The Biomarker Guide Second Edition Volume 1
Cambridge University Press0521781582 - The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History,Second EditionK. E. Peters, C. C. Walters and J. M. MoldowanFrontmatterMore informationThe Biomarker GuideSecond EditionVolume 1The second edition of The Biomarker Guide is a fully updatedand expanded version of this essential reference. Now in twovolumes, it provides a comprehensive account of the role thatbiomarker technology plays both in petroleum exploration andin understanding Earth history and processes.Biomarkers and Isotopes in the Environment and HumanHistory details the origins of biomarkers and introduces basicchemical principles relevant to their study. It discusses analytical techniques, and applications of biomarkers to environmentaland archeological problems.The Biomarker Guide is an invaluable resource for geologists, petroleum geochemists, biogeochemists, environmentalscientists, and archeologists.K enneth E. Peters is currently Senior Research Geologist atthe US Geological Survey in Menlo Park, California, where heis involved in three-dimensional petroleum system modeling forthe North Slope of Alaska, the San Joaquin Basin, and elsewhere.He has 25 years of research experience with Chevron, Mobil,and ExxonMobil. Ken taught formal courses in petroleum geochemistry and thermal modeling both in industry and at various universities. He was Chair of the Organic GeochemistryDivision of the Geochemical Society (2001–2004).C lifford C. Walters is Senior Research Associate withthe ExxonMobil Research and Engineering Company, where hemodels oil generation and reservoir transformations, geomicrobiology, and processes of solids formation. He has over 20 yearsof industrial experience, including research at Sun Explorationand Production Company, and Mobil.J. M ichael Moldowan is Professor (Research) in theDepartment of Geological and Environmental Sciences atStanford University. He joined Chevron’s Biomarker Groupin 1974, which, under the leadership of the late Dr. WolfgangK. Seifert, is largely credited with pioneering the application ofbiological marker technology to petroleum exploration. Cambridge University Presswww.cambridge.org
Cambridge University Press0521781582 - The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History,Second EditionK. E. Peters, C. C. Walters and J. M. MoldowanFrontmatterMore informationThe Biomarker GuideSecond EditionI. Biomarkers and Isotopes in the Environmentand Human HistoryK. E. PetersUS Geological Survey, Menlo Park, CA, USAC. C. WaltersExxonMobil Research & Engineering Co.,Corporate Strategic Research, Annandale, NJ, USAJ. M. MoldowanDepartment of Geological and Environmental Sciences,School of Earth Sciences, Stanford, CA, USA Cambridge University Presswww.cambridge.org
Cambridge University Press0521781582 - The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History,Second EditionK. E. Peters, C. C. Walters and J. M. MoldowanFrontmatterMore informationpublished by the press syndicate of the university of cambridgeThe Pitt Building, Trumpington Street, Cambridge, United Kingdomcambridge university pressThe Edinburgh Building, Cambridge CB2 2RU, UK40 West 20th Street, New York, NY 10011-4211, USA477 Williamstown Road, Port Melbourne, VIC 3207, AustraliaRuiz de Alarcón 13, 28014 Madrid, SpainDock House, The Waterfront, Cape Town 8001, South Africahttp://www.cambridge.orgC Chevron Texaco Exploration and Production Company 1993First edition C Cambridge University Press 2005Second edition This book is in copyright. Subject to statutory exceptionand to the provisions of relevant collective licensing agreements,no reproduction of any part may take place withoutthe written permission of Cambridge University Press.First published 1993 by Prentice Hall, Inc.Second edition published 2005 by Cambridge University PressPrinted in the United Kingdom at the University Press, CambridgeTypeface Ehrhardt 9.5/12 ptSystem LATEX 2ε [tb]A catalog record for this book is available from the British LibraryLibrary of Congress Cataloging in Publication dataPeters, Kenneth E.The biomarker guide. – 2nd ed. / K. E. Peters, C. C. Walters, and J. M. Moldowan.p. cm.Includes bibliographical references and index.Contents: 1. Biomarkers in the environment and human history – 2. Biomarkers in petroleum systems and Earth history.ISBN 0 521 78158 21. Petroleum – Prospecting. 2. Biogeochemical prospecting. 3. Biochemical markers. I. Walters, C. C. (Clifford C.)II. Moldowan, J. M. (J. Michael), 1946– III. Title.TN271.P4P463 2004622 .1828–dc222003065416ISBN 0 521 78158 2 hardback vol. 1ISBN 0 521 83762 6 hardback vol. 2ISBN 0 521 83763 4 set of two vols. Cambridge University Presswww.cambridge.org
Cambridge University Press0521781582 - The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History,Second EditionK. E. Peters, C. C. Walters and J. M. MoldowanFrontmatterMore informationDedicated toVanessa, Brent, and MiwokJohnetMary Cambridge University Presswww.cambridge.org
Cambridge University Press0521781582 - The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History,Second EditionK. E. Peters, C. C. Walters and J. M. MoldowanFrontmatterMore informationContentsAbout the authorsPrefacePurposeAcknowledgmentspage ixxixvixviiChiralityOptical activityNaming asymmetric centers (R, S, α,and β)StereoisomerizationStereochemistry of selected biomarkersExercisePART I BIOMARKERS ANDISOTOPES IN THE ENVIRONMENTAND HUMAN HISTORY1 Origin and preservation of organicmatterIntroduction to biomarkersDomains of lifePrimary productivitySecondary productivityPreservation of organic matterOrganic components in rocksOxic versus anoxic depositionSedimentation rate and grain sizeLacustrine versus marine depositionalsettingsTemporal and regional distributions ofsource rocks2 Organic chemistryAlkanes: the sigma bondAlkenes: the pi bondAromatics: benzeneStructure notationThree-dimensional projections totwo-dimensional spaceAcyclic alkanesAcyclic alkenesMonocyclic alkanesMulti-ringed cycloalkanesThe isoprene ruleAromatic hydrocarbonsHeteroatomic moleculesStereochemistry and nomenclature3 Biochemistry of biomarkersLipid membranesMembrane lipidsLipid membrane fluidityBiosynthesis of terpenoidsHopanoids and sterols in the biosphereand geospherePorphyrins and other biomarkers ofphotosynthesisCarotenoids333589910134 Geochemical screeningSource-rock screening: quality andquantitySource-rock screening: thermalmaturityGeochemical logs and source potentialindexReconstruction of original source-rockgenerative potentialTests for indigenous bitumenDetection of petroleum in prospectivereservoir rocksCrude oil screeningReservoir continuity and filling historySurface geochemical exploration usingpiston coresSample quality, selection, and storageGeochemical rock and oil standardsAppendix: derivation of 109111113116117vii Cambridge University Presswww.cambridge.org
Cambridge University Press0521781582 - The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History,Second EditionK. E. Peters, C. C. Walters and J. M. MoldowanFrontmatterMore informationviiiContents5 Refinery oil assaysBasic oil assaysAdvanced oil assaysPetroleum refiningBiomarkers in refinery products1191201271291346 Stable isotope ratiosStandards and notationStable carbon isotope measurementsStable carbon isotope fractionationConverting δ values using differentstandardsApplications of stable carbon isotope ratiosCompound-specific isotope analysisSulfur and hydrogen isotopes1361361371387 Ancillary geochemical methodsDiamondoidsC7 hydrocarbon analysisCompound-specific isotope analysis oflight hydrocarbonsMolecular modelingFluid inclusions1571571628 Biomarker separation and analysisOrganization of a biomarker laboratorySample clean-up and separationsInternal standards and preliminaryanalysesZeolite molecular sievesGas chromatography/mass spectrometryMass spectra and compoundidentificationBiomarker quantitation1981981999 Origin of petroleumHistorical backgroundDeep-earth gas hypothesisAbiogenic hydrocarbon gasesThermogenic hypothesis25225225325625910 Biomarkers in the environmentEnvironmental markersOil spills Cambridge University Processes affecting the fate of marine oilspillsMitigation of oil spillsModeling marine oil spillsOil spills on landUnderground leakageToxicity of petroleumEnvironmental chemistry field andlaboratory proceduresChemical fingerprinting of oil spillsAnalysis of biomarkers and polycyclicaromatic hydrocarbons in oil-spillstudiesApplications of biomarkers andpolycyclic aromatic hydrocarbons tooil-spill studiesBiomarkers and the Exxon Valdezoil spillGasoline and other light fuels aspollutantsNatural gas as a pollutantBiomarkers in smoke27928228328328328428728929429830531231531911 Biomarkers in archeologyThe ages of manOrigins and transport of petroliferousmaterials in antiquityArcheological gums and resinsBiomarkers in artArcheological wood tars (pitch)Paleodiets and agricultural practicesArcheological beeswaxBiomarkers and manuring practicesArcheological DNAAncient proteinsArcheological narcoticsBiomarkers and interdisciplinary studies322322Appendix: geologic time 334338344346347349350352www.cambridge.org
Cambridge University Press0521781582 - The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History,Second EditionK. E. Peters, C. C. Walters and J. M. MoldowanFrontmatterMore informationAbout the authorsKenneth E. Peters is currently Senior ResearchGeologist at the US Geological Survey in Menlo Park,California, where he is involved in one-dimensional(1D), two-dimensional (2D), and three-dimensional(3D) petroleum system modeling of the North Slopeof Alaska, the San Joaquin Basin, and elsewhere. Heattained B.A. and M.A. degrees in geology from University of California, Santa Barbara, and a Ph.D. in geochemistry from University of California, Los Angeles,(UCLA) in 1978. His experience includes 15 years withChevron, 6 years with Mobil, and 2 years as Senior Research Associate with ExxonMobil. Ken taught formalcourses in petroleum geochemistry and thermal modeling for Chevron, Mobil, ExxonMobil, Oil and Gas Consultants International, and at various universities, including University of California, Berkeley, and StanfordUniversity. He served as Associate Editor for OrganicGeochemistry and the American Association of PetroleumGeologists Bulletin. Ken and co-authors received theOrganic Geochemistry Division of the Geochemical Society Best Paper Awards for publications in 1981 and1989. He served as Chair of the Gordon Research Conference on Organic Geochemistry (1998) and Chair ofthe Organic Geochemistry Division of the GeochemicalSociety (2001–2004).Clifford C. Walters received Bachelor degreesin chemistry and biology from Boston University in1976. He attended the University of Maryland, wherehe worked on the chemistry of Martian soil and conducted field and laboratory research on metasedimentsfrom Isua, Greenland, the oldest sedimentary rockson Earth. After receiving a Ph.D. in geochemistry in1981, Cliff continued with postdoctoral research on theorganic geochemistry of Precambrian sediments andmeteorites. He joined Gulf Research and Developmentin 1982, where he implemented a program in biologicalmarker compounds. In 1984, he moved to Sun Exploration & Production Company, where he was responsible for technical service and establishing biomarkergeochemistry and thermal modeling as routine exploration tools. Mobil’s Dallas Research Lab hired Cliffin 1988, where he became Supervisor of the Geochemical Laboratories in 1991. He is now Senior ResearchAssociate with ExxonMobil Research and EngineeringCompany, where he conducts work on the modeling ofoil generation and reservoir transformations, geomicrobiology, and processes of solids formation. Cliff published numerous papers, served as Editor of the ACSGeochemistry Division from 1990 to 1992, and is a current Associate Editor of Organic Geochemistry.J. Michael Moldowan attained a B.S. in chemistryfrom Wayne State University, Detroit, Michigan, and aPh.D. in chemistry from the University of Michigan in1972. Following a postdoctoral fellowship in marine natural products with Professor Carl Djerassi at StanfordUniversity, he joined Chevron’s Biomarker Group in1974. The Chevron biomarker team, led by the lateDr. Wolfgang K. Seifert in the mid 1970s to early 1980s,is largely credited with pioneering the application of biological marker technology to petroleum exploration.Mike joined the Department of Geological and Environmental Sciences of Stanford University as Professor (Research) in 1993. In 1986, he served as Chair ofthe Division of Geochemistry of the American Chemical Society, and he has twice been awarded the OrganicGeochemistry Division of the Geochemical Society BestPaper Award for publications he co-authored in 1978and 1989.ix Cambridge University Presswww.cambridge.org
Cambridge University Press0521781582 - The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History,Second EditionK. E. Peters, C. C. Walters and J. M. MoldowanFrontmatterMore informationPrefaceBiological markers (biomarkers) are complex molecularfossils derived from biochemicals, particularly lipids, inonce-living organisms. Because biological markers canbe measured in both crude oils and extracts of petroleumsource rocks, they provide a method to relate the two(correlation) and can be used by geologists to interpretthe characteristics of petroleum source rocks when onlyoil samples are available. Biomarkers are also useful because they can provide information on the organic matter in the source rock (source), environmental conditions during its deposition and burial (diagenesis), thethermal maturity experienced by rock or oil (catagenesis), the degree of biodegradation, some aspects ofsource rock mineralogy (lithology), and age. Becauseof their general resistance to weathering, biodegradation, evaporation, and other processes, biomarkers arecommonly retained as indicators of petroleum contamination in the environment. They also occur with certain human artifacts, such as bitumen sealant for ancient boats, hafting material on spears and arrows, burialpreservatives, and as coatings for medieval paintings.Biomarker and non-biomarker geochemical parameters are best used together to provide the mostreliable geologic interpretations to help solve exploration, development, production, and environmentalor archeological problems. Prior to biomarker work,oil and rock samples are typically screened using nonbiomarker analyses. The strength of biomarker parameters is that they provide more detailed informationneeded to answer questions about the source-rockdepositional environment, thermal maturity, and thebiodegradation of oils than non-biomarker analysesalone.Distributions of biomarkers can be used to correlate oils and extracts. For example, C27 -C28 -C29 steranesor monoaromatic steroids distinguish oil-source families with high precision. Cutting-edge analytical techniques, such as linked-scan gas chromatography/massspectrometry/mass spectrometry (GCMS/MS) provide sensitive measurements for correlation of light oilsand condensates, where biomarkers are typically in lowconcentrations. Because biomarkers typically containmore than 20 carbon atoms, they are useful for interpreting the origin of the liquid fraction of crude oil, butthey do not necessarily indicate the origin of associatedgases or condensates.Different depositional environments are characterized by different assemblages of organisms and biomarkers. Commonly recognized classes of organisms include bacteria, algae, and higher plants. For example,some rocks and related oils contain botryococcane, abiomarker produced by the lacustrine, colonial algaBotryococcus braunii. Botryococcus is an organism thatthrives only in lacustrine environments. Marine, terrigenous, deltaic, and hypersaline environments also showcharacteristic differences in biomarker composition.The distribution, quantity, and quality of organicmatter (organic facies) are factors that help to determinethe hydrocarbon potential of a petroleum source rock.Optimal preservation of organic matter during and after sedimentation occurs in oxygen-depleted (anoxic)depositional environments, which commonly lead toorganic-rich, oil-prone petroleum source rocks. Various biomarker parameters, such as the C35 homohopaneindex, can indicate the degree of oxicity under whichmarine sediments were deposited.Biomarker parameters are an effective means torank the relative maturity of petroleum throughout theentire oil-generative window. The rank of petroleum canbe correlated with regions within the oil window (e.g.early, peak, or late generation). This information canprovide a clue to the quantity and quality of the oil thatmay have been generated and, coupled with quantitative petroleum conversion measurements (e.g. thermalmodeling programs), can help evaluate the timing ofpetroleum expulsion.xi Cambridge University Presswww.cambridge.org
Cambridge University Press0521781582 - The Biomarker Guide: Biomarkers and Isotopes in the Environment and Human History,Second EditionK. E. Peters, C. C. Walters and J. M. MoldowanFrontmatterMore informationxiiPrefaceBiomarkers can be used to determine source andmaturity, even for biodegraded oils. Ranking systemsare based on the relative loss of n-alkanes, acyclicisoprenoids, steranes, terpanes, and aromatic steroidsduring biodegradation.Biomarkers in oils provide information on thelithology of the source rock. For example, the absenceof rearranged steranes can be used to indicate petroleumderived from clay-poor (usually carbonate) sourcerocks. Abundant gammacerane in some petroleum appears to be linked to a stratified water column (e.g.salinity stratification) during deposition of the sourcerock.Biomarkers provide information on the age of thesource rock for petroleum. Oleanane is a biomarkercharacteristic of angiosperms (flowering plants) foundonly in Tertiary and Upper Cretaceous rocks and oils.C26 norcholestanes originate from diatoms and can beused to distinguish Tertiary from Cretaceous and Cretaceous from older oils. Dinosterane is a marker for marine dinoflagellates, possibly distinguishing Mesozoicand Tertiary from Paleozoic source input. Unusual distributions of n-alkanes and cyclohexylalkanes are characteristic of Gloeocapsomorpha prisca found in earlyPaleozoic samples. 24-n-Propylcholestane is a markerfor marine algae extending from at least the Devonianto the present.Continued growth in the geologic, environmental,and archeological applications of biomarker technologyis anticipated, particularly in the areas of age-specificbiomarkers, the use of biomarkers to indicate sourceorganic matter input and sedimentologic conditions,correlation of oils and rocks, and understanding theglobal cycle of carbon. New developments in analyticalmethods and instrumentation and the use of biomarkers to understand petroleum migration and kinetics arelikely. Finally, early work suggests that biomarkers willcontinue to grow as tools to understand production,environmental, and archeological problems.HOW TO USE THIS GUIDEThe Biomarker Guide is divided into two volumes. Thefirst volume introduces some basic chemical principlesand analytical techniques, concentrating on the studyof biomarkers and isotopes in the environment and human history. The second volume expands on the usesof biomarkers and isotopes in the petroluem industry, Cambridge University Pressand investigates their occurrence throughout Earthhistory.The Biomarker Guide was written for a diverseaudience, which might include the following:r students of geology, environmental science,
chemistry and thermal modeling both in industry and at var- . First published 1993 by Prentice Hall, Inc. . Modeling marine oil spills 283 Oil spills on land 283 Underground leakage 283 Toxicity of petroleum 284 Environmental chemistry field and laboratory procedures 287
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