Organometals and Organometalloids. Occurrence and Fate in the Environment

Title Page
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Half Title Page
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Copyright
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ACS Symposium Series......Page 5
FOREWORD......Page 6
To Frederick Challenger......Page 7
DEDICATION......Page 9
PREFACE......Page 11
PdftkEmptyString......Page 0
1 Biosynthesis of Organometallic and Organometalloidal Compounds......Page 14
Biological Methylation of Arsenite and Arsenate......Page 15
The Metabolism of Some Sulphur Compounds in Mould Cultures......Page 16
Selective Methylation......Page 17
The Development of Ideas on The Mechanism of Biological Methylation......Page 18
Search for Methanol in Arsenical Liquid Cultures of S. brevicaulis......Page 20
Attempts to Methylate Derivatives of Elements other than Arsenic......Page 21
Metabolism of Selenium Compounds......Page 23
Co-Enzyme M (2-Mercaptoethanesulphonic Acid)......Page 24
Speculations on the Biosynthesis of Co-enzyme M......Page 25
Ability of Metals for Incorporation into Living Systems......Page 26
The Biological Degradation of Organo-derivatives of Mercury......Page 29
Acknowledgements......Page 30
References......Page 31
Discussion......Page 34
Evolution of Respiration Chains......Page 36
Respiration in Thiobacilli......Page 38
Involvement of Arsenic in Respiratory Processes......Page 40
Reduction of Sulfate......Page 41
Reduction of Arsenate......Page 42
Alkylation of Metals and Metalloids......Page 43
Formation of Carbon-Metal and Carbon-Metalloid Bonds......Page 46
Literature Cited......Page 49
3 Occurrence of Biological Methylation of Elements in the Environment......Page 52
Experimental......Page 53
Results and Discussion......Page 54
Literature Cited......Page 63
Discussion......Page 64
Introduction......Page 67
Acknowledgements......Page 73
Discussion......Page 74
Decomposition of Organolead Compounds in Water......Page 78
Toxicity of Organolead and Organothallium Compounds......Page 80
Biomethylation of Pb2+ and Organolead Compounds.......Page 81
Mechanistic Considerations......Page 88
Significance of Biomethylation of T1+ and Pb2+......Page 91
Literature Cited......Page 92
Discussion......Page 93
6 Bioorganotin Chemistry: Stereo- and Situselectivity in the Monooxygenase Enzyme Reactions of Cyclohexyltin Compounds......Page 95
Results......Page 96
Discussion......Page 100
Acknowledgments......Page 104
Discussion......Page 105
Methanogenic Bacteria......Page 107
Alkylation of Metals......Page 110
Arsine Biosynthesis......Page 111
Arsenic transformation in anaerobic ecosystems.......Page 115
Aerobic Methylation of Arsenic......Page 118
The Mechanism of the Aerobic Methylation of Arsenic......Page 121
Arsenic Cycle in the Environment......Page 122
BIBLIOGRAPHY......Page 125
Discussion......Page 126
8 Arsenic Uptake and Metabolism by the Alga Tetraselmis Chui......Page 129
Literature Cited......Page 140
Discussion......Page 141
9 The Chemistry of Organometallic Cations in Aqueous Media......Page 143
Reactions Involving Cleavage of the Metal-Carbon Bonds......Page 144
Reactions in Which the Metal-Carbon Bonds Remain Intact......Page 146
Future Prospects......Page 156
Literature Cited......Page 159
Silicon: Occurance and Distribution......Page 162
Silicon as an Organo Group Donor......Page 163
Environmental Considerations......Page 166
Literature Cited......Page 167
Discussion......Page 168
11 Influence of Environmental Parameters on Transmethylation between Aquated Metal Ions......Page 171
Experimental Methods......Page 172
Results and Discussion......Page 173
Acknowledgements......Page 195
Literature Cited......Page 196
Discussion......Page 198
A. Metathetical Exchange......Page 201
B. Successive Reactions......Page 204
C. Reaction of K2PtCl4 with Methylcobalamin......Page 207
Discussion......Page 208
A. Metathetical Demethylation......Page 209
B. Redox Demethylation......Page 210
Acknowledgments......Page 211
Literature Cited......Page 212
Discussion......Page 213
13 Mechanisms for Alkyl Transfers in Organometals......Page 218
I. Organometals as Electron Donors—Ionization Potentials......Page 220
II. Electrophilic Cleavage of Organometals—Quantitative Effects of Alkyl Groups......Page 227
III. Electron Transfer Cleavage of Organometals with Hexachloroiridate(IV)......Page 232
IV. Delineation of Electrophilic and Electron Transfer Mechanisms......Page 239
V. Homolytic Displacements in Alkyl Transfers......Page 242
Literature Cited......Page 245
Discussion......Page 247
14 Pathways for Formation of Transition Metal-Carbon Bonds in Protic Media......Page 248
Literature Cited......Page 256
Discussion......Page 258
Results and Discussion......Page 260
Literature Cited......Page 273
Discussion......Page 274
Introduction......Page 277
I. Equilibria......Page 279
II. Kinetics of Disproportionation......Page 284
III. Distribution of Ammoniacal Chloramines......Page 286
References and Notes......Page 290
17 Chlorination and the Formation of N-Chloro Compounds in Water Treatment......Page 291
Discussion......Page 303
The Reaction Model......Page 305
Experimental......Page 306
Results and Discussion......Page 308
Conclusions......Page 323
Literature Cited......Page 324
Discussion......Page 325
Introduction......Page 327
Experimental Methods and Calculations......Page 328
Discussion......Page 333
Discussion......Page 337
Complexes of British anti-Lewisite and other Thiols......Page 340
Biological Behaviour of Diphenylmercury......Page 346
Acknowledgements......Page 348
Literature Cited.......Page 349
21 Mercury, Lead, and Cadmium Complexation by Sulfhydryl-Containing Aminoacids. Implications for Heavy-Metal Synthesis, Transport, and Toxicology......Page 352
L-Cysteine and DL-Homocysteine Complexes......Page 355
Comparison of Binding Preferences for Inorganic Mercury, Cadmium and Lead (11).......Page 360
METHYLATION AND DEMETHYLATION OF LEAD......Page 364
Literature Cited......Page 367
Discussion......Page 369
22 Release Mechanisms of Organotin Toxicants from Coating Surfaces: A Leaching Model for Antifouling Coatings......Page 372
Details Of The Leaching Model......Page 374
Experimental Section......Page 376
Results and Discussion......Page 377
Literature Cited......Page 381
Discussion......Page 382
Humic and Fulvic Acid......Page 385
Complexation......Page 387
Rate of Complex Formation and Dissociation......Page 390
Heterogeneous Phase Interactions......Page 392
Chemical Speciation......Page 393
Transport......Page 394
Literature Cited......Page 396
Discussion......Page 398
Introduction......Page 401
The Organotin Literature......Page 402
Historical......Page 403
Organotins in the Environment......Page 404
Biological Effects of Exposure......Page 418
Discussion......Page 436
Acknowledgment......Page 437
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B......Page 440
C......Page 441
D......Page 443
E......Page 444
F......Page 445
H......Page 446
I......Page 447
M......Page 448
O......Page 452
P......Page 454
R......Page 455
S......Page 456
T......Page 458
W......Page 459
Z......Page 460