Reviews of Environmental Contamination and Toxicology VOLUME 109 Reviews of Environmental Contamination and Toxicology ContmuatlOn of Residue Reviews Editor George W. Ware EditorIal Board F Bro-Rasmussen. Lyngby, Denmark DG Crosby, DavIs, Call forma G H Hudson, OvenJse. BelgIUm H Frehse, Leverkusen-Bayerwerk. Germany H F Lmskens, NIJmegen, The Netherlands o Hutzmger, Bayreuth, Germany N N Melmkov. Moscow. U S S R M L Leng. Midland. Michigan R Mestres. Montpelller. France D P Morgan, Oakdale, Iowa P De Pletn-Tonelll, Milano, Italy Foundmg Editor FrancIs A. Gunther VOLUME 109 Springer-Verlag New York Berlin Heidelberg London Paris Tokyo Coordinating Board of Editors GEORGE W. WARE, Editor Reviews of Environmental Contamination and Toxicology College of Agriculture University of Arizona Thcson, Arizona 85721, USA (602) 621-7201 HERBERT N. NIGG, Editor Bulletin of Environmental Contamination and Toxicology Agncultural Research and Education Center Umversity of Florida 700 Expenmental Station Road Lake Alfred, Florida 33850, USA (813) 956-1151 ARTHUR BEVENUE, Editor Archives of Environmental Contamination and Toxicology 35 Fifteenth Avenue San Mateo, California 94402, USA (415) 572-1029 New York 175 Fifth Avenue, New York, NY 10010, USA Heidelberg 6900 Heidelberg 1, Postfach 105 280, West Germany Library of Congress Catalog Card Number 62-18595 ISSN 0179-5953 © 1989 by Sprmger-Verlag New York Inc Softcover replint of the hardcover 1st edilion 1989 Ail lights reserved. This work may not be translated or copied in whole or m part without the written permission of the publisher (Springer-Verlag, 175 Fifth Avenue, New York, New York 10010, USA), except for blief excerpts in connection with reviews or scholarly analYSIS. Use m connectIon With any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed IS forbidden. The use of general descriptive names, trade names, trademarks, etc. in this publicatIon, even if the former are not especially identIfied, is not to be taken as a sign that such names, as understood by the Trade Marks and Merchandise Marks Act, may accordingly be used freely by anyone ISBN-13: 978-1-4684-7088-8 e-ISBN-13: 978-1-4684-7086-4 DOl: 10.1 007/978-1-4684-7086-4 Foreword Global attention in scientific, industrial, and governmental commumtles to traces of toxic chemicals in foodstuffs and in both abiotic and biotic environ ments has justified the present triumvirate of specialized publications III this field: comprehensive reviews, rapidly published progress reports, and archival documentations. These three publications are Illtegrated and scheduled to pro vide in international communication the coherency essential for nonduplicative and current progress in a field as dynamic and complex as environmental con tamination and toxicology. Until now there has been no journal or other publica tion series reserved exclusively for the diversified literature on "toxic" chemicals in our foods, our feeds, our geographical surroundings, our domestic animals, our wildlife, and ourselves. Around the world immense efforts and many talents have been mobilized to techmcal and other evaluations of natures, locales, magnitudes, fates, and toxicology of the persisting residues of these chemicals loosed upon the world. Among the sequelae of this broad new emphasis has been an inescapable need for an articulated set of authoritative publications where one could expect to find the latest important world literature produced by this emerging area of science together with documentation of pertinent ancil lary legislation. The research director and the legislative or administrative adviser do not have the time even to scan the large number of technical publications that might con tain articles important to current responsibility; these individuals need the back ground provided by detailed reviews plus an assured awareness of newly developing information, all with minimum time for literature searching. Simi larly, the scientist assigned or attracted to a new problem has the requirements of gleaning all literature pertinent to his task, publishing quickly new develop ments or important new experimental details to inform others of findings that might alter their own efforts, and eventually publishing all his supporting data and conclusions for archival purposes. The end result of this concern over these chores and responsibilities and with uniform, encompassing, and timely publication outlets in the field of environ mental contamination and toxicology is the Springer-Verlag (Heidelberg and New York) triumvirate: Reviews of Environmental Contamination and Toxicology (Vol. 1 in 1962 as Residue Reviews through Vol. 97 in 1986) for basically detailed review articles concerned with any aspects of chemical contaminants, including Foreword VI pesticides, in the total environment with their toxicological considerations and consequences. Bulletin of Environmental Contamination and Toxicology (Vol. 1 in 1966) for rapid publication of short reports of significant advances and discoveries in the fields of air, soil, water, and food contamination and pollution as well as methodology and other disciplines concerned with the introduc tion, presence, and effects of toxicants in the total environment. Archives of Environmental Contamination and Toxicology (Vol. 1 in 1973) for important complete articles emphasizing and describing original experimental or theoretical research work pertaining to the scientific aspects of chemical contaminants in the environment. Manuscripts for Reviews and the Archives are in identical formats and are sub ject to review, by workers in the field, for adequacy and value; manuscripts for the Bulletin are also reviewed but are published by photo-offset to provide the latest results without delay. The individual editors of these three publications comprise the joint Coordinating Board of Editors with referral within the Board of manuscripts submitted to one publication but deemed by major emphasis or length more suitable for one of the others. Coordinating Board of Editors Preface Despite attempts by the media to convince us our surroundings are under con tlllual chemical assault and not faring well, there is abundant evidence that most chemicals are degraded or dissipated in our not-so-fragile environment. Yet, we must contend with leaking underground fuel tanks, movement of nitrates and nitntes into our groundwater reservoirs, Illcreasing air pollution in our large cities, and seemingly frequent contamination of our food and animal feeds with pesticides, industrial chemicals, and bacterial toxins. Without continulllg surveillance and intelligent controls, some of these chemi cals could at times conceivably endanger the environment, wildlife, and the pub hc health. Ensuring safetY-ill-use of the many chemicals involved in our highly industrialized culture is a dynamic challenge, for the old established materials are continually being displaced by newly developed molecules more acceptable to environmentalists, toxicologists, and federal and state regulatory agencies. These matters are of genuine concern to increasing numbers of governmental agencies and legislative bodies around the world, for some of these chemicals have resulted in a few mishaps from improper use. Adequate safety-in-use evalua tions of any of these chemicals persisting into our air, drinking water, and food stuffs are not simple matters, and they incorporate the considered judgments of many individuals highly trained in a variety of complex biological, chemical, food technological, medical, pharmacological, and toxicological disciplines. It IS hoped that Reviews of Environmental Contamination and Toxicology will continue to serve as an integrating factor both in focusing attention upon those matters requiring further study and in collating for variously trained readers present knowledge in specific important areas involved with chemical contami nants in the total environment. This and previous volumes of "Reviews" illustrate these objectives. Because manuscripts are published in the order in which they are received in final form, it may seem that some important aspects of analytical chemistry, bioaccumulation, biochemistry, human and animal medicine, legisla tion, pharmacology, physiology, regulation, and toxicology are being neglected. To the contrary, these apparent omissions are recognized, and some pertinent manuscripts are in preparation. However, the field is so large and the interests in it are so varied that the editor and the Editorial Board earnestly solicit sug gestions of topics and authors to help make this international book-series even more useful and informative. Reviews of Environmental Contamination and Toxicology attempts to provide conCise, critical reviews of timely advances, philosophy, and significant areas of VIIi Preface accomplished or needed endeavor in the total field of foreign chemicals in any segment of the environment, as well as toxicological implications. These reviews are either general or specific, but properly they may lie in the domains of analyti cal chemistry and its methodology, biochemistry, human and animal medicine, legislation, pharmacology, physiology, regulation, and toxicology. Certain affairs in the realm of food technology concerned specifically with pesticide and other food-additive problems are also appropriate subject matter. The justification for the preparation of any review for this book-series is that it deals with some aspect of the many real problems arising from the presence of any "foreign" chemicals in our surroundings. Thus, manuscripts may encompass those matters in any country. Added plant or animal pest-control chemicals or their metabolites that may persist into food and animal feeds are within this scope. The so-called food additives (substances deliberately added to foods for flavor, odor, appearance, and preservation, as well as those inadvertently added during manufacture, packing, distribution, and storage) are also considered con sidered suitable review material. In addition, chemicals contaminant in any manner to air, water, soil, or plant or animal life are within this purview and these objectives. Manuscripts are normally contributed by invitation but suggested topics are welcome. Preliminary communication with the editor is recommended before volunteered reviews are submitted in manuscript form. College of Agriculture GWW. University of Arizona Tucson, Arizona Table of Contents Foreword V 00 Preface Vll 0000 MIcrobial Metabolism of Pesticides and Structurally Related Compounds IAN Co MACRAE 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Predicting Pesticide ResIdues to Reduce Crop Contamination EoI. SPYNU 89 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Association of Official Analytical Chemists: 1964-1988 HELEN L. REYNOLDS 109 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Subject Index 137 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Microbial Metabolism of Pesticides and Structurally Related Compounds Ian C. MacRae* Contents IntroductIOn 2 II Methodology 2 III Microbial metabolism of specific groups of pesticides 5 A. Halogenated hydrocarbons and related substances 5 I Chlordane 5 2 DDT 23 3 Hexachlorocyclohexane 23 4 Mlrex 24 5. Oxy-denvatives 24 6 Halogenated aromatics 24 7 Hydrocarbons 25 B Organophosphates 26 I. Chlorpynfos 26 2 Coumaphos 26 3 Dlazmon 26 4. FemtrothlOn and Femtrooxon 27 5 FensulfothlOn. 27 6 Methyl parathIOn 28 7 ParathIOn . 28 8 Glyphosate. 30 9. Miscellaneous organophosphates 30 C Carbamates. . 31 I. Carbary I .... 31 2 Carbofuran. 32 3 Miscellaneous carbamates 33 o ThlOcarbamates 34 I Dlallate and tnallate . 34 2. EPTC .. . 35 E Tnazmes .. . 35 I. Atrazme . 35 2 Metamitron 36 3 Prometryn and ametryn 36 'Department of MicrobIOlogy, Umverslty of Queensland, St Lucia, Bflsbane, Australia, 4067 © 1989 Spnnger-Verlag New York Inc Reviews of EnVironmental ContaminatIOn and Toxicology, Vol 109 2 I.e. MacRae F. Phenoxy compounds . . . . 36 G. Phenols . . . 41 I. Pentachlorophenol ... 41 2. Phenol and substituted phenols. 42 3. Chlorophenols 45 H. Anihnes .... 47 I. Amides. 49 1. Urea pesticides . . .51 K. Metallo- and metallo-orgamc compounds ..... 51 L. Pyrethrotds . ... .... ..... .. . 52 M. Miscellaneous pesticIdes and related compounds. 52 IV Bound pestICIde resIdues 55 V. Removal of pesticIdes from soIl and water 60 VI. Summary .. 67 VII. References. 67 I. Introduction Synthetic organic pesticides have been in widespread use for more than 40 years, and during that period, their use has contributed greatly to increased world wide food production and improved human and animal health. However, these successes have not been without their side effects such as toxicities to non target species, including humans, and the production of persistent residues in soil and water. The importance of microorganisms in the degradation and detoxication of pes ticides was soon established, and biodegradation, chiefly by microorganisms, was recognized as a major means of destroying these chemicals in soil and water. This review brings together published literature in the period 1981 to 1987 on the metabolism of pesticides and structurally related compounds in soil and water. Reviews on pesticide degradation in general, published during this period, include those of Alexander (1981,1985), Hutzinger and Veerkamp (1981), Mat sumura (1982), Sethunathan et al. (1982), Slater and Bull (1982), Dagley (1983), Ghisalba (1983), Leisinger (1983), Motosugi and Soda (1983), and Barik (1984). During this period much has happened in research on pesticide metabolism. New methods and new approaches to old problems have been devised, and in some cases their use has led to the confirmation and expansion of earlier knowledge. Genetic engineering has become a promising tool for those con cerned with detoxication of soil and water and the disposal of toxic wastes, and soil microbes appear to have learned new tricks, such that enhanced degradation of pesticides has become a serious problem in some areas. II. Methodology The traditional approach to microbial biodegradation studies often involved batch enrichment culture, followed by the isolation of pure cultures of micro-