Chromatography in the petroleum industry

Chromatography in the petroleum industry

Org. Geochem. Vol. 23, No. 7, pp. 709-710, 1995 ~ Pergamon 0146-6380(95)00038-0 Copyright © 1995 Elsevier Science Ltd Printed in Great Britain. Al...

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Org. Geochem. Vol. 23, No. 7, pp. 709-710, 1995

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Pergamon

0146-6380(95)00038-0

Copyright © 1995 Elsevier Science Ltd Printed in Great Britain. All rights reserved 0146-6380/95 $9.50 + 0.00

BOOK REVIEWS

An Introduction to Organic Geochemistry,by S. D. KILLOPS and V. J. KILLOPS. J. Wiley and Sons Inc., New York.

to the more technical material used in the text. Although the cover of this book has the "geo" of geochemistry in bold letters, the emphasis and the choice o f topics is towards chemical rather than geological aspects. I suspect that this reflects the bias of the authors' backgrounds and the types of students they have taught. Topics that might reasonably be expected in an organic geochemistry course given to geologically oriented students, such as the use of wireline logs to locate source rocks, source rock deposition in a sequence stratigraphic framework or inorganic-organic diagenetic relationships, are not (or only extremely briefly) covered. Also, there is no real discussion of the reasons why oil and gas are thought to be derived ultimately from biogenic organic matter. Many students and oil company geologists have read the theories proposed for an abiogenic origin by people such as Thomas Gold and C. Warren Hunt in the popular press and want to know why these authors are considered to be on the fringe of science. Overall, the book achieves most of the authors' objectives. It can be recommended as a possible textbook for students taking a chemically oriented course, and would be useful background for geological students as well. This book is unlikely to appeal to "professional petroleum geochemists" because of its conciseness and the availability of other, more thorough and applied publications.

The stated intentions of the authors is to "attempt to present a readily accessible, up-to-date and integrated introduction to organic geochemistry, at a reasonable price". It is aimed at undergraduate and postgraduate students with the assumption that they have some basic background chemistry. The book has eight chapters. Chapter 1 is entitled "Production and Fate of Organic Matter". It deals briefly with the carbon cycle and the evolution of the major contributors to organic matter found in sediments. The "Chemical Composition of Biogenic Matter" is discussed in some detail in Chapter 2. The authors should be complimented in this chapter for trying to explain the chemical nomenclature used to identify the compounds mentioned, such as carbohydrates, fatty acids, etc. Chapter 3 is concerned with the "Conditions for the Accumulation o f Organic-Rich Sediments". Topics discussed include the factors influencing primary production and the preservation of organic matter, and the environments favourable for organic carbon accumulation. "The Formation of Humic Material, Coal and Kerogen" is covered in Chapter 4. This includes a discussion of the currently favoured theories of kerogen formation (i.e., the classical biopolymers~geomonomers---, geopolymers version and the selective preservation model), as well as kerogen classification and changes in kerogen structure with maturation. Chapter 5 deals with the generation, migration and composition of petroleum. It also includes a brief and somewhat unsatisfactory discussion of kinetic models of petroleum formation that concentrates mostly on TTI calculations. For some reason, a section on the assessment of petroleum source rocks is in this chapter and not in the preceding kerogen chapter. One annoying aspect of this section is that it perpetuates the myth of source rocks occurring with TOC contents less than 1%. Besides empirical evidence, a number of recent papers have presented evidence that explains why rocks with such low TOC contents are unlikely to be oil source rocks. The next two chapters look at biomarkers in recent sediments and then in ancient sediments and oils. These topics are covered in some detail and in a fairly readable way. The final chapter is unusual for organic geochemistry textbooks which have tended to concentrate on petroleum geochemistry, as it is on the "'Environmental Behaviour of Anthropogenic Organic Compounds". Amongst the topics covered are the influence of man on the carbon cycle including some discussion of the factors influencing global warming, halocarbons and ozone depletion, and the impact of chlorinated compounds such as DDT and PCBs on the environment. I congratulate the authors for including this topic. Based on my own experience, this section could have been expanded. One of the reasons that organic geochemistry is becoming more widely taught is that the environmental aspect is, at present, more popular with students than the petroleum aspect. The book provides a concise overview on most aspects of organic geochemistry, in a reasonably cheap (US$41.95) paperback form with plenty of figures. The book is theoretically based. Few examples are given and no problems provided. Boxes are used to provide some background OG

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Geological Survey of Canada, Calgary, Canada

M A R T I N G. F O W L E R

Chromatographyin thePetroleumIndustry,Edited by E. R. A D L A R D . Journal of Chromatography Library, Vol. 56. Elsevier Science B.V., Amsterdam. 1995. 452pp. ISBN 0-444-89776-3, Hardbound. Price DFL. 435.00/US$ 248.50. A large portion of organic geochemical research relies on chromatographic separations, and the landmark 1979 volume Chromatography in Petroleum Analysis, edited by K.H. Altegelt and T.H. Gouw, occupies a cherished position among our discipline's fundamental references. Chromatography in the Petroleum Industry, edited by E.R. Adlard, is the first volume in 16 years dedicated to this topic. This book (Volume 56 of the Journal of Chromatography Library) is not a set of reprints, but a collection of 14 original articles written by experts in their field. The articles vary from literature reviews to detailed descriptions of specific chromatographic techniques. Although the authors clearly had considerable freedom in the manner that they approached their topics, the volume has been edited carefully so that the text, figures, tables, and references have a uniform style. Most of the chapters are current, with references as late as 1993; however, the style used for listing these references is not to my liking, as titles are not included. The articles are arranged by chromatographic technique. The first four chapters deal with refinery-related applications. The next five are on gas chromatography (GC). This is followed by two chapters on supercritical fluid chromatography (SFC) and individual chapters on liquid chromatography (LC), data processing, and capillary electrophoresis (CE). Although not all of the 709

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Book Reviews

chapters are pertinent to the typical reader of Organic Geochemistry, most have some relevance. The opening chapter by C.J. Cowper is one of the most comprehensive in the book, offering both a historical perspective and a detailed description of the various gas chromatographic techniques used for the analysis of C,-C~0 hydrocarbon and non-hydrocarbon gases. The methods depicted range from single packed columns, to hybrid multi-detector systems involving elaborate column switching, to rapid microcolumn instrumentation. Each procedure is illustrated with a chromatogram showing the achieved separation, and a flow diagram is provided for every system that uses multiport valves. A. Barker's comprehensive review of modern chromatographic analysis of waxes deals with refined and synthetic long chained (C40-C90+) n-alkanes, although the high temperature GC, SFC, and size exclusion chromatography (SEC) techniques are applicable to studies of high molecular weight hydrocarbons in the geosphere. The other two refinery-related chapters are literature reviews of simulated distillation (D.J. Abbott) and hydrodynamic chromatography of polymers (J. Bos and R. Tijssen). The gas chromatography section begins with an article by S.J. Rowland and A.T. Revill on chromatography in petroleum geochemistry. Rather than attempt to be comprehensive, the authors of this all-too-short chapter summarize some recent advances in pyrolysis-GC, separation techniques, and hyphenated-methods. On too many topics of major importance, such as biomarkers and compound-specific isotope analyses, the reader is referred to previous reviews and other sources. Fortunately, the references for the period of 1988-1992 are extensive. While the shallow treatment of petroleum geochemistry is disappointing, the chapter provides pointers to other sources. The next three chapters are thorough and complete descriptions of element-specific GC detectors: the oxygen flame ionization detector (A. Sironi and G.R. Verga), the microwave plasma spectrometer (A. de Wit and J. Beens), and the sulfur chemiluminescence detector (R.S. Hutte). Each paper explains the theory and mechanics of the element-specificity, the day-to-day operations, and the limitations of the detector. Tables of model compound response factors and numerous chromatograms are included. Anyone engaged in method development utilizing these detectors could save themselves considerable time and wasted effort by studying these articles. The final chapter in this section is on multi-dimensional GC (H. Mahler, T. Maurer, and F. Miiller). Multi-column systems using mechanical valving and valveless flow switching are described, though the authors do not hide their preference for the latter method. The improvements in speed and separation that can be achieved by multi-column techniques, such as backflushing, stopped flow, recycling, and heart cutting, are adequately explained and illustrated. The authors' approach is to convey the power and potential of these techniques and to provide a procedure for evaluating the benefits that one could gain from multi-column GC. Descriptions of specific applications in the detail that would permit the reader to replicate the methods are left to the referenced publications. Two papers involving supercritical fluid extraction (T.P. Lynch) and chromatography (J. Roberts) have some overlap, but are mostly complementary reviews of the current

literature. Combined, these chapters provide thorough descriptions of SCF instrumentation, solvent selection, interfacing to detectors, and hyphenated techniques. Most of the illustrated applications are directed at refinery-related analyses (e.g. hydrocarbon group-type and aromatic-ring separation and simulated distillation). There are fewer applications of SFC to natural samples, though the potential is apparent (e.g. hydrocarbon separations beyond C~40can be achieved in under 30 minutes.) The single chapter on liquid chromatography (A.C. Neal) is a literature review. Following a description of typical HPLC instrumentation and a fairly thorough review of the numerous detectors is the author's summary of applications (limited mostly to refinery-related topics). None of these applications are illustrated with example chromatograms. LC applications to organic geochemistry are ignored, with no mention of petroporphyrins, organic acids, or other functionalized lipids. Although this is consistent with the book's focus on industry-related separations, the narrow interpretation restricts this chapter's utility. Researchers involved with the analysis of PAH may find new methods for consideration. The last two chapters seem slightly out of place. One article, by N. Dyson is on electronic data processing. All major aspects of modern data collection, integration, and reporting are described; this information is as applicable to spectroscopy or any other time-dependent data as it is to chromatography. Dyson should be complemented for focusing on the errors and limitations that afflict automatic data processing procedures. This disclosure is much more helpful than repeating the idealized situations found in most technical manuals. The last chapter is on capillary electrophoresis (T. Jones and G. Bondoux), a technique used widely in pharmaceutical and biochemical research but with limited application in petroleum characterization. The inherent molecular complexity of the geosphere often drives geochemists towards the forefront of chromatographic techniques. Chromatography in the Petroleum Industry will prove to be a valuable reference to readers of Organic Geochemistry engaged in chromatographic analyses. The volume, nevertheless, is not as comprehensive as I would have wished. Little to no information is provided on the assorted mass spectrometric and infrared detectors that comprise many of our hybrid chromatographic systems. The volume ignores many of the newer stationary bonded phases that extend the range of available polarity, chiral GC and LC separations, advances in instrumentation such as injection techniques and electronic pressure control, and thin layer chromatography. Moreover, the scope of the book prevents the inclusion of chromatography of functionalized lipids from modern sediments. While I can strongly recommend purchase of this book by academic and industrial libraries, its high cost and restricted appeal will limit possession by individuals. Chromatography in the Petroleum Industry is available by direct purchase from the publisher at either P.O. Box 211, 1000 AE Amsterdam, The Netherlands (31-0205803-642) for Dfl. 435.00 or P.O. Box 945 Madison Square Station, New York, NY 10159-0945 (1-212-633-3650) for US$248.50.

Mobil Research CLIFFORD C. WALTERS & Development Corporation, 13777 Midway Road, Dallas, TX 75244-4312, U.S.A.