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Arsenic Water Technology Partnership

Developing a New Class of Ion


Exchangers for Selective Removal of
Arsenic and Exploring an Engineered
Approach for Treatment and Reuse of
Spent Regenerant Brine and for
Enhanced Stability of Process Waste
Residuals
Developing a New Class of Ion Exchangers for Selective Removal of
Arsenic and Exploring an Engineered Approach for Treatment and
Reuse of Spent Regenerant Brine and for Enhanced Stability of
Process Waste Residuals

Prepared by:
Dongye Zhao (Principal Investigator), Thomas Steinwinder, Byungryul An,
and Mark O. Barnett
Department of Civil Engineering, Auburn University, Auburn, AL 36849

And
Timothy A. Kramer
Texas A&M University, College Station, TX 77843

Jointly Sponsored by:


Awwa Research Foundation
6666 West Quincy Avenue, Denver CO 80235-3098

and

U.S. Department of Energy


Washington, D.C. 20585-1290

Published by:

WERC, a Consortium for Awwa Research Foundation


Environmental Education and
Technology Development at
New Mexico State University

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About the Awwa Research Foundation

The Awwa Research Foundation (AwwaRF) is a member-supported, international,


nonprofit organization that sponsors research to enable water utilities, public health
agencies, and other professionals to provide safe and affordable drinking water to
consumers.

The Foundation’s mission is to advance the science of water to improve the quality of
life. To achieve this mission, the Foundation sponsors studies on all aspects of drinking
water, including supply and resources, treatment, monitoring and analysis, distribution,
management, and health effects. Funding for research is provided primarily by
subscription payments from approximately 1,000 utilities, consulting firms, and
manufacturers in North America and abroad. Additional funding comes from
collaborative partnerships with other national and international organizations, allowing
for resources to be leveraged, expertise to be shared, and broad-based knowledge to be
developed and disseminated. Government funding serves as a third source of research
dollars.

From its headquarters in Denver, Colorado, the Foundation’s staff directs and supports
the efforts of more than 800 volunteers who serve on the board of trustees and various
committees. These volunteers represent many facets of the water industry, and contribute
their expertise to select and monitor research studies that benefit the entire drinking water
community.

The results of research are disseminated through a number of channels, including reports,
the Web site, conferences, and periodicals.

For subscribers, the Foundation serves as a cooperative program in which water suppliers
unite to pool their resources. By applying Foundation research findings, these water
suppliers can save substantial costs and stay on the leading edge of drinking water
science and technology. Since its inception, AwwaRF has supplied the water community
with more than $300 million in applied research.

More information about the Foundation and how to become a subscriber is available on
the Web at www.awwarf.org.

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DISCLAIMER

This study was jointly funded by the Awwa Research Foundation (AwwaRF) and the
U.S. Department of Energy (DOE) under Grant No. DE-FG02-03ER63619 through the
Arsenic Water Technology Partnership. The comments and views detailed herein may
not necessarily reflect the views of the Awwa Research Foundation, its officers, directors,
affiliates or agents, or the views of the U.S. Federal Government and the Arsenic Water
Technology Partnership. The mention of trade names for commercial products does not
represent or imply the approval or endorsement of AwwaRF or DOE. This report is
presented solely for informational purposes.

Copyright 2006
By Awwa Research Foundation
and Arsenic Water Technology Partnership

All Rights Reserved

Printed in the U.S.A.

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ACKNOWLEDGEMENTS

This report is the product of a collaborative effort between the members of the Arsenic
Water Technology Partnership and was made possible by funds from congress and the
drinking water community. A special thanks to U.S. Senator Pete Domenici for his
support and assistance in helping to develop low-cost, energy efficient solutions for the
removal of arsenic from drinking water.

The research team is grateful to AWWARF project manager, Albert Ilges, and to the
Project Advisory Committee (PAC) for their advice and assistance throughout the
project. We are particularly indebted to Mr. John Balliew from El Paso Water Utilities
(the participating water utility), El Paso, TX, for his assistance with the semi-pilot scale
testing of the proposed technology for treating arsenic contaminated water from El Paso.

Partial in-kind support was provided by the participating El Paso Water Utilities, and the
Department of Civil Engineering of Auburn University.

The team is also grateful to our lab technician, Mr. Jinling Zhuang, for his technical
assistance during this study.

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CONTENTS

LIST OF TABLES………………………………………………………………………ix

LIST OF FIGURES……………………………………………………………….…….xi

FOREWARD...................................................................................................................xiv

ACKNOWLEDGMENTS……………………………………………………………..xiv

EXECUTIVER SUMMARY………………………………………………………….xvi

CHAPTER 1: INTRODUCTION…………………………………………………...1

1.1 Overview………………………………………………………………………….1

1.2 Objectives………………………………………………………………………...1

1.3 Arsenic Chemistry……………………………………………………………….2

1.4 Arsenic Origins…………………………………………………………………..3

1.5 Health Risks and Occurrence…………………………………………………...3

1.6 Legislation and Standards………………………………………………………3

1.7 Arsenic Removal Technology………………………………………...…………4

1.8 The Concept of Polymeric Ligand Exchange…………………………………..4

CHAPTER 2: SYNTHESIS OF POLYMERIC LIGAND EXCHANGERS……..8

2.1 Preparation of DOW 3N-Cu…………………………………………………..…….8

2.2 Synthesis of PLEs Based on Non-Functionalized Polymeric Sorbents (XAD)…...8

2.2.1 Materials……………………………………………………………………………8

2.2.2 Functionalization of XAD Copolymers………………………………..……...9


2.2.3 Copper Loading and Copper Capacity Measurement…………………..…12

CHAPTER 3: SORPTION AND DESORPTION OF ARSENATE USING


VARIOUS POLYMERIC LIGAND EXCHANGERS: BENCH-
SCALE TESTS ……………………………………………………..14

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3.1 Materials…………………………………………………………………………….14

3.2 Experimental Methods…………………………………………………………..…15

3.2.1 Equilibrium Sorption Tests…………………………………………………..15


3.2.2 Fixed–Bed Column Tests……………………………………………………..15
3.2.3 pH Effect………………………………………………………………………16
3.2.4 Kinetic Tests…………………………………………………………………..16
3.2.5 Resin Regeneration and Reuse………………………………………………16

3.3 Chemical Analysis…………………………………………………………………..16

3.4 Results and Discussion……………………………………………………………...17

3.4.1 Equilibrium Isotherms and Arsenate Adsorption…………………….........17


3.4.2 Breakthrough Behaviors……………………………………………………..20
3.4.3 Effect of pH……………………………………………………………………23
3.4.4 Kinetic Test……………………………………………………………………24
3.4.5 Regeneration and Reuse of PLEs………………….………………………...28

CHAPTER 4: ENGINEERED TREATMENT OF SPENT REGENERATION


BRINE………………………………………………………..……...33

4.1 Introduction……………………………………………………………….........33

4.2 Experimental Methods and Materials………………………………………...33

4.2.1 Preparation of Simulated Spent Brine…………………………………..33


4.2.2 Treatment of Spent Brine………………………………………………...33
4.2.3 pH and Aging Effect on Arsenic Removal………………………………34
4.2.4 Calcium Addition…………………………………………………………34
4.2.5 Regeneration with Treated Brine………………………………………..34

4.3 Results and Discussion………………………………………………………….34

4.3.1 As Removal from Spent Brine…………………………………………...35


4.3.2 Treated Brine Reuse……………………………………………………...38

CHAPTER 5: STABILIZATION OF SOLID WASTE RESIDUAL……………42

5.1 Introduction…………………………………………………………………….42

5.2 Materials and Methods…………………………………………………………42

5.2.1 Preparation of Arsenic-Laden Solid waste/Sludge……………………..42


5.2.2 Arsenic-Leaching Tests…………………………………………………..43

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5.2.3 Effect of Fe and Ca on Arsenic Stability………………………………..43
5.2.4 Effects of Aging and Temperature on Stability………………………...44

5.3 Results…………………………………………………………………………...44

5.3.1 Effect of Fe and Ca on Stability………………………………………….44


5.3.2 Effect of Aging and Temperature on Stability………………………….47

5.4 Discussion and Conclusions……………………………………………………55

CHAPTER 6: PRELIMINARY SEMI-PILOT SCALE TESTING OF THE PLE


TECHNOLOGY …………………………………………………...57

6.1 Experimental Procedures………………………………………………………57


6.2 Preliminary Column Run results……………………………………………...57

REFERENCES………………………………………………………………………….59

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LIST OF TABLES

Table 2-1 Properties of parent polymer matrices………………………………….... 9

Table 2-2 Maximum copper loading of the chelating resins………………………... 13

Table 2-3 Effect of chloromethylation time on maximum copper loading capacity


of di(2-picolyl)amine-functionalized XAD1180………………………… 13

Table 3-1 Salient properties of various ion exchange resins used in this study…….. 14

Table 3-2 The model-fitted Langmuir parameters (Q, b), and experimentally
determined arsenate/sulfate binary separation factor (αAs/S)…………… 19

Table 4-1 As remaining in solution after treatment and % initial As removed at


different Fe/As molar ratio and pH 6, 7, and 9. Initial As in brine was
310-350mg/L……………………………………………………………... 35

Table 4-2 Characteristics of three treated brine batches used for


regeneration…………................................................................................. 39

Table 5-1 Fe addition for stability tests……………………………........................... 43

Table 5-2 Calcium addition for stability tests……………………………………..... 44

Table 5-3 TCLP and WET results for effect of Fe addition on stability…………..... 45

Table 5-4 Amount of Ca added to each sample and the resulting effect on
extraction by TCLP (µg/L) and WET (mg/L)............................................ 46

Table 5-5 As remaining in brine and %As removed is shown after treatment where
contact time was 2, 20, and 60 days…………………………………….... 47

Table 5-6 Results of TCLP and WET tests for treatment at 2, 20, and 60 days.
Fe/As was held at 10 and pH adjusted to 5.5-6.5. Results of 3050B (acid
digestion) are also shown………………………………………………… 49

Table 5-7 Results of TCLP and WET reported in mg-As extracted per kg-sample
are shown for different aging periods (2, 20, or 60 days) and temperature
(5, 35, and 50ºC). Results of Method 3050B showing total As in sample
in mg-As per g-sample are also give…………………………………....... 50

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LIST OF FIGURES

Figure 1-1 A conceptualized illustration of the functional group of a PLE …….. 6

Figure 1-2 Breakthrough histories of phosphate and competing ions with DOW
3N-Cu (PLE)………………………………………………………… 6

Figure 1-3 Phosphate breakthrough curves with a commercial resin (IRA-958)


and DOW 3N-Cu…………………………………………………….. 7

Figure 2-1 Schematic and key reactions in synthesizing PLEs based on


polystyrene-DVB XAD polymers…………………………………… 11

Figure 2-2 Schematic and key reactions in synthesizing PLEs based on acrylic
polymers............................................................................................... 12

Figure 3-1 Arsenate sorption isotherms for DOW 3N-Cu and two conventional
SBA resins (IRA 900 and IRA 958) in the presence of competing
sulfate ions (Symbols: observed data; lines: Langmuir model fits)..... 17

Figure 3-2 Arsenate sorption isotherms for XAD1180-3N-Cu and XAD7HP-


3N-Cu in the presence of competing sulfate ions. (Symbols:
observed data; lines: Langmuir model fits)………………………….. 18

Figure 3-3 Breakthrough histories of arsenate and sulfate in a simulated multi-


component system using a standard SBA resin, IRA 900………….... 21

Figure 3-4 Breakthrough histories of arsenate and competing anions in a


simulated multi-component system using a polymeric ligand
exchanger, DOW 3N-Cu…………………………………………...... 22

Figure 3-5 Breakthrough histories of arsenate and competing anions in a multi-


component system using a polymeric ligand exchanger, XAD1180-
3N-Cu…............................................................................................... 22

Figure 3-6 Breakthrough histories of arsenate and competing anions in a multi-


component system using a polymeric ligand exchanger, XAD7HP-
3N-Cu…............................................................................................... 23

Figure 3-7 Arsenic uptake by DOW 3N-Cu as a function of solution


pH…………………………………………………………………..... 24

Figure 3-8 Experimental and model-simulated arsenate sorption kinetics of


DOW 3N-Cu. (Symbols: observed data; line: model simulation)…... 26

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Figure 3-9 Experimental and model-simulated arsenate sorption kinetics of
XAD1180-3N-Cu. (Symbols: observed data; line: model simulation) 27
Figure 3-10 Experimental and model-simulated arsenate sorption kinetics of
XAD7HP-3N-Cu. (Symbols: observed data; line: model simulation). 27

Figure 3-11 Arsenic elution profile during regeneration of saturated DOW 3N-
Cu using 4% NaCl (w/w) at pH 4.1, 7.0, and 9.1, respectively…....... 28

Figure 3-12 Arsenic elution profile during regeneration of saturated XAD1180-


3N using 4% NaCl (w/w) at pH 9.0……………………………......... 30

Figure 3-13 Arsenic elution profile during regeneration of saturated XAD1180-


3N-Cu using 6% NaCl (w/w) at pH 10…………………………….... 30

Figure 3-14 Arsenic elution profile during regeneration of saturated XAD7HP-


3N-Cu using 6% NaCl (w/w) at pH 10…………………………….... 31

Figure 3-15 Arsenic elution profile during regeneration of saturated XAD7HP-


3N-Cu using 8% NaCl (w/w) at pH 10…………………………….... 31

Figure 3-16 Comparing the equilibrium arsenate sorption (qe) of fresh and
regenerated DOW 3N-Cu under otherwise identical conditions.
(note: a. One cycle consists of one saturation run and subsequent
regeneration run; b. each point represents mean of duplicates, the
maximum standard deviation was 1.60)…………………………....... 32

Figure 4-1 Percentage arsenate removed from a simulated regenerant brine as a


function of the Fe/As molar ratio. Experiments were carried out at
pH 6, 7, and 9, respectively. Initial As concentration was 310-
350mg/L……………………………………………………………... 36

Figure 4-2 Percentage As removal at Fe/As 5-40. Three Ca additions are


shown, Ca/Fe 0, 0.5, and 1.5. Equilibrium pH was ~6………………. 37

Figure 4-3 Effect of pH on Arsenate removal from brine at a fixed Fe/As molar
ratio of 5 (filled circles) or 20 (open circles)………………………... 38

Figure 4-4 Elution history of arsenic during regeneration of DOW 3N-Cu using
a treated brine. Approximately 68% arsenic recovery was achieved
after ~34 bed volumes (BVs)………………………………………... 39

Figure 4-5 Elution history of arsenic during regeneration of DOW 3N-Cu using
a treated brine. Approximately 86% arsenic recovery was achieved
after ~34 bed volumes (BVs)……………………………………....... 40

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Figure 4-6 Elution history of arsenic during regeneration of DOW 3N-Cu using
a treated regeneration brine. Nearly 100% recovery of resin capacity
is achieved after 18 BVs…………………………………………....... 41

Figure 5-1 Extracted As in both TCLP-ext (left axis) and WET (right axis)
extraction fluids is shown as a function of iron addition. Data
represent mean of duplicates. Leaching tests were carried out 30-100
days after the sludge samples were air-dried………………………... 45

Figure 5-2 As concentration in TCLP and TCLP-ext extraction fluid with Ca


addition of 0, 15, 45, 75, and 105 mmol in a 500mL batch test. Data
are given as mean of duplicates. Leaching tests were carried out 20-
50 days after the sludge samples were air-dried…………………...... 46

Figure 5-3 Concentration of As in WET extraction fluid with Ca additions of 0,


15, 45, 75, and 105 mmol in a 500 mL batch. Data represent mean
of duplicates. Leaching tests were carried out 20-50 days after the
sludge samples were air-dried……………………………………….. 47

Figure 5-4 Percentage As removal as a function of aging (contact time) ranging


from 2 to 60 days. The brine treatment consisted of a Fe/As molar
ratio of 5 at pH 6-7 and at room temperature………………………... 48

Figure 5-5 Percentage As extracted by TCLP test for arsenic-laden sludge


samples that were aged (in their slurry form) for 2, 20, and 60 days,
respectively. Slurry aging was carried out at room 25 oC. Data
represent mean of duplicates. Leaching tests were carried out within
8 days after the slurry samples were air-dried……………………….. 49

Figure 5-6 Percentage As extracted by WET for arsenic-laden sludge samples


that were aged (in their slurry form) for 2, 20, and 60 days,
respectively. Aging was carried out at 25 oC. Data represent mean of
duplicates. Leaching tests were carried out within 8 days after the
sludge samples were air-dried……………………………………...... 50

Figure 5-7 TCLP results for samples aged for 2, 20, and 60 days and at 5, 25,
35, and 50ºC, respectively. Data represent mean of duplicates. Error
bars represent standard deviation. Leaching tests were carried out
within 8 days after the sludge samples were air-dried……………..... 51

Figure 5-8 Percentage of total As leached by TCLP for sludge samples aged for
2, 20, and 60 days, respectively, and at 5 and 50 oC, respectively.
Data represent mean of duplicates. Error bars represent standard
deviation. Leaching tests were carried out within 8 days after the
sludge samples were air-dried……………………………………...... 52

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Figure 5-9 WET results for samples aged (in their slurry forms) for 2, 20, and
60 days, respectively, and at 5, 25, 35, and 50ºC, respectively. Data
represent mean of duplicates. Error bars represent standard
deviation. Leaching tests were carried out within 8 days after the
sludge samples were air-dried………………………………….......... 53

Figure 5-10 Comparison of As leachability as a function of slurry aging and at


5ºC (filled circles) and 50ºC (open circles). Data represent mean of
duplicates. Error bars represent standard deviation. Leaching tests
were carried out within 8 days after the sludge samples were air-
dried……………………………………….......................................... 54

Figure 5-11 Percentage As extracted by WET as a function of temperature. All


three aging periods indicate that leachability decreases with
increased temperature. Data represent mean of duplicates. Error bars
represent standard deviation. Leaching tests were carried out within
8 days after the sludge samples were air-dried……………………… 54

Figure 6-1 Arsenate and sulfate breakthrough histories during a semi-pilot scale
fixed-bed column run using DOW 3N-Cu for treating a
contaminated well water from El Paso Water Utility………..……… 58

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FOREWORD

The Awwa Research Foundation is a nonprofit corporation that is dedicated to the


implementation of a research effort to help utilities respond to regulatory requirements
and traditional high-priority concerns of the drinking water community.

The Arsenic Water Technology Partnership (AWTP) program is a partnership between


AwwaRF, Sandia National Laboratories (SNL) and WERC, a Consortium for
Environmental Education and Technology Development at New Mexico State University
that is funded by DOE and the Awa Research Foundation. The goal of the program is to
provide drinking water utilities, particularly those serving small and rural communities,
with cost-effective solutions for complying with the new 10 ppb arsenic MCL. This goal
is being met by accomplishing three tasks: 1) bench-scale research to minimize
operating, energy and waste disposal costs; 2) demonstration of technologies in a range of
water chemistries, geographic locales, and system sizes; and 3) cost effectiveness
evaluations of these technologies and education, training, and technology transfer.

The AWTP program is designed to bring new and innovative technologies developed at
the laboratory and bench-scale to full-scale implementation and to provide performance
and economic information under actual operating conditions. Technology transfer of
research and demonstration results will provide stakeholders with the information
necessary to make sound decisions on cost-effective arsenic treatment.

AwwaRF participates in the overall management of the program, helps to facilitate the
program’s oversight committees, and administer the laboratory/bench-scale studies. SNL
conducts the pilot-scale demonstrations and WERC oversees the education, training,
economic analysis, and outreach activities associated with this program.

Walter J. Bishop Robert Renner


Chair, Board of Trustees Executive Director
Awwa Research Foundation Awwa Research Foundation

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ACKNOWLEDGMENTS
The research team is grateful to AWWARF project manager, Albert Ilges, and to
the Project Advisory Committee (PAC) for their advice and assistance throughout the
project. We are particularly indebted to Mr. John Balliew from El Paso Water Utilities
(the participating water utility), El Paso, TX, for his assistance with the semi-pilot scale
testing of the proposed technology for treating arsenic contaminated water from El Paso.
The primary funding for this Phase-I research was provided by AWWARF
(Project 3076). Partial in-kind support was provided by the participating El Paso Water
Utilities, and the Department of Civil Engineering of Auburn University.
The team is also grateful to our lab technician, Mr. Jinling Zhuang, for his
technical assistance during this study.

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EXECUTIVE SUMMARY

Introduction

The new arsenic (As) Maximum Contaminant Level (MCL) of 10 μg/L will impact
~4,100 water utilities serving nearly 13 million people nationwide, with an estimated
compliance cost of ~$600 million per year using current treatment technologies.
Although the ion exchange (IX) technology is identified by EPA as one of the best
available technologies for arsenic removal, conventional IX processes suffer from two
major constraints: 1) the sorption capacity is severely retarded by ubiquitous competitive
anions such as sulfate; and 2) large volumes of hazardous residuals are produced due
primarily to frequent regeneration. Consequently, innovative IX materials are urgently
needed for developing cost-effective IX processes for arsenic removal. This exploratory
research addresses the urgent needs for enhanced arsenic removal in small drinking water
systems. The research objectives are to:

• Develop and characterize a new class of innovative ion exchange (IX) materials,
referred to as polymeric ligand exchangers or PLEs, which can remove As(V) highly
selectively even in the presence of high concentrations of competing ions and requires
much less regenerant brine (<10% of the brine need of conventional IX resins); and
• To explore an engineered approach for brine treatment, which allows for reuse of the
spent brine and production of environmentally safe arsenic-laden solid waste.

Materials and Procedures

Five representative PLEs, designated as DOW 3N-Cu, XAD1180-3N-Cu, XAD1180-


2N-Cu, XAD7HP-3N-Cu, and XAD7HP-2N-Cu, were synthesized and studied in details.
DOW 3N-Cu was prepared by loading Cu(II) ions onto a commercially available
chelating resin (DOW 3N), whereas the other two sorbents were synthesized by loading
Cu(II) ions onto two chelating resins prepared by modifying two different polymer
matrices XAD1180 and XAD7HP, respectively. For comparison, two commercial strong-
base anion (SBA) exchange resins (IRA 900 and IRA 958) were also studied.
Isotherm tests were carried out in a series of batch experiments and in the presence of
high concentrations of sulfate as competing anions to determine the equilibrium arsenate
sorption capacity for the resins. Isotherm tests also resulted in the binary arsenate-to-
sulfate separation factors for comparing the relative affinity of various sorbents.
A series of bench-scale fixed-bed column tests and a semi-pilot scale column run
were carried out to study breakthrough behaviors of arsenate and various competing ions.
Regeneration of the exhausted PLE was also conducted in the same column
configuration.
To minimize the brine need and reduce the production of process waste, the
treatability and reusability of spent regeneration brine were studied. Ferric chloride was
used to precipitate/co-precipitate arsenic in a simulated spent brine solution containing
arsenate (300 mg/L), sulfate (600 mg/L), bicarbonate (5 meq/L), and NaCl (4% w/w).
Arsenic removal at various Fe/As molar ratios, pH, and aging time was tested in multiple

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batch reactors. After optimal conditions were determined, the spent brine was treated and
the supernatant separated from the precipitates. Upon pH adjustment to 9-10, the
recovered supernatant was reused for regeneration.
To reduce As leachability from the resultant process waste sludge, an engineered
procedure was developed by testing and optimizing the factors (Fe/As molar ratio, Ca
addition, reaction contact time or aging, and temperature) that affect the leachability of
arsenic. Both the standard TCLP and the California Waste Extraction Test (WET) were
employed to determine the stability of the residuals resulting from various treatments.

Results

All PLEs demonstrated orders of magnitude greater selectivity for arsenate than the
commercially available standard SBA resins (IRA 900 and IRA 958). Among the three
PLEs studied in detail, DOW 3N-Cu appears to be the most promising PLE to achieve
highly selective removal of arsenate in the presence of high concentrations competing
anions such as sulfate. Because of the high arsenate selectivity, the arsenate capacity of
DOW 3N-Cu is 17 times greater than that for the standard SBA resins based on the
Langmuir capacity coefficient. In contrast, the standard SBA resins are more selective for
sulfate over arsenate, resulting in much lower arsenate capacity.
Fixed-bed column experiments confirmed that the high arsenic capacity and
selectivity of the PLEs. While the standard SBA resin (IRA 900) showed a higher
selectivity for sulfate over arsenate. The breakthrough curves indicate the following
completely different affinity sequences: SO42- > HAsO42- > Cl- for IRA 900, but HAsO42-
>> HCO3- > SO42- > Cl- for the PLEs. Because of the high arsenate selectivity, most of
the PLEs’ sorption capacity is used for arsenate uptake. Compared to the standard SBA
resins, DOW 3N-Cu can treat over 6,000 bed volumes of contaminated water, which is
over 10 times more than that for a standard SBA resin, which means that the regeneration
frequency for the PLE is only 1/10 that for standard SBA resins. The high arsenate
selectivity and capacity of DOW 3N-Cu was confirmed in a semi-pilot scale fixed-bed
experiment using field contaminated water from El Paso Water Utility.
In addition to the high arsenate selectivity, the PLEs also exhibit reasonably fast
sorption kinetics. The diffusivity value (D) for DOW 3N-Cu was determined to be ~1.0 x
10-7 cm2/s, which is comparable to that for standard macroporous ion exchange resins.
Despite the high arsenate selectivity, the PLEs are amenable to highly efficient
regeneration using brine. For example, more than 96% of the arsenate capacity for DOW
3N-Cu can be recovered using 22 bed volumes of 4% (w/w) NaCl at pH 9.1.
Furthermore, the same regenerant brine can be repeatedly used seven times without any
treatment but pH adjustment, which further cuts down the brine need and results in a very
small volume of the exhausted brine.
Because of the minimal use of regenerant brine, arsenate is concentrated in a small
volume of exhausted brine, allowing for further physical-chemical treatment of the waste
brine in a cost-effective manner.
Treatment of the spent brine is geared toward 1) reuse of the spent brine, and 2)
enhanced stability (less arsenic leachability) of the final arsenate-laden solid waste.
Nearly all (>99%) of As in the spent brine can be removed using FeCl3 at a Fe/As molar
ratio of 2 or greater and at pH up to 7. When a Fe/As molar ratio of 10 or higher is used,

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the high arsenic removal was achieved over the pH range of 3-11. When the treated brine
was stored (aged) in contact with As-laden precipitates over prolonged times (up to 90
days), the removal efficiency remained unchanged. Upon pH adjustment, the treated
brine was able to completely regenerate an exhausted column, recovering 100 % of the
resin capacity in only 22 BVs.
Arsenic leachability from the process waste sludge was investigated by the standard
TCLP and as well as the California WET. It was observed that the current and predicted
future TCLP standard for waste disposal can be easily satisfied at a Fe/As molar ratio of 5
or greater. To further reduce the arsenic leachability, effects of various factors such as
Fe/As molar ratio, calcium addition, aging, and temperature on arsenic leachability were
investigated. When the Fe/As molar ratio was increased from 5 to 15, the arsenic
leachability was reduced by 98% (TCLP) and 93% (WET). Furthermore, it was observed
that the presence of low concentrations of calcium (30-150 mmol/L) can further increase
the stability of the process sludge. When the treated sludge was wet-aged from 2 to 20
days at 25oC, a 10% drop in leached As was observed. When wet-aged for 20 days or
longer, an increase in the aging temperature from 25oC to 50oC reduced the WET-
leachable arsenic by more than 23%. The results suggest that moderate aging and thermal
treatment of the process waste sludge may greatly enhance the stability of the waste
residuals.

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CHAPTER 1. INTRODUCTION

1.1 Overview

The presence of arsenic (As) in the U.S. waters is widespread. It was estimated
that 14% of groundwater sources exceeded 5 µg/L in various regions of the U.S. (Focazio
et al., 1999). The U.S. EPA estimates that approximately 2% of the U.S. population
receives drinking water containing > 10 µg/L As (Holm, 2002), and the Natural
Resources Defense Council estimates that ~56 million people in the U.S. drinking water
with As at unsafe levels.
Arsenic has been associated with various cancerous and non-cancerous health
effects. According to a recent report by the National Academy of Science (NAS) and
National Research Council (NRC), even at 3 µg/L of As, the risk of bladder and lung
cancer is between 4 and 7 deaths per 10,000 people. At 10 µg/L, the risk increases to
between 12 and 23 deaths per 10,000 people (NRC, 2001). In addition, As can cause high
blood pressure and diabetes (NRC, 2001).
Ion Exchange (IX) is currently an EPA-identified best available technology
(BAT) for removal of As(V) (EPA, 2000a). However, current commercial SBA resins
suffer from poor selectivity for arsenic. Due to the strong competition from some
ubiquitous anions such as sulfate, the arsenic capacity of SBA resins is prohibitively
retarded (Clifford, 1999). For example, the binary arsenate/sulfate separation factor for a
typical SBA resin was reported to be ~0.5 (a separation factor of less than 1 indicates the
resin’s preference toward the competing ions) (Clifford, 1999). As a result, the As
breakthrough occurs before sulfate, and chromatographic peaking of As, i.e. effluent
concentration exceeds influent concentration, is often observed (Kim et al., 2003).
Due to the lack of As-selectivity, current IX processes require frequent
regeneration. As a result, large amounts of regenerant brine are needed, which in turn
results in large volumes of As-laden process residuals (EPA, 2001a; EPA, 2002). The
spent regenerant brine and the associated waste residuals contain high levels of As, and
often fall into the category of hazardous waste that is subject to stringent disposal and
management requirements under the clean water act (CWA) and the Resource
Conservation Recovery Act (RCRA).

1.2 Objectives

The proposed research plan addresses the urgent technology need for cost-
effective arsenic (As) removal from drinking water and for minimizing the environmental
impacts of process waste residuals. The overall goal of this project was to develop an
innovative, selective ion exchange (IX) process that: 1) removes As(V) highly selectively;
and 2) minimizes the volume and As-leachability of process waste residuals. The specific
research objectives were to:

1). Prepare and characterize a new generation of IX materials, referred to as polymeric


ligand exchangers (PLEs), for highly selective removal of As(V) under normal

1
drinking water conditions (pH, ionic strength, competing ligands, metal ions, and
dissolved organic matter (DOM));
2). Test the regenerability of the PLEs and reusability of the spent regenerant; and
3). Develop an engineered approach to treat the spent regenerant and to minimize the
volume and As-leachability of process waste residuals.

The proposed study will test the following four key hypotheses:

1). PLE’s of high As(V) selectivity and capacity can be prepared based on high capacity
chelating ion exchange resins, which are either commercially available or can be
synthesized by modifying and functionalizing commercially available polymeric
matrices;
2). PLEs can remove As(V) much more effectively than conventional IX materials under
normal drinking water conditions in terms of sorption selectivity, capacity and
kinetics;
3). PLEs can be regenerated efficiently using brine, and the same regenerant brine can be
used multiple times without major treatment; and
4). As in spent brine can be effectively co-precipitated using iron and the process can be
engineered to increase the long-term stability and decrease the As leachability of the
final process residuals. After treatment, the spent brine can be reused.

1.3 Arsenic Chemistry

Arsenic (As) is a naturally occurring element present in rock, soils, water, and
biota. Often described as a metalloid, As is the 33rd element on the periodic table and
ranks 52nd in average concentration in the earth’s crust (Demayo, 1985). As is commonly
found in the natural environment in inorganic form as an oxyanion in two valence states,
As(V) (arsenate) or As(III) (arsenite) (Vaughan, 1993). The ratio of As(V) to As(III) is a
function of the pH and redox conditions of the system (Masscheleyn et al., 1991; Marin
et al., 1993). The equilibria for both As(V) and As(III) are give in equations (1)-(6) along
with their respective acid disassociation constants (O’Neill, 1990).

Arsenic acid, As(V)

H3AsO4 + H2O ↔ H2AsO4- + H3O+ pKa=2.20 (1-1)


H2AsO4- + H2O ↔ HAsO42- + H3O+ pKa=6.97 (1-2)
HAsO42- + H2O ↔ AsO43- + H3O+ pKa=11.53 (1-3)

Arsenous Acid, As(III)

H3AsO3 + H2O ↔ H2AsO3- + H3O+ pKa=9.22 (1-4)


H2AsO3- + H2O ↔ HAsO32- + H3O+ pKa=12.13 (1-5)
HAsO32- + H2O ↔ AsO33- + H3O+ pKa=13.4 (1-6)

The most thermodynamically stable compounds of As in the natural water


environment (pH 6~8) are H3AsO3 for arsenite and H2AsO4- or HAsO42- for arsenate

2
(Smith et al., 1998). Arsenate is the more common species under oxidizing conditions
(Eh>200mV and pH 5-8) making it the ubiquitous species in surface waters (Smith et al.,
1998).

1.4 Arsenic Origins

Arsenic can be released into the environment through both natural and human
activities. The common natural sources of As include volcanic activity, erosion of As-
bearing sediments and rocks, and forest fires (EPA, 2001). The anthropogenic sources of
As are widespread and can be categorized in the following manner: Industry, mining,
agriculture, and other sources (Smith et al., 1998). Manufacture of ceramics, glass,
electronics, pigments, cosmetics, fireworks, and steel production are some of the major
constituents of industrial As use. Mining and smelting of Pb, Zn, Cu, and Au ores acts as
a source of As which is a natural component of each. From the 19th century until
recently, inorganic arsenic compounds have been a major component of pesticides and
herbicides used in agriculture. Other anthropogenic sources include fly ash from coal
burning, tannery wastes, and lumber treatment (Smith et al, 1998).

1.5 Health Risks and Occurrence

Exposure to arsenic has been known to pose severe adverse health effects on
humans. Two major exposure pathways are ingestion of As-containing food and
consumption of As-contaminated drinking water (ATSDR, 2000). Cancer of the kidney,
lungs, skin, bladder, nasal passages, liver, and prostate has been linked to long-term
exposure to arsenic in drinking water (EPA, 2001). In 1999, the National Research
Council released a report concluding that consumption drinking water contaminated with
As (even at low concentrations) has harmful cardiovascular, neurological, reproductive,
respiratory, hepatic, hematological, diabetic, and dermal effects (NRC, 1999). Even at As
levels 10 µg/L the risk of death due to lung and bladder cancer is 12 to 23 deaths per
10,000 people (NRC, 2001).
Arsenic contamination of drinking water sources is widespread throughout the
world and has been reported to have caused As toxicity problems in countries such as the
United States, Germany, Chile, Argentina, the United Kingdom, Taiwan, India, and
Bangladesh (ATSDR, 2000). The United States Geological Survey (USGS) has
estimated that 14% of groundwater sources exceed 5 µg/L (Focazio et al., 1999), while
the EPA states that approximately 2% of the US population receives drinking water
containing >10 µ/L As (Holm, 2002). The Natural Resources Defense Council also
estimates that 56 million people in the United States are exposed to unsafe levels of As in
drinking water (Mushak, 2000).

1.6 Legislation and Standards

The first legislative effort to minimize the harmful effects of water pollution
occurred in 1972 with the passing of the Federal Water Pollution Control Act
Amendments which later became known as the Clean Water Act. Control of arsenic in
drinking water began in 1975 when the EPA established the first maximum

3
contamination level (MCL) for As at 50 µg/L. The Safe Drinking Water Act as amended
in 1996 requires the U.S. Environmental Protection Agency to issue a new drinking water
standard for As. In response to this risk concern, the U.S. Environmental Protection
Agency (EPA) has adopted a maximum contaminant level (MCL) for arsenic of 10 µg/L.
The new MCL will become effective January 2006. To meet the more stringent drinking
water standards, existing treatment systems will have to be upgraded or new systems
installed.

1.7 Arsenic Removal Technology

In general, three types of treatment technologies are commonly cited for As


removal, including modified conventional treatment (MCT) (Chwirka et al., 2004;
Ghurye et al., 2004; Clifford et al., 2003; Fan et al., 2003; Brandhuber and Amy, 1998;
McNeill and Edwards, 1997; Hering and Elimelech, 1996; Scott et al., 1995), sorption
using activated alumina (AA) (Wang et al., 2002), standard ion exchange resins (IX)
(Clifford, 1999), granular ferric hydroxide (GFH) (Sperlich et al., 2005; Badruzzaman et
al., 2004; Driehaus et al., 1998), or granular ferric oxide (GFO) (Westerhoff et al., 2005;
Manna et al., 2003), or iron-coated sand (Benjamin et al., 1996), and reverse osmosis
(RO) (EPA, 2002). The treatment cost increases in the order of: MCT << AA or IX < RO
(Chen et al., 1999). MCT employs various coagulants to enhance As removal in a
conventional water treatment process. However, it is extremely difficult to meet the new
MCL using MCT alone. Therefore, additional treatment such as microfiltration is often
required (Ghurye et al., 2004). Other processes such as IX using SBA resins or AA
adsorption or RO are less cost-competitive due to lack of selectivity for As, frequent
regeneration requirements and production of large volumes of As-laden process residuals
(EPA, 2000b). GFH and GFO are relatively cheaper sorbents, and they are often used as
‘disposable’ sorbents (i.e. no regeneration and reuse are attempted). However, the process
may result in large volumes of arsenic-laden sorbents, which will require additional
handling and disposal.
To meet the urgent technology needs, a number of other technologies were also
explored, including electro-coagulation (Kumar et al., 2004), polymer inclusion
membrane process (Ballinas et al., 2004), mesoporous alumina sorption (Kim et al.,
2004), activated mud (Genc-Fuhrman et al., 2004) and ferrihydrite crystallization process
(Richmond et al., 2004). However, these new techniques are in the developmental stage.
Consequently, innovative cost-effective treatment processes are urgently needed (Han et
al., 2003).

1.8 The Concept of Polymeric Ligand Exchange

The concept of ligand-exchange-based separation was first introduced by


Helfferich (1962). Generally, a PLE is composed of: a) a cross-linked hosting resin that
can firmly bind with a transition metal such as copper and iron, and b) metal ions that are
immobilized to the functional groups of the hosting resin. While sharing many common
features with standard ion exchangers, a ligand exchanger employs transition metal ions
as its terminal functional groups. As a result, ligand exchange involves concurrent Lewis
acid-base (LAB) interactions (metal-ligand complexation) and electrostatic interactions

4
between the fixed metal ions and target anionic ligands. While conventional anion
exchangers’ selectivity for various anions is governed by electrostatic interactions, the
affinity of a PLE is predominated by both the ligand strength and ionic charge of the
ligands.
In his pioneer work, Helfferich (1962) prepared some of the very first PLEs by
loading a transition metal (Ni or Cu) onto commercial cation exchange resins. Because
the charges of the loaded metal ions are neutralized by the negative charges of the resins’
functional groups, the PLEs could only sorb some neutral ligands such as ammonia and
diamine (Helfferich, 1962). Later, Chanda et al. (1988) prepared a new PLE for selective
removal of arsenic by loading ferric ions onto a weak base chelating resin (known as
DOW 3N) with di(2-picolyl)amine groups. They observed that this PLE was able to
remove ~140 bed volumes (BVs) of arsenate-laden water and the saturated PLE can be
regenerated using 1 M of NaOH. However, because of the weak Lewis acid
characteristics of ferric ions, the amount of Fe3+ loaded was low. As a result, the PLE’s
capacity for arsenate was very limited. Moreover, the loaded iron was nearly completely
stripped off the hosting resin during regeneration and reloading of Fe3+ was necessary
after each cycle of operation. Realizing the critical drawbacks of Fe3+ ions, Ramana and
SenGupta (1992) prepared a PLE by loading Cu2+ onto a weak base chelating resin
(known as DOW 2N) with 2-picolylamine groups. Since Cu2+ is a much stronger Lewis
acid than Fe3+, which is in accord with the Irving and Williams order, a much greater
metal-loading capacity was observed. The copper loaded DOW 2N showed orders of
magnitude greater selectivity for arsenate and selenate in the presence of competing
sulfate ions than commercial SBA resins.
To achieve selective removal of phosphate, Zhao and SenGupta (1997) developed
and characterized a model PLE, referred to as DOW 3N-Cu, by loading Cu2+ ions onto
the chelating resin DOW 3N resin. Compared to DOW 2N, DOW 3N contains one more
(2-picolyl)amine group per functional group. As a result, the copper capacity for DOW
3N nearly doubles that for DOW 2N (Henry et al., 2004). DOW 3N-Cu showed
unusually high selectivity for phosphate in the presence of high concentrations of sulfate,
chloride, nitrate and bicarbonate (Zhao and SenGupta, 1998). Figure 1-1 depicts the
functional group of such a PLE (designated as DOW 3N-Cu), where a chelating resin
containing nitrogen as electron donor atoms is employed as the metal hosting polymer.
Metal ions (Cu2+) are firmly immobilized on the polymer surface by covalently bonding
with the N donor atoms. Since the nitrogen atoms are predominately in their free base
form at pH >3 (Zhao, 1997), the positive charges of loaded Cu2+ ions remain available to
interact with anions in the aqueous phase. Moreover, since only a fraction of the copper’s
6 coordination bonding sites are consumed for binding copper onto the polymer surface,
the immobilized Cu2+ ions remain capable of complexing with target ligands from the
aqueous phase. Consequently, the Cu2+-tailored PLE can interact with anionic ligands
such as arsenate in the aqueous phase through concurrent Lewis acid-base interaction
(metal-ligand complexation) and electrostatic interactions. Compared to conventional
strong base anion exchangers where electrostatic interaction governs the resins’
selectivity, PLE’s selectivity sequence is strongly controlled by the ligand characteristics
of anions due to the additional Lewis-acid-base interaction.

5
Polystyrene with N-Donor Atoms
(Chelating Functionality)
N N

Coordinate Bonding
Cu2+ Immobilized Metal Ions

Electrostatic Interaction Lewis Acid-Base


Interaction
Ln- Target Ligands from Aqueous Phase

Figure 1-1. A conceptualized illustration of the functional group of a PLE

The PLE’s unusually high selectivity toward strong ligands is due to strong
interactions between the resins’ metal functional groups (Lewis acid) and the target
ligand’s electron donor atoms (Lewis base) (Zhao and SenGupta, 2000; 1998a; 1998b;
Zhao, 1997). Strong ligands such as phosphate and arsenate will be preferred by a PLE
over sulfate, which virtually reverses the selectivity sequence of commercial SBAE
resins.

Figure 1-2. Breakthrough histories of phosphate and competing ions with DOW 3N-Cu
(PLE).

6
P in Effluent (mg/L)

Figure 1-3. Phosphate breakthrough curves with a commercial resin (IRA-958) and
DOW 3N-Cu.

Selective removal of phosphate (HPO42-) was achieved using DOW 3N-Cu (Zhao
and SenGupta, 2000; 1998; Zhao et al., 1998; Zhao, 1997). Figure 1-2 shows the
breakthrough histories of phosphate and various competing anions in a bench-scale fixed-
bed run (Zhao and SenGupta 1998). The selectivity sequence follows the order: HPO42-
> HCO3- > SO42-, which essentially reverses the affinity sequence for standard ion
exchange resins where SO42- > HPO42- > HCO3-. Figure 1-3 compares phosphate
breakthrough curves using one of the best commercial resins (IRA-958) and DOW 3N-
Cu. The treatment capacity of the PLE is nearly 5 times greater than that of the
conventional ion exchanger under identical water quality conditions.
Given that arsenate is an even stronger ligand than phosphate, we hypothesize that
similar concept will work even better (with higher capacities) for arsenate. Because of
the strong coordination bond between arsenate and immobilized Cu2+ ions, both free
arsenate ions and complexed arsenic species (it is common that arsenate may be present
in complexation with other metals such as Fe3+ in water) in solution can also be removed
by PLEs – an unparalleled advantage of PLEs compared to commercial resins.

The arsenate/sulfate exchange reaction can be depicted by eqn (1).

R-Cu2+SO42- + HAsO42- Æ R-Cu2+HAsO42- + SO42- (1-7)

where R is the resin matrix carrying the immobilized Cu2+ ion as its functional group.

Due to the extremely strong metal-ligand interactions between Cu2+ and nitrogen
donor atoms in the host polymer, DOW 3N-Cu exhibited very low copper bleeding when
used for phosphate removal from both drinking water and municipal wastewater. Under
the extreme regeneration conditions where ~10 bed volumes of 6% NaCl at pH of 4.5
were applied, the total copper loss from the bed was less than 0.01% (Zhao, 1997; 1995).

7
CHAPTER 2. SYNTHESIS OF POLYMERIC LIGAND
EXCHANGERS

In this study, a total of six PLEs were prepared in our laboratory, including a
copper-loaded PLE based on the chelating resin, DOW 3N, and five other PLEs based on
commercially available XAD resins, which were first functionalized in our laboratory.
For the sake of comparison, two commercially available strong-base anion exchange
(SBA) resins (IRA 900 and IRA 958) were also included in this study.

2.1 Preparation of DOW 3N-Cu

DOW 3N-Cu was prepared by loading Cu2+ ions onto a commercial chelating ion
exchange resin (DOW 3N), purchased from Aldrich (Milwaukee, WI, USA). The copper
loading procedures used by Zhao and SenGupta (1998) were slightly modified. In brief,
DOW 3N was first conditioned through cyclic acid and base washing using 1N HCl and
1N NaOH, respectively. Upon rinsing using DI water, the resin was equilibrated with
0.1% (w/w) copper solution at pH 3.5-4.0 for two weeks. Analytical grade CuCl2 •2H2O
(Aldrich, Milwaukee, WI, USA) was used for preparing the copper solution. The resin-to-
solution ratio was approximately 1:200 (w/w). To enhance copper loading, the resin-
solution mixture was intermittently heated at 70 oC for ~4 hours every other day and then
placed back at ambient temperature (~21 oC). (Note: mild heating can cause resin
swelling and enhance aging, thereby enhancing the copper loading kinetics and stability).
To avoid oxidation of the resin matrix, nitrogen gas was blown in the solution during
heating. Upon completion, the copper loaded resin was thoroughly rinsed using DI water
and air dried for use.

2.2 Synthesis of PLEs Based on Non-Functionalized Polymeric Sorbents (XAD)

A total of four new PLEs based on two representative XAD matrices


(XAD1180and XAD7HP) were prepared to explore the effect of matrix properties on the
selective removal of arsenate. To facilitate copper loading, the XAD resins were first
functionalized with, respectively, two functional monomers (2-picolylamine and di(2-
picolyl)amine) as illustrated below.

2.2.1 Materials

Non-functionalized, macroporous polymer beads Amberlite® XAD1180 and


XAD7HP were purchased from Sigma Aldrich (Milwaukee, WI) and were used as the
starting polymeric matrices for making the new PLEs. Table 2-1 summarizes the key
physical properties of these polymeric sorbents. XAD1180 is composed of polystyrene
copolymers crosslinked with divinylbenzene (DVB), whereas XAD7HP is a crosslinked
poly(methyl methacrylate), i.e. a polyacrylic polymer. Because of the different matrices,
XAD7HP behaves much more hydrophilic than XAD1180. Both XAD sorbents have
relatively large pore sizes compared to other currently available macroporous resins. Two
nitrogen-rich monomers (di(2-picolyl)amine and 2-picolylamine) were used to

8
functionalize the XAD resins for their known high affinity toward copper ions. Di(2-
picolyl)amine was purchased from Richman Chemicals (Lower Gwynedd, PA), and 2-
picolylamine from Sigma Aldrich. All solvents and other chemicals were also from
Sigma Aldrich.

Table 2-1. Properties of parent polymer matrices.


MATRIX POLYMER PARTICLE SURFACE POROSITY MEDIUM PORE
TYPE SIZE (MM) AREA (ML/ML) SIZE (NM) /
(M2/G) DISTRIBUTION
XAD1180 PS/DVB 0.35 – 0.60 ≥ 500 ≥ 0.60 45 / narrow
(macroporous beads)
XAD7HP Acrylic 0.56 – 0.71 ≥ 380 ≥ 0.50 35 / narrow
(macroporous beads)
Source: Information provided by the manufacturer, Rohm and Haas Co., Philadelphia,
PA.

The XAD resins contained moisture and small amounts of sodium carbonate.
Before functionalization, the resins were conditioned through the following successive
procedure: 1) rinse the resins with DI water, 2) rinse for ~4 hours using 0.5 N HCl, 3)
rinse three more times with DI water, 4) rinse with methanol, and 5) air dry and then
oven dry at 70 °C until the weight no longer changed.

2.2.2 Functionalization of XAD Copolymers

Functionalization of styrene-divinylbenzene copolymers, XAD1180, involved two


steps of reactions: 1) chloromethylation of available aromatic rings in the copolymer, and
2) the immobilization of pyridine-containing functional groups through reactions between
the chloromethyl groups on the polymer and the amine groups of the ligand compounds.
Chloromethylation of XAD1180 was carried out via two methods. In Method A,
the polymer beads were soaked in chloromethyl methyl ether (5 mLper gram of resin) at
room temperature for 30 minutes. Anhydrous SnCl4 (0.2 mL per gram of resin) was then
added as catalyst while stirring. The reaction flask was then set in an oil bath with
temperature set in the range of 35 to 55 ºC. The reaction mixture was stirred for 1 to 5
hours. At the end of the reaction, the mixture was quenched by dropwise addition of
methanol under stirring until the mixture was cooled to room temperature. The liquid was
then separated from the resin, and the resin was washed successively with acetone, DI
water, and methanol.
In Method B, a mixture of thionyl chloride and dimethoxymethane (5:6 v/v) was
used as the reagent for in-situ generation of chloromethyl methyl ether, and anhydrous
SnCl4 was also used as the catalyst. The reagent mixture and catalyst amounts were kept
at 8 mL and 0.2 mL per gram of resin, respectively. The resin was first soaked with
reagent mixture for 20 minutes, and then SnCl4 was added dropwise while the resin and
reagent mixture was under stirring and cooling. The reaction temperature was controlled
below 40 ºC. When all the catalyst was added, the reaction vessel was placed into a 35
ºC or 40 ºC oil bath, allowing for reaction (under stirring) to continue for predetermined
times (0.5 to 5 hours). Then the mixture was quenched by dropwise addition of methanol

9
under stirring until the mixture was cooled, the liquid was then separated from the resin,
and the resin was successively washed with acetone, DI water, and methanol.
In both methods, the chloromethylated resins were rinsed with DI-water, air-
dried, and oven-dried at 70 ºC. The resin weight gain was measured to determine the
degree of chloromethylation. Based on chloromethylation measurements and the
subsequent ligand functionalization tests, Methods A and B showed similar results.
However, because Method B avoids the direct use of chloromethyl methyl ether, which is
a carcinogen, Method B was used in all subsequent chloromethylation tests in this study.
The general chloromethylation reaction is depicted as follows:

SOCl2 and CH3OCH2OCH3

SnCl4

CH2Cl

Immobilization of the chelating functional groups was carried out by reacting the
chloromethylated polymer beads with the functional ligands 2-picolylamine or di(2-
picolyl)amine. The amination was carried out in the presence of a mixture of toluene and
dimethylformamide (DMF) (2:1 v/v) as the solvent. The molar ratio of a ligand and the
chloromethyl group was kept at 2:1. The resin, ligand, and solvents were mixed in a dry
Erlenmeyer flask connected with a condenser, and all the reactions were carried out in 95
ºC oil bath for 24 hours under gentle stirring. Upon completion, the functionalized resins
were thoroughly washed with acetone and methanol and then air-dried. The reaction
scheme is shown below:

R
HN R'

(R,R' = pyridine ligand) CH2


CH2Cl
N
R R'

The ligand-grafted beads were then washed using DI water, and copper loading was
then performed in the same manner as for DOW 3N. The resultant chelating resins were
designated as XAD1180-3N and XAD1180-2N, respectively, where 3N indicates the
di(2-picolyl)amine functional groups (three nitrogen atoms per functional group),
whereas 2N refers to the 2-picolylamine groups (two nitrogen atoms per functional
group). Cu(II) was then loaded to the functionalized XAD sorbents to yield the
corresponding PLEs, XAD1180-3N-Cu and XAD1180-2N-Cu, respectively.
Figure 2-1 shows the schematic and key reactions in synthesizing PLEs based on
PS/DVB polymers. Note that the product before copper loading is also a valuable
chelating resin, which is of value for removal of heavy metals from water.

10
a XAD1180 2N-Cu

R
Chloromethyl methyl ether HN R CuCl2

FeCl3, CH2Cl2 R,R=pyridine ligand CH2 CH2 CH2


CH2Cl N R N Cu2+ N R
R R R R

Chloromethylation Amination Copper Loading

Figure 2-1. Schematic and key reactions in synthesizing PLEs based on polystyrene-
DVB XAD polymers.

Functionalization of acrylic copolymer, XAD7HP, was carried out through the


aminolysis of the ester groups in the polymer matrix through the amine group of 2-
(picolyl)amine or di(2-picolyl)amine. Dimethyl sulfoxide (DMSO) was used as the
solvent. The ligand to polymer ratio was 1:1 (w/w), and 5 ml of DMSO was used per
gram of polymer. The resin, ligand, and solvent were loaded in a dry Erlenmeyer flask,
which was then heated in oil bath while stirring and under nitrogen purging. The bath
temperature was gradually raised from room temperature to 170 ºC during the first hour
of the reaction. Then the reaction was kept at 170 ºC for 4 hours. The reaction was then
cooled down, and the resin was successively washed with DI water, 0.1N HCl aqueous
solution, and DI water. The reaction scheme is depicted as follows:

CH 3 CH 3
CH 2 C Di(picolyl)am ine CH 2 C
C O C O
O
CH 3 N
CH 2 CH 2

N N

The resultant chelating resins are designated as XAD7HP-3N and XAD7HP-2N,


respectively. Cu(II) was then loaded on the resins to yield the corresponding PLEs,
XAD7HP-3N-Cu and XAD7HP-2N-Cu.

11
Figure 2-2 shows the schematic and key reactions in synthesizing PLEs based on
polyacrylic polymers. Note that PLEs based on PA-polymers are expected to show better
resistance to organic fouling.

a XAD7HP 2N-Cu

CH3
CH3
CH2 C
CH3 CH2 C
C O
CH2 C Di(2-pycolyl)amine C O CuCl2 N
C O N CH2 CH2
CH2 CH2
O
CH3 Catalyst N N
N N
2+
Cu

Figure 2-2. Schematic and key reactions in synthesizing PLEs based on acrylic polymers.

2.2.3 Copper Loading and Copper Capacity Measurement

All the functionalized resin samples were conditioned according to the following
procedure: 4 hours of equilibration with 0.1 N HCl aqueous solution, washing with DI
water, 4 hours of equilibration with 0.1 N NaOH aqueous solution, and washing with DI
water. The resins were then loaded with copper by equilibrating with CuCl2 solution (1%
w/w of Cu, 30 mL solution per gram of resin) under shaking for 2 days. The resin color
turned to blue-green upon copper loading. The copper-loaded resins were then thoroughly
washed with DI water and air-dried for uses.
To measure the maximum copper loading capacity, ~0.12 gram of a copper-
loaded resin was mixed with 15 mL of ammonium hydroxide solution (4 wt.% of NH3),
and the mixture was shaken for one day to strip off the copper from the resin. The amount
of copper in the stripping solution was then measured by the absorbance at 630 nm using
UV-Vis spectrometer (Hewlett Packer UV-Vis 8453), and copper uptake was calculated.
Table 2-2 lists the copper uptake capacity for the four XAD-based chelating
resins and for the commercial chelating resin, DOW 3N. The copper capacity for five of
the resins (except XAD7HP-3N) ranged between 1.2 and 1.4 meq/g. Despite the
considerable differences in the properties (polymer type and surface area) of the parent
polymers (Table 1), the resultant chelating resins do not differ significantly in their
copper capacity. This observation suggests that the sorption capacity of the XAD-based
chelating resins may be limited by the extremely high crosslinkage (~40%) of these

12
polymers. Although the high crosslinkage greatly increases the surface area of the resins,
it reduces the size of the pores. The pore size may be further reduced during the
functionalization of the resins. As a result, the final copper uptake capacity of the XAD-
based chelating resins was lower than that for DOW 3N-Cu (Note: DOW 3N has a much
smaller surface area (~139 m2/g), but larger mean pore size (~250 Å) (Zhao, 1997)).

Table 2-2. Maximum copper loading of the chelating resins


Chelating Resin Functional group Maximum Cu-
Loading Capacity
(mg/g)
XAD1180-2N 2-Picolylamine 40
XAD1180-3N Di(2-picolyl)amine 39
XAD7HP-2N 2-Picolylamine 44
XAD7HP-3N Di(2-picolyl)amine 26
DOW 3N Di(2-picolyl)amine 90

In addition, we found that the optimal reaction time in chloromethylation should


be controlled at ~1.5 hours, which gave the greatest copper capacity, as shown in Table
2-3.

Table 2-3. Effect of chloromethylation time on maximum copper loading capacity of


di(2-picolyl)amine-functionalized XAD1180.
Chloromethylation 35 ºC, 35 ºC, 35 ºC, 35 ºC, 40 ºC,
Time 0.5 1 hour 1.5 2 hours 5 hours
hour hours
Weight Gain after
Chloromethylaton 18 20 21 22 24
(%)
Max. Cu-Loading
Capacity (mg/g 30 35 39 33 26
resin)

13
CHAPTER 3. SORPTION AND DESORPTION OF ARSENATE
USING VARIOUS POLYMERIC LIGAND
EXCHANGERS: BENCH-SCALE TESTS

Removal of arsenate, or As(V), using various PLEs is tested through a set of


equilibrium, kinetic and column experiments. The result was compared to two commonly
used standard SBA resins. While all PLEs demonstrated high selectivity for arsenate in
the presence of other competing anions such as sulfate and chloride, DOW 3N-Cu
showed the highest arsenic selectivity and capacity, and thus, was studied in more details.
DOW 3N-Cu was able to treat ten times more water per operating cycle than the standard
SBA resins, and can be easily regenerated using 4% (w/w) of NaCl.

3.1 Materials

A total of eight sorbents were tested for arsenate removal, including DOW 3N-
Cu, the five XAD-based PLEs, and two commercial SBA resins (IRA 900 and IRA 958).
Tables 3-1 summarizes the salient properties of these sorbents. Before use, the resins
were conditioned following the standard acid-base washing procedures as described
above. All resins were initially in the chloride form.

Table 3-1. Salient properties of various ion exchange resins used in this study.
Sorbent DOW 3N IRA 900 IRA 958
Rohm and Haas
DOW Chemical Rohm and Haas
Manufacturer Philadelphia, PA,
Midland, MI, USA Philadelphia, PA, USA
USA
R R R'
Functional CH2 N CH2
CH3 N CH3 CH3 N CH3
Group N N
CH3 CH3

- CH2 – CH – CH2 - - CH2 – CH – CH2 - - CH2 – CH – CH2 -

C=O
Matrix
(R or R’) HN – CH2 – CH2

Polystyrene, Polystyrene, Polyacrylic,


Macroporous Macroporous Macroporous
Capacity
2.98a) 3.6a) 3.4a)
(meq/g)
BET Surface
139a) N/A N/A
Area (m2/g)

14
The following chemicals (all in analytical grades) were purchased from Fisher
Scientific (Pittsburgh, PA, USA): FeCl3, NaOH, NaHCO3, Na2SO4, and NaCl. Reagent
grade of sodium hydrogen arsenate (Na2HAsO4•7H2O) was purchased from (Aldrich,
Milwaukee, WI, USA).

3.2 Experimental Methods

3.2.1 Equilibrium Sorption Tests

Batch isotherm tests were carried out for various PLEs as well as for the
commercial SBA resins. In all cases, 60 mL glass vials with Teflon-lined screw caps
were used for the equilibrium tests. The tests were initiated by adding known masses
(0.004 g to 0.15 g) of a resin to 50 mL of a solution containing an initial concentration of
10 mg/L as As and 100 mg/L sulfate. The mixture was then shaken on a rotating tumbler
for 7 days, which was sufficient to reach equilibrium as confirmed through separate
kinetic tests. The initial pH of the solution was ~7.5, and pH during equilibration was
kept in the range of 7.0-7.5 through intermittent adjusting using dilute NaOH or HCl until
final equilibrium was reached. At equilibrium, water samples were taken from each vial
and analyzed for As and sulfate remaining in water. Arsenic or sulfate uptake was then
calculated based on the mass balance equation,

V ( Co − Ce )
qe = (3-1)
M

where qe is the equilibrium mass uptake of As by a sorbent (mg/g), V is the solution


volume (L), Co and Ce are the initial and final concentration of arsenic or sulfate in
solution, respectively (mg/L), and M is the mass of a sorbent added (g). All tests were
carried out at room temperature (~21 oC).

3.2.2 Fixed-Bed Column Tests

The breakthrough behaviors of arsenate as well as various competing anions were


tested for DOW 3N-Cu, IRA 900, XAD1180-3N-Cu, and XAD7HP-3N-Cu, respectively,
in a fixed-bed configuration and in the down-flow mode. The experimental set-up
included a Plexiglass column (11 mm in diameter and 25 cm in length), an Accuflow
Series II high-pressure liquid chromatography stainless steel pump, and an Eldex
automatic fraction collector. Approximately 5 mL of a resin was used in each run.
Simulated contaminated water was introduced in the resin bed in a down-flow mode. The
major compositions in the influent water were as follows: for IRA 900, As = 75 μg/L,
SO42- = 1.9 meq/L, Cl- = 2.4 meq/L, and pH = 8.3; for DOW 3N-Cu: As = 94 μg/L, SO42-
= 1.0 meq/L, HCO3- = 0.50 meq/L, Cl- = 1.3 meq/L, and pH = 8.6. For the XAD-based
PLEs, the influent feeding solution containing 97 µg/L as As(V), 47 mg/L as sulfate, 82
mg/L as chloride, 6.5 mg/L as bicarbonate, and pH of 7.5 was passed on the packed
column to down-flow direction with constant flow rate (1.2 mL/min). In all cases, a
constant flowrate of 1.2 mL/min was maintained, which translates to an empty bed
contact time (EBCT) of 4.1 minutes, and a superficial liquid velocity (SLV) 3.0 m/hr.

15
Samples were collected in 22 mL tubes using a fraction collector and then analyzed
within 24 hours.

3.2.3 pH Effect

The pH effect on equilibrium uptake of arsenate was tested for DOW 3N-Cu in a
similar fashion to that in the isotherm tests. However, the final solution pH was adjusted
to span from 2.8 to 11 (each vial had a different pH). Each testing vial contained 50 mL
solution with an initial As of 8.3 mg/L and SO42- of 86 mg/L. The sorption was initiated
upon the addition of ~0.020 g of air-dried DOW 3N-Cu to each vial.

3.2.4 Kinetic Tests

Batch kinetic tests were conducted to test the arsenic sorption rate and determine
the effective intraparticle diffusivity for DOW 3N-Cu, XAD1180-3N-Cu, XAD7HP-3N-
Cu. The experiment was initiated by adding 0.95 g of the sorbent into 2 L of a solution
containing 0.92 mg/L As and 100 mg/L sulfate and at an initial pH of 8.0. The solution
pH was adjusted intermittently by adding small amounts of dilute NaOH to keep the
solution pH within 7.0-7.5, where pH effect on the PLE’s uptake was minimal (see
Section 3.4). During the experiment, the resin-solution mixture was intensively agitated
on a shaker to eliminate the possible film diffusion limitation on the mass transfer
process. At predetermined time intervals, water samples (~2 mL/each) were taken and
analyzed for As. The As uptake at various times was then determined through mass
balance calculations.

3.2.5 Resin Regeneration and Reuse

Regeneration of arsenic loaded DOW 3N-Cu, XAD1180-3N-Cu, and XAD7HP-


3N-Cu were carried out in the same fixed-bed column configuration and in the co-current
flow mode. In search for an optimal regenerant recipe, a 4% (w/w) NaCl solution at pH
4.1, 7.0, and 9.1 was tested in separate column runs. The operating hydrodynamic
conditions were maintained identical for all cases, including an empty bed contact time
(EBCT) of 22 minutes and a superficial liquid velocity (SLV) of 14 m/hr.
Sorption capacity of DOW 3N-Cu that was subjected to up to 8 saturation-
regeneration cycles was compared to that of the virgin DOW 3N-Cu. The equilibrium
sorption of As was tested in the same manner as described in the isotherm tests, with the
following conditions: initial As = ~10 mg/L, initial SO42- = 100 mg/L, resin weight = 0.01
g, solution volume = 50 mL, final pH = 7.0-7.5. The optimum regenerant (i.e. 4% NaCl at
pH = 9.1) was employed to regenerate the resin after each use.

3.3 Chemical Analysis

Arsenic and copper were analyzed using a Perkin Elmer Atomic Adsorption
Spectrophotometer in the graphite mode, which has a detection limit of 3 μg/L as As.
Solution pH was measured using an Orion pH meter (model 520A). Sulfate and chloride

16
ions were analyzed using a Dionex Ion Chromatograph (Model DX-120). Bicarbonate
was analyzed with a UV- Persulfate TOC Analyzer (Phoenix 8000).

3.4 Results and Discussion

3.4.1 Equilibrium Isotherms and Arsenate Adsorption

As mentioned before, one of the critical limitations for current SBA resins is its
lack of selectivity and low sorption capacity for arsenate especially in the presence of
some omnipresent anions such as sulfate. To probe the PLEs’ sorption capacity, arsenate
sorption isotherms were constructed for DOW 3N-Cu, XAD1180-3N-Cu, and XAD7HP-
3N-Cu, respectively, in the presence of an initial sulfate concentration of 100 mg/L. For
comparison, arsenic isotherms were also measured for the two commercial SBA resins
(IRA 900 and IRA 958) under otherwise identical conditions. The equilibrium pH was
maintained at 7.0-7.5 in all cases to minimize the pH effect on the uptake (see Section
3.4.3). Figures 3-1 and 3-2 show the observed (symbols) and simulated (lines) isotherms
for these sorbents.

50
pH ( equilbirium): 7.0-7.5
2-
Conc.of SO4 : 92.3 mg/L
40
qe (mg/g)

30
DOW 3N-Cu

20

10
IRA 958

IRA 900
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Ce (mg/L)

Figure 3-1. Arsenate sorption isotherms for DOW 3N-Cu and two conventional SBA
resins (IRA 900 and IRA 958) in the presence of competing sulfate ions. (Symbols:
observed data; lines: Langmuir model fits)

17
14
pH ( equilbirium): 7.0-7.5
12 SO42-: 97.3 mg/L

10
qe (mg/g)

6
XAD 1180-3N-Cu
4 XAD 7HP-3N-Cu

0
0 2 4 6 8 10
Ce (mg/L)
Figure 3-2. Arsenate sorption isotherms for XAD1180-3N-Cu and XAD7HP-3N-Cu in
the presence of competing sulfate ions. (Symbols: observed data; lines: Langmuir model
fits)

The classical Langmuir model was employed for fitting the experimental data
(Zhao et al., 1995),

bQC e
qe = (3-2)
1 + bC e

where qe is the equilibrium As uptake (mg/g), Ce is the equilibrium concentration of As in


water (mg/L), and b and Q are the Langmuir affinity and capacity coefficients,
respectively. The non-linear fitting was performed using the SigmaPlot8.0. Table 3-2
lists the model-fitted b and Q values. Table 3-2 reveals that all PLEs showed much
greater arsenate sorption capacity than the commercial SBA resins. Among the PLEs,
DOW 3N-Cu offers the greatest sorption capacity. It is especially noteworthy that the
Langmuir capacity (Q) for DOW 3N-Cu is almost 17 times greater than for the standard

18
SBA resins. Although the total reported capacity of the SBA resins is greater than the
PLEs, very little fraction of the capacity is used for arsenate uptake due to the fierce
competition of sulfate, i.e. lack of arsenate selectivity for the SBA resins.

Table 3-2. The model-fitted Langmuir parameters (b, Q), and experimentally determined
arsenate/sulfate binary separation factor (αAs/S).
Resin Q(Standard Error) b (Standard Error) αAs/ S
(mg/g) (L/mg) (Standard deviation)
DOW 3N-Cu 92(8.2) 0.20(0.028) 12(0.73)
IRA 958 5.5(0.36) 6.1(1.5) 0.10(0.026)
IRA 900 4.5(0.51) 4.1(2.1) 0.20(0.057)
XAD1180-3N-Cu 24(8) 0.13(0.078) 7.4(0.54)
XAD7HP-3N-Cu 18(4.4) 0.15(0.077) 4.9(0.84)

The binary separation factor has been commonly used to compare the relative
affinity of a sorbent for various competing sorbates. In a binary system, the
arsenic/sulfate separation factor (αAs/S) is defined as:

q As C S
α As / S = (3-3)
C As q S

where q and C represent the concentration of As in the polymer phase and in the aqueous
phase, respectively; As and S in the subscripts denote arsenic and sulfate, respectively. In
general, a value of αAs/S of greater than unity indicates the resin’s preference toward
arsenic over sulfate, while the opposite is true if αAs/S is less than unity. The greater the
αAs/S value, the more selective is the resin for arsenate. Based on the experimental
equilibrium sorption data in Figures 3-1 and 3-2 the average separation factor was
calculated for the resins and is given in Table 3-2. The mean αAs/S value of DOW 3N-Cu
is ~12, which is more than two orders of magnitude greater than that for the SBA resins
and clearly indicates the resin’s high selectivity toward arsenate over sulfate. The
unusually high selectivity for arsenic was also true for the XAD-based PLEs although the
total capacity was not as great as for DOW 3N-Cu.
The substantially improved As selectivity of DOW 3N-Cu and other PLEs is
attributable to the concurrent Lewis acid-base interaction and electrostatic interactions
between arsenate and the immobilized Cu2+ ions at the sorbent-sorbate interface. Under
the experimental conditions, mono-hydrogen arsenate (HAsO42-) is considered the
predominant arsenate species (see Section 3.3 for details). HAsO42- is a divalently
charged, bidentate ligand, and a strong Lewis base (donor of electron lone pairs). The
competing sulfate is also a divalently charged ligand, but it is a much weaker Lewis base.
Consequently, interactions between arsenate and the immobilized Cu2+ ions involve both
Lewis acid-base interaction (or inner-sphere complexation) and ion pairing (or
electrostatic interactions), while interactions between sulfate and the Cu2+ ions is
predominantly ion paring. It is noteworthy that Lewis acid-base interaction also enhances

19
the electrostatic interactions between arsenate and the loaded Cu2+ ions. This is because
the inner-sphere complexation occurs over a much shorter distance than outer sphere
complexation, and the electrostatic interactions within the much shortened distance are
much stronger in accord with the Coulomb’s law. Consequently, DOW 3N-Cu offered
much greater affinity for arsenate over sulfate. For the commercial SBA resins, the
quaternary amine functionalities (RN+(CH3)3) take up anions predominately through
electrostatic interactions, i.e., the ligand strength of an anion does not play a role in
sorption affinity. Therefore, SBA resins are not selective for arsenate.
The underlying mechanism for the enhanced arsenate sorption by DOW 3N-Cu
can also be revealed by inspecting the fundamental thermodynamic driving forces, i.e.,
the overall standard free energy change (ΔGoo). For arsenate sorption by DOW 3N-Cu,
ΔGoo is composed of two synergistic terms as shown in eqn (4):

ΔGOo = ΔG EL
o
+ ΔG LAB
o
(3-4)

where ΔGoEL is due to electrostatic interactions and ΔGoLAB is to the Lewis acid-base
interaction (i.e. metal-ligand complexation). Compared to arsenate, other anions such as
sulfate, nitrate and chloride are much weaker ligands, namely, only ΔGoEL in eqn (4) is
operative, thus the resultant driving force (ΔGoo) for these anions is much smaller than
that for arsenate. Commercial SBA resins interact with anions through only electrostatic
interactions (i.e., ΔGoLAB ≈ 0). Therefore, DOW 3N-Cu is able to take advantage of the
strong ligand characteristics of arsenate over other competing anions and to achieve
highly selective removal of arsenate.

3.4.2 Breakthrough Behaviors

Figures 3-3 and 3-4 show the breakthrough histories of arsenate and other
competing anions during the fixed-bed column experiments using IRA 900 and DOW
3N-Cu, respectively. In all cases, lab-simulated water was used in the influent. Figure 3-
3 shows that for IRA 900, the sulfate breakthrough occurred ~100 bed volumes (BVs)
later than the arsenate breakthrough, confirming the resin’s greater affinity for sulfate
over arsenate. Figure 3-3 also reveals a sharp chromatographic peaking of the arsenate
breakthrough curve, which again indicates that this commercial SAB resin favors sulfate
much more than arsenate. Due to the strong competition from sulfate, IRA 900 can treat
only ~600 BVs of contaminated water per operation cycle (a cycle = saturation run +
regeneration run). The breakthrough sequence of the anions reveals the following
selectivity order for IRA 900:

SO42- > HAsO42- > Cl- (3-5)

Field data from Albuquerque, NM, USA, showed that As breakthrough took place
typically within ~450 BVs using SBA commercial resins (Clifford, 1999).
In contrast, a completely different breakthrough behavior was observed when
DOW 3N-Cu was used. Figure 3-4 shows that all three competing anions broke through
before 500 BVs. Based on the new MCL value of 10 μg/L for As, arsenate breakthrough
did not occur until after 6,000 BVs, i.e. the PLE can treat over 10 times more water than

20
IRA 900 before arsenate breakthrough occurs. A minor chromatographic peaking of
sulfate was observed. The breakthrough sequence indicates the following selectivity
sequence:

HAsO42- >> HCO3- > SO42- > Cl- (3-6)

It is noteworthy that the monovalent bicarbonate displayed slightly greater affinity


over the divalent sulfate, which is not surprising given that bicarbonate is a stronger
ligand than sulfate.

7
EBCT: 4.1 min
Influent
6 SLV: 3.0 m/hr
pH: 8.33
CI-: 2.39 meq/L
5 SO42-: 1.91 meq/L
As
As: 75.3 ug/L
4
C/C0

2 Cl-

1
2-
SO4
0
0 200 400 600 800 1000 1200 1400 1600
Bed Volumes
Figure 3-3. Breakthrough histories of arsenate and sulfate in a simulated multi-
component system using a standard SBA resin, IRA 900.

Figures 3-5 and 3-7 show the breakthrough curves with two XAD-based PLEs.
Although the total capacity of these PLEs is much lower than that for DOW 3N-Cu or the
SBA resins, all of the XAD-based PLEs were able to treat ~800-900 bed volumes of
arsenic contaminated water, which is more than that for the SBA resins. In all cases,
competing anions (chloride, sulfate, bicarbonate) broke through within ~50 bed volumes
(BV), whereas the breakthrough of arsenic occurred at about 800-900 BVs.

21
3.0
EBCT: 4.1 min Influent
2.5 SLV: 3.0 m/hr pH: 8.62
Cl-: 1.3 meq/L
SO42-: 0.83 meq/L
2.0
Cl- HCO3-: 0.50 meq/L
As: 94 μg/L
C/C0

1.5

1.0
SO42-
HCO3-
0.5
As

0.0
0 2000 4000 6000 8000 10000 12000
Bed Volumes

Figure 3-4. Breakthrough histories of arsenate and competing anions in a simulated


multi-component system using a polymeric ligand exchanger, DOW 3N-Cu.

2.0
Resin: XAD 1180-3N Influent
EBCT: 2.5 min pH: 7.9
SLV: 3.0 m/hr Cl-: 2.1 meq/L
1.5 SO42-: 0.96 meq/L
As: 97 μg/L
HCO3-: 0.58 meq/L
C/C0

1.0

0.5

0.0
0 200 400 600 800 1000 1200 1400
Bed Volume

Figure 3-5. Breakthrough histories of arsenate and competing anions in a multi-


component system using a polymeric ligand exchanger, XAD1180-3N-Cu.

22
3.5
XAD 7HP-3N
Influent
3.0 EBCT: 4.1 min
pH: 7.65
SLV: 3.0 m/hr -
Cl : 2.1meq/L
2-
2.5 SO4 : 0.96meq/L
As: 97μg/L
-
2.0 - HCO3 : 0.58meq/L
C/C0

Cl
1.5

1.0
SO42-
-
0.5 HCO3
As

0.0
0 200 400 600 800 1000
Bed Volumes

Figure 3-6. Breakthrough histories of arsenate and competing anions in a multi-


component system using a polymeric ligand exchanger, XAD7HP-3N-Cu.

3.4.3 Effect of pH

As in any ion exchange process, the PLE’s selectivity for various competing
ligands can be strongly impacted by solution pH. Solution pH can affect the PLE’s
arsenic uptake in two different aspects. First, solution pH governs the speciation of
arsenate, resulting in arsenate species (H3AsO4, H2AsO4-, HAsO42-, and AsO43-) of
different ionic charges and ligand characteristics. Second, the hydroxyl anions become
aggressively formidable competitors for the ligand exchange sites as solution pH goes up.
Figure 3-7 shows the observed arsenate uptake data as a function of the
equilibrium solution pH. Note that sulfate at an initial concentration of 86 mg/L was
present for all points tested. Figure 3-7 indicates that the optimal arsenate uptake occurs
in the pH range of ~6.0-~8.0, with the peak uptake being at pH ~7.0. At pH < 4.0 or pH >
11, there was virtually no uptake of arsenate observed. It is also interesting that As uptake
started increasing at pH ~4.0 almost in proportion to the increasing formation of the
bidentate hydrogen arsenate species (HAsO42-). However, the As uptake drops sharply as
pH exceeds ~8.0.

From a practical view point, the optimal pH range of 6.0-8.0 is quite novel. Since
the pH value for most natural waters falls in this range (Sawyer, 1978), there is no need
to adjust source water pH to achieve the PLE’s maximal sorption capacity.

23
3.0

2.5

2.0
q (meq/g)

1.5
e

1.0

0.5

0.0
0 2 4 6 8 10 12 14
pH in Solution

Figure 3-7. Arsenic uptake by DOW 3N-Cu as a function of solution pH.

3.4.4 Kinetic Test

In a prior study on phosphate sorption, Zhao and SenGupta (2000) identified that
intraparticle diffusion is the rate-limiting step during sorption of phosphate to DOW 3N-
Cu. They also determined the effective intraparticle diffusivity for phosphate to be 1.0 x
10-8 cm2/s. Given the molecular analog between phosphate and arsenate, the intraparticle
diffusivity is determined in a similar manner. Figures 3-8 through 3-10 present the
changes in As concentration in solution during the transient sorption of As by various
PLEs in a continuously stirred batch reactor.
For intraparticle-diffusion-controlled process, sorption rates are often modeled
based on the Fick’s second law. For spherical beads, the governing equation is given as
(Crank, 1975; Zhao and SenGupta, 2001)

∂q ∂ 2 q 2 ∂q
= D( 2 + ) (3-7)
∂t ∂r r ∂r

where r is the radial coordinate and q(t, r) is the solid-phase arsenic concentration at time
t. Under the experimental conditions, the following initial and boundary conditions apply:

q(0) = 0 at 0 ≤ r ≤ a (3-8)

24
∂q/∂r = 0 at r = 0 (3-9)

(∂q/∂r)(3D M /a) = -V (∂C/∂t) at r = a (3-10)

where a is the mean radius of the resin beads, which was determined to be ~0.22 mm, M
is the mass of the resin added, and V is the solution volume, which is considered constant
during the course of the experiment.
The above experimental system conforms to the scenario where diffusion takes
place in a well-stirred solution of limited volume (Crank, 1975). The solution given by
Crank (1975) as the fractional attainment of equilibrium (F),

q( t ) ∞
6α ( α + 1 ) exp( − Dq n2 t / a 2 )
F= = 1− ∑ (3-11)
q∞ n =1 9 + 9α + q n2α 2

where q∞ is the arsenate uptake by DOW 3N-Cu at infinite time (i.e. at equilibrium), the
parameter α is expressed in terms of the final fractional uptake of arsenate as

Mq ∞ 1
= (3-12)
Vo C o 1 + α

where Vo and Co are initial solution volume and initial arsenate concentration in solution,
respectively. The qn’s are the non-zero roots of

3q n
tan q n = (3-13)
3 + αq n2

The form of eqn (3-13) is convenient in bracketing the roots in well-defined


intervals as determined by the tan function, which allows for simple root finding using
the method of bisection.
The aqueous phase concentration at time t, C(t), was determined using the
following mass-balance equation:

Mq(t) = V [C o - C(t)] (3-14)

The best fit of the model to the experimental kinetic data in Figures 3-8 through
3-10 was achieved by adjusting the diffusivity value (D) until the sum of the squared
error is minimized, which yields a diffusivity value of 1.0 x 10-7 cm2/s for DOW 3N-Cu,
2.0 x 10-6 cm2/s for XAD1180-3N-Cu, and 3.0 x 10-6 cm2/s for XAD7HP-3N-Cu. Based
on these numbers, the sorption rate of DOW 3N-Cu is quite comparable to that of
standard macroporous ion exchange resins, while the XAD-based PLEs demonstrated a
more than one order of magnitude faster kinetics. This observation suggests that the
arsenate sorption sites of the XAD-based PLEs are much more easily accessible. This
kinetic advantage adds value to the XAD-based PLEs. For example, these relatively low-

25
capacity PLEs may be more resistant to organic fouling, and thus, may perform better for
treating water that contains high strength of dissolved organic matter.

1.0
pH: 7.0-7.5
Experiment
As = 0.92 mg/L
0.8 2-
SO4 = 100 mg/L Model
Conc. of As (mg/L)

-7 2
D = 1.0 x 10 cm /sec
0.6

0.4

0.2

0.0
0 2 4 6 8 10 12
Time (hr)

Figure 3-8. Experimental and model-simulated arsenate sorption kinetics of DOW 3N-
Cu. (Symbols: observed data; line: model simulation)

26
6
Resin: XAD1180-3N-Cu
5 pH: 7.0-7.5 Experiment
-6 2
D = 2.0 x 10 cm /sec
Conc.of As (mg/L)
Model
4

0
0 2 4 6 8 10 12 14 16
Time (hr)
Figure 3-9. Experimental and model-simulated arsenate sorption kinetics of XAD1180-
3N-Cu. (Symbols: observed data; line: model simulation)

5
Resin: XAD 7HP-3N
pH: 7.0-7.5 Experiment
-6 2
4 D = 3.0 x 10 cm /sec
Model
Conc.of As (mg/L)

0
0 2 4 6 8 10 12
Time (hr)
Figure 3-10. Experimental and model-simulated arsenate sorption kinetics of XAD7HP-
3N-Cu. (Symbols: observed data; line: model simulation)

27
3.4.5 Regeneration and Reuse of PLEs

Form the standpoints of both cost-effectiveness and environmental friendliness, it


is highly desirable that an ion exchange resin be amenable to efficient regeneration using
cheapest possible regenerant. Furthermore, it is even more beneficial if the spent
regenerant can be recycled and reused. Multiple reuses of regenerant brine can further
reduce the brine needs and cut down the volume of process waste residuals. Minimizing
process waste residuals is currently gaining increasing attention in the U.S. due to the
much tightened regulations on the waste discharge.
Regeneration of arsenate-saturated DOW 3N-Cu was tested in the same fixed-bed
configuration. Figure 3-11 compares arsenate elution profile and recovery during
regeneration using 4% (w/w) NaCl at pH 4.1, 7.0, and 9.1, respectively. As expected
from the results on pH effect (Figure 3-7), greater regeneration efficiency was observed
at either acidic or alkaline pH than at neutral pH. At pH 9.1, more than 96% of sorbed
arsenate was recovered within 22 bed volumes of the regenerant. For comparison,
regeneration of As-saturated IRA 900 was also tested using 4% NaCl at pH 9.1 (data not
shown), and the results showed that under the same conditions, it took ~15 BVs of the
regenerant to achieve a 95% of arsenate recovery.

2000
1800 pH: 9.1
Recovery: 96%
1600 pH: 4.1
Conc.of As (mg/L)

1400 Recovery: 60%


pH: 7.0
1200 Recovery: 68%
1000
800 Resin: DOW 3N-Cu
Regenerant: 4% NaCl
600 EBCT: 22 min
400
200
0
0 10 20 30 40 50 60
Bed Volumes

Figure 3-11. Arsenic elution profile during regeneration of saturated DOW 3N-Cu using
4% NaCl (w/w) at pH 4.1, 7.0, and 9.1, respectively.

28
Figures 3-12 and 3-13 shows that the regeneration efficiency for XAD1180-3N-
Cu was only 49% using 4% NaCl at pH 9.0; however, over 90% arsenate capacity was
recovered using the concentration of NaCl is raised to 6% and pH to 10. Figures 3-14
and 3-15 show that for the hydrophilic PLE, XAD7HP-3N-Cu, a higher NaCl
concentration (8%) is required to achieve 100% regeneration of the resin.
Equations (3-15) through (3-17) illustrate the regeneration reaction stoichiometry
at the specified pH:

At pH ~4.1

R-Cu2+HAsO42- + 2Cl- + H+ R-Cu2+ Cl-2 + H2AsO4- (3-15)

At pH ~7.0

R-Cu2+HAsO42- + 2Cl- + xH+ R-Cu2+ Cl-2 + (1-x)HAsO42- + x H2AsO4- (3-16)

At pH >9.1

R-Cu2+HAsO42- + Cl- + OH- R-Cu2+ (Cl-)(OH-) + HAsO42- (3-17)

Evidently, the participation of OH- in the ligand exchange reaction at alkaline pH


greatly enhanced the regeneration efficiency.
For practical viability, the PLE should be amenable to multiple cycles of
operation without significant capacity drop. Figure 3-16 compares the equilibrium
arsenic sorption capacity of virgin DOW 3N-Cu and when it was subjected to up to 8
consecutive operating cycles (a cycle = a saturation run + a regeneration run). Evidently,
the regenerated DOW 3N-Cu did not show any significant capacity drop compared to its
fresh form. The fact that the arsenic capacity of the PLE was essentially unchanged over
multiple cycles indicated that the copper leakage was minimal during both saturation and
regeneration runs. Indeed, direct measurement of copper eluted showed that the copper
leakage per operation cycle (saturation and regeneration) was less than 0.01% of total
copper loaded.
The spent regenerant was repeatedly used for regeneration for seven times with
only pH adjustment (pH 9.2-10), and more than 95% of recovery was consistently
observed. After the regenerant was used for eight times, the recovery was dropped to less
than 50%. Earlier, Clifford et al. (2003) reported that spent brine can be reused for three
times without chloride makeup for efficient regeneration of a commercial SBA resin.

29
500

Resin: XAD1180-3N-Cu
400 Regenerant: 4% NaCl
Conc.of As (mg/L)
pH: 9.0
EBCT: 22 min
300 Recovery: 49%

200

100

0
0 5 10 15 20 25
Bed Volumes

Figure 3-12. Arsenic elution profile during regeneration of saturated XAD 1180-3N
using 4% NaCl (w/w) at pH 9.0.

700

600
Resin: XAD1180-3N-Cu
Conc.of As (mg/L)

500 Regenerant: 6% NaCl


pH: 10
EBCT: 22min
400 Recovery: 90%

300

200

100

0
0 10 20 30 40 50 60
Bed Volumes
Figure 3-13. Arsenic elution profile during regeneration of saturated XAD1180-3N-Cu
using 6% NaCl (w/w) at pH 10.

30
350

300 Resin: XAD7HP-3N-Cu


Regenerant: 6% NaCl
Conc.of As (mg/L)
pH: 10
250 EBCT: 22 min
Recovery: 64%
200

150

100

50

0
0 10 20 30 40
Bed Volume
Figure 3-14. Arsenic elution profile during regeneration of saturated XAD7HP-3N-Cu
using 6% NaCl (w/w) at pH 10.

700
XAD 7HP-3N-Cu
600 Regenerant: 8% NaCl
pH: 10
Conc.of As (mg/L)

500 EBCT: 22 min


Recovery: 100%
400

300

200

100

0
0 10 20 30 40 50
Bed Volume

Figure 3-15. Arsenic elution profile during regeneration of saturated XAD7HP-3N-Cu


using 8% NaCl (w/w) at pH 10.

31
40

30
qe (mg/g)

20

10

0
fresh 1 2 3 4 5 6 7 8
Cycle

Figure 3-16. Comparing the equilibrium arsenate sorption (qe) of fresh and regenerated
DOW 3N-Cu under otherwise identical conditions. (note: a. One cycle consists of one
saturation run and subsequent regeneration run; b. each point represents mean of
duplicates, the maximum standard deviation was 1.60)

32
CHAPTER 4. ENGINEERED TREATMENT OF SPENT
REGENERATION BRINE

4.1 Introduction

The high arsenic selectivity, sorption capacity, and regeneration efficiency of


DOW 3N-Cu enables arsenate to be concentrated in a small volume (< 1% of water
treated) of spent regenerant. This affords the spent regenerant to be further treated using
simple physical-chemical methods. It is highly desired that the final arsenic-laden process
waste be highly stable and the spent regenerant brine be reused. To achieve these goals,
ferric chloride is used to remove arsenate from the spent regeneration brine via co-
precipitation-adsorption. Earlier, Clifford (1999) reported that arsenic in a 1.0 N NaCl
brine can be lowered from 90 to less than 5 mg/L at a Fe(III) dose of 12 times the
stoichiometric amount. Ferric chloride addition has been studied in depth for drinking
water treatment (Hering, 1996). However, there have been few detailed studies pertaining
to the factors that affect the arsenic removal from brine, the stability of the resultant
arsenic solid waste, and the reusability of the treated brine. The experiments in Chapters
4 and 5 were designed to determine the optimum conditions for effective arsenate
removal from spent regeneration brine, to maximize the stability of arsenic-laden process
waste, and to test the reusability of the treated brine.

4.2 Experimental Methods and Materials

4.2.1 Preparation of Simulated Spent Brine

To conduct brine treatment experiments, spent regeneration brine (SRB) was


simulated based on analysis of the spent brine collected from column tests preformed on
a PLE resin. The brine was reused for regeneration of the resin multiple (up to seven)
times until finally reaching its capacity. The average composition of the spent brine was:
As = 300 mg/L, SO42- = 600 mg/L, HCO3- = 305 mg/L, and NaCl = 4% (w/w) (or 24 g/L
as Cl-). One-liter batches of the SRB were prepared by adding analytical grade Sodium
Arsenate, Sodium Sulfate, Sodium Bicarbonate, and Sodium Chloride to MilliQ
deionized water. All compounds were purchased from Fisher Scientific except the
sodium arsenate which was purchased from Sigma-Aldrich.

4.2.2 Treatment of Spent Brine

SRB was treated by co-precipitation/sorption via iron salt addition. Anhydrous


ferric chloride (FeCl3) purchased from Fisher Scientific was used for the batch
experiments. Multiple batch experiments were performed to determine the optimal
conditions and process for brine treatment. First, the effect of ferric chloride addition
was studied using 125 mL Nalgene HDPE bottles, each of which was filled with 100 mL
of the SRB. FeCl3 was then added to the SRB solutions at the Fe/As molar ratio of 1, 2,
5, 10, 15, 20, 25, 30, and 40, respectively. Bottles were placed on a gang mixer operated
at 200 rpm for ~2 hours. After the mixing period, the precipitate was allowed to settle for

33
~1 hour. The pH of the supernatant was determined using an Orion pH meter (model
520A), and the pH adjusted to 6, 7, and 9 using 1N sodium hydroxide (NaOH) or 1N
hydrochloric acid (HCl) (Fisher Scientific). Solutions were allowed to equilibrate for ~24
hours. Supernatant samples were taken, centrifuged, and filtered with 0.45µm syringe
filter. Then, duplicates were analyzed for arsenic using a Perkin-Elmer Graphite Furnace
AA.

4.2.3 pH and Aging Effect on Arsenic Removal

The disposal and treatment conditions for the process residuals can vary widely
and can change with time. Residuals may be stored from days to years before disposal
(Meng et al., 2001; Parks et al., 2003). Lagoons and landfill may become anoxic and the
brine contact time with sludge may vary. The effect of pH on the treatment process was
studied in the pH range ~3-11 and a fixed Fe/As molar ratio of 5 and 20, respectively.
The solution pH was controlled with 1N NaOH and 1N HCl. After a 2-day equilibration
period, the final pH was recorded and the supernatants prepared and analyzed for As
content.
To test the ageing effect, 100 mL of SRB batches treated with a Fe/As ratio of 15
were allowed to age in contact with the brine for 2, 20, 60, 90, 200, and 350 days,
respectively. Varying the aging period may reveal if mechanisms with slower kinetics
actively affect As mobilization or immobilization.

4.2.4 Calcium Addition

Some researchers have suggested that calcium addition to the arsenic treatment
process can reduce the leachability of the resultant solid residual (Parks, et al., 2003;
Bothe and Brown, 1999; Jing et al., 2003). Before considering the effects that calcium
had on the stability of the residual, we tested the effects of calcium on As removal from
SRB. Again, 100mL batch samples were prepared as in the FeCl3 addition experiments.
However, calcium was added in the solutions in the treatment process at two different
Ca/Fe molar ratios: 1.5 and 0.5. Calcium hydroxide (Ca(OH)2) was used as the calcium
source. Upon equilibration, supernatants were prepared as before and duplicates were
analyzed for As content. The final pH was kept between 6.0 and 7.0.

4.2.5 Regeneration with Treated Brine

To test the reusability of the treated SRB, three 500 mL batches of SRB were
treated at a fixed Fe/As ratio of 15 and at a pH of 6 for the first two batches and 9 for the
last. After precipitation is completed, the treated brine supernatant was removed and a 10
mL sample (in duplicates) was analyzed for As content. Concentration of the remaining
As in the three treated brine batches was 130, 20, and 45 µg/L. The treated brine was
then used in a column regeneration run of an exhausted PLE resin (DOW 3N-Cu)
following the regeneration procedure described before.

4.3 Results and Discussion

34
4.3.1 Arsenic Removal from Spent Brine

Batch tests exploring the effects of both iron addition and pH on the arsenic
removal from the brine solution was investigated and the optimal conditions were
identified. Figure 4-1 shows the percentage As removal as a function of pH and Fe/As
molar ratio. At an equilibrium pH of 6 or 7, over 99% of initial As (~350mg/L) was
removed from the brine at a Fe/As molar ratio or 2 or higher. Table 4-1 exhibits the
concentration of As remaining in solution after the treatment process. At pH 9, a
minimum Fe/As molar ratio of 10 is needed to achieve the same removal. Batch tests
carried out in a wider pH range revealed that pH has a major effect on As removal and is
the controlling factor when low (≤5) Fe/As ratios are used.

Table 4-1. Arsenic remaining in solution after treatment and percentage As removed at
different Fe/As molar ratio and at pH 6, 7, and 9. Initial As in brine was 310-350mg/L.
pH 6 pH 7 pH 9
Fe/As Mean As % As Mean As % As Mean As % As
Remaining Removed Remaining Removed Remaining Removed
(µg/L) (µg/L) (µg/L)
1 70115.0 80.5 49545.0 86.22 82455.0 77.07
2 316.1 99.91 503.1 99.86 45050.0 87.47
5 153.85 99.96 155.5 99.95 10835.0 96.3
10 34.0 99.99 47.64 99.98 759.8 99.73
15 21.25 99.99 42.3 99.99 329.4 99.88
20 24.75 99.99 22.05 99.99 127.69 99.95
25 54.5 99.99 33.8 99.99 158.95 99.94
30 23.35 99.99 40.04 99.99 83.52 99.97
40 21.5 99.99 34.15 99.99 75.49 99.97

35
Effect of Fe Addition on As Removal

100

95
% As Removal

90

pH 6
pH 7
85
pH 9

80

75
0 10 20 30 40

Fe/As Molar Ratio


Figure 4-1. Percentage arsenic removed from a simulated regenerant brine as a function
of the Fe/As molar ratio. Experiments were carried out at pH 6, 7, and 9, respectively.
Initial As concentration was 310-350 mg/L.

Figure 4-2 shows compares As removal as a function of Fe/As molar ratios and at
various doses of calcium (as Ca/Fe molar ratios) and at a final pH between 6.0 and 7.0.
Evidently, there is no statistically significant difference in arsenic removal in the
presence of 0 and 1.5 mol Ca per mol Fe. The presence of 0.5 mol of Ca per mol of Fe at
the Fe/As ratio of 5 exhibits a minor (<1%) removal drop but no difference is observed
when Fe/As molar ratio is greater than 10. The fact that high concentrations of calcium
do not increase the removal of arsenate suggests that direct metal-arsenate precipitation
may not be the primary mechanism in arsenic removal, rather sorption arsenate to iron
oxide/hydroxide and subsequent co-precipitation are likely the predominant mechanisms
for arsenate removal from brine. Although calcium addition did not affect arsenic
removal significantly, it does affect the stability (or leachability) of the resultant arsenic
precipitates as illustrated later on in this chapter.

36
Effect of Ca addition on As Removal

100

99
% As Removal

98

97
No Ca
Ca/Fe 0.5
96 Ca/Fe 1.5

95
0 10 20 30 40 50

Fe/As (mol/mol)

Figure 4-2. Percentage As removal at Fe/As 5-40 and in the presence of various Ca
concentrations, Ca/Fe = 0, 0.5, and 1.5. Equilibrium pH was ~6.

Figure 4-3 shows the pH effect on arsenic removal from brine in the pH range 3-
11 and at a Fe/As molar ration of 5 and 20, respectively. Greater than 95% As removal
was achieved using a Fe/As molar ration of 5 within the pH range of 3~8. When the
Fe/As molar ratio is increased to 20, >95% As removal was achieved across the entire pH
range tested. These results suggest that at relatively low doses of iron (e.g. at Fe/As molar
ration < 5), the removal rate is pH dependent, and there is an optimal pH range (e.g. 3~8).
The progressively reduced removal at pH > 8.0 indicates that arsenate and hydroxyl
anions are competing for the sorption sites, and as pH increases, the competition from
hydroxyl anions becomes stronger, and consequently arsenate uptake by iron hydroxides
is diminished. However, at higher iron doses, i.e. in the presence of excessive sorption
sites for arsenate, the pH effect becomes less appreciable.

37
Effect of pH on Arsenate Removal
100

80
% As Removal

Fe/As 5
Fe/As 20
60

40

20

2 4 6 8 10 12

pH

Figure 4-3. Effect of pH on Arsenate removal from brine at a fixed Fe/As molar ratio of 5
(filled circles) or 20 (open circles).

The observed optimal pH range in these experiments agrees with that determined
by Hering et al. for As(V) removal from drinking using FeCl3 addition (1999). The
researchers observed 100% As(V) removal between pH 4~7.5 after which the removal
efficiency decreased sharply. Although the initial conditions differ (As(V)=20µg/L and
FeCl3 4.9mg/L), the concurring observations indicate that the mechanisms that control
removal at low As concentrations and low ionic strength also prevail in the extreme
conditions.

4.3.2 Treated Brine Reuse

In general, regenerant brine accounts for a major fraction of overall process cost
for a typical ion exchange process. The treated brine contains trace levels of arsenic
(<150 µg/L), and its discharge is subject to stringent environmental regulations such as
the RCRA, and will demand extra cost. However, if it is reused, the benefits are two
folds: first, the reuse of the treated brine can greatly cut down the cost for fresh brine, and
second, the reuse greatly cuts down the volume of potentially hazardous process waste
residuals to be discharged.
To test the reusability of the treated brine for regeneration of exhausted PLEs, the
supernatant in each treatment batch was collected by pipettes without disturbing the
arsenic-laden precipitates. Upon adjustment of the supernatant pH ~9.0-10, the treated

38
brine was reused for another regeneration run of Arsenate-laden bed of DOW 3N-Cu.
Table 4-2 shows the compositions of the three batches of treated brine and the
corresponding regeneration efficiency when it is used for regeneration of DOW 3N-Cu at
pH 9 or 10.

Table 4-2. Characteristics of three treated brine batches used for regeneration.
Batch # Treatment pH Remaining As Adjusted pH % PLE
in Treated Capacity
Brine (µg/L) Recovery
1 9 130 9.0 68
2 6 20 9.0 86
3 6 45 10 100

Figures 4-4 and 4-5 show the elution history of a regeneration run using the
treated brine from batches 1 and 2, respectively. Clearly, the presence of 130 µg/L As in
the treated brine inhibits recovery of arsenate capacity, with an arsenic recovery of only
68% using 34 bed volumes of the treated brine. However, when the As remaining in
solution is reduced to 20 µg/L, the recovery is increased to 86%.

1400
Regenerant: Treated Brine (130 μg/L As)
1200 pH: 9.1
EBCT: 16.7min
Recovery: 68 %
Conc.of As(mg/L)

1000

800

600

400

200

0
0 10 20 30 40 50
BV
Figure 4-4. Elution history of arsenic during regeneration of DOW 3N-Cu using a
treated brine. Approximately 68% arsenic recovery was achieved after ~34 bed volumes
(BVs).

39
1800
1600 Regenerant: 4% NaCl including 20 μg/L As
pH: 9.0
1400 EBCT: 16.7min
Conc.of As(mg/L) Recovery: 86 %
1200

1000

800

600
400

200

0
0 10 20 30 40 50
BV
Figure 4-5. Elution history of arsenic during regeneration of DOW 3N-Cu using a treated
brine. Approximately 86% arsenic recovery was achieved after ~34 bed volumes (BVs).

Figure 4-6 shows that when a higher pH (10) is used, the full arsenate capacity is
recovered with only 18 bed volumes of the treated brine (batch 3). The compositions of
the treated brine were: As = ~50 μg/L, and Cl- = 30 g/L, with sulfate and bicarbonate
being about the same before and after the brine treatment. The main difference between
batch 2 and 3 is the adjusted pH for the regeneration run. Although batch 3 had slightly
more As remaining in treated brine, increasing the adjusted pH from 9 to 10 allowed the
recovery of about 100% of the resin capacity. Note that due to addition of FeCl3, chloride
was increased by ~25%, which favors the subsequent regeneration efficiency with only
18 bed volumes of the treated brine.

40
1400

1200 Resin: DOW 3N-Cu


Regenerant: Treated spent brine
pH: 10
Conc.of As (mg/L) 1000 EBCT: 17 min
Recovery: 100%
800

600

400

200

0
0 10 20 30 40 50
Bed Volumes

Figure 4-6. Elution history of arsenic during regeneration of DOW 3N-Cu using a treated
regeneration brine. Nearly 100% recovery of resin capacity is achieved after 18 BVs.

41
CHAPTER 5. STABILIZATION OF ARSENIC-LADEN PROCESS
WASTE SLUDGE

5.1 Introduction

As environmental regulations become increasingly stringent, the cost for handling


and disposal of water treatment process waste residuals is becoming an increasingly
important issue. For the PLE-based technology to be viable the volume of the final
process waste that leaves the plant must be small and the arsenic leachability must be
minimal.
Because of the unusually high arsenic selectivity and the easy regenerability of
the PLEs, direct reuse of the spent regenerant, and treatment and reuse of the spent brine,
the PLE-based technology offers several key advantages: 1) it can treat 10 times more
water than conventional ion exchange resins before arsenic breakthrough, which can
potentially cut down the brine need by over 80%; 2) the same brine can be reused
repeatedly for 7 times with only pH adjustment, which further reduces the brine needs;
and 3) the exhausted brine can be treated to allow for recover and reuse of over 90% of
the spent brine and to yield a small volume (<10% of the brine used), highly
concentrated, and stable waste sludge that can be safely discharged. This chapter presents
an optimized recipe to maximize the arsenic stability in the process waste precipitates/
sludge.
Some recent literatures indicate that there is a need to further study the
interactions/reactions that occur with treatment residuals in their disposed environments
such as landfills and lagoons. In measuring the contaminant leachability from solid
wastes, the viability of currently used methods has been questioned. For instance, Ghosh
and others (2004) exhibited that the commonly used EPA Toxicity Characteristic
Leaching Procedure (TCLP) does not simulate true landfill conditions. Furthermore, the
authors suggested that the TCLP underestimates the leachable As from solid residuals
under certain landfill conditions (Ghosh, 2004). Arsenic is mobilized from drinking
water treatment solids in anoxic environments due to the dissolution and reduction of
ferric hydroxides (Meng et al. 2001). The presence of calcium has been shown to further
immobilize As (Parks et al., 2003; Bothe and Brown, 1999). Jing and others studied the
leachability of treatment adsorbents such as, granular ferric hydroxide (GFH) and
granular ferric oxide (GFO), and observed that leaching of As was lowest at pH 5-7
(2005). However, there has been little information available on factors that affect the
arsenic leachability for the process waste residuals derived from regenerant brine
treatment.

5.2 Experimental Methods and Materials

5.2.1 Preparation of Arsenic-Laden Solid Waste/Sludge

Simulated spent regeneration brine was prepared in the same manner as described
in Chapter 4. However, larger (500 mL) volumes of simulated brine were used to produce
ample volumes of solid precipitates for subsequent arsenic leaching tests. The brine

42
treatment and sludge production was carried out using 1-L Nalgene HPDE bottles. The
treatment conditions were varied to probe the effect of Fe/As molar ratio, Ca addition,
pH, temperature, and aging on the arsenic stability of the resultant sludge. All sludge
samples were air-dried and tested in a dry state.

5.2.2 Arsenic-Leaching Tests

Three standard testing methods were followed to determine the As leachability


and thus relative stability of the As-laden solid precipitates, including the Toxicity
Characteristic Leaching Procedure(TCLP), extended TCLP or TCLP-ext, and the
California Waste Extraction Test (WET) as illustrated below.

1) TCLP was preformed according to EPA method 1311. In brief, 1 g of


solid sample and 20 mL of TCLP fluid #1 were placed into
scintillation vials. TCLP fluid #1 was made by adding 5.7 mL glacial
CH3CH2OOH and 64.3 mL of 1N NaOH to 500 mL DI water and
diluting to 1L with DI water. The final pH of the solution was
4.93±0.05 (EPA, 1992). The vials were placed on an end-over-end
mixer and mixed for 18+1 hours to allow for extraction equilibrium.
2) TCLP-ext was preformed by modifying EPA method 1311. In this
case, the extraction period of this procedure was modified from 18+1
hours to 30+1 hours in order to assure the extraction equilibrium.
3) WET was preformed following the method prescribed by the
California Department of Health Services (SOP No. 910). In brief, a
citrate buffer extraction solution was prepared and purged with
nitrogen gas. The 0.2M citrate solution was prepared by dissolving
42.0 g monohydrate citric acid in 950 mL of DI water. The solution
was titrated to pH 5 with 50% NaOH and diluted to 1 L with DI water
(California Department of Health Services, 1990). Dry As-laden
sludge samples were placed in 25 mL scintillation vials. All samples
were prepared by the same procedure with duplicates and an extraction
period of 40 hours. Some headspace was left in the scintillation vials.

5.2.3 Effects of Fe and Ca on Arsenic Stability

Effects of Fe addition on the stability/leachability of As was studied using 500 mL


batch tests. Fe was added to SRB at the metal/As molar ratio of 5, 10, and 15. Duplicates
were used in all cases to assure data quality. Tables 5-1 gives the conditions used in the
brine treatment.

Table 5-1. Fe doses in the tests on the effect of Fe/As ratio on the arsenic stability.
Sample Fe/As ratio Sample size (mL) Fe-addition (mmol)
ts-13-05 5 500 3.4
ts-13-10 10 500 6.87
ts-09-15 15 500 10.31

43
The resultant precipitates were air-dried for one week and then pulverized with a
set of mortar and pestle. The arsenic leaching tests were then preformed to determine the
leachable As under various conditions.
Note that the age (i.e. the time the sample sits there before the leaching tests) of
the air-dried solid samples may differ for different samples. Therefore, the stability data
obtained from different sets may vary due to the potential aging effect of the dried
samples. The approximate aging time of the dried solid samples are given for individual
experimental sets (in Figure captions). More detailed studies on the effect of aging of the
dried solids on the arsenic stability are on-going.
The effect of Ca on the stability was examined by adding various amounts of
calcium hydroxide to the FeCl3 treatment process at a fixed Fe/As molar ratio of 15.
Table 5-2 gives the experimental conditions.

Table 5-2. Calcium doses in the tests on Ca effect on arsenic stability.

Sample Fe/As ratio Sample size (mL) Ca-addition (mmol)


ts-09-15 15 500 0
ts-12-Ca2 15 500 15
ts-12-Ca1 15 500 45
ts-14-Ca3 15 500 75
ts-14-Ca4 15 500 105

5.2.4 Effects of Aging and Temperature on Stability

In a separate set of experiments, the sludge-brine contact time was varied at 2, 20,
60, 90, 200, and 350 days to test the aging effects on the arsenic leachability. Fe/As molar
ratio was held constant at 10 and the final pH of the treatment process was adjusted to
5.5-6.5. These experiments were carried out at room temperature (~25ºC). In addition,
brine treatment was performed at temperatures 5, 35, and 50ºC to test the temperature
effects on stability.
TCLP and WET were then performed, respectively, on the dried sludge samples
obtained under various treatment conditions to determine the leachable As.

5.3 Results

5.3.1 Effects of Fe and Ca on Arsenic Stability

Figure 5-1 presents the arsenic concentration in the extracting fluids for solid
samples obtained at a Fe/As molar ratio of 5, 10, and 15, respectively. The TCLP-ext
results indicate a 92% and 98% decrease in extractable arsenic when the Fe/As molar
ratio was increased from 5 to 10 and 5 to 15 respectively. When the more aggressive
WET method was applied, an 89% and 93% decrease was observed in extractable arsenic
when the Fe/As ratio was increased from 5 to 10 and 15, respectively. Based on these

44
observations, it appears that treating the brine using iron at a Fe/As molar ratio of 10 can
not only effectively remove arsenic from the concentrated brine, it also leads to the
production of stable solid waste residuals. The arsenic concentration in the extracting
fluid at Fe/As of 10 was 55.7µg/L for TCLP, which was far below the anticipated
regulation value of 500 µg/L.

Table 5-3. TCLP and WET results for effect of Fe addition on stability.
Effect of Fe-addition on sludge stability
Fe-
Fe/As Sample addition % TCLP WET
Sample ratio size (mL) (mmol) removal (µg/L) (mg/L)
ts-13-05 5 500 3.4 99.96 683.8 371.8
ts-13-10 10 500 6.87 99.97 55.7 39.65
ts-09-15 15 500 10.31 99.99 12.525 27.47
Concentration of Arsenic in Extration Fluid - TCLP

800 800

Concentration of Arsenic in Extration Fluid-WET


600 600
TCLP-ext (μg/l)
WET (mg/l)

mg/L
μg/L

400 400

200 200

0 0
0 5 10 15 20

Fe:As molar ratio (mol:mol)

Figure 5-1. Extracted As in both TCLP-ext (left axis) and WET (right axis) extraction
fluids is shown as a function of iron addition. Data represent mean of duplicates.
Leaching tests were carried out 30-100 days after the sludge samples were air-dried.

Figure 5-2 exhibits the concentration of extractable As as a function of Ca


addition measured by the TCLP and TCLP-ext, respectively. Evidently, low calcium
additions increase the relative stability of the arsenic-laden sludge. The TCLP extractable

45
arsenic was reduced by 79% when 15 mmol of Ca was added to the sludge obtained at a
Fe/As molar ratio of 15. Similarly, the WET extractable arsenic decreased by 57% when
15 mmol Ca was added. This observation was confirmed by the WET results shown in
Figure 5-3. Interestingly, as the Ca addition increased, both TCLP and WET extractable
arsenic increased. Therefore, Ca decreases As leachability only in a given range of
addition.

Table 5-4. Amount of Ca added to each sample and the resulting effect on extraction by
TCLP (µg/L) and WET (mg/L).
Effect of Ca-addition on sludge stability
Ca-
Fe/As Sample addition TCLP WET
Sample ratio size (mL) (mmol) %removal (µg/L) (mg/L)
ts-09-15 15 500 0 99.99 12.525 27.47
ts-12-Ca2 15 500 15 99.97 2.62 11.84
ts-12-Ca1 15 500 45 99.99 11.99 13.29
ts-14-Ca3 15 500 75 >99.9 26.42 11.87
ts-14-Ca4 15 500 105 >99.9 37.71 23.98

Effect of Calcium on Sludge Stability


50
Concentration of Arsenic in Extractant (μg/l)

TCLP
TCLP-ext
40

30

20

10

0
0 20 40 60 80 100 120

Ca addition (mmol)

Figure 5-2. As concentration in TCLP and TCLP-ext extraction fluid with Ca addition
of 0, 15, 45, 75, and 105 mmol in a 500mL batch test. Data are given as mean of
duplicates. Leaching tests were carried out 20-50 days after the sludge samples were air-
dried.

46
Calcium Effect on Sludge Stability (Waste Extraction Test)

Concentration of Arsenic in Extraction Fluid (mg/l)


30

WET
25

20

15

10

0
-20 0 20 40 60 80 100 120 140

Ca addition (mmol)

Figure 5-3. Concentration of As in WET extraction fluid with Ca additions of 0, 15, 45,
75, and 105 mmol in a 500 mL batch. Data represent mean of duplicates. Leaching tests
were carried out 20-50 days after the sludge samples were air-dried.

5.3.2 Effects of Aging Time and Temperature on Stability

Arsenate removal from simulated brine exceeded 99.5% at all three aging periods
(2, 20, and 60 days). A slight decrease in removal was observed with time, but the total
change between 2 and 60 days was only 0.2%. Table 5-5 and Figure 5-4 present the
results of batch tests at 25ºC and at a Fe/As molar ratio of 5 for treatment.
Table 5-5 indicates that the aqueous concentration of As increased as aging time
increased, but very little change in removal efficiency was observed between 2 and 60
days. Aging batch tests for 200 and 350 days are still in progress.

Table 5-5. As remaining in brine and percentage arsenic removal after treatment where
contact time was 2, 20, and 60 days.
Aging Time Fe/As Final pH Mean Aqueous As % As Removal
(days) (µg/L)
2 5 7.05 260.0 99.89
20 5 6.31 430.9 99.82
60 5 6.36 716.2 99.7

Figure 5-4 indicates only a slight drop (~0.2%) in removal efficiency between 2
and 60 days. While this slight drop seems statistically insignificant, 0.2% represents an
increase of ~460 µg/L As in the aqueous phase, it appears that a small fraction of arsenic

47
sorbed in the solid phase is being slowly released back in the aqueous phase. Note that
the aging was conducted in the original slurry and no water was removed.

Aging Effect on Removal

99.8
% Arsenate Removal

99.6

99.4

99.2
25 degrees C

99.0
0 20 40 60

Time (days)
Figure 5-4. Percentage As removal as a function of aging (contact time) ranging from 2
to 60 days. The brine treatment consisted of a Fe/As molar ratio of 5 at pH 6-7 and at
room temperature.

Both the TCLP and WET indicate an increase in stability after 20 days followed
by a slight decrease in stability after 60 days. Table 5-6 indicates that while the % As
extracted between 20 and 60 days increased (decrease in stability), the concentration of
As in the extractant solution actually decreased (33.55 to 23.78 µg/L for TCLP and
712.82 to 672.65 mg/L for WET). This is due to the difference in total As content in
different samples as determined by EPA method 3050B. Table 5-6 also shows 3050B
results for each sample. The WET demonstrated that 10% less arsenate was leached
when the sludge was aged for 20 days. After 60 days of aging, the WET indicated that
~4% more arsenate was leached than during a 20 day aging period. Figures 5-5 and 5-6
show the effect of the aging period on stability as characterized by either the TCLP or
WET. The samples for both figures were prepared at a Fe/As molar ratio of 10 and
treated at a pH 6-7 and aged at 25ºC.

48
Table 5-6. TCLP and WET tests for arsenic sludge samples treated for 2, 20, and 60
days, respectively. Fe/As was held at 10 and pH adjusted to 5.5-6.5. Results of 3050B
(acid digestion) are also shown.
TCLP Results
Aging Time Fe/As Final As content in Leached As % As extracted by
(days) pH solid (mg/kg) TCLP (µg/L) TCLP (mean)
2 10 6.02 27450 44.05 0.0028
20 10 5.85 28650 33.55 0.0022
60 10 6.3 24400 23.78 0.0024

WET Results
Time Fe/As Final As content in Leached As WET % As extracted by
(days) pH solid (mg/kg) (mg/L) WET (mean)
2 10 6.02 27450 950.60 34.69
20 10 5.85 28650 712.80 24.93
60 10 6.3 24400 672.65 27.57

Aging Effect on Stability (TCLP)

0.0032

0.0030

0.0028
% As Extracted

0.0026

0.0024

0.0022

0.0020

0.0018
25 degrees C

0.0016
0 10 20 30 40 50 60 70

Slurry Aging Time (Days)


Figure 5-5. Percentage As extracted by TCLP test for arsenic-laden sludge samples that
were aged (in their slurry form) for 2, 20, and 60 days, respectively. Slurry aging was
carried out at room 25oC. Data represent mean of duplicates. Leaching tests were carried
out within 8 days after the slurry samples were air-dried.

49
Aging Effect on Sludge Stability (WET)
38

36 25 Degrees C

% Arsenate Extracted (WET)


34

32

30

28

26

24

22
0 10 20 30 40 50 60 70

Time (days)

Figure 5-6. Percentage As extracted by WET for arsenic-laden sludge samples that were
aged (in their slurry form) for 2, 20, and 60 days, respectively. Aging was carried out at
25oC. Data represent mean of duplicates. Leaching tests were carried out within 8 days
after the sludge samples were air-dried.

All three temperature ranges except 35ºC showed an increase in stability between
2 and 20 days aging period. Results for 5º and 50ºC exhibited a further increase in
stability after 60 days aging period. The two extremes of the temperature range exhibit
the most obvious trend in temperature and time effect. Table 5-7 shows the data for the
aging and temperature effect experiments. Duplicate results are shown for both the
TCLP and WET for 2, 20, and 60 day aging periods at three different temperatures (5, 35,
and 50ºC). Results for 25ºC are shown in Table 5-6.

Table 5-7. TCLP and WET results in mg-As extracted per kg-sample (air-dried) for the
sludge samples that were aged (in their slurry forms) for 2, 20, or 60 days, and at
temperatures 5, 35, and 50ºC, respectively. Results of Method 3050B showing total As in
the samples in mg-As per g-sample are also given.

TCLP WET 3050B


Time (mean) (mean) (mean)
Sample Fe/As (days) Temp C mg/kg 1dup 2dup mg/kg 1dup 2dup mg/g
19-35-60 10 60 35 0.532 0.543 0.521 3641 3702 3580 26
21-5-60 10 60 5 0.319 0.38 0.258 9709.5 9089 10330 22
20-50-60 10 60 50 0.381 0.367 0.395 1414 1325 1503 26
20-35-20 10 20 35 0.53 0.53 0.53 7107.5 6440 7775 23.8
21-5-20 10 20 5 0.52 0.52 0.52 8440.5 8450 8431 23.4
23-50-2 10 2 50 0.545 0.54 0.55 7245 6799 7691 23.8
23-35-2 10 2 35 0.47 0.42 0.52 9523 9535 9511 26.9
24-5-2 10 2 5 0.56 0.51 0.61 10070 10360 9780 23.8
24-50-20 10 20 50 0.42 0.41 0.43 1674.5 1665 1684 25

50
Figure 5-7 shows the effect of time on stability at different temperatures (TCLP
results). Figure 5-8 compares the two extremes of the temperature range. TCLP results
at both 5º and 50ºC showed a steady decrease in leached arsenate (increase in stability)
with time. At 2 and 20 days aging periods, the sludge aged at 50º exhibited better
stability, but after 60 day aging period at both 5º and 50ºC, ~the same amount of arsenic
was leached.

Aging Effect on Stability at 5 degrees Celsius Aging Effect on Stability at 25 degrees Celsius
(TCLP) (TCLP)

0.0028 0.0032

0.0026
0.0030
5 degrees
0.0024

% Arsenic Leached
% Arsenic Leached

0.0028
0.0022
0.0026
0.0020

0.0018 0.0024

0.0016
0.0022
0.0014
0.0020
0.0012
0.0018 25 degrees
0.0010

0.0008 0.0016
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70

Time (Days) Time (Days)


(a) (b)

Aging Effect on Stability at 35 degrees Celsius Aging Effect on STability at 50 degrees Celsius
(TCLP) (TCLP)

0.0023 0.0024

0.0022 50 degrees
0.0022
% Arsenic Leached
% Arsenic Leached

0.0021

0.0020
0.0020

0.0019 0.0018

0.0018
0.0016

0.0017

0.0014
0.0016 35 degrees

0.0015 0.0012
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70

Time (Days) Time (Days)


(c) (d)

Figure 5-7. TCLP results for samples aged for 2, 20, and 60 days and at 5, 25, 35, and
50ºC, respectively. Data represent mean of duplicates. Error bars represent standard
deviation. Leaching tests were carried out within 8 days after the sludge samples were
air-dried.

51
Aging Effect on Stability at 5 and 50 Degrees C
(TCLP)

0.0028

0.0026 5 degrees
50 degrees
0.0024
% Arsenic Leached

0.0022

0.0020

0.0018

0.0016

0.0014

0.0012

0.0010
0 10 20 30 40 50 60 70

Time (days)

Figure 5-8. Percentage of total As leached by TCLP for sludge samples aged for 2, 20,
and 60 days, respectively, and at 5 and 50oC, respectively. Data represent mean of
duplicates. Error bars represent standard deviation. Leaching tests were carried out within
8 days after the sludge samples were air-dried.

The WET results indicate an increase in stability at all four temperatures when the
aging period was extended from 2 days to 20 days. At 35ºC and 50ºC, a further increase
in stability was observed when the aging period was increased from 20 days to 60 days.
Figures 5-9 shows the effect of slurry aging on the residual stability at temperatures 5º,
25º, 35º, and 50ºC respectively.

Aging Effect on Stability at 5 degrees Celsius Aging Effect on Stability at 25 degrees Celsius
(WET) (WET)

50 38

5 degrees C
48 36
25 degrees C
% Arsenic Extracted

% Arsenic Extracted

46 34

44 32

42 30

40 28

38 26

36 24

34 22
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70

Time (days) Time (days)


(a) (b)

52
Aging Effect on Stability at 35 degrees Celsius Aging Effect on Stability at 50 degrees Celsius
(WET) (WET)

35
40

35 degrees C 30
50 degrees C

% Arsenic Extracted
35
% Arsenic Extracted

25

30
20

25
15

20
10

15 5

10 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70

Time (days) Time (days)


(c) (d)

Figure 5-9. WET results for samples aged (in their slurry forms) for 2, 20, and 60 days,
respectively, and at 5, 25, 35, and 50ºC, respectively. Data represent mean of duplicates.
Error bars represent standard deviation. Leaching tests were carried out within 8 days
after the sludge samples were air-dried.

Comparing the results for aging at 5º and 50ºC indicated a clear enhancement in
arsenic stability at elevated temperatures. Figure 5-10 compares the aging effect on
stability at these two temperatures. The WET indicates that the most stable temperature
for aging is 50ºC and for an aging period of 60 days. Even after 20 days, the stability at
50ºC exceeds that of all other temperatures for all aging periods.
Figure 5-11 shows the effect of temperature on stability at the three different
aging periods 2, 20, and 60 days. All three aging periods showed an overall increase in
stability as the temperature increased from 5º to 50ºC. This figure exhibits that a 20 day
aging period combined with a moderate temperature of 50 oC can greatly enhance the
arsenic stability.

53
Effect of Aging on Stability at 5 and 50 Degrees C
(WET)

60

5 degrees C
50 50 degrees C
% As Extracted

40

30

20

10

0
0 10 20 30 40 50 60 70

Time (days)
Figure 5-10. Comparison of As leachability as a function of slurry aging and at 5ºC
(filled circles) and 50ºC (open circles). Data represent mean of duplicates. Error bars
represent standard deviation. Leaching tests were carried out within 8 days after the
sludge samples were air-dried.

Effect of Temperature on Stability at 2, 20, and 60 day


Aging Period (WET)

60

50 2 days
20 days
% Arsenic Extracted

60 days
40

30

20

10

0
0 10 20 30 40 50 60

Temperature (Celsius)
Figure 5-11. Percentage As extracted by WET as a function of temperature. All three
aging periods indicate that leachability decreases with increased temperature. Data
represent mean of duplicates. Error bars represent standard deviation. Leaching tests were
carried out within 8 days after the sludge samples were air-dried.

54
5.4 Discussion and Conclusions

The stability of the arsenic-laden process sludge was observed to increase at


moderately elevated temperatures and at increased aging period. These results reveal
information about the reactions occurring and their kinetic characteristics. It has been
well recognized that there are multiple reactions occurring in the arsenic removal and
aging process, with a fast reaction (e.g. adsorption) step followed by slower kinetic steps
such as intra-particle diffusion and/or surface precipitation. Our results support the
hypothesis that the second slower kinetic steps may enhance the stability of the solid
residual. An earlier study on phosphate adsorption by Zhao and Stanforth (2001)
suggested that the slow fraction of phosphate is exchangeable rather than the fast
(adsorbed) fraction. If the slow fraction of phosphate removal was governed by intra-
particle diffusion then this fraction would not be available for exchange. Zhao and
Stanforth hypothesized that surface precipitation may govern the slow fraction allowing it
to be exchangeable. Since phosphate and arsenate ions behave similarly in an aqueous
environment, it can be hypothesized that surface precipitation may account for the
second, slower reaction observed in our study.
These results also indicate a positive relationship between stability and
temperature. This relationship suggests that the kinetic nature of the second reaction is
temperature dependant. More concisely, stability increases with both increased
temperature and time. These results elucidate the optimal conditions for an engineered
process for the treatment and stabilization of the solid waste residual resulting from spent
regeneration brine treatment.
The TCLP extracts very little arsenic from the solid residual (<0.005%), even
when the solid contains >25 mg/g arsenic. Therefore, it may not adequately reflects the
leachability of arsenic in samples subjected to various treatments. On the other hand, the
California WET is much more powerful and extracts more easily measurable and
comparable amounts (5-50% available As). For example, after a 60 day aging period at
room temperature, the As concentration in the TCLP extraction fluid was 23.78 µg/L
while the concentration in the WET extraction fluid was 672,650 µg/L. Therefore, it is
suggested that these facts be kept in mind when using TCLP results to make comparisons
between the effects of specific parameters. The As concentration in the WET leachate
was two orders of magnitude greater than the test limit (5 mg/L).
The authors would like to point out a discrepancy in the WET results from two
different data sets presented in Tables 5-3 and 5-6, where WET was employed to
determine the leachable As in sludge samples prepared with varied Fe addition (section
5.3.1), and for sludge samples of different aging periods (section 5.3.2). While Method
3050B confirms that the total As in both data sets is about the same (20~25 mg-As/g
sludge), the arsenic in the extractant differed by over one order of magnitude. This is
likely due to the difference in the aging of the dried sludge samples (i.e. the time the
dried samples sit before the leaching tests, or dry-aging). Our preliminary data suggest
that the strongest effect of the dry-aging on the arsenic stability appeared during the first
week, it became stable after 20 days. Detailed quantitative investigations are in progress.
Based on the results presented the following conclusions have been made:

1) Optimal pH for nearly completely removing arsenic from spent brine is 3-7.

55
2) Highly efficient (>99%) As removal from spent brine can be achieved at Fe/As
molar ratio ≥2 at pH 6-7.
3) Brine can be reused for regeneration after arsenic removal, and essentially no
liquid hazardous waste residuals leave the plant.
4) Contact time (i.e. the slurry aging) has little measurable effect on As removal
from brine.
5) WET and TCLP show a decrease (~10% WET) in leached arsenic after aging for
20 days as opposed to 2 days at room temperature (25ºC).
6) In general, the arsenic stability increases (leachability decreases) with both
increased temperature and aging period.
7) Based on the WET and TCLP results, 60 days of aging of the wet sludge and at a
moderately elevated temperature 50ºC can greatly reduce the arsenic leachability.
8) The WET is much more powerful than the TCLP with a concentration of As in
extraction fluid 4 orders of magnitude greater than the latter.
9) A second, kinetically limited process appears occurring, leading to the decrease in
the arsenic leachability.

56
CHAPTER 6. PRELIMINARY SEMI-PILOT SCALE TESTING OF
THE PLE TECHNOLOGY
This chapter summarizes the preliminary results pertaining to the practical
effectiveness of the PLE for selective removal of arsenic from real-contaminated water
when tested on a semi-pilot scale. The primary goal was to confirm the effectiveness of
the new ion exchange material and the proposed engineered process for treating the
process waste residual. However, it was not attempted to optimize the operating
conditions at this stage. This part of work was conducted at Texas A&M with the help of
our collaborator, the El Pass Water Utility, TX.

6.1 Experimental Procedures

An arsenic-contaminated field water from Well 303, El Paso Water Utility, TX,
was used in the semi-pilot scale testing of the PLE technology. The experimental
conditions for the fixed-bed column run are specified as follows:

- PLE: DOW 3N-Cu


- Field water: Well 303, El Paso Water Utility, TX (165 gallons)
- Initial concentration of As : 16.4 μg/L
- Initial concentration of sulfate : 137 mg/L
- Bed volume of resin : 120 cm3(mL)
- Bed volume of column : 330 cm3(mL)
- Flow rate : 24 mL/min
- EBCT : 5 min
- Influent pH : 8.66
- Effluent pH : 6.18
- Column size
• Diameter: 35 mm
• Length of column: 360 mm
• Length of resin filled: 145mm

The tests were performed using fixed-bed column experiments. The resins were
supported by glass wool. Natural arsenic-containing feed water from El Paso Water
Utility was placed in 55 gallon bottle. A Peristaltic pump equipped with flow rate
controllers was used to feed the bed. The field water was fed to the column in a
downflow mode. The effluent from the columns was collected at pre-determined time
intervals and analyzed for arsenic(V), sulfate, chloride, and pH. Arsenic(V) analysis was
performed using a Graphite Furnace Atomic Adsorption Spectrometry. Sulfate and
chloride were analyzed using a Dionex ion chromatograph.
The same set-up was used for regeneration of the arsenic-laden PLE.
Regeneration of spent columns was performed in an upflow mode and at an EBCT of 30
min.

57
6.2 Preliminary Column Run Results

Figure 6-1 shows the breakthrough histories of arsenate and sulfate under the
field-water conditions. Although the operating conditions (e.g. EBCT) were not
optimized and despite the high influent pH and the presence high concentrations of
sulfate, about 3400 bed volumes water can be treated before arsenic breakthrough. The
results confirmed the resin’s high selectivity for arsenate over sulfate – sulfate
breakthrough took place at less than 300 bed volumes. The preliminary results warrant
further pilot-scale testing and process optimization.

sulfate and arsenic breakthrough curve

20 160

Sulfate Influnet:
pH = 8.66 140
As(V) = 16 ug/L
SO42- = 137 mg/L
15 120

100

SO42-(mg/L)
As(ug/L)

10 80

60
Arsenate
5 40

20

0 0
0 1000 2000 3000 4000

Bed Volume

Figure 6.1. Arsenate and sulfate breakthrough histories during a semi-pilot scale
fixed-bed column run using DOW 3N-Cu for treating a contaminated well water from El
Paso Water Utility.

In addition, the semi-pilot testing also confirmed that the PLE can be highly
effectively regenerated using 4% NaCl at Ph >9.0. Over 90% of recovery was achieved
within 15 bed volumes of the regenerant.

58
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