Is Arsenic an Aphrodisiac?

5.6.3 Vera Renczi 5.6.4 Madame Popova 5.6.5 Johann Hoch 5.6.6 The Arsenic Gang 5.6.7 The Grandmothers of Nagyrev 5.6.8 Dr. Michael Swango 5.6.9 Donald...

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Is Arsenic an Aphrodisiac? The Sociochemistry of an Element William R. Cullen University of British Columbia, Vancouver BC, Canada

RSC Publishing

Contents Chapter 1 Medicinal Arsenic: Toxic Arsenic

J.I The Element 1.2 Mineral Medicine 1,2.1 Theophrastus PhiJippus Aureolus Bombastus von Hohenheim, aka Paracelsus 1.3 Arsenic Eaters of Styria 3.4 Fowler's Solution 3.5 Acute PromyeJocytic Leukemia (APL) 1.6 The Organoarsenicals 1.6.1 Robert Bunsen 1.6.2 Paul Ehrlich 1.6.3 The Golden Age of Organoarsenicals 1.6.4 African Sleeping Sickness 1.7 The Darker Side: Toxicity 1.8 Arsenicosis and Cancer 1.9 Biomarkers 1.9.1 Urine 1.9.2 Hair 1.9.3 Finger and Toe Nails 1.9.4 Saliva 10 Animal Models 11 Chelate Compounds and Chelating Agents 1.1 (. 1 Chelation Therapy 12 Some Historical Connections 1.12.1 Charles Darwin 1.12.2 Karin Blixen aka Isak Dinesen

!s Arsenic an Aphrodisiac? The Sociochemistry of an Element % WjlJjam R C u | ] e n CO William R. Cullen 2008

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1 2 6 7 13 20 22 22 24 28 31 33 35 38 38 39 40 40 41 41 43 43 43 46

Contents

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1.12.3 Alexander Borodin, Professional Organic Chemist and Amateur Composer References

46 47

Chapter 2 Arsenic Where You Least Expect It 2.1 Animal Feed Additives 2.2 Heartworm 2.3 Pesticides and Herbicides 2.3.1 Lead and Calcium Arsenates 2.4 Arsenic Trioxide 2.4.1 The Black Death 2.5 Wood Preservation 2.5.1 Chromated Copper Arsenate (CCA) 2.5.2 Disposal of Treated Wood 2.5.3 Alternatives to CCA 2.6 Monomethylarsonic Acid and Dimethylarsinic Acid 2.6.1 Use in the USA 2.6.2 Canada 2.7 OBPA 2.8 Arsenic in Other Products and Processes 2.8.1 Ironitc 2.8.2 Gallium Arsenide 2.8.3 Glass Making 2.8.4 Embalming 2.8.5 Taxidermy 2.8.6 Pigments 2.9 Some Historical Connections 2.9.1 Clare Boothe Luce 2.9.2 The Peak Family 2.9.3 King George ITI References

58 60 61 61 63 63 67 67 72 74 75 75 76 78 78 78 79 80 81 85 87 88 88 89 90 92

Chapter 3 Arsine, Seheele's Green, Gosio Gas, and Beer 3.1 Arsine 3.2 Scheele's Green 3.3 Arsenical Wallpaper 3.3.1 Coal Tar Dyes and the Decline of Arsenical Colours 3.4 Medical Problems 3.5 Wallpaper Dust or Gas? 3.6 Gosio Gas 3.7 The Regulation of Arsenic, the "Verdant Assassin" 3.8 Other Assassins

99 103 105 106 107 109 110 112 113

Contents

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3.9 Frederick Challenger 3.10 The Toxicity of Gosio Gas 3.11 Sick-Building Syndrome? 3.12 The Manchester Beer Incident 3.13 An Historical Connection. William Morris References Chapter 4

Arsenophobia: A Connection between the Deaths of Infants and Napoleon I 4.1 4.2

Sudden Infant Death Syndrome The Toxic-Gas Hypothesis 4.2.1 The Reaction 4.2.2 The Turner Commission 4.2.3 The Back-to-Sleep Campaign 4.3 The Limerick Report 4.3.1 Antimony Biomethylation 4.3.2 Report Summary 4.4 Dr. T. J. Sprott 4.4.1 Sheep Skins 4.5 Other Proponents of the Toxic-Gas Hypothesis 4.6 Toxicity and Related Considerations 4.7 The Death o{ Napoleon I of France 4.7.1 Was it the Arsenic in the Wallpaper? 4.7.2 The Autopsy 4.7.3 Arsenic Poisoning? 4.7.4 The "Real" Cause of Napoleon's Death 4.7.5 Who Did It? 4.8 Some Analytical and Chemical Problems 4.8.1 The Preservation of the Corpse 4.8.2 The Lethal Phase 4.8.3 The Hair Analysis 4.9 The Overall Picture 4.9.1 Sources of Arsenic 4.9.2 Wine and Water 4.9.3 Self-medication 4.9.4 Arsenical Smoke and Preservatives 4.9.5 Arsenical Straws 4.10 Medical Evidence References Chapter 5

115 1IX 120 120 124 127

130 131 133 134 135 3 37 138 139 140 141 143 144 145 145 146 147 151 152 152 152 153 153 155 157 157 158 158 160 l6 ° '"'

Arsenic and Crime: The Law of Intended Consequences 5.1 5.2

Introduction Ancient Times

166 f67

Contents

5.3 5.4

5.5

5.6

5.7

5.8

5.9

5.10 5.11

European Excess: The Age of Arsenic 5.3.1 Italy of the Borgias and the Medicis 5.3.2 France: The Poisons Affair Forensic Science 5.4.1 Mary Blandy 5.4.2 James Marsh 5.4.3 Marie Lafarge 5.4.4 The Arsenic Act of 1851 5.4.5 Madeleine Smith 5.4.6 Thomas Smethurst 5.4.7 Florence Maybrick 5.4.8 Herbert Armstrong 5.4.9 Marie Besnard Public Perceptions 5.5.1 Arsenic and Old Lace 5.5.2 Crime Fiction 5.5.3 Portrait of a Poisoner Some Serial Killers 5.6.1 Mary Ann Cotton, Britain's First Serial Killer 5.6.2 The Black Widows of Liverpool 5.6.3 Vera Renczi 5.6.4 Madame Popova 5.6.5 Johann Hoch 5.6.6 The Arsenic Gang 5.6.7 The Grandmothers of Nagyrev 5.6.8 Dr. Michael Swango 5.6.9 Donald Harvey Delivery Systems 5.7.1 Food and Drink 5.7.2 The Poisoned Shirt 5.7.3 Application via a Prophylactic 5.7.4 The Poisoned Maiden 5.7.5 The Poisoned Ring 5.7.6 The Poisoned Candle Public Arsenic Attacks 5.8.1 Japanese Curry 5.8.2 Campus Coffee 5.8.3 Church Picnic Two Ongoing Cases 5.9.1 A Political Poisoning 5.9.2 Cynthia Sommer Bezoars, Unicorns and Food Tasters Some Historical Connections 5.11.1 Zachary Taylor 5.11.2 Wolfgang Amadeus Mozart

167 168 170 171 172 173 174 176 178 181 183 185 187 188 189 190 191 192 192 193 194 194 195 195 195 196 197 197 197 198 198 198 199 199 199 199 200 201 202 202 203 205 207 207 208

Contents

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5.11.3 References

Pyotr ilyich Tchaikovsky

209 TJO

Chapter 6 Arsenic at War: Mass Murder 6.1 Introduction 6.2 The First Chemical Weapons Conventions 6.3 World War I: The Gas War 6.3.1 Mustard Gas 6.3.2 Blue Cross 6.3.3 Arsenical Agents: The Second Generation 6.3.4 Tactics of Chemical Warfare 6.4 The US Enters the Fray 6.4.1 Lewisite 6.4.2 Phenarsazine Chloride 6.5 Arsenical Chemical-Warfare Agents 6.6 Casualties of the Chemical War 6.6.1 The Combatants 6.6.2 Civilian Casualties 6.7 The Aftermath 6.7.1 The Humane War? 6.7.2 Public Reaction 6.8 Living with Chemical Weapons 6.8.1 The Geneva Convention 6.8.2 The German Reaction 6.8.3 Spain in Morocco 6.8.4 Italy in Ethiopia (Abyssinia) 6.8.5 Japan in China 6.9 WWII - The Gas War That Never Happened 6.9.1 The Buildup in Europe 6.9.2 Russia 6.9.3 The United States 6.9.4 Canada 6.9.5 The European Experience 6.9.6 The War in the Pacific 6.10 Human Guinea Pigs 6.10.1 The Allies 6.10.2 Japan and Germany 6.10.3 The Nuremberg Code of 1947 and its Aftermath 6.11 The Vietnam War 6.1 LI Agent Blue 6.11.2 Adamsite and Other Tear Gases 6.11.3 Health Effects 6.11.4 The Public Reaction 6.12 The Chemical Weapons Convention

215 217 ? 17 221 223 224 225 226 227 228 232 233 233 234 234 234 235 239 239 240 240 241 242 244 244 245 245 246 250 251 252 252 254 254 257 257 259 259 260 261

Contents

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6.13 The Cleanup 6.13.1 The Early Years 6.13.2 Post-WWII 6.13.3 Japan 6.13.4 Domestic Ocean Dumping 6.14 Disposal of Stockpiles 6.14.1 Russia 6.14.2 United States 6.15 Some Special Problems 6.15.1 Munster, Germany 6.15.2 Spring Valley, US 6.15.3 Bowes Moor, UK 6.15.4 China 6.15.5 Albania 6.15.6 Other Recent Deployments of Chemical Weapons 6.16 Conclusions References

263 263 264 266 266 267 267 268 270 270 271 272 272 273 274 275 277

Chapter 7 Arsenic and the Environment 7.1

Introduction 7.1.1 Arsenic in the Atmosphere 7.1.2 Arsenic in the Pedosphere 7.1.3 Arsenic in the Hydrosphere 7.2 Arsenic in the Biosphere 7.2.1 Arsenic in Seafood 7.2.2 Analysis of Arsenic Species (Speciation) in Living Organisms 7.2.3 Distribution of Arsenic Species in the Living Environment 7.2.4 Where do Arsenosugars and Arsenobetaine Come From? 7.2.5 Arsenic Accumulators and Hyperaccumulators 7.3 Arsenic in Our Food and Water 7.3.1 Essentiality 7.3.2 Arsenic Market Baskets 7.3.3 The Effect of Cooking 7.3.4 More on Rice 7.3.5 Hijiki and Other Algal Products 7.3.6 Bottled Water 7.3.7 Metabolites 7.4 Bioavailability and Bioaccessibility 7.4.1 Sequential Selective Extraction (SSE) 7.4.2 Gastrointestinal Models

287 288 288 288 289 289 290 294 296 299 300 301 302 304 304 305 308 310 310 312 312

Contents

7.5 Arsenic in the Anthrosphere 7.5.1 Gold Prospecting 7.6 Arsenic Trioxide and the Giant Mine, Yellowknife NT, Canada 7.6.1 Giant Mine: An Underground Cleanup? 7.6.2 Giant Mine: Surface Cleanup 7.7 American Smelting and Refining Company. Asareo 7.7.1 The Everett and Tacoma Smelters 7.7.2 The Globe Smelter: Some Unexpected Relief 7.8 A Transboundary Dispute: Teck Cominco vs. US EPA 7.9 More Woes 7.9.1 Some Other Surfaces Affected by Mining 7.9.2 Nickel Arsenide 7.10 Arsenic in Energy Sources 7.10.1 Coal 7.10.2 Arsenical Peppers 7.10.3 The Oil Sands of Alberta 7.10.4 The Sydney Tar Ponds: Arsenic as an Environmental Hammer 7.10.5 Cleaning Up 7.10.6 Monitored Natural Attenuation 7.11 Microbes and Arsenic 7.11.1 More - but very Small Arsenic Eaters References

Chapter 8

313 314 315 317 318 319 319 321 321 322 322 323 324 324 326 327 328 329 331 332 333 339

Accidental Exposure to Arsenic: The Law of Unintended Consequences 8.1 Introduction 8.2 West Bengal and Bangladesh: The Devil's Water 8.2.1 The Green Revolution 8.2.2 Bangladesh 8.2.3 The Affected 8.2.4 Where does the Bangladesh Arsenic Come From? 8.3 Professor Dipankar Chakraborti 8.3.1 Field Testing Kits 8.4 Arsenic Mitigation in Bangladesh 8.4.1 Dhaka, Bangladesh, January 2002 8.4.2 Arsenic-Mitigation Technologies 8.4.3 Verification of Mitigation Technologies 8.4.4 The Grainger Challenge Prize 8.4.5 Nanoparticles 8.4.6 Other Arsenic-Mitigation Methods

349 350 350 351 354 355 358 360 362 362 364 365 367 369 369

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Contents

8.5

Where Are We Now? 8.5.1 Treatment Options for the Afflicted 8.5.2 Arsenic Mitigation 8.6 Taiwan 8.6.1 Southwestern Taiwan 8.6.2 Northern Taiwan 8.7 Vietnam and Elsewhere in the East 8.7.1 Vietnam 8.7.2 Nepal 8.7.3 China and Japan 8.8 South America 8.8.1 Argentina 8.8.2 Chile 8.9 Africa 8.10 Europe 8.11 North America 8.11.1 Mexico 8.11.2 8.11.3 8.11.4 8.11.5

The US Standard for Drinking Water Setting the US MCL Cost/Benefit Analysis The MCL Revisited sited

370 370 371 373 373 373 374 374 374 374 375 375 375 3 6 ? 378 379 379 379 381 383 385 385

8-13 The Canadian Maximum Acceptable concentration (MAC^

8-J4 T h e O p p o r t u m_* t s K n ) c k LI

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K

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E l Epilogue

References

388 389

Subject Index 398