Petroleum and Coal. Source Rocks

fraction. The kerogen fraction of any organic-rich rock contains the bulk ofthe organic carbon and can be thought of as that fraction which remains af...
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Source Rocks R. Paul h i l p

School of Geology and Geophysics, Univemty of Oklahoma, Noman, Oklahoma 73079 petroleum zones using this technique. In the course of source Source rocks are the organic-rich rocks responsible for the sourcing of oil or natural gas. Such rocks generally have relatively rock appraisal, a great deal of emphasis is place upon the high total organic carbon (TOC) content and may be at varying extraction and Characterization of the soluble organic matter. Traditionally, the extraction process has involved some form of levels of thermal maturity. A source rock can be divided into two solvent extraction system using a wide variety of solvent mixtures. main parts, namely, the organic fraction and the inorganic, or In the past few years, several papers have started to appear mineral matrix. The organic fraction can be further divided into describing the use of supercritical fluid extraction (SFE) using a solvent-extractable fraction and solvent-insoluble, or kerogen, COzwith and without modi6ers to extract the organic matter from fraction. The kerogen fraction of any organic-rich rock contains source rocks. Greibrokk et al. (F3) described a multistage SFE the bulk of the organic carbon and can be thought of as that process for the extraction of source rocks and its application to fraction which remains after the soluble organic material has been Kimmeridge clay and Posidonia shale formation samples. The removed by extraction and the insoluble mineral matrix has been extractions were performed with COz alone and also mixed with removed by dissolution with various acids. Kerogen generally small amounts of 2-propanol, CS, or THF added to increase yields. represents more than 90% of the total organic fraction in the A similar approach using only COZto extract organic matter from original source rocks. Despite this, kerogens have not been a peat, low-rank coal and a bituminous oil shale was described by analyzed to the same extent as the soluble fractions due to the Martin et al. (F4). Selectivity and yields using the SFE approach practical daculties in analyzing this highly insoluble organic were studied by Skurdal et al. (F5)using both tar mats and source material. Most of the commonly used techniques for kerogen rocks in a multistage extraction process. The extracts were characterization generally involve some type of solubilization prior collected on CISsorbent cartridges prior to analysis. The use of to an analytical step. The most commonly used degradation thermal extraction processes coupled directly with GC has also technique at the present time is some sort of pyrolysis combined received some attention, and Bjoroey et al. (F6) described a with either gas chromatography (GC) or gas chromatography/ hydrocarbon analyzer that could be used at the well site or in the mass spectrometry (GC/MS). Previously, oxidation was the laboratory for the direct characterization of source rock hydromethod of choice for degradation,but this approach has not been carbons. used as much in recent years. Direct characterization of the After the extraction process, regardless of whether SFE or kerogen fraction typically involves some sort of spectroscopic solvent extraction is used, the extracts need to be fractionated technique such as solid-state NMR electron spin resonance 0, and subsequentlyanalyzed typically by GC or GC/MS. Harriman or Fourier transform IR (F7) gave a general review of the role of gas chromatography in In the following discussion, the first part will review papers petroleum exploration, and Le Tran and Phillippe (F8) also published in the last two years and concerned with the characreviewed the use of GC in an article concerned with characterizaterization of the solvent-solublefractions of the source rocks. The tion of oil and rock extracts. Fractionation of the initial extracts second part will review recent developments in the characterizahas traditionally involved the use of well-defined chromatography tion of the insoluble fraction, including techniques that are methods such as column chromatography,thin-layer chromatogconcerned with both the degradation kerogens and spectroscopic raphy, or high-performance chromatography. Wang et al. (F9, characterization of the kerogen fractions. F10) have described a rapid, reliable, and effective method for the separation of petroleum into aliphatic and aromatic hydrocarSOURCE ROCK EXTRACTS A source rock consists of three major phases: (i) extractable bons using a 3-g silica gel glass microchromatography column. organic material; (ii) insoluble organic material or kerogen; (iii) The procedure yielded very clean separations for light Alberta mineral matter. For the purposes of this review, emphasis is crude oils, and up to 50 mg of oil could be quantilied with this placed on the two phases containing the organic matter. The technique. A column chromatography technique to fractionate source rock is one of the most important factors in any search aromatic compoundsfrom ancient and recent sediments to provide for new hydrocarbon resources. Poor-quality source rocks will access to the distribution of isomeric compounds in various not produce any oil, overmature source rocks will have already alkylated aromatic families was described by Budzinski et al. generated their hydrocarbon charge, and immature rocks may (F11).The distributions were used for assessment of the origin not have reached the oil or gas generation stage. Hence, it is and maturity of the organic matter in recent and ancient sediimportant in any exploration program to be able to qualitatively ments. Until recently, the upper temperature limits for most and quantitatively characterize the organic content of any potential conventional GC columns was in the range of 300-350 "C, source rocks. Bertrand et al. (Fl) reviewed the methods available meaning that for the most part hydrocarbons up to approximately to evaluate geochemical parameters related to source rock C ~could O be determined by GC. More recently the advent of highappraisal and their application to petroleum prospecting. A more temperature GC columns with phases stable up to 460 "C has specific approach to detect and evaluate hydrocarbons in source lead to the determination of hydrocarbons up to CIWand above. rocks by fluorescence microscopy was described by Alpern et al. Del Rio and Philp provided one of the first descriptions of the (FZ).Monochromatic fluorescence parameters of hydrocarbons use of these columns to determine high molecular weight trapped in the embedding resin could be determined and corhydrocarbons in various crude oils and waxes (F1Z).Van Aarssen related with selected geochemical parameters. Application to real et al. (F13)also used this approach to study high molecular weight case studies showed that it was possible to directly detect mature substances in resinites as possible precursors of specific hydroAnalytical Chernisfty, Vol. 67, No. 12, June 15, 1995

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carbons in fossil fuels. Hydrocarbon fractions from source rocks typically are extremely complex mixtures of a wide variety of compounds. Further simplification of these fractions can be undertaken with various procedures such as molecular sieving. A variety of molecular sieves have been described in the literature for the attempted isolation of specitic compounds or compound classes, and Armanios et al. (2714) described the shape-selective sorption of petroleum hopanoids by ultrastable Y zeolite. This sieve permitted the separation of the hopanoids based on the shape and size of their carbon skeletons. Aramnios et al. (F15) also demonstrated the use of the same sieve as a stationary phase in a liquid chromatography procedure using pentane as the liquid phase. The fractions obtained were isolated by GUMS. It was observed in the case of samples derived from higher plant sources that it was possible to obtain fractions particularly enriched in bicadinanes, a-spiroterpane, oleananes, and taraxastanes. Cadinanes and homocadinanes could also be enriched by this procedure. There have been many papers written over the past two decades concerned with the discovery and use of biomarkers in crude oils and source rocks, and many of these have been listed in the previous versions of this review. Recently, Ourisson and Albrecht (F16) reviewed the history of the discovery of hopane and its derivatives in plants and the identification of the gechopanoids in sedimentary organic matter and crude oils. The various uses of the hopane distributions in petroleums are discussed as well as some recent applications to archeology. The origin and occurrence of one specific group of hopanes, namely, the 25norhopanes, are discussed in detail by Blanc and Connan (F17). The article concludes that the 25norhopanes are preexisting biomarkers whose concentrations are enhanced by selective biodegradation of the more readily degradable homologs or regular hopanes. A number of non-hopanoid pentacyclic terpanes derived from higher plant precursors have been compared and characterized using electron impact mass spectrometry and tandem mass spectrometry (2718). It was observed that the collision-activated decomposition spectra and electron impact mass spectra showed the greatest similarities at collision energies between -15 and -20 eV. Porphyrins have been used extensively for a variety of geochemical purposes, and Lash (F19) discussed the geochemical origins of both benzoporphyrins and tetrahydrobenzoporphyrins from a number of oil shales and oils. Possible mechanisms for the formation of these benzoporphyrins were also discussed in this paper. Ocampo et al. (F20)described the use of petroporphyrins in oil/oil and oil/source rock correlation studies and compared the results with those obtained from terpanes and steroids. It was observed that the terpane and steroid distributions suggested a common origin for the oils examined whereas the porphyrin distributions were strikingly different and suggested that the oils had different origins, history, or both. Sundararaman and Moldowan (F21) describe a comparative study between samples of various maturities based on steroid and vanadylporphyrin parameters, including a new parameter suitable for use at higher levels of maturity. Mechanisms responsible for changes in various porphyrin maturation parameters were discussed by Sundararaman (F22). The ratios vary as a result of differences in rates of decomposition of the DPEP and ETIO porphyrins as well as variations in rate of release of bound ETIO porphyrins from the kerogen during the early stages of diagenesis. Pretorius 344R

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et al. (F23)have discussed the development of a high-temperature GWinductively coupled plasma mass spectrometer interface and its use for the system for the analysis of synthetic and geological metalloporphyrins. In other studies related to source rock extracts, Price 0724) has described the thermal stability of hydrocarbons in nature. It was concluded that organic matter metamorphic reactions proceed by reaction kinetics other than first order and thus the effect of geologic time appears to have been overestimated in organic matter metamorphism. Price (F24) also proposed that strong decreases in CIS+ hydrocarbon concentrations in fine-grained rocks with type I11 organic matter over Ro 0.9-1.35% are probably due to intense primary migration and loss of hydrocarbons to drilling muds during the trip uphole in drilling operations. Fan et al. (F25) provided a review of biomarkers associated with nonmarine crude oils from China which also included some information on organosulfur compounds and stable isotope characteristics of these samples. Thiophenic compounds in Sunniland oils and source rocks from the South Florida Basin have been discussed by Xng and Fan (F26) and used for correlation purposes along with the hydrocarbon biomarkers. A comprehensive petrological and geochemical study of peat samples from a raised bog in Kalimantan (Borneo) has been described by Dehmer (F27). The study was initiated to illustrate changes during peatification. It was observed that peats from the margins of the raised bog were more decomposed than peats from the center of the bog. The effects of an igneous intrusion on the organic geochemistry of a siltstone and an oil shale horizon in the Midland Valley of Scotland were studied by George (F28). Maturity parameters based on the alkylnaphthalene and alkylphenanthrene isomer ratios were more suitable for studying maturity variations in heat-affected samples than those based on the commonly used aliphatic biomarkers. These aromatic compounds survive to higher ranks, and the isomer ratios continue to change at the higher levels of maturiw. Altbach and Fitzpatrick (F29)used two-dimensional NMR spectroscopy to identify conjugated olefins in fossil fuel liquids such as shale oils. The most recent technique to be used in the study of source rock extracts and crude oils is the combined gas chromatograph/ isotope ratio mass spectrometer, which permits the determination of the isotopic composition of individual components in very complex mixtures. Several papers have appeared in the literature using this approach. Chicarelli et al. (F30) described the carbon and nitrogen isotopic compositions of alkylporphyrins from the Triassic Serpiano oil shale and discussed possible origins for these compounds on the basis of the isotope compositions. Bjoroey et al. (F31) studied variations in the stable isotope compositions of individual hydrocarbons as a function of &cia1 maturity and noted an enrichment in the I3C content of alkanes, isoprenoids, and terpenoids at higher levels of maturity. A similar approach was used by Wilhelms et al. (F32) in a comparative study of the stable carbon isotopic composition of the crude oil alkanes and associated crude oil asphaltene pyrolysate alkanes. Results indicated possible differences in the sources for the alkanes in the oils vs n-alkyl moieties in the asphaltenes. Mycke et al. (F33) undertook a similar study but performed the pyrolysis in a microscale sealed vessel and measured the isotopic composition of specific gases and nongaseous components. A relationship between the isotopic composition of pyrolytically generated CO?

and the depositional paleoenvironments of the candidate source rocks was observed. SOURCE ROCK MATURATION AND KEROGEN CHARACTERIZATION In many applications,it is necessary to artificially mature source rock samples in the laboratory in order to predict the types of products they might generate at depths in a basin below that penetrated by the drill bit. Various methods have been developed over the years and reviewed in previous versions of this article. Landais et al. (F34) have described both off-line and on-line methods for characterizing products generated during artiticial maturation of organic matter using contined pyrolysis. Confined pyrolysis has also been used by Blanc and Connan (F35) to study the generation and expulsion of hydrocarbons from a Paris Basin Toarcian source rock. It was observed that high-pressure conditions favored the expulsion of polar/macromolecular compounds and had a negative effect on hydrocarbon generation from organic matter. Analysis of confined pyrolysis effluents by thermodesorption multidimensional gas chromatography has been described by Gerard et al. (F36),using artificially matured samples from both the Paris Basin and the Mahakam delta. FT-IR was used to monitor chemical modifications taking place in the organic and inorganic components during pyrolysis of Kerosene Creek oil shale and products of demineralization (F37). With increasing pyrolysis temperatures, a progressive decrease in the signal intensity of the CH2 and CH3 vibrations was observed as well as in the carbonyl and carboxylic peaks. Flash pyrolysis can also be used to characterize the insoluble organic matter of sediments, rocks, and coals. Seeley (F38) described this approach coupled with a gas chromatographequipped with a He microwaveinduced plasma for detection by atomic emission spectrometry. Simultaneous multielement detection was achieved with a photodiodearray detector. Qualitative information indicating the occurrence and distribution of these elements in the samples can be used to gauge the relative stage of diagenetic evolution of the samples and provide information on their depositional environment. Rowland et al. (F39) also used pyrolysis GC with an atomic emission detector to characterize organic-rich Pliestocene diatomaceous sedimentsfrom upwelling sedimentsoff Peru. Stout and Idn (F40) described the use of lasers in organic petrology and geochemistry for the purposes of obtaining UV laser-induced fluorescence spectra for model compounds and macerals, which contain more chemically significant information than conventional spectra. IR laser-inducedextraction of microquantities of organic-rich shales was also discussed along with IR laser-induced pyrolysis of small quantities of coals and kerogens. This latter approach produces structurally signiiicant primary pyrolysis products characteristic of the maceral materials. Wilkins et al. (F41) described the use of fluorescence alteration of macerals measured with the laser Raman microprobe to overcome some of the problems associated with vitrinite reflectance suppression. Examples of the approach were provided using samples from coal seams in the Sydney Basin and also samples from an oil well from the northwest shelf of Australia. The insoluble organic or kerogen fraction of source rocks has been studied by a variety of nondestructive techniques. In particular I3C and proton solid-state NMR spectroscopieshave been used extensively to provide structural and geochemical information on various aspects of kerogens as well as coals and oil shales (F42-F48). Similar approaches have also been used

for the evaluation of liquidcontaining samples or discriminating fluid phases in the Brea sandstone (F49-F51), Scanning electron microscopy has also been used in a few studies to obtain information on the distribution of organic matter in source rocks (F52). Bishop et al. (F53) also used this approach along with Os04 staining to demonstrate that significant concentrations of organic matter in some sediments was adsorbed by the clay minerals. Transmission micro-FT-IRspectroscopy has been used by Landais et al. (F54) to identify and characterizedifferent types of organic matter in four torbanites of various geographic origins and provided much greater insight into the origin of these materials than available from previously used analytical methods. The past few years have seen the discovery of new structures, termed ultralaminae, in kerogens from numerous oil shales and source rocks originating from the selective preservation of the nonhydrolyzable biomacromolecules present in thin outer walls of certain algae. Derenne et al. (F55) detected nonhydrolyzable amides in this material, whose distribution varied depending on the marine or lacustrine origin of the considered samples. These protected amide groups can also account for the production of n-alkylnitriles during pyrolysis of ultralaminae-containing kerogens. The characterization of the insoluble fraction of a source rock, at least for the purposes of petroleum potential, typically involves some type of pyrolytic degradation. The pyrolysis may be directed at the determination of bulk parameters using a technique such as Rock-Eva1 pyrolysis or more specific fingerprinting using a pyrolysis method combined with either GC or GC/MS. Bordenave et al. (F56) published a review with 57 references which discussed most of the pyrolysis techniques available for the characterization of source rocks. Tang and Stauffer (F57) described a novel py-GC technique called multiple cold trap pyrolysis gas chromatography, which permitted the collection of pyrolysis products generated over narrow temperature intervals in an array of cryogenic traps. Each fraction represents a thermal slice that can be to calculate kinetic parameters of complex reactions such as thermal cracking of kerogens, coals, solid bitumens, polymers, and biopolymers. Burnham (F58) compared pyrolysis kinetics obtained from rapid open pyrolysis experiments for the Bakken shale, determined activation energies, and predicted the midpoint of oil generation to be 130-140 "C for a geological heating rate of 3 "C/myr. Nonisothermal pyrolysis experiments on an immature Toarcian oil shale sample performed by Lillack and Schwochau (F59) provided evolution profiles of individual alkanes (CI-C,) and alkenes (CZ-Cd). Evaluation of the experimental evolution profiles with a kinetic model, implying a discrete activation energy distribution, yielded more probable kinetic parameters and geological hydrocarbon temperatures commonly accepted for natural gas generation. Dembicki (F60)described the effects of the mineral matrix on the determination of kinetic parameters using modified Rock-Eva1 pyrolysis. It was concluded that the mineral matrix can play a major role in this process and that the organically richest sample or one from a nonrepresentative lithofacies may yield misleading results and adversely influence the outcome of modeling studies based on them. On the contrary, Vucelic et al. (F61)concluded on the basis of a variety of techniques that the effect of the indigenous mineral components in the pyrolysis of the Aleksinac oil shale was very low and that the principal changes in their organic matter should be attributed to thermal rather than to catalytic cracking. Activation energy Analytical Chemistry, Vol. 67, No. 12, June 15, 1995

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distribution of organic matter isolated from source rocks and determined using a nonisothermal pyrolysis technique was described by Sundararaman et al. (F62). Optimal results were obtained when pyrolysis experiments were performed at two or three widely differing heating rates. Bailey (F63) described a furnace system to combust and oxidize the organic matter in a source rock to COZ and hence determine the hydrocarbon potential of the rock from these data. Del Rio et al. (F64) characterized kerogens and asphaltenes from three oil shales taken from increasing depths of the same deposit. Major products included alkanes, alkenes, and sulfurcontaining compounds. The latter were only present in the kerogen fractions and totally absent from the asphaltene pyrolysis products. It was proposed that breakdown of sulfur-sulfur and carbon-sulfur bonds may occur preferentially in the kerogen macromolecule rather than breakdown of carbon-carbon bonds to give rise to asphaltenes. Goni and Eglinton (F65) used py-GC combined with an isotope ratio mass spectrometer to determine the isotopic composition of hydrocarbons and phenols produced from pyrolysis of natural bioploymers and sedimentary kerogens. Despite the widespread heterogeneity, the isotopic values of individual aliphatic and phenolic pyrolysis products can be related to the total organic carbon in kerogens and used to trace its biological sources. The effects of the maceral composition on the pyrolytic behavior of kerogens has been studied by Ishiwatari et al. (F66). Particular emphasis was placed on variations in the phenol content of the pyrolysis products from three different types of kerogens. As the vitrinite content increased, so did the phenolic content of the pyrolysis products. Py-MS can be used to evaluate gas evolution profiles from source rocks, oil shales, coals, or asphaltenes (F67). The temperature of maximum evolution rate of individual hydrocarbon gases could be used to characterize the type of kerogen from which they were derived. Limitations of Rock-Eva1 pyrolysis for the purposes of characterizing the main source rock intervals on the northwest shelf of Australia was recognized by Scott (F68). As a result, he used py-GC to obtain a better method for the estimation of the type of products of the kerogen breakdown as a result of maturation. Asphaltenes are also partially insoluble in many organic solvents and are also suitable for characterization by methods involving pyrolysis combined with GC, GC/MS, or simply MS. Wilhems et al. (F69) used pyrolysis combined with field ionization mass spectrometry to characterize asphaltenes derived from oils from different source rocks and reservoir core extracts kom tar mat containing petroleum reservoirs. The results permitted correlations to be made between the molecular weight of the asphaltenes and the maturity of the samples from which they were derived. In addition to the use of pyrolysis for the purpose of characterization of the insoluble organic matter, it is also possible to utilize chemical degradation techniques for the purposes of kerogen structural characterization. Dragojlovic et al. (F7O) characterized ester and ether moieties in kerogens from the Aleksinac oil shale using hydrolysis and ruthenium tetraoxide oxidation. A number of type I kerogens of different geographic origins were characterized by Vitorovic et al. (F71) using alkaline KMn04. The results obtained permitted improved structural differentiation of seemingly similar kerogens. A 15step alkaline permanganate degradation of the Moroccan Timahdit oil shale was performed by Ambles et al. (F72). The results were used to postulate the possible structure for the kerogen and to determine 346R

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the nature of possible products trapped in the kerogen matrix. Barakat (2773)used alkaline hydrolysis to obtain more information on the structural entities bound to the macromolecular structure of the Monterey kerogen. The significance of the lipid composition from these reactions was discussed in terms of lipid diagenesis and the biomarker distributions. Prior to kerogen analysis or characterization it is often necessary to remove the mineral matrix, and a variety of methods are available for this purpose. Colling and Nolte (F74) described a novel method for the isolation of the kerogen from a mineral sample in a pressurized reaction vessel. The method permits reaction at '2 atm and provides for the removal of all liquids without significant loss of sample solids. In another approach, Acholla and Orr (F75) determined that treatment of kerogen with aqueous acidic chromous chloride results in the quantitative removal of pyrite without causing significant alteration of the organic matter. The method is especially suitable for the preparation of pyrite-free chemically unaltered kerogen required for the evaluation of petroleum source rocks. Inorganic and organic associations of trace elements in the kerogen of the New Albany shale were studied by the analysis of kerogen fractions and a mineral residue obtained by density separation (F76). The results indicated that a measure of the degree of association of various elements has possible applications in oil source rock correlations. In addition to characterizing kerogens by various degradation techniques, optical techniques play an important role in the characterization of kerogens. Thompson-Rizer (F77) discussed the optical description of amorphous kerogen in both thin sections and isolated kerogen preparations of Precambrian to Eocene shale samples. It was observed that while specific biological precursors of kerogen may be significantly dhYerent between the Precambrian and Phanerozoic, the mode of degradation and preservation in shales appears to be similar. It is concluded that more Precambrian organic-rich rocks need to be studied optically to venfy the hypothesis that Precambrian kerogens are mostly amorphous. The best way to completely describe amorphous kerogens is to use both isolated kerogen strewn slides and whole rock polished thin sections. Other methods used to study kerogens include elemental analyses, XRD, and infrared spectroscopy (F78);the nitrogen chemistry of kerogens and bitumens was studied using X-ray absorption near-edge structure (XANES) spectroscopy to determine the nitrogen chemical structures present; differences were found between the kerogens and bitumens from the same source rock, indicating that bitumen analysis cannot replace kerogen analysis at least for nitrogen chemistry (F79). Five nuclear microprobe spectroscopic modes were combined to study the relationship between organic matter and the mineral host matrix in petroleum environments (FSO). Use of laser ablation Fourier transform ion cyclotron resonance mass spectrometry to study kerogens, raw oil shale, and carbonaceous residues from kerogen pyrolysis produced fullerenes with masses up to m / z 4000. It is proposed that the changes in the aromatic nature of the kerogen residues with increasing pyrolysis temperatures are directly related to the ease of fullerene formation (F81). The use of clay minerals as geothermometers based on the empirical relationships between clay mineral transformations and temperature has been reviewed by Pollastro (F82). Particular attention was directed toward the illite/smectite (I/S) relationship, and good agreement was observed between changes in ordering of I/S and calculated maximum burial temperatures of hydrocarbon maturity, suggest-

ing that I/S is a reliable semiquantitative geothermometer and an excellent measure of thermal maturity. Atomic force microscopy has also been applied to small clay particles of illite/smectite from North Sea Jurassic shale and used to obtain information about the thickness, size, and surface structure of mixed layers of illite/smectite which can provide new insight into their formation (F83). The use of nuclear methods in petroleum geology has been reviewed by Gottikh et al. (F84). It was proposed that such methods combined with the more conventional approaches allow a more efficient solution of geological correlations and identification of areas of increased rock permeability. Tomographic methods for qualitative visualization to quantitative core analyses have been described by both Kantzas et al. (F85)and Coles and Muegge (F86). Khorasani and Michelson (F87) discussed the processes involved in the thermal evolution of sulfur-richand -poorbitumens such as wurtzilite and albertite,as well as the relationship between reflectance of solid bitumens and vitrinite reflectance and the application of bitumen reflectance and bireflectance in estimating the paleothermal conditions in petroleum and ore-bearing sediments and its application in ore prospecting. A quantitative model for the prediction of the occurrence of marine sliciclastic source rocks and their organic content has been developed by Schwarzkopf (F88). The model is based on parameters derived from organic matter supply to the photic zone of the ocean, water depth, sedimentation rate, and preservation conditions. The potential of the model to quantify source rock quality, uncertainties in source rock prediction, and source quality risk values to be used in appraisal of sedimentary basins and prospects is demonstrated using examples of recent sediment samples from the Peru continental margin and ancient sediments from the Lower Toarcian Shale, Germany. Richard Paul Phil is a rofessor of petroleum geochemistry in the School of Geology. an .Gee ysics at the University of Oklahqma in Norman. He receaved has B. c an chemastry in 1968fiom the Unaversaty ofdberdeen, Scotland, and his Ph.D. in organic chemistry in 1972fiom the University of Sydney, Australia. His research has been directed at the application of organic and analytical chemistry tofossilfuel research, in particular, determination of compounds known as biological markers present in oils, coals, and oil shales. A second area o research has been the characterization ofsource rocks, coals, and oil sha es using microscale pyrolysis techniques combined directly with gas chromatography/mass spectrometry.

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