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CO-TREATMENT

OF

LANDFILL

LEACHATE

AND

SETTLED DOMESTIC WASTEWATER USING COMPOSITE


ADSORBENT IN SEQUENCING BATCH REACTOR

AMIN MOJIRI

UNIVERSITI SAINS MALAYSIA

2014

CO-TREATMENT OF LANDFILL LEACHATE AND


SETTLED DOMESTIC WASTEWATER USING COMPOSITE
ADSORBENT IN SEQUENCING BATCH REACTOR

by

AMIN MOJIRI

Thesis submitted in fulfillment of the


requirements for the degree of
Doctor of Philosophy

December 2014

ACKNOWLEDGMENT

I wish to express my profound gratitude to God (Allah); the Allah gave me the ability
and patience to accomplish my education.
I would like to appreciate my supervisor, Professor Hamidi Bin Abdul Aziz,
who has inspired and accompanied me throughout the stage of my study to the
smallest details. His constant guidance, subjective criticism, continuous support, and
great inspiration throughout the duration of my research are most valued. Also, I
would like to appreciate my co-supervisor, Dr. Nastaein Q. Zaman.
I also want to thank all technicians of Environmental Lab at School of Civil
Engineering. They have helped me a lot during the experiments. I also appreciate
Institute of Postgraduate Studies (IPS), USM because they provided funding and
fellowship during my education. And I would like to express my gratitude to the
Universiti Sains Malaysia (USM) for providing the research grant (Grant no.
1001/PAWAM/8045052) for this study and all their support.
Finally, this thesis is dedicated to my family. I really appreciate my father
Engr. Abdolkhalegh Mojiri, mother Masoumeh Khosravinejad, and my brother Engr.
Ehsan Mojiri. I sincerely thank you because of all your understanding, trust,
encouragement, and faith during the years of study.

ii

TABLE OF CONTENTS

ACKNOWLEDGMENTS

Page
ii

TABLE OF CONTENTS

iii

LIST OF TABLES

xiii

LIST OF FIGURES

xvi

LIST OF PLATES

xxi

LIST OF ABBREVIATIONS

xxii

ABSTRAK

xxiii

ABSTRACT

xxv

CHAPTER 1- INTRODUCTION
1.1

Background of the study

1.2

Problem statement

1.3

Objectives

1.4

Scope of the study

1.5

Thesis organization

CHAPTER 2- LITERATURE REVIEW


2.1

Introduction

2.2

Sanitary landfill

2.2.1

11

Category based on operating purposes

iii

2.2.2

Category based on landfill structure

12

2.3

Landfill leachate

13

2.4

Landfill leachate treatment technologies

16

2.5

Biological methods

16

2.5.1

Anaerobic method

16

2.5.2

Aerobic method

18

2.5.3

Some types of bioreactors

18

2.6

2.5.3.1 Upflow anaerobic sludge blanket

18

2.5.3.2 Upflow anaerobic filter

18

2.5.3.3

Anaerobic hybrid reactor

19

2.5.3.4

Membrane bioreactor

19

2.5.3.5

Activated sludge system

19

2.5.3.6

Sequencing batch reactor

21

A.

Advantages and disadvantages of SBR

22

B.

Additional information on SBR

23

Physical/chemical methods

24

2.6.1

Chemical precipitation

24

2.6.2

Chemical oxidation

25

2.6.2.1
2.6.3

Fenton treatment

25

Coagulationflocculation or flocculationprecipitation

iv

25

2.6.4

Membrane filtration

26

2.6.4.1

Microfiltration

26

2.6.4.2

Ultrafiltration

26

2.6.4.3

Nanofiltration

27

2.6.4.4

Reverse Osmosis (RO)

27

2.6.5

Electrochemical treatment

2.6.5.1

27

Electrooxidation

28

2.6.6

Ion exchange

28

2.6.6

Adsorption

29

2.7 Adsorption isotherms

30

2.7.1

Langmuir isotherm

31

2.7.2

Freundlich isotherm

32

2.7.3

Adsorption efficiency of adsorbents in wastewater

33

treatment
2.8 Wastewater treatment by ion exchanges and adsorbents

34

2.9

37

Wastewater treatment by composite adsorbent

2.10 Co-treatments of landfill leachate and wastewater

38

2.11 Main parameters for anaerobic and aerobic treatments

41

2.11.1 F/M ratio

41

2.11.2 Hydraulic retention time

42

2.11.3 Flow rate

43

2.11.4 Organic loading rate

43

2.12 Response Surface Method (RSM)

44

2.13 Summary

46

CHAPTER 3 - MATERIALS AND METHODS


3.1

Introduction

48

3.2

Case study sites

48

3.2.1

48

Semeling Landfill, Sungai Petani

3.2.1.1

Site description

48

3.2.1.2

Sampling procedures

50

3.2.2

Bayan Baru Sewage Treatment Plant (BBSTP)

51

3.2.2.1

Site description

51

3.2.2.2

Sampling procedures

52

3.3

Analytical methods

53

3.4

Reactor characteristics in all experiments

54

3.5

ZELIAC preparation with activated carbon and zeolite

56

3.6

Sludge acclimatization for batch/optimization and continuous

57

SBR experiments
3.7

Pre-SBR experiments

58

3.7.1

58

Batch/shaking experiments

3.7.1.1 PZ dosage

59

vi

3.7.1.2 Settling time

59

3.7.1.3 Summary of batch/shaking experiments

59

3.7.2
3.8

Batch/optimization experiments (design experiments)

60

Continuous SBR experiments

64

3.8.1

Normal-SBR

65

3.8.2

PZ-SBR

65

3.8.3

PAC-SBR

65

3.8.4

PZE-SBR

66

CHAPTER 4 - RESULTS AND DISCUSSIONS

4.1

Introduction

67

4.2

Characteristics of landfill leachate in Semeling, Sungai Petani

67

4.3

Domestic wastewater and activated sludge characteristics

70

4.4

Pre-SBR experiments

72

4.4.1

72

Batch/shaking experiments

4.4.1.1 Settling time

73

4.4.1.2 PZ Production and PZ Dosage

75

A. PZ Production

75

B.

Optimal PZ dosage (mg/L)

75

C.

Adsorption isotherm

76

vii

D.

Langmuir isotherm

77

E.

Freundlich isotherm

81

4.4.2

ZELIAC,Zeolite and Activated Carbon Characteristics

85

4.4.3

Batch/optimization experiments

92

4.4.3.1 Design of experiments by response surface

92

methodology
4.4.3.2 Operation and performance of the reactors

92

4.4.3.3 Normal SBR reactors

98

i)

Colour removal

98

ii) COD removal

98

iii) NH3-N removal

99

iv) Phenols removal

99

v)

99

Iron removal

vi) Manganese removal

100

vii) Nickel removal

100

viii) Cadmium removal

100

4.4.3.4 PZ-SBR reactors (PZ supplemented SBR)


i)

Colour removal

109
109

ii) COD removal

109

iii) NH3-N removal

109

viii

iv) Phenols removal

110

v)

110

Iron removal

vi) Manganese removal

110

vii) Nickel removal

111

viii) Cadmium removal

111

4.4.3.5 PAC-SBR reactors (PAC supplemented SBR)


i)

Colour removal

120
120

ii) COD removal

120

iii) NH3-N removal

120

iv) Phenols removal

121

v)

121

Iron removal

vi) Manganese removal

121

vii) Nickel removal

122

viii) Cadmium removal

122

4.4.3.6 PZE-SBR reactors (powdered zeolite supplemented

131

SBR)
i)

Colour removal

131

ii) COD removal

131

iii) NH3-N removal

131

iv) Phenols removal

132

ix

v)

4.4.4

Iron removal

132

vi) Manganese removal

132

vii) Nickel removal

133

viii) Cadmium removal

133

Comparing the four types of reactors

4.4.4.1 Comparing contact time, aeration rate and leachate

142
142

to wastewater mixing ratio in optimum condition by


RSM
4.4.4.2 Comparing the removal of colour, COD, ammonia

143

and phenols in optimum condition by RSM

4.4.4.3

A)

Colour removal

144

B)

COD removal

145

C)

Ammonia removal

145

D)

Phenols removal

146

Comparing the Fe, Mn, Ni and Cd in optimum

148

condition by RSM

4.5

A)

Fe removal

149

B)

Mn removal

150

C)

Ni removal

151

D)

Cd removal

152

Variation of DO inside reactors

153

4.6

4.5.1

Effect on contact time on DO in reactors

154

4.5.2

Effect of aeration rate on DO in the reactors

156

Statistical analysis and comparing results

158

4.6.1

158

Statistical analysis

4.7 HRT, F/M and OLR in four reactors in optimization experiments

4.8

169

4.7.1 Hydraulic Retention Time (HRT)

169

4.7.2 Organic Loading Rate (OLR)

170

4.7.3 Mixed Liquor Suspended Solid (MLSS)

171

4.7.4 The F/M Ratio

172

Continuous experiments results

172

4.8.1 Performance of reactors in pollutants removal

174

4.8.1.1

Colour, COD, ammonia, phenols, and sulfide

174

removal
4.8.1.2 Fe, Mn, Ni, Cd and Cr (VI) removal

175

4.8.1.3 Nitrification and denitrification process

176

A)

Nitrification

177

B)

Denitrification

177

CHAPTER 5- CONCLUSION AND RECOMMENDATIONS


5.1

Conclusions

179

5.2

Recommendations

180

xi

REFERENCE

181

APPENDIX A: Literature Review and Batch/Shaking Experiments

198

APPENDIX B: Adsorption Isotherms and Raw data

199

LIST OF PUBLICATIONS

204

xii

LIST OF TABLES

Page
Table 2-1

Benefits and disadvantages of sanitary landfills

11

Table 2-2

Total Landfills in Malaysia (Source: National Solid Waste


Management Department, 2014)

12

Table 2-3

Classification of landfill structures

12

Table 2-4

A view of rill erosion formed in dispersive clays (Vakili,


2008)

13

Table 2-5

Characteristics of leachate generated from decomposition of


MSW in developing countries

15

Table 2-6

Landfill leachate classification versus age

15

Table 2-7

Treatment of different types of wastewaters by using the


SBR process (Source: Aziz et al., 2011)

22

Table 2-8

Time for fill, settle, draw and idle phases in SBR studies

22

Table 2-9

Application ZELIAC and its compounds to treat wastewater

38

Table 3-1

Analytical methods

54

Table 3-2

The values of raw materials to prepare 1 ton of ZELIAC

57

Table 3-3

Coded and actual values of variables for normal-SBR, PZSBR, PAC-SBR, and PZE-SBR

63

Table 3-4

Experimental variables for SBRs

64

Table 3-5

Details of continuous SBR experiments

66

Table 4-1

Semeling Petani Landfill Leachate Characteristics

69

Table 4-2

Bayan Baru, Penang, Domestic Wastewater and Activated


Sludge Characteristics

41

xiii

(Source: Aziz, 2011)

Table 4-3

Langmuir equation for colour, COD and ammonia

78

Table 4-4

Langmuir equation for Fe, Mn and Ni

78

Table 4-5

Freundlich equation for colour, COD and ammonia

81

Table 4-6

Freundlich equation for Fe, Mn and Ni

82

Table 4-7

Langmuir and Freundlich equations for current study

85

Table 4-8

Powdered PZ, PAC and PZE Characteristics

86

Table 4-9

XRF results for ZELIAC

86

Table 4-10

XRF results for zeolite

89

Table 4-11

Experimental variables and results for the Normal-SBR

94

Table 4-12

Experimental variables and results for the PZ-SBR

95

Table 4-13

Experimental variables and results for the PAC-SBR

96

Table 4-14

Experimental variables and results for the PZE-SBR

97

Table 4-15

The value of factors and responses at optimum conditions

142

Table 4-16

ANOVA results for response parameter (about colour, COD,


ammonia and phenols)

160

Table 4-17

ANOVA results for response parameter (about metals)

161

Table 4-18

Minimum and maximum HRT in four reactors in


optimization experiments

170

Table 4-19

Minimum and maximum OLR in four reactors in


optimization experiments

170

Table 4-20

Minimum and maximum MLSS in four reactors in


optimization experiments

171

Table 4-21

Minimum and maximum F/M in four reactors in


optimization experiments

172

xiv

Table 4-22

Operation parameters in continuous experiments

173

Table 4-23

Characteristics of landfill leachate and domestic wastewater

173

Table 4-24

Removal efficiency of color, COD, ammonia, phenols and


sulfide

175

Table 4-25

Concentrations of color, COD, ammonia, phenols and


sulfide after treatment

175

Table 4-26

Average removal efficiency of Fe, Mn, Ni, Cd and Cr (VI)

175

Table 4-27

Average concentrations of Fe, Mn, Ni, Cd and Cr (VI) after


treatment

176

xv

LIST OF FIGURES
Page
Figure 2-1

Schematic of basic aspects of a sanitary landfill (Source:


UNEP, 2005)

11

Figure 2-2

Classification of landfill structures (source: Aziz, 2011;


Environmental Control Pollution Center, Osaka Prefecture,
2009)

14

Figure 2-3

Diagram of landfill leachate treatment techniques (based on


Abbas et al., 2009 and Renou et al., 2008)

17

Figure 2-4

Representation of the main units in the biological stage of


the activated sludge system (Source: Sperling, 2007)

20

Figure 3-1

Methodology flow chart

49

Figure 3-2

Semeling Landfill site (Source: Google maps)

50

Figure 3-3

Leachate collection

51

Figure 3-4

Aerial view of BBSTP and its various units (source: Aziz,


2011; Penang, Bayan Lepas; 05 18' 58"N, 100 17' 38"E)

52

Figure 3-5

Aeration tank and sampling of return activated sludge at the


site

53

Figure 3-6

Schematic of the SBR arrangement in batch/optimization


and continuous SBR experiments

55

Figure 3-7

Sludge acclimatization

57

Figure 3-8

Pre-SBR experiments

58

Figure 4-1

Phases of normal SBR (Source: Mahvi, 2008)

74

Figure 4-2

Effect of Settling Time on DO in SBR

74

Figure 4-3

Removal parameters versus PZ-SBR dosage

76

xvi

Figure 4-4

Langmuir isotherm regression for (a) colour, (b) COD and


(c) NH3-N

79

Figure 4-5

Langmuir isotherm regression for (a) Fe, (b) Mn and (c) Ni

80

Figure 4-6

Freundlich isotherm regression for (a) colour, (b) COD and


(c) NH3-N

83

Figure 4-7

Freundlich isotherm regression for (a) Fe, (b) Mn and (c) Ni

84

Figure 4-8

XRD Results for ZELIAC

87

Figure 4-9

SEM images from surface of ZELIAC

88

Figure 4-10

SEM images from surface of zeolite

90

Figure 4-11

SEM images from surface of activated carbon

91

Figure 4-12

The 3D surface plots of colour removal in Normal-SBR

101

Figure 4-13

The 3D surface plots of COD removal in Normal-SBR

102

Figure 4-14

The 3D surface plots of ammonia removal in Normal-SBR

103

Figure 4-15

The 3D surface plots of phenols removal in Normal-SBR

104

Figure 4-16

The 3D surface plots of Fe removal in Normal-SBR

105

Figure 4-17

The 3D surface plots of Mn removal in Normal-SBR

106

Figure 4-18

The 3D surface plots of Ni removal in Normal-SBR

107

Figure 4-19

The 3D surface plots of Cd removal in Normal-SBR

108

Figure 4-20

The 3D surface plots of colour removal in PZ-SBR

112

Figure 4-21

The 3D surface plots of COD removal in PZ-SBR

113

Figure 4-22

The 3D surface plots of ammonia removal in PZ-SBR

114

Figure 4-23

The 3D surface plots of phenols removal in PZ-SBR

115

xvii

Figure 4-24

The 3D surface plots of Fe removal in PZ-SBR

116

Figure 4-25

The 3D surface plots of Mn removal in PZ-SBR

117

Figure 4-26

The 3D surface plots of Ni removal in PZ-SBR

118

Figure 4-27

The 3D surface plots of Cd removal in PZ-SBR

119

Figure 4-28

The 3D surface plots of color removal in PAC-SBR

123

Figure 4-29

The 3D surface plots of COD removal in PAC-SBR

124

Figure 4-30

The 3D surface plots of ammonia removal in PAC-SBR

125

Figure 4-31

The 3D surface plots of phenols removal in PAC-SBR

126

Figure 4-32

The 3D surface plots of Fe removal in PAC-SBR

127

Figure 4-33

The 3D surface plots of Mn removal in PAC-SBR

128

Figure 4-34

The 3D surface plots of Ni removal in PAC-SBR

129

Figure 4-35

The 3D surface plots of Cd removal in PAC-SBR

130

Figure 4-36

The 3D surface plots of colour removal in PZE-SBR

134

Figure 4-37

The 3D surface plots of COD removal in PZE-SBR

135

Figure 4-38

The 3D surface plots of ammonia removal in PZE-SBR

136

Figure 4-39

The 3D surface plots of phenols removal in PZE-SBR

137

Figure 4-40

The 3D surface plots of Fe removal in PZE-SBR

138

Figure 4-41

The 3D surface plots of Mn removal in PZE-SBR

139

Figure 4-42

The 3D surface plots of Ni removal in PZE-SBR

140

Figure 4-43

The 3D surface plots of Cd removal in PZE-SBR

141

Figure 4-44

Comparing contact time (h) in the reactors in optimum


condition

142

Figure 4-45

comparing aeration rate (L/min) in the four reactors in


optimum condition

143

xviii

Figure 4-46

Comparing leachate to wastewater mixing ration (%) in the


four reactors in optimum condition

143

Figure 4-47

Comparing color removal (%) in the reactors in optimum


condition

144

Figure 4-48

Comparing COD removal (%) in the reactors in optimum


condition

145

Figure 4-49

Comparing ammonia removal (%) in the four reactors in


optimum condition

146

Figure 4-50

Comparing phenols removal (%) in the four reactors in


optimum condition

147

Figure 4-51

Comparing Fe removal (%) in the reactors in optimum


condition

150

Figure 4-52

Comparing Mn removal (%) in the reactors in optimum


condition

151

Figure 4-53

Comparing Ni removal (%) in the reactors in optimum


condition

152

Figure 4-54

Comparing Cd removal (%) in the reactors in optimum


condition

153

Figure 4-55

Effect of contact time on DO in the reactors (aeration rate


0.5 L/min; combined leachate to wastewater; 50%)

155

Figure 4-56

Effect of contact time on DO in the reactors (aeration rate


4.0 L/min; combined leachate to wastewater; 50%)

155

Figure 4-57

Effect of contact time on DO in the reactors (aeration rate


7.5 L/min; combined leachate to wastewater; 50%)

156

Figure 4-58

Effect of aeration rate on DO in the reactors (contact time


2h; combined leachate to wastewater; 50%)

157

Figure 4-59

Effect of aeration rate on DO in the reactors (contact time


12h; combined leachate to wastewater; 50%)

157

Figure 4-60

Effect of aeration rate on DO in the reactors (contact time


22h; combined leachate to wastewater; 50%)

158

xix

Figure 4-61

Design-expert plot; predicted vs. actual values plot for


colour

162

Figure 4-62

Design-expert plot; predicted vs. actual values plot for COD

163

Figure 4-63

Design-expert plot; predicted vs. actual values plot for


ammonia

164

Figure 4-64

Design-expert plot; predicted vs. actual values plot for


phenols

165

Figure 4-65

Design-expert plot; predicted vs. actual values plot for Fe

166

Figure 4-66

Design-expert plot; predicted vs. actual values plot for Mn

167

Figure 4-67

Design-expert plot; predicted vs. actual values plot for Ni

168

Figure 4-68

Design-expert plot; predicted vs. actual values plot for Cd

169

Figure 4-69

Minimum and maximum MLSS in four reactors in


optimization experiments

171

Figure 4-70

The concentration of NH3-N, NO2-N and NO3-N in raw


leachate and reactors

178

xx

LIST OF PLATES
Page
Plate 3-1: Powdered ZELIAC

61

Plate 3-2: Powdered activated carbon

61

Plate 2-3: Powdered zeolite

61

xxi

LIST OF ABBREVIATIONS

PZ

Powdered ZELIAC;

PAC

Powdered Activated Carbon;

PZE

Powdered Zeolite;

SBR

Sequencing Batch Reactor;

HRT

Hydraulic Retention Time;

OLR

Organic Loading Rate;

XRF

X- ray fluorescence;

XRD

X-ray diffraction;

SEM

Scanning Electron Microscope;

xxii

OLAHAN BERSAMA LARUT LESAPAN KAMBUS TANAH DAN AIR


SISA DOMESTIK TERENAP MENGGUNAKAN PENJERAP KOMPOSIT
DALAM REAKTOR KELOMPOK BERTURUTAN

ABSTRAK
Reaktor kelompok berturutan (SBR) merupakan satu daripada sistem olahan
biologi yang digunakan dalam olahan air sisa. Kajian ini menyelidiki olahan bersama
larut lesapan kambus tanah Semeling, Sg. Petani dan air sisa domestik Bayan Baru,
dengan menambah bahan penjerap baru (ZELIAC serbuk, PZ), karbon teraktif
serbuk (PAC) dan zeolite serbuk (PZE) ke dalam sistem SBR. Beberapa parameter
seperti BOD, COD, ammonia, phenol dan logam dalam larut lesapan kambus tanah
Semeling melepasi standard pelepasan efluen yang dibenarkan semasa kajian ini.
ZELIAC dibentuk oleh zeolite, karbon teraktif, batu kapus, debu sekam padi dan
simen Portland. Unsur dan kompaun utama ZELIAC adalah SO2, CaO, dan C. Dalam
kajian ini, saiz penjerap adalah dalam julat 75 m ke 150 m. Kaedah Tindak Balas
Permukaan (RSM) dan Reka bentuk Komposit Tengah (CCD) digunakan dalam
penentuan keadaan optimum parameter tak bertindakbalas termasuk kadar
pengudaraan (L/min), masa sentuhan (h) dan nisbah campuran larut lesapan ke air
sisa (%; v/v). Untuk analisis proses aerobik, lapan parameter boleh-ubah diukur, iaitu
Keperluan Oksigen Kimia (COD), warna, nitrogen-ammonia (NH3-N), phenol, Fe,
Mn, Ni dan Cd. Parameter-parameter ini dipilih berdasarkan sorotan literatur serta
kepekatan bahan cemar ini melebihi yang lain dalam larut lesapan. Pada keadaan
optimum kadar pengudaraan (4.32 L/min), nisbah larut lesapan ke air sisa (20%), dan
masa sentuhan (12.68 jam) untuk SBR, kecekapan penyingkiran warna, NH3-N,
COD, phenol, Fe, Mn, Ni dan Cd adalah masing-masing 55.95%, 45.81%, 98.42%,

xxiii

33.83%, 45.03%, 38.85%, 44.64% dan 43.79%. Ini berbanding dengan pada keadaan
optimum kadar pengudaraan (4.21 L/min), nisbah larut lesapan ke air sisa (20%), dan
masa sentuhan (11.65 jam) untuk PZ-SBR, kecekapan penyingkiran warna, NH3-N,
COD, phenol, Fe, Mn, Ni dan Cd adalah masing-masing 84.74%, 72.35%, 99.54%,
61.93%, 79.58%, 73.32%, 79.28%, dan 76.94%. Berdasarkan parameter-parameter
optimum, eksperimen diulangi sebanyak lima kali dan nisbah F/M, masa tahanan
hidraulik (HRT), Kadar Beban Organik (OLR), dan oksigen terlarut (DO) diukur
dalam reaktor. Dalam eksperimen berterusan, keputusan menunjukkan PZ-SBR
memberikan kecekapan penyingkiran yang lebih baik bagi semua parameter yang
dikaji berbanding PAC-SBR, PZE-SBR dan SBR. PZ-SBR juga berpotensi lebih
baik dalam penyingkiran warna dan logam berat.

xxiv

CO-TREATMENT OF LANDFILL LEACHATE AND SETTLED DOMESTIC


WASTEWATER USING COMPOSITE ADSORBENT IN SEQUENCING
BATCH REACTOR
ABSTRACT
The sequencing batch reactor (SBR) is one of the biological treatment systems
used in wastewater treatment. This study investigated the co-treatment of Semeling
Sg. Petani landfill leachate and Bayan Baru domestic wastewater by adding a new
adsorbent material (powdered ZELIAC; PZ), powdered activated carbon (PAC), and
powdered zeolite (PZE) to the SBR system. Some parameters such as BOD, COD,
ammonia, phenols, and metals in Semeling landfill leachate, were above the
allowable effluent standards during this study. ZELIAC was prepared using zeolite,
activated carbon, limestone, rice husk ash, and Portland cement. The primary
elements and compounds in ZELIAC are SO2, CaO, and C. In the current study, the
size of the adsorbents ranged from 75 m to 150 m. Response Surface
Methodology and Central Composite Design were used to determine the optimum
conditions of the independent variables, including aeration rate, contact time, and
ratio of leachate to wastewater mixture. To analyze the aerobic process, eight
dependent parameters, namely, chemical oxygen demand (COD), color, ammonianitrogen (NH3-N), phenols, Fe, Mn, Ni, and Cd were measured. Under optimal
conditions of aeration rate (4.32 L/min), leachate to wastewater ratio (20%), and
contact time (12.68 h) for the SBR, reduction efficiencies for color, NH3-N, COD,
phenols, Fe, Mn, Ni, and Cd were 55.95%, 45.81%, 98.42%, 33.83%, 45.03%,
38.85%, 44.64%, and 43.79%, respectively. By contrast, at the optimal conditions of
aeration rate (2.41 L/min), leachate to wastewater ratio (20%), and contact time
(11.65 h) for PZ-SBR, reduction efficiencies for color, COD, NH3-N, phenols, Fe,
xxv

Mn, Ni, and Cd were 84.74%, 72.35%, 99.54%, 61.93%, 79.58%, 73.32%, 79.28%,
and 76.94%, respectively. The experiments were run five times using the optimum
parameters (continues SBR experiment). F/M Ratio, hydraulic retention time,
organic loading rate, and DO were monitored in the reactors. In continues
experiments, the results indicated that the PZ-SBR showed higher efficiencies in
reducing all parametric values under investigation compared with PAC-SBR, PZESBR, and SBR. The PZ-SBR also has a higher potential for reducing color and
removing heavy metals.

xxvi

CHAPTER 1
INTRODUCTION
1.1 Background of the study
In the majority of countries, sanitary landfills are the prevalent way of solid
waste disposal. This method has benefits; however, its main drawbacks is leachate
production, that should be managed well. Malaysia currently has 296 landfills
(National Solid Waste Management Department, 2014). Unfortunately, most of these
landfills are old dumpsites with no environmental control. The leachate is mostly
released directly into water sources without any treatment. This act poses a threat to
neighboring ecosystems, especially places in which landfills are situated upstream of
water systems (Aziz et al., 2011a). Without proper treatment, a landfill leachate
greatly increases water pollution because it penetrates through the soil and subsoil,
therefore, hazardous components should comply with discharge standards (Aziz et
al., 2011a).
Landfill

leachates

are

wastewater

products

that

have

considerable

environmental effects. High concentrations of certain contaminants are a dangerous


characteristic of leachates. Urban landfill leachates contain contaminants that are
separated into four key groups as follows: (1) dissolved organic matter, (2) inorganic
compounds (e.g., calcium, potassium, sodium, ammonium, calcium, magnesium,
sulfates, chlorides, and iron) (3) heavy metals (e.g., nickel, lead, copper, chromium,
cadmium, and zinc), and (4) xenobiotic organic materials (Tengrui et al., 2007).
Leachates are created when water penetrates into landfill waste, carrying with
it certain forms of pollutants such as ammonianitrogen (NH3N), biochemical
oxygen demand (COD), colour, biological oxygen demand (BOD5), suspended
solids, and metals. The leachate composition depends on the deposited waste, landfill

age, hydrology of the site, landfill operations, and landfill type. High concentrations
of suspended solids, BOD5, COD, ammonic-nitrogen, and metals are commonly
present in leachate (Foul et al., 2009).
As the landfill age increases, the biodegradable portion of organic
contaminants in the leachate decreases because of anaerobic disintegration.
Therefore, developed leachate normally includes more resistant organics than young
leachate. A young landfill leachate (age < 5 years) is usually characterized by high
COD (30000 mgL-1to 60000 mgL-1) and BOD (4000 mgL-1to 13000 mgL-1), high
ratio of BOD5/COD (0.4 to 0.7), relatively high amounts of ammonia (< 400 mgL-1),
and pH < 6.50. Mature landfill leachate (age > 10 years) is usually characterized by
high amounts of ammonia (>400 mgL-1), mildly high COD (< 4000 mgL-1), and a
low BOD5/COD ratio of less than 0.1 (Aziz et al., 2011b). In the first year of landfill
operations, free volatile fatty acids represent the most abundant group of organic
materials, and their rapid reduction occurs as the landfill ages. Ammonium nitrogen
levels increase in leachate over time. The level in mature landfill leachate is between
2000 and 3000 mg NNH4/dm3 (Klimiuk and Kulikowska, 2004). The group with the
highest integrity with increasing age resembles a fulvic material with its relatively
high carboxyl and aromatic hydroxyl group densities. Particular organic compounds
recognized in leachate are phthalates, pesticides, furans, halogenated aromatics,
polycyclic

aromatic

hydrocarbons,

and

napthalensulfonates

(Klimiuk

and

Kulikowska, 2004; Aziz, 2011). Landfill leachate treatment methods include


biological, physicalchemical, membrane separation, and thermal treatment
processes. Physicalchemical methods include adsorption, flocculationcoagulation,
flotation, ion exchange, chemical oxidation, and air stripping (Aziz et al., 2014).

Anaerobic and aerobic processes have been shown effective in treating landfill
leachate (Klimiuk and Kulikowska, 2004; Aziz et al., 2014). The activated sludge
system is one of the most common aerobic systems employed in leachate treatment
(Amirossadat, 2014). The sequencing batch reactor (SBR) is common in the
treatment of domestic, urban, dairy, industrial, synthetic, and slaughterhouse
wastewaters, as well as landfill leachates (Aziz et al., 2011a).
The fill, react, settle, draw, and idle phases in the SBR process occur in a single
tank. Recent modifications have been made to the original SBR design. SBR has
been employed to treat leachates with the low BOD5/COD ratio of 0.09 to 0.37 (Guo
et al., 2010). Aziz et al. (2011b) reported that SBRs are less effective in treating
landfill leachate than in treating urban and industrial wastes because of the low
BOD5/COD ratio and the high ammonia concentration of leachates. Therefore,
adsorption methods are employed as supplements in a SBR to increase the efficiency
in the removal of organic matter, ammonia, heavy metals, and other pollutants (Aziz
et al., 2011a, b). Aziz et al. (2011c) used a powdered activated carbon (PAC)supplemented SBR process to increase leachate-treatment efficiency. PAC-SBR
performed better in removing the main contaminants (e.g., COD, colour, ammonia,
phenols, and iron) from the landfill leachate.
Previous studies (Bashir et al., 2010; Aziz, 2011) indicate that adsorption is an
effective method for leachate treatment. A landfill leachate containing mixtures of
inorganic and organic species require adsorbents that can eliminate a variety of
contaminants (Renou et al., 2008). Activated carbon, zeolite, and activated alumina
are examples of adsorbents. Low-cost adsorbents include peat, limestone, and rice
husk ash. Activated carbon provides an attachment surface for microorganisms for
bioregeneration (Halim et al., 2012; Halim et al., 2013). Activated carbons are

known to be the most effective adsorbents of organic contaminants in the aqueous or


gaseous phases. Zeolite is a commonly used natural ion exchanger to eliminate
ammonia and other inorganic contaminants from leachates or wastewater (Halim et
al., 2010).
Halim et al. (2009) studied the removal of ammonia and COD from semiaerobic landfill leachates using the low-cost activated carbonzeolite adsorbent; the
results showed an increase in the percentage of ammonia (37%) adsorbed and a
higher reduction in COD (57.5%). A number of studies (i.e., Kulbat et al., 2003;
Mohan and Gandhimathi, 2009; Yan-jiao et al., 2010; Abdullah, 2010; Risnawati and
Damanhuri, 2010; Kamarudzaman et al., 2011; Chaari et al., 2011) have verified that
the use of adsorbents can remove a considerable amount of pollutants (e.g., metals)
from wastewater and landfill leachates.
Foul et al. (2009) studied landfill leachate treatment by limestone and activated
carbon in columns and batches. Lime et al. (2010) indicated that PAC and rice husk
ash are effective in removing nitrogen from landfill leachates. Based on the results of
previous studies, a new adsorbent called ZELIAC was produced in this study; which
has the characteristics of all the above mentioned adsorbents (Halim et al., 2010).
Furthermore, ZELIAC is considered both an adsorbent and ion exchanger; thus,
improving the performance of the SBR. Treating landfill leachate via biological
methods is difficult because of its low ratio of BOD5/COD, high ammonia content,
and the presence of heavy metal ions (Nesaj et al., 2007). Hence, Nesaj et al. (2007
and 2008) suggested co-treatment of landfill leachate and wastewater. A number of
researchers (Pelivanoski et al., 2009; Yu et al., 2010; Capodici et al., 2014) studied
the removal of contaminants, such as COD, ammonia, and metals, in the co-

treatment of leachate and wastewater using biological and physicalchemical


methods.
In this study, landfill leachate was mixed with wastewater and then treated by a
ZELIAC-augmented SBR technique to increase the biodegradability ratio of landfill
leachate and improve the SBR process.

1.2 Problem statement


Leachate management is one of the most critical parts of planning, design,
operation, and long-term management of urban solid waste (USW) landfills (Halim
et al., 2010). The performance of leachate treatment methods primarily depend on
leachate composition. Highly biodegradable compounds (i.e., young leachate) are
traditionally treated biologically; hence, the activated sludge process is commonly
employed. Metals are commonly removed using chemical or physical treatments. No
single method is applicable for all types of leachates to date. Researchers worldwide
continue to work on improving treatment systems. The SBR is a popular activated
sludge system in which the reactions occur in a single tank. As a biological method,
its performance is normally limited to the reduction of organics (i.e., BOD and
COD). The capability of a SBR to treat landfill leachate is lower than urban and
manufacturing wastes because of the low biodegradability and the high concentration
of ammonia in landfill leachate (Aziz et al., 2011c). Various workers have
investigated SBR modifications. The SBR has been applied to treat leachates
(Laitinen et al., 2006; Guo et al., 2010, Aziz, 2011). Studies have investigated the
addition of adsorbents, (i.e., activated carbon) to activate sludge in the SBR at the
end of the biological treatment of leachates (Foo and Hameed, 2009; Aziz et al.,
2011b; Aziz et al., 2011c; Aziz et al., 2012). On the basis of the literature (Bashir et

al., 2010; Aziz, 2011; Aziz et al. 2011a), the main contaminants in leachate are COD,
colour, ammonia, phenols, and metals; these contaminants can be removed using
biological and physicalchemical methods.
The treatment of domestic wastewater is well established. The SBR system has
been well accepted worldwide, including Malaysia. Channeling landfill leachates
into domestic wastewater treatment plants has been practiced for many years
(Capodici et al., 2014). However, limited information on the co-treatment of landfill
leachates with urban wastewater is available to date.The use of the SBR for this cotreatment has been very limited. A SBR augmented by activated carbon has been
investigated for leachate treatment (Aziz, 2011). The USM team developed a new
composite medium called ZELIAC as a landfill leachate treatment. ZELIAC was
prepared using different types of low-cost materials (e.g., limestone, zeolite,
activated carbon, burnt rice husk, and Portland cement as a binder) (Halim et al.,
2010). The team used ZELIAC to reduce levels of certain parameters and remove
contaminants (e.g., COD and ammonia) from semi-anaerobic landfill leachates.
ZELIAC is a favorable alternative to the expensive activated carbon. In the
present research, ZELIAC was investigated as a supplement in the SBR for the cotreatment of domestic wastewater and landfill leachates. Powdered ZELIAC-SBR
(PZ-SBR) for landfill leachates and domestic wastewater treatment has the
characteristics of all adsorbents used in previous studies. A comparison of the
performances of PZ-SBR, PAC-SBR, and powdered zeolite-SBR (PZE-SBR) has not
been reported. This study aims to fill this knowledge gap in the SBR process.
One of the most important properties in the SBR is the settling time. Before the
effluent is withdrawn, settling of biomass takes place. Sludge that has not settled
within the given settling time could be washed out of the reactor (Tay et al., 2006). In

literature, different settling times have been suggested. In some studies, several
researchers have suggested a settling time of 2 h (Jian, 2008; Chan et al., 2011),
whereas Bu et al (2010) and Aziz et al. (2011a) suggested 1.5 h. Others suggested
between 30 min and 18 h of settling (Qin et al., 2004; Kumar and Subramanian,
2014). Some researchers showed that the settling time can be reduced by adding
adsorbents in the reactors (Lee and Lim, 2003; Aziz, 2011). Thus, in the current
study, shorter settling hours were used to optimize the SBR process.

1.3 Objectives
The objectives of this study include the following:
1. To characterize leachate at the Semeling Landfill Site in Sg. Petani, Kedah,
Malaysia and domestic wastewater from the Bayan Baru Sewage Treatment Plant.
2. To optimize the settling time and dosage of PZ in batch/shaking experiments
of fixed ratios of leachatedomestic wastewater samples, which are used in pre-SBR
experiments for co-treatment;
3. To determine the optimum parameters [i.e., contact time, leachate to
wastewater mixing ratio (L/W), and aeration rate] via pre-SBR experiments and
Response Surface Methodology (RSM) using different configurations of SBR
systems (SBR, PZ-SBR, PAC-SBR, and PZE-SBR) and to test their performance on
removal of colour, COD, ammonia, phenols, Fe, Mn, Ni, and Cd; and
4. To compare the performance of the different SBRs (SBR, PZ-SBR, PACSBR, and PZE-SBR) at the optimum conditions pre-determined in (2) and (3) on the
removal of colour, COD, ammonia, phenols, sulfide, Fe, Mn, Ni, Cd, and Cr tested.

1.4 Scope of the study


The scope of this study includes:
(1) Raw leachate samples were gathered from the Sungai Petani landfill site.
Leachate samples were gathered and characterized during both dry and wet days.
(2) Domestic wastewater and returned activated sludge samples were gathered
from the Bayan Baru wastewater treatment plant. The samples were characterized.
(3) ZELIAC was freshly prepared in accordance with the previously published
ratio (Halim et al., 2010). ZELIAC, powdered activated carbon, or powdered zeolite
was added in the SBR, and their performances were compared.
(4) Leachate/domestic wastewater parameters tested were limited to colour,
COD, ammonia, phenols, Fe, Mn, Ni, and Cd.

1.5 Thesis organization


This thesis is written in five chapters: Chapter 1 explains the background of the
study, the problem statement, objectives, pioneering statements, and scope of the
study. Chapter 2 presents the literature review, which includes research on sanitary
landfill, landfill leachate, and landfill leachate treatment technologies (e.g.,
biological methods for wastewater treatment and physical-chemical methods,
adsorption isotherms, and response surface method for optimization experiments).
Chapter 3 describes the Sungai Petani landfill leachate, Bayan Baru wastewater,
ZELIAC

preparation,

Pre-SBR

experiments

(batch/shaking

experiments,

batch/optimization experiments), and continuous SBR experiments. Chapter 4


presents the results and discussion on Pre-SBR experiments (batch/shaking
experiments and batch/optimization experiments) and continuous SBR experiments
(repeated experiments). Chapter 5 presents the conclusions and recommendations.

CHAPTER 2
LITERATURE REVIEW
2.1. Introduction
This chapter includes sections that are useful in designing and conducting
experiments. The first section describes a sanitary landfill. The second focuses on
landfill leachate and wastewater treatment technologies, including biological
methods and physicalchemical methods. Furthermore, important equations related
to biological design are presented and discussed. The third section reviews studies on
ion-exchange and adsorption methods for wastewater treatment and adsorption
isotherms. In the fourth section, studies on the co-treatment of landfill leachates and
domestic wastewaters are summarized. The design of experiments by RSM to
optimize operational parameters is examined in the final section.

2.2 Sanitary landfill


The rapid growth in volume and forms of solid and hazardous wastes as a
result of continuous economic development, industrialization, and urbanization is an
increasing problem faced by domestic and local governments in ensuring an efficient
and sustainable waste management. In 2006, the estimated total volume of municipal
solid waste (MSW) generated internationally reached 2.02 billion tons, indicating a
7% annual rise since 2003. Between 2007 and 2011, the rise in universal generation
of urban waste was estimated at 37.3%, equivalent to an increase of approximately
8% per year (UNEP, 2009). Landfills should be designed and operated in such a
manner that wastes can be isolated from the environment until being rendered safe
after being subjected to biological, chemical, and physical decay processes. A
sanitary landfill is assessed based on environmental risk evaluation; planned size;
9

designed cell advance; extensive site preparation; full leachate management; daily
and final cover; full gas management; compaction; fence and gate; maintained record
of waste volume, type, and resource; and absence of scavenging and trading. A main
component of isolation is the management and treatment of leachates. Several
methods can be employed to attain isolation of leachates from the surrounding
environment depending on available resources. The methods range from prevention
of leachate generation to sophisticated leachate treatment systems and controlled
release of leachates to the environment (Liermann, 2009).
In the design of a the sanitary landfill, a dumping site should meet the
following basic criteria: (1) compaction of wastes, (2) daily covering of wastes with
soil or other materials to minimize their impact on the outside environment, and (3)
control and prevention of negative effects on the health of the community and
environment (e.g., odors, polluted water supplies, and so on) (UNEP, 2005). The
basic design and operating aspects of a sanitary landfill in terms of routes of impact
outside the fill and the three basic conditions are shown in Figure 2.1. The
advantages and disadvantages of sanitary landfills are shown in Table 2.1.
Malaysia has approximately 296 landfills (Table 2.2) as of this writing, and the
majority are old dumpsites (National Solid Waste Management Department, 2014).
Most of these landfills are only disposal grounds without environmental treatment
facilities. Leachates are released straight into water resources, which threatens the
neighboring ecosystems, particularly in places where landfills are situated upstream
of water systems (Aziz et al., 2011a). The two classification systems for landfills in
Malaysia are as follows:

10

Table 2-1: Benefits and disadvantages of sanitary landfills


Advantages

Disadvantages

Simply dumping procedure

Production of highly polluted leachate

Low cost

Production of highly methane gas

Landscape-restoring impact on holes


from mineral working

Figure 2.1: Schematic of basic aspects of a sanitary landfill (Source: UNEP, 2005)

2.2.1 Category based on operating purposes


The four levels of improvement for landfills are shown in Table 2.3 (Aziz,
2011; Manaf et al., 2009). Malaysia has 296 disposal sites, among which 131 are
closed, and 165 are still operating. Most of these landfills cannot be classified as
Level 4 because they do not have any facility for collecting and treating leachates
(National Solid Waste Management Department, 2014).

11

Table 2-2: Total Landfills in Malaysia


State

Still Operating

Closed Landfills

Total

Johor

14

23

37

Kedah

15

Kelantan

13

19

Melaka

Negeri Sembilan

11

18

Pahang

16

16

32

Perak

17

12

29

Perlis

Pulau Pinang

Sabah

19

21

Sarawak

49

14

63

Selangor

14

22

Terengganu

12

20

WP Kuala Lumpur

WP Labuan

Total

165

131

296

(Source: National Solid Waste Management Department, 2014)

Table 2-3: The four levels of improvement aimed for landfills


Level

Details

Controlled disposal

Sanitary landfill with daily cover

Sanitary landfill with leachate excursion

Sanitary landfill with leachate treatment facilities

2.2.2 Category based on landfill structure


Many types of landfill sites have been classified based on the literature review.
Table 2.4 and Figure 2.2 show the types of landfill sites.

12

Table 2.4: Classification of landfill structures


No.
Type
Details
1
Anaerobic
Disposed solid wastes are filled in dug areas of plane field
landfill
or valley. The wastes are filled with water under anaerobic
conditions.
2
Anaerobic
Anaerobic landfill with sandwich-shaped cover. Conditions
sanitary landfill of disposed wastes are similar to the conditions of Type 1.
3
Improved
This type has a leachate collection system at the bottom of
anaerobic
the landfill site. Other parameters are the same as those of
sanitary landfill the anaerobic sanitary landfill. The conditions are anaerobic
and moisture content is significantly less than that in the
anaerobic sanitary landfill.
4
Semi-aerobic
The leachate collection pipe is larger than that of the
landfill
improved sanitary landfill. The openings of the pipes are
surrounded by air and the pipe is covered with small
crushed stones. Moisture content in disposed solid waste is
low. Oxygen is supplied to solid waste from the leachate
collection pipe.
5
Aerobic landfill Aside from the leachate collection pipe, air supply pipes are
attached and air is able to mix with the solid waste. Thus,
the landfill becomes more aerobic than semi-aerobic.
Source: Aziz (2011)

2.3 Landfill leachate


Leachates are generated when moisture mixes with refuse in a landfill;
pollutants are dissolved into the liquid phase, after which they accumulate and then
percolate. Leachates vary from one landfill to another in the short- and long-terms
periods because of variations in climate, hydrogeology, and waste composition.
Improvements in landfill engineering are intended to reduce leachate production and
collection, as well as improve treatment prior to discharge (Visvanathan et al., 2000).
Landfill leachates are considered as wastewater that has the strongest
environmental impact. The most significant feature of leachates is the high
concentrations of particular contaminants.

13

Figure 2.2: Classification of landfill structures (source: Aziz, 2011; Environmental


Control Pollution Center, Osaka Prefecture, 2009)

14

Urban landfill leachates consist of contaminants that can be classified into four
main groups as follows: (1) dissolved organic matter; (2) inorganic compounds such
as calcium, potassium, sodium, ammonium, calcium, magnesium, sulfates, and
chlorides; (3) iron and heavy metals such as nickel, lead, copper, chromium,
cadmium, and zinc; and (4) xenobiotic organic materials (Aziz et al., 2011a; Tengrui
et al., 2007). Tables 2.5 and 2.6 list the characteristics of leachates generated from
disintegration of MSW in developing countries and landfill leachate classification
versus age, respectively.

Table 2.5: Characteristics of leachate generated from decomposition of MSW in


developing countries
Parameter

Range of values (mg/L)

Parameter

4.5 to 9
300 to 11,500
20 to 40,000
500 to 60,000
10 to 250
100 to 5,000
10 to 2,500
50 to 4,000
40 to 1,150
0 to 42,300
6 to 2,700
0 to 22,800

Organic N
Ammonia NH3
Nitrite nitrogen NO2
Nitrate nitrogen NO3
Total nitrogen
Total phosphate
Sulphate (SO42)
Manganese
Total iron
Copper
Lead
Zinc

pH
Alkalinity (CaCO3)
BOD5
COD
Calcium
Chloride (Cl)
Potassium
Sodium
Magnesium
TDS
Total SS
Hardness
Source: UNEP (2005)

Range of values
(mg/L)
10 to 4,250
30 to 3,000
0 to 25
0.1 to 50
50 to 5,000
0.1 to 30
20 to 1,750
0.03 to 65
3 to 2,100
4 to 1,400
8 to 1,020
0.03 to 120

Table 2.6: Landfill leachate classification versus age


Parameter
Age (years)
pH
COD (mg/L)
BOD5/COD
Organic compound

Young
<5
<6.5
>10,000
>0.3
80% volatile fatty
acids (VFA)

Heavy metals
Biodegradability

Low to medium
Important

Intermediate
5 to 10
6.5 to 7.5
4,000 to 10,000
0.1 to 0.3
5% to 30% VFA +
humic and fulvic
acids
Low
Medium

Source: Ngo et al. (2008)

15

Old
>10
>7.5
<4,000
<0.1
Humic and fulvic
acids
Low
Low

2.4 Landfill leachate treatment technologies


In general, the following landfill leachate treatment techniques are available:
(1) spray irrigation on abutting grassland, (2) leachate recirculation through the
landfill, (3) sewage and leachate co-treatment, (4) leachate vaporization by landfillgenerated methane as fuel, as well as (5) biological or physicalchemical treatment
(Mojiri, 2011).
The primary methods of landfill leachate treatments include physicalchemical
and biological treatment processes. In general, combinations of physical, chemical,
and biological techniques are applied because of the difficulty in obtaining
satisfactory results by a single method (Aziz, 2011). Physicalchemical methods are
frequently required for the treatment of mature and recalcitrant leachates. Figure 2.3
presents a diagram of various landfill leachate technologies.

2.5 Biological methods


2.5.1 Anaerobic method
Anaerobic methods are a sustainable and appropriate wastewater treatment
system for developing countries; it is a simple and cost-effective technology that is
gaining acceptance for the treatment of a variety of wastewaters (Alptekin, 2008). An
anaerobic method is a biological process wherein bacteria breaks down organic
matter in environments with minimal or no oxygen. Anaerobic methods are an
enclosed version of the anaerobic breakdown of organic waste in a landfill that
releases methane, which can be efficiently controlled (Friends of the Earth, 2007).

16

Figure 2.3: Diagram of landfill leachate treatment techniques (based on Abbas et al.,
2009 and Renou et al., 2008)

17

2.5.2 Aerobic method


The word aerobic refers to the characteristic of being in the presence of air
(oxygen). Aerobic treatment methods occur in the presence of air and utilize
microorganisms called aerobes that use molecular or free oxygen to assimilate
organic impurities, that is, convert them into carbon dioxide, water, and biomass
(Mittal, 2011).

2.5.3 Some types of bioreactors


2.5.3.1 Upflow anaerobic sludge blanket
The upflow anaerobic sludge blanket (UASB) reactor was constructed in the
Netherlands in the early 1970s (Lettinga et al., 1980). This reactor originally
proposed by Lettinga was one of the earliest systems in which development of a
granular biomass was observed. Excellent sludge retention is ensured in the UASB
reactor because of the superb settling characteristics of the granular biomass and the
presence of a specially designed three-phase (biogas, water, and biomass) separator
device in the upper part of the reactor system (Mai, 2006).

2.5.3.2 Upflow anaerobic filter


Anaerobic filters have been used successfully for the treatment of dilute
wastewater with COD-removal efficiencies between 60% and 80% depending on the
hydraulic retention time (HRT) used (Alptekin, 2008). The upflow anaerobic filter
maintains the biomass immobilized over a fixed support, which enables the
maintenance of high cellular retention times even when operating at low HRT.

18

2.5.3.3 Anaerobic hybrid reactor


The anaerobic hybrid reactor, which combines the sludge blanket in the lower
slice and the filter in the upper part, has been reported to enhance the advantages of
using the UASB and upflow filter while minimizing their limitations (Kumar et al.,
2007).

2.5.3.4 Membrane bioreactor


The

membrane

bioreactor

technique

employs

activated

sludge

and

microfiltration (MF) or ultrafiltration (UF) membranes with pore sizes ranging


typically between 10 nm and 0.5 m (Battilani et al., 2010).

2.5.3.5 Activated sludge system


A biological wastewater treatment method increases the rate of waste
disintegration. Activated sludge is added to the wastewater, and the combination is
aerated and agitated. After a certain period, the activated sludge is allowed to settle
by sedimentation and is disposed (wasted) or reused (returned to the aeration tank).
A highly economical wastewater treatment method is advantageous for all
members of a community. The activated sludge method has the benefit of producing
a high-quality effluent at reasonable operating and maintenance costs. The activated
sludge method uses microorganisms that feed on organic pollutants in wastewater;
thus, producing a high-quality effluent. The basic principle behind all activated
sludge processes lies on the aggregation of particles as microorganisms grow. These
particles (floc) are allowed to settle to the bottom of the tank, leaving a relatively
clear liquid free of organic material. Basically, screened wastewater is blended with
varying amounts of recycled liquid, including a high proportion of organisms taken
19

from a secondary clarifying tank, which becomes a product called mixed liquor. This
mixture is stirred and injected with large quantities of air to provide oxygen and keep
solids in suspension. After a certain period, the mixed liquor flows to a clarifier,
where it is allowed to settle. A portion of the bacteria is eliminated as it settles, and
the partially treated water flows for further treatment (Pipeline, 2013).
The activated sludge method is extensively applied around the world for
treatment of domestic and industrial wastewaters in situations where high effluent is
necessary and space is limited. However, the activated sludge system is heavily
mechanized in contrast to the other systems; thus, involving more complex operating
procedures. Another disadvantage is the consumption of electrical energy for
aeration (Sperling, 2007). Figure 2.4 shows the main units in the biological stage of
the activated sludge system.

Figure 2.4: Representation of the main units in the biological stage of the activated
sludge system (Source: Sperling, 2007)

Activated sludge methods come in several forms such as the conventional


(plug flow) activated sludge process, the extended aeration activated sludge method
(extended aeration), contact stabilization, step feed, complete mix, and SBRs.

20

2.5.3.6 Sequencing batch reactor


Research on SBRs started in the 1970s, which was concurrent with the
development of other discontinuous processes. A SBR is a comprehensive mixactivated sludge method without a secondary clarifier. A number of different
sequences are completed within the aeration basin. Aeration and clarification are
accomplished in one tank (Alkhaddar et al., 2005). One of the benefits of these batch
systems is that they can be easily adjusted for constant variations in the
concentrations of contaminants (Liermann, 2009). The literature reports that different
biological treatment methods were used for treatment of wastewater and leachates.
SBR is a type of biological treatment. SBRs differ from activated sludge plants
because SBRs band all treatment phases and processes into a single basin.
Conventional methods use on different tanks. In many investigations, the SBR was
applied for the treatment of domestic, urban, dairy, industrial, synthetic, and
slaughterhouse wastewaters and landfill leachates as shown in Table 2.7 (Laitinen et
al., 2006; Moncls et al., 2009; Aziz et al., 2011c). The phases of SBRs, namely, fill,
react, settle, as well as draw and idle, are described below (Vignesawarna et al.,
2004), whereas Table 2.8 shows the time for phases in SBR studies.
(1) In the fill phase, the influent wastewater is added to the biomass that remained
in the reactor from previous cycle.
(2) Aeration is the primary feature of the react phase, which occurs when the
reactor is full.
(3) Aeration is stopped in the settle phase, and the separation of solids occurs at
the bottom.
(4) Draw and Idle: Treated wastewater is withdrawn in the draw phase. Idle time
can be used to waste sludge or perform backwashing of the jet aerator.

21

Table 2-7: Treatment of different types of wastewaters by using the SBR process
No.

Type

Contaminants

Landfill leachate

2
3

Landfill leachate
Municipal wastewater

Dairy wastewater

Textile effluent

Wool dyeing effluents

Slaughterhouse wastewater

Abattoir effluent

Tannery wastewater

10

Synthetic wastewater

COD
Ammonium
Phosphate
COD
Biochemical oxygen demand
Total SS
Ammonia
COD
Total solids
Volatile solids
Total nitrogen
Total organic carbon
Colour
COD
Biochemical oxygen demand
COD
Total nitrogen
Total phosphorus
Nitrogen
Phosphorus
COD
Ammonia
Biochemical oxygen demand
COD
Total nitrogen
Total phosphorus

Removal
(%)
75
44
44
<83
98
90
89
80.2
63.4
66.3
38.3
66
94
79 to 91
91 to 99
96
96
99
85.5
90
80 to 82
83 to 89
97.7
94.9
71.4
55.9

(Source: Aziz et al., 2011)

Table 2-8: Time for fill, settle, draw and idle phases in SBR studies
Type of Wastewater

Fill

Settle

Draw and Idle

Reference

(min)

(min)

(min)

Leachate

20

90

10

Aziz (2011)

Synthetic Wastewater

20

105

12

Azimi et al. (2005)

Leachate

10

70

10

Timur and and Ozturk (1999)

Leachate

25

15

Laetinen et al. (2006)

Leachate

30

90

30

Bu et al. (2010)

(a) Advantages and disadvantages of SBR


The main advantages of the SBR process are as follows: (1) simple
construction, (2) the plant can fit into virtually any shape, (3) flow through plants

22

requires regular-shaped sites, (4) fewer channels and pipe work, (5) easily scalable,
and (6) can be adapted for nitrification and denitrification.
The main disadvantages of the SBR methods are as follows (Mace and
Alvarez, 2002; USEPA, 1999): (1) a higher level of complexity is required
(compared with conventional systems), especially for larger structures, for timing
units and controls; (2) a higher level of maintenance (compared with conventional
systems) associated with more complex controls, automated switches, and automated
valves is required; (3) the potential to discharge floating or settled sludge during the
draw or decant phase with certain SBR configurations; (4) the potential requirement
for equalization after the SBR, depending on the downstream processes; and (5)
batch feeding from storage or bio-selectors required to control bulking.

(b) Additional information on SBR


Janczukowicz et al. (2001) investigated the settling properties of activated
sludge from a SBR. Results of the study showed satisfactory settling properties of the
sludge. A low sludge volume index (SVI; 3060 mL/g SS) was responsible for the
drastic and rapid sedimentation, which shortened the settling phase to less than 1 h.
Moreover, the low SVI prevented the sludge from bulking. High concentrations of
dissolved oxygen in the aeration tank during the reacting phase resulted in minimal
sludge biomass growth, which is vital in sludge dumping of a wastewater treatment
plant.
Mahvi et al. (2005) investigated the feasibility of continuous flow SBR for
synthetic wastewater treatment. The results showed that the reduction efficiencies
reached by the system were 97.7%, 94.9%, 85.4%, 71.4%, and 55.9% for BOD5,
COD, TKN, total N, and total P, respectively.

23

In many investigations, the SBR has been applied for the treatment of leachates
with low BOD5/COD ratios of 0.09 to 0.37. The capability of the SBR in treating
leachates is lower than in treating municipal and industrial wastes because leachates
have low biodegradability ratio and high concentration of heavy metals, COD, and
NH3N. In the reported studies, an adsorption method was supplemented to the SBR
process to increase the elimination efficiencies of organic matter, heavy metals,
NH3N, and other pollutants. Aziz et al. (2011b) investigated landfill leachate
treatment by PACSBR method and optimization by RSM. Results indicated that the
PACSBR showed superior performance over the SBR in terms of removal
efficiencies.

2.6 Physical/chemical methods


The reduction of floating materials, colloidal particles, colour, and toxic
compounds using flotation, coagulation/flocculation, adsorption, chemical oxidation,
and air stripping are physical and chemical processes. Physicalchemical treatments
for landfill leachates are employed in addition to the treatment line (pretreatment or
last purification) or treatment of a specific contaminant (stripping of ammonia)
(Renou et al., 2008).

2.6.1 Chemical precipitation


Chemical precipitation is generally employed as a pretreatment to eliminate
high-strength ammonium nitrogen (NH4+N) (Renou et al., 2008). Chemical
precipitation has been used to remove non-biodegradable organic combinations, such
as NH3N, and heavy metals from landfill leachates, because of its capability and
simplicity, and the equipment is inexpensive. During chemical precipitation,

24

dissolved ions in the solution are converted to the insoluble solid phase via chemical
reactions.

2.6.2 Chemical oxidation


Chemical oxidation processes were developed at different sites over the past
few years. A mixture of oxidizing agents, such as ozone or hydrogen peroxide and
ultraviolet (UV) light, is applied. This mixture exhibits high oxidation rates for
leachate COD. The method involves using a mixing chamber for the leachate and
oxidizing agent to form an influent of a chamber with UV lamps.

2.6.2.1 Fenton treatment


The Fenton process has been widely studied in recent years, and analyses
indicate that it is one of the most cost-effective alternatives for leachate treatment
among the potential physicochemical technologies (Deng, 2007). Fenton oxidation is
one of the advanced oxidation processes with high efficiency and low capital. Fenton
oxidation involves a mixture of H2O2 and ferrous salts that can generate aggressive
hydroxyl radicals at ambient temperatures (Gotvajn et al., 2011).

2.6.3 Coagulationflocculation or flocculationprecipitation


The coagulationflocculation has been used for the removal of nonbiodegradable organic compounds and heavy metals from landfill leachates. The
coagulation process destabilizes colloidal particles using a coagulant. To increase
particle size, coagulation is usually followed by flocculation of the unstable particles
for easy settling. This method facilitates the removal of SS and colloidal particles
from a solution (Kurniawan et al., 2006).
25

2.6.4 Membrane filtration


A membrane is a material that creates a thin barrier that can selectively resist
the movement of different constituents of a fluid; thereby affecting the separation of
the constituents (Visvanathan et al., 2000). Different membrane filtration techniques,
namely, MF, UF, nanofiltration (NF), and reverse osmosis (RO), are used in landfill
leachate treatments.

2.6.4.1 Microfiltration
MF with pore sizes of 0.05 microns to 10 microns is used to capture microbial
cells, small particles, and large colloidal particles. This method is not suitable as a
stand-alone treatment for leachates. MF is recommended as a pretreatment process
with other membrane processes (i.e., UF, NF, or RO) or in combination with ten
chemical treatment processes to remove suspended matter and colloids. Piatkiewicz
et al. (2001) employed this method in the pre-filtration stage and obtained COD
reduction rates of 25% to 35%.

2.6.4.2 Ultrafiltration
UF is a selective method that uses pressures of up to 10 bar. This technique
efficiently removes suspended matter either by direct filtration or biological
treatment to replace the sedimentation unit. UF is significantly dependent on the
material of the membrane. Syzdek and Ahlert (1984) proposed that this process
might prove useful as a pretreatment method in RO. UF can be used to eliminate
leachate components with larger molecular weight that tend to foul RO membranes
(Rautenbach et al., 1997; Bohdziewicz et al., 2001).

26

2.6.4.3 Nanofiltration
NF has been used in removing recalcitrant organic compounds and heavy
metals from landfill leachate because of its unique properties between UF and RO
membranes. NF also has the capability to remove particles with a molecular weight
greater than 300 Da and inorganic substances through electrostatic interactions
between ions and membranes. The action of this membrane lies in its surface charges
that permit charged solutes smaller than the membrane pores to be rejected along
with larger neutral solutes and salts (Kurniawan et al., 2006).

2.6.4.4 Reverse Osmosis (RO)


RO is one of the developments in leachate treatment over the past decade.
However, in contrast to biological treatment, RO is a separation process with two
streams, namely a low contaminated permeate stream and a highly contaminated
concentrate stream. Biological pretreatment may be necessary for leachates from the
acetic phase to prevent increased precipitation, passage of small molecules through
the membrane, and increased fowling on the surface of the membrane. Separation of
ammonium by RO is often insufficient (Stegmann et al., 2005).

2.6.5 Electrochemical treatment


Electrochemical methods have been used for the treatment of organic materials
with high toxicity and low biological degradability. Electrochemical methods, such
as electrocoagulation, electro-oxidation, and electro-photo-oxidation, have been
frequently applied for treatment of wastewaters from textile, tannery, and oil
industries. Treatment of landfill leachates by electrochemical methods is another

27

important research area. The electrooxidation method was specifically examined in


most of the studies in this field (Deng, 2007).

2.6.5.1 Electrooxidation
Electrochemical oxidation has become promising in wastewater treatment
primarily because of its effectiveness and ease of operation. This process has
significant efficacy in degrading refractory pollutants, such as cyanide, EDTA, and
aniline, as well as in reducing colour (Chiang et al., 1995).

2.6.6 Ion-exchange
Ion-exchange is a reversible interchange of ions between the solid and fluid
phases without changing the structure of the solid. This treatment can effectively
eliminate traces of metal impurities to meet the increasingly strict discharge
standards in developed countries. Prior to ion-exchange, the leachate should be
subjected to biological treatment (Kurniawan et al., 2006).
Solid ion exchange particles can be classified as natural inorganic particles
(zeolites) and synthetic organic resins fabricated from high-molecular-weight
polyelectrolytes (Bashir et al., 2010). Development of ion exchange resins and
characterization of naturally occurring ion exchange materials have demonstrated
numerous possible applications of the technology in water and wastewater treatment
(Wang and Peng, 2010).
The ion-exchange technique offers such benefits as the capability to handle
shock loadings and operate over a wide range of temperatures. Some of the most
popular and widely available natural ion exchangers are zeolites, which consist of an
aluminosilicate molecular structure with weak cationic bonding sites. The use of

28

natural zeolites has been avoided in processes that require high purity or consistency
because of the irregularities and impurities. Zeolites are hydrated aluminosilicates
comprising silica and aluminum tetrahedra that are mutually bound by chemical
covalent bonds of common oxygen atoms (Mojiri, 2011).

2.6.7 Adsorption
Adsorption is the most widely used technique for the removal of recalcitrant
organic compounds from landfill leachates. Adsorption is a mass transfer process by
which a substance is transferred from the liquid phase to the surface of a solid and
then bound by physical or chemical interactions or both (Kurniawan et al., 2006).
Regardless of the initial concentration of organic matter, adsorption of contaminants
on the activated carbon column or powder results in better reduction in COD than
that by chemical methods. However, adsorption requires frequent regeneration of
columns or an equivalently high consumption of PAC. Adsorption by activated
carbon has been used with biological methods for effective treatment of landfill
leachates. Non-biodegradable organics, inert COD, and colour may be reduced to
acceptable levels for biologically treated landfill leachates (Renou et al., 2008).
The adsorption technique is an efficient and a promising fundamental approach
in wastewater treatment processes (Foo and Hameed, 2009). This technique is
employed as a phase of integrated chemicalphysicalbiological method for leachate
treatment, or simultaneously with a biological process. The most commonly applied
adsorbent is granular-activated carbon (GAC) or PAC (Mojiri, 2011).
Adsorption using GAC or PAC has been widely considered for the removal of
organic and inorganic contaminants from polluted wastewater because of its inherent

29

physical properties, large surface area, microporous structure, high adsorption


capacity, and surface reactivity (Kurniawan et al., 2006).
Rodriguez et al. (2004) studied the efficiency of PAC and different resins in
reducing non-biodegradable organic matter from landfill leachates. Activated carbon
presented the highest adsorption capacity, with an 85% COD decrease and a residual
COD of 200 mgL1 (Renou et al., 2008).

2.7 Adsorption isotherms


An adsorption isotherm is a graphical representation of the relationship
between the quantity adsorbed by a unit weight of adsorbent (e.g., activated carbon)
and the amount of adsorbate remaining in a test medium at equilibrium, as well as
the distribution of adsorbable solutes between the liquid and solid phases at various
equilibrium concentrations (Desta, 2013).
An adsorption isotherm is an invaluable curve that explains the phenomenon
governing the retention (or release) or mobility of a substance from the aqueous
porous media or aquatic environment in a solid stage at constant temperature and pH.
The adsorption equilibrium (ratio between the adsorbed amount with that remaining
in the solution) is attained when an adsorbate-containing phase has been in contact
with the adsorbent for a sufficient period, in which the adsorbate concentration in the
bulk solution is in a dynamic balance with the interface concentration. The
mathematical correlation, which has a vital role in the modeling analysis, operational
design, and utilization of the adsorption systems, is depicted by graphically
expressing the solid phase against its residual concentration (Foo and Hameed,
2009).

30

The amount of adsorbate at equilibrium [qe (mg/g)] can be calculated to


determine the removal percentage of adsorbate (Kamaruddin et al., 2013):

(Eq. 2-1)
where Co and Ce (mg/L) are the initial and equilibrium liquid-phase concentrations of
the adsorbate, respectively; V is the volume of the solution (L); and W is the mass of
the adsorbent used (g).
The Langmuir and Freundlich isotherms are two of the best-known adsorption
isotherms. These isotherms have been originally derived for the adsorption of gases
by solids (Aydin et al., 1996).

2.7.1 Langmuir isotherm


The Langmuir equation establishes the relationship between the coverage or
adsorption of molecules on a solid surface and the gas pressure or concentration of a
medium above the solid surface at a fixed temperature (Aziz et al., 2012).
The Langmuir isotherm model assumes a monolayer adsorption on a
homogeneous surface. The main assumptions of the Langmuir isotherm are as
follows (Czepirski et al., 2003):
(a) Adsorption occurs only at specific localized places on the surface, and the
saturation coverage corresponds to complete occupancy of these sites.
(b) Each site can accommodate only one molecule or atom.
(c) The surface is energetically homogenous, and no interaction occurs
between neighboring adsorbed molecules or atoms.
(d) No phase transitions occur.
The Langmuir adsorption isotherm is defined as follows:

31

(Eq. 2-2)
where x/m is the mass of adsorbate adsorbed/unit mass of adsorbent (mg adsorbate
per g adsorbent), a and b is the empirical constants, and Ce is the equilibrium
concentration of the adsorbate in solution following adsorption (mg/L).

2.7.2 Freundlich isotherm


The Freundlich equation or Freundlich adsorption isotherm is a curve that
establishes the relationship between the concentration of a solute on the surface of an
adsorbent and the concentration of the solute in the fluid. In 1909, Freundlich
proposed an empirical expression of the isothermal variation of the quantity of gas
adsorbed with pressure using the unit mass of the solid adsorbent. This equation is
known as the Freundlich adsorption isotherm or Freundlich adsorption equation. Two
well-established adsorption isotherms are available as follows: the Freundlich
adsorption isotherm and the Langmuir adsorption isotherm. In this study, the amount
of mass adsorbed is plotted against the temperature, which provides an idea of the
variation of adsorption with temperature (Aziz et al., 2012). The Freundlich equation
can be written as follows (Hamdaoui and Naffrechoux, 2007):
(Eq. 2-3)
where KF is a constant that signifies the relative adsorption capacity of the adsorbent
(mg1(1/n)L1/ng1) and n is a constant that represents the intensity of the adsorption.
Operating with constant initial concentration C0 and variable weights of
adsorbent is essential to determine the maximum adsorption capacity; thus, ln qm is
the extrapolated value of ln q for C = C0. According to Halsey (1952, quoted in
Hamdaoui and Naffrechoux, 2007)

32

(Eq. 2-4)
where C0 is the primary concentration of the solute in the bulk solution (mg L1) and
qm is the Freundlich maximum adsorption capacity (mgg1).

2.7.3 Adsorption efficiency of adsorbents in wastewater treatment


Desta (2013) investigated the Langmuir and Freundlich isotherms for the
adsorption of textile metal ions onto Teff Straw (Eragrostis tef) agricultural waste.
Aziz et al. (2012) studied the efficiency of activated carbon in landfill leachate
treatment using the Langmuir and Freundlich isotherms. Results showed that the
maximum adsorption capacities for ammonia nitrogen (NH3N), colour, and COD
from the Langmuir adsorption isotherm were 5.63 mg/g, 25.30 Pt.Co/g, and
13.21 mg/g, respectively, whereas those for the Freundlich adsorption isotherm were
6 mg/g, 46.29 Pt.Co/g, and 15.41 mg/g, respectively. The Freundlich isotherm values
for NH3N, colour, and COD were higher than the Langmuir isotherm values.
Kamaruddin et al. (2013) studied the adsorption isotherms to explain the
performance of activated carbon and its relationship with COD or colour. Results
showed that the Freundlich and Langmuir isotherms can explain the reduction in
COD and colour because of high regression (R2). A number of studies regarding
adsorption isotherms and kinetics exist in the literature (Hamdaouia and
Naffrechoux, 2007; Mitta et al., 2007; Alagumuthu et al., 2010).

33

2.8. Wastewater treatment by ion exchanges and adsorbents


In literature, researchers have suggested the addition of low-cost adsorbents in
bioreactors for landfill leachate treatment for the following reasons:(1) To improve
biological treatment and remove refractory organic compounds (Cecen et al., 2003).
(2) The toxicity of the leachate often inhibits nitrification, which results in the
unsatisfactory removal of NH3N. In this case, the effectiveness of PAC, rice husk
ash, or other similar materials added in reducing nitrification inhibition is well
documented (Lim et al., 2010).
Aziz et al. (2011) investigated landfill leachate treatment by PACSBR.
Results showed that the PACSBR was better than SBR in removing pollutants.
Under optimum conditions with an aeration rate of 1 L/min and a contact time of 5.5
h, the PACSBR achieved 64.1%, 71.2%, 81.4%, and 1.33% reduction of COD,
colour, NH3N, and TDS, respectively.
Jung et al. (2004) investigated the NH3N removal by using zeolite in the SBR
(ZeoSBR). Results showed that the ZeoSBR can enhance nitrogen removal
efficiency by up to 33%.
He et al. (2007) improved SBR efficiency by the addition of powdered zeolite.
A higher degree of nitrogen removal was observed in the test reactor compared with
that in the control reactor because zeolite adsorbed NH4+N and improved
simultaneous nitrification and de-nitrification. Moreover, the addition of zeolite
powder is helpful in the inhibition of sludge bulking.
Foul et al. (2009) investigated the anaerobic landfill leachate treatment by
activated carbon and limestone through batch and column studies. An activated
carbonlimestone (15:25 by volume) mixture was applied in the primary treatment
process. For the first five days, more than 86% of the colour and COD, 95% of iron,

34

and 48% of ammoniacal nitrogen were reduced by the mixture in the batch study,
whereas the reductions in the colour and COD, iron, and ammoniacal nitrogen were
70%, 80%, and 90%, respectively, in the column study.
Thornton et al. (2007) investigated ammonium removal from a solution by ion
exchange onto MesoLite. Results indicated that a maximum equilibrium volume of
49 g NH4+Nkg1 media is achievable under experimental conditions. A detailed
examination of the data reveals that increasing the solution concentration and contact
time results in the best performance at an optimum pH between 6 and 7.
Sarioglu (2005) investigated the removal of ammonium from municipal
wastewater using natural Turkish (Dogantepe) zeolite. Results showed that the cation
exchange capacity of Dogantepe zeolite was 164.62 meq/100 g. These findings
showed that Dogantepe zeolite can be used to remove ammonium from wastewater.
Rahmani and Mahvi (2008) investigated the use of ion exchange for the
removal of ammonium by biological regeneration of zeolite. They demonstrated that
the cation exchange capacity was 10.06 (in the breakthrough point), and 18.38 mg
NH4+g-1 zeolite is the total capacity. Results showed that nitrification was
accelerated by increasing MLVSS concentration while maintaining nitrate
concentration in the solution. The results achieved by bioregeneration of zeolite
exhibited an efficiency of 87.7% to 99.8% for 3.5 h to 5.5 h. Nitrifying sludge can be
used for several cycles because regeneration was achieved with high nitrate
concentrations, and the system can be an economical method of removing NH4+ from
effluents.
Chang et al. (2009) studied the characteristics of zeolite media in NH 4+N
removal in a biological aerated filter (BAF) for the treatment of textile wastewater.

35

Results showed that the use of natural zeolites in a BAF for the treatment of textile
wastewater is feasible.
Wang et al. (2007) studied the removal of low-concentration ammonia in water
by ion-exchange using Namordenite. They showed that ammonia uptake by Na
mordenite was minimally influenced by the operating temperature in the range of
278333 K and the coexistence of K+ and Na+ in the water. By contrast, coexistent
Ca2+ and Mg2+ significantly lowered the efficiency of the Namordenite for ammonia
removal.
Samad et al. (2004) investigated phosphate removal from municipal
wastewater using different adsorbents. They showed that calcium carbonate is more
suitable for the phosphate removal from wastewater, and low pH values and high
temperatures enhance the removal of phosphate.
Bashir et al. (2010) investigated the application of RSM to optimize NH3N
removal from semi-aerobic landfill leachate using ion exchange resin. They
demonstrated that ion exchange resins can be used to remove NH3N efficiently
from semi-aerobic stabilized landfill leachate.
Sarudji and Mangkoedihardjo (2007) investigated cement and clay treatment
for organic-matter-containing leachates. The efficiency of clay in removing organic
matter was approximately 50% of the cement efficiency. However, clay increased the
biodegradability of treated leachate up to 20%, whereas cement decreased the
leachate biodegradability to the same degree.
These studies showed that low-cost adsorbents, such as activated carbon,
zeolite, rice husk ash, calcium carbonate, and limestone, have been used in landfill
leachate treatment. The current study focuses on a new adsorbent composed of all the
aforementioned adsorbents.

36

2.9 Wastewater treatment by composite adsorbent


Various composite adsorbents have been developed by different researchers for
the removal of specific pollutants.
The USM team has developed a new composite called ZELIAC as a cheap
material in landfill leachate treatment. ZELIAC consists of zeolite, activated carbon,
limestone, rice husk ash and Portland cement. Table 2.9 shows the functions of these
adsorbents in the removal of pollutants from wastewater.
The USM team studied the removal of ammonia and reduction of COD in a semiaerobic landfill leachate using low-cost activated carbonzeolite adsorbent, and the
results showed an increase in the percentage of ammonia (37%) and COD (57.5%)
adsorbed (Halim et al., 2009; 2010).

37

Table 2-9. Application ZELIAC and its compounds to treat wastewater


Type of Wastewater

Type of Adsorbent

Reference

Heavy metals removal from

Husk Ash and zeolite

Salam et al. (2011)

Heavy metals removal from

Zeolite and Protland

Ok et al. (2007)

wastewater

cement

Wastewater

Low cost adsorbents and

wastewater

MEng (2012)

Protland cement (as a


binder)
Heavy metals removal from

Zeolite

Dursun and Pala (2007)

Municipal wastewater

Activated carbon

Azhari (2010)

Municipal wastewater

Activated carbon

Boehler et al. (2012)

Municipal wastewater

Activated carbon

Salman (2009)

Heavy metals removal from

Husk Ash

Hegazi (2013)

Rice Husk Ash

Anand et al. (2014)

Rice Husk Ash

Abbas et al. (2013)

Limestone and activated

Dhas (2008)

wastewater

wastewater
Heavy metals removal from
wastewater
Phenols removal from
wastewater
Textile wastewater

carbon
Municipal wastewater

Limestone

Efendy (2010)

Removal of ammoniacal

ZELIAC

Halim et al. (2009, 2010)

nitrogen and COD from semiaerobic landfill leachate

2.10 Co-treatments of landfill leachate and wastewater


In literature, researchers have suggested the co-treatment of landfill leachates
and wastewater for the following reasons:
(1) Landfill leachate treatment using biological methods is difficult because of
the high COD/BOD ratio, high ammonium content, and the presence of heavy metal
ions (Nesaj et al., 2007). (2) Landfill leachates are frequently treated in combination

38

with sewage in urban wastewater treatment plants. However, the demand for separate
treatment and disposal of landfill leachates has increased because of stricter
regulations on nitrogen discharge and problems with the potential effects of
recalcitrant leachate constituents in the biological treatment phase.(Diamadopoulos et
al., 1997; Nesaj et al., 2008). (3) The co-treatment process has been preferred
because of low maintenance and low operating costs. (Abbas et al., 2009).
Co-treatment was mainly conducted using aerobic-based processes. Under
these conditions, the reported reductions in COD and TA were approximately 90 %
(Ceen and Akta, 2004; Ferraz et al., 2014; Fudal Ksiazek et al., 2011; Yu et al.,
2010).
Swierxzynska et al. (2012) investigated the co-treatment of landfill leachate
with municipal wastewater in MSBR through the following methods. The process
was conducted in an MSBR fitted with an inner capillary microfiltration PVDF
membrane. The feed was pumped from the storage tank into the MSBR with a
volume of 15 L. The treated effluent was then COD into the capillaries and pumped
into an effluent storage tank. The feed of the reactor comprised synthetic wastewater
and 5% (by volume) landfill leachate. Results showed that the co-treatment of
landfill leachates and domestic wastewater can significantly enhance the efficiency
in the reduction of COD, total nitrogen, NO3, and total phosphorus.
Kalka (2012) studied the reduction of landfill leachate toxicity in a combined
treatment with municipal wastewater. In the study, the leachate and wastewater were
mixed using different ratios ranging from 1% to 10% (v/v), and the activated sludge
in reactors I and II were adjusted according to the increase in the concentration of
landfill leachate in the influent (1% and 10%). Significant declines in COD, BOD5,
and ammonia were observed during biological treatment.

39

Litas et al. (2012) examined the use of a submerged membrane batch reactor
for the co-treatment of landfill leachates and domestic wastewater. COD reduction
efficiencies of up to 98% were observed. Similarly, NH4+N removal efficiencies
reached up to 99%.
Yu et al. (2010) investigated the combined treatment of domestic wastewater
with landfill leachate by using the A2/O process. The average reduction efficiencies
of NH4+N, TN, and COD were 96.5%, 61.0%, and 81.7%, respectively.
Ferraz et al. (2014) investigated the co-treatment of landfill leachate and
domestic wastewater by using a submerged aerobic biofilter. The reduction
efficiencies of COD and BOD were 98% and 80%, respectively.
Neczaj et al. (2008) investigated the SBR system for the co-treatment of
landfill leachate and dairy wastewater through the following process. Two laboratory
scale reactors were used to examine leachate and dairy co-treatment efficiency. The
reactors were constructed with plexiglass; each reactor had a height 30 cm height,
diameter of15 cm, and a total volume of 5 L. The reactors were supplied with oxygen
from a fine bubble air diffuser to maintain a dissolved oxygen concentration above
3 mg/L in the oxic phase. Magnetic stirrers were employed for mixing. A set of two
peristaltic pumps was used to feed and discharge the effluent in both reactors. The
reactors were operated at room temperature (1820 C). The cycle time of the
reactors was 24 h and consisted of five distinct stages: aerobic fill, aerobic react,
anoxic react, settle, and draw. Various operating stages were investigated to increase
treatment efficiency. The second SBR (SBR 2) system was operated at feeding
condition of leachate dilution of 25% by volume with a dairy wastewater and with
4 g/L sludge concentration, whereas the first reactor (SBR 1) was seeded with raw
dairy wastewater. Both systems were inoculated with sludge collected from the

40

municipal wastewater treatment plant in Czestochowa. COD reduction efficiencies


reached 98.2%. Similarly, total nitrogen removal efficiencies reached 70%.
Neczaj et al. (2007) investigated the impact of sonication on the treatment of
mixed landfill leachate and urban sewage in an SBR by the following process. Two
cylindrical aeration tanks with a height of 30 cm, diameter of 15 cm, and total
volume of 5 L were employed throughout the study. The wastewater in the tank was
aerated using an air pump and diffuser to keep the concentration of dissolved oxygen
above 2 mgL-1 in the oxic stage. A peristaltic pump was employed for influent feed,
waste sludge, and effluent draw. The content of the reactor was blended with a
magnetic stirrer. Temperature, pH, and DO were continuously monitored by relevant
probes. The reactor was operated in 24 h batch cycles. The initial volume of the
culture in the tank was 1 L, which was completed to 4 L with the addition of
wastewater containing 10% v/v leachate. Raw wastewater and landfill leachate were
refrigerated at 4 C to retard biological decomposition. The blended wastewater was
then seeded with activated sludge to obtain mixed liquor suspended solids at a
concentration of 3500 mgL-1. The sludge was collected from the same wastewater
treatment plant from which the domestic wastewater was also obtained. Results
showed significant improvement in the reduction rates of COD and nitrogen
compounds in the reactor.

2.11 Main parameters for anaerobic and aerobic treatments


2.11.1 F/M ratio
The F/M ratio basically refers to the loading rate divided by the concentration
of volatile suspended solids (biomass) in the digester (kg COD/kg VSSday). For any
given loading, efficiency can be enhanced by lowering the F/M ratio and increasing

41

the biomass concentration in the digester. In addition, the efficiency can be enhanced
by decreasing the loading for any given biomass concentration. F/M can be
calculated as follows (Latif, 2011):

(Eq. 2-5)
where organic loading rate is the COD of the influent stream (kg COD/Lday),
volatile solid is the volatile suspended solid concentration in the reactor (kg-VSS/L),
and F/M is expressed as kg COD/kg VSSday.

(Eq. 2-6)
where Q is wastewater flow(m3/d), BOD is wastewater BOD(g/m3), V is the
liquid volume in the aeration tank (m3), and MLSS is the mixed liquor-suspended
solids (g/m3.

2.11.2 Hydraulic retention time


Hydraulic retention time (HRT) calculation before the experiments is also an
important to obtain the total time required by the liquid to degrade. The HRT is
critical in anaerobic digestion as it indicates the time required for the liquid to remain
in the digester. HRT is calculated as follows (Latif, 2011):

(Eq. 2-7)
where HRT is the hydraulic retention time (d), OLR is the organic loading rate i
(kg COD/Lday), and CODin is the influent COD (kg COD/L).

42

(Eq. 2-8)
where V is the reactor volume (L) and Q is the total daily flow (L/d).

2.11.3 Flow rate


The HRT and flow rate determine the exact influent stream from the feed inlet
to the outlet. Normally, the flow rate is controlled by a peristaltic pump with hoses of
different diameters. The flow rate is determined based on the working volume of the
reactor. The flow rate is calculated as follows (Latif, 2011):

(Eq. 2-9)
where Q is the wastewater flow (m3/day), BOD is the wastewater BOD (g/m3),
V is the liquid volume of the aeration tank, and MLSS is the mixed liquor suspended
solids (g/m3).

(Eq. 2-10)
where Q is the flow rate of the influent (L/d), Vw is the working volume of the reactor
(L), and HRT is the hydraulic retention time (d).

2.11.4 Organic loading rate


OLR is defined as the weight of organic matter per day applied over a surface
area (e.g., pounds of BOD5 per day per square foot). BOD5 is a measure of the
oxygen needed to degrade the organic matter dissolved in the wastewater over 5 d
and is reported as mg/L of oxygen. Measuring BOD5 is one technique in determining
43

the amount of readily degradable organic matter in sewage. The first stage in
calculating organic loading is the conversion of BOD5 in mg/L to pounds/gal.
OLRs for fine media fixed-film systems, such as septic leach fields, mounds,
and sand bioreactors, range from 0.00025 lbs BOD5/ft2/d to 0.0012 lbs BOD5/ft2/d
(Zhou and Mancl, 2007).

(Eq. 2-11)
where OLR is the organic loading rate (kg/m3d), total COD is the total
chemical oxygen demand (kg/m3); and HRT is the hydraulic retention time (d).

2.12 Response Surface Method (RSM)


Design and analysis of experiments (DOE) have been widely used in planning,
analyzing, and running experiments in different areas, such as wastewater treatment,
food analysis, material production, and medication intake, which helps researchers
achieve their objective with less effort, cost, and time. The application of DOE in
wastewater industries has increased because it enables efficient data collection and
reduces error by excluding non-significant factors from the experiment, as well as
increasing the accuracy of the results to the target range. Three basic principles
should be considered in using experimental design, namely, replication,
randomization, and blocking. The well-known RSM consists of mathematical and

44

statistical techniques that are useful for modeling and analyzing problems. This
method aims to optimize response by determining the best operating conditions of
the input variables (independent variables) that influence the response. Optimization
is a procedure that determines the best target output for a process, which is conducted
with a series of experiments testing a range of values and combinations of all factors.
Optimization may involve maximizing, minimizing, and maintaining the target
within the range depending on the objective (Lim et al., 2014).
The RSM and Central Composite Design (CCD) were used to demonstrate the
nature of the response surface in the experimental design and clarify the optimum
conditions of the independent variables. CCD was established using the Design
Expert Software (6.0.7). Eq. (2-12), an empirical second-order polynomial model,
accounts for the behavior of the system, which is expressed as follows:
k

i 1

i 1

ii j

o i .X i i i X i 2

ij

X i X j ... e

(Eq. 2-12)

where Y represents the response, Xi and Xj represent the variables; 0 represents


a constant coefficient; j, jj, and ij represent the interaction coefficients of the
linear, quadratic, and second-order terms, respectively; k is the number of studied
factors; and e represents the error. ANOVA was used to analyze fully the results
obtained via the Design Expert Software. The design included k2 factorial points
supported by 2k axial points and a center point, where k represents the number of
variables (Mojiri et al., 2013a, b).
A number of researchers used RSM to optimize pollutant removal from
leachates and wastewater (Aghamohammadi et al., 2007 Ghafari et al., 2009; Bashir
et al., 2010; Mohajeri et al., 2010; Umar et al., 2011; Aziz, 2011; Aziz et al., 2011a;
Aziz et al., 2011b; Adlan et al., 2011). These studies showed that RSM is an
45

effective method for the investigation of contaminant-removal efficiencies from


wastewater.

2.13 Summary
The sanitary landfill is the most widely used USW management method (Aziz,
2011). Currently, approximately 296 landfills are located in Malaysia, most of which
are old dumpsites without environmental treatment facilities. Leachate is generated
when moisture enters the refuse in a landfill, and the pollutants are dissolved into the
liquid phase that eventually flows (Visvanathan et al., 2000). Landfill leachates have
been shown to contain a wide variety of toxic and polluting components. The
leachate generated from a landfill site will vary in volume and composition
depending on the age of the site and the stages of biodegradation attained.
There are many treatment methods for leachate and wastewater. The main
applicable methods of landfill leachate treatment include physicalchemical,
biological, and membrane separation techniques. Biological methods for treating of
wastewater, such as SBR, are common. In literature, SBR has been used to treat
landfill leachates and wastewater; however, the capability of the SBR in treating
landfill leachate was lower compared to treating urban wastes because of the low
BOD5/COD ratio and the high concentration of NH3N in landfill leachates. Previous
studies reported that adsorption methods can be used to supplement the SBR process
to increase the removal efficiencies of organic matter, heavy metals, NH3N, and
other pollutants. On the basis these studies, low-cost adsorbents, such as activated
carbon, zeolite, rice husk ash, calcium carbonate, and limestone have been used in
landfill leachate treatment. However, research on the use of an adsorbent that has all
the properties of these low cost materials is lacking. Therefore, the current study

46

focused on a new adsorbent composed of the aforementioned adsorbents.


Furthermore, some researchers suggested co-treatment of landfill leachate and
wastewater to improve biological treatment and remove refractory organic
compounds. Research on the co-treatment of leachate and wastewater using
adsorbents added in bioreactors is lacking. Therefore, the current study focused on
co-treatment of landfill leachates and domestic wastewater using a new adsorbent
that supplemented an SBR process.

47

CHAPTER 3
MATERIALS AND METHODS
3.1 Introduction
This chapter contains four main parts. The first part presents the collection and
characterization of leachate samples from Semeling Landfill (Sungai Petani),
domestic wastewater, and returned activated sludge from Bayan Baru Wastewater
Treatment Plant. The second part presents pre-SBR experiments, including
batch/shaking experiments to optimize the settling time and dosage of powdered
ZELIAC

(PZ)

(fixed

leachatedomestic

wastewater

ratio

sample)

and

batch/optimization experiments to optimize contact time, leachate-to-wastewater


mixing ratio, and aeration time. The third part presents the preparation of ZELIAC,
activated carbon and zeolite. The last part presents continuous SBR experiments
based on optimum parameters from pre-SBR experiments. The methodology flow
chart of this study is summarized in Figure 3.1.

3.2 Case study sites


3.2.1 Semeling Landfill, Sungai Petani
3.2.1.1 Site description
The landfill site (geographical coordinates 0543N and 10029E) is located in
Sg. Petani Kedah, Malaysia. Semeling Landfill receives approximately 350 tons to
400 tons of solid wastes daily as measured by a weight bridge. This open dumping
site has been actively utilized since 1990. The total landfill area of Semeling is 11.24
ha. The site lacks treatment and gas control facilities.

Leachate samples were

collected from Semeling Landfill (Figure 3.2) from May 2012 to March 2013.

48

Figure 3-1. Methodology flow chart

49

Figure 3-2. Semeling Landfill site (Source: Google maps)

3.2.1.2. Sampling procedures


Ten leachate samples were collected from Semeling Landfill (0543N and
10029E) from May 2012 to March 2013. The samples were collected in 24 L
plastic containers. Sampling was performed at approximately 30 cm depth from the
surface (Aziz, 2011). Figure 3.3 provides the leachate collection. The pond from
which the leachate samples were collected exhibits continuous flow; thus, the
collected samples represent the entire generated leachate. The collected samples were
immediately transferred to the laboratory (Lab. 1 at School of Civil Engineering,
USM) and maintained in a cold room at 4 C to minimize biological and chemical
reactions (Aziz et al., 2011c; APHA, 2005). YSI 556 Multiprobe System (YSI
Incorporated, USA) was utilized to record the pH, temperature (C), electrical
conductivity (ms/cm), salinity (g/L), and TDS (%) at the site.

50

Figure 3-3: Leachate collection

3.2.2 Bayan Baru Sewage Treatment Plant (BBSTP)


3.2.2.1 Site description
The returned activated sludge and domestic wastewater employed in this study
were collected from BBSTP in Penang, Malaysia. BBSTP, which was constructed in
January 2004, is situated close to the Penang Airport. The plant consists of a
preliminary treatment basin, a clarifier, a modified oxidation ditch, sludge thickening
and dewatering components, and a sludge storage tank. The project provides for a
population equivalent (PE) of 200,000 in Bayan Baru with an average design flow of
45000 m3/d (Aziz, 2011). Figure 3.4 shows an aerial view of BBSTP.

51

Figure 3-4: Aerial view of BBSTP and its various units (source: Aziz, 2011; Penang,
Bayan Lepas; 05 18' 58"N, 100 17' 38"E)

3.2.2.2 Sampling procedures


Ten samples of returned activated sludge and domestic wastewater were
collected from BBWTP in 24 L plastic containers. Wastewater samples were
collected at the effluent of the final clarifier (supernatant liquid; Figure 3.4).
Sampling was performed from June 2012 to March 2013. The collected samples
were immediately transferred to the laboratory and maintained in a cold room at 4 C
to minimize biological and chemical reactions (APHA, 2005). Figure 3.5 shows the
aeration tank of BBWTP and sampling of returned activated sludge.

52

Figure 3-5: Aeration tank and sampling of return activated sludge at the site
3.3 Analytical methods
All tests were conducted in accordance with the Standard Methods for the
Examination of Water and Wastewater (APHA, 2005). YSI 556 Multiprobe System
(YSI Incorporated, USA) was utilized to record the pH, temperature (C), electrical
conductivity (ms/cm), salinity (g/L), TDS (%), and oxidation reduction potential
(mV) values. A spectrophotometer (DR/2500 and DR/2800 HACH) was employed to
measure the contents of phenols (mg/L), colour (Pt. Co), total phosphorus
(PO43 mg/L), ammonia NH3N (mg/L), total nitrogen (mg/L), nitrite (mg/L),
chemical oxygen demand (COD, mg/L), sulfide (mg/L S2), total organic carbon
53

(mg/L TOC), total iron (mg/L Fe), copper (mg/L Cu), manganese (mg/L Mn),
aluminum (mg/L Al), zinc (mg/L Zn), chromium (mg/L Cr), and nickel (mg/L Ni).
ICP (ICP Varian, OES 715) was utilized to measure the levels of cadmium (mg/L
Cd), molybdenum (mg/L Mo), cobalt (mg/L Co), magnesium (mg/L), lithium (mg/L
Li), and calcium (mg/L CaCO3). The leachate parameters that were characterized are
shown in Table 3.1.

Table 3-1: Analytical methods


Parameters
phenols (mg/L)
Total solids
NH3-N (mg/L)
Total phosphorus
(mg/L)
Sulfide (mg/L)
Colour (Pt. Co)

Methods
4-Aminontipyrine method, DR/2800 HACH spectrometer, Method
8047
Method 2540B [8]
Ammonia nitrogen-Nessler method, HACH DR/2800 spectrometer,
Method 8038
Phos Ver 3 with Acid persulfate digestion method, HACH DR/2800
spectrometer, Method 8190
Sulfide, Methylene Blue method, HACH DR/2800 spectrometer,
Method 8131
Method 2120C [8], HACH DR/2800 spectrometer, Method 8025

Chemical oxygen
demand (COD) (mg/L)

Method 5220D, HACH DR/2800 spectrometer

Iron (mg/L)

Ferro Ver method, HACH DR/2800 spectrometer, Method 8008

Zinc (mg/L)

Zinc, Zincon method, HACH DR/2800 spectrometer, Method 8009

pH

YSI MOS (YSI Incorporated; www.YSI.com

Temperature ()
EC (ms/cm)
Salinity (g/L)
TDS

3.4 Reactor characteristics in all experiments


Six 2000 mL beakers were employed throughout the study. Each beaker had a
working volume of 1200 mL, an inner diameter of 113 mm, and a height of 200 mm.
A magnetic stirrer placed at the bottom of the reactors was used to mix the media.

54

The experiments were conducted at room temperature. An air pump (YASUNAGA


Air Pump Inc., China) was used to provide the air. The characteristics of the air
pump (model LP-60A, serial number 08110014) were as follows: voltage of 240 V,
frequency of 50 Hz, input power of 61 W, pressure of 0.012 MPa, and air volume of
60 L/min. The air flow speed was manually regulated with an air flow meter (Dwyer
Flow Meter, model RMA-26-SSV). Figure 3.6 shows a schematic of the SBR
arrangement in continuous and repeated experiments.

Figure 3-6: Schematic of the SBR arrangement in batch/optimization and continuous


SBR experiments

55

3.5 ZELIAC preparation with activated carbon and zeolite


Fresh ZELIAC was prepared in accordance with previous findings on the
mixture (Halim et al., 2009). Zeolite, activated carbon, limestone, rice husk ash, and
Portland cement were ground, made to pass through a 300 m mesh sieve, and then
mixed. The mixing percentages and estimating cost of ZELIAC are shown in Table
3.2. Based on this table, the estimated cost of ZELIAC per ton is around 2582 RM.
The mixture was evenly poured into the mold after the addition of water. After 24 h,
the materials were removed from the mold and soaked in water for 3 d for curing.
After allowing them to dry within 2 d, the materials were crushed and sieved. The
prepared ZELIAC was subjected to XRF, XRD, and autosorb testing in accordance
with APHA (2005). XRF and XRD were conducted at the School of Materials and
Minera Resources Engineering, USM, with XRF/EDX Casio and an X-ray
diffractometer (Bruker), respectively. Autosorb testing was performed at Lab. 2,
School of Civil Engineering (USM), with Quantachrome AS1wintm, version 2.02.
Powdered ZELIAC (PZ), powdered activated carbon (PAC), and powdered zeolite
(PZE) with sizes ranging from 75 m to 150 m (passed sieve no. 100 and retained
on sieve no. 200) were utilized as adsorbents in the PZ-SBR, PAC-SBR, and PZESBR systems, respectively. A similar size range was used by Aghamohammadi et al.
(2007) and Aziz et al. (2011a). The autosorb testing of adsorbents was performed at
Lab. 2, School of Civil Engineering (USM), with Quantachrome AS1wintm, version
2.02.

56

Table 3-2: The values of raw materials to prepare one ton of ZELIAC
Raw Materials

Value (Ton)

Zeolite
Limestone
Activated carbon
Rice husk ash
Portland cement
Water
ZELIAC

459.40
153.20
43.80
43.80
300.00
30.00
-

Price per ton


(RM)*
5000
100
6500
Free
320
600.00
-

Unit Price
(RM)
2297
15.32
284.70
96.00
2693.02

*Based on purchasing made by the School of Civil Engineering, USM laboratory in


2013

3.6 Sludge acclimatization for batch/optimization and continuous SBR


experiments
In accordance with the study of Aziz et al. (2011c), 120 mL (10%) of the
collected landfill leachate was mixed with approximately 1080 mL of activated
sludge (90%). After the termination of the reaction and settling phases, 120 mL of
the supernatant was removed. Additional 120 mL of raw leachate was added to the
reactor in another cycle. This procedure was sustained for at least 10 d to allow the
system to adapt to the experimental condition. The adjusted sludge was later utilized
as seed in the SBRs. Figure 3.7 shows the procedure of sludge acclimatization.

Figure 3-7: Sludge acclimatization

57

3.7 Pre-SBR experiments


The optimum experimental parameters were examined. The experiments were
divided into batch/shaking and batch/optimization experiments. In the former, the
optimum ZELIAC dosage and settling time were determined. In the latter, the
optimum aeration rate (L/min), optimum leachate-to-wastewater mixing ratio (v/v;
%), and contact time (h) were determined.
The pre-SBR experiments were conducted in the mentioned reactors at room
temperature. pH was maintained at approximately 6 to 9 during the experiments.
Most bacteria grow well within the pH range of 6 to 9 (Tortora, 2010). Figure 3.8
shows the reactors in the pre-SBR experiments.

Figure 3-8: Pre-SBR experiments

3.7.1 Batch/shaking experiments


The selected parameters for the batch/shaking experiments were PZ dosage and
settling time. After 5 SBR runs, the optimum values of the above mentioned
parameters were determined.

58

3.7.1.1 PZ dosage
Selection of the optimum PZ dosage was conducted with 2000 mL beakers
(working value of 1200 mL). Different amounts (i.e., 1, 2, 3, 5, 7, 10, and 20 g/L) of
PZ were added to the beakers. Selection of the optimum PZ dosage was based on the
optimum removal of colour, NH3N, and COD in the beakers.

3.7.1.2 Settling time


The SBR phases include fill, react, settle, draw, and idle (Mahvi, 2008).
Settling times of 4.08h (0.17d) to 68.1h (2.84d) were used in the SBR process
according to the literature. DO concentration decreases during settling time in the
reactor. DO reduction to less than 1 mg/L is useful for denitrification (Aziz, 2011).
Settling times of 0, 0.5, 1, 1.5, 2, 3, 4, and 6 h were employed according to the
literature (Aziz, 2011; Wang et al., 2009; Li et al., 2008). DO was measured at these
times. Selection of the optimum settling time was based on DO concentration. Table
2.8 showed the time for SBR phases in some researches

3.7.1.3 Summary of batch/shaking experiments


Settling times of 0.5, 1, 1.5, 2, 3, 4, and 6 h were employed according to the
literature. Different amounts (i.e., 1, 2, 3, 5, 7, 10, and 20 g/L) of PZ were added to
the beakers. The optimum ZELIAC dosage was 3 g/L as indicated by the removal of
colour, NH3N, and COD in the beakers. This optimum dosage was also used for
PAC-SBR and PZE-SBR. The selected settling time was 90 min according to DO
reduction. This settling time was used for normal-SBR, PZ-SBR, PAC-SBR, and
PZE-SBR.

59

3.7.2 Batch/optimization experiments (design experiments)


The SBR phases include fill, react, settle, draw, and idle (Aziz et al., 2011a). In
all experiments, the durations of fill and mix (20 min), draw and idle (10 min), and
settle (90 min) were fixed. The selection of these conditions was based on the
findings of previous literature (Mahvi, 2008Aziz, 2011; Aziz et al., 2011a). Different
aeration rates of 0.5, 4, and 7.5 L/min (Aziz et al., 2011a); contact times of 2, 12, and
22 h (Aziz et al., 2012); and leachate-to-wastewater ratios of 20% to 80% (v/v) were
applied to normal-SBR, PZ-SBR, PAC-SBR, and PZE-SBR. The beakers were filled
with 120 mL (10%) of the adjusted sludge and 1080 mL (90%) of the domestic
wastewater and Sungai Petani Landfill leachate (in different ratios). To increase the
biodegradability ratio, channeling was performed by mixing the landfill leachate with
the wastewater and sludge. This process was performed in accordance with the
method described by Neszaj et al. (2008).
The reactors were divided into four groups that consist of six reactors each for
SBR (normal-SBR), PZ-SBR (PZ-augmented SBR), PAC-SBR (PAC-augmented
SBR), and PZE-SBR (PZE-augmented SBR). Based on the batch/shaking
experiments, 3.24 g of PZ, PAC, and PZE (i.e., PZ dosage = 3 g/L) were added to
PZ-SBR, PAC-SBR, and PZE-SBR reactors before aeration, respectively. The PZ,
PAC, and PZE used for the adsorption of pollutants in PZ-SBR, PAC-SBR, and
PZE-SBR were pre-dried at 103 C to 105 C with a size of 75 m to 150 m
(passed sieve no. 100 and retained on sieve no. 200). Plates 3.1, 3.2, and 3.3 show
PZ, PAC, and PZE, respectively.

60

Plate 3-1: Powdered ZELIAC

Plate 3-2: Powdered activated carbon

Plate 3-3: Powdered zeolite


The removal efficiencies of COD, NH3N, colour, phenols, Fe, Mn, Ni, and Cd
were determined by measuring the target parameters before and after treatment.
Removal efficiency was calculated using the following equation:

61

Removal (%) =

(Eq. 3-1)

where Ci and Cf are the initial and final concentrations of the parameters,
respectively.
Central composite design (CCD) and response surface methodology (RSM)
were applied to design the experiments and data analysis. CCD was implemented
with Design Expert Software Version 6.0.7. RSM was employed to control the
optimum process parameters. RSM involves mathematical and statistical methods
suitable for the modeling and analysis of problems, in which responses of interest are
affected by several variables; the goal is to optimize these responses (Aziz et al.,
2011b). The total number of experiments for the three factors was determined to be
20 (=2k+2k+6), where k is the number of factors (k = 3). Each factor only has three
levels; thus, the appropriate model is the quadratic model shown in Eq. (2).
k

i 1

i 1

i j

Y i X i i X i 2 ij X i X j e

(Eq. 3-2)

where Y is the response; Xi and Xj are the variables; 0 is a stable coefficient;


j, jj, and ij represent the interaction coefficients of linear-, quadratic-, and secondorder terms, respectively; k is the number of analyzed parameters; and e is the error.
The results were investigated through ANOVA in Design Expert Software Version
6.0.7.
Each of the three operating variables was considered at three levels: low (1),
central (0), and high (+1). CCD and RSM were applied to evaluate the relationship
between the most significant operating variables, namely, aeration rate (L/min),
contact time (h), and leachate-to-wastewater ratio (%), and their responses
(dependent variables). The objective of this procedure is to optimize the operating
variables and their responses (Mojiri et al., 2013a). Different contact times (2, 12,

62

and 22 h), aeration rates (0.5, 4, and 7.5 L/min), and leachate-to-wastewater ratios
(80, 50, and 20 v/v %) were used in four reactors. The leachate-to-wastewater ratio
was 20% to 80% (v/v) in the SBRs. A similar range was used in previous studies
(Qasim and Chiang, 1994; een and akroglu, 2001; Cecen and Aktas, 2001;
Cecen et al., 2003; Neszaj et al., 2007; Neszaj et al., 2008; Litas et al., 2012; Cecen
et al., 2013; Capodici et al., 2014).
To conduct an adequate analysis of the aerobic process, the removal of the
eight dependent parameters (colour, COD, ammonia, phenols, Fe, Cd, Ni, and Mn)
was measured as responses. 3D plots with respective contour plots were obtained
from the experimental results. The effects of the interaction of the three factors on
the responses were then analyzed (Tables 3.3 to 3.4).

Table 3-3: Coded and actual values of variables for normal-SBR, PZ-SBR, PACSBR, and PZE-SBR
Factors

Unit

Levels of variables
-1

Aeration Rate

L/min

0.5

4.0

7.5

Aeration time (Contact

12

22

20

50

80

Time)
Wastewater Mixing
Ratio

63

Table 3-4: Experimental variables for SBRs


Run

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

Aeration
Rate
(L/min)
4.0
7.5
0.5
0.5
0.5
0.5
4.0
7.5
4.0
4.0
7.5
4.0
7.5
4.0
0.5
7.5
4.0
4.0
4.0
4.0

Contact
Time (h)
12
22
22
22
12
2
12
12
2
22
22
12
2
12
2
2
12
12
12
12

Leachate to
Wastewater
Ratio (%)
80
20
80
20
50
20
50
50
50
50
80
50
80
50
80
20
50
50
20
50

3.8 Continuous SBR experiments


Continuous SBR experiments were conducted in the six reactors. Six 2000 mL
beakers were utilized. Each beaker had a working volume of 1200 mL, an inner
diameter of 113 mm, and a height of 200 mm. A magnetic stirrer placed at the
bottom of the reactors was used to mix the media. The experiments were conducted
at room temperature. An air pump (YASUNAGA Air Pump Inc., China) was used to
provide the reactors with air. The parameters of the air pump (model LP-60A, serial
no. 08110014) were as follows: voltage of 240 V, frequency of 50 Hz, input power
of 61 W, pressure of 0.012 MPa, and air volume of 60 L/min. The air flow speed was
manually regulated with an air flow meter (Dwyer Flow Meter, model RMA-26SSV). In the continuous SBR experiments, the reactors were filled with 120 mL of
the returned sludge (10% of the working volume) and 1080 mL of mixed leachate

64

and wastewater (90% of the working volume). The reactors were divided into four
groups, namely, normal-SBR, PZ-SBR, PAC-SBR, and PZE-SBR.
The continuous SBR experiments were performed based on optimum
parameters (settling time, adsorbents dosage, contact time, aeration rate, and
leachate-to-wastewater mixing ratio). The hydraulic retention time, organic loading
rate, food-to-microorganism ratio, and DO were monitored in the continuous SBR
experiments.

3.8.1 Normal-SBR
The reactors were filled with 120 mL of the returned sludge (10% of the
working volume) and 1080 mL of mixed leachate and wastewater (90% of the
working volume). The details of the continuous SBR experiments are shown in Table
3.5.
3.8.2 PZ-SBR
The reactors were filled with 120 mL of the returned sludge (10% of the
working volume) and 1080 mL of mixed leachate and wastewater (90% of the
working volume). In accordance with the batch experiments, 3.24 g of PZ (i.e., PZ
dosage = 3 g/L) was added to the PZ-SBR reactor before aeration. The details of the
continuous SBR experiments are shown in Table 3.5.

3.8.3 PAC-SBR
The reactors were filled with 120 mL of the returned sludge (10% of the
working volume) and 1080 mL of mixed leachate and wastewater (90% of the
working volume). In accordance with the preliminary experiments, 3.24 g of PAC

65

(i.e., PAC dosage = 3 g/L) was added to the PAC-SBR reactor before aeration. The
details of the continuous SBR experiments are shown in Table 3.5.

3.8.4 PZE-SBR
In the current research, the source of zeolite is from Indonesia (Supplier:
TANGKAS LAKSANA SDN BHD (837809-V; No. 29, Tingkar 2, Jalan Permatang
Rawa 1, Kawasan Perniagaan Permatang Rawa, 14000 Bukit Mertajam, Pulau
Pinang). The reactors were filled with 120 mL of the returned sludge (10% of the
working volume) and 1080 mL of mixed leachate and wastewater (90% of the
working volume). In accordance with the batch experiments, 3.24 g of PZE (i.e., PZE
dosage = 3 g/L) was added to the PZE-SBR reactor before aeration. The details of
the continuous SBR experiments are shown in Table 3.5. These details are based on
the optimum parameters determined in the pre-SBR and RSM experiments.

Table 3-5: Details of continuous SBR experiments


No.

1
2
3
4
5
6
7
8
9

Parameter

Settling time (min)


Adsorbent dosage (g/L)
Aeration time (Contact time; h)
Aeration rate (L/min)
Leachate/wastewater ratio (v/v;
%)
Cycle time (h)
OLR (kg/m3.d)
HRT (d)
MLSS (mg/L)

NormalSBR
90
12.68
4.32
20
15.5
1.00
0.72
1510

66

Value
PZPAC-SBR
SBR
90
90
3
3
11.65
12.82
2.41
3.07
20
20

PZESBR
90
3
12.60
1.82
20

15.5
1.00
0.72
7613

15.5
1.00
0.72
6205

15.5
1.00
0.72
6516

CHAPTER 4
RESULTS AND DISCUSSIONS
4.1 Introduction
This chapter is composed of five sections. The characteristics of Semeling
landfill leachate are presented in the first section. The characteristics of domestic
wastewater and returned activated sludge are discussed in the second section. The
pre-SBR experiments, which include the batch/shaking and batch/optimization
experiments (experiments were designed by RSM to optimize operational parameters
in SBR process), are described in the third and fourth sections. The continuous
experiments in this study are shown in the fifth section.

4.2 Characteristics of landfill leachate in Semeling, Sungai Petani


Table 4.1 shows the characteristics of Semeling landfill leachate. The leachate
parameters are compared with the values prescribed by the Environmental Quality
(Control of Pollution from Solid Waste Transfer Station and Landfill) Regulations
2009, Malaysian Environmental Quality Act 1974.
The landfill leachate being studied has a high concentration of COD (1301
mg/L). The BOD5 was 269 mg/L, thereby yielding a BOD5/COD ratio of 0.20. The
average value of colour was 1690 Pt.Co. The NH3N concentration was 532 mg/L.
The average concentration of phenols was high (1.69 mg/L). The concentrations of
metals such as iron (Fe), manganese (Mn), nickel (Ni), and cadmium (Cd) were 6.03,
1.98, 4.94, and 2.71 mg/L, respectively.
The concentration of COD, BOD5, colour, phenols, NH3N, Fe, Mn, Ni, Cd,
and chromium exceeded the values prescribed by the Environmental Quality
(Control of Pollution from Solid Waste Transfer Station and Landfill) Regulations
67

2009, Malaysian Environmental Quality Act 1974. Meanwhile, temperature, pH


level, and sulfide concentration were within the allowable limit.
Aziz et al. (2011a) reported that mature landfill leachate (age >10 years)
usually contains a high amount of NH3N (>400 mg L-1), a moderately high COD
(<4000 mg L-1), and a low BOD5/COD ratio (<0.1). Chaari et al. (2011) stated that
nearly 10% of metals in leachate from dumping sites are free metal ions. As the
landfill ages, the biodegradable portion of organic contaminants in the leachate
decreases as a result of the anaerobic decomposition in the landfill site (Aziz et al.,
2012).
Aziz et al. (2012) reported that the Kulim landfill leachate had the following
characteristics: the pH level was 8.02; the concentration of COD was 1295; the
BOD5/COD ratio was 0.20; and the amount of NH3N, phenols, and total Fe was
562, 1.54, and 3.82, respectively. These data are almost consistent with the
characteristics of the Semeling landfill leachate.

68

Table 4-1: Semeling Petani Landfill Leachate Characteristics


No.

Parameter

Leachate

Leachate

Leachate

Standard

minimum

maximum

average value

discharge limit

value

value

for leachate a

Temperature (C)

26.9

30.0

28.7

40

pH

6.75

8.92

8.25

6-9

EC (ms/cm)

3.18

9.92

4.94

Salinity (g/L)

2.00

4.27

3.10

Total solids (mg/L)

1743

9641

5723

Suspended solids (mg/L)

113

1218

710

50

Total Hardness (mg/L

742

2411

1912

CaCO3)
8

Colour (Pt. Co)

1017

2432

1690

100

BOD5 (mg/L)

137

931

269.0

20

10

COD (mg/L)

714

2993

1301

400

11

BOD5/COD

0.19

0.37

0.20

0.05

12

TDS (%)

3.11

6.18

5.72

13

ORP (mV)

5.0

13.9

11.6

14

MLVSS/MLSS

16

Nitrite (mg/L NO2-N-HR)

13.00

139.8

54.1

17

Total phosphorus (mg/L

9.3

129.7

17.8

3-

PO4 )
18

NH3-N (mg/L)

291.0

984.0

532.0

5.0

19

Total organic carbon (mg/L

19.3

67.1

44.2

TOC)
20

Sulfide (mg/L)

0.19

0.53

0.30

0.5

21

Total iron (mg/L)

4.32

9.18

6.03

5.0

22

Total manganese (mg/L)

1.00

2.39

1.98

0.20

23

Total Zinc (mg/L)

1.00

2.67

1.89

2.0

24

Total copper (mg/L)

0.88

2.09

1.17

0.20

25

Total aluminum (mg/L)

0.020

0.10

0.034

26

Total nickel (mg/L)

3.13

6.27

4.94

0.20

27

Total chromium (mg/L)

0.09

0.47

0.21

0.20

28

Total cobalt (mg/L)

0.13

0.97

0.81

29

Total lithium (mg/L)

0.09

0.89

0.64

30

Total molybdenum (mg/L)

0.16

0.91

0.78

31

Total cadmium (mg/L)

1.17

3.89

2.71

0.01

32

Total calcium (mg/L)

89.13

159.31

121.45

33

Total magnesium (mg/L)

16.11

39.14

25.34

34

Phenols (mg/L)

1.11

1.91

1.69

0.001

a Environmental Quality (Control of Pollution from Solid Waste Transfer Station and Landfill) Regulations 2009, under the
Laws of MalaysiaMalaysia Environmental Quality Act 1974

69

4.3 Domestic wastewater and activated sludge characteristics


The characteristics of domestic wastewater and returned activated sludge
characteristics are given in Table 4.2. The obtained parameters were compared
against Environmental Quality (Sewage, Industrial Effluents) Regulation 2009,
Malaysian Environmental Quality Act 1974, Standards A and B.
The domestic wastewater characteristics in terms of pH, BOD5, COD,
BOD5/COD, NH3-N, phenols, total iron, total manganese, total nickel, and total
cadmium were 6.87 mg/L, 64.2 mg/L, 156 mg/L, 0.41, 149 mg/L, 0.04 mg/L, 1.21
mg/L, 0.67 mg/L, 0.51 mg/L, 0.39 mg/L.
The concentration of COD, sulfide, phenols and iron, manganese, nickel and
cadmium were more than standard A in Environmental Quality (Sewage and
Industrial Effluents) Regulation 2009, Malaysian Environmental Quality Act 1974.
However, temperature, and pH were within the allowable limit.
The pH, BOD5, COD, BOD5/COD, NH3-N, phenols, total iron, total
manganese, total nickel, and total cadmium were 6.60, 87.5, 218, 0.40, 160, 0.07,
1.95, 0.91, 0.78 and 0.39, respectively in the activated sludge. Aziz (2012) reported
the concentration of pH, EC, TDS, salinity, total solid, MLSS, ORP and COD, NH3N were 6.75, 2.02 ms/cm, 1.31 %, 1.03 g/L, 11540 mg/L, -39.6 mV, 4055 mg/L, and
143 mg/L, respectively, in Bayan Baru Wastewater Treatment Plant, Penang,
Malaysia. These data approximately are in line with returned activated sludge
characteristics in the present study.

70

Table 4-2: Bayan Baru, Penang, Domestic Wastewater and Activated Sludge
Characteristics
No.

Parameter

Temperature

wastewater

wastewater

wastewater

Standard discharge

Activated

minimum

maximum

average

limit for wastewater

Sludge

value

value

value

Standard

Standard

value

25.9

29.2

28.6

40.0

40.0

28.6

(C)
2

pH

6.00

7.29

6.87

6.0-9.0

5.5-9.0

6.60

EC (ms/cm)

0.76

2.10

1.00

1.09

Salinity (g/L)

0.01

0.04

0.02

0.03

Total solids

10711

50.0

100.0

9234

(mg/L)
6

Suspended
solids (mg/L)

Total Hardness
(mg/L CaCO3)

Colour (Pt. Co)

6.00

BOD5 (mg/L)

51.23

102

59.2

20.0

50.0

87.5

10

COD (mg/L)

79.0

239

149

50.0

100.0

218

11

BOD5/COD

0.36

0.42

0.39

0.40

12

TDS (%)

0.91

1.39

1.03

1.44

13

ORP (mV)

-126.0

14

MLVSS/MLSS

0.82

16

Nitrite (mg/L

7.39

19.24

10.1

56.17

118.61

81.13

5.0

10.0

NO2-N-HR)
17

Total
phosphorus
(mg/L PO43-)

18

NH3-N (mg/L)

100.1

192.0

149.0

5.0

5.0

160.0

19

Total organic

19.29

47.3

29.0

36.0

carbon (mg/L
TOC)
20

Sulfide (mg/L)

0.390

0.810

0.600

0.50

0.50

0.654

21

Total iron

0.79

4.32

1.21

1.0

5.0

1.95

(mg/L)

71

Continue of Table 4-2: Bayan Baru, Penang, Domestic Wastewater and Activated
Sludge Characteristics
No.

Parameter

wastewater
minimum
value

wastewater
maximum
value

wastewater
average
value

22

Total
manganese
(mg/L)
Total Zinc
(mg/L)
Total copper
(mg/L)
Total
aluminum
(mg/L)
Total nickel
(mg/L)
chromium
Hexavalent
(mg/L)
chromium
Trivalent
(mg/L)
Total cobalt
(mg/L)
Total lithium
(mg/L)
Total
molybdenum
(mg/L)
Total cadmium
(mg/L)
Total calcium
(mg/L)

0.34

2.17

0.67

0.91

2.91

1.71

1.0

1.0

1.89

0.32

2.17

1.11

0.20

1.0

1.82

0.01

0.12

0.031

0.047

0.32

0.81

0.51

0.20

1.0

0.78

0.07

0.23

0.12

0.05

0.05

0.12

0.06

0.42

0.23

0.20

1.0

0.02

0.05

0.02

0.27

0.06

0.57

0.51

0.52

0.06

0.42

0.30

0.33

0.12

0.56

0.39

0.01

0.02

0.39

18.31

45.12

25.11

102.0

23
24
25

26
27

28

29
30
31

32
33

Standard discharge
limit for wastewater
Standard Standard
A
B
0.20
1.0

Activated
Sludge
average
value
0.91

4.4 Pre-SBR experiments


The pre-SBR experiments consist of the batch/shaking and batch/optimization
experiments.

4.4.1 Batch/shaking experiments


In the batch/shaking experiments, the selected parameters were powdered
ZELIAC (PZ) dosage and settling time. The best values of these parameters were

72

determined by conducting several SBR runs. The details of the batch/shaking


experiments are provided in the following sections.
The SBR system consists of the fill, react, settle, draw, and idle phases. In all
of the experiments, the duration of fill and mix (20 min), as well as that of draw and
idle (10 min), was fixed in accordance with the literature (Cecen and Aktas, 2004;
Neczaj et al., 2007; Neczaj et al., 2008; Aziz et al., 2011a; Aziz et al., 2011b).
The settling time and dosage of powdered ZELIAC (PZ) in batch/shaking
experiments to be used in fixed leachate-domestic wastewater ratio sample. The
selection of optimal settling time and PZ dosage was conducted using 2000 mL
beakers (working value was 1200 mL).

4.4.1.1 Settling time


The SBR phases consist of fill, react, settle, draw, and idle (Figure 4.1; Mahvi,
2008). In the reactor, DO concentration decreases with increasing settling time.
Reducing DO to less than 1 mg/L benefits the denitrification process (Aziz, 2011).
Different settling times (i.e., 0.5, 1, 1.5, 2, 3, 4, and 6 h) were employed in
accordance with the literature (Li et al., 2008; Wang et al., 2009; Aziz, 2011). DO
was measured at these times. The best settling time was selected based on DO
concentration.
Figure 4.2 and Table A.1 show that after 1.5 h of settling time, DO tends to
become constant. The selected settling time was 90 min, which is nearly consistent
with the values reported by Bu et al., 2010; Chan et al., 2010; and Lim et al., 2010
Aziz 2011.

73

Figure 4-1: Phases of normal SBR (Source: Mahvi, 2008)

DO (mg/L)
7

DO (mg/L)

6
5

4
3

DO (mg/L)

2
1
0
1

Settling Time (h)

Figure 4-2: Effect of Settling Time on DO in SBR

The settling time uses a major hydraulic selection pressure on the microbial
community. In fact, at a long settling time, poorly settling sludge flows cannot be
effectively withdrawn, and they may outcompete granule-forming bioparticles. As a
result, aerobic granulation could fail in an SBR run at longer settling times (Arrojo,
2007). As shown in Table 2.8, the settling time in many investigations was around 90
min.

74

4.4.1.2 PZ Production and PZ Dosage


A. PZ Production
ZELIAC was produced from zeolite, activated carbon, limestone, rice husk ash,
and Portland cement. All of these components were ground, passed through a 300
m mesh sieve, and then mixed (Table A.2). The mixture was then evenly poured in
a mold after water was added. After 24 h, the materials were removed from the mold
and soaked in water for 3 d to facilitate the curing process. After the materials were
left to dry for 2 d, they were crushed and passed through a sieve. Table 4.8 shows the
characteristics of the ZELIAC with the autosorb (Quantachrome AS1wintm, version
2.02) test.

B. Optimal PZ dosage (mg/L)


The selection of the optimal PZ dosage was conducted using 2000 mL beakers
(working value was 1200 mL). Different amounts of PZ (i.e., 1, 2, 3, 5, 7, 10, 15, and
20 g/L) were added to the beakers. The best PZ dosage was selected based on the
optimal removal of colour, NH3N, and COD in the beakers. Removal efficiencies
increased when the PZ dosage was increased from 0 g/L to 3 g/L (Figure 4.3). Figure
4.3 and Table A-2 show that when the PZ dosage exceeded 3 g/L, the removal
efficiencies tend to become constant or decrease. Thus, the selected optimal PZ
dosage was 3 g/L.
The colour removal efficiency increased with increasing PZ dosage up to 3
g/L. At a PZ dosage greater than 3 g/L, the colour removal efficiency decreased.
Aziz (2011) reported that increased PAC dosage resulted in dark colors in reactors,
thereby causing the decreased colour removal efficiency.

75

The NH3N and COD removal efficiencies were increased by increasing the
PZ dosage from 0 mg/L to 3 mg/L. When PZ dosage exceeded 3 mg/L, the removal
efficiency of NH3N and COD became fixed.

50

1200

45

Removal (%)

35

800

30

600

25
20

400

15

200

10

Concentration (mg/L)

1000

40

Color Removal (%)

Ammonia Removal
(%)
COD Removal (%)
Color (Pt. CO)
Ammonia (mg/L)

-200
0

10
15
PZ dosage (g/L)

20

25

COD (mg/L)

Figure 4-3: Removal parameters versus PZ-SBR dosage

C. Adsorption isotherm
Adsorption refers to the adhesion of atoms, ions, biomolecules, or molecules of
gas, liquid, or dissolved solids to a surface (Aziz et al., 2012):

(Eq. 4-1)

where qe is the quantity of solute adsorbed per unit weight of adsorbent (mg/g),
Co is the initial adsorbate concentration, Ce is the equilibrium adsorbate
concentration (mg/L), V is the volume of solution (L), and M is the mass of the
adsorbent (g).
Langmuir and Freundlich isotherms were used in this study to show the
characteristics of PZ adsorption.

76

D. Langmuir isotherm
Surface adsorption onto a solid is classified into two broad categories:
physisorption and chemisorption. Physisorption is a non-specific loose binding of the
adsorbate to the solid through van der Waalstype interactions. Multilayered
adsorption is possible, and it is easily disrupted by increasing temperatures.
Chemisorption involves a more specific binding of the adsorbate onto the solid
(Altig, 2013).

(Eq. 4-2)

where x/m is the mass of the adsorbate adsorbed per unit mass of adsorbent
(mg adsorbate per g activated carbon), a and b are the empirical constants, and Ce is
the equilibrium concentration of adsorbate in the solution after adsorption (mg/L).
Figure 4.4 and Figure 4.5 show the Langmuir isotherm regression for (a)
colour, (b) COD, and (c) NH3N and (a) Fe, (b) Mn, and (c) Ni. Tables 4.3 and 4.4
show the constants and correlation coefficients, the R2 values attained from the
Langmuir isotherm for colour, as well as the concentration of COD, NH3N, Fe, Mn,
and Ni. The dimensionless equilibrium parameters RL can be used to express the
characteristics of the Langmuir isotherm (Isa et al., 2007). RL is shown in Tables 4.3
and 4.4. The adsorption of colour, COD, and NH3N by ZELIAC follows the
Langmuir adsorption isotherm based on R2.
The R2, b, and Q for colour were 0.8992, 3.99, and 128.2, respectively. R2 =
0.938 colour removal from leachate with activated carbon was reported by Aziz et al.
(2012). Kamaruddin et al. (2013) reported Q = 100 for colour removal from textile
wastewater by activated carbon.
The R2, b, and Q for COD were 0.9476, 0.16, and 67.65, respectively.
Kamaruddin et al. (2013) reported R2 = 0.800, Q = 61.72, and b = 0.001 for COD
77

removal from wastewater by activated carbon. Aziz (2011) reported R2 = 0.902 and b
= 0.18 for COD removal by activated carbon.
The R2, b, and Q for NH3N were 0.9923, 0.19, and 36.49, respectively. Aziz
(2013) reported R2 = 0.995 and Q = 19.36 for NH3N removal from aqueous
solution.

Table 4-3: Langmuir equation for colour, COD and ammonia


Parameters

Q (mg/g)

R2

Colour
COD
NH3-N

128.20
67.56
36.49

3.99
0.16
-0.19

0.8992
0.9476
0.9923

Isotherm
Type
2.6(10-4)
7.7(10-3)
-0.019

Favorable
Favorable
Unfavorable

The R2, b, and Q for Fe were 0.8177, 8.15, and 0.700, respectively.
Abdulrasaq and Basiru (2010) reported R2 = 0.882 and Q = 0.09 for Fe removal by
coconut husk.
The R2, b, and Q for Mn were 0.9743, 3.18, and 0.198, respectively. The R2, b,
and Q for Ni were 0.9824, 5.52, and 0.386, respectively. Desta (2013) reported R2 =
0.998 and b = 0.189 for Ni removal from wastewater by activated carbon.

Table 4-4: Langmuir equation for Fe, Mn and Ni


Parameters

Q (mg/g)

R2

Fe
Mn
Ni

0.700
0.198
0.386

-8.15
3.18
-5.52

0.8177
0.9743
0.9824

0<RL<1 = Favorable; R<1= Unfavorable (Isa et al., 2007)

78

Isotherm
Type
-0.19
0.13
-0.04

Unfavorable
favorable
Unfavorable

1/(x/m)

0.012
0.01
0.008
0.006
0.004
0.002
0

y = 0.2614x + 0.0078
R = 0.8992
0

0.002

0.004

0.006

0.008

0.01

0.012

1/(Ce)

(a)
0.0164
0.0162
0.016
0.0158
0.0156
0.0154
0.0152
0.015

y = 0.0911x + 0.0148
R = 0.9476

0.005

0.01

0.015

0.02

1/(x/m)

(b)

0.0265
0.026
0.0255
0.025
0.0245 y = -0.1469x + 0.0274
0.024
R = 0.9923
0.0235
0
0.005
0.01

0.015

0.02

0.025

0.03

1(Ce)
(c)
Figure 4-4: Langmuir isotherm regression for (a) colour, (b) COD and (c) NH3-N

79

1.4
1/(x/m)

1.35
1.3
1.25
y = -0.1921x + 1.4267
R = 0.8177

1.2
1.15
0

0.2

0.4

0.6

0.8

1.2

1.4

1/(Ce)

(a)

1/(x/m)

4.8
4.6
4.4

y = -0.203x + 5.0464
R = 0.9743

4.2
4
0

1/(Ce)
(b)

2.5
1/(x/m)

2
1.5
1
y = -0.4694x + 2.5898
R = 0.9824

0.5
0
0

0.5

1.5

1(Ce)
(c)
Figure 4-5: Langmuir isotherm regression for (a) Fe, (b) Mn and (c) Ni

80

E. Freundlich isotherm
The Freundlich equation or Freundlich adsorption isotherm, an adsorption
isotherm, is a curve that relates the concentration of a solute on the surface of an
adsorbent to the concentration of the solute in the liquid with which it is in contact
(Aziz et al., 2012). The Freundlich equation can be written as follows (Hamdaoui
and Naffrechoux, 2007):

(Eq. 4-3)

where KF is a constant indicative of the relative adsorption capacity of the


adsorbent (mg1(1/n) L1/n g1) and n is a constant indicative of the intensity of the
adsorption.
Figures 4.6 and 4.7 show the Freundlich isotherm regression for (a) colour, (b)
COD, and (c) NH3N and (a) Fe, (b) Mn and (c) Ni. Tables 4.5 and 4.6 show all the
constants and correlation coefficients and R2 values attained from the Freundlich
isotherm for colour, COD, and NH3N and Fe, Mn, and Ni.
The R2, 1/n, and Kf for colour were 0.9602, 0.174, and 43.48, respectively.
Gupta et al. (2005) reported approximately Kf = 0.030 and R2= 0.94 for adsorption
colour by ash. The R2, 1/n, and Kf for COD were 0.9916, 0.062, and 47.20,
respectively. El-Naas et al. (2010) reported Kf = 0.71 and 0.60 and R2= 0.98 and 0.99
for COD removal from wastewater by activated carbon. The R2, 1/n, and Kf for NH3
N were 0.9799, 0.084, and 56.87, respectively. Aziz (2011) reported 1/n = 0.56, R2
= 0.99, and Kf = 20 for NH3N removal by activated carbon.
Table 4-5: Freundlich equation for colour, COD and ammonia
Parameters
Colour
COD
NH3-N

Kf (mg/g (L/mg)1/n)
43.48
47.20
56.87

1/n
0.174
0.062
-0.084

81

n
5.76
16.08
-11.90

R2
0.9602
0.9916
0.9799

Table 4-6: Freundlich equation for Fe, Mn and Ni


Parameters
Fe
Mn
Ni

Kf (mg/g (L/mg)1/n)
0.23
0.49
0.48

1/n
-0.116
-0.0868
-0.2756

N
-8.57
-11.52
-3.62

R2
0.9219
0.9599
0.9292

The R2, 1/n, and Kf for Fe were 0.9219, 0.116, and 0.23, respectively. Akl et
al. (2013) reported Kf = 0.28 and R2 = 0.99 for Fe adsorption by activated carbon.
The R2, 1/n, and Kf for Mn were 0.9599, 0.0868, and 0.49, respectively. Akl et
al. (2013) reported Kf = 0.35 and R2 = 0.95 for Mn adsorption by activated carbon.
The R2, 1/n, and Kf for Ni were 0.9292, 0.2756, and 0.48, respectively. Kaur
et al. (2012) reported Kf = 0.66 and R2= 0.91 for Ni adsorption by some activated
carbon that was produced by agriculture residues. Al Dwairi and Al-Rawajfeh (2012)
reported Kf = 0.54 and R2 = 0.967 for Ni adsorption by zeolite.
Table 4.7 shows the Langmuir and Freundlich equations for the present study.
Tables 4-4 to 4-6 show that the adsorption of colour, COD, NH3N, Fe, Mn, and Ni
follows the Langmuir and Freundlich isotherms because of high R2.

82

2.1

log (x/m)

2.08

y = 0.1736x + 1.6333
R = 0.9602

2.06
2.04
2.02

2
1.98
1.96

0.5

1.5

2.5

log (Ce)

log (x/m)

(a)
y = 0.0622x + 1.6736
R = 0.9916

1.82
1.815
1.81
1.805
1.8
1.795
1.79
1.785
1.78

0.5

1.5

2.5

1.5

2.5

log (Ce)

(b)

log (x/m)

1.63 y = -0.0843x + 1.7566


R = 0.9799
1.62

1.61
1.6

1.59
1.58
0

0.5

log (Ce)
(c)

Figure 4-6: Freundlich isotherm regression for (a) colour, (b) COD and (c) NH3-N

83

0
-0.1 -0.02 0

0.1

0.2

0.3

0.4

y = -0.1166x - 0.0875
R = 0.9219

-0.04

log (x/m)

-0.2

-0.06
-0.08
-0.1

-0.12
-0.14

log (Ce)

(a)
-0.63

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0
-0.64

log (x/m)

y = -0.0868x - 0.6921
R = 0.9599

-0.65

-0.66
-0.67

-0.68

log (Ce)

(b)

0
-0.3

-0.2

-0.1

log (x/m)

-0.1

0.1

0.2

y = -0.2756x - 0.3186
R = 0.9292

-0.2
-0.3
-0.4
log (Ce)
(c)

Figure 4-7: Freundlich isotherm regression for (a) Fe, (b) Mn and (c) Ni

84

Table 4-7: Langmuir and Freundlich equations for current study


Parameters
General form

Langmuir equation

Freundlich equation

Colour
COD
Ammonia
Fe
Mn
Ni

4.4.2 ZELIAC, Zeolite and Activated Carbon Characteristics


The results of the XRF and XRD analyses of ZELIAC are shown in Table 4.9
and Figure 4.3, respectively. Zeolite and activated carbon are both present in the
ZELIAC; thus, ZELIAC can act both as an adsorbent and an ion exchanger. The
SEM images of PZ are presented in Figure 4.4, which show that PZ has numerous
pores.
In this study, PZ with size ranging from 75 m to 150 m (passing sieve no.
100 and retained on sieve no. 200) was used as adsorbent in the PZSBR. Aziz et al.
(2011c) reported the optimal parameters in treating landfill leachate with the use of
powdered activated carbon (PAC)-augmented SBR technology. The characteristics
of PAC are as follows: size: 75 m to 150 m; BET surface area: 902.04 m 2/g;
micropore volume: 0.21 cm3/g; and the average pore diameter (4 V/A by Langmuir):
17.51 A.

85

Table 4-8: Powdered PZ, PAC and PZE Characteristics


Unit
Surface Area Data
MultiPoint BET
m2/g
Langmuir surface area
m2/g
BJH method cumulative adsorption surface area
m2/g
DH method cumulative adsorption surface area
m2/g
t-method external surface area
m2/g
t-method micropore surface area
m2/g
DR method micropore area
m2/g
Pore Volume Data
Total pore volume for pores with Diameter less than
ml/g
4.06 nm at P/P0= 0.501894
BJH method cumulative adsorption pore volume
ml/g
DH method cumulative adsorption pore volume
ml/g
t-method micropore volume
ml/g

PZ

PAC
Value

PZE

67.60
132.80
9.638
10.19
34.21
33.38
115.30

585.70
960.70
18.32
19.38
86.81
498.90
930.30

49.36
94.80
6.404
6.770
24.20
25.17
83.05

0.0402

0.3283

0.0289

0.0099
0.0101
0.0180

0.0188
0.0192
0.2714

0.0663
0.0675
0.0132

0.0409
0.0317
0.0322

0.3306
0.3051
0.3071

0.0295
0.0228
0.0232

2.384
3.652
3.652
1.760
0.3675
0.4532

2.242
3.374
3.374
1.180
36.75
45.32

2.348
3.666
3.666
1.740
0.3675
0.4523

Parameter

DR method micropore volume


ml/g
HK method cumulative pore volume
ml/g
SF method cumulative pore volume
ml/g
Pore Size Data
Average pore Diameter
nm
BJH method adsorption pore Diameter (Mode DV(d))
nm
DH method adsorption pore Diameter (Mode Dv9d))
nm
DA method pore Diameter (Mode)
nm
HK method pore Diameter (Mode)
nm
SF method pore Diameter (Mode)
nm

Table 4-9: XRF results for ZELIAC


Compounds/elements
C
CaO
SiO2
Al2O3
Fe2O3
K2O
MgO
Na2O
P2O5
SO3
Others

Composition (%)
14.350
32.401
42.002
7.300
1.502
1.005
1.000
0.100
0.030
0.030
0.280

The XRF and XRD results indicate the compounds and elements that exist in
ZELIAC. Table 4.9 and Figure 4.3 show that the major compounds and elements in
ZELIAC are SiO2 (42.0%), CaO (32.4%), and C (14.3%). Co is found in ZELIAC
because of the presence of limestone, whereas, SiO2 is found in ZELIAC because of
the presence of cement and zeolite. Based on some researches, SiO2 is one of the

86

most elements in the Portland cement (Ali et al., 2008; Stefanidou and Papayianni,
2012; Collodetti et al., 2014). Also the zeolite has a high amount of SiO2 based on

Figure 4-8: XRD Results for ZELIAC

Table 4.10.

87

Figure 4-9: SEM images from surface of ZELIAC

88

The SEM images show that numerous pores exist on the surface of ZELIAC.
These pores increase the surface area of ZELIAC. Kopac and Bozgeyik et al. (2010)
reported that the adsorption capacity of adsorbents increased by increasing surface
area.
Zeolite and activated carbon characteristics are shown in Table 4.8. Table 4.10
shows the XRF testing for zeolite.

Table 4-10: XRF results for zeolite


Compounds/elements
SiO2
Al2O3
CaO
K2O
Fe2O3
MgO
Na2O
TiO2
MnO
Others

Composition (%)
67.39
10.41
5.17
4.16
3.92
1.18
1.18
0.45
0.10
6.04

Most compounds in the zeolite are Al2O3 and SiO2 this is in line with findings
of Mustain et al. (2014). Zeolite consist of an aluminosilicate molecular structure
with weak cationic bonding sites (Mojiri, 2011) so the most elements in the zeolite
are Al and Si. The aluminosilicate molecular structure with weak cationic bonding
sites of zeolite are shown by Figure 4.10. This structure is useful for ion exchange.
Activated carbon is commonly used to adsorb natural organic compounds, taste
and odor compounds, and synthetic organic chemicals in drinking water treatment
(Devorak, 2013; Lin et al., 2010). Figure 4.11 shows the SEM image from surface of
powdered activated carbon. This figure shows the pores on the surface of activated
carbon.

89

Figure 4-10: SEM images from surface of zeolite

90

Figure 4-11: SEM images from surface of activated carbon

91

4.4.3 Batch/optimization experiments


4.4.3.1. Design of experiments by response surface methodology
As mentioned in section 3.7.2, response surface methodology (RSM) and
central composite design (CCD) were used to demonstrate the nature of the response
surface in the experimental design and clarify the optimum conditions of the
independent variables.

In the current study, variables include contact time (h),

aeration rate (L/min), leachate to wastewater mixing ratio (%; v/v), and their
responses include different contact times (2, 12, and 22 h), aeration rates (0.5, 4, and
7.5 L/min), and leachate to wastewater mixing ratios (80, 50, and 20 v/v %) which
were used in the SBR and PZSBR methods. To perform an adequate analysis of the
aerobic procedure, eight dependent parameters (COD, NH3N, colour, phenols, total
Fe, total Mn, total Ni, and total Cd) were selected as responses. Mojiri et al.
(2013a,b), Aziz et al. (2012), Umar et al. (2011), Adlan et al. (2011), Bashir et al.
(2010), Ghafari et al. (2009), and Aghamohammadi et al. (2007) used RSM for
optimization parameters.

4.4.3.2 Operation and performance of the reactors


The reactors were divided into four groups consisting of six reactors each for
SBR (normal SBR), six reactors each for powdered ZELIAC-SBR (PZ augmented
SBR), six reactors each for powdered activated carbon-SBR (PAC augmented SBR)
and six reactors each for powdered zeolite-SBR (PZE augmented SBR). Based on
batch/shaking experiments, 3.24 g of PZ, PAC and PZE (i.e., the dosage = 3 g/L)
were added to each PZ-SBR, PAC-SBR and PZE-SBR reactor before aeration. The
PZ, PAC and PZE used for the adsorption of pollutants in the PZ-SBR, PAC-SBR
and PZE-SBR were pre-dried at 103 C to 105 C with a size of 75 m to 150 m
92

(passing sieve no. 100 and retained on sieve no. 200). Table 4.3 shows the features of
the ZELIAC, activated carbon and zeolite with the autosorb (Quantachrome
AS1wintm, version 2.02) test. The beakers (reactors) were filled with 120 mL (10%)
of adjusted sludge and 1080 mL (90%) of domestic wastewater and Sungai Petani
landfill leachate (in different ratios), with a mixing ratio of 20% to 80% (v/v). To
increase the biodegradability ratio, channeling method can be used via mixing
landfill leachate with wastewater and sludge. The aerobic co-treatment of landfill
leachate and domestic wastewater was studied by een and Akta (2004). Also the
joint treatment of landfill leachate with municipal wastewater using submerged
membrane bioreactor was studied Hasar et al. (2009). Neszaj et al. (2008) studied the
sequencing batch reactor system for the co-treatment of landfill leachate and dairy
wastewater. In this study, the researchers mixed landfill leachate and dairy
wastewater with sludge.
Some studies reported the addition of adsorbents, such as activated carbon, to
activate sludge and SBR at the end of the enhancement of the biological treatment of
landfill leachate (Foo and Hameed, 2009; Aziz et al., 2011b; Aziz et al., 2011c).
The removal efficiencies were observed by measuring the target parameters
before and after the treatment process. The removal efficiency was calculated based
on the following equation (Eq. 2)
Removal (%) =

(Eq. 4-4)

where Ci and Cf are the initial and final concentrations of the parameters,
respectively. Table 4.11, Table 4.12, Table 4.13 and Table 4.14 show the
experiments results of Normal-SBR, PZ-SBR, PAC-SBR and PZE-SBR.

93

94

Aeration
rate
(L/min)

4.0
7.5
0.5
0.5
0.5
0.5
4.0
7.5
4.0
4.0
7.5
4.0
7.5
4.0
0.5
7.5
4.0
4.0
4.0
4.0

Run

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

12
22
22
22
12
2
12
12
2
22
22
12
2
12
2
2
12
12
12
12

Contact
time (h)
80
20
80
20
50
20
50
50
50
50
80
50
80
50
80
20
50
50
20
50

Leachate to
wastewater
mixing ratio
(%; v/v)
38.11
55.46
35.13
52.30
52.49
47.29
46.29
48.31
44.11
49.10
30.00
46.00
27.43
47.21
29.10
49.10
45.91
45.25
58.26
44.98

Colour
rem.
(%)
38.73
40.17
25.64
41.29
40.14
43.19
41.18
39.40
44.24
40.66
25.65
42.11
32.45
41.18
30.70
46.29
40.71
40.84
43.29
40.63

COD rm.
(%)
82.13
92.29
71.26
90.18
79.73
87.49
96.04
89.18
79.44
94.11
79.48
96.03
90.00
95.14
76.11
90.50
95.17
94.13
96.11
95.61

Ammonia
rem.
(%)
21.95
30.19
14.97
30.91
26.95
29.33
29.76
26.13
24.43
30.98
16.11
30.98
13.93
29.42
16.98
23.28
30.18
28.91
33.17
30.23

Phenols
rem.
(%)
19.71
43.14
18.22
42.61
36.97
40.83
38.91
35.51
38.03
36.04
16.70
37.78
16.82
38.91
16.97
40.71
37.99
37.88
45.59
36.58

Fe rem.
(%)
18.64
35.11
17.20
36.80
30.25
36.62
32.59
28.53
29.19
29.69
15.93
32.93
15.68
31.78
16.83
35.91
32.61
32.24
37.96
31.72

Mn rem.
(%)

Table 4-11: Experimental variables and results for the Normal-SBR

19.44
42.81
17.93
43.77
32.22
42.43
32.91
31.92
32.68
32.89
15.62
32.43
14.94
32.98
17.22
42.01
32.87
31.99
44.62
32.78

Ni rem.
(%)

18.42
41.69
17.71
42.31
31.97
42.73
32.41
30.72
30.77
31.63
15.22
31.92
14.77
32.22
17.71
41.83
32.11
32.41
43.48
32.62

Cd rem.
(%)

95

Aeration
rate
(L/min)

4.0
7.5
0.5
0.5
0.5
0.5
4.0
7.5
4.0
4.0
7.5
4.0
7.5
4.0
0.5
7.5
4.0
4.0
4.0
4.0

Run

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

12
22
22
22
12
2
12
12
2
22
22
12
2
12
2
2
12
12
12
12

Contact
time (h)
80
20
80
20
50
20
50
50
50
50
80
50
80
50
80
20
50
50
20
50

Leachate to
wastewater
mixing ratio
(%; v/v)
68.15
78.57
62.39
82.31
74.31
78.85
77.11
74.31
75.59
75.26
65.47
77.84
65.53
79.31
66.61
79.59
78.60
75.31
86.46
75.58

Colour
rem.
(%)
52.34
67.94
50.22
69.40
67.38
73.30
66.52
63.07
65.30
63.52
56.29
66.06
53.22
66.40
48.72
69.53
68.22
66.29
71.18
67.12

COD rm.
(%)
89.06
95.21
79.42
96.89
90.88
96.11
95.98
93.10
96.04
91.13
82.74
94.89
79.52
95.97
80.67
97.00
92.11
92.00
98.27
91.09

Ammonia
rem.
(%)
46.29
61.63
48.17
63.71
55.13
62.34
53.25
52.89
55.13
55.13
47.29
52.18
45.23
52.88
46.01
60.61
52.37
52.64
62.23
51.93

Phenols
rem.
(%)
43.59
76.48
44.27
78.21
72.33
78.88
72.53
71.49
71.77
71.77
37.76
71.58
43.51
71.94
45.69
76.48
74.51
73.66
80.06
72.32

Fe rem.
(%)

Table 4-12: Experimental variables and results for the PZ-SBR

43.51
70.39
44.56
71.58
59.77
73.21
61.85
60.58
60.92
61.06
39.31
63.69
42.29
62.60
45.67
71.63
59.81
62.89
73.38
62.86

Mn rem.
(%)

41.31
76.74
38.55
77.30
56.78
79.09
60.83
58.79
58.79
58.89
36.58
61.24
37.02
57.78
38.88
75.19
58.81
60.58
78.11
60.41

Ni rem.
(%)

39.59
72.10
38.11
74.31
56.24
76.57
59.38
56.24
57.20
57.89
36.06
57.57
36.17
57.71
39.57
74.74
59.99
60.48
76.37
59.60

Cd rem.
(%)

96

Aeration
rate
(L/min)

4.0
7.5
0.5
0.5
0.5
0.5
4.0
7.5
4.0
4.0
7.5
4.0
7.5
4.0
0.5
7.5
4.0
4.0
4.0
4.0

Run

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

12
22
22
22
12
2
12
12
2
22
22
12
2
12
2
2
12
12
12
12

Contact
time (h)
80
20
80
20
50
20
50
50
50
50
80
50
80
50
80
20
50
50
20
50

Leachate to
wastewater
mixing ratio
(%; v/v)
51.53
70.65
50.98
72.64
53.98
73.23
55.91
55.19
56.31
54.37
48.98
56.77
50.23
54.87
51.93
72.19
53.11
55.31
75.30
57.09

Colour
rem.
(%)
45.93
62.41
43.73
64.91
55.23
63.17
58.03
57.11
56.59
55.01
42.03
57.63
41.13
55.03
42.42
62.41
54.41
56.03
67.43
56.03

COD rm.
(%)
78.96
95.72
78.21
97.41
92.93
97.73
93.43
87.96
93.18
90.88
76.06
91.19
77.44
89.63
79.41
96.78
91.29
90.46
97.69
90.40

Ammonia
rem.
(%)
23.91
44.08
22.89
48.31
36.25
45.63
36.17
34.30
34.93
36.43
21.47
36.72
20.89
34.02
22.19
45.01
36.60
34.98
47.82
35.64

Phenols
rem.
(%)
31.49
51.13
30.96
52.11
37.04
57.91
43.75
39.17
41.04
42.42
29.04
43.43
29.97
43.06
30.39
46.86
43.99
43.75
60.06
43.91

Fe rem.
(%)

Table 4-13: Experimental variables and results for the PAC-SBR

26.11
49.06
23.98
49.27
32.70
51.19
40.49
34.94
31.70
37.22
21.31
40.13
22.24
39.71
23.13
43.24
39.89
39.98
52.55
41.82

Mn rem.
(%)

23.96
47.21
22.90
47.61
32.10
51.09
40.91
36.15
30.10
39.16
20.74
39.96
21.21
40.93
21.76
41.51
40.91
39.88
55.40
40.44

Ni rem.
(%)

26.00
48.74
24.13
49.94
32.16
51.73
40.15
35.17
31.16
39.19
22.02
40.14
23.43
40.02
23.00
43.63
41.02
40.41
56.53
42.00

Cd rem.
(%)

97

Aeration
rate
(L/min)

4.0
7.5
0.5
0.5
0.5
0.5
4.0
7.5
4.0
4.0
7.5
4.0
7.5
4.0
0.5
7.5
4.0
4.0
4.0
4.0

Run

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

12
22
22
22
12
2
12
12
2
22
22
12
2
12
2
2
12
12
12
12

Contact
time (h)
80
20
80
20
50
20
50
50
50
50
80
50
80
50
80
20
50
50
20
50

Leachate to
wastewater
mixing ratio
(%; v/v)
54.13
71.42
51.93
74.88
61.93
73.09
62.61
60.04
61.17
62.11
50.00
64.13
49.23
63.81
52.21
70.00
62.82
63.00
75.91
62.79

Colour
rem.
(%)
42.11
60.09
39.91
61.72
56.93
62.00
57.77
56.11
56.14
55.63
39.90
56.81
40.16
57.93
41.13
59.41
57.18
57.03
63.13
57.42

COD rm.
(%)
78.72
88.94
77.92
92.74
84.93
96.13
84.13
83.61
84.17
84.31
77.37
84.47
79.11
83.64
79.43
89.01
84.13
83.97
94.93
84.03

Ammonia
rem.
(%)
24.27
41.76
23.87
45.13
34.67
42.14
36.91
35.32
36.13
35.47
21.49
36.00
23.17
37.18
23.07
42.84
36.43
36.43
43.63
35.88

Phenols
rem.
(%)
31.96
59.11
31.01
63.03
47.18
61.70
52.96
45.00
49.19
49.13
29.90
52.84
30.02
53.11
31.90
56.18
53.44
53.11
65.08
53.04

Fe rem.
(%)

Table 4-14: Experimental variables and results for the PZE-SBR

33.13
54.76
31.72
57.09
41.19
55.76
49.13
39.00
42.99
42.09
28.74
47.79
27.31
49.00
28.94
51.56
48.06
47.91
59.93
47.91

Mn rem.
(%)

32.17
58.38
30.43
61.27
47.83
60.00
50.14
46.40
47.13
46.11
25.14
48.09
26.19
47.11
27.77
47.97
49.01
49.92
63.18
48.71

Ni rem.
(%)

30.91
56.11
28.89
57.24
44.73
56.26
46.81
41.97
44.12
44.64
28.04
46.74
27.17
46.99
27.99
52.93
47.13
47.27
60.41
48.00

Cd rem.
(%)

4.4.3.3 Normal SBR reactors


The Figures 4.12 to 4.19 show the pollutants removal by Normal-SBR. The
results will be discussed in Section 4.4.4.

i) Colour removal
In this study, the minimum and maximum colour removal efficiencies obtained
by the SBR reactors were 27.43% (contact time = 2 h, aeration rate = 7.50 L/min,
and leachate to wastewater ratio = 80%) and 58.26% (contact time = 12 h, aeration
rate = 4.0 L/min, and leachate to wastewater ratio = 20%), respectively, as shown in
Table 4.11. In the Normal-SBR method, an optimal colour removal efficiency of
56.88% was obtained at 15.29 h contact time, an aeration ratio of 7.50 L/min, and
20.00% leachate to wastewater ratio. Figure 4.12 shows the colour removal by
Normal-SBR.

ii) COD removal


Table 4.11 shows that the removal efficiency of Normal-SBR varied from
25.64% (contact time = 22 h, aeration rate = 0.5 L/min, and leachate to wastewater
ratio = 80%) to 46.29% (contact time = 2 h, aeration rate = 7.5 L/min, and leachate to
wastewater ratio = 20%). In the Normal-SBR method, an optimal COD removal
efficiency of 46.36% was obtained at 9.29 h contact time, an aeration ratio of 4.43
L/min, and 21.01% leachate to wastewater ratio. Figure 4.13 shows the COD
removal by Normal-SBR.

98

iii) NH3-N removal


The NH3-N removal using Normal-SBR has been showed by Figure 4.14.
Table 4.11 shows that the removal efficiency of Normal-SBR varied from 71.26%
(contact time = 22 h, aeration rate = 0.5 L/min, and leachate to wastewater ratio =
80%) to 96.11% (contact time = 12 h, aeration rate = 4.0 L/min, and leachate to
wastewater ratio = 20%). This result is in agreement with the finding of Aziz et al.
(2011b, c). In the Normal-SBR method, an optimal NH3N removal efficiency of
97.97% was obtained at 14.15 h contact time, an aeration ratio of 5.09 L/min, and
23.95% leachate to wastewater ratio.

iv) Phenols removal


The phenols removal using Normal-SBR has been showed by Figure 4.15. The
minimum and maximum phenol removal efficiencies obtained in this study by the
Normal-SBR reactors were 13.93% (contact time = 2 h, aeration rate = 7.50 L/min,
and leachate to wastewater ratio = 80%) and 33.17% (contact time = 12 h, aeration
rate = 4.0 L/min, and leachate to wastewater ratio = 20%), respectively (Table 4.11).
In the Normal-SBR method, an optimal phenol removal efficiency of 34.23% was
obtained at 20.41 h contact time, aeration ratio of 3.61 L/min, and 22.59% leachate to
wastewater ratio.

v) Iron removal
Figure 4.16 shows the iron removal by Normal-SBR. The removal
effectiveness of Normal-SBR varied from 16.70% (aeration rate = 7.5 L/min, contact
time = 22 h, and leachate to wastewater ratio = 80%) to 45.59% (aeration rate = 4.0
L/min, contact time = 12 h, leachate to sewerage ratio = 20%) (Table 4.11). The
99

optimum Fe removal of Normal-SBR (45.12%) was attained at an aeration rate of


3.97 L/min, contact time of 15.24 h, and leachate to sewerage ratio of 20%.

vi) Manganese removal


Figure 4.17 shows the manganese removal by Normal-SBR. In the current
study, the lowest and highest Mn removal effectiveness attained by Normal-SBR
reactors was 15.68% (contact time = 2 h, aeration rate = 7.50 L/min, leachate to
wastewater ratio = 80%) and 37.96% (contact time = 12 h, aeration rate = 4.0L/min,
leachate to wastewater ratio = 20%), respectively (Table 4.11). The optimum Mn
removal of Normal-SBR (38.17%) was attained at an aeration rate of 5.47 L/min,
contact time of 12.87 h, and leachate to wastewater ratio of 21.25%.

vii) Nickel removal


The nickel removal using Normal-SBR has been showed by Figure 4.18. The
removal effectiveness of Normal-SBR varied from 14.94% (aeration rate = 7.5
L/min, contact time = 2 h, and leachate to wastewater ratio = 80%) to 44.62%
(aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater ratio = 20%)
(Table 4.10). The optimum nickel removal of Normal-SBR (44.62%) was attained at
an aeration rate of 3.21 L/min, contact time of 12.26 h, and leachate to wastewater
ratio of 20.05%.

viii) Cadmium removal


The cadmium removal using Normal-SBR has been showed by Figure 4.19. In
this study, the lowest and highest Cd removal effectiveness attained by Normal-SBR
reactors was 14.77% (aeration rate = 7.50 L/min, contact time = 2 h, leachate to
100

wastewater ratio = 80%) and 43.48% (aeration rate = 4.0 L/min, contact time = 12h,
leachate to wastewater ratio = 20%), respectively (Table 4.11). The optimum Cd
removal of Normal-SBR (43.52%) was attained at an aeration rate of 1.57 L/min,
contact time of 7.99 h, and leachate to wastewater ratio of 20.12%.

Figure 4-12: The 3D surface plots of colour removal in Normal-SBR

101

Figure 4-13: The 3D surface plots of COD removal in Normal-SBR

102

Figure 4-14: The 3D surface plots of ammonia removal in Normal-SBR

103

Figure 4-15: The 3D surface plots of phenols removal in Normal-SBR

104

Figure 4-16: The 3D surface plots of Fe removal in Normal-SBR

105

Figure 4-17: The 3D surface plots of Mn removal in Normal-SBR

106

Figure 4-18: The 3D surface plots of Ni removal in Normal-SBR

107

Figure 4-19: The 3D surface plots of Cd removal in Normal-SBR

108

4.4.3.4 PZ-SBR reactors (PZ supplemented SBR)


The Figures 4.20 to 4.27 show the pollutants removal by PZ-SBR. The results
will be discussed in Section 4.4.4.

i) Colour removal
The minimum and maximum colour removal efficiencies obtained by the PZSBR reactors were 62.39% (contact time = 22 h, aeration rate = 0.50 L/min, and
leachate to wastewater ratio = 80%) and 86.46% (contact time = 12 h, aeration rate =
4.0 L/min, and leachate to wastewater ratio = 20%), respectively (Table 4.12). In the
PZ-SBR method, an optimal colour removal efficiency of 85.15% was obtained at
contact time of 13.65 h, aeration ratio of 3.58 L/min, and 20.00% leachate to
wastewater ratio.

ii) COD removal


The removal efficiencies of PZ-SBR varied from 50.22% (contact time = 2 h,
aeration rate = 0.5 L/min, and leachate to wastewater ratio = 80%) to 73.30%
(contact time = 22 h, aeration rate = 0.5 L/min, and leachate to wastewater ratio =
20%) (Table 4.12). An optimum COD removal efficiency of 73.33% was achieved in
the PZ-SBR method at 6.36 h contact time, aeration ratio of 1.23 L/min, and 20.0%
leachate to wastewater ratio.

iii) NH3-N removal


The removal efficiency of PZ-SBR varied from 79.42% (contact time = 22 h,
aeration rate = 0.5 L/min, and leachate to wastewater ratio = 80%) to 98.27%
(aeration rate = 4.0 L/min, contact time = 12 h, aeration rate = 0.5 L/min, and
109

leachate to wastewater ratio = 20%) (Table 4.12). In the PZ-SBR method, an optimal
ammonia removal efficiency of 98.63% was obtained at 7.24 h contact time, an
aeration ratio of 2.64 L/min, and 26.54% leachate to wastewater ratio.

iv) Phenols removal


The minimum and maximum phenol removal efficiencies obtained by the PZSBR reactors were 45.23% (contact time = 2 h, aeration rate = 0.50 L/min, and
leachate to wastewater ratio = 80%) and 63.71% (contact time = 22 h, aeration rate =
0.50 L/min, leachate to wastewater ratio = 20%) (Table 4.12). In the PZ-SBR
method, an optimal phenol removal efficiency of 63.71% was obtained at an aeration
ratio of 0.52 L/min, 21.96 h contact time, and 20.07% leachate to wastewater ratio.

v) Iron removal
The removal effectiveness of PZ-SBR varied from 37.76% (aeration rate = 7.5
L/min, contact time = 22 h, and leachate to wastewater ratio = 80%) to 80.06%
(aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater ratio = 20%)
(Table 4.12). The optimum Fe removal of PZ-SBR (80.06%) was attained at an
aeration rate of 1.71 L/min, contact time of 12.87 h, and leachate to sewerage ratio of
25.73%.

vi) Manganese removal


The lowest and highest Mn removal effectiveness attained by PZ-SBR reactors
was 39.31% (aeration rate = 7.50 L/min, contact time = 22 h, leachate to wastewater
ratio = 80%) and 73.38% (aeration rate = 4.00 L/min, contact time = 12 h, leachate to
wastewater ratio = 20%), respectively (Table 4.12). The optimum Mn removal of PZ110

SBR (73.38%) was attained at an aeration rate of 3.92 L/min, contact time of 7.71 h,
and leachate to wastewater ratio of 20.69%.

vii) Nickel removal


The removal effectiveness of PZ-SBR varied from 36.58% (aeration rate = 7.5
L/min, contact time = 2 h, and leachate to wastewater ratio = 80%) to 78.09%
(aeration rate = 0.50 L/min, contact time = 2.0 h, leachate to wastewater ratio = 20%)
(Table 4.12). PZ-SBR attained its optimum nickel removal (79.10%) at an aeration
rate of 3.22 L/min, contact time of 9.15 h, and leachate to wastewater ratio of
20.22%.

viii) Cadmium removal


The lower and highest Cd removal effectiveness attained by PZ-SBR reactors
was 36.06% (aeration rate = 7.50 L/min, contact time = 2 h, leachate to wastewater
ratio = 80%) and 76.57% (aeration rate = 0.50 L/min, contact time = 2.0 h, leachate
to wastewater ratio = 20%), respectively (Table 4.11). The optimum Cd removal of
PZ-SBR (76.59%) was attained at an aeration rate of 3.68 L/min, contact time of
15.31 h, and leachate to wastewater ratio of 20.03%.

111

Figure 4-20: The 3D surface plots of colour removal in PZ-SBR

112

Figure 4-21: The 3D surface plots of COD removal in PZ-SBR

113

Figure 4-22: The 3D surface plots of ammonia removal in PZ-SBR

114

Figure 4-23: The 3D surface plots of phenols removal in PZ-SBR

115

Figure 4-24: The 3D surface plots of Fe removal in PZ-SBR

116

Figure 4-25: The 3D surface plots of Mn removal in PZ-SBR

117

Figure 4-26: The 3D surface plots of Ni removal in PZ-SBR

118

Figure 4-27: The 3D surface plots of Cd removal in PZ-SBR

119

4.4.3.5 PAC-SBR reactors (PAC supplemented SBR)


The Figures 4.28 to 4.35 show the pollutants removal by PAC-SBR. The
results will be discussed in Section 4.4.4.

i) Colour removal
The removal effectiveness of PAC-SBR varied from 48.98% (aeration rate =
7.5 L/min, contact time = 22 h, and leachate to wastewater proportion= 80 %) to
75.30% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.13). In PAC-SBR, the optimum colour removal
effectiveness of 74.39% was attained at the aeration proportion of 3.55 L/min, 4.94 h
contact time, and 20.00% leachate to wastewater proportion.

ii) COD removal


The removal effectiveness of PAC-SBR varied from 41.13% (aeration rate =
7.5 L/min, contact time = 2 h, and leachate to wastewater proportion= 80 %) to
67.43% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.13). In PAC-SBR, the best possible COD removal
effectiveness of 66.47% was attained at the aeration proportion of 3.34 L/min, 12.69
h contact time, and 20.00% leachate to wastewater proportion.

iii) NH3-N removal


The removal effectiveness of PAC-SBR varied from 76.06% (aeration rate =
7.5 L/min, contact time = 22 h, and leachate to wastewater proportion= 80 %) to
97.37% (aeration rate = 0.50 L/min, contact time = 2 h, leachate to wastewater
proportion= 20 %) (Table 4.13). In PAC-SBR, the optimum ammonia removal
120

effectiveness of 58.57% was attained at the aeration proportion of 3.84 L/min, 2.35 h
contact time, and 22.34% leachate to wastewater proportion.

iv) Phenols removal


The removal effectiveness of PAC-SBR varied from 20.89% (aeration rate =
7.5 L/min, contact time = 2 h, and leachate to wastewater proportion= 80 %) to
48.31% (aeration rate = 0.50 L/min, contact time = 22 h, leachate to wastewater
proportion= 20 %) (Table 4.13). In PAC-SBR, the best possible phenols removal
effectiveness of 48.31% was attained at the aeration proportion of 1.30 L/min, 19.27
h contact time, and 20.00% leachate to wastewater proportion.

v) Iron removal
The removal effectiveness of PAC-SBR varied from 20.04% (aeration rate =
7.5 L/min, contact time = 2 h, and leachate to wastewater proportion= 80 %) to
60.06% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.13). In PAC-SBR, the best possible Fe removal
effectiveness of 58.38% was attained at the aeration proportion of 2.94 L/min, 9.18 h
contact time, and 20.00% leachate to wastewater proportion.

vi) Manganese removal


In the present research, the least and most Mn removal effectiveness attained
by PAC-SBR reactors was 21.31% (contact time = 22 h, aeration rate = 7.50 L/min,
leachate to wastewater proportion= 80 %) and 52.55% (contact time = 12 h, aeration
rate = 4.0 L/min, leachate to wastewater proportion= 20 %), respectively (Table
4.13). In PAC-SBR, the best possible Mn removal effectiveness of 52.60% was
121

attained at the aeration proportion of 4.31 L/min, 15.82 h contact time, and 20.34%
leachate to wastewater proportion.

vii) Nickel removal


The removal effectiveness of PAC-SBR varied from 20.74% (aeration rate =
7.5 L/min, contact time = 22 h, and leachate to wastewater proportion= 80 %) to
55.40% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.13). In PAC-SBR, the best possible Ni removal
effectiveness of 54.69% was attained at the aeration proportion of 3.28 L/min, 13.78
h contact time, and 20.00% leachate to wastewater proportion.

viii) Cadmium removal


In the present research, the least and most Cd removal effectiveness attained by
PAC-SBR reactors was 22.02% (aeration rate = 7.50 L/min, contact time = 22 h,
leachate to wastewater proportion= 80 %) and 56.53% (aeration rate = 4.0 L/min,
contact time = 12 h, leachate to wastewater proportion = 20 %), respectively (Table
4.13). In PAC-SBR, the best possible Cd removal effectiveness of 56.33% was
attained at an aeration proportion of 3.37 L/min, 14.48 h contact time, and 20.00 %
leachate to wastewater proportion.

122

Figure 4-28: The 3D surface plots of colour removal in PAC-SBR

123

Figure 4-29: The 3D surface plots of COD removal in PAC-SBR

124

Figure 4-30: The 3D surface plots of ammonia removal in PAC-SBR

125

Figure 4-31: The 3D surface plots of phenols removal in PAC-SBR

126

Figure 4-32: The 3D surface plots of Fe removal in PAC-SBR

127

Figure 4-33: The 3D surface plots of Mn removal in PAC-SBR

128

Figure 4-34: The 3D surface plots of Ni removal in PAC-SBR

129

Figure 4-35: The 3D surface plots of Cd removal in PAC-SBR

130

4.4.3.6 PZE-SBR reactors (powdered zeolite supplemented SBR)


The Figures 4.36 to 4.43 show the pollutants removal by PZE-SBR. The results
will be discussed in Section 4.4.4.

i) Colour removal
The removal effectiveness of PZE-SBR varied from 49.23% (aeration rate =
7.5 L/min, contact time = 2 h, and leachate to wastewater proportion= 80 %) to
75.91% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.14). In PZE-SBR, the optimum colour removal
effectiveness of 75.95% was attained at the aeration proportion of 2.17 L/min, 18.89
h contact time, and 20.00% leachate to wastewater proportion.

ii) COD removal


The removal effectiveness of PZE-SBR varied from 39.90% (aeration rate =
7.5 L/min, contact time = 22 h, and leachate to wastewater proportion= 80 %) to
63.13% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.14). In PZE-SBR, the optimum COD removal
effectiveness of 63.28% was attained at the aeration proportion of 1.97 L/min, 10.31
h contact time, and 20.01% leachate to wastewater proportion.

iii) NH3-N removal


The removal effectiveness of PZE-SBR varied from 77.37% (aeration rate =
7.5 L/min, contact time = 22 h, and leachate to wastewater proportion= 80 %) to
94.93% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.14). In PZE-SBR, the optimum ammonia removal
131

effectiveness of 95.76% was attained at the aeration proportion of 0.50 L/min, 3.05 h
contact time, and 20.00% leachate to wastewater proportion.

iv) Phenols removal


The removal effectiveness of PZE-SBR varied from 21.49% (aeration rate =
7.5 L/min, contact time = 22 h, and leachate to wastewater proportion= 80 %) to
43.63% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.14). In PZE-SBR, the optimum phenols removal
effectiveness of 44.68% was attained at the aeration proportion of 1.87 L/min, 22.00
h contact time, and 20.00% leachate to wastewater proportion.

v) Iron removal
The removal effectiveness of PZE-SBR varied from 29.90% (aeration rate =
7.5 L/min, contact time = 22 h, and leachate to wastewater proportion= 80 %) to
65.08% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.14). In PZE-SBR, the optimum Fe removal effectiveness
of 65.11% was attained at the aeration proportion of 3.63 L/min, 13.63 h contact
time, and 21.14% leachate to wastewater proportion.

vi) Manganese removal


The least and most Mn removal effectiveness attained by PZE-SBR reactors
were 27.31% (aeration rate = 7.50 L/min, contact time = 2.0 h, leachate to
wastewater proportion= 80 %) and 59.93% (aeration rate = 4.00 L/min, contact time
= 12.00 h, leachate to wastewater proportion= 20.00 %), respectively (Table 4.14). In
PZE-SBR, the optimum Mn removal effectiveness of 60.77% was attained at the
132

aeration proportion of 2.57 L/min, 8.77 h contact time, and 20.14% leachate to
wastewater proportion.

vii) Nickel removal


The removal effectiveness of PZE-SBR varied from 25.14% (aeration rate =
7.5 L/min, contact time = 22 h, and leachate to wastewater proportion= 80 %) to
63.18% (aeration rate = 4.0 L/min, contact time = 12 h, leachate to wastewater
proportion= 20 %) (Table 4.14). In PZE-SBR, the optimum Ni removal effectiveness
of 63.19% was attained at the aeration proportion of 1.61 L/min, 13.40 h contact
time, and 21.13% leachate to wastewater proportion.

viii) Cadmium removal


The least and most Cd removal effectiveness attained by PZE-SBR reactors
was 27.17% (aeration rate = 7.50 L/min, contact time = 2 h, leachate to wastewater
proportion= 80 %) and 60.41% (aeration rate = 4.00 L/min, contact time = 12 h,
leachate to wastewater proportion= 20%), respectively (Table 4.14). In PZE-SBR,
the optimum Cd removal effectiveness of 60.41% was attained at an aeration
proportion of 2.76 L/min, 15.39 h contact time, and 20.03% leachate to wastewater
proportion.

133

Figure 4-36: The 3D surface plots of colour removal in PZE-SBR

134

Figure 4-37: The 3D surface plots of COD removal in PZE-SBR

135

Figure 4-38: The 3D surface plots of ammonia removal in PZE-SBR

136

Figure 4-39: The 3D surface plots of phenols removal in PZE-SBR

137

Figure 4-40: The 3D surface plots of Fe removal in PZE-SBR

138

Figure 4-41: The 3D surface plots of Mn removal in PZE-SBR

139

Figure 4-42: The 3D surface plots of Ni removal in PZE-SBR

140

Figure 4-43: The 3D surface plots of Cd removal in PZE-SBR

141

4.4.4 Comparing the four types of reactors


4.4.4.1 Comparing contact time, aeration rate and leachate to wastewater
mixing ratio in optimum condition by RSM
Based on the Table 4.15 and Figure 4.44 to Figure 4.54, the landfill leachate to
wastewater mixing ratio (%) was 20% in all reactors. The contact time (h) was 11.65,
12.60, 12.68 and 13.49h in PZ-SBR, PZE-SBR, Normal-SBR and PAC-SBR,
respectively. The aeration rate (L/min) was 1.82, 2.41, 2.86 and 4.32 in PZE-SBR,
PZ-SBR, PAC-SBR and Normal-SBR, respectively.

Table 4-15: The value of factors and responses at optimum conditions


Reactor

NormalSBR
PZSBR
PACSBR
PZESBR

Aeration
Rate
(L/min)
4.32

Factors
Contact Leachate to
Time
Wastewater
(h)
Ratio (%)
12.68
20.00

Colour
Rem.
(%)
55.95

COD
Rem.
(%)
45.81

Ammonia
Rem.
(%)
98.42

Responses
Phenols
Fe
Rem.
Rem.
(%)
(%)
33.83
45.03

Mn
Rem.
(%)
38.85

Ni
Rem.
(%)
44.64

Cd
Rem.
(%)
43.79

2.41

11.65

20.00

84.74

72.35

99.54

61.93

79.58

73.32

79.28

76.94

3.07

12.82

20.00

74.16

66.47

97.71

47.75

58.27

54.28

54.66

56.23

1.82

12.60

20.00

76.06

63.30

94.60

44.09

65.08

60.67

63.52

59.97

Figure 4-44: Comparing contact time (h) in the reactors in optimum condition

142

Aeration Rate (L/min)

5
4
3

2
1
0
Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Leachate to Wastewater Mixin


Ratio (%)

Figure 4-45: comparing aeration rate (L/min) in the four reactors in optimum
condition

20

15
10
5
0
Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Figure 4-46: Comparing leachate to wastewater mixing ration (%) in the four
reactors in optimum condition
4.4.4.2 Comparing the removal of colour, COD, ammonia and phenols in
optimum condition by RSM
Table 4.1 shows that the Semeling leachate contained high-intensity colour
(1690 Pt. Co), and high concentrations of COD (1301 mg/L) and NH3N (532
mg/L). An average of 269 mg/L was recorded for the BOD5 value (Table 4.1),
providing a low biodegradability ratio (BOD5/COD) of 0.20 (age >15 years). And
also the concentration of phenols was 1.92 mg/L.
Some studies (Aziz, 2011; Dhas, 2008) showed the adding some adsorbent into
bioreactors could increase the contaminants removal efficiency. So PZ-SBR, PAC-

143

SBR, and PZE-SBR had more performance comparing Normal-SBR in efficiency of


colour, COD, ammonia, and phenols removal. There are zeolite, lime stone, activated
carbon in PZ so it has the characteristics all of them. So the performance of PZ is
more than PAC and PZE.

A) Colour removal
As Aziz et al. (2011) explained, colour is a common contaminant in landfill
leachate. The decomposition of some organic matters like humic acid may cause the
water to be yellow, brown or black. Different techniques are employed for colour
removal. They include chemical precipitation, adsorption via granular activated
carbon, radiation, nanoltration, ozonation, UV photolysis, chemical coagulation,
anaerobic process, and biological treatment with different additives, uidized biofilm
process, and advanced oxidation with UV/H2O (Aziz et al., 2007).
Base on the Table 4.15 and Figure 4.47, the colour removal was 84.74%,
76.06%, 74.16% and 55.95% in PZ-SBR, PZE-SBR, PAC-SBR and Normal-SBR,
respectively. PZ-SBR is more efficiency in colour removal.

Colour rem. (%)

Colour removal
100
80
60
40

20
0
Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Figure 4-47: Comparing colour removal (%) in the reactors in optimum condition

144

B) COD removal
COD is defined as the amount of oxygen required to completely oxidize
organic constituents to carbon dioxide and water (Tchobanoglous et al., 1991). The
decrease in BOD5/COD ratio results also in the decrease in treatment efficacy
(Kulikowska and Kliminuk, 2004). Dhas (2008) reported that the mixture of
activated carbon and limestone provides an alternative for COD removal.
Base on the Table 4.15 and Figure 4.48, the COD removal was 84.74, 72.35%,
63.30% and 45.81% in PZ-SBR, PAC-SBR, PZE-SBR and Normal-SBR,
respectively. PZ-SBR is more efficiency in COD removal.

COD removal

COD rem. (%)

80
60
40
20
0

Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Figure 4-48: Comparing COD removal (%) in the reactors in optimum condition

C) Ammonia removal
Leachates with high NH4+-N content are generally difficult to treat in a
conventional biological treatment process (Li et al., 1999). The presence of high
levels of NH3N in landfill leachate over a long period is one of the most significant
problems faced by landfill operators. This high amount of unprocessed NH3N can
lead to the reduction of the performance efficiency of the biological treatment
methods, acceleration of eutrophication, and increase of dissolved oxygen reduction.
145

Thus, NH3N is extremely poisonous to aquatic organism (Bashir et al., 2010).


Previous study (Li and Zhao, 1998) confirmed that high NH4+-N concentration can
remarkably affect the performance of a conventional activated sludge procedure (Li
et al., 1999).
Base on the Table 4.15 and Figure 4.49, the ammonia removal was 99.52%,
98.42%, 97.71% and 94.60% in PZ-SBR, Normal-SBR, PAC-SBR and PZE-SBR,
respectively. All reactors have approximately same performance in ammonia
removal. Aziz (2011) reported the majority of NH3-N was removed biologically.

Ammonia removal
Ammonia rem. (%)

100
98
96

94
92
Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Figure 4-49: Comparing ammonia removal (%) in the four reactors in optimum
condition

D) Phenols removal
Landfill leachate contains a large number of dangerous compounds, such as
aromatics, halogenated compounds, heavy metals, phenols, pesticides, and
ammonium, which are considered dangerous even in small amounts. The harmful
effects of these compounds are often caused by multiple and synergistic effects.
Phenolic compounds released into the environment are particularly of high concern
because of their potential toxicity. These compounds detected in the leachate include

146

cresols, phenol, and substituted as well as chlorinated phenols. Cresols and phenol,
which are short-chain phenols previously reported by Benfenati et al. (1999) in
leachates of urban and industrial landfills, originate from various types of wastes.
Phenol and its substitutes are commonly produced by the transformation of several
pesticides (Varank et al., 2011). Kurata et al. (2008) measured 41 kinds of phenols in
three landfill sites in Japan. The results achieved in the present study agree well with
the literature (Kurata et al., 2008; Aziz et al., 2011). In this study, the 4aminoantipyrine method was used to measure phenols and determine all orthosubstituted and meta-substituted phenols or napthols, but not the para-substituted
phenols.
Base on the Table 4.15 and Figure 4.50, the phenols removal was 61.93%,
47.75%, 44.09% and 33.83% in PZ-SBR, PAC-SBR, PZE-SBR and Normal-SBR,
respectively. PZ-SBR is more efficiency in phenols removal.

Phenols removal
Phenols rem. (%)

80
60
40
20

0
Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Figure 4-50: Comparing phenols removal (%) in the four reactors in optimum
condition

147

4.4.4.3 Comparing the Fe, Mn, Ni and Cd in optimum condition by RSM


The past century has witnessed a rapid increase in industrial activity. This rapid
growth has resulted in more complex toxic waste. Many industrial processes produce
effluents that contain metal. Heavy metal pollution has been a major environmental
crisis primarily because metals tend to remain and collect in the ecosystem. Various
industries use toxic metals such as arsenic, mercury, zinc, copper, lead, nickel, and
cadmium (Sewvandi and Adikary, 2011; Palanisamy and Nomanbhay, 2005).
The main sources of heavy metals in landfills are fluorescent tubes,
pharmaceuticals, photographic chemicals, detergents, individual care goods, garden
pesticides, waste oil, batteries, paint, electronic waste, electrical tools, and wood
treated with dangerous substances, among other household wastes (Slacka et al.,
2005; Mohan and Gandhimathi, 2009). Heavy metals in the form of free cations or in
labile complexes (which can disintegrate easily) commonly have a more destructive
impact on marine life than metal in non-labile complexes because the free metal
shape is extremely mobile and can simply absorb onto or permeate the tissue of
aquatic beings. According to literature, less than 10% of metals in dumping site
leachate are free metal ions (Chaari et al., 2011).
Recent studies have focused on heavy metal elimination from aqueous
solutions. Heavy metals are eliminated by using different methods such as biological
methods, ion exchange, solvent extraction, chemical precipitation, reverse osmosis,
or adsorption (Yan-jiao et al., 2010). Malakahmad et al. (2011) used SBR for the
removal of Hg2+ and Cd2+ from synthetic petrochemical factory wastewater. Ion
exchange is a superior alternative method of eliminating heavy metals. However, it
entails high costs. Absorption technologies that use natural materials as adsorbents
are a possible method of eliminating heavy metals in sewerage (Cervera et al., 2003).

148

The efficiency of PZ in metals removal is more than other adsorbents because


it has the characteristics of zeolite, activated carbon, limestone, and cement together.
Ion-exchange processes have been widely used to remove heavy metals from
wastewater due to their many advantages, such as high treatment capacity, high
removal efficiency and fast kinetics (Fu and Wang, 2011). Many studies have
demonstrated that zeolites exhibit good cation-exchange capacities for heavy metal
ions under different experimental conditions (Motsi et al., 2009; Ostroski et al.,
2009; Taffarel and Rubio, 2009). The PZE-SBR performance was more than PACSBR performance in metals removal because zeolite is an ion exchanger.

A) Fe removal
Iron is a typical component of the Earths surface, and its concentration in the
ecosystem varies. Iron is a constant pollutant because it cannot be destroyed or
eliminated. Human activities have considerably altered biogeochemical cycles and
equilibrium of many metals. Primary anthropogenic resources of iron are different
industrial sources, such as current and past mining activities, steel manufacturing,
smelters and foundries, and various resources such as piping, components of goods,
and combustion side effects (Mojiri et al., 2011).
Base on the Table 4.15 and Figure 4.51, the Fe removal was 79.58%, 65.08%,
58.27% and 45.03% in PZ-SBR, PZE, PAC-SBR and Normal-SBR, respectively.
PZ-SBR is more efficiency in Fe removal.

149

Fe removal

Fe rem. (%)

80
60

40
20
0
Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Figure 4-51: Comparing Fe removal (%) in the reactors in optimum condition

B) Mn removal
Manganese (Mn) ions are released in wastewaters by numerous industries, such
as pyrolusite (MnO2) treatment, ink and dyes, glass and ceramics, paint and varnish,
steel alloy dry cell batteries, fireworks and match manufacturing, and galvanized
metal waste processing plants (Taffarel and Rubio, 2009). Taffarel and Rubio (2009)
investigated Mn2+ ion removal through adsorption onto natural and activated Chilean
zeolites. This procedure was able to remove Mn efficiently.
Base on the Table 4.15 and Figure 4.52, the Mn removal was 73.32%, 60.67%,
54.28% and 38.85% in PZ-SBR, PZE, PAC-SBR and Normal-SBR, respectively.
PZ-SBR is more efficiency in Mn removal.

150

Mn removal

Mn rem. (%)

80
60
40
20
0
Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Figure 4-52: Comparing Mn removal (%) in the reactors in optimum condition

C) Ni removal
Base on the Table 4.15 and Figure 4.53, the Ni removal was 79.28%, 63.52%,
54.66% and 44.64% in PZ-SBR, PZE, PAC-SBR and Normal-SBR, respectively.
PZ-SBR is more efficiency in Ni removal.
Nickel is a toxic heavy metal that occurs naturally and is used in many
industrial applications. In addition, nickel is an embryotoxin and teratogen. High Ni
levels affect human health and cause headache, dry cough, nausea, tightness of the
chest, dizziness, vomiting, rapid respiration, shortness of breath, chest pain, extreme
weakness, and cyanosis (Pandey et al., 2007). Al-Dwairi and Al-Rawajfeh (2012)
investigated the elimination of cobalt and nickel from wastewater by using
inexpensive Jordan bentonite and zeolite. Their findings indicate that zeolite can be
used to remove cobalt and nickel from wastewater.

151

Ni removal

Ni rem. (%)

80
60
40
20
0
Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Figure 4-53: Comparing Ni removal (%) in the reactors in optimum condition

D) Cd removal
Cadmium pollution is mainly caused by the following: (i) Ni/Cd battery
manufacturing that might release Cd++ and Ni++ into groundwater through
unprocessed aqueous wastes or unmanaged disposal of consumed batteries; (ii)
cadmium plating, which releases cyanide; and (iii) cadmium that is released directly
to the ground and then to groundwater sources in a cultivated region in which
cadmium-rich phosphate-based fertilizers are used. Non-ferrous metal mines are
another major contributor of cadmium to the marine ecosystem. Pollution can result
from mine drainage water, ore processing wastewater, leachate, tailing pond
overflow, and flow of rainfall from a mining area (Nosier, 2003). Bai and
Bartkiewicz (2009) studied elimination of cadmium from sewerage by using ion
exchange resin
Base on the Table 4.15 and Figure 4.54, the Cd removal was 76.94%, 59.97%,
56.23% and 43.79% in PZ-SBR, PZE, PAC-SBR and Normal-SBR, respectively.
PZ-SBR is more efficiency in Cd removal.

152

Cd removal

Cd rem. (%)

80
60
40
20
0
Normal-SBR

PZ-SBR

PAC-SBR

PZE-SBR

Figure 4-54: Comparing Cd removal (%) in the reactors in optimum condition

4.5 Variation of DO inside reactors


In order to metabolize food and reproduce, each microorganism (or bug) must
have at least 0.1 to 0.3 mg/L DO. Most plants maintain about 2 mg/L of DO so the
bugs contained inside the floc can also get oxygen. If the DO is less than 2 mg/L, the
bugs in the center of the floc may die since the bugs on the outside of the floc use up
the DO first. If this happens, the floc breaks up. If DO content is too low, the
environment is not stable for these bugs and they will die due to anaerobic zones, the
sludge will not be properly treated (Water and Wastewater Industry, 2009).
The dissolved oxygen (DO) control is the most widely-spread in real-life, since
the DO level in the aerobic reactors has significant influence on the behavior and
activity of the heterotrophic and autotrophic microorganisms living in the activated
sludge. The dissolved oxygen concentration in the aerobic part of an activated sludge
process should be sufficiently high to supply enough oxygen to the microorganisms
in the sludge, so organic matter is degraded and ammonium is converted to nitrate.

153

On the other hand, an excessively high DO, which requires a high airflow rate, leads
to a high energy consumption and may also deteriorate the sludge quality. A high DO
in the internally recirculated water also makes the denitrification less efficient.
Hence, both for economical and process reasons, it is of interest to control the DO
(Holenda et al., 2008).
The DO (mg/L) concentration at the beginning and ending of SBR process
were less than 1 mg/L which is in line with findings of Aziz (2011) and Li et al.
(2008). Two different concentration of DO (greater than 2 mg/L and less than 1
mg/L) are mandatory (Aziz, 2011; Surampalli et al., 1997). So the DO concentration
in the all reactors was suitable for occurring both nitrification and denitrification
process. A quick increase of DO curves in the reactors was because of beginning of
react phase. Also, rapid decrease of DO curves for aeration rate process and start
settling phase in the SBRs. Figures 4.55 to 4.60 show DO variation inside the
reactors. The DO concentration was in order PZ-SBR> PAC-SBR> PZE-SBR>
Normal-SBR. The DO concentration in PZ-SBR was higher than others. PZ assisted
in decreasing the pollutants in the leachate. The adsorbents could reduce a part of
SBR operational cost due to saving DO (Aziz, 2011).

4.5.1 Effect on contact time on DO in reactors


The effects of contact time on DO concentration are shown in Figures 55 to 57.
DO concentrations were higher at the beginning of react phase and after that
decreasing gradually.

154

12
SBR-a
SBR-b

10

SBR-c
PZ-SBR-a

DO (mg/L)

PZ-SBR-b
PZ-SBR-c

PAC-SBR-a
PAC-SBR-b

PAC-SBR-c
PZE-SBR-a

PZE-SBR-b

PZE-SBR-C

0
0

10

15

20

25

30

4-55: Effect of contact time on DO in the reactors (aeration rate 0.5 L/min; combined
leachate to wastewater; 50%)
a= 2.0h; b= 12h and c= 22h of contact time

14
SBR-a

12

SBR-b
SBR-c

10

DO (mg/L)

PZ-SBR-a
PZ-SBR-b

PZ-SBR-c
PAC-SBR-a

PAC-SBR-b
PAC-SBR-c

PZE-SBR-a
PZE-SBR-b

PZE-SBR-C

0
0

10

15

20

25

30

4-56: Effect of contact time on DO in the reactors (aeration rate 4.0 L/min; combined
leachate to wastewater; 50%)
a= 2.0h; b= 12h and c= 22h of contact time

155

16
14

SBR-a
SBR-b

12

SBR-c
PZ-SBR-a

DO (mg/L)

10

PZ-SBR-b
PZ-SBR-c

PAC-SBR-a
6

PAC-SBR-b
PAC-SBR-c

PZE-SBR-a
PZE-SBR-b

PZE-SBR-C

0
0

10

15

20

25

30

4-57: Effect of contact time on DO in the reactors (aeration rate 7.5 L/min; combined
leachate to wastewater; 50%)
a= 2.0h; b= 12h and c= 22h of contact time

4.5.2 Effect of aeration rate on DO in the reactors


The effects of aeration rate on DO concentration are shown in Figures 58 to 60.
Increasing aerations resulted in a higher DO concentration in all reactors. It is in line
with findings of Aziz (2012) and Li et al. (2008).

156

14

12

SBR-a
SBR-b

10

SBR-c

DO (mg/L)

PZ-SBR-a
PZ-SBR-b

PZ-SBR-c
PAC-SBR-a

PAC-SBR-b
PAC-SBR-c

PZE-SBR-a
PZE-SBR-b

PZE-SBR-C

0
0

4-58: Effect of aeration rate on DO in the reactors (contact time 2h; combined
leachate to wastewater; 50%)
a= 0.5 L/min; b= 4 L/min and c= 7.5 L/min

16
SBR-a

14

SBR-b
12

SBR-c
PZ-SBR-a

DO (mg/L)

10

PZ-SBR-b
PZ-SBR-c

PAC-SBR-a
6

PAC-SBR-b
PAC-SBR-c

PZE-SBR-a
PZE-SBR-b

PZE-SBR-C
0
0

10

15

4-59: Effect of aeration rate on DO in the reactors (contact time 12h; combined
leachate to wastewater; 50%)
a= 0.5 L/min; b= 4 L/min and c= 7.5 L/min

157

16
SBR-a

14

SBR-b
12

SBR-c
PZ-SBR-a

DO (mg/L)

10

PZ-SBR-b
PZ-SBR-c

PAC-SBR-a
6

PAC-SBR-b
PAC-SBR-c

PZE-SBR-a
PZE-SBR-b

PZE-SBR-C
0
0

10

15

20

25

30

4-60: Effect of aeration rate on DO in the reactors (contact time 22h; combined
leachate to wastewater; 50%)
a= 0.5 L/min; b= 4 L/min and c= 7.5 L/min

4.6 Statistical analysis and comparing results


4.6.1 Statistical analysis
ANOVA results for response parameters about colour, COD, ammonia and
phenols have been shown in the Table 4.16, and also it has been shown about metals
in the Table 4.17. The Table 4.16 and Table 4.17 illustrated the reduced quaratic
models in terms of actual factors and it also showed other statistical parameters. All
models were significant at the 5% confidence level. The lack of fit (LOF) describes
variation the data well. LOF is significant, if the model does not fit the data well. The
coefficient of determination (R2) provides the proportion of total variation in the
response predicted by the model. R2 values close to 1 desirable, and a high R2
coefficient ensures adequate modification of the quadratic model to the experimental

158

data. The Adequate precision (Adeq P) compares the range of predicted values at the
design points to the mean prediction error. Adeq. P greater than 4 shows adequate
model inequity (Aziz, 2011). All Adeq P were more than 4 authorizing that all
predicted models could be used to navigate the design space defined by the CCD.
Figures 61 to 68 displayed the predicted versus actual value plots of response
parameters for all reactors. These plots signify sufficient agreement between real
data and the ones achieved from the models. The coefficient of variance (CV) is the
ratio of the standard error of estimate to the average of observed response defined by
the reproducibility of the model. If the CV is more than 10%, then it is considered
reproducible (Aziz, 2011; Bashir et al., 2010).

159

160

Response

Final equation in the rms of actual factor


Prob.

R2

Adj. R2 Adec. P.
SD

CV

Table 4-16: ANOVA results for response parameter (about colour, COD, ammonia and phenols)
PRESS

Colour

46.45 + 0.695A + 1.276B 0.013C 0.009A2 0.039B2 0.002C2


0.0001 0.9416 0.8889 14.18
2.84 6.37 403.84
0.007AB 0.014AC 0.001C
2
2
2
41.68 + 2.496A + 0.074B + 0.043AC 0.267A 0.006B 0.002C
COD
0.0003 0.9148 0.8381 11.89
2.31 5.92 370.62
0.021AB 0.0002AC 0.001BC
SBR
2
2
2
82.34 + 3.868A + 1.293B 0.087C 0.443A 0.031B 0.008C
Ammonia
0.0001 0.7952 0.6110
7.97
4.81 5.44 471.16
0.023AB + 0.20AC 0.008BC
2
2
2
26.19 + 1.227A + 0.723B + 0.716C 0.276A 0.221B 0.002C +
Phenols
0.0001 0.9824 0.9666 25.77
1.11 4.27
81.53
0.034AB + 0.005AC 0.003BC
2
2
2
83.43 + 1.644A + 0.574B 0.248C 0.244A 0.018B 0.00002C
Colour
0.0001 0.9630 0.9298 18.82
1.65 2.20 272.69
0.011AB + 0.005AC 0.002BC
2
2
75.68 0.833A 0.006B 0.0009C 0.030A 0.004B + 0.013AB +
COD
0.0001 0.9784 0.9589 23.54
1.48 2.32 133.52
PZ0.018AC + 0.004BC
2
2
2
SBR
98.74 + 1.763A + 0.193B 0.128C 0.239A 0.013B 0.001C +
Ammonia
0.0001 0.9088 0.8268 10.97
2.54 2.77 422.01
0.006AB + 0.003AC + 0.001BC
2
2
2
69.02 0.499A 0.297B 0.275C + 0.021A 0.013B + 0.00001C
Phenols
0.0001 0.9824 0.9665 24.99
1.05 1.94
41.79
0.001AB + 0.002AC + 0.0007BC
2
2
2
93.53 + 0.743A + 0.072B 1.196C 0.100A 0.004B + 0.008C
Colour
0.0001 0.9886 0.9783 27.67
1.29 2.21
61.31
0.004AB 0.0007AC 0.0002BC
2
2
2
67.99 + 0.794A + 0.443B 0.267C 0.105A 0.016B 0.0008C
COD
0.0001 0.9805 0.9629 22.18
1.52 2.77
98.60
0.007AB + 0.0003AC + 0.0001BC
PAC2
2
2
98.72 + 0.512A 0.140B + 0.053C 0.089A + 0.004B 0.003C
SBR
Ammonia
0.0001 0.9857 0.9729 26.70
1.20 1.34
54.29
0.003AB 0.001AC 0.0005B
2
2
2
52.79 + 0.419A + 0.253B 0.359C 0.082A 0.006B 0.0004C
Phenols
0.0001 0.9943 0.9892 41.62
0.91 2.61
49.15
0.013AB + 0.002AC 0.0001BC
2
2
2
82.53 + 0.854A + 0.436B 0.570C 0.170A -.014B + 0.002C +
Colour
0.0001 0.9978 0.9959 72.57
0.51 0.83
11.78
0.002AB + 0.001AC 0.001BC
2
2
2
60.11 + 0.045A + 0.329B + 0.167C 0.061A 0.013B 0.005C +
COD
0.0001 0.9991 0.9982 95.77
0.34 0.64
2.94
PZE0.006AB + 0.003AC 0.0007BC
2
2
2
SBR
105.09 0.735A + 0.028B 0.500C 0.046A 0.005B + 0.002C +
Ammonia
0.0001 0.9817 0.9652 26.32
0.99 1.17
91.30
0.011AB + 0.011AC + 0.00008BC
2
2
2
44.00 + 0.830A +0.217B 0.085C 0.869A 0.002B -0.002C
Phenols
0.0001 0.9961 0.9926 51.02
0.64 1.58
26.59
0.023AB+ 0.0004AC 0.001BC
2
2
2
*Prob.: Probability of error; R : Coefficient of determination; Adj. R : Adjusted R ; Adec. P.: Adequate precision; SD: Standard deviation; CV: Coefficient of
PRESS: Predicted residul error sum of square; Prob. LOF: Probability of lack of fit
**In final equations, where A is Aeration rate (L/min); B is contact time (h); and C is leachate to wastewater mixing ratio (%;v/v)

SBR
Type

variance;

0.1991

0.0014

0.9235

0.8519

0.7440

0.6550

0.3897

0.7093

0.1797

0.2913

0.0369

0.4616

0.0866

0.0161

0.0007

0.0015

Prob.
LOF

161

Response

Final equation in the rms of actual factor


Prob.

R2

Adj. R2 Adec. P.

Table 4-17: ANOVA results for response parameter (about metals)


SD

CV

PRESS

Fe

37.91 + 1.328A + 0.377B + 0.222C 0.156A2 0.011B2 0.006C2


0.0001 0.9947 0.9899 40.70
0.99 2.94
60.17
0.002AB 0.002AC 0.001BC
2
2
2
37.38 + 0.870A + 0.357B 0.038C 0.012A 0.015B 0.002C
Mn
0.0001 0.9930 0.9867 37.69
0.88 3.04
32.50
0.003AB + 0.0001AC + 0.0004BC
SBR
2
2
2
47.60 + 0.890A + 0.203B 0.266C 0.106A 0.005B 0.001C
Ni
0.0001 0.9979 0.9960 67.66
0.61 1.95
18.70
0.002AB 0.002AC 0.0003BC
2
2
2
48.04 + 0.504A + 0.208B 0.278C 0.067A 0.009B 0.001C +
Cd
0.0001 0.9994 0.9989 131.15 0.31 1.02
5.49
0.00AB 0.004AC + 0.0004BC
2
2
2
68.55 + 0.550A + 0.331B + 0.677C 0.064A 0.009B 0.012C
Fe
0.0001 0.9963 0.9929 48.13
1.20 1.80 120.03
0.013AB 0.005AC 0.002BC
2
2
2
75.48 + 0.943A + 0.089B 0.144C 0.104A 0.004B 0.003C
Mn
0.0001 0.9913 0.9836 34.13
1.39 2.33
92.63
PZ0.005AB 0.006AC 0.005BC
2
2
2
SBR
90.44 + 0.823A + 0.135B 0.660C 0.147A 0.007B + 0.001C +
Ni
0.0001 0.9947 0.9899 41.94
1.42 2.43 120.03
0.011AB + 0.007AC 0.0002BC
2
2
2
87.65 + 1.075A + 0.025B 0.596C 0.163A 0.006B 0.0002C +
Cd
0.0001 0.9958 0.9920 47.65
1.21 2.11
63.01
0.003AB 0.001AC + 0.001BC
2
2
2
69.54 + 1.677A + 0.069B 0.786C 0.371A 0.009B + 0.003C +
Fe
0.0001 0.9652 0.9340 18.40
2.30 5.46 655.53
0.030AB + 0.011AC + 0.0004BC
2
2
2
58.89 + 1.439A + 0.760B 0.661C 0.279A 0.027B + 0.002C +
Mn
0.0001 0.9647 0.9329 18.55
2.55 6.89 550.33
0.021AB + 0.005AC 0.001BC
PAC2
2
2
58.38 + 1.540A + 0.857B 0.651C 0.318A 0.033B + 0.001C +
SBR
Ni
0.0001 0.9508 0.9065 15.91
3.17 8.63 925.34
0.027AB + 0.008AC 0.0006BC
2
2
2
61.69 + 2.021A + 0.822B 0.811C 0.361A 0.029B + 0.003C +
Cd
0.0001 0.9594 0.9230 17.35
2.83 7.55 702.44
0.015AB + 0.009AC 0.001BC
2
2
2
67.03 + 1.823A + 0.372B 0.311C 0.340A 0.011B 0.001C +
Fe
0.0001 0.9869 0.9751 28.05
1.82 3.75 162.18
0.008AB + 0.007AC 0.002BC
2
2
2
64.51 + 2.603A + 0.637B 0.622C 0.390A 0.023B + 0.001C +
Mn
0.0001 0.9755 0.9535 22.91
2.15 4.87 229.28
PZE0.001AB + 0.002AC 0.0001BC
2
2
2
SBR
63.56 + 0.126A + 0.925B 0.291C 0.187A 0.027B 0.001C +
Ni
0.0001 0.9830 0.9677 25.14
2.08 4.55 611.09
0.019AB + 0.009AC 0.004BC
2
2
2
63.16 + 1.319A + 0.509B 0.412C 0.229A 0.017B 0.0005C +
Cd
0.0001 0.9965 0.9933 55.55
0.86 44.22 48.29
0.007AB + 0.003AC 0.0009BC
2
2
2
*Prob.: Probability of error; R : Coefficient of determination; Adj. R : Adjusted R ; Adec. P.: Adequate precision; SD: Standard deviation; CV: Coefficient of
PRESS: Predicted residul error sum of square; Prob. LOF: Probability of lack of fit
**In final equations, where A is Aeration rate (L/min); B is contact time (h); and C is leachate to wastewater mixing ratio (%;v/v)

SBR
Type

variance;

0;0351

0.0398

0.0016

0.0010

0.6629

0.8661

0.5953

0.8607

0.4969

0.4122

0.4511

0.3834

0.2108

0.0722

0.0424

0.2994

Prob.
LOF

Figure 4-61: Design-expert plot; predicted vs. actual values plot for colour

162

Figure 4-62: Design-expert plot; predicted vs. actual values plot for COD

163

Figure 4-63: Design-expert plot; predicted vs. actual values plot for ammonia

164

Figure 4-64: Design-expert plot; predicted vs. actual values plot for phenols

165

Figure 4-65: Design-expert plot; predicted vs. actual values plot for Fe

166

Figure 4-66: Design-expert plot; predicted vs. actual values plot for Mn

167

Figure 4-67: Design-expert plot; predicted vs. actual values plot for Ni

168

Figure 4-68: Design-expert plot; predicted vs. actual values plot for Cd

4.7 HRT, F/M and OLR in four reactors in optimization experiments


4.7.1 Hydraulic Retention Time (HRT)
Minimum and maximum HRT are shown in Table 4.18. Aziz et al. (2011a)
used 3.34 d; and 1 d, 0.5 d, 0.33 d and 0.25 d of HRT were used by Fabregas (2004),
Andreottola et al. (2001), and Dangcong et al. (2001). Also, different HRT from
19.17d to 2.7h was reported by Chan et al. (2009). The minimum and maximum
169

HRT of this study were 0.18 to 1.11d and they are in the ranges which were
mentioned in above. HRT values were determined by the following equation:

Where, V= reactor volume, L; Q= total daily flow, L/d

Table 4-18: Minimum and maximum HRT in four reactors in optimization


experiments
Types
PZ-SBR
PAC-SBR
PZE-SBR
Normal-SBR

HRT concentrations (d)


Minimum
Maximum
0.18
1.11
0.18
1.11
0.18
1.11
0.18
1.11

4.7.2 Organic Loading Rate (OLR)


OLR values were determined by the following equation:

where, OLR= organic loading rate, kg/m3.d; Total COD= total chemical
oxygen demand, kg/m3; HRT= hydraulic retention time, d
Minimum and maximum OLR are shown in Table 4.19. The 6, 12, 24, 48 and 96
g/m3d of OLR were used by Aygun et al. (2008). Babaee and Shayegan (2011) used
1.4, 2 and 2.75 kg/m3d in their study. So in current study, OLR is in the range.

Table 4-19: Minimum and maximum OLR in four reactors in optimization


experiments
Types
PZ-SBR
PAC-SBR
PZE-SBR
Normal-SBR

OLR concentrations (kg/m3)


Minimum
Maximum
0.21
10.62
0.21
10.62
0.21
10.62
0.21
10.62

170

4.7.3 Mixed Liquor Suspended Solid (MLSS)


Mixed liquor suspended solids (MLSS) is the concentration of suspended
solids, in an aeration tank during the activated sludge process, which occurs during
the treatment of waste water. The units MLSS is primarily measured in are
milligrams per liter (mg/L). MLSS is an important part of the activated sludge
process to ensure that there is a sufficient quantity of active biomass available to
consume the applied quantity of organic pollutant at any time (Aziz, 2011).
MLSS concentrations were monitored during this study. Adsorbents caused
increasing MLSS values. This is in line with findings of Leong et al. (2011); Gao et
al. (2011) and Aziz (2011). Maximum and minimum MLSS values in PZ-SBR, PACSBR, PZE-SBR and Normal-SBR were shown in Table 4.20 and Figure 4.69.

Table 4-20: Minimum and maximum MLSS in four reactors in optimization


experiments
Types

MLSS concentrations (mg/L)


Minimum
Maximum
6809
7923
6152
7010
5842
6804
1205
1969

PZ-SBR
PAC-SBR
PZE-SBR
Normal-SBR

8000
7000
MLSS (mg/L)

6000
5000

Min

4000

Max

3000

2000
1000

0
PZ-SBR

PAC-SBR

PZE-SBR

Normal-SBR

Figure 4-69: Minimum and maximum MLSS in four reactors in optimization


experiments

171

4.7.4 The F/M Ratio


Maximum and minimum F/M values in PZ-SBR, PAC-SBR, PZE-SBR and
Normal-SBR were showed in Table 4.21. F/M ratios were determined by the
following equation:

where, Q= wastewater flow (m3/day); BOD= wastewater BOD (g/m3); V=


liquid volume of aeration tank (m3); MLSS= mixed liquor suspended solid (g/m3)

Table 4-21: Minimum and maximum F/M in four reactors in optimization


experiments
Types
PZ-SBR
PAC-SBR
PZE-SBR
Normal-SBR

F/M concentrations
Minimum
6809
6152
5842
1205

Maximum
7923
7010
6804
1969

4.8 Continuous experiments results


The experiments were replicated based on obtained optimum parameter from
the batch and optimization experiments. Each kind of reactor ten times was run based
on the obtained optimum operation parameters.
The removal efficiency of some pollutants such as colour, COD, ammonia,
phenols, Fe, Mn, Ni, Cd, Cr (VI) and sulfide were monitored. The operation
parameters are shown in Table 4.22. The some vital characteristics of used Sungai
Petani leachate and domestic wastewater in the continuous experiments were as
following (Table 4.23):

172

Table 4.22: Operation parameters in continuous experiments


No.

Parameter

1
2
3

Settling time (min)


Adsorbent dosage (g/L)
Contact time (min)

4
5
6

Aeration rate (L/min)


Leachate/wastewater ratio (v/v; %)
Cycle time (min)

7
8
9
10
11
12

Time for Filling and Mixing (min)


Time for Draw and Idle (min)
OLR (kg/m3.d)
HRT (d)
MLSS (mg/L)
F/M

Normal-SBR
90
760
(12.68h)
4.32
20
930
(15.5h)
30
49
1.00
0.72
1510
0.25

Value
PZ-SBR PAC-SBR
90
90
3
3
699
769
(11.65h) (12.82h)
2.41
3.07
20
20
930
930
(15.5h)
(15.5h)
30
30
111
10
1.00
1.00
0.72
0.72
7613
6516
0.05
0.06

PZE-SBR
90
3
756
(12.60h)
1.82
20
930
(15.5h)
30
24
1.00
0.72
6105
0.06

Table 4-23: Characteristics of landfill leachate and domestic wastewater


No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

Parameter
Temperature (C)
pH
EC (ms/cm)
Colour (Pt. Co)
BOD5 (mg/L)
COD (mg/L)
Nitrite (mg/L NO2-N-HR)
Total phosphorus (mg/L PO43-)
NH3-N (mg/L)
Sulfide (mg/L)
Total iron (mg/L)
Total manganese (mg/L)
Total nickel (mg/L)
chromium VI (mg/L)
Total cadmium (mg/L)
Phenols (mg/L)

Leachate
28.5
7.65
3.73
1261
269.0
726
50.18
22.11
417.0
0.300
7.23
1.18
5.44
0.21
3.11
1.84

Wastewater
27.9
6.91
1.13
6.00
64.2
116
9.26
98.18
149.0
0.600
2.65
0.65
0.31
0.17
0.32
0.10

Based on Table 4.22, the settling time was 90 min in the continuous SBR
experiments; the same range was used by Wang et al., 2009; Li et al., 2008; Aziz
(2011), and Trabelsi et al. (2013).
Based on Table 4.22, the cycle time was 15.5 h in the continuous SBR
experiments; the various ranges were used by researchers. Aziz (2011) used 8h of
cycle time; Neczaj et al. (2007) used 24h of cycle time; and Swierczynska et al.

173

(2012) used 12h of cycle time. The 16h of cycle time is in the ranges which were
used by researchers.
Based on Table 4.22, the HRT was 0.72 d in the continuous SBR experiments;
the various ranges were used by researchers. Aziz et al. (2011a) used 3.34 d; the 1 d,
0.5 d, 0.33 d and 0.25 d of HRT were used by Fabregas (2004); Andreottola et al.
(2001), and Dangcong et al. (2001). Also different HRT from 19.17d to 2.7h was
reported by Chan et al. (2009). The HRT of this study was 0.74 d is in the ranges
which were used by researchers.
Based on Table 4.22, the OLR was 1.00 kg/m3.d in the continuous SBR
experiments. The 6, 12, 24, 48 and 96 g/m2d of OLR were used by Aygun et al.
(2008). Babaee and Shayegan (2011) used 1.4, 2 and 2.75 kg/m3d in their study. So
OLR in current research is in the range.

4.8.1 Performance of reactors in pollutants removal


4.8.1.1 Colour, COD, ammonia, phenols, and sulfide removal
The averages of removal efficiency and the pollutants concentrations are
shown in Table 4.24 and Table 4.25, respectively. The PZ-SBR had the highest
performance to removal of colour, COD, ammonia, phenols and sulfide among the
others. And also the PAC showed the higher performance to remove COD, ammonia,
phenols and sulfide comparing with PZE-SBR and Normal-SBR. But colour was
removed more by PZE-SBR comparing with PAC-SBR and Normal-SBR. This is in
line with the findings of the current study in optimum experiments.

174

Table 4-24: Removal efficiency of color, COD, ammonia, phenols and sulfide
Types

NormalSBR
PZSBR
PACSBR
PZESBR

Colour
removal
(%)
47.78

COD
removal
(%)
44.29

Ammonia
removal
(%)
88.41

Phenols
removal
(%)
32.56

Sulfide
removal
(%)
39.28

87.18

73.84

97.69

67.71

74.13

69.23

62.19

92.37

45.29

61.32

71.14

58.24

90.89

43.31

56.39

Table 4-25: Concentrations of colour, COD, ammonia, phenols and sulfide after
treatment
Types

NormalSBR
PZSBR
PACSBR
PZESBR

Colour
intensity
(Pt. Co)
658

COD
concentration
(mg/L)
404.5

Ammonia
concentration
(mg/L)
48.3

Phenols
concentration
(mg/L)
1.24

Sulfide
concentration
(mg/L)
0.18

162

194.7

9.6

0.59

0.07

388

274.5

31.8

1.00

0.11

364

303.0

37.9

1.04

0.13

4.8.1.2 Fe, Mn, Ni, Cd and Cr (VI) removal


The removal efficiency and the pollutants concentrations are shown in Table
4.26 and Table 4.27, respectively. The PZ-SBR had the highest performance to
removal of metals among the others. And also the PZE-SBR showed the higher
performance to remove metals comparing with PAC-SBR and Normal-SBR.

Table 4-26: Average removal efficiency of Fe, Mn, Ni, Cd and Cr (VI)
Types

NormalSBR
PZSBR
PACSBR
PZESBR

Fe
removal
(%)
39.24

Mn
removal
(%)
38.17

Ni
removal
(%)
38.91

Cd
removal
(%)
39.18

Cr (VI)
removal
(%)
38.15

82.25

78.71

82.13

80.18

79.24

58.92

55.28

54.29

56.18

55.24

68.18

62.19

64.32

66.23

66.37

175

Table 4-27: Average concentrations of Fe, Mn, Ni, Cd and Cr (VI) after treatment
Types

NormalSBR
PZSBR
PACSBR
PZESBR

Fe
concentration
(mg/L)
4.39

Mn
concentration
(mg/L)
0.72

Ni
concentration
(mg/L)
3.23

Cd
concentration
(mg/L)
1.89

Cr (VI)
concentration
(mg/L)
0.13

1.28

0.25

0.97

0.61

0.04

2.97

0.52

2.49

1.36

0.09

2.30

0.44

1.94

1.05

0.07

Argun (2008) reported 93.6% removal of nickel by batch experiments and


using clinoptilolite. Khan et al. (2004) have reported 85% and 99% removal
cadmium and chromium (VI) by rice husk as adsorbent. The results of current study
are approximately in line with their studies.

4.8.1.3 Nitrification and denitrification process


The reaction of biological nitrogen removal consisted of nitrification and
denitrification, which were accomplished by nitrifying and denitrifying bacteria,
respectively. Nitrifying bacteria are generally considered aerobic microorganisms,
whereas denitrifying bacteria are considered anaerobic. Thus, in previous studies, the
nitrogen removal process was always conducted in more-than-two separate reactors,
such as an anoxic/aerobic (A/O) system and an anaerobic/anoxic/aerobic (A/A/O)
system. In recent years, numerous studies have demonstrated the non-assimilation
loss of nitrogen. Researchers have found that, in a special environment,
denitrification could also be achieved under aerobic conditions (i.e., aerobic
denitrification) (Rong et al., 2007; Kong and Li, 2004).
In biological degradation, DO is important not only for COD removal, as
shown by orthogonal tests, but also for NH3N removal. Different bacteria reportedly
have different ranges of suitable DO concentration. Aziz (2011) reported that
176

denitrification requires a low DO concentration (less than 1 mg/L). Two different


concentrations of DO (less than 1 mg/L and more than 2 mg/L) are essential. As
mentioned in Section 4.5, the DO (mg/L) concentrations at the beginning and end of
the SBR process were less than 1 mg/L.

A. Nitrification
Nitrification is a microbial process by which ammonia is sequentially oxidized
to nitrite and then to nitrate. In the first phase of nitrification, ammonia-oxidizing
bacteria oxidize ammonia to nitrite according to equation (1), Nitrosomonas is the
most commonly identified genus associated with this step (EPA, 2007).
NH3 + O2

NO2 + 3H++ 2e

B. Denitrification
Denitrification is the process by which nitrates are reduced to gaseous nitrogen
by facultative anaerobes. Facultative anaerobes, such as fungi, can flourish under
anoxic conditions because they break down oxygen-containing compounds (e.g.,
NO3-) to obtain oxygen. The organisms that perform this process are called
denitrifiers. In general, they are heterotrophic bacteria that metabolize readily
biodegradable substrate under anoxic conditions by using nitrate as the electron
acceptor. If oxygen is available, these bacteria consume it for metabolism before they
use the nitrate. Therefore, dissolved oxygen concentrations must be minimized for
the denitrification process to function professionally (EPA, 2007).
The concentration of NO2N in raw leachate was 54 mg/L (Figure 4.70). The
oxidation of NH3N was confirmed by increasing the NO2N concentrations during
the treatment process in the reactors.

177

The NO3N concentration for leachate was 19 mg/L. The concentrations of


NO3N were 428, 379, 362, and 368 mg/L for normal SBR, PZSBR, PACsupplemented SBR (PACSBR), and powdered zeolitesupplemented SBR (PZE
SBR), respectively. Surampalli et al. (1997) reported nitrobacter oxidized NO2 to
NO3.

Concentration (mg/L)

1000
800

Raw Leachate
Normal-SBR

600

PZ-SBR
400

PAC-SBR
PZE-SBR

200
0
NH3-N

NO2-N

NO3-N

Figure 4-70: The concentration of NH3-N, NO2-N and NO3-N in raw leachate and
reactors
The oxidation of ammonia to NO2-N and oxidation of NO2-N to NO3-N for
leachate sample collected from SBRs is clear in Fig. 4.70. Normally, a part of NO2-N
and NO3-N was removed by Adsorbents-SBR in comparing with SBR.This is in line
with findings of Aziz (2011); Aktas and Cecen, (2001) and Surampalli et al. (1997).

178

CHAPTER 5
CONCLUSIONS AND RECOMMENDATIONS
5.1 Conclusions
The characteristics of the wastewater (from Bayan Baru Wastewater Treatment
Plant) and Semeling landfill leachates were studied. The average levels of different
parameters, such as colour, COD, NH3N, phenols, Fe, Mn, Ni, and Cd, exceeded
the levels prescribed by the 2009 Regulations of the Malaysian Environmental
Quality Act of 1974 (2009).
ZELIAC was produced in the concrete laboratory of the School of Civil
Engineering, USM. ZELIAC consists of zeolite, activated carbon, limestone, rice
husk ash, and Portland cement. The optimum settling time and dosage of powdered
ZELIAC (PZ) in batch/shaking experiments of fixed leachatedomestic wastewater
ratio samples were monitored. According to the batch/shaking experiments, the
optimum settling time and PZ were 90 min and 3 g/L, respectively.
RSM and CCD were used to elucidate the nature of the response surface in the
experimental plan and determine the optimum settings of the independent variables
[aeration rate (L/min), contact time (h), and leachate to wastewater ratio (%; v/v)]
and their reactions. To study the aerobic process, eight dependent factors (COD,
ammonia, colour, phenols, Fe, Mn, Ni, and Cd) were evaluated. The results indicated
that PZSBR removed pollutants more efficiently than SBR, PACSBR, and PZE
SBR. Under optimal conditions of aeration rate (2.41 L/min), leachate to wastewater
ratio (20%), and contact time (11.65 h) for PZSBR, the reduction efficiencies for
colour, NH3N, COD, phenols, Fe, Mn, Ni, and Cd were 84.74%, 72.35%, 99.54%,
61.93%, 79.58%, 73.32%, 79.28%, and 76.94%, respectively.

179

At the end of this study, the experiments were replicated (continuous


SBR/experiment) based on the obtained optimum parameters. The PZ-SBR removed
pollutants more than the other reactors as evidenced by the continuous
SBR/experiment. The reduction efficiency for colour, COD, ammonia, phenols,
sulfide, Fe, Mn, Ni, Cd and Cr were 87.18%, 73.84%, 97.69%, 67.71%, 74.13%
82.25%, 78.71%, 82.13%, 80.18%, and 79.24%, respectively.
In conclusion, the PZSBR exhibited higher performance in treating leachates
and wastewater, and the system has a higher potential to reduce colour, ammonia,
and metals.

5.2 Recommendations
Finally, the following points are suggested for other researchers:
1) ZELIAC is a new low-cost adsorbent that has been used in leachate and
wastewater treatment. Thus, many investigations should be carried out to explore its
performance in pollutant removal. The researchers can use it in other wastewater
treatment systems and methods.
2) In this study, ZELIAC showed a good performance in removing pollutants
that are distinct in colour and in removing metals. As such, strongly recommend
performing further studies to increase the performance of this adsorbent such as
adding new materials like powdered shell into ZELIAC.
3) Other operation factors should be investigated such as organic loading rate,
F/M ratio, solid retention time for leachate treatment by using sequencing batch
reactors. Moreover, also recommend more responses from molybdenum, copper,
calcium, cobalt, chromium, aluminum and sulfide to be investigated by other
researchers.

180

REFERENCES
Abbas, M. N., Husain, A. A., and Abbas, F. S. (2013) phenol removal from
wastewater using rice husk. Diyala Journal for Pure Sciences, 9(4), 51-60.
Abbas, A. A., Jingsong, G., Ping, L. Z., Ya, P. Y., and Al-Rekabi, W. S. (2009).
Review on landfill leachate treatments. Journal of Applied Sciences Research, 5(5):
534545.
Abdullah, S. B. (2010) Heavy Metals Removal from Industries Wastewater by Using
Seaweed through Biosorption Process. BSc Thesis, Faculty of Civil Engineering &
Earth Resources, University Malaysia Pahang.
Abdulrasaq, O. O., and Basiru, O. G. (2010) Removal of copper (II), iron (III) and
lead (II) ions from Mono-component Simulated Waste Effluent by Adsorption on
Coconut Husk. African Journal of Environmental Science and Technology, 4(6),
382-387.
Adlan M. N., Palaniandy, P., and Aziz, H. A. (2011) Optimization of coagulation and
dissolved air flotation (DAF) treatment of semi-aerobic landfill leachate using
response surface methodology (RSM). Desalination, 277(1-3): 7482.
Aghamohammadi, N., Aziz, H. A., Isa, M. H., and Zinatizadeh, A. A. (2007)
Powdered activated carbon augmented activated sludge process for treatment of
semi-aerobic landfill leachate using response surface methodology. Bioresource
Technology, 98: 35703578.
Akl, M. A., Yousef, A. M., and AbdElnasser, S. (2013) Removal of Iron and
Manganese in Water Samples Using Activated Carbon Derived from Local AgroResidues. Journal of Chemical Engineering & Process Technology, 4, 1-10.
Al-Dwairi, R. A., and Al-Rawajfeh, A. E. (2012) Removal of cobalt and nickel from
wastewater by using Jordan low-cost zeolite and bentonite. Journal of the University
of Chemical Technology and Metallurgy, 47, 69-76.
Ali, M. S., Khan, I. A., Hossain, M. I. (2008) chemical analysis of ordinary Portland
cement of Bangladesh. Chemical Engineering Research Bulletin, 12, 7 -10
Alkhaddar, R. M., Phipps, D. A., and Cheng, C. (2005) Today and Tomorrow!
Research Prospects for Aerobic Biological Liquid Waste Treatment for Reduction of
Carbon Load. Official Publication of the European Water Association (EWA), pp:18.

181

Alptekin, E. E. (2008) Anaerobic Treatment of Dilute Wastewaters. PhD Thesis,


Environmental Engineering Dep., Middle East Technical University.
Altig, J. (2013) The Langmuir Adsorption Isotherm. Physical Chemistry Laboratory,
Revision
2.0,
pp.
1-7,
CHEM
331L,
Available
at:
http://infohost.nmt.edu/~jaltig/Langmuir.pdf
Amirossadat, Z. (2014) Introduction of preliminary and Secondary Treatments.
Wastewater Engineering: Advanced Wastewater Treatment Systems, IJSR Pub,
Malaysia.
Anand, S. A., Nagarajappa, D. P., Sanjeev, S., and Ramu, S. (2014) Removal of
Hexavalent Chromium From Simulated Waste Water Using Rice Husk Ash as
Carbon Adsorbent. International Journal of Innovative Research in Science,
Engineering and Technology, 3(7), 14428-14432.
Andreottola, G., Foladori, P., and Ragazzi, M. (2001) Online control of a SBR
system for nitrogen removal from industrial wastewater. Water Science and
Technology, 43, 93-100.
APHA. (2005) Standard Methods for the Examination of Water and Wastewater,
21st ed., American public health association, Washington DC.
Argun, M. E. (2008) Use of clinoptilolite for the removal of nickel ions from water:
kinetics and thermodynamics. Journal of Hazardous Materials, 150, 587e595.
Arrojo, A. A. (2007) Advances systems for biological treatment of high nitrogenloaded wastewater. USC, pp: 312
Aydin, A. H., Guzel, F., and Tez Z. (1996) Investigation of adsorption isotherms
used for wool dyeing by aqueous extraction of cehri fruit (fructus rhamni petiolari)
and dyeing of wool and silk accompanied by various mordants. Tr. J. of Chemistry,
20, 283-288.
Aygun, A., Nas, B., and Berktay, A. (2008) Influence of High Organic Loading
Rates on COD Removal and Sludge Production in Moving Bed Biofilm Reactor.
Environmental Engineering Science, 25(9), 1311-316.
Azhari, M. F. L. B. (2010) the effectiveness of activated carbon from coconut shell
as wastewater pollutant removal. Bachelor Thesis, Universiti Malaysia Pahang.

182

Aziz, S. Q. (2011) Landfill leachate treatment using powdered activated carbon


augmented sequencing batch reactor (SBR) process. PhD thesis, School of Civil
Engineering, Universiti Sains Malaysia, Malaysia.
Aziz, H. A., Alias, S., Adlan, M. N., Faridah, A. H., Asaari, M. S., and Zahari, M. S.
(2007) Colour removal from landll leachate by coagulation and occulation
processes. Bioresource Technology, 98, 218220.
Aziz, S. Q., Aziz H. A., Bashir, M. J. K., and Mojiri, A. (2014) Municipal Landfill
Leachate Treatment Techniques: An Overview. Wastewater Engineering: Advanced
Wastewater Treatment Systems, IJSR Publications.
Aziz, S. Q., Aziz, H. A., and Yusoff, M. S. (2011a) Optimum Process Parameters for
the Treatment of Landfill Leachate using Powdered Activated Carbon Augmented
Sequencing Batch Reactor (SBR) Technology. Separation Science and
Technolology, 46, 112.
Aziz, S. Q., Aziz, H. A., and Yusoff, M. S. (2011b) Powdered activated carbon
augmented double react-settle sequencing batch reactor process for treatment of
landfill leachate. Desalination, 277, 313320.
Aziz, S. Q., Aziz, H. A., Yusoff, M. S., and Bashir, M. J. K. (2011c) Landfill
leachate treatment using powdered activated carbon augmented sequencing batch
reactor (SBR) process: optimization by response surface methodology. Journal of
Hazardous Materials, 189, 404-413.
Aziz, S. Q., Aziz, H. A., Yusoff, M. S., Bashir, M. J. K., and Umar, M. (2011d)
Leachate Characterization in semi-aerobic sanitary landfills: A comparative study.
Journal of Environmental Management, 91, 2608-2614.
Aziz, S. Q., Aziz, H. A., Yusoff, M. S., Mojiri, A., and Amr, S. S. A. (2012)
Adsorption isotherms in landfill leachate treatment using powdered activated carbon
augmented sequencing batch reactor technique: Statistical analysis by response
surface methodology. International Journal of Chemical Reactor Engineering, 10(1).
Aziz, H. A., Hin, L. T., Adlan, M. N., Zahari, M. S., Alias, S., Abufoul, A. A. M.,
Selamat, M.R., Bashir, M.J.K., Yusoff, M.S., and Umar, M. (2011) Removal of
High-Strength Colour from Semi-Aerobic Stabilized Landfill Leachate via
Adsorption on Limestone and Activated Carbon Mixture. Research Journal of
Chemical Science, 1(6), 1-7.
Babaee, A., and Shayegan, J. (2011) Effect of organic loading rates (OLR) on
production of methane from anaerobic digestion of vegetables waste. World
Renewable Energy Congress, 8-13 May, Sweden.
183

Bai, Y., and Bartkiewicz, B. (2009) Removal of Cadmium from Wastewater Using
Ion Exchange Resin Amberjet 1200H Columns. Polish Journal of Environmental
Studies, 18, 1191-1195.
Bashir, M. J. K., Aziz, H. A., Yusoff, M. S., and Adlan, M. N. (2010) Application of
response surface methodology (RSM) for optimization of ammoniacal nitrogen
removal from semi-aerobic landfill leachate using ion exchange resin. Desalination,
254, 154-161.
Battilani, A., Steiner, M., Andersen, M., Back, S. N., Lorenzen, J., Schweitzer, A.,
Dalsgaard, A., Forslund, A., Gola, S., Klopmann, W., Plauborg, F., and Andersen,
M. N. (2010) Decentralised water and wastewater treatment technologies to produce
functional water for irrigation. Agricultural Water Management, 98, 385402.
Benfenati, E., Pierucci, P., Fanelli, R., Preiss, A., Godejohann, M., and Astratov, M.
(1999) Comparative studies of the leachates of an industrial landfill by gas
chromatographymass spectrometry, liquid chromatographynuclear magnetic
resonance and liquid chromatographymass spectrometry. J. Cromatogr, 831, 243
56.
Boehler, M., Zwickenpflug, B., Hollender, J., Ternes, T., Joss, A., and Siegrist, H.
(2012) Removal of micropollutants in municipal wastewater treatment plants by
powder-activated carbon. Water Science and Technology, 66(10), 2115-2121.
Bohdziewicz, J., Bodzek, M., and Gorska, J. (2001) Application of pressure-driven
membrane techniques to biological treatment of landfill leachate. Process
Biochemistry, 36, 641-646.
Bu, L., Wang, K., Zhao, O. L., Wei, L. L., Zhang, J., and Yang, J. C. (2010)
Characterization of dissolved organic matter during landfill leachate treatment by
sequencing batch reactor, aeration corrosive cell-Fenton, and granular activated
carbon in series. Journal of Hazardous Materials, 179, 1096-1105.
Capodici, M., Di Trapani, D. and Viviani, G. (2014) Co-treatment of landfill leachate
in lab scale sequencing batch reactors: analysis of system performance and biomass
activity by means of respirometric techniques. Water Science & Technology,
doi:10.2166/wst.2014.005.
een F., and Akta, O. (2004) Aerobic Co-Treatment of Landfill Leachate with
Domestic Wastewater. Environmental Engineering Science, 21(3), 303-312.
Cecen, F., and Aktas, O. (2001) Effect of PAC addition in combined treatment of
landfill leachate and domestic wastewater in semi-continuously fed batch and
continuous-flow reactors. Water SA., 27 (2), 177.
184

een F., akroglu, D. (2001) Impact of landfill leachate on the co-treatment of


domestic wastewater. Biotechnology Letters, 23: 821826.
Cecen, F., Erdincler, A., and Kilic, E. (2003) Effect of powdered activated carbon
addition on sludge dewaterability and substrate removal in landfill leachate
treatment. Advances in Environmental Research, 7, 707-713.
Cervera, M. L., Arnal, M. C., and De la Guardia M. (2003) Removal of heavy metals
by using adsorption on alumina or chitosan. Anal Bioanal Chem., 375, 820825.
Chaari, I., Medhioub, M., and Jamoussi, F. (2011) Use of Clay to Remove Heavy
Metals from Jebel Chakir Landfill Leachate. Journal of Applied Sciences in
Environmental Sanitation, 6(2), 143-148.
Chan, Y. J., Chong, M. F., and Law, C. L. (2010) Biological treatment of
anaerobically digested palm oil mill effluent (POME) using a lab scale sequencing
batch reactor. Journal of Environmental Management, 91, 1738-1746.
Chan, Y. J., Chong M. F., and Law, C. L. (2011) Optimization on thermophilic
aerobic treatment of anaerobically digested palm oil mill effluent (POME).
Biochemical Engineering Journal, 55(3), 193-198.
Chan, Y.J., Chong, M.F., Law, C.L., and Hassell, D.G. (2009) A review on
anaerobicaerobic treatment of industrial and municipal wastewater. Chemical
Engineering Journal, 155, 1-18.
Chang, W., Tran, H., Park, D., Zhang R., and Ahn, D. (2009) Ammonium nitrogen
removal characteristics of zeolite media in a Biological Aerated Filter (BAF) for the
treatment of textile wastewater. Journal of Industrial and Engineering Chemistry, 15,
524-528.
Chiang, L. C., Chang, J. E., and Wen, T. C. (1995) Indirect Oxidation Effect in
Electrochemical Oxidation Treatment of Landfill Leachate. Water Research, 29(2),
671-678.
Collodetti, G., Gleize, P. J. P., Monteiro, P. J. M. (2014). Exploring the potential of
siloxane surface modified nano-SiO2 to improve the Portland cement pastes
hydration properties. Construction and Building Materials, 54, 99105
Czepirski, L., Balys, M. R., Komorowska-Czepirska, E. (2003) Some generalization
of Langmuir adsorption isotherm. Intrnational Journal Chemistry, 3(14), Article 14.

185

Dangcong, P., Bernet, N., Delgense, J. P, and Moletta, R. (2001) Simultaneous


organic carbon and nitrogen removal in a SBR controlled at low dissolved oxygen
concentration. Journal of Chemical Technology and Biotechnology, 76, 553-558.
Deng, Y. (2007) Physical and oxidative removal of organics during Fenton treatment
of mature municipal landfill leachate. Journal of Hazardous Materials, 146, 334
340.
Desta, M. B. (2013) Batch Sorption Experiments: Langmuir and Freundlich Isotherm
Studies for the Adsorption of Textile Metal Ions onto Teff Straw (Eragrostis tef)
Agricultural Waste. Journal of Thermodynamics, Article ID 375830, 6 pages.
Dhas, J. P. A. (2008) Removal of COD and Colour from Textile Wastewater Using
Limestone and Activated Carbone, MSc Thesis, University Sains Malaysia.
Diamadopoulos, E., Samara, P., Dabou, X., and Sakellaropouls, G. P. (1997)
Combined treatment of landfill leachate and domestic sewage in sequencing batch
reactor. Water Science and Technology, 36: 6168.
Dursun, S., and Pala, A. (2007) Lead pollution removal from water using a natural
zeolite. J. Int. Environmental Application & Science, 2(1-2), 11-19.
Dvorak, B. I. (2013) Drinking Water Treatment: Activated Carbon Filtration.
University of Nebraska Lincoln, G1489.
Efendy, N. S. B. S. (2010) Municipal Wastewater Treatment Using Constructed
Wetland And Limestone. Bachelor Thesis, Universiti Malaysia Pahang.
El-Naas, M. H., Al-Zuhair, S., and Alhaija, M. A. (2010) Reduction of COD in
renery wastewater through adsorption on date-pit activated carbon. Journal of
Hazardous Materials, 173, 750757.
Environmental Quality (Control of Pollution from Solid Waste Transfer Station and
Landfill) Regulations, under the Laws of MalaysiaMalaysia Environmental Quality
Act, 1974. 2000.
Environmental Quality (Sewage and Industrial Effluents) Regulations, under the
Laws of MalaysiaMalaysia Environmental Quality Act, 1974. 2009.
EPA. (2007) Wastewater Management Fact Sheet, Denitrifying Filters. EPA 832-F07-014.

186

Fabregas, T. V. (2004) SBR technology for wastewater treatment: suitable


operational conditions for nutrient removal. PhD Thesis, Universitit de Girona.
Foo, H. Y., and Hameed, B. H. (2009) An overview of landfill leachate treatment via
activated carbon adsorption process. Journal of Hazardous Materials, 171, 5460.
Foul, A. A. and Aziz, H. A., Isa, M. H., and Hung, Y. T. (2009). Primary treatment
of anaerobic landfill leachate using activated carbon and limestone: batch and
column studies. International Journal Environment and Waste Management, 4, 282290.
Friends of the Earth. (2007) Briefing Anaerobic digestion. 26-28 Understood Street,
London N1 7JQ. pp7.
Fu, F., and Wang, Q. (2011) Removal of heavy metal ions from wastewaters: A
review. Journal of Environmental Management, 92, 407-418.
Gao, D., Liu, L., Liang, H., and Wu, W. M. (2011) Comparison of four enhancement
strategies for aerobic granulation in SBR. Journal Hazardous Materials, 186, 320327.
Ghafari, S., Aziz, H. A., Isa, M. H., and Zinatizadehd, A. A. (2009) Application of
response surface methodology (RSM) to optimize coagulationflocculation treatment
of leachate using poly-aluminum chloride (PAC) and alum. Journal of Hazardous
Materials, 163, 650656.
Gotvajn, A. Z., Konan, J. Z., and Cotman, M. (2011) Fenton's oxidative treatment
of municipal landfill leachate as an alternative to biological process. Desalination,
275, 269275.
Guo, J. S., Abbas, A. A., Chen, Y. P., Liu, Z. P., Chen, P. (2010). Treatment of
landfill leachate using a combined stripping, Fenton, SBR, and coagulation process.
Journal of Hazardous Materials, 178, 699705.
Gupta, V. K., Ali, I., Saini, V. K., Gerven, T. V., Van der Bruggen, B., and
Vandecasteele, C. (2005) Removal of Dyes from Wastewater Using Bottom Ash.
Ind. Eng. Chem. Res., 44, 3655-3664.
Halim, A. A., Aziz, H. A., Johari, M. A. M., Ariffin, K. S., (2010) Comparison study
of ammonia and COD adsorption on zeolite, activated carbon and composite
materials in landfill leachate treatment. Desalination, 262: 31-35.

187

Halim, A. A., Aziz, H. A., Johari, M. A. M, Ariffin, K. S., Bashir, M. J. K. (2012)


Semi-Aerobic Landfill Leachate Treatment Using CarbonMinerals Composite
Adsorbent. Environmental Engineering Science, 29(5): 306-312.
Halim, A. A., Aziz, H. A., Johari, M. A. M., Ariffin, K. S., and Hung, Y. T. (2009)
Removal of ammoniacal nitrogen and COD from semi-aerobic landfill leachate using
low-cost activated carbonzeolite composite adsorbent. International Journal of
Environment and Waste Management, 4 (3/4), 399-411.
Halim, A. A., Latif, M. T., and Ithnin, A. (2013) Ammonia Removal from Aqueous
Solution Using Organic Acid Modified Activated Carbon. World Applied Sciences
Journal, 24 (1), 01-06.
Halsey, G. D. (1952) The role of surface heterogeneity. Adv. Catal., 4, 259269.
Hamdaoui, O., and Naffrechoux E (2007) Modeling of adsorption isotherms of
phenol and chlorophenols onto granular activated carbon Part I. Two-parameter
models and equations allowing determination of thermodynamic parameters. Journal
of Hazardous Materials, 147, 381-394.
Hasar, H., Ipek, U., and Kinaci, C. (2009) Joint treatment of landfill leachate with
municipal wastewater by submerged membrane bioreactor. Water Science &
Technology, 60(12), 31213127.
Hegazi, H. A. (2013) Removal of heavy metals from wastewater using agricultural
and industrial wastes as adsorbents. HBRC Journal, 9(3), 276-282.
Holenda, B., Domokos, E., Redey, A., and Fazakas, J. (2008) Dissolved oxygen
control of the activated sludge wastewater treatment process using model predictive
control. Computers and Chemical Engineering, 32, 12701278.
Isa, M. H., Lang, L. S., Assari, F. A. H., Aziz, H. A., Ramli, N. A., and Dhas, J. P. A.
(2007) Low cost removal of disperse dyes from aqueous solution using palm ash.
Dyes and Pigments, 74, 446-453.
Janczukowicz, W., Szewczyk, M., Krzemieniewski, M., and Pesta, J. (2001) Settling
Properties of Activated Sludge from a Sequencing Batch Reactor (SBR). Polish
Journal of Environmental Studies, 10(1), 15-20.
Jian, A. (2008) Study on Paper Mill Wastewater Treatment by SBR. Journal of South
China Normal University, 1(2): 25-26.

188

Kalka, J. (2012) Landfill Leachate Toxicity Removal in Combined Treatment with


Municipal Wastewater. The Scientific World Journal, Article ID 202897, 7 pages.
Kamaruddin, M. A., Yusoff, M. S., and Ahmad M. A. (2013) Treatment of semiaerobic landfill leachate using durian peel-based activated carbon adsorptionOptimization of preparation conditions. Intrnational Journal of Energy and
Environmental, 3(2), 223-236.
Kaur, R., Singh, J., Khare, R., Cameotra, S. S., and Ali, A. (2012) Batch sorption
dynamics, kinetics and equilibrium studies of Cr(VI), Ni(II) and Cu(II) from aqueous
phase using agricultural residues. Applied Water Science, 3, 207218.
Khan, N. A., Ibrahim, S., and Subramaniam, P. (2004) Elimination of Heavy Metals
from Wastewater Using Agricultural Wastes as Adsorbents. Malaysian Journal of
Science, 23, 43 51.
Klimiuk, E., and Kulikowska, D. (2004) Effectiveness of Organics and Nitrogen
Removal from Municipal Landfill Leachate in Single and Two-Stage SBR Systems.
Polish Journal of Environmental Studies, 13(5), 525-532.
Kong, Q. X., and Li, J. Y. (2004) The progress on biological nitrogen removal via
aerobic denitrification. Environment and Health, 21(3), 189191.
Kopac, T., and Bozgeyik, K. (2010) Effect of surface area enhancement on the
adsorption of bovine serum albumin onto titanium dioxide. Colloids and Surfaces B:
Biointerfaces, 76, 265271
Kulbat, E., Olaczuk-Neyman, K., Quant, B., Geneja, M., and Haustein, E. (2003)
Heavy Metals Removal in the Mechanical-Biological Wastewater Treatment Plant
Wschd in Gdask. Polish Journal of Environmental Studies, 12, 635-641.
Kulikowska, D., and Klimiuk, E. (2004) Removal of Organics and Nitrogen from
Municipal Landfill Leachate in Two-Stage SBR Reactors. Polish Journal of
Environmental Studies, 13, 389-396.
Kumar, G. S., Gupta, S. K., and Gurdeep, S. (2007) Anaerobic Hybrid Reactor - A
Promising Technology for the Treatment of Distillery Spent Wash. Journal of Indian
School of Mines., 11 (1), 25-38.
Kumar, R., and Subramanian, K. (2014). Treatment of Paper and Pulp Mill Effluent
using Sequential Batch Reactor. International Conference on Biological, Civil and
Environmental Engineering (BCEE-2014), March 17-18, Dubai (UAE).

189

Kurniawan, T. A., Lo, W., and Chan, G. Y. S. (2006) Physico-chemical treatments


for removal of recalcitrant contaminants from landfill leachate. Journal Hazardous
Materials, B129, 80100.
Kurata, Y., Ono, Y., and Ono, Y. (2008) Occurrence of phenols in leachates from
municipal solid waste landfill sites in Japan. Journal of Material Cycles and Waste
Management, 10, 144152.
Laitinen, N., Luonsi, A., and Vilen, J. (2006) Landfill leachate treatment with
sequencing batch reactor and membrane bioreactor. Desalination, 191: 8691.
Latif, M. A. (2011) Application of Upflow Anaerobic Sludge Blanket (UASB)
Reactor for Waste and Wastewater Treatments with Biogas Production. M.Sc Thesis,
Faculty of Civil and Earth Resource, University Malaysia Pahang.
Lee, K. M, and Lim, P. E. (2003) Treatment of phenolic wastewater using
agricultural wastes as an adsorbent in a sequencing batch reactor. Water Science and
Technology, 47(10):41-47.
Leong, M. L., Lee, K. M., Lai, S. O., and Ooi, B. S. (2011) Sludge characteristics
and performances of the SBR at different influent phenol concentration.
Desaliniation, 270, 181-187.
Lettinga, G., Hobma, S. W., Klapwijk, A., Velsen, A. F. M. V., and Zeeuw, W. D.
(1980) Use of the Upflow Sludge Blanket (USB) reactor concept for biological
wastewater treatment. Biotechnology and Bioengineering, 22, 699-734.
Li, T., Chen, W., and Wang, L. (2010) Particle properties in granular activated
carbon filter during drinking water treatment. Journal of Environmental Science
(China), 22(5): 681-8.
Li, J. P, Healy, M. G., Zhang, X., Norton, D., and Rodgers, M. (2008) Effect of
aeration rate on nutrient removal from slaughterhouse wastewater in intermittently
aeration sequencing batch reactors. Water and Air Soil Pollution, 192.
Li, X. Z., and Zhao, Q. L. (1998) Inhibition of microbial activity of activated sludge
by high strength of ammonia-nitrogen in leachate. Presented in 19th IAWQ Biennial
International Conference and Inhibition, 21-26 June, Vancouver (Canada).
Li, Z., Zhao, Q. L., and Hao, X. D. (1999) Ammonium removal from landfill
leachate by chemical precipitation. Waste Management, 19, 409-415.251-261.

190

Liermann, T. A. (2009) Fiji Islands Naboro Landfill Leachate Quality Analysis and
the Applicability of Developed versus Small Island Developing State Discharge
Standards. MSc Thesis of Environmental Engineering, Michigan Technological
University.
Lim, P. E., Lim, S. P., Seng, C. E., and Noor, A. M. (2010) Treatment of landfill
leachate in sequencing batch reactor supplemented with activated rice husk ash as
adsorbent. Chemical Engineering Journal, 159, 123-128.
Lim, Y. L., Ho, Y. C., and Alkarkhi, A. F. M. (2014) Application of Optimization in
Wastewater Treatment. Wastewater Engineering: Types, Characteristics and
Treatment Technologies, IJSR Publications, Malaysia.
Litas, G. C., Zouboulis, A. I., Zaboulis, D., and Samaras, P. (2012) The use of a
submerged membrane batch reactor (S.M.B.R) for co-treatment of landfi ll leachates
and domestic wastewater. Desalination and Water Treatment, 39, 284-290.
Mace, S., and Alvarez, J. M. (2002) Utilization of SBR Technology for Wastewater
Treatment: An Overview. Ind. Eng. Chem. Res., 41, 5539-5553.
Mahvi, A. H. (2008) Sequencing Batch Reactor: A Promising Technology in
Wastewater Treatment. Iran. J. Environ. Health. Sci. Eng., 5(2), 79-90.
Mahvi, A. H., Brown, P., Vaezi, F., and Karakani, F. (2005) Feasibility of
Continuous Flow Sequencing Batch Reactor in Synthetic Wastewater Treatment.
Journal of Applied Sciences, 5 (1), 172-176.
Mai, H. N. P. (2006) Integrated Treatment of Tapioca Processing Industrial
Wastewater: Based on Environmental Bio-Technology. PhD Thesis Wageningen
University, Wageningen, the Netherlands.
Malakahmad, A., Hasania, A., Eisakhanib, M., and Isa, M. H. (2011) Sequencing
Batch Reactor (SBR) for the removal of Hg2+ and Cd2+ from synthetic
petrochemical factory wastewater. Journal of Hazardous Materials, 191, 118125.
MEng, J. L. (2012) Removal of phosphorus from water using treated Acid Mine
Drainage solids and pellets made thereof. PhD Thesis, School of Engineering,
Cardiff University.
Mittal, A. (2011) Biological Wastewater Treatment. Water Today, 32-44.

191

Mohajeri, S., Aziz, H. A., Isa, M. H., Zahed, M. A., and Adlan, M. N. (2010)
Statistical optimization of process parameters for landfill leachate treatment using
electro-Fenton technique. Journal of Hazardous Materials, 176, 749-758.
Mohan, S., and Gandhimathi, R. (2009) Removal of heavy metal ions from
municipal solid waste leachate using coal fly ash as an adsorbent. Journal of
Hazardous Materials, 169, 351359.
Mojiri, A. (2011) Review on Membrane Bioreactor, Ion Exchange and adsorption
Methods for Landfill Leachate Treatment. Australian Journal of Basic and Applied
Sciences, 5(12), 1365-1370.
Mojiri, A., Aziz, H. A., Aziz, S. Q., Selamat, M. R. B., Gholami, A., and Aboutorab,
M. (2013a) Phytoremediation of soil contaminated with nickel by Lepidium sativum;
optimization by response surface methodology. Global NEST Journal, 15, 69-75.
Mojiri, A., Aziz, H. A., Zahed, M., Aziz, S. Q., and Selamat, M. R. B. (2013b)
Phytoremediation of Heavy Metals from Urban Waste Leachate by Southern Cattail
(Typha domingensis). International Journal of Scientific Research in Environmental
Sciences, 1(4), 63-70.
Moncls, H., Puig, S., Coma, M., Bosch, A., Balaguer, M. D., and Colprim, J. (2009)
Nitrogen removal from landfill leachate using the SBR technology. Environ
Technology, 30(3): 283-90.
Motsi, T., Rowson, N. A., and Simmons, M. J. H. (2009) Adsorption of heavy metals
from acid mine drainage by natural zeolite. Int. J. Miner. Process, 92, 42-48.
Mustain, A., Wibawa, G., Nais, M. F., and Falah, M. (2014) synthesis of zeolite naa
from low grade (high impurities) indonesian natural zeolite. Indo. J. Chem., 14 (2),
138142.
National Solid Waste Management Department. (2014) ringkasan tapak pelupusan
sisa pepejal di Malaysia. http://www.kpkt.gov.my/jpspn_2013/
Neczaj, E., Kacprzak, M., Kamizela, T., Lach, J., and Okoniewska E. (2008)
Sequencing batch reactor system for the co-treatment of landfill leachate and dairy
wastewater. Desalination, 222, 404409
Neczaj, E., Kacprzak, M., Lach, J., and Okoniewska, E. (2007) Effect of sonication
on combined treatment of landfill leachate and domestic sewage in SBR reactor.
Desalination, 204, 227233

192

Ngo, H. H., Guo, W. and Xing, W. (2008) Applied technologies in municipal solid
waste landfill leachate treatment. Encyclopedia of Life Support Systems (EOLSS),
pp: 17.
Nosier, S. A. (2003) Removal of Cadmium Ions from Industrial Wastewater by
Cementation. Chem. Biochem. Eng. Q., 17, 219224.
Ok, Y. S., Yang, J.E., Zhang, Y. S., Kim, S. J., and Chung, D. Y. (2007) Heavy
metal adsorption by a formulated zeolite-Portland cement mixture. Journal of
Hazardous Materials, 147, 9196.
Ostroski, I.C., Barros, M.A.S.D., Silvab, E.A., Dantas, J.H., Arroyo, P.A., and Lima,
O.C.M. (2009) A comparative study for the ion exchange of Fe(III) and Zn(II) on
zeolite NaY. Journal of Hazardous Materials, 161, 1404-1412.
Palanisamy, K., and Nomanbhay, S.M. (2005) removal of heavy metal from
industrial wastewater using chitosan coated oil palm shell charcoal. Electronic
Journal of Biotechnology, 8, 43-53.
Pandey, P. K., Choubey, S., Verma, Y., Pandey, M., Kamal, S. S. K., and
Chandrashekhar, K. (2007) Biosorptive Removal of Ni(Ii) from Wastewater and
Industrial Effluent. Int. J. Environ. Res. Public Heal., 4, 332-339.
Piatkiewicz, W., Biemacka, E., and Suchecka, T. (2001) A Polish Study: Treating
Landfill leachate with membranes. In: Filtration and Separation, vol 38, 6th edn, pp.
22-23.
Pipeline. (2013) Phosphorus and Onsite Wastewater Systems. Small Community
Wastewater Issues Explained to the Public, Vol. 23.
Pelivanoski, P., Donevska, K., and Sofronievska, D. (2009) Wastewater and Landfill
Leachate Treatment Plant for the Municipality of Centar upa. International
Symposium on Water Management and Hydraulic Engineering Ohrid/Macedonia, 15 SeptembeR.
Qasim, B. R., and Chiang, W. (1994) Sanitary Landfill Leachate: Generation,
Control and Treatment. CRC Press. USA
Qin L., Liu, Y., Tay J. H. (2004) Effect of settling time on aerobic granulation in
sequencing batch reactor. Biochemical Engineering Journal, 21(1), 47-62.

193

Rahmani, A. R., and Mahvi, A. H. (2008) Use of Ion Exchange for Removal of
Ammonium: A Biological Regeneration of Zeolite. Global NEST Journal, 8(2), 146150.
Rautenbach, R., Vossenkaul, K., Linn, T., and Katz, T. (1997) Waste water treatment
by membrane processes-New development in ultrafiltration, nanofiltration and
reverse osmosis. Desalination, 108(13), 247253.
Renou, S., Givaudan, J. G., Poulain, S., Dirassouyan, F., and Moulin, P. (2008)
Landfill leachate treatment: Review and opportunity. Journal of Hazardous
Materials, 150, 468493.
Risnawati, I., Damanhuri, T. P. (2010) Institute Technology Bandung. Faculty Civil
and Environmental Engineering, SW5-1 to SW5-11.
Rodriguez, J., Castrillon, L., Maranon, E., Sastre, H., and Fernandez, E. (2004)
Removal of non-biodegradable organic matter from landfill leachates by adsorption.
Water Research, 38, 32973303.
Rong, Q., Kun, Y., and Zhao-xiang, Y. (2007) Treatment of coke plant wastewater
by SND fixed biofilm hybrid system. Journal of Environmental Sciences, 19, 153
159.
Samad, H. Y., Mustafa, S., Naila, B., Naeem, A., Hamid A., and Dilara, B. (2004)
Phosphate removal from municipal wastewater by different adsorbents. Jour. Chem.
Soc. Pak., 26(3), 286-287.
Salam, O. E., Reiad, N. A., and ElShafei, M. M. (2011) A study of the removal
characteristics of heavy metals from wastewater by low-cost adsorbents. Journal of
Advanced Research, 2, 297303.
Sarudji, D., and Mangkoedihardjo S. (2007) Cement and clay treatment for organic
matter containing leachate. World Applied Sciences Journal, 2(4), 387389.
Sarioglu, M. (2005) Removal of ammonium from municipal wastewater using
natural Turkish (Dogantepe) zeolite. Separation and Purification Technology, 41(1),
1-11.
Sewvandi, G. A., and Adikary, S. U. (2011) Removal of Heavy Metals from
Wastewater
Using
Chitosan.
http://management.kochitech.ac.jp/ssms_papers/sms11-5519_f7ef9ac7c0fc35b5704c4fdba8c7e34a.pdf.

194

Slacka, R. J. Gronowb, J. R., and Voulvoulisa, N. (2005) Household hazardous waste


in municipal landfills: contaminants in leachate. Science of the Total Environmental,
337, 119137.
Sperling, M. V. (2007) Activated Sludge and Aerobic Biofilm Reactors. IWA
Publishing, pp 322.
Stefanidou, M., Papayianni, I. (2012) Influence of nano-SiO2 on the Portland cement
pastes. Composites: Part B, 43, 27062710
Stegmann, R., Heyer, K. U., and Cossu, R. (2005) Leachate Treatment. Proceedings
of Tenth International Waste Management and Landfill Symposium, Cagliari, Italy;
3 - 7 October.
Surampalli, R.Y., Tyagi, R.D., Scheible, O.K., and Heidman, J.A. (1997).
Nitrification, denitrification and phosphorus removal in SBR. Biorecource
Technolology, 61, 151-157.
Swierczynska, A., Sochacki, A., Bohdziewicz, J. (2012) Co-treatment of landfill
leachate with municipal wastewater in MSBR: Lab-scale and simulation study. The
Silesian University of Technology, No. 2/2012.
Syzdek, A. C., and Ahlert, R. C. (1984) Separation of landfill leachate with
polymeric ultrafiltration membranes. J. Hazard. Mater., 9(2), 209-220.
Taffarel, S. R., and Rubio S. R. (2009) On the removal of Mn2+ ions by adsorption
onto natural and activated Chilean zeolites. Minerals Engineering, 22, 336343.
Tay, J. H., Tay, S. T. L., Yu, L., Yeow, S.K., and Ivanov, V. (2006) Biogranulation
Technologies for Wastewater Treatment: Microbial granules. Elsevier, pp: 273.
Tchobanoglous, G., Burton F. L., and Stensel, H. D. (1991) Metcalf & Eddy, Inc.
Wastewater Engineering: Treatment and Reuse. Metcalf & Eddy, Inc.
Tengrui, L., Al-Harbawi, A. F., Bo, L. M., Jun, Z., and Long, X. Y. (2007)
Characteristics of Nitrogen Removal from Old Landfill Leachate by Sequencing
Batch Biofilm Reactor. American Journal of Applied Science, 4 (4), 211-214.
Thornton, A., Pearce P., and Parsons S. A. (2007) Ammonium removal from solution
using ion exchange on to MesoLite, an equilibrium study. Journal Hazardous
Materials, 147, 883-889.

195

Timur, H., and Ozturk, I. (1999) Anaerobic sequencing batch reactor treatment of
landfill leachate. Water Research, 33 (15): 32253230.
Tortora A (2010). Microbial Growth. Biol 3400, Course Notes, 12 April, University
of Lethbridge, Canada.
Trabelsi I., Salah, S., and Ounaeis, F. (2013) Coupling short-time sequencing batch
reactor and coagulationsettling process for co-treatment of landfill leachate with
raw municipal wastewater. Arab Jounal of Geoscience, 6, 20712079.
Umar, M., Aziz, H. A., and Yusoff, M. S. (2011) Assessing the chlorine disinfection
of landfill leachate and optimization by response surface methodology (RSM).
Desalination, 274(1-3), 278283.
UNEP. (2009) Developing Integrated Solid Waste Management Plan. Volume 1:
Waste Characterization and Quantication with Projections for Future. pp 73.
UNEP. (2005) Solid Waste Management. (Volume I). pp 524.
http://www.unep.or.jp/ietc/Publications/spc/solid_waste_management/index.asp
[Accessed March 3, 2013]
USEPA. (1999) Wastewater, Technology Fact Sheet: Sequencing Batch Reactors.
U.S Environmental Protection Agency, Office of Water, Washington, D.C., EPA
932-F-99-073.
Uygur, A., and Kargi, F. (2004) Biologicaol nutrient removal from pre-treated
landfill leachate in a sequencing batch reactor. Journal of Environ Management, 71,
914.
Varank, G., Demir, A., Yetilmezsoy K., Bilgili, M. S., Top, S., and Sekman, E.
(2011) Estimation of transport parameters of phenolic compounds and inorganic
contaminants through composite landll liners using one-dimensional mass transport
model. Waste Management, 31: 22632274.
Vignesawarna, S., Sundaravadivel, M., and Chaudhary, D. S. (2004) Sequencing
batch reactor: principles, design/operation and case study. Water and Wastewater
Treatment Technology, Encyclopedia of life support systems
Visvanathan, C., Ben Aim, R., and Parameshwaran, K. (2000) Membrane Separation
Bioreactors for Wastewater Treatment. Critical Reviews in Environmental Science
and Technology, 30(1), 1-48.

196

Water and Wastewater Industry. (2009) Dissolved Oxygen Measurement in


Wastewater Treatment. Application Data Sheet, ADS 4950-01/rev.G.
Wang, Y., Kmiya Y., and Okuhara, T. (2007) Removal of low-concentration
ammonia in water by ion-exchange using Na-mordenite. Water Research, 41, 269276.
Wang, S., and Peng, Y. (2010) Natural zeolites as effective adsorbents in water and
wastewater treatment. Chemical Engineering Journal, 156(1), 11-24.
Wang, Y., Peng Y., and Stephenson, T. (2009) Effect of influent nutrient ratios and
hydraulic retention time (HRT) on simultaneous phosphorus and nitrogen removal I a
two-sludge sequencing batch reactor process. Bioresource Technology, 100, 35063512.
Yan-jiao, G., Li-hong, Z., Jian, Z., and Yong, Z. (2010) Heavy Metal Removal from
Synthetic Landfill Leachate Using Oyster Shells Adsorbent. 978-1-4244-71614/10/$26.00 IEEE.
Zhou, L., and Mancl, K. (2007) Calculating Loadings Rates for Design of Small
Flow Onsite Wastewater Treatment Systems Hydraulic vs. Organic Loading. The
Ohio State University, pp: 2.

197

Appendix A: Literature Review and Batch/Shaking Experiments


A-1: Leachate to wastewater mixing ratio in the literature review
No.
1
2
3
4
5
6

Leachate (%)
50
20 to 50
25
10 to 50
5 to 25
5 to 20

Wastewater (%)
50
80 to 50
75
90 to 50
95 to 75
95 to 80

Type of wastewater
Domestic wastewater
Domestic wastewater
Dairy wastewater
Synthetic wastewater
Domestic wastewater
Domestic wastewater

7
8
9

6.7 to 20
50
< 55

93.3 to 80
50
> 55

Domestic wastewater
Domestic Wastewater
Domestic wastewater

Reference
Litas et al. (2012)
Neczaj et al. (2007)
Neczaj et al. (2008)
Capodici et al. (2014)
Cecen et al. (2003)
een and akroglu
(2001)
een and Aktas (2001)
Uygur and Kargi (2004)
Qasim and Chiang (1994)

Table A-2: Effect of settling time on DO concentration in SBR


Settling Time (h)
0
0.5
1
1.5
2
3
4
6

DO (mg/L)
5.82
2.11
0.98
0.51
0.52
0.52
0.51
0.48

Table A-3: Removal parameters versus PZ-SBR dosage


PZ
ZELIAC
0
1
2
3
5
7
10
15
20

Color
Removal
(%)
0
10.07
22.01
37.90
36.97
36.34
36.34
33.43
33.95

Ammonia
Removal
(%)
0
15.37
28.86
42.39
45.25
45.25
45.25
45.47
45.47

COD
Removal
(%)
0
7.54
15.70
24.35
26.94
28.31
26.94
28.06
28.06

198

PZ
ZELIAC
(g/L)
0
1
2
3
5
7
10
15
20

Color
(Pt. Co)

Ammonia
(mg/L)

COD
(mg/L)

963
867
751
598
607
613
613
641
634

272.0
230.2
193.5
156.7
149.1
148.9
148.9
148.3
148.3

809
748
682
612
591
580
591
582
582

Appendix B: Adsorption Isotherms and Raw data

Table A-4: The isotherm data for color


PZ dosage
(g/L)

Color
(Pt. Co)

Adsorbate (Ce) by
PZ (Pt. Co)

Volume
(L)

0
1
2
3

963
867
751
598

0
96
212
365

1
1
1
1

PZ dosage
(g/L)

COD
(mg/L)

Adsorbate (Ce) by
PZ (mg/L)

Volume
(L)

0
1
2
3

809
748
682
612

0
61
127
197

1
1
1
1

PZ dosage
(g/L)

NH3-N
(mg/L)

Adsorbate (Ce) by
PZ (mg/L)

Volume
(L)

0
1
2
3

272.0
230.2
193.5
156.7

0.0
41.8
78.5
115.3

1
1
1
1

PZ dosage
(g/L)

Fe
(mg/L)

Adsorbate (Ce) by
PZ (mg/L)

Volume
(L)

0
1
2
3

6.34
5.51
4.76
4.13

0.00
0.83
1.58
2.21

1
1
1
1

PZ dosage
(g/L)

Mn
(mg/L)

Adsorbate (Ce) by
PZ (mg/L)

Volume
(L)

0
1
2
3

2.09
1.86
1.64
1.46

0.00
0.23
0.45
0.63

1
1
1
1

PZ dosage
(g/L)

Ni
(mg/L)

Adsorbate (Ce) by
PZ (mg/L)

Volume
(L)

0
1
2
3

4.31
3.74
3.37
2.94

0.00
0.57
0.94
1.37

1
1
1
1

qe (mg/g)
or
x/m (mg/g)
96.00
106.00
121.67

Table A-5: The isotherm data for COD


qe (mg/g)
or
x/m (mg/g)
61.00
63.50
65.67

Table A-6: The isotherm data for NH3-N


qe (mg/g)
or
x/m (mg/g)
41.80
39.25
38.10

Table A-7: The isotherm data for Fe


qe (mg/g)
or
x/m (mg/g)
0.83
0.79
0.73

Table A-8: The isotherm data for Mn


qe (mg/g)
or
x/m (mg/g)
0.23
0.22
0.21

Table A-9: The isotherm data for Ni

199

qe (mg/g)
or
x/m (mg/g)
0.57
0.47
0.45

200
12
2

7.5

0.5

0.5

0.5

0.5

4.0

7.5

4.0

4.0

7.5

4.0

7.5

4.0

0.5

7.5

4.0

4.0

4.0

4.0

10

11

12

13

14

15

16

17

18

19

20

12

12

12

12

12

12

22

22

12

12

22

22

22

12

4.5

Run

Contact time
(h)

Aeration rate
(L/min)

50

20

50

50

20

80

50

80

50

80

50

50

50

50

20

50

20

80

20

80

Leachate to
wastewater
mixing ratio
(%; v/v)

930

705

925

914

860

1198

892

1226

913

1183

860

944

874

907

891

803

806

1096

752

1046

Colour
rem.
(Pt. Co)

772.4

737.8

769.7

771.3

698.7

901.5

765.2

878.8

753.1

967.3

772.0

725.4

788.4

765.2

739.0

778.7

763.8

967.4

778.4

797.1

COD rm.
(mg/L)

23.3

20.7

31.2

25.7

50.5

127.0

25.8

53.2

21.1

109.2

31.3

109.3

57.5

21.0

66.5

107.8

52.2

152.8

41.0

95.0

Ammonia
rem.
(mg/L)

1.17

1.12

1.20

1.17

1.29

1.40

1.19

1.45

1.16

1.41

1.16

1.27

1.24

1.18

1.19

1.23

1.16

1.43

1.16

1.31

Phenols
rem.
(mg/L)

Table A-10: Raw data for the Normal-SBR

3.82

3.28

3.74

3.73

3.57

5.00

3.68

5.01

3.75

5.02

3.85

3.73

3.88

3.68

3.56

3.80

3.46

4.93

3.42

4.84

Fe rem.
(mg/L)

1.35

1.22

1.34

1.33

1.26

1.64

1.35

1.66

1.32

1.66

1.39

1.40

1.41

1.33

1.24

1.38

1.25

1.63

1.28

1.61

Mn rem.
(mg/L)

3.32

2.73

3.35

3.31

2.86

4.12

3.31

4.20

3.33

4.16

3.31

3.32

3.36

3.31

2.84

3.34

2.77

4.05

2.82

3.97

Ni rem.
(mg/L)

1.82

1.53

1.83

1.83

1.57

2.23

1.83

2.30

1.84

2.29

1.85

1.87

1.87

1.83

1.55

1.84

1.56

2.23

1.58

2.21

Cd rem.
(mg/L)

201
12
2

7.5
0.5
0.5
0.5
0.5
4.0
7.5
4.0
4.0
7.5
4.0
7.5
4.0
0.5
7.5
4.0
4.0
4.0
4.0

10

11

12

13

14

15

16

17

18

19

20

12

12

12

12

12

12

22

22

12

12

22

22

22

12

4.5

Run

Contact time
(h)

Aeration rate
(L/min)

50

20

50

50

20

80

50

80

50

80

50

50

50

50

20

50

20

80

20

80

Leachate to
wastewater
mixing ratio
(%; v/v)

413

229

417

362

345

564

350

582

374

583

418

412

434

387

365

434

299

635

362

538

Colour
rem.
(Pt. Co)

427.7

374.9

438.5

413.4

396.4

667.1

437.1

608.6

441.5

568.6

474.6

451.4

480.4

435.5

347.3

424.3

398.1

647.6

417.1

620.0

COD rm.
(mg/L)

47.4

9.2

42.5

41.9

15.9

102.8

21.4

108.9

27.1

91.8

47.1

21.0

36.7

21.3

20.6

48.5

16.5

109.4

25.4

58.2

Ammonia
rem.
(mg/L)

0.81

0.63

0.80

0.81

0.66

0.91

0.79

0.92

0.80

0.89

0.75

0.75

0.79

0.78

0.63

0.75

0.61

0.87

0.64

0.90

Phenols
rem.
(mg/L)

Table A-11: Raw data for the PZ-SBR

1.26

1.20

1.58

1.53

1.41

3.27

1.69

3.40

1.71

3.75

1.70

1.70

1.71

1.65

1.27

1.66

1.31

3.36

1.41

3.40

Fe rem.
(mg/L)

0.73

0.53

0.73

0.79

0.56

1.07

0.74

1.14

0.71

1.20

0.77

0.77

0.78

0.75

0.53

0.79

0.56

1.09

0.58

1.11

Mn rem.
(mg/L)

1.95

1.08

1.94

2.03

1.22

3.01

2.08

3.11

1.91

3.13

2.02

2.03

2.03

1.93

1.03

2.13

1.12

3.03

1.14

2.89

Ni rem.
(mg/L)

1.09

0.64

1.07

1.08

0.68

1.63

1.14

1.72

1.14

1.73

1.14

1.15

1.18

1.10

0.63

1.18

0.69

1.67

0.75

1.63

Cd rem.
(mg/L)

202
12
2

7.5
0.5
0.5
0.5
0.5
4.0
7.5
4.0
4.0
7.5
4.0
7.5
4.0
0.5
7.5
4.0
4.0
4.0
4.0

10

11

12

13

14

15

16

17

18

19

20

12

12

12

12

12

12

22

22

12

12

22

22

22

12

4.5

Run

Contact time
(h)

Aeration rate
(L/min)

50

20

50

50

20

80

50

80

50

80

50

50

50

50

20

50

20

80

20

80

Leachate to
wastewater
mixing ratio
(%; v/v)

725

417

755

792

470

812

762

841

730

862

771

738

757

745

452

778

462

828

496

819

Colour
rem.
(Pt. Co)

572.0

423.7

572.0

593.1

489.0

749.1

585.0

765.8

551.2

754.1

585.3

564.7

557.9

546.0

479.1

582.4

456.5

732.0

489.0

703.4

COD rm.
(mg/L)

51.0

10.8

50.7

46.3

17.1

109.5

55.1

120.0

46.8

127.3

48.5

36.2

64.0

34.9

12.0

37.6

13.7

115.9

22.76

111.9

Ammonia
rem.
(mg/L)

1.08

0.88

1.09

1.07

0.92

1.31

1.11

1.33

1.06

1.32

1.07

1.10

1.11

1.07

0.91

1.07

0.87

1.30

0.94

1.28

Phenols
rem.
(mg/L)

Table A-12: Raw data for the PAC-SBR

3.38

2.40

3.39

3.37

3.20

4.19

3.43

4.22

3.41

4.27

3.47

3.55

3.66

3.39

2.53

3.79

2.88

4.16

2.94

4.13

Fe rem.
(mg/L)

1.15

0.93

1.18

1.19

1.12

1.52

1.19

1.53

1.18

1.55

1.24

1.35

1.28

1.17

0.96

1.33

1.00

1.50

1.00

1.46

Mn rem.
(mg/L)

2.94

2.20

2.96

2.91

2.88

3.86

2.91

3.89

2.96

3.91

3.00

3.45

3.15

2.91

2.41

3.35

2.58

3.80

2.60

3.75

Ni rem.
(mg/L)

1.57

1.17

1.61

1.59

1.52

2.08

1.51

2.07

1.62

2.11

1.64

1.86

1.75

1.62

1.30

1.83

1.35

2.05

1.38

2.00

Cd rem.
(mg/L)

203

Aeration rate
(L/min)
4.5
7.5
0.5
0.5
0.5
0.5
4.0
7.5
4.0
4.0
7.5
4.0
7.5
4.0
0.5
7.5
4.0
4.0
4.0
4.0

Run

10

11

12

13

14

15

16

17

`8

19

12

12

12

12

12

12

22

22

12

12

12

22

22

22

12

Contact time
(h)

50

20

50

50

20

80

50

80

50

80

50

50

50

50

20

50

20

80

20

80

Leachate to
wastewater
mixing ratio
(%; v/v)

629

407

625

628

507

808

612

858

606

845

640

656

675

632

455

643

424

812

483

775

Colour
rem.
(Pt. Co)

553.9

479.6

559.0

557.0

528.0

765.8

547.3

778.5

561.9

781.9

577.2

570.6

571.0

549.4

494.3

560.3

498.0

781.7

519.2

753.1

COD rm.
(mg/L)

84.9

26.9

85.2

84.4

58.4

109.4

87.0

111.1

82.6

120.3

83.4

84.2

87.1

84.4

20.5

80.1

38.6

117.4

58.8

113.2

Ammonia
rem.
(mg/L)

1.08

0.95

1.07

1.07

0.96

1.30

1.06

1.29

1.08

1.32

1.09

1.07

1.09

1.06

0.97

1.10

0.92

1.28

0.98

1.27

Phenols
rem.
(mg/L)

Table A-13: Raw data for the PZE-SBR

2.82

2.10

2.82

2.80

2.64

4.10

2.82

4.21

2.84

4.22

3.06

3.06

3.31

2.83

2.30

3.18

2.22

4.16

2.46

4.10

Fe rem.
(mg/L)

1.03

0.79

1.03

1.02

0.95

1.40

1.00

1.43

1.03

1.41

1.14

1.12

1.20

1.00

0.87

1.16

0.84

1.35

0.89

1.32

Mn rem.
(mg/L)

2.53

1.81

2.47

2.51

2.57

3.56

2.61

3.64

2.56

3.69

2.66

2.61

2.64

2.46

1.97

2.57

1.91

3.43

2.05

3.35

Ni rem.
(mg/L)

1.40

1.07

1.42

1.43

1.27

1.95

1.43

1.97

1.44

1.95

1.50

1.51

1.57

1.44

1.18

1.49

1.15

1.92

1.18

1.87

Cd rem.
(mg/L)

PUBLICATIONS
Journals
1) Mojiri A., Aziz H.A., Zaman N.Q, Aziz S.Q., Zahed M.A. (2014). Powdered
ZELIAC augmented SBR process for co-treatment of landfill leachate and
domestic wastewater. Journal of Environmental Management, 139: 1-14
(Elsevier; IF= 3.18).
2) Mojiri A., Aziz H.A., Zaman N.Q, Aziz S.Q., Zahed M.A. (2014). Metals
Removal from Municipal Landfill Leachate and Wastewater Using Adsorbents
Combined with Biological Method. Desalination and Water Treatment, In
Press (Taylor & Francis; IF=0.987).
3) Mojiri A., Aziz H.A., Zaman N.Q., Aziz S.Q. (2012). A Review on Anaerobic
Digestion, Bio-reactor and Nitrogen Removal from Wastewater and Landfill
Leachate by Bio-reactor. Advances in Environmental Biology, 6(7): 21432150. (ISI and SCOPUS)
4) Mojiri A., Aziz H.A, Aziz S.Q. (2013). Trends in Physical-Chemical Methods for
Landfill Leachate Treatment. International Journal of Scientific Research in
Environmental Sciences, 1(2): 16-25.

Book
1) Mojiri A., Aziz H.A. (2014). Wastewater Engineering: Advanced Wastewater
Treatment Systems. Publisher: IJSR Publications, Malaysia

Book Chapter
1) Mojiri A., Ramli S.F.B. (2015). Introduction to Leachate Treatment. Control and
Treatment of Landfill Leachate for Sanitary Waste Disposal, IGI Global. In
Press.

204

International Conferences
1) Mojiri, A., Aziz, H.A., Zaman, N.Q., Aziz, S.Q. (2013). Landfill Leachate and
Urban Wastewater Treatment by Powdered Zeliac Augmented Sequencing
Batch Reactor Process. The Twenty-Eighth International Conference on Solid
Waste Technology and Management, March 10-13, 2013, Philadelphia, PA,
USA.

205