EFFECTS OF LANDUSE CHANGES TO WATER QUALITY AND GREEN MUSSELS (Perna viridis) DUE TO DEVELOPMENT ALONG DANGA-PENDAS COASTAL AREA NORLIYANA BINTI ADNAN A project report submitted in partial fulfillment of the requirements for the award of the degree of Master of Engineering (Civil - Environmental Management) Faculty of Civil Engineering Universiti Teknologi Malaysia November 2009 iii DEDICATION “…To Whom I Love and Those Who Love Me…” I sorrowfully dedicate this project to loving memory of my mother, grandmother and grandfather Mak, Tok and Aki May their souls rest in peace Special dedicate to my beloved parent, sisters and little brother. Abah, Along, K. Linda, K. Ayu, K. Awin, Wan and family My sweetheart Syed and Friends for all the love, prayers, sacrifices, patience, supports and encouragement iv ACKNOWLEDGEMENT Alhamdullillah… First of all I thank the almighty Allah for his endless Grace and Blessing on me to fulfill this project. For the successful of this work and my study, I am entirely indebted to many their love, support, sacrifices and encouragement. First and foremost, I would like to express my heartfelt gratitude to my Project Supervisor Dr. Shamila Azman for the guidance, constant encouragements and invaluable help given to me during my project study. I am also very thankful to my co-supervisor, Assoc. Prof Dr. Razali Ismail for his support. The assistance and co-operation during this study, provided by the staffs of the Faculty of Civil Engineering and Faculty of Science, UTM, especially Mr. Mohd. Daniel is also deeply acknowledged. Special thanks are extended to all lecturers of Environmental Engineering Department, master and undergraduate students who as direct and indirectly involved in this project and study. Also, I would like to thank to all my course mate for MAK 2008/2009 for their supports. I would also like to thank my parents, sisters and brother for their prayers and encouragement. The love, patience, supports and encouragement by my dearest, also gratefully acknowledged. Last, but not least, I would like to thank all the wonderful individuals who have, one way or another, generously contributed their knowledge, expertise and talents. v ABSTRACT The effects of landuse changes have become significant with reduction in water quality and thus affecting aquatic life in their ecosystem. A large area in Johor Straits starting from Singapore-Malaysia Second Link Bridge to Danga Bay have been identified as a suitable location for the expansion of mussels and caged-fish industries by the National Fisheries Institute of Malaysia. However, this area has been chosen as a part of the massive development projects of Iskandar Development Region (IDR). Therefore this would definitely increase the level of pollutants in coastal water. The objectives of this study are to determine the effects of landuse changes to water quality along this river as well as to analyze the effects of water quality on green mussels (Perna viridis). This study was carried out along DangaPendas coastal area with eleven sampling points for water quality and four mussels sampling points. Study parameters include dissolved oxygen (DO), temperature, salinity, pH, ammoniacal nitrogen, total dissolved solid (TDS), biochemical oxygen demand (BOD), chemical oxygen demand (COD) and heavy metals for zinc, lead, cadmium and nickel. Sampling was carried out from November 2008 to April 2009. All water and mussels samples were then analyzed in laboratory based on the standard procedures. In order to observe the variation on landuse change, satellite image; Landsat TM and ETM for year 1991, 2000, 2005 and 2008 were used. Processes includes geometric correction, atmospheric correction, images classification and change detection were carried out for each image to obtain the final output of landuse changes statistics. Results obtained from the processes and laboratory analysis indicate that there were reduction in water quality especially in heavy metals when compared to Interim National Water Quality Standard (INWQS) and Interim National Marine Water Quality Standard (INMWQS) with increased of build-up and open area due to development. Lead and cadmium recorded in green mussel were mostly higher than the permissible limit allowed by Malaysian Food Regulation 1985 whereas zinc concentration was below than the limit. Generally, there are significant relationship between landuse and water quality and thus with green mussel. As development increased, quality of water decreased and heavy metals accumulation in green mussel were also increased. The severity of the water quality along study area was classified as slightly polluted and proper management and prevention planning should be carried out to preserve the coastal environment. vi ABSTRAK Kesan perubahan gunatanah amat berkait rapat dengan penurunan kualiti air dan secara tidak langsung mempengaruhi ekosistem hidupan akuatik. Kawasan sepanjang Selat Tebrau dari Jambatan Link-Kedua Malaysia-Singapura hingga ke Teluk Danga telah dikenal pasti sebagai kawasan yang sesuai bagi perkembangan industri kupang dan ikan sangkar oleh Lembaga Kemajuan Ikan Malaysia. Namun demikian, kawasan ini juga telah dipilih sebagai salah satu kawasan pembangunan besar-besaran dibawah Wilayah Pembangunan Iskandar (WPI) yang dijangka akan meningkatkan bahan cemar ke dalam air di pesisiran pantai tersebut. Objektif kajian ini adalah untuk menganalisis kesan perubahan gunatanah terhadap kualiti air dan analisa kesan kualiti air terhadap kupang hijau (Perna viridis). Kajian ini telah dijalankan di sepanjang kawasan persisiran Danga-Pendas merangkumi 11 stesen persampelan air dan empat stesen persampelan kupang. Parameter yang terlibat dalam kajian ini adalah oksigen terlarut (DO), suhu, kemasinan, pH, nitrogen ammonia, jumlah pepejal terlarut (TDS), permintaan oksigen biokimia (BOD), permintaan oksigen kimia (COD) dan logam berat seperti zink, plumbum, cadmium dan nikel. Kajian ini telah dijalankan pada November 2008 hingga April 2009. Kesemua sampel air dan kupang dianalisis di makmal berdasarkan kaedah piawai. Dalam memantau variasi perubahan guna tanah, imej satelit, Landsat TM dan ETM bagi tahun 1991, 2000, 2005 dan 2008 telah digunakan. Proses seperti pembetulan geometri, pembetulan atmosfera, topengan, pengkelasan imej dan penentuan perubahan telah dijalankan bagi mendapatkan hasil akhir statistik perubahan guna tanah di kawasan kajian. Hasil yang diperolehi dari pemprosesan dan analisis makmal menunjukkan penurunan terhadap kualiti air terutama bagi logam berat dibandingkan dengan Interim National Water quality Standard (INWQS) dan Interim National Marine Water Quality Standard (INMWQS) dengan penambahan kawasan pembangunan bandar dan kawasan terbuka. Pada masa yang sama juga, plumbum dan kadmium yang direkodkan dalam kupang kesemuanya adalah melebihi tahap minimum berbanding Malaysian Food Regulation 1985 manakala kandungan zink adalah kurang dari tahap tersebut. Secara amnya, terdapat kaitan antara perubahan guna tanah terhadap kualiti air dan kupang. Dengan penambahan pembangunan, terdapat penurunan terhadap kualiti air dan logam berat yang menumpuk dalam kupang juga bertambah. Dari pemerhatian, tahap pencemaran air di sepanjang kawasan kajian adalah sedikit tercemar dan pengurusan and pelan pencegahan yang sewajarnya haruslah dilakukan bagi memelihara kawasan persekitaran persisiran pantai ini. vii CONTENT CHAPTER 1 TITLE PAGE DECLARATION ii DEDICATION iii ACKNOWLEDGEMENT iv ABSTRACT v ABSTRAK vi CONTENTS vii LIST OF TABLES xiii LIST OF FIGURES xv LIST OF ABBREVIATIONS xix LIST OF APPENDICES xxi INTRODUCTION 1.1 Introduction 1 1.2 Problem Statement 3 1.3 Objectives 4 1.4 Scope of Study 5 1.5 Significant of Study 6 viii 2 LITERATURE REVIEW 2.1 Introduction 7 2.2 Danga – Pendas Coastal Area 7 2.2.1 9 Water Quality at Danga- Pendas Coastal Area 2.2.2 The Distribution of P.viridis 10 at Danga-Pendas coastal area 2.2.3 Existing and Future Planning Landuse 12 2.3 Iskandar Development Region (IDR) 13 2.4 Landuse Impact to Water Quality 16 2.5 Water Quality Parameters and Heavy Metals 17 2.5.1 Dissolved Oxygen (DO) 17 2.5.2 Temperature 18 2.5.3 pH 19 2.5.4 Salinity 20 2.5.5 Total Dissolved Solid (TDS) 20 2.5.6 Biochemical Oxygen Demand (BOD) 21 2.5.7 Chemical Oxygen Demand (COD) 21 2.5.8 Nutrients 22 2.5.8.1 Ammoniacal nitrogen 22 Heavy Metals 23 2.5.9.1 Nickel (Ni) 23 2.5.9.2 Zinc (Zn) 24 2.5.9.3 Lead (Pb) 24 2.5.9.4 Cadmium (Cd) 25 2.5.9 2.6 Water Quality Standard 25 2.6.1 26 Interim National Water Quality Standard (INWQS) 2.6.2 Interim National Marine Water Quality 26 Standard (INMWQS) 2.6.3 2.7 Water Quality Index (WQI) 27 Asian Green Mussel, Perna viridis 28 2.7.1 31 P.viridis as Bioindicator and ix Biomonitor 2.7.2 Heavy Metal Contamination on Green 32 Mussels (Perna viridis) 2.7.3 Studies of Heavy Metal Contaminants in 33 Green Mussels at Johor Rivers and Estuaries 2.8 Remote Sensing and Geographic Information 34 System (GIS) 2.8.1 Remote Sensing 34 2.8.1.1 Remote Sensing Data Landsat 39 Thematic Mapper (TM) and Enhanced Thematic Mapper (ETM) 2.8.2 2.9 3 Geographic Information System (GIS) 41 Integration of Remote Sensing and GIS 42 2.9.1 Landuse Monitoring Using Satellite Data 43 2.9.2 Landuse Change Detection 44 METHODOLOGY 3.1 Introduction 45 3.2 Literature Review 45 3.3 Data Collection and Sampling 46 3.4 Sampling Processes and Laboratory Analysis 46 3.4.1 Study Area and Sampling Stations 47 3.4.2 Sampling Frequency and Parameters 50 Analyzed 3.4.3 Sampling Techniques 51 3.4.4 Laboratory Analysis 52 3.4.4.1 Sample Pretreatment 52 3.4.4.2 Laboratory Analysis for BOD, 53 COD and Ammoniacal Nitrogen 3.4.4.3 Laboratory Analysis for Heavy Metals 3.5 54 Integrated Remote Sensing and GIS 55 3.5.1 55 Remote Sensing Data, Landsat TM x 3.5.2 4 Landuse Extraction from Satellite Imagery 57 3.5.2.1 Geometric Correction 58 3.5.2.2 Atmospheric Correction and Masking 59 3.5.2.3 Subset 60 3.5.2.4 Image Classification 60 3.5.3 Landuse Change Detection 61 3.7 Flowchart of Methodology 63 EFFECT OF LANDUSE ON WATER QUALITY 4.1 Introduction 64 4.2 Landuse Classification 64 4.2.1 Landuse Classification for 1991 65 4.2.2 Landuse Classification for 2000 66 4.2.3 Landuse Classification for 2005 67 4.2.4 Landuse Classification for 2008 68 4.3 Landuse Change Detection 69 4.3.1 Differential in 1991 and 2008 images 70 4.3.2 Statistical Difference 74 4.3.2.1 Statistical Changes Report for 75 1991 and 2005 4.3.2.2 Statistical Changes Report for 76 2005 and 2008 4.4 Analysis of Water Quality 77 4.4.1 77 Physical and Chemical Water Quality Parameters 4.4.1.1 Dissolved Oxygen (DO) 78 4.4.1.2 Temperature 79 4.4.1.3 Salinity 79 4.4.1.4 pH 81 4.4.1.5 Total Dissolved Solids (TDS) 82 4.4.1.6 Ammoniacal Nitrogen 82 4.4.1.7 Biochemical Oxygen Demand (BOD) 83 xi 4.4.2 4.5 4.4.1.8 Chemical Oxygen Demand (COD) 85 Heavy Metals 86 4.4.2.1 Zinc (Zn) 86 4.4.2.2 Lead (Pb) 88 4.4.2.3 Cadmium (Cd) 89 4.4.2.4 Nickel (Ni) 90 Analysis of Previous Water Quality Data Compared 92 to Present Data 4.6 Analysis on the Effects of Landuse Change to 99 Water Quality along Danga-Pendas coastal area 5 EFFECT OF WATER QUALITY ON GREEN MUSSELS (Perna viridis) 5.1 Introduction 102 5.2 Analysis on Effects of Water Quality on Green 102 Mussels Vs Water Samples 5.2.1 5.2.2 5.3 Physical Parameters 103 5.2.1.1 Dissolved Oxygen (DO) 103 5.2.1.2 Salinity 104 5.2.1.3 Temperature 105 5.2.1.4 pH 107 5.2.1.5 Total Dissolved Solids (TDS) 108 5.5.1.6 Ammoniacal Nitrogen 109 5.5.1.7 Biochemical Oxygen Demand (BOD) 110 5.5.18 Chemical Oxygen Demand (COD) 111 Heavy Metals 111 5.2.2.1 Cadmium (Cd) 112 5.2.2.2 Lead (Pb) 114 5.2.2.3 Zinc (Zn) 115 Comparison of Cd, Pb and Zn Concentrations 117 in P.viridis from Previous Studies 5.4 Effects of Water Quality on Green Mussel 122 xii 6 CONCLUSIONS AND RECOMMENDATIONS 6.1 Conclusions 124 6.2 Recommendations 126 REFERENCES 128 Appendix A – D 145 - 162 xiii LIST OF TABLES TABLES NO. TITLE PAGE 2.1 Salinity represents the types of water. 20 2.2 INWQS Classification 26 2.3 DOE- INMWQS parameters and standard 27 2.4 Water Quality Index 28 2.5 Scientific classification of Perna viridis 28 2.6 Description of seven elements in remote sensing 36 Processes 2.7 Landsat satellite sensor characteristic and specification 39 2.8 Landsat’s band descriptions 40 3.1 Data collection and sampling 46 3.2 Coordinates of the eleven sampling stations at the study area 48 3.3 Date of sampling 51 3.4 Recommended condition for Flame Atomic Absorption 55 Spectrophotometer 3.5 Landsat TM Specifications 57 3.6 Projection specifications 59 3.7 Coordinates for image subset. 60 4.1 Overall statistical landuse for 1991, 2000, 2005 75 and 2008 4.2 Statistical changes based on landuse types between 76 2005 and 1991 4.3 Statistical changes based on landuse types between 77 2005 and 2008 4.4 Water quality data for year 1991, 2006 and 2009 5.1 Guidelines of maximum permissible limits of heavy 94 118 xiv metals (µg/g) in seafood from different countries 5.2 Mean concentration of Cd, Pb and Zn in P.viridis collected from Pantai Lido in present and previous studies. 119 xv LIST OF FIGURES FIGURE NO. 2.1 TITLE PAGE (a) Location of Danga-Pendas coastal area 8 (b) Developed Danga coastal area (c) Mangrove along Pendas coastal area (d) Development progress of IDR near coastal area of Nusajaya. 2.2 Figure shows the tributaries which empty into 9 Danga – Pendas coastal area. 2.3 (a) Green mussels harvested area from satellite view. 11 (b) and (c) show the harvested mussels along Danga-Pendas Area. 2.4 Existing landuse along Danga-Pendas coastal area 12 2.5 Existing landuse types along Danga-Pendas. 13 2.6 Proposed land use under IDR 14 2.7 Proposed for major development of coastal zone 15 under Iskandar Development Region 2.8 Development of IDR near Tebing Runtuh 16 2.9 Green Mussel 29 2.10 The geographical distribution of P.viridis worldwide 30 2.11 Seven elements in remote sensing processes consisting of 35 A is energy source or illumination, B is radiation and the atmosphere, C is interaction with the target, D is recording of energy by the sensor, E is transmission, reception and processing, F is interpretation and analysis and G is applications 2.12 Example of (a) spatial variations (b) spectral 38 xvi resolution and (c) temporal resolution in remote sensing data. 2.13 Data integration from different forms of input through GIS 42 3.1 Flowchart of sampling and laboratory works 47 3.2 Location of study area with eleven sampling stations 48 3.3 Sampling station S2 at Sungai Danga estuary 49 3.4 Sampling station M1 for mussels collection station near 49 Sungai Melayu estuaries 3.5 Sampling stations M3 for mussel’s collection 50 3.6 Sampling station M4 and S9 near Nusajaya area 50 3.7 (a) YSI-USA multiparameter probe (b) HACH DR 54 5000 Spectrophotometer for water quality analysis 3.8 Perkin Elmer model Analyst 400 Atomic Absorption 54 Spectrometer 3.9 Landsat TM and ETM images 56 3.10 Flowchart of Landuse Classification 58 3.11 Flowchart of Landuse Change Detection. 62 3.12 Overall flowchart of methodology 63 4.1 Landuse classification for 1991 66 4.2 Landuse classification for 2000 67 4.3 Landuse classification for 2005 68 4.4 Landuse classification for 2008 69 4.5 Series of landuse types at Johor Bahru city center 71 4.6 Series of landuse information at Sungai Danga and 72 Sungai Skudai estuaries. 4.7 Series of landuse information at Nusajaya. 73 4.8 Landuse information at Sungai Pendas coastal area. 74 4.9 DO concentration measured at station S1 to S11 from 78 November 2008 to April 2009. 4.10 Temperature level measured at station S1 to S11 from 79 November 2008 to April 2009. 4.11 Salinity measured at station S1 to S11 from November 80 2008 to April 2009. 4.12 pH measured at station S1 to S11 from November 2008 81 xvii to April 2009. 4.13 TDS concentration measured at station S1 to S11 from 82 November 2008 to April 2009. 4.14 Ammoniacal nitrogen concentration measured at station 83 S1 to S11 from November 2008 to April 2009. 4.15 BOD concentration measured at station S1 to S11 from 84 November 2008 to February 2009. 4.16 COD concentration measured at station S1 to S11 from 86 November 2008 to February 2009. 4.17 Zinc concentration measured at station S1 to S11 from 87 November 2008 to April 2009. 4.18 Lead concentration measured at station S1 to S11 from 89 November 2008 to April 2009. 4.19 Cadmium concentration measured at station S1 to S11 90 from November 2008 to April 2009. 4.20 Nickel concentration measured at station S1 to S11 from 91 November 2008 to April 2009. 4.21 Water quality data at Danga and Pendas area for year 1991, 96 2006 and 2009 (a) pH (b) temperature (c) DO and (d) ammoniacal nitrogen (AN). 4.22 Heavy metals concentration data at Danga and Pendas 98 area for year 1991, 2006 and 2009 (a) zinc (b) cadmium (c) lead and (d) nickel. 4.23 Concentration of manufacturing in and outer of 100 Johor Bahru. 5.1 DO concentration at mussel sampling stations, M1 to 104 M4 from November 2008 to April 2009. 5.2 Salinity level at mussel sampling stations, M1 to M4 from 105 November 2008 to April 2009. 5.3 Water temperature at mussel sampling stations, M1 to 106 M4 from November 2008 to April 2009. 5.4 pH at mussel sampling stations, M1 to M4 from November 107 2008 to April 2009. 5.5 TDS concentration at mussel sampling stations, M1 to 108 xviii M4 from November 2008 to April 2009. 5.6 Ammoniacal nitrogen concentration at mussel sampling 109 stations, M1 to M4 from November 2008 to April 2009. 5.7 BOD concentration at mussel sampling stations, M1 to M4 110 from November 2008 to February 2009. 5.8 COD concentration at mussel sampling stations, M1 to 111 M4 from November 2008 to April 2009. 5.9 Cadmium concentration in water and P.viridis samples at 113 mussel sampling stations, M1 to M4 from November 2008 to April 2009. 5.10 Lead concentration in water and P.viridis samples at mussel 114 sampling stations, M1 to M4 from November 2008 to April 2009 5.11 Zinc concentration in (a) water and (b) P.viridis samples 116 at mussel sampling stations, M1 to M4 from November 2008 to April 2009. 5.12 Cadmium concentration in P.viridis samples at Pantai Lido 120 from 1991 to 2009 5.13 Lead concentration in P.viridis samples at Pantai Lido 121 from 1991to 2009. 5.14 Zinc concentration in P.viridis samples at Pantai Lido from 1991to 2009. 121 xix LIST OF ABBREVIATIONS µg - micro gram AN - Ammoniacal nitrogen BOD - Biochemical Oxygen Demand Cd - Cadmium COD - Chemical Oxygen Demand DDDW - Double Distilled Deionised Water DEIA - Detail Environmental Impact Assessment DN - Digital Number DO - Dissolved Oxygen DOE - Department of Environment DOF - Department of Fisheries ETM - Enhanced Thematic Mapper g - gram GCP - Ground Control Point GIS - Geographic Information System GPS - Global Positioning System ha - Hectares IDR - Iskandar Development Region INMWQS - Interim Marine National Water Quality Standard INWQS - Interim National Water Quality Standard JUPEM - Jabatan Ukur dan Pemetaan Malaysia m - meter MACRES - Malaysia Center for Remote Sensing mg - milligram Mid-IR - Middle Infrared NA - Not Available NH3 - Ammonia xx Ni - Nickel NIMPIS - National Introduced Marine Pest Information System NIR - Near Infrared NO2 - Nitrite NO3 - Nitrate NST - New Straits Times P.viridis - Perna viridis Pb - Lead ppm - part per million ppt - part per thousand RADAR - Radio Detection and Ranging ROI - Region of Interest RSO - Rectified Skew Orthomorphic SEC - Special Economic Corridor SJER - South Johor Economic Region SPOT - Systeme pour l’Observation de la Terre TDS - Total Dissolved Solids TM - Thematic Mapper US EPA - United State Environmental Protection Agency USGS - United State Geological Survey WQ - Water quality WQI - Water Quality Index xxi LIST OF APPENDICES APPENDIX TITLE PAGE A Water Quality Standard 145 B Laboratory Analysis 147 C Accuracy Assessment for Landuse Classification 152 D Water Quality Data 154 CHAPTER 1 INTRODUCTION 1.1 Introduction Landuse changes are very significance with changes from pure green land area to developed urban area. Most of the countries in the world face the same dilemma where the initial landuse have to be transformed as the populations, technologies and economics increases. In Malaysia, landuse has undergone many changes since the country achieved its independence in 1957. Landuse changes were driven by a number of economical, socio-political and biophysical factors. Over the last two decades, the evolution of landuse became drastic in the urban and rural areas. Especially, more land areas have been displaced or converted to nonagricultural activities particularly for industry, housing and commercial activities (Khaled, 2005). In Malaysia, for example, the total urban population has increased to 59 percent in the year 2000 (Hadi, 2000) and some of the states in Peninsular Malaysia has achieved the urbanization level of developed countries with 80 percent of total population. Foreign and local investment in the agricultural, commercial and mining sectors are the main factors leading to the growth of urban population in Malaysia. Most urban areas in developing countries are located on the coast or on major rivers in Malaysia. The uncontrolled growth of urban development has adversely affected Malaysian river basin ecosystems (Jahi and Nordin, 1996). The same problem is being faced in Johor, it is one of the most developed state in Malaysia and the one 2 closest to Singapore, it also faces massive development especially along the coastal area in South of Johor. One of the projects under rapid progress which lead to rapid changes in landuse, water quality and aquaculture life is the development of Iskandar Development Regions (IDR). Iskandar Development Regions or also known as South Johor Economic Region (SJER) is a developing corridor in the South Johor region. From a physical planning perspective, SJER is defined as a geographic area in the southern part of Johor that will benefit from economic opportunities that will be promoted within the region. Iskandar Malaysia is planned to become Southern Peninsular Malaysia’s most developed region where it includes living, entertainment, environment and business (SJER CDP, 2006). The new development of SJER will cause massive impact to water quality of the river along the area involved. The Johor Straits waterway leads into two open waters which are the Straits of Malacca on the west and the South China Sea on the east (SJER CDP, 2006). Specifically, it will affect the discharge to the nearest river at Johor Straits such as Sungai Melayu, Sungai Pendas and Sungai Skudai. This may be one of the contributing factor to drastic reduction in water quality. The changes of water quality will also affect the aquatic life living in the river along this area such as the green mussel. Green mussels (Perna viridis) occur widely in shallow waters along the west coast of Peninsular Malaysia. It have become a food resource and Malaysia once exporter green mussel. The green mussel is harvested commercially in the IndoPacific region as a human food resource due to its dense and fast growth (Knott and De-Victor, 2007). P.viridis can have economic, ecological and human health impact. Human consume mussels as it is a cheap source of protein and tasty. Besides of economic importance, it is also edible therefore analysis of mussels is important to provide information about possible contaminants or toxicity level that may harm public health. Green mussel is important as a bioindicator because it is an efficient filter feeder and has been used widely as bio-indicator species for pollutants (Sivalingam, 1977). P. viridis has become the best candidate for bioindicator surveys in South-East Asia since 1980’s (Phillips, 1980). While, other important factor which had led to the use of green mussels as a biomonitoring agent for heavy metals is that 3 they are commercially an important seafood species worldwide (Farrington et al., 1987). 1.2 Problem Statement Currently, the coastal area of Danga-Pendas is affected by rapid development of Danga Bay and Iskandar Development Region (IDR). These massive developments will cause changes in landuse types along this area. The changes in landuse also affect the water quality of rivers, estuaries and coastal water. This is due to the discharge from industry, agriculture or sewage such as suspended sediments, pathogens, nutrients, heavy metals and oil. Urban areas also diffuse sources of suspended sediments, pathogens, nutrients and pesticides in agricultural land uses. Many of these anthropogenic influences are part of a larger process of catchment landuse change that can affect water quality in both rivers and lakes as well as downstream estuarine and coastal waters. IDR is a developing corridor in the South Johor region. IDR covers a land size of 2217 sq. km which is estimated to have 1.35 million people or 43% of Johor’s population. Four of five Flagship Zones of the focal points in IDR will be located in the Nusajaya-Johor Bahru-Pasir Gudang corridor also known as the Special Economic Corridor (SEC). The development of newly developing IDR will cause massive impact to river water quality along this area. It will affect the discharge to the nearest river such as Sungai Melayu, Sungai Pendas and Sungai Skudai. Effluent from several polluted rivers in Johor Bahru such as Sungai Melayu, Sungai Skudai and Sungai Segget may also be one of the contributing factor to the drastic reduction in water quality. Water quality of these rivers will decrease with increase of nutrients and heavy metals. From previous studies carried out by Department of Environment (DOE), the Water Quality Index (WQI) for Sungai Danga and Sungai Skudai were classified as Class III according to DOE-WQI. The main pollutants are organics, ammoniacal 4 nitrogen, nitrate, phosphate, faecal coliform and a number of heavy metals such as iron, nickel and mercury which are above the levels recommended by the proposed Interim National Marine Water Quality Standards (INMWQS) (DOE, 2007). The new developing SJER will boost up the pollutants such as nutrient and heavy metal discharge to these rivers thus resulting in reduction of water quality and low WQI. The changes of water quality will also affect the aquatic lives living in the river along this area such as green mussel. Green mussel has been identified as potential organism for aquaculture in Pacific Island (Uwate et al., 1984). In Malaysia, Johor is the largest state producing P.viridis and produces approximately 92% of total mussel’s production. The National Fisheries Institute of Malaysia have identified a large area in Johor Straits estuaries starting from the Singapore-Malaysia second link to Danga Bay as a suitable area for the expansion of mussels and caged-fish industry. P.viridis occurs in estuarine or coastal water which are rich with plankton, warm water in range of 26 to 32˚C with high salinity around 27-33 ppt (Hickman, 1989; Power, 2004).The growth rates of P.viridis are mostly influenced by environmental factor such as temperature, food availability such as chlorophyll and also water movement. Generally, the pollution from the effluent may affect changes in the condition of water quality along this area. Specifically, valuable water ecosystems in this area especially green mussel, P.viridis will also be affected. Thus it will disrupt the growth and reduces the production rate of P.viridis. 1.3 Objectives The objectives of this study are: i. To determine the effect of landuse changes on water quality along Danga-Pendas coastal area using Remote Sensing and Geographic Information System (GIS) 5 ii. To analyze the effects of water quality on green mussels (Perna viridis) along Danga-Pendas coastal area. iii. To assess the severity of pollution level due to massive development along Danga-Pendas coastal area. 1.4 Scope of Study The scope of this study consists of collecting samples at designated stations, extensive laboratory analysis on water quality and green mussel, data processing using integrated technology of remote sensing and GIS and finally analysis of the results. Sampling were carried out along the coastal and estuary from Danga Bay coastal area up to the Second Link Bridge. Sampling was conducted monthly starting from September 2008 to April 2009. The samples were then tested in laboratory and analyses were carried out based on validated standard procedures. The parameter analyzed in this study includes physical, nutrient and heavy metals analysis. Physical data comprise of dissolved oxygen (DO), temperature, pH, total dissolved solid (TDS), salinity, biochemical oxygen demand (BOD) and chemical oxygen demand (COD). Nutrient was analyzed for ammoniacal nitrogen and specifically lead, cadmium, nickel and zinc for heavy metals. Data processing were then applied using typical remote sensing and GIS’s software. Landsat TM satellites data for series of 1991 to 2008 were used in order to evaluate landuse changes and water quality effects. For remote sensing processing purposes, software such as Envi 4.2 and Erdas Imagine 9.1 were used. As for GIS processing purposes, ArcView 3.2 and ArcGIS 9.2 softwares were used to process the data. All the results were then analyzed in term of environmental monitoring such as effect of landuse changes to water quality and the effect of changes in water quality to mussel’s growth. 6 1.5 Significant of Study Effects of landuse changes are very significant contributor to changes in water quality of rivers, estuaries or coastal waters. This is because the replacement of the existing landuse to other development landuse which is mostly urban area will create large interference in term of pollutants such as organics, pesticides and chemicals residues which lead to polluted river. Therefore it is important to study the correlation between the changes of landuse due to the development and its impact on water quality as well as green mussel along Johor straits. The correlation can be used to monitor the water quality along the straits which also may lead to other effects in environmental aspects and disturb the aquatic ecosystem. Green mussel is an economically important seafood for Malaysia where it may lead to million in revenues in domestic consumption or exports. Beside that, the capability of modern technology such as GIS and remote sensing in adapting with the environmental aspects gives more valuable results. This then can be used as a basis monitoring and future prediction. Among others, the main importance of this study is to ensure that sustainability of the environment is still maintained and controlled along with the development. CHAPTER 2 LITERATURE REVIEW 2.1 Introduction This chapter explains the background related to studies on the impacts of nutrient, heavy metals and pollutant from development to water quality and green mussels. The information on water quality, monitoring landuse change as well as integration analysis using remote sensing and GIS will also be included. 2.2 Danga – Pendas Coastal Area Danga-Pendas coastal area is situated along the south coast of Johor. From the observation, Danga areas are more developed than Pendas area with the urbanization and expansion of Danga Bay. Most of Pendas area are still covered with vegetation and view along the coastal area are green with such a healthy mangrove trees. There are also some parts near Sungai Bahan which have been developed with slight IDR progresses. Most of the local resident along this area work either as fisherman or with aquaculture such as fish, prawns or mussels. Figure 2.1 shows the location of Danga-Pendas coastal area. 8 Peninsular Malaysia Danga Johor Pendas (a) (b) (c) (d) Figure 2.1:: (a) Location of Danga-Pendas Danga Pendas coastal area (b) development along Danga coastal area (c) Mangrove along Pendas coastal area and (d) development progress of IDR near coastal area of Nusajaya. 9 There are several tributaries along Danga-Pendas coastal area. Major tributaries which empty into this area are Sungai Pendas, Sungai Melayu and Sungai Skudai. Other tributaries are Sungai Danga, Sungai Perepat and Sungai Bahan. Figure 2.2 shows the number of tributaries entering into the Danga-Pendas coastal area. Sungai Skudai Sungai Melayu Sungai Perepat Sungai Danga Sungai Bahan Sungai Pendas Figure 2.2: Figure shows the tributaries which empty into Danga - Pendas coastal area. Previous studies reported that Sungai Skudai and Sungai Segget are among the four most polluted rivers in Johor. The other two rivers are Sungai Tukang Batu and Sungai Ayer Baloi (DOE, 2007). Sungai Skudai have been polluted by domestic wastes and industrial discharge especially ammoniacal nitrogen throughout the years. While the main pollutants for Sungai Segget is from the waste discharge of small industries which contain dyes and grease which are released into the drainage systems and hence flow into Sungai Segget (DOE, 2007). 2.2.1 Water Quality at Danga- Pendas Coastal Area From DOE DEIA report, coastal seawater was found to satisfy Class III of the Water Quality Index (DOE-WQI). The main pollutants are organics, ammoniacal 10 nitrogen, nitrate, phosphate, faecal coliform and a number of heavy metals such as iron, nickel and mercury. The faecal coliform counts in the sea water were about 200 times higher than the level recommended by the INMWQS (DEIA report). From other reports in New Strait Times, hydrologist, Dr Low Kwai Sim said that pollution in this area is so bad that it could pose a health hazard unless concerted efforts are made to break the Malaysia-Singapore Causeway and flush out the “dead water” (NST, 2006). She also said the pollutants accumulated over the years and trapped on both sides of the 82-year-old crossing could not be flushed out to the open sea. The two "dead water" bodies flanking the Causeway will have the worst ecological conditions of any waterway or rivers in the country if left in the present state. The danger is that if the Causeway is not demolished to allow for the free flow of tides and currents, the pollution level will begin to impact the lives of people (NST, 2006). 2.2.2 The Distribution and Harvested of P.viridis at Danga-Pendas coastal area Since early 80’s harvesting activities of P.viridis in Malaysia is always confined to Southern Johor. Most of the mussels are mostly harvested by the villagers. Large green mussel is a common species found at inter-tidal areas of the Johor Straits. The culture of shellfish from spat collected from areas of natural spat fall is a potentially profitable activity for coastal residents. Figure 2.3 shows the harvested green mussels area along Danga-Pendas estuary. 11 Green Mussels Harvested Area (a) (b) (c) Figure 2.3: Figure (a) Green mussels harvested area from satellite view. (b) and (c) shows mussels aquaculture along Danga-Pendas Area. 12 2.2.3 Existing and Future Planning Landuse Existing landuse along Danga-Pendas coastal area are mostly covered with mangrove plant. There are only a few parts which have been developed such as Danga estuaries (Danga Bay) and part of Pendas area located at Second-Link Bridge. Other parts along this area are still maintained with green mangrove area and residential area which are located just near the coastal water. Figure 2.4 shows the existing landuse along Danga-Pendas area, whereas Figure 2.5 shows landuse map along the area. (a) (b) (c) Figure 2.4: Existing landuse along Danga-Pendas coastal area 13 Figure 2.5: Existing landuse types along Danga-Pendas. (Source: SJER, CDP 2025) Danga-Pendas coastal area plan will receive a wide range of developments by 2025. This is due to the planning of Iskandar Development Regions (IDR) which envelops along Johor Straits starting from Sungai Pulai to the end of Tanjung Langsat at the east of Johor coastal area. Planning involves the development of parks, waterfronts, ports and free access zones regions. 2.3 Iskandar Development Regions (IDR) The Danga-Pendas area have received heavy development these recent years. The development involves all aspects of socio-economics and urban planning. One of the biggest and progressive development engaged in this area is the new South Johor Economic Region (SJER). SJER is one of the 8th Malaysia Plan in order to improve technology and future economics in the South East Asia region. 14 From a physical planning perspective, SJER is defined as a geographic area in the southern part of Johor that will benefit from the economic opportunities that will be promoted within the region (SJER CDP, 2006). Iskandar Malaysia is planned to become Southern Peninsular Malaysia’s most developed region where it includes living, entertainment, environment and business. The area covers 221 634.1 hectares (2 216.3 sq. km) involving five jurisdiction of Majlis Bandaraya Johor Bahru (MPJB), Majlis Perbandaran Johor Bahru Tengah (MPJBT), Pasir Gudang Local Authority, Majlis Perbandaran Kulai (MPK) and Majlis Daerah Pontian (MDP). Figure 2.6 shows the proposed landuse development under IDR. Figure 2.6: Proposed landuse under IDR (Source: SJER CDP 2025, www.wpi.com.my) 15 The coastal zone for IDR encompasses the waters of Johor Straits within Malaysian boundary and a 3 km inland zone along the coastline of Johor Straits, which also lies within the Special Economic Corridor (SEC). Special Economic Corridor (SEC) consists of four focal points that will be located in Nusajaya - Johor Bahru-Pasir Gudang area. It extends all the way into Pontian and Kota Tinggi where the Johor Straits waterway leads into two open waters which are the Straits of Malacca on the west and the South China Sea on the east (SJER CDP, 2006). Figure 2.7 shows the proposed major development of coastal zone under IDR. Figure 2.7: Proposed for major development of coastal zone under Iskandar Development Region (Source: SJER CDP 2025, www.wpi.com.my) The development would not only create an attractive new feature for the city but would also provide the opportunity to create new public spaces for the benefit of the growing population. From the proposed coastal zone physical planning provided by Khazanah National, 100 acres of parks and open spaces would be created, in addition to another 180 acres of land for mixed use development and infrastructure which have already been created. The opportunity to reshape the coastal area will result in a new and vibrant waterfront that will link Johor Bahru City Centre to 16 Danga Bay development. The Johor Bahru Coastal development will reclaim 250 metres of land to create a new shoreline. While, Nusajaya will create a seamless work and living environment between Johor and Singapore (SJER CDP, 2006). Figure 2.8 shows IDR development near Tebing Runtuh which is one of the study location. Figure 2.8: Development of IDR near Tebing Runtuh – under construction 2.4 Landuse Impact to Water Quality By definition, landuse is the development of land for any use. It also mean human modification of natural environment into built environment. Agricultural and urban land uses are widely known to impair water quality in streams and other water bodies (US EPA, 2000). However, landuse change beyond the metropolitan fringe is increasingly recognized as an emerging mode of development in critical need of ecological and water quality assessments (Theobald, 2004). Basically, agriculture or urban landuse has both direct and indirect impacts on water resources. Some impacts result from the direct modification or destruction of streams, lakes and wetlands. Other impact occur primarily offsite due to changes in the quality and quantity of runoff from urban development and construction activities (Dreher and Price, 1992). 17 Landuse areas generate both nonpoint and point sources pollution. Point sources that have an impact on surface water include industrial and municipal waste discharges which those that affect groundwater quality include leaky underground storage facilities, as well as miscellaneous accidental spills of organic or inorganic contaminants. Nonpoint sources include runoff or infiltration of water from roads, industrial areas and golf courses. Contaminants include metals, industrial organic chemicals, nutrients and pesticides. Naturally vegetated areas are increasingly converted to agricultural and urban cover, however it is important to look at the impact of these transformations on water quality (Lohani, 2008). 2.5 Water Quality Parameters Water quality measurements include physical, chemical and biological characteristics of water. The complexity of water quality as a subject is reflected in many types of measurements of water quality indicators. Some water quality measurement can be done on site during sampling process mean while other more complex parameters can be obtained by laboratory analysis. Simple measurements that can be made on-site are temperature, pH, dissolved oxygen, conductivity and salinity. More complex measurements that must be made in a laboratory setting requires water sample to be collected, preserved, and analyzed at the laboratory such as biological oxygen demand (BOD), chemical oxygen demand (COD), suspended sediment and all heavy metals components. Water quality parameters provide important information about the health of a water body. The following is a brief description of some commonly used parameters. 2.5.1 Dissolved Oxygen (DO) Dissolved oxygen (DO) analysis measures the amount of gaseous oxygen (O2) dissolved in an aqueous solution. Oxygen gets into water by diffusion from the surrounding air, by aeration and as a waste product of photosynthesis. In simple, DO 18 refer to the amount of oxygen that is present in the water. It is measured in units of milligrams per liter (mg/L), or milligrams of oxygen dissolved in a liter of water. The amount of oxygen that can dissolve in water is strongly limited by the temperature of the water. The colder the water, the more oxygen it can hold. The concentration of DO is high if the water quality is good (CRC Sugar, 2002). There are several factors that affects DO levels in water body. Among the factors are volume and velocity of water flowing in the water body. In slow, stagnant waters, oxygen only enters the top layer of water. While deeper water is often low in DO concentration due to decomposition of organic matter by bacteria that live on or near the bottom of the reservoir. Climate and season also affects DO level where the colder the water, the more oxygen can be dissolved in the water. Therefore, DO concentrations at one location are usually higher in the winter than in the summer (CRC Sugar, 2002). Other factors that also influence DO are the concentration of dissolved or suspended solids, amount of nutrients and type and number of organisms in water body. Oxygen is more easily dissolved into water with low levels of dissolved or suspended solids. Nutrients can also lead to increased plant growth. This can lead to high DO concentrations during the day as photosynthesis occurs, and low DO concentrations during the night. The types of organisms present in plant, bacteria or fungi affects the DO concentration in a water body. If many plants are present, the water can be supersaturated with DO during the day, as photosynthesis occurs. Concentrations of oxygen can decrease significantly during the night, due to respiration (Metcalf and Eddy, 2004). 2.5.2 Temperature Temperature impacts both chemical and biological characteristics of surface water. It affects the DO level in water, photosynthesis of aquatic plants, metabolic rates of aquatic organisms, and the sensitivity of these organisms to pollution, 19 parasites and disease. Variables that affect a waterway temperature include the color of water, depth, amount of shade from shoreline vegetation and also volume of water. Most heat warming surface waters comes from the sun, thus waterways with dark-colored water or those with dark muddy bottoms absorb heat best. However, deep waters usually are colder than shallow waters simply because they require more time to warm up. Trees overhanging a lake shore or river bank shades the water from sunlight. Some narrow creeks and streams are almost completely covered with overhanging vegetation during certain times of the year. The shade prevents water temperatures from rising too fast on bright sunny days. As for the volume of water, more water there is, the longer it takes to heat up or cool down (CRC Sugar, 2002). 2.5.3 pH pH is a measure of acidic or alkaline basic nature of water. The concentration of the hydrogen ion [H+] activity in a solution determines the pH. The balance of positive hydrogen ions (H+) and negative hydroxide ions (OH-) in water determines how acidic or basic the water is. In pure water, the concentration of positive hydrogen ions is in equilibrium with the concentration of negative hydroxide ions, and the pH measures exactly 7. The pH of water determines the solubility which is amount that can be dissolved in the water and biological availability which is the amount that can be utilized by aquatic life of chemical constituents such as nutrients like phosphorus, nitrogen, and carbon also heavy metals such as lead, copper, cadmium, and etc. A pH range of 6.0 to 9.0 appears to provide protection for the life of freshwater fish and bottom dwelling invertebrates. Rivers in Malaysia have pH values lower than 7.0 with 60% of them are in the average of pH 6.0 to 8.5 (Jarvie et al., 2006). 20 2.5.4 Salinity Salinity is a measure of the mass of dissolved salts or ionic constituents in a given mass of solution and usually expressed as parts per thousand (ppt). The electrical conductivity of seawater is strongly dependent on its salinity. The degree of salinity can represent the classification of seawater. It can be divided into freshwater, brackish water, saline and brine water. Table 2.1 shows the salinity measurement for each of them. Table 2.1: Salinity represents the types of water. Water salinity Fresh Water 2.5.5 Brackish Water Saline Water Brine < 0.05 % 0.05 – 3 % 3–5% >5% < 0.5 ppt 0.5 – 30 ppt 30 – 50 ppt > 50 ppt Total Dissolved Oxygen (TDS) Total Dissolved Solids (TDS) refers to all of the constituents dissolved in water. Dissolved solids refer to any minerals, salts, metals, cations or anions dissolved in water. The term TDS often used interchangeably with the term salinity. Total dissolved solids (TDS) comprise of inorganic salts (principally calcium, magnesium, potassium, sodium, bicarbonates, chlorides and sulfates) and some small amounts of organic matter that are dissolved in water. TDS can also represent the water according its content. Freshwater correspond to TDS content which is lower than 1000 mg/L. TDS of 1000 to 10000 mg/L will represent brackish water. While for salty water TDS is about 10000 to 100000 mg/L. TDS above 100000 mg/L are represented for brine water (US EPA, 2000). 21 2.5.6 Biochemical Oxygen Demand (BOD) Biochemical oxygen demand (BOD) is a measure of the quantity of oxygen used by microorganisms such as aerobic bacteria in the oxidation of organic matter. When organic matter decomposes, microorganisms such as bacteria and fungi feed upon this decaying material and eventually the matter becomes oxidized. BOD measures the amount of oxygen consumed by microorganisms in the process of decomposing organic matter in water. The harder the microorganisms work, the more oxygen they use and the higher the measure of BOD, leaving less oxygen for other life in the water (Vynavi, 2005). The test for BOD is especially important in waste water treatment, food manufacturing, and filtration facilities where the concentration of oxygen is crucial to the overall process and end products. High concentrations of dissolve oxygen (DO) predict that oxygen uptake by microorganisms is low along with the required break down of nutrient sources in the medium of sample. On the other hand, low DO readings signify high oxygen demand from microorganisms, and can lead to possible sources of contamination depending on the process. 2.5.7 Chemical Oxygen Demand (COD) Chemical oxygen demand (COD) test is commonly used to indirectly measure the amount of organic compounds in water. Most cations of COD determine the amount of organic pollutant found in surface water such as lakes and river, making COD a useful measure of water quality. It is expressed in milligrams per liter (mg/L), which indicates the mass of oxygen consumed per liter of solution. Older references may express the units as part per million (ppm). It is a measure of the capacity of water to consume oxygen during the decomposition of organic matter and the oxidation of inorganic chemicals such as ammonia and nitrite. COD measurements are commonly made on samples of waste waters or of natural waters contaminated by domestic or industrial waste and COD is related to BOD. 22 However, BOD only measures the amount of oxygen consumed by microbial oxidation and is most relevant to waters rich in organic matter. It is important to understand that COD and BOD do not necessarily measure the same types of oxygen consumption. For example, COD does not measure the oxygen-consuming potential associated with certain dissolved organic compounds such as acetate. However, acetate can be metabolized by microorganism and would therefore be detected in an assay of BOD. In contrast, the oxygen-consuming potential of cellulose is not measured during a short term BOD assay, but it is measured during a COD test (Nathanson, 1986). 2.5.8 Nutrients Nutrients, nitrogen and phosphorus are essential for plant growth. High concentrations indicate potential for excessive weed and algal growth. Total nutrients are made up of a dissolved component and an organic component, which is bound to carbon. Ammoniacal nitrogen is one of the nutrients which are important to take into consideration. 2.5.8.1 Ammoniacal Nitrogen Ammonia (NH3) refers to inorganic substance that is found in abundance on surface water, soil and easily catered through plant tissue decaying and composed of animal waste. Ammonia that is rich with nitrogen will be oxidized to nitrite (NO2-) by soil bacteria; Nitrosomonas with the absence of high dissolve oxygen in water. Then, nitrification occurs when Nitrobacter bacteria oxidize the nitrite to form nitrate (NO3-) (Cech, 2003). Surface water may be polluted when ammonia level reach 0.1 mg/L and when the level increase to 0.2 mg/L, water bodies are considered no longer a safe place for aquatic life because of high toxicity. There are a lot of contributors to increase ammonia level in river. Improper management of sewerage services, animal waste especially pig farm and waste from palm oil mill are the main contributors. The decay of dead algae and other organic material can also produce ammonia that 23 can be toxic to many forms of aquatic life. According to Jack (2006), when dissolved oxygen decrease, ammonia levels tend to increase. Ammonia is also recognize as the number one killer of tropical fish. As the level of ammonia rises, the death rate climbs even higher. Ammonia affects fish by causing the blood to lose its ability to carry oxygen. This creates stress and lowers the resistance of fish to such recurrent bacterial infections such as fin and tail rot, body slime, eye cloud, mouth fungus, and body sores (Nurhidayah, 2007). 2.5.9 Heavy Metals Toxic metals can be present in industrial, municipal, and urban runoff which can be harmful to humans and aquatic life. Increased in urbanization and industrialization are to blame for an increased level of trace metals, especially heavy metals in our waterways. The toxicity of metals is dependent on their solubility which in turn depends heavily on pH and on the presence of different types of anions and other cations. The heavy metals linked most often to human poisoning are lead, mercury, arsenic and cadmium. Other heavy metals, including copper, zinc, and chromium, are actually required by the body in small amounts, but can also be toxic in larger doses. Brief descriptions of heavy metals are discussed as follows. 2.5.9.1.Nickel (Ni) Nickel is a transition metal with a lustrous, metallic and silvery with a gold tinge appearance. Boiling point and atomic number of nickel is 2913ºC and 28 respectively. Nickel plays numerous roles in the biology of microorganisms and plants. Nickel compounds are hazardous because it is suspected to be carcinogenic for example nickel sulfide fume and dust is believed to be carcinogenic. Nickel levels in water varies as for sea water the concentration is 0.1 to 0.5µg/L, drinking water and surface water concentrations average is less than 20µg/L and 15 to 20µg/L, respectively. The concentration of Ni in shellfish ranging from 0.2 to 2.2ppm (wet 24 weight) has been determined in hardshell clams and 0.5 to 1.9ppm in eastern oysters (Stephan and Shetty, 1981). 2.5.9.2Zinc (Zn) Zinc having the atomic number 30 and it is a transition metal with bluish pale grey solid appearance. Boiling point for zinc is 907ºC. Zinc mainly applies in platting to prevent corrosion and rust of other metal. Zinc is an essential nutrient, necessary for sustaining all life. Green mussels assimilate 21 to 36% of zinc from ingestion of five species of marine phytoplankton. (Chong and Wang, 2000). The US recommendated dietary allowance of zinc from puberty on wards is 11 mg for males and 8 mg for females. Zinc deficiency may also be associate with a lot of chronic illness such as sickle cell disease, liver disease and renal disease. Even though zinc is an essential requirement for a healthy body, too much zinc can be harmful (Vazquez et al., 1999). 2.5.9.3Lead (Pb) Lead is a soft, malleable, poor metal also considered to be one of the heavy metals. Lead has a bluish-white color when freshly cut, but tarnishes to a dull grayish color when exposed to air. It has a shiny chrome-silver luster when melted into a liquid (Sax, 1976). Seawater contains trace amounts of lead (2 to 30 ppt). On average rivers contain between 3 and 30 ppb of lead. Phytoplankton contains approximately 5 to 10 ppm lead (dry mass), freshwater fish approximately 0.5 to 1000 ppb, and oyster approximately 500 ppb. Lead and lead compounds are generally toxic pollutants. Lead (II) salts and organic lead compounds are most harmful ecotoxicologically. Lead salts are attributed to water hazard Class 2, and consequently are harmful. The same applies to lead compounds such as lead acetate, lead oxide, lead nitrate, and lead carbonate. Lead limits plant chlorophyll synthesis. Nevertheless, plants can take up high levels of lead up to 500 ppm from soils. Higher concentrations negatively influence plant 25 growth. Through plant uptake, lead enters food chains. Consequently, lead pesticide application is prohibited in most countries. Lead accumulates in organisms, sediments and sludge (Vynavi, 2005). 2.5.9.4 Cadmium (Cd) Cadmium is a metal found in natural deposits as ores containing other elements. The greatest use of cadmium is primarily for metal plating and coating operations, including transportation equipment, machinery and baking enamels, photography and television phosphors. It is also used in nickel-cadmium and solar batteries and in pigments. Nowadays, about 70 percent of cadmium produced worldwide is used in nickel-cadmium (nicad) batteries. Nicad batteries can be used over and over. When a nicad battery has lost some or all of its power, it is inserted into a unit that plugs into an electrical outlet. Electricity from the outlet recharges the battery (US EPA, 2000). Cadmium occurs naturally in zinc, lead, copper and other ores which can serve as sources to ground and surface waters, especially when in contact with soft, acidic waters. Major industrial releases of cadmium are due to waste streams and leaching of landfills, and from a variety of operations that involve cadmium or zinc. In particular, cadmium can be released to drinking water from the corrosion of some galvanized plumbing and water main pipe materials (US EPA, 2000) 2.7 Water Quality Standard Standard is a term for an established norm or requirement. Water quality standard refers to the standard applied and required for water quality in every water levels such as river, lake or marine. There are numerous numbers of standards establish for water quality whether by international or local agency. The aim of water quality standard is to ensure that the quality and specifications of water quality in river, lake or marine water are safe for human uses. In Malaysia, some of the 26 standard used in water quality include Water Quality Index (WQI), Interim National Water Quality Standard (INWQS) and Interim National Marine Water Quality Standard (INMWQS). 2.6.1 Interim National Water Quality Standard (INWQS) Based on Interim National Water Quality Standard (INWQS) evaluation, there are six main classes which comprise of Class I, IIA, IIB, III, IV and V. All the classes are recommended and classified based on water quality parameters concentration that suits the classes (refer Appendix A).Table 2.2 shows the INWQS classification. Table 2.2: INWQS classification (DOE, 1986) Classes Class I Descriptions Water supply I – No treatment needed (except disinfection and boiling only) Class IIA Water supply II – Conventional treatment Fishery II – sensitive aquatic species 2.6.2 Class IIB Recreational use with body contact Class III Extensive treatment. Moderately tolerant species Class IV Irrigation Class V Unsuitable for specified beneficial use Interim National Marine Water Quality Standard (INMWQS) Interim National Marine Water Quality Standard (INMWQS) is the standard review specifically for marine water. This standard provides the standard concentration of selected water quality parameters regarding marine water. Table 2.3 shows INMWQS parameters and standards. 27 Table 2.3: Department of Environmental’s INMWQS parameters and standard (DOE, 1986) Parameters 2.6.3 Standard E. coli (MPN/100ml) 100 Oil & Grease (mg/l) 0 Suspended Solids (mg/l) 50 Cadmium (mg/l) 0.01 Chromium (mg/l) 0.5 Lead (mg/l) 0.1 Nickel (mg/l) 0.01 Copper (mg/l) 0.1 Water Quality Index (WQI) Water Quality Index (WQI) is specifically used to classify river water. The index range from 0 to 100 where the values of WQI have to be calculated from six water quality parameters. Among the six parameters are DO, BOD, COD, ammoniacal nitrogen, suspended sediment and pH. All parameters are based on the concentration in mg/l except for pH. These concentrations then are multiply with its weight and calculated to get the final WQI index value. Equation 2.1 shows the calculation for WQI. Table 2.4 shows the WQI index table with its range and degree of pollution. WQI = (0.22*SIDO) + (0.19*SIBOD) + (0.16*SICOD) + (0.15*SIAN) + (0.16*SISS) + (0.12*SIPH) Equation 2.1 where SI refers to sub index for each parameters in table (refer Appendix A). 28 Table 2.4: Water Quality Index (DOE, 1986) 2.7 WQI range Degree of Pollution < 31.0 Severely Polluted 31.0 – 51.9 Slightly Polluted 51.9 – 76.5 Moderate 76.5 – 92.7 Clean >92.7 Very Clean Asian Green Mussel, Perna viridis The Asian Green Mussel, Perna viridis (Linnaeus, 1758) is a kind of species from the family of Mytililidae. The classification of P.viridis is as shown in Table 2.5; Table 2.5: Scientific classification of Perna viridis (Source: National Introduced Marine Pest Information System (NIMPIS, 2000) Scientific Classification Name Kingdom Animalia Phylum Mollusca Class Bivalvia SubClass Lamellibranchia Order Mytiloida Family Mytilidae Genus Perna Species viridis (Linnaeus, 1758) The ranges of P.viridis are from 80 to 100 mm in length which occasionally reach 165 mm (Rajagopal, 2006). Green mussels are bivalves, which typically have two hinged shells closed by one or two adductor muscles. A strong ligament holds the two valves together at the hinge (Knott and De-Victor, 2007). The family 29 Mytilidae, to which this species belongs, is characterized by narrow, elliptical, fanshaped, thin valves which are of the same size (NIMPIS, 2000). The shell of P. viridis is bright green as a juvenile, and become darker to brown with green edges as it matures (USGS, 2008). The inner shell surface is bluish green and smooth, and the adductor muscle is kidney shaped. Figure 2.9: Green Mussels (P.viridis) Sexes in this species is separated where fertilization occur externally. Spawning occur generally twice a year between early spring and late autumn. However, in Thailand and Philippines spawning occurs year round (Walter, 1982). In Malaysia, spawning typically occurs twice a year which is in April and September. Sexual maturity normally occurs at 15 to 30 mm shell length that is 2 to 3 months age. The life cycle for P.viridis is typically 2 to 3 years (Power et al., 2004). Although the reported native thermal range of the green mussel is broad, reduced temperatures have been demonstrated to significantly have negatively impact on their growth rates. The native habitat of P.viridis is the Indo-Pacific region, primarily along Indian and southeast Asian coasts. Figure 2.10 shows the geographical distribution of P.viridis in the world. 30 Introduced Native Unknown Figure 2.10: Geographical distribution of P.viridis worldwide. (Source: National Introduced Marine Pest Information System (NIMPIS)) The optimum habitats for green lipped mussels are within settlements with the depth of 0 to 4 meters depth. However, it may live in a settlement up to 10 meters depth. Within a square meter there may be a presence of 35000 mussels in the some place. Good adaptations of green mussels make it able to survive at a broad range of temperature (7 to 37.5ºC) and salinities for a short period. It is primarily found in estuarine habitats with salinities optimum range from 27 to 33 ppt. P.viridis is also able to tolerate both hyper saline condition 80 ppt to reduced salinities until 12 ppt. Green mussels occur in environments with temperatures ranging from 10 to 35ºC and exhibit optimal response at temperatures between 26ºC and 32ºC (Power et al., 2004). This species is an efficient filter feeder, feeding on small zooplankton, phytoplankton and other suspended fine organic material. Numerous species preys on P.viridis are crustaceans, fish, seastars and molluscs (octopus). It is also a food source for human and aquaculture species throughout south-east Asia. P.viridis also has ecologically impact. Ecologically, P. viridis is able to out compete many other fouling species, causing changes in community structure and trophic relationships. P.viridis has also been recorded with high levels of accumulated toxins and heavy metals and is linked to shellfish poisoning in humans (NIMPIS, 2000). 31 2.7.1 P.viridis as Bioindicator and Biomonitor Biomonitor is an animal or plant that is sensitive to changes in the environment and thereby helps us to assess the overall health of its habitat. It describes species that accumulate trace metals or other substances in their tissues and therefore can be used to monitor the bioavailability of these substances in a particular environment (Wagner and Boman, 2004). Biomonitors exclusively provide time integrated measures of the bioavailable levels of substances (Camusso et al., 1994) a feature that makes them superior compared to water or sediment samples. As we can see, minor variation in the environment may lead to wide differentiation in the concentration of water or sediments sample. To assess heavy metal contamination in the marine environment different types of organisms may be used, such as seaweeds and filter-feeding mollusks. Bivalve mollusks have an ability to accumulate heavy metals to various orders of magnitude with respect to the levels found in their environment (Rainbow et al., 2000). On the other hand, bioindicator is an organism that functions as a signpost or calendar, indicating environmental factor such as seasonal change or proximity of a vital resource. It gives us a single piece of information such as the presence of water, whereas biomonitor help us to measure long term trends. Green mussels can be used as both biomonitor and bioindicator. Because of green mussel is an efficient filter feeder, it has been used widely as bioindicator species for pollutants (Sivalingam, 1977). Since the 1980’s, the best candidate for bioindicator surveys in South-East Asia is the green-lipped mussel Perna viridis (Phillips, 1980). Due to the wide distribution of green-lipped mussel Perna viridis in the coastal waters of the Asia-Pacific region (Tanabe, 2000) it is also regularly used as a biomonitoring agent for scientific purposes. Yet, there are criteria to be fulfilled in order to be a biomonitor such as the capacity to accumulate pollutants without being killed by the encountered levels, and sedentariness in order to be representative of the area (Wagner and Boman, 2004). Furthermore, biomonitors should be abundant and available in the area of study throughout the years, sufficiently longlived, tolerant of natural environmental fluctuations and pollution, and be of a reasonable size to provide enough tissue for analysis (Yap et al., 2004a). 32 In addition, one of the major requirements is that all species to be used as bioindicators should exhibit the same correlation in their elemental contents with those in the surrounding marine environment namely water. The body burdens of trace metals in most bivalves have been used to identify and map areas with exceedingly high levels of trace metals and organic pollutants, hence they can be used as biomonitors for aquatic environment. 2.7.2 Heavy Metal Contamination on Green Mussels (Perna viridis) Green mussels provide a cheap source of protein for human consumption. For P. viridis, it had been reported that there are about 60% protein in every 100 g (dry weight) of mussel soft tissues (Choo and Ng, 1990). From the nutritional point of view, mussel is an important food source for supplying essential trace metals such as Ca, Fe and certain vitamins such as niacin, thiamin and riboflavin (Cheong and Lee, 1984). Moreover, fish and shellfish may also contain polyunsaturated n-3 fatty acids which are biologically important and have been associated with a decreased risk of cardiovascular disease (Kromhout et al., 1985; Yap et al., 2004a). From the toxicological point of view, excessive consumption of metalcontaminated seafood may cause toxicity to humans. Since heavy metals are inorganic chemicals that are non-biodegradable, cannot be metabolized and will not break down into harmless forms (Kromhout et al., 1985), the measurement of levels of metals in the soft tissues of P.viridis is becoming more significant. They could simply accumulate through time, becoming more and more of a toxic threat as their concentrations increase. Levels of metals above the permissible limits would certainly create a notorious food image from the public health point of view. Chronic exposure to heavy metals such as Cu, Pb and Zn is associated with Parkinson’s disease and the metals might act alone or together over time to cause the disease (Gorell et al., 1997). Some metals, such as Cd and Pb, have long been known to accumulate within the aquatic food chain. 33 Mussels have been well known to accumulate a wide range of contaminants in their soft tissues (Goldberg et al., 1978). Intertidal areas are natural habitats of marine mussels and they are usually close to estuaries. Therefore, the chance of exposure to many contaminants from land-based activities through the riverine system as well as sea-based sources, is high (Yap et al., 2004a). 2.7.3 Studies of Heavy Metal Contaminants in Green Mussels at Johor Rivers and Estuaries There are a number of studies carried out regarding the level, distributions and concentrations of heavy metals contaminant in green mussels in this area. Previous studies reported that, the critical metals that lead to green mussel’s contamination are Cd, Cu, Pb and Zn. Yap et el., (2003), found that the concentration of heavy metals in these area are higher above the baseline literature of Tomlinson Pollution Load Index (PLI). The Tomlinson Pollution Load Index (PLI) was selected because it can be used as an index of bioavailability of heavy metals for mussels in coastal waters (Tomlinson et al., 1980; Angula, 1996; Yap et el., 2003). Aminah et al., (2003) reported regarding their study of the application of green mussels as bioindicator in assessing pollution at coastal area of Peninsular Malaysia. It can be valuable method for monitoring pollution in coastal sediment due to some trace and heavy metal elements. The feeding habits of this species heavy and trace elements present in the sediment makes them potential bioindicators. P. viridis have also demonstrated to be a good bioindicator for Cr. Based on studies done by Ibrahim (1993), marine aquatic life along South Johor coastal areas are contaminated by many chemicals and heavy metals. It is so relevant since most of rivers in these areas are used for wastewater and industrial waste discharge. Moreover, the advanced and popular industrial country, Singapore is just around the corner. It can also be one of the possibilities that contribute to heavy metals pollution in the area. 34 2.8 Remote Sensing and Geographic Information System (GIS) Remote sensing and geographic information system (GIS) can be powerful tools in analyzing landuse change thus can also monitor water quality of river. The combined use of GIS and Remote Sensing with other statistical techniques, such as modeling offers a lot of promise in water quality analysis (Lohani et al., 2008). Furthermore, they are also capable in monitoring the production of green mussels. With integration in using these technologies, water quality parameters that are important for mussel growth such as chlorophyll-a, salinity, temperature, pH and water depth are identified and analyzed in order to monitor the mussel production area. 2.8.1 Remote Sensing Remote sensing is the science and art of obtaining information about an object, area or phenomenon through the analysis of data required by a device such as by way of aircraft, spacecraft, satellite, buoy or ship that is not in contact with the object, area, or phenomenon under investigation (Lillesand and Kiefer, 2000). It is parallel with the definition given by Natural Resources Canada (NRC) which defined remote sensing as the science of acquiring information about the earth's surface without actually being in contact with it. This is done by sensing and recording reflected or emitted energy and processing, analyzing, and applying that information. There are two kinds of remote sensing, which are passive and active. Passive sensors detect natural radiation that is emitted or reflected by the object or surrounding area being observed. Reflected sunlight is the most common source of radiation measured by passive sensors. Examples of passive remote sensors include film photography, infra-red, charge-coupled devices and radiometers. Active sensor, on the other hand, emits energy in order to scan objects and areas whereupon a passive sensor then detects and measures the radiation that is reflected or backscattered from the target. RADAR is an example of active remote sensing where 35 the time delay between emission and return is measured, establishing the locations, height, speed and direction of an object (Lillesand and Kiefer, 2000). Most of remote sensing, processes involve interaction between incident radiation and the targets of interest. This is exemplified by the use of imaging systems where seven elements are involved (CCRS). Figure 2.11 shows the fundamental of seven important elements in remote sensing processes (Lillesand and Kiefer, 2000). All the seven elements are tabulated in Table 2.6. Figure 2.11: Seven elements in remote sensing processes consisting of A is energy source or illumination, B is radiation and the atmosphere, C is interaction with the target, D is recording of energy by the sensor, E is transmission, reception, and processing, F is interpretation and analysis and G is applications (source: Lillesand and Kiefer, 2000). 36 Table 2.6: Description of seven elements in remote sensing processes (Lillesand and Kiefer, 2000). Elements Descriptions Energy source or The first requirement for remote sensing is to have an illumination (A) energy source which illuminates or provides electromagnetic energy to the target of interest. Radiation and the As the energy travels from its source to the target, it will atmosphere (B) come in contact with and interact with the atmosphere it passes through. This interaction may take place a second time as the energy travels from the target to the sensor. Interaction with the Once the energy makes its way to the target through the target (C) atmosphere, it interacts with the target depending on the properties of both the target and the radiation. Recording of energy After the energy has been scattered by, or emitted from the by the sensor (D) target, we require a sensor to collect and record the electromagnetic radiation. Transmission, The energy recorded by the sensor has to be transmitted, reception, and often in electronic form, to a receiving and processing processing (E) station where the data are processed into an image in form of hardcopy or digital. Interpretation and The processed image is interpreted, visually and/or analysis (F) digitally or electronically, to extract information about the target which was illuminated. Applications (G) The final element of the remote sensing process is achieved when we apply the information we have been able to extract from the imagery about the target in order to better understand it, reveal some new information, or assist in solving a particular problem. 37 Generally, the quality of remote sensing data consists of its spatial, spectral, radiometric and temporal resolutions as discussed below (Ranganath et al., 2007). i. Spatial resolution Spatial resolution is the size of a pixel that is recorded in a raster image typically as pixels may correspond to square areas ranging in side length from 1 to 1000 meters. Figure 2.12 (a) show different spatial resolution of satellite images. ii. Spectral resolution Spectral resolution is the number of different frequency bands recorded usually, this is equivalent to the number of sensors carried by the platforms. For example, Landsat collection consists of seven bands, including several in the infrared spectrum. Figure 2.12 (b) show different spectral resolution of satellite images. iii. Radiometric resolution Radiometric resolution is the number of different intensities of radiation the sensor is able to distinguish. Typically, this ranges from 8 to 14 bits, corresponding to 256 levels of the gray scale and up to 16,384 intensities or shades of color, in each band. iv. Temporal resolution Temporal resolution is the frequency of flyovers by the satellite or plane, and is only relevant in time-series studies or those requiring an averaged or mosaic image. Figure 2.12 (c) show different temporal resolution of satellite images. 38 (a) (b) (c) Figure 2.12: Example of (a) spatial variations (b) spectral resolution and (c) temporal resolution in remote sensing data. (Source: Ranganath et al., 2007) Remote sensing are applied for sustainable agriculture, ocean color and fishery, water security, environmental assessment and monitoring, disaster monitoring and mitigation, weather and climate studies, infrastructure development and etc (Ranganath et al., 2007). 39 2.8.1.1 Remote Sensing Data Landsat TM and ETM The Thematic Mapper (TM) is an advanced, multispectral scanning, earth resources sensor designed to achieve higher image resolution, sharper spectral separation, improved geometric fidelity, and have greater radiometric accuracy and resolution. This sensor also images a swath that is 185 km (115 miles) wide with each pixel in a TM scene represents a 30 m x 30 m ground area, except in the case of the far-infrared band 7. Band 7 in TM sensor uses a larger 120 m x 120 m pixel. The TM sensor has seven bands that simultaneously record reflected or emitted radiation from the earth's surface. Table 2.7 lists a brief description of sensor specification in LandsatTM (Lillesand and Kiefer, 2000). Table 2.7: Landsat satellite sensor characteristic and specification (Lillesand and Kiefer, 2000). Spatial Resolution 30 meters Orbit 705 +/- 5 km (at the equator) sun-synchronous Orbit Inclination 98.2 +/- 0.15 Orbit Period 98.9 minutes Grounding track Repeat Cycle 16 days (233 orbits) Resolution 15 – 90 meters Band 1 (Blue) : 0.45 – 0 52 µm 2 (Green) : 0.52 – 0.60 µm 3 (Red) : 0.63 – 0.69 µm 4 (NIR) : 0.76 – 0.90 µm 5 (NIR) : 1.55 – 1.75 µm 6 (TIR) : 10.40 – 12.50 µm 7 (MIR) : 2.08 – 2.35 µm Landsat Enhanced Thematic Mapper (ETM) stresses the provision of data continuity with Landasat 5-TM. The characteristics and number of bands are similar to Landsat TM. However, Landsat ETM requires advanced one bands with make it 8 bands with addition of panchromatic bands. The wavelength of this band is 0.52 - 40 0.90 µm with 15 m resolution. Table 2.8 show the 7 bands description with addition of 8th band laid in Landsat ETM. Table 2.8: Landsat’s band descriptions (Lillesand and Kiefer, 2000). Band Descriptions Band 1 Band 1 is in the visible portion of the electromagnetic spectrum that corresponds with blue-green light. The principal applications are for coastal mapping, differentiation of soil/vegetation or deciduous/coniferous. Band 2 Band 2 is in the visible portion of the electromagnetic spectrum that corresponds with green light. Green reflectance is from healthy vegetation. Band 3 Band 3 is in the visible portion of the electromagnetic spectrum that corresponds with red light. This is used to show chlorophyll absorption for plant species differentiation. Band 4 Band 4 is in the Near Infrared (NIR) portion of the electromagnetic spectrum. This form of radiation is reflected to a high degree off leafy vegetation, since chlorophyll has a high albedo in this band. It is used for biomass surveys and water body delineation. Band 5 Band 5 is in the Middle Infrared (Mid-IR) portion of the electromagnetic spectrum. This portion of the spectrum is sensitive to variations in water content in both leafy vegetation and soil moisture. Band 6 Band 6 is in the Thermal Infrared portion of the electromagnetic spectrum. Thermal infrared is radiation that is detected as heat energy; therefore, the thermal IR band effectively measures the temperature of the surfaces it scans. Using this band, researchers can discriminate and help assist with drought planning, flood forecasting, and agricultural assessment. Band 7 Band 7 is in the Middle Infrared (Mid-IR) portion of the electromagnetic spectrum. This portion of the electromagnetic spectrum is sensitive to moisture and thus responds to the moisture contents in soils and vegetation. Hydrothermal mapping can detect plant stress. Band 8 This band is used to merge with other spectral band to enhance the spatial resolution of the data. 41 2.8.2 Geographic Information System (GIS) GIS is a computer system capable of capturing, storing, analyzing, and displaying geographically referenced information that is data identified according to location. Practitioners also define GIS as a system that includes procedures, operating personnel and spatial data that go into the system (USGS, 2007). Ranganath et al. (2007) defined GIS as a computer assisted system for capture, storage, retrieval, analysis and display of spatial data and non-spatial attribute data. Analysis models comprise of simple user defined views to complex stochastic models. Some of these are reclassifications, aggregation, overlays, suitability analysis, network and route analysis, optimization, allocation or sitting. The power of a GIS comes from the ability to relate different information in a spatial context and to reach a conclusion about this relationship. Most of the information in the world contains a location reference and placing that information at some point on the globe. Applications of GIS range from simple database query systems to complex analysis and decision support systems. GIS techniques are playing an increasing role in facilitating integration of multi-layer spatial information with statistical attribute data to arrive at alternate developmental scenarios. A GIS makes it possible to link, or integrate, information that is difficult to associate through any other means. Thus, a GIS can use combinations of mapped variables to build and analyze new variables. Figure 2.13 shows the capability of GIS in data integration. 42 Figure 2.13: Data integration from different forms of input through GIS. (Source: USGS, 2007) A critical component of GIS is its ability to produce graphics on the screen or on paper to convey the results of analyses to people who make decisions on resources. Wall maps, interactive maps and other graphics can be generated, which allow the decision makers to visualize and thereby understand the results of analyses or simulations of potential events. 2.9 Integration of Remote Sensing and GIS Developments of remote sensing and GIS technologies have lead to the betterment of mapping and interpretation techniques as a means of understanding and effectively managing the present resources for sustainability. Remote sensing is a powerful technique for surveying, mapping and monitoring earth resources. This technique has become indispensable and increasingly more meaningful because of the synoptic coverage of satellites over large areas rendering its cost and time effectiveness. Furthermore, in areas that are difficult to access, this technique is perhaps the only method of obtaining the required data more affectivity. In addition of GIS, the analysis of mechanisms of landuse pattern changes and monitoring plays an important role in not only forecasting changes but also formulating local development policies (Lillesand and Kiefer, 2000). 43 2.9.1 Landuse Monitoring using satellite data Landuse refers to the purpose the land serves for example recreation, wildlife habitat or agriculture. One of the important applications of remote sensing is the generation of landuse and landcover maps from satellite imagery. Compared to more traditional mapping approaches such as terrestrial survey and basic aerial photointerpretation, land-use mapping using satellite imagery has the advantages of low cost, large area coverage, repetitively, and computability (Franklin, 2001). Consequently, land-use information products obtained from satellite imagery such as land-use maps, data and GIS layers have become an essential tool in many operational programs involving land resource management. Remote sensing application has very powerful tools in accessing landuse information. By the use of remotely sensed data, information of landuse are available for various times, resolutions and ranging from general to specifically landuse types based on the application needed. There is a number of researches done in extracting landuse information using various multispectral satellite images such as Landsat TM, SPOT, IKONOS, aerial photograph and so on. It have been proved that the use of this application give numerous benefits and advantages. Remotely sensed data are able to provide time series landuse information which is important in monitoring aspect. This is the main advantage of satellite data which offer large range of landuse monitoring. Beside, the resolutions of the data range from small, fine and to the higher ones. Users or researchers can choose suitable data based on the application of landuse itself. Where else, the information generate can also be decided by user whether it is generally classified of specifically classified landuse information. Landuse studies using remote sensing data have received immense attention worldwide due to their importance in global climate change analysis (Cihlar, 2000). Both human-induced and natural land cover changes can influence global change because of its interaction with terrestrial ecosystem (Miller and Pool, 2002), 44 biodiversity (Sala et al., 2000) and landscape ecology (Reid et al., 2000). In addition, it reflects the impacts of humans on environment at various temporal and spatial scales (Lopez et al., 2001). Therefore, accurate and up-to-date landuse information is essential for environmental planning to understand the impact on terrestrial ecosystem and to achieve sustainable development. 2.9.2 Landuse Change Detection Change detection is the process that helps in determining the changes associated with landuse and landcover properties with reference to geo-registered multi temporal remote sensing data. Landuse and landcover change can play a vital role in environmental changes and contribute to global change (Meyer and Turner, 1991; Dale, 1997). Beside that, the study of the landuse patterns and the monitoring of changes are also very important for economic planning and country development. (Lwin and Ryosuke, 1997). The basis of using remote sensing data for change detection is that changes in landuse result in changes in radiance values which can be remotely sensed. Techniques to perform change detection with satellite imagery have become numerous as a result of increasing versatility in manipulating digital data and increasing computer power. Landcover can be altered by forces other than anthropogenic. Natural events such as weather, flooding, fire, climate fluctuations and ecosystem dynamics may also initiate modifications on land cover. Globally, landcover today is altered principally by direct human use which is by agriculture and livestock raising, forest harvesting and management and urban and suburban construction and development. There are also incidental impacts on land cover from other human activities such as forest and lakes damaged by acid rain from fossil fuel combustion and crops near cities damaged by tropospheric ozone resulting from automobile exhaust (Meyer, 1995). CHAPTER 3 METHODOLOGY 3.1 Introduction This chapter explains the methodology and steps taken in this study. It can be divided into four main tasks. The methodology starts with collection of information from primary sources and secondary sources (literature review). The second task is data collection and sampling including primary data and historical data. The third task is sampling processes and laboratory test. In this stage, processes consist of the collection of water quality parameters and green mussel and laboratory analysis. The final task involves process of integrated remote sensing and GIS technology application on water quality along study area. This process will be carried out using several remote sensing and GIS software. 3.2 Literature Review Methodology starts with gathering and collection of information related with this study in order to understand the processes and methodology that will be used. The reviews is based on primary and secondary sources such as journal articles and previous dissertations, textbooks and articles from Department of Fisheries (DOF) Malaysia, Department of Environment (DOE) or other related departments, newspapers and internet to find the relevant background information. 46 3.3 Data Collection and Sampling Data collection involves the collection of primary and secondary data that were used in this study. Primary data includes the data from sampling process, laboratory works and satellite images. Secondary data consist of historical water quality data from various years gathered from journals, dissertations and research conducted at the study area. Additional information on green mussels, water quality and landuse were also gathered from related Departments. Table 3.1 shows data collection and sampling. Table 3.1: Data collection and sampling Data Source Year Satellite Images MACRES, 1991,2000,2005 Landsat.org/TRFIC 2008 Sampling Present Journals, Dissertations, Research 1991- 2008 Water Quality Reports, DOE Sampling Present Journals, Research Reports 1991- 2008 Landuse Map JUPEM 1991 Topography Map JUPEM 2002 Green Mussels 3.4 - Edisi 2-PPNM Sheet 175 - Edisi 2-PPNM Sheet 174 Sampling Processes and Laboratory Works Sampling process entail the data collection for water quality parameters includes in-situ and laboratory test. Several considerations in this process are 47 sampling stations, sampling techniques and laboratory analysis for water quality parameters. Figure 3.1: Flowchart of sampling and laboratory works 3.4.1 Study Area and Sampling Stations This study was carried out along the coastal and estuaries area starting from Danga Bay to Second Link Bridge. The area involved is 11 km with total eleven sampling stations and four mussels collection stations. Eleven sampling stations were identified along Danga to Pendas coastal area starting from Sungai Skudai estuaries and ends at Tanjung Kupang which is near to Second Link Johor-Singapore Bridge. Figure 3.2 to 3.6 shows the location of study area with the sampling points followed by Table 3.2 showing the sampling stations coordinates. 48 S1 Water Quality Sampling Points M1 Mussels Sampling Points Johor Bahru Singapore Figure 3.2: Location of study area with eleven sampling stations. Table 3.2: Coordinates of the eleven sampling stations at the study area. Sampling Stations 1 Sungai Skudai Estuaries 2 3 Sungai Danga Estuaries 4 5 Sungai Melayu Estuaries 6 Coordinate Code N 01 28.265 E103 43.039 S1 N 01 28.011 E103 43.150 S2 N 01 28.108 E103 43.433 S3 N 01 27.662 E103 43.855 S4 N 01 27.454 E103 43.459 S5 N 01 27.328 E103 41.719 S6 7 Nusajaya N 01 27.574 E103 41.308 S7 8 Tebing Runtuh N 01 26.825 E103 41.603 S8 9 N 01 26 348 E103 40.640 S9 10 Tanjung Kupang N 01 24.544 E103 39.440 S10 11 Second Link (Tanjung N 01 22.225 E103 38.139 S11 Kupang) 49 Figure 3.3: Sampling station S2 at Sungai Danga estuary. (a) (b) Figure 3.4: Sampling station M2 for mussels collection station near Sungai Melayu estuaries. 50 Figure 3.5: Sampling stations M3 for mussel’s collection Figure 3.6: Sampling station M4 and S9 near Nusajaya area 3.4.2 Sampling Frequency and Parameters Analyzed Sampling were carried out six times for a period of 6 months from November 2008 to April 2009 (refer Table 3.3). The sampling strategy incorporated frequent collections in order to adequately define transient changes in the concentration of the constituents being measured. Each time sampling commenced from the upper 51 reaches of the river and estuaries at Sungai Skudai (S1) and Sungai Danga up to the Sungai Pendas (S11) nearest to Second Link Bridge. Table 3.3: Date of sampling Sampling Month Date Samples November 2008 20th November 2008 Water and Mussels December 2008 12th December 2008 Water and Mussels th January 2009 14 January 2009 Water and Mussels February 2009 18th February 2009 Water and Mussels March 2009 21st March 2009 Water and Mussels April 2009 25th April 2009 Water and Mussels A total of 12 water quality parameters were studied involving physical, nutrient and heavy metals. The parameters measured are dissolved oxygen (DO), pH, temperature, salinity, biochemical oxygen demand (BOD), chemical oxygen demand (COD), total dissolved solids (TDS), ammoniacal nitrogen and several heavy metals parameters such as lead (Pb), cadmium (Cd), nickel (Ni) and zinc (Zn). 3.4.3 Sampling Techniques Grab sampling method was adopted in this study. Location of each sampling points were affirmed using Global Positioning System (GPS). Water was sampled at all station however mussels were only sampled at selected stations. In this aspect, water quality parameters and green mussels were taken for samples. In water sampling for water quality analysis, parameters such as DO, pH, salinity and temperature were recorded at each station. Other basic water quality parameters such as TDS, BOD, COD were analyzed in the laboratory. Heavy metal parameters were also sampled and analyze by Atomic Absorption 52 Spectrophotometer. Water sample was acidified to pH less than 2 with concentrated nitric acid. Wild mussels were also collected from selected areas nearest to the water collection points. Green mussels obtained were aqua-cultured green-mussels. A random number of green mussels of several sizes were collected. The different sizes of green mussels then were grouped according to their estimated age. All mussels were digested before analyzing for nutrients and heavy metals. Green mussels then were weighed and digested using wet basis method. Polyethylene sampling bottle 1 liter was used for water samples whereas mussels were transported in polyethylene bags. Generally, all polyethylene and glassware used in the experiment was pre-cleaned and rinsed with double deionised distilled water (DDDW) to remove any possible trace of contaminants prior to use. 3.4.4 Laboratory Analysis Laboratory analysis were carried out for both water and mussel samples. Water samples were analyzed for its physical parameter and nutrients. Both samples were analyzed for heavy metals in order to evaluate the precedence of the metals in both water and mussels. 3.4.4.3 Sample Pretreatment Before both samples were analyzed in laboratory test, they need to be treated in order to be able for them be analyzed in the lab. 53 i) Mussels Pre-Treatment Collected P.viridis was group according to size and before mussels are shucked, the external shell surface was thoroughly cleaned with brush and water to remove all sand and dirt, adhering to the shell to prevent contamination of composite samples. It was then thawed and shucked where the flesh was collected in a clean dish and homogenized by mixing. Green mussels (2g) were weighed and digested using wet basis. Green mussels were digested using a modified reflux system by digesting it overnight using hot plate. Digested samples were then filtered and diluted using DDDW to ensure the acid in the sample is less than 5%. Digestion method adopted from APHA 3030E which is a nitric acid digestion method (refer Appendix B). 3.4.4.4 Laboratory Test for BOD, COD and Ammoniacal nitrogen Parameters such as DO, pH, salinity and temperature were recorded at each station using YSI model 556 MPS multi probe system. Analysis for COD and nutrient were carried out in the laboratory using standard procedures. Figure 3.7 shows the instruments used for analysis. i) Biochemical Oxygen Demand (BOD) measurement The concentration of BOD was determined based on the Standard Method APHA 5210-B procedures (Appendix B). ii) Chemical Oxygen Demand (COD) measurement The concentration of COD was determined based on the Standard Method APHA 5220-C procedures (Appendix B). iii) Ammoniacal nitrogen (AN) measurement The concentration of AN was determined based on the Standard Method APHA 4500-NH3 procedures using HACH DR 5000 Spectrophotometer (Appendix B). 54 (a) (b) Figure 3.7: (a) YSI-USA multiparameter probe (b) HACH DR 5000 Spectrophotometer for water quality analysis. 3.4.4.5 Laboratory Analysis for Heavy Metals Heavy metals were determined using Flame Atomic Absorption Spectrometer (Perkin Elmer model Analyst 400) (Figure 3.8). Perkin Elmer HGA 900 Graphite Furnace Atomic Absorption Spectrometer was used in analyzing arsenic. Shimadzu analytical balance and GQ calibrated volumetric flasks were used for preparation of all metal standard stock solution. Figure 3.8: Perkin Elmer model Analyst 400 Atomic Absorption Spectrometer for heavy metals extraction and analysis. Analysis was done using air – acetylene flame atomic absorption spectroscopy for all metals. Operating condition for each metal are shown in Table 3.4. 55 Table 3.4: Recommended condition for Flame Atomic Absorption Spectrometer Perkin Elmer Analyst 400 Metal Wavelength, nm Slit width, nm Characteristic Concentration Check Lead 283.30 0.7 20.0 Nickel 232.00 0.2 7.0 Zinc 213.86 0.7 1.0 Cadmium 228.80 0.7 1.5 The concentrations of metals in the samples were determined by referring to standards calibration curve which was prepared in standards preparation (refer Appendix B) 3.5 Integrated Remote Sensing and GIS Processing of remote sensing data was carried out by integrating both remote sensing and GIS. Remote Sensing and GIS can be a powerful tool in analyzing landuse change thus can also monitor water quality of the river. The combined use of GIS and Remote Sensing with other statistical techniques, such as modeling offers much promise in water quality analysis (Lohani, 2008). Satellite imageries and historical water quality data were used in analyzing the Western Johor estuarine system due to landuse effects. In this part, it requires the used of some remote sensing and GIS software such as Erdas Imagine, ArcGIS and ArcView also the used of satellite images such as Landsat TM and ETM. 3.5.1 Remote Sensing Data, Landsat TM and ETM Remote sensing data for various years were gathered from Malaysia Remote Sensing Agency (MACRES). Various year data were used to see the landuse changes 56 at the study area. Landsat TM and ETM were used as the main remote sensing data in this study. Landsat TM and ETM images gathered from MACRES are from year 1991 to 2008. Landsat TM and ETM are chosen because of the advantages of this data in large spatial resolution of 30m which can cater the study area with fine spectral resolution. It has seven bands which can cater the analysis from ground which was used for landuse extraction and water for analysis of water quality. Figure 3.9 shows scenes of Landsat satellite images from 1991 to 2008. Table 3.5 shows Landsat TM classification. (a) (b) (c) (d) Figure 3.9: Landsat TM and ETM images for (a)1991 (b)2000 (c) 2005 (d) 2008 57 Table 3.5: Landsat TM Specifications 1991 2000 2005 2008 Landsat-5 Landsat-7 Landsat-5 Landsat-7 ETM TM ETM TM 125/59 125/59 125/59 125/59 11 March 28 April 28 January 24 February 2008 1991 2000 2005 Layer 6 layers 6 layers 6 layers 6 layers Pixel Size 30.0 m 30.0 m 30.0 m 30.0 m Data Type Unsigned- Unsigned- Unsigned- Unsigned-8bit 8bit 8bit 8bit Format GeoTIFF GeoTIFF GeoTIFF GeoTIFF Source MACRES MACRES MACRES Landsat.org/TRFIC Specifications Satellite Path/Row Date 3.5.2 Landuse Extraction from Satellite Imagery For extraction of landuse, processing of satellite images was carried out in several stages. Each image goes through several processing such as geometric correction, atmospheric correction, subset to particular coordinate and ROI selection before obtaining landuse information image. Figure 3.10 display the flowchart for landuse classification. 58 Figure 3.10: Flowchart of Landuse Classification 3.5.2.1 Geometric Correction Geometric correction was used to correct the geographical location and projection of the images to be same as on the earth surface. All the raw remote sensing data, contains geometry effect that been produced by earth curve, atmospheric effects and panoramic effects. The main reason for performing geometric correction is to correct this effect so that the image will be rectified in a proper way. Geometric correction involves the changes of the original data for preprocessing by considering the position pixel and system parameter such as number of ground control points (GCP) and type of interpolation method (Jensen, 1996). It is also known as rectification process. Both satellite images need to be rectified to the real coordinate as stated in the Topographic Map. Topographic Map in year 2002 was used as the base map in running the process. In order to rectify the images, several similar points (GCP) from 59 both image and map were identified. Coordinates of each point that has been identified from the image were then replaced by the corrected coordinate from the map. The images were then resampled based on polynomials to the preferred projection. In processing data in this study, type of projection used for all the satellite images are RSO Malaya Meters. The details specification of this projection is shown in Table 3.6. Table 3.6: Projection specifications Projection Rectified Skew Orthomorphic (RSO) Natural Origin False-Easting 804671.299775 False-Northing 0.00000 Scale Factor -0.999840 Azimuth -36.974209 Origin Longitude 102.250 Origin Latitude 4.00 Linear Unit Meter Datum Kertau 3.5.2.2 Atmospheric Correction and Masking The next step to be taken is atmospheric correction. Atmospheric correction was used to reduce atmospheric effects in images since these images are taken from the outer space. The objective of atmospheric correction is to retrieve the surface reflectance that characterizes the surface properties from remotely sensed imagery by removing the atmospheric effects (Jensen, 1996). Atmospheric correction has been shown to significantly improve the accuracy of image classification. Then the heavy cloud should be mask out so that it will not appear and affect the digital values (DN) for further processing. In this process, the DN values for cloud were identified by the infra-red band. Infra-red band (band 4) was used because it can be the best band which can differentiate clearly cloud with other features in the image. The values were then run in a modeler maker, which is one of the Erdas Imagine software function used to calculate and model the data. 60 3.5.2.3 Subset Due to the large size of Landsat images, it was discovered that the best way to serve the images and data on study area was to take subsets of the larger image swaths taken by the Landsat satellite. All the images then were subset only to the area required for this study. Each image was subset to the designated subset coordinate as shown in Table 3.7. Table 3.7: Coordinates for image subset. Upper Left X 618545.00 Upper Left Y 170471.00 Lower Right X 645965.00 Lower Right Y 146711.00 3.5.2.4 Image Classification Region of Interest (ROI) are the process selection for the representative pixels from each landuse classes. Selection of ROI is the main important part before further classification process. Six classes were developed which consist of mangrove, urban and development area, cultivation area, forest or scrubs, open area and water bodies. Classification processes were then carried out to obtain landuse information from various years of data. The type of classification algorithm used in this study is Maximum Likelihood. The Maximum Likelihood decision rule assigns each pixel having pattern measurement or features X to the class c whose units most probable or likely to have given rise to feature vector x (Jensen, 1996). In this process, each pixel of the images were determined or represented by landuse types such as water bodies, ground, forest, urban and so on. It is also considers that each statistic for ROI for each class which is normally distributed. 61 To get the classification probability of pixel which represent class i, and it has vector feature f, then the probability for this class p (i|f) can be measured using Bayes condition (Schowengerdt, 1997). P (i|f) = p (f|i) p (i) P (f) Where ; (Equation 3.1) P (f) = ∑ p (f|i) p (i) Conditional result is based on the probability on the posterior state as Equation 3.1. Then pixel is classified to the class if the posterior probability is higher than other classes. If p (f|i) > p (j|f), for all j≠i Then pixel is classified as class i. The results then were verified by accuracy assessment for classification. Accuracy assessment is important whenever it is required to validate the derived or measured parameters compared to the ground truth data. Type of assessment done was error matrix consist of producer’s and user’s accuracy, overall accuracy and kappa statistics. Producer’s accuracy corresponds to error of omission (exclusion) while user’s accuracy refers to error of commission (inclusion). Kappa statistic is a measure of the proportional or percentage improvement by the classifier over a purely random assignment to classes. 3.5.3 Landuse Change Detection For change detection process, both landuse classification images chosen for changes that have been produced were used. It is important to take notes that, both images need to be registered to the same projection which enable them to be 62 processed correctly. The process was done using the designated features for change detection using post-classification comparison image. Post-classification comparison change detection method is the most commonly used quantitative method. It requires rectification and classification of each remotely sensed image. These two maps are then compared on pixel-by-pixel basis using a change detection matrix (Jensen, 1996). This kind of method is easy to understand. The advantage include the detailed from-to (before to after) information that can be extracted and the fact that the classification map for the next base year is already completed. However, the accuracy of the change is dependent on the accuracy of the two separate classifications that are required (Jensen, 1996). Figure 3.11 shows the flowchart of the landuse change detection. Figure 3.11: Flowchart of Landuse Change Detection. 63 3.6 Flowchart of Methodology The overall flowchart of methodology is shown in Figure 3.12. Figure 3.12: Overall flowchart of methodology CHAPTER 4 EFFECT OF LANDUSE ON WATER QUALITY 4.1 Introduction This chapter shows and explains the results obtained from the works carried out on the effects of landuse to water quality along Danga-Pendas coastal area. The results can be classified to several phase of output such as landuse classification using image processing for year 1991 and 2008, the analysis of the landuse change and water quality from 1991, 2005 and 2009 and also analysis of difference in water quality due to landuse change. The final output included in this chapter are landuse maps for 1991 to 2008, statistic and analysis of landuse change, water quality and analysis of changes in water quality due to landuse change. 4.2 Landuse Classification Landuse classification process were carried out for year 1991, 2000, 2005 and 2008 which are considered to be relevant changes to landuse along Danga-Pendas area. After several image processing such as geometric correction, atmospheric correction, subset and classification were done, landuse maps for each significant year for this area were obtained. The landuse image was classified into six types of major landuse classes which are mangrove area, urban and developed area, open area, forest or scrubs area, cultivation and water bodies. Landuse classes were chosen 65 based on the most relevant and main landuse covered. Two standard criteria were used to assess the accuracy of the classifications which consist of overall accuracy and kappa statistics. The overall accuracy was defined as the total number of correctly classified pixels divided by the total number of reference pixels (total number of sample points) (Rogan et al., 2002). On the other hand, kappa coefficient was defined as a statistical measure of accuracy that ranges between 0 and 1, it measures how much better the classification is compared to randomly assigning class values to each pixel (Miller and Pool, 2002). 4.2.1 Landuse Classification for 1991 Figure 4.1 shows the landuse classification map that has been derived from image classification process using Erdas Imagine software. As we can observe from the figure, most of the developed areas are distributed at the main area of Johor Bahru and part of Singapore area (brown color). Whereas the majority of Johor areas are covered with cultivation area. Cultivation area consists of oil palm and rubber plantation area where there are also some mix plants. Open area can be seen at several parts in urban area. Along Danga-Pendas coastal area, mangrove and scrubs are the main landuse types present in 1991. Only several parts in Danga coastal area are developed within the town and residential area. 66 Figure 4.1: Landuse classification for 1991 In order to validate the accuracy of landuse classification that has been obtained from the processing, assessment of the map was carried out. By the used of accuracy assessment for classification, overall classification accuracy obtained was 80 % with overall kappa statistics of 0.6918. A detail on accuracy assessment is shown on Appendix C (i). 4.2.2 Landuse Classification for 2000 Figure 4.2 represent landuse map for year 2000. The same landuse types or classes were developed. In comparison to year 1991 landuse map, major changes have been observed especially in urban/ developed, open area and scrubs. There are lines of new developed road, open area for developing region and the main difference is the development of Second Link Bridge in Pendas. Overall accuracy for 2000 landuse classification was 76.47% with kappa statistic of 0.6699. A detail on accuracy assessment is shown on Appendix C (ii). 67 Second-Link Bridge Figure 4.2: Landuse classification for 2000 4.2.3 Landuse Classification for 2005 Result for landuse classification for 2005, display a dense urban/ developed area compared to open area as shown in Figure 4.3. Most of the open area that existed in year 2000, have been change into developed area. As illustrated in the figure, Johor Bahru areas are more intense with development where most of the areas are brown in color. Overall accuracy for year 2005 landuse classification was calculated as 82.35% with kappa statistic of 0.7560. A detail on accuracy assessment is shown on Appendix C (iii). 68 Figure 4.3: Landuse classification for 2005 4.2.4 Landuse Classification of year 2008 Figure 4.4 illustrates the landuse for latest image captured in 2008 for Johor Bahru area. The Landsat image for 2008 has some interference with stripping line which consists of no data. This problem is due to an error in the detector or scanner of the satellite which caused the detector or scanner unable to detect and scan the ground for specific lines. This however did not affect other scanlines where they can still be processes to obtain landuse map. Besides lacking of data in some parts, the image was also heavy covered and distributed with cloud. Although the clouds have been masked and detected as unclassified, their appearance still gives some effect to the landuse information. From the figure, there are much more difference in landuse compared to year 2005. The obvious IDR development region which is in progress can be seen clearly as an open area in this figure. The region has been classified as an open area because 69 it is still under the progress which consists of site clearing, earthwork, demolition and also development of new buildings that requires the area to be cleared in open area. Figure 4.4: Landuse classification for 2008 Overall accuracy for 2008 landuse classification was 81.25% with kappa statistic of 0.7348. The result of accuracy assessment obtained was quite good. It represents that more than 80% of the image have been correctly classified as the actual landuse types as in ground. Detail on accuracy assessment report is enclosed in Appendix C (iv). 4.3 Landuse Change Detection Digital change detection is the process helps in determining the changes associated with landuse and landcover properties with reference to geo-registered multi temporal remote sensing data (Yacouba et al., 2009). The application of landuse change using remote sensing data and techniques have been used in worldwide and become as one of the valuable method in monitoring the landuse 70 changes. From the applications of remote sensing, results were obtained in two parts which consist of image changes and statistical changes. Image changes will illustrate the change in landuse against years in term of graphics. Generally, results of image change can be seen visually. This process was carried out using remote sensing software. While on the other hand, statistical changes shows more specifically the measured information for each landuse class in terms of area and percentages differences. The determination statistical changes were carried out using GIS software, ArcView 3.2. 4.3.1 Differential in 1991 to 2008 images In the initial process, we need to figure out in general the changes that have taken place along Danga-Pendas in a long time frame. Figure 4.5 shows the differentiation series of landuse information from 1991 to 2008. As illustrated in the images, there are an obvious changes on landuse that can be monitored. In early 1991, the urban/ developed areas are not as dense as developed areas in 2005 and 2008. Furthermore, the open area that existed in 1991 became lesser in late 2000. This is because most of the open areas have been developed as urban areas. Beside that, some of the mangroves that existed in the estuaries in 1991 become lesser and lesser in 2000, 2005 and 2008. 71 1991 2000 (a) (b) 2005 2008 (c) (d) Figure 4.5: Series of landuse types for year (a) 1991 (b) 2000 (c) 2005 and (d) 2008 at Johor Bahru city center. Along Sungai Danga and Sungai Skudai estuaries, there are variations of landuse changes that can be observed. From Figure 4.6, most of the mangrove area that was present in 1991 becomes lesser in 2005 and 2008. The area was also recovered by scrubs and urban/ developed area. On the other hand, clear water bodies observed in 1991 were less with the presence of boats and marine water activities such as aquaculture, fishing and boating. In addition, there were no particular land lines that can be observed in Sungai Skudai estuary. It can be clearly observed starting from year 2000 to 2008. These circumstances could be due to the embankment of the bay for development. 72 1991 (a) (b) 2005 (c) 2000 2008 (d) Figure 4.6: Series of landuse information at Sungai Danga and Sungai Skudai estuaries for year (a) 1991 (b) 2000 (c) 2005 and (d) 2008. At other parts near Tebing Runtuh and Nusajaya, there were obvious changes on landuse from 1991 to 2008 (refer Figure 4.7). The initial scrubs and cultivation landuse types of the area in 1991 have been developed to open area in 2000 and become built up in 2005. In 2008, the area received rapid changes due to the development of IDR. From Figure 2.8 in 2008, it can be seen clearly the open area of IDR development which is still in construction progress. 73 1991 2000 (a) (b) 2005 2008 (c) (d) Figure 4.7: Series of landuse information at Nusajaya for year (a) 1991 (b) 2000 (c) 2005 and (d) 2008. Danga to Pendas area, which is located at the end of the study area covers the Sungai Pendas estuary. The obvious growth of the area is due to the development of Second-Link Bridge which connects Malaysia and Singapore. The expansion of the bridge gives numerous changes to the surrounding landuse of the area. First, there were slightly build-up areas in earlier 1991 and 2000 (refer Figure 4.8). However it can be seen undoubtedly that there were some developments through out this area. Nevertheless, the mangrove land area still exists 74 1991 2000 (a) (b) 2005 2008 (c) (d) Figure 4.8: Landuse information at Sungai Pendas coastal area for year (a)1991 (b) 2000 (c) 2005 and (d) 2008. 4.3.2 Statistical Differences of Landuse Changes Landuse changes can also be evaluated using statistical approach where each of the landuse type was analyzed in order to see difference of area between year. The results were obtained in area of changes (ha) and the initial area (ha) for each class for each year. Results for four years of landuse change is represented on Table 4.1. For further studies, only significant year were considered such as year 1991, 2005 and 2008 where statistical landuse changes were analyzed. Comparison between before and after 2005 to 2008 image is very important since the development of IDR region began in 2006. 75 Table 4.1: Overall statistical landuse for 1991, 2000, 2005 and 2008 along DangaPendas area including Singapore Class Landuse Area (ha) 1991 2000 2005 2009 Mangrove 2 311.92 2 596.68 2 273.67 1 371.78 Water Body 7 055.01 7 322.22 7 473.51 5 027.94 17 878.50 21 257.28 22 103.46 28 713.51 4 235.40 9 560.43 9 121.50 4 209.51 30 742.20 23 611.05 21 407.13 20 862.57 2 923.74 4 816.71 2 923.74 3 479.04 Urban/Developed Forest/Scrubs Cultivation Area Open Area 4.3.2.1 Statistical Changes Report for 1991 and 2005 There are major landuse difference obtained between 1991 and 2005. From Table 4.2, cultivation area experienced major changes with a total of 9,335.07 ha (30.36%) followed by urban/ developed at 4,224.96 ha (23.63%) and forest/scrubs at 4,886.07 ha (15.36%). Image difference represents the changes of landuse types whether it more or less than before. The negative sign means that the areas are reduced while the positive represent increase in the area. Based on the table, mangrove, open area and cultivation types become lesser in 2005 compare to 1991. While scrubs and developed types have greatly increased. This may be due to openings for cultivation and open area for new development to become urban area. 76 Table 4.2: Statistical changes based on landuse types between 2005 and 1991 along Danga-Pendas area including Singapore Class Changes 1991-2005 1991 (ha) Mangrove Water Body Urban/Developed Forest/Scrubs Cultivation Area Open Area 2005 (ha) Difference (ha) Difference (%) 2 311.92 2 273.67 - 38.25 - 1.65 7 055.01 7 473.51 418.50 5.93 17 878.50 22 103.46 4 224.96 23.63 4 235.40 9 121.50 4 886.10 15.36 30 742.20 21 407.13 - 9 335.07 - 30.36 2 923.74 2 923.74 -156.78 - 5.36 Note : + increase in area - reduction in area 4.3.2.2 Statistical Changes Report for 2005 and 2008 The landuse changes between 2005 and 2008 are significant to the development of IDR. The IDR project region was set up and initiated in 2006. As mentioned and illustrated in Figure 4.7, there are major differences in the image with the opening of the new area. Review based on Table 4.3, shows that the open area and urban/developed become the largest changes compared to other landuse types. Open area with an increase of 553.30 ha (18.99%) is very significant since there are many parts of Danga-Pendas area opened for new development or constructions based on IDR plan. Urban/ developed have also been recorded as major increased with 6,610.05 ha (29.91%) since progress of development due to IDR and the expansion of Johor town such as Danga Bay. Scrubs shows a large reduction with 4,912.47 ha (53.86%) compared to other landuse types followed by mangrove with 901.89 ha (39.66%), water body at 2,445.57 ha (32.72%), and cultivation area with 554.56 ha (2.50%). 77 Table 4.3: Statistical changes based on landuse types between 2005 and 2008 along Danga-Pendas area including Singapore. Class Changes 2005-2008 2005 (ha) Mangrove Water Body Urban/Developed Forest/Scrubs Cultivation Area Open Area 2008 (ha) Difference (ha) Difference (%) 2 273.67 1 371.78 -901.89 - 39.66 7 473.51 5 027.94 -2 445.57 - 32.72 22 103.46 28 713.51 6 610.05 29.91 9 121.50 4 209.51 -4 912.47 - 53.86 21 407.13 20 862.57 -544.56 - 2.50 2 923.74 3 479.04 555.30 18.99 Note : + increase in area - reduction in area 4.4 Water Quality Analysis Water quality along Danga-Pendas coastal area was obtained from samplings that were carried out from November 2008 to April 2009. The six months sampling were conducted to see the variation of water quality parameters due to sampling stations. Eleven sampling stations were analyzed starting from the upper Danga estuary to final station which is close to SecondLink Bridge. Analysis was carried out based on physical, nutrient and heavy metals components. Results were then compared with Malaysian Interim National Water Quality Standard (INWQS) and Malaysia Interim National Marine Water Quality Standard (INMWQS). 4.4.1 Physical and Chemical Water Quality Parameters Physical and chemical water quality parameters include in this study are dissolved oxygen (DO), pH, salinity, temperature, ammoniacal nitrogen biochemical oxygen demand (BOD) and chemical oxygen demand (COD). 78 4.4.1.1 Dissolved Oxygen (DO) The content of oxygen is an important indicator of the pollution of a water body. DO depend on several factors, some of which are the amount of rainfall, saltiness of the water, the amount of decomposition in the water, the amount of plant life in the water, type of rock in riverbed and presence of pollutants. The study of oxygen content plays quite an important role, when evaluating the conditions of the habitation in a water body (Vynavi, 2005). Figure 4.9 shows the variation in DO level along Danga-Pendas sampling stations. Station S1 to S5 which is from Sungai Skudai estuaries to Sungai Melayu estuaries showed lower DO levels compared to Sungai Perepat to Sungai Pendas. This maybe due to the development of Danga and Skudai areas which tend to discharge many pollutants thus decreasing the DO level. Compared to the area from Sungai Perepat to Sungai Pendas, there is not much development found and most of the areas were covered with natural mangrove. The time and day also can affect the solubility of oxygen in water bodies. The more hours of daylight there are, the more photosynthesis may takes place, resulting in higher concentration of oxygen in midday. All sampling in this study were done during daytime starting in the morning at station S1 and end in midday at station S11. 5.00 4.50 4.00 DO (mg/L) 3.50 Nov 3.00 Dec 2.50 Jan 2.00 1.50 Feb 1.00 Mar 0.50 Apr 0.00 1 2 3 4 5 6 7 8 9 10 11 Sampling Stations Figure 4.9: DO concentration measured at station S1 to S11 from November 2008 to April 2009. 79 4.4.1.2 Temperature The temperature of water is one of the most important characteristics that determines to a considerable extent, the trends and tendencies of changes in the river water quality. Increased water temperature will decrease the solubility of dissolved oxygen. Water temperature above 27ºC is unsuitable for public use and at above 32ºC it would be considered unfit for public use (Chapman, 1992). Temperature influences directly the amount of dissolved oxygen that is available to aquatic organisms. Water temperature affects the rates of all chemical and biological process. Figure 4.10 shows the results for temperature obtain from sampling. Temperature measured for all stations ranged from 27.75ºC to 30.00ºC. April 2009 have the lowest temperature range for most of the stations. While temperature measured in February 2009 state the highest for most of the stations. 30.50 Temperature ( ºC) 30.00 29.50 Nov 29.00 Dec 28.50 Jan 28.00 Feb 27.50 Mar 27.00 Apr 26.50 1 2 3 4 5 6 7 8 9 10 11 Sampling Stations Figure 4.10: Temperature level measured at station S1 to S11 from November 2008 to April 2009. 4.4.1.3 Salinity One major characteristic of an estuaries system is the variation in the distribution of water salinity. Many processes, physical, chemical or biological are related to salinity. Salinity is important in coastal waterways for several reasons. Salinity is a dynamic indicator of the nature of the exchange system. The salinity of 80 water within estuary determines how much fresh water was mixed with seawater. sea Salinity is also an important determinant de of mixing regime because of the density variation associated with with salinity variation, salinity stratification tends to inhibit inhibi vertical mixing in an estuary which can have important implications for dissolved oxygen concentrations (Wright, 2003). Salinity is the main index of mixture of seawater with water from major rivers. It can reflect the types of water and also may influence the measurement of other water quality parameters such as DO and pH. Figure 4.11 shows the salinity measured during sampling. The values of salinity seems to fluctuates at four earliest stations ions (S1 to S4) and more stable for the rest of the station. station The three lowest stations (S1, S4 and S5) are located in the points near the river mouth. Salinity increase from the river mouth to the coastal areas. Three lower stations (S1, S4 and S5) were probably obably situated at the river mouths, whereas the rest were recorded a bit far from the river mouths thus higher results obtained due to the influence of seawater. 30.00 25.00 Salinity (ppt) Nov 20.00 Dec 15.00 Jan 10.00 Feb Mar 5.00 Apr 0.00 1 2 3 4 5 6 7 8 9 10 11 Sampling Stations Figure 4.11:: Salinity measured at station S1 to S11 from November 2008 to April 2009. 81 4.4.1.4 pH pH is another important parameter which affect water quality. A change in the pH of water can alter the behavior of other chemicals in the water. The altered water chemistry may affect aquatic plants and animals. Heavy metals such as cadmium, lead and chromium dissolve more easily in more acidic water. This is important because many heavy metals also become more toxic when dissolved in water (Mesner and Geiger, 2005). The measured pH levels correspond to sampling stations were shown in Figure 4.12. As seen in the figure, the trends of pH levels were constant and stable. The reading of pH levels is in the range of 7.38 to 9.65. Human activities can also affect pH values. Several human activities that can affect the changes in pH are from polluted precipitation which is also known as acid rain. It increases the acidity of surface water near many industrial or large urban areas. The main contributors to acid rain are sulfuric acid produced by coal burning industries and nitric acid that is produced by automobile engines. Furthermore, dumping industrial pollutants directly into waters is also known as point source pollution which can have intense and immediate effects on the pH of a water body (Mesner and Geiger, 2005). 10 pH 9.5 9 Nov 8.5 Dec 8 Jan 7.5 Feb 7 Mar 6.5 Apr 6 1 2 3 4 5 6 7 8 9 10 11 Sampling Stations Figure 4.12: pH measured at station S1 to S11 from November 2008 to April 2009. 82 4.4.1.5 Total Dissolved Solids Total dissolved solid (TDS) is one of the parameters analyzed in the laboratory. The result is illustrated in Figure 4.13, where there is not much variation in TDS values along the coastal area. The values are less in contrast to the average range from 21.00 mg/L to 26.5 mg/L. TDS values are a bit higher at three stations, S1, S2 and S3. This may be due to the deposit of pollutants and sediments entering from the developed Danga and Skudai area. However, the readings had become stable for the next stations. The amount of solids in water affects the clarity of the water where the more TDS concentration, the cloudier and turbid the water. Fortunately, overall TDS values satisfy Class 1 DOE-INWQS where all stations recorded less than 500 mg/L. 30.00 TDS (mg/L) 25.00 20.00 Nov 15.00 Dec Jan 10.00 Feb Mar 5.00 Apr 0.00 1 2 3 4 5 6 7 8 9 10 11 Sampling Stations Figure 4.13: TDS concentration measured at station S1 to S11 from November 2008 to April 2009. 4.4.1.6 Ammoniacal Nitrogen Ammoniacal nitrogen parameter represents pollution from farm wastes, agricultural waste and domestic sewage effluent (Margerat, 1986; Peavy, 1986). Ammoniacal nitrogen is often found in water as a result of the discharge of sewage effluent and the high levels adversely affect the quality of water for fisheries. The result for ammoniacal nitrogen is illustrated in Figure 4.14. The range of ammoniacal 83 nitrogen during sampling was from 0.012 mg/L to 1.137 mg/L. It is shown that the values of ammoniacal nitrogen decreased as it approaches Pendas area. It is quite high at S1 and S3, which maybe due to the discharge of ammonia since ammoniacal nitrogen occurs partly in the form of ammonium ions and partly as ammonia. The highest concentration of ammoniacal nitrogen is observed at Station S1 (Sungai Skudai) possibly due the discharge of pollutants of this river where Sungai Skudai is known among the most polluted river in Johor. According to Pollution Influx Observed at Continuous Water Quality Station done by Department of Environment Malaysia, the main pollution sources in Sungai Skudai are domestic sewage or latex based industry effluent which high causes ammoniacal nitrogen concentration. This value reflects the deterioration of water quality at Sungai Skudai (Farihah, 2009). Ammonical Nitrogen (mg/L) 1.2 1 Nov 0.8 Dec 0.6 Jan Feb 0.4 Mar 0.2 Apr 0 1 2 3 4 5 6 7 8 9 10 11 Sampling Stations Figure 4.14: Ammoniacal nitrogen concentration measured at station S1 to S11 from November 2008 to April 2009. 4.4.1.7 Biochemical Oxygen Demand (BOD) Biochemical oxygen demand (BOD) is measurement of the amount of oxygen that bacteria will consume while decomposing organic matter under aerobic conditions. BOD analysis is advantageous as it provides a direct measure of oxygen in the environment (Law, 1981). The dissolved oxygen level in water is greatly affected by the content of biochemical oxygen demand. Elevated organic matter in 84 river waters increases the biochemical oxygen demand (BOD) to oxidize the organic matter (Vynavi, 2005). In this study however, the data for BOD and COD were only available for four samplings occasions which is from November 2008 to February 2009. Figure 4.15 show the results for BOD against sampling stations for November 2008 to February 2009. As illustrated on the figure, the range of BOD concentration in water samples was 4.6 mg/L to 6.7 mg/L. The water samples analyzed for earlier stations near Danga and Skudai recorded higher BOD concentrations. BOD concentrations for December 2008 and January 2009 were higher for most of the sampling stations. This might be due to decrease in brackish water levels which renders the water less turbulence due to less high wind and rain that can increase dissolution of DO into the water. As DO concentration decreases, oxygen demand will increase for the use of bacteria to carried out degradation process. High BOD values indicate a good deal of high oxygen demanding organic matter was present to be decomposed due to the discharge from industrial areas, sewage treatment plant, housing and urban areas (Vynavi, 2005). Generally, the BOD concentrations satisfy Class III of INWQS. 7 6.5 6 BOD (mg/L) 5.5 5 Nov 4.5 Dec 4 Jan 3.5 Feb 3 2.5 2 1 2 3 4 5 6 7 8 9 10 11 Station Figure 4.15: BOD concentration measured at station S1 to S11 from November 2008 to February 2009. 85 4.4.1.8 Chemical Oxygen Demand (COD) Chemical oxygen demand (COD) is a test of oxygen demand in which the organic matter is chemically oxidized instead of being biologically oxidized. COD values are higher than BOD values because this chemical test oxidizes all of the organics present in the water samples, while the BOD test which is a biological test is selective to organisms and microorganisms present in the water samples (Greenberg et al., 1979). Elevated organic matter in river waters increases the chemical oxygen demand to decompose chemicals. Increased COD levels in river waters was attributed to the increase of organic matter and inorganic chemicals in river waters from agriculture, urban run-off and industrial discharge (Wandan and Zabik, 1996) Figure 4.16 show the concentration of COD in both November 2008 to February 2009. The trends of the COD concentration shows increase against stations. The lowest concentration was recorded at the first station and starts gradually to increase up to until station S9 for December 2008. While November reading also have quite similar trend but there were reduction in COD values in station S6 and S7 and then increase at S8 to S11. The range of COD values was 834 mg/L to 3850 mg/L. COD test shows that oxygen usage was high in water samples. High COD results may be due to high salt content in the water samples, which causes precipitation with the added reagents as shown after reflux the solution obtained is cloudy. COD vials used might affect the results due to reuse of vials that is not cleaned or scratch causing diffraction of wavelength in colorimeter (Yap, 2009). 86 4500 4000 COD mg/L 3500 3000 Nov 2500 Dec 2000 Jan 1500 Feb 1000 500 0 1 2 3 4 5 6 7 8 9 10 11 Stations Figure 4.16: COD concentration measured at station S1 to S11 from November 2008 to February 2009. 4.4.2 Heavy Metals Heavy metals are pollutants that are hazardous to human and aquatic life. The concentration of heavy metals in water could be influenced by several environmental aspects which indirectly effects the contamination or accumulation. Tides are one of the factors which also indirectly affect the concentration values. However, based on the study done by Ibrahim (1993) at similar study area, he reveals that tides have less influence on the distribution of heavy metals in water. Therefore the influences of tides were neglected in this study. There are several types of heavy metals analyzed in this study with each of them having significant aspect related to human and development activities. 4.4.2.1 Zinc (Zn) Zinc is an essential nutrient, necessary for sustaining life. Although zinc is known as an ubiquitous element in nature, it is supposed that about 96% of its release into the global environment is the result of anthropogenic activities, like electroplating, smelting and ore processing, corrosion from alloys and galvanized 87 surfaces as well as erosion from agriculture land (Landner and Reuther, 2004). Most of the activities that originates zinc to water comes from the development of industrial and agricultural activities which so significant to Johor Bahru. Zinc concentration in water samples along Danga-Pendas area are varies with month. Based on Figure 4.17, the three earliest months (November 2008 to January 2009) were more consistence and lower compare to the other three months later (February to April 2009). The distribution values of Zn for February to April 2009 show that the concentrations become lesser or decreased when it approaches Pendas coastal area. The concentration of Zn is higher at several stations and increased at S2 before declining until the last station. The range of Zn observed was from 0.011 mg/L to 0.65 mg/L. Unfortunately, the concentration of Zn in water along this area were higher compared to the quality criteria concentration that was recommended for Zn in marine and estuarine waters set by U.S EPA which is 0.09 mg/L (Wu et al., 2008). Compared to the permissible limits of INWQS for Zn which is 0.5 mg/L, nearly all samples are under the limits. Only several samples in station S2 and S3 recorded higher than the permissible limits. 0.7 0.6 Zn (mg/L) 0.5 Nov 0.4 Dec 0.3 Jan 0.2 Feb Mar 0.1 Apr 0 1 2 3 4 5 6 7 8 9 10 11 Stations Figure 4.17: Zinc concentration measured at station S1 to S11 from November 2008 to April 2009. . 88 4.4.2.2 Lead (Pb) Typically, seawater contains trace amounts of lead (2 to 30 ppt) while an average river contain between 3 and 30 ppb. Mining, smelting and other industrial emissions and combustion sources and solid waste incinerators are the primary sources of lead. Another source of lead is paint chips and dust from buildings built before 1978 and from bridges that source of this metal (Sax, 1974). Lead is one of the significant metals which affect the water quality along study area since Johor Bahru is among one of the active industrial towns in Malaysia. Lead is a hazardous metals that also contaminates water samples. Figure 4.18 shows the variations of Pb concentration in water were much similar to the variations of Zn concentration. The concentrations were highest at the earlier stations such as in S2 (Sungai Danga estuaries) and S3 as illustrated. The concentration starts to decrease moving towards the final station. Range of Pb concentration in water along Danga-Pendas coastal area was 0.09 mg/L to 3.23 mg/L where both the lowest and highest concentration were recorded in the same month, i.e February 2009. The higher concentrations in earlier stations were due to effluent discharges from sewage treatment plant, pig farms and industries which are the main contributors (Vynavi, 2005). Nevertheless, most of the concentrations of Pb recorded did not meet the Malaysia Interim National Marine Water Quality Standard (INMWQS) which is 0.1 mg/L. This situation gives consequences that the quality of Danga-Pendas coastal water is heavily polluted with Pb thus could affect the aquatic life as well as human health. 89 3.500 Pb (mg/L) 3.000 2.500 Nov 2.000 Dec 1.500 Jan Feb 1.000 Mar 0.500 Apr 0.000 1 2 3 4 5 6 7 8 9 10 11 Stations Figure 4.18: Lead concentration measured at station S1 to S11 from November 2008 to April 2009. 4.4.2.3 Cadmium (Cd) The concentration of cadmium in water samples along Danga-Pendas is illustrated in Figure 4.19. The trends of the concentrations were different for the first three months i.e in November 2008 to January 2009 and the next three months in February 2009 to April 2009. Based on the graph, the first three months show more stable and constant Cd concentration readings compared to concentration to the last three final months. The concentration in February to April 2009 recorded more similar trend as observed for Zn and Pb. The concentration tends to be higher at the earlier stations and decreased when approaching the final station in Pendas. The range of Cd concentration was from 0.019 mg/L to 0.505 mg/L. The highest Cd concentration was recorded at S3 in Danga and the lowest concentration was recorded at the final station, S11 in Pendas. The same situation was observed for Cd, where most of the Cd levels recorded exceeded the Interim National Marine Water Quality Standard (INMWQS) that limits the Cd concentration in water at 0.1 mg/L. Cadmium compounds enter the water bodies from the discharge of effluents from paint manufacturing industries where cadmium is used to produce excellent colour from rechargeable batteries (Herber, 1994). Other major sources of Cd in river water are from sewerage treatment plants, pig farms and manufacturing industries (Erdawati, 1997; IWK, 2000; Mazlin et al., 2000). Cadmium can escape from 90 landfills where trash is buried and seep into the ground and groundwater. From there, it can become part of food and water that humans and animals ingest. 0.6 Cd (mg/L) 0.5 Nov 0.4 Dec 0.3 Jan Feb 0.2 Mar Apr 0.1 0 1 2 3 4 5 6 7 Stations 8 9 10 11 Figure 4.19: Cadmium concentration measured at station S1 to S11 from November 2008 to April 2009. 4.4.2.4 Nickel (Ni) Result for nickel concentrations in water is presented in Figure 4.20. As shown on the graph, there were predictable trends for the concentration of Ni against stations along Danga-Pendas. The concentration of Ni increased at the first three earlier stations (S1 to S3) before decrease towards station S4. Then the concentrations gradually increase again for few stations and start to decrease at station S8 and S9. The observed concentration then increase up to the final station in Pendas. The range of the concentration was 0.08 mg/L to 0.51 mg/L. The concentration limit of Ni given in Interim National Water Quality Standard (INWQS) is 0.1 mg/L. Based on the results obtained, nearly all of the samples exceeded the limit. 91 0.6 0.5 Ni (mg/L) 0.4 Nov Dec 0.3 Jan 0.2 Feb 0.1 Mar Apr 0 1 2 3 4 5 6 7 8 9 10 11 Stations Figure 4.20: Nickel concentration measured at station S1 to S11 from November 2008 to April 2009. The overall water quality along Danga-Pendas coastal area that have been measured shows that the status of water is average. For some physical and chemical parameters such as DO, pH and ammoniacal nitrogen, the average value only satisfy Class II and III of INWQS. However, the result for TDS satisfies Class I of INWQS. The most critical parameter that affects water quality along the study area was heavy metals. Although there was only four heavy metal parameters that were analyzed in this study, nearly all the metals shows high concentration level. Judging against four metals, three of them, nickel, cadmium and lead were above the permissible levels of INWQS and INMWQS. Conversely, zinc recorded good result as all of the samples analysed fulfilled INWQS limit. Stations located at Sungai Danga, Sungai Skudai and Sungai Melayu estuaries, S1 to S5 show higher (worst) physical, chemical and heavy metals concentrations. This might be due to the developed town and domestic area which tend to discharge pollutants to this area. Furthermore, agricultural activities in several parts of the study area such as at Sungai Melayu also give an impact to water quality of this area since the usage of fertilizers tends to run off to this area compared to Pendas. 92 The concentration and levels of pollutants in water were also influenced by physical and biological environment. Tides also play an important role in analyzing water quality parameters since there were different in concentration due to different types of tide. However, based on the study done by Ibrahim (1993) at similar study area, the tides have less influence to the concentration of water quality parameters in water. Beside, rainfall distributions also play a part in assessing water quality. Wet season is believed to give more effects of the concentration of pollutant to water than in dry season. However, in this study, there is no significant relation due to the statement. As observed, most of the parameters especially heavy metals were recorded higher in dry seasons compared to wet seasons. 4.5 Analysis of Previous Water Quality Data Compared to Present Data Analyses of the previous water quality data are useful in order to observe the variation and differentiation in water quality along Danga-Pendas coastal area. It is also helpful in analyzing the effects of landuse changes on water quality generally and to see the effects of the development to water quality for these times specifically. Previous water quality data have been obtained from several studies that have been done along this area. Water quality data from 1991 and early 2006 were used in analyzing the status of water quality along Danga-Pendas coastal area. Two most significant areas along Danga-Pendas were chosen in order to evaluate the variations of water quality in these selected years. The first one is located at Danga station and another one at Pendas station. Danga station is considered very significant since there were a lot of development in the area since 1991. The major development is urbanization of Danga Bay and the surrounding areas was predicted to show high impact on water quality along this area. On the other hand, Pendas station was significant as this area received less development compared to Danga area. Water quality parameter that were compared and analyzed in this study includes several physical and chemical data such as pH, temperature, dissolved oxygen (DO) and ammoniacal nitrogen (AN) for three years. Other physical and 93 chemical water quality data was not analyzed since there were limited sources and references. Heavy metal data was also analyzed in order to see the variation trend and the effects due to development (landuse change) and also to correlate with their concentration on mussels as analyzed and discussed in more on Chapter 5. Some of the heavy metal parameters analyzed were zinc, cadmium, lead and nickel. Table 4.4 show the availability description and reference of the data acquired from several previous studies. Whereas Figure 4.21 and 4.22 illustrate the comparison graphs of some physical, chemical and heavy metals data for 1991, 2006 and 2009. Table 4.4: Water quality data for year 1991, 2006 and 2009 Water Quality Parameters Year Station Physical and Chemical pH References Heavy Metals Temp DO AN Zn Cd Pb Ni (ºC) (mg/L) (mg/L (mg/L) (mg/L) (mg/L) (mg/L) ) 1991 2006 2009 Danga 0.76 30.5 2.75 NA 31.428 0.082 0.773 NA Gunasegaran (1991); Pendas NA NA NA NA 16.092 0.059 0.596 NA Ibrahim (1993) Danga 8.15 28.8 5.46 0.443 0.243 0.001 0.90 0.008 Ridhuan (2006); Pendas 7.97 NA 5.68 0.187 NA NA NA NA Shaiful (2006) Danga 8.59 29.00 3.12 0.242 0.339 0.282 2.253 0.332 Pendas 8.68 29.28 4.33 0.560 0.753 0.107 0.430 0.214 Current study NA – Not Available 94 95 As illustrated in Figure 4.21(a) and (b), the pH and temperature trend for 1991 to 2009 is constant and much more similar. However, there was a slight increase in pH from 1991 to 2009. The lowest pH for Danga estuaries area was recorded in 1991 at 7.64 and increase up to 8.59 in 2009. The same trend was also observed in Pendas area, where the pH values increased from 7.97 in 2006 to 8.68 in 2009. The variation against year for temperature can only be observed for Danga station since there were not enough data acquired for temperature for Pendas area. Temperature recorded in 1991 was slightly higher at 30.5ºC compared to year 28.8ºC at 2006 and 29.0ºC at 2009. The temperature recorded was 28.8ºC in 2006 before increasing to 2009. In 2009, the temperature values for Danga and Pendas nearly the same with a difference of 0.28ºC. Figure 4.21(c) and (d) represent the concentration of dissolved oxygen and ammoniacal nitrogen in water for year 1991, 2006 and 2009. As illustrated in the figure, the concentrations of dissolved oxygen in water were higher in 2006 compared to both 1991 and 2009. However, the lowest DO reading was recorded in 1991 at Danga area at only 2.75 mg/L. This shows that the area might be polluted at the specific time. In 2006, the concentration of DO at both Danga and Pendas areas increase to 5.46 mg/L and 5.68 mg/L respectively. However in 2009, DO level at Danga and Pendas was recorded at 3.12 mg/L and 4.33 mg/L respectively. Although the concentration of DO was higher in 2006, but the level only satisfy of Class II Interim National Water Quality Standard (INWQS). In 2009, the DO level only satisfy Class III of INWQS which indicate that the water quality level for the areas are in average condition. However, the trend of ammoniacal nitrogen concentration differs with increasing years. In Danga, the concentration decreased from 0.433 mg/L in 2006 to 0.242 mg/L in 2009. Meanwhile for Pendas area an increase from 0.19 mg/L in 2006 to 0.56 mg/L in 2009 was detected. Danga station recorded high ammoniacal nitrogen concentration which might be due to discharge of industrial and domestic waste from the developed Danga Bay, Johor Bahru town and the surrounding area. Furthermore there was also discharge of agricultural run offs from the cultivated area 96 near Danga estuaries. Compared to Pendas which was less developed there was less human activities that influenced to the ammoniacal nitrogen concentration. 10 pH 8 6 Danga 4 Pendas 2 NA 0 1991 2006 2009 Year (a) 35 Temperature ( ºC) 30 25 20 Danga 15 Pendas 10 5 NA 0 1991 NA 2006 2009 Year (b) 6 DO (mg/L) 5 4 3 Danga 2 Pendas 1 NA 0 1991 (c) 2006 Year 2009 0.6 AN (mg/L) 0.5 0.4 0.3 Danga 0.2 Pendas 0.1 0 NA 1991 2006 2009 Year (d) Figure 4.21:: Water quality data at Danga and Pendas area for year 1991, 2006 and 2009 for (a) pH (b) temperature (c) DO and (d) ammoniacal nitrogen (AN). 97 Figure 4.22 shows the graph of zinc, cadmium, lead and nickel concentrations for water samples in the Danga-Pendas area. There are no data available for Pendas area in 2006 for Zn, Cd, Ni and Pb. As observed in 1991, 2006 and 2009, the concentrations of heavy metals recorded were higher at Danga station compared to Pendas station. The highest heavy metals concentrations for Cd, Pb and Ni detected in 2009. As illustrated in Figure 4.22(a), the concentration of Zn in Danga area was highest in 1991 with 31.43 mg/L and decreased to 0.24 mg/L in 2006 and increased to 0.34 mg/L in 2009. The concentration of Zn for Pendas area also show a decreasing trend from 16.09 mg/L in 1991 to 0.75 mg/L observed in 2009. The reduced concentrations trend of Zn might be due to less influence from agricultural run offs. Cadmium concentrations as shown on Figure 4.22(b) have higher concentration in 2009 compared to 1991. At Danga station, Cd concentration in 1991 was 0.082 mg/L compared to 0.0001 mg/L in 2006. Then, the concentration increased to 0.282 mg/L in 2009. Although Cd concentration in Pendas was much lower compared to Danga, increase in concentration was observed from 1991 to 2006 i.e at 0.059 mg/L and 0.107 mg/L respectively. The current Cd concentration is slightly higher than the limit set by INMWQS at 0.1 mg/L. Figure 4.22(c) illustrates the concentration of lead in water for Danga and Pendas area in 1991, 2006 and 2009. The trend for Pb concentration was similar to Cd concentration. For Danga station, the lowest Pb level recorded in 2006 was at 0.773 mg/L and increased in 2009 to 2.253 mg/L. However, Pendas station show a slight decrease in 2009 compared to 1991. Nickel concentration is shown in Figure 4.22(d) for Pendas and Danga in 2009 and for Danga only in 2006. Data is not available for nickel in 1991 both in Pendas and Danga and in 2006 for Pendas only. In Danga area, the concentrations increased from 0.008 mg/L in 2006 to 0.332 mg/L in 2009. Both Pb and Ni concentration in 2009 exceeded the required permissible level of 0.1 mg/L. 98 35 Zn (ppm) 30 25 20 Danga 15 Pendas 10 5 NA 0 1991 2006 2009 Year (a) 0.3 Cd (ppm) 0.25 0.2 0.15 Danga 0.1 Pendas 0.05 NA 0 1991 2006 2009 Year (b) 2.5 Pb (ppm) 2 1.5 Danga 1 Pendas 0.5 NA 0 1991 2006 2009 Year (c) 0.35 0.3 Ni (ppm) 0.25 0.2 Danga 0.15 Pendas 0.1 0.05 NA 0 1991 2006 Year 2009 (d) Figure 4.22:: Heavy metals concentration data at Danga and Pendas area for year 1991, 2006 and 2009 (a) zinc (b) cadmium (c) lead and (d) nickel. 99 4.6 Analysis on the Effects of Landuse Changes to Water Quality along Danga-Pendas Coastal Area Studies on landuse and landcover-water quality relationship has been studied for a long time by researchers (Reth et al., 1996; Allan et al, 1997; Johnson et al, 1997, Basnyat et al., 1999, Yunus et al., 2003). Such studies revealed that the type and severity of water contamination is often directly related to human activities, which can be quantified in terms of the intensity and type of landuse in the source areas of water to streams and aquifers. One of the most important factors that can affect the quality of a water body is the landuse within its watershed. Urban sprawl (particularly the paving of large segments of landscape) can have significant and usually negative impacts on water resources. Although growth and landuse change may be inevitable in many communities, the way in which growth takes place affects its impact on water quality. Based on the results obtained from both integrated landuse and also observed water quality data, the negative effects of landuse changes to water quality cannot be resisted. As years passes by, we can see the reduction or decrease in natural land surface. Mangrove and forested area have shown significant decrease with increase in developed build-up and agricultural area. At the same time, decrease in quality of coastal water was also detected. Metals, specifically recorded extensive increase in water concentration to increase of build-up area. This situation is significantly related to land-based activities such as domestic and industrial wastes. The type of landuse which represent the land-based activities showed significant accumulation results. The increase of industrial development and agricultural will also increase heavy metals accumulation to the water (Yunus et al., 2003). The relationship of landuse-water quality can also be proven based on location of area observed. In more developed areas of Danga, the level of water quality parameters recorded for most of all the sampling carried out in 2009 or by previous studies is worst compared to the water quality observed in Pendas area. This may be due to rapid increase in population and industrial facilities around the main town of Danga and Johor Bahru. Heavy metals in untreated municipal and industrial 100 wastewater discharged directly into canals and rivers will eventually find their way to marine environment. The levels of water quality for most of the parameters recorded in 2009 are higher than 1991 and 2006. This indicates that the development of the surrounding land may have impact on water quality along Danga area. The increase in build-up area with numerous landuse practices can affect the quality of streams and coastal water in various ways. Industrial activities may discharge their effluents directly into streams and coastal water. Moreover, Johor plays an important role as an industrial state. Figure 4.23 illustrate the types of manufacturing industry in Johor for year 2005. Most of these sectors play a part in using heavy metals and thus affecting the water quality of the surrounding area. Furhermore, increase in agriculture sector also degraded the water quality along this area as fertilizers and pesticides applied to cultivated area can wash into streams. In addition, the new development of IDR might also degrade the water quality. The rapid and massive development may introduce pollutants along this area since the development takes place just beside the coastal area of the Danga-Pendas. Figure 4.23: Concentration of manufacturing sectors in and outer of Johor Bahru. (Source: SJER, 2005) There is also no doubt that pollution from neighbouring country, Singapore can degrade water quality in Danga-Pendas coastal area since the straits is narrow and located in the middle of Malaysia-Singapore which acts as a boundary for both countries. Singapore which is one of the most developed countries in this region is 101 also well-known as an industrial country that might influence decrease in water quality along this area. In order to assess the effect of development in Singapore, an integrated landuse change maps derived earlier also includes Singapore land area. CHAPTER 5 EFFECT OF WATER QUALITY ON GREEN MUSSELS (Perna viridis) 5.1 Introduction This chapter focuses on the effects of water quality on green mussels (P.viridis) along Danga-Pendas coastal area. This area has been proven as Malaysia’s best breeding place for P.viridis by Fisheries Institute of Malaysia. P.viridis is a type of mollusks that is considered as highly nutritious seafood. However, the undergoing rapid development in Pendas-Danga area may affect the water quality as well as P.viridis’s quality along this area. In this chapter, analyses on mussel include heavy metal contaminants in water and green mussels. 5.2 Analysis on Effects of Water Quality on Green Mussels Vs Water Samples Analysis on the effect of contaminants on green mussels was compared to the concentration in water samples in order to see the correlation between them. Mussels were not sexed, as sex has been found to be an unimportant factor in influencing contaminant concentrations in P.viridis (Bayen et al., 2004). Although P.viridis may be affected by seasonal variation, Malaysia is not a temperate country with four seasons, therefore it does not play an important role in the study (Yap, 2009). 103 The study has taken into consideration of both in-situ measurement and laboratory analysis. Parameters measured in-situ such as DO, salinity, temperature and pH while laboratory analysis involves of ammoniacal nitrogen and heavy metals. All the parameters were analyzed to see the correlation on water samples and mussel’s contamination. 5.2.1 Physical Parameters Physical parameters are among the most important factors for living organism in water bodies. This is because the suitability of growth condition and survival of organisms relys on the condition of the physical aspects of the water. DO, salinity, temperature and pH are the most significant parameters that represent water condition. Biologically, P.viridis habitats are primarily found at estuarine and coastal water which is warm (27ºC to 32ºC) and have high salinity ranging from 27 to 33 ppt (Hickman, 1989). 5.2.1.1 Dissolved Oxygen (DO) Dissolved oxygen is one of the important components needed by the underwater organism. The minimum amount of dissolved oxygen required to sustain a variety of living organism is 5g/m3. From the viewpoint of living organisms, no gas is more important than oxygen. Because all heterotrophs use oxygen for their respiration, it tends to be removed continuously from water. This means that it can enter water through solution at the air-water interface or through photosynthesis by aquatic plants. High level of animal activity, coupled with an active detritus food chain, can withdraw a large amount of oxygen from the water (Vynavi, 2005). As shown in Figure 5.1, the concentration of DO measured gradually increased from station M2 as it approaches the last station M4. The value however does not differ much. Dissolved oxygen available for P.viridis is usually affected by the presence of chromium. In which, the oxygen consumption of P.viridis decreased 104 with increasing exposure duration of chromium (Vijayavel, 2007). However, the DO values measured are lower than the average of 5 mg/L. The reduction of DO concentration may also be due to nutrient enrichment of water column from mussels excretory products (Ferreira et al., 2008; Rlliot et al., 2008). 4.50 DO (mg/L) 4.00 Nov Dec 3.50 Jan 3.00 Feb Mar 2.50 Apr 2.00 M1 M2 M3 M4 Stations Figure 5.1: DO concentration at mussel sampling stations, M1 to M4 from November 2008 to April 2009. 5.2.1.2 Salinity Salinity is a major factor influencing the distribution and physiology of aquatic life in marine systems. Variation of salinity affects the growth, survival and metabolic physiology of organism (Blackmore and Wang, 2003). Increase in dissolved salts will also decrease the amount of dissolved oxygen (Wright, 2003). Figure 5.2 shows the results of salinity measured in-situ for a series of six months. All stations show the same variation of concentration. The salinity measured at the M1 decrease for station M2 before increasing again in station M3 and M4. The last station, station M4 recorded high salinity due to the influence of salts content from the open sea. The range of salinity values measured was 22.55 ppt to 24.66 ppt. Salinity suitable for shellfish water is 12 ppt to 38 ppt (European Parliament, 2006). P.viridis has a broad salinity range from 17 ppt to 33 ppt (NIMPIS, 2000). 105 Hickman (1989) reported that the primary growing habitat for P.viridis is within the range of 27 ppt to 33 ppt. However, numerous studies have shown that there is an increase in metal uptake by aquatic organisms at reduced salinities condition (Rajagopal, 1998). 25.00 24.50 Salinity (ppt) 24.00 Nov 23.50 Dec 23.00 Jan 22.50 Feb 22.00 Mar 21.50 Apr 21.00 M1 M2 M3 M4 Stations Figure 5.2: Salinity level at mussel sampling stations, M1 to M4 from November 2008 to April 2009. 5.2.1.3 Temperature Temperature plays a vital role in chemical and biochemical reactions. The metabolic rate of aquatic organisms is related to water temperature. In warm waters, respiration rates increase leading to increase in oxygen consumption. Thus, growth rate of aquatic organisms will also increases. This can lead to increase in decomposition of organic matter, water turbidity, macrophyte growth and algal blooms, especially when nutrient conditions are suitable (Jackson and Jackson, 1996). Toxic chemicals made more soluble by higher temperature may present an additional hazard to the organisms in the water (US EPA, 1986). Higher temperature increases the toxicity of many substances such as heavy metals or pesticides, whilst the sensitivity of the organisms to toxic substances also increases (Vynavi, 2005). 106 Different aquatic organisms have different abilities to live on temperature variations in water. Temperature plays a key role in influencing the reproductive activity of P.viridis (Rajagopal et al., 1998). Figure 5.3 shows the result for temperature measurement. Temperature values ranged from 28.21ºC to 29.9ºC during sampling. P.viridis also has a wide range temperature tolerance at 11ºC to 32ºC (NIMPIS, 2000). However, the optimum temperature for P.viridis biological habitat is in warm water ranging from 27ºC to 32ºC (Hickman, 1989). Although the thermal range of the green mussel is broad, reduced temperature can give significantly negative impacts on growth rates. Lower temperature and lower salinity will induce spawning. Total mortality was reported after 24 hour exposure at 33°C and 35°C (Sivalingam, 1977). Previous study conducted had proven that there are inter-relation between temperatures, salinity with concentration of metal accumulation in green mussels. High temperature and lower water salinity will increase the filtration rate of mussels, which leads to a rapid accumulation of metal contents. Effect of high temperature towards the concentration of heavy metals in water is similar where higher temperatures generally imply higher solubility of metal salt (Wong et al., 2000). 30.50 Temperature ( ºC) 30.00 Nov 29.50 Dec 29.00 Jan 28.50 Feb 28.00 Mar 27.50 Apr 27.00 M1 M2 M3 M4 Station Figure 5.3: Water temperature at mussel sampling stations, M1 to M4 from November 2008 to April 2009. 107 5.2.1.4 pH pH is another important water quality parameter that can be measured in-situ. The pH of water has an important influence on living organisms and on any use of the water. If the water is too acidic and too alkaline, there will be very limited aquatic life. It also affects the growth habitat and survival of P.viridis. Study done by Vijayavel (2009) showed that the mortality of mussels increased with decreasing pH and increasing hardness and alkalinity variables. In contrast, the mortality decreased with increasing pH and decreasing hardness and alkalinity values. A decrease in pH would increase metal availability, rendering itself to greater uptake by organisms and can cause physiological damage to aquatic life (Connell and Miller, 1984). From Figure 5.4, there was not much variation in pH level, the values are recorded in the range of 7.61 to 9.59. Each sampling station recorded similar pH values and trend. The difference can be seen in terms of month, where the period of December 2008 and January 2009 pH reading was the highest compared to the other months. 12 10 Nov pH 8 Dec Jan 6 Feb 4 Mar Apr 2 0 M1 M2 M3 M4 Stations Figure 5.4: pH at mussel sampling stations, M1 to M4 from November 2008 to April 2009. 108 5.2.1.5 Total Dissolved Solids (TDS) Total Dissolved Solids (TDS) are solids in water that can pass through a filter. TDS is a measure of the amount of material dissolved in water. This material can include carbonate, bicarbonate, chloride, sulfate, phosphate, nitrate, calcium, magnesium, sodium, organic ions, and other ions. A certain level of these ions in water is necessary for aquatic life. Changes in TDS concentrations can be harmful because the density of the water determines the flow of water into and out of an organism's cells. However, if TDS concentrations are too high or too low, the growth of many aquatic lives can be limited which will cause death. Figure 5.5 shows the result of TDS values against mussel sampling stations. The values are in the range of 22.61 mg/L to 24.64 mg/L and a bit lower at the earliest station and increased when approaching final station. The dissolved solid represent the cloudiness or turbidity of water. It affects the amount of light entering the water and thus restricts photosynthesis process. Therefore it also affects the amount of dissolved oxygen that indirectly will affect the organism living including P.viridis. 25.00 TDS (mg/L) 24.50 24.00 Nov 23.50 Dec 23.00 Jan 22.50 Feb 22.00 Mar 21.50 Apr 21.00 M1 M2 M3 M4 Stations Figure 5.5: TDS concentration at mussel sampling stations, M1 to M4 from November 2008 to April 2009. 109 5.2.1.6 Ammoniacal Nitrogen The concentration of ammoniacal nitrogen against sampling stations is illustrated in Figure 5.6. The trend of the concentration observed is shown in decreasing trend when approaching towards the final station. The sources of ammoniacal nitrogen in water originate from the discharge of ammonia such as from agricultural activities. The range of ammoniacal nitrogen in water at mussel sampling stations was 0.012 mg/L to 0.199 mg/L. An average of the ammoniacal nitrogen concentration measured in this study does not comply with the Malaysia Interim National Water Quality Standard (INWQS) which is at 0.1 mg/L. Although shellfish aquaculture does not require additional food unlike other forms of marineculture (Zhang et al., 2009) and less serious than finfish farming, sedimentation of feces, pseudo feces and fall-off beneath the shellfish farms could effectively lead to organic enrichment, which is generally similar to finfish marineculture (Shanmugam et al., 2007). The urine and feces from the aquatic animals can cause high content of ammoniacal nitrogen in water. Besides that, the increase of nitrogen and phosphorus loading into water may by virtue increase primary production and be associated with enhanced shellfish growth (Ferreira et al., 2007). Ammoniacal-N (mg/L) 0.25 0.2 Nov Dec 0.15 Jan 0.1 Feb Mar 0.05 Apr 0 M1 M2 M3 M4 Stations Figure 5.6: Ammoniacal nitrogen concentration at mussel sampling stations, M1 to M4 from November 2008 to April 2009. 110 5.2.1.7 Biochemical Oxygen Demand (BOD) BOD levels are used as indicators of organic pollution in water quality monitoring (Law, 1981). A low BOD reading means either that the water is clean or that the organisms have been killed by toxic pollutants. The results for water samples of BOD and COD at mussel’s stations were only available for four months, November 2008 to February 2009. Figure 5.7 shows the concentration of BOD against mussel collection stations. The BOD values for November 2008 increased starting from M2 to the final station. Whereas the BOD values for December 2008 is more stable where there are no much variations on the concentration against stations. The ranges for BOD values at four mussel stations were 4.6 mg/L to 5.8 mg/L. As more organic waste is available, the growth of bacteria will increase and decrease the DO level as the organics are decomposed by microbes. High amounts of nutrients and organic matters left on seabed can exceed the carrying capacity of water. Overall the BOD values satisfy Class III of INWQS. 7 6 BOD (mg/L) 5 Nov 4 Dec 3 Jan 2 Feb 1 0 M1 M2 M3 M4 Stations Figure 5.7: BOD concentration at mussel sampling stations, M1 to M4 from November 2008 to February 2009. 111 5.2.1.8 Chemical Oxygen Demand (COD) Figure 5.8 shows the concentration of COD against mussel’s stations from November 2008 to February 2009. As illustrated in the figure, the values were a bit higher in M2 and increase starting from station M2 to M4. In December 2008 to February 2009 water samples shows an increasing trend while in November 2008 samples show a small decrease. The ranges of COD values were 1992 mg/L to 3640 mg/L. High COD values is due to the excessive discharge of organic matter and inorganic chemicals from agriculture, urban areas and industries from the surroundings into the coastal water. It could also be due to analytical interference from chloride in seawater. 4000 3500 COD (mg/L) 3000 2500 Nov 2000 Dec 1500 Jan 1000 Feb 500 0 M1 M2 M3 M4 Stations Figure 5.8: COD concentration at mussel sampling stations, M1 to M4 from November 2008 to April 2009. 5.2.2 Heavy Metals P.viridis is known as the main bioindicator and biomonitor of heavy metals especially in Asian countries such as Singapore, Thailand and India (Vijayavel, 2009). Three major heavy metals that were analyzed in this study are Pb, Cd and Zn. 112 Most of the studies carried out at international level and specifically in Malaysia regarding P.viridis used the three metals as their main analysis (Monawwar, 2002; Yap et al., 2002; Aminah, 2003; Yap et al., 2003; Chee et al., 2003; Yap et al., 2004a; Liu and Kueh, 2005). Cd, Pb and Zn are widely distributed in the coastal environment, both from natural geological processes and anthropogenic activities, this is of much interest to public health, since the metals are readily accumulated in the soft tissues of P.viridis (Yap et al., 2002). For the used of analysis in this study, only the concentrations of adult mussels (7 to 9 cm) were analyzed using dry weight basis. The relative importance of water and food for metal bioaccumulation in mussels is not influence by mussel’s size. This is because the influx rates of most metal from water and food both decrease in a similar fashion with increasing size (Yap et al., 2005b). In order to see the significant correlation of Cd concentration between seawater and green mussel, water samples were also been collected at mussels stations (M1 to M4). 5.2.2.1 Cadmium (Cd) Figure 5.9 show the comparison of cadmium (Cd) concentrations in water and P.viridis for each mussel sampling stations. The levels of Cd in mussels were high although the ambient seawater that they were exposed to have low Cd levels. The untreated waste from the industries may be one of the factors that enhanced the accumulation of Cd in mussels. Gradual decreasing trends were observed for concentration of Cd in water samples. The concentrations were higher at the earlier station of M1 and decreased when approaching the last station, M4. The high concentration of Cd at the earliest station may be due to the untreated waste from the industries discharged from the tributaries of Sungai Skudai, Sungai Danga, Sungai Melayu and part of Sungai Segget. The first three months (November 2008 to January 2009) shows more constant concentration values compared to the next three months (February 2009 to April 2009) which is higher. Concentrations Cd in February to April 2009 water samples exceeds the Interim National Water Quality Standard (INWQS) for Malaysia that is at 0.1 mg/L for Cd. 113 The concentration of Cd in P.viridis resulted in different trend for mussel samples. Lowest concentration of Cd in P.viridis was obtained at station M1 and the highest gain at station M2. Then it starting to decrease when move towards the last station, M4. The range of Cd concentration in P.viridis is from 0.11 µg/g to 1.21 µg/g. In comparison with the permissible limits set by the Malaysian Food Regulation (1985) for Cd (1.00 µg/g), there was one sample of P.viridis that exceeded the limit while the others were still under the limit. 1.4 1.2 1 Cd 0.8 Water 0.6 Mussel 0.4 Nov Dec Jan Feb Mar Apr Nov Dec Jan Feb Mar Apr M4 Nov Dec Jan Feb Mar Apr M3 Nov Dec Jan Feb Mar Apr M2 0 M1 0.2 Stations Figure 5.9: Cadmium concentration in water and P.viridis samples at mussel sampling stations, M1 to M4 from November 2008 to April 2009. From Figure 5.9, we can see that the concentrations of Cd in water decreased from station M1 at Danga to station M4 at Pendas area. In comparison with concentration of Cd in P.viridis, most of the samples recorded higher concentration than in water. However the concentrations of Cd in P.viridis for all samples in April 2009 were clearly lower than the ambient water that they were exposed to. This indicates that the valve closure in response to the toxic levels of metal exposures and thus preventing accumulation of metals inside the soft tissue of the mussels. Even though less metal were accumulated in the soft tissue, the homeostatic mechanisms to counteract the acute metal exposures seemed to have been used up and this 114 resulted in permanent disturbed metabolic function (Abel and Papoutsoglou, 1986; Yap et al., 2004b). 5.2.2.2 Lead (Pb) Figure 5.10 shows the comparison between the concentration of Pb in water and Pb levels in P.viridis for each station. From the figure, there are obviously seen that the concentration of Pb in mussels were much higher than the concentration in water. Compare to Cd, the values of concentration for Pb in mussels were higher than the average concentration of Cd in P.viridis. Generally, there are no exact trends observed between the concentration of Pb in water and mussels. 30.0 25.0 Pb 20.0 15.0 Water Mussel 10.0 5.0 Stations Nov Dec Jan Feb Mar Apr M4 Nov Dec Jan Feb Mar Apr M3 Nov Dec Jan Feb Mar Apr M2 Nov Dec Jan Feb Mar Apr M1 0.0 Figure 5.10: Lead concentration in water and P.viridis samples at mussel sampling stations, M1 to M4 from November 2008 to April 2009. Concentration of Pb in water samples shows decreasing trend for most of the months. The trend is quite similar to Cd concentration, where the highest level was at the first station, M1. The reading then starts to decrease when approaching the final station, M4. Only sample on February 2009 which turn to increase at M3 before rapidly decreasing at the final station. The range of Pb concentration in water 115 samples were 0.12 mg/L to 3.21 mg/L. The higher Pb concentrations in the earlier stations were plausibly related to the discharge of effluents from the nearby domestic and industrial inputs. For all sampling stations in all months, none of the levels complies with the Interim Water Quality Standard (INWQS) which is at 0.1 mg/L. Concentration of Pb in mussels samples is shown in the same figure. Pb concentration does not differ much except for several sampling occasions that began to fluctuate. Generally, most of the Pb levels were below 10 µg/g and only several readings show results higher than that. P.viridis showed a wide range of Pb concentrations. The ratios of the highest to the lowest values among sites were 2.10 µg/g to 24.23 µg/g during the study period. Significantly, higher concentrations of Pb in P.viridis were found in M2 (near to Sungai Perepat) where as lower concentrations were recorded at final station, M4 (near to Pendas). Compared to the limits set by Malaysian Food Regulation (1985), the permissible limit allowed for Pb concentration is 2.00 µg/g. Pb levels for all sampling exceeded the regulation thus meaning that it may be harmful to health since P.viridis is a source of seafood in Malaysia. 5.2.2.3 Zinc (Zn) The comparison of zinc content in mussels and seawater is shown in Figure 5.11 (a) and (b). Results for Zn are more interesting since it clearly differs from both previous heavy metals correlations. The concentrations of Zn in P.viridis were obviously higher than in water. The ranges between both concentrations were too high. The high Zn concentration could be due to Zn being needed for metabolism in the different soft tissues of P.viridis (Viarengo et al., 1985) although it might also be regulated (Phillips, 1985). Zinc is one of the essential metals for marine organisms and it increases the enzymatic activity (Vallee, 1978). Zinc concentrations in tissues of marine organism are usually much higher and more variable than concentration of other metals. The concentration of Zn in water samples as shown in Figure 5.11(a) was found between 116 0.034 mg/L to 0.56 mg/L. Generally, the trend of concentration for Zn is much similar to Cd concentration trend. The highest concentration of Zn as expected was found at the first station, M1 (0.142 mg/L to 0.56 mg/L). While the lowest levels of Zn is at the final station, M4. Van de Berg (1987) reported that, increases in dissolved and suspended fractions of zinc in estuarine water were identified in the mixing zone between fresh and brackish water. The increases were attributed to the increase in residence time of zinc in estuary compared to freshwater. The concentrations of Zn are lower at the ocean surface than in deeper water (Bruland et al., 1978). 0.6 Zn (mg/L) 0.5 Nov Dec 0.4 Jan 0.3 Feb 0.2 Mar Apr 0.1 0 M1 M2 M3 M4 Stations (a) 120 100 Nov Zn (µg/g) 80 Dec 60 Jan Feb 40 Mar 20 Apr 0 M1 M2 M3 M4 Stations (b) Figure 5.11: Zinc concentration in (a) water and (b) P.viridis samples at mussel sampling stations, M1 to M4 from November 2008 to April 2009. 117 Uptake of Zn by P.viridis was dependent on both salinity and temperature (Conti and Cecchetti, 2003). The absorption of zinc by aquatic animals tends to be from water rather than food. Only dissolved zinc tends to be bioavailable, and bioavailability depends on the physical and chemical characteristics of the environment and biological processes (Bruland et al., 1978). Result of the concentration of Zn for P.viridis is shown in Figure 5.11(b). The concentration of Zn in P.viridis varied slightly among the study sites where the ratios of the highest to the lowest Zn concentration being 21.1 µg/g to 98.45 µg/g during study period. These indicates that the spatial distribution of this metal was not fairly uniform due to area and months. Slightly higher concentration of Zn was found at station M1 where average from all sampling was higher than the other stations average. November 2008 became the highest accumulation of Zn compared to other months. In comparison with the permissible limits by Malaysian Food Regulation (1985) for Zn, all of the Zn level does not exceed the permissible level of 100 µg/g. Based on the heavy metals concentration in P.viridis measured in DangaPendas coastal area, it is possible to report that the contamination of Cd and Zn is not serious. However, concentration levels of Pb are quite high which exceed the Malaysian recommended permissible limit on food sources. High levels of Pb found in the P.viridis in this region were plausibly related to discharge of effluents from the nearby domestic and industrial inputs. 5.3 Comparison of Cd, Pb and Zn Concentrations in P.viridis from Previous Studies In order to see the variation of heavy metals concentration in P.viridis, data for Cd, Pb and Zn concentration from a series of years were gathered. A large number of sampling stations were analyzed by the previous studies and only significant stations related with this study area were considered. Pantai Lido station was the one selected for analyzing the concentration for Cd, Pb and Zn in this study. Table 5.1 is the list of the maximum permissible limits of heavy metals in seafood from different countries. The list can be used as guideline to evaluate quality of Malaysia seafood especially P.viridis. While Table 5.2 is the comparison of metal 118 concentrations in P.viridis collected from the present study and those from the previous studies (Ibrahim, 1993; Yap et al., 2002, Yap et al., 2003; Chee et al., 2009). Detail analysis on the variation of the concentration of Cd, Pb and Zn in P.viridis collected in Pantai Lido will be illustrated as graphs of Cd, Pb and Zn against year in Figure 5.12, 5.13 and 5.14. Table 5.1: Guidelines of maximum permissible limits of heavy metals (µg/g) in seafood from different countries (Adapted from Yap et al., 2004a) Location Cd Pb Zn Permissible limits by Malaysian Food Regulation (1985) 1.00 2.00 100.0 International Council for the Exploration of the Sea 1.80 3.0 - 5.00 10.0 250 - 6.67 667 3.7 1.7 - Australian Legal Requirement (NHMRC, 1987) 10.0 - 750 Permissible limit set by the Hong Kong Environmental 2.00 6.00 - (ICES, 1988) Maximum permissible levels established by Brazilian Ministry of Health (ABIA, 1991) Permissible limit set by Ministry of Public Health, Thailand (MPHT, 1986) Food and Drug Administration of the United State (USFDA, 1990) Protection Deoartment (HK EPD, 1997) 119 Table 5.2: Mean concentration of Cd, Pb and Zn in P.viridis collected from Pantai Lido in the present and previous studies. Year Cd (µg/g) Pb (µg/g) Zn(µg/g) Reference 1991 NA NA 16.143 Ibrahim (1993) ± 1.107 1998 2000 2006 2009 0.70 3.30 80.89 ± 0.07 ± 0.27 ± 2.24 0.68 4.03 116.9 (0.36-1.53) (1.83-8.98) (68.1-165) 1.179 22.812 67.767 (0.86-1.53) (6.47-35.2) (47.6-92.8) 0.26 6.89 59.632 (0.041-0.39) (4.30-8.43) (45.2-76.52) Yap et al.(2002) Yap et al.(2003) Chee et al.(2009) Current study Figure 5.12 show the concentration of Cd in P.viridis against year. As seen in the graph, the concentrations increased up to 1.18 µg/g in 2006 and decreased to the lowest level of 0.26 µg/g in 2009. Year 1998 to 2000 show more constants Cd concentration levels with an average of 0.68 µg/g to 0.70 µg/g. It start to increase in 2006 due to the discharge of domestic and industrial wastes entering this area from Sungai Skudai, Sungai Danga and Sungai Segget. Moreover, 2006 is the starting year of IDR development area (SJER CDP, 2006). The aggressive and massive development progress might be one of the reasons which contribute to higher Cd concentration in this area. However the present study shows drastic reduction of Cd concentration in P.viridis for this area which is possibly due to the intensive prevention program in IDR development by the developers and government. Although most of the concentration is quite high, it is still under the permissible limit set by Malaysia Food Regulation (1985) which is 1.0 µg/g. Only samples on 2006 recorded Cd concentration more than that. In comparison with regulation from other countries, the concentrations of Cd were under the limits. 120 1.4 1.2 Cd (µg/g) 1 0.8 0.6 Cd 0.4 0.2 0 NA 1991 1998 2000 2006 2009 Year Figure 5.12: Cadmium concentration in P.viridis samples at Pantai Lido from 1991 to 2009 Concentrations of Pb in P.viridis against year from 1991 to 2009 is shown in Figure 5.13. The trend of Pb concentration in P.viridis is much similar to the trend observed for Cd concentration where the values increased from 1998 to 2006 and decreased in 2009. The highest Pb value recorded in 2006 with 22.8 µg/g and the lowest Pb value obtained in early 1998 with 3.30 µg/g. Due to the similar trend for both heavy metals, the possibly reasons of the high Pb concentration may be similar to the reasons found in Cd concentration. Even though the trend is much similar, the level of Pb concentration in P.viridis is much higher. Based on the Malaysian Food Regulation (1985), none of the samples were under the limit of 2.00 µg/g. The concentration of Pb seems to be very critical as the comparison comparison with regulation and guidelines from other countries shows that the values were still within and above the limits. 121 25 Pb (µg/g) 20 15 10 Pb 5 0 NA 1991 1998 2000 2006 2009 Year Figure 5.13: Lead concentration in P.viridis samples at Pantai Lido from 1991 to 2009. Zn is another heavy metals which is critical to aquatic organisms. The concentration trends for Zn were obviously different than Cd and Pb. The concentrations started to increase from year 1991 to 2000 and gradually decreased in 2006 and 2009. The highest concentration obtained for Zn was in 2000 at 116.9 µg/g while the lowest levels recorded was in 1991 at 16.14 µg/g. Generally, although the concentrations of Zn were higher for most of the year, it is still under the permissible limit set by Malaysian Food Regulation (1985) which is 100 µg/g. Comparison made to other guidelines shows that the concentrations of Zn in P.viridis were far below the limits which indicate that they are safe as a food source. 140 120 Zn (µg/g) 100 80 60 Zn 40 20 0 1991 1998 2000 2006 2009 Year Figure 5.14: Zinc concentration in P.viridis sampless at Pantai Lido from 1991 to 2009. 122 5.4 Effects of Water Quality on Green Mussel The intertidal areas are natural habitats of marine mussels and they are usually close to estuaries. Therefore, the chance of exposure to many contaminants from land-based activities through the riverine system as well as sea-based sources, is high (Yap et al., 2004b). The elevated levels of metals found in the intertidal and marine aquatic life especially P.viridis could be due to land-based activities and the areas semi-enclosed topography which may aggravate the pollution problem in general. Moreover, the rapid development of IDR which plan to end in 2025 will be the main contributor to drastic boost of heavy metals in this region. Trace metals are available to aquatic animals through uptake from both dissolved and dietary phases (Inglis and Gust, 2003). P.viridis are filter feeders and tends to bioaccumulate heavy metals in their tissue. The heavy metals could simply accumulate through time, becoming more toxic threat as their concentrations increase since heavy metals are inorganic chemicals that are non-biodegradable, cannot be metabolized and will not break down into harmless forms (Yap et al., 2004b). Consumption of metal-contaminated P. viridis may also cause toxicity to humans. Other environmental factors are also contributing factors which influence the accumulation of metals in P.viridis. The factors include temperature, pH, tides, velocity, wind direction and rain. However, based on the study done by Ibrahim (1993), at the same area, these factors have less influence on the levels of metals accumulation by marine organisms including P.viridis. Based on the analysis and results of effects of water quality on green-mussel, there are no exact correlation that can prove the statement of the effects of water quality to this species directly. However, there are significant relations observed, as the concentration of pollutant such as heavy metals increased, the concentration of that particular pollutant in green mussel, P.viridis were also increased. As bioaccumulator and filter-feeder, green mussels accumulate heavy metals and toxins in its tissues up to hundreds of times more concentrated compared to its habitat. 123 According to Farrington (1987), green mussels have the capability to accumulate the excess of heavy metals from seawater up to 100,000 times higher than the seawater. In mussels, they can induce metallothionein-like proteins to defend against heavy metals or in some cases, mineral concretions can be a way of storage for heavy metals in the soft tissue of mussels (Phillips and Rainbow, 1993). This has been the reason why mussel can accumulate high levels of metals (Yap et al., 2004b). However, exposed to higher concentration in heavy metals can also effect the growth of green mussels. Study reviewed by Yap et al., (2004b) revealed that, the percentage of mortality for young mussels (3 to 4 cm) were high when the concentration of heavy metals in water was high. This indicate that the higher concentration of pollutants in water, can effect the quality of green mussels itself as it may be consumed by human as food sources, but it can also effects the growth of young green mussels as they might die. CHAPTER 6 CONCLUSION AND RECOMMENDATIONS 6.1 Conclusion Studies over the last three decades have clearly demonstrated that landuse has direct and indirect impacts on water quality, stream characteristics, aquatic habitat, macroinvertebrates, and fish. Although the exact mechanisms for these impacts at specific sites is not always immediately obvious, the impacts have been demonstrated to be due to altered hydrology and its water quality and aquatic habitat, both at the individual site and at surrounding scale. In this study, the changes in landuse also affects water quality of the surrounding water bodies. The levels of water quality decreased with increase in development along Danga-Pendas coastal area especially. The reduced water quality status has major impact with increase in pollutants, nutrients and heavy metals. Thus, these will also have effects on green mussel, P.viridis either directly or indirectly. Monitoring of landuse change along Danga-Pendas provide useful information in analyzing the effects to water quality along this area. Remote sensing and Geographic Information System (GIS) techniques can be used to monitor the conversion of landuse types Landuse studies using remote sensing data have received immense attention worldwide due to their importance in global change analysis With time series information and wide range coverage make it useful in monitoring the landuse change thus helpful in analyzing the effects on water quality. 125 As a result, we can see the degradation in water quality levels in comparison with INWQS, with the increase of build-up or development along Danga-Pendas coastal area. Build-up or developed area have recorded major increased trend with changes about 4224.96 ha (23.63%) between 1991 to 2005 and 6610.05 ha (29.91%) within three years from 2005 to 2008. Forest/ scrubs, cultivation area and mangrove recorded the highest reduction trend. Mangrove area decreased at a total of 41.31% from 1991 to 2008. Forest/ scrubs and cultivation area changed 38.5% and 32.86% respectively. Along with the increase of developed area and decreased in vegetated area (forest, cultivation and mangrove), there were reduction in water quality levels, where most psychochemical water quality parameter satisfies class II and III of INWQS while most of the heavy metals exceeded INMWQS limits. As well as the landuse change affects the water quality, the degradation of water quality also affects aquatic life such as P.viridis in their ecosystem. Based on the analysis, there was no exact correlation found between the concentrations of trace metals in water with green mussels collected from the time being. However, there was significant relation when high concentrations of metals were recorded in water, there were also higher concentrations of those metals in green mussels. As bioaccumulator and bioindicator, P.viridis is able to accumulate up to hundreds times of the concentrations in water itself. The degradation of water quality level due to landuse, might also give significant impact to P.viridis since they can accumulate high concentration of pollutants thus making it hazardous to human as food source. It also effects the growth of young P.viridis exposed to high metals concentrations. This may influence the distribution of P.viridis as a native species laid along DangaPendas coastal area. In assessing the severity of the development along Danga-Pendas coastal area for the time being, there are huge landuse changes especially in Johor Bahru town and Nusajaya area which involved IDR development. Based on the SJER planning, by the time of development ends in 2025, there would be vast landuse changes in Danga-Pendas and all along the coastal area of south Johor. The worst is that, most 126 of the development will directly and indirectly affects the water quality along this region. Overall the levels of water quality in this area are slightly polluted. There were several parameters especially metals recorded in higher concentration as they should be based on the INWQS and INMWQS. Extensive care and prevention methods should be applied especially for IDR development in order to limit direct access of pollutants to coastal water which affects water quality and mussels. This is because there would be more landuse changes that will decrease water quality levels and affect mussels by the end of its progress. As a conclusion, there are significant effects of landuse changes on reducing water quality levels along Danga-Pendas coastal area. As the area of land-based activities such as development and agriculture increased, there was decrease in water quality levels. Although there were no exact correlation of water quality on mussels, but several previous studies have revealed small relation of water quality on mussel’s accumulation and growth. 6.2 Recommendations Regarding the processes and results obtained in this study, there are several recommendations that can be applied in order to get better results and analysis concerning the effect of landuse changes in water quality and green mussels along this area. The recommendations include; i) The effects of water quality due to development and landuse changes along this area also need to take into consideration pollutants originating from Singapore. The information of landuse types, land-based activities might be required to support the study. If possible sampling should be conducted nearest to the coastal area of Singapore. 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Assessment of the local environmental Impact of Intensive Marine Shellfish and Seawees Farming – Application Aquaculture.287;304-310. of MOM System in Sungo Bay-China. 145 APPENDIX A WATER QUALITY STANDARD a) INTERIM NATIONAL WATER QUALITY STANDARD Parameters Unit Temperature o C pH I IIA IIB III IV V - normal - normal - - 6.5 - 8.5 6-9 6-9 5-9 5-9 - Conductivity uS/cm 1000 1000 - - 6000 - Colour Pt -CO 15 150 150 - - - DO mg/L 7 5-7 5-7 3-5 <3 <1 BOD mg/L 1 3 3 6 12 >2 COD mg/L 10 25 25 50 100 > 100 Oil & Grease mg/L natural 40; nil nil - - - Dissolved solids mg/L 500 1000 - - 4000 - Suspended solids mg/L 25 50 50 150 300 > 300 Turbidity NTU 5 50 50 - - - Ammoniacal – N mg/L 0.1 0.3 0.3 0.9 2.7 > 2.7 nil nil nil - - - nil nil nil - - Floatables Odour Salinity 10 -3 0.5 1 - - 2 - E. coli MPN/100mL 10 100 400 5000 5000 - Total coliform MPN/100mL 100 5000 5000 50000 50000 > 50000 Hardness mg/L natural 250 250 - - - K mg/l natural - - - - - F mg/l natural 1.5 1.5 10 1 >1 NO3 mg/l natural 7 7 - 5 >5 P mg/L natural 0.2 0.2 0.1 - - S mg/L natural 0.05 0.05 0.001 - - Cd mg/L natural 0.01 0.01 0.01 0.01 > 0.01 Cu mg/L natural 1 1 - 0.2 > 0.2 Fe mg/L natural 0.3 0.3 1 1-5 >5 Pb mg/L natural 0.05 0.05 0.02 5 >5 Mn mg/L natural 0.1 0.1 0.1 0.2 > 0.2 Ni mg/L natural 0.05 0.05 0.9 0.2 > 0.2 146 b) WQI-SI FORMULA Parameters Value Subindex Equation (SI) COD If X = < 20 SICOD = 99.1 – 1.33X If X > 20 SICOD = 103 x [E]-0.0157X - 0.04X If X = <5 SIBOD = 100.4 – 4.32X If X >5 SIBOD = 108 x [E]-0.055X – 0.1X If X = < 0.3 SIAN = 100.4 – 4.32X If 0.3 < X < 4 SIAN = 94 x [E]-0.573X – 5(X-2) If X = > 4 SIAN = 0 If X = < 100 SISS = 97.5 x [E]-0.00676X + 0.7X If 100 < X < 1000 SISS = 71 x [E]-0.0016X – 0.015X If X= > 1000 SISS = 0 If X < 5.5 SIpH = 17.2 – 17.2X + 5.02X2 If 5.5 = < X < 7 SIpH = -242 + 95.5X – 6.67X2 If 7 = < X <8.75 SIpH = -181 + 82.4X – 6.05X2 If X = > 8.75 SIpH = 536 – 77X + 2.76X2 BOD AN SS pH DO X = DO (mg/L) * 12.6577 If X = < 8 SIDO = 0 If 8 > X SIDO = -0.395 + 0.030X2 – 0.00019X3 Note: (1) X is concentration of parameter in unit mg/L, except for pH and DO (2) x is symbol of multiply (3)SIDO, SIBOD, SICOD, SIAN, SISS and SIpH are the Sub Index (SI) of the respective water quality parameters which isused to calculate the Water Quality Index (WQI). 147 APPENDIX B LABORATORY ANALYSIS a) MUSSEL DIGESTION (DRY WEIGHT) i) Sample Preparation Weigh about 5 g of sample (dry weight) into a digestion tube. Add 5 mL of HNO3 and then 5 mL of H2SO4 to the sample. Allow the reaction to proceed. When the reaction slows, place the tubes in a hot-block digestion apparatus and heat at a low temperature (60°C) for 30 min. Remove the tubes from the hot block, allow to cool, add 10 mL of HNO3, return tubes to digestion rack and heat slowly to 120°C. Increase the temperature to 150°C. Remove the tubes when the samples go black, allow to cool, then add 1 mL of H2O2. A vigorous reaction may occur. Return the tubes to the block. Repeat the H2O2 additions until the samples are clear. Remove the tubes and make up to 50 mL with deionized water. Most elements can be determined directly; however, to determine Pb and Cd, solvent extraction is used to concentrate these elements. Take 40 mL of the digest and make up to 100 mL; add 5 mL of APDC and 5 mL of MIBK. Shake vigorously for 5 min. Determine Pb and Cd in the MIBK phase. ii) Analysis Standards should be treated in the same way as samples. It is important that the standards contain the same amount of acid as the samples, especially H2SO4, as it will have a viscosity effect that will suppress sensitivity. Make up stock solutions as explain in the heavy metals analysis. 148 b) BIOCHEMICAL OXYGEN DEMAND (BOD) ANALYSIS Biochemical Oxygen Demand (BOD5) was determined as soon upon return to laboratory. BOD5 was determined as the difference between initial and 5-days oxygen concentration in bottles at 20°C (following APHA 5210 B method). Samples were diluted five times and seeded. i) Preparation of BOD reagent For preparation of phosphate buffer solution, potassium dihydrogen phosphate (KH2PO4) (8.5 g), dipotassium hydrogen phosphate (K2HPO4) (21.75 g), disodium hydrogen phosphate heptahydrate (Na2HPO4 7H2O) (33.4 g), and ammonium chloride (NH4Cl) (1.7 g) were dissolved in distilled water (about 500 mL) and diluted to 1 liter. The pH of this buffer should be 7.2 and checked with a pH meter. Magnesium sulfate solution was prepared by dissolving magnesium sulfate heptahydrate (MgSO4 7H2O) (22.5 g) in distilled water and diluted to 1 liter. Preparation of calcium chloride solution was done by dissolving anhydrous calcium chloride (CaCl2) (27.5 g) in distilled water and diluted to 1 liter. While ferric chloride solution was prepared by dissolving ferric chloride hexahydrate (FeCl3 6H2O) (0.25 g) in distilled water and diluted to 1 liter. All the reagents were discarded if there were any sign of biological growth in the storage bottle. ii) Preparation of dilution water The distilled water used for dilution water must be of high grade and free from contaminants (such as copper and chlorine) which could inhibit the growth of bacteria. Each of phosphate buffer, magnesium sulfate solution, calcium chloride solution and ferric chloride solution (1mL, 1mg/L) were added in volumetric flask (1000 mL). Double distilled deionized water was added until the mark. iii) BOD5 analysis 149 Sample (60 mL) was placed into the BOD bottle (300 mL). A small amount of seed (2 mL) was added directly to the sample and dilution water was added until the mouth of the bottle. The initial DO content of each sample was determined by using the DO meter together with the blank dilution water. The DO meter was calibrated before being used. The bottles were placed in the incubator at 20°C, dark and incubate for five days. After the five days, another dissolved oxygen reading (mg/L) was taken using the DO meter. BOD5 was calculated based on the equation. BOD5, mg/L = [(DO1 – DO2) – (S1 – S2)] X DF BOD5 = Biochemical Oxygen Demand DO1 = Initial dissolved oxygen concentration of sample (mg/L) DO5 = Sample dissolved oxygen concentration after five days (mg/L) S1 = Initial dissolve oxygen concentration of blank (mg/L) S2 = Blank dissolved oxygen concentration after five days (mg/L) DF = Dilution factor c) CHEMICAL OXYGEN DEMAND (COD) ANALYSIS Chemical oxygen demand (COD) test is commonly used to indirectly measure the amount of organic compounds in water. Most applications of COD determine the amount of organic pollutants found in surface water, making COD a useful measure of water quality. It is expressed in milligrams per liter (mg/L), which indicates the mass of oxygen consumed per liter of solution.COD value was determined using Hach 5000 Spectrophotometer (HACH, 2005) based on Standard Method APHA 5220-C procedures. i) Turn on the COD reactor. Preheat to 150OC. Place the plastic shileed in front of the reactor. ii) Pipet 3 mL of COD reagent into the vial. iii) Hold the vial at 45O angle and pipet 2.00 mL of sample into the vial. iv) Replace the vial cap tightly. Rinse the COD vial with deionized water and wipe the vial clean with a paper towel. 150 v) Hold the vial by the cap and over a sink. Invert gently several times to mix the contents. Place the vial in the preheated COD reactor. The vial will become very hot during mixing. vi) Prepared a blank by repeating step 2 to 5. For blank use deionized water as sample. Place the blank in the preheated COD reactor. vii) Heats the vials for 2 hours. viii) After 2 hours, turn off the reactor and wait about 20 minutes for the vials to cool to 120OC or less. ix) Invert each vial several times while still warm. Place the vial into a rack. Wait until the vials have cooled to room temperature. x) d) Use HACH DR 5000 Spectrophotometer to get the result. AMMONIACAL NITROGEN ANALYSIS All the reagents used in the analysis of ammoniacal nitrogen test were manufactured by Merck with analysis reagents grad. The method was analogous to EPA 350.1 and APHA 4500-NH3 D. The procedures comprised of the preparation of sample and standard solution are described below. i) Standard preparation Ammonium (NH4+) Standard Solution (1000 mg/L) was diluted to stock solution (100 mg/L) by double distilled deionized water. To prepare standard solution with concentration 0.5 mg/L, stock solution (250 µL) was pipetted by using micropipette with capacity 100-1000 µL into the test tube diluted with double distilled deionized water until the volume reached 5 mL. ii) Sample preparation Pretreated sample (5 mL) was pipetted into a test tube and reagent NH4-1 (0.6 mL) and sodium hydroxide solution (1 mL, 5 mol/L) was added and mixed. 1 level microspoon of reagent NH4-2 was then added and shaked vigorously until the reagent was completely dissolved. The solution was left for five minutes for reaction (time A) to occur. Next, 151 reagent NH4-3 (4 drops) was added, mixed and left to stand for another five minutes for reaction (time B) to complete. Blank solution was also prepared by using double distilled deionized water instead of sample but treated using the same procedure as the sample. iii) Instrumental analysis The ammoniacal nitrogen in the samples was filled into the cell and measured using HACH DR5000 Spectrometer programmed as HACH Program 2460 N-Ammonia LR TNT, with UV wavelength 655.0 nm. e) HEAVY METALS The standard operational procedures from APHA and US EPA with certain modification adapted to the working environment was applied to increase the data reliability. Applied Standard Operational Procedures Standard method APHA Method APHA 3111 Preparation of working solutions method APHA 311 1 B Direct Air Acetylene Flame Method (Atomic Absorption Spectrometer) US EPA 3005 A Acid digestion of water samples method i) Reagents and Solutions Double distilled deionized water and high purity reagents were used for all preparations of standards and sample solutions. Cuprum and Plumbum (MERCK) stock solutions 1000 mg/L were used in preparation of standard solutions. Nitric acid, HNO3 and hydrochloric acid, HCl manufactured by HmbG Chemicals were used for extraction method. 152 ii) Preparation of working solution The Pb, Cd, Zn and Ni standard solutions were used as a reference in determining metal concentration in samples. The standards were prepared from certified atomic absorption reference standards. Dilution of stock solutions were performed to obtained the desired concentration standard solutions. Dilution was made based on the following calculation: M1V1 = M2V2 M1 = Concentration of stock standard solution (mg/L) V1 = Volume of stock solution needed (mL) M2 = Concentration of desired standard solution (mg/L) V2 = Final volume of the desired standard solution (mL) iii) Sample preparation Preparation of water samples by acid digestion was adapted from US EPA 3005A standard method. A measured of well mixed sample (50 mL) was transferred into a clean beaker (100 mL). HNO3 (2 mL ) and HCl (5 mL ) were added into the beaker and covered with watch glass. The sample was heated at 95 ± 5 °C until the volume was reduced to about 15 mL. The sample was then filtered and the filtrate was collected in volumetric flask (50 mL), followed by careful adjusted volume with double distilled deionized water to 50 mL. iv) Instrumentation A Perkin Elmer Model AAnalyst 400 Flame Atomic Absorption Spectrometer was used for determination of metals in samples. The AAS was equipped with hollow cathode lamps with specified wavelength and air acetylene burner. The instrumental settings were 153 made based on the manufacturer’s manual guideline. The detection method was adapted from standard method APHA 311 1 B Direct Air Acetylene Flame Method. APPENDIX C ACCURACY ASSESSMENT REPORTS FOR 1991, 2000, 2005 and 2008 CLASSIFICATION i) Accuracy Assessment for 1991 Landuse Classification ii) Accuracy Assessment for 2000 Landuse Classification 154 iii) Accuracy Assessment for 2005 Landuse Classification iv) Accuracy Assessment for 2008 Landuse Classification 155 APPENDIX D WATER QUALITY DATA (a) Sampling Data – Water Stations (Water Quality Data) i) Station S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 Temperature (ºC) Nov 2008 29.50 29.30 29.18 29.50 29.47 29.48 29.36 29.21 29.00 29.90 29.40 Dec 2008 29.30 28.90 28.63 29.10 29.60 29.36 29.20 29.90 28.40 28.60 29.10 Months Jan 2009 29.10 28.70 28.50 28.90 29.10 28.20 28.57 28.64 28.67 29.72 29.30 Feb 2009 29.53 29.65 29.39 29.56 29.65 29.55 29.65 29.67 29.64 29.99 29.60 Mar 2009 29.47 29.21 29.18 29.45 29.47 29.52 29.27 29.35 29.36 29.46 29.60 Apr 2009 28.21 27.81 27.75 28.21 28.35 28.90 28.55 28.75 28.64 28.45 28.44 156 ii) Station S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 iii) Dissolved Oxygen (mg/L) Nov 2008 2.81 3.31 2.31 3.31 2.95 3.71 3.81 3.66 4.37 4.37 4.33 Station S1 S2 S3 Months Jan 2009 2.65 3.21 3.11 3.22 2.52 3.47 3.51 4.01 4.21 4.27 4.22 Feb 2009 2.95 3.32 3.33 3.11 3.71 4.05 4.11 4.25 4.21 4.35 4.35 Mar 2009 2.06 2.33 2.32 2.32 2.38 4.03 3.99 4.21 4.31 4.48 4.23 Apr 2009 2.66 3.22 3.11 3.11 3.20 4.09 4.21 4.44 4.22 4.22 4.12 Salinity (ppt) Station Nov 2008 S1 18.17 S2 23.21 S3 23.55 S4 19.21 S5 19.75 S6 24.37 S7 24.56 S8 24.32 S9 24.44 S10 25.61 S11 25.45 iv) Dec 2008 2.85 3.32 3.31 3.31 2.81 4.05 4.05 4.51 4.32 4.31 4.44 Dec 2008 19.05 23.15 23.12 19.31 19.66 23.32 23.66 24.66 24.61 24.66 24.71 Months Jan 2009 19.55 23.65 23.26 22.78 21.46 23.22 23.76 24.21 24.26 25.66 24.61 Feb 2009 20.25 23.25 22.36 20.05 19.91 22.77 23.44 23.41 23.45 23.44 23.71 Mar 2009 Apr 2009 18.87 19.20 23.45 23.22 22.35 23.21 19.44 19.40 19.10 19.05 23.25 23.41 23.21 23.44 23.44 24.50 23.64 24.10 23.52 24.55 23.55 24.65 Dec 2008 9.24 9.27 9.19 Months Jan 2009 9.65 9.62 9.62 Feb 2009 8.67 8.71 8.83 Mar 2009 8.44 8.32 8.23 pH Nov 2008 7.38 7.52 7.57 Apr 2009 8.18 8.12 8.19 157 S4 S5 S6 S7 S8 S9 S10 S11 v) 7.55 7.61 7.76 8.12 7.96 8.01 8.34 8.57 9.26 9.33 9.34 9.36 9.33 9.21 9.25 9.22 8.31 8.35 8.26 8.24 8.19 8.16 8.18 8.24 8.12 8.09 8.07 8.13 8.13 8.06 8.11 8.14 Dec 2008 24.67 26.45 26.46 21.46 24.61 22.10 22.61 24.67 24.47 22.86 22.73 Months Jan 2009 24.02 25.41 24.16 23.10 22.40 23.59 23.10 24.55 25.45 23.41 23.59 Feb 2009 23.81 24.90 24.70 23.21 23.70 22.94 22.55 23.67 23.67 23.33 24.43 Months Jan 2009 0.558 0.199 0.320 0.149 0.244 0.083 0.073 0.092 0.082 0.043 0.036 Feb 2009 0.446 0.162 0.119 0.250 0.214 0.096 0.081 0.056 0.067 0.054 0.096 Mar 2009 24.50 25.20 26.47 24.00 23.57 23.20 23.42 24.67 24.07 23.20 24.00 Apr 2009 23.71 24.45 23.32 23.40 23.21 23.21 22.46 23.57 23.61 24.07 24.68 Ammoniacal-nitrogen Station Nov 2008 S1 0.311 S2 0.241 S3 0.223 S4 0.080 S5 0.126 S6 0.020 S7 0.012 S8 0.023 S9 0.022 S10 0.045 S11 0.023 vii) 8.65 8.58 8.72 8.56 8.55 8.67 8.66 8.68 Total Dissolved Solid (TDS) (mg/L) Station Nov 2008 S1 26.40 S2 24.67 S3 24.55 S4 23.98 S5 24.20 S6 22.09 S7 22.99 S8 23.56 S9 24.55 S10 23.56 S11 23.98 vi) 9.58 9.54 9.59 9.52 9.53 9.54 9.57 9.61 Dec 2008 0.965 0.410 0.965 0.162 0.453 0.132 0.095 0.081 0.061 0.078 0.075 Mar 2009 1.137 0.199 0.762 0.230 0.230 0.076 0.091 0.045 0.033 0.056 0.076 Biochemical Oxygen Demand (BOD)(mg/L) Station S1 S2 Nov 2008 5.2 5.4 Months Dec 2008 6.2 6.5 Jan 2009 6.5 6.2 Feb 2009 5.1 5.4 Apr 2009 0.513 0.24 0.424 0.156 0.231 0.074 0.066 0.024 0.078 0.062 0.035 158 S3 S4 S5 S6 S7 S8 S9 S10 S11 viii) Station S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 x) Station S1 S2 5.4 5.4 5.6 5.6 5.2 5.3 5.4 5.6 5.7 6.2 6 5.9 5.8 5 5.6 5.3 4.9 5 5.2 5.9 5.4 5.7 5.3 5.2 5 4.6 4.9 Chemical Oxygen Demand (COD) (mg/L) Station S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 . ix) 5 4.6 5 4.6 5.3 5.6 4.9 5.8 6 Nov 2008 976 1672 2370 2164 2642 1992 1526 2400 2745 2646 2840 Months Dec 2008 836 2405 2150 2255 2400 3315 3470 3640 3850 3000 3745 Jan 2009 834 2404 2088 2232 2284 3215 3745 3125 3480 3470 3647 Feb 2009 1076 1980 2210 2098 2265 2552 3065 3120 3350 3186 3264 Zinc (mg/L) Nov 2008 Dec 2008 0.201 0.209 0.245 0.209 0.287 0.214 0.178 0.165 0.198 0.211 0.121 0.102 0.098 0.098 0.031 0.021 0.052 0.034 0.019 0.011 0.034 0.032 Months Jan 2009 0.201 0.207 0.214 0.112 0.209 0.087 0.078 0.076 0.088 0.112 0.1 Feb 2009 0.218 0.216 0.234 0.187 0.271 0.111 0.122 0.131 0.103 0.09 0.09 Mar 2009 0.43 0.65 0.55 0.43 0.45 0.19 0.2 0.23 0.18 0.11 0.1 Apr 2009 0.421 0.512 0.45 0.395 0.43 0.315 0.334 0.21 0.2 0.11 0.12 Months Jan 2009 0.560 0.980 Feb 2009 2.650 3.230 Mar 2009 1.910 2.230 Apr 2009 2.930 3.000 Lead (mg/L) Nov 2008 1.510 0.990 Dec 2008 2.030 3.090 159 S3 S4 S5 S6 S7 S8 S9 S10 S11 1.090 1.650 1.210 0.440 0.540 0.250 0.890 0.560 0.210 xi) 3.090 0.890 2.780 1.780 0.450 0.320 0.210 0.340 0.220 2.430 2.090 2.210 0.230 0.900 0.340 0.450 0.090 0.120 2.250 1.650 1.700 1.340 1.230 0.780 0.320 0.830 0.230 3.050 2.780 2.800 0.780 0.560 0.350 0.780 0.550 0.670 Months Jan 2009 0.09 0.12 0.08 0.06 0.07 0.05 0.07 0.07 0.04 0.05 0.05 Feb 2009 0.41 0.44 0.46 0.36 0.41 0.32 0.22 0.18 0.17 0.18 0.15 Mar 2009 0.45 0.48 0.47 0.38 0.44 0.28 0.265 0.14 0.13 0.125 0.1 Apr 2009 0.475 0.49 0.505 0.41 0.465 0.355 0.24 0.2 0.24 0.23 0.175 Months Jan 2009 0.19 0.21 0.24 0.26 0.22 0.25 0.25 0.22 0.17 0.27 0.25 Feb 2009 0.32 0.35 0.33 0.2 0.18 0.27 0.21 0.2 0.21 0.19 0.12 Mar 2009 0.45 0.48 0.47 0.38 0.44 0.28 0.265 0.14 0.13 0.125 0.1 Apr 2009 0.475 0.49 0.505 0.41 0.465 0.355 0.24 0.2 0.24 0.23 0.175 Cadmium (mg/L) Station Nov 2008 Dec 2008 S1 0.065 0.07 S2 0.08 0.08 S3 0.058 0.05 S4 0.053 0.042 S5 0.05 0.061 S6 0.042 0.041 S7 0.04 0.044 S8 0.033 0.033 S9 0.028 0.019 S10 0.026 0.028 S11 0.019 0.02 xii) Nickel (mg/L) Station Nov 2008 S1 0.2 S2 0.19 S3 0.22 S4 0.25 S5 0.16 S6 0.21 S7 0.24 S8 0.16 S9 0.13 S10 0.19 S11 0.17 (b) 1.200 1.230 0.490 0.210 0.440 0.670 0.540 0.210 0.240 Dec 2008 0.08 0.27 0.28 0.25 0.1 0.23 0.24 0.25 0.24 0.28 0.28 Sampling Data –Mussel Stations (Water and Mussel Data) - Water Samples i) Temperature (ºC) 160 Stations M1 M2 M3 M4 ii) Stations M1 M2 M3 M4 iii) Nov 2008 29.48 29.50 29.50 29.00 Dec 2008 29.90 29.50 29.45 28.40 Months Jan 2009 28.80 28.40 28.45 29.14 v) Stations M1 M2 M3 M4 vi) Mar 2009 29.44 29.46 29.48 29.44 Apr 2009 28.70 28.35 28.21 28.53 Dissolved Oxygen (mg/L) Nov 2008 2.66 2.56 3.31 4.27 Dec 2008 2.56 2.45 3.31 4.33 Months Jan 2009 2.50 2.65 3.45 4.30 Feb 2009 2.66 2.72 3.32 4.15 Mar 2009 2.56 2.51 3.53 4.21 Apr 2009 2.98 2.75 3.66 4.26 Salinity (ppt) Months Stations Nov 2008 Dec 2008 Jan 2009 M1 23.95 23.55 23.32 M2 23.65 23.21 23.71 M3 24.14 23.21 22.71 M4 24.65 24.55 24.66 iv) Total Dissolved Solid (mg/L) Stations M1 M2 M3 M4 Feb 2009 29.64 29.53 29.71 29.45 Nov 2008 23.32 23.50 23.52 24.64 Dec 2008 22.46 22.61 23.51 24.07 Months Jan 2009 23.30 23.40 23.39 23.10 Feb 2009 22.78 22.91 22.73 23.56 Mar 2009 22.65 22.55 23.10 23.66 Feb 2009 23.20 23.20 22.91 23.05 Mar 2009 24.02 23.60 23.20 23.68 Feb 2009 0.199 0.13 0.1 0.08 Mar 2009 0.172 0.126 0.076 0.06 Apr 2009 23.32 23.44 23.61 24.62 Apr 2009 23.20 23.10 23.21 23.11 Ammoniacal-nitrogen (mg/L) Nov 2008 0.05 0.07 0.02 0.012 Dec 2008 0.165 0.156 0.125 0.074 Months Jan 2009 0.169 0.102 0.062 0.027 BOD (mg/L) Station M1 M2 Months Nov 2008 5 4.6 Dec 2008 Jan 2009 5.6 5.9 5.6 5.8 Feb 2009 5.4 5.7 Apr 2009 0.178 0.102 0.067 0.034 161 M3 M4 vii) 5.3 5.6 Months Nov 2008 2642 1992 2400 2470 Dec 2008 2400 3315 3640 3000 5.6 4.6 5.2 4.6 Jan 2009 2284 3215 3125 3470 Feb 2009 2265 2552 3120 3186 COD (mg/L) Station M1 M2 M3 M4 - 5.6 5.8 Water and Mussel Samples i) Zinc Water Nov 2008 0.142 0.112 0.109 0.045 M1 M2 M3 M4 Dec 2008 0.142 0.112 0.123 0.034 Mussel Nov 2008 Dec 2008 M1 76.23 56.45 M2 90.21 23.45 M3 98.45 45.32 M4 66.34 21.10 ii) Cadmium (ppm) Water M1 M2 M3 M4 Nov 2008 0.042 0.04 0.033 0.028 Dec 2008 0.041 0.044 0.033 0.019 Mussel Nov 2008 0.22 1.21 0.89 0.23 M1 M2 M3 M4 iii) Dec 2008 0.21 0.89 0.98 0.63 Lead (ppm) Months (mg/L) Jan 2009 Feb 2009 0.167 0.209 0.123 0.123 0.198 0.112 0.098 0.103 Mar 2009 0.56 0.28 0.22 0.17 Apr 2009 0.37 0.37 0.355 0.19 Months (µg/g) Jan 2009 Feb 2009 45.34 67.34 48.00 57.78 34.23 24.43 24.56 21.33 Mar 2009 67.23 32.00 21.34 24.56 Apr 2009 45.2 32.00 21.3 22.2 Months (mg/L) Jan 2009 Feb 2009 0.061 0.28 0.041 0.265 0.044 0.14 0.033 0.13 Months (µg/g) Jan 2009 Feb 2009 0.22 0.29 0.67 0.78 0.23 0.43 0.45 0.21 Mar 2009 0.387 0.335 0.335 0.125 Mar 2009 0.29 0.98 0.45 0.23 Apr 2009 0.38 0.37 0.355 0.3 Apr 2009 0.33 0.23 0.21 0.11 162 Water M1 M2 M3 M4 Nov 2008 1.020 1.320 1.200 0.380 Dec 2008 2.670 0.980 0.210 0.780 Mussel M1 M2 M3 M4 (c) Nov 2008 6.23 12.21 11 7.5 Dec 2008 8.27 6.78 5.43 3.45 Months (mg/L) Jan 2009 Feb 2009 0.980 1.990 0.450 0.980 0.240 3.210 0.320 0.120 Months (µg/g) Jan 2009 Feb 2009 5.43 8.27 6.78 6.32 4.34 5.34 3.45 3.45 Mar 2009 1.430 1.400 1.200 0.340 Apr 2009 1.230 1.020 1.030 1.020 Mar 2009 8.43 24.23 5.12 5.23 Apr 2009 4.3 5.4 6.3 2.1 Water Quality Data from Previous 1991, 2006 and Present Studies Year 1991 2006 2009 pH Danga Pendas 7.64 8.15 8.59 NA 7.97 8.68 Temp(ºC) Danga Pendas 30.50 28.80 29.00 NA NA 29.27 DO (mg/L) Danga Pendas 2.75 5.46 3.12 NA 5.68 4.33 AN(mg/L) Danga Pendas NA 0.443 0.242 NA 0.187 0.560 Year Zinc (mg/L) Danga Pendas Cadmium (mg/L) Danga Pendas Lead (mg/L) Nickel (mg/L) Danga Pendas Danga Pendas 1991 2006 2009 31.428 16.092 0.243 NA 0.339 0.753 0.082 0.001 0.282 0.773 0.900 2.253 0.059 NA 0.107 0.596 NA 0.430 NA 0.008 0.033 NA NA 0.214