Title Page

ABSTRACT

국문 초록

Contents

CHAPTER 1. General introduction 22

1.1. Characteristics of environmental metal pollution 23

1.2. Application of metal stable isotopes in environmental studies 25

1.2.1. Cu isotopes 25

1.2.2. Zn isotopes 25

1.2.3. Pb isotopes 26

1.2.4. Approach of metal stable isotopes as an environmental forensic tool 27

1.3. Objectives 28

CHAPTER 2. Copper, zinc and lead isotopic delta values and isotope ratios of various geological and biological reference materials 30

2.1. Introduction 31

2.2. Experimental procedure 32

2.2.1. Sample preparation 32

2.2.2. Column chemistry 33

2.2.3. Isotope measurement by MC-ICP-MS 35

2.3. Results and discussion 36

2.3.1. Chromatographic separation of Cu/Zn and Pb 36

2.3.2. Precision and bias of Cu, Zn, and Pb isotopes 42

2.3.3. Cu, Zn and Pb delta values and isotope ratios of thirty-three commercial RMs 46

2.4. Conclusions 53

CHAPTER 3. Characteristics of potentially toxic elements and multi-isotope signatures (Cu, Zn, Pb) in non-exhaust traffic emission sources 54

3.1. Introduction 56

3.2. Materials and methods 58

3.2.1. Sample collection and PTEs analysis 58

3.2.2. Cu, Zn, and Pb isotope analysis 59

3.3. Results and discussion 60

3.3.1. PTEs concentrations of non-exhaust traffic emission sources 60

3.3.2. Cu, Zn, and Pb isotopic signature of non-exhaust traffic emission sources 65

3.3.3. Multi-isotope approach as a useful tool for identifying metal pollution sources 71

3.4. Conclusions 76

CHAPTER 4. Toxic metal concentrations and Cu-Zn-Pb isotopic compositions in tires 77

4.1. Introduction 78

4.2. Materials and methods 80

4.2.1. Toxic metal analysis 80

4.2.2. Cu, Zn, and Pb isotope analysis 81

4.3. Results and discussion 82

4.3.1. Toxic metal concentrations 82

4.3.2. Cu isotopic composition 85

4.3.3. Zn isotopic composition 87

4.3.4. Pb isotopic composition 88

4.3.5. Application of multi-isotopes as a useful tool for source identification in urban environments 90

4.4. Conclusions 92

CHAPTER 5. Characteristics of potentially toxic elements, risk assessments, and isotopic compositions (Cu‒Zn‒Pb) in the PM10 fraction of road dust in Busan, South Korea 93

5.1. Introduction 94

5.2. Materials and methods 96

5.2.1. Study area 96

5.2.2. Sampling and measurement of PTEs 96

5.2.3. Pollution and ecological risk assessments 97

5.2.4. Heath risk assessment 99

5.2.5. Measurement of Cu, Zn, and Pb isotopes 101

5.3. Results and discussion 101

5.3.1. Characteristics of PTEs in road dust (〈10 μm) 101

5.3.2. Pollution source and environmental impact of PTEs in the PM10 fraction of road dust[이미지참조] 110

5.4. Conclusions 117

CHAPTER 6. Multi-isotope signatures (Cu, Zn, Pb) of different particle sizes in road-deposited sediments: A case study from industrial area 119

6.1. Introduction 120

6.2. Material and methods 122

6.2.1. Study area and sample collection 122

6.2.2. Heavy metal analysis 123

6.2.3. Cu, Zn and Pb isotopes analysis 124

6.2.4. Heavy metal loadings on a grain size fraction 125

6.3. Results and discussion 126

6.3.1. Heavy metal concentrations in different RDS size fractions and TSS 126

6.3.2. Cu isotopic compositions of different RDS size fractions 131

6.3.3. Zn isotopic compositions of different RDS size fractions 134

6.3.4. Pb isotopic compositions of different RDS size fractions 136

6.3.5. Relationship between different RDS size fractions and TSS in runoff 137

6.3.6. Application of multi-isotopes as a useful tool for source identification in RDS studies 141

6.4. Conclusions 144

CHAPTER 7. Investigations of Pb and Cu isotopes to trace contamination sources from the artificial Shihwa Lake in Korea 145

7.1. Introduction 146

7.2. Methods 147

7.2.1. Study area 147

7.2.2. Heavy metals, Cu and Pb isotope analysis 147

7.3. Results 149

7.3.1. Heavy metal concentrations in stream sediments 149

7.3.2. Pb and Cu isotopic compositions 150

7.4. Discussion 152

7.4.1. Difference in metal concentrations between streams 152

7.4.2. Tracing metal pollution sources using Pb and Cu isotopes 153

7.5. Conclusions 157

CHAPTER 8. A nationwide survey of trace metals and Zn isotopic signatures in mussels (Mytilus edulis) and oysters (Crassostrea gigas) from the coast of South Korea 158

8.1. Introduction 159

8.2. Materials and methods 161

8.2.1. Sampling 161

8.2.2. Trace metal analysis 163

8.2.3. The biota sediment accumulation factor (BSAF) 165

8.2.4. Zn isotope analysis 166

8.3. Results and discussion 168

8.3.1. Trace metal concentrations in mussels, oysters, and surface sediments 168

8.3.2. Correlation of trace metals between bivalve mollusk tissues and sediments 174

8.3.3. Zn isotopic signatures in mussels and oysters 178

8.4. Conclusions 183

CHAPTER 9. Conclusions 184

REFERENCES 189

APPENDIXES 253

CURRICULUM VITAE 286

Table 2.1. Instrumental setting by MC-ICP-MS (Neptune Plus, Thermo Scientific). 35

Table 2.2. Average recovery percentage of the Cu, Fe, and Zn separation for first column... 39

Table 2.3. Average recovery percentage of the Pb separation using eight reference materials. 41

Table 2.4. Comparison of Cu and Zn isotope data from this study with previously reported values. 45

Table 2.5. Cu, Zn and Pb isotope compositions of eighteen geological reference materials... 47

Table 3.1. Summary of mean and standard deviation values for PTEs concentrations (mg/kg) in brake pad, brake dust, curb, asphalt, road paint,... 64

Table 3.2. Cu, Zn, and Pb isotope compositions of brake pad, brake dust, curb, asphalt,... 66

Table 3.3. Cu, Zn, and Pb isotope compositions of brake pad, brake dust, curb, asphalt,... 67

Table 4.1. Mean (standard deviation in parentheses) of toxic metal concentrations... 83

Table 4.2. Comparisons of the mean, minimum, and maximum values of the Cu, Zn, and... 86

Table 5.1. Classification of enrichment factor (EF) and potential ecological risk factor... 98

Table 5.2. Key parameters for the health risk assessment through three pathways used in... 100

Table 5.3. Comparison of mean values for PTEs concentrations (mg/kg) in PM10 of road...[이미지참조] 102

Table 5.4. The results of hazard quotient (HQ) and hazard index (HI) of non-carcinogenic... 109

Table 5.5. Pearson's correlation of the potentially toxic elements in PM10 of road dust....[이미지참조] 111

Table 6.1. Means and standard deviations (1s) of heavy metal concentrations in six different particle sizes of RDS and TSS in runoff in this study. 127

Table 6.2. Comparison of mean, minimum and maximum values for Cu, Zn, and Pb... 130

Table 8.1. Trace metals (mg/kg dry weight) with certified reference materials for SRM 1566b, (oyster tissue) SRM 2976, and BCR-668 (mussel tissue). 164

Table 8.2. Trace metals (mg/kg dry weight) with certified reference materials for MESS-... 165

Table 8.3. Average, minimum and maximum (in parenthesis) concentration of trace metals in mussels, oysters, and sediments (mg/kg dry weight) and comparison... 169

Table 8.4. Average, minimum and maximum (in parenthesis) concentration of trace metals in mussels, oysters, and sediments (mg/kg wet weight) of this study and... 170

Table 8.5. Matrix of Pearson's correlation coefficient among trace metals in mussels. 172

Table 8.6. Matrix of Pearson's correlation coefficient among trace metals in oysters. 173

Table 8.7. The average of concentrations and isotopic compositions (‰) of Zn in mussels,... 179