Professional Documents
Culture Documents
BY
IN
ENVIRONMENTAL MANAGEMENT
NOVEMBER, 2014
BY
A dissertation submitted to
School of Business Administration
OF
DOCTOR OF PHILOSOPHY
IN
ENVIRONMENTAL MANAGEMENT
November, 2014
2
Treatment of Sewage Wastewater using Different
Techniques for the Reduction of Pollution Load
and its Application for Irrigation Purpose
BY
Dissertation Committee:
________________________
Chairman
________________________
Member
________________________
Member
Rector
National College of Business
Administration & Economics
3
DECLARATION
4
DEDICATED
TO
5
ACKNOWLEDGEMENT
All admiration and thanks are for my Allah, the Almighty, the Sublime, the
only Creator of the universe and source of knowledge and ingenuity who blessed
me with health, thoughts, talented teacher, helping friends and opportunity to
complete this study. I offer my meekly thanks to Holy Prophet ( Peace Be Upon
Him) the nimbus, the beacon, whose moral and spiritual teaching illuminated my
heart, mind and thrived my thoughts towards achieving high ideas of life.
At the last I am highly obliged to my wife and Kids who suffered during my
research work.
6
RESEARCH COMPLETION CERTIFICATE
7
SUMMARY
Rapid increase in population and Industrial development has increased the wastewater
volume, declining the water resources and adjoining environment due to inappropriate
management. In developing world including Pakistan, industrial and municipal wastewaters are
being used for the irrigation of crops or discharged into canals, rivers. Present study was
conducted to evaluate the Combined Laboratory wastewater of PCSIR, Lahore, sewage effluents
being disposed of in the city sewer which is being used for agriculture in the area of Lahore for
growing vegetables, fodder which affects the quality of food, soils and crops.
The quality of combined laboratory wastewater was assessed. Large variations were found
in water quality. The irrigation quality of combine wastewater was poorest with respect to
various parameters including pH, COD, BOD, sulphide and the concentration of heavy metals
was also above the FAO limits. There was accumulation of heavy metals in soils receiving
wastewater for irrigation. The total metal contents in soil follow the order Cd > Ni >Cr>Zn. The
sequential extraction procedure developed by Tessier was used to demarcate four metal fractions;
exchangeable, acid soluble, reducible, oxidisiable and residual. Fractionation procedure showed
that all the metals except Cd were dominant in the residual fraction. It was observed that the
concentration of all studied toxic metals in edible part of the vegetables was above the
permissible level. The meaningful positive correlation was observed between concentrations of
metal in vegetables. t was observed that the practice of using wastewater in irrigation for
growing vegetables and other crops is non-sustainable.
In order to study the bioavailability and uptake of Cd, Cr and Ni in sandy soils, with two
levels of organic matter by Cucumber, Tomato and Maize was studied in field experiments. It
has been investigated that the characteristic of soil, such as texture, and organic matter contents
affect the mobility of the metal added. The transfer of metals to plants was higher in sandy soil
and differs among plant species. The non-essential elements Cd, Cr and Ni can shift into the
edible parts of Cucumber, Tomato and Maize.
8
LIST OF PUBLICATIONS
1. Butt, M. T., Ahmed .A. S. and, Athar. M. (2012). Treatment of Domestic Wastewater
Using Different Low Cost Materials
Pak. J. Sci.Ind.Res.Ser.Phys.Sci.2012.55 (2)112-116.
9
LIST OF ABBREVIATION
Abbreviation Description
AAS Atomic Absorption Spectrophotometer
AOAC Association of Official Analytical Chemists
APHA American Public Health Association
BOD5 Biochemical Oxygen Demand
Combined wastewater Laboratory Wastewater + Domestic Wastewater
Ca2+ Calcium
Cd Cadmium
CEC Cation Exchange Capacity
Cl- Chlorides
Co32- Carbonates
COD Chemical Oxygen Demand
Cr Chromium
Ec Electrical Conductivity
ECe Electrical Conductivity of Soil Saturation Extract
FAO Food and Agriculture Organization
HCO3- Bicarbonates
K+ Potassium
Pb+ Lead
m.moleL1- Mille mole charge per liter
mg.Kg1- Milligram per Kilogram
mg.L1- Milligram per Liter
Mg2+ Magnesium
Na+ Sodium
NEQS National Environmental Quality Standards
Ni Nickel
OM Organic Matter
Radiation Micro wave Radiation
PCSIR Pakistan Council for Scientific and Industrial Research
RSC Residual Sodium Carbonate
R1 Reading 1
R2 Reading 2
R3 Reading 3
SAR Sodium Absorption Ratio
SBR Sequence Batch Reactor
SO42- Sulphate
SBR Sequence Batch Reactor
TDS Total Dissolved Solids
TSS Total Suspended Solids
WASA Water And Sewerage Agency
Zn Zinc
10
ANNEXURE I, TABLE OF CONTENTS
Page
Declaration 4
Dedication 5
Acknowledgement 6
Research Completion Certificate 7
Summery 8
list of Publications 9
List of Abbreviations 10
Table of Contents 11
CHAPTER :1 Introduction 13
CHAPTER :2 Literature Review 17
Amis and Objectives 24
CHAPTER :3 Research Mythology 25
3.1 Different Treatment Techniques Available for Waste Water 25
3.2 Collection of Combined Waste Water Samples 25
3.3 Coagulation 25
3.4 Adsorption 26
3.5 Ozonation 26
3.5.1 Waste Water Treatment by Ozone 27
3.5.2 Decolourisation 28
3.5.3 Ozone doze for COD 28
3.54 Detoxification 28
3.5.5 Disinfection 28
3.5.6 COD and BOD Reduction 29
3.5.7 Sludge Reduction 29
3.5.8 Phosphorus Removal by Slag 29
3.6 Metals Removal by Adsorption Method 30
3.6.1 Preparation of Adsorbent 30
CHAPTER :4 Results and Discussions 32
4 Study by Activated Carbon and Ash 32
4.1 Results and Discussion 32
4.2 Different Treatments for Combined Laboratory Waste Water 35
4.3 Removal and Recovery of Phosphorus From Combined Laboratory Waste Water 50
4.4 Initial Ammonia Concentration Effect 83
4.5 Effect of Initial pH 85
4.6 Effect of Radiation Contact Time 86
4.7 Conclusion 87
4.8 Heavy Concentration in Combined Laboratory Waste Water 90
4.9 Results and Discussion 116
4.10 Pollution Load of Combined Laboratory Waste Water Temperature, pH, BOD,COD 117
4.11 Irri Irrigation Quality pH, Electrical Conductivity, Total Suspended Solids, Total 118
Dissolved Solids, Chloride, SAR, RSC
4.12 Total Nitrogen, Total Phosphorus 119
4.13 Heavy Metals 119
4.14 Conclusion 120
4.15 Raw Combined Laboratory Waste Water Irrigation Impacts on Soils and Vegetables 121
4.16 Total Concentration and Fractionation of Metals in Combined Laboratory Waste 123
Water Irrigated Soils
11
4.17 Cadmium 126
4.18 Nickel 139
4.19 Chromium 140
4.20 Zinc 140
4.21 Cadmium 140
4.22 Nickel 141
4.23 Chromium 142
4.24 Zinc 142
4.25 Correlation Analysis 142
4.26 Conclusion 143
4.27 Role of Soil Texture and Organic Matter 143
4.28 Effect on Crop Yield 144
4.28.1 Cucumber, Tomato and Maize 148
4.28.2 Cucumber 148
4.28.3 Tomato 149
4.28.4 Maize 149
4.28.5 Nickel 151
4.29 Metals in Post-Crop Soils 152
4.30 Cadmium 152
4.31 Nickel 153
4.32 Chromium 153
4.33 Transfer Factor of Heavy Metals from Soil to Plants 153
4.34 Conclusion 154
4.35 Restrictions 154
4.36 Need for Further Study 154
Pictures 155
References 156
12
CHAPTER 1
INTRODUCTION
Quality of drinking-water is a major concern of human health in developing
and developed countries. Cities are expanding at an unbelievable rate worldwide.
Presently world urban population comprises of 2.8 billion, which will rise to 3.8
billion in 2015 and to 4.5 billion in 2025 (WHO 1996). Pakistan is the 6 th most
thickly populated country in the world with 184.35 million peoples that are
prospective to an increase up to 221 million by 2025 and will achieve nearly 5 th
position in the world in terms of total population in 2050 (PEPA 1997; PES 2012,
2013). It had been estimated that over a billion people do not gain access to the safe
drinking water. Almost 80% of diseases were due to a poor water quality which
might lead to nearly 1.7 million victims annually, particularly in the developing
countries (UNDP 1996; WHO 1996).
It had also been calculated that the accessibility of safe drinking water in
Pakistan for public utilisation had already been decreased in 2005 from 5300 m 3 per
capita to 1100 m 3 (IUCN 2005, IUCN 2009; PEPA 1997; PES 2012, 2013). Since
Pakistan is emaciating its natural resources quickly, if water resources are not
handled appropriately it might surmount a water scarceness country in near future.
(i.e., a country where clean available water is below 1,000 m 3 per capita) (IUCN
2005, IUCN 2009; PEPA 1997; PES 2012, 2013). It has been investigated that
Pakistan’s total water availability per capita ranked at 26 th level in the dead-last-list
among the 26 Asian countries (FAO 2002). It has been ascertained that nearly all the
major towns in Pakistan that have sewage disposal systems, the waste water is
frequently used for agriculture purpose. In those towns, where sewage water is not
used for irrigation purposes, it is disposed of in surface water bodies like irrigation
canals. In an investigation, it has been detected that about 28 m 3 sec -1 wastewater
from the city of Lahore was being consented into the river Ravi without any
treatment. It has further been estimated that it will rise to 35 m 3 sec -1 by year 2017
(Saeed and Bahzad 2006).
The utilisation of municipal wastewater for agricultural purposes is an old
practice in many countries like China, Mexico and Vietnam. It became more
significant under a deficiency of fresh water resources that are often fa ced by arid
and semi-arid countries around the world (Asano and Levine 1996). There are many
benefits in using the municipal wastewater for agriculture purposes. It furnishes not
only a trustworthy water supply to the agriculture products, mostly in dry ar eas of
low earings but also reprocessing of nutrients, thus cutting down the need of farmers
to invest in fertilizers. Phosphorus and nitrogen compounds which are mostly
demonstrated in urban and industrial wastewater are essential nutrients for plants,
could also be a vital financial benefit. Abbas et al., (2007) and Bose and
Bhattacharyya (2008) indicated that the direct use of wastewater for agriculture
often precludes pollution in rivers and other water bodies. This is therefore, an
economical method for dumping off effluents and disposition of urban wastewater in
13
most of the areas of Pakistan because all types of wastewater moving into a single
drain and there is no separate drainage system for both industrial and domestic
wastewater (Abbas et al., 2007; Bose and Bhattacharyya 2008). The sewage water
mainly consists inorganic, organic matter, floating or suspended insoluble particles
etc. The organic matter present in urban and industrial wastewater included fatty
materials, carbohydrates, proteins, their breakdown products, detergents and other
different natural and synthetic chemicals. Furthermore industrial activities and
manufacturing of essential commodities frequently bring forth enormous volume of
wastewater as effluents containing heavy metals and other toxicants, which
deteriorate the quality of aquatic systems (Abbas et al., 2007; Bose and
Bhattacharyya 2008).
Long term diligence of irrigation with wastewater is known to increase
significantly the metals content of soil particularly the heavy metal contentedness.
Metal particles due to their non-degradeable nature often congregated in soils and in
environment which reaches to a toxic level (Kumar et al., 2007). Irrigation with
wastewater bearing toxic metals not only contaminates agricultural soils, but also
adversely effect the safety and quality of food materials. It also exhibits serious
threats to the safety of environments. At ample concentration, they affect the
metabolic process and embarrass the plant growth. Heavy metals are usually toxic
for the floral life and contaminate crops (Chung et al., 2011; Mapanda et al., 2005;
Noor-ul et al., 2013). Most of the heavy metal particles which could be transferred
through plant materials are usually toxic due to their solubility in water. Small
quantities of heavy metals have uncongenial consequences on human beings and
animals due to the lack of a suitable removal system from the body. Heavy metals
particles contaminate diet and reduce some essential nutrients in the body that
initiate many diseases (Arora et al., 2008; Khan et al., 2008b; Krishna et al., 2009;
Lei et al., 2008; Muchuweti et.al., 2006; Zakir et al., 2009).
Due to the non-biodegradable nature, long half-lives and their potentials for
building-up their concentrations in different body parts, heavy metals are very
injurious. Most of the heavy metal particles are colossally toxic because of their
solubility in water. Even small amount of heavy metal ions has inauspicious effects
on man and animals probably due to a nonexistence of appropriate mechanism for
their elimination from the body. (Arora et al., 2008; Krishna et al., 2009; Lei et
al.,2008). The inauspicious effects of the irrigation with untreated sewage
wastewater on the ecosystem, specially on urban ecosystem, on the health of human
being and grazing animals have been investigated by many research workers (Arora
et al., 2008; Chung et al., 2011; Jan et al., 2010a; Jan et al., 2010b; Khan et al.,
2008a; Khan et al., 2008b; Krishna et al., 2009; Lei et al., 2008; Mapanda et al.,
2005; Muchuweti et al., 2006; Noor-ul et al., 2013; Pasha et al., 2010; Sharma et al.,
2008; Zakir et al., 2009; Zhang et al., 2005).
A common persuasion of the research workers and policy makers in different
countries of the world is that the use of raw sewage water is not satisfactory and
could only be utilized after an appropriate treatment is given. Many treatment
technologies have been devised to treat industrial wastewater. The most significant
technologies consist of coagulation and flocculation process; membrane filtration
and oxidation process. All these processes are quite complex, expensive and time
consuming. They also required trained manpower (Amuda et al., 2006; Amuda and
Ibrahim 2006). The prodigious high price of activated carbons has given a boost for
14
economical alternatives. Cost effective adsorbents such as wood, bone, nut shells,
processed peat and biomass have been reported by many research workers for the
elimination of organic pollutants and heavy metals ions from the wastewater of
several industries (Hussein et al., 2004). Pulverized fuel ash, furnace slag, ordinary
port land cement, coal cinder, iron oxide and related cement blends were used to
remove and recover phosphate from aqueous solution (Aleksandra et al., 2006; Zeng
et al., 2004). Jian et al., (2009) investigated that the phosphate adsorption capacity
of the tailings depended on many factors like contact time, initial phosphate
concentration and pH. With an increase in pH of the medium, recovery of phosphate
was observed to about 13–14% which was possible due to a strong bonding between
the adsorbed PO 4 -3 and iron oxides which ultimately decreasing the phosphate
adsorption (Jian et al., 2009). Xiong et al., (2008) on the other hand, depicted the
used of furnace steel slag for the recovery of phosphates and various factors such as
adsorbent dose, pH and temperature that effect the removal of phosphates. They
further demonstrated the removal of about 62–79% of total phosphates and 71–82%
of dissolved phosphorus from secondary effluents by this method (Xiong et al.,
2008). According to them, high ability and low cost were the main factors for choice
of steel slag, for the removal of phosphate from both the urban and industrial
wastewater (Xiong et al., 2008). Presently in Pakistan, only three or four treatment
plants are working and treating the sewage wastewater to a primary level.
During this study coagulation, flocculation, activated sludge, ozonisations and
adsorption techniques were used for the removal of COD, BOD, total suspen ded
solids, dissolved solids, trace metals and heavy metals. Converter slag was used for
the treatment / removal of nitrogen and phosphorus from wastewater. Coagulation,
flocculation and sedimentation process tests were employed using Jar tests
technique. The polymer was used as a coagulant aid and FeCl 3 as a coagulant.
Wastewater samples were treated and their sludge was measured. This research
project was designed to select the most suitable single technique or a combination of
techniques that could give rise to a high quality, treated wastewater in a relatively
shorter time for the disposition into water bodies or for the agricultural utilisation. It
has been estimated that water employed for various purposes such as laboratory,
washing, bathing, gardening/ agricultural usage and for consumption purposes is
about one hundred thousand gallons daily while the superfluous or otiose water
generated from it, is approximately 40 thousand gallons (Naz et al., 2012). Naz et
al., (2012) also analysed the wastage water from the PCSIR laboratories complex
Lahore and reached to a conclusion that this was consisted of residential, black
water from toilets, gray water from bath, kitchen’s waste -water generated from the
research activities in the laboratories which was disposed of in the local sewer
system without any treatment (Naz et al., 2012). Keeping in view the importance of
metal contamination of soils and crops during the agricultural usage of sewage and
industrial effluents and also all other health hazardous parameters in mind this
research project was innovated.
15
AIMS AND OBJECTIVES
Since the use of raw sewage water is not acceptable; not only for irrigation
purposes and for both flora and fauna population in different areas of Pakistan but
also for the consumption and other purposes for human beings. Furthermore the
metal particles and ions, present in it are deleterious for all the living creatures
present in different parts of Pakistan. It is thus laudable to organise such a research
project that deals with the reduction of pollution impact divulged by the sewage
water by some suitable low-cost treatment, evaluation of treated wastewater, its
effects on soil and crop yield and its reuse for irrigation. Recovery of the nutrients
and appraising the possibility of heavy metal uptake by locally growing crops such
as cucumber, tomato and maize after using wastewater will be another aliquot of the
project.
16
CHAPTER 2
LITERATURE REVIEW
Many research workers described various techniques for the treatments of
wastewater and for the removal of metal particles and ions. Murtaza et al., (2010)
were of opinion that although the raw sewage water was a good source of plant
nutrients for agricultural lands in developing countries but might affect food chain
quality, specifically the cadmium which was the most toxic metal particularly for
leafy vegetables. Rajesh et al., (2007) analysed the metal contents from the samples
of wastewater that were used for irrigation and found a high concentration of metal
ions like Ni, Cd, Cu, Zn, Pb, Cr, and Mn. They concluded that the higher levels of
such metal ions contaminate vegetables and often create possible health risks.
Similarly, the municipal and industrial wastewater was examined by Rahm ani (2007)
and estimated different concentration of COD, BOD, TSS, SO 4 -2 , Cl -1 , HCO 3 -1 , and
N-NO 3 , TDS, SAR and heavy metals such as Cu, Mn, Cr, Co, Cd and Zn. Zhou and
Smith (2002) and Gori et al., (2004) depicted the speedy growth of populace in an
area along with the identification of various pollutants in water mainly due to the
industrial activities. They also outlined the relationship of the water resources with
respect to their usage among the population and also their diminution.
The utilization of various techniques for the removal of metals particles and
also heavy metal ions from the municipal and industrial wastewater were
investigated by many workers (Manu et al., 2008; Rahmani 2007; Rajesh et al.,
2007). Zhou and Smith (2002) used UV radiation, membrane filtration and advanced
oxidation technique for making the wastewater re-useable. They also compared their
own techniques with the existing traditional ones and concluded that these exhibited
a superior protection of public health and for the environment. Since wastewater
could be a source of nutrients; their effectiveness depends on the crop type and
levels of soil fertility but Gori et al., (2004) demonstrated that the sewage
wastewater bring down the fertilizer demands and increases the crop yields. The
benefits and disadvantages of their technologies with limits were also portrayed by
them (Zhou and Smith 2002). Metcalf and Eddy (2003), Gogate and Pandit (2004)
and Ong et al., (2005) on the other hand exploited various other techniques such as
adsorption, bio-degradation, batch reactor techniques and oxidation technique for the
removal of toxic industrial wastewater pollutants and powdered activated carbon
along with the dried activated sludge were used for the removal of toxic metals
particles and ions like Cu, Cd, Ni, Zn, and Cr from polluted wastewater. These
research workers also revealed that the activated carbon and activated sludge had
higher removal capacity of these ions as compared to the dried sludge (Gogate and
Pandit 2004; Metcalf and Eddy 2003; Ong et al., 2005). Similarly phosphate
particles and ions were removed from wastewater by Zeng et al., (2004) after the
utilisation of fly ash, furnace slag, port land cement, coal cinder, iron oxide and
related cement blends.
Pelino (2007), Reungoat et al., (2010) and Sanchez-Polo et al., (2006) made
use of ozonisations techniques solitary or combined with activated carbon, while
Cox (2007) applied ion exchange material resin for getting rid of organic contents,
17
partially degraded organic matter, heavy metal particles and other harmful ions from
the municipal and industrial wastewater. Such ozone treated disinfected water after
taste improvement was claimed to be suitable for drinking purposes (Cox 2007;
Pelino 2007; Reungoat et al., 2010). Sajjad and Javed (2009) applied coagulation,
flocculation and sedimentation techniques, where they used alum in combination
with C-492 polymer (cationic) for the treatment of wastewater from tannery industry
and removed about 99.7% turbidity of pollutants.
Many research workers worked on the removal of phosphorus either in the
form of crude particles or as ions from the wastewater by using different techniques
e.g., Berg et al., (2005) used a crystallization process by seed induced technique
through phosphorus precipitation and procured nearly 100% recovery of this metal
while Yim and Kim (2005) used furnace slag, blast furnace and converter slag for
the removal of this metal and secured nearly 99.1% phosphorus metal retrieval while
Andy et al., (2006) removed only 77% of phosphorus efficiency from the municipal
and industrial wastewater through the precipitation and adsorption techniques.
Similarly Kim et al., (2006) abstracted 80% of phosphorus from wastewater after
utilization of powdered converter slag as a seed material, where they regarded the
concentration of Ca 2+ , dosage of slag, temperature, pH, hydraulic retention time and
crystallization process as the chief effective factors. Yim and Kim (2005) further
concluded that their technique had technical and economic vantages over the other
three seeded materials. In an alike manner, Aleksandra et al., (2006) utilized furnace
steel slag and serpentine for the removal of phosphorus by considering the hydraulic
retention time, adsorption, precipitation and filter-bed-techniques and obtained a
100% recovery. Jiangang et al., (2007) and Chen et al., (2007) investigated the
sorption capacities and composition of fly ashes. The fly ashes containing higher and
medium calcium content at neutral pH values used by these workers indicated better
results for removal of phosphates when compared with the fly ashes of low calcium
concentrations. They further came to a conclusion about the phosphorous absorption
by fly ash which was achieved by calcium and iron constituents. According to
Jiangang et al., (2007) and Chen et al., (2007) the fly ashes of low calcium
concentrations usually immobilize small quantities of phosphate at all the used pH.
Steel slag with a mechanism of a magnetic type separation through an ion exchange
was also exploited by Xiong et al., (2008) to remove phosphate from the synthetic
solutions. Under the influences of the factors like adsorbent dose, pH and
temperature, the rate of removal of phosphate was nearly 79 to 82%. According to
Xiong et al., (2008) the low cost and higher ability of steel slag, nominate its
selection easy for phosphate removal from synthetic solution and real wastewater.
Jian et al., (2009) on the other hand, used converter slag–coal-cinder-columns for
the removal of phosphorous and other pollutants and indicated that the phosphate
adsorption capacity of tailings had many factors such as initial phosphate
concentration, contact time and pH. Yang et al., (2009) used converter slag–coal-
cinder-columns for the removal of dissolved phosphorus, total phosphorus, COD,
NH 4 + – N and other pollutants from wastewater.
The effectiveness of FeCl 3 and polymer for coagulation process to decrease
the trace metals such as Pb, Cd, Fe, Cr, Ni and Zn from the municipal and industrial
wastewater was estimated by Amuda et al., (2006) who employed coagulation
flocculation process for these intentions. According to these authors, these methods
were complex, high-priced due to eminent expenses of activated carbon, time
18
consuming and usually required competent man power. These expensive parameters
did not dissuade other research workers who were encouraged to search for some
low-cost substitutes for the remove of pollutants from the municipal and industrial
wastewater (Amuda et al., 2006). Kivisaari (2009) easily isolated Al 3+ and Fe 3+ ions
from the industrial wastewater by a process of hydrolysis through the use of
coagulants which constituted insoluble sediments with these metal ions. Kisibi
(2006) utilized H 2 O 2 in a dose of 1.5 ml per litre of wastewater as a potent oxidising
agent which was able to remove COD, BOD and organic compounds to about 85%.
Nitrogen contaminants in the form of COD, T-P, NH4+ -N and T-N were removed by
Zhang et al., (2005) with usual hydraulic loading as high as 8 cm d −1 . Soon-An et
al., (2010) used activated carbon, activated sludge and dried sludge for the
adsorption of Cu, Cd, Ni, Zn and Cr from artificial solutions and their capability to
eliminate heavy metals. They concluded that the activated sludge had a better
adsorption capacity than dried sludge. Kadhum et al., (2011) used inorganic polymer
for coagulation process, such as Poly-Aluminum-Silicate-Chloride for the treatment
of paper and pulp wastewater. According to Kadhum et al., (2011), PASIC was
better than the other coagulants. COD and turbidity were removed by them almost
90% at 40 mg/L dose and at pH 7. Naz et al., (2012) who used conventional
sequencing batch-reactor-technique along with aeration and settling technique in the
same treatment reactor at laboratory scale, indicated a reduction in COD, BOD and
TSS to 95 to 99%. Macova et al., (2010) compared the metal isolation results
obtained by bio-analytical methods with chemical methods.
A number of research workers carried out an investigation on the metals on
vegetables grown on contaminated soil and their effect on the human beings and
animal’s health. Yang et al., (2011) demonstrated the possible health threat due to
daily consumption of heavy metals like Pb, Zn, Mn, Cu, Cd and Cr via vegetables in
Chongqing district of China. They also indicated that the concentration of Pb and Cd
when exceeded the safety limits (as given by FAO/WHO and Chinese regulations) it
become harmful to the human’s health. Monu et al., (2008) demonstrated the
presence of heavy metals like iron, manganese, copper and zinc in vegetables grown
after using the wastewater. They detected the highest concentrations of Fe and Mn in
mint and spinach and Cu and Zn in carrot. Their findings were found to be below the
permissible maximum acceptable levels by the FAO (2002). Alexander et al., (2006)
indicated an unusually differences in the metal contents of vegetables cultivars for
various pollutants when compared with the controlled materials. They had grown six
vegetables in soil containing Cd, Cu, Pb and Zn. Similar trends were detected in
leafy vegetables. They further established that the carrot and pea cultivars exhibited
significant differences in the concentrations of Cd and Cu that were accumulated
along with Zn. Leguminous plants indicated a low accumulation while the
Umbelliferous and Liliaceous plant had moderate accumulators of such metal ions
(Alexander et al., 2006). Tiwari et al., (2008) investigated the concentration of
metals in ten vegetables that were irrigated with mixed industrial effluent. They
showed that higher quantities of metals were present in soil irrigated with effluent
than soil irrigated with tube well water. Tube well water showed the concentration
of As, Cr and Pb below the limits. Five out of ten vegetable species i.e., spinach,
radish, tomato, chili and cabbage irrigated with mixed industrial effluent showed
high buildup and translocation of metals (such as As, Cd, Cr, Pb and Ni) in their
edible portions.
19
Junli et al., (2013) analysed the heavy metals concentration in various soil
surface samples of Pearl River Delta (PRD) in China and found CdO, CuO, PbO and
Zn. They further showed that DTPA extractable Cd was negatively linked to the pH
of soil and it was a key factor for Cd accumulation in vegetables, especially in stem
and leaves as compared to the fruits which was ultimately the health risk
components for human beings and animal consumption. Noor-ul et al., (2013) of
District Mardan in Pakistan, found about eight heavy metals such as Cu, Ni, Zn, Cr,
Fe, Mn, Co and Pb in their local soils when irrigated with contaminated wastewater.
Such metal ions were accumulated in a substantial quantities in cultivated vege tables
species like Allium cepa (Onion), Allium sativum (Garlic), Solanum lycopersicum
(Tomato) and Solanum melongena (Brungle). According to them, the amounts of
heavy metals present in the cultivated species, grown under the wastewater were
found to have higher than the WHO/FAO permissible limits. The persons consuming
these vegetables were liable to be on a severe health rick.
20
CHAPTER 3
Sr # Materials Sr # Materials
1. Activated carbon 20. Converter slag
2. Fly ash 21. Soils
Ethylene di amine tetra acetic acid
3. 22. Seeds
(EDTA)
4. Diethyl di thio carbamates 23. Lycemeters
5. Acetone chloroform (2:5) 24. Ozone Generator
Hydrochloric acid analytical
6. 25. Phosphate solution
Grade 37 %
7. Nitric acid analytical Grade 65% 26. Sample collector
8. Charcoal modified 27. Plastic bottles
9. Whattman filter paper No.42 28. Treatment tanks
10. Zinc acetate salt 29. Plastic containers
11. Lead acetate salt 30. Rubber pipe
12. Cadmium Chloride 31. Dosing pumps
13. Chromium chloride 32. Tube well water
14. Ferric chloride Commercial grade 33. Raw wastewater
Sulphuric acid analytical Grade 98
15. 34. Treated wastewater
%
Sodium hydroxide analytical
16. 35. Magnet bar
Grade
17. Ammonia solution
18. Hydrogen per oxide
19. Microbes for treatment
21
(B) LIST OF GLASSWARE
Sr # Glass Ware
1. Beakers 100ml,250ml,500ml,1000ml
2. Conical flask 250ml,500ml
3. Cylinders 50ml,100ml,1000ml
4. Pipets 1ml,2ml,5ml,10ml,25ml
5. Glass columns
6. China dishes
7. Watch glass
S. # INSTRUMENTS
1. Atomic Absorption spectrometer
2. pH meter
3. Turbidity meter
4. Conductivity meter
5. Oven
6. Mechanical stirrer
7. Mechanical Shaker
8. Tinto meter
9. Treatment Plant
10. UV Lamp
22
3. TREATMENT METHODS USED IN THE STUDY
3.1.1 COLLECTION OF COMBINED WASTEWATER SAMPLES
Combined wastewater composite samples were collected from the main disposal of
PCSIR Laboratories complex to the Water and Sewerage Agency (WASA) system and physical
parameters were analysed on site and chemical parameters were analysed after transportation of
samples to the Laboratory (APHA, 2005).
Pollutants like organic, inorganic contaminants, and heavy metals from wastewater were
removed by adsorbents like activated carbon, through adsorption process on mixture of granular
activated carbon and powdered activated carbon (Snyder et al., 2003). Ternes et al., (2002)
reported, activated carbon successfully removed the mainstream pollutants. The best choice for
adsorbent might be a combination of different materials; however the most effective ratio has not
been determined (Koh et al., 2008; Rebhunm et al.,1 971).
In this research work Analytical grade powdered activated carbon of Merck (Germany)
was use and fly ash (pulverised fuel ash) of natural coal from Olympia power plant and was used
for treatment of wastewater. Laboratory scale batch experiments was carried out using powdered
activated carbon and fly ash (pulverised fuel ash) for different contact times 30 to 300 minutes
and at a constant starring speed of 300 rpm at equal intervals of time for reduction of Chemical
Oxygen Demand (COD) along with a blank experiment (sample without adsorbent)
To avoid the matrix interventions a step for sample pre-treatment and separation was
recommended by Unob et al., 2005 estimated by flame atomic absorption Model 240, Varian
Australia; Suvardhan et al., 2003). Subsequently, various procedures have been established for
the pre-concentration. These techniques are ion exchange, coagulation, flocculation co-
precipitation, liquid-liquid extraction, resin chelation, electrochemical deposition, and solid -
phase extraction (Juang and Shiau, 2000; Amuda and Alade, 2006; Amuda et al., 2006). These
techniques have a few drawbacks such as, inadequate metal removal, high demand of reagents,
energy requirements, and toxic sludge production along with waste products (Ahalya et al.,
2003; Wu et al., 2000; Rhazi et al., 2002; Ngah et al., 2004; Unob et al., 2005).
Pre-concentration of samples in this study was made by solid-liquid extraction method.
The adsorbent prepared in this study was more effective to eliminate heavy metals from
wastewaters through adsorbent. This technique has an advantage over the other techniques due to
its sludge free, complete removal of toxic metals even from the solution at low concentration.
This study was made by using modified charcoal and results were much better for removal of
metals (Cd, Ni, Cr, Zn) from wastewater.
Modified Charcoal was prepared by soaking with 3.0 ml/l ethylene di amine tetra acetic
acid (EDTA) for 48 hours. This was done to improve uptake of these heavy metals. These metals
(Cd, Ni, Cr, Zn) were extracted as metal diethyl di thio carbamates with 2:5 acetone-chloroform
23
by varying pH from 1 to 8. The solution pH was adjusted using 0.5 molar NaOH or analytical
grade concentrated HCl. These metals were then adsorbed on a 4 g modified charcoal Colum in
ratio 4:2:1 mixture of Tetra hydro furan, Ethylene glycol and 6.0 molar HCl. Consecutive elution
was affected with 6.0 molar HCl for ((Cd, Ni, Cr, Zn) while 2.0 molar HNO3 was used for Zn.
The elements in elutes were analysed by flame atomic absorption spectrophotometer.
One g of the powdered1 samples were taken and shaken with 100 mg/l of a metal ion
solution whose concentration was 1mg/ml. The samples were shaken using orbital shaker made
of PCSIR for different time of 25 minutes to 200 minutes at 200 rpm. After each interval of 25
minutes, sample was taken off and then filtered through Whattman filter paper No. 42 and the
filtrate was collected in plastic bottles and stored in a refrigerator before analysis. The sample
were analysed for the heavy metals using flame atomic absorption spectrophotometer.
This lab scale experiment was made on batch modes for the adsorption ability study with
different concentrations of heavy metals: 5,10,15,20,25,30,35,40 mg/l for various heavy metals
100mg/l of different concentrations of 5,10,15,20,25,30,35,40 mg/l were taken in volume metric
flasks of 250 ml and 1 g of sample was added in each flask and then placed on the shaker at 200
rpm for 100 minutes for constant contact time of 24 hours. The adsorbent solution was made by
filtration through Whattman filter paper No. 42 and then these samples were stored in a
refrigerator. The remaining metal concentrations were also determined using flame atomic
absorption spectrophotometer.
3.2.5 OZONIZATION
Basic Principal: Treatment with Ozone converts solid waste to remediable liquid waste.
The bacterial cell wall is composed of cellular material which is attacked by ozone and liberated
COD is turned back to the sink where the bacteria reduce the COD. Resultantly, sludge is
reduced. Extra properties attained by treatment with ozone are removal of foaming, reduction in
colour, surfactants and a sharp decline in filamentous bacteria.
Ozone treatment experiments were executed at laboratory scale at batch level. The
treatment unit consists of tube shaped glass column with 200 cm height and 4 cm dia. A porous
diffuser with a porosity size 6, 10–16 mm was placed at the lower end of the treatment reactor
for circulation of ozone. The ozone was produced by a locally made ozone generator at a rate of
5 gm/ minute. The ozone dose concentration applied for experiment was 5.0–25.0 mg O3/L.
Sanchez-Polo et al.,2006 reported in his study the used of ozone 25 – 80 g/m3 for less than 200
mg/l and 50 – 500 g/m3 for greater than 200 mg/l for 5 – 30 minutes varies with COD
concentration.
In these experiments ozone and hydrogen peroxide were used in combination, at high pH.
Hydrogen peroxide is an oxidant. But when UV is used in combination ozone the organics are
broken into CO2 and H2O.
All experiments were carried out in one litre batch at room temperature, applying the
corresponding contact times of 2–20 minutes for reaction. The sample was aerated to remove
remaining ozone from the sample to avoid toxic effects and impacts of dissolved ozone. The
ozone concentration was estimated with two different methods. The total ozone concentration in
the inlet and outlet was estimated by titration method USEPA, 2003 using calcium iodide and
Na2S2O3. The remaining ozone was determined in liquid phase at 258 nm by a
spectrophotometer method (model 200 analytic Jena, Germany). The comparison of results from
two different methods showed the same accuracy. Chemical Oxygen Demand with open reflux
method and colour with Tinto meter (Lovibound model no PFX 995, UK) were determined. For
colour estimation, distilled water was used as standard. Then, a linear regression equation of
24
absorbance against colour was obtained: Y = 0.0004X + 0.0021 with an R2 of 0.9998 (Y is the
absorbance and X is the colour value). The valid range of colour was recorded between 0 to
100.total organic carbon was estimated with TOC analyser and total nitrogen was estimated with
Kjeldahl method. Samples were filtered using o.45 µm fibre glass filter paper for TOC
determination. After initial TOC determination, samples were kept at 20°C for 5 days to analyse
the Biodegradable Dissolved Organic Carbon (BDOC). After 5 days incubation at 20°C the
samples were again filtered through 0.45 µm fibre glass filter paper. The difference between
initial and final values of TOC was considered as the BDOC of the water, while the turbidity of
the samples was measured using a turbidity meter model no LP2000-11. The treatment of
Laboratory wastewater by ozonisation is recommended. The study has proved the potential to
remove the pollutants effectively from Laboratory wastewater by ozonisation. Advanced
oxidation Ozone-based processes can be applied for diverse matrices of wastewater for
treatment. Now its use in waste water treatment has been established. This delay perhaps could
be due to the lack of user’s confidence on ozone. It is not used very widely in Pakistan for
treatment however, the pressure by supervisory authorities of industries, like the Environmental
Protection Agency (EPA) and Pakistan Environmental Protection Authority (PEPA) to look for
proper treatment to meet standards have made optional industry to think for ozone. Ozone is a
very prominent oxidizing agent, next to OH radicals. Ozone can be used with several other
oxidizing agents with improved efficacy. An oxidization agent like, UV at high pH and ozone
improves the oxidation process.
Ozone use in water and wastewater treatment will control the treatment. Simply
explaining conventional water and waste water treatment will be dependent upon following the
process:
a) Preliminary treatment such as screening.
b) Primary treatment.
c) Secondary treatment as activated sludge and secondary sedimentation.
d) Tertiary treatment including decolouration, disinfection, COD reduction.
The use of ozone has been found very useful for following.
1) Decolourisation
2) Deodorization
3) Detoxification
4) Disinfection
5) COD/BOD reduction
6) Sludge Reduction
3.5.2 DECOLOURISATION
The disposal of coloured wastewater and increasing cost of waste water treatment are
becoming unaffordable. Due to affordability option ozone treatment is becoming more and more
attractive. As results of decolourization, ozone treatment brings benefits such as disinfection and
reduction in BOD, COD. The use of ozone in treatment also reduces the odour. Ozone treated
water and waste water produces residuals and treatments are carried out in an environment
friendly way.
3.5.4 DETOXIFICATION
Some of the more common toxic substances are found in industrial and municipal
wastewater. Ozone treatment is most effective for elimination of pollutants. The removal rates
25
are greater than 90% for most compounds at relatively low doses of 3 to 10 mg. Ozone is the best
available and reliable technology for large scale applications.
3.5.5 DISINFECTION
Ozone dosage of 5 g /m3 removes coli forms from waste water and dosage of 15 g/m3
removes parasite (Sanchez-Polo et al ., 2006).
Advantages of using ozone
a) No harmful by- products are produced when treated with ozone.
b) Removal of unpleasant odours.
c) Increasing demand of water for re-users.
a. The Choice of treatment technology is made on the bases of the following criteria.
b. The flow rate of wastewater.
c. The pollution load as COD concentration mg/l.
d. COD concentration from 10–1200 mg/l and flow rate of 1M3/HR to 10000M3/HR
e. The choice of this treatment will exclusively depend on the COD concentration.
The thumb rule for ozone demand is 0.7-1.1 grams of ozone per gram of COD
eliminated.
The use of ozone for wastewater treatment reduced sludge production from 40 to 45% in
wastewater treatment, which reduces sludge handling cost. The ozone dose rate used was 0.01 to
0.1 gm/Kg of solids removal.
3.5.3 COAGULATION
The coagulants used for wastewater treatment were aluminium sulphate, ferrous sulphate,
ferric sulphate and ferric chloride. The ferric and ferrous based coagulants were used in the range
of 4.5 to 5.5 pH and aluminium based coagulants were applied at pH range of 5.5-6.5. Different
doses of ferric chloride and alum (0.01-0.5) mg/l were used with as single coagulant and in
combination with each other in different ratios with slow stirring speed and settling time of 30
minutes 24 hours. Four coagulants were used for treatment namely FeCl3, AlCl3, Alum,
FeSO4.Five different samples were treated with each coagulant and blend of coagulant. The
blend of coagulant FeCl3+AlCl3 was found best
This study was conduction to choose a suitable material for seed crystallization for the
removal of phosphorus using converter slag. Phosphorus removal was conducted to estimate the
effectiveness of the material as seeding agents. Converter slag was investigated. Waste water is
pumped into a main treatment tank and then coagulants were injected through dosing pump with
speed adjustment connected to coagulant containing tank and treatment tank at the optimal dose
calculated from the laboratory scale study. A plastic pipe 1″dia was connected to the submersible
pump placed in the main tank and the other side of plastic pipe was connected to treatment tank.
26
The prompt mixing of the sewage and the coagulant was carried out by mechanical stirrer, after
mixing, flocculation takes place and bigger flocks are formed. The sedimentation takes place at
an inner zone. The sludge settles down in the hopper at the base of the treatment tank. Deposited
sludge is then shifted through a valve in to sludge tank. The treated wastewater is shifted to a
storage tank and then used for irrigation purpose. This modified technology for pre-treatment of
wastewater is discussed by Ibrahim et al., 2012.
27
CHAPTER 4
RESULTS AND DISCUSSION
4.1 ACTIVATED CARBON AND ASH (STUDY-1)
Annexure I, table 1 shows that the domestic wastewater is highly polluted with the
organic load and suspended particles. Organic load is measured in terms of (COD) Chemical
Oxygen Demand and BOD (Biochemical Oxygen Demand) values. The (COD) Chemical
Oxygen Demand concentration is much higher than the permissible limits.
Annexure II, fig.1 represents the percentage removal of (COD) Chemical Oxygen Demand
for different contact times both by the ash and commercial activated carbon. The results obtained
show that (COD) Chemical Oxygen Demand removal has been achieved to the extent of more
than 98 % by activated carbon and 67 % by ash at a maximum time period of 250 minutes .The
results show that the trend of percentage (COD) Chemical Oxygen Demand reduction with ash
was comparable to that of commercial activated carbon. The smooth and independent nature of
curve indicates formation of cover on adsorb ate on the outer surface of the adsorbent (Rebhunm
et al.,1 971).A blank sample was also used which showed 25 percent removal of (COD)
Chemical Oxygen Demand as shown in Annexure II, fig .1. Blank is defined as sample without
adsorbents.
Annexure II, fig. 2 shows the effect of various does of ash and activated carbon on the
percentage (COD) Chemical Oxygen Demand reduction by ash and also compared its trend with
that of commercial activated carbon. It was observed that the maximum percentage of (COD)
Chemical Oxygen Demand removed was 79.31 % by ash dose of 60 g/l and 98.59 % by activated
carbon dose of 50 g/l. After that the equilibrium was set up by further addition of adsorbent
dose. Ash shows fairly the same trend to that of commercial activated carbon. The trend of dose
effect on percentage (COD) Chemical Oxygen Demand reduction both by ash and activated
carbon are also presented. The results in Annexure II fig. 2 show the tremendous increase in
percentage (COD) Chemical Oxygen Demand removal with the increment of adsorbent dose,
owing to the increase in the number of sites (Nelson et al., 1969; Eye et al.,1970). At lower
doses, the significant small adsorption is possibly due to the saturation of active sites with adsorb
ate molecules. A blank experiment was also carried out and their results are presented in
Annexure II fig 2.
Annexure II, fig. 3 indicates the effect of pH on percentage (COD) Chemical Oxygen
Demand reduction by ash and commercial activated carbon. The runs were taken at the constant
initial COD concentration, adsorbent dose and the contact time. The results indicate that at all pH
values below 4.0 the ash has consistently higher adsorption capacity for (COD) Chemical
Oxygen Demand. There is more than 80% drop in (COD) percentage by ash. At high pH the
capacity of adsorbent reduces. The better adsorption of (COD) Chemical Oxygen Demand by ash
at low pH may be attributed to the large numbers of H+ ions present, which in turn neutralize the
negatively charged adsorbent surface, thereby reducing hindrance to the diffusions of organics in
the wastewater. On the contrary low adsorptions i.e. low (COD) Chemical Oxygen Demand
removal observed at pH values higher than 4 are attributed to the presence of excessive OH - ions
in the system, causing increased hindrance to diffusion of organic ions in the system.
Effect of adsorption dose on % COD reduction by ash, activated carbon and without
adsorbent (blank) oxides of aluminum, calcium, silicon, iron are abundant in fly ash (Banerjee
1995; Rebhunm et al.,1971).The hydroxylate surfaces of these oxides in aqueous medium
undergo dissociation resulting in increased number of sites for the adsorption of (COD)
28
Chemical Oxygen Demand. Similar observations pertaining to color, organic and chromium
removal have been reported in the literature. The blank experiment was also carried out and
results are shown in Annexure fig 3.
In this study 44 samples were collected, initial 11 samples were analysed to assess the
pollution load of Laboratory waste-water of PCSIR laboratories complex Lahore. The next
remaining 33 samples were characterized after using different treatment techniques. In these 33
samples first 11 samples were aerated for a fixed time (one hour) at a constant speed without any
separation of suspended floating material but the Bio-Chemical Oxygen Demand (BOD) was not
reduced as required in National Environmental Quality Standards (NEQS). Sample results were
100 % out of NEQS. In second treatment the sludge/ settleables were separated and oxidation
was done for a fixed time (one hour) at a constant speed, four samples results (36.3%) were in
the limits of NEQS and 7 samples (63.4%) were out of National Environmental Quality
Standards (NEQS).In the third phase of biological treatment combined with air oxidation using
organisms present in the waste-water after sedimentation all the 11 samples characterized for
Bio-Chemical Oxygen Demand (BOD) were 100 % in the limits of National Environmental
Quality Standards (NEQS).
After first treatment 100 % (11) samples were out of NEQS limits, after second treatment
4 out of 11 samples result were within the NEQS limits but after the third treatment 11 out of 11
(100 %)were within the NEQS limits for Chemical Oxygen Demand (COD). The appearance of
raw combined laboratory waste-water was of dirty colour. The fermentation and degradation
occurred due to enormous qualities of bacteria and colloids were completely devoid of dissolved
oxygen. All the results of chemical analysis were above the National Environmental Quality
Standards (NEQS) fixed by Ministry of Environment, Government of Pakistan. The Standards
are given in Annexure I, table.No-1.The results of raw effluent samples are given in Annexure II,
fig. 1-6 and after treatment results are presented in Annexure II, figs. 8, 10-19 and for ammonia
removal treatment results are given Annexure II, fig.16 -87. After primary and secondary
treatment to influent waste-water was colour less, transparent, odour free. All the compounds in
the waste-water were broken down into stable inorganic and organic compounds. Dissolved
oxygen was present in effluent with concentrations 1 to 2 mg/L, which is in compliance with
NEQS. BOD5, COD values before and after sedimentation and biological treatment are given in
Annexure II, fig.7 and Annexure II, fig.8. Removal of Bio-Chemical Oxygen Demand (BOD) in
primary sedimentation is 40-50% and secondary sedimentation 90-95% this removal of BOD is
comparable with NEQS. The BOD and COD removal before and after sedimentation shows 95
% removal efficiency, which is in accordance to the limits defined in NEQS and National
Environmental Policy of Pakistan.
The metals concentrations Cd, Ni, Cr, Zn before and after treatment are given in Annexure
II, fig. 90-97. Average temperature variations during the first and second year are given in
Annexure II, fig 98.Variation in pH values during first and second year are represented in
Annexure II fig. 101, Results of phosphorus present in wastewater collected samples during first
and second year are given in Annexure II, fig. 102.
The turbidity of laboratory wastewater samples was measured using the Hanna turbidity
meter and before measurement instrument was calibrated using calibration standards are
presented in Annexure II, fig.12. The results of turbidity removal are given in Annexure II, fig.
13, 14, 15, 16.
29
Four coagulants were used for treatment namely FeCl3, AlCl3, Alum, FeSO4. Treatment
of thirty samples was made and the results of these samples are presented in each figure. Five
different samples were treated with each coagulant and blend of coagulant.AlCl3 showed best
results decreasing turbidity from 39.7 to 11.51 NTU, FeCl3 was the second best coagulant
showing the turbidity results in decreasing order 47.48 to 11.8 NTU. The blended form of
coagulants was FeCl3+AlCl3, AlCl3+Alum, Alum+FeCl3, FeSO4+AlCl3, FeSO4+AlCl3. The
blended solution FeCl3+AlCl3 reduced the turbidity from 48 to 12.73 NTU and second blend
AlCl3+Alum showed the second best results reducing turbidity 45.21 to 18.55 NTU in Annexure
II, fig 14.
The results AlCl3 and FeCl3 shows good and almost similar results but after overnight
settling time results were excellent and alum showed also good results in decreasing order of
turbidity 54 to 26.45 NTU,48 to 22 NTU,45 to 17.54 NTU, and after overnight settling time 33
to 4 NTU but FeSO4 showed increasing trend in turbidity. The results of coagulant and blended
coagulant are in presented in Annexure II, fig.14 and15 and with different settling time are 4 to 5
hours. The results of blended FeCl3+AlCl3 after one, two and three hours settling time were best.
The blend of AlCl3+alum showed also similar trend and the blend of alum+FeCl3 after overnight
settling time was excellent. The same coagulants and its blended form were used for TSS
removal and results are given in Annexure II, fig 17, 18 and 19. AlCl3 was found best coagulant
for TSS removal 278 to 6 mg/L, in blended form of AlCl3+alum, showed similar results but alum
+ FeCl3 showed excellent results.
The physical properties and chemical composition of the seed crystal material used in the
phosphorus study is given in Annexure I, table.17.
The phosphorus was estimated using the method no AOAC960, (2005) but the
concentration of phosphorus was very low and it was not possible to make recovery of
phosphorous from laboratory wastewater.
To attain the ammonia nitrogen removal from laboratory wastewater in a suitable way, the
factors under investigation were initial ammonia concentration, contact time and effect of
radiation concentration. During this study no air was used for ammonia nitrogen removal, since it
has very small effect on ammonia nitrogen removal as explained by Lin et al., 2009. The
percentage of ammonia removal from laboratory wastewater with different contact time from one
to five minutes is presented in Annexure II, figs 16(a) to 18(a) and 19 to 87 at different values
using micro wave of 700 watt.
In this experiment, Different ammonia concentrations were tested (25, 40, 55, 70, 85, and
100 mg NH3-N/l) at pH values of 9, 10, and 11 with different radiation contact times from 1 to 5
minutes. Annexure II, fig 34 to 52 for ist year and Annexure II, figs 59 to 76 shows the effect of
initial ammonia concentration and residual ammonia concentration at pH 9, 10, 11 and radiation
contact time for different time intervals1 to 5 minutes.
It is explained from Annexure II, figs 16 to 52 that ammonia nitrogen removal percentage
increases as concentration of ammonia nitrogen increases along with increase in pH value of
wastewater. At a pH value of 11 and a radiation time of 5 minutes in Annexure II, fig 45 shows
90% removal and Annexure II, fig 51 with removal of ammonia nitrogen 92 %.
30
The same trend was recorded for other radiation times such as 1, 2, 3, 4 and 5 and other
values of pH 9 and 10. The benefit of this finding is the ability to determine the initial
concentration of ammonia nitrogen at which residual ammonia nitrogen concentration can be
achieved. Maximum residual ammonia nitrogen concentration decreases as pH value and
radiation time increases. According to Environmental Standards of Pakistan the treated
wastewater can be disposed to water bodies and can be used to recharge the under groundwater.
The residual ammonia nitrogen concentration decreases as the treatment time increases
along with pH value from 9 to 11.
During this experiment it was also observed that the initial concentration does not affect
the removal percentage of the sample. The maximum nitrogen removal percentage was 91.29 %
with a standard deviation (STD) of ±0.02%. Similar results were obtained for other radiation
contact times.
The ammonia nitrogen removal percentage is inversely proportion to residual ammonia
nitrogen similar conclusion was observed by Cheung et al 1997 .The conclusion of experiment is
that for each radiation time and pH value there is an average removal percentage irrespective of
initial ammonia nitrogen concentration .
Radiation contact time in 1, 2, 3, 4, 5 minutes at pH values of 9, 10, and 11. The percentage
removal of ammonia nitrogen at different pH values 9 is 11.99% and two minutes contact time
is 27.02% , three minutes contact time is 33 %, four minutes contact times is 64.99 % ,five
minutes contact time is 88.25% at different pH values 9 and at pH values10 with contact time
1to 5minutes contact time removal was 17.38, 37%,43% ,75.08% and 89.32 % and at pH 11 with
19.23%,46.33%,74.43%,88.25% and 91.29 % .
The effect of pH was studied by fixing the initial ammonia concentration and radiation
contact time at particular values whereas pH with different values 9, 10, and 11. The experiment
observation shows the trend that removal rate of ammonia increases with the increase in pH.
When the pH was 9 and radiation contact time was 4 minutes and ammonia nitrogen removal
was 64.99% and residual ammonia nitrogen was 35.01 % when the pH was 10, and 11,
respectively. So there was a considerable increase in ammonia nitrogen removal per each
additional pH unit. Similar trend was observed for all values during this experiment and for all
radiation contact times of 1 to 5 minutes. During this entire experiment highest removal rate was
obtained at a pH 11 as compared to pH 9 and 10.
Lin et al., (2009) reported 98% ammonia nitrogen removal rate from industrial wastewater
at pH 11 at 3 minute radiation contact time.
This was observed during this research that higher ammonia nitrogen mass transfer rate
obtained by higher driving force developed by the great difference between initial and final
ammonia nitrogen concentrations. On the results obtained during this experiment it can be
determined that the ammonia removal characteristic at lower concentrations as those existing in
laboratory wastewater are different from the removal characteristic at higher concentrations as in
industrial wastewater .
Lin et al reported that ammonia nitrogen removal rates increases with increase in pH value.
In basic pH value of solution, non-volatile NH4 + converts to volatile NH3+.When the
percentage of the volatile NH3 increases, the removal efficiency of ammonia by heating
increases. Using the solution at pH 9, 10, 11, the volatile ammonia percentage in solution was
11.99 to 91.25%, respectively. So, the volatile ammonia available in ammonia solution at pH 11
is greater than at pH 9 and 10
31
This explains the higher ammonia removal percent’s at pH of 11 as compared to pH values
of 9 and 10. It is also understood from the formula that increasing pH from 11 to 12 did not add a
substantial increase on the available volatile NH3 per cent (increased from 91.25% to 93.7%
only). Hence, increasing the pH from 11 to 12 is not economically beneficial since this will
require the addition of vibrant amount of ammonia solution while not adding significant
improvement on the removal efficiency of ammonia. Based on that, pH 11 is suggested to be the
optimum pH value for removing ammonia from wastewater.
During this experiment the radiation contact time effect was studied, by fixing the initial
pH value and initial ammonia concentration at particular values whereas the value of radiation
time was increased in the range of 1 to 5 minutes. The experimental trend shown during this
study was that ammonia concentration decreased nonlinearly with the increase of radiation
contact time, when the initial pH was fixed at 11, and the initial ammonia concentration was
fixed at 40.11 mg NH3-N/l, the ammonia concentration decreased to 3.49 mg NH3-N/l after 5
minute radiation contact time while it decreased to 3.39 mg NH3-N/l after 4 minutes.
The pH value and ammonia initial concentration are illustrated in Annexure II, figs 57, 63
and 68. The values of the coefficients K, L and M depend on pH and initial ammonia
concentration. These formulae are valid for radiation time in the range of 1 to 5 minutes and for
initial ammonia concentration in the range of 25 to 40 mg NH3-N/l. It is also interpreted from
the data that no major reduction of ammonia concentration was achieved when the radiation time
was increased beyond 4 minutes regardless of the pH value or the initial ammonia
concentrations. For example, for an initial ammonia concentration of 40.11 mg NH3-N/l, the
residual ammonia concentrations was 4.96, 4.50, and 4.35 mgNH3-N/l at radiation contact times
of 4, 4.5 and 5 minutes, respectively. This indicates that as Annexure I, table state residual
ammonia concentration is achieved after 4 minutes of radiation. Therefore, it is concluded that
the optimum radiation contact time for the removal of ammonia is 4 minutes for the pH range 9
to 11 and for initial ammonia nitrogen concentrations in the range of 25 to 40.11 mg NH3-N/l.
4.7 CONCLUSION
This study was carried out to discover the ammonia nitrogen removal from combined
wastewater using micro wave radiation technique. The effects of initial ammonia nitrogen
concentration, pH, and radiation contact time, were studied. Increasing radiation time together
with pH had utmost substantial effect on removal of ammonia nitrogen. Using 700 Watt Micro
Wave radiation energy, and 100 ml synthetic and real wastewater samples, 91.29 ± 0.2%
ammonia nitrogen removal was achieved after 4 min radiation at pH value of 11. Similar
ammonia nitrogen removal efficiency (90.5±1%) was achieved with real wastewater samples that
were treated under the similar conditions of pH and radiation contact time. Thus, the prime
ammonia removal from synthetic and real wastewater by Micro Wave radiation technique was
attained at pH 11 and radiation contact time of 4 minutes .The ammonia removal efficiency in
the lower range concentration (25-40.11 mg NH3-N/l) is found to be lower than the removal
efficiency in the higher range. Micro Wave radiation is proved to be an effective alternative
technique for the removal of ammonia nitrogen from laboratory wastewater.
32
Environmental burden is increasing on many resources of our environment including soil,
water and crops. The metal contamination study is essential for the pollution load assessment,
nature and level of contamination in the environment. Commonly soils are irrigated with
untreated sewage and industrial effluents in third world countries like Pakistan; this common
practice also affects the quality of soil, water and plants. This study was design to evaluate the
quality of combined laboratory wastewater that was used for growing vegetables. The effects of
raw wastewater on soil irrigation and crops were assessed. The metals uptake relationship by
plants and the metal concentration was also explored. The uptake of Cd, Ni and Cr, Zn by Maize
and cucumber and tomato was evaluated 2008 to December 2009 according to APHA method
(APHA, 2005). The combined laboratory wastewater samples were investigated for irrigation
use, pollution load, nutrient values and for metal contamination following the standard methods
described by the American Public Health Association (2005), the metal concentration was
determined with the help of atomic absorption (Varian, Spectra AA-240).
During this study the temperature was recorded for samples on sampling site. The average
temperature for each month ranged from 10.5ºC-36ºC (Annexure II, fig.100).The lower and
higher values were recorded in winter and summer.
The pH of combined laboratory wastewater ranged from 7.58-8.45 and 8.00-8.58 first,
second year. Generally the wastewater pH was neutral with small variation in samples was
observed round the year.
The pollution load of organic matter is measured by the COD and BOD5 analysis. The
average values of COD and BOD5 are given in (Annexure II, fig. 9, 10). The average values for
COD and BOD5 of combine laboratory wastewater for first year (265-414mg/l) and second year
are (366-989mg/l).The National Environmental Quality Standards (NEQS) for COD and BOD5
are 150 mg/l, 80 mg/l. The combined wastewater has COD and BOD higher values than the
permissible standard limits and contamination of combine laboratory wastewater was greater
than domestic wastewater. The cause of higher COD and BOD was the discharge of different
untreated industrial wastewater samples into the sewer system.
Time based variations in combined laboratory wastewater in these parameters such as
BOD5, COD, Temperature and pH, are shown in Annexure II, figs 9, 10, 100, 101. The
temperature was in low range in winter and higher range in summer. No sequential difference
was seen with respect to combined wastewater pH concentration remained neutral. The average
temperature and pH values of combine wastewater were according to NEQS 1997.Average
results of quality parameters were comparable to BOD, COD, these results were higher than
NEQS devised for wastewater. The pH of combine wastewater was in the range which may be
influenced due to lower temperature of combined laboratory wastewater during this time spell.
The organic matter in combined wastewater is broken down by microorganisms into organic
acids consequently which changes the pH of combined wastewater. When we compare the
quality of combined wastewater and domestic wastewater, the combine wastewater was more
contaminated than domestic wastewater. Results of organic pollutant are comparable with other
studies as referred in literature by (Tiwana et al., 1987) Indian, Iranian and Jordanian
researchers.
4.11 IRRIGATION QUALITY PARAMETERS pH, EC, TDS, TSS, CHLORIDE, SAR,
RSC
Usually, water used for irrigation is classified into different categories according to their
qualities that provide a rough estimate of probable hostile effects on crop produce and growth.
33
There are three categories of irrigation water according to FAO guidelines; the irrigation water
has three different grades toward severity (i) none (ii) Slight to moderate (iii) severe. These are
applicable under normal field conditions prevailing in most irrigated areas. The pH range for
normal irrigation water is 6.5 to 8.4 pH range for domestic wastewater is 7.08 to 8.1 which is
within normal range. Whereas the pH of combined wastewater ranges between7.57 to 8.60
slightly goes beyond the FAO limits given in guide lines.
The average total suspended solids (TSS) in combined laboratory wastewater are from
119.73mg/l to 322.22 mg/l. The TSS may be due to silt and organic matter. The total dissolved
solids are an important factor in irrigation water quality which describes the quality of water. The
electrical conductivity and total dissolved solids of combined laboratory wastewater ranges 1200
µs/cm to 1900 µs/cm and 717 mg/l to 988 mg/l respectively.
The results of combined wastewater are on higher side according to FAO guidelines. High
concentration of chlorides creates problems and is detrimental for crops. The chlorides of
combine laboratory wastewater range between 3.25-12.0 m.eq.L-1.The chlorides of domestic
sewage ranges in the safe range while in combine laboratory sewerage it exceeds the limit of
10.0 mg/l.
The sodium adsorption ratio (SAR) is a useful index for assessing the sodium risk of water
used for irrigation. The critical value for SAR is > 9.0. Above this value there is danger of
sodium hazard. The SAR of combined laboratory wastewater lies in the second category of FAO
limits i.e. limitation on use was slight to moderate. While combined laboratory wastewater
values range between 3.25 to12.0 and make it unfit for irrigation. Residual Sodium carbonate in
domestic wastewater lies in the normal range while combine laboratory wastewater have RSC
values between 2- 10 and this high value lies in the third category i.e. restriction on use is severe.
The higher values of parameter such as pH values, chloride, SAR and RSC in combine
laboratory wastewater make it unfit for use in crop growing. The results were on higher side in
wintertime due to less release water. The laboratory waste water available does not meet
agricultural water standards.
The nutrients are available in variety of forms in combine laboratory wastewater with
seasonal and concentration variations. The total nitrogen average concentration in combined
wastewater ranges from 18.44 mg/l to 40.11 mg/l respectively. The concentration of total
nitrogen and total phosphorus for combine laboratory wastewater ranged from 18.44 to
40.11mg/l and 0.94 to 2.98 mg/l Annexure II, figs.19 to 87. In water total nitrogen is formed by
different combinations total Nitrogen and total phosphorus concentrations were ranged from
29.66mg/l to 40.11 mg/l in first year and from 18.66 mg/l to 33.10 mg/l in second year
wastewater samples. The concentration of nitrogen in combine wastewater was almost similar
with slight variation. While the ammonia nitrogen in samples was within the NEQS limit of 40.0
mgL-1.Total phosphorus was lower in concentration in combine wastewater samples. The origin
of nitrogen in combined sewerage is human’s excreta and is present in the form of organic
nitrogen. The organic nitrogen is broken into ammonia, ammonia to nitrite by microorganisms
and bacteria. The higher concentration of BOD is due to the covered sewer system which makes
the system oxygen deficient.
34
Heavy metals in combined laboratory wastewater lies in the standards set by the
Government of Pakistan for waste water disposal and FAO standard for irrigation. Cadmium
results were in the range of 0.004 mg/l to 0.059 mg/l shown in the Annexure II, figs.90 to 93,
Cadmium limit in NEQS is 0.1mg/l the results of combined laboratory wastewater are within the
NEQS for wastewater but these are above the FAO limit is 0.01 mg/l. Nickel was found in the
range of 0.01 mg/l to 0.213 in samples of combined wastewater, these maximum samples are
within the NEQS limits (1.0mg/l) and one sample is above FAO limit of (0.2mg/l) and maximum
samples are within FAO samples. Chromium concentration lies between 0.008 mg/l to 0.873mg/l
presented in Annexure II, figs 92 and 97 while NEQS limit is 0.1mg/l and FAO limit is 0.01 mg/l
which exceeds the NEQS and FAO limits for chromium. Zinc was 0.013 mg/l to 0.108 mg/l
presented in Annexure II, figs 93 and 95, The NEQS limit for wastewater is 5 mg/l and FAO
limit is 2 mg/l.
This may be due to wastewater generated by testing of different samples tested in different
divisions/ sections and disposal of this wastewater without any treatment into sewer system of
PCSIR laboratories complex Lahore. The heavy metal concentration in raw combined laboratory
wastewater.is moving towards higher side day by day as observed in study but as compared with
Rai and Tripathi, (2007) studied in industrial wastewater in Lotha village. Gupta et al., 1986 has
reported that the concentration of heavy metals in wastewater varied depending upon the type of
industry and wastewater come from. The result of this study shows variations and inconsistent
patron of heavy metals presence in combined laboratory wastewater.
4.14 CONCLUSION
The combine laboratory wastewater collected from PCSIR, S sewage system during this
study period exceeded the permissible limits for BOD, COD. However the combine laboratory
wastewater was the worst according to NEQS. The combined laboratory wastewater was not
suitable for irrigation and it would have to make possible its safe use by treatment. The
agricultural guidelines impose restriction on the use of this wastewater for agricultural purpose.
The combine laboratory wastewater was unfit with respect to pH, chloride and was rated in
“severe quality on use” group. The nutrient value of combine laboratory wastewater few samples
were exceeding the limit with respect to ammonia and remaining was within the limits. The
combined laboratory wastewater sample were contaminated with heavy metals, cadmium was
within the NEQS limit but exceeds the FAO limits but chromium is above the NEQS and FAO
limits, one sample exceeds the NEQS limits and same is the case in FAO limits. All the results of
zinc were within the NEQS limits and FAO limits set by the National and International Standards
(NEQS, FAO), while in laboratory wastewater the concentration of all the metals except
chromium is higher than the standards and could pose a threat to crop and soil environment then
35
human health. In almost all developing countries like Pakistan, farmers consider wastewater as a
valuable resource because of its higher yield.
Soil samples from upper surface (0-20cm) were collected from three sites which were
irrigated with tube well water (control), Combined laboratory wastewater and treated combined
laboratory wastewater, Three fields were selected one was irrigated with tube-well water and
would be considered as control. Second field was irrigated with raw combined laboratory
wastewater. Third field was irrigated with treated combine laboratory wastewater and vegetables
tomato, cucumber and maize were grownup and the samples from these corresponding fields
were collected from where soil samples were collected. The quality of the soil was silt type.
The pH of soil ranges from 7.33 to 8.51 with an average value of 7.44. Irrigation with
combined laboratory wastewater decomposed the organic matter due to lowering the pH. The
Electrical Conductivity of soil was with an average value of 2.30dSm-1. The increase in
Electrical Conductivity could be endorsed to the addition of significant quantity of dissolved
salts through the combined laboratory wastewater. The average concentration of organic matter
in soil was higher than 1.06% as compared to PSI 0.80% soil. The quantity of organic matter
was increased due to irrigation with wastewater rich in nutrients with high BOD which reduces
its decomposition and increases organic matter. SAR of all soils has the value of SAR below 15,
and varied from 8.30, 9.15 and 8.56 with mean value of 8.67. These results are comparable with
the results of (Ghafoor et al., 1996) reported SAR values of soils below 15 for soils irrigated with
domestic wastewater. The increase in Cat ion Exchange Capacity of soils may be due to soil
irrigation with combined laboratory wastewater which increases the clay contents in soils.
Frequent use of combined laboratory wastewater could accumulate metals into soil. Soil is
a sink for heavy metals due to its high holding capacities reported by Nolan et al., 2003. The soil
properties such as pH, electrical conductivity and organic carbon are the factors that governed
the metal concentration in soil. Shift of heavy metals combined laboratory wastewater to soil and
later uptake and build up in eatable part of vegetables, soil shows a direct path for absorption of
heavy metals into food chain. The total metal content is a poor indicator for their bioavailability
because these properties depend on the chemical factors of soil. The outflow of soil by means of
chemical extracts is a commonly used method to measure the concentration of heavy metals in
soil. Single and sequential extraction method has been applied to identify plant available form of
heavy metals in soil. The sequential extraction method is very widely used and reliable method
which distributes metal into five portions (F1) exchangeable (F2) bound to carbonates (F3)
reducible (F4) bound to organic matter (oxidisiable) and (F5) residual.
4.17 CADMIUM
36
The concentration of total cadmium in Field (F1) soil ranged from (drinking water) 0.1 to
0.75 (Annexure I, table 72) 2.61-6.60 (Raw combined laboratory wastewater Annexure I, table
77) and (Treated combined laboratory wastewater Annexure I, table 81) 0.22-1.07 with an
average value of 0.461mg/ Kg-1, average value of 4.07mg/ Kg-1 and 0.439 mg/ Kg-1 while
allowed Limit is 0.5mg/Kg-1.Normally above this limit of 0.5 mg/Kg-1 total cadmium in soil is
known as symbol of soil contamination. In this research three fields were selected field (Fa),
field (Fb), and field (Fc). Field (Fa) was irrigated with tube well water, field (Fb) was irrigated
with raw combined laboratory wastewater and field (Fc) was irrigated with treated wastewater
three crops (cucumber, Tam too and maize) were grown in these three fields. In comparison of
these three fields the concentration of Cd was high in field (Fb), which may be due to irrigation
with raw combined laboratory wastewater that contain cadmium higher then acute level.
The metals in wastewater are added from the samples tested in different sections/divisions
of PCSIR Laboratories complex Lahore sent for testing from various industries such as dyes
,pigments, metal coatings, plastic materials, cement industries, electroplating and batteries the
wastewater produced during testing process of samples and washing of apparatus, wastewater
generated during this testing is being disposed of without any treatment, which makes the
possibility of cadmium accumulation in effluent irrigated fields. The results of cadmium in raw
combined laboratory wastewater irrigated field, the soil samples collected from field (Fb) by
Tessier's sequential extraction procedure are given in Annexure I, table 77. Cadmium
concentration (mg/Kg-1) in different fractions was 0.05 to 0.40 with mean value of 0.105, 0.039
to 1.45 with mean value of 0.638, 0.46 to 0.65 with mean value of 0.556,0.05 to 0.61 with mean
value of 0.469 and 1.10 to 4.10 with mean value of 2.165 for exchangeable, carbonate, reducible,
oxidisiable and residual fractions respectively. Considering species in first two fractions
(F1+F2), exchangeable and carbonate bound in (Fb) soil samples are potentially available to
plants and are mobile. The species in these fractions can be called bioavailable species of
cadmium the observed concentration of bioavailable species was 21.03% of the total metal
concentration. Cadmium is unnecessary metal of no benefit to human beings and is life-
threatening element due to its easy merger in the food chain and its general bio toxicity reported
by Girard, 2005).
Earlier studies also support the findings that cadmium uptake from soil by plants is
relatively comfortable reported in literature that Cd is concentrated in first three extraction steps
(almost 42%). Cadmium in five fractions was found in the order exchangeable > carbonate
bound then in reducible > oxidisiable > residual order. The bioavailable species (F1+F2) of Cd in
field soil (Fb) is only 2.57 and 15.68% , while the residual fraction is 53.19% The trend of five
fractions at this site is as follows residual > carbonate > Reducible > oxidisiable >exchangeable.
Higher concentrations of metals in mobile fractions in the polluted soil indicate higher mobility
of metals due to human activities .There is a chance that irrigation with raw combined
laboratory wastewater results in addition of Cd in soil. This was recommended to the adding of
fertilize to enrich the soil reported in literature chromium in different fractions in the order:
residual > reducible oxidisiable > nitric acid extractable. Samples coming from different
industries for testing in various sections/divisions of PCSIR Laboratories complex Lahore. The
wastewater generated during this testing disposed in sewer system without any treatment.
4.18 NICKEL
Total Nickel contents in soils ranged from 7.63 to 18.92 with average value of 12.52 mg/g-
1 (Annexure I, table 78). All studied soils of (Fa, Fb, and Fc) contained total Nickel below the
permissible limit of 25 mg/Kg-1. The total Ni concentration in soils that are irrigated with
37
wastewater from last few years ranged from 1.10- 4.10 (Annexure I, table 78) with average value
of 1.21 mg /Kg-1. In soil samples the Ni concentration range was 0.83-1.80 with mean value of
2.162; 1.20-5.40 with mean value of 1.74; 1.05-3.62 with mean value of 2.05; 0.08-1.91 with
mean value of 1.30 and 3.20-8.720 with mean value of 6.22 mg/Kg-1 in exchangeable, carbonate
bound, reducible, oxidisiable and residual fractions respectively. The Ni concentration was
highest (49.68%) in residual fraction followed by reducible fraction (28.91%), carbonate bound
(13.90) then oxidisiable fraction (10.38%) and least in exchangeable fraction (9.66%). The same
trend was found in other soils samples. Metals bound to residual fraction are higher may be due
to metals associated with silicate minerals and are expected to be chemically stable and
biologically unavailable. The Researcher, Narwal et al., (1998) found 51% of the total Ni
associated with residual fraction, but they reported higher Ni in residual fraction than that with
carbonates.
4.19 CHROMIUM
The total concentration of chromium in this study ranged from 0.16 to 1.40 with average
value of 1.02 mg/Kg-1 (Annexure I, table 79) in soil the chromium concentration was below the
hazardous level of 200 mg/Kg-1 as reported standard value by (Hua main et al.,1999). The
concentration of Cr in different fractions of raw combined laboratory wastewater irrigated soil.
The decreasing order of residual > carbonate > exchangeable > oxidisiable > reducible. It was
also found the most common forms of chromium as in the residual form followed by organic
form. Very low concentration of Cr was found in exchangeable and reducible forms in surface
soil samples taken from soils used in this study. Chromium enter in wastewater from chromium
compounds, mostly in chromium (III) or chromium (VI) produced by chrome plated , dyes ,
pigments and leather and wastewater samples , sent by various industries for testing in PCSIR.
4.20 ZINC
Total Zinc concentration (Annexure I, table 80) in soils under different vegetables ranged
from 0.03-0.80 mg/.Kg-1 and about 42.80% (Annexure I, table 84) soils contained Zn below the
permissible limit of 80 mg/Kg-1. It was observed that all the soils under raw combined
laboratory wastewater for irrigation had total Zn below the permissible limit.
While concentration of Zn in tube well water irrigated soil was 0.50 mg /Kg-1 which
indicate that soils irrigated with raw combined laboratory wastewater have higher level of metal
and also higher level in surface soils as compared to subsurface soil. In soil samples Zn
concentration (mg/Kg-1) in different fractions was in the decreasing order of residual (42.80
mg/Kg-1) > oxidisiable (22.64 mg/Kg-1) > reducible (20.27 mg /Kg-1) >Carbonate bound (11.69
mg/Kg-1) > exchangeable (5.37 mg/Kg-1). In the soil under study bioavailable Zn concentration
was 5.01% of the total concentration.
The common use of zinc in industry is to coat iron, steel and other metals to avoid rusting
and corrosion. Zinc oxide is also used in producing rubber. Zinc sulfide and zinc oxide are used
to make ceramics, white paints and etc. Zinc acetate, Zinc chloride, and zinc sulfate are used in
preserving wood and in dyeing fabrics. Zinc compounds are used by the pharmaceutical industry
as ingredients in some common products, such as vitamin supplements, sun blocks, diaper rash
ointments, deodorants and antidandruff shampoos.
38
4.21 Cadmium
The concentration of cadmium in edible part of vegetables i.e. Cucumber (leaves), Tam
too, Maize at fields ranged from 0.05 to 0.40 with an average value of 0.105 mg/Kg-1 While the
concentration of Cd in maize collected from field irrigated with raw combined laboratory
wastewater ranged between 0.03 -0.25 with average value 0.141 mg Kg-1 (Annexure I, table 79).
This increase could be due to high contents of Cd which is due to continuous application of raw
combined laboratory wastewater. This may be due to the fact that concentration of bioavailable
Cd was 21.03%. In Cucumber leaves, Cd was above the critical level of 0.01 mg/Kg-1WHO
(1996).
Boon and Soltan 1992 reported higher concentration of Cd in leaves of lettuce, cabbage,
and broccoli. Jaffer and Saleem 1987 also reported similar results in radish, carrot, beans and
spinach collected from different areas of Punjab, KPK and Azad Kashmir, Pakistan.
Din et al., 2001 reported Cd ranged from 0.1 -1.58 ppm in different vegetables collected
from different industrial areas of Punjab. It accumulates in kidney and liver. It induces cell injury
and death by interfering with calcium (Ca) regulation in biological systems. It causes bones to
become brittle.
4.22 NICKEL
The concentration of nickel ranged from 0.03 to 0.026 mg/Kg-1 in vegetables. Maximum
uptake (2.04 mg/Kg-1) of Ni was by leaves, while uptake by fruits was lower 0.025, 0.022 and
0.026 by Cucumber, Tomato Maize respectively. The average Ni concentration in maize was
0.024 mg/Kg-1 and was within permissible of 10 mgKg-1 for food items by WHO, (1996).
Jaffer and Saleem 1987 also reported similar results in different areas of Punjab, NWFP
and Kashmir, Pakistan.
4.23 CHROMIUM
The uptake of Cr was maximum (2.35 mg/Kg-1) by cucumber leaves followed by tomato
with an average value of 1.8 mg/Kg-1, the maize has chromium concentration ranged from 0.00
to 0.14 mgKg-1 with average value of 0.10 mg/Kg-1. The cucumber and tomato contained Cr
below the permissible limit of 1.3 mgKg-1 recommended for food stuff by WHO (1996). In
general leaves accumulated more Cr than fruits. This partitioning of metal among the plant parts
reflects some mechanisms controlling ion translocation within the plant parts Maliwal et
al.,2008.
4.24 ZINC
The Zinc concentration ranged from 2.20 – 8.80 mg/Kg-1 (Annexure I, table 80) in
different vegetables grown using raw combined laboratory wastewater. Maximum zinc
concentration was observed (8.80 mg/Kg-1) in cucumber leaves. The average uptake of Zinc by
maize collected was 4.17mg/Kg-1. Zinc concentration in all studied samples from fields (Fa, Fb,
and Fc) was below the permissible limit of 5.0 mg/Kg-1(WHO, 1996).
Ahmed et al (1998) also observed higher concentration of Zn in sewage irrigated
cucumber and Tomato.
39
4.25 CORRELATION ANALYSIS
The results of correlation between metal concentration in plant and different fraction of
soil. The most important application of chemical fractionation of metals in soils is to estimate
their bioavailability for different tissues of plants. Different forms of metals in soils extracted by
chemical reagents were usually assessed for their availabilities to plants based on correlation
between metal concentration in the plant tissue and different fraction of metals in soil. If the
accumulations of any element by a plant correlate significantly with the extractable fraction of
soil, it can be assumed that this fraction of metal is readily available to plants. In this study,
correlation analysis was performed between different chemical fractions (F1, F2, F3, F4, and F5)
and total concentration of metal in soil and the metal accumulated in edible part of cucumber,
tomato and maize. Correlation coefficients (r) were estimated with 95% confidence level. The
positive correlation indicates the bioavailability of these metal fractions to plant. The highest
correlation coefficients between plants and soil samples were obtained from F1 (exchangeable)
and F2 (acid soluble) fractions of the Tessier et al., (1979), which indicate the availability of
these plants. These findings are similar with already reported in literature.
4.26 CONCLUSION
The present study concludes that irrigation with raw combined laboratory wastewater
increased the toxic heavy metal concentration in soil and plants at field (Fb). While the field (Fa)
and (Fc) was used as control the level of heavy metal accumulation in soil is less. The raw
combined laboratory wastewater irrigation increases total metal concentration which also
increases bioavailability of metals. The raw combined laboratory wastewater metals have
prolonged residence times in soil and higher residual bioavailability. This highlights the need to
treat the combined laboratory wastewater to minimize the addition of metals to soils and to
understand the principal method of metal concentrations in the soil solution and their
acclimatization in plants. It may be concluded from these results that the use of raw combined
laboratory wastewater for irrigation will not only pollute the soils and will also adversely effect
on human and animal health through introducing heavy metals into their food chain.
The use of untreated combined laboratory wastewater is the main source of soil
contamination with heavy metals. In developing countries like Pakistan, wastewater irrigation is
a common exercise. Untreated wastewater used for irrigation is rich in organic matter and many
food nutrients along with heavy metals. Mostly concentrations of heavy metals in raw combined
laboratory wastewater are not within permissible limits. Rattan et al., (2005) reported in his study
that Long term irrigation with such effluents could result in soil contamination to phytotoxic
levels. Hamon, (1995) Reported dissolved organic carbon can also be absorbed by plant roots
along with metals it bound and this can increase the metal uptake. (Hooda et al.,1994a ; Basta et
al.,1999 ; Stacey et al., 2001) in their studies reported a tendency for sludge bound metals to
become more soluble and available for plant as the added organic matter decomposes.
In Pakistan wastewater is used for growing high value crops like vegetables and fodder.
However, raw sewage contains heavy metals in variable concentrations that have to lead soil and
crop contamination. Soil factors that may influence metal solubility and movement in bio solids
40
amended or wastewater irrigated soil include pH, total metal concentration, texture, and organic
matter. Heavy metal reactions in soils and their uptake by plants can be modified with the use of
certain amendments like farmyard manure, lime, inorganic phosphorus compounds are easily
available for soil application and can be cost effective. Soil properties especially texture is also
very important in determining the availability of metals to crops (Stacey et al., 2001; Dowdy
1983).
This experiment was conducted in CEPS, PCSIR Labs. Complex, Lahore, from 2008-2009.
Veget6ables cucumber, Tomato maize was grown in sandy soil texture. These soils were
contaminated with Cd, Cr and Ni 10, 50 and 50 mg/kg-1 respectively. 4 percent Organic matter
was mixed thoroughly into soil and then filled into Lysi meters. The lysi meters made of PVC
were used in this study that have 80 cm height and 40 cm diameter. The lysi meter soil was
incubated for 30 days at room temperature. Water content in soil was maintained to 35% of water
field capacity by Tensio meter installed in lysi meters. Cucumber and Tomato seeds were planted
at field. 16 seeds of Cucumber and Tomato in each lysi mter were planted and after emergence
thinned to 8 per lysi meter. The extra seedling were crushed and mixed into the same lysi meter.
Fertilizers NPK as urea, potassium and di ammonium phosphate were applied.
At maturity, plant data was recorded. After harvesting the crop, data for biomass was
recorded. Plant samples were washed with deionized water to remove external contamination,
then samples were oven dried at 60±10ºC plant material were analyzed for metals after digestion
in acid mixture AOAC, (2005).
The average data of cucumber, Tomato and maize grown in the sandy soil Cd, 50.0
mg/Kg-1, Ni and Cr was added to soils. When averaged, yield of Cucumber, Tomato and maize
was maximum Cucumber, 225 gm, Tomato 25gm, maize 250 gm irrigated with tube well water,
Cucumber 990gm, Tomato 90 gm, Maize 1020gm irrigated with treated laboratory wastewater,
cucumber 870 gm, Tomato 60 gm, Maize 820gm,irrigated with raw laboratory wastewater
respectively. The yield of these three crops was observed the difference in tube well water,
treated and raw laboratory wastewater is that no of fruits were higher and healthy. Tube well
water (Control) > Treated laboratory wastewater>Raw laboratory wastewater .The treated
combined Laboratory wastewater increased the yield of crops.
4.28.2 CUCUMBER
The average data of Cucumber, Tomato and Maize yield grown in three different soils
with three levels of 10% O.M. 4 % O.M and zero % O.M then 10 mg/Kg-1 of Cd, 50.0 mg/Kg-1
of Ni and Cr were added to soil of Lysimeters used in this study.
Average, yield of Cucumber was maximum (68 gm), Tomato (71gm), Maize (45gm) in
soil with 4% organic matter. In same soil with 10% O.M. the yield of Cucumber was (97 gm),
Tomato (91gm) and Maize (64gm), in soil without OM the yield of Cucumber was (45 gm),
Tomato (64gm) and Maize (48.85gm) respectively.
41
In Cadmium, Chromium and Nickel treated soils the reduction in yield was observed
sandy soil without O.M. For Ni treatment there was less decrease in yield.
4.28.3 TOMATO
Tomato yield was pointedly affected by Chromium applied soil; however the effect was
prominent in soil with 10% OM and without OM soil. Maximum yield of tomato (97 gm) was
observed in soil with 4% organic matter followed by O.M 10% and soil without O.M. Ni has no
any noticeable effect of tomato yield. Results showed that Cd had hostile effect on tomato in soil
without O.M.
4.28.4 MAIZE
The application of chromium and Nickel in the soil without OM affected maize yield
negatively. The effect of metal addition on plant can be clearly illustrated by the values of the
tolerance index Ti. The tolerance index may be defined as follow:
The above mentioned Equation indicates plant tolerance Index. The Ti value is 1, there is
no effect on growth, When Ti value is higher than 1 there is a favorable effect, and when Ti
value is less than 1 the growth is reduced by metal application (Cottenie et al., 1983). The value
of tolerance index for these metals in soil decreased in the following order Cd >Cr > Ni in
Cucumber, Tomato and Maize. The soil without OM, with 4 % OM, with 10% OM the order was
observed in the similar order. The value is equal with and without O.M. The result indicates that
the uptake of Cr was maximum in sandy soil without OM followed by sandy soil with 4% OM
and least in soil with 10% OM. The uptake was greater in the soil without OM and then in soil
with 4% O.M. and least in soil with 10 % OM. The chromium uptake in cucumber was higher as
compared with uptake by tomato and Maize. The chromium concentration increases as
percentage of OM increases in soil. The results show that uptake was high in soil without OM
and decreased the uptake of metal in soil as OM in soil increases. The maximum uptake was by
cucumber, followed by tomato and least in maize.
4.28.5 NICKEL
Nickel is an essential element of plant diet but it might hinder plant growth by impairing
process of plant metabolism at higher concentrations in plants. The uptake of Ni was maximum
by cucumber in sandy soil with O.M. The minimum uptake of Ni was in soil with 10% O.M. The
uptake of Ni in soil without OM was greater (0.82 mg/Kg-1) and less (0.81 mg/Kg-1) in soil with
4 % O.M. The maximum uptake by cucumber was in soil with zero % O.M. followed by with
4% O.M and then 10% OM in same soil. The same trend was found that the uptake was greater
in the absence of O.M as compared to same soil with different percentages of O.M. The effect of
organic matter and soil texture was prominent in this study. The uptake was maximum in sandy
soil which may be due to the higher adsorption properties of clay. It was observed that OM
decreases the uptake of Ni.
The role of Organic matter is impartially different in controlling uptake of trace metal by
plants depending upon whether it is soluble in folic acid or insoluble in humic acid. The metal
42
cation uptakes are hindered effectively by organic matter. On the other hand the organic metal
complexes made by soluble organics increase the carrying capacity of soil solutions at any
particular pH for metal cations (W.H.O, 1996). Furthermore, humic substances are easily
adsorbed by soil components, and could change their surface adsorption characteristics resulting
in increase or decrease the metal retention.The addition of O.M could increase metal uptake. The
increase was greater in sandy soil than in clay soil.
After the harvest of vegetables the soil samples were collected from each Lysi meter for
the study of different fractions of metal.
4.30 CADMIUM
The Cd was in traces in initial soils. After adding metal salts and O.M 4% into soils,
incubating it and then were planted. These amendments affected the distribution of Cd in soils.
The Tessier et al.,1979 fractionation scheme was adopted to study the distribution of metals after
harvesting the crops and it showed that in soil without organic matter the exchangeable fraction
of Cd was 1.3% followed by 2.9 % in carbonate bound fraction, 1.6 % in reducible fraction, 2.1
% in oxidisiable fraction and 3.7 % in residual fraction. The highest concentration of Cd was in
carbonate fraction i.e. 40.7% while in same soil with treatment of 4% O.M the highest fraction
was also carbonate bound 31.3 %. The metals of the solid phase component can be grouped into
the readily labile, potentially labile and non-labile. Metals of the exchangeable fraction are freely
labile, whereas those of carbonate bound, reducible and organic fractions are potentially
available and highly dependent on soil properties and environmental factors.
4.31 NICKEL
The total concentration of Ni added into soils was 50 mg/Kg-1. While in native soils the
concentration of Ni was in traces 0.8mg/k soils. On the basis of distribution of Ni in different soil
it is evident that the Nickel is mainly distributed in reducible fraction and the results are in
compatible with other findings reported by Han et al., (1997); McLaren et al., (1993) that added
Cu, Ni and Zn were transferred from exchangeable and carbonate fraction to reducible fraction.
4.32 CHROMIUM
43
as compared to naturally contaminate soil reported in literature, from the trends observed during
this study that Chromium has highest binding capacity, Ni has lesser and Cd have lowest and the
availability of Cd, Cr and Ni was highest in sandy soil.
4.33 ZINC
Zinc is a heavy metal of much interest since it is a plant micronutrient as well as potential
contaminant in soils. In soil solution the specification of Zn and thus free Zn activity determined
the plant availability of Zn as a micronutrient and its characteristic as heavy metal contaminant.
Total Zinc concentration (Annexure I, table 80) in soils under different vegetables ranged
from 2.20 to 8.80 mg.Kg-1 and about 42.80% soils contained Zn above the permissible limit of
80 mg.Kg-1 203. Adhikari et al., 1998 reported in India that all the soils under city effluent
irrigation had total Zn above the permissible limit. Haq et al., 2004 reported in his study zinc
concentration in effluent irrigated soils were higher in upper 0 to 20cm soil depth. While
concentration of Zn in tube well water irrigated soil was 1.50 mg Kg-1 which indicate that soils
irrigated with effluents have higher level of metal and also higher level in surface soils as
compared to subsurface soil. In soil samples Zn concentration (mg.Kg-1) in different fractions
was in the decreasing order of residual (5.2 mg.Kg-1) > oxidisiable (2.7 mg.Kg-1) > reducible
(2.21 mg.Kg-1) > Carbonate bound (1.60 mg.Kg-1) > exchangeable (0.80 mg.Kg-1). Soils have
Zn concentration within limit. Similar trend was observed in this study as reported by Zyrin et
al., 1976; Mirchev. 1978 ; Kuo et al., 1983). The results show the mobility and bioavailability of
this element was slow.
4.35 CONCLUSION
Crops like cucumber, tomato, and maize can accumulate heavy metals Cd, Ni, Cr, and Zn
in their tissues. Commonly, uptake is increased in plants that are grown in increased soil
pollution. These experiments were performed to gain insight about the mobility and
bioavailability of Cd, Cr and Ni,Zn with respect to plant species and soil type. It has been
observed that characteristic of soil, such as texture, and organic matter contents affect the
mobility of the metal added. The transfer of metals to plant was higher in sandy soil and differs
among plant species of the three vegetables under study, uptake of metal was highest in
cucumber followed by tomato and least in maize.
4.36 RESTRICTIONS
This study has evaluated the pollution level in laboratory sewer system, evaluating
the pollution level and explaining sources of pollution.
44
4.37 NEED FOR FURTHER STUDY
Soil properties meaningfully affect metals availability and their toxicity to soil. There are
no soil standards in Pakistan with reference to metals in soil and the standards of other
countries may not be valid in local conditions, because soils in Pakistan vary in chemical
and physical properties. This will lead to the development of National guidelines for
development of soil standards with respect to metal levels.
All wastewater drains of Lahore city ultimately discharges into River Ravi. The water
quality in these drains is directly linked to its impact on river Ravi. Later on a detailed study
of monitoring of river Ravi is suggested, this will measure the actual situation of pollution.
Wastewater irrigation is common practice throughout Pakistan. Long term application of
poor quality water may affect soil productivity. A detailed study is required to develop
irrigation water quality standards.
REFERENCES:
Abbas, S. T., Sarfraz, M., Mehdi, S. M. and Hassan, G. (2007): Trace elements
accumulation in soil and rice plants irrigated with the contaminated water.
Soil Tilla. Res. 94, 503–509.
Adhikari, S., Mitra, A., Gupta, S. K. and Banerjee, S. (1998): Pollutant metal contents of
vegetables irrigated with sewage water.
J. Indus. Soc. Soil Sci. 46, 153–155.
Ahmed, M. Y., Ahmad, M. R., Ahmad, N. and Sarfraz. M. (1998): Final report of ARP -
IIProject. (1991-1997) Biochemistry section. Ayub Agri. Res. Inst. Faisalabad,
Pakistan, p. 55.
45
extraction procedure for fractionation of Cd.
J. Soil Sci. Soc. Amer. 63, 1650–1658.
Aleksandra, D., Christiane, F., Robert, P. C. and Ves, Y. (2006): Phosphorus Removal by
electric arc furnace steel slag and serpentine.
Water Res. 40, 1547–1554.
Ali, M. and Deo, N. (1992): Effect of pH on adsorption process of chromium (VI) with a
new low cost adsorbent.
Intern. J. Environ. Pollu. 12, 202–209.
Amuda, O. S., Amoo, I. A., Ipinmoroti, K. and Ajayi, O. (2006): Coagulation, flocculation
process in the removal of trace metals present in industrial waste water.
J. Appl. Sci. Environ. Manag. 10, 159–162.
Andy, N. Sh., Ibrahim, E., Alexsandra, D., Steven, P., Richard, G., Haverkamp, S. and
Bilby. C. (2006): Phosphorus removal by an active slag filters a decade of full scale
experience.
Water Res. 40, 113–118.
Anotniadis, V. and Alloway, B. J. (2002): The role of dissolved organic carbon in the
mobility of Cd, Ni and Zn in sewage sludge-amended soils.
Environ. Pollu. 11, 515 –521.
21st
APHA (2005): Standard Methods for Examination of Water and Wastewater.
Edition,American Public Health Association, USA, P. 5.
Arora, M., Kiran, B., Rani, S., Rani, A., Kaur, B. and Mittal, N. (2008): Heavy metal
accumulation in vegetables irrigated with water from different sources.
Food Chem. 111, 811–815.
Asano, T. and Levine, A. D. (1996): Wastewater reclamation, recycling and reuse. Past,
present and future.
Water Sci. Techno. 15, 107–119.
Bahemuka, T. E. and Mubofu, E. B. (1999): Heavy Metals in edible green vegetables grown
along the sites of Sinza, Tanzania.
46
Food Chem. 66, 63–66.
Barrow, N.T. (1986): Testing and mechanistic model II. The effect of time and temperature
in the reaction of Zn with a soil.
J. Soil. Sci. 37, 277–286.
Bashir. F., Tariq, M., Hammad, K. M., Ahmed, K. R. and Sadia, A. (2014): Fraction of
heavy metals and their uptake by vegetables growing in soils irrigated with sewage
effluent. Turk.
J. Eng. Environ. Sci. 38, 1–10
Berg. U., Donnert, D., Ehbrecht, A., Bumiller, W., Kusche, E., Weidler, P. G. And
Uesch,R. N. (2005): Active filtration for the elimination and recovery of phosphorus
from waste water. Colloids and surfaces A.
Physicochem. Engin. Aspe. 265, 141–148.
Blumethal, U. J., Mara, D. D., Peasey, A., Ruiz-Palcios, G. and Scott, R. (2000):
Guidelines for microbiological quality of treated wastewater used in agriculture.
Recommendations for revising WHO guidelines. Bull. WHO 78, 1104–1116.
Boon, D. Y. and Soltanpour, P. N. (1992): Lead, cadmium and zinc contamination of Aspen
garden soils and vegetation.
J. Environ. Qua. 21, 82–86.
Bose, S. and Bhattacharyya, A. K. (2008): Heavy metal acc umulation in wheat plant grown
in soil amended with industrial sludge.
Chemosph. 70, 1264–1272.
Butt, M. T., Imtiaz, N. and Shafiq,T. (2012): Treatment of domestic wastewater using low
cost materials.
Pak. J. Sci. Ind. Res. 55, 112–116.
Chen, J., Kong, H., Wu, D., Xuechu, C. D. Z. and Sun, Z. (2007): Phosphate
immobilization from aqueous solution by fly ashes in relation to their composition.
J. Hazar. Mat. 139, 293–300.
Chung, B. Y., Song, C. H., Park, B. J. and Cho, J. Y. (2011): Heavy metals in brown
rice(Oryza sativa L.) and soil after long-term irrigation of wastewater discharged from
domestic sewage treatment plants.
47
Pedosphere. 21, 621–627.
Clark, J. W., Vies-man, W. and Hammer, M. J. (1977): “Water supply and pollution
control.” Harper and Row, New York, USA, pp. 169.
Cobb, G. P., Sands, K., Waters, M. and Dorward, K. E. (2000): Accumulation of heavy
metals by vegetables grown in mine wastes.
Environ. Toxicol. Chem. 19, 600–607.
Cox, M. (2007): “Ion Exchange”. In: “A guide book on the treatment of effluents from the
mining, metallurgy, paper, plating and textile industries”. Cox. M., Negre, P. and
Yurramendi, L.(Editors) Inés net Tecnalia, San Sebastian, Spain. pp. 255–266.
Das, C. P. and Pataki, L. N. (2000): Use of industrial waste for reduction of COD from
paper mill effluent.
Ind. J. Environ. 43, 2 –27.
De-ska, J., Kot, W. A. and Namiesnik, J. (2004): Fate and analysis ´of pharmaceutical
residues in the aquatic environment.
Crit. Rev. Analy. Chem. 34, 51–67.
Din, S., Salariya, A. M., Hafeez, J., Yasin, M. and Ashraf, M. (2001): Heavy metal
contents of some vegetables collected from fields irrigated with polluted water.
Pak. J. Sci. Res. 53, 103–107.
Dowdy, R. H. and Volk, V. V. (1983): “Movement of heavy metals in soils” In: “ Chemical
mobility and reactivity in soil systems”. Soil Science Society of America and
American Society of Agronomy, Madison, USA, pp. 229–240.
Edwards, J. D, (1995): “Industrial Wastewater Treatment”, CRC Press, Inc., Boca Raton,
Florida, USA, pp. 233.
Ensink, J. H. J., Hock, W., Matsuno, Y., Munir, S. and Aslam, R. (2002): Use of untreated
wastewater in Peri-Urban agriculture in Pakistan, Risk Opport. Res. Rep. 64. IWMI, Sri
Lanka.
Eye, D. J. and Basu , T. K. (1970): The use of fly ash in municipal waste treatment.
J. Water Pol. Con. Feder. 42, 125–135.
Faiqun, M., Othman, F., Sohaili, J. and Fauzia, Z. (2007): Removal of COD and turbidity to
improve wastewater quality using electro-coagulation technique. Malay.
48
J. Analy. Sci. 11, 198–205.
Ghafoor, A., Rauf, A. and Arif, M. (1996): Soil and plant health irrigated with Paharang
drain sewage effluent at Faisalabad, Pakistan.
J. Agric. Sci. 33, 73–76.
Ghafoor, A., Rauf, A. and Muzaffar, M. (1995): Irrigation with Mudhuana drain water.
Impact on soil and vegetables at Faisalabad, Pakistan
J. Drain. Reclam. 7, 7–12.
Gharbi, F., Rejeb, S., Ghorbal, M. H. and Morel, J. L. (2005): Plant response to copper
toxicity as affected by plant species and soil type.
J. Plant Nitra. 28, 379–392.
Gori, R., Lubello, C., Ferini, F. and Nicese, F. (2004): Reclaimed municipal wastewater as
source of water and nutrients for plant nurseries.
Water Sci. Techn. 50, 69–75.
Greville, A. S. (1997): How to select a chemical coagulant and flocculent. Alberta Water
and Wastewater Operators Association 22 nd Annual Seminar, p.10.
Gupta, A. P., Antil, R. S. and Singh, A. (1986): Composition of some sewer wastewater and
their effects on soil properties. “Proceeding of National seminar on monitoring and
control of environmental pollution”, Chandigarh. Punjab, India. pp.419–425.
Gupta, G. S., Prasad, G., Singh, V. N. (1990): Removal of chrome dye from aqueous
solutions by mixed adsorbents, fly ash and coal.
Water Res. 24, 45–50.
49
Hamon, R. E., Lorenz, S. E., Holm, P. E., Christensen, T. H. and McGrath, S. P.(199 5):
Changes in trace metal species and other components rhizosphere during the growth of
radish.
Plant Cell Environ. 18, 749–756.
Hamon, R. E., Naidu, R. and Correll, R. (1998): Long term changes in Cd bioavailability in
soil.
Environ. Sci. Techno. 32, 3699–3703.
Han, F. X. and Bannin, A. (2000): Long term transformation of Cd, Co, Cu, Ni, Zn, V,Mn
and Fe in the native arid zone soils under saturated conditions.
Communi. Soil Sci. Plant Ana. 28, 635–350.
Hoek, V. D., Ul-Hassan, M., Ensink, J. H. J., Feenstra, S., Raschid-Sally, L., Munir,
S.,Aslam, R., Ali, N., Hussain, R. and Matsuno, Y. (2002): “ Urban wastewater”. A
case study from Haroonabad. Report No .63. Intern. Water Manag. Inst., IWMI,
Colombo, Sri Lanka.
Hooda, P. S. and Alloway, B. J. (1994a): The plant availability and DTPA extractability of
trace metals in sludge amended soils.
Sci. Tot. Environ. 149, 39–51.
Hooda, P. S. (1997): Plant availability of heavy metals in soils previously amended w ith
heavy application of sewage sludge.
J. Sci. Food Agricu. 73, 446–454.
Hough, R. L., Breward, N., Young, S. D., Tye, A. M. and Thornton, I. (2004): Assessing
potential risk of heavy metal exposure from consumption of home produced vegetables
by urban populations.
Environ. Heal. Persp. 112, 215–221.
Huamain, C., Chunrong, Z., Cong, T. and Yongguan, Z. (1999): Heavy metal pollution in
soils in China. Status and counter measures. Ambio. 28, 130–134.
Hughes, M. N. and Poole, R. K. (1991): Metal speciation and microbial growth,the hard
and soft facts.
J. Microbio. 137, 724–725.
Hussein. H., Ibrahim. S. F., Kandeel. K. and Moawad, H. (2004): Bio -sorption of heavy
metals from wastewater using pseudomonas.
Biotechno. 7, 24-29.
50
IUCN. (2005): Drinking water sector. Principles and application of membrane. In:“ Paper
for ACS. IUCN-ACS”. (Support Unit.15), Bio-reactors in water and wastewater
treatment.
IUCN. (2009): Drinking water. In: “Environmental Fiscal Reform”, Government of NWFP,
Abbottabad, Pakistan.
Jaffar, M. and Saleem, M. (1987): Concentration of selected toxic trace metals in some
vegetable and fruits of local origin.
Pak. J. Agricu. Sci. 24, 140–145.
Jan, F. A., Ishaq, M., Ihsanullah, I. and Asim, S. M. (2010a): Multivariate statistical
analysis of heavy metals pollution in industrial area and its comparison with relatively
less polluted area. A case study from the City of Peshawar and Lower Dir district,
J. Hazar. Mater. 176, 609–616.
Jan, F. A., Ishaq, M., Khan, S., Ihsanullah, I., Ahmad, I. and Shakirullah, M. (2010b):A
comparative study of human health risks via consumption of food crops grown on
wastewater irrigated soil (Peshawar) and relatively clean water irrigated soil (Lower
Dir).
J. Hazar. Mater. 179, 612–621.
Jian, Y., Wang, S., Zhibo, Lu. and Shanjie, L. (2009): Converter slag–coal cinder
columns for the removal of phosphorous and other pollutants.
J. Hazar. Mater. 168, 331–337.
Jiangang, C., Hainan, K., Deyi, W., Xuechu, C., Dalei, Z. and Zhenhua, S. (2007):
Phosphate immobilization from aqueous solution by fly ashes in relation to their
composition.
J. Hazar. Mater. B139, 293–300.
Junli. H., Fuyong, W., Sheng, C. W., Xiaolin, S., Xiangui, L. and Ming, H.
W.(2013):Phyto-availability and phyto-variety determine the bioaccumulation risk of
heavy metal from soils, focusing on Cd contaminated vegetable farms around the Pearl
River Delta, China.
Ecotoxicol. Environ. Saf. 91, 18–24.
Kadhum M. S., Hayder A. A., Ali, A. A. (2011): Treatment of pulp and paper mill
wastewater by poly-aluminum-silicate-chloride (pasic) through coagulation-
flocculation process. Al-Qadisiya
J. Engin. Sci. 4, 546–555.
Kahlown, M. A., Ashraf, M., Hussain, M., Salam, H. A. and Bhatti, A. Z. (2006):
Impact assessment of sewerage and industrial effluents on water resources, soil crops
and human health in Faisalabad, Pakistan. “ Research report No. 6(of Pakistan Council
of Research in Water Resources (PCRWR)” Islamabad, Pakistan.
Khan, S., Aijun, L., Zhang, S., Hu, Q. and Zhu, Y. G. (2008a): Accumulation of polycyclic
aromatic hydrocarbons and heavy metals in lettuce grown in the soils contaminated
with long-term wastewater irrigation.
J. Hazar. Mater. 152, 506–515.
Khan, S., Cao, Q., Zheng, Y. M., Huang, Y. Z. and Zhu, Y. G. ( 2008b): Health risks of
heavy metals in contaminated soils and food crops irrigated with wastewater in
Beijing, China.
Environ. Pol. 152, 686–692.
Kim, E. H., Lee, D. W., Hwang, H. K. and Yim, S. (2006): Recovery of phosphates from
wastewater using converter slag. Kinetics analysis of a completely mixed phosphorus
crystallization process.
Chemosphere. 63, 192–201.
Kisibi, M. (2006): Chemical oxidation with hydrogen peroxide for domestic wastewater
treatment.
Hem. Engine. J. 119, 161–165.
Koohestanian, A., Hosseini, M. and Abbasian, Z.(2008): The separation method for
removing of colloidal particles from raw water.
Amer. Eur. J. Agric. Environ. Sci. 4, 266–273.
Kumar, S. R., Agrawal, M. and Marshall, F. (2007): Heavy metal contamination of soil and
vegetables in suburban areas of Varanasi, India.
Ecotoxicol. Environ. Safe. 66, 258–266.
Kuo, S., Hielman, P. E. and Barker, S. A. (1983): Distribution and forms of copper,zinc,
cadmium, iron and manganese in soils near a copper smelter.
Soil Sci. 135, 101–109.
Lee, S. H., Lee. S. O., Jang, K. L. and Lee, T. H. (2001): Microbial flocculent from
Arcuadendron SP-49.
Biotechno. Let., 17, 95–105.
Leeuwen, A. V., Pipe-Martin, J. C. and Lehmann, R. (2003): The South Caboolture Water
Reclamation Process. Ozone.
Sci. Engine. 25, 107–120.
Lei, M., Liao, B., Zeng, Q., Qin, P. and Khan, S. (2008): Fraction distributions of lead,
cadmium, copper, and zinc in metal contaminated soil before and after extraction with
disodium ethylene diamine-tetra-acetic acid.
Commun. Soil Sci. Plant Ana. 39, 1963–1978.
Liskowitz, J. W., Cham, P. C., Trattner, R. and Shieh, M. (1980): “ Leach-ate treatment
utilizing fly ash clay mixture”. In: Proceedings of National conference on hazardous
and toxic waste management, New Jersey, USA, 2, 515–544.
Ma, H., Xiaorong, W. and Chuanbo, Z. (2003): Cr. accumulation and phyto-availability in
Alba-line soils contaminated by tannery sludge.
Chem. Spec. Bioavail. 15, 15–22.
Macova, M., Escher, B. I., Reungoat, J., Cars, W. S., Keller, L., Chue, A. J., Keller,B.and
Muller, J. F. (2010): A monitoring the biological activity of micro pollutants during
advanced wastewater treatment with ozonation and activated carbon filtration.
Water Res. 44, 477–492.
Macova, M., Escher, B. I., Reungoat, J. S. A. C., Cars, W., Chue, L., Keller, J. and
Mueller, J. (2010): Monitoring the biological activity of micro pollutants during
advanced wastewater treatment with ozonation and activated carbon filtration.
Water Res., 44, 477–492.
Maliwal, G. L., Patel, K. P., Patel, K. C. and Patel, N. N. (2004): Effect of continuous
irrigation of mixed industrial effluent on soil and crops.
Pol. Res. 23, 169–172.
Mantovi, P. G., Bonnazi, E., Maestri, E. and Marmiroh, N. (2003): Accumulation of copper
and zinc from liquid manure in agricultural soils and crop plants.
Plant Soil. 250, 249–257.
Mapanda, F., Mangwayana, E. N., Nyamangara, J. and Giller, K. E. (2005): The effect of
long-term irrigation using wastewater on heavy metal contents of soils under
vegetables in Harare, Zimbabwe.
Agricu. Ecosys. Environ. 107, 151–165.
Mara, D. and Cairn, C. S. (1989): Guidelines for the safe use of wastewater and excreta in
agriculture. WHO and UNEP report, Geneva, Switzerland.
53
Mattina, M. I., Musante, C. and White, J. C. (2003): Concurrent plant uptake of heavy
metals and POP’s from soil.
Environ. Pol. 124, 375–378.
McLaren, R. G. and Ritchie, G. S. P. (1993): The long term fate of copper fertilizer applied
to a lateristic sandy soil in Western Australia.
Aust. J. Soil Res. 93, 39–50.
Miner, G. S., Gutierrez, R. and King, L. D. (1997): Soil factors affecting plant
concentration of Cd, Cu and Zn on sludge amended soils.
J. Environ. Qual. 26, 989–994.
Mirchev, S. (1978): Zinc and copper compounding forms in chernozems and forest soil.
Soil Sci. Agrochem. 13, 75–85.
Monu, A., Bala K., Shweta, R., Anchal, R., Barinder, K., Neeraj, M. (2008): Heavy metal
accumulation in vegetables irrigated with water from different sources.
Food Chem. 111, 811–815.
Muchuweti, M., Birkett, J. W., Chinyanga, E., Zvauya, R., Scrimshaw, M. D. and Lester,J.
N. (2006): Heavy metal content of vegetables irrigated with mixtures of wastewater
and sewage sludge in Zimbabwe. Implications for human health
Agricul. Ecosys. Environ. 112, 41–48.
Muller, M. and Anke, M. (1994): Distribution of Cd in the food chain of Cd exposed area
and the health risks of general population.
Sci. Tot. Environ. 156, 151–158.
Murtaza, G., Ghafoor, A., Qadir, M., Owens, G., Aziz, M. A., Zia, M. and Saifullah, H.
(2010): Disposal and use of sewage on agricultural lands in Pakistan. A review.
Pedo-sphere, 20, 23–34.
Myer, E and Shaw, R. (2006): “The turbidity tube”. Simple and accurate measurement
of turbidity in the field. In: Thesis, Master of Science, Michigan Technological
University, USA.
Nelson, M., Guarino, C. F. J. (1969): The use of fly ash in municipal waste trea tment.
J. Water Pol. Cont. Feder. 41, 1905–1911.
Nolan, A. L., Lombi, E. L. and McLaughlin, M. J. (2003): Metal bio -accumulation and
toxicity in soils, Why Bother with speciation.
Austr. J. Chem. 55, 77–91.
Noor-ul, A., Anwar, H., Sidra, A. and Shumaila, B. (2013): Accumulation of heavy
metals in edible parts of vegetables irrigated with waste water and their daily intake to
adults and children in District Mardan, Pakistan.
Food Chem. 136, 1515–1523.
Oliver, I. W., Hass, A., Merrington, G., Fine, P. and McLaughlin, M. J. (2005): Copper
availability in seven Israeli soils incubated with and without biosolids.
J. Environ. Qual. 34, 508–513.
Ong, S. A., Lim, P. E., Seng, C., Hirata, M. and Hano, T. (2005): Effects of Cu (II) and Cd
(II) on the performance of sequencing batch reactor treatment system.
Proc. Bio-chem. 40, 453–460.
PES. (2012, 2013): “Population, Labour Force and Employment”. Pakistan Economic
Survey. Chapter 6 and 12. pp.155–166, 215–228.
Palumbo, B., Angelone, M., Ballanca, A., Dazzi, C., Hauser, S., Neri, R. and Wilson,
J.(2000): Influence of inheritance and pedogeneses on heavy metal distribution on soils
of Sicily, Italy.
Geo. derma. 95, 247–266.
Pasha, Q., Malik, S. A., Shaheen, N. and Shah, M. H. (2010): Investigation of trace metals
in the blood plasma and scalp hair of gastrointestinal cancer patients in comparison
with controls.
Clinica Chi. Mica. Acta. 411, 531–539.
Pelino, M. (2007): “A guide book on the treatment of effluents from the mining, metallurgy,
paper, plating and textile industries”. Cox, M. M., Négré, P. and Yurramendi, L.
(Editors). Inasmet tecnalia, San Sebastian, Spain. pp.75–136.
PEPA (1997): “National Environmental Quality Standards for municipal and liquid
industrial effluents”. The Gazette of Pakistan. Islamabad, Pakistan.
55
Pesscod, M. B. and Arar, A. (1988): Treatment and use of sewage effluent for irrigations.
In: “Food and Agriculture of United Nations”. Butterworth Publisher, London. p.182.
Rahmani, H. R. (2007): Use of industrial and municipal effluent water in Esfahan Province,
Iran.
Sci. Res. Essay 2, 84–88.
Rai, P. K. and Tripathi, B. D. (2007): Heavy metals in industrial wastewater, soil and
vegetables in Lotha village.
Toxicol. Environ. Chem. 1-11.
Rajesh, K. S., Madhoolika, A. and Fiona, M. (2007): Heavy metal contamination of soil
and vegetables in suburban areas of Varanasi, India.
Ecotoxicol. Environ. Safe. 66, 258–266.
Rattan, R. K., Datta, S. P., Chhonkar, P. K., Suribabu, K. and Gingh, A. K. (2005): Long
term impact of irrigation with sewage effluents on heavy metal content in soils, crops
and ground water. A case study.
Agricul. Ecosys. Environ. 109, 310–322.
Reungoat, J., Macova, M., Escher, B. I., Cars-well, S., Mueller, J. F. and Keller, J. (2010):
Removal of micro pollutants and reduction of biological activity in a full scale
reclamation plant using ozonation and activated carbon filtrat ion.
Water Res. 44, 625–637.
Rowell, D. L. (1994): Method and Application. In: “Soil Science”. Longman Publishers,
Singapore.
Sahu, R., Dahiya, R. P. and Gadgill, K. (2002): Fly-ash based low cost method for COD
removal from domestic wastewater. In: 5 t h “Annual International Conference”. Centre
for Energy Studies, Indian Institute of Technology. New Delhi, India. pp. 191 –195.
Sahuquillo, A., Lopen-Sanchez, J. F., Rubio, R. S. (1999): Use of CRM for extractable
metals to assess sources of uncertainty in the BCR three stage sequential extraction
procedure.
Analyt. Chim. Acta 382, 317–327.
Sajjad, H. and Javed, A. A. (2009): Coagulation flocculation studies of tan nery wastewater
56
using combination of alum with cationic and anionic polymers.
J. Hazar. Mater. 168, 1035–1040.
Sharma, R. K., Agrawal, M. and Marshall, F. M. (2008): Heavy metal (Cu, Zn , Cd and Pb)
contamination of vegetables in urban India. A case study in Varanasi
Environ. Pol. 154, 254–263.
Sinha, S., Pandey, K., Gupta, A. K. and Bhatt, K., (2005): Accumulation of metals in
vegetables and crops grown in the area irrigated with river water.
Bul. Environ. Contam. Toxicol. 74, 210–218.
Soon-An, O., Eiichi, T., Makoto, H. and Tadashi, H. (2010): Adsorption and toxicity of
heavy metals on activated sludge.
Sci. Asia 36, 204–209.
Stacey, S., Merrington, G. and McLaughlin, M. J. (2001): The effect of aging bio-solids on
the availability of cadmium and zinc in soil.
Europ. J. Soil Sci. 52, 313–321.
Tessier, A., Campbell, P. G. C. and Bisson, M. (1979): Sequential extract ion procedures for
the speciation of particulate trace metals.
Analyt. Chem. 51, 844–850.
Tiwari. K. K., Singh, N. K., Patel, M. P., Tiwari, M. R., Rai, U. (2008): Metal
57
contamination of soil and translocation in vegetables growing under industrial
wastewater irrigated agricultural field of Vadodara, Gujarat, India.
Chemosphere 71, 1301–1307.
Tyksinski, W., Wlodzimierz, B. and Maciej, B. (2002): Effect of organic substance in the
substrate on the contents of Cd in edible part of vegetable crops.
Roczniki Akademii Rolnicze W. Poznaniu 341, 3–9.
UNDP. (1996): “Human Development Report”. United Nation Development Program New
York, Oxford University Press, Lodon. pp. 1–10.
Ure, A. M., Quevauviller, P., Muntau, H. and Greipink, B. (1993): Speciation of heavy
metal in soils and sediments. An account of the improvement and harmonization of
extraction techniques undertaken under the auspices of the BCR of the commission of
the European communities,
Internat. J. Environ. Analy. Chem. 51, 135–151.
Vijender, S. R. I., Dahiya, R. P. and Gadgil, K. (2002): Fly ash based low cost method for
COD removal from domestic waste water. Centre for Energy Studies, Indian Institute
of Technology, New Delhi, India, Map India p. 273.
WHO. (1996): “Guidelines for drinking water quality, Health criteria and other sup -porting
information”. Mastereom / Wiener Verlag-800.
Xiong, J., He, Z., Mahmood, Q., Lu, D., Yang, X. and Islam, E. (2008): Phosphate removal
from solution using steel slag through magnetic separation.
J. Hazar. Mater. 152, 211–215.
Yang, J., Su, W., Zhibo, L., Jian, Y. and Shanjie, L. (2009): Converter slag–coal cinder
columns for the removal of phosphorous and other pollutants.
J. Hazar. Mater. 168, 331–337.
Yang, Q. W., Xu, Y., Liu, S. J., He, J. F. and Long, F. Y. (2011): Concentration and
potential health risk of heavy metals in market vegetables in Chongqing, China.
Ecotoxicol. Environ. Saf. 74, 1664–1669.
Yang, Z. F. S., Li, H. F. and Jiang, R. F. (2009): Accumulation of cadmium in the edible
parts of six vegetable species grown in Cd-contaminated soils.
J. Environ. Manag. 90, 1117–1122.
Yim, S., Kim, E. H. (2005): A comparative study of seed crystals for the phosphorus
crystallization process.
Environ. Techno. 25, 741–750.
58
Zakir, S. N., Ihsanullah, I., Shah, M. T., Iqbal, Z. and Ahmad, A. (2009): Comparison of
heavy and trace metals levels in soil of Peshawar basin at different time intervals.
J. Chem. Soc. Pak. 31, 246.
Zakria, V. (2005): “Water and Environmental Sustain-ability”. In: World Bank, paper 4.
Zeng, L., Xiaomei, L. and Jindun, L. (2004): Adsorptive removal of phosphate from
aqueous solutions using iron oxide tailings.
Water Res. 38, 1318–1326.
Zhang, J., Huang, X., Liu, C., Shi, H., Hu, H. (2005): Nitrogen removal enhanced by
intermittent operation in a subsurface wastewater infiltration system.
Ecolog. Engine. 25, 419–428.
Zheng, N., Wang, Q. and Zheng, D. (2007): Health risk of Hg, Pb, Cd, Zn, and Cu to the
inhabitants around Huludao Zinc Plant in China via consumption of vegetables.
Sci. Total Environ. 383, 81–89.
59
Annexure-I
Tables
60
Table No.1
Average characteristics of combined wastewater
Table No. 2
Variation in pH of raw wastewater during 1st year
61
Table No. 3
Variation in pH of wastewater after sedimentation during 1st year
Table No. 4
Variation in pH of Wastewater after Biological Treatment during 1st year
62
Table No. 5
Variation in Conductivity of Raw Waste Water during 1st Year
Table No.6
Variation in Conductivity of Raw Waste Water during 2nd Year
63
Table No. 7
Variation in TSS of Raw Waste Water during 1st Year
Table No. 8
Variation in TSS of raw wastewater during 2nd year
64
Table No. 9
Variation in Total Dissolved Solids of Raw Waste Water during 1st Year
Table No. 10
Variation in Total Dissolved Solids of Raw Waste Water during 2nd Year
65
Table No. 11
Variation in COD of Raw Waste Water during 1st Year
Table No. 12
Variation in COD of Raw Waste Water during 2nd Year
66
Table No. 13
Variation in COD after Sedimentation during 1st Year
Table No. 14
Variation in COD after Sedimentation during 2nd year
67
Table No. 15
Variation in BOD after Biological Treatment during 2nd Year
Table No. 16
Variation in COD after Biological Treatment during 2nd Year
Table No. 17
Chemical Composition and Physical Properties of Seed Crystal Material
68
Table No. 18
Experimental Conditions of Influent for Phosphorus Removal
Phosphorus
2 Synthetic solution 21±3 8.5-9.5 40-70 8-10 2 1
Removal
Phosphorus
3 Real wastewater 20±4 8.0-9.0 55-65 0.5-0.8 2 1
Removal
ND: Not Detected
Table No. 19
The Main Factors that affect Reaction are pH Value and Radiation Contact time
Table No 20
Removal of Ammonia Nitrogen with Different Contact Times at pH 10 1st Year
Table No. 22
Metals in Laboratory Wastewater in First Year
Cadmium (Cd) mg/l Nickel (Ni) mg/l Chromium (Cr) mg/l Zinc (Zn) mg/l
0.013 0.089 0.008 0.029
0.028 0.05 0.016 0.031
0.004 0.034 0.036 0.026
0.004 0.037 0.036 0.026
0.045 0.039 0.013 0.086
0.049 0.05 0.022 0.108
0.007 0.025 0.115 0.073
0.059 0.073 0.171 0.013
0.038 0.01 0.113 0.01
0.021 0.01 0.055 0.042
0.014 0.213 0.052 0.036
0.011 0.019 0.042 0.033
70
Table No. 23
Cadmium in Raw Wastewater before Sedimentation in 1st Year
Table No. 24
Cadmium in Wastewater after Sedimentation in 1st Year
71
Table No. 25
Cadmium in Wastewater after Biological Treatment in 1st Year
Table No. 26
Cadmium in Wastewater after Chemical Treatment in 1st Year
72
Table No. 27
Cadmium in Wastewater after Different Treatments in 1st Year
Sr. Month Before Sedimentation After After Biological After chemical
No Cd mg/l sedimentation Treatment Treatment
Cd mg/l Cd mg/l Cd mg/l
1 Jan 0.013 0.01 0.006 0.002
2 Feb 0.027 0.02 0.018 0.012
3 Mar 0.004 0.00 0.001 0.001
4 April 0.004 0.00 0.002 0.002
5 May 0.045 0.042 0.038 0.031
6 June 0.048 0.042 0.036 0.033
7 July 0.008 0.005 0.003 0.002
8 Aug 0.058 0.053 0.047 0.042
9 Sept 0.037 0.032 0.029 0.022
10 Oct 0.021 0.018 0.013 0.011
11 Nov 0.014 0.01 0.008 0.004
12 Dec 0.011 0.008 0.005 0.002
Table No. 28
Nickel in Raw Wastewater before Sedimentation in 1st Year
73
Table No. 29
Nickel in Wastewater after Sedimentation in 1st Year
Table No. 30
Nickel in Wastewater after Biological Treatment in 1st Year
74
Table No. 31
Nickel in Wastewater after Chemical Treatment in 1st Year
Table No. 32
Nickel in Wastewater after Different Treatments in 1st Year
75
Table No. 33
Chromium in Raw Wastewater before Sedimentation in 1st Year
Table No. 34
Chromium in Wastewater after Sedimentation in 1st Year
76
Table No. 35
Chromium in Wastewater after Biological Treatment in 1st Year
Table No. 36
Chromium in Wastewater after Chemical Treatment in 1st Year
77
Table No. 37
Chromium in Wastewater after Different Treatments in 1st Year
Table No. 38
Zinc Concentration in Laboratory Wastewater before Sedimentation in 1st Year
78
Table No. 39
Zinc Concentration in Laboratory Wastewater after Sedimentation in 1st Year
Table No. 40
Zinc Concentration in Wastewater after Biological Treatment in 1st Year
Sr. Month Zn Zn Zn Average Sd Results
No mg/l mg/l mg/l Results Zn
R1 R2 R3 Zn mg/l
mg/l
1 Jan 0.021 0.019 0.018 0.019 ±0.002 0.019±0.002
2 Feb 0.027 0.026 0.025 0.026 ±0.001 0.026±0.003
3 Mar 0.023 0.021 0.022 0.022 ±0.001 0.022±0.001
4 April 0.018 0.016 0.017 0.017 ±0.001 0.017±0.001
5 May 0.055 0.053 0.051 0.053 ±0.002 0.053±0.002
6 June 0.088 0.086 0.084 0.086 ±0.002 0.086±0.002
7 July 0.061 0.062 0.059 0.061 ±0.002 0.061±0.002
8 Aug 0.009 0.007 0.008 0.008 ±0.001 0.008±0.001
9 Sept 0.007 0.005 0.006 0.006 ±0.001 0.006±0.001
10 Oct 0.036 0.035 0.033 0.035 ±0.002 0.035±0.002
11 Nov 0.024 0.026 0.025 0.025 ±0.001 0.025±0.001
12 Dec 0.028 0.027 0.026 0.027 ±0.001 0.027±0.001
79
Table No. 41
Zinc Concentration in Wastewater after Chemical Treatment in 1st Year
Table No. 42
Zinc Removal from Wastewater with Different Treatments in 1st Year
80
Table No. 43
Metals in Laboratory Wastewater during 2nd Year
Cadmium (Cd) mg/l Nickel (Ni) mg/l Chromium (Cr) mg/l Zinc (Zn) mg/l
0.033 0.067 0.21 0.032
0.038 0.045 0.019 0.031
0.024 0.054 0.049 0.042
0.032 0.077 0.029 0.061
0.024 0.029 0.022 0.067
0.059 0.017 0.027 0.088
0.039 0.046 0.170 0.055
0.049 0.053 0.168 0.069
0.026 0.049 0.870 0.092
0.034 0.048 0.066 0.034
0.044 0.89 0.048 0.047
0.033 0.39 0.059 0.039
Table No. 44
Cadmium in Raw Wastewater before Sedimentation in 2nd Year
81
Table No. 45
Cadmium in Raw Wastewater after Sedimentation in 2nd Year
Table No. 46
Cadmium in Raw Wastewater after Biological Treatment in 2nd Year
82
Table No. 47
Cadmium in Raw Wastewater after Chemical Treatment in 2nd Year
Table No. 48
Cadmium in Wastewater after Different Treatments in 2nd Year
83
Table No. 49
Nickel in Raw Wastewater before Sedimentation in 2nd Year
Table No. 50
Nickel in Raw Wastewater after Sedimentation in 2nd Year
84
Table No. 51
Nickel in Raw Wastewater after Biological Treatment in 2nd Year
Table No. 52
Nickel in Raw Wastewater after Chemical Treatment in 2nd Year
85
Table No. 53
Nickel in Wastewater after Different Treatments in 2nd Year
Table No. 54
Chromium in Raw Wastewater before Sedimentation in 2nd Year
86
Table No. 55
Chromium in Raw Wastewater after Sedimentation in 2nd Year
Table No. 56
Chromium in Wastewater after Biological Treatment in 2nd Year
87
Table No. 57
Chromium in Raw Wastewater after Chemical Treatment in 2nd Year
Table No. 58
Chromium in Wastewater after Different Treatments in 2nd Year
88
Table No. 59
Zinc Concentration in Laboratory Wastewater before Sedimentation in 2nd year
Table No. 60
Zinc Concentration in Laboratory Wastewater after Sedimentation in 2nd Year
89
Table No. 61
Zinc Concentration in Wastewater after Biological Treatment in 2nd Year
Table No. 62
Zinc Concentration in Wastewater after Chemical Treatment in 2nd Year
90
Table No. 63
Zinc Removal in Wastewater after Different Treatments during 2nd Year
Table No. 64
Variation in pH of Raw Combined Wastewater in 1st Year
91
Table No. 65
Variation in pH of Combined Wastewater in 2nd Years
Table No. 66
Phosphorus Concentration in Combined Wastewater in 1st Year
92
Table No. 67
Phosphorus Concentration in Combined Wastewater in 1st Year
Table No. 68
Variation in pH of Raw Wastewater during the 1st & 2nd Year
93
Table No. 69
Some Physiochemical Properties of Tube Well Irrigated Soil
O.M
Vegetable Site pH SAR CEC(cmolKg-1 ECe(dSm-1
(%)
7.22 6.43 4.4 0.51 1.28
Cucumber Fa 7.12 5.48 8.0 0.68 1.18
7.25 4.31 4.8 0.67 1.41
7.44 6.32 3.43 0.48 1.05
Tomato Fa 7.33 5.34 3.65 0.70 1.44
7.54 7.45 4.25 0.43 0.98
7.77 4.49 2.69 0.75 1.65
Maize Fa 7.56 3.81 2.44 0.61 2.02
7.24 4.29 2.69 0.86 1.52
Max 7.77 7.45 8.0 0.86 1.44
Min 7.12 4.31 2.44 0.43 0.98
Average 7.39 5.32 4.04 0.63 1.39
S.D 0.15 0.82 0.85 0.12 0.21
Table No. 70
Some Physiochemical Properties of Raw Combined Laboratory Wastewater Irrigated Soil
O.M
Vegetable Site pH SAR CEC(cmolKg-1 ECe(dSm-1
(%)
7.66 8.23 7.5 0.85 2.32
Cucumber Fb 7.72 8.58 6.5 0.89 2.31
7.98 8.21 8.3 0.91 2.41
7.74 9.32 5.8 0.69 2.11
Tomato Fb 7.73 8.29 6.3 0.79 2.28
8.06 9.45 7.5 0.76 2.46
7.83 9.22 7.3 0.88 2.22
Maize Fb 7.72 9.35 6.4 0.83 2.44
7.45 9.11 7.4 0.87 2.65
Max 8.06 9.45 8.3 0.91 2.65
Min 7.45 8.21 5.8 0.69 1.01
Average 7.77 8.86 7.0 0.83 2.36
S.D 0.18 0.321 0.78 0.04 0.15
94
Table No. 71
Some Physiochemical Properties of Treated Combined Laboratory Wastewater
Irrigated Soil
Table No. 72
Concentration (mg/kg) in Different Fractions of Soil Samples from Cucumber, Tomato, Maize
Fields Receiving Tube Well Water for Irrigation
Vegetables Field Exchangeable Carbonate Reducible Oxidisiable Residual Proportion
Drinking (Fa) (F1) (F2) (F3) (F4) (F5) of Total
Water
S1 0.03± 0.02 0.00 ± 0.0 0.01± 0.05 0.04 ± 0.09 0.02 ±0.01 0.10 ± 0.02
S2 0.02 ± 0.11 0.01 ± 0.12 0.02 ±0.19 0.05 ± 0.11 0.03 ±0.22 0.13 ± 0.75
S3 0.01 ± 0.08 0.02 ± 0.12 0.01 ±0.06 0.07 ± 0.10 0.04 ±0.24 0.15 ± 0.60
Cucumber S4 0.05 ± 0.07 0.04 ± 0.11 0.05 ±0.11 0.07± 0.09 0.03 ±0.22 0.24 ± 0.60
S5 0.07 ± 0.13 0.05 ± 0.09 0.07 ±0.12 0.09 ± 0.08 0.06 ±0.15 0.34 ± 0.56
S6 0.06 ± 0.11 0.06 ± 0.13 0.09 ±0.10 0.06± 0.07 0.08 ±0.14 0.34 ± 0.55
S1 0.09 ± 0.14 0.05 ± 0.14 0.02 ±0.14 0.07± 0.11 0.05 ±0.13 0.28 ± 0.66
S2 0.13 ± 0.18 0.11 ± 0.14 0.10 ±0.15 0.12 ± 0.09 0.08 ±0.11 0.54 ± 0.67
S3 0.14 ± 0.16 0.12 ± 0.12 0.13 ±0.28 0.15 ± 0.09 0.06 ±0.13 0.60 ± 0.78
Tomato
S4 0.10 ± 0.09 0.15 ± 0.09 0.10± 0.18 0.14 ± 0.09 0.08±0.18 0.57 ± 0.63
S5 0.14 ± 0.08 0.19 ± 0.16 0.12 ±0.08 0.13 ± 0.11 0.04± 0.15 0.66 ± 0.58
S6 0.11 ± 0.07 0.14 ± 0.11 0.11 ±0.09 0.12 ± 0.08 0.11 ±0.12 0.59 ± 0.45
S1 0.07 ± 0.11 0.06 ± 0.12 0.08 ±0.05 0.03± 0.09 0.04 ±0.10 0.28 ± 0 .47
S2 0.16 ± 0.13 0.12 ± 0.15 0.14 ±0.08 0.12 ± 0.13 0.13± 0.10 0.75 ± 0.59
S3 0.13 ± 0.12 0.14 ± 0.11 0.13 ±0.11 0.12 ± 0.15 0.15 ±0.17 0.67 ± 0.66
Maize
S4 0.14 ± 0.11 0.14 ± 0.13 0.16 ±0.13 0.14 ± 0.11 0.12 ±0.12 0.61 ± 0.75
S5 0.17 ± 0.16 0.16 ± 0.13 0.14 ±0.08 0.11 ± 0.08 0.12 ±0.12 0.74 ± 0.57
S6 0.13 ± 0.11 0.15 ± 0.12 0.16 ±0.12 0.09 ± 0.12 0.11 ±0.13 0.71 ± 0.48
Min 0.01 0.00 0.1 0.08 0.03 0.10
Max 0.17 0.19 0.16 0.45 1.14 0.75
Mean 0.097 0.095 0.091 0.095 0.075 0.461
Proportion of Total 21.04 20.61 19.74 20.61 16.27
95
Table No. 73
Concentration of Metals (mg/Kg) in Different Fractions of Soil Samples from Cucumber,
Tomato, Maize Receiving Drinking Water for Irrigation
Tube Well Water Cucumber, Tomato, Maize Proportio
Field (Fa) S1 S2 S3 S4 S5 S6 Ave n of total
0.00 ±00 0.00±0.00 0.00±0.00 0.09±0.02 0.00±00 0.01±0.11 0.016 0.94
0.00±.00 0.00± 0.00 0.00±0.00 0.00±00 0.00±00 0.09±0.14 0.015 0.88
Cd F1 0.01±0.03 0.01±0.25 0.01±0.14 0.02±0.14 0.01±0.23 0.01±0.03 0.012 0.70
0.01±0.02 0.02±0.06 0.06±0.03 0.07±0.06 0.02±0.04 0.02±0.03 0.033 0.19
0.00±0.00 0.01±0.21 0.01±0.11 0.02±0.10 0.01±0.02 0.01±0.05 0.010 0.59
Mean 0.017
0.00±0.00 0.01±0.13 0.01±0.10 0.01±0.13 0.02±0.1 0.01±0.15 0.010 1.67
0.01±0.13 0.00±0.00 0.01±0.14 0.02±0.22 0.01±0.24 0.01±0.25 0.010 1.67
Ni F1 0.00±0.00 0.01±0.25 0.01±0.12 0.00±0.00 0.01±0.23 0.0±0.00 0.005 0.83
0.0±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.01±0.00 0.00±0.00 0.002 0.33
0.01±0.20 0.01±0.14 0.00±0.00 0.01±0.15 0.01±0.14 0.00±0.00 0.006 1.00
Mean 0.006
0.01±0.14 0.01±0.15 0.02±0.15 0.00±0.12 0.00±0.21 0.01±0.15 0.008 0.62
0.00±0.00 0.01±0.08 0.01±0.14 0.00±0.27 0.00±0.00 0.00±0.00 0.003 0.23
Cr F1 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.000 0.00
0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.000 0.00
0.01±0.01 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.00±.00 0.002 0.15
Mean 0.013
0.01±0.11 0.01±0.14 0.00±0.00 0.00±0.08 0.01±0.11 0.01±0.11 0.007 2.33
0.01±0.13 0.02±0.35 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.001 0.33
Zn F1 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.02±0.15 0.003 1.00
0.01±0.12 0.01±0.16 0.00±0.00 0.00±0.00 0.00±0.00 0.00±0.00 0.003 1.00
0.02±0.36 0.00±0.00 0.01±0.00 0.00±0.00 0.01±0.00 0.00±0.00 0.006 2.00
Mean 0.003
Table No. 74
Sequential Extraction Method of Tessier for Metal Speciation from Soil
96
Table No. 75
Characteristics of Soils used in Study
Table No. 76
Chemical Composition of Tube Well Water used for the Experiment
97
Table No. 77
Cadmium Concentration (mg/Kg) in Different Fractions of Soil Samples from Cucumber,
Tomato, and Maize Receiving Raw Combined Laboratory Wastewater for Irrigation
98
Table No. 78
Nickel Concentration (mg/Kg) in Different Fractions of Soil Samples from Cucumber, Tomato,
Maize Receiving Raw Combined Laboratory Wastewater for Irrigation
99
Table No. 79
Chromium Concentration (mg/Kg) in Different Fractions of Soil Samples from Cucumber,
Tomato, and Maize Fields Receiving Raw Combined Laboratory Wastewater for Irrigation
Vegetables
Field Exchangeable Carbonate Reducible Oxidisiable Residual
Tube Well Total
(Fa) (F1) (F2) (F3) (F4) (F5)
Water
S1 0.03± 0.02 0.02 ± 0.5 0.01± 0.6 0.04± 0.10 0.06 ±0.08 0.16
S2 0.11 ± 0.11 0.42 ± 0.12 0.08 ±1.23 0.11 ± 0.13 0.16 ±1.22 0.88
S3 0.09 ± 0.20 0.27 ± 0.22 0.14 ±0.16 0.21 ± 0.18 0.38 ±0.29 1.09
Cucumber
S4 0.08 ± 0.26 0.00± 0.24 0.03 ±0.12 0.10± 0.21 0.63 ±0.21 0.84
S5 0.10 ± 0.22 0.13 ± 0.49 0.06 ±0.22 0.14 ± 0.18 0.59 ±1.35 1.02
S6 0.11 ± 1.33 0.21 ± 0.23 0.06 ±0.12 0.10± 0.27 0.38 ±1.29 0.86
S1 0.19 ± 1.25 0.25 ± 1.24 0.06 ±0.25 0.17± 1.14 0.45 ±0.26 1.12
S2 0.15 ± 1.58 0.31 ± 0.16 0.11 ±1.15 0.12 ± 1.11 0.48± 1.31 1.17
S3 0.25 ± 1.36 0.33 ± 0.21 0.05 ±0.22 0.13 ± 0.35 0.56 ±1.19 1.32
Tomato
S4 0.14 ± 1.11 0.09 ± 0.19 0.4 ± 0.18 0.25 ± 0.19 0.46±1.28 1.34
S5 0.24 ± 2.20 0.32 ± 0.36 0.10 ±0.38 0.17 ± 1.31 0.46± 1.58 1.29
S6 0.21 ± 1.06 0.34 ± 1.18 0.07 ±2.11 0.24 ± 1.08 0.54 ±1.51 1.40
S1 0.09 ± 1.33 0.26 ± 2.31 0.09 ±0.18 0.08± 1.11 0.34 ±1.16 0.86
S2 0.12 ± 2.21 0.20 ± 1.82 0.07 ±1.15 0.09 ± 2.21 0.31 ±1.10 0.79
S3 0.19 ± 1.18 0.34 ± 1.11 0.03 ±1.10 0.06 ± 1.16 0.41 ±1.77 1.03
Maize
S4 0.14 ± 1.11 0.29 ± 1.35 0.08 ±2.13 0.11 ± 1.21 0.45 ±2.22 1.07
S5 0.17 ± 1.46 0.24 ± 1.22 0.08 ±1.03 0.10 ± 1.04 0.34 ±1.31 0.93
S6 0.13 ± 1.21 0.27 ± 1.41 0.06 ±1.11 0.13 ± 1.11 0.41 ±1.23 1.00
Min 0.03 0.00 0.01 0.04 0.06 0.16
Max 0.25 0.42 0.14 0.25 0.63 1.40
Mean 0.141 0.243 0.088 0.131 0.412 1.012
Proportion of Total 13.93 24.01 8.70 12.94 40.71
100
Table No. 80
Zinc (mg/Kg) in Different Fractions of Soil Samples from Cucumber, Tomato, Maize
Fields Receiving Raw Combined Laboratory Waste Water for Irrigation
101
Table No. 81
Cadmium (mg/Kg) in Different Fractions of Soil Samples from Cucumber, Tomato, Maize
Fields Receiving Treated Combined Laboratory Wastewater for Irrigation
Treated
Field Exchangeable Carbonate Reducible Oxidisiable Residual
Waste Total
(Fb) (F1) (F2) (F3) (F4) (F5)
Water
S1 0.08 ± 0.42 0.42 ± 1.33 0.62 ± 1.18 0.05 ± 0.26 1.44 ±2.18 2.61
S2 0.05 ± 1.50 1.20 ± 1.11 0.46 ± 1.19 0.53 ± 1.17 2.52± 1.33 4.76
S3 0.09 ± 1.61 1.45 ± 2.15 0.55 ± 1.26 0.43 ± 1.61 3.56 ± 1.82 6.08
Cucumber S4 0.06 ± 2.16 0.50 ± 2.31 0.63 ± 1.56 0.36 ± 1.32 2.10 ± 1.31 3.65
S5 0.09 ± 1.41 0.59 ± 1.12 0.51 ± 2.03 0.37 ± 1.39 3.22 ± 1.45 4.78
S6 0.05 ± 1.15 0.65 ± 1.55 0.64 ± 1.66 0.55 ± 1.52 3.40 ± 1.23 5.29
S1 0.08 ± 2.35 0.62 ± 1.59 0.55 ± 1.31 0.62 ± 1.32 2.51 ± 1.21 4.38
S2 0.40 ± 1.56 0.55 ± 1.12 0.52 ± 1.25 0.58 ± 0.45 1.10 ± 1.11 3.15
S3 0.05 ± 1.18 0.52 ±1.08 0.61 ± 1.24 0.61 ± 2.22 3.11 ± 2.12 4.90
Tomato
S4 0.06 ± 1.51 0.46 ±2.12 0.65 ± 1.33 0.59 ± 1.32 4.10 ± 1.5 5.86
S5 0.11 ± 1.11 0.54 ± 1.11 0.48 ± 1.28 0.61 ± 1.41 1.20 ± 1.12 2.94
S6 0.05 ± 2.20 0.40 ± 1.13 0.52 ± 1.08 0.42 ± 1.62 2.22 ± 2.03 3.61
S1 0.11 ± 1.24 0.51 ± 1.22 0.54 ± 1.81 0.46 ± 1.81 1.10 ± 1.33 2.72
S2 0.07 ± 1.18 0.41 ± 1.12 0.51 ± 1.35 0.58 ± 1.08 1.33 ± 1.24 2.90
S3 0.21 ± 1.33 0.38 ± 1.32 0.58 ± 1.18 0.41 ± 1.23 1.22 ± 1.52 2.88
Maize
S4 0.18 ± 1.41 0.53 ± 1.44 0.44 ± 1.35 0.33 ± 1.14 1.24 ± 2.33 2.72
S5 0.09 ± 1.16 0.39 ± 1.23 0.58 ± 1.14 0.42 ± 1.33 2.40 ± 1.56 6.60
S6 0.06 ± 1.23 1.20 ± 1.06 0.46 ± 1.88 0.53 ± 1.28 1.20 ± .38 3.45
Min 0.05 0.39 0.46 0.05 1.10 2.61
Max 0.40 1.45 0.65 0.61 4.10 6.60
Mean 0.105 0.638 0.556 0.469 2.165 4.07
Proportion of Total 2.57 15.68 13.66 11.52 53.19
102
Table No. 82
Nickel Concentration (mg/Kg) in Different Fractions of Soil Samples from Cucumber, Tomato,
Maize Receiving Treated Combined Laboratory Waste water for Irrigation
Treated
Field Exchangeable Carbonate Reducible Oxidisiable Residual
Waste Total
(Fb) (F1) (F2) (F3) (F4) (F5)
Water
S1 0.08 ± 0.42 0.42 ± 1.33 0.62 ± 1.18 0.05 ± 0.26 1.44 ±2.18 2.61
S2 0.05 ± 1.50 1.20 ± 1.11 0.46 ± 1.19 0.53 ± 1.17 2.52± 1.33 4.76
S3 0.09 ± 1.61 1.45 ± 2.15 0.55 ± 1.26 0.43 ± 1.61 3.56 ± 1.82 6.08
Cucumber S4 0.06 ± 2.16 0.50 ± 2.31 0.63 ± 1.56 0.36 ± 1.32 2.10 ± 1.31 3.65
S5 0.09 ± 1.41 0.59 ± 1.12 0.51 ± 2.03 0.37 ± 1.39 3.22 ± 1.45 4.78
S6 0.05 ± 1.15 0.65 ± 1.55 0.64 ± 1.66 0.55 ± 1.52 3.40 ± 1.23 5.29
S1 0.08 ± 2.35 0.62 ± 1.59 0.55 ± 1.31 0.62 ± 1.32 2.51 ± 1.21 4.38
S2 0.40 ± 1.56 0.55 ± 1.12 0.52 ± 1.25 0.58 ± 0.45 1.10 ± 1.11 3.15
S3 0.05 ± 1.18 0.52 ±1.08 0.61 ± 1.24 0.61 ± 2.22 3.11 ± 2.12 4.90
Tomato
S4 0.06 ± 1.51 0.46 ±2.12 0.65 ± 1.33 0.59 ± 1.32 4.10 ± 1.5 5.86
S5 0.11 ± 1.11 0.54 ± 1.11 0.48 ± 1.28 0.61 ± 1.41 1.20 ± 1.12 2.94
S6 0.05 ± 2.20 0.40 ± 1.13 0.52 ± 1.08 0.42 ± 1.62 2.22 ± 2.03 3.61
S1 0.11 ± 1.24 0.51 ± 1.22 0.54 ± 1.81 0.46 ± 1.81 1.10 ± 1.33 2.72
S2 0.07 ± 1.18 0.41 ± 1.12 0.51 ± 1.35 0.58 ± 1.08 1.33 ± 1.24 2.90
S3 0.21 ± 1.33 0.38 ± 1.32 0.58 ± 1.18 0.41 ± 1.23 1.22 ± 1.52 2.88
Maize
S4 0.18 ± 1.41 0.53 ± 1.44 0.44 ± 1.35 0.33 ± 1.14 1.24 ± 2.33 2.72
S5 0.09 ± 1.16 0.39 ± 1.23 0.58 ± 1.14 0.42 ± 1.33 2.40 ± 1.56 6.60
S6 0.06 ± 1.23 1.20 ± 1.06 0.46 ± 1.88 0.53 ± 1.28 1.20 ± .38 3.45
Min 0.05 0.39 0.46 0.05 1.10 2.61
Max 0.40 1.45 0.65 0.61 4.10 6.60
Mean 0.105 0.638 0.556 0.469 2.165 4.07
Proportion of Total 2.57 15.68 13.66 11.52 53.19
103
Table No. 83
Chromium Concentration (mg/Kg) in Different Fractions of Soil Samples from Cucumber,
Tomato, and Maize Fields Receiving Treated Combined Laboratory Wastewater for Irrigation
Raw
Field Exchangeable Carbonate Reducible Oxidisiable Residual
Waste Total
(Fb) (F1) (F2) (F3) (F4) (F5)
Water
S1 0.05 ± 1.12 0.07 ± 1.22 0.13 ± 1.29 0.16 ±1.12 0.17 ± 1.65 0.58
S2 0.09 ± 0.25 0.10 ± 0.23 0.07 ± 1.21 0.08 ± 1.14 0.07 ± 1.45 0.41
S3 0.02 ± 1.32 0.05 ±1.20 0.08 ± 1.23 0.09 ± 1.41 0.08 ± 1.85 0.32
Cucumber S4 0.00 ± 0.00 0.01 ± 1.26 0.02 ± 1.49 0.08 ± 1.15 0.04 ± 1.44 0.15
S5 0.02 ±1.41 0.02 ± 1.22 0.03 ± 1.11 0.04 ± 1.23 0.06± 1.66 0.17
S6 0.03 ± 1.49 0.04 ± 1.35 0.07 ± 1.23 0.05 ± 1.35 0.03 ± 1.42 0.22
S1 0.00 ± 0.00 0.00 ± 0.00 0.03 ±1.22 0.04 ± 1.31 0.05 ± 1.45 0.12
S2 0.01 ± 1.21 0.02 ± 1.22 0.03 ± 1.20 0.04 ± 1.20 0.04 ± 1.14 0.13
S3 0.02 ± 1.34 0.03 ± 1.31 0.04 ± 1.31 0.05±1.52 0.05 ± 1.03 0.19
Tomato S4 0.00 ± 1.21 0.02 ± 1.27 0.05 ± 1.25 0.02 ± 1.36 0.06 ± 1.33 0.15
S5 0.00 ± 1.24 0.00 ± 0.00 0.00 ± 0.00 0.04 ± 1.25 0.03 ± 1.36 0.07
S6 0.04 ± 1.17 0.03 ± 1.15 0.04 ± 1.21 0.05 ± 2.61 0.06 ± 1.59 0.22
S1 0.01 ± 1.15 0.02 ± 1.11 0.05 ± 1.38 0.06 ± 1.22 0.05 ± 2.2 0.19
S2 0.02 ± 1.51 0.01 ± 1.20 0.00 ± 0.00 0.01 ± 1.61 0.05 ± 1.60 0.09
S3 0.03 ± 1.30 0.05 ± 0.62 0.06 ± 1.22 0.02 ± 1.22 0.03 ± 1.31 0.19
Maize S4 0.02 ± 1.15 0.04 ± 1.52 0.02 ± 1.51 0.03 ± 1.40 0.01 ± 1.15 0.12
S5 0.00 ± 0.00 0.02 ±1.31 0.01 ± 1.26 0.01 ± 1.21 0.05 ± 1.31 0.09
S6 0.00 ± 0.00 0.00 ± 0.0 0.03 ± 1.51 0.02 ± 1.11 0.06 ± 1.22 0.11
Min 0.00 0.00 0.00 0.01 0.01 0.07
Max 0.09 0.10 0.13 0.16 0.17 0.22
Mean 0.02 0.029 0.042 0.049 0.055 0.195
Proportion of Total 10.26 14.87 21.54 25.13 28.21
104
Table No 84
Zinc (mg/Kg) in Different Fractions o
f Soil Samples from Cucumber, Tomato, Maize Fields Receiving Treated Combined Laboratory
Wastewater for Irrigation
105
Table No.85
Metal Concentration (mg/kg) in Different Fractions of Soil Samples from Cucumber, Tomato,
Maize Fields Receiving Raw Combined Waste Water for Irrigation
106
Table No.86
Metal Concentration (mg/Kg) in D
Different Fractions of Soil Samples Receiving Treated Combined Laboratory Waste Water for
Irrigation
Table No. 87
Treated Combined Laboratory Wastewater Cucumber with 4% O.M (Lysimeter-1)
107
Table No.88
Untreated Combined Laboratory Wastewater Plants Cucumber Without 10%O.M (Lysimeter-1)
Table No.89
Tube Well Water Plants Cucumber without O.M (Control Lysimeter-1)
Table No.90
Treated Combined Laboratory Wastewater plants Tomato with 4%O.M (Lysimeter-2)
Table No. 91
Untreated combined Laboratory wastewater plants Tomato with 10% O.M (Lysimeter -2)
Table No.92
Drinking water plants Tomato without O.M (Control Lysimeter -2)
108
Table No.93
Treated combined Laboratory wastewater plants Maize with 4% O.M (Lysimeter -3)
Table No.94
Untreated Combined Laboratory Wastewater Plants Maize with 10% O.M (Lysimeter -3)
Table No.95
Tube well Water Plants Maize without O.M (Control Lysimeter-3)
Table No.96
Cucumber yield in Different Soils (gm. Lysimeter -1)
Table No.97
Tomato Yield in Different Soils (gm. Lysimeter-2)
109
Table No 98
Maize Yield in Different Soils (gm. Lysimeter-3)
Table No.99
Tolerance Index for Soils Treated with Cd, Cr and Ni
Metal O.M Cucumber Tomato Maize Mean
0% 0.94 0.92 0.82 0.89
Cd 4% 0.96 0.93 0.83 0.92
10% 0.98 0.94 0.86 0.93
0% 0.29 0.31 0.21 0.27
Cr 4% 0.37 0.29 0.27 0.42
10% 0.47 0.33 0.29 0.46
0% 0.82 0.42 0.21 0.55
Ni 4% 0.84 0.43 0.23 0.50
10% 0.86 0.54 0.24 0.55
Table No.100
Cadmium Concentration (mg/Kg-1) in Cucumber, Tomato and Maize
in Soils without OM, with 4% OM and with 10% OM in soil
Treatment Without OM With 4% OM With 10% OM
Control 0.00 0.03 0.05
Cucumber 3.24 12.42 14.02
Tomato 4.51 4.62 6.26
Maize 7.41 9.03 9.38
Table No.101
Cr Concentration (mg.Kg-1) in Cucumber, Tomato and Maize in Soils
Without OM, with 4% OM and with 10% OM in soil
Treatment Without OM With 4% OM With 10% OM
Control 0.02 0.06 0.09
Cucumber 1.21 1.01 0.98
Tomato 1.31 1.90 1.63
Maize 1.22 1.95 1.85
Table No.102
Ni Concentration (mg.Kg-1) in Cucumber, Tomato and Maize in Soils
Without OM, with 4% OM and with 10% OM in soil
110
Annexure-II
Figures
111
Fig.1. Effect of contact time on % Reduction COD by ash, activated Carbon and without adsorbent (blank).
Fig .2.Effect of pH on % reduction COD by ash, activated carbon and blank (without adsorbent)
100
% Reduction COD
80
60
40
20
0
20 25 30 35 40 45 50 55 60 65 70 75
Fig.3. Effect of adsorption dose on % COD reduction by ash, activated carbon and without adsorbent (blank).
112
pH raw wastewater pH after sedimentation pH after biological treatment
8
7.5
pH 7
6.5
6
Jan Feb March April May June July August Sept Oct Nov Dec
Fig'4 Months
113
114
Fig .11 Treatments with Coagulants
115
Fig. 14: Turbidity Removal using Different blended solution
116
117
118
Ammonia Nitrogen mg/l Removal %
50
Ammonia Nitrogen Removal %
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 18(a) Removal of Ammonia Nitrogen with Two min Treatment time at
pH 9 1st year
40
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 19(a) Removal of Ammonia Nitrogen with Three min Treatment time at
pH 9 1st year
119
Ammonia Nitrogen mg/l Removal %
70
100
90
80
70
60
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 21 Removal of Ammonia Nitrogen with Five min Treatment at pH 9
1st year
100
90
80
70
60
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 22 Removal of Ammonia Nitrogen with Different contact times at pH
9 1st year 120
Ammonia Nitrogen Removal%
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 24 Ammonia Nitrogen Removal with Two min Treatment time at pH 9
2nd year
70
60
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 25 Ammonia Nitrogen Removal with Three min Treatment time at pH 9 121
2nd year
Ammonia Nitrogen mg/l Removal %
100
60
40
20
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 26 Ammonia Nitrogen Removal with Four min Treatment time at
pH 9 2nd year
80
60
40
20
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 27 Removal of Ammonia Nitrogen with Five min Treatment time
at pH 9 2nd year
100
80
60
40
20
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 28 Ammonia Nitrogen Removal with Different contact times at
pH 9 2nd year
122
Ammonia Nitrogen mg/l Removal %
45
40
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 30 Removal of Ammonia Nitrogen with Two min Treatment time
at pH 10 1st year
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 31 Removal of Ammonia Nitrogen with Three min Treatment
time at pH 10 1st year
123
Ammonia Nitrogen mg/l Removal %
100
Ammonia Nitrogen removal %
80
60
40
20
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 33 Removal of Ammonia Nitrogen with Five min Treatment time
at pH 10 1st year
100
90
80
70
60
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 34 Removal of Ammonia Nitrogen with Different Treatment times at
pH 10 1st year
124
Ammonia Nitrogen Removal
Ammonia Nitrogen mg/l Removal %
40
% 30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 35 Removal of Ammonia Nitrogen with one min Treatment
time at pH 10 2nd year
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 36 Removal of Ammonia Nitrogen with Two min Treatment time at pH
10 2nd year
100
90
80
70
60
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 37 Removal of Ammmonia Nitrogen with Four min Treatment time
at pH 10 2nd year
125
Ammonia Nitrogen mg/l Removal %
90
80
70
60
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 39 Removal of Ammonia Nitrogen with Five min Treatment time at
pH 10 2nd year
100
90
80
70
60
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec 126
Fig 40 Ammonia Nitrogen removal with Different Treatment times at pH 10
2nd year
Ammonia Nitrogen mg/l Removal %
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 42 Removal of Ammonia Nitrogen with Two min Treatment time at pH
11 1st year
70
60
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 43 Removal of Ammonia Nitrogen with Three min Treatment time at pH 127
11 1st year
Ammonia Nitrogen mg/l Removal %
100
Ammonia Nitrogen removal %
80
60
40
20
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 44 Removal of Ammonia Nitrogen with Four min Treatment time at pH 11
1st year
100
90
80
70
60
50
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 46 Removal of Ammonia Nitrogen with Different contact times and 128
pH 11 1st year
Ammonia Nitrogen mg/l Removal %
35
Ammonia Nitrogen Removal % 30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 47 Removal of Ammonia Nitrogen with one min Treatment
time at pH 11 2nd year
40
30
20
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 48 Removal of Ammonia Nitrogen with Two min Treatment time at pH 11
2nd year
80
60
40
20
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 49 Removal of Ammonia Nitrogen With Three min Treatment time at pH
11 2nd year
129
Ammonia Nitrogen mg/l Removal %
80
60
40
20
0
Jan Feb Mar April May June July Aug Sept Oct
Fig 50 Removal of Ammonia Nitrogen with Four min Treatment time at pH 11
2nd year
80
60
40
20
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 51 Removal of Ammonia Nitrogen with Five min Treatment time at pH 11
2nd year
130
Ammonia Nitrogen mg/l Residual Ammonia Nitrogen mg/l
45
Residual Ammonia Nitrogen mg/l 40
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 53 Residual Ammonia Nitrogen with one min Treatment time at pH 9 1st year
40
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 54 Residual Ammonia Nitrogen with Two min Treatment time at pH 9 1st year
40
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 55 Residual Ammonia Nitrogen with Three min Treatment time at pH 9 131
1st year
Ammonia Nitrogen mg/l Residual Ammonia Nitrogen mg/l
45
40
Ammonia Nitrogen mg/l
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
40
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig. 57 Residual Ammonia Nitrogen with Five min Treatment time at
pH 9 1st year
132
Ammonia Nitrogen mg/l Residual Ammonia Nitrogen mg/l One min
Residual Ammonia Nitrogen mg/l Two min Residual Ammonia Nitrogen mg/l Three min
Residual Ammonia Nitrogen mg/l Four min Residual Ammonia Nitrogen mg/l Five min
45
Residual Ammonia Nitrogen mg/l
40
35
30
25
20
15
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 58 Residual Ammonia Nitrogen with different conctact times at pH 9 1st year
40
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 59 Residual Ammonia Nitrogen with one min Treatment
time at pH 10 1st year
133
Ammonia Nitrogen m g/l Residual Ammonia Nitrogen mg/l
45
40
35
Ammonia Nitrogen mg/l
30
25
20
15
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 61 Res idual Ammonia Nitrogen with Three min Treatment time at pH 11 1s t year
40
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 62 Residual Ammonia Nitrogen with Four min Treatment Time at pH
10 1st year
134
Total Nitrogen mg/l Residual ammonia Nitrogen mg/l
45
40
Ammonia Nitrogen mg/l
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov
Fig 63 Residual Ammonia Nitrogen with Five min Treatment time at pH 10 1st year
45
Residual Ammonia Nitrogen mg/l
40
35
30
25
20
15
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 64 Residual Treatment of Ammonia with different Treatment times at pH 10
1st year
135
Ammonia Nitrogen mg/l Residual Ammonia mg/l
45
Ammonia Nitrogen mg/l 40
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 65(a) Residual Ammonia Nitrogen with one min Treatment time at pH 11 1st
year
136
Ammonia Nitrogen mg/l Residual Ammonia Nitrogen mg/l
45
137
138
139
Ammonia Nitrogen Residual Ammonia Nitrogen mg/l one min
Residual Ammonia Nitrogen mg/l Two min Residual Ammonia Nitrogen mg/l Three min
Residual Ammonia Nitrogen mg/l Four min Residual Ammonia Nitrogen mg/l Five min
35
30
Ammonia Nitrogen mg/l
25
20
15
10
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 75 Residual Ammonia Nitrogen with different Treatment time at pH 9 2nd year
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 76 Residual Ammonia Nitrogen removal with one min Treatment time at pH 10 2nd
year
140
141
Ammonia Nitrogen mg/l Residual ammonia mg/l one min
Residual ammonia mg/l Two min Residual ammonia mg/l Three min
Residual Ammonia Nitrogen mg/l
Residual ammonia mg/l Four min Residual ammonia mg/l Five min
35
30
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 81 Residual Ammonia Nitrogen with different contact times at pH 10 2nd
year
25
20
15
10
5
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig 83 Residual Ammonia Nitrogen with Two min Treatment time at pH 11 2nd year
142
143
Cadimium (Cd) mg/l Nickle (Ni) mg/l Chromium (Cr) mg/l Zinc (Zn) mg/l
0.25
Metals concentration mg/l
0.2
0.15
0.1
0.05
0
1 2 3 4 5 6 7 8 9 10 11 12
Fig 90. Different metals concentration in raw combined wastewater during Ist
year
144
Befor sedimentation After sedimentation
After Biological Treatment After Chemical Treatment
0.07
Cd concentration mg/l
0.06
0.05
0.04
0.03
0.02
0.01
0
Month Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig. 91. Cadmium Removal after different treatments in wastewater during Ist
year
0.5
0.4
0.3
0.2
0.1
0
Jan Feb Mar April May June July Aug Sept Oct Nov
Fig. 92. Nickel Removal after different treatments of wastewater during Ist year
0.18
0.16
0.14
Chromium mg/l
0.12
0.1
0.08
0.06
0.04
0.02
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig.93 Chromium Removal after different treatment from wastewater in Ist year
145
Before Sedimentation Zn mg/l After sedimentation Zn mg/l
After Biological Treatment Zn mg/l After chemical Treatment Zn mg/l
0.12
Zn Concentration mg/l
0.1
0.08
0.06
0.04
0.02
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig.94. Zinc Removal from wastewater during different Treatments in Ist year
Cadmium (Cd) mg/l Nickel (Ni) mg/l Chromium (Cr) mg/l Zinc (Zn) mg/l
1
0.9
0.8
Metals concentration mg/l
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
1 2 3 4 5 6 7 8 9 10 11 12
Fig.95. Different metals concentration in raw combined wastewater during 2nd
year
0.2
0.15
0.1
0.05
0
Month Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig.96. Cadmium Removal after different treatments in wastewater during 2nd year
146
Before Sedimentation Ni mg/l After sedimentation Ni mg/l
After Biological Treatment Ni mg/l After chemical Treatment Ni mg/l
0.09
0.08
0.07
Ni concentration mg/l
0.06
0.05
0.04
0.03
0.02
0.01
0
Jan Feb Mar April May June July Aug Sept Oct Nov Dec
Fig.97 Nickel Removal after different treatments from wastewater during 2nd year
147
Average 1st year Temp Average 2nd year Temp
40
35
30
Temperature ° C
25
20
15
10
0
Month Jan Feb March April May June July August Sept Oct Nov Dec
Fi g 100. Va ri ation i n tempreture va lue during Ist & 2nd year
8
7.8
7.6
7.4
7.2
7
3
Phasphrous mg/L
2.5
1.5
0.5
0
Jan
Feb
March
April
May
June
July
August
Sept
Oct
Nove
Dec
148
Fig.102. Variation in phasprrous during the Ist & 2nd year
149
150