ACS SYMPOSIUM SERIES 654 Environmental Biomonitoring Exposure Assessment and Specimen Banking g s.or001 2 | http://pubs.ack-1997-0654.fw K. S. SuHberaaltmh Caanniaadna, EDITOR 1b er 1, 200.1021/ G. V. Iyengar, EDITOR b1 ctooi: Biomineral Sciences International Inc. Od 6 on 997 | 31 34.1y 5, 63.Ma 89.1ate: y D d bon deati Developed from a symposium sponsored by the ac wnloPubli International Chemical Congress of Pacific Basin Societies Do and the ACS Division of Environmental Chemistry, Inc., at the 1995 International Chemical Congress of Pacific Basin Societies American Chemical Society, Washington, DC In Environmental Biomonitoring; Subramanian, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. QH 541.15 .I5I525 1997 Copy 1 International Chemical Congress of Pacific Basin Environmental biomonitoring Library of Congress Cataloging-in-Publication Data International Chemical Congress of Pacific Basin Societies (1995: Honolulu, Hawaii) Environmental biomonitoring: exposure assessment and specimen banking / K. S. Subramanian, G. V. Iyengar, editors. p. cm.—(ACS symposium series, ISSN 0097-6156; 654) "Developed from a symposium sponsored by the International g Chemical Congress of Pacific Basin Societies and the ACS Division of s.or001 ECnovnigrroensms oenf tPala cCifhicem Biastsriny, S Ioncci.e,t aiets ,t hHe o1n9o9l5u luIn, tHeranwaatiioi,n Dale Ccehmembeicra 1l 7-22, 2 | http://pubs.ack-1997-0654.fw 199IInS5cB."luN d 0es- 8b4ib1l2io-g3r4a7p7h-ic9a l references and indexes. 1b 1. Indicators (Biology)—Congresses. 2. Environmental er 1, 200.1021/ moIn. itSourbinrga—maCnoianng,r eKs.s esS.. , 1944- . II. Iyengar, G. V. (Govindaraja V.) b1 ctooi: III. Title. IV. Series. Od 6 on 997 | 3Q6H3.57431'6.135—.I5dIc52215 1995 96-48151 31 CIP 34.1y 5, 63.Ma 89.1ate: This book is printed on acid-free, recycled paper. y D d bon deati ac wnloPubli Copyright © 1997 American Chemical Society Do All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per-chapter fee of $17.00 plus $0.25 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale of pages in this book is permitted only under license from ACS. Direct these and other permission requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA In Environmental Biomonitoring; Subramanian, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Advisory Board ACS Symposium Series Robert J. Alaimo Cynthia A. Maryanoff Procter & Gamble Pharmaceuticals R. W. Johnson Pharmaceutical Research Institute Mark Arnold University of Iowa Roger A. Minear 2 | http://pubs.acs.org k-1997-0654.fw001 ADUPfnariziivveneriddr Csa iBmteyna tokBrafe olTr s Reene sneeasrscehe AUVOTnimani&vtckeT erUa snBrritatbey mPla lon eL faNc a-IoCblalroilhnaaraoamrmitosoap rsiaeuisg n 1b ber 1, 2010.1021/ NRaovbael rRte sFe.a rBchra dLyab, oJrra.t ory UGneioverrgseit yW o.f RMoicbheigratns ctooi: Mary E. Castellion North Carolina State University Od 6 on 997 | ChemEdit Company John R. Shapley 31 34.1y 5, Margaret A. Cavanaugh University of Illinois 63.Ma National Science Foundation at Urbana-Champaign 89.1ate: Arthur B. Ellis Douglas A. Smith y D d bon University of Wisconsin at Madison Concurrent Technologies Corporation deati wnloaPublic UGnuivnedrasi tIy. oGf Keoarngsa s LD.u SPoonmt asundaram Do Madeleine M. Joullie Michael D. Taylor University of Pennsylvania Parke-Davis Pharmaceutical Research Lawrence P. Klemann William C. Walker Nabisco Foods Group DuPont Douglas R. Lloyd Peter Willett The University of Texas at Austin University of Sheffield (England) In Environmental Biomonitoring; Subramanian, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Foreword IHE ACS SYMPOSIUM SERIES was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of this series is to publish comprehensive books developed from symposia, which are usually "snapshots g in time" of the current research being done on a topic, plus s.or001 some review material on the topic. For this reason, it is neces­ 2 | http://pubs.ack-1997-0654.fw ptshareroy p totoBhspaeeifdtc o trhtaeaen b dalp esaf ypoomref r pscco oobsmneiut pemprnue-thbsb elainsissesh idevr edebv noaieseos wksq euidsoic fpkf oultyhrt eau asnpc dppoeorlolrse psccirbtoiialnoetten.r n.a ecsSt,so mthtoee 1b er 1, 200.1021/ proaupnedrs ouatr et hee xsccluodpeed o fa tt heth viso lupmoien.t , Ina nadd doittihoenr,s a adrrea fta dodfe eda ctho b1 paper is peer-reviewed prior to final acceptance or rejection. Octodoi: This anonymous review process is supervised by the organiz­ 6 on 997 | er^) of the symposium, who become the editor(s) of the book. 31 The authors then revise their papers according to the recom­ 34.1y 5, mendations of both the reviewers and the editors, prepare 63.Ma camera-ready copy, and submit the final papers to the editors, 89.1ate: who check that all necessary revisions have been made. y D d bon As a rule, only original research papers and original re­ deati view papers are included in the volumes. Verbatim reproduc­ ac wnloPubli tions of previously published papers are not accepted. Do ACS BOOKS DEPARTMENT In Environmental Biomonitoring; Subramanian, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Preface ENVIRONMENTAL BIOMONITORING has become an important tool for identifying and instituting remedies to the threat of contamination of the biosphere. The available information suggests that current pollutant lev­ els have become stressful to a large number of sensitive flora and fauna, as well as to human beings. The deleterious impacts, both real and per­ ceived, of natural and man-made pollutants have created the need to g monitor their release and subsequent movement through the physical and 012 | http://pubs.acs.or1/bk-1997-0654.pr001 bmaeisntxtiatoespentnloniocttstgaueiulisot cre nepa f lro teoirocsnb ovleebemianremrvopilnsyinor g mnoc iendaefnmoeuntcnssteaue tnildsfo te iafcdsb lua ytchtro iovexonne en itent lahlnoomaevfbn, ii icnromaoeatn nniocdmtsn s yit erstoteontxhesrtmirp.ic onoasugn Ing tst athesohn. o adutso mIt n a, bo tshhesnaeeecdi soatdowslmimtrtho ei reo nlnandnotn,.e x dcioin eofecs unsrhsaev uraiymsrs ouinabntngo­­ 22 1, 10 Environmental biomonitoring involves several aspects of environmen­ October doi: 10. tpaol llhuetaalntths, ainncdl utdheinirg tmhee tadbeotleirtmesi,n aetxipoons uarned aisdseenstsimficeantti,o ann odf lmowea sleuvreemls eonft 6 on 997 | of biological markers of exposure. Another important facet of environ­ 34.13y 5, 1 bmaennktianlg .b iAom sopneictiomrienng biasn kth ea ctesm aesr gai nbgri dfgieel dc oonfn eecntvinirgo nremael-ntitmal e smpeocnimitoern­ 3.Ma 89.16ate: ing wThitihs fubtouorek tries ndb-amseodn itoonri ngth aec tisvyimtiepso. sium entitled "Environmental y D d bon Biomonitoring and Specimen Banking", held at the 1995 International deati Chemical Congress of Pacific Basin Societies (Pacifichem '95) in Hono­ ac wnloPubli lulu, Hawaii, on December 17-22, 1995. The purpose of the book is to o assimilate current developments in the diverse field of environmental and D human health. In particular, we have highlighted recent developments in monitoring strategies, exposure assessment, bioindicators (or biomarkers), and specimen banking. The term "environmental biomonitoring", as used in this book, refers to the measurement and identification of pollutants and their metabolites in environmental and biological media. The term "media" refers to the environments in which the pollutants are present. The term "biological monitoring" is used when the concentration of a pollutant or its metabol­ ite is monitored in a human indicator medium such as blood, urine, hair, saliva, or the placenta. Although the emphasis of the book is on moni­ toring the biosphere in the context of public health, monitoring efforts related to occupational exposure are also touched upon because of their ix In Environmental Biomonitoring; Subramanian, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. methodological relevance. A group of internationally renowned research­ ers was assembled to address these issues and to facilitate an assessment of the state-of-the-art of the field of environmental biomonitoring and specimen banking. The book is organized into four sections: monitoring, exposure assessment, bioindicators, and specimen banking. Chapter 1 provides a comprehensive overview of the subject of environmental biomonitoring to set the tone of the book. Other chapters in the book have been developed from only 23 of the 60 papers presented at the symposium in order to avoid an incoherent collection of papers and to synchronize the flow of information from one chapter to the next. The mix of review papers, original research manuscripts, and reports of new work presented here best reflect the current state of the subject. This book represents a g modest beginning of our efforts to achieve a comprehensive perspective 012 | http://pubs.acs.or1/bk-1997-0654.pr001 mieoanfnn etavetnlhirTytreeaoths ilnctef iima sneclclg edio enc nnaohttacnefel ednm e b tnsaiuis vnostidoremry ffou ,hon tlenhm caielitline otnn hbirttc.oih anaoellgW k ib r aci eosnhm hmdehoam oosnuppinylsedei tt cr aoyatinmhr,p diapne etengv ca t.oab hllr eaoite ngodrky e i,sqa ncdmugieee.e nrsdsttsi iscw tiisinnl let io,nf i antthndhe de t hrefeiinsea vlldbmirsoo ooonkff­ 22 1, 10 October doi: 10. KE.n vSi. roSnUmBeRnAtMal AHNeIaAlNth Directorate 6 on 997 | Postal Locator 0800B3 31 Health Canada 34.1y 5, Tunney's Pasture, Ottawa 3.Ma 6 Ontario K1A 0L2, Canada 89.1ate: y D d bon G. V. IYENGAR deati Biomineral Sciences International Inc. ac wnloPubli 6202 Maiden Lane o Bethesda, MD 20817 D August 17, 1996 x In Environmental Biomonitoring; Subramanian, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Chapter 1 Environmental Biomonitoring and Specimen Banking Bioanalytical Perspectives G. V. Iyengar1 and K. S. Subramanian2 1Biomineral Sciences International Inc., 6202 Maiden Lane, Bethesda, MD 20817 2Environmental Health Directorate, Postal Locator 0800B3, Health 2 | http://pubs.acs.org k-1997-0654.ch001 wTbCahiadsenies al hydfe asoa,tr ult Tdhriu iesnidkmn sepuayabs'cssjtee csPotsa.mf sTtteouhnxretei. pc , rIOisnmu tbtatahsrwtyias an gc,oc eoOasln n htietneaxr rteti,ho ie rse K tceo1en Andveti r0voLeanld2omv,p aeC nnrceatenl isaia sdb ialnae 1b ber 1, 2010.1021/ qaCnuoaanlnystetiitqciueasel nctohlyef ,m ciiths hteramys i hcbaaevlesen minpa odstiessi sbiultee ps t,ro a cbqtoiucdaaynl-t iftfoluy i mdcsoe,an stfauomroedi nv aeanrntysd s smuaciarhl.l Octodoi: as pesticides, other organic and inorganic constituents, metals, and 36 on 1997 | seomlvpehnats isa ndd udrriungg retshiidsu esd eivne loouprm eennvtairlo npmheanste. Hiso wpevlaecre, dm uocnh 34.1y 5, instrumentation, while factors affecting the "total quality" of a 63.Ma bioenvironmental investigation tend to be overlooked. Unless other 89.1ate: tools for risk assessment such as sound biomonitoring programs y D (real-time and long-term) based on environmental epidemiological d bon concepts are properly used in generating data, interpreting the adecati significance of these findings will continue to be a challenge. wnloPubli Therefore, dedicated efforts are needed for (i) consolidating the Do biologic basis for selection of specimens for environmental surveillance, (ii) developing strategies for long-term preservation of sampled materials, (iii) accomplishing harmonization of analytical measurements, and (iv) recognizing the multidisciplinary expertise, for understanding the pollution trends and to provide a reliable basis for health risk assessment in exposure situations. The concern about toxic substances in the biosphere and the need for developing strategies to eliminate or minimize the health hazards caused by these pollutants is well recognized. This is particularly relevant in the context of the estimated 60,000 or so chemicals of industrial consequence, of which only a handful are © 1997 American Chemical Society In Environmental Biomonitoring; Subramanian, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. 2 ENVIRONMENTAL BIOMONITORING currently being examined for their environmental impact (1). For example, pesticides (chlorinated hydrocarbons and their degradation products) are ubiquitous in ecosystems. There is evidence in Finland that although the use of DDT and its derivatives ended in the early 1970s, these compounds are still encountered in trace amounts in fish (2). Thus, contaminants such as pesticides, polycyclic aromatic hydrocarbons, halogenated hydrocarbons, heavy metals and other trace elements, enter the food chain through various sources (e.g. anthropogenic) in the biosphere. The organic pesticides are generally highly stable, lipophilic substances that tend to accumulate in adipose tissues over time, culminating in environmental toxicity and mutagenic changes. The above mentioned events call for stringent measures for environmental surveillance, but the scenario is not easy to comprehend; there are too many g chemicals and practically endless routes of exposure requiring comprehensive 2 | http://pubs.acs.ork-1997-0654.ch001 piscsHscpou ohenrnwecscomuieemtii vetvte eshen(r det,fsr o aatmsrcona mk umyail nostemisngd eoif istossnoshcrir toihiopanrurlltgmi-li.nn t ceaMaglrnar mypso ser r eoxeatspgorp eorvpoansermfuodr r,asp ec)tossh hhl eaeltoun osust d atxla idnentp tencsbr-olo.eou bv Tfdidi-ohsitenhitesoigescinge- itasn do rpexeftrdo niooc rtba iftfon lraieet cnmstmara oitslienys oe pwttnithec aecbaort lorfie av tcnhneaov t pm irprresoperkaonseileltpm leatfrinureimcaclnltheyete. 1b ber 1, 2010.1021/ pr(eirdeoevvnaitdliufeyasit neag dlsaootnuagn -drtee trrbmoass ptirsee cntfidovsre )l yea vsea xlautneaantlidyostn ic taholef c atshpceoa bpiebl iitooilefos g diiamctaapl roaevfcfceeu.c mtTsh ueloa ftai bovinlai,rt yiao nutods ctooi: pollutants. Od 36 on 1997 | basis foTrh seerleefcotrieo,n doefd aicpaptreodp reifaftoer tss paerceim neeneds efdo rf oenr v(iir)o cnomnseonltiadla stiunrgv ethilela bnicoel,o g(iiic) 34.1y 5, developing strategies for long-term preservation of sampled materials, (iii) 63.Ma accomplishing harmonization of analytical measurements, and (iv) recognizing the 89.1ate: multidiscilpinary expertise (3) to evaluate pollution trends. The benefits are: y D improvements in problem oriented analytical approaches, establishment of d bon reliable baseline values for numerous chemical constituents in selected deati ac environmental media, and a proven experimental tool for assessment of the wnloPubli environmental health criteria. These aspects will be addressed in the following Do sections. Chemicals in the Environment Inorganic constituents: From the environmental pollution point of view, various anthropogenic activities, especially the burning of fossil fuels required in various industrial operations, are a major source of several toxic trace elements, including Se (4). Among these, As, Cd, Hg, and Pb deserve special mention since they have profound effects on both domestic animals and human beings. Froslie and co-workers (5) have shown that heavy-metal contamination of natural surface soils from atmospheric deposition occurs even at very long distances from the major point source. Several examples of human exposure to As, Cd, Hg, and Pb have been recorded in the scientific literature. It is known, for instance, that sections of In Environmental Biomonitoring; Subramanian, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. 1. IYENGAR & SUBRAMANIAN Bioanalytical Perspectives 3 human populations from the south and far east Asia such as Japan, Taiwan and the Philippines have high levels of As in their blood, milk or hair (6). The source of As is linked to the consumption of fish which is a significant component of an average diet. The As content of the soil also plays a role. Among the innumerable sources of industrial pollution, gasoline is the major source of environmental Pb in those countries where unleaded petrol is not mandatory. In many urban populations blood-Pb levels have been shown to be well over 200 ng/mL (6). This figure may be compared with the moderate or low levels of 90 ng/mL in Japan and Sweden, or even lower levels of 30 ng/mL observed in remote parts of Nepal and the interior regions of Venezuela (6). Similarly, urban mothers have been shown to secrete more Pb into their milk than their corresponding rural controls (7). A common problem is faced by young g children who ingest several mg of soil (along with paint scrapings and house dust) 2 | http://pubs.acs.ork-1997-0654.ch001 nnpSsPioaiebn, tnr cTui -nedirf toaaaailoytnk d ldirees e vsV bsnoeuy.o lul Thttrbi chunaeeimgsasses .aiidy nsnT a stohpoi snego e npperairiuvnfoeileacucarliatsy siwn osebtilnii sydeos xeoe ehntnfsrai tvasnsi-ima grdimon aiuencptntermlaede raeseaysn r esoctetadhfxal inpp alpdodrbresi'oosnuhu bgrditsle a et ooiomtlnfoyr ie Pfcni abn hohct utetua ondkomxd neiiarlnc eynoi dtp fyP-se fsbkdioon,ei lidalbdle tiu trcaaotinab cntado eslfv ss io(oe et8t l hhtdA)hae.sl etr,, 1b October 1, 20doi: 10.1021/ saamnndde lhtaeanriIs rt intnhhecaaarsnre aCadslleisud oj -oc Nbof aenupetropnoo latsro e. i pAno3 Rr2ftiu evtmdeim -aftonehlisada t iie nnxsc ucrhbreeajaetisecre dts c hionirng euthserienidnrti anlerg(yv0 e .iA2lns5 s o t h(fv6 esA. 4 sv8 vii ncsn i ntg3hi/1temy i nrL ogu)f/r miwCnLaeus ) 36 on 1997 | dexepmoosnusrter atetdo (9th)i.s Anealleymsiesn ot f threes ublotdinyg b ufrrdoemn ofC Aus- ocrleea rlsym ineldtiicnagt eda cetxicveitsiseisv.e 34.1y 5, Environmental air particulate analyses have shown a correlation between As and 63.Ma Cu near smelters. 89.1ate: Cadmium is a toxic industrial environmental pollutant. Tobacco smoking y D is a significant contributor to the high levels of Cd found in smokers. Blood levels ded bation of Cd in smokers are higher than in those in nonsmokers by a factor of 3 to 12 ac (6). Excess exposure to Cd can cause renal tubular damage and obstructive lung wnloPubli disease. The amount of Cd transferred from soil to plant to animal or human can Do be of concern, especially where sewage sludge is used to fertilize the soils (10,11). The degree of risk depends on several factors: type of food affected (e.g. commonly consumed foods and foods consumed in large quantities) by the application of the sludge, soil pH and the amount of Cd entering the soil. Sea-food is a major source of Hg intake. For example, it has been shown that Alaskan Eskimo mothers have rather high concentrations of this element in placenta, hair, blood and milk (12). It is also known that these concentrations of Hg are directly proportional to the quantity of seal meat consumed. Subjects who consumed seal meat daily had the highest levels of Hg (12). This brings into focus considerations of infant nutrition since breast-fed babies of these mothers are potentially subjected to toxic doses of Hg. Mineral oil contains about 0.2 ^g/g of Se whereas coal contains as much as 3 /xg/g, and in some exceptional cases levels can be much higher (4,13,14). In Environmental Biomonitoring; Subramanian, K., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997.