17
MASS SPECTROMETRY IN ENVIRONMENTAL SCIENCES
MASS SPECTROMETRY IN ENVIRONMENTAL SCIENCES
MASS SPECTROMETRY IN ENVIRONMENTAL SCIENCES
Edited by
F. W KARASEK University of Waterloo Waterloo, Ontario, Canada
O. HUTZINGER University of Bayreuth Bayreuth, Federal Republic of Germany
and
S. SAFE University of Guelph Guelph, Ontario, Canada and Texas A&M University College Station, Texas, U. S.A.
PLENUM PRESS. NEW YORK AND LONDON
Library of Congress Cataloging in Publication Data
Main entry under title:
Mass spectrometry in environmental sciences.
Bibliography: p. Includes index. 1. Environmental chemistry - Technique.
Analysis. I. Karasek, Francis W., 1919-TD193.M37 1984
2. Mass spectrometry. 3. Pollutants. II. Hutzinger, O. III. Safe, S. 628.5 84-13469
ISBN-13: 978-1-4612-9445-0 DOl: 10.1007/978-1-4613-2361-7
e-ISBN-13: 978-1-4613-2361-7
© 1985 Plenum Press, New York
Softcover reprint of the hardcover 1st edition 1985
A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher
CONTRIBUTORS
E. ATLAS Department of Chemistry, Texas A&M University, College Station, Texas, U.S.A.
H. M. BALBA Uniroyal Chemical Co., Naugatuck, Connecticut, U.S.A. D. A. BIRKHOLZ Environmental Protection Service, Western and
Northern Region, Edmonton, Alberta, Canada R. K. BOYD Department of Chemistry, University of Guelph, Ontario,
Canada J. A. BUCKLEY SCIEX, Thornhill, Ontario, Canada J. T. BURSEY Analytical and Chemical Sciences, Research Triangle
Institute, Research Triangle Park, North Carolina, U.S.A. R. E. CLEMENT Laboratory Services Branch, Ontario Ministry of the
Environment, Ontario, Canada W. R. DAVIDSON SCIEX, Thornhill, Ontario, Canada J. M. DESMARCHELIER CSIRO Division of Entomology, Canberra,
Australia RALPH C. DOUGHERTY Department of Chemistry, Florida State U ni
versity, Tallahassee, Florida, U.S.A. J. B. FRENCH SCIEX, Thornhill, Ontario, Canada G. A. EICEMAN Department of Chemistry, New Mexico State Univer
sity, Las Cruces, New Mexico, U.S.A. E. Ch. Th. CEVERS Institute of Applied Chemistry TNO, Utrecht, The
Netherlands C. S. ClAM Department of Chemistry, Texas A&M University, College
Station, Texas, U.S.A. C. V. HAMPTON Chemical Analysis Research Department, Scientific
Research Laboratory, Ford Motor Company, Dearborn, Michigan, U.S.A.
O. HUTZINCER Departments of Ecological Chemistry and Geochemistry, University of Bayreuth, Federal Republic of Germany
BO JANSSON Special Analytical Laboratory, National Swedish Environment Protection Board, Solna, Sweden
F. W. KARASEK Department of Chemistry, University of Waterloo, Ontario, Canada
v
VI CONTRIBUTORS
M. J. LACEY CSIRO Division of Entomology, Canberra, Australia L. M. UBBEY Department of Food Science and Technology, Oregon
State University, Corvallis, Oregon, U.S.A. D. C. G. MUIR Department of Fisheries and Oceans, Freshwater In
stitute, Winnipeg, Manitoba, Canada K. OUE Laboratory of Environmental and Toxicological Chemistry,
University of Amsterdam, Amsterdam, The Netherlands FRANCIS I. ONUSKA National Water Research Institute, Canada Centre
for Inland Waters, Burlington, Ontario, Canada E. D. PELUZZARI Analytical and Chemical Sciences, Research Tri
angle Institute, Research Triangle Park, North Carolina, U.S.A. N. M. REID SCIEX, Thornhill, Ontario, Canada B. D. RIPLEY Provincial Pesticide Residue Testing Laboratory, Ontario
Ministry of Agriculture and Food, University of Guelph, Ontario, Canada
S. SAFE The Guelph-Waterloo Centre for Graduate Work in Chemistry, Department of Chemistry, University of Guelph, Ontario, Canada
R. A. SCANLAN Department of Food Science and Technology, Oregon , State University, Corvallis, Oregon, U.S.A.
D. SCHUETZLE Chemical Analysis Research Department, Scientific Research Laboratory, Ford Motor Company, Dearborn, Michigan, U.S.A.
H.-R. SCHULTEN Fachhochschule Fresenius, Wiesbaden, Federal Republic of Germany
J. SPARUNG The Guelph-Waterloo Centre for Graduate Work in Chemistry, Department of Chemistry, University of Guelph, Ontario, Canada
D. L. STRUBLE Agriculture Canada Research Station, Lethbridge, Alberta, Canada
SI-EN SUN Institute of Environmental Chemistry, Academia Sinica, Peking, China
GORAN SUNDSTROM Special Analytical Laboratory, National Swedish Environmental Protection Board, Solna, Sweden
J. A. SWEETMAN Statewide Air Pollution Research Center, University of California, Riverside, California
B. A. THOMSON SCIEX, Thornhill, Ontario, Canada G. R. B. WEBSTER Pesticide Research Laboratory, Department of Soil
Science, University of Manitoba, Winnipeg, Manitoba, Canada
PREFACE
During the past ten years a variety of methods involving mass spectrometry have been developed for the analysis of environmentally important compounds. Much has been accomplished in that period to solve some of the important problems in the field. Growth of this methodology and its accomplishments has reached the point where an individual scientist can no longer have an in-depth knowledge of all the areas involved. We have attempted to provide this in-depth picture to those scientists concerned by having the important topics treated by experts in the subject matter.
In order to provide all the relevant material in one volume we begin with the general topics which provide the basic background material necessary to understand the techniques discussed in the in-depth topics. These general chapters are kept brief, containing only the essentials needed by the working scientist to deal with the practical applications. References in these chapters are chosen to permit a more complete study of each chapter.
The concept for this book was developed during the activities of two of the editors under a NATO travel grant. These editors gratefully acknowledge this support which made the initial planning of this book possible.
The editors would like to thank the individual authors of each chapter for their cooperation and generously giving of their time for this project.
vii
F. W. KARASEK
O. HUTZINGER
S. SAFE
CONTENTS
1. GENERAL PRINCIPLES OF ANALYTICAL MASS SPECTROMETRY
R. K. Boyd
1. Introduction .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2. Vacuum System.. . . . .... . . ......... .... ... .... ..... ....... 2 3. Sample Introduction ...................................... 3 4. Ionization of Sample ...................................... 3
4.1. Electron Impact (EI) ................................. 4 4.2. Chemical Ionization (CI) ............................. 4 4.3. Field Ionization (FI) ................................. 5 4.4. Field Desorption (FD) ................................ 5 4.5. Secondary Ion Mass Spectrometry (SIMS) ............. 6 4.6. Fast Atom Bombardment (FAB) ...................... 6 4.7. Desorption Chemical Ionization (DCI) ................. 6 4.8. Negative Chemical Ionization (NCI) ................... 7 4.9. Atmospheric Pressure Ionization (API) ................ 7
4.10. Californium-252 Plasma Desorption ................... 7 5. Analyzer Systems ......................................... 7
5.1. Quadrupole Mass Filters ............................. 8 5.2. Single-Focusing Magnetic Analyzers ................... 9 5.3. Double-Focusing Magnetic Sector Instruments ......... 11 5.4. Ion Cyclotron Resonance (ICR) Spectrometers ......... 12 5.5. Time-of-Flight (TO F) Instruments .................... 12
6. Ion Detectors ............................................. 13 6.1. Discrete-Dynode Electron Multiplier. . . . . . . . . . . . . . . . . . . 13 6.2. Continuous-Electrode Electron Multiplier
(Channeltron) ....................................... 13 6.3. Photographic Plates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 6.4. Faraday Cup ........................................ 14 6.5. Amplification and Recording of Mass Spectra .......... 14
7. Special Techniques. . . . .. .. . . . ... . .... . ... . . .... ... ........ 14 7.1. Specific-Ion Detection................................ 14 7.2. Mass Spectrometry/Mass Spectrometry (MS/MS) ........ 15 7.3. Quantitation ........................................ 16
ix
x CONTENTS
7 A. Mass Measurement References ....................................................... .
16 17
2. GAS CHROMATOGRAPHY/MASS SPECTROMETRY/ COMPUTER INSTRUMENTATION
R. E. Clement and F. W. Karasek
1. Introduction.............................................. 21 2. Basic Components ........................................ 22
2.1. Gas Chromatograph Column ......................... 24 2.2: GC Injection Modes ................................. 25 2.3. GC/MS Interface .................................... 26 204. Mass Spectrometry-Sample Ionization ................ 29
3. Mass Spectrometer Analyzers .............................. 32 4. GC/MS Applications ....................................... 37 5. Computer Techniques ..................................... 38 6. Special Instrumentation ................................... 44
References ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3. FIELD DESORPTION AND FIELD IONIZATION
H.-R. Schulten and Si-en Sun
1. Introduction .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 2. Principle and Techniques.... .................. . ........... 50 3. Application to Environmental Analysis ...................... 54
3.1. Air................................................. 54 3.2. Natural Aerosols .................................... 55 3.3. Food and Body Fluids ............................... 59 304. Water .............................................. 64 3.5. Ultratrace Analysis for Metals in Environmental Samples 73
References ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4. POSITIVE AND NEGATIVE CHEMICAL IONIZATION MASS SPECTROMETRY
Ralph C. Dougherty
1. Introduction ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 1.1. Chemical Ionization Mass Spectrometry ............... 77 1.2. Negative Chemical Ionization Mass Spectrometry ....... 80
2. Applications ............ ',' . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 2.1. Studies of Chemical Reactivity ........................ 83 2.2. Studies of Complex Biological Molecules............... 84 2.3. Analysis of Complex Mixtures ........................ 87
References ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
CONTENTS
5. USE OF PYROLYSIS/GAS CHROMATOGRAPHY/MASS SPECTROMETRY IN ENVIRONMENTAL ANALYSIS
H. M. Balba
xi
1. Introduction.............................................. 93 2. Common Methods of Pyrolysis ............................. 93
2.1. Hot Ribbon or Filament Pyroprobes ................... 94 2.2. Curie-Point Pyroprobes .............................. 94 2.3. Furnace-Heated Tube ............................... 95
3. General Techniques..... .................................. 95 3.1. Use of Pyrolysis in the Analysis of Bound Residues
of Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 3.2. Characterization of Soil Organic Matters. . . . . . . . . . . . . . . 98
References .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
6. ATMOSPHERIC PRESSURE CHEMICAL IONIZATION MASS SPECTROMETRY
J. B. French, B. A. Thomson, W. R. Davidson, N. M. Reid, and J. A. Buckley
1. Introduction.............................................. 101 2. The Development of APCI Mass Spectroscopy ............... 102 3. Ion Source Design and Characteristics ...................... 105 4. Chemical Ionization at Atmospheric Pressure ................ 108 5. Environmental Applications of APCIIMS .................... 113 6. Conclusions .............................................. 119
References ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
7. MASS SPECTRAL RETRIEVAL AND INTERPRETATION SYSTEMS
F. W. Karasek and R. E. Clement
1. Introduction.............................................. 123 2. Use of Published Indexes .................................. 124 3. Computer Spectra Matching via Dedicated System ........... 127 4. Computer Spectra Matching via Remote Terminal ........... 130
4.1. PEAK Search ....................................... 130 4.2. KB Search .......................................... 131 4.3. PBM Search ........................................ 131
5. Computerized Interpretation of a Mass Spectrum ............ 132 6. Application to Analytical Problems. . . . . . . . . . . . . . . . . . . . . . . . . . 132
6.1. Illustration of Search Procedures ..................... 133 6.2. Eight-Peak Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134 6.3. PEAK Search ....................................... 134 6.4. Probability-Based Matching. . . . . . . . . . . . . . . . . . . . . . . . . . . 134
xii CONTENTS
6.5. Interpretation Using STIRS ........................... 135 7. Structure Determination ................................... 137
References ...... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
8. GAS CHROMA TOGRAPHnMASS SPECTROMETRY IN WATER POLLUTION STUDIES
E. D. Pellizzari and J. T. Bursey
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139 2. Computer-Assisted Analysis ................................ 139
2.1. Qualitative Analysis .................................. 139 2.2. Quantitative Analysis ................................ l41
3. Studies to Improve Quantitative Analyses ................... 142 4. Water Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143 5. A New Horizon in Comprehensive Analysis ................. 143
5.1. Sample Handling.................................... 149 5.2. Internal Standards.. . .... .. .. ..... ......... ... ....... 149
6. Isolation of Organics ...................................... 151 6.1. Extract Processing ................................... 153 6.2. Gas Chromatography ................................ 153 6.3. Qualitative Analysis .................................. 153 6.4. Quantitative Analysis ................................ 154
7. Quality Assurance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155 References ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
9. GAS CHROMATOGRAPHY/MASS SPECTROMETRY IN AIR POLLUTION STUDIES
D. Schuetzle and C. V. Hampton
1. Introduction.............................................. 159 2. Sampling Techniques... . ..... . ..... ......... .... .... ... ... 161 3. Extraction Techniques. . ..... . .... . ...... ....... ........... 161
3.1. Filter Samples....................................... 161 3.2. Adsorbent Samples .................................. 162
4. Fractionation ............................................. 162 5. Bioassay Screening ........................................ 164 6. GC/MS/Computer Analysis. . . ..... . .... . ........ ........ ... 164
6.1. Gas Chromatography ................................ 170 6.2. Sample Derivatization ................................ 170 6.3. Sample Introduction ................................. 172 6.4. Column Selection .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173 6.5. GC/MS Interfaces ................................... 176 6.6. Packed Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176 6.7. Capillary Columns................................... 176 6.8. Mass Spectrometry .................................. 177
CONTENTS xiii
6.9. Ionization Modes .................................... 177 6.10. Instrument Operation Modes ......................... 177
7. Data Analysis ............................................. 180 7.1. Qualitative Analysis .................................. 180 7.2. Quantitative Analysis ................................ 182
8. Recent and Future Developments. . . . . . . . . . . . . . . . . . . . . . . . . . . 189 References ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
10. POLYCYCLIC AROMATIC HYDROCARBONS
J. A. Sweetman and F. W. Karasek
1. Introduction.............................................. 195 2. Electron Impact Mass Spectrometry. . . . . . . . . . . . . . . . . . . . . . . . . 197
2.1. Polycyclic Aromatic Hydrocarbons .................... 197 2.2. Alkyl-Polycyclic Aromatic Hydrocarbons............... 198 2.3. Hetero-Polycyclic Aromatic Hydrocarbons ............. 200 2.4. Derivatives of Polycyclic Aromatic Hydrocarbons ....... 200
3. Gas Chromatography/Mass Spectrometry .................... 203 4. Soft Ionization Techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 204
References ......................................................... 205
II. POLYCHLORINATED BIPHENYLS
C. R. B. Webster and D. A. Birkholz
I. Mass Spectra of Pure Compounds .......................... 209 1.1. Electron Impact Mass Spectrometry ................... 209 1.2. Positive Chemical Ionization Mass Spectrometry ........ 215 1.3. Negative Chemical Ionization Mass Spectrometry....... 215
2. Gas Chromatography/Mass Spectrometry/Data System ........ 220 2.1. Gas Chromatography/Mass SpectrometrylData System
(GC/MSIDS) Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 220 2.2. Subset Data Acquisition Techniques ................... 221
3. Analysis of PCBs by Glass Capillary GC/MS ......... . . . . . . . .. 225 4. GClMS of PCBs in Biological Samples..... .................. 229 5. PCB Metabolites .......................................... 236
5.1. Hydroxylated PCB Metabolites ....................... 236 5.2. Hydroxylated Monochlorobiphenyls ................... 239 5.3. Hydroxylated Dichlorobiphenyls ...................... 241 5.4. Hydroxylated Tetrachlorobiphenyls ................... 244 5.5. Hydroxylated Pentachlorobiphenyls ................... 245 5.6. Hydroxylated Hexachlorobiphenyls ................... 246 5.7. Sulfur-Containing Metabolites of PCBs ................ 247 5.8. Methylthio-PCBs .................................... 247 5.9. Methylsulfonyl-PCBs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 247
References ......................................................... 253
XlV CONTENTS
12. POLYCHLORODIBENZO-p-DIOXINS AND POLYCHLORODIBENZOFURANS
G. R. B. Webster, K. Olie, and O. Hutzinger
1. Electron Impact Mass Spectra .............................. 257 2. Chemical Ionization Mass Spectra .......................... 260
2.1. Positive Chemical Ionization .......................... 260 2.2. Negative Chemical Ionization ......................... 260
3. Atmospheric Pressure Ionization (API) Mass Spectrometry .... 263 4. Metastable Ions ........................................... 264 5. Interfering Compounds in Electron Impact Mass Spectra
of PCDDs and PCDFs ..................................... 265 5.1. Compounds Interfering with 2,3,7,8-TCDD ............ 265 5.2. Potentially Interfering Compounds for PCDDs
and PCDFs ......................................... 269 6. Direct-Probe Analytical Techniques ......................... 274
6.1. Electron Impact..................................... 274 6.2. Chemical Ionization ................................. 274
7. GC/MS Methods .......................................... 274 7.1. Analysis of PCDDs and PCDFs by Packed-Column
GC/MS ............................................. 274 7.2. Analysis of PCDDs and PCDFs by Capillary GC/MS ..... 274 7.3. Tetrachlorodibenzo-p-Dioxins . . . . . . . . . . . . . . . . . . . . . . . .. 282
8. Qualitative and Quantitative Methods-GC/MS/MS ........... 285 8.1. Chromatographic Cleanup and Qualitative
Methods ............................................ 285 8.2. Quantification with SIM and Internal Standards. . . . . . .. 286 8.3. Perchlorination ........... . . . . . . . . . . . . . . . . . . . . . . . . . .. 286 8.4. High-Resolution versus Low-Resolution Mass Spectral
Techniques ......................................... 286 9. Metabolites of PCDDs and PCDFs .......................... 287
9.1. Hydroxylated PCDDs as Their Methyl Ethers .......... 287 9.2. Hydroxylated PCDFs as Their Methyl Ethers .......... 290 9.3. PCDD Metabolites ................................... 290
References ......................................................... 294
13. DDT AND RELATED COMPOUNDS
Goran Sundstrom and Bo Jansson
I. Introduction .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 297 2. Electron Impact Spectra ................................... 298
2.1. DDT and Derivatives Containing Chlorophenyl Groups.. . . ... . . . .... . ......... .... ................. 298
2.2. Metabolites Oxygenated in the Aromatic Rings; Amino Acid Conjugates .............................. 303
2.3. Sulfur-Containing Metabolites ........................ 304 2.4. Photoproducts ...................................... 304
CONTENTS xv
2.5. Related Compounds ................................. 305 3. Ion Kinetic Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 306 4. Chemical Ionization Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 307 5. Field Desorption (FD) Spectra .............................. 308 6. Mass Fragmentography .................................... 308
References ......................................................... 309
14. VOLATILE HALOCARBONS
G. A. Eiceman
I. Introduction .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 311 1.1. Chlorofluorocarbons ................................. 311 1.2. Trihalomethanes and Similar Compounds ............. 314
2. Mass Spectrometry of Halocarbons ......................... 317 3. Instrumentation for Analysis ............................... 322 4. Chlorofluorocarbons in Atmospheric Samples ... . . . . . . . . . . . .. 322 5. Volatile Halocarbons in Water. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 325
5.1. Introduction ........................................ 325 5.2. Direct Aqueous Injection ............................. 326 5.3. Liquid-Liquid Extraction ............................ 329 5.4. Headspace Analysis .................................. 332 5.5. Direct Sampling ..................................... 332 5.6. Theoretical ......................................... 333 5.7. Dynamic Headspace Sampling ........................ 334 5.8. Origins ............................................. 334
References ......................................................... 338
15. PHTHALATES AND RELATED PLASTICIZERS
E. Atlas and C. S. Giam
l. Introduction ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 341 2. Occurrence of Plasticizers in Environmental Samples ......... 343 3. Analytical Aspects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 344 4. Mass Spectral Properties ................................... 345
4.1. Phthalates .......................................... 345 4.2. Phosphate Esters .................................... 347 4.3. Other Plasticizers: Adipates, Sebacates, Citrates,
Phthalyl Glycolates, Trimellitates ...................... 350 References ......................................................... 350
16. ORGANOMETALLIC COMPOUNDS
E. Ch. Th. Gevers
I. Introduction .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 353 2. Mass Spectrometry ........................................ 355 3. Arsenic .................................................. 356
xvi CONTENTS
4. Mercury.................................................. 356 5. Tetraalkyltin and Tetraalkyllead Compounds ................ 358 6. Tin...................................................... 359 7. Lead..................................................... 362
References ......................................................... 364
17. MASS SPECTROMETRY OF CARBAMATES, THIOCARBAMATES, DITHIOCARBAMATES, UREA, THIOUREA, AND CARBOXANILIDE PESTICIDES
Francis I. Onuska
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 367 2. Mass Spectrometry of Carbamates .......................... 368
2.1. EI Mass Spectrometry of Carbamates ........ . . . . . . . . .. 368 2.2. CI Mass Spectrometry of Carbamates ..... . . . . . . . . . . . .. 369 2.3. Other Ionization Methods for Carbamates ............. 373
3. Thiocarbonates ........................................... 373 4. Thiocarbamates ......... . ..... ....................... ..... 375
4.1. Dithiocarbamates .................................... 376 4.2. Thiuramdisulfides ................................... 381
5. Urea and Thiourea Herbicides ............................. 383 5.1. N-Phenylureas ...................................... 385 5.2. Thioureas .......................................... 389 5.3. Carboxanilides ...................................... 392 5.4. Trifluralin .......................................... 400
References ......................................................... 403
18. MASS SPECTROMETRY OF CHLORINATED POLYCYCLIC HYDROCARBON PESTICIDES
Francis I. Onuska
1. Introduction.............................................. 405 2. Dimethanonaphthalenes ................................... 405
2.1. Dieldrin ............................................ 409 2.2. Endrin ............................................. 410 2.3. Dieldrin and Aldrin ................................. 412 2.4. Isodrin, Heptachlor, Heptachlor Epoxide, Nonachlor,
and Chlordanes ..................................... 413 2.5. Mirex and Kepone .................................. 413 2.6. Toxaphene ......................................... 419
References ......................................................... 421
19. TRIAZINE HERBICIDES
D. C. G. Muir
1. Introduction.............................................. 423
CONTENTS xvii
2. Atrazine and Simazine ..................................... 423 3. Methoxy-s-Triazines ....................................... 427 4. Cyanazine, Cyanatryn, and Procyazine ...................... 428 5. Cyprazine ................................................ 429 6. Terbutryn . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 430 7. Dialkylamino-Substituted Chloro-s-Triazines ................. 431 8. Hexazinone .............................................. 431 9. Metribuzin ............................................... 432
References ......................................................... 434
20. OTHER HERBICIDES: DIPHENYL ETHERS, DINITROANILINES, DINITROPHENOLS, SUBSTITUTED BENZOIC ACIDS, PHOSPHONATES, URACILS, AND DIPYRIDYLIUMS
D. C. G. Muir and G. R. B. Webster
1. Diphenyl Ether Herbicides ................................. 437 1.1. Introduction ........................................ 437 1.2. Fluorodifen ......................................... 437 1.3. Diclofop-Methyl ..................................... 439 1.4. Oxyfluoren, Nitrofen, and CNP ... ..... ........... .... 440
2. Dinitroaniline and Dinitrophenol Herbicides. . . . . . . . . . . . . . . .. 441 2.1. Introduction........................................ 441 2.2. Dinitroanilines ...................................... 443 2.3. Dinitrophenols ...................................... 445
3. Substituted Benzoic Acid and Benzonitrile Herbicides ........ 446 3.1. Introduction ........................................ 446 3.2. Chloramben ........................................ 446 3.3. Bromoxynil ......................................... 447 3.4. Dicamba ............................................ 448
4. Phosphonate Herbicides ................................... 448 4.1. Introduction ........................................ 448 4.2. Glyphosate .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 448
5. Uracil Herbicides ......................................... 450 5.1. Introduction ........................................ 450 5.2. Terbacil and Bromacil ............................... 450
6. Pyridylium Herbicides ..................................... 451 6.1. Introduction ........................................ 451 6.2. Diquat, Paraquat, and Cyperquat ..................... 451
References ......................................................... 453
21. ORGANOPHOSPHORUS COMPOUNDS
J. M. Desmarchelier and M. J. Lacey
1. Mass Spectrometry as a Tool in Analytical Chemistry ......... 455 2. General Principles of the Mass Spectra of OPs ............... 457
xviii CONTENTS
3. EI Mass Spectra of OPs ....... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 458 3.1. Proportion of Ion Current Containing
Phosphorus Ions .................................... 458 3.2. Molecular Ion Abundance ............................ 460 3.3. Losses of Radicals (RO) From A or B ................... 461 3.4. Loss of (R-H) ...................................... 461 3.5. Loss of Mass 32 (S) .................................. 461 3.6. Maximization of PXH Groups ........................ 461 3.7. P(S)-OR versus P(O)-SR .............................. 462
4. Procedures for Quantitative Mass Spectroscopy .............. 463 5. Detection of Metabolites in MR Analysis of Phosphorus Acids
and Hydrogen Phosphites ................................. 464 6. Positive-Ion Chemical Ionization (PCI) ...................... 466 7. Negative Ionization (NI) and Negative-Ion Chemical Ionization
(NCI) .................................................... 467 8. Desorption and Ionization Techniques ...................... 468 9. Phosphorylation in the Analysis of Amines, Phenols, Alcohols,
and Thiols ............................................... 469 10. Mass Spectroscopy in Analysis of OPs-An Overview ......... 469
References ......................................................... 471
22. FUNGICIDES
B. D. Ripley
1. Introduction.............................................. 475 2. Analytical Considerations .................................. 476
2.1. Electron Ionization .................................. 479 2.2. Other Ionization Processes ........................... 480 2.3. Authenticated Standards ............................. 482
3. Analytical Applications .................................... 483 4. Confirmation of Structure ................................. 489 5. Breakdown and Metabolic Studies .......................... 490 6. Systemic Fungicide Studies ................................. 493
References ......................................................... 501
23. PYRETHROIDS
J. M. Desmarchelier and M. J. Lacey
1. Analysis of Pyrethroids .................................... 505 2. General Principles for Applications of Mass
Spectroscopy (MS) ........................................ 507 3. EI Mass Spectra of Pyrethroids ............................. 508 4. Positive-Ion Chemical fonization (PCI) Mass Spectra
of Pyrethroids ............................................ 512 5. Negative-Ion Chemical Ionization (NCI) .................... 517 6. Structural Characterization and MS/MS ..................... 518
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 518
CONTENTS XIX
24. MASS SPECTROMETRY OF SOME FEMALE LEPIDOPTERAN SEX PHEROMONES AND RELATED COMPOUNDS
D. L. Struble
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 521 2. Gas-Liquid Chromatography/Mass Spectrometry
(GLC/MS) Instrumentation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 522 3. Mass Spectrometry of Saturated and Unsaturated
Long-Chain Aliphatic Alcohols, Acetates, and Aldehydes ..... 523 3.1. Mass Spectrometry of Alcohols, Acetates,
and Aldehydes ...................................... 523 3.2. Chemical Ionization of Saturated and Unsaturated
Long-Chain Alcohols, Acetates, and Aldehydes ......... 525 3.3. CI (Nitric Oxide) .................................... 528 3.4. Negative Chemical Ionization (NCI) of Saturated and
Unsaturated Alcohols, Acetates, and Aldehydes ........ 529 4. Mass Spectrometry of Derivatives of Unsaturated Compounds 529
4.1. Hydrogenation or Deuteration ........................ 529 4.2. Ozonolysis .......................................... 530 4.3. Epoxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 530 4.4. Silylation ........................................... 533 4.5. Methoxymercuration-Demercuration ................. 533 4.6. Trimethylsilyloxy and O-Isopropylidene Derivatives. . . .. 534
References ......................................................... 534
25. MASS SPECTROMETRY OF N-NITROSAMINES
L. M. Libbey and R.A. Scanlan
1. Introduction.............................................. 537 2. Dialkyl N-Nitrosamines .................................... 538 3. Heterocyclic N-Nitrosamines ............................... 540 4. Alicylcic N -N itrosamines ................................... 541 5. Aromatic Nitrosamines .................................... 542 6. Nonvolatile N-Nitrosamines ................................ 543 7. Mass Spectrometry for the Confirmation of
N-Nitrosamines ........................................... 545 References ......................................................... 548
26. OTHER INDUSTRIAL POLLUTANTS AND NATURAL TOXINS
S. Safe and J. Sparling
1. Industrial Pollutants 2. Fungal and Plant Toxins .................................. .
References ........................................................ .
Appendix .............................. ........................... . Index .............................................................
551 554 557
559 565
