POLLUTION STUDY AND BIOREMEDIATION OF HEAVY METAL IN AQUEOUS AND SEDIMENT PHASES OF SUNGAI PINANG RIVER BASIN
by
FARAH NAEMAH BINTI MOHD SAAD
Thesis submitted in fulfillment of the requirements
for the degree of
Doctor of Philosophy
June 2013 ACKNOWLEDGEMENTS
First and foremost, all praise to Allah that by His will, I am finally able to finish up my thesis.
My sincere appreciation and deep gratitude to my supervisor, Prof. Dr. Nik Norulaini Nik
Ab. Rahman and Associate Prof. Dr. Abbas Fadhl Mubarek Al-Karkhi, my co-supervisor for their valuable guidance, advice, suggestion, constructive criticisms and utmost support throughout the research.
My sincere thanks is extended to the staff of related goverment agencies which are the
Department of Drainage and Irrigation (DID), Department of Environment (DOE) and
Penang Municipal Council for allowing me to browse through the related and important reports, maps and data during the research study.
I dedicated my utmost gratitude and thanks to my late father, Mohd Saad b. Ahmad, my mother, Mahiya bt. Mahmud and my lovely husband, Khairul b. Mohd Arshad for their constant support, understanding, love and motivation throughout the study. Not forgetting my brothers, sister in-laws and those from both sides of my family for their support and understanding.
My special thanks to my colleagues and friends who have spent some of their precious time, support and knowledge in helping me throughout this study especially Pn. Fatehah, Cik Fera,
Pn. Yana, Cik Zuhida, En. Abu Hanipah, Pn. Shalima, Pn. Sabariah and En. Jamilul Firdaus at the School of Industrial Technology. Thanks are in order to En. Fazli, En. Khairul and En.
Sazali where their technical assistances are appreciated.
Last but not least, my appreciation to Universiti Malaysia Perlis (UniMAP) and Ministry of
Higher Education for offering me their Academic Staff Training Scheme (ASTS) fellowship to continue my post-graduate study.
ii
TABLE OF CONTENTS
Page
Acknowledgements ii
Table of Contents iii
List of Figures ix
List of Tables xiii
List of Plates xvi
List of Abbreviations xviii
List of Symbols xxii
Abstrak xxiii
Abstract xxvi
CHAPTER 1 - INTRODUCTION
1.1 General. 1
1.2 Water Quality of Rivers in Malaysia. 1
1.3 Sungai Pinang River Basin. 4
1.4 Sources of River Pollution. 6
1.5 Water Quality Management System. 9
1.6 Heavy Metals in River Water and Sediments. 10
1.7 Bioremediation study. 12
1.8 Problem statement. 14
1.9 Objectives of study. 15
1.10 Outline of Thesis Structure. 15
CHAPTER 2 – LITERATURE REVIEW
2.1 River Water Quality and Catchment Management. 17
2.2 Water Quality and Pollution of Rivers in Malaysia. 21
iii
2.2.1 Major Water Pollution of Rivers. 23
2.3 Sources of Pollution. 25
2.3.1 Point Sources 27
2.3.2 Non-point Sources 30
2.4 Water and Sediment Quality
2.4.1 Water Quality 37
2.4.2 Water Quality Assessment 37
2.4.3 Sediment Quality 38
2.4.4 Sediment Quality Assessment 40
2.4.5 Heavy Metals in the environment. 41
2.4.6 Sources of Heavy Metals 42
2.4.7 Toxicology of Heavy Metals 45
2.4.8 Heavy Metals Pollution Assessment 47
2.4.9 Pollution of Heavy Metals in the Environment 48
2.5 Bioremediation 49
2.5.1 Bioremediation of Heavy Metals in the Sediment 51
2.6 Summary of literature review. 53
CHAPTER 3 – MATERIALS AND METHODS
3.1 Study Area 55
3.2 Sampling location 55
iv
3.3 Water sampling methodology. 58
3.4 Water sample handling and analysis. 58
3.5 Water Quality Index (WQI) 60
3.6 Sediment samplings and handlings. 63
3.6.1 pH of sediments 64
3.6.2 Moisture content 64
3.6.3 Particle size distribution 64
3.6.4 Sediments total organic carbon 65
3.6.5 Nutrients content 65
3.6.6 Metal content 65
3.7 Sediment Quality Assessment 66
3.8 Identification of pollution sources. 70
3.9 Bioremediation treatment procedure.
3.9.1 Microbiological study. 70
3.9.2 River sediment characteristics. 71
3.9.3 Bacteria preparation. 71
3.9.4 Bacteria counting. 72
3.9.5 Bioremediation experimental design. 72
v
CHAPTER 4 – RESULTS AND DISCUSSION
4.1 Description of the study area. 74
4.1.1 River systems in the state of Penang. 74
4.1.2 Background of the Study Area. 75
4.1.3 Climate, Weather and Geological Characteristics of Study Area 78
4.1.4 Water Pollution in Sungai Pinang. 81
4.2 Water Quality Assessment. 82
4.2.1 Parameters classification on eight sampling locations of 82
Sungai Pinang catchment area during dry and wet seasons.
4.2.2 Parameter characteristics at eight sampling locations 90
in Sungai Pinang catchment.
4.2.3 Water quality index of selected sampling locations. 96
4.2.4 Correlation matrix of water quality parameters for 99
eight sampling locations during dry and wet seasons.
4.3 Sediment Quality.
4.3.1 Physical characteristics of sediment samples. 103
4.3.2 Chemical characteristics of sediment samples. 106
4.3.3 Correlation matrix of sediment quality parameters. 115
4.4 Land use and sources of pollution. 117
4.5 Heavy metals content in water and sediment of
Sungai Pinang and its tributaries.
vi
4.5.1 Heavy metals concentration in water and sediment 127
phases of selected sampling locations within Sungai Pinang.
4.5.2 Descriptive analysis of heavy metals in water and sediment 141
samples of selected locations within Sungai Pinang and
its tributaries.
4.5.3 Correlation coefficient matrix of heavy metals concentrations 145
with water quality parameters during dry and wet seasons, and
with sediment properties of Sungai Pinang and its tributaries.
4.5.4 Assessment of heavy metal contamination in water and 150
sediment samples of selected sampling locations within
Sungai Pinang compared to quality guidelines.
4.5.5 Assessment of heavy metals contamination in sediments of 155
sampling locations within Sungai Pinang and its
tributaries by using indices.
4.6 Bioremediation Study.
4.6.1 Identification of the unknown bacteria. 164
4.6.2 Bioremediation of heavy metals in sediment.
4.6.2.1 Characteristics of sediment sample for bioremediation of 168
heavy metals.
4.6.2.2 Bioremediation of heavy metals in sediment sample based 169
on different treatment techniques.
vii
CHAPTER 5 - CONCLUSIONS AND RECOMMENDATION 180
REFERENCES
APPENDICES
viii
LIST OF FIGURES
Page
Figure 1.1 Status of water quality monitored at selected river monitoring 2
stations in Malaysia
Figure 1.2 River water quality trend (2005-2009) 3
Figure 1.3 Sungai Pinang River Basin. 5
Figure 2.1 Components of IRBM 19
Figure 2.2 The distribution of the point source of water pollution 22
recorded by DOE in 2009.
Figure 2.3 Sources and sinks of heavy metals in environment. 43
Figure 2.4 Different microbial processes for metal uptake and 52
sequentration.
Figure 3.1 Sampling sites of the study area: Sungai Pinang and its 57
tributaries. Arrow indicates water flow direction.
Figure 4.1 Location of the study area within dotted red lines. 76
Figure 4.2 Geological map of the study area. 80
Figure 4.3 Water quality status for river basins of Peninsular Malaysia 81
in 2008.
Figure 4.4 Pollutant concentration patterns of DO, BOD5, COD, AN, pH and 84 TSS recorded by each sampling station within Sungai Pinang
during (a) dry and (b) wet seasons.
ix
Figure 4.5 The mean of water quality index recorded by selected sampling 97
location within Sungai Pinang River Basin for dry and
wet seasons.
Figure 4.6 pH value of sediment collected from selected locations 107
within Sungai Pinang river basin.
Figure 4.7 The percentage of moisture content measured in sediment 108
from Sungai Pinang and its tributaries.
Figure 4.8 The percentage of total organic carbon in sediment taken 110
Sungai Pinang and its tributaries.
Figure 4.9 The amount of total Kjeldahl nitrogen (TKN) measured in 112
sediment taken from Sungai Pinang and its tributaries.
3- Figure 4.10 Pollutant concentration pattern of phosphorus (PO4 ) in sediment 113 collected from Sungai Pinang and its tributaries.
Figure 4.11 Types of sewage treatment plants in study area. 122
Figure 4.12 Locations of sewage treatment plants within the study area. 124
Figure 4.13 Type of industries identified within Sungai Pinang and its 125
tributaries.
Figure 4.14 a The mean concentrations of cadmium in water samples of 129
Sungai Pinang and its tributaries during dry and rainy seasons.
Figure 4.14 b The mean concentrations of cadmium in sediment samples 129
of Sungai Pinang and its tributaries.
x
Figure 4.15 a The mean concentrations of lead in water samples of Sungai 131
Pinang and its tributaries during dry and rainy seasons.
Figure 4.15 b The mean concentrations of lead collected from sediment 132
samples of Sungai Pinang and its tributaries.
Figure 4.16 a The mean concentrations of zinc in water samples of Sungai 134
Pinang and its tributaries during dry and rainy seasons.
Figure 4.16 b The mean concentrations of zinc in sediment samples of Sungai 134
Pinang and its tributaries.
Figure 4.17 a The mean concentrations of copper in water samples of Sungai 138
Pinang and its tributaries during dry and rainy seasons.
Figure 4.17 b The mean concentrations of copper in sediment samples of Sungai 138
Pinang and its tributaries.
Figure 4.18 a The mean concentrations of iron in water samples of Sungai 139
Pinang and its tributaries during dry and rainy seasons.
Figure 4.18 b The mean concentrations of iron in sediment samples of Sungai 140
Pinang and its tributaries.
Figure 4.19 The boxplots of Cd, Pb, Cu, Zn and Fe in water samples from 8 142
sampling locations during (a) dry and (b) wet seasons.
Figure 4.20 Boxplots of Cd, Pb, Zn, Cu and Fe in sediment collected from 144
eight sampling locations within Sungai Pinang and its tributaries.
xi
Figure 4.21 The enrichment factor of heavy metals in sediment of eight 156
sampling locations.
Figure 4.22 The average geoaccumulation index of Sungai Pinang and its 158
tributaries.
Figure 4.23 The pollution load index of heavy metals in sediment of Sungai 161
Air Hitam 3 (SAH3), Sungai Air Putih (SAP), Sungai Dondang
(SD), Sungai Air Hitam 2 (SAH2), Sungai Air Hitam 1 (SAH1),
Sungai Air Terjun (SAT), Sungai Jelutong (SJ) and
Sungai Pinang (SP).
Figure 4.24 The modified degree of contamination of heavy metals in 163
sediment of eight sampling locations within Sungai Pinang.
Figure 4.25 Identification of (a) Rhodococcus erythropolis and (b) Bacillus 167
cereus using rRNA sequences.
Figure 4.26 Remediation of heavy metals by natural attenuation technique 170
in non-sterilized sediment sample.
Figure 4.27 Remediation of heavy metals based on bioaugmentation 172
techniques on sterilized sediment sample.
Figure 4.28 Remediation of heavy metals based on bioaugmentation 173
techniques on non-sterilized sediment sample.
Figure 4.29 Conceptual model of biological degradation processes in the soil. 179
xii
LIST OF TABLES
Page
Table 1.1 Statutory point and nonpoint sources of pollution 6
Table 2.1 Typical pollutants, sources and related impacts. 26
Table 2.2 EPA’s Conventional and Non-conventional Pollutants Categories. 30
Table 2.3 Potential anthropogenic sources of selected trace elements in the 44 environment.
Table 2.4 Potential health effects caused by some metals found in human 46
body fluids.
Table 2.5 A summary of species most commonly affected by toxicities of 47
selected trace elements.
Table 3.1 Details of the location of sampling points of the rivers within 56
Sungai Pinang river basin.
Table 3.2 Parameters tested and method of analysis. 59
Table 3.3 Best-fit equations for the estimation of various sub-index values. 61
Table 3.4 DOE water quality classification based on water quality index. 62
Table 3.5 DOE water quality index classification. 62
Table 3.6 Water classes and uses. 63
Table 3.7 Enrichment factor (EF) values in relation to enrichment indicator. 67
Table 3.8 Geoaccumulation index (Igeo) in relation to pollution category. 68
Table 3.9 The contamination level of metals and their intensities. 68
xiii
Table 3.10 The classification and description of the modified degree of 69 contamination.
Table 4.1 River basin and its tributaries in the state of Penang. 74
Table 4.2 Water quality index for river basins in Penang. 75
Table 4.3 The sub-districts of Sungai Pinang catchment area. 77
Table 4.4 Physical parameters of Sungai Pinang river basin. 78
Table 4.5 Seasons and months during the study area. 79
Table 4.6 Pollutant concentrations of parameters tested during dry and wet 91
seasons by selected sampling stations within Sungai Pinang.
Table 4.7 Correlation matrix of water quality parameters of selected 100
sampling locations during (a) dry and (b) wet seasons.
Table 4.8 The particle size distribution of sediment collected from Sungai 104
Pinang and its tributaries.
Table 4.9 Correlation matrix of sediment chemical parameters of selected 115
sampling locations within Sungai Pinang catchment.
Table 4.10 List of land use identified within sampling locations. 119
Table 4.11 Correlation matrix of elements and water quality parameters 146
of eight sampling locations during (a) dry and (b) wet seasons.
Table 4.12 Correlation coefficient matrix between the concentrations 148
of heavy metals and sediment properties of Sungai Pinang
and its tributaries.
xiv
Table 4.13 Mean concentrations of elements in water obtained from 151
sampling locations during dry and wet seasons with comparison
to water quality standards.
Table 4.14 The average of heavy metal concentrations in sediment of 154
selected sampling locations and its comparison with sediment
quality guidelines.
Table 4.15 The contamination factor of cadmium, lead, zinc, copper and 160
iron in sediment of eight sampling stations.
Table 4.16 The physical-chemical properties of sediment samples. 168
Table 4.17 Mean of total percentage of elements reduction within study 175
period according to element tested, treatment and bacteria dosage.
xv
LIST OF PLATES
Page
Plate 4.1 The untreated wastewater from slaughterhouse released into 86
the river.
Plate 4.2 A sewer pipe that discharge domestic wastewater effluent into 94
the river.
Plate 4.3 Sediment sample collected at Sungai Pinang during sampling 106
activities.
Plate 4.4 Floatable solid wastes seen at the Sungai Pinang. 113
Plate 4.5 Wastes from food stall, restaurant, car wash center and 120
automobile workshop located in the sampling locations
discharged into the drain.
Plate 4.6 Location of slaughterhouse (in red ring) adjacent to Sungai 121
Pinang discharged its wastes containing fats, bloods and light
solid matters into the river.
Plate 4.7 Floatable solid wastes in the river trapped at the trash boom 127
in Sungai Pinang.
Plate 4.8 The municipal wastewater discharged from the drains into 136
the river.
Plate 4.9 Bacterial shapes of (a) coccus sp. and (b) basillus sp. are 166
clearly seen after using staining technique.
xvi
APPENDICES
Appendix A- Water quality parameters of Sungai Pinang and its tributaries during dry and rainy seasons.
Appendix B- Physical and chemical characteristics of sediment samples collected from selected locations within Sungai Pinang.
Appendix C- List of pollution sources within Sungai Pinang and its tributaries.
Appendix D- The heavy metal concentrations in water and sediment samples of Sungai Pinang and its tributaries.
Appendix E- Bioremediation study of sediment contaminated with heavy metals.
xvii
LIST OF ABBREVIATIONS
AN Ammoniacal Nitrogen
ANZECC Australian and New Zealand Environment and Conservation Council
APHA American Public Health Association
ARMCANZ Agriculture and Resource Management Council of Australia and New
Zealand
BOD Biochemical Oxygen Demand
CCC Criteria Continuous Concentration
CCME Canadian Council of Ministers of the Environment
CMC Criteria Maximum Concentration
COD Chemical Oxygen Demand
DEAT Department of Environmental Affairs and Tourism
DF Dilution Factor
DFID Department of International Development
DID Department of Drainage and Irrigation
DO Dissolved Oxygen
DOC Dissolved Organic Carbon
DOE Department of Environment
DWAF Department of Water Affairs and Forestry
EB L14 Endophytic Bacteria L14
EC Electrical Conductivity
xviii
EDPHK Environmental Protection Department, the Government of Hong
Kong
EPA Environmental Protection Agency
ES Average Shales
FAAS Flame Atomic Spectrophotometer
FP Fine Particles
GEC Glisten Environmental Consultants
INWQS Interim National Water Quality Standards
IRBM Integrated River Basin Management
IST Individual Septic Tank
ISQG Interim Sediment Quality Guidelines
IWK Indah Water Consortium
JCSS Jelutong Central Sewerage System
LCEL Lower Chemical Exceedance Level
MC Moisture Content
MCo Municipal Council
MPPP Majlis Perbandaran Pulau Pinang
NA Natural Attenuation
NGOs Non-Government Organizations
NHDES New Hampshire Department of Environmental Services
PAHs Poly-Aromatic Hydrocarbons
xix
PAI Pesticide Active Ingredients
PCBs Polychlorinated Biphenyl
PE Population Equivalents
PEL Probable Effect Levels
POC Particulate Carbon
SOD Sediment Oxygen Demand
SS Suspended Solids
STP Sewerage Treatment Plant
SQGs Sediment Quality Guidelines
TDS Total Dissolved Solids
THM Trihalomethane
TKN Total Kjeldahl Nitrogen
TOC Total Organic Carbon
TSS Total Suspended Solid
USDA United States Department of Agriculture
USEPA United State Environmental Protection Agency
UAE United Arab Emirates
UCEL Upper Chemical Exceedance Level
WDNR Wisconsin Department of Natural Resources
WHO World Health Organization
xx
WQI Water Quality Index
WRC Water Research Commission
WWF World Wildlife Fund
xxi
LIST OF SYMBOLS x weight before drying (g) y weight after drying (g)
C total metal concentration (mg/kg)
R concentration read with AAS (mg/L) v volume of balance of nitric acid and hydrogen peroxide (mL)
W weight of sediment sample (g)