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At least 19 recordsLinked to original sources

High concentration methane hydrate in a silt reservoir from the deep-water Gulf of Mexico

We present results from 30 quantitative degassing experiments of pressure core sections collected during The University of Texas-Gulf of Mexico 2-1 (UT-GOM2-1) Hydrate Pressure Coring Expedition at Green Canyon Block 955 in the deep-water Gulf of Mexico as part of The University of Texas at Austin–US Department of Energy Deepwater Methane Hydrate Characterization and Scientific Assessment. The hydrate saturation ( S h ), the volume fraction of the pore space occupied by hydrate, is 79% to 93% within sandy silt beds (centimeters to meters in thickness) between 413 and 442 m below seafloor in 2032 m water depth. Sandy silt intervals are characterized by high compressional wave velocity ( V p ) (2515–3012 m s −1 ) and are interbedded with clayey silt sections that have lower S h (2%–35%) and lower V p (1684–2023 m s −1 ). Clayey silt intervals are composed of thin laminae of silts with high S h within clay-rich intervals containing little to no hydrate. Degassing of single-lithofacies sections reveals higher-resolution variation in S h than is possible to observe in well logs; however, the average S h of 64% through the reservoir is similar to well log estimates. Gas recovered from the hydrates during these experiments is composed almost entirely of methane (99.99% CH 4 , <100 ppm C 2 H 6 on average), with an isotopic composition (δ 13 C: −60.4‰ and −63.6‰ Vienna Peedee belemnite and δ 2 H: −178.2‰ and −179.0‰ Vienna standard mean ocean water) that suggests the methane is primarily from a microbial source. A subset of six degassing experiments performed using very small pressure decrements indicates that the salinity within these samples is close to the average seawater concentration, suggesting that hydrate either formed slowly or formed during a rapid event at least tens of thousands of years before present.

Texas, Louisiana

Compression behavior of hydrate-bearing sediments

This work experimentally explores porosity, compressibility, and the ratio of horizontal to vertical effective stress ( K 0 ) in hydrate-bearing sandy silts from Green Canyon Block 955 in the deep-water Gulf of Mexico. The samples have an in situ porosity of 0.38 to 0.40 and a hydrate saturation of more than 80%. The hydrate-bearing sediments are stiffer than the equivalent hydrate-free sediments; the K 0 stress ratio is greater for hydrate-bearing sediments relative to the equivalent hydrate-free sediments. The porosity decreases by 0.01 to 0.02 when the hydrate is dissociated at the in situ effective stress. We interpret that the hydrate in the sediment pores is a viscoelastic material that behaves like a fluid over experimental time scales, yet it cannot escape the sediment skeleton. During compression, the hydrate bears a significant fraction of the applied vertical load and transfers this load laterally, resulting in the apparent increased stiffness and a larger apparent K 0 stress ratio. When dissociation occurs, the load carried by the hydrate is transferred to the sediment skeleton, resulting in further compaction and a decrease in the lateral stress. The viewpoint that the hydrate is a trapped viscous phase provides a mechanism for how stiffness and stress ratio ( K 0 ) are greater when hydrate is present in the porous media. This study provides insight into the initial stress state of hydrate-bearing reservoirs and the geomechanical evolution of these reservoirs during production.

Louisiana

Meter-scale lithofacies cycle and controls on variations in oil saturation, Wolfcamp A, Delaware and Midland Basins

Typical meter-scale lithofacies cycles from the Wolfcamp A in the Delaware and Midland Basins comprise basal carbonate facies overlain by calcareous or siliceous mudrocks. Siliceous mudstones are the most organic-rich facies with high total organic carbon ( TOC > 3 wt. %), whereas thin carbonate beds have the lowest organic matter (OM) content among the lithofacies present ( TOC TOC, programmed pyrolysis analysis, and residual gas analysis from rock crushing. Oil saturation index ( OSI ) (the amount of free oil normalized by TOC ; OSI = S 1 × 100/ TOC ) is used as an indicator of oil enrichment or depletion in the reservoir, where S 1 is volatile oil in programmed pyrolysis (temperature = 300°C). Both TOC -lean carbonate and TOC -rich mudstone lithofacies have high OSI in these meter-scale cycles (average OSI is 124.5 mg HC/g TOC for carbonate beds), indicating that migrated oil is present. Residual gas analyses show lower dryness values (C 1 /C 1–5 ) and higher oil indicator values (100 × C 4+5 /C 1–5 ) in TOC -lean carbonate beds compared to the TOC -rich mudstones, likely indicating a cumulative oil and gas charging effect through source rock maturation. Oil and gas generated at different stages of thermal maturation were partially expelled from OM-rich siliceous/calcareous mudstones into adjacent OM-lean carbonate beds. This study shows oil expulsion from source to adjacent carbonate beds is a key factor in variations of oil saturation in the Wolfcamp A.

AAPG Bulletin

Reevaluation of thermal maturity and stages of petroleum formation of the Mississippian Barnett Shale, Fort Worth Basin, Texas

New data including measured reflectance (% R o ), programmed open-system pyrolysis data, and kerogen elemental analyses obtained on the Mississippian Barnett Shale in the Fort Worth Basin, Texas, indicate that secondary-gas generation starts at 1.5% R o and not at the previously prescribed 1.1% R o . Oil-cracking kinetic parameters derived from pyrolysis experiments in the presence and absence of water indicate that secondary-gas generation will not occur at a thermal maturity as low as 1.1% R o and requires a minimum thermal maturity of 1.5% R o . This difference is especially important in using the Barnett Shale as an analog for evaluating other possible shale-gas plays. The new reflectance measurements have a good relationship with hydrogen indices (HIs) and compare well with other published data sets. However, the relationship does not compare well with the previously published data used to prescribe 1.1% R o as the start of secondary-gas generation in the Barnett Shale. This discrepancy is attributed to differences in measured % R o values and not attributed to differences in the HI values. Lack of publicly available information on the previously reported % R o values makes it difficult to ascertain the reason for their lower values. These lower % R o values also have impact on the previously prescribed relationship for estimating % R o from the temperature at maximum yield by programmed open-system pyrolysis ( T max ). As a result, the new data do not agree with a previously described relationship, and the considerable scatter makes the new relationship unreliable. However, the relationship between the HI and % R o has less scatter, which indicates that HI offers a better proxy in calculating % R o than T max for the Barnett Shale. Comparison of various programmed open-system pyrolysis methods (i.e., Rock-Eval II, Rock-Eval 6, Source Rock Analyzer, and Hawk) indicates that variations in HI are within ±10% of one another. An HI of at least 44 mg/g total organic carbon is prescribed as a more certain limit for the start of secondary-gas generation and prospective in situ gas-shale accumulations.

Texas

Geologic models underpinning the 2018 US Geological Survey assessment of hydrocarbon resources in the Eagle Ford Group and associated Cenomanian–Turonian strata, United States Gulf Coast, Texas

The availability of new geologic and production data has greatly increased since 2010, when the US Geological Survey (USGS) last assessed undiscovered, technically recoverable oil and gas resources in the Cenomanian–Turonian (CT) Eagle Ford Group (EFG) across Texas. This new information facilitated an updated assessment of undiscovered continuous oil and gas resources in the Eagle Ford and associated CT strata. Literature and USGS research data were used to build the geologic models for the assessment units (AUs). The USGS defined six continuous AUs within the EFG: (1) Eagle Ford Marl Continuous Oil, (2) Eagle Ford Marl Continuous Gas, (3) Submarine Plateau-Karnes Trough Continuous Oil, (4) Submarine Plateau-Karnes Trough Continuous Gas, (5) CT Mudstone Continuous Oil, and (6) CT Mudstone Continuous Gas. An additional AU, the CT Slope Continuous Gas AU, was defined but not quantitatively assessed. The boundaries of these AUs were defined by thickness, lithofacies, thermal maturity, regional geology, and the spatial distribution of productive fairways. The resulting total mean estimates for undiscovered, technically recoverable resources for these six AUs are 8.5 billion bbl of oil and 66 trillion ft 3 of gas. These results for both oil and gas resources are within the top five volumes of previously assessed continuous accumulations in the United States and attest to the importance of the EFG and associated CT strata as a significant source of petroleum well into the future.

Texas

Pressure coring operations during The University of Texas-Gulf of Mexico 2-1 (UT-GOM2-1) Hydrate Pressure Coring Expedition in Green Canyon Block 955, northern Gulf of Mexico

In May 2017, The University of Texas Hydrate Pressure Coring Expedition Gulf of Mexico 2-1 (UT-GOM2-1) drilled two adjacent holes in Green Canyon Block 955 in the deep-water Gulf of Mexico as part of The University of Texas at Austin and US Department of Energy Deepwater Methane Hydrate Characterization and Scientific Assessment. Expedition operations included testing two configurations of a rotary pressure-coring tool in a gas hydrate–bearing formation. In the first hole, an extended core barrel (cutting shoe) configuration of the Pressure Coring Tool with Ball Valve (PCTB-CS) was deployed, and in the second hole, the PCTB face bit configuration (PCTB-FB) was deployed. The PCTB-CS successfully recovered and maintained pressure for only one core out of eight deployments. A series of incremental modifications were made during and after the PCTB-CS deployment period that impacted the operations of the subsequent PCTB-FB deployments. Thus, in the second hole, the PCTB-FB successfully recovered and maintained pressure within the hydrate stability zone for 11 cores out of 13 deployments. The PCTB cored gas hydrate–bearing sandy silt interbedded with non–hydrate-bearing clayey silt within the main reservoir. The PCTB also recovered long intervals of unbroken, high-quality core with preserved sedimentary structures. We recovered one pressure core 130 m (437 ft) above the main hydrate reservoir in the silty clay. Pressure coring is the only available technology for recovering intact cores from sediment that is normally disturbed by gas expansion, dissolution, or dissociation; this allows a wide range of scientific measurements to be obtained with minimal disturbance to the core sediment fabric. Analysis of pressure cores has the potential to illuminate the in situ properties, gas saturation, and gas composition of a wide range of reservoirs including unconventional shale systems.

AAPG Bulletin

Determining the source and genetic fingerprint of natural gases using noble gas geochemistry: a northern Appalachian Basin case study

Silurian and Devonian natural gas reservoirs present within New York state represent an example of unconventional gas accumulations within the northern Appalachian Basin. These unconventional energy resources, previously thought to be noneconomically viable, have come into play following advances in drilling (i.e., horizontal drilling) and extraction (i.e., hydraulic fracturing) capabilities. Therefore, efforts to understand these and other domestic and global natural gas reserves have recently increased. The suspicion of fugitive mass migration issues within current Appalachian production fields has catalyzed the need to develop a greater understanding of the genetic grouping (source) and migrational history of natural gases in this area. We introduce new noble gas data in the context of published hydrocarbon carbon (C 1 ,C 2+ ) ( 13 C) data to explore the genesis of thermogenic gases in the Appalachian Basin. This study includes natural gases from two distinct genetic groups: group 1, Upper Devonian (Marcellus shale and Canadaway Group) gases generated in situ, characterized by early mature ( 13 C[ C1 C2 ][ 13 C 1 13 C 2 ]: &ndash;9 ), isotopically light methane, with low ( 4 He) (average, 1 10 3 cc/cc) elevated 4 He/ 40 Ar and 21 Ne / 40 Ar (where the asterisk denotes excess radiogenic or nucleogenic production beyond the atmospheric ratio), and a variable, atmospherically (air-saturated&ndash;water) derived noble gas component; and group 2, a migratory natural gas that emanated from Lower Ordovician source rocks (i.e., most likely, Middle Ordovician Trenton or Black River group) that is currently hosted primarily in Lower Silurian sands (i.e., Medina or Clinton group) characterized by isotopically heavy, mature methane ( 13 C [C1 &ndash; C2] [ 13 C 1 13 C 2 ]: 3 ), with high ( 4 He) (average, 1.85 10 3 cc/cc) 4 He/ 40 Ar and 21 Ne / 40 Ar near crustal production levels and elevated crustal noble gas content (enriched 4 He, 21 Ne , 40 Ar ). Because the release of each crustal noble gas (i.e., He, Ne, Ar) from mineral grains in the shale matrix is regulated by temperature, natural gases obtain and retain a record of the thermal conditions of the source rock. Therefore, noble gases constitute a valuable technique for distinguishing the genetic source and post-genetic processes of natural gases.

New York

Thermogenic hydrocarbons in unconsolidated sediment of Eel river basin, offshore northern California

Thermally produced hydrocarbons were recovered from unconsolidated sediment ponded within a bathymetric depression on the surface of a shale diapir in the offshore Eel River Basin of northern California. Evidence that the hydrocarbons are thermogenic consists of the following: (1) very high concentrations of hydrocarbon gases, particularly ethane through butanes (C 2 -C 4 ); (2) methane having a carbon isotopic composition (relative to the PDB standard) of −43 and −44 per mil; (3) presence of gasoline-range (C 5+ ) hydrocarbons; and (4) presence of a complex mixture of heavy hydrocarbons (C 15+ ) with n-alkanes having a petroleumlike distribution. This mixture of gaseous and liquid hydrocarbons likely originated deep within the basin and migrated to the surface through fractures and faults developed during the emplacement of the diapir. The presence of thermogenic hydrocarbons in unconsolidated surface sediment indicates that conditions for petroleum generation have existed within this offshore basin.

California

High-porosity Cenozoic carbonate rocks of South Florida: Progressive loss of porosity with depth

Porosity measurements by borehole gravity meter in subsurface Cenozoic carbonates of south Florida reveal an extremely porous mass of limestone and dolomite which is transitional in total pore volume between typical porosity values for modern carbonate sediments and ancient carbonate rocks. A persistent decrease of porosity with depth, similar to that of chalks of the Gulf Coast, occurs in these rocks. We make no attempt to differentiate depositional or diagenetic facies which produce scatter in the porosity-depth relationship; the dominant data trends thus are functions of carbonate rocks in general rather than of particular carbonate facies. Carbonate strata with less than 20% porosity are absent from the rocks studied here. Aquifers and aquicludes cannot be distinguished on the basis of porosity. Although aquifers are characterized by great permeability and well-developed vuggy and even cavernous porosity in some intervals, they are not exceptionally porous when compared to other Tertiary carbonate rocks in south Florida. Permeability in these strata is governed more by the spacial distribution of pore space and matrix than by the total volume of porosity present. Dolomite is as porous as, or slightly less porous than, limestones in these rocks. This observation places limits on any model proposed for dolomitization and suggests that dolomitization does not take place by a simple ion-for-ion replacement of magnesium for calcium. Dolomitization may be selective for less porous limestone, or it may involve the incorporation of significant amounts of carbonate as well as magnesium into the rock. The great volume of pore space in these rocks serves to highlight the inefficiency of early diagenesis in reducing carbonate porosity and to emphasize the importance of later porosity reduction which occurs during the burial or late near-surface history of limestones and dolomites.

Florida

Tectonic evolution of Gulf of Anadyr and formation of Anadyr and Navarin basins

New seismic reflectionand refraction data reveal that Anadyr basin is separated from Navarin basin by Anadyr ridge, a southeast-northwest-trending bedrock high that is characterized by high-amplitude, short-wavelength magnetic anomalies. Anadyr ridge may be an offshore extension of the melange belt underlying the Koryak Range. Sonobuoy refraction data indicate that the velocity profile of strata in East Anadyr trough is similar to that in Navarin basin. Structurally, the basins are different.

Siberia

Underpressure in Mesozoic and Paleozoic rock units in the Midcontinent of the United States

Potentiometric surfaces for Paleozoic strata, based on water well levels and selected drill-stem tests, reveal the control on hydraulic head exerted by outcrops in eastern Kansas and Oklahoma. From outcrop in the east, the westward climb of hydraulic head is much less than that of the land surface, with heads falling so far below land surface that the pressure:depth ratio in eastern Colorado is less than 5.7 kPa/m (0.25 psi/ft). Permian evaporites separate the Paleozoic hydrogeologic units from a Lower Cretaceous (Dakota Group) aquifer, and a highly saline brine plume pervading Paleozoic units in central Kansas and Oklahoma is attributed to dissolution of Permian halite. Underpressure also exists in the Lower Cretaceous hydrogeologic unit in the Denver Basin, which is hydrologically separate from the Paleozoic units. The data used to construct the seven potentiometric surfaces were also used to construct seven maps of pressure:depth ratio. These latter maps are a function of the differences among hydraulic head, land-surface elevation, and formation elevation. As a consequence, maps of pressure:depth ratio reflect the interplay of three topologies that evolved independently with time. As underpressure developed, gas migrated in response to the changing pressure regime, most notably filling the Hugoton gas field in southwestern Kansas. The timing of underpressure development was determined by the timing of outcrop exposure and tilting of the Great Plains. Explorationists in western Kansas and eastern Colorado should not be surprised if a reservoir is underpressured; rather, they should be surprised if it is not.

Arkansas, Colorado, Kansas, Iowa, Missouri, Nebras

Comprehensive pressure core analysis for hydrate-bearing sediments from Gulf of Mexico Green Canyon Block 955, including assessments of geomechanical viscous behavior and nuclear magnetic resonance permeability

Quantifying the petrophysical and geomechanical properties of gas hydrate reservoirs is essential for understanding the natural hydrate system and predicting gas production behavior for future resource development. Pressure-core analysis tools were used to characterize methane hydrate–bearing sediments recovered from the Gulf of Mexico Green Canyon Block 955, under an international collaboration with The University of Texas and the National Institute of Advanced Industrial Science and Technology. Pressure-core samples were successfully transferred from Austin, Texas to Sapporo, Japan. Index property measurements (grain size, grain density, hydration number, gas composition, thermal conductivity), along with triaxial compression, consolidation, and permeability tests with a nuclear magnetic resonance (NMR) analyzer were conducted. Compression tests at different strain rates confirmed a strain rate dependence for hydrate-bearing sediment, and an equation for predicting strength as a function of hydrate saturation and strain rate is proposed. Compression and swelling indices were obtained from high-effective stress consolidation tests. Furthermore, secondary compression coefficients for hydrate-bearing sediments were obtained, suggesting that hydrate exhibits creeping behavior on timescales of minutes to hours. A relatively high initial permeability of a few millidarcys was confirmed. In addition, the first NMR signal measurement was performed on a hydrate-bearing pressure core to acquire the NMR transverse or spin-spin ( T 2 ) distribution. Results confirm that the Schlumberger Doll Research model and Timur-Coates model predictions underestimate permeability measured directly via fluid flow. Permeability estimated using specific surface values derived from NMR T 2 distributions is in good agreement with flow test results. Finally, an extended Timur-Coates model was proposed and predicts intrinsic permeability with high accuracy.

Texas

Pressure coring a Gulf of Mexico deep-water turbidite gas hydrate reservoir: Initial results from The University of Texas–Gulf of Mexico 2-1 (UT-GOM2-1) Hydrate Pressure Coring Expedition

The University of Texas Hydrate Pressure Coring Expedition (UT-GOM2-1) recovered cores at near in situ formation pressures from a gas hydrate reservoir composed of sandy silt and clayey silt beds in Green Canyon Block 955 in the deep-water Gulf of Mexico. The expedition results are synthesized and linked to other detailed analyses presented in this volume. Millimeter- to meter-scale beds of sandy silt and clayey silt are interbedded on the levee of a turbidite channel. The hydrate saturation (the volume fraction of the pore space occupied by hydrate) in the sandy silts ranges from 79% to 93%, and there is little to no hydrate in the clayey silt. Gas from the hydrates is composed of nearly pure methane (99.99%) with less than 400 ppm of ethane or heavier hydrocarbons. The δ 13 C values from the methane are depleted (−60‰ to −65‰ Vienna Peedee belemnite), and it is interpreted that the gases were largely generated by primary microbial methanogenesis but that low concentrations of propane or heavier hydrocarbons record at least trace thermogenic components. The in situ pore-water salinity is very close to that of seawater. This suggests that the excess salinity generated during hydrate formation diffused away because the hydrate formed slowly or because it formed long ago. Because the sandy silt deposits have high hydrate concentration and high intrinsic permeability, they may represent a class of reservoir that can be economically developed. Results from this expedition will inform a new generation of reservoir simulation models that will illuminate how these reservoirs might be best produced.

Texas, Louisiana

Chemometric differentiation of crude oil families in the San Joaquin Basin, California

Chemometric analyses of geochemical data for 165 crude oil samples from the San Joaquin Basin identify genetically distinct oil families and their inferred source rocks and provide insight into migration pathways, reservoir compartments, and filling histories. In the first part of the study, 17 source-related biomarker and stable carbon-isotope ratios were evaluated using a chemometric decision tree (CDT) to identify families. In the second part, ascendant hierarchical clustering was applied to terpane mass chromatograms for the samples to compare with the CDT results. The results from the two methods are remarkably similar despite differing data input and assumptions. Recognized source rocks for the oil families include the (1) Eocene Kreyenhagen Formation, (2) Eocene Tumey Formation, (3–4) upper and lower parts of the Miocene Monterey Formation (Buttonwillow depocenter), and (5–6) upper and lower parts of the Miocene Monterey Formation (Tejon depocenter). Ascendant hierarchical clustering identifies 22 oil families in the basin as corroborated by independent data, such as carbon-isotope ratios, sample location, reservoir unit, and thermal maturity maps from a three-dimensional basin and petroleum system model. Five families originated from the Eocene Kreyenhagen Formation source rock, and three families came from the overlying Eocene Tumey Formation. Fourteen families migrated from the upper and lower parts of the Miocene Monterey Formation source rocks within the Buttonwillow and Tejon depocenters north and south of the Bakersfield arch. The Eocene and Miocene families show little cross-stratigraphic migration because of seals within and between the source rocks. The data do not exclude the possibility that some families described as originating from the Monterey Formation actually came from source rock in the Temblor Formation.

AAPG Bulletin

Chemical and isotopic changes in Williston Basin brines during long-term oil production: An example from the Poplar dome, Montana

Brine samples were collected from 30 conventional oil wells producing mostly from the Charles Formation of the Madison Group in the East and Northwest Poplar oil fields on the Fort Peck Indian Reservation, Montana. Dissolved concentrations of major ions, trace metals, Sr isotopes, and stable isotopes (oxygen and hydrogen) were analyzed to compare with a brine contaminant that affected groundwater northeast of the town of Poplar. Two groups of brine compositions, designated group I and group II, are identified on the basis of chemistry and 87 Sr/ 86 Sr ratios. The solute chemistry and Sr isotopic composition of group I brines are consistent with long-term residency in Mississippian carbonate rocks, and brines similar to these contaminated the groundwater. Group II brines probably resided in clastic rocks younger than the Mississippian limestones before moving into the Poplar dome to replenish the long-term fluid extraction from the Charles Formation. Collapse of strata at the crest of the Poplar dome resulting from dissolution of Charles salt in the early Paleogene probably developed pathways for the ingress of group II brines from overlying clastic aquifers into the Charles reservoir. Such changes in brine chemistry associated with long-term oil production may be a widespread phenomenon in the Williston Basin.

Montana

Integrated geochemical approach to determine the source of methane in gas hydrate from Green Canyon Block 955 in the Gulf of Mexico

Massive volumes of gas are sequestered within gas hydrate in subsurface marine sediments in the Gulf of Mexico. Methane associated with gas hydrate is a potentially important economic resource and a significant reservoir of carbon within the global carbon cycle. Nevertheless, uncertainties remain about the genetic source (e.g., microbial, thermogenic) and possible migration history of natural gas incorporated into hydrate. Previous studies have primarily used the hydrocarbon molecular (CH 4 /C 2 H 6 +) and isotopic (δ 13 C-CH 4 , δ 2 H-CH 4 ) compositions of natural gas to address these uncertainties. However, hydrocarbon tracers are altered by mixing, oxidation, secondary methanogenesis, or fluid migration, which presents challenges when deciphering the mechanisms responsible for methane formation and accumulation. To evaluate the genetic source of natural gases from Green Canyon Block 955 (GC 955), east of the Sigsbee escarpment, we collected and analyzed samples from the first pressurized hydrate-bearing sediment cores collected from a coarse-grained hydrate reservoir in the Gulf of Mexico. Gas samples were analyzed for hydrocarbon gas (C 1 –C 5 ), major gas (e.g., N 2 , CO 2 ), and noble gas (He-Xe) abundance and isotopic (e.g., δ 13 C-CH 4 , δ 2 H-CH 4 , δ 13 C-CO 2 , δ 15 N-N 2 , 3 He/ 4 He, 4 He/ 20 Ne) compositions. We determined that natural gas in hydrates from this location are predominantly of primary microbial origin (conservatively at least 76%) and are formed by the hydrogenotrophic (CO 2 reduction) methanogenesis pathway. We also note increased thermogenic proportions (∼6%) in a hydrate-bearing layer below the main hydrate-bearing interval (separated by a 5-m water-bearing layer). Our results suggest that microbial methane may be abundant below the base of gas hydrate stability at GC 955.

Louisiana

Thermal-maturity limit for primary thermogenic-gas generation from humic coals as determined by hydrous pyrolysis

Hydrous-pyrolysis experiments at 360°C (680°F) for 72 h were conducted on 53 humic coals representing ranks from lignite through anthracite to determine the upper maturity limit for hydrocarbon-gas generation from their kerogen and associated bitumen (i.e., primary gas generation). These experimental conditions are below those needed for oil cracking to ensure that generated gas was not derived from the decomposition of expelled oil generated from some of the coals (i.e., secondary gas generation). Experimental results showed that generation of hydrocarbon gas ends before a vitrinite reflectance of 2.0%. This reflectance is equivalent to Rock-Eval maximum-yield temperature and hydrogen indices (HIs) of 555°C (1031°F) and 35 mg/g total organic carbon (TOC), respectively. At these maturity levels, essentially no soluble bitumen is present in the coals before or after hydrous pyrolysis. The equivalent kerogen atomic H/C ratio is 0.50 at the primary gas-generation limit and indicates that no alkyl moieties are remaining to source hydrocarbon gases. The convergence of atomic H/C ratios of type-II and -I kerogen to this same value at a reflectance of indicates that the primary gas-generation limits for humic coal and type-III kerogen also apply to oil-prone kerogen. Although gas generation from source rocks does not exceed vitrinite reflectance values greater than , trapped hydrocarbon gases can remain stable at higher reflectance values. Distinguishing trapped gas from generated gas in hydrous-pyrolysis experiments is readily determined by of the hydrocarbon gases when a -depleted water is used in the experiments. Water serves as a source of hydrogen in hydrous pyrolysis and, as a result, the use of -depleted water is reflected in the generated gases but not pre-existing trapped gases.

AAPG Bulletin

Geochemically distinct oil families in the onshore and offshore Santa Maria basins, California

The purpose of this work is to identify genetic affinities among 48 crude oil samples from the onshore and offshore Santa Maria basins. A total of 21 source-related biomarker and stable carbon isotope ratios among the samples were assessed to assure that they were unaffected by secondary processes. Chemometric analysis of these data identifies six oil families with map and stratigraphic distributions that reflect organofacies variations within the Miocene Monterey Formation source rock. The data comprise a training set that was used to create a chemometric decision tree to classify newly collected oil samples. Three onshore families originated from two synclines, which may contain one or more pods of thermally mature source rock. Multiple biomarker parameters indicate that the six oil families achieved early oil window maturity in the range of 0.6%–0.7% equivalent vitrinite reflectance. The offshore oil samples consist of one family from Point Pedernales field and two families from the “B” prospect. Geochemical characteristics of these families indicate origins under differing water column and sediment oxicity and carbonate versus siliceous and detrital input in ‘carbonate,’ ‘marl,’ and ‘shale’ organofacies like those in the lower calcareous–siliceous, carbonaceous marl, and clayey–siliceous members of the Monterey Formation elsewhere in coastal California. The corresponding lithofacies and organofacies appear to be linked to the early–middle Miocene climate optimum and subsequent paleoclimatic cooling after circa 14 Ma, a systematic up-section increase in the stable carbon isotope composition of related oil samples, decreased preservation of calcium carbonate shells from planktic foraminifera and coccoliths, and increased preservation of clay-sized siliceous shells of diatoms and radiolarians. The results show that organofacies within the Monterey source rock are responsible for many of the geochemical differences between the oil families. This paleoclimate–organofacies model for crude oil from the Monterey Formation can be used to enhance future exploration efforts in many areas of coastal California.

California