RESIDUE REVIEWS VOLUME 96 RESIDUE REVIEWS Reviews of Environmental Contamination and Toxicology Editor FRANCIS A. GUNTIlER Assistant Editor JANE DAVIES GUNTIlER Riverside, California ADVISORY BOARD F. BRa-RAsMUSSEN, Lyngby, Denmark D. G. CROSBY, Davis, California' S. DORMAL-VAN DEN BRUEL, Bruxelles, Belgium C. L. DUNN, Wilmington, Delaware' H. FREHSE, Leverkusen-Bayerwerk, Germany K. FuKuNAGA, Tokyo, Japan' H. GEISSBfun.ER, Basel, Switzerland o. HUTZINGER, Bayreuth, Germany H. F. LINSKENS, Nijmegen, The Netherlands N. N. MELNlKov, Moscow, U.S.S.R. • R. MESTRES, Montpellier, France P. DE PIETRI-TONELLI, Milano, Italy· I. ZIEGLER, MOOchen, Germany VOLUME 96 SPRINGER-VERLAG NEW YORK BERLIN HEIDELBERG TOKYO 1985 Coordinating Board of Editors FRANCIS A. GUNTHER, Editor Residue Reviews Department of Entomology University of California Riverside, California 92521 HERBERT N. NIGG, Editor Bulletin of Environmental Contamination and Toxicology Agricultural Research and Education Center University of Florida 700 Experimental Station Road Lake Alfred, Florida 33850 ARTHUR BEVENUE, Editor Archives of Environmental Contamination and Toxicology 1515 Nuuanu Avenue Queen Tower 104 Honolulu, Hawaii 96817 All rights reserved. No part of this book may be translated or reproduced in any form without written permission from Springer-Verlag. © 1985 by Springer-Verlag New York Inc. Softcover reprint of the hardcover 1st edition 1985 Library of Congress Catalog Card Number 62-18595. Printed in the United States of America. 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. New York: 175 Fifth Avenue, New York, N.Y. 10010 Heidelberg: 6900 Heidelberg 1, Postfach 105 280, West Germany ISSN 0080-181X ISBN-13: 978-1-4612-9580-8 e-ISBN-13: 978-1-4612-5140-8 DOl: 10 .1007/978-1-4612-5140-8 Foreword Worldwide concern in scientific, industrial, and governmental com munities over traces of toxic chemicals in foodstuffs and in both abiotic and biotic environments has justified the present triumvirate of specialized publications in this field: comprehensive reviews, rapidly published progress reports, and archival documentations. These three publications are integrated and scheduled to provide in international communication the coherency essential for nonduplicative and current progress in a field as dynamic and complex as environmental contamination and toxicology. Until now there has been no journal or other publication series reserved exclusively for the diversified literature on "toxic" chemicals in our foods, our feeds, our geographical surroundings, our domestic animals, our wild life, and ourselves. Around the world immense efforts and many talents have been mobilized to technical 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 authorita tive publications where one could expect to find the latest important world literature produced by this emerging area of science together with documentation of pertinent ancillary legislation. The research director and the legislative or administrative advisor do not have the time even to scan the large number of technical publications that might contain articles important to current responsibility; these individuals need the background provided by detailed reviews plus an assured awareness of newly developing information, all with minimum time for literature searching. Similarly, the scientist assigned or attracted to a new problem has the requirements of gleaning all literature pertinent to his task, publishing quickly new developments or important new experimental details to inform others of findings that might alter their own efforts, and eventually publishing all his supporting data and con clusions 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 environmental contamination and toxicology is the Springer-Verlag (Heidelberg and New York) triumvirate: Residue Reviews (vol. 1 in 1962) for basically detailed review articles concerned with any aspects of residues of pesticides and other chemical contaminants in the total environment, including toxico logical considerations and consequences. vi Foreword 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 contami nation and pollution as well as methodology and other disciplines concerned with the introduction, 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 Residue Reviews and the Archives are in identical formats and are subject to review, by workers in the field, for adequacy and value; manuscripts for the BuUetin are also reviewed but are pub lished by photo-offset to provide the latest results without delay. The individual editors of these three publications comprise the Joint Co ordinating 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 That residues of pesticide and other contaminants in the total environ ment are of concern to everyone everywhere is attested by the reception accorded previous volumes of "Residue Reviews" and by the gratifying enthusiasm, sincerity, and efforts shown by all the individuals from whom manuscripts have been solicited. Despite much propaganda to the con trary, there can never be any serious question that pest-control chemicals and food-additive chemicals are essential to adequate food production, manufacture, marketing, and storage, yet without continuing surveillance and intelligent control some of those that persist in our foodstuffs could at times conceivably endanger the public health. Ensuring safety-in-use of these many chemicals is a dynamic challenge, for established ones are continually being displaced by newly developed ones more acceptable to food technologists, pharmacologists, toxicologists, and changing pest control requirements in progressive food-producing economies. These matters are of genuine concern to increasing numbers of gov ernmental agencies and legislative bodies around the world, for some of these chemicals have resulted in a few mishaps from improper use. Ade quate safety-in-use evaluations of any of these chemicals persisting into our foodstuffs 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 "Residue Reviews" will continue to serve as an integrating factor both in focusing attention upon those many residue matters requiring further attention and in collating for variously trained readers present knowledge in specific important areas of residue and related endeavors involved with other chemical contaminants in the total environment. The contents of this and previous volumes of "Residue Reviews" illustrate these objectives. Since manuscripts are published in the order in which they are received in final form, it may seem that some important aspects of residue analytical chemistry, biochemistry, human and animal medicine, legislation, pharmacology, physiology, regulation, and tOxicology are being neglected; to the contrary, these apparent omis sions 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 editors and the Advisory Board earnestly solicit suggestions of topics and authors to help make this international book-series even more useful and informative. viii Preface "Residue Reviews" attempts to provide concise, critical reviews of timely advances, philosophy, and significant areas of accomplished or needed endeavor in the total field of residues of these and other foreign chemicals in any segment of the environment, as well as toxicological im plications. These reviews are either general or specific, but properly they may lie in the domains of analytical chemistry and its methodology, bio chemistry, human and animal medicine, legislation, pharmacology, physi ology, 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, which are involved in allowing pesticide and other plant-protecting chemicals to be used safely in producing, storing, and shipping crops. Added plant or animal pest-control chemicals or their metabolites that may persist into meat and other edible animal products ( milk and milk products, eggs, etc.) are also residues and are within this scope. The so-called food additives (substances deliberately added to foods for flavor, odor, appearance, etc., as well as those inadvertently added during manufacture, packaging, distribution, storage, etc.) are also considered suitable review material. In addition, contaminant chemicals 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 editors is neces sary before volunteered reviews are submitted in manuscript form. Department of Entomology F.A.G. University of California J.D.G. Riverside, California August 30, 1985 Table of Contents Samples used for interlaboratory studies of methods for pesticide residues analysis in foodstuffs By NIGEL A. SMART ••••••••••••••••••••••••••••••.•.••• 1 Cadmium in aquatic food webs By STRATFORD H. KAy .................................. 13 Behavioral responses of birds to pesticides and other contaminants By D. B. PEAKALL ...............•......•............... 45 Protocol guidelines for the investigations of photochemical fate of pesticides in water, air, and soils By GHULAM GHAUS CHOUDHRY and G. R. BARRIE WEBSTER . . . 79 Subject Index ............................................... 137 Samples used for interlaboratory studies of methods for pesticide residues analysis in foodstuffs By NIGEL A. SMARf* Contents I. Introduction ...................................................... . II. Requirements for samples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 2 III. Samples containing organochlorine insecticides .......................... 4 IV. Samples containing organophosphorus insecticides. . . . . . . . . . . . . . . . . . . . . . .. 5 V. Samples containing fungicides .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 7 VI. Samples containing other pesticides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 7 VII. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 8 Summary .............................................................. 8 References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 8 I. Introduction Interlaboratory studies of analytical methods for residues of pesticides in foods may be of several types. Laboratories may each use exactly the same procedure on aliquots of the same homogeneous gross sample (sub-samples baving been sent to each); these are termed collaborative studies. Secondly, laboratories may use their own routine procedure on aliquots of the same homogeneous gross sample (sub-samples having been sent to each); these are termed cooperative or check sample studies. Thirdly, laboratories may use several procedures on samples of their own and report "in-house" comparisons, termed assessments. Definitions of types of interlaboratory studies in the context of residues methods have been discussed in depth by Burke (1979). Planning interlaboratory studies depends on the purpose for which they are intended. Full collaborative studies of accepted methods in routine use can be planned to give realistic estimates of repeatability and reproducibility (ISO 1981). In many areas of analytical control, collaborative testing is generally *Ministry of Agriculture, Fisheries and Food, Agricultural Science Service, Harpen den Laboratory, Hatching Green, Harpenden, Hertfordshire, AL5 2BD, U.K. © 1985 by Springer-Verlag New York, Inc. Residue Reviews, TVlume 96. 2 Nigel A. Smart considered to be an integral requirement for method standardization (Taylor 1984). Less rigorous collaborative study between development laboratories can give valuable precision information on methods being evaluated as standards or for official recommendation. Check-sample studies aim to give a measure of the correctness of results which laboratories are obtaining in routine determinations, irrespective of the method used. The Joint FAD/WHO Food and Animal Feed Contamination Monitoring Programme Analytical Quality Assurance of Monitoring Data (WHO 1981 and 1983) is an example of this approach. Statistical evaluation of data on methods from interlaboratory studies has been the subject of an international standard (ISO 1981) and discussion (for example: Egan and West 1982, Hamaker 1984, Youden and Steiner 1975). Assessment of analyst performance, as distinct from method performance, from collaborative study has been discussed by Malanoski (1982). It is important to realize the practical constraints that have governed the choice of sample type for interlaboratory studies of pesticide residues methods reported in the literature and to examine the possibilities for progress in the future. II. Requirements for samples Substrates should have incurred the pesticide residues under examination in practical 'field' situations. Examples of this are from spray applications on fruit trees or bushes or on vegetable plots or from the tissues of animal or avian species that have ingested a contaminated feed. However, it is far from easy to arrange suitable samples. There are certain basic requirements which must be met for each sample: (1) it must be possible to prepare homogeneous samples for sub sampling to laboratories (or to reasonably approximate to this), (2) the substrate must be sufficiently stable to be sent to the laboratories concerned and of being stored for up to several weeks without decomposition, (3) the pesticide resi dues in the substrate must be sufficiently stable to be sent to the laboratories concerned and of being stored for several weeks without decomposition, and (4) unusual storage facilities or transport arrangements to comply with (2) or (3) should, preferably, not be necessary.) Some substrates are sufficiently stable for months or years and, when homo genized or well-mixed, have provided acceptable samples for collaborative analysis. Animal fats (Ault and Spurgeon 1984, Carr 1970, Eidelman 1967, Greve and Grevenstuk 1974b, Holden 1970, Johnson 1965, Malone and Burke 1969, Snelson 1976, Thier 1978 and 1984, Arbeitsgruppe "Pestizide" 1975, Panel on Determination of Organochlorine Residues in Foodstuffs of Animal Origin 1979), vegetable fats (Eidelman 1967, Greve and Grevenstuk 1974a, Editor's note: See, however, Kawar, N.S., G.C. de Batista, F.A. Gunther. 1973. I Pesticide stability in cold-stored plant parts, soils, and dairy products, and in cold-stored extractives solutions. Residue Reviews 48, 45-77.