HEAVY METAL POLLUTION OF WATER AND SEDIMENTS IN THE RIVERS OF HANOI, VIETNAM, AND ITS EFFECTS ON THE QUALITY OF AGRICULTURAL SOIL AND CROPS Nguyen Thi Lan Huong 2008 HEAVY METAL POLLUTION OF WATER AND SEDIMENTS IN THE RIVERS OF HANOI, VIETNAM, AND ITS EFFECTS ON THE QUALITY OF AGRICULTURAL SOIL AND CROPS By Nguyen Thi Lan Huong A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Bioproduction and Environmental Sciences Kyushu University Fukuoka, Japan 2008 ii Acknowledgements First of all, I am extremely grateful to my advisor Prof. Masami Ohtsubo for accepting me as his PhD student and his patience, guidance and support during my study. I am deeply thankful to thanks Associate Prof. Loretta Li (University of British Columbia, Canada) for her counsel and many valuable suggestions towards accomplishing this dissertation.
I would also like to Associate Prof. Shin-Ichiro Wada and Associate Prof. Takahiro Higashi (Kyushu University, Japan) for their many helpful comments towards the writing of this thesis. I also wish to express my gratitude to Dr Motohei Kanayama and Ms.
Akiko Nakano for their assistance with ordering supplies and helping me in the laboratory procedures. I am very grateful to Ministry of education, culture, sports, science and technology, Government of Japan for providing the scholarship for this study. At last but above all, I am greatly indebted to my parents, husband, son and friends for their love, encouragement, and endless support. i TABLE OF CONTENTS ABSTRACT.
X LIST OF FIGURES. V LIST OF TABLES. VII CHAPTER 1 INTRODUCTION .1 STATEMENT OF THE PROBLEM.2 SCOPE OF OBJECTIVES .4 ORGANIZATION OF THESIS. 10 CHAPTER 2 ASSESSMENT OF WATER QUALITY AND ITS SUITABILITY FOR THE TO LICH AND KIM NGUU RIVERS IN HANOI CITY .3 RESULTS AND DISCUSSION .1 Chemical properties of water.
Heavy metal pollution assessment. Suitability for Irrigation Water.4 CONCLUSIONS AND RECOMMENDATION. 25 CHAPTER 3 HEAVY METAL CONTAMINATION OF RIVER SEDIMENTS IN HANOI, VIETNAM .2 MATERIALS AND METHODS .1 Materials and Field Sampling .1 Chemical and Physical Properties of Sediment .2 Semi-quantitative estimates of mineralogical composition .3 Total heavy metal concentration .4 Selective Sequential Extraction .5 Batch leaching test .3 RESULTS AND DISCUSSION .3 Clay Mineralogical Characterization .4 Impact of Industrial Activities on the Quality of Sediment .5 Correlation between Organic Matter and Heavy Metal Concentration in Sediment .5 Distribution of Heavy Metal in Sediment Fractions .6 Leachibility and Mobility of Heavy Metals in the Sediments .4 CONCLUSIONS AND RECOMMENDATION. 56 CHAPTER 4 IMPACT OF RIVER POLLUTION ON AGRICULTURAL SOILS AND VEGETABLES IN A SUBURBAN AREA OF HANOI, VIETNAM.2 MATERIALS AND METHODS .1 Irrigation Water, Sampling Site and Soil Samples .1 Chemical and Physical Properties of Agricultural Soils .2 Heavy Metal Concentration.5 Batch Leaching Test .3 RESULTS AND DISCUSSION .1 Properties of Agricultural Soil .2 Heavy Metal Concentration of Soil .3 Mobility of Heavy Metal .5 Leaching Heavy Metals from Contaminated Soils .6 Fractionated Heavy Metals and Potential Leachability .7 Heavy Metal Concentration in Vegetable .8 Soil Plant Transfer Coefficients.
93 CHAPTER 5 HEAVY METAL CONTAMINATION OF SOIL AND RICE IN WASTEWATER-IRRIGATED PADDY FIELD IN A SUBURBAN AREA OF HANOI VIETNAM. 2 MATERIALS AND METHODS .1 Materials and Sampling Site .1 Chemical and Physical Properties of Soil .2 Determination of Total Metal Concentration. Selective Sequential Extraction (SSE) of Heavy Metals. RESULTS AND DISCUSSION.1 Properties of the Paddy Soil .2 Heavy Metal Concentration in the Soil .3 Heavy Metal Association with Soil Fractions .4 Heavy Metal Adsorption Capacity of Paddy Soils .5 Potential Leachability of Heavy Metals .6 Fractionated Heavy Metals and Potential Leachability.
128 CHAPTER 6 CONCLUSIONS AND RECOMMENDATIONS .2 RECOMMENDATIONS FOR THE FUTURE WORK. 138 iv LIST OF FIGURES Figure 1.1 Location of sampling sites and factories .2 Relationship between total and water-soluble concentration and metal retained in suspended solid. The XRD patterns of the <2µm clay fraction of SD10, representing sediment sample of the To Lich and Kim Nguu Rivers in Hanoi. Spacing is in nm.
Treatments: a, Mg-saturation and glycerol-solvation; b, Mg-saturation and air- drying; c, K-saturation and air-drying; d, K-saturation and heating at 5000C. Correlation between organic matter content and total heavy metal concentration organic fraction concentration .4 Heavy metal extracted via SSE from sediment samples .5 Average percentage of the respective heavy metal concentrations for each fraction of the sediments at all sampling sites, the variation of metal concentration due to the sampling sites is also indicated .6 Changes in the concentration of leached heavy metals by repeated washings with de-ionized water and the solutions of nitric acid, acetic acid and EDTA.7 Correlation between leached metal concentration and total metal concentration for the sediment samples subjected to leaching with water, acid and EDTA .8 Average of the ratio of leached metal concentration to total metal concentration for the sediment samples subjected to leaching with water, acid and EDTA. Variation in the ratio from average is also indicated for the respective metal types and leaching solutions. 9 Relationship between metal concentration of fraction and leached metal concentration of using different leaching solutions of sediment samples .10 Correlation between organic matter content and the ratio of leached metal concentration to total metal concentration for the sediment samples subjected to leaching with different types of solution.
2 Heavy metal extracted via SSE from soil samples .3 Average percentage of the respective heavy metal concentrations for each fraction of the soil samples, the variation of metal concentration due to the sampling sites is also indicated .4 (a) Characteristics of Cd, Cr and Cu adsorption of Agricultural soil .4 (b) Characteristics of Ni. Pb and Zn adsorption of Agricultural soil.5 (a) Freundlich and Langmuir adsorption isotherm models .80 for Cd, Cr and Ni of agricultural soil.5 (b) Freundlich and Langmuir adsorption isotherm models.81 for Ni, Pb and Zn of agricultural soil .6 Changes in the concentration of leached heavy metals by repeated washings with de-ionized water and the solutions of nitric acid, acetic acid and EDTA.7 Correlation between leached metal concentration and total metal concentration for the soil samples subjected to leaching with water, acid and EDTA.8 Average of the ratio of leached metal concentration to total metal concentration for the soil samples subjected to leaching with water, acid and EDTA.9 Comparison of leached metal concentration for different treatments with sequentially fractionated heavy metal concentration in soil samples.10 Correlation between total heavy metal concentrations in the soils and vegetables .1 Location of soil and rice grain sampling.2 XRD patterns for the < 2µm clay fractions of the soil sample (S8). Spacing is in nm; Treatments a: Mg-saturation and glycerol – solvation, b: Mg-saturation and air-drying, c: K-saturation and air-drying, d: K-saturation and heating at 500oC.3 The metal concentration of soil samples following by distances from the road.4 Heavy metal extracted via SSE from soil samples.5 Average percentage of the respective heavy metal concentrations for each fraction of the soil samples, the variation of metal concentration due to the sampling sites is also indicated .6 (a) Characteristics of Cd, Cr and Cu adsorption of paddy soil .6 (b) Characteristics of Ni, Pb and Zn adsorption of paddy soil .7(a) Freundlich and Langmuir adsorption isotherm models. 115 for Cd, Cr and Cu of paddy soil .7(b) Freundlich and Langmuir adsorption isotherm models.
116 for Ni, Pb and Zn of paddy soil.8 Changes in the concentration of leached heavy metals by repeated washings with de-ionized water and the solutions of nitric acid, acetic acid and EDTA.9 Correlation between leached metal concentration and total metal concentration for the soil samples subjected to leaching with water, acid and EDTA.10 The average of the ratio of leached metal concentration to total metal concentration for soil samples subjected to leaching with water, acid and EDTA .11 Comparison of leached metal concentration for different treatments with sequentially fractionated heavy metal concentration in soil samples .12 Comparing between heavy metals leaching capacity by different solutions of sediment and soils .13 Comparing between leaching capacity of heavy metals of different solutions of sediment and soils .14 Correlation between heavy metal concentration in soil and rice grain. 126 vi LIST OF TABLES Table 2.1 Chemical properties in the water of the To Lich and Kim Nguu Rivers .2 Correlation coefficient between chemical properties of water.3 Heavy metal concentration in water from the To Lich and Kim Nguu Rivers .4 Heavy metal concentration in suspended solid (g/kg).5 Information on the industry in the areas of the water sampling sites and the total heavy metal concentrations of water .1 Sediment sample location and relationship between the types of industry and metal concentration in the sediment. 2 Chemical and physical properties of sediment samples .3 Mineral contents (%) in the <2 µm clay fraction of sediment samples.1 Chemical and physical properties of soil samples taken at different from the canal .2 Mineral contents (%) in the <2 mm clay fraction of soil samples .3 Total heavy metal concentration of soil samples (mg/kg).4 Distribution coefficient Kd (ml/g) for agricultural soil.5 Total heavy metal concentration in vegetable (mg/kg) .6 The range of transfer coefficients of metals and their suggested coefficient range.1 Chemical and physical properties of soil samples .2 Relative mineral contents in the <2µm clay fractions .3 Total heavy metal concentration in soil samples.4 Distribution coefficient Kd (ml/g) for soil. 5 Total heavy metal concentration of rice grain (mg kg-1) and transfer coefficient.
Concentration of sequentially fractionated Cd of Sediments (mg kg-1). Concentration of sequentially fractionated Cr of Sediments (mg kg-1). Concentration of sequentially fractionated Cu of Sediments (mg kg-1). Concentration of sequentially fractionated Ni of Sediments (mg kg-1).
Concentration of sequentially fractionated Pb of Sediments (mg kg-1). Concentration of sequentially fractionated Zn of Sediments (mg kg-1). Concentration of sequentially fractionated Cd of Agricultural soil (mg kg-1). Concentration of sequentially fractionated Cr of Agricultural soil (mg kg-1).
Concentration of sequentially fractionated Cu of Agricultural soil (mg kg-1). Concentration of sequentially fractionated Ni of Agricultural soil (mg kg-1). Concentration of sequentially fractionated Pb of Agricultural soil (mg kg-1). Concentration of sequentially fractionated Zn of Agricultural soil (mg kg-1).
Concentration of sequentially fractionated Cd of Paddy soil (mg kg-1). Concentration of sequentially fractionated Cr of Paddy soil (mg kg-1). Concentration of sequentially fractionated Cu of Paddy soil (mg kg-1). Concentration of sequentially fractionated Ni of Paddy soil (mg kg-1).
Concentration of sequentially fractionated Pb of Paddy soil (mg kg-1). Concentration of sequentially fractionated Zn of Paddy soil (mg kg-1). Adoption Isotherm of Cd of Sediment. Adoption Isotherm of Cr of Sediment.
Adoption Isotherm of Cu of Sediment. Adoption Isotherm of Ni of Sediment. Adoption Isotherm of Pb of Sediment. Adoption Isotherm of Zn of Sediment.
Adoption Isotherm of Cd of Agricultural soil. Adoption Isotherm of Cr of Agricultural soil. Adoption Isotherm of Cu of Agricultural soil. Adoption Isotherm of Ni of Agricultural soil.
Adoption Isotherm of Pb of Agricultural soil. Adoption Isotherm of Zn of Agricultural soil. Adoption Isotherm of Cd of Paddy soil. Adoption Isotherm of Cr of Paddy soil.
Adoption Isotherm of Cu of Paddy soil. Adoption Isotherm of Ni of Paddy soil. Adoption Isotherm of Pb of Paddy soil. Adoption Isotherm of Zn of Paddy soil.
Leached concentration of Cd by different solutions of 5 times washing of Sediment (mg kg-1). Leached concentration of Cr by different solutions of 5 times washing of Sediment (mg kg-1). Leached concentration of Cu by different solutions of 5 times washing of Sediment (mg kg-1). Leached concentration of Ni by different solutions of 5 times washing of Sediment (mg kg-1).
Leached concentration of Pb by different solutions of 5 times washing of Sediment (mg kg-1). Leached concentration of Zn by different solutions of 5 times washing of Sediment (mg kg-1). Leached concentration of Cd by different solutions of 5 times washing of Agricultural soil (mg kg-1).