Environmental Chemistry and Toxicology of Mercury

Guangliang Liu, PhD, is Research Scientist in the Department of Chemistry and Biochemistry, Florida International University, where he manages the Mercury Laboratory. Yong Cai, PhD, is Professor in the Department of Chemistry and Biochemistry, Florida International University. He has been working on environmental chemistry and the geochemistry of mercury for almost twenty years. Nelson O'Driscoll, PhD, is Canada Research Chair in Environmental Biogeochemistry and Associate Professor in the Department of Earth and Environmental Science, Acadia University.

PREFACE xiii ACKNOWLEDGMENTS xv

CONTRIBUTORS xvii

1 OVERVIEW OF MERCURY IN THE ENVIRONMENT 1
Guangliang Liu, Yong Cai, Nelson O’Driscoll, Xinbin Feng, and Guibin Jiang

1.1 Introduction / 1

1.2 Toxicity and Health Risks of Mercury Exposure / 2

1.3 Sources of Mercury / 2

1.4 Overview of Mercury Biogeochemical Cycling / 7

1.5 Structure of the Book / 8

1.6 Concluding Remarks / 9

References / 9

PART I ANALYTICAL DEVELOPMENTS 13

2 ADVANCES IN SPECIATION ANALYSIS OF MERCURY IN THE ENVIRONMENT 15
Yanbin Li, Yongguang Yin, Guangliang Liu, and Yong Cai

2.1 Introduction / 15

2.2 Sample Preparation for Hg Speciation in Environmental Samples / 16

2.3 Application of GC Technique in Hg Speciation Analysis / 32

2.4 Application of HPLC Technique in Hg Speciation Analysis / 36

2.5 Application of Capillary Electrophoresis Techniques in Hg Speciation Analysis / 39

2.6 Application of X-Ray Absorption Spectroscopy in Probing Chemical Microenvironment of Hg / 40

2.7 Application of Stable Isotope Dilution Technique in Mercury Speciation Analysis / 41

2.8 Summary / 43

References / 44

3 MEASURING GAS PHASE MERCURY EMISSIONS FROM INDUSTRIAL EFFLUENTS 59
Samuel J. Ippolito, Ylias M. Sabri, and Suresh K. Bhargava

3.1 Introduction / 59

3.2 Standardized Methods for Measuring Mercury / 72

3.3 Mercury Continuous Emission Monitors (CEMs) / 81

3.4 Future Outlook / 95

References / 96

PART II SPECIATION AND TRANSFORMATION 111

4 ATMOSPHERIC CHEMISTRY OF MERCURY 113
Che-Jen Lin, Pattaraporn Singhasuk, and Simo O. Pehkonen

4.1 Introduction / 113

4.2 The Overall Picture / 114

4.3 Chemical Transformations in the Gas Phase / 118

4.4 Chemical Transformations in the Aqueous Phase / 131

4.5 Redox Chemistry at the Interface Between the Atmosphere and Earth’s Surfaces / 136

4.6 Atmospheric Implications of the Identified Redox Pathways / 139

4.7 Future Research Needs / 143

References / 144

5 MICROBIAL TRANSFORMATIONS IN THE MERCURY CYCLE 155
Chu-Ching Lin, Nathan Yee, and Tamar Barkay

5.1 Introduction / 155

5.2 Mercury Methylation / 158

5.3 Methylmercury Degradation / 168

5.4 Redox Cycling of Inorganic Hg / 169

5.5 Conclusions / 179

References / 180

6 PHOTOREACTIONS OF MERCURY IN AQUATIC SYSTEMS 193
Emma E. Vost, Marc Amyot, and Nelson J. O’Driscoll

6.1 Significance of Mercury Photoreactions / 193

6.2 Concepts in Mercury Photoreactions / 194

6.3 Current Methods in Mercury Photochemistry / 209

6.4 Summary / 211

References / 212

7 CHEMICAL SPECIATION OF MERCURY IN SOIL AND SEDIMENT 219
Ulf Skyllberg

7.1 Introduction / 219

7.2 Physicochemical Properties, Oxidation States, Chemical Forms, Structures, and Concentrations of Mercury in the Environment / 220

7.3 Aqueous Phase: Major Ligands and Their Affinities for Mercury(II) / 222

7.4 Liquid and Solid Phases of Mercury in Soils and Sediments / 229

7.5 Reactions of Mercury(II) with Soil and Sediment Particle Surfaces / 231

7.6 Stabilization of Nanoparticulate Mercury(II) Sulfides by Natural Organic Matter / 237

7.7 Solubility and Chemical Speciation of Mercury(II) in Soils and Sediments / 237

7.8 Methods for Studying the Chemistry of Mercury(II) in Soils and Sediments / 248

7.9 Future Research Needs / 249

References / 252

8 THE EFFECTS OF DISSOLVED ORGANIC MATTER ON MERCURY BIOGEOCHEMISTRY 259
Chase A. Gerbig, Joseph N. Ryan, and George R. Aiken

8.1 Introduction / 259

8.2 Dissolved Organic Matter / 260

8.3 Field Observations / 263

8.4 Effects of DOM on Mercury Distributions Between Solution and Particles / 265

8.5 Mercury Binding Strength / 268

8.6 Mercury Binding Environment / 271

8.7 Methylmercury Binding Strength and Environment / 274

8.8 DOM and Mercury Mineral Dissolution / 276

8.9 DOM and Mercury Mineral Precipitation / 280

References / 284

9 TRACKING GEOCHEMICAL TRANSFORMATIONS AND TRANSPORT OF MERCURY THROUGH ISOTOPE FRACTIONATION 293
Holger Hintelmann and Wang Zheng

9.1 Introduction / 293

9.2 Fractionation of Mercury Isotopes in Environmental Processes / 300

9.3 Hg Isotope Variations in Nature / 315

9.4 Summary / 319

References / 320

PART III TRANSPORT AND FATE 329

10 ATMOSPHERIC TRANSPORT OF MERCURY 331
Oleg Travnikov

10.1 Introduction / 331

10.2 General Concepts of Mercury Cycling in the

Atmosphere / 331

10.3 Methods for Studying Atmospheric Mercury Transport / 336

10.4 Assessments of Airborne Mercury Pollution / 342

10.5 Knowledge Gaps / 354

References / 356

11 ADSORPTION OF MERCURY ON SOLIDS IN THE AQUATIC ENVIRONMENT 367
Guangliang Liu, Yanbin Li, and Yong Cai

11.1 Introduction / 367

11.2 Adsorption of Mercury on Solids / 369

11.3 Role of Colloids in Mercury Adsorption / 374

11.4 Concluding Remarks / 380

References / 381

12 EXCHANGE OF ELEMENTAL MERCURY BETWEEN THE OCEANS AND THE ATMOSPHERE 389
Asif Qureshi, Matthew Macleod, Elsie Sunderland, and Konrad Hungerbu¨ hler

12.1 Introduction / 389

12.2 Models of Gas Exchange of Elemental Mercury at the Air–Sea Interface / 390

12.3 Field Studies of Ocean-To-Air Fluxes of Mercury / 398

12.4 Rate Constants for Reduction and Oxidation of Mercury Species in Ocean Waters / 400

12.5 Modeling Studies Estimating Oceanic Air–Sea Exchange / 411

12.6 Conclusions and Future Directions / 415

References / 416

13 EXCHANGE OF MERCURY BETWEEN THE ATMOSPHERE AND TERRESTRIAL ECOSYSTEMS 423
Mae Sexauer Gustin

13.1 General Overview / 423

13.2 Methods and Tools Applied for Measurement and Understanding of Air–Terrestrial Surface Exchange / 425

13.3 Measured Fluxes / 433

13.4 Conclusions / 442

References / 444

PART IV BIOACCUMULATION, TOXICITY, AND METALLOMICS 453

14 BIOACCUMULATION AND BIOMAGNIFICATION OF MERCURY THROUGH FOOD WEBS 455
Karen Kidd, Meredith Clayden, and Tim Jardine

14.1 Introduction / 455

14.2 Mercury in Aquatic and Terrestrial Organisms / 457

14.3 Mercury within Organisms / 464

14.4 Factors Affecting Mercury in Biota / 465

14.5 Biomagnification of Mercury Through Food Webs / 474

14.6 Mercury Stable Isotopes in Bioaccumulation Studies / 481

14.7 Case Study—Kejimkujik National Park and Historic Site, Nova Scotia, Canada / 482

14.8 Conclusions / 484

References / 485

15 A REVIEW OF MERCURY TOXICITY WITH SPECIAL REFERENCE TO METHYLMERCURY 501
Mineshi Sakamoto, Katsuyuki Murata, Akiyoshi Kakita, and Masanori Sasaki

15.1 Introduction / 501

15.2 Global Mercury Emission into the Atmosphere / 502

15.3 Metabolism and Toxicity of Chemical Forms of Mercury / 503

15.4 Risk Assessment of Prenatal Exposure to Methylmercury / 509

15.5 Risks and Benefits of Fish Consumption for Brain Development / 510

15.6 Exceptional Methylmercury Exposure Through Rice / 510

15.7 Summary / 511

References / 511

16 METALLOMICS OF MERCURY: ROLE OF THIOLAND SELENOL-CONTAINING BIOMOLECULES 517
Feiyue Wang, Marcos Lemes, and Mohammad A.K. Khan

16.1 Introduction / 517

16.2 Metallomics of Mercury / 517

16.3 Mercury and Methylmercury Complexes with Thiol-Containing Biomolecules / 519

16.4 Mercury and Methylmercury Binding to Selenol-Containing Biomolecules / 522

16.5 Lability of Mercury or Methylmercury Complexes with Thiols or Selenols / 524

16.6 Thiol-Containing Biomolecules in the Uptake and Metabolism of Mercury / 526

16.7 Selenium Aided Biomineralization of Mercury and Methylmercury / 529

16.8 Analytical and Modeling Approaches / 531

16.9 Conclusion / 538

References / 538

17 HUMAN HEALTH SIGNIFICANCE OF DIETARY EXPOSURES TO METHYLMERCURY 545
Anna L. Choi and Philippe Grandjean

17.1 Introduction / 545

17.2 Methylmercury Exposure / 546

17.3 Nutrients in Fish and Seafood / 548

17.4 Major Prospective Cohort Studies / 549

17.5 Health Effects / 552

17.6 Cardiovascular Outcomes / 555

17.7 Nutrient and Methylmercury Exposure as Predictors of Developmental Outcomes / 556

17.8 Confounding Variables / 557

17.9 Risk Assessment and Exposure Imprecision / 558

17.10 Conclusions / 559

References / 561

INDEX 569