Molecular Markers in Environmental Geochemistry

431 Pages·1997·39.25 MB·English

by  Robert P. Eganhouse (Eds.)

ACS SYMPOSIUM SERIES 671
Molecular Markers
in Environmental Geochemistry
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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
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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
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ded bation Copyright © 1997 American Chemical Society
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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
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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
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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
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34.1y 1, papers are included in the volumes. Verbatim reproductions of
63.Jul previously published papers are not accepted.
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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
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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
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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
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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
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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
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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
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ctooi: (including contaminant assemblages). The last section is the largest. The lead
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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
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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.
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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
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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
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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
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ctooi: led to the discovery in 1934 of a geochemical class of compounds having the
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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
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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.