Lake-type controls on petroleum source rock potential in nonmarine basins Alan R. Carroll and Kevin M. Bohacs ABSTRACT Based on numerous empirical observations of lacustrine basin strata, we propose a three-fold classification of lacustrine facies associations that accounts for the most important features of lacustrine petroleum source rocks and provides a predictive framework for exploration in nonmarine basins where lacustrine facies are incompletely delineated. (1) The fluvial-lacustrine facies association is characterized by freshwater lacustrine mudstones interbedded with fluvial-deltaic deposits, commonly including coal. Shoreline progradation dominates basin fill, resulting in the stacking of indistinctly expressed cycles up to 10 m thick. In map view, the deposits may be regionally widespread but laterally discontinuous and contain strong facies contrasts. Transported terrestrial organic matter contributes to mixed type I–III kerogens that generate waxy oil (type I kerogen is hydrogen rich and oil prone; type III kerogen is hydrogen poor and mainly gas prone). The Luman Tongue of the Green River Formation (Wyoming) and the Honyanchi Formation (Junggar basin, China) provide examples of this facies association, which is also present in the Songliao basin of northeastern China, the Central Sumatra basin, and the Cretaceous Doba/Doseo basins in westcentral Africa. (2) The fluctuating profundal facies association represents a combination of progradational and aggradational basin fill and includes some of the world’s richest source rocks. Deposits are regionally extensive in map view, having relatively homogenous source facies containing oil-prone, type I kerogen. Examples include the Laney Member of the Green River Formation (Wyoming), the Lucaogou Formation (Junggar basin, China), the Bucomazi Formation (offshore west Africa), and the Lagoa Feia Formation (Campos basin, Brazil). (3) The evaporative facies association represents dominantly aggradational fill related to desiccation cycles in saline to hypersaline lakes and may include evaporite and eolianite deposits. Sublittoral organic-rich mudstone facies are relatively thin but may be Copyright !2001. The American Association of Petroleum Geologists. All rights reserved. Manuscript received December 15, 1998; revised manuscript received June 28, 2000; final acceptance August 31, 2000. AAPG Bulletin, v. 85, no. 6 (June 2001), pp. 1033–1053 1033 AUTHORS Alan R. Carroll ! Department of Geological and Geophysical Sciences, University of Wisconsin, 1215 W. Dayton St., Madison, Wisconsin, 53706; carroll@geology.wisc.edu Alan R. Carroll has been an assistant professor at the University of Wisconsin, Madison, since 1996, specializing in sedimentary basins in western China and the western United States. He received geology degrees from Carleton College (B.A. degree, 1980), the University of Michigan, Ann Arbor (M.Sc. degree, 1983), and Stanford University (Ph.D., 1991). He worked as an exploration geologist for Sohio (1983–1986) and a research geologist for Exxon Production Research Company (1991– 1995). He is an associate editor of the AAPG Bulletin. Kevin M. Bohacs ! ExxonMobil Upstream Research Co., 2189 Buffalo Speedway, Houston, Texas, 77252; kmbohac@upstream.xomcorp.com Kevin M. Bohacs is a sedimentologist and stratigrapher with the Petroleum Geochemistry section of ExxonMobil Upstream Research Company (URC) in Houston, Texas. He received his B.Sc. (honors) degree in geology from the University of Connecticut in 1976 and his Sc.D. degree in experimental sedimentology from M.I.T. in 1981. At URC, he leads the application of sequence stratigraphy and sedimentology to organic-rich rocks from deep sea to swamps and lakes in basins around the world. As a research associate, his primary focus is to keep the geo- in geochemistry, integrating field work, subsurface investigation, and laboratory analyses. He has written numerous articles on the stratigraphy and sedimentology of mudrocks, hydrocarbon source rocks, and lake systems. He was co-recipient of the AAPG Jules Braunstein Memorial Award for best poster session paper in 1995 for work on coal sequence stratigraphy and the AAPG International Paper Award in 1998 and was an AAPG Distinguished Lecturer for 1999– 2000. ACKNOWLEDGEMENTS This article benefited from discussions with many individuals, including S. C. Brassell, Y. Y. Chen, R. Cunningham, D. J. Curry, G. Genik, K. S. Glaser, G. J. Grabowski Jr., G. B. Hieshima, G. H. Isaksen, B. J. Katz, M. R. Mello, K. Miskell-Gerhardt, J. E. Neal, P. Olsen, D. J. Reynolds, C. Scholz, and K. O. Stanley. G. J. Grabowski and H. B. Lo collected some of the data used in this article. M. Wartes provided useful comments on an early draft of the manuscript. Field studies in the Junggar basin in 1987, 1988, and 1992 were funded by the Stanford-China Industrial Affiliates, a group of companies that included AGIP, Amoco, Anschutz, BHP Petroleum, Chevron, Conoco, ElfAquitaine, Enterprise Oil, Exxon, Mobil, Occidental, Pecten, Phillips, Sun, Texaco, Transworld Energy International, and Unocal. Conoco provided additional support for this article. The Donors of The Petroleum Research Fund, administered by the American Chemical Society, also provided support for this research. We thank Exxon Production Research Co. for permission to publish this article. J. A. Curiale, B. J. Katz, B. Wiggins, and an anonymous reviewer all provided very helpful reviews. 1034 Lacustrine Petroleum Source Rocks quite rich and widespread. The highest organic enrichment coincides with the deepest lake stages. Low input of land plant organic matter results in minimal lateral contrasts in organic content. In some cases a distinctive type I-S (sulfur-rich) kerogen may generate oil at thermal maturities as low as 0.45% vitrinite reflectance equivalent. Examples include the Wilkins Peak Member of the Green River Formation (Wyoming), the Jingjingzigou Formation (Junggar basin, China), the Jianghan and Qaidam basins (China), and the Blanca Lila Formation (Argentina). INTRODUCTION The deposits of nonmarine sedimentary basins account for a growing segment of current petroleum exploration and exploitation opportunities, especially in areas of rapid market growth such as China, southeast Asia, and western Africa. The specific techniques needed for locating, assessing, and developing hydrocarbon reserves within lacustrine basins remain relatively undeveloped compared to those for marine systems, and they constitute a significant source of financial risk (cf. Sladen, 1994). This uncertainty stems not from a lack of data on lacustrine systems, but instead from their great sedimentologic complexity, as evident from numerous studies of modern and ancient lakes. Furthermore, most lacustrine source rock models have focused on inferred climatic controls (e.g., Eugster and Kelts, 1983; Talbot, 1988), although paleoclimate modeling has had only limited success in predicting the actual occurrence of organic-rich lacustrine facies (e.g., Barron, 1990). Fortunately, some of the complexity evident in modern lakes resolves itself in ancient lacustrine deposits, resulting in the expression of three commonly recurring motifs in the lithology and stratigraphy of lacustrine deposits. For example, Bradley (1925) was able to generalize a trend within the heterogeneous Eocene Green River Formation (Utah, Colorado, and Wyoming) from “relatively shallow fresh-water lakes,” to “depositional basins that alternately flooded and evaporated either partially or completely,” and finally to a period when “the lakes became playa-like” and evaporites precipitated. A similar division, based on geography rather than on geologic time, was proposed over 60 years later by Olsen (1990) for the widespread lacustrine deposits of the Triassic–Jurassic Newark Supergroup (eastern United States). Olsen idealized lacustrine facies associations as either Richmond-type, Newark-type, or Fundy-type and proposed that these associations reflect differences in climatically controlled basin hydrology. Mello et al. (1988) developed similar concepts involving organic facies, subdividing Brazilian source rocks into freshwater and brackish-saline lacustrine facies based on relative concentrations of biological marker compounds that are sensitive to lake salinity and organic matter input. Others have characterized biomarker distributions indicative of hypersaline lacustrine source rocks (e.g., Jiang and Fowler, 1986). Carroll and Bohacs (1995, 1999) proposed a classification of ancient lake basins into three end-member types that correspond to commonly recurring lacustrine facies associations. The terms “overfilled,” “balanced-fill,” and “underfilled” lake basins refer to the balance between tectonically controlled potential accommodation and climatically controlled water plus sediment supply. A unique advantage of this model is that it permits broad characteristics of hydrocarbon source rock richness and gas vs. oil generation to be predicted from limited geologic observations of nonsource sedimentary facies (typically encountered on structure and along basin margins). This information can also be incorporated into basin thermal history models to estimate the timing of generation. Several previous studies have presented overviews of lacustrine petroleum source rocks (e.g., Powell, 1986; Katz, 1988, 1990; Kelts, 1988; Mello et al., 1988; Mello and Maxwell, 1990; Williams et al., 1995). This article is the first to classify petroleum source rocks in accordance with the lake-type classification of Carroll and Bohacs (1995, 1999), and one of very few to systematically integrate detailed observations of lacustrine sedimentary facies with geochemical data on organic facies. We emphasize detailed, nonbiased sampling of carefully described stratigraphic intervals as the basis for interpreting the geologic controls on organic enrichment. In contrast to previous work, the model we present suggests specific, practical techniques for predicting source rock richness, distribution, oil vs. gas potential, and generation timing based on sparse geochemical or geologic data. Conversely, our model permits broad aspects of the tectonic and climatic history of nonmarine basins to be predicted in part from the character of petroleum and of source rock extracts. Such data may be very useful in assessing other exploration play elements, such as reservoir distribution and quality, migration pathways, fault timing, and basin thermal history. Two important intervals of lacustrine strata are used for illustrative purposes in this article: the carbonate-rich Eocene Green River Formation of the Washakie basin (Wyoming) and the predominantly silicic Upper Permian lacustrine formations of the Junggar basin (northwest China). Despite gross differences in geologic age, lithology, and paleogeography, the same three idealized facies associations are recognized in both cases and in many other lake basins. The petroleum generative characteristics of mudrocks within each of these facies associations differ significantly from each other and must be considered for successful exploration of nonmarine basins. LACUSTRINE SEDIMENTARY FACIES ASSOCIATIONS Lacustrine deposits may be characterized according to (1) their sedimentary facies, fauna, and flora, (2) their internal stratigraphic relations (such as parasequence stacking), and (3) the character of associated deposits. In particular, evidence for open vs. closed basin hydrology and the presence and nature of depositional cyclicity provide the fundamental bases for categorizing ancient lake systems according to types. Note that these types represent end-member ideals and as such need not be 100% representative of any one occurrence. Furthermore, the interpretation of depositional cycles necessarily implies simultaneous observation of several different subfacies, resulting in time averaging of diachronous but evolutionary depositional environments. The concept of lake type as applied to ancient deposits therefore may not be directly applicable to modern lakes, for which only a synoptic or snapshot view is available. The Green River Formation in Wyoming consists of approximately 2500 m of Eocene lacustrine and associated alluvial strata deposited in several foreland basins adjacent to Laramide-style uplifts (Sullivan, 1985; Roehler, 1992) (Figure 1). Late Permian basin subsidence resulted in the preservation of more than 5000 m of nonmarine facies in the southern Junggar basin, including more than 1000 m of organic-rich lacustrine mudstone (Liao et al., 1987; Carroll et al., 1990, 1992, 1995; Wartes et al., 1998) (Figure 2). Three lacustrine facies associations may be identified within both deposits, as detailed subsequently: the fluvial-lacustrine facies association, the fluctuating profundal facies association, and the evaporative facies association. Fluvial-Lacustrine Facies Association The Luman Tongue consists of freshwater to mildly alkaline facies deposited in the Washakie basin as the earliest lacustrine phase of the Green River Formation (Roehler, 1992; Horsfield et al., 1994) (Figure 1). As such, it resembles the Black Shale facies of the Green River Formation in the Uinta basin, a source of petroleum in Altamont-Bluebell and other fields (Fouch, 1975; Ruble and Philp, 1998). The Luman Tongue contains generally poorly expressed, shallowing-upward packages (parasequences) that were deposited by processes of shoreline progradation (Figure 3). Where evident, the base of these parasequences Carroll and Bohacs 1035 Miles 0 Km UT ID WY 0 100 ROCK SPRINGS UPLIFT 200 300 400 500 700 800 UT 42˚ ID WY Washakie Basin WYOM ING TH RUST East Fresh GREAT DIVIDE BASIN ROCK SPRINGS 800 UPLIFT 900 1000 Figure 3C 1100 1200 WASHAKIE BASIN 41˚ UINTA MOUNTAINS Evap. SAND WASH BASIN Wilkins Peak Member WY CO Luman Tongue (Figure 3A) GREAT DIVIDE BASIN GREEN RIVER BASIN 0 Saline lacustrine Flood plain Mudflat/saline lacustrine Freshwater lacustrine Evaporite/saline lacustrine Figure 3A UINTA MOUNTAINS Coal Luman Tongue 111˚ 400 200 300 110˚ Figure 1. Location, sedimentary facies, and isopach maps of the Green River Formation in Wyoming, modified from Roehler (1992). 109˚ SAND WASH BASIN 108˚ RA ER RE AD M Sandstone 100 SI 100 200 41˚ 250 km (156 miles) ROCK 300 SPRINGS100 UPLIFT WASHAKIE 200 300 BASIN UT CO UT 42˚ ID WY Fresh COAL WYOM ING TH RUST Alkal. lake Water Chemistry: Lower 2500 m (8200 feet) Lwr. LaClede Bed (Figure 3B) 300 RA ER RE AD M Alkal. Wilkins Peak Member (Figure 3C) Eocene 500 600 700 400 100 WY CO SI Middle Laney Member 0 200 SAND WASH BASIN UT CO Rock Springs Uplift Figure 3B 41˚ Laney Member Green River Basin WASHAKIE BASIN 600 100 UINTA MOUNTAINS West 0 RA ER RE AD M 0 50 GREEN RIVER BASIN UT CO N 100 GREAT DIVIDE BASIN SI Lacustrine Petroleum Source Rocks USA Map Area 42˚ WYOM ING TH RUST 1036 Isopach contour interval = 100" WY CO 107˚ is typically a sharp surface overlain by organic-rich calcareous mudstone and shale or organic-poor bioturbated mudstone and siltstone (Horsfield et al., 1994; Bohacs, 1998). These facies grade upward into littoral coquinas, small sandy deltas, and occasional thin coals. Flood-plain and fluvial facies also are common. Cyclicity caused by lake-level fluctuation is subtle or absent, consistent with relatively open lakebasin hydrology. The laterally equivalent and superjacent Niland Tongue of the Wasatch Formation contains predominantly lake-plain to alluvial deposits (including coals) and is closely related to the Luman Tongue (Figure 1). The Hongyanchi Formation in the southern Junggar basin consists of interbedded profundal mudstone, siltstone, limestone, and fluvial sandstone and conglomerate (Carroll et al., 1992, 1995) (Figures 2, 4). It too lacks any strongly expressed depositional cyclicity, although indistinct deepening and shoaling depositional trends on the scale of 10 m or more are evident. Mudstone units are commonly slightly calcareous and laminated in places but are commonly homogenous. Amalgamated fluvial sandstone and conglomerate beds may reach thicknesses up to tens of meters, recording channeled flow within well-developed stream systems. Desiccation cracks and other evidence of prolonged subaerial exposure are absent. Limestone beds 20 to 50 cm thick occur in places and generally comprise argillaceous micrite without visible fauna; they may be algal in origin. Coals are not present in the Hongyanchi Formation, but overlying fluvial units do contain fragments of petrified wood that have coaly residues (Carroll et al., 1992). The aforementioned features are common to many other hydrologically open lake basins, such as the Richmond and several other basins filled by elements of the Newark Supergroup. Olsen (1990) characterized Richmond-type basins as containing significant coals and bioturbated shallow-water and fluvial facies and thick intervals of laminated siltstone. Evidence for subaerial exposure is absent, consistent with high precipitation/evaporation ratios. Other examples of this fluvial-lacustrine facies association include the Paleocene of the Fort Union Formation in Wyoming (Liro and Pardus, 1990), some Cretaceous units in the Songliao basin of northeastern China (Yang et al., 1985; Xue and Galloway, 1993; D. Li et al., 1995), some Paleocene intervals in the Central Sumatra basin (Kelley et al., 1995), and the Cretaceous strata of the Doba/Doseo basins in west-central Africa (Genik, 1993). Fluctuating Profundal Facies Association The lower LaClede Bed of the Laney Member of the Green River Formation consists of alkaline lake deposits that are widely distributed over the greater Green River basin (Roehler, 1992; Horsfield et al., 1994) (Figures 1, 3). It resembles similar facies in the Parachute Creek Member of the Green River Formation in Utah and Colorado, which, although immature with respect to petroleum generation, constitutes the well-known Green River oil shale deposits. In contrast to the Luman Tongue, the lower LaClede Bed contains welldefined parasequences that record major lake desiccation and flooding (Horsfield et al., 1994). The parasequences typically begin with algal and oolitic facies, followed by deposition of finely laminated organic-rich calcareous shale. Subsequent evaporative contraction of the lake resulted in a gradual vertical increase in dolomicrite, magadii-type chert, and efflorescent crusts of saline minerals, typically culminating in mud-crack horizons. During uncommonly humid phases, limited progradation of fluvial clastic facies occurred at the lake margins, resulting in mixed aggradational/progradational stratal geometries. The Lucaogou Formation (Junggar basin, China) consists primarily of profundal laminated mudstone and occasional siltstone interbeds and includes the most organic-rich facies in the southern Junggar basin (Carroll et al., 1992; Carroll, 1998) (Figures 2, 4). The Lucaogou Formation is predominantly siliciclastic, with the exception of occasional nodular dolomite. Distinct 1–4 m scale cycles occur near its base and are punctuated by mud-cracked desiccation surfaces. These cycles grade upward into the most organic-rich interval of the Lucaogou Formation, where there are no obvious signs of subaerial exposure. Cyclicity continues to be expressed, however, as variations in the thickness and preservation of lamina. Flooding surfaces have not been identified within this interval; therefore, lamina thicknesses appear to record varying input of clay and silt in an area distant from any shoreline (Carroll, 1998). These variations in detrital grainsize may in turn be linked to fluctuating lake level. Occasional centimeter-scale graded beds record fine-grained turbidite deposition, and minor soft-sediment slumping is common. Fluctuating profundal facies were also described by Van Houten (1962) in the Newark and related basins. Olsen (1990) attributed these cycles to lake level changes driven by Milankovitch-scale climate changes in basins where long-term water inflows were closely Carroll and Bohacs 1037 LAKE MARGINAL FACIES Hongyanchi Fm. measured section (Figure 4A) 1300 86 84 90 88 100 ? 0 1200 46 JUNGGAR BASIN CHINA 50 0 FLUVIAL FACIES HONGYANCHI FORMATION 1400 500 Karamay 1100 1 ? ? 1000 ? 1000 5 5 KELAMEILI SHAN 50 0 45 JUNGGAR 900 1000 10 500 BASIN ? 46 10 00 800 150 0 LUCAOGOU FORMATION DEEP LAKE FACIES ? 44 44 700 ? NORTH 600 N 2000 T U TIAN 50 KM BOGDA SHAN ? SHAN 88 86 500 Upper Permian Sandst. and Congl. (approximate) Permian Lake Deposits (approximate) Pre-Permian Outcrops T TIANCHI SECTION 300 1 5 20 TOC (%) 0m U URUMQI SECTION LAMINATED ORGANIC-RICH MUDSTONE MUDSTONE LIMESTONE COVERED INTERVAL TOC < 0.5% JINGJINGZIGOU FM. SILTSTONE TO SANDST. DEEP LAKE FACIES 700 LUCAOGOU FORMATION DEEP Lucaogou Fm. meas. section (Figure 4B) 200 100 1038 U Urumqi measured section T Tianchi measured section 800 600 500 400 LAKE MARGINAL FACIES LAKE MARGINAL FACIES 400 300 200 100 0m 1 5 20 TOC (%) Lacustrine Petroleum Source Rocks Jingjingzigou Fm. measured section (Figure 4C) Oil Fields Thrust belts 00 10 5 Upper Permian Thickness (m) Mesozoic-Cenozoic Thickness (km) balanced by outflows. Van Houten cycles possess extreme lateral continuity, except where they intersect basin-marginal alluvial fans. The ratio of organic-rich to organic-poor units in the Newark basin, however, is relatively low compared to the lower LaClede Bed or Lucaogou Formation. The preservation of fine laminae implies the lack of burrowing in fauna or resuspension of bottom sediments by currents. Laminated intervals, therefore, are interpreted to have been deposited in water depths below storm wave base, and anoxic conditions prevail below the sediment-water interface (Olsen, 1990). Similar profundal facies also occur in the Bucomazi Formation offshore west Africa (Burwood et al., 1995) and in the Lagoa Feia Formation offshore Brazil (Campos basin) (Trinidade et al., 1995). Evaporative Facies Association The Wilkins Peak Member of the Green River Formation (Figures 1, 3) encompasses a wide variety of facies, ranging from alluvial fan and sheetflood sandstone to laminated oil shale (e.g., Bradley and Eugster, 1969; Smoot, 1983). This member is best known, however, for its bedded trona and halite, which are interpreted to have been deposited in evaporative playas (Eugster and Surdam, 1973; Eugster and Hardie, 1975). Basin-center deposits record dominantly aggradational stacking of organic-rich mudstone facies during lake flooding and carbonate and evaporite facies during lake desiccation. The basin-center organic-rich mudstone facies grade vertically and laterally into littoral and supralittoral deposits of dolomitic and siliciclastic mudstone and grainstone facies that have desiccation cracks and evaporitic minerals or their replacements (Bohacs, 1998). The lake-margin lithofacies intertongue with carbonate and siliciclastic sandstone and mudstone facies probably deposited in alluvial-fan and fluvial systems. The basin-center evaporite beds lap marginward onto subaerially exposed lake and lake-margin strata. Laterally equivalent eolian reworked grainstone and mudstone facies are uncommon. Figure 3C illustrates the distribution of lithologies in a representative vertical section. Stratigraphic relationships among littoral and lake-plain facies are complex be- cause of interactions between sheetfloods and rising lake levels (Smoot, 1983). The Jingjingzigou Formation (Junggar basin, China) (Figures 2, 4) consists of dolomitic gray and gray-green mudstone, medium gray to dark gray mudstone, wave-rippled dolomitic siltstone, and finegrained sandstone (Carroll et al., 1992; Carroll, 1998). Although evaporite minerals are absent from basinmarginal outcrop exposures, possible evaporite pseudomorphs occur. Displacive dolomite nodules ranging in size from 1 to 10 cm are common, particularly within the upper parts of siltstone beds. Shoalingupward lacustrine cycles 10 to 2 m thick occur throughout the measured section. Tabular siltstone and sandstone beds ranging from 20 to 50 cm in thickness appear at the base of many of the cycles. Minor scour at the base of siltstone and sandstone beds is common, as is soft-sediment loading into underlying mudstone. The sandstone beds are interpreted to represent relatively unconfined, episodic flows across a lake plain during onset of flooding and lacustrine transgression. Mudstone facies typically possess relatively thick, discontinuous, wavy laminae (#1 mm) and commonly grade upward into poorly laminated or homogenous intervals. Thin intervals ($10 cm) of submillimeter scale laminae occur rarely. Abundant mud cracks, commonly sand or silt-filled, occur near cycle tops and attest to frequent subaerial exposure and desiccation. Although the composition of Wilkins Peak evaporites is unusual, evaporative lake facies occur in many other lacustrine basins. For example, desiccation cycles in parts of the Fundy and similar basins of the Newark Supergroup include shallow lake and playa facies and are associated with gypsum nodules, salt-collapse structures, and eolian dunes (Hubert and Mertz, 1984; Smoot and Olsen, 1988). Other examples include the Blanca Lila Formation (Pleistocene of Argentina) (Vandervoort, 1997) and deposits within several Tertiary basins in China (e.g., Fu et al., 1986). LACUSTRINE ORGANIC FACIES Each of the sedimentary facies associations described previously correspond to distinctive organic facies as Figure 2. Location of Junggar basin Permian lacustrine facies (modified from Carroll et al., 1992, and Carroll, 1998). Master sections from Tianchi and Urumqi are aligned according to an approximate lithostratigraphic correlation between these localities. Permian isopach contours represent the Jingjingzigou, Lucaogou, and Hongyanchi Formations but do not include the entire Upper Permian interval. Carroll and Bohacs 1039 A. Luman Tongue B. Lower LaClede Bed, Laney Member C. Wilkins Peak Member xxxxx xxxxx xxxxx (36) Ss MSs SMs Ms Sh xxxxx !15 m 30 0 0 %TOC 1000 HI 50 ft 10 m xxxxx xxxxx xxxxx xxxxx xxxxx xxxxx xxxxx Ss MSs SMs Ms Sh 0 0 30 0 %TOC 1000 HI Scour (42) Ss MSs SMs Ms Sh (48) 0 30 0 %TOC 1000 HI 0 LEGEND Mudstone Trough cross-beds Intraclast conglomerate Current ripples Evaporite Wave ripples Stylolites Combined-flow ripples Concretions Climbing ripples Oolite Planar lamination Stromatolite Ss Sandstone Flaser or lenticular bedding Plant fossils MSs Muddy sandstone Convolute bedding Ostracods SMs Sandy mudstone Fining-upward bed Molluscs Ms Mudstone Mudcracks Fish Sh Coal xxxxx Tuff Laminated Mudstone Sandstone Limestone Evaporite Shale Flooding surface Figure 3. Green River Formation measured sections from (A) outcrop of Luman Tongue at Hiawatha locality (21-T12N-R100W), (B) outcrop of lower LaClede Bed of the Laney Member at Trail Dugway locality (18-T14N-R99W), and (C) core of Wilkins Peak Member from the UPR 41–43 well (23-T17N-R109W; see Figure 1 for locations). TOC " total organic carbon (%); HI " Rock-Eval hydrogen index (mg/g). Legend M 30 submillimeter laminated mudstone nonlaminated mudstone limestone mud cracks (desiccation) laminated mudstone (>1mm) siltstone dolomitic concretions mud intraclasts FS = Flooding surface M 13 M 12 12 11 11 10 10 20 9 9 FS 8 8 FS 7 FS 6 FS FS FS FS 5 7 6 5 10 FS 4 4 FS 3 FS Carroll and Bohacs FS 2 3 2 1 1 FS 0 deep shallow Water Depth 0 0 0 1 2 3 4 5 0 % TOC A. Hongyanchi Formation 1000 HI (mg/g) 0 fine coarse Lamination 10 20 0 % TOC B. Lucaogou Formation 1000 HI (mg/g) deep shallow Water Depth 0 1 2 3 % TOC 4 5 1000 0 HI (mg/g) C. Jingjingzigou Formation 1041 Figure 4. Measured sections from (A) Hongyanchi Formation at Urumqi, (B) Lucaogou Formation at Tianchi, and (C) Jingjingzigou Formation at Tianchi (modified from Carroll, 1998; see Figure 2 for locations). determined from such features as total organic carbon (% TOC), Rock-Eval hydrogen indices (HIs), visual kerogen descriptions, pyrolysis products, and biomarker geochemistry. Biomarkers, or biological marker compounds, are complex molecular fossils derived from once-living organisms (Peters and Moldowan, 1993). They have the capacity to provide detailed qualitative information on organic matter input, water column oxygenation, and thermal maturity. A unique advantage of biomarkers over other geochemical measurements is that the same compounds are found in both rock extracts and expelled oils, making it possible to interpret source rock depositional environments in cases where the rocks themselves are inaccessible. Biomarkers are also commonly used to assess the relative salinity of source rock depositional environments, based on the partial record they provide of the types of organisms that were present. This information can be correlated with physical characteristics that suggest a particular salinity range, such as abundant mud cracks or the presence of evaporites. It should be noted, however, that in this context, terms such as “fresh”, “brackish”, “saline”, or “hypersaline” do not normally imply specific solute concentrations, but instead represent interpreted relative salinity levels. The following discussion summarizes the application of several biomarker parameters to the interpretation of lacustrine depositional environments and organic matter sources; see Peters and Moldowan (1993) for more detailed documentation. Table 1 summarizes bulk organic matter and biomarker parameters for Green River Formation and Junggar basin samples, as well as data reported for other lacustrine units. These occurrences are subdivided into algal-terrestrial, algal, and algal-hypersaline organic facies. Note that for each facies, considerable variation may occur in a given biomarker parameter, both within one unit and among different units. This variation results from differing lake ecologies, differing levels of thermal maturity, heterogeneous depositional environments, and possibly different analytical methods used by different workers. Because only limited stratigraphic data are available in most of the studies cited, some reported occurrences probably also include samples from more than one organic facies. Despite these uncertainties, however, each organic facies exhibits a distinct pattern when all the parameters are considered together. Algal-Terrestrial Organic Facies The fluvial-lacustrine facies association corresponds to algal-terrestrial organic facies in the Luman and Niland 1042 Lacustrine Petroleum Source Rocks tongues and in the Hongyanchi Formation. The majority of TOC values in Luman Tongue and Niland Tongue mudstone facies lie between 2 and 8% (Figures 3A, 5A), but some coaly samples exceed 50% TOC (Figure 6). Rock-Eval hydrogen indices (HIs) for individual samples from a continuous section of the Luman and Niland tongues are highly variable (Table 1). Their average HI is 310, in sharp contrast to type I kerogen HI values that range between 600 and 900 and can exceed 1000 (e.g., Graham et al., 1990). Closer examination suggests the presence of two distinct organic matter populations within these units; one population averages 4.87% TOC and HI # 500, and the other averages 9.34% TOC and HI $ 500 (Figure 6). Visual kerogen descriptions indicate that organic macerals likewise contain two populations; they are dominated by alginite but also contain varying proportions of vitrinite (Horsfield et al., 1994). Luman Tongue and Niland Tongue source rocks, therefore, record mixed aquatic and terrestrial organic matter input. Population 1 samples are tightly clustered around a linear regression line representing HI 805 (Figure 6), attesting to the constancy of organic matter type within these samples. Variation in their TOC content likely resulted in part from higher dilution of organic matter by silt and clay. Population 2 samples are much more widely scattered around a line representing HI 324, suggesting a more heterogenous mixture of aquatic and terrestrial organic matter. Biomarker concentrations in extracts from the Luman Tongue and Niland Tongue are indicative of relatively oxic freshwater environments that have mixed input of aquatic and terrestrial organic matter (Table 1). Analysis of kerogen structure via pyrolysis–gas chromatography techniques indicates that at higher thermal maturities, Luman Tongue mudstone would generate waxy oil (Horsfield et al., 1994). The TOC values in the Hongyanchi Formation are lower on average than the Luman and Niland tongues (Figures 4A, 5B), although values up to 7.7% have been reported (Carroll et al., 1992). The TOC and HI values are also lower in part because of significantly greater thermal maturity of the Hongyanchi Formation (Figure 5A, B). Overall organic matter composition appears similar to the Luman and Niland tongues, although too few samples have been collected for a full assessment. HI ranges from 58 to 444. The highest organic enrichments correspond to more profundal intervals, whereas the lowest enrichments correspond to massive limestone and mudstone (Figure 4A). Vitrinite and inertinite combine 200 40 15 B. Hongyanchi Formation 35 S2 (mg/g) n = 171 mean %TOC = 7.09 std. dev. = 8.63 Ro = 0.35-0.45% 100 n = 27 mean %TOC = 2.72 std. dev. = 1.85 Ro = 0.86-1.09% 30 25 9 y = 3.87x - 4.79 r 2 = 0.57 20 y = 3.10x - 9.23 r 2 = 0.78 12 6 15 Frequency A. Luman and Niland tongues >24% 10 3 5 0 0 0 200 15 15 C. Laney Member D. Lucaogou Formation 10 9 y = 8.30x - 7.58 r 2 = 0.95 100 n = 69 mean %TOC = 4.41 std. dev. = 4.64 Ro = 0.77-0.88% 12 Frequency S2 (mg/g) n = 91 mean %TOC = 7.84 std. dev. = 3.71 Ro = 0.40% y = 8.61x - 9.91 r 2 = 0.98 6 5 3 0 0 200 0 8 60 F. Jingjingzigou Formation S2 (mg/g) n = 201 mean %TOC = 4.09 std. dev. = 3.86 Ro = 0.20-0.45% 40 y = 7.90x - 2.87 r 2 = 0.97 100 7 n=8 mean %TOC = 1.44 std. dev. = 0.40 Ro = 0.88-0.91% 50 6 5 y = 5.60x - 2.55 r 2 = 0.82 30 4 3 Frequency E. Wilkins Peak Member 20 2 10 1 0 0 0 0 5 10 15 20 25 % TOC 0 5 10 15 20 25 % TOC Figure 5. Percent TOC (determined by LECO) vs. Rock-Eval S2 (points), and % TOC histograms (gray shading) for samples from six lacustrine petroleum source rock units. The slope of the linear regression lines multiplied by 100 gives the average Rock-Eval HI for each population, corrected for adsorption of pyrolysates on the rock matrix (cf. Langford and Blanc-Valleron, 1990). Ro " vitrinite reflectance in oil for each population. Note that vitrinite reflectances for the Junggar basin samples (B, D, and F) have been affected by outcrop oxidation and thus may be slightly higher than equivalent unweathered rocks (Carroll, 1998). to average 48% of visible kerogen; the remainder is mostly weakly fluorescent amorphous material. Biomarker distributions include features typical of fresh- water, suboxic depositional environments that have mixed terrestrial and aquatic organic matter input (Table 1). Carroll and Bohacs 1043 1044 Lacustrine Petroleum Source Rocks Table 1. Selected Geochemical Characteristics of Lacustrine Source Rocks and Oils* Basin Formation % Ro % TOC HI Pristane/Phytane** b-carotane Steranes Tricyclic Index** Gamma. Index Hopane/Steranes Algal-Terrestrial Organic Facies (Fluvial-Lacustrine Facies Association) Wyoming, Luman Tongue (rocks)† Junggar basin (W. China), Hongyanchi Fm. (rocks)†† Brazil basins (rocks and oils)‡ Gabon Kissenda shale‡‡ Phisanulok basin (Thailand; oils)§ C. Sumatra basin (rocks and oils)§§ 0.35–0.45 1.0–59.2 55–985 1.5–4.8 not detected 0.86–1.09 0–8 58–365 1.5–4.1 trace C29 # C27 ! C28 abundant 4-methyl C29 # C27 # C28 0.4–0.7 "6.5% $779 #1.3 not detected C29 ## C27 0.65–0.72 0.6–2.2 93–458 0.8–1.2 not detected n.a. n.a. n.a. 2.7–4.0 not detected 0.4–0.8 0.7–9.2 110–946 2.2–3.2 (not reported) (negligible) 1.0–4.0 48–71 4–11 2.6–7.7 30–100 20–40 5–15 C27 # C29 " C28 abundant 4-methyl C29 ## C28 # C27 (not reported) 7–35 4.2–17.5 (negligible) (negligible) 28.1–47.5 not detected? C29 # C28 % C27 abundant 4-methyl 12–27 4–6 3.8–7.7 0.1–0.5 present (not reported) (high) 0.4–0.8 79–85 19–36 2.5–5.2 100–200 20–70 5–15 (not reported) 13–150 1.5–7.7 Algal Organic Facies (Fluctuating Profundal Facies Association) Wyoming, Laney Member (rocks)† Junggar basin (W. China), Lucaogou Fm. (rocks)†† Brazil basins (rocks and oils)‡ Bucomazi shales (Angola) organic-rich zone (rocks)|| 0.40 1.5–17.1 52–1003 0.77–0.88 0–23 481–766 1.0–1.6 present C29 # C27 # C28 abundant 4-methyl C29 ! C28 ## C27 0.4–0.8 "9 "900 #1.1 present C29 # C27 0.56–0.81 2–24 #700 (not reported) (not reported) C27 # C29 ! C28 Hypersaline-Algal Organic Facies (Evaporative Facies Association) Wyoming, Wilkins Peak Member (rocks)|| || Junggar basin (W. China) Jingjingzigou Fm. (rocks)†† Junggar basin (W. China) Karamay trend (oils)# Jianghan basin (E. China) (rocks and oils)## 0.20–0.45 4.1–19.0 0.88–0.91 0.8–2.0 n.a. 0.45–0.55? 32–1001 0.1–1.1 abundant C29 # C28 ## C27 6–21 8–82 0.2–2.0 129–477 0.8–1.1 n.a. n.a. 0.9–2.3 "6.6 712–838 0.1–0.5 abundant to dominant abundant to dominant present C29 # C28 # C27 79–245 15–34 1.7–7.1 C29 ! C28 # C27 260–580 31–56 0.7–2.2 C27 # C29 # C28 7–28 35–216 0.3–2.4 *% Ro " vitrinite reflectance in oil; % TOC " total organic carbon; HI " Rock-Eval Hydrogen Index; Tricyclic Index " 100(C23 tricyclic terpane/C30 17#(H), 21b(H)-hopane); Gamma. Index " gammacerane/C30 17#(H), 21b(H)-hopane; Hopane/Steranes " C30 17#(H), 21b(H)-hopane/C29 20S # 20R 14#(H), 17#(H)-steranes; n.a. " not applicable. **Ratio strongly affected by thermal maturity. † Horsfield et al. (1994). †† Carroll (1998). ‡ Mello et al. (1988). ‡‡ Kuo (1994). § Kulwadee and Philp (1991). §§ Kelley et al. (1995). || Burwood et al. (1992, 1995). || || this study. # Clayton et al. (1997). ## Fu et al. (1986), Philp and Fan (1987), Peters et al. (1996). Carroll and Bohacs 1045 200 Luman + Niland Tongues S2 (mg/g) Population 1 n = 86 mean %TOC = 4.87 std. dev. = 1.54 Population 2 n = 85 mean %TOC = 9.34 std. dev. = 11.76 y = 8.05x - 8.08 r 2 = 0.94 100 y = 3.24x - 1.01 r 2 = 0.86 HI > 500 HI < 500 0 0 10 20 30 40 50 60 % TOC Figure 6. Percent TOC vs. S2 plot for Luman Tongue and Niland Tongue samples. The samples have been divided into two populations according to HI, and separate linear regression lines have been calculated for each population. Algal-terrestrial organic facies elsewhere typically have moderately high TOC contents (!1–10%) and mixed type I–type III kerogens (Table 1) and commonly occur in association with fluvial deposits and coal. High molecular weight n-alkanes (waxes) are major constituents of both rock extracts and oils because of input of protective tissues from higher land plants (Tissot and Welte, 1984) and membrane lipids from certain classes of freshwater algae (Goth et al., 1988; Tegelaar et al., 1989). Selective enrichment in these compounds may also result from selective bacterial degradation of other components in oxic to suboxic depositional environments (Powell, 1986). High pristane/phytane ratios (Table 1) result both from higher land plant input and oxic depositional conditions. High hopane/sterane ratios record bacterial degradation of relatively abundant terrestrial organic matter. Algal Organic Facies The fluctuating profundal facies association typically includes extremely organic-rich laminated mudstone facies containing abundant algal-derived organic matter. The TOC values in the lower LaClede Bed of the Laney Member of the Green River Formation are as great as 20%, and the average HI is 830 (Figures 3B, 5C). Alginite is the principal organic maceral (Horsfield et al., 1994). Subsidiary vitrinite and intertinite, 1046 Lacustrine Petroleum Source Rocks however, also occur in the highest TOC bluebeds, suggesting that these units were deposited during times of enhanced terrestrial runoff. Ectogenic meromixis as a result of increased inflow of fresh surface water has been proposed as a mechanism for promoting salinity stratification (Boyer, 1982), which in turn may have helped preserve organic matter. Biomarker distributions are consistent with predominantly aquatic organic matter input in saline lakes with anoxic bottom waters (Table 1). Maximum Lucaogou Formation organic enrichment occurs in laminated mudstone, interpreted as anoxic profundal facies (Graham et al., 1990; Carroll et al., 1992). Organic richness is highly variable within the Lucaogou Formation, ranging from less than 0.5% to greater than 20% TOC and is highest in submillimeter laminated intervals (Carroll, 1998) (Figures 4B, 5D). The lower average TOC values in the Lucaogou Formation compared with the lower LaClede Bed may in fact reflect more statistically representative sampling of the Lucaogou Formation. Average Rock-Eval HI values over this interval are essentially identical with the lower LaClede Bed (Figure 5C, D), and both are consistent with relatively homogenous type I kerogen. Fluorescent amorphous material dominates Lucaogou Formation kerogens, averaging 58% of visible organic matter, and attests to probable algal input (Carroll, 1998). Very light d13C values in extracts of the richest samples (Carroll, 1998) are inconsistent with the hypothesis that organic richness is controlled by high primary productivity, but correlations between productivity and organic richness have been reported in other basins (e.g., Curiale and Gibling, 1994). The absence of subaerial exposure surfaces, presence of fish fossils, and modest elevation of b-carotane and gammacerane in Lucagogou Formation extracts (Table 1) together are consistent with deposition within a salinitystratified lake. Algal organic facies in other basins represent some of the world’s richest lacustrine source rocks and contain mostly type I kerogen that has HI values that typically reach maxima in the 600–900 range and may exceed 1000 (Espitalié et al., 1977). Lower HI values reflect temporal variations in primary productivity (e.g., Curiale and Stout, 1993), degree of watercolumn anoxia (Demaison and Moore, 1980), and experimental artifacts arising from Rock-Eval pyrolysis (Katz, 1983; Langford and Blanc-Valleron, 1990). Extracts and oils are commonly rich in n-alkanes derived from membrane lipids of aquatic organisms. The distribution of n-alkanes may differ from freshwater fa- 5 S2 (mg/g) 4 y = 8.67x - 3.90 r 2 = 0.90 Frequency 6 100 3 2 1 0 0 10 Supralittoral n = 25 mean %TOC = 3.23 std. dev. = 2.94 100 6 y = 7.58x - 2.67 r 2 = 0.96 4 Frequency 8 S2 (mg/g) 2 0 0 40 Littoral 35 n = 86 mean %TOC = 1.84 std. dev. = 1.11 30 y = 8.00x - 3.27 r 2 = 0.92 20 15 Frequency 25 100 10 5 0 0 Sublittoral n = 76 mean %TOC = 7.33 std. dev. = 4.22 10 8 100 6 y = 7.83x - 1.82 r 2 = 0.96 4 Frequency Oil shales in the Wilkins Peak Member of the Green River Formation are thinner and slightly less areally extensive than those in the lower LaClede Bed but contain equally high maximum organic enrichments (up to 18% TOC) (Bohacs, 1998) (Figure 5E). The TOC contents in the Wilkins Peak Member vary widely but are generally lowest in littoral and lake-plain mudstone facies and highest in sublittoral mudstones and shales (Figure 7). These relationships demonstrate that the highest organic enrichments occur when the lakes were deepest. Note that average HI values in the Wilkins Peak Member (determined from S2 /TOC plots) are essentially identical for each environment, indicating very little lateral contrast in organic matter type. Amorphous organic matter, derived from algal or bacterial sources, dominates visible organic matter, confirming very low input from land plants. Some of the most organically enriched strata occur just above the major flooding surface at the base of each sequence (Figure 3C). Biomarker distributions are consistent with deposition under hypersaline, anoxic conditions (Table 1), although certain biomarker ratios (e.g., pristane/phytane ratios) may also reflect low thermal maturity. Organic enrichment in the Jingjingzigou Formation mudstone is relatively low (TOC less than 2%) (Figures 4C, 5F). Total organic carbon is highest in medium and dark gray laminated mudstones and drops to less than 1.0% in nonlaminated facies. Rock-Eval HI values reach a maximum of 477, suggesting oxidation of organic matter prior to burial. The Jingjingzigou Formation contains high proportions of amorphous 7 n = 14 mean %TOC = 1.11 std. dev. = 0.43 S2 (mg/g) Hypersaline Algal Organic Facies 8 Lake Plain/Alluvial S2 (mg/g) cies, however, in having lower odd-carbon-number preference and less abundant n-C30# components. Pristane/phytane ratios are typically close to or less than 1.0, reflecting lower terrestrial input, anoxic depositional conditions, and possibly elevated salinity. Other biomarker characteristics reflect the contributions of specific classes of aquatic organisms, as evidenced by the presence of moderate amounts of b-carotane, elevated tricyclic terpanes, and gammacerane. Gammacerane is a commonly cited indicator of salinity (e.g., Mello et al., 1988), although more recent work with compound-specific isotopic analysis suggests that gammacerane may in fact record input from bacterial communities living at or below the chemocline in stratified lakes (Schoell et al., 1994; Sinninghe Damsté et al., 1995). 2 0 0 0 5 10 15 20 %TOC Figure 7. Percent TOC histograms for core samples from the Wilkins Peak Member, subdivided according to interpreted depositional environment. Carroll and Bohacs 1047 kerogen, presumably of algal or bacterial origin (Carroll, 1998). Minor vitrinite, inertinite, and alginite make up the remainder of the visible kerogen. Biomarker distributions are commonly dominated by bcarotane, which has been associated with shallow, hypersaline lakes in which certain highly specialized organisms occur (Murphy et al., 1967; Hall and Douglas, 1983; Brassell et al., 1988; Duncan and Hamilton, 1988; ten Haven et al., 1988). Hypersaline organic facies commonly feature lower overall TOC values than do brackish-saline facies, although relatively thin intervals of high TOC occur during periods of maximum lake expansion. Mixtures of type I and type III kerogens appear to result from varying degrees of preservation of aquatic organic matter and from the admixture of minor terrestrial material. Maximum HI values equal or exceed those seen in algal organic facies (Table 1), but average values tend to be lower. Biomarker distributions reflect low-diversity assemblages of highly specialized organisms living under harsh environmental conditions. Pristane/phytane ratios substantially below 1.0 may result either from anoxic depositional conditions in a stratified, hypersaline lake, or from contributions from halophilic bacteria (Goosens et al., 1984). b-carotane is commonly an abundant to dominant constituent, as are elevated concentrations of tricyclic terpanes and gammacerane (Table 1). Hopane/sterane ratios are typically low. In addition to the examples cited previously, hypersaline lacustrine organic facies are known from several Tertiary basins in China (Shi et al., 1982; Fu et al., 1986; Sheng et al., 1987; Brassell et al., 1988; R. Li et al., 1988, 1992; Z. Chen et al., 1994; J. Chen et al., 1996; Peters et al., 1996) and in Spain (e.g., Salvany and Ortı́, 1994; Sanz et al., 1994). DISCUSSION: PETROLEUM GENERATION FROM LACUSTRINE SOURCE ROCKS Bradley (1925) noted that for certain members of the Green River Formation, “large volumes of microscopic plants and perhaps also animals accumulated.” Studies of oil-shale facies of the Mahogany ledge of the Parachute Creek Member led to the recognition of type I lacustrine kerogen, characterized by high atomic H/C ratios and HI (van Krevelen, 1961; Espitalié et al., 1977). Subsequent experience has shown, however, that kerogens in many modern and ancient lake systems differ from type I, and that type I is not even representative of all members of the Green River For1048 Lacustrine Petroleum Source Rocks mation. For example, modern east African lakes preserve organic matter ranging from type I to type III (Katz, 1988, 1990; Talbot, 1988). Recent studies have demonstrated that these distinctions are critical not only for estimating the relative quality and quantity of oil and gas that may be generated, but also for determining the timing of hydrocarbon generation (e.g., Anders et al., 1992; Tegelaar and Noble, 1994; Peters et al., 1996). The following discussion considers generative characteristics of mixed type I–III kerogen typical of the algal-terrestrial organic facies (fluvial-lacustrine facies association), type I kerogen typical of algal organic facies (fluctuating profundal facies association), and type I-S kerogen that has been reported in association with some hypersaline-algal organic facies (evaporative facies association). Oil and Gas Generation from Mixed Type I–III Kerogens Tegelaar and Noble (1994) demonstrated through pyrolysis experiments that vitrinite-dominated (terrestrial) kerogen generally generates hydrocarbons over a broader range of temperatures than do most algaldominated kerogens and that generation continues well above the range of temperatures associated with generation from algal-dominated kerogen. This result suggests that given the same burial and thermal history, mixtures of aquatic and terrestrial organic matter should generate petroleum over a broader range of thermal maturities than purely algal source facies. Data from the Uinta basin in Utah are consistent with this hypothesis. Oils in the Altamont-Bluebell fields were sourced primarily from freshwater lake facies of the lower Green River and underlying formations that resemble the Luman Tongue (Fouch, 1975; Ruble and Philp, 1998). Based on Rock-Eval transformation ratios, light hydrocarbon yields, and atomic H/C ratios, hydrocarbon generation from these facies occurred in the deep Uinta basin over a broad range of thermal maturities, ranging from approximately 0.70 to 1.35 % Ro (Anders et al., 1992). Uinta basin oils are solid at surface temperatures because of their very high wax content. High wax content and pour point are also associated with freshwater lacustrine source rocks in the Central Sumatra basin (Kelley et al., 1995), in the Songliao basin of north China (Yang et al., 1985), in central African rift basins (Genik, 1993), and in some Brazilian rift basins (Mello et al., 1988; Mello and Maxwell, 1990). Minor amounts of natural gas are also common in oil fields sourced by mixed type I–III mixed kerogens (e.g., Clem, 1985; Rice et al., 1992; Genik, 1993; Kelley et al., 1995), but the sources of these gases have not been clearly established. Oil Generation from Type I Kerogen Waples (1980) and Sweeney et al. (1987) showed that type I kerogens generate oil over a very narrow range of thermal maturities, reflecting little variation in chemical bond type within these homogenous kerogens. Tegelaar and Noble (1994) found that the onset of oil generation from Green River type I kerogen should occur between 0.8 and 0.9% Ro, and peak generation is at 0.95–1.05% Ro. The overall oil window (defined by 10–90% kerogen transformation ratios) thus spans only about 0.3% Ro on average, or less than 30&C based on a 1&C/m.y. heating rate. They found that the peak generation other type I kerogens also generate over a very narrow range of thermal maturities, although the absolute thermal maturity at which generation begins could vary widely. They calculated that the onset of oil generation could range between 0.54 and 0.96% Ro and concluded that bulk chemical composition alone was not sufficient to predict generation timing. Using pyrolysis–gas chromatography techniques to better discern kerogen chemical structures, they found that two other factors influence generation timing: (1) the types and mixtures of biomacromolecules preserved, and (2) organic sulfur content. Whether absolute generation timing can be accurately determined from bulk chemical measurements such as Rock-Eval HIs is, therefore, currently unclear. Type I kerogens generate paraffinic oils produced from the Karamay and associated fields in the Junggar basin (Clayton et al., 1997). Karamay oils are low in sulfur, and except where biodegraded, contain abundant n-alkanes that have molecular weights less than C30. A similar n-alkane distribution was reported for oils sourced from type I kerogen in the Campos basin of Brazil (Mello et al., 1988; Mello and Maxwell, 1990). The distribution of n-alkanes in oils generated from type I kerogens may vary widely, however, and are subject to modifications related to thermal maturity and biodegradation. Early Generation from Type I-S Kerogen? Several Tertiary lacustrine basins in China contain oils that appear to have been generated at lower thermal maturities than are normally associated with the breakdown of typical marine or lacustrine kerogens. Such oils have been reported from onshore extensions of the Bohai Bay basin (Shengli oil field) (Shi et al., 1982; Z. Chen et al., 1994), the Dongpu basin (R. Li et al., 1988, 1992), the Jianghan basin (Fu et al., 1986; Sheng et al., 1987; Brassell et al., 1988; Peters et al., 1996), and the Qaidam basin (Huang et al., 1991) and are commonly associated with saline or hypersaline source rocks. Based on source rock–oil correlations and biomarker maturity measurements, significant generation appears to have occurred from these rocks at vitrinite reflectance values as low as 0.45%. Several molecular maturity measurements, including the ratios of 20S/(20S # 20R) desmethyl steranes and 22S/(22S # 22R) homohopanes, provide confirmation of the low thermal maturity of these oils. Jianghan basin oils, for example, commonly have 20S sterane ratios as low as 0.17–0.24, in contrast to the observation by (Mackenzie et al., 1980) that petroleum generation from marine type II kerogen begins at values of about 0.40. Likewise, Jianghan oils have C32 22S hopane ratios as low as 0.44 (Fu et al., 1986), in contrast to values of approximately 0.50–0.55 that typically mark the onset of petroleum generation from marine kerogens. If these low maturities are representative of a significant fraction of the total petroleum generation, then exploration models for basins containing such oils must allow for earlier generation of oil relative to trap formation and other play elements. Two explanations have been offered for these lowmaturity oils. The first is that they do not represent thermal degradation of kerogens at all, but instead result from degradation and migration of original soluble organic matter that was never incorporated into kerogen. For example, certain coals and carbonaceous shales rich in higher land plant remains (particularly from conifers) may contain abundant resins (soluble organic matter), which may be expelled as liquids (Snowdon and Powell, 1982; Stout, 1995). Huang et al. (1991) invoked such an explanation for Qaidam basin light oils and condensates that have 20S sterane maturity ratios of 0.18–0.23. X. Li et al. (1998) proposed that two distinct pulses of petroleum generation occurred in the East China Sea basin, the first occurring at less than 0.55% Ro and the second between 0.55 and 1.30% Ro. Resinite derived oils reported from Canada are naphthenic (high percentage of hydrocarbons having ring structures) rather than paraffinic, but different resin types and varying proportions of resinite relative to other macerals may partly account for more paraffinic oils in China. Carroll and Bohacs 1049 Another important consideration is the potential volumetric significance of oil generated from resins, which typically comprise relatively low percentages of the total organic matter (Tissot and Welte, 1984). Saline or hypersaline lacustrine facies would be expected to contain relatively little resinous land plant organic matter. For example, oils in the Shengli field are thought to represent transformation of less than 10% of the total organic matter present in the source rocks (Cheng Keming, Research Institute of Petroleum Exploration and Development, Beijing, 1997, personal communication). Further volumetric data on the Shengli oil field and other accumulations of low maturity oils are needed to determine whether expulsion of biogenic bitumen is adequate to account for the known oil reserves. A second and possibly complementary explanation is that low-maturity oils result from thermal degradation of a distinctive type I-S (sulfur-rich) kerogen. type I-S kerogen is defined as having an HI above 600 and a S/C atomic ratio greater than 0.04 (Sinninghe Damsté et al., 1993; Peters et al., 1996). Jianghan basin oils are generally high in sulfur (3.59–12.91%) (Sheng et al., 1987), and aromatic organosulfur compounds are abundant (Philp and Fan, 1987; Sheng et al., 1987). Peters et al. (1996) presented experimental kinetic data showing that the type I-S kerogen in Jianghan hypersaline lacustrine source rocks reacts quickly to thermal stress, in a manner similar to marine type II-S kerogen in the Monterey Formation. Type II-S kerogens have been demonstrated to generate oil at lower thermal exposures than other kerogens (Orr, 1986). Hydrous pyrolysis experiments using Monterey kerogens provide evidence that this generation actually occurs via a two-step process (Baskin and Peters, 1992). In the first step, cleavage of relatively weak S–C bonds generates heavy bitumen that is retained on the kerogen matrix. Thermal degradation of this bitumen at slightly higher temperatures results in the expulsion of oil. Thus, this model appears to combine elements of the “oil from resins” model discussed previously with thermal degradation of an uncommonly reactive sulfur-rich kerogen. Low maturity Monterey Formation oils, however, have low API gravities and are dominated by asphaltenes and resins, whereas Jianghan oils are dominantly paraffinic (Philp and Fan, 1987). More work is clearly needed to resolve the actual generation mechanisms responsible for low-maturity oils in China. Type I-S kerogens appear to result from diagenetic sulfurization rather than from biological in1050 Lacustrine Petroleum Source Rocks put of organosulfur compounds. Sheng et al. (1987) identified long-chain normal alkyl-thiophenes and alkyl-thiolanes, long-chain isoprenoid-thiophenes and isoprenoid-thiolanes, and benzothiophenes in sulfurrich oils. The distribution of these compounds mirrors that of the corresponding alkanes, leading Sheng et al. (1987) to conclude that the sulfur compounds originated through diagenetic reactions between elemental sulfur and sulfides with phytol, fatty acids, and alcohols. The apparent rarity of type I-S kerogen may stem from the fact that most lake waters have low sulfate concentrations relative to marine systems and that in siliciclastic lacustrine systems there is commonly excess iron available to form pyrite or other sulfides. These limitations, however, may be overcome if sulfide scavengers such as Fe and Mn are scarce, especially if sulfate supply to the basin is unusually high. For example, Sinninghe Damsté et al. (1993) documented type I-S kerogen in two Tertiary Spanish oil shales, which they interpreted as having formed as a result of weathering of Triassic evaporites. Sulfate from the evaporites was microbially reduced in a freshwater lake and incorporated into previously deposited remains of Botryococcus braunii algae. A more common setting for type I-S kerogen is probably in evaporative lakes where siliciclastic sediment input is low and evaporative concentration of sulfate occurs. In the Chinese basins, the oil source rocks are closely associated with gypsum and other evaporites and have biomarker characteristics indicative of anoxic saline to anoxic hypersaline environmental conditions (Shi et al., 1982; Fu et al., 1986; Philp and Fan, 1987; Sheng et al., 1987; Brassell et al., 1988; Huang et al., 1991; Z. Chen et al., 1994). CONCLUSIONS 1. Three end-member lacustrine facies associations have been observed to recur in widely disparate geographic settings and over a wide range of geologic time: fluvial lacustrine, fluctuating-profundal, and evaporative. Significant differences exist among each of the these associations in terms of oil vs. gas generation and the timing of petroleum generation relative to basin thermal history. These associations can be used to make first-order predictions of petroleum generation type (oil vs. gas) and timing from limited geologic data on nonsource facies. Conversely, geochemical analysis of source rocks or oils may aid in predicting lacustrine paleoenviron- ments and the likely distribution and quality of reservoir and seal facies. 2. Lacustrine source rocks display a high degree of geochemical heterogeneity relative to marine facies, therefore their complete characterization requires analysis of a relatively large number of samples selected at fixed, regular intervals. Selective sampling of a few particularly rich beds may lead to erroneous conclusions concerning overall generative potential. 3. No typical lacustrine source rock or oil exists. The default-value kerogen properties and kinetics sometimes used in basin modeling are therefore of limited utility. For optimal precision, detailed kinetic measurements should be made from immature equivalents of the suspected source facies, if possible, and should be supported by molecular maturity measurements from source rock extracts and generated oils. REFERENCES CITED Anders, D. E., J. G. 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