Thesis

Low Cost Municipal Wastewater Treatment
By
Zulfiqar Ahmad Bhatti

SP05-R67-003
Ph.D. Thesis
COMSATS Institute of Information Technology

Abbottabad - Pakistan
March, 2011
COMSATS Institute of Information Technology
A Thesis Presented to
COMSATS Institute of Information Technology, Abbottabad
In partial fulfillment
of the requirement for the degree of
Ph.D.
(Environmental Sciences)
By

CIIT/SP05-R67-003/ABT
March, 2011
ii
A Post Graduate Thesis submitted to the Department of Environmental Sciences

as partial fulfillment of the requirement for the award of Degree of Ph.D.
Name
Registration Number
CIIT/SP05-R67-003/ABT
Supervisor
Prof. Dr. Iftikhar Ahmad Raja
Department of Environmental Sciences
Abbottabad, Campus.
COMSATS Institute of Information Technology (CIIT)
Abbottabad, Campus.
March, 2011
iii
Final Approval
This thesis titled

By

Has been approved
For the COMSATS Institute of Information Technology, Abbottabad
External Examiner: __________________________________________

Dr Ghulam Jilani
Associate Professor, Soil Sciences and Water Conservation
Supervisor: ________________________________________________
Dr. Iftikhar Ahmad Raja
Foreign Professor
Dean: ________________________________________________
Prof. Dr. Arshad Saleem Bhatti
Dean (Faculty of Sciences)
iv
Declaration
I Zulfiqar Ahmad Bhatti hereby declare that I have produced the work presented in this
thesis, during the scheduled period of study. I also declare that I have not taken any
material from any source except referred to wherever due. If a violation of HEC rules
on research has occurred in this thesis, I shall be liable to punishable action under the
plagiarism rules of the HEC.
Date: _________________
Signature of the student:

____________________
(Zulfiqar Ahmad Bhatti)
(CIIT/SP05-R67-003/ABT)
Certificate
It is certified that Mr. Zulfiqar Ahmad Bhatti has carried out all the work related to this
thesis under my supervision at the Department of Environmental Sciences, CIIT
Abbottabad.
Supervisor:
Dr. Iftikhar Ahmad Raja

Department of Environmental Sciences
CIIT Abbottabad
Submitted through:
Dr. Arshad Pervez

Head, Department of Environmental Sciences
CIIT, Abbottabad
Prof. Dr. Ishtiaq Jadoon

Chairman, Department of Environmental Sciences
CIIT, Abbottabad
vi
DEDICATION
To Almighty ALLAH and the Holy Prophet

Muhammad (P.B.U.H)
&
My Loving Mother (Hafeeza Iftikhar) and Wife

(Farhana Maqbool)
vii
ACKNOWLEDGEMENTS
Its really hard to express my feelings upon achieving the biggest milestone in my life.
The first and profound gratitude goes to Almighty Allah. All praises for Almighty
Allah- the most benevolent, ever merciful and compassionate, the creator of universe
who awarded me strength, good health and confidence throughout my endeavor. I
extend my humblest and enthusiastic words of thanks to His Holy prophet Muhammad
(Blessing and peace be upon him) who is forever source of light and guidance for all
the humanity.
I would like to extend my sincere gratitude to the CIIT research grant Islamabad for
young scientist who provided funds for research to complete PhD.
I am deeply indebted to my Supervisor Professor Dr Iftikhar Ahmad Raja for
accepting and providing me a chance to work as a Doctoral student under his dynamic
supervision and able guidance during my studies. I personally feel that professor Dr
Iftikhar Ahmad Raja is really a loving teacher and kind person who encourage me in
all success and failures.
I am cordially thankful to Dr Qaisar Mahmood for his kind help in start up of up flow
anaerobic sludge blanket reactor. I wish to express my cordial thanks and gratitude to
all individuals and COMSATS institute of information technology Abbottabad that
have contributed to make this study a success and make this dissertation possible.
Especial thanks to Ir Prof Dr Willy Verstraete, Ghent University Belgium, who
suggested me to study this treatment option.
I am also thankful to Dr. Zahid Mehmood who guided me at the beginning of my
research work. I would be failing in my duties if I do not pay cordial tribute to my
colleagues, friends and well wishers especially Dr Muhammad Ahmad Farooqui, Dr
Javaid Jahan Baluch, Dr Amir Haider Malik, Dr Rubina Farooq, and Dr Ather
Farooq Khan and many others whose name I could not write due to shortage of space
and time.
It gives me great pleasure to express my deepest gratitude to my lab mates, Farhana
Maqbool, Sulman, Naveed, Mirbaz, Jamil Khan, Irum Shahzadi, Maria Siddique,
Naim Rashid, Faisal Mustafa and Nosheen Mirza. I am also thankful to all
viii
laboratory attendants Saboor, Maroof and Naeem facilitating in handling equipments

and collection of samples.
With a deep sense of honor, I am highly thankful to my affectionate parents, brothers,
sisters and all of my family members whose hands always rise in pray for my brilliant
future. I am grateful and indebted to my late father who always encouraged throughout
my educational career.
May Allah bless all of us and may this contribution be
beneficial for the welfare of humanity and the survival of human race.

March, 2011
ix
ABSTRACT
LOW COST MUNICIPAL WASTEWATER TREATMENT
The present study on low-cost treatment of combined municipal wastewater (MWW)
containing food industry effluents by up-flow anaerobic sludge blanket (UASB) in
combination with advanced oxidation process (AOP) as post treatment of UASB
effluent can be summarized as under:
Chemically enhanced primary treatment was first tested in the research to select best
coagulant to reduce the pollutant load of MWW. Various coagulants viz. FeCl3,
Moringa oleifera seed extract and alum were compared for their suitability to treat
MWW. Different concentrations (4~32 mg L-1) were applied in a series of batch
treatment process mode at 600-620 rpm stirring for five minutes. It was observed that
alum was effective in reducing the chemical oxygen demand (COD) up-to acceptable
level but above the optimized dose of alum total dissolved solids (TDS) were found
increasing at greater extent. There was an increase of TDS when the level of alum was
increased above the optimized value of 32 mg L-1. The highest rate of pollutants
removal load was observed when 22 to 30 mg L-1 of alum was used. Therefore, alum
concentration in the range of 22 to 30 mg L-1 was an optimum dose for MWW
treatment. Removal of COD and Ortho-Phosphorus can be possible with increased
dose of alum but the cost of alum and increase of TDS shows less relatively favorable.
Another low-cost option to compare with chemically enhanced primary
treatment (CEPT) was to test waste H2O2 (40%) to treat domestic wastewater, where
direct treatment of MWW was given as batch process by 40% waste H2O2. Waste
H2O2 proved as powerful oxidant in minimizing the organic load of MWW. The
optimum dose of waste H2O2 was found as 2.5 ml L-1 which significantly (p < 0.05)
reduced biological oxygen demand (BOD5) and COD in 120 min, thus meeting the
national environmental quality standards (NEQS) for MWW. The results revealed that
disinfection capacity of 40% waste H2O2 @ 2.5 ml L-1 caused significant reduction of
fecal coliform populations to less than half of the initial value while treating MWW. It
was proved most successful and economical removal of COD and microbial load. The
most attractive outcome in this regard is using waste from one industry to treat
municipal waste. The drawback in this regard, infrequent supply of waste H2O2 from
industry can stop the treatment process.
Some industries were selected to treat their wastewater. Carwash industry was
one of them whose effluent was not studied often. This wastewater contained high
content of oil 83 mg L-1 and COD >1000 mg L-1. Due to presence of oil it was not
feasible to treat directly with alum or H2O2. Therefore aeration was added as
pretreatment step to bring oil content to the surface where it was scraped out from
aeration tank. Effluent from aeration tank was further treated with alum in second step
and H2O2 at third step. Treatment efficiency was 96% oil, COD, turbidity and TDS
were reduced upto 93%, 94% and 74%, respectively. The present approach was proved
cost effective and requires less space without any pH control. Only costly factor was
aeration to separate the oil, other than aeration it can be more expensive to separate.
Thus the treatment process can be applied on pilot scale to further evalute its
efficiency.
The present study also compared the effectiveness of used and fresh H2O2 to
treat the domestic waste and to reduce the alum dose for chemical sedimentation. It
was observed that used waste 40% H2O2 was very effective and economical. Fresh
35% H2O2 can be purchased Rs 40/L from the market but used waste 40% H2O2 can be
obtained only from specific industries where it used for disinfection. Using 40% waste
H2O2 was found very effective to reduce COD, turbidity and microbial load. An
addition step was merged into H2O2 was ultra violet (UV) light to speed up the
reaction. The proposed system was consists of two major step where first sediments
was settled down with alum and decant from first step was used to treat with H2O2 and
UV in the same tank. This proposed system was effective (p < 0.05) to treat domestic
wastewater but carwash and food industry wastewater may require other treatment
steps need to be added. The combination of H2O2 with UV light was found very
effective (p < 0.05) to decrease BOD, COD, and turbidity and coliform bacteria in
MWW. Waste H2O2 generated from an industrial process of disinfection was found
more effective in the treatment of domestic wastewater than fresh 35% H2O2. The
waste H2O2 can be applied in combinations with UV light to treat domestic wastewater
effectively.
The UASB reactor was used to treat mixed MWW at hydraulic retention time
24-48 hrs and at an average temperature 25-34C. The aim was to test two stage
xi
treatment concept for low cost MWW treatment as UAB in first stage and waste H2O2
40% 2 ml L-1 of UASB effluent at second stage.
Moreover, the effect of
micronutrients on the treatability of UAB was also investigated. After start up with
glucose for first 15 days (first stage), the reactor was fed with macro and
micronutrients synthetic nutrients influent (SNI) for 45 days (second stage). The
maximum substrate removal rate was same 0.07 d-1 for both glucose and SNI. Removal
efficiency of total suspended solids (TSS), COD, total nitrogen (TN), ortho phosphorus
(Ortho-P) and Turbidity as 73%, 99%, 84%, 19% and 67%, respectively. Waste H2O2
was found successful in NH4+ removal during post treatment where 80% nitrogen was
removed. Low cost integrated treatment using UASB and H2O2 was found an excellent
novel treatment choice for mixed MWW in developing countries.
Anaerobic treatment in combination with post treatment of advanced oxidation
process was employed to test the treatability of integrated process for confectionary
wastewater mixed with MWW. Reactor was inoculated with 10 year old septic tank
sludge and started up with glucose, macro and micro nutrients. The system was
operated at 25-30C, hydraulic retention time (HRT) 48 hrs for 25 days with post
treatment with 40% waste H2O2. This waste H2O2 was collected from industrial
process after disinfection of packaging material. Reactor performance was evaluated
by pre and post treatment analysis for COD, TSS, TDS, and turbidity and their removal
efficiencies were up to 98.6%, 91%, 50% and 81%, respectively. Reactor achieved its
full efficiency after feeding diluted wastewater at the value of 1/5, 1/3, 1/2 and 1/0 for
5 7 days each. Reactor achieved full efficiency in 25 days removing 98% COD from
mixed wastewater. A batch peroxide treatment process was also added to reduce the
turbidity and to increase the dissolved oxygen (DO) of treated effluent. The strategy
was found quite applicable for the treatment of combined industrial and municipal
effluents.
Key words: Upflow anaerobic sludge blanket, advanced oxidation process, chemically
enhanced primary treatment, national environmental quality standards.
xii
Table of Contents
Chapter 1: Introduction .............................................................................................. 1

1.1
INTRODUCTION ......................................................................................................... 2
1.2
LOW COST TREATMENT OPTION FOR PAKISTAN ...................................................... 4
1.2.1
Sewage treatment ................................................................................................................ 4
1.2.2
Process overview ................................................................................................................. 4
1.3
PRE-TREATMENT....................................................................................................... 5
1.3.1
Screening ............................................................................................................................. 5
1.3.2
Grit removal ........................................................................................................................ 5
1.3.3
Primary treatment ................................................................................................................ 5
1.4
SECONDARY TREATMENT ......................................................................................... 6
1.5
UP-FLOW ANAEROBIC TREATMENT REACTOR ......................................................... 6
1.6
OTHER MUNICIPAL WASTEWATER TREATMENT OPTIONS....................................... 7
1.6.1
Activated sludge .................................................................................................................. 7
1.6.2
Surface-aerated basins......................................................................................................... 7
1.6.3
Membrane bioreactors......................................................................................................... 7
1.6.4
Rotating biological contactors ............................................................................................ 8
1.6.5
Lagooning............................................................................................................................ 8
1.6.6
Constructed wetlands .......................................................................................................... 9
1.6.7
Nutrient removal ................................................................................................................. 9
1.7
TERTIARY TREATMENT .......................................................................................... 11
1.7.1
Filtration ............................................................................................................................ 11
1.7.2
Disinfection ....................................................................................................................... 11
1.8
AIMS OF THIS STUDY .............................................................................................. 12
2 Chapter 2: Literature Review .............................................................................. 17

2.1
2.1.1
CHARACTERISTICS OF MUNICIPAL WASTEWATER/DOMESTIC WASTEWATER ...... 18

Storm water and combined wastewater ............................................................................ 19
2.2
NEWLY IDENTIFIED TOXICANTS IN TREATED DOMESTIC WASTEWATER .............. 20
2.3
TREATMENT OPTIONS ............................................................................................. 21
2.3.1
Primary sedimentation ...................................................................................................... 21
2.3.2
Physico-chemical treatment .............................................................................................. 23
2.4
COLLOIDAL CHEMISTRY OF WASTEWATER ........................................................... 24
2.5
COAGULATION IN WATER TREATMENT ................................................................. 24
xiii
2.6
CHEMICALLY PRIMARY TREATMENT OF WASTEWATER ........................................ 25
2.6.1
Financial benefits of CEPT ............................................................................................... 26
2.6.2
Efficiency of organic and inorganic coagulants ............................................................... 26
2.7
OILY WASTEWATER TREATMENT WITH COAGULATION/FLOCCULATION ............. 29
2.8
USE OF CEPT SLUDGE AS ADSORBENT .................................................................. 29
2.9
EFFECT OF POLYMERIC FLOCCULENT PRODUCED FROM PLASTIC WASTE ............ 30
2.10
COMBINE CHEMICAL AND BIOLOGICAL LOW COST TREATMENT SYSTEMS .......... 31
2.11
ADVANCE OXIDATION PROCESSES IN MUNICIPAL WASTEWATER TREATMENT.... 33
2.11.1
Municipal wastewater treatment with H2O2 ................................................................ 34
2.11.2
Fenton reagent in AOP ................................................................................................. 35
2.11.3
Textile effluent treatment with AOP ........................................................................... 36
2.12
SLUDGE DIGESTION WITH H2O2.............................................................................. 36
2.13
ANAEROBIC TREATMENT OF MUNICIPAL WASTEWATER TREATMENT.................. 37
2.13.1
Hydrolysis..................................................................................................................... 38
2.13.2
Acetogenesis and Acid Formation ............................................................................... 38
2.13.3
Methanogenesis ............................................................................................................ 39
2.13.4
Start up of up flow anaerobic sludge blanket (UASB) reactor ................................... 39
2.13.5
Start up of UASB reactor without inoculation ............................................................ 45
2.13.6
Function of micro-nutrients during start-up of UASB ................................................ 46
2.13.7
Operational data and micronutrient requirement ......................................................... 47
2.13.8
Gas utilization............................................................................................................... 48
2.13.9
Industrial wastewater treatment by UASB .................................................................. 49
2.14
CONCLUSIONS ......................................................................................................... 50
3 Chapter 3: .............................................................................................................. 61
Municipal Wastewater Treatment by Coagulation ................................................ 61
3.1
INTRODUCTION ....................................................................................................... 63
3.2
MATERIALS AND METHODS.................................................................................... 65
3.2.1
Collection of MWW.......................................................................................................... 65
3.2.2
Batch experiments ............................................................................................................. 65
3.2.3
Analytical procedures ....................................................................................................... 65
3.3
RESULTS AND DISCUSSIONS ................................................................................... 65
3.3.1
Effect of various coagulants on COD ............................................................................... 65
3.3.2
Effect of various coagulants on TDS ................................................................................ 67
3.3.3
Effect of reaction time and alum level on TSS ................................................................ 68
3.3.4
Effect of alum on ortho-phosphate and nitrogen .............................................................. 70
3.3.5
Effect of alum on turbidity ................................................................................................ 72
3.4
ECONOMIC ASPECTS ............................................................................................... 73
xiv
3.5
CONCLUSIONS ......................................................................................................... 73
4 Chapter 4: .............................................................................................................. 77
Municipal Wastewater Treatment by Waste Hydrogen Peroxide
4.1
INTRODUCTION ....................................................................................................... 79
4.2
4.2.1
Wastewater sampling ........................................................................................................ 80
4.2.2
Optimization of H2O2 dose ............................................................................................... 80
4.2.3
Treatment system .............................................................................................................. 81
4.2.4
Microbial count ................................................................................................................. 81
4.2.5
4.2.6
Graphical work .................................................................................................................. 82
4.3
RESULTS AND DISCUSSION ..................................................................................... 82
4.3.1
BOD removal .................................................................................................................... 82
4.3.2
COD removal .................................................................................................................... 83
4.3.3
BOD5/COD ratios and biodegradability of MWW .......................................................... 84
4.3.4
Turbidity removal.............................................................................................................. 86
4.3.5
Effect on PH after addition of H2O2 ................................................................................. 88
4.3.6
Economic aspects .............................................................................................................. 88
4.4
CONCLUSIONS ......................................................................................................... 88
5 Chapter 5: .............................................................................................................. 91
Integrated Carwash Wastewater Treatment by Hydrogen Peroxide
5.1
INTRODUCTION ....................................................................................................... 93
5.2
5.2.1
Wastewater and waste H2O2 collection ............................................................................ 94
5.2.2
Experimental design .......................................................................................................... 94
5.2.3
5.3
RESULTS AND DISCUSSIONS ................................................................................... 95
5.3.1
Aeration for oil water separation ...................................................................................... 95
5.3.2
Effects of treatment on turbidity of CWW ....................................................................... 97
5.3.3
Influence of alum treatment on COD removal ................................................................. 97
5.3.4
Effects on TDS after alum treatment ................................................................................ 98
5.3.5
Effect of treatment on pH of CWW .................................................................................. 99
5.3.6
Effect of treatment on dissolved oxygen (DO) of CWW ............................................... 100
5.3.7
Influence of H2O2 addition on CWW ............................................................................. 100
5.4
CONCLUSIONS ....................................................................................................... 102
6 Chapter 6: ............................................................................................................ 105

xv
Municipal Wastewater Treatment by Physico-Chemical Processes

6.1
INTRODUCTION ..................................................................................................... 107
6.2
MATERIAL AND METHODS ................................................................................... 108
6.2.1
Wastewater sampling ...................................................................................................... 108
6.2.2
Optimization of H2O2 dose ............................................................................................. 109
6.2.3
Treatment system ............................................................................................................ 109
6.2.4
Microbial count ............................................................................................................... 110
6.2.5
Analytical procedures ..................................................................................................... 110
6.3
RESULTS AND DISCUSSIONS ................................................................................. 111
6.3.1
Effect on pH .................................................................................................................... 111
6.3.2
Changes in turbidity ........................................................................................................ 112
6.3.3
Effect on COD and BOD after treating with 35% fresh H2O2/UV and 40% waste
H2O2/UV ........................................................................................................................................ 113

6.3.4
6.4
Microbial activity ............................................................................................................ 115
CONCLUSIONS ....................................................................................................... 115
7 Chapter 7: ............................................................................................................ 118

Municipal Wastewater Treatment by Integrated System
7.1
INTRODUCTION ..................................................................................................... 120
7.2
OBJECTIVES .......................................................................................................... 121
7.3
MATERIALS AND METHODS.................................................................................. 122
7.3.1
Start up of UASB reactor ................................................................................................ 122
7.3.2
Determination of substrate uptake rate, biodegradable fractions and growth yield ...... 123
7.3.3
7.4
RESULTS AND DISCUSSIONS ................................................................................. 126
7.4.1
Effect of glucose during UASB start up period ............................................................. 126
7.4.2
COD removal efficiency from glucose and SNI ............................................................ 127
7.4.3
Substrate uptake rate during start up with glucose and SNI .......................................... 130
7.4.4
UASB effluent treatment with waste H2O2 .................................................................... 134
7.4.5
Performance of reactor at different HRT ........................................................................ 136
7.5
ECONOMIC ASPECTS ............................................................................................. 138
7.6
CONCLUSIONS ....................................................................................................... 139
8 Chapter 8: ............................................................................................................ 144

Sequential Two Stages Anaerobic and H2O2 Treatment of Confectionary
Wastewater
8.1
INTRODUCTION ..................................................................................................... 146
xvi
8.2
MATERIALS AND METHODS.................................................................................. 147
8.2.1
Wastewater Sample ......................................................................................................... 147
8.2.2
Treatment design ............................................................................................................. 147
8.2.3
8.3
RESULTS AND DISCUSSION ................................................................................... 149
8.3.1
Use of H2O2 to polish UASB effluent ............................................................................ 154
8.3.2
Comparison with other processes ................................................................................... 155
8.4
CONCLUSIONS ....................................................................................................... 156
9 Chapter 9: ............................................................................................................ 160

Major Findings and Future Recomendations
9.1
MAJOR FINDINGS .................................................................................................. 161
9.2
FUTURE RECOMMENDATIONS .............................................................................. 164
xvii
List of Figures
Figure 2.1 CEPS-UASB (Kologo, 1999) ..................................................................... 31
Figure 2.2 Schematic of the low investment sewage treatment concept with zeolite
installation ................................................................................................... 32
Figure 2.3 The UASB reactor ...................................................................................... 42
Figure 2.4 Biological conversions in aerobic and anaerobic systems ......................... 42
Figure 2.5 Anaerobic decomposition of organic matter (Zehnder et al., 1982) .......... 43
Figure 3.1 Location of MWW sampling site in Abbottabad city ................................ 64
Figure 3.2 Decrease in COD after treating with various coagulants ........................... 66
Figure 3.3 Effect of various coagulants on TDS of MWW ......................................... 67
Figure 3.4 Effect of different concentrations of alum on TDS of MWW.................... 68
Figure 3. 5 Effect of alum treatment reaction time on TSS of MWW......................... 69
Figure 3.6 Effect of different concentrations of alum on removal percentage of TSS
from MWW ................................................................................................. 70
Figure 3.7 Effect of different concentrations of alum on removal percentage of TSS
from MWW ................................................................................................. 71
Figure 3.8 Effect of different concentrations of alum on removal percentage of total
kjeldahl nitrogen of MWW ......................................................................... 72
Figure 3.9 Effect of different concentrations of alum on the removal of turbidity in
MWW .......................................................................................................... 72
Figure 4.1 BOD reduction during treatment ................................................................ 82
Figure 4.2 COD removal during treatment .................................................................. 83
Figure 4.3 The variation of BOD/COD ....................................................................... 84
Figure 4.4 COD and turbidity percentage removal ...................................................... 85
Figure 4.5 Changes in pH during treatment ................................................................. 86
Figure 5.1 Schematic diagram of a multi-stage treatment of carwash wastewater ...... 95
Figure 5.2 Effect of aeration on oil contents of CWW ................................................ 96
Figure 5.3 Turbidity reduction of CWW after alum dosing ........................................ 96
Figure 5.4 COD Reduction (mg L-1) of CWW at different application rates of alum . 98
Figure 5.5 Effect of treatment on TDS of CWW ......................................................... 99
Figure 5.6 Effect of treatment on pH of CWW ........................................................... 99
Figure 5.7 Effect of treatment on DO of CWW......................................................... 100
xviii
Figure 5.8 Removal percentage of TDS, COD, Turbidity and Oil contents from CWW
.................................................................................................................................... 101
Figure 6.1 Major steps involved in MWW treatment ................................................ 110
Figure 6.2 Effect of fresh H2O2 treatment on pH with the passage of time ............... 112
Figure 6.3 Decrease in turbidity after treating with alum and H2O2/UV, (Raw WW
represents raw wastewater, NS = Natural Sedimentation) ...................... 113
Figure 6.4 Reduction of COD and BOD after treating with 35% fresh and 40% waste
H2O2 along with UV light (Raw WW represents raw wastewater, NS =
Natural Sedimentation) ............................................................................ 114
Figure 7.1 UASB followed by chemical oxidation with 40% hydrogen peroxide. P1=
peristaltic feed pump, P2 = peristaltic recycle pump ............................... 125
Figure 7.2 pHi (influent), pHe (effluent) comparison during start-up of UASB, using
glucose as a sole nutrient ......................................................................... 126
Figure 7.3 pHi and pHe comparison for synthetic influent used for startup after
addition of micronutrients ........................................................................ 126
Figure 7.4 COD and BOD percentage removal comparison ..................................... 127
Figure 7.5 CODi (influent) and CODe (effluent) comparison................................... 128
Figure 7.6 COD influent and COD effluent form fifteenth day with SNI ................. 129
Figure 7.7 Percent COD removal using SNI in UASB.............................................. 130
Figure 7.8 CODe and Glucose as substrate uptake .................................................... 132
Figure 7.9 Comparison of substrate uptake rate of SNI and glucose......................... 132
Figure 7.10 SNI effects on biodegradable fraction and substrate uptake rate. .......... 133
Figure 7.11 Effects of glucose on Fb and U and substrate uptake rate ...................... 133
Figure 7.12 Effect on ammonium, nitrate and nitrite after treating UASB effluent with
H2O2 ......................................................................................................... 137
Figure 8.1 UASB followed by chemical oxidation with 40% hydrogen peroxide. P1=
peristaltic feed pump, P2 = peristaltic recycle pump ............................... 148
Figure 8.2 COD influent, UASB effluent and H2O2 treated effluent with COD removal
mg L-1. PI =Phase one, PII= Phase two, PIII= Phase three, PIV= Phase
four, PV= Phase five. ............................................................................... 152
Figure 8.3 COD removal efficiency, peroxide COD removal can be considered as total
COD percent removal .............................................................................. 153
Figure 8.4 pH comparison of UASB effluent and H2O2 effluent .............................. 153
xix
List of Tables
Table 2-1 Average composition of domestic sewage (Verstraete, 2004). *DW: dry
weight .......................................................................................................... 18
Table 2-2 Size spectrum for waterborne particle ......................................................... 23
Table 2-3 Comparison of removal efficiencies ............................................................ 27
Table 2-4 Hospital wastewater comparison with urban wastewater ............................ 29
Table 2-5 Main advantages and disadvantages of UASB reactor................................ 41
Table 2-6 Function of macro and micro nutrients in anaerobic digestion ................... 47
Table 2-7 Working goal (NEQS) ................................................................................. 48
Table 2-8 Important parameter for MWW treatment in UASB ................................... 48
Table 3-1 The economic analysis of various treatment options for MWW ................. 74
Table 4-1 Pre-experiment Analysis ............................................................................. 80
Table 4-2 The economic analysis of various treatment options for MWW ................. 87
Table 5-1 Characteristics of the raw car wash wastewater .......................................... 94
Table 5-2 Characteristics of the car wash wastewater before and after the treatment.
*Below Detection Limit ......................................................................... 102
Table 6-1 Pre and post experimental Analysis .......................................................... 109
Table 7-1 Composition of synthetic influent (SNI) ................................................... 124
Table 7-2 Component of trace element solution ........................................................ 124
Table 7-3 Parameters (mg L-1) used to start up UASB reactor .................................. 124
Table 7-4 Standard allowable limits for effluent discharge ....................................... 124
Table 7-5 Average characteristics of raw MWW and effluent of various treatment
steps. BDL = Below detection limit ....................................................... 135
Table 7-6 UASB effluent treatment with H2O2 at optimized dose 2.0 ml L-1 ........... 136
Table 7-7 Comparison of UASB HRT start up with different inoculums ................. 138
Table 7-8 The economic analysis of various treatment options for MWW ............... 139
Table 8-1 Parameters used to treat industrial wastewater .......................................... 148
Table 8-2COD removal comparison, in COD mg L-1................................................ 151
Table 8-3 Treatment efficiency .................................................................................. 152
Table 8-4 Lethal ammonia concentrations at different pH, and its exposure ............ 155
Table 8-5 Treatment efficiency comparison of different investigators treating
carbohydrate type wastewater on the basis of COD percent removal ....... 156
xx
LIST OF ABBREVIATIONS
Area
AOP
Advanced oxidation process
Alum
Al2SO48H2O, Al2SO416H2O
BOD
Biological oxygen demand
NH3
Ammonia
CEPT
Chemically enhanced primary treatment
CEPS
Chemically enhanced primary sedimentation
COD
Chemically oxygen demand
CWW
Car wash wastewater
DWW
Domestic wastewater
DFAF
Down flow anaerobic filter
DMM
Domestic wastewater
DO
Dissolved oxygen
EE2
17 Ethynylestradiol
E1
Estrone
E2
17-estradiol
E3
16 , 17 -estradiol
Fb
Biodegradable fraction
GAC
Granulated activated carbon
HRT
Hydraulic retention time
HOW
Heavy oil wastewater
HO2-
Per hydroxy
MABR
Membrane aerated biofilm
NEQS
National environmental quality standard

xxi
MWW
Municipal wastewater
NTU
Naphelomatric turbidity unit
NO2-
Nitrite
NO3-
Nitrate
OLR
Organic loading rate
ORP
Oxidation reduction potential
Ortho-P
Ortho Phosphorus
O3
Ozone
PAQs
Polyphosphate accumulating organisms
PZSS
Polyzine silicate
PAC
Poly aluminium chloride
PFC
Poly ferric chloride
PPCPs
Pharmaceuticals and personal care product
rpm
revolution per minutes
Flow rate
RBC
Rotating biological reactor
SS
Suspended solids
Substrate uptake rate
SNI
Synthetic nutrients influent
TDS
Total dissolved solids
TKN
Total Kjeldhal Nitrogen
TN
Total nitrogen
TSS
Total suspended solids
UASB
Up flow anaerobic sludge blanket
UAB
Up flow anaerobic bioreactor
UV
Ultra violet
xxii
VSS
Volatile suspended solids
WEMOS
Water extracts moringa oleifera seed
WWTP
Wastewater treatment plant
Volume
VFA
Volatile fatty acid
xxiii
Chapter 1: Introduction
Domestic/Municipal Wastewater Loads/Flow Rates with
Respect to Abbottabad and Pakistan
1.1 Introduction
Pakistans current population is of 187 million and is expected to grow up to
approximately 221 million by the year 2025 (PDP, 2011; Khan, 2007). The vast
increasing population of Pakistan putting great affect on the water quality which is
required for meeting the industrial, domestic and agricultural needs. Pakistan is
exhausting its water resources and if this is not managed properly then Pakistan will
become water deficit country. Ground water and surface water quality is not
satisfactory and it is continuously deteriorating due to untreated municipal, industrial
wastewater discharge into surface water and usage of insecticides and fertilizers in
agriculture forms. Monitoring the water quality and its management is not sufficient.
Water availability per capita has declined to 1000 m3 from 5,600 m3 (Khan, 2007;
IUCN, 2009).
Water pollution has increased according to different investigators and
surveyors. Polluted water is found more around the big cities and industrial areas.
Deterioration of water quality often caused by synthetic organic toxic chemicals
especially from tanneries, textile industries and municipal wastewater where it causes
spreading of water borne diseases. Sewage treatment is a process of reducing or
removing of contaminants up to acceptable level (Chandio, 1998).
The public water requirement has raised many folds as population is
increasing, industrial growth and bringing more area under cultivation to meet the
increasing demand of agricultural products. All the above factors forced the water
managers to explore the existing freshwater resources. It has been estimated that
about 27% of worlds population do not have access to clean drinking water (Chandio
and Abdullah, 1998).
The conditions become more adverse in developing countries, where there is
lack of resources and the water protection schemes are of least priority. Study by,
Zahid and Baig (1997) concluded that about 80% people living in main cities of
Pakistan lack access to clean potable water. The environmental profile of Pakistan
indicates that about 40% of deaths are related to waterborne diseases spread by water
pollution, mainly due to the sewage and industrial wastewater contamination to
drinking water distribution systems.
Continuing urbanization, growing populations and increasing industrialization
have increased water consumption and correspondingly generating higher volumes of
2
wastewater. Untreated wastewater and poor solid waste management are threats to
human health and natural environment. Regrettably, the public and the private sectors,
in developing countries including Pakistan, are not focusing their attention to the
wastewater treatment practices on domestic and industrial level. Lack of interest in
controlling water born diseases, which causes severe environmental and health
problems. Most of the wastewater is not treated and with the expansion of urban
settlements without wastewater treatment facilities, it will continue to adversely
impact the natural environment and public health. Worst impacts are evident in areas
which are close to industrial sites.
Saeed and Bahzad (2006), reported that more than 28 m3 sec-1 wastewater was
being disposed off in to the River Ravi without any treatment from second largest city
of Pakistan. The river pollution is frequently associated with the disposal of untreated
effluents from municipal, industrial and agricultural wastes and the natural streams
are always considered as an easy way to dispose off many kinds of effluents. The
peoples psychology is that the wastes are washed away and are not visible after
dumping sites.
A study by Balfours (1987) revealed that about 18 m3 sec-1 of wastewater from
Lahore city was being disposed off into the river Ravi and it is estimated that
wastewater flow would increase to 35 m3 sec-1 by the year 2017. This wastewater is
accompanied by a BOD load of 240 mg L-1.
Municipal and industrial wastewater reclamation constitutes a vast potential of
supplementing current and future water supplies. Recent technological advancement
has shown that it is not only practically possible but economically feasible to use
reclaimed water for many purposes including human.
It is difficult to propose conventional systems of wastewater treatment to
apply for the treatment of MWW in Pakistan, because there is no separate drainage
system for domestic and industrial wastewater. All types of wastewater moving into
single drain. Therefore there is tremendous need to select a most economical
treatment system which should be able to treat MWW containing industrial
wastewater as well. There are many options to use natural biological, CEPT and AOP
need to be tested to select one most appropriate and economical system. Some times
simple CEPT, direct treatment with H2O2, H2O2/UV and anaerobic treatment process
may require individually and with combination to overcome the high variation in
3
COD receiving in municipal wastewater stream. Separate installation of treatment

facility at each source may not be feasible to overcome this problem at present status.
Over a billion people around the world lack access to safe drinking water, with
around 80% of all diseases are due to poor drinking water qualities in developing
countries this lead to 1.7 million deaths annually (UNDP, 1996). In Pakistan, water
availability has already fallen from 5000 m3 per capita to 1,100 m3 in 2005 (IUCN,
2005). According to government statistics, 88% of the districts urban population and
62% of rural residents have access to water supply. But only 33% people have water
supply at their homes and 67% rely on outdoor sources. Water quality analysis report
200506, 55% samples were found with coliform contamination (Akram, 2005;
IUCN, 2009).
1.2 Low Cost Treatment Option for Pakistan

1.2.1 Sewage treatment
Components which need to remove can be chemical, biological and physical
contaminants. The main purpose is to produce effluent or sludge acceptable to
discharge into open drains or reuse. These pollutants accidently or intentionally
contaminate the water (Nidal, 2008; Tajrishy, 2005).
1.2.2 Process overview

Municipal wastewater can be treated adjacent to source points such as septic
tanks at home, biofilter and aerobic treatment at industrial or large scale community
wastewater treatment. Wastewater is collected from different sources via sewage lines
and pumps to transport and transferred to treatment plant. Treatment criteria and
standard are subject to provincial and federal government. Some wastewater treatment
processes are required specialized technique in treatment process.
Three steps involved in municipal wastewater treatment which are primary,
secondary and tertiary. Primary treatment is a process where wastewater collected in a
tank and allows for natural sedimentation, where 50 to 70 % pollutants are removed.
Most of these are heavy sediments while other lighter components like fat which float
on surface. Settled sludge and lighter particles are separated for secondary treatment.
In this step dissolved and suspended solids are removed. This treatment process
performed by mixed biological species in a controlled environment. In this step after
4
degradation of organic pollutants by microbes, later on these microbes are needed to

be removed prior to discharge. Tertiary treatment is a next step which is advance
treatment option. Some time this treated water is disinfected with chemical or UV
light to reduce microbial load before discharging to wet land or rivers and streams,
where it can be safely used for irrigation purposes in agriculture fields, parks and
green lands (Roland, 1997).
1.3 Pre-treatment
Pretreatment is a process where solids are separated before clogging the pumps
and clarifiers in secondary treatment.
1.3.1 Screening
Sewage wastewater is anxious to eliminate all materials carried in the
wastewater channels. These objects are to remove wood pieces, rags, glass, fruit,
vegetable waste and tampons etc. This can be done by using bar screen, raked bar
screen which commonly used in modern wastewater treatment plant. In small and
common wastewater treatment plants manually cleaning screens are used. Its raking
action can be performed according to deposition of objects on the bar screen and flow
rate. Collected or separated solids are disposed in the land filled areas or incinerated
(Hammer, 2004; Roland, 1997).
1.3.2 Grit removal

Degritter is a process in which incoming wastewater velocity is reduced to allow
sand, stones to settle. Majority of the various suspended and dissolved solids remain
in the wastewater. A sand washer with conveyor is installed in the system to separate
sand and transport to a container for disposal. Some time this grit is incinerated, or
sends to a land filling sites.
1.3.3 Primary treatment

In primary treatment sewage water is collected in to tanks known as
sedimentation tank. This tank is large enough where wastewater is allowed for few
hours to give the chance for complete natural sedimentation. Oil and other floating
objects are removed by scrapper. In this process after sedimentation more
homogenous liquid is separated where it is biologically treated and sludge separately
digested to make fit for agriculture used. This settling tank equipped with scrapers
5
which moves very slowly 5mm/min speed to collect the sludges and to avoid remix in
above liquid (Hammer, 2004; Roland, 1997).
1.4 Secondary Treatment

Design of secondary treatment is to degrade the organic mass present in the
wastewater, mostly dissolved and homogenous liquid. Mostly wastewater treatment
plants treat this water with aerobic processes. The effective usages of this process are
oxygen and substrate which is required by the microorganisms and protozoa as a feed.
When substrate is exhausted this microbe form flocks and settled down. Secondary
treatment has classification i) fixed film ii) suspended growth. Fixed film system
where microbial growth supported on a object such rotating biological contactor and
other is trickling filter where microbes has attached growth on stones or any material
specifically designed to use in their filter. In activated sludge system biomass should
be well mixed and require less space then trickling filter. But advantage in trickling
filter deal with more reduction of organic material and dissolved solids.
Roughing filter are used to treat diversified organic loads, such as wastewater
from industries especially food industry where it has high organic load in wastewater.
Wastewater fed into this at very high speed which is designed to face high organic
load as well. Air is required to supply oxygen to create aerobic conditions and to
reduce the odour. During final step biological flock are settle down and this water has
lower level of organic material and suspended matter.
1.5 Up-flow Anaerobic Treatment Reactor

These are reactors where anaerobic microbial species are used to contact with
substrate moving upward direction in a slow moving velocity without disturbing the
sludge. It is successfully in use at different organic rich industrial wastewater
treatment plants.
It can be briefly described as process in which substrate in water passes through
sludge bed containing biomass. This sludge is present in the form of granular or
flocculent form. Influent enters into the system from bottom of the reactor and left
from upper side of the reactor. Uplift velocity of the influent is very critical to allow
sufficient time to uptake substrate through the biomass without uplifting the sludge
granules. The most attractive treatment system due to its no sludge excess sludge
6
production because substrate converted into biogass (Aiyuk, 2004; Ghangrekar, 2005;
Jules, 2011).
1.6 Other Municipal Wastewater Treatment Options

1.6.1 Activated sludge
Activated sludge covers many different mechanisms where oxygen is used to
enhance the growth and then lack of substrate flock formation occurs. In this process
ammonia converted into nitrite, nitrate and nitrogen gas which goes into atmospheric
air (Verstraete, 2004; Tchobanoglous, 2003).
1.6.2 Surface-aerated basins

In biological treatment of wastewater, oxygen is used to perform microbes
actively. In the surface aerated basin 80 to 90% of BOD can be removed. The basin
normally has depth of 1.5 to 5 meters where motor pumps are used for aeration
floating hanged on surface of water in the middle of the tank (Beychok, 1987).
In such type of basin aeration provide two functions i) transferring air (oxygen)
for microbial oxidation reaction. Secondly they provide the force to move air and
distributed homogenously and also forcing solid to move and contact with microbes
and oxygen. Typically through this system the air distributed at the rate of 1.8 to 2.7
Kg O2 KW-1h-1. In this system air is not properly mixed as in activated sludge system,
thats reason it is not as efficient as activated sludge system. Oxidation reaction in this
treatment system is very effective when temperature range is 4oC 32oC and at higher
temperature rate of reaction is high and slow down at lower temperature
(Middlebrooks, 1982; Beychok, 1987).
1.6.3 Membrane bioreactors

Membrane bioreactor is actively of two treatment processes, one is activated
sludge system and other is membrane liquid solid separation process.
The great benefit of this system is to control the poor settling of sludge in
conventional activated system (CAS). This allow reactor operate at high rate of
mixed liquor suspended solids (MLSS) than CAS. The CAS has limitation in sludge
settling due to aeration limitations. The process operate in the range of 8000-12000
mg L-1 MLSS whereas CAS at 2000-3000 mg L-1.
In the membrane bioreactor process, the raised biomass concentration allows

very effective removal of soluble and particulate organic biodegradable materials with
higher loading rates. Thus, increased Sludge Retention Times (SRTs) exceeding more
than fifteen days is required to ensure complete nitrification even if the temperature is
cold.
The operating and building of a MBR is usually more than conventional
wastewater treatment, however, as the technology is getting popular and has achieved
wider acceptance throughout the industrial wastewater and MWW treatment, the lifecycle costs have been gradually decreasing. The small impression of MBR, and the
good quality effluent produced, makes useful for water reuse applications (Verstraete,
2004).
1.6.4 Rotating biological contactors

Rotating biological contactors (RBCs) are secondary treatment process, which
are vigorous and ability to surge with organic load. RBC first time introduced in
Germany, 1960, and since then refined and proved to be a reliable operating until. In
rotating disc support the microbes to expose with atmospheric air and nutrients from
wastewater which breakdown organics presents in wastewater. As micro-organisams
grow and build up biofilm on the disk and later this sloughed off due to shear forces
generated during circular motion in wastewater. In the next step RBC effluent is
then passed through final clarifiers where microbial flocks settle down. In the same
tank sludge is scrapped from bottom and clarified for treatment to use in appropriate
application.
Some kind of similar biological filtration has become trendy in home aquarium
purification as well as filtration. In the system water is cascaded on the wheal of fibermesh before using media filter. This fiber mesh wheel rotates and gets contact with
air, supporting growth of biofilm on the mesh fiber wheel. This can be good system to
remove aquarium waste such as urea and ammonia released by the fish or other
animals in aquarium (Leslie, 1998).
1.6.5 Lagooning
It provides improvement in wastewater quality by providing oxygen through
photosynthesis
of
macrophytes.
These
macrophytes
create
highly
aerobic
environment. Zooplankton such as daphnia and rotifer play important role in filtering
in lagoon. These species greatly remove the fine particulates (Hammer, 2004).
1.6.6 Constructed wetlands

It provides improvement in wastewater quality by providing oxygen through
photosynthesis
of
macrophytes.
These
macrophytes
create
highly
aerobic
environment. Zooplankton such as daphnia and rotifer play important role in filtering
in lagoon. These species greatly remove the fine particulates (Hammer, 2004).
Constructed wetland is fed in at the inlet and moved in laminar regime through
porous medium until it reaches the outlet zone where it is collected before the outlet.
During this flow regime wastewater is in contact with aerobic, anoxic and anaerobic
zones. Rhizomes and plant roots releases the oxygen and develop aerobic conditions.
Constructed wetlands have long been used for domestic and MWW (Vymazal, 2009;
Cooper et al., 1996; Brix, 2003).
1.6.7 Nutrient removal

Mostly wastewater contains nutrients like nitrogen and phosphorus at high level.
These nutrients causes eutrophication in such aquatic environment, in extreme
condition, eutrophicated reservoir converted into bogs. These nutrients enhance the
rapid growth of algae and algal bloom.
The algae numbers are unsustainable and eventually most of them die. The
overgrowth of algae in aquatic environments causes decrease in oxygen level of the
water due to which most or all of the animals die, which creates more organic matter
for decomposition by bacteria. In addition to deoxygenating, some algal species
produce toxins that contaminate drinking water supplies. Different treatment
processes are required to remove nitrogen and phosphorus. Removal of nutrients has
been studied by different reactors. Sequential batch reactor for biological nutrient
removal from MWW was found very effective in reducing BOD, TSS and ammonium
nitrogen 98%, 90% and 89% at 12 hours cycle time. It consists of a sequencing
operation including the steps of fill, react, settle, decant and idle (Kargi, 2003).
1.6.7.1 Nitrogen removal
The removal of nitrogen is effected through the biological oxidation of nitrogen
from ammonia (nitrification) to nitrate, followed by denitrification, the reduction of
9
nitrate to nitrogen gas. Nitrogen gas is released to the atmosphere and thus removed
from the water.
Nitrification itself is a two-step aerobic process, each step facilitated by a
different type of bacteria. The oxidation of ammonia (NH3) to nitrite (NO2) is most
often facilitated by Nitrosomonas sp. Nitrite oxidation to nitrate (NO3), though
traditionally believed to be facilitated by Nitrobacter sp., is now known to be
facilitated in the environment almost exclusively by Nitrospira sp (Verstraete, 2004).
Denitrification requires anoxic conditions to encourage the appropriate
biological communities to form. It is facilitated by a wide diversity of bacteria. Sand
filters, lagooning and reed beds can all be used to reduce nitrogen, but the activated
sludge process, membrane-aerated biofilm reactor (MABR) (if designed in a good
way) can do the job the most easily. An electron donor is needed since denitrification
is the reduction of nitrate to dinitrogen gas. This can be, depending on the wastewater,
organic matter (from faeces), sulfide, or an added donor like methanol. Sometimes the
change of toxic ammonia to nitrate alone is referred to as tertiary treatment (Terada et
al., 2003).
1.6.7.2 Phosphorus removal
To avoid algal growth phosphorus removal is important because it serves as
limiting nutrient. It is important to remove phosphorus particularly when their
concentration guides to fouling of reverse osmosis equipment (Landner, 1976).
Phosphorus removal is also biologically possible. Specific bacteria like
polyphosphate accumulating organisms (PAOs) accumulate phosphorus upto 20%
in cell mass. When these are enriched with phosphorus then separated from
wastewater which has high value of fertilizer. Phosphorus removal can also be
possible by using coagulants/flocculants such as ferric chloride, alum and lime. This
treatment option may lead to sludge production in excessive amount. It is more
reliable than biological treatment. Chemical removal is easier and economical to
remove. On single tank can be enough for whole treatment. When mixing takes place
and important thing is proper mixing to form flock with coagulant/flocculant. This
process has also advantage in reducing the time of sedimentation (Verstraete, 2004).
10
Chemical precipitation of Phosphorus removal can also be achieved by, usually

with salts of iron (e.g. ferric chloride), aluminum (e.g. alum), or lime. This may lead
to excessive sludge productions as hydroxides precipitates and the added chemicals
can be expensive. Chemical phosphorus removal requires significantly (p < 0.05)
smaller equipment footprint, is easier to operate and is often more reliable than
biological phosphorus removal. Phosphorus, in the form of a phosphate rich sludge,
once removed, may be stored in a land fill or reuse in fertilizer (Tchobanoglous, 2003;
Broughton, 2008).
1.7 Tertiary Treatment

The tertiary treatment is final treatment stage; its purpose is to raise the effluent
quality before it is discharged to the receiving environment (sea, river, lake, ground,
etc.). At any treatment plant more than one tertiary treatment process may be used. If
disinfection is practiced, it is always the final process. It is also called "effluent
polishing". It includes micron filtration, ozonation, reverse osmosis and UV treatment
(IBWA, 1995).
1.7.1 Filtration
Much of the residual suspended matter is removed by sand filter and activated
carbon also removes residual toxins.
1.7.2 Disinfection
Disinfection is a process where microbial population is reduced in water to
safely discharge the treated water into environment. Disinfection efficiency depends
also on raw water quality where to judge the type of disinfection need to be used.
Cloudy water protects microbes against UV light treatment or when contact time is
not sufficient. Low doses of disinfectant and flow rate has substantial effect during
disinfection. Disinfection methods are ozonation, chlorination and UV light.
Chloramine disinfectant is used for drinking water disinfection but not used in
wastewater treatment due to its persistence property in environment. In North
America it is still used for disinfection. It has one disadvantage, reaction between
chlorine and residual organic matter produces carcinogenic compounds chlorinated
organic compounds and these residual are also toxic to the aquatic species. So there is
need to treat treated water with chemical to dechlorinate (Verstraete, 2004).
11
The UV light replaces the chlorine, iodine and other disinfectant. In this
treatment no chemicals are used no byproducts are observed to be hazardous.
Radiation from UV damages the genetic material of virus, bacteria and pathogens.
Only disadvantage of UV lamp is required regular maintenance and proper cleaning
of UV lamp sleeve to allow radiation pas through. It is very important that
microorganisms must not get any protection from UV light (mostly solids left in
pretreatment may provide protection to microbes against UV. The UV light has
become more and more popular in developing countries as well as in developed
countries due to its efficient disinfection and awareness enhanced about chlorination
residual organics in the wastewater and in receiving water body. (IBWA, 1995).
Ozone is produced from oxygen in the presence of voltage potential. Ozone is
highly reactive and unstable. It oxidizes mostly all organics present in water and
inactivating microorganisms. Ozone is much safer than chlorine. Chlorine need to
store in very safe area because it can be very dangerous incase of accidental spillage.
Ozone produces less disinfection products. It is safer than chlorine as it produces at
the site by ozone generator as required (Pillai, 2009).
1.8 Aims of This Study

The aim of this research work was to investigate the best treatment option for
a combined MWW which is mixed with industrial wastewater. Therefore, MWW has
large variations in their types of pollutants such as domestic, restaurants, carwash and
carbohydrates from confectionary waste. It was highly desirable to bring forward a
treatment technique which should efficiently remove the pollutants from MWW
containing industrial wastewater. For the treatment of such types of MWW, the work
was divided in three parts. In first part chemical treatment was applied by using
oxidizing agents such as H2O2, organic and inorganic coagulants separately in batch
treatments. Chapters included in first parts were 3 to 5 where optimization of
coagulant and oxidizing agent was studied. In chapters 7 and 8 integrated treatment
results were presented where anaerobic treatment UASB was combined with
advanced oxidation process using H2O2 in a series to see treatment effects of MWW
and confectionary wastewater.
The present study was conducted to achieve the
following objectives;
12
1. To select the most effective and locally available coagulant to enhance the
sedimentation of MWW. The dose of selected coagulants [Al2 (SO4)3, FeCl3,
and Moringa oleifera seed extract] were optimized to see the efficient removal
of settle able solids and colloidal particles in the MWW.
2. The study also aimed to explore the effectiveness of used H2O2 (40%) and
alum as integrated treatment to reduce the BOD, COD of MWW and CWW
separately. As MWW in Pakistan also mixed with carwash industry
wastewater. Therefore aim was to explore the possibility of integrated
treatment concept for carwash wastewater to an acceptable level. To discharge
effluent from carwash into drains to contribute less pollution load.
3. To see the best effectiveness of two different application rates (35% and 40%)
of H2O2 during treatment of MWW. The specific objectives in this regard
were to compare the effectiveness of used (40%) and fresh (35%) H2O2 to
treat the MWW.
4. The last part of this research was aimed to evaluate UASB reactor start up
with glucose, synthetic nutrients and its kinetics along with and coupling
effect of UASB and chemical.
13
References
Aiyuk, S. & Verstraete, W. (2003). Sedimentological evolution in an UASB treating,

a new representative synthetic sewage, at low loading rates. Bioresource
Technology. 93, 269-278.
Akram, K., Aslam, T. and Hifza, R. (2005). Water Quality Report, Pakistan Council
for Research in Water Resources. Pakistan Council for Research in Water
Resources.
Balfours, A. (1987). Lahore wastewater treatment project. Balfours consulting
engineers Lahore.
Beychok, M. R. (1971). Performance of surface-aerated basins. Chem. Eng. Prog.
Symposium Series. 67 (107), 322339.
Brix, H., Arias, C. A. and Johansen, N. H. Experiments in a two-stage constructed
Wetland system: nitrification capacity and effects of recycling on nitrogen
removal. In: Vymazal, J. (Ed.), Wetlands-Nutrients, Metals and Mass Cycling.
Backhuys Publishers, Leiden, The Netherlands., pp. 237-258 (2003).
Broughton, A. Pratt, S. & Shilton, A. (2008). Enhanced biological phosphorus
removal for high-strength wastewater with a low bCOD: ratio, Biores.
Technol. 99, 1236-1241.
Chandio, B. A. & Abdullah, M., 1998, Proceeding of National Workshop on Quality
of Drinking Water, Pakistan Council of Research in Water Resources,
Islamabad.
Cooper, P. F., Job, G. D., Green, M. B. & Shutes, R.B.E. (1996). In: Reed beds and
constructed wetlands for wastewater treatment. pp. 50-100. WRc Publications,
Medmenham, Marlow, UK.
Ghangrekar, M. M. (2005). Design of an UASB Reactor, Guest article, Department of
Civil Engineering, Indian institute of technology, Kharagpur India.
Hammer, M. J. (2004). In: Water and wastewater technology, pp. 477-479. Prentice
hall of India, 4th edition.
IBWA. (1995). In: Plant technical manual, International bottled water association,
pp. 40-45. Revised edition.
IUCN. (2009). Drinking Water, Environmental Fiscal Reform in Abbottabad,
Government of NWFP, Pakistan.
IUCN. (2005). Drinking Water Sector Paper for ACS. IUCN-ACS Support Unit.
14
Principles and Application of Membrane Bioreactors in Water and Wastewater

Treatment.
Jules, B. V., Anaerobic Industrial Wastewater Treatment: Perspectives for Closing
Water and Resource Cycles. Wageningen University, The Netherlands.
Online: accessed date 14-02-2011.
http://www.leaf-water.org/NR/rdonlyres/4A15A40D-2A88-4E10-A389D500766033F5/89155/LeAFLetterNo6.pdf
Kargi, F. & Uygur, A. (2003). Nutrient loading rate effects on nutrient removal in a
five-step sequencing batch reactor. Process Biochem. 39, 507-512.
Khan, F. J. & Javed, Y. (2007). Delivering Access to Safe Drinking Water and
Adequate Sanitation in Pakistan. Working paper No. 21. Pakistan Institute of
Development Economics.
Landner, L. (1976). Eutrophication of Lakes, Causes Effects and Means for Control,
with Emphasis on Lake Rehabilitation, Swedish Water and Air Pollution
Research Laboratory, Stockholm, Sweden.
Lesliegrady, C. P., Glenn, T., Saigger & Henry, C. L., (1998). In: Biological
Wastewater Treatment, pp.100-159. (2nd edition) CRC Press.
Middlebrooks, E. J. (1982). Wastewater Stabilization Lagoon Design, Performance
and Upgrading. McMillan Publishing Company New York.
Online
available
article:
accessed
date
01/08/2009
http://search.barnesandnoble.com/Wastewater-Stabilization-Lagoon.
Nidal, M. (2008). High strength sewage treatment in UASB reactor and an integrated
UASB- digester system. Bioresource Technol. 99 (16), 7531-7538.
PDP, Pakistan Demographics Profile. (2011). Online: accessed date 20/03/2011.
http://www.indexmundi.com/pakistan/demographics_profile.html
Pillai, K. C., Kwon, T. O. & Moon S. I. (2009). Degradation of wastewater from
terephthalic acid manufacturing process by ozonation catalyzed with Fe2+,
H2O2 and UV light: Direct versus indirect ozonation reactions, Applied
Catalysis B: Environmental. 91, 319-328.
Roland, L. (1997). In: Theory and practice of water and wastewater treatment. pp
660-665. John Wiley & Sons, Inc.
Saeed, M. M. & Bahzad, A. (2006). Simulation of contaminant transport to mitigate
environmental effect of wastewater in River Ravi, Pakistan J. Water Resour.
10(2), 4-52.
Tajrishy, M. & Abrishamchi, A. (2005), Integrated approach to water and wastewater
management for Tehran, Iran. Water Conservation, Reuse, and Recycling:
Proceedings of the Iranian-American Workshop, pp 217-227. National
Academies Press.
15
Tchobanoglous, G., Burton, F. L., Stensel, H. D. Metcalf & Eddy. (2003). In:
Wastewater engineering: treatment and reuse. pp. 350-400. International
edition. McGrawHill.
Terada, A., Hibiya, K., Nagai, J., Tsuneda, S. & Kirata, A. (2003). Nitrogen removal
characteristics and Biofilm analysis of a membrane aerated biofilm reactor
applicable to high strength nitrogenous wastewater treatment, J. Biosci.
Bioeng. 95(2), 170-178.
UNDP, United Nation Development Programme. (1996). Human Development
Report. New York, pp 1-10, Oxford University Press.
Verstraete, W. In: Biological Treatment of drinking water. Environmental
biotechnology. Department of microbial ecology, Ghent University Gent,
Belgium. pp. 1-100 (2004).
Vymazal, J. (2009). The use constructed wetlands with horizontal sub-surface flow
for various types of wastewater. Ecol. Eng. 35, 1-17.
Zahid, H. and Baig, M. A. (1997). Pollution of Lahore canal water in the city
premises processing of NSMTOC, 97. Article on Environmental Pollution, pp
24-26.
16
2 Chapter 2: Literature Review

Comparison of Different Treatment Options in Municipal
Wastewater Treatment
17
2.1 Characteristics of Municipal Wastewater/Domestic Wastewater

Wastewater is produced by community after domestic use. Components of
wastewater vary place to place and type of industry discharges. A different industry
produces different type of wastewater. Several food industries produces mostly organic
rich while textile and tanneries industry produces toxic wastewater. Domestic wastewater
mostly contains waste from home garden, kitchen and bathroom. Other than this any
wastewater can be generated intentionally or unintentionally from houses. Sanitary
wastewater contains commercial, domestic and institutional or similar kind of amenities.
Normally this type of water is generated is approximately 400 liters per person (Almeida,
1999; Campos, 1996) and common important parameters are indicated in Table 2-1.
Table 2-1 Average composition of domestic sewage (Verstraete, 2004). *DW: dry weight
Parameters
COD (mg L-1)
BOD5 (mg L-1)
bCOD (mg L-1)
Total N (mg L-1)
Total P (mg L-1)
Total solids (mg *DW L-1 )
Suspended solids (mg *DW L-1)
(mg COD L-1)
Detergents (mg L-1)
pH
Raw
Wastewater
After primary
treatment
500
300
460
40
15
1000
250
332
20
6.8-8
350
200
300
35
12
800
100
133
20
7.2
After
Secondary
treatment
50
10
15
30
10
700
10
13
2
7
Gray water arises from domestic washing operation such as hand basins, kitchen
sinks and washing machines but specifically exclude foul or black water sources (toilet,
bidets and urinals) Physically, wastewater is usually characterized by a grey colour,
musty odour (Verstraete, 2004; Verstraete, 1999) and most important analysis parameters
included are ammonia, nitrate, phosphate, total and suspended solids and volatile
suspended solids (Almeida, 1999). Solids in water are 30% in suspended form and 70%
dissolved form. In wastewater treatment dissolved solids can be removed by biological
treatment and during advance treatment, membrane filtration can be used. Wastewater
18
composes of organic inorganic and various gasses which are present in dissolved form.
These organics compose of mostly grease, fat, protein, oil and pesticides or some other
components depending upon pollutant source. Domestic wastewater consists of 50% of
organic and inorganic part. Mostly wastewater contains more dissolved solid than other
solids. These dissolved solids are more difficult to remove. These dissolved solids make
part of 80-90% of inorganic components and 50-60% is organic dissolved form. Mostly
common gasses found are known as hydrogen sulfide, nitrogen, carbon dioxide and
oxygen. Hydrogen sulfide, methane and ammonia are formed due to decomposition of
organics present in wastewater (Metcalf and Eddy, 2004, Verstraete, 1999).
Wastewater contain many different type of microorganisms but the most which
are concerned in classification regarding wastewater treatment and some plants like
mosses, ferns and seed plants. Most important microbial community which likes to be
considered in treatment is protozoa, algae and bacteria. Most of pathogen enters in
wastewater from human who are suffering from different diseases or carrier of diseases.
In denitrification of these pathogens are difficult and time consuming. Coliform which is
easier to test are good indicator of presence of these pathogens but does not accurately
indicate the presence or absence of pathogen. These could be finding also in effluent
concentration of raw wastewater. Fecal coliform raw wastewater found in hundred
thousands to tens of millions in 100 ml of sample.
2.1.1 Storm water and combined wastewater

Rain water or storm water find their way through natural flow to a receiving water
body. In urban areas rain water is collected through sever times. Some areas are designed
separately to collect only rain water while mostly sewer lines are used to collect both
types, rain water and sewer water. The composition of storm water is consisting of rain
water composition and the area where it has been in contacted. Most of this type of runoff
consists of clayey solids and biological oxygen demand is quite low. Numerous bacterial
loads due to animal waste washout during natural flow of rain water. It is better to have
separate drain lines for storm water otherwise heavy increase in solids are contributing in
additional load in wastewater treatment. As storm water is high in its flow which can
washout the all sludge in sedimentation tank if it is allowed to flow through drains of
19
wastewater treatment plant. Wastewater in dry weather conditions consists of sanitary

wastewater. In rainy days domestic wastewater composition is changed as it diluted with
rain water and this is amplified with contaminants.
2.2 Newly Identified Toxicants in Treated Domestic Wastewater

Toxics found in wastewater pass through wastewater treatment facilities that have
not been designed to remove them and can interfere with their operation. In a biological
treatment process toxic materials can upset a treatment process or even kill the biological
community and make the process ineffective.
MWW treatment plants design especially for the removal of organic compounds by
natural sedimentation, coagulation process and by biological degradation process. There
are many other toxic compounds which are not affecting the wastewater treatment
process but it has effect on endocrine disrupting (Rudder, 2004; Korner, 2000). These
compounds are endogenous hormones estrone (E1), 17- estradiol (E2) and 16 , 17 estriol (E3), the synthetic harmone 17-ethynylestradiol (EE2) and octylphenol
(Desbrow, 1998). The removal of pharmaceuticals and personal care products (PPCPs),
however, require more study to identify its presence in MWW. Use of pharmaceutical
products has increased in our daily life, however if these compounds are available in
water exceeding 1g L-1 could have clear effect on hormone-disrupting. E1, E2 and
endogenous estrogens excreted by women at concentration of 10 to 100 g L-1 and EE2
which is present in synthetic contraceptive pills (Snyder, 1999) has long persistence in
environment with dissipation time 20-40 days in river system (Jurgens, 2002). Estrogenic
study was conducted both in vitro and in vivo studies showed an extremely potent
estrogen (Lange, 2001). EE2 released from the body in the form of conjugated as
glucoronides and sulfates. It becomes active again during passage of wastewater
treatment process by microbial conjugation (Panter, 1999). Therefore EE2 should be
considered as endocrine disrupter compound of great concern. New strategy was explored
by using manganese oxide (MnO2) as an oxidizing agent (Wang, 1999). Endocrine
disruptor compounds are difficult to remove during secondary treatment process therefore
a cost efficient technique was developed to prevent spread of 17 ethynylestradiol by
using granulated activated carbon (GAC) and MnO2 granules. The removal percentage of
20
EE2 through filter of sand, GAC and MnO2 was 17.3%, 99% and 81% (Rudder, 2004).
This topic is getting more interest due to possible negative role of this compound
including hormonal imbalance (feminization) and altered reproductive success such as in
fish and avians (Janz, 1996; Jobling, 1998; Desbrow, 1998). It is also observed in beast,
testicular and prostate gland cancer. Moreover neurological dysfunction cases were
identified in human. These events took place at low environment concentration (Purdom,
1994; Russo, 2002). The EE2 can be tested after oxidation or anaerobic treatment and
with combination of both.
2.3 Treatment Options

2.3.1 Primary sedimentation
The primary objective of sedimentation is to remove readily settle able solids and
floating material which are suspended. Primary sedimentation is a first step in further
wastewater treatment process. Efficiently designed primary sedimentation tanks should
remove 50 to 70 percent COD. Almost all wastewater treatment plants use natural
primary sedimentation in order to remove self settle able sediments in circular or
rectangular design (Droste, 2004; Masters, 2004). When wastewater enters into primary
sedimentation tank, it slows down horizontal flowing velocity and suspended solids
gradually sink to the bottom. It is designed to provide 1.5 to 2.5 hours of detention
(Metcalff, 2004). Among different treatment steps, natural sedimentation is most
commonly used particularly for small communities (Bonnet, 1996). If it is properly
designed 40-50% of specific pollution in municipal wastewater could be controlled.
Settled sludge is removed by slow moving scrapper 5mm/s from bottom (Verstraete,
2004; Metcalff, 2004). Improper and inadequate design causes poor settling, overload to
biofilters and lead to prolong treatment (Fan, 2007). Most of the treatment plants do not
incorporate the latest technology to deal with sedimentation processes. A very good
understanding of hydraulics is required to design sedimentation to replace old circular
and rectangular sedimentation tanks. Recent research on sedimentation process has
completed to predict the flow pattern and settling of solids in different shapes of
sedimentation tanks. To increase the efficiency of particle removal a longitudinal
sedimentation basin was designed which proved vital in sedimentation, working
21
successfully in Europe with less maintenance. In term of settling this tank was more
efficient in dealing with larger particles than smaller particles. In this tank influent creates
recirculation eddy near the pump with generation of turbulence at the inlet and outlet weir
of the sedimentation basin which inhibit the settling. This study was proved to be an
improvement in sedimentation of larger particles (Al-Sammarraee, 2009). The efficiency
of the sedimentation tank to reduce the BOD and TSS depends on 1) eddy current of
incoming fluid 2) wind induced in open tank 3) convection heat current 4) density
gradient developed due to cold or warm water which results hindering in movement of
water from bottom to the surface (Metcalf and Eddy, 2004; Al-Sammarraee, 2009).
Generally temperature of the water under treatment is one factor which needs to be
considered during sedimentation treatment. Highest wastewater flow towards wastewater
treatment during summer and when water is cold flow reaches at its lowest. When the
temperature decreases rate of settling decreases and therefore at low temperature
detention time should be increased to allow sufficient time for settling. Sedimentation can
be speedup by the addition of coagulants/flocculants (Well, 1998). In another study,
temperature had a significant effect on cohesive settling in sedimentation basin and
settling velocity increases with temperature (stocks law), (Lau, 1994). Differences in
temperature significantly effect on mixing. It may be due to density gradient develops
stratification after change in temperature and causes poor mixing (Mehmood, 2005).
A computational fluid dynamics model was studied by Goula, to assess the effect of
influent temperature variation on solids settling in sedimentation tank. This model was
used against real sedimentation basin and then assesses the significance of influent
temperature variations. Results shows that with increase in temperature cause buoyant
plume rising which changes the direction of circular current clockwise to anticlockwise
countercurrent thus the particles remain in suspension. This led to decrease percent
removal of particle size of 250 m from 99.5% to 76.0% during sedimentation (Goula,
2007).
22
2.3.2 Physico-chemical treatment

Domestic wastewater treatment in developing countries needs especial attention in
relation to low-cost, low energy, low maintenance and high performance systems that
contribute to environmental sustainability by producing safe and able to be used in
agriculture for crop production. Many other treatment techniques like activated sludge
systems, bio-membrane filtration are expensive to adopt in developing countries. Natural
treatment system is very good and environmental friendly but the problem is space,
constructed wetland need more space which is too expensive in the cities. Therefore a
treatment technique is desirable which should be economical and requires less space to
work efficiently. A combination of chemically enhanced primary treatment and up flow
anaerobic sludge blanket should be considered for domestic wastewater treatment as an
alternative to activated sludge system (Gautam, 2007).
Chemical treatment may be used as a pre treatment or post treatment with anaerobic
treatment in order to enhance the sedimentation and biodegradability of the domestic
wastewater. Coagulation/flocculation is commonly used process in which charge on
particles is neutralized and flocculation to describe the uniting particles into large units.
Colloidal particles that cause color and turbidity in which solid-liquid, liquid-liquid
interface play a vital role in stabilizing the colloidal impurities found in wastewater.
Colloids can also be formed from organic compounds, clay particles by soil erosion and
soap solution etc which cause turbidity in wastewater Table 2-2. These are difficult to
remove from water because it is so small to pass through filter pore and not settle by
gravitational force. Colloidal particles range up to the maximum size of 1m.
Table 2-2 Size spectrum for waterborne particle
Water borne particles

Molecules
Colloids
Suspended particles
Bacteria
Algae
Virus
23
Size m
10 to 10-6
10-5 to 10-85
10-6 to 10-25
10-65 to 10-55
10-6 to 10 -45
10-9 to 10 -72
-10
Colloidal particles in wastewater can be destabilized with coagulants/flocculent

agents like alum, FeCl3 and lime by 1) reducing the repulsion forces 2) particle
destabilization which can be achieved by double layer compression, adsorption and
charge neutralization, enmeshment in a precipitate and adsorption and interparticle bridge
(Benefield, 1982). Salts of Al (III) and Fe (III) are commonly used as coagulants in water
and wastewater treatment.
2.4
Colloidal Chemistry of Wastewater
Life in cell takes place by the colloidal system due to small size of particle 0.1 to 0.001 of
micron diameter. In colloidal system particles are dispersed in a continuous medium and
it is called dispersed phase and the medium in which they present is called dispersing
phase. Colloidal system is most difficult to remove from wastewater impart turbidity to
the water; therefore its removal is important for consumer acceptance to other use or
drink. Colloidal particles carry a charge negative or positive and alike charge repel each
other thus prevent coagulation. These identical charges are responsible for colloidal
stability and cause turbidity in water which is acquired by isomorphic replacements
within the crystal lattice. Silica atom is replaced by an Al atom, resulting net negative
charge on the particle. Colloidal particles in aqueous media adsorb anion and acquire a
negative charge. Ionization of surface sites may possible to develop charge on it. Protein
acquires charge after ionization of carboxyl or amino group and ionization depends on
pH. Due to presence of negative charge on all particles they develop network scattered
throughout the systems which cause turbidity and difficult to remove.
2.5 Coagulation in Water Treatment

Four mechanisms involved in coagulation process ionic layer compression,
adsorption and charge neutralization, entrapment in a flocculent mass and last is
adsorption & inter particle bridging. Identical charges on colloidal particles repel each
other to makes scattered network in water. How can repulsive forces are reduced to bring
opposite charge particle close in order to destabilize the colloidal particle network. Most
common coagulant used in wastewater treatment is alum. There are four mechanisms
involved in i) ionic layer compression ii) Adsorption and charge neutralization iii)
24
Entrapment in a flocculent mass and iv) adsorption and inter-particle bridging. In ionic
layer compression diffuse layer of colloidal particle is compressed resulting more
opposite charge particle moving to colloidal particle making diffuse layer length. This
makes wander wall force increased and particle gets attracted. Second mechanism is
adsorption and charge neutralization. When alum in water it forms aqua metallic ion
which has high affinity with colloidal particles which results no diffuse layer left on
colloidal particle. In this way particles come together and form agglomerates. Excess
dose of alum in wastewater treatment results destabilization of particles and increase the
turbidity. Optimization of dose is very important before applying the coagulant to
wastewater treatment tank. Third step is entrapment in flocculent mass sweep coagulation
where alum is being dissociated in Al and sulphate at high dose. These coagulant form
coagulants and start moving entrapping other colloidal particles and settling down. Last is
adsorption and inter particle bridging; polymers molecules attached to colloidal particles
at one or possibly more than one sites by columbic attraction. If both have similar charge
then tail extends in to bulk of solution and attached to vacant opposite charge site. This
bridging formation result in flock formation and settle down. So coagulation is a process
involving particles destabilization followed by mixing to promote collisions between
colloidal and polymer or charge species. In this research work alum treatment was
studied and compared with other coagulants. The best coagulant alum was found
effective (p < 0.05) in COD removal of MWW. Other coagulant FeCl3 and Moringa
oleifera was not found suitable for this type of MWW containing industrial, domestic and
commercial wastewater (Kologo, 2001; Metcalf, 2004).
2.6 Chemically Primary Treatment of Wastewater

Chemically Enhanced Primary Treatment is the process of sedimentation which is
enhanced by the addition of coagulants to shorten the sedimentation process. The
chemicals clump the suspended particles and gather via the processes of coagulation and
flocculation. The particles aggregate and settle faster due to increase in density and
thereby increase the treatment efficiency. The coagulants which are utilized in CEPT are
FeCl3, FeSO4 and aluminum sulfate and there are no metals residual left in the supernatant
(Metcalf et al., 2004).
25
The CEPT is an interesting process, over the activated sludge treatment because
that we do not need large investment to build an entire activated sludge treatment plant.
CEPT can provide alternate sample for developing region and remote area instead of
using expensive biological treatment. It is possible to meet effluent criteria using this
method with limited technology and operational costs. CEPT does not reach the effluent
quality as activated sludge system does, but it has several advantages such as low
operating and capital cost. In activated sludge system separate treatment is required for
the nitrogen removal (nitrification and denitrification) and also requires separate
phosphorus removal steps including aerobic and anaerobic treatment (Herlman et al.,
1999). Whereas in CEPT process, phosphorus can be reduced by the addition of FeSO4
either combining with other coagulant or can be used separately in the same
sedimentation tank (Metcalf et al., 2004).
2.6.1 Financial benefits of CEPT

The CEPT process permits to enhance the sedimentation in the basin at high
overflow rate along with maintain high removal of suspended solids. In such treatment
process required small treatment facility which certainly reduces the operational/capital
cost. CEPT operational cost is more than primary treatment and half of the secondary
treatment. In activated sludge system it costs Rs. 7000/- per person per year in developed
countries. This cost is two times less in the collective treatment system of CEPT and
UASB (Verstraete, 2004).
2.6.2 Efficiency of organic and inorganic coagulants

The CEPT can perform to remove TSS, COD and Phosphorus in a same primary
sedimentation tank while biological treatment requires separate steps to remove
phosphorus and nitrogen but may achieve higher removal efficiency. Control of Nitrogen
and phosphorus is important to avoid eutrophication (Yin, 2009). CEPT effectively
removes phosphorus, which is usually the limiting nutrient in fresh water systems Table
2-3. In our country the primary objective of water sanitation system is to reduce pollution
results in less water born diseases. Due to the high levels of morbidity incurred by water
borne illnesses, CEPT is the least expensive method of treatment in which the effluent
can be appropriately treated by organic and inorganic coagulant (Harleman et al., 1999).
26
Table 2-3 Comparison of removal efficiencies
Types of treatment processes
TSS (%)
BOD (%)
TP (%)
TN (%)
Conventional Primary Treatment
55
35
20
15
Conv. Primary and Secondary treat.
91
85
30
31
CEPT
85
57
85
37
Natural coagulant can be used also to treat drinking water. In Zambia people are
encouraged to grow more Moringa trees to produce more natural coagulant from this tree.
This natural coagulant may be used to treat domestic wastewater at primary stage
(Nakhata, 2001).
In another study by Guida, (2007) alum optimization was tested to treat five different
MWW, i) Cuma, ii) Marcianese, iii) Nola, iv) San Giovanni, v) University pilot plant
wastewater. A series of jar test was performed with 150 and 450 mg L-1 alum dose at pH
ranging from 4 to 10 of COD varied from 330 mg L-1 to 560 mg L-1. Results show that in
Nola plant 45% of COD level was decreased but when 150 mg L-1 alum was used 79%
removal achieved. At pH 10 COD removal efficiency was decreased drastically.
Insufficient COD removal was observed in the Cuma and university pilot plant
wastewater even at an alum dose of 450 mg L-1 whereas in Nola and S. Giovanni plants
using 150 mg L-1 alum was sufficient to reduce the COD upto 160 mg L-1 and TSS 80 mg
L-1 within limits (Guida, 2007). It means wastewater characteristics important for
effective use of alum dose.
In another research work (Feo, 2008) it was studied in selection of best coagulant
to treat urban wastewater. Eight different coagulant aluminium sulfate, ecofloc 614,
ecofloc 616, ecofloc CP, ecofloc SA 7, ferric chloride, poly aluminium chloride and
sodium aluminate with dose of 10, 20 up to 50 mg L-1 was used. The cost of coagulant,
COD removal percentage and pH variation was studied. The best coagulant, Ferric
chloride, was identified for maximum 85.4% of COD removal and 7 to 20 % variation in
pH. Most expensive coagulant cost 1.6 to 1.7 euro/kg with COD removal efficiency was
less than 85.4 % of ferric chloride. In this study Aluminium sulfate was not found in good
27
percentage COD removal in urban wastewater treatment with maximum efficiency of

49.9% at dose of 50 mg L-1. Poor COD removal efficiency was observed with Ecofloc
6.2% at 50 mg L-1 while at dose of 20 mg L-1 maximum removal of 28.3% COD
indicated. Other all coagulants were observed as increasing dose with increase in COD
removal but due to cost of coagulant and effluent quality it was not feasible to exceed the
treatment dose (Feo, 2008). In that study simple criteria was used to observe the different
coagulant effects at different doses to see the effects on COD removal efficiency,
coagulant cost, sludge volume at 2 hr and pH percentage variation. In this proposed
system of chemically assisted primary sedimentation can be replaced if coagulant added
as coagulation for 5 minutes, flocculation for 5 minutes and sedimentation 120 minutes
and then discharge for secondary treatment (Feo, 2008; Harleman, 1999).
In developing countries most of the hospital waste is mixed with domestic/MWW which
can be another problem in combine treatment system because presence of antibiotics,
chemicals, dyes, reagents and drug components can harm the active microbial species
(Table 2-4). These species are involved in decomposition of organic waste in wastewater.
In the presence of pharmaceutical compounds only physico-chemical treatment can be
effective. Treatment of hospital waste mixed with domestic waste was treated with FeCl3.
Results show that coagulant dose of 175 mg L-1 was optimized where maximum COD
removal 98% was observed and no further decrease in COD with increasing dose was
observed. Filtration was followed by chemical treatment to remove suspended solids. To
disinfect the water calcium hypochlorite as disinfectant was used and observed further
decrease in COD up to 16 mg L-1 and another disinfection option is UV light treatment
for hospital waste before discharging into surface water and coastal water. This shows
physico-chemical treatment of hospital waste as best option. For the selection of best
coagulant jar test is necessary to match the coagulant with wastewater treatment for the
maximum COD removal at optimized low dose.
28
Table 2-4 Hospital wastewater comparison with urban wastewater
Pollutnats ( mg L-1)
Urban effluent
Hospital effluent
TOC
BOD
COD
Suspended solids
160
220
500
300
211
603
855
225
Source, (Emmanuel et. al, 2001)
2.7 Oily Wastewater Treatment with Coagulation/Flocculation

Some type of wastewater contains heavy oil such type of wastewater discharged
especially from carwash industry and oil producing industries, along with oil it contains
dissolved and suspended solids. To treat or recycling such wastewater is great challenge
for separating oil. Due to presence of oil and solid, COD of this waste water increased
more than 1000 mg L-1. Some coagulants such as poly zinc silicate (PZSS) is a new
type of coagulant which was used in combination with poly acrylamide (PAM) to
remove oil from wastewater. It was observed to remove 95% of oil by using above
combination at dose of COD mg L-1. But poly ferric chloride (PFC) and poly aluminum
chloride (PAC) at the dose of 600 and 450 mg L-1 reduce the oil 51% and 95%
respectively. In the same study 90% of oil removal was achieved at 0.2 mg L-1 by the APAM. Coagulant A-2350 is a PAM (anion) has very high molecular weight. This is
effective against HOW and solid removal. A2350 has high mass and form flock with
negatively charged particles. The sedimentation rate by PZSS is greater than PAC. The
settling rate of 20 min where PZSS was used in combination with A-PAM, remove 99%
of oil. In another combination of PAC with A-PAM achieve the 99% oil removal. It was
observed from results that PZSS was great effective than PAC. Other combination was
also observed very successful with removal efficiency 99% of solids & oil when PFC &
A-PAM were used together (Zeng, 2008).
2.8 Use of CEPT Sludge as Adsorbent

CEPT is effective treatment of sewage especially in mega cities with high
concentration of chemical sludge also contained metal hydroxide. The focus on CEPT
process now might be the cost of chemical and disposal of chemical sludge. The
29
objective of this research work was to obtain a product from the CEPT sludge with high
adsorption capacity. FeCl3 was applied as the effective adsorbent for the removal of
turbidity, COD and total phosphorus. It was applied between the concentration of 0.2 to 3
g L-1. The removal efficiency was turbidity 83%, COD 48.8% and total phosphorus 89%.
It shows FeCl3 is the effective adsorbent in sludge has the role of destabilization and
condensation nuclei that ultimately help in settling the suspended particles and removal
from sludge (Xu, 2005).
2.9 Effect of Polymeric Flocculent Produced from Plastic Waste

A new technique was introduced to purify wastewater with high turbidity by
coagulation and flocculation processes using waste polysterene. Surface water has
suspended particles and turbidity. It can be removed by using waste polystrene containing
additives that were converted into a polymeric flocculent by chemical modification. To
evaluate the effectiveness of flocculants a synthetic wastewater was used in four jar
apparatus. That jar contains the alum, polyelectrolytes and then the solution is allowed to
settle for a small time. The reaction of sulfonation allows the attachment of sulfonic
groups to the polymer chains. In this reaction sulphur tri oxide was formed by sulphuric
acid used. The reaction is more efficient when a desiccant agent is used such as P2O5.
This agent allows sulfuric acid to be more concentrated in sulphur trioxide. If
P2O5 is
absent there will be no change on polymer. The presence of additives have an influence
on sulfonation. The large degree of turbidity was observed for 0.1ppm dose of
polyelectrolyte synthesized from waste polystyrene. No other parameters were indicated
in this study (Bekri-Abbes, 2007).
In CEPT process minimal coagulant dose range (5-10 mg L-1) is used and these
chemicals are very small parts of sludge after sedimentation. As sludge production is high
in CEPT this is indication of maximum removal solids from wastewater and this is a ideal
goal of CEPT. After CEPT next step is less costly due to most part of solids removed in
previous step. The most effective use of CEPT is to work on very broad range of
temperature which can be easily implemented (Herlman et al., 2001).
30
2.10 Combine Chemical and Biological Low Cost Treatment Systems

The MWW contains 40 to 50% of COD in terms of suspended solids (Metcalf,
2004). These solids are not easily hydrolyzed in anaerobic system and continuously
feeding of such solids in wastewater increases the sludge volume. The main advantage of
anaerobic sludge blanket is to produce less sludge with better COD removal efficiency
and if sludge volume increases in short period than the COD removal efficiency
decreases. Excess sludge need to replace affecting the sludge bed (Mergaert, 1992;
Verstraete, 1999; Sayed, 1995). Natural sedimentation process can remove 40 to 50%
suspended solids before feeding to UASB reactor. Suspended solids usually take a day to
settle down to remove resistant part of the solids (Elmitwalli, 1999). To reduce the
settling time coagulant can be used to enhance the sedimentation (NDabigengesere,
1998). This step requires additional care to control the pH of influent for UASB. This
system can be more feasible where MWW blend of domestic, industries and hospital
discharge. This treatment system consists of mixing tank and same can be used for
sedimentation as well.
A study on CEPT-UASB combination by (Kologo, 1999) wastewater treatment
system consists of 20 liters working volume and UASB reactor working volume 1.2
liters. Two combinations were compared i) FeCl3 as coagulant were used in CEPT and
its decant was fed to UASB ii) Moringa oleifera extract were used in CEPT and its
decant fed to UASB Figure 2.1. Results showed that 50% COD, 75% SS and 79%
phosphate phosphorus were removed when FeCl3 were used in CEPT tank and in next
step CEPT effluent were fed to UASB with removal efficiency of COD 54%, SS 51%
and phosphate phosphorus values increased due to mineralization of the phosphorus.
UASB reactor was found successful in removal of soluble COD 55% than CEPT only
24%. Moringa oleifera was not found successful in removing Phosphate phosphorus and
COD.
Figure 2.1 CEPS-UASB (Kologo, 1999)
31
In developing countries MWW assimilate wastewater from different sources other

than the definition of the MWW. CEPT can help to remove suspended solids and UASB
receive fewer loads, which may help to avoid recycling. In present study MWW in
Abbottabad was observed suspended solids SS >100 mg L-1 and direct fed to UASB at
HRT 12 hr was found to be successful removal of COD followed by disinfection with
waste H2O2 (40%).
Same methodology was adopted by Sunny Aiyuk using FeCl3, alum, Allied colloids
(anionic), Allied colloids Zetag (cationic), Synthofloc H-PWG (anionic), Praestol
(cationic), caldic calfloc (anionic), Betz-Benelux (cationic) and other were tested with
series of jar test to treat domestic wastewater. These tests were carried to select the best
combination of coagulant/flocculant for chemically enhanced primary treatment. The best
combination was found i) FeCl3 allied colloid E10 (anionic) ii) Alum Betez-Benelux
1558 E (cationic) decreased COD 138 and 144 mg L-1from initial 522 mg L-1of domestic
wastewater. Using selected combination of coagulants in CEPT was removed TSS 85%,
COD 73%, BOD 66%, TKN 23% and PO4-P 80% and total removal with UASB 88%,
91%, 71%, 99% and 75%. In this study effluent after UASB treatment was further
treated with zeolite to reduce ammonium to produce good quality irrigation water figure
2.2 (Aiyuk, 2004). Zeolite was effective after UASB removing 100% ammonium ions
and before UASB it was effective only 45% removal. Interstitial spaces of zeolite allow
to replace cations by ammonium through ion exchange. It was regenerated after two
when it was installed after the UASB. Higher removal efficiency was due to longer
exposure time with zeolite as UASB effluent release slowly with 0.4 g COD L-1, 10h
HRT.
Figure 2.2 Schematic of the low investment sewage treatment concept with zeolite installation
32
In another study on domestic wastewater SS 165 mg L-1, COD 320 mg L-1, TKN 33
mg L-1 and PO4-P 5 mg L-1 after days 41 to 154 removal efficiency of COD and SS were
70 and 81%. In this case no CEPT was used to remove SS and no sludge accumulation
was observed for 160 days. In this case SS was 165 mg L-1 (Kologo, 2001) where no
CEPT was found necessary but in the study by Sunny, 2004 SS more than 200 mg L-1
where CEPT was found to be necessary to improve COD removal efficiency of UASB
reactor. In Abbottabad MWW, SS was found not more than 150 mg L-1 therefore it was
not necessary to add CEPT before UASB treatment. In our results it was observed 99%
COD removal efficiency.
2.11 Advanced Oxidation Processes in Municipal Wastewater

Treatment
Treatment of wastewater comes through diverse and complicated steps where
transferring of contaminants from one medium to another is not acceptable. Exploring
simple technology to overcome complicated treatment steps is another task but H2O2 can
be an effective oxidizing agent. It is powerful oxidizer known stronger than chlorine,
chlorine dioxide and through catalyst it can convert into hydroxyl radicals (OH). It is
also formed by the sunlight reacting with water which is a natural purification system in
environment. It has no problem in release of gasses and its residue is left in water. It is
also a product of metabolite of many organisms and decomposes into water and oxygen.
Reason to choose is its simple application e.g. pH, temperature, dose and reaction time. It
was first commercially produced in 1800s, its uses in textile, paper, food, electronics and
petrochemical. In 1970 it was tested in MWW and industrial wastewater treatment. Its
application in different types of wastewater treatment is still carried on for odor control,
BOD/COD removal, organic oxidation, metals oxidation controlling biofouling of
membrane filters (USperoxide, 2009; Ksibi, 2006), While cost to chemical oxidation to
treat wastewater is expensive than physical and biological treatment (Ksibi, 2006). Its
reuse option can be explored in different industrial processes where it is used in one
process and further not allowed in same process. For example its uses in tetrapak industry
during disinfecting the packaging material at recommended concentration of 35% at high
33
temperature 100C. The changes take place in its concentration during the process where
concentration increases 40% which is not allowed to use further for disinfection of
packaging material. To use 40% waste H2O2 in wastewater treatment had been studied in
this research work to find its effect on COD reduction.
2.11.1 Municipal wastewater treatment with H2O2

In the study of Kisibi, 2006 chemical oxidation with H2O2 for domestic
wastewater/MWW carried out to cope with the shortage in arid to semi-arid areas of
Tunisia. Aerobic biological treatment and chemical oxidation using H2O2 as oxidants
allowed the effective control of organic load, offensive odor and foaminess in domestic
wastewater. The majority of organic compounds found to be destroyed by H2O2 oxidation
process, giving 85% reduction of COD and BOD5/COD ratio changes from 0.106 to 0.47.
The control during the experiments was achieved by adjusting the H2O2 concentration
relative to COD load. The optimized dose determined in this study was equal to 1.5 ml of
H2O2 per liter of wastewater with COD greater than 300 350 mg L-1. The oxidation of
sulfide into sulfates by H2O2 was demonstrated by the decrease in total sulfides
concentration and the increase of sulfates during the per oxidation reaction. Iron salt did
not have a significant effect on the treatment efficiency. Disinfection of domestic
wastewater was also observed by the use of H2O2 a substantial decrease in bacterial
number. Sulfide reduced after mixing of H2O2 for 200 min from initial value of 8 mg L-1
to 4 mg L-1 but sulfate was increased from 1 to 1.3 g L-1. In both cases when treated with
H2O2/Fe2+ and biological process separately the concentration of sulfide was increased
and sulfate decreased. This indicates that sulfide and sulfate are inversely proportional.
During sulfide oxidation sulfate produced with decrease in pH.
These reactions proceed according to following equations
SO42- + 8e- + 4H2O S2-+8OHS2- + 4H2O2 SO42- + 4H2O
SO32- + H2O2 SO42- + H2O
HSO3- + H2O2 HSO4- + H2O
34
2.11.2 Fenton reagent in AOP

In AOP Fenton reagent successfully used in wastewater and pre-treatment of
wastewater. It is consisted of ferrous salt with H2O2 in acidic conditions which allow the
production of hydroxyl radicals. It depends on temperature, H2O2 concentration and Fe2+
concentration.
Fe2+ + H2O2 Fe3+ + OH- + OH
Fe3+ reacts with H2O2 and hydroperoxyl radical in the so-called Fenton-like reaction,
which leads to regenerating Fe 2+ also react with organic radicals
Fe3+ + H2O2 Fe 2+ + HO2 + H+
Fe3+ + H2O2 Fe 2+ + O2 + H+
Fe3+ + R Fe 2+ + R+
These reactions have short reaction time and can be beneficial for high COD removal.
In another study of pre oxidation of an extremely polluted wastewater with the
help of Fentons reaction was studied by means of an experimental design, influenced by
operational parameters including temperature, ferrous ion and H2O2 concentration. The
optimal values of H2O2 and ferrous ion concentrations were 3 and 0.3 molar, respectively
and resulted in 56.4% of COD reduction. It was found that temperature indicate slight
positive change in COD removal. During first 10 minutes of Fenton reaction, COD
removal was 90% achieved. This might be very interesting to the industrialist because it
reduces COD in very short period of time. It is also considered as good pretreatment of
wastewater, where BOD is difficult (Martinez, 2003).
In another study, H2O2/UV process for the treatment of domestic wastewater was
successfully carried out. Pretreatment was studied before AOP in order to reduce the
turbidity. Alum was used between 20 100 mg L-1 with optimum pH results best COD
and turbidity removal at room temperature. Remaining supernatant was then treated using
H2O2/UV experiments. The results indicated that neither plain sedimentation nor
filtration showed substantial results, but alum at optimum pH of 7 and dose of 60 mg L-1
showed applicable reduction in COD 39% and turbidity 84%. This resulted in better
35
effluent COD as opposed to raw wastewater. In the next step of AOPs the rate of
hydroxyl radical generation by H2O2/UV system was studied on pH dependant and
concentration of the oxidant. Proper value of these parameters was therefore being
chosen carefully. H2O2/UV process resulted over a 95% removal for COD with no sludge
generation and high power UV lamp significantly decreases the reaction time (Yonar,
2006).
2.11.3 Textile effluent treatment with AOP

In the treatment of textile effluent, it was investigated that the treatability of real textile
effluents
using several systems involving advanced oxidation processes such as
H2O2/UV, UV/TiO2, UV/TiO2/H2O2 and H2O2/Fe2+/ UV. The efficiency decreased in

combination as indicated following: UV/TiO2/H2O2 > H2O2/Fe2+/ UV > UV/TiO2 >
H2O2/UV. The efficiency of these treatment techniques was studied and reduction level
of UV absorbance of treated water, organic nitrogen and COD reduction and
minerlization was indicated by ammonium formation as well as nitrate and sulfate ions.
The results show the relationship of TiO2 and H2O2 are better treatment to remove
organic pollutants from textile industry. Treatment efficiency of Fenton proved to be
slow process and give more complex kinetics than using TiO2. In all experiments
decolorization was fast even with only H2O2 treatment (Garcia, 2007). The problem in
treatment of industrial wastewater is not solved successfully in allover the world. Where
even any industrialist get chance to discharge without treatment they will do because
incentives are not there for them.
Although, rules and regulations exist but lack of implementation and absence of
proper monitoring results in problem persistence. Throughout Pakistan industrial
approach towards environment is the same. BOD levels in watercourses receiving these
wastes are as high as 800 mg L-1 and mercury levels over 5 mg L-1. Consequently,
hundreds of tons of fish are killed causing a loss of millions of rupees (CWRAS, 2005).
2.12 Sludge Digestion with H2O2

The combined effect of H2O2 and Fentons reagent were investigated to see the
aerobic sludge digestion. It made possible mineralization of sludge and reduces the
36
duration time of the process. Fentons reagents showed higher oxidation potential
compared with H2O2 and, as a consequence, better efficiency in aerobic digestion.
Fentons reagent also improved sedimentation properties of sludge and decreased soluble
COD. The important advantage of Fentons reagent application is that it may initiate the
oxidation process more effectively than H2O2. Such conclusions are based on VSS, COD
and ORP (oxidation reduction potential) analysis. The apparent disadvantage of Fentons
reagent application, however, is the additional formation of chemical sediment and the
fact that overdose of a reagent may cause decomposition of sludge flocs and, as
consequence, increases turbidity and some problems with sludge dewatering springs up.
When Fentons reagent is applied for a long time or when high doses are applied, it is
affected by colorization of liquid caused by iron salt addition (Barbusinski, 2003).
2.13 Anaerobic Treatment of Municipal Wastewater Treatment

In Biological treatment aerobic process in which, oxygen is required for bacteria to
break down and assimilate the waste. The process through which oxygen is applied called
aeration makes aerobic treatment of wastewater very expensive. Although this treatment
can achieve efficiency more than 95% but to run in developing countries is difficult due
to high maintenance cost (Boschier, 1993; Grin, 1983). Therefore the need to take up
such treatment systems should fulfill many requirements, like non sophisticated
equipment, simple design, low operating cost and high treatment efficiency. Anaerobic
treatment should be considered for domestic and food industry wastewater as an
alternative to conventional aerobic technology especially for developing countries.
There is no use of oxygen in an anaerobic treatment process. During fermentation
process, organic compounds are oxidized and other inorganic carbon dioxide used as
electron (hydrogen) acceptors (Droste, 2004) figure 2.4, Table 2-5. The use of electron
releases chemically bound energy used by anaerobes for their growth. The growth of
anaerobes can be slow; however this does not indicate low processing of substrate.
Anaerobic process involves diverse composite consortium of microorganisms. These
microbial species involved could be divided into Hydrolysis, acetogenesis & acid
formation and methanogenesis.
37
2.13.1 Hydrolysis
Hydrolysis is break down process of complex soluble and insoluble into smaller
molecules that can be transported into the cell and metabolize after penetration through
the cell membrane of the fermentative bacteria. Complex material converted into dissolve
material by the action of exoenzymes released by the hydrolytic fermentative bacteria.
Hydrolysis process of complex compounds is a slow process that depends on several
factors (Lettinga et al., 1996) e.g. temperature of the reactor, residence time of the
substrate in reactor, pH, substrate composition (lignin, carbohydrate, concentration of
NH4+ - N,
protein and fat contents) and size of particles. Soluble product metabolize
inside the cell of fermentative bacteria converted into simpler compounds excreted by
cell. These compounds are volatile fatty acids, carbon dioxide, lactic acid, alcohols,
hydrogen, ammonia and hydrogen sulfide besides new bacterial cells. Species belong to
clostridia comprises Bacteroidaceaea, found in digestive tracts responsible to degrade
sugars and amino acids.
2.13.2 Acetogenesis and Acid Formation

The end product of hydrolysis is organic acid (acetic acid), hydrogen and carbon
dioxide low molecular compounds. During the formation of propionic acid and acetic
acid significant amount of hydrogen is formed by acetic acid bacteria which decrease the
pH in aqueous medium (Droste, 2004). Other bacteria produce butyric and propionic acid
as well as other low molecular weight compounds. These microorganisms can tolerate
against broad range of environmental conditions with optimal pH 5-6 while digester
normally operates at pH 7. Acid former can create unfavorable condition for
methanogenic bacteria if the system is not properly controlled. However at controlled
condition like pH hydrogen and carbon dioxide is taken up by methaongenic bacteria to
produce methane. At least 50% of the biodegradable matters are converted into propionic
and butyric acids and later on acetogenic bacteria convert these products into acetic acid
and hydrogen.
38
2.13.3 Methanogenesis
Formation of methane during anaerobic digestion is an end product. Acetoclastic (or
acetophilic) bacteria utilize acetic acid to convert into methane and carbon dioxide
(Droste, 2004).
CH3COOH
CH4 + CO2
They use specific substrate like acetic acid, hydrogen/carbon dioxide, carbon monoxide,
methanol and formic acid. Two types of methanogenic groups involve, one use acetic
acid or methanol, other hydrogen and carbon dioxide groups named as aceticlastic and
hydrogenotrophic methanogens. Two genera involve Methanosarcina and Methanocaeta
while methanocaeta is more sensitive to pH with longer retention time and produce lower
yields of methane than Methanosarcina (anaerobic reactor) than Methanosarcins.
Methanocaeta
develop
filaments
which
is
important
in
granule
formation.
Methanosarcina are grouped together forming coccus packages and use hydrogen and
methylamine. Methane former are fastidious in their requirement of growth and
metabolism then acid former therefore methane is produced generally. Optimum pH is
7.0 and activity decreases when pH falls out of range 6.0-8.0. Due to continuous
production organic acid is responsible for environmental stress on methane formers
because methane formers fail to convert organic acids in to hydrogen.
4H2 + CO2
CH4 + 2H2O
2.13.4 Start up of up flow anaerobic sludge blanket (UASB) reactor

The UASB was developed by Lettinga et al., 1980 and successfully used to treat
domestic municipal and industrial wastewater. Inoculation with granules for an UASB
reactor is an expensive operation. Self inoculation can be economical and to date most
research on self inoculation of UASB reactors have been reported. These results motivate
start up without inoculation but takes some weeks to develop (Tare et al., 1997; Draaijer
et al., 1992; Schellinkhout and Osorio 1994; Lettinga et al., 1993). During start up period
COD reduction ranging between 24 to 80% and during this period less/no biogas
39
production reported. Supplementation of such reactors was started to reduce the start up
period after the development of UASB.
UASB requires a special flow regime in order to provide sufficient time for
substrate to contact with sludge to assimilate. The great attraction of UASB reactor is low
sludge, maintenance, and investment. Post and pretreatment might be required for UASB
to reduce suspended solids, odor, remaining nutrients etc. This technology offers some
advantages and disadvantages. Suitable pH to run the reactor in normal mode is 6.3 to
7.8, COD between 250 mg L-1 and 400 mg L-1 an upper limit of COD is not known (Gate,
2001).
Normally influent enters into reactor from bottom and effluent exits from the top
of the reactor. Influent follows the up-flow movement contacting with sludge. Deflector
and baffle is installed in upper part of the reactor to prevent sludge discharge and upward
movement inside the reactor and it also helps sludge to sink back. Gas collector slightly
dips into water from the top of the reactor where gas accumulates and finds their path to
gas discharge and collector. Upper portion where gas is collected and effluent discharges
is called settling zone, transition zone where water separates from sludge and digestion
zone consists of sludge blanket.
Anaerobic reactor UASB is divided into four compartments: settling, gas-liquid
separator fluidized and sludge bed. Organic compounds in wastewater are hydrolyzed and
acidified by hydrolytic and acidogenic bacteria figure 2.5. The successful operation
requires a highly active biomass in the form of granules with good settling properties.
Excess sludge is periodically removed otherwise sludge bed fluidized zone decreases.
40
Table 2-5 Main advantages and disadvantages of UASB reactor
Advantages
Disadvantages
Low space required
Demand for know-how
Possibility to captured methane in
Economically not feasible in colder
enclosed system
climate at temperature lower than 15C
Low odour emission
In complete removal of pathogens; post
Hygienic advantages
treatment is required to solve this problem
Low mechanization
Longer start up period to reach maximum
Low but high quality sludge production
efficiency
Low demand for operational means,
Lack of process knowledge
control and maintenance

Low investment and operational cost
The most of the pilot scale UASB operated at 7-19C and COD removal
efficiency 55-77% and hydraulic retention times of 4-72 h. Other hand full scale
installations have been reported, operating at high temperature 20-30 C as this
temperature is suitable for anaerobic treatment. These installations are in Sao Paulo and
Saumare in Brazil, Kanpur and Mirzapur in India, Bucaramanga and cali in Colombia.
Most of them operated at an HRT more than 4 h but never exceeded of 20 h (Kalogo,
1999).
Different polymers have been used to reduce the UASB start up period. Moringa
oleifera is a tropical plant belonging to the family Moringaceae. Water extract Moringa
oleifera seed (WEMOS) was found effective in flocculation of organic matter. Currently
it is used to treat drinking water, where it was found as good coagulating agent (Kalogo,
2001). WEMOS contained active agents are dimeric cationic proteins, molecular
weight13 kDa. The WEMOS contains several types of carbon sources e.g. carbohydrates,
lignin, lipids and other nutrients like N, P and metal ions which support microbial
growth.
41
Figure 2.3 The UASB reactor
Figure 2.4 Biological conversions in aerobic and anaerobic systems
42
Figure 2.5 Anaerobic decomposition of organic matter
43
It was observed that start-up period shortened up to 20% as compared to control

when domestic wastewater fed at COD of 320 mg L-1 and suspended solids 165 mg L-1.
There was increase in acidogenic, methanogenic and biogas production. WEMOS was
found to be effective against growth of the coccoid bacteria and growth of microbial
nuclei which was found in supporting granulation process (Kalogo*, 2001). The
experiment results of Ghangrekar, (2005) indicate that organic loading rate and sludge
loading rate between 2.0-4.5 kg COD m-3 and 0.1-0.25 kg COD kg-1 VSS d, help in
developing good characteristic sludge for the removal of organics in wastewater
(Ghangrekar, 2005). Study of physical and biological performance of UASB reactor
during its start up period, it was observed in removal 65% COD and 73% of suspended
solids. This performance was achieved in 6 weeks of operation, second period after 14
weeks expressed by biogass released. Therefore in this study process optimization
focuses on shortened start up period. Reactor showed three phases, first phase low
biochemical activity, almost no biogas production and invariability of the effluent pH. It
was confirmed by the low VSS/SS ratio observed during first 6 week. It appeared
beginning weeks of the reactor were evident in removal of COD and SS due to
interception in the reactor. It has observed by many researchers that UASB reactor can
perform good removal of COD without biogas generation (Kalogo and Verstraete, 1999).
The drop of pH, increase of volatile fatty acid and gas bubble formation are features of
acidogenic during second phase (after six weeks). Biogas produced at that time dissolved
in effluent leaving the reactor. After 22 weeks 80% total COD, 60% of soluble COD and
90% suspended solids removed, at 29C with an HRT of 4 hrs, while 68% of total COD
removed was due to an interception. Start up operation of biological reactor without
inoculation is possible and long time (14 weeks) required for effective biological
degradation (Kalogo, 2001). Presence of suspended solids in MWW negatively
influences the methanogenic activity and the chemical oxygen demand. This can be a
problem for many anaerobic wastewater treatment systems such as expanded granular
sludge bed, the up flow anaerobic sludge blanket, anaerobic hybrid reactor and hydrolysis
up-flow sludge bed. An integrated treatment concept was studied for anaerobic treatment
of domestic wastewater. In this approach continuous stir tank reactor combined with
UASB to remove settle able solids in primary sedimentation and then fed to UASB. The
44
principal advantage is to lower the negative effect of suspended solids in the UASB
reactor; producing effluent of high quality for irrigation.
2.13.5 Start up of UASB reactor without inoculation

Reactor start up, Raw domestic wastewater naturally contains some anaerobic and
facultative anaerobic, it may be economical to start the reactor without inoculation. Self
inoculation of UASB during domestic wastewater treatment at temperature 19-23C and
HRT 20-40h COD removal efficiency was 60% in beginning and later increased to 75%
after 6 months, it was observed quite feasible (Grin et al., 1983). Later, Barbosa and Sant
Anna (1989) found excellent results of self inoculated UASB reactor treating domestic
wastewater with 4h HRT at 18-28C, 1 mm diameter of granules were developed after
one month. In nine months the size was increased up to 8 mm with COD removal of
74%. However, in none of the full-scale UASB reactors were observed granulation with
self inoculated treating domestic wastewater but their COD removal efficiency greater
than 80%. Some researchers Gnanadipathy and polprasert (1993) and Wang (1994)
observed poor inoculation. Granule formation in self inoculated reactor still needs further
investigation to make UASB reactor more reliable and exploring the ideal conditions for
bacterial cell aggregate into granules (Lettinga et al., 1983; Schmidt and Ahring, 1996).
Integrated treatment approach for wastewater treatment: A new approach in MWW
treatment to control suspended solids in influent of UASB and reducing the COD load to
the reactor, it can be successful in tropical areas. This integrated treatment concept
includes chemically enhanced sedimentation to remove suspended solids in the form of
sludge. Coagulant dosed to improve the removal of suspended solids so that CODs/VSS
ratio increased which facilitates in wastewater treatment by UASB reactor. Sludge from
sedimentation tank is digested separately with main objective of producing energy. Odor
problems have been reported which may be an important factor in selection of UASB
reactor. The principal advantages of anaerobic system are recovery of energy, lowering
the negative effects of suspended solids, production of good quality effluent for irrigation
and a compact treatment system (Kalogo, 1999).
45
2.13.6 Function of micro-nutrients during start-up of UASB

Role of micro-nutrients during start-up of UASB: Microbial species in UASB
reactor can be enriched with rich nutrient synthetic wastewater in order to achieve
maximum efficiency in short time period (Mahmood, 2007). Presence of macro and
micro-nutrients also help in removal of propionic acid in anaerobic digestion process.
Propionic acid is a recalcitrant which is difficult to degrade by biological means. In the
presence of supplemented macro and micro nutrients stimulate the anaerobic reactor
efficiency to remove propionic acid. A shock of high concentration of propionic acid
could harm the anaerobic species in reactor. On the contrary, gradual increase in organic
loading rate eliminates the propionic acid at high rate. Three phases of this experiment
without nutrients, with macro-nutrients and with macro & micro both nutrients; remove
3g, 18.1g and 32.8g of propionic acid. This shows that the presence of macro and micro
nutrients is clearly essential for the high removal of propionic acid during anaerobic
digestion (Ma, 2009). When a single micronutrient zero valence Fe was used, it showed
that UASB improve the removal of COD by 21% as compared to control reactor (Xu,
2005) Table 2-6.
Ammonia may cause process inhibition which is formed during the fermentation
process. This process inhibition favored by high pH. It starts formation when pH
increases above 7.5 and when its concentration increases from above 40 mg L-1 and
temperature above 30C. To avoid sludge bed washout from the reactor, the up-flow
velocity shouldnt exceed from 0.2 to 1 m h-1. it can be calculated as:
V= Q/A
V= H/HRT
Higher up-flow velocity better for sludge and mixing reactor but always there is
limitation not exceeding the up-flow velocity limits. For the growth of granules up-flow
velocity is 0.25 to 0.8 m h-1.
46
Table 2-6 Function of macro and micro nutrients in anaerobic digestion
Nutrients
Macro
Nutrients
Nitrogen
Phosphorus
Potassium
Sulfur
Micro
Nutrients
Cobalt
Copper
Iron
Molybdenum
Nickel
Selenium
Zinc
Main function
Unit
Supplement
Protein synthesis
Nucleic acid synthesis
Cell wall permeability
Numerous enzymes
COD/N
COD/P
COD mg g-1
COD mg g-1
>100/1.25
>100/0.25
5-450
10 to 2000
Corrinoids,CODH
Hydrogenase, SODM
Ligand, Sulfides, CODH
Inhibits Sulfur reducer,
FDH
Synthesis of F430,
essential for SRB
Fatty acid metabolism,
FDH
Hydrogenase, FDH,
CODH
g g-1 COD
g g-1 COD
g g-1 COD
g g-1 COD
100-1000
5-650
500-8500
65-300
g g-1 COD
10-13500
g g-1 COD
20-600
g g-1 COD
10-1250
CODH: carbon monoxide dehydrogenase; SODM: superoxide dismutase; FDH:

formate dehydrogenase; SRB: sulfate reducing bacteria.
2.13.7 Operational data and micronutrient requirement

To run UASB reactor in good operational conditions, some average parameters are
required given in Table 2-8 to achieve working goals Table 2-7. All micro organisms
require nitrogen for their growth. In wastewater nitrogen is present in the form of
ammonium-nitrogen and nitrate-nitrogen.
Methanogens require minimum nitrogen concentration of not less than 0.3 g L-1. If
the concentration decreases growth reduces drastically. For the growth, nucleic acid
synthesis and maintenance of the cell phosphorus is also important. The need of
phosphorus is 20% of the required nitrogen or 2.2% of volatile suspended solids. Less
availability of phosphorus may cause washout of sludge.
47
Table 2-7 Working goal (NEQS)
S. No.
Parameters
1
TemperatureoC
2
pH
3
5-days BOD at 20oC
4
COD (mg L-1)
5
Total suspended solids (mg L-1)
6
Total dissolved solids (mg L-1)
7
Grease and oil (mg L-1)
8
Sulphate (mg L-1)
9
Sulphide (mg L-1)
10
Phosphate (mg L-1)
11
Total nitrogen (mg L-1)
11
Total toxic metal (mg L-1)
Source, (Stoll, 1996; Aslam, 2007)
Standards
40
6.0-10.0
80
150
150
3500
10
600
1
2
15
2
Phosphorus is supplemented in term of KH2PO4 and K2HPO4 which serves as

phosphate buffer. Calcium has very good effect on flocculation process of the anaerobic
sludge. It also helps in granulation of the anaerobic sludge process at 0.15 g L-1. Copper,
molybdenum, zinc and manganese are necessary trace elements. Zinc is important for the
growth of methanogen (Singh, 1999). These trace elements can be added separately to
improve the efficiency of the reactor FeCl36H2O, ZnCl2, MnCl24H2O and CuCl22H2O.
Table 2-8 Important parameter for MWW treatment in UASB
Parameters
HRT (Hydraulic retention time) (h)
Up-flow velocity (m h-1)
Charge per volume (kg CODm-3 d-1)
Nitrogen (g L-1 )
Phosphorus (%)
Value
4-20
0.2-1
0.4-3.6
0.3
2.2 of cell volatile solids
2.13.8 Gas utilization

In UASB reactor, produced biogas should be trapped and use in burning process,
due to its high potential in global warming biogas not to be released into open
environment. There is a rapidly increasing demand of biogas due to increase in fuel cost,
improving the concept in use of renewable energy sources; production is possible in scale
48
sites. Compressed biogas can be used as fuel for vehicles which can be used, as same
existing technique is used for compressed natural gas. Application in vehicles requires
compression to high pressure (> 3000 psi).
2.13.9 Industrial wastewater treatment by UASB

Due to high energy supplemental chemicals and large amount of sludge production,
in conventional system, is less beneficial to the industry. Therefore anaerobic process is
viable alternative for the treatment of rich carbon wastewater. Such food industry
carrying high organic wastewater depletes dissolved oxygen which results in affecting
aquatic ecosystem. In a study it was reported COD removal efficiency 98% in UASB
with down flow anaerobic filter removal above 50%. Total COD removal with
combination was 99% during treating confectionary wastewater. Study on slaughter
house wastewater, an average value of COD 8000 mg L-1, was treated with UASB and
achieved COD removal efficiency 71% (Ruiz, 1997). Study of Kalyuzhnvi on cheese
whey wastewaters, in the laboratory and pilot reactor of UASB under mesophilic (35C)
and submesophilic (20-30C) conditions was tested with COD loading rate 28.5 and 9.5 g
COD L-1 day. Treatment efficiency higher than 90% was found to remove COD
(Kalyuzhnyi, 1997). Removal of 80% COD efficiency was achieved by the anaerobic
filter with pall ring bed process operated on ice cream wastewater with organic loading
rates around 6 kg COD m-1day-1. UASB reactor gave the poorest performance (COD
removal 50%) and granulation was not successfully achieved (Hawkes, 1994). It shows
that UASB has poor efficiency when treating the wastewater from ice-cream industry.
Another study was done on confectionary wastewater treatment by UASB reactor with
hydraulic retention time of 2-4 days. Reactor efficiency was measured by analyzing
COD, volatile fatty acid, pH, biogas production and study of its composition. Removal
efficiency 98% was observed with organic loading rate of 12.5 kg m-1day-1. An
additional anaerobic system named down flow anaerobic filter (DFAF) was added to
improve organic matter removal efficiency or as finishing step. Granulated sludge was
collected from another UASB reactor. During the first week UASB operation reached
60% of COD removal efficiency at 0.2 kg m-1 day-1organic loading rate and it was
increased gradually in 8 week upto 3 kg m-1 day-1. When organic loading rate was
49
increased upto 4.7 kg m-1day-1the efficiency was decreased to less than 50%. This
indicates that UASB reactor was working efficiently when loading rate was 3 kg m-1day1
or below. When it is more than 4kg m-1day-1the efficiency starts to decrease. It can be
recovered by decreasing the organic loading rate below 2 kg m-1day-1 upto 9 weeks.
DFAF was attached next to UASB so it was completely dependent upon treating
efficiency of the UASB. If the COD removal efficiency increases, loading rate decreases
for DFAF. In case when UASB is working below 50% efficiency then further combine
treatment with DFAF may attain COD removal efficiency more than 90%. This study
shows single treatment with UASB do not meet typical discharge limits and composite
system remove 99% COD 0.3 g L-1 while not yet dischargeable (Beal, 2000).
Same
conclusion was made by Rafael Borja while studying treatment of palm oil mill effluent
in UASB reactor. Rate of loading was gradually increased from 16.6 g L-1 d-1 to 60 g L-1
d-1 at hydraulic retention time of 0.9 days. Results showed that 90% reduction of COD
was observed at loading rate 16.6 g L-1 d-1 and removal efficiency started decreasing till
last loading rate of 60 g L-1 d-1. This reactor acclimated as acetic acid production at the
rate of 4.1 g L-1 d-1 when loading rate of 16.6 g L-1 d-1 adjusted in a period of 100 days.
This treatment system of UASB consisted of two stages UASB. Granule formation was
observed after the 90 days in both reactors which were acclimated rapidly to the
wastewater of palm oil mill effluent and tolerant to a suspended solid concentration of 5.4
g L-1 (Borja, 1996). A study by Caixeta proved efficient treatment was observed of
wastewater from meat processing plants when operated with organic load in the range of
2.7 10.8 kg COD m-1 day-1removed COD 85-90% with HRTs of 22, 18 and 14 h,
respectively (Caixeta, 2002).
2.14 Conclusions
CEPT in combination with UASB were successfully used in warmer climate. But
due to high sludge production during CEPT and slow start up of UASB, it still needs
improvements. In developing countries like Pakistan cost of some coagulant some time
difficult to afford high volume wastewater treatment.
50
Advanced oxidation process can be effective in simple treatment process along with
CEPT or UASB. Newly identified compounds like ethylestrdiol can not be eliminated by
conventional treatment processes as it was observed to disrupt endocrine system.
Microbial load in effluent remains high in biological treatment system.
Oxidation of UASB effluent with chemical is an attractive integrated treatment
concept when using waste H2O2 to reduce the chemical cost. It might help in developing
countries to use one waste to treat other waste.
UASB reactor has some limitations in start up to achieve maximum efficiency in
short period of time. Still more research is required to see the effects of synthetic
nutrients to shorten the start up period. Micro nutrients are important for protein
synthesis, nucleic acid synthesis, enzymes and main attraction of using UASB in
developing countries for efficient process performance.
51
References
Almeida, M. C., Butler, D. & friedler, E. (1999). At-source domestic wastewater quality.
Urban Water. 1, 49-55.
Al-Sammarraee, M., Chan, A., Salim, S. M. & Mahabaleswar, U. S. (2009). Large-eddy
simulations of particle sedimentation in a longitudinal sedimentation basin of a
water treatment plant. PartI: Particle settling performance, Chem. Eng. J. 152,
307-314.
Aiyuk, S. Amoako, J., Raskin, L., Haandel, A. V. & Verstraete, W. (2004). Removal of
carbon and nutrients from domestic wastewater using a low investment, integrated
treatment concept. Water Res. 38, 3031-3042.
Aslam, M.M., Malik, M., Baig, M.A. & Iqbal, J. (2007). Treatment performance of
compost based and gravel-based vertical flow wetlands operated identically for
refinery wastewater treatment in Pakistan. Ecol. Eng. 30, 34-42.
Beal, L. j. & Raman, D. R. (2000). Sequential two-stage anaerobic treatment of
confectionary wastewater. J. Agr. Eng. Res. 76, 211-217.
Benefield, L. D., Judkins, J. F. & Weand, B. L. (1982). In: Process chemistry for water
and wastewater treatment. pp. 191-210. Prentice- Hall, Englewood Cliffs, N.J.
Borja, R., Banks, C. J. & Sanchez, E. (1996). Anaerobic treatment of palm oil mill
effluent in a two-stage up-flow anaerobic sludge blanket (UASB) system. J.
Biotechnol. 45, 125-135.
Boschier, J. A. (1993). Criteria for assessing appropriate technology for sewage treatment
and disposal. Water Sci. Technol. 27 (1), 11-18.
Barbosa, A. & Sant Anna, Jr. G. L. (1989). Treatment of raw domestic sewage in an
UASB reactor. Water Res. Technol. 27, 75-82.
Bekri-Abbes, I., Bayoudh, S. &
Baklouti, M. (2007). A technique for purifying
wastewater with polymeric flocculant produced from waste plastic, Desalination.

204, 198-203.
52
Barbusinski, K. & Filipek, K., (2003). Aerobic sludge digestion in the presence of
hydrogen peroxide and Fentonss Reagent. Pol. J. Environ. Stud. 12, 35-40.
Bonnet, J. L., Groliere, C. A., Bohatier, J., Sargos, D., Pepin, D. & Fourneret, G. (1996).
Validation of laboratory pilot plants for wastewater treatment by natural pond
sedimentation, comparison with a reference plant. Sci. Total Environ. 193, 37-47.
Caixeta, C. E. T., Cammarota, M. C. & Xavier, A. M. F. (2002). Slaughterhouse
wastewater treatment: evaluation of a new three-phase separation system in a
UASB reactor. Bioresource Technol. 81, 61-69.
Campos, H. M. & Sperling, M. (1996). Estimation of domestic wastewater characteristics
in a developing country based on socio economic variables. Water Sci. Technol.
34, 71-77.
CWRAS. (2005). Country waster resources assistance strategy: disseminatin workshop,
Islamabad, September 19, 2005. Online, Accessed date 04/09/2009.
http://www.worldbank.org.pk/
Desbrow, C., Routledge, E. J., Brighty, G. C., Sumpter, J. P. & waldock, M. (1998).
Identification of estrogenic chemicals in STW effluent. 1. Chemical fractionation
and in vitro biological screening. Environ. Sci. Technol. 32 (11), 1549-1558.
Droste, R. L. (2004). In: Theory and practice of water and wastewater treatment. pp.
291-308. John Wiley & Sons, Inc.
Draaijer, H., Maas Jaw, Schaapman, J. E. & Khan, A. (1992). Performmance of the
5MLD UASB reactor for sewage treatment at Kampur, India. Water Sci. Technol.
25, 123-133.
Emmanuel, E., Blanchard, J.-M., Keck, G., Perrodin, Y. (2001). Chemical, bilogical and
ecotoxicological characterisation of hospital effluents. pp. 31-33. De chets
Sciences et Techniques, revue francophone de cologie, industrielle, No 222e`
me trimestre.
53
Elmitwalli, T. A., Zandvoort, M. H., Zeeman, G., Bruning, H. & Lettinga, G. (1999).
Low temperature treatment of domestic wastewater sewage in upflow anaerobic
sludge blanket and anaerobic hybrid reactors. Water Sci. Technol. 39, 177-186.
Fan, L. Xu, N., Ke, X. & Shi, H. (2007). Numerical simulation of secondary
sedimentation tank for urban wastewater. J. Chin. Inst. Chem. Eng. 38, 425-433.
Feo, G. D., Gisi, S. D. & Galasso, M. (2008). Definition of a practical multi-criteria
procedure for selecting the best coagulant in a chemically assisted primary
sedimentation process for the treatment of urban wastewater. Desalination. 230,
229-238.
Gate. (2001). Anaerobic treatment of municipal wastewater in UASB-reactor, Technical
information, Naturgerechte technologienm Bau-und wirtschaftsberatung. Online
Accessed
date
20/12/2008.
http://www.sswm.info/category/implementation-
tools/wastewater
Goula, A. M., Kostoglou, M., Karapantsios, T. D. & Zouboulis, A. I. (2008). The effect
of influent temperature variations in a sedimentation tank for potable water
treatment-a computational fluid dynamics study. Water Res. 45, 3405-3414.
Garcia, J. C.,Oliverira, J. L., Silva, A. E. C. & Oliverira, C. C. (2007). Comparative study
of the degradation of real textile effluents by photocataltic reactions involving
UV/TiO2/H2O2 and UV/Fe2+/ H2O2 systems. J. Hazard. Mater. 147, 105-110.
Ghangrekar, M. M., Asolekar, S. R. & Joshi, S. G. (2005). Characteristics of sludge
developed under different loading conditions during UASB reactor start-up and
granulation. Water Res. 39, 1123-1133.
Gnanadipathy, A. & Polprasert, C. (1993). Treatment of domestic wastewater with UASB
reactor. Water Sci. Technol. 38, 189-196.
Grin, P. C., roersma, R. D. & Lettinga, G. (1983). Anaerobic treatment of raw sewage at
lower teremertures, In: proceedings of the European symposium on anaerobic
wastewater treatment (AWWT), ed. Van Brink, W. J. 335-347. Noordwijkerhout.
ISSN 0194-3925.
54
Gautam, A. K, Kumar, S. & Sabumon, P. C. (2007). Preliminary study of physicochemical treatment options for hospital wastewater. J. Environ. Manag. 83, 298306.
Guida, M., Mattei, M., Rocca, C. D., Melluse, G. & Meric, S. (2007). Optimization of
alum-coagulation/flocculation for COD and TSS removal from five municipal
wastewater. Desalination. 211, 113-127.
Harleman, D. R. F. & Murcott, S. (1999). The role of physical chemical wastewater
treatment in the Mega-Cities of the developing world. Water Sci. Technol. 40 (45), 75-80.
Harleman, D. R. F. & Murcott, S. (2001). CEPT - an innovative approach to urban
wastewater treatment in the developing world, Department of Civil and
Environmental Engineering, Massachusetts Institute of Technology, Cambridge,
UK.
Online:
Accessed
date
12/04/2009.
http://www.zetatalk3.com/docs/Waste_Water/Sewage_Treatment_Chagnon_Intro
duction_to_CEPT_2002.pdf
Hawkes, F. R. Donnelly, T. & Anderson, G. K. (1995). Comparative performance of
anaerobic digesters operating on ice-cream wastewater. Water Res. 29, 525-533.
Janz, D. M. & Bellward, G. D. (1996). In ovo 2, 3, 7, 8- tetrachlorodibenzo- p-dioxin
exposure in three avian species: 2. Effects on estrogen receptor and plasma sex
steroid hormones during the perinatal period. Toxicol. Appl. Pharm. 139, 292-300.
Jurgens, M. D., Holthaus, K. I. E., Johnson, A. C., Smith, J. J. L., Hethridge, M. &
Williams, R. J. (2002). The potential for estradiol and ethinylestradiol degredation
English rivers. Env. Toxicol. Chem. 21 (3), 480-488.
Jobling, S., Nolan, M., Tyler, C. R., Brighty, G. & Sumpter, J. P. (1998). Widespread
sexual disruption in wild fish. Env. Sci. Technol. 32 (17), 2498-2506.
Kalyuzhnyi, S. V., Martinez, E. Perez & Martinex, J. R. (1997). Anaerobic treatment of
high-strength cheese-whey wastewaters in laboratory and pilot UASB-reactors.
Bioresource Technol. 60, 59-65.
55
Korner, W., Bolz, U., Submith, W., Hiller, G., Schuller, W., Hanf, V. & Hagenmaier, H.
(2000). Input/output balance of estrogenic active compounds in a major municipal
sewage plant in Germany. Chemosphere. 40, 1131-1142.
Kalogo, Y., MBassiguie Seka, A. & Verstraete, W. (2001). Enhancing the start-up of a
UASB reactor
treating domestic wastewater
by adding a water extract of
Moringa oleifera seeds. Appl. Microbiol. Biot. 55, 644-651.

Kalogo*, Y., Mbouche, J. H. & Verstraete, W. (2001). Physical and biological
performance of self inoculated UASB reactor treating raw domestic sewage, J.
Env. Eng. 127(2), 179-183.
Kalogo, Y. & Verstraete, W. (1999). Development of anaerobic sludge bed (ASB) reactor
technologies for domestic wastewater treatment: motives and perspectives. J.
Micro. Biotechnol. 15, 523-534.
Kalogo, Y., Mbouche, J. H. & Verstraete, W, (2001). Physical and biological
performance of self inoculated UASB reactor treating raw domestic sewage
Journal of Environmental Engineering. 127(2), 179-183.
Ksibi, M. (2006). Chemical oxidation with hydrogen peroxide for domestic wastewater
treatment. Chem. Eng. J. 119, 161-165.
Lange, R., Hutchinson, T. H., Croudace, C. P., Siegmund, F., Schwein, H., Hampe, P.,
Panter, G. H. & Sumpter, J. P. (2001). Effects of the synthetic estrogen 17
Ethinylestradiol on the life-cycle of the fathead minnow (pimephales promelas).
Env. Toxicol. Chem. 20 (6), 1216-1227.
Lau, Y. L. (1994). Temperature effect on settling velocity and deposition of cohesive
sediments. J. Hydrol Eng. ASCE. 118 (6), 849-867.
Lettinga, G., Van Velsen, A. F. M., Hobma, S. W., De Zeeuw, W. & Klapwijk, A.
(1980). Use of the upflow sludge blanket (UASB) reactor concept for biological
wastewater treatment, especially for anaerobic treatment. Biotechnol. Bioeng. 22,
699-734.
56
Lettinga, G. De Man, A. Vanderlast, A. R. M. Wiegant, W. Van Knippenber, K. Frijns, J.

& Van Buuren, J. C. L. (1993). Anaerobic treatment of domestic sewage and
wastewater. Water Sci. Technol. 27, 67-73.
Lettinga, G. (1996). Sustainable integrated biological wastewater treatment. Water Sci.
Technol. 3(33), 85-98.
Lettinga, G., Roersma, R. & Grin, P. (1983). Anaerobic treatment of raw domestic
sewage at ambient temperature using a granular bed UASB reactor. Biotechnol.
Bioeng. 25, 1701-1723.
Mahmood, F., Pimblett, J. G., Grace, N. O. & Grayman, W. M. (2005). Evaluation of
water mixing characteristics in distribution system storage tanks. J. Am. Water
Works Ass. 97 (3), 74-88.
Mahmood, Q. (2007). In: Process performance, optimization and microbiology of anoxic
sulfide biooxidation using nitrite as electron acceptor. pp. 44-69. PhD dissertation.
Masters, G. M. (2004). In: Introduction to environmental engineering and science.
Pearson education. pp. 268-274. Second edition.
Ma, J., Mungoni, L. J., Verstraete, W. & Carballa, M. (2009). Maximum removal rate of
propionic acid as a sole carbon source in UASB reactors and the importance of
the macro- and micro nutrients stimulation. Bioresource Technol. 100, 34773482.
Martinez, N. S. S. & Fernandez, J. F. (2003). Pre-oxidation of an extremely polluted
industrial wastewater by the Fentons reagent. J. Hazard. Mater. B101, 315-322.
Metcalf and Eddy. (2004). In: Wastewater engineering, treatment disposal reuse. pp.
1334-1338. Mc Graw-Hill, Inc, New York.
Mergaert, K., Vanderhaege, B. & Verstraete, W. (1992). A review. Application and
trends of anaerobic pre-treatment of municipal wastewater. 26, 1025-1033.
Nakhata, G. F. (2001). Moringa as an alternative to aluminium sulphate (in drinking
water). 27th WEDC Conference, Lusaka, Zambia.
57
NDabigengesere, A. and Narasiah, K. S. (1998). Use of Moringa oleifera seeds as a

primary coagulant in wastewater treatment. Env. Technol. 19, 789-800.
Panter, G. H., Thompson, R. S., Beresfor, N. & Sumpter, J. P. (1999). Transformation of
a non-estrogenic steroid metabolite to an estrogenically active substance by
minimal bacterial activity. Chemosphere. 38 (15), 3579-3596.
Purdom, C. E., Hardiman, P. A., Bye, V. V. J., Eno, N. C., Tyler, C. R. & Sumpter, J. P.
(1994). Estrogenic effects of effluents from sewage treatment works. Chem. Ecol.
8(4), 275-285.
Ruiz, I., Veiga, M. C., DeSantiago, P. & Blfizquez, R. (1997). Treatment of
slaughterhouse wastewater in a UASB reactor and an anaerobic filter.
Russo, J. Tahin, Q. Lareef, M. H. Hu, Y. F. & Russom, I. H. (2002). Neoplastic
transformation of human breast epithelial cells by estrogens and chemicals
carcinogens. Env. Mol. Mutagen. 39 (2-3), 254-263.
Rudder, D. D., Wiele, T. V., Dhooge, W., Comhaire, F. & Verstraete, W. (2004).
Advanced water treatment with manganese oxide for the removal of 17 ethynylestradiol. Water Res. 38 (1), 184-192.
Singh, R. P., Kumar, S. & Ojha, C. S. P. (1999). Nutrient requirement for UASB process:
a review. Biochem. Eng. J. 3, 35-54.
Snyder, S. A., Keith, T. L., Verbrugge, D. A., snyder, E. M., Gross, t. S., Kannan, K. &
Giesy, J. P. (1999). Analytical methods for detection of selected estrogenic
compounds in aqueous mixtures. Environ. Sci. Technol. 33 (16), 2814-2820.
Schellinkhou, A. Osorio, E. (1994). Long term experience with the UASB technology for
sewage treatment on large scale, In: Proceedings of the international symposium
on anaerobic digestion. RSA Litho, Cape Town, 251-252.
Schmidt, J. E. & Ahring, B. K. (1996). Granular sludge formation in up flow anaerobic
sludge blanket (UASB) reactors. Biotechnol. Bioeng. 49, 229-246.
58
Sayed, S. K. I. A. & Fergala, M. A. A. (1995). Two stage UASB concept for treatment of
domestic sewage including sludge stabilization processes. Water Sci. Technol. 32,
55-63.
Stoll, U. (1996). Liquid effluent treatment sewage sludge management and industrial
effluent standards. Resour. Conc. Recycle.16, 113-133.
Tare, V. Mansoor, A. M. Jawed, M. (1997). Biomethanation in domestic and industrial
waste treatment- an Indian scenario. In: Proceedings of the 8th International
Conference on Anaerobic Digestion 2. IAWQ, Pergamon Press, Sendai, 255-262.
USperoxide. (2009). specializing in hydrogen peroxide for environmental and in
industrial application: Online Access date 07/09/2009;
http://www.h2o2.com/intro/properties.html.
Verstraete, W. & Vandevivere, P. (1999). A review. New and broader applications of
anaerobic digestion. Criticals reviews, Env. Sci. Technol. 28, 151-173.
Verstraete, W. (2004). In: Environmental biotechnology. Department of microbial
ecology. pp. 1-100. Ghent University Gent, Belgium.
Wang, D., Shin, J. Y., Cheney, M. A., Spostito, g. & Spiro, T. G. (1999). Manganese
dioxide as a catalyst for oxygen independent atrazine dealkylation Env. Sci.
Technol. 33(18), 3160-3165.
Well, S. A. & Laliberte, D. M. (1998). Water temperature gradients in circular clarifiers.
Water Env. Feder. 6, 1274-1279.
Xu, G. R., Zhang, W. T. & Li, G. B. (2005). Adsorbent obtained from CEPT sludge in
wastewater chemically enhanced treatment. Water Res. 39, 5175-5185.
Yin, K, 2009, Ratio of nitrogen to phosphorus in the Pearl River and effects in the
estuarine coastal water: nutrient management strategy in Hong Kong. Phys.
Chem. Earth, Accepted manuscript.
Yonar, T., Kestioglum K. & Azbar, N. (2006). Treatability studies on domestic
wastewater using H2O2/UV process, Applied Catalysis B: Environmental, 67,
223-228.
59
Zeng, Y., Yang, C. Zhang, J. & Pu, W. (2008). Feasibility investigation of oily
wastewater
treatment
by
combination
of
zinc
coagulation/flocculation. J. Hazard. Mater. 147, 991-996.
60
and
PAM
in
3 Chapter 3:
Municipal Wastewater Treatment by Coagulation
61
Abstract
Three coagulants viz. alum, FeCl3 and Moringa oleifera seed extract were
compared for treating MWW. The wastewater samples were collected from a drain near
the Murree Road in Abbottabad city. The initial treatment depicted that alum was a
suitable coagulant, while the other two caused color development and increased COD in
the effluent. Subsequently, wastewater samples were treated with graded concentrations
(4~32 mg L-1) of alum in batch series, and shacked at 600-620 rpm for five minutes. The
treated samples were analyzed for various water quality parameters to examine the
effective coagulation and flocculation process in the wastewater. There was an increase
in TDS and electrical conductivity with the increasing levels of alum above the optimized
values (22 to 30 mg L-1). The proposed primary treatment strategy of wastewater
treatment with alum is suitable for reducing the pollutants load in the sewer system.
Key words; Chemical oxygen demand, Total dissolved solids, Total suspended solids,
Total Kjeldahl nitrogen
62
3.1 Introduction
Wastewater generally contains a wide variety of colloidal impurities, which are
not settled by gravitation in natural sedimentation process and can pass through the pores
of most common filtration media. These colloidal particles are present in wastewater in
well-stabilized form. The removal of colloids and suspended solids (SS) from wastewater
needs destruction of the stabilizing forces leading to coagulation. Destabilization can be
achieved by double layer compression, adsorption and charge neutralization, enmeshment
in a precipitate and adsorption and inter-particle bridging (Benefield, 1984). Municipal
wastewater contains SS and TDS, which increase the COD and reduce the DO
concentration. Primary treatment is the first stage of wastewater treatment that removes
floating solids, and generally removes 50-70% of the SS and 40-50% of the associated
COD in the wastewater.
Natural sedimentation takes longer time to remove a part of the resistant fraction
of the SS. Synthetic coagulants are efficient for SS and COD removal from domestic
wastewater within reasonably short time (Kologo, 1999). Sedimentation is high when
particle size is greater than 50 m and lesser below 2 m size (Benefield, 1984;
Tchobanoglous, 2003). For low strength wastewater (COD < 500 mg L-1) alum treatment
can also be important in the removal of SS and TDS.
Use of various coagulants to reduce the amount of SS from wastewaters is called
CEPT that shortens the sedimentation process to 2 or 3 hours. The use of CEPT is a time
saving and handy technique (Xu, 2005; Joaquin et al., 2007). An additional benefit of
CEPT is the removal of nitrogen and phosphorus along with SS removal in the same
sedimentation tank (Guida, 2007). The CEPT process also allows the reduction of organic
matter from wastewater (Nakhata, 2001; Tchobanoglous, 2003, Koogo, 1999). It allows
the sedimentation basins to operate at higher flow rates, while still maintaining the
efficient removal of COD.
The treatment infrastructure can be smaller for CEPT, which reduces capital
costs. The present research work was undertaken to test various coagulants such as Al2
(SO4)3, FeCl3, and Moringa oleifera seed extract to settle down the organic matter and to
63
optimize the concentration of a suitable coagulant for the efficient removal of settleable
solids and colloidal particles in the MWW.
Figure3.1 Location of MWW sampling site in Abbottabad city
64
3.2 Materials and Methods

3.2.1 Collection of MWW
The MWW samples were collected fortnightly from the open flowing stream of
MWW near the Murree Road in Abbottabad city (Figure 3.1) during February 2007 to
February 2008 between 10:00 a.m. to 12:00 noon. These samples were brought to the
laboratory within 30 minutes and stored for subsequent experiments. This MWW also
contains small quantities of industrial wastewaters originating from small industrial areas
of Abbottabad.
3.2.2 Batch experiments

Batch experiments were carried out by stirring the coagulant treated MWW
samples at 600-620 rpm for 5 minutes (Aiyuk, 2004). During these tests, various
concentrations of three coagulants viz. alum, FeCl3 and Moringa oleifera seed extract
were mixed (4, 8, 12, 16, 20, 24, 25, 28, 32, 50 and 75 mg L-1, respectively) with
subsequent stirring for 5 minutes and then settling for 3 hours. After three hours of
sedimentation, supernatant was subjected to COD, Ortho-P, pH, TSS, TDS, and TKN
determination.
3.2.3 Analytical procedures

Raw and coagulated samples were analyzed for their COD, TDS, pH, TKN and
Ortho-P according to the standard methods (APHA, 2005). For COD determination
closed reflux, calorimetric method included digestion at 150oC for 2 hours in COD vials
followed by spectrophotometer reading at 530 nm (APHA, 2005). The pH was measured
using a digital pH meter (HANNA, HI 991003 Sensor Check pH), TDS and conductivity
by HANNA, HI9835 Microprocessor for conductivity/TDS. Moringa oleifera seed
extract was obtained by dissolving grinded seeds in water and then filtered (Kologo,
2001).
3.3 Results and Discussions

3.3.1 Effect of various coagulants on COD
Alum was found to be more efficient in reducing the COD as compared to M.
oleifera seed extract and FeCl3 (Figure 3.2) shows that alum and FeCl3 displayed almost
65
similar behavior in removing COD; however, application of 8 ml L-1 and higher doses of
M. oleifera seed extract caused an increase in the COD. The M. oleifera dose of 32 ml L-1
caused an increase of COD concentration. The COD decreased with all of the used
concentrations of alum and FeCl3 treatment. Figure 3.2 clearly showed that a significant
COD removal rate was obtained by using alum. Application of 24 mg L-1 of FeCl3 did not
cause further decrease in COD and the curve became almost flat. Alum dose up to 32 mg
L-1 showed considerable decrease in COD i.e. it decreased from 210 mg L-1 to 100 mg L1
. Based on this observation of COD, we selected alum for further investigation. Other
advantages of using alum are its easy availability, low cost and ease of handling.
Figure 3.3 shows the concentrations of COD after alum treatment in different samples.
Seven samples collected at various intervals were run to see the effectiveness of alum for
the COD removal. Decrease of COD level in treated wastewater continued until the last
dose of 32 mg L-1 was applied. It was observed that alum dose and COD removal
efficiency had a linear relation.
Figure 3.2 Decrease in COD after treating with various coagulants
Alum treatments at the concentration range of 24 to 32 mg L-1 resulted in the

effluent COD values that were within the limits of National Environmental Quality
Standards (NEQS) (GOP, 2000). It was also observed that after applying alum at 30
mg L-1, TDS started increasing. The excessive use of alum could reduce the COD level
effectively but it might decrease the pH along with increasing TDS in the effluent
66
(Sarkar, 2006). The excessive alum dose in wastewater treatment might release more
aluminum species and could result in higher aluminum in drinking water which may
cause the Alzheimers disease when the aluminum was above 200 gL-1 (Sarkar, 2006;
Johnson et al, 2005). Therefore, the optimum dose of aluminum sulphate was found as 28
mg L-1 to obtain maximum COD removal efficiency.
3.3.2 Effect of various coagulants on TDS

Comparison of TDS removal after treating with M. oleifera seed extract, FeCl3
and alum has been shown in Figure 3.4. A linear decrease/increase in TDS was observed
as enhanced rates of coagulants were added. TDS started increasing after applying 8
ml L-1 of M. oleifera seed extract. In case of FeCl3 and alum, TDS increased by treating
MWW with their concentrations above 24 mg L-1 and 28 mg L-1, respectively. However,
alum treatment caused lesser increase in TDS as compared with FeCl3 and M. oleifera
seed extract application. Increase in TDS was seen with increasing coagulant rates. This
indicated that alum was highly reactive and formed flocks for settling. The FeCl3
treatment produced color in the effluent which was unacceptable.
Figure.3.3 Effect of various coagulants on TDS of MWW
With the increasing alum doses, TDS also increased. One of our objectives was to
find optimum alum dose where no increase in TDS could happen. Figure 3.5 shows that
there was no increase in TDS up to alum dose of 30 mg L-1; however, at 50 mg L-1 of
67
alum dose TDS started to increase again. It was also observed that cleaner decant formed
at higher doses of alum. The increase in TDS may cause hydrolysis of alum forming
strong acids, which enhance the ionic strength of the medium (results not shown).
Therefore, we limited the dose between 20 and 30 mg L-1.
3.3.3 Effect of reaction time and alum level on TSS

In the next step, alum mediated optimum reaction time was determined. During
these experiments, the samples were drawn at three stages after the alum application in
MWW viz. after 1, 2 and 3 hours of sedimentation. During the first hour, removal rate
was not high, and the highest removal rate was observed after 3 hours; therefore, the
optimum reaction time was regarded as 3 hours. The removal rates of TSS were also
measured after each hour and at each rate of alum (Figure 3.5).
Figure3.4 Effect of different concentrations of alum on TDS of MWW
When dissolved in water, alum produces positively charged cations and

negatively charged colloidal particles that form flocks. When flock size of > 200 m is
attained; the flocks begin settling (Heinzman, 1994; Tchobanoglous, 2003). Allowable
limit of TSS is 35 mg L-1 in the municipal effluents. When alum dose of 24 mg L-1 was
applied, a maximum removal of 50% TSS from MWW was attained. After three hours of
68
sedimentation, not much decrease in TSS was observed and at 32 mg L-1 52% removal of
TSS was observed.
The TSS removal was also significantly (p < 0.05) affected by the addition of
alum which showed promising results where the TSS removal of 67% was achieved.
Most of the samples contained TSS > 100 mg L-1. Natural sedimentation lasts for 6 hours
or even more to settle down the suspended solids. The settling of suspended solids can be
effectively enhanced by alum addition. Suspended solids removal is important before
secondary treatment. It is evident in Figure 3.6 that the alum addition of 20 mg L-1 of
alum dose was not much effective and enough to decrease the suspended solids load. The
alum treatment resulted in the highest removal of 70% TSS (Figure 3.5).
The allowable TSS limit in the effluent is 35 mg L-1 (Harleman, 2001). During the
coagulation and flocculation process, some part of the dissolved solids also settles down
under the large flock settling. The advantage of alum treatment is that it produces less
sludge than other coagulant like lime. When alum is added to wastewater, the following
reaction takes place (Tchobanoglous, 2003, Guida, 2007):
Figure 3. 5 Effect of alum treatment reaction time on TSS of MWW
69
Al2 (SO4)318H2O +3Ca(HCO3)2 3CaSO4+2Al(OH)3+6CO2+18H2O

The insoluble aluminum hydroxide is a gelatinous flock that settles down, sweeping out
the suspended material (Kim, 2008).
Figure3.6 Effect of different concentrations of alum on removal percentage of TSS from MWW
3.3.4 Effect of alum on ortho-phosphate and nitrogen

The natural sedimentation process might not help in the reduction of
ortho-phosphate (ortho-P), but total Kjeldahl-nitrogen (TK-N) was reduced from 14 to 11
mg L-1 (Figure 3.7 and 3.8). The addition of one mole alum will precipitate one mole of
phosphate (Tchobanoglous, 2003, Kim, 2007). Reduction of TKN may take place along
with the settling of organic matter due to natural sedimentation process. With natural
sedimentation process only 0.04 mg of ortho-P was reduced. Ortho-P can be easily taken
up by the aquatic species because it may be present in dissolved form. As the
concentration of alum increased from 4 through 32 mg L-1, the ortho-P started to
precipitate and settled down with sludge. The highest removal of 8 mg L-1 for Ortho-P
was recorded when treated with 32 mg L-1 of alum (Figure 3.7). The excessive quantities
of Ortho-P may result in the eutrophication of water bodies, thus chemical coagulation
70
can be an effective way to reduce the chances of eutrophication. For the phosphorus
reduction, alkalinity, pH, quantity and nature of suspended solids are the important
factors that may be considered during wastewater treatment. The desired pH is 6 to 7.5
along with sufficient alum dose for obtaining the optimum results. Sarkar, 2006; Pinotti,
2001; Aiyuk et al., 2004 demonstrated that the maximum removal of total phosphorus
occurred at pH 8.
Figure 3.7 Effect of different concentrations of alum on removal percentage of TSS from MWW
We observed that optimized alum dose was not sufficient for the removal of
ortho-P to meet the NEQS (Figure 2.7; Chapter 2). Increase in alum dose to reduce the
ortho-P resulted in an increase of the effluents TDS. Eutrophication may start at 1 mg L-1
of available phosphorus. Nitrogen to phosphorus ratio of 10-16:1 is ideal for
eutrophication (Zheng, 2004). Our main target was to reduce the COD up-to acceptable
level. It is suggested that secondary treatment is required in order to reduce Ortho-P
concentrations in the treated effluents. Addition of 24 mg L-1 alum did not significantly
(p > 0.05) remove TK-N. The highest TK-N removal rate was observed during initial
alum treatment and at higher alum doses removal rate was not significant (Figure 3.8).
71
Figure 3.8 Effect of different concentrations of alum on removal percentage of total kjeldahl nitrogen
of MWW
3.3.5 Effect of alum on turbidity

Turbidity in wastewater is caused by suspended and dissolved solids. More than
80% removal of turbidity was observed at alum dose of 32 mg L-1. Alums in wastewater
Figure 3.9 Effect of different concentrations of alum on the removal of turbidity in MWW
72
treatment undergo a series of hydrolysis processes producing charged species which

interact with negatively charged colloidal particles causing them to destabilize. These
destabilized particles form flocks or bridges reducing the turbidity of wastewater by
settling down. The NEQS for acceptable turbidity is >5 NTU. The highest turbidity
reduction was observed when 32 mg L-1 alum level was used (Figure 3.9).
3.4 Economic Aspects

Wastewater treatment system requires considerable cost. Its most important costly
factors are operation; maintenance, sludge treatment and its disposal. Small treatment
facility such as less than 10,000 I.E is more costly. A total investment cost of about 150$
per capita is an average. About half is for building construction and remaining consists on
electrical and mechanical devices. The construction and running cost vary considerably.
The total cost for treatment is 60$/y on the basis of that one inhabitants produce 180 liters
of wastewater per day and treatment cost range around 0.7 $/m3. These figures only give
order of magnitude ( 3-1).
3.5 Conclusions
Effects of various coagulants viz. FeCl3, Moringa oleifera seed extract and alum
were studied for their suitability to treat MWW. Different concentrations (4~32 mg L-1)
were applied in a series of batch mode at 600-620 rpm stirring for five minutes. There
was an increase of TDS when the level of alum was increased above the optimized value
of 32 mg L-1. The highest rate of pollutants removal load was observed when 22 to 32 mg
L-1 of alum was used. Therefore, alum concentration in the range of 22 to 32 mg L-1 was
an optimum dose for MWW treatment.
73
Table 3-1 The economic analysis of various treatment options for MWW
74
References
Aiyuk, S., Amoako, J., Raskin, L., Haandel, A. V. & Verstraete, W. (2004). Removal of
carbon and nutrients from domestic wastewater using a low investment, integrated
APHA, American Public Health Association. (2005). Standard methods for the
examination of water and wastewater (21st Edition), American Public Health
Association, Inc., New York USA.
Benefield, L. D. Judkins J. F. & Weand, B. L. (1984). Process chemistry for water and
wastewater treatment. pp 193-199. Prentice-Hall, Inc., Englewood Cliffs, New
Jersey.
GOP, Government of Pakistan. 2000. National Environmental Quality Dtandards for
Municipal and Liquid Industrial Effluents, The Gazette of Pakistan, Ministry of
Environment, Local Government and Rural Development, Islamabad, S.R.O. 549
(I)/2000, 24.
Guida, M., Mattei, M., Rocca, C. D., Malluso, G & Meric, S. (2007), Optimization of
alum-coagulation/flocculation for COD and TSS removal from five municipal
wastewater. Desalination. 211, 113-127.
Harleman, D. R. F. & Murcott, S. (2001). CEPT- an innovative approach to urban
wastewater treatment in the developing world, Department of Civil and
Environmental Engineering, Massachusetts Institute of Technology, Cambridge,
UK.
Heinzman, B. (1994). Coagulation and flocculation of storm water from a separate swer
system- a new possibility for enhanced treatment. Water Sci. Technol. 29 (12),
267-278.
Joaquin, R. & Teresa, G. (2007). Aluminium sulfate as coagulant for highly polluted cork
processing wastewaters: removal organic matter. J. Hazard. Mater. 148, 15-21.
Johnson, V. J., Kim, S. H. & Sharma, R. P. (2005). Aluminium-malotolate induces
apoptosis and necrosis in neuro-2a cells: potential role for p53 signalling. Toxicol.
Sci. 83, 329-339.
Kalogo, Y., Ska, A. M. & Verstraete, W. (2001). Enhancing the start-up of a UASB
reactor treating domestic wastewater by adding a water extract of Moringa
oleifera seeds. Appl. Microbiol. Biotechnol. 55, 644-651.
75
Kologo, Y. & Verstraete, W. (1999). Technical feasibility of the treatment of domestic

wastewater by a CEPS-UASB system. Env. Technol. 21, 55-65.
Kim, J. Y. & Sansalone, J. J. (2008). Zeta potential of clay-size particles in urban
rainfallrunoff during hydrologic transport. J. Hydrol. 356, 163-173.
Nakhata, G. F. (2001). Moringa as an alternative to aluminium sulphate (in drinking
water). 27th WEDC Conference, Lusaka, Zambia.
Pinotti, A. & Zaritzky, N. (2001). Effect of aluminium sulfate and cationic
polyelectrolytes on the destabilization of emulsified wastes. Water Manag. 21,
535-542.
Sarkar, B., Chakrabarti, P. P. & Vijaykumar, A. (2006). Wastewater treatment in dairy
industries-possibility of reuse. Desalination. 195, 141-152.
Tchobanoglous, G., Burton, F. L., Stensel, H. D., Metcalf & Eddy. (2003). In:
Wastewater Engineering: treatment and reuse. pp. 361-411. International Edition.
McGrawHill.
Xu, G. R., Zhang, W. T. & Li, G. B. (2005). CEPT an innovative approach to urban
wastewater treatment in the developing world. Water Rres. 39. 5175 5185.
Zheng, P., Xu, X. Y. & Hu, B. L. (2004). New theory and technology for biological
nitrogen removal. Science Press, Beijing.
76
4 Chapter 4:
Municipal Wastewater Treatment by Waste Hydrogen Peroxide
77
Abstract
Wastewater treatment is a challenging task in order to meet the demands of everincreasing human population and industrial development. AOPs show promising results
if applied to wastewater treatment. Waste H2O2 (40%) collected from a food industry
after tetra pack disinfection was employed in batch experiments to oxidize MWW.
Various H2O2 doses (1, 1.5, 2 and 2.5 ml L-1) were applied to evaluate its influence on
COD, BOD5, pH, turbidity and fecal coliforms. With the increasing H2O2 concentration,
BOD5 and COD significantly (p< 0.05) reduced to70 and 93 mg L-1, respectively, along
with 51.72% reduction of turbidity at 2.5 ml L-1 of H2O2 thus meeting the NEQS. No
significant change in pH was observed during the application of 40% waste H2O2 which
fluctuated in the range of 8.31-8.46.
Keywords: Advanced oxidation process, Biological oxygen demand, BOD5/COD,
Chemical oxygen demand, H2O2
78
4.1
Introduction
Fresh and pure water is one of the basic necessities of growing world population
on earth. Pakistan mostly located in arid to semi-arid region with scarce water supplies
thus needs to collect and treat the wastewater (World Bank, 2008). Available water
resources are continuously depleting with constantly increasing discharge of wastewater,
thus, recycling MWW can be an effective choice for coping with water shortage. The
amount of discharged wastewater has profound effect on the environmental quality,
especially on water bodies and prospects of future generations. Hence, sustainable use of
available water will not only minimize adverse environmental impacts but also avoid
depletion of available pure water resources.
Wastewater treatment is a challenging task in order to meet the demands of everincreasing human population, sustainable agriculture and industrial development. For
wastewater, several treatments options exist, whose application depends on specific
objectives of cleaned wastewater reuse (Geissen, 2000). For wastewater treatment,
advance processes like chlorination and ozonation are compact and guarantee a better
quality of water produced (Bull, 1990; Ksibi, 2006) but they are expensive.
In AOPs; oxidation potential of hydroxyl group, of very reactive and short-lived
oxidants is utilized. Use of H2O2 is one of the AOPs techniques used alone (De Morais,
2005; Ksibi, 2006) or with some catalyst i.e., iron (Glaze, 1987), or UV light (Lazarova
et al., 2000; Liotta, 2009; Fernando, 1997) or O3 (Millero, 1989), which result in
reduction of BOD and COD of wastewater. Thus, current research was conducted, as an
attempt, to check the effectiveness of H2O2, as a strong oxidizing agent, in overall
reduction of organic load of MWW of Shaikhulbandi, Abbottabad, Pakistan.
H2O2 is used in many industries to disinfect the packaging material (Olmez,
2009). Use of H2O2, in tetra pack aseptic packaging of juices and milk, is important to
disinfect the packaging material Tetra Brik Aseptic (TBA) machine. Use of 37% H2O2 is
recommended for disinfection purpose. After production period of 100 hours, the
concentration of H2O2 is increased upto 40% which is not reused in TBA machine and is
drained into water bodies.
79
Statistics revealed that the cost of chemical treatment of domestic or MWW is

quite expensive (Song, 1992); however, such treatment is very efficient and time saving.
The addition of H2O2 to treat domestic wastewater has been demonstrated previously
(Ksibi, 2006); however, the use of fresh H2O2 can be very costly. It was hypothesized that
waste H2O2 generated from food industry in Pakistan could be employed to treat
domestic wastewater which might be a cost efficient and quite feasible idea.
The specific objective of the present research was to explore the effectiveness of
used H2O2 40% to reduce the BOD and COD of MWW.

4.2.1 Wastewater sampling
Municipal wastewater samples were collected from Shaikhulbandi Abbottabad,
Pakistan. For this purpose, 50 L container was cleaned thoroughly which was rinsed
thrice with running MWW before taking sample. After sample collection it was corked
and taken to the laboratory for further analysis and treatment. Its main characteristics are
given in Table 4-1. Waste 40% H2O2 was collected from drain of TBA machine in a food
factory located in Hattar Industrial Estate, Hattar near Abbottabad.
Table 4-1 Pre-experiment Analysis
Parameter
Value
pH
8.14
-1
202
-1
COD (mg L )
327
BOD/COD
0.62
BOD (mg L )
4.2.2 Optimization of H2O2 dose

The wastewater comprised of effluents from kitchen, washrooms, washing,
laundry etc. It contained a large quantity of organic pollution with BOD5/COD 0.7- 0.9
(Verstrate, 1998 and George, 2004). In order to evaluate the optimum amount of used
80
40% H2O2 for BOD, COD removal and fecal coliform reduction, a series of experiments
were conducted with various H2O2 concentrations i.e., 1, 1.5, 2 and 2.5 ml L-1. In these
experiments, BOD and COD were measured throughout the reaction period of 0, 30, 60,
90, and 120 min.
4.2.3 Treatment system

A mixer with variable rotational speed of 0-500 rotations per minute (rpm) was
used to mix the sample thoroughly. One-liter of raw municipal wastewater was treated in
batch reactor at mixing speed of 500 rpm. Four different concentrations of 40% H2O2 i.e.
1, 1.5, 2 and 2.5 ml L-1 were applied to various samples of wastewater, with continuous
stirring at 500 rpm. Changes in BOD and COD, for each tested sample were recorded, at
time intervals of 30, 60, 90 and 120 minutes after the addition of 40% H2O2. All the
experiments were conducted at ambient temperature of 25 + 2 0C.
4.2.4 Microbial count

Luminar flow hood along with the membrane filter technique was used for
microbial analysis (Verstraete, 1998). For this purpose, various dilutions (10-3 to 10-6)
were made of the wastewater sample. Nutrient agar was used as solidifying medium in
sterilized petri dishes. 100 mL diluted MWW sample was filtered through filter paper
(0.45 m porosity) and incubated at 35oC for 24 h. The colonies were counted under the
compound microscope at magnification power of 10-15 X.

All the analytical procedures used were the standard methods for water and
wastewater analysis (APHA, 2005). Wastewater samples were analyzed prior to and after
the treatment with used 40% H2O2. The BOD5 was measured by using standard method
(APHA, 2005), COD was determined by closed reflux colorimetric method using digester
(HACH - LTG 082.99.40001) (APHA, 2005). The wastewater sample, digestion solution
and sulphuric acid were digested in vials for two hours at 150oC. After digestion,
absorbance was measured at wavelength 605 nm in a spectrophotometer (LOVIBOND
tintometer GMBH, 44287 DORTMUND). The pH meter (HANNA, HI 991003) was
used for pH determination. H2O2 was measured according to Tetra Pak Technical data
81
manual by using hydrometer and temperature. The H2O2 value was obtained after
connecting temperature and hydrometer reading on third scale of H2O2 W/W (Tetra Pak,
2008).
4.2.6 Graphical work

Graphical work was carried out using Sigma PlotTM v.10.
4.3 Results and Discussion

4.3.1 BOD removal
The effects of various H2O2 concentrations on BOD removal have been shown in
Figure 4.1. It was evident that initial 202 mg L-1 BOD changed significantly (p < 0.05)
after applications of 40% H2O2 at different concentrations i.e., 1, 1.5, 2 and 2.5 ml L-1
measured at various intervals throughout the reaction period.
Figure 4.1 BOD reduction during treatment
Treatment of 1 ml L-1 used 40% H2O2 reduced BOD by 10 mg L-1, in first 30 min.
The highest decrease to 60 mg L-1 BOD was observed after 120 min of application of 2.5
82
ml L-1 H2O2. By increasing the concentration of used 40% H2O2 to 1.5, 2 and 2.5 ml L-1,
BOD values were reduced at a very rapid rate in first 30 min The maximum BOD
reduction was observed at highest concentration of used H2O2 treatment, in first 30
minutes and later BOD reduction rate was slower. Perhaps most of the reaction occurred
in the first phase, mixing and homogenization resulted in complete H2O2 consumption in
120 minutes (Figure 4.1). Percentage reduction of BOD was highest at 2.5 ml L-1 H2O2
i.e. 70% and was least at 1 ml L-1 after 120 minutes.
Figure 4.2 COD removal during treatment
4.3.2 COD removal

The results showed that the addition of H2O2 significantly (p< 0.05) reduced COD
of domestic wastewater. The COD reduction had a linear relationship with the addition of
H2O2. The effects of H2O2 addition on the COD content of MWW have been illustrated in
Figure 4.2. The results suggested that COD removal was strongly affected by applied
dose of H2O2. The application of 1 ml L-1 40% H2O2 reduced 36 mg L-1 COD (11%), in
first 30 min The dose of 1 ml H2O2 seemed quite insufficient in reducing COD burden as
it caused COD reduction of just 93 mg L-1 (46%) after 2 h. The maximum COD reduction
was observed when applying 2.5 ml L-1 H2O2, where COD value reduced to 93 mg L-1,
83
after 2hrs. By increasing the dose of 40% H2O2 from 1 to 1.5, 2 and 2.5 ml L-1, COD
values, reduced rapidly in first 30 min; however, subsequent COD reduction was at a
slow rate in next 2 hrs, revealing that mixing and homogenization may have affected
COD reduction in comparison to BOD5 of MWW. The COD values decreased with the
increasing dose of 40% H2O2 and reached to 93 mg L-1 after 2 h of treatment, which
satisfied the NEQS. Thus, the use of H2O2 only is particularly efficient for COD removal
in this case. These results prove the degrading action of the waste H2O2 for the organic
matter of the wastewater. Based on these results, we achieved the purification of the
MWW by the waste H2O2.
Figure 4.3 The variation of BOD/COD
4.3.3 BOD5/COD ratios and biodegradability of MWW

The MWW was treated under operational conditions: (initial pH = 8.14 at reaction
temperature of 25 C) using various concentrations of H2O2. BOD5/COD ratios of
effluents obtained after each treatment were measured and have been presented in Figure
4.3. The initial BOD5/COD ratio of raw wastewater was around 0.6 which indicated its
biodegradability. The effluent treated with 2.5 ml L-1 of used H2O2 (40%) increased the
84
ratio to 0.8 after 30 minutes of H2O2 application then it stabilized around 0.7. Therefore,
the biodegradability of domestic wastewater was improved greatly. Lower amounts of
H2O2 caused lowering of BOD5/COD ratio as illustrated in Figure 4.3. The active forms
of oxidants are released from H2O2 in the form of OH- and HO2- produced resulting
increase in BOD5/COD ratio (Metcalf & Eddy, 2003; Ksibi, 2006).
For MWW treatment the effect of three coagulants viz. alum, FeCl3 and Moringa
oleifera seed extract were investigated. The wastewater samples were taken from the
Abbottabad city drain near Murree road. the first treatment illustrate that alum was most
appropriate coagulant, while the other two produced color and also increased the COD of
the effluent. Finally, in the batch series wastewater samples were treated with graded
concentrations (4~32 mg L
-1
) of alum. To determine the effective coagulation and
flocculation process in the wastewater, the treated samples were investigate for various
water quality parameters. TDS and electrical conductivity were increased with the
increasing levels of alum above the optimum values (22 to 30 mg L -1 (IHP, 2008; Song,
1992; Ksibi, 2006).
Figure 4.4 COD and turbidity percentage removal
85
4.3.4 Turbidity removal

In the Figure 4.4. the effect of various concentrations of H2O2 treatment on
turbidity was observed after oxidation of organic matter. H2O2 is a week acid and has
strong oxidizing properties and is therefore a powerful bleaching agent. The rate of
decomposition is dependent on the temperature and concentration of H2O2. Using 1 ml L1
H2O2 treatment caused 74.13% reduction in turbidity with 43 naphelometric turbidity
units (NTU). At 1.5 ml H2O2 per liter, 67.24% turbidity was reduced and only 51.72%
(26 NTU) reduction was observed at 2 ml of H2O2. A sharp slope in Figure 4.4 shows
that the maximum effective dose in reducing turbidity was 2.5 ml L-1. Turbidity
decreased with decrease in COD indicating that oxidation of organics took place in
pH
wastewater.
Figure 4.5 Changes in pH during treatment
Reduction of turbidity by H2O2 was almost at same rate as COD removal as

evident from Figure 4.4. Use of H2O2 efficiently reduced the COD and turbidity.
Treatment of MWW with 2.5 ml H2O2 resulted in more turbidity reduction compared
with COD. Our preliminary experiments indicated that further addition of peroxide was
86
not efficient to reduce the turbidity but was effective in COD and fecal coliform
reduction (results not shown).
87
4.3.5 Effect on pH after addition of H2O2

The changes of pH after the addition of 40% waste H2O2 have been illustrated in
Figure 4.5. No significant change in pH was observed after dosing with 1 ml L-1 40%
H2O2 and during first 30 minutes pH was increased from 8.14 to 8.17 and reached upto
8.31 in 2 hrs. But at 1.5 ml L-1, pH increased, from 8.14 to 8.37 in 2 hrs. Similarly, doses
of 2 and 2.5 ml L-1 caused an increase in pH from 8.42-8.46. Increase in pH, at different
doses of 40% H2O2 might be due to oxidation by H2O2, which resulted in release of some
bases.
4.3.6 Economic aspects

Wastewater treatment system requires considerable cost. This treatment process
where waste peroxide (Rs. 5L-1) was used which is cheaper than alum as explain in
chapter 3. In Table 4-2 three comparisons are indicated with percentage cost again
aerobic and CEPT. Most costly factors are pumps, screen and sand trap, H2O2, motors
and electricity. Motors and electricity may be considered as more costly because mixing
with H2O2 can last for one hour. Small treatment facility such as less than 10,000 I.E is
more costly, as discussed in previous chapter. A total investment cost of about 150$ per
capita is an average. About half is for building construction and remaining consists on
electrical and mechanical devices. The construction and running cost vary considerably.
The total cost for treatment is 40$y-1 on the basis of that one inhabitants produce 180
liters of wastewater per day and treatment cost range around 0.4 $m-3 when using
peroxide single stage treatment process, this number only give order of magnitude (Table
4-2).
4.4 Conclusions
Waste H2O2 used 40%, proved as powerful oxidant, in minimizing the organic
load of MWW. The optimum dose of waste H2O2 was found as 2.5 ml L-1 which
significantly (p< 0.05) reduced BOD5 and COD in 120 min, thus meeting the NEQS for
MWW. The results revealed that disinfection capacity of 40% waste H2O2 at application
rate 2.5 ml L-1 caused significant reduction of fecal coliform populations to less than half
of the initial value while treating MWW.
88
References
APHA, American Public Health Association, Inc. (2005). Standard methods for the
examination of water and wastewater (21st Ed.), New York, USA.
Bull, A. R. & McManamon, J. T. (1990). Destruction of inorganic pollutants in
wastewater with hydrogen peroxide, Emerging technology in hazardous waste
management, American chemical society, Washington, DC.
De Morais, J. L. & Zamora, P. P. (2005). Use of advanced oxidation processes to
improve the biodegradability of mature landfill leachates. J. Hazard. Mater.
B123, 181-186.
Fernando, J., Beltran, J. M. (1997). Ozone-UV radiation-Hydrogen peroxide oxidation
technologies [EB/OL]. Online: Access date [2009-10-24].
http://www.crcnetbase.com/doi/abs/10.1201/9780203912553.ch1
Geissen, S.U. Water demand in arid countries: an opportunity to reduce environmental
pollution, in: Mediterranean Area Proceedings of the International Conference
WATRAMA, Tunis. (2000).
George, T. (2004). In: Wastewater engineering treatment and reuse. pp. 1196-1200. 4th
edition.
Glaze, W.H. (1987). The chemistry of water treatment processes involving ozone,
hydrogen peroxide, and ultraviolet radiation. Ozone-Sci. Eng. 9, 335-342. Online:
Accessed date 17/10/2008.
http://www.scribd.com/doc/7164171/DK2874CH1.
IHP, Introduction to Hydrogen Peroxide. Online: accessed on 27/12/2008.
http://www.h2o2.com/intro/overview.html.
treatment, Tunisia. Chem. Eng. J. 119, 161165.
Lazarova, V., Cirelli, G., Jeffrey, P., Salgot, M., Icekson, N. & Brissaud, F. (2000).
Enhancement of integrated water management and water reuse in Europe and the
Middle East. Water Sci. Technol. 42, 193202.
Liotta, L. F., Gruttadauria, M., Di Carlo, G., Perrini, G. & Librando, V. (2009).
Heterogeneous catalytic degradation of phenolic substrates: Catalysts activity. J.
Hazard. Mate. 162, 588-606.
89
Metcalf & Eddy. (2003). In: Wastewater engineering treatment and reuse. pp. 11961202. McGraw-Hill.
Millero, F.J., LeFerriere, A., Fernandez, M., Hubinger, S. & Hershey, J.P. (1989).
Oxidation of H2S with H2O2 in natural waters. Env. Sci. Technol. 23, 209213.
Olmez, H., Kretzschmar, U. (2009). Potential alternative disinfection methods for
organic fresh-cut industry for minimizing water consumption and environmental
impact. LWT- Food Sci. Technol. 42, 686-693.
Song, N.T., & Hiraoka, M. (1992). Anaerobic treatment of sewage sludge treated by
catalytic wet air oxidation process in up flow anaerobic sludge blanket reactors.
Water Sci. Technol. 26, 867895.
Tetra Pak Technical data manual. (2008). Hydrogen peroxide, Doc. No.OM-27717260101 pp 8-9.
Verstrate, W. (1998). In: Microbial ecology. Practical course notes, Ghent University
Belgium.
World Bank. Online: accessed date 22/05/2011.
worldbank.org.pk/WBSITE/EXTERNAL/COUNTRIES/SOUTHASIAEXT.
90
5 Chapter 5:
Integrated Carwash Wastewater Treatment by Hydrogen
Peroxide
91
Abstract
Car wash wastewater (CWW) contains petroleum, hydrofluoric acid, ammonium
bifluoride products, paint residues, rubber, phosphates, oil, grease and volatile organic
compounds (VOCs). The present study dealt with various investigations conducted for
the treatment of CWW. A treatment system of five liters capacity was designed in the
laboratory. Due to high load of oil and grease, CWW was aerated and scum was
removed. Alum was used as coagulant in primary treatment which resulted 93% and 97
% reduction in COD and turbidity. During secondary treatment CWW was further treated
with waste H2O2 which resulted in further 71% and 83% reduction in COD and turbidity,
respectively. Other desirable changes were also observed in pH, TDS, conductivity and
DO contents. It was concluded that designed system could be effectively used to treat
carwash wastewater that could be reused in the same station.
Keywords: Car wash wastewater, coagulation, waste H2O2, chemical oxygen demand,
turbidity
92
5.1 Introduction
Water is one of the most precious needs for life on earth. Scarcity of water can be
handled if proper planning is set for wastewater treatment, reuse or discharge into aquatic
system. In developed countries, carwash industry is conscious of the needs for recycling.
Developing courtiers are still behind to develop conscious for their wastewater produced
by carwash industries. Cars that are washed in the street can pollute streams, rivers, bays
and estuaries (Huybrechts et al., 2002). The soaps, oil and grimes that run off the car into
the gutters, go into the storm water system. Storm water unlike the water that enters the
sewers does not undergo treatment before it is discharged into waterways. Any pollutants
in storm water end up in our lakes, rivers, harbors and oceans, and are considered nonpoint source pollution (EPA, 1994).
Wastewater from car washing stations contains a number of impurities such as
sand and dust, free oil, grease, oil/water emulsion, carbon, asphalt, salts, surfactants and
organic matter, which is discharged directly into municipal sewage treatment plant
(Hamada and Miyazaki, 2004). A non the average, 100 liters water is generated per car
and at least 10 m3 of water is discharged from a car wash station per day, there is still a
large amount of water consumed in city. Due to the amount of the water and complexity
of the water quality, from a viewpoint of environmental protection and effective
utilization of water resources, reuse of carwash water is an important subject.
Furthermore, a small space and high efficient treatments are required due to the limited
space of car wash station and high reuse water quality for car washing.
The wastewater generated from the carwash is discharged into the sewage system
without any treatment. The treatment of such wastewater needs diverse methods, which
can be economical as well as effective. A cellulose acetate hollow fiber type ultra
filtration membrane was used to enhance the process for the treatment and reuse of the
wastewater (Toyozo and Miyazaki, 2004). A carwash recycling and reuse system was
also designed by Al-Odwani et al., (2007). In another study nanofilteration retaining
surfactants were used to reduce organic components (Boussu et al., 2006).
93
The aim of this study was to explore the possibility of integrated treatment concept
for carwash wastewater to an acceptable level so that it can be discharged into water
bodies.
Table 5-1 Characteristics of the raw car wash wastewater
Parameters
pH
Conductivity (S/cm)
TDS ( mg L-1)
TS ( mg L-1)
Salt (%)
DO ( mg L-1)
Turbidity (NTU)
COD ( mg L-1)
Oil contents ( mg L-1)
Characteristics
8.750.05
1289.60.577
644.330.55
5855.6610
2.50.01
Nil to 0.900.002
7721
10192
83.70.3

5.2.1 Wastewater and waste H2O2 collection
The wastewater samples were collected from a service station in Abbottabad, Pakistan.
H2O2 was collected from a food industry where it was used already in a disinfection
process. The characteristics of CWW are summarized in Table 5-1.
5.2.2 Experimental design

Experimental setup was divided into two parts: i) Physical treatment, and ii)
Chemical treatment. In order to remove excess oil content which might interfere with the
further chemical treatment, aeration was applied for one hour and scum was removed
manually with scrapper.
During aeration grit and other unwanted pollutants were
removed after foam moving to the surface. The experimental design has been given in
Figure 5.1.
Aeration tank was linked with second tank containing a mixing apparatus with a
rotation speed set at 480-500 rpm. In mixing chamber alum was added and mixed. The
tanks were made up of glass-fiber material with capacity of 1.5 liters each. For chemical
treatment, Al2(SO4)3.16H2O was used and optimized by using concentration of 10, 20 mg
L-1 to 80 mg L-1, after the removal of oil. Last tank was used to mix waste H2O2 (40%)
94
with the optimized dose of 2.5-3 ml L-1. The experiments for wastewater treatment were
carried out at the ambient temperature (25oC).

Raw and treated samples were analyzed for their COD, TDS, pH, turbidity etc
according to the standard methods (APHA, 2005). For COD determination closed reflux,
calorimetric method included digestion at 150oC for 2h in COD vials followed by
spectrophotometer reading at 530 nm (APHA, 2005). The pH was measured using a
digital pH meter (HANNA, HI 991003 Sensor Check pH), TDS and conductivity by
HANNA, HI9835 Microprocessor for conductivity/TDS.

5.3.1 Aeration for oil water separation
The main objective to administer aeration system was to remove oil content from
wastewater. Air bubbles developed at the bottom of the aeration chamber might have
entrapped the oil at the wall of bubbles carrying oil to the surface. After 90 minutes of
aeration 96.3% of oil content was removed (Figure 5.2). The maximum removal took
place during first 15 minutes (49.22%) and consequent to decrease of the concentration of
oil from wastewater removal efficiency also decreased. The difference in the densities
between oil and water helped to move oil upwards, where it was removed by scraper.
Figure 5.1 Schematic diagram of a multi-stage treatment of carwash wastewater
95
Figure 5.2 Effect of aeration on oil contents of CWW
Figure 5.3 Turbidity reduction of CWW after alum dosing
96
5.3.2 Effects of treatment on turbidity of CWW

The wastewater generated after car washing contains detergents, shampoo and diesel,
the materials which make the carwash wastewater very turbid. The present treatment
strategy resulted in reducing turbidity from 772 NTU to 33 NTU, showing a 96%
reduction when 80 mg L-1 of alum was added (Figure 5.3). From initial turbidity value of
772 NTU an alum dose of 10 mg L-1 caused turbidity reduction to 289 NTU. Increasing
alum dose to 20 mg L-1 and 30 mg L-1 showed no appreciable decrease in turbidity
(62.85% and 66.58%, respectively). During coagulation, suspended particles are
destabilized to promote their agglomeration producing larger particles that can be readily
removed during subsequent treatment processes. In many cases, dissolved organic
substances may be absorbed on the surface of suspended solids particles and are
therefore, removed as well. Colloidal size particles typically carry an electrical charge
(Metcalf and Eddy, 2003). When used at relatively low doses (< 5 mg L-1), charge
neutralization (destabilization) is believed to be the primary mechanism involved. At
higher dosages, the primary coagulation mechanism is entrapment.
5.3.3 Influence of alum treatment on COD removal

The COD reduction was very promising (Figure 5.4). The initial COD of raw
wastewater sample was 1019 mg L-1. The decrease in COD concentration had a direct
relation with the increasing alum. With the increase of alum concentration to 30, 40 up-to
80 mg L-1 resulted in respective COD reductions to 681, 601, 180 and 70 mg L-1. The
COD reduction percentage of 92.35% was observed at 80 mg L-1 of alum concentration
showing that alum was a very efficient coagulant for COD reduction. Total COD
reduction, after combined effect of aeration, alum treatment and peroxide oxidation, was
94.43%. The quality of treated effluent met the NEQS and thus could be discharged into
ambient environment. Increased alum doses above 80 mg L-1 might cause an increase in
TDS (Bhatti, 2009) due to release of excessive aluminum species into wastewater if
sufficient opposite charged particles were not available (Baisali 2005).
97
Figure 5.4 COD Reduction (mg L-1) of CWW at different application rates of alum
5.3.4 Effects on TDS after alum treatment

Total dissolved solids of CWW decreased after treating with integrated treatment
alum and waste H2O2. Overall, TDS reduction was up to 9.94% at 40 mg L-1 of alum
dose. It implied that treatment with alum alone was not affective (Figure 5.5). There was
some limitation in TDS reduction using alum. The hydrolysis of Al2(SO4).16H2O in
aqueous medium results in production of some positively charged mono and polynuclear
species. These positively charged compounds react with colloids attained with negative
ions present in the wastewater. These combined hydroxides settled down by the gravity
force and help in reduction suspended solids and COD. The increase of TDS might be
possible if free mono or polynuclear species do not combine with colloidal particles due
to very few or positive species (Baisali, 2005). Increase in TDS is only possible if free
available charged species are left in decant. The CWW sample may show same response
after treating with alum at different concentrations. It was observed only 13% reduction
in TDS occurred at 80 mg L-1 alum dose followed by waste H2O2 treatment. Thus treated
wastewater after the addition of alum and waste H2O2 may show little hardness and
additional methods are required to remove its hardness.
98
5.3.5 Effect of treatment on pH of CWW

The pH of the treated wastewater decreased after the addition of alum and it
increased again when H2O2 was added in CWW. Optimum particle removal by sweep
flock occurs in the pH range of 7 to 8 with alum (Metcalf and Eddy, 2003). The CWW
was treated with optimized dose of 80 mg L-1 of alum with COD removal 82.33% where
post treatment pH observe was 7.2
Figure 5.5 Effect of treatment on TDS of CWW
Figure 5.6 Effect of treatment on pH of CWW
99
. The combination of alum prior to waste H2O2 addition seemed quite feasible as
alum addition caused pH decrease around 7.5 and it increased again when H2O2 was
added. Treatment combination was found very effective in COD reduction; color
removal, odor and pH control (Figure 5.6).
5.3.6 Effect of treatment on dissolved oxygen (DO) of CWW

Adequate dissolved oxygen is necessary for optimum water quality. Alum
treatment resulted in the rise of DO to its minimum required level in CWW (Figure 5.7).
Temperature is also important factor for the solubility of oxygen in water as well as
dissolved organic solids. Increase in organic matter utilizes oxygen for chemical reaction.
In present study, alum and H2O2 treatment of CWW caused an increase in DO to 4.20
mg L-1 from an initial level of 0 mg L-1.
Figure 5.7 Effect of treatment on DO of CWW
5.3.7 Influence of H2O2 addition on CWW

The present study involved waste H2O2 treatment subsequent to alum addition.
The alum acted as a coagulant while waste H2O2 was an oxidant. After the aeration and
coagulation treatment phase of CWW, it was further treated with 3 ml L-1 of waste H2O2,
while it was continuously stirred with an electric mixer at 480 rpm. The time period for
its treatment was 2 hours (Figure 5.8). Significant reduction in these parameters was
recorded.
100
Figure 5.8 Removal percentage of TDS, COD, Turbidity and Oil contents from CWW
In the present age of water crisis, it is highly desirable to treat and conserve large
amounts of wastewaters generated from carwash industry that can be reused in same
industry or in agriculture. To address this problem various reuse systems for carwash
water such as sand filtration (Nakajima et al, 1986), absorption (Okumura and Onoue,
1978), ozone (Camilo et al.,1999) and biological (Suzuki et al., 2000) treatments have
been previously developed and commercialized. Nevertheless, most of these systems are
not satisfactory for the quality of reuse water, especially because of the difficulty in
perfect removal of both particles and oil-water emulsion (Hamada and Miyazaki, 2004).
A small space and low-cost treatments are required for the reuse of carwash water
(Hamada and Miyazaki, 2004). Pretreatment using a conventional flocculating agent
before the membrane system has been well known as a technique to remove fouling
substances and make permeation flux increase (Harris et al., 1976; Lahoussine-Turcaud
et al., 1990a; Lahoussine-Turcaud et al., 1990b; Winfield, 1976). If this technique is
directly applied to the reuse of carwash water, a large space, pH control and large amount
of several kinds of flocculating agents are necessary because it is difficult to remove the
oil-water emulsion completely that is in carwash wastewater (Hamada and Miyazaki,
2004).
101
Table 5-2 Characteristics of the car wash wastewater before and after the treatment. *Below
Detection Limit
Parameters
pH
Conductivity (S/cm)
Characteristics Before
Characteristics After
Treatment
Treatment
8.75
7.50.05
1289.6
9605.00
TDS (mg L-1)
644.33
5515.70
TS (mg L-1)
5855.66
53840
Salt (%)
2.5
20.20
DO (mg L-1)
BDL* to 0.90
4.01.00
Turbidity (NTU)
772
430.50
COD (mg L-1)
1019
702.65
Oil contents (mg L-1)
83.7
3.10.11
Please note that the each value represents average of three independent determinations.
The uniqueness of the present study was that we applied aeration initially that
effectively removed more than 95% oil content from CWW. Aeration was followed by
alum addition as a coagulant. Finally, waste H2O2 was applied to oxidize most of COD
from CWW. The effect of treatment strategy on the characteristics of CWW has been
shown in Table 5-2. It is evident that the present approach is cost effective and requires
less space without any pH control. However, little concern is the hardness of treated
wastewater which needs some treatment before it can be reused.
5.4 Conclusions
The integrated treatment processes for CWW consisting of aeration, alum and
waste H2O2 reduced the 96% of the oil contents from carwash wastewater. Other
parameters like COD, turbidity and TDS were reduced upto 93%, 94% and 74%,
respectively. The present approach is cost effective and requires less space without any
pH control. Thus the treatment process can be applied on pilot scale to further evalute its
efficiency.
102
References
Al-Odwani, A., Ahmed, M. & Bou-Hamad, S. (2007). Carwash water reclamation in
Kuwait. Desalination. 206, 17-28.
APHA, American Public Health Association, Inc. (2005) Standard methods for the
Baisali, S., Chakrabarti, P. P., Vijaykumar, A. & Kale, V. (2005). Wastewater treatment
in dairy industries- possibility of reuse. Desalination. 195, 141-152.
Bhatti, Z. A., Mahmood, Q., Raja, I. A., 2009. Sewage water pollutants removal
efficiency correlates to the concentration gradient of amendments. J. Chem. Soc.
Pakistan. 31, 665-673.
Boussu, K., Kindts, C., Vandecasteels, C. & Van der Bruggen, B. (2006). Applicability of
nanofiltration in the carwash industry. Sep. Purif. Technol. 54, 139-146.
Camilo, V., Gonzalo, A. & Kirby, M. (1999). A new high efficiency automatic car wash
water recycling system.
In: WEF/Purdue Industrial Wastes Conference,
Indianapolis, USA. 938-954.
EPA, EPA's polluted brochure EPA-841-F-94-005, US Gov. (1994).
Hamada, T., Miyazaki, Y., (2004). Reuse of carwash water with a cellulose acetate
ultrafiltration membrane aided by flocculation and activated carbon treatments.
Desalination. 169, 257-267.
Harris, F., Humphreys, G. & Spiegler, K. (1976). Reverse osmosis (hyperfiltration) in
water desalination. Mem. Sep. Proc. 1, 122-186.
Huybrechts, D., De Baere, P., Van Espen, L., Wellens, B. & Dijkmans, R. (2002). Best
available techniques for carwash and truckwash, BBT study VITO:
http://www.emis.vito.be.
Lahoussine-Turcaud, V., Wiesner M.R. & Bottero, J.Y. (1990). Fouling in tangentialflow ultrafiltration: the effect of colloid size and coaguration pretreatment. J.
Mem. Sci. 52, 173-190.
Lahoussine-Turcaud, V., Wiesner, M.R., Bottero, J.Y. & Mallevialle, J. (1990).
Coagulation pretreatment for ultrafiltration of a surface water. J. AWWA. 82, 7681.
103
Metcalf & Eddy. (2003). In: Wastewater engineering treatment and reuse. pp. 1196-1202.
McGraw-Hill.
Nakajima, T., Kurosaki B. & Udagawa, H. (1986). Carwash wastewater treatment. Patent
No. 61020324, JP.
Okumura, M. & Onoue, K. (1978). In: Proc. 53rd Annual Meeting of Sen-i Gakkai,
Tokyo, 171.
Suzuki, M., Umehara, T., Tsukamoto, K. & Tsukahara, H. (2000). Recycle device of car
washing machine waste water and recycle method of car washing machine
guttation, Patent No. 2000000585, JP.
Toyozo, H. & Miyazaki, Y. (2004). Reuse of carwash water with a cellulose acetate
ultrafiltration membrane added by flocculation and activated carbon treatments.
Desalination. 169, 257-267.
Winfield, B. (1976). Waste treatment with reverse osmosis membranes. Mem. Sep.
Biotechnol. 1. 355-373.
104
6 Chapter 6:
Municipal Wastewater Treatment by Physico-Chemical
Processes
105
Abstract
Dilemmas like water shortage, rapid industrialization, growing human population and
related issues have seriously affected human health and environmental sustainability. For
conservation and sustainable use of our water resources, innovative methods for
wastewater treatment are continuously being explored. AOPs show a promising approach
to meet specific objectives of MWW treatment. The MWW samples were pretreated with
Al2(SO4)38H2O (Alum) at different doses 4, 8, 12 to 50 mg L-1 to enhance the
sedimentation. The maximum COD removal was observed at alum treatments in range of
28 to 32 mg L-1 without increasing TDS. TDS were found to increase when the alum dose
was increased from 3240 mg L-1. In the present study, the optimum alum dose of 30
mg L-1 for 3 hours of sedimentation and subsequent integrated H2O2/UV treatment was
applied (using 2.5 ml L-1 of 40% waste H2O2 and 35% fresh H2O2 separately). Organic
and inorganic pollutants, contributing towards COD, BOD, turbidity and TDS were
degraded by H2O2/UV. About 93% COD, 90% BOD and 83% turbidity reduction
occurred when 40% waste H2O2 was used. After using fresh H2O2, COD, BOD and
turbidity reduction was 63%, 68% and 86% respectively. Complete disinfection of
coliform bacteria occurred by using 40% H2O2/UV. The most interesting part of this
research was to compare the effectiveness of waste H2O2 with fresh H2O2. Waste H2O2
generated from an industrial process of disinfection was found more effective in the
treatment of MWW than fresh 35% H2O2.
Keywords: Advanced oxidation process, biological oxygen demand, biodegradable
fraction, chemical oxygen demand, integrated chemical treatment, waste H2O2
106
6.1 Introduction
Chemically enhanced methods, in conjunction with AOP provides an efficient and
promising alternative to conventional methods for the treatment of MWW. These
techniques can be used in combination with the conventional methods to increase the
overall performance of the wastewater treatment plant (WWTP). Various studies have
shown that AOPs can be utilized to decompose substances such as insecticides, dyes,
surfactants and organochlorides into relatively harmless substances such as carbon
dioxide and water (Fox, 1993; Yonar, 2006). Treatment with alum beforehand may
further enhance the wastewater treatment using AOPs. Velasco et al., (2007), studied the
effect of aluminum sulphate and Poly Aluminium Chloride (PAC1) as a coagulant for the
removal of dissolved organic carbon of surface waters. It was found that the efficiency of
alum was highly dependant on operational conditions such as pH and dose. The pH tends
to affect the solubility of aluminum in coagulation, which is favored under more acidic
conditions since acceptable residual aluminum concentration is achieved, whereas
aluminum solubility increases and therefore pH effect must be balanced (Sarkar, 2005).
ln another study, alum and aluminum hydroxide was used for the removal of phosphates
from wastewater, which are the major contributors of the eutrophication of water bodies
(Georgantas and Grigoropoulou, 2007). Alum was found to be a better chemical for
phosphate removal even though the active coagulant formed was Al(OH)3. Temperature
did not affect alum action but aluminum hydroxide showed variations with the change of
temperature.
In Tunisia, the DWW was proposed to be treated using H2O2 so as to meet the
problem of water shortage and recycle the wastewater for further reuse. According to the
research, 30% H2O2 increase the biodegradability of some water pollutants and an
optimum dose of 2.5 ml L-1 was sufficient to destroy majority of the risks even though it
may vary according to the amount of organic matter present in water. COD reduction
achieved was about 85%. Significant decrease in BOD5 was also observed as well as
exponential inactivation of fecal coliform was achieved (Verstaete, 1998; Ksibi, 2006;
Rosal, 2008). In another research, DWW was treated in batch and continuous mode using
H2O2/UV/O3. Beforehand, the water was pretreated using three different methods for
107
turbidity removal, which might hinder the effect of the latter treatment, namely; plain
sedimentation. The results showed that neither plain sedimentation nor filtration showed
substantial results, but aluminum sulfate at an optimum pH of 7 and optimum dose of 60
mg L-1 showed appreciable reduction in COD (39%) and turbidity (84%). This resulted
in better effluent COD as opposed to raw wastewater. No doubt, H2O2 concentration was
an important parameter, and the greatest decrease in COD was found to be at 100 mg L-1.
The process greatly reduced the reaction time due to UV lamps and enormous decrease in
the amount of residual COD. In addition, the water microbial count was also significantly
reduced (Yonar et al., 2006; Teresa et al., 2006). In another study, use of ozone increased
the level of hydroxyl radicals and increased the rate of degradation of organic pollutant in
DWW (Legrini et al., 1993).
However, the use of fresh H2O2 may be costly. Moreover, the H2O2 alone or in
combination with alum coagulation can not effectively remove microbial loads from
treated MWW which would be reused. The specific objectives of this study were to
compare the effectiveness of used and fresh H2O2 to treat the MWW and to reduce the
alum dose for chemical sedimentation. The combination of H2O2 with UV light was
investigated to observe the effectiveness of integrated treatment of organic matter.

6.2.1
Wastewater sampling
MWW samples were obtained from Shaikhul-bandi Abbottabad, Pakistan. For
this purpose, 50 L plastic container was conditioned properly using running MWW. After
sample collection it was corked and taken to the laboratory for further analysis and
treatment. Its characteristics are given in Table 6-1. Waste H2O2 was collected from drain
of Tetra Brik Aseptic (TBA) machine in a food factory located in Hattar Industrial Estate,
Hattar near Abbottabad, Pakistan. During TBA machine operation fresh 35% H2O2 is
changed to 40% H2O2 which is wasted and drained. MWW comprised of effluents from
kitchen, washrooms, washing, laundry etc.
MWW contained a large quantity of organic pollution with 0.9 biodegradable
fractions (George, 2004). UV lamp was used for ultraviolet disinfection with
108
specification of 240 280 nanometers, 16000 32000 microwatt-second per square with
water depth range 2 to 3 inches, brand light source USA.
Table 6-1 Pre and post experimental Analysis
Parameters
pH
TDS (mg L-1)
COD (mg L-1)
BOD (mg L-1)
Turbidity
(NTU)
Raw WW
Alum
treatment
8.50.05
7.90.20
60015.00 58035.00
2953.20
1325.00
2000.50
882.00
18615.00
484.50
Fresh 35 (%)
H2O2
Treatment
9
504
98.66
58
24
Waste 40 (%)
H2O2
Treatment
7.8
572
20
19
30
6.2.2 Optimization of H2O2 dose

In order to evaluate the optimum amount of 40% H2O2 for BOD, COD removal
and total plate count reduction, a series of experiments were conducted with optimized
doses of alum and then treated with H2O2, 28 to 32 mg L-1 and 2.5 ml L-1. During
pretreatment alum was tested as 4, 8, 12 to 50 mg L-1, the alum dose between 28 to 32
mg L-1 was found the most effective in the removal of COD and BOD without increasing
TDS of effluent. In these experiments, BOD, COD removal and reduction of total plate
count were measured throughout the reaction period of 30, 60, 90, and 120 min.
6.2.3 Treatment system

A mixer with variable rotational speed of 0-500 rotations per minute (rpm) was
used to mix the sample thoroughly. One-liter of raw MWW was treated in batch reactor
at mixing speed of 500 rpm. As a first step, it was treated with alum dose 28-32 mg L-1
during chemically enhanced primary sedimentation (CEPS) and decant of CEPS was
used further to treat with two different concentrations of H2O2 /UV (35% fresh H2O2 and
40% waste or used H2O2), at the concentration (v/v) of 2.5 ml L-1 applied to various
samples of wastewater, with continuous stirring at 500 rpm. Before to start mixing, at
time zero, 35% and 40% H2O2 doses were separately added and samples were drawn at
time intervals of 30, 60, 90 and 120 minutes after the addition to test their effectiveness.
All the experiments were conducted at ambient temperature of 25+2oC. Figure 6.1 shows
the process flow sheet and the treatment outline.
109
6.2.4 Microbial count

The membrane filter technique was used for microbial analysis (Verstrate, 1998).
For this purpose, various dilutions (10-3 to 10-6) were made of the wastewater sample.
Nutrient agar (2%) was used as solidifying medium in sterilized petri dishes. 100 mL
diluted MWW sample was filtered through filter paper (0.45m porosity) and incubated
at 35oC for 24 h. The colonies were counted under the compound microscope at
magnification power of 10-15 X (Results are not shown).
Figure 6.1 Major steps involved in MWW treatment

wastewater analysis (APHA). Wastewater samples were analyzed prior to and after the
treatment with 40% waste and 35% fresh H2O2 during separate treatment. BOD5 was
measured by using standard method (APHA, 2005), COD was determined by closed
reflux colorimetric method using digester (HACH - LTG 082.99.40001) (APHA). The
wastewater sample, digestion solution and sulphuric acid were digested in vials for two
hours at 150oC. After digestion, absorbance was measured at wavelength 605 nm in a
spectrophotometer (LOVIBOND tintometer GMBH, 44287 DORTMUND). The pH
meter (HANNA, HI 991003) was used for pH determination. The H2O2 was measured
according to Tetra Pak Technical data manual by using hydrometer and temperature.
H2O2 value was obtained after connecting temperature and hydrometer reading on third
scale of H2O2 W/W (Tetra pack). Fresh H2O2 was purchased from local market 35%
concentration. Various steps of the treatment have been illustrated in process steps below:
110
1) Domestic Wastewater collection (Sample)

2)
Natural Sedimentation For 1hour
Alum treatment 30 mg L-1 (3 hrs sedimentation)
3) Chemical oxidation of CEPS effluent with

Waste H2O2 40% (collected from Food Industry) and 35% fresh H2O2
i. Sample collected after 30 minutes of mixing
ii. Sample collected after 60 minutes of mixing
iii. Sample collected after 90 minutes of mixing
4. Sample collected after 120 minutes of H2O2

A) Steps involved in proposed treatment process of low cost treatment of
domestic wastewater

6.3.1 Effect on pH
During high turbidity and subsequent alum dosing, the MWW pH is likely to drop
because alum reacts with carbonates and hydroxyl species therefore removing base from
solution. Upon its addition to water, calcium and magnesium bicarbonate alkalinity reacts
with the alum to form an insoluble aluminum hydroxide precipitate. Owing to its acidic
nature of alum, its addition to the wastewater slightly decreases the pH from 8.03 to
about 7.4 after the addition of alum 28-32 mg L-1 (Figure 6.2).
The changes in pH with respect to time were inconsequential. Only a slight
increase in pH was observed which may be due to the oxidation of organic dissolved
solids in effluent. The pH changed from about 7.4 to 7.8 after 120 minutes when using
waste H2O2 and 8 to 8.7 pH with fresh H2O2 (Figure 6.2). The pH indicates the
degradation reaction occur due to mixing of H2O2 and leads basic by product like HCO3111
(pH8). It seemed that pH values of MWW did not fluctuate significantly (p < 0.05) after
dosing with alum and subsequent treatment with H2O2 and thus should not be considered
in the process design.
Figure 6.2 Effect of fresh H2O2 treatment on pH with the passage of time
6.3.2 Changes in turbidity

Natural sedimentation and CEPS with alum greatly reduced the turbidity of wastewater.
By increasing the dose of alum, turbidity was reduced to 71.08% (Figure 6.3) from 166
NTU to 48 NTU. The basic purpose of the alum addition was to form flocks and remove
enough particulate matter to make further disinfection with H2O2 more effective. During
subsequent step, H2O2/UV treatment could be effective only if particulate matter had
removed in CEPS process. Turbidity removal in the range of 82.7% to 86.36% was
observed after treating with 40% waste H2O2 and 35% fresh H2O2 when mixed for 120
minutes at a retention time of 12 hours. Figure 6.3 showed that fresh H2O2 was more
effective to reduce the turbidity when compared with waste H2O2. Turbidity removal with
alum (71.08%) was observed in CEPS process and second further decrease in turbidity
after 120 minutes of mixing with H2O2. This figure shows that the maximum effect of
fresh H2O2 was observed in reduction of turbidity while in Table 6-1 waste H2O2 was
most effective against COD and BOD removal than the turbidity.
112
Figure 6.3 Decrease in turbidity after treating with alum and H2O2/UV, (Raw WW represents raw
wastewater, NS = Natural Sedimentation)
6.3.3 Effect on COD and BOD after treating with 35% fresh H2O2/UV and
40% waste H2O2/UV
Noteworthy reduction in the COD and BOD of the MWW was seen more
effective reduction by 40% waste peroxide treatment. Figure 6.4 shows that both BOD
and COD reductions were different when treating the wastewater samples with two
different concentration of peroxide separately. Natural sedimentation and alum treatment
had similar effects as shown in the Figure 6.4. Reduction in COD and BOD observed was
upto 87% and 89% after the 30 minutes mixing of 40% waste H2O2 and both parameters
reduced further to 96 and 90% after 60 minutes of mixing. After 120 minutes no further
decrease in COD and BOD was observed. COD reduction was very sharp with in 30
minutes mixing of 40% waste peroxide. Effective reduction in COD and BOD occurred
by treating same sample with 35% fresh H2O2 after 120 minutes of mixing. In this
treatment, the use of fresh H2O2/UV caused continuous decrease of COD and BOD
after120 minutes of mixing. While using waste H2O2/UV treatment, there was continuous
decrease in COD and BOD values till 60 minutes as 20 and 19 mg L-1, after 60 minutes
no further decrease was observed. It indicated that using waste H2O2 was effective for 60
minutes than fresh H2O2. Where as the obtained results of COD and BOD were 98 mg L-1
and 58 mg L-1 with fresh H2O2 showing effective results after 120 minutes. H2O2 is one
113
of the most powerful known oxidizer and results in the formation of hydroxyl radicals
(OH), which reacts with the pollutants such as iron, sulfide, solvents and gasoline as well
as pesticides present in MWW, thus, reducing the contamination level in water. UV
radiation provides the necessary energy for carrying the various chemical, physical and
biological processes for the oxidizing the pollutants. These oxidations entail an array of
direct and indirect photoreactions which are initiated by the absorbed UV radiation.
Moreover, UV light can also disinfect the water samples.
Figure 6.4 Reduction of COD and BOD after treating with 35% fresh and 40% waste H2O2 along
with UV light (Raw WW represents raw wastewater, NS = Natural Sedimentation)
Table 6-1 shows the characteristics of MWW prior to and after integrated
chemical treatment. A comparison of degradability of fresh and waste H2O2 has been
given in Figure 6.4. It is clear that when using 40% waste H2O2 with UV light, 30
minutes of mixing can be sufficient for the reduction of COD and BOD while fresh
peroxide with UV needs more than 2.5 ml of peroxide and a longer time to reach the 90%
removal efficiency. In another study (Kisibi, 2006) more than 90% COD removal
efficiency was achieved by 3 ml of fresh peroxide without using UV light. In previous
studies (Bhatti et al., 2009), alum alone was not sufficient to decrease COD and BOD.
114
6.3.4 Microbial activity

UV treatment with peroxide can easily inactivate, even with low H2O2 doses,
chlorine resistant species such as Giardia and Cryptosporidium which a dangerous human
pathogens. UV is a green technology as it is chemical free and produces no disinfection
byproducts. Hence, the most significant effect was observed during the inactivation of
fecal coliform, which decreased to 0 CFU/10ml after 60 minutes of peroxide/UV
treatment (Results are not indicated). Even after 30 minutes the microbial count had
fallen to 4 CFU/10ml of wastewater. Using primary and secondary wastewater treatment
processes alone for the reduction of enteric organism my results in 90-99.9% elimination,
and tertiary treatment may further decimate these pathogens, the treated wastewater could
still be contaminated by high microbial numbers. Henceforth, further disinfection of this
treated wastewater may be necessary. For this purpose, integrated H2O2/UV treatment
can be used.
The present investigation showed that CEPS may not be sufficient alone to treat
complex wastewaters especially industrial effluents. Some additional treatment
technologies especially anaerobic/aerobic treatments may be employed for the effective
treatment. Further research work is required to investigate the unit cost of operations.
6.4 Conclusions
The present study compared the effectiveness of used and fresh H2O2 to treat the
MWW and to reduce the alum dose for chemical treatment. The combination of H2O2
with UV light was found very effective to decrease BOD, COD, turbidity and coliform
bacteria in MWW. Waste H2O2 generated from an industrial process of disinfection was
found more effective in the treatment of MWW than fresh 35% H2O2. The waste H2O2
can be applied in combinations with UV light to treat MWW effectively.
115
References
Bhatti, Z. A., Mahmood, Q. & Raja, I. A. (2009). Sewage water pollutants removal
efficiency correlates to the concentration gradient of amendaments. J. Chem. Soc.
Pakistan. 31(4), 665-673.
Fox, M. A. & Dulay, M. T. (1993). Heterogeneous photocatalyst. Chemical Reviews. 93,
341-358.
Georgantas, D. A. & Grigoropoulou, H. P. (2007). Orthophosphate and metaphosphate ion
removal from aqueous solution using alum and aluminum hydroxide. J. Colloid.
Interf. Sci. 315, 70-79.
George, T. (2004). In: Wastewater engineering treatment and reuse. pp. 1196-1200. 4th
edition.
Kisibi. M. (2006). Chemical oxidation with hydrogen peroxide for domestic wastewater
Legrini, O., Oliveros, E. & Braun, A. M. (1993). Photochemical processes for water
treatmet. Chem. Rev. 93, 671-698.
Rosal, R., Rodriguez, A., Perdigon-Melon, J., Peter, A. & Garcia-Calvo, E. (2008).
Oxidation of dissolved organic matter in the effluent of a sewage treatment plant
using ozone combined with hydrogen peroxide (O3/H2O2). Chem. Eng. J. 149,
311-318.
Sarkar, B., Chakrabarti, P. P. & Vijaykumar, A. (2006). Wastewater treatment in dairy
industries-possibility of reuse. Desalination. 195, 141-152.
Teresa, Z., Gunther, G. & Fernando, H. (2006). Chemical oxygen demand reduction in
coffee wastewater through chemical flocculation and advanced oxidation
processes. J. Env. Sci. 19(3), 300-305.
Velasco, U. & Juan, R. (2007). Enhanced coagulation under changing alkalinity- hardness
conditions and its implications on trihalomethane precursors removal and
relationship with UV absorbance. Sep. Purif. Technol. 55, 368 - 380.
Verstraete, W. (1998). In: Microbial ecology, practical course notes. pp. 20-30. Ghent
University
Belgium.
116
Yonar, T., Kadir, K. and Nuri, A. (2006). Treatability studies on domestic wastewater
using H2O2/UV process, Applied Catalysis. Environmental. 67, 223-228.
117
7 Chapter 7:
Municipal Wastewater Treatment by Integrated System
118
Abstract
The UASB reactor was used to treat mixed MWW at hydraulic retention time 2448 hrs and at an average temperature 25-34C. The aim was to test two stage treatment
concept for low cost MWW treatment as UASB in first stage and waste H2O2 40% 2
ml L-1 of UASB effluent at second stage. Moreover, the effect of micronutrients on the
treatability of UASB was also investigated. After start up with glucose for first 15days
(first stage), the reactor was fed with macro and micronutrients as SNI for 45 days
(second stage). The maximum substrate removal rate was same 0.07 d-1 for both glucose
and SNI. Removal efficiency of TSS, COD, TN, ortho-P and turbidity as 73%, 99%,
84%, 19% and 67%. Waste H2O2 was found successful in NH4+ removal during post
treatment where 80% nitrogen was removed. Low cost integrated treatment using UASB
and H2O2 was found an excellent novel treatment choice for mixed MWW in developing
countries.
Key words: Anaerobic treatment, COD removal, MWW, post treatment, waste H2O2
119
7.1 Introduction
Up-flow anaerobic bioreactor (UAB) reactor has been used since last decade to
treat sewage water due to its easy and low operating cost. However to shorten its start up
period reactor is often inoculated with active microorganisms/ granules otherwise it takes
more than three months or longer to achieve full efficiency (Lettinga, 1993). Its
application can be more with renewable energy production when treating rich organic
wastewater such as food industry wastewater (Boe et. al., 2008; La Motta et al., 2008).
At present, The UAB system is facing challenges in shortens the start up period
and guarantee high purification efficiency. Some reasons for this can be ascribed to a lack
of information on selection of sludge, kinetics involved during start up of low and high
strength wastewater treatment. Environmental factors can also effect on process kinetics
and substrate removal (Singh, 1999).
Anaerobic process includes principally three metabolic phases i.e. hydrolysis,
acidogenesis and methanogenesis (Cohen et al., 1982). Micro and macro nutrients
supplementation could be very effective in reducing startup period and achieving high
COD removal efficiency. Macro-nutrients such as nitrogen, potassium, phosphorus and
magnesium are required for activation or functioning of microorganisms. Micro-nutrients
such as nickel, cobalt and iron are known for their role as biochemical cofactors for
methane production (Speece, 1996). So it is possible that supplementation of macro and
micro-nutrients can enhance the organic matter degradation during anaerobic digestion.
The rate at which the organic matter converts or removes in any bioreactor is
governed by two main interconnected factors: the performance of the microbiological
processes and the hydrodynamics of the reactor. Biological wastewater treatment always
involves more than one phase working at the same time. In the normal operation of both
aerobic and anaerobic bioreactors, the liquid, solid and gaseous phases interact with each
other. Due to this, different factors such as mixing intensity, temporal and spatial
variations of mixing, degree of material segregation, gas bubbling pattern and intensity
all influence the hydrodynamic behavior of three phase reactors (Ottino and Khakhar,
2000; Bailey and Ollis, 1986). The hydrodynamic behavior of UASBs is also related to
the type of influent feeding device, up flow velocity, sludge bed depth and sludge
120
blanket height. Van der Meer and Heertjes, 1983, assumed that the fluid which flow in
the settling compartments of an UASB followed a laminar regime and the sludge bed and
sludge blanket were completely mixed, although the sludge bed volume could also have
dead spaces, bypassing and returning flows (Pena, 2006). UASB reactor was found poor
removal of total ammonium nitrogen and total kjeldahl nitrogen 1 mg L-1 each in UASB
effluent (Aiyuk, 2004).
Like other nutrients, it is important to remove nitrogen from wastewater due to
several environmental and health risks. Sources of nitrogen species in wastewaters is
from wastewater treatment plants, excessive use of swine manure, leachate and industrial
discharge (Van Hulle, 2005). During chlorination of drinking water carcinogenic
compounds may be formed. Therefore it is important to remove nitrogen as well along
with other noxious pollutant. A two steps treatment system was proposed to reduce
pollutant to acceptable level using low treatment cost. When treating such low organic
content in MWW with COD 200-500 mg L-1 UASB reactor offer great promise
especially for developing countries.
Moreover, during UASB treatment, nitrogen and phosphate remove to limited
extent during anaerobic treatment, so additional treatment is required when nitrogen and
phosphours removal is necessary. To overcome this problem AOP was installed where
waste H2O2 was used to see the effect on nitrogen and orthophosphate. This waste 40%
H2O2 was collected from a food industry where it was used to disinfect the packaging
material before juice packaging. During disinfection its concentration increased upto 40%
from 35% due to high temperature. The proposed strategy consists of UASB treatment
and then treatment with waste 40% H2O2.
7.2 Objectives
The objectives of the study were to evaluate some kinetics parameters of UASB,
effect of glucose, effect of micro and macro-nutrients for reactor start up. To study the
treatment effect on total nitrogen and orthophosphate removal during post treatment of
AOP using 40% waste H2O2. The overall treatment concept proposed as Low Cost
Municipal Wastewater Treatment.
121

7.3.1 Start up of UASB reactor
The whole treatment process was performed in a room where maximum and
minimum temperature was observed 35C and 15C during May to June. Both reactor and
mixing tank were connected with tubing to transfer the liquid. Reactor and mixing tank
was constructed with 5 mm thick transparent acrylic material. Inner diameter 11.7 cm and
total height 43.5 cm and recycling effluent was collected from 36.5 cm height and total
volume 4.6 liters with working volume 4.4 liters. The reactor had total five ports, three at
upper most part on right and left side of the reactor which was used for effluent collection
and recycling of the effluent. Upper most right side port was used to collect UASB
treated effluent for chemical oxidation process and center top over port was left for gas
collection.
Furthermore clogging of recycle pipe may cause bursting of the pipe which can
spill the reactor effluent. Failure of main recycle pipe leads to direct the fluid through
overflow standpipe. Recycling increases the liquid up-flow velocity in the reactor and
dilutes the influent moving inside the reactor. Therefore re-adjusting the HRT may
require. Two liters capacity jar, made with acrylic material, received UASB effluent for
oxidation to polish the effluent by H2O2 in batch system. H2O2 was added at the rate of 2
ml L-1. Optimization of H2O2 was reported in chapter third and fourth.
The reactor started up with single nutrient glucose for fourteen days (stage I) at
HRT of 48 hrs. Reactor parameters are summarized in Table 7-3. Sludge was collected
from a domestic septic tank located near COMSATS University Abbottabad. It was
opened after 10 years of its working condition. Synthetic nutrient influent composition
has been shown in Tables 7-1 & 7-2. The pH was adjusted with 1N NaOH and HCl
solutions for synthetic glucose and macro and micro-nutrients solution. For the initial two
weeks, it was not fed with any nutrients and only glucose was fed as carbon source. After
15 days, it was fed with micro and macronutrients (Stage II). Reactor was kept in a
separate room with day and night temperature fluctuations of 10C (20-30C) and it was
operated in a continuous mode. After 39 days HRT was reduced to 24 hrs from 48 hrs
with same loading rate to see the effect of glucose, macro and micro-nutrients. After
122
achieving stable COD removal of 99.90%, it was shifted to MWW and later on food
industry wastewater, which was being discharged directly into sewage system.
7.3.2 Determination of substrate uptake rate, biodegradable fractions and

growth yield
These parameters were determined after fitting the experimental data to equations
below.
U
Fb
S S e
.X
BODe
0.65 CODe
S Se
E o
So
100
BOD5 bCOD
Fb
0.65 COD COD
(1)
(2)
(3)
(4)
Where, U= specific substrate utilization rate (d-1); = HRT (h); So= influent COD (mg
L-1); Se= effluent COD (mg L-1); X =average VSS (mg L-1) concentration in reactor;
Fb = biodegradable fractions; BODe= Five day biochemical oxygen demand of effluent

(mg L-1), CODe = Chemical oxygen demand of effluent (mg L-1), E = removal efficiency
in (%) Fb = biodegradable fraction, bCOD= biodegradable chemical oxygen demand
(Mathiewu, 2000; Verstraete, 2005).
Previous investigation by Subramanyam, (2007) reactor was operated from 100 to
1000 mg L-1 of glucose with 8 hrs HRT and removal efficiency was 95%. In this study
microbial seed was collected from full scale UASB plant. In present study seed sludge
was collected from an underground septic tank at natural conditions with inflow and
outflow of toilet waste at home. Two liters of sludge filled in UASB reactor (Figure 7.1)
and started feeding with glucose for 14 days and later other essential nutrients were added
to increase the desired population of microorganisms. Addition of nutrients helps to
increase the active biomass. Higher active biomass results in higher COD removal rate.
Following table indicates the composition of synthetic influent containing trace elements
123
fed to the UASB reactor. The glucose solution was prepared as 0.5 g L-1 in distilled water
with average obtained COD 250300 mg L-1.
Table 7-1 Composition of synthetic influent (SNI)
Synthetic influent
Concentration
NaHCO3
Trace element solution
MgCl2
KH2PO4
(NH4)2SO4
1g L-1
1 ml L-1
1g L-1
1g L-1
0.24g L-1
Table 7-2 Component of trace element solution
Components g L-1
Components g L-1
Components g L-1
Na2-EDTA
FeCl24H2O
3.58
CoCl26H2O
0.5
NaOH
11
MnCl22H2O
2.5
(NH4)6Mo7O244H2O
0.5
CaCl22H2O
7.34
ZnCl2
1.06
CuCl22H2O
0.14
Table 7-3 Parameters (mg L-1) used to start up UASB reactor

Parameter
Value
Temperature (C)
Volume of reactor (L)
Volume of influent (L d-1 )
Concentration of influent (mg COD L-1 )
Mass loading rate (g COD L-1 hr-1 )
Hydraulic loading rate (L L-1 day-1)
Hydraulic retention time (hrs)
Upflow velocity (cm h-1)
20-30
4.6
2.16
300-350
0.144
0.48
48
0.05
Table 7-4 Standard allowable limits for effluent discharge
Working
Goal
mg L-1
COD
BOD
Kjel-N
NH4+
NO3-
PO4-
TN
SS
125
25
<10
15
35
These nutrients (MgCl2, KH2PO4, (NH4)2SO4 and trace elements) were compared with
glucose fed as influent nutrients in reactor.
124

the treatment with UASB and 40% H2O2. COD was determined by closed reflux
colorimetric method using digester (HACH - LTG 082.99.40001), (APHA, 2005), the
wastewater sample, digestion solution and sulphuric acid were digested in vials for two
hours at 150oC. After digestion, absorbance was measured at wavelength 605 nm in a
spectrophotometer (LOVIBOND tintometer GMBH, 44287 DORTMUND). The pH was
measured immediately after collection without stirring to prevent loss of CO2 from the
sample; such losses may cause changes in pH. The pH meter (HANNA, HI 991003)
was used for determination. H2O2 was measured according to Tetra Pak Technical data
manual by using hydrometer and temperature. H2O2 value was obtained after connecting
temperature and hydrometer reading on third scale of H2O2 W/W (Tetra Pak, 2008).
Figure 7.1 UASB followed by chemical oxidation with 40% hydrogen peroxide. P1= peristaltic feed
pump, P2 = peristaltic recycle pump
Kjeldahl nitrogen is the sum of organic nitrogen and ammonia nitrogen. Semimicro-Kjeldahl method (4500-Norg) digestion was performed for one hour and two at 200
and 300C followed by distillation was used where sum of organic and ammonia nitrogen
was measured. For NO3 and NO2 WAGSTECH KIT was used for determination.
Ammonia was measured by titrimetric method (4500-NH3 C).
125

7.4.1 Effect of glucose during UASB start up period
Concentration of glucose was added at rate of 0.5 g L-1 in tap water which was
equivalent to COD value of 250-350 mg L-1. Reactor efficiency was monitored to check
the effect of glucose on its reduction of startup period. Reactor sludge was allowed to
grow on glucose as substrate for first 15 days.
Figure 7.2 pHi (influent), pHe (effluent) comparison during start-up of UASB, using glucose as a sole
nutrient
Figure 7.3pHi and pHe comparison for synthetic influent used for startup after addition of
micronutrients
126
It was observed that reactor pH remain between 7 and 7.5 till day 6 and decreased to
below 6.7 during days 7th14th, which was a clear indication of acid formation. No
acidification was observed during first 5 day and later immediate decline in pH was
observed due to acid formation (Vadlani, 2008). The pH was monitored regularly for
influent and effluent from day 1 to 15 when only glucose was added as nutrient. The
changes in pH were observed after two days when influent pH was 7.3 and same day
effluent pH was observed 7.4. The effluent pH remained higher than the influent pH till
day 5 and after 7th day it dropped very sharply and remains below than influent value till
day 14 (Figure 7.2).
The maximum COD removal was observed around pH 7 even during start up of
reactor (first fourteen days with glucose as nutrient) where COD removal efficiency was
less than 70%. It was observed COD removal efficiency improves with pH above 6.8
feeding SNI. Same trend of pH was observed during first week of start up with glucose
influent and SNI.
7.4.2 COD removal efficiency from glucose and SNI

COD and BOD removal efficiency during first five days was lower than 60% but
after 6th day removal efficiency increased 80% and remained between 80 to 70% except
day 11 where maximum removal efficiency was 85%. Feeding of glucose influent to the
reactor for 14 days showed BOD removal was parallel to COD removal rate Figure 7.4.
Figure 7.4 COD and BOD percentage removal comparison
127
In Figure 7.5 where comparison of COD removal efficiency has been indicated of
glucose influent which shows acceptable removal of COD after six days and it remained
below 100 mg L-1 but removal efficiency did not exceed 80%. In study by Subramanyam,
2007 using glucose as a primary nutrient for start up, 75% COD removal was observed
during start up.
Figure 7.5 CODi (influent) and CODe (effluent) comparison
In another study by Zhou, 2006 UASB reactor was fed by three kinds of different
substrates, glucose, skimmed milk and mixed volatile fatty acids (VFAs). In this study
extracellular polymer production was investigated with surface charge of different
substrate which effect on granulation. The pH was adjusted to 7.4 in mesophillic
conditions, big stout granules formed with glucose as substrate. The maximum COD
removal efficiency was achieved 90%. In another study where sucrose was fed with
diluted leachate to the laboratory scale UASB reactor, sucrose was also found to be
decreasing the pH of the reactor from 7.2-4.7 which inhibit the reactor efficiency (Eng,
1986). Sucrose as reducing sugar converts into glucose and fructose where glucose was
further used as carbon source. Glucose as carbon source was also studied by Majumder,
2007 to treat wastewater containing 2-chlorophenol and 2,4-dichlorophenol. Glucose was
observed good carbon source and removal efficiency of 2-chlorophenol was 93.7%. This
showed that glucose was much better carbon source to remove 2-chlorophenol and
highest gas production 76.1% as compared to other carbon source nutrient used. Sodium
128
formate, sodium propionate, glucose and methanol were used separately in the feed as cosubstrate.
Figure 7.6 COD influent and COD effluent form fifteenth day with SNI
The most interesting results of COD removal 80% in present study were achieved
after one week of reactor start up using only glucose as carbon source for the
microorganisms. Glucose served as better carbon source which was easily biodegradable
to form acetate and good carbon source for active biomass. As compared to other studies
where glucose was used as carbon source during start up of reactor for 1) granulation, 2)
removal effect of specific compounds and 3) removal of COD and other studies showed a
maximum COD removal rate of 75% where reactor was seeded from full scale UASB
reactor.
During second stage start up process where synthetic influent was used in same
reactor (Figure 7.6) it was clear that COD removal was more than 90% and after 30 day
of start with synthetic influent COD removal was 95% and it remained till 49 days.
Comparing glucose and SNI (Figure 7.9) during start up showed that using glucose as
influent (first stage) removed COD value of 70% while in SNI (Second stage) influent
COD removal was > 95% during first 30-45 days. After 19 days of feeding with SNI,
effluent COD was below 50 mg L-1 and after 31 day effluent COD was detected < 4 mg
L-1.
129
Figure 7.7 Percent COD removal using SNI in UASB
HRT was maintained 48 hr for both glucose and SNI. Glucose in synthetic wastewater
increased the specific methanogenic activity (Vadlani, 2008). COD removal efficiency
was found much greater with SNI than glucose only (Figure 7.5, 7.6). Percent COD
removal was indicated in Figure 7.7 from day 15 to 45 during second stage.
Study by Kalogo (2001); Kalogo and MBassiguie (2001) on self inoculated
reactor treating domestic wastewater, the reactor achieved a removal efficiency of up to
65% of COD and 73% suspended solids and indicated that removal of matter was mainly
due to interception in the reactor. Many studies have mentioned that UASB digesters
need to be inoculated with flocculent sludge whereas self-inoculation was another
alternative for start-up. Without using seed during start-up of reactor considered to be
feasible after 6 12 weeks at HRT about 6 h and temperature above 20C (Lettinga et al.,
1993). In another study by Alvarez, (2006) start-up without inoculum for 120 days, 58%
total COD removal at temperature 15C and HRT 11 hrs. It is concluded from present
research self inoculated UASB reactor can achieve the maximum COD removal
efficiency in 4 weeks if sludge was used from domestic septic tank. No granules were
observed in four weeks period and maximum removal efficiency was achieved.
7.4.3 Substrate uptake rate during start up with glucose and SNI
Yield coefficient was supposed to be constant due to same feeding rate of glucose
as COD 250-300 mg L-1 was added. In this experiment a slight drop in pH was observed
130
due to glucose conversion to acid as indicated in Figure 7.2. During first five days
substrate uptake rate was lower and COD was higher in effluent more than 100 mg L-1.
After five days substrate uptake rate increased and effluent COD started to decrease at
same rate. After six days there was maximum removal of substrate uptake was observed
and with a maximum COD removal. During first five days active biomass was not
present therefore substrate uptake rate was low. With continuous feed of substrate at
same flow rate and concentration non-active biomass was washed out from anaerobic
reactor. At the same time, active biomass increased which accumulated inside the reactor.
This substrate uptake rate helped in adaptation of specific activity like enzyme production
for degradation of volatile fatty acids (VFA) (Vadlani, 2008). Specific uptake rate was
calculated from VSS, HRT and reactor volume. Substrate uptake rate improved after 6th
day and remained same till 14 days (Figure 7.8). If mass loading rate, upflow velocity or
HRT increased, active biomass may wash or need to acclimatize with new load.
Typically bacteria with a high substrate affinity (low Ks) found to be less efficient than
those who have low substrate affinity but high Ks value (Verstrate, 2004). This was
proved from Figure 7.8 where substrate uptake rate increase after four days for glucose.
SNI uptake increased after 22 days and COD removal rate was observed 99% while 80
85% for glucose solution. Anaerobic species in reactor having high affinity with glucose
(stage I) as compare to SNI where anaerobic species showed less affinity with SNI but
removal rate of COD was higher than glucose. After 20 days, reactor reached to its full
efficiency but it was kept feeding with SNI till 35 days to make this reactor ready for
MWW. This MWW had very uncertain variation in COD values due to industrial
discharge in sewage system. It was observed that affinity with substrate was very
important for the maximum COD removal efficiency and to shorten start up period for
the maximum COD removal rate. Other researchers have not reported the effect of
substrate affinity on COD removal. Low substrate affinity may have positive effect on
COD removal than those with high substrate affinity. In present study it was observed
synthetic nutrients gave low substrate affinity than glucose. It may be possible that
glucose quickly assimilate in microbial cells and after 7 days uptake rate was slow while
SNI was very effective in assimilation of nutrients present in SNI. This experiment was
conducted to replace blend of different nutrients with single carbon source (glucose) and
131
it proved that single glucose may not be enough to reduce the reactor start-up time and
COD removal efficiency (Figure 7.9). Start up with SNI was found in 35 days with COD
removal efficiency 99.9%.
Figure 7.8 CODe and Glucose as substrate uptake
The division of biodegradable fractions was first intorduced to explain oxygen

demand in wastewater treatment system (Dold et al., 1986). Biodegradable substrate
consumed and growth of heterotroph biomass occurs which result in decrease in
biodegradable fraction and uptake rate increase of heterotrophic biomas.
Figure 7.9 Comparison of substrate uptake rate of SNI and glucose
132
Figure 7.10 SNI effects on biodegradable fraction and substrate uptake rate.
A clear representation in Figure 7.10 showed that biodegradable fraction (Fb)

decrease which indicates organic matter present in effluent are reduced as uptake rate of
biomass increased. Decrease in Fb is also possible by contacting of organic solids into the
reator bed. It was important to point out that except COD other parameters like Fb and
oxygen uptake can be good information providing parameters to identify the remaining
organic fraction which were degradable or not.
Figure 7.11 Effects of glucose on Fb and U and substrate uptake rate
133
Stage I, when only glucose feeding was studied for fourteen days biodegradeable
fractions and substrate uptake was compared in Figure 7.8 and Figure 7.11 during
glucose feeding for 14 days. In these figures it is clear substrate uptake rate increased
after 6 days but there was no clear decrease in biodegradeable fractions except day 10
where Fb 0.7 and other 13 days it remained in range of 0.8 and 0.9. In case of SNI, Fb
decreased after 19 days and remain below 0.5 in Figure 7.10. It is fraction which is as
readily accessible as molecules such as glucose and acetate (Verstraete, 2004). In
untrated MWW these fractions are normally found greater than 0.9 and it should be
below 0.4 after biological treatment. During first three days glucose uptake rate was less
and effluent may contained a Fb from influent and sludge washing. After five days
substrate uptake rate was same from 0.06 0.08 per day. On 10th day there was only one
value obtained with minimum biodegradable fraction found in effluent, which seems to
be not normal as compared with (Fb and U) other values obtained during 14 days.
VSS/TSS ratio decreased to 0.65 from 0.9 after 7 days and then remained below 0.4.
7.4.4 UASB effluent treatment with waste H2O2

We used previously optimized dose of waste H2O2 for the treatment of effluents
of UASB reactor. Small dose of hydrgen peroxide was found very effective in removal of
total nitrogen removal (79% efficiency) and combined removal rate of total nitrogen was
84% with 5 mg L-1 effluent concentration. The removal of other parameters like TSS,
COD, TN and trubidity was 73%, 99%, 84% and 67.5%. This proposed treatment option
was found very effective in COD and nitrogen removal but Ortho-P was not removed to
an acceptable level (Table 7-5). Secondary treatment step with H2O2 conductivity and
TDS was not removed greater rate but COD was found oftenly below the detection limits.
All these treatment process was performed at HRT 48 hrs. This showed that post
treatment proces with hydrogne peroxide was very effective to reduce the turbidity and
total nitrogen to an acceptable local standard. Nitrogen removal was also studied by
Nikolic, (2005) where denitrification with a reaction between equal amounts ammonium
and nitrite to form nitrogen gas. It showed complete removal of nitrogen but effects due
pH value, temperture and some compounds in leachate have an inhibition effect on the
reacion.
134
Table 7-5 Average characteristics of raw MWW and effluent of various treatment steps. BDL =
Below detection limit
Parameters
Raw wastewater
UASB
H2O2 treatment
Removal efficiency
TSS
112 10
42 5.89
30 4
73.21%
VSS
80 10
31 3.54
12 4
85%
TDS
493 14
421 10
477.6 3
3.2%
Conductivity
9938
841 7
957 3
3.62%
VSS/TSS
0.71
0.73
0.4
COD
290 6.69
31.5 4.43
BDL
99.9%
AN
2.42
6.050.80
0.1
95.86%
NO3-N
3.52 0.4
2.47 1
1.7 0.2
51.7%
NO2-N
2.04 0.3
1.79 0.5
0.26 0.1
87.25%
TK-N
24 2
14.58 1
30.5
87.5%
T-N
31.98 1
24.89 2
5.06 0.4
84.17%
Ortho-P
6.87 0.2
5.34 1
5.51 1
19.79%
pH
7.25 1
7.42 1
7.5 1
Turbidity
40 3
28 3
13 3
67.5%
Ammoinium nitrogen which is toxic to aquatic species was oxidized with H2O2.
Table 7-6 showed that there was decrease in ammonium nitrogen after 30 minutes of
mixing but later on it was found slight increase in its concentration and after 120 minutes
0.1 was observed. Nitrate nitrogen was only parameter which was found increasing as
reaction proceeded and nitrite and ammonium nitrogen were foud decreasing with
mixing time. It seemed that nitrification was more dominant than denitrification. It was
also reported that some chemical has been already used for nitrification and
denitrification process. Sabzalim, 2006 reported denitrification of nitrate using Zn and
sulfamic acid treating ground water.
NO3 + Zn + H+ + H2 NSO3H
N2 + SO42- + Zn2+ + 2H2O
The oxygen released from the dissociation of H2O2 might have caused the oxidation of
ammonium to nitrate.
During anaerobic treatment inorganic components such as NH4+ is removed to a
limited extent. Many additional systems have been proposed to remove NH4+ from UASB
effluent. In another study zeolite and duckweed plants were used to reduce the NH4+ from
UASB effluent in two different studies (Aiyuk et al., 2004; El-Shafai, 2007). Problem
135
with zeolite are two hours mixing and recharging of used zeolite. In this study NH4+ was
passed through a column charged with 1.2 kg of zeolite system attached after UASB
reactor proved to be efficient with 99% removal than the zeolite column installed before
UASB reactor, 47% efficiency (Aiyuk, 2004). In another study by El-Shafai (2007),
where duck weed ponds were used after UASB reactor to remove NH4+ with 98%
efficiency. The disadvantage of this system is only that it requires large area for
duckweed ponds where three ponds were used to achieve efficiency. In the present study
waste H2O2 was used after UASB reactor to meet discharging standards. Possible
reaction after addition of H2O2 as given below, ammonium was converted into nitrate
which was less toxic (Table 7-6, Figure 7.12).
Table 7-6 UASB effluent treatment with H2O2 at optimized dose 2.0 ml L-1
Time
NH4-N
NO3
NO2
Conductivity
TDS
COD
Temp
0 min
0.22
1.30
0.68
989.00
487.00
31.00
30.70
30 min
0.06
0.78
0.11
970.00
484.00
31.00
31.40
60 min
0.15
1.76
0.23
948.00
473.33
20.00
31.26
90 min
0.13
1.92
0.48
922.00
460.00
BDL
30.60
120 min
0.10
1.70
0.26
910.50
455.50
BDL
30.80
Over all total nitrogen removal was 84% with effluent concentration was 5 mg L-1 after
peroxide treatment which was value below the permissible limit of Pakistan
environmental protection Agency (PEPA) discharging standards. The maximum nitrogen
removal was observed after peroxide treatment which might be due to post treatment of
oxidation process.
7.4.5 Performance of reactor at different HRT

Two HRT i.e. 48 hrs and 24 hrs were tested to see the efficiency of COD removal,
after completion of start up period in four weeks. It was observed that HRT below 24 hrs
was found to disturbing the settled sludge in the reactor. It can be argued that no
granulation occurred against the low HRT. Increase in uplifting velocity of influent 0.1
cmhr-1 lifted the sludge bed. It took more time to develop granules to stand against high
uplifting velocity. Average COD reduced to 31.50 mg L-1 at 48 hrs HRT was observed
136
and it was 74 mg L-1 at 24 hrs HRT with 99% removal efficiency. No change was
observed in turbidity, TDS, conductivity and pH. Other parameters were required to
study more to see the effect on total nitrogen after UASB. Many researchers have worked
to see the effect on treatment efficiency at lowest HRT. Mahmood (2007) observed 85%
nitrate removal efficiency with zero ammonia in effluent at 24hrs HRT and sulfide
removal 99% at 0.1day HRT. In this study sludge was collected from anaerobic
methanogenic reactor. In present research work 85% total nitrogen and 95% ammonia
removal was observed at HRT 1-2d where inoculum was collected from domestic septic
tank.
Figure 7.12 Effect on ammonium, nitrate and nitrite after treating UASB effluent with H2O2
Table 7-6 shows that UASB reactor achieved full efficiency in shorter time period
when granular sludge was selected during start up other wise it take three months to
achieve maximum efficiency (Yu, 2001; Zhou, 2006; Kalogo, 2001). It is clear from
Table 7-7 during start up of UASB reactor the maximum removal efficiency of 95% was
observed with cattle manure as inoculums. it is clear from present research that domestic
septic tank sludge achieved the maximum COD removal efficiency of 95-99% in only
eight weeks at HRT of 24-48 h. Granulation was not included in this part of the study due
to mixed MWW was used. Many researchers have indicated that maximum removal
137
efficiency relates with granulation formation which takes three months. It is clear
domestic septic tank sludge could be very effective in removal of COD form domestic
and MWW unless it was not mixed with other industrial toxic wastewater.
Table 7-7 Comparison of UASB HRT start up with different inoculums
HRT
Inoculums source
6d
24 h
24 h
10-11 h
3h
24-48h
Self inoculation
Granular sludge
Cattle manure
Digested sludge
Digested sludge
Domestic septic tank
sludge
COD Removal
efficiency
84%
86%
90-95%
63-73%
90-92%
99%
Reference
Bodkhe, 2009
Ramakrishnan, 2007
Akila, 2007
Alvarez, 2005
Singh, 1996
Present study
7.5 Economic Aspects

In Table 7-8 it is indicated that integrated treatment, as discussed in this chapter,
has approximate 50% less cost than conventional wastewater treatment. In this process
UASB effluent was treated with waste hydrogen peroxide. Important factors which make
this process less costly than aerobic treatment are indicated in table. As waste H2O2 is
used in this process to further reduce the COD from UASB effluent, therefore cost of
H2O2 is included. This treatment option can be used for small treatment facility such as
less than 10,000 I.E where it may not be as expensive as aerobic treatment cost. A total
investment cost of about 100$ per capita is an average. About half is for building
construction and remaining consists on electrical and mechanical devices. The
construction and running cost vary considerably. The total cost for treatment is
approximately 40$/y on the basis of information given in Table 7-8 that one inhabitants
produce 180 liters of wastewater per day and treatment cost range around approximately
0.5 $/m3. These figures only give order of magnitude.
138
7.6 Conclusions
During start up of UASB, glucose and SNI were used to activate the acetogenic
and methanogenic microbial species. These species were found low affinity with SNI and
high affinity with glucose which resulted in treatment efficiency was higher in removing
COD from 95% and 85%. These influents, SNI and glucose solution was fed separately
to the reactor for 114 days (phase I) and 1545 days (Phase II). This system was
139
designed to face broad variations in COD feed because MWW contained both industrial
and domestic wastewater.
In this study combination of UASB with AOP was tested to see the effect on
COD, TN and Ortho-P. This proposed system was found very successful in removal of
COD 99% and TN 84% at low investment cost. Orhto-P removal did not reach up-to
working goal. In this regard phosphorus and nitrogen both were not in ratio 15:1 for
eutrophication. As proposed treatment system was successful to reduce total nitrogen to
acceptable limits which could be effective to obstruct eutrophication. Excessive Orthophosphorus alone has less consequence on eutrophication. In this regards combining
UASB with waste 40% H2O2 was to contrive successful combination with less treatment
cost. This combination was successfully used to treat MWW in the laboratory with of
67% turbidity removal, 95% ammonium, 85% VSS, 84% Total nitrogen and COD 99%
removal.
Addition of AOP after UASB was found very successful in order to reduce the
nitrogen species by oxidation process. Optimized dose of 2 ml L-1 of 40% H2O2 was used
to treat UASB effluent. There was poor ortho-phosphorus removal by UASB treatment.
Considerable work in this regard was to use waste H2O2 to polish the UASB effluent by
reducing TN, Turbidity and microbial load.
140
References
Aiyuk. S., Amoako. J., Raskin. L.,VanHaandel. A. & Verstraete. W. (2004). Removal of
carbon and nutrients form domestic wastewater using a low investment, integrated
Akila, G. & Chandra, T.S. (2007). Performance of an UASB reactor treating synthetic
wastewater at low temperature using cold adapted seed slurry. Process Biochem.
42, 466-471.
Alvarez, J. A., Ruiz, I., Gomez, M., Presas, J. & Soto, M. (2006). Start-up alternatives
and performance of an UASB pilot plant treating diluted municipal wastewater at
low temperature. Bioresource Technol. 97, 1640-1649.
Bailey, J. E. & Ollis, D. F. (1986). In: Biochemical engineering fundamentals. McGrawHill int, Nw York.
Bodkhe, S.Y. (2009).A modified anaerobic baffled reactor for municipal wastewater
treatment. J. Env. Manage. 90, 2488-2493.
Boe, K., Steyer, J. P. & Angelidaki, L. (2008). Monitoring and control of the biogas
process based on propionate concentration using online VFA measurement, Water
Sci. Technol. 57(5), 661-666.
Cohen, A., Breure, A., Van Andel, J. G. & van Deursen, A. (1982). Influence of phase
separation on the anaerobic digestion of glucose-II: stability and kinetic reponse
to shock loadings. Water Sci. Technol. 57(5), 687-692.
Dold, P. L., Bagg, W. K. & Marais, GvR. (1986). Measurement of the readily
biodegradable COD fraction (Sbs) in municipal wastewater by ultrafiltration
UCT, Report No. W57., Department of civil engineering, university of Cape
Town, Rondebosh, 7700, South Africa.
El-Shafai, S. A., El-Gohary, F. A., Nasr, F. A., Van der Steen, N. P. & Gijzen, H. j.
(2007). Nutrient recovery from domestic wastewater using a UASB-duckweed
ponds system. Bioresource Technol.. 98, 798-807.
Eng, S. C., Fernandes, X. A. & Paskins, A. R. (1986). Biochemical effects of
administering shock loads of sucrose to a laboratory-scale anaerobic (UASB)
effluent treatment plant. Water Research. 20, 789-794.
Kalogo Y., MBouche, J. H. and Verstraete, W. (2001). Physical and biological
performance of self inoculated UASB reactor treating raw domestic sewage. J.
Environ. Eng. 127 (2), 179-183.
141
Kalogo, Y., MBassiguie, A. & Verstraete, W. (2001). Enhancing the start-up of a USB
reactor treating domestic wastewater by adding a water extract of Moringa oleifer
seeds. Appl. Microb. Biotechnology. 55, 644-651.
La Motta, E. J., Padron, H., silva, E., Luque, J., Bustillos, A. & Corzo, P. (2008). Pilot
plant comparison between the AFBR and the UASB reactor for municipal
wastewater pretreatment. J. Env. Eng. 134(4), 265-272.
Lettinga, G., de Man, A., van der Last, A. R. M., Wiegant, W., van Knippenberg, K.,
Fijns, J. & Van Buuren, J. C. L. (1993). Anaerobic treatment of domestic sewage
and wastewater. Water Sci. Technol. 27(9), 67-73.
Mahmood, Q., 2007, Process performance, optimization and microbiology of anoxic
sulfide biooxidation using nitrite as electron acceptor, PhD dissertation. pp. 44-69.
Majumder, P. S. & Gupta, S. K. (2007). Effect of carbon sources and shock loading on
the removal of chlorophenols in sequential anaerobic-aerobic reactors.
Mathiewu, S. & Etienne, P. (2000). Estimation of wastewater biodegradable COD
fractions by combining respirometric experiments in various So/XO ratios. Water
Res. 34 (4), 1233-1246.
Methanol, (2009), http://www.methanol.org/pdf/MethanolDenitrification.pdf
Nikolic, A. & Hultman, B. (2005). Chemical denitrification for nitrogen removal from
landfill leachate. Water Sci. Technol. 52(10-11), 509-516
Ottino, J. M. & Khakhar, D. V. (2000). Mixing and segregation of granular materisls.
Anal. Rev. Fluid Mechan. 32, 55-91.
Pena, M. R., Mara, D.D. & Avella, G. P. (2006). Dispersion and treatment performance
analysis of an UASB reactor under different hydraulic loading rates. Water Res.
40, 445-452.
Ramakrishnan, A. & Gupta, S.K. (2006). Anaerobic biogranulation in a hybrid treating
phenolic waste. J. Hazard. Mater. B137, 1488-1495.
Sabzalim, A., Gholami, M., Yazdanbakhsh, A., Musavi, B. & Mirzaee, R. (2006).
Chemical denitrification of nitrate from groundwater via sulfamic acid and zinc
metal. Iran. J. Env. Heal. Sci. Eng. 3(3), 141-146.
Singh, K.S., Harada, H. & Virarghavan, T. (1996). Low strength wastewater treatment by
a UASB reactor. Bioresource Technol. 55, 187-194.
Singh, R. P., Kumar, S. & Ojha, C. S. P. (1999). Nutrient requirement for UASB process:
a review. Biochem. Eng. J. 3, 35-54.
Speece, R. E. (1996). In: Anaerobic biotechnology for industrial wastewater. pp. 31-57.
Archae press, Nashville, Tenn.
142
Subramanyam, R. & Mishra, I. M. (2007). Biodegradation of catechol (2-hydroxy

phenol) bearing wastewater in an UASB reactor. Chemosphere. 69, 816-824.
Tetra Pak Technical data manual. (2008). Hydrogen peroxide, Doc. No.OM-27717260101, 8-9.
Vadlani, P. V. & Ramachandran, K. B. (2008). Evaluation of UASB reactor performance
during start-up operation using synthetic mixed-acid waste. Bioresource Techno.
99, 8231-8236.
Van der Meer, R. R. & Heertjes, P. M. (1983). Mathematical description of anaerobic
treatment of wastewater in upflow reactors. Biotechnol. Bioeng. XXV, 25572566.
Van Hulle, S. W. H. (2005). Modelling simulation and optimization of Autotrophic
nitrogen removal processes. PhD thesis. pp. 8-9.
Verstraete, W. (2005). In: Environ. Biotech. Proc. pp. 1-30. Ghent University, Belgium.
Yu, H. Q., Fang, H. H. P. & Tay, J. H. (2001). Enhanced sludge granulation in upflow
anaerobic sludge blanket (UASB) reactors by aluminum chloride. Chemosphere.
44, 31-36.
Zhou W., Imai, T. Ukita, M., Sekine, M. & Higuchi, T. (2006). Triggering forces for
anaerobic granulation in UASB reactors. P. Biochem. 41, 36-43.
143
8 Chapter 8:
Sequential Two Stages Anaerobic and H2O2 Treatment of
Confectionary Wastewater
144
Abstract
Anaerobic treatment in combination with post treatment of advanced oxidation
process was employed to test the treatability of integrated process for confectionary
wastewater mixed with MWW. Reactor was inoculated with 10 year old septic tank
sludge and started up with glucose, macro and micro nutrients. The system was operated
at 25-30C, HRT 48 hrs for 25 days with post treatment with 40% waste H2O2. This
waste H2O2 was collected from industrial process after disinfection of packaging
material. Reactor performance was evaluated by pre and post treatment analysis of COD,
TSS, TDS, and turbidity. Their removal efficiencies were up to 98.6%, 91%, 50% and
81%, respectively. Reactor achieved its full efficiency after feeding diluted wastewater as
1/5, 1/3, 1/2 and 1/0 for 5 7 days each. Reactor achieved full efficiency in 25 days
removing 98% COD from mixed wastewater. A batch peroxide treatment process was
also added to reduce the turbidity and to increase the DO of treated effluent. The strategy
was found quite applicable for the treatment of combined industrial and municipal
effluents.
Keywords: Anaerobic reactor, advanced oxidation process, macro and micro nutrients,
dissolved oxygen, hydraulic retention time.
145
8.1
Introduction
Confectionary industries are growing very fast in Pakistan for their acceptable
products both for children and elder of all ages. Quantity of wastewater produced by
these industries is not as high as produced by other food industries but organic pollutant
load is very high, which is a major problem of this wastewater. Such wastewater if
discharged into normal sewage system or surface water then it rapidly increases the COD
and decrease the DO of water bodies. This high load of COD reduces the aesthetic values
of freshwater system (Spellman, 2003).
The
employment
of
activated
sludge
systems
requires
energy,
coagulants/flocculants or oxidizing agents along with sludge handling. Pakistan is facing

serious energy crisis and especially when load shedding is frequent during long summers.
Such situation may hamper the treatment plant. UASB can be an alternate against
activated sludge systems for carbon rich-wastewaters. Anaerobic systems have less
energy requirement for wastewater treatment. Moreover, in anaerobic system less
biomass is produced and 6 to 10 times less sludge is produced which reduces the sludge
disposal costs. UASB might be an economical option to replace primary and secondary
treatment steps (Gohil, 2005; Tandukar, 2007; Seghezzo, 1998). UASB is designed in
such a way that up flow velocity of wastewater is much slower than granules settling
velocity.
In case of high-suspended solids present in wastewater an integrated treatment
option can be economical option, like chemically enhanced primary treatment CEPTUASB. Such treatment option can fulfill requirements like non-sophisticated equipment,
high treatment efficiency, simple design and less operating and capital cost (Aiyuk,
2004). UASB is designed in such a way that upflow velocity of wastewater is much
slower than granules settling velocity.
Effluent from UASB can be further treated to remove turbidity, COD, microbial
load and increase DO. In this study 40% waste hydrogen was used, which was collected
from nearby industry where it was used to disinfect the juice packaging material and then
after use it was discharged into sewage drains. This discarded 40% waste H2O2 was
tested on UASB effluent to polish it. Addition of neutralizing agents is needed for
146
confectionary wastewater, caustic normally used to adjust the pH close to neutral. It can
be an extra operational cost in this system (Romli et al., 1994).
This study had three main objectives;
1) To treat high load of organic waste from biscuits and confectionary
wastewater mixed with MWW,
2) To study the feeding effect of diluted wastewater, 1/5 dilution, 1/3 dilution,
dilution and undiluted, to achieve treatment efficiency in short time,
3) To examine the effect of waste 40% H2O2 on treated UASB effluent.

8.2.1 Wastewater Sample
Wastewater sample was collected from a mixing point of industrial (Biscuits &
Confectionary) and MWW as required after every two weeks and stored at 5C. Five
liters clean container was used and each sample was taken during peak hours of
production (between 11:00 am to 2:00 pm). Dilution was prepared to feed low strength
wastewater to the reactor during first week and later undiluted sample was fed. To avoid
unfavorable consequences, reactor was not fed directly with industrial wastewater.
Sodium hydroxide was added to reduce the acidity of the sample. Confectionary
wastewater was highly acidic with pH 4 due to excessive use of acetic acid in candy
product. Before direct feeding of industrial wastewater, reactor was fed with glucose,
macro and micro-nutrients for 49 days to enhance the treatment efficiency during start up
period (the results have been mentioned in the previous chapter).
8.2.2 Treatment design

The reactor starts up and its features (Table 8-1) were described in previous
chapter. The UASB effluent was further treated with 40% H2O2 to oxidize the remaining
pollutants. Reactor was continuously fed with peristaltic pump (longer pump YZ1515x,
Baoding Longer Precision Pump Co., Ltd.) at the rate of 1.6 ml/min. Organic loading rate
was increased as 1/5th, 1/4th, 1/3rd, 1/2nd dilution and later on undiluted feeding to reactor.
Effluent from UASB discharge f was fed to chemical oxidation tank see Figure 8.1.
147
Table 8-1 Parameters used to treat industrial wastewater

Parameter
Value
Temperature (C)
20-30
Volume of reactor (L)
4.6
-1
Volume of influent (Ld )
2.16
Concentration of influent (mg COD L-1 )
300-2500
-1
Mass loading rate (g COD L . hr)

-1
Hydraulic loading rate (LL .day)

Hydraulic retention time (hrs)
-1
Upflow velocity (cmh )
0.144
0.48
48
0.05

the treatment with UASB and 40% H2O2. Chemical oxygen demand (COD) was
determined by closed reflux colorimetric method using digester (HACH - LTG
082.99.40001), (APHA, 2005), the wastewater sample, digestion solution and sulphuric
acid were digested in vials for two hours at 150oC.
Figure 8.1 UASB followed by chemical oxidation with 40% hydrogen peroxide. P1= peristaltic feed
pump, P2 = peristaltic recycle pump
148
After digestion, absorbance was measured at wavelength 605 nm in a

spectrophotometer (LOVIBOND tintometer GMBH, 44287 DORTMUND). The pH was
measured immediately after collection without stirring to prevent loss of CO2 from the
sample, such losses may cause increase in pH. The pH meter (HANNA, HI 991003)
was used for determination. H2O2 was measured according to Tetra Pak Technical data
manual by using hydrometer and temperature. H2O2 value was obtained after connecting
temperature and hydrometer reading on third scale of H2Os W/W (Tetra Pak, 2008).
8.3 Results and Discussion

First day of first week COD removal was only 22% may be due to rich
carbohydrate wastewater when industrial wastewater was diluted with 80% distilled
water. This dilution was prepared to feed the reactor to make the specific anaerobic
species more active to start decompose the organic rich influent. High organic load may
wash out sludge from the reactor. By the end of first week of UASB reactor fed with 1/5th
distilled water diluted effluent showed only 79% removal efficiency (Table 8-2, Figure
8.2). The maximum removal efficiency was observed after seven days but after 5 days
efficiency decreased again. Effluent from UASB was further treated with waste 40%
H2O2 to further improve the effluent quality. During first five days, secondary treatment
with peroxide was found very effective and maximal removal of 22% was observed.
Later on till day 25 continuous decrease in removal efficiency was observed while using
H2O2. Peroxide treatment was performed at the rate of 2 ml L-1 of UASB effluent for
sixty minutes mixing. Reactor came into good COD removal efficiency may be due to 1)
sludge collected from 10 year old septic tank 2) start up with glucose, macro and micronutrients for 32 days and then it was fed with MWW up to 54 days. Relatively low COD
removal of only 22% was observed during first week when industrial wastewater was
diluted with 80% distilled water. This dilution was prepared to feed the reactor to make
the specific anaerobic species more active to start decompose the organic rich influent.
Direct feeding of high organic load may be risky to wash out sludge from the
reactor. The maximum removal efficiency was observed after seven days but after 5 days
removal efficiency decreased again. The effluent from UASB was further treated with
waste 40% H2O2 to further improve the effluent quality. During first five day of
149
secondary treatment with peroxide was found very effective and maximal 22% removal
was observed. Later on till day 25 continuous decrease was observed in removal
efficiency with H2O2. Peroxide treatment was performed at the rate of 2 ml L-1 of UASB
effluent for sixty minutes of mixing. There was interesting removal rate shown in the
Figure 8.2, 8.3 where COD removal by peroxide and UASB reactors were similar.
Improving removal efficiency was observed in second week. From day 8 to 12 influent
was diluted with 70% distilled water and 30% sample. The maximum removal of 92%
was observed by anaerobic reactor during second week and only 1 to 5% was observed
for H2O2 treatment. During week 3rd anaerobic COD removal efficiency was increased
upto 94 to 96% and total COD removal after treating with H2O2 was 98%. This increase
in COD removal during 4th week achieved was considerable as the organic load increased
after conditioning of the reactor sludge with passage of time. HRT was kept 24 hr
throughout to see the effect of dilution effect on biomass to acclimatize the specific
carbohydrates rich wastewater. After three weeks it was observed that reactor was ready
to be fed with high strength wastewater. The only disadvantage seen through these
experiments was to increase in 10% sludge volume after four weeks. The COD removal
efficiency was also investigated by Beal (2000) where two anaerobic reactor UASB and
down flow anaerobic filter was used. In present study we used waste 40% H2O2 which
was found more effective than fresh available one. Using waste H2O2 was found more
effective to inactivate the microbes and increase in DO. UASB effluent has almost no DO
with high microbial load (results not shown). There was another advantage to use waste
H2O2 was 80% reduction in turbidity while only 28% turbidity removal efficiency was
found for UASB (Table 8-3).
150
Table 8-2COD removal comparison, in COD mg L-1

days
Dilution of
Influent
UASB
COD
COD after
Total COD
influent
COD
effluent
removal %
peroxide
removal %
COD
treatment
1/5th dilution
250.00
193.00
22.80
148.46
40.08
1/5th dilution
216.00
146.00
32.41
97.33
54.94
1/5th dilution
216.00
116.00
46.30
89.23
58.69
1/5th dilution
216.00
80.00
62.96
61.54
71.51
1/5th dilution
258.00
117.00
54.65
83.57
67.61
1/5th dilution
258.00
69.00
73.26
53.08
79.43
1/5th dilution
227.00
47.00
79.30
36.15
84.07
1/3rd dilution
229.00
42.00
81.66
32.31
85.89
1/3rd dilution
321.00
73.00
77.26
56.15
82.51
10
1/3rd dilution
328.00
57.00
82.62
43.85
86.63
11
1/3rd dilution
660.00
66.00
90.00
50.77
92.31
12
1/3rd dilution
663.00
48.00
92.76
36.92
94.43
13
1/2 dilution
681.00
51.00
92.51
39.23
94.24
14
1/2 dilution
687.00
87.00
87.34
66.92
90.26
15
1/2 dilution
682.00
102.00
85.04
78.46
88.50
16
1/2 dilution
1080.00
90.00
91.67
69.23
93.59
17
1/2 dilution
1075.00
70.00
93.49
53.85
94.99
18
1/2 dilution
1060.00
58.00
94.53
44.62
95.79
19
Direct feed
1089.00
41.00
96.24
31.54
97.10
20
Direct feed
1093.00
419.00
61.67
322.31
70.51
21
Direct feed
1080.00
238.00
77.96
183.08
83.05
22
Direct feed
2545.00
143.00
94.38
95.33
96.25
23
Direct feed
2498.00
91.00
96.36
70.00
97.20
24
Direct feed
2558.00
104.00
95.93
48.00
98.46
25
Direct feed
2544.00
88.00
96.54
42.82
98.53
151
Table 8-3 Treatment efficiency

UASB %
Parameters
Raw
UASB
ww
effluent
treatment
efficiency
H2O2 treatment
Treatment
2 ml L-1
efficiency
pH
4.60
6.10
7.10
TDS ( mg L-1)
880.00
648.00
26.36
441.00
50%
COD ( mg L-1)
2500.00
88.00
96.48
48.00
98.50%
TSS ( mg L-1)
443.00
96.00
78.33
44.00
91%
VSS ( mg L-1)
171.00
51.00
28.17
21.00
70%
VSS/TSS
0.1603
0.5313
0.4773
Turbidity (NTU)
200.00
62.00
69.00
38.00
81%
DO ( mg L-1)
0.00
0.00
6.00
Figure 8.2 COD influent, UASB effluent and H2O2 treated effluent with COD removal mg L-1. PI
=Phase one, PII= Phase two, PIII= Phase three, PIV= Phase four, PV= Phase five.
152
Figure 8.3 COD removal efficiency, peroxide COD removal can be considered as total COD percent
removal
The pH adjustment was done with 1N NaOH before feeding to the anaerobic reactor.
Due to recycling, rapid biomass accumulation was observed where volume of the sludge
was increased 10% after 20 days when influent fed to reactor without dilution. Biomass
measurement
was
made
during
the
last
days
treatment.
Figure 8.4 pH comparison of UASB effluent and H2O2 effluent
153
of
sample
Organic loading rate (OLR) was increased gradually from diluted sample to
undiluted, during first week OLR was 0.144 g L-1 d-1, second week 0.288 g l-1, second
last week 0.518 g l-1 d-1 and last week 1.2 g l-1 d-1. Increase of VSS/TSS ratio of the
UASB reactor from 0.38 to 0.53 was observed in the last week of reactor operation which
was actually an increase in of active biomass. VSS are useful in control of wastewater
treatment operation because it offers a rough approximation of the amount f organic
matter found in solid fraction of wastewater, sludge and industrial waste.
Confectionary wastewater was characterized by acidic pH (4-5 in range),
therefore; it was important to adjust the pH before feeding to the reactor to avoid
inactivation of acetogenic and methanogenic species present in reactor. Figure 8.4 clearly
indicates that UASB effluent pH was reduced after feeding diluted and undiluted
confectionary wastewater. Post treatment with H2O2 was found effective in neutralizing
the pH of UASB effluent. This indicated that the organic degradation reactions and
mineralization with peroxide lead to basic pH producing by-products like HCO3- (Ksibi,
2006; Perkowski, 2003).
8.3.1 Use of H2O2 to polish UASB effluent

H2O2 produces water and oxygen when it dissolved in water which decomposes
the organic matters (Lenntech, 2009).
2 H2O2
2H2O + O2
H2O2 is unstable and breaks down into single oxygen atom and a water molecule.
Atomic oxygen is very reactive that forming stable oxygen molecule increase the level of
dissolved oxygen (Hinchee, 1991). This atomic oxygen also degrades the remaining
organic matter left after UASB treatment. Due to its bleaching effect turbidity was
reduced to acceptable limits. UASB effluents do not contain dissolved oxygen. Post
treatment with H2O2 can regain the dissolved oxygen upto 6 ppm (Bhatti, 2009). Peroxide
converted the ammonium nitrogen to nitrate nitrogen. In water ammonia is present in unionized and ionized form depending on pH and temperature. It is toxic for the more
sensitive salmon fish (see Table 8-4). H2O2 had been used in many studies to treat dyes in
textile industrial wastewater. Where it was reported to decolorize upto 90% of dyes using
large quantity (20 dm3) wastewater (Perkowski, 2003; Lettinga, 1978). Due to
154
effectiveness of oxidative reactions of H2O2, it proved to be effective in reduction of

turbidity, deodorization and disinfection of domestic and industrial wastewater treatment
(Yonar, 2006). H2O2 converts the ammonium nitrogen to nitrate which is less toxic to
aquatic species. Another economical approach studied by (Aiyuk, 2004; Kalogo, 2001)
was using zeolite to remove ammonium nitrogen.
Table 8-4 Lethal ammonia concentrations at different pH, and its exposure
mg L-1 LC 50 salmon fish
pH
Duration
Total
ammonia
ammonia
6.5
7
7.5
1-hr
14.3
0.036
4-day
0.73
0.002
1-hr
11.6
0.093
4-day
0.74
0.006
1-hr
7.3
0.181
4-day
0.74
0.019
This option had a disadvantage that zeolite needed recharging. In present study H2O2 was
used that just required single dose of 2 ml L-1of application and complete mixing.
8.3.2 Comparison with other processes

The results obtained in this study were compared with other studies treating sugar,
confectionary, tomato and carrot blanching wastewater. The maximum treatment
efficiency of 99% removal of COD was reported by Kalyuzhnyi, (1997) treating
wastewater from whey producing industry from initial COD value of 5000-77000 mg L-1
(Table 8-5). The lowest COD removal efficiency of 70% was reported by Cail, (1985)
treating cane juice. In present study 98% COD removal was achieved treating biscuit and
confectionary wastewater and same results were reported by Beal, (2000) treating
confectionary wastewater only. Except Cail, (1985) and Hawkes, (1995) were achieved
COD removal efficiency of 70%; while others achieved more than 90% COD removal
efficiency (Table 8-5).
155
Table 8-5 Treatment efficiency comparison of different investigators treating carbohydrate type
wastewater on the basis of COD percent removal
Treatment
efficiency,
percentage
Wastewater type
27000
> 70
cane juice
1995
22000
88
sugar cane juice
Hawkes et al.,
1995
50000
70
sugar cane molasses
UASB
Beal et al.,
2000
30000
98
confectioanry plant
UASB
Gohil et al.,
2005
15000
95
tomato processing
UASB
Present study
2009
25000-30000
98.6
biscuits and
confectionary
UASB
Lapisto et al.,
1997
9000-27600
90
carrot blanching
UASB
Kalyuzhnyi et al.,
1997
5000- 77000
95-99
Whey
Reactor
type
Author
Year
UASB
Cail and Barford
1985
UASB
Driessen et al.,
UASB
COD
-1
mg L
8.4 Conclusions
Confectionary wastewater contains high load of organic mostly starch which is
used as major ingredient in candy production. UASB treatment was found to achieve
98% COD removal after 25 days. During 25 days wastewater dilution was fed to
gradaully acclimatize the anaerobic species to high loading of organic industrial waste.
The system was fed as 0.00144 kg CODL-1.d-1S. hr at hydraulic retention time of 24 hrs.
the reduced COD was 48 mg L-1 which met discharging standards of NEQs.
156
References
Aiyuk, S., Amoako. J., Raskin. L., VanHaandel. A. & Verstraete. W. (2004). Removal of
carbon and nutrients form domestic wastewater using a low investment, integrated
treatment concept. Water. Res. 38, 3031-3042.
APHA, American Public Health Association, Inc., Standard methods for the examination
of water and wastewater (21st Ed.), New York, USA.
Beal, L. J. & Raman, D. R. (2000). Sequential Two-stage anaerobic treatment of
confectionary wastewater. J. Agri. Eng. Res. 76, 211-217.
Bhatti, Z. A., Mahmood, Q. & Raja, I. A. (2009). Sewage water pollutants removal
efficiency correlates to the concentration gradient of amendaments. J. Chem. Soc.
Pakistan. 31(4), 665-673.
Cail, R. G. & Barford, J. P. (1985). A comparison of an upflow floc (tower) digester and
UASB system treating cane juice stillage. Agri. Wastes. 15, 291-299.
Driessen, W. J. B. M., Tielbaard, M. H. & Veereijken, T. L. F. M. (1995). Experience on
anaerobic treatment of distillery effluent with the UASB process. Water. Sci.
Technol. 30(12), 193-201.
Gohil, A. & Nakhla G. (2005). Treatment of tomato processing wastewater by an upflow
anaerobic sludge blanket-anoxic-aerobic system. Biores. Technol. 97, 21412152.
Hawkes, F. R., Donnelly, T. & Anderson, G. K. (1995). Comparative performance of
anaerobic digesters operating on ice-cream wastewater. Water Res. 29(2), 525533.
Hinchee, R. E., Downey, D. C. & Aggarwal, R. K. (1991). Use of hydrogen peroxide as
an oxygen source for in situ biodgradation. J. Hazard. Mater. 27, 287-299.
157
Kalogo, Y., MBouche, H. J. & Verstraete, W. (2001). Physical and biological

performance of self-inoculated UASB reactor treating raw domestic sewage. J.
Env. Eng. 127, 179-183.
Kalyuzhnyi, S., Fedorovich, V. & Nozhevnikova, A., (1997), Anaerobic treatment of
liquid fraction of hen manure in UASB reactors, Bioresource Technol. 65, 221225
Lapisto , S.S. & Rintala, J. A. (1997). Start-up and operation of laboratory scale
thermophilic anaerobic sludge blanket reactors treating vegetable processing
wastewater. J. Chem. Techno. Biot. 68, 331-339.
Lenntech, 2009, Accessed on 01/12/2009.
http://www.lenntech.com/why_the_oxygen_dissolved_is_important.htm#ixzz0SZ
b99ySg
Lettinga, G. (1978). Feasibility of anaerobic digestion for the purification of industrial
wastewaters. In: Fourth European sewage and refuse symposium, Munich, pp.
226-256.
Perkowski, J. & Kos, L. (2003). Decolouration of model dyehouse wastewater with
advanced oxidation process. Fibres. Text. East. Eur. 11, 3(42), 67-71.
Romli, M., Greenfield, P.F. & Lee, P.L. (1994). Effect of recycle on a two-phase highrate anaerobic wastewater treatment system. Water Res. 28(2), 475-482.
Seghezzo, L., Zeeman, G., VanLier, J. B., Hamelers, H. V. M. & Lettinga, G. (1998).
The anaerobic treatment of sewage in UASB and EGSB reactor: A review.
Spellman, F. R., (2003), In: Handbook of water and waste treatment plant operations,
lewis publisher, 365.
158
Subramanyam, R. & Mishra, I. M. (2007). Biodegradation of catechol (2-hydroxy

phenol) bearing wastewater in an UASB reactor. Chemosphere. 69, 816-824.
Tandukar, M., Ohashi, A. & Harada, H. (2007). Performance comparison of a pilot-scale
UASB and DHS system and activated sludge process for the treatment of
municipal wastewater, Water Res. 41, 2697-2705.
Tetra Pak Technical data manual, (2008). Hydrogen peroxide, Doc. No.OM-27717260101. pp 8-9.
Vadlani, P.V. & Ramachandran, K. B. (2008). Evaluation of UASB reactor performance
during start-up operation using synthetic mixed-acid waste. Bioresource Technol.
99, 8231-8236.
Yonar, T., Kestioglu, K. & Azbar, N. (2006). Treatability studies on domestic wastewater
using UV/H2O2 process, applied catalysis B: Environmental. 67, 223-228.
159
9 Chapter 9:
Major Findings and Future Recommendations
160
9.1 Major Findings

The present study on low-cost treatment of combined MWW containing food industry
effluents by UASB in combination with AOP as post treatment of UASB effluent can be
concluded as under:
1. Chemically enhanced primary treatment was first tested in the research to
select best coagulant to reduce the pollutant load of MWW. Various
coagulants viz. FeCl3, Moringa oleifera seed extract and alum were compared
for their suitability to treat MWW. Different concentrations (4~32 mg L-1)
were applied in a series of batch treatment process mode at 600-620 rpm
stirring for five minutes. It was observed that alum was effective in reducing
the COD up-to acceptable level but above the optimized dose of alum TDS
were found increasing at greater extent. There was an increase of TDS when
the level of alum was increased above the optimized value of 32 mg L-1. The
highest rate of pollutants removal load was observed when 22 to 30 mg L-1 of
alum was used. Therefore, alum concentration in the range of 22 to 30 mg L-1
was an optimum dose for MWW treatment. COD and Ortho-Phosphorus
removal can be possible with increased dose of alum but the cost of alum and
increase of TDS shows less relatively favorable.
2. Another low-cost option to compare with CEPT was to test waste H2O2 (40%)
to treat domestic wastewater, where direct treatment of MWW was given as
batch process by 40% waste H2O2. Waste H2O2 proved as powerful oxidant in
minimizing the organic load of MWW. The optimum dose of waste H2O2 was
found as 2.5 ml L-1 which significantly (p< 0.05) reduced BOD5 and COD in
120 min, thus meeting the NEQS for DWW. The results revealed that
disinfection capacity of 40% waste H2O2 @ 2.5 ml L-1 caused significant
reduction of fecal coliform populations to less than half of the initial value
while treating DWW. It was proved most successful and economical removal
of COD and microbial load. The most attractive outcome in this regard is
using waste from one industry to treat municipal waste. The drawback in this
161
regard, infrequent supply of waste H2O2 from industry can stop the treatment
process.
3. Some industries were selected to treat their wastewater. Carwash industry was
one of them whose effluent was not studied often. This wastewater contained
high content of oil 83 mg L-1 and COD >1000 mg L-1. Due to presence of oil it
was not feasible to treat directly with alum or H2O2. Therefore aeration was
added as pretreatment step to bring oil content ton the surface where it was
scraped out from aeration tank. Effluent from aeration tank was further treated
with alum in second step and H2O2 at third step. Treatment efficiency was 96%
oil, COD, turbidity and TDS were reduced upto 93%, 94% and 74%,
respectively. The present approach was proved cost effective and requires less
space without any pH control. Only costly factor was aeration to separate the
oil, other than aeration it can be more expensive to separate. Thus the treatment
process can be applied on pilot scale to further evalute its efficiency.
4. The present study compared the effectiveness of used and fresh H2O2 to treat
the domestic waste and to reduce the alum dose for chemical sedimentation. It
was observed that used waste 40% H2O2 was very effective and economical.
Fresh 35% H2O2 can be purchased Rs 40/L from the market but used waste
40% H2O2 can be obtained only from specific industries where it used for
disinfection. Using 40% waste H2O2 was found very effective to reduce COD,
turbidity and microbial load. An addition step was merged into H2O2 was UV
light to speed up the reaction. The proposed system was consists of two major
step where first sediments was settled down with alum and decant from first
step was used to treat with H2O2 and UV in the same tank. This proposed
system was effective to treat domestic wastewater but carwash and food
industry wastewater may require other treatment steps need to be added. The
combination of H2O2 with UV light was found very effective to decrease BOD,
COD, and turbidity and coliform bacteria in MWW. Waste H2O2 generated
from an industrial process of disinfection was found more effective in the
treatment of domestic wastewater than fresh 35% H2O2. The waste H2O2 can
162
be applied in combinations with UV light to treat domestic wastewater

effectively.
5. Up-flow anaerobic sludge blanket (UASB) reactor was used to treat mixed
MWW at hydraulic retention time 24-48 hrs and at an average temperature 2534C. The aim was to test two stage treatment concept for low cost MWW
treatment as UAB in first stage and waste H2O2 40% 2 ml L-1 of UAB effluent
at second stage. Moreover, the effect of micronutrients on the treatability of
UAB was also investigated. After start up with glucose for first 15days (first
stage), the reactor was fed with macro and micronutrients (SNI) for 45 days
(second stage). The maximum substrate removal rate was same 0.07 d-1 for
both glucose and SNI. Removal efficiency of total suspended solids (TSS),
chemical oxygen demand (COD), total nitrogen (TN), Ortho-P and Turbidity as
73%, 99%, 84%, 19% and 67%. Waste H2O2 was found successful in NH4+
removal during post treatment where 80% nitrogen was removed. Low cost
integrated treatment using UAB and H2O2 was found an excellent novel
treatment choice for mixed MWW in developing countries.
6. Anaerobic treatment in combination with post treatment of advanced oxidation
process was employed to test the treatability of integrated process for
confectionary wastewater mixed with MWW. Reactor was inoculated with 10
year old septic tank sludge and started up with glucose, macro and micro
nutrients. The system was operated at 25-30C, HRT 48 hrs for 25 days with
post treatment with 40% waste H2O2. This waste H2O2 was collected from
industrial process after disinfection of packaging material. Reactor performance
was evaluated by pre and post treatment analysis of COD, TSS, TDS, and
turbidity. Their removal efficiencies were up to 98.6%, 91%, 50% and 81%,
respectively. Reactor achieved its full efficiency after feeding diluted
wastewater as 1/5, 1/3, 1/2 and 1/0 for 5 7 days each. Reactor achieved full
efficiency in 25 days removing 98% COD from mixed wastewater. A batch
peroxide treatment process was also added to reduce the turbidity and to
increase the DO of treated effluent. The strategy was found quite applicable for
the treatment of combined industrial and municipal effluents.
163
9.2 Future Recommendations

The present study of removal of COD ammonium and SS has proven to be very
promising for practical implementation in industry as well as for MWW treatment. It can
be more attractive when using waste from one industry to treat other industry waste.
Following recommendations should be considered for future work on UASB treatment in
combination with 40% waste H2O2.
1. Same type of reactor needs to acclimiate with high COD load such as 25000 mg
L-1 because some food industries espacially confectionary discharge at >4500 mg
L-1 with recycling. Handling such high load COD effluent could also pass through
increased sludge bed hight to avoid recylcing.
2. Wastewater with high COD due to excess of carbohydrates in effluent can be
employed in biohydrogen and biogas production. In this case it is assumed that
biogass production will be more feasible.
3. UASB reactor face challenges in the development of a successful application of
high strenght wastewater and treatment under psychrophyllic and mesophyllic
environment. There is lack of information regarding kinetics involved during
high, low temperature and high strength wastewater. In case of high organic load
as in confectionary industry then informationn on rates of waste utilization, half
velocity constant, decay rate and growth yeild will be obligatory to implement
this integrated treatment design. Process kinetics should also deal with
environmental factors effecting the treatment efficiency.
4. Different HRT still need to be investigated thoroughly. The treatment under very
HRT will be highly desirable to apply high organic loading. Using same sludge
collected from septic can be used to study extremely low HRT when treating
municipal and confectionary wastewater.
5. Post treatment with waste 40% H2O2 was used to treat UASB effluent for
municipal and confenctionary wastewater. There are still need to explore the
mechanism of nitrogen and phosphate removal during post treatment advanced
oxidation processes.
164
Curriculum Vitae
Name:
Qualification:
B.Sc (hons) Agriculture, Agriculture University Faisalabad

MSc. Food Preservation Engineering,
Katholieke university Leuven Belgium.
MSc. Environmental Sciences,
Ghent University Belgium.
Correspondence
address:
Environmental Sciences Department,
COMSATS Institute of Information Technology,
Tobe Camp Abbottabad. 22060.
Emails:
zabhatti@ciit.net.pk
bhattizulfqar@yahoo.com
List of publication in international SCI journals
Zulfiqar Ahmed Bhatti, Qaisar Mahmood, Iftikhar Ahmad Raja, Zahid

Mahmood Khan, Amir Haider Malik, (2010), Chemical Oxidation of Carwash
Industry Wastewater as Efforts to Decrease Water Pollution, Journal of Physics
and chemistry of the earth, Published. Online available.
Zulfiqar Ahmed Bhatti, Qaisar Mahmood, Iftikhar Ahmad Raja, Zahid

Mahmood Khan, Amir Haider Malik (2010) Integrated Chemical Treatment of
Domestic Wastewater Using Waste Hydrogen Peroxide and Ultraviolet Light,
Journal of Physics and chemistry of the earth, Published. Online available.
Zulfiqar Ahmad Bhatti, Qaisar Mahmood, Iftikhar Ahmad Raja, Farhana

Maqbool, (2010), Low Cost Municipal Wastewater Treatment Options for
Pakistan, A review, A Journal of Science for Development, 15(1), 71-78.
Naim Rashid, Qaisar Mahmood, Zulfiqaar Ahmad Bhatti, Noshin Mirza., Jamil
Khan, (2010) Precipitation Chelation of Cyanide Complexes in Electroplating
Industry, Int. J. Environ. Res., 4(4): 735-373.
Zulfiqar Ahmad Bhatti, Qaisar Mahmood, Iftikhar Ahmad Raja, (2009), Sewage
Water Pollutants Removal Efficiency Correlates to the Concentration Gradient of
Amendments, Jour. Chem. Soc. Pak, (31) 665-673.
165
Jamil Khan, Rehana Rashid, Naim Rashid, Zulfiqar Ahmed Bhatti, Nadeem
Bukhari, Muhammad Aurangzaib Khan and Qaisar Mahmood., (2010),
Assessment of Selected Organotin Complexes Against Plnat Pathogen Fungi
sarhad J Agric., 26(1): 65-68.
Amir Haider Malik, Zahid Mahmood Khan, Qaisar Mahmood, Sadia Nasreen,
Zulfiqar Ahmad Bhatti; (2009), Perspective of low cost arsenic remediation of
drinking water in Pakistan and other countries, Journal of Hazardous Material,
(168) 1-12.
Sajid Hussain Shah., Donglei Wou, Qaisar Mahmood, Zulfiqar Ahmad Bhatti,
(2010), Low temperature conversion of plastic waste into light hydrocarbon,
Journal of Hazardous Material,179: 15-20.
Farhana Maqbool, Zulfiqar Ahmad Bhatti, Amir Haider Malik, Arshad Pervez
and Qaisar Mahmood, (2011), Effect of Landfill Leachate on the Water Quality of
the Salhad Stream in Abbottabad, Pakistan, Int. J. Environ. Res, V. 5(2):491-500
(ISI, IF=0.737).
List of publication in international conferences
Maqbool Farhana, Zulfiqar Ahmad Bhatti, Amir Haider Malik, Qaisar

Mahmood, Xu Ying and Zhenyu, Wang, Statistical analysis of water quality
parameters of Salhad stream affected by landfill leachate, SETACAP Asia /
Pacific 2010 annual meeting, Guangzhou, China.
Zulfiqar Ahmad Bhatti, Qaisar Mahmood, Iftikhar Ahmad Raja, Rao Naim,
Farhana Maqbool, (2009), Treatment and reuse of industrial wastewater using
advanced oxidation process, ESDev-2009,805-810.(Poster competition winning
paper)
Farhana Maqbool, Zulfiqar Ahmad Bhatti, Amir Haider Malik, (2009),

Comparison of Salhad Stream Water Quality in Dry and Wet Seasons, ESDev2009, COMSATS, Abbottabad, Pakistan
Asad Ashraf, Qaisar Mahmood, Zulfiqar Ahmad Bhatti, (2009), Water

softening and pathogenic microbial removal from drinking water, ESDev-2009,
776-782.
NaimRashid, Zulfiqar Ahmad Bhatti (2009), Bio-hydrogenase a source of

renewable energy: the optimization of various factors, ESDev-2009, 435-439.
Farhana Maqbool, Amir Haider Malik, Zulfiqar Ahmad Bhatti, Arshad Pervez,
(2009), Physicochemical Water Quality Seasonal Variations of the Salhad Stream,
South Abbottabad, North Pakistan, 24th International Conference on solid Waste
Technology and Management held in Philadelphia, PA, U.S.A. on March 15-18,
2009.
Farhana Maqbool, Amir Haider Malik, Zulfiqar Ahmad Bhatti, Arshad Pervez,
(2009), Effect of Solid Waste Disposal on the Microbiological Water Quality of
166
Salhad Stream South Abbottabad, North Pakistan, 24th International Conference

on Solid Waste Technology and Management held in Philadelphia, PA, U.S.A. on
March 15-18, 2009.
Zulfiqar Ahmad Bhatti, Zahid Mahmood Khan, (2007); Fatty Acids Changes in
Endive Roots (Cichorium intybus) During Chilling Environment, ESDev- 2007,
613-622.
Zufliqar Ahmad Bhatti, Iftikhar Ahmad Raja, (2007), Particle Settling in

Continuous Flow Primary Sedimentation Tank Designed for Laboratory Scale
Municipal Wastewater Treatment, ESDev 2007, 860-869.
Zulfiqar Ahmad Bhatti, Iftikhar Ahmad Raja, (2005), Emission of VOC from
Fat Rendering Plant, ESDev-2005
Zulfiqar Ahmad Bhatti, Iftikhar Ahmad Raja, (2005), Water Purification Using
Micron Filtration and Ozonation for Ground Water, ESDev-2005, 1837-1866.
Saleem Farooq Shaukat, Zulfiqar Ahmad Bhatti, (2005), Removal of Chromium

from Industrial Effluents by Sono-Electrolysis Process, ESDev-2005, 827- 832.
167

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Low Cost Municipal Wastewater Treatment

Zulfiqar Ahmad Bhatti

COMSATS Institute of Information Technology

COMSATS Institute of Information Technology

Low Cost Municipal Wastewater Treatment

COMSATS Institute of Information Technology, Abbottabad

Zulfiqar Ahmad Bhatti

Low Cost Municipal Wastewater Treatment

A Post Graduate Thesis submitted to the Department of Environmental Sciences

Zulfiqar Ahmad Bhatti

Low Cost Municipal Wastewater Treatment

Zulfiqar Ahmad Bhatti

External Examiner: __________________________________________

Signature of the student:

Dr. Iftikhar Ahmad Raja

Dr. Arshad Pervez

Prof. Dr. Ishtiaq Jadoon

To Almighty ALLAH and the Holy Prophet

My Loving Mother (Hafeeza Iftikhar) and Wife

laboratory attendants Saboor, Maroof and Naeem facilitating in handling equipments

May Allah bless all of us and may this contribution be

Zulfiqar Ahmad Bhatti

Moreover, the effect of

Chapter 1: Introduction .............................................................................................. 1

LOW COST TREATMENT OPTION FOR PAKISTAN ...................................................... 4

Sewage treatment ................................................................................................................ 4

Process overview ................................................................................................................. 4

Grit removal ........................................................................................................................ 5

Primary treatment ................................................................................................................ 5

SECONDARY TREATMENT ......................................................................................... 6

UP-FLOW ANAEROBIC TREATMENT REACTOR ......................................................... 6

OTHER MUNICIPAL WASTEWATER TREATMENT OPTIONS....................................... 7

Activated sludge .................................................................................................................. 7

Rotating biological contactors ............................................................................................ 8

Constructed wetlands .......................................................................................................... 9

Nutrient removal ................................................................................................................. 9

TERTIARY TREATMENT .......................................................................................... 11

AIMS OF THIS STUDY .............................................................................................. 12

2 Chapter 2: Literature Review .............................................................................. 17

CHARACTERISTICS OF MUNICIPAL WASTEWATER/DOMESTIC WASTEWATER ...... 18

NEWLY IDENTIFIED TOXICANTS IN TREATED DOMESTIC WASTEWATER .............. 20

TREATMENT OPTIONS ............................................................................................. 21

Primary sedimentation ...................................................................................................... 21

Physico-chemical treatment .............................................................................................. 23

COLLOIDAL CHEMISTRY OF WASTEWATER ........................................................... 24

COAGULATION IN WATER TREATMENT ................................................................. 24

CHEMICALLY PRIMARY TREATMENT OF WASTEWATER ........................................ 25

Financial benefits of CEPT ............................................................................................... 26

Efficiency of organic and inorganic coagulants ............................................................... 26

OILY WASTEWATER TREATMENT WITH COAGULATION/FLOCCULATION ............. 29

USE OF CEPT SLUDGE AS ADSORBENT .................................................................. 29

EFFECT OF POLYMERIC FLOCCULENT PRODUCED FROM PLASTIC WASTE ............ 30

COMBINE CHEMICAL AND BIOLOGICAL LOW COST TREATMENT SYSTEMS .......... 31

ADVANCE OXIDATION PROCESSES IN MUNICIPAL WASTEWATER TREATMENT.... 33

Municipal wastewater treatment with H2O2 ................................................................ 34

Fenton reagent in AOP ................................................................................................. 35

Textile effluent treatment with AOP ........................................................................... 36

SLUDGE DIGESTION WITH H2O2.............................................................................. 36

ANAEROBIC TREATMENT OF MUNICIPAL WASTEWATER TREATMENT.................. 37

Acetogenesis and Acid Formation ............................................................................... 38

Start up of up flow anaerobic sludge blanket (UASB) reactor ................................... 39

Start up of UASB reactor without inoculation ............................................................ 45

Function of micro-nutrients during start-up of UASB ................................................ 46

Operational data and micronutrient requirement ......................................................... 47