Molecular Markers in Environmental Geochemistry PDF
Preview Molecular Markers in Environmental Geochemistry
ACS SYMPOSIUM SERIES 671 Molecular Markers in Environmental Geochemistry g acs.orw001 bs.1.f u7 p6 p://7-0 htt99 2 | k-1 Robert P.E ganhouse, 1b EDITOR er 1, 200.1021/ U.S. Geological Survey b1 ctooi: Od 6 on 997 | 31 34.1y 1, 3.ul 6J 89.1ate: y D d bon deati ac wnloPubli o D Developed from a symposium sponsored by the Divisions of Environmental Chemistry, Inc., and Geochemistry, Inc. American Chemical Society, Washington, DC In Molecular Markers in Environmental Geochemistry; Eganhouse, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Library of Congress Cataloging-in-Publication Data Molecular markers in environmental geochemistry / Robert P. Eganhouse, editor. p. cm.—(ACS symposium series, ISSN 0097-6156; 671) "Developed from a symposium sponsored by the divisions of Environmental Chemistry, Inc., and Geochemistry, Inc., at the 212th National Meeting of the American Chemical Society, Orlando, Florida, August 25-29, 1996." g Includes bibliographical references and indexes. acs.orw001 ISBN 0-8412-3518-X bs.1.f u7 p6 1. Environmental geochemistry—Congresses. 2. Biochemical markers— p://7-0 Congresses. htt99 2 | k-1 I. Eganhouse, Robert P. (Robert Paul), 1948- . II. American Chemical 1b er 1, 200.1021/ SS(2oo1cc2iieethttyy:.. 1 DD99iivv6ii:ss iiOoonnrl aoonffd EGone, voFicrlhao.en)m mViestn.r Styae.l r CiIeVhs..e mAmisterryi.c aIInI .C Ahmemeriiccaaln S Cochieetmyi.c aMl eeting b1 Octodoi: QE516.4.M65 1997 6 on 997 | 628—dc21 97-166C2IP5 31 34.1y 1, 3.ul 89.16ate: J This book is printed on acid-free, recycled paper. y D ded bation Copyright © 1997 American Chemical Society ac ownlo Publi AClolp Ryrigighhtts ARcets eirsv aeldlo.w Reedp rfoogrr ainptherinc aclo upsyein ogn blye,y ponrodv itdheadt tpheartm ait tpeedr- cbhya pSteecrt ifoene so 1f0 $71 7o.r0 010 p8lu osf $t0h.e2 5U .pSe. r D 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 permissions 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 Molecular Markers in Environmental Geochemistry; Eganhouse, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Advisory Board ACS Symposium Series Mary E. Castellion Omkaram Nalamasu ChemEdit Company AT&T Bell Laboratories g bs.acs.or1.fw001 AUnritvheursrit By .o fE Wlliissc onsin at Madison KPuirndaume U Pnaivrekrs ity u7 p6 p://7-0 Jeffrey S. Gaffney Katherine R. Porter htt99 Argonne National Laboratory Duke University 2 | k-1 1b Gunda I. Georg er 1, 200.1021/ University of Kansas DThoe uDgAlSa sG Aro.u Spm, Initch. ctoboi: 1 Lawrence P. Klemann Martin R. Tant Od 6 on 997 | Nabisco Foods Group Eastman Chemical Co. 31 3.34.1uly 1, RUnicivherasritdy Nof. MLoisseopuprik y MParikceh-Daealv iDs .P hTaarmylaocre utical d by 89.16on Date: J CR.y RWne.ts heJaoiarhc nAhso .I nnM sPtiahtuartyrema nacoefuft ical LeRroesyea Brc.h T ownsend deati University of Michigan wnloaPublic RUnoigveerrs itAy. o Mf Iillnineoairs William C. Walker o D at Urbana-Champaign DuPont Company In Molecular Markers in Environmental Geochemistry; Eganhouse, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Foreword THE 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 in time" of the current research being done on a topic, plus some review material on the topic. For this reason, it is necessary that the papers be published as quickly as possible. g Before a symposium-based book is put under contract, the bs.acs.or1.fw001 panrodp ofsoerd tcaobmlep orefh ceonnstievnetnse siss reovfi ewtheed fcoorl laepcptiroonp.r iaSteonmeses ptoap tehres toapriec pu67 excluded at this point, and others are added to round out the scope of p://7-0 the volume. In addition, a draft of each paper is peer-reviewed prior to htt99 2 | k-1 final acceptance or rejection. This anonymous review process is ber 1, 20110.1021/b teshudepit eorrerv(csios)me odmf btehyne d tbahoteioo kno.sr g Toahnfe ib zaeourtt(hhs o)tr hsoe f t hrteehvnei ereswyvemisrsep otahsneiduir m tph,a ewp eehrdosi taobcrescc,oo rmpdrieen pgtah rtoee ctooi: camera-ready copy, and submit the final papers to the editors, who Od 36 on 1997 | checAk sth aat arulll en,e coensslyar yo rriegvinisailo nrse sheaavrec hb epeanp merasd ea.n d original review 34.1y 1, papers are included in the volumes. Verbatim reproductions of 63.Jul previously published papers are not accepted. 89.1ate: y D d bon ACS BOOKS DEPARTMENT deati ac wnloPubli o D In Molecular Markers in Environmental Geochemistry; Eganhouse, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Preface MOLECULAR MARKERS ARE EXTREMELY POWERFUL TOOLS that can provide information about sources of organic matter and the physical, chemical, and biological processes that act on them. They become particularly valuable when there is no direct means of establishing the contribution of a nonspecific pollutant or when it is of interest to know whether the target g or1 compounds have undergone alteration following release to the environment. 2 | http://pubs.acs.k-1997-0671.pr00 gUtecrnheanevoifnmiocrihronitsnegutmms n aefiitsonnetr tlr yaymol,, r agpamnar oytnoeb ilrycelme ecmau gIrls seau..or s cACemh oteh antmehrsrkeieese q trstrusoay em ncwhteolea yrtnri, a tm ctrheteleael,ra r iogtzgeneerdllo yy twh afiutis henf elfndiowoesflt diiecn,p endhudviar ivssruib odueynudn ma teilelnsr n vrewetsiacrietoleah nonr cmrtflhogye ra nmnboteiaancell n 1b ber 1, 2010.1021/ ratheIrn grOacdtuoable. r 1993, almost exactly 20 years after first entering the nascent ctooi: field of environmental organic geochemistry, I was fortunate to participate in a Od 6 on 997 | bwroorukgshhto pto gspeothnesro rae dh abnyd ftuhle oIfn teexrpnearttiso nfaolr Athteo mpiucr pEonseer goyf Adegveenlcoyp.i nTgh ae wmoerektiinngg 31 34.1y 1, document for the coastal pollution monitoring program in the Mediterranean 3.ul Sea. Participants were asked to provide detailed analytical procedures and 6J by 89.1n Date: pmroolgercaumlamr amtiacr kgeursi dienl itnhees mfoorn itiomripnlgem preongtaratimon. Uopfo na rvetaurrientiyn g otfo manyth lraobpoorgaetonriyc wnloaded Publicatio iRmn aatyrhkneee rrUs, ,n aiibnteo hdui tsS ttcahatees sem, fIeo ehrt aidndeg ld.i nisMecauatsiroksin ow noasfs cw oaialtshsot aa li nvptieosirlteliusnttgeio dAn uipnsr ottrbhalelei amunss es c oiofeffn Stmiysotd,l neMecyua lriankr o D relation to the presence of submarine wastewater outfalls (c/. Chapter 20). It was at this time that the idea for an international meeting, focused on molecular markers and their many applications in environmental geochemistry, crystallized in my mind. The time was right, it seemed to me, for such a meeting. That idea culminated in a symposium presented at the 212th National Meeting of the American Chemical Society, titled "Application of Molecular Markers in Environmental Geochemistry", jointly sponsored by the ACS Divisions of Environmental Chemistry, Inc., and Geochemistry, Inc., in Orlando, Florida, August 25-29, 1996. The symposium consisted of 54 oral and 22 poster presentations delivered by scientists from many countries. My initial concept for the symposium was limited to one class of molecular markers, those derived ix In Molecular Markers in Environmental Geochemistry; Eganhouse, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. from human sources (i.e., anthropogenic markers). However, the scope of the meeting quickly expanded as John Volkman and Peter Nichols, members of the "Australian connection", suggested that modern and ancient biological markers should also be included. The format for the symposium was set with the addition of contaminant assemblages, complex mixtures such as the polychlorinated biphenyls and polycyclic aromatic hydrocarbons, that can serve as powerful molecular process probes. The four theme areas were recent biogenic markers, anthropogenic markers, fossil biomarkers, and contaminant assemblages. The symposium papers were presented by a diverse international cast of scientists representing a variety of disciplines, including organic geochemistry, environmental chemistry, atmospheric chemistry, microbial ecology, and marine biology. Because of this diversity and limitations imposed by traditional disciplinary boundaries, many of these scientists had not previously come in contact with each other. Thus, it became the primary objective of the meeting to facilitate interdisciplinary discussion and foster scientific collaboration. As g or1 judged by the many collaborations and communications initiated or enhanced 12 | http://pubs.acs.bk-1997-0671.pr00 bdednooutocrhiuknuTm.gs oi Te aanshantm eadl ta iroreaoganffetd ew esrer yex rmttwhee peniil ontl, ss ofyiturihmndmedep r fo.pco sHoarimrnuettminarcicti,b p euoi,at tft nih owttishnsa,es sb I ofs aroyod kmmes.uc p icodtchseeeidsu s mf.to h uEharamt spb srbooeemlvdeieeno n urefseodltly albo imnywe e-dtunh pteii no nartanehwdde ber 1, 2010.1021/ tchoenmteem paorreaarsy. bHioogwenevice rm, atrhkee rsb, ofookss ili sb ioormgaarnkizeersd, ainndto anotnhlryo pothgreeneic smecatrikoenrss: ctooi: (including contaminant assemblages). The last section is the largest. The lead Od 6 on 997 | tchheamptee ra roefa ,e wachhe rseebcyti osanl i(ein.et .c, ocnhcaepptetsr sa r2e, i8ll,u satnradt e1d2 )w oitfhf eerxs amanp loevse frrvoimew o nogf otihnagt 31 34.1y 1, or recent research. These overview chapters are highly recommended for readers 3.ul wishing to learn about the big picture in a given subject area before delving into 6J by 89.1n Date: tChhea pmteorrse 8s paencdif i1c2 s uablsjoec ct omntaatitne rs tfrouucntudr ailn aspupbesnedqiuceenst tchhaat pstherosu lodf ptrhoavte s eucsteifounl.. wnloaded Publicatio Amotlhotehleroc uaugplahpr l itmchaiastri okbneorsos y,k e ctco otvone trbaaiegn esd iisescx onavmeecpreelsedss.a rHoilfoy w mineacvnoeymr ,o ptfhl eetth eie,n atkenrndeo stwthenedr earep aaprdleei crda wtoiuoilbnl tslf eiosnfsd o D that the references provided in each chapter serve as a valuable guide to the literature. In some respects, this book and the symposium upon which it is based represent a benchmark. They reflect the fact that the field of environmental organic geochemistry is beginning to show signs of maturity. It is my hope that this book will adequately convey some of the most exciting recent advances in this rapidly evolving field and thereby stimulate further research and interaction. If we have done our job correctly, the international flavor of the meeting and the excitement of the participants will be apparent to readers. The tremendous support and efforts of symposium participants and authors has made this an extremely enjoyable and deeply satisfying professional experience for me. x In Molecular Markers in Environmental Geochemistry; Eganhouse, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Acknowledgments Many organizations and individuals deserve credit for the success of the symposium and the development of this book. I thank the symposium participants and authors, whose efforts made this book possible. For their important conceptual contributions and continuing encouragement, I extend special thanks to John Volkman, Peter Nichols, and Mark Rayner. Jim Pontolillo and Bonnie Hower provided day-to-day editorial services and valuable advice, and R. P. Eganhouse, Sr., contributed to the design of the cover. I sincerely appreciate the financial assistance given by the ACS Divisions of Environmental Chemistry, Inc., and Geochemistry, Inc.; as well as the moral support of program chairs Martha Wells, Tim Eglinton, and George Luther. Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this activity (ACS- PRF30870-SE). ACS-PRF funds were used to facilitate foreign travel for some g of the non-U.S. speakers. I gratefully acknowledge the support of the U.S. or1 2 | http://pubs.acs.k-1997-0671.pr00 bvdGoeeertooeykrl mo.s hgiFoinciranatt laip olSelnyru i,ro svdeIe rsyv p oeadf yu at risimt nraigebn. u thitnees pptilora antEniodinnwg fa oorrdf tthhGee. scWyommopopodles, ituiJomrn., aownf dhb otishgee p erloidfjieetwcintsog r wko fi atthhniidns ber 1, 20110.1021/b UR12O.S2B.0 E1GR eSTou lPno.rg iEiscGea AVl NSaHullrOevyUe DyS Eri ve ctooi: Reston, VA 20192 Od 6 on 997 | 31 March 12, 1997 34.1y 1, 3.ul 6J by 89.1n Date: wnloaded Publicatio o D xi In Molecular Markers in Environmental Geochemistry; Eganhouse, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. Chapter 1 Molecular Markers and Environmental Organic Geochemistry: An Overview Robert P. Eganhouse U.S. Geological Survey, 12201 Sunrise Valley Drive, Reston, VA 20192 g ubs.acs.or71.ch001 It is said that we live in an Information Age. Yet, throughout Man's tenure on Earth p6 p://7-0 the ambient environment has been providing information on a continual basis. In the 2 | httk-199 ccahseem oicfa olsl.f acStoor,y i na nedss etansctee, swenes ehsa,v ien fboeremna tuiosinn gis c shuepmpilcieadl cauneds dtoet edcitsecdri mini nthatee foarmmo nogf 1b er 1, 200.1021/ vwairnieo utsa sstuinbgs.ta] ncIens tfhoirs thboeo ekn twireet yw oillf obuer incotelrleecstteivde ienx itshteen cdee.t ec[tAio ng ooofd ae xpaamrtipcluel aisr Octobdoi: 1 pcarotevgidorey i noffo crmheamtiiocnal sa,b mouotl esocuurlcaers mofa orkrgearnsi,c t hmaatt ecrainal,. u nSdoemr aep mproolpecriualtaer c mircaurmkesrtsa nacrees , 6 on 997 | produced by humans either intentionally or inadvertently, whereas others are strictly 31 biosynthetic. The characteristic shared by all molecular markers is the fact that their 34.1y 1, structures are linked to specific origins. Thus, the observation of one of these 63.Jul compounds in the environment necessarily signals the presence of a specific source 89.1ate: material. In principle, when several markers are found, one can begin to unravel by n D contributions made by multiple sources (source apportionment). This becomes ded atio particularly relevant when non-specific contaminants are also present because the wnloaPublic mdifafrekreenrst scoaunr cbees . used to indirectly estimate contributions of contaminants made by o D The chapters to follow examine a variety of molecular markers having diverse origins. However, for purposes of organization we have placed markers into three general categories. Contemporary Biogenic Markers (Chapters 2-7) are compounds synthesized by microorganisms and/or vascular plants that are used as cellular constituents. These can be found in living organisms themselves, or, if persistent, as residues that have undergone little or no alteration in the modern environment. The second category, Fossil Biomarkers (Chapters 8-11), includes compounds that are present in fossil fuels and ancient sediments as a result of the burial of biogenic organic matter and its subsequent alteration. As such, these markers have clear structural relations to contemporary biogenic markers. The last category we have called Anthropogenic Markers (Chapters 12-26). These compounds fall into two general classes based on their real or perceived toxicity and source specificity. The first is This chapter not subject to U.S. copyright. Published 1997 American Chemical Society 1 In Molecular Markers in Environmental Geochemistry; Eganhouse, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997. 2 MOLECULAR MARKERS IN ENVIRONMENTAL GEOCHEMISTRY populated by synthetic (or sometimes natural) organic compounds which are not considered to be pollutants per se but whose presence in the modern environment is directly related to human activity. Examples include the fecal sterol, coprostanol, and synthetic surfactants used in commercial detergents. The second class of anthropogenic markers is composed of contaminant assemblages which are known to be toxic and whose pervasive presence in the environment is entirely or primarily attributable to industrial activity. These include such compounds as the PCBs (polychlorinated biphenyls) and PAHs (polycyclic aromatic hydrocarbons), toxaphene and chlorinated pesticides. In the chapters to follow the reader will see how these various types of markers can be used to gain a better understanding of our contemporary environment and to assess the impact of human activities on it. Many types of information can be derived from studies of these molecules, information that frequently cannot be bs.acs.org 1.ch001 ocaolbsntoatai anmse idmn abonyltes cc uothlnaevrm e'pnsretiolovcneeass.ls b piIornog btehoeicssh' .e semniscea lt haepyp rosearcvhee sn ootr obnyly d iarse csto euxrcame iinnadtiicoanto orfs tbhuet u7 p6 2 | http://k-1997-0 Historical Perspective er 1, 2010.1021/b mwOoroirlgkei cnbu yloa Afr l ftmrheead rTk'Mereroi blcesoc onuncla ethrp etM ocoragmrakenesicr f rcCoomonns ttchiteuepe dnt.it ssc ioOpflui nsrhe a coluefrs ro,e rbngitat unmaicpe pngreseo cacinahtdeiom cnir sutodryfe . tohEilesa rly b1 ctooi: led to the discovery in 1934 of a geochemical class of compounds having the Od 6 on 997 | tceotrraep ymrroolelec uslatrru csttururect,u trhese, pTetrreoibpos rpphroyproinsse d(V t)h. atB tahsee dp eotnro psiomrpihlayrritiiness wbeetrwe eaecntu tahlelyir 31 34.1y 1, derived from chlorophylls synthesized by ancient plants (Figure 1). He hypothesized 3.ul that following death, cellular constituents of plants such as the tetrapyrrole pigments 6J by 89.1n Date: ufonrd ethrgeose a t rsaenrsifeosr mofa tbioiongse oacrhee mcoilclaecl ttirvaenlsyf orremfearrtieodn st o( 2a)s. d[iTahgee nperosciess sbeys greesopcohnesmibisltes .] wnloaded Publicatio Wrsetamhbeilneree a(roaslr i ztshetaedb ivdliauzsreitdn )gm m adjoioalrgeicetyunl ees(si«s m , 9at9hy.e9 b %feu )np droeafsme brevinoetladol g (i5ac)rac.l lhyWit ephcretoundr etuh cioes dfo scoocmrugraesn ooicvf e tmrh geae ttomelroo griiesc Do time, a type of 'molecular' fossil (4) is formed, the presence of which offers strong evidence of a biological origin. The pathway proposed by Treibs between a recognizable biological precursor and a diagenetic product was highly significant at the time because it established the first unequivocal molecular evidence for the biological origin of petroleum and simultaneously ushered in the era of molecular organic geochemistry. In the context of the present book, his findings provide a compelling demonstration of the utility of the molecular marker approach in explaining complex natural phenomena. Environmental Organic Geochemistry: Formative Years (1950-70). Between the time of Treibs' original reports and the early 1950s progress in the field of organic geochemistry continued to be limited by the low resolving power and poor sensitivity of available analytical technologies. It was only with great difficulty that individual compounds could be isolated from complex matrices and identified at trace levels. In Molecular Markers in Environmental Geochemistry; Eganhouse, R.; ACS Symposium Series; American Chemical Society: Washington, DC, 1997.
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