Multi-isotope approach (Cu-Zn-Pb) for tracing metal pollution sources into the marine environment|RISS 상세보기

다국어 초록 (Multilingual Abstract)

In the marine environment, metal pollution sources mainly originated from terrestrial regions, move to streams via rainfall runoff, and then flow into the marine environments or enter it via atmospheric diffusion. Metal pollution in marine and coastal environments has been reported worldwide, particularly Cu, Zn, and Pb pollution. Accurate information on the metal pollution sources is needed to prevent and manage metal pollution in marine environments. However, it is difficult to trace pollution sources accurately only through metal concentration studies due to the complexity of environmental pollution. A new analytical tool is needed to solve this environmental problem. Metal stable isotopes are used to trace pollution sources accurately and evaluate the contributions of each pollutant. However, marine samples have lower metal concentrations than terrestrial samples and contain large amounts of salt, which interferes with isotope analysis and thus makes it difficult to analyze metal stable isotopes. Since metal pollution in marine environments is closely related to terrestrial and atmospheric environments, it is essential to develop chemical separation methods for metal stable isotopes that can be applied to various environmental samples. Therefore, isotope methodology with high accuracy and precision for Cu, Zn, and Pb stable isotopes was developed to produce high-quality isotope data. Based on this method, this paper presents the isotopic compositions of Cu, Zn, and Pb from various pollution sources entering the marine environment originating from terrestrial regions, and investigates whether pollution sources can be distinguished. The applicability of metal stable isotopes in marine organisms was also investigated.
The column separation method developed here gave Cu, Zn, and Pb yields over 99.2%. This method can be applied to various environmental samples. This study provides Cu, Zn, and Pb isotope data of thirty-three geological and biological reference materials used worldwide. Among the metal pollutants entering marine environments, the metal concentrations and isotopic compositions for Cu, Zn, and Pb in non-exhaust traffic emission sources (brake pad, asphalt, curb, road paint, tire, and brake dust) and fine road dust (PM10) in Busan were presented for the first time. These isotopic compositions distinguished the non-exhaust emission sources from each other and showed that each metal pollutant came from different sources.
Road-deposited sediments (RDS) are transported to marine environments through rainfall runoff. Therefore, this study investigated the relationship between size-fractionated RDS and total suspended solids (TSS) in rainfall runoff, and showed that less than 63 μm of RDS were entered into streams and marine environments by rainfall runoff. Various metal pollution sources exist in industrial areas. Metal concentrations and stable isotopes of Cu and Pb in the stream sediments of the Shihwa National Industrial Complex, which has the most industrial facilities in South Korea, were studied. RDS transported through rainfall runoff greatly affected Cu and Pb isotopic compositions in stream sediments. In addition, the Zn isotopic compositions in surface sediments and marine organisms (oysters and mussels) collected from the coast of South Korea are presented, and the relationship between sediments and marine organisms is investigated. Oysters are more suitable for biomonitoring metal contamination than mussels and can be used for monitoring and managing coastal environments and ecosystems.
Multi-isotopic compositions (Cu, Zn, and Pb) and their combination can distinguish different pollution sources. This study also presented the metal stable isotopes of potential pollution sources entering the marine environment (non-exhaust emission sources, RDS, and stream sediments) and those in marine environmental samples (surface sediments, oysters, and mussels); such data are scarce worldwide. Environmental studies using metal stable isotopes and the application of multi-isotopes will play an important role in managing metal pollution sources and understanding biogeochemical processes.

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목차 (Table of Contents)

Contents
Contents I
List of Figures VII
List of Tables XI

Contents
Contents I
List of Figures VII
List of Tables XI
Chapter 1. General introduction 1
1.1. Characteristics of environmental metal pollution 2
1.2. Application of metal stable isotopes in environmental studies 4
1.2.1. Cu isotopes 4
1.2.2. Zn isotopes 4
1.2.3. Pb isotopes 5
1.2.4. Approach of metal stable isotopes as an environmental forensic tool 6
1.3. Objectives 7
Chapter 2. Copper, zinc and lead isotopic delta values and isotope ratios of various geological and biological reference materials 9
2.1. Introduction 10
2.2. Experimental procedure 11
2.2.1. Sample preparation 11
2.2.2. Column chemistry 12
2.2.3. Isotope measurement by MC-ICP-MS 14
2.3. Results and discussion 15
2.3.1. Chromatographic separation of Cu/Zn and Pb 15
2.3.2. Precision and bias of Cu, Zn, and Pb isotopes 21
2.3.3. Cu, Zn and Pb delta values and isotope ratios of thirty-three commercial RMs 25
2.4. Conclusions 32
Chapter 3. Characteristics of potentially toxic elements and multi-isotope signatures (Cu, Zn, Pb) in non-exhaust traffic emission sources 33
3.1. Introduction 35
3.2. Materials and methods 37
3.2.1. Sample collection and PTEs analysis 37
3.2.2. Cu, Zn, and Pb isotope analysis 38
3.3. Results and discussion 39
3.3.1. PTEs concentrations of non-exhaust traffic emission sources 39
3.3.2. Cu, Zn, and Pb isotopic signatures of non-exhaust emission sources 44
3.3.3. Multi-isotope approach as a useful tool for identifying metal pollution sources 50
3.4. Conclusions 55
Chapter 4. Toxic metal concentrations and Cu-Zn-Pb isotopic compositions in tires 56
4.1. Introduction 57
4.2. Materials and methods 59
4.2.1. Toxic metal analysis 59
4.2.2. Cu, Zn, and Pb isotope analysis 60
4.3. Results and discussion 61
4.3.1. Toxic metal concentrations 61
4.3.2. Cu isotopic composition 64
4.3.3. Zn isotopic composition 66
4.3.4. Pb isotopic composition 67
4.3.5. Application of multi-isotopies as a useful tool for source identification in urban environments 69
4.4. Conclusions 71
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 72
5.1. Introduction 73
5.2. Materials and methods 75
5.2.1. Study area 75
5.2.2. Sampling and measurement of PTEs 75
5.2.3. Pollution and ecological risk assessments 76
5.2.4. Health risk assessment 78
5.2.5. Measurement of Cu, Zn, and Pb isotopes 80
5.3. Results and discussion 80
5.3.1. Characteristics of PTEs in road dust (<10 μm) 80
5.3.1.1. Concentrations of PTEs 80
5.3.1.2. Pollution assessment of PTEs 86
5.3.1.3. Ecological risk assessments 87
5.3.1.4. Health risk assessments 87
5.3.2. Pollution source and environmental impact of PTEs in the PM10 fraction of road dust 89
5.3.2.1. Statistical analysis 89
5.3.2.2. Elemental ratios 91
5.3.2.3. Cu, Zn, and Pb isotopic compositions 92
5.4. Conclusions 96
Chapter 6. Multi-isotope signatures (Cu, Zn, Pb) of different particle sizes in road-deposited sediments: A case study from industrial area 98
6.1. Introduction 99
6.2. Materials and methods 101
6.2.1. Study area and sample collection 101
6.2.2. Heavy metal analysis 102
6.2.3. Cu, Zn and Pb isotopes analysis 103
6.2.4. Heavy metal loadings on a grain size fraction 104
6.3. Results and discussion 105
6.3.1. Heavy metal concentrations in different RDS size fraction and TSS 105
6.3.2. Cu isotopic compositions of different RDS size fractions 110
6.3.3. Zn isotopic compositions of different RDS size fractions 113
6.3.4. Pb isotopic compositions of different RDS size fractions 115
6.3.5. Relationship between different RDS size fractions and TSS in runoff 116
6.3.6. Application of multi-isotopes as a useful tool for source identification in RDS studies 120
6.4. Conclusions 123
Chapter 7. Investigations of Pb and Cu isotopes to trace contamination sources from the artificial Shihwa Lake in Korea 124
7.1. Introduction 125
7.2. Methods 126
7.2.1. Study area 126
7.2.2. Heavy metals, Cu and Pb isotope analysis 126
7.3. Results 128
7.3.1. Heavy metal concentrations in stream sediments 128
7.3.2. Pb and Cu isotopic compositions 129
7.4. Discussion 131
7.4.1. Differences in metal concentrations between streams 131
7.4.2. Tracing metal pollution sources using Pb and Cu isotopes 132
7.5. Conclusions 136
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 137
8.1. Introduction 138
8.2. Materials and methods 140
8.2.1. Sampling 140
8.2.2. Trace metal analysis 142
8.2.3. The biota sediment accumulation factor (BSAF) 144
8.2.4. Zn isotope analysis 145
8.3. Results and discussion 147
8.3.1. Trace metal concentrations in mussels, oysters, and surface sediments 147
8.3.2. Correlation of trace metals between bivalve mollusk tissues and sediments 153
8.3.3. Zn isotope signatures in mussels and oysters 157
8.4. Conclusions 162
Chapter 9. Conclusions 163
References 168
Appendixes 232
Curriculum vitae 265
Acknowledgements 272

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