 km2. The climate of the area is classified as tropical monsoon climate and wet. The average
annual rainfall is about 1470 mm and mostly occurs during south-west and north-east monsoon season from
mid-June to end of October. The mean monthly temperature ranges from 29 to 46 °C and the mean monthly
humidity varies from 41 to 86%, while the mean monthly wind speed varies from 2.6 to 26 km/h. The study
area is mostly occupied by the laterite and alluvium geologic formation which contribute to the essential
source of groundwater in the basin. The major aquifers present in the study area consist of fine sand,
medium sand, coarse sand and coarse sand with pebbles; the medium to coarse sand being the predominant
formation.
FIGURE 1. Map of the study area with location of sites selected for recharge estimation.
Data Collection. The daily rainfall data of six rainfall stations in the study area were collected for 21 years
(1990-2010) from the Department of Agriculture, Puri, Odisha. The groundwater-level data of 13
28
observation wells (wells tapping uppermost unconfined aquifer) were collected for 15 years (1997-2011)
from the Central Groundwater Board (CGWB) and Groundwater Survey and Investigation (GWS&I),
Bhubaneswar, Odisha. The lithological data of the study area were collected from the Odisha Lift Irrigation
Corporation (OLIC), Bhubaneswar, Odisha. The meteorological data such as relative humidity, wind speed,
duration of sunshine hours, maximum and minimum air temperature have been collected for 2000-2010
period at Bhubaneswar and Puri stations from India Meteorological Department, Pune.
Methods Investigated for Groundwater Recharge Estimation. Two methods have been selected to
estimate groundwater recharge in the study area: (1) the water-table fluctuation method, and (2) water-
balance approach using Visual HELP model. These methods have been selected based on the availability
of data and the hydrogeological setting of the study area. A brief description of these two methods is
presented below.
Water-Table Fluctuation Method. The water table fluctuation (WTF) technique is mainly applied to
shallow water tables (unconfined aquifers) that display sharp water level rises and declines (Healy and
Cook, 2002; Scanlon et al., 2002). It is based on the principle that rises in groundwater levels in unconfined
aquifers are due to recharge water reaching at the water table. The net recharge is calculated as (Healy and
Cook, 2002):
dh ∆h
R = ∆SGW = S y = Sy (1)
dt ∆t
Where, R = groundwater recharge, ∆SGW = groundwater storage variation, Sy = specific yield, h =

water level and t = time. In this study, the net groundwater recharge was computed at 13 observation wells
for 11 years (2000-2010) using Eqn. (1). Specific yield values obtained from pumping test data analysis
were used for estimating net recharge.
Visual HELP Water-Balance Model. Visual HELP was developed by the U.S. Army Waterways
Experiment Station to compute the water balance of landfills (Schroeder et al., 1994). It is a “quasi-two-
dimen-sional” model that routes rainfall falling on the land to components of evapotranspiration, runoff,
storage, and vertical infiltration (recharge) for a layered soil column (Schroeder, et al., 1994). The
expression used for estimating groundwater recharge by HELP model (based on the conservation of mass
principle) as follows:
R = P - (ET +R +ΔS) (2)
Where, R = recharge; P = precipitation; ET = evapotranspiration ; R = direct runoff ; and ΔS =

change in storage.
In this study, water-balance equation (Eqn. 2) was applied by Visual HELP model and site-specific
groundwater recharge was estimated at 8 selected sites for the period 2000-2010. Mean annual groundwater
recharge was calculated from rainfall under the influence of soil properties, solar radiation, air temperature,
wind speed, and vegetative properties. Therefore, input data used by the model in this study were monthly
precipitation, monthly temperature, average wind speed, relative humidity, solar radiations, soil properties,
and land cover. The spatial distribution of land use/land cover in the study area comprises of six major land
use/land cover categories namely, agricultural land, dense forest, degraded forest, wasteland, settlements,
and rivers and water bodies. The depth and formation of the soil profile at each of the 8 sites were obtained
from the detailed stratigraphy analysis. The soil classes found in the study area are: silty loam, clayey loam,
coarse sand, very fine sand and sandy loam. The soil properties of the selected sites in the study area were
obtained from Water Technology Centre for Eastern Region Bulletin (Singh et al., 2002). Moreover, the
29
runoff calculated from the SCS curve number was used by Visual HELP model, while evapotranspiration
was calculated from Penman–Monteith equation.
Spatial Prediction of Groundwater Recharge. The spatio-temporal variability of the recharge is of great
importance for water management applications (Scanlon et al., 2002) can successfully be obtained by
combining the recharge estimation technique with the Geographic Information System (Sophocleous,
1991). In this study, the point estimates of net recharge (mean annual recharge) by both WTF technique
and Visual HELP model were interpolated using geostatistical modeling and GIS in order to determine the
spatial distribution of groundwater recharge over the study area.
RESULTS AND DISCUSSION
Results of Groundwater Recharge Estimation by WTF Method and Visual HELP Model. The annual
variation of recharge estimated by WTF method at 13 observation wells for 11-year period (2000-2010) is
presented in Figs. 2(a,b). It is evident from this figure that maximum amount of recharge is obtained at site
O-1 for the year 2006 and 2004 [Fig. 2(a)], whereas lowest amount of recharge is obtained at Site O-20 for
the year 2007 [Fig. 2(b)]. Figure 3 shows the annual variation of recharge estimated by Visual HELP model
at 8 sites for 11-year period (2000-2010). Clearly, maximum amount of recharge is found at Puri Sadar in
the year 2000 and 2001 due to highest rainfall in these years, while Gop-II has lowest amount of recharge
in the year 2002 and 2006 due to scanty rainfall. Thus, it can be inferred that groundwater recharge responds
well to the rainfall events.
FIGURE 2(a,b). Annual variation of recharge (WTF method) at 13 observation wells

for 2000-2010 periods.
Moreover, the mean annual recharge for the 13 observation wells as estimated by WTF method is
shown in Figure 4(a) together with error bars of standard errors. It is apparent from Figure 4(a) that the
maximum recharge occurs at Site O-1 during 11 years, while little groundwater recharge occurred at Site
O-20. Further, the variation in recharge over 11 years is highest at Site O-1 followed by O-2, O-7 and O-
19, while O-8 shows smaller amount of variation in recharge over 11-year periods. On the other hand, for
the Visual HELP model [Figure 4(b)], the variation in recharge is highest at Puri Sadar, followed by
Satyabadi and the remaining six sites shows almost equal variation of recharge over 2000-2010 periods.
30
FIGURE 3. Annual variation of recharge (Visual HELP model) at 8 sites for 2000-2010 periods.
FIGURE 4. Variation of Mean Annual Recharge estimated by (a) WTF method (b) Visual HELP model.
31
FIGURE 5. Spatial distribution of mean annual recharge by: (a) WTF method and (b) Visual HELP
model.
32
Spatial Distribution of Groundwater Recharge. The mean annual groundwater recharge in the study area
estimated by WTF method varies from 55.1 to 348 mm/yr as observed from Figure 5(a). It is apparent from
this figure that a net recharge rate of 87.7-120.2 mm/yr is predominant in the study area, followed by 282.9-
348 mm/yr found in the northern portion of the study area. Moreover, the recharge estimates from WTF
shows a wide range of variability of recharge over the study area. However, recharge estimates from Visual
HELP model indicates less variability in recharge distribution (196.6-326.1 mm/yr) over the study area as
compared to WTF method, as shown in Figure 5(b). Further, the majority of the north-west portion and
some parts of the central portion have the highest estimate of groundwater recharge from the water-balance
model, i.e., 297.4-326.1 mm/yr
CONCLUSIONS
In this study, groundwater recharge has been estimated by using two methods, viz., water-table
fluctuation (WTF) method and Visual HELP water-balance model considering both site-specific and
spatially distributed groundwater recharge. In WTF method, the site-specific recharge was computed at 13
observation wells for 11 years (2000-2010), whereas in water-balance approach, the Visual HELP model
was used to estimate the point estimate of groundwater recharge at 8 selected sites for 11 years (2000-2010).
Then, spatial distributions of groundwater recharge are determined by interpolating the point estimates of
recharge in GIS environment. Comparison of results from the above two methods indicated that the estimates
of mean annual recharge for the 11-year period range from 55.1 to 348 mm/year and from 196.6 to 326.1
mm/year for WTF method and Visual HELP model, respectively. Thus, the WTF method shows a high range
of spatial variability as compared to Visual HELP model. However, the most of the groundwater recharge in
the study area was found to occur during the monsoon season. The techniques used in this study are easy to
implement, widely available and do not require complex hydrogeologic modeling. Moreover, the results
presented in this paper, can also provide input to the construction and calibration of groundwater flow
simulation models, which is essential for sustainable management of groundwater resources.
ACKNOWLEDGEMENTS
The authors are very grateful to the Department of Agriculture, Puri, Odisha, Central Groundwater
Board (CGWB), Groundwater Survey and Investigation (GWS&I), Bhubaneswar, Odisha, and India
Meteorological Department, Pune for providing necessary data for the present study.
REFERENCES
Flint, A. L., L. E. Flint, and E. M. Kwicklis. 2002. “Estimating recharge at Yucca Mountain, Nevada, USA:
comparison of methods.” Hydrogeology Journal. 10(1): 180-204.
Healy, R. W., and P. G. Cook. 2002. “Using groundwater levels to estimate recharge.” Hydrogeology
Journal. 10: 91-109.
Heppner, C. S., J. R. Nimmo, G. J. Folmar, W. J. Gburek, and D. W. Risser. 2007. “Multiple-methods
investigation of recharge at a humid region fractured rock site, Pennsylvania, USA.” Hydrogeology
Journal. 15: 915-927.
Misstear, B. D. R., L. Brown, and P. M. Johnston. 2009. “Estimation of groundwater recharge in a major
sand and gravel aquifer in Ireland using multiple approaches.” Hydrogeology Journal. 17: 693-706.
Rivard, C., Y. Michaud, R. Lefebvre, C. Deblonde, and A. Rivera. 2008. “Characterization of a regional
aquifer system in the Maritimes Basin, eastern Canada.” Water Resources Management. 22: 1649-1675.
Scanlon, B. R., R. W. Healy, and P. G. Cook. 2002. “Choosing appropriate techniques for quantifying
groundwater recharge.” Hydrogeology Journal. 10(1): 18-39
Schroeder, P. R., C. M. Lloyd, and P. A. Zappi. 1994. The Hydrologic Evaluation of Landfill Performance
(HELP) Model. User’s guide for version 3. Interagency Agreement No. DW21931425.
33
Singh, R., D. K. Kundu, and H. N. Verma. 2002. Hydro-physical Characteristics of Orissa Soils and their
Water Management Implications. Research Bulletin No. 12, Water Technology Centre for Eastern
Region, (Indian Council of Agricultural Research), Bhubaneswar, Orissa, 751023, India.
Sophocleous, M.A. 1991. “Combination the soil water balance and water-level fluctuation methods to
estimate natural groundwater recharge: Practical aspects.” Journal of Hydrology. 124: 229-241.
Sophocleous, M.A. 2005. “Groundwater recharge and sustainability in the High Plains aquifer in Kansas,
USA.” Hydrogeology Journal. 13(2): 351-365.
34
EVAPORATION REDUCTION BASED DESIGN OF WATER PONDS SURFACE 1072

AREAS USING PALM FRONDS
Ibrahim H. Elsebaie
(Civil Engineering Department, College of Engineering, King Saud University, Saudi Arabia;
elsebaie@ksu.edu.sa.)
ABSTRACT: The limited water supply and the increased future demand necessitate the importance of
optimum use of water resources which might be obtained through reduction of water losses. The reduction
of evaporation losses has recently received increasing attention because of the increase in water demand
and the decrease in water availability. Therefore, the aim of this research is to use a new technique that can
save evaporation water losses as a non-conventional water resource.
To know the efficiency of this technique (Palm Fronds cover) in our arid zones, an experimental
setup consisted of four pans with two different cross sections (rectangular and square). The setup included
also study the effect of the shape and the cover pattern on the rate of the evaporation losses.
The daily observations during 41 days reduced the losses by evaporation and the rates of reduction
of the evaporation are remarkable and are more than 45 % for the half covered compared to the open pan.
And the strips covered reduce the evaporation compared to the open pan by more than 60%. It could be
concluded from the research that water evaporation can be reduced and controlled using environmentally
safe techniques.
Keywords: Evaporation, Palm Fronds, arid zones, water resources.
INTRODUCTION
Water is the most precious natural resource in the world, especially in Saudi Arabia with arid
climate and limited resources of surface water. Management of water by reducing the evaporation rates will
optimize the amount of water that may perhaps support the ever-growing domestic, agricultural, and
industrial demands. Evaporation losses from small reservoirs affect their water storage efficiency.
Evaporation from open water bodies such as wetlands, reservoirs and lakes often represents the largest loss
in their local hydrological budget, yet its quantification still continues to be a theoretical and practical
challenge in surface hydrology.
Limited renewable water resources characterize the Kingdom of Saudi Arabia, due to its
geographical location and climatic conditions. In fact, renewable water resources of the kingdom are
significantly less as compared to non–renewable water resources due to low annual precipitation and
therefore, require greater attention for development and management for long-term utilization.
Considering the importance of optimal utilization of renewable water resources, therefore, the
government was constructing dams on some of the valleys in order to benefit from the establishment of
such dams.
But one of the challenges of water management in arid regions is to reduce the huge amount of
water loss through evaporation from water surfaces of dam reservoirs and lakes due to extremely high
evaporation rates.
Saudi Arabia Experiences high evaporation rate with an annual rate ranges between 2500 to 3000
mm. on the other hand, rainfall annual rate ranges from 100 to 150 mm, which shows the need for water
conservation though evaporation reduction techniques. One way of evaporation rate reduction might be
activated by designing ponds surface areas which give the minimum evaporation .
35
Many materials, either chemicals or physical covers, were developed to reduce evaporation from
open water surfaces. Those materials are designed to suit certain climatic conditions. some are economically
feasible but may have negative environmental impacts. There has been an increased focus on evaporation
control techniques which can be applied to water storage due to severe drought conditions in many parts of
the world (Anonymous, 2003). In a similar study Barnes (1993) found that monolayer is potentially most
effective in conditions where the rate of evaporation is high.
Cooley (1983) carried out a study to determine the effect of long-term exposure on the evaporation
reduction efficiency of five floating cover materials. He has shown that evaporation reduction efficiencies
ranged from 36% to about 84% depending on cover type.
Palm tree is considered to be one of the most important commercial crops widely distributed across
the Saudi Arabia capable of withstanding extremely hot weather conditions of the arid region (Al-Juruf et
al., 1988). The number of trees in the Kingdom is estimated to be over 21 million. These trees are estimated
to yield about 210,000 tons of fronds (Al Gassim Dates Factory, 2011).
The study by Alvarez et al. (2006) on different types of shading meshes reveals that the shading of
pan induced a significant decrease of the daily evaporation rate, ranging from 50% for the aluminized screen
to near 80% for the coloured-polyethylene meshes.
Craig et al. (2007) observed that the use of physical cover was able to reduce evaporation substantially,
they suggested that these types of covers would be more effective with small reservoirs (less than 10 ha in
size). However the physical covers can also be used for large reservoirs but it could be uneconomical.
The study by Ikweiri et al. (2008) conducted study beside the Omar Muktar reservoir to test the
effect of the monolayer technique to reduce the evaporation in comparison to the cost of the local water that
are lost by evaporation.
Recent study done by Al-Hassoun et al. (2009) on impounding reservoirs found that the average
reduction in evaporation using the floating cover made up of palm leaves was 63% for the fully covered
pool while for the half covered pool it was 26% only.
Another study by Al-Hassoun et al. (2011) on effectiveness of using palm fronds in reducing water
evaporation showed that evaporation reduction from the fully covered pool was about 55%, while that from
the half covered pool was about 26%. Also in their study, water quality analysis showed that fronds have
no serious effect on water quality.
Shamshad and AlShaikh (2013) conducted study on the Use of palm fronds as shaded cover for
evaporation reduction to improve water storage efficiency. They observed that the average reduction in
evaporation in the covered pan (with single layer of cover) was about 47% as compared to the evaporation
from the open pan. However, the average reduction in evaporation in the covered pan (with double layer of
cover) was about 58% as compared to the evaporation from the open pan.
Present study proposes the use of Palm fronds as strips covered and half covered for the reduction of
evaporation from the open water surface.
Experimental Setup. The study deals with the effect of surface area, shape and the cover pattern on
evaporation reduction. For this purpose, two different surface areas (rectangular and square) are tested.
Two different configuration pattern for the cover were used, one of them half covered by palm fronds and
the other configuration use strips. These configurations were made for the four tanks. Details of these tanks
are given in Table (1).
The material used for cover was locally available palm fronds which are a massive agriculture
waste and environmental friendly by-product in Saudi Arabia, one of the strip is shown in Fig. (1). Shaded
cover reduces the energy available for evaporation; reduces wind action over the water surface and traps
humid air under the cover, all factors that contribute to evaporation.
36
Data Collection. A large amount of data were collected during the study period (42 days), but only the
most important data and results have been presented herein. These data include measurement of water levels
in tanks, evaporation depths and some meteorological data (i.e temperature, Humidity and wind speed), as
well as some other data were recorded (i.e water conductivity, Dissolved oxygen (DO)). One example of
the recorded data for the square tank with strips cover were summarized and presented in Table (2)
Table (1). Tested surface area

Tank No Tank shape Area (m2) Dimensions (L x W x D)
1 Rectangle 1 0.67x1.5x0.5
(strips covered)
2 Rectangle 1 0.67x1.5x0.5
(Half covered)
3 Square 0.5 0.707x0.707x0.5
(strips covered)
4 Square 0.5 0.707x0.707x0.5
(Half covered)
Strip sample
Figure 1: One of the strip used for square tank
Evaporation was measured by measuring changes in water level in the tank. This was done
manually with point gauge. The data were recorded at 9:30 am and 2:00 pm every other day. The amount
of evaporation is a function of temperature, humidity, wind and other ambient conditions. In order to relate
evaporation to wind current or expected conditions, data of continuous ambient temperature as well as the
amount of water passed with evaporation were recorded with the help of a nearby weather station. Water
was added into the tanks to substitute the evaporation when water level in the tank was dropped to 20 cm.
37
The experimental observations revealed that the evaporation rate was directly affected by the
ambient temperature as the rate of evaporation was higher during the day time (when ambient temperature
was higher) while it was less or minimum in the evening and night.
Figs. (2 and 3) represent the overall percentage reduction in evaporation using strips layer of palm
fronds as cover compared to the one without cover for the rectangular ad square tanks. It was observed that
the average reduction in evaporation in the covered rectangular tank (with strip layer of cover) were about
60% and 66% for rectangular and square respectively when compared to the evaporation from the open
tanks (same dimensions).
Table (2). Recorded data for square tank with strips cover
after water air air air Wind
Time Evaporation DO Humidity
Conductivity temperature temperature temperature temperature Humidity(max) Humidity(Min) Speed
(days) depth (CM) rain (MG\L) (Avg)
(ms\cm) ( max ) ( min ) ( Avg ) (km\h)
0 0 7.53 1072 26.9 31 16 23.5 42 19 29 4

2 0.9 7.22 1068 25.7 30 16 23 59 14 37 11
5 1.7 7.08 1060 25 30 14 22 51 12 31 6
6 3 6.77 1073 21.7 30 15 22.5 48 12 30 7
after
11 1.5 3.76 1094 17.3 22 14 18 94 59 80 13
rain
13 2 4.22 1062 18.2 23 18 20.5 94 64 84 6
17 0.4 6.55 1055 19 23 9 16 88 11 54 3
18 1 6.83 1065 20.4 26 9 17.5 87 10 50 1
20 1.9 7.02 1099 22.6 29 11 20 82 7 40 5
25 4 6.92 1164 14.8 25 10 17.5 88 18 58 8
27 4.8 6.88 1189 19.9 29 10 19.5 76 5 38 4
31 6.6 7.19 1260 20.6 27 13 20 94 20 62 5
32 6.8 7.04 1275 20.4 28 13 20.5 94 8 52 5
34 8 7.16 1332 14.7 17 8 12.5 59 29 44 12
after
39 9.8 7.21 1428 8.8 12 4 8 65 16 43 15
rain
after
40 9.5 7.51 1411 10.5 16 7 11.5 76 17 45 7
rain
41 10.3 7.64 1465 11.7 17 6 11.5 57 12 31 6
50
45
Evaporation depth (CM)
40
35
30
25
20
15
10
5
0
1 11 21 31 41 51
time (days) In the period from 7 Nov to 18 Dec
Rectangle with strips coverd Rectangle without cover
.
Figure 2: Comparison between rectangle tank with strips cover and without cover
Figs. (4 and 5) show Comparison of evaporation depth for the different patterns for the four the two
tanks. The results showed that in case of rectangular shape, the strips covered reduced the evaporation by
38
23 % more compared to the half covered. But in case of square shape, the strips covered reduced the
evaporation by 19 % more compared to the half covered
In comparison with recent study done by Shamshad and AlShaikh (2013), where the evaporation
daily avg. = 9.5±0.11 mm (open pan) on same month (March).
The half covered rectangle reduce the evaporation compared to the open pan by 50%, and the strips covered
rectangle reduce the evaporation compared to the open pan by 61%.
The half covered square reduce the evaporation compared to the open pan by 60%, and the strips covered
square reduce the evaporation compared to the open pan by 67%.
In comparison with recent study done by Shamshad and AlShaikh (2013), where the evaporation
daily avg. = 7±0.17 mm (open pan) on same month (November). The strips covered rectangle reduce the
evaporation compared to the open pan by 57%. The strips covered square tank reduce the evaporation
compared to the open pan by 64%.
50
45
Square with strips coverd
40
Evaporation depth (CM)
35
30
25
20
15
10
5
0
1 11 21 31 41 51
time (days) In the period from 7 Nov to 18 Dec
Figure 3: Comparison between square tank with strips cover and without cover
12
Evaporation depth (cm)
10
8
6
4
2
0
0 48 96 144 192 240 288 336 384 432 480 528 576
Time (hours)
rectangle half covered rectangle strips covered
Figure 4: Comparison of evaporation depth for the rectangle tank
39
9
8
evaporation depth (cm) 7
6
5
4
3
2
1
0
0 48 96 144 192 240 288 336 384 432 480 528 576
Time (hours)
square half covered square strips covered
Figure 5: Comparison of evaporation depth for the square tank
CONCLUSIONS
The daily observations during 41 days reduced the losses by evaporation and the rates of reduction
of the evaporation are remarkable and are more than 45 % for the half covered compared to the open pan.
It was observed that the average reduction in evaporation in the covered rectangular tank (with strip layer
of cover) were about 60% and 66% for rectangular and square respectively when compared to the
evaporation from the open tanks (same dimensions). This is approximately 15% higher as compared to
percentage evaporation reduction by use of half layer cover.
Significant results obtained in comparison the results of this study to the study done by Shamshad
and AlShaikh (2013) in two months. The strips covered reduce the evaporation by about 57% and 64% for
rectangular and square tanks respectively when compared to the open pan.
Palm tree is considered to be one of the most important commercial crops and is widely distributed
across the country. Palm fronds and leaves are considered as disposed waste after pruning. Therefore, it is
recommended to use palm fronds as cover for open water surfaces to reduce evaporation as it is a good use
of disposed waste, is environmental friendly and is capable of withstanding extremely hot weather
conditions of the arid region.
ACKNOWLEDGEMENT
The research was carried out at the Department of Civil Engineering, College of Engineering, King Saud
University, Riyadh, KSA.
REFERENCES
Al Gassim Dates Factory <http://www.gassimdates.com/ index.php?action=pages&id=28>.

Al-Hassoun, S.A., Mohammed, T.A., Nurdin, J., 2009. Evaporation reduction from impounding reservoirs
in arid areas using palm leaves. J. Eng. Appl. Sci. 4, 247–250.
Al-Hassoun, S.A., AlShaikh, A.A., Al Rehaili, A.M., Misbahuddin, M., 2011. Effectiveness of using palm
fronds in reducing water evaporation. Can. J. Civil Eng. 38 (10), 1170–1174, 10.1139/l11-071.
40
Al-Juruf, R.S., Ahmed, F.A., Alam, I.A., 1988. Development of heat insulating material using date palm
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41
HYDRAULIC FRACTURING: A LOOK AT EFFICIENCY AND THE ENVIRONMENTAL

EFFECTS OF FRACKING
Emily C. Jackson and David E. Dismukes

(Louisiana State University, Baton Rouge)
ABSTRACT: The use of hydraulic fracturing techniques in unconventional oil and gas development has
resulted in an energy revolution that is dramatically changing the outlook for U.S. energy supplies and
prices. Yet, with these new developments come a number of concerns regarding the environmental and
human health effects that can be a negative consequence of these new hydrocarbon extraction techniques.
The three most cited concerns are those associated with air emissions from onsite combustion, large levels
of water use, and the possible intrusion of fluids and chemicals into surface and groundwater from hydraulic
fracturing activities. This research provides well-specific estimates of major air emissions, water use, and
the chemical composition and usage levels for the Haynesville shale utilizing operator-specific data reported
to the Louisiana Department of Natural Resources as well as voluntary reports on water use included in the
industry-supported Frac Focus on-line database. This research provides a three-component inventory of
major air pollutants, water use and chemical use over the rapid Haynesville shale development period from
2007-2013. The annual inventory is then compared to other statewide and local air emissions, water use
and chemical discharges and finds that while Haynesville-related uses and discharges are generally small
relative to statewide data, local impacts can differ and warrant closer monitoring. This research also shows
some positive environmental “learning-by-doing” effects: that is, operators are becoming more efficient at
their water use, air emissions, and chemical uses as they drill more wells and garner more experience in the
emerging play. Those operators with greater levels of experience (i.e., those that drill more wells) are
relatively more efficient at reducing some, but not all, of the environmental impact of their activities than
those operators drilling fewer wells.
INTRODUCTION
Hydrocarbons are typically located in geologic formations that are commonly classified as being
“conventional” or “unconventional” in nature. Conventional hydrocarbons are those typically extracted
from soft, relatively porous and permeable rock formations from vertically-drilled wells of varying depths.
Unconventional hydrocarbons, however, come from a variety of differing geologic formations that includes
various types of sands and shales. Unconventional hydrocarbon development from shale plays also tend to
utilize a form of high pressure, artificial stimulation, known as “hydraulic fracturing” that utilizes water,
chemicals, and various propants (typically silica) to extract natural gas from shale formations found
thousands of feet below earth’s surface (Comen, 2012). This additional form of stimulation is necessary
since these unconventional resources are typically located in formations where the porosity is smaller, and/or
tighter, than those found in conventional reservoirs. As of 2009, 50 percent of all U.S. natural gas production
originated from unconventional reservoirs and is expected to increase to 60 percent by 2035 (EPA, 2004).
This energy revolution is now starting to migrate into areas known to hold a form of “shale crude oil” that
is also prolific in nature, and leading to a possible scenario where the U.S. could be energy independent by
the end of the decade (Smith, 2013).
An unconventional well goes through a number of development phases. First, an appropriate site
must be selected. Site preparation represents the second phase of the development process where roads to
a drilling site are installed, pads are constructed, supporting equipment and buildings are moved on-site, and
prepared for the next critical phase: drilling. The drilling component of a typical unconventional shale well
has both a vertical and horizontal phase. The vertical phase is comprised with drilling a well that looks
similar to “conventional” wells to a depth at which the thick layer of shale has been identified through
geological surveys and analyses. This vertical segment usually ranges at depths of between 8,000 to 16,000
feet. The well then transitions to a horizontal segment that can span a distance of between 4,000 to 6,000
feet. The horizontal well segment runs parallel with the formation adding additional well exposure in order
42
to recover a greater amount of hydrocarbons. The well (vertical and horizontal segments) is completed by
inserting and cementing various protective casings that help to secure the well, maintain its integrity, and to
prevent fluids/gas leaching into the surrounding sub-surface.
Hydraulic fracturing begins after the well is drilled and cased and utilizes millions of gallons of
usually fresh water, often pumped from a nearby source, and stored on site for future use over a fracturing
process that usually spans a few weeks (EPA, 2004). Several chemicals, often referred to as “fracturing
fluids,” are added to the water. The chemical composition of the fluids vary by region but can often include
hydrochloric acid, ethylene glycol, ammonium persulfate, citric acid, and even diesel, benzene, and arsenic
(Coman, 2012) and are used for a variety of reasons that range from reducing pipe corrosion and fouling, to
assisting in the fracturing process (Loris, 2012). A “proping” agent, usually coated silica (sand), is added
to the fracturing fluid solution and used primarily to help keep the fractures made in the shale formation
open.
The fracturing fluid solution is mixed at a 90:9:1 ratio of water: sand: chemicals, respectively
(Coman, 2012). This solution is then injected down into the well at extremely high pressures that forces the
shale formation to crack, allowing the sand to maneuver into the cracks and keep them open, releasing the
natural gas back to the surface. The length of the fracturing process is a function of the number of “cycles”
that are actual fractured, where each cycle is a function of the horizontal length of the well: the longer the
horizontal portion of the well, the greater the number of cycles that can be fractured. While the number of
cycles will vary depending upon the geologic formation and the operator, a typical horizontal well will
utilize about 12 cycles, requiring a fracturing process that runs from between 2 to 30 days.
The process of fracturing uses drills, chemicals, heavy equipment, water, and many other things that
do not naturally belong in the area raising considerably environmental concerns, the most important of which
are typically associated with water use and the potential for chemical/fluid migration into ground water
aquifers. Air pollution is also an important environmental concern given the wide range of combustion and
compression activities that occur at a typical unconventional drilling and production site. Other
environmental factors such as quality of life around fracking sites, seismic activity, and health of the workers
are important but not at the forefront of fracturing issues.
DATA AND METHODS

The Haynesville shale region is the study area for this research. The Haynesville share is comprised
of about 9,000 square miles in Louisiana and Texas and is considered a major natural gas producing shale
play in the United States (Mauck 2013). The play was formed from deposits dating back to about 150 million
years ago during the Upper Jurassic age when water covering the region receded and sediments were
deposited ultimately leading to the development of the formation (Environ, 2013). The Haynesville Shale,
has an average thickness of between 200 to 300 feet, is located about two miles below the Earth’s surface,
and is estimated to have technically recoverable resources of 251 trillion cubic feet (TCF) of natural gas
(Geology.com, 2013).
Unconventional well-specific data for the Haynesville shale was collected from multiple sources
for the time period of its most recent active development (2007-2013). The Louisiana Department of Natural
Resources (LDNR) supports an online database (called “SONRIS”) that includes information such as: true
vertical depth (TVD); measured depth (MD); lateral length; well status (active, inactive, etc.); as well as
spud and completion dates (LDNR, 2013). Fracturing stages were not reported directly by LDNR but were
estimated assuming one stage for every 328 feet of lateral section (Roy, et al., 2013). Thus, an estimated
lateral length (TVD less MD) divided by 328 provides an estimated number of fracturing stages per well.
Water and chemical use data was obtained from the online chemical disclosure registry, Frac Focus,
for each year in which such information was available (FracFocus.com, 2013). Since information for all
wells was not available, Monte Carlo-based simulation methods were used to estimate water and chemical
use where such information was missing. Total water use per well was estimated using a two-step process
where (1) well-specific water use statistics were matched to wells in the SONRIS data set for 819 reported
wells and (2) water use for the remaining 1,487 active wells, with no water use reported, was estimated
using the known range from the reported water use statistics. Chemical use data was similarly generated,
first by matching the known chemical use statistics to those in the SONRIS data set, then the proportion of
43
wells that used the chemical was found and extrapolated to all Haynesville wells and finally, using the
known concentration reported, estimates were simulated for the 707 wells with no report.
Air emission estimations were developed using similar equations such as those presented by Roy et
al. (2013) and Environ (2013). These equations were developed for two specific activities: one for drilling
activities and the second for fracturing activities. In addition, two other sets of equations were developed to
estimate air emissions from heavy duty truck traffic and completion venting. The primary air pollutants
associated with drilling and fracturing activities are NOX, CO, VOC, PM, SOX, CO2, and CH4.
ESTIMATED RESULTS AND DISCUSSION
Water Use Results The summary results in Table 1 show that estimated water use per well increases
throughout the period of investigation until about 2012 when drilling activity decreased in reaction to the
dramatic reduction in natural gas prices.
Table 1: Haynesville Shale Water Use per Well Water use increases prior to 2012 are a
Standard function of both increased drilling activity and
Year Average Minimum Maximum
Deviation
longer lateral lengths used in the wells that
--------------------------- Gallons ---------------------------
were drilled during this period. For instance,
2007 3,691,802 2,231,004 5,019,403 1,145,206 drilling activity increased by 1,883 percent
2008 3,460,253 625,464 5,592,848 1,207,282
2009 3,564,946 1,517,919 6,590,304 1,174,089
between 2007 to 2011 (the peak drilling year).
2010 4,054,394 478,513 11,868,486 1,509,802 Lateral lengths increased by 73 percent over
2011 5,463,441 367,290 34,258,678 2,383,943 the same time period.
2012 4,976,308 510,384 14,365,376 2,648,553 The drop in per-well water use from
2011 indicates the possibility of operator
learning-by-doing effects. Reduced per-well water use could indicate that operators are becoming more
efficient at using water in drilling related activities as the scope of their basin-specific experience expands.
Although all companies were found to increase their water usage throughout the years on a per well basis,
the bigger companies increased their use at a much slower rate than smaller companies.
Figure 1 shows local water use for hydraulic fracturing activities compared to other water uses
within the local parishes in which Haynesville activity has been concentrated. Estimates provided here show
that three parishes (each of which are relatively small) have estimated hydro-fracturing-related water uses
that far exceed local municipal or industrial use.
6
Total Water Use
5 Fracturing
Billion Gallons
Figure 1: Local Parish Hydro-fracturing Water Use

Relative to Other Local Uses (million gallons).
On a total state-wide basis, water use for fracturing was relatively low ranking about 8th among all
major Louisiana industries. Fracturing-related water uses were 0.05 percent of power-generation related
water uses (for cooling purposes). However, there is a big difference between the water use for power
generation purposes and fracturing: fossil fueled power generation-related water use is returned to the
system, whereas water used for fracturing is permanently disposed and not re-injected into the system.
44
Chemical Use Results. Estimated chemical uses focused on three relative potent chemicals that can be
included in fracturing fluids and include hydrochloric acid (HCl), phenol, and quaternary ammonium salts
(quats). Table 2 provides the descriptive statistics for each chemical type as well as its usage frequency (in
probability terms). For instance, 34.4 percent of the wells in the Haynesville shale either reported, or were
estimated to have used HCl in their drilling fluids over the 2007-2013 time period.
These concentrations can also be transformed into gallons used for each fracturing job. This research
estimated that, on average, a well using HCl used 12,489 gallons of the chemical, a well using phenol used
5,219 gallons, and a well using quats used 1,220 gallons. While it is true that these chemicals can become
highly diluted in a fracturing application given their mixture with about 5.6 million gallons of water, their
toxicity and ability to degrade the
Table 2: Chemical Concentrations (Gallons) and Usage Probability
environment is still relatively high.
Standard
Chemical Average Minimum Maximum Probability Phenol and quats are labeled in EPA’s
Deviation
toxicity category 1 and 3, respectively,
-------------------------- Gallons -------------------------
making them a potential threat to
HCL 0.206 0.001 0.417 0.119 34.400 human health and becoming highly
Phenol 0.086 0.003 0.181 0.049 8.000 toxic in the aquatic environment.
Quats 0.020 0.000 0.040 0.012 7.500
Table 3: Estimated Drilling-Related Air Emissions (Tons per Well) Air Emission Results. Air
emissions were calculated for all
Drilling NOX CO VOC PM SO X CO2 CH4
wells drilled and completed in the
2007 11.50 6.23 0.72 0.359 0.019 2.78 0.0017
2008 10.58 5.73 0.66 0.331 0.018 2.56 0.0016
Haynesville Shale from 2007 to
2009 9.73 5.27 0.61 0.304 0.016 2.35 0.0014 October 2013. Well specific, or
2010 9.95 5.39 0.62 0.311 0.017 2.40 0.0015 shale specific, data was used when
2011 10.03 5.43 0.63 0.313 0.017 2.42 0.0015 available, otherwise simulation
2012 9.77 5.29 0.61 0.305 0.016 2.36 0.0014 results were entered and emission
2013 9.89 5.35 0.62 0.309 0.017 2.39 0.0015
estimations were developed.
Table 3 shows estimated drilling emissions on a tons per well basis. The emissions show a slight
drop from 2007/2008 to 2009/2010 and then rise again in 2011, followed by a drop in the next two years.
Table 4: Estimated Hydro-Fracturing-Related Air Emissions (Ton per Well) Table 4 shows that 2011 is
also the same year in which per-
Fracturing NOX CO VOC PM CH4
well emission rates are their
2007 0.0620 0.0388 0.0101 0.0042 0.0038 highest during the 2007-2013. The
2008 0.0574 0.0359 0.0093 0.0039 0.0035
per-well emissions peak in this
2009 0.0600 0.0375 0.0097 0.0040 0.0037
2010 0.0616 0.0385 0.0100 0.0042 0.0038 year is attributable to the fact that
2011 0.0632 0.0395 0.0103 0.0043 0.0039 (1) drilling was at its highest level
2012 0.0646 0.0404 0.0105 0.0044 0.0039 in terms of both the number of
2013 0.0654 0.0409 0.0106 0.0044 0.0040 wells drilled in that year, but also
(2) there were a large number of both small and large companies drilling wells in that peak year (2011).
The implications this has for measuring the efficiency of air emissions will be discussed in the later section
of this paper.
Table 5
Table 5: Comparative Emissions, Drilling v. Fracturing (Per Well Basis)
summarizes the per well
Activity NOx CO VOC PM SOx CO2 CH4 air emission rates per
Drilling 10.03 5.432 0.63 0.313 0.017 2.42 0.001 pollutant type indicating
Fracturing 0.085 0.053 0.014 0.006 NA NA 0.005 the drilling related
activities clearly drive
overall air emissions relative to hydraulic fracturing. Thus, from air emissions perspective, there is not a
considerable amount of difference between the air emissions associated with conventional activities and
unconventional activities, holding total drilling depth constant.
Air emissions were compared to other major industries in the State. The pollutant of major concern
in these comparisons would be that for NOx where unconventional drilling activities, given their scale and
scope, were found to rival those of chemical and allied product manufacturing in Louisiana. Some air
45
emission efficiencies, or “learning by doing” impacts, are indicated in the results. Those companies drilling
a larger number of unconventional wells appear to emit fewer pollutants (on a per well basis) during the
fracturing stage of well development. Only the fracturing stage was looked at because that was the only
stage where per well, and thus per company, data was available.
CONCLUSIONS
This research is unique since it uses a more accurate range or well-specific parameters for the
environmental impacts of unconventional oil and gas activities. This is also the first attempt at estimating
a broader range of environmental impacts that include air emissions, water use, and adverse chemical uses.
The empirical results indicate that the Haynesville Shale is a major emitter of air pollutants but at
levels considerably lower than other major industries in Louisiana. While unconventional hydro-fracturing
activities use a considerable amount of water, this use is moderate at the state-wide level. However, for
three of the smaller parishes investigated in this research, this increased water use has been considerable
and warrants continued observation.
The chemicals used in fracturing should be handled with care because of the amount used and the
relative toxicity to the environment and humans of each chemical. It is shown that the Haynesville Shale
has become more efficient in unconventional drilling activities by decreasing drilling time, increasing lateral
lengths and stages to recover more resources. Though still of concern, environmental effects have lessened
from big companies because they have decreased their air emissions and slowed their water use per well
over time.
ACKNOWLEDGEMENTS
The authors wish to acknowledge and thank the LSU Center for Energy Studies at LSU for the
financial support for this research. The authors also thank Siddhartha Narra for his technical assistance in
several parts of this project.
REFERENCES
Coman, Hannah. "Balancing the Need For Energy And Clean Water: The Case For Applying Strict Liability
In Hydraulic Fracturing Suits." Boston College Environmental Affairs Law Review 39.1 (2012): 131-
160. Academic Search Complete. Web. 26 Nov. 2012.
Environ. “Emissions from Natural Gas Exploration and Production Activity in the Haynesville Shale.”
Environ. January 2013.
Geology.com. “Haynesville Shale: News, Map, Video, Lease and Royalty Information.” Geology.com.
Web. 2 Oct. 2013. <http://geology.com/articles/haynesville-shale.shtml>.
Loris, Nicolas. “Hydraulic Fracturing: Critical for Energy Production, Jobs, and Economic Growth.” 28
Aug. 2012. The Heritage Foundation. Web. 12 Feb. 2013. <http://www. heritage.org/research/reports>.
Mauck, Keith. “What is the Haynesville Shale?” GoHaynesvilleShale.com. Web. 2 Oct. 2013.
<http://www.gohaynesvilleshale.com/notes/Haynesville_Shale>.
Roy, Anirban A. Adams, Peter J. & Robinson, Allen L. “Air Pollution Emissions from the Development,
Production, and Processing of Marcellus Shale Natural Gas.” Journal of the Air & Waste Management
Association, 2013, Vol 64(1), 19-37, DOI: 10.1080/10962247.2013.826 151.
Smith, Grant. “U.S. to Be Top Oil Producer by 2015 on Shale, IEA Says.” Bloomberg, 12 Nov. 2013. Web.
7 April 7, 2014. < http://www.bloomberg.com/news>.
U.S. Environmental Protection Agency. “EPA Hydraulic Fracturing of Coalbed Methane Reservoirs Study.”
2004. Web. 26 Oct. 2012. <http://water.epa.gov/type/groundwater
/uic/class2/hydraulicfracturing/wells_hydrowhat.cfm>.
U.S. Department Of Energy. “Shale Gas Glossary.” United States Department of Energy. Web. 2 Oct. 2013.
http://energy.gov/sites/prod/files/2013/04/f0/shale_gas_glossary.pdf.
46
CORRELATIONS BETWEEN CHLORINATED ALIPHATIC HYDROCARBONS AND

ENVIRONMENTAL VARIABLES IN A CONTAMINATED GROUNDWATER IN SHANGHAI,
CHINA
Lu Qiang*, Li Hui, Lin Kuang Fei, and Liu Yong Di

(East China University of Science and Technology, Shanghai, China)
With the development of manufacturing in China's Yangtze River Delta, processing enterprises has exposed
a large number of enterprise-situ soil and groundwater contamination incidents during the process when
industry layout adjusted and moved out subsequently land transferred and re-circulated. Chlorinated
aliphatic hydrocarbons (CHs) as a cleaning solvent in manufacturing plants widely contaminated soil and
groundwater due to its extensive usage and inappropriate disposal practices. Natural attenuation reactions
of anaerobic aquifers contaminated with CHs always take place and it has become a research hotspot.
This study focused on correlations between CHs and Environmental variables in a shallow
groundwater contaminated by 1,1,1-Trichloroethane (1,1,1-TCA) in Shanghai, to characterize the natural
attenuation law of CHs. Site data from monitoring wells are presented and analyzed. The results showed
that less chlorinated products including 1,1-dichloroethane (1,1-DCA), 1,1-dichloroethene (1,1-DCE),
chloroethane (CA), and vinyl chloride (VC) were found, CA and VC were accumulated. The plumes
distribution of contaminated groundwater covered an area about 5,000 m2 and located in the 4-8 m clay bed
underground, including about 50 m3 dense non-aqueous phase liquid (DNAPL). Heatmap of multifactorial
analysis for CHs and environmental variables showed that it was a significant negative correlation (P<0.001)
between Fe2+ and 1,1,1-TCA, 1,1-DCA, 1,1-DCE, while a significant positive correlation (P<0.001)
between Fe2+ and CA, VC. Cl- showed a similar phenomenon. In conclusion, the correlation between CHs
and Fe2+, and/or Cl-, could become a useful tool for charactering the natural attenuation of CHs in
contaminated groundwater.
47
REMEDIATION OF ACIDIC GROUNDWATER USING A SODIUM BICARBONATE

INJECTION SYSTEM
Christina Brown, Paul Marotta (AquAeTer, Inc., 215 Jamestown Park, Suite 100
Brentwood, TN 37027, USA)
David Wall (Highland Technical Services, Inc., 528 Mineral Trace, Hoover, AL 35244, USA)
Teresa Jordan (Tierra Solutions, Inc., Two Tower Center, Floor 10, East Brunswick, NJ 08816, USA)
Christina DeJarlais (Boulder Environmental Consulting, 3938 West Boulder Lane, Perry, MI 48872, USA)
Highly acidic groundwater required remediation at a site in Alabama consisting of a closed impoundment
(slurry wall and multi-media cap) adjacent to a River. The Alabama Department of Environmental
Management (ADEM) requested that the facility develop a corrective action plan to raise the pH levels
exterior to the slurry wall to at least 5.5 standard units (S.U.). A low-cost, low-maintenance sodium
bicarbonate injection system was installed at the Site. The monitoring data demonstrate successful
neutralization of the aquifer and movement of the injected solution over distances as far as 200 feet, as well
as cross gradient. The data also confirm that mixing was adequate for the groundwater neutralization
process and that precipitation formation did not impede groundwater flow or alkalinity distribution. Two
years post-injection, the pH levels have remained above the targeted pH of 5.5.
The delivery system was designed to feed the sodium bicarbonate solution into the injection well
by gravity from 3,000 gallon above ground storage tanks. This low-maintenance design eliminated the need
for pumps, electrical supply, or other equipment. Overall, the system had very minimal startup costs and
essentially no maintenance costs. The ability to easily relocate the injection to optimal locations within the
aquifer was a significant benefit of the design and a key to the success of this remediation system. In total,
approximately 901,000 gallons of saturated bicarbonate were injected versus the predicted amount of
913,000 gallons of saturated solution, indicating the ability to accurately estimate the required amount of
solution required to meet the remediation goal at the Site within 1%.
48
A COMPARATIVE STUDY OF ENHANCED BIOREMEDIATION TECHNIQUES FOR A BTEX

COMPOUND (TOLUENE) IN CONTAMINATED GROUNDWATER
Shreejita Basu*, B. K. Yadav, Anuj Mathur* and Shashi Mathur *

*(Indian Institute of Technology,Delhi, India)
(Indian Institute of Technology, Roorkee, India)
ABSTRACT: Bioremediation is an ecofriendly technology for removing petroleum derived contaminants

like BTEX. BTEX group of chemical contaminants consists of benzene, toluene, ethylbenzene and three
isomers of xylene. The natural attenuation of these compounds by indigenous microorganisms is quite slow.
Many studies have shown success with enhanced or engineered bioremediation which accelerates the natural
process. The objective of this study was to investigate the biodegradation of a BTEX (Toluene) under four
different bioremediation techniques. In the first case natural biodegradation of toluene was studied using
polluted groundwater collected near an oil refinery in India. In the second case biostimulation was studied
by mixing the collected groundwater with domestic wastewater in equal proportions. To study the remaining
cases, small scale wetland with plants of Canna genralis was developed in the laboratory without and with
the presence of toluene in the rhizosphere. The wetland system with toluene was used for developing the
pre-grown microbial cultures to enhance the degradation rate of the BTEX. Plant-enhanced biostimulation
was studied by adding the polluted groundwater to the root-zone water of the wetland system developed
without presence of toluene.Then biostimulation was coupled with bioaugmentation, by mixing the
groundwater with root-zone water of the wetland system developed in presence of toluene. A comparative
account of these different bioremediation techniques is presented for their respective rates of biodegradation,
duration of lag phases, and the total time of degradation. It is seen that the plant enhanced bioremediation
technique has a faster rate as compared to natural bioremediation. The results of these experiments can be
beneficial in framing the engineered bioremediation plan for BTEX contaminated groundwater systems.
INTRODUCTION
Huge amounts of hydrocarbon contaminants are released into the environment as a result of
anthropogenic activities. Emissions from the industries can still be controlled but accidental spillage from
tankers, pipelines and storage tanks are unavoidable circumstances which keep occurring now and then
(Salleh et al.,2003).Petroleum hydrocarbons are the most widespread contaminants in soil and water
(Margesin,2001).Amongst such hydrocarbons, several components are biodegradable, some are recalcitrant
and others have intermediate biodegradability (Tyagi et.al 2011).Hydrocarbons like non-aqueous phase
liquids (NAPLs) exist as a separate, immiscible phase from the aqueous(dissolved) and gas phases(air).They
are specifically classified as either light non aqueous phase liquids (LNAPLs), having densities less than
that of water or dense non aqueous phase liquids (DNAPLs), which have densities greater than that of water
(Newell 1995).LNAPL’s include gasoline, BTEX, diesel fuel, MTBE, alcohols and most non-halogenated
petroleum derived liquids, while DNAPL’s include chlorinated solvents such as trichloroethylene(TCE),
perchloroethylene (PCE) and carbon tetrachloride (TCA).These chemicals have varying degree of solubility
in water.BTEX (benzene, toluene, ethyl benzene, xylene), amongst LNAPL’s have high solubility in water
which causes them to spread in the sub-surface widely(Margesin et al.,2003) and pose a long term
groundwater contamination problem.These contaminants can dissolve into groundwater, adsorb to aquifer
sediments, volatilize and diffuse through the unsaturated zone, or subject to natural attenuation including
physical phenomena, chemical and biological processes(Lahvis et al.1999).Owing to the toxicity of these
compounds it is inevitable to look for remediation options that are environmentally benign.
Over the past few decades various remediation techniques have come into the limelight.The removal
of such mono aromatics from soil-water systems can be done by chemical methods like use of dispersants,
49
chemical oxidation, photo catalysis remediation (Mascolo et.al,2007).Some physical techniques like
physical containment, booming and skimming, mechanical removal, water flushing and sediment
relocation(Zhu et. al 2004).Also electro remediation, air sparging, carbon adsorption, filtration, adsorption
by zeolites are used widely (Daifullah and Girgis,2003; Ranck et. al,2005; Yang et. al, 2005). Pump and
treat is feasible only if substantial amount can be recovered from contaminated aquifer (Udell et al. 1995).
Use of high pressure, hot water and burning can lead to destruction of indigenous biota and air pollution.
The use of co-solvents has its disadvantage in respect to its efficacy and toxicity concern for long period of
time (USEPA, 1998). The other promising treatment option is through biological processes like
bioremediation, biodegradation in reactors, phyto-remediation and wetlands (Rozkov et al.,1999; Langwaldt
and Puhakka,2000; Vidali,2001; Lynch and Moffat,2005; Wallace and Kadlec,2005; Farhadian et al.,2006;
Martıńez et al., 2007).Bioremediation is a popular cost effective technique and causes no harm to the
contaminated ecosystem as compared to the chemical and physical methods (Yang et al. 2009).It can be ex-
situ which physically remove the contaminated material and treat it at a separate treatment facility or insitu
which treats the contaminated material in place itself (Iwamoto,2001).Mostly it has been used as a
secondary/complementary polishing method after applying a conventional mechanical remediation step to
remove the bulk of the contamination. However over the last decade bioremediation has been found as the
primary procedure for clean up of low-level hydrocarbon spills and for sensitive areas where conventional
clean up techniques are not feasible (Zhu et.al,2004).Petroleum products like BTEX are proven to be easily
degraded in the aerobic environment.(Smith, 1990; Zylstra, 1994). Natural attenuation is successful for
BTEX present in groundwater and their 90% of removal is attributed to the intrinsic biodegradation process
(Kao and Prosser, 2001;Barton, 2000;Grossl 2000, Spadaro, 2000).But, natural attenuation is a very slow
process and the removal in most cases is not complete.Thus in order to make it faster, engineered/enhanced
bioremediation is practiced using additives to the natural environmental media.The engineered
bioremediation include strategies involving the addition of seeded cultures, bio augmentation or addition of
nutrients, bio stimulation, that hold the promise of epitomising in situ bioremediation.
The response of bio stimulation and bio augmentation towards degradation of hydrocarbons present
in oil are a mixture of successes and failures. Bioremediation strategies have been applied to clean up spills
from petroleum products under a broad range of environmental conditions like soil and groundwater
systems, marine shorelines, surface water etc. Many studies have compared the performance of
bioaugmentation and biostimulation and found that the nutrient addition alone was more efficient than
adding microbial seeds. (Jobson et.al, 1974, Lee et. al., 1997; Venosa et al., 1996).The key role in the
success of bioremediation in contaminated soil-water systems is played by microorganisms and various
environmental parameters which affect their growth like nutrients, air,moisture content, temperature
etc.Many researchers have proven that plants can play a role in actively promoting microbial restoration of
chemically contaminated soils and water due to continuously supplying of basic nutrients for microbial
growth because of fixation and exudation processes (USEPA, 1992; Aprill and Sims, 1990; Davis et al.,
1993; Narayanan et al., 1998b; Zhang et al., 1996).The aim of this study was to find the most-effective
feasible way of remediating the BTEX contaminated groundwater collected from an oil refinery site using
enhanced bioremediation,in combination with plants.

Contaminated groundwater from two different hand-pumps in vicinity of Panipat refinery in
Haryana, India was used. The collected groundwater was left open under ventilation hood to remove all
volatile components and was later used as a primary source of toluene degraders. The primary treated
domestic wastewater was collected from the campus of Indian Institute of Technology (IIT) Delhi. Both the
groundwater and the domestic wastewater were stored in cold storage at 4°C in 20 L containers for further
utilization.A stock was prepared dissolving toluene (Merck with 99.9% purity) in distilled water to its
solubility limits (≃ 490 mg/L) at room temperature.Batches of 120 ml capacity were assembled by adding
appropriate volume of stock solution to get required initial concentration of 8 mg/L.Based on simple mass
balance, a headspace of about 110 ml was provided to maintain aerobic condition throughout the
experimental period for degrading the total added toluene in all the batches. Viton stoppers (Centurion
Scientific, India) sealed with aluminum crimp were used to prevent any leakage of toluene. In each batch
appropriate amount of groundwater, wastewater and/or wetland water were used to make a final volume of
50
10 ml.Sterile batches were prepared by adding 60 µL of 10g/L of HgCl2, in order to observe the abiotic
losses.After closing batches air tightly, 160 µL of toluene stock was injected through the stopper with a gas
tight syringe. They were then thoroughly shaken and were incubated on orbital platform having 150 rpm.All
the batches were covered with a black cloth at room temperature to prevent interference of light.
Preliminary batch experiments were run first at room temperature to test the toluene degradability
of the microbiota present in the groundwater.The amount of HgCl2 for sterilization purpose, and liquid
sampling interval were also determined by the preliminary batch experiments.Two sets of batch experiments
were then conducted at room temperature by maintaining the initial substrate concentration as 8 mg/L. A
set of two small wetlands were developed using 40 litre of viton coated containers packed with pea gravels
of 0.4 cm size. Plants of Canna generalis were grown in the containers in laboratory premise of IIT Delhi
where abundant sunlight was present during the day time. The collected domestic wastewater was used as
growing media in both of the wetlands. In one wetland, no toluene was added and approximately 50 mg/L
of toluene concentration was maintained in another wetland for initial five weeks and allowed to attenuate
in the last week of the experiment.Similarly, a total acclimatization time of six weeks was provided to the
second wetland before utilizing the rhizospheric water for batch experiments.Viton tubes with a small
diameter were attached to the top and bottom outlets of both the wetlands for adding water lost due to
evapotranspiration and for collecting the rhizospheric water samples.Only groundwater was taken for the
first case,a mixture (1:1) of groundwater and domestic wastewater was taken in the second case and a
mixture (1:1) of groundwater and rhizospheric water of wetlands developed without and with presence of
toluene was taken as 3rd and 4th cases for batch experiments.
The concentration of toluene in the liquid sample was calculated from their peak area on GC/FID
spectra based on standard calibration curve. Triplicate live batches were used along with sterile batches.
Samples of 4 µL were taken out periodically using 10 µL syringes (Hamilton) for measuring the toluene
concentration using a Nucon gas chromatograph (model 5765) equipped with a flame ionization detector
(FID). A chromatopak stainless steel column (6% ft, 1/8 inch metal WIHP, 80/100 mesh) was used. Nitrogen
was employed as the carrier gas at a flow rate of 25 ml/min. Air and hydrogen with a flow rate of 20 ml/min
are used for FID. The temperature of injection port, oven and detector port were kept 150°C, 120°C, and
150°C respectively.

The graph in Fig. 1 is plotted between normalized (C/Co) toluene concentrations and time of
progression. The sterile batch showed a little deviation from its initial concentration due to abiotic losses of
the substrate. The experimental results of natural biodegradation (Case 1) show that toluene concentration
decreases slowly with time and a total time period of 26 hours is taken by indigenous microbes to degrade
the entire BTEX mass in groundwater. For biostimulation (Case 2), there was neither significant increment
in rate of degradation, nor, depreciation in time of degradation by addition of wastewater. This shows that
collected groundwater has sufficient nutrients during the entire phase of degradation for the added mass of
contaminant.The case of plant-assisted biostimulation(Case 3) gave faster degradation rate. Narayanan et
al. (1998b) emphasized that plant roots exude a wide range of compounds varied from amino acids, sugars
and carbohydrates to essential vitamins which act as growth and energy substrates for the microbes. This
means that root exudates work as the most favorable carbon source to toluene degraders and hence play a
crucial role in biostimulating of rhizospheric microorganisms. Another important finding of this case is the
shorter duration of lag phase, for plant-assisted biostimulation. Thus it is prominent that roots exudates are
the most favorable carbon source for indigenous microbes and hence are capable to degrade the target
pollutants with small time of acclimatization. In case of bioaugmentation and biostimulation (Case 4),the
lag phase was negligible and the degradation time was shortest as in Fig.2.This technique had the maximum
rate of degradation in comparison to natural biodegradation. So it is confirmed from our findings that root
zone plays a positive role in quick acclimatization and growth of BTEX degraders in polluted water systems.
It is consistent with the previous study by Weishar et. al. (2009) who observed that vegetated BTEX
contaminated site had more BTEX degrading population than the barren contaminated land. (Chi-Wen Lin
et al, 2010, Gomez et. al,2006).The rhizosphere water collected from the first wetland was deprived of
toluene degraders as it was developed without presence of toluene. The second wetland was acclimatized
with toluene and, therefore, the rhizosphere water was rich in toluene degraders.This explains the reason of
51
shorter lag time of case 4 as compared to case 3 . Thus, the batch experiments representing different
techniques of bioremediation using the wetland system without and with presence of toluene provided
valuable results on the impact of rhizospheric zone in the bioremediation strategy for the BTEX
contaminated sites.
1.2
1
0.8
Sterile
С/ 0.6 Case 1
C₀ 0.4 Case 2
Case 3
0.2 Case 4
0
-0.2 0 5 10 15 20 25 30
Time in hour
Figure 1. Attenuation and degradatuion time of toluene in four different cases of bioremediation
SUMMARY AND CONCLUSION

Out of the four techniques, the rate of degradation of toluene is found as: Natural
degradation<Biostimulation < Plant-assisted biostimulation < combination of bioaugmentation and
biostimulation. The results showed that, the rate of toluene degradation increases dramatically in cases of
plant-assisted bioaugmentation and biostimulation.This highlights the importance of rhizosphere in quick
acclimatization of microorganisms for remediation of BTEX contaminated water resources.
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54
INTERACTIONS OF ARSENIC DESORPTION AND INDIGENOUS BACTERIAL ACTIVITY

IN SHALLOW GROUNDWATER SYSTEM
Zuoming Xie*, Guangming Ouyang, Yanxin Wang, Xiaoyan Sun and Dong Yang
(School of Environmental Studies, China University of Geosciences, 430074 Wuhan, P. R. China)
In this work, bacterial activity in enhanced arsenic environment and arsenic desorption by bacteria were
investigated. Three different types of soil sediments, mealy sand, loamy sand and clay loam were chosen
with high arsenic in shallow groundwater. The results showed that arsenic desorption rate was related to
bacterial activities and soil texture. Under the same bacterial activities, arsenic desorption rate was the
highest from mealy sand, and lowest from clay loam. However, bacterial activity in sediments was just
reverse. The bacterial activity was strongest in clay loam under the same arsenic content, and weakest in
mealy sand. The results in this study also demonstrated that concentrations of arsenic accumulated in
bacterial cells had remarkable difference between from As(III) solution and from As(V) solution.
55
OPTIMIZATION OF FLUORIDE REMOVAL FROM ALUMINIUM SMELTER

CONTAMINATED GROUND WATER
Sleap S.B, Turner B.D, KrabbenhØft K, Sloan S.W

(Centre for Geotechnical and Materials Modelling and Australian Research Council Centre of Excellence
for Geotechnical Science and Engineering, The University of Newcastle, Callaghan, N.S.W., 2308,
Australia)
Aluminium is one of the most widely used metals on the planet. It is primarily produced by the electrolytic
reduction of alumina in a cryolite bath. During the process, components of the cryolite, metals and other
chemicals are slowly absorbed by the carbon linings. The foremost constituents, which are absorbed in the
reduction process are; sodium, fluoride and cyanides. The carbon linings break down over time and must be
replaced. When the linings infused with the by-products of the smelting process are removed they become
known as spent potlining (SPL). SPL is a designated hazardous solid waste of the aluminum manufacturing
process, which requires appropriate management, storage, treatment and disposal.
Historical SPL storage practices at Hydro Aluminium Kurri Kurri, a now decommissioned
aluminium smelter located in the Hunter Valley region of New South Wales, Australia, has led to
contamination of groundwater in a localized shallow aquifer on the plant site. The purpose of this research
was to investigate remediation options which were both environmentally sound and economically feasible.
A four phase geo-remediation plan was developed: Phase 1, extensive site characterization using a
variety of Cone Penetration Testing (CPT) techniques and groundwater monitoring. Phase 2, the design and
optimization of a Permeable Reactive Barrier (PRB) to prevent further contamination of the aquifer. Phase
3, utilising the natural hydraulic gradient to remove contaminated groundwater. Phase 4, determining the
optimum method of fluoride removal from the extracted contaminated groundwater.
The optimum location for both the PRB and injection bores, were determined via site
characterization. Pilot scale testing of the proposed PRB concluded that CO2(g) injected into a calcite barrier
was effective in removing >90% of fluoride. Extensive investigations of the kinetics of fluoride removal
from SPL leachate in a calcite/CO2 system revealed that optimum removal occurred with pCO2 ~60%,
utilising calcite with a fraction size < 150µm, whilst being vigorously stirred. Increasing the temperature to
400C increased the rate of fluoride removal, indicating the importance of seasonal fluctuations on the
remediation process.
Conservative experimental results indicate that 92% fluoride removal can be rapidly achieved under
the optimal conditions with up to 97% removal achieved given enough contact time. Assuming an average
fluoride concentration of 700 mg/L across the site, 95% removal leaves a residual of 35 mg/L, a figure on
target with the regulatory treatment level.
The direct disposal option of untreated groundwater by local waste operators would cost between
$250,000AU to $292,000AU per ML. Direct untreated disposal of SPL leachate is not seen to be financially
viable. Given the presence of an estimated 120ML of raw leachate, direct disposal would cost in excess of
$30,000,000AU. This figure does not take into account the residual volume requiring treatment from
desorption from the soil over time.
Using the optimization method developed, and based raw materials (excluding plant and equipment
capital costs, setup costs, labor or depreciation, etc.), it is estimated that treatment costs of SPL leachate
from the site will be in the order of $8,000AU per ML. Residual sludge volume may require landfilling.
However, fluorite (CaF2) may be able to be extracted from the sludge at an appropriate purity to be sold on,
further reducing the cost of remediation.
56
A PILOT SCALE PERMEABLE REACTIVE BARRIER FOR THE TREATMENT OF SPENT

POTLINER CONTAMINATED GROUNDWATER
Turner B.D*, Sleap S.B, KrabbenhØft K, Sloan S.W

(Centre for Geotechnical and Materials Modelling and Australian Research Council Centre of Excellence
for Geotechnical Science and Engineering, The University of Newcastle, Callaghan, N.S.W., 2308,
Australia)
A major concern with contaminated sites is their potential for off-site environmental effects by the leaching
of contaminants to adjacent lands and groundwater aquifiers. As groundwater underlies 60% of Australia
(some 5,226,440 square kilometres) it is therefore a vital source of water that is constantly under threat of
contamination. The use of in situ engineering treatment methods such as permeable reactive barriers (PRB’s)
is a cost effective and environmentally sound method of removing contamination from point sources. PRB’s
are passive walls containing a chemically active material that reacts with groundwater contaminants as they
pass through the barrier. However, reactive barriers still have many technical uncertainties associated with
them, especially in regard to their long term performance.
Spent potliner (SPL), a by-product of the aluminium smelting process, is listed by various
environmental bodies including the US EPA as a designated hazardous waste primarily due to the high
levels of leachable fluoride, cyanide and pH (>9.5). World-wide it is estimated that the total amount of SPL
produced is approximately one million tonnes per year with the bulk of this being stored in purpose built
storage facilities. At the Hydro Aluminium smelter near Kurri Kurri, NSW, Australia, SPL was dumped by
previous owners in an unlined waste repository from 1969 to 1992 resulting in localized contamination of
the groundwater aquifer with high levels of fluoride.
This project utilized the groundwater remediation test facility at the University of Newcastle,
Australia to assess the use of calcite as a reactive barrier substrate for the remediation of fluoride from
groundwater contaminated with SPL leachate. The facility houses a 3.0m x 2.0m x 1.3m high pilot cell that
can be configured with up to 40 individual cells to represent a reactive barrier installation. Pilot tests were
setup to examine optimal methods of injecting CO2 gas for pH control and thereby fluoride removal.
Methods included injection upstream of, and directly into, the calcite barrier using slow release gas
permeable tubing or high flow injection using ~50mm diameter spear point installations.
Over a period of 28 days, approximately 26,000 litres of actual SPL contaminated groundwater (pH
9.5; [F-] ~500 mg/L) was allowed to flow through a simple aquifer of clean sand and a single barrier of
calcite (1.8m high x 1.3m wide x 0.3m thick). Contaminant data (fluoride, pH, electrical conductivity, and
major cations and anions) were collected at defined intervals (~6 hourly) in a 1-dimensional array from
upstream of the barrier, 3 points within the barrier, and 2 points downstream. Data was also periodically
collected from within the barrier to characterize chemical changes vertically.
Results show that, following breakthrough (based on the non-reactive chloride tracer), little or no
fluoride was removed due to inhibition by an as yet undefined reaction between the SPL leachate and the
calcite substrate as previously reported by the authors. Injection of 100% CO2 upstream of the barrier has
very little effect on fluoride removal, whilst injection directly into the calcite barrier showed that >90%
fluoride removal can be attained with the added benefit of removing the coffee coloured taint from the SPL
contaminated groundwater. Changes in the porosity of the calcite barrier were also examined using cores
obtained by injection of resin into a 100mm diameter tube inserted into the calcite barrier before and after
testing. Results indicate that after 28 days and 26,000L of leachate there was no significant change in the
porosity of the calcite barrier.
57
RESIDUES OF VETERINARY ANTIBIOTICS IN ENVIRONMENTAL WATERS IN CENTRAL

JIANGHAN PLAIN, CHINA
Tong Lei, Wang Yanxin, Liu Hui, Li Minjing

(School of Environmental Studies, China University of Geosciences, Wuhan, China)
Antibiotics have been widely used in livestock industries since the early 1990s in China. Despite the positive
effects, the overuse of antibiotics in livestock feed leads to high concentrations of antibiotics and their
metabolites in the waste. Therefore, these drugs and their metabolites can eventually enter ground and
surface waters following the common practice of applying manure to agricultural fields. In the present study,
the occurrence of antibiotics in surface water and groundwater in a vulnerable aquifer was investigated. The
study area locates in the central part of Jianghan Plain, Hubei, China (near Yangtze River, southwestern part
of Wuhan city). Low, flat and crisscrossed by rivers and lakes, Jianghan Plain is famous of its agriculture in
animal husbandry, fishery and planting industry. The Yangtze River and other located rivers recharge and
discharge into groundwater because the hydraulic head of the confined aquifer is equivalent to the surface
water.
A total of 25 groundwater and 9 surface water samples were collected from Shahu County, Jianghan
Plain. Surface waters were collected as a grab sample from near fishponds and main rivers, including East
Wuhu Lake, Tongshun River, Kuige River and Lvfeng River, which flowed across the town. Groundwater
samples were sucked from hand tube wells. The in situ filtration (0.45 μm) was adopted after sampling and
antibiotics were measured immediately by solid-phase extraction and Liquid chromatography tandem mass
spectrometry. Nineteen antibiotics belong to four groups, sulfonamides (SMs), fluoroqinolones (FQs),
tetracyclines (TCs) and macrolides (MLs) were all detected at least once in surface water and groundwater
in study area. For each compound appeared in different sample sites, it obviously that surface water has
been polluted heavier than groundwater. Chlorotetracycline, doxycycline and enrofloxacin were the three
antibiotics with high concentrations and high relevance ratios in two kinds of water samples. Frequency of
detection as high as 100% was found in most macrolide compounds, interestingly, the detected
concentrations of which were less than 5 ng/L. High frequency of detection represents widespread use of
these compounds in fish ponds or animal husbandry near the main rivers in Shahu County. Antibiotics
concentrations in groundwater were highly variable across wells. The differences in residue levels and
detection frequency for antibiotics mentioned above could be attributed to variations in dosage levels of
animals and metabolic characteristics in the environment.
58
PREDICTION OF COUNTY-LEVEL NEW CONTAMINATION CASES FROM HISTORIC

GROUNDWATER CONTAMINATION CASES THROUGH DATA DEPENDENT MODELING
Qing Li, Fengxiang Qiao, and Yu Lei (Texas Southern University, Houston, Texas, USA)
ABSTRACT: Groundwater is one of the most important natural resources associated with the environment,
public health, welfare, and long-term economic growth. Billions of populations rely on the groundwater for
their daily activities. However, thousands of contamination cases have been documented in many
groundwater reports. The primary contaminants are artificial products such as gasoline and diesel. To protect
the important water resource, a series of efforts have been exerted including enforcement and remedial
actions. Every year, the Texas Groundwater Protection Committee (TGPC) publishes a “Join Groundwater
Monitoring and Contamination Report” described historic and new contamination cases in each county,
which is an important data source for the prediction and design of prevention strategies. In this paper, a data
dependent modeling (DDM) approach is proposed to predict the county-level new contamination cases
(NCC). A case study with contamination information from Harris County in Texas was conducted to
illustrate the modeling and prediction process with promising results. The one-step prediction error is 1.5%,
while the two-step error is 12.1%. The established model is applicable for the use at county-level, state level,
and even country level, while the prediction results could be a kind of reference during decision-making
process.
INTRODUCTION
According to the Environmental Protection Agency (EPA), 97 percent of the rural population
depends on groundwater for drinking in Unite States, and 40 percent of people living in United States use
groundwater in their daily life for drinking, cooking, cleaning, irrigation, and other types of activities
(Moody, 2014). Groundwater has been considered as the safest fresh water resource. However, the
groundwater is confronting depletion and contamination has been threatening its supplies (Konikow, 2013).
As a matter of fact, except the saltwater intrusion, contamination is more likely to occur in natural recharge
process for groundwater. Specifically, in rainwater harvesting, many pollutants may be brought into
groundwater by penetration with surface water and eventually deteriorate its quality. The pollutants mainly
are the artificial products, such as gasoline, oil, road salts, and chemicals, with which they will pose
enormous health effects. For instance, people may suffer from diseases such as hepatitis and dysentery
through drinking contaminated groundwater from septic tank waste, and they may be poised by toxins that
leached into well water supplies. Other long term effects such as certain types of cancer may be resulted
from the exposure to the contaminated groundwater. Many efforts have been made to protect the
groundwater resources from deterioration, including enforcement and remedial action. Nevertheless, there
are still many new groundwater contamination cases recorded every year. Furthermore, groundwater
remediation is a complicated and a time-consuming work due to its location, in soil pore spaces, and in the
fractures of rock formations. Prevention is always better than cure, while prediction is essential for
preventive strategies. There are many methodologies dedicated to the prediction of specific contamination
in groundwater for protection purpose. For instance, Hossain et al. (2013) developed the arsenic
contamination risk map using a combination of classification tree and Geographic Information System (GIS)
technology. United States Geological Survey (USGS) scientists developed a methodology based on the age
of oil and gas wells, the type of soil, the distance from wetlands and streams, and the density of the wells in
the area to predict the likelihood of contamination. However, less research has been conducted on the
relationship between the historical contamination cases and new cases that potentially take place in
groundwater in the near future. This calls for a novel method to predict the new contamination cases in a
region.
RESEARCH OBJECTIVES
59
This study intends to develop a data dependent model (DDM) to predict the number of new
contamination cases (NCC) at county-levels. The base data are the existing contamination cases from the
Texas Commission on Environmental Quality (TCEW) in annual Join Groundwater Monitoring and
Contamination Reports (JGMCR). The proposed model is tested by a case study in Harris County, USA.
THE SOURCE DATA

The Texas Groundwater Protection Committee (TGPC) services to bridge gaps between existing
state groundwater programs, and to optimize water-quality protection by improving coordination among
agencies involved in groundwater activities. The TGPC publishes Annual JGMCR based on the activities
of ten coordinated organizations, including the Texas Commission on Environmental Quality (TCEQ), the
Texas Water Development Board (TWDB), the Railroad Commission of Texas (RCT), and the Department
of State Health Services (DSHS). The report provides the annual status of groundwater monitoring
associated with the regulatory, planning, and administrative programs of state agencies and local
groundwater conservation districts. Also, it reports the annual status of documented groundwater
contamination reasonably suspected of having been caused by activities under the jurisdiction of those
programs.
Specifically each year, in the table of groundwater contamination case descriptions, there are eleven
columns including the information on county, division, indication of new case, file name, file number, case
location, contamination description, date occurred, enforcement status, data quality, and section number.
They are reported by the Texas Natural Resource Conservation Commission.
These tables reveal that the main contaminations in groundwater are solvent, gasoline, volatile organic
compounds (VOCs), and related petroleum products. What’s more, the tables also demonstrate the progress
of enforcement and remedial action for existing individual case, and conformed new contamination cases
(NCC) occurred each year. This is a primary data source to build up the suitable prediction mechanism for
NCC.
DATA DEPEDENT MODELING OF CONTAMINATION NEW CASES
Mathematical Representation. In order to better understand how the NCC various each year, and to better
model such variation for prediction purpose, a mathematical notation system for NCC observation is
defined. A discrete series = , ,…, is used to denote the number of successively observed
NCC in a region (e.g., a county in Texas), where i represents the year observed, n is the total number of
observations that is also the number of years covered, and is observed at a uniform sampling interval
(e.g., once a year). The series is called a time series since all samples are collected chronically. As it
might be very difficult to physically describe all factors that may affect the series , one feasibly way to
model such series is to seek for a suitable model to capture the autocorrelations between those successive
observations. The data dependent modeling procedure is capable of simulating and predicting a stationary
time series (Pandit, 1991; Qiao and Yang, 1998; Qiao, 2010).
The Data Dependent Model. One traditional data dependent model is the famous ARMA(n, m) model
(Pandit, 1991), where AR(n) is the auto-regression of n observed data, and MA(m) represents the moving
average with order m. The expanded expression of the ARMA(n, m) model is in Equation 1.
=∅ +∅ + ⋯+ ∅ + − + + ⋯+ (1)
In Equation (1), is the NCC at year t, means the NCC at ith year before year t, while is a sequence
of uncorrelated variables or shocks, following an independent normal distribution: ~ 0, . ∅
and are the coefficients of and that can be calibrated from observed data sets. All terms
on the right hand side of equation (1) are related to auto-regression, while all terms are related to
! " and # " using algorithms such as the Forward-

moving average.
The coefficients ∅ and can be calibrated as ∅
Backward algorithm (FB), the Least Squares algorithm (LS), the Yule-Walker algorithm (YW), the Burg's
60
algorithm (BURG), and the geometric lattice method (GL) (Pandit and Wu, 1983). With the calibrated
coefficients, the NCC number at year t can be estimated as:
!
# =∅ !
+∅ !
+ ⋯+ ∅ −# +# + ⋯+ # $ (2)
where, = − # , n and m are orders of auto-regression and moving average parts, respectively,
while the prediction error % at step t is . If multiple ARMA models are involved, the goodness of models
can be examined through indexes such as the Akaikes Final Prediction Error (FPE).
FPE = ) ∗ 1 + 2 ∗ -/ (3)
where ) is a loss function, d is the number of estimated parameters, and N is the number of estimation data
samples. The detailed FPE calculation can be found in Pandit and Wu (1983) and Pandit (1991).
Modeling Steps. By definition, a stationary time series should come from a stationary stochastic process,
where the mean is constant and can be assumed as zero without loss of generality (Pandit and Wu, 1983).
However, there is no any evidence that the observed NCC series is a stationary one. There could be
deterministic trend(s) mixed inside the series. Therefore, the observed NCC series could be decomposed
into two parts. One part represents the mean of the series, accounting for the non-stationary trend by one or
multiple deterministic functions. The second part is a stochastic part with zero mean so that it can be
modeled by a data dependent scheme. This yields out three corresponding modeling steps.
Step one: to ascertain the trend(s) of observed series by using curve fitting methods (such as Sine/Cosine,
exponential, power, logarithmic, linear, and polynomial functions), and calculate the residual series after
curve fittings.
Step two: to employ the data dependent approach and construct an ARMA(n, m) model by employing the
residual series from step one, and predict the values for next one or more step(s). For this research, the next
step means the next year.
Step three: to re-construct the predicted values by combining the estimation(s) from trend(s) and the
prediction from ARMA(n, m) model.
CASE STUDY
Case Selection. This paper uses the NCC from Harris County in Texas to illustrate the proposed prediction
procedure. The groundwater in Texas accounts for 60 % of all water used for domestic, municipal, industrial,
and agricultural purposes, while 28% of drinking water is from groundwater, serving over millions of
Texans (TGPC, 2013). Based on the 2010 census, Harris County is the most populous county in Texas and
the third in the U.S. (Mackun et al., 2011). Besides, there are numerous petroleum industries in this county,
resulting in a large amount of groundwater contaminations.
Identifying Deterministic Trends. The NCC data from year 1997 through 2012 were carefully retrieved
from the JGMCR (TGPC, 1998-2013) and are potted in Figure 1. The solid line is the observed NCC for
Harris County and the dashed line is the curve fitting using a Cosine function, representing a periodical
variation of contaminations and even the behind production and economics in the region. There are two
peeks occurring in years 1997 and 2008, and the fitted Cosine function can be written as in Equation (4).
NCC123 = 58.5 ∗ COS 2π/: ∗ ; − 1997 + 142 (4)
where, t is the year of analysis, and T = 11 years is the oscillation cycle in year.
By removing the Cosine trend from the observed NCC series, the residuals are plotted as the solid
line in Figure 2. It contains a decreasing trend that can be fitted by a Logarithm function in Equation (5) and
is also the dotted line in Figure 2.
NCC?@A = −43.04 ∗ LN t − 1997 + 73.977 (5)
61
The new residual subtracting the Logarithm function with zero mean is plotted in Figure 2 as the
dash line and is denoted as Residual0, which is the series for data dependent modeling.
350
NCC Data
300
COS-fitting
250
CNC Numbers
200
150
100
50
0
1997 1999 2001 2003 2005 2007 2009 2011
Year
FIGURE 1. The observed NCC solid line and the fitted Cosine (COS) dash line for Harris County.
150
Residual Residual0 Logarithmic
100
CNC Residuals
50
-50
-100
1997 1999 2001 2003 2005 2007 2009 2011
Year
FIGURE 2. The further curve fitting using a Logarithm function and the resulted residuals.
Data Dependent Modeling of Residuals. After removing two deterministic trends (Cosine and Logarithm,)
several ARMA (n, m) models were constructed from the series residual0: ARMA(1, 0), ARMA (0, 1),
ARMA(2, 0), ARMA (1, 1), ARMA (0, 2), ARMA (2, 1), ARMA (0, 3), ARMA (2, 2), and ARMA(0, 4).
Figure 3 lists the FPEs of all ARMA models, where ARMA (0, 4) is spotted with the lowest FPE and can
also be denoted as MA(4).
9000
8000
7000
6000
5000
FPE
4000
3000
2000
1000
0
1, 0 0, 1 2, 0 1, 1 0, 2 2, 1 0, 3 2,2 0, 4
ARMA (n, m)
FIGURE 3. Comparison of different data dependent models via FPE values.
The predicted value E with calibrated parameters can be calculated using Equation (6).
E = − 0.2327 F − 0.08476 F − 0.2246 F H + 0.8756 F I (6)
62
With the information of the first 14 years (1997-2010) for modeling, the predictions for years 2011 and 2012
of the constructed MA (4) model (as is shown as the dashed line in Figure 4) are very close to the residual0
series from observed ones (the solid line in Figure 4).
Prediction Errors. By recovering the two trends for both Cosine trend and the Logarithm trend, the one
step prediction of NCC in year 2011 is 66 (vs. the observed NCC 65) with a relative error of 1.5%. The two
step prediction of NCC for year 2012 is 111 (vs. the observed one 99) with a relative error of 12.1%.
100
80 Residual0
60 ARMA(0, 4) prediction
40
Residual0
20
0
-20
-40
-60
-80
1997 2002 2007 2012
Year
FIGURE 4. Comparison between predicted (years 2011 and 2012) and residual0 series.
Computer Program. Most of the above modeling and prediction procedures are implemented through a
self-coded program in computer language MATLAB, while the “Statistics” and “Economics” toolboxes
were used durin programming. By feeding different input data, the compiled program is capable of modeling
and predicting NCC numbers and other similar variables at different levels.
Discussion. The observed NCC can be decomposed into three parts. First, the Cosine trend NCC123 in
Figure 1 and Equation (4) could be a reflection of the economics and production cycle of 11 years with four
stages, which could be expansion, crisis, recession, and recovery. This fits to the Juglar cycle in economics
with an investment cycle of 7 to 11 years identified by Juglar (1862). Within the Juglar cycle, one can
observe oscillations of investments into fixed capital. A recent research employing spectral analysis
confirmed the presence of Juglar cycles in world Gross domestic product (GDP) dynamics (Korotayev and
Tsirel, 2010).
Second, the Logarithm value NCC?@A in Figure 2 and Equation (5) represents a decreasing trend of NCC
due to the implication of possible innovative technologies and/or more strict government policies in
environmental protection. This is a part leading to the decreasing of contamination from groundwater, and
the trend of decreasing since late 2010s is not as strong as that in late 1990s.
Third, the stochastic part E is represented by the MA(4) model in Equation (6). This part senses the residual
non-deterministic trends and grasps the dependency of successive data series, so as to increase the precision
of forecasting. The total prediction should combine the estimates from all three parts from Equations (4)-
(6).
CONCLUSION
In this paper, a data dependent approach is proposed to model and predict the county-level
contamination new cases in Texas. Deterministic trends are firstly removed, followed by a modeling
procedure to ascertain the best fit ARMA model. A case study on 16 years’ NCC numbers in Harris County
was conducted and the one step prediction error was only 1.5% (actually only one more case predicted).
However, the two step prediction error increased to 12.1%. With more years’ NCC observations
accumulated, the prediction errors could be even smaller. While the proposed approach was tested using
information from Harris County of Texas, the fundamental method could be employed in other counties,
states, and even countries. With the prediction from such method, relevant stakeholders, agencies, and
government could be able to propose and implement suitable countermeasures in advance so as to mitigate
the negative impacts of those contaminations on groundwater.
63
ACKNOWLEDGEMENTS
Supports for this research by the U.S. National Tier 1 University Transportation Center (UTC)
TranLIVE and the U.S. National Science Foundation (NSF) CREST #1137732 are gratefully acknowledged.
REFERENCES
Environmental Protection Agency (EPA). 1984. Ground-Water Protection Strategy. Washington, D.C.
Hossain. M. and P. Mongkut. 2013, “Groundwater Arsenic Contamination Risk Prediction Using GIS and
Classification Tree Method” Elsevier, Engineering Geology, volume 156, April 2013, pages 37-45.
Juglar. C. 1862. Des Crises Commerciales et Leur Retour Periodique En France, En Angleterre, et aux
Etats-Unis. Paris: Guillaumin. (French).
Konikow, L.F. 2013. Groundwater Depletion in the United States (1900−2008). U.S. Geological Survey
Scientific Investigations Report. 2013−5079, 63 p.
Korotayev, A. V., and Tsirel, S. V. 2010. “A Spectral Analysis of World GDP Dynamics: Kondratieff
Waves, Kuznets Swings, Juglar and Kitchin Cycles in Global Economic Development, and the 2008–
2009 Economic Crisis.” Structure and Dynamics. Vol.4. #1. P.3-57.
Mackun. P and S. Wilson. 2011. Population Distribution and Change: 2000 and 2010. 2010 Census Briefs
Moody. D. W. 2014. Environmental Protection Agency (EPA). “#3: Sources and Extent of Groundwater
Contamination”, Groundwater and public policy leaflet series.
http://dnr.wi.gov/topic/Groundwater/documents/pubs/gwcntsrcs.pdf. Date accessed: April 29, 2014.
Pandit, S. M. 1991. Modal and Spectrum Analysis: Data Dependent Systems in State Space.
Pandit, S. M. and S.M. Wu. 1983. Time Series and System Analysis with Applications, John Willey and
Sons, Inc. New York, NY.
Qiao, F. 2010. Intelligent Data Dependent Modeling of Traffic Flow: Solving Problems in Traffic Flow
Classification, Simulation, and Control. ISBN-10: 3-8383-2906-6. Publisher: Lap Lambert Academic
Publishing. 244 pages.
Qiao, F. and H. Yang. 1998. “A Dynamic Data System Approach to Simulate Freeway Traffic Flow.” Post-
proceedings of the 8th World Conference on Transportation Research, Antwerp, Belgium, July 12-17.
Texas Groundwater Protection Committee (TGPC). 1998-2013. Join Groundwater Monitoring and
Contamination Report 1997-2012.
Texas Groundwater Protection Committee (TGPC). n.d. “Groundwater Facts & References”
file:///D:/University/ICEST_2014/groundwater/TGPC_GW_Facts_References.pdf. Date accessed:
April 29, 2014
64
EXPLORING THE INFLUENCE OF DISSOLVED ORGANIC MATTER ON PHOSPHORUS

MOBILITY IN GROUNDWATER
Christine A. Rumsey, Darwin L. Sorensen, David K. Stevens, and Joan E. McLean

(Utah Water Research Laboratory, Logan, UT, USA)
Phosphorus (P) concentrations in the shallow, unconfined aquifer at Pineview Reservoir, Utah indicate
increased phosphorus transport is occurring in groundwater. Because of known septic system influence in
shallow groundwater, a set of sorption experiments was completed to determine whether the presence of
dissolved organic matter (DOM) influences P sorption and increases P mobility.
A P only and a P + DOM isotherm were completed for two types of aquifer sediments. Initial P
concentrations of 0, 1, 2, 5, 7, and 10 mg PO4-P/L were chosen to simulate environmentally relevant
conditions. For the P + DOM isotherm, 15 mg C/L was spiked into the DOM artificial groundwater solution.
Aquifer sediments were collected from two locations around the reservoir to be used in sorption
experiments. Sediments represented coarse-grained and fine-grained sediments. Artificial groundwater was
prepared to match the principal cation and anion concentrations of groundwater at the two sampling
locations. DOM used in sorption experiments was obtained by concentrating DOM from groundwater at
the two sample sites using reverse osmosis and dialysis. Dialyzed DOM concentrates were characterized
using DOC, UV/visible absorption spectrum, proteins, sugars, and fatty acid concentration.
Results suggest that at the environmentally relevant levels of P and DOM used in experiments,
DOM did not create a notable effect on P sorptive behavior. Final DOM was composed of relatively large
biomolecules and had a more aromatic, hydrophobic, and humic nature than the original groundwater. These
larger molecular weight molecules, including sugars and proteins, had a minimal effect on P sorption.
Factors such as saturated sorption sites and the effects of historic septic system loading are more likely the
reasons soluble P is present in the shallow unconfined aquifer at PVR.
65
AN ANALYSIS OF GROUNDWATER CHEMISTRY OF HOT SPRINGS IN THE

SOUTPANSBERG BASIN IN SOUTH AFRICA
Ayanda Shabalala*, A.P.K. Nyabeze and Zuko Mankayi

(Council for Geoscience, Pretoria, Gauteng, RSA)
Groundwater aquifer and water chemistry of hot springs were investigated to understand the geothermal
potential of the Soutpansberg Basin. Water sampling was carried out at five hot springs namely Tshipise,
Dopeni, Mphephu, Sagole and Siloam. Water quality parameters were measured in situ using portable,
multi-sensor meters. Cations were analyzed using inductively coupled plasma optical emission spectrometry
(ICP-OES) and anions by ion chromatography (IC). The hot springs were found to be enriched in sodium,
bicarbonate and chlorine with very low concentrations of other element species. The chemical composition
of Tshipise, Sagole and Siloam thermal springs indicates the same source of origin of Na-Cl-HCO3 waters,
typical of deep circulating groundwater. Chemical analysis of the ground water revealed that the water does
not have any indication of pollution. High temperatures of 59.4, 51.2 and 46.0 ◦C were recorded at Siloam,
Tshipise and Dopeni hot springs respectively. The relatively high temperature and the deep groundwater
circulation are factors that support the geothermal potential of the Soutpansberg Basin.
66
ATMOSPHERIC REACTIVE NITROGEN DEPOSITION ONTO COASTAL REGIONS

IN CHINA
Xiaosheng Luo and Xuejun Liu*

(China Agricultural University, Beijing, China)
With the increasing reactive nitrogen (Nr) creation and emissions, more and more Nr enter into the coasting
sea by nitrogen deposition and lead to eutrophication of the coasting ocean and harmful alga bloom in the
ocean occurred frequently. To determine the present conditions of atmospheric Nr deposition in coasting sea
of China, six coasting sampling sites were selected to monitor Nr concentrations in air and precipitation as
well as their dry and wet deposition in 2011. Atmospheric concentrations of NH3, HNO3, NO2, pNH4+, and
pNO3- were 1.97-4.88, 0.46-1.22, 3.03-7.09, 2.24-4.90, 1.13-2.63 µg N m-3 at Dalian, Changdao,
Linshandao, Fenghua, Fuzhou and Zhanjiang sampling sites, respectively. NO3--N and NH4+-N
concentrations ranged from 0.46 to 1.67 mg N L-1 and 0.47 to 1.31 mg N L-1 in rain samples at the six
sampling sites, respectively. Dry N deposition was 13.0-34.1 kg N ha-1 yr-1 and total N deposition was 27.2-
55.6 kg N ha-1 yr-1 at the six coastal sampling sites. Average N dry deposition account for 55.8% of the total
deposition, and NH3 and NO2 contribute 67.1% for the total dry deposition. Applying the half N deposition
rate in this study for the four Seas (Bohai Sea, Yellow China Sea, East China Sea and South China Sea)
around China, the total N wet and dry deposition can amount to 6.2 Tg N yr-1, reflecting a huge
environmental nutrient input onto the ocean.
67
NUTRIENT LOAD PREDICTIONS IN STREAMS USING LS-SVM AND WAVELET-ANN
Raj Mohan Singh
(Department of Civil Engineering, Motilal Nehru National Institute of Technology,

Allahabad-211004, INDIA; E-mail: rajm@mnnit.ac.in; rajm.mnnit@gmail.com)
ABSTRACT: Rise in nutrients concentrations have been a persistent problem in streams rivers throughout
the world. Estimates of nutrient fluxes are necessity as well as challenges for water quality management.
The observation of nutrient loads (of nitrogen and/or phosphorous) from watershed into river or stream
system is not straight forward but complex function of hydrology, geology, and land use of the region.
There are statistical approaches to predict the nutrients loads in rivers. Development of models based on
temporal observations may improve understanding the underlying hydrological processes complex
phenomena of nutrient concentrations in river. Present work utilized temporal patterns extracted from
temporal observations of monthly flow data and nitrogen loads using wavelet theory. Performance results
show that time series least square support vector results are comparatively better than ANN model results
for predicting the monthly nutrient load. Model efficiency on testing data set is 32 percent for Wavelet-
ANN model whereas 35 percent for LS-SVM (least square support vector machine) when only one input
(discharge) is used.
Keywords. Wavelet-ANN, Time series modeling, Wavelet transforms, Nutrients, Nitrogen,
load prediction.
INTRODUCTION
Rivers have been central to the growth of societies throughout recorded history. Their fertile
floodplains produced, and continue to produce, high yields from agricultural crops. The rivers yielded high
harvests of fish, and river ecologists have learned that fish production, too, is linked to the productive
floodplain [Junk et al., 1989]. Both nitrogen and phosphorus have complex cycles that are mediated by
physical, chemical, and biotic processes in the water and in the soil [Brady and Weil, 2008].These processes
are modulated by temperature and water conditions. Therefore, nitrogen and phosphorus cycles are expected
to be affected by the timing of floodplain inundation. Excessive addition of nutrients, usually nitrogen and
phosphorus (N and P), to natural water is usually refers as eutrophication [Jorgenson and Richardson, 1996].
Rise in nutrient concentrations can result in locally high algal, phytoplankton, and macrophyte
biomass that have negative impacts on aquatic habitat and biota. Additionally, the transport of these nutrients
can lead to degradation of downstream water bodies, such as lakes, reservoirs, and estuaries [USEPA, 2000].
Noteworthy examples of problems associated with elevated nutrient concentrations vary from
eutrophication of lakes and reservoirs to hypoxia (low concentrations or absence of dissolved oxygen) [Saad
et al., 2002].
Nutrient enrichment results in the excessive growth of plants including phytoplankton in surface
waters. In recent years, eutrophication has been recognized as an important issue for environmental concern.
It becomes one of the most serious water pollution problems (Lee and Arega, 1999; Su and Dong, 1999).
Eutrophication can stimulate rapid algal growth, resulting in massive algal glooms. High biomass during
algal blooms may initiate significant ecological problems and cause harmful effects in the biota of the region
(Scholten et al., 2005). Some typical problems include anoxia condition of the water, change in bio-
community and food-web, deterioration of the water quality and adversary effects on the recreational use of
the water. Anoxia or hypoxia induced by algal blooms would cause declines in fishery production, major
changes in species composition, and distortions of sex ratio of some fish (Shang et al., 2006). In the water
supply source the organic matter excreted from algae cannot be effectively removed by enhanced
coagulation and filtration, and hence it is difficult to control the formation of disinfection by-products in
drinking water (Cheng and Chi, 2003).
68
The gradual accumulation of water quality data records over the past few decades has increased the
value of these data for examining long-term trends. However, on many major rivers of different countries,
infrequent sampling of most pollutants makes flux estimates and their analysis difficult. The present work
utilized the monthly data for the Idaho River to estimate the nitrogen loads using Wavelet ANN conjunction
model.
Transport of nutrient into river or streams is complex function of hydrology of the region and land
use patterns in a given river or stream basin which are difficult to quantify accurately. Development of
models based on temporal observations may improve understanding the underlying hydrological processes
in such complex phenomena. Recently, artificial neural network (ANN) as a non-linear inter-extrapolator is
extensively used by hydrologists (Nourani et al., 2009). ANNs may not be able to cope with nonstationary
data if preprocessing of the input and/or output data is not performed. Therefore, in this study, a new
combined model was developed for monthly nitrogen load prediction based on wavelet decomposition and
ANN techniques. The aim of combining the wavelet and ANN models is to improve the accuracy of nutrient
load prediction.
Present work utilized temporal patterns extracted from temporal observations of monthly nutrient
load series using wavelet theory. These patterns are then utilized by an artificial neural network (ANN). The
wavelet-ANN conjunction model is then utilized to predict the monthly nitrogen load in a stream. The
application of the proposed methodology is illustrated with real data pertaining to Indian River system.
ARTIFICIAL NEURAL NETWORK

The ANN is a broad term covering a large variety of network architecture, the most common of
which is a multilayer perceptron feedforwrd network with back propagation algorithm [Rumelhart et al.,
1986]. There is no definite formula that can be used to calculate the number of hidden layer(s) and number
of nodes in the hidden layer(s) before the training starts, and usually determined by trial-and-error
experimentation. The back propagation algorithm is used for training of the feed forward multi-layer
perceptron using gradient descent (Bishop, 1995; Singh et al., 2004). Present paper utilized Levenberg-
Marquardt (LM) backpropagation algorithm to optimize the weights and biases in the network. LM
algorithm is more powerful and faster than the conventional gradient descent technique (Hagan and Menhaj,
1994; Kisi, 2007). Basics and details of ANN are available in literature (Haykin, 1994).
LEAST SQUARES SUPPORT VECTOR MACHINE (LSSVM)

Support vector machine (SVM) is based on statistical learning theory as proposed by Vapnik and
Chervonenkis (1971) and discussed in detail by Vapnik (1995). It is a Kernel-based technique available in
the field of machine learning (Cortes and Vapnik, 1995). It is one of the most sophisticated nonparametric
machine learning approach available with various applications and many different configurations (Burges,
1998) depending upon the kernel and optimization method used. SVM has been applied successfully to time
series prediction as seen in the works of Tay and Cao (2001), Thiessen and Van Brakel (2003) and Misra et
al. (2009). Some of the application of SVM have also been carried out in hydrological and water resources
planning (Wang et al., 2009; Asefa et al., 2006; Lin et al., 2006; Dibike et al., 2001; Liong and
Sivapragasam, 2002; Yu et al., 2006). The standard SVM is solved using quadratic programming methods.
However, this method is often time consuming and has a high computational burden because of the required
constrained optimization programming.
Least squares support vector machines (LSSVM), as a modification of SVM was introduced by
Suykens and Vandewalle (1999) and Suykens et al. (2002). LSSVM is a simplified form of SVM that uses
equality constraints instead of inequality constraints and adopts the least squares linear system as its loss
function, which is computationally attractive. Besides that, it also has good convergence and high precision
(Samsudin et al. 2011). Hence, this method is easier to use than quadratic programming solvers in SVM
method. Extensive empirical studies (Wang and Hu, 2005) have shown that LSSVM is comparable to SVM
in terms of generalization performance. This LS-SVM formulation modifies Vapnik’s SVM (Vapnik, 1995)
at two points. First, LS-SVM takes equality constraints instead of inequality constraints. Second, the error
variable ei was introduced in the sense of least-square minimization. These error variables play similar role
as the slack variables in SVM formulation such that relatively small errors can be tolerated (Suykens et al.
2002). The major advantage of LSSVM is that it is computationally very cheap besides having the important
69
properties of the SVM. LSSVM has been successfully applied in diverse fields (Afshin et al., 2007; Lin et
al., 2005; Sun and Guo, 2005; Gestel et al., 2001). However, application of LSSVM in the water resource
filed is limited (Yunrong and Liangzhong, 2009; Samsudin et al. 2011; Bhagwat and Maity, 2013 etc).
The LSSVM is a new technique for regression. In this technique, the predictor is trained by using a
set of time series historic values as inputs and a single output as the target value. The first step would be to
consider a given training set of n data points , - (xi is the input vector; di is the desired value and n is
data size). SVM approximates the function in the following form
J = KL +M (1)
Where L is the high dimensional feature space which is mapped from the input space x. Values of w and
b are estimated by minimizing the regularized risk function in the feature space with a squared loss (Suykens
et al., 2002):
S
NOP Q K, % = K R K + ∑ U % (2)
Subject to the equality constraints:
V = KL +M+% (3)
where γ is the regularization constant parameter; and ei is error vector for xi in optimizing the trade-off
between minimizing the training errors and minimizing the model’s complexity.
The solution is obtained after constructing the Lagrange:
) K, M, %, ∝ = Q K, % − ∑ U ∝ K R L +M+% −V (4)
With Lagrange multipliers αi, the conditions for optimality are obtained by partially differentiating with
respect to w, b, ei and αi,:
XY
XZ
=0→K=∑U ∝ L (5)
XY
X\
=0→∑U ∝ =0 (6)
XY
X]^
= 0 →∝ = _% (7)
XY
X∝^
= 0 → KRL +M+% −V =0 (8)
From the set of Equations (5)–(8), w and e can be eliminated and finally, the estimated values of b and αi
can be obtained by solving the linear system. Replacing w in Equation (1) from Equation (5), the kernel
trick may be applied as follows using Mercer’s condition (Mercer, 1909; Vapnik, 1995; Courant and Hilbert,
1953):
à , b c = L R
.L b (9)
Here, the kernel trick means a way to map the observations to an inner product space, without actually
computing the mapping and it is expected that the observations will have a meaningful linear structure in
that inner product space.
This finally leads to the following LSSVM model for function estimation:
Vd = ∑ U e à , b c + M (10)
where αi, b are the solution to the linear system. Any function that satisfies Mercer’s condition can be used
as the kernel function. K(xi , xj ) is defined as the kernel function. The value of the kernel is equal to the
70
inner product of two vectors Xi and Xj in the feature space L and L b that is, à , b c = L ×
L b . The structure of a LSSVM is shown in Fig. 1.
Generally speaking, there is no general guiding principle for choosing a kernel function (Li et al.,
2010). The widespread use of kernel functions includes radial basis function (RBF), linear, sigmoid and
polynomial ones. For these four kernel functions, in general, the RBF kernel function is a reasonable first
choice (Liu et al., 2009). This kernel function nonlinearly maps samples (data patterns) into a higher-
dimensional space. So, unlike the linear kernel, it can handle the case when the relation between class labels
and attributes is nonlinear. The second reason is that the RBF kernel function has a less number of
hyperparameters which influences the complexity of model selection. Finally, the RBF kernel has fewer
numerical difficulties (Caydas¸ and Ekici, 2012; Avci, 2012; Comak and Arslan, 2012). In comparison
with some other feasible kernel functions, the radial basis function (RBF) is more compact and is able to
shorten the computational training process and improve the generalization performance of LS-SVM, a
feature of great importance in designing a model (Suykens and Vandewalle 1999). Aksornsingchai and
Srinilta (2011) studied support vector machine with polynomial kernel and with radial basis function (RBF)
kernel and found that RBF is more accurate for statistical downscaling. Also, many studies have
demonstrated the favourable performance of the RBF (Choy and Chan 2003; Dibike et al. 2001; Han and
Cluckie 2004; Liong and Sivapragasam 2002; Yu and Liong 2007). Therefore, the RBF kernel function is
employed in this study. The RBF kernel function can be expressed as:
` , = exp jk ‖ − ‖ (11)
where is the kernel function parameter of the RBF kernel. The symbol ‖m‖ is the norm of the vector V
and thus, ‖ − ‖ is basically the Euclidean distance between the vectors x and xi. In the context of
nitrogen prediction, xi is the new vector of time series inputs (flow and/or total nitrogen concentration),
based on which total nitrogen load prediction (Vd ) is made. Values of yi (observed) and Vdn (predicted) are
compared to assess the model performance. Details of Methodology are presented in Fig. 1.
Fig.1. Schematic of support vectors methodology
WAVELET ANALYSIS
Wavelet analysis allows the use of long-time intervals for low frequency information and shorter
intervals for high frequency information. Wavelet analysis is capable of revealing aspects of original
data like trends, breakdown points, and discontinuities that other signal analysis techniques might
miss. Furthermore, it can often compress or denoise a signal. Basics of wavelets are available in
literature (Daubechies, 1998; Kang and Lin, 2007; Mallat, 1998). Discrete wavelet transform (DWT)
71
operates two sets of function (scaling and wavelets) viewed as high-pass and low-pass filters (Fig. 2). The
original time series are passed through high-pass and low-pass filters and separated at different scales. The
time series is decomposed into one comprising its trend the approximation and one comprising the high
frequencies and the fast events (the detail). In the present study, the detail coefficients (D) and approximation
(A) subtime series are obtained using MATLAB wavelet tool box (MATLAB, 2004).
Fig. 2. Decompositions of time series data into DWT components
WAVELET-ANN CONJUNCTION MODEL FOR NITROGEN NUTRIENTS

Wavelet-ANN conjunction model utilized wavelet decomposed coefficients ob-tained from wavelet
analysis to the ANN technique for daily sediment load prediction as shown in Fig.3.
Fig.3. Wavelet-ANN conjunction Model for Nitrogen Nutrients
First, the measured daily time series, Q (discharge) (m3/s) and/or N(Nitrogen nutrients, NO2 +NO3)
(mg/l) were decomposed into smulti-frequency time series comprising of details (low scale, high frequency)
- Qd1(t); Qd2(t);…; Qdi(t) for discharge and Nd1(t); Nd2(t);…; Ndi(t); and approximate (high scale, low
frequency) – QA(t) for discharge and NA(t) by DWT. The representation di presents the level ‘i’
decomposed details time series and ‘A’ denotes approxi-mation time series. The decomposed Q(t) and N(t)
time series were utilized as in-puts to the ANN model and the original time series of observed nutrient load
at the next step N(t+1) is output to the Wavelet-ANN model (Fig. 3).
Model Evaluation Criteria. The performances of the developed models are evaluated based on some
performance indices in both training and testing set. Varieties of performance evaluation criteria are
available which could be used for evaluation and inter comparison of different models. Following four
performance indices represented as correlation coefficient (R), root mean square error (RMSE), model
efficiency (Nash–Sutcliffe Coefficient, MENash) [Nash and Sutcliffe, 1970], and Index of agreement (IOA)
are selected in this study based on relevance to the evaluation process.
n
∑ ( Xai − Xai )( Xpi − Xpi )
i =1 (12)
R=
n 2 n
∑ ( Xai − Xai ) ∑ ( Xpi − Xpi) 2
i =1 i =1
1 n
RMSE = ( ∑ ( Xai − Xpi ) 2 ) (13)
n i =1
72
n 2
∑ ( Xai − X pi )
ME Nash ( E ) = 1.0 − i =1 (14)
n 2
∑ ( X ai − Xai)
i =1
n 2
∑ ( Xai − X pi )
IOA = 1.0 − i =1 (15)
n
[
∑ ( X ai − Xai ) + ( X pi − Xpi )]2
i =1
where Xai and Xpi are measured and computed values of atrazine concentration values in streams; Xai and
Xpi are average values of Xai and Xpi values respectively; i represents index number and n is the total
number of years of measurement.
Application LS-SVM and Wavelet-ANN Conjunction Model. The developed models require
uninterrupted time series data pertaining to flow and Nitrogen load at a gauging station for calibration and
verification periods. The data derived from the Iowa River at the Wapello, IA site (USGS Station Number
05465500; basin area (sq mi): 12,499; latitude: 41°10′48′′; longitude: 091°10′57′′) were employed to train
and test all the models developed in this study. The monthly time series of Q and N (NO2 +NO3) for this
station were downloaded from the USGS web server (http://toxics.usgs.gov/pubs/of-2007-
1080/sub_basins/IOWAWAPE. Monthly. xls). Monthly data from October 1978 to September 1997 (20
yrs) and the data from October 1997 to September 2005 (8 years) were used as training and testing sets,
respectively.
RESULTS AND DISCUSSIONS

One of the most important steps in developing a satisfactory forecasting model such as ANN and
LSSVM models is the selection of the input variables. In this study, the nine input structures which having
various input variables are trained and tested by LSSVM and ANN. For LS-SVM and Wavelet-ANN
conjunction models are implemented on MATLAB platform. For developing the time series LS-SVM
models, three input conditions are considered- first, when flow data is input Three time series After loading
the data, hyper-parameters gamma and sigma squared are tuned. Final values of parameters obtained are
The function values and corresponding parameters values are shown in Table-. After 10 iterations, back
propagation ANN training algorithm is implemented for obtaining the optimal ANN architecture with the
internal parameters as: number of epoch=1000; momentum coefficient=0.8.
Table 1. Training and testing errors for WANN conjunction model and TANN
Models Performance statistics
(Trainlm) Training R RMSE E IOA
/Testing
WANN 1 Training 0.671 4.6E+03 0.450 0.777
2-2-1 Testing 0.578 5.4E+03 0.326 0.700
W-LS-SVM Training 0.746 4.2E+03 0.5568 0.8381
Testing 0.598 5.34E+03 0.3466 0.7311
T-LS-SVM Training 0.549 5.2E+03 0.301 0.669
Testing 0.486 5.8E+03 0.23 0.579
TANN 1 Training 0.556 5.2E+03 0.309 0.669
1-2-1 Testing 0.498 5.8E+03 0.238 0.596
In addition, optimum combinations of transfer functions in the hidden and output layer are obtained
with ‘trainlm’ function for Levenberg- Marquardt (LM). Performance of Wavelet–ANN (WANN)
conjunction model is compared with actual time series (without wavelet decomposition) ANN model
(TANN). Two WANN models, WANN 1 and WANN 2 are developed. WANN-1 model has two inputs
(wavelet decomposition-approximation and details coefficients of discharge data at time t by wavelet
transform DWT Haar wavelet level 1). The output for WANN 1 model is Nitrogen concentration in the river
73
at time t+1. Two TANN models, TANN 1 and TANN 2, are also developed. TANN 1 model has one in-put
i.e. actual discharge at time t and one output (nitrogen load at time t+1. The TANN 2 model has two inputs
i.e. both actual discharge and nitrogen load at time t. The output is same as TANN 1 model. Thus, output of
all the models is same. Two LS-SVM models are developed: one having input-output similar to TANN and
second having input-output similar to WANN.
Experimentation with varying number of hidden nodes and training algorithm are performed. The
error statistics of best performing WANN and TANN models in training and testing are shown in Table 1.
LS-SVM with time series (T-Ls-SVM) out performs the time series ANN whereas wavelet When both
discharge and sediment data are employed in nitrogen prediction, results improve LS-SVM (W-LS-SVM)
out performs the wavelet ANN modelthe considerably. WANN2 model (4-3-1) outperforms TANN2 (2-2-
1) as evident from performance statistics presented in Table 1.
CONCLUSIONS
The study presents the general framework for evaluating nutrients load in a river system.
Methodology for wavelet-ANN conjunction model for nitrogen load prediction in rivers is demonstrated
through illustrative real monthly discharge and nitrogen concentration data. The values of statistical
performance evaluation criteria indicate the WANN time series model is able to simulate the complex
nitrogen transport event in rivers. Wavelet decomposition improved the results considerably. Model
efficiency on testing data set is 32 percent for Wavelet-ANN model whereas 35 percent for LS-SVM (least
square support vector machine) when only one input (discharge) is used. Multi levels of wavelet
decomposition may further improve the testing results.
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76
THE STUDY OF DESTRUCTIVE EFFECTS OF WASTEWATER CAUSED BY THE

ACTIVITIES OF LEATHER MANUFACTURING FACTORIES IN TEHRAN
Shobeiri Seyed Mohammad1, Kavei Behrouz2, Shotorbani Azarmir Marjan3, Alireza Bassiri4, Nazari
Batoul5
1
Department of Environmental Education, Payame Noor University, P.O.Box: 19395-4697, Tehran, Iran.
2
Department of Statistics, Sanjesh Organization, Tehran, Iran.
3
4
5
Department of Medical Sciences, University of Ahvaz, Iran.
Considering the fact that water is the single most important and vital element, and there is no replacement
for it and having access to a desired amount and quality is of essence, the conservation of water quality and
quantity has to be of the utmost priority. With the rise of the development trends and the formation of
industrial development plans in developing countries, the state of the environment in such countries have
started to raise concerns. Unfortunately, along with the gradual depletion of the size of available water
resources, various types of pollution add to the existing problems within water resources. Different
industries produce different types of pollution with their wastewater whose entry to the environment without
refinement could cause irreparable damages. One of the major industries emitting industrial wastewater is
leather industry. This industry gives off wastewater which is also used for its additives. The parts and wastes
of the skin itself contain a lot of pollutants like high BOD5, intense color, soluble salt, chemicals and high
PH. Thus, leather industry wastewater needs to undergo a careful and meticulous refinement for the fact that
it contains three types of physical, chemical and biological pollution so that the damage inflicted upon the
environment would subside. The most effective step to protect the environment is to assess people’s
performance and behavior to achieve basic principles of sustainable living; a sustainable development that
depends on sustaining the earth would not be possible unless a sustainable economy, a sustainable society
and a sustainable utilization are realized. The present study aimed to help improve the conditions and
function of refineries by studying destructive effects of wastewater caused by the activities of leather
manufacturing factories in Tehran, by evaluating the competency of the managers in this industry and by
proposing solutions to problems so that an important step to achieving a sustainable development is taken.
For this purpose, with objective observation using a checklist, existing methods will be weighed.
Regrettably, the performance of leather industry refineries in Tehran is not favorable and it is not near
standards and there is no refining carried out practically. The best solution considering the current status is
to follow methods that help decrease the creation of wastewater until refineries are operational. Also, with
optimal management, the consumption of substances like chromium, which causes the most damage to the
environment in this regard, should be cut down so less of this substance enters wastewater networks and the
environment.
77
THEORETICAL ANALYSIS OF POLLUTANT-MIXING ZONE FOR RIVERS WITH VARIANT

LATERAL DIFFUSION COEFFICIENT
Zhou-Hu Wu (Qingdao Technological University, Qingdao, Shandong, P. R. China)

Wen Wu (Queen's University. Kingston, Ontario, Canada)
ABSTRACT: For point constant source in straight-bank wide open channel, analytical solution for the
pollutant concentration distribution under variant lateral diffusion coefficient condition was obtained by
solving simplified two-dimensional transport equation, in which the advection in longitudinal direction and
the diffusion in lateral direction had been taken into consideration. The calculation method for pollutant
mixing zone was investigated. Theoretical formulas for the maximum length, maximum width and the
corresponding longitudinal coordinate of the maximum width of the pollutant mixing zone had been
deduced, as well as its area and the contour-curve formulas of its outer boundary. Further discussion had
focused on the effects of variant lateral diffusion coefficient on the morphology of the pollutant mixing
zone.
INTRODUCTION
Generally speaking, wastewater discharged from industrial, municipal or other resources cannot
meet the environmental quality standards. It causes the formation of dilution/diffusion zone of pollutants
where their concentration exceeds the environmental quality standards, so called pollutant mixing zone.
ZHANG YL, et al. (1993) concludes that when the wastewater quality exceeds the environmental quality
standards, pollutant mixing zone is acceptable as long as its area keeps relatively small.
One of the pollutant mixing zone technical procedure manuals (drafts), for instance, was proposed
by Idaho Department of Environmental Quality in 2008. It includes the mixing zone rules, mixing zone
approval process, monitoring, incomplete versus complete mixing, mixing zone determinations and water
quality modeling etc (Idaho Department of Environmental Quality, 2008). WU Z H, et al (2009, 2011)
developed an analytical pollutant mixing zone calculation method for constant lateral diffusion coefficient
cases such as wide, rectangular and straight rivers. The analytical formula for geometric scales and mixing
zone area were then obtained based. The formula clearly showed the constitutive relations between the
affecting factors. Moreover, it also led to a standard curve formula describing the boundary of the pollutant
mixing zone. The results were proved by the data of the simultaneous monitoring of both the water
environment and the hydrology/water quality pollution load carried out by Huang Z L, et al. (2006) in the
Three Gorges of the Yangtze River in China, before the dam and reservoir were built. The predicted
pollutant mixing zone boundary curve agreed very well with the measured fields near the discharging exit
of the Fuling Phosphate Fertilizer Factory. Discrepancy, however, appeared in predicting the pollutant
mixing zone near the municipal sewage outfall of Huangshaxi City by the Yangtze River. The difference
was due to the variant lateral diffusion coefficient during the transport of pollutant near Huangshaxi City
municipal sewage outfall, rather than the constant assumption used in the method: the shallows on the shore
near the outfall, as where the beginning of the diffusion happened, were dominant by small-scale vortices
which resulted in smaller diffusion coefficient; as the diffusion cloud moved further from the bank and
became bigger, the affects of larger-scale vortices were enhanced thus the diffusion coefficient became
larger correspondingly.
In this paper, we developed an analytical method for pollutant mixing zone calculation for variant
lateral diffusion under constant point source riverbank discharging condition. The simplified two-
dimensional advection-diffusion transport equation is solved to give the analytical solution of pollutant
concentration fields. The solving procedures have been explored. The results provide analytical formula for
geometric scales and mixing zone area, as well as the standard curve equation for the boundary of pollutant
mixing zone. The impact of variant lateral diffusion coefficient on pollutant mixing zone morphology was
analyzed.
78
PRINCIPLES AND METHODS

Turbulence consists of vortices of various scales. Generally speaking, the large-scale vortices play
the major role in the transport of momentum, mass and heat (XIA ZH.1982). The longer the pollutants being
discharged from the outfall, the further they get diffused, which causes them more likely to be transported
by the large-scale vortices in the main stream. Therefore, by assuming the river lateral diffusion coefficient
being proportion to the diffusion distance x, the variant lateral diffusion coefficient can be written as follows
(FISCHER H B, et al. 1979):
α
E y ( x) = γ y x y
(1)
in which γy and αy are positive constants.
Put the formula (1) into the simplified two-dimensional advection-diffusion equation, we have:
2
∂C α ∂ C
(2)
U =γ yx y
∂x ∂y 2
arrange formula (2) to get:
∂C γ y ∂ 2C (3)
U (1+α y )
=
∂x 1 + α y ∂y 2
let X = x (1+α ) , E = γ y (1 + α y ) , thence Formula (3) transforms into:
y
∂C ∂ 2C (4)
U =E 2
∂X ∂y
According to FISCHER H B, et al. (1979), under the condition of the constant point source, the
analytical solution of Formula (4) is:
m Uy 2 (5)
C ( X , y) = exp(− )
H πEUX 4 EX
put X, E into Formula (5) and simplified it to get:
m 1+α y (1 + α y )Uy 2
C ( x, y ) = exp( − ) (6)
(1+α y ) (1+α y )
H πU γ yx 4γ y x
in which x is the longitudinal direction along the river flow oriented from the sewage outfall; y is lateral
direction perpendicular to x, pointing to the opposite shore of the outfall; m is discharge intensity with
dimension [M/T]; U is the mean flow velocity in the mixing zone with dimension [L/T]; H is mean depth
of mixing zone with dimension [L].
Formula (6) indicates that the lateral concentration of pollutants discharged from the river bank has
semi-normal distribution. The maximum concentration near the bank (Cm) decays as the - (1 + α y ) 2 -th
power of distance x and the concentration distribution variance is σ y 2 = 2γ y x (1+α ) [U (1 + α y )] . Assuming the
y
summation of the background concentration (Cb) and the concentration allowed to increase caused by the
pollutant discharge (Cd) is the standard concentration (Cs) in the water environmental function zone, we
have Cd = Cs − Cb . Then the iso-concentration contour of Cd surrounding the region indicates the pollutant
mixing zone. From Formula (6) we can deduce the formula for iso-concentration contours as the outer
boundary of the pollutant mixing zone as:
m 1+ α y (1 + α y )Uy 2
Cd = exp(− ) (7)
(1+α ) (1+α )
H πU γ y x y 4γ y x y
Let y=0 in Formula (7), theoretical formula for the maximum length of pollutant mixing zone is:
1 + α y m 2 /(1+α y )
Ls = ( ) (8)
πUγ y HCd
taking derivative of each term in both sides of formula (7) and let dy dx = 0 , we obtained the theoretical
formula of the maximum width of pollutant mixing zone and its longitudinal coordinate:
79
(1+α y )
2γ y Ls 2 m , −1 /(1+α y )
bs = = Lc = Ls e (9)
(1 + α y )eU πe HUCd
−1
Thus the positive constant (αy) in the variant lateral diffusion coefficient is α y = ln (Ls Lc ) −1. It can
be determined onsite by the ratio of the corresponding coordinates of the maximum length and width of
the pollutant mixing zone measured at the bank. Put Formula (8) and (9) into Formula (7), the contour-
curve formula of the pollutant mixing zone outer boundary is obtained as follows:
y x (1+α ) x (1+α ) x (1+α ) x (1+α )
( ) 2 = −e( ) y ln( ) y , or y = bs − e( ) y ln( ) y (10)
bs Ls Ls Ls Ls
Take definite integral of Formula (10) in x direction in the range of [0, Ls], formula for the area of
the pollutant mixing zone is:
Ls x (1+α y ) x (1+α ) (11)
S= ∫0
bs − e (
Ls
) ln( ) y dx
Ls
substitute the variables as x L s = ζ and then η = ζ (3+α y ) 2 , simplify formula (11) and noticed
1
∫0 ln(η )dη = π 2 in table of integrals, the theoretical formula for pollutant mixing zone area will be:
−1
πe 2(1 + α y ) πe 2(1 + α y )
S= Lsbs = µLsbs , µ = (12)
3+αy 3+αy 3+αy 3+α y
here μ is area coefficient that only decreases monotonically with the increasing of αy. The lateral diffusion
coefficient will be a constant when αy=0. The maximum area coefficient μ = 0.795 is exactly the same as
the results of WU Z H, et al. (2009) for constant lateral diffusion coefficient cases.

It can be known from Formula (10) that the shape of pollutant mixing zone outer boundary as
defined by the standard dimensionless iso-concentration curve is only determined by αy . The lateral diffusion
coefficient is constant when αy=0. The corresponding longitudinal coordinate of the maximum width is
Lc=Ls/e=0.368Ls. The standard curve equation and the calculated conditions are consistent with the results
of WU Z H, et al. (2011). When αy =0.443, the corresponding longitudinal coordinate of the maximum width
is Lc=0.50Ls. The widest section is in the middle of the pollutant mixing zone. When αy>0.443, the
corresponding longitudinal coordinate of the maximum width is Lc=(0.50～1.0)Ls. The widest section is
between the middle section and the end section. Plots of the dimensionless curve of pollutant mixing zone
by riverbank discharge are shown in Figure 1 for αy=0, 0.5, 1, 2.
1
Dimensionless lateral
0.8
coordinate y /b s
0.6 αy=0
αy=0.5
0.4 αy=1
αy=2
0.2
0
0 0.2 0.4 0.6 0.8 1
Dimensionless longitudinal coordinate x /L s
FIGURE 1 Dimensionless curves show the shape of pollutant mixing zone by riverbank discharge
As can be seen from Figure 1, the shape of riverbank discharge pollutant mixing zone is semi-
elliptical. When αy = 0, the shape is blunt near the outfall while gradually becoming sharper downstream.
As αy increases, the region near the outfall becomes sharper while the downstream end gets blunter. Studies
have shown that with the increase of the constant αy of variable lateral diffusion coefficient, the location of
80
the maximum width of pollutant mixing zone moves downstream along the longitudinal coordinate Ls/e.
This finding consists with our assumption that the further the diffusion distance, the greater the chances of
pollutants got transported by large-scale vortices, thus the larger the lateral diffusion coefficient.
The length-width ratio of the pollutant mixing zone by riverbank discharge can be described by
the ratio between the maximum length and the maximum width of the pollutant mixing zone. The ratio can
be obtained from formula (9):
Ls (1 + α y )eULs e(1 + α y )
= = Pe (13)
αy
bs 2γ y Ls 2
α
here E L = γ y Ls is the characteristic lateral diffusion coefficients. Pe = ULs E Ls is the Peclet number
y
s
physically represents the ratio of the longitudinal advection and the lateral diffusion of materials. Formula
(13) shows that the length-width ratio of the pollutant mixing zone by bank discharge is proportional to
(Pe)1/2. When the longitudinal advection effect is stronger than the lateral diffusion, the length-width ratio
of the pollutant mixing zone is larger. Thus the pollutant mixing zone presents a long and narrow shape.
WU Z H, et al.(2011) observed the pollutant mixing zone in the outfall’s by one starchy factory in
Guangfu river. Using the theory obtained above, αy=0 and the lateral diffusion coefficient Ey=constant
γy=0.27 m2/s, the pollutant mixing zone of this starch factory can be described by the standard curve equation
based on formula (10) as follows:
2
 y x  x
  = −e ln   (14)
5 32  32 
HUANG Z L, et al. (2006) provided the concentration filled contours of NH3-N measured in
Yangtze River at Huangshaxi outfall in dry season (shown in figure 2) The measured maximum length,
maximum width and its corresponding longitudinal coordinate of pollutant mixing zone are given in Table
1 for concentration of NH3-N being 0.33, 0.40 and 0.50mg/L.
FIGURE 2 Concentration filled contours of NH3-N measured in Huangshaxi outfall during dry season. Outer
boundaries predicted by this study are also plotted.
TABLE 1 Sewage pollutant mixing zone characteristic parameters and lateral diffusion coefficient of Huangshaxi outfall
Iso-concentration Max. length Max. width Longitudinal
Items Area S/m2 ELs/(m2s-1)
Value Ls/m bs/m coordinate Lc/m
0.33 269.7 120.0 204.8 --- ---
Measured
values 0.40 204.8 75.0 126.5 --- ---
0.50 112.7 45.3 73.0 --- ---
0.33 271.4 116.7 186.6 21193.3 136.6
Theoretical
0.40 196.7 75.0 135.3 9871.5 74.7
fitted values
0.50 112.7 43.4 77.5 3272.9 30.3
The mean flow velocity is 0.75, 0.72 and 0.50 m/s for NH3-N=0.33, 0.40 and 0.50mg/L respectively,
calculated based on the measured cross-section velocity distribution in sewage mixing zone of Huangshaxi.
Using the theoretical formula obtained above, the calculation formula for the variant lateral diffusion
coefficients of the Huangshaxi outfall when αy=1.67, γy=0.0114 is (in metric units):
α
E y = γ y x y = 0.0114x 1.67 (15)
81
Put αy=1.67 into Formula (10), we can obtain the standard curve equation of the outer boundary of
the pollutant-mixing zone of Huangshaxi outfall shown in Figure 2 as filled contours.
y x x
( ) 2 = − e( ) 2.67 ln( ) 2.67 (16)
bs Ls Ls
Ls and bs here are fitted values for the maximum length and maximum width. The theoretical curves of three
pollutant mixing zones boundaries predicted by Formula (16) are also shown in Figure 2.
CONCLUSIONS
(1) We proposed the analytical solution of the simplified two-dimensional transport equation for
the pollutant concentration distribution in riverbank discharge cases under variant lateral diffusion
coefficient condition. The theoretical formulas for the maximum length, maximum width and its
corresponding longitudinal coordinate, as well as the area of the pollutant mixing zone are obtained.
(2) Shape of the pollutant mixing zone in the riverbank discharging cases only depends on the
constant αy defining the variant lateral diffusion coefficients. The lateral diffusion coefficient is constant
when αy=0. The standard curve equation in dimensionless form of the pollutant mixing zone’s outer
boundary we deduced has simple form and is convenient and practical.
(3) The length-width ratio of the pollutant mixing zone in riverbank discharge is proportional to
(Pe)1/2. The larger the Peclet number is, the longer and narrower the pollutant mixing zone is.
ACKNOWLEDGEMENTS
This research is supported by the National Natural Science Foundation of China (51379097).
REFERENCES
FISCHER H B, IMBERGER J, LIST E J, et al. 1979. Mixing in inland and coastal waters. Academic Press,
New York, NY.
HUANG Zhen-li, LI Yu-liang, CHEN Yong-can, et al. 2006. Water quality prediction and water
environmental carrying capacity calculation for Three Gorges reservoir. China Water Resources and
Hydropower Press, 168-177, Beijing, China.
Idaho Department of Environmental Quality. 2008. Mixing Zone Technical Procedures Manual (DRAFT).
Idaho Department of Environmental Quality, Boise, USA.
WU Zhou-hu, JIA Hong-yu. 2009. Analytic method for pollutant mixing zone in river. Advances in Water
Science, 20(4): 544-548. (in Chinese).
WU Zhou-hu, WU Wen, WU Gui-zhi. 2011. Calculation Method of Lateral and Vertical Diffusion
Coefficients in Wide Straight Rivers and Reservoirs. Journal of Computers, 6(6):1102-1109.
XIA Zhen-huan. 1982. Turbulence mechanics. Hydraulic Engineering Department of Tsinghua University,
Beijing, China.
ZHANG Yong-liang, LI Yu-liang. 1993. A guide to analytical solution of pollutant mixing zone. Ocean
Press, Beijing, China.
82
EFFECT OF TEXTILE EFFLUENT ON GERMINATION AND GROWTH OF GRAMS
Monika Chandel, S.K. Tank

(Department of Biosciences, Veer Narmad South Gujarat University, Surat, Gujarat, India)
ABSTRACT: Surat is located at 21.17 N latitude and 72.8300 E longitude. There are more than 500 textile
industries involved in dyeing and printing in Surat city which generates lot of effluent. The textile industry
waste is one of the most toxic and pollute water resources. Not only the amount of water which is being
used by the textile industry gets polluted but also the effluent which is fed into the water bodies pollutes the
surface water. The present study focuses on the dreadful effects of textile waste water on germination and
growth of Chickpea. The different concentration of effluent was taken [20%, 40%, 60%, 80%] and seeds
were grown. In lower concentration the germination ratio and growth are relatively higher than the control,
but gradual decrease in the germination of seeds, seedling growth with increase in effluent concentration
was observed. The best germination and seedling growth was observed in 20% concentration with growth
promoting effect, and significantly better than control. The effect on root and shoot length were observed
and on the overall growth along with secondary root emergence and branches. Thus the textile mill effluent
can be safely used for irrigation purposes with proper treatment and dilution at 20%.
Key Words. Textile Effluent, Grams, Growth , Germination, Toxicity.
INTRODUCTION
Increasing pollution of natural waters with waste effluents arising from various industries has
become serious problem in Surat, as textile industrial growth and development have been on the increase.
In Gujarat diamond and textile industry represent an important economic sector. Surat is located at 21.17 N
latitude and 72.8300 E longitude. There are more than 500 textile industries involved in dyeing and printing
in Surat city which generates lot of effluent. Due to the nature of its operations which requires large amount
of water, most of the waste generated ends up in the nearby Pandesara khadi (water stream) thereby altering
its natural state as regard quality.
Industrial effluents are undesired by-products of economic development and technological
advancement. When such wastes are improperly discharged off, they imperil human health and the
surrounding environment. Effluents from textile industries are complex mixtures of chemicals varying in
quantity and quality. These industries generate both organic and inorganic waste mixed with waste waters
from the production process, which leads to change in both biological and chemical parameters of the
receiving water bodies. Now the industries are well developed and a large number of small textile
processing units are scattered all over the country. Wet processes like bleaching, dyeing and screen printing
are being carried out by these industries. Textile processes requires large volumes of fresh water after the
cloth processing operations. The wastewater volume varies from mill to mill. The combined wastewater
volume from Indian textile mills lies in the range of 86 to 247 liters with an average 172 liter per kg of cloth
produced. Their effluents constitute a major part of the total industrial effluents in India. On an industrial
scale the effluents resulting from the dyeing and printing operations of textile mills are managed through
primary or secondary wastewater treatment. Whatever the pollution source may be, soils can act as a sink
of heavy metals but three main kinds of ecological risks are associated to this fact are:
• the loss of productivity in the soil compartment,
• the pollution of ground-water due to metal leaching, and
• the accumulation of pollutants in food-chain, with effects on vegetation and animals, including humans
In India, the abundance of soils with low organic matter content, favours the use of industrial
wastewaters containing organic matter as an organic amendment and nutrient supply to soil. Although the
benefits of wastewater use in irrigation are numerous but precautions should be taken to avoid short and
long-term environmental risks related. Earlier studies have shown that the effect of an industrial effluent
83
vary from crop to crop. So it is essential to study the effect of industrial effluents on individual crops before
their use in agricultural fields.
Sample Collection and Treatment. Water sample were collected from textile industry in Surat city from
Pandesara region, into clean plastic containers. The water sample was immediately evaluated in its crude
natural state for physiochemical variables.
Seeds of chickpea were obtained and used for study. Seeds were planted on loam soil in pots. The
soil was kept moist by adding water when necessary.
Seeds Treatment. Chickpea seeds were subjected to sterilization before planting so that they become free
of any fungal infection. They were sterilized with 0.01% solution of mercury chloride for 1 minute and then
washed under running tap water for 2 to 3 minutes and then with distill water twice for 3minutes.Seedlings
were then soaked in different concentration of textile effluent 0%, 20%, 40%, 60% and 80% respectively
for 24 hours. These seedlings were then transferred to pots containing similar concentrations of effluent.
They were allowed to grow for 15 days after germination to enable them attain an appreciable height range
of 15 to 20 cm. Five germplasm were taken for study and each individual were observed for germination.
The effluent water sample were provided as and when necessary but equally to all germplasm in all the
concentration and control plants received equal amount of water devoid of effluent. At the end of the
treatment period, plants were harvested and various parameters were evaluated. All analyses were replicated
4 times unless otherwise stated.
Root Growth Determination. Uprooted plants were thoroughly washed with clean water and the main root
length was measured. Also, root architecture was visually examined.
Dry Weight Determination. Harvested plants were washed thoroughly in a running tap water to remove
soil particles. After rinsing with distilled water, they were placed in labeled paper bags and oven dried at
80°C for 72 hours. The dried samples were weighed using a digital top loading weighing balance to
determine the dry weight.
Growth inhibition was measured in relation to the control mean:
% inhibition = 100 × 1- ‫ ג‬treated
‫ ג‬control
RESULTS
Physicochemical Characteristics of the Water Sample. The results of the physicochemical variables of
the water sample are as shown in Table 1 together with the limit values accepted by the regulatory authority.
The water samples Fe and Pb levels were found to be higher than the reference standards, hence violating
the discharge limits.
Growth. The effects of the treated textile effluent on the root growth of chickpea are shown in Photo1,
Figure 1 and Figure 2. The root growth of Grams was markedly affected by the textile treated effluent. At
the end of the experiment period, the control plants showed a primary root length of 110 mm while the
treated plants had a mean value of 70mm, a difference that was significant. There was marked difference in
the root architecture between the control plants and those that received treated effluents. The roots of control
plants appeared thicker with more numerous lateral roots compared to the treated plants. The dry weight
data clearly showed that treated effluent had significant inhibitory effect on Grams as treated plants
accumulated less biomass compared to the control plants. The treated effluent caused 57% growth inhibition
in 40% effluent (Wins et al., 2010) relative to the control plants. It was observed that in 20% effluent seeds
84
showed delay in germination but after few days there was sudden increase in germination (Panaskar et al.,
2011) and also in growth. Seeds germinated in 100% effluents but did not survive for longer period (Garg
et al., 2008).
TABLE 1. Characteristics of the water sample from Pandesara Khadi polluted with treated effluent from a
textile industry compared with WHO standards
S/N Parameters Mean levels detected WHO standards
1. Temperature 29°C -
2. Colour Reddish Brown -
3. pH 6.7 7 to 8.5
4. Total solids 3810 mg/l 1500 mg/l
5. Total Suspended Solid 2240 mg/l -
6. Total Dissolved Solid 1570 mg/l -
7. Aluminium 0.20 mg/l 1mg/l
8. Cadmium 0.196 mg/l 0.005mg/l
9. Chromium 0.181 mg/l 0.05mg/l
10. Copper 0.113 mg/l 1mg/l
11. Iron 37.266 mg/l 0.3mg/l
12. Lead 2.13 mg/l 0.1mg/l
13. Nickel 0.869 mg/l 0.1mg/l
14. Zinc 0.248 mg/l 5.0mg/l
CONTROL 0% EFFLUENT 20 % EFFLUENT 40 % EFFLUENT
PHOTO 1. Control and Experimental Samples
DISCUSSION
The present study demonstrate that treated textile effluent water sample affected growth and
biomass and also photosynthetic pigments and also many other biochemical reactions occurring in seedlings
during germination process. The results imply that treated textile effluent cause biotoxicity on organisms.
These effects could be the result of high salt content and heavy metals in the treated textile effluent. For
clarification the textile effluent was analyzed for various physicochemical parameters and was found that it
contains high concentrations of Fe and Pb and the total solid content was far above the recommended
standards. These studies are of immense importance because these waters are used for agricultural and
85
domestic purposes. The study proves that the treated textile effluent which is directly fed into water streams
is not safe for use in agriculture and other household domestic purposes.
140
120
Length (mm) 100
80 Control
60
20%effluent
40
40%effluent
20
0
2 day 4day 6day 8day 10day 12day 14day
Days
FIGURE 1. Graph showing Root length Vs. Number of days
300
250
Length (mm)
200
150 Control
100 20%effluent
50 40%effluent
0
2day 4day 6day 8day 10day 12day 14day
Days
FIGURE 2. Graph showing Shoot Length Vs. Number of days
5
No. of seeds germinated
4 Control
3 20% Effluent
40%Effluent
2
60%Effluent
1
80%Effluent
0
1day 2day 3day 4day 5day
No. of Days
FIGURE 3. Graph showing No. of Seed Germination Vs No. of Days
86
CONCLUSION
The data obtained from this study indicated that the treated effluents from the textile industry as
they are directly discharged into the water stream contain toxic compounds. These compounds contaminate
the surface water, thereby making it unfit for irrigation and drinking. Therefore proper treatment of effluent
water and enforcement of pollution control by the regulatory authority on the discharge of textile waste
water into water streams should be done. The ecological and human health safety of continual discharge of
this textile effluents into water streams are undoubtedly under threat.
The present study focuses on treatment of textile wastewater and properly treated water in particular
concentration can be used for irrigation purpose (Hali R., et al., 2012) and would be helpful to farmers in a
country like India were it could solve 50% of the irrigation problems.
REFERENCES
Garg V., K., Kaushik P. 2008. “Influence Of Textile Mill Wastewater Irrigation On The Growth Of Sorghum
Cultivars.”Applied Ecology and Environment Research 6(2): 1-12.
Panaskar D., B., and Pawar R., S. 2011. “Effect Of Textile Mill Effluent On Growth Of Vigna Unguiculata
And Pisum Sativum Seedlings.” Indian Journal of Science and Technology 4(2): 266-272.
Wins A., Murugan M. 2010. “Effect Of Textile Mill Effluent On Growth And Germination Of Black Gram-
Vigna mungo (l.) Hepper.” International Journal of Pharma and Biosciences 1(1): 1-7.
Hali R., Malaviya P., Sharma N. 2012. “Impact Of Dyeing Industry Effluent On Germination And Grwth
Of Pea (Pisum sativum).” Journal of Environmental Biology 33:1075-1078.
87
MONITORING OF CYANOTOXIN AND T&O COMPOUND PRODUCING CYANOBACTERIA

IN DRINKING WATER RESERVOIRS USING QPCR METHOD
Y.-T. Chiu, S.-L. Lin, Tsair-Fuh Lin* (National Cheng Kung University, Tainan City, Taiwan),
H.-.K. Yen (Meiho University, Pingdong, Taiwan)
Cyanobacteria are a group of microorganisms present in many drinking water sources around the world. As
some of the microorganisms are producers of cyanotoxins, such as microcystins (MCY) and
cylindrospermopsin (CYN), and taste and odor (T&O) compounds, such as 2-methylisoborneol (2-MIB)
and trans-1,10-dimethyl-trans-9-decalol (geosmin), presence of toxin- and odorant-producing cyanobacteria
may pose additional health risk and aesthetic issues for people. Therefore, quantification of cyanotoxins,
T&O compounds and the producing species in water sources is necessary for proper management of
drinking supplies. Conventionally, microscopy, gas chromatograph, and liquid chromatograph are employed
to determine the producing species, T&O compounds, and cyanotoxins, respectively. However, these
methods require experienced personnel, sophisticated instrumentation, and/or long turn-around time.
Compared to the conventional methods, bio-molecular methods, such as quantitative polymerase chain
reaction (qPCR), may provide the information of functional gene concentrations of targeted cyanobacterial
metabolites in short time, offering additional information and time for the management of water supplies.
In this study, a qPCR based method was developed for the quantification of MCY, CYN, geosmin
and 2-MIB producing cyanobacteria present in drinking water sources in Taiwan. Primer and probe sets
were first designed and tested with isolated cyanobacteria species, including producers and non-producers
of the targeted metabolites. The designed primer/probe sets were proved to be able to quantify producers of
the targeted cyanotoxins and T&O compounds in fortified natural water. Then, the method was applied in
quantifying the toxin- and odorant-producing species in 38 drinking water reservoirs in Taiwan. The qPCR
data obtained in the reservoir samples were compared with cyanotoxins and T&O compound concentrations
measured with the conventional methods. Good correlations between the concentrations of the producers
and corresponding toxins or T&O compounds were obtained. The results indicate that the qPCR based
approach may offer a quick and specific detection method for the monitoring of cyanotoxin and T&O
compound producing cyanobacteria in water sources.
88
A Novel Flow-cell for in situ Spectrophotometric Detection of Contaminants in Water Samples
Emanuele Reggiani, Richard Bellerby, Kai Sørensen

(Norwegian institute for water reasearch, NIVA, Norway)
A flow-cell for automated water sampling and spectrophotometric analysis has been designed and
fabricated. The PTFA flowcell features 8ml sampling volume, up to 80mm light-path, possibility to feed the
cuvette with two different light sources. A set of reagents may be injected and stirring is possible through
an embedded magnetic flea. Temperature of the sample is continuosly monitored by a mini glass-
encapsulated thermistor, and can be adjusted by a miniature silicon heating pad. Water inlet and outlet are
protected against backflow through low-pressure stop-valves. The cuvette features also fittings for PMMA
fiber optic sensors that will be developed in the future. The cuvette has been tested in a fully unattended
mode supported by custom electronics during seawater pH monitoring campaigns, aiming to early detect,
with extreme precision, very small changes in ocean biogeochemistry in proximity of CO2 storage sites.
89
A MICROFLUIDIC COLORIMETRIC ANALYSER FOR PH IN WATER
John Cleary, Deirdre Cogan, Thomas Phelan, Kamil Jankowski and Dermot Diamond
(Dublin City University, Dublin, Ireland)
This paper describes the latest stage in the development of a microfluidic platform for autonomous
monitoring of environmental water quality. The current project focusses on developing and integrating
colorimetric methods for pH and in order to provide a low cost, autonomous monitoring system for this
important water quality parameter. pH measures the acidity or basicity of water. Most aquatic animals are
adapted to a range of 6.5–8.0 (close to neutral, pH 7.0). Low pH can also allow toxic substances such as
ammonia to become more available for uptake by aquatic plants and animals, greatly increasing their
effective toxicity. pH is commonly measured in industrial and municipal wastewaters as well as in
monitoring of drinking water, of surface waters such as rivers and lakes, and in many industrial processes.
The pH analyser which has been developed can be deployed in online or autonomous modes, and
utilises a combination of microfluidic technology, colorimetric reagent chemistry, LED and photodiode-
based optical detection systems; and wireless communications. pH is measured using a mixture of
colorimetric pH indicators, optimised to give a response over the pH range 4.0–10.0, which covers the range
of pH values commonly encountered in monitoring of surface waters, drinking water and many wastewaters.
Dual LED light sources and a single photodiode detector are used to measure light absorbance at appropriate
wavelengths (430 and 570 nm). Results from laboratory and field testing of the pH analyser will be
presented.
90
SUSTAINING SAFE DRINKING WATER SUPPLY IN DEVELOPING COUNTRIES: LEBANON

CASE STUDY
Mey Jurdi (American University of Beirut, Beirut Lebanon)

Sami Ramia (American University of Beirut)
Samira Korfali (Lebanese American University, Beirut, Lebanon),
Rola Ajib, Sara Chehab and Aya Issa (American University of Beirut)
The provision of sustainable access to safe drinking water and improved sanitation is one of the time
bounded targets of the Millennium Development Goal 7 that aims through the Water for Life Decade (2005-
2015) to cut in half the proportion of people without sustainable access to safe drinking water and improved
sanitation. On March 2012, at the 6th World Water Forum, the UN Water announced that the water supply
target to reduce by half the global population with no access to improved water sources has been met; still
the major challenge for developing countries remains ensuring that sustainable quantities (Basic Water
Requirements) are accessible and determining the quality and safety of the water supplies.
In Lebanon achieving this goal is not mostly challenged by the coverage of the piped water
distribution network, but by the quality and sustainability of the provided service. The intermittent
distribution of the piped water supply, the deficient quality and quality monitoring and quality control leads
to lack of trust in the provided service and impacts domestic water use. This consequently results in heavy
dependence on complementary water sources (private wells, water springs, bottled water, vended water and
cistern water) of unsafe and mostly undetermined water quality.
Results of the study emphasize that the provision of sustainable access to safe domestic water supply
is challenged by the type and quality of the provided service; the intermittent distribution of the piped water
supply, the prevailing quality and quality control measures, deficient quality monitoring, nonexistent water
safety plans and the lack of trust that leads to heavy dependence on unsafe complementary water sources.
Results also reflect on wide variability in the quality of piped water supplies that vary in physical, chemical
and microbiological quality and reflect mostly on exposure to major sources of pollution specifically
sewage, leachate of solid waste dump sites, agriculture run off and industrial solid waste and wastewater
effluents. Additionally, the condition of water reservoirs and distribution networks contributes to the water
contamination profile mainly due to the corrosion of the old poorly maintained networks and the resulting
sewage infiltration.
As such, the management of the quality of water supply is a challenging task in the absence of
sufficient technical and financial resources. What is more important is the will to commit to this process
under the prevailing administrative bureaucratic system. Still, insuring the quality and safety of the water
supply is a must and all efforts should be channeled to achieve this objective.
91
BIOLOGICAL DESALINATION OF SEAWATER USING MARIN MICROALGA Scenedesmus

sp. and Chlorella vulgaris
E. Sahle-Demessie, Ashraf Aly Hassan, Amy Zhao

(U.S. EPA, Office of Research and Development, NRMRL, 26 W. Martin Luther King Drive, Cincinnati,
OH 45268, UA)
With the increasing water demand and the scarcity of renewable natural water resources, desalination of
seawater has become essential in providing water requirements especially in dry regions. Seawater
desalination technology requires a large amount of energy which is typically generated from fossil fuels.
The combustion of fossil fuels emits greenhouse gases and, is implicated in climate change. However, there
are various types of algae or macrophytes which sequester the salts in their bodies and remove them from
solution. Biological mechanisms to remove sodium chloride (NaCl) from seawater using halophytes algae
are investigated. Various halophyte micro or macro-algae are screened and selected based on the degree of
salt tolerance, transportation rates, biomass production, nutrient requirements, ease of propagation and lipid
yield of the biomass. Two types of algae namely; Scenedesmus sp. and Chlorella vulgaris have proven this
concept and showed salt removal up to 30%. Salts are accumulated within the cell for the species of
Chlorella autotrophica as part of the osmoregulatory physiology of the cells. Removal of salinity was
observed based on conductivity measurements in both species and all media types. Growth was examined
under different salt types, salt concentrations and nutrient types. The effect of environmental conditions
(including salinity) on chemical and physical cell-wall properties were analyzed and optimum condition
were develop a controllable cell-aggregation protocol to facilitate rapid removal of the halophytes from the
desalted water.
92
ANALYSIS FOR ATMOSPHERIC WATER FOR DRINKING
Qing XIA and Shu GENG

(School of Environment and Energy, Peking University, China)
Condensed atmospheric water could be used as drinking water resource. Atmospheric water samples were
collected in six different areas of Shenzhen, China: industrial area, commercial area, road, residential area,
green land, and school. Following chemistry of atmospheric water were investigated: electrical conductivity
(EC), pH, six anions (F−, Cl−, NO2−, NO3−, SO42−, PO43−), five cations (Na+, NH4+, K+, Mg2+, Ca2+), total
organic carbon (TOC), total bacterial count, and nine trace metals (Cr, Mn, Ni, Cu, Zn, As, Se, Cd, Pb).
Results of quality analyses met drinking water standards in China, and European Commission, except NO2−
and total bacterial count. After filtration treatment, all indicators for water quality were better than drinking
water standards and even tap water. The potential of using atmospheric moisture as drinking water resource
will be discussed in this presentation.
93
SOURCE WATER PROTECTION FOR DRINKING WATER PRODUCTION: A EUROPEAN

RIVER MEMORANDUM
Peter G. Stoks1 and Ina Brüning2 (1. Association of Rhine Water works RIWA, Groenendael 6, 3439 LV
Nieuwegein, The Netherlands; 2. International Association of Water works in the Rhine Basin IAWR,
Himmelgeister Landstrasse 1, 40589 Düsseldorf, Germany)
From the seventies of last century the waterworks along the Rhine river in Europe (International Association
of Waterworks in the Rhine basin, IAWR) have been active in the improvement of the Rhine water quality.
The ultimate goal has always been a source water quality that allows the production of perfect drinking
water using simple treatment only. This view has also been adopted by the International Rhine Commission
ICPR.
Already in 1973 IAWR published a Rhine Memorandum stating quality demands that would help
reach that goal. Interestingly, those very demands were subsequently used by the European Union as the
basis of a Directive on the abstraction of surface water for dinking water production (75/440/EC). Several
updates of this memorandum were published over the years. In 2008 other associations of water works,
along the Danube and the Meuse, also endorsed the underlying philosophy and the memorandum was
broadened to the Danube-, Meuse- and Rhine Memorandum.
The Commissioner of DG Environment in the EU, when confronted with this memorandum
suggested to include more European rivers used for drinking water production and in 2013 the European
River Memorandum was published, representing over 170 utilities in 17 European countries, with well over
115 million consumers.
The most important aspects of this memorandum are quality objectives for not otherwise regulated
variables as groups, and demands and suggestions to (political) decision makers on the achievement of the
desired water quality based on the preautionary approach. A distinction is made between pollutants that
show biological activity (such as, e.g. pharmaceuticals or biocides) as well as pollutants for which such
information is not currently available (such as many metabolites and degradation products) and other
pollutants. The former type of pollutants should not exceed 0.1 ug/L in the source waters, the latter group
should not exceed 1 ug/L. A motivation based on scientific criteria for these demands and objectives is also
given.
The ICPR has recently reconfirmed its former statement that the Rhine should, ultimately, allow
drinking water production using simple treatment and in the Netherlands some of the approaches stated in
this memorandum have already been incorporated into legislation.
94
COMMUNITY WATER SUPPLY AND TREATMENT PROJECT IN CAMEROON:

CHLORINATOR DESIGN AND DEVELOPMENT
Kristen Chorney* and Sam Miller**

(Wilkes University, Wilkes-Barre, PA, USA)
During May 2013, a team from Wilkes University and the University of Pennsylvania’s chapter of Engineers
Without Borders visited The Ngyen-Mbo and Bome Spring Distribution System. This system supplies
drinking water to the people of the Bome Valley in the Northwestern region in Cameroon. Years of neglect
left the water contaminated with sediment and pathogenic microorganisms contributing to health problems
in the surrounding area. The team of students and local workers did maintenance on the system to clean it
and water testing was conducted. Based on the results of these tests, a water treatment system was chosen
to improve the quality of the water. This system is the CTI 8 Chlorinator. At Wilkes University, a model of
the chlorinator was built and tested. Aqua Chem® chlorine tablets were used as the source for chlorine. The
chlorinator was tested at different flow rates and a new chlorine tablet was used during each trial. These
tablets were weighed before and after testing to obtain a dissolving rate of the tablet. The flow rates were
2.4 gal/min, 0.92 gal/min, and 0.72 gal/min. Results indicate that larger flowrates hinder dissolution of
chlorine in the chlorinator as it provides lesser reaction time. It was concluded that when the flow rate is
too high (greater than 2.4 gal/min) there is not enough time for the chlorine to properly dissolve in the
chlorinator. During moderate to slow flow rates, the residual chlorine concentrations fluctuated, but were
generally at safe levels. Initial results indicate that the designed chlorinator has the potential to offer a
practical solution to providing potable water in many of the underdeveloped communities across the globe.
Results and a discussion of the study will be presented in detail in the poster.
95
VULNERABILITY ASSESSMENT OF SMALL COMMUNITY WATER SYSTEMS IN PUERTO

RICO
Adaíl Alicea-Martínez, Rafael A. Rios

(University of Puerto Rico, Río Piedras Campus, San Juan, Puerto Rico, USA)
In Puerto Rico, about 3% of the population (about 125,000 persons) gets its drinking water from
approximately 250 small community water systems. This community water systems began their life in the
1950’s in the rural parts of the island because there was no public aqueducts in these remote and
mountainous parts. These aqueducts were very simple and rudimentary in design but at the present time
have fairly advanced methods of distribution, storage and treatment (disinfection) but the topographical
conditions remain basically the same. The remote location of these aqueducts together with the threat of
hurricanes, tropical storms and earthquakes characteristic of Puerto Rico’s location in the Caribbean requires
a vulnerability assessment of these systems to minimize damage in the eventuality of these and other events
such as terrorism acts. The objective of this study was to assess both the vulnerability (probability of
damage) and criticality (if damage occurs, what is its impact on functionality) of 40 community water
systems using a methodology, developed by the authors specific for these systems. The purpose of the study
was to determine the degree of vulnerability and what can be done to minimize it in the event of a natural
or man made disaster. An emergency response plan was developed for each system. A scale from 0 (very
low risk) to 30 points (very high risk) was used for both vulnerability and criticality. The results showed
that the majority of the systems had high risk value for vulnerability and criticality. However, an analysis
of the results showed that the methodology failed to take into account factors such as economic means of
the community and its members, number of persons served and the management capabilities of the system
which may have flawed the absolute value of the criticality and vulnerability of each individual system.
96
AN INDEPENDENT INVESTIGATION INTO THE PHYSICO-CHEMICAL PURIFICATION

CAPACITY OF GRAVITY FED HOME WATER TREATMENT DEVICES SUPPLIED IN
SOUTH AFRICA
Cherie Ann Kruger, Tobias George Barnard* and Natasha Hodgkinson (Water and Health Research
Centre, University of Johannesburg, Doornfontein, South Africa), Cathleen Bartie (Immunology, NHLS,
Constitution Hill, South Africa)
Recent outbreaks of cholera and other waterborne diseases in Southern Africa have resulted in a public
perception that tap water is not safe for drinking purposes (Lang, 2007). As a result, the use of gravity fed
(jug and counter top) home water treatment devices (HWTDs) in the domestic and occupational setting is
increasing rapidly (Ahammed and Meera, 2010; Kaiser, 2010). Most of these devices are sold over the
counter and consumers buy these products in good faith on the basis of claims of their efficiency made
during marketing and advertising campaigns, and with the expectation that the device will remove 90-100%
of all harmful microorganisms (Berney et al., 2008; Varbanets et al., 2009). However, very often the claims
made in the manufactures brochures are not substantiated by independent research (Fengyi et al., 2009).
Thus a need existed for an independent exploratory study to evaluate a representative number of gravity fed
HWTDs sold in South Africa against the claims that are made by their manufacturers and in sales brochures.
This was done by sourcing a representative number of gravity fed HWTDs currently available on
the market and testing them independently with physico-chemical (free chlorine, conductivity, pH, turbidity,
TDS and particulate size exclusion) water contaminant testing listed in the “South African National
Standards” (SANS) 241:2006 (Drinking Water) to the certification standards recommended by the United
States of America, National Sanitation Foundation (NSF).
A general pattern of results was observed within this study as the gravity fed HWTDs potentially
did improve the water quality in terms of free chlorine removal, but in terms of conductivity, pH, turbidity,
TDS and particulate size exclusion the devices tested performed rather poorly, reporting on average a less
than 10% removal efficiency rate. The conclusive findings from this study suggest that gravity fed HWTDs
sold in South Africa cannot adequately treat water to a level deemed safe for human consumption and
requires further investigation.
97
IMPROVING SURFACE WATER QUALITY OF AGRICULTURAL WATERSHED USING

PLANNED INTERVENTION MICROWATERSHED APPROACH
Durga D. Poudel*
(University of Louisiana at Lafayette, Louisiana, USA)
Nonpoint source pollution and water quality impairment is a major environmental problem worldwide. Most
research studies on nonpoint source pollution are either at the field plot level or in a larger watershed level.
Often water quality monitoring studies are done at a large watershed, and results are generalized. The Texas
Institute for Applied Environmental Research (TiAER) at Tarleton State University, Texas, has developed
the Planned Intervention Microwatershed Approach (PIMA) for addressing agricultural nonpoint source
pollution. The TiAER defines a microwatershed as an area within a watershed, incorporating anywhere from
3,000 to 20,000 acres, with identifiable hydrologic boundaries. According to TiAER, by dealing with small
areas, watershed coordinators can reduce landuse variables and more readily identify the sources of pollutant
loads. In order to design and implement a microwatershed project in southwestern Louisiana, Vermilion
Soil and Water Conservation District led an initiative for building cooperative partnership with landowners
and homeowners, Louisiana Department of Agriculture and Forestry, USDA Natural Resource
Conservation Service, Acadiana RC&D, Louisiana Department of Environmental Quality, Louisiana State
University AgCenter, Louisiana Cooperative Extension Service, TiAER, University of Louisiana at
Lafayette, USDA Farm Service Agency, Coulee Baton Gravity Drainage District, Vermilion Parish Police
Jury, Gulf of Mexico Program, local agricultural enterprises and businesses, and Louisiana Department of
Natural Resources. A plan for voluntary application of various conservation measures and Best Management
Practices (BMPs) on the land by landowners and homeowners in addressing water quality problem of Coulee
Baton Microwatershed was developed.
As a part of the large-scale plan, a water quality monitoring study to assess surface water quality
and to identify factors associated with the variability of surface water quality was launched in the Coulee
Baton Microwatershed. Seven water quality monitoring sites were identified in the mcirowatershed. Field
installation for monitoring included the installation of 6712 ISCO samplers, 4230 ISCO Bubble Flow
Meters, 674 ISCO Rain Gauges with tipping bucket, solar panel, and battery. Water samples were collected
for 66 rain events from September 24, 2009 to August 9, 2011. Laboratory determinations of water samples
included TSS, BOD5, NO3-N, NO2-N, SRP, TP, TKN, Cl, Fl, SO4, and fecal coliform. Field measurements
included the determination of temperature, DO, turbidity, conductivity, and pH using YSI Sonde. Dissolved
oxygen level ranged between 1.2 mg/L to 14.1 mg/L, BOD5 level ranged between 2 mg/L to 40.1 mg/L, TS
concentration ranged between 35 mg/L to 5,719 mg/L , and TDS concentration ranged between 56 mg/L to
4,356 mg/L. Turbidity values for the Coulee Baton microwatershed ranged between 4.23 NTU to 1,864.1
NTU. Fecal coliform count ranged between 400 MPN/100 mL to as high as 17 million MPN/100 mL.
However, fecal coliform counts were reduced dramatically following the implementation of septic system
installation project by Acadiana RC&D in the microwatershed. These results clearly indicate that there are
heavy fluxes of pollutants in the microwatershed which are obviously related to landuse types and
agricultural practices. Principal component and factor analyses resulted in sediments, dissolved substances,
nutrients, temperature, and fecal matters as the major factors associated with surface water quality variability
in this microwatershed. Watershed managers and researchers can utilize PIMA for developing a highly
coordinated, multidisciplinary, and participatory water quality monitoring projects and BMPs
implementation programs to improve surface water quality of agricultural watersheds.
98
AN ANALYTICAL MODEL FOR POLLUTANTS TRANSPORT IN THE ROSETTA BRANCH

OF THE NILE RIVER, EGYPT
Mohamed Mostafa* and Robert W. Peters

(University of Alabama at Birmingham, AL, USA)
This research is being performed on the Rosetta branch of the Nile River, Egypt. The Rosetta branch
receives pollution loadings from domestic, industrial, and agricultural activities which are located along its
path. The primary objective of this research project is to develop an analytical model of Rosetta branch
pollution using MATLAB software. This model can be used to predict water quality and assess the
downstream distance affected by pollutant releases. Additionally, this model is considered a reliable tool for
water quality management in affected areas. Water samples were collected along the Rosetta Branch, and
from drains discharging into the Rosetta Branch to compare actual values with experimentally obtained.
Water samples were analyzed for different parameters which include biochemical oxygen demand (BOD),
chemical oxygen demand (COD), pH, total organic carbon (TOC), total dissolved solids (TDS), total
suspended solids (TSS), dissolved oxygen (D.O.), and temperature.
The main sources of pollution were studied to identify the most appropriate ways to reduce pollution
and improve water quality in the Rosetta branch. El-Rahawy drain is the main source of pollution along the
Rosetta branch, where it receives water from the Abu-Rawash and Zenen wastewater treatment plants
(WWTPs). Wastewater from El-Rahawy drain contains an average COD concentration of about 270 mg/L
and an average D.O. concentration of about 1.45 mg/L. The Abu-Rawash WWTP receives sewage
exceeding the absorptive capacity of the plant. Therefore, excess sewage is discharged directly to El-
Rahawy drain without even primary treatment, which leads to increase water pollution in the Rosetta branch.
This research addressed an attempt to improve Abu-Rawash WWTP effluent water quality by using
aluminum chloride (AlCl3) with injections of carbon dioxide (CO2). Jar tests were performed to estimate the
coagulant dosage required to reach acceptable treatment. Application of 0.6 mg/L of aluminum chloride
with injection of CO2 reduced the COD concentration at El-Rahawy drain from 270.0 mg/L to 112.0 mg/L.
Another approach involves discharging 780,000m3 of water daily from the Al-Buhairi Water Canal (flows
perpendicular to El-Rahawy drain and parallel to the Rosetta branch) to El-Rahawy drain reduced the COD
concentration at El-Rahawy drain from 112.0 mg/L to 80.0 mg/L and increased the D.O. concentration from
1.45 mg/L to 3.20 mg/L, which in turn will lead to improved water quality in the Rosetta branch.
99
POLYCHLORINATED BIPHENYLS (PCBs) IN INDUSTRIAL AND MUNICIPAL EFFLUENTS:

CONCENTRATIONS, CONGENER PROFILES, AND PARTITIONING ONTO
PARTICULATES
Aparna Balasubramani and Hanadi S. Rifai (University of Houston, Houston, TX, USA)
Nathan L. Howell (West Texas A&M University, Canyon, TX, USA)
ABSTRACT: The Houston Ship Channel (HSC) is one of the nation’s largest and most active ports with
shipping, petrochemical facilities and refineries, along with other industrial activities that have historically
used polychlorinated biphenyls (PCBs). Municipal and industrial wastewater discharges from these
industries are presumed to be a source of PCBs into natural water systems. This study examined wastewater
effluent samples that were collected from 16 different locations in the Houston area in the summer of 2009
to describe the magnitude and specificity of this source to the Galveston Bay Estuary. All 209 PCB
congeners were quantified using high resolution gas chromatography/high resolution mass spectrometry
(HRGC/HRMS) using the USEPA method 1668A. Various analyses examined the distributions of all 209
PCB congeners and homologs, the differences between the industrial and municipal effluents, and the
distribution of PCBs between the dissolved and suspended phases. This study is the first to quantify all 209
PCB congeners in wastewater effluents in Houston, Texas and the results presented stress the need for a
more rigorous approach for managing total PCBs since partitioning within the water column affects the truly
dissolved concentration that is bioavailable to biota and organisms in the Channel.
INTRODUCTION
Polychlorinated biphenyls (PCBs) belong to the class of persistent organic pollutants (POPs) and
are widely present in the environment. Due to their persistence, PCBs are found in almost all water bodies,
which makes these compounds both an environmental concern and a human health concern (Breivik et al.
2004). Major sources of organic pollutants in the environment include aerial deposition, surface runoff,
domestic and industrial wastewater effluents (Stevens et al. 2003). Previous studies (Barrick 1982,
Eganhouse and Kaplan 1982, Shannon et al. 1977) have confirmed that another significant source of toxic
contaminants like PCBs in the environment is treated effluents discharged from both wastewater treatment
plants and industries.
Characterization of PCBs from both industrial and municipal facilities has been described in a few
studies in the literature, with the earliest being done in the Canadian lower Great Lakes by Shannon et al.
(1977), in which they found that 66% removal of PCBs was observed in the secondary treatment of
wastewater, and that the removal was mainly due to the settling of PCBs in sludge. Blanchard et al. (2004),
Guo et al. (2009), and Pereira and Kuch (2005) have examined the distribution of a limited number of
congeners and homologs in sewage sludge that was obtained from various urban and industrial wastewater
treatment plants. Though various studies (Durell and Lizotte 1998, Rodenburg et al. 2011, Vogelsang et al.
2006) have addressed the presence of PCBs in wastewater effluents, there exists many data gaps with respect
to the nature and character of PCBs being discharged into natural water systems. Hence, identifying these
data gaps and determining the nature and character of PCBs discharged from this point source is very critical.
In order to address the aforementioned gapl, this study characterized the concentrations and
distribution of all 209 PCB congeners in effluents from 16 wastewater treatment plants and industrial
facilities that discharge into the Houston Ship Channel (HSC) in Texas. The main objectives of monitoring
the effluents were to determine the concentrations of all the 209 PCB congeners and homologs, and assess
the differences in the congener signatures between the different types of effluents. The study also determined
the distribution of PCBs between the dissolved and suspended phases and analyzed how organic carbon
affected the partitioning of PCBs between the two phases.

The samples were taken directly from six industries (I1, I2, I3, I4, I5, and I6), six municipal
wastewater treatment plants (WWTP1, WWTP2, WWTP3, WWTP4, WWTP5, and WWTP6), two
100
industrial wastewater treatment plants (O3, and O4), one refuse system (O1), and one special warehousing
facility (O2), as close to the discharge point into the receiving stream as possible, (see FIGURE 2). The 16
outfalls were selected from a total of 26 potential PCB point source dischargers into the HSC based on their
proximity to the HSC and PCB hot spots in water, sediment, or fish; nature of receiving stream; type of
industry; the known history of spill events within the facility; and the rate of discharge relative to the
receiving waters.
FIGURE 2. Location of the sampled effluent outfalls.
High volume sampling was used to collect the samples whereby 200 liters of water for each sample was
pumped through a pre-cleaned glass fiber filter containing a 1 µm filter then through a XAD2 resin contained
in a stainless steel column. The mass retained on the filter was considered to be the suspended fraction, and
the mass collected on the XAD2 resin was treated as the dissolved fraction. Also, for each of the samples, a
separate grab sample was collected and analyzed for total suspended solids (TSS), dissolved organic carbon
(DOC), and total organic carbon (TOC).
All 209 PCB congeners were quantified using high resolution gas chromatography/high resolution
mass spectrometry (HRGC/HRMS) using USEPA method 1668A (USEPA 1999). Each of the 17 samples
(16 parent samples + 1 duplicate) consisted of 164 PCB analytes and hence, a large amount of data was
generated, sorted, summed, visualized and statistically analyzed using Microsoft Excel 2007.
PCB Congener Patterns. The number of detects obtained in both dissolved and suspended phases in the
various effluents, percent detection, and congeners that exhibited maximum concentrations at each of the
effluent outfalls is presented in TABLE 1. It can be observed from TABLE 1 that 12 out of the 17 effluent
101
outfalls had greater than 50% detection in the dissolved matrix whereas only 7 out of the 17 effluent outfalls
had greater than 50% detection in the suspended matrix. The congener PCB-008 was among the highest
three congeners in 14 of the dissolved effluent samples whereas PCB-129/128/163 exhibited the highest
concentration in 14 of the suspended effluent samples.
TABLE 1. Number of detects and the three congeners that showed the maximum concentrations in the
dissolved and suspended phases for all effluents.
Three highest concentration PCB
Facility Number of detects %Detects analytes
Suspended Suspended
Dissolved phase Dissolved phase Dissolved Suspended phase
phase (>1µm) phase (>1µm) phase (>1µm)
110/115, 129/138/163,
I1 116 102 71 62 110/115, 52, 95 90/101/113
I2 74 23 45 14 8, 4, 1 15, 209, 8
129/138/163, 110/115,
I3 77 83 47 51 11, 8, 44/47/65 118
129/138/163, 153/168,
I4 87 108 53 66 1, 8, 3 180/193
44/47/65, 61/70/74/76,
I5 99 84 60 51 4, 8, 11 52
129/138/163, 110/115,
I6 87 97 53 59 8, 4, 15 153/168
129/138/163, 153/168,
WWTP1 88 28 54 17 11, 4, 8 90/101/113
129/138/163,
WWTP1-DUP 85 29 52 18 8, 4, 11 90/101/113, 110/115
WWTP2 64 2 39 1 4, 8, 1 209 (all other NDs)
129/138/163, 11,
WWTP3 103 72 63 44 11, 52, 20/28 110/115
11, 129/138/163,
WWTP4 61 40 37 24 11, 20/28, 31 153/168
129/138/163, 153/168,
WWTP5 106 66 65 40 11, 8, 18/30 147/149
153/168, 129/138/163,
WWTP6 83 47 51 29 8, 4, 11 147/149
129/138/163, 153/168,
O1 107 100 65 61 8, 4, 18/30 180/193
129/138/163,
O2 114 101 70 62 8, 4, 18/30 61/70/74/76, 153/168
129/138/163,
O3 73 29 45 18 8, 4, 1 90/101/113, 209
129/138/163, 147/149,
O4 89 62 54 38 4, 8, 11 153/168
Total PCBs (∑209) and Homolog Concentrations. It can be seen from FIGURE 3 that the total PCB
(∑209) concentration in the dissolved medium ranged from 1.01 ng/L to 8.12 ng/L whereas it ranged
between 2.03 ng/L and 31.19 ng/L in the suspended medium. It was noted that the concentrations were
relatively constant in industrial effluents whereas more variable in the municipal and other effluents in both
the dissolved and suspended media. While municipal wastewater treatment plants did not have the highest
concentration of total PCBs, they were the largest contributors to natural water systems because of the
relatively larger volume of effluents discharged on a daily basis. PCB homolog concentrations at all the
effluent outfalls were also analyzed to see if they followed any pattern like the total PCB (∑209)
concentrations. It was observed that relatively high concentrations were exhibited by lower chlorinated
homologs (mono-CBs through hexa-CBs) with dichlorobiphenyls exhibiting the highest concentration at
most of the effluent outfalls. An interesting observation was that at one of the industrial wastewater
treatment plant (O4) nonachlorobiphenyls peaked higher than octa-CBs and deca-CBs, which was different
102
from what had been observed in a previous study (Guo et al. 2009), and this could be attributed to the fact
that maybe the source and transport of PCBs into this wastewater treatment plant was different from the rest
of the facilities.
FIGURE 3. Total PCBs (∑209) concentration at each of the effluent outfalls in the dissolved and
suspended phase. (Non-detects = ½ MDL).
FIGURE 4. Suspended fraction in water at all the effluent outfalls plotted against log Kow obtained from
103
Hawker and Connell (1988) for the detected concentrations in the suspended and dissolved phases. The
distribution of TSS and TOC is also shown.
Suspended Fraction Vs log Kow and Partitioning onto Particulates. The suspended fraction was
calculated only for the detected concentrations in all the 17 effluent outfalls, by dividing the suspended
concentration by the sum of dissolved and suspended concentration of the same congener. The suspended
fraction values ranged from 0.0011 to 0.979 across the effluents, as seen in FIGURE 4. Although, as
expected, the higher the log Kow, the higher the suspended fraction, it was observed that suspended fractions
varied widely depending on the TSS and TOC concentrations at the outfalls (see FIGURE 4). High
suspended fractions observed at the municipal wastewater treatment plants were due to the high TSS
concentrations at these facilities, whereas high suspended fractions were noticed in the petrochemical
industries when the TSS and TOC concentration at that outfall was similar. The major conclusion derived
from this analysis was that though log Kow was a good indicator of the partitioning of PCBs, it alone was
not sufficient to understand the partitioning of PCBs since it did not give any information about the level of
TOC and/or TSS or the type of effluent stream, water quality indicators that determine the extent to which
specific congeners are present predominantly in the dissolved or suspended phase. Hence, based on these
results, the need for a detailed understanding of the role played by TSS and the various fractions of carbon
in effluent outfalls to control the contamination of POPs in natural water systems is deemed to be critical.
CONCLUSIONS
Apart from being the first study to quantify all 209 PCB congeners in wastewater effluents in
Houston, Texas, other interesting observations can be made. It was observed that total PCBs (∑209)
concentrations in the suspended medium were four times higher than the total PCB (∑209) concentrations
seen in the dissolved medium, and the difference in the concentrations seen at various plants confirmed that
treatment levels affected the PCBs in dissolved and suspended media very differently. This difference could
be because of the variable sourcing of PCBs in the influent or the actual treatment processes within the
plants or the chemical make-up of the effluent (organic carbon fractions, TSS). It was also observed that
lower chlorinated congeners dominated the homolog concentrations, with dichlorobiphenyls exhibiting the
highest concentration at most of the outfalls. Lastly, it was noticed that suspended fractions of PCBs, for the
same congener, varied widely amongst the different effluent outfalls, and the log Kow was not the only
deciding factor for the suspended fraction and that other parameters like TSS, TOC, DOC, and POC played
a very important role in the partitioning of PCBs. Hence, the results that were obtained from this study stress
the importance for development of a more rigorous approach that includes understanding of the chemical
make-up of effluent waters and their organic carbon fractions, because controlling total PCBs from a water
quality standpoint alone is not sufficient to predict the impact of PCBs on biota in natural water systems.
ACKNOWLEDGMENTS
This research was funded by the Texas Commission on Environmental Quality (TCEQ), and the
United Stated Environmental Protection Agency (USEPA). Their support is gratefully acknowledged.
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Tissue by HRGC/HRMS." Washington, D.C: USEPA National Office: 133.
Vogelsang, C., M. Grung, T. G. Jantsch, K. E. Tollefsen and H. Liltved (2006). "Occurrence and removal
of selected organic micropollutants at mechanical, chemical and advanced wastewater treatment plants
in Norway." Water Research 40(19): 3559-3570.
105
CHARACTERISTICS OF OPTIMIZATION PROBLEMS FOR COASTAL GROUND WATER

MANAGEMENT
Karen Ricciardi
(University of Massachusetts Boston, Boston, Massachusetts, USA)
This research reveals the characteristics of optimization problems applied to coastal ground water
management used as a source of fresh water. Coastal ground water aquifers generally consist of fresh water
underlain by salt water. When this fresh water is extracted from the aquifer, the salt water is often drawn
into the fresh water zone. If the salt water is drawn into the well, then the well is contaminated and can no
longer be utilized as a source of fresh water. The movement of the fresh water- salt water interface in
response to ground water extraction can be predicted using mathematical models that are solved using
computationally intensive algorithms. In this research the ground water flow model MODFLOW coupled
with the principles of the Ghyben-Herzberg approach are used to model the fresh water- salt water interface
in a hypothetical model. This approach models the interface as a sharp front, and provides a conservative
estimate of the interface response to ground water pumping. While this response is conservative, the
nonlinear effects of the response are consistent with more complex models, and it is for this reason that this
approach provides a means by which the characteristics of an optimization problem for coastal aquifer
management can be analyzed.
An optimization problem is formulated that examines the minimum risk of salt water intrusion into
active pumping wells that supply a fixed amount of fresh water from a coastal aquifer. The management
decisions in this problem include assigning pumping rates at available well locations throughout the aquifer.
To analyze this optimization problem, a large number of management designs are randomly generated. For
each design, the ground water model is used to predict the response of the aquifer to the design. Along with
the pumping rates assigned to each well, the risk of salt water intrusion is recorded. The risk is quantified
by the predicted proximity of the salt water interface to the well. Low risk designs are analyzed using a
clustering algorithm to differentiate designs according to well activation. Each cluster is then analyzed
using statistical measures. The results of this analysis reveal characteristics of the objective function that
are particular challenges to solving optimization problems using traditional algorithms. This optimization
problem is challenged with the presence of multiple locally optimal solutions that approximate piecewise
linear features that are non-differentiable close to the local solutions.
These results of this analysis are two-fold. By examining the solution space of the optimization
problem in the proposed manner, for this problem a wide range of low risk management solutions for coastal
aquifer management is revealed. These solutions are variable in the number of wells, the quantities of
pumping from the wells and the location of the wells in the management design. If the globally optimal
solution is desired, this research reveals characteristics of the objective function that are useful for
predetermining the derivative free optimization algorithm and the parameters of that algorithm that will
determine the global optimal in an efficient manner.
106
QUANTIFYING E. coli DISCHARGE FROM ONSITE SEWAGE FACILITIES IN THE

DICKINSON BAYOU WATERSHED, TEXAS
Derek Morrison1, Clyde Munster1, R. Karthikeyan1, John Jacob2

1
( Texas A&M University, Department of Biological and Agricultural Engineering, College Station, TX
77843, USA; 2Texas A&M University, Texas Sea Grant, 1250 Bay Area Blvd., Suite C, Houston, TX
770058, USA)
Since 1996, the bacteria levels in Dickinson Bayou have been considerably higher than the state limit of 126
bacteria / 100 mL for recreational waters. One hypothesis is that failing onsite sewage facilities (OSSFs) in
the nearby residential areas are causing an increase of E. coli concentrations in Dickinson Bayou. Three
water quality monitoring stations were installed in Dickinson Bayou to quantify E. coli in surface runoff.
There are two types of OSSFs in the watershed; aerobic and anaerobic systems. Aerobic systems disperse
the treated effluent by spraying the surface of the soil while anaerobic systems discharge untreated effluent
into the soil from gravel drainage trenches. This project will determine if either of the two types of OSSFs
is contributing to the elevated E. coli concentrations in Dickinson Bayou. Two of the monitoring sites were
placed in a neighborhood that uses OSSFs. The third monitoring station was a control site placed in a
neighborhood that is connected to a municipal wastewater treatment plant with no OSSFs. Each monitoring
site is equipped with a flow meter and an automatic sampler. Rainfall – runoff relationships were established
for each monitoring station. Water quality samples were obtained during runoff events at each monitoring
station and analyzed for E. coli concentrations. Runoff events were characterized as either wet, average, or
dry antecedent moisture conditions. The rainfall-runoff relationships and the E. coli concentrations in the
runoff will be presented in this presentation.
107
IMPACT OF SOIL TYPE ON THE SALT ACCUMULATION DUE TO RECYCLED WATER

IRRIGATION
Muhammad Muhitur Rahman*, Dharma Hagare and Basant Maheshwari (University of Western
Sydney, Penrith, NSW, Australia)
Peter Dillon (CSIRO Land and Water, Glen Osmond, SA, Australia)
In the recent years, recycled (reclaimed) water is increasingly being used for irrigating open, sports and
agriculture fields. Salt accumulation study due to reclaimed water irrigation in urban open spaces is a new
area compared to wastewater irrigation. Reclaimed water has more acceptability to use in irrigation
compared to untreated wastewater. However, the current, but limited, literature suggests that there is an
increased risk of salt accumulation in the vadose zone of the soil, which is irrigated with recycled water.
This is due to the presence of high levels of salt in the recycled water as compared to that of town water
supply. In this study, a laboratory column study was carried out to investigate the accumulation of salt in
the vadose zone due to continuous application of recycled water over a period of 100 days. Two types of
soil samples having the irrigation history of 9 and 18 years were collected from paddocks located in
Hawkesbury Water Reuse Scheme (HWRS), Australia.
Salt mass balance from the column study showed that the total cumulative leached salt mass was
less than that was applied. Thus indicating an increasing pattern of salt mass stored in soil profile. Impact
of soil type on salt accumulation at 0.2 m depth below the soil surface was evident. It was observed that
loamy sand soil had higher accumulation (about 10%) of salt compared to the loam soil. Salt accumulation
in both the soils was monitored in terms of bulk electrical conductivity by a dielectric sensor. However, bulk
electrical conductivity was observed to depend on volumetric water content. Therefore, an equation was
developed to convert bulk electrical conductivity to soil water electrical conductivity using the data that is
specific to soil type. Soil water electrical conductivity is widely used as the means to express soil salinity.
The equation predicted the soil water electrical conductivity in loamy sand soil with 98% and in loam soil
with 88% efficiency. The result from this experiment will assist in developing the salt management
strategies for these paddocks, which may be applied for other fields which are irrigated with recycled water.
108
DIVERSITY OF AQUATIC FLORA IN RELATION TO WATER QUALITY IN KOLLERU

LAKE, ANDHRA PRADESH, INDIA
P. Brahmaji Rao
(Acharya Nagarjuna University, Andhra Pradesh, India)
Kolleru Lake is the largest natural fresh water lake in India. Ramsar Convention was the first to identify the
lake in coastal Andhra Pradesh as a wetland. It is located between two major deltas of river Godavari on
the east and Krishna on the west. The lake (Long 810 - 40’ to 800 – 20’ East, Lat 170 – 25’ to 160 – 28’ north)
has an area of 954 Sq. Kms.. The present study is aimed to reveal the aquatic flora of Kolleru Lake and
nature of water quality depends on presence of diversity of aquatic flora at different field stations. Methods
of study based on important value index (IVI) of aquatic flora as a indicator to know the nature of water
either fresh or brackish.
Aquatic floral analysis to identify the species status, dominance and diversity variations among 17
field stations. Methods used to compute the frequency, dominance and abundance. Based on values
Important Value Index (IVI) was calculated. Highest IVI value for aquatic flora is Eichornia (76.7) at
seventeen field stations, Atapaka and minimum IVI for the species is Nymphaea (3.6) at third filed station
Prathikollalanka. plant species present or absent at field station was varied based on water quality.
Observations on Eichornia which is present in all field stations except in 12th field station known as
Upputeru Bridge. At Upputeru the Eichornia was not observed, because the outflow of the Kolleru lake
water leads to Bay of Bengal, there it may be slight variation in the fresh water becoming brackish water.
The observed reason of pharagmitis is absent at three field stations was due to undisturbed continuous water
flow.
109
DIVERSITY OF AQUATIC FLORA IN RELATION TO WATER QUALITY IN KOLLERU

LAKE, ANDHRA PRADESH, INDIA
P. Brahmaji Rao
Department of Environmental Sciences,
Acharya Nagarjuna University, Guntur, Andhra Pradesh, India
ABSTRACT: Kolleru Lake is the largest natural fresh water lake in India. Ramsar Convention was the first
to identify the lake in coastal Andhra Pradesh as a wetland. It is located between two major deltas of river
Godavari on the east and Krishna on the west. The lake (Long 810 - 40’ to 800 – 20’ East, Lat 170 – 25’ to
160 – 28’ north) has an area of 954 Sq. Km. The present study is aimed to reveal the aquatic flora of Kolleru
Lake and nature of water quality depends on presence of diversity of aquatic flora at different field stations.
Methods of study based on important value index (IVI) of aquatic flora as an indicator to know the nature
of water either fresh or brackish. Aquatic floral analyses were conducted to identify the species status,
dominance and diversity variations among 17 field stations. Methods used to compute the frequency,
dominance and abundance. Based on values Important Value Index (IVI) was calculated. Highest IVI value
for aquatic flora is Eichornia (76.7) at seventeen field stations, Atapaka and minimum IVI for the species is
Nymphaea (3.6) at third filed station Prathikollalanka. Plant species present or absent at field station was
varied based on water quality. Observations on Eichornia which is present in all field stations except in
12th field station known as Upputeru Bridge. At Upputeru the Eichornia was not observed, because the
outflow of the Kolleru lake water leads to Bay of Bengal, there it may be slight variation in the fresh water
becoming brackish water. The observed reason of pharagmitis is absent at three field stations was due to
undisturbed continuous water flow.
INTRODUCTION
The catchment area of the Kolleru lake is 4763 sq. km At 3 MSL to + 10 MSL. The lake is directly
fed by two seasonal rivulets Budameru and Tammileru (East and West branches) besides Ramileru and
Gunderu and 30 inflowing channels and drains. Upputeru in the southeastern end of the lake is the only
natural outlet draining the lake waters at Perentalakanuma into the Bay of Bengal after traversing 50 Km.
Several studied were carried out in different wetland of India. The aquatic vegetation of Kolleru
Lake was studied by Seshavatharam et. al., (1982). Floristic environment of Lake Kolleru, Seshagirirao
et.al., (1987), the vegetation in Kolleru was studied by Venkateswarlu (1993). Limnology and primary
productivity of the plankton community of Niland Lake, Kashmir was studied by Khan and Zutshi (1980).
A comparative study of plankton population of some typical water bodies of Jammu and Kasmir studied by
Kaul et. al., (1978). An integrated ecological approach of the lake Kolleru Development Authourity by
Mangapathirao (1987), Annon (1987).
MATERIAL AND METHODS

The main objective of this study was to find out the abundance of the macrophytes at selected
stations in the lake in relation to the ambient water quality and aquatic flora nature. Pilot studies have shown
that the lake supports a variety of hydrophytes which can be categorised as the emergent plants (Scirpus,
Typha, Phragmites, Eclipta); Submerged forms (Vallisneria, Ottelia, Hydrilla, Chara, Nitella); Free
floating forms (Salvinia, Eichornia, Pistia) etc. Cluster analysis (Bray Curtis) was done to identify
ecological groups by using the software tool “PAST”. Clusters were developed in two way method for both
aquatic flora and water quality parameters (Macfadyen and Ford, 1984).
Vegetation analysis has been done by lying transects / quadrates of selective sizes (10 m x 10 m) in
the study area. Raunkiaer (1934) indicates the number of sampling units. The numbers of plants present in
each transect / quadrates were counted. Plant materials collected during sampling are identified with the
help of standard herbaria of the Botanical Survey of India and Gamble volumes of the Department of Botany,
Acharya Nagarjuna University, Guntur. Finally, the Frequency, density, Relative frequency, Relative
110
density of each plant were calculated. At each station 5 transects / quadrates were laid down in an area of
two square kilometres and the frequency, of each plant were calculated.

The study carried out to estimate the aquatic
flora in and around Kolleru lake were observed and
identified 17 plant species from 17 field stations
(Table 1). Species dominance of aquatic flora based
on IVI values among the field stations were estimated
(Table 2). Species-Wise Distribution Pattern of
Aquatic Flora Present among Field Stations are
analysed (Table 3) and station wise status of flora and
degree of maturity of plant community is established
based on the percent frequency of all the species
(Table 4).
FIGURE 1. Study area of Lake Kolleru
First field station is MONDUKODU which is
having 90 cm depth and having significant geographical and ecological features. Thus each field station
was described in study area and tabulated. In this station 6 species of aquatic flora. Among the six species,
the dominant species are Eichornia and Phragmites with a maximum IVI value of 44.44. The lowest IVI
value 5.40 was exhibited by Alternanthera, Nymphaea. The highest MIV 100 was observed in Eichornia,
Ipomea and Phragmites and the lowest MIV 40.
Second field station is GUDIWAKA LANKA, having a depth of 85 cms. Among aquatic flora, 8
species of each were observed. Of the 8 species of aquatic flora, maximum IVI value was exhibited by
Eichornia 33.9 and minimum was shown by Alternanthera 5.48. The highest MIV was exhibited by
Eichornia, Ipomea and Vallisneria (100) and the minimum was shown by Alternanthera and Ottelia (40).
Third field station observed is PRATHIKOLLA LANKA which is having a depth of 110 cms. In
this station, 9 species of aquatic flora species were observed and identified. The analysis was done as, among
9 species, the dominant one is Hydrilla with a maximum IVI value of 29.47, and lowest IVI value was
noticed with Nymphaea (3.6). The highest MIV 100 was observed in Eichornia, Vallisneria, Salvinia, Chara
and Hydrilla. The lowest MIV 40 was noticed in Nymphaea.
CHETTUNNAPADU is the fourth field station had 6 Species of aquatic flora were identified and
its depth is 55 cms. Of the six aquatic species, Eichornia is dominant with a maximum IVI value of 47.46.
The Lowest IVI Value was noticed with Ottelia (8.64) .The highest MIV 100 was observed in Eichornia,
Ipomea and Nitella. The lowest MIV 40 was observed in Ottelia.
The fifth selected location is PEDAYADLAGADI. It depth is 70 cms .One can view the beauty of
the lake to a certain extent from this location.8 Species of aquatic flora were observed in this location. Of
the 8 species of aquatic flora, Eichormia is having the maximum IVI value of 39.20. The highest MIV 100
was observed in Eichornia, Ipomea and Nitella. The lowest IVI value 4.80, lowest MIV 40 was observed in
Nymphaea.
KOVVADALANKA is the sixth field station, having a depth of 45 cms. 6 Species of aquatic flora
were observed. Of the 6 species, Pistia is dominant having the maximum IVI value of 45.58. The highest
MIV 100 was noticed in Eichornia, Ipomea and Pistia and the lowest MIV 40 was observed in Nitella.
The Seventh field station is DEVICHINTAPADU. Maximum depth (130 cms) was observed here.
4 species of aquatic flora were observed. Of the 4 species of aquatic flora, Eichormia is dominant having
maximum IVI value i.e., 54.78.Phragmites is having the lowest IVI value i.e. 23.19.The highest MIV 100
was observed in Eichormia and Pistia. The lowest MIV 40 was noticed in Vallisneria.
VEGILAMALLI is the eighth field station. Its depth is 85 cms. 4 Species of aquatic flora were observed.
Of the 4 species of aquatic flora, Eichornia is dominant having maximum IVI value 63.00, and highest MIV
100, Nitella is having the lowest IVI value 17.00, and lowest MIV (40).
The ninth field station is CHATAKAYA. It depth was 100 cms.8 Species of aquatic flora were
observed. Of the 8 species in the aquatic flora, Salvinia is dominant having the maximum IVI value of 44.21,
and highest MIV 100. The minimum IVI value 8.95 and lowest MIV 40 were exhibited by Scirpus, Ottelia,
111
and Typha. BHUJABALAPATNAM was the tenth field station. The depth was 80 cms. 7 Species of aquatic
flora were observed. Of the 7 species, Eichornia is dominant, exhibited a maximum IVI value of 42.42,
highest relative frequency 30. The minimum IVI value 10.30 and lowest MIV 40 were observed in
Nymphaea and scirpus. The highest MIV 100 was noticed in Eichornia and Salvinia.
KOLLETIKOTA was the eleventh field station which has a depth of 100 cms. 8 species of aquatic
flora were observed. Of the 8 species of aquatic flora, Nitella is dominant having the maximum IVI value
44.21, and the minimum IVI value 6.05, were observed in Typha. The highest MIV 100 was obtained in
Nitella and the lowest 60 was noticed in Ottellia, Typha and Eclipta.
UPPUTERU BRIDGE was the twelfth station. It has a depth of 50 cms. 6 species of aquatic flora
were observed. Of the 6 species of aquatic flora, the maximum IVI value was exhibited by Ipomea (36.00).
The Minimum IVI value (13.14) was exhibited by Vallisneria (13.14) and Potamogeton. The highest MIV
100 was noticed in Ipomea and Alternanthera and the lowest value 60 was observed in Ottelia, Vallisneria,
Potamogeton, Ecilipta and Typha.
SIDDHAPURAM is thirteenth station. It has a depth of 55 cms.4 Species of aquatic flora were
observed. Of the 4 species of aquatic flora, the maximum IVI value (89.58) was shown by Salvinia. The
minimum IVI Value 6.05 was exhibited by Typha. The highest MIV 100 was observed in Eichornia,
Ipomea, Salvinia and Typha.
ADAVIKOLANU is the fourteenth field station. It has depth is 45 cms. 5 Species of aquatic flora
were observed. Of the 5 species of aquatic flora, Phragmites is dominant having, the maximum IVI value
49.23.The minimum IVI value 15.73, was shown by Ipomea and Pistia. The highest MIV 100 was shown
by Eichornia and Salvinia. The minimum MIV 60 was noticed in Ipomea, Chara and Pistia.
THOKALAPALLI is the fifteenth Station. It has a depth of 40 cms. 6 Species of aquatic flora were
observed. Pistia is dominant having the maximum IVI value 44.0. The minimum IVI value 9.71 was shown
by Alternanthera, Nitella. The Highest MIV 100 was observed in Eichornia and Pistia. The lowest MIV
20 was noticed in Alternanthera.
CHINAYADLAGADI is the sixteenth station. It has a depth of 70 cms. 6 Species of aquatic flora
were observed. Of the 6 species of aquatic flora, Eichornia is dominant having the maximum IVI 36.13.
The minimum IVI 14.84 was shown by Ipomea and Nymphaea. The highest MIV 100 was observed in
Eichornia and Typha. The lowest MIV 60 was noticed in Ipomea, Nymphaea and Hydrilla.
The seventeenth station in ATAPAKA. It has a depth of 120 cms. 3 species of aquatic flora were
observed. Eichornia is dominant exhibited the maximum IVI 76.67. The other two species Ipomea, Eclipta
exhibited minimum IVI value 42.50 (Ipomea). Eclipta and minimum MIV 40 were noticed in Ipomha.
Table 1. Systematic position of the species present in Kolleru lake
S.No. Family Name of the Species Vernacular name

1 Pontederiaceae Eichornia crassipes Gurrapu Decca
2 Convolvuloceae Ipomea aquatica Thulakada
3 Gentianaceae Nymphoides indicum Nymphoides
4 Amaranthaceae Alternanthera sessilis Ponnagantikura
5 Nymphaeacebily Nymphaea nouchali Kaluva
6 Cyperaceae Scirpus cernuus Fairy lights
7 Hydrocharitaceae Ottelia alismoides Duck lettuce Nir Veneki
8 Characeae Chara connivens Convergent stone wort
9 Hydrocharitaceae Vallisneria spiralis Navvaru nachu/Tape grass
10 Salviniaceae Salvinia aurticulata Pilli adugu
11 Araceae Pistia stratiotes Budaga tamara
12 Nymphaeaceae Nitella Sps. Stone wort
13 Potamogetonaceae Potamogeton nodosus Long leaf pond weed
14 Asteraceae Eclitpa alba Guntagalagara
15 Typhaceae Typha angustata Jambu
16 Poaceae Phragmites karka Kikkisa
17 Hydrocharitaceae Hydrilla verticillata Nachu
112
Table 2. Species dominance of Aquatic flora based on IVI values

among the field stations in Kolleru Lake
Potamogeton nodosus
Alternanthera sessilis
Nymphoides indicum
Nymphaea nouchali
Salvinia aurticulata
Eichornia crassipes
Hydrilla verticillata
Vallisneria spiralis
Ottelia alismoides
Phragmites karka
Chara connivens
Ipomea aquatica
Typha angustata
Scirpus cernuus
Pistia stratiotes
Eclitpa alba
Nitella Sps.
Field Station
Mondukodu 44 33 9.7 5.4 5.4 0 0 0 0 0 0 0 0 0 0 44.4 0
Gudiwakalanka 34 27 9.9 5.5 0 0 11 0 18.1 0 0 0 0 0 12.4 27.1 0
Prathikollalanka 18 0 0 0 3.6 6.5 14.5 14.7 22.1 22.1 0 0 0 0 0 12.2 29.5
Chettunnapadu 48 36 18 0 0 0 8.6 0 0 0 0 23.7 0 0 0 9.8 0
Pedayadlagadi 39 25 9.2 0 4.8 0 5.2 0 0 19.2 0 0 0 0 7.2 23.2 0
Kovvadalanka 36 36 0 0 10.7 0 0 0 0 0 45.6 7.9 0 0 0 7 0
Devichintapadu 55 0 0 0 0 0 0 0 29.6 0 0 40 0 0 0 23.2 0
Vegilamalli 63 0 0 0 24 0 0 0 0 44.2 0 17 0 0 0 33.3 0
Chatakaya 16 16 0 0 0 8.9 8.9 0 0 0 28.2 0 0 0 8.9 17.5 0
Bhujabalapatnam 42 19 14 0 10.3 10.3 0 0 17.6 0 0 0 0 0 0 30.3 0
Kolletikota 13 11 0 0 0 0 10.1 0 0 0 0 44.2 0 8.1 6.1 28.4 14.2
Uppeteru Bridge 0 36 0 28 0 0 17.5 0 13.1 0 0 0 13.1 0 0 30.9 0
Siddhapuram 23 20 0 0 0 0 0 0 0 53.3 0 0 0 0 0 37.1 0
Adavikolanu 33 16 0 0 0 0 0 23.6 0 0 15.7 0 0 0 0 49.2 0
Thokalapalli 40 21 0 9.7 0 0 21.9 0 0 0 44 9.7 0 0 0 0 0
Chinayadlgadi 36 15 0 23.4 14.8 0 0 0 0 0 0 0 0 0 27.1 0 29.7
Atapaka 77 43 0 0 0 0 0 0 0 0 0 0 0 42.5 0 0 0
Table 3. Species-Wise Distribution Pattern of Aquatic Flora Present

among Field Stations in Kolleru Lake
Name of the
S.
Plant 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
No.
Species
1 Eichornia + + + + + + + + + + + - + + + + +
2 Ipomea + + - + + + - - - + + + + + + + +
3 Nymphoides + + - + + - - - - + - - - - - - -
4 Alternanthere + + - - - - - - - - - + - - + + -
5 Nymphaea + - + - + + - + + + - - - - - + -
6 Scirpus - - - - - - - - + - - - - - - - -
7 Ottelia - + + + + - - - - + + + - - + - -
8 Chara - - + - - - - - + - - - - + - - -
9 Vallisneria - + + - - - + - - + - + - - - - -
10 Salvinia - - + - + - - - + - - - + - - - -
11 Pistia - - + - - + - - - - - - - + + - -
12 Nitella - - - + - + + + + - + - - - + - -
13 Potamogeton - - - - - - - - - - - + - - - - -
14 Eclitpa - - - - - - - - - - + - - - - - +
15 Typha - + - - + - - - + - + - - - - + -
16 Phragmites + + + + + + + + + + + + + + - - -
17 Hydrilla - - + - - - - - - - + - - - - + -
Total 6 8 9 6 8 6 4 4 8 7 8 6 4 5 6 6 3
113
Table 4. Maturity Index Values (MIV) of aquatic flora present

among field stations in Kolleru lake
Species vs Frequency %
Field
Station 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Eichornia 100 100 100 100 100 100 100 100 60 100 80 0 100 100 100 100 60
Ipomea 100 100 0 100 100 100 0 0 60 60 80 100 100 60 80 60 40
Nymphoides 60 60 0 60 60 0 0 0 0 60 0 0 0 0 0 0 0
Alternanthere 40 40 0 0 0 0 0 0 0 0 0 100 0 0 40 80 80
Nymphaea 40 0 40 0 40 60 0 60 0 40 0 0 0 0 0 60 60
Scirpus 0 0 60 0 0 0 0 0 40 40 0 0 0 0 0 0 0
Ottelia 0 40 60 40 60 0 0 0 40 0 60 60 0 0 60 0 0
Chara 0 0 100 0 0 0 0 0 0 0 0 0 0 60 0 0 0
Vallisneria 0 100 100 0 0 0 40 0 0 80 0 60 0 0 0 0 0
Salvinia 0 0 100 0 80 0 0 0 100 100 0 0 100 100 0 0 0
Pistia 0 0 0 0 0 100 100 0 60 60 0 0 0 60 100 0 0
Nitella 0 0 0 100 100 40 60 40 0 0 100 0 0 0 40 0 0
Potamogeton 0 0 0 0 0 0 0 0 0 0 0 60 0 0 0 0 0
Eclitpa 0 0 0 0 0 0 0 0 0 0 60 0 0 0 0 0 40
Typha 0 60 0 0 60 0 0 0 40 0 60 0 0 0 0 100 0
Phragmites 100 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Hydrilla 0 0 100 0 0 0 0 0 0 0 100 0 0 0 0 60 0
Total 440 500 660 400 600 400 300 200 400 540 540 380 300 380 420 460 280
MIV 73 71 83 80 75 80 75 67 57 68 77 76 100 76 70 77 56
Physico- chemical analysis: Water quality of Kolleru lake was analyzed based on parameters like pH,
temperature, conductivity, turbidity, total solvents, BOD, COD, alkalinity etc (Table 5). The readings of
such parameters help us to determine the condition of the lake compared to the standard values of the
parameters. The readings of these parameters of the water sample were indicate that almost all the points
got the above standard level value which indicates that the water quality is in deterioration stage. COD is
also very high which could be attributed to the influx of untreated or partially treated sewage water.
FIGURE 2. Graph showing Alkalinity, Chlorides and Hardness among 17 field stations
The depth of the lake ranges from 45cm to 130cm, the pH value ranges from 7.5 to 8.2, Conductivity
value ranges from 456 to 710 and Turbidity ranges from 11 to 22. Whereas the remaining parameters i.e.
DO, BOD and COD concentration levels vary among the 17 field stations was shown in the figure 1.
114
Similarly the relation between alkalinity, hardness and Chloride concentrations are predominantly correlated
among the field stations were shown in the figure 2. The Phosphate and Nitrate concentrations more or less
equal to all field stations whereas Sulphates are drastically ranging from one field station to another (figure
3). The similar studies on nutrient path way of Lake Kolleru ecosystem was described by Mangapathirao K
(1987).
FIGURE 3. Graph showing Phosphates, Nitrates and

Sulphate concentrations among 17 field stations
0 0 0 0 0 0 0 0 0 0 0 0 14.2 0 29.7 0 29.5 Hydrilla

0 0 0 12.4 7.2 0 0 0 0 0 8.9 0 6.1 0 27.1 0 0 Typha
0 0 5.4 5.5 0 0 0 0 0 9.7 0 0 0 0 23.4 28 0 A lternanthera
47.5 42.4 44.4 33.9 39.2 33.3 63 23.3 35.8 40 16.1 54.8 13.4 76.7 36.1 0 17.7 Eicho rnia
35.6 18.6 33.3 27.1 25.2 15.7 0 20 35.8 20.7 16.1 0 11.4 42.5 14.8 36 0 Ipo mea
9.8 30.3 44.4 27.1 23.2 49.2 33.3 37.1 7 0 17.5 23.2 28.4 0 0 30.9 12.2 P hragmites
23.7 0 0 0 0 0 17 0 7.9 9.7 0 40 44.2 0 0 0 0 Nitella
18.2 13.9 9.7 9.9 9.2 0 0 0 0 0 0 0 0 0 0 0 0 Nympho ides
0 17.6 0 18.1 0 0 0 0 0 0 0 29.6 0 0 0 13.1 22.1 Vallisneria
8.6 0 0 11 5.2 0 0 0 0 21.9 8.9 0 10.1 0 0 17.5 14.5 Ottelia
0 0 0 0 19.2 0 44.2 53.3 0 0 0 0 0 0 0 0 22.1 Salvinia
0 10.3 5.4 0 4.8 0 24 0 10.7 0 0 0 0 0 14.8 0 3.6 Nymphaea
0 0 0 0 0 15.7 0 0 45.6 44 28.2 0 0 0 0 0 0 P istia
0 0 0 0 0 23.6 0 0 0 0 0 0 0 0 0 0 14.7 Chara
0 10.3 0 0 0 0 0 0 0 0 8.9 0 0 0 0 0 6.5 Scirpus
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 13.1 0 P o tamo geto n
0 0 0 0 0 0 0 0 0 0 0 0 8.1 42.5 0 0 0 Eclitpa
1Mondukod
2Gudiwaka
9Chatakay
17Atapaka
16Chinaya
5Pedayadl
6Kovvadal
10Bhujaba
14Adaviko
13Siddhap
15Thokala
12Uppeter
4Chettunn
8Vegilama
7Devichin
3Prathiko
11Kolleti
FIGURE 4. Cluster analysis (Bray –Curtis Two way analysis) among 17 Field stations based on IVI
value of aquatic flora
115
55 85 70 45 100 100 80 45 50 55 40 70 120 110 85 130 90 Depth

112 142 175 184 143 197 186 186 164 153 132 116 175 214 213 232 243 CHLORIDE
256 276 414 437 354 445 324 434 537 476 423 398 387 437 365 243 235 SULP HATE
327 365 389 412 423 465 436 498 487 476 543 514 532 302 345 324 316 COD
312 334 354 367 387 397 368 454 416 412 542 476 523 235 321 298 276 B OD
394 521 494 245 278 289 427 456 527 547 478 284 357 567 632 623 384 A LKA LINITY
325 426 524 578 435 654 623 643 487 465 367 365 547 723 689 713 843 HARDNESS
563 567 612 632 497 512 423 385 543 476 532 578 523 456 643 621 598 CONDUCTIVITY
670 680 700 710 670 670 650 650 680 660 670 690 670 650 710 700 700 T.D.S
1.25 1.26 1.56 1.82 1.42 1.67 1.32 1.65 1.89 1.76 1.58 1.48 1.43 1.76 1.43 1.1 1.24 P HOSP HA TE
3.2 3.3 3.3 3.4 3.5 3.7 3.6 4 3.9 3.8 4.1 4 4.1 3.1 3.2 3.1 3.1 DO
7.6 7.7 7.7 7.5 7.5 7.5 7.6 7.6 7.7 7.7 7.6 7.5 7.5 7.8 8.2 7.8 7.6 pH
32 37 36 32 43 34 41 27 25 32 31 27 58 28 26 34 35 NITRA TE
19 20 21 22 18 18 11 14 20 17 19 20 19 16 22 22 21 TURBIDITY
Concentrations
1Mondukod
2G udiwaka
9Chatakay
16Chinaya
17Atapaka
5Pedayadl
6Kovvadal
10Bhujaba
14Adaviko
13Siddhap
15Thokala
12Uppeter
4Chettunn
8Vegilama
7Devichin
3Prathiko
11Kolleti
FIGURE 5. Cluster analysis (Bray–Curtis Two way analysis) among 17 Field stations based on
water quality
Table 5: Physico-Chemical analysis of water among field stations in Kolleru lake

CONDUCTIVITY
ALKALINITY
PHOSPHATE
TURBIDITY
Field Station
CHLORIDE
HARDNESS
SULPHATE
Depth (Cm)
NITRATE
T.D.S
COD
BOD
DO
pH
Mondukodu 90 7.6 700 21 598 3.1 276 316 384 243 843 1.24 35 235
Gudiwakalanka 85 8.2 710 22 643 3.2 321 345 632 213 689 1.43 26 365
Prathikollalanka 110 7.8 650 16 456 3.1 235 302 567 214 723 1.76 28 437
Chettunnapadu 55 7.6 670 19 563 3.2 312 327 394 112 325 1.25 32 256
Pedayadlagadi 70 7.7 700 21 612 3.3 354 389 494 175 524 1.56 36 414
Kovvadalanka 45 7.5 710 22 632 3.4 367 412 245 184 578 1.82 32 437
Devichintapadu 130 7.8 700 22 621 3.1 298 324 623 232 713 1.1 34 243
Vegilamalli 85 7.7 680 20 567 3.3 334 365 521 142 426 1.26 37 276
Chatakaya 100 7.5 670 18 497 3.5 387 423 278 143 435 1.42 43 354
Bhujabalapatnam 80 7.6 650 11 423 3.6 368 436 427 186 623 1.32 41 324
Kolletikota 100 7.5 670 18 512 3.7 397 465 289 197 654 1.67 34 445
Uppeteru Bridge 50 7.7 680 20 543 3.9 416 487 527 164 487 1.89 25 537
Siddhapuram 55 7.7 660 17 476 3.8 412 476 547 153 465 1.76 32 476
Adavikolanu 45 7.6 650 14 385 4 454 498 456 186 643 1.65 27 434
Thokalapalli 40 7.6 670 19 532 4.1 542 543 478 132 367 1.58 31 423
Chinayadlgadi 70 7.5 690 20 578 4 476 514 284 116 365 1.48 27 398
Atapaka 120 7.5 670 19 523 4.1 523 532 357 175 547 1.43 58 387
116
The present study results of IVI values of aquatic flora and water quality concentrations among 17
field stations ware given in the tables. The relation between water quality and aquatic flora were drawn by
the statistical approach – Bray – Curtis cluster analysis method by using PAST software. The similarity
among aquatic flora in Thokalapally and Kovadalanka, Pedayadlagadi and Gudiwakalanka,
Bhujabalapatnam and Mondukodu. The variance is high in Prathikollalanka (figure 4). Similarly water
quality analysis concentrations were also statistically worked out. The results indicates that Thokalapally
and Kovadalanka, Siddhapuram and Vegilamalli, Pedayadlagadi and Gudiwakalanka, Bhujabalapatnam and
Mondukodu. The only one field station i.e. Vegilamalli is having high IVI value consisting the more number
of species among all field stations (figure 5).
CONCLUSION
Floral analyses were conducted to identify the species status, dominance and diversity variations
among 17 field stations. Methods used to compute the frequency, dominance and abundance. Based on
values Important Value Index (IVI) was calculated. Highest IVI value for aquatic flora is Eichornia (76.7)
at seventeen field stations, Atapaka and minimum IVI for the species is Nymphaea (3.6) at third filed station
Prathikollalanka. Species presence or absent at each field station were compared among all stations by
Maturity Index Value (MIV) was evolved.
Present study findings revealed distribution of plant species present or absent at field station was
varied based on water quality. Observations on Eichornia which is present in all field stations except in
12th field station known as Upputeru Bridge. At Upputeru the Eichornia was not observed, because the
outflow of the Kolleru lake water leads to Bay of Bengal, there it may be slight variation in the fresh water
becoming brackish water. The observed reason of pharagmitis is absent at three field stations was due to
undisturbed continuous water flow.
ACKNOWLEDGMENTS:
My deep sense of gratitude to Prof K.V. Rao, Vice Chancellor, Acharya Nagarjuna University,
Guntur for permitting to do the research work and encouragement in my career. I also thank to A.P. Forest
Department for providing logistic support.
REFERENCES
Amyan Macfadyen, E. D. Ford (1984). Advances in Ecological Research, Volume 14 Academic Press, 245
pp.
Annon. 1987. Master plan for Kolleru Lake Development, An integrated Ecological approach. Office of the
Kolleru Lake Development, Kaikalur, 1987, 255pp.
Kaul, V. 1977. Limnological Survey of Kashmir lakes with reference to trophic status and conservation Int.
J.Ecol. Environ. Sci. 3: 29-44.
Kaul, V., D.N. Fotedar, A.K. Pandit and C.L. Trisal 1978. A comparative study of plankton population of
some typical fresh water bodies of Jammu and Kashmir State. Environ. Physiol. Ecol. Plants. 249-269.
Khan, M.A. and D.P. Zutshi 1980. Contributions to High Altitude Limnology of the Himalayan system. I.
Limnology and primary productivity of the plankton community of Niland Lake. Kashmir.
Hydrobiologia 75(2): 103-112.
Mangapathi Rao, K. 1987. Master Plan for Kolleru lake development - An integrated ecological approach.
Office of the Kolleru lake development authority, Kaikaluru, Government of Andhra Pradesh.
Mangapathi Rao, K. 1987. The nutrient path way in Kolleru lake ecosystem. Proc National seminal on
aquatic biology. Andhra University, Waltair.
Raunkiaer, C. 1934. The life forms of plants and statistical geography. Claredon, Oxford, pp.632.
Seshavataram. V.B.S.M. Dutt and P.Venu.1982. .An ecological study of the vegetation of Kolleru lake.
Bulletin Botanical survey of India. 24(11-4): 70-75pp.
Seshavataram.V. and P. Venu.1981. Some observations on the ecology of Kolleru lake. International J.
Ecol. Enuviron. Sci. 7: 35-44pp.
Seshavatharam.V. and Venu. P. 1982. Ecological Studies of the Vegetations of Kolleru Lake. Bull.
Botanical Survey of India 24(1-4): 70–75.
117
Venkateswarlu V (1993) Floristic Environment of Lake Kolleru, Kolleru Lake - Environmental Status (Past
and Present), EM International publishers, 87pp.
118
STUDY ON WATER QUALITY VARIATION DURING RAINFALL RUNOFF EVOLUTION

PROCESS IN A CITY RESIDENTIAL DISTRICT
Huaien Li*, Jiake Li and Zengchao Liu

(State Key Laboratory of Eco-Hydraulic Engineering in Shaanxi, Xi'an University of Technology, Xi’an,
Shaanxi, China)
In order to investigate the water quality variation and pollution characteristics of runoff during rainfall runoff
evolution process, water quality of undisturbed rain, roof runoff, road and outlet runoff for 6 events were
monitored in 2011 in a residential district in Xi’an city, Shaanxi, China. The results showed that: 1) the
water quality of undisturbed rain was better than that of roof runoff and outlet runoff, and the water quality
of road runoff was worst; 2) road runoff were seriously polluted with a higher average concentration for
COD, ammonia nitrogen and TN; 3) the pollution of rainfall runoff has first flush effect in a certain degree,
the concentrations of pollutants such as SS, COD and TN in the initial stage were higher than the later in a
rainfall runoff process; 4) the larger the number of antecedent dry days for rainfall event, the higher
concentration of pollutants in runoff; and 5) the grass strip between building and road can partly reduce the
concentration of pollutant such as COD and TN.
119
LOW COST AUTONOMOUS SENSING PLATFORMS FOR THE DIRECT DETERMINATION

OF NUTRIENTS IN WATER
Deirdre Cogan, John Cleary, Kamil Jankowski and Dermot Diamond (Dublin City University, Glasnevin,
Dublin 9, Ireland)
Mark Bowkett (T.E. Laboratories, Tullow, Carlow, Ireland)
ABSRACT: There is a growing need for low cost, remote sensing systems which can be deployed in situ
in sufficiently large numbers to ensure that data on key water quality parameters is readily available. The
challenges facing this ideal of monitoring include the cost of these platforms and the inability to “deploy
and forget” due to limited long term stability and maintenance requirements. Microfluidic technology has
great potential as a solution to the increasing demand for environmental monitoring, by producing
autonomous chemical sensing platforms at a price level that creates a significant impact on the existing
market. The development of sensing platforms for ammonia and nitrate in water and wastewater are being
investigated. Our approach is to combine microfluidics with simplified colorimetric chemical assays; low
cost LED/photodiode-based optical detection systems; and wireless communications. In order to drive down
the cost of these devices, it is vital to keep the fluidic handling requirement as simple as possible, as
multistage methods are expensive to implement as well as being less reliable in long-term deployments.
Colorimetric methods for nitrate and ammonia have been modified eliminating several steps previously
associated with the methods to facilitate their implementation into an autonomous platform, resulting in a
rapid and simple measurement procedure.
INTRODUCTION
Environmental sensors have great potential as a solution to the increasing demand for environmental
monitoring.(Diamond, 2004) Presently, the challenges facing this ideal of environmental monitoring include
the cost of these platforms and the inability to “deploy and forget” due to limited long term stability and
automated platform maintenance requirements. The objective of this research is to produce a self-sustaining
platform at a price level that creates a significant impact on the existing market. This will lead to the
development of compact autonomous instruments for in situ continuous monitoring of remote locations over
long deployable lifetimes (Cleary et al., 2010). The focus will be on critical factors like miniaturisation of
the device and minimisation of the reagent consumption. Developing this class of environmental monitoring
technology will require a multidisciplinary approach involving electronics, wireless communications,
environmental science, engineering and materials science with microfluidics playing a key role. Currently,
monitoring for nutrients in our waters such as nitrate and ammonia is based on in situ manual sampling
followed by laboratory analysis using standard laboratory instrumental and/or wet chemical methods. This
results in the infrequent monitoring of water at a fewer number of locations than is desirable, as it is time
consuming, expensive, non-scalable and requires skilled personnel.
Despite the enormous activity both into sensor networks and into the development of improved
chemical sensors over the past decade, there has been virtually no penetration of chemical sensing platforms
into widely distributed sensor network deployments, although the key challenges have been repeatedly
emphasised (Diamond, 2004). Approaches to water quality monitoring of nutrient levels like nitrate and
ammonia have been the subject of much research over many years. However these well-established
laboratory methods are making little progression into practical adoption for autonomous field based
instruments. Cost is a major factor of this, as reagent based analysers can cost up to €15,000 per unit
(Microlab autonomous phosphate analyser retails at ca. €20K per unit, including vat, in Ireland, Micro Mac-
1000 costing ca. €18,000; autonomous instruments from YSI, and HACH are similarly priced), mainly due
to the need to incorporate expensive fluidic handling components, like pumps and valves, which can
represent approximately 60% of the total component cost. The clear message from these numbers is that
chemical sensors and biosensors do not meet the specifications for large-scale deployments, due to price,
performance and reliability issues.
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Therefore, in order to drive down the cost of ownership of these devices, it is imperative to keep the
fluidic handling requirement as simple as possible, as complex, multistage approaches are correspondingly
challenging and expensive to implement due to a high purchase price, as well as being less reliable in long-
term deployments due to high maintenance costs. This research therefore, focuses on the simplifying the
colorimetric methods of nitrate and ammonia for simple, inexpensive and reliable integration into sensing
platforms.
NITRATE DETECTION
The first use of a direct nitrate analyser using chromotropic acid has been developed (Cogan et al.,
2013). A simplified chromotropic acid method eliminating several steps previously associated with this
method is employed in the platform. In a sulphuric acid medium, chromotropic acid reacts with nitrate ions
and produces a characteristic yellow colour associated with an absorbance band in the visible region (λmax
= 430 nm). The modified method allows for nitrate determination over the linear range 0.9 – 80 mg/L nitrate
with a limit of detection of 0.73 µg/L nitrate. Validation was achieved by analysing water samples from
various sources including groundwater, trade effluent and drinking water by the modified method and by
ion chromatography. The method was implemented on a flow analysis platform shown in figure 1
incorporating a low cost paired emitter-detector diode (PEDD) as the optical detector. An excellent
correlation coefficient of 0.993 was obtained between the modified method and ion chromatography. The
modified chromotropic acid method represents a rapid, simple, low cost technique for the direct
determination of nitrate in water.
FIGURE 5. Nitrate Analyser and PEDD Detection System. (1) Reagent storage (2) Sample storage (3)
Peristaltic micro pumps containing Santropene® tubing (4) Waste storage (5) Tygon® tubing (6) PEDD
flow cell (7) Mixing junction (8) Wixel microcontroller with breakout board containing wireless serial
link and data logger (9) Glass flow cell (10) Detector LED at 630 nm (11) Emitter LED at 430 nm (12)
Waste line (Tygon tubing).
Nitrate sensors currently on the market predominantly use direct UV spectrophotometric screening,
electrodes, or the cadmium reduction method, which in turn can be quite costly and/or prove difficult to
implement due to the relatively intricate procedures involved, probability of interferences present and the
limited detection ranges associated with various methods. There is therefore a major appeal to integrate this
simple, direct method for the determination of nitrate into an autonomous platform. An area of concern that
has been emphasized with this method is the use of 96% sulphuric acid (ca. 18 M) that must be present in
the chromotropic acid reagent for effective formation of the nitrate complex. The strongly acidic
environment drastically constrains the materials that can be used to store and move the reagent in the fluidic
system. It is therefore of major interest to ensure the reliability and robustness of the materials used within
the sensing platform. The materials such as the Tygon tubing used within the previous flow analysis platform
had a shelf life of approximately two weeks of extensive use as the chemical compatibility was quite poor
and resulted in a melting and discolouration effect.
121
As a result an extensive study of over one year was performed on the chemical compatibility of the
sulphuric acid and chromotropic acid reagent with various materials. Although this may seem relatively
trivial, the managing and understanding of the fluidic components is key in realising a fully reliable
deployable platform. The results are shown in table 1 and figure 2.
TABLE 1. Chemical Compatibility Results.
Material Compatibility
Polypropylene Severe effect

Polyurethane Severe effect
PTFE (Teflon) Excellent
PVC (Polyvinyl chloride) Severe effect
Silicone Severe effect
Tygon® Severe effect
Tygon® Fuel(Lubricant) Tubing Severe effect
Neoprene Severe effect
Santoprene® Severe effect
Viton® Excellent
FIGURE 2. Effects of ~98 % Sulphuric acid and chromotropic acid complex on various materials
FIGURE 3(A). Calibration curve from 0–80 mg/L NO3- and chromotropic acid complex. The standard
deviations as represented as error bars (n=3). FIGURE 3(B). Field deployable platform for the detection of
nitrate using chromotropic acid (1) robust and waterproof housing; (2) reagent and standard storage bags;
(3) 12 V battery; (4) optical detection enclosure; (5) peristaltic pumps containing Viton Tubing.
Viton® tubing is a brand of synthetic rubber and fluoropolymer elastomer from DuPont
Performance Elastomers L.L.C. showing excellent resistivity to the chromotropic acid reagent.
Subsequently, Viton tubing was incorporated into the peristaltic micro pump (Series 100, Williamson
Manufacturing Company Ltd) previously used in the flow analysis platform, and set to continuously deliver
122
sample and reagent via the Viton tubing over a one month period. Following the successful performance of
the one month trial, the pump delivered reagent and sample to the mixing junction where the coloured
complex formed passed through the PEDD detection system (O’ Toole et al., 2005) in a modified glass flow
cell (Brand Ltd Cat. No.7477 15) for a period of 37 days. A calibration plot (figure 3A) was obtained and
shown below using nitrate standards up to 80 mg/L NO3-.
These results shown are significant as the extremely high content and aggressive nature of the
sulphuric acid is no longer an issue for a field deployable platform. Although the chemistry has been
previously optimised and validated in a previous study, this study on the chemical compatibility with plastics
is noteworthy and will allow for the reliable integration into an autonomous platform shown in figure 3(B).
AMMONIA DETECTION
It is now evident that in order to maintain and acquire a reliable, reproducible and robust sensing
platform, the fluidic handling strategies must remain as simple as possible. For the determination of
ammonia, the Berthelot method was employed. In this method, an intensely blue coloured compound,
indophenol, is formed in the presence of ammonia, hypochlorite and phenol catalysed by sodium
nitroprusside. The most utilised variation of the Berthelot method incorporates a three step reagent process
with the addition sequence and reaction time of the variants of this method playing an important role in the
colour formation (Daridon et al., 2001). This method could prove problematic to implement in a low-cost
fluidic monitoring platform due to the multiple stages involved. It was therefore imperative to simplify the
Berthelot method to allow for easy integration into an autonomous platform while maintaining satisfactory
analytical results. Phenol was replaced with sodium salicylate due to the high toxicity and reactivity of
phenol. In a sodium hydroxide medium, the Berthelot reagent reacts with ammonium ions (NH4+) to produce
a characteristic green colour (λmax at 660 nm arising from the use of salicylate rather than phenol). Recent
studies simplified this to a two-stage reagent reaction sequence for the determination of ammonia in air.
(Bianchi et al., 2012) This method was further developed for the determination of ammonia in water by
employing a reagent pre-mix stage immediately prior to addition of the sample at a 1:1 v/v reagent to sample
ratio. Reagent 1 (R1) contains 6.906g of sodium salicylate and 0.225g of sodium nitroprusside in 250 ml of
0.5 mol l-1 sodium hydroxide solution while reagent 2 (R2) contains 7.5 ml of sodium hypochlorite (10-15
% available chlorine, used as received, Sigma-Aldrich 425044), 7.5 ml of 1 mol l-1 sodium hydroxide in 250
ml volumetric flask with deionised water. Both reagents were protected from direct sunlight by storing under
amber coloured glass.
FIGURE 4(A). Schematic of the analyser and microfluidic chip. FIGURE 4(B). Calibration curve using
the ammonia microfluidic chip from 0-12 mg/L NH4+ Berthelot complex. The standard deviations are
represented as error bars (n=3).
This approach is necessary as the complete reagent mixture (R1+R2) is not stable, and must be
freshly generated in-situ in order to obtain reproducible and accurate results. Following the optimisation of
the measurement parameters, a validation process was implemented using 6 samples from various
environmental sources. The samples were split, and parallel assays independently performed at the T.E.
Laboratory site. The modified Berthelot method was performed and compared to reference measurements
123
obtained using ion chromatography where an excellent correlation coefficient was obtained between the
modified Berthelot method and ion chromatography.
Figure 4(A) is a schematic of the microfluidic chip and illustration of the operating platform that
was designed for the modified Berthelot reaction, showing the basic design and operation. The fluidic
system comprises of sample intake, filtering unit, storage units for standards, reagents and waste and
pumping system (comprising of pumps and valves) which controls the transport and mixing of the sample,
standards and reagent; microfluidic detector chip; and waste storage. The pumping system comprises of 4
syringe pumps and check valves which were designed and built in-house and stepper motors with a total
component cost of €74.00. This fluidic system controls the syringe plungers are used to deliver the sample
and reagent via Tygon® tubing (I.D. 4.6 mm, Sigma Aldrich, Ireland) to the microfluidic mixing and
detection chip.
The optical detection system consists of a 660 nm LED (light emitting diode) with a photodiode
detector which enables an absorbance reading to be carried out on the ammonia/Berthelot complex. The
control and data layer consists of a microcontroller (MSP430, Texas Instruments) which controls the
operation of the pumping system and optical detector, a micro-SD card (COM-08163, Sparkfun Electronics)
for data storage; and a Wixel (WRL-10665, Sparkfun Electronics) for wireless communication using 2.4
GHz Radio. Power is provided by a 12 V, 4 Ah lead acid battery for autonomous operation, or by a mains
power adapter for online operation. Reagents R1 and R2 are pumped into the reagent mixing channel in the
microfluidic chip in a 1:1 v/v R1 to R2 ratio and the resulting mixture delivered to the sample mixing channel
at a 1:1 v/v sample to reagent ratio and then pumped into the detector chip. The microfluidic chip shown in
figure 4(A) was designed and built in-house, which is fabricated from UV-bonded layers of PMMA (poly
methyl-methacrylate) into which a 0.5 mm channel has been formed by micro-milling. One side of the
channel is adjacent to a mirrored surface. The 660 nm LED is oriented so that the light emitted is directed
across the microfluidic channel, and reflected by the mirrored surface back across the channel to the
photodiode, which converts the light intensity into a corresponding ADC value. The optical pathlength
through the sample is effectively doubled so that the absorbance signal is increased in accordance with
Beer’s law (Equation 1) without needing to increase the physical pathlength or affecting the sample volume.
Beer’s law states that:
A = ƐcL (1)
Where A is absorbance, Ɛ is the extinction coefficient of the absorbing species, c is concentration, and L is
pathlength. The method gave a linear response to ammonia concentrations up to 12 mg L-1 NH4+ after which
the absorbance plateaus shown in figure 4(B).
SIMPLIFIED COLORIMETRIC METHODS

Although the colorimetric methods for the determination of ammonia and nitrate have been
modified for the purpose of integrating into an autonomous platform, the methods also show great potential
as rapid, simple and reliable lab bench methods. A study was conducted in the University of Sao Paulo
(USP), Pirassununga, Brazil where case studies are on-going in the areas of nutrient detection in various
water bodies such as waste water treatment plants, aquaculture aquariums and freshwater systems. The
campus location was found to be ideal for monitoring such nutrients with these simple and rapid methods
in the areas of waste water treatment, aquaculture studies and agriculture science, all of which require daily
water quality monitoring. The monitoring was primarily focussed on an anaerobic-aerobic fixed bed
bioreactor designed in USP that treats waste water effluent from a dairy farm located on campus. The
bioreactor is part of an on-going long term study within USP and the manual monitoring of nutrients such
as nitrate and ammonia play a crucial role in determining the overall performance of the bioreactor.
Most of the routine water quality monitoring is currently carried out using HACH reagents and
instrumentation (HACH DR 2800 spectrophotometer). Although this allows for easy and rapid
determination of nutrients in water, discrepancies can arise as certain methods (including nitrate
determination) can be sensitive to different mixing techniques and concentrations ranges associated with
some of the HACH methods can be quite limited. As the chromotropic acid and the modified Berthelot
method are based on standard methods and show excellent correlation with ion chromatography, the
124
chromotropic acid method and the Berthelot method were compared daily to the on-going measurements
achieved by USP, results for the nitrate and ammonia levels are shown in table 2. Various discrepancies
can be found between the different methods mainly due to the limited ranges that the HACH methods offer
but also due to the errors/inconsistencies in mixing the HACH reagents with sample that may vary from
person to person. As a result, these methods will now be continued for water quality monitoring within the
USP campus on a regular basis.
TABLE 2. Comparison of results from anaerobic-aerobic fixed bed bioreactor.

Bioreactor
Nitrate Ammonia
HACH HACH
Modified
Chromotropic Handheld Handheld
Sample Run HACH DR 2800 Sample Run Nesslerization Berthelot
Acid Method colorimeter DR colorimeter
Method
900 DR 900
1 59.22 73.21 70 1 Out of Range 21.689 Out of Range
2 70.88 45.5 43.877 2 6.8 10.03 12.8
3 2.5 6.54 8.1 3 19.24 31.72 6.99
4 25.69 26.2 8 4 0.13 10.5 16
5 0.5 0.66 0.5
CONCLUSION
The long-term deployment of chemical analysers is hindered by the lack of robust and reliable
chemical sensing platforms. While much research is focused on the development of prototype sensors work
must be achieved in transcending this research into the real analytical world. The progress in automated
flow injection analysis (FIA) systems is prohibited by large sample volumes which results in high
consumption of reagents and standards. The focus has now turned to microfluidics for the miniaturisation
of these analytical techniques.(Marle & Greenway, 2005) Through the miniaturisation of these devices and
keeping the fluidic design as simple as possible, the overall reliability of the systems can be improved while
reducing cost.
The major focus is on real deployments with these modified approaches for in situ environmental
monitoring. The emphasis will be on the real issues related to the analytical approach and sampling within
environmental waters and in particular, keeping the sensor platform operating autonomously over time.
ACKNOWLEDGEMENTS
The authors wish to thank the QUESTOR Centre (grant code DCU9/11/14) and Enterprise Ireland
(grant code IP/2011/0103).
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using an autonomous microfluidic sensor." Paper presented at the Sensors Applications Symposium
(SAS), 2010 IEEE, 36-40.
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in Analytical Chemistry, 24(9), 795-802. doi:http://dx.doi.org/10.1016/j.trac.2005.08.003
O’ Toole, M., Lau, K. T., & Diamond, D. (2005). "Photometric detection in flow analysis systems using
integrated PEDDs." Talanta, 66(5), 1340-1344. doi:10.1016/j.talanta.2005.01.054
126
QUAL2K WATER QUALITY ANALYSIS AND SOURCE LOCATIONS IDENTIFICATION: A

CASE STUDY OF NORTH BUFFALO STREAM
Jenberu Feyyisa, Shoou-Yuh Chang, Samuel Massie

(North Carolina Agricultural and Technical State University, Greensboro North Carolina, 27401, USA)
City waters are suffering from waste release that grows at an alarming rate. QUAL2K is a framework that
helps simulate the water quality of streams and rivers. It approximates complex physical, chemical and
biological processes of streams and rivers through a simplified representation. By considering the stream as
one-dimensional, steady-state and non-uniform flow, QUAL2K calculates water quality kinetics for the
stream/river under consideration. It involves setting up of model components; reaches, elements, hydraulic
and kinetic parameters, initial conditions for hydrodynamic and water quality simulation. This model is used
to simulate one of the impaired waters of North Carolina, North Buffalo stream against its designated
purpose (aquatic life propagation). The 20.5 kilometer of North Buffalo stream channel was divided into six
(6) reaches and one hundred and four (104) elements each with 200 m. Before modeling water quality,
hydraulic parameters of the stream reaches were simulated and predicted for two different flow seasons of
the year, summer and winter. Based upon the calibrated stream channel hydraulic parameters, we obtained
good agreement between calibration of August 2, 2007 and prediction for January 4, 2007 with their
respective measurements. The model approximates waste load locations for the selected critical flow
condition and also indicates DO condition along the stream reaches and segments.
127
TECHNICAL, FINANCIAL AND ADMINISTRATIVE CAPACITY EVALUATIONS AND

IMPROVEMENT OF SMALL COMMUNITY WATER SYSTEMS IN PUERTO RICO
Adaíl Alicea-Martínez, Rafael A. Rios (University of Puerto Rico Río Piedras, Environmental Sciences
Department, San Juan, Puerto Rico, USA)
ABSTRACT: In Puerto Rico, 3% of the population gets its drinking water from approximately 250 small
community water systems, that are managed by the communities but still have to fully comply with the Safe
Drinking Water Act and state regulations. This study had a duration of two years and its objective was the
evaluation of 48 community water systems in Puerto Rico with a Capacity Development Form (CDF) which
measures their technical, administrative and financial capacity and combines it into a total capacity rating.
There was an initial and final evaluation to measure changes in capacity once the needs where identified at
the beginning and a circuit rider program was implemented. A scale from 0 to 100% was used to measure
each capacity. It was found that on average the aqueducts had a total capacity of 47% at the beginning, but
at the end they improved on the three categories. The level of improvement varied with factors like the level
of commitment of the community leader with the aqueduct, the economic means of the community and the
education of its members. These factors, which are numerically intangible because they have to do with
environmental justice more that with numbers, were not assessed by the CDF.
INTRODUCTION
Water conservation is important for drinking, food confection, and recreational uses because it is a
limited source and is essential to life. Water quality can be compromised because of infectious agents, toxics
and other hazardous compounds (WHO, 2010a). The World Health Organization (2013) established that for
2011 around 768 million people used unimproved sources of drinking water and 83% of the population
without access to better sources of water lived on rural areas. People from rural areas get their drinking
water from small community water systems that are managed by operators who typically are members of
the community and lack training in the system. (WHO, 2010b).The United States Environmental Protection
Agency (USEPA) has established that 300.2 million people in the United States obtain their potable water
from 52,873,000 community water systems (USEPA, 2010).
In Puerto Rico, 3% of the population obtains potable water from small community water systems
and 97% from the Puerto Rico Aqueducts and Sewer Authority (PRASA) (DOH, 2008). PRASA, which is
the only entity in the United States that serves practically a whole state, is a public corporation created on
1945, (“Ley de Acueductos y Alcantarillados de Puerto Rico” Act Num. 40, May 1, 1945, as amended)
whose purpose is to provide an adequate drinking water service to the people of Puerto Rico (PRASA,
2014). However, the other 3% of the population has been excluded because the construction and operation
of PRASA aqueducts in distant and rural areas was not economically feasible. In the 1950’s people from
the rural areas who lacked access to potable water decided to do by themselves the construction of
community water systems to get drinking water (Marti, et al., 2004). A community water system is defined
as a water system on rural areas operated by the residents of the community (DOH, 2008) commonly known
in Puerto Rico as Non-Puerto Rico Aqueducts and Sewer Authority (Non-PRASA). Typically a Non-
PRASA system is composed of a source of water, a storage tank and a distribution line (Figure 1). At the
present time, there are approximately 250 Non-PRASA systems that provide potable water to approximately
125, 000 persons. These systems have evolved and improved over time depending on the population and
the resources of the community. They vary from one another, some of them with more than one source of
water and storage tanks, with disinfection processes and others with more than one distribution line (Figure
2).
There have been significant efforts to develop drinking water quality standards and better
infrastructure for public potable water systems, but there are still public health risks related to poor water
quality. Specifically, small rural aqueducts are more vulnerable to water related illnesses than public water
systems (WHO, 2010a). However, although some of them have improved, because of the increase on
128
population due to the immigration from urban to rural areas and the increase on federal and state regulations,
the Non-PRASA systems are confronting problems, specifically on complying with the Safe Drinking Water
Act (SDWA) (Martí, et. al., 2004).
FIGURE 1. Photos of Water Source (Well), Storage Tank and Distribution Line.
FIGURE 2. Aerial Photo of a Community Water System (Non-PRASA System) in Barranquitas, Puerto
Rico including five water sources (four underground and one superficial), f
our storage tanks and a community office.
In 1996, Congress amended the SDWA with the purpose of assisting the states and the public water
systems to provide safe drinking water. The 1996 amendments established a program that encouraged the
strengthening of technical, administrative and financial capacity of water systems for the purpose of
129
providing safe drinking water (USEPA, 2012a). The U.S. Environmental Protection Agency (2012b) states
that a capacity development program in small community water systems provides a framework in which
both the governmental agencies and the small aqueducts work in collaboration with one another to have the
tools necessary for the systems to achieve the needed capacity and comply with SDWA regulations.
This study had a duration of two years. The objective was to evaluate 48 community water systems
using a capacity development evaluation form at the beginning and at the end of the study. The purpose was
to measure if there was an improvement on the three capacities after a circuit rider program was
implemented and an action plan was developed with the community’s inputs.

We used a Capacity Development Evaluation Form developed by the Department of Health, Potable
Water Division of Puerto Rico, to perform the evaluation of 48 community water systems around the island
(Figure 3). We performed two evaluations, one at the beginning of the project and another at the end. We
wanted to measure their technical, administrative and financial capacity to determine the status of the
aqueducts at the beginning of the study. A scale from 0 to 100% was used to determine each capacity and a
total capacity for the aqueducts. The technical capacity is the physical and operational ability of a system to
meet the regulatory requirements for drinking water, the administrative capacity is the system's ability to
conduct its administrative matters so that the system can achieve and maintain compliance and the financial
capacity is the system's ability to acquire and maintain sufficient financial or economic resources to enable
it to achieve and maintain compliance with the Safe Drinking Water (DOH, 2010) (Figure 4). The Capacity
Development Evaluation form includes questions related to the following areas: infrastructure, system
operation, sampling, reports, organization system, embedding system, budget procedure, budget and
income.
FIGURE 3. Municipalities (shaded) in which the capacity evaluation was performed

on 48 Community Water Systems.
During the two year period, a Circuit Riders Program was implemented by the Department of
Health, Potable Water Division, in which trained personnel routinely visited the aqueducts to help them
improve their systems. At the end of the study we wanted to measure if there was a change on the three
capacities. All the evaluations were provided to the managers or leaders of the aqueducts. After the first
evaluations were performed an action plan was designed for each system individually. In this way, the
community played an active role in the prioritization of the necessities that had to be addressed to make the
system comply, with the periodic assistance of technical personnel.
RESULTS
The results were based on the technical, administrative and financial capacity of the systems. We
calculated an average for the 48 community water systems for the first evaluation and the final evaluation,
after implementing the Circuit Riders Program and developed an action plan for each community. The first
130
evaluation on technical capacity presented an average of 59.25%, while at the end the average was 70.95%,
showing an increase of 11.70%. The administrative capacity presented an average of 40.86% at the
beginning, while at the end the value was 58.81%, showing an increase of 17.95%. The financial capacity
was 39.47% for the initial evaluation whereas the final evaluation presented an average of 42.90% with an
increase of 3.43%. Figure 5 shows the average capacity per area at the beginning and at the end of the two
year period for the 48 community water systems.
FIGURE 4: Technical, Administrative (Managerial) and Financial Capacity Development Process.
100
90
80
Percentage (%)
70
60
50
40
30
20
10
0
Beginning End of Beginning End of Beginning End of
of Study Study of Study Study of Study Study
Administrative
Technical Capacity Financial Capacity
Capacity
Average 59.25 70.95 40.86 58.81 39.47 42.9
FIGURE 5. Technical, Administrative and Financial Capacity Average at the Beginning

and at the End of the Study for 48 Community Water Systems in Puerto Rico.
After each capacity rating was calculated for each community, we calculated a total capacity for
each community. Then, we determined an average for the 48 communities for the total capacity values. At
the beginning of the study the average for total capacity was 46.66% but after giving advise and routine
131
visits to the managers of the aqueducts, we obtained a value of 57.69% in the final evaluation with an
increase of 11.03% in total capacity (Figure 6).
100
90
80
70
60
50
40
Percentage (%)
30
20
10
0
Beginning of Study End of Study
Total Capacity
Average 46.66 57.69
FIGURE 6. Total Capacity Average for 48 Community Water Systems in Puerto Rico.
DISCUSSION AND CONCLUSIONS

It is hoped that each aqueduct will get a value near 100% for each capacity and a total capacity
value. As the system is closer to 100%, we can say that the aqueduct is complying with state and federal
regulations. After completing the evaluations and getting information from the leaders on the community
and the aqueducts, we gathered informal data in addition to the one included on the Capacity Development
Form. We concluded that there are several factors that could be affecting the final results of the evaluation
but has nothing to do with the water quality of the small water system. The Capacity Development Form
included questions related as to the legal titles of the land on with the source of water and/or storage tanks
were constructed. The construction of the aqueducts started in the 1950's and land owners donated the land
(without legal documents) to the community to build their systems. At the present time, it is almost
impossible to find those persons or their family that could complete the legal documents to donate the land
to the community. Another example is related to the need for a certified operator for the systems. The state
and federal regulations establish that the aqueducts must have a certified operator managing their systems.
To get the certification, it is required that the person must have 15 college credits on sciences or
mathematics, even if they pass the test. Many of the leaders of the aqueducts only have a high school
education at most. So, it is difficult to get the leaders to accomplish that requirement. There are some of
them that passed the certified operator test but the governmental agencies did not give them the certification
because they do not have the college credits, even when they have the knowledge and skills necessary to
work with the aqueduct safely and maintain a high standard of water treatment. These are just two examples
of several questions that made the aqueducts score low on capacity but had nothing to do with the water
quality. The Capacity Evaluation Form has no room to take into consideration aspects like the ones
mentioned above but that affect the final capacity. There should be a revision of the Capacity Form to
include aspects specific for these community water systems. These aspects have more to do with
environmental justice than with numbers and will affect the final results, producing figures far from the
reality of each community.
ACKNOWLEDGMENTS
This research was supported by NSF IGERT Grant # 0801577. We would like to thank the
Department of Health, Potable Water Division and the communities that allowed us access to their systems.
132
REFERENCES
Department of Health of Puerto Rico. 2008. “Informe Anual de Violaciones Sistemas Públicos de Agua
Potable Puerto Rico 2008”. Retrieved on January 26, 2014 from http://www.salud.gov.pr/Informacion/
Documents/InformeAnualdeviloacionesAguaPotable2008.pdf
Department of Health of Puerto Rico. 2010. “Desarrollo de Capacidad: Manual Dirigido a Sistemas
Comunales Pequeños de Agua Potable para Desarrollar y Mantener Capacidad Técnica, Financiera y
Administrativa”.
“Ley de Acueductos y Alcantarillados de Puerto Rico” Act Num. 40 from May 1, 1945, as amended.
“Maps of 78 Municipalities of Puerto Rico”. Retrieved on March 26, 2014, from,
http://mapsof.net/map/map-of-the-78-municipalities-of-puerto-rico.
Martí, J. A., R.E. Renta and C. Velázquez. 2004. “Actualización del Inventario: Sistemas de Acueductos
Independientes en Puerto Rico (Non-PRASA)”. Retrieved on February 1, 2014, from
http://www.bvsde.paho.org/bvsAIDIS/PuertoRico29/martir.pdf
Puerto Rico Aqueduct and Sewer Authority. 2014. “Nuestra Autoridad”. Retrieved on February 26, 2014,
from http://www.acueductospr.com/NUESTRAAUTORIDAD/vision.htm
U.S. Environmental Protection Agency. 2010. Fiscal Year 2010 Drinking Water and Ground Water
Statistics. Report EPA 817K11001.
U.S. Environmental Protection Agency. 2012a. The Safe Drinking Water Act Amendments of 1996.
http://water.epa.gov/lawsregs/guidance/sdwa/theme.cfm
U.S. Environmental Protection Agency. 2012b. What is Capacity Development?
http://water.epa.gov/type/drink/pws/smallsystems/basicinformation.cfm#what_is_capacity_developme
nt
World Health Organization, Water sanitation and health. 2010a. Small community water supply
management. Retrieved on December 8, 2013, from http://www.who.int/water_sanitation_health/
dwq/smallcommunity/en/index.html
World Health Organization 2010b. Small and Safe: Investing in small community water supplies will reduce
waterborne disease outbreaks and overall costs. Retrieved on February 5, 2014, from
http://www.who.int/water_sanitation_health/ WHS_WWD2010_small_systems_2010_4_en.pdf?ua=1
World Health Organization. 2013. Progress on sanitation and drinking-water - 2013 update. Retrieved on
April 26, 2014, from http://apps.who.int/iris/bitstream/10665/81245/1/9789241505390_eng.pdf
133
SIMULTANEOUS REMOVAL OF AMMONIA AND NITRATE BY ELECTROLYTIC

DECOMPOSITION AS TERTIARY TREATMENT
Jing Ding, Wei Li, Qingliang Zhao, Kun Wang and Junqiu Jiang
(Harbin Institute of Technology, Harbin, Heilongjiang Province, China)
ABSTRACT: To mitigate eutrophication risk caused by nitrogen species left in domestic wastewater
effluent, nutrient compounds that are not removed after biological treatment should be eliminated by a
tertiary treatment. In this paper, a divided electrochemical cell with cation membrane was developed for
simultaneous anodic ammonia oxidation and cathodic nitrate reduction. The performance of electrochemical
process with different chloride ion concentration was investigated. A mathematical model developed from
the variations of parameters results was presented, and fits the experimental ammonia removal results well.
Chloride exerted the strong influence on the oxidation rate of ammonia and the presence of free chlorine
showed indirect oxidation mechanism was predominant in anodic compartment. The influence of chloride
on nitrate reduction rate was less than that on ammonia removal. Nitrate reduction was fitted to pseudo-first
order equation with the values of kinetic constants (0.11-0.84 L/Ah) obtained. The main product of
electrolytic decomposition was nitrogen gas, since the total nitrogen in wastewater decreased due to a high
removal of 74%. These results clearly showed the potential of this electrochemical system to serve as a
tertiary wastewater treatment for simultaneous removal of ammonia and nitrate.
INTRODUCTION
Aqueous nitrogen species left in domestic wastewater effluent are one of the nutrient sources in
environmental nature water (Pernet-Coudrier et al., 2012). In some specific area, nutrient species still need
to be further removed and the concentration needs to go to a lower level to mitigate eutrophication risk to
the environment. The residual ammonia in the domestic effluent could be further removed or decomposed
by treatments such as activated carbon adsorption, breakpoint chlorination, ion exchange, electrochemical
oxidation and so on (Xiao et al., 2009). Electrochemical process has been the focus by many researchers as
its advantages of high efficiency, no sludge operation, small area occupied and relatively low cost (Li et al.,
2009; Souza-Garcia et al., 2009; Fan et al., 2013). Previous studies have attempted to investigate the
feasibility of anodic ammonia oxidation (Panizza and Cerisola, 2004; Vanlangendonck et al., 2005; Kapałka
et al., 2010; Gendel and Lahav, 2012) or cathodic nitrate reduction (Szpyrkowicz et al., 2006; Mattarozzia
et al., 2013; Dortsiou et al., 2013) separately, and the combined performance of cathodic reduction for nitrate
and anodic oxidation for ammonia and nitrite to improve the selectivity from nitrate to nitrogen and the
efficiency of electrochemical denitrification. (Reyter et al., 2010; Fan et al., 2013). However, rare
information is available about the combination of anodic and cathodic decomposition for simultaneous
removal of both ammonia and nitrate in wastewater. Thus, the objective of this study was to investigate the
capability of total nitrogen (TN) elimination in the two-chamber electrolysis system separated by cation
membrane. The influence of chloride ion for ammonia and nitrate removal was also revealed so as to obtain
the removal mechanism and kinetic.

Batch experiments were performed in a laboratory scale. The electrochemical reactor was
constructed with Ru-Ir-Sn/Ti anode and graphite felt cathode by Pyrex glass (60mm×60mm). The reactor
was comprised anodic and cathodic chamber which were pressed up onto either side of a cation
membrane. The simulated effluent was stored in a glass vessel and continuously recirculated in anodic and
cathodic chamber by two peristaltic pumps. The synthetic solution was prepared with NaCl, (NH4)2SO4 and
NaNO3. Electrolysis process was carried out at constant current density and ambient temperature.
Samples were taken after fixed time interval, but the decrease in pollutant concentration as well as
the evolution of other parameters in the following section was represented against the specific electrical
charge (Q), which is calculated according to electrolysis time and current density. It could represent a means
of comparing the efficiency of the process at different scales, regardless of current density applied.
134
Ammonia, nitrate, nitrite, TN, chloride and free chlorine were analyzed for the samples collected.
Ammonia was measured by Nessler reagent spectrophotometry. Nitrate, nitrite and chloride ions were
measured by ion chromatography (Dionex ICS3000) with a Dionex Ion Pac AS11-HC 4×250 mm Anion
Exchange column, using KOH as eluent at 1 mL/min. TN was quantified by carbon analyzer (Shimadzu
TOC-VCPN). Free chlorine was measured with the N, N-diethylp-phenylenediamine (DPD) ferrous
titrimetric method.
Ammonia Oxidation. In order to investigate ammonia oxidation rate, 10 experiments were carried out, the
design and results of which are described in Table1, and the model based on 1stOpt software developed
from the experimental results is expressed as in Eq.(1). The results indicated that ammonia removal rate was
positively influenced by the chloride ion, as the free chlorine, including Cl2, HOCl and OCl- which was
generated around the anode and dependent on chloride concentration. Conversely, the increase of initial
ammonia concentration had negative effect on ammonia removal. This result was in accordance with the
previous studies which had reported ammonia oxidation rate (k) primarily depends on the parameters of
current density, chloride concentration and ammonia concentration (Vanlangendonck et al., 2005). Indirect
oxidation by free chlorine was the main mechanism for ammonia removal, simplified as reaction Eqs. (2-4)
(Kapałka et al., 2010). Ammonia removal rate in this study was calculated with increased Q, which was
regardless of the variation of current density.
+
NH 4 −1.389 Cl - 0.65
k = 0.677 × ( ) ×( ) R2=0.9976 （1）
14 35.5
Where Cl- represented the chloride concentration (mg/L-Cl), and NH4+ was the initial ammonia
concentration (mg/L-N).
2Cl-→Cl2 +2 e- （ 2）
Cl2 +H2O→HOCl+ Cl-+H+ （ 3）
2NH4++3HOCl→N2 +3H2O +5H+ +3Cl- （ 4）
In the domestic effluent, nitrate was left with ammonia after biological nitrification and
denitrification. The investigation of ammonia electrooxidation in the presence of nitrate was essential. Fig.1
showed the comparison of experimental results and model estimations for ammonia oxidation when
ammonia and nitrate simultaneously exists in the system. The result of model simulation in Eq.(1) coincided
with the experiment and shown similar patterns for the ammonia removal when Cl- was 450 and 990 mg/L.
A larger deviation of removal tendency was indicated in Fig.1 when Cl- was 90mg/L, which was attributed
to the existence of nitrate in the system.
TABLE 1. Ammonia oxidation rate obtained in the design of experiments with variable parameters
Cl-(mg/L-Cl) NH4+(mg/L-N) Ammonia oxidation rate(k, mg/Ah)
1 200 10 33.292
2 40 20 6.414
3 80 20 13.962
4 200 20 27.52
5 300 20 33.818
6 400 20 38.21
7 200 40 20.54
8 800 40 46.228
9 200 100 12.34
10 2000 100 64.34
135
1
Experiment-90mg/L Cl
Experiment-450mg/L Cl
0.8 Experiment-990mg/L Cl
Model-90mg/L Cl
Model-450mg/L Cl
0
0.6
+
Model-990mg/L Cl
NH4 /NH4
+
0.4
0.2
0
0 0.5 1 1.5 2
Q（Ah/L）
FIGURE 1. Experimental and model estimation for ammonia removal as Q increased with the change of
chloride (Initial Ammonia: 20mg/L-N; Initial Nitrate: 20mg/L-N)
The presence of free chlorine in anodic chamber with different concentration chloride ions was
shown in Fig.2. Free chlorine was maintained at less than 3mg/L with chloride 90mg/L. At chloride
450mg/L, the amount of free chlorine was lower than 10mg/L, followed by linear increasing with Q after
0.5Ah/L, when ammonia had been removed totally. Similar increase trend of free chlorine was also found
in chloride 990mg/L. This verified indirect oxidation was predominant mechanism in anodic compartment,
and the produced chlorine reacted with ammonia rapidly. Electric charge would be used to continuously
produce free chlorine, and then free chlorine was enriched without ammonia in the system according to the
Eq. (3-4).
80
90mg/L Cl
450mg/L Cl
（
990mg/L Cl
Free Chlorine (mg/L-Cl)
60
3
y = 40.944x - 6.1032
2
40 R = 0.9909
y = 38.58x - 15.112
2
R = 0.9776
20
0
0 0.5 1 1.5 2
Q（Ah/L）
FIGURE 2. Free chlorine generation in the solution as a function of chloride
Nitrate Reduction. Fig.3 presented the nitrate reduction as the function of chloride concentration with or
without ammonia in the system. Kinetic estimation according to pseudo first order kinetic model, as
expressed in Eq.(5), was also shown in Fig.3 and the results of simulation was given in Table.2. The kinetic
constant varied from 0.11 to 0.84 L/Ah. Szpyrkowicz reported that nitrate reduction process in the cathodic
chamber followed the Eqs. (5-7) (Szpyrkowicz et al., 2006). Ammonia in the electrolysis system seemed to
exert negative influence to nitrate reduction, due to the Eq.(7). Less influence of chloride was found on
nitrate reduction than ammonia oxidation, attributed to different reaction mechanisms.
136
−
（NO3 ）t
- ln −
= kt (5)
（NO3 ）0
1
0.9
0.8
NO 3 /NO 3 0
-
0.7
-
0.6 450mg/L Cl
990mg/L Cl
90mg/L Cl
0.5 90mg/L CL no ammnoina
0.4
0 0.5 1 1.5 2 2.5 3 3.5
Q（Ah/L）
FIGURE 3. Experimental and kinetic estimation for nitrate reduction as Q increased with the change of
chloride (Initial Nitrate: 20mg/L-N)
NO3-+H2O+2e-→NO2- +2OH- (6)

NO3-+5H2O+6e-→NH3 +7OH- (7)
NO3-+2H2O+5e-→1/2N2 +6OH- (8)
TABLE 2. Nitrate reduction constant with the variation of chloride and ammonia
Cl-(mg/L-Cl) NO3-(mg/L-N) NH4+(mg/L-N) k(L/Ah) R2
1 90 20 20 0.2675 0.9495
2 450 20 20 0.1106 0.9441
3 990 20 20 0.1228 0.9786
4 90 20 0 0.8356 0.9648
1
90mg/L Cl
0.8 450mg/L Cl
990mg/L Cl
0.6
TN/TN0
0.4
0.2
0
0 0.5 1 1.5 2 2.5 3 3.5
Q（Ah/L）
FIGURE 4. The elimination of TN as Q increased with the change of chloride
137
Total Nitrogen Removal. It was noticed that nitrate reduction in cathodic chamber may cause the derivation
of ammonia and nitrite, as shown in Eqs. (6-7). Therefore, TN concentration was essential to be determined
to inspect the conversion of nitrogen species in aqueous phase to nitrogen gas. Fig.4 presented TN removal
as Q increased with different chloride concentration, and the results indicated that the conversion from
ammonia and nitrate to nitrogen gas in this system was efficient, with the highest TN removal of 74% at the
end of experiment. The efficiency of TN removal increased with chloride concentration, due to the positive
effect of chloride to ammonia removal.
CONCLUSIONS
This study demonstrated that chloride had positive influence on ammonia removal in anodic
chamber, as the ammonia was oxidized by an indirect mechanism via free chlorine. The removal model
satisfactorily fitted the experimental results when chloride concentration was 450 and 990mg/L. The
occurrence and increase of free chlorine as Q increased verified the rapid reaction of ammonia and chlorine.
Nitrate reduction in the cathodic chamber followed pseudo first order kinetic, with the kinetic constant
varied from 0.11 to 0.84 L/Ah. 74% removal efficiency of TN was achieved in the system, which provided
the feasibility of the system on the conversion of the different nitrogen species to nitrogen gas.
ACKNOWLEDGEMENTS
This research was funded by Project 51121062 (National Creative Research Groups) supported by
National Nature Science Foundation of China, the National Critical Scientific and Technological Project of
Water Pollution Control and Management (2012ZX07201003-002).
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139
EFFECTS OF APPLICATION TIME OF EXTERNAL ELECTRIC FIELD ON ANAMMOX

BIOMASS ACTIVITY
Sen Qiao, Xin Yin, Jiti Zhou

(Dalian University of Technology, Dalian, China)
ABSTRACT: In this study, the effects of different application time of external electric field were studied
in two identical UASB reactors. The effects of three kinds of distribution modes in the total electric field
applied time of 12h/24h at 2V/cm were investigated. When the impulse application time of electric field
was 3h, 6h and 12 h in one cycle, the nitrogen removal rates increased 18.7%, 27.4% and 8.5%, respectively,
compared with control experiment. Moreover, after the reactor with electric field was running smoothly at
the optimal condition (6 h application-6 h resting) for about 215 days, the TN nitrogen removal rate reached
a high value at 6468 g-N/m3/d, which was 45% much higher than that of the control. The increase of crude
enzyme activities demonstrated to be the main reason for the enhancement of nitrogen removal on the
anammox process. Additionally, transmission electron microscope observation proved the morphological
change of anammox biomass under electric field application, which might contribute to the substrate rapid
turnover and more storage.
INTRODUCTION
Anaerobic ammonium oxidation (anammox) has already been recognized as an innovative nitrogen
removal technology for wastewater treatment (Mulder et al., 1995). Compared with the conventional
biological processes (nitrification-denitrification), anammox process offers significant advantages such as
no demand for oxygen and organic carbon, low sludge production and reduced CO2 or N2O emissions (Op
den Camp et al. 2006). However, extremely slowly growth rate of anammox bacteria with a doubling time
of 11-20 days (Strous et al. 1999) causes the longer start-up period. Consequently, enhancing the activity of
anammox bacteria or shortening the start-up period of anammox reactors is a subject of great interest and
challenge.
Recently, external electric field might be another effective approach to enhance biomass activity.
The application of electric fields for influencing cell biology was a readopted topic in biological field for
several decades. The specific sensitivity of biological cells towards electric fields was since then being
exploited for various purposes such as cell growth, cell killing, diagnostics, sensing devices, healing or gene
transfer purposes (Amarjargal et al. 2013). When cells are exposed to electric fields, the polarization of the
cell membrane and its components takes place, which may further lead to the following phenomena, such
as rotation, cell membrane permeability and osmotic imbalance (Barnes et al. 2007). Moreover, some
researchers have showed that the activation of enzyme would be possible by pulsed electric field treatment
(Takayuki et al. 2007). Additionally, bioelectrical systems were also used to improve the growth rate of
aerobic iron oxidation microorganisms and anaerobic lithotrophic iron reduction microorganisms (Ohmura
et al. 2002). Thus, external electric field could increase the activity of various biomass including the enzyme
activity enhancement and cell growth according to the literatures mentioned above. Therefore, we could
deduce that the external electric field might exert the similar effects on anammox biomass. However, until
now there existed no related-reports focusing on the application of electric field on the activity of anommox
biomass.
Our preliminary batch experimental results demonstrated that anamox biomass activity could be
increased by external electric field (2 V/cm). However, 24 h continuous application would definitely depress
anammox biomass activity at the range between 1 and 4 V/cm (Qiao et al., 2013). Thus, the main aim of
this study was to investigate the effects of external electric field on the activity of anammox biomass with
relatively shorter application time. Furthermore, we also explored the effects mechanism, such as the
variation of crude enzyme activity and cell morphology.
140
The anammox biomass used for continuous experiments originated from a laboratory-scale
anammox upflow column reactor in our lab. Anammox bacteria of KSU-1 strain (AB057453.1) accounted
for about 70-75% of the total biomass in seed biomass by FISH observation. Two identical upflow fixed-
bed column reactors, R1 (the control reactor, without electric field application) and R2 (with electric field
application), were applied for continuous experiments. The working volumes were about 0.5 L with the
inner diameter of 5 cm and the height of 25 cm. All the reactors contained 50 g (wet weight) anammox
biomass resulting in an initial MLVSS concentration of 4920 mg/L for each reactor.
Our preliminary experimental results demonstrated
that anamox biomass activity could be increased by external
electric field (2 V/cm). However, 24 h continuous
application would definitely depress anammox biomass
activity at the range between 1 and 4 V/cm (Qiao et al.,
2013). We predicted that application time was another key
factor to influence anammox biomass activity besides the
electric intensity. Hence, the application time of external
electric field was determined as 12 h per day in this study.
For operational convenience, the application time and
resting time was set as 3h-3h, 6h-6h, 12h-12h in one cycle,
respectively. The applied electric field intensity of the
whole continuous experiments was determined as 2V/cm
based on our preliminary experimental results. The detailed
running conditions of R2 were shown in Table 1.
Fig. 1. Schematic diagram of two identical
anammox reactors, R2 with electric field Table 1. The detailed running conditions of R2 during the
application and R1 without electric field. whole continuous experiments.
Application modes Mode 1 Mode 2 Mode 3 Mode 2

Phase I II III IV
Application time--resting time 3h-3h 6h-6h 12h-12h 6h-6h
Cycles/day 4 2 1 2
Application time per day 12h/24h
Concentrations of nitrite and nitrate were determined by using an ion-exchange chromatography

(ICS-1100, DIONEX, AR, USA) with an IonPac AS18 anion column after filtration with 0.22 µm pore size
membranes. NH4+-N, MLSS and MLVSS concentrations were measured according to the Standard Methods
(APHA 1995). Enzyme activity of hydrazine dehydrogenase was determined according to the methods
described by Shimamura et al. (2007). The hydrazine dehydrogenase activity was expressed as μmol of
cytochrome c reduced/mg protein/min. Nitrate reductase (Nar) activity was assayed in accordance with the
methods recorded by Meincke et al. (1992) by measuring the consumption of nitrite. Nitrite reductase (Nir)
activity was assayed on the basis of the methods described by Hira et al. (2012).

Firstly, we investigated the effects of different application modes during three phases in continuous
experiments. The relationship of different application modes and the corresponding anammox activities is
presented in Fig. 2. Compared with the control experiment, there was an observable increase of nitrogen
removal performance with the application time of 12 h per day (the applied electric field of 2V/cm). The
enhancement of biological activity changed with the impulse application time of the electric field. At the
end of phase I (mode 1), the TN removal efficiency of R2 was 71%, which was about 18.3% higher than
that of R1. Subsequently, the nitrogen removal efficiency continued to increase after the impulse application
time enhanced to 6 h (mode 2). On the running day of 30, the TN removal efficiency of R2 climbed up to
78%, while that of R1 kept quite stable at about 62% in the end of phase II. But when the impulse application
141
250 300
A I II III B I II III
200 250
200
NH4 -N (mg/l)
150 inf.NH 4 + -N
NO2 -N (mg/l)
inf.NO 2 --N
eff.NH 4 + -N of R1 150 eff.NO 2 --N of R1

+
100
-
eff.NH 4 + -N of R2 eff.NO 2 --N of R2
100
50
50
0
0 10 20 30 40 50 0 10 20 30 40 50
Time (day) Time (day)
60
55
C 1400
D
50
NLR, NRR (mg-TN/m /d)

3
45 1200
NLR
40
NO3 -N (mg/l)
NR R of R1
35 1000 NR R of R2
30
-
- 800
25 eff.NO 3 -N of R1
20 -
eff.NO 3 -N of R2
15 600
0 10 20 30 40 50 0 10 20 30 40 50
Time (day) Time (day)
Fig. 2. Comparison of nitrogen removal performance of two reactors in different

phases.
120 160
A 140
B
100
120 in f. N O 2 - -N
i n f.N H 4 + -N
80 100 e ff. N O 2 - -N o f R 1
e ff.N H 4 + -N o f R 1
-N (mg/l)
e ff. N O 2 - -N o f R 2
NO -N (mg/l)
60 e ff.N H 4 + -N o f R 2 80
+
60
4
40
NH
-
2
40
20 20
0 0
50 100 150 200 250 300 50 100 150 200 250 300
T im e ( d a y) T im e ( d a y )
40
35
C 9000 D
7500 N LR
NLR,, NRR (mg-TN/m /d)
30 N R R of R 1
3
N R R of R 2
25 6000
NO -N (mg/l)
20
4500
-
3
15
e f f.N O 3 - - N o f R 1
10 3000
e f f.N O 3 - - N o f R 2
5 1500
0
50 100 150 200 250 300 0 50 100 150 200 250 300
T im e ( d a y) T im e ( d a y)
Fig. 3. Comparison of nitrogen removal performance of two reactors in phase IV.
time beyond 6h in one cycle, the activity of anammox biomass did not result in further increase rather
showed a decreasing trend. During phase III, there has been a decline in the total nitrogen removal efficiency
142
of R2 with 72% after the impulse application time increased to 12 h in one cycle (mode 3). The continuous
experimental results demonstrated that application time of external electric field distinctly played a key role
on the activity of anammox biomass. The peak positive effect of electric field at application mode 2
(application-rest time: 6h-6h). Thus, this mode (mode 2, applicaton-resting time: 6h-6h,) was utilized for
the following continuous experiments (phase IV) to examine its long-term effects on the activity of
anammox biomass.
Table 2. crude enzyme activities of both reactors during different phases.

Phase I II III IV
Sampling day (day15) (day30) (day45) day 80 day140 day 200 day260
R1 1.12 1.14 1.18 1.02 1.40 1.59 1.70
Crude HDH Activity
(µM nitrite/min/mg protein) R2 1.76 1.84 1.36 0.95 2.09 2.39 2.92
Crude NIR activity R1 23.35 24.26 26.29 23.07 27.62 30.41 34.82
(µM nitrite/min/mg protein) R2 31.89 34.52 28.10 27.38 35.34 46.53 50.78
R1 1.70 1.80 1.98 1.80 2.10 2.75 3.26
Crude NAR activity (µM
cytochrome c/mg protein/min) R2 2.31 2.73 2.45 1.86 2.43 3.60 4.59
In phase IV, HRT shortening was applied as the main method to increase the NLRs of both reactors
with the constant influent substrates concentrations. As shown in Fig.3, the NRRs of both reactors were 867
and 1002 g-N/m3/d, respectively. The inhibition of anammox biomass in R2 due to the mal-effects of
external electric field during phase III resulted in the almost same nitrogen removal performance of both
reactors. From phase IV, the NRR of R2 presented a rapid enhancement and could kept continuous and
stable better nitrogen removal performance than that of R1. For instance, the NRR of R2 increased to only
one week after the application mode returned to mode 2 (6 h application-6 h resting), which was about
16.7% than that of R1 in the same period. In the following running days, the nitrogen removal performance
always showed to be always higher than those of R1. In the end of phase IV, the NLR of two reactors
increased to 8641 g-N/m3/d. While the NRRs of both reactors reached 4470 and 6468g-N/m3/d, respectively.
And the latter was about 45% higher than that of the former. In our study, these two reactors were operated
at the similar condition except the external electric field application or not, but there presented so much
difference in nitrogen removal performance between them. Hence, these results implied that appropriate
external electric field application might be the main reason for this difference in nitrogen removal
performance.
Anammox process involved several key enzymes for converting ammonium to dinitrogen gas, such
as nitrate reductase (NAR), nitrite reductase (NIR), hydrazine oxidoreductase (HZO), hydrazine
dehydrogenase (HDH), and hydrazine hydrolase (HH) (Kartal et al. 2011). Among them, HDH might be the
key enzyme responsible for converting N2H4 into the final N2 (Kartal et al. 2011). Table 2 described the
variation of crude HDH activities of both reactors during different phases. Obviously, with the electric field
applied, the crude HDH activities were enhanced greatly at all three phases in different impulse application.
The peak value of 1.84 µmol cyto c reduced/min/mg protein was 1.36 folds as high as that of control reactor
within 45 days’ operation, which was achieved under mode 2 (6 h application-6 h resting) at the end of
phase II. During phase III, the crude HDH activity appeared a downward trend, and dropped to 1.36 µmol
cyto c reduced/min/mg protein under mode 3 (mode 3, 12h-12h). In phase IV, the crude HDH activity of
two reactors were measured on day 80, 140, 200 and 260 similarly, the crude HDH activity exhibited the
similar changing situation with that of hemc c contents as our speculation above. At the end of phase IV on
day 260, the crude HDH activity with electric field of optimal condition in R2 was increased to 2.92 cyto c
reduced/min/mg protein. The peak value was about 3.1 and 1.6 folds as much as those of seed sludge and
R1.
Besides, the effects of electric field on the other key enzymes were also studied, such as nitrate
reductase and nitrite reductase of anammox bacteria. Similarly to the crude HDH activity, the peak value of
the crude NIR activity of 34.2 and NAR activity of 2.73 μM NO2--N/mg protein/min all were observed at
143
the impulse continuous application time of 6h (mode 2). And then the crude NIR and NAR activity appeared
decrease trends at the impulse continuous application time of 12h (mode 3). Furthermore, during 215 days’
cultivation (from day 45 to day 260), the crude NIR activity in R2 was from 27.38 increased to 50.38 NO2-
-N/mg protein/min and the NAR activity was from 1.86 increased to 4.59 NO2--N/mg protein/min, which
was about 45.8% and 41% higher than those of R1 on day 260, respectively. Thus, the crude enzyme activity
of anammox bacteria might be closely affected by electric field, which further promoted the nitrogen
removal performance.
Fig. 3. Comparison of the TEM observations on both reactors on day 200. A, C were samples taken
from R1; B, D were samples taken from R2
Samples of both reactors at day 200 (in phase IV) were taken for TEM observation, as shown in
Fig. 3. The distribution of bacterial flora of two reactors showed evident differences. Compared Fig. 6A
with Fig. 6B, it was obvious that the anammox bacteria was aggregated in R2 with electric field, displaying
a compact cluster of cells in structure, while it presented a dispersed texture in R1, showing low cell-density
in view. Considering the increase of 16S rRNA anammox bacterial copy numbers and the higher cell-
density, it further confirmed that the application of electric field on the appropriate condition had a
significantly positive effect on the growth rate of anammox biomass. Some cells of the two reactors showed
irregular shape, the reason might be the long operation and high nitrogen loading. Besides, with electric
field application, there existed a lot of curvatures and compartments inside anammoxosome from Fig 6D.
The curvatures and so many compartments may be used to increase the membrane surface available for the
enzyme involved in catabolism, such as the ATPases and cytochromes c proteins. The increase of
anammoxosome membrane surface would provide more area to accommodate more cytochrome c or other
key enzymes. Thus, the enhanced cytochrome c could exert their function as activity center. Therefore, the
variation of anammox cell structure by external electric field application might be in favor of the enzyme
catalytic and the substrate transition, and further affected the TN removal performance of anammox
biomass.
CONCLUSIONS
In this study, the application of electric field of 2V/cm at the application time of 12/24h in an UASB
reactor effectively improved the TN removal performance on the anammox reactor. When the continuous
application time of 6h in one cycle was supplied to reactor, nitrogen removal rate increased 45%
dramatically in 265 days. Besides, the applied electric field under the appropriate condition could promote
the crude enzyme activity. TEM photographs indicated that the electric field could result in the variation of
cell density and structure.
ACKNOWLEDGEMETNS
This work was supported by the Natural Science Foundation of China (Nos. 21377014, 51008045),
Science and Technology Research Projects of Liaoning Provincial Department of Education (No.
L2013026).
144
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of the anaerobic ammonium-oxidizing (anammox) bacteria. Biochem. Soc. Trans., 34, 174-178.
Ohmura, N., Matsumoto, N., Sasaki, K., Saiki, H., 2002. Electrochemical regeneration of Fe(III) to support
growth on anaerobic iron respiration, Appl. Envrion. Microbiol., 68, 405-407.
Qiao, S., Yin X., Zhou, J.T., Furukawa K., 2013. Inhibition and recovery of continuous electric field
application on the activity of anammox biomass, Biodegradation., DOI 10.1007/s10532-013-9677-7.
Strous, M., Fuerst, J.A., Kramer, E.H.M., Logemann, S., Muzyer, G., van de Pas-Schoonen, K.T., Webb,
R., Kuene, J.G.., Jetten, M.S.M., 1999. Missing lighotroph identified as new planctomycete, Nature,
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145
ANAEROBIC OXIDATION OF AMMONIUM COUPLED TO ELECTRICITY PRODUCTION

IN A MICROBIAL ELECTROLYSIS CELL
Bo Qu* and Bin Fan

(Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, China)
The oxidation of ammonium is a critical step of biological nitrogen removal from ammonium-rich
wastewater. Here we report that ammonium can be anaerobically oxidized with anodes as the electrons
acceptor in microbial electrolysis cells (MECs). Enrichment cultures attached to the anode surface were
established from a freshwater sediment inoculum with the anode as the sole electron acceptor and
ammonium as the sole electron donor. The oxidation of ammonium was coupled to the electrical current
production. Nitrate was the main product that accounted for approximately 95% of ammonium consumed,
but nitrite was also detectable. Shuttling assays indicated that some soluble microbial metabolites as redox
mediators were involved in electron transfer to the electrode. Analysis of 16S ribosomal RNA gene
sequences showed that the anode was dominated by Nitrosomonas europaea (40.3%) and the genus
Empedobacter (34.7%). In order to further investigate the mechanism responsible of anaerobic ammonium
oxidation and current production, a pure culture of Nitrosomonas europaea was inoculated into the anode
chamber of the same MEC. The cells could oxidize ammonium and transfer electrons to the anode when the
cell-free filtrate of medium from anode chamber of enrichment culture was used as the medium or the
humate analog anthraquinone-2, 6-disulfonate (AQDS) was added as a redox mediator, suggesting that
Nitrosomonas europaea can anaerobically oxidize ammonium with transfer of electrons to an electrode via
electron shuttling. These results demonstrate a novel pathway of biological ammonium oxidation, and have
potential applications in nitrogen wastewater treatment.
146
EFFECT OF BAMBOO BIOCHAR ON FERTILITY AND NUTRIENT LEACHING OF A

SANDY PEAR ORCHARD SOIL IN SOUTHEAST CHINA
Lou Liping 1,2, George A.Sorial2

1. Department of Environmental Engineering, Zhejiang University, Hangzhou, Zhejiang, China
2. Department of Biomedical, Chemical, and Environmental Engineering, University of Cincinnati,
Cincinnati, OH 45221-0012, USA
Biochar has been described as a prosperous method to improve soil fertility and sequester carbon, so it is of
considerable interest in the field of Sustainable Agriculture and Environment. In this study, incubation
experiment and column leaching experiment has been conducted to quantify the effect of different content
of bamboo biochar (BBC) (0, 0.1, 0.3, 0.5, and 1.0% (wt/wt)) on the mineralization of organic fertilizer and
the nutrient leaching in a sandy pear orchard soil. According to C, N and P mass balance analysis, the more
BBC was added to soil, the more C, N and P contents were retained after two experiments. Compared with
the control, the addition of 1.0% BBC to soil retained 1.85, 0.30 and 0.063 mg g-1 C, N and P, respectively.
Furthermore, the influence of BBC on nitrogen was great, because the addition of 1.0% BBC not only
increased the concentration of soil N by 11.84% in the manure mineralisation due to enhance microbial
biomass and enzymes activity, but also reduced the cumulative content of soil N leach-loss by 43.90% in
the leaching process because of its adsorption. BIOLOG analysis indicated that in BBC-amended soils the
soil microbial functional diversity and the utilization of characteristic carbon substrates increased, which
should be a key factor in enhancing the mineralization of chicken manure. For example, in the 1.0% BBC
treatment, the average well color development (AWCD), substrate richness (S) and the three functional
diversity indices (Shannon index (H’), Simpson index (D) and McIntosh index (U)) were 3.63, 1.73, 1.19,
1.05 and 2.94 times of the control respectively, and the utilization of seven characteristic carbon substrates
increased by 5 to 452 times. The results supported that BBC is a promising soil ameliorant and addition of
BBC to soil will be a new method to control agriculture nonpoint source pollution.
147
CHANGES OF BACTTERIAL COMMUNITY DIVERSITY IN OXIC-SETTLING-

ANAEROBIC (OSA) ACTIVATED SLUDGE PROCESS
Lianpeng Sun, Jinxin Tan, Xiaoyu Yu, Lili Chen

(Sun Yat-sen University, Guangzhou, China)
ABSTRACT: Operation of a conventional OSA process was modified by alternately recirculating

supernatant and settled sludge. PCR amplification-TGGE fingerprint profiles were employed for studying
the microbial communities of the two processes in an effort to further illuminate the biological mechanisms
utilized by SBR-OSA systems to reduce sludge production. The results showed that the modified method
of operation reduced sludge production by 11.8% compared to the conventional one. The anaerobic sludge
bacterial communities from the two OSA systems were about hundred percent similar as determined by
transverse comparison, however, the aerobic sludge bacterial communities were only 80% similar during
the last stage of the experiments, and the bacterial communities in the two aerobic activated sludge reactors
were distinctly different.
Keywords: oxic-settling-anaerobic process; bacterial community diversity; sludge reduction;
TGGE;
INTRODUCTION
The oxic-settling-anaerobic (OSA) process was initially applied to modify the traditional activated
sludge wastewater treatment process in the 1990s, and some researchers (Chudoba et al., 1992; Wei et al.,
2003; Sun et al., 2010 ) discovered that it could result in a decrease of 30%~60% in excess sludge
production. The fundamental principle of the OSA process is to incorporate a sidestream anaerobic
bioreactor to the Activated Sludge process. Research has shown that this results in reduced sludge
production via various biological mechanisms such as energy uncoupling, sludge anaerobic digestion, etc
(Chudoba et al., 1992; Saby et al., 2003).Although many investigators have researched the mechanisms of
excess sludge reduction by the OSA process, no consensus explanation currently exists, and several different
factors have been implicated (Chudoba et al., 1992; Saby et al., 2003; Sun et al., 2010). However, regardless
of the biological mechanism(s) involved, it is likely that the process results in significant changes in the
sludge microbial population, and there is a need to elucidate these changes. It has been shown that
conventional methods for studying microbial diversity, such as plating on selective media, are unreliable,
because only a small fraction of the bacterial species present in the natural habitat will grow on synthetic
media. However, molecular analysis of natural microbial communities using bacterial 16S rRNA
amplification-temporal temperature gradient gel electrophoresis (TTGE) can solve these problems and has
been widely applied for the study of microbial diversity. Though the TGGE techniques have some
shortcoming (Hill et al., 2000; La Montagne et al., 2002; Kisand and Wikner, 2003), for instance, a single
band can frequently include several different species when profiling mixed environmental communities, it
remains the most efficient methodology for the determination of relative differences or temporal changes in
microbial community structure in environmental samples.
In this study, a modified SBR-OSA process was established instead of the conventional one, so that
the sludge bacterial community structure would be changed to a significant extent. The modified SBR-OSA
process has different operational parameters, and has more sludge reduction than the control system. And it
is hypothesized that the bacteria community diversity between the two processes were different for the
different operational condition, it was postulated that making the changes and accomplishing improved
sludge reduction in the modified OSA process would increase the population of slowly growing bacteria
such that they could be detected and identified. Analysis of PCR-TTGE banding patterns were performed
for biomass developed in each of the two SBR-OSA processes used to measure and compare the richness
and evenness of the two bacterial communities.
148
Experimental systems. Two sets of SBR-OSA process systems were established, a control system (OSA-
1) and an experimental system (OSA-2). The control system consisted of a conventional SBR with a
sidestream anaerobic reactor, i.e. a conventional SBR-OSA system. Settled sludge was cycled from the SBR
to the anaerobic reactor for anaerobic digestion, and then recycled back to the SBR before sludge wasting.
The experimental system (OSA-2) had the same basic configuration, but was operated differently by cycling
the anaerobic sludge back to the SBR only once every three days and cycling settled supernatant back the
rest cycles. The aerobic reactors of these two systems were separately defined as “O-1” and “O-2”, while
the anaerobic reactors were defined as “A-1” and “A-2”. The complete operation cycle for the SBRs was 6
hours, resulting in 4 cycles per day for each of the two systems. These SBR laboratory systems were fed
artificial sewage which consisted of peptone, glucose, CH3COONa, NH4Cl, KH2PO4, KHSO4, NaHCO3,
CaCl2, MgSO4, FeCl3, Al2(SO4)3 and other microelements, as shown in Table 1.
TABLE 1. Chemical compositions of sewage

The volume of the both aerobic reactors was 4L and
Item Average concentration (mg/L)
HRTs were controlled at 2 days, while the SRT of the two COD 450
anaerobic reactors was maintained at 5 days and 15 days, TN 80
respectively. In OSA-1, 25mL (about 2.5% by volume) of NH4+ 40
aerobic sludge (at the late stage of settling) went into the TP 15
SS 30
anaerobic reactor A-1 via a peristaltic pump in each cycle, and Fe3+ 10
the same volume of anaerobic sludge in A-1 was pumped to the Al3+ 10
aerobic reactor simultaneously. In OSA-2, 25mL of aerobic Mg2+ 20
sludge (at the late stage of settling) was pumped to the Ca2+ 20
anaerobic reactor A-2 in each cycle. The same volume of pH 6.5~7.5
anaerobic sludge was pumped to O-2 every 3 days, while supernatant was returned to O-2 the rest days.
Prior to cycling supernatant from A-2 to O-2, magnetic stirring in A-2 was stopped for settling one hour
before recirculation.
The activated sludge was obtained from an SBR laboratory system fed by artificial sewage, and
maintained at Sun Yat-sen University. The raw sludge, used as seed sludge, was taken from the secondary
sedimentation tank of an A2/O process in Lie De sewage treatment plant, Guang Zhou. After acclimation to
an intermittent aeration mode, the cultivated sludge was seeded into both of the systems. Then nitrogen was
put into the anaerobic reactors to exclude air, and guarantee an anaerobic environment. The room
temperature was about 25 centigrade degree during the experiments. The concentration of MLSS was from
2500-4500mg/L, and no sludge was wasted during the experiments.
Activated sludge DNA extraction method. The activated sludge was sampled four times from each reactor
after the systems were started up, the first day of starting up, 65, 141 and 207 days of operation. The method
of DNA extraction and purification were done according to Yu (2011). DNA concentration was determined
spectrophotometrically at the absorbance (A) of 260 nm. The purity of DNA was estimated
spectrophotometrically by analyzing A260/A230 and A260/A280 ratios to determine contamination by
humic acid and protein, respectively. The size of the isolated DNA fragment was determined by agarose
(1.0%) gel electrophoresis using 1 kb DNA marker. The gel was stained with 0.5 µg/ mL SYBR Green agent
and photographed under UV light.
PCR amplification of 16S Rdna and TTGE. The PCR reaction system was amplified using the following
：Primer-1(10 μmol/ L) 0.25μL, Primer-2(10 μmol/L) 0.25μL, dNTPs (10 mmol/L) 1μL, PCR Buffer 5μL,
DNA template 2μL, Taq polymerase (2U/μL) 1μL, Sterile double distilled water 40.5μL. The reaction
procedures were as follows: (1) predegeneration at 94 for 4 minutes; (2) denaturation at 94 for 1 minute;
(3) annealed at 50 for 1 minute; (4) extended at 72°C for 1 minute. Then, 30 cycles were repeated from
step (2) to step (4). PCR products were electrophoresed at a constant voltage of 150 V for 3 h, with a thermal
gradient from 40 ºC to 55 ºC. The initial electrophoresis time was 1.5 h, and it was later extended to 3 h.
Then photos were taken with a diascoptic lighting imaging system, and the intensities of the TGGE bands
were analyzed.
149
Instruments and reagents. The following instruments were employed in the research: Alpha HP imaging
system (Alpha Co., US); Tgradient PCR (Whatman Biometra Co., Germany); TGGE system (Whatman
Biometra Co., Germany); VCX130PB ultrasonic processor (Sonics Co., US); Forma 700 freezer (Thermo
Electro Co., US); electrophoresis apparatus (Liuyi Co., China). Materials and reagents include: Primer-1 for
PCR reaction (Beijing Genomics Institute, China): 357F-GC-clamp 5'-CGC CCG CCG CGC CCC GCG
CCC GGC CCG CCG CCC CCG CCC CCC TAC GGG AGG CAG CAG-3'; Primer-2: 518R 5'-ATT ACC
GCG GCT GCT GG-3', corresponding to positions on the Escherichia coli 16S rRNA gene (rrs) sequence
(Gomes et al., 2001). The aim of inserting G-C gens-clamps in the primer sequence is to raise the efficiency
of gens separating in TGGE gel bands (Don et al., 1991). dNTPs (Takara Co., Japan). Taq DNA Polymerase
(New Probe Co., China) andultraviolet spectrophotometer (Bio-Rad, US) were also used for analysis.

The bacterial populations in the aerobic and anaerobic reactors were separately analyzed, and are
discussed separately. The aerobic population results will be presented and discussed first.
Changes of aerobic activated sludge bacterial community diversity. The two SBRs were operated with
different styles, and it was assumed the composition of the microbial populations in two systems would be
different. The results obtained by TGGE fingerprint (Figure 1 (a)) and strength analysis of the aerobic
activated sludge microbes communities are shown in Figure 1. To make it convenient for intuitive and clear
analysis of the TGGE profiles, dendrograms were developed, shown in Figure1 (b). Number 1 represents
the first sample of O-1, and Numbers 2, 3 and 4, respectively, represents the second, third and fourth sample.
Number 1＇、2＇、3＇、& 4＇respectively represent the first, second, third and forth sample from O-2.
Lane t was used to show all of the obtained bands. In Figure 1 (b), thicker dendritic lines represent stronger
signals of bands in the TGGE fingerprint profiles, and also represent a higher quantity of a specific kind of
bacterial.
When the profiles are compared
vertically, it can be seen from lane 1~4
that the structure of the aerobic microbial
community varied as time went on: band
1 and band 2 appeared in lane 2, while
band 3 started to appear in lane 3. More
species in the microbial community
appeared with time (refer to Table 2).
Band 5~9 appeared in lane 4. Table 2
shows that lane 3 and lane 4 were
hundred percent similar, illustrating that
the structure of bacterial community was
basically stable and the dominant species
changed no more starting from lane 3 (or
sometime between lane 2 and lane 3).
From lane 1＇~4＇, changes happened
among the structure of the bacterial
community: bands 1, 2, & 4 appeared
starting in lane 2 ＇ , and species
abundances kept increasing. Bands 5~9 FIGURE 1. TGGE finger atlas for aerobic sludge ((a) TGGE
always existed in the 4 lanes. It can be fingerprint profiles; (b) dendrogram)
concluded that the structure of the
bacterial community was reasonably stabile starting in lane 3’.
Compared transversely, Lane 1 and 1＇were for sludge samples taken on the day the systems were
started. Because the sludge in O-1 and O-2 were cultivated under the same conditions, the bands of these
two lanes are hundred percent similar, which verified the precision of the TGGE technique used during these
experiments. When the structure of the bacterial communities in the aerobic sludge zone of the two systems
150
became stable, lane 4 and lane 4＇were only 80% similar, indicating that a considerable diversity existed in
the structure of the aerobic microbial communities in the 2 systems. Band 3 appeared exclusively in lane 3
and 4, and band 4 appeared only in lane 3＇and 4＇. Moreover, according to Table 2, similarity between
lane 2 and lane 3 was 88.9%, and was 77.8% between lane 2＇and 3＇, meaning that the sludge in O-1
needed less time to become stable than the sludge in O-2.
TABLE 2. Comparability index of TGGE bands and Richness value (Rs) for the aerobic bacterial populations
Item 1 2 3 4 1＇ 2＇ 3＇ 4＇
Lane 1 100
Lane 2 75.0 100
Lane 3 66.7 88.9 100
Lane 4 66.7 88.9 100 100
Lane 1＇ 100 75.0 66.7 66.7 100
Lane 2＇ 85.7 87.5 77.8 77.8 85.7 100
Lane 3＇ 66.9 88.9 80.0 80.0 66.7 77.8 100
Lane 4＇ 66.9 88.9 80.0 80.0 66.7 77.8 100 100
Number of bands 6 8 9 9 6 7 9 9
Rs (%) 60 80 90 90 60 70 90 90
When Li L. et al. (2004) analyzed the structure of sludge microbial community in coking
wastewater, abundant and strong bands were obtained. However, in this study, bands in Figure 1 were
relatively less abundant by contrast, as expected, mainly because the nutritional composition of coking
wastewater was more complex than the wastewater used for these experiments. Thus, the highly stable
nutritional composition of the artificial sewage used resulted in a less diverse microbial population than the
one obtained using the industrial wastewater.
The sludge reduction rate between the two systems was compared by the sludge observed yield.
The sludge observed yield was determined over a given range of operation (200d) as the MLSS
increase/COD used, using all the data over the range of operation for which the yield was calculated. The
sludge observed yield in conventional system and modified system was 0.11 and 0.09 mg MLSS / mg COD,
respectively. So sludge mass reduction in the modified SBR-OSA process was 11.8% greater than that in
the conventional one, showing that the difference was related directly to the aerobic sludge characteristics
in the two systems.
It was assumed that there was one or more species of slowly growing bacteria in the sludge initially
placed in the aerobic tanks of the SBR-OSA system, and it (they) would have an improved opportunity to
become a greater fraction of the activated
sludge in the modified OSA process than in
the conventional OSA process because of
the longer total SRT. In Figure 1, the
microbial structure difference between lane
4 and lane 4＇verified that the activated
sludge bacteria of the two systems were
obviously different and that the hypothesis
of an increased population of slow growers
is very probable, and, therefore, is
proposed. However, it needs to be
confirmed by verifying the growing
characteristics and functions of the bacteria
described by lane 4 of Figure 1 using
metagenome techniques. This activity is
proposed for future study.
Changes of anaerobic activated sludge

bacterial community diversity. TGGE
fingerprints and strength analysis of FIGURE 2. TGGE finger atlas for anaerobic sludge ((a) TGGE
fingerprint profiles; (b) dendrogram)
151
anaerobic sludge bacterial communities are illustrated in Figure 2. Aerobic activated sludge was placed
into the anaerobic reactors. When aerobic biomass is placed in an anaerobic environment, the structure of
the microbial community necessarily must make fundamental changes to adapt. The changes that occurred
during experiments can be seen in Figure 2.
When the atlas is compared vertically, it can be seen that significant changes happened to the bands
from lane 1 to lane 4, as the aerobic sludge adapted to the anaerobic conditions during system operation.
From lane 1 to lane 2, the time interval was 65 days, and the structure of the microbial community changed
fundamentally. Table 3 showed that the comparability index of TGGE bands and Richness values for
anaerobic bacteria population.
Table 3 shows that the similarity between these 2 lanes was only 11.1%, and only band 1 appeared
in both lanes as well as in all 4 lanes. Consequently, this result suggested that the bacteria corresponding to
band 4 were amphimicrobe. Lane 2 was 50.0% similar to lane 3, indicating that bacterial community
structure of the anaerobic sludge wasn’t yet stable after the systems had operated for 65 days. Lane 3 and
lane 4 were hundred percent similar, illustrating that the anaerobic bacteria community was relatively stable
during this stage. Bands 2, 4, 5, 7 and 8 appeared in lane 3 and lane 4, indicating that some of the bacterial
species could only grow and reproduce when the systems were operated for a long time. Bands 3, 6 and 7
appeared starting in lane 2, which indicated that could these 3 species of bacteria grow by providing
relatively relaxed anaerobic reaction conditions, which means a relatively wide rage, temperature rage and
so on. From lane 1 to lane 4, the structure of the bands changed greatly, and there was a similarity of only
7.7% between the two lanes, and indicating that anaerobic reaction conditions had been achieved. The same
conclusion could be applied to lanes 1＇~ 4＇, for similarity between lane 1＇and 4＇also was only 7.7%.
Bands 2, 3, 5, and 6 started to appear from lane 2＇. Bands 4 and 7 appeared in lane 3＇and band 8 appeared
only in lane 4＇, indicating that some of the species required more rigorous conditions for growth, such as
greater reaction times and more strict anaerobic conditions.
TABLE 3. Comparability index of TGGE bands and Richness values (Rs) for anaerobic bacteria population
Item 1 2 3 4 1＇ 2＇ 3＇ 4＇
Lane 1 100
Lane 2 11.1 100
Lane 3 7.7 50.0 100
Lane 4 7.7 50.0 100 100
Lane 1＇ 100 11.1 7.7 7.7 100
Lane 2＇ 10.0 50.0 62.5 62.5 10.0 100
Lane 3＇ 8.3 66.7 87.5 87.5 8.3 71.4 100
Lane 4＇ 7.7 50.0 100 100 7.7 62.5 87.5 100
Number of bands 6 4 8 8 6 5 7 8
Rs (%) 46.2 30.8 61.5 61.5 46.2 38.5 53.8 61.5
When compared transversely, it is observed that lane 1 and lane 1＇were hundred percent similar,
as was the similarity between lane 1 and lane 1＇of the aerobic sludge TGGE profiles (Figure 2). These
four samples were from the same sludge, and were, therefore, cultivated under the same conditions.
Therefore, it was expected that the structures of the microorganism communities would be the same, and
this was confirmed in this study, further illustrating that TGGE techniques can analyze the microorganism
community diversity precisely. The similarity between lane 3 and lane 4 was 100%, and was 87.5% between
lane 3＇and lane 4＇. It can be seen that sludge in A-1 needed less time to achieve relatively stable
ecological structure than sludge in A-2. This was because anaerobic reactor A-1 was operated using the
traditional sludge-in and sludge-return mode of OSA operation, while anaerobic reactor A-2 was operated
with a longer time between sludge return events because only supernatant was recirculated most of the time.
It may be that the imbalance between the aerobic sludge entering and leaving A-2 resulted in longer times
for the anaerobic environment of A-2 to reach stability, and for the bacterial community to reach stability.
Lane 4 and lane 4＇were hundred percent similar, showing that at the end of the experiment, the structures
of the two anaerobic microbial communities were basically the same. Thus, the separate operating
conditions had no impact on the final structure of the anaerobic sludge microbial community of the two
OSA systems, but it took more time for the modified OSA process to get stable than the conventional one.
152
CONCLUSION
The majority of OSA investigations have mainly focused on process operating conditions and
sludge production ratios to seek the mechanism of excess sludge reduction. This investigation explored
changes in the bacterial community structure of two OSA processes operated under different anaerobic
sludge return conditions to gain new insights into the possible mechanism of excess sludge reduction.
(1) By means of TGGE fingerprint profiles changes in the sludge microbial community structures
of the two SBR-OSA systems were investigated. It was shown that the microbial community structure of
the sludge in two systems changed with time operation, and finally reached steady-state stability. During
the last period of the experiments, microbial community structures of sludge in the two aerobic reactors
were 80% similar. Based on this result, a slowly-growing dominant bacteria hypothesis was proposed as a
mechanism of excess sludge production in OSA systems.
(2) The results suggested that different operating methods could change the structure of aerobic
sludge community even when treating the same wastewater. The similarity of the sludge communities in
two anaerobic reactors was 100%, indicating that changing the operating method had no obvious impacts
on the structure of the anaerobic sludge community.
(3) Although drawbacks may exist in use of PCR-TGGE techniques, they are still very useful and
accurate for the investigation of the diversity of bacterial communities. During the research in this study,
the TGGE techniques provided very precise results.
(4) As artificial wastewater was used in this study, the number of bacterial species was relatively
small. It is recommended that sewage be used for further research. Also, metagenomes techniques should
be used to accurately identify the slowly-growing dominant bacteria that developed in the aerobic sludge of
this investigation, i.e. the microorganism corresponding to lanes 4 and 4＇.
ACKNOWLEDGEMENTS
This work was supported by the Science & Research Program of Guangdong (Contract No.
2012B091000029 and 2012A032300005), the Science & Research Program of Foshan (Contract No.
2012AA100091 and 2012HY100531), and the Science & Research Program of Chancheng District
(Contract No. 2012B1002). We would like to thank Dr. C. W. Randall from Virginia Polytechnic Institute
and State University for English-language and professional editing.
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154
IDENTIFICATION AND CHARACTERIZATION OF DYE DEGRADER MICROBES IN

MICROBIAL GRANULAR SLUDGE TREATING SYNTHETIC TEXTILE WASTEWATER
K. Muda*, A. Aris*, M.R.Salim*, Z. Ibrahim**, M.Z Nawahwi**.(*Department of Environmental

Engineering, Faculty of Civil Engineering, Universiti Teknologi Malaysia, 81310, Skudai, Johor,
Malaysia; **Department of Biological Sciences, Faculty of Biosciences and Bioengineering, Universiti
Teknologi Malaysia, 81310, Skudai, Johor, Malaysia)
Microbial granular sludge has been successfully developed in sequential batch reactor system treating
synthetic textile wastewater. The system was operated in sequential batch reactor system under intermittent
anaerobic and aerobic reaction mode. The hydraulic retention time of the system was set at 6 hours. A total
of twelve microorganisms have been successfully isolated as pure culture bacteria from the microbial
granular sludge developed in synthetic textile wastewater in the sequential batch reactor system. All of the
twelve pure bacteria cultures isolated were further screened for the ability of dye degradation and
autoaggregation, specific COD and dye degradation rates. All of the isolated microbes showed high color
removal performance varying between 78 - 92% with specific color degradation rate ranging from 0.04-
0.42 mg/g/h. However the removal performance for COD was relatively moderate with the percentage of
15-56% and specific COD degradation rate varies between 0.29 to 4.4 mg/g/h. The percentage of
autoaggregation and surface hydrophobicity among the isolated microbes showed a wide variation ranging
from 18.5 ± 1.8 to 97.3 ± 1.4 and 12.5 ± 2.7 o 97.3 ± 1.4, respectively. Based on the results obtained, six
bacteria isolated from the microbial granules were identified through the molecular techniques involving
bacteria isolation, PCR amplification process characterization and finally determination of taxonomic and
phylogenetic class of bacteria isolates via 16S rDNA sequence analysis. The six bacteria successfully
identified were Pseudomonas veronii, Bacillus cereus, three species of Pseudomonas sp. and Enterobacter
sp. All of these bacterial show the ability in degrading colored wastewater and were characterized as
facultative anaerobes.
155
COMPOST BIOREMEDIATION OF OIL SLUDGE BY USING DIFFERENT MANURES

UNDER LABORATORY CONDITIONS
Ubani Onyedikachi 1*, Atagana Harrison Ifeanyichukwu 2, and Thantsha Mapitsi Silvester 3
(1. Department of Environmental Sciences, University of South Africa, Pretoria, 0003, South Africa; 2.
Institute for Science and Technology Education, University of South Africa, Pretoria, 0003, South Africa;
3. Department of Microbiology and Plant Pathology, University of Pretoria, Pretoria, 0083, South Africa).
This study was conducted to measure the reduction in polycyclic aromatic hydrocarbons (PAHs) content in
oil sludge by co-composting the sludge with pig, cow, horse and poultry manures under laboratory
conditions. Four kilograms of soil spiked with 800g of oil sludge was co-composted differently with each
manure in a ratio of 2:1 (w/w) spiked soil: manure and wood-chips in a ratio of 2:1 (w/v) spiked soil: wood-
chips. Control was set up similar as the one above but without manure. Mixtures were incubated for 10
months at room temperature. Compost piles were turned weekly and moisture level was maintained at
between 50% and 70%. Moisture level, pH, temperature, CO2 evolution and oxygen consumption were
measured monthly and the ash content at the end of experimentation. Bacteria capable of utilizing PAHs
were isolated, purified and characterized by molecular techniques using polymerase chain reaction-
denaturing gradient gel electrophoresis (PCR-DGGE), amplification of the 16S rDNA gene using the
specific primers (16S-P1 PCR and 16S-P2 PCR) and the amplicons were sequenced. Extent of reduction of
PAHs was measured using automated soxhlet extractor with Dichloromethane as the extraction solvent
coupled with gas chromatography/mass spectrometry (GC/MS). Temperature did not exceed 27.5OC in all
compost heaps, pH ranged from 5.5 to 7.8 and CO2 evolution was highest in poultry manure at
18.78µg/dwt/day. Microbial growth and activities were enhanced. Bacteria identified were Bacillus,
Arthrobacter and Staphylococcus species. Results from PAH measurements showed reduction between 77
and 99%. Co-composting of spiked soils with animal manures enhanced the reduction in PAHs.
Interestingly, all bacteria isolated and identified in this study were present in all treatments, including the
control.
156
IDENTIFICATION AND CHARACTERIZATION OF OIL SLUDGE DEGRADING BACTERIA

ISOLATED FROM COMPOST
Ubani Onyedikachi 1*, Atagana Harrison Ifeanyichukwu 2, and Thantsha Mapitsi Silvester 3, Adeleke
Rasheed 4
(1. Department of Environmental Sciences, University of South Africa, Pretoria, 0003, South Africa; 2.
Institute for Science and Technology Education, University of South Africa, Pretoria, 0003, South Africa;
3. Department of Microbiology and Plant Pathology, University of Pretoria, Pretoria, 0083, South
Africa; 4. Institute for Soil, Climate and Water, Agricultural Research Council, Pretoria, South Africa)
Oil sludge components (polycyclic aromatic hydrocarbons, PAHs) have been found to be cytotoxic,
mutagenic and potentially carcinogenic and microorganisms such as bacteria and fungi can degrade the oil
sludge to less toxic compounds such as carbon dioxide, water and salts. In the present study, we isolated
different bacteria with PAH-degrading potentials from the co-composting of oil sludge and different animal
manure. These bacteria were isolated on the mineral base medium and mineral salt agar plates as a growth
control. A total of 31 morphologically distinct isolates were carefully selected from 5 different compost
treatments for identification using polymerase chain reaction (PCR) of the 16S rDNA gene with specific
primers (16S-P1 PCR and 16S-P2 PCR). The amplicons were sequenced and sequences were compared
with the known nucleotides from the gene bank database. The phylogenetical analyses of the isolates showed
that they belong to 3 different clades namely Firmicutes, Proteobacteria and Actinobacteria. These bacteria
identified were closely related to genera Bacillus, Arthrobacter, Staphylococcus, Brevibacterium,
Variovorax, Paenibacillus, Ralstonia and Geobacillus species. The results showed that Bacillus species were
more dominant in all treated compost piles. Based on their characteristics these bacterial isolates have high
potential to utilise PAHs of different molecular weights as carbon and energy sources. These identified
bacteria are of special significance in their capacity to emulsify the PAHs and their ability to utilize them.
Thus, they could be potentially useful for bioremediation of oil sludge and composting processes.
157
EFFECT OF ACID TREATMENT ON SEWAGE SLUDGE DERIVED CARBONS FOR

CATALYTIC WET PEROXIDE OXIDATION
Yang Yu, Huangzhao Wei, Yamin Wang, Li Yu, Wentian Jiang, Songbo He, Chenglin Sun*
(Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, P. R. China)
Nowadays, an increasing amount of sewage sludge generated by wastewater treatment plant has been an
essential environmental problem. Sewage sludge pyrolysis is considered as an interesting disposal and
develops rapidly since it is effective in reducing the volume of sludge and producing bio-oil. Sewage sludge
derived carbon (SW) could be formed during pyrolysis of sewage sludge, which contains a high content of
iron and could be employed as the catalyst in catalytic wet peroxide oxidation (CWPO). CWPO is a Fenton-
like oxidation reaction and has been widely used on the treatment of industrial wastewater containing non-
biodegradable organic pollutants. Only several studies had been carried out in CWPO reaction with SW,
however, it has not been reported about the surface modified SW in CWPO reaction. In our study, extruded
SWs treated with different kinds of acid were studied in CWPO continuous reaction. Furthermore, the effect
of surface functional groups on catalytic activity was discussed.
The results showed that the FTIR spectra of SWs treated with nitric acid, sulfuric acid and perchloric
acid exhibited a sharp and prominent peak at 1633 cm-1, which attributed to a high content of C=O or
carboxyl groups. They performed better catalytic activity in CWPO. When the initial concentration of m-
cresol was 100 mg· L-1 and H2O2 was 541 mg·L-1, m-cresol conversion reached 76%, 98% and 93%,
respectively, after 384 h continuous reaction at room temperature and LHSV of 1 h-1. However, m-cresol
conversion was only 4% and 27% for SW and SW treated with HCl, respectively. The pH of the effluent in
CWPO was also analyzed, the results indicated that the effluent by SWs treated with different acid had a
lower pH about 3.5-4.0, whereas the effluent by SW was 8.2-11.4. The low pH was caused by the
degradation intermediates of m-cresol such as fumaric acid, pyruvic acid, acetic acid and so on. The
elements content of SWs treated with different acid were analyzed, the results implied that iron might play
a main role in m-cresol degradation.
158
APPRAISAL OF CERTAIN ANAEROBIC DIGESTION STUDIES
Ram Pal Singh* and P. Pal

(Department of Civil Engineering, MNNIT, Allahabad-211004, U.P., INDIA)
ABSTRACT: From time to time, discussions of various concepts related to anaerobic digestion have
surfaced in the literature. With due recognition to the complexity of the pathways of anaerobic digestion
and participation of a wide variety of microorganisms, there has been a substantial growth of studies to
understand, model and improve the process performance. While doing so, the available literature has been
utilised to have information pertaining to kinetic parameters, conversion factors, distribution factors, etc.
Appraisal of various studies on anaerobic digestion indicated certain inconsistencies in the literature with
regard to the use of kinetic parameters and conversion factors. With this in view, the present study focuses
on the prevailing inconsistencies in anaerobic digestion studies. On various occasions, the concepts related
to anaerobic digestion have been discussed in the literature. For the purpose of this study, the same has been
excluded here to avoid repetitions. From the study, it is very evident that use of kinetic parameters from
literature in anaerobic systems’ modelling needs care and attention.
Key Words. stoichiometric coefficients, anaerobic digestion, chemical oxygen demand (COD),
kinetic parameters, microorganisms.
INTRODUCTION
The importance of anaerobic digestion process is well recognised in the literature. In the last few
decades, several studies on anaerobic digestion have shed light on the understanding of the process
performance for a variety of wastes. The role of experimental studies has been also remarkable as these
provide useful information regarding various kinetic parameters which are essential to the modelling of
anaerobic digestion systems. Associated with these developments in anaerobic digestion literature, there
have been also inconsistencies which may often be a source of misunderstanding and confusion to the
research workers, designers and operators of anaerobic digestion systems. From the review of the literature
(Lawrence and McCarty (1969), Lettinga et al. (2001), and Rumana et al.(2000)), it has been found that the
inconsistencies are apparent in the adoption of the kinetic parameters, use of conversion parameters, and
representation of stoichiometric relationships in the modelling of anaerobic digestion process. With this in
back ground, the present study addresses some of these issues and provides necessary framework for the
future studies on anaerobic digestion. For the purpose of illustrating the prevalent inconsistencies in the
literature, the study is organised in the following sections.
KINETIC PARAMETERS
Kinetic parameters are essential for defining the rate of biochemical reactions. In the literature, a
variety of rate expressions have been provided. Among these, the Monod kinetics is extensively studied and
for this reason, only the kinetic parameters pertaining to the Monod kinetics have been considered. As per
Monod kinetics, one needs to know a set of five parameters. The parameter k indicates the amount of
substrate utilised per unit mass of biomass per day. Ks indicates the half saturation constant, which is the
minimum concentration of limiting substrate at which the specific growth rate is 50% of the maximum
specific growth rate of microorganisms. Y represents the biomass yield coefficient and is defined as the
amount of biomass produced per unit mass of substrate utilized. µmax is the maximum specific growth rate
(i.e, maximum rate of change of biomass concentration per unit biomass concentration) and kd is the rate of
decay of microorganisms. Using these kinetic parameters, one can model the correspondence between the
substrate and the biomass.
In case of anaerobic digestion, one may not always encounter a single substrate situation. In fact
when a complex organic waste contains a variety of substrates, there may be a need to define kinetic
parameters with respect to each contributing substrate. Alternatively, all these substrates can be represented
in terms of any of these substrates. For example, in the case of anaerobic reactions utilising mixture of
159
volatile fatty acids, i.e., acetic, propionic, and butyric acids etc., some investigators have represented such
mixture of volatile acids in terms of a single substrate, i.e., acetic acid (Lawrence and McCarty, 1969).
Although, such a representation may lead to much simplification in the modelling of anaerobic digestion
systems, it may have its own limitations as will be discussed later in this paper.
TABLE 1. Comparison of kinetic constants as per Pavlostathis and Gomez (1991), adopted from
Lawrence & McCarty, (1969) for acetic, propionic and butyric acids as substrate
Kinetic constants from

Kinetic Constants Pavlostathis and Gomez Kinetic constants from
Comparison
↓ (1991), adopted from Lawrence & McCarty (1969)#
Lawrence & McCarty (1969)
Substrate Acetic Propionic Butyric Acetic Propionic Butyric
Remarks
→ Acid acid acid acid acid Acid
k, mgCOD/mgVSS.d
T=35°C 8.7 7.7 8.1* 8.7 7.7 8.3 k values for butyric
T=30°C 5.1 --- --- 5.1 --- --- acid are different.
T=25°C 5.0 7.8 --- 5.0 7.8 ---
Ks, mgCOD/l Slight difference in
T=35°C 165 60 13 165 60 13 Ks value for
T=30°C 356 --- --- 356 --- --- propionic acid at
T=25°C 930 1145* --- 930 1143* --- 25°C.
values are slightly
µmax, d-1 different for acetic
T=35°C 0.357 0.313 0.354 0.348c 0.3234c 0.390c acid at 35°C, but
T=30°C 0.275 --- --- 0.275 --- --- large differences for
T=25°C 0.250 0.358 --- 0.25 0.398 --- propionic and butyric
acids
Y, mgVSS / mgCOD
slight difference in
T=35°C 0.041 0.042 0.047 0.04** 0.042** 0.047**
the value for acetic
T=30°C 0.054 --- --- 0.054 -- ---
acid at 35°C.
T=25°C 0.05 0.051 --- 0.05 0.051 ---
kd, d-1
difference in the
T=35°C 0.015 0.010 0.027 0.019 0.01 0.027
value for acetic acid
T=30°C 0.037 --- --- 0.037 --- ---
at 35°C.
T=25°C 0.011 0.040 --- 0.011 0.04 ---
# - k and Ks values are expressed as equivalent concentration of acetic acid, * - value is not equal to that
mentioned by Lawrence and McCarty (1969); **- unit, mg/mg; c- computed values, µmax = k.Y
Probably the first study to obtain the kinetic parameters for a variety of wastes , i.e., acetic, propionic and
butyric acids can be credited to Lawrence and McCarty (1969). Table 1 shows the values of the some of the
kinetic parameters documented by Lawrence and McCarty (1969). It is interesting to see that these
coefficients have found applications in subsequent studies of Costello et al (1991a, 1991b) and Pavlostathis
and Gomez (1991). It is pertinent here to describe the adoption of kinetic parameters of Lawrence and
McCarty (1969) by subsequent investigators. In order to see the equivalence and comparison of kinetic
constants and their evaluations, it is essential to critically analyse them.
Maximum Specific Substrate Utilization Rate (K). The maximum specific substrate utilization rate (k-
values) is expressed by Lawrence and McCarty (1969) in terms of equivalent concentrations of acetic acids.
The values of k at 350C for acetic, propionic and butyric acids respectively are reported as 8.7, 7.7, and 8.3
mg COD to CH4/mg-d, as given in Table 1. To convert these values in terms of mg COD/mg.d, one needs
to make use of conversion factors of 1.067, 0.8 and 0.533 as per Table 2 for acetic, propionic and butyric
acids respectively.
160
In the study of Costello et al. (1991b), each substrate has been assigned a rate kinetics and thus, a
separate set of kinetic parameters. If one considers the reaction of propionic acid, the value of k to be used
should have been in terms of mmol of propionic acid/mg VSS.d. Unfortunately, this is not the case in
Costello et al. (1991b) who have used the k in terms of mmol of equivalent concentration of acetic acid/mg
biomass.d as explained below in Table 3.
TABLE 2. Conversion factor for equivalent methane COD
g methane COD/ mole g methane COD/g (as acetic

Substrate Reactions considered
of substrate consumed acid) of substrate consumed
Acetic acid CH3COO- + 2H2O→ CH4 + HCO3- 1×64 = 64 64/60 = 1.067
Propionic CH3CH2COO- + 1/2H2O→
(3/4)×64 = 48 48/60 = 0.800
acid CH3COO- + 3/4 CH4 + 1/4 CO2
Butyric CH3CH2CH2COO- + HCO3- →
(1/2)×64 = 32 32/60 = 0.533
acid 2CH3COO- + 1/2 CH4 + 1/2 CO2
To have a proper understanding of the implications of converting different wastes into equivalent
acetic acid concentration, one needs to consider the reactions of acetic, propionic and butyric acids as
documented under by Lawrence and McCarty (1969), i.e.
Acetic acid
CH3COO- + 2H2O → CH4 + HCO3- (1)
Propionic acid
CH3CH2COO- + 1/2H2O→ CH3COO- + 3/4 CH4 + 1/4 CO2 (2)
CH3COO- + 2H2O→ CH4 + HCO3- (3)
Overall reaction
CH3CH2COO- + 3/2H2O→ 7/4 CH4 + 1/4 CO2 + HCO3- (4)
TABLE 3. Equivalent conversion and comparison of kinetic constants used by Costello et al. (1991)
with those from Lawrence & McCarty, (1969) for acetic, propionic and butyric acids as substrate
Equivalent conversion of values
Cons- Kinetic constants as reported by Kinetic constants value
used by Costello et al. (1991)
tants Costello et al. (1991), adopted from As per Lawrence & McCarty
and comparison with those of
↓ Lawrence & McCarty (1969) (1969) #
Lawrence & McCarty (1969)
Subs-
Acetic Propio-nic Butyr-ic Acetic Propi- Butyr-ic Acetic Propio- Butyr-ic
trate
Acid acid acid Acid onic acid acid Acid nic acid acid
→
8.1 0.18×60 0.16×60 0.26×60
k, 0.18 0.16 0.26 9.6 15.6
mg/ = 10.8* = 9.6 = 15.6
mmol/mg.d mmol/mg.d mmol/mg.d mg/mg.d mg/mg.d
mg.d mg/mg.d mg/mg.d mg/mg.d
2.57×60 0.53×60 0.083×60
154
Ks, 2.57 mM 0.53 mM 0.083 mM 32 mg/l 5 mg/l = 154.2 = 31.8 = 4.98
mg/l
mg/l mg/l mg/l
2.5/(60× 5.0/(74× 7.5/(88×
2.5 mg/ 5.0 mg/ 7.5 mg/ 0.04** 0.042** 0.047** 1.066) 1.512) 1.816)
Y
mmol mmol mmol mg/mg mg/mg mg/mg = 0.039 =0.045* = 0.047
mg/mg mg/mg mg/mg
0.01 0.03 0.019 0.01 0.027 almost approx.
kd 0.02 d-1 equal
d-1 d-1 d-1 d-1 d-1 equal equal
# - k and Ks values are expressed as equivalent concentration of acetic acid
*
- Value is not equal to that mentioned by Lawrence and McCarty (1969)
**
- expressed as mg biological solids produced per mg COD converted to methane
Butyric acid
161
CH3CH2CH2COO- + HCO3- → 2CH3COO- + 1/2 CH4 + 1/2 CO2 (5)

2CH3COO- + 2H2O→ 2CH4 + 2HCO3- (6)
Overall reaction
CH3CH2CH2COO- + 2H2O → 5/2 CH4 + 1/2 CO2 + HCO3- (7)
and the reactions for glucose degradation as mentioned by Denac et al. (1988), i.e.
C6H12O6 → CH3CH2CH2COOH + 2CO2 + 2H2 (8)
C6H12O6 + 2H2 → 2CH3CH2COOH + 2H2O (9)
C6H12O6 + 2H2O→ 2CH3COOH + 4H2 + 2CO2 (10)
CH3CH2CH2COOH +2H2O→ 2CH3COOH + 2H2 (11)
CH3CH2COOH +2H2O→ CH3COOH + 3H2 + CO2 (12)
CH3COOH → CH4 + CO2 (13)
4H2 + CO2 → CH4 + 2H2O (14)
It can be seen that in the case of acetic acids only CH4 is produced while in the case of propionic
acid, hydrogen is also produced, which may further contribute to CH4 formation as per Eq. (14). This
contribution may be as high as 20-30% of the total methane production (Denac et al, (1988), Pantea ad
Romocea(2008)). Thus, equivalent representation of other acids (except acetic acid) may not be fully
justified. It is interesting to see from the study of Lawrence and McCarty (1969) that ionic reactions do not
represent the formation of hydrogen and hence, the H2-based CH4 production.
From Table 3, one can also note that in case of acetic acid, the value of k used by Costello et al.
(1991b) as 0.18 mmol/mg.d in their model validation is incorrect as its conversion to equivalent acetic acid
concentration works out to be 10.8 mg/mg.d which is different from the value of 8.1 mg/mg.d as reported
by Lawrence and McCarty (1969).
The values of k mentioned by Pavlostathis and Gomez (1991) are illustrated in Table 1. Although
these values are expressed in terms of mgCOD/mgVSS.d, these are truly the values of Lawrence and
McCarty (1969) expressed in units of mgCOD to CH4/mg.d except for butyric acid. Thus, adoption of such
values might lead to the errors in computations/predictions in modelling of high rate anaerobic treatment
systems due to incorrect use of original values of Lawrence and McCarty (1969).
Half Saturation Constant (Ks). Similar is the case with the Ks values which are expressed in equivalent
acetic acid concentrations. These values can be used only when different volatile fatty acids are expressed
in terms of equivalent acetic acid concentration. It is interesting to see that Costello et al (1991b) have not
treated different substrates into equivalent acetic acids in their simulations of anaerobic digester’s
performance (Table 3). If one considers the propionic acid as substrate, the units of Ks must be expressed in
terms of mass of propionic acids consumed per litre. Similar is the case in the study of Pavlostathis and
Gomez (1991) as can be seen in Table 1.
Maximum Specific Growth Rate (µ µmax). The parameter µmax is generally expressed as (k.Y). However,
one can see the incorrect evaluation of µmax values of Pavlostathis and Gomez (1991), which are different
than the computed values as marked with superscript (c) in Table 1.
Biomass Yield Coefficient (Y). The value of Y as reported by Costello et al. (1991b) presents another
interesting scenario. Contrary to k and Ks values which were expressed in terms of equivalent acetic acid
concentration, the biomass yield has been reported in terms of mmol of the actual substrate as can be seen
from Table 3.
The relative magnitude of specific biomass yields in different volatile fatty acids also presents an
interesting situation. Considerations of the following reactions can be used for having certain idea regarding
the theoretical yield with respect to synthesis of biomass having cell composition as C5H7NO2 or C5H9O3N.
Following Moletta et al. (1986) approach for synthesis of biomass C5H7NO2 from acetic acid, one can have
the following possible reactions:
5CH3COOH + 2 NH3 → 2 C5H7NO2 + 6 H2O (15)
3CH3CH2COOH + CO2+ 2NH3 → 2C5H7NO2 + 4 H2O + H2 (16)
CH3CH2CH2COOH + CO2+ NH3 → C5H7NO2 + 2H2O (17)
162
10H2 + 5CO2+ NH3 → C5H7NO2 + 8H2O (18)

5C6H12O6 + 6NH3 → 6C5H7NO2 + 18H2O (19)
Considering the reactions of glucose degradation and Eqs. (8) to (14), one can write the following overall
reactions for synthesis of biomass C5H7NO2 from different acids including Eq. (19), as given below:
3CH3CH2CH2COOH + NH3 → C5H7NO2 + 5CH4 + 2CO2 (20)
4CH3CH2COOH + CO2+ 2NH3 → 2C5H7NO2 + 4 H2O + 2CH4 (21)
6CH3COOH + 2 NH3 → 2 C5H7NO2 + CH4 + CO2 + 6 H2O (22)
14H2 + 6CO2+ NH3 → C5H7NO2 + CH4 + 10H2O (23)
Similarly for a biomass composition C5H9O3N, the individual reactions in case of different acids
can be written after Costello et al. (1991a) as under:
5CH3COOH + 2 NH3 → 2 C5H9O3N + 4 H2O (24)
3CH3CH2COOH + CO2+ 2NH3 → 2C5H9O3N + 2H2O + H2 (25)
CH3CH2CH2COOH + CO2+ NH3 → C5H9O3N + H2O (26)
10H2 + 5CO2+ NH3 → C5H9NO3 + 7H2O (27)
Considering the reactions of glucose degradation and Eqs. (15) to (19), one can write the following overall
reactions for synthesis of biomass C5H9O3N from different acids, as given below:
6CH3COOH + 2 NH3 → 2C5H9NO3 + CH4 + CO2 + 4H2O (28)
2CH3CH2COOH + NH3 → C5H9O3N + H2O + 2CH4 (29)
3CH3CH2CH2COOH + NH3 +H2O → C5H9O3N + 5CH4 + 2CO2 (30)
14 H2+ 6CO2+ NH3 → C5H9O3N + CH4 + 9H2O (31)
Using Eqs. (15) to (31), the theoretical yield can be computed. Denac et al. (1988) and Buffière et
al. (1995) indicate that yield coefficient in case of butyrate, acetate and H2 are all equal to 0.029, while in
case of propionic acid the yield coefficient is 50% lower , i.e., 0.014. Such variability in yield coefficients
is neither observed in Lawrence and McCarty, (1969) nor in the estimation of theoretical yields. Normally,
one would expect that the theoretical value of biomass yield from a particular acid is of the same order for
butyric and acetic acids in comparison to its experimental yields of acetic or butyric acids. Although such
agreement is apparent for the values of biomass yield for different acids in Lawrence and McCarty (1969),
the experimental value present another view regarding the relative importance of biomass yield among
different acids and thus, one needs to be careful while using these biomass yield estimates.
CONVERSION FACTORS
A variety of conversion factors exist in the literature on anaerobic digestion. In the study, focus will
be on the conversion factor of 1.3 g COD per g biomass as mentioned by Bryers, (1985), using biomass
formula C5H7NO2 as basis. If this conversion factor is used in the following reaction of Graf and Andrews
(1971) as given below:
CH3COOH + 0.032NH3 → 0.032C5H7NO2 + 0.92CH4 + 0.92CO2 + 0.096H2O (32)
From the above reaction, one can see that 1 g acetic acid ≡ (113x0.032/60) g biomass + 0.92x16/60) gCH4.
But as per Bryers (1985), the biomass with composition C5H7NO2 has an equivalent COD of 1.3 g COD/ g
biomass, Therefore, 1 g acetic acid ≡ (0.032x113x1.3/60) g COD + (16x4x0.92/60) gCH4-COD = 1.0596g
COD ≈ 1.06 g COD, which is contrary to the reported COD value of 1 g acetic acid as 1.067 g COD.
Similarly, by using a conversion factor of 1.3 in reaction (32), one obtains an equivalent acetic acid
COD of 0.979 g COD/g acetic acid. This shows that the COD conversion factor of 1.3 g COD/ g biomass
as mentioned by Bryers (1985), is inaccurate. Further, considering the following reactions from the literature
(MetCalf and Eddy, (1997) and Nykova et al. (2002)):
C5H7NO2 + 5O2 → 5CO2 + 2H2O +NH3 + energy (33)
(1 g cells ≡ 160/113 = 1.4159 ≈ 1.42 g COD)
C5H9O3N + 5O2 → 5CO2 + 3H2O +NH3 + energy (34)
(1 g cells ≡ 160/131 = 1.2214 ≈ 1.22 g COD)
From Eq. (33), one observes that the theoretically correct conversion factor for biomass C5H7NO2
is 1.42 g COD/ g biomass. Use of this conversion factor also leads to correct estimates of 1g acetic acid
COD equivalence as 1.067. Although, the average of the two compositions of cells lead to 1.33 g COD per
g cells, it may not be appropriate to use it arbitrarily in reactions. Further, the value of 1.42 g COD per g
163
cell or 1.22 g COD per g cell shall be used depending upon the representative cell compositions as C5H7NO2
or C5H9O3N in reactions under considerations. Thus, the value of 1.3 g COD per g biomass for cell
composition C5H7NO2 used by Bryers (1985) is questionable.
Similar is the case with the Bhatti et al. (1996), who have mentioned that 1 g TOC is equivalent to
1.4 litres of CH4 and 1 g Methanol TOC as 2.67 g COD. Considering the conversion reaction of methanol
to CH4 as per Florencio et al. (1995),
4CH3OH → 3CH4 + HCO3- + H+ + H2O (35)
From reaction (35), it can be seen that 128 g methanol (4 moles of methanol) ≡ 3 mol methane. As 1 mole
methane equals 22.4 litres at standard temperature and pressure (STP), hence,1g methanol equals
3x22.4/128 L CH4 = 0.525 L CH4 at STP. As 1 g methanol TOC = 1x12/32 g C/ g methanol = 0.375 g C/ g
methanol, and 1 g Methanol TOC = 0.525/0.375= 1.4 L CH4 at STP. In fact, 1 g TOC does not have any
sense. From the values of Bhatti et al. (1995), it can be seen that 1 g TOC should have been mentioned as
1 g methanol TOC.
Similarly, if one considers the following reactions of acetic acid and methanol for the purpose of
computing their COD values,
CH3COOH + 2O2 → 2CO2 + 2H2O (36)
2CH3OH + 3O2 → 2CO2 + 4H2O (37)
One can find from reaction (36) that 1 g acetic acid TOC = 1.066/0.4 = 2.67 g COD. Here, a
factor 0.4 appears in denominator because 1 mol acetic acid TOC = 2x12 g C and 1 g acetic acid TOC =
2x12/60 = 0.4 g C/g acetic acid. Similarly, from reaction (37), one can find that 1 g Methanol TOC =
1.5/0.375 = 4.0 g COD (1 g Methanol = 1.5 gCOD). Thus, the value suggested by Bhatti et al. (1995) that 1
g methanol TOC = 2.67 g COD, appears incorrect.
YIELD COEFFICIENT OF CO2

Determination of yield coefficients of CO2 in various reactions of different acids also becomes
relevant in modelling of CO2 production in anaerobic digestion. As the COD of CO2 is zero, Denac et al.,
(1988) represented the yield of CO2 in unit of mole/g COD. Considering the case of acetic acid, one mol
acetic acid leads to production of 1 mol of CO2; thus yield is 1 mol CO2/1 mol acetic acid = 1 mol/64 g COD
= 1.5625×10-2 mol/g COD. In the same manner, the yield coefficients in case of propionic acid, H2 and
glucose can be obtained as 8.929×10-3, 1.5625×10-3, and 6.944×10-3 respectively in view of different
reactions (Eqs. (12), (14) and (10)). Considering the mass balance equation for CO2 production as given by
Denac et al. (1988) in Eq. (15) of their research paper, one can find the incorrect use of some of these yield
coefficients; particularly for H2 and glucose, which has been taken as 1.563 and 9.945×10-3 respectively.
EQUIVALENT REPRESENTATION
With respect to the kinetic parameters, it was emphasized that different volatile acids can be represented in
terms of equivalent acetic acid concentration. Table 4 presents the approach of Lawrence and McCarty,
(1969), in which the equivalent representation of different volatile acids has been reported.
TABLE 4. Acetic acid equivalent conversion of propionic and butyric acid concentrations as
mentioned by Lawrence & McCarty, (1969)
Volatile Fatty acids as Substrate feed concentration (reported value)

substrate mg/ l mg/l as acetic acid mg COD/l
Propionic acid (T=35°C) 1925.0 1925×60/74 = 1560.8 (1560) 1925×1.512 = 2910.6 (2910)
Propionic acid (T=25°C) 3715.0 3715×60/74 = 3012.2 (3010) 3715×1.512 = 5617.08 (5620)
Butyric acid (T=35°C) 2280.0 2280×60/88 = 1554.54 (1555) 2280×1.816 = 4140.48 (4140)
Note: 1.512 is the COD conversion factor for propionic acid and 1.816 for butyric acid (Dinopoulou et al.,
1988). Here the equivalent conversion has molar basis.
In fact, in the representation of Lawrence and McCarty, (1969), the emphasis has been on the
equality of moles. Contrary to the conversion values reported in columns 3 and 4 of Table 4, one can see
that the number of moles of acetic acid are same as the number of moles of propionic acid. However, this
164
approach may not necessarily represent the equality of COD values. In fact, when the conversion is done,
the reciprocal of molecular weight of the propionic to acetic acids, the resulting values tend to give a closer
COD matching. Table 5 shows an alternative method for acetic acid equivalent conversion of propionic and
butyric acid concentrations.
The computations shown in Table 5 above show that by multiplying with a factor of 1.15, one can
have the same COD representation in case of propionic as well as equivalent acetic acid concentration.
TABLE 5. An alternative method for acetic acid equivalent conversion of propionic and butyric acid
concentrations as mentioned in Lawrence & McCarty, (1969)
Substrate feed concentration (given value)

mgCOD /l mgCOD /l mg COD/l
Volatile acid as
mg/ l as acetic acid as given acid f = (b)/(a) as given acid
substrate
(a) (b) (a)x f
Propionic acid 1925×1.066×74/60
1925.0 1925×1.512 = 2910.6 1.15 2910.5
(T=35°C) = 2530.86
3715.0 3715×1.512 = 5617.08 1.15 5616.9
(T=35°C) = 4884.23
3715.0 3715×1.512 = 5617.08 1.15 5616.9
(T=25°C) = 4884.23
Butyric acid 2280×1.066×88/60
2280.0 2280×1.816 = 4140.48 1.16 ≈ 1.15 4099.4
(T=35°C) = 3564.70
Note: 1.066, 1.512 and 1.816 are the COD conversion factors for acetic, propionic and butyric acids
respectively (Dinopoulou et al., 1988).
CONCLUSIONS
This paper considers an appraisal of few studies on kinetic parameters for anaerobic digestion and
anaerobic systems modelling. The results indicated certain inconsistencies in the literature with regard to
the use of kinetic parameters, and conversion factors. With this in view, the present study focuses on the
prevailing inconsistencies in anaerobic digestion studies. Incorrect kinetic parameters were used in recent
anaerobic system’s modelling studies. Such inconsistencies in kinetic parameters will certainly lead to
erroneous predictions in modelling and simulations of anaerobic digestion systems. It is believed that the
points focussed in this study on inconsistencies prevailing in the literature, will prove useful in better
modelling and simulations of anaerobic digestion systems with use of correct kinetic constants.
ACKNOWLEDGEMENTS
Author is grateful to Director, MNNIT, Allahabad, U.P., India and MHRD, New Delhi for his
encouragement and providing full support in preparation of this manuscript.
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166
APPLYING STATIC MAGNETIC FIELD ON PHYSICAL PROPERTIES OF ACTIVATED

SLUDGE: OPTIMIZATION THROUGH RESPONSE SURFACE METHODOLOGY
Nur Syamimi Zaidi*, Khalida Muda and Johan Sohaili

(Universiti Teknologi Malaysia, Johor Bahru, Johor, Malaysia)
ABSTRACT: One of the main challenging issues for activated sludge is the poor settleability that
consequently affect the effluent quality. Batch tests were conducted to estimate the optimal conditions for
improving the settleability of activated sludge under static magnetic field (SMF). A four-factor central
composite design (CCD) was implemented to investigate the main and interaction effects of the variables
while response surface methodology (RSM) was utilized for process optimization. Four independent
variables, viz. magnetic field (15.0 – 88.0 mT), exposure time (0.5 – 48.0 h), biomass concentration (2000
– 4000 mg/L ) and mixing intensity (200 – 400 rpm) were applied and quadratic model was built to predict
the responses. Analysis of variance (ANOVA) was used to evaluate the significance of the independent
variables and their interactions with p-values of less than 0.05. At the optimum conditions of 88.0 mT
magnetic field, 16.5 h exposure time, 2800 mg/L biomass concentration and 300 rpm mixing intensity, the
responses – turbidity reduction, aggregation and settling velocity achieved its maximum values of 92%,
99% and 0.011 cm/s, respectively. The element analysis showed that the applied SMF could enhance the
settling property of the activated sludge through the improvement on its aggregation capability. These
suggest that the SMF is reliable in accelerating the activated sludge settleability, thus potential to enhance
the performance efficiency of the wastewater treatment systems.
INTRODUCTION
Performance of activated sludge system is always relies on a good solid-liquid separation (Clauss
et al., 1998). Even though the system has been the most commonly used technology in treating municipal
and industrial wastewaters, its stable operation is still plagued by the separation and settling problems. Such
problem can lead to the deterioration of the effluent quality, sludge wash-out, and further potential to
collapse the overall treatment system performances (Martins et al., 2004; 2011). Hence, it is a necessity to
investigate for a favorable strategy that able to enhance the property of activated sludge mainly on its settling
and separation process.
One of the strategies that can be implemented is by applying static magnetic field (SMF). This
application was reported to significantly influence the bacterial activity in heterogeneous sewage, resulted
in the enhanced performances of organic compound biodegradations (Yavuz and Çelebi, 2000; Ji et al.,
2010; Łebkowska et al., 2011). The implementation of 7 mT reduced the formaldehyde (FA) concentration
and COD by 30% and 26%, respectively (Łebkowska et al., 2011). Yavuz and Çelebi (2000) also observed
that the substrate removal rate was initially increased by strengthening the magnetic field, reaching a
maximum at 17.8 mT, but decreased with a further increase of the intensity. Liu et al. (2008) applied
magnetic field in an anammox upflow system, thus resulted in significant nutrient removal. The study which
varied the magnetic field between 16.8 and 218.0 mT observed a maximum increase of nitrogen removal
by 30% at 60 mT. Apparently, an excessively strong magnetic field could harmed the bacteria while the low
field intensity has no or less effect to the bacteria. Such evidences show that there is lack of confirmation
findings on the suitable range of magnetic field that can possibly enhance the separation and settleability of
the activated sludge biomass, hence improving the removal performances of the treatment system.
Despite many studies conducted on the SMF application towards activated sludge, there are still
lack of understandings on the influence of magnetic field, exposure time, biomass concentration and mixing
intensity in enhancing the separation and settling property of activated sludge. While the important of these
factors has been qualitatively studied, most studies have not yet explored the potential interactions between
the factors. The traditional method, known as the one-factor-at-a-time (OFAT) does not fully explore all
phenomena that could possibly occur and may cause misinterpretation of the results (Montogomery, 2005;
Kusic et al., 2010; Dopar et al., 2011). Therefore, the aim of this study is to investigate the influence of
167
magnetic field, exposure time, biomass concentration and mixing intensity on the separation and settling
property of activated sludge in terms of turbidity reduction, aggregation and settling velocity. The central
composite design (CCD) approach was employed to quantitatively analyze the effects of those factors, the
interactions between them and to indicate any correlation between the factors and the responses. It is
expected that the optimal operating factors resulting from these batch tests may offer important reference
values for later continuous flow experiments.
Experimental Procedures. A total volume of 500 mL containing mixture of measured wet volume
activated sludge biomass (2000 – 4000 mg/L) and raw wastewater was mixed in a glass flask that placed in
a shaker. The shaker was fabricated to allow an installation of the permanent magnets of sizes 100 x 50 x 5
mm, arranged at all four surfaces of the flask in alternate order. The mixture of the activated sludge was
exposed to the magnetic field ranging from 15.0 to 88.0 mT within exposure time of 0.50 to 48.00 h. The
initial values of the responses (i.e. turbidity reduction, aggregation and settling velocity) were initially
measured before the batch tests started. Throughout the experiments, the mixture was mixed under a
specified mixing intensity (200 to 400 rpm). After the magnetic exposure, the mixture was allowed to idle
for 10 min before 10 mL of the liquid samples were collected and analyzed for final turbidity. The exposed
sludge of 10 mL was also taken to be measured for the final settling velocity.
Analytical Methods. All tests were conducted according to Standard Methods for the Examination of Water
and Wastewater (APHA, 2005) – MLSS with method 2540B and settling velocity with method 2710E. A
spectrophotometer (DR5000 HACH) was used for measuring COD (mg/L).YSI 556 MPS (YSI
incorporated, USA) was used for recording the values of pH, temperature (°C) and dissolved oxygen (mg/L)
for BOD purposes. Turbidity parameter (FNU) was measured using Milwaukee Turbiditimeter. As for
aggregation, the parameter was measured in terms of turbidity. After the reaction under magnetic field was
stopped, turbidity of 10 mL MLSS was measured immediately and recorded as turbidity at 0 min (T0). The
final/residual turbidity (Ti) of the supernatant is then measured after 10 min. The aggregation ability (Ag%)
can be calculated as; Ag% = [(T0 - Ti)/ T0] x 100%.
Experimental Design. The magnetic field, exposure time, biomass concentration and mixing intensity were
identified as the set of four independent process variables that been investigated due to the influence on the
responses, viz. turbidity reduction, aggregation and settling velocity of activated sludge. The CCD method
was adopted to decide the number of batch test experiments to be performed for optimization of the process
variables. For a design of four independent variables (n = 4), each with two different levels, the total number
of experiments (N) was calculated as; N = (2n + 2n + nc) = 24 + (2 x 4) + 6 = 30. This includes the standard
2n factorial points with their origin at the centre, 2n axial points fixed at a distance (α) from the centre to
generate the quadratic terms and nc replicate points at the centre (Myers and Montgomery, 2001). After the
range of each of the process variables have been defined, the limits are coded at ± 1 for factorial points, 0
for centre point and ± α for axial points. In this study, α for axial points was set to 1.0 (also known as face-
centered) due to the consideration that region of interest is approximately same as region of operatibility
(Kraber, 2002). Thus, the limit for axial points were eventually same as the factorial points. The selected
process variable with their limits are given in Table 1.
Table 1. Process control variables and their limits

Factorial Star points* Centre point
Variables
-1 +1 -1 +1 0
A: Magnetic field (mT) 15.0 88.0 15.0 88.0 51.5
B: Exposure time (hours) 0.50 48.00 0.50 48.00 24.25
C: Biomass concentration (mg/L) 2000 4000 2000 4000 3000
D: Mixing intensity (rpm) 200 400 200 400 300
* Limit for star points is the same as factorial due to the consideration of α = 1.0 (face-centered)
168
Response Surface Analysis of Turbidity Reduction, Aggregation and Settling Velocity. The results
were statistically analysed using full quadratic terms, which include linear, square and interactional terms
with the aid of Design-Expert® (version 6.0.4). The results of the analysis of variance (ANOVA) for the
responses are summarised in Table 2.
Table 2. p-values of the response surface modeling analysis

p-values
Term
Turbidity reduction Aggregation Settling velocity
A: Magnetic field 0.0023 < 0.0001 0.0368
B: Exposure time < 0.0001 < 0.0001 0.8716
C: Biomass concentration 0.0027 < 0.0001 0.6287
D: Mixing intensity 0.0097 0.7578 0.2654
A2 0.4374 0.9901 0.2488
B2 0.0446 0.0003 0.0676
C2 0.4656 0.9422 -a
D2 0.4319 0.7828 0.0309
AxB 0.0421 0.0007 -a
AxC 0.6691 0.0063 -a
AxD 0.0521 0.3195 -a
BxC 0.0361 0.0016 0.4606
BxD 0.1690 0.7408 0.4606
CxD 0.6244 0.2380 -a
R-squared value 92.6% 94.4% 61.8%
a
Eliminated value resulted from the improved model
With respect to the turbidity reduction, the results show that all the linear terms, square term in
exposure time, interactional term between magnetic field and exposure time, as well as between exposure
time and biomass concentration are significant. The analysed R-squared value of 92.6% indicates the
acceptability of the model. The best statistical model that describes the relationship between turbidity
reduction and the variables (magnetic field, exposure time, biomass concentration and mixing intensity) is
given in Eq. (1).
Turbidity reduction = +96.40 + 7.09*A + 18.14*B + 6.92*C – 5.73*D – 4.06*A2 – 11.16*B2 – 3.81*C2 –
4.11*D2 – 4.56*A*B – 0.89*A*C + 4.32*A*D – 4.72*B*C + 2.96*B*D 1.02*C*D (1)
Figure 1 shows the contour and surface plot of the defined model (exposure time and biomass
concentration) for the turbidity reduction. This interaction has the most significant p-values (0.0361)
compared to the other interaction model terms. The figure clearly shows that as the exposure time increased,
turbidity reduction is also increased. Such observation can be explained in terms of magnetic memory
retained by the activated sludge particles throughout the reaction period. As the exposure time of the
particles towards magnetic field increased, their positive and negative charges may become highly in
charged. This could increase the possibility of the collision between particles thus, potential to enhance the
coagulation and further reducing the turbidity (Higashitani et al., 1992; 1993; Johan, 2003). The increment
in turbidity reduction is also governed by the effect of biomass concentration. Similar as the exposure time,
the plot also shows that as the biomass concentration increased, turbidity reduction is also increased. This
can be reasoned due to the existance of microorganisms that been supplied with respect to the activated
sludge biomass. Lots of microorganisms during the reaction period could improved the reduction in turbidity
as more ‘workers’ are available to degrade the particles’ contaminants. Positive effects gave by both
parameters (exposure time and biomass concentration) allow the interaction to result in significant
enhancement on the turbidity reduction.
169
Statistical model as shown in Eq. (2) was also developed to relate the magnetic field, exposure time,
biomass concentration and mixing intensity to aggregation.
Aggregation = +98.87 + 3.39*A + 5.89*B +3.36*C – 0.20*D – 0.021*A2 – 7.62*B2 – 0.12*C2 +

0.46*D2 – 2.82*A*B – 2.09*A*C – 0.68*A*D – 2.53*B*C – 0.22*B*D – 0.81*C*D (2)
(a) (b)
Figure 1. (a) Contour plot and (b) response surface plot representing the relationship between the
exposure time, biomass concentration and turbidity reduction
(a) (b)
Figure 2. (a) Contour plot and (b) Three-dimensional response surface plot show the relationship between
the magnetic field, exposure time and aggregation
As shown in Table 2, linear term of magnetic field, exposure time and biomass concentration,
square term in exposure time, interactional terms between magnetic field and exposure time, magnetic field
and biomass concentration, as well as exposure time and biomass concentration are significant in influencing
the aggregation of activated sludge. Figure 2 illustrate the relationship of the most significant model term
(magnetic field and exposure time) on aggregation with p-value of 0.0007. Based on the figure, at low
magnetic field of 15.0 mT, an increase in exposure time resulted in drastic increment of aggregation from
about 83.0% to 98.6%. However, the increment is in concave shape indicates that further increase in
170
exposure time would lead to the decrease in aggregation. This could be due to the ability of microorganisms
in sustaining high magnetic effect as a result of longer exposure time. Some of the microorganisms can only
sustain low level of magnetic effect. If this level is exceeded, the microorganisms may act adversely, thus
show reverse effect to the activated sludge property (Yavuz and Çelebi, 2000; Zaidi et al., 2014). Contrary,
an increase in magnetic field illustrated increment on aggregation (at low exposure time of 0.50 h) in more
saddle shape. This type of surface plot suggested that the increment was in more progressive manner, thus
showing that the aggregation enhancement of activated sludge is more stable under such condition (Chin et
al., 2006).
For the response of settling velocity, p-values of the model terms that been listed in Table 2 are the
terms that obtained after the statistical model been improved. The purpose of the improvement is because
the initial model was insignificant. As a result, the p-value of the model was improved from 0.1208 (not
significant) to 0.0082 (significant). The R-squared value of this model is still slightly lower (61.8%)
compared to the R-squared value for turbidity reduction (92.6%) and aggregation (94.4%). The only
significant model terms are linear term of magnetic field and square term of mixing intensity. Whereas, the
interactional terms viz. exposure time and biomass concentration as well as exposure time and mixing
intensity are both insignificant with obtained p-values of 0.4606. Nonetheless, the best statistical model that
can be used to represent the settling velocity within the range of the experimental conditions in this study is
shown in Eq. (3) below.
Settling velocity = + 0.011 + (1.139 x 10-4)*A + (8.333 x 10-6)*B + (2.5 x 10-5)*C – (5.833 x 10-5)*D +
(1.523 x 10-4)*A2 – (2.477 x 10-4)*B2 – (2.977 x 10-4)*D2 + (4.063 x 10-5)*B*C – (4.062 x 10-5)*B*D
(3)
Experimental Condition Optimization. The optimization of experimental conditions was identified by

considering whether the turbidity reduction, aggregation and settling velocity were higher than the
arbitrarily chosen constraint values. According to the model, the predicted optimized conditions occurred at
magnetic field of 88.0 mT, 16.5 h exposure time, 2800 mg/L of biomass concentration and at mixing
intensity of 300 rpm. These conditions resulted in 92.1% of turbidity reduction, almost 100% (≈ 99.99%)
of aggregation and 0.011 cm/s of activated sludge settling velocity. In order to verify the optimization result
obtained from Design-Expert, batch test experiments were carried out in triplicate using the obtained
optimum conditions. Average turbidity reduction of 89.1%, aggregation of 97.8% and settling velocity of
0.011 cm/s were recorded against the predicted optimum responses. Although there are differences between
the predicted and experimental values of the responses after optimization, the deviation was still in well
agreement.
CONCLUSIONS
This study investigated the advantage of static magnetic field (SMF) and their optimized
experimental conditions for improving the physical properties of activated sludge. Under the optimal
condition of 88.0 mT magnetic field, 16.5 h exposure time, 2800 mg/L biomass concentration and 300 rpm
mixing intensity, the maximum turbidity reduction, aggregation and settling velocity of 92.1%, 99.99% and
0.011 cm/s, respectively, were obtained. Overall, the element analysis evidenced that the applied SMF could
enhance the settling property of the activated sludge through the improvement on its aggregation capability.
These suggest that the SMF is reliable in accelerating the activated sludge settleability, thus potential to
enhance the removal performance efficiency of the wastewater treatment systems.
ACKNOWLEDGEMENT
The authors thank the Ministry of Science, Technology and Innovation (MOSTI) and Universiti
Teknologi Malaysia (UTM) for financially support this research (Grant Project No: 4S032).
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171
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on formation of CaCO3 particles”. J. Coll. Int. Sci., 156: 90-95.
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photooxidation processes for the minimization of organic load of colored wastewater applying the
response surface methodology”. J. Hazard. Mater. 183: 189 – 202.
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172
LIFE CYCLE ASSESSMENT OF A MUNICIPAL WASTEWATER TREATMENT PLANT- A

CASE STUDY IN KINMEN, TAIWAN
Huan-Yu Shiu and Pei-Te Chiueh

(National Taiwan University, Taipei, Taiwan)
Life cycle assessment (LCA) was used to evaluate the environmental benefits and impacts associated with
the treatment of a wastewater treatment plant in Kinmen, Taiwan. CML 2000 model was selected as the life
cycle impact assessment tool using SimaPro software. The objective of this study is to compare current
treatment process with other proposed advanced treatment processes. The system boundary of present LCA
includes operation and maintenance phase, sludge treatment and disposal, and water reuse. The results show
that the impact of water reuse does not lead to substantial environmental impact in most of the LCA impact
categories. Water reuse is recommended for water-stressed situations, especially for Kinman which is an
outlying island. Digested sludge for agricultural applications can reduce the eutrophication potential impact
and have benefits for agriculture. The study reveals main environmental loading process of wastewater
treatment and provided an approach for supporting the choice of treatment process.
173
EVALUATION OF BACTERIA AND METALS IN SEWAGE DUMP SITE IN JOS-NIGERIA
Yakubu, Juliet M
(Federal University, Wukari-Nigeria) and Agarry O. O (University of Abuja, Nigeria)
The bacterial load and heavy metal content was carried out on a domestic sewage dump to determine the
suitability of the soil for agricultural use as is the current practice. The total viable mean colony of the 17
bacterial species detected ranged from 214.3-229.7 for soil sample; 709-779 for soil-sewage sample and
406.3-451 for deep-pit sample cells/plate. All the isolates were mesophilic showing a decrease in number
below and above 31oC. Inductively coupled Plasma Optical Emission Spectrum was used to detect 11
metals including As, Cr, Cu, Fe, K, Na, P, Sb, Se and Zn in the sludge in order to assess the pollutants and
determine the suitability of the soil for agricultural purposes. The data generated showed no hazard so far
for the direct use of such domestically generated sewage for agricultural use as biofertiliser.
174
THE EFFECT OF EPS ON MIXED LIQUOR CHARACTERISTICS AND MEMBRANE

FOULING IN UCT¬MBR PROCESS
Qiongyuan Dong, Xiaonan Feng∗, Tao Tao, Lin Chen, Junhong Zhou and Guohong Yang
a
( School of Environmental Science and Engineering, Huazhong University of Science and Technology,
Wuhan, 430074, China)
ABSTRACT: This study investigated the effect of extracellular substances (EPS) which was represented
by different MLSS concentrations on mixed liquor characteristics and membrane fouling in the UCTMBR
process. The system has operated for two months on the stable nutrient removal with complete sludge
retention before investigation. The characteristics of mixed liquor in terms of EPS, soluble microbial
products (SMP), particle size distribution (PSD), UV254 and Zeta potential were investigated in order to
evaluate their correlation with membrane fouling. It was found that the concentration of EPS and SMP
increased in the order of MLSS 4852 < 6326 < 7590 < 8793 mg/l, then the membrane fouling increase
significantly. The correlation between flux, TMP with mixed liquor characteristics followed the order of
protein content in EPS < MLSS < polysaccharide content in SMP. And the parameters of UV254, PSD, Zeta
potential were positively correlated with fouling.
INTRODUCTION
Membrane bioreactor (MBR) process has been approved to be effective and extensively used in
water and wastewater treatment. It is well know that MBR technology have many advantages over
conventional activated sludge processes, including better quality effluent, higher mixed liquor suspended
solid (MLSS) concentration, longer sludge retention time (SRT), and lower sludge production (Miura et al.,
2006; Rosenberger et al., 2002). Moreover, since the decreased of membrane cost and the shortage of water
resource, it has induced more and more researches and applications of MBR process for biological
wastewater treatment and reclamation. However, membrane fouling is one of the critical technical
difficulties for the pollutant efficiently removal stable and control the cost (Trussell et al., 2007; Zhiqiang
et al., 2006).
Given the lower sludge production of MBR, there is great interest in the complete sludge retention
of MBR system (Delai Sun et al., 2007; Ersu et al., 2010; Sridang et al., 2008). It has been verified the
operation parameters of SRT has great impact on fouling (Al-Halbouni et al., 2008; Le-Clech et al., 2006).
In the submerged MBR process, the sludge suspension was the primary cause fouling. And the near-zero
sludge discharge systems would directly affect the properties of sludge suspension. The sludge properties
such as extracellular polymeric substance (EPS), soluble microbial products (SMP), floc size, Zeta potential
and other parameters have complicated relations with membrane fouling. Ahmed et al. (Ahmed et al., 2007)
have observed the low SRT (20d) would produce higher bound EPS which was adversely to membrane
performance. Meng et al. (Meng et al., 2009) have concluded that the SRT has effect on the production of
EPS and the optimum for membrane fouling control should range at 20–50 d.
Recently membrane fouling was focus on operation optimization and membrane cleaning. Few
researches investigated the fundamental causes of fouling in near-zero sludge discharge UCT-MBR process.
This study aims to investigate the correlation of MLSS with the mixed liquor characteristics, and analysis
the decisive factors of membrane fouling through correlation models.
Experimental Set-up and Operation Conditions. The configuration of UCT-MBR used in this study
composed of anaerobic, anoxic and aerobic reactors with 7L, 12.5L and 16L working volume respectively.
The membrane modules of hollow fiber (Suzhou Litree UF Membrane Technology Co., Ltd, China), with
*
Corresponding author. Tel.: +86-27-87792152; Fax: +86-27-87792101.
E-mail address: fxnhust@163.com (X. Feng).
175
effective filtration area of 0.75 m2, were immersed in aerobic reactors. And the nominal pore size of
membranes is 0.02 μm. The permeate generation was extracted by peristaltic pump with negative pressure
on the membrane. Microporous aeration tubes were installed underneath the membrane modules to supply
dissolved oxygen as well as to mitigate membrane fouling in the aerobic reactor. The anaerobic and anoxic
reactors are equipped with mixers for fluid mixing. In the anoxic a baffle is set to divide the reactor into
two parts with volume ratio of 1:2. The internal recycles of the mixed liquor included recycle I (RI) and
recycle II (RII), which continually from aerobic to anoxic front and anoxic rear-end to anaerobic separately.
The flow rate of RII and RI were 100% and 150% of influent, respectively. The operation conditions were
set at optimum parameters by 70 days debugging. And there no sludge was discharged during the debugging.
The four levels of MLSS concentrations in aerobic were designed as 4500, 6000, 7500 and 9000
mg/L. The measured values were 4852, 6326, 7590 and 8793 mg/L. The dissolve oxygen (DO)
concentration was determined and controlled at 0.5-2mg/l, 4.4-5mg/l in anoxic and anaerobic reactor
respectively. ORP value were -180～-270, -30～76, and 80～153 mV in anaerobic, anoxic and aerobic
reactors.
Raw Wastewater. Synthetic wastewater fed to the reactor contained sodium acetate, NH4Cl, and KH2PO4
served as nutrients of carbon, nitrogen and phosphorus, respectively. The mineral solution consisted with
30 mg/L MgSO4.7H2O and 10 mg/L CaCl2 was also added into the wastewater. The concentration of total
organic carbon (TOC), NH4+-N and total P (TP) of the synthetic wastewater were 47.62±3.61, 28.62±4.2
and 4.66±1.6, respectively. And the pH of raw wastewater was 8.77.
Analytical Methods. Samples were collected from the aerobic reactor and permeate effluent under steady-
state conditions. The MLSS, NH4+–N and total phosphate (TP) was measured according to Standard
Methods (APHA 1998). The aerobic sludge mixed liquor were sampled and filtered through 0.45 μm filters
for detected of SMP, UV254. EPS were extracted following the procedure of centrifugation (4800 r/min) for
10 min, then heated at 80℃ for 20 min, then filtered through 0.45μm filters and analyzed. The components
of EPS contain polysaccharides (EPSC), proteins (EPSP) and other components, which include humic acids
and nucleic acids. Polysaccharides were determined according to Dubois et al. (1956) and proteins were
determined according to the method of modified Folin-phenol described by Froelund et al. (1995). In this
experiment, the concentration of TOC represents the total amount of EPS, and other components of EPS
were calculated by EPS subtract polysaccharides and proteins contents. DO, ORP and pH were measured
using DO and pH meters (YSI, USA). And the membranes flux and transmembrane pressure (TMP) were
monitored daily.
Statistical Analysis. Statistical analysis was carried out by using the Pearson correlations of SPSS 11.0
software. Pearson’s correlation coefficient (rp) was used for estimated the correlations between every two
parameters. The rp ranges between －1 and +1, where means perfect negative and positive correlations
respectively, while 0 means an absence of a relationship.
Factors analysis method was used for all parameters correlation analysis. The KMO (Kaiser-Meyer-
Oklin Measure of Smapling Adequacy) and Bartlett Sphericity Test were used firstly to determine the
original variables whether suitable or not for the use of factors analysis method.
Variation of EPS Concentrations. As shown in FIGURE 1A, the total amount of EPS concentration
increased as MLSS increased from 4852 to 8793 mg/l. The protein was the major composition of EPS and
its percentage was 83%~90% (FIGURE 1B), and similar result has been reported in high SRT system by
Liao et al (Liao et al., 2001). The results indicated that an increase of MLSS could lead to the change of
sludge mixed liquor properties.
The amount of EPS and its composition was determined by the production and degradation of
microorganism. On one hand the higher organic load lead to microbial growth and store the organics into
intracellular polymer. However, as the MLSS concentration gradually increased to more than 7590 mg/L,
microorganism was in endogenous stage for organic substances became insufficient, then EPS increased
176
sharply and other substances also release. Meanwhile, most extracellular secretion of high molecular
substance were rejected by ultrafiltration membrane and degraded as residence time increased. The contrary
aspects contributed to the growth platform at MLSS of 8793 mg/l.
(B) 100 Polysaccharide Protein Others

(A) 50 50
E-Polysaccharide
E-Protein
40 Others 40 80
Concentration (mg/l)
EPS (mg/g.VSS)
EPS
Percentage (%)
30 30 60
20 20 40
10 10 20
0 0 0
4852mg/l 6326mg/l 7590mg/l 8793mg/l 4852mg/l 6326mg/l 7590mg/l 8793mg/l
MLSS MLSS
FIGURE 1. Effect of MLSS on EPS and its composition production. (A) Concentrations, (B) Percentage.
Soluble Microbial Products (SMP). The compositions of SMP were similar to EPS and the FIGURE 2
illustrated polysaccharide was the major substance of 57%~63%. As shown in FIGURE 2, the total amount
of SMP was markedly increased as MLSS increasing and the same trend of polysaccharide. The increased
concentration of SMP was ascribed to membrane rejection and microorganism endogenous respiration
production. The organic substance of influent was synthetic at low and constant concentration, as the MLSS
increased it became insufficiently and microorganism used polysaccharide and protein of SMP as carbon
resources. When the concentration of MLSS achieved to certain degree, the production and degradation of SMP
reached balanced, then the concentration of SMP tended stability.
12 16
Polysaccharide
Protein 14
10
Others
12
Concentration (mg/L)
SMP
8
10
SMP (mg/L)
6 8
6
4
4
2
2
0 0
4852mg/l 6326mg/l 7590mg/l 8793mg/l
MLSS
FIGURE 2 Effect of MLSS on the concentration of SMP and its compositions.
TABLE 1. Pearson’s correlation coefficient (rp) between MLSS concentration and sludge properties
MLSS
rp p
EPS 0.856 0.000
EPSC 0.408 0.063
EPSP 0.863 0.000
SMP 0.787 0.000
SMPC 0.749 0.000
SMPP 0.429 0.052
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The concentration of MLSS showed significant positive effect on the production of EPS (rp = 0.856;
p = 0.000) and SMP (rp = 0.787; p = 0.000). The EPSP also showed positive correlation with MLSS and
was the most significant parameters in TABLE 1. However, EPSC and SMPP did not show significant
correlation between MLSS probably due to the dominant composition of EPS and SMP were protein and
polysaccharide, separately.
TABLE 2. Coefficient matrix of component score

COMPONENT
MLSS 0.134
EPS 0.137
EPSP 0.149
EPSC 0.129
EPSP/EPSC -0.081
SMP 0.123
SMPP 0.107
SMPC 0.11
SMPP/SMPC 0.061
Zeta potential 0.033
Cake layer of Zeta 0.129
SMP-UV254 -0.131
The compositions of SMP and EPS were similarly while the proportion of each component was
different. There may be existed internal relations in the production, dissolution, degradation between SMP
and EPS. In addition, researcher have pointed that part of SMP was dissolved EPS (Lin et al., 2014). It was
concluded that MLSS influenced EPS significantly and EPS dissolution is the main way to produce SMP,
whereas SMP was mainly affected by the EPS and MLSS together.
Factors Analysis of Mixed Liquor Characteristics. The mixed liquor characteristics parameters including
MLSS, EPS, EPSP, EPSC, EPSP/EPSC, SMP, SMPP, SMPC, SMPP/SMPC, Zeta potential, Cake layer of Zeta,
and UV254 of SMP (SMP-UV254). The software of SPSS was carried out for factors analysis and the results
were showed in TABLE 2. The extraction method adopt principal component and one component was
extracted in TABLE 2.
The all eleven parameters effect for the overall level of mix liquor was lowers than 0.2 (TABLE 2).
It indicated that each parameter has strong correlations in the mix liquor. Generally, the mixed liquor
characteristics are a dynamic process of factors interaction and MLSS is a public factor of influence. In
addition, EPS is the closely related index with MLSS.
Membrane Fouling Correlation Analysis. Based on the correlation analysis, SMP was affected by EPS
and MLSS together. The effect fundamental parameters of membrane fouling were MLSS and SMP. During
the experiment, the hollow fiber membrane flux was large and there was no obviously decline. In order to
avoid the potential risk of measuring error and really reflect the correlation of membrane fouling and mixed
liquor characteristics. Multivariate correlation analysis was adopted to make a statistics about the influence
of MLSS and SMP concentration to the transmembrane pressure (TMP). Previous research considered that
there lies in an exponential relationship between membrane mass transfer resistance and the concentration
of MLSS and SMP. The correlation equation was assumed as follows (Eq1). The regression equation
obtained by this method showed as Eq2.
TMP = k·MLSSa·SMPb (1)

TMP = 0.6121·MLSS0.1281·SMP0.0751 (2)
The Eq2 showed positive correlations between TMP and the concentration of MLSS and SMP.
However, SMP has less effect to the TMP compared with the MLSS. As FIGURE 3 showed, the measuring
value of TMP compared with its simulation value to test the accuracy of the regression equation. Results
indicated that the simulation value of TMP was in agreement with the measuring value, and the average
relative error was 7.84%. Therefore the regression equation was effectively.
178
17.5
measured
17.0 simulated
16.5
TMP (KPa)
16.0
15.5
15.0
14.5
14.0
0 5 10 15 20 25 30 35 40 45
Sample number
FIGURE 3 The comparison of measured and simulated values
CONCLUSIONS
This paper investigated mixed liquors characteristics and membrane fouling in UCT-MBR process.
Based on the results illustrated in this study, the following conclusions can be drawn:
The concentration of EPS and SMP of mixed liquor increased as MLSS concentration increasing
from 4500 mg/l to 9000 mg/l. The major component of EPS and SMP is protein and polysaccharide
respectively. The concentration of MLSS has significant positive effect on the production of EPS and SMP.
EPS is mainly affected by MLSS, and SMP influenced by EPS and MLSS together.
MLSS and SMP are the fundamental parameters affect membrane fouling. Multivariate correlation
equation is TMP = 0.6121·MLSS0.1281·SMP0.0751.
REFERENCES
Ahmed, Z., J. Cho, B. Lim, K. Song, and K. Ahn. 2007. “Effects of sludge retention time on membrane
fouling and microbial community structure in a membrane bioreactor.” J. Membr. Sci. 287: 211-218
Al-Halbouni, D., J. Traber, S. Lyko, T. Wintgens, T. Melin, D. Tacke, A. Janot, W. Dott, J. Hollender.
2008. “Correlation of EPS content in activated sludge at different sludge retention times with membrane
fouling phenomena.” Water Res. 42: 1475-1488
Delai Sun, D., S. Loong Khor, C. Teck Hay, J. O. Leckie. 2007. “Impact of prolonged sludge retention time
on the performance of a submerged membrane bioreactor.” Desalination. 208: 101-112
Ersu, C.B., S.K. Ong, E. Arslankaya, Y. Lee. 2010. “Impact of solids residence time on biological nutrient
removal performance of membrane bioreactor.” Water Res. 44: 3192-3202
Le-Clech, P., V. Chen, T. A. G. Fane. 2006. “Fouling in membrane bioreactors used in wastewater
treatment.” J. Membr. Sci. 284: 17-53
Liao, B.Q., D.G. Allen, I. G. Droppo, G. G. Leppard, S. N. Liss. 2001. “Surface properties of sludge and
their role in bioflocculation and settleability.” Water Res. 35: 339-350
Lin, H., M. Zhang, F. Wang, F. Meng, B. Liao, H. Hong, J. Chen, W. Gao. 2014. “A critical review of
extracellular polymeric substances (EPSs) in membrane bioreactors: Characteristics, roles in membrane
fouling and control strategies.” J. Membr. Sci. 460: 110-125
Meng, F., S. Chae, A. Drews, M. Kraume, H. Shin, F. Yang. 2009. “Recent advances in membrane
bioreactors (MBRs): Membrane fouling and membrane material.” Water Res. 43: 1489-1512
Miura, Y., Y. Watanabe, S. Okabe. 2006. “Membrane Biofouling in Pilot-Scale Membrane Bioreactors
(MBRs) Treating Municipal Wastewater: Impact of Biofilm Formation.” Environ. Sci. Technol. 41:
632-638
Rosenberger, S., U. Krüger, R. Witzig, W. Manz, U. Szewzyk, M. Kraume. 2002. “Performance of a
bioreactor with submerged membranes for aerobic treatment of municipal waste water.” Water Res. 36:
413-420
179
Sridang, P. C., A. Pottier, C. Wisniewski, A. Grasmick. 2008. “Performance and microbial surveying in
submerged membrane bioreactor for seafood processing wastewater treatment.” J. Membr. Sci. 317:
43-49
Trussell, R. S., R.P. Merlo, S. W. Hermanowicz, D. Jenkins. 2007. “Influence of mixed liquor properties
and aeration intensity on membrane fouling in a submerged membrane bioreactor at high mixed liquor
suspended solids concentrations.” Water Res. 41: 947-958
Zhiqiang, C., W. Qinxue, W. Jianlong. 2006. “High rate aerobic treatment of synthetic wastewater using
enhanced coagulation high-performance compact reactor (EC-HCR).” Biochem. Eng. J. 31: 223-227
180
AN APPROACH FOR SELECTION OF WASTEWATER TREATMENT UNITS USING

ANALYTICAL HIERARCHY PROCESS
Nekram Rawal* and A.K.Sachan

(Department of Civil Engineering, MNNIT, Allahabad-211004, U.P., INDIA)
ABSTRACT: there are several established and time tested technologies available for treatment of municipal
wastewater. Each technology has its own merits depending on its suitability and fulfillment of requirements
and a set of criteria. This paper focuses to evaluate suitability of wastewater treatment technologies in
different situations. The analytical hierarchy process (ahp), a known multi-criteria decision-analysis
approach, has been incorporated to subsequently develop a decision support tool to select most suitable
wastewater treatment technology for treating municipal wastewater with effluent quality conforming to
indian standards. Quantitative weightings from the ahp are used to identify alternative systems that have
similar outcomes in meeting the systems objective, but may have different cost structures, reliability and
effluent quality. Three known technologies options were primarily taken for selection of wastewater
treatment technologies, trickling filter system, waste stabilization pond and activated sludge process. The
result obtained by ahp approach shows that option with waste stabilization pond is the best treatment
technology among all other treatment process in terms of economic parameters.
Key words. analytical hierarchy process (ahp), trickling filter, waste stabilization pond, activated
sludge process.
INTRODUCTION
In presently designers, engineers and constructors are working hard to find the solution of selecting
such a design alternative which is technically feasible, sustainable and at the same time economic in the
long run. There are several established and time tested technologies available for treatment of municipal
wastewater. Each technology has its own merits and demerits depending on its suitability and fulfillment of
requirements and a set of criteria. Several methods have so far been developed, tried and tested to select the
best option based on the above set goals. The Analytical Hierarchy Process (AHP) is one of the method
that provides a significantly better economic assessment of the long term cost effectiveness of a project
with the merits and demerits of mutually exclusive design options . It is a systematic, analytical process
developed by Satty, T.L.; Kearns, K.P. (1985) has been applied to a wide variety of decisions and the human
judgment process (Lee et al.,2001). This technique is one of the MCDA (Multi Criteria Decision Analysis)
methods with many capabilities used in different scientific disciplines and suitable for solving complicated
issues such as resources allocation, project design, planning for urban development, maintenance
management (Cook et al., 1984). Decision maker then find out simple pair wise comparison judgments
throughout the hierarchy to arrive at overall priorities for the alternatives suggested (Higgs, 2006). The
decision problem may involve social, political, technical, and economical factors. AHP analysis make it
useful tool for environmental sustainability assessment and decision-making (Schmoldt et al.,2001). In
environmental performance field studies, AHP has been widely employed such as; environmental impact
assessment (Ramanathan, 2001), environmental quality indexing (Solnes, 2003), environmental
vulnerability assessment (Tran et al.,2002), energy resources (Ramanathan et al.,1995), environmental
impacts of manufacturing (Pineda-Henson et al.,2002), landfill site selection problem (Mummola, 1996),
land use pattern (Malczewski et al.,1997), and resource allocation of agricultural activities (Alphonce,
1997). The AHP helps people cope with the intuitive, the rational and the irrational. At the end of the
process, decision makers are fully cognizant of how and why decision was made, with results that are
meaningful, easy to communicate and actionable. In this paper, an attempt is made to select the best design
option of wastewater treatment technology treating 12MLD plant of municipal wastewater of semi-urban
locality of India.
181
TECHNOLOGY OPTIONS
The selection of treatment technology for municipal treatment eventually depends upon wastewater
characteristics, treatment objectives as translated into desired effluent quality and the environmental
condition. All treatment technology options lower the quality of effluent conforming to Indian standards. In
this study, the three options of treatment technology are taken for consideration for AHP analysis. These
three options are:- (i) Option A: Trickling filter is now almost universally adopted wastewater treatment
process. Rate of filter loading is high, as such requiring lesser land areas and smaller quantities of filter
media for installation. (ii) Option B: Waste Stabilization Ponds are well-established methods and having
many advantages includes simplicity, low cost of construction, low maintenance, low energy consumption,
robustness, and sustainability. (iii) Option C: Activated sludge process is in use since the early 1900s. The
operational advantages are, lesser land area required, head loss in the plant is low, greater flexibility in
operation, permitting control on the quality of effluent.
FIGURE 1. AHP principles and its steps
TABLE 1. Pair-wise comparison scale for AHP preferences

Verbal Judgments of Numerical
Numerical Rating Verbal Judgments of Preferences
Preferences Rating
5 Strongly preferred 9 Extremely preferred
4 Moderately to strongly 8 Very strongly to extremely
3 Moderately preferred 7 Very strongly preferred
2 Equally to moderately 6 Strongly to very strongly
1 Equally preferred
Reciprocals of the
If factor i has one of the above non-zero numbers assigned to it when compared to factor
above non zero
j, then j has the reciprocal value when compared with i.
numbers
METHODOLOGY
The analytical hierarchy process (AHP) developed by Saaty (1980) deals with the complex decision
making problems, which involves many attributes/variables and some sort of subjectivity. The principles of
AHP and its steps (Hambali et al.,2009) shown in Figure 1. It offers a pair-wise comparison of components
182
of the systems, precisely if the attributes are objective or provide the scaling if the attributes are subjective
in nature. The comparisons are made for each variable and sub variables and the matrix is constructed by
the preferences are quantified by using a nine-point scale of comparisons and is given in Table 1[1].
FIGURE 2. Hierarchy of the project
Development of Hierarchy. A three level hierarchy decision process suggested by Zeng et al., 2007 shown
in Figure 2. The overall goal is to select the most suitable wastewater technology is presented at the top
level of the hierarchy. The second level represents the criteria’s that influence selection of a wastewater
treatment technology.
Develop Pair-Wise Comparison Matrix. The all matrices are developed pair-wise comparisons as shown
in Table 2, eigenvectors or the relative weights (the degree of relative importance amongst the elements),
global weights, and the maximum eigenvalue ( λmax ) for each matrix are then calculated.
TABLE 2. Comparative judgment matrix for selection of best wastewater treatment technology
Technology Options
Criteria
A (TF) B (WSP) C (ASP)
Capital cost(CC) Higher Highest High
Operation & Maintenance cost (O&M) Higher Lowest Highest
Ability to handle flow variation(ATH) Good Moderate Fair
Reliability(R) Very good Very good Good
Effluent quality (E) Moderate Good Very good

The methodology demonstrated for treating 12 MLD municipal wastewater of semi urban area at
Kalyani located 40 km from Kolkata, India. The study is carried out to evaluate suitability of wastewater
treatment technologies by AHP.
Development of Pair-wise Comparison Matrices: The decision makers have to indicate preference or
priority for each decision alternatives. Table 3 shows the pair-wise comparison matrices for each criteria i.e
capital cost, operation and maintenance cost, Ability to handle flow variation, reliability and effluent
quality of treatment option and Table 4 shows pair-wise comparison matrix for all five criteria in terms of
importance of each in contributing to the overall goal.
Calculation of Priority Vector: The Table 5 shows the priority vector for each criteria of treatment option
and Table 6 shows the priority vector for all five criteria in terms of importance of each in contributing. The
elements in each row are multiplied with each other and then the nth root (where n is the number of elements
in the row. Next the numbers are normalized by dividing them with their sum.
183
TABLE 3. Pair-wise comparison matrix
Options A B C
Capital cost
A 1 3 1/2
B 1/3 1 1/3
C 2 3 1
Operation & Maintenance
A 1 1/3 2
B 3 1 3
C 1/2 1/3 1
Ability to handle flow variation
A 1 3 4
B 1/3 1 3
C 1/4 1/3 1
Reliability
A 1 1 3
B 1 1 3
C 1/3 1/3 1
Effluent quality
A 1 1/3 1/4
B 3 1 1/2
C 4 2 1
TABLE 4. Pair-wise comparison matrix for five criteria
Ability to
Capital Operation & Effluent
handle flow Reliability
cost Maintenance quality
variation
CC 1 2 4 4 2
O&M 1/2 1 3 3 2
ATH 1/4 1/3 1 2 1/3
R 1/4 1/3 1/2 1 1/3
E 1/2 1/2 3 3 1
Consistency Ratio (CR): The value of CR is less than or equal to 0.05 for 3x3 matrices and less than or
equal to 0.10 for 5x5 matrix in all five criteria, it means that the matrix is acceptable or indicates a good
level of consistency in the comparative judgments represented in each matrix.
Development of Overall Priority ranking of all the Design Options: The criteria priorities and the
priorities of each decision alternative relative to each criterion are combined in order to develop an overall
priority ranking of all the alternatives that is termed as the decision matrix shown in Table 8.
The overall rank of the design options against calculations done using the AHP analysis, the Option
B, Waste Stabilization Pond system is the best wastewater treatment technology and having very high
overall priority vector among the criteria.
CONCLUSIONS
184
Analytical Hierarchy Process (AHP) recommends that option with waste stabilization pond is the
best treatment technology among Trickling Filter and Activated Sludge Process treatment technology in
terms of all other economical parameters.
TABLE 5. Priority Vector

Options Capital cost Priority vector
A (1x3x1/2)1/3 1.145 0.333
1/3
B (1/3x1x1/3) 0.481 0.140
C (2x3x1)1/3 1.816 0.528
Sum 3.442 1.000
Operation and maintenance cost
A (1x1/3x2)1/3 0.874 0.250
B (3x1x3)1/3 2.079 0.594
1/3
C (1/2x1/3x1) 0.550 0.157
Sum 3.503 1.000
Ability to handle flow variation
A (1x3x4)1/3 2.288 0.614
B (1/3x1x3)1/3 1.000 0.268
C (1/4x1/3x1)1/3 0.437 0.117
Sum 3.725 1.000
Reliability
A (1x1x3)1/3 1.442 0.429
B (1x1x3)1/3 1.442 0.429
C (1/3x1/3x1)1/3 0.481 0.143
Sum 3.365 1.000
Effluent quality
A (1x1/3x1/4)1/3 0.437 0.122
B (3x1x1/2)1/3 1.145 0.320
C (4x2x1)1/3 1.999 0.558
Sum 3.580 1.000
TABLE 6. Priority vector for the five criteria

Geometric mean value Priority vector
CC (1x1/2x3x3x1/2)1/5 1.176 0.202
O&M (2x1x3x3x2)1/5 2.048 0.352
ATH (1/3x1/3x1x2x1/3)1/5 0.594 0.102
1/5
R (1/3x1/3x1/2x1x1/3) 0.450 0.077
E (2x1/2x3x3x1)1/5 1.552 0.267
Sum 5.820 1.000
TABLE 7. The Consistency Ratio (CR)

Sl. no Criterion Consistency ratio Remark
1 Capital cost 0.05= 0.05 Consistent
2 Operation & Maintenance 0.048<0.05 Consistent
3 Ability to handle flow variation 0.05 = 0.05 Consistent
4 Reliability 0.003<0.05 Consistent
5 Effluent quality 0.016<0.05 Consistent
6 For all Criteria under consideration 0.042<0.10 Consistent
185
TABLE 8. Decision matrix for selection of design options

CC O&M ATH
Option R (0.077) E (0.267) OP Ranking
(0.202) (0.352) (0.102)
A 0.333 0.250 0.614 0.429 0.122 0.284 3
B 0.140 0.594 0.268 0.429 0.320 0.383 1
C 0.528 0.157 0.117 0.143 0.558 0.334 2
REFERENCES
Satty, T.L., and Kearns, K.P. 1985. "Analytical Planning: The Organization of Systems", Pergamon, Oxford.
Lee, W.B., Lau, H., Liu, Z., and Tam, S. (2001). “A fuzzy analytical hierarchy process approach in modular
product design”. Journal of Expert System, 18(7): 32-42.
Cook, T., P. Falchi and R. Mariano, (1984). An urban allocation model combining time series and analytic
hierarchical methods. Manage. Sci., 30: 198-208.
Higgs, G., 2006. “Integrating multi-criteria techniques with geographical information systems in waste
facility location to enhance public participation.” Journal of Waste Management and Resarch, 24(3):
105-117.
Schmoldt, D.L., Kangas, J. &Mendoza, G.A. (2001). "Basic principles of decision making in natural
resources and the environment", in: Schmoldt, D.L., Kangas, J., Mendoza, G.A. &Pesonen, M. (Eds.),
The Analytic Hierarchy Process in Natural Resource and Environmental Decision Making, Managing
Forest Ecosystems Series, (3). Kluwer Academic Publishers, Dordrecht, 1-15.
Ramanathan, R. (2001). "A note on the use of the analytic hierarchy process for environmental impact
assessment". Journal of Environmental Management, 63: 27-35.
Solnes, J. (2003). "Environmental quality indexing of large industrial development alternatives using AHP".
Environmental Impact Assessment Review, 23: 283-303.
Tran, L.T., Knight, C.G., O’Neill, R.V., Smith, E.R., Riitters, K.H. &Wickham, J. (2002). "Fuzzy decision
analysis for integrated environmental vulnerability assessment of the midatlantic region".
Environmental Management, 29: 845-859.
Ramanathan, R. &Ganesh, L.S. (1995). "Energy resource allocation incorporating qualitative and
quantitative criteria: an integrated model using goal programming and AHP". Socio- Economic
Planning Sciences, 29: 197-218.
Pineda-Henson R., Culaba, A.B. &Mendoza, G.A. (2002). "Evaluating environmental performance of pulp
and paper manufacturing using the analytic hierarchy process and lifecycle assessment". Journal of
Industrial Ecology, 6: 15-28.
Mummola, G. (1996). "An analytic hierarchy process model for landfill site selection". Journal of
Environmental Systems, 24: 445-465.
Malczewski, J., Moreno-Sanchez, R., Bojorquez-Tapia, L.A. &Ongay-Delhumeau, E. (1997). "Multicriteria
group decision-making model for environmental conflict analysis in the cape region, Mexico". Journal
of Environmental Planning and Management, 40, 349-374.
Alphonce, C.B. (1997). "Application of the analytic hierarchy process in agriculture in developing
countries". Agricultural Systems, 53: 97-112.
Satty, T.L., (1980). "Analytic Hierarchy Process", McGraw-Hill, New York.
Hambali, A., Sapuan, S. M., Ismail, N., and Nukman, Y. (2009). “Application of Analytical Hierarchy
Process in the design concept selection of automotive composite bumper beam during the conceptual
design stage.” Journal of Scientific Research and Essay. 4(4): 198-211.
Zeng, G.; Jiang, R.; Huang, G.; Xu, M. and Li J. )2007) “Optimization of wastewater treatment alternative
selection by hierarchy grey relational analysis", Journal of Environmental Management, 82: 250–259.
186
STRUCTURE AND FUNCTION OF DOMINANT MICROBIAL COMMUNITY IN ENHANCED

AEROBIC GRANULAR SLUDGE PROCESS
Liang Zhu1,2, Xiangyang Xu1,2, Xin Dai1, Jiaheng Zhou1

(1. Department of Environmental Engineering, Zhejiang University, Hangzhou 310058, China; 2.
Zhejiang Province Key Laboratory for Water Pollution Control and Environmental Safety, Hangzhou
310058, China)
Aerobic granular sludge has a compact physical structure which favors the excellent settlement and high
biomass enrichment to simplify the separation of mixed liquor and reduce footprint demand, and is named
as “The Next Generation Wastewater Treatment”. Instability problem of aerobic granule is still existed
during the long-term operation, and the microbial mechanism needs to be explored. Two kinds of step-
aeration methods were used to enhance aerobic granular sludge process, and the structure and function of
dominant microbial community of aerobic granular sludge were studied.
Results showed that DO decreased immediately after aeration intensity reduced directly during
aerobic starvation stage, and granular sludge disintegrated and washed out. Extracellular protein (PN)
changed obviously in granular sludge, and the PN/PS ratio decreased to about 2. Granular sludge was not
stable under the low DO level and sludge PN content varied variously. After the application of gradient
decrease of aeration intensity during aerobic starvation stage, DO decreased slowly and maintained at 4.5-
5.0 mg•L-1 finally. The hydrophobicity and intensity of aerobic granule increased obviously. The stable
granular structure, low biomass yield and high removal efficiency of enhanced process were achieved, along
with the PN increasing modestly and PN/PS ratio increasing to above 7. Thereinto, the aromatic protein-
like (especially tryptophan protein with Amide III and primary structure) favors microbial aggregation and
sludge granulation using 3D-EEM and FTIR.
After the direct decrease of aerobic intensity, Shannon index of sludge microbial community varied
from 4.76 to 3.92, which indicated that the irreversible wash-out of functional microbes resulted in the
disintegration of granular sludge. The predominant proportion of Proteobacteria decreased from 45% to
23%, while the proportion of Bacteroidetes increased from 31% to 63%. Thereinto, Leadbetterella spp.
appeared and became the absolute dominant species at instable granule with proportion of 45%. After
gradient decrease of aerobic intensity during aerobic starvation, the microbial diversity of granular sludge
recovered with the Chao and Shannon index increasing to 3925 and 5.79. Zoogloea spp., Thauera spp. and
Nitrospira spp. became dominant species in the stable granule. The location of Zoogloea spp. with the
function of EPS secretion was consistent with the distribution of PN in granular sludge. Results demonstraed
that the enhanced aerobic granule process with the gradient decrease of aeration intensity during aerobic
starvation stage favors the formation and structure stability of aerobic granular sludge.
187
BIOGENIC MANGANESE OXIDE GENERATION AND Mn(II) REMOVAL BY MANGANESE

OXIDIZING BACTERIA USING RESPONSE SURFACE METHODOLOGY
Shalu and Narsi R. Bishnoi* (Department of Environmental Science and Engineering, Guru Jambheshwar
University of Science & Technology, Hisar 125001 Haryana, India)
ABSTRACT: This study presents the isolation and screening of manganese (II) oxidizing bacteria from
wastewater samples of electroplating industrial effluent and its application as a potential biosorbent to
remove Mn(II) ions from aqueous solution in a batch system. A statistical approach, the response surface
methodology is used to determine the optimum conditions for the generation of biogenic manganese oxides
and manganese removal using manganese oxidizing bacterial strain Mn 21. Based on the statistical analysis;
the maximum biogenic manganese oxide formation and manganese removal was obtained 64.90% and
96.90% at pH 8, temperature 300C and 10 days incubation time. We can achieve a maximum removal and
Mn oxide formation upto 108.9% and 71.1% respectively at optimal conditions of pH 8.0, temperature
31.70C and incubation time of 9.7 days having maximum desirability. The analysis of variance (ANOVA)
of Box–Behnken design showed that the proposed quadratic model fitted experimental data very well with
coefficient of correlation r2 to be 0.9821, 0.9744 for manganese removal and manganese oxide formation
respectively.
INTRODUCTION
Microorganisms (bacteria and fungi) that oxidize Mn(II) to Mn(III/IV) oxides are known as Mn-
oxidizing microorganisms, this specific type of sorbent with biological origin is represented by biogenic
manganese oxides, are believed to be the most abundant and highly reactive Mn oxide phases in the
environment. The rate of biogenic Mn(II) oxidation is faster than abiotic Mn(II) oxidation rates (Tebo et al.
2004). The microbial Mn(II) oxidation occurs by an enzymatic pathway (Francis et al. 2001). These biogenic
Mn oxides are precipitated on cell surfaces. They are extensively used in remediation of heavy metals
[Cu(II), Co(II), Cd(VI), Zn(II), Ni(II), Cr (III), Pb(II), As(III) and U(VI)] from metal-contaminated soils
and waters (Meng et al., 2009; Ivarsson et al., 2011; Watanabe et al ., 2012). Due to the higher surface area
and higher binding energy per unit area, biogenic Mn oxides have a higher capacity for sorption of metal
ions than abiogenic Mn oxides (Nealson et al., 2002).
Response surface methodology (RSM) is a collection of mathematical and statistical techniques
for modelling and analysis of problems in which a response of interest is influenced by set of independent
variables (Khuri, 2006; Singh et al., 2012). Main advantages of optimization by RSM to conventional
method are reduction of experimental trials in providing sufficient information for statistically valid results
and evaluation of the relative significance of parameters and their interactions (Moghaddam et al. 2011). It
is well suited approach to study the main and interactive effects of distinct variable and optimization of the
process. Response surface methodology was applied to the Box-Behnken experimental design (Khuri,
2006). The main goal of the study was to isolate the manganese oxidising bacteria; prepare biogenic
manganese oxides and its application as a potential biosorbent to remove Mn(II) ions from aqueous solution
in a batch system.
Sample Collection. Wastewater samples were collected from electroplating industry, Neel Metal Ltd.
Gurgaon, Haryana, India.
Strain isolation and Screening. The Mn oxidising bacteria were isolated from metals contaminated soil
samples through enrichment culture techniques by Mn-oxidation media and screened on the basis of their
ability to produce brown Mn oxide-encrusted colonies on plates. The presence of Mn oxides was confirmed
using the colorimetric dye Leucoberbelin blue (LBB).
188
Statistical Optimisation Study. The experiments were conducted to optimize pH, temperature and contact
time for the formation of biogenic manganese oxides and sorption of Mn(II) ions in batch process. For
optimization, 20 ml of Mn-oxidation broth media in 30 ml culture tubes containing 1 ml of inoculums of
bacterial strains with varying pH range from 7.0 to 9.0, temperature range from 300C to 350C and incubation
time range from 1-10 days (d) with initial concentration of 3 mM of Mn(II) ions were incubated in incubator.
Biological Mn(II) oxidation proceeds much more rapidly than abiotic Mn(II) oxidation under slightly
alkaline pH conditions. The pH value of solution was adjusted using 0.1 M HCl or 0.1 M NaOH solution.
For incubation time, bacterial growth (optical density OD) was monitored at regular time interval of 1, 5.5
and 10th day at 620 nm using UV-spectrophotometer. After the fixed interval of time, 1 ml culture sample
was withdrawn and centrifuged at 12000 r.p.m. and filtered to measure Mn (II) concentration using atomic
absorption spectrophotometer (GBC-932 plus). The amount of Mn(II) removed from the solution was
calculated as
Mn(II) removal %=[(Mn(II) initial -Mn(II) final)/Mn(II)initial]×100% ...(1)
To determine the amount of Mn(II) absorbed to the generated Mn oxides, metal precipitates were
washed with deionized water and subsequently mixed with 10 mL of 20 mM CuSO4 for 12 h at 300C on a
rotary shaker at 150 r.p.m (Tani et al., 2004), then centrifuged and filtered to measure Mn(II) concentration
using AAS. The residue was then washed with deionized water and treated with 10 mL of 20 mM
hydroxylamine hydrochloride (NH2OH.HCl) for 12 h at 300C on a rotary shaker at 150 r.p.m. to estimate
the amount of solid Mn oxides produced by strains.
TABLE 1. The experimental domain factors and levels for the Box–Behnken design
Code Name of Factors Factor Range and Levels (Coded)
−1 0 +1
A Temperature 30 32.5 35
B pH 7 8 9
C Contact Time 1 5.5 10
TABLE 2. Experimental Design with Actual Factors and Results of the Box–Behnken Model
Standard Run Factors Responses
A Temp B C- Incubation Mn Mn Absorbed Mn Oxide
0
C pH Time (Days) removal % % %
15 1 32.5 8 5.5 38.7 11.6 27.1
3 2 30 9 5.5 47.3 15.4 31.9
16 3 32.5 8 5.5 37.5 10.8 26.7
9 4 32.5 7 1 7.23 15.6 33.6
14 5 32.5 8 5.5 40.66 10.2 30.46
4 6 35 9 5.5 6.2 1.9 4.3
7 7 30 8 10 96.9 32 64.9
6 8 35 8 1 4.6 1.92 2.68
1 9 30 7 5.5 34.8 10.4 24.4
13 10 32.5 8 5.5 35.9 9.8 26.1
12 11 32.5 9 10 79 26 53
17 12 32.5 8 5.5 43.8 12.2 31.6
11 13 32.5 7 10 74.8 29 45.8
10 14 32.5 9 1 6.2 0.3 5.9
2 15 35 7 5.5 32.4 10.8 21.6
5 16 30 8 1 9.7 3.2 6.5
8 17 35 8 10 83.1 27.6 45.5
Establishment of Response Surfaces. The Box–Behnken design model was established on the basis of
Design Expert software (Stat Ease, 8.0.7.1 trial version) for the optimization of biosorption process. The
189
experimental design was applied after selection range of each variable (maximum and the minimum) as
shown in Table 1. The obtained response and run experiments were shown in Table 2.
Statistical Analysis. The quadratic equation model for predicting the optimal point was expressed according
to Eq. (2).
Yi = a0 +ΣaiXi +ΣaiiX ii 2 +ΣaijXiXj + e ... (2)
where Yi (i = 3) is the predicted response, i.e. Mn removal, biosorption of Mn (II) and biogenic manganese
oxide, a0 is the constant coefficient, ai is the ith linear coefficient, aii is the ith quadratic coefficient and aij is
the different interaction coefficients of the model; XiXj are the coded independent variables related to the
factors, and e is the error of model. However, in this study, the independent variables were coded as A, B
and C. Thus, the second-order polynomial equation can be presented as follow:
Y (% absorption; % Removal and % Mn oxide) = a0 + aiA + aiB + aiC + aiA2 + aiB2+aiC2 + aijA ∗ B +
aijA ∗ C + aijB ∗ C ...(3)
In this study, the removal of Mn (II), absorption of Mn (II) and Manganese oxide produced was
processed for Eq. (3) including ANOVA to obtain interaction between process variables and response. The
quality-of-fit of polynomial model was expressed by the coefficient of determination r2 and statistical
significance was checked by F-test in the programme. The residual error, pure error and lack-of-fit were
calculated from the repeated measurements (Myers and Montgomery, 2002).
Statistical analysis and validation and response surface models. The optimization study of Mn(II)
removal, manganese oxide formation and absorption of Mn (II) onto generated Mn oxide was carried out
with response surface methodology. Table 2 shows the results of BBD experiments for studying the effect
of three independent variables along with the predicted mean and observed responses. The regression
equation coefficients were calculated and data was fitted to a second-order polynomial equations. According
to the designed experimental data, the second-order polynomial equation was used to find out the
relationship between variables and response.
Mn Removal= +53.31+0.20*A+1.18* B+37.76*C-9.68*A*B-3.18*A*C+1.31*B*C +2.32*A2-5.45* B2-

6.05* C2 ... (4)
Mn Absorbed= +16.12+0.15*A+3.47*B+11.20*C-6.72*A* B-2.03*A*C+1.83* B*C+5.85*A2+0.90* B2-
4.55* C2 ... (5)
Mn Oxide = + 29.19-2.95*A-0.29*B+24.82* C-1.20*A*B- 1.40*A*C+1.73*B*C+3.09*A2-1.73*
B2+0.11* C2 ...(6)
The analysis of variance (ANOVA) was used in order to ensure a good model. The test for
significance of regression model and the results of ANOVA are presented in Table 3. Prob > F less than
0.05 indicated that model terms are significant for Mn(II) removal, adsorption of Mn (II) and manganese
oxide formation. Non-significant value of lack-of-fit is good for validation in quadratic model. The predicted
r2 and adjusted r2 values 0.9821 and 0.8892, 0.9098 and 0.7938, 0.9744 and 0.9414 for Mn(II) removal,
absorption of Mn (II) and manganese oxide formation by bacterial strain Mn 21, are in reasonable agreement
with the value of r2, which is closer to 1.0, indicates the better fitness of model in the present experimental
data (Khuri, 2006).
Optimization of Variables. The effect of interacting variables: temperature, pH, and incubation time on
Mn (II) removal, adsorption of Mn (II) and manganese oxide formation were analyzed on the basis of
quadratic polynomial Eqs. (4) – (6) of response surface methodology. First, temperature (P > 0.0001) had a
positive effect on removal, absorption of Mn (II) and Mn oxide formation [Eqs. (4) – (6)]. The increase in
removal, absorption of Mn (II) ions and Mn oxide formation with increase in temperature is due to either
the higher affinity of sites for metal or an increase in binding sites on the biomass. pH and incubation time
were also the most important factors (P > 0.0001) and had a positive effect on removal and absorption of
190
Mn (II) [Eqs. (4) and (5)] and linear negative effect on biogenic manganese oxide [(Eq. (6) ] from aqueous
solution by bacterial strain Mn 21.
TABLE 3. Analysis of variance for RSM variables fitted to quadratic model.

Bacterial strain Mn 21
Responses Source Sum of Squares df Mean Square F-Value P- Value Prob>F
Model 12145.64 9 1349.52 15.26 0.0008 Significant
Mn Removal
Residual 618.92 7 88.42
Lack of Fit 181.34 3 60.45 0.55 0.6732 not significant
Pure Error 437.58 4 109.39
Cor Total 12764.56 16
2
r 0.9821
adjusted r2 0.8892
Mn Absorbed Model 1534.71 9 170.52 7.84 0.0064 Significant
Residual 152.2 7 21.74
Pure Error 114.45 4 28.61
Cor Total 1686.91 16
2
r 0.9098
2
adjusted r 0.7938
Model 5072.83 9 563.65 29.54 < 0.0001 significant
Mn Oxide
Residual 133.54 7 19.08
Pure Error 23.62 4 5.9
Cor Total 5206.38 16
r2 0.9744
2
adjusted r 0.9414
A B C
FIGURE1. 3D-surface plot showing the interactive of pH and temperature (0C) on: (A) % removal of
Mn(II), (B) % absorption of Mn (II), and (C) % Mn Oxide formation by bacterial strain Mn 21.
The susceptibility of response to two interacting variables can be included by three-dimensional

graphs by holding other variable at central values. The interactive effect of two independent variables with
191
another variable being at fixed level on removal and absorption of Mn (II) ions and Mn oxide formation
with bacterial culture were shown in 3D surface plots.
A B C
FIGURE2. 3D-surface plot showing the interactive of temperature (0C) and Incubation time on: (A) %
removal of Mn(II), (B) % absorption of Mn (II), and (C) % Mn Oxide formation by bacterial strain Mn 21.
A B C
FIGURE3. 3D-surface plot showing the interactive of pH and Incubation time on: (A) % removal of Mn(II),
(B) % absorption of Mn (II), and (C) % Mn Oxide formation by bacterial strain Mn 21.
Myers and Montgomery (2002) described multiple response method called desirability. It reflected
the desirable ranges for each response (di). The simultaneous objective function is a geometric mean of all
transformed responses. Table 4 showed the desirability of optimised parameters for maximized goal.
TABLE4. Desirability of Optimised Parametrs

Number Temperature pH Incubation Mn Mn Mn Desirability
Time Removal Absorbed Oxide
1 31.7 8.0 9.7 108.9 32.3 71.1 1.0 Selected
2 30.5 8.5 9.2 107.8 42.4 68.2 1.0
3 30.1 9.0 9.8 116.2 82.7 94.7 1.0
4 31.7 8.2 9.6 107.4 34.4 73.3 1.0
5 32.0 7.9 9.9 112.1 32.2 72.6 1.0
CONCLUSIONS
On the basis of RSM using the Box–Behnken design, we found that values of “Prob > F” less than
0.05 indicate that model terms have significant effect on Mn removal and absorption of Mn (II) ions and
oxide formation by bacterial strain Mn 21. The predicted r2 and adjusted r2 values were obtained closer to
1.0 indicates the better fitness of model. The higher removal of Mn was achieved because of absorption of
Metal ions on biogenic manganese oxide formed by bacterial strain Mn 21, as they posses higher surface
area and higher binding energy per unit area. From the significant model and mathematical evaluation, RSM
approach proved to be a very useful and accurate methodology to optimize biosorption process and need to
apply at pilot scale for industrial wastewater treatment.
ACKNOWLEDGEMENTS
This work is supported by University Grant Commission, Basic Scientific Research, New Delhi.
REFERENCES
192
Francis, C. A., E. M. Co, and B. W. Tebo. 2001. Enzymatic manganese(II) oxidation by marine a-
proteobacterium. Appl Environ Microbiol 67: 4024–4029.
Ivarsson, M., C. Broman, and N.G. Holm. 2011. Chromite oxidation by manganese oxides in subseafloor
basalts and the presence of putative fossilized microorganisms. Geochem. Transac. 12:5
Khuri A. I. 2006. (Ed): “Response surface methodology and related topics”. Singapore: World Scientific.
Meng Y.T., Y. M. Zheng, L.M. Zhang, and J. Z. He. 2009. Biogenic Mn oxides for effective adsorption of
Cd from aquatic environment. Environ. Poll. 157: 2577–2583.
Moghaddam S.S., M.R. A. Moghaddam, and M. Arami. 2011. “Response surface optimization of acid red
119 dye from simulated wastewater using Al based waterworks sludge and polyaluminium chloride as
coagulant”. J Environ Manage. 92:1284–1291.
Myers, R.H., and D.C. Montgomery. 2002. “Response Surface Methodology Process and Product
Optimization Using Designed Experiments”, 2nd ed., John Wiley, New York.
Nealson, Y. M., L. W. Lion, M. L. Shuler, and W. C. Ghiorse. 2002. Effect of oxide formation mechanisms
on lead adsorption by biogenic manganese (hydr)oxides, iron (hydr)oxides, and their mixtures. Environ.
Sci. Technol. 36: 421–425.
Singh A., Manju, S. Rani, and N.R. Bishnoi. 2012. “Malachite green dye decolorization on immobilized
dead yeast cells employing sequential design of experiments”. Ecol. Engg. 47: 291– 296.
Tani, Y., M. Ohashi, N. Miyata, H. Seyama, K. Iwahori, and M. Soma. (2004). “Sorption of Co(II),
Ni(II), and Zn(II) on biogenic manganese oxides produced by a Mn-oxidizing fungus, strain KR21–
2”. J Environ Sci Health A Tox Hazard Subst Environ Engg. 39: 2641–2660.
Tebo, B. M., J. R. Bargar, B. G. Clement, G. J. Dick, K. J. Murray, D. Parker, R. Verity, and S. M. Webb.
2004. Biogenic manganese oxides: properties and mechanisms of formation. Annu. Rev. Earth
Planetary Sci. 32:287–328.
Watanabe J., Y. Tani, M. Naoyuki, S. Haruhiko, S. Mitsunobu, and H. Naitou. 2012. Concurrent sorption
of As(V) and Mn(II) during biogenic manganese oxide formation. Chem. Geol. 306–307: 123–128.
193
REDUCTION OF VINASSE SOYBEAN POLLUTION USING DIFFERENT STRAINS OF THE

GENUS Cupriavidus necator
Elizabeth dos Santos Costa Alexandre, Luiz Gustavo Lacerda, Marco Aurélio da Silva Carvalho Filho
(Universidade Positivo, Curitiba, PR, Brazil)
Soybean vinasse is an effluent generated from the process of alcohol recovering from molasses. It has a high
chemical oxygen demand (COD) and high toxicity hence It cannot be treated as a common waste effluent .
Due to the environmental problems and complications that wastewater can generate at the plant, there is a
challenge regarding this effluent treatment. Nowadays in Brazil, are obtained 10,000 L.day-1 of ethanol to
generate a daily volume of 220,000 L.day-1 of soybean vinasse, in the only producing ethanol plant from
soybean processing. The prevalence of this effluent in the environment represents a new central basis for
research and studies related to environmental management. This work was developed to evaluate the
reduction of the pollution load in soybean vinasse. Two treatments were tested (culture medium) using two
strains of the genus Cupriavidus, including NRRL B - 2804 and NRRL B - 4383 and a strain
of Pseudomonas oleovorans NRRL B -778 . The COD of soybean vinasse was 155.18 g.L-1. It was
conducted a preliminary study in soybean vinasse concentrations and evaluated the parameters such as
biomass production in dry matter content, temperature and cell growth of microorganisms suitable for use.
Treatments were applied and conducted in two culture media MC1 and MC2 using tests in 500 mL
Erlenmeyer flask with 150 mL capacity of culture medium for each finned treatment. The cultures were
prepared with soybean vinasse diluted to 30%, modified nutrient broth supplemented with hydrolyzed rice
husk, and MC1 was distinguished from the MC2 by subtracting the mineral medium (MM) of its
composition. At the end of the study, two strains were selected C. necator NRRL B – 2804, NRRL B – 4383
respectively and 36 experimental units were prepared. The results of COD decrease and biomass formation
in MC1 and MC2 were evaluated statistically by Tukey test and Levene using ANOVA for discrimination
means and verification of homogeneity among treatments. The maximum reduction of COD obtained for
MC1 and MC2 inoculated with the strain C. necator NRRL B- 2804 , respectively was 72% and 65 % of
removal for cultivation in orbital shaker at 180 rpm, 30°C within the initial COD before vinasse treatment.
The medium inoculated with strain MC2 C. necator NRRL B- 4383 was selected and fermented in a
bioreactor - fermenter BIO - TEC 7.5 L for 72 h with 66% of COD removal under the same conditions. The
presence of polyhydroxyalkanoates (PHAs) derived from biomass in the medium inoculated with the strain
MC2 C. necator NRRL B - 2804 was identified by the fusing temperature of 173°C confirmed in the
literature. The COD reduction obtained for the soybean vinasse using culture media containing industrial
waste, proved to be a promising treatment for new perspectives with a focus on environmental management,
to the conditions applied in this study could be improved by optimization of the bioprocess used.
194
THE APPLICATION OF NITRIFICATION-DENITRIFICATION PROCESS TO ENHANCE

TREATMENT EFFICIENCY IN LIVESTOCK WASTEWATER
B. S. Lee, S. S. Ton
(Department of Environmental Engineering and Science, Feng Chia University, Taichung, Taiwan)
ABSTRACT: Owing to the pattern of livestock farming in Taiwan is concentrate feeding. High amount of
organic and nitrogen content are therefore concentrated in the discharge wastewater. After releasing, it will
consume dissolved oxygen of the natural water and cause toxicity effect to the aquatic organisms directly.
Eventually it will downgrade the environmental quality. Currently the traditional three-stage treatment
process only transfer nitrogen pollutants into nitrite and nitrate, but can’t remove them completely from the
livestock wastewater. Hence, the objective of this study is to enhance the treatment efficiency of nitrogen
pollution by integrating nitrification and denitrification processes altogether. In our study, partial aeration
process and an anaerobic soil adsorption system are applied to fulfill this purpose.
As a result both the organic contents and nitrogen contents are decreased. The concentration of BOD
and COD is decreasing from 132.4 to 53.5 mg/L and 257.2 to 136.8 mg/L, respectively. The concentration
of ammonia nitrogen, TKN and TN is decreasing from 539.9 to 105.7 mg/L, 617.9 to 117.5 mg/L and 618.0
to 142.4 mg/L, respectively. The removal efficiency of ammonia nitrogen, TKN and TN are 80.4%, 81.0%
and 77%, respectively. Compare to the results of traditional three-stage treatment, the removal efficiency of
nitrogen contents is as much as twice the amount.
Furthermore, the effluent of our system is fulfilled the criteria of regulatory effluent standards. The
nitrification-denitrification systems in this study not only reduce the environmental loading of swine manure
wastewater discharge but also provide an alternative for water resource reusing.
Keyword: livestock wastewater, nitrification, denitrification, effluent standards, traditional three-
stage treatment
INTRODUCTION
Due to gradual increasing of meat consumption in the daily life, leading to livestock flourish. With
the increased in the number of breeding, the water pollution in our environment has become increasingly
serious. Livestock wastewater contained high concentrations of organic matter, suspended solids and
nitrogen contaminants (Lee and Shoda, 2008). Without proper treatment and discharged directly into natural
water bodies will consume a lot of dissolved oxygen and causing eutrophication.
In Taiwan, livestock wastewater treatment process is divided into three stages, namely solid-liquid
separation, anaerobic fermentation and aerobic treatment processes. With the above-mention steps, the
organic matters can be removed effectively and the ammonia can be oxidized to nitrite and nitrate effectively
in livestock wastewater. However, without follow up anaerobic reaction, further reduction of nitrogen
pollutants can’t be reached. Therefor high total nitrogen concentrations still remain in its discharge water.
In conventional pollution control technology, the use of aerobic and anaerobic bacteria to promote
nitrification and denitrification reaction in order to achieve nitrogen pollutants removal has been studied for
several decades, and its technology has become mature. Since nitrification is a kind of biochemical reaction,
easily affected by environmental factors such as temperature, dissolved oxygen, pH, and so on.
Denitrification is just the opposite reaction of nitrification. Under anaerobic conditions, nitrite and nitrate
serve as electron acceptor and are reduced to nitrogen gas by denitrifying bacteria.
Carbon source is also a key factor affecting whether the denitrification can be carried out completely.
Organic carbon in wastewater served as the electron donors, although carbon deficiency can lead to poor
denitrification efficiency, excessive carbon also causing methane bacteria become the dominant species,
thus making methane fermentation as the major reaction.
In the past two decades, by controlling the amount of dissolved oxygen and use of other microbial
species, many emerging pollution control technologies have been proposed, such as single reactor high
activity ammonia removal over nitrite, SHARON; anaerobic ammonia oxidation, ANAMMOX; SHARON-
ANAMMOX; completely autotrophic nitrogen removal over nitrite, CANON and oxygen limited
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autotrophic nitrification-denitrification, OLAND.

Although emerging technologies can be effectively completed the purpose of nitrogen pollutants
removal, CANON and OLAND are less applicable to wastewater containing organic substances. While
using single tank as reactor, make these methods difficult to control various operation conditions. It also has
the limitation in handling of ammonia concentration. Anaerobic ammonia oxidation bacteria are not easy to
domestication, and the proliferative rate is also slow, limiting the applicability of the ANAMMOX.
Research indicates that the use of constructed wetlands for the treatment of organic matter and nitrogen
pollutants in livestock and domestic sewage wastewater is feasible (Morgan, 2008). Although wetland can
effectively oxidation of organic matter and ammonia nitrogen, the death of aquatic plants released pollutants
back again. Clogging in subsurface flow system, results in the loss of its decontamination capabilities. Soil
absorption system can make up for this shortcoming. Saturated with moisture in the soil, it provides an
anaerobic environment which is enough to produce the occurrence of denitrification. Related studies show
the soil absorption system can be up to 90% for total nitrogen removal efficiency (Andreadakis, 1987; Lei
et al., 2013).
By utilizing the nitrification and denitrification in the experiment not only removed the nitrogen
pollutants in the wastewater but also substituted the final settling tank of traditional wastewater treatment
unit, and enhancing the efficiency of the wastewater treatment.
MATERIALS AND METHOD

Figure 1 is the design of the treatment system. There are five operation units in the system, including
raw water tank, first oxidation tank, second oxidation tank, mixing tank, and soil treatment unit. The volume
of the raw water tank is 80L and the volume of the first oxidation tank, second oxidation tank, and mixing
tank are all 8L. The soil treatment unit was separated into four parts, namely the bottom buffer zone, lower
sand filter, gravel packed column, top sand filter. The total volume of soil treatment unit is 4.71 L.
FIGURE 1. The design of the wastewater treatment system
The wastewater of the experiment was sampling from the pig farm in Qingshui District of the
Taichung city. Wastewater was taken at the effluent of the anaerobic digestion tank from the livestock farms.
The wastewater was stored in the raw water tank and a peristaltic pump was used to drive them into the first
oxidation tank. The movement of water from oxidation tanks to mixing tank was carried out by overflow.
The second peristaltic pump was used to inject the water into the soil treatment unit. Aeration was applied
to the first and second oxidation tank to increase the dissolved oxygen. The surviving dissolved oxygen was
continuously consumed in the mixing tank to protect the anaerobic condition of the soil treatment unit.
The wastewater was supplied twice a day with a volume of 4L, totally 8 L/d. Total HRT was 3.5
days. The aeration rate was 1.0L/min and 0.5L/min, and 24 hours continuously. Temperature, Conductivity,
Dissolved Oxygen (DO) and Oxidation-Reduction Potential (ORP) were monitored in the experiment.
196
Biological Oxygen Demand (BOD), Chemical Oxygen Demand (COD), Nitrite-Nitrogen (NO2--N), Nitrate-
Nitrogen (NO3--N), Ammonia-Nitrogen (NH3-N), Total Kjeldahl Nitrogen (TKN) and total nitrogen (TN)
were analyzed or calculated to evaluate the removal efficiency of the system.
RESULTS AND DISCUSION
Results of Monitoring. The temperature were maintained at 24℃. The DO concentration of first and
second oxidation tank were stable at 2-4 mg/L by aerating. The ammine was combined with hydrogen ions
as the organic nitrogen was decomposed, and the pH value would be increasing to 8.49 in the first oxidation
tank, and the pH value decreased to 8.04 in the mixing tank, and the reaction received the H+ and increased
the pH value from 8.04 to 8.10 during the de-nitrification in the soil treating unit.
The ORP were different from the nitrification and de-nitrification, during the nitrification and de-
nitrification, the DO concentration and the concentration of the nitrogen pollutants were varied, and it would
be changed the ORP and conductivity. In the experiment, ORP increased to 3-5 mV in the aerobic condition
and decreased to -146.8 mV in the soil treating unit with anaerobic environment. It was helpful to enhance
efficiency of nitrification with aerobic environment in the first and second oxidation tank to transform
ammonia nitrogen to nitrite and nitrate, and transformed nitrite and nitrate to nitrogen in the soil treating
unit with anaerobic condition, and the results indicated that the conductivity decreased from 4782 to 2643
µS/cm.
Results of Analyzing. After treatment, the BOD and COD were decreasing from 132.4 and 270.3 mg/L to
53.5 and 149.9 mg/L, the efficiency were 60% and 45%, respectively. The concentration of ammonia
nitrogen and total Kjeldahl nitrogen were decreasing from 553.0 and 639.4 mg/L to 140.1and 156.2 mg/L,
the efficiency were 74.7% and 75.6%, respectively. The concentration of total nitrogen was decreasing from
639.5 mg/L to 178.5 mg/L, the efficiency was up to 72.1%. The concentration of SS was reducing from 45.3
mg/L to 4 mg/L and the removal efficiency was up to 91.1%.
The Effect of Dissolved Oxygen to Nitrification and De- Nitrification. The system was using nitrification
and denitrification to reduce the concentration of nitrogen pollutants. From the raw water tank to the second
oxidation tank were nitrification process with aerobic condition; from second oxidation tank to the soil
treatment unit were denitrification process with anaerobic condition.
FIGURE 2. The concentration changing and tendency of ammonia nitrogen, nitrite, and nitrate during
nitrification
Nitrification consuming oxygen, therefore increased the dissolved oxygen could improve the
efficiency. Figure 2 showed that the concentration changing and tendency of ammonia nitrogen, nitrite, and
197
nitrate during the nitrification. The concentration of ammonia nitrogen was decreasing from 553.0 mg/L to
209.7 mg/L as increased the concentration of dissolved oxygen to 3.66 and 2.93 mg/L in first and second
oxidation tank, respectively. The concentration of nitrite and nitrate were increasing to 32.93 and 34.85
mg/L respectively.
FIGURE 3. The concentration changing and tendency of ammonia nitrogen, nitrite, and nitrate during de-
nitrification
Denitrification was anaerobic reaction, and it could transform nitrite and nitrate to nitrogen.
Therefore the concentration of ammonia nitrogen would not be got the apparent changing. Figure 3 was the
concentration changing and tendency of ammonia nitrogen, nitrite, and nitrate during denitrification. After
denitrification, the concentration of nitrite and nitrate were reducing from 32.93 and 34.85 mg/L to 3.23 and
19.01 mg/L, the removal efficiency of ammonia nitrogen and total nitrogen were up to 74.7% and 72.1%.
According to the results, the system had significant function for removing nitrogen pollutants of the
livestock wastewater.
CONCLUTIONS
1. Providing enough dissolved oxygen to transform ammonia nitrogen to nitrite and nitrate in the
oxidation tank is very helpful to promote the efficiency of the denitrification.
2. After treatment, the removal efficiency of ammonia nitrogen and total nitrogen were up to 72-75%.
3. Although the removal efficiency of ammonia nitrogen and total Kjeldahl nitrogen were similar to
traditional wastewater treatment, the removal efficiency of the total nitrogen was as much as twice the
amount.
4. The innovated treatment system not only reduced the environmental loading of swine manure
wastewater discharge but also provide an alternative for water resource reusing.
REFERENCES
Amit, S and Rupali, G., 2004, Developments in wastewater treatment methods, Desalination, 167, 55-63.
Andreadakis, A. D., 1987, Organic matter and nitrogen removal by an on site sewage treatment and
disposal system Water Res. 21, 559-565.
Boonsong, K., Piyatiratitvorakul, S. and Patanaponpaiboon, P., 2003, Potential use of mangrove plantation
as constructed wetland for municipal wastewater treatment. Water. Sci. and Technol., 48(5), 257-266.
Lee, H. M. Shoda, 2008, Removal of COD and color from livestock wastewater by the Fenton method.
Hazardous Materials 153(3), 1314-1319.
Lei, Z. F., Wu, T., Zhang, Y. Liu, X., Wan, C. L., Lee, D. J., Tay, J. H., 2013, Two-stage soil infiltration
198
treatment system for treating ammonium wastewaters of low COD/TN ratios, Bioresource Technology,
128, 774-778.
Morgan, J. A., Martin, J. F., 2008, Performance of an ecological treatment system at three strengths of dairy
wastewater loading, Ecological Engineering, 33, 195-209.
Zedler, J. B. and Kercher, S., 2005, Wetland Resources: Status, Trends, Ecosystem Services, and
Restorability, Annual Review of Environment and Resources, 30, 39-74.
199
REFINERY WASTEWATER TREATMENT: A CHALLENGE TOWARDS ZERO LIQUID

DISCHARGE
Farid Benyahia
(Qatar University, Doha, Qatar)
Crude oil and condensate refineries generate a large amount of wastewater that has both process and non-
process origins. Depending on the type of crude oil, composition of condensate and treatment processes, the
characteristics of refinery wastewater vary according to a complex pattern. The design and operation of
modern refinery wastewater treatment plants are challenging and are essentially technology driven. In this
investigation, the sources of wastewater pollutants have been traced to specific sources and operations, and
suitable treatment technologies identified. Modern powerful tools such image analysis have been employed
to characterize oil droplet sizes in oily wastewater and immobilized cell technology considered in biological
reactor design for wide spectrum chemical pollutant degradation.
The existing wastewater treatment facility in the Arabian Gulf at a GCC refinery consists of
separating immiscible hydrocarbons and settleable material from water that is ultimately diluted with sea
water and discharged into the marine environment.
Wastewater characterization has shown the presence of polyaromatic compounds, phenols and cobalt in the
treated stream that is currently diluted by sea water and discharged into the sea. The dilution does not
degrade or eliminate these, thus making a strong case for the design and implementation of further treatment
processes that should include biological reactors.
A biomass extraction method was developed to harvest Pseudomonas P. and Baccili S. cells from a
commercial biological product and acclimate them to a source of carbon rich in phenol, prior to
immobilizing them in a suitable gel. This acclimated biomass has been successfully employed to biodegrade
most of the highly toxic and recalcitrant pollutants found in refinery wastewater.
The current volume of discharged water into the sea, excluding the new load from the new units,
amounts to approximately 1.5 million cubic meters per annum. This substantial amount can be usefully
reused or recycled for various applications. In order to achieve this goal, the existing treatment process must
undergo significant upgrades and must include advanced biological treatment unit and physical adsorption
units.
200
EXAMINING PROCESS WASTEWATER TREATMENT AND GREY WATER FOOTPRINT OF

BIOFUEL PRODUCED VIA FAST PYROLYSIS AND HYDROTREATING
May Wu
(Argonne National Laboratory, Lemont Illinois, United States)
Choices of biorefinery wastewater treatment can affect biofuel sustainability. This study examines the
feasibility of treating wastewater generated from a model fast pyrolysis and hydrotreating biorefinery in a
municipal wastewater treatment facility. Biorefinery capacities from 38 to 341 million liters per year (MLY)
and wastewater streams of varying concentrations of ammonia nitrogen (NH3-N), biological oxygen demand
(BOD), and total suspended solids (TSS) were examined. Results indicate the wastewater from 38 MLY
biorefinery with a BOD concentration of 500 mg/L or less and a NH3-N concentration of 50 mg/L or less
can be effectively treated at a removal efficiency of 85%. At 95 MLY biorefinery, the wastewater stream
feasible for the treatment reduced to 300 mg/L BOD and 30 mg/L NH3-N. The treatment cost varied from
$12,000 to $30,000 annually. Grey water footprint was established for the wastewater by introducing a
concept of maximum allowable grey water footprint and net grey water footprint to encompass regulated
discharge limits from point sources. Net grey water footprint was up to 1 L NO3-N / L biofuel produced;
0.04 L/L for BOD; and nil for ammonia and TSS. Findings from this study contribute to a deep
understanding of key considerations in biorefinery development.
201
ISOLATION OF A Lysinibacillus STRAIN B1-CDA SHOWING POTENTIALS FOR

BIOREMEDIATION OF ARSENIC CONTAMINATED WATER
Aminur Rahman*, Noor Nahar, and Abul Mandal (University of Skövde, Skövde, Sweden)
Jana Jass (Örebro University, Örebro, Sweden)
Toxic chemicals discharged into nature as wastes by industries and due to agriculture and mining activities,
severely contaminate the environment and lead to the development of various lethal diseases in both humans
and animals such as cancers, neurological and vascular disorders, and system-wide organ damage and
failure. For example, only in Bangladesh and India approximately 300 million people are exposed to arsenic
contamination on a daily basis through drinking water and/or by consumption of foods. The main objective
of this study was to identify and isolate arsenic resistant bacteria that can be used for removing arsenic from
the contaminated environment. Here we report a soil borne bacterium, B1-CDA that can serve this purpose.
B1-CDA was isolated from the soil of a cultivated land in Chuadanga district located in the south-west
region of Bangladesh. The morphological, biochemical and 16S rRNA analysis suggested that the isolate
belongs to Lysinibacillus sphaericus. The minimum inhibitory concentration (MIC) value of the isolate is
500 mM (As) as arsenate. TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) and ICP-MS
(Inductively Coupled Plasma-Mass Spectrometry) analysis confirmed intracellular accumulation and
removal of arsenics. Arsenic accumulation in cells amounted to 5.0 mg/g of the cells dry biomass and thus
reduced the arsenic concentration in the contaminated liquid medium by as much as 50%. These results
indicate that B1-CDA has the potential for remediation of arsenic from the contaminated water. We believe
the benefits of implementing this bacterium to efficiently reduce arsenic exposure will not only help to
remove one aspect of human arsenic poisoning but will also benefit livestock and native animal species.
Therefore, the outcome of this research will be highly significant for people in the affected area and also for
human populations in other countries that have credible health concerns as a consequence of arsenic-
contaminated water.
202
EFFECTS OF ZINC ON GERMINATION, SEEDLING GROWTH AND NUTRIENT CONTAIN

OF RAUVOLFIA SERPENTINE.
Patel Kailash P, Vyas Milvee K, Patel Parimal M, Patel Kalpesh M

(Department Of Biosciences, V.N.S.G. University, Surat-395007 India)
ABSTRACT: The global heavy metal pollution is increasing in the environment due to increase in the
number of industries. The industrial waste water contains heavy metals like, cadmium, lead, zinc, cobalt
and chromium. Present work is an attempt to investigate the effects of heavy metal zinc on the germination
and growth of Rauvolfia serpentine Benth. ex. Kurz. – a medicinal plant used in the treatment of high and
low blood pressures, snake bites, psoriasis, etc. The seeds of this plant were grown in different concentration
of zinc sulfate in order to assess the effect of zinc on seed germination growth and nutritional (Total sugars
and Protein) changes. The results indicated that the lower concentration showed increase in germination,
seedling growth and nutritional contain. The higher level has reducing effects on these parameters and
decreased the growth.
Key Words: Heavy metal, Zinc, Total sugar and protein, Rauwolfia serpentine
INTRODUCTION
The polluted water discharged by many industries contains heavy metals like ferrous, nickel, zinc,
cadmium, copper, etc. Zinc plays an important role in activation of enzymes, protein synthesis, and
metabolism of lipid, carbohydrate and nucleic acids (Marshner, 1986 ; Pahlsson, 1989). However, when
zinc is present in excess amount in plant organs, it causes. Significant change in growth processes and
mineral nutrition (De Vos et al., 1991, Chaoui et al., 1997). The aim of present study has been to explain
the effect of various zinc concentrations on germination, growth rate, biomass and nutrient contents in
Rauvolfia serpentine a medicinal plant.
MATERIAL AND METTIODS

The seeds of Rauvolfia serpentine were collected from the plant naturally growing in the Vyara
Forest of South Gujarat, India. The Seeds were germinated in various zinc sulphate solutions with 10, 25,
50, 100, 150 mgl-¹ concentrations in separate Petri dishes. The seed germinated in distilled water was
control.
The percentage of germination, growth, fresh weight and dry weight of root and shoot, and changes
in protein and total sugar contents were investigated after ten days. The results were the mean readings of
five replicates. The estimation of protein was carried out by the method of Lowry et al., (1951) and of total
sugar by following the method Nelson (1944).
RESULTS
The percentage of seed germination was higher than control at lower can concentration of zinc
(Table 1). The growth of seedling was higher than control when the plants were treated with lower
concentration of zinc as, there was more increase in the length of root and shoot at lower concentration (10
and 25 mgl-¹).
The higher concentration of zinc has reduced the germination percentage and has adverse effect on
the growth of seedling as the length of root and shoot was lower than control (Table 1).Similarly the fresh
weight and any Wight of root and shoot was increased of lower concentration but has reducing effect when
concentration was increased in the treatment (Table 2).
The treatment of lower concentration of zinc increased the total sugar content which was gradually
decreased by an increase in the concentration of zinc (Table 2).
Protein content was increased when the plants were treated with 10 and 25 mgl-¹ zinc but increase
in concentration has reduced the content (Table 2).
203
Table 1. Effect of zinc on germination, growth of root, shoot and fresh and dry weight
Zinc Germination Root Shoot Root Shoot Root Shoot
concentration (Percentage) length length Fresh Fresh day day
(mgl-¹) (Cm) (cm) Weight Weight weight weight
(gm) (gm) (gm) (gm)
Control 95 4.9 13.8 0.82 2.21 0.15 0.38
10 98 5.8 15.9 1.09 2.91 0.18 0.44
25 96 5.2 14.0 0.91 2.42 0.16 0.40
50 87 4.3 12.9 0.76 1.90 0.11 0.34
100 72 3.8 11.5 0.68 1.85 0.09 0.29
150 65 2.6 9.8 0.54 1.63 0.06 0.20
Table 2. Effect of zinc on nutrient content.

Zinc Concentration (mgl-¹) Total Sugar (mgg -¹) Protein (mgg -¹)
Control 3.22 12.32
10 3.85 15.45
25 3.46 13.14
50 2.90 10.38
100 2.52 8.66
150 2.10 7.23
DISCUSSION
Heavy metal plays important rote in governing germination and growth of plants. Their effects on
plants are dependent on the amount of heavy metals taken up from the given environment. Germination and
seedling growth are valuable stages in the life of plants (Vange et al., 2004.) Present study showed that zinc
at lower concentration had a beneficial effect on germination and growth as explained by Reichman (2002).
Zinc at higher concentration has adverse effect on seed germination. Similar decrease in seed
germination was also observed in cluster been due to zinc treatment by Mahalakshmi and Vijayarengan
(2003) and Mahmood et al., (2005). This was probably due to alteration of selection permeability properties
of cell membrane. The reduction in the growth of root and shoot might be due to the effect of zinc on
hydrolytic enzyme activities resulting into less availability of nutritional materials for radical and pumnle
affecting the length of seedlings (Shafia, 2008).
Zinc increased total sugar content at lower level but total sugar content showed a decreasing trend
with progressive increase in zinc concentration in treatment similar to wheat leaves (Lanaras et al., 1993).
According to Robie et al., (1992) such decrease might be due to role of zinc on the enzymatic reactions
related to the carbohydrate catabolism.
Protein content was higher at lower level of zinc further the pragsortion was decreased with an
increase in zinc concentration in the treatment. The observed decline in protein content is an agreement with
findings of Zengin and Kirbag (2007). The decrease in protein content by excess zinc may be due to binding
of metals with the sulfhydryl group of protein and causing adverse effect in the normal protein form.
REFERENCES
[1] Chaoui, A., Mazhoudi, S., Ghorbal, M. H., Elferjani, F., 1997. Cadium and zinc induction of lipid
peroxidation and effect on antioxidant enzyme activities in bean (Phaseolus vlgaris L.). Plant Sci. 127
: 139 - 147.
[2] De Vos, C. H. R., Schat, H., De Waal, M. A. M., Voorja, R., Ernst, W. H. O. 1991. Increased resistance
to copper - induced damage of root cell plasma lemma in copper tolerant Silene cucubalus. Physiol.
Plant. 82 : 523 - 528.
204
[3] Lanaras, T., Moustakas, M., Symeonidis, L., Diamantoglou, S. and Kerataglis, S. 1993. Plant metal
content, growth responses and some photosynthetic measurements on field - cultivated wheat growing
on ore bodies enriched in. Cu. Physiol. Plant. 88 : 307 - 314.
[4] Lowry, O. H., Rosebrough, N. J., Farr, A. L. and Randall, R. J. 1951. Protein measurement with Folin
phenol reagent. J. Biol. Chem. 193 : 265 - 275.
[5] Mahalakshmi, G. and Vijayarengan, P. 2003. Ettects of zinc on germinating seeds of three plants species.
Nature Environ. Pollut. Tech. 2 : 117 -119.
[6] Mahamood, S., Hussain, A., Saeed, Z. and Athar, M. 2005. Germination and seedling growth of corn
(Zea mays L.) under verying levels of copper and zinc. Int. J. Environ. Sci. Tech. 2 : 269 - 274.
[7] Marschner, H. 1986. Mineral nutrion of higher plants. Academic press, New York.
[8] Nelson, N. 1944. A photometric adaption of the Somogyi method for the determination of glucose. J.
Biol. Chem. 153 : 375 - 380.
[9] Pahlsson, A. M. B. 1989. Toxicity of heavy metals (Zn, Cu, Cd, Pb) to vascular plants. Water Air Soil
Pollut. 47 : 287 - 319.
[10] Reichman, S. M. 2002. The response of plant to metal toxicity : A review of focusing on copper,
manganese and zinc. Austr. Minerals Energy Environ. Found. Melbourne, Australia : 7.
[11] Robie, M. H., Eleiwa, M. E., Aboseoud, M. A. and Khalil, K. M. 1992. Effect of nickle on the content
of carbohydrate and some mineral in corn and broad bean plant. J. K. A. U. Sci. 4 : 37.
[12] Shafia, M., Zafar, I. M. and Athar, M. 2008. Effect of lead and cadmium on germinations and seedling
growth of Leucaena leucocephala. J. Appl. Sci. Environ. Manage. 12 : 61 - 66.
[13] Vange, V., Hevchand, I., Vandvik, V. 2004. Does seed mass and family affect germination and juvenile
performance in Knautia arvensis L. A study using failure time methods. Acta Oecol. 25 : 169 - 178.
[14] Zengin, F. K. and Kirbag, S. 2007. Effect of copper on chlorophyll, proline, protein and ascorbic acid
level of sunflower (Helianthus annus L.) seedlings. J. Environ. Biol. 28 : 561 - 566.
205
SYNTHESIS AND CHARACTERIZATION OF CU(II) IMPRINTED NANOPARTICLES BASED

ON POLYETHYLENEIMINE FOR SELECTIVE RECOGNITION OF COPPER
Jin Jia and Shengji Luan (Peking University Shenzhen Graduate School, Shenzhen, Guangdong, China);
Aihua Wu* (PKU-HKUST Shenzhen-HongKong Institution, Shenzhen, Guangdong, China)
The selective adsorption and recovery of metal ions were important issues for both water treatment and
sample preparation for quantification. Cu(II) imprinted nanoparticles were synthesized by imprinting
technique to achieve selectivity for Cu(II). Chemical crosslinking based on polyethyleneimine (PEI) and
amino epichlorohydrin was introduced after imprinting process and under vigorous stirring for 3 hours. A
systematically synthesis conditions including dosage of PEI and imprinted copper (II) ions were
investigated. The morphologies of imprinted nanoparticles were spherical in shape with uniform size
distribution illustrated by field emission scanning electron microscope. The result indicated
morphologies, adsorption capacity and selectivity were influenced by dosage ratio. The selectivity
coefficients of the nanoparticles for Cu(II)/Cr(III) and Cu(II)/Zn(II) are 5.21 and 21.00, respectively. In
addition, no obvious decrease was observed after up to five adsorption cycles, indicating that the Cu(II)
imprinted nanoparticles were of high stability and could be used as effective and selective adsorbents in
treatment of water and metallurgical industry.
206
ADSORPTION OF Pb(II) ON NANOSCALE IRON-OXIDE DOPED GRANULAR ACTIVATED

CARBON
Zhihua Xu, Daofang Zhang* and Weifang Chen

(University of Shanghai for Science and Technology, Shanghai, China, 200093)
ABSTRACT: A nanoscale iron-oxide doped granular activated carbon (Fe-GAC) was synthesized through
a simple precipitation protocol and tested for adsorption of Pb(II) in water. Adsorption isotherms and
kinetics studies indicated that iron-oxide doping obviously increased the adsorption of Pb(II) by GAC
though the iron-oxide doping slowed down the adsorption rates to some extent. In addition, the isotherm
data fitted well with Langmuir model which indicated that Pb(II) removal was mostly single layer adsorption
while kinetics results revealed that the adsorption followed pseudo-second-order model. Batch experiments
were also carried out to investigate the effects of iron content and solution pH on Pb(II) removal. The results
indicated that iron content and solution pH both had significant impacts on the adsorption. The highest Pb(II)
adsorption capacity was achieved by GAC doped with 17% of iron. In comparison, GAC with higher or
lower iron content decreased the Pb(II) adsorption. Adsorption of Pb(II) was less favorable at low pH than
neutral pH range. Thermodynamic analysis further showed that Pb(II) adsorption was spontaneous and
exothermic under the experiment conditions. The results obtained demonstrate that Fe-GAC is a promising
and effective material for Pb(II) pollution control in water.
INTRODUCTION
As one of the common treatment methods for heavy metals, adsorption process has the
characteristics of high efficiency, low operation and maintenance cost and many selective cost-effect
adsorbents (Lee et al., 2012). Although granular activated carbon (GAC) with high specific surface area,
abundant pore structure, massive functional groups and excellent mechanical strength is usually used as
superior adsorbent for organic substance removal, it has only a small quantity of adsorptive capacity for
heavy metals in aqueous phase (Erto et al., 2013; Sotelo et al., 2014). Nanoscale iron oxides have been
widely used as adsorptive materials for removing heavy metals pollutants due to their strong affinity for
heavy metals (Ahmed et al., 2013). However, as the size of iron oxides reached nanoscale level, their high
surface energy easily leads to unstable status which is prone to agglomeration due to the Van der Waals
force or other interactions (Pradeep et al., 2009), and the high adsorptive capacity of nanoscale iron oxides
might reduce or even lose. Moreover, they are very difficult to be employed in fixed beds or some other
flow systems as to their poor stability, excessive pressure drops and weak mechanical strength. In this
research, GAC was employed as the supporter which was doped by nanoscale iron oxides. The hybrid
composition is a potential orient for removing heavy metals by taking full advantages of both of their merits.
The aim of this study was to prepare a new nanoscale iron-oxides doped GAC for removing Pb(II).
Adsorption isotherm, kinetics and thermodynamic experiments were conducted. The effects of iron content
and pH on Pb(II) adsorption were also examined in details.
Preparation. Nanoscale iron-oxide doped granular activated carbon (Fe-GAC) was synthesized by a simple
precipitation process. Firstly, 5 g GAC was added to 0.5 L of 1 mol/L NaOH solution. Secondly, a certain
quantity (6.25-25 g) of Fe2(SO4)3 was added to the solution then put on a shaker at 298 K for several hours.
Thirdly, the mixture was heated at 313 K for 48 h. Lastly, Fe-GAC was separated by filtration and washed
thoroughly. The solid particles were desiccated at 378 K for 24 h and sealed prior to use. For example, the
GAC loaded with 5% mass content of iron and the GAC without iron were named as Fe@5-GAC and GAC,
respectively.
207
Characterization. The samples were observed with transmission electron microscopy (TEM, Hitachi
Model H-800, Japan). The BET surface area and pore volume were analyzed by N2 Adsorption-Desorption
tests (Micromeritics ASAP-2020, USA). pHpzc of all samples were measured by titration method proposed
by Noh and Schwarz (Noh et al., 1990).
Batch experiments. Adsorption isotherm tests at different pHs (3-6) were conducted by adding 0.1 g of
adsorbent to100 mL of solution with different Pb(II) initial concentrations (0.1-160 mg/L) at 298 K for 24
h. The pH was adjusted by 0.1 mol/L of NaOH or HCl solution. Adsorption kinetics tests were carried out
by adding 0.01 g of adsorbent to each of 16 Erlenmeyer flasks containing 100 mL of 1 mg/L Pb(II) solution
at 298 K, pH 6.0. Samples at different adsorption time were taken periodically from 0 to 24 h. Adsorption
thermodynamics tests were conducted by adding 0.1 g of adsorbent to100 mL of solution with different
Pb(II) initial concentrations (5-150 mg/L) for 24 h at 288K, 298K and 308K, respectively.
Chemical analysis. Heavy metals concentrations were analyzed by an Atomic Absorption

Spectrophotometer (AAS, TAS-990, PERSEE). To determine the iron-loaded content, Fe-GAC was
calcined in muffle furnace at 773 K for 3 h and the resultant ash was dissolved in 20 ml 2 mol/L HCl for 24
h.
Adsorption isotherm and effect of iron content. The loading of iron had positive effect on Pb(II)
adsorptive capacity to some extent. The experiment data fitted well with Langmuir isotherm model which
indicated that the Pb(II) removal was more likely to be single layer adsorption. The Langmuir constants
(qmax, KL and R2) of GAC and Fe-GACs are listed in Table 1. Fe@17-GAC loaded with 17% iron content
showed the qmax of 29.94 mg/g. Higher or lower iron content actually caused some decrease in adsorptive
capacity. Fe@10-GAC and Fe@27-GAC, loaded with 10% and 27% iron content, had the qmax of 26.39 and
27.10 mg/g, respectively. This phenomenon might be due to the reason that: (1) insufficient nanoscale iron-
oxides did not absolutely occupy the surface and the pores of GAC, there was still efficient active sites for
loading iron oxide to enhance the adsorptive capacity; (2) excessive nano-scale iron oxides on the surface
and in the pores of GAC led to aggregation of nano particles, which caused smaller adsorptive capacity. It
can be concluded that the optimum iron content was about 17%, which manifested the highest adsorptive
capacity. Table 1 also lists the BET surface area and total pore volume of GAC and Fe-GACs. With the
increase of iron content, the pores of GAC were gradually covered by nanoscale iron oxides. The
significantly decrease in surface area and pore volume was due to the loading of nanoscale iron oxides. Fig.
1 is the TEM images of GAC and Fe@17-GAC. Compared with GAC, dash area of Fe@17-GAC further
showed that nanoscale iron oxides were successfully doped in the pores of GAC.
Adsorption isotherms and effect of pH. Since Fe@17-GAC showed the highest adsorptive capacity for
Pb(II). Only GAC and Fe@17-GAC were tested for the following experiments. Fig. 2 and 3 show the
adsorption isotherms at different pHs with GAC and Fe@17-GAC, respectively. Table 2 lists the langmuir
isotherm constants at different pHs from 3 to 6. With the incresse of pH, adsorptive capacity increased for
both GAC and Fe@17-GAC accordingly, which indicated that adsorption process was favorable at high pH
range. pHpzc is defined as the pH where the surface net charge of adsorbent is zero. When solution pH was
lower than pHpzc, the surface was positive charge and interacted with negative species, on the contrary, when
solutions pH was higher than pHpzc, the surface was positive charge and interacted with positive species
(Chen et al., 2012). In this study, GAC had a pHpzc of 7.55, at pH<pHpzc, the net surface charge was negative
and formed repulsion force between GAC surface and Pb(II) which existed as Pb2+ and Pb(OH)+ (Lee et al.,
2012). With increase of pH from 3 to 6, the repulsion force decreased gradually, which resulted in obviously
increasing adsorption of Pb(II). Fe@17-GAC had a pHpzc of 9.11 due to the loaded nanoscale iron oxides.
Similarly, with increase of pH from 3 to 6, the repulsion force decreased gradually, which resulted in the
significantly increased adsorption of Pb(II). The adsorptive capacity of Fe@17-GAC was higher than that
of GAC, which proved that nanoscale iron oxides has good affinity to Pb(II) adsorption. Moreover,
electrostatic attraction was not the only force for Pb(II) adsorption, ion exchange and surface complexation
208
also contributed to the adsorption process (Lee et al., 2012). In addition, iron concentration was monitored
to study the stability of Fe@17-GAC during the experiments. When pH was 3, only less than 0.25% of the
loaded iron in GAC was dissolved into the solution. No iron content was detected at higher pH (4-6). This
fully indicated that nanoscale iron oxide was very stable in the pores of Fe@17-GAC.
TABLE 1. Characteristics of GAC and Fe-GACs

Sample Iron content BET surface Total pore volume Langmuir isotherm model
(%) area (cm3/g) (cm3/g)
qmax(mg/g) KL(L/mg) R2
GAC 0 1103 0.68 22.78 0.20 0.99
Fe@10-GAC 10 1044 0.54 26.39 0.36 0.99
Fe@17-GAC 17 963 0.50 29.94 0.25 0.99
Fe@27-GAC 27 877 0.45 27.10 0.18 0.99
FIGURE 1. TEM images of (a) GAC and (b) Fe@17-GAC

qe (mg/g)
pH=3
pH=4
pH=5
pH=6
Ce (mg/L)
FIGURE 2. Adsorption isotherms of GAC at different pHs
209
qe(mg/g)
pH=3
pH=4
pH=5
pH=6
Ce(mg/L)
FIGURE 3 Adsorption isotherms of Fe@17-GAC at different pHs
TABLE 2. Langmuir isotherm constants for GAC and Fe@17-GAC at different pHs
Sample pH Langmuir
qmax (mg/g) KL (L/mg) R2
GAC 3 0.11 9.8 0.92
4 10.30 0.15 0.99
5 18.69 0.10 0.98
6 22.78 0.20 0.99
Fe@17-GAC 3 0.26 2.71 0.99
4 14.06 0.06 0.94
5 19.23 0.34 0.99
6 29.94 0.25 0.99
Adsorption kinetics. GAC and Fe@17-GAC were studied to compare their adsorption kinetics. Fig. 4
shows the adsorption kinetics of GAC and Fe@17-GAC for Pb(II) adsorption. Table 3 lists the adsorption
constants by fitting pseudo-first-order and pseudo-second-order models. Compared to pseudo-first-order
model, the adsorption data fitted the pseudo-second-order model well, and the R2 was much more than 0.98.
However, the loaded nanoscale iron oxide had an adverse effect on the adsorption rate. For GAC, the
adsorption rate was 0.0060 g/mg min, while that of Fe@17-GAC was 0.0005 g/mg min. This results was in
consistent with the decrease of BET surface area that loaded iron oxides might cause obstacle for Pb(II)
diffusion to the active adsorption sites and reduced the adsorption rate.
TABLE 3. Adsorption kinetics constants of GAC and Fe@17-GAC

Sample Pseudo-first-order Pseudo-second-order
K1(min-1) R2 K2(g/mg min) R2
GAC 0.0037 0.88 0.0060 0.99
Fe@17-GAC 0.0023 0.92 0.0005 0.98
Adsorption thermodynamics. The adsorption thermodynamic parameters of GAC and Fe@17-GAC are
listed in Table 4. Compared to GAC, due to nanoscale iron oxides doped in Fe@17-GAC, the negative value
of △G0 increased, indicating that it was more favorable to the spontaneous process. The negative values of
△H0 for both adsorbents revealed the exothermic nature of adsorption process, while the positive entropy
changes (△S0) showed the much better affinity for Pb(II) adsorption and the increase of disorderness.
210
Therefore, although the nature of adsorption was not changed for both adsorbents, the changes of
thermodynamic parameter values (△G0,△H0,△S0) proved that the loaded nanoscale iron oxides obviously
favored the Pb(II) adsorption.
Percentage of removal(%)
GAC
t(min)
FIGURE 4. Adsorption kinetics of GAC and Fe@17-GAC
TABLE 4. Adsorption thermodynamic parameters of GAC and Fe@17-GAC

Sample Temperature(K) KL(L/mg) △G0(KJ/mol) △H0(KJ/mol) △S0(KJ/mol K)
GAC 288 0.22 -25.70 -18.56 0.04
298 0.15 -25.65
308 0.13 -26.21
Fe@17-GAC 288 0.64 -28.25 -11.51 0.06
298 0.54 -28.78
308 0.47 -29.41
CONCLUSION
Nanoscale iron oxides modification was proven to be effective for enhancing the Pb(II) adsorptive
capacity. The optimum loaded iron content was about 17%. GAC adsorbed 22.78 mg Pb(II)/g, while
Fe@17-GAC could adsorb 29.94 mg Pb(II)/g though the addition of nanoscale iron oxides reduced the
adsorption rate to some extent. The adsorption process was pH-dependent and near neutral pH range was
more favorable. The stability of loaded iron was excellent in the pH range of 3 to 6. Adsorption process was
spontaneous and exothermic. This study revealed that Fe-GAC was a potential and effective adsorbent for
removal of Pb(II) in aqueous phase.
ACKNOWLEDGEMENTS
This work was supported by Shanghai Science and Technology Development Fund for
Environmental Protection (No.2012-03).
REFERENCES
Ahmed, M. A., S. M. Ali, S. I. El-Dek and A. Galal, 2013. “Magnetite-hematite nanoparticles prepared by
green methods for heavy metal ions removal from water”. Materials Science and Engineering: B, 178
(10): 744-751.
Chen, W. F., Z. Y. Zhang, Q. Li, and H. Y. Wang, 2012. “Adsorption of bromate and competition from
oxyanions on cationic surfactant-modified granular activated carbon (GAC)”. Chemical Engineering
Journal, 203: 319-325.
211
Erto, A., L. Giraldo, A. Lancia and J. C. Moreno-Piraján, 2013. “A Comparison Between a Low-Cost
Sorbent and an Activated Carbon for the Adsorption of Heavy Metals from Water”. Water, Air, & Soil
Pollution, 224 (4). (DOI: 10.1007/s11270-013-1531-3)
Lee, S. M., C. Laldawngliana and D. Tiwari, 2012. “Iron oxide nano-particles-immobilized-sand material
in the treatment of Cu(II), Cd(II) and Pb(II) contaminated waste waters”. Chemical Engineering Journal,
195-196: 103-111.
Noh, J. S. and J. A. Schwarz, 1990. “Effect of HNO3 treatment on the surface acidity of activated carbons”.
Carbon, 28 (5): 675-682.
Pradeep, T. and Anshup, 2009. “Noble metal nanoparticles for water purification: A critical review”. Thin
Solid Films, 517 (24): 6441-6478.
Sotelo, J. L., G. Ovejero, A. Rodríguez, S. Álvarez, J. Galán and J. García, 2014. “Competitive adsorption
studies of caffeine and diclofenac aqueous solutions by activated carbon”. Chemical Engineering
Journal, 240: 443-453.
212
SYNTHESIS AND CHARACTERIZATION OF HIGH ORDERED MESOPOROUS CARBON

(OMC) USING POLYACRYLAMIDE FOR RESORCINOL REMOVAL
Wan Shou, Hanlong Ren, Chong Ren and Daniel Dianchen Gang
(University of Louisiana at Lafayette, LA, USA)
ABSTRACT: Polyacrylamide (PAM) is first time used as carbon source to synthesize ordered mesoporous
carbon (OMC) material. A common mesoporous silica (SBA-15) was used as the template, in which
acrylamide was filled and polymerized into PAM through aqueous solution, followed with a carbonization
process. The OMC was obtained by removing of the silica framework using hydrofluoric acid. The
transmission electron microscopy (TEM) showed the high ordered structure of the OMC, where channels
are parallel to each other with a uniform diameter ranging from 3 to 9 nm. The TEM images indicate that
the OMC is a good replicate of the SBA-15 with hexagonal framework. The absorption capacity of OMC
for resorcinol removal was evaluated with an improvement of 26% when compared with commercial
activated carbon.
INTRODUCTION
Resorcinol, as a typical phenolic compound, is widely applied in production of synthetic resins,
plastics, polymers, dyes and pharmacies as raw materials or intermediates. However, phenolic compounds
are highly toxic and hazardous to living organisms, high oxygen demand, and poor in degradability, making
them as an acute pollutant. Therefore, the effective removal of phenol and its derivatives from aqueous
environment has drawn widely attention of both researchers and government.
In order to remove phenolic compounds, various methods have been developed recently, including
biodegradation (Parmar et al. 2012), membrane separation (Anemir et al. 2013), adsorption (Guo et al.
2013), extraction and so on (Rahmanian et al. 2014). However, among all the methods, adsorption appears
to be the best candidate for overall treatment, especially for the effluents with moderate and low
concentrations. The nature of the adsorbent like pore structure, functional groups, polarity and aqueous
solubility determine the adsorption capacity, thus, numerous research has been conducted to fabricate novel
materials (Cansado et al. 2012; Liu et al. 2012; Xie et al. 2012) to improve adsorption efficiency of phenolic
compounds through creating geometrical and chemical heterogeneity of adsorbents. As a promising
candidate, ordered mesoporous carbons (OMCs) have gained increasing interests for application in
adsorption due to their special properties like uniform mesopores with tunable large size (2-50 nm), large
specific surface areas (up to 1800 m2g-1) and higher hydrothermal resistance compared with mesoporous
silica materials and other materials (Liu et al. 2012; Ryoo et al. 2001; Yu et al. 2002). Also, OMCs have
shown an unprecedented adsorption performance towards a wide range of inorganic and organic pollutants
with fast adsorption kinetics. Generally, heteroatoms contained in functional groups can be indirectly
induced in OMCs through post-treatment using functionalizing agents or coated with OMC as a composite
(Liang et al. 2008), or directly incorporated in the precursor as carbon source. However, due to the relatively
low reactivity of carbon surface, post-treatment complicates the process and increases the cost. Meanwhile,
post-treatment accompanied with using of nitric acids or other chemicals may generate secondary pollution.
On the other hand, post-modification results in low bonding densities, and may damage the carbon surface
or meso-structure (Liang et al. 2008), like shrinking the mesopore size, reducing surface area and pore
volume, and damaging the ordered pore structure. In contrast, fabricating OMC polymer composite is a
cleaner and more effective method (Choi and Ryoo, 2003), but it is easy to cause pore blockage. However,
if such functional groups can be incorporated in the carbon precursor and kept after carbonization, the
desired OMC manufacturing process will become more straightforward and environmental-friendly.
There are two main routes to synthesize well-controlled OMCs: one is soft template synthesis, in
which block copolymers are directly self-assembled as templates for generation of porous carbon structures,
then OMCs are obtained through cocondensation and carbonization (Liang and Dai, 2006); the other is hard
template synthesis, in this method, mesoporous silica is pre-synthesized as a mold and then filled with
213
carbon precursor, followed with carbonization and subsequent template removal using sodium hydroxide or
hydrofluoric acid. In this study, SBA-15 was employed as a hard template to prepare OMC. Acrylamide
(AM), due to its carbon-carbon double bond, amide group, and its wide range of chemical reactions, was
chosen as a monomer to polymerize polyacrylamide (PAM) as carbon source. PAM is a broadly applied
flocculant for wastewater treatment; however, its application as a carbon precursor to synthesize OMC for
resorcinol removal is first time investigated. Silica mesoporous templates with different channel widths
were synthesized by tuning the reaction time and temperature to fabricate OMCs and compare their
adsorption capacities. Also, the influence of template to monomer ratio (SBA-15:AM) on the OMC structure
and adsorption capacity was studied.
Synthesis of Silica Template and OMC. The synthesis of SBA-15 was performed according to the report
by Guo et al. (2013). Typically, 100 ml of concentrated hydrochloride acid (HCl, 37%) was added into 525
ml of distilled water, and then 20 g of triblock copolymer Pluronic P123 (EO20PO70EO20, BASF) was added
as surfactant to direct the formation of mesoporous structure. Subsequently, 46.5 ml of
tetraethylorthosilicate (TEOS, 98%, Aldrich) was added after the complete dissolving of above mixture.
Then the resulting mixture was vigorously stirred to form a homogeneous solution. After the reaction at
certain conditions (40˚C for 4 h denoted as SBA-15-1, 50˚C for 6 h denoted as SBA-15-2, and 60˚C for 8 h
denoted as SBA-15-3), the suspension was aged in 90 ˚C water bath for 24 h. Then the solid product was
filtered and washed using 80~90 ˚C distilled water, and dried in an oven at 105 ˚C overnight. After drying,
the product was calcined in furnace with air at 550 ˚C for 8 h.
The synthesis of OMC was accomplished by in situ polymerization of acrylamide (AM) in the
mesopores of SBA-15 template in an aqueous solution. Typically, 10 g of AM (≥99%, Aldrich) was mixed
with different amount of SBA-15 powder in 20 ml distilled water. After the mixture was homogenous, 0.05g
of 2, 2-azobisiobutyronitrile (AIBN, Aldrich) was added as a free radical initiator. The resulting mixture
was then transferred into 65 ˚C water bath with continuously stirring for the in situ polymerization.
Afterwards, the composite material was dried in oven at 200 ˚C overnight and subsequently carbonized at
700 ˚C (8 h) in a tubal furnace (Thermo Scientific) under N2 atmosphere. Then, the template was removed
using hydrofluoric acid (HF, 48%, Aldrich). The mixture was filtered and washed with 1000 ml distilled
water to obtain OMC. Afterwards, OMCwas dried in oven around 100 ˚C overnight. The OMC obtained
using 3g, 2g and 1g SBA-15 were denoted as OMC-3X, OMC-2X and OMC-1X, where X ranges from 1 to
3, denoting the batch of different SBA-15 templates. For example, OMC-23 means OMC synthesized using
2g of SBA-15-3.
Static Adsorption. In order to evaluate the adsorption capacities of OMCs on resorcinol, batch adsorption
experiments were conducted as following procedure: resorcinol solution (100ml) with concentration of
5mg/L was poured in both experimental and control conical flask; all the samples were placed in an E 24
Incubator Shaker (New Brunswick Scientific) at 200 rpm at room temperature; after 24 h, the conical flasks
were removed and the solutions were filtered. The control was used as reference to establish the initial
concentration for the solutions containing OMCs. The filtered solution was analyzed for the final
concentration of resorcinol. The adsorption capacities of OMCs were measured by Cary 50 UV-visible
spectrophotometer (Varian) setting wavelength of 500 nm at room temperature. The amount resorcinol
adsorbed by OMCs was determined by subtracting the final concentration from the initial concentration
r − rs t
with the following formula:
q=
N
Where, q is the adsorption capacity (mg/g); Ci is the initial concentration of resorcinol in solution (mg/L);
Cf is the final concentration of resorcinol in treated solution (mg/L); V is the volume of the solution taken
(L); M is the weight of the adsorbent OMCs (g).
214
Morphology of SBA-15 and OMCs. Transmission electron microscope (TEM) was employed to
characterize the mesoporous structure of SBA-15 and OMC with acceleration voltage of 80 kV using a
Hitachi 7600. TEM images of SBA-15 are exhibited in Figure 1, together with the change of channel
diameter corresponding to reaction condition (time and temperature). It is noticed that by increasing the
heating temperature and time in the reaction solution can increase the channel diameter from 3 nm to 9 nm
(maximum ca. 10 nm). All the diameters were measured by ImageJ, with standard deviations around 0.5
nm. TEM images inserted in Figure 1 display the parallel mesopores of SBA-15 viewed from (110)
direction.
18
Channel Diameter (nm)
15
12
9
6
9
3 6
3
0
SBA-15-1 (40˚C, 4h) SBA-15-2 (50˚C, 6h) SBA-15-3 (60˚C, 8h)
FIGURE1. The influence of reaction condition on SBA-15 channel diameter.
a b c
FIGURE2. TEM images of OMCs duplicated from (a) SBA-15-1 (b) SBA-15-2 and (c) SBA-15-3.
The corresponding OMCs replicas of SBA-15 are illustrated in Figure 2, all the meso-structures,
with parallel ordered channels, are analogous to their templates; however, the channel diameters are smaller
than their template about 1 nm, probably resulting from the shrinkage of carbon/silica composite material
during carbonization and removal of host silica (Lee et al. 2002). Also, TEM images viewed from
perpendicular direction of SBA-15 and OMC are shown in Figure 3, showing the hexagonal structure,
similar to previous report (Choi and Ryoo, 2003). It is found the addition of SBA-15 of 2g and 3g resulted
in the same mesoporous structure, further proving that the OMC structure was the replica of its silica
template. However, it is very interesting that using 1g of SBA-15 resulted in totally different structure of
carbon materials. In that case, we failed to obtain OMC, but some hollow nanofiberlike carbons were
observed, which was mentioned by Lee et al. (2002).
FT-IR Measurement. Functional groups and chemical bonds were detected by Fourier transform infrared
spectroscopy (FT-IR) using a PerkinElmer Spectrum 100 FT-IR Spectrometer. As shown in Figure 4, the
five OMCs show similar spectra. The small bands ranging from 3500 to 3950 cm-1 can be related to the
stretching vibration of –OH, C-H and N-H. The bands emerging in the region between 1910 and 2370 cm-1
can be attributed to C-O (Cansado et al. 2012). The strong peaks centered on 1700 cm-1 are typical vibration
due to C=O stretching. The stretching of C-H gives rise of the bands near 860 and 930 cm-1. The peak near
1460 cm-1 may be caused by the stretching vibrations of C-N (Jung et al. 2004). All the samples show similar
215
peak distribution, revealing the existence of C, N, H and O elements. The existence of N, H and O may
enhance the interactions between adsorbent and pollutant through weak molecular force, such as hydrogen-
bond.
a b
FIGURE 3. TEM images of SBA-15 (a) and OMC (b) viewed from the (100) direction.
C: 66.95%
N: 20.64%
O: 12.40%
FIGURE 4. FT-IR spectra of OMCs. FIGURE 5. Energy-dispersive X-ray spectroscopy of

OMC.
Energy-dispersive X-ray Spectroscopy (EDS) Analysis. EDS analysis of OMCs were conducted in a
JEOL 6300 Scanning Electron Microscope (SEM). Figure 5 indicates the existence of three main elements
(C, N and O). The absence of H may result from its small atomic weight. However, the percentage of H can
be deducted from the percentages of C, H and O, accounting about 0.01%. This result further proves the
way to introduce nitrogen from the carbon precursor is feasible.
TABLE 1 Specific surface area of SBA-15 and OMCs

Sample SBA-15-1 SBA-15-2 SBA-15-3
(m2/g) 561 597 493
Sample OMC-21 OMC-31 OMC-22 OMC-32 OMC-23
(m2/g) 474 362 408 427 369
Specific Surface Area of SBA-15 and OMCs. Specific surface areas were obtained using a Micromeritics
FlowSorb III Surface Area Analyzer through nitrogen adsorption-desorption method. As displayed in Table
216
1, these results are similar to previous report (Yuan et al. 2008). It is believed that template with higher
specific surface area can result in higher specific surface area OMC; however, the trend in actual data is not
obvious, which may result from the shrinkage and collapse during the process of carbonization and the
etching of template. It is noticed that the final surface area of OMC was affected by the amount of added
template, this may attribute to the change of purity: if the monomer is less than enough to fill the template,
the meso-structure may not be well-ordered; on the contrary, if the monomer exceeds the amount to fill the
template, part of the carbon material will lose the meso-structure. Therefore, more research is needed to
optimize the ratio between monomer and template. Compared with silica templates, the specific surface area
of OMCs decreased due to the shrinkage of structure.
FIGURE 6 Comparison of adsorption capacities of Norit AC and different OMCs.
Resorcinol Adsorption Study. The adsorption capacities for resorcinol removal of different OMCs were
compared with the commercial GAC shown in Figure 6. All OMCs have higher adsorption capacity than
GAC (27mg/g), ranging from 28mg/g to 34mg/g. Among these OMCs, OMC-22 has the highest
improvement, about 26%, compared with GAC. It is noticed OMCs replicated from SBA-15-2 has better
adsorption capacity than the other two, while the ones made from SBA-15-1 have the lowest adsorption
capacity. The ratio of SBA-15 to AM does not show significant influence on the adsorption capacity in the
investigated cases, however, it is believed that the ratio between template and monomer can affect the purity
of OMC, thereby impacting the adsorption capacity. Based on these results, it can be concluded that specific
surface area affects the adsorption capacity for resorcinol removal but may not be the only impact factor,
namely, high surface area may not guarantee high adsorption capacity.
CONCLUSIONS
PAM was first time used as carbon precursor to synthesize ordered mesoporous carbon materials.
By tuning the reaction conditions, channel diameters of SBA-15 were adjusted from 3 to 9 nm. Well-ordered
mesostructures of SBA-15 and OMC were observed under TEM. The ratio between monomer and template
can directly affect the final structure of obtained carbon materials; however, the ratio should be further
studied to clarify the influence and optimize the process. FTIR and EDS analysis demonstrated that nitrogen
element was successfully introduced in the final OMC, proving the feasibility of designing OMC from the
carbon precursor. The adsorption capacity of developed OMCs showed a considerable improvement
(maximum about 26%) when compared with commercial activated carbon. This work provides a new
method to design OMC from the carbon precursor.
ACKNOWLEDGEMENTS
This work was supported by the Louisiana Board of Regents under BORSF (2010-2015)-LaSpace
and by NASA under award NNX10AI40H.
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218
ADSORPTION OF PHENOL ONTO LOW COST ADSORBENT: OPTIMIZATION OF

ADSORPTION PROCESS PARAMETERS
Ingole Ramakant S. and Lataye Dilip H.

(Department of Civil Engineering, VNIT Nagpur- 440010 India)
ABSTARCT: In the present study an activated carbon prepared from babool saw dust (BAC) has been used
for the removal of phenol from aqueous solution. Taguchi design of experiment technique has been applied
to optimize the significant parameters in adsorption process. Batch adsorption study was carried out to
evaluate the effect of significant parameters, viz. Parameter A: adsorbent dose (m), B: initial concentration
(C0), C: temperature (T) and D: contact time (t) on the removal of phenol from the aqueous solution. The
adsorption capacity qt (mg g-1) of BAC has been considered as response characteristic and optimized by
using Taguchi Orthogonal Array (OA) for L9 (4 factors 3 level, 34) design. Three levels of each parameter
were decided as: adsorbent dose: 0.2, 0.5 and 0.8 g, initial concentration: 100, 200 and 300 mg L-1,
temperature: 293, 303 and 313 K and contact time: 30, 60 and 90 min. The levels of each parameter were
decided from the batch study performed earlier. From the experimental study it is observed that the
Parameter A has highest influence at level 1, B at level 3, C at level 1 and D at level 2 (A1B3C1D2). The
analysis of variance (ANOVA) shows that, parameter B is the most significant with 57.14% contribution to
the qt. The parameter A is also significant with 39.93% contribution to qt. Confirmation experiment at
optimal levels (A1B3C1D2) of the parameters validated the effectiveness of Taguchi design of experimental
technique for adsorption of phenol. The percent removal of phenol at the optimized conditions was found
to be 31.52% with total uptake of 23.64 mg/g of BAC at optimal condition. The result of the study showed
that, Taguchi’s design of experiment technique can be applied for the optimization of adsorption process
parameters.
INTRODUCTION
Due to fast depletion of the fresh water resources, the world is facing problem of deficiency of fresh
water. Various industrial and domestic activities have polluted surface and ground water to the greater
extent. The industries continuously discharge heavy metals, phenolic compounds and other toxic substances
and hence the treatment and removal of these organic and inorganic pollutants from water has become the
global issue.
Phenol is both anthropogenic and naturally occurring compound which is found in nature in some
foods, human and animal waste and due decomposition of organic materials. Phenols are widely used for
the production of wide varieties of resins including phenolic resins which are used as a construction material,
for automobiles and appliances, epoxy resins and adhesives. It is also used in the production of caprolactum
(used in the manufacturing of Nylon 6 and other synthetic fibers). Phenol is used as a slimicide (toxic to
bacteria and fungi characteristic slimes), as a disinfectant and in medicine preparation such as over the
counter treatment for sore throats [Cherifi et al., 2011]. The phenolic compounds enter into the stream or a
water source as a discharge of wastewater from industries such as high temperature coal conversion,
petroleum refining, phenol production industries, explosive manufacturing industries, fertilizer industries,
dye manufacturing industries, resins and plastic industries. Such aromatic hydroxyl compounds are
considered priority pollutants since they are harmful to organism even at low concentration
[Ahmaruzzaman, 2008]. As per the Indian standards, phenol content in drinking water should not be more
than 0.002 mg/L. Phenol is soluble in water, oils, carbon disulphide and numerous organic solvents. It is
toxic and mutagenic substance at high concentration and may be absorbed through skin. Phenols are
biodegradable, colourless to white when pure and has distinct odour i.e. sickeningly sweet and tarry and can
catch fire.
Recently numerous approaches have been studied for the development of most economical and
effective technology to reduce contamination in waste water and to improve the quality of the treated
effluent. Adsorption is an effective and economic method for phenolic compound bearing wastewater
treatment. Adsorption is transfer of ion from liquid phase to solid phase. Basically adsorption is mass
transfer process by which substance is transferred from one phase to other phase and bound by physical or
219
chemical interaction. The high quality effluent can be obtained in adsorption along with simplicity and
flexibility in design and operation. In addition adsorption is sometime reversible hence adsorbent can be
regenerated by suitable desorption process.
Activated carbon (AC) is the adsorbent widely used for the removal of phenolic compounds [Lu
and Sorial, 2009]. Its usefulness derives from its large micropore and mesopore volume and the resulting
high surface area. Recently the sources of coal based AC are depleted resulting in the increase of price
[Ozkaya, 2005]. Hence searching for low cost and easily available adsorbent to remove phenolic compounds
has become a main research focus. Agricultural waste and some natural organic materials have been studied
as adsorbent for the removal of aromatic compounds from wastewater [Vazquez, 2007]. Due to their ample
quantity, agriculture waste have low economic value additionally their deposition is contributing in the
significant environmental degradation. Agriculture waste is low ash content and reasonably hard hence is
rich source of AC. The waste material having rigidity such as shell of fruits like nuts, peanuts, dates, olives,
almonds however the waste generated from cereals like rice, coffee, soybean, maize, sugarcane bagasse,
coir pith and various seed waste are used as adsorbents [Ahmaruzzaman, 2008]. It is possible to obtain AC
with different pore texture by varying activation conditions. It can be chemically activated by using
chemicals like H3PO4 and KOH as activating agents [Lin and Juang, 2009].
In the present study babul activated carbon (BAC) prepared from babul sawdust is used as an
adsorbent for the removal of phenol from aqueous solution. Adsorption of phenol like any other adsorption
process is always affected by several parameters such as adsorbent dose (m), initial concentration (C0),
contact time (t) and temperature (T) hence these parameters need to be optimized for the maximum
adsorption of phenol. In batch study, the adsorption parameters are optimized by varying one and keeping
another parameters constant which does not take into account the effect of interaction of other parameters
on the sorption process. Fractional factorial design based on Taguchi’s orthogonal array can be a very
effective methodology to investigate the effects of multiple parameters as well as potential interactions
between these parameters in a time and cost effective manner [Taguchi and Wu, 1979; Shrivastava et al.,
2007; Lataye et al. 2008, 2009; Rai et al. 2012, 2013].
The selected response characteristic i.e. the total adsorption capacity ( qtot ) of BAC for phenol is
optimized the parametric values affecting sorption. The average values and the signal to noise (S/N) ratio
of the quality response characteristic for each parameter at three levels of values have been calculated from
experimental data. The response curves have been graphically represented to reflect any change in the
quality characteristic and S/N ratio with the variation in process parameters. These response curves are used
to study the effects of various parameters on the response characteristics. Contribution of each parameter in
the adsorption process has been calculated by using the analysis of variance (ANOVA) on the experimental
data.
Adsorbent Preparation. Babul sawdust obtained from local sawmill in Nagpur, India was sieved through IS
sieve to obtain size fraction of (250 μ to 500 μ). The sawdust was washed 4-5 times with double distilled water
to remove impurities such as dust, ash etc. First the washed material was kept for sun dry for about 24 hrs and
then it was kept in hot air oven at the temperature of 105°C for about 2 hrs. About 100 gm of dried sawdust
was mixed with 100 ml of orthophosphoric acid and it was kept for 24 hrs. The char produced after 24 hrs was
then activated in muffle furnace by maintaining the temperature of 400 to 450 °C inside for 1 hr. The activated
carbon was again washed with double distilled water till the complete acid gets removed. Subsequently the
washed activated carbon was air dried and afterwards kept in hot air oven at temperature of 105°C for 2-3 hrs
and used for adsorption study.
Adsorbate. All chemicals used in the present study were of AR grade. Phenol (chemical formula: C6H5OH,
molecular weight: 94.11 gm/mole and wavelength, λmax: 270 nm) was procured from Upper India Scientific,
Nagpur, India. One gram of crystalline phenol was taken and mixed well in doubled distilled water (DDW) to
prepare the stock solution of 1000 mg/L concentration. The stock solution was diluted subsequently to prepare
the test solutions of desired concentration as and when required.
220
Analytical measurements. The experiments were carried out in stoppered 250 ml conical flasks. The loss of
phenol due to evaporation was checked time to time and found that there is no loss of phenol during the
experiment and analysis. The concentrations of phenol from aqueous solutions were determined by UV-VIS
Spectrophotometer (UV2450, SHIMADZU) at wavelength 270 nm. The graph plotted between absorbance and
phenol concentration was used as standard graph for the determination of phenol concentration of treated
solutions. For higher phenol concentrations, the solution was diluted with Doubled distilled water (DDW) for
the accurate concentration determination.
Taguchi’s Design of Experimental Methodology. Taguchi’s design strategy has been used in the present
study. The various parameters and their ranges were decided on the basis of the detailed experiment carried
out earlier for phenol removal by BAC. The process parameters having significant impact on adsorption
process are given in TABLE 1. As shown in TABLE 1, four parameters each at three level were used in
Taguchi’s L9 (3)4 orthogonal array and the 9 experiments were carried out in triplicate under the same
condition (Roy, Ranjit 1990).
TABLE 1: Process parameters for adsorption study of phenol onto BAC using Taguchi’s
Orthogonal Array
Factors Parameter Units Level
1 2 3
A Dose (m) g/50 ml 0.2 0.5 0.8
B Initial Concentration (C0) mg/L 100 200 300
C Temperature (T) Kelvin 293 303 313
D Contact Time (t) min 30 60 90
Batch adsorption studies. For each experimental run the aqueous solution of known concentration of
phenol was prepared and 50 ml of each sample was taken in 250 ml conical flask with a glass stopper
containing known amount of BAC (m). These mixtures were then agitated at the shaking speed of 150±5
rpm in a temperature controlled orbital shaking incubator (REMI Instrument, Mumbai, India) for desired
temperature of (293, 303 and 313 K) for different contact time (30, 60 and 90 min). The samples were
withdrawn at desired time interval and filtered using filter paper and analyzed for the residual concentration
of phenol. Total phenol uptake on the surface of BAC adsorbent qtot (mg/g) was calculated using following
relationship,
3
qtot = ∑ (C0,i − Ce,i )V / W (1)
i =1
Where, C o,i and Ce,i are the initial and the equilibrium concentration in mg/L of phenol, V is the volume
(L), W is the weight (g) of the adsorbent.
Analysis of Experimental data. The ‘higher is better’ quality characteristic was used in the analysis of
experimental data. The plot of response curve, analysis of variance (ANOVA) for raw data and S/N ratios
data were used for the analysis of result and to predict the sorption performance. The mean of the response
characteristic (μ) at the optimal condition was estimated as,
μ = T + (A 2 - T) + (B2 -T)=A 2 +B2 -T (2)

Where, T is the overall mean of response, A 2 and B 2 represents the average values of response at second
level of parameters A and B respectively.
The estimation of µ is only a point estimate based on the average of results obtained from the
experiment. The statistical range defined as the confidence interval (CI) of the statistical parameter is a
maximum and minimum value between which the true mean, µ should fall at some stated level of
221
confidence. The confidence interval is of two types, CIPOP which is for the entire population, and CICE which
is for only a sample group of experiments carried out under specified conditions. These confidence intervals
are defined as:
CI POP =
Fα (1, f e ) Ve (3)
neff
 1 1 (4)
CI CE = Fα (1, f e )Ve  + 
n
 eff R 
Where, Fα (1, f e ) = F ratio at confidence level of (1-α) against the DOF and error DOF f e ,
Ve = error variance (ANOVA)
N (5)
neff =
1 + [total DOF associated in the estimate of the mean]
N = total number of results and, R = sample size for confirmation experiment
It can be seen from Eq. (4) that as R approaches infinity, i.e., the entire population, the value 1/R
approaches zero then CI CE = CI POP . As R approaches 1, CICE becomes more. In order to confirm that the
optimal parametric values determined by using Taguchi’s methodology are valid, a selected number of
confirmatory sorption experiments are carried out under optimal conditions. The average of the results of
the confirmation experiments is then compared with the anticipated average based on the optimal parameters
and levels tested by Taguchi’s methodology. If the deviation between actual and determined qtot by
Taguchi’s methodology is within 5%, it can be confirmed that the optimal parametric values determined by
Taguchi’s design are valid.
Effect of Process Parameter. The experiments were performed as per the Taguchi’s L9 Orthogonal array
and the values are shown in FIGURE 1. The FIGURE 1 also reveals that, the adsorbent dose (m) at level 1,
the initial concentration (C0) at level 3, temperature (T) at level 1 and the contact time (t) at level 2 have
highest influences on adsorption capacity ( qtot ).
20 30
18
25
16
14
20
12
S/N Ratio (dB)
qtot (mg/g)
10 15
8
10
6
4 qtot 5
S-…
2
0 0
0.2 0.5 0.8 100 200 300 293 303 313 30 60 90
Factors
FIGURE 1. Effect of process parameter on qtot and S/N ratio adsorption of phenol on BAC.
222
The difference between influence at level 2 and level 1 (L2−L1) of each parameter indicates that
initial concentration has the largest influence on qtot in comparison to other parameters (TABLE 2 and
TABLE 3).
TABLE 2: Average and main effects of qtot values for BAC- raw and S/N data
Factors Raw Data Main Effects S/N Effects Main Effects
L1 L2 L3 L2 - L1 L3 - L2 L1 L2 L3 L2 - L1 L3 - L2
A 17.33 12.56 9.02 -4.78 -3.53 17.32 21.31 18.26 3.99 -3.04
B 7.81 13.34 17.76 5.53 4.42 17.10 22.21 24.77 5.12 2.56
C 13.65 12.70 12.56 -0.95 -0.14 22.39 21.46 20.24 -0.93 -1.22
D 12.12 13.81 12.98 1.69 -0.83 21.66 21.13 21.29 -0.53 0.15
TABLE 3: Summary of parameter having highest influence on qtot values for BAC
Adsorbent Raw Data Main Effects (Raw S/N data Main Effects
(Avg Value) Data) (Avg Value) (S/N Data)
L1 L2 L3 L2 - L1 L3 - L2 L1 L2 L3 L2 - L1 L3 - L2
BAC A D B B B C B B B B
The contribution of the individual parameters is weighed to enforce the control on adsorptive
removal of phenol. ANOVA results for raw and S/N ratio data with desired response characteristic ( qtot )
are given in TABLE 4 for adsorption of phenol onto BAC. The F ratios obtained from ANOVA for raw data
and S/N ratio show that all parameters are statically significant at 95% confidence limit for qtot as desired
response characteristic.
TABLE 4: ANOVA of qtot and S/N ratio data adsorption of phenol onto BAC
Pure Sum of
Percentage
Total variance DOF, Variance V Variance Square
Factors Contribution
of each factor, S f (Sf/ fA) Ratio, F (S’A)= SA-
P (Pa=SA*100/ST
fA*Ve
A 313.09 2.00 156.55 1399.10 312.87 39.93
B 447.63 2.00 223.81 2000.29 447.40 57.14
C 6.32 2.00 3.16 28.24 6.10 0.00
D 12.88 2.00 6.44 57.55 12.66 1.54
Error 2.01 18.00 0.11 1.00 1.12 1.39
Total 781.93 26.00 390.07 100.00
TABLE 4 shows that Initial concentration (parameter B) is the most significant parameter with
57.14% contribution to raw data and adsorbent dose (parameter A) is the second most significant parameter
with 39.93% contribution. Temperature (parameter C) and contact time (parameter D) has the very less
significance to the S/N ratio data for adsorption study. The significant process parameters affecting the
removal of phenol by BAC and their optimal levels (as already selected) are A1, B3, C1 and D2.
Confirmation Experiment. Three confirmation experiments were carried out for adsorption of phenol on
to BAC at the selected optimum level (A1 B3 C1 D2). The average value of qtot (mg/g) from three
experiments and predicted value by Taguchi’s method were compared. The experimental value of qtot was
23.56 mg/g which is very closed to the value obtained by Taguchi’s method. It is found that the qtot from
confirmatory experiments is within 95% of CI . It may, however, be noted that the optimal parametric values
are valid within the specified range of process parameters only and that any extrapolation/interpolation must
be verified through additional experiments.
223
CONCLUSIONS
The adsorption process parameters adsorbent dose, initial concentration, temperature and contact
time at three levels with a Taguchi’s design of OA layout of L27 (34) could be optimized with the higher-is-
better quality character with 27 sets of experiments only. All the factors considered in the experimental
design with qtot as the desired response characteristic are statistically significant at 95% confidence limit.
The BAC shows the potential for adsorption of phenol at a concentration of 300 mg/L with the sorption
capacity of 23.64 mg/g with the removal of 31.52 % at optimum condition. The Taguchi’s design of
experimental methodology can be used in the fixed bed adsorption study to optimize the parameters like
flow rate, diameter of column etc. and the optimized conditions like pH and temperature can be used in the
fixed bed adsorption study.
REFERENCES
Ahmaruzzaman, Md. 2008. “Adsorption of phenolic compounds on low-cost adsorbents: A review.”

Advances in Colloid and Interface Science 143: 48–67.
Cherifi, H., Hanini, S. and Bentahar, F. 2006. “Adsorption of phenol from wastewater using vegetal as a
new adsorbent.” Desalination, 244: 177-187.
Lataye, D. H., Mishra, I. M., and Mall, I. D. 2008. “Multicomponent Sorptive Removal of Toxics-Pyridine,
2-Picoline and 4-Picoline from Aqueous Solution by Bagasse Fly Ash: Optimization of Process
Parameters.” Ind. Eng. Chem. Res., 47(15): 5629-5635.
Lataye, D. H., Mishra, I. M., and Mall, I. D. 2009. “Multicomponent Sorption of Pyridine and its Derivatives
from Aqueous Solution onto Rice Husk Ash and Granular Activated Carbon.” ASCE: Practice
Periodical of Hazardous, Toxic, and Radioactive Waste Management, 18(4): 218-228.
Lu, Q., and Sorial, G.A. 2009. “Comparative study of multi-component adsorption of phenolic compounds
on GACs and ACFs.” Journal of Hazardous Materials, 167: 89-96.
Lin, S.H., and Juang, R.S. 2009. “Adsorption of phenol and its derivatives from water using synthetic resins
and low cost natural adsorbents: A review.” Journal of Environment Management, 90: 1336-1349.
Ozkaya, B. 2006. “Adsorption and Desorption of phenol on activated carbon and a comparison of isotherm
models.” Journal of Hazardous Materials, B129: 158-163.
Rai, S., Lataye, D. H., Chaddha, M. J., Mishra, R. S., Mahendiran, P., Mukhopadhyay, J., Yoo, C. K., and
Wasewar, K. L. 2013. “An Alternative to Clay in Building Materials: Red Mud Sintering Using Fly Ash
via Taguchi’s Methodology.” Advances in Materials Science and Engineering, Volume 2013, Article
ID 757923, 7 pages, http://dx.doi.org/10.1155/2013/757923.
Rai, S., Wasewar, K.L., Lataye, D.H., Mishra, R.S., Puttewar, S.P., Chaddha, M.J., Mahindran, P., and
Mukhopadhyay J. 2012. “Neutralization of red mud with pickling waste liquor using Taguchi's design
of experimental methodology.” Waste Manag Res., 30(9): 922-930.
Roy, Ranjit 1990. A primer on the Taguchi Method. 1st Edition, SME Society of Manufacturing Engineers,
USA.
Shrivastava V.C., Mall I.D. and Mishra I.M. 2008. “Optimization of parameters for adsorption of metal ions
onto rice husk ash using Taguchi’s experimental design methodology.” Chemical Engineering Journal,
140: 136-144.
Taguchi, G. and Wu, Y.I. 1979. “Off line quality control, Central Japan quality control Association.”
Nagoya, Japan.
Vazquez, G., Gonzalez, A., Garcıa, A.I., Freire, M.S., and Antorrena, G. 2008. “Adsorption of phenol on
formaldehyde-pretreated Pinus Pinaster bark: Equilibrium and kinetics.” Biresources Technology, 98:
1535-1540.
224
REMOVAL OF DICLOFENAC SODIUM AND CARBAMAZEPINE FROM WATER BY

REGENERABLE GRANULAR CARBON NANOTUBES/ALUMINA ADSORBENTS
Shubo Deng*, Haoran Wei, Bin Wang, Jun Huang, Gang Yu

(Tsinghua University, Beijing, China)
Carbon nanotubes (CNTs) are expected to be ideal adsorbents for organic pollutants in aqueous solution,
but their nanoscale size makes them difficult to be separated from water and their aggregation in water
decreases their sorption capacity. The primary objectives of this study are to prepare a granular CNTs-based
adsorbent to remove the typical pharmaceuticals, and regenerate the spent adsorbent and simultaneously
decompose the adsorbed pollutants by a simple thermal regeneration.
A novel granular CNTs/alumina (Al2O3) hybrid adsorbent with good sorption and regeneration
properties was successfully prepared by mixing CNTs with surfactant Brij 35 and pseudo boehmite,
followed by calcining to remove surfactant and form porous granules. Alumina binder increased the
mechanical strength, hydrophilicity and porosity of the granular adsorbent, while the dispersed CNTs in the
granular adsorbent were responsible for the sorption of declofenac sodium (DS) and carbamazepine (CBZ).
Scanning electron microscopy (SEM) showed that the CNTs and Al2O3 were mixed well and the porous
structure was formed in the granular adsorbent. The high surface area and appropriate pore size of granular
CNTs/Al2O3 adsorbent were favorable for sorption. The sorption of DS decreased with increasing solution
pH, while pH had little effect on CBZ sorption. The maximum sorption capacities of CBZ and DS on the
CNTs/Al2O3 adsorbent were 157.4 and 106.5 µmol/g according to the Langmuir fitting. Moreover, the spent
CNTs/Al2O3 adsorbent can be thermally regenerated at 400oC in air due to the thermal stability of CNTs.
The removal of CBZ and DS changed a little in the initial reuse cycles and then kept relatively constant until
tenth cycles. The adsorbed CBZ and DS were decomposed in the regeneration process. This regenerable
adsorbent may find potential application in water or wastewater treatment for the removal of some
micropollutants such as pharmaceuticals.
225
FLUORIDE BIOSORPTION WITH MODIFIED EICHHORNIA CRASSIPES AND TYPHA

ELEPHANTINA
Suvendu Manna, Prosenjit Saha, Debasis Roy*, Basudam Adhikari, Ramkrishna Sen
(Indian Institute of Technology-Kharagpur, Kharagpur-721302, West Bengal, India)
Eichhornia crassipes (EC) and Typha elephantina (TE) has been used in this study for fluoride removal
from water. The data indicate that the untreated and treated biomass to be potentially effective in removing
fluoride. About 85 % of fluoride present within distilled water spiked with 5 mg/l NaF could be removed
using only 1.0 g/50 ml of treated EC and 1.5 g/50ml of treated TE biomass. The same amount of untreated
EC and TE in comparison removed 52 % and 60 % of fluoride present from distilled water containing 5 mg/l
NaF. The fluoride removal rate of the treated EC and treated TE biomass were found to be 1.6 and 1.4 times
higher than those of activated alumina, respectively. Thermodynamic analysis indicated that the fluoride
removal by EC and TE is a physical adsorption process. The process appears to be more economical
compared to other fluoride removal processes and has a greater adsorption capacity than other processes.
Moreover, the process does not produce sludge, increase water hardness, or release hazardous leachates.
Fluoride removal appears to be mainly driven by hydrogen bonding between fluoride and hydroxyl groups
of biomass. The treated biomass exhibited higher fluoride removal efficiency than their untreated
counterparts due to higher surface area which enhance the intra-particle diffusion of fluoride.
226
REMOVAL OF CHROMIUM (VI) BY ETHYL CELLULOSE TREATED WITH POLYANILINE
Bin Qiu, Cuixia Xu, Suying Wei, Zhanhu Guo

(Lamar University, Beaumont, TX, USA)
Ethyl cellulose (EC) functionalized by polyaniline (PANI) with 5.0, 10.0 and 20.0 wt % of PANI loadings
were prepared by dissolving the ethyl cellulose and PANI in formic acid simultaneously. The composites
of PANI and EC (PANI/EC) was used as an adsorbent for Cr(VI) removal form wastewater. The Cr(VI)
removal efficiency increased with an increase in PANI loading. PANI/EC with a PANI loading of 20.0 wt
% can be completely remove Cr(VI) with an initial concentration of 2000 μg/L with 5 min, which is much
faster than the ethyl cellulose (>1 h). The PANI/EC exhibited a better Cr(VI) removal efficiency in the
acidic solutions than in the basic solutions. The PANI/EC follows the pseudo-second-order behavior. The
adsorption isotherm study demonstrated that the adsorbents follow Langmuir model with a calculated
maximum adsorption capacity of 36.8 mg/g for the 20.0 wt % PANI/EC, which is much higher than that of
cellulose (10 mg/g). The Cr(VI) removal mechanisms explored by FT-IR and XPS involve the reduction of
Cr(VI) to Cr(III) by both of PANI and cellulose.
227
SYNTHESIS AND CHARACTERIZATION OF MODIFIED ORDERED MESOPOROUS

CARBONS FOR TOTAL ORGANIC CARBON (TOC) MODEL COMPOUND (RESORCINOL)
REMOVAL
Hanlong Ren, Wan Shou, Chong Ren and Dianel Dianchen Gang
(University of Louisiana at Lafayette, LA, USA)
ABSTRACT: Ordered mesoporous carbons (OMCs) play an important role in adsorption, catalysis,
separation and purification in recent decades. Surface Modification is an important method to improve the
adsorption capacity of the OMCs. In this research, OMCs were made with different ratio of SBA-15 and
Acrylic acid, then they were modified by using immersion methods with four different aqueous solutions:
10% Ammonium Hydroxide, 10% Sodium Hydroxide, 1 mol/L Aluminum Chloride, and 0.02 g/ml Urea
solution. Synthesis of the transmission electron microscopy (TEM) showed the products were highly
ordered hexagonal structure. Fourier transform infrared spectroscopy (FT-IR) analysis indicated that the
functional groups were introduced into the surface of the modified OMCs, which affected of the adsorption
capacity. Using Resorcinol (a typical total organic carbon (TOC) model compound) to test the adsorption
behavior of the four modified OMCs, From our results, OMC produced by 3:1 ratio of SBA-15 and Acrylic
acid solution get a better adsorption capacity than the other ratio products, and the Ammonium Hydroxide
solution modified OMC showed the best adsorption capacity compared with the other three, the evaluation
showed the adsorption trend is: Ammonium Hydroxide > Urea solution > Sodium Hydroxide ≈ Aluminum
Chloride.
INTRODUCTION
Ordered mesoporous carbon (OMC) materials are generally fabricated using periodic inorganic
silica templates (A.-H. Lu, 2006). Compared with the regular activated carbon-based materials, OMC
materials have a higher adsorption capacity and faster adsorption kinetics. Historically, activated carbon
used for contaminant adsorption has been limited by slow contaminant diffusion kinetics and the
inaccessibility of sorption sited, ordered mesoporous carbon, on the other hand, can reduce the limited
effects by controlled pore size formation and increased the surface area (A.B. Fuertes, 2004). These show
great potential for environmental improvement for the ability to remove inorganic and organic contaminants
from liquid and gas. So more and more environmentalists shows great interests on the OMC material as a
replacement of granular activated carbon (GAC) used in the waste water treatment system.
In general, the mesoporous structure of the OMC are highly depend on the carbon precursor and the
silica template, as well as the synthetic conditions (H. Yang, 2005). It’s apparently both the surface
chemistry and the pore structure of the synthetic materials play a cooperative role in the specific application.
To improve the performance of the adsorption, one important innovative method is the modification of both
the surface chemistry and pore structure (Vinke, P, 1994).
Modified OMCs are primarily inspired from the modification of the activated carbon materials.
Function group introduced to the surface of the OMCs has been concluded in various ways: oxidation,
reduction, electrode method. In our investigation, we try to use different ratio of SBA-15 and carbon
precursor to make the ordered mesoporous carbon, which aimed to improve the pore size structure of the
material. On the modification procedure, we combine both the immersion and microwave method to
introduce the function group to upgrade the adsorption capacity of the OMCs.
Preparation of Silica Template and Ordered Mesoporous Carbons (OMCs). The silica templates (SBA-
15) were synthesized under an acid condition. Pluronic P123, as the organic structure-directing agent (D.
Zhao, 1988), was mixed with hydrochloride acid solution (6%) and magnetic stir for 1hr. Then, 46.5 ml of
tetraethyl orthosilicate (98%) was added to the homogenous solution with vigorous stirring for 10 min. After
228
that, the mixture was placed in a water bath for 4 h at 40 °C, followed by aging for 24 h under 90 °C. The
resulting solid product was washed with 80 ~ 90 °C hot distilled water, and dried in an oven at 105 °C
overnight. After drying, the product was calcined in a muffle furnace with sufficient oxygen gas at 550 °C
for 8 h.
The synthesis of OMC was accomplished in situ polymerization of acrylic acid in the mesoporous
structure of the silica template. 90 ml of acrylic acid (>99%) was added into 180 ml of distilled water to
form the acid aqueous solution. Then, based on three different ratio (1:1; 2:1; 3:1) of silica template and
acrylic acid, we made three sample with SBA-15(3 g, 6 g, 9 g) and acid solution (90 ml) by magnetic stir.
After 30 minutes, 0.1 g of 2.2-azobisisobutyronitrile (AIBN) was added as a free radical initiator. Put the
mixture in the water tank (70 °C) to heat for situ polymerization. The resulting composite was dried by oven
at 200 °C overnight. Afterwards, the sample was carbonized under N2 flow at a temperature ramp rate of 5
°C/min to 700 °C for 8 h. The carbide was immersed in 50 ml 48% HF at room temperature with magnetic
stirring for 24 h to remove the silica template. The OMC was then washed with distilled water (1500 ml) to
remove the residual HF and dried in the oven at 90 ~100 °C overnight.
Modification of the Ordered Mesoporous Carbons (OMCs). The modification of the ordered
mesoporous carbons (OMCs) is mainly based on the immersion test. In our experiment, four different
aqueous solution was introduced to treat the OMCs: 10% Ammonium Hydroxide, 10% Sodium Hydroxide,
1 mol/L Aluminum Chloride, and 0.02 g/ml Urea solution.
Mix the OMC (1 g) with 100 ml aqueous solution and put the flask in the incubator shaker, set the
condition (60 °C, 110r/min) and work for 2.5 h. Filter the modified OMC at the ends of shaking, the solid
product was then calcined in the protection of N2 at 700 °C for 3 h. After that, the carbonized sample was
stirred and washed with 1 L distilled water at 80 °C for 1 h. Then the sample was filtered and oven dried at
105 °C overnight (Moreno-Castilla C, 1997).
Batch Adsorption Study. The adsorption studies were conducted at 25 °C with the pH of 7 by using
resorcinol solution. One blank was used as reference to establish the initial concentration for the solutions
containing OMCs. The mixture of OMC and resorcinol solution was placed in a shaker (200 rpm, room
temperature). After 24 h, the conical flasks were removed and solution filtered (Q. Liao, 2008). The filtered
solution was analyzed for the final concentration of resorcinol. The amount resorcinol adsorbed by OMCs
can be determined by subtracting the final concentration from the initial concentration using the following
r − rs t
formula:
q=
N
Where, q is the adsorption capacity (mg/g); Ci is the initial concentration of resorcinol in solution (mg/L);
Cf is the final concentration of resorcinol in treated solution (mg/L); V is the volume of the solution taken
(L); M is the weight of the adsorbent OMCs (g).
RESULTS and DISCUSSION
Transmission Electron Microscopy. Transmission electron microscopy (TEM) analysis confirms the well-
ordered hexagonal arrays of 2-D mesoporous channels of the SBA-15 silica template. TEM images of the
silica show that the silica template exhibits order structure. Fig. 1 is the TEM images of the silica template
and ordered mesoporous carbon (OMC). Fig. 1(a) illustrates the parallel array of SBA-15 template and the
diameter of silica rods is about 10 nm. Fig. 1(b) (c) (d) showed the different ratio of SBA-15 and Acrylic
acid solution made OMCs. OMC1 is 1:1 ratio, OMC2 is 2:1 ratio, and OMC3 is 3:1 ratio. It can be seen that
the pore size of ordered mesoporous carbon is about 15 nm which is almost the same with that of SBA-15.
The structure of ordered mesoporous carbon is faithfully duplicates the structure of the silica template. And
different ratio of SBA -15 and acrylic acid made OMCs showed almost the same structure.
BET Surface Area Measurements. The specific surface areas of SBA-15 templates and OMCs were
measured by nitrogen adsorption–desorption. The analysis showed in Table.1. From the results, we can find
229
the OMC3 has a larger surface area compared with the OMC2 and OMC1. The tendency is OMC3 > OMC2
> OMC1. Also, the SBA-15’s surface area falls between the OMC2 and OMC1, this probably indicates the
acrylic acid solution is not saturated with the SBA-15 during the OMC1 synthesis. Immersing method
modification has a significance influence on the specific surface area because all the modified OMC3
materials have larger SSA than the original OMC3.
a b
c d
FIGURE 1. TEM images of SBA-15 and ordered mesoporous carbon: (a) SBA-15 (b) OMC1 (c) OMC2
(d) OMC3
TABLE 1. Specific surface Area of the OMCs and SBA-15

Sample SBA-15 OMC 1 OMC 2 OMC 3
m2/g 524.81 467.02 572.58 580.71
Sample OMC3-NaOH OMC3-Urea OMC3-NH3H2O OMC3-
AlCl3
m2/g 646.67 661.88 665.69 676.53
OMC1
OMC2
OMC3
FIGURE 2. FT-IR spectra of different ratio SBA-15 and Acrylic solution made OMCs
FT-IR Analysis. FT-IR spectral analysis allows the identification of different functional groups on the
surface of ordered mesoporous carbon (Fig.2). A set of peaks and small bands emerging in the region
between 3600 and 3900 cm−1 can be attributed to the C-H stretch. The strong peaks showed in 2000 ~ 2400
cm−1 and around 1050 cm-1 could be related to C-O group. The C=O stretching vibrations related to COOH
230
group can be found around 1700 cm-1. The band located at 1580 cm-1 is assigned to stretching of the C=C
bond due to the incomplete situ polymerization. From the figure, all OMCs has the same trends and
stretching, so the surface function group is almost same for different ratio made OMCs (I.P.P. Cansado,
2012).
a b
OMC3
OMC3
OMC3-NaOH OMC3-NH3H2O
1 1
c d
OMC3
OMC3
OMC3-Urea OMC3- AlCl3
FIGURE 3. The FT-IR spectra of OMC and Modified OMCs
The FT-IR analysis of original ordered mesoporous carbon and modified OMC3 were conducted in
the Fig.3. Function groups were changed from different solution modification. Graph (a) showed the NaOH
solution had improved the CH stretching from the C=C group at around 1400 cm-1, 890 cm-1. Graph (b)
showed the NH3H2O had weaken the COOH group around the 2400 cm-1. Graph (c) showed the Urea
solution had strengthened the C=C group at 890 cm-1 and weaken the COOH group at 2400 cm-1 at the same
time. Graph (d) showed the AlCl3 solution had introduced different OH group at 3600~4000 cm-1 stretching,
meanwhile, it strengthened the C=O group at 1600 cm-1 and C=C group at 890 cm-1 (Piotr A, 2008).
a Adsorption Capacity(mg/g) Adsorption Capacity(mg/g) b

40 39
38
35 37 38
37
30 36 37 37
33 35
25 34 35 35
25 33
20 23 32 33
31
15 30
10
5
0
OMC1 OMC2 OMC3 GAC
FIGURE4. Adsorption Capacity of Different OMCs and Granular Activated Carbon
Adsorption Study. The adsorption capacities of Granular activated carbon and four different ordered
mesoporous carbon for resorcinol removal are shown in Fig. 4(a). It can be seen the tendency is OMC1 <
GAC < OMC2 < OMC3. Because all three ordered mesoporous carbon have the same surface function
231
group from the FT-IR analysis, so the main factor for this adsorption phenomenon is the various specific
surface area. The synthesis of OMC1 may be under unsaturated ratio of SBA-15 and Acrylic acid solution.
The OMC2 and OMC3 have saturated synthesis procedure which has more effective structure and larger
surface area so that their adsorption capacity is far higher than GAC.
The adsorption capacities of four modification of OMC3 are shown in Fig. 4(b). We can find only
the NH3H2O solution has increased the adsorption capacity of the ordered mesoporous carbon. This should
mainly reasoned the changed of the surface function group. Another reason is the acid-base property.
Because the resorcinol solution shows weak acid, so the alkaline solution modification has a better
adsorption capacity than the acid solution, and the change of the function group is according to this rule.
CONCLUSION
Ordered mesoporous carbon prepared at three different ratio of SBA-15 and Acrylic acid solution
were try to find the better ratio of the synthetic materials, and the OMC (3:1) has a higher specific surface
area due to the saturated structure. The TEM shows the SBA-15 and OMCs are highly ordered in hexagonal
structure and the modification did not damage the ordered structure. Based on the acid-base property,
NH3H2O immersing modification has increased the OMC’s adsorption capacity by changing the surface
function group of the ordered mesoporous carbon.
ACKNOWLEDGEMENT
This work was supported by the Louisiana Board of Regents under BORSF (2010-2015) LaSpace
and by NASA under award NNX10AI40H.
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D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Fredirckson, B.F. Chemlka, G.D. Stucky, “Triblock copolymer
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I. P.P. Cansado, P.A.M. Mourão⁎, A.I. Falcão, M.M.L. Ribeiro Carrott, P.J.M. Carrott, “The influence of
the activated carbon post-treatment on the phenolic compounds removal” Fuel Processing Technology
103 (2012): 64-70
Moreno-Castilla C, Carrasco-Marin F, Maldonado-Hodar FJ, Rivera-Utrilla J, “Effects of non-oxidant and
oxidant acid treatments on the surface properties of an activated carbon with very low ash content”,
Carbon. 36 (1997):145-151.
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ordered mesoporous carbons via a chemical oxidation approach” Microporous and Mesoporous
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Q. Liao, J. Sun, L. Gao, “Adsorption of chlorophenols by multiwalled carbon nanotubes treated with HNO3
and NH3” Carbon 46 (2008): 533-5
P. Vinke, M. van der Eijk, M. Verbree, A. F. Voskamp, H. van Bekkum, "Modification of the surfaces of a
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232
CHARACTERIZATION AND ABSORPTION BEHAVIOR OF AMMONIA AND METHYLENE

BLUE BY BIOCHAR DERIVED FROM COMMON REED.
Fengmin Li, Lun Lu*, and Zhi Liang

(Ocean University of China, Qingdao, Shandong, China)
Application of biochars to wastewater is suggested as a promising way for improving water quality. To
investigate the effect of pyrolysis temperature on biochar properties and the absorption behavior of ammonia
nitrogen and methylene blue, biochars were produced from anaerobically digested common reed at different
temperature.
The mass yield of biochar decreased with increasing pyrolysis temperature from 45.2% of the initial
dry weight at 300 °C to 30.0% at 600 °C, similar trend was found in terms of the content of H and O in
biochar. On the contrary, the C content and ash in biochar increased with increasing pyrolysis temperature,
and the pH value increased with increasing pyrolysis temperature from 6.48 at 300 °C to 10.01 at 600 °C.
The surface areas of biochars were 3.50, 4.20, and 2.37 at 300, 400, and 500 °C, respectively, however,
significantly high value of 192.60 was obtained when the pyrolysis temperature is 600 °C. Fourier transform
infrared spectroscopy results showed that no significant difference of function groups in biochars was found
between different temperatures.
Batch experiments were carried out for the sorption of ammonia and methylene blue onto biochars.
Specific factors considered in laboratory adsorption experiment included pyrolysis temperature (300, 400,
500 and 600 °C) and solid/solution ratio. Langmuir and Freundlich models both fit adsorption isotherms
well. Low-temperature biochars (≤400°C) showed appreciable ammonia adsorption, and the calculated
maximum monolayer adsorption capacity of ammonia was found to be 0.79mg/g for biochar derived at 300
°C, additionally, biochar derived at 500 °C showed the maximum monolayer adsorption capacity of 5.03
mg/g for methylene blue. The best solid/solution ratio for ammonia and methylene blue absorption was
0.8g/15ml and 0.05/12ml, respectively. Furthermore, significant reduction of ammonia release was found
when the biochar was applied to simulated river water contained contaminated sediment (p<0.01).
These results suggest that anaerobically digested common reed could be employed as low-cost
feedstock materials to produce high quality biochars, which could be used as adsorbents to remove ammonia
and methylene blue simultaneously in wastewater treatment.
233
ADSORPTION OF NICOTINE ON MAGNETICALLY SEPARABLE ORDERED

MESOPOROUS CARBONS IN AQUEOUS SOLUTION
Hsin-Yu Lin, Ya-hsuan Liou and Pei-Te Chiueh

(National Taiwan University, Taipei, Taiwan)
Nicotine (3-substituted pyridine, C10H14N2) is a highly toxic alkaloid which has been found in municipal
wastewater and claimed for a serious concern. Adsorption of nicotine on different adsorbents has been
examined and revealed the feasibility for removing nicotine from aqueous solution. Therefore, a novel
material, ordered mesoporous carbons (OMCs) with embedded metallic nickel (Ni) nanoparticles, was
synthesized to be used as adsorbents for improving the adsorption of nicotine in this study. The material
was prepared by a simple and low temperature (50℃) hydrothermal method which makes nickel particles
homogeneously dispersed in the carbon matrices, while the pore mesostructure remained intact. In addition,
the adsorption mechanism between OMC-Ni and nicotine were also investigated by different pHs and
temperature conditions. The results showed that the adsorption behavior was dependent on the isoelectric
point of OMC-Ni as well as the characteristic of nicotine. The amounts of adsorbed nicotine were
determined and interpreted by adsorption isotherm models. The OMC-Ni composites are demonstrated to
be effective molecular adsorbents for magnetic separation.
234
CLEANING METAL CONTAMINATED WATER USING PYROLYZED BANANA PEELS
Bluyé Demessie1, E. Sahle-Demessie2*, George A. Sorial1

(1. School of Energy, Environmental, Biological, and Medical Engineering, Environmental Engineering
Program, University of Cincinnati, Cincinnati, OH, USA; 2. Office of Research and Development,
National Risk Management Research Laboraotry, U.S. Environmental Protection Agency, Cincinnati, OH,
USA)
Adsorption of Cu(II), Pb(II), As(V), and Bacteria on banana peel that was sun-dried, ground and pyrolyzed
was studied and compared with that of commercial activated carbon, F-400. The morphology, physical, and
chemical properties of the adsorbents were measured. Pyrolysis of dried banana peels formed a porous,
large surface area adsorbent with strongly negative surface charges. A factorial design of 18 experiments
at two levels of four factors including mass of adsorbent, pH of the solution, tumbling time and initial Cu(II)
concentration, and two central points, were performed for each adsorbent. The equilibrium adsorption data
were analyzed, and the data for all the system compared with different isotherms: Langmuir, Freundlich,
Radke-Prausnitz, Dubinin–Radushkevich, and Reddlich-Peterson. Sorption kinetics obeyed pseudo-second
order equation. Fixed-bed column studies were undertaken to evaluate the performance of pyrolyzed banana
peel in removing Cu(II), Pb(II), As(V), and Bacteria, under varying operating conditions. The Thomas
model, the Bohart and Adams, Yoon–Nelson model, Clark model, Bed-depth/service time analysis (BDST)
model sorption model were employed to determine characteristic parameters such as depth of exchange
zone, time required for exchange zone to move its own height, adsorption rate, and adsorption capacity,
useful for process design. Extracting Cu(II), Pb(II), As(V), and Bacteria from contaminated water using
pyrolyzed banana peel is a low cost, efficient, and sustainable approach.
235
ION EXCHANGE/ADSORPTION/DESORPTION TO RECOVER NUTRIENTS FROM

CONVENTIONAL&SEGREGATED STREAMS OF DOMESTIC WASTEWATER
FOR FURTHER USE AS FERTILZER
Bilsen BELER BAYKAL

(Istanbul Technical University, Department of Environmental Engineering, Istanbul, TURKEY)
ABSTRACT: Sorption processes may be used to recover nutrients from domestic wastewater and its
segregated stream yellow water, which is mainly human urine. When clinoptilolite is employed as the solid
phase, while nitrogen in the form of ammonium can be recovered successfully when conventional combined
domestic wastewater is handled, it is possible to recover both ammonium and phosphorus when the liquid
phase is yellow water, or human urine. Efficiencies of recovery exceed 90% when conditions are favorable.
Through this route, not only wastewater will be used as a source of fertilizers, but also domestic wastewater
will be freed off its two of the problematic components (nitrogen and phosphorous).
INTRODUCTION
With the rising concern in sustainability, controlled use of resources and resource recovery has
been gaining more and more attention year by year. Ecological sanitation (ECOSAN) and stream
segregation options for wastewater management, which recommend segregated collection of domestic
wastewater at the source and processing of each stream to recover valuable material they contain, are recent
concepts to contribute to these efforts. Recovery of nutrients is one of the major topics within this realm.
The greatest majority of nutrients in domestic wastewater come from urine which constitutes about 1 % by
volume. Yellow water is one of the segregated streams of domestic wastewater and it consists mainly of
human urine. When segregation is not performed, urine mixes into the entire volume of domestic wastewater
to dissipate nutrients it contains into the entire volume.
One person excretes about 11 g N/day through urine. This corresponds to about 80 % of nitrogen in
conventional domestic wastewater. Likewise, around 1 gram of phosphorus is excreted by each person every
day, and this is about half of that discharged in domestic wastewater (Wach, 2007). These two nutrients
make up one of the foremost problems arising from domestic wastewater as they lead to eutrophication, not
to mention other problems like ammonia toxicity on fish and potential nitrate problem with drinking water.
Indeed nitrogen and phosphorus cause serious problems in terms of environmental pollution, yet they are
two of the primary elements of plant fertilizers which are required to produce crops to feed the seven billion
inhabitants of the globe. It has been reported that together with potassium therein, the global fertilizer
equivalent of human urine, amounts up to about 35% of the world demand. It had also been reported that
human excreta, i.e. urine and feces, produced on an annual basis contains that quantity of nitrogen-
phosphorus-potassium which is required to produce about 200 kg of cereals per person per year, which to a
large extent comes from urine (Wach, 2007). Hence, while human urine contains the majority of
problematic nutrients both as a segregated stream of yellow water and as a contributor of conventional
domestic wastewater from the perspective of pollution, it is a significant source of fertilizers too.
Most of the work in the literature on recovery of plant nutrients/fertilizers from household
wastewater is devoted to phosphorus recovery and struvite precipitation from urine. However, adsorption
and ion exchange using the natural zeolite clinoptilolite, followed by subsequent release through desorption
is an effective method for recovering both phosphorus and nitrogen from urine. When the same processes
are applied to conventional domestic wastewater, a comparable amount of nitrogen recovery may be
expected.
Clinoptilolite, which is used in agriculture as a soil conditioner, is a natural zeolite which is highly
selective towards ammonium. Additionally, it is a good adsorbent. For nutrient recovery both from
conventional combined domestic wastewater and from yellow water, nitrogen and/or phosphorus are first
loaded onto clinoptilolite through adsorption/ion exchange processes to be concentrated upon the solid
phase. Further use of the solid phase thus produced (exhausted clinoptilolite) is suggested as fertilizer where
plant nutrients concentrated on the surface are made available to plants upon elution into either irrigational
236
water or rain water through desorption. The governing processes in this practice are sorption processes,
namely, ion exchange, adsorption and desorption.
The aim of this paper is to review and discuss how sorption processes can be used in turning a waste,
i.e domestic wastewater, into a useful product, i.e. fertilizer. Within the scope of this paper, ion exchange/
adsorption/desorption will be discussed as a successful method for recovering plant nutrients from domestic
wastewater to convert what is conventionally known as a “waste” into a valuable source, while providing
an alternative route for pollution control. Specifically, recovery of nitrogen and phosphorus from
conventional domestic wastewater and one of its segregated streams, i.e. yellow water will be addressed
with emphasis on the latter.
OVERVIEW OF NUTRIENT RECOVERY FROM YELLOW WATER/CONVENTIONAL

DOMESTIC WASTEWATER AND SORPTION PROCESSES
Several processes have been proposed to recover nutrients from source separated yellow water, i.e.,
human urine. Struvite precipitation seems to be the most frequently studied process within those lines, and
a collection of papers may be found in the literature addressing this topic, for example, Ganrot et. al (2007)
and Ronteltap et. al. (2007). Through this method, phosphorus in urine may be recovered to a large extent
with minor amounts of accompanying ammonium recovery. The level of ammonium recovery is low in this
process, and frequently the nitrogen remaining in the liquid phase is removed through
nitrification/denitrification, not recovered (Zeeman et al 2008; de Graaff, et. al., 2011). This leads to a
waste of this valuable plant nutrient as it is converted into nitrogen gas which cannot be used by plants
directly.
Domestic Exhausted
wastewater / Adsorption clinoptilolite
yellow water
+ Clinoptilolite (alternative
Ion exchange
fertilizer)
(1) Removal/Loading
Exhausted
clinoptilolite Tap water Desorption Nutrient
(alternative + (irrigation) or
recovery
fertilizer) applied rain water
on soil
(2) Recovery
FIGURE 1. The concept of the use of sorption processes for nutrient recovery
In contrast to the loss of the majority of nitrogen with struvite precipitation, successful results of
ammonium recovery had been reported through processing with the natural zeolite clinoptilolite (Beler
Baykal et al., 2004; Bayram, 2005; Ganrot, 2007). Additionally, the process has given motivating results
for phosphorus removal from human urine (Kocaturk and Beler Baykal, 2012; Allar and Beler Baykal, 2013)
This phenomenon is highlighted by a combination of sorption processes, i.e., ion exchange/adsorption
followed by desorption, through which plant nutrients may be recovered to be used further as fertilizer for
agricultural and/or landscape purposes.
Although there are several successful examples of ammonium removal from domestic wastewater
through ion exchange with clinoptilolite in the literature (Beler Baykal et al, 1996; Beler Baykal and Guven,
1997; Beler Baykal, 1998; Nguyen and Tanner, 1998; Gisvold et al., 2000; Hedstrom 2001; Hedstrom and
Amofah, 2011), work on the recovery of nutrients through this route from combined domestic wastewater
is very limited. Nevertheless, Sari (2010) and Beler Baykal and Sari (2011) have shown that the process
was equally effective in terms of efficiency of nutrient recovery specifically for ammonium when combined
wastewater was employed instead of yellow water.
For nutrient recovery both from conventional combined domestic wastewater and from yellow
water, N and/or P are first loaded onto clinoptilolite through sorption processes to be concentrated upon the
237
solid phase. Further use of the solid phase, i.e. exhausted clinoptilolite, is suggested as fertilizer following
elution of the concentrated plant nutrients on the surface into either irrigational water of rain water, to be
made available to plants, as illustrated in the Figure 1.
Clinoptilolite is an effective cation exchanger which is especially selective for ammonium and the
process through which ammonium is removed is ion exchange (Yurtoglu,2007). Hence the form of nitrogen
which will undergo this reaction is the cationic form, i.e. ammonium. Since phosphorus will only exist in
the anionic form as phosphate, removal through ion exchange is not possible, and the governing reaction is
most likely adsorption, since clinoptilolite is also a good adsorbent. Finally, plant nutrients are made
available to plants through desorption from the surface with tap water during irrigation or rain water during
precipitation events, both of which are practically free of both ammonium and phosphates.
One important issue here is the successful execution of both ion exchange/adsorption and desorption
processes when final use as fertilizer is intended. Ion exchange/adsorption leg will be necessary for
removing plant nutrients from yellow water or conventional domestic wastewater, but this process by itself
is not sufficient to claim recovery for further use as fertilizer since those nutrients have to be released from
the surface to be made available to plant, and this is done through desorption.

In the experiments which are reviewed here, nitrogen and phosphorus in the liquid phase, either
urine or conventional domestic wastewater, is first transferred onto the solid phase, i.e. clinoptilolite,
subsequently they are eluted from the surface to be used further as fertilizer. Typical compositions are
presented in Table 1. The basic experimental set-up consists of a column used for loading the zeolite with
nutrients by processing with the wastewater, either conventional domestic wastewater or yellow water. After
exhaustion of clinoptilolite, the nutrient rich feed, domestic wastewater or yellow water, is terminated and
the column is then fed with tap water to mimic the case with irrigation. In this second step, nutrients on the
surface of the exhausted clinoptilolite are eluted into the tap water. This step is crucial as only after elution
can nutrients be readily used by plants.
The ion exchanger/adsorbent used is the natural zeolite, clinoptilolite, which is an aluminosilicate
which acts as a cation exchanger highly selective towards ammonium. Additionally, it is a good adsorbent.
Application of clinoptilolite in agriculture as a soil conditioner is common. The specific clinoptilolite used
was from Gordes region of Turkey with a typical cation exchange capacity range of 2.2 -2.6 meq/g. and the
typical composition was given by the manufacturer as 68.3% SiO2, 12.55% Al2O3, 1.03% Fe2O3, 0.02%
TiO2, 2.33% CaO, 1.09% MgO, 0.88% Na2O and 2.32% K2O. Preconditioning with sodium chloride was
applied to obtain the sodium form of the ion exchanger, which provides the highest capacity (Yurtoglu,
2009).
TABLE 1. Typical compositions of domestic wastewater (from the sewer line of the university) and
urine, all in mg/l unless otherwise stated
Parameter Domestic wastewater Fresh urine Stored urine

TKN 30-40 5700-7100 5750-7100
Ammonium 25-30 300-500 5700-7050
Total P 2-3 400-700 300-600
Ortho P 1-2 250-550
Potassium 9-14 200-1600 1200-1600
pH (pH units) 7-8 6-7 9-9.5
Electrical conductivity (µS/cm) 900-1000 15000-17000 33000-37000
COD 100-150 6500-7500
One important issue to observe for maintaining effective removal is to provide nitrogen in the liquid
phase in ionic form as ammonium. Although more of the nitrogen in conventional wastewater occurs as
ammonical nitrogen, the form of nitrogen in freshly excreted urine is organic, specifically urea to a great
extent, as may be observed from Table 1. Hence, urea has to be converted into ammonium first for the ion
exchange process to be effective. This can be accomplished through urea hydrolysis which may take days
238
to about a month to be completed depending upon prevailing conditions. In actual practice this occurs during
storage of urine which is recommended for hygienic purposes anyway. One other significant issue is the pH
as ammonical nitrogen is almost completely in the ionic form below pH 8 but will change to ammonia as
pH is increased. At higher pH’s like 10 or above, the predominant form is ammonia which will not undergo
ion exchange. For effective operation, pH’s below 8 is recommended.
RESULTS & DISCUSSION

When nutrients from yellow water or domestic wastewater are to be recovered via sorption proceses
with clinoptilolite, first ammonium and other plant nutrients are loaded onto the zeolite through adsorption
and/or ion exchange. Through this route, not only plant nutrients can be transferred from the liquid phase
onto the solid phase to be recovered in due time but also problematic nutrients are removed from the liquid
phase as clinoptilolite is exhausted. This will not only permit isolation of fertilizer ingredients from a natural
and renewable resource, i.e., from urine that is separately collected from the rest of the domestic wastewater
at its point of origin, but also free the domestic wastewater from the majority of nutrients in a sustainable
fashion as exhaustion occurs. The exhausted clinoptilolite may then be used as fertilizer provided that plant
nutrients can be released from the solid phase. This time the sorption process in action will be desorption.
It is proposed that the product, i.e. exhausted clinoptilolite, be applied onto the soil as
fertilizer. If the exhausted clinoptilolite is to be used as a solid phase fertilizer, plant nutrients on
the surface have to be released through desorption to make them available to plants. So the transfer
of nutrients from human urine onto clinoptilolite is a necessary condition. However, it is not
sufficient for claiming that the product is an effective fertilizer. Hence not only the removal through
adsorption/ion exchange but also desorption for the release of nutrients are essential for the
functioning of the product as a fertilizer.
Table 2 is prepared as a simple summary and a compact means of comparison. Nitrogen and
phosphorus are nutrients which can both be removed from yellow water and released back into irrigational
water. However, K is successfully removed from yellow water but not released into irrigational water. With
domestic wastewater, nitrogen can be recovered successfully but potassium and phosphorus cannot be
recovered appreciably.
Sorption processes are equilibrium processes and while higher liquid phase concentrations are
expected to result in higher surface concentrations, the concentration of the target adsorbate/ion in the liquid
phase plays an important role on desorption. The reason for negligible phosphorus recovery is probably due
to the very low concentration of this element in domestic wastewater at around 2-3 mg/L as compared to
that in urine with several hundred mg/L, as may be observed from Table 1. In terms of potassium, removals
up to 99% have been attained (Beler Baykal et al., 2009); however, no recovery could be observed upon
contacting with tap water, which mimics conditions of irrigation. This was due to the fact that tap water
was almost devoid of ammonium with concentrations lower than 0.5 mg/L but was relatively richer in
potassium with concentrations reaching 4 mg/L and would not permit the release of this ion upon desorption.
TABLE 2. Overall recoveries for nutrients from domestic wastewater and urine*
Ammonium Phosphorus Potassium
Domestic wastewater 86 – 94 % negligible < 10 %

Human urine 86 – 96 94- 96 % none with tap water
* Prepared based on Beler Baykal & Sari (2011), Beler Baykal et al (2011), Kocaturk & Beler
Baykal (2012)
Initial loading was previously demonstrated to be a priority parameter in the success of the process
and efficiencies exceeding 94% had been reported at initial loadings up to 10 mg ammonium/g clinoptilolite
in terms of ammonium, while 84% removal could be achieved with a loading of 15 mg ammonium /g
239
clinoptilolite (Beler Baykal et al., 2009). As initial loadings go beyond that value, overall efficiencies
decrease further.
Although recovery of nitrogen both from combined domestic wastewater and urine, and recovery
of phosphorus were demonstrated to be effective, the best way of measuring their potential is to test them
upon plants. Preliminary experiments performed on the landscape plant ficus elastica and grass have
provided data to demonstrate that the product, i.e clinoptilolite exhausted with nutrients from wastewater
was at least as effective as synthetic fertilizers.
CONCLUSIONS
Through the use of a series of sorption processes, “used water”, which is conventionally named as
“wastewater”, is not only cleared of two of its foremost pollutants, nitrogen and phosporus, but also used
as a source of fertilizers.
Lab scale experiments have revealed that over 90 % of both N and P can be removed both from
conventional and segregated domestic wastewater using clinoptilolite. Within this context, N should be
maintained in the form of ammonium as ion exchange is the predominating process in nitrogen removal,
and that initial loading of nutrients upon clinoptilolite is a major issue. From the perspective of release of
both nutrients from the exhausted clinoptilolite, over 90 % of the nutrients removed from conventional and
from yellow water could also be removed to be made available to plants. Preliminary experiments on ficus
elastica and grass have provided promising results to show that clinoptilolite exhausted with nutrients in
domestic wastewater were at least as effective as synthetic fertilizers.
In conclusion, ion exchange/adsorption followed by desorption provides a successful route for
recovering plant nutrients from domestic wastewater, in the conventional combined form and as a segregated
stream, i.e. yellow water, to convert what is conventionally known as a “waste” into a valuable source
while providing an alternative for pollution control, serving a two way benefit.
REFERENCES
Allar, A. D. and B. Beler Baykal. (2013) Phosphorus Recovery from Source Separated Human Urıne upon
Processıng with Clınoptılolıte. WEF/IWA Nutrient Removal and Recovery 2013, Vancouver, Canada.
Bayram, S. (2005) The Use of Clinoptilolite for Recovering Plant Nutrients From Separately Collected
Human Urine. MSc Thesis, Istanbul Technical University, Institute of Science and Technology, Istanbul,
Turkey (in Turkish with an extended summary in English).
Beler Baykal, B. 1998. Clinoptilolite and Multipurpose Filters for Upgrading of Effluent Ammonia Quality
Under Peak Loads. Water Sci. Technol., 37 (9): 234.
Beler Baykal, B. and D. Akca Guven. 1997. Performance of Clinoptilolite Alone and in Combination with
Sand Filters for the Removal of Ammonia Peaks from Domestic Wastewater. Water Sci. Technol., 35
(7): 47.
Beler Baykal, B., A. D. Allar, and S. Bayram. 2011. Nitrogen Recovery from Source Separated Human
Urine Using Clinoptilolite and Preliminary Results of its Use as Fertilizer. Water Sci. Technol. 63(4):
811-817.
Beler Baykal, B., S. Bayram, E. Akkaymak and S. Cinar, S. 2004. Removal of Ammonium from Human
Urine Through Ion Exchange with Clinoptilolite And Its Recovery for Further Reuse. Water Sci.
Technol., 50 (6): 149.
Beler Baykal, B., N. P. Kocaturk, A. D. Allar and B. Sari. 2009. The Effect of Initial Loading on the
Removal of Ammonium and Potassium from Source Separated Human Urine via Clinoptilolite. Water
Sci. Technol., 60 (10): 2515.
Beler Baykal, B., M. Oldenburg, and I. Sekoulov. 1996. The Use of Ion Exchange in Ammonia Removal
Under Constant and Variable Loads. Environ. Technol., 17, 717.
Beler Baykal, and B. Sari. 2011. An Investigation on the Recovery of Plant Nutrients from Clinoptilolite
Exhausted with Domestic Wastewater, IWA Small& Decentralized Wastewater Treatment Systems,
Venice 2011, April 18-22 2011, Venice, Italy.
Beler Baykal, B. Sari, N. P. Kocaturk, A. D. Allar. 2011. A Comparative Study of the Recovery of
Ammonium from Clinoptilolite Exhausted with Conventional Domestic Wastewater and with Source
240
Separated Human Urine, WEF/IWA International Conference on Nutrient Recovery and Management,
January 9-12 2011, Miami, USA.
de Graaff, M., G. Zeeman, H. Temmink and C. J. N. 2011. Resource recovery from Black Water Total
Concept and Outlook, WEF/I IWA Small& Decentralized Wastewater Treatment Systems, Venice
2011, April 18-22 2011, Venice, Italy.
Ganrot, Zs., G. Dave and E. Nilsson. 2007. Recovery of N and P from Human Urine by Freezing, Struvite
Precipitation and Adsorption to Zeolite and Active Carbon. Bioresource Technol., 98, 3112.
Gisvold, B., H. Odegaard and M. Follesdal. 2000. Enhanced Removal of Ammonium by Combined
Nitrification/Adsorption in Expanded Clay Aggregate Filters. Water Sci. Technol., 41 (4-5): 107.
Hedstrom, A. 2001. Ion Exchange of Ammonium in Zeolites: A Literature Review. J. Environ Eng.-ASCE,
127 (8): 673.
Hedstrom, A. and L. Rastas Amofah. 2008. Adsorption and Desorption of Ammonium by Clinoptilolite
Adsorbent in Municipal Wastewater Treatment Systems. J. Environ. Eng. Sci., 7 (1): 53.
Nguyen, M.L. and J.Tanner, 1998. Ammonium Removal from Wastewaters Using Natural New Zealand
Zeolites, New Zealand Journal of Agricultural Research, 41, 427-446.
Roneltap, M., M. Maurer and W. Gujer, W. 2007. Struvite PrecipitataionThermodynamics in Source-
separated Urine Water esearch 41(5): 977-984.
Sari, B. 2010. An Investigation on the Removal and Recovery of Plant Nutrients from Domestic Wastewater
Using Clinoptilolite, MSc Thesis, Istanbul Technical University, Institute of Science and Engineering
(In Turkish with a summary in English).
Wach F. G. 2007. SustainableWater Management and Ecological Sanitation, Zer0-M Lecture documents,
TUBITAK MAM, Gebze Turkey
Yurtoglu, A. 2007. The Effect of Mineralogical Characteristics on the Ammonium Removal
Capacities of Turkish Clinptilolites, MSc Thesis, Istanbul Technical University, Institute of Science and
Technology, Istanbul, Turkey (in Turkish with an extended summary in English).
Zeeman, G., K. Kujawa, T. de Mes, T., L. Hernandez, M. de Graaff, L. Abu-Ghunmi, L., A. Mels, B.
Meulman,H. Temmink, Buisman, C., J. van Lier, J and G. Lettinga, G. 2008. Anaerobic treatment as
a core technology for energy, nutrients and water recovery from source-separated domestic
waste(water), Water Sci. Technol., 57(8), 1207 12012.
241
ELUCIDATING THE ROLE OF PHENOLICS IN THE EFFECTIVENESS OF DOM

ADSORPTION ON ACTIVATED CARBON
Liang Yan and George. A. Sorial*

(University of Cincinnati, Cincinnati, OH, USA)
This research was conducted to investigate the impact of the presence of phenolics on the adsorption
capacity of DOM. Firstly, to enhance the adsorption of dissolved natural organic matter (DOM), two novel
tailored activated carbons (BC-41-OG and BC-41-MnN) with favorable physicochemical characteristics
were successfully prepared by applying systematically chemical and thermal treatment. Isotherm tests were
performed for both humic acid (HA) and phenolics on two novel tailored activated carbons and a commercial
activated carbon F400. The presence of phenolics display a significant effect on hindering the adsorption of
HA, however; the physicochemical characteristics of novel activated carbons (surface metal oxides and
mesoporosity) can play an important role in alleviating this effect. In contrast, F400, with a relatively lower
mesoporosity and surface basicity as compared to the developed adsorbents, was severely impacted by the
oligomerization of phenolic compounds.
242
REMOVAL OF FLUORIDE FROM WATER USING CHEMICALLY MODIFIED JUTE
Basudam Adhikari, Suvendu Manna, Prosenjit Saha, Debasis Roy, Ramkrishna Sen
(Indian Institute of Technology Kharagpur, WB, India)
ABSTRACT: Possibility of removing fluoride present in water using inexpensive, plant-based biosorbents
has been studied. The data indicate that untreated and transesterified jute could be effectively used as
biosorbents for removing fluoride. In essence, the process is an endothermic and spontaneous physical
adsorption driven by hydrogen bonding, protonation and van der Waals forces. Relevant batch study results
indicate that up to 98 % of F− present in distilled water spiked with 5 mg/L NaF could be removed using
only 0.8 g of transesterified jute biosorbent. In comparison, untreated jute could remove only 42 % of F−.
Although the process efficiency was higher at pH of about 5, transesterified jute biosorbent was found
capable of removing F− at a pH between 3 and 8. The F− removal efficiency of the transesterified jute was
found to be 1.8 times higher than that of untreated jute and 2.3 times that of activated alumina. The
biosorbents could be regenerated by washing with mild acid solution and the fluoride captured could be
immobilized in a virtually insoluble solid form. The process of fluoride removal by transesterified jute is
also advantageous because it does not produce sludge, increase water hardness, or release hazardous
leachates.
INTRODUCTION
Fluoride in groundwater originates from natural, fluorine-containing geological sources such as
granite, basalt, syenite, and shale (Apambire et al. 1997) or from industrial sources such as aluminum
smelters, ceramic and semiconductor industries, brick and iron works and beryllium extraction plants
(Reardon et al. 2000). Around 300 million people around world are reportedly consuming water with
fluoride concentrations above the WHO limits causing them to suffer from health problems (WHO, 1984;
Venkobachar et al. 1997).
Precipitation and coagulation of fluoride ions with alum, lime and calcium is often used for
removing fluoride from water (Venkobachar et al. 1997). Leached aluminum ions found in treated water
obtained from this process could be hazardous to human health (George et al., 2010). Fluoride has also
been removed from water through ion exchange, electro dialysis and reverse osmosis (Ndiaye et al., 2005),
although these processes are expensive to operate and maintain. All these processes generate bulk amounts
of toxic sludge, which are difficult to dispose.
Fluoride removal using activated alumina adsorbent has attracted attention of researchers for its
relatively high fluoride removal efficiency (Ghorai and Pant, 2005; Popat et al., 1994). Although the
activated alumina based fluoride removal process appears to be the most widely used in industrial and public
water supply, concerns about potential health hazard due to the presence are being raised by researchers
over recent years (George et al., 2010). Also, the process for manufacturing activated alumina adsorbent is
energy intensive and expensive. Bone charcoal, plant biomass charcoal, red soil, powdered brick, fly ash,
and serpentine mineral have also been used as adsorbents to remove fluoride from water (Mwaniki, 1992;
Sinha et al. 2003; Chidambaram et al., 2003). Low fluoride removal efficiency of these adsorbents
necessitates frequent adsorbent regeneration and scale removal. These processes also generate bulk amounts
of toxic sludge. Also, many of the adsorbents used in these processes are produced from energy intensive
processes.
An inexpensive, eco-friendly adsorbent with F− removal efficiency comparable to that of the
activated alumina based process could therefore be a preferable alternative. In this paper, jute treated with
inexpensive process was investigated for their potential F− removal efficiency.
243
Biomass and Its Processing. Locally sourced bust fiber of jute (Chorcorus olitorius) were washed with
distilled water, dried at 85±2 °C and chopped mechanically in a mixer grinder. Portions of these biomasses
were immersed in 0.5 % (w/v) aqueous NaOH (E. Merck, India) solution for 30 min at 30±2 °C followed
by steam treatment at 103 kPa for 30 min. Thereafter, the alkali treated biomasses were washed with
distilled water to bring down the pH to 7.0. A portion of alkali treated jute fibers was kept immersed for 15
min within an alkaline aqueous emulsion of neem oil and phenolic resins (pH 8), prepared by mixing sodium
hydroxide, cashew nut shell liquid, resorcinol, neem (Azadirachta indica) oil and formaldehyde in ratio
0.5:1:2:5:2 (by weight). Subsequently, the treated biomass was dried and cured at 105 ± 5 ºC for 1 h, washed
with ethanol to remove unreacted reagents and oven dried at 70 ± 2 ºC for 24 h.
Characterization of Biomass. Surface area of the biomass was measured following ASTM C204-07
(ASTM, 2007). For estimating point to zero charge, pHPZC, 0.5 g (dry) of the untreated or transesterified
jute powder was shaken separately with 50 mL aqueous NaCl solutions (0.01 M) within pH of 2 to 8 in a
shaker incubator (Scigenics, India model Orbitek LE) over 24 h at 35 °C and 120 rpm. The resulting pH
change, ∆pH , is plotted against the initial pH. The pHPZC is obtained from this plot as the pH value at the
zero value of ∆pH (Mullet et al., 1999).
Estimation of Fluoride. Fluoride in water was estimated by mixing F− containing water with lanthanum
alizarin fluoride blue solution in 1:10 (v:v) ratio and measuring the optical density at 570 nm in
spectrophotometer (Systronics 106) following USEPA 340.3 (1971). The reagents needed to prepare the
alizarin fluoride blue solution, viz., ammonium acetate, sodium carbonate, acetic acid, lanthanum oxide,
ammonium hydroxide, and alizarin blue indicator – were procured from Merck (India).
Batch Study. Batch study for investigating the influence of pH, temperature, contact time and biomass
amount on fluoride removal from water was carried out by mixing the biomass with 50 mL of distilled water
spiked with 5.0 mg/L of NaF and shaking at 120 rpm. Liquid sample was collected periodically for analysis
of F−. The F− removal efficiency, η (%), was calculated using
η = (Ci − Ct ) Ci × 100 (1)

−
where Ci and C t are the F concentrations at the beginning of an experiment and that at time t, respectively.
Non leachable polypropylene containers manufactured by Tarsons (India) were used in this study. Influence
of competitive anions on fluoride removal efficiency was also investigated by increasing the concentration
of anions, which are commonly present in groundwater, viz. carbonate, biocarbonate, sulfate, phosphate and
nitrate, in the distilled water spiked with 5 mg/L of fluoride.
Biomass Type and Particle Size. Amongst the biomasses used, transesterified jute was found to be the
most effective in removing F− (Table 1) from water.
Table 1. F− removal (%) from NaF (5 mg/L) spiked distilled water for 0.5 g of
biomass per 50 mL of influent (mean of three tests, std. dev. < 10 % of mean)
F− removal (%) of biomass for different particle size (μm)
Biomass
below 150 151-300 301-600 above 1000
Untreated Jute 42 31 39 32
Alkali treated Jute 59 46 46 45
Transesterified Jute 72 58 55 51
244
The removal efficiency,η, was also found to be maximum for biomasses with finer particle size.
The influence of physical and chemical environmental parameters on η for untreated and transesterified jute
powders were investigated further.
Influence of pH. F− removal efficiency was found to maximize at pH of 4 and 5 for untreated and
transesterified jute powders, respectively (Figure 1a). Removal efficiencies at other pH values were smaller.
pHPZC measured in this study indicated that the biomass surfaces were positively charged at pH below 4.2
for untreated jute powder and below 6.8 for transesterified jute powder due to protonation of surface groups.
It, therefore, appears that protonation of hydroxyl and carbonyl groups of untreated and transesterified jute
powder surfaces caused by H+ ions present in water contributed most for F− removal. Maliyekkal et al.
(2006) also observed a similar dependence of η on pH while removing fluoride from water with activated
alumina adsorbent and offered protonation of surface groups of the adsorbent as a possible explanation.
Although the process works well in acidic pH, transesterified jute biosorbent was found to remove F− over
pH between 3 and 8 (Figure 1a).
Figure 1. Influence of pH (a), biomass (b), temperature (c), time (d) and competitive anions (e) on
fluoride removal
Influence of Biomass Amount. Fluoride removal efficiency increased with increased biomass amounts
(Figure 1b). The increase in η was possibly due to increasing availability of active biomass sites with
increased biomass amount. Although η did not increase beyond 98 % because of relative lack of F− ions in
water vis-à-vis adsorbent amount. Also η for transesterified jute rose more steeply with increasing biomass
amount compared to that of untreated jute. A possible explanation for this observation is that the fatty acyl
chains grafted on cellulose macromolecules during transesterification led to the availability of a relatively
higher number of sites for F− capture.
Influence of Temperature. Fluoride removal efficiency was found to increase with temperature until about
35 °C and decrease thereafter (Figure 1c). The initial increase is possibly due to the endothermic nature of
the sorption mechanism responsible for F− removal (Gao et al., 2009) and/or enhanced F− diffusion rate
through the pores of biosorbent at higher temperatures (Wang et al, 2005). Reduction in F− removal
efficiency at temperatures higher than 35 °C was possibly because of weakening of attraction between F−
and biosorbent at higher temperatures (Sharma and Tomar, 2011).
Influence of Time. The F− removal efficiency of untreated and transesterified jute increased significantly
over the initial 180 min (Figure 1d). Thereafter no significant increase in η was noticed. This observation
could be explained by saturation of available active sites of biomass surface with F− within the first 180 min.
Influence of Competitive Ion. F− removal efficiency of treated and untreated biomass was found to
decrease with increasing concentrations of CO32−, HCO3−, NO3−, PO43− and SO42− (Figure 1e). The decrease
was most remarkable for HCO3− and SO42−. Hu et al. (2003) reported similar relative impacts of these anions
while studying F− removal with aluminum electrode and anion exchange membrane. Inhibited protonation
245
due to HCO3− related alkalinity and greater affinity of SO42− to protonated sites relative to other anion species
possibly caused HCO3− and SO42− to affect η more remarkably (Jolly, 1991).
Isotherms. To understand the interaction between F− and biomass, the batch study results were fitted to the
following form of Langmuir (1918) isotherm:
1 qe = 1 (k a × qm × Ce ) + 1 qm (2)
where qe is the amount of solute sorbed at steady state, k a is a constant that measures the net enthalpy, q m
is the estimated amount of solute that saturates a unit dry mass of sorbent, and Ce is the residual
concentration of the solute at steady state.
Batch study data were also fitted to the following form of Freundlich (1906) isotherm:
log qe = log k f + (log C e ) n (3)
where, parameters k f and 1/n relate to sorption capacity and sorption intensity, respectively.
The correlation coefficient, r2, values (Table 2) indicated that the data were fitted satisfactorily for
both the isotherms signifying that the fluoride removal process was surface driven.
Table 2. Isotherm and rate kinetic parameters and goodness of fit

Langmuir and Freundlich isotherm
Biomass ka qm kf
r2 1/n r2
(L.mg-1) (mg.g-1) (mg.g-1)
Untreated 2.14 2.7 0.90 1.76 0.57 0.85
Transesterified 1.40 4.2 0.98 1.94 0.64 0.96
The r2 value obtained from Langmuir isotherm is higher than that of the Freundlich isotherms,
indicating that the fluoride adsorption process by the jute biomasses was driven by monolayer adsorption.
The q m value for transesterified jute based process, 4.2 mg/g, was 2.3 times higher than that for the activated
alumina based process. It could therefore be inferred that a certain mass of transesterified biomass would
capture a larger mass of F− compared to an equivalent amount of activated alumina.
Table 3. Comparison of jute-based process with other alternatives

Cost
Sorbent (References) Disadvantages
($/kL)
Alum and lime (Venkobachar 1 to 2 (a) Process needs active maintenance, (b)
et al., 1997) Sludge generation, and (c) Increases water
hardness
Activated / modified alumina 1 to 3 (a) Expensive and energy intensive sorbent
(Venkobachar et al., 1997; production, (b) Al3+ released in water is
Popat et al., 1994; potentially hazardous (George et al., 2010), and
Maliyekkal et al., 2006) (c) spent sorbent difficult to dispose
Activated Charcoal 1 (a) Works at pH < 3, and (b) sorbent production
(Mwaniki, 1992) expensive and energy intensive
Red soil, brick powder, fly ash 1 (a) Low removal capacity, and (b) sorbent
(Chidambaram et al., 2003) regeneration is difficult
Water hyacinth activated High (a) Energy intensive sorbent production, (b)
charcoal (Sinha et al., 2003) works at pH < 3, and (c) high process and
sorbent regeneration costs
Reverse osmosis (Ndiaye et High (a) Expensive, and (b) continuous energy
al., 2005) requirement
Electro-coagulation (Ghosh et 0.9 (a) Electrode replacement per cycle and (b) Al3+
al., 2011) released in water
Transesterified jute biosorbent 0.6 ─
246
Sorption Energy. Sorption processes with enthalpy change, ΔH0, of less than 40 kJ/mol are often inferred
to be physical adsorption and ones with higher values to be chemical adsorption (Kara et al., 2003; Gao et
al., 2009). The ΔH0 values of jute based fluoride removal process at temperatures between 25 °C and 45 °C
were estimated from the the van’t Hoff equation, viz.,
ln(q e / C e ) = ∆S 0 R − ∆H 0 RT (4)
where, ΔS0 is entropy change, R is the universal gas constant and T is the absolute temperature scale (Kelvin).
The estimated ΔH0 was 30 kJ.mol−1, which indicated that the process was a physical adsorption. The positive
value of ΔH0 increased because the process was endothermic in nature (Gao et al., 2009). The change in
Gibbs free energy, ∆G0 was similarly estimated from
∆G 0 = − RT ln ( qe Ce ) (5)
leading to ∆G 0 ≈ −6.9 kJ.mol−1 at 308 K with the negative sign indicating the process to be spontaneous
(Sharma and Tomar, 2011).
Techno-Economic Status. Comparison of process costs of jute biosorbent-based F− removal with

alternative processes indicates the biosorbent-based process to be less expensive (Table 3). The biosorbent-
based process is also advantageous because it does not produce sludge, increase water hardness, or release
fluoride in alarming concentration.
CONCLUSIONS
F− removal process based on untreated and transesterified jute biosorbent has been developed. The
process involves physical adsorption to capture the fluoride ions from water. F− adsorption capacity of
transesterified jute was found to be higher than those of untreated jute as well as activated alumina.
Although the process works well in pH 5, transesterified jute biosorbent was found to remove F− from water
over pH between 3 and 8. The biosorbent could be regenerated by mild acid wash and the captured F− was
found to be amenable to immobilization in a virtually insoluble solid form. The process is inexpensive in
comparison to alternative F− removal processes.
ACKNOWLEDGEMENT
The second author would like to thank CSIR, India for the financial support he has received as a
Senior Research Fellow during this study.
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Apambire, W.B., Boyle, D.R., Michel, F.A., 1997. “Geochemistry, genesis, and health implications of
fluoriferous groundwaters in the upper regions of Ghana”. Environ. Geochem. 33:13–24.
ASTM, 2007. Standard test methods for fineness of hydraulic cement by air-permeability apparatus. ASTM
C204-07. West Conshohocken, PA, USA: American Society for Testing and Materials.
Chidambaram, S., Ramanathan, A.L., Vasudevan, S., 2003. “Fluoride removal studies in water using natural
materials”. Water SA. 29(3):339–344.
Freundlich, H.M.F., 1906. “Über die adsorption in lösungen.” J. Phys. Chem. 57:385–470.
Gao, S., Sun, R., Wei, Z., Zhao, H., Li, H., Hu, F., 2009. “Size-dependent defluoridation properties of
synthetic hydroxyapatite.” J. Fluorin Chem. 130:550–556.
George, S., Pandit, P., Gupta, A.B., 2010. “Residual aluminium in water defluoridated using activated
alumina adsorption – Modeling and simulation studies.” Water Res. 44:3055–3065.
Ghorai, S., Pant, K.K., 2005. “Equilibrium, kinetics and breakthrough studies for adsorption of fluoride on
activated alumina.” Sep. Purif. Technol. 42:265–271.
Ghosh, D., Medhi, C.R., Purkait, M.K. 2011. “Techno-economic analysis of the electrocoagulation of
fluoride containing drinking water. Toxicol.” Environ. Chem., 93(3):424–437.
Hu, C.Y., Lo, S.L., Kuan, W.H., 2003. “Effects of co-existing anions on fluoride removal in
electrocoagulation (EC) process using aluminum electrodes.” Water Res. 37:4513–4523.
247
Jolly, W.L. 1991. “Modern Inorganic Chemistry,” 2nd ed. McGraw-Hill, New York.
Kara, M., Yuzer, H., Sabah, E., Celik, M.S., 2003. “Adsorption of cobalt from aqueous solutions onto
sepiolite.” Water Res. 37:224–232.
Langmuir, I., 1918. “The adsorption of gases on plane surfaces of glass, mica and platinum.” J. Am. Chem.
Soc. 40:1361–1403.
Maliyekkal, M.S., Sharma, K.A., Philip, L. 2006. “Manganese-oxide-coated alumina: A promising sorbent
for defluoridation of water.” Water Res. 40:3497–3506.
Mullet, M., Fievet, P., Szymczyk, A., Foissy, A., Reggiani, C.J., Pagetti, J., 1999. “A simple and accurate
determination of the point of zero charge of ceramic membranes.” Desalination 121:41–48.
Mwaniki, D.L., 1992. “Fluoride sorption characteristics of different grades of Bone charcoal, based on batch
tests.” J. Dental Res. 71:1310–1315.
Ndiaye P.I., Moulin P., Dominguez L., Millet J.C., Charbit F., 2005. “Removal of fluoride from electronic
industrial effluent by RO membrane separation.” Desalination 173:25–32.
Popat, K.M., Anand, P.S., Dasare, B.D., 1994. ”Selective removal of fuoride ions from water by the
aluminium form of the aminomethylphosphonic acid-type ion exchanger.” React. Polym. 23:23–32.
Reardon, E.J., Wang, Y., 2000. “A Limestone Reactor for fluoride removal from wastewaters.” Environ.
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Sinha, S., Pandey, K., Mohan, D., Singh. P.K., 2003. “Removal of fluoride from aqueous solutions by
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Sharma, P., Tomar, R., 2011. “Sorption behavior of nanocrystalline MOR type zeolite for Th(IV) and Eu(III)
removal from aqueous waste by batch treatment.” J. Colloid. Interface. Sci. 362:144–156.
USEPA, 1971. “Fluoride by cholorimetry. Method no 340.3.” United States Environment protection
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Venkobachar, C., Iyengar, L., Mudgal, A. K., 1997. “Household defluorination of drinking water using
activated alumina.” In Dahi, E., Nielson M.J. (Eds.) Proceedings of 2nd International workshop on
fluorosis prevention and defluoridation of drinking water. Nezreth, Ethiopia, pp138–145.
Wang, S., Boyjoo, Y., Choueib, A., Zhu, Z.H., 2005. “Removal of dyes from aqueous solution using fly
ash and red mud.” Water Res. 39:129–138.
WHO, 1984. “Fluorine and fluorides.” Environmental Health Criteria 36, World Health Organization,
Geneva.
248
EFFECT OF EFFLUENT ORGANIC MATTER ON ORGANIC MICROPOLLUTANTS

SORPTION ONTO ACTIVATED CARBON
Caroline Soares-Pereira (LEESU, Créteil, France)1, Romain Mailler1, Adèle Bressy1, Emilie Caupos1,
Lila Boudahmane1, Mohamed Saad1, Johnny Gasperi1, Vincent Rocher (SIAAP, Colombes, France),
Gilles Varrault1
Wastewater treatment plants (WWTPs) discharges are a major pathway for the introduction of
micropollutants (MPs) to surface waters. To reduce the release of these substances into the aquatic
environment, advanced treatment processes, such as activated carbon adsorption can achieve higher and
more consistent MPs removal (Ternes et al., 2002; Margot et al., 2013). Activated carbon is often used in
drinking water, its pollutant removal efficiency has been assessed and effect of natural organic matter
(NOM) on pollutant sorption has been taken into account (Bjelopavlic et al., 1999; Newcombe et al., 2002;
Quinlivan et al., 2005; Humbert et al., 2008). In the case of WWTPs, use of activated carbon is much more
recent and the effect of effluent organic matter (EfOM) onto pollutants sorption is much less documented.
Prior knowledge acquired with NOM cannot be totally transposed because of the different physico-chemical
properties between NOM and EfOM. For example, EfOM is much less aromatic and present much more
nitrogen-containing functional groups than NOM (Pernet-Coudrier et al., 2011). These differences may
result in different effect of EfOM onto pollutant sorption compared to NOM and then further research is
required to determine the influence of EfOM on activated carbon MPs adsorption. The overall objectives of
this research are to develop a better understanding of the influence of EfOM on the sorption capacity of
powder activated carbon (PAC) and to enable this knowledge to be applied in tertiary wastewater treatment.
We focused our study on sulfamethoxazole (SMZ) which is a pharmaceutical product and on polycyclic
aromatic hydrocarbons (PAHs) which are common wastewater contaminants with very different physico-
chemical properties. These study has been carried out in the framework of a research program which aims
to assess the activated carbon adsorption as tertiary wastewater treatment in the “Seine Centre” WWTP
(900 000 equivalent inhabitant) in Parisian conurbation.
In a first step the PAC and EfOM were characterized. Electron microscopy, X-ray diffraction, BET
surface areas, micropore volumes and pore size distributions were determined and the point of zero charge
was assessed. Dissolved organic matter was characterized by UV-visible and 3D fluorescence
spectroscopies and its partition according to hydrophobic, transphilic and hydrophilic fractions was
determined (by fractionation on XAD resins).
In a second step, adsorption phenomenon was studied. Sorption of SMZ and PAH onto PAC has
been studied in the presence of EfOM or without EfOM. Isotherms were conducted with adsorbent PAC (at
10 to 1000 mg/l) in the presence of EfOM from Seine Centre WWTPs discharge. Stock solutions of 14C-
labeled sulfamethoxazole or PAH cocktail, composed with 16 Priority PAH were added to yield an initial
concentration of 500 ng/l. Langmuir and Freundlich adsorption isotherms were applicable and their
constants were evaluated. A mixing time of one week was sufficient to reach adsorption equilibrium. Upon
equilibration, adsorbents were separated from the liquid by filtration through glass microfiber GF/F filters
(pore size = 0.7 μm; Whatman) and SMZ and PAH in liquid phase were respectively measured by liquid
scintillation counting and gas chromatography/tandem mass spectrometry assay (GC/MS/MS).
Supplementary experiments were performed at different pH, ionic strength and in the presence of different
DOM natures for better understanding of the mechanisms and factors affecting the pollutant sorption onto
PAC.
For each molecule, removal rates are clearly dependent on DOM natures and on the chemical
properties of the substances (charge and hydrophobicity). The difference on the adsorption and role on the
fate of organic contaminants may be due to the possible fractionation of DOM and change of surface
chemistry of PAC due to EfOM coating. The perspective of this work is to supply a better management of
activated carbon tertiary treatment in order to help on the development of models for predicting the fate of
MPs through WWTPs.
249
REMOVAL OF EMERGING MICROPOLLUTANTS FROM WWTP DISCHARGES: IS

ACTIVATED CARBON ADSORPTION SUITABLE FOR WASTEWATER APPLICATION?
Romain Mailler (LEESU, Créteil, France)1, Johnny Gasperi1, Yves Coquet (SAUR, Guyancourt,
France)2, Cécile Cren-Olivé (ISA, Villeurbanne, France)3, Nathalie Cartiser3, Sifax Zedek1, Steven
Deshayes (LCPP, Paris, France)4, Adèle Bressy1, Emilie Caupos1, Régis Moilleron1, Ghassan Chebbo1 and
Vincent Rocher (SIAAP, Colombes, France)5
Despite conventional treatments, many micropollutants, such as pharmaceuticals, personal care products,
heavy metals, artificial sweeteners, etc., are still present in wastewater treatment plant (WWTP) discharges
at ng/L or µg/L range, representing a threat for the environment (Rogers 1996, Heberer 2002). Tertiary
treatments are currently developed because some micropollutants are resistant to primary and biological
treatments. Different kinds of technologies (membranes, oxidative processes, etc.) already exist, adapted
from drinking water industry. Adsorption on activated carbon is one of the most interesting regarding its
simplicity, efficiency for micropollutants (Margot et al. 2013, Boehler et al. 2012) and reasonable costs
(0.16 - 0.18 €/m3 ; (Abegglen and Siegrist 2012)).
In this context, the LEESU (Water, Environment and Urban Systems Laboratory), as a part of the
OPUR (Observatory of Urban Pollutants) research program and in close partnership with the SIAAP
(Parisian public sanitation service), launched this study on the CarboPlus® process (SAUR). This activated
carbon adsorption unit (1200 m3/d) is currently operating in a full-scale Parisian WWTP and is studied in
order to i) characterize its efficiency for both micropollutants and routine wastewater parameters (particles,
organic matter, carbon, nitrogen, phosphorus), and ii) examine the sorption mechanisms and the different
influencing parameters.
The process consists in a contact reactor where an activated carbon bed is fluidized by coagulant
and flocculant injection. In addition to powdered activated carbon (PAC), a new type of activated carbon
was tested. This innovative micro-grain has an intermediary size (300 - 400 µm) between powder (< 50 µm)
and grain (> 1 mm), is regenerated and can easily be recycled by the supplier, resulting in operation
simplification (no chemicals, higher solid retention time), cost reductions and avoiding the waste carbon
handling issue. Considering this, the selection of the process configuration (PAC or micro-grain) will then
be possible depending on each site situation and treatment requirements.
The study is organized in 3 phases. The first phase consists in an optimization of the pilot, where
different configurations (PAC dose, hydraulic retention time and nature of carbon) are tested, while the
second phase operates at a fixed configuration. Finally, the third phase allows testing the micro-grain
configuration. 30 inlet/outlet sampling campaigns are planned for a total period of 19 months. For each
campaign, a large number of organic pollutants (n=105) and heavy metals (n=17) are measured, including
pharmaceuticals, hormones, pesticides and regulated micropollutants. In addition, complementary analyses
were carried out during phase 2, including artificial sweeteners (n=4), parabens and triclosan (n=7), PAHs
(n=16) and phtalates (n=4). Routine wastewater parameters (dissolved organic carbon - DOC, biological
oxygen demand - BOD, total suspended solids, total nitrogen, total phosphorus, etc.) are also measured to
better understand and explain the performances.
This communication aims at presenting both micropollutants and routine wastewater parameters
results from phases 1 and 2 (PAC configuration), and the first results from phase 3 (micro-grain
configuration). Preliminary results tend to highlight a significant removal of micropollutants, especially
pharmaceuticals (40-90%), even for the most hydrophilic (log KOW < 4) ones such as antibiotics and beta-
blockers. The process allows an improvement of the macro-pollutants treatment, particularly DOC (25%),
BOD (38%) and UV absorbance at 254 nm (20-25%). Moreover, a clear influence of the PAC dose injected
and the hydraulic retention time can be highlighted. In addition, since micropollutants, DOC and UV-254
absorbance removals appears to be well correlated, the potential of using UV-254 measure as a control tool
of the process efficiency (SAUR patent) will be evaluated.
#1024, #1091
250
BIOSORPTION OF HEAVY METALS FROM AQUEOUS SOLUTION BY BACTERIA

Staphylococcus aureus and Bacillus spp.
Patel Ritixa, Tank Shantilal

(Department of Biosciences,Veer Narmad South Gujarat University,Surat – 395007, Gujarat, India)
ABSTRACT: Contamination of ground water and surface water by heavy metals is of concern for the
portability of water. Due to rapid industrialization, the frequency of water getting contaminated by heavy
metals is increasing. Biosorption is cheap and ecofriendly approach that utilizes microbes to concentrate
and to decontaminate water. Screened Staphylococcus aureus and Bacillus spp. were evaluated for
biosorption ability for Copper and Iron ions. It was found that bacteria were able to decontaminate water
with 95% of efficacy. Bacteria will have wide application in future and also should evaluate further. This
will be advantageous for effluent treatment plant to recover important heavy metals with low cost.
Key Words. Biosorption, Aqueous solution, Bacteria, Copper, Iron
INTRODUCTION
Due to the increased industrialization the amount and complexity of toxic waste effluents have
remarkably increased. Millions of gallon of water containing toxic heavy metals are generated annually
from several metal processing industries and discharged into the water bodies which are creating large
impact on the environment and public health. Removal of metals and their recovery is one of the major
concerns in sewage and industrial effluent treatment. The heavy metal of widespread concern to human
health are Hg, Cd, Pb, As, Cr, and Zn. It is estimated that over one billion human beings are currently
exposed to elevated concerntration of toxic metals and metalloids in the environment and several million
people may be suffering from subclinical metal poisoning.
Conventional methods for metal removal from aqueous solution include chemical precipitation, ion
exchange, adsorption process, membrane process, crystallization and electrochemical treatment, concerning
the cost, technical complexity and limitation of conventional methods make the alternative biological
methods more appealing. Various heavy metal ions have been concentrated, reduced and biosorped using
different biomaterils like algea, fungi, bacteria and activated sludge (Ashok et al., 2010; Mythili and
Karthikeyan, 2011; Razmovski and Sciban, 2008; Pavani and Sunil Kumar, 2013; Shookoohi et al., 2009).
Biological methods for metal removal include (1) Sorption of metal ions onto the surface of
microorganisms. (2)Intracellular uptake of metal ions and (3) Chemical transformation of metals on various
types of biomass has been introduced as a cost effective method. Biosorption can be defined as the selective
sequestering of metal soluble species that result in the immobilization of the metals by microbial cells. One
potential method was microbially catalyzed reduction of Fe(III) which was reported by number of
bacteria(Ashok et al., 2010; Mahendra and Maria, 2013).
Iron the common contaminant enters the water bodies like electroplating, mining, steel processing
etc. In galvanize industry metal plating and plating attribute to elevated iron concerntration..The presence
of copper ions in water poses serious environmental and human health hazards because of their toxicity,
tendency to bioaccumulate and abundance and persistance in environment. In this work, Staphylococcus
aureus and Bacillus species are used to test their ability for iron and copper uptake.
The main objective of this study was to investigate the potential of Staphylococcus aureus and
Bacillus species to accumulate the heavy metals and to use as bioremediating agent in situ. The effect of pH
on metal removal was also studied. This study is an attempt to provide a multipurpose alternative for waste
water treatment.
MATERIAL AND METHOD
Bacteria and Media: Bacterial species Staphylococcus aureus and Bacillus spp. isolated from soil sample
collected from galvanize industry. Cells were cultured in nutrient broth: beef extract 3.0g/L, peptone
251
10.0g/L, sodium chloride 5.0g/L and final pH adjusted to 7.4 – 7.6. Strains were maintained by subculturing
on nutrient agar. The cultures were stored at 4oC between transfer and subcultured before experimental use.
Microscopic and biochemical tests were applied to these isolates according to Bergy’s manual of systemic
bacteriology to determine the genus to which the isolates belong.
Metal solution: Heavy metals solutions of Fe(III) and Cu(II) were prepared with certain modification
(Deepti et al., 2012). A synthetic liquid media (1% Trypton, 0.5% Yeast extract and 0.5% NaCl) containing
150 mg/L of each Fe and Cu ions was prepared from their respective stock solutions (1000 mg/L). Chemicals
used for preparing these stock solutions were ferric chloride and copper sulphate. Stock solutions were
prepared using deionised water. Prior to addition, both the stock solution of metals and liquid media were
autoclaved separately at 1210C for 20 min. All the additions were performed aseptically.
Effect of pH on Biosorption: Experiments of heavy metals biosorption were carried out with certain
modification (Deepti et al., 2012) in the batch mode in the Erlenmeyer flasks containing 50 ml of synthetic
multi-element solution (15 mg % of each metal). Preior to addition of biosorbent inoculum to the solution
the samples were adjusted to different pH values viz. pH- 3,4,5,6,7,8 using 1M HCl and 1M NaOH
solutions. Samples were inoculated with overnight grown cultures of Staphylococcus aureus and Bacillus
spp. and incubated at 120 rpm for 48 hrs at 300C. After incubation period the cells were harvested by
centrifugation for 30 min at 5000 rpm. The residual metal concentration were measured by Atomic
Absorption Spectrophotometer (AAS).
RESULT AND DISCUSSION

Recent studies indicate that microbes might be used to remediate metal contamination by removing
metals from contaminated water or waste stream, srquestering metals in soils and sediments or solublizing
metals to aid in their extraction. This is primarily accomplished by biosorption of metals or enzymatically
catalyzed changes in the metal redox state.
The two isolates identified as Staphylococcus aureus and Bacillus spp according to Bergy’s manual
of systemic bacteriology were used for the biosorotion of heavy metals Iron and Copper. The pH of the
aqueous solution play an important role for metal sorption as it influences both the bacterial surface
chemistry as well as solution chemistry of soluble metal ions. Different metals show different pH optima
for their biosorption.
Table 1 shows the biochemical tests results for characterization of isolated microbes.
TABLE 1. Biochemical test of isolated microorganisms

Sr. Indole MR VP Citrate Urease Catalase Nitrate Oxidase Identified
No utilisation test Test reduction Organism/
1 - - + + - + + + Staphylococcus
aureus
2 - + - - - + + - Bacillus spp
Figure 1 shows % removal of heavy metals iron and copper by Staphylococcus aureus at pH
3,4,5,6,7,8. The maximum biosorption of iron was found at pH 5 and for copper ion it was found at pH-7
with removal efficacy of 93.7% and 80% respectively. These results are similar with previous researcher
report (Deepti et al., 2012).
Whereas figure 2 shows % removal of iron and copper ion by Bacillus spp. Maximum biosorption
of iron was found at pH-5 and for copper ion it was found at pH-4 with removal efficacy of 80% and 82%
respectively.
The result suggests that acidic pH was optimum for biosorption of iron and copper ion. Hence, both the
isolates have been identified as potential microbes for their application in metal removel in effluent
treatment.
252
The cell wall of Gram positive bacteria are efficient metal chelators and in Bacillus spp. The
carboxyl group of the glutamic acid of peptidoglycan was the major site of metal deposition. Teichoic and
teichuronic acids were important binding sites in Bacillus licheniformis. Staphylococcus aureus is also a
Gram positive bacterium and it has similar cell wall properties as of other Gram positive bacteria.
The possible mechanism of iron and copper ion removal by bacteria, isolated from galvanize
industry wastewater has been evaluated. Both the Staphylococcus aureus and Bacillus spp. Showed
excellent ability to reduce iron(93.7% and 80%) and copper ion(80% and 82) respectively. Hence, both the
isolates have been identified as potential microbes for their ability to reduce heavy metals from the industrial
wastewater.
100
% removal of metal ions
80
60
40 % removal of Fe
% removal of Cu
20
0
3 4 5 6 7 8
pH
FIGURE 1. % removal of Fe and Cu ions by Staphylococcus aureus
90
80
% removal of metal ions
70
60
50
40 % removal of Fe
30
% removal of Cu
20
10
0
3 4 5 6 7 8
pH
FIGURE 2. % removal of Fe and Cu ions by Bacillus spp
CONCLUSION
The microbes play a vital role in the biosorption of heavy metals. The present study demonstrated
the use of Staphylococcus aureus and Bacillus spp. in the waste water treatment. The process would not only
be economical but also eco-friendly and multipurpose as an alternative to conventional methods of
biosorption of heavy metals. This catabolic potential of microbes is enormous and is advantageous to
mankind for a cleaner and healthier environment through biosorption. However, further research is needed
to establish the process with specific attention.
ACKNOWLEDGEMENT
253
The authors are grateful to Department of Biosciences, Veer Narmad South Gujarat University,
Surat, Gujarat for his support, encouragement and for providing facility of total metal analysis.
REFERENCES
[1] Deepti P. S., Chandrashekhar J. C., and Rama K. B., 2012. “Biosorption of Heavy Metals from Aqueous
Solution using Bacillus licheniformis.”International Journal Pure and Applied Science and Technology,
10(2):12-19.
[2] Mythili, K., and Karthikeyan, B., 2011. “Bioremediation of Chromium [Cr(VI)] In Tannery Effluent
Using Bacillus spp and Staphylococcus spp.” International journal of Pharmaceutical & Biological
Archives. 2(5):1460-1463.
[3] Ashok, K., BalwantSingh B., Joshi V. D., 2010. “Biosorption of Heavy Metals by four acclimated
microbial species, Bacillus spp., Pseudomonas spp., Staphylococcus spp. and Aspregillus niger.”
Journal of Environmental Sciences, 4(12):97-108.
[4] Mahendra, A., Maria, L. K., 2013. “Binding Mechanism and Biosorption Characteristics of Fe(III) by
Pseudomonas sp. cells.” Journal of Water Sustainability. 3(3):117-131
[5] Shokoohi, R., Saghi, M. H., Ghafari, H. R., Hadi, M., 2009. “Biosorption of Iron from Aqueous Solution
by Dried Biomass of Activated Sludge”. Iranian Journal of Environmental Health Science &
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[6] Razmovski, R., and Sciban, M., 2008. “Iron(III) Biosorption by Polyporous squamosus.” African
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[7] Pavani, K.V., and Sunil Kumar N., 2013. “Adsorption of Iron and Synthesis of Iron Nanoparticles by
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254
ADSORPTION OF URANIUM, STRONTIUM AND CESIUM IN RADIOACTIVE

WASTEWATER BY MODIFIED ATTAPULGITE
Jie Yang, Na Guo, Jingsheng Wang, Haiyang Chen

(College of Water Sciences, Beijing Normal University, Beijing, China)
ABSTRACT: Natural attapulgite was modified in order to study the adsorption of U(VI), Sr(II) and Cs(I)
in wastewater. Both iron and magnesium salts were used as modifiers and the adsorptive properties also
were compared. The modified attapulgite with iron salt (I-ATP) had a better adsorption performance for
Sr(II) than the modified one with magnesium salt (M-ATP), while, they had basically same adsorption
capacity for U(VI) and Cs(I). The adsorption capacities of modified attapulgite had been examined in
batch experiments as a function of contact time, pH, temperature, oscillation rate, and solution
concentration. Linear method was applied for fitting adsorption data with Freundlich and Langmuir
isotherm equations. The enthalpy, Gibbs free energy and entropy for the adsorption of radionuclides
on modified attapuligte have been also calculated. It is found that adsorption processes of U(VI), Sr(II)
and Cs(I) on modified attapulgite were physical adsorption.
INTRODUCTION
With the long-term uranium mining in China, a large amount of low level radioactive effluent was
produced by nuclear industry facilities or nuclear power stations, which will reach to approximately
3,6000 m3 until 2020 and urgently need to be disposed (L. Xu, 2011). Thereinto, uranium, strontium
and cesium are the most abundant radionuclides in nuclear fission products that account for absolute
proportion (A.M. El-Kamash, 2008). These long-lived radionuclides are regarded as hazardous elements
for the environment and human health owing to their high chemical toxicity and radiation poisoning
(Z.J. Yi et al., 2013). Therefore, the safe disposal of the nuclear wastes, especially the radioactive
waste originating from the reprocessing of spent nuclear fuels, is a matter of great relevance and importance
(M.S. Murali and J.N. Mathur, 2002). Among all the technologies, the deep geological disposal is regarded
as one adequate way, which can provide appropriate protection for humans and environment. However,
the radionuclides may leak out and be transported with moving groundwater to cause irreparable harm
in certain constitution. In order to control the radionuclides from spreading outside, the study on backfill
and block materials in repository is urgently in need. And the low permeability, high sorption capacity
and plasticity characteristics of clays make them can be used as alternative barrier to radionuclide
migration (S.A. Adeleye et al., 1994).
Attapulgite (ATP) is a hydrated magnesium aluminum silicate present in nature as a fibrillar
silicate clay mineral containing ribbons of a 2:1 structure (J. Huang et al., 2007). Numerous studies have
been reported on the adsorption of inorganic and organic pollutants from aqueous solution by natural or
modified attapulgite (J.Zhang et al., 2009; J.H. Potgieter et al., 2006). T.Y. Chi et al. (2012) found that the
equilibrium absorption capacity of Co(II) on natural attapulgite is 5.04 mg/g and it is affected by contact
time, pH value, solid to liquid ratio, ionic strength, and contamination of fulvic acid. Compared with
the adsorption capacities of Sr(II) in natural attapulgite and modified attapulgite in previous literatures,
the latter is twice as much as the former (J.M. Wang and C.F. Yi, 2006 and 2012). Totally, natural and
modified attapulgite are very promising in application of radionuclides adsorption as new material.
In order to explore the adsorption ability of attapulgite to radionuclides, it was modified by iron
and magnesium salt (I-ATP and M-ATP) for the first time and applied to adsorb U(VI), Sr(II) and Cs(I) in
this study. The effect of contact time, pH, temperature, oscillation rate, and solution concentration were
analyzed. And thermodynamic parameters also were calculated to characterize the adsorption property.

The powder attapulgite was of 200 mesh size with a purity of 95%, obtained from Jiangsu, PR
China (Xuyi Huahong mining Co., Ltd). The U(VI) stock solution (1,000 mg/L) was offered by
255
Beijing Research Institute of Chemical Engineering and Metallurgy, and the Cs(I) and Sr(II) stock
solutions (1,000mg/L) were prepared by CsCl (Shanghai times biotechnology Co., Ltd) and SrCl2
(Tianjin bodi chemical Co., Ltd). FeCl3·6H2O and MgCI2·6H2O were fisher chemical (Shanghai
jinshan jingwei chemical Co., Ltd). Hydrochloric acid (HCl, 36-38%) and sodium hydroxide (NaOH) were
analytical reagent grade (Sinopharm Chemical Reagent Co.,Ltd, China). All the solutions were prepared
with distilled water.
The powder attapulgite was dispersed in distilled water with iron and magnesium salts
(FeCl3·6H2O and MgCI2·6H2O) at a fixed concentration, respectively. The suspensions were stirred for
30 min under magnetic stirring (H01-1B, Shanghai Mei Yingpu Instrument Manufacturing Co., Ltd, China)
at pH 7 (Orion 818, Thermo Scientific, America). Then the resulting suspensions were separated by
centrifuging at 3300r/min for 15min (SORVALL Biofuge primo R, Xiamen, China) which were washed
repeatly to remove the water soluble particles and then were filtered. The modified attapulgite was dried
(DHG-9123A, Hengyi Shanghai) at 313 K for 36-48 h, crushed and sieved to the particle size of 100-
mesh screen.
The batch adsorption experiments were conducted in a series of 50 mL conical flasks with 10 mL
of U(VI), Sr(II) and Cs(I) solutions at different concentrations, varying from 10.0 to 100.0 mg/L. The
solutions were mixed with 0.5000 g I-ATP and M-ATP, respectively, and before mixing with the adsorbent,
the pH of solutions were adjusted by 1 mol/L NaOH and 1.0 mol/L HCl. The samples were mechanically
shaken at fixed temperature and rotate speed for 48 h on a rotating shaker (ZHWY-100D/103D,
ZHCHENG, Shanghai, China). The supernatant solution was then centrifuged at 4000 rpm for 15 min. The
residual concentrations of Sr(II) and U(VI) were determined by inductively coupled plasma emission
spectrometer (ICP-ASE) (Elan 5000, Perkin-Elmer Sciex, America) and the residual concentration of Cs(I)
were determined by inductively coupled plasma emission spectrometer (ICP-MS) (SPECTRO AROCOS
EOP, SPECTRO Analytical Instruments GmbH, Germany).

The effect of the contact time, pH, temperature, oscillation rate, and solution concentration were
analyzed by a series of batch experiments. The results showed that the adsorption performances of U(VI),
Sr(II) and Cs(I) by modified attapulgtes were largely affected by contact time and pH value, while other
factors had just a slight effect on the adsorption capacity or even not.
120
120
100
100
removal rate (%)
80
removal rate (%)
80
60 60
40 40
20 20
0 0
0 10 20 30 40 50 0 20 40 60
Time (h) Time (h)
(A) (B)
Sr(II) Cs(I) U(VI)
FIGURE 1. Effect of contact time on sorption of radionuclides on I-ATP (A) and M-ATP (B)
Adsorption experiments were carried out in different contact times (0.5 h, 1 h, 3 h, 6 h, 12 h, 24

h, 48 h) with an adsorbent dose (0.5000 g) at pH 7 and temperature 298 K. It is observed (Fig. 1). The
absorbance of radionuclides on I-ATP and M-ATP were increased with contact time. The initial adsorption
rate of radionuclides on the modified attapulgites was rapid and thereafter gradual. The adsorption
256
equilibrium of U(VI) on the modified attapulgites was reached after 30 min and the U(VI) removal was
approximately 100%. The adsorption equilibrium of Sr(II) and Cs(I) on the modified attapulgites was
reached after 24 h and the removals of Sr(II) and Cs(I) on I-ATP and M-ATP were 86.3%, 90.0%, 67.8%
and 92.3%, respectively. It was noteworthy that 90% of the adsorbance of Sr(II) and Cs(I) on the modified
attapulgite occurred in the first 6 h. Therefore, I-ATP and M-ATP both were efficient adsorbents for the
removal of U(VI), Sr(II) and Cs(I).
120 120
100 100
removal rate (%)

removal rate (%)
80 80
60 60
40 40
20 20
0 0
0 5 10
pH 0 5 pH 10 15
(A) (B)
Sr(II) Cs(I) U(VI)
FIGURE 2. Effect of pH on sorption of radionuclides on I-ATP (A) and M-ATP (B)
The adsorption performances of radionuclides by adsorbents were investigated with a wide pH range
of 1.0-13.0 (Fig. 2). It was observed that each radionuclide sorption process was dependent on the initial pH
of the solution and the uptake increases with the increase of value below pH value of 7.0. For the amount of
H+ would compete with radionuclides, so the adsorption sites were decreased. The highest uptake of U(VI)
by the modified attapulgites was observed at pH range of 7.0-13.0. And the monovalent hydrolyzed ions,
such as UO2OH+ and (UO2)3(OH) +, occured as the dominant uranium species which had competitive
adsorption with H+ at low pH (Pinaki Sar et al., 2004). The highest5 uptake of U(VI) at pH 7.0-13.0 was
due to the predominance of (UO2)3(OH)5+, (UO2)3(OH)3+, and UO2OH+ which will be more complex
with the modified attapulgite. At the highest pH value (13.0) the increased sorption of Sr(II) by the modified
attapulgite could be due to the formation of SrCO3 precipitate.
In order to study the surface properties and affinity of the adsorbents, it was important to utilize
the isotherms to describe the relationship between adsorbate amount on adsorbents and the concentration
of dissolved adsorbate in the liquid at equilibrium (J. Peric et al., 2004). The sorption data of radionuclides
at 298 K was fitted by the linear form of the Langmuir isotherm equation:
ρe 1 ρ+e
=
qe K L q m qm (1)
The sorption data was also fitted to the Freundlich isotherm equation:
(2)
257
where ρe= equilibrium mass concentration (mg/L); qe= equilibrium adsorption capacity (mg/g); qm=
monolayer adsorption capacity (mg/g); KL= affinity constant related to the energy of adsorption (L/mg);
KF= Freundlich constant related to the adsorption capacity of sorbent; 1/n= Freundlich exponent related to
adsorption intensity (dimensionless). The results were shown in Tab.1.
TABLE 1. The Langmuir and Freundlich constants for the adsorption of radionuclides on ATP
I-ATP M-ATP
Element Langmuir Freundlich Langmuir Freundlich
T
(K)
R2 qm KL RL R2 KF 1/n R2 qm KL RL KF 1/n
U(VI) 0.83 1.20 4.95 0.002 0.38 0.09 0.81 0.41 3.16 2.81 0.002 0.92 0.22 6.62
Sr(II) 298 0.96 1.60 2.15 0.005 0.67 0.37 0.12 0.72 1.14 5.07 0.004 0.56 0.39 0.04
Cs(I) 0.99 1.68 0.18 0.051 0.81 0.28 0.10 0.89 0.95 1.20 0.016 0.80 0.43 0.42
The correlation coefficients (R2) indicated that the adsorptions of U(VI), Sr(II) and Cs(I) on I-ATP were
fit in with the Langmuir isotherm better than Freundlich isotherm. While, the adsorption of U(VI) on M-
ATP was better fitted in with Freundlich isotherm, and the adsorptions of Sr(II) and Cs(I) by it were
better fitted in with Langmuir isotherm.
In order to gain insight into the thermodynamic nature of sorption process, several
thermodynamic parameters for adsorption were calculated and shown in Tab.2. ΔH and ΔS were
calculated from the slope and intercept of the plot of lnK versus 1/T.
ln K = −∆H / RT + ∆S / R (3)
And the standard Gibbs free energies(ΔG) were calculated by equation (4):
∆G = −RT ln K (4)
TABLE 2. Thermodynamic parameters of radionuclides at different temperature

I-ATP M-ATP
element ΔG((KJ/mol)) ΔG((KJ/mol))
ΔH ΔS ΔH ΔS
KJ/mol J/mol·k kJ/mol J/mol·k
278K 288K 298K 313K 278K 288K 298K 313K
U(VI) 9.327 40.834 -1 -3.3 -3.963 -2.4 5.234 4.732 4.236 3.488 3.71 3.976
Sr(II) 17.301 63.856 -0.2 -1.2 -1.905 -2.5 16.831 66.95 -1.49 -2.21 -4 -3.62
Cs(I) 11.669 24.776 4.92 4.53 4.141 4.01 14.357 48.409 -1.04 -0.56 -0.4 -
0 .6
ΔG in the adsorption processes of U(VI) and Sr(II) on I-ATP were negative at all temperatures, which
indicated the feasibility of process and spontaneous nature of adsorption. So were the adsorption
processes of Sr(II) and Cs(I) on M-ATP. The absolute value of ΔH in all process was less than 41kJ/mol,
so all of adsorption processes belonged physical adsorption.
CONCLUSIONS
I-ATP and M-ATP have remarkable adsorption property to U(VI), Sr(II) and Cs(I).
Furthermore, I-ATP has better adsorption capacity for Sr(II) than M-ATP, and they have basically same
adsorption capacity for U(VI) and Cs(I). The adsorption performances of U(VI) and Sr(II) on the
modified attapulgite are largely affected by pH value and contact time, and the adsorption performance will
258
rising with the increasing of pH under acid condition. However, they are slightly affected by
temperature, oscillation rate and solution concentration.
So far, the research in this paper focused on the modification methods of attapulgite and the
chemistry factors of the adsorption performance, but research about the adsorption mechanisms of
radionuclides on attapulgite are still insufficient. The reveal of adsorption mechanism will help to
find out better modification methods accurately and the relative research need to be enhanced in the future.
ACKNOWLEDGEMENTS
This work was financially supported by the Natural Science Foundation of China (No.
41372233).
REFERENCES
L Xu. 2011. “The review of nuclear radioactive waste treatment and disposal in China”. Defence
Science & Technology Industry. 05: 35-37.
A.M. El-Kamash. 2008. “Evaluation of zeolite A for the sorptive removal of Cs+ and Sr2+ ions from
aqueous solutions using batch and fixed bed column operations”. Journal of Hazardous Materials.
151(2-3): 432-445.
Z. J. Yi, J. Yao, F. Wang and H. L. Chen. 2013. “Removal of uranium(VI) from aqueous solution by
apricot shell activated carbon”. Journal of Radioanalytical and Nuclear Chemistry. 295(3): 2029-2034.
M.S. Murali and J.N. Mathur. 2002. “Sorption characteristics of Am(III), Sr(II) and Cs(I) on bentonite and
granite”. Journal of Radioanalytical and Nuclear Chemistry. 254(1): 129-136.
S.A. Adeleye and P.G. Clay. 1994. “Sorption of caesium, strontium and europium ions on clay
minerals”. Journal of Materials Science. 29(4): 954-958.
J.H. Huang, Y.F. Liu, Q.Z. Jin, X.G. Wang and J. Yang. 2007. “Adsorption studies of a water soluble dye,
Reactive Red MF-3B, using sonication-surfactant-modified attapulgite clay”. Journal of Hazardous
Materials. 143(1-2): 541-548.
J.H. Potgieter, S.S. Potgieter-Vermaak and P.D. Kalibantonga. 2006. “Heavy metals removal from
solution by palygorskite clay”. Minerals Engineering. 19(5): 463-470.
J. Zhang, S.D. Xie and Yuh-Shan Ho. 2009. “Removal of fluoride ions from aqueous solution using
modified attapulgite as adsorbent”. Journal of Hazardous Materials. 165(1-3): 218-222.
T.Y. Chi, Y.T. Chen, D.D. Shao, W. Zhang and X. Liu. 2012. “Sorption of Co(II) on attapulgite：
effects of time, solid-to-liquid ratio, pH, ionic strength and humic acid”. Journal of Radioanalytical
and Nuclear Chemistry. 34(6): 347-351.
J.M. Wang and F.C. Yi. 2006. “Studies on adsorption capacity of modified attapulgite to simulated
nuclide strontium”. Technology of Water Treatment. 32(10): 25-28
J.M. Wang and F.C. Yi. 2012. “Competitive adsorption properties and characterization of mineral
materials to Sr2+ and Cs+”. Atomic Energy Science and Technology. 46 (2): 165-171
Pinaki Sar, Sufia K. Kazy and S.F.D Souza. 2004. “Radionuclide remediation using a bacterial
biosorbent”. International Biodeterioration & Biodegradation. 54(2-3): 193-202
J. Peric, M. Trgo and N. Vukojevic Medvidovic. 2004. “Removal of zinc, copper and lead by natural
zeolite-a comparison of adsorption isotherms”. Water Research. 38(7):1893-1899
259
BIOINSPIRED GRADIENT-STRUCTURE FIBERS FOR WATER COLLECTION AT MICRO-

AND NANO-LEVEL
Yongmei Zheng
(Beihang University, Beijing 100191, PR China)
Biological surfaces in natural environment that collect water have evolved unique mechanisms, such as the
capture silk of the cribellate spider, which collects water through a combination of multiple gradients in a
periodic spindle-knot structure after wet-rebuilding process. Such structures drive tiny water droplets
directionally toward the spindle-knots for highly efficient water collection. Inspired by the roles of micro-
and nanostructures in the water collecting ability of spider silk, a series of functional fibers with unique
wettability has been designed by using nanotechnology-related coating methods, where the “spindle-
knot/joint” structures demonstrate the cooperation of multiple gradients in driving tiny water drops. Water
can be collected at the micro- and nano-level, for instance, the geometrical-engineered thin fibers display a
much higher water capturing ability than normal fibers in fog flows. The bead-on-string heterostructured
micro-fibers are capable of intelligently responding to environmental changes in humidity, investigated
inside environmental scanning electron microscopy. The tiny water droplets can be controlled the transport
in directions by designing the temperature, photo, rough-responded surfaces on fibers. The continuous size
spindle-knots fiber can realize the droplet transport in a long distance for water collection in efficiency. The
studies pave a route to design new materials that can be extended into fields of fog-water engineering in
special humid environment.
*Email: zhengym@buaa.edu.cn
260
ADVANCED OXIDATION METHODS-FENTON PROCESS FOR DYE REMOVAL IN

TEXTILE WASTEWATER
Macid Nurbas* and B. Sirin Kutukcuoglu

(Eskisehir Osmangazi University, Eskisehir, Turkey)
The wastewater originated from textile and dye industries causes serious pollution and damages the
ecological balance. So treatment of textile wastewater is important. Advanced oxidation methods like
Fenton process draw attention for dye removal in textile wastewater. In Fenton process low concentration
of Fe+2 and H2O2 uses and this Fenton reagents generate OH radicals which get high oxidation potential
Fenton process is very effective, less polluting, non-toxic and harmless reagent are used at low
concentration, so chosen for the treatment of colored water.
In this study, degradation of azo dyes like Acid Red 88(AR 88) was investigated by Fenton process.
Study was completed in two stages. At the first stage, aqueous solutions which was prepared by Acid Red
88 dye, was decolorized by Fenton process and determined the optimum conditions for effective
discoloration. At the second stage of study, Fenton process was repeated by continuous system. It was
found that efficiency of degradation obtain was about % 99.5 for batch and continuous systems. The
experimental results showed that the Fenton's reagent was effective for the degradation of acid red 88 dye
with a low concentrations of H2O2 and Fe2+ ion.
261
UNCONVENTIONAL OIL CONTAMINATED INDUSTRIAL EFFLUENT TREATMENT BY

CATALYZED HYDROGEN PEROXIDE AND SODIUM PERSULFATE
Niina Dulova, Eneliis Kattel, Marika Viisimaa, Anna Goi, Deniss Klauson, and Marina Trapido (Tallinn
University of Technology, Tallinn, Estonia)
Alar Saluste and Taavo Tenno (University of Tartu, Tartu, Estonia)
ABSTRACT: Ferrous ions activated hydrogen peroxide and persulfate were studied for the treatment of
industrial effluent heavily contaminated with unconventional oil (shale oil) rich in water soluble phenols.
Laboratory studies were conducted to evaluate and compare the wastewater treatment efficacy as well as
the potential of the subsequent biological treatment. The Fenton process demonstrated greater organic load
removal, biodegradability improvement and toxicity reduction than activated persulfate system. On the
other hand, the use of activated persulfate process was more favorable due to the exothermic effect intrinsic
to the Fenton reaction, which resulted in fast increase in temperature of the wastewater, along with excessive
foam formation. Overall, the application of a COD/oxidant/Fe2+ weight ratio of 1/0.4/0.075 resulted in COD
removal of 58 and 50%, the BOD7/COD ratio increase up to 0.3 and 0.23, and in 6.5-fold and 2.9-fold EC50
increase for H2O2/Fe2+ and S2O82-/Fe2+ process, respectively. The stepwise addition of the oxidant and
activator was favorable for the Fenton process and resulted in negligible wastewater treatment efficacy
improvement in activated persulfate system. The chemically pre-treated effluent, preferably diluted by
domestic wastewater, could be subsequently subjected to conventional biological treatment.
INTRODUCTION
Oil shale is an immature source-rock which contains relatively large amounts of organic matter
with elemental composition including mainly carbon, hydrogen, oxygen and small amounts of sulfur and
nitrogen. During the thermal processing of such material by a hot recycled solids technology it is heated to
500-550 °C to yield unconventional oil by pyrolysis. By-products of this process are gas, process water and
solid residue. Wastewater effluents of an oil shale thermal treatment can be characterized as follows:
wastewater from hydraulic ash removal, phenolic water and precipitation water from the industrial site. The
first wastewater is used in a closed cycle and the phenolic wastewater, which is formed during the
condensation of vapor, is directed to boilers for further incineration. However, due to the high energy cost
the scale of incineration is quite limited. Thus, to solve the problem of the phenolic wastewater processing
the alternative solution for its treatment has to be found.
The application of advanced oxidation technologies (AOTs) is a viable solution for destruction of
virtually all persistent organic pollutants presented in industrial highly loaded wastewater (Klavarioti et al.,
2009; Martins et al., 2011; Oller et al., 2011). The AOTs strength relies on the generation of the highly
reactive hydroxyl radicals (•OH) which are considered to react fast and non-selectively with the majority of
organic contaminants. The oxidation of organic pollutants by persulfate (S2O82-) has been studied as an
alternative to conventional •OH-based AOTs (Chen and Su, 2012; Hussain et al., 2012; Fang et al., 2013;
Moussa and Serge, 2014). The decomposition of persulfate via heat, ultrasound or UV light activation,
transition metal activation, alkaline activation (pH>10), or peroxide activation proceed with the generation
of more powerful sulfate free radicals (SO4•-) (Tsitonaki et al., 2010; Chen and Su, 2012). Different from
hydroxyl radicals, sulfate radicals are more selective for oxidizing unsaturated bond and aromatic
constituents (Chu et al., 2011).
In this study, the efficacy of the Fenton process and S2O82-/Fe2+ system as the advanced chemical
treatment of the unconventional oil heavily contaminated industrial effluent was assessed and compared.
262
The objective was to reduce the organic content, increase the biodegradability and reduce the toxicity
making the subsequent biological treatment more practical. The Fenton process is one of the most attractive
wastewater treatment methods among the conventional AOTs because of its high efficacy in organic
contaminants removal and harmless reagents (Eqs. (1) and (2)) used to generate •OH (Bautista et al., 2008;
Trapido et al., 2009). However, the Fenton treatment has a few restrictions during its application for a highly
loaded wastewater purification, including: elevated temperatures due to the exothermic nature of the Fenton
reaction (Eq. (1)) and excessive foam production through CO2 and O2 evolution, the latter is a result of
thermal decomposition of H2O2 (Bautista et al., 2008).
Fe2+ + H2O2 → Fe3+ + •OH + HO- (1)
Fe3+ + H2O2 → Fe2+ + HO2• + H+ (2)
The application of treatment methods based on similarly powerful, but less aggressive S2O82-/SO4•-
may help to overcome the above-mentioned problems. The reaction of S2O82- with Fe2+ for the generation
of sulfate free radicals (Eq. (3)) is similar to the Fenton reaction (Eq. (1)) and probably the most preferable
for environmental protection application among other activation techniques (Tsitonaki et al., 2010).
Fe2+ + S2O82- → Fe3+ + SO4•− + SO42- (3)
The results obtained within this study enlarge the knowledge of the ferrous ion activated persulfate
applicability to treat highly loaded wastewater and give valuable information for subsequent use in in-situ
chemical oxidation (ISCO) practice.
Chemicals and Materials. Hydrogen peroxide (PERDROGEN™, ≥30%), sodium persulfate (Na2S2O8,
≥99%) and ferrous sulfate heptahydrate (FeSO4∙7H2O, ≥99%) were purchased from Sigma-Aldrich. All
other chemicals were of reagent grade and used without further purification. Ultrapure water (Millipore
Simplicity® UV System) was used to prepare the stock solutions.
The studied effluent was a phenolic wastewater formed during a condensation of vapor from an oil
shale thermal processing obtained from an oil shale thermal treatment plant (the wastewater is rich in
phenols such as phenol, p-cresol, dimethylphenols, resorcinol, 5-methylresorcinol and 2,5-
dimethylresorcinol). The phenolic wastewater was characterized by a high organic load (COD 39700±1700
mg/L, DOC 9010±25 mg/L), a low biodegradability (BOD7/COD 0.14), a high concentration of total
phenols (730±15 mg/L), an alkaline pH value (8.88±0.04), an extremely high acute toxicity to Daphnia
magna (EC50 0.34±0.03%) along with a high inhibition of oxygen consumption by activated sludge (IC50
1.7%) and nitrification efficacy (IC50 0.35%).
Experimental Procedure. All the Fenton and persulfate oxidation trials were performed in batch mode
and in non-buffered solutions at ambient room temperature (21±1 °C). Wastewater samples (0.5 L) were
treated in 1 L cylindrical glass reactor with a permanent agitation speed (400 rpm) for a period of 24 h. The
activator (FeSO4·7H2O) was added first, and after its complete dissolution the oxidation was initiated by
adding H2O2 or S2O82- at once. A stepwise addition of the activator, oxidant (H2O2 or S2O82-) and
activator/oxidant after 0, 30 and 60 min of oxidation was examined as well. The pH of the wastewater
samples was not adjusted in the subsequent treatment, if not specified otherwise. The oxidation was stopped
by addition of NaOH (10 M) to adjust the treated samples pH to ~9. This process was followed by a settling
period of 24 h. Finally, the supernatant was collected for further analysis. The experiments on wastewater
oxidation with non-activated hydrogen peroxide and persulfate were conducted in identical reactors and
treatment conditions for the respective activated oxidation trials. All experiments were duplicated; the
results of the analysis are presented as the mean with a standard deviation.
263
Analytical Methods. The chemical oxygen demand (COD) was determined with a closed reflux
colorimetric method (APHA, 2005). A 7-day biochemical oxygen demand (BOD7) was determined
according to APHA (2005). The pH was measured using a digital pH meter (Schott CG-840, Germany).
The residual hydrogen peroxide concentration in the treated samples was measured by a spectrophotometric
method with Ti4+ (Eisenberg, 1943) by a Heλios-β UV/VIS spectrophotometer (Thermo Electron
Corporation, USA). The residual persulfate concentration in the treated samples was measured
spectrophotometrically at 446 nm with o-dianisidine (Sof’ina et al., 2003). The dissolved organic carbon
(DOC) was measured in filtered (Puradisc Aqua, 0.45 μm, CA membrane) wastewater samples by a TOC
analyzer multi N/C® 3100 (Analytik Jena, Germany). The acute toxicity of the initial and treated samples
to Daphnia magna (Cladocera, Crustacea) was measured with DAPHTOXKIT F™ MAGNA
(MicroBioTest Inc, Belgium) by a 24-h toxicity test. The measurements on inhibition of oxygen
consumption by activated sludge and nitrification efficiency were performed according to ISO 8192 (2007)
and ISO 9509 (1989), respectively.

During the iron-activated hydrogen peroxide or persulfate treatment of wastewater samples, both
the oxidation and coagulation of ferric-hydroxy complexes contribute to the removal of the organic
contaminants. In this study, all measurements of the observed parameters were performed after 24-h
oxidation followed by 24-h sedimentation.
FIGURE 1. COD removal and the BOD7/COD ratio versus the COD/H2O2/Fe2+ weight ratio in the
Fenton treatment.
The optimization of oxidant to contaminant ratio is an essential step in improvement of the Fenton-
based oxidation treatment efficacy. The results of the treatment of wastewater with different COD/H2O2
weight ratios are presented in Fig. 1. In these trials, the weight ratio of H2O2/Fe2+ was maintained at 5:1,
which is the optimal for a highly loaded wastewater treatment (Trapido et al., 2009). An increase in the
H2O2/COD ratio led to an improvement in organic load removal (COD, DOC) and biodegradability
(BOD7/COD) of the treated wastewater samples. Irrespective of hydrogen peroxide dose applied, the
mineralization was lower than COD removal. Thus, at a COD/H2O2/Fe2+ w/w/w of 1/0.4/0.075 the reduction
in DOC was twice less effective (29%) than COD removal (58%). For higher H2O2/COD ratios the
mineralization extent was more substantial but with a similar difference in COD and DOC removal, thus,
264
the treatment at a COD/H2O2/Fe2+ w/w/w of 1/1.15/0.23 resulted in 51 and 22% residual DOC and COD,
respectively. No traces of residual hydrogen peroxide were detected in the treated wastewater samples
indicating the complete utilization of H2O2 at the studied treatment conditions. The results of non-activated
hydrogen peroxide oxidation at a COD/H2O2 w/w 1/0.4 indicated no organic load reduction and more than
85% of unused H2O2 in the wastewater sample after 24 h of treatment.
The effect of H2O2/Fe2+ weight ratio was studied in order to assess potential to reduce the final
ferric sludge amount (Fig. 1). Both a 2-fold increase and decrease in Fe2+-activator amount resulted in less
than 5% change in COD reduction, negligible changes in mineralization extent, but essentially lower the
BOD7/COD ratio indicating the reasonability of a H2O2/Fe2+ weight ratio of 5:1.
The main problem in the H2O2/Fe2+ process application was the temperature increase and foam
formation immediately after the Fenton oxidation initialization. The temperature increase in 10 °C and foam
formation up to 25% of the initial sample volume was observed during the wastewater treatment at a
COD/H2O2/Fe2+ w/w/w of 1/0.4/0.075. Such a moderate increase in temperature actually favors the Fenton
treatment efficacy. However, further increase in H2O2 dose resulted in severe temperature rise and more
aggressive foam formation. Accordingly, the temperature increase in more than 50 °C and foam formation
up to 300% of the initial sample volume was observed during the oxidation at a COD/H2O2/Fe2+ w/w/w of
1/1.15/0.23. Hence, in the case of a full-scale phenolic wastewater treatment by the Fenton process, the
addition of defoaming agent as well as temperature monitoring may be required to control the foam
production and the exothermic reaction.
The stepwise addition is an option to improve the Fenton treatment by controlling the •OH
scavenging effect essential to systems with Fe2+ or H2O2 excess (Trapido et al., 2009). The optimization of
the oxidation process was done by a stepwise addition of H2O2, Fe2+, and H2O2/Fe2+. The phenolic
wastewater treatment with the H2O2 and H2O2/Fe2+ added in 3 steps at a COD/H2O2/Fe2+ w/w/w of
1/0.4/0.075 resulted in additional 9 and 5% COD and DOC removal, respectively, along with up to 10%
biodegradability improvement. Additionally, a considerable decrease in temperature rise (more than 40%)
and foam formation (up to 50%) was observed during the wastewater oxidation with the stepwise reagents
addition. The Fe2+ addition divided into 3 steps proved ineffective technique to improve the wastewater
treatment efficacy, mainly due to the lower pH reduction at the very beginning of the oxidation and
scavenging of the •OH by the excess of H2O2.
FIGURE 2. COD removal and the BOD7/COD ratio versus the COD/S2O82-/Fe2+ weight ratio in the
persulfate treatment.
265
The iron-activated persulfate treatment of the wastewater demonstrated lower organic load removal
and biodegradability improvement than the Fenton process (Figs. 1 and 2). On the other hand, the complete
exclusion of foam formation and only negligible increase in temperature (2-4 °C) during the oxidation
making the S2O82-/Fe2+ process a viable solution to treat highly contaminated phenolic wastewater. To
optimize the Fe2+-activated persulfate oxidation the effect of different oxidant and activator doses (Fig. 2)
as well as pH adjustment to acidic values was studied. The COD removal and mineralization remained near
identical in trials with a COD/S2O82- w/w of 1/0.4 irrespective of a S2O82-/Fe2+ w/w applied. A 2-fold
increase in S2O82- dose up to a COD/S2O82- w/w of 1/0.8 resulted in additional 10% COD removal.
Unexpectedly, the results of non-activated persulfate treatment at a COD/S2O82- weight ratio indicated
considerable COD removal (47%). On the other hand, the mineralization was higher in the case of activated
persulfate treatment and was 11, 24 and 39% at a COD/S2O82-/Fe2+ w/w/w of 1/0.4/0, 1/0.4/0.075 and
1/0.8/0.15, respectively. The BOD7 removal was steady in all persulfate trials resulting in a lower
BOD7/COD ratio after treatment at a COD/S2O82-/Fe2+ w/w/w of 1/0.8/0.15. Only traces of S2O82- and more
than 25% of unreacted S2O82- were detected in the treated wastewater after application of the activated and
non-activated persulfate, respectively. The adjustment of pH to ~3 was assumed to improve the treatment
efficacy, but the results showed negligible improvement in COD, DOC and BOD7 removal.
Lower treatment efficacy of the iron-activated persulfate compared to the Fenton process could be
explained by lack in direct reduction of Fe3+ to Fe2+ by oxidant as it is presented in Eq. (2) in the case of
the Fenton systems. Moreover, the sulfate radical also reacts with Fe2+ and rapidly converts it to Fe3+
through Eq. (4).
SO4•− + Fe2+ → Fe3+ + SO42- (4)
2+ 3+ •−
Thus, the oxidation of Fe to Fe occurs not only in the generation of SO4 , but also in the
conversion of SO4•− to SO42-. The newly generated SO4•− reacts immediately through the competitive
reaction (Eqs. (3) and (4)) with the contaminant and excess Fe2+ resulting in a lower treatment efficiency.
In order to control the reaction presented in Eq. (4), the stepwise S2O82-, Fe2+, and S2O82-/Fe2+ addition was
also studied. The results indicated a negligible additional COD removal, but up to 6-8% of additional
mineralization for all systems. The BOD7 removal in the stepwise addition systems was higher and resulted
in a lower biodegradability of the treated samples compared to the trial with all reagents added at once.
TABLE 1 The acute toxicity to Daphnia magna (EC50, %).

COD/oxidant/Fe2+, w/w/w H2O2 S2O82-
initial 0.34±0.03
1/0.2/0.04 0.58±0.05 -
1/0.4/0 - 0.51±0.04
1/0.4/0.0375 1.02±0.1 1.32±0.09
1/0.4/0.075 2.21±0.2 0.97±0.07
1/0.4/0.075, oxidant/Fe2+ in 3 steps 4.24±0.3 1.14±0.1
1/0.4/0.15 4.86±0.48 1.12±0.11
1/0.6/0.12 3.41±0.33 -
1/0.8/0.15 4.83±0.43 1.09±0.09
1/1.15/0.23 5.93±0.48 -
The direct application of conventional activated sludge treatment to the studied wastewater was
limited due to the high level of pollution and toxicity. To assess the options available for subsequent
biological treatment of the chemically pre-treated wastewater the acute toxicity to Daphnia magna along
with the inhibition of oxygen consumption by activated sludge and nitrification efficacy were evaluated.
266
The results of the acute toxicity to Daphnia magna, presented in Table 1, indicated relation between
the toxicity reductions in the Fenton pre-treated wastewater samples and the dose of reagents applied. Thus,
the detoxification extent improved with an increase in H2O2/COD and decrease in H2O2/Fe2+ w/w ratio.
Irrespective of a COD/S2O82-/Fe2+ w/w/w applied, the toxicity reduction was similar in the treated samples
and generally lower than in the Fenton pre-treated samples. The most feasible and reasonable treatment of
the phenolic wastewater proved the Fenton treatment at a COD/H2O2/Fe2+ w/w/w of 1/0.4/0.075, which
resulted in more than 67% COD removal, BOD7/COD ratio of 0.32, moderate temperature rise and foam
formation, and more than 12-fold decrease in acute toxicity. The evaluation of inhibition of oxygen
consumption by activated sludge and nitrification efficiency of this chemically pre-treated sample indicated
5-fold and 24-fold increase in IC50, respectively.
Although the acute toxicity and inhibition effect was significantly reduced after the advanced
chemical treatment, the treated wastewater remained rather toxic. Accordingly, the application of properly
optimized ferrous ions activated hydrogen peroxide or persulfate may be recommended as an oxidation step
prior biological treatment of the effluent mixed with domestic/municipal wastewater by a conventional
activated sludge system.
CONCLUSIONS
The result of this study indicated the feasibility of both activated oxidants to reduce organic load
and acute toxicity as well as improve the biodegradability of the heavily contaminated phenolic wastewater.
In general, the Fenton process demonstrated higher treatment efficacy than ferrous ions activated persulfate
system, but was characterized by a temperature increase and excessive foam formation. The persulfate
proved a feasible alternative oxidant due to reasonable treatment conditions and sustainable treatment of
the wastewater. The presence of ferrous ions for activation of persulfate improved the mineralization of the
organic contaminant and toxicity reduction but resulted in similar to non-activated persulfate COD removal
and final biodegradability. The stepwise addition of the reagents was favorable for the Fenton treatment of
highly loaded wastewater treatment. In general, the application of advanced chemical pre-treatment proved
an effective option to improve the overall wastewater quality and increase the possibility of the subsequent
biological treatment of the effluent, rather diluted by less polluted domestic/municipal wastewater. The
results of this study are unique and could provide important information for further implementation in
heavily contaminated wastewater treatment as well as ISCO practice.
ACKNOWLEDGMENTS
This research was supported by the European Union through the European Regional Development
Fund project CHEMBIO (code 3.2.0802.11-0043).
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268
EFFICIENT DECHLORINATION OF 2,4-DICHLOROPHENOL IN AN AQUEOUS MEDIA

WITH A MILD pH USING A Pd/TiO2NTs/Ti CATHODE
Jiang-Kun Du, Jian-Guo Bao*

(State Key Laboratory of Biogeology and Environmental Geology,
China University of Geosciences, Wuhan, 430074, China)
*
(Corresponding author, bjianguo@cug.edu.cn)
ABSTRACT: In this study, we investigated the use of a palladium-loaded titania nanotubes that were
fabricated on a titanium plate (Pd/TiO2NTs/Ti) for electrochemical dechlorination of 2,4-chlorophenol in
an aqueous solution. The surface structure of the Pd/TiO2NTs/Ti electrode were characterized by field-
emission scanning electron microscope (FESEM). We found that the Pd0 nanoparticles were evenly
dispersed on titania nanotubes arrays with 9.33% of its content on the surface. An effective degradation
efficiency of up to 91% was achieved within 60 min at a cathode potential of -0.7 V (vs. SCE) and initial
pH of 5.5. The effects of the applied cathode potential and initial pH on the degradation efficiency were
studied in detail. Interestingly, a weak acid environment was more favorable since very low and very high
pHs were not conducive to the dechlorination process. The intermediates analysis showed that the
Pd/TiO2NTs/Ti electrode was able to selectively and completely remove chlorine from 2,4-dichlorophenol,
since only phenol was detected as the product. The present work presents a good alternative technique for
eliminating persistent chlorophenols in polluted wastewater.
Keywords. Pd; TiO2 nanotubes; chlorophenols; electrocatalytic dechlorination; wastewater
treatment.
INTRODUCTION
Chlorophenols, which are included in the list of priority pollutants by the United States
Environmental Protection Agency, are important intermediates in the industrial production of commercial
herbicides and other chloro-pesticides. They are very toxic and may pose a great threat to the endocrine
systems of both humans and animals (Abe and Tanaka 1997; Olaniran and Igbinosa 2011). Many methods,
such as adsorption, biodegradation, advance oxidation, reductive dechlorination, etc., have been proposed
to treat chlorophenol-contaminated wastewater (Dąbrowski et al. 2005; Olaniran and Igbinosa 2011; Karci
et al. 2012; Du et al. 2013). Adsorption is not cost-efficient, and further treatment is needed after this
processes, during which there is a potential risk of second pollution (Sun et al. 2012b). Biodegradation of
chlorophenols is hard since chlorophenols are toxic to microorganisms (Olaniran and Igbinosa 2011).
Advanced oxidation is an efficient and easily controlled approach to destroying the benzene ring of the
chlorophenols, but some chlorinated byproducts may be even more toxic since the chlorine cannot be easily
removed (Sharma et al. 2010). The toxicity of chlorophenols is strongly associated with the amount of
chlorination (Pera-Titus et al. 2004). Generally, chlorophenols with higher levels of chlorination are more
toxic and more resistant to oxidative degradation (Czaplicka 2004). Therefore, the removal of chlorine from
aromatic compounds could decrease the toxicity and improve the biodegradability or oxidative
degradability. Reductive dechlorination is considered a promising method for selectively removing chlorine
atoms from aromatic compounds. Among these reductive dechlorination techniques, electrochemical
dechlorination is more favorable because the process is easy to control, amenable to automation, highly
efficient, and environmentally sustainable (Zheng et al. 2012; Mitoma et al. 2009).
In a typical electrocatalytic system, the active H atoms, which are produced from the decomposition
of in-situ generated H2 on the electrode surface, are proposed to be the main reactive species for C-Cl bond
269
cleavage (Sun et al. 2012a; Sun et al. 2012b). The electrode material and its surface features are the principal
variables that govern the production of the reactive atomic H, which is available for reduction reactions
(Xu et al. 2013; Xu et al. 2012; Sun et al. 2010). The desired properties can be achieved by using palladium-
modified electrodes since the hydrodechloriantion is more favorably catalyzed by low hydrogen over-
potential metals (Wang and Wang 2009; Chen et al. 2004). Additionally, palladium is an ideal material for
hydrogen adsorption. Very recently, palladium-modified electrodes were frequently prepared using carbon
materials, such as carbon felt (Wang and Wang 2009, 2007) and carbon nanotubes (Cui et al. 2008), as the
supporting substrate due to their low cost and chemical inertness. Although these Pd/C electrodes showed
a good reactivity towards chlorophenols, they may face the problem of low electrocatalytic durability
because carbon corrosion would result in the detachment of the catalyst from the cathode substrate (Huang
et al. 2011; Ferreira et al. 2005). Therefore, considerable efforts have been made to identify more durable
and robust non-carbon support materials. Titania nanotubes (TiO2NTs) are potentially an ideal cathode
substrate because of their desirable electronic property, good mechanical resistance, and high chemical
stability (Quan et al. 2005). Anodic oxidation on a titanium substrate produces ordered TiO2NTs on which
more active sites could be available for palladium attachment because of the rough electrode surface.
Furthermore, it has been reported that this TiO2NT microstructure is very beneficial for achieving a higher
binding strength between the deposited nanoparticles and the base material (Xie et al. 2013; Zhao et al.
2009). Even though various metal-modified titanium nanotubes have been used for pollutant oxidation,
only a few studies have focused on electrode chlorination. Xie et al. (2013) first reported the good
electrocatalytic activity for the Pd-loaded Ti/TiO2 nanotube array cathode for trichloroethylene reduction
in groundwater, showing superior performance for trichloroethylene transformation when compared to
common cathodes (Xie et al. 2013). Nevertheless, this material has never been proven to be effective for
the treatment of wastewater containing chlorophenols, since industrial wastewater treatment have different
technique requirements with respect to groundwater remediation. It is unknown if this novel electrode has
acceptable performance for the dechlorination of chlorophenols since the molecular structure and
compound characteristic of chlorophenols are different from trichloroethylene.
In this paper, TiO2NTs/Ti were fabricated by anodic oxidation, and palladium nanoparticles were
electrodeposited onto the TiO2NTs/Ti arrays (Pd/TiO2NTs/Ti). Both TiO2NTs/Ti and Pd/TiO2NTs/Ti were
characterized using FESEM. An aqueous solution spiked with 2,4-dichlorophenol (2,4-DCP) was selected
as the model industrial wastewater. The transformation of 2,4-DCP in the electrolytic system was
investigated by using self-made Pd/TiO2NTs/Ti as the cathode. The objective of the present study was to
evaluate the suitability and performance of Pd/TiO2NTs/Ti electrode for 2,4-DCP dechlorination under
different experimental conditions, such as pH value, cathode potential value, electrolytes types, and
electrolytes endurance. In addition, the mechanism of 2,4-DCP electrodechlorination by the Pd/TiO2NTs/Ti
cathode was elucidated.
Chemicals and Reagents. 2,4-DCP (99.0%), 2-chlorophenol (2-CP, ≥99%), 4-chlorophenol (4-CP, ≥99%),
and phenol were purchased from Sigma-Aldrich. Palladium acetate (Pd>47.4%) was purchased from
Shaanxi Kaida Chemical Engineering Co., Ltd., China. The Pt plate (1 cm length, 1 cm width and 0.1 mm
thickness, Wuhan Corrtest, China) and Ti plate (2 cm length, 1cm width and 0.5 mm thickness, Shaanxi
Kaida Chemical Engineering Co., Ltd., China) were used as the electrodes. All solutions were prepared
using Millipore-Q water with a resistivity of 18.2 mΩ·cm.
Preparation of TiO2NTs/Ti and Pd/TiO2NTs/Ti Electrodes. TiO2NTs/Ti supports were fabricated by

anodization of Ti plates in NH4F electrolyte (Prakasam et al. 2007). Prior to anodization, the Ti plate was
polished using sandpaper, cleaned by sonicating in deionized (DI) water for 10 min, then dried in an air
270
stream, and subsequently immersed in a mixed acid solution (VHF:VHNO3:VH2O=1:4:5) for 30 min to remove
oily pollutants. Next, the titanium plate was cleaned successively in acetone and DI water for 10 min each
in an ultrasonic bath, and then dried in vacuum for another 30 min. After the above treatments, the Ti plates
were subjected to electrode anodization to synthesize the TiO2NTs/Ti supports. In this process, a two-
electrode configuration was applied with the pretreated Ti plate used as the anode and the Pt plate used as
the cathode and had a 1 cm spacing. The DC power supply (GPC-6030D, Taiwan Guwei Electronic Ltd.,
Inc., Taiwan) was connected to a multimeter and interfaced to a controlling computer. The anodization
process was carried out under a constant voltage of 30 V in 250 mL of a glycerine solution containing 1.25
g NH4F and 7.5 mL DI water. The electrolyte was stirred continuously at 150 rpm using a magnetic stirrer.
The whole anodization process continued for 2 hours. The color of Ti plate changed from purple to blue to
green and then, finally, to pink. The above anodization was repeated five times before processing to the
next step. All experiments were conducted at room temperature, viz. 20.0 ℃. The anodized samples with a
porous structure were washed and sonicated in DI water to remove surface remnants. Then, the as-anodized
samples were annealed in a Muffle furnace maintained at 500 ℃ for 2 hours in order to improve the
crystalline properties and remove the remnants or barrier oxide layer.
Pd/TiO2NTs/Ti electrodes were prepared by the electro-deposition of Pd on the as-prepared
TiO2NTs/Ti support. In a typical process, the TiO2NTs/Ti substrate was used as the cathode and a Pt plate
was used as the anode. Both electrodes were immersed in the electrolyte solution consisting of 4.5 mM
Pd(OAc)2 and 50 mM Na2SO4. Then, Pd nanoparticles were electrodeposited onto the TiO2NTs/Ti surface
under a constant current of 20 mA for 15 min until the electrolyte became colorless. The as-prepared
Pd/TiO2NTs/Ti was washed using DI water and dried in a vacuum oven.
Dechlorination Experimental Procedures. 2,4-DCP dechlorination experiments were carried out in an

undivided compartment cell in a batch mode. A piece of a Pt plate was used as the anode and the as-prepared
TiO2NTs/Ti or Pd/TiO2NTs/Ti electrode was used as the cathode with an exposure area of 2 cm2. The
distance between two electrodes was 2 cm. A saturated calomel electrode (SCE) was used as the reference
electrode. The synthetic supporting electrolyte (250 mL) consisted of 50 mmol/L Na2SO4 and 20 mg/L 2,4-
DCP as the initial concentration for each trial. The pH of the electrolyte was adjusted to 5.5 using H2SO4
or NaOH solutions. The electrolyte solution was continually stirred using a Teflon-coated magnetic bar
during the experiments to allow for the equilibration of 2,4-DCP in the solution. A constant potential was
maintained during the electrolysis. Different potentials were applied to test the effect of cathode potential
on 2,4-DCP dechlorination. Additionally, the solution pH was adjusted by H2SO4 or NaOH for the
experiments testing the effect of different initial pH values. At predetermined time intervals, 2 mL of the
aqueous solution was taken and filtered through a 0.22-μm membrane filter (Shanghai General Reagent
Factory, China). All experiments were carried out in triplicate to ensure the reproducibility of the results.
Additionally, in order to further understand the dechlorination byproducts, as well as the working
mechanism, the 2,4-DCP was dechlorinated in a divided electrolytic system with two compartments that
were connected by a salt bridge filled with 3% agar solution saturated with K2SO4. All other conditions
were identical to above experiments.
Characterization and Analysis. The FESEM characterization of the as-prepared and used Pd/TiO2NTs/Ti
electrodes was carried out on a diffractometer (D/max-1200, Japan). The morphologies of the TiO2NTs/Ti
and Pd/TiO2NTs/Ti were measured using a FEI Nova 400 FESEM from Netherlands (Peabody, MA). The
concentration of 2,4-DCP was analyzed using a Shimadzu HPLC equipped with an SPD-15C UV-Vis
detector. A C-18 reverse-phase chromatographic column was utilized for the HPLC. The mobile phase
consisted of a mixture of 1% acetic buffer and methanol at a 40:60 (v/v) ratio. The mobile phase flow rate
was fixed at 1 mL/min. The detection wavelength for 2,4-DCP and the dechlorination products was 278
271
nm. The byproducts were identified by comparing the retention time of the peak appearance between the
experimental byproducts and standard chemicals.
Characterization of the Pd/TiO2NTs/Ti Catalyst. FESEM images show highly ordered and well aligned
morphologies of the TiO2 nanotubes array grown on the surface of Ti plate after anodization and annealing
(Fig. 1(a)). In addition, a banding distribution of columnar structure with a high density is shown in the
cross-section of the film. From the microstructure of the TiO2 nanotubes, it can be observed that the inner
pore diameters of the nanotubes were in range of 50–100 nm and the typical nanotube lengths were 2–3
μm. Regarding the morphology of the Pd species, small particles were observed on the Pd/TiO2NTs/Ti
surface, as shown in Fig. 1(b). The palladium were exhibited in the form of clusters of globules.
Fig. 1. Cross-sectional FESEM images of: (a) TiO2NT; and (b) Pd/TiO2NTs/Ti.
1.0
0.8
0.6
Pd/TiNT
C/C0
TiNT
0.4
0.2
0.0
0 20 40 60 80 100 120
Time (min)
Fig. 2. Removal of 2,4-DCP with Pd /TiO2NTs/Ti or Ti/TiO2NTs cathode at -0.7 V. Reaction conditions
were based on 20 mg/L 2,4-DCP and 50 mM Na2SO4 background electrolyte.
272
Reductive Dechlorination of 2,4-DCP by Pd/TiO2NTs/Ti Cathodes. The performance of the

Pd/TiO2NTs/Ti cathode was investigated in a batch mode in an undivided compartment. With the
eletrocatalytic drive of Pd nanoparticles, 90.8% of 2,4-DCP disappeared from the aqueous solution (Fig.
2). However, without palladium-loading, the removal efficiency of 2,4-DCP by the TiO2NTs/Ti electrode
could be negligible under the same experimental conditions. This result proves the indispensable catalytic
role of Pd nanoparticles in 2,4-DCP dechlorination.
(a) (b) 0.05

1.0
0.04
0.8
0.03
0.6
k (min )
-1
C/C0
0.02
0.4
-0.7 V
-0.6 V 0.01
0.2
-0.5 V
-0.4 V
0.0 0.00
0 10 20 30 40 50 60 -0.4 -0.5 -0.6 -0.7
Time (min) Potential vs. SCE (V)
Fig. 3 (a) 2,4-DCP dechlorination at different cathode potentials; and (b) The relationship between
pseudo-first-order kinetics and cathode potential. (Electrolyte: 50 mM Na2SO4 and 20 mg/L 2,4-DCP; pH
5.5)
The reductive dechlorination of 2,4-DCP under different cathode potentials was evaluated in an
undivided compartment. The dechlorination process almost finished within the first 60 min, and the cathode
potential could have a substantial influence on the rate of the dechlorination reaction (Fig. 3(a)). The
pseudo-first-order kinetic model described the dechlorination process of 2,4-DCP with Pd/TiO2NTs/Ti
cathode well. When the cathode potential was -0.4 V, the 2,4-DCP removal efficiency was only 26.25%
after 60 min, indicating that the potential was not high enough to create sufficient reactive hydrogen atoms
for 2,4-DCP dechlorination. Meanwhile, the direct reduction by the Pd/TiO2NTs/Ti cathode may dominate
the transformation process, which was proposed to be driven by electron tunneling or by the formation of
a chemisorbed complex with the cathode (Brewster 1954). When the cathode potential was increased to a
larger value, the removal efficiency reached a much higher level (greater than 80%). The degradation
efficiencies was 83.15%， 90.76%， and 91.11% when the dechlorination potential was -0.5 V, -0.6 V, and
-0.7V, respectively. This could have been due to the increasing generation of reactive hydrogen atoms
adsorbed on the palladium surface, which accelerated the dechlorination rate. However, we also noted that
the dechlorination tendency did not change significantly when the cathode potential was more negative than
-0.6 V. This discrepancy is also shown in Fig. 3(b). The pseudo-first-order kinetic rate constant values of
2,4-DCP dechlorination at -0.6 V and -0.7 V were 0.04665 and 0.04435 min-1, respectively, clearly
indicating a similar reaction rate. Comparable results have been reported for the electrocatalytic
hydrodechlorination of pentachlorophenol at a Pd/MWCNTs/graphite electrode, where the hydrogen
evolution was supposed to be the main reason for the limited reaction rate promotion as the cathode
potential increase (Cui et al. 2008). With a further increase in cathode potential, the generation capacity of
reactive hydrogen atoms on the Pd/TiO2NTs/Ti cathode reached a maximum, while the hydrogen evolution
accelerated, leading to a decrease in the dechlorination efficiency. This demonstrated that there was a
cathode potential threshold value, and it is hard to further promote hydrodechlorination rate whenever the
cathode potential exceeded this threshold value due to the competition from hydrogen evolution.
273
1.0
0.8
0.6
C/C0
0.4
pH=3
0.2 pH=5.5
pH=10
0.0
0 10 20 30 40 50 60
Time (min)
Fig. 4. Effect of pH on 2,4-DCP degradation in the Pd/TiO2TNTi electrolysis system. (Electrolyte: 50
mM Na2SO4 and 20 mg/L 2,4-DCP; cathode potential: -0.7 V)
To evaluate the effect of pH on the dechlorination efficiency of 2,4-DCP, the initial pH of

electrolyte solution was adjusted to three representative pH values at 3.0, 5.5, 10.0. The results shown in
Fig. 4. indicate that the initial pH of the electrolyte can notably influence the electrocatalytic dechlorination
performance. It also revealed that an acid electrolyte solution is able to achieve a higher degradation
efficiency. For instance, only 20.76% of the 2,4-DCP was removed within 120 min when the initial pH of
electrolyte was adjusted to 10.0, but a nearly complete dechlorination was achieved after 60 min when the
initial pH was 5.5. This was not surprising since the system could not supply enough reactive hydrogen
atoms at a low H+ concentration. According to Sun et al. (2012b), a low initial pH not only can increase the
removal efficiency and current efficiency, but it can also bring the final pH to almost neutral since the pH
value would increase when dechlorination finished (Sun et al. 2012b). Nevertheless, a total of 75% of the
2,4-DCP was removed when the initial pH was 3.0. This removal efficiency was smaller than that achieved
at pH 5.5. This seems to be an uncommon result when compared to previous reports, which have shown
that a more acidic condition could promote the dechlorination reaction (Cui et al. 2008; Sun et al. 2013).
However, Sun et al. (2012b) also noted that the dechlorination efficiency increased gradually as the solution
pH decreased, and then became stable after the pH reached a threshold value (Sun et al. 2012b). In addition,
Xu and his coworkers (2012) reported that, while the dechlorination efficiency of chloroacetic acids remain
similar in H2SO4, Na2SO4, and NaOH aqueous solutions, a higher current efficiency can be achieved in
alkaline aqueous solutions because of less molecular hydrogen evolution (Xu et al. 2012). Different model
contaminants and dechlorination systems may be responsible for the differential results reported in the
literature. Here, we noticed that more bubbles were generated during the experiment with an initial pH of
3. Therefore, we assumed that more vigorous hydrogen evolution may have taken place when a high cathode
potential and a low pH value were used in the system at the same time, thus leading to a significant reduction
in dechlorination efficiency and current efficiency.
Electrodechlorination Mechanism. To further understand the mechanism of dechlorination, 2,4-DCP and

phenol solutions were electrolyzed for 120 min by the Pd/TiO2NTs/Ti electrode in the cathode
compartment, and the intermediates products were detected by HPLC. According to published reports, 2,4-
DCP has form three main byproducts, including 2-chlorophenol, 4-chlorophenol, and phenol, after
dechlorination (Sun et al. 2013; Sun et al. 2010). Phenol is usually found as the final product of
274
chlorophenols. Additionally, 2-chlorophenol would be the main intermediate product of 2,4-DCP in the
first minutes of decay since the C-Cl bond at the para position shows higher reactivity than the bond at the
ortho position, thus leading to faster reductive cleavage of the C-Cl bond at para position (Sun et al. 2012b;
Wang et al. 2013). However, we detected phenol, but not monochlorophenols, in the present work (shown
in Fig. 5). This may be due to the high eletrocatalytic activity of the Pd/TiO2NTs/Ti cathode and that the
2,4-DCP could be quickly and completely dechlorinated before it detached from the electrode. Additionally,
good mass balance was achieved, indicating that the phenol could not be further degraded by the
Pd/TiO2NTs/Ti cathode. On this basis, we proposed a possible mechanism for the eletrodechlorination of
2,4-DCP based on the Pd/TiO2NTs/Ti cathode (Fig. 6).
1.0
0.8
0.6 2,4-DCP
Phenol
C/C0
0.4 Mass Balance
0.2
0.0
0 20 40 60 80 100 120
Time (min)
Fig. 5. Dechlorination byproducts of 2,4-DCP in the cathodic compartment of a divided electro-system
connected by a salt bridge. (Electrolyte: 50 mmol/L Na2SO4 and 20 mg/L 2,4-DCP; applied cathode
potential: -5.0 V; initial pH: 5.5)
Fig. 6. Proposed dechlorination mechanism and pathway of 2,4-DCP on the Pd/TiO2NTs/Ti cathode
surface.
275
The good degradation performance of the electrolytic system can be attributed to the following
sequence of reactions: (i) the 2,4-DCP and water molecules can be adsorbed onto the surface of the
Pd/TiO2NTs/Ti cathode; (ii) a small fraction of 2,4-DCP may be directly reduced by the Pd/TiO2NTs/Ti
cathode, while H3O+ or H+ ions could get an electron from the cathode and be transformed into H2, which
could be adsorbed on the palladium particles and decomposed to powerful reducing species—reactive
hydrogen atoms; and (iii) the rest chlorinated pollutants were completely catalytically dechlorinated by the
reactive hydrogen atoms, and then the final byproducts detached from the electrode surface. It should be
noted that pH would play an indispensable role during these process. A solution with a very low pH or very
high pH would not produce sufficient reactive hydrogen atoms. A weakly acid solution would maximize
the dechlorination potential of the novel system since a perfect balance between the reactive hydrogen atom
generation and hydrogen evolution is beneficial to 2,4-DCP dechlorination.
CONCLUSIONS
Pd/TiO2NTs/Ti was prepared and used to degrade 2,4-Dichlorophenol in an aqueous solution.
Palladium nanoparticles were highly dispersed in the TiO2NTs arrays with an amorphous structure.
Efficient dechlorination of 2,4-DCP with a removal efficiency of 91% within 60 min was achieved in the
Pd/TiO2NTs/Ti electrode system when the cathode potential was -0.7 V and the initial pH of the electrolyte
was 5.5. A very low or very high pH of the electrolyte solution was not beneficial to electroreductive
dechlorination. Additionally, the reductive dechlorination of 2,4-DCP followed pseudo-first-order kinetics
during the 60 min reaction. As a high-efficient catalyst, the Pd/TiO2NTs/Ti cathode can effectively produce
active H atoms to accelerate the reductive reaction. The main intermediate of 2,4-DCP dechlorination in
the cathodic compartment was determined to be phenol. In summary, the Pd/TiO2NTs/Ti electrode
exhibited promising electrocatalytic capability for the dechlorination of 2,4-DCP, but further work still
needs to be done to develop strong binding between the Pd nanoparticles and TiO2NTs substrate.
ACKNOWLEDGEMENTS
This work was financially supported by the Hubei Provincial Science and Technology Department
with grant No.2006AA305A05.
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278
TREATABILITY OF AQUEOUS ALCOHOL ETHOXYLATES SOLUTION BY

ELECTROCOAGULATION AND COAGULATION
Çisem E.*, Kabdaşlı, I., Tunay O. and Ölmez-Hancı, T.

(Istanbul Technical University, Istanbul, Turkey)
Alcohol ethoxylates (AEs) are a class of non-ionic surfactants widely used as detergents, emulsion
stabilizers, foaming agents and wetting enhancers. These properties allow large industrial application as
additives in the formulation of pesticides, pharmaceuticals, paints and cosmetics, as well as in mineral
separation, biotechnology etc. Although there is no known toxic effect of AEs, their concentrations are
often relatively high in aquatic environment.
Coagulation is a treatment method which has been investigated on both domestic and industrial
wastewaters. Considering the above mentioned facts, in the present experimental study, chemical and
electrocoagulation (EC) of aqueous poly (oxyethylene) (4) loryl ether (commercial name Brij30®) being
selected as a model AE was investigated. The degradation extent has been evaluated by measurements of
mother compound, Brij30. Coagulation-flocculation process derived in different coagulant (FeCl3)
concentrations varing between 100 and 1000 mg/L, at pH 6.5 and Brij 30 concentration of 20 mg/L. The
second process was electrocoagulation process using stainless steel electrodes and NaCl as electrolyte.
Electrocoagulation experiments were conducted at original pH of 20 mg/L Brij30 solution (~ 6), various
NaCl concentrations (500, 1000, 1500, 2000 mg NaCl/L) and two current densities (9,3 and 18,6 mA/cm2).
In chemical coagulation process the least Brij 30 removal was observed with 25% in 100 mg/L
FeCl3 dosage and the highest Brij30 removal efficiency was achieved with 39% in 750 mg/L FeCl3 dosage.
Higher removal efficiencies are observed for electrocoagulation. After 180 minute electrocoagulation with
500 mg/L NaCl initial electrolyte concentration, 70% and 60% of Brij30 removal was achieved for current
density of 18.6 mA/cm2 and 9.3 mA/cm2, respectively. Under stable current density (18.6 mA/cm2),
increasing NaCl concentration from 500 to 1000 mg/L increased the Brij30 removal from 73% to 94%.
Contrary to this result, no removal was observed for 1500 or 2000 mg/L NaCl electrolyte concentration.
279
REMOVAL OF CHROMIUM CR(VI) FROM WASTEWATER

USING SAUDI ACTIVATED BENTONITE
Saad Said Al-Shahrani

(King Abdulaziz University, Jeddah, Saudi Arabia)
In this study, removal of Cr(VI) from wastewater using Saudi activated clay (bentonite) was investigated
in a batch adsorption system. The removal characteristics were investigated under various operating
variables such as contact time, solution pH, clay dosage and initial metal concentration. It was found that
adsorption of Cr(VI) ions on Saudi activated bentonite was relatively fast and the equilibrium was achieved
after 30 min. Adsorption was also dependent on solution pH where Cr(VI) removal percentage decreased
with increasing solution pH. Moreover, The results showed that increasing the initial Cr(VI) concentration
decreased Cr(VI) removal percentage due to saturation of clay with Cr(VI) ions. The adsorption isotherm
data were well fitted with both the linearized Langmuir and Freundlich models. Furthermore, the value of
the mean free energy determined with the D–R equation showed that adsorption process is chemisorptions.
Cr(VI) adsorption into Saudi activated bentonite was well represented by the pseudo-second-order kinetic
model.
280
Chromium (VI) Removal by a Fe-Mn Binary Oxide with and without H2O2
Si-Hyun Do* (Soongsil University, Seoul, Republic of Korea)

Yong-Jae Kwon (Hanyang University, Seoul, Republic of Korea)
Chromium (VI) removal by a Fe-Mn binary oxide with and without H2O2 was investigated. Several binary
oxides (i.e. Fe immobilized Mn oxide (Fe-Mn binary oxide), Mn immobilized Fe oxide (Mn-Fe binary
oxide), co-precipitation of Fe and Mn (Fe(II)Mn(II) binary oxide)) were applied. With H2O2, Fe-Mn binary
oxide showed the higher Cr(VI) removal (i.e. possibly through reduction and adsorption). When 0.02 g of
Fe-Mn binary oxide was reacted with 40 μM of H2O2, Cr(VI) was removed as much as 15 μM, which was
75% of initial Cr(VI) (i.e. 20 μM). Without H2O2, Fe(II)Mn(II) binary oxide showed the higher Cr(VI)
adsorption, which was about 24% of initial Cr(VI). Moreover, When 0.16 g of Fe(II)Mn(II) binary oxide
was used, 92% of Cr(VI) was adsorbed. To achieve higher Cr(VI) removal, the modified system will be
presented.
281
Electrochemical Advanced Oxidation Process for Optimal Decontamination of Phenolic

Wastewater Containing Inorganic Species
Nuhu Dalhat Muazu*, Gulraiz Khan and Nabil Jarrah

( Environmental Engineering Department, University of Dammam, Dammam 31451, Saudi Arabia)
Global increase in industrial activities is leading to significant production of phenolic wastewater effluents.
Phenolic wastewaters from a number of industries are major sources of release of inorganic species such as
cyanide, sulfide, ammonium, thiocyanate etc into the ecosystem. Presence of elevated concentrations of
these inorganic pollutants in phenolic wastewater effluents renders improper discharge of such wastewaters
liable to leading to detrimental environmental consequences and could also posing greater challenge for
effective decontamination of the wastewater.
In this work, electrochemical treatment of phenolic wastewater containing NH4+, CN- and S2- in
different single, binary, ternary and quaternary mix matrixes using Boron Doped Diamond (BDD) anodes
at bench-scale is presented. Under different experimental conditions the evolutions of phenol, phenol
oxidation intermediates and the inorganic species were monitored in relation to energy and current
efficiencies. Results obtained showed that generation and accumulation of toxic oxidation byproducts that
completely render the EAOP using BDD electrodes ineffective could be avoided via appropriate
optimization of process operating conditions. The degradation kinetics of phenol as well as the inorganic
species in the different mix matrixes were pseudo-first order in nature with the kinetics been reduced mainly
as result of decline in the BDD anodes’ activities. This study demonstrated the viability of EAOP using
BDD anodes as alternative treatment means for effective decontamination of phenolic wastewater
containing inorganic species.
282
CONTINUOUS TREATMENT OF ESTROGENS THROUGH POLYMERIZATION AND

REGENERATION OF ELECTROLYTIC CELLS
Vo Huu Cong, Sota Iwaya and Yutaka Sakakibara*
(Waseda University, Tokyo, Japan. sakaki@waseda.jp)
ABSTRACT: Continuous experiments were conducted to treat estrogens such as Estrone (E1), 17β-
estradiol (E2) and 17α-ethynyl estradiol (EE2) using an electrolytic reactor equipped with multi-packed
granular glassy carbon electrodes. Experimental results showed that E1, E2 and EE2 were oxidized in the
range of 0.5-1mA and were removed efficiently through electro-polymerization on the granular electrodes.
Polymer formed during continuous treatment was quickly decomposed and electrodes were regenerated
completely by OH radicals produced through the reduction of ozone. Overall energy consumptions were
less than 10 Wh/m3, demonstrating extremely low energy consumptions. A mathematical model developed
based on the polymer formation and regeneration could represent general trends in time series data observed
in experiments.
INTRODUCTION
Removals of trace pollutants such estrogenic compounds have drawn much attention due to its
toxicity to aquatic life forms at trace concentration (ng/L). The ecological effects of estrogenic compounds
such as 17β-estradiol (E2) and 17α-ethynyl estradiol (EE2) were reported in the range of 0.2 to 10 ng/L
(Tilton et al., 2005; Lei et al., 2013). However, residues of these compounds were detected at high
concentrations in many countries. E1 was reported in the range of 48-100 ng/L in Austria (Clara et al.,
2005), Canada (Servos et al., 2005) and Japan (Nakada et al., 2006). High concentrations of E2 and EE2
were measured in Austria, Taiwan and Turkey (Clara et al., 2005; Chen et al., 2007; Can et al., 2014).
Elimination of these compounds in effluents of sewage treatment plants (STP) before discharge into
receiving water is important to conserve the ecosystem.
It was demonstrated that electrochemical oxidation of estrogens occurred in the range of 0.45-0.8
V corresponding to an oxidation current peak of 90 µA (about 10-4 mA/cm2) at 0.73 V (Cong et al., 2014).
However, further deposition of estrogens onto electrode surface was inhibited due to polymer formation
(Cong and Sakakibara, 2014). In order to enhance removal efficiency, glassy carbon electrodes (GCE) were
used because it has high specific area and electrochemical conductivities. In batch treatments, removals of
E1, E2 and EE2 were possible by an application of electric current in the range of 0.1-1.5 mA. In literature,
it is hardly found papers emphasized on the treatment of estrogenic compounds employing electro-
polymerization process.
In this study, removal stability of E1, E2 and EE2 by a granular glassy carbon electrode reactor was
investigated. The removal performance was compared with that of Pt/Ti electrode reactor, which has been
proved possible to remove EDCs containing E2. In addition, most important operating conditions such as
applied electric current, hydraulic retention time, anode materials were evaluated. In addition, maintenance
of the electrolytic system is very important for practical concern; therefore, electrode regeneration and
continuous removals of estrogens were evaluated.
Materials. Estrone (CAS 58-05023), 17β-estradiol (CAS 58-04043) and 17α-ethynyl estradiol (CAS 57-
63-6) were used as natural and synthetic estrogens. N,O-Bis(trimethylsilyl) trifluoroacetamide (BSTFA)
with 1% trimethylsilane (TMS) and Pyridine were used as derivatives and catalyst to enhance detection of
283
mass ion (m/z) of each estrogen. BPA-d14 was used as surrogate. Chemicals were purchased from Wako
Chemical Company, Japan. A stock solution containing 1 mg/mL of E1, E2, EE2 and BPA-d14 was made
in acetone 5000 and kept in refrigerator at 0℃.
Apparatus. FIGURE 1 shows the interior of reactor and its configurations in continuous treatments of
estrogens. The reactor consists of two compartments filled up with glassy carbon (or Pt/Ti) granular anodes
and a Pt/Ti mesh as cathode. The average size of GCE was 3 mm. The surface area of mesh-type electrode
was about 20 cm2. The reactors were made of stainless equipped with Teflon sheet to prevent adsorption.
Total liquid volume and surface area of anodes were about 500 mL and 2,000 cm2, respectively. A part of
liquid inside anode compartments
was recycled for completely mixed
conditions. The cathode and anode
chambers were separated by a
porous Teflon sheet and glass beads.
Multi-anodes were connected with a
direct current (DC) supply at
constant current mode. The synthetic
estrogen solutions were fed
continuously to the reactor using a
peristaltic pump.
FIGURE 1. experimental apparatus in continuous experiment
Operating Conditions. The removal performances were evaluated under different operating conditions
such as electric current (Run 1), hydraulic retention time (Run 2), electrode materials (Run 3), water matrix
(with/without humic substances) (Run 4), and long-term treatment with regenerations of electrolytic
systems (Run 5). Synthetic estrogens were prepared in 10 mM Na2SO4. TABLE 1 shows the experimental
conditions of continuous experiments.
TABLE 2. experimental condition of continuous experiments
Run Feed Influent HRT Current Reactor Recycle

No. solution Conc. (min) (mA) (electrode) rate
(µg/L) (mL/min)
1 EE2 296 180 1, 0.1, 1 Pt/Ti 500
2 EE2 100 180, 90, 180 1 GC 500
3 E1, E2, EE2 100 180 1 Pt/Ti and GCE 500
4 EE21) 1 180 1 GC 400
5 EE2 100 180 1 GC 500
Analysis. In chemical analysis of estrogens, 100 mL of influent and effluent samples were extracted with
20 mL of ethyl acetate 5000 after adding BPA-d14, 10 g NaCl and 0.2 mL of 1 mol/L HCl solution.
Extracted samples were dehydrated using Na2SO4 (anhydrous). After concentrated using a rotary
evaporator, estrogen samples were dried under a gentle nitrogen stream and filled up to 0.5 mL.
Derivatizations of E1, E2, and EE2 were obtained using BSTFA (1%TMS) catalyzed by pyridine. Internal
standard method was applied to calibrate concentrations of E1, E2 and EE2 from 1-200 µg/L. All analyses
were carried out by GC/MS QP5050 (Shimadzu, Japan).
284
Mathematical Model. In the continuous experiment, the same kinetic approach was applied to the
electrochemical removals of trace estrogens (Sakakibara et al., 2010). From an assumption that overall
removal rates of estrogens are governed by mass transfer rates; the removals in continuous treatment can
be represented by the following Eq. (1).
v1^
V v
= Q Cx − C − K ?z AC (1)
where, V (mL) is liquid volume of reactor, Q (mL/min) is feed flow rate, C0i (µg/L) and Ci (µg/L) are the
influent and effluent concentrations of estrogen i, KLi (cm/sec) is mass transfer coefficient and A (cm2) is
total surface area. At steady state conditions, Eq. (1) is simplified to the following algebraic equation (2):
1^
=
1|^ }~•€ . .•‚ƒ
(2)
where, a (cm-1) is specific surface area of working electrode, and HRT (hour) is hydraulic retention time.
Removal Efficiency. Removal efficiencies (RE) were calculated based on the observed effluent and
influent and represented in equation (3):
‡| ‡
„… % = ‡|
× 100 (3)
RESULTS
Influences of Electric Current. FIGURE 2 demonstrates the removal efficiency of 296 µg/L EE2 by
granular Pt/Ti electrolytic reactor in the range of 0.1-10 mA. Observed results demonstrate that EE2 was
effectively removed at 96%-98% at 1mA within 2 days. As electric current was set at 0.1mA (day 5), the
removal efficiency decreased to 66%-81%. However, when the electric current increases to 10 mA (two
orders), RE was slightly increased to 84%-88%. This result indicates that electric current at 1 mA could be
sufficient for removal of estrogen (EE2). It was reported that removals of estrogens were governed by the
mass transfer rate-limiting step and not driven by the electric current (Sakakibara et al., 2010; Cong et al,
2014). In addition, Nagata et al. (2005) suggested optimal electric current about 0.5 mA could be applied
to remove trace EDCs using same reactors. This result suggests that an electric current from 0.5 mA to 1
mA could be applied for treatment of high loading rate of estrogens.
RE (EE2 Influent) RE (EE2 Effluent) RE (EE2 Influent) RE (EE2 effluent)
90
Removal efficiency (%)
90
Removal effciency (%)
70 70
50 I= 10 mA 50
I= 1 mA HRT= 180 min HRT= 180 min
30 I= 0.1 mA HRT= 90 min
30
10
10
-10
-10
0 3 6 9 12 15 18 21 24 27
0 2 4 6 8 10
Time (d) Time (d)
FIGURE 2. Continuous removal of EE2 by Pt/Ti FIGURE 3. Continuous removal of EE2 by GCE
reactor reactor
285
E2 Influent (GC) E2 Effluent (GC) Equation 2

E1 Effluent (Pt/Ti) E2 Effluent (Pt/Ti)
Concentraion (Ci/C0i) 1.2
1.0
0.8
0.6
0.4
0.2
0.0
0 5 10 15 20 25 30
Time (d)
FIGURE 4. Continuous removals of E1 and E2 by Pt/Ti and GC electrode reactors
Influences of Hydraulic Retention Time. Hydraulic retention time is a crucial factor influenced removal
performance of estrogens. FIGURE 3 demonstrate the removal efficiencies of 100 µg/L EE2 at 180 min,
90 min, and 180 min. It was shown that 87%-90% were removed within 4 days at HRT 180 min. When the
HRT was set at 90 min, the removal efficiency has reduced to 72%-75% but tended to increase (80%) after
two days. To confirm the influence of HRT on removal efficiency and stability, HRT was reset at 180 min.
Observed concentration in effluents were similar to the previous treatments. On the other hand, influent
concentrations were observed around 100 µg/L suggest that removals of EE2 were made through
electrochemical oxidation process. It was demonstrated that HRT plays an important role to removal
efficiencies; however, further studies using higher specific area materials should be conducted.
Influences of Electrode Materials. Sakakibara et al. (2010) reported that it was possible to remove 0.01-
0.1 µg/L E2 at 1 mA using Pt/Ti electrolytic reactor. In this study, the same reactors were used to evaluate
removal performances of 100 µg/L E1 and E2 by Pt/Ti and GCE reactors. FIGURE 4 illustrates removals
of E1 and E2 at 1mA in the course of 18-30 days. Observed results reveal the removals of E1 and E2 was
in good agreement with the mathematical model (Eq. 2), indicating that removals of E1 and E2 were also
governed by mass transfer rate even the influent concentration was 3-4 orders of magnitude higher in the
former study (Sakakibara et al., 2010). The removal efficiency achieved about 97%-99% meanwhile that
of E1 was reached 90%-99% from day 2 of operation. The result suggests that E1 and E2 could be
effectively removed by Pt/Ti electrolytic reactor. In addition, glassy carbon electrodes were used to evaluate
the removal performance in comparison with Pt/Ti electrode reactor. As shown, removal performance of
the GCE reactor achieved very stable in the course of 30 days of operation.
Influences of Co-Substances. Removal performances of 1 µg/L EE2 in without/with presences of co-

substances (1 mg/L-TOC) is shown in FIGURE 5. Observed results show a stable removal of 1 µg/L EE2
in the courses of 90 days operation. After 52 days continuous treatment, 1 mg/L-TOC of humic acid was
added in the feeding solution as co-substances. As shown, the same removal performance was observed in
30 days even co-substances were existed in the reactor. In this study, electric current density was very low;
therefore OH production might be negligible. Electricity was consumed for direct oxidation of EE2 on
surface of electrode.
From day 90 of operation, observed residue of EE2 in effluent starts rising. We supposed that glassy
carbon might be passivated during the treatment process. In former study, Cong and Sakakibara (2014)
reported a significant change of chemical elements on surface of Pt/Ti and GCEs before and after 4 hrs of
treatment. Therefore, electrodes were taken for morphology examine.
286
Influent (no HA) Effluent (no HA) Influent (with HA) Effluent (with HA)
1.2
Concentration (μg/L) 1.0
0.8
0.6
0.4
0.2
0.0
0 20 40 60 80 100
Time (d)
FIGURE 5. Continuous removals of EE2 with/without co-substances
Morphology of Electrode. The GCEs were taken after 90 days continuously treatment of 1µg/L of EE2.
Electrode morphology was analyzed by a scanning electron microscope (SEM). Visualization analyses of
the surface were carried out at 10,000x of magnification. FIGURES 6A and 6B demonstrate a change in
surface morphology of electrode before and after 90 days. FIGURE 6B shows a thin layer of substances
(approx. 1µm) that is not appeared in the new electrode (FIGURE 6A). This thin polymerized layer may
attribute to the ineffective removal of EE2 after 85 days of operation.
1 µm
A) New GCE B) GCE after 90 days treatment

FIGURE 6. glassy carbon surfaces A) before and B) after continuous treatments
Continuous Treatments and Regeneration of Electrodes. EE2 is one of the strongest estrogenic
compounds, thus, elimination of its toxicity is great of concern. Continuous treatment of synthetic solution
contained 100 µg/L EE2 in 10 mM Na2SO4 was experimentally conducted using granular glassy carbon
electrolytic reactor in the course of 135 days. The removal performance is shown in FIGURE 7. As shown,
observed stable influent and effluent concentrations indicate that removal of EE2 was made by
electrochemical oxidation process. The removal of EE2 experienced three stages, of which the first state
shows a stable removal of EE2, and then second stage takas place with increasing of effluent concentration
approaching influent, the third stage dedicates to the steady state of no EE2 removal.
Upon the point of no removal, effluent concentrations were at steady state for 12 days. This
suggested no removal of EE2 was achieved once the electrode completely passivated. Electrode
regenerations (Reg 1 and Reg 2) were conducted in presence of 1.8 mg/L and 3.0 mg/L dissolved ozone
combined with change of polarization for 120 min and 30 min, respectively. After regenerations, EE2 was
removed effectively for a period of 50 days. This result has indicated two important points: 1) possibility
of an application of ozone for regeneration of electrolytic reactor for continuous treatment of estrogenic
287
compounds through electro-polymerization, and 2) periodically regeneration could be predicted with

enhanced technique to quantify the mass deposition from a known influent concentration of pollutants.
EE2 Influent (100µg/L) EE2 Effluent

120
Reg 1 Reg 2
Concentration (µg/L)
100
80
60
40
20
0
0 20 40 60 80 100 120
Time (d)
FIGURE 7. Continuous removals of EE2 by GCE reactor and electrode regeneration
Removal efficiencies of E1, E2 and EE2 were achieved up to 98%, but energy consumption was
observed in the range of 1-10 Wh/m3, which are 4 - 5 orders of magnitude lower. From these results, we
concluded that the present electrochemical process would be an alternative removal of estrogens.
CONCLUSIONS
Electrochemical oxidations and continuous removals of E1, E2, and EE2 were possible with
extremely low current electricity at 0.5 to 1 mA (corresponding to 2.5×10-4 to 5.0×10-4 mA/cm2). Hydraulic
retention time has slightly influenced on removal efficiency and stability of the electrolytic system. In
continuous treatment, removal efficiencies of E1, E2 and EE2 achieved more than 98% in the case of trace
condition (1 µg/L). At high loading rate (100 µg/L), removal of EE2 achieved 91%-98% in the course more
than 30 days. It was thought that estrogen removals were made through polymerizations of estrogens, while
the decomposition of polymer formed (or regeneration of electrode) was possible by using ·OH radicals
produced through the reduction of ozone. Electric energy consumption was observed in the range of 1-
10Wh/m3. From these results, we concluded that the present electrochemical process would be an
alternative removal of estrogens.
ACKNOWLEDGMENTS
This research was supported in part by the Grant-in-Aid for Scientific Research (B) (No.
24360219), the Ministry of Education, Culture, Sports, Science and Technology (MEXT) and Waseda
University Grants for Special Research Project (No. 2013A-887).
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289
ASSESSMENT OF COMETABOLIC BIODEGRADATION POTENTIAL OF DICLOFENAC IN

THE PRESENCE OF ACETATE UNDER ANAEROBIC CONDITIONS
Sevgi Sari, Emel Topuz, Egemen Aydin, Didem Okutman Tas*

(Istanbul Technical University, Maslak, Istanbul, Turkey)
Diclofenac has been increasing concern due to its increasing detection in environmental samples as a result
of rising global consumption. Diclofenac has been identified as a threat in the water cycle because of its
low removal rate during wastewater treatment processes (Huber et al., 2012). Therefore, additional
treatment options should be considered in wastewater treatment plants to enhance diclofenac removal
efficiency. The aim of this research is to investigate the cometabolic removal efficiency of diclofenac under
anaerobic conditions using acetate as a readily biodegradable carbon source.
Batch reactors were set up using a fermentative/methanogenic culture which was previously
acclimated to diclofenac and fed with glucose as a carbon source. The culture was kept in the dark in a 22ºC
constant temperature room and was stirred once a day. Batch biotransformation assay was conducted as
five culture series in triplicate 200-mL serum bottles which were sealed with Teflon-lined septa and flushed
with nitrogen gas. Diclofenac in the samples was concentrated with OASIS HLB SPE cartridges (200 mg,
6 cc) (Waters, Millford, MA, USA) and measured with LC-MS/MS (Thermo Accela UPLC coupled with
Thermo Quantum Access tandem MS, USA) according to the method explained in Topuz et al. (2013).
Methane and carbon dioxide concentrations were determined by a GC unit (Agilent Technologies, Model
7890A).
The batch reactors were initiated by feeding the cultures with acetate (370 mg/L) and diclofenac
(50 µg/L) dissolved in methanol leading to a chemical oxygen demand (COD) of 1100 mg/L. After the first
amendment 80 mL CH4 production was observed in the culture. For the following feeding cycles the
reactors were amended with only acetate and approximately 30 mL methane production was measured at
the end of the feeding cycle which was very close to theoretical methane production (28 mL). COD removal
and methane production rate were higher in the reactors amended with acetate compared to the reactors fed
with glucose. Moreover, composition of biogas in terms of methane (80%) was higher in the cultures
amended with acetate compared to the reactors amended with glucose (70%). 75% of acetate was consumed
in 8 days for the first feeding. Higher acetate removal rate was observed for the following feeding cycles.
For the first feeding cycle 25% diclofenac removal was achieved in 8 days. However, at the end of the
incubation period the concentration of the diclofenac reached to the initial concentration. This increase
might be occurred because of the conversion of some of the biotransformation products of diclofenac to the
main compound as a result of the decrease in the carbon source. Although the culture was fed with acetate
for the following feeding cycles diclofenac degradation was not observed.
290
GRAPHENE-HAPTEN-BASED NANOSENSOR FOR ULTRASENSITIVE DETECTION OF

BISPHENOL A WITH AN OPTOFLUIDIC BIOSENSING PLATFORM
Feng Long* (Renmin University of China, Beijing, China)

Hanchang Shi (Tsinghua University, Beijing, China)
Two-dimensional graphene-based materials have emerged as promising transducers in diverse analytical

devices owing to its extraordinary optical, electrical, mechanical, and transport properties. Functionalized
with biomolecules (e.g. antibody or DNA), graphene-based biosensor have been widely used in
immunoassay, medical imaging, clinical/diagnostic assays, and biomolecular binding assay. However, both
experiments and simulations have indicated that when biomolecules, whose function relies on a specific
tertiary or quaternary structure, are immobilized onto graphene, the significant conformational changes and
loss of function have been demonstrated.
Combining the advantages of evanescent wave fiber optic sensor and microfluidic technology, a
facile and robust all-fiber optofluidics-based immunoassay platform was developed for rapid and
ultrasenstive detection of bisphenol A (BPA). BPA, a xenoestrogenic endocrine-disrupting chemical, has
been widely detected in environment and food. Through conjugating animated graphene with 4,4-bis-(4-
hidroxyphenyl) valeric acid (BVA, a structural analogue of BPA with a carboxyl group), hapten-grafted
graphene was employed as the immunological recognition of Cy3-labeled anti-BPA antibody as well as for
optical transduction, which could avoid the above-mentioned drawbacks.
Based on graphene’s excellent quenching capability toward various organic dyes, we designed a
fluorescence resonance energy transfer based competitive immunoassay method for detection of BPA.
When fluorescence labeled anti-BPA antibodies were selectively bound to the graphene-BPA nanosensor,
a reduction in the fluorescence emission of fluorescence labeled on antibodies by graphene was detected.
Based on the mechanism of competitive immunoassay, a high BPA concentration of sample reduces the
amount of fluroescence-labeled antibodies bound with graphene-BPA nanosensor, and thus a high
fluorescence singal was detected. The BPA quantified as 0.5 μg/L to 100 μg/L, with a detection limit of
0.06 μg/L. The potential interference of an environmental sample matrix was assessed by spiked samples,
and the recovery of BPA ranged from 90% to 120% with relative standard deviation values of < 9.1%.
The proposed sensing system has good characteristics, such as high sensitivity and selectivity, easy
operation, rapidity, robustness, portability, use of a small sample volume, and cost effectiveness. With the
use of different graphene-based nanosensors conjugated with other haptens, the proposed method can be
further developed for the rapid and sensitive monitoring of other small analytes in various application fields
ranging from environmental and biochemical to biomedical areas.
291
EFFECT OF FRESHWATER RELEVANT CONDITIONS ON THE AGGLOMERATION OF

TITANIUM DIOXIDE NANOPARTICLES
Emel Topuz* and Laura Sigg (Eawag- Swiss Federal Institute of Aquatic Science and Technology,
Dübendorf, Zurich, Switzerland)
İlhan Talınlı (Istanbul Technical University, Maslak, Istanbul, Turkey)
Titanium dioxide (TiO2) nanoparticles are used in various kinds of consumer products and they might enter
freshwater sources as a result of release from products. Agglomeration is one of the major processes
affecting the fate of nanoparticles in aquatic environment. Therefore, this study aims to evaluate
agglomeration of TiO2 nanoparticles in various freshwater relevant media including ions, natural organic
matters (NOM), surfactants and/or their combinations over 1 week.
Ionic media solutions were prepared by using NaCl, KCl, CaCl2, MgCl2, Na2CO3, NaNO3 or
Na2SO4 at concentrations to get 10 mM of ionic strength which is very close to freshwater conditions.
Humic acid, fulvic acid, sodium dodecyl sulphate and alkyl ethoxylate medium were prepared at
concentrations of 15 mg/L, 10 mg/L and 5 mg/L. Freshwater was simulated with the combinations of a
special ionic medium including CaCl2 (2mM), MgSO4 (0.4 mM), Na2CO3 (0.8 mM) and KNO3 (0.5 mM)
and NOMs (5 mg/L) and surfactants (1 mg/L). Daily prepared 1 mg/L of TiO2 solution was spiked to these
media and pH was adjusted to around 8.5. They were shaken at 100 rpm for one hour. Z-average size (based
on intensity mean) as hydrodynamic diameter and zeta potential was measured for duplicate samples with
Zetasizer (Nano ZS, Malvern Instruments) after 1 hour, 1 day and 1 week. Results were verified with NTA
(NanoSight LM10) measurements.
Monovalent (Na+, K+) and divalent cations (Ca++, Mg++), monovalent (Cl-, NO3-) and divalent
anions (CO32-, SO42-) were compared by using their solutions with chloride and sodium, respectively. Z-
average size of TiO2 suspended in the original solution was measured as 317±85 nm. Monovalent cations
were not as effective as divalent cations for the agglomeration over 1 week. However, Z-Average size of
TiO2 in the presence of K+ were slightly higher than in the presence of Na+ over 1 week which might be
due to the larger hydrated diameter of K+ than Na+ promoting agglomeration. TiO2 agglomerated from 400
nm to 800 nm over 1 day in the presence of divalent cations which might readily screen the surface charge
of TiO2 and compress the EDL leading to agglomeration. Chloride (when it is present with monovalent
cations) and CO32- might be effective for stabilizing TiO2, since NaNO3 and Na2SO4 lead to higher sizes in
1 week. Mean size in Ca(NO3)2 medium was high and similar to the CaCl2 medium; however, mean size in
CaCO3 medium was low and similar to the Na2CO3 medium. Moreover, zeta potentials of TiO2 with high
mean sizes were closer to zero surface charge than the others. Although Z-average sizes of TiO2 in the
suspension of NOMs and surfactants were fluctuating slightly for 1 hour and 1 day, they were always lower
than the Z-average size of original TiO2 suspension after 1 week which shows the dispersing effect of
organic matters. Average sizes for 1 hour and 1 day samples of TiO2 suspended in ionic medium mixed
with one component suggest that NOM and surfactants may act as stabilizer for a short time. However,
results in 1 week were very similar to the results for ionic medium itself which shows that agglomeration
up to 1 µm might be inevitable over 1 week in spite of presence of NOMs or surfactants. However, fulvic
acid seems to be effective for stabilizing TiO2 around 600 nm even for 1 week when it is present in fresh
water simulated medium with other NOM or surfactants. The combinations without fulvic acid resulted in
higher average sizes.
In conclusion, TiO2 nanoparticles might agglomerate around 500 nm in 1 day and over micrometer
in 1 week in most of the freshwater media and settle to the sediment over time leading to exposure of
benthic organisms. However, carbonate ions or fulvic acid could stabilize TiO2 nanoparticles in 1 week.
292
USING PERSULFATE ACTIVATED BY AN EMPLACED ZONE OF IRON NANOPARTICLES

TO TREAT A TRICHLOROETHYLENE SOURCE ZONE
Mohammed A. Al-Shamsi (National Centre for Environmental Technology, King Abdulaziz City for
Science & Technology, Kingdom of Saudi Arabia)
Neil R. Thomson (Department of Civil & Environmental Engineering, University of Waterloo,
Waterloo, Ontario, Canada)
Recently, metal nanoparticles have attracted attention as promising peroxygen activators for the rapid
and effective remediation of organic contaminants. In this work, a one-dimensional physical
model experiment was designed to investigate the mobility of the metal nanoparticles in porous media,
and the potential use of metal nanoparticles as peroxygen activators for in situ treatment of source
zones. We found that our synthesized nano-Pd-Fe0 particles were mobile in a non-geological porous
medium and relatively immobile in a geological porous medium. In addition, we observed that
iron-based bimetallic nanoparticles were able to remain in suspension in an ideal aqueous system
much longer (>6 weeks) than iron-based monometallic nanoparticles (<1 hour). To overcome the
nano-Pd-Fe0 particle delivery issue in geological porous media, an activation zone approach was
adopted. Nano-Pd-Fe0 particles were injected in order to create a zone to activate persulfate for
the treatment of a trichloroethylene source zone. Trichloroethylene mass destruction was only 9 %
higher in the nano-Pd-Fe0 activated persulfate system compared to the non-activated persulfate system
as revealed by a short duration chloride concentration spike in the effluent. In addition, the nano-
Pd-Fe0 activation zone was rapidly deactivated after being exposed to persulfate as visually observed
by a color change, indicating that the longevity of the activation zone is limited.
293
MATHEMATICAL SIMULATION OF NANO SIZED ALUMINUM PHAGES TO PURIFY

WATER
V.K. Katiyar* (Indian Institute of Technology, Roorkee)

Rohit Agarwal (Dehradun Institute of Technology, Dehradun)
The nano particles can be easily used to purify the water easily and effectively. This is what shown in this
paper. This is being supported by the mathematical modeling of nano sized aluminum phages in the river
water. The water of the Ganga is taken as a reference to the application. The research is useful for the
industries which deal in the water purification. The method discussed is cheaper to the other methods
available for the purification of water for drinking. The effectiveness of the method comprises of the
removal micro-organism from the water. The general size of the phages present in the water is of the order
of 300X10-9 m or 300nm.
294
INTERACTION OF BACTERIAL BIOFILMS WITH ENGINEERED NANOPARTICLES
Hengye Jing and George A. Sorial (University of Cincinnati, Cincinnati, OH, USA)
Ashraf Aly Hassan, Endalkachew Sahle-Demessie and Christina Bennett-Stamper (USEPA, Cincinnati,
OH, USA)
Biofilms are surface-associated and highly-stratified microbial communities, commonly existing in natural
environment and water distribution systems. Studying the interaction between nanoparticles (NPs) and
biofilms will help to better understand the fate and transport of NPs in the environment and evaluate its
risks to aquatic ecosystem. In this study, the interaction and diffusion of NPs within biofilms of
Pseudomonas fluorescens and Mycobacterium smegmatis were evaluated. SEM and TEM images provided
the information on distribution of Ag-NPs penetration through the biofilm and the adsorption sites within
the biofilm. Batch sorption kinetics studies were conducted to understand the influence of water pH, ionic
strength, initial concentration of NPs and disaffects of dispersant coating. SurPASS zeta potential analyzer
helped to determine the surface charge changing while NPs occupied the sorption sites on biofilm surface.
Atomic force microscopy (AFM) and laser scanning microscopy (LSM) provided a 3-D graphic structure
of biofilm. By applying FilmTracerTM LIVE/DEAD biofilm Viability Kit, LSM also allowed estimation of
live and dead bacteria within the biofilm when exposed to Ag-NPs.
295
EVALUATING STABILITY AND STRUCTURAL CHANGES OF NANOCOMPOSITES AND

DEVELOPING METHODS TO EVALUATE THE RELEASE OF NANOPARTICLES
Amy Zhao1, E. Sahle-Demessie1, Heidi Grecsek2, (1U.S. EPA, Office of Research and Development,
NRMRL, 26 W. Martin Luther KingDrive , Cincinnati, OH 45268, USA; 2PerkinElmer Inc. 6159 NW
32nd. Ave., Boca Raton FL 33496, USA)
This study aims in better understanding of the environmental risks of long term use of carbon composites
and the influence of fillers on the extent of chemical photo-degradation depending on the combination of
polymer and filler. The UV weathering of nano-composites and methods of characterizing structural
changes and the potential of release of nano-particles from the composite matrix will be focused. The
increase in structural breakdown and possible release of nano-particles caused by brittleness of the matrix
material is being analyzed using thermo-gravimetric analysis (TGA) coupled with GC-MS, and the changes
in glass transition temperatures using differential scanning calorimeter. To provide insight to the stability
and kinetics of structural changes of UV weathering measurement of the light emitted through chemo-
luminescence is used to determine the concentration of the excited polymer matrix elements. These results
are compared with other characterization techniques, FTIR, electron microscopy (SEM and TEM) and X-
ray diffraction analysis, XPS, and AFM, to measure changes with increase dose of UV-Light. The release
of nano-materials to water and gas phase will be measured to determine potential release to air or rain wash
using single particles ICP-MS (SP-ICP-MS) from metal based nano-materials and TEM for lyophilized
samples. Tests are be made to simulate release of nano-particles during wash cycles of textile nano-
composite (mostly polyamides) that have been environmentally aged.
296
PREPARATION OF A NOVEL MAGNETIC NANOPARTICLE ADSORBENT AND ITS

ADSORPTION BEHAVIOR OF ARSENIC IN GROUNDWATER
Shuqiong Kong, Yanxin Wang*, Qinhong Hu* and Abass K. Olusegun

(State Key Laboratory of Biogeology and Environmental Geology and School of Environmental Studies,
China University of Geosciences, Wuhan, 430074, P. R. China)
A novel magnetic nanoparticle adsorbent kaolinite loaded magnetite was prepared by an improved
precipitation method. It is easily recovered by magnetic field achieving solid/liquid separation. The removal
of arsenic in contaminated groundwater on the adsorbent is evaluated in this study. With the measured
surface area by BET method is 213 m2/g, the removal efficiency of it for arsenic is more than 99.2 % at pH
7.0. The adsorption kinetics is well fitted with pseudo-second-order, as well as Weber–Morris model.
Results show that arsenic adsorption on it is predominantly regulated by surface diffusion in initial 10 min,
followed by intraparticle diffusion in later stage. The adsorbbent exhibits a strong adsorption affinity to
arsenic, and the adsorption isotherms are well described by Freundlich and Redlich–Peterson models. A
thermodynamic analysis indicates that the adsorption is spontaneous and endothermic. Adsorption site
energy analysis illustrates a distribution of adsorption energy, revealing the heterogeneous distribution
nature of adsorption energy on the adsorbent for arsenic removal. This study proves the adsorbent as a
promising adsorbent for arsenic removal in contaminated groundwater.
297
SURFACE CHEMISTRY OF IRON-IMPREGNATED MINERAL OXIDES AND CATALYTIC

ACTIVITY FOR OXIDATION OF AQUEOUS CONTAMINANTS
Weile Yan and Yue Li*

(Texas Tech University, Lubbock, TX, USA)
Iron-based catalysts have attracted special interest among researchers owing to its benign nature, abundant
presence in the natural environment, and strong catalytic activity for redox transformation of organic
contaminants. Extensive studies have been conducted to understand reactions catalyzed by single-phase
iron oxides; however, the reactivity of surface-anchored iron species on common mineral colloids, such as
amorphous or crystalline silica and aluminum oxide, is not well understood. In this study, we sought to
understand the fundamental relationship between the surface chemistry of Fe(III)-impregnated silica and
alumina surfaces and their catalytic activity in activating environmental oxidants such as dissolved oxygen
and hydrogen peroxide. Specifically, we employed surface analysis techniques such as high-resolution X-
ray electron spectroscopy (HR-XPS), atomic force microscope (AFM) and diffuse-reflectance UV-Vis
spectroscopy to comprehensively characterize the molecular structure, surface coverage, and nature of
Fe(III) dispersion on micron and nanometer-scale silica and alumina particles. Aqueous adsorption
experiments were conducted to quantify the mass loading of iron on different mineral particles. The
catalytic activity of these Fe(III)-amended particles was evaluated in batch reactions using phenol or
benzoic acid as prototypic organic contaminants in the presence of H2O2. It was found that, while coating
the mineral solids with small amounts of Fe(III) has led to appreciable reactivity in the breakdown of the
probe compounds, the catalytic activity of the solids correlates more strongly with the molecular structure
and surface dispersion of Fe(III) than with the absolute Fe(III) loadings. Furthermore, the important surface
chemistry characteristics identified are strongly influenced by the nature of the mineral particles as well as
the solution conditions during Fe(III) deposition. These findings provide new insights into the formulation
of efficient and environmentally-benign catalysts for water decontamination or purification applications.
298
ELECTROCATALYTIC CHARACTERISTICS OF HYBRID MWCNTS AND GNPS WITH

DIFFERENT SURFACE MORPHOLOGY
Yanping Cui (China University of Geosciences (Wuhan), Wuhan, Hubei Province, China;
Northeastern University, Boston, MA, USA)
Yu Zhu, Yaohui Wang and Yanyan Qin (China University of Geosciences (Wuhan), Wuhan, Hubei
Province, China)
ABSTRACT: Electrocatalytic characteristics with different surface morphology of hybrid gold

nanoparticles and multi-walled carbon nanotubes were studied in this paper by detecting uric acid (UA) and
ascorbic acid (AA) in water. Gold nanoparticle fabricated on multi-walled carbon nanotubes
(GNPs/MWCNTs) and multi-walled carbon nanotubes assembled on gold nanoparticles arrays
(MWCNTs/GNPs) were synthesized by seed-mediated growth approach. The wet chemical method
guaranteed the direct attachment of mono-dispersed gold nanoparticles and multi-walled carbon nanotubes
modified on tin oxide (ITO) surfaces. Electrocatalytic characteristics of two hybrid nanocomposites were
tested by oxidation behaviors of UA and AA on modified electrodes. Electrocatalytic characteristics of
these hybrid electrodes were proved dramatically different to UA and AA which were depended on both its
surface characteristic and objects.
INTRODUCTION
The modification of hybrid materials providing extensive applications in the determination of
biomolecules such as choline, cholesterol, and dopamine (Qin et al., 2010; Eguílaz et al., 2011; Jia et al.,
2011), has been demonstrated. The employment of multi-walled carbon nanotubes (MWCNTs) evidently
brings the benefits of high reactive surface area, high electrical conductivity and good chemical stability
for the electrochemical reactions. Generally, gold nanoparticles (GNPs) have been voted as one of the most
popular nanomaterials in electrode modification, because of its large specific surface area, good
biocompatibility and dramatic catalytic properties. Nanocomposites of GNPs and MWCNTs have become
the favorite materials as the electrocatalyst due to their unique dimensions and catalytic activities.
Based on our group’s previous work (Cui et al. 2010, 2007, 2007), wet chemical methods were
used to fix gold nanoparticles and MWCNTs directly onto substrate. Results revealed different
nanomaterials have unique electrocatalysis effects to different objects. So, with those experimental
procedures, GNP and MWCNTs hybrid materials were prepared with different surface morphology and
applied for investigating the electrochemical behavior of small biomolecules.

Cetyltrimethylammonium bromide (CTAB), Uric acid (UA) and Ascorbic Acid (AA) were
purchased from sigma. MWNTs was got from Nanjing Xianfeng NANO Materials Tech Co. Ltd. (Nanjing,
China). All other solvents and chemicals were of analytical grade. Stock solutions of uric acid, and ascorbic
acid were freshly prepared as required in 0.20 mol/L phosphate buffer solutions (PBS) at the desired pH
(7.0). All solutions were prepared with purified water (18.3MX cm, Dubuque, USA).
Electrochemical experiments were carried out on CS300 electrochemical workstation (Wuhan
Kesite Instrument Co., China) with a three-electrode cell. A platinum wire was employed as the counter
electrode. All potentials were referred to saturated calomel electrodes (SCE). Bare or modified indium tin
oxide electrodes (2.5 mm diameter) were used as working electrodes.
The gold nanoparticle arrays were fabricated upon ITO substrates, based on a modified seed
mediated growth approach (Zhang et al., 2005). MWCNTs were formed a homogeneous MWNTs/Nafion
299
solution (Cheng et al., 2008) then directly dropped onto substrate. MWCNTs-GNPs-ITO and GNPs-
MWCNTs-ITO modified electrodes were obtained by different modification sequence of GNPs and
MWCNTs.
A 45
e
30
i/μA
c
15
d
b
0 a
0.0 0.3 0.6 0.9 1.2

E/V
B 60
c
e
b
45 d
i/μA
a
30
15
0.0 0.3 0.6 0.9 1.2

E/V
FIGURE1. CVs on Bare ITO (a), GNPs/MWCNTs /ITO (b), MWCNTs/ITO (c), GNPs/ITO (d),
MWCNTs/GNPs/ITO (e) for 1 mol/L UA(A),and 5 mol/L AA (B). Scan Rate: 50 mV/s.
To characterize the electrochemical features of two as-prepared composites, the electro oxidation
behavior of UA and AA on the bare ITO, MWCNTs or GNPs modified ITO electrodes was studied by
cyclic voltammetry (CV).The catalytic activity of two hybrid electrodes were observed for the
electrochemical oxidation of UA and AA were showed as Fig. 1 A and Fig. 1 B.
300
To UA oxidation process, MWCNTs/GNPs/ITO modified electrode exhibited dramatically

synergistic effect of MWCNTs and GNPs. Compared with GNPs/ITO, the oxidation Ipa of UA on
MWCNTs/GNPs/ITO increased almost 3 times accompanied with 210 mV oxidation Epa decrease. When
compared with MWCNTs/ITO, although the oxidation Epa of UA on MWCNTs/GNPs/ITO has no change,
the oxidation Ipa increased 60.0%. This proved MWCNTs/GNPs/ITO exhibited the synergetic
electrocatalytic effects of MWCNTs and GNPs to oxidation of UA. With the comparison with oxidation
results on GNPs/MWCNTs/ITO, MWCNTs/GNPs/ITO exhibited significantly catalysis to UA with
150mV Epa decrease and Ipa 3 times increase, which indicated that MWCNTs has special effects on UA.
While, to the electro oxidation of AA on MWCNTs/GNPs/ITO modified electrode has similar
oxidation behavior with on MWCNTs/ITO without obviously oxidation Epa and Ipa changes. It means
MWCNTs/GNPs/ITO hybrid modified electrode only provided the characteristics of MWCNTs, instead of
synergetic effects. At the same time, compared with GNPs/MWCNTs/ITO, the oxidation of AA on
MWCNTs/GNPs/ITO has a 190 mV Epa decrease with little Ipa change. These results indicated although
MWCNTs has more electrocatalytic effects than GNPs to AA electrooxidation, the hybrid
MWCNTs/GNPs/ITO can not provide synergetic effects to AA as to UA.
CONCLUSIONS
Surface characteristic effects on electrocatalytic ability of hybrid nanomaterial were studied with
different objects. Hybrid MWCNTs and GNPs modified electrode showed dramatic synergistic effect only
to UA. While, to AA, the electro catalysis properties of hybrid modified electrode only depended on the
outside material. These results provide more detailed in electrocatalytic mechanism of hybrid
nanomaterials.
ACKNOWLEDGEMENTS
This work was supported by National Natural Science Foundation of China (No: 40902070), and
Fundamental Research Funds for the Central Universities (No: CUG110414).
REFERENCES
Cheng, Y. X., Y. J. Liu, J. J. Huang, Y. Z. Xian, W. Zhang, Z. H. Zhang, L. T. Jin. 2008. “Rapid
amperometric detection of coliforms based on MWNTs/Nafion composite film modified glass carbon
electrode”. Talanta, 75: 167-171.
Cui, Y. P., C. Z. Yang, W. H. Pu, M. Oyama, J. D. Zhang. 2010. “The Influence of Gold Nanoparticles on
Simultaneous Determination of Uric Acid and Ascorbic Acid”. Analytical Letters, 43: 22-33.
Cui, Y. P., C. Z. Yang, W. Zeng, M. Oyama, W. H. Pu, Y. Q. Zheng, J. D. Zhang. 2007. “Three Dimensional
Monolayer of 3-Mercaptopropionic Acid Assembled on Gold Nanoparticles for Electrochemical
Determination of Trace Cu(II)”. Analytical Letters, 40: 2151-2160.
Cui, Y. P., C. Z. Yang, W. Zeng, M. Oyama, W. H. Pu, J. D. Zhang. 2007. “Electrochemical Determination
of Nitrite Using a Gold Nanoparticles-modified Glassy Carbon Electrode Prepared by the Seed-
mediated Growth Technique”. Analytical Sciences, 23: 1421-1425.
Eguílaz, M., R. Villalonga, L. Agüí, P. Yáñez-Sedeño. 2011. “Gold nanoparticles:
Poly(diallyldimethylammonium chloride)–carbon nanotubes composites as platforms for the
preparation of electrochemical enzyme biosensors: Application to the determination of cholesterol”
Journal of Electroanalytical Chemistry, 661: 171–178.
Jia, D., J. Y. Dai, H. Y. Yuan. 2011. “Selective detection of dopamine in the presence of uric acid using a
gold nanoparticles-poly (luminol) hybrid film and multi-walled carbon nanotubes with incorporated
β-cyclodextrin modified glassy carbon electrode”. Talanta, 85: 2344–2351.
301
Lin, A. J., Y. Wen, L. J. Zhang. 2011. “Layer-by-layer construction of multi-walled carbon nanotubes, zinc
oxide, and gold nanoparticles integrated composite electrode for nitrite detection”. Electrochimica Acta
, 56: 1030–1036.
Qin, X., H.C. Wang, X.S. Wang. 2010. “Amperometric biosensors based on gold nanoparticles-decorated
multiwalled carbon nanotubes-poly(diallyldimethylammonium chloride) biocomposite for the
determination of choline”. Sensors and Actuators B , 147: 593–598.
Sadek, A. Z., V. Bansal, D. G. McCulloch. 2011. “Facile, size-controlled deposition of highly dispersed
gold nanoparticles on nitrogen carbon nanotubes for hydrogen sensing”. Sensors and Actuators B, 160:
1034–1042.
Zhang, J. D., M. Oyama. 2005. “Gold nanoparticle arrays directly grown on nanostructured indium tin
oxide electrodes: Characterization and electroanalytical application”. Analytica Chimica Acta, 540:
299–306.
Zhang, R. L., Q. F. Wang, L. Zhang. 2008. “The growth of uncoated gold nanoparticles on multiwalled
carbon nanotubes”. Colloids and Surfaces A: Physicochem. Eng. Aspects, 312: 136–141.
Zhang, R. Y., M. Hummelgård, H. Olin. 2009. “Simple and efficient gold nanoparticles deposition on
carbon nanotubes with controllable particle sizes”. Materials Science and Engineering B, 158: 48–52.
302
VISIBLE-LIGHT RESPONSIVE PHOTOCATALYTIC FUEL CELL BASED FOR

SIMULTANEOUS WASTEWATER TREATMENT AND ELECTRICITY GENERATION
Jing Bai, Jinhua Li, Suqin Jiang and Baoxue Zhou*

(Shanghai Jiao Tong university, Shanghai, China)
A visible-light driven photocatalytic fuel cell (PFC) system comprised of TiO2/BiVO4 photoanode and
Cu2O/TiO2/Pt photocathode was estatablished for organic compounds degradation with simultaneous
electricity generation. The central idea for its operation is the mishmatched Fermi levels between the two
photoelectrodes. Under solar irradiation, the interior bias voltage produced for the Fermi level difference
between photoelectrodes, drives photoelectrons of TiO2/BiVO4 photoanode to combine with photoholes of
Cu2O/TiO2/Pt photocathode through external circuit thus generating electricity. In the meantime, organics
are decomposed by photoholes remained at BiVO4/TiO2 photoanode. In this manner, the electron/hole pairs
separations at two photoelectrodes are facilitated to release the holes of TiO2/BiVO4 photoanode and
electrons of Cu2O/TiO2/Pt photocathode. The results demonstrated that various model compounds
including phenol, Rhodamine B, and Congo red can be successfully decomposed in this PFC system, with
the degradation rate after 5 h operation were obtained to be 65%, 70%, and 81%, respectively. The
consistent operation for continuous water treatment with the electricity generation at a long time scale was
also confirmed from the result. The proposed PFC system provides a self-sustained and energy-saving way
for simultaneous wastewater treatment and energy recovery
303
LOW GRADE HEAT: AN UNDERUSED ENERGY SOURCE FOR DESALINATION USING

MEMBRANE DISTILLATION
Farid Benyahia
(Qatar University, Doha, Qatar)
The demand for fresh water supplies in the Arabian Gulf continues to increase significantly due to
population and economic growth in the region. In Qatar, freshwater is produced mainly by thermal
desalination combined with power plants. This indicates that both hot concentrated reject brines and low
grade waste heat are available and currently discarded. Membrane distillation (MD) is a hybrid thermal
membrane process that works at relatively low temperatures and can therefore utilize low grade heat to
generate a vapor pressure difference across a hydrophobic membrane to produce a high quality distillate
from high salinity brines. Membrane distillation appears to be an attractive technology to increase
freshwater production in Qatar and the GCC as a whole. An investigation into the potential utilization of
low grade heat in selected power and desalination plants indicated that up to 1.4 million cubic meters of
good quality distilled water can be produced with no significant carbon footprint. Experiments on a
laboratory MD setup utilizing high salinity feed brines from the power and desalination plants investigated
showed that the distillate TDS was less than 3 ppm and was thus of excellent quality for a broad range of
application, industrial or domestic. This work clearly identified the excellent potential to integrate
membrane distillation desalination with petrochemical industries in the Arabian Gulf to exploit the vast
amount of low grade heat to produce quality freshwater with negligible carbon footprint.
304
AIR POLLUTION
AND
AIR QUALITY CONTROL
305
PERFORMANCE OF AEROSOL SAMPLING INLET FROM AIRCRAFT PLATFORM
Baoqing Wang*, Shu Yao, Zebei Wang, Ronghui Chen, Shuai Yin
(College of Environmental Science and Engineering, Nankai University, Tianjin 300071, China)
ABSTRACT: An aerosol sampling inlet was designed for collecting and measuring aerosol from aircraft
platform. CFD was used to perform flow and efficiency simulation for the aerosol sampling inlet. The inlet
makes use of diffuser to slow the sample flow from aircraft airspeeds near 50 m/s to 5 m/s without
generating turbulence. Three different particle aerodynamic diameters (1, 2.5and 10μm), ranging from
ultra-fine to coarse particle ranges, are used to investigate the relationship between particle size and each
transmission efficiency. The aerosol transmission efficiency of sampling inlet at airspeed 50m/s is 77.7%,
76.4% and 64.4% for different particle aerodynamic diameters 1, 2.5and 10μm, respectively. Results of this
study show that CFD simulation can be useful for improving the optimum aircraft-carried aerosol sampling
inlet.
*Email: wangbaoqing@nankai.edu.cn
INTRODUCTION
Aerosol particles are related with many environmental and climate phenomenon. They can reflect
light and affect the Earth's radiation balance, have adverse effects on human health and transmission
pollutants in the global scope. Thus it is important to monitor and analysis the physical characteristics (e.g.,
concentration, particle size distribution, chemical composition) and the spatial and temporal distribution of
the aerosol particles[i][ii]. As remote sensing technologies can not directly measure the properties of aerosol
particles, aircraft-carried aerosol sampling platform has become a new and challenging way for collecting
and measuring aerosols.
In this study, we use the CFD (Computational Fluid Dynamics) method to simulate and optimize
the design of the aerosol sampling inlet, and discuss the performance of sampling inlet[iii]. The inlet makes
use of a diffuser to slow the sample flow from near 50 m/s (aircraft airspeed) to 5 m/s (sampling flow speed)
without generating turbulence. The results proved that the aerosol transmission efficiency for sampling inlet
is acceptable.
METHOD
The aerosol sampling inlet is the vital part of the whole sampling system. It could change the
particle size distribution of aerosols and influence the accuracy of sampling results. The inlet should
decelerate the airflow from near 50 m/s (aircraft airspeed) to 5 m/s (sampling flow speed), minimize the
loss of aerosol particles to ensure representativeness, and reduce the size to avoid its influence on aircraft
manipulation.
Isokinetic sampling can be achieved using a diffusion channel with a shroud deflector. Design of
the diffusion channel should consider reasonable shape and expansion angle[iv]. Sharp edged inlet can
minimize the sampling loss caused by inertia and bounce of aerosols[v][vi]. Half expansion angle larger than
4° will cause flow separation and turbulence which would change flow direction[vii][viii].
The sampling flow rate of the sampling system is set to be 100 L/s, and the sampling flow speed
and aircraft airspeed is set to be 5 m/s and 50 m/s respectively. Thus the front and backend diameter of the
diffusion channel is calculated to be 6.52 mm and 20.60 mm respectively. CFD method is then used to
simulate and optimize the design of expansion angle, the shroud deflector and the bending radius of the
inlet.
306
Fig. 1. Schematic of the computational domain of the sampling inlet
Fig. 2. The particles trajectory at bending radius 100, 150, 200, 250 and 300mm
307
Fig.1 shows schematic of the computational domain of the sampling inlet. To ensure sufficient flow
movement, the distance between the front and the back of the domain and the inlet is the same and twice
the length of the inlet, respectively. The diameter of the computational domain is 6 times the diameter of
the inlet.
The major factor that influence the transmission efficiency of aerosol particles passing through the
inlet are bending ratio and particle diameter[ix]. The bending ratio is defined as the ratio of bending radius
to tube radius. Fig.2 shows the particles trajectory of various bending radius 100, 150, 200, 250 and 300mm.
Table 1 shows the particles transmission efficiency of various bending radius for 10-μm-diameter
particles. Transmission effiency increases with the increasing bending radius, and it’s close to 100% when
the radius is 300 mm. So bending radius of 300 mm is chosen in final design.
Table 1. The particles transmission efficiency of various bending radius for

10-μm-diameter particles
Bending radius(mm) Bending ratio Transmission efficiency(%)
100 4.85 92.28
150 7.28 93.07
200 9.71 94.97
250 12.14 98.98
300 14.56 99.72
Several half expansion angles were simulated to observe airflow conditions in the diffusion channel
and 3.5°is considered to be an appropriate value. The location and size of the shroud was also simulated
and the overall design is showed in Fig.3.
Fig. 3. Schematic diagram of the sampling inlet
RESULTS
As the aerosol sampling platform could operate at different flight attitude, airspeed and airflow
angle, the performance of the sampling inlet is also simulated under different conditions.
Fig. 4 shows the velocity distribution at the entrance of the inlet at 1 km and 3 km height,
respectively. It shows that the flow state inside the inlet kept steady from 1 km to 3 km height, so the
sampling inlet could work well at flight attitude of the sampling platform.
308
Fig. 5 shows the velocity contour of the flow when airflow has an 8° angle for the sampling inlet
without shroud. Fig,6 shows the velocity contour of the flow when air flow has an 8° angle for the sampling
inlet with shroud. It suggests that with the presence of shroud deflector, the flow is still parallel to the inlet
and isokinetic sampling is achieved.
Table 2 shows the transmission efficiency of aerosol particles of different diameter at different
airspeed. The efficiency decreases with increasing airspeed and particle diameter, but the overall
performance of the sampling inlet is quite acceptable.
Fig. 4. Velocity distribution at the entrance of the inlet at 1 km and 3 km height
Fig. 5. Velocity contour of the flow when airflow has an 8° angle for the sampling inlet without
shroud
CONCLUSIONS
In this study, we use the CFD method to simulate and optimize the design of the aerosol sampling
inlet. Factors such as bending ration, expansion angle and size and location of the shroud deflector are
considered during the simulation. It proved that the sampling inlet can work well at different flight attitude,
airspeed and with the presence of airflow angle. The aerosol transmission efficiency of the sampling inlet
at airspeed 50 m/s is 77.7%, 76.4% and 64.4% for particle diameter 1, 2.5and 10μm, respectively. The result
309
is quite acceptable and it shows that CFD simulation can be a useful tool to optimize the design of aircraft-
carried aerosol sampling inlet.
Fig. 6. Velocity contour of the flow when airflow has an 8° angle for the sampling inlet with shroud
Table 2. Transmission efficiency of aerosol particles of different diameter at different

airspeed（
（ %）
Airspeed(m/s)
Particle diameter(μm)
40 50 60
1 77.9 77.7 75.7

2.5 77.7 76.4 75
10 68.7 64.4 60.3
ACKNOWLEDGMENTS
This work was financially supported by National major scientific instrument equipment
development special (2011YQ060111).
REFERENCES
1. Rasool, S. I. and Schneider, S. H. (1971) Atmospheric carbon dioxide and aerosols: effects of large
increases on global climate. Science 173, 138-141.
2. Brunekreef, B.and Holgate,S.T: Air Pollution and Health, The Lancet, 360, 1233-1244, 2002. 1100
3. FLUENT Inc., 2005. FLUENT 12.6 User’s Guide.
4. Huebert, B. J., Lee, G. and Warren, W. L. (1990) Airborne aerosol inlet passing efficiency
measurements. J. geophys.Res. 95, 16369-16381.
5. McFarland, A. R., Ortiz, C. A., Moore, M. E., Deotte, R. E. Jr. and Somasundaram, S. (1989). A
shrouded aerosol sampling probe. Environ. Sci. Technol. 23, 1487-1492.
310
6. Wilson, J.C. and W.R. Seebaugh, Measurement of Aerosol from Aircraft in Aerosol Measurement:
Principles, Techniques, and Applications, ed. P.A. Baron and K. Willeke, (Wiley-Interscience,
2001).
7. Schlichting, H. (1987) Boundary Layer Theory, 7th Edition. McGraw-Hill, New York.
8. Twohy C.H., Aerosol Sci. and Tech., 29, (1998) 261-280.
9. Crane, R. I., and R. L. Evans, 1977: Inertial deposition of particles in a bend pipe. J. Aerosol Sci.,
8, 161–170
311
APPLICATION OF FACTAL ANALYSIS TO ASSESS OF AIR POLLUTANT EMISSION

RATES IN OPENCAST COAL MINES- AN INNOVATIVE APPROACH
Mrinal K.Ghose
(Department of Biotechnology, West Bengal University of Technology, Kolkata,- 700064, India)
To maintain the energy demand, opencast mining has been growing at a phenomenon rate in India.
However, it creates high air pollution problem within the work zone areas and disperses along with
the wind. Regulatory requirements for air quality impact assessment are discussed. This paper
examines the utility of air pollutant emission rates due to mining for evaluating the impact on
environment and a large opencast coal project of BCCL was chosen for the study. The paper
focuses on the use of emission factor data for the quantification of mine dust, development of factal
analysis for the estimation of emission rates and their dispersion potential in the area. The study
area was also being polluted by the surrounding industrial activities. It discusses the application of
factal analysis technique to evaluate the actual contribution of air pollutants due to a project in
question. . Approach for the selection of air monitoring stations and methods adopted for air quality
survey for factal analysis have been described. Four season data were generated and they were
critically analyzed on the basis of dominant wind directions at different seasons. From the
monitoring data obtained for factal analysis the emission rates of mining activities have been
determined A set of empirical formulae has been developed by considering the major influencing
parameters for the estimation of SPM, SO2 and NOx emission rates for the whole mine. The results
obtained from these three different methods are found to be comparable and the methodology can
be accepted as a guideline for the assessment of emission rate. Applications of this innovative
approach are immense may help the practicing mine environmental engineers and mine managers
to get prior information on the likely impact on air quality and the methodology adopted can be
applicable on an industrial scale for various sites.
Keywords. Coking coal, emission factor, dominant wind, monitoring, factal analysis,
empirical formula
312
PLS-PATH MODEL ANALYSIS FOR UNDERSTANDING THE CAUSE-EFFECT

RELATIONSHIP OF GROUND LEVEL OZONE CONCENTRATION
A. K. Gorai* (Birla Institute of Technology, Mesra, Ranchi, India)

F. Tuluri and P. B. Tchounwou (Jackson State University, Jackson, USA)
Ground‐level ozone (O3) is produced by a complex chain of atmospheric chemical reactions that depend on
precursor emissions from natural and anthropogenic sources. Ground‐level ozone concentration in a
particular location is also governed by local weather and climatic factors. In this work an attempts was
made to explore a Partial Least Squares Path Modelling (PLS-PM) approach to quantify the inter-
relationship between local conditions (weather and primary air pollution) and ground level ozone
concentrations.
PLS-PM has found increased applications in many fields due to its ability to handle complex
models. A PLS path modelling algorithm is introduced and applied to ground-level ozone concentration
analyses at Gulfport, Mississippi area in US. The model was run in plspm package of r 3.0.2 software for
the analysis.
In the present analysis, three latent variables were selected: PRC (photochemical reaction catalyst),
MP (meteorological factor), and OPP (other primary air pollutants). The three latent variables have 14
indicators for the analysis - PRC has two [SR1 represents extraterrestrial radiation on horizontal surface
in W/m2, and SR2 represents extraterrestrial radiation normal to the sun in W/m2], , MP has nine [TEMP
(Temperature in °F), DP (Dew point temperature in °F), HUM (Relative humidity in percentage), PRES
(Pressure in inch), VIS (Visibility in distance mile), MWS (Maximum wind speed in miles/hr), AWS
(Average wind speed in miles/hr), PREC (Precipitation in inch), and WD (Wind direction in degrees)] and
OPP has three [NOx (Daily Maximum 1-hour NO2 concentration in ppb), PM2.5 (24 hour average
particulate matter less than 2.5μm size in μg/m3), and SO2 (Daily Maximum 1-hour SO2 concentration in
ppb)]. The model results revealed that PRC has significant direct impact on ground level ozone
concentration but very small overall effects. This is because PRC has significant indirect negative impact
on GLO via MP. Thus, when both direct and indirect effects are taken into account, PRC emerges as having
the weakest effect on GLO. The third block OPP (other pollutant parameters) has also positive impact on
ground level ozone concentration.
*Email: amit_gorai@yahoo.co.uk
313
INTRA-URBAN SPATIAL AND TEMPORAL COMPARISON OF FINE AND QUASI-

ULTRAFINE PARTICLES IN HOUSTON, TEXAS
Yuncan Guo, Masoud Afshar, and Inkyu Han

(University of Texas Health Science Center School of Public Health, Houston, TX, USA)
Evidences have shown that fine particulate matter (PM2.5; aerodynamic particle size less than 2.5µm) and
ultrafine particles (aerodynamic particle size less than 100nm) are associated with adverse health outcomes
for general and susceptible urban populations. The characterization of fine and coarse PM has been widely
documented, however, limited evidence is available on spatial and temporal variation of size-segregated
PM including ultrafine particles.
To characterize spatial and temporal variations of size-segregated PM in Houston, Texas, USA, we
have collected size-segregated PM, including size>2.5µm, 1.0-2.5µm, 0.5-1.0µm, 0.25-0.5 µm, and quasi-
ultrafine particles (quasi-UFP, PM<0.25 µm) on the roof of University of Texas School of Public health
(UTSPH) and at an US EPA National Ambient Air Quality Monitoring Station located at Clinton Dr. in
Houston, TX from January to September 2013. At each site, a cascade impactor was deployed on the same
day. Size-segregated PM samples were being collected simultaneously at both sites weekly.
Weekly average concentrations of fine PM were higher at Clinton site than UTSPH (14.2 and
10.5µg/m3 respectively, P<0.012), and weekly average concentrations of quasi-UFP were higher at Clinton
site than UTSPH (5.8 and 4.6µg/m3 respectively, P<0.008). Results showed that average quasi-UFP
concentration represents 40.4% of fine PM mass concentration at Clinton site and 43.7% at UTSPH. The
weekly averages of fine PM were higher in warm season at both sites (Clinton: 15.7µg/m3, UTSPH:
11.7µg/m3) than cool season (Clinton: 12.6µg/m3, UTSPH: 8.9µg/m3). The weekly averages of quasi-UFP
were also higher in warm season at both sites (Clinton: 6.0µg/m3, UTSPH: 5.0µg/m3) than cool season
(Clinton: 5.4µg/m3, UTSPH: 4.0µg/m3).
Results showed that fine and quasi-UFP mass concentrations are spatially and temporally different
between two sites. The elevated levels of size-segregated PM in Clinton site may be attributed to both
industrial and mobile sources, while those in UTSPH are attributed to general urban sources. In our ongoing
study, we plan to perform source apportionment analysis by analyzing organic chemical species at both
sites.
314
NON-PARAMETRIC REGIONALIZED MODEL PERFORMANCE EVALUATION OF PM2.5

CHEMICAL TRANSPORT MODELS
Jeanette Reyes and Marc Serre

(University of North Carolina, Chapel Hill, NC, USA)
The EPA employs a vast monitoring network to measure ambient PM2.5 concentrations across the United
States. However, there are several areas of the country with sparse monitoring. One means to fill in these
monitoring gaps is to use PM2.5 modeled estimates from chemical transport models (CTMs). CTMs are
able to provide complete spatial coverage but are subject to systematic bias and inherent variability due to
model uncertainty. Multiyear studies across the United States are challenging because the bias and model
performance of CTMs are not uniform over such large space/time domains. Bias changes regionally and
temporally. To address this issue we introduce a model performance evaluation for PM2.5 CTMs that is
regionalized and non-parametric. This model performance evaluation leads to a bias correction that is
regionalized, and allows to combine bias corrected CTM outputs with observational data, resulting in a
hybrid PM2.5 estimate that has the accuracy of observation data along with the coverage of modeled data.
The regionalized bias correction approach is non-parametric and is therefore more flexible at characterizing
model performance than approaches that rely on parametric relationships and assume homoscedasticity of
CTM predictions errors. Observational data and bias corrected CTM data are combined using the Bayesian
Maximum Entropy (BME) method of modern spatiotemporal geostatistics in order to quantify uncertainty
at unmonitored locations in space and time. Incorporating modeled data along with observational data better
characterizes PM2.5 variability and reduces estimation uncertainty compared with using observational data
alone.
315
ON-LINE MEASUREMENT OF AEROSOL FROM DESULFURIZATION FLUE GAS BASED

ON AEROSOL MASS SPECTROMETRY
Pan Danping, Guo Yanpeng, Bao Jingjing, Yang Linjun

（Southeast University, Nanjing, China）
The formation of aerosol has been the bottleneck constraints for the development of ammonia flue gas
desulfurization and off-line analysis methods can not veritably reflect the formation characteristics. Using
aerosol mass spectrometry, the size and chemical composition of aerosol were investigated on-line.
Experiments on the analysis of the aerosol formation and the effect of different desulfurization slurries used
to start the test, oxidation degree of desulfurization slurry and pH value were carried out. As the results
show, the main composition of aerosol is sulfate and ammonium salt, and the size of aerosol particles mainly
ranges from 0.1 to 0.4µm. NH4HSO4 and NH4HSO3 exist in the aerosol formed by the reaction between
gaseous NH3 and SO2 under the condition of high humidity. The composition of aerosol formed by
entrainment and evaporation of desulfurization slurry is mainly (NH4)2SO4 and some (NH4)2SO3. Starting
the test by ammonium hydroxide, NH4HSO4 and NH4HSO3 exist in the aerosol, while (NH4)2SO4 and
(NH4)2SO3 are the main part when starting the test by saturated ammonium sulfate. Without oxidation of
desulfurization slurry, the composition of aerosol is mainly SO32- and the amount of SO42- increases
significantly after oxidation. With the pH value of desulfurization slurry getting higher, the amount of SO32-
increases.
316
METABOLIC CHARACTERISTICS AND COMMUNITY DIVERSITIES OF AIRBORNE

MICROBES AT DIFFERENT FUNCTIONAL REGIONS IN QINGDAO IN WINTER
WU Dengdeng and SONG Zhiwen*

(Qingdao Technological University, Qingdao, China)
To determine the metabolic characteristics and community diversity of airborne microbes in different
functional regions of Qingdao in winter, sampling sites were set up in five different functional regions
(urban streets, a coastal area, drinking water source area, municipal landfill, and artificial wetlands).
Airborne microbes were then collected using an SAS ISO100 air sampler in January 2013 and their carbon
source metabolic characteristics, functional diversity, and relationship with environmental factors were
systematically analyzed by the BIOLOG method. The results revealed significant differences in carbon
metabolic profiles of air microbial communities from the five locations. When metabolism was stable, the
average well color developments of samples from the coastal area and drinking water source area were
0.302 and 0.21, respectively, whereas those of artificial wetlands, urban streets, and municipal landfill were
0.063, 0.025, and 0.034, respectively. Therefore, the levels of carbon metabolism in the coastal area and
drinking water source area were higher than those at other locations. The Shannon indexes and Simpson
indexes at the five different functional regions were similar. However, the McIntosh indexes at the coastal
area and drinking water source area were higher than those at other locations. Overall, the microbial
diversity and dominant species differed among functional regions, but microflora was distributed more
evenly in the coastal area and drinking water source area. Among the five locations, carbon catabolic types
and levels in the coastal area and drinking water source area were richer and higher than those in the
artificial wetlands, urban streets, and municipal landfill. Overall, the airborne microbes in various functional
areas had high carbohydrate and carboxylic acid metabolism, and air microbial communities in the coastal
and drinking water source areas had better ability to metabolize polymers, carbohydrates, carboxylic acids,
and amino acids than those in the artificial wetlands, urban streets, and municipal landfill. The
characteristics of carbon metabolism revealed regional differences that were mainly caused by carboxylic
acids. Specifically, urban streets, municipal landfills, and artificial wetlands had similar metabolic
characteristics, and could be classified together. Additionally, coastal and drinking water source areas had
different characteristics, and could be classified respectively. Environmental factors such as wind speed,
temperature, and humidity may affect carbon utilization to a certain degree; however, the dominant factors
will differ among environments. The results of canonical correspondence analysis (CCA) showed that wind
speed and the carbon metabolism of the coastal area and drinking water source area were positively
correlated, while they were negatively correlated with temperature and humidity. However, urban streets,
municipal landfill, and artificial wetlands were positively correlated with temperature and humidity and
negatively correlated with wind speed. The BIOLOG method could provide a large amount of multi-
dimensional data, compare carbon metabolic characteristics of the microbial community between samplers,
and reflect characteristics of the carbon metabolic diversity of airborne microbes objectively and generally,
making it an ideal method for studying functional diversity of airborne microbes.
317
SOURCE IDENTIFICATION OF ATMOSPHERIC PARTICULATE MATTER USING

RADIOCARBON AND MOLECULAR SOURCE MARKERS
Hyun-Min Hwang (Texas Southern University, TX, USA)

Bruce A. Buchholz (Lawrence Livermore National Laboratory, CA, USA)
Thomas M. Young (University of California, Davis, CA, USA)
To improve understanding of the sources of atmospheric carbonaceous particulate matter (PM), size-
resolved PM (0.056 to1.8 µm) and time-resolved bulk PM10 collected from a site in Sacramento, California
were analyzed for radiocarbon and source markers such as levoglucosan, alkanes, and elemental carbon
(EC). The contributions of modern (non-fossil) carbon sources were much greater than that from fossil
carbon sources in all samples. Radiocarbon and source marker measurements confirm that the greater
contribution of non-fossil carbon sources in November samples was due to residential wood combustion.
Results of the present study provide additional evidence that wood combustion was likely a significant
source of EC in November samples, which demonstrates that using EC as a diesel emission tracer may not
be appropriate in areas where wood combustion could be a confounding source of EC. Levoglucosan to
organic carbon (Levo/OC) ratios in all PM10 samples showed a strong negative correlation with fossil
carbon content. Fossil originated carbonaceous PM10 could account for about 40% of the total carbonaceous
PM10 in the study area when the contribution from wood combustion is zero. The results of the present
study demonstrate the value of combining radiocarbon and conventional source markers for more robust
and detailed source attributions for ambient PM.
318
AIR POLLUTANT WATCH LIST OF TEXAS – PORT ARTHUR AS AN EXAMPLE
Tara Capobianco, Darrell McCant, Ross Jones

(Texas Commission on Environmental Quality, Austin, TX, USA)
The Texas Commission on Environmental Quality (TCEQ) establish the Air Pollutant Watch List of Texas
(APWL) to address areas of the state where air toxics were persistently monitored at levels of potential
concern, and the TCEQ uses the APWL to reduce air toxic levels by properly focusing its resources on
areas in the state with the greatest need. The TCEQ added Port Arthur to the APWL to address persistent,
elevated annual average concentrations of the air toxic benzene at the TCEQ’s City Service Center (CSC)
monitor, located just northwest of the industrial complexes in Port Arthur. Since Port Arthur’s inclusion on
the APWL in 2001, several sources in the APWL area have implemented improvements that led to
reductions of benzene emissions. The TCEQ’s Toxicology Division (TD) establishes conservative
screening values called air monitoring comparison values (AMCVs) to evaluate ambient air toxic data and
the AMCV for benzene is 1.4 parts per billion by volume (ppb). Annual average benzene concentrations
below 1.4 ppb are not expected to be associated with any long-term adverse health effects. This value was
derived using TD’s scientifically-rigorous effects screening level (ESL) guidelines, which was scrutinized
through a scientific peer review and public comment process.
The annual average benzene concentration exceeded or equaled the long-term, health based AMCV
for benzene from 1997 to 2001 at the CSC monitor. Subsequently, the annual average benzene
concentrations for the years 2002 through 2005 were above the previous long-term AMCV of 1.0 ppb, but
had decreased and were below the current long-term AMCV of 1.4 ppb. Since 2005, monitored
concentrations have decreased significantly, and the 2006 and 2007 annual average benzene concentrations
were below both old and new long-term AMCVs; however, the 2008 annual average benzene concentration
exceeded the current long-term AMCV with a value of 1.9 ppbv, which was the highest annual average
concentration observed at that monitor. Thus, Port Arthur remained listed on the APWL, and the TCEQ
encouraged further reductions in the area. Since 2008, the annual average concentrations have decreased
once again, and the 2009 and 2010 annual average benzene concentrations were 0.8 ppb and 1.0 ppb,
respectively. The annual average benzene concentration at the City Service Center monitor was 0.6 ppb in
2011 and was 0.5 ppb in 2012.
In addition, there is both a TCEQ- and industry- sponsored stationary monitoring networks in Port
Arthur and six are in or near the APWL area. These network monitors take ambient volatile organic
compound measurements hourly and once every sixth-day 24-hour and all, including TCEQ’s CSC monitor,
have reported annual average benzene concentrations below TCEQ’s long-term screening value. The CSC
monitor has reported this decline for four consecutive calendar years and ten of the last eleven calendar
years. The TCEQ has determined that benzene concentrations can reasonably be expected to be maintained
below levels of potential concern and proposes to remove Port Arthur from the APWL. Companies located
in the APWL areas are required to comply with Title 30 Texas Administrative Code §101.10, Emissions
Inventory Requirements, which requires owners or operators of certain stationary sources to submit an
annual emissions inventory to the TCEQ. These companies are required to report all of their actual air
emissions each year, including all authorized and unauthorized emissions. The stationary monitoring
network includes six monitors that take ambient benzene measurements in Port Arthur.
As part of the delisting process, the TCEQ conducted a public meeting to receive comments on the
proposed delisting of Port Arthur from the APWL. While the TCEQ is in the process to remove Port Arthur
from the APWL, monitoring in the area will continue to ensure that no issues arise.
319
ATMOSPHERIC POLLUTION IN A NORTH AFRICAN CITY: THE CEUTA PARADIGMA
S. Garcia Dos Santos *, R. Fernández Patier, M.A. Sintes Puertas, A. Aguirre Alfaro, J. Alonso Herreros
and S. Guevara Hernández
(Instituto de Salud Carlos III, Madrid. Spain)
R. Benarroch Benarroch and J.M. Cantón Gálvez
(Consejería de Sanidad y Consumo. Ceuta. Spain)
Ceuta a Spanish city which have 65 000 inhabitants is located in the south shore line of the Gibraltar strait.
This city has not a network to measure its air quality. So, to fulfill the EU Directive 2008/50/EC provisions,
three field work campaigns were performed between 2010 and 2013 for of NO2, O3, VOC (benzene, toluene,
etilbenzene, m+p-xilene and o-xilene) and particles (PM10 and PM2,5). The pollutants were chosen
because most of them are either EU legislation or have been described as ozone precursors. The campaigns
were done in 2010/11 (fall-winter), 2012 (spring) and 2013 (summer). Gaseous species were sampled (55
points) by radial diffusive samplers during 7 days (NO2 and VOC) and 15 days (O3). Those points were
inside of a net (200 m x 200 m) which covered all Ceuta area. While NO2 was analyzed by
espectrofotometry, O3 was measured by ion chromatography and VOC by gas chromatography. PM10 and
PM2,5 particles were continuously sampled (60 to 90 days a year) for 24 h period, in a site located in the
middle of the city, using European reference samplers, described by EN 12341 and EN 14907 European
standards. Both gas and particles were analyzed under the EN ISO/IEC 17025 standard quality system for
which, the laboratory has been accredited by ENAC (Spanish Accreditation Body), since 2000. The
campaigns showed, for gaseous species, a different pollutant behavior and higher spatial distribution. While
NO2 and O3 presented very high levels, VOC (including benzene) resulted in relative low ones. During
2013, NO2 concentrations (50 sampling points) have showed 11 µg/m3 ± 8 µg/m3, with the highest value
(48 µg/m3) in the city downtown. On the other hand, the ozone had a mean level of 114 µg/m3 ± 68 µg/m3
with a maximum valium of 549 µg/m3 in an urban zone east of the city center. Notice, the ozone results
were obtained as a 15 days mean value so, the mean the O3 alert population level of 240 µg/m3 (EU
Directive) should be commonly exceeded, by larger. Similar results for NO2, O3 and VOC were found
during the 2011 (not for O3) and 2012 campaigns. The high ozone concentrations should be the results not
only of local photochemical reactions but also due to its transport from both tropospheric top layers and
surface long range, both typically of the Mediterranean Sea basin. As expected from scientific literature,
PM10 and PM2,5 levels were strongly dependent of Saharan episodes, during the three campaigns.
Although PM10 and PM2,5 levels could meet the required EU limit values, they exceeded the health WHO
guideline value of 10 µg/m3. Those results showed the importance of ozone as well as particles as the main
atmospheric pollutants in this area. Moreover, both are producing an important health risk on the population
of Ceuta and this fact could be extrapolated to the all nearby North African cities. Finally, the study showed
that in North African cities air quality networks are urgently needed to evaluate the atmospheric pollution,
to set a number of measures to decrease the actual exposure of population.
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OCCUPATIONAL EXPOSURE TO CHEMICALS IN NAIL SALONS
Tasneem Islam, Margaret Back, Katherine Chin, Morgan Dashko, Alisa Feinswog, Aliza Heeren, Ben
Krause, Molly Pearlman, Maia Rodriguez-Semp, Madeline Rosenberg, Emily Scharf, Shanlai Shangguan,
Emily Weisfeld, Brett Aronson, Joseph Allen, Matt Fragala, Theodore Myatt, James Stewart, Laura
Goldin
(Brandeis University, Waltham, MA, USA)
The nail salon industry has become one of the fastest growing categories of Asian American businesses;
there are about 350,000 nail technicians working in the U.S. and Vietnamese hold 40% of the licenses
across the country. (Quach et al. 2011; OSHA 2013) Many of these workers are Vietnamese women of
childbearing age who are exposed to a wide range of potentially harmful chemicals in their daily work. In
nail salons, the chemicals that are most harmful to health are found predominantly in the nail products (i.e.
polishes, removers, gels and acrylic nails) and cleaning supplies. Key ingredients in these products can be
mislabeled or unidentified. The true composition of these nail products typically include compounds such
as dibutyl phthalate, formaldehyde, and toluene, commonly named the “toxic trio” because of their known
carcinogenic traits and ability to cause reproductive harm. This study aims to determine the composition of
the air quality in nail salons in the greater-Boston area to assess the acute chemical exposure and associated
health risks that these nail technicians face.
Air monitoring data was collected over an approximate eight-hour workday in 15 nail salons within
Boston and Greater-Boston area, and consisted of two parts. The first part involved the use of sampling
media to test for personal and area exposure to four volatile organic compounds (VOCs): acetone,
formaldehyde, toluene, and ethyl methacrylate (EMA). Second, the salon’s ventilation was quantified by
measuring the levels of carbon dioxide (CO2) and particulate matter (PM2.5). Lastly, a questionnaire and
observation log was completed upon arrival and departure from the sample sites that revealed qualitative
information on salon characteristics. In addition to our in-salon workday testing, video exposure monitoring
of acrylic and lacquer manicure procedures was correlated with simultaneous recordings of total volatile
organic compound (TVOC) levels to provide a visual understanding of the chemical exposure a nail
technician experiences while performing typical nail procedures.
Twelve out of the fifteen (80%) salons tested revealed formaldehyde levels higher than the 0.75
ppm OSHA Permissible Exposure Limits (PELs) for either personal or area testing. Our data shows a strong
correlation between low acetone concentrations and mechanical ventilation; this finding was not as
pronounced for formaldehyde. Some salons had levels of CO2 that indicated they did not meet the ASHRAE
ventilation standard of 800 ppm for nail salons. EMA was detected in only one salon. In that salon, the
EMA concentration exceeded EPA’s health-based guideline for EMA. Video exposure monitoring with co-
located TVOC measurements revealed very high TVOC concentrations during specific activities.
Future studies should analyze the presence of other toxic chemicals, such as methyl methacrylate
(MMA), which was banned and replaced with EMA, to analyze its presence in common nail products.
Additional testing should be conducted to confirm the measurements of formaldehyde obtained. Finally,
there should be further support, education, research, and promotion for safer, healthier alternative materials
for nail technicians to use.
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SOURCE APPORTIONMENT OF INDOOR PM2.5 AT SANTIAGO, CHILE
Héctor Jorquera and Francisco Barraza

(Pontificia Universidad Católica de Chile, Santiago, Chile)
A simultaneous indoor and outdoor PM2.5 campaign has been carried out at Santiago, Chile (6 million
inhabitants, 33.5°S, 70.6°W) in spring 2012. Paired input and output samplers were used for measuring
elemental and EC/OC composition in Teflon and quartz filters, respectively. A total of 47 households at
Downtown Santiago were analyzed; socioeconomic status was included in the campaign design.
Indoor PM2.5 concentrations are higher due to household activities such as cooking and cleaning
and habits like smoking; mean outdoor and indoor PM2.5 concentrations were 18.5 and 21.6 µg/m3,
respectively; mean I/O ratio was 1.20 (σ=0.51). The infiltration factor was estimated by the sulfur tracer
methods as 0.80 (±0.03); this value is higher than in USA studies because of higher air exchange rates in
Santiago (1-8 h-1) due to poor construction standards and lack of air conditioning.
Positive Matrix factorization (PMF) was applied to the indoor PM2.5 chemical composition data.
Source identification was carried out by inspection of key species in source profiles and by comparison
with published source profiles found in Santiago. We have identified seven sources; four of them are
outdoor contributions: secondary sulfates: 2.8 (±0.5) µg/m3, outdoor soil, 2.9 (±0.7) µg/m3, motor vehicles:
5.5 (±1.0) µg/m3, and marine aerosol: 2.6 (±0.3) µg/m3; the three indoor sources are: indoor soil, 1.8 (±0.2)
µg/m3, cooking: 5.0 (±0.6) µg/m3 and smoking: 0.9 (±0.4) µg/m3. The highest contribution is from motor
vehicles (26%) followed by cooking (23%) and outdoor soil (13%). Organic carbon explains most of the
higher indoor values found in PM2.5 mass concentration.
Therefore, indoor sources should be considered in future policies oriented to reducing population
exposure to PM2.5. The outdoor sources contributing to indoor PM2.5 have already been identified for
Santiago; only wood burning does not show up because the campaign was carried out in the warm season.
322
ATMOSPHERIC CARCINOGENIC POLYCYCLIC AROMATIC HYDROCARBONS IN

HOUSTON, TX, USA: PINE NEEDLES AS PASSIVE SAMPLERS
Sharmila Bhandari and Hyun-Min Hwang

(Texas Southern University, Houston, TX, USA)
Vehicle emissions contain carcinogenic contaminants, especially PAHs (polycyclic aromatic

hydrocarbons). PAHs with molecular weight of 278 and 302 have been gaining more attention due to their
higher cancer potency. This study measured HMW (high molecular weight) PAHs (5 rings or more) in pine
needles that have not been analyzed commonly to assess atmospheric distribution of PAHs and their
sources. Some of these target PAHs are known 10 times more carcinogenic than benzo[a]pyrene, which has
been used as a reference PAH. Pine needle samples collected from the Houston area (total 30 sites) were
analyzed for HMW PAHs using a GC-MS. Total concentrations of HMW PAHs (more than 25 PAHs) in
pine needles samples varied from 31 to 762 ng/g (wet wt.). Benzo[b + j + k]fluoranthenes were most
abundant and followed by indeno[1,2,3-cd]pyrene and benzo[ghi]perylene. Although concentrations of
dibenzo[ah]anthracene and dibenzo[al]pyrene were lower than other HMW PAHs, they accounted for more
than 50% of the total cancer potency because their cancer potency equivalency factors are 5 and 10 times
of benzo[a]pyrene. PAH patterns and ratios of selected PAHs indicated that vehicle emission is the primary
source. PAH concentrations had a positive correlation with distance from highways and/or busy traffic
ways, providing additional evidence that vehicle emission is the primary source of PAHs in the Houston
area. This study suggests that people who live in the inner city area are exposed to higher levels of PAHs.
323
EFFECTIVENESS OF LOW EMISSION ZONES: ANALYSIS OF THE CHANGES IN FINE

DUST CONCENTRATIONS (PM10) IN 19 GERMAN CITIES
1
Peter Morfeld, 2David.A. Groneberg, and 3Michael Spallek (1. University of Cologne, Rüttenscheider Str.
1-3, 45128 Essen, Germany; 2. Goethe-University, 60590 Frankfurt/Main, Germany; 3. Berlin and Institute
for Occupational Health, Charité University Medicine Berlin, Fritschestrasse 35, 10627 Berlin, Germany)
Background: It is unknown and disputed whether there is a reduction of fine dust values caused by the
introduction of low emission zones (LEZs).
Methods: Analyses of PM10-concentrations were performed that covered LEZs from 19 German
cities (Augsburg, Berlin, Dortmund, Duisburg, Düsseldorf, Essen, Frankfurt a. M., Hannover, Herrenberg,
Ilsfeld, Karlsruhe, Köln, Ludwigsburg, Mannheim, München, Reutlingen, Stuttgart, Tübingen, Wuppertal)
and investigated the effect of “tier 1” until the end of 2009, i.e., only allowing vehicles of improved emission
group 2 or higher (with “sticker”) to enter the LEZ. For the period from about 2005 until the end of 2009
continuous half-hour measurement values as well as gravimetrically determined daily measurements of
PM10 were collected. The analysis consisted of four pairwise corresponding measurement values as matched
quadruples of two index- and two reference values. (Index stations are inside, reference stations measure
outside the LEZ). One index value and the simultaneous reference value were measured during the active
LEZ period, the other pair of values was measured before introducing the LEZ. The pairs of values had a
difference in time of 364 days or a multiple of 364 days keeping the season, weekday and time of day
constant within the quadruple. Differences in index values were regressed on differences in reference values
while meteorological parameters (height of the inversion base, amount of precipitation, wind velocity),
school holidays, period of environmental bonus paid, periods when trucks were bolt out as well as baseline
data at index and reference stations were taken into account as covariates in so-called “fixed effects”
regression analyses of the quadruples (difference score method in the two-period case). The statistical
approach was successfully validated in advance to the study in an analysis of simulated data from FU Berlin.
Results: 2,110,803 quadruples of continuous PM10 and 15,735 gravimetric quadruples were
identified leading to 61,169 quadruples based on daily PM10 averages. The analyses showed that best LEZ
effect estimates for fine dust reduction were (at all index stations) ≤ 0.2 μg/m3, i.e., a relative PM10 reduction
≤ 1%. Best estimates at all index stations near traffic (excluding urban background and industry index
stations) were below 1 μg/m3 (less than 5%, resp).
Conclusions: Effects were smaller than predicted prior to the introduction of LEZs. This study is
the first that investigated comprehensively the effectiveness of “tier 1”-LEZs in Germany on PM10-
reduction with a homogeneous approach in data collection and analysis and considering most relevant
confounding factors.
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A COMPARATIVE STUDY OF ECONOMIC EVALUATION METHODS ON PM2.5

HEALTH IMPACT
Hao Yin, Linyu Xu

(Beijing Normal University, Haidian District, Beijing, China)
PM2.5 pollution nowadays in the worldwide attracts great attention due to its serious health deterioration
and economic loss. Comparing PM2.5 health economic loss evaluation methods utilized by scientists
worldwide is of interest in enhancing the air quality control, health impact assessment management. A
comparison of four economic evaluation methods, including Amended human capital approach (AHC),
Willingness to pay method (WTP), Cost of illness (COI) and Friction cost approach (FCA), were conducted
to analyze the differences, merits and limitations. AHC is a very applicable and convenient method, in terms
of data availability, for the PM2.5 health economic loss evaluation. WTP is the only way to reflect the
thoroughly economic loss caused by PM2.5 pollution, including human physical loss and spiritual loss.
COI and FCA focus on cost of illness and production loss due to diseases caused by pollution. Results
showed that health economic loss results calculated by AHC approach were usually lower than that by WTP
method. Former study results showed that the average economic health costs were about 120-264 $/year in
Beijing, China with AHC approach, while a study in Sweden showed that the mean WTP for a 50%
reduction of air pollution was about 2230 $/year. Despite the fact that the study areas are quite different,
this study deems that the large difference of economic loss value is mainly due to the ignorance of spiritual
loss and lower GDP per capita in AHC approach. WTP measure is imperative for policy makers to decide
the public investment and policy instrument for eliminating PM2.5 health impacts, while AHC method is
helpful for environmental PM2.5 pollution compensation.
325
IMPACTS OF VEHICLE TO INFRASTRUCTURE COMMUNICATION TECHNOLOGIES ON

VEHICLE EMISSIONS
Qing Li, Fengxiang Qiao, and Lei Yu

(Texas Southern University, Houston, Texas, USA)
ABSTRACT: Global warming and climate change have been always a critical issue for current and future
generations, which calls for the development of innovative technologies such as clean car, renewable
energy, ecological driving, and connected vehicles. Based on the Environmental Protection Agency (EPA)
newly released emission model MOVES, the change of speed and acceleration should greatly affect the
Vehicle Specific Power (VSP) and the Operation Mode Identification Number (OMID) distributions, which
will yield out different emission estimations. The Vehicle-to-Infrastructure (V2I) communication
Technology is capable of improving driving performance and smooth speeds and acceleration rates. In this
paper, the impacts of the V2I system on vehicle emissions are explored. A Radio Frequency Identification
(RFID) based V2I technology is employed to provide audio message to drivers who are approaching
intersections in the situations of sun glare and work zones. Impacts on speed and acceleration rates, as well
as VSP, OMID distributions and resulted vehicle emissions with and without V2I system are analyzed
through in-simulation driving tests. The results show that the V2I system can not only improve safety but
also mitigate vehicle emissions.
INTRODUCTION
Since 1880, the earliest year for comprehensive worldwide temperature records available, global
average temperature in the period of 2001 and 2010 is the warmest. The consequences of warming include
the increased atmospheric moisture leading to severe precipitation and floods, and high heat stress to land-
crops and plants die. Even worse, the land is no longer able to hold in water and eventually desertification
and drought are formed. What’s more, the warming has been accompanied with significant and harmful
effects on human health, environment, and communities, such as the disruptions of food supply, less fresh
water available, plant and animal endangering extinct, and more frequent and intense heat waves. It is a
scientific consensus that human activities are the primary driver for the global warming, which is attributed
to greenhouse gases. Human activities are responsible for almost all of the increase in greenhouse gases in
the atmosphere over the last 150 years (Solomon et al., 2007). According to Environmental Protection
Agency (EPA), transportation has been one of the largest sources (approximately 28%) for greenhouse
gases emissions produced by human activity in The U.S. The automobile in The U.S. accounts for 30% of
the world’s automobiles and contributes 45% of the world’s automotive CO emissions (DeCicco et al.,
2006). Moreover, annual increased vehicle mileages and lower fuel efficiency, comparing with international
level, play a crucial role in the contribution of CO emissions. With regards to this, many affordable and
clean vehicle technologies have been proposed and applied in the improvement of fuel economy in vehicles,
such as hybrids-electric vehicles, electric cars, and advanced biofuels. To maximize the fuel economy and
corresponding reduces vehicle emissions, eco-driving is newly proposed, which refers to drive in a smart,
smooth and safer pattern, instead of aggressive driving maneuvers. This has been considered as the most
cost-effective method of improving road safety, reducing vehicle emissions, as well as minimizing fuel
consumption. In 1995, a National Research Council report noted that aggressive driving with many
accelerations is responsible for 15 times higher CO emissions and 14 times higher hydrocarbonds (HC)
emissions than the normal driver on the same trip (NRC et al., 1995). Ten years later, El-Shawarby et al.
(2005) further proved that as the aggressiveness of acceleration maneuvers increased, the fuel consumption
and emissions rates increased significantly. Later on, Ahn and Rakha (2008) specifically demonstrated that,
25% of total CO emissions and 28% of fuel consumption levels are caused by 10% of the most aggressive
driving maneuvers of typical trip. Furthermore, McKinsey (2009) estimated that teaching drivers to eco-
326
drive can improve actual fuel efficiency by an average of 17%. In addition, the vehicle-to-infrastructure
(V2I) communication provided real-time traffic situations and smart advices that have been widely applied
in Intelligent Transportation System (ITS). With such system, drivers are able to plan ahead for better
driving maneuvers, in terms of dynamic driving speeds and acceleration rates. Though the V2I system is
mainly dedicated for safety purposes, it is believed that the system may enable significant environmental
benefits, especially vehicle emissions. The amount of emission changes can be estimated based on the EPA
newly released model MOVES (EPA, 2009). The change of speed and acceleration rates should greatly
affect the Vehicle Specific Power (VSP) distribution and the corresponding Operation Mode Identification
Number (OMID) distribution. Such change will yield out different estimations of vehicle emissions. In this
paper, the impacts of a Radio Frequency Identification (RFID) based V2I technology on vehicle emissions
and fuel consumption are explored, while vehicles are approaching a work zone and a signalized
intersection with sun glare, respectively.
IMPACTS OF VEHICLE EMISSIONS ON HUMAN HEALTH AND THE ENVIRONMENT

Vehicle emissions are the byproducts from engine fuel combustion process and the evaporation of
fuel, including unburned HC, nitrogen oxides (NO‰ ), carbon monoxide (CO), sulfur oxide (SO‰ ), volatile
organic compounds (VOCŠ), and particulate matter (PM). A number of studies have shown that the exposure
to these emissions may lead to serious health effects and extreme environments.
Effects on Health. Probably no one would argue that the automobile is one of the major contributors to
urban air pollutions especially in the U.S., where most people rely on their own private vehicles for daily
activities. Meanwhile, vehicle emissions have been considered as toxic and carcinogenic air pollutants,
which raise the concerns for the health of the public. In practice, the vehicle emissions may impair human
health directly or indirectly. For instance, the HC reacts with nitrogen oxides and sunlight to form ground-
level ozone, namely smog. The smog irritates the eyes, damages the lungs, and aggravates respiratory
problems. Children and the elderlies are especially vulnerable to the smog. Even worse, a number of
exhausts HC are toxic and may cause cancer potentially. The carbon monoxide (CO2) reduces the flow of
oxygen in the bloodstream and is particularly dangerous to the persons with heart disease. Moreover, the
fine particulate matter (e.g., PM2.5) can be especially damaging, because of its small particles that are easily
inhaled and its toxic components such as polycyclic aromatic hydrocarbons (PAH) and heavy metals. Some
of the VOCs, such as such as benzene and 1, 3-butadiene, are caner causing agents. Though its current levels
in the environment are small, they are precursors to ozone and secondary particulate matter formation.
Effects on the Environment. Many studies have demonstrated that vehicle emissions are responsible for
a number of adverse environmental effects, such as photochemical smog, acid rain, and global warming.
Smog can inhibits plant growth and cause widespread damage to crops and forests. Acid rain may change
the pH value of waterways and soils thereby harm the organisms that rely on these resources. Global
warming may result in the increase of average temperatures around the world, extreme weather events, and
shift in climate patterns worldwide. Though carbon dioxide does not impair human health directly, it may
make contribution to global warming when its amount emitted by human activities is greater than natural
absorption system.
COUNTERMEASURES TO MITIGATE VEHICLES EMISSIONS
Less Utilize Fossil Fuel. Many countermeasures have been applied to reduce vehicle emissions from motor
vehicles. The most effective way is definitely to less utilize fossil fuel by either expanding the use of
renewable energy or encouraging alternative transportation modes. Renewable energy is referred to cleaner
and less dependent on coal and other fossil fuels, such wind power, solar energy, geothermal energy,
hydrokinetic energy, corn-based ethanol biofuel, and so on. However, the application of the renewable
energy is often associated with costly innovative technologies such as the hybrids-electric vehicles, electric
327
cars, and mobile electricity auto charger. On the other hand, alterative transportation modes, such as bus,
train, or bike, can be considered as a feasible solution. But this requires associated transportation facilities
and system that provides accessible public transportation network, and dedicated pedestrians and cycle
paths. This is more suitable to the dense cities such as Washington, DC and New York. For areas where the
population density is rather low (e.g. most urban areas in the U.S. including Houston,) the choice of other
modes of transportation is quite limited, and motor vehicles are still the major transportation mode.
Increase Vehicle Fuel Efficiency. From another standpoint, maximizing mileage for each gallon of fuel
consumption can mitigate vehicle emissions as well, which can be simply achieved by regular maintenance,
properly inflated tires, and fuel-efficient driving habits. Comparing with others methods, cultivation of fuel-
efficient driving habits is the most complicated. Fuel-efficient driving habits are similar to the concept of
eco-driving, driving moderately with limited idling and keeping moving with less acceleration. Based on
previously mentioned studies, eco-driving pattern is able to increase mileage for each gallon of fuel
consumption (Kurani et al., 2013, Wu et al., 2011, Stillwater et al., 2012). However, people’s driving
pattern is diverse and quite subject to individual performance, which depends on many factors, such as
personality, driving experience, driving skills, and so on. With the application of V2I system, the driving
patterns can be guided towards desired ones such as the eco-driving pattern. This is because the V2I system
enhances the communication between vehicles and traffic infrastructure (e.g. traffic signal, signs, and
control devices), especially in areas with safety threat such as work zones or signalized intersection with
visual disturbance. Drivers can be aware of the changing or fuzzy situations earlier, and be able to prepare
to stop or change lane at right time and space locations. In this way, the excessive acceleration or sudden
brake can possibly be avoided and eventually travel speeds are regulated within a desired range. Such
driving pattern is more likely to be beneficial to fuel efficiency as well.
Control Driving Speeds and Vehicle Specific Power (VSP). To estimate emissions from mobile sources,
MOVES has been developed by EPA’s Office of Transportation and Air Quality (OTAQ). The estimation
of vehicle emissions is based on the Operating Mode Bins distribution, which is calculated by Vehicle
Specific Power (VSP), grade, acceleration rates, and driving speeds (see Equation 1).
VSP = v ∗ 1.1 ∗ a + 9.81 ∗ grade% + 0.132 + 0.000302 ∗ v H (1)
Equation (1) tells that the acceleration rates and speeds are proportional to the VSP. The
classification of opMode ID (OMID) is also defined by MOVES with the binning standard of VSP,
acceleration rates, and speeds. The distribution of OMID is essential for the estimation of vehicle emissions
in MOVES. Therefore, vehicle emissions can be mitigated by updating the distribution of OMID through
controlling driving speeds and acceleration rates.
ADVANCED V2I TECHNOLOGY TO REDUCE EMISSIONS

The vehicle-to-infrastructure (V2I) communication provides wireless exchange of critical dynamic
traffic situation and operational data between vehicles and roadside infrastructures. Specifically, the data
exchanged between vehicles and infrastructures will be calculated for the identification of special situations
to safety and emissions in advance. Drivers will receive the identified critical situations before entering. A
typical example is to deliver the signal phase and timing information to drivers with active safety advisories
and warming, with which they are able to react to the situation early and smoothly. Smooth driving is the
feature of eco-driving. Based on the OMID distribution, the vehicle emission rates present lower
significantly at a certain range of speeds and VSP. In this respect, V2I system can guide drivers for target
eco-driving.
The concept of the eco-driving has been applied in one of the Applications for the Environment:
Real-Time Information Synthesis (AERIS) program, Eco-Signal Operations by the U.S. Department of
Transportation. Concretely, connected vehicle technologies are used to decrease greenhouse gases and
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criteria air pollutant emissions on arterials by reducing idling, reducing the number of stops, reducing
unnecessary accelerations and decelerations, and improving traffic flow at signalized intersections.
SCENARIOS DESIGN AND TESTS

Considering the fact that participants may undertake high risk of collisions with other vehicles or
pedestrians during on-road tests, a driving simulator is used in the experiment to verify the impacts of V2I
system on vehicle emissions. Designed scenarios include signalized intersections and work zones.
Signalized Intersections. A track of approximately 1,000 meters in an industrial area with three
intersections was generated in scenarios (see Figure 1). The distance between intersections is about 300
meters, while the posted speed limit is 72 km/h (20m/s). Each subject was the only driver on the track.
Subjects were required to drive through the three intersections in three different situations: no sun glare no
V2I, with sun glare no V2I, and with sun glare and V2I.
With the V2I system, drivers received audio messages about the real-time signal while approaching
a signalized intersection under a visual disturbance of sun glare. The location they received audio messages
depends on the play time of the message (1 sec), driving speeds, perception-reaction time, and minimum
sight distance for signal visibility. 2.5 seconds was chosen as the perception-reaction time (Chang et al
1985). The minimum sight distance was 140 meters for the posted speed limit 72 km/h ( 20 •⁄‘ )
(MUTCD, 2009). Therefore, drivers received the audio message at 210 meters away from the third
intersection ( 1.0 + 2.5 × 20 •/‘ + 140 • = 210 •).
Audio messages
FIGURE 1. Layout of test route with and without V2I and sun glare.
Work Zones. In this set of test, subjects drove twice through a short work zone with two lanes in one
direction for different scenarios: with traditional sign control only, and with both traffic signs and the V2I
guidance (see Figure 2). The posted speed limit was changed from 72 km/h (45mph) to 48 km/h (30mph or
13.33m/s) when approaching the work zone. With the V2I system, drivers were instructed by audio
messages relevant control information. This is in addition to the traditional traffic signs. They received
audio messages at the distance of 70 meters and 107 meters for traffic sign and risk warning, respectively.
These distances considered stop distance instructed by 2009 MUTCD and the reaction-time 2.5 seconds.
FIGURE 2. Layouts of two scenarios at work zone (with and without audio messages).
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Participants. Totally thirty subjects were recuited for the driving simulator tests. The recuitment was based
on Houston’s demographics from 2010 census. The porportion of subjects regading gender, age, and
education background was adjusted for the legal driving age in the U.S. Fifteen male and fifteen femal
subjects aged above eighteen years old with valid C class drive licenses participated in the test. Specifically,
twenty-six subjects were between the ages of eighteen and sixty-four, while four subjects were seniros aged
sixty-five plus. Twenty-one subjects had obtained high school and associated degrees, while nine obtained
bachelor’s degree or higher. All subjects have self-reported that they have normal, or corrected-to-normal
vison, and don’t have any problem with hearing.
IMPACTS OF V2I ON VEHICLE EMISSIONS
Emissions at Signalized Intersection with Sun Glare. The VSP is calculated by Equations (1) with the
dynamic driving speeds, acceleration rates and grades recorded. The vehicle emission rates occurring at the
simulator tests were estimated by a Nissan Altima car manufactured in 1999 with the mileage of 80,000
miles. The emissions estimation results are shown in Figure 3. Within each emission factors (CO , CO, HC,
and NO‰ ), there are three bars representing the emission rates for three different scenarios.
FIGURE 3. Vehicle emission rates related to driving directions at intersections.
Except for CO, the emission rates at a normal situation (no sun glare and no V2I system) are 20%
to 80% higher than the others. This implies that the normal driver behaviors are not beneficial to the air
quality at the intersections. As a contrary, the emissions rates under a sun glare without V2I are slightly
lower. However, seven of the thirty (23%) subjects ran red-light unconsciously, as some of them were either
too late to stop or couldn’t realize the upcoming signalized intersection due to the visual impairment of sun
glare. It can be imagined that the emissions rates could be lower without idling, braking or excessive
acceleration. Surprisingly, with the V2I system, the emissions rates were significantly lower than others.
This phenomenon is acceptable, since the V2I system provides audio instructions to guide subjects for safer
and smoother driving. For the CO emission, the emission rate under a sun glare effect without the V2I
system is the highest, while there is rare difference found in the situations between no glare and glare
without the V2I system. As a matter of fact, the byproduct of CO is resulted from incomplete combustion.
The CO is supposed to be transferred to CO2.
Emissions at Work Zone. Figure 4 illustrates the comparison of vehicle emissions with and without the
help of V2I system while driving through a work zone with a sudden pedestrian’s crossing. Obviously, with
the V2I system, vehicles emit lower emissions. Specifically, the four main emission factors (CO2, CO, COx
and HC) are apparently reduced, particularly the CO2 emissions. Approximately 350 gram per vehicle in
total is emitted, which is 24% less than the emission caused by a vehicle with no V2I system.
CONCLUSIONS
In this research, the impacts of V2I system on emissions were tested using a driving simulator.
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Results show that, the sun glare may impair subject’s visions so that they may drive erratically and even
commit red-light offense unconsciously. The sun glare effect brings out 23% of the subjects to run red-light.
The V2I system can assistant subjects to drive steadily, thereby producing lower vehicle emissions.
Moreover, the V2I system is able to guide subjects to driving through a work zone safer and smoother,
particularly in high-risk situations (e.g., worker’s crossing in this test). Meanwhile, the audio instruction
and/or warming messages favor the reduction of vehicle emissions. Thus, the V2I system is not only able
to secure a safer driving, but also make an important contribution to air quality.
FIGURE 4. Vehicle emissions with and without V2I warning system.
ACKNOWLEDGEMENTS
TranLIVE and the U.S. National Science Foundation (NSF) CREST #1137732 are gratefully
acknowledged.
REFERENCES
Ahn, K. and H. Rakha. 2008. “The Effects of Route Choice Decisions on Vehicle Energy Consumption and
Emissions.” Transportation research Part D, Transport and environment. 13(3): p. 17.
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Driver Behavior.” The Journal of Transportation Research Board, 1027: 20-30.
DeCicco, J.and F. Fung. 2006. Global Warming on the Road the Climate Impact of America’s Automobiles.
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Frey, H.C., B. Liu. 2013. “Development and Evaluation of a Simplified Version of MOVES for Coupling
with a Traffic Simulation Model.” The Journal of Transportation Research Board. Paper 13-1201,
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Intergovernmental Panel on Climate Change (IPCC). 2007. Summary for Policymaker. 4th Assessment
Report, Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA.
Kurani, K.S., T. Stillwater and M. Jones, 2013, Ecodrive I-80: A Large Sample Fuel Economy Feedback
Field Test Final Report, Report: ITS-RR-13-15, Davis, CA.
McKinsey & Company. 2009. Roads Toward a Low-Carbon Future: Reducing CO2 Emissions From
Passenger Vehicles in the Global Road Transportation System. New York City, NY.
National Research Council (NRC). 1995. Expanding Metropolitan Highways: Implications for Air Quality
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National Research Council (NRC). 1995. “Expanding Metropolitan Highways: Implications for Air Quality
and Energy Use.”.Transportation Research Board. viii, 387.
Stillwater, T. and K.S. Kurani. 2012, “Goal Setting, Framing, and Anchoring Responses to Ecodriving
Feedback.” Transportation Research Part F: Traffic Psychology and Behaviour, 19: 85–96.
Environmental Protection Agency (EPA). 2009. EPA Releases MOVES 2010 Mobile Source Emissions
Model: Questions and Answers. Guides EPA-420-F-09-073, Washington, D.C.
Wu, C, G. Zhao and B. Ou. 2011. “Fuel Economy Optimization System with Applications in Vehicles with
Human Drivers and Autonomous Vehicles.” Transportation Research Part D: Transportation and
Environment. 16(7): 515-524.
332
A SPATIAL AND TEMPORAL ANALYSIS OF AIR POLLUTION IN NANNING
Bo Wei1, Fengxiang Qiao1, Zhihu Huang2, Juan Ma2, Qing Li1, Sicong Zhu1, and Lei Yu1
( Texas Southern University, Houston, TX, USA; 2 Nanning Environmental Monitoring Centre, Nanning,
1
Guangxi, China)
ABSTRACT: In the last decade, the Department of Environmental Protection in Guangxi Zhuang
Autonomous Region, China has introduced a series of strategies and policies aimed at reducing air
pollutants. However, there is a lack of appropriate feedback to gauge whether the strategies are working
effectively. In this study, we collected daily respirable particulate matter (PM10) mass concentration data
from 5 air pollution monitoring stations in Nanning city, Guangxi, China over a 6-year period from January
2007 to December 2012 to identify spatial and temporal variations and trends. Statistical results show that
particulate matter (PM) are the major pollutant in Nanning city, the daily average of PM10 level over the
period 2007-2012 exceeded the WHO-recommended annual mean limit 20μg/m3 and the first grade of the
annual mean limit 40μg/m3 of the ambient air quality standards (GB3095-2012). The seasonal distribution
characteristics of monthly variation decreased in the sequence of: winter, autumn, spring, and summer. The
causes of PM level in Nanning were analyzed. Corresponding countermeasures and suggestions about
strategies formulation and implementation were discussed. This study can be a reference to analyze
government strategies with the spatiotemporal distribution and annual changes of PM.
INTRODUCTION
With the advance of China-ASEAN Free Trade Area, Guangxi plays a more important strategic
role as a communicating hub connecting southwest China, south China, central China and ASEAN markets.
As the capital city of Guangxi, China, The City of Nanning has achieved rapid development in the recent
decade. Nanning’s dramatic economic rise, rapid industrial development, population growth, construction
and demolition projects, and the increase of travel demand flow have critically affected the atmospheric
environment. Major pollutants of urban air pollution in Nanning include SO2, NO2, CO, O3 and particulate
matters (PM), where PM is the main pollutants of air pollution in Nanning (Liu, 2012). Scientific research
has proven that PM is very harmful to the environment, climate, and human health. Particulates with the
sizes of less than 10mm are able to absorb more toxic substances than coarse particles, and can enter the
human body and go deep into the lungs through respiration, which not only decreases the function of the
respiratory and cardiovascular systems, but also increases pollution-related disease mortality (Makkonen et
al., 2010).
Discovering how the PM concentration is temporally and spatially distributed is an important
problem in reducing pollution with effective measures. Spatial characteristics can help to identify
interesting spatial patterns from the spatial distribution of PM concentration, while temporal characteristics
of PM concentration observations can be used to discover its period and trend.
During the period of China’s 11th five-Year Plan (the 11th FYP, 2006-2010), the concentration of
respirable particulate matter (PM10) in Nanning is more than 60μg/m3 and increased year by year (Huang,
2013). These values are much higher than the air quality guidelines (AQG) of annual mean 20μg/m3
recommended by the World Health Organization (WHO, 2006). As a result of these large PM10
concentration values, the Nanning government adopted several measures to improve air quality, including
adjusting industrial structures, promoting low carbon economic development and promoting energy
conservation and emission reduction. Nanning's air quality and the effects of adopted measures are of
particular interest to the public in recent years.
In this research, the daily data were collected over a 5-year period to analyze the spatial and
temporal characteristics of PM10 mass concentration since 2007 in Nanning. The objective of spatial and
temporary analyses of PM observations in Nanning City was to understand the pollution trend of air quality,
333
which is important to the government in developing effective policies and standards to protect the public
health and environment. All of these results will further be beneficial to the Department of Environmental
Protection in Guangxi Zhuang Autonomous Region, China to determine which air pollution sources pose
the greatest exposure risks and threats to human health.
DTAT PREPARATION
There are five air pollution monitoring sites (Qingshan, Zhenning, Nongxiao, Beihu, Downtown)
installed by the Nanning Environmental Monitoring Centre, Guangxi, China. The sites network covers
urban, peri-urban and suburban districts in typical regions, and represents the whole city's air quality very
well (Fig. 1). During the period of January 1st, 2007 through December 31st, 2012, the PM10 samples were
collected at those five air pollution monitoring sites. Sampling and analysis follow “the Air and the Exhaust
Gas Monitoring and Analysis Methods of the 4th edition update” and “Technical Specifications for
Installation and Acceptance of Ambient Air Quality Continuous Automated Monitoring System for PM10
and PM2.5” (HJ/T 193-2005), which are designed by Ministry of Environmental Protection of the People’s
Republic of China. As some of the samples were invalid or missing due to mechanical failures or bad
weather, a total of 10,420 valid PM10 mass concentrations data (2007-2012) were collected. The spline
interpolation was used to control data quality, especially for missing data. The data impairing rate is:
540/10,960=5%.
DATA PROCESSING
By exploring the daily records from the five stations, it was found that a rather large number of
records from some sites interwove together, where the concentration at one station was not always higher
or lower than another station, and it was hard to separate the sites with a linear plane. It is similar to the
classical K-means, and the kernel K-means method maps the original data to a higher dimensional feature
space, where the data can be easily separated linearly (Campbell, n.d.).
The calculation and illustration of Monthly Variation Factors (MVF) can follow Equation (1):
˜
•̅—,^
Nt“b =
,”
˜
•̅^
(1)
where, Nt“b is the monthly variation factor for location i and month j in year y.
,”
Nt“b
,”
reflects the variation of PM observation in a particular month related to the yearly average
values. A big Nt“b
,”
value means the PM observations at this particular month is higher than the yearly
average.
OVERVIEW OF THE DATASET

The daily PM10 mass concentrations for the five stations over the period 2007–2012 are summarized
in Table 1. The daily PM10 mass concentration varies greatly, ranging from less than 2.0μg/m3 to more than
500μg/m3. The lowest measured mass concentration was 2.0μg/m3, which occurred at Nongxiao site. The
median and mean concentrations during the full time span indicate the average degree of pollution for every
station.
WHO-recommended AQG, the average annual PM10 should be less than 20μg/m3; and the average
24-hour PM10 mass concentration should be less than 50μg/m3. However, this standard is too strict for many
developing countries. Ministry of Environmental Protection of the People’s Republic of China revised the
original ambient air quality standards (GB3095-2012) on September 30th, 2011, revised standard by
tightening the limits of PM10 concentration; the first grade of the annual mean limit and 24-hour mean is
40μg/m3 and 50μg/m3, respectively, the second grade of annul mean is 70μg/m3, and the second grade of
24-hour mean limit is 150μg/m3. In view of this, all those sites had a mean PM10 mass concentration greater
334
than 50μg/m3. Although it reached the national second grade standard, people of Nanning exposed to a
higher long-term mortality risk relative to the AQG level.
Table 1. Statistical summary of the daily PM10 concentrations at the five sites in Nanning City, Gunagxi,
China.
Statistical summary (μg/m3)
Sites
Min Median Mean Max Std.
Qingshan 5.0 52.0 63.6 394.0 40.6
Zhenning 8.0 63.0 76.0 504.0 47.3
Nongxiao 2.0 58.0 66.4 247.0 41.9
Beihu 3.3 56.0 68.1 301.0 47.8
Downtown 3.0 47.0 56.8 239.0 38.8
SPACIAL AND TEMPORAL ANALYSES OF PM

With the steady and faster development of economy, the GDP increase around 13% a year-on-year,
the PM10 mass concentration is increasing as a whole. As the annual trend of the PM10 mass concentration
for each site showed in Figure 1, the concentration of PM decreased sharply from 2007-2009, and increased
from 2009-2011, then decreased in 2012. Beihu is the site with the largest change of concentration
(56.0μg/m3), followed by Nongxiao (41μg/m3), and Zhenning (37μg/m3). In 2009, the global economy was
affected by a serious of unprecedented international financial crisis. Although a series of macro-control
strategies had been applied by the Central Government of China, Nanning economy was still stabilized and
the PM mass concentration reduction proves the global economic crisis impact on industries’ manufacturing
and the market.
FIGURE 1. Trends of PM in terms of means and variances from year 2007-2012 at five different sites in
Nanning City, China.
335
MVF at Zhenning MVF at Qingshan

2.50
2.50
2.00 2.00
2007 2007
1.50 2008 1.50 2008
Axis Title
Axis Title
2009 2009
1.00 2010 1.00 2010
2011
2011
0.50 0.50 2012
2012
0.00 0.00
Jan
Feb
Sep
Nov
Oct
Mar
Apr
Dec
May
Jun
Aug
Jul
Jan
Mar
Apr
May
Nov
Aug
Dec
Feb
Jun
Sep
Jul
Oct
MVF at Nongxiao MVF at Beihu
2.50 2.50
2.00 2.00 2007

2007
2008
2008 1.50
Axis Title
1.50
Axis Title
2009
2009
2010
1.00 2010 1.00
2011
2011
0.50 0.50 2012
2012
0.00 0.00
Dec
Apr
Jan
Feb
May
Aug
Sep
Nov
Jul
Oct
Mar
Jun
Mar
Apr
Dec
May
Jan
Aug
Feb
Jun
Jul
Sep
Nov
Oct
MVF at Downtown
2.50
2.00
2007
1.50 2008
Axis Title
2009
1.00 2010
2011
0.50
2012
0.00
Dec
Mar
Apr
Jan
Feb
May
Jun
Aug
Sep
Nov
Jul
Oct
FIGURE 2. Monthly Variance Factor (MAVs) for year 2007-2012 at all locations in Nanning City,
Guangxi, China.
The Beihu site and Nongxiao site are located in Xixiangtang distinct, the Zhenning site is located
in Jiangnan distinct. From the spatial analysis of the temporal trend of PM10 mass concentration of the sites,
the major pollution source distributed in Jiangnan distinct and Xixiangtang distinct of Nanning city. A
large number of industrials are located in the south and west of the city, and these factories might emit
various kinds of pollutants. The spatial analysis of the five stations revealed the spatially heterogeneous
nature of PM10 pollution across the city. Pollution in the south region and west region are heavier than in
the eastern regions, while it is lighter than that in the northern regions. Many people live in suburban areas
while working in the center of the city, which also enhances the traffic burden in urban and peri-urban areas.
336
Therefore, more traffic pollution was produced. The evidence was showed on the annual concentration
change of PM in down monitoring site with the vehicle number in the city increased gradually.
Air pollution of Nanning City is typically coal burning resulted (Hu, 2003). Major sources of PM
in Nanning include emissions from manufacturing facilities, industrial boilers and kiln, automobile exhaust,
and soil-derived aerosols are additional sources. Construction fugitive dust contributed great impacts on the
high annul mean concentration of PM10 (63.6μg/m3) over the downtown in Qingshan district, which should
be a control site during 2007-2010. After those real estate projects were completed gradually, the
concentration of PM10 went down.
MONTHLY VARIATION PATTERNS

The seasonal variations are obvious by the monthly variation patterns at each site. In Figure 2,
winter is the season with the highest PM10 mass concentration, the seasonal distribution characteristics of
monthly variation had the decreasing trend of winter, autumn, spring, and summer．This is in accordance
with the other results in Nanning (Cheng et al., 2013). Meteorological factors have the greatest influence
on the diffusion and transport of air pollutants (EPA, 2003). An investigation (Mo et al. 2008) on the
relationship of ambient PM10 levels and meteorological parameters showed that there is a negative
correlation between PM10 density and the essential factors such as the precipitation, temperature, wind
velocity, and moderate inverse relation with relative humidity.
DISCUSSION AND RECOMMENDATIONS

During the 11th FYP of China, the most effective measures so far seem to be on the industrial sector,
particularly for SO2 reduction in power plants. Compared to the 10th FYP of China, the emissions of industry
pollution in Nanning city was reduced by 32.1%, of which the SO2, industrial soot and dust were reduced
by 1.22%, 81.0% and 53.3%, respectively. Very detailed requirements and regulations have been issued by
the provincial and local governments for the 12th FYP, also more than 290 seriously polluting enterprises
were closed from 2010-2012. However, the PM mass concentration of the air fluctuated around 65μg/m3
from 2007-2012. In addition, the vehicle emission should be increased with the vehicle numbers jumped
from 475,300 in 2007 to 1643,727 by the end of 2012, the situation of PM reduction for Nanning in the 12th
FYP is very critical. Many issues such as the vehicle emission control, the fugitive dust of construction and
demolition management, and the effective control strategies on nearby industries need to be addressed for
further clean air programs. The study results from the content of PM to indicate the possible source of
respirable particle should be useful for the government to effectively alleviate PM pollution.
CONCLUSIONS
Nanning city, nicknamed as the “Green City,” has traditionally a good reputation for its clean air
but now is with pollution alerts. Nanning received an orange alert for the smog on Dec. 6, 2013. Nanning
still has a long way to go in order to achieve its 12th FYP targets whereby the spatial and temporal analysis
of PM pollution. Facing the mounting pressure, the effective measures need to be developed to address the
PM reduction. Further improvement of pollution reduction may optimize the economic structure, to develop
low-carbon economy, to promote the utilization of environmental friendly technologies, and to improve the
personnel appraisal system to provide stronger incentives for achieving pollution reduction. Furthermore,
agriculture sources need to be taken into the consideration during the 12th FYP.
ACKNOWLEDGEMENTS
This research is partially supported by the Nanning Environmental Monitoring Centre, Gguangxi,
China. Supports by the U.S. National Tier 1 University Transportation Center (UTC) TranLIVE and the
U.S. National Science Foundation (NSF) CREST #1137732 are also gratefully acknowledged. Zhihu
Huang and Juan Ma’s significant contributions on field sampling and laboratory analysis are highly
recognized.
337
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Condition in Nanning”. Journal of Meteorological Research and application, 29(1):55-56.
World Health Organization. 2006. “Air quality guidelines—global update 2005, Summary of risk
assessment”. 9.
338
VEHICLE EMISSION ANALYSIS AT RESTAURANT DRIVE THROUGH FACILITIES WITH

DIFFERENT CONFIGURATIONS
Keziah Hill1, Azimi Mehdi, Fengxiang Qiao, and Lei Yu

ABSTRACT: Although shopping at drive throughs are more convenient; the facilities have negative impact
on air quality. Drive-through users stay in their vehicles, and have the engine running. An idling vehicle
waiting in line at a drive-through facility has negative effects that people usually do not recognize; it wastes
gas, harms air quality, and increases greenhouse gas emissions. As a result, the produced emissions may
cause respiratory-related health effects. This study examines emission factors at three fast food restaurants
in Houston, TX, with different drive-through configurations. By driving on each facility in two different
times of the day (peak and non-peak hours), instantaneous speed and acceleration of vehicles were collected
on a second-by-second basis using Global Positioning System (GPS) devices. Vehicle Specific Power
(VSP) values were calculated, using the instantaneous speed and acceleration, and were used to obtain the
operating mode distribution bins based on the definition provided by the EPA (Environmental Protection
Act) MOtor Vehicle Emission Simulator (MOVES). The vehicle emissions were calculated by applying the
operating mode binning approach. The emission factors analyzed in this study are Carbon Monoxide (CO),
Carbon Dioxide (CO2), Oxides of Nitrogen (NOx), and Hydrocarbons (HC). The study identifies which
drive-through configuration (in terms of number of stops and number of lanes) causes more emission.
INTRODUCTION
Drive-through facilities have become integral parts of not only restaurants but also other businesses
such as banks, pharmacies, ATMs, coffee shops, and dry cleaning facilities. Drive throughs bring in an
average of 70% of revenue at fast food restaurants. With the use of technology, drive-through facilities are
made much more convenient and faster for customers. However, few people consider the negative impacts
that the facilities have on the air quality and human being health. Recent studies has shown that a vehicle
produces double Carbon Monoxide (CO) when it is idle for a long period of time, and the vehicles burn
around 50 million gallons of gasoline a year, or 0.7 gallons an hour when they idle at drive-through windows
(Rohrlich, 2010).
The restaurant drive throughs may be different in size, number of lanes, and stops; however they
all serve the customers who stay in their vehicles with engines on during food purchase. In recent years,
drive-though facilities have been designed in such a way to make services faster and to bring in more money
by adding more lanes. Adding lanes make it easier to accommodate more customers with driving vehicles.
It allows more cars to be served, and as a result, there would be more vehicle idlings and stops. The more
people use drive throughs, the number of idling vehicles increases. These changes produce more emission
and impact the air quality. Figure 1 shows a sample of a standard drive through designed with two lanes
and two stops.
Drive-through facilities produce vehicle emissions. A study conducted in Massachusetts University
showed that on an average day at a McDonald’s drive through, 272 cars and 131 trucks used the drive-
through lane. The cars and trucks spent an average of 1,539 and 698 minutes idling, respectively, which
was determined to be 10,704.4 grams of emission released daily only in that specific location (Cowie,
2013). A good design of drive-through facilities in terms of configuration of lanes and number of stops
would be able to reduce the emissions significantly. The goal of this research study is to identify which
drive-through configurations (in terms of number of stops and number of lanes) causes more emission.
1
The first author of the paper is a full-time student.
339
Furthermore, the landscaping around the study location will be observed in this study since landscaping
around the drive-through facilities may reduce the emission. Trees and plants make their food from carbon
dioxide (CO2) in the atmosphere. In other words, they also absorb CO2 and other dangerous gasses and
replenish the atmosphere with the oxygen. Trees also trap and hold particle pollutants that can damage
human lungs (see Figure 2).
Menu Pick-up window

BBoard
Speake
r
Menu 2
FIGURE 1. A sample design of a drive-through restaurant

(http://www.mainstreetmenus.com/DefaultFilePile/Mainstreet/Literature/SellSheets)
FIGURE 2: Process of how trees remove gaseous pollutants

(http://www.epa.gov/climatechange/climate-change-waste/life-cycle-diagram.html)

To conduct this research study, a couple of steps were taken in order to determine the locations for
data collection and also the best method of the study to retrieve more accurate results. Three fast food
restaurants were selected in Houston, TX for data collection. When choosing the restaurants, considerations
340
such as location of restaurant, size of facility, number of existing lanes in drive throughs, and number of
stops in drive throughs were taken into account. The restaurants selected for this study were McDonald’s
(located at 9805 South Main St., Houston, TX), Chick-fil-A (located at 5001 Beechnut St., Houston, TX),
and Jack in the Box (located at 3601 Old Spanish Trail, Houston, TX). A traffic study (traffic count) was
conducted during both peak and non-peak hours to identify the traffic volume during different time of the
day. Finally, two time periods were selected: 11:00 a.m. to 1:00 p.m. as peak hours, and 2:30 p.m. to 4:30
p.m. as non-peak hours. By driving at drive-through facilities and using a GPS device, instantaneous speed
and acceleration data were collected at each location. The GPS data were used to calculate the emissions at
each location (restaurant) by applying the VSP and Operating Mode ID binning procedure. VSP is defined
as instantaneous tractive power per unit vehicle mass:
VSP = v × (1.1 a + 0.132) + 0.000302 v3
where:
v is the vehicle speed (m/s), and
a is the vehicle acceleration (m/s2)
Operating Mode ID refers to operating mode bins that represent braking, idling, and varying levels of the
vehicle’s VSP and speed. Based on the definition provided by the U.S. EPA (Environmental Protection
Act) MOtor Vehicle Emission Simulator (MOVES), a vehicle operating mode is broken down into 23 bins.
Bins 0 and 1 represent breaking and idling. Bins 11 to 16 represent driving with speed lower than 25 mph.
Bins 21 to 30 represent driving with speed between 25 mph to 50 mph. Bins 33 to 40 represent driving with
speed 50 mph and greater. When operating mode ID bins were obtained, they were combined with the
emission rates collected with Portable Emission Measuring System (PEMS) (Tao and Yu, 2012), and the
total emissions were estimated. Emission factors analyzed in this study are Carbon Monoxide (CO), Carbon
Dioxide (CO2), Oxides of Nitrogen (NOx), and Hydrocarbons (HC). Table 1 lists the emission rates for
each operating mode bin collected with PEMS.
TABLE 1. Emissions rates of operating mode bins collected with PEMS (Tao and Yu, 2012)
341
Three restaurants were selected with different drive-through designs. Chick-fil-A has two lanes
with two stops, McDonald’s has one lane with three stops, and Jack in the Box has one lane with two stops.
The purpose of this study is to analyze the effects of drive-through facilities at fast food restaurants on
emission outputs of light-duty vehicles.
1200
1000
Emission Factor 800
600
400
200
0
CO2 (g) CO (mg) HC (mg) NOx (mg)
Chick-fil-A 413.41 1051.77 588.04 759.89
McDonald's 336.19 818.31 468.39 641.85
Jack in the Box 230.88 494.97 325.32 452.67
FIGURE 3. Emission during non-peak hours, day 1
3500
3000
Emission Factor
2500
2000
1500
1000
500
0
Chick-fil-A 350.31 549.3 488.15 740.89
McDonald's 725.03 3216.9 1076.08 942.2
Jack in the Box 460.2 2038.91 689.26 592.61
FIGURE 4. Emission during non-peak hours, day 2
2000
1800
1600
1400
1200
Emission Factor
1000
800
600
400
200
0
Chick-fil-A 915.91 1851.9 1289.42 1833.3
McDonald's 185.41 483.37 262.39 338.71
Jack in the Box 304.64 598.32 430.67 615.14
FIGURE 5. Emission during peak hours, day 1.
342
Figures 3 and 4 show the estimated emission factors for each light-duty vehicle using the drive-
through facilities at three study locations during non-peak hours (in two different days). On day 1, Chick-
fil-A had the highest emission factors. Furthermore, Chick-fil-A emission factors on day 1 was higher than
day 2. The reason is the traffic volume was heavier on day 1 which increased the idling time and resulted
in more emissions. Also one lane was closed on that day. On day 2, there were not so many vehicles in
Chick-fil-A during the non-peak hours, and the average waiting time for the vehicles was less than one
minute. McDonald’s had the second highest emission on day 1, and the highest on day 2. On day 2,
McDonald’s had a higher traffic volume, and the waiting time was longer than day 1. In terms of
landscaping, there were more trees and flowers surrounding Jack in the Box.
Figures 5 and 6 show the estimated emission during peak hours on day 1 and day 2. During the
peak hours of day 1, McDonald’s had the lowest idling time and had the lowest emission factors. However,
it has the highest emission on day 2. The reason is, at McDonald’s location, the traffic volume was higher
on day 2 compared to day 1. The high traffic resulted in longer waiting time and more emission. Emission
at Chick-fil-A was high on day 1 because both of the drive-through lanes were open. Opening two lanes
caused a longer waiting time since it allowed more vehicles to place orders at the same time.
4500
4000
3500
3000
Emission Factor
2500
2000
1500
1000
500
0
Chick-fil-A 628.38 1643.37 898.59 1140.11
McDonald's 940.76 4169.85 1409.62 1212.5
Jack in the Box 817.48 3621.12 1224.03 1053.04
FIGURE 6. Emission during peak hours, day 2.
CONCLUSION
Chick-fil-A location had the most traffic on day 1 during peak and non-peak hours. The emissions
were higher at this facility during non-peak hours versus peak hours. The reason was one of the lanes in the
drive-through facility was closed during non-peak hours, however the number of the vehicles using the
drive through between 2:30 p.m. and 4:30 p.m. was still considerable. Due to this fact, there was increase
in waiting time, and vehicles emitted more pollutions. During the peak hours, McDonald’s had the highest
emissions since this drive-through facility had three stops. The result of the study shows that Jack in the
Box seems to have the best drive-through configuration (one lane, two stops) since the related emission
factors was the lowest (considering the traffic and the number of vehicles used the facility) during both
non-peak hours and peak hours.
ACKNOWLEDGEMENTS
Supports for this research study by the Department of Transportation Studies at Texas Southern
University and the Innovative Transportation Research Institute (ITRI) are gratefully acknowledged.
REFERENCES
Cowie, A. 2013. Don’t Drive Through. http://www.aboutmyplanet.com/environment/dont-drive-through.
343
Jimenez-Palacios, J. L. 1999. Understanding and Quantifying Motor Vehicle Emissions with Vehicle
Specific Power and TILDAS Remote Sensing. Ph.D. Dissertation, Massachusetts Institute of
Technology, Cambridge, MA.
Lai, J., L. Yu, G. Song, P. Guo, and X. Chen.2013. “Development of City-Specific Driving Cycles for
Transit Buses Based on VSP Distributions: Case of Beijing.” Journal of Transportation Engineering.
139(7): 749-757.
Lashgari,A. 2013. Trees and Air Quality. http://www.arb.ca.gov/research/ecosys/tree-aq/tree-aq.htm
Mattingly, S. P., M. L. Sattler, H. Bhatt, S. Sumitsawan, N. Pala-en, and P. Parikh. 2009. “A Model for
Estimating NOx Emission Reductions after Closing Drive-Thrus.” In TRB 88th Annual Meeting
Compendium of Papers. Paper No 09-3489.
Rohrlich, J. 2010. Why Drive-Thru Windows Are Crucial to Fast Food.
http://www.minyanville.com/businessmarkets/articles/drive-thrus-emissions-fast-food-
mcdonalds/5/12/2010/id/28261.
Sickels, R. C. 2004. The 1940s (American Popular Culture through History). Greenwood Press.
Tao, F., and L. Yu. 2012. “Effects of Driving Behavior on Vehicle Emission: A Case Study in Houston,
Texas.” In TRB 91st Annual Meeting Compendium of Papers. Paper No 0852.
Zhai, H., H. C. Frey, and N. M. Rouphail. 2008. “A Vehicle-Specific Power Approach to Speed- and
Facility-Specific Emissions Estimates for Diesel Transit Buses.” Environmental Science & Technology.
42(21): 7985–7991.
344
PREDICTION OF POLLUTANT CONCENTRATION THROUGH THE CONSOLIDATION OF

MULTIPLE AIR DISPERSION MODELS USING A SUPERENSEMBLE
Shoou-Yuh Chang and Frank Gronwald

(North Carolina A&T University, Greensboro, NC, USA)
Determining the level of air pollution is a modern day necessity for government regulators and
industrialized sources. Air dispersion models are often used to determine the concentration of a pollutant.
However changing conditions and several assumptions made by the models limit their accuracy at various
times. This research proposed combining four different air dispersion models (Gaussian Plume, Variable
K Theory, Box, and AFTOX) into a superensemble. Since the superensemble is typically more accurate
than its member models, the end result should be a more accurate prediction under any condition. In the
interest of evaluating performance, the change in accuracy was measured through RMSE calculations and
the change in precision was measured through calculating the Brier Score. It was found that in the
prediction of ™ the superensemble produced average reduction of 58.2% (mean RMSE) and a 41.9%
(Brier Score) from the other models. In š™ prediction, the superensemble produced average reductions of
49.3% (mean RMSE) and a 46.2% (Brier Score) from the lowest model.
345
EFFECTS OF QUARRY OPERATION PROCES

SES TO AIR QUALITY IN ISTANBUL CEBECI ZONE ACCORDING TO PM10 EMISSIONS
Kadir Alp1, İsmail Toröz1, Edip Avşar2, Ezgi Erdogan1,Banu Özlem1, İlker Akmirza1*
(1 Istanbul Technical University, Istanbul, Turkey
2
Çanakkale Onsekiz Mart University, Çanakkale –Turkey)
ABSTRACT: Nowadays air quality measurements and evaluations are playing significant role especially
in the districts where settlement and industry stands side by side. In this sense, facilities where quarry
operations are conducted may cause a high level of dust and PM emissions. Within this project a residental
area (Cebeci/İstanbul) that is covered with quarry establishments was investigated according to air quality
standards of Turkey. PM10 and dust emissions from 15 quarry operation processes were analyzed in details.
Air quality monitoring stations were established to determine PM emissions and solution alternatives were
investigated in detail to decrease PM emissions in quarry operations. For this purpose, PM10 measurements
were done at representative points and the results indicated that the measured levels were 3-5 times higher
than the other points in Istanbul at the same time span. During the 112 days of measurements PM10
parameters have exceeded the European Union and Turkey’s standards. These results indicate that
unsupervised operation of the facilities negatively affect the region air quality. Solution alternatives were
investigated and it has been found that turning crushing-shifting units into close systems and moisturizing
roads inside the quarries, and turning the roads into asphalt roads can reduce the emission from quarry
operations.
INTRODUCTION
Air pollution, in its most general sense, can be described as a corruption of the natural composition
of the air or an increase in the concentration of unwanted particles in the air. Main pollutants among these
sources can be listed as:
• Particulate matter (PM)
• Sulphur dioxide (SO2)
• Carbon monoxide (CO)
• Nitrogen oxides (N0x)
• Hydrocarbons (VOC’s)
As listed on the top particulate matter is one of the criteria air pollutant parameters and mainly
released to do atmosphere while combustion of fossil fuels, industrial activities (mine quarries, crushing-
sifting facilities) and traffic. Particles may cause lung and heart diseases. Fine particles can even reach
alveoles of lungs and heavy materials in these particles like lead can directly mix in blood.
Within this project Cebeci region which is the 19th largest region of Istanbul and contains 15
neighborhoods, aggregate quarries and 2 rivers, was investigated. In Cebeci after the 1970s, due to the fast
and unplanned urbanization, quarries surrounded by settlements. Because of this situation, complaints about
PMs in this region have been increased year by year. Generally Cebeci region has total surface extent of
the stone quarries of 830 hectares, and workable reserve extent is 215 hectares. According to 2013 data, it
is stated that the workable visible reserve is approximately 850 million tons that consisted of 419 million
tons of sand stone and 438.94 million tons of limestone. The total reserve is approximately 2.15 billion
tons. Annual production is known to be 30 million tons. Furthermore there are 7 concrete plants and 7
asphalt facilities are operated within the stone quarries as well. Total daily capacity of 15 active stone
quarries in the region is calculated as 108,000 tons per day. South, east, and west of the stone quarries are
surrounded with settled areas and dwelling houses; thus, the effect of stone quarries on air quality gains
346
importance [2] In the last 4-5 years, many efforts conducted for determining the contribution of aggregate
quarries to this problem and solutions to diminish them are accelerated. The first aim of this work was
determining the air quality in the region by means of measurement and the second aim was determining the
precautions that can decrease the effects of the quarries on the air quality. [1-3, 4, 5] .

Selecting of the representative sampling points for measurement of PM emissions consist one of
most important point of the study. In this case some technical criterias are also taken into consideration and
four main criteria are determined for presentative sampling.
• Annual dominant direction of wind,
• Location of electric sources for the measurement devices,
• Location of buildings around the measurement point,
• Security of measurement devices
According to this criterias the air quality measurement work were conducted by Tübitak Marmara
Research Center at 4 points between 16.07.2012-18.09.2012.
Table 1a. Measurement points and coordinates.
Point Description of the Point Coordinates
1 Halk ekmek 410.6.531 N; 280.52.565 E
2 Constabulary Management 410.6.904 N; 280.51.764 E
3 Habipler 410.7.410 N; 280.50.636 E
4 Cebeci village 410.7.3341 N; 280.52.837 E
Selected points’ locations are supposed to allow them to reflect the effect of the emissions from the
aggregate quarries as they are on the dominant direction of wind. Location of measurement points are given
in Figure 1.
Figure 1. Locations of quarries and measurement points.

Air quality measurements can be conducted via manual and automatic systems. Manual systems
are generally used for the measurement of particulate matter and SO2. Beta Gauge Method was used for
347
PM10 emissions and Bulk Sampling method was used for layed dust [4]. General measurement methods and
standards of equipment are given in the Table 1b.
Table 1b. Parameters, measurement methods and standards
Parameter Measurement Methods Measurement

Standard
PM10 Beta Gauge Method (Automatic) EN 12341
Layed Dust Bulk sampling TS 2341
In Turkey; The Regulation of Control the Air Pollution Caused by Industrial Activities came into
force on 03.07.2009 with Official Gazette number 27277 According to regulation limit values of PM10 and
the settled dust parameters summarized in Table 2.
Table 2. In the facility area, Long Term, Short Term Limit Values and Gradual Reduction
YEAR
Limit value
Parameter Time [µg/m3]
2008 2009 2010 2011 2012 2013
Particulate STL 300* 300 260 220 180 140 100

Material on the air
(PM 10) LTL 150* 150 132 114 96 78 60
STL 650* 650 598 546 494 442 390

Settled Dust
LTL 350* 350 322 294 266 238 210
*Limit values will be reduced until the target values of 2014 are reached equally and annually.

An aggregate quarry is a process where dust and particulate matter emission released to atmosphere
in a high level. At the beginning of the process, the sources in the mine are crushed by explosion in order
to be fit for the process of crushing and sifting. Loaded on to lorries, crushed materials are carried to
crushing-sifting unit and materials are crushed further according to size of end product. Later, materials are
stored and delivered to the customers via transportation. Throughout the process, during the crushing-
sifting, storing and transportation, dust and particulate matter emissions are emitted to the atmosphere.(6,7)
According to RCAPCIA Table 12.6, it is possible to calculate total emission quantity by multiplying the
emission quantity with various emission factors. An example case of reducing emission level in aggregate
quarries with controlled precautions is shown on Table 3.
In order to determine emission effect levels of aggregate quarries in İstanbul Sultangazi Cebeci
district on the settlement areas located around, current situation is revealed by measuring the settled dust at
4 different points and PM10 measurements at 2 different points between the dates 16.07.2012-18.09.2012.
Observed values are compared to the limit values set by The Regulation of Control of Air Pollution Caused
by Industrial Activities. According to the above mentioned regulation, PM10’s Short Term Emission limit
value is 140 µg/m3 and Long Term Emission limit value is 78 µg/m3. According to the data collected as a
result of the measurements, daily results of PM10 measurement at point 1 and 2 are given in Figure 2 and 3.
348
Between the dates 19-20-25-31.07.2012, on 13.08.2012 and 17.9.2012 LTL (KVS) values, and on
20.07.2012 and 13.08.2012 STL (UVS) values are surpassed for measurement at point 1.
Table 3. Emission of an Aggregate Quarry with 100tons per hour Capacity
Example emission calculation for
Emission Factors 100 ton/hour capacity %
Sources kg/ton (kg/hour) Reduction
Uncontrolled Controlled Uncontrolled Controlled
Crushing 0.08 - 8 0 100
Removal 0.025 0.0125 2.5 1.25 50
Loading 0.01 0.005 1 0.5 50
Transport 0.7 0.35 5.6 2.8 50
(total distance double
journey)
(kg/km per vehicle)
Unloading 0.01 0.005 1 0.5 50
Storing 5.8 2.9 0.58 0.29 50
First Crusher 0.243 0.0243 24.3 2.43 90
Second Crusher 0.585 0.0585 58.5 5.85 90
Total Emission 101.48 13.62 86.6
150
140
130
120 PM10 KVS
110
100
90
PM10 µg/m3
80
70
60
50
40
30
20
10
0
19.7.12
21.7.12
25.7.12
27.7.12
30.7.12
01.8.12
03.8.12
13.8.12
15.8.12
17.8.12
21.8.12
23.8.12
25.8.12
28.8.12
30.8.12
13.9.12
15.9.12
Date 18.9.12
Figure 2. PM measurement conducted at point 1 and comparison with limit values
800 PM10 KVS UVS

750
700
650
600
550
500
450
PM10 µg/m3
400
350
300
250
200
150
100
50
0
09.8.12
11.8.12
13.8.12
15.8.12
17.8.12
19.8.12
21.8.12
23.8.12
25.8.12
27.8.12
29.8.12
31.8.12
13.9.12
15.9.12
17.9.12
Date
Figure 3. PM measurement conducted at point 2 and comparison with limit values

At point 2, except for the dates 21 and 22.08.2012 STL (KVS) are surpassed every day, and except
for the dates 20-21-22.08.2012 LTL (UVS) are surpassed every day. It is also observed that measurement
349
results are relatively lower in the point 2 between the dates 20-22 of August when is an official holiday in
Turkey and traffic level near the measurement point was very low. One month of settled dust sampling
results at points 1-2-3 and 4 are given in Table 3b.
Table 3b. Settled dust results of 4 points
Point result STL (KVS)
µg/m2.day µg/m2.day
1 561
2 222
3 1501 442
4 151
Table 4: Wind speed, direction and stability classes throughout the measurement process
a. Wind rose b. Stability class rose
c. Wind speed and stability class distribution histograms
Speed and direction of wind and stability classes which are important for the interpretation of
measurement results are given in Table 4. During the measurement process, the wind has dominantly blown
in northern directions, from north, north-east and north-west. When stability classes are taken into
consideration, it is visible that unstable or close to neutral situations are more common and this situation
increases the level of vertical mixture yet as the distance of emission in the horizontal level is decreased,
maximum concentrations are seen in the areas closer to the sources (8).
350
In terms of settled dust results, it is visible that point 2 which has higher PM results has a lower
average of dust when compared to number 1. Number 4 has the lowest values. Number 3 has the highest
values in terms of settled dust.
CONCLUSION AND EVALUATION

When measurement results are evaluated, it is observed that measurement point 2, Constabulary
Control Center surpasses limitation of RCAPCIA Table 2 in terms of PM parameters of both STL (KVS)
and LTL (UVS) (Illustration 2). As a result of the measurements Constabulary Control Center’s average
PM10 emission is determined as 323 µg/m3.
However, at point 1 (Halk Ekmek), average PM10 emission is determined as 65 µg/m3 and as lower
than both LTL (UVS) and STL (KVS) (Illustration 3).This situation can be explained that measurement
point is located opposed side of dominant wind direction and doesn’t affected from PM10 emissions. As it
seen in Table 4 dominant wind direction is also determined as “North-East – North Winds” according to by
the closest Kilyos meteorological data station with drawn illustrations. It is understood that PM emissions
from Cebeci aggregate quarries are dominant on the wind direction and that is the reason why measurement
points 2 especially affected from PM10 emissions. Also measurement point 2 located very close the traffic
and the emission resulted from the vehicles that carrying excavated materials from quarry operations also
increase the PM10 emission concentration.
Generally the effects of the facilities has been observed at the point 1 and 3 with the increasing
concentration of settled dust and in addition to at the point 2 high PM level and low settled dust
concentration has been observed that indicates impact of the traffic from the road.
An example calculation presents that if the emissions in the facilities are controlled, emissions of
the facility can be reduced up to 80%. One of the main precautions in the aggregate quarries is to control
the emission from turning crushing processes. Shifting units into close systems and including dust
controlling units (water spraying) inside. Also moisturizing roads inside the quarries, turning the roads into
asphalt roads can prevent the dust emission resulted from the vehicles. Moisturizing the stocked materials
in order to prevent dust emission and covering them with baleclothes can also reduce the emission from
facilities up to 80% and this way can solve the air pollution problem.
Interpreting the gathered PM results according to the WHO Air Quality Guideline clearly shows
that these results indicate possible and very important effects on human health. These effects of the PM
are not limited to only human beings. The particle materials present in the outdoor air does not only harm
the outdoor buildings, furniture, plants, and animals; but also it negatively affects the indoor air quality of
the places where people live and work. Activities of the stone quarries also negatively affect the agricultural
fields and forests nearby. It is observed that in the settlements around to the stone quarries, the plants are
covered with dust and they look as if they are not alive. As the dust in the air falls on the surface with
precipitation, the resulted mud causes serious pollution in the settlements. For these reasons, necessary
precautions must be taken in this kind of facilities.
REFERENCES
[1] Refik Saydam Hıfzıssıha Center Web Page, http://www.rshm.saglik.gov.tr/hki/pdf/hava.pdf

[2] The Regulation of Control of Air Pollution Caused by Industrial Activities (RCAPCIA) (Official
Gazette date and number: 03.07.2009-27277)
[3] US Environmental Protection Agency Web Page, http://www.epa.gov/oar/oaqps/gooduphigh/
good.html#1
[4] Ministry of Environment and Urban Planning Web Page, http://www.lab-cevreorman.gov.tr
/sayfadetay.asp?turid=20
[5] Ministry of Environment and Urban Planning Web Page, http://www.havaizleme.gov.tr/hava.html
351
[6] Babatunde Saheed Bada, Kofoworola Amudat Olatunde & Oluwafunmilayo Abidemi AKande. Air
Quality Assessment in the Vicinity of Quarry Site, Environment and Natural Resources Research; Vol.
3, No. 2; 2013.
[7] Tony Byrd, Mary Stack, Ambrose Furey, The assessment of the presence and main constituents of
particulate matter ten microns (PM10) in Irish, rural and urban air, Atmospheric Environment 44 (2010)
75–87
[8] I. Toroz, K. Alp, E. Avsar, İ. Akmirza, B. Ozlem, 2013. Investigation the effects of Cebeci quarries on
environmental air quality (in Turkish) Istanbul Technical University Environmental Engineering Dept
Technical Report, Report no and date: 1206-1216, 14.03.2013.
352
SCENARIO MODELING AS A TOOL FOR MULTI-POLLUTANT POLICY DEVELOPMENT

IN CALIFORNIA
Joshua Cunningham and Nicole Dolney

(California Air Resources Board, Sacramento California, U.S.A.)
California policymakers are now leveraging scenario modeling as an important tool for policy development,
particularly to evaluate transportation strategies that simultaneously address the multiple pollutant
challenges in the state. To meet federal ozone standards, current estimates are that NOx emissions need to
be reduced, relative to 2010 levels, 80% by 2023 and 90% by 2032 in the South Coast and San Joaquin
Valley. State law requires greenhouse gas (GHG) emissions to return to 1990 levels by 2020, and
California’s long-term GHG reduction goal is an 80% reduction from 1990 levels by 2050. Achieving
these multiple emissions targets by the various deadlines will require aggressive strategies including
efficiency improvements, cleaner conventional combustion, advanced technology, alternative fuels, and
reduced vehicle activity.
Scenario planning tools allow policymakers to evaluate a wide range of emission reduction
strategies as regulatory requirements and incentive programs are being developed. The objective of this
project has been to fully develop the Air Resources Board (ARB) Vision Model to identify and analyze
multiple strategies that maximize both criteria and GHG emission reductions. Over the next several years,
California air quality, transportation, and energy agencies will need to make decisions that set the direction
for how multi-pollutant goals will be met.
The ARB Vision model is an emissions and energy use inventory projection tool with varying
choices of emission reduction strategies, and includes vehicle stock turn-over characterization for the on-
road sectors. Initially influenced by the Argonne National Laboratory Vision model, the ARB model is
substantially different with the inclusion of non-road mobile sectors, full well-to-wheel criteria emissions
using CA-specific emission factors, and emissions and activity allocation at local county levels.
Several scenarios have been explored with an example in the left figure below that conveys the
potential deep reductions in NOx emissions with aggressive strategies. Light duty vehicles (LDV) will
need to be largely electrified, which will require a range of technology options depending on vehicle size
and range attributes. Low carbon, advanced biofuels are an important strategy to be utilized, but will have
supply limits for the CA market. Heavy duty and non-road sectors will need to focus on cleaner
conventional engines, including a transition to natural gas, knowing electrification strategies will be
important but more limited than in the LDV sector. Concurrently, fuel and electricity production needs to
increasingly come from low carbon sources, going well beyond current California policy requirements,
primarily to address the GHG targets. The figure on the right shows the emission reductions from a range
of strategies for HDVs, highlighting varying benefits between NOx vs. GHGs emissions.
To cofront the transformation required in the transportation and energy sectors, policymakers will
need to carefully coordinate multiple policy instruments, including public incentives, regulatory
requirements, and regional planning. Scenario planning tools help policymakers evaluate the wide range
of strategies that are possible for this complex future portfolio.
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THE USE OF LOCALLY MANUFACTURED ACTIVATED CARBON FILTERS FOR INDOOR

AIR QUALITY IMPROVEMENT
Abdullah M. Al-Qahtani, Waleed H. Al- Rwaily

(King Faisal University, SA)
Gulf area climate is very hot and dry in summer and for this reason air-conditioning has widely been
applied. However health problems related to human respiratory system associated with air-conditioning
systems and indoor air quality appear more frequently.
Citizens of Gulf area spend most of their time indoors surrounded by sources of air pollution:
consumer products, gas appliances, building materials, cigarettes, and furniture can all contribute to air
quality problem.
Activated carbon, also called activated charcoal, is a form of carbon processed from carbonaceous source
materials such as nutshells, peat, wood, and other sources to be riddled with small, low volume pores that
increase the surface area available for adsorption or chemical reactions. Due to its high degree of micro
porosity, just one gram of activated carbon has a surface area in excess of 500 m2, thus can be used for
effective improvement and treatment of indoor air.
This work involve the experiments aiming to improve indoor air quality using activated carbon
filters made from local material , in particular dates' stones. Different gases such carbon dioxide (CO2),
sulphur dioxide (SO2), nitric oxide (NO), nitrogen dioxide (NO2), respirable particulate matter (PM 2.5 and
PM10 ), formaldehyde (HCHO) and VOC, were passed through different layers of activated carbon to
evaluate the performance of their removal or concentration reduction.
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SOURCE APPORTIONMENT OF SELECTED HEAVY METALS IN AEROSOL SAMPLES

COLLECTED FROM SEBELE, BOTSWANA
Alfred S. Likuku*, Gilbert K. Gaboutloeloe and Khumoetsile B. Mmolawa

(Botswana College of Agriculture, Private Bag 0027, Gaborone, Botswana)
Problem statement: Bush fires and dust in the dry winter months establish moderately high background
levels of aerosols. Emissions into the atmosphere by copper mines, coal mines and vehicular emissions are
all possible sources of air pollution with heavy metals. Although there has been assessment and monitoring
of heavy metals and their air pollution in Brazil, Europe, America and other places, there is little
documentation about concentration of heavy metals in aerosols in Botswana.
Approach: A total of 63 aerosol samples were collected at the Botswana College of Agriculture and were
analysed for concentrations of Al, Co, Cu, Fe, Pb, Mn, Ni and Zn in filtrate using a Flame Atomic
Absorption Spectrometer (Varian SpectrAA 220 FS). Statistical receptor models were applied to investigate
potential sources of the studied metals.
Results: Data exhibited enhanced enrichments of Zn (EFg = 76), Al (EFg = 14391), Co (EFg = 19), Cu
(EFg = 5), Pb (EFg = 3) and Ni (EFg = 2), which were attributed to contributions from non-crustal sources,
whereas Mn, and Fe (EFg < 2) were attributed to crustal origin, such as airborne dust. Data were subjected
to factor analysis (FA) twice. From FA-1, two principal components (PC) were revealed. PC-1 showed high
positive loadings of Pb, Zn, Ni, and Al, whereas PC-2 had loadings for Fe and Mn. On the other hand, FA-
2 had three principal components. PC-1 from FA-2 showed strong loadings for Cu, Fe and Mn. FA-2 had
strong loadings of Pb, Al and Zn, whereas loadings for PC-3 were comprised of Ni and Co. the difference
between loadings of FA-1 and FA-2 suggested possibilities of mixed origins of the 6 studied metals. Finally,
air mass back-trajectory analysis showed that during the sampling period, there were only 5 cluster groups
that represented significantly different transport pathways of aerosol samples, where only Zn and Ni mean
concentrations revealed dependence on geographical origin of aerosol samples.
Conclusion: Results of the analysed concentrations of Al, Co, Cu, Fe, Pb, Mn, Ni and Zn in aerosol samples
showed that the presence of Fe and Mn in the atmosphere in the ambient air of Sebele is mainly due to
contributions from lithogenic sources. Pb, Ni, Co, Al and Zn exist because of anthropogenic sources,
whereas, Cu, exist b analysis because of mixed origins. Trajectory analysis further shows that the
anthropogenic Zn and Ni could also be present in the air sampled due to air mass transportation from distant
sources.
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STUDY ON AN OZONE EPISODE OVER THE PEARL RIVER DELTA, CHINA
Jin SHEN1,2,3,*, Hao CHEN 1,XueSong WANG1,JinFeng LI1,Wei LV1, LuanYuan2,3,Liuju ZHONG
2&YuanHang ZHANG 1
1. College of Environmental Sciences and Engineering, Peking University, Beijing;
2. Guangdong Environmental Monitoring Center, Guangzhou
3. State Environmental Protection Key Laboratory of Regional Air Quality Monitoring
*Corresponding author: e-mail:15120092912@163.COM; telephone: 86-020-28368524
ABSTRACT: The north and southeast Pearl River Delta (PRD) was usually upwind clean area in autumn.
Serious ozone pollution there in the mid-late Oct 2008 was first discovered and analyzed. Trajectory
analysis, process analysis, ozone source apportionment tech and sensitive analysis were taken to study
this episode. Under the influence of weak south wind, the precursors emitted in Guangzhou and Foshan
were transported to north/northeast PRD and formed ozone there, which resulted in ozone concentration
reaching more than 100 ppb. As the wind direction transited to the northerly, the precursors emitted in
the central/west PRD and transported to the northeast PRD, were transported to its south, and caused
severe ozone pollution in the southeast PRD. The ozone contributed by chemical process reached more
than 20 ppb/h in Jinguowan. More than 40 ppb ozone was contributed by the precursors emission in the
central/west PRD during the ozone episode. The ozone was highly sensitive to the precursors emission in
the PRD region in the episode. This episode showed complex regional pollution characteristic in the PRD.
If the wind field in PRD was changed from southwesterly to northerly, the risk of ozone pollution in the
north and southeast PRD increased.
INTRODUCTION
The Pearl River Delta (PRD) in south China, where the economy and society are relatively
developed, with dense cities and large population, experiences rapid development and serious regional air
pollution (Zhang et al. 2008). Increased pollution control efforts in recent years were taken, and discharge
of primary pollutants were controlled to some extent, however, Ozone pollution has intensified (Chan and
Yao 2008).
Long-range pollution transport has caught much attention over the world (Lee et al., 2000;
Redington and Derwent, 2002; Abdalmogith and Harrison, 2005; Shan et al., 2009). The trans-boundary
ozone pollution also caused much argument in the PRD. During the serious polluted episodes in Hong
Kong, ozone was mainly contributed by the transport from mainland China (Lam et al., 2005; Huang et
al., 2005). Zhang et al. (2008) and Wang et al. (2010) pointed out that there was significant regional
pollution characteristic in the PRD.The relation between the concentration of ozone and its precursors
was generally nonlinear, and in different environments, the responds of ozone to the change of NOx or
VOC were very different (Murphy et al., 2006; Yoo and Park, 2010). The ozone formation was generally
VOC-limited in urban areas and NOx-limited in village areas (Shao et al. 2009; Song et al. 2010; Wang et
al., 2008).
In hot seasons, the averaged ozone concentration was relatively low. But under the influence of
tropical cyclone or sea-land breeze, there were some ozone episodes in the PRD (Ding et al. 2004; Huang
et al. 2005; Jiang et al. 2008; Fan et al. 2008). Ozone pollution in the PRD was generally most serious in
spring and autumn (So and Wang 2003). The ozone concentration in the southwest PRD and the Pearl
River Estuary (PRE) was highest for most of the days in autumn. And the ozone concentration in the north
and east PRD was relatively low in October (Wang et al. 2010). However, there was a serious ozone
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episode (October 2008) in the north and east PRD which is deemed to be a clean rural and background
area, and the understanding of it is still inadequate currently. Among the former studies in the PRD,
there was no report discovering serious ozone pollution in the east and north PRD in autumn. Hence, in-
depth study of this episode is of great importance for the scientific research of regional ozone pollution
and pollution control. This study mainly focused on this episode and analyzed the origin and development
of this episode.
Few studies of ozone episodes quantitatively figured out the ozone contribution by the emission
of precursors in different regions and emission sectors. This paper integrated the meteorological process
analysis, pollution process analysis, ozone source apportionment tech, and sensitivity analysis to give a
quantitativecomprehensive understanding of the unusual pollution episode in clean areas.
MATERIALS ANDMETHODS
Description of the Models and Tools. To get a better understanding of the process and characteristics of
the ozone episode in October 2008, both modeling and monitoring data were used. The ozone monitoring
stations were located in different parts of the PRD which could reflect the basic characteristics of the
regional atmospheric pollution (Figure 1).The observed data captured a pollution episode in the “clean”
area.
Trajectory model HYSPLIT was used for the analysis of the source and pathway of polluted air
mass, with the meteorological data from NOAA (http://ready.arl.noaa.gov/HYSPLIT.php). Moreover,
The Comprehensive Air quality Model with extensions (CAMx version 5.20) (ENVIRON, 2009) was
used. The detailed model configuration and model evaluation can be found in the paper of Shen (2011).
FIGURE 1. Distribution of monitoring sites

(Note: GDEMC is short for the Guangdong Environmental Monitoring Center)
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FIGURE 2. Technical route
Technical Route. Simulation results and monitoring data of ozone and wind field supported each other.
Meteorological condition and trajectoryanalysis gave qualitative analysis of the movement of certain air
mass, which could partly explain the high ozone episode. Meanwhile, air quality model with extensional
tools quantified the ozone apportionment and sensitive characteristics (Figure 2). The Integrated Process
Rate analysis (IPR) (Zhang et al, 2009) implemented in CAMx calculated the contribution to ozone
concentration of each physical and chemical process.The Ozone Source Apportionment Technology
(OSAT) quantified ozone contribution from different regions and various emission source sectors, and
the Geographic Ozone Assessment Technology (GOAT) determined where the ozone was formed
(Morris et al., 1998; Morris et al., 2001). The (High-order) Decoupled Direct Method (DDM or HDDM)
(Gao et al., 1995; Hakami et al., 2003; Cohan et al., 2005) was used for ozone sensitive study.
Ozone Pollution Episode. Both the observation and simulation data showed that the ozone concentration
in a regional station in the east PRD (Jinguowan in Huizhou) was below 65 ppb in most of the time on
Oct, which exhibited the low ozone concentration characteristic of upwind area. However, there was an
ozone pollution episode on the 23rd, with ozone exceeded 100 ppb in the afternoon (Figure 3 A).
Moreover, similar circumstance happened in the north PRD (e.g. Tianhu, Figure 3 B) on the 21st and
22nd.
FIGURE 3. Time series of observed (black) and simulated ozone concentrations by CAMx (red) in
October, 2008
The north and northeast PRD was traditional upwind area with relatively low ozone
concentration at most of the time in autumn. But the ozone pollution was very serious in the two regions
from 21st to 23rd, Oct 2008. With southerly wind, the high ozone zone appeared in the north PRD in the
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afternoon of the 21st and 22nd, but it appeared in the central and southeast PRD on the 23rd with higher
ozone concentration under the influence of northerly wind (Figure 4). Under the universal influence of
northeast wind from 24th Oct, the ozone distribution became typical again, with high ozone
concentration in west and southwest PRD and low ozone concentration in north and east PRD.
FIGURE 4. Simulated ozone concentration and wind field over the PRDat 14:00 Beijing time from
21st to 24thOctober, 2008
Meteorological Condition during the Ozone Episode. The surface air pressure in the south China was low
in 21st and 22nd Oct, while the surface pressure in the southeast sea of China was relatively high, which
caused that southerly wind prevailed in the PRD (Figure 5). Cold air was affecting the north and northwest
China in the morning of the22nd, with strong wind and drop in the temperature. Meanwhile, the south
China began being affected by the high pressure system from the north. The cold air moved to the south
rapidly and reached the Nan Ling Mountain in the morning of the 23rd, and arrived at Guangdong
province later. The wind direction changed into northerly from the north to the south of Guangdong
province gradually. There was a cold front moving across the PRD on 23rd, with weak surface
northerly wind. The warm and wet airflow in the south climbed above the meteorological front, and
caused the formation of thermal inversion layer and steady stratified atmosphere, which weighted against
the diffusion and transference of air pollutants. Besides, under the influence of the northerly wind, the
air pollutants transported to the northeast PRD before would be brought back to the south again. In this
situation, serious ozone pollution would happen in the relatively clean area, namely, north and southeast
parts of the PRD one after another.
The routine and strengthened meteorological monitoring data over the PRD fitted well with the
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regional meteorological analysis above. Most of the area in the PRD was dominated by southerly wind
in the 21st and 22nd Oct. But from the 23rd on, northerly and northeasterly wind were the dominant wind
in the PRD (Figure 6). During the 22nd and 23rd, the transition of wind direction from southerly to
northerly occurred earlier in the north PRD (e.g. Tianhu) than in the middle and southeast PRD (e.g.
GDEMC and Jinguowan), which showed the movement of cold air from the north PRD to the south PRD.
FIGURE 5. Surface synoptic situation (14:00 Beijing time) in the East Asia from 21st to 24th Oct
2008
Trajectory Analysis during the Ozone Episode. The air mass in the lower atmosphere in the afternoon of
the 22nd Oct in Tianhu mainly passed Guangzhou city, without passing through other major emission
source areas(Figure 7 A). It indicated that the ozone pollution in the northeast PRD was chiefly contributed
by the precursors’ emission in urban Guangzhou.
The ozone concentration in the southeast PRD on the 23rd Oct was much higher than the usual.
Backward trajectory showed that the air mass in the lower atmosphere in Jinguowan in the afternoon of
23rd Oct mainly passed through the central PRD, also the west Pearl River Estuary and the northeast
PRD(Figure 7 B), which indicated that the precursors emitted in the central and west PRD first transported
to the northeast PRD and then moved to the southeast PRD and caused serious ozone pollution there.
Forward trajectory analysis also showed that the air mass in urban Guangzhou in the 22nd, first
transported to the northeast PRD, and then moved to the east and southeast PRD (Figure 8 A and B). So
the serious ozone pollution in the north PRD on the 22nd and the east PRD on the 23rd was originated
from the precursors’ emission in Guangzhou. From the 23rd on, the air mass in the central PRD mainly
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moved to the south directly (Figure 8 C and D). The precursors emission in Guangzhou on the morning
of 23rd principally affected the west coast of the Pearl River Estuary, and the emission in Dongguan mainly
affected the east coast of the estuary (Figure 8 C and D).
FIGURE 6. Wind velocities of three stations from 20th to 26th Oct 2008
FIGURE 7. Backward trajectory analysis (10, 100, 500 m; 48hours)
Process Analysis. The contribution of different process to the ozone in the lower layers varied at different
time. Generally, chemistry process was part of the source of ozone in Tianhu during the daytime, but it
consumed ozone in the nighttime (Figure 9 A). Vertical and lateral ozone transport in the lower layers
also varied much as time went by. Due to the relatively weak transport and strong chemical formation of
ozone in Tianhu, the net ozone change in the daytime of 22nd was higher, which caused serious ozone
pollution on the 22nd.
The ozone in Jinguowan in the late October was chiefly affected by vertical and lateral transport.
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The contribution of chemical process to ozone was relatively low except on the 23rd. However, the
contribution of chemical process had a relatively high contribution to ozone during the daytime of the
23rd (reached more than 20 ppb/h at noon) (Figure 9 B), which showed that under the influence of
ozone precursors’ transport, ozone formation in Jinguowan was much stronger. And the rate of ozone
change was larger than usual, with averaged increase rate of 19.1 ppb per hour in the morning from 8:00
to 12:00. Affected by a weak downward current on the 23rd, ozone in the upper layers transported to the
lower layers. Meanwhile, ozone transported out via the lateral boundary of the grid containing Jinguowan
and exported ozone to the downwind area and aggravated the ozone pollution in the southeast PRD.
FIGURE 8. Forward trajectory analysis (10, 100, 500 m. 48hours)
Detailed process analysis showed the transition of the distribution of different lateral boundaries
between the 22nd to the 23rd (Figure 10). The ozone in Tianhu (north PRD)on the 22nd was partly
transported from the south and west, which outstripped the amount transported out via the north and east
boundaries and caused rapid increased in ozone concentration in the afternoon (Figure 10 A).However,
with the change of wind direction, the ozone and its precursors in the north PRD was transported to the
south and west, which caused the ozone concentration in southeast PRD (e.g. Jinguowan) increased much
on the 23rd(Figure 10 B). Meanwhile, the ozone was transported out from the south boundary of
Jinguowan to the south PRD.
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FIGURE 9. Process analysis for Tianhu(A) and Jinguowan(B) from Oct 21-24, 2008 (layers 1 to 3,
~80m)
FIGURE 10. Detailed process analysis for Tianhu(A) and Jinguowan(B) from Oct 21-24, 2008
(layers 1 to 3, ~80m)
FIGURE 11. Administrative districts of the PRD
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Ozone Source Apportionment. OSAT and GOAT modules were used. The third domain was divided into
55 parts according to administrative districts (Figure 11). The blue one is the Pearl River Estuary. The
emission was distributed into eight categories, namely natural emission, biomass burning, traffic
exhaust, solvent use and storage, residential emission and waste disposal, large point sources, non-solvent
industrial emissions and other non-mainstream sources.
Generally, about 30-40 ppb ozone in autumn in the traditional upwind areas, such as Tianhu in
the north PRD and Jinguowan in the southeast PRD, was from the outside of the PRD simulated domain
(Figure 12 and 13). Apart from the boundary transport, the ozone in the north and east PRD was mainly
from local precursors’ emission. But on the 22nd, there was an ozone episode in the north PRD, the ozone
in Tianhu reached more than 100 ppb in the afternoon. And the ozone contribution of precursors’
emission in urban Guangzhou was more than 40 ppb at noon. The contribution of other places also
increased (Figure 12 A). Most of the ozone in the north PRD was formed locally (Figure 13 A), which
indicated that the precursors emitted from the urban Guangzhou and other areas transported to the north
PRD and generated ozone there.
FIGURE 12. Ozone source apportionment in Tianhu (A) and Jinguowan (B) from 20 to 26 Oct
The surface wind field changed from southerly to northerly between the 22nd and 23rd over the
PRD. In the afternoon of the 22nd, the ozone contribution of Dongguan and Shenzhen to Jinguowan
increased (Figure 12 B). However, due to the sunshine became weak in the afternoon; the ozone formation
was not so strong that the ozone concentration was not too high (below 80 ppb). And the precursors went
on transporting from the northeast of the PRD to the south at night. NO consumed the ozone much at the
night of the 22nd. So the ozone concentration in the Jinguowan before the sunrise of the 23rd was very
low (below 10 ppb). The ozone concentration increased rapidly after the sunrise of 23rd because of the
abundance of the precursors transported from the north (Figure 12 B). And the precursors were mainly
emitted from the urban Guangzhou and the west PRD. But the precursors were not transported directly
to the Jinguowan. They were first transported to the northeast PRD and then moved to the south, which
was consistent with the results of trajectory analysis. Most of the ozone in Jinguowan was formed in
Huizhou (Figure 13B), which demonstrated that the precursors from Guangzhou et al transported to the
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east PRD and generated ozone locally.
FIGURE 13. Formation places for ozone in Tianhu (A) and Jinguowan (B) during 20 -26 Oct
In the north PRD in the afternoon of 22nd and in the southeast PRD in the afternoon of 23rd when
the ozone pollution was most serious, the precursors emitted in urban Guangzhou, especially from traffic
section, contributed most to the ozone in these two situations (Figure 14 A and C).
There was about 32 ppb ozone in Tianhu in the afternoon was from the precursors emission in
urban Guangzhou, and about 35ppb ozone was generated in Conghua County where Tianhu is located,
which demonstrated that the precursors emitted in Guangzhou were transported to the north and generated
ozone there (Figure 14 A and B). Similar situation happened in Jinguowan (Figure 14 C and D), where
a considerable proportion of ozone was from the precursors emited in every districts of Guangzhou City
and Foshan City in the central PRD. And the ozone was mainly formed in Boluo County where Jinguowan
is located.
The NOx and VOCs concentration in the two stations was high at night before the most polluted
period. However, the NOx and VOCs concentration was gradually reducing after the sunrise and reached
the lowest in the afternoon (Figure 15 and 16). During the high ozone episode, it was usually VOC-sensitive
regime. Therefore, the VOCs contributed more for the high ozone concentration. And the contribution of
VOCs from urban Guangzhou and Foshan to Tianhu increased much in the daytime of the 22nd (Figure
16A). Despite the percentage of the contribution of VOCs from urban Guangzhou and Foshan was less
than that of north and east GZ, the higher relative incremental reactivity of the VOCs from urban area
contributed more to the ozone, which was shown in the ozone source apportionment.
The NOx and VOCs from Guangzhou and Foshan accumulated in Tianhu during the night of the
22nd to the morning of the 23rd was transported to the southeast PRD(Figure 15 and 16). So the
contribution to NOx and VOCs in Jinguowan from Guangzhou (including Panyu and north and east GZ)
and Foshan City gradually increased from the morning of the 23rd on. The NOx contributed proportion
by Guangzhou and Foshan reached 21%~34% around noon. The exotic VOCs with high relative
incremental reactivity contributed much to the ozone in Jinguowan even though the amount was not as
big as the local VOCs. Although Shenzhen and Dongguan contributed most of the NOx and VOCs
to Jinguowan at the night between the 22nd and 23rd, these precursors were transported out around the
sunrise and they did not contributed much to the ozone episode on the 23rd. And as the wind direction has
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been changed to the northerly on the 23rd, these precursors from Shenzhen and Dongguan would reach
the south and southeast PRD and caused serious ozone pollution combining the fresh emission.
FIGURE 14. Ozone source apportionment at 14:00 in Tianhu (A,B) on the 22nd and Jinguowan
(C,D) on the 23rd (The legend above was for A and C)
FIGURE 15. NOx source apportionment in Tianhu (A) and Jinguowan (B) during 20 -26 Oct
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FIGURE 16. VOCs source apportionment in Tianhu (A) and Jinguowan (B) during 20 -26 Oct
FIGURE 17. Ozone source apportionment in Tung Chung (A,B) and Tangjia (C,D) at 14:00 of the
23rd (The legend was the same as Figure 13)
Apart from the southeast PRD, the large regions near the Pearl River Estuary were also serious
polluted by ozone in the afternoon of the 23rd. The regions east to the PRE (e. g. Tung Chung in HK)
was mainly affected by the Dongguan and Shenzhen Cities, and traffic exhaust contributed most ozone,
followed by the solvent emission (Figure 17 A). However, most of the ozone in the regions west to the
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PRE (e. g. Tangjia in the Zhuhai City) was contributed by the emission in Guangzhou City, especially
Panyu District (about 28 ppb) (Figure 17 C). The contribution proportion of solvent emission was not as
high as in the east coast, but the contribution of other non-mainstream source was ranked as the second
largest contributor. For both regions, though the precursors were from quite different sources, most of
the ozone was formed in the PRE (about 40-60ppb) (Figure 17 B and D).
In short, the precursors emitted in the central PRD on the 22nd first transported to the northeast
PRD and caused ozone pollution there. As the wind direction changed from southerly to northerly, the
precursors in the northeast PRD was transported to the south on the 23rd, and resulted in serious ozone
pollution in the southeast PRD. Meanwhile, the high ozone concentration on the 23rd in the regions west
to the PRE was mainly contributed by the precursors’ emission in Guangzhou, and ozone in the regions
east to the PRE was mainly from the emission in Dongguan and Shenzhen Cities. The PRE was an
important place for ozone formation.
Ozone Sensitive Analysis. HDDM was run to calculate the first- and second-order NOx and VOC sensitive
coefficients, which help determine the extent of sensitivity of ozone to its precursors. If the first-order
sensitive coefficient was greater than 0, ozone concentration would increase with the increase of this
factor, and vice versa.
FIGURE 18. First-order precursors emission sensitive coefficients in Tianhu and Jinguowan during
the ozone episode
The sensitivity of ozone to regional precursors’ emission in the PRD simulated domain was studied. The
first-order VOC sensitive coefficient (Svoc) in Tianhu was much higher on the 22nd than on the 23rd and
24th (Figure 18 A), which showed that the ozone concentration in Tianhu was much more sensitive to
the regional VOC emission during the ozone episode on the 22nd. Similar circumstance happened in
Jinguowan on the 23rd. As for the first-order NOx sensitive coefficient (SNOx), it was negative in the
morning and positive in the afternoon for both stations in the episodes, which indicated that NOx
emission reduction would increase the ozone in the morning, but reduce ozone in the afternoon. Usually,
the magnitude of SNOx was less than that of Svoc, which showed that reducing VOC emission was more
effective for ozone pollution control than NOx emission reduction. But in the afternoon of the 23rd, the
SNOx and Svoc in Jinguowan were in similar magnitude and the values were large. It showed that the
ozone in Jinguowan was sensitive to both NOx and VOC emission. After the afternoon of the 23rd, the
ozone in both stations showed little sensitivity to VOC or NOx emission, with Svoc and SNOx ~0. It
showed the characteristic of upwind clean areas.
During the ozone episode, stations in the north and southeast PRD showed certain sensitivity to
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the precursors emission in the PRD, which demonstrated that the ozone episode was partly caused by
the emission in the PRD, but not by the areas outside the PRD. And after the episode, the ozone showed
little sensitivity to the emission in the PRD, which indicated that, the ozone in the north and southeast
PRD was nearly not related to the emission in the PRD. The results of DDM were consistent with the
analysis above.
Incorporating the first- and second-order sensitive coefficients, the responds of ozone to the
change of VOCs and NOx emission were quantified. The ozone at 14:00 of the 22nd in Tianhu could be
reduced by about 27 ppb if both the NOx and VOCs emission was reduced by 50%, but at the same time
of the 23rd, similar reduction of the PRD precursors emission only resulted in less than 1 ppb ozone
reduction(Figure 19 A and B). Reducing NOx or VOC had similar effect to ozone reduction. 50% NOx
reduction caused about 23 ppb ozone reduction on the 22nd, and 50% VOC reduction resulted in about
18 ppb ozone reduction. It showed that during the ozone episode in Tianhu on the 22nd, reduction of
precursors emitted in the PRD would reduce the ozone remarkably. But after this episode, the ozone
concentration in Tianhu was stable and nearly not responded to the change of emission in the PRD.
FIGURE 19. Response of ozone at 14:00 to the change of regional VOCs and NOx emission (the color
bar means ozone change, with the unit ppb. A and B stand for the situation in Tianhu on the 22nd and
23rd; C and D stand for the situation in Jinguowan on the 22nd and 23rd.)
The ozone concentration was much higher on the 23rd than on the other days in Jinguowan. And
the response of ozone in Jinguowan to the PRD emission change was greater on the 23rd. Reducing NOx
emission was more effective for ozone control than reducing VOCs. For instance, 50% VOC reduction
only resulted in about 6 ppb ozone reduction in Jinguowan at 14:00 of the 23rd, but 50% NOx reduction
resulted in about 24 ppb ozone reduction(Figure 19 D).
On the whole, when ozone pollution episode happened, the ozone in the high ozone zone was very
sensitive to the emission change in the PRD, which indicated that the high ozone episode in the north and
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southeast PRD in fall was originated from the precursors emission in the PRD, and reducing the emission
in the PRD would help relieve the ozone pollution.
CONCLUSIONS
Generally, northerly or northeasterly wind prevailed in the PRD in autumn, and the north and east
PRD was traditional low ozone region. However, high ozone event happened in the north and southeast
PRD one after another during the mid-later October 2008, with the ozone concentration in the afternoon
reached more than 100 ppb, which was much higher than the usual (about 60 ppb). And it was the first time
discovering ozone pollution in these regions in autumn.
During the ozone episode, the PRD was first controlled by low pressure system, and southerly
wind prevailed in most parts of the PRD. The precursors’ emission in central PRD, especially Panyu
District and urban area in Guangzhou city contributed 36.7ppbozone to the episode in the north PRD.
But 51.3ppb ozone in the north PRD was generated locally.
With a high pressure system moved from north China to south China during the 22nd to 23rd Oct,
the PRD was dominated by northerly wind gradually. The precursors which had been transported to
the northeast PRD was moved to the south again and resulted in heavy ozone pollution in the southeast
PRD on the 23rd. The ozone in the southeast PRD was contributed by the precursors’ emission in the
central and west PRD on the 22nd, and mainly formed in the east PRD on the 23rd. The chemical process
contributed much more ozone in Jinguowan at noon of the 23rd (reached more than 20 ppb/h on average
at noon) than at other time. The ozone pollution in the south PRD was also very severe on the 23rd, and it
was originated from the precursors emitted in the central PRD on the 23rd with a contribution of about
30 ppb from Guangzhou and Foshan, and the ozone was mainly generated in the PRE.
About 40 ppb ozone in the afternoon was from the outside of the PRD simulated domain, which
showed relatively high ozone background concentration in the PRD. Usually the ozone in the north and
east PRD was not sensitive to the precursors emitted in the PRD. But it was very sensitive during the
ozone episode. So the ozone episode was mainly contributed by the emission in the PRD. NOx emission
reduction was more effective for ozone control in the east PRD in the afternoon. But NOx reduction had
negative effect for ozone concentration in the morning. VOC emission reduction was also effective in the
high ozone situation. Traffic emission in the central PRD should be taken as priority for regional ozone
pollution control.
If the wind direction changed much in a relatively short time, the polluted air mass which was
transported far from the emission source would be brought back, combining with new emission, large
areas near the emission source region would be affected by severe ozone pollution. This phenomenon was
not limited in the seashore area which is affected by the land-sea breeze. And it also happened in a larger
scale. If the PRD was controlled by low pressure system and then cold high pressure moved from the
north China to the south, the risk of ozone pollution in north and southeast PRD increased.
ACKNOWLEDGEMENTS
This work was supported by the National Natural Science Foundation of China under grant No.
41303075, namely, “Properties of new particle formation and the roles of secondary compounds in PRD
region”.
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372
STYRENE DEGRADATION BY BIOTRICKLING FILTERS WITH MIXED AND

SINGLE PACKINGS
Ailing Ren, Huanhuan He, Bin Guo, Xi Lv
(College of Environmental Science and Engineering, Hebei University of Science and Technology,
Shijiazhuang 050018, China)
ABSTRACT: Biodegradation of styrene vapour was investigated in two different packings filled biofilter
inoculated with a mixed microbial population. Two identical laboratory-scale biotrickling filters were filled
respectively with pyrocarbon-sawdust and ceramic-raschig-rings-sawdust mixed packings, and operated in
parallel. The results showed that the filter filling with pyrocarbon-sawdust packings had higher rate of bio-
film formation and removal efficiency of styrene than that of ceramic-raschig-rings-sawdust packings. The
optimum operating conditions were: an inlet gas concentration of 50 to 450 mg/m³, an empty bed residence
time (ebrt) of 21.6 to 43.2 s, a maximum removal load of up to 153.1 g/(m³·h), and a gas-liquid ratio q/l of
110.7 to 55.3. The stability of the biofilter was evident from the fast response of the biofilter to shutdown
and re-startup.
Key words: Biotrickling filter; filler; styrene.
INTRODUCTION
Styrene is not only polluting the atmosphere, but also causing harm to the human body. Since its
teratogenic, carcinogenic, and mutagenic effects have been reported in the literature [1], measures must be
taken.Methods of degrading Volatile Organic Compounds (VOC) contain adsorption, absorption,
combustion, condensation, corona, light oxidation decomposition, and the plasma[2,3], etc. As a safe and
efficient VOC purification method, biological purification methods are gaining more extensive attention
both at home and abroad.[4-6]. For chemical plants, installing biotrickling filters would create not only higher
treatment effects, but also easy operation and lower cost of process management. In addition, secondary
pollution is avoid[7,8]. At present, research into biological trickling filters mainly focuses on biological
treatment topics, modelling of the reaction kinetics, filter medium packings, equipment and process
conditions, and genetic strain breeding advantages, etc.
There has been a large number of studies examining the performance of the filters’ packings. Jang[9]
investigated the removal of styrene gas in biofilter using an organic packing material of peat and an
inorganic ceramic packing . The maximum styrene elimination capacities were 236 and 81 g·m-3·h-1,
respectively. Singh[10] studied the biodegradation of toluene vapour in a polyurethane packed biofilter.
Depending upon initial loading rates, removal efficiencies ranged from 68.2 % to 99.9 % during steady
state operations. Yuan and Guo[11] carried out a pilot study using combination packings which contained
coke and plastic rings to treat styrene waste gas. In the start-up process, the removal rate was 30% to 45%,
with the highest removal rates potentially amounting to 90 %.
In this study, two identical laboratory-scale biotrickling filters were filled with pyrocarbon-sawdust
mixed packings and sawdust single packings, and operated in parallel. This paper mainly discussed and
compared the purification performances of two biotrickling filters via experiments involving the
microbiological purification of styrene-containing waste gas. These investigations could be helpful for
biotrickling filters to degrade styrene in industrial application.
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Materials
Seed cultures. The culture came from the secondary sedimentation tank of an urban sewage plant
in Shijiazhuang, China. It was aerated for 20 hours and allowed to rest for 4 hours in every day.
Packings. Biotrickling filters A was filled with the sawdust-pyrolytic carbon mixture and sawdust
as microbial carrier while filter B filled with ceramic raschig rings and sawdust.
Nutrients. The nutrient solution containing: 50 mg of urea, 150 mg of KH2PO4, 225 mg of MgSO4,
275 mg of CaCl2·2H2O, 25 mg of FeSO4, 2.0 mg of ZnSO4, 0.4 mg of MnSO4·H2O, and 0.4 mg of
CuSO4·5H2O in 1 L of water was prepared and supplied periodically over the filter media to maintain an
adequate moisture content and supply additional nutrients to the microbial population.
Methods
Experimental set-up. The schematic diagram of the experimental set-up is shown in Fig. 1. the
apparatus comprised two similar laboratory-scale biotrickling filters, A and B. Filters A and B were filled
with a sawdust-pyrolytic carbon mixture, and sawdust only, respectively.
Fig. 1. Experimental set-up

a: air compressor, b: valve, c: air flask ,d: pollutant chamber,e: surge flask, f: rotameter,
g: biotrickling filter, h: absorption flask, i: submersible pump, j: nutrient solution
Table 1. Time scheme for styrene degradation experiments

Inlet Operatin
EBRT
Phase of experiment concentration GLR g time
(s)
(mg/m³) (day)
Acclimatization 100 - 200 57.6 70 - 80 25
I 43.2 10
(inlet concentration 50 - 1500 21.6 70 - 80 10
Continuous
and EBRT) 14.4 10
degradation
II 110.7 -
400 43.2 10
(GLR) 36.9
Decommissioning Shutdown period — — — 3
and recovery Restart operation 300 - 400 43.2 70 - 80 15
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The experimental set-up included two sets of circulation system: gas and liquid, in which a reflux
mode of operation was adopted. Each section of the column was provided with gas sampling ports. A fresh
air stream was divided into two portions downstream from the compressor, then flowed into the air flask
and pollutant chamber separately under rotameter-based control. When the fresh air and pure styrene were
homogeneously mixed in the surge flask, the gas mixture entered both A and B respectively. When it
contacted with the biofilm in the rising process, the styrene-containing gas was purified. After purification,
the gas flowed into the absorption flask from the upper air exhaust. The nutrient solution in the lower trough
was pumped to the tower’s top by submersible pump, and then sprayed onto the packings through water
distribution devices to provide N, P, and other nutrients indispensable for microbial growth. Samples of
outlet gas were collected from the sampling ports and analysed by a GC-14C(SHIMADZU, Japan). Gas
samples were collected with a 1 mL syringe.
Time Scheme. The sequence of operating conditions of the biotrickling filters was described in
Table 1. The two biotrickling filters were operated mainly in three phases: acclimatisation period,
continuous degradation experiments, and decommissioning and recovery experiments.
Comparison of Two Biotrickling Filters’ Performance. The quick dredge method was adopted to
achieve the goal of biofilm formation and acclimatization. The removal rate was determined daily. The
purifying effect of the biotrickling filters during their acclimatisation period is shown in Fig. 2.
Fig. 2. Purification efficiency during acclimatization period
From Fig. 2 it may be seen that in the first week, the removal rates in A and B were both below
20%. Filter A showed a higher removal efficiency in this early period, then fell sharply to a lower level.
Until the 11th day, the purification efficiency of filter A was greater than 80%. However, filter B need 15
days to complete its acclimatisation. From this point on, filter A was superior to filter B. This was mainly
due to its larger porosity and the specific surface area of the pyrolytic carbon in filter A. In the initial
acclimatisation period, the biotrickling filter could remove part of the styrene reliant upon the physical
adsorption of the pyrolytic carbon; microbial degradation was weak. When physical adsorption reached
saturation, the majority of the styrene was discharged from the outlet directly and untreated, so the detected
removal rate was significantly reduced. This also provided the reasons for the low removal rate of filter B
in its early acclimatisation period (1 to 9 days).
Influence of Styrene Concentration. Fig. 3 shows that at equal inlet concentrations, the total removal
efficiency decreased with decreasing EBRT, the removal ratio of filter A was higher than filter B by 5% to
15%, thus evidencing its superiority. With increasing inlet concentration, the removal efficiency fell
375
sharply. When Cin ≥ 1000 mg/m³, EBRT ≤ 21.6 s, the purification efficiencies of both A and B dropped
below 50%, filter B even reached a low of 23%. The removal efficiency of filter A was always higher than
that of filter B. When EBRT and GLR were at specific values thereof, the removal efficiency dropped with
increasing inlet concentration. This was because the higher the inlet concentration, the greater the extent of
microbial metabolism needed. However, the ability of microbial metabolism was limited: the higher inlet
concentration, the greater amount of untreated styrene discharged thus leading to a reduced efficiency. In
conditions of equal inlet concentration and GLR, with an increased gas flow rate, the EBRT decreased, and
the microorganisms had insufficient time to resolve the pollutants. Some styrene gas was exhausted without
microbial metabolism, leading to a reduced purification efficiency.
Fig. 3. Influence of styrene concentration in inlet gas phase and gas loading
A B
Fig. 4. Influence of total inlet load on total removal load
Influence of Total Inlet Load on Total Removal Load. Fig. 4 shows the influence of the total inlet load
on the total removal load of the biotrickling filter. When the styrene inlet load was below 49.75 g/ (m³·h),
the majority of the styrene could be removed by the two biotrickling filters. With increasing inlet load, the
removal ability also increased. However, when the styrene inlet load increased, the removal load stabilised
at a higher level and no longer increased. The maximum styrene removal loads were 153.1 g/(m³·h) and
109.6 g/(m³·h) for filters A and B respectively. The removal of styrene by biotrickling filters was a mass
transfer control process. When inlet load increased, the biological membrane on the packings could
encounter more styrene gas so that more styrene be removed, thus the biochemical removal quantity
376
increased significantly. When the removal load increased to the maximum, the formation of dynamic
equilibrium appeared because of the limited metabolic capacity of the biological system and
microorganism.
Influence of Gas-Liquid Ratio. Fig. 5 showed the influence of GLR on removal efficiency.It proved that
when the inlet concentration was determinated, changing the GLR had no significant effect on the removal
efficiency of the two biotrickling filters. The increase in the quantity of liquid sprayed could lead to
performance reduction because large volumes of liquid would washed and then removed a significant
quantity of microorganisms, leading a decline in their removal rate. However, when the quantity of liquid
sprayed was insufficient, the system’s humidity decreased, thus affecting the normal metabolism of the
microorganisms, which resulted in the removal rate declining. Considering the economic issues and
removal efficiency of the biological trickling filter, in actual operations, it is proper to provide a certain
amount of nutrient solution which is able to humidify the surface of the packings and provide adequate
nutrients for microorganisms.
Fig. 5. Influence of gas-liquid ratio (GLR) on removal efficiency
Decommissioning and Recovery. The shut-down and restart experiments were conducted (Fig. 6). Within
the first 5 h, the styrene removal rate fluctuated within the range 10% to 30%. Then the removal efficiency
of the two biotrickling filters greatly improved, by 14 h, removal efficiencies were both above 90 %. The
restart capacity of filter A was slightly higher than that of B. This was mainly because there were rich bio-
facies in the internal pores of the pyrolytic carbon packings. When the filter was shut-down, the
microorganisms on the packing surface went into dormancy or became enfeebled, and died. The
carbonaceous packings had favourable moisturizing effects, they could maintain a given moisture content
for a longer time which was helpful in sustaining microorganic life[12], so those microbes existing in the
interior of the pyrolytic carbon packing could still continue their growth over that period. It was thus easier,
and quicker, to restart filter A than B.
377
Fig. 6. Shut-down and restart operation
CONCLUSIONS
Biofilter filled with pyrolytic carbon-sawdust packings could achieve the goal of dynamic biofilm
and startup in about 10 days, and the removal efficiency during both acclimatization and ecommissioning-
recovery period is better than that of ceramic raschig rings and sawdust.
Proper operating conditions were: an inlet concentration of 50 to 450 mg/m³, a residence time of
21.6 to 43.2 s, the biggest removal load could reach 153.1 g/(m³·h), a gas-to-liquid ratio of between 110.7
and 55.3. In the whole process the purification efficiency could reach 92 % to 100 %.
ACKNOWLEDGMENTS
This research is supported by the Natural Science Foundation of Hebei (No.B20132081681).
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379
TREATMENT OF DYNAMIC MIXTURE OF N-HEXANE, BENZENE, AND METHANOL IN

AN INTEGRATED SCHEME OF CYCLIC ADSORPTION/ DESORPTION BEDS AND
TRICKLE BED AIR BIOFILTER
Abderrahman Zehraoui and George A. Sorial*

(University of Cincinnati, Cincinnati, OH, USA)
A mixture of benzene, n-hexane and methanol was fed into two parallel trickling bed air biofilters (TBABs)
at different wave ratios. TBAB “A” was preceded by an integrated system of a cyclic 2-bed
adsorption/desorption unit. The primary goal of the study was to maintain long-term, stable, and consistent
high performance of these VOCs in the TBAB.
Both TBABs were fed with four different square waves (I, II, III, and IV) in the influent VOCs
concentrations (low and high peaks for waves “I” to “III”, a medium wave was added for wave “IV”).
TBAB “A” was receiving a constant feed of the average value of a weighted time of the square wave as its
influent, while TBAB “B” (the control) was directly subjected to the high, low, and medium(only for wave
“IV”) peaks.
The experimental results have shown that n-hexane elimination in TBAB “A” was steady and high
performance was obtained (removal efficiency varied from 80 to 93%), while TBAB “B” demonstrated
erratic performance in n-hexane removal (removal efficiency varied from 20 to 90%). As for benzene
elimination, both TBABs exhibited high efficiency in their elimination (more than 95% in removal
efficiency) for the square waves “I” to “III”. For wave “IV”, TBAB “A” showed a performance of 87% in
removal efficiency while it was around 73% for TBAB “B”. For methanol elimination, both TBABs
exhibited high removal efficiency (more than 95%). For all influent waves, the cyclic beds buffered the
fluctuating influent load and the followed biofilter had a continuous and stable loading. On the contrary,
the control biofilter suffered from the frequent change in loading rates and could not resist the alteration in
the influent VOCs loads that negatively influenced their uptake for metabolism by the microorganisms.
380
REMOVAL OF CHLOROFORM AS A MODEL TRIHALOMETHANE IN THE PRESENCE OF

CO METABOLITE AND / OR SURFACTANT BY USING ANAEROBIC BIOTRICKLING
FILTER
Bineyam Mezgebe* and George Sorial (Department of Biomedical, Chemical and Environmental
Engineering, Environmental Engineering Program, University of Cincinnati, Cincinnati, OH, United
States)
Ashraf Aly Hassan and Endalkachew Sahle-Demessie (Office of Research and Development, NRMRL,
U.S. Environmental Protection Agency, Cincinnati, OH, United States)
Harmful disinfection byproducts (DBPs) such as Trihalomethanes (THMs) and Haloacetic acids (HAAs)
are formed due to the chlorination of potable water. Many of these created compounds are volatile organic
compounds (VOCs). Water aeration and adsorption on activated carbon are traditionally used for their
removal. In this study, by using chloroform as a model THMs, an integrated bio-technology was proposed.
The technology uses gas stripping of DBPs and treating the gas phase with a Biotrickling filter (BTF)
system. Biological removal of chloroform is intrinsically limited by its hydrophobic nature and low
bioavailability. This study demonstrated the presence and ability of ethanol as a co metabolite to stimulate
biodegradation of chloroform. Similarly, it investigated the effects of additions of surfactants to enhance
the bioavailability of hydrophobic chloroform in order to increase its elimination capacity. As a result, the
use of co metabolite improved the performance of the BTF by providing a 60% removal efficiency of
chloroform. Moreover the addition of surfactant, Tomadol 25 - 7 as a co solvent in the nutrient solution fed
to the BTF increased the removal efficiency of chloroform to 64%. The study will be further evaluated by
introducing the other THMs, bromodichloromethane and dibromochloromethane, with chloroform.
381
WRESTLING WITH FENCELINE FUGITIVES: NUISANCE AIR MONITORING
Ben Bolton*, John Siler, and Rick Bolton.

(EnSafe, Inc. Nashville, TN, USA)
Monitoring air at the property boundaries has become necessary as community nuisance complaints and
class action litigation increases. State agencies wrestle with how to address fugitive air emissions from
various sites. Some states are now requiring fenceline air monitoring during remediation projects or to
evaluate nuisance situations. We will discuss 2-3 cases where real time air monitoring was used to
determine fenceline concentrations and alert site owners to potential concerns. Pollutants such as dust
(PM10 and PM2.5) and ammonia (NH3) were measured using wind data and portable air monitors.
382
CHARACTERIZATION OF PM2.5-BOUND NITRATED AND OXYGENATED PAHS IN DIESEL

EXHAUST PARTICLES
Meiling Hou, Wanglai Cen, Jianjun Li, Huaqiang Yin* (Sichuan University, National Engineering
Research Center for FGD, Chengdu, Peoples R China)
Yangjun Wang ( Shanghai University, Shanghai, Peoples R China)
The objective of this study is to separate the target components by using normal-phase high performance
liquid chromatography (HPLC) technique, together with gas chromatography/mass spectrometer (GC/MS)
to determine polycyclic aromatic hydrocarbons (PAHs), nitrated polycyclic aromatic hydrocarbons (nitro-
PAHs) and oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs).
In this project, we use the collection on the engine dyno test system in the exhaust gas of diesel
engine emission particulate sample, for which through analysis of the PAHs, nitro- and oxygen- PAHs,
came to some conclusions. These study used four kinds of oil: the Ⅱ -0 # automotive diesel, the Ⅳ 0#
automotive diesel, the Ⅳ-10# automotive diesel, the Ⅳ 0# emulsified diesel oil. These oils have different
sulphur content.
Surrogate standards consisting of naphthalene-d8, acenaphthylene-d10, phenanthrene-d10,
chrysene-d12, perylene-d12, 9-nitroanthracene-d9, 6-nitrochrysene-d11 were spiked onto the filters prior
to extraction. Then, the filters were ultrasonically extracted with dichloromethane (DCM). The extracts
were filtered, concentrated and separated by silica–alumina column. Fraction I (40 mL of hexane) was
discarded, while fraction II (100 mL of DCM-hexane (1:1)), which contained the parent PAHs and nitro-
and oxy-PAHs, was collected and reduced almost to dryness, then dissolved with n-hexane. Internal
standards hexamethylbenzene and 1-nitropyrene-d9 were added separately for the detection of parent PAHs
and nitro- and oxy-PAHs.
PAHs and nitro- and oxy-PAHs in all samples were separated using normal-phase high
performance liquid chromatography (HPLC) and analyzed using gas chromatography/mass spectrometer
(GC/MS). The mass spectrometer was operated in electron impact ion (EI) mode and selected ion
monitoring (SIM) for parent PAHs, and electron capture negative ion (ECNI) mode and SIM for nitro- and
oxy-PAHs. The identification of each compound was based on the mass spectra of reference standards.
Among 4 samples, the Ⅳ 0# emulsified diesel oil lowest in sulfur, released low-concentration
particles and minimal toxicity of PAHs, however, the emission of PAHs increased significantly.
For the Ⅱ -0 # automotive diesel, the Ⅳ 0# automotive diesel, and the Ⅳ-10# automotive diesel,
nitro-and oxy –PAHs reduced in direct proportion to the amount of sulfur. As to emulsified diesel bearing
least sulfur, nitro- and oxy – PAHs increased while particles decreased.
383
DAILY AND SEASONAL VARIATIONS OF VOLATILE ORGANIC COMPOUNDS AND

CARBONYLS IN THE ATMOSPHERE OF MONTERREY, MEXICO
H. Lizette Menchaca and Alberto Mendoza*

(Tecnológico de Monterrey, Monterrey, NL, Mexico)
The high concentrations of volatile organic compounds (VOCs) in urban atmospheres are of great interest.
These species are precursors of secondary gas-phase and aerosol-phase pollutants, whilst some of them
have adverse effects on human health. Anthropogenic activities emit large quantities of VOCs into the
atmosphere. For example, the use of vehicles and the transport of fuels generate emissions of ethene,
acetylene, isopentane, benzene, toluene, and other gasoline components; the use of solvents generates
emissions of toluene, hexane, octane, and nonane, among others. Isoprene and monoterpenes are the most
reactive natural COVs in the lower atmosphere.
Carbonyls are also common components of urban atmospheres and are of great importance in the
physical-chemical processes of the troposphere. They are emitted directly into the environment by
anthropogenic sources such as automotive vehicles (mainly formaldehyde, acetaldehyde and
crotonaldehyde), carbon burning (benzaledhyde), trash burning, industrial processes, such as the
manufacture of furniture (formaldehyde), and the use of solvents (acetone). The sources can also be natural.
For example, formaldehyde, acetaldehyde, and acetone are emitted by forest trees. Carbonyls are also
produced in the environment from the photo-oxidation of VOCs. Since carbonyls are the most abundant
photolyzed compounds in the atmosphere, they are an important source of ozone (O3), peroxyacetyl nitrate
(PAN) and secondary organic aerosol. In addition, carbonyls have adverse health effects: some irritate the
respiratory system or are proven carcinogenic substances.
In Mexico, the study of VOCs or carbonyls in the atmosphere has been very limited. This work
seeks to describe the levels of VOCs and carbonyl compounds in the atmosphere of Monterrey, Mexico, in
order to understand their daytime and seasonal variations. Monterrey is the third largest metropolitan area
in the country and the second largest industrial center. The concentrations of 10 carbonyls, two ketones and
29 VOCs were measured in downtown Monterrey, Mexico, in the spring and fall of 2011 and 2012.
Carbonyl samples were collected following EPA’s Method TO-11 method. The sampling train included a
heated ozone scrubber pre-conditioner followed by Sep-Pak DNPH-Silica® cartridges to capture the
carbonyls. VOC samples were collected using SUMMA®-polished stainless steel containers (6L) following
EPA’s Method TO-14. Chemical analysis for carbonyls and VOCs was conducted using HPLC/UV-Vis
and GC/MS equipment, respectively.
Formaldehyde, acetaldehyde and acetone were the most abundant carbonyls. The concentrations
showed marked daytime trends with maximum values between 10:00-14:00 hrs, when photochemical
activity is intense. The highest levels of carbonyls were observed in the fall. A bivariate statistical analysis
showed that the concentrations of carbonyls are caused primarily by emissions from mobile sources and
secondary production. The high order aldehydes (>C5) did not show significant correlations with O3,
indicating a primary origin. With respect to the VOCs, the highest concentrations occurred in the fall
(probably associated to lower temperatures and wind speeds) and there were no significant differences
between the spring measurements of both years. The VOC concentrations reached their lowest levels
between 14:00-18:00, a period subsequent to the highest amounts of sunlight, where they react to form
secondary contaminants. The correlations between VOC species gave evidence of a predominance of
mobile sources, fugitive fuel emissions and use of solvents as possible sources of the majority of these
compounds. Upon analysis of the COV-O3-NOx and Carbonyls-O3-NOx relationships, it was found that
the Monterrey atmosphere is controlled by a VOC-sensitive regime.
384
Characteristics of Greenhouse Gas Emission in the Yellow River Delta Wetland
Qingfeng Chen*, Junjian Ma, Hongyan Yang, Wenguo Dong

(Shandong Academy of Sciences, Jian, China)
Wetland ecosystem is one of the major types of territorial ecosystems and important carbon “sink” on the
earth. It is estimated that the wetland ecosystem contains about 15% of total carbon emission in the global
territorial ecosystems. Global climate change has become one of the greatest challenges for sustainable
development of the world economy and the international society. It is quite necessary to explore the carbon
reduction ways. Now, the two main carbon-cutting ways are industrial carbon reduction and natural carbon
sequestration. However, most of the research focuses on the former one. The Yellow River Delta wetland
is the most integrated, broadest, youngest wetland ecological system in China. Due to the affection by
human activities, the wetland is under a degraded risk and urgently require for ecological restoration.
Moreover, the wetland is an influenced and responsive region of global change because of its unique water-
heat effect and greenhouse gas metabolic process. In this study, five typical salt marsh plant communities
were selected to study the characteristics of greenhouse gas emission of the wetland. The results indicated
that the greenhouse gas emission, especially for the CO2 and CH4, showed a distinctly spatial variation. The
concentration of CO2 decreases from the coastal to the inland in the Yellow River delta wetland. An
opposite trend was also observed for the concentration of CH4. The relationship of the soil moisture with
CH4 emissions was positive correlation, but that to CO2 emissions was negative correlation. In addition,
there was a linear correlation (y=0.0196x+0.0252，R2=0.9872) between the content of Fe and Mn in the
soil. The work contributes to the protection of new-born frangibility, typical habitat and biodiversity in the
wetland ecological system. It is also beneficial for investigating the influence of the wetland carbon storage
change on the terrestrial ecosystem carbon cycle and the global climate change.
385
A MONITORING STUDY ON FINE AND COARSE PARTICULATE MATTER AT

CONSTRUCTION SITES
Harmonie A. Hawley* (University of Texas at Tyler, Tyler, TX, USA), James Miller and
Brian O’Dell (California State University, Fullerton, Fullerton, CA, USA)
*hhawley@uttyler.edu
ABSTRACT: A handheld Lighthouse® Airborne Particle Counter Model 3016 6-channel with fine and
coarse particulate matter (PM) adaptation was used to monitor ambient concentrations of PM at six
locations. Three construction sites and an upwind background site for each construction site were
monitored. Two of the construction sites were buildings: one was an apartment building and the other was
a gas station. The third site was an area being prepared for construction of a roadway. Data was collected
during construction and at off-construction hours. Background locations were chosen to be in the general
area of the construction, predominantly upwind of the construction sites during sampling times, and having
similar geographic characteristics.
Statistical analysis is used to compare the fine and coarse PM concentrations between the
background sites and their respective construction sites. This data suggests that construction activities have
a negative impact on local air quality during construction activities. However, the PM does not appear to
effect relatively large areas and tends to be localized to the construction site. The air pollution also did not
linger for relatively long periods of time and subsided once the construction activity was stopped. Fine PM
and coarse PM were not found to follow the same patterns.
INTRODUCTION
The focus of this study was to assess the impact of construction activities on local air quality by
monitoring particulate matter (PM). Particulate matter with an aerodynamic diameter of 10 micrometers or
less is referred to as coarse PM (PM10) and particulate matter with an aerodynamic diameter of 2.5
micrometers or less is referred to as fine PM (PM2.5). All six of the field sites were located in the South
Coast Air Basin in Southern California. This area is one of the most heavily PM polluted air basins in the
United States and is in non-attainment status as specified by the National Ambient Air Quality Standards
regulated by the United States Environmental Protection Agency (EPA) and by the California Air
Resources Board (CARB) standards (Hawley and Vu, 2012). CARB estimated that in the year 2012, 11
percent of PM10 and 3.9 percent of PM2.5 in the state of California originated from construction and
demolition activities (CARB, 2013).
The 24-hour standard set by the EPA for PM2.5 is 35 μg/m3 and the PM10 24-hr standard is 150
μg/m . The CARB 24-hour standard for PM10 is 50 μg/m3. In January, 2013 the EPA lowered the limit for
3
the annual average of PM2.5 to 12 μg/m3, which is the same limit set by CARB. The PM10 annual average
set by CARB is 20 μg/m3. Due to the lowering of the EPA standard from 15 μg/m3 to 12 μg/m3 for the
annual average of PM2.5, states may need to improve air quality to meet the more stringent requirements.

A Lighthouse® Airborne Particle Counter 3016 6-channel with fine and coarse PM mass adaptation
was used to monitor ambient concentrations of PM at several construction sites. Handheld particle counters
are easier to use and provide faster results compared to traditional particulate matter sampling methods
(Hawley and Vu, 2012). Each sample was collected for five to ten minutes continuously. The readings
were taken at 1-minute intervals; the reported values are the average of the 1-minute readings for the
continuous sampling period on each sample date.
386
Two separate field campaigns were conducted. The first field campaign ran from February 9, 2012
to April 12, 2012 and the samples were collected two times per week. Samples were collected at two
construction sites and two background sites, with each background site corresponding to a construction site.
All four sites were located in Fullerton, CA. The first site was an apartment building under construction in
the phases of carpentry, drywall, and flooring (FAB). The second site was an expansion to a highway in
the process of cutting and drilling concrete, foundation work, and placement of steel supports (FHW). The
background sites (FABB and FHWB, respectively) were located approximately one-quarter mile from the
active sites.
The second field campaign ran from June 21, 2012 to August 21, 2012 and samples were collected
two times per week. Samples were collected at an active construction site (IrvineC) and a background site
(IrvineB) that had no construction activity. The construction activity was a highway expansion and
involved excavation. Both sites were located in Irvine, CA in public areas. All background sites for both
field campaigns were chosen to be in traditionally upwind locations from the sites with construction
activity.
Statistical Analyses were conducted on the paired data to establish differences between the
construction site and its respective background site. Linear correlations were determined by plotting the
two sites against each other and determining the coefficient of determination (R2). An R2 value of 1
indicates a perfect correlation and a 0 indicates no correlation between the data sets. Moore et al. (2009)
suggest that the R2 is a more appropriate test for temporal variation than spatial variation in ambient samples
as high correlations can be seen in data that varies by a consistent factor.
In order to address the limitations with R2 values two additional statistical analyses were conducted
on the paired data sets. Analysis of Variance (ANOVA) was used to assess if the construction site and the
background site were statistically different at the 95% confidence level. The tests were conducted in
Microsoft Excel® and if the P-value was less than α (0.05) the sample sets were determined to be
statistically different (Paykov and Hawley, 2013).
A third statistical test, the coefficient of divergence (COD), was performed on the paired data to
estimate heterogeneity between the paired construction-background sets. The COD is calculated with
equation 1.
k
a•^— •^• c
r™ b› =œ ∑ U k (1)
a•^— }•^• c
In this equation xij is the ith concentration measured at site j for a specified sampling period, the
two different sites are represented as j and k, and n is the number of observations. The COD ranges from 0
when the concentrations are the same to 1 where the concentrations are divergent (Wilson et al., 2005;
Hawley and Vu, 2012). Wilson et al. (2005) suggest that a COD of 0.20 or greater indicates heterogeneity
between two sites. The data was compared by the date the samples were collected for all three analyses,
therefore if one location was missing a sample it was deleted from all statistical analyses.
RESULTS
In general, the construction sites and the background sites followed the same trends as shown in
Figures 1 through 3. The EPA 24-hour standard is shown in the Figures for comparison to the daily
construction and background data. When there was no construction activity at the construction site, the PM
concentrations fell to similar values as the background site. It is important to note that the data was not
always collected during active construction. When construction was active increases were seen in the
construction PM concentrations. However, when construction was not active the levels were close to the
background levels. This indicates transport of the particulates off-site or rapid deposition and that the PM
levels in the vicinity rapidly dropped once construction activity was ceased. It is important to note that
open piles of dirt were not visible at the sites. The PM2.5 24-hour standard was exceeded by both the
387
construction and background sites at the Irvine location on June 12. The PM10 standard was exceeded at
FHW on February 23, but was not exceeded by the background site.
FIGURE 1. Fine and Coarse PM data at FAB
FIGURE 2. Fine and Coarse PM data at FHW
FIGURE 3. Fine and Coarse PM data at Irvine
388
DISCUSSION
Table 1 presents basic statistical data on the Fine PM and Coarse PM at the sampling locations.
The fine PM at the construction sites were similar to the background sites. The largest difference was at
FHW where the average fine PM was 50% higher at the construction site than at the background site. Larger
differences were seen with the coarse PM data between the construction and background sites. This is the
same trend estimated by CARB that construction activities have a higher influence on coarse PM than on
fine PM (CARB, 2013). The FHW had the highest coarse PM difference with the construction site being
over twice the value of the background site. The other two construction sites had higher coarse PM by 15%
to 40%. If the maximum value at FHW (739.76 μg/m3) was removed from the average coarse PM over the
study period the average is 40.8 µg/m3 which would be the lowest percent difference compared to its
background site of the three construction sites monitored. The Interquartile Range outlier test showed that
the fine and coarse PM values collected on that day were high outliers (Burns et al., 2005). However, as
the high outliers for fine PM and coarse PM occurred on the same sampling date, there could have been an
abnormally high PM source.
TABLE 1. PM2.5 and PM10 concentrations (bold values exceed standards)

FAB FABB FHW FHWB IrvineC IrvineB
Average 10.97 10.47 15.76 10.78 22.25 20.59
PM2.5
Max 29.36 27.02 66.89 19.48 51.95 50.74
(μg/m3)
Min 5.53 5.50 5.10 6.30 9.87 8.77
Average 53.30 38.18 110.75 40.81 73.25 64.04
PM10 121.62
Max 56.55 739.76 62.66 134.41 124.9
(μg/m3)
Min 20.91 20.79 21.61 27.20 22.22 34.42
The average PM concentration data for the each sampling period was compared to the EPA and
CARB annual average standards. The PM2.5 was exceeded at two construction sites and one background
site as shown in Table 1. The CARB PM10 standard was exceeded at all construction and background sites
regardless of whether or not the outlier value was included at FHW. Thus, even if the construction activities
were completely controlled (i.e. background levels), the area would still not meet the CARB standard for
PM10. This indicates that other sources of coarse PM would need to be lowered to meet the CARB standard.
Hawley and Vu (2012) conducted a study on PM levels in Fullerton, CA about one year before this study
and also found that the PM10 levels exceeded the CARB annual standard.
Muleski et al. (2005) reported that the type of construction activity influences the particulates
emitted, with earth moving being the most important construction contributor to particulates. Chow et al.
(1999) also found that PM10 concentrations were higher with construction activities that generated dust such
as excavation. In addition, Chow et al. (1999) found that construction activities at different locations
generated varying levels of PM10. The first field campaign of this study was not conducted during earth
moving or similar activities. One of the construction activities at the second sampling site was earth
excavation, but the PM levels were similar to background levels. The sampling location may have been
too far from the actual construction activity during the second field campaign. As opposed to sampling
adjacent to the earth moving activities, the sampling location was set up across a creek from the construction
site due to accessibility issues.
Table 2 presents the results of the three statistical analyses conducted on the paired construction-
background site data. In each data set the linear correlations were lower for coarse PM than for fine PM.
This indicates that there is a larger difference between the construction sites and the background sites for
389
coarse PM and the particles emitted during construction are, therefore, in the larger size fraction. The same
was found for the ANOVA and COD data. The coarse PM had lower P-values and higher COD values,
both indicating a larger difference between the coarse PM than between the fine PM data sets.
TABLE 2. Statistical Analyses between construction sites and their paired background sites
FAB FHW Irvine
PM2.5 0.96 0.86* 0.93
Linear Correlations, R2
PM10 0.41 0.56* 0.91
ANOVA Result—Difference, PM2.5 No, 0.84 No, 0.42 No, 0.81
P-value PM10 No, 0.059 No, 0.33 No, 0.49
PM2.5 0.075 0.25 0.09
COD
PM10 0.20 0.33 0.09
*the maximum value was removed for the linear correlations; without the removal of the maximum value
the linear correlations were 0.02 and 0.01, respectively.
The ANOVA results indicate that there is no difference between the construction site and the
background site mean concentrations for any of the sites nor for either PM size fraction. The P-value was
close to the alpha for the Fullerton construction site for the coarse PM data, indicating there may be a
difference.
The COD results indicate that the fine PM is homogeneous at all sites. If a COD greater than 0.2
or greater indicates heterogeneity (Wilson et al., 2005), then the coarse PM at both of the construction sites
are determined to be different. The same two sites had the lowest R2 values and the lowest P-values for the
ANOVA test. This shows discrepancies in the statistical tests. If the maximum values were removed from
the construction and background site, as was done with the linear correlations, the P-values from the
ANOVA for fine and coarse PM are 0.70 and 0.95, respectively, and the CODs are 0.09 and 0.16,
respectively. The ANOVA P-values are different, however the result of no difference is the same as when
the maximum values were used. The CODs, however are lower and now fall into the homogeneous
category.
All three statistical tests indicate that the construction sites was not statistically different than the
background sites for either coarse or fine PM. This is the opposite of the results found in Chow et al. (1999)
and the estimates reported by CARB (2013). This could be due to the conditions under which this study
was conducted thereby not capturing construction emissions during excavation type activities.
The COD values found in this study are similar to other studies conducted in the Southern
California area. Although the other studies did not focus on construction activities, they provide a spatial
comparison to this study. Hawley and Vu (2012) studied four sites in Fullerton, CA that were located
within a small area (less than 0.5 miles or 0.8 km); the CODs for PM10 ranged from 0.10 to 0.17 and the
CODs for PM2.5 ranged from 0.05 to 0.26, which are generally higher than seen in this study. A restaurant
site was determined to be the cause of the higher PM2.5 concentrations that resulted in the CODs above 0.25
(Hawley and Vu, 2012). Pinto et al. (2004) studied PM2.5 concentrations over a three county range in
Southern CA in 1999-2000. The CODs ranged from 0.14 to 0.26; these are higher than this study, but
similar to Hawley and Vu (2012). The reason could be due to the differences in local emission sources or
the spatial differences between the sites in the two studies. Pakbin et al. (2010) monitored PM between the
10 and 2.5 µm size range in Los Angeles, CA from 2008 to 2009. The CODs between the urban sites
monitored were 0.10 to 0.18. The CODs found in the Pakbin et al. (2010) study were similar to the CODs
for PM10 found in this study.
390
CONCLUSIONS
In conclusion, construction influences on air quality appear to occur in the immediate vicinity of
the construction site and dissipate rapidly once construction activity is halted. This study showed that it is
important to take the measurements while construction activity is occurring. These field campaigns were
designed based on sampling dates and not correlated in advance with the construction activities. Therefore,
the true construction influences may not have been captured during the sampling periods. In addition, the
sampling location for construction activities should be very close to the construction site.
This study showed that regardless of construction activities the PM10 concentrations did not meet
the specified CARB standards. Controlling construction emissions would bring the area closer to
compliance with air quality regulations, but alone would need reduce the concentrations to below standard
levels.
REFERENCES
Burns, Malcolm J.; Nixon, Gavin J.; Foy, Carole A.; Harris, Neil. 2005. “Standardisation of Data from
Real-Time Quantitative PCR Methods—Evaluation of Outliers and Comparison of Calibration
Curves.” BMC Biotechnol. 31: 1-13.
California Air Resources Board (CARB). Almanac Data: One Year, Many Pollutants, 2013; available at
http://www.arb.ca.gov/ei/emsmain/emsmain.htm (accessed 2014).
Chow, Judith C.; Watson, John G.; Green, Mark C.; Lowenthal, Douglas H.; DuBois, David W.; Kohl,
Steven D.; Egami, Richard T.; Gillies, John; Rogers, C. Fred; Frazier, Clifton A.; Cates, William. 1999.
“ Middle- and Neighborhood-Scale Variations of PM10 Source Contributions in Las Vegas, Nevada.”
J. Air & Waste Management Assoc. 49 (6): 641-654.
Hawley, Harmonie; Vu, Diep. 2012. “Air Quality on a Southern California University Campus in the
Spring, 2011 Semester.” In (Ed.), Environmental Science and Technology, 2012 Volume 1. George
Sorial and Jihua Hong, Eds. American Science Press, Houston, USA, pp 1-604, 2012. ISBN:
9780976885351.
Moore, Katharine; Krudysz, Margaret; Pakbin, Payam; Hudda, Neelakshi; Sioutas, Constantinos. 2009.
“Intra-Community Variability in Total Particle Number Concentrations in the San Pedro Harbor Area
(Los Angeles, California).” Aerosol Science and Technology. 43: 587-603.
Muleski, Gregory E.; Cowherd, Chatten Jr.; Kinsey, John S. 2005. “Particulate Emissions from
Construction Activities.” J. Air & Waste Management Assoc. 55: 772-783.
Pakbin, Payam; Hudda, Neelakshi; Cheung, Ka Lam; Moore, Katharine F.; Sioutas, Constantinos. 2010.
“Spatial and Temporal Variability of Coarse (PM10-2.5) Particulate Matter Concentrations in the Los
Angeles Area.” Aerosol Sci. Technol. 44:514-525.
Paykov, Oksana; Hawley, Harmonie A. 2013. “A Protein-Retention Method for Specific Surface Area
Determination of Soil.” Geotechnical Testing J. 36 (4): 606 -611.
Pinto, Joseph P.; Lefohn, Allen S.; Shadwick, Douglas S. 2004. “Spatial Variability of PM2.5 in Urban
Areas in the United States.” J. Air & Waste Management Assoc. 54: 440-449.
Wilson, J. Gaines; Kingham, Simon; Pearce, Jamie; Sturman, Andrew P. 2005. “A Review of Intraurban
Variations in Particulate Air Pollution: Implications for Epidemiological Research.” Atmos. Environ.
39: 6444-6462.
391
2012 AIR QUALITY IN ALBERTA OIL SANDS COMMUNITY OF FORT MCKAY VERSUS
CANADIAN URBAN LOCATIONS
Warren Kindzierski* and Md. Aynul Bari

(University of Alberta, Edmonton, Alberta, Canada)
Negative public perception exists about environmental quality related to oil sands development in
northeastern Alberta, Canada. A current belief is that air quality in the region is poor and is adversely
affected by these developments. Fort McKay is a small community of less than 1,000 people located within
10 km of several active oil sand developments. This community is important in terms of the real influence
that these developments have on air quality in the region for several reasons. It is the closest location where
a community of people lives with respect to active and planned oil sands developments that have large open
pit surface mines, and petroleum upgrading and processing facilities. The state of air quality observed here
provides the best representation for consideration of impacts posed to a population.
This presentation will highlight results of a recent study of several air quality parameters that are
continuously monitored in Fort McKay (SO2, NO2, O3, PM2.5, and total hydrocarbon). Cumulative
frequency distribution plots and box and whisker plots of 1-hour concentrations in Fort McKay during 2012
were constructed for these pollutants and compared to data from several urban residential locations in
Canada where similar air pollutants are continuously monitored: Edmonton, Alberta (a residential location),
Toronto, Ontario (downtown and residential location) and Hamilton, Ontario (downtown and residential
location).
As seen in previous years, monitoring results for 2012 show that these urban Canadian residential
locations show greater impact to air quality than that observed in Fort McKay for NO2, O3, and total
hydrocarbon. Interpretation of results for PM2.5 are confounded by occurrence of forest fires in which hourly
concentrations exceeded 200 μg/m3 in Fort McKay in 2012; however past analysis have indicated that the
urban locations show greater impact compared to Fort McKay. SO2 is a good marker of fossil fuel
combustion activities associated with upgrading activities. One-hour SO2 concentrations at Fort McKay
were higher than Edmonton residential for 12% of time and Toronto residential for 8% of time in 2012.
However, 1-hour SO2 concentrations at Hamilton downtown and residential were higher than at Fort
McKay >99% of time. Hamilton is a medium-sized city (population 520 000) with a wide range of industry
including two major steel mills. SO2 was not monitored at Toronto downtown.
392
DEVELOPMENT OF VEHICLE EMISSION DATABASE FOR AIR QUALITY ANALYSES
Po-Hsien Kuo, Fengxiang Qiao, and Lei Yu

ABSTRACT: Vehicle emission has significant impacts on air quality, which are affected by complicate
factors. It is almost impossible to have one or several simple models to actually depict the relationships
between vehicle emissions and their associated driving activities, roadway conditions, and even human
behaviors. Environmental Protection Agency (EPA) has released a series emission estimation models
including MOVES. However these models are normally based on limited vehicle emission tests. EPA
strongly suggests incorporating as much as possible local information as inputs, and suggests continuing to
test more. Texas Southern University has been using the Portable Emission Measurement System (PEMS)
to have generated a large amount of vehicle emission data pool. In this research, a dynamic vehicle emission
database is established storing information including vehicles’ information, environmental information,
tested emission, and other relevant information. The developed database will also allow users at various
levels to access. K-12 students can acquire better knowledge on Transportation and environment
engineering. College students can use it for more knowledge learning and research opportunities.
Researchers from academics, industry, and government can use it for better technology applications,
decisions makings, and policy proposals. With more surveillance data collected, the database could be even
improved with more applicability.
INTRODUCTION
Vehicle emission is one of the largest sources to influence the air quality in the world, which not
only damages the environment but also causes serious adverse health issues of human bodies. It is not easy
to build up a perfect simulator to predict the accurate emission by using one or more models. Two famous
models by Environmental Protection agency (EPA) are currently used to predict emissions. This first one
is the Motor Vehicle Emission Simulator (MOVES) with the purpose of estimating emissions for mobile
sources covering a broad range of pollutants and allows multiple scale analysis (EPA, 2014). The second
one is MOBILE6, an emission factor model for predicting emission factors from cars, trucks, buses, and
motorcycles under various conditions (EPA, 2013). Although there are several simulators help to predict
the possible emissions, these models are all based on restricted vehicle emission tests on limited test beds.
Those models are not friendly enough to some junior level users because of complex parameters that are
necessary filled in models.
According to the Intergovernmental Panel on Climate Change (IPCC) report, emissions from
transportation could rise by 71 percent from 2010 levels by 2050, while the scientific consensus holds that
the world needs to reduce overall greenhouse gas emissions 80 percent by then. The transportation sector
is projected to be the fastest growing source of greenhouse gas emissions in the world (Snyder, 2014).
Vehicle emissions could be more and more serious and harm human’s health if lacking of the awareness of
the hazardous situation to occur in the near future.
OBJECTIVE
The objective of this research is to define the parameters and estimate an online emission database
system to manage all collected information and also assist different users for various usages.
PROCEDURE OF CONSTRUCTING EMISSION DATABASE SYSTEM

The procedure to construct an Emission Database Management System can be summarized into
five steps.
393
Step 1. Data Collection. Both vehicle and emission information should be recorded through the
Portable Emission Measurement System (PEMS) or similar one(s). To gather better and sufficient
information with higher and lower rpm and speeds, drivers would be asked to drive on different roadway
facilities including highways and local areas.
Step 2. Data Preparation. The required input parameters and output emission data should be
prepared including: vehicle speed, time period, vehicle types, location, and all emissions measured. These
will be the key parts of the emission database.
Step 3. Define Parameters. Due to the excessive and complex of data collected, it would be more
practical to classify some parameters into meaningful phases. For example, time period would be classified
to peak hours and non-peak hours. Location could be classified into highways, arterial roads, ramps, and
streets. Vehicle types would be classified to trucks and passenger cars.
Step 4. Construct Emission Database Table. Based on all available parameters and emission
values, the emission database table can be created.
Step 5. Develop MySQL Database Management System. Base on the database table create from
step 4, the database table can be imported into the MySQL program, and the php language can be used to
design a webpage to bridge the MySQL and the Web.
The Online Emission Database System uses a quick convenient method to evaluate the possible
emission based on factors such as vehicle types, traffic demand, and environmental information. It is a good
way to help the different level users (K-12, college students, researchers, government, and engineers) to
learn knowledge, develop applications, and/or conduct relevant research.
TOOLS
A PEMS was used to measure real time emissions. The online webpage and database system are
communicated and controlled by MySQL and phpMyadmin.
The Equipment PEMS. The PEMS is a lightweight moving laboratory that used to collect second by
second data while vehicles are moving. Emission testing with PEMS has become one of the key elements
of the European emissions legislation (IET 2012). The data collected by PEMS include date, time,
revolutions per minute (RPM), engine temperature, fuel consumption, pressure, speed, exhaust mass flow
meters, weather, Global Positioning System (GPS), and so on. The information of vehicle performance
could be collected by using two different methods. The first method is to use sensors to connect sparker
plug and air filter, which is near the engine of vehicle for the collection of vehicle information. Another
method is to use the On-board Diagnostics II (OBD II) device that can be directly connected through a plug
inside the vehicles. The emission information can be obtained by using a cable with sensors to plug into the
exhaust pipe. So that the quantity of Hydro carbon (HC), Carbon Monoxide (CO), Carbon Dioxide (CO2),
and Nitrogen Oxides (NOx) Particulate Matter (PM) can be measured.
Software: MySQL & phpMyAdmin. The MySQL is an open source relational database management
system. It could be generally used to manage abundance data in most operation systems. The phpMyAdmin
is open source software that is written in php intended to administrate the MySQL by using the web browser.
They play important roles in managing, modifying, creating, and deleting the tables and/or rows/columns
in the database.
DATA COLLECTION AND PREPARATION

The Innovative Transportation Research Institute at Texas Southern University uses the PEMS to
test vehicle emissions in Houston metropolitan areas, which has generated a large amount of vehicle
emission data pool form year 2004 to 2011. The original data are already classified into five different tables
while exported from the PEMS. The tables include drivers table, emission table, vehicle table, bag sum
table and weather table. As there are some non-meaningful information and leaking data, the tables should
be re-designed and re-constructed to be workable tables so as to rationally include all necessary information
394
such as all emissions, vehicle type, consumption, dates, hours, speed, GPS, and so on. Table 1 and Table 2
in this paper illustrate the original data tables, including: the drivers table (Table 1(a)), the emission table
(Table 1(b)), the vehicle table (Table 2(a)), and the weather table (Table 2(b)). Table 3 and Table 4 present
the clear vehicle, local condition and emission related tables which have been reorganized. The information
includes most useful parameters such as time, vehicle type, vehicle speed, temperature, RPM, pressure,
emission…etc. In this database table, a total of 135,426 data are listed covering years 2004 to 2011. The
data in 2004 from database has been used in to evaluate on-road vehicle emission and activity data in
Houston, Texas (Qiao et al., 2005). In 2012 the database also used to analyze how the driver’s driving
behaviors influence the vehicle emissions (Tao and Yu, 2012). Furthermore, Hill et al. used the database to
investigate the effect between the drive-through routes and vehicle emission at different restaurants (2014).
TABLE 1. The original database Table for drivers and emission information
(a) Drivers information (b) Emission information
TABLE 2. The original database Table for vehicle and weather information
(a) Vehicle information (b) Weather information
TABLE 3. Vehicle, local condition and emission database Table
395
TABLE 4. Vehicle, local condition and emission related database Table
DEVELOPING MYSQL DATABASE MANAGEMENT SYSTEM

When the vehicle, local condition and emission related database table are constructed, the prepared
database table is imported to the database system MySQL. Then, the webpage is designed and programed
by using the php language, which can be used to connect MySQL with the webpage. In the Online Emission
Database System, selected parameters were used to present the emission results. In this study, four
parameters including the time period (peak or off peak hours), the facility types (roadway or Highway), the
vehicle speed (mile per hour), and the vehicle type (LDGV or Truck) were selected to be the major inputs
that were related to emissions (NOx, CO, HC, CO2, PM). Figure 1 shows the webpage designed by the php
language and the web browser used is Firefox.
FIGURE 1. The webpage of online emission database system.
Base on the webpage presented, four blank inputs and one emission are needed to fill in values or
information by users. The “time period” would have two sections which users have to select either “peak
hour” or “off peak hour”, per users’ actual needs. According to the City of Houston Public Works &
Engineering Department, the peak hours are from 6am to 9am in the morning and 4pm to7pm in the
396
afternoon for weekdays. The second input “facility type” is to type in highway or local road in this project.
Third input is the vehicle speed and the users need to fill how the vehicle speeds in this project such as 35
or 50 mile per hour. In this database system, there are two vehicle types: light duty gas vehicle (LDGV)
and heavy duty diesel vehicle (HDDV), which can be selected as the fourth input. For emission parameters,
if users do not fill any specific emission, all emission factors (CO2, CO, PM, HC) will be tabulated after
the download key is selected. If a user wishes to choose a specific pollutant such as Hydrocarbons (HC) or
Carbon Monoxide (CO), he or she needs to select “HC” or “CO” to inquire.
CONCLUSIONS
In this research, the Online Emission Database System was used to provide real vehicle emissions
based on given local conditions (weather info), vehicle physical features (vehicle info), and roadway facility
types. The database includes 135,426 records from PEMS including all information about drivers, weathers,
vehicles, local conditions and emissions. All data are organized into different suitable database tables,
which include several possible input parameters. Four essential input parameters (time period, facility types,
vehicle speed, and vehicle type) are selected, which are related to emissions directly. The developed
database system can not only benefit research and engineering fields, but also educate students and the
public on environmental issues. In the future, the travel distance would be added to predict the fuel
consumption and vehicle emissions in total. With more data record appended, the Online Emission
Database System would be more efficient and powerful.
ACKNOWLEDGEMENTS
TranLIVE, the U.S. National Science Foundation (NSF) CREST #1137732 are gratefully acknowledged.
REFERENCES
Institute for Energy and Transport (IET). 2012. Real-world emissions and activity monitoring of engines
and vehicles in support to the European Emissions control legislation. Last update: 2012.
http://iet.jrc.ec.europa.eu/pems/portable-emissions-measurement-systems-pems, Accessed Date: April
22, 2014.
Intergovernmental Panel on Climate Change (IPCC). 2014. Last update: 2014. http://www.ipcc.ch/
Accessed Date: April 22, 2014.
United States Environmental Protection Agency (US EPA). 2014. MOVES (Motor Vehicle Emission
Simulator). Last update: 2014. http://www.epa.gov/otaq/models/moves/, Accessed Date: April 20,
2014.
United States Environmental Protection Agency (US EPA). 2013. MOBILE6 Vehicle Emission Modeling
Software. Last update: 2013. http://www.epa.gov/otaq/m6.htm#m60, Accessed Date: April 20, 2014.
Qiao F., L. Yu, and M. Vojtisek-Lom. 2005. “Collection and Evaluation of On-Road Vehicle Emission and
Activity Data in Houston”. Transportation Research Board, 1941:60-71. National Research Council,
Washington, DC, 2005.
Snyder, T. 2014. Transit Union and Sierra Club Join Forces for Earth Day and Beyond STREETBLOG
USA.http://usa.streetsblog.org/2014/04/15/transit-union-and-sierra-club-join-forces-for-earth-day-
and-beyond/, Accessed Date: April 18, 2014.
Tao, F. and L. Yu. 2012. “Effects of Driving Behaviors on Vehicle Emissions: Case Study in Houston,
Texas”. Proceedings of the 2012 Annual Meeting of Transportation Research Board, No. 12-0852 -
C10 National Research Council, Washington, DC, 2012.
Hill, K., F. Qiao, M. Azimi, and L. Yu. 2014. “Impacts of Restaurant Drive-Through Configurations on
Vehicle Emissions”. Proceedings of the 2014 Annual Meeting of Transportation Research Board, No.
14-4659. National Research Council, Washington, DC.
397
VEHICLE EMISSION ESTIMATION WHILE PICKING UP PASSENGERS AT AIRPORT

TERMINALS
Larry Hill, Fengxiang Qiao, Keziah Hill, and Lei Yu

(Texas Southern University, Houston, Texas, USA)
ABSTRACT: Air population is in steady increase as more and more vehicles are running on transportation
infrastructure systems. At airport terminals when drivers pick up passengers, vehicles are there waiting in
lines with the engine idling, waiting to retrieve their friends or relatives. Plenty of people that has traveled
and entered the airport terminals may have even caught the smells of the emissions that are being released
into the air by those idling vehicles. This research is to investigate the amount of emissions each car is
releasing into the air at airport terminals through field studies, and estimate the amount of emissions caused
by these vehicles. Two airports in Houston, TX were selected for field studies: William P. Hobby Airport
and George Bush Intercontinental Airport. The field data were collected using floating car method together
with the geolocation record of testing vehicles from Global Positioning Systems (GPS). Speeds and
acceleration rates of idling and cycling vehicles at terminals under different time periods and different time
periods were recorded with different traffic demands and different waiting time. Based on the studies, this
paper proposed a one-hour parking free policy so as to eliminate the number of idling vehicles at terminals.
BACKGROUND OF RESEARCH
The population in metropolitan areas is on a steady increase and more and more pedestrians are
buying vehicles. With the growing number of vehicles being put on roads and highways, big problems are
created that affect the quality of air that we are breathing, including at airport terminals. When passengers
are being picked up at these terminals, vehicles waiting in line with the engine running, waiting to retrieve
their friend or relative, generate emissions. A plenty of people have traveled and entered the airport terminal
by smelling the emissions that are being released into the air by those vehicles.
The purpose of this research is to propose a one hour of free policy for picking and dropping of
passengers so vehicles will not be idling all the time. The data process consists of the floating car method
and Global Positioning Systems (GPS) to record down speeds and acceleration rates of idling and cycling
vehicles at terminals under different time periods and different time periods and different traffic demands
with different waiting time. These speeds and acceleration rates can then be synthesized into Vehicle
Specific Power’s (VSP) values, which will yield out corresponding VSP distribution and Operational Mode
(OM) distributions at terminals. By utilizing the Environmental Protection Agency (EPA) newly approved
emission estimation model MOVES (Motor Vehicle Emission Simulator), the following greenhouse gases
(e.g. NOx, CO, CO2, HC) as well as fuel consumptions can be easily estimated.
We hope that it can have a positive impact within the airport system because the air quality is very
important to the welfare of the people that it affects. By implementing this strategy into the laws and
regulations, this will cut down on the emissions and give the environment an economic boost. With all the
different chemicals that are being released there has to be a great consideration to make the world that we
live in that much more safer and sufficient to human life.
AIR POLLUTIONS AND EFFECTS

Air pollutants are substances that adversely affect the environment by interfering with climate, the
physiology of plants, animal species, entire ecosystems, as well as with human property in the form of
agricultural crops or man-made structures. We list climate at the top of the list to reflect the fact that global
climate change has been recognized as one of the most important environmental challenges to be faced by
humanity in the 21st century. In this context certain climate forcing agents—the most important one being
carbon dioxide—which otherwise cause no harm to living organisms, should be added to the list of “classic”
398
pollutants, along with such compounds as oxides of nitrogen or sulfur. On the other hand, climate research
has linked certain compounds long recognized as air pollutants (for instance black carbon) to the warming
of climate, thus providing one more reason for their control.
Air pollutants can originate from natural or anthropogenic (man-made) sources, or both. Examples
of natural sources of pollution include volcanic eruptions or wind erosion. Emissions from internal
combustion engines are an exemplary source of anthropogenic pollution. Some sources of pollution, such
as forest fires, can be related to both natural phenomena and human activities.
Atmospheric reactions can transform primary pollutants into different chemical species. These
reactions can produce both harmless compounds and secondary air pollutants that may be more harmful
than their precursors. The world’s most important air pollutants, their sources, and known or suspected
environmental effects are listed in Table 1 (Sher, 1998).
TABLE 1 Air Pollutants, their Sources, and Effects

Pollutant Natural Source Anthropogenic Source Environmental Effect
Primary pollutants that produce
High temperature fuel
photochemical smog, acid rain,
Nitrogen oxides (NO Lightning, soil combustion—motor
and nitrate particulates.
+ NO2) bacteria vehicles, industrial, and
Destruction of stratospheric
utility
ozone. Human health impact.
Combustion of biofuels Reduced atmospheric visibility.
Forest fires, wind
such as wood, and fossil Human health impact. Black
Particulates erosion, volcanic
fuels such as coal or carbon particulates contribute to
eruption
diesel global warming.
Coal combustion, ore
Volcanic eruptions smelters, petroleum
Sulfur dioxide Acid rain. Human health impact.
and decay refineries, diesel engines
burning high-sulfur fuels
Lightning,
Secondary pollutant Damage to plants, crops, and
photochemical
Ozone produced in man-made products. Human
reactions in the
photochemical smog health impact.
troposphere
Rich & stoichiometric
Carbon monoxide Unnoticeable combustion, mainly from Human health impact
motor vehicles
Animal respiration,
Fossil fuel and wood
Carbon dioxide decay, release from Most common greenhouse gas
combustion
oceans
Non-methane Biological Incomplete combustion, Primary pollutants that produce
hydrocarbons (VOC) processes solvent utilization photochemical smog
Anaerobic decay,
Natural gas leak and
Methane cud-chewing Greenhouse gas
combustion
animals, oil wells
Chlorofluorocarbons Solvents, aerosol Destruction of stratospheric
None
(CFC) propellants, refrigerants ozone
399
Table 1 contains the chemicals that have greatest impact on the eco-system: Ozone (O3), Carbon
monoxide (CO), Nitrogen dioxide (NO2), Lead (Pb), Particulate matter below 10 µm (PM10), and Oxides
of sulfur (SOx). They are the chemicals that are being released into the atmosphere and having a very
profound effect on the atmosphere.
METHODOLOGY AND TESTS

This research has shed light on the growing problem with the quality of air that we breathe.
Studying the effects of emissions from the vehicles in the terminals at the airports, should prompt people
to become more aware that the air we are breathing is harmful. This is why implementing an hour of free
parking will cut down on the amounts of pollutants being taking in and also contributing to health problems.
Based on how the operations are handled and the research that has been conducted. Taken this research
study to the board members and getting this detailed stage of the research added to the policy will help in a
great way. By using the GPS tracking device, we were able to make the proper calculations to determine
just how much emissions is being released into the atmosphere. The effects of emissions go much farther
than the airports one should consider the surrounding areas that have all sorts of people with health issues,
including kids. Table 2 shows how the number of cars was divided that were making more trips around the
terminals at peak and non-peak hours.
TABLE 2. Count list based on test sites and trips
FIGURE 1. One of the terminals for the test (https://www.google.com/search? pictures of airport
terminals at bush intercontinental)
EMISSION ESTIMATIONS
400
With the car following tests in Houston airports, the recorded geo-location information from GPS
devices were retrieved while the speed and acceleration rates were calculated. Based on binning standard
of the EPA’s new emission estimation model MOVES, the VSP distribution and the associated emission
rates in the operating mode 30 bins were calculated. The information of the test vehicle is a Nissan Altima
with year 1999 and mileage 80,000 mile.
The emission rates used for emission estimation in this paper was derived based on the properties
of this vehicle, where the emission database were prepared though the various on-road test to this vehicle
using the Portable Emission Measurement System (PEMS).
The emission estimated at airport terminals are listed in Figure 2. The passenger-pick-up vehicles
could produce less emission if vehicles drive less at around terminals. If partial of the vehicles can park in
a nearby parking lot (normally the hourly parking lot), the emissions at terminals could be greatly reduced.
250.00
195.45
200.00
150.00
112.51
100.00 77.32
47.29
50.00
0.00
CO2 (g/hr) CO (mg/hr) HC (mg/hr) NOx (mg/hr)
FIGURE 2. Emission rates in a terminal of William P. Hobby Airport, Houston.
CONCLUSIONS
In this research, the emissions at airport terminals from passenger-pick-up vehicles were estimated
based on the geo-location information from GPS devices by a floating car method. The Drivers average
cycling time around terminals were obtained from a questionnaire survey. The emissions were estimated
based on the real world emission measurement database, and the operating mode bin was calculated based
on the EPA new model emission MOVES. Further in-depth tests and analyses will be conducted. It is
recommended to implement suitable management strategies such as the ONE HOUR FREE PARKING
policy to reduce the emissions at airports. Also other tests are currently in progress to make this research
much more suitable, we believe that this research will continue to evolve because this is a stepping stone
to better ways of making the airport terminals better to operate. Once all the data is finally collected the
information will be much more accurate and solid enough to present to the policy writers and the FAA
board members to make this research apart of every day operation.
REFERENCES
Yu, L., Li, X., and Zhuo, W. (2003). Airport Related Traffic and Mobile Emission Implications. Texas
Department of Transportation. Report No: 4317-1.
Simaiakis,H. MIT Journal 2011. Demonstration of Reduced Airport Congestion through Pushback Rate
Control. Report No. ICAT-2011-2 (January 2011). Cambridge, MA: MIT International Center for Air
Transportation, Department of Aeronautics & Astronautics, Massachusetts Institute of Technology.
401
Lin, S. “Residential proximity to large airports and potential health impacts in New York State”. Int Arch
Occupy Environ Health 817797–804.8042008. doi: doi: 10.1007/s00420-007-0265-1.
Tonne C, Melly S, Mittleman M, Coull BA, Goldberg R, Schwartz J. 2007. A case-control analysis of
exposure to traffic and acute myocardial infarcion. Environ Health Perspect 115:53–5.Sher, E.
402
EFFECTIVE APPROACHES FOR PUBLIC COMMUNICATION OF AIR QUALITY RESULTS

FROM TWO ENVIRONMENTAL DREDGING PROJECTS
Scott Manchester and Matt Traister

(O’Brien & Gere, Syracuse, New York and Cincinnati, Ohio, USA)
Introduction/Objectives. Two environmental sediment dredging projects, one in upstate New York and one
in northern Indiana, each involved dredging and storage of about 2 million cubic yards of sediment into
consolidation and disposal facilities. Each project’s dredged sediment contained contaminants with potential
to result in hazardous air emissions to the local community. Therefore, each project developed a
comprehensive community air quality monitoring (AQM) program to evaluate air emissions from dredging,
sediment handling and containment activities. In addition, to address air quality concerns expressed from
each local community prior to project commencement, each AQM program made provisions to continually
communicate the results to the community. This presentation overviews each project’s AQM program, and
discusses the approaches used meet project stakeholder’s needs to effectively communicate to the local
community air quality levels throughout the dredging project.
Methods/Approach. Both the New York and Indiana short-term AQM programs featured real-time
continuous air monitoring and automated data collection - the Indiana AQM program monitoring
naphthalene and dust around the 1.6-mile perimeter of a confined disposal facility (CDF), and the New York
AQM program measuring total VOCs and dust along eight total miles of work perimeters in two work areas
spaced four miles apart.
Both AQM programs developed systems to post data to a public interactive website, allowing the
community to review air quality levels and compare to pre-established work perimeter limits. The Indiana
approach consisted of graphs of real-time air quality levels, with levels above limits highlighted on the
graph. The New York approach posted graphs of validated air quality data on the day following collection,
and comments were included on the graphs explaining any results above limits.
Results/Conclusions. Both the New York and Indiana AQM programs effectively used internet websites to
continuously and efficiently keep the community informed on air quality levels during dredging activities.
Each program’s website provided the community a pathway for daily review of: 1) instrument operational
status and data capture, and 2) adherence to air quality limits. As a result, the health and safety of the
community was continually communicated and assured throughout dredging activities.
403
METHANE SLIP EMISSION TREATMENT BY PT/PD/AL2O3 WASHCOATED MONOLITH

WITH SPATIAL CONCENTRATION MEASUREMENTS
Gregory Bugosh, Vencon Easterling, Michael Harold*

(University of Houston, Houston, TX, USA)
Advances in drilling technology have led to low-price domestic natural gas, increasing the economic
incentive for natural gas powered engines. Increased utilization of natural gas to power vehicles in the form
of compressed natural gas (CNG) and liquefied natural gas (LNG) has already begun and is expected to
accelerate. Natural gas vehicles typically have lower emissions of particulate matter (PM), NOx and SOx,
especially compared to older diesel powered vehicles. Engine exhaust emissions of non-methane
hydrocarbons (NMHCs) and CO are treated by catalytic oxidation on precious metal catalysts. The
oxidation catalysts are particularly effective for lean burn vehicles which have excess O2 in the exhaust.
However, with the primary component of natural gas being methane (CH4), a small but significant amount
of CH4 fuel survives the combustion chamber and “slips” into the exhaust. With global warming potential
approximately 20 times that of CO2, CH4 is a potent greenhouse gas (GHG), and regulations are expected
to become more stringent. For this reason, development of CH4 oxidation catalysts and emission control
systems are needed. The objective of this study is to carry out a detailed experimental study of CH4
oxidation on supported Pt/Pd catalysts, which have been reported to be the most effective catalysts
developed to date.
Simulated exhaust was treated on a bench-scale monolithic catalytic reactor equipped with FTIR
and spatially-resolved mass spectrometer (SpaciMS). The CH4 conversion and product distribution were
measured over a range of catalyst temperatures and CH4/O2 feed ratios. The CH4 conversion versus O2 feed
concentration shows a complex dependence characterized by a clockwise hysteresis loop for O2
concentrations at or below the CH4/O2 = 0.5 stoichiometric point. This loop has a peak in CH4 conversion
at low O2 feed concentrations, which can exceed the CH4 conversion at high O2 conditions. The CH4
conversion is minimal (<10%) at low O2 feeds until O2 is lowered below a critical concentration, at which
point the reaction achieves light-off. When O2 feed is increased following light-off, the increased
conversion (~90% at 538°C) is sustained. The CH4 conversion thus displays hysteresis depending on
direction of O2 increase or decrease. Additional increase in O2 concentration leads to a sharp drop in the
conversion back to the low conversion branch. This loss in CH4 conversion is attributed to oxygen
poisoning of the active catalyst sites. The O2 feed concentrations for light-off and quenching are dependent
on temperature and reactant feed concentrations. When light-off is achieved at the low O2 conditions, the
CH4 oxidation is supplemented by CH4 reforming, which contributes to increased CH4 conversions overall.
Reforming activity does decrease with time on-stream, but the activity can be quickly restored by subjecting
the catalyst to O2 feeds above the quenching point, followed by lowering O2 feed to achieve light-off at
restored high conversion. SpaciMS is performed to further increase the understanding of the reaction
progression through the length of the monolith. CH4 combustion to CO2 and H2O occur in the front portion
of the catalyst, followed by reforming to CO and H2 in the back portion of catalyst. Introduction of CO to
the feed sheds further insight on the progression of reactions: CO reacts first and then consumes a portion
of the O2, enabling the CH4 conversion light-off at increased O2 feed conditions. The data are interpreted
with a phenomenological model involving the reversible oxidation of Pd to PdO.
404
PREDICTING SO2 OXIDATION OVER A PT/AL2O3 DIESEL OXIDATION CATALYST
Tayebeh Hamzehlouyan*, Chaitanya S. Sampara and William S. Epling

(University of Houston, Houston, TX, USA)
Diesel oxidation catalysts (DOCs) oxidize CO, NO and unburned hydrocarbons present in the diesel exhaust
gas. NO oxidation is a desired reaction since the higher NO2 to NO ratios improve the regeneration of soot
filters as well as the performance of NOx abatement systems, both located downstream of the DOC. DOCs
are typically composed of Pt or Pt/Pd blends with both precious metals susceptible to different extents of
sulfur poisoning. SO2 is the expected fuel sulfur combustion product coming out of the engine. With high
levels of O2 and H2O in the diesel exhaust, SO2 oxidation over the DOC is expected, with sulfuric acid
formation also possible. It has been observed that SO3 leads to more severe deactivation compared to SO2.
Therefore, SO2 oxidation over the DOC is an undesired reaction which needs to be understood in order to
predict the deactivation behavior of the DOC as well as that of the downstream catalysts.
In the present work, an SO2 oxidation experimental study was performed and a kinetic model was
developed in order to describe SO2 oxidation over a Pt/Al2O3 oxidation catalyst. A monolith supported
Pt/Al2O3 (50 g/ft3 Pt) catalyst was used in the experiments. A separate reactor, upstream of the main reactor,
was used to generate SO3 when SO3 was required in the feed for the kinetic and deactivation studies. For
all experiments, the outlet gas concentrations were measured using a MKS MultiGas MG-2000 FT-IR
analyzer. An apparent activation energy of 98.8 kJmol-1 was measured when SO3 was present in the feed.
Reaction orders of 0.88 and -0.24 were obtained for SO2 and O2, respectively, and the SO3 reaction order
was found to be -0.42 demonstrating its inhibition effect.
A microkinetic model based on a Langmuir-Hinshelwood mechanism was proposed for the
catalytic oxidation of SO2 on Pt/Al2O3 and a one dimensional steady state model was developed for a single
channel of a monolith. A plug flow reactor model was assumed and the set of algebraic differential
equations was solved at various temperatures to predict the SO2 conversion as a function of temperature. A
set of kinetic parameters, taken from the literature, was used in solving the reactor model where some
parameters were fit to match the experimental data. A separate set of experimental data which was not
included in the parameter optimization was used to validate the kinetic model.
The relative importance of each step in the reaction mechanism was studied at different
temperatures to identify the rate determining step (RDS). According to the model, at temperatures below
300°C, O2 adsorption/desorption is the RDS, whereas at higher temperatures the surface reaction between
the adsorbed SO2 and oxygen becomes the RDS. The model predictions imply that, at low temperatures,
SO3 inhibits SO2 oxidation through occupation of the active sites required for oxygen adsorption, verifying
the higher activation energy observed in the presence of SO3 in the feed. The modeling results revealed that
the relative importance of the individual rates in the mechanism as well as the surface coverages were
strongly temperature dependent.
405
WHY SILVER/MESOPOROUS SILICA CATALYST IS UNIQUE FOR CO AND HCHO

CATALYTIC OXIDATION ELIMINATION?
Zhenping Qu*, Dan Chen and Xiaodong Zhang

(Key Laboratory of Industrial Ecology and Environmental Engineering, School of Environmental
Sciences and Technology, Dalian University of Technology, Dalian, 116024, China)
The elimination HCHO and CO at low temperatures is an important subject for the environmental
protection. Catalytic oxidation using heterogeneous catalysts has proven to be an efficient and practical
technology for controlling VOCs emission. The success of this approach greatly relies on the properties of
the catalyst. The preparation of high dispersion nanocatalysts by the regular nano pore channels of
mesoporous silica, such as MCM-41 and SBA-15 and so on, has turned into a hot issue in heterogeneous
catalysis. As a matter of fact, silver catalysts have showed great catalytic activity even at lower temperature
in many reactions, for example, hydrogenation of unsaturated aldehydes, partial oxidation of methanol to
formaldehyde, and oxidative coupling of methane to ethane and ethylene, CO oxidation, NOx elimination
and so on. Although silver is a noble metal, its resource is more abundant compared with that of platinum,
and thus its price is much lower. Therefore, silver catalysts have great potential to be the outstanding
catalyst in catalytic elimination of the VOCs.
According to the previous studies, there existed four kinds of silver species on the supports,
including metallic Ag particles (Ag0) with subsurface oxygen species, isolated Ag+ ions, well dispersed
Ag2O and Ag δn + clusters on Ag based catalysts supported on different supports (MCM-41, SBA-15, NaY,
SiO2 and TiO2). No activity for HCHO oxidation was observed on any supports, and silver particles with
subsurface oxygen (Oγ) in bulk were more active for the adsorption and activation of HCHO. The
mesoprous silica such as MCM-41, SBA-15 supported silver catalysts gave new adsorption sites for HCHO,
and it was easily activated at lower temperatures and showed better surface reaction activity for HCHO
oxidation. In our study, the mechanism of HCHO catalytic oxidation in Ag catalysts was systematically
studied by in situ FT-IR and TPSR experiments. The formation of the formate ad-species was found to be
not only derived from the HCHO(a) dissociation adsorption along with the OH consumption but also from
the disproportionation of dioxymetylene (DOM) active ad-species. In addition, we found CO species were
the main reaction intermediates for HCHO oxidation on Ag based catalysts, and the formation and
dissociation of CO obviously promoted the HCHO catalytic oxidation. It was our first time to report that
after the oxygen (900oC)-hydrogen (300oC) pretreatment in cycle mode, an excellently catalytic activity
(T100%=22oC) was obtained on the 1.42 wt% Ag/SBA-15 catalyst. Also, it was evident that the oxygen
adsorbate-induced decrease in the surface-free energy at 900oC induces the evaporated silver atoms to be
redeposited on the support, and meanwhile diffuse into the channels of SBA-15, forming more highly
dispersed small silver particles inside the channels, which at last played an important effect on the higher
catalytic activity for CO in Ag catalysts. That is, the excellent activity for HCHO and CO catalytic oxidation
for our silver catalysts could be ascribed to the unique subsurface oxygen formation and the strong metal-
support interaction (SMSI) between Ag and mesoporous silica such as MCM-41 and SBA-15.
406
THE SO2 REMOVAL METHOD OF A SULFURIC ACID PROCESS EXHAUSTS GAS
Jianjun LI and Huaqiang YIN (Sichuan University, ChengDu, China)

Xin LI (Chengdu Guohua Environmental Technology Co., Ltd, ChengDu, China)
This paper describes a new method of sulfuric acid exhausts gas treatment - the method of catalysis. When
the concentration of SO2 in the flue gas was less than 1700 mg/Nm3, the SO2 emission concentration is less
than 20mg/m3. The by-product of 30%sulfuric acid was acquired.
The exhaust gas from the sulfuric acid plant in a suitable reaction temperature was flowed into the
desulfurization system by the blower , mixed with the amount of steam in the pipe. The SO2, H2O, O2 in
the flue gas were changed into H2SO4 by catalytic in desulfurization tower, the SO2 of exhaust emission
was removed. When the desulfurization catalytic in the tower was adsorbed saturated in adsorption. The
catalyst can be regeneration washed with the water, and the activity was resumed after the catalyst
regeneration. When the acid reaches a certain concentration, it will return into sulfuric acid recycling
system.
When the exhaust gas temperature was at 70 ℃, the concentration of SO2 was with 600-
1700mg/Nm3. The SO2 concentration in outlet desulfurization tower is less than 20mg/m3, and the dust
≤5mg/m3. The process was applied in Chinese Hubei Daye Nonferrous Metals Co., Ltd. with 970,000t/a
sulfuric acid plant. The flow of flue gas is 34 × 104Nm3 / h. It was finished in August 2011.
The exhaust gas desulfurization rate is about 99%. The desulfurization tower were designed into
two diameters of 8m and 9m, and the high are 32m, using the gas-solid reactor, the project covers is about
950m2. The towers were using non-metallic material to prevent acid corrosion. All equipment and pipes
touched with the acid, the material was used the phenolic resin or polypropylene.
According to GB26132-2010, the SO2 emission concentration was changed from 860 to 400mg/m3, this
new technology satisfied in the desulfurization.
407
CHARACTERIZING AIR POLLUTANT EFFECTS CAUSED BY EXTRA COMMUTING TIME

DUE TO HOUSING PRICE FACTOR
Ling Liu, Fengxiang Qiao, and Lei Yu

ABSTRACT: Vehicle emission is one of the major sources of urban air pollutions. A large amount of gross
vehicle emissions are generated by commuting vehicles between residential houses and commuters’ work
places. Home buyers generally prefer to purchase their residential houses that are relatively cheaper in the
cost of relatively longer commuting time. People will only count for the additional travel time spent, fuel
costs, and other similar factors, with less concerns about additional air pollutions possibly generated. In
cities with populations between 15,000 and 1,000,000, the increase of one additional minute of average
commuting time will be associated with 1.9 dollars less housing price per square foot (p-value: 0.038) (Qiao
et al., 2014). In this paper, the air pollutants caused by additional travel time due to housing price factors
are characterized numerically. Air pollutants such as CO, CO2, NO2, NO, NOx, SO2 and fuel consumptions
were estimated by MOVES. Recommendations were proposed to governments so as to more efficiently
reduce mobile source air pollutions in metropolitan areas through joint efforts by government, agencies,
and industry from multiple fields including land use, housing market, transportation management,
environment protections, and law enforcement.
INTRODUCTION
While new vehicle engine technologies and new fuel sources have already reduced the amount of
pollutants from each individual vehicle, pollutions are, obviously, significantly affected by the relative
positions of residential houses and work places.
MOVES (Motor Vehicle Emissions Simulator) is a computer program designed by the US
Environmental Protection Agency (EPA), which incorporates substantial new emissions test data and
accounts for changes in vehicle technology and regulations as well as improved understanding of in-use
emission levels and the factors that influence them. Also, MOVES has a completely new software
framework that includes many new features and provides much more flexibility for input and output options
than MOBILE6.2. New input options in MOVES and changes in the way MOVES handles existing
information may appear to create significant new information burdens for states preparing submissions for
SIP and conformity related purposes.
In this paper, MOVES is used to estimate air pollution emissions from mobile sources, to get the
estimated emission inventory in nonpeak hours and peak hours in 2014 and 2004. The peak hour is 6AM
to 9AM and non-peak hour is selected as 12PM to 3PM. In order to focus on indentifying the air pollutant
effects caused by extra commuting time, passenger cars are selected for emission estimations.

Four largest metropolitan areas are selected in Texas, Houston, Dallas/Ft Worth, San Antonio and
Austin (illustrated in Figure 1). Per U.S. Census Bureau, Houston is the fourth largest city in the nation
with a population of 2.16 million, while other areas are also major metropolitan areas in Texas.
The reasons why these four largest metropolitan areas were selected are threefold. First, these
metropolitan areas constitute more than 60% of total population in Texas in 2012. The counties where the
metropolitan areas are located are among the most populous in the United States. For instance, Harris county
and Dallas county are ranked 3rd and 9th respectively by population. The effect of urban spatial structure on
housing prices in these areas also has implications for other large cities in the U.S. Second, housing prices
in Texas were more robust than other states during the most recent financial crisis. Prices of housing in
these four areas most likely reflect the fundamentals of housing market rather than speculative bubbles.
408
Third, the number of cities for any one metropolitan area, which is the sample size, is too small to draw
upon any stable statistical relationship. According to large sample theory, precise statistical inference can
only be obtained when the sample size is large enough. Hence we use data from four metropolitan areas
rather than focus on just one.
Figure 1. Geometrical locations of the four Texas metropolitan areas. The four yellow squares
denote: 1-Houston, 2-San Antonio, 3-Austin, 4-Dallas.
In practice, 8 counties were picked up that consist most of the territory. For Houston, we pick
Brazoria, Fort Bend, Galveston, and Harris County; for Dallas/Fort Worth, Dallas and Tarrant County; for
Austin, Travis County, and for San Antonio, Bexar County. We use County Level data to get the emission
inventory in 8 counties.

Table 1 and Table 2 show the changes of vehicle emission from 2004 to 2014. Table 1 shows the
changes in Peak hours. Table 2 shows the changes in Nonpeak hours. The emission level for 8 counties is
estimated to decrease.
The decrease of emission reflects that due to the economy recession, there is less VMT in 2014
than in 2004, in which year it was prosperous in economy. Also, new vehicle engine technologies and new
fuel sources have already reduced the amount of pollutants from each individual vehicle given driving same
distance in the same time period.
Table 3 shows that the emissions in peak hours are much more than those in nonpeak hours in 2014.
Table 4 shows the emissions in peak hours are much more than those in nonpeak hours in 2004. The
numbers in Table 3 are a little larger than the numbers in Table 4.
From Table 3, we can see that Harris County and Dallas County have the higher numbers than
others, while Brazoria has the lowest number in all 8 counties. The higher numbers in Dallas County and
409
Harris County reflect that the higher the population density in the area, the more emission in this area; the
lower the population density in the area, the less emission in this area.
TABLE 1. Peak Hour 2014 v.s. 2004

Peak CO2 CO NO2 NO NOx SO2 TotalEnergy Distance
Compare KiloTon KiloTon KiloGram KiloTon KiloTon KiloGram BillonJoule KiloMile
Brazoria -2.35% -26.18% -18.17% -8.15% -8.52% -84.61% -2.35% -0.83%
Fort Bend -2.32% -26.10% -17.73% -7.97% -8.34% -84.62% -2.32% -0.83%
Galveston -2.28% -26.67% -17.62% -7.92% -8.28% -84.61% -2.28% -0.83%
Harris -2.29% -21.13% -10.92% -2.19% -2.51% -84.55% -2.29% -0.83%
Dallas -2.32% -21.22% -11.26% -2.64% -2.96% -86.26% -2.32% -0.83%
Tarrant -2.34% -21.13% -11.28% -2.65% -2.97% -86.26% -2.34% -0.83%
Travis -2.32% -32.16% -18.62% -9.04% -9.40% -88.67% -2.32% -0.83%
Bexar -2.32% -33.73% -20.63% -11.31% -11.66% -90.39% -2.32% -0.83%
Total -2.31% -24.36% -13.53% -4.59% -4.92% -86.78% -2.31% -0.83%
TABLE 2. Nonpeak Hour 2014 v.s. 2004

Nonpeak CO2 CO NO2 NO NOx SO2 TotalEnergy Distance
Compare KiloTon KiloTon KiloGram KiloTon KiloTon KiloGram BillonJoules KiloMiles
Brazoria -2.03% -29.34% -17.48% -7.93% -8.30% -84.56% -2.03% -0.83%
Fort Bend -2.02% -28.96% -17.17% -7.75% -8.12% -84.51% -2.02% -0.83%
Galveston -2.02% -28.91% -17.08% -7.69% -8.05% -84.61% -2.02% -0.83%
Harris -2.00% -22.77% -10.24% -1.74% -2.07% -84.50% -2.00% -0.83%
Dallas -2.05% -23.04% -11.08% -2.52% -2.85% -86.23% -2.05% -0.83%
Tarrant -2.05% -23.02% -11.10% -2.53% -2.86% -86.22% -2.05% -0.83%
Travis -2.03% -35.30% -18.24% -8.91% -9.26% -88.62% -2.03% -0.83%
Bexar -2.01% -37.32% -20.10% -11.09% -11.43% -90.37% -2.01% -0.83%
Total -2.03% -26.71% -13.17% -4.41% -4.74% -86.73% -2.03% -0.83%
TABLE 3. Peak v.s. Nonpeak 2014

Peak V.S. CO2 CO NO2 NO NOx SO2 TotalEnergy Distance
Nonpeak
2014 KiloTon KiloTon KiloGram KiloTon KiloTon KiloGram BillonJoule KiloMile
Brazoria 12.53% 43.92% 1.57% 5.74% 5.60% 12.59% 12.53% 6.47%

Fort Bend 21.08% 49.89% 9.04% 12.30% 12.19% 20.61% 21.08% 14.03%
Galveston 23.60% 46.96% 10.50% 13.35% 13.24% 23.95% 23.60% 17.21%
Harris 25.28% 50.47% 11.85% 14.77% 14.67% 25.28% 25.28% 18.83%
Dallas 29.52% 62.54% 25.48% 27.05% 27.00% 29.58% 29.52% 19.97%
Tarrant 29.56% 64.52% 25.88% 27.49% 27.43% 29.53% 29.56% 19.68%
Travis 25.65% 55.99% 17.64% 20.09% 20.01% 25.52% 25.65% 17.07%
Bexar 25.69% 54.34% 13.47% 16.32% 16.22% 25.74% 25.69% 17.69%
Total 26.66% 56.23% 17.50% 19.92% 19.83% 26.62% 26.66% 18.54%
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TABLE 4. Peak v.s. Nonpeak 2004

Peak V.S. CO2 CO NO2 NO NOx SO2 TotalEnergy Distance
Nonpeak
2004 KiloTon KiloTon KiloGram KiloTon KiloTon KiloGram BillonJoule KiloMile
Brazoria 12.90% 37.77% 2.43% 5.99% 5.86% 12.95% 12.90% 6.47%

Fort Bend 21.45% 44.08% 9.79% 12.57% 12.46% 21.49% 21.45% 14.03%
Galveston 23.94% 42.47% 11.23% 13.62% 13.53% 24.00% 23.94% 17.21%
Harris 25.65% 47.35% 12.70% 15.29% 15.19% 25.66% 25.65% 18.83%
Dallas 29.88% 58.77% 25.74% 27.20% 27.15% 29.88% 29.88% 19.97%
Tarrant 29.93% 60.55% 26.13% 27.64% 27.59% 29.94% 29.93% 19.68%
Travis 26.02% 48.77% 18.19% 20.26% 20.18% 26.01% 26.02% 17.07%
Bexar 26.09% 45.99% 14.22% 16.62% 16.53% 26.09% 26.09% 17.69%
Total 27.03% 51.38% 17.99% 20.15% 20.07% 27.02% 27.03% 18.54%
Comparing Table 4 and Table 3, we can see that most of the numbers in Table 3 are decreasing a
little bit. This may reflect that new vehicle engine technologies and new fuel sources have already reduced
the amount of pollutants from each individual vehicle given driving same distance in the same time period.
This paper tries to characterize the air pollutants caused by additional travel time due to housing
price factors numerically. We could get preliminary results of air pollutants caused by additional travel time
due to housing price factors. In recent years, due to the economy recession from 2007 and the economy has
not gone back to the level of 2004 (but close to the level of 2004), the housing price, the VMT (commuting
by passenger cars) in the county, the population density just change a little. These make a little change in
emission inventories between 2014 and 2004.
This paper also tries to find out how much emission generates in one minute per vehicle in peak
hour and nonpeak hour. Based on the scope of this paper, we just get the rough results on this.
TABLE 5. Emission Inventory per Vehicle per Minute in 2004 and 2014
CO2 CO NO2 NO NOx SO2 TotalEnergy Distance
Year
(Gram) (Gram) (Gram) (Gram) (Gram) (Gram) (Joules) (Miles)
2004 peak 8.71 0.28 0.00 0.04 0.04 0.00 121.16 0.02
2014 peak 8.51 0.21 0.00 0.03 0.04 0.00 118.36 0.02
2004
6.85 0.19 0.00 0.03 0.03 0.00 95.38 0.02
nonpeak
2014
6.72 0.14 0.00 0.03 0.03 0.00 93.45 0.02
nonpeak
From Table 5, we can see that in 2004 the difference of emission per vehicle per minute between
peak hour and nonpeak hour is very big in NO2. In peak hour the emission is 51.38% more than that in
nonpeak hour in 2004. And in 2014, it is 56.23%, even bigger.
When we compare the emission in peak hour between 2004 and 2004, we found that the SO2 and
CO change a lot. SO2 dropped dramatically by 86.78% from 2004 to 2014 in peak hour, and by 86.73%
from 2004 to 2014 in nonpeak hour. CO dropped by 24.36% from 2004 to 2014 in peak hour, and by
26.71% from 2004 to 2014 in nonpeak hour.
CONCLUSIONS
In cities with population between 15,000 and 1,000,000, the increase of one additional minute of
411
average commuting time will be associated with 1.9 dollars less housing price per square foot (p-value:
0.038) (Qiao et al., 2014). And one more minute in peak hour generates CO2 8.51 grams, CO 0.21 grams,
NO 0.04 grams, NOX 0.04 grams in 2014 in these 8 Counties; one more minute in nonpeak hour generates
CO2 6.72 grams, CO 0.14 grams, NO 0.03 grams, NOX 0.03 grams 2014 in these 8 Counties.
Forecasting of future air pollutants has important health and policy-making implications. Using
MOVES as the forecasting instrument gives us some advantage over existing research. We find that the
simulated future emission from passenger cars will increase due to the economy prospect in the next few
years, which reflects the projected economic and population growth in this area.
ACKNOWLEDGEMENTS
The authors acknowledge that this research is supported in part by the United States Tier 1
University Transportation Center TranLIVE, and the National Science Foundation (NSF) under grants
#1137732. The opinions, findings, and conclusions or recommendations expressed in this material are those
of the author(s) and do not necessarily reflect the views of the funding agencies.
REFERENCES
Qiao, F., L. Liu, W. Long and L. Yu. 2014. “Impacts of Average Commuting Time on Housing Prices in
Texas Suburban Cities”, Proceedings of the 93rd Transportation Research Board Annual Meeting,
Transportation Research Board of the National Academies, Washington, DC, Jan 12-16, 2014.
Brodere, J. M. 2009. “E.P.A. MOVES to Curtail Greenhouse Gas Emissions”. The New York Times.
Emission Reduction Plan, 2008, City of Houston, Texas.
Motor Vehicle Emission Simulator (MOVES): Users Guide for MOVES2010b, 2012, U.S. Environmental
Protection Agency.
U.S. Environmental Protection Agency. 2010. MOVES2010 Highway Vehicle, Population and Activity
Data.
U.S. Environmental Protection Agency. 2010. Technical Guidance on the Use of MOVES2010 for Emission
Inventory Preparation in State Implementation Plans and Transportation Conformity.
U.S. Environmental Protection Agency. 2012. “Use of Data from Development of Emission Rates for the
MOVES Model,” Assessment and Standards Division Office of Transportation and Air Quality.
Younglove, T., G. Scora, and M. Barth. 2005. Transportation Research Record: Journal of the
Transportation Research Board, No. 1941, Transportation Research Board of the National Academies,
Washington, D.C., 2005, pp. 51–59.
412
MODELLING OF ROAD TRAFFIC NOISE DURING JOURNEYS IN MUMBAI

METROPOLITAN REGION, INDIA
Vishal Konbattulwar, Saurav Jain, and Nagendra R. Velaga

(Indian Institute of Technology (IIT) Bombay, Powai, Mumbai, India-400 076. India)
Problem statement: Due to increasing urbanization and growing traffic levels, Indian metro cities are more
and more confronted with the need to deal with the impact of noise in day-to-day life. In a survey conducted
by the Central Pollution Control Board, India, found that noise levels in all Indian metro cities are more
than permissible limit. In Indian metro cities like Mumbai, to a great extent day-to-day travel and
commuting could be considered as a predominant daily activity which leads to exposure to very high noise
pollution. Unlike most of the developed world, in India, in addition to vehicle engine noise and noise due
to interaction between road surface and tyres, most of source of noise is due to vehicle horn. Due to lack of
proper traffic system, driver discipline, high traffic volumes and congestion, drivers horn very often
throughout the journeys. Traffic noise causes health risk for passengers (e.g., increase the risk of ischemic
heart disease, including myocardial infarction etc) and also one of the reasons for many ill effects like high
blood pressure, fatigues, less efficiency at work and mental stress. Various research papers have proposed
a range of models to quantify the traffic noise levels at different traffic volumes, locations and at different
times. However, as far as authors are aware, there is no model developed to analyse the traffic noise level
experienced by a passenger inside the vehicle for Indian conditions and for different modes of transport
(e.g., non AC bus, AC car and two wheeler, etc).
Aim of the study: The primary aim of the study is to analyse and model traffic noise level experienced by
passengers inside the vehicles for Indian conditions and for different modes of transport.
Study area and Data collection: In this study, various routes of the Mumbai Metropolitan Region (MMR)
are selected with each having different traffic volumes, vehicular compositions and speeds etc. Various
modes of transport like buses and cars (with and without air conditioning facility), autos and two-wheelers
are being considered. In-vehicle traffic noise levels are measured along the routes during peak and non-
peak hours with the help of a noise meters and a GPS palmtop.
Method, analysis and result: After data collection, the data is processed in a GIS software and different
parameters (e.g., geographical location, type of road etc) are extracted. As a GPS palmtop carried out during
experiments, when the data is processed in a GIS software, it is easy to extract all the required parameters
along with noise levels. With the data what we have collected so far, about 24.2% of time the noise levels
go above 90dB. Further data collection is scheduled in Dec 2013. In this research project, a model which
could give the noise level which a person inside the vehicle will be exposed to during various conditions of
traffic and modes of transport. Multiple regression analysis will be done to analyse the traffic noise at a
particular location as a dependent variable. Many explanatory variables will be taken for formulating the
model such as traffic characteristics, vehicle classes, time of travel and various other location
characteristics. The validity of the model will be examined using several criteria such as the difference
between the observed value and the estimated value along with various other statistical tests in this study.
413
GLOBAL WARMING
AND
CLIMATE CHANGE
414
ADAPTATION OF AGRICULTURAL SECTOR TO THE IMPACTS OF CLIMATE CHANGE

IN ARID REGIONS: REALLOCATION OF IRRIGATION WATER AMONG THE
COMPETITIVE ADVANTAGE CROPS
Ahmed M. Alabdulkader2 (King Abdulaziz City for Science and Technology, Riyadh, Saudi Arabia)
Fawzi S. Awad and Ahmed I. Al-Amoud (King Saud University, Riyadh, Saudi Arabia)
ABSTRACT: Reallocation of agricultural water resources among competitive advantage crops in Saudi
Arabia was investigated at the aim to develop practical adaption programs to combat the potential
consequences of climate change. Special attention was given to optimize the reallocation of water resources
among the key production areas of date-palm trees. Mathematical sector modeling approach was applied
to produce an optimal allocation plan of water resources among the key production areas of date-palm trees
in Saudi Arabia that rationalize the water use and maximize the net returns. Results showed that there is a
need to consider growing date-palm trees in the regions of competitive water use advantages in the national
adaption programs (NAP) in Saudi Arabia.
Key words: national adaption program, net returns, mathematical sector modeling.
INTRODUCTION
Agriculture sector is among the most vulnerable sectors to the impacts of climate change, and its
vulnerability becomes more evident in arid and semi-arid regions. The significant role of the agricultural
sector is highly recognized worldwide as a key driver to achieve sustainable economic, social and
environmental development, accordingly, the international community, in particular, developing countries
has placed a special consideration to mitigate the impacts of climate change on agriculture sector and to
adapt to its impacts in a sustainable manner. One of selected planned adaptation actions in the agricultural
sector is the adjustment of planting dates and crop variety, crop relocation (IPCC, 2007), and more efficient
use of water including improved agricultural practices, irrigation management, and resilient agriculture
(IPCC, 2014) . Adaptation refers to “ adjustments in ecological, social, or economic systems in response to
actual or expected climatic stimuli and their effects or impacts. Also, it refers to changes in processes,
practices, and structures to moderate potential damages or to benefit from opportunities associated with
climate change” (UNFCCC, 2014).
This paper discusses action taken in Saudi Arabia to reallocate agricultural water resources among
competitive advantage crops aiming to develop practical adaption programs to combat the potential
consequences of climate change. Special attention was given to optimize the reallocation of water resources
among the key production areas of date-palm trees using a mathematical sector model.
The review of literature showed great efforts to address the adaptation of agriculture to the impacts of
climate change (Luke et al., 2014; Ariel, 2013; Al-abdulkader, et al., 2012. Marshall, 2013; Scott, 2102;
Dênis, 2012; Jerry, 2012; Malcolm, 2012; Khan, 2011; Quiggin, 2010; Nelson 2009).
STUDY AREA
Saudi Arabia is located in the far south west Asia, between 16.5°N–32.5°N Latitude and 213.75°–
236.25° Longitude (Map 1). It covers an area of approximately 2.25 million km2 and has a population of
about 28 million. It has an average annual rainfall of less than 150 mm in most parts. Extreme heat and
aridity are characteristic of most of Saudi Arabia with high temperatures often exceed 45 c° and low
precipitation which cause concomitant increase in the evapo-transpiration rate, a reduction in soil moisture
and erosion of the soil, which adversely affect agricultural products and water resources. Less than 2 per
cent of Saudi Arabia’s total area is arable land (PME, 2011).
2 akader@kacst.edu.sa
415
Map 1: Saudi Arabia in the world Map (http://en.wikipedia.org/wiki/Saudi_Arabia)
Saudi Arabia has a sensitive ecosystem for any level of climate change and most regions are highly
vulnerable to such changes, especially to desertification processes and water resources. In most regions,
climate change, as represented by a temperature increase, would elevate the levels of reference
evapotranspiration by about 1-4.5% at a 1ºC increase, and by about 6-19.5% at a 5ºC increase. Crop
irrigation water demands would rise by about 602 and 3,122 MCM at 1ºC and 5ºC increases, respectively.
The expected yield losses of different varieties of field crops (including cereals, vegetables, and forage
crops) and fruit trees (including date-palm trees) will range from 5% to more than 25%. In many regions,
water demand exceeds the sustainable levels of water supply. Conventional strategies to increase water
supply can no longer meet growing needs, and are unable to cope with the uncertainty arising from
increased climate variability and climate change. Sustained efforts are therefore needed to manage water
demand among economic sectors (PME, 2011).
Map 2. Observed temperature change based on trend over 1901-2012 (IPCC, 2014).
416
Map 3. Projected temperature change based on different emission scenarios (IPCC, 2014).
PROBLEM STATEMENT
Agriculture sector has been recognized as the most consuming sector of water resources in Saudi
Arabia, representing an average of about 86 per cent of the total water supply throughout the last three
decades. Around 72 per cent of the water consumed by agriculture sector was pumped from a nonrenewable
water resources (Figure, 1). Accordingly, the main objectives of the agricultural and water sectors will be
realized through adaptation of the following policies and targets (MoEP, 2010):
- Determining the agricultural crops to be grown and the associated water demand, within the
strategic framework of rational use of water.
- Expanding use of reclaimed wastewater for agricultural purposes.
- Continuing efforts to achieve ecological balance through combating desertification, and
conservation and development of pastures and forests.
- Enhancing competitiveness of agricultural activities, especially of small and medium-sized farms,
and softening terms of investment in agriculture.
- Encouraging innovation and supporting agricultural R&D.
- Intensifying methods of rationalization of water uses for all purposes.
- Achieving a balance between water development and water consumption.
- Expanding the application of advanced methods and technologies to both production and
consumption.
- Expediting issuance of the National Water Plan.
- Developing appropriate mechanisms for determining the shares of various uses of water.
- Promoting integrated management of water resources and water demand.
- Upgrading the scientific, technical and development capacities of the human resources operating
in the sector.
- Intensifying efforts to provide water and sanitation services reliably at high levels of efficiency.
- Working towards issuing new water tariffs to incentivize rational use of water for all purposes and
its conservation.
- Encouraging the private sector to invest in this sector by providing incentives and simplifying
procedures.
- Encouraging the trend towards reliance on renewable energy sources by the sector, particularly
solar energy.
417
25
20
15
10
0
1975 1980 1985 1990 1995 2000 2005 2010 2015 2020
Total demand of water total supply of water

Demand for agricultural water total supply non-renewable groundwater
Figure (1). Water demand for Agricultural VS. total supply of non-renewable water in Saudi
Arabia – 1975-2014 (MoEP, 1975-2010).

Date-palm crop grown in seven major cropping-production regions (study regions) in Saudi Arabia
were considered to optimize the cropping pattern in accordance with the regional competitive advantage.
Appling Alabdulkader et al., 2012 approach, the market structure was visualized in this study as having
two supply regions. Both regions compete to satisfy the national demand of date-palm crop. These supply
regions represents: i) supply from major date-palm cropping-production regions or study regions, and ii)
supply from outside study regions or the rest of the nation. At a given price, supply from study regions
would represent the difference between quantity demanded and quantity supplied from outside study
regions.
A mathematical sector model has been formulated to achieve the ultimate objective of this study
using LINGO optimizer modeling program (2008), a popular and reliable software used for solving
optimization models. The mathematical formulation of the formulated sector model comprised four key
components: objective function, resource constraints, national commodity balance, and national trade
balance.
The objective function of the sector model was to determine the optimal one-year cropping pattern
of date-palm in accordance with the competitive advantage in the major date-palm cropping-production
regions in Saudi Arabia. The model maximized the net annual return subject to the limited water supply
and arable land, given marketing and trade balance constraints.
J R
Z y = ∑ f (W jy ) −∑ C jry X jry − I jy + E jy for all j, r (1)
j =1 r =1
Where,
Z y = Net economic return, in terms of US $ year-1.
f (W jy ) = Welfare function which measures the area under excess demand equation for jth crop in
year y.
C jry = Average cost for the jth crop in rth study region, in terms of US $ ton-1.
X jry = Average yield for jth crop in rth study region, in terms of tons hectare-1.
I jy = Net national imports for jth crop in year y, in terms of tons.
E jy = Net national exports for jth crop in year y, in terms of tons.

J = Date-palm crop
R = 1, 2, 3, … 9 study areas
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The resource constrains ensured that the amount of the limited resources used in the production
process did not exceed the available levels of resources. Two key resource constraints were applied in the
model: water supply and arable land. Water supply constraint was presented in tow forms: a monthly water
supply and an annual water supply. The monthly water supply was used to overcome the seasonality of
production and to ensure that the irrigation water requirements of date-palm in study areas did not exceed
the available monthly water supply. While, the annual water supply constraint ensured that the annual
irrigation water requirements for date-palm in study areas did not exceed a specific quantity of water
annually. The mathematical illustration of the resource constrains was presented as follows:
∑
a t X jry ≤ birt
j ijr
for all i, r (2)
∑a j
y
wjr X jry ≤ wry for all r (3)
Where,
aijrt = Input-output coefficients that states the amount of ith resources required to produce one
hectare of jth crop in rth study region in time t.
X jry = Annual yield for jth crop in rth study region in terms of ton per hectare.
birt = Maximum amount of ith resource available in rth study region in time t.
y
a wjr = Irrigation water requirements (w) for jth crop in rth study region in year y.
wry = Maximum water supply in year y in rth study region.

I = Irrigation water requirement, and arable lands
T = 1, 2, 3 … 12 months
For date-palm, the national commodity balance comprised three key elements. These were average supply
in study areas ( GS jry ), net national import ( NI jny ) or net national export ( NE jny ), and excess national
demand ( Ed jny ). The national commodity balance for the net-imported date-palm aimed at ensuring that
the sum of the study areas’ supplies and the net national import was greater than or equal to the excess
national demand. On the other hand, the national commodity balance for the net-exported date-palm aimed
at ensuring that the sum of the regional supplies was greater than or equal to the excess demand plus net
national exports for date-palm. The national commodity balance was illustrated mathematically for the net-
imported and for the net-exporting date-palm, respectively, as follows:
Ed jny − NI jny − GS jry ≤ 0 (4)
Ed jny + NE jny − GS jry ≤ 0 (5)
Where,
Ed = Excess national demand for the jth crop in year y
y
jn
NI jny = Net national imports for the jth crop in year y
GS jry = Average production for the jth crop in year y
Ed dny = Excess national demand for exporting date-palm in year y.
NEdny = Net national exports for exporting date-palm (d) in year y
GS dry = Average production of exporting date-palm (d) in year y

The national trade balance ensured that the net national import ( NI jny ) for date-palm did not exceed a
maximum limit for net national imports ( I jny ) annually, and the net national export ( NE jny ) for date-palm
did not exceed a maximum limit for net national exports ( E jny ) annually. The national trade balance could
be illustrated mathematically as follows:
NI jny ≤ I jny (6)
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NE jny ≤ E jny (7)

Where,
NI = Net national imports for jth crop in year y
y
jn
I jny = Maximum limits for net national imports for jth crop in year y
NE jny = Net national exports for jth crop in year y
E jny = Maximum limits for net national exports for jth crop in year y
Table (1) shows the key input-output coefficients for the mathematical sector model including the average
values of the followings: yield, market price, production cost, and crop water requirements for date-palm
trees in the study regions in Saudi Arabia (Al-Amoud et al., 2010).
Around 40 farms were field-surveyed and some statistical year books were investigated to calculate
the required input-output coefficients.
TABLE 1. Mathematical programming sector model input-output coefficients in Saudi Arabia –

Date-palm crop.
Average Average Average
Average Net
market production Annual water
yield return
Regions price costs requirements
(ton ha-1) (US $ ton-1) (US $ ha-1) (US $ ha-1) (cm yr-1ha-1)
5.96 1245.33 3622.13 3800.05 5466

Riyadh
6.85 1066.67 2528.80 4777.87 6202
Makkah
5.33 2590.22 4336.27 9469.61 7231
Madenah
4.53 1955.56 5721.10 3137.59 5369
Qassem
11.30 1562.96 3099.20 14562.28 5371
Eastern
5.20 856.67 2457.87 1996.80 5682
Alwadi
5.23 1644.45 3582.67 5017.78 4832
Najran
Sources: Al-Amoud, et al. (2010), Ministry of Agriculture (2007), Ministry of Agriculture official
website. www.agrwat.gov.sa/public/portal, and Food and Agriculture Organization. www.fao.org.

Optimizing the cropping pattern of date-palm trees in Saudi Arabia in accordance with the regional
competitive advantage showed a great potential of Saudi Arabia to adapt to climate change and to
restructure its cropping pattern for date-palm trees in accordance with its limited water resources and arable
lands and to generate high net annual return equivalent to about 881.76 million US$ year-1 compared to
about 660.98 million US$ year-1 for the base year. In addition, the return for water use will increase in
average from 0.97 US$ cm-1 in base year to about 1.31 US$ cm-1 in the optimized date-palm trees cropping
pattern, (Table 2).
The optimized date-palm cropping pattern, also, would provide Saudi Arabia the opportunity to
reduce the date-palm cropping areas by about 4 per cent, from about 118,250 hectares to about 113,446
hectares and the water demand by about 1 per cent, from 681.06 million cubic meters a year to about 674.27
million cubic meters a year.
In terms of allocated cropping area among the considered study regions, the optimized date-palm
cropping pattern was given the priorities to grow date-palm in the Eastern region and Madenah region with
an allocated area equivalent to about 127 per cent and 54 per cent of the total cropping areas in Saudi
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Arabia, respectively, and to reduce the allocated areas in Riyadh region for date-palm by about 82 per cent
and Qassem region by 48 per cent, (Table 3).
TABLE 2. Annual net return for optimized date-palm cropping pattern vs. base year date-palm
cropping pattern in Saudi Arabia*
Difference
Optimized Return on water
Net return Base-year base vs. optimized cropping
Regions model use
area
(million US$ yr-1
(US$ ha-1 ) (million US$ yr-1 ) (million US$ yr-1 ) (per cent) (US$ cm-1 )
)
Riyadh 3800.05 137.94 25.49 (112.45) (82) 0.70
Makkah 4777.87 46.82 85.52 38.70 83 0.77
Madenah 9469.61 178.03 274.22 96.19 54 1.31
Qassem 3137.59 109.19 56.66 (52.53) (48) 0.58
Eastern 14562.28 164.55 374.28 209.73 127 2.71
Alwadi 1996.80 7.89 10.11 2.22 28 0.35
Najran 5017.78 16.56 55.47 38.91 235 1.04
Total 660.98 881.75 220.78 1.07
*Source: study analysis. Numbers between brackets are negative signed
Similarly, the optimized water requirements for date-palm cropping pattern showed a potential
reduction in water use by about 82 per cent in Riyadh region and about 48 per cent in Qassem region in
association with the reduction in the allocated area of date-palm in both regions, Table (4).
TABLE 3. Optimized date-palm cropping pattern vs. base year date-palm cropping pattern in
Saudi Arabia
Relative importance of Relative importance of Difference
Optimized
Base- base year date-palm optimized date-palm Base year vs.
date cropping
year cropping area at a cropping area at a optimized cropping
Regions area
national level national level area
(per
(ha) (per cent) (ha) (per cent) (ha)
cent)
Riyadh 36300 30.7 6709 5.9 (29,591 (82)
Makkah 9800 8.3 17899 15.8 8,099 83
Madenah 18800 15.9 28958 25.5 10,158 54
Qassem 34800 29.4 18059 15.9 (16,741) (48)
Eastern 11300 9.6 25702 22.7 14,402 127
Alwadi 3950 3.3 5064 4.5 1,114 28
Najran 3300 2.8 11055 9.7 7,755 235
Total 118250 100 113446 100 (4,804) (4.1)
CONCLUSIONS
Saudi Arabia is among the most vulnerable countries to the impact of climate change. Optimizing
the cropping pattern of date-palm trees in Saudi Arabia in accordance with the regional competitive
advantage showed a great potential of Saudi Arabia to adapt to climate change and to restructure its
cropping pattern in accordance with its limited water resources and arable lands and to generate high net
annual return equivalent to about 881.76 million US$ year-1 compared to about 660.98 million US$ year-1
for the base year, accordingly, the return for water use would increase in average from 0.97 US$ cm-1 in
base year to about 1.31 US$ cm-1 in the optimized date-palm cropping pattern. The optimized date-palm
cropping pattern, also, would provide Saudi Arabia the opportunity to reduce the date-palm cropping areas
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by about 4 per cent, from about 118,250 hectares to about 113,446 hectares and the water demand by about
1 per cent, from 681.06 million cubic meters a year to about 674.27 million cubic meters a year. The
findings of this research project are significant and will be of a great interest not only to researchers working
in the field but will also appeal to decision makers and to a broader audience.
TABLE 4. Optimized water requirements for date-palm cropping pattern vs. base year date-palm
cropping pattern in Saudi Arabia
Water Base-year water Optimized water Water saving
Regions requirements1 requirements requirements (base year vs. optimized)
(cm yr-1 ha-1) (million cm yr-1) (million cm yr-1) (million cm yr-1 ) (per cent)
5,466 198.42 36.67 (161.74) (82)
Riyadh
6,202 60.78 111.01 50.23 83
Makkah
7,231 135.94 209.40 73.45 54
Madenah
5,369 186.84 96.96 (89.88) (48)
Qassem
5,371 60.69 138.05 77.35 127
Eastern
5,682 22.44 28.77 6.33 28
Alwadi
4,832 15.95 53.42 37.47 235
Najran
Total 681.06 674.28 (6.79) (1.00)
ACKNOWLEDGMENT
The authors of this study are delighted to King Abdulaziz City for Science and Technology
(KACST) – Saudi Arabia for its enormous financial fund and encouragement.
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ADAPTATION OF FIELD CROPS TO CLIMATE CHANGES IMPACT
Tawfik* M.M., Thalooth A.T., E. M. Abd El Lateef, B. B. Mekki, Amany , A. Bahr and Magda , H.
Mohamed (Field Crops Research Dept. National Research Centre, Dokki ,Giza, Egypt)
The high sensitivity of field crops to climate conditions and the great uncertainty on the combined effects
of increasing CO2 concentration and projected changes in temperature and especially in rainfall patterns on
crops reveals the necessity to better understand the impacts of future climate for implement appropriate
adaptation and mitigation strategies in agriculture, to increase production and food security. Increase
temperatures in the northern hemisphere will have positive impacts on production of field crops. On the
contrary, in the southern Hemisphere, it is expected that, the increase of temperature will negatively affect
the crop production and water use efficiency. It is also expected to change the geographical distribution
map of the agricultural crops. Researchers predict that about 20-30% of plant species in the world will
extinct if the average temperature has risen one degree only. The agricultural sector is expected to be
affected strongly by these circumstances and also the productivity of the different crops will be affected by
rising temperature and increasing of the carbon dioxide in the atmosphere which will affects the
physiological needs of different crops such as rates of photosynthesis, respiration and evaporation, as well
as plant requirement from water and fertilizer and susceptibility to disease and time required for maturity.
It also expected that climatic region will change, resulting in the change crops map distribution, sowing
dates and productivity. Agricultural production is likely to be negatively affected by climate change starting
from the effect on natural, chemical and biological properties of the soil or through the spread of pests,
insects, diseases and other problems as well as the quantity and quality of crop production, especially in
low income and high rates of poverty countries, as they are highly affected by the impacts of droughts,
floods and hurricanes.
A recent option is (climate smart agriculture) practice which helps to protect the framers from the
adverse effects of climate changes, provide means to reduce greenhouse gases, sequester carbon in the soil,
use precision agricultural systems, increase the productivity on a sustainable basis and building resilience
in facing the environmental pressures to help farmers to adapt to climate change. All these objects can be
accomplished through climate smart agriculture practices which enhance the content of soil organic matter
and improve its capacity to retain water. Thus can strengthen the resilience of agricultural crops to face the
environmental pressures, tolerate the negative impact of climate change and conserve environment, as well
as improving crop production.
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INFLUENCE OF ENSO ON RAINFALL, STREAM FLOW AND VEGETATION IN PRANHITA

CATCHMENT, INDIA
Rajashree Vinod Bothale (National Remote Sensing Centre, Hyderabad, India)

Yashwant B Katpatal (Visvesvaraya National Institute of Technology, Nagpur, India)
ABSTRACT: Influence of El Niño Southern Oscillation (ENSO) on spatial and temporal variation in
rainfall, stream-flow and vegetation was studied at watershed scale. Analysis of long term annual rainfall
data (1970 - 2011) for Pranhita catchment, India identified three homogeneous rainfall regions by statistical
and spatial clustering and Upper Wardha watershed falls in one homogeneous region. Detailed analysis
during 2001 to 2011 using daily rainfall data, stream flow data and vegetation data from MODIS sensor
showed influence of ENSO events on different parameters. Rainfall distribution graphs during El Niño
event are characterized by peak and valley shape, early occurrence of rain followed by dry spell. Heavy
rains were generally observed during onset of monsoon which continued throughout the season in La Nina
years. Negative anomalies in rainfall and vegetation were observed in El Niño years. During rainy season
the effect of ENSO events is similar for El Niño and La Niña with deviation patterns in vegetation being
almost same for both the events. The average stream flow is higher during La Niña year. Both seasonal and
non-seasonal flows have negative correlation with ENSO indices. The study has captured the impact of
ENSO events even at watershed scale.
INTRODUCTION
ENSO is a pattern that occurs at irregular interval affecting the climate around the World. ENSO
shifts between the cool phase (La Niña) and warm phase (El Niño) and the neutral state irregularly within
a two to seven year period. Allan et al.(1996) showed that drier condition are introduced in India during El
Niño phase and wetter conditions are introduced during La Niña phase. ENSO influences the climate in
any region. The effect of two El Niños or two La Niñas is unlikely to be exactly same. ENSO effects on
the resources could be identified by studying the changes which have taken place during the events. By
identifying and describing the relationship between ENSO events and the parameters which are affected by
ENSO, a method could be developed to predict the impact of future ENSO events (IRI). Impact of ENSO
events could be studied by analysing set of hydrological, economic or other variables over shorter durations
of time. This will help in understanding climatic variability. The variables could be rainfall, crop yield,
water in the reservoir, status of forest etc.
Impact of ENSO on rainfall, vegetation and streamflow has been studied by many researchers all
over the World (Anyamba et al., 2002, Africa; Chandimala & Zubair, 2007, Srilanka; Shisanya et al., 2011,
Kenya; Sharda et al.,2012, Alabama, Bothale & Katpatal, 2014, India). Impact of ENSO undulations over
India has been studied by many researchers. Although, severe droughts in India have been associated with
El Niño events, El Niño does not always produce droughts (Kumar et al., 2006). In 1997 which was strong
El niño year, India experienced higher than normal rainfall and in 2002 which was weak El Niño year, the
Indian monsoon presented a deficit on rainfall (Maity and Kumar, 2006). Bhuvaneswari et al. (2013)
studied the Impact of El Niño/Southern Oscillation on Hydrology and Rice Productivity in the Cauvery
Basin, India and showed that an El Niño episode is correlated with rainfall, hydrology and rice productivity
in the Cauvery river basin. In general ENSO related studies are being carried out at national and regional
scale which provide regional outlook to the possible impact but for the inputs needed at larger scale for
decision making, it is imperative to study the impact at larger scale. The present study is carried out to
understand the impact of the past ENSO events on rainfall, vegetation and stream flow in the Upper Wardha
watershed in Pranhita catchment, India and to provide valuable inputs to watershed planners for
management of water resources.
STUDY AREA
Pranhita catchment (75050’ to 80058’ E, 18010’ to 21055’ N & elevation range 98 m to 1116 m)
in Godavari basin of India which lies in the Eastern Maharashtra and covers 1,08,352sq km was selected
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for regionalization of annual rainfall. Upper Wardha watershed, which lies in homogeneous zone identified
within Pranhita catchment was selected for detailed study. Kharif season (June-October) and rabi season
(November – March) are two major cropping patterns. Kharif crop depends mostly on rainfall. Normal
rainfall variation over the study area varies from 849 mm to 1095 mm. Majority of rainfall occurs in the
rainy (June – October) season.
FIGURE 1: Study area with a) Location map of Godavari basin, b) DEM and rainfall stations for
Pranhita catchment, c) Upper Wardha watershed. Circles represent raingauge stations and triangle
denotes gauge site.
Regionalisation based on yearly rainfall. To identify homogeneous rainfall regions in the Pranhita
catchment, annual rainfall data pertaining to 131 stations for the period 1970 – 2011 (Obtained from Indian
Meteorological Department) was used. After subjecting the data to basic quality checks, visual and
graphical checks, homogeneity tests were carried out to identify break in data caused by non-climatic
factors resulting from instrument recalibration or a linear trend resulted from a gradual but constant
degradation of the sensor. Based on the combined analysis of Mann Kendall test (MKT) (Mann, 1945;
Kendall, 1975), Pettitt test (PT) (Pettitt, 1979), the Standard Normal Homogeneity Test (SNHT),
(Alexandersson, 1986), Buishand range test (BT) (Buishand, 1982) and Von Neumann ratio test (VNRT)
(Von Neumann, 1941) 14 stations which failed the hypothesis for three or more tests were rejected.
Clustering in spatial domain was carried out for data regionalisation using yearly rainfall data. The
Agglomerative Hierarchical Clustering (AHC) technique has been used which is a bottom-up clustering
method where clusters have sub-clusters. It creates a nested tree structure from a dissimilarity matrix and
goes on combining all the objects (117 stations here) into sub clusters. In the present study there are 42
(years) observations and 117 variables (Stations). The proximity between two objects is measured by
measuring similarity or dissimilarity on dendrogram plot. Euclidian distance dissimilarity is used for
clustering. In spatial domain clustering, Australian National University’s Digital Elevation Model
Algorithm (ANUDEM) algorithm is used for spatial interpolation of the data. The number of clusters used
are same as obtained by dendrogram plot of statistical clustering. For deriving clusters, ISODATA
(Iterative Self Organizing Data Analysis Technique) clustering algorithm is used to classify the dataset into
homogenous groups. It uses partitioning clustering algorithm to generate various partitions which are
optimized for intra-cluster similarity and inter –cluster dissimilarity. Partitioning clusters result in exact
number of desired clusters. The partitions are independent of each other. The regions identified by both
the methods were tested for homogeneity using L-moment approach (Hosking & Wallis, 1997).
Analysis of daily rainfall data. Daily rainfall data for the period 2001 – 2011 for 13 stations influencing
the Upper Wardha watershed from Department of Agriculture, Government of Maharashtra
(http://www.mahaagri.gov.in/rainfall/index.asp) was summed in accordance with 16 day composite
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vegetation index data. Comparison was made between the fortnightly rainfall values for different rainfall
stations. Percent anomaly map in rainfall were generated after converting the point data to surface data
using ANUDEM algorithm and TOPOGRID function in ArcINFO (ArcGIS) and comparison was made
with long term normal for El Niño and La Niña years. ENSO characterisation based on the Oceanic Niño
Index (ONI) (based on SST departures from average in the Niño 3.4 region) showed the presence of normal
conditions in 2001, 2003, 2005 and 2008. The El Niño conditions prevailed in 2002 (Medium), 2004
(Weak), 2006 (Weak) and 2009 (Medium) where as La Niña conditions prevailed in 2007 (Medium), 2010
(Strong) and 2011 (Weak). Station wise analysis was also carried out to know the variability of each station
with normal during ENSO events.
Vegetation data from MODIS satellite and analysis. Understanding the spatial variability of vegetation
is possible through satellite derived data. Growing season Normalised Difference Vegetation Index (NDVI)
has a near linear relationship with rainfall. Time series of this index is used in understanding vegetation
and its response to change in rainfall. Seasonal to interannual dynamics of rainfall is better understood by
temporal NDVI data. MOD13Q1 product (16 days global 250 m vegetation index)downloaded from
www.earthexplorer.usgs.gov was used in the analysis. To understand the time response of agriculture and
forest, few sample points were selected all over the study.
Stream flow data. The study area is drained by river Vardha and its tributaries and the data records of gauge
site Hirwa are used in the analysis. Daily stream flow data was made available by Central Water
Commission for the period 2001 to 2011. Majority of rainfall occurs in the rainy season which spans
between June to October months. A correlation analysis was carried out between rainfall and runoff for
different years.

AHC method of clustering clearly divided all the stations into three distinct groups on dendrogram
which shows the attributes distances between each pair of merged classes sequence (Figure 2). Longer the
line on dendrogram, greater is the difference between clusters. Based on the separability of clusters shown
in the Figure 2, three clusters are retained in spatial clustering. The identified clusters are shown in Figure
3. Region #1 is characterized by moderate rainfall zone, Region #2 by very high rainfall zone and Region
#3 by high rainfall zone. L-moment statistics was calculated for all the groups identified by cluster analysis.
Discordancy measure for three regions was 0.17, 0.96 and 0.27. Homogeneity measure H1 was calculated
as -0.845, -0.357 and -0.262 for three zones respectively. Both the measures suggest that the identified
zones are homogeneous in nature. Trend analysis shows a positive trend in Region #1 which was also
confirmed by Mann Kendall Test. Upper Wardha watershed is selected for detailed analysis which lies fully
in Region #1.
Daily rainfall data is analysed and the rainfall pattern for few stations is shown in Figure 4. The
plots show a clear cut pattern in rainfall variation with ENSO events. Rainfall patterns in the years 2002,
2004, 2006 and 2009 show presence of multimodal rainfall curve. There is even delay in occurrence of
rainfall.
Strong La Niña year of 2010 exhibit a bell shaped curve with more rainfall across the stations in
the study area. Few stations in the La Niña year 2011 also show similar pattern but since the intensity of
the event was less, the effect is not very predominant. Total monsoon season rainfall is around 25% more
than the normal rainfall for La Niña years. El Niño years has received 27% less rains in 2004 and 2009.
The reduction was 21% and 14% in 2002 and 2006 respectively . Rainfall anomaly map shows the
deviation with long term normal. Total anomaly pattern was divided in six categories (Figure 5). Negative
anomalies are seen in El Niño years of 2002, 2004, 2006 and 2009 and positive anomalies are seen in La
Niña years.
To study the response of vegetation during ENSO years, MODIS derived NDVI images were used.
Deviation from normal was calculated by first getting average image from a total of 203 images. Spatial
distribution of vegetation anomaly map is given in Figure 6 for two El Niño years and three La Niña years
during rainy season. Study area is dominated by negative vegetation anomaly in El Niño years and positive
anomaly during La Niña years particularly in the start of growing season. In the beginning of rainy season,
El Niño years show more negative deviation in comparison to La Niña years. During rainy season the
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effect of ENSO events is similar for El Niño and La Niña with deviation patterns being almost same for
both the events.
FIGURE 2: Dendrogram (Cluster tree) for the 117 FIGURE 3: Regionaliosation of the rainfall
stations. Number in square on the tree branches stations in the Pranhita catchment
represents the cluster.
FIGURE 4: Rainfall variation over the years for few raingauge stations in the study area. Left
figure is for El Niño years and right figure corresponds to La Niña years.
Correlation between rainfall values and the average NDVI values over 200 agriculture points
distributed in the study area show a lag time of 15 days for maximum correlation for rainy season. An
increasing trend in the correlation was observed when correlation was calculated using entire year data.
NDVI values calculated over 38 sample points over forest did not show any impact of ENSO events.
Analysis of rabi and kharif crop productivity showed that the a strong La Niña event resulted in good
rabi productivity.
Figure 7 shows the relation between rainfall, runoff, and ENSO indices for rainy season (June-
October) and non-rainy season (November – May). The average streamflow is higher during La Niña year.
Seasonal and non-seasonal both the flows have negative correlation with NINO indices ONI and NINO3.4.
Strong La Niña event of 2010 has been captured very well by rainfall and runoff and also NINO index.
Correlation of ENSO indices is more with stream flow in comparison with rainfall. This is due to
rainfall occurring only in few months. The occurrence of dry anomaly in the year will affect the rainfall
and subsequent runoff. A dry anomaly in rainy season will result in drastic reduction of rainfall. A wet
anomaly in May – June may expedite the onset of rainfall and its volume but the rainfall will be absorbed
by the dry soil.
SUMMARY AND CONCLUSION

ENSO influences the climate variability on the scale of seasons to year to few years. Its effects
are different from one episode to the next, depending on the strength and structure of ENSO. ENSO
can enhance or reduce the normal seasonal variations in climate. The present study has analysed the impact
of ENSO conditions at watershed scale. Since the impacts of ENSO can be very subtle, a large Pranhita
catchment was regionalized using statistical and spatial method of clustering. Based on combined analysis,
428
entire catchment was divided into three regions. The identified regions were checked for homogeneity using
L-Moment approach. The detailed study was carried out in Upper Wardha watershed which lies within
Region #1 having a positive trend in annual rainfall.
(FIGURE 5) (FIGURE 6)
FIGURE 5: Rainfall anomaly map. Left column shows anomaly during El Niño years and right
column shows anomaly during La Niña years
FIGURE 6: Pattern of vegetation anomaly map over the study area for different dates in rainy
season
To understand the impact of ENSO on parameter, MODIS derived data along with daily rainfall
data and river flow data were used (2001-2011). From the analysis it became clear that year to year
variability in rainfall, streamflow and vegetation coincides with ENSO events with dryer conditions being
observed during El Niño years. The La Niña years experienced wetter conditions. The response of
watershed variables is dependent upon intensity of ENSO events. Predominant effect is seen during strong
events. A multimodal, less rainfall is observed during El Niño events. La Niña years have received more
and continuous rainfall resulting in bell shaped curve of rainfall. Knowledge about the pattern of rainfall
during ENSO events will be useful in determining onset of monsoon, probable volume of rainfall, length
of growing season and recession of monsoon which is necessary requirements for planners and managers
429
dealing with agriculture and water resources. Information about deviation from normal rainfall will be
helpful for agriculture planning which is rainfall dependent.
FIGURE 7: Stream flow and rainfall at Hirwa gauge site with ONI and Nino3.4 Index for a)
rainy season and b) Non rainy season
ACKNOWLEDGEMENT
The first author wishes to thank Director, NRSC, Hyderabad for giving the opportunity to present
paper in the conference.
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Geosciences, 2011, 2, 36-47
430
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431
PERFORMANCE COMPARISON OF METHODS FOR TEMPORAL PRECIPITATION

DOWNSCALING: THE KUNMING CASE
Hua Bai, Siyu Zeng, Jining Chen, Xin Dong

(Tsinghua University, Beijing, China)
ABSTRACT: Investigating potential impacts of climate change on urban drainage system requires
downscaling the daily precipitation given by the climate models into sub-daily results. There are two
important steps in this temporal precipitation downscaling, i.e. the selection of distribution forms of annual
maximum precipitation series and the determination of scale invariance options, which needs particular
attentions since the different combinations may lead to controversial results. This paper aims to identify an
appropriate combination to apply the downscaling processes for Kunming city, by the way of comparing
their corresponding performances. Three most cited distributions (Generalized Extreme Value (GEV),
Gamma, and Log-Normal), and two scale invariance options (simple and two-stage scaling) are considered.
For the simple scaling, the scaling parameter is fixed as one constant, in contrast, as to the two-stage one,
the calculation is divided into two stages using two separated parameters. Based on the quantitative
comparison of the four selected statistical indicators, GEV distribution and simple scaling method is finally
recommended to Kunming city. Since distinctions exist among the various selections of downscaling
options and the best fitted combination is case dependent, it is suggested that the performance evaluation
on a specific temporal precipitation downscaling process be a necessary step before its practical application.
Key Word. Climate change, temporal downscaling, urban drainage system, intensity-duration-
frequency relationship, statistical evaluation
INTRODUCTION
The issue of climate change impacts on urban drainage system attracted a lot of attention in recent
decade, since the densely populated urban areas with a high speed economic development (especially in
developing countries) are extremely vulnerable in the face of torrential rainfall (Berggren et al., 2012;
Keupers and Willems, 2013; Nie et al., 2009). Currently, General Circulation Models (GCMs) and Regional
climate models (RCMs) are the main tool for the projections of future precipitation, and to explore the
potential climate change impacts on urban drainage systems, temporal downscaling should be applied to
the precipitation outputs of GCMs or RCMs, since its temporal resolution is too course for system
simulation. At the same time, intensity-duration-frequency (IDF) relationships are mostly hired to provide
the information of rainfall properties to evaluate the design storm for hydrological infrastructures (Nguyen
et al., 2010; Willems and Vrac, 2011). Therefore, before the application of climate change impact
assessment in urban drainage systems, the IDF curves, which derived through the downscaled climate
model results, should be validated in the first place. And the performance comparison of different temporal
downscaling methods with the aim of selecting an appropriate one is crucial.
Temporal scaling with the aim of deriving IDF curve has been extensively studied in former
researches, and the discussion of the issue falls into two main stages. On one hand, the property of scale
invariance has been explored and discussed to explain the variability of a number of hydrological process,
such as river networks, surface and groundwater flows and precipitation (Michele et al., 2002). And these
literatures mainly published in the previous 1990s and even earlier (Fedder, 1988; Lovejoy and Schertzer,
1985). For instance, Rosso and Burlando proposed a simple scaling formulation of IDF curve in 1990, and
subsequently introduced a general distribution-free framework based on log-normal model, considering
both the conservative (sample scaling) as well as the dissipative (multiple scaling) nature of storm rainfall,
to derive IDF relationships in 1996 (Burlando and Rosso, 1996; Rosso, 1990). Furthermore, Menabde et
al. (1999) determined the scaling relationship of intensity with duration in terms of the parameters of the
Gumbel probability distribution, and Michele et al. (2002) considered the scaling properties of the rainfall
random field in time and space and derive the relationships that link mean rainfall intensity with area and
duration.
432
On the other hand, with the persistent research progress achieved on climate change, potential
impact on urban drainage system was concerned by downscaling the climate model outputs. Temporal
downscaling, with the main goal of deriving the sub-daily rainfall information from the daily data, was thus
widely applied according to the scale invariance property. Rodríguez et al. (2013) investigated the potential
changes of IDF relationships due to climate change in the metropolitan area of Barcelona, and two temporal
downscaling methods have been applied to obtain sub-daily rainfall data from the simulated daily rainfall
series. Nguyen et al. (2007) employed the scaling General Extreme Value (GEV) distribution to describe
the relationships between daily extreme precipitations and sub-daily extreme precipitations as a temporal
downscaling procedure. Moreover, different downscaling methods may lead to controversial results, so that
the performance comparison has been given a lot of attentions with the aim of selecting a more appropriate
one for local usage. For example, Okonkwo and Mbajiorgu (2010) have developed IDF curves for South
Eastern Nigeria using two methods (Graphical and Statistical), and compared the results consequently. The
results indicated that IDF data developed from the two methods were very close for the lower return periods
of 2 to 10 years, but differ for higher return periods of 50 to 100 years although the difference was not
significant.
Focusing on the two important steps in scale-invariance-based temporal precipitation downscaling,
i.e. the possibility distribution selection and determination of scale invariance options, this paper examined
the performances of different ways to convert the daily rainfall intensities into IDF curves. Three possibility
distributions and two scale invariance options were tested for the scaling properties, and four statistical
indicators were employed for the quantitative evaluation. On the basis of the precipitation data in Kunming
city, China, the appropriate combination was identified and recommended to apply the downscaling process
for local usage.
METHODOLOGY
The concepts of scaling and multi-scaling provide insights to the apparent complexities of
hydrological phenomena, through simple mathematical formulations (Michele et al., 2002). Fedder (1988)
defined that a scaling distribution function f(x) is scaling if the following equation exists ,which provides a
fundamental basis of temporal downscaling (Fedder, 1988). Burlando and Rosso (1996) demonstrated a
power law form of IDF relationship can be derived from the scale invariance concept (Burlando and Rosso,
1996), shown as Equation (2):
f x = C λ × f λx (1) Pv = λ × ¡¢v (2)
where λ∈[0,1], indicates the scale parameter. Pd and Psd represents the series of annual maximum rainfall
intensity at daily scale and sub-daily scale, respectively. And β represents the scaling exponent.
As the Eq. (3) indicated, the scale invariance of the distributions results in the equality of their
moments of order q. If the scale function is linear, K(q)= βq, the process is a simple scaling; otherwise the
process is multi-scale. In order to calculate the value of β, we can simply take the logarithm of both sides
of Eq. (3), which transforms it into Eq. (4):
〈¡v¥ 〉 = λ§ ¥
× 〈¡¢v 〉
¥
(3) ¨©ªa¡v c = K q logλ × loga¡¢v c
¥ ¥
(4)
In this form, the function of scaling exponent, is regarded as the slope of the relationship between
the log-transformed values of annual maximum series and the scale parameter, and could be obtained from
the log-log plot.
Once β is determined, the hourly rainfall intensity of various durations (1, 3, 6, 12, 18 and 24 hours)
could be calculated by the values of daily precipitation with the corresponding λ (1/24, 1/8, 1/4, 1/2, and
1). Repeat this process for different return periods (1, 2, 3, 5, 10, 15, 20, 25 years), the required IDF curve
could be drawn.
Since different distribution forms of annual maximum daily (AMD) precipitation allow diverse
daily rainfall intensities as input for temporal downscaling, and disparate scale invariance assumptions
influence how to determine the scaling exponent β, so in this paper, three most cited forms of possibility
distributions, i.e., Gamma, GEV, and Log-Normal, are considered for comparison. Meanwhile, two scale
invariance options including a simple scaling (or linear scaling) and a two-stage scaling (i.e. piecewise-
433
linear fitting) are tested. For the simple scaling, β is fixed as one constant during a whole day. As to two-
stage scaling, IDF calculation is divided into two stages using different parameter β1 and β2. The constant
β1 is used for computing intensities of rainfall lasting less than 6 hours, while the constant β2 for the
precipitation duration between 6 hours and 24 hours.
The IDF calculation for Kunming City involves 5 types of return periods (2, 5, 10, 15, and 25 years)
and 8 rainfall durations (1, 2, 3, 6, 10, 12, 18, 24 hours). For the sake of quantitative performance evaluation,
four indicators are used: mean bias error (MBE), root mean square error (RMSE), index of agreement (d)
and coefficient of determination (R2), showed as Equations (5) – (8). And the frame of reference for
comparison is the local existing IDF relationship obtained by the storm intensity formula, which is shown
as the Eq. (9).
x.´
MBE = ∑ UUIx V ° − V (5) RMSE = ² ∑ UUIx V ° − V ³ (6)
∑¶·¸| µ
^·¹ ”^ ”^
k ∑¶·¸| ”^µ ”^ k
- = 1 − ∑¶·¸| |”^ ”»¼½ |}|”^µ ”»¼½ | k (7) „ = 1 − ∑¶·¸|
^·¹
” ”»¼½ k
(8)
^·¹ ^·¹ ^
Where yi is observed values, yi’ is calculated values, yavg is the mean of observations.
. } I.I¿ÀÁ
i= } I.I |.Â|
(9)
In which, i stands for the rainfall intensity (mm/hour), P is return period (year), and t represents duration
(hour).
STUDY AREA AND DATA

Kunming city is located in the southwest part of China (
), within the latitude-longitude range of 102.10oE-103.40oE and 24.23oN -26.22oN, and is the
capital of Yunnan province with a population of 6.44 million (Province, 2011). The climate is
predominately subtropical monsoon, and wet and dry season are distinctively clear in a year. The mean
annual precipitation is approximately 980 mm, and the average temperature is around 15oC with a tight
fluctuation. The statistical analyses of annual rainfall depth and the monthly distribution amount, based on
the local meteorological records from 1951 to 2011, is shown as FIGURE 7 and FIGURE 8, respectively.
FIGURE 6. Descriptive map of Kunming city
The data used for temporal downscaling were provided by the National Climate Center, China
Meteorological Administration (CMA, http://www.nmic.gov.cn/), and included two sections: observed
434
daily precipitation values and hourly rainfall intensities. Firstly, the series of AMD precipitation, which
stands for the maximum rainfall series in a year, was extracted from the dataset of 1951-2011, and fitted by
the three selected possibility distributions. Subsequently, annual maximum values of hourly intensities
(duration of 1, 3, 6, 12 and 24) were obtained from the local observation records of 2003-2011, for the
determination of scaling exponent according to the corresponding computational equations.
FIGURE 7. 61-yrs observed annual FIGURE 8. The monthly distribution of

precipitation in Kunming city (1951-2011) average rainfall depth (1951-2011)

FIGURE 9 illustrated the fitted AMD precipitations and observations under different return
periods. It demonstrated clearly that, for low return period simulations (smaller than 10-year), all three
distribution forms shown the suitability with relative error controlled within 3%. However, for extreme
values, only GEV distribution provided acceptable results while the other two failed in high prediction
errors. With regard to the value of 25-year return period, the relatively error was negative 5%, 21% and
28% for GEV, Gamma and Log Normal distributions, separately. Since the fitted form of possibility
distribution plays the role of f(x) in Eq. (1), its accuracy determines the following computed IDF values
directly. In other words, it is necessary and important to compare and validate several candidates before
applying one for downscaling usage.
FIGURE 10 indicates the computed five orders of the moments of the annual maximum rainfall
intensities due to various durations. The slopes of the straight line fitting these points give the value of the
scaling exponent for each order moment, and the parameter β of simple scaling then estimated with these
slopes. In FIGURE 10, the piecewise-linear fitting was applied and the correlation coefficient for each
fitting were computed for illustrating the two-stage phenomenon and the calculation of β1 and β2 as well.
FIGURE 9. Comparison of AMD FIGURE 10. Moments for 5 different values

precipitation with different return periods of q of the annual maximum rainfall intensity
FIGURE 11 demonstrated the calculated IDF curves with return periods of 2-year and 25-year for
instance, typically representing drizzle and extreme events, respectively. The colour and symbol
combinations of the lines expressed the downscaled results using different temporal downscaling methods.
435
First of all, it shown clearly that disparities among IDF results caused by different downscaling options
exists, and the extent was increasing when return period increasing. Secondly, as to the IDF curves of 2-
year return period, the values of rainfall intensities based on the simple scaling matched the SIF values
well, with relative errors controlled within 5%. Meanwhile, the main disagreement rooted in the selection
of scale invariance option, although the curves obtained from multiple scaling did not appear to be much
different when the rainfall duration bigger than 6 hour. On the other hand, the situation of 25-year return
periods exhibits a much less concise and explicit image, not only the variance between the results computed
according to the different scale invariance options still exist, but also the disparities of various fitted
distributions shown up. All of these results suggested that the performance comparison of temporal
downscaling method is significance before one appropriate one was selected the local practice.
FIGURE 11. IDF curves comparison with different return periods
TABLE 3 reports the values of statistical indicators for the performance comparison of different
methods. All the four indicators shown that the results calculated by simple scaling is better than multiple
scaling. And moreover, the values of MBE indicated that all the results obtained by different methods are
smaller than the SIF values to some extent. Overall, the combination of GEV distribution and simple scaling
has overwhelming advantage than the others, and is recommend consequently.
TABLE 3. Performance comparison of different downscaling methods

NO. Items MBE RMSE d R2
1 LogNorm-Simple -1.86 3.13 0.9890 0.9599
2 GEV-Simple -0.59 1.42 0.9980 0.9917
3 Gamma-Simple -1.18 1.66 0.9971 0.9887
4 LogNorm-TwoStage -4.98 8.46 0.8865 0.7073
5 GEV-TwoStage -3.03 5.86 0.9531 0.8597
6 Gamma-TwoStage -4.44 7.52 0.9145 0.7687
CONCLUSION
The aim of this study was to compare the performances of different temporal downscaling methods
for climate change impacts investigations on urban drainage system. The six tested integrated methods were
on the basis of the combination of three possibility distributions and two scale invariance options. The
results indicated that, for fitting the distribution forms, there is no big difference among the three candidates
for the rainfall intensities with the return periods smaller than 10-year, but the performance varied a lot for
the extreme event where the relative error could be as much as 28% for the 25-year return period values.
As to the scale invariance options, the simple scaling appeared to be more reliable according to the
comprehensive assessment, and multiple scaling mainly underestimated the precipitation intensities with
the durations bigger than 6 hours. At last, based on the used precipitation data and selected evaluation index,
it was found that GEV distribution combining simple scaling performs best, and thus was recommended
for Kunming city.
436
ACKNOWLEDGMENT
This work was fully supported by the 2012 University of Nairobi-International Development
Research Centre (IDRC) Research Grants on Innovative Application of ICTs in Addressing Water-related
Impacts of Climate Change. We all gratefully acknowledge the help of Asian Management and
Development Institute (AMDI) during the research.
REFERENCES
Berggren, K., et al., 2012. Hydraulic Impacts on Urban Drainage Systems due to Changes in Rainfall
Caused by Climatic Change. Journal of Hydrologic Engineering 17(1): 92-98.
Burlando, P., Rosso, R., 1996. Scaling and multiscaling models of depth-duration-frequency curves for
storm precipitation. Journal of Hydrology 187: 45-64.
Fedder, J., 1988. Fractals. Plenum Press, New York.
Keupers, I., Willems, P., 2013. Impact of urban WWTP and CSO fluxes on river peak flow extremes under
current and future climate conditions. Water science and technology : a journal of the International
Association on Water Pollution Research 67(12): 2670-2676.
Lovejoy, S., Schertzer, D., 1985. Generalized scale invariance and fractal models of rain. Water Resources
Research(21): 1233-1250.
Menabde, M., et al., 1999. A simple scaling model for extreme rainfall. Water Resources Research 35(1):
335-339.
Michele, C.D., et al., 2002. IDAF (intensity-duration-area frequency) curves of extreme storm rainfall a
scaling approach. Water science and technology : a journal of the International Association on Water
Pollution Research 45(2): 83-90.
Nguyen, V.T., et al., 2010. Optimal rainfall temporal patterns for urban drainage design in the context of
climate change. Water science and technology : a journal of the International Association on Water
Pollution Research 62(5): 1170-1176.
Nguyen, V.T.V., et al., 2007. A statistical approach to downscaling of sub-daily extreme rainfall processes
for climate-related impact studies in urban areas. Water Science & Technology: Water Supply 7(2):
183-192.
Nie, L., et al., 2009. Impacts of climate change on urban drainage systems – a case study in Fredrikstad,
Norway. Urban Water Journal 6(4): 323-332.
Okonkwo, G.I., Mbajiorgu, C.C., 2010. Rainfall intensity-duration-frequency analysis for Southeastern
Nigeria. Agric Eng Int: CIGR Journal 12(1): 22-30.
Province, S.B.o.Y., 2011. Yunnan Statistical Yearbook 2011. China Statistics Press, Beijing.
Rodríguez, R., et al., 2013. Influence of climate change on IDF curves for the metropolitan area of
Barcelona (Spain). International Journal of Climatology: n/a-n/a.
Rosso, R.a.B., P., 1990. Scale invariance in temporal and spatial rainfall (abstract). Proceedings XV
General Assembly European Geophysical Society. Annales Geophysicae, Copenhagen, p. P. 145.
Willems, P., Vrac, M., 2011. Statistical precipitation downscaling for small-scale hydrological impact
investigations of climate change. Journal of Hydrology 402(3-4): 193-205.
437
BETTER TO SAVE A MW RATHER TO GENERATE A MW
Mehboob Alam Khan, Asif Hussain Siddiqui, Abdul Fawad

(K-Electric Limited, Opp Shaheen Complex, Adjacent to I.I Chundrigar Road, Karachi, Pakistan)
To mitigate adverse affects of Climate change we must conserve Energy, The impact of Energy
Conservation & Efficiency improvement is equivalent to installation of Power Generation Plant thus
reducing GHG emissions
Power shortage is one of the major challenges that are being encountered globally. Conservation
of energy is an effective and economical solution to cater the increasing electricity demand as compared to
electricity generation. Increasing generation has a profound impact on the excessive emission of greenhouse
gases (GHGs). In this paper, Energy conservation and improvement of Energy Efficiency is used as a tool
to influence the electricity demand curves (Reduction in present consumption of Electricity) thus reduction
in GHG emissions. A considerable decline in the monthly power demand is observed by implementing the
suggested solution which is equivalent to a power generation plant it helps in reduction of GHG emissions
on sustainable basis. The solutions presented are also an effective way to cater the gap between electricity
supply and demand.
K-Electric (Formerly KESC) is proactively working on this subject and formulated a department
of Energy Conservation with an aim to improve system Efficiency and to conserve valuable power. KE
also formulated a Climate Change policy with the following pillars/steps towards sustainability. KE
Climate Change Policy is to protect, conserve, preserve & improve the environment for the prevention &
control of pollution & to promote sustainable development.
 Energy Efficiency & GHG emission reduction

 Renewable Energy Infrastructure
 Energy Conservation
 Environment compliance and green zone development
Methods adopted by ECD-KE to improve Energy Efficiency and save valuable power.
• Energy Audits/technical consultancy

• Power factor improvement consultancy
• Projects installation and commissioning
• Alternate & Renewable Energy Projects.
• Technical Lectures at Universities/colleges
• Workshops /seminars (Mass Awareness)
• BTL activities
• Members of technical committees ( PSQCA,ENERCON ,EDB) to formulate Efficiency standards
• Research projects with NED and other institutes.
438
THE INTERACTIONS OF ROCK WITH CO2 AND BRINE UNDER CO2 SEQUESTRATION
CONDITIONS
Y. Soong*, L. Zhang, B. H. Howard, S. W. Hedges, R. Warzinski, R. Dilmore, D. J. Soeder, R. T.

McClendon and M. L. Gray (National Energy Technology Laboratory, DOE, Pittsburgh, PA, USA)
I. Haljasmaa and D. Crandall (URS, Pittsburgh, PA, USA)
Deep saline aquifers are reported to have the largest estimated capacity for CO2 sequestration. The Mount
Simon sandstone in the Midwest region of the U.S. is recognized as a promising candidate host reservoir
for carbon sequestration. The Mount Simon is a deep saline aquifer and is a primary reservoir target for
large scale carbon dioxide injection tests due to its proximity to CO2 sources, favorable depth, thickness,
permeability, porosity, and the presence of the overlying Eau Claire Formation as a seal. The Midwest
Geological Sequestration Consortium (MGSC) has selected the Mount Simon as the reservoir at its major
demonstration project. While the Mount Simon Sandstone has ideal reservoir characteristics in some areas,
there are significant variations in porosity, permeability, and mineralogy. Therefore, knowledge of possible
geochemically-induced changes to the porosity and permeability of host CO2 storage sandstone and seal
rock will enhance our capability to predict CO2 storage capacity and long-term reservoir behavior.
An experimental study of the potential interaction of CO2/brine/rock in saline formations in a static
system under CO2 sequestration conditions was conducted. Chemical interactions in the Mount Simon
sandstone environment upon exposure to CO2 mixed with brine under sequestration conditions were
studied. Samples were exposed to the estimated in-situ reaction conditions for six months. The experimental
parameters used were two core samples of Mount Simon sandstone; Illinois Basin model brine; temperature
of 85 °C, pressure of 23.8 MPa, and CO2. Micro-CT, CT, XRD, SEM, petrography, and brine, porosity,
and permeability analyses were performed before and after the exposure. Preliminary permeability
measurements obtained from the sandstone sample showed a significant change after it was exposed to
CO2-saturated brine for six months. This observation suggests that mineral dissolution and mineral
precipitation could occur in the host deposit altering its characteristics for CO2 storage over time. In
addition, a numerical simulation of porosity and permeability evolution of Mount Simon sandstone under
the same experimental conditions was conducted with the use of reactive transport modeling code
CrunchFlow. The comparison of experimental observations and simulation results will be discussed.
439
BIOREMEDIATION AND BIOTRANSFORMATION OF CO2 USING BIOCATALYST
Bhagat Chintan, Tank Shantilal, Bhavsar Sunilkumar, Dudhagara Pravin

(Department of Biosciences, Veer Narmad South Gujarat University, Surat-395007, Gujarat, India)
ABSTRACT: The advent of industrial and fossil fuel brought many advances in human life. On the other
hand it has deteriorated the environment and drive to rapid imbalance of Carbon. It is necessary to reduce
CO2 level to “safer” level. A biomimetic approach designed for sequestration of CO2 which resemble that
CO2 scrubber system. Approach utilizes the biocatalyst, Carbonic anhydrase that serves to catalyze the
hydration reaction of CO2 for subsequent fixation to stable mineral carbonates. Microbial Carbonic
anhydrase (CA) was isolated from the marine bacteria Alcaligenes faecalis species. It was able to grow
optimally at 5% CO2 saturated environment, Optimum CO2 hydration neutral pH and 35 °C temperature.
Furthermore, cations including 50 mM of each ZnCl2, KCl and CaCl2 were found to increase the enzyme
activity, specifically; 50mM ZnCl2 increased the activity nearly 2.3 fold. The enzyme was reported to
remain active against the high concentration of inhibitor, suggest the aptness for an on-site application. The
laboratory prototype was designed using the marine water as a source of the Ca+2 and enzyme mediated
reaction was performed using carbonated water and consequential calcite product was analyzed by SEM
and EDX. Further bacterial colonies capable to form calcite encrust. Calcite is valuable and better
supplement used with cement in the construction work.
Key Words. Carbonic anhydrase, Carbon sequestration, Calcite, Scanning Electron Microscopy
(SEM)
INTRODUCTION
Industrialization and fossil fuel accounts nearly 60 percent of CO2 emission (Kupriyanova et al.,
2007). Increasing the awareness of environment pollution and climate change apply positive pressure to
reduce CO2 to ‘safe’ level. Due to the limited scope of physical and chemical methods, there is an urgent
need for new approach that provides long term fate for storage. Biomimetic approach mimics the natural
phenomena of weathering using biological catalyst, carbonic anhydrase (CA), which offers obvious appeal
for long-term storage of CO2. Moreover, carbonates are thermodynamically stable, environmentally benign
and weakly soluble in water, thus minimizing the concerns over the monitoring requirements and long-term
fate of CO2 (Liu et al., 2005). The holistic approach at large scale requires a robust carbonic anhydrase
(CA) functioning at an alkaline pH and wide range of temperatures with appreciable tolerance to cations,
anions and other inhibitors.
Seawater has been considered as a potent supply source for calcium ions to form CaCO3 particles
(Bond et al., 2001). Thus, carbonic anhydrase can be useful for biotransformation of CO2 to CaCO3 using
seawater. Carbonic anhydrase is a Zinc metalloenzyme reported to be present in animals, plants and
microorganisms that catalysis CO2 hydration with typical reaction rate between 104 and 106 reactions per
second (Heck et al., 1994; Karlsson et al., 1998). Very limited numbers of bacterial species have been
reported for the fixation of large quantities of CO2 into CaCO3 by biomimetic approach.
Biomimetic CO2 sequestration by CAs is promising approach and holds an vast advantage over
other existing sequestration methods. It also provides a point source solution which does not require any
involving one of the fastest enzymes ever known (Liu et al., 2005; Druckenmiller and Maroto-Valer, 2005).
The aim of the proposed research was to investigate the carbonic anhydrase production and the
ability to form the mineral crust. In vitro evaluation of the Carbonic anhydrase was carried out to find out
the optimum function, activity and stability in various conditions along with CO2 sequestration.
MATERIAL AND METHODS

Isolation of bacteria was carried out on nutrient agar (NA) plates (pH 7.2). Primary screening for
esterase enzyme was performed by chromogenic substrate using 3mMpara-nitrophenyl acetate (pNPA)
(Ramaman et al., 2009). Based on the color development and intensity of the yellow color in the medium
selected best colony was screened for further study.
440
For carbonic anhydrase activity, pure culture was used inoculated in nutrient broth (NB) (pH 7.2)
and was incubated at 37°C in shaking condition at 120 RPM. Cells were harvested after 48 hours and cell
mass were collected by centrifugation at 10000 RPM for 10 minutes at 4°C. The cells were lysed using a
20mMGlycin-NaOH buffer (pH 9.0) followed by centrifugation at 5000 RPM at 4°Cfor 10 minutes to
obtain the crude extract of carbonic anhydrase. The carbonic anhydrase activity was estimated with the
modification of Alder et al., Method (Alder et al., 1972).
Enzyme activity was estimated as: (tT)-1 – (tS)-1/ X,
Where, tT and tSare the times in seconds required for a change in optical density in the presence (tT)
and absence (tS) of X mg of cell extract. Where, X is mg of protein content of the cell extract. Total Protein
concentrations were determined by the method of Folin-Lowary (Lowry et al., 1951).
To investigate CO2 tolerance pure culture of bacteria was inoculated in NB and culture was
incubated at specific CO2 concentration ranging from 0.035% to 5%. After 48 hours of incubation, optical
density (OD) of culture was measured at 660 nm.
To check calcite production, Culture was streaked on nutrient agar plates containing 0.75% CaCl2
(Stocks-Fischers et al., 1999) and incubated at 37ºC temperature for 2 days. Colonies were observed under
stereomicroscope.
The stability of the enzyme was monitored by Demir et al., method with certain modification
(Demir et al., 2001). Crude enzyme extract was incubated for 24 hrs at 37ºC with respective buffers ranging
from pH 7.0 to 9.0 followed by the residual activity measurement. Thermostability of the enzyme was
measured by pre-incubating crude enzyme extract for 30 min at 25ºC to 45ºC. Enzyme activity was
determined as residual activity.
Effects of cations were analyzed using Ramanan et al. with certain modification (Ramaman et al.,
2009). Three different concentrations, 50mM, 100mM and 200mM, of each cations were used to examine
the effect on carbonic anhydrase activity. The enzyme was incubated for 30 min with cations and its residual
activity was measured .
Four different concentration of widely used inhibitor, Sulfanilamide, was used to study the effect
of inhibition of the crude enzyme by incubating it at 37 ºC for 30 min (Alber and Ferry, 1994).The residual
enzyme activity was determined under standard assay conditions to find the IC50value.
Calcite synthesis was carried out with and without enzyme by the addition of sea water. Formation
of calcite production was collected by centrifugation followed by drying and analyzed by Scanning Electron
Microscope (SEM) and Energy Dispersive X-ray (EDX).
RESULT AND DISSCUSION

Carbonic anhydrase has wide distribution in prokaryotes (Smith et al., 1999). Potent isolate NAR8
was selected based on development of yellow color due to the yellow product (p-NP) formation around the
colonies as shown in Figure 1. Isolate was identified as Alcaligenes faecalis by decoding the 16srRNAgene
sequence followed by similarity search in GenBank.
Figure 1. Plate assay of culture exhibiting CA activity with yellow product of p-NP formed around the
colonies
The isolate was found to grow optimally at 5% CO2 and exhibited decline growth at 7.5 % CO2
(Figure 2). This indicates capnophilic nature of isolate and less number of capnophiles was evaluated. Large
cubic particles were found to aggregate in colony grown on solid media supplemented with CaCl2 indicating
441
the CaCO3 encrusts (Figure 3). This result was similar to earlier reports (Chen et al., 2008; Dick et al.,
2006).
The effect of pH on the stability of crude CA was examined in two different buffer systems, 20mM
Tris-HCl buffer (pH 6.5–8.5) and glycine–NaOH buffer (pH 9.0). The enzyme was found to retain
maximum activity at pH 7.0 while more than 94% enzyme activity was retained at pH 7.5, nearly70%
enzyme activity was found at pH 8.0 and half of the activity was found at pH 9.0 after 24 hours of incubation
at 37ºC (Figure 4). Thermostability of the enzyme was measured at various temperatures ranging from 25oC
to 45oCfor 30 min in 20mM Tris-HCl buffer (pH 7.0). There was a progressive decline in the stability of
CA following an increased in temperature ranging from 35oC to 45oC. The enzyme showed optimum
activity at 35oC. While, there was a drastic decline in the residual activity at 40oC and 45oC temperature
(Figure 5).
0.7
Absorbance at 660nm
0.6
0.5
0.4
0.3
0.2
0.1
0
0.035 2.5 5 7.5
% CO2
FIGURE 2. Growth kinetics in presence of CO2 FIGURE 3. Mineral crust of Calcium carbonate
2 2
CA acitivity (U/mg of
CA acitivity (U/mg of
1.5 1.5
protein)
protein)
1 1
0.5 0.5
0 0
6.5 7 7.5 8 8.5 9 25 30 35 40 45
pH Temperature (OC)
FIGURE 4. Effect of pH on Enzyme activity FIGURE 5. Effect of temperature on enzyme activity
TABLE 1. Effect of metal ion on enzyme activity

Residual activity (%) after 30 minutes
Concentration NaCl KCl ZnCl2 MgCl2 CaCl2 FeCl3
of ions
0 mM 100 100 100 100 100 100
50mM 66.6 150 233 50 150 43
100mM 100 100 300 25 66.6 25
200mM 233 25 400 12 43.2 20
Three different concentrations of each cations were used to test the CA activity after 30 min
incubation (Table 1). All the cations are essential for the optimum activity of the enzyme.Zn+2 were found
442
to greatly stimulate the enzyme activity. Except Fe+3 and Mg+2, all were reported to support the enzyme
activity. These results were found similar to previous researcher (Tripp et al., 2004; Sharma et al., 2008).
Four different concentrations of Sulphanilamide (0.1mM, 0.5mM, 1mM and 2.0mM) were tested
and result indicated good stability at each tested concentration of inhibitor. In the presence of 0.1 mM
concentration of inhibitor, negligible inhibition was found even IC50 value was also found greater than
2.0mM (Table 2).
There were differences in the size and morphology of CaCO3 crystals induced by enzymatic
process (Figure 6). The CaCO3 crystal morphologies induced by enzyme was rough-surface flower shaped
whereas, smooth-surface cubic crystals of CaCO3displayed in control reaction. Energy Dispersive X-Ray
Analysis (EDX) shows that Ca, C and O are major elements. These results were similar with past
researchers (Li et al., 2005).
TABLE 2. effect of inhibitor on enzyme activity

Concentration of inhibitor Residual activity (%) IC50value
0.1mM 91.30 >2 mM
0.5mM 82.60
1.0mM 65.21
2.0mM 53.17
FIGURE 6 A- cube shaped particle formed without enzyme, B- flower shaped particle formed in the
presence of enzyme, C- EDX profile of calcite powder
CONCLUSION
This study provides perspective for isolation of carbonic anhydrase from marine ecosystem for
biomimetic CO2 sequestration. The study investigates physicochemical factors to be important for active
and on site applicable CA isolation for carbon mineralization. It has been known that microorganisms play
an important role in promoting calcite precipitation. Positive Influence of CO2 on growth was evaluated.
Study of bacterial CA is one of the important biomimetic approaches for CO2 sequestration. Calcite
precipitation by bacterial CA leads to the formation of different types of calcite particles that can be used
as a supplementary material in the construction of the building.
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anhydrase.” Energy & Fuels. 15(2):309–16.
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Carbonate Minerals with Unusual Morphologies and Structures.” Crystal Growth & Design. 9(2):743–
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of a calcium carbonate layer on degraded limestone by Bacillus species.” Biodegradation. 17(4):357–
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Druckenmiller, M. L., and Maroto-Valer, M. M., 2005. “Carbon sequestration using brine of adjusted pH
to form mineral carbonates.” Fuel Processing Technology. 86(14–15):1599 – 1614.
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of mouse carbonic anhydrase V.” Journal of Biological Chemistry. 269(40):24742–6.
Karlsson, J., Clarke, A. K., Chen, Z-Y., Hugghins, S. Y., Park, Y-I., Husic, H. D., 1998.” A novel α-type
carbonic anhydrase associated with the thylakoid membrane in Chlamydomonas reinhardtii is required
for growth at ambient CO2.” EMBO J. 17(5):1208–16.
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Ramanan, R., Kannan, K., Sivanesan, S. D., Mudliar, S., Kaur, S., Tripathi, A. K., 2009. “Bio-sequestration
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444
SPACE DISTRIBUTION OF CARBON EMISSIONS IN CHINA
Mi Hong, Zhang Tiantian, Zhou Wei

(Zhejiang University, Hangzhou, China)
China is the largest emitor of carbon dioxide, and its total emissions keeps increasing quickly. There is
spacial imbalance on population distribution and economic activity, so the great difference existes in carbon
emissions of every provinces. We proposes concept of carbon emission per unit area (CEPUA), which can
measure the responsibility of carbon emissions of different regions more scientifically and more
objectively. With calculation model which is recommend by IPCC, and the data of population, areas of
every province, we calculate national total emissions, provincial carbon emissions per capita(CEPC),
provincial CEPUA in China from 1995-2010. Further more, we analyse the associated patterns of the
population, economy, CEPC and CEPUA. The space distribution of China’s carbon emissions is in the
shape of the letter T. Regions of China’s “high per person and unit area carbon emissions are in Beijing,
Tianjin, Shanghai, Liaoning, Hebei, Shandong, Shanxi, Jiangsu, and Zhejiang. Whereas, regions with “high
per person and low unit area carbon emissions are in Inner Mongolia, Ningxia, Xinjiang, Hei Longjiang
and Jilin. Regions with “high per person and unit area carbon emissions” and “high per person and low unit
area carbon emissions” constitute the shape of the letter “T”. Among them, along the vertical axis of T
shape are densely-populated and economy-developing provincial-level administrative regions which
dominate the China’s economy development.
445
446

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Environmental

Environmental Science and Technology 2014 Vol. 1

Includes bibliographical references

Printed in the United States of America

American Science Press, Houston, USA

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