Radium content of oil- and gas-field produced waters in the northern Appalachian Basin (USA)—Summary and discussion of data

USGS Publications Warehouse

Rowan, E.L.; Engle, M.A.; Kirby, C.S.; Kraemer, T.F.

2011-01-01

Radium activity data for waters co-produced with oil and gas in New York and Pennsylvania have been compiled from publicly available sources and are presented together with new data for six wells, including one time series. When available, total dissolved solids (TDS), and gross alpha and gross beta particle activities also were compiled. Data from the 1990s and earlier are from sandstone and limestone oil/gas reservoirs of Cambrian-Mississippian age; however, the recent data are almost exclusively from the Middle Devonian Marcellus Shale. The Marcellus Shale represents a vast resource of natural gas the size and significance of which have only recently been recognized. Exploitation of the Marcellus involves hydraulic fracturing of the shale to release tightly held gas. Analyses of the water produced with the gas commonly show elevated levels of salinity and radium. Similarities and differences in radium data from reservoirs of different ages and lithologies are discussed. The range of radium activities for samples from the Marcellus Shale (less than detection to 18,000 picocuries per liter (pCi/L)) overlaps the range for non-Marcellus reservoirs (less than detection to 6,700 pCi/L), and the median values are 2,460 pCi/L and 734 pCi/L, respectively. A positive correlation between the logs of TDS and radium activity can be demonstrated for the entire dataset, and controlling for this TDS dependence, Marcellus shale produced water samples contain statistically more radium than non-Marcellus samples. The radium isotopic ratio, Ra-228/Ra-226, in samples from the Marcellus Shale is generally less than 0.3, distinctly lower than the median values from other reservoirs. This ratio may serve as an indicator of the provenance or reservoir source of radium in samples of uncertain origin.

Physical and chemical characterization of Devonian gas shale. Quarterly status report, October 1-December 31, 1978

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zielinski, R.E.; Nance, S.W.

On shale samples from the WV-6 (Monongalia County, West Virginia) well, mean total gas yield was 80.4 ft/sup 3//ton. Mean hydrocarbon gas yield was 5.7 ft/sup 3//ton, 7% of total yield. Methane was the major hydrocarbon component and carbon dioxide the major nonhydrocarbon component. Oil yield was negligible. Clay minerals and organic matter were the dominant phases of the shale. Illite averages 76% of the total clay mineral content. This is detrital illite. Permeation of methane, parallel to the bedding direction for select samples from WV-5 (Mason County, West Virginia) well ranges from 10/sup -4/ to 10/sup -12/ darcys. Themore » permeability of these shales is affected by orgaic carbon content, density, particle orientation, depositional facies, etc. Preliminary studies of Devonian shale methane sorption rates suggest that these rates may be affected by shale porosity, as well as absorption and adsorption processes. An experimental system was designed to effectively simulate sorption of methane at natural reservoir conditions. The bulk density and color of select shales from Illinois, Appalachian and Michigan Basins suggest a general trend of decreasing density with increasing organic content. Black and grayish black shales have organic contents which normally exceed 1.0 wt %. Medium dark gray and gray shales generally have organic contents less than 1.0 wt %.« less

Methane Occurrence in a Drinking Water Aquifer Before and During Natural Gas Production from the Marcellus Shale

NASA Astrophysics Data System (ADS)

Saiers, J. E.; Barth-Naftilan, E.

2017-12-01

More than 4,000 thousand wells have punctured aquifers of Pennsylvania's northern tier to siphon natural gas from the underlying Marcellus Shale. As drilling and hydraulic fracturing ramped up a decade ago, homeowner reports of well water contamination by methane and other contaminants began to emerge. Although made infrequently compared to the number of gas wells drilled, these reports were troubling and motivated our two-year, prospective study of groundwater quality within the Marcellus Shale Play. We installed multi-level sampling wells within a bedrock aquifer of a 25 km2 area that was targeted for shale gas development. These wells were sampled on a monthly basis before, during, and after seven shale gas wells were drilled, hydraulically fractured, and placed into production. The groundwater samples, together with surface water samples collected from nearby streams, were analyzed for hydrocarbons, trace metals, major ions, and the isotopic compositions of methane, ethane, water, strontium, and dissolved inorganic carbon. With regard to methane in particular, concentrations ranged from under 0.1 to over 60 mg/L, generally increased with aquifer depth, and, at some sites, exhibited considerable temporal variability. The isotopic composition of methane and hydrocarbon ratios also spanned a large range, suggesting that methane origins are diverse and, notably, shift on the time scale of this study. We will present inferences on factors governing methane occurrence across our study area by interpreting time-series data on methane concentrations and isotopic composition in context of local hydrologic variation, companion measurements of groundwater chemistry, and the known timing of key stages of natural gas extraction.

Adsorption of xenon and krypton on shales

NASA Technical Reports Server (NTRS)

Podosek, F. A.; Bernatowicz, T. J.; Kramer, F. E.

1981-01-01

A method that uses a mass spectrometer as a manometer is employed in the measurement of Xe and Kr adsorption parameters on shales and related samples, where gas partial pressures were lower than 10 to the -11th atm, corresponding adsorption coverages are only small fractions of a monolayer, and Henry's Law behavior is expected and observed. Results show heats of adsorption in the 2-7 kcal/mol range, and Henry constants at 0-25 C of 1 cu cm STP/g per atmosphere are extrapolated. Although the adsorption properties obtained are variable by sample, the range obtained suggests that shales may be capable of an equilibrium adsorption with modern air high enough to account for a significant fraction of the atmospheric inventory of Xe, and perhaps even of Kr. This effect will nevertheless not account for the factor-of-25 defficiency of atmospheric Xe, in comparison with the planetary gas patterns observed in meteorites.

Determination of elemental composition of shale rocks by laser induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Sanghapi, Hervé K.; Jain, Jinesh; Bol'shakov, Alexander; Lopano, Christina; McIntyre, Dustin; Russo, Richard

2016-08-01

In this study laser induced breakdown spectroscopy (LIBS) is used for elemental characterization of outcrop samples from the Marcellus Shale. Powdered samples were pressed to form pellets and used for LIBS analysis. Partial least squares regression (PLS-R) and univariate calibration curves were used for quantification of analytes. The matrix effect is substantially reduced using the partial least squares calibration method. Predicted results with LIBS are compared to ICP-OES results for Si, Al, Ti, Mg, and Ca. As for C, its results are compared to those obtained by a carbon analyzer. Relative errors of the LIBS measurements are in the range of 1.7 to 12.6%. The limits of detection (LODs) obtained for Si, Al, Ti, Mg and Ca are 60.9, 33.0, 15.6, 4.2 and 0.03 ppm, respectively. An LOD of 0.4 wt.% was obtained for carbon. This study shows that the LIBS method can provide a rapid analysis of shale samples and can potentially benefit depleted gas shale carbon storage research.

Coal Rank and Stratigraphy of Pennsylvanian Coal and Coaly Shale Samples, Young County, North-Central Texas

USGS Publications Warehouse

Guevara, Edgar H.; Breton, Caroline; Hackley, Paul C.

2007-01-01

Vitrinite reflectance measurements were made to determine the rank of selected subsurface coal and coaly shale samples from Young County, north-central Texas, for the National Coal Resources Database System State Cooperative Program conducted by the Bureau of Economic Geology at The University of Texas at Austin. This research is the continuation of a pilot study that began in adjacent Archer County, and forms part of a larger investigation of the coalbed methane resource potential of Pennsylvanian coals in north-central Texas. A total of 57 samples of coal and coaly shale fragments were hand-picked from drill cuttings from depths of about 2,000 ft in five wells, and Ro determinations were made on an initial 10-sample subset. Electric-log correlation of the sampled wells indicates that the collected samples represent coal and coaly shale layers in the Strawn (Pennsylvanian), Canyon (Pennsylvanian), and Cisco (Pennsylvanian-Permian) Groups. Coal rank in the initial sample subset ranges from lignite (Ro=0.39), in a sample from the Cisco Group at a depth of 310 to 320 ft, to high volatile bituminous A coal (Ro=0.91) in a sample from the lower part of the Canyon Group at a depth of 2,030 to 2,040 ft.

Preliminary source rock evaluation and hydrocarbon generation potential of the early Cretaceous subsurface shales from Shabwah sub-basin in the Sabatayn Basin, Western Yemen

NASA Astrophysics Data System (ADS)

Al-Matary, Adel M.; Hakimi, Mohammed Hail; Al Sofi, Sadam; Al-Nehmi, Yousif A.; Al-haj, Mohammed Ail; Al-Hmdani, Yousif A.; Al-Sarhi, Ahmed A.

2018-06-01

A conventional organic geochemical study has been performed on the shale samples collected from the early Cretaceous Saar Formation from the Shabwah oilfields in the Sabatayn Basin, Western Yemen. The results of this study were used to preliminary evaluate the potential source-rock of the shales in the Saar Formation. Organic matter richness, type, and petroleum generation potential of the analysed shales were assessed. Total organic carbon content and Rock- Eval pyrolysis results indicate that the shale intervals within the early Cretaceous Saar Formation have a wide variation in source rock generative potential and quality. The analysed shale samples have TOC content in the range of 0.50 and 5.12 wt% and generally can be considered as fair to good source rocks. The geochemical results of this study also indicate that the analysed shales in the Saar Formation are both oil- and gas-prone source rocks, containing Type II kerogen and mixed Types II-III gradient to Type III kerogen. This is consistent with Hydrogen Index (HI) values between 66 and 552 mg HC/g TOC. The temperature-sensitive parameters such as vitrinite reflectance (%VRo), Rock-Eval pyrolysis Tmax and PI reveal that the analysed shale samples are generally immature to early-mature for oil-window. Therefore, the organic matter has not been altered by thermal maturity thus petroleum has not yet generated. Therefore, exploration strategies should focus on the known deeper location of the Saar Formation in the Shabwah-sub-basin for predicting the kitchen area.

Reservoir characteristics of coal-shale sedimentary sequence in coal-bearing strata and their implications for the accumulation of unconventional gas

NASA Astrophysics Data System (ADS)

Wang, Yang; Zhu, Yanming; Liu, Yu; Chen, Shangbin

2018-04-01

Shale gas and coalbed methane (CBM) are both considered unconventional natural gas and are becoming increasingly important energy resources. In coal-bearing strata, coal and shale are vertically adjacent as coal and shale are continuously deposited. Research on the reservoir characteristics of coal-shale sedimentary sequences is important for CBM and coal-bearing shale gas exploration. In this study, a total of 71 samples were collected, including coal samples (total organic carbon (TOC) content >40%), carbonaceous shale samples (TOC content: 6%-10%), and shale samples (TOC content <6%). Combining techniques of field emission scanning electron microscopy (FE-SEM), x-ray diffraction, high-pressure mercury intrusion porosimetry, and methane adsorption, experiments were employed to characterize unconventional gas reservoirs in coal-bearing strata. The results indicate that in the coal-shale sedimentary sequence, the proportion of shale is the highest at 74% and that of carbonaceous shale and coal are 14% and 12%, respectively. The porosity of all measured samples demonstrates a good positive relationship with TOC content. Clay and quartz also have a great effect on the porosity of shale samples. According to the FE-SEM image technique, nanoscale pores in the organic matter of coal samples are much more developed compared with shale samples. For shales with low TOC, inorganic minerals provide more pores than organic matter. In addition, TOC content has a positive relationship with methane adsorption capacity, and the adsorption capacity of coal samples is more sensitive than the shale samples to temperature.

Application of binomial-edited CPMG to shale characterization

USGS Publications Warehouse

Washburn, Kathryn E.; Birdwell, Justin E.

2014-01-01

Unconventional shale resources may contain a significant amount of hydrogen in organic solids such as kerogen, but it is not possible to directly detect these solids with many NMR systems. Binomial-edited pulse sequences capitalize on magnetization transfer between solids, semi-solids, and liquids to provide an indirect method of detecting solid organic materials in shales. When the organic solids can be directly measured, binomial-editing helps distinguish between different phases. We applied a binomial-edited CPMG pulse sequence to a range of natural and experimentally-altered shale samples. The most substantial signal loss is seen in shales rich in organic solids while fluids associated with inorganic pores seem essentially unaffected. This suggests that binomial-editing is a potential method for determining fluid locations, solid organic content, and kerogen–bitumen discrimination.

Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities.

PubMed

Drollette, Brian D; Hoelzer, Kathrin; Warner, Nathaniel R; Darrah, Thomas H; Karatum, Osman; O'Connor, Megan P; Nelson, Robert K; Fernandez, Loretta A; Reddy, Christopher M; Vengosh, Avner; Jackson, Robert B; Elsner, Martin; Plata, Desiree L

2015-10-27

Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency's maximum contaminant levels, and low levels of both gasoline range (0-8 ppb) and diesel range organic compounds (DRO; 0-157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation.

Elevated levels of diesel range organic compounds in groundwater near Marcellus gas operations are derived from surface activities

PubMed Central

Drollette, Brian D.; Hoelzer, Kathrin; Warner, Nathaniel R.; Darrah, Thomas H.; Karatum, Osman; O’Connor, Megan P.; Nelson, Robert K.; Fernandez, Loretta A.; Reddy, Christopher M.; Vengosh, Avner; Jackson, Robert B.; Elsner, Martin; Plata, Desiree L.

2015-01-01

Hundreds of organic chemicals are used during natural gas extraction via high-volume hydraulic fracturing (HVHF). However, it is unclear whether these chemicals, injected into deep shale horizons, reach shallow groundwater aquifers and affect local water quality, either from those deep HVHF injection sites or from the surface or shallow subsurface. Here, we report detectable levels of organic compounds in shallow groundwater samples from private residential wells overlying the Marcellus Shale in northeastern Pennsylvania. Analyses of purgeable and extractable organic compounds from 64 groundwater samples revealed trace levels of volatile organic compounds, well below the Environmental Protection Agency’s maximum contaminant levels, and low levels of both gasoline range (0–8 ppb) and diesel range organic compounds (DRO; 0–157 ppb). A compound-specific analysis revealed the presence of bis(2-ethylhexyl) phthalate, which is a disclosed HVHF additive, that was notably absent in a representative geogenic water sample and field blanks. Pairing these analyses with (i) inorganic chemical fingerprinting of deep saline groundwater, (ii) characteristic noble gas isotopes, and (iii) spatial relationships between active shale gas extraction wells and wells with disclosed environmental health and safety violations, we differentiate between a chemical signature associated with naturally occurring saline groundwater and one associated with alternative anthropogenic routes from the surface (e.g., accidental spills or leaks). The data support a transport mechanism of DRO to groundwater via accidental release of fracturing fluid chemicals derived from the surface rather than subsurface flow of these fluids from the underlying shale formation. PMID:26460018

Chemical analysis and geochemical associations in Devonian black shale core samples from Martin County, Kentucky; Carroll and Washington counties, Ohio; Wise County, Virginia; and Overton County, Tennessee

USGS Publications Warehouse

Leventhal, Joel S.

1979-01-01

Core samples from Devonian shales from five localities in the Appalachian Basin have been analyzed for major, minor, and trace constituents. The contents of major elements are rather similar; however, the minor constituents, organic C, S, PO4, and CO3, show variations by a factor of 10. Trace elements Mo, Ni, Cu, V, Co, U, Zn, Hg, As, and Mn show variations that can be related graphically and statistically to the minor constituents. Down-hole plots show the relationships most clearly. Mn is associated with CO3 content, the other trace elements are strongly Controlled by organic C. Amounts of organic C are generally in the range of 3-6 percent, and S is in the range of 2-5 percent. Trace-element amounts show the following general ranges (ppm, parts per million)- Co, 20-40; Cu,40-70; U, 10-40; As, 20-40, V, 150-300; Ni, 80-150; high values are as much as twice these values. The organic C was probably the concentrating agent, whereas the organic C and sulfide S created an environment for preservation or immobilization of trace elements. Closely spaced samples showing an abrupt transition in color from black to gray and gray to black shale show similar effects of trace-element changes, that is, black shale contains enhanced amounts of organic C and trace elements. Ratios of trace elements to organic C or sulfide S were relatively constant even though deposition rates varied from 10 to 300 meters in 5 million years.

Effects of experimental parameters on the sorption of cesium, strontium, and uranium from saline groundwaters onto shales: Progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, R.E.; Arnold, W.D.; Case, F.I.

1988-11-01

This report concerns an extension of the first series of experiments on the sorption properties of shales and their clay mineral components reported earlier. Studies on the sorption of cesium and strontium were carried out on samples of Chattanooga (Upper Dowelltown), Pierre, Green River Formation, Nolichucky, and Pumpkin Valley Shales that had been heated to 120/degree/C in a 0.1-mol/L NaCl solution for periods up to several months and on samples of the same shales which had been heated to 250/degree/C in air for six months, to simulate limiting scenarios in a HLW repository. To investigate the kinetics of the sorptionmore » process in shale/groundwater systems, strontium sorption experiments were done on unheated Pierre, Green River Formation, Nolichucky, and Pumpkin Valley Shales in a diluted, saline groundwater and in 0.03-mol/L NaHCO/sub 3/, for periods of 0.25 to 28 days. Cesium sorption kinetics tests were performed on the same shales in a concentrated brine for the same time periods. The effect of the water/rock (W/R) ratio on sorption for the same combinations of unheated shales, nuclides, and groundwaters used in the kinetics experiments was investigated for a range of W/R ratios of 3 to 20 mL/g. Because of the complexity of the shale/groundwater interaction, a series of tests was conducted on the effects of contact time and W/R ratio on the pH of a 0.03-mol/L NaHCO/sub 3/ simulated groundwater in contact with shales. 8 refs., 12 figs., 15 tabs.« less

Use of arsenic and REE in black shales as potential environmental tracers in hydraulic fracturing operations

NASA Astrophysics Data System (ADS)

Yang, J.; Torres, M. E.; Haley, B. A.; McKay, J. L.; Algeo, T. J.; Hakala, A.; Joseph, C.; Edenborn, H. M.

2013-12-01

Black shales commonly targeted for shale gas development were deposited under low oxygen concentrations, and typically contain high As levels. The depositional environment governs its solid-phase association in the sediment, which in turn will influence degree of remobilization during hydraulic fracturing. Organic carbon (OC), trace element (TE) and REE distributions have been used as tracers for assessing deep water redox conditions at the time of deposition in the Midcontinent Sea of North America (Algeo and Heckel, 2008), during large-scale oceanic anoxic events (e.g., Bunte, 2009) and in modern OC-rich sediments underlying coastal upwelling areas (e.g., Brumsack, 2006). We will present REE and As data from a collection of six different locations in the continental US (Kansas, Iowa, Oklahoma, Kentucky, North Dakota and Pennsylvania), ranging in age from Devonian to Upper Pennsylvanian, and from a Cretaceous black shale drilled on the Demerara Rise during ODP Leg 207. We interpret our data in light of the depositional framework previously developed for these locations based on OC and TE patterns, to document the mechanisms leading to REE and As accumulation, and explore their potential use as environmental proxies and their diagenetic remobilization during burial, as part of our future goal to develop a predictive evaluation of arsenic release from shales and transport with flowback waters. Total REE abundance (ΣREE) ranged from 35 to 420 ppm in an organic rich sample from Stark shale, KS. PAAS-normalized REE concentrations ranged from 0.5 to 7, with the highest enrichments observed in the MREE (Sm to Ho). Neither the ΣREE nor the MREE enrichments correlated with OC concentrations or postulated depositional redox conditions, suggesting a principal association with aluminosilicates and selective REE fractionation during diagenesis. In the anoxic reducing environments in which black shales were deposited, sulfide minerals such as FeS2 trap aqueous arsenic in the crystal lattice, but As is also known to bind to the charged surfaces of clay minerals. Our arsenic concentration data show that the highest abundances (up to 70 ppm) are found in sediments with the highest total sulfur concentration (to 2.6 ppm), but there was no clear correlation with organic carbon or aluminosilicate content. We compare our results with preliminary data from a series of flowback waters sampled from ten producing wells in Pennsylvania and from high-pressure high-temperature experimental leaching of Marcellus shale samples.

The Shublik Formation and adjacent strata in northeastern Alaska description, minor elements, depositional environments and diagenesis

USGS Publications Warehouse

Tourtelot, Harry Allison; Tailleur, Irvin L.

1971-01-01

The Shublik Formation (Middle and Late Triassic) is widespread in the surface and subsurface of northern Alaska. Four stratigraphic sections along about 70 miles of the front of the northeastern Brooks Range east of the Canning giver were examined and sampled in detail in 1968. These sections and six-step spectrographic and carbon analyses of the samples combined with other data to provide a preliminary local description of the highly organic unit and of the paleoenvironments. Thicknesses measured between the overlying Kingak Shale of Jurassic age and the underlying Sadlerochit Formation of Permian and Triassic age range from 400 to more than 800 feet but the 400 feet, obtained from the most completely exposed section, may be closer to the real thickness across the region. The sections consist of organic-rich, phosphatic, and fossiliferous muddy, silty, or carbonate rocks. The general sequence consists, from the bottom up, of a lower unit of phosphatic siltstone, a middle unit of phosphatic carbonate rocks, and an upper unit of shale and carbonate rocks near the Canning River and shale, carbonate rocks, and sandstone to the east. Although previously designated a basal member of the Kingak Shale (Jurassic), the upper unit is here included with the Shublik on the basis of its regional lithologic relation. The minor element compositions of the samples of the Shublik Formation are consistent with their carbonaceous and phosphatic natures in that relatively large amounts of copper, molybdenum, nickel, vanadium and rare earths are present. The predominantly sandy rocks of the underlying Sadlerochit Formation (Permian and Triassic) have low contents of most minor elements. The compositions of samples of Kingak Shale have a wide range not readily explicable by the nature of the rock: an efflorescent sulfate salt contains 1,500 ppm nickel and 1,500 ppm zinc and large amounts of other metals derived from weathering of pyrite and leaching of local shale. The only recorded occurrence of silver and 300 ppm lead in gouge along a shear plane may be the result of metals introduced from an extraneous source. The deposits reflect a marine environment that deepened somewhat following deposition of the Sadlerochit Formation and then shoaled during deposition of the upper limestone-siltstone unit. This apparently resulted from a moderate transgression and regression of the sea with respect to a northwest-trending line between Barrow and the Brooks Range at the International Boundary. Nearer shore facies appear eastward. The phosphate in nodules, fossil molds and oolites, appears to have formed diagenetically within the uncompacted sediment.

The pore structure and fractal characteristics of shales with low thermal maturity from the Yuqia Coalfield, northern Qaidam Basin, northwestern China

NASA Astrophysics Data System (ADS)

Hou, Haihai; Shao, Longyi; Li, Yonghong; Li, Zhen; Zhang, Wenlong; Wen, Huaijun

2018-03-01

The continental shales from the Middle Jurassic Shimengou Formation of the northern Qaidam Basin, northwestern China, have been investigated in recent years because of their shale gas potential. In this study, a total of twenty-two shale samples were collected from the YQ-1 borehole in the Yuqia Coalfield, northern Qaidam Basin. The total organic carbon (TOC) contents, pore structure parameters, and fractal characteristics of the samples were investigated using TOC analysis, low-temperature nitrogen adsorption experiments, and fractal analysis. The results show that the average pore size of the Shimengou shales varied from 8.149 nm to 20.635 nm with a mean value of 10.74 nm, which is considered mesopore-sized. The pores of the shales are mainly inkbottle- and slit-shaped. The sedimentary environment plays an essential role in controlling the TOC contents of the low maturity shales, with the TOC values of shales from deep to semi-deep lake facies (mean: 5.23%) being notably higher than those of the shore-shallow lake facies (mean: 0.65%). The fractal dimensions range from 2.4639 to 2.6857 with a mean of 2.6122, higher than those of marine shales, which indicates that the pore surface was rougher and the pore structure more complex in these continental shales. The fractal dimensions increase with increasing total pore volume and total specific surface area, and with decreasing average pore size. With increasing TOC contents in shales, the fractal dimensions increase first and then decrease, with the highest value occurring at 2% of TOC content, which is in accordance with the trends between the TOC and both total specific surface area and total pore volume. The pore structure complexity and pore surface roughness of these low-maturity shales would be controlled by the combined effects of both sedimentary environments and the TOC contents.

Lightweight aggregate production from claystone and shale in Bangladesh

USGS Publications Warehouse

Parker, Norbert A.; Khan, M.A.

1976-01-01

Muffle furnace tests were made on samples of clay, claystone, and shale collected in the Chittagong and Dacca areas of East Pakistan to determine their amenability to bloating for the commercial production of light-weight aggregate. Several areas, sampled in some detail, were selected for investigation because of their proximity to market, and accessibility to fuel and electricity. Muffle furnace tests show that the clay, claystone, and shale are natural bloaters at temperatures in the 1700? to 2200? F range, and do not require additives. The most desirable deposit, insofar as producing a strong aggregate is concerned, can be determined only by pilot-kiln testing and by crushing-strength tests made on concrete test cylinders. Reserves of suitable raw material are large in both the Chittagong and Dacca areas.

Hierarchical Pore Morphology of Cretaceous Shale: A Small-Angle Neutron Scattering and Ultrasmall-Angle Neutron Scattering Study

DOE PAGES

Bahadur, J.; Melnichenko, Y. B.; Mastalerz, Maria; ...

2014-09-25

Shale reservoirs are becoming an increasingly important source of oil and natural gas supply and a potential candidate for CO 2 sequestration. Understanding the pore morphology in shale may provide clues to making gas extraction more efficient and cost-effective. The porosity of Cretaceous shale samples from Alberta, Canada, collected from different depths with varying mineralogical compositions, has been investigated by small- and ultrasmall-angle neutron scattering. Moreover these samples come from the Second White Specks and Belle Fourche formations, and their organic matter content ranges between 2 and 3%. The scattering length density of the shale specimens has been estimated usingmore » the chemical composition of the different mineral components. Scattering experiments reveal the presence of fractal and non-fractal pores. It has been shown that the porosity and specific surface area are dominated by the contribution from meso- and micropores. The fraction of closed porosity has been calculated by comparing the porosities estimated by He pycnometry and scattering techniques. There is no correlation between total porosity and mineral components, a strong correlation has been observed between closed porosity and major mineral components in the studied specimens.« less

Fractal Characteristics of Pores in Taiyuan Formation Shale from Hedong Coal Field, China

NASA Astrophysics Data System (ADS)

Li, Kunjie; Zeng, Fangui; Cai, Jianchao; Sheng, Guanglong; Xia, Peng; Zhang, Kun

For the purpose of investigating the fractal characteristics of pores in Taiyuan formation shale, a series of qualitative and quantitative experiments were conducted on 17 shale samples from well HD-1 in Hedong coal field of North China. The results of geochemical experiments show that Total organic carbon (TOC) varies from 0.67% to 5.32% and the organic matters are in the high mature or over mature stage. The shale samples consist mainly of clay minerals and quartz with minor pyrite and carbonates. The FE-SEM images indicate that three types of pores, organic-related pores, inorganic-related pores and micro-fractures related pores, are developed well, and a certain number of intragranular pores are found inside quartz and carbonates formed by acid liquid corrosion. The pore size distributions (PSDs) broadly range from several to hundreds nanometers, but most pores are smaller than 10nm. As the result of different adsorption features at relative pressure (0-0.5) and (0.5-1) on the N2 adsorption isotherm, two fractal dimensions D1 and D2 were obtained with the Frenkel-Halsey-Hill (FHH) model. D1 and D2 vary from 2.4227 to 2.6219 and from 2.6049 to 2.7877, respectively. Both TOC and brittle minerals have positive effect on D1 and D2, whereas clay minerals, have a negative influence on them. The fractal dimensions are also influenced by the pore structure parameters, such as the specific surface area, BJH pore volume, etc. Shale samples with higher D1 could provide more adsorption sites leading to a greater methane adsorption capacity, whereas shale samples with higher D2 have little influence on methane adsorption capacity.

Review of rare earth element concentrations in oil shales of the Eocene Green River Formation

USGS Publications Warehouse

Birdwell, Justin E.

2012-01-01

Concentrations of the lanthanide series or rare earth elements and yttrium were determined for lacustrine oil shale samples from the Eocene Green River Formation in the Piceance Basin of Colorado and the Uinta Basin of Utah. Unprocessed oil shale, post-pyrolysis (spent) shale, and leached shale samples were examined to determine if oil-shale processing to generate oil or the remediation of retorted shale affects rare earth element concentrations. Results for unprocessed Green River oil shale samples were compared to data published in the literature on reference materials, such as chondritic meteorites, the North American shale composite, marine oil shale samples from two sites in northern Tibet, and mined rare earth element ores from the United States and China. The Green River oil shales had lower rare earth element concentrations (66.3 to 141.3 micrograms per gram, μg g-1) than are typical of material in the upper crust (approximately 170 μg g-1) and were also lower in rare earth elements relative to the North American shale composite (approximately 165 μg g-1). Adjusting for dilution of rare earth elements by organic matter does not account for the total difference between the oil shales and other crustal rocks. Europium anomalies for Green River oil shales from the Piceance Basin were slightly lower than those reported for the North American shale composite and upper crust. When compared to ores currently mined for rare earth elements, the concentrations in Green River oil shales are several orders of magnitude lower. Retorting Green River oil shales led to a slight enrichment of rare earth elements due to removal of organic matter. When concentrations in spent and leached samples were normalized to an original rock basis, concentrations were comparable to those of the raw shale, indicating that rare earth elements are conserved in processed oil shales.

Controls on Methane Occurrences in Aquifers Overlying the Eagle Ford Shale Play, South Texas.

PubMed

Nicot, Jean-Philippe; Larson, Toti; Darvari, Roxana; Mickler, Patrick; Uhlman, Kristine; Costley, Ruth

2017-07-01

Assessing natural vs. anthropogenic sources of methane in drinking water aquifers is a critical issue in areas of shale oil and gas production. The objective of this study was to determine controls on methane occurrences in aquifers in the Eagle Ford Shale play footprint. A total of 110 water wells were tested for dissolved light alkanes, isotopes of methane, and major ions, mostly in the eastern section of the play. Multiple aquifers were sampled with approximately 47 samples from the Carrizo-Wilcox Aquifer (250-1200 m depth range) and Queen City-Sparta Aquifer (150-900 m depth range) and 63 samples from other shallow aquifers but mostly from the Catahoula Formation (depth <150 m). Besides three shallow wells with unambiguously microbial methane, only deeper wells show significant dissolved methane (22 samples >1 mg/L, 10 samples >10 mg/L). No dissolved methane samples exhibit thermogenic characteristics that would link them unequivocally to oil and gas sourced from the Eagle Ford Shale. In particular, the well water samples contain very little or no ethane and propane (C1/C2+C3 molar ratio >453), unlike what would be expected in an oil province, but they also display relatively heavier δ 13 C methane (>-55‰) and δD methane (>-180‰). Samples from the deeper Carrizo and Queen City aquifers are consistent with microbial methane sourced from syndepositional organic matter mixed with thermogenic methane input, most likely originating from deeper oil reservoirs and migrating through fault zones. Active oxidation of methane pushes δ 13 C methane and δD methane toward heavier values, whereas the thermogenic gas component is enriched with methane owing to a long migration path resulting in a higher C1/C2+C3 ratio than in the local reservoirs. © 2017, National Ground Water Association.

Estimating emissions of toxic hydrocarbons from natural gas production sites in the Barnett Shale region

NASA Astrophysics Data System (ADS)

Marrero, J. E.; Townsend-Small, A.; Lyon, D. R.; Tsai, T.; Meinardi, S.; Blake, D. R.

2015-12-01

Throughout the past decade, shale gas operations have moved closer to urban centers and densely populated areas, contributing to growing public concerns regarding exposure to hazardous air pollutants (HAPs). These HAPs include gases like hexane, 1,3-butadiene and BTEX compounds, which can cause minor health effects from short-term exposure or possibly cancer due to prolonged exposure. During the Barnett Shale Coordinated Campaign in October, 2013, ground-based whole air samples revealed enhancements in several of these toxic volatile organic compounds (VOCs) downwind of natural gas well pads and compressor stations. Two methods were used to estimate the emission rate of several HAPs in the Barnett Shale. The first method utilized CH4 flux measurements derived from the Picarro Mobile Flux Plane (MFP) and taken concurrently with whole air samples, while the second used a CH4 emissions inventory developed for the Barnett Shale region. From these two approaches, the regional emission estimate for benzene (C6H6) ranged from 48 ± 16 to 84 ± 26 kg C6H6 hr-1. A significant regional source of atmospheric benzene is evident, despite measurement uncertainty and limited number of samples. The extent to which these emission rates equate to a larger public health risk is unclear, but is of particular interest as natural gas productions continues to expand.

Organic matter from the Bunte Breccia of the Ries Crater, southern Germany: investigating possible thermal effects of the impact

NASA Astrophysics Data System (ADS)

Hofmann, P.; Leythaeuser, D.; Schwark, L.

2001-07-01

In order to determine thermal effects of the Ries impact, southern Germany, on organic matter in its ejecta blanket, the maturity of organic matter of Posidonia Shale components from the Bunte Breccia at Harburg and Gundelsheim is compared with the maturity of organic matter of a reference section of Posidonia Shale outside the impact site at Hesselberg. Three black shale samples from the Bunte Breccia were identified as corresponding to the organic matter-rich Posidonia Shale based on the molecular composition of extractable organic matter. They show n-alkane patterns with a maximum of n-C 17, a predominance of odd over even n-alkanes in the range from n-C 26 to n-C 35, a dominance of unsaturated sterenes over steranes and monoaromatic over triaromatic steroids, and contain isorenieratene. The maturity of the organic matter from the Bunte Breccia samples corresponds to 0.32-0.35% random vitrinite reflectance ( Rr) and a spectral red/green quotient ( Q) of 0.32-0.34. The organic matter from the Bunte Breccia is more mature than the Posidonia Shale sample from the reference site Hesselberg (0.25% Rr; 0.21 for Q). The thermal overprint is presumed to be too high to be explained by differences in the burial history prior to the impact alone and is, therefore, attributed to processes related to the displacement of the Bunte Breccia.

Oxidation and mobilization of selenium by nitrate in irrigation drainage

USGS Publications Warehouse

Wright, W.G.

1999-01-01

Selenium (Se) can be oxidized by nitrate (NO3-) from irrigation on Cretaceous marine shale in western Colorado. Dissolved Se concentrations are positively correlated with dissolved NO3- concentrations in surface water and ground water samples from irrigated areas. Redox conditions dominate in the mobilization of Se in marine shale hydrogeologic settings; dissolved Se concentrations increase with increasing platinum-electrode potentials. Theoretical calculations for the oxidation of Se by NO3- and oxygen show favorable Gibbs free energies for the oxidation of Se by NO3-, indicating NO3- can act as an electron acceptor for the oxidation of Se. Laboratory batch experiments were performed by adding Mancos Shale samples to zero- dissolved-oxygen water containing 0, 5, 50, and 100 mg/L NO3- as N (mg N/L). Samples were incubated in airtight bottles at 25??C for 188 d; samples collected from the batch experiment bottles show increased Se concentrations over time with increased NO3- concentrations. Pseudo first-order rate constants for NO3- oxidation of Se ranged from 0.0007 to 0.0048/d for 0 to 100 mg N/L NO3- concentrations, respectively. Management of N fertilizer applications in Cretaceous shale settings might help to control the oxidation and mobilization of Se and other trace constituents into the environment.

Effect of organic matter properties, clay mineral type and thermal maturity on gas adsorption in organic-rich shale systems

USGS Publications Warehouse

Zhang, Tongwei; Ellis, Geoffrey S.; Ruppel, Stephen C.; Milliken, Kitty; Lewan, Mike; Sun, Xun; Baez, Luis; Beeney, Ken; Sonnenberg, Steve

2013-01-01

A series of CH4 adsorption experiments on natural organic-rich shales, isolated kerogen, clay-rich rocks, and artificially matured Woodford Shale samples were conducted under dry conditions. Our results indicate that physisorption is a dominant process for CH4 sorption, both on organic-rich shales and clay minerals. The Brunauer–Emmett–Teller (BET) surface area of the investigated samples is linearly correlated with the CH4 sorption capacity in both organic-rich shales and clay-rich rocks. The presence of organic matter is a primary control on gas adsorption in shale-gas systems, and the gas-sorption capacity is determined by total organic carbon (TOC) content, organic-matter type, and thermal maturity. A large number of nanopores, in the 2–50 nm size range, were created during organic-matter thermal decomposition, and they significantly contributed to the surface area. Consequently, methane-sorption capacity increases with increasing thermal maturity due to the presence of nanopores produced during organic-matter decomposition. Furthermore, CH4 sorption on clay minerals is mainly controlled by the type of clay mineral present. In terms of relative CH4 sorption capacity: montmorillonite ≫ illite – smectite mixed layer > kaolinite > chlorite > illite. The effect of rock properties (organic matter content, type, maturity, and clay minerals) on CH4 adsorption can be quantified with the heat of adsorption and the standard entropy, which are determined from adsorption isotherms at different temperatures. For clay-mineral rich rocks, the heat of adsorption (q) ranges from 9.4 to 16.6 kJ/mol. These values are considerably smaller than those for CH4 adsorption on kerogen (21.9–28 kJ/mol) and organic-rich shales (15.1–18.4 kJ/mol). The standard entropy (Δs°) ranges from -64.8 to -79.5 J/mol/K for clay minerals, -68.1 to -111.3 J/mol/K for kerogen, and -76.0 to -84.6 J/mol/K for organic-rich shales. The affinity of CH4 molecules for sorption on organic matter is stronger than for most common clay minerals. Thus, it is expected that CH4 molecules may preferentially occupy surface sites on organic matter. However, active sites on clay mineral surfaces are easily blocked by water. As a consequence, organic-rich shales possess a larger CH4-sorption capacity than clay-rich rocks lacking organic matter. The thermodynamic parameters obtained in this study can be incorporated into model predictions of the maximum Langmuir pressure and CH4- sorption capacity of shales under reservoir temperature and pressure conditions.

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

2014-01-01

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas- and liquids-rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make qualitative and semi-quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II-S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = -215.2 per mille (V-SMOW), ranging from - 271.8 per mille for the Marcellus Shale to -51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of -89.7 per mille, ranging from -156.0 per mille for the Barnett Shale to -50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H-bearing compounds play in terrestrial shale paleo-environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Multiscale study for stochastic characterization of shale samples

NASA Astrophysics Data System (ADS)

Tahmasebi, Pejman; Javadpour, Farzam; Sahimi, Muhammad; Piri, Mohammad

2016-03-01

Characterization of shale reservoirs, which are typically of low permeability, is very difficult because of the presence of multiscale structures. While three-dimensional (3D) imaging can be an ultimate solution for revealing important complexities of such reservoirs, acquiring such images is costly and time consuming. On the other hand, high-quality 2D images, which are widely available, also reveal useful information about shales' pore connectivity and size. Most of the current modeling methods that are based on 2D images use limited and insufficient extracted information. One remedy to the shortcoming is direct use of qualitative images, a concept that we introduce in this paper. We demonstrate that higher-order statistics (as opposed to the traditional two-point statistics, such as variograms) are necessary for developing an accurate model of shales, and describe an efficient method for using 2D images that is capable of utilizing qualitative and physical information within an image and generating stochastic realizations of shales. We then further refine the model by describing and utilizing several techniques, including an iterative framework, for removing some possible artifacts and better pattern reproduction. Next, we introduce a new histogram-matching algorithm that accounts for concealed nanostructures in shale samples. We also present two new multiresolution and multiscale approaches for dealing with distinct pore structures that are common in shale reservoirs. In the multiresolution method, the original high-quality image is upscaled in a pyramid-like manner in order to achieve more accurate global and long-range structures. The multiscale approach integrates two images, each containing diverse pore networks - the nano- and microscale pores - using a high-resolution image representing small-scale pores and, at the same time, reconstructing large pores using a low-quality image. Eventually, the results are integrated to generate a 3D model. The methods are tested on two shale samples for which full 3D samples are available. The quantitative accuracy of the models is demonstrated by computing their morphological and flow properties and comparing them with those of the actual 3D images. The success of the method hinges upon the use of very different low- and high-resolution images.

Shale characterization on Barito field, Southeast Kalimantan for shale hydrocarbon exploration

NASA Astrophysics Data System (ADS)

Sumotarto, T. A.; Haris, A.; Riyanto, A.; Usman, A.

2017-07-01

Exploration and exploitation in Indonesia now are still focused on conventional hydrocarbon energy than unconventional hydrocarbon energy such as shale gas. Tanjung Formation is a source rock of Barito Basin located in South Kalimantan that potentially as shale hydrocarbon. In this research, integrated methods using geochemical analysis, mineralogy, petrophysical analysis and seismic interpretation has been applied to explore the shale hydrocarbon potential in Barito Field for Tanjung formation. The first step is conducting geochemical and mineralogy analysis to the shale rock sample. Our analysis shows that the organic richness is ranging from 1.26-5.98 wt.% (good to excellent) with the depth of early mature window of 2170 m. The brittleness index is in an average of 0.44-0.56 (less Brittle) and Kerogen type is classified into II/III type that potentially produces oil and gas. The second step is continued by performing petrophysical analysis, which includes Total Organic Carbon (TOC) calculation and brittleness index continuously. The result has been validated with a laboratory measurement that obtained a good correlation. In addition, seismic interpretation based on inverted acoustic impedance is applied to map the distributions of shale hydrocarbon potential. Our interpretation shows that shale hydrocarbon potential is localized in the eastern and southeastern part of the study area.

Observations of the release of non-methane hydrocarbons from fractured shale.

PubMed

Sommariva, Roberto; Blake, Robert S; Cuss, Robert J; Cordell, Rebecca L; Harrington, Jon F; White, Iain R; Monks, Paul S

2014-01-01

The organic content of shale has become of commercial interest as a source of hydrocarbons, owing to the development of hydraulic fracturing ("fracking"). While the main focus is on the extraction of methane, shale also contains significant amounts of non-methane hydrocarbons (NMHCs). We describe the first real-time observations of the release of NMHCs from a fractured shale. Samples from the Bowland-Hodder formation (England) were analyzed under different conditions using mass spectrometry, with the objective of understanding the dynamic process of gas release upon fracturing of the shale. A wide range of NMHCs (alkanes, cycloalkanes, aromatics, and bicyclic hydrocarbons) are released at parts per million or parts per billion level with temperature- and humidity-dependent release rates, which can be rationalized in terms of the physicochemical characteristics of different hydrocarbon classes. Our results indicate that higher energy inputs (i.e., temperatures) significantly increase the amount of NMHCs released from shale, while humidity tends to suppress it; additionally, a large fraction of the gas is released within the first hour after the shale has been fractured. These findings suggest that other hydrocarbons of commercial interest may be extracted from shale and open the possibility to optimize the "fracking" process, improving gas yields and reducing environmental impacts.

Geologic and hydraulic characteristics of selected shaly geologic units in Oklahoma

USGS Publications Warehouse

Becker, C.J.; Overton, M.D.; Johnson, K.S.; Luza, K.V.

1997-01-01

Information was collected on the geologic and hydraulic characteristics of three shale-dominated units in Oklahoma-the Dog Creek Shale and Chickasha Formation in Canadian County, Hennessey Group in Oklahoma County, and the Boggy Formation in Pittsburg County. The purpose of this project was to gain insight into the characteristics controlling fluid flow in shaly units that could be targeted for confinement of hazardous waste in the State and to evaluate methods of measuring hydraulic characteristics of shales. Permeameter results may not indicate in-place small-scale hydraulic characteristics, due to pretest disturbance and deterioration of core samples. The Dog Creek Shale and Chickasha Formation hydraulic conductivities measured by permeameter methods ranged from 2.8 times 10 to the negative 11 to 3.0 times 10 to the negative 7 meter per second in nine samples and specific storage from 3.3 times 10 to the negative 4 to 1.6 times 10 to the negative 3 per meter in four samples. Hennessey Group hydraulic conductivities ranged from 4.0 times 10 to the negative 12 to 4.0 times 10 to the negative 10 meter per second in eight samples. Hydraulic conductivity in the Boggy Formation ranged from 1.7 times 10 to the negative 12 to 1.0 times 10 to the negative 8 meter per second in 17 samples. The hydraulic properties of isolated borehole intervals of average length of 4.5 meters in the Hennessey Group and the Boggy Formation were evaluated by a pressurized slug-test method. Hydraulic conductivities obtained with this method tend to be low because intervals with features that transmitted large volumes of water were not tested. Hennessey Group hydraulic conductivities measured by this method ranged from 3.0 times 10 to the negative 13 to 1.1 times 10 to the negative 9 meter per second; the specific storage values are small and may be unreliable. Boggy Formation hydraulic conductivities ranged from 2.0 times 10 to the negative 13 to 2.7 times 10 to the negative 10 meter per second and specific storage values in these tests also are small and may be unreliable. A substantially higher hydraulic conductivity of 3.0 times 10 to the negative 8 meter per second was measured in one borehole 30 meters deep in the Boggy Formation using an open hole slug-test method.

Trace element partitioning during the retorting of Julia Creek oil shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patterson, J.H.; Dale, L.S.; Chapman, J.f.

1987-05-01

A bulk sample of oil shale from the Julia Creek deposit in Queensland was retorted under Fischer assay conditions at temperatures ranging from 250 to 550 /sup 0/C. The distributions of the trace elements detected in the shale oil and retort water were determined at each temperature. Oil distillation commenced at 300 /sup 0/C and was essentially complete at 500 /sup 0/C. A number of trace elements were progressively mobilized with increasing retort temperature up to 450 /sup 0/C. The following trace elements partitioned mainly to the oil: vanadium, arsenic, selenium, iron, nickel, titanium, copper, cobalt, and aluminum. Elements thatmore » also partitioned to the retort waters included arsenic, selenium, chlorine, and bromine. Element mobilization is considered to be caused by the volatilization of organometallic compounds, sulfide minerals, and sodium halides present in the oil shale. The results have important implications for shale oil refining and for the disposal of retort waters. 22 references, 5 tables.« less

Standardization of vitrinite reflectance measurements in shale petroleum systems: How accurate are my Ro data?

USGS Publications Warehouse

Hackley, Paul C.

2014-01-01

Vitrinite reflectance generally is considered the most robust thermal maturity parameter available for application to hydrocarbon exploration and petroleum system evaluation. However, until 2011 there was no standardized methodology available to provide guidelines for vitrinite reflectance measurements in shale. Efforts to correct this deficiency resulted in publication of ASTM D7708-11: Standard test method for microscopical determination of the reflectance of vitrinite dispersed in sedimentary rocks. In 2012-2013, an interlaboratory exercise was conducted to establish precision limits for the measurement technique. Six samples, representing a wide variety of shale, were tested in duplicate by 28 analysts in 22 laboratories from 14 countries. Samples ranged from immature to overmature (Ro 0.31-1.53%), from organic-rich to organic-lean (1-22 wt.% total organic carbon), and contained Type I (lacustrine), Type II (marine), and Type III (terrestrial) kerogens. Repeatability values (difference between repetitive results from same operator, same conditions) ranged from 0.03-0.11% absolute reflectance, whereas reproducibility values (difference between results obtained on same test material by different operators, different laboratories) ranged from 0.12-0.54% absolute reflectance. Repeatability and reproducibility degraded consistently with increasing maturity and decreasing organic content. However, samples with terrestrial kerogens (Type III) fell off this trend, showing improved levels of reproducibility due to higher vitrinite content and improved ease of identification. Operators did not consistently meet the reporting requirements of the test method, indicating that a common reporting template is required to improve data quality. The most difficult problem encountered was the petrographic distinction of solid bitumens and low-reflecting inert macerals from vitrinite when vitrinite occurred with reflectance ranges overlapping the other components. Discussion among participants suggested this problem could not be corrected via kerogen concentration or solvent extraction and is related to operator training and background. Poor reproducibility (0.54% absolute reflectance, related to increased anisotropy?) in the highest maturity sample (Ro 1.53%) suggests that vitrinite reflectance is not a highly reliable parameter in such rocks. Future work will investigate opportunities to improve reproducibility in similar high maturity, organic-lean shale varieties.

Source rock potential of middle cretaceous rocks in Southwestern Montana

USGS Publications Warehouse

Dyman, T.S.; Palacas, J.G.; Tysdal, R.G.; Perry, W.J.; Pawlewicz, M.J.

1996-01-01

The middle Cretaceous in southwestern Montana is composed of a marine and nonmarine succession of predominantly clastic rocks that were deposited along the western margin of the Western Interior Seaway. In places, middle Cretaceous rocks contain appreciable total organic carbon (TOC), such as 5.59% for the Mowry Shale and 8.11% for the Frontier Formation in the Madison Range. Most samples, however, exhibit less than 1.0% TOC. The genetic or hydrocarbon potential (S1+S2) of all the samples analyzed, except one, yield less than 1 mg HC/g rock, strongly indicating poor potential for generating commercial amounts of hydrocarbons. Out of 51 samples analyzed, only one (a Thermopolis Shale sample from the Snowcrest Range) showed a moderate petroleum potential of 3.1 mg HC/g rock. Most of the middle Cretaceous samples are thermally immature to marginally mature, with vitrinite reflectance ranging from about 0.4 to 0.6% Ro. Maturity is high in the Pioneer Mountains, where vitrinite reflectance averages 3.4% Ro, and at Big Sky Montana, where vitrinite reflectance averages 2.5% Ro. At both localities, high Ro values are due to local heat sources, such as the Pioneer batholith in the Pioneer Mountains.

Investigating Rare Earth Element Systematics in the Marcellus Shale

NASA Astrophysics Data System (ADS)

Yang, J.; Torres, M. E.; Kim, J. H.; Verba, C.

2014-12-01

The lanthanide series of elements (the 14 rare earth elements, REEs) have similar chemical properties and respond to different chemical and physical processes in the natural environment by developing unique patterns in their concentration distribution when normalized to an average shale REE content. The interpretation of the REE content in a gas-bearing black shale deposited in a marine environment must therefore take into account the paleoredox conditions of deposition as well as any diagenetic remobilization and authigenic mineral formation. We analyzed 15 samples from a core of the Marcellus Shale (Whipkey ST1, Greene Co., PA) for REEs, TOC, gas-producing potential, trace metal content, and carbon isotopes of organic matter in order to determine the REE systematics of a black shale currently undergoing shale gas development. We also conducted a series of sequential leaching experiments targeting the phosphatic fractions in order to evaluate the dominant host phase of REEs in a black shale. Knowledge of the REE system in the Marcellus black shale will allow us to evaluate potential REE release and behavior during hydraulic fracturing operations. Total REE content of the Whipkey ST1 core ranged from 65-185 μg/g and we observed three distinct REE shale-normalized patterns: middle-REE enrichment (MREE/MREE* ~2) with heavy-REE enrichment (HREE/LREE ~1.8-2), flat patterns, and a linear enrichment towards the heavy-REE (HREE/LREE ~1.5-2.5). The MREE enrichment occurred in the high carbonate samples of the Stafford Member overlying the Marcellus Formation. The HREE enrichment occurred in the Union Springs Member of the Marcellus Formation, corresponding to a high TOC peak (TOC ~4.6-6.2 wt%) and moderate carbonate levels (CaCO3 ~4-53 wt%). Results from the sequential leaching experiments suggest that the dominant host of the REEs is the organic fraction of the black shale and that the detrital and authigenic fractions have characteristic MREE enrichments. We present our conclusions on the impact of depositional setting and diagenetic remobilization and authigenic mineral formation on the REE system in the Marcellus Shale.

A new laboratory approach to shale analysis using NMR relaxometry

USGS Publications Warehouse

Washburn, Kathryn E.; Birdwell, Justin E.; Baez, Luis; Beeney, Ken; Sonnenberg, Steve

2013-01-01

Low-field nuclear magnetic resonance (LF-NMR) relaxometry is a non-invasive technique commonly used to assess hydrogen-bearing fluids in petroleum reservoir rocks. Measurements made using LF-NMR provide information on rock porosity, pore-size distributions, and in some cases, fluid types and saturations (Timur, 1967; Kenyon et al., 1986; Straley et al., 1994; Brown, 2001; Jackson, 2001; Kleinberg, 2001; Hurlimann et al., 2002). Recent improvements in LF-NMR instrument electronics have made it possible to apply methods used to measure pore fluids to assess highly viscous and even solid organic phases within reservoir rocks. T1 and T2 relaxation responses behave very differently in solids and liquids; therefore the relationship between these two modes of relaxation can be used to differentiate organic phases in rock samples or to characterize extracted organic materials. Using T1-T2 correlation data, organic components present in shales, such as kerogen and bitumen, can be examined in laboratory relaxometry measurements. In addition, implementation of a solid-echo pulse sequence to refocus T2 relaxation caused by homonuclear dipolar coupling during correlation measurements allows for improved resolution of solid-phase protons. LF-NMR measurements of T1 and T2 relaxation time distributions were carried out on raw oil shale samples from the Eocene Green River Formation and pyrolyzed samples of these shales processed by hydrous pyrolysis and techniques meant to mimic surface and in-situ retorting. Samples processed using the In Situ Simulator approach ranged from bitumen and early oil generation through to depletion of petroleum generating potential. The standard T1-T2 correlation plots revealed distinct peaks representative of solid- and liquid-like organic phases; results on the pyrolyzed shales reflect changes that occurred during thermal processing. The solid-echo T1 and T2 measurements were used to improve assessment of the solid organic phases, specifically kerogen, thermally degraded kerogen, and char. Integrated peak areas from the LF-NMR results representative of kerogen and bitumen were found to be well correlated with S1 and S2 parameters from Rock-Eval programmed pyrolysis. This study demonstrates that LFNMR relaxometry can provide a wide range of information on shales and other reservoir rocks that goes well beyond porosity and pore-fluid analysis.

Updated methodology for nuclear magnetic resonance characterization of shales

NASA Astrophysics Data System (ADS)

Washburn, Kathryn E.; Birdwell, Justin E.

2013-08-01

Unconventional petroleum resources, particularly in shales, are expected to play an increasingly important role in the world's energy portfolio in the coming years. Nuclear magnetic resonance (NMR), particularly at low-field, provides important information in the evaluation of shale resources. Most of the low-field NMR analyses performed on shale samples rely heavily on standard T1 and T2 measurements. We present a new approach using solid echoes in the measurement of T1 and T1-T2 correlations that addresses some of the challenges encountered when making NMR measurements on shale samples compared to conventional reservoir rocks. Combining these techniques with standard T1 and T2 measurements provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen, kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed oil shale samples to examine the solid and highly viscous organic phases present during the petroleum generation process. The solid echo measurements produce additional signal in the oil shale samples compared to the standard methodologies, indicating the presence of components undergoing homonuclear dipolar coupling. The results presented here include the first low-field NMR measurements performed on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in pyrolyzed oil shale.

Updated methodology for nuclear magnetic resonance characterization of shales

USGS Publications Warehouse

Washburn, Kathryn E.; Birdwell, Justin E.

2013-01-01

Unconventional petroleum resources, particularly in shales, are expected to play an increasingly important role in the world’s energy portfolio in the coming years. Nuclear magnetic resonance (NMR), particularly at low-field, provides important information in the evaluation of shale resources. Most of the low-field NMR analyses performed on shale samples rely heavily on standard T1 and T2 measurements. We present a new approach using solid echoes in the measurement of T1 and T1–T2 correlations that addresses some of the challenges encountered when making NMR measurements on shale samples compared to conventional reservoir rocks. Combining these techniques with standard T1 and T2 measurements provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen, kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed oil shale samples to examine the solid and highly viscous organic phases present during the petroleum generation process. The solid echo measurements produce additional signal in the oil shale samples compared to the standard methodologies, indicating the presence of components undergoing homonuclear dipolar coupling. The results presented here include the first low-field NMR measurements performed on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in pyrolyzed oil shale.

Field and Lab-Based Microbiological Investigations of the Marcellus Shale

NASA Astrophysics Data System (ADS)

Wishart, J. R.; Neumann, K.; Edenborn, H. M.; Hakala, A.; Yang, J.; Torres, M. E.; Colwell, F. S.

2013-12-01

The recent exploration of shales for natural gas resources has provided the opportunity to study their subsurface geochemistry and microbiology. Evidence indicates that shale environments are marked by extreme conditions such as high temperature and pressure, low porosity, permeability and connectivity, and the presence of heavy metals and radionuclides. It has been postulated that many of these shales are naturally sterile due to the high pressure and temperature conditions under which they were formed. However, it has been shown in the Antrim and New Albany shales that microbial communities do exist in these environments. Here we review geochemical and microbiological evidence for the possible habitation of the Marcellus shale by microorganisms and compare these conditions to other shales in the U.S. Furthermore, we describe the development of sampling and analysis techniques used to evaluate microbial communities present in the Marcellus shale and associated hydraulic fracturing fluid. Sampling techniques thus far have consisted of collecting flowback fluids from wells and water impoundments and collecting core material from previous drilling expeditions. Furthermore, DNA extraction was performed on Marcellus shale sub-core with a MoBio PowerSoil kit to determine its efficiency. Assessment of the Marcellus shale indicates that it has low porosity and permeability that are not conducive to dense microbial populations; however, moderate temperatures and a natural fracture network may support a microbial community especially in zones where the Marcellus intersects more porous geologic formations. Also, hydraulic fracturing extends this fracture network providing more environments where microbial communities can exist. Previous research which collected flowback fluids has revealed a diverse microbial community that may be derived from hydrofrac fluid production or from the subsurface. DNA extraction from 10 g samples of Marcellus shale sub-core were unsuccessful even when samples were spiked with 8x108 cells/g of shale. This indicated that constituents of shale such as high levels of carbonates, humic acids and metals likely inhibited components of the PowerSoil kit. Future research is focused on refining sample collection and analyses to gain a full understanding of the microbiology of the Marcellus shale and associated flowback fluids. This includes the development of an in situ osmosampler, which will collect temporally relevant fluid and colonized substrate samples. The design of the osmosampler for hydraulic fracturing wells is being adapted from those used to sample marine environments. Furthermore, incubation experiments are underway to study interactions between microbial communities associated with hydraulic fracturing fluid and Marcellus shale samples. In conclusion, evidence suggests that the Marcellus shale is a possible component of the subsurface biosphere. Future studies will be valuable in determining the microbial community structure and function in relation to the geochemistry of the Marcellus shale and its future development as a natural gas resource.

Carbonate concretions as a significant component of ancient marine carbon cycles: Insights from paired organic and inorganic carbon isotope analyses of a Cretaceous shale

NASA Astrophysics Data System (ADS)

Loyd, S. J.

2014-12-01

Carbonate concretions often occur within fine-grained, organic-rich sedimentary rocks. This association reflects the common production of diagenetic minerals through biologic cycling of organic matter. Chemical analysis of carbonate concretions provides the rare opportunity to explore ancient shallow diagenetic environments, which are inherently transient due to progressive burial but are an integral component of the marine carbon cycle. The late Cretaceous Holz Shale (~80 Ma) contains abundant calcite concretions that exhibit textural and geochemical characteristics indicative of relatively shallow formation (i.e., near the sediment-water interface). Sampled concretions contain between 5.4 and 9.8 wt.% total inorganic carbon (TIC), or ~45 and 82 wt.% CaCO3, compared to host shale values which average ~1.5 wt.% TIC. Organic carbon isotope compositions (δ13Corg) are relatively constant in host and concretion samples ranging from ­-26.3 to -24.0‰ (VPDB). Carbonate carbon isotope compositions (δ13Ccarb) range from -22.5 to -3.4‰, indicating a significant but not entirely organic source of carbon. Concretions of the lower Holz Shale exhibit considerably elevated δ13Ccarb values averaging -4.8‰, whereas upper Holz Shale concretions express an average δ13Ccarb value of -17.0‰. If the remaining carbonate for lower Holz Shale concretions is sourced from marine fluids and/or dissolved marine carbonate minerals (e.g., shells), a simple mass balance indicates that ~28% of concretion carbon was sourced from organic matter and ~72% from late Cretaceous marine inorganic carbon (with δ13C ~ +2.5‰). Upper Holz Shale calculations indicate a ~73% contribution from organic matter and a ~27% contribution from inorganic carbon. When normalized for carbonate, organic contents within the concretions are ~2-13 wt.% enriched compared to host contents. This potentially reflects the protective nature of cementation that acts to limit permeability and chemical destruction of organic material. These data imply that concretion growth in shallow sediments can act as a significant and long-term sink for both marine inorganic and organic carbon.

Paleoceanographic Inferences from Carbon and Nitrogen Isotopic Compositions of Cenomanian Black Shales from DSDP/ODP Sites 367, 530, 603, 641, 1257-1261, and 1276 in the Atlantic Ocean

NASA Astrophysics Data System (ADS)

Yum, J.; Meyers, P. A.; Bernasconi, S. M.; Arnaboldi, M.

2005-12-01

The mid-Cretaceous (Cenomanian- Turonian) was characterized as a peak global greenhouse period with highest sea level, highest CO2 concentration in atmosphere and low thermal gradients from the poles to the equator. The depositional environment of the organic-carbon-rich black shales that typify this period remains an open question. A total of 180 Cenomanian- Turonian core samples were selected from multiple ODP and DSDP sites in the Atlantic Ocean: 530 (Cape Basin), 603 (Hatteras Rise), 641 (Galicia Bank), 1257-1261 (Demerara Rise), 1276 (Newfoundland Basin). Total organic carbon and nitrogen concentrations and isotopic compositions were measured to investigate variations in the proto-Atlantic Ocean paleoceanographic conditions that contributed to the origin of the black shales for this period. These new data were combined with existing data from Sites 367 (Senegal Rise), 530, and 603. Both the black shales and the organic-carbon-poor background sediments (less than 1 percent) have carbon isotope values between -29 to -22 permil. The C/N ratios of the background sediments are low (less than 20) compared to those of the black shales (20-40). Nitrogen isotope values range from 0 to 4 permil in the background samples. All black shales have similarly low nitrogen isotope values that range between -4 to 0 permil. These exceptionally low values are inferred to reflect the productivity of blue green algae and cyanobacteria under strongly surface stratified oceanic conditions. Although carbon isotope and C/N values of black shales show almost similar patterns at each location, there are site-specific shifts in these data that could be related to the amount of continental run off and/or the effect of latitude. Our multi-site comparison suggests that specially stratified depositional environments that could produce and accumulate the abnormally high carbon concentrations in sediments occurred throughout the proto-Atlantic ocean during the mid-Cretaceous. However, regional factors affected the amount and origin of organic matter delivered to each location.

Experimental study of CO2 effect on shale mechanical properties in the processes of complete strain-stress and post-failure tests

NASA Astrophysics Data System (ADS)

Wang, Y.; Ji, J.; Li, M.

2017-12-01

CO2 enhanced shale gas recovery has proved to be one of the most efficient methods to extract shale gas, and represent a mutually beneficial approach to mitigate greenhouse gas emission into the atmosphere. During the processes of most CO2 enhanced shale gas recovery, liquid CO2 is injected into reservoirs, fracturing the shale, making competitive adsorption with shale gas and displacing the shale gas at multi-scale to the production well. Hydraulic and mechanical coupling actions between the shale and fluid media are expected to play important roles in affecting fracture propagation, CO2 adsorption and shale gas desorption, multi-scale fluid flow, plume development, and CO2 storage. In this study, four reservoir shale samples were selected to carry out triaxial compression experiments of complete strain-stress and post failure tests. Two fluid media, CO2 and N2, were used to flow through the samples and produce the pore pressure. All of the above four compression experiments were conducted under the same confining and pore pressures, and loaded the axial pressure with the same loading path. Permeability, strain-stress, and pore volumetric change were measured and recorded over time. The results show that, compared to N2, CO2 appeared to lower the peak strength and elastic modulus of shale samples, and increase the permeability up two to six orders of magnitudes after the sample failure. Furthermore, the shale samples were dilated by CO2 much more than N2, and retained the volume of CO2 2.6 times more than N2. Results from this study indicate that the CO2 can embrittle the shale formation so as to form fracture net easily to enhance the shale gas recovery. Meanwhile, part of the remaining CO2 might be adsorbed on the surface of shale matrix and the rest of the CO2 be in the pore and fracture spaces, implying that CO2 can be effectively geo-stored in the shale formation.

Experimental study on the influence of slickwater on shale permeability

NASA Astrophysics Data System (ADS)

Liu, Zhonghua; Bai, Baojun; Zhang, Zheyu; Tang, Jing; Zeng, Shunpeng; Li, Xiaogang

2018-02-01

There are two diametrically opposite views of the influence of slickwater on shale permeability among scholars at home and abroad. We used the shale outcrops rock samples from the Lower Silurian Longmaxi Formation in Sichuan Basin. The permeability of these dry samples before and after immersion in different solution systems were tested by pulse attenuation method. The experimental results show that the impregnation of different slickwater components and standard salt solution can promote the increase of the permeability of shale samples. The stress sensitivity of shale samples after liquid immersion is medium weak to weak. The sample stress sensitivity is weak after soaked by the synergist solution and Drag reducing agent solution, and the sensitivity of the sample stress is medium weak after immersed by the standard saline solution, defoamer solution and antiswelling solution; The Ki/K0 of the shale sample after liquid immersion on σi/σ0 is consistent with the exponential stress sensitive evaluation model. With the increase of soaking time, the increase of sample permeability increases first and then decreases.

43 CFR 3935.10 - Accounting records.

Code of Federal Regulations, 2011 CFR

2011-10-01

... processing plant and retort; (3) Mineral products produced and sold; (4) Shale oil products, shale gas, and... mined or processed and of all products including synthetic petroleum, shale oil, shale gas, and shale..., DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) MANAGEMENT OF OIL SHALE EXPLORATION AND LEASES Production...

Results of chemical analyses of soil, shale, and soil/shale extract from the Mancos Shale formation in the Gunnison Gorge National Conservation Area, southwestern Colorado, and at Hanksville, Utah

USGS Publications Warehouse

Tuttle, Michele L.W.; Fahy, Juli; Grauch, Richard I.; Ball, Bridget A.; Chong, Geneva W.; Elliott, John G.; Kosovich, John J.; Livo, Keith E.; Stillings, Lisa L.

2007-01-01

Results of chemical and some isotopic analyses of soil, shale, and water extracts collected from the surface, trenches, and pits in the Mancos Shale are presented in this report. Most data are for sites on the Gunnison Gorge National Conservation Area (GGNCA) in southwestern Colorado. For comparison, data from a few sites from the Mancos landscape near Hanksville, Utah, are included. Twelve trenches were dug on the GGNCA from which 258 samples for whole-rock (total) analyses and 187 samples for saturation paste extracts were collected. Sixteen of the extract samples were duplicated and subjected to a 1:5 water extraction for comparison. A regional soil survey across the Mancos landscape on the GGNCA generated 253 samples for whole-rock analyses and saturation paste extractions. Seventeen gypsum samples were collected on the GGNCA for sulfur and oxygen isotopic analysis. Sixteen samples were collected from shallow pits in the Mancos Shale near Hanksville, Utah.

Effect of confining pressure on diffusion coefficients in clay-rich, low-permeability sedimentary rocks.

PubMed

Xiang, Y; Al, T; Mazurek, M

2016-12-01

The effect of confining pressure (CP) on the diffusion of tritiated-water (HTO) and iodide (I - ) tracers through Ordovician rocks from the Michigan Basin, southwestern Ontario, Canada, and Opalinus Clay from Schlattingen, Switzerland was investigated in laboratory experiments. Four samples representing different formations and lithologies in the Michigan Basin were studied: Queenston Formation shale, Georgian Bay Formation shale, Cobourg Formation limestone and Cobourg Formation argillaceous limestone. Estimated in situ vertical stresses at the depths from which the samples were retrieved range from 12.0 to 17.4MPa (Michigan Basin) and from 21 to 23MPa (Opalinus Clay). Effective diffusion coefficients (D e ) were determined in through-diffusion experiments. With HTO tracer, applying CP resulted in decreases in D e of 12.5% for the Queenston Formation shale (CP max =12MPa), 30% for the Georgian Bay Formation shale (15MPa), 34% for the Cobourg Formation limestone (17.4MPa), 31% for the Cobourg Formation argillaceous limestone (17.4MPa) and 43-46% for the Opalinus Clay (15MPa). Decreases in D e were larger for the I - tracer: 13.8% for the Queenston shale, 42% for the Georgian Bay shale, 50% for the Cobourg Formation limestone, 55% for the Cobourg Formation argillaceous limestone and 63-68% for the Opalinus Clay. The tracer-specific nature of the response is attributed to an increasing influence of anion exclusion as the pore size decreases at higher CP. Results from the shales (including Opalinus Clay) indicate that the pressure effect on D e can be represented by a linear relationship between D e and ln(CP), which provides valuable predictive capability. The nonlinearity results in a relatively small change in D e at high CP, suggesting that it is not necessary to apply the exact in situ pressure conditions in order to obtain a good estimate of the in situ diffusion coefficient. Most importantly, the CP effect on shale is reversible (±12%) suggesting that, for argillaceous rocks, it is possible to obtain D e values that are representative of the in-situ condition by conducting measurements on re-pressurized samples that were obtained with standard drilling practices. This may not be the case for brittle rock samples as the results from limestone suggest that irreversible damage occurred during the pressure cycling. Copyright © 2016 Elsevier B.V. All rights reserved.

Impact of Oxidative Dissolution on Black Shale Fracturing: Implication for Shale Fracturing Treatment Design

NASA Astrophysics Data System (ADS)

You, L.; Chen, Q.; Kang, Y.; Cheng, Q.; Sheng, J.

2017-12-01

Black shales contain a large amount of environment-sensitive compositions, e.g., clay minerals, carbonate, siderite, pyrite, and organic matter. There have been numerous studies on the black shales compositional and pore structure changes caused by oxic environments. However, most of the studies did not focus on their ability to facilitate shale fracturing. To test the redox-sensitive aspects of shale fracturing and its potentially favorable effects on hydraulic fracturing in shale gas reservoirs, the induced microfractures of Longmaxi black shales exposed to deionized water, hydrochloric acid, and hydrogen peroxide at room-temperature for 240 hours were imaged by scanning electron microscopy (SEM) and CT-scanning in this paper. Mineral composition, acoustic emission, swelling, and zeta potential of the untreated and oxidative treatment shale samples were also recorded to decipher the coupled physical and chemical effects of oxidizing environments on shale fracturing processes. Results show that pervasive microfractures (Fig.1) with apertures ranging from tens of nanometers to tens of microns formed in response to oxidative dissolution by hydrogen peroxide, whereas no new microfracture was observed after the exposure to deionized water and hydrochloric acid. The trajectory of these oxidation-induced microfractures was controlled by the distribution of phyllosilicate framework and flaky or stringy organic matter in shale. The experiments reported in this paper indicate that black shales present the least resistance to crack initiation and subcritical slow propagation in hydrogen peroxide, a process we refer to as oxidation-sensitive fracturing, which are closely related to the expansive stress of clay minerals, dissolution of redox-sensitive compositions, destruction of phyllosilicate framework, and the much lower zeta potential of hydrogen peroxide solution-shale system. It could mean that the injection of fracturing water with strong oxidizing aqueous solution may play an important role in improving hydraulic fracturing of shale formation by reducing the energy requirements for crack growth. However, additional work is needed to the selection of highly-effective, economical, and environmentally friendly oxidants.

4D synchrotron X-ray imaging to understand porosity development in shales during exposure to hydraulic fracturing fluid

NASA Astrophysics Data System (ADS)

Kiss, A. M.; Bargar, J.; Kohli, A. H.; Harrison, A. L.; Jew, A. D.; Lim, J. H.; Liu, Y.; Maher, K.; Zoback, M. D.; Brown, G. E.

2016-12-01

Unconventional (shale) reservoirs have emerged as the most important source of petroleum resources in the United States and represent a two-fold decrease in greenhouse gas emissions compared to coal. Despite recent progress, hydraulic fracturing operations present substantial technical, economic, and environmental challenges, including inefficient recovery, wastewater production and disposal, contaminant and greenhouse gas pollution, and induced seismicity. A relatively unexplored facet of hydraulic fracturing operations is the fluid-rock interface, where hydraulic fracturing fluid (HFF) contacts shale along faults and fractures. Widely used, water-based fracturing fluids contain oxidants and acid, which react strongly with shale minerals. Consequently, fluid injection and soaking induces a host of fluid-rock interactions, most notably the dissolution of carbonates and sulfides, producing enhanced or "secondary" porosity networks, as well as mineral precipitation. The competition between these mechanisms determines how HFF affects reactive surface area and permeability of the shale matrix. The resultant microstructural and chemical changes may also create capillary barriers that can trap hydrocarbons and water. A mechanistic understanding of the microstructure and chemistry of the shale-HFF interface is needed to design new methodologies and fracturing fluids. Shales were imaged using synchrotron micro-X-ray computed tomography before, during, and after exposure to HFF to characterize changes to the initial 3D structure. CT reconstructions reveal how the secondary porosity networks advance into the shale matrix. Shale samples span a range of lithologies from siliceous to calcareous to organic-rich. By testing shales of different lithologies, we have obtained insights into the mineralogic controls on secondary pore network development and the morphologies at the shale-HFF interface and the ultimate composition of produced water from different facies. These results show that mineral texture is a major control over secondary porosity network morphology.

The controls on the major and trace element variation of shales, siltstones, and sandstones of Pennsylvanian-Permian age from uplifted continental blocks in Colorado to platform sediment in Kansas, USA

NASA Astrophysics Data System (ADS)

Cullers, Robert L.

1994-11-01

Shales, siltstones, and sandstones of Pennsylvanian-Permian age from near the source in Colorado to those in the platform in eastern Colorado and Kansas have been analyzed for major elements and a number of trace elements, including the REEs. The near-source sandstones are significantly more enriched (Student t-test at better than the 99% confidence level) in SiO 2 and Na 2O concentrations and more depleted in Al 2O 3, Fe 2O 3 (total), TiO 2, Th, Hf, Sc, Cr, Cs, REEs, Y, and Ni concentrations and La/Co and La/Ni ratios than the near-source shales and siltstones, most likely due to more plagioclase and quartz and less clay minerals in the sandstones than in the shales and siltstones. There are no significant differences in K 2O and Sr concentrations and Eu/Eu∗, La/Lu, La/Se, Th/Sc, Th/Co, and Cr/Th ratios between the near-source sandstones and the near-source shales and siltstones. Samples of the Molas, Hermosa, and Cutler formations near the source that were formed in different environments in the same area contain no significant difference in Eu/Eu∗, La/Lu, La/Sc, Th/Sc, Th/Co, and Cr/Th ratios, so a generally silicic source and not the environment of deposition was most important in producing these elemental ratios. For example, Cr/Th ratios of near-source shales, siltstones, and sandstones range from 2.5 to 17.5 and Eu/Eu∗ range from 0.48 to 0.78, which are in the range of sources of sediments derived from mainly silicic and not basic sources. Near-source shales and siltstones contain significantly higher (Student t-test) and more varied concentrations of most elements (Al 2O 3, Fe 2O 3, MnO, TiO 2, Ba, Th, Hf, Ta, Co, Sc, REEs, Nb, Y) but significantly lower concentrations of Na 2O and Eu/Eu∗ than platform shales and siltstones in Kansas (e.g., La = 65.7 ± 40 and Eu/Eu∗ = 0.55 ± 0.07 in near-source shales and siltstones and La = 23.7 ± 8.7 and Eu/Eu∗ = 0.64 ± 0.08 in platform shales and siltstones). The SiO 2 and CaO concentrations are not significantly different in platform shales and siltstones compared to the near-source shales and siltstones, so dilution of other minerals by quartz and calcite is not the main reason for the lower concentration of most elements in the platform relative to the near-source shales and siltstones. Rather the lesser concentrations of most elements in clay minerals of the platform shales and siltstones can account for the lower concentration of most elements compared to corresponding near-source shales and siltstones. The lower concentrations of many elements in clay minerals in the platform shales and siltstones may be a result of having been derived from recycling of clay minerals from older rocks. The greater homogeneity of elemental concentrations of the platform shales and siltstones compared to those in the source is also consistent with homogeneous mixing of such recycled material. Also there is no significant difference in Th/Sc, La/Co, Th/Co, La/Ni, and Cr/Th ratios of the near-source sedimentary rocks in Colorado to the platform shales and siltstones in Kansas, and the latter are also consistent with derivation from mostly silicic source rocks.

Alkaline modified oil shale fly ash: optimal synthesis conditions and preliminary tests on CO2 adsorption.

PubMed

Reinik, Janek; Heinmaa, Ivo; Kirso, Uuve; Kallaste, Toivo; Ritamäki, Johannes; Boström, Dan; Pongrácz, Eva; Huuhtanen, Mika; Larsson, William; Keiski, Riitta; Kordás, Krisztián; Mikkola, Jyri-Pekka

2011-11-30

Environmentally friendly product, calcium-silica-aluminum hydrate, was synthesized from oil shale fly ash, which is rendered so far partly as an industrial waste. Reaction conditions were: temperature 130 and 160°C, NaOH concentrations 1, 3, 5 and 8M and synthesis time 24h. Optimal conditions were found to be 5M at 130°C at given parameter range. Original and activated ash samples were characterized by XRD, XRF, SEM, EFTEM, (29)Si MAS-NMR, BET and TGA. Semi-quantitative XRD and MAS-NMR showed that mainly tobermorites and katoite are formed during alkaline hydrothermal treatment. Physical adsorption of CO(2) on the surface of the original and activated ash samples was measured with thermo-gravimetric analysis. TGA showed that the physical adsorption of CO(2) on the oil shale fly ash sample increases from 0.06 to 3-4 mass% after alkaline hydrothermal activation with NaOH. The activated product has a potential to be used in industrial processes for physical adsorption of CO(2) emissions. Copyright © 2011 Elsevier B.V. All rights reserved.

Cretaceous shales from the western interior of North America: sulfur/carbon ratios and sulfur-isotope composition.

USGS Publications Warehouse

Gautier, D.L.

1986-01-01

Sulphur/carbon ratios in cores of selected Cretaceous marine shales average 0.67, a value greater than that observed in recent marine sediments and much higher than global values calculated for the Cretaceous. This may be ascribed to generally low levels of bioturbation and enhanced efficiency of sulphate reduction due to low oxygen levels in Cretaceous seaways. Isotopic compositions of pyrite sulphur vary systematically with level of oxygenation of the depositional environment and therefore with organic carbon abundance and type of organic matter. Samples with >4% organic carbon are extremely depleted in 34S (mean delta 34S -31per mille) and contain hydrogen-rich organic matter. Samples containing <1.5% organic carbon display relatively 'heavy' but wide-ranging delta 34S values (-34.6 to +16.8per mille) and contain hydrogen-poor organic matter. Samples with intermediate amounts of organic carbon have average delta 34S of -25.9per mille and contain both types of organic matter. Relations between the nature of these shales, and their sedimentation rate and depositional environment are discussed.-L.C.H.

Organic substances in produced and formation water from unconventional natural gas extraction in coal and shale

USGS Publications Warehouse

Orem, William H.; Tatu, Calin A.; Varonka, Matthew S.; Lerch, Harry E.; Bates, Anne L.; Engle, Mark A.; Crosby, Lynn M.; McIntosh, Jennifer

2014-01-01

Organic substances in produced and formation water from coalbed methane (CBM) and gas shale plays from across the USA were examined in this study. Disposal of produced waters from gas extraction in coal and shale is an important environmental issue because of the large volumes of water involved and the variable quality of this water. Organic substances in produced water may be environmentally relevant as pollutants, but have been little studied. Results from five CBM plays and two gas shale plays (including the Marcellus Shale) show a myriad of organic chemicals present in the produced and formation water. Organic compound classes present in produced and formation water in CBM plays include: polycyclic aromatic hydrocarbons (PAHs), heterocyclic compounds, alkyl phenols, aromatic amines, alkyl aromatics (alkyl benzenes, alkyl biphenyls), long-chain fatty acids, and aliphatic hydrocarbons. Concentrations of individual compounds range from < 1 to 100 μg/L, but total PAHs (the dominant compound class for most CBM samples) range from 50 to 100 μg/L. Total dissolved organic carbon (TOC) in CBM produced water is generally in the 1–4 mg/L range. Excursions from this general pattern in produced waters from individual wells arise from contaminants introduced by production activities (oils, grease, adhesives, etc.). Organic substances in produced and formation water from gas shale unimpacted by production chemicals have a similar range of compound classes as CBM produced water, and TOC levels of about 8 mg/L. However, produced water from the Marcellus Shale using hydraulic fracturing has TOC levels as high as 5500 mg/L and a range of added organic chemicals including, solvents, biocides, scale inhibitors, and other organic chemicals at levels of 1000 s of μg/L for individual compounds. Levels of these hydraulic fracturing chemicals and TOC decrease rapidly over the first 20 days of water recovery and some level of residual organic contaminants remain up to 250 days after hydraulic fracturing. Although the environmental impacts of the organics in produced water are not well defined, results suggest that care should be exercised in the disposal and release of produced waters containing these organic substances into the environment because of the potential toxicity of many of these substances.

Porosity of the Marcellus Shale: A contrast matching small-angle neutron scattering study

USGS Publications Warehouse

Bahadur, Jitendra; Ruppert, Leslie F.; Pipich, Vitaliy; Sakurovs, Richard; Melnichenko, Yuri B.

2018-01-01

Neutron scattering techniques were used to determine the effect of mineral matter on the accessibility of water and toluene to pores in the Devonian Marcellus Shale. Three Marcellus Shale samples, representing quartz-rich, clay-rich, and carbonate-rich facies, were examined using contrast matching small-angle neutron scattering (CM-SANS) at ambient pressure and temperature. Contrast matching compositions of H2O, D2O and toluene, deuterated toluene were used to probe open and closed pores of these three shale samples. Results show that although the mean pore radius was approximately the same for all three samples, the fractal dimension of the quartz-rich sample was higher than for the clay-rich and carbonate-rich samples, indicating different pore size distributions among the samples. The number density of pores was highest in the clay-rich sample and lowest in the quartz-rich sample. Contrast matching with water and toluene mixtures shows that the accessibility of pores to water and toluene also varied among the samples. In general, water accessed approximately 70–80% of the larger pores (>80 nm radius) in all three samples. At smaller pore sizes (~5–80 nm radius), the fraction of accessible pores decreases. The lowest accessibility to both fluids is at pore throat size of ~25 nm radii with the quartz-rich sample exhibiting lower accessibility than the clay- and carbonate-rich samples. The mechanism for this behaviour is unclear, but because the mineralogy of the three samples varies, it is likely that the inaccessible pores in this size range are associated with organics and not a specific mineral within the samples. At even smaller pore sizes (~<2.5 nm radius), in all samples, the fraction of accessible pores to water increases again to approximately 70–80%. Accessibility to toluene generally follows that of water; however, in the smallest pores (~<2.5 nm radius), accessibility to toluene decreases, especially in the clay-rich sample which contains about 30% more closed pores than the quartz- and carbonate-rich samples. Results from this study show that mineralogy of producing intervals within a shale reservoir can affect accessibility of pores to water and toluene and these mineralogic differences may affect hydrocarbon storage and production and hydraulic fracturing characteristics

Availability and quality of ground water, southern Ute Indian Reservation, southwestern Colorado

USGS Publications Warehouse

Brogden, Robert E.; Hutchinson, E. Carter; Hillier, Donald E.

1979-01-01

Population growth and the potential development of subsurface mineral resources have increased the need for information on the availability and quality of ground water on the Southern Ute Indian Reservation. The U.S. Geological Survey, in cooperation with the Southern Ute Tribal Council, the Four Corners Regional Planning Commission, and the U.S. Bureau of Indian Affairs, conducted a study during 1974-76 to assess the ground-water resources of the reservation. Water occurs in aquifers in the Dakota Sandstone, Mancos Shale, Mesaverde Group, Lewis Shale, Pictured Cliffs Sandstone, Fruitland Formation, Kirtland Shale, Animas and San Jose Formations, and terrace and flood-plain deposits. Well yields from sandstone and shale aquifers are small, generally in the range from 1 to 10 gallons per minute with maximum reported yields of 75 gallons per minute. Well yields from terrace deposits generally range from 5 to 10 gallons per minute with maximum yields of 50 gallons per minute. Well yields from flood-plain deposits are as much as 25 gallons per minute but average 10 gallons per minute. Water quality in aquifers depends in part on rock type. Water from sandstone, terrace, and flood-plain aquifers is predominantly a calcium bicarbonate type, whereas water from shale aquifers is predominantly a sodium bicarbonate type. Water from rocks containing interbeds of coal or carbonaceous shales may be either a calcium or sodium sulfate type. Dissolved-solids concentrations of ground water ranged from 115 to 7,130 milligrams per liter. Water from bedrock aquifers is the most mineralized, while water from terrace and flood-plain aquifers is the least mineralized. In many water samples collected from bedrock, terrace, and flood-plain aquifers, the concentrations of arsenic, chloride, dissolved solids, fluoride, iron, manganese, nitrate, selenium, and sulfate exceeded U.S. Public Health Service (1962) recommended limits for drinking water. Selenium in the ground water in excess of U.S. Public Health Service (1962) recommended limit of 10 micrograms per liter for drinking water occurs throughout the reservation but principally in the central part. Of the 265 wells and springs sampled, 74 contained water with selenium concentrations in excess of the recommended limit. Selenium concentrations exceeded 10 micrograms per liter principally in water from aquifers in the San Jose and Animas Formations. The maximum selenium concentration determined during the study was 13,000 micrograms per liter in a sample obtained from the San Jose Formation. The only known documented case of human selenium poisoning caused by drinking ground water occurred on the reservation.

Effects of rock mineralogy and pore structure on stress-dependent permeability of shale samples

PubMed Central

Al Ismail, Maytham I.; Zoback, Mark D.

2016-01-01

We conducted pulse-decay permeability experiments on Utica and Permian shale samples to investigate the effect of rock mineralogy and pore structure on the transport mechanisms using a non-adsorbing gas (argon). The mineralogy of the shale samples varied from clay rich to calcite rich (i.e. clay poor). Our permeability measurements and scanning electron microscopy images revealed that the permeability of the shale samples whose pores resided in the kerogen positively correlated with organic content. Our results showed that the absolute value of permeability was not affected by the mineral composition of the shale samples. Additionally, our results indicated that clay content played a significant role in the stress-dependent permeability. For clay-rich samples, we observed higher pore throat compressibility, which led to higher permeability reduction at increasing effective stress than with calcite-rich samples. Our findings highlight the importance of considering permeability to be stress dependent to achieve more accurate reservoir simulations especially for clay-rich shale reservoirs. This article is part of the themed issue ‘Energy and the subsurface’. PMID:27597792

Mineralogy and geochemistry of the Lower Cretaceous siliciclastic rocks of the Morita Formation, Sierra San José section, Sonora, Mexico

NASA Astrophysics Data System (ADS)

Madhavaraju, J.; Pacheco-Olivas, S. A.; González-León, Carlos M.; Espinoza-Maldonado, Inocente G.; Sanchez-Medrano, P. A.; Villanueva-Amadoz, U.; Monreal, Rogelio; Pi-Puig, T.; Ramírez-Montoya, Erik; Grijalva-Noriega, Francisco J.

2017-07-01

Clay mineralogy and geochemical studies were carried out on sandstone and shale samples collected from the Sierra San José section of the Morita Formation to infer the paleoclimate and paleoweathering conditions that prevailed in the source region during the deposition of these sediments. The clay mineral assemblages (fraction < 2 μm) of the Sierra San José section are composed of chlorite and illite. The abundance of illite and chlorite in the studied samples suggest that the physical weathering conditions were dominant over chemical weathering. Additionally, the illite and chlorite assemblages reflect arid or semi-arid climatic conditions in the source regions. K2O/Al2O3 ratio of shales vary between 0.15 and 0.26, which lie in the range of values for clay minerals, particularly illite composition. Likewise, sandstones vary between 0.06 and 0.13, suggesting that the clay minerals are mostly kaolinte and illite types. On the chondrite-normalized diagrams, sandstone and shale samples show enriched light rare earth elements (LREE), flat heavy rare earth elements (HREE) patterns and negative Eu anomalies. The CIA and PIA values and A-CN-K plot of shales indicate low to moderate degree of weathering in the source regions. However, the sandstones have moderate to high values of CIA and PIA suggesting a moderate to intense weathering in the source regions. The SiO2/Al2O3 ratios, bivariate and ternary plots, discriminant function diagram and elemental ratios indicate the felsic source rocks for sandstone and shale of the Morita Formation.

Porosity evolution during weathering of Marcellus shale

NASA Astrophysics Data System (ADS)

Gu, X.; Brantley, S.

2017-12-01

Weathering is an important process that continuously converts rock to regolith. Shale weathering is of particular interest because 1) shale covers about 25% of continental land mass; 2) recent development of unconventional shale gas generates large volumes of rock cuttings. When cuttings are exposed at earth's surface, they can release toxic trace elements during weathering. In this study, we investigated the evolution of pore structures and mineral transformation in an outcrop of Marcellus shale - one of the biggest gas shale play in North America - at Frankstown, Pennsylvania. A combination of neutron scattering and imaging was used to characterize the pore structures from nm to mm. The weathering profile of Marcellus shale was also compared to the well-studied Rose Hill shale from the Susquehanna Shale Hills critical zone observatory nearby. This latter shale has a similar mineral composition as Marcellus shale but much lower concentrations of pyrite and OC. The Marcellus shale formation in outcrop overlies a layer of carbonate at 10 m below land surface with low porosity (<3%). All the shale samples above the carbonate layer are almost completely depleted in carbonate, plagioclase, chlorite and pyrite. The porosities in the weathered Marcellus shale are twice as high as in protolith. The pore size distribution exhibits a broad peak for pores of size in the range of 10s of microns, likely due to the loss of OC and/or dissolution of carbonate during weathering. In the nearby Rose Hill shale, the pyrite and carbonate are sharply depleted close to the water table ( 15-20 m at ridgetop); while chlorite and plagioclase are gradually depleted toward the land surface. The greater weathering extent of silicates in the Marcellus shale despite the similarity in climate and erosion rate in these two neighboring locations is attributed to 1) the formation of micron-size pores increases the infiltration rate into weathered Marcellus shale and therefore promotes mineral weathering; 2) the pyrite/carbonate ratio is higher in the Marcellus shale than in Rose Hill shale, and thus excess acidity generated through pyrite oxidation enhances the dissolution of silicates. We seek to use these and other observations to develop a global model for shale weathering that incorporates both mineral composition and porosity change.

Multiscale properties of unconventional reservoir rocks

NASA Astrophysics Data System (ADS)

Woodruff, W. F.

A multidisciplinary study of unconventional reservoir rocks is presented, providing the theory, forward modeling and Bayesian inverse modeling approaches, and laboratory protocols to characterize clay-rich, low porosity and permeability shales and mudstones within an anisotropic framework. Several physical models characterizing oil and gas shales are developed across multiple length scales, ranging from microscale phenomena, e.g. the effect of the cation exchange capacity of reactive clay mineral surfaces on water adsorption isotherms, and the effects of infinitesimal porosity compaction on elastic and electrical properties, to meso-scale phenomena, e.g. the role of mineral foliations, tortuosity of conduction pathways and the effects of organic matter (kerogen and hydrocarbon fractions) on complex conductivity and their connections to intrinsic electrical anisotropy, as well as the macro-scale electrical and elastic properties including formulations for the complex conductivity tensor and undrained stiffness tensor within the context of effective stress and poroelasticity. Detailed laboratory protocols are described for sample preparation and measurement of these properties using spectral induced polarization (SIP) and ultrasonics for the anisotropic characterization of shales for both unjacketed samples under benchtop conditions and jacketed samples under differential loading. An ongoing study of the effects of kerogen maturation through hydrous pyrolysis on the complex conductivity is also provided in review. Experimental results are catalogued and presented for various unconventional formations in North America including the Haynesville, Bakken, and Woodford shales.

Geology of the Devonian Marcellus Shale--Valley and Ridge province, Virginia and West Virginia--a field trip guidebook for the American Association of Petroleum Geologists Eastern Section Meeting, September 28-29, 2011

USGS Publications Warehouse

Enomoto, Catherine B.; Coleman, James L.; Haynes, John T.; Whitmeyer, Steven J.; McDowell, Ronald R.; Lewis, J. Eric; Spear, Tyler P.; Swezey, Christopher S.

2012-01-01

Detailed and reconnaissance field mapping and the results of geochemical and mineralogical analyses of outcrop samples indicate that the Devonian shales of the Broadtop Synclinorium from central Virginia to southern Pennsylvania have an organic content sufficiently high and a thermal maturity sufficiently moderate to be considered for a shale gas play. The organically rich Middle Devonian Marcellus Shale is present throughout most of the synclinorium, being absent only where it has been eroded from the crests of anticlines. Geochemical analyses of outcrop and well samples indicate that hydrocarbons have been generated and expelled from the kerogen originally in place in the shale. The mineralogical characteristics of the Marcellus Shale samples from the Broadtop Synclinorium are slightly different from the averages of samples from New York, Pennsylvania, northeast Ohio, and northern West Virginia. The Middle Devonian shale interval is moderately to heavily fractured in all areas, but in some areas substantial fault shearing has removed a regular "cleat" system of fractures. Conventional anticlinal gas fields in the study area that are productive from the Lower Devonian Oriskany Sandstone suggest that a continuous shale gas system may be in place within the Marcellus Shale interval at least in a portion of the synclinorium. Third-order intraformational deformation is evident within the Marcellus shale exposures. Correlations between outcrops and geophysical logs from exploration wells nearby will be examined by field trip attendees.

Investigation of the physico-chemical and mechanical properties of hard brittle shales from the Shahejie Formation in the Nanpu Sag, northern China

NASA Astrophysics Data System (ADS)

Xiangjun, Liu; Jian, Xiong; Lixi, Liang; Yi, Ding

2017-06-01

With increasing demand for energy and advances in exploration and development technologies, more attention is being devoted to exploration and development of deep oil and gas reservoirs. The Nanpu Sag contains huge reserves in deep oil and gas reservoirs and is a promising area. In this paper, the physico-chemical and mechanical properties of hard brittle shales from the Shahejie Formation in the Nanpu Sag in the Bohai Bay Basin of northern China were investigated using a variety of methods, including x-ray diffraction analysis, cation exchange capacity (CEC) analysis, contact angle measurements, scanning electron microscope observations, immersion experiments, ultrasonic testing and mechanical testing. The effects of the physico-chemical properties of the shales on wellbore instability were observed, and the effects of hydration of the shales on wellbore instability were also examined. The results show that the major mineral constituents of the investigated shales are quartz and clay minerals. The clay mineral contents range from 25.33% to 52.03%, and the quartz contents range from 20.03% to 46.45%. The clay minerals do not include montmorillonite, but large amounts of mixed-layer illite/smectite were observed. The CEC values of the shales range from 90 to 210 mmol kg-1, indicating that the shales are partly hydrated. The wettability of the shales is strongly water-wetted, indicating that water would enter the shales due to the capillary effect. Hydration of hard brittle shales can generate cracks, leading to changes in microstructure and increases in the acoustic value, which could generate damage in the shales and reduce their strength. With increasing hydration time, the shale hydration effect gradually becomes stronger, causing an increase in the range of the acoustic travel time and decreases in the ranges of cohesion and internal friction angles. For the hard brittle shales of the Nanpu Sag, drilling fluid systems should aim to enhance sealing ability, decrease drilling fluid filter loss and increase the amount of clay-hydration inhibitor used.

Bacterial physiological diversity in the rhizosphere of range plants in response to retorted shale stress. [Agropyron smithii Rydb; Atriplex canescens (Pursh) Nutt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Metzger, W.C.; Klein, D.A.; Redente, E.F.

1986-10-01

Bacterial populations were isolated from the soil-root interface and root-free regions of Agropyron smithii Rydb. and Atriplex canescens (Pursh) Nutt. grown in soil, retorted shale, or soil over shale. Bacteria isolated from retorted shale exhibited a wider range of tolerance to alkalinity and salinity and decreased growth on amino acid substrates compared with bacteria from soil and soil-over-shale environments. Exoenzyme production was only slightly affected by growth medium treatment. Viable bacterial populations were higher in the rhizosphere and rhizoplane of plants grown in retorted shale than in plants grown in soil or soil over shale. In addition, a greater numbermore » of physiological groups of rhizosphere bacteria was observed in retorted shale, compared with soil alone. Two patterns of community similarity were observed in comparisons of bacteria from soil over shale with those from soil and retorted-shale environments. Root-associated populations from soil over shale had a higher proportion of physiological groups in common with those from the soil control than those from the retorted-shale treatment. However, in non-rhizosphere populations, bacterial groups from soil over shale more closely resembled the physiological groups from retorted shale.« less

Using Neutrons to Study Fluid-Rock Interactions in Shales

NASA Astrophysics Data System (ADS)

DiStefano, V. H.; McFarlane, J.; Anovitz, L. M.; Gordon, A.; Hale, R. E.; Hunt, R. D.; Lewis, S. A., Sr.; Littrell, K. C.; Stack, A. G.; Chipera, S.; Perfect, E.; Bilheux, H.; Kolbus, L. M.; Bingham, P. R.

2015-12-01

Recovery of hydrocarbons by hydraulic fracturing depends on complex fluid-rock interactions that we are beginning to understand using neutron imaging and scattering techniques. Organic matter is often thought to comprise the majority of porosity in a shale. In this study, correlations between the type of organic matter embedded in a shale and porosity were investigated experimentally. Selected shale cores from the Eagle Ford and Marcellus formations were subjected to pyrolysis-gas chromatography, Differential Thermal Analysis/Thermogravimetric analysis, and organic solvent extraction with the resulting affluent analyzed by gas chromatography-mass spectrometry. The pore size distribution of the microporosity (~1 nm to 2 µm) in the Eagle Ford shales was measured before and after solvent extraction using small angle neutron scattering. Organics representing mass fractions of between 0.1 to 1 wt.% were removed from the shales and porosity generally increased across the examined microporosity range, particularly at larger pore sizes, approximately 50 nm to 2 μm. This range reflects extraction of accessible organic material, including remaining gas molecules, bitumen, and kerogen derivatives, indicating where the larger amount of organic matter in shale is stored. An increase in porosity at smaller pore sizes, ~1-3 nm, was also present and could be indicative of extraction of organic material stored in the inter-particle spaces of clays. Additionally, a decrease in porosity after extraction for a sample was attributed to swelling of pores with solvent uptake. This occurred in a shale with high clay content and low thermal maturity. The extracted hydrocarbons were primarily paraffinic, although some breakdown of larger aromatic compounds was observed in toluene extractions. The amount of hydrocarbon extracted and an overall increase in porosity appeared to be primarily correlated with the clay percentage in the shale. This study complements fluid transport neutron imaging studies, to explain the physics and chemistry of fluid-rock behavior. Research supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division and the Bredesen Center at the University of Tennessee.

Geology of uranium in the Chadron area, Nebraska and South Dakota

USGS Publications Warehouse

Dunham, Robert Jacob

1961-01-01

The Chadron area covers 375 square miles about 25 miles southeast of the Black Hills. Recurrent mild tectonic activity and erosion on the Chadron arch, a compound anticlinal uplift of regional extent, exposed 1900 feet of Upper Cretaceous rocks, mostly marine shale containing pyrite and organic matter, and 600 feet of Oligocene and Miocene rocks, mostly terrestrial fine-grained sediment containing volcanic ash. Each Cretaceous formation truncated by the sub-Oligocene unconformity is stained yellow and red, leached, kaolinized, and otherwise altered to depths as great as 55 feet. The composition and profile of the altered material indicate lateritic soil; indirect evidence indicates Eocene(?) age. In a belt through the central part of the area, the Brule formation of Oligocene age is a sequence of bedded gypsum, clay, dolomite, and limestone more than 300 feet thick. Uranium in Cretaceous shale in 58 samples averages 0.002 percent, ten times the average for the earths crust. Association with pyrite and organic matter indicates low valency. The uranium probably is syngenetic or nearly so. Uranium in Eocene(?) soil in 43 samples averages 0.054 percent, ranging up to 1.12 percent. The upper part of the soil is depleted in uranium; enriched masses in the basal part of the soil consist of remnants of bedrock shale and are restricted to the highest reaches of the ancient oxidation-reduction interface. The uranium is probably in the from of a low-valent mineral, perhaps uraninite. Modern weathering of Cretaceous shale is capable of releasing as much as 0.780 ppm uranium to water. Eocene(?) weathering probably caused enrichment of the ancient soil through 1) leaching of Cretaceous shale, 2) downward migration of uranyl complex ions, and 3) reduction of hydrogen sulfide at the water table. Uranium minerals occur in the basal 25 feet of the gypsum facies of the Brule formation at the two localities where the gypsum is carbonaceous; 16 samples average 0.066 percent uranium and range up to 0.43 percent. Elsewhere uranium in dolomite and limestone in the basal 25 feet of the gypsum facies in 10 samples averages 0.007 percent, ranging up to 0.12 percent. Localization of the uranium at the base of the gypsum facies suggests downward moving waters; indirect evidence that the water from which the gypsum was deposited was highly alkaline suggests that the uranium was leached from volcanic ash in Oligocene time.

Compaction trends of full stiffness tensor and fluid permeability in artificial shales

NASA Astrophysics Data System (ADS)

Beloborodov, Roman; Pervukhina, Marina; Lebedev, Maxim

2018-03-01

We present a methodology and describe a set-up that allows simultaneous acquisition of all five elastic coefficients of a transversely isotropic (TI) medium and its permeability in the direction parallel to the symmetry axis during mechanical compaction experiments. We apply the approach to synthetic shale samples and investigate the role of composition and applied stress on their elastic and transport properties. Compaction trends for the five elastic coefficients that fully characterize TI anisotropy of artificial shales are obtained for a porosity range from 40 per cent to 15 per cent. A linear increase of elastic coefficients with decreasing porosity is observed. The permeability acquired with the pressure-oscillation technique exhibits exponential decrease with decreasing porosity. Strong correlations are observed between an axial fluid permeability and seismic attributes, namely, VP/VS ratio and acoustic impedance, measured in the same direction. These correlations might be used to derive permeability of shales from seismic data given that their mineralogical composition is known.

A comparative study of removal of fluoride from contaminated water using shale collected from different coal mines in India.

PubMed

Biswas, Gargi; Dutta, Manjari; Dutta, Susmita; Adhikari, Kalyan

2016-05-01

Low-cost water defluoridation technique is one of the most important issues throughout the world. In the present study, shale, a coal mine waste, is employed as novel and low-cost adsorbent to abate fluoride from simulated solution. Shale samples were collected from Mahabir colliery (MBS) and Sonepur Bazari colliery (SBS) of Raniganj coalfield in West Bengal, India, and used to remove fluoride. To increase the adsorption efficiency, shale samples were heat activated at a higher temperature and samples obtained at 550 °C are denoted as heat-activated Mahabir colliery shale (HAMBS550) and heat-activated Sonepur Bazari colliery shale (HASBS550), respectively. To prove the fluoride adsorption onto different shale samples and ascertain its mechanism, natural shale samples, heat-activated shale samples, and their fluoride-loaded forms were characterized using scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction study, and Fourier transform infrared spectroscopy. The effect of different parameters such as pH, adsorbent dose, size of particles, and initial concentration of fluoride was investigated during fluoride removal in a batch contactor. Lower pH shows better adsorption in batch study, but it is acidic in nature and not suitable for direct consumption. However, increase of pH of the solution from 3.2 to 6.8 and 7.2 during fluoride removal process with HAMBS550 and HASBS550, respectively, confirms the applicability of the treated water for domestic purposes. HAMBS550 and HASBS550 show maximum removal of 88.3 and 88.5 %, respectively, at initial fluoride concentration of 10 mg/L, pH 3, and adsorbent dose of 70 g/L.

Sylhet-Kopili/Barail-Tipam Composite Total Petroleum System, Assam Geologic Province, India

USGS Publications Warehouse

Wandrey, Craig J.

2004-01-01

The Sylhet-Kopili/Barail-Tipam Composite total petroleum system (TPS) (803401) is located in the Assam Province in northeasternmost India and includes the Assam Shelf south of the Brahmaputra River. The area is primarily a southeast-dipping shelf overthrust by the Naga Hills on the southeast and the Himalaya Mountain range to the north. The rocks that compose this TPS are those of the Sylhet-Kopili/Barail-Tipam composite petroleum system. These rocks are those of the Eocene-Oligocene Jaintia Group Sylhet and Kopili Formations, the Oligocene Barail Group, the Oligocene-Miocene Surma and Tipam Groups. These groups include platform carbonates, shallow marine shales and sandstones, and the sandstones, siltstones, shales, and coals of deltaic and lagoonal facies. Source rocks include the Sylhet and Kopili Formation shales, Barail Group coals and shales, and in the south the Surma Group shales. Total organic content is generally low, averaging from 0.5 to 1.8 percent; it is as high as 9 percent in the Barail Coal Shales. Maturities are generally low, from Ro 0.45 to 0.7 percent where sampled. Maturity increases to the southeast near the Naga thrust fault and can be expected to be higher in the subthrust. Generation began in early Pliocene. Migration is primarily updip to the northwest (< 5 to 15 kilometers) along the northeast-trending slope of the Assam Shelf, and vertical migration occurs through reactivated basement-rooted faults associated with the plate collisions. Reservoir rocks are carbonates of the Sylhet Formation, interbedded sandstones of the Kopili Formation and sandstones of the Barail, Surma, and Tipam Groups. Permeability ranges from less than 8 mD (millidarcies) to as high as 800 mD in the Tipam Group. Porosity ranges from less than 7 percent to 30 percent. Traps are primarily anticlines and faulted anticlines with a few subtle stratigraphic traps. There is also a likelihood of anticlinal traps in the subthrust. Seals include interbedded Oligocene and Miocene shales and clays, and the thick clays of the Pliocene Gurjan Group.

Oil-shale data, cores, and samples collected by the U.S. geological survey through 1989

USGS Publications Warehouse

Dyni, John R.; Gay, Frances; Michalski, Thomas C.; ,

1990-01-01

The U.S. Geological Survey has acquired a large collection of geotechnical data, drill cores, and crushed samples of oil shale from the Eocene Green River Formation in Colorado, Wyoming, and Utah. The data include about 250,000 shale-oil analyses from about 600 core holes. Most of the data is from Colorado where the thickest and highest-grade oil shales of the Green River Formation are found in the Piceance Creek basin. Other data on file but not yet in the computer database include hundreds of lithologic core descriptions, geophysical well logs, and mineralogical and geochemical analyses. The shale-oil analyses are being prepared for release on floppy disks for use on microcomputers. About 173,000 lineal feet of drill core of oil shale and associated rocks, as well as 100,000 crushed samples of oil shale, are stored at the Core Research Center, U.S. Geological Survey, Lakewood, Colo. These materials are available to the public for research.

Neutron Scattering Measurements of Carbon Dioxide Adsorption in Pores within the Marcellus Shale: Implications for Sequestration.

PubMed

Stefanopoulos, Konstantinos L; Youngs, Tristan G A; Sakurovs, Richard; Ruppert, Leslie F; Bahadur, Jitendra; Melnichenko, Yuri B

2017-06-06

Shale is an increasingly viable source of natural gas and a potential candidate for geologic CO 2 sequestration. Understanding the gas adsorption behavior on shale is necessary for the design of optimal gas recovery and sequestration projects. In the present study neutron diffraction and small-angle neutron scattering measurements of adsorbed CO 2 in Marcellus Shale samples were conducted on the Near and InterMediate Range Order Diffractometer (NIMROD) at the ISIS Pulsed Neutron and Muon Source, STFC Rutherford Appleton Laboratory along an adsorption isotherm of 22 °C and pressures of 25 and 40 bar. Additional measurements were conducted at approximately 22 and 60 °C at the same pressures on the General-Purpose Small-Angle Neutron Scattering (GP-SANS) instrument at Oak Ridge National Laboratory. The structures investigated (pores) for CO 2 adsorption range in size from Å level to ∼50 nm. The results indicate that, using the conditions investigated densification or condensation effects occurred in all accessible pores. The data suggest that at 22 °C the CO 2 has liquid-like properties when confined in pores of around 1 nm radius at pressures as low as 25 bar. Many of the 2.5 nm pores, 70% of 2 nm pores, most of the <1 nm pores, and all pores <0.25 nm, are inaccessible or closed to CO 2 , suggesting that despite the vast numbers of micropores in shale, the micropores will be unavailable for storage for geologic CO 2 sequestration.

Methane baseline concentrations and sources in shallow aquifers from the shale gas-prone region of the St. Lawrence lowlands (Quebec, Canada).

PubMed

Moritz, Anja; Hélie, Jean-Francois; Pinti, Daniele L; Larocque, Marie; Barnetche, Diogo; Retailleau, Sophie; Lefebvre, René; Gélinas, Yves

2015-04-07

Hydraulic fracturing is becoming an important technique worldwide to recover hydrocarbons from unconventional sources such as shale gas. In Quebec (Canada), the Utica Shale has been identified as having unconventional gas production potential. However, there has been a moratorium on shale gas exploration since 2010. The work reported here was aimed at defining baseline concentrations of methane in shallow aquifers of the St. Lawrence Lowlands and its sources using δ(13)C methane signatures. Since this study was performed prior to large-scale fracturing activities, it provides background data prior to the eventual exploitation of shale gas through hydraulic fracturing. Groundwater was sampled from private (n = 81), municipal (n = 34), and observation (n = 15) wells between August 2012 and May 2013. Methane was detected in 80% of the wells with an average concentration of 3.8 ± 8.8 mg/L, and a range of <0.0006 to 45.9 mg/L. Methane concentrations were linked to groundwater chemistry and distance to the major faults in the studied area. The methane δ(1)(3)C signature of 19 samples was > -50‰, indicating a potential thermogenic source. Localized areas of high methane concentrations from predominantly biogenic sources were found throughout the study area. In several samples, mixing, migration, and oxidation processes likely affected the chemical and isotopic composition of the gases, making it difficult to pinpoint their origin. Energy companies should respect a safe distance from major natural faults in the bedrock when planning the localization of hydraulic fracturation activities to minimize the risk of contaminating the surrounding groundwater since natural faults are likely to be a preferential migration pathway for methane.

Rock Magnetic Cyclostratigraphy of the Mid-Cretaceous Greenhorn Limestone, South-Central Colorado---Influence of Orbitally Induced Climate Variability for Chornostratigraphy

NASA Astrophysics Data System (ADS)

Sellers, T.; Geissman, J. W.; Jackson, J.

2015-12-01

We are testing the hypothesis that depositional processes of the mid-Cretaceous Greenhorn Limestone were influenced by orbitally-driven climate variations using rock magnetic data. Correlation of the data, including anhysteretic remanent magnetization (ARM), magnetic susceptibility, isothermal remanent magnetization in different DC fields to saturation, and hysteresis properties, from three continuously exposed sections of the full Greenhorn Limestone provides detailed spatial distribution for the depositional processes and magnetic mineral climate encoding. The Greenhorn Limestone includes the Lincoln Limestone, Hartland Shale, and the Bridge Creek Limestone members and consists of calcareous shales and limestones representing near maximum depths in the Cretaceous interior seaway. The sections, each about 30 m thick, extend from the upper Graneros Shale, through the Greenhorn Formation, to the lower Carlisle Shale, with samples collected at a two to five cm interval and are located at Badito, CO; north of Redwing, CO; and at the Global boundary Stratotype Section and Point (GSSP) at Lake Pueblo, CO. Our over 1000 samples were hand crushed to granule size pieces and packed into 7cc IODP boxes. Bulk magnetic susceptibility, anhysteretic remanent magnetization (ARM) intensity at different peak AF levels, and isothermal remanent magnetization (IRM) intensity record variations in magnetic mineral concentration and are proxies to determine orbital scale cycles and precise stratigraphic correlation between sections. ARM intensities in a peak field of 100 mT at both sites range between 1.2 x 10-3 and 1.3 x 10-4 A/m and better define periodic variation within the Greenhorn Limestone displaying differences in ferromagnetic mineral content of detrital origin. Magnetic susceptibility, which ranges from 3.5 x 10-2 to 2.86 x 10-3, also shows periodic variation with a strong correlation among the three sections. Saturation IRM at 100 mT ranges from 3.2 x 10-1 to 1.1x 10-2 A/m shows periodic variation with the greatest variability in the Bridge Creek Member. Preliminary spectral analysis of each data set indicates a dominant cyclicity that is of considerably lower frequency than the limestone/shale couplets characteristic of Greenhorn Limestone.

Variations in petrophysical properties of shales along a stratigraphic section in the Whitby mudstone (UK)

NASA Astrophysics Data System (ADS)

Barnhoorn, Auke; Houben, Maartje; Lie-A-Fat, Joella; Ravestein, Thomas; Drury, Martyn

2015-04-01

In unconventional tough gas reservoirs (e.g. tight sandstones or shales) the presence of fractures, either naturally formed or hydraulically induced, is almost always a prerequisite for hydrocarbon productivity to be economically viable. One of the formations classified so far as a potential interesting formation for shale gas exploration in the Netherlands is the Lower Jurassic Posidonia Shale Formation (PSF). However data of the Posidonia Shale Formation is scarce so far and samples are hard to come by, especially on the variability and heterogeneity of the petrophysical parameters of this shale little is known. Therefore research and sample collection is conducted on a time and depositional analogue of the PSF: the Whitby Mudstone Formation (WMF) in the United Kingdom. A large number of samples along a ~7m stratigraphic section of the Whitby Mudstone Formation have been collected and analysed. Standard petrophysical properties such as porosity and matrix densities are quantified for a number of samples throughout the section, as well as mineral composition analysis based on XRD/XRF and SEM analyses. Seismic velocity measurements are also conducted at multiple heights in the section and in multiple directions to elaborate on anisotropy of the material. Attenuation anisotropy is incorporated as well as Thomsen's parameters combined with elastic parameters, e.g. Young's modulus and Poisson's ratio, to quantify the elastic anisotropy. Furthermore rock mechanical experiments are conducted to determine the elastic constants, rock strength, fracture characteristics, brittleness index, fraccability and rock mechanical anisotropy across the stratigraphic section of the Whitby mudstone formation. Results show that the WMF is highly anisotropic and it exhibits an anisotropy on the large limit of anisotropy reported for US gas shales. The high anisotropy of the Whitby shales has an even larger control on the formation of the fracture network. Furthermore, most petrophysical properties are highly variable. They vary per sample, but even within a sample on a mm-scale, large variations in e.g. the porosity occur. These relatively large variations influence the potential for future shale gas exploration for these Lower Jurassic shales in northern Europe and need to be quantified in detail beforehand. Compositional analyses and rock deformation experiments on the first samples indicate relatively low brittleness indices for the Whitby shale, but variation of these parameters within the stratigraphy are present. All petrophysical analyses combined will provide a complete assessment of the potential for shale gas exploration of these Lower Jurassic shales.

43 CFR 3905.10 - Oil shale lease exchanges.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 43 Public Lands: Interior 2 2011-10-01 2011-10-01 false Oil shale lease exchanges. 3905.10 Section... MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Lease Exchanges § 3905.10 Oil shale lease exchanges. To facilitate the recovery of oil shale, the BLM may consider land...

EVALUATION OF THE EFFECTS OF WEATHERING ON A 50-YEAR OLD RETORTED OIL-SHALE WASTE PILE, RULISON EXPERIMENTAL RETORT, COLORADO.

USGS Publications Warehouse

Tuttle, Michele L.W.; Dean, Walter E.; Ackerman, Daniel J.; ,

1985-01-01

An oil-shale mine and experimental retort were operated near Rulison, Colorado by the U. S. Bureau of Mines from 1926 to 1929. Samples from seven drill cores from a retorted oil-shale waste pile were analyzed to determine 1) the chemical and mineral composition of the retorted oil shale and 2) variations in the composition that could be attributed to weathering. Unweathered, freshly-mined samples of oil shale from the Mahogany zone of the Green River Formation and slope wash collected away from the waste pile were also analyzed for comparison. The waste pile is composed of oil shale retorted under either low-temperature (400-500 degree C) or high-temperature (750 degree C) conditions. The results of the analyses show that the spent shale within the waste pile contains higher concentrations of most elements relative to unretorted oil shale.

Integrating SANS and fluid-invasion methods to characterize pore structure of typical American shale oil reservoirs.

PubMed

Zhao, Jianhua; Jin, Zhijun; Hu, Qinhong; Jin, Zhenkui; Barber, Troy J; Zhang, Yuxiang; Bleuel, Markus

2017-11-13

An integration of small-angle neutron scattering (SANS), low-pressure N 2 physisorption (LPNP), and mercury injection capillary pressure (MICP) methods was employed to study the pore structure of four oil shale samples from leading Niobrara, Wolfcamp, Bakken, and Utica Formations in USA. Porosity values obtained from SANS are higher than those from two fluid-invasion methods, due to the ability of neutrons to probe pore spaces inaccessible to N 2 and mercury. However, SANS and LPNP methods exhibit a similar pore-size distribution, and both methods (in measuring total pore volume) show different results of porosity and pore-size distribution obtained from the MICP method (quantifying pore throats). Multi-scale (five pore-diameter intervals) inaccessible porosity to N 2 was determined using SANS and LPNP data. Overall, a large value of inaccessible porosity occurs at pore diameters <10 nm, which we attribute to low connectivity of organic matter-hosted and clay-associated pores in these shales. While each method probes a unique aspect of complex pore structure of shale, the discrepancy between pore structure results from different methods is explained with respect to their difference in measurable ranges of pore diameter, pore space, pore type, sample size and associated pore connectivity, as well as theoretical base and interpretation.

Talaromyces sayulitensis, Acidiella bohemica and Penicillium citrinum in Brazilian oil shale by-products.

PubMed

de Goes, Kelly C G P; da Silva, Josué J; Lovato, Gisele M; Iamanaka, Beatriz T; Massi, Fernanda P; Andrade, Diva S

2017-12-01

Fine shale particles and retorted shale are waste products generated during the oil shale retorting process. These by-products are small fragments of mined shale rock, are high in silicon and also contain organic matter, micronutrients, hydrocarbons and other elements. The aims of this study were to isolate and to evaluate fungal diversity present in fine shale particles and retorted shale samples collected at the Schist Industrialization Business Unit (Six)-Petrobras in São Mateus do Sul, State of Paraná, Brazil. Combining morphology and internal transcribed spacer (ITS) sequence, a total of seven fungal genera were identified, including Acidiella, Aspergillus, Cladosporium, Ochroconis, Penicillium, Talaromyces and Trichoderma. Acidiella was the most predominant genus found in the samples of fine shale particles, which are a highly acidic substrate (pH 2.4-3.6), while Talaromyces was the main genus in retorted shale (pH 5.20-6.20). Talaromyces sayulitensis was the species most frequently found in retorted shale, and Acidiella bohemica in fine shale particles. The presence of T. sayulitensis, T. diversus and T. stolli in oil shale is described herein for the first time. In conclusion, we have described for the first time a snapshot of the diversity of filamentous fungi colonizing solid oil shale by-products from the Irati Formation in Brazil.

Preliminary evaluation of the shale gas prospectivity of the Lower Cretaceous Pearsall Formation in the onshore Gulf Coast region, United States

USGS Publications Warehouse

Enomoto, Catherine B.; Scott, Kristina; Valentine, Brett J.; Hackley, Paul C.; Dennen, Kristin; Lohr, Celeste D.

2012-01-01

Recent work by the U.S. Geological Survey indicated that the Lower Cretaceous Pearsall Formation contains an estimated mean undiscovered, technically recoverable unconventional gas resource of 8.8 trillion cubic ft in the Maverick Basin, South Texas. Cumulative gas production from horizontal wells in the core area of the emerging play has exceeded 5 billion cubic ft since 2008. However, very little information is available to characterize the Pearsall Formation as an unconventional gas resource beyond the Maverick Basin in the greater Gulf Coast region. Therefore, this reconnaissance study examines spatial distribution, thickness, organic richness and thermal maturity of the Pearsall Formation in the onshore U.S. Gulf states using wireline logs and drill cuttings sample analysis. Spontaneous potential and resistivity curves of approximately forty wireline logs from wells in five Gulf Coast states were correlated to ascertain the thickness of the Pearsall Formation and delineate its three members: Pine Island Shale, James Limestone or Cow Creek Limestone, and Bexar Shale, in ascending stratigraphic order. In Florida and Alabama the Pearsall Formation is up to about 300 ft thick; in Mississippi, Louisiana, Arkansas, and East Texas, thickness is up to as much as 800 ft. Drill cuttings sampled from 11 wells at depths ranging from 4600 to 19,600 feet subsurface indicate increasingly oxygenated depositional environments (predominance of red shale) towards the eastern part of the basin. Cuttings vary widely in lithology but indicate interbedded clastics and limestones throughout the Pearsall Formation, consistent with previous regional studies. Organic petrographic and geochemical analyses of 17 cutting samples in the Pearsall Formation indicate a wide range in thermal maturity, from immature (0.43% Ro [vitrinite reflectance]) in paleo-high structural locations to the peak oil window (0.99% Ro) in the eastern portion of the Gulf Coast Basin. This is in contrast to dry gas thermal maturity throughout the Pearsall Formation in the South Texas Maverick Basin. Organic carbon content is low overall, even in immature samples, with a range of 0.17 to 1.08 wt.% by Leco in 22 Pearsall Formation samples. The pyrolysis output range was 0.23 to 2.33 mg hydrocarbon/g rock. The thermal maturity and Rock-Eval pyrolysis data and organic petrologic observations from this study will be used to better focus specific areas of investigation where the Pearsall Formation may be prospective as an unconventional hydrocarbon source and reservoir.

Halogenation of Hydraulic Fracturing Additives in the Shale Well Parameter Space

NASA Astrophysics Data System (ADS)

Sumner, A. J.; Plata, D.

2017-12-01

Horizontal Drilling and Hydraulic fracturing (HDHF) involves the deep-well injection of a `fracking fluid' composed of diverse and numerous chemical additives designed to facilitate the release and collection of natural gas from shale plays. The potential impacts of HDHF operations on water resources and ecosystems are numerous, and analyses of flowback samples revealed organic compounds from both geogenic and anthropogenic sources. Furthermore, halogenated chemicals were also detected, and these compounds are rarely disclosed, suggesting the in situ halogenation of reactive additives. To test this transformation hypothesis, we designed and operated a novel high pressure and temperature reactor system to simulate the shale well parameter space and investigate the chemical reactivity of twelve commonly disclosed and functionally diverse HDHF additives. Early results revealed an unanticipated halogenation pathway of α-β unsaturated aldehyde, Cinnamaldehyde, in the presence of oxidant and concentrated brine. Ongoing experiments over a range of parameters informed a proposed mechanism, demonstrating the role of various shale-well specific parameters in enabling the demonstrated halogenation pathway. Ultimately, these results will inform a host of potentially unintended interactions of HDHF additives during the extreme conditions down-bore of a shale well during HDHF activities.

Creep of Posidonia and Bowland shale at elevated pressures and temperatures

NASA Astrophysics Data System (ADS)

Herrmann, Johannes; Rybacki, Erik; Sone, Hiroki; Dresen, Georg

2017-04-01

The fracture-healing rate of artificial cracks generated by hydraulic fracturing is of major interest in the E&P industry since it is important for the long-time productivity of a well. To estimate the stress-induced healing rate of unconventional reservoir rocks, we performed deformation tests on Bowland shale rocks (UK) and on Posidonia shales (Germany). Samples of 1cm diameter and 2cm length were drilled perpendicular to the bedding and deformed in a high pressure, high temperature deformation apparatus. Constant strain rate tests at 5*10-4*s-1, 50 MPa confining pressure and 100˚ C temperature reveal a mainly brittle behaviour with predominantly elastic deformation before failure and high strength of low porosity (˜2%), quartz-rich (˜42 vol%) Bowland shale. In contrast, the low porosity (˜3%), carbonate- (˜43 vol%) and clay-rich (˜33 vol%) Posidonia shale deforms semi-brittle with pronounced inelastic deformation and low peak strength. These results suggest a good fracability of the Bowland formation compared to the Posidonia shale. Constant load (creep) experiments performed on Bowland shale at 100˚ C temperature and 75 MPa pressure show mainly transient (primary) deformation with increasing strain rate at increasing axial stress. The strain rate increases also with increasing temperature, measured in the range of 75 - 150˚ C at fixed stress and confinement. In contrast, increasing confining pressure (from 30 to 115 MPa) at given temperature and stress results in decreasing strain rate. In contrast, Posidonia shale rocks are much more sensitive to changes in stress, temperature and pressure than Bowland shale. Empirical relations between strain and stress that account for the influence of pressure and temperature on creep properties of Posidonia and Bowland shale rocks can be used to estimate the fracture healing rate of these shales under reservoir conditions.

Experimental investigation on the fracture behaviour of black shale by acoustic emission monitoring and CT image analysis during uniaxial compression

NASA Astrophysics Data System (ADS)

Wang, Y.; Li, C. H.; Hu, Y. Z.

2018-04-01

Plenty of mechanical experiments have been done to investigate the deformation and failure characteristics of shale; however, the anisotropic failure mechanism has not been well studied. Here, laboratory Uniaxial Compressive Strength tests on cylindrical shale samples obtained by drilling at different inclinations to bedding plane were performed. The failure behaviours of the shale samples were studied by real-time acoustic emission (AE) monitoring and post-test X-ray computer tomography (CT) analysis. The experimental results suggest that the pronounced bedding planes of shale have a great influence on the mechanical properties and AE patterns. The AE counts and AE cumulative energy release curves clearly demonstrate different morphology, and the `U'-shaped curve relationship between the AE counts, AE cumulative energy release and bedding inclination was first documented. The post-test CT image analysis shows the crack patterns via 2-D image reconstructions, an index of stimulated fracture density is defined to represent the anisotropic failure mode of shale. What is more, the most striking finding is that the AE monitoring results are in good agreement with the CT analysis. The structural difference in the shale sample is the controlling factor resulting in the anisotropy of AE patterns. The pronounced bedding structure in the shale formation results in an anisotropy of elasticity, strength and AE information from which the changes in strength dominate the entire failure pattern of the shale samples.

Lower Cody Shale (Niobrara equivalent) in the Bighorn Basin, Wyoming and Montana: thickness, distribution, and source rock potential

USGS Publications Warehouse

Finn, Thomas M.

2014-01-01

The lower shaly member of the Cody Shale in the Bighorn Basin, Wyoming and Montana is Coniacian to Santonian in age and is equivalent to the upper part of the Carlile Shale and basal part of the Niobrara Formation in the Powder River Basin to the east. The lower Cody ranges in thickness from 700 to 1,200 feet and underlies much of the central part of the basin. It is composed of gray to black shale, calcareous shale, bentonite, and minor amounts of siltstone and sandstone. Sixty-six samples, collected from well cuttings, from the lower Cody Shale were analyzed using Rock-Eval and total organic carbon analysis to determine the source rock potential. Total organic carbon content averages 2.28 weight percent for the Carlile equivalent interval and reaches a maximum of nearly 5 weight percent. The Niobrara equivalent interval averages about 1.5 weight percent and reaches a maximum of over 3 weight percent, indicating that both intervals are good to excellent source rocks. S2 values from pyrolysis analysis also indicate that both intervals have a good to excellent source rock potential. Plots of hydrogen index versus oxygen index, hydrogen index versus Tmax, and S2/S3 ratios indicate that organic matter contains both Type II and Type III kerogen capable of generating oil and gas. Maps showing the distribution of kerogen types and organic richness for the lower shaly member of the Cody Shale show that it is more organic-rich and more oil-prone in the eastern and southeastern parts of the basin. Thermal maturity based on vitrinite reflectance (Ro) ranges from 0.60–0.80 percent Ro around the margins of the basin, increasing to greater than 2.0 percent Ro in the deepest part of the basin, indicates that the lower Cody is mature to overmature with respect to hydrocarbon generation.

43 CFR 3900.5 - Information collection.

Code of Federal Regulations, 2011 CFR

2011-10-01

... MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Oil Shale... information. (b) Respondents are oil shale lessees and operators. The requirement to respond to the... extent and specific characteristics of the Federal oil shale resource. The BLM will use the information...

The organic geochemical characterization: An indication of type of kerogen and maturity of early - Mid Jurassic shale in the Blue Nile formation

NASA Astrophysics Data System (ADS)

Shoieba, Monera Adam; Sum, Chow Weng; Abidin, Nor Syazwani Zainal; Bhattachary, Swapan Kumar

2018-06-01

The heterogeneity and complexity of shale gas has become clear as the development of unconventional resources have improved. The Blue Nile Basin, is one of the many Mesozoic rift basins in Sudan associated with the Central African Rift System (CARS). It is located in the eastern part of the Republic of Sudan and has been the major focus for shale gas exploration due to the hydrocarbon found in the basin. But so far no success of discovery has been achieved because the shale gas potentiality of the study area is still unknown. The objective of this study is to assess the type of kerogen and maturity of the shale samples from the Blue Nile Formation within the Blue Nile Basin. This was done by employing organic geochemical methods such as pyrolysis gas chromatography (Py-GC) and petrographic analysis such as vitrinite reflectance (Ro%). Ten representative shale samples from TW-1 well in the Blue Nile Formation have been used to assess the quality of the source rock. Pyrolysis GC analysis indicate that all the selected shale samples contain Type II kerogen that produces oil and gas. The Blue Nile Formation possesses vitrinite reflectance (Ro%) of 0.60-0.65%, indicating that the shale samples are mature in the oil window.

Effects of processed oil shale on the element content of Atriplex cancescens

USGS Publications Warehouse

Anderson, B.M.

1982-01-01

Samples of four-wing saltbush were collected from the Colorado State University Intensive Oil Shale Revegetation Study Site test plots in the Piceance basin, Colorado. The test plots were constructed to evaluate the effects of processed oil shale geochemistry on plant growth using various thicknesses of soil cover over the processed shale and/or over a gravel barrier between the shale and soil. Generally, the thicker the soil cover, the less the influence of the shale geochemistry on the element concentrations in the plants. Concentrations of 20 elements were larger in the ash of four-wing saltbush growing on the plot with the gravel barrier (between the soil and processed shale) when compared to the sample from the control plot. A greater water content in the soil in this plot has been reported, and the interaction between the increased, percolating water and shale may have increased the availability of these elements for plant uptake. Concentrations of boron, copper, fluorine, lithium, molybdenum, selenium, silicon, and zinc were larger in the samples grown over processed shale, compared to those from the control plot, and concentrations for barium, calcium, lanthanum, niobium, phosphorus, and strontium were smaller. Concentrations for arsenic, boron, fluorine, molybdenum, and selenium-- considered to be potential toxic contaminants--were similar to results reported in the literature for vegetation from the test plots. The copper-to-molybdenum ratios in three of the four samples of four-wing saltbush growing over the processed shale were below the ratio of 2:1, which is judged detrimental to ruminants, particularly cattle. Boron concentrations averaged 140 ppm, well above the phytotoxicity level for most plant species. Arsenic, fluorine, and selenium concentrations were below toxic levels, and thus should not present any problem for revegetation or forage use at this time.

Micromorphologic evidence for paleosol development in the Endicott group, Siksikpuk formation, Kingak(?) shale, and Ipewik formation, western Brooks range, Alaska

USGS Publications Warehouse

Dumoulin, Julie A.; White, Tim

2005-01-01

Micromorphologic evidence indicates the presence of paleosols in drill-core samples from four sedimentary units in the Red Dog area, western Brooks Range. Well-developed sepic-plasmic fabrics and siderite spherules occur in claystones of the Upper Devonian through Lower Mississippian(?) Kanayut Conglomerate (Endicott Group), the Pennsylvanian through Permian Siksikpuk Formation (Etivluk Group), the Jurassic through Lower Cretaceous Kingak(?) Shale, and the Lower Cretaceous Ipewik Formation. Although exposure surfaces have been previously recognized in the Endicott Group and Kingak Shale on the basis of outcrop features, our study is the first microscopic analysis of paleosols from these units, and it provides the first evidence of subaerial exposure in the Siksikpuk and Ipewik Formations. Regional stratigraphic relations and geochemical data support our interpretations. Paleosols in the Siksikpuk, Kingak, and Ipewik Formations likely formed in nearshore coastal-plain environments, with pore waters subjected to inundation by the updip migration of slightly brackish ground water, whereas paleosols in the Kanayut Conglomerate probably formed in a more distal setting relative to a marine basin.

43 CFR 3930.10 - General performance standards.

Code of Federal Regulations, 2011 CFR

2011-10-01

... MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) MANAGEMENT OF OIL SHALE EXPLORATION AND LEASES Management of Oil Shale Exploration Licenses and Leases § 3930.10 General performance standards. The operator... adversely affect the recovery of shale oil or other minerals producible under an oil shale lease during...

Minor-element composition and organic carbon content of marine and nonmarine shales of Late Cretaceous age in the western interior of the United States

USGS Publications Warehouse

Tourtelot, H.A.

1964-01-01

The composition of nonmarine shales of Cretaceous age that contain less than 1 per cent organic carbon is assumed to represent the inherited minor-element composition of clayey sediments delivered to the Cretaceous sea that occupied the western interior region of North America. Differences in minor-element content between these samples and samples of 1. (a) nonmarine carbonaceous shales (1 to 17 per cent organic carbon), 2. (b) nearshore marine shales (less than 1 per cent organic carbon), and 3. (c) offshore marine shales (as much as 8 per cent organic carbon), all of the same age, reveal certain aspects of the role played by clay minerals and organic materials in affecting the minor-element composition of the rocks. The organic carbon in the nonmarine rocks occurs in disseminated coaly plant remains. The organic carbon in the marine rocks occurs predominantly in humic material derived from terrestrial plants. The close similarity in composition between the organic isolates from the marine samples and low-rank coal suggests that the amount of marine organic material in these rocks is small. The minor-element content of the two kinds of nonmarine shales is the same despite the relatively large amount of organic carbon in the carbonaceous shales. The nearshore marine shales, however, contain larger median amounts of arsenic, boron, chromium, vanadium and zinc than do the nonmarine rocks; and the offshore marine shales contain even larger amounts of these elements. Cobalt, molybdenum, lead and zirconium show insignificant differences in median content between the nonmarine and marine rocks, although as much as 25 ppm molybdenum is present in some offshore marine samples. The gallium content is lower in the marine than in the nonmarine samples. Copper and selenium contents of the two kinds of nonmarine rocks and the nearshore marine samples are the same, but those of the offshore samples are larger. In general, arsenic, chromium, copper, molybdenum, selenium, vanadium and zinc are concentrated in those offshore marine samples having the largest amounts of organic carbon, but samples with equal amounts of vanadium, for instance, may differ by a factor of 3 in their amount of organic carbon. Arsenic and molybdenum occur in some samples chiefly in syngenetic pyrite but also are present in relatively large amounts in samples that contain little pyrite. The data on nonmarine carbonaceous shales indicate that organic matter of terrestrial origin in marine shales contributes little to the minor-element content of such rocks. It is possible that marine organic matter, even though seemingly small in amount in marine shales, contributes to the minor-element composition of the shales. In addition to any such contribution, however, the great effectiveness in sorption processes of humic materials in conjunction with clay minerals suggests that such processes must have played an important role as these materials moved from the relatively dilute solutions of the nonmarine environment to the relatively concentrated solution of sea water. The volumes of sea water sufficient to supply for sorption the amounts of most minor elements in the offshore marine samples are insignificant compared to the volumes of water with which the clay and organic matter were in contact during their transportation and sedimentation. Consequently, the chemical characteristics of the environment in which the clay minerals and organic matter accumulated and underwent diagenesis probably were the most important factors in controlling the degree to which sorption processes and the formation of syngenetic minerals affected the final composition of the rocks. ?? 1969.

Fundamental Study of Disposition and Release of Methane in a Shale Gas Reservoir

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yifeng; Xiong, Yongliang; Criscenti, Louise J.

The recent boom in shale gas production through hydrofracturing has reshaped the energy production landscape in the United States. Wellbore production rates vary greatly among the wells within a single field and decline rapidly with time, thus bring up a serious concern with the sustainability of shale gas production. Shale gas production starts with creating a fracture network by injecting a pressurized fluid in a wellbore. The induced fractures are then held open by proppant particles. During production, gas releases from the mudstone matrix, migrates to nearby fractures, and ultimately reaches a production wellbore. Given the relatively high permeability ofmore » the induced fractures, gas release and migration in low-permeability shale matrix is likely to be a limiting step for long-term wellbore production. Therefore, a clear understanding of the underlying mechanisms of methane disposition and release in shale matrix is crucial for the development of new technologies to maximize gas production and recovery. Shale is a natural nanocomposite material with distinct characteristics of nanometer-scale pore sizes, extremely low permeability, high clay contents, significant amounts of organic carbon, and large spatial heterogeneities. Our work has shown that nanopore confinement plays an important role in methane disposition and release in shale matrix. Using molecular simulations, we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~ 30 - 47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. The long-term production decline appears controlled by the second stage of gas release. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3 - 35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. We have successfully established experimental capabilities for measuring gas sorption and desorption on shale and model materials under a wide range of physical and chemical conditions. Both low and high pressure measurements show significant sorption of CH 4 and CO 2 onto clays, implying that methane adsorbed on clay minerals could contribute a significant portion of gas-in-place in an unconventional reservoir. We have also studied the potential impact of the interaction of shale with hydrofracking fluid on gas sorption. We have found that the CH 4-CO 2 sorption capacity for the reacted sample is systematically lower (by a factor of ~2) than that for the unreacted (raw) sample. This difference in sorption capacity may result from a mineralogical or surface chemistry change of the shale sample induced by fluid-rock interaction. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs.« less

Detailed description of oil shale organic and mineralogical heterogeneity via fourier transform infrared mircoscopy

USGS Publications Warehouse

Washburn, Kathryn E.; Birdwell, Justin E.; Foster, Michael; Gutierrez, Fernando

2015-01-01

Mineralogical and geochemical information on reservoir and source rocks is necessary to assess and produce from petroleum systems. The standard methods in the petroleum industry for obtaining these properties are bulk measurements on homogenized, generally crushed, and pulverized rock samples and can take from hours to days to perform. New methods using Fourier transform infrared (FTIR) spectroscopy have been developed to more rapidly obtain information on mineralogy and geochemistry. However, these methods are also typically performed on bulk, homogenized samples. We present a new approach to rock sample characterization incorporating multivariate analysis and FTIR microscopy to provide non-destructive, spatially resolved mineralogy and geochemistry on whole rock samples. We are able to predict bulk mineralogy and organic carbon content within the same margin of error as standard characterization techniques, including X-ray diffraction (XRD) and total organic carbon (TOC) analysis. Validation of the method was performed using two oil shale samples from the Green River Formation in the Piceance Basin with differing sedimentary structures. One sample represents laminated Green River oil shales, and the other is representative of oil shale breccia. The FTIR microscopy results on the oil shales agree with XRD and LECO TOC data from the homogenized samples but also give additional detail regarding sample heterogeneity by providing information on the distribution of mineral phases and organic content. While measurements for this study were performed on oil shales, the method could also be applied to other geological samples, such as other mudrocks, complex carbonates, and soils.

Graphite Black shale of Vendas de Ceira, Coimbra, Portugal

NASA Astrophysics Data System (ADS)

Quinta-Ferreira, Mário; Silva, Daniela; Coelho, Nuno; Gomes, Ruben; Santos, Ana; Piedade, Aldina

2017-04-01

The graphite black shale of Vendas de Ceira located in south of Coimbra (Portugal), caused serious instability problems in recent road excavation slopes. The problems increased with the rain, transforming shales into a dark mud that acquires a metallic hue when dried. The black shales are attributed to the Devonian or eventually, to the Silurian. At the base of the slope is observed graphite black shale and on the topbrown schist. Samples were collected during the slope excavation works. Undisturbed and less altered materials were selected. Further, sampling was made difficult as the graphite shale was covered by a thick layer of reinforced concrete, which was used to stabilize the excavated surfaces. The mineralogy is mainly constituted by quartz, muscovite, ilite, ilmenite and feldspar without the presence of expansive minerals. The organic matter content is 0.3 to 0.4%. The durability evaluated by the Slake Durability Test varies from very low (Id2 of 6% for sample A) to high (98% for sample C). The grain size distribution of the shale particles, was determined after disaggregation with water, which allowed verifying that sample A has 37% of fines (5% of clay and 32% of silt) and 63% of sand, while sample C has only 14% of fines (2% clay and 12% silt) and 86% sand, showing that the decrease in particle size contributes to reduce durability. The unconfined linear expansion confirms the higher expandability (13.4%) for sample A, reducing to 12.1% for sample B and 10.5% for sample C. Due the shale material degradated with water, mercury porosimetry was used. While the dry weight of the three samples does not change significantly, around 26 kN/m3, the porosity is much higher in sample A with 7.9% of pores, reducing to 1.4% in sample C. The pores size vary between 0.06 to 0.26 microns, does not seem to have any significant influence in the shale behaviour. In order to have a comparison term, a porosity test was carried out on the low weatherable brown shale, which is quite abundant at the site. The main difference to the graphite shale is the high porosity of the brown shale with 14.7% and the low volume weight of 23 kN/m3, evidencing the distinct characteristics of the graphite schists. The maximum strength was evaluated by the Schmidt hammer, as the point load test could not be performed as the rock was very soft. The maximum estimated values on dry samples were 32 MPa for sample A and 85 MPa for sample C. The results show a singular material characterized by significant heterogeneity. It can be concluded that for the graphite schists the smaller particle size and higher porosity make the soft rock extremely weatherable when decompressed and exposed to water, as a result of high capillary tension and reduced cohesion. They also exhibit high expansion and an enormous degradation of the rock presenting a behaviour close to a soil. The graphite black schist is a highly weatherable soft rock, without expansive minerals, with small pores, in which the porosity, low strength and low cohesion allow their rapid degradation when decompressed and exposed to the action of Water.

An in situ FTIR step-scan photoacoustic investigation of kerogen and minerals in oil shale.

PubMed

Alstadt, Kristin N; Katti, Dinesh R; Katti, Kalpana S

2012-04-01

Step-scan photoacoustic infrared spectroscopy experiments were performed on Green River oil shale samples obtained from the Piceance Basin located in Colorado, USA. We have investigated the molecular nature of light and dark colored areas of the oil shale core using FTIR photoacoustic step-scan spectroscopy. This technique provided us with the means to analyze the oil shale in its original in situ form with the kerogen-mineral interactions intact. All vibrational bands characteristic of kerogen were found in the dark and light colored oil shale samples confirming that kerogen is present throughout the depth of the core. Depth profiling experiments indicated that there are changes between layers in the oil shale molecular structure at a length scale of micron. Comparisons of spectra from the light and dark colored oil shale core samples suggest that the light colored regions have high kerogen content, with spectra similar to that from isolated kerogen, whereas, the dark colored areas contain more mineral components which include clay minerals, dolomite, calcite, and pyrite. The mineral components of the oil shale are important in understanding how the kerogen is "trapped" in the oil shale. Comparing in situ kerogen spectra with spectra from isolated kerogen indicate significant band shifts suggesting important nonbonded molecular interactions between the kerogen and minerals. Copyright © 2011 Elsevier B.V. All rights reserved.

Hydrothermal, biogenic, and seawater components in metalliferous black shales of the Brooks Range, Alaska: Synsedimentary metal enrichment in a carbonate ramp setting

USGS Publications Warehouse

Slack, John F.; Selby, David; Dumoulin, Julie A.

2015-01-01

Trace element and Os isotope data for Lisburne Group metalliferous black shales of Middle Mississippian (early Chesterian) age in the Brooks Range of northern Alaska suggest that metals were sourced chiefly from local seawater (including biogenic detritus) but also from externally derived hydrothermal fluids. These black shales are interbedded with phosphorites and limestones in sequences 3 to 35 m thick; deposition occurred mainly on a carbonate ramp during intermittent upwelling under varying redox conditions, from suboxic to anoxic to sulfidic. Deposition of the black shales at ~335 Ma was broadly contemporaneous with sulfide mineralization in the Red Dog and Drenchwater Zn-Pb-Ag deposits, which formed in a distal marginal basin.Relative to the composition of average black shale, the metalliferous black shales (n = 29) display large average enrichment factors (>10) for Zn (10.1), Cd (11.0), and Ag (20.1). Small enrichments (>2–<10) are shown by V, Cr, Ni, Cu, Mo, Pd, Pt, U, Se, Y, and all rare earth elements except Ce, Nd, and Sm. A detailed stratigraphic profile over 23 m in the Skimo Creek area (central Brooks Range) indicates that samples from at and near the top of the section, which accumulated during a period of major upwelling and is broadly correlative with the stratigraphic levels of the Red Dog and Drenchwater Zn-Pb-Ag deposits, have the highest Zn/TOC (total organic carbon), Cu/TOC, and Tl/TOC ratios for calculated marine fractions (no detrital component) of these three metals.Average authigenic (detrital-free) contents of Mo, V, U, Ni, Cu, Cd, Pb, Ge, Re, Se, As, Sb, Tl, Pd, and Au show enrichment factors of 4.3 × 103 to 1.2 × 106 relative to modern seawater. Such moderate enrichments, which are common in other metalliferous black shales, suggest wholly marine sources (seawater and biogenic material) for these metals, given similar trends for enrichment factors in organic-rich sediments of modern upwelling zones on the Namibian, Peruvian, and Chilean shelves. The largest enrichment factors for Zn and Ag are much higher (1.4 × 107 and 2.9 × 107, respectively), consistent with an appreciable hydrothermal component. Other metals such as Cu, Pb, and Tl that are concentrated in several black shale samples, and are locally abundant in the Red Dog and Drenchwater Zn-Pb-Ag deposits, may have a partly hydrothermal origin but this cannot be fully established with the available data. Enrichments in Cr (up to 7.8 × 106) are attributed to marine and not hydrothermal processes. The presence in some samples of large enrichments in Eu (up to 6.1 × 107) relative to modern seawater and of small positive Eu anomalies (Eu/Eu* up to 1.12) are considered unrelated to hydrothermal activity, instead being linked to early diagenetic processes within sulfidic pore fluids.Initial Os isotope ratios (187Os/188Os) calculated for a paleontologically based depositional age of 335 Ma reveal moderately unradiogenic values of 0.24 to 0.88 for four samples of metalliferous black shale. A proxy for the ratio of coeval early Chesterian seawater is provided by initial (187Os/188Os)335 Ma ratios of four unaltered black shales of the coeval Kuna Formation that average 1.08, nearly identical to the initial ratio of 1.06 for modern seawater. Evaluation of possible sources of unradiogenic Os in the metalliferous black shales suggests that the most likely source was mafic igneous rocks that were leached by externally derived hydrothermal fluids. This unradiogenic Os is interpreted to have been leached by deeply circulating hydrothermal fluids in the Kuna basin, followed by venting of the fluids into overlying seawater.We propose that metal-bearing hydrothermal fluids that formed Zn-Pb-Ag deposits such as Red Dog or Drenchwater vented into seawater in a marginal basin, were carried by upwelling currents onto the margins of a shallow-water carbonate platform, and were then deposited in organic-rich muds, together with seawater- and biogenically derived components, by syngenetic sedimentary processes. Metal concentration in the black shales was promoted by high biologic productivity, sorption onto organic matter, diffusion across redox boundaries, a low sedimentation rate, and availability of H2S in bottom waters and pore fluids.

Neutron scattering measurements of carbon dioxide adsorption in pores within the Marcellus Shale: Implications for sequestration

USGS Publications Warehouse

Stefanopoulos, Konstantinos L.; Youngs, Tristan G. A.; Sakurovs, Richard; Ruppert, Leslie F.; Bahadur, Jitendra; Melnichenko, Yuri B.

2017-01-01

Shale is an increasingly viable source of natural gas and a potential candidate for geologic CO2sequestration. Understanding the gas adsorption behavior on shale is necessary for the design of optimal gas recovery and sequestration projects. In the present study neutron diffraction and small-angle neutron scattering measurements of adsorbed CO2 in Marcellus Shale samples were conducted on the Near and InterMediate Range Order Diffractometer (NIMROD) at the ISIS Pulsed Neutron and Muon Source, STFC Rutherford Appleton Laboratory along an adsorption isotherm of 22 °C and pressures of 25 and 40 bar. Additional measurements were conducted at approximately 22 and 60 °C at the same pressures on the General-Purpose Small-Angle Neutron Scattering (GP-SANS) instrument at Oak Ridge National Laboratory. The structures investigated (pores) for CO2 adsorption range in size from Å level to ∼50 nm. The results indicate that, using the conditions investigated densification or condensation effects occurred in all accessible pores. The data suggest that at 22 °C the CO2 has liquid-like properties when confined in pores of around 1 nm radius at pressures as low as 25 bar. Many of the 2.5 nm pores, 70% of 2 nm pores, most of the <1 nm pores, and all pores <0.25 nm, are inaccessible or closed to CO2, suggesting that despite the vast numbers of micropores in shale, the micropores will be unavailable for storage for geologic CO2 sequestration.

Shale gas impacts on groundwater resources: insights from monitoring a fracking site in Poland

NASA Astrophysics Data System (ADS)

Montcoudiol, Nelly; Isherwood, Catherine; Gunning, Andrew; Kelly, Thomas; Younger, Paul

2017-04-01

Exploitation of shale gas by hydraulic fracturing (fracking) is highly controversial and concerns have been raised regarding induced risks from this technique. The SHEER project, an EU Horizon 2020-funded project, is looking into developing best practice to understand, prevent and mitigate the potential short- and long-term environmental impacts and risks from shale gas exploration and exploitation. Three major potential impacts were identified: groundwater contamination, air pollution and induced seismicity. This presentation will deal with the hydrogeological aspect. As part of the SHEER project, four monitoring wells were installed at a shale gas exploration site in Northern Poland. They intercept the main drinking water aquifer located in Quaternary sediments. Baseline monitoring was carried out from mid-December 2015 to beginning of June 2016. Fracking operations occurred in two horizontal wells, in two stages, in June and July 2016. The monitoring has continued after fracking was completed, with site visits every 4-6 weeks. Collected data include measurements of groundwater level, conductivity and temperature at 15-minute intervals, frequent sampling for laboratory analyses and field measurements of groundwater physico-chemical parameters. Groundwater samples are analysed for a range of constituents including dissolved gases and isotopes. The presentation will focus on the interpretation of baseline monitoring data. The insights gained into the behaviour of the Quaternary aquifer will allow a greater perspective to be place on the initial project understanding draw from previous studies. Short-term impacts will also be discussed in comparison with the baseline monitoring results. The presentation will conclude with discussion of challenges regarding monitoring of shale gas fracking sites.

Surface water geochemical and isotopic variations in an area of accelerating Marcellus Shale gas development.

PubMed

Pelak, Adam J; Sharma, Shikha

2014-12-01

Water samples were collected from 50 streams in an area of accelerating shale gas development in the eastern U.S.A. The geochemical/isotopic characteristics show no correlation with the five categories of Marcellus Shale production. The sub-watersheds with the greatest density of Marcellus Shale development have also undergone extensive coal mining. Hence, geochemical/isotopic compositions were used to understand sources of salinity and effects of coal mining and shale gas development in the area. The data indicates that while some streams appear to be impacted by mine drainage; none appear to have received sustained contribution from deep brines or produced waters associated with shale gas production. However, it is important to note that our interpretations are based on one time synoptic base flow sampling of a few sampling stations and hence do account potential intermittent changes in chemistry that may result from major/minor spills or specific mine discharges on the surface water chemistry. Copyright © 2014 Elsevier Ltd. All rights reserved.

Comparative study of microfacies variation in two samples from the Chittenango member, Marcellus shale subgroup, western New York state, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balulla, Shama, E-mail: shamamohammed77@outlook.com; Padmanabhan, E., E-mail: eswaran-padmanabhan@petronas.com.my; Over, Jeffrey, E-mail: over@geneseo.edu

This study demonstrates the significant lithologic variations that occur within the two shale samples from the Chittenango member of the Marcellus shale formation from western New York State in terms of mineralogical composition, type of lamination, pyrite occurrences and fossil content using thin section detailed description and field emission Scanning electron microscope (FESEM) with energy dispersive X-Ray Spectrum (EDX). This study is classified samples as laminated clayshale and fossiliferous carbonaceous shale. The most important detrital constituents of these shales are the clay mineral illite and chlorite, quartz, organic matter, carbonate mineral, and pyrite. The laminated clayshale has a lower amountmore » of quartz and carbonate minerals than fossiliferous carbonaceous shale while it has a higher amount of clay minerals (chlorite and illite) and organic matter. FESEM analysis confirms the presence of chlorite and illite. The fossil content in the laminated clayshale is much lower than the fossiliferous carbonaceous shale. This can provide greater insights about variations in the depositional and environmental factors that influenced its deposition. This result can be compiled with the sufficient data to be helpful for designing the horizontal wells and placement of hydraulic fracturing in shale gas exploration and production.« less

Developing a shale heterogeneity index to predict fracture response in the Mancos Shale

NASA Astrophysics Data System (ADS)

DeReuil, Aubry; Birgenheier, Lauren; McLennan, John

2017-04-01

The interplay between sedimentary heterogeneity and fracture propagation in mudstone is crucial to assess the potential of low permeability rocks as unconventional reservoirs. Previous experimental research has demonstrated a relationship between heterogeneity and fracture of brittle rocks, as discontinuities in a rock mass influence micromechanical processes such as microcracking and strain localization, which evolve into macroscopic fractures. Though numerous studies have observed heterogeneity influencing fracture development, fundamental understanding of the entire fracture process and the physical controls on this process is still lacking. This is partly due to difficulties in quantifying heterogeneity in fine-grained rocks. Our study tests the hypothesis that there is a correlation between sedimentary heterogeneity and the manner in which mudstone is fractured. An extensive range of heterogeneity related to complex sedimentology is represented by various samples from cored intervals of the Mancos Shale. Samples were categorized via facies analysis consisting of: visual core description, XRF and XRD analysis, SEM and thin section microscopy, and reservoir quality analysis that tested porosity, permeability, water saturation, and TOC. Systematic indirect tensile testing on a broad variety of facies has been performed, and uniaxial and triaxial compression testing is underway. A novel tool based on analytically derived and statistically proven relationships between sedimentary geologic and geomechanical heterogeneity is the ultimate result, referred to as the shale heterogeneity index. Preliminary conclusions from development of the shale heterogeneity index reveal that samples with compositionally distinct bedding withstand loading at higher stress values, while texturally and compositionally homogeneous, bedded samples fail at lower stress values. The highest tensile strength results from cemented Ca-enriched samples, medial to high strength samples have approximately equivalent proportions of Al-Ca-Si compositions, while Al-rich samples have consistently low strength. Moisture preserved samples fail on average at approximately 5 MPa lower than dry samples of similar facies. Additionally, moisture preserved samples fail in a step-like pattern when tested perpendicular to bedding. Tensile fractures are halted at heterogeneities and propagate parallel to bedding planes before developing a through-going failure plane, as opposed to the discrete, continuous fractures that crosscut dry samples. This result suggests that sedimentary heterogeneity plays a greater role in fracture propagation in moisture preserved samples, which are more indicative of in-situ reservoir conditions. Stress-strain curves will be further analyzed, including estimation of an energy released term based on post-failure response, and an estimation of volume of cracking measure on the physical fracture surface.

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

2013-01-01

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

Distribution and variation of the inorganic fraction of Devonian to Bashkirian black shales in the north-western part of the Dniepr-Donets Basin, Ukraine

NASA Astrophysics Data System (ADS)

Wegerer, Eva; Sachsenhofer, Reinhard; Misch, David; Aust, Nicolai

2016-04-01

Mineralogical data of 112 core samples from 12 wells are used to investigate lateral and vertical variations in the lithofacies of Devonian to Bashkirian black shales in the north-western part of the Dniepr-Donets-Basin. Sulphur and carbonate contents as well as organic geochemical parameters, including TOC and Hydrogen Index have been determined on the same sample set within the frame of an earlier study (Sachsenhofer et al. 2010). This allows the correlation of inorganic and organic composition of the black shales. Aims of the study are to distinguish between detrital and authigenic minerals, to relate the lithofacies of the black shales with the tectono-stratigraphic sequences of the Dniepr-Donets Basin, to contribute to the reconstruction of the depositional environment and to relate diagenetic processes with the thermal history of the basin. Mineral compositions were determined primarily using XRD-measurements applying several measurement procedures, e.g. chemical and temperature treatment, and specific standards. Major differences exist in the mineralogical composition of the black shales. For example, clay mineral contents range from less than 20 to more than 80 Vol%. Kaolinite contents are significantly higher in rocks with a Tournaisian or Early Visean age than in any other stratigraphic unit. This is also true for two Lower Visean coal samples from the shallow north-westernmost part of the basin. Chlorite contents reach maxima in uppermost Visean and overlying rocks. Quartz contents are often high in Upper Visean rocks and reach maxima in Bashkirian units. Feldspar-rich rocks are observed in Devonian sediments from the north-western part of the study area and may reflect the proximity to a sediment source. Carbonate contents are typically low, but reach very high values in some Tournaisian, Lower Visean and Serpukhovian samples. Pyrite contents reach maxima along the basin axis in Tournaisian and Visean rocks reflecting anoxic conditions. Mixed layer minerals are dominated by illite. Their presence in samples from depth exceeding 5 km reflects the low thermal overprint of Paleozoic rocks in the north-western Dniepr-Donets-Basin.

Atmospheric emission characterization of Marcellus shale natural gas development sites.

PubMed

Goetz, J Douglas; Floerchinger, Cody; Fortner, Edward C; Wormhoudt, Joda; Massoli, Paola; Knighton, W Berk; Herndon, Scott C; Kolb, Charles E; Knipping, Eladio; Shaw, Stephanie L; DeCarlo, Peter F

2015-06-02

Limited direct measurements of criteria pollutants emissions and precursors, as well as natural gas constituents, from Marcellus shale gas development activities contribute to uncertainty about their atmospheric impact. Real-time measurements were made with the Aerodyne Research Inc. Mobile Laboratory to characterize emission rates of atmospheric pollutants. Sites investigated include production well pads, a well pad with a drill rig, a well completion, and compressor stations. Tracer release ratio methods were used to estimate emission rates. A first-order correction factor was developed to account for errors introduced by fenceline tracer release. In contrast to observations from other shale plays, elevated volatile organic compounds, other than CH4 and C2H6, were generally not observed at the investigated sites. Elevated submicrometer particle mass concentrations were also generally not observed. Emission rates from compressor stations ranged from 0.006 to 0.162 tons per day (tpd) for NOx, 0.029 to 0.426 tpd for CO, and 67.9 to 371 tpd for CO2. CH4 and C2H6 emission rates from compressor stations ranged from 0.411 to 4.936 tpd and 0.023 to 0.062 tpd, respectively. Although limited in sample size, this study provides emission rate estimates for some processes in a newly developed natural gas resource and contributes valuable comparisons to other shale gas studies.

Factors controlling Li concentration and isotopic composition in formation waters and host rocks of Marcellus Shale, Appalachian Basin

USGS Publications Warehouse

Phan, Thai T.; Capo, Rosemary C; Stewart, Brian W.; Macpherson, Gwen; Rowan, Elisabeth L.; Hammack, Richard W.

2015-01-01

In Greene Co., southwest Pennsylvania, the Upper Devonian sandstone formation waters have δ7Li values of + 14.6 ± 1.2 (2SD, n = 25), and are distinct from Marcellus Shale formation waters which have δ7Li of + 10.0 ± 0.8 (2SD, n = 12). These two formation waters also maintain distinctive 87Sr/86Sr ratios suggesting hydrologic separation between these units. Applying temperature-dependent illitilization model to Marcellus Shale, we found that Li concentration in clay minerals increased with Li concentration in pore fluid during diagenetic illite-smectite transition. Samples from north central PA show a much smaller range in both δ7Li and 87Sr/86Sr than in southwest Pennsylvania. Spatial variations in Li and δ7Li values show that Marcellus formation waters are not homogeneous across the Appalachian Basin. Marcellus formation waters in the northeastern Pennsylvania portion of the basin show a much smaller range in both δ7Li and 87Sr/86Sr, suggesting long term, cross-formational fluid migration in this region. Assessing the impact of potential mixing of fresh water with deep formation water requires establishment of a geochemical and isotopic baseline in the shallow, fresh water aquifers, and site specific characterization of formation water, followed by long-term monitoring, particularly in regions of future shale gas development.

The effect of moisture on the methane adsorption capacity of shales: A study case in the eastern Qaidam Basin in China

NASA Astrophysics Data System (ADS)

Wang, Lu; Yu, Qingchun

2016-11-01

This study investigated the effects of moisture on high-pressure methane adsorption in carboniferous shales from the Qaidam Basin, China. The shale characteristics, including the organic/inorganic compositions and pore structure (volume and surface) distribution, were obtained using various techniques. Gibbs adsorption measurements were performed over a pressure range up to 6 MPa and temperatures of 308.15 K on dry samples and moisture-equilibrated samples to analyze the correlations between organic/inorganic matter, pore structure, and moisture content on the methane sorption capacity. Compared to dry samples, the sorption capacity of wet samples (0.44-2.52% of water content) is reduced from 19.7 ± 5.3% to 36.1% ± 6.1%. Langmuir fitting is conducted to investigate moisture-dependent variations of adsorbed methane density, Langmuir pressure, and volume. By combining the pore volume and surface distribution analyses, our observations suggested that the main competition sites for CH4-H2O covered pores of approximately 2-7 nm, whereas the effective sites for methane and water were predominantly distributed within smaller (<4 nm) and larger pores (>10 nm), respectively. Regarding the compositional correlations, the impact of moisture on the amount of adsorbed methane shows a roughly linearly decreasing trend with increasing TOC content ranging from 0.62 to 2.88%, whereas the correlation between the moisture effect and various inorganic components is more complicated. Further fitting results indicate that illite/smectite mixed formations are closely related to the methane capacity, whereas the illite content show an evident connection to the pore structural (volume and surface) variations in the presence of moisture.

Rates and Mechanisms of Oil Shale Pyrolysis: A Chemical Structure Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fletcher, Thomas; Pugmire, Ronald

2015-01-01

Three pristine Utah Green River oil shale samples were obtained and used for analysis by the combined research groups at the University of Utah and Brigham Young University. Oil shale samples were first demineralized and the separated kerogen and extracted bitumen samples were then studied by a host of techniques including high resolution liquid-state carbon-13 NMR, solid-state magic angle sample spinning 13C NMR, GC/MS, FTIR, and pyrolysis. Bitumen was extracted from the shale using methanol/dichloromethane and analyzed using high resolution 13C NMR liquid state spectroscopy, showing carbon aromaticities of 7 to 11%. The three parent shales and the demineralized kerogensmore » were each analyzed with solid-state 13C NMR spectroscopy. Carbon aromaticity of the kerogen was 23-24%, with 10-12 aromatic carbons per cluster. Crushed samples of Green River oil shale and its kerogen extract were pyrolyzed at heating rates from 1 to 10 K/min at pressures of 1 and 40 bar and temperatures up to 1000°C. The transient pyrolysis data were fit with a first-order model and a Distributed Activation Energy Model (DAEM). The demineralized kerogen was pyrolyzed at 10 K/min in nitrogen at atmospheric pressure at temperatures up to 525°C, and the pyrolysis products (light gas, tar, and char) were analyzed using 13C NMR, GC/MS, and FTIR. Details of the kerogen pyrolysis have been modeled by a modified version of the chemical percolation devolatilization (CPD) model that has been widely used to model coal combustion/pyrolysis. This refined CPD model has been successful in predicting the char, tar, and gas yields of the three shale samples during pyrolysis. This set of experiments and associated modeling represents the most sophisticated and complete analysis available for a given set of oil shale samples.« less

A non-zircon Hf isotope record in Archean black shales from the Pilbara craton confirms changing crustal dynamics ca. 3 Ga ago.

PubMed

Nebel-Jacobsen, Yona; Nebel, Oliver; Wille, Martin; Cawood, Peter A

2018-01-17

Plate tectonics and associated subduction are unique to the Earth. Studies of Archean rocks show significant changes in composition and structural style around 3.0 to 2.5 Ga that are related to changing tectonic regime, possibly associated with the onset of subduction. Whole rock Hf isotope systematics of black shales from the Australian Pilbara craton, selected to exclude detrital zircon components, are employed to evaluate the evolution of the Archean crust. This approach avoids limitations of Hf-in-zircon analyses, which only provide input from rocks of sufficient Zr-concentration, and therefore usually represent domains that already underwent a degree of differentiation. In this study, we demonstrate the applicability of this method through analysis of shales that range in age from 3.5 to 2.8 Ga, and serve as representatives of their crustal sources through time. Their Hf isotopic compositions show a trend from strongly positive εHf initial values for the oldest samples, to strongly negative values for the younger samples, indicating a shift from juvenile to differentiated material. These results confirm a significant change in the character of the source region of the black shales by 3 Ga, consistent with models invoking a change in global dynamics from crustal growth towards crustal reworking around this time.

Cr(VI)/Cr(III) and As(V)/As(III) ratio assessments in Jordanian spent oil shale produced by aerobic combustion and Anaerobic Pyrolysis.

PubMed

El-Hasan, Tayel; Szczerba, Wojciech; Buzanich, Günter; Radtke, Martin; Riesemeier, Heinrich; Kersten, Michael

2011-11-15

With the increase in the awareness of the public in the environmental impact of oil shale utilization, it is of interest to reveal the mobility of potentially toxic trace elements in spent oil shale. Therefore, the Cr and As oxidation state in a representative Jordanian oil shale sample from the El-Lajjoun area were investigated upon different lab-scale furnace treatments. The anaerobic pyrolysis was performed in a retort flushed by nitrogen gas at temperatures in between 600 and 800 °C (pyrolytic oil shale, POS). The aerobic combustion was simply performed in porcelain cups heated in a muffle furnace for 4 h at temperatures in between 700 and 1000 °C (burned oil shale, BOS). The high loss-on-ignition in the BOS samples of up to 370 g kg(-1) results from both calcium carbonate and organic carbon degradation. The LOI leads to enrichment in the Cr concentrations from 480 mg kg(-1) in the original oil shale up to 675 mg kg(-1) in the ≥ 850 °C BOS samples. Arsenic concentrations were not much elevated beyond that in the average shale standard (13 mg kg(-1)). Synchrotron-based X-ray absorption near-edge structure (XANES) analysis revealed that within the original oil shale the oxidation states of Cr and As were lower than after its aerobic combustion. Cr(VI) increased from 0% in the untreated or pyrolyzed oil shale up to 60% in the BOS ash combusted at 850 °C, while As(V) increased from 64% in the original oil shale up to 100% in the BOS ash at 700 °C. No Cr was released from original oil shale and POS products by the European compliance leaching test CEN/TC 292 EN 12457-1 (1:2 solid/water ratio, 24 h shaking), whereas leachates from BOS samples showed Cr release in the order of one mmol L(-1). The leachable Cr content is dominated by chromate as revealed by catalytic adsorptive stripping voltammetry (CAdSV) which could cause harmful contamination of surface and groundwater in the semiarid environment of Jordan.

43 CFR 3900.10 - Lands subject to leasing.

Code of Federal Regulations, 2011 CFR

2011-10-01

... MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Oil Shale Management-Introduction § 3900.10 Lands subject to leasing. The BLM may issue oil shale leases under this...

Characterization of raw and burnt oil shale from Dotternhausen: Petrographical and mineralogical evolution with temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thiéry, Vincent, E-mail: vincent.thiery@mines-douai.fr; Université de Lille; Bourdot, Alexandra, E-mail: alexandra.bourdot@gmail.com

The Toarcian Posidonia shale from Dotternhausen, Germany, is quarried and burnt in a fluidized bed reactor to produce electricity. The combustion residue, namely burnt oil shale (BOS), is used in the adjacent cement work as an additive in blended cements. The starting material is a typical laminated oil shale with an organic matter content ranging from 6 to 18%. Mineral matter consists principally of quartz, feldspar, pyrite and clays. After calcination in the range, the resulting product, burnt oil shale, keeps the macroscopic layered texture however with different mineralogy (anhydrite, lime, iron oxides) and the formation of an amorphous phase.more » This one, studied under STEM, reveals a typical texture of incipient partial melting due to a long retention time (ca. 30 min) and quenching. An in-situ high temperature X-ray diffraction (HTXRD) allowed studying precisely the mineralogical changes associated with the temperature increase. - Highlights: • We present oil shale/burnt oil shale characterization. • The Posidonia Shale is burnt in a fluidized bed. • Mineralogical evolution with temperature is complex. • The burnt oil shale is used in composite cements.« less

Selenium in soil, water, sediment, and biota of the lower Sun River area, West-Central Montana

USGS Publications Warehouse

Nimick, David A.; Lambing, John H.; Palawski, Donald U.

1993-01-01

A U.S. Department of the Interior study started in 1990 examined the source, movement, fate, and possible biological effects of selenium associated with irrigation drainage from the Sun River Irrigation Project in west-central Montana. Concentrations of total selenium in soil samples ranged from 0.1 to 8.5 micrograms per gram; the maximum concentrations were measured in nonirrigated areas overlying geologic formations containing seleniferous shale. In irrigated areas, concentrations of dissolved selenium in ground water flowing toward Freezeout Lake ranged from less than 1 to 18 micrograms per liter (??g/L) in terrace gravel and from 1 to 190 ??g/L in glacial deposits derived from seleniferous shale. Concentrations of total selenium ranged from less than 1 to 180 ??g/L in surface irrigation drainage, and from less than 1 to 1,000 ??g/L in natural flows from nonirrigated land. Selenium concentrations in water from lakes generally were less than the aquatic-life criterion for chronic toxicity. The range of selenium concentrations in bottom sediment of lakes was similar to that of local soils. However, biological samples indicate that selenium is accumulating through the aquatic food chain. Selenium concentrations indicative of biological risk were exceeded in at least 80 percent of the freshwater-invertebrate, bird-egg, and bird-liver samples collected from all wetland sites.

Chapter 5: Geologic Assessment of Undiscovered Petroleum Resources in the Waltman Shale Total Petroleum System,Wind River Basin Province, Wyoming

USGS Publications Warehouse

Roberts, Steve B.; Roberts, Laura N.R.; Cook, Troy

2007-01-01

The Waltman Shale Total Petroleum System encompasses about 3,400 square miles in the Wind River Basin Province, Wyoming, and includes accumulations of oil and associated gas that were generated and expelled from oil-prone, lacustrine shale source rocks in the Waltman Shale Member of the Paleocene Fort Union Formation. Much of the petroleum migrated and accumulated in marginal lacustrine (deltaic) and fluvial sandstone reservoirs in the Shotgun Member of the Fort Union, which overlies and intertongues with the Waltman Shale Member. Additional petroleum accumulations derived from Waltman source rocks are present in fluvial deposits in the Eocene Wind River Formation overlying the Shotgun Member, and also might be present within fan-delta deposits included in the Waltman Shale Member, and in fluvial sandstone reservoirs in the uppermost part of the lower member of the Fort Union Formation immediately underlying the Waltman. To date, cumulative production from 53 wells producing Waltman-sourced petroleum exceeds 2.8 million barrels of oil and 5.8 billion cubic feet of gas. Productive horizons range from about 1,770 feet to 5,800 feet in depth, and average about 3,400 to 3,500 feet in depth. Formations in the Waltman Shale Total Petroleum System (Fort Union and Wind River Formations) reflect synorogenic deposition closely related to Laramide structural development of the Wind River Basin. In much of the basin, the Fort Union Formation is divided into three members (ascending order): the lower unnamed member, the Waltman Shale Member, and the Shotgun Member. These members record the transition from deposition in dominantly fluvial, floodplain, and mire environments in the early Paleocene (lower member) to a depositional setting characterized by substantial lacustrine development (Waltman Shale Member) and contemporaneous fluvial, and marginal lacustrine (deltaic) deposition (Shotgun Member) during the middle and late Paleocene. Waltman Shale Member source rocks have total organic carbon values ranging from 0.93 to 6.21 weight percent, averaging about 2.71 weight percent. The hydrocarbon generative potential of the source rocks typically exceeds 2.5 milligrams of hydrocarbon per gram of rock and numerous samples had generative potentials exceeding 6.0 milligrams of hydrocarbon per gram of rock. Waltman source rocks are oil prone, and contain a mix of Type-II and Type-III kerogen, indicating organic input from a mix of algal and terrestrial plant matter, or a mix of algal and reworked or recycled material. Thermal maturity at the base of the Waltman Shale Member ranges from a vitrinite reflectance value of less than 0.60 percent along the south basin margin to projected values exceeding 1.10 percent in the deep basin west of Madden anticline. Burial history reconstructions for three wells in the northern part of the Wind River Basin indicate that the Waltman Shale Member was well within the oil window (Ro equal to or greater than 0.65 percent) by the time of maximum burial about 15 million years ago; maximum burial depths exceeded 10,000 feet. Onset of oil generation calculated for the base of the Waltman Shale member took place from about 49 million years ago to about 20 million years ago. Peak oil generation occurred from about 31 million years ago to 26 million years ago in the deep basin west of Madden anticline. Two assessment units were defined in the Waltman Shale Total Petroleum System: the Upper Fort Union Sandstones Conventional Oil and Gas Assessment Unit (50350301) and the Waltman Fractured Shale Continuous Oil Assessment Unit (50350361). The conventional assessment unit primarily relates to the potential for undiscovered petroleum accumulations that are derived from source rocks in the Waltman Shale Member and trapped within sandstone reservoirs in the Shotgun Member (Fort Union Formation) and in the lower part of the overlying Wind River Formation. The potential for Waltman-sourced oil accumulations in fan-delta depos

Geochemical and mineralogical sampling of the Devonian shales in the Broadtop synclinorium, Appalachian basin, in Virginia, West Virginia, Maryland, and Pennsylvania

USGS Publications Warehouse

Enomoto, Catherine B.; Coleman, James L.; Swezey, Christopher S.; Niemeyer, Patrick W.; Dulong, Frank T.

2015-01-01

The presence of conventional anticlinal gas fields in the study area that are productive from the underlying Lower Devonian Oriskany Sandstone suggests that an unconventional (or continuous) shale gas system may be in place within the Marcellus Shale in the study area. Results of this study indicate that the Marcellus Shale in the Broadtop synclinorium generally is similar in organic geochemical nature throughout its extent, and based on the sample analyses, there are no clearly identifiable high potential areas (or “sweet spots”) in the study area. This report contains analyses of 132 outcrop and well drill-cuttings samples.

43 CFR 3931.80 - Core or test hole samples and cuttings.

Code of Federal Regulations, 2011 CFR

2011-10-01

... OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) MANAGEMENT OF OIL SHALE.... The records must include a log of all strata penetrated and conditions encountered, such as water, gas... operation or any deposit of oil, gas, other mineral substances, or ground water. (c) Operators may convert...

Pore-Scale X-ray Micro-CT Imaging and Analysis of Oil Shales

NASA Astrophysics Data System (ADS)

Saif, T.

2015-12-01

The pore structure and the connectivity of the pore space during the pyrolysis of oil shales are important characteristics which determine hydrocarbon flow behaviour and ultimate recovery. We study the effect of temperature on the evolution of pore space and subsequent permeability on five oil shale samples: (1) Vernal Utah United States, (2) El Lajjun Al Karak Jordan, (3) Gladstone Queensland Australia (4) Fushun China and (5) Kimmerdige United Kingdom. Oil Shale cores of 5mm in diameter were pyrolized at 300, 400 and 500 °C. 3D imaging of 5mm diameter core samples was performed at 1μm voxel resolution using X-ray micro computed tomography (CT) and the evolution of the pore structures were characterized. The experimental results indicate that the thermal decomposition of kerogen at high temperatures is a major factor causing micro-scale changes in the internal structure of oil shales. At the early stage of pyrolysis, micron-scale heterogeneous pores were formed and with a further increase in temperature, the pores expanded and became interconnected by fractures. Permeability for each oil shale sample at each temperature was computed by simulation directly on the image voxels and by pore network extraction and simulation. Future work will investigate different samples and pursue insitu micro-CT imaging of oil shale pyrolysis to characterize the time evolution of the pore space.

Molybdenum Enrichment in the 3.2 Ga old Black Shales Recovered by Dixon Island-Cleaverville Drilling Project (DXCL-DP) in Northwestern Pilbara, Western Australia

NASA Astrophysics Data System (ADS)

Yamaguchi, K. E.; Kiyokawa, S.; Naraoka, H.; Ikehara, M.; Ito, T.; Suganuma, Y.; Sakamoto, R.; Hosoi, K.

2010-12-01

To obtain drillcores of Mesoarchean black shales with negligible modern weathering, we conducted continental drilling at Cleaverville coast in Pilbara, Western Australia. We recovered 3.2Ga sulfidic black shales of the Cleaverville Group from three drillholes (~200m in total), namely DX, CL1, and CL2. Information on the geology of the drilling site has been reported [1, 2]. Here we report the discovery of Mo enrichment in the 3.2Ga DXCL-DP black shales. We analyzed total chemical compositions of forty black shale samples from drillcore DX and fifty-six of those from CL1 and CL2. Molybdenum concentrations for DX samples ranged from 0.3 to 12.9ppm (Avg±1σ= 1.8±1.9ppm), and those for CL1 and CL2 (combined) ranged from 0.8 to 3.3ppm (Avg±1σ= 1.4±0.4ppm). The highest concentration of Mo occurs in Corg-rich sample, and is comparable to that of the contemporaneous Fig Tree Group in South Africa [3, 4]. The highest concentration of Mo in the DXCL-DP samples, ~13ppm, is lower than that found in the 2.5 Ga Mt. McRae Shale of the Hamersley Group, Western Australia (maximums are ~17ppm [5], and ~40ppm [6]). However, it is much higher, by thirteen times, than the average Mo concentration in the Phanerozoic shales (1ppm [7]). No significant enrichment of Mo was expected to occur in the before-GOE black shales if pO2 was as low as <10-6 PAL. Sulfur isotope analysis revealed, based on the variable δ34S values (-1.9 ~ +26.8‰), that bacterial sulfate reduction was so extensive in the 3.2Ga deep marine environments that sulfate utilization by sulfate-reducers was near completion [8]. Production of bacteriogenic sulfide would have enhanced fixation of dissolved Mo into sulfide minerals in sediments. This is rather a common process occurring in oxygen-depleted environments in the modern ocean ([9]). A combined enrichment of Mo, Corg, and S, together with high δ34S values for a sedimentary formation may be used as a strong evidence for operation of modern-day style sedimentary Mo enrichment. This further implies that oxygenation of the atmosphere and (at least the surface) oceans was significant during deposition of the sediments, ~800Ma earlier than commonly thought ([10]). Operation of present-day style geochemical cycle of Mo in the Mesoarchean surface environments suggests early evolution of atmosphere, oceans, and microbial biosphere. References: [1] Kiyokawa et al, 2006, GSAB 118: 3-22. [2] Yamaguchi et al, 2009, Sci. Drill. 7: 34-37. [3] Yamaguchi, 2002, Ph.D. dissertation, Penn State Univ. [4] Yamaguchi & Ohmoto, 2002, GSA Abstract [5] Naraoka et al, 2001, 4th Int'l Archaean Symp., Perth. [6] Anbar et al, 2007, Science 317: 1903-1906. [7] Vine & Tourtelot, 1970, Econ. Geol. 65: 253-272. [8] Sakamoto et al, 2010, Fall AGU Mtg. [9] Morford & Emerson, 1999, GCA 63: 1735-1750. [10] Bekker et al, 2004, Nature 427: 117-120.

The effect of maturation on the configuration of pristane in sediments and petroleum

NASA Technical Reports Server (NTRS)

Patience, R. L.; Rowland, S. J.; Maxwell, J. R.

1978-01-01

The absolute stereochemistry of pristane in a sample of contemporary marine zooplankton, Messel shale (Germany) and Djatibarang (Java) crude has been determined by gas chromatographic methods. The relative stereochemistry in Irati shale (Brazil), Green River (U.S.) crude, Halibut (Australia) crude has also been determined, and confirmed for a sample of the Green River shale. The stereoisomer distributions indicate a loss of stereospecificity of the phytol-derived 6(R), 10(S) pristane with increasing geological maturation. For example, the least mature geological sample, the Eocene Messel shale, contains solely the 6(R), 10(S) isomer, whereas a mature sample, Djatibarange crude, contains 50% of the 6(R), 10(S) isomer and 25% of each of the 6(R), 10(R) and 6(S), 10(S) isomers.

Pyrite framboid diameter distribution in the Lower Oligocene black shales of the Vrancea Nappe as an indicator of changes in redox conditions, Eastern Outer Carpathians, Romania

NASA Astrophysics Data System (ADS)

Wendorff, Małgorzata; Marynowski, Leszek; Rospondek, Mariusz

2016-04-01

Studies of recent and ancient sediments revealed that the diameter distribution of pyrite framboids may be reliably used to characterise oxygen-restricted environments and distinguish ancient euxinic conditions (water column hydrogen sulphide bearing thus oxygen-free) from anoxic, non-sulfidic or dysoxic (oxygen-poor) conditions. Such diagnoses are of great importance when reconstructing palaeoenvironments in ancient basins and the processes of source rocks formation. During Oligocene to early Miocene time an extensive accumulation of organic matter (OM)-rich sediments occurred in the entire Paratethys including the Carpathian Foredeep, which was closed forming fold-thrust belt of the Outer Carpathians. These OM-rich black shales are represented by so-called Menilite shales, widely considered as hydrocarbon source rocks, which constitute as well a detailed archive for palaeoenvironmental changes. The purpose of this preliminary study is to characterise the depositional environment of the Lower Oligocene black shales basing on the pyrite framboid diameter distribution. Five samples of finely laminated black shales were selected from the Nechit section outcropping in the Bistrica half-window of the Vrancea Nappe in the Eastern Outer Carpathians, E Romania. At least 100 framboid diameters were measured on polished blocks using scanning electron microscope in a back-scattered electron mode. Framboids from four samples starting from the lowermost part of the section exhibit a narrow range of diameters from 1.0 to 11.5 μm; mean value ranges from 3.65 to 4.85 μm. Small-sized framboids (< 6 μm) account for 70% up to 91% of all framboids, while large framboids (>10 μm) are absent or rare (max. 2%). Within the sample from the uppermost part of the section framboids reveal more variable sizes, 2 - 25 μm, with mean value of 6.63 μm. Small framboids are still numerous (54%), however the amount of framboids >10 μm increases to 15%. The domination of small framboids with narrow size range in analysed samples, as well as lamination of rocks, suggest domination of anoxic / euxinic conditions during sedimentation of the Menilite shales. The transition into dysoxic bottom-water conditions can be evidenced by increased amount of larger framboids (up to 25 μm) in the upper part of the section. It has been concluded that framboids growing at interface of oxic/euxinic water column are in general smaller and less variable in size than framboids from sediments overlained by oxic or dysoxic water column. In the presented case, the prevalence of small framboids indicates that the water column euxinia could have developed, at least temporarily, during the deposition. Although the euxinia did not reached the photic zone as it reconstructed based on the occurrence of isorenieratane and its derivatives, e.g. C19 aryl isoprenoid in equivalent rocks from many locations of the Outer Carpathians. These biomarkers are derived from carotenoids biosynthesised by the photosynthetic green sulphur bacteria (Chlorobiaceae), anaerobic organisms requiring light and hydrogen sulphide for growth.

Effects of processed oil shale on the element content of Atriplex cancescens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, B.M.

1982-01-01

Samples of four-wing saltbush were collected from the Colorado State University Intensive Oil Shale Revegetation Study Site test plots in the Piceance basin, Colorado. The test plots were constructed to evaluate the effects of processed oil shale geochemistry on plant growth using various thicknesses of soil cover over the processed shale and/or over a gravel barrier between the shale and soil. Generally, the thicker the soil cover, the less the influence of the shale geochemistry on the element concentrations in the plants. Concentrations of 20 elements were larger in the ash of four-wing saltbush growing on the plot with themore » gravel barrier (between the soil and processed shale) when compared to the sample from the control plot. A greater water content in the soil in this plot has been reported, and the interaction between the increased, percolating water and shale may have increased the availability of these elements for plant uptake. Concentrations of boron, copper, fluorine, lithium, molybdenum, selenium, silicon, and zinc were larger in the samples grown over processed shale, compared to those from the control plot, and concentrations for barium, calcium, lanthanum, niobium, phosphorus, and strontium were smaller. Concentrations for arsenic, boron, fluorine, molybdenum, and selenium - considered to be potential toxic contaminants - were similar to results reported in the literature for vegetation from the test plots. The copper-to-molybdenum ratios in three of the four samples of four-wing saltbush growing over the processed shale were below the ratio of 2:1, which is judged detrimental to ruminants, particularly cattle. Boron concentrations averaged 140 ppM, well above the phytotoxicity level for most plant species. Arsenic, fluorine, and selenium concentrations were below toxic levels, and thus should not present any problem for revegetation or forage use at this time.« less

Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noack, Clinton W.; Jain, Jinesh C.; Stegmeier, John

In this paper, we studied the geochemistry of the rare earth elements (REE) in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In thesemore » samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.« less

Rare earth element geochemistry of outcrop and core samples from the Marcellus Shale

DOE PAGES

Noack, Clinton W.; Jain, Jinesh C.; Stegmeier, John; ...

2015-06-26

In this paper, we studied the geochemistry of the rare earth elements (REE) in eleven outcrop samples and six, depth-interval samples of a core from the Marcellus Shale. The REE are classically applied analytes for investigating depositional environments and inferring geochemical processes, making them of interest as potential, naturally occurring indicators of fluid sources as well as indicators of geochemical processes in solid waste disposal. However, little is known of the REE occurrence in the Marcellus Shale or its produced waters, and this study represents one of the first, thorough characterizations of the REE in the Marcellus Shale. In thesemore » samples, the abundance of REE and the fractionation of REE profiles were correlated with different mineral components of the shale. Namely, samples with a larger clay component were inferred to have higher absolute concentrations of REE but have less distinctive patterns. Conversely, samples with larger carbonate fractions exhibited a greater degree of fractionation, albeit with lower total abundance. Further study is necessary to determine release mechanisms, as well as REE fate-and-transport, however these results have implications for future brine and solid waste management applications.« less

Nanometer-Scale Pore Characteristics of Lacustrine Shale, Songliao Basin, NE China

PubMed Central

Wang, Min; Yang, Jinxiu; Wang, Zhiwei; Lu, Shuangfang

2015-01-01

In shale, liquid hydrocarbons are accumulated mainly in nanometer-scale pores or fractures, so the pore types and PSDs (pore size distributions) play a major role in the shale oil occurrence (free or absorbed state), amount of oil, and flow features. The pore types and PSDs of marine shale have been well studied; however, research on lacustrine shale is rare, especially for shale in the oil generation window, although lacustrine shale is deposited widely around the world. To investigate the relationship between nanometer-scale pores and oil occurrence in the lacustrine shale, 10 lacustrine shale core samples from Songliao Basin, NE China were analyzed. Analyses of these samples included geochemical measurements, SEM (scanning electron microscope) observations, low pressure CO2 and N2 adsorption, and high-pressure mercury injection experiments. Analysis results indicate that: (1) Pore types in the lacustrine shale include inter-matrix pores, intergranular pores, organic matter pores, and dissolution pores, and these pores are dominated by mesopores and micropores; (2) There is no apparent correlation between pore volumes and clay content, however, a weak negative correlation is present between total pore volume and carbonate content; (3) Pores in lacustrine shale are well developed when the organic matter maturity (Ro) is >1.0% and the pore volume is positively correlated with the TOC (total organic carbon) content. The statistical results suggest that oil in lacustrine shale mainly occurs in pores with diameters larger than 40 nm. However, more research is needed to determine whether this minimum pore diameter for oil occurrence in lacustrine shale is widely applicable. PMID:26285123

Nanometer-Scale Pore Characteristics of Lacustrine Shale, Songliao Basin, NE China.

PubMed

Wang, Min; Yang, Jinxiu; Wang, Zhiwei; Lu, Shuangfang

2015-01-01

In shale, liquid hydrocarbons are accumulated mainly in nanometer-scale pores or fractures, so the pore types and PSDs (pore size distributions) play a major role in the shale oil occurrence (free or absorbed state), amount of oil, and flow features. The pore types and PSDs of marine shale have been well studied; however, research on lacustrine shale is rare, especially for shale in the oil generation window, although lacustrine shale is deposited widely around the world. To investigate the relationship between nanometer-scale pores and oil occurrence in the lacustrine shale, 10 lacustrine shale core samples from Songliao Basin, NE China were analyzed. Analyses of these samples included geochemical measurements, SEM (scanning electron microscope) observations, low pressure CO2 and N2 adsorption, and high-pressure mercury injection experiments. Analysis results indicate that: (1) Pore types in the lacustrine shale include inter-matrix pores, intergranular pores, organic matter pores, and dissolution pores, and these pores are dominated by mesopores and micropores; (2) There is no apparent correlation between pore volumes and clay content, however, a weak negative correlation is present between total pore volume and carbonate content; (3) Pores in lacustrine shale are well developed when the organic matter maturity (Ro) is >1.0% and the pore volume is positively correlated with the TOC (total organic carbon) content. The statistical results suggest that oil in lacustrine shale mainly occurs in pores with diameters larger than 40 nm. However, more research is needed to determine whether this minimum pore diameter for oil occurrence in lacustrine shale is widely applicable.

Potential reduction in terrestrial salamander ranges associated with Marcellus shale development

USGS Publications Warehouse

Brand, Adrianne B,; Wiewel, Amber N. M.; Grant, Evan H. Campbell

2014-01-01

Natural gas production from the Marcellus shale is rapidly increasing in the northeastern United States. Most of the endemic terrestrial salamander species in the region are classified as ‘globally secure’ by the IUCN, primarily because much of their ranges include state- and federally protected lands, which have been presumed to be free from habitat loss. However, the proposed and ongoing development of the Marcellus gas resources may result in significant range restrictions for these and other terrestrial forest salamanders. To begin to address the gaps in our knowledge of the direct impacts of shale gas development, we developed occurrence models for five species of terrestrial plethodontid salamanders found largely within the Marcellus shale play. We predicted future Marcellus shale development under several scenarios. Under scenarios of 10,000, 20,000, and 50,000 new gas wells, we predict 4%, 8%, and 20% forest loss, respectively, within the play. Predictions of habitat loss vary among species, but in general, Plethodon electromorphus and Plethodonwehrlei are predicted to lose the greatest proportion of forested habitat within their ranges if future Marcellus development is based on characteristics of the shale play. If development is based on current well locations,Plethodonrichmondi is predicted to lose the greatest proportion of habitat. Models showed high uncertainty in species’ ranges and emphasize the need for distribution data collected by widespread and repeated, randomized surveys.

Baseline groundwater quality in national park units within the Marcellus and Utica Shale gas plays, New York, Pennsylvania, and West Virginia, 2011

USGS Publications Warehouse

Eckhardt, David A.V.; Sloto, Ronald A.

2012-01-01

Groundwater samples were collected from 15 production wells and 1 spring at 9 national park units in New York, Pennsylvania, and West Virginia in July and August 2011 and analyzed to characterize the quality of these water supplies. The sample sites generally were selected to represent areas of potential effects on water quality by drilling and development of gas wells in Marcellus Shale and Utica Shale areas of the northeastern United States. The groundwater samples were analyzed for 53 constituents, including nutrients, major inorganic constituents, trace elements, chemical oxygen demand, radioactivity, and dissolved gases, including methane and radon-222. Results indicated that the groundwater used for water supply at the selected national park units is generally of acceptable quality, although concentrations of some constituents exceeded at least one drinking-water guideline at several wells. Nine analytes were detected in concentrations that exceeded Federal drinking-water standards, mostly secondary standards that define aesthetic properties of water, such as taste and odor. One sample had an arsenic concentration that exceeded the U.S. Environmental Protection Agency maximum contaminant level (MCL) of 10 micrograms per liter (μg/L). The pH, which is a measure of acidity (hydrogen ion activity), ranged from 4.8 to 8.4, and in 5 of the 16 samples, the pH values were outside the accepted U.S. Environmental Protection Agency secondary maximum contaminant level (SMCL) range of 6.5 to 8.5. The concentration of total dissolved solids exceeded the SMCL of 500 milligrams per liter (mg/L) at four sites. The sulfate concentration exceeded the SMCL of 250 mg/L concentration in one sample, and the fluoride concentration exceeded the SMCL of 2 mg/L in one sample. Sodium concentrations exceeded the U.S. Environmental Protection Agency drinking water health advisory of 60 mg/L at four sites. Iron concentrations exceeded the SMCL of 300 μg/L in two samples, and manganese concentrations exceeded the SMCL of 50 μg/L in five samples. Radon-222 concentrations exceeded the proposed U.S. Environmental Protection Agency MCL of 300 picocuries per liter in eight samples.

The flux of radionuclides in flowback fluid from shale gas exploitation.

PubMed

Almond, S; Clancy, S A; Davies, R J; Worrall, F

2014-11-01

This study considers the flux of radioactivity in flowback fluid from shale gas development in three areas: the Carboniferous, Bowland Shale, UK; the Silurian Shale, Poland; and the Carboniferous Barnett Shale, USA. The radioactive flux from these basins was estimated, given estimates of the number of wells developed or to be developed, the flowback volume per well and the concentration of K (potassium) and Ra (radium) in the flowback water. For comparative purposes, the range of concentration was itself considered within four scenarios for the concentration range of radioactive measured in each shale gas basin, the groundwater of the each shale gas basin, global groundwater and local surface water. The study found that (i) for the Barnett Shale and the Silurian Shale, Poland, the 1 % exceedance flux in flowback water was between seven and eight times that would be expected from local groundwater. However, for the Bowland Shale, UK, the 1 % exceedance flux (the flux that would only be expected to be exceeded 1 % of the time, i.e. a reasonable worst case scenario) in flowback water was 500 times that expected from local groundwater. (ii) In no scenario was the 1 % exceedance exposure greater than 1 mSv-the allowable annual exposure allowed for in the UK. (iii) The radioactive flux of per energy produced was lower for shale gas than for conventional oil and gas production, nuclear power production and electricity generated through burning coal.

Experimental Investigation of Mechanical Properties of Black Shales after CO₂-Water-Rock Interaction.

PubMed

Lyu, Qiao; Ranjith, Pathegama Gamage; Long, Xinping; Ji, Bin

2016-08-06

The effects of CO₂-water-rock interactions on the mechanical properties of shale are essential for estimating the possibility of sequestrating CO₂ in shale reservoirs. In this study, uniaxial compressive strength (UCS) tests together with an acoustic emission (AE) system and SEM and EDS analysis were performed to investigate the mechanical properties and microstructural changes of black shales with different saturation times (10 days, 20 days and 30 days) in water dissoluted with gaseous/super-critical CO₂. According to the experimental results, the values of UCS, Young's modulus and brittleness index decrease gradually with increasing saturation time in water with gaseous/super-critical CO₂. Compared to samples without saturation, 30-day saturation causes reductions of 56.43% in UCS and 54.21% in Young's modulus for gaseous saturated samples, and 66.05% in UCS and 56.32% in Young's modulus for super-critical saturated samples, respectively. The brittleness index also decreases drastically from 84.3% for samples without saturation to 50.9% for samples saturated in water with gaseous CO₂, to 47.9% for samples saturated in water with super-critical carbon dioxide (SC-CO₂). SC-CO₂ causes a greater reduction of shale's mechanical properties. The crack propagation results obtained from the AE system show that longer saturation time produces higher peak cumulative AE energy. SEM images show that many pores occur when shale samples are saturated in water with gaseous/super-critical CO₂. The EDS results show that CO₂-water-rock interactions increase the percentages of C and Fe and decrease the percentages of Al and K on the surface of saturated samples when compared to samples without saturation.

Synthesis and analysis of jet fuels from shale oil and coal syncrudes

NASA Technical Reports Server (NTRS)

Antoine, A. C.; Gallagher, J. P.

1976-01-01

The technical problems involved in converting a significant portion of a barrel of either a shale oil or coal syncrude into a suitable aviation turbine fuel were studied. TOSCO shale oil, H-Coal and COED coal syncrudes were the starting materials. They were processed by distillation and hydrocracking to produce two levels of yield (20 and 40 weight percent) of material having a distillation range of approximately 422 to 561 K (300 F to 550 F). The full distillation range 311 to 616 K (100 F to 650 F) materials were hydrotreated to meet two sets of specifications (20 and 40 volume percent aromatics, 13.5 and 12.75 weight percent H, 0.2 and 0.5 weight percent S, and 0.1 and 0.2 weight percent N). The hydrotreated materials were distilled to meet given end point and volatility requirements. The syntheses were carried out in laboratory and pilot plant equipment scaled to produce thirty-two 0.0757 cu m (2-gal)samples of jet fuel of varying defined specifications. Detailed analyses for physical and chemical properties were made on the crude starting materials and on the products.

An exploratory study of air emissions associated with shale gas development and production in the Barnett Shale.

PubMed

Rich, Alisa; Grover, James P; Sattler, Melanie L

2014-01-01

Information regarding air emissions from shale gas extraction and production is critically important given production is occurring in highly urbanized areas across the United States. Objectives of this exploratory study were to collect ambient air samples in residential areas within 61 m (200 feet) of shale gas extraction/production and determine whether a "fingerprint" of chemicals can be associated with shale gas activity. Statistical analyses correlating fingerprint chemicals with methane, equipment, and processes of extraction/production were performed. Ambient air sampling in residential areas of shale gas extraction and production was conducted at six counties in the Dallas/Fort Worth (DFW) Metroplex from 2008 to 2010. The 39 locations tested were identified by clients that requested monitoring. Seven sites were sampled on 2 days (typically months later in another season), and two sites were sampled on 3 days, resulting in 50 sets of monitoring data. Twenty-four-hour passive samples were collected using summa canisters. Gas chromatography/mass spectrometer analysis was used to identify organic compounds present. Methane was present in concentrations above laboratory detection limits in 49 out of 50 sampling data sets. Most of the areas investigated had atmospheric methane concentrations considerably higher than reported urban background concentrations (1.8-2.0 ppm(v)). Other chemical constituents were found to be correlated with presence of methane. A principal components analysis (PCA) identified multivariate patterns of concentrations that potentially constitute signatures of emissions from different phases of operation at natural gas sites. The first factor identified through the PCA proved most informative. Extreme negative values were strongly and statistically associated with the presence of compressors at sample sites. The seven chemicals strongly associated with this factor (o-xylene, ethylbenzene, 1,2,4-trimethylbenzene, m- and p-xylene, 1,3,5-trimethylbenzene, toluene, and benzene) thus constitute a potential fingerprint of emissions associated with compression. Information regarding air emissions from shale gas development and production is critically important given production is now occurring in highly urbanized areas across the United States. Methane, the primary shale gas constituent, contributes substantially to climate change; other natural gas constituents are known to have adverse health effects. This study goes beyond previous Barnett Shale field studies by encompassing a wider variety of production equipment (wells, tanks, compressors, and separators) and a wider geographical region. The principal components analysis, unique to this study, provides valuable information regarding the ability to anticipate associated shale gas chemical constituents.

Mineralogical characterization of selected shales in support of nuclear waste repository studies: Progress report, October 1987--September 1988

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, S. Y.; Hyder, L. K.; Baxter, P. M.

1989-07-01

One objective of the Sedimentary Rock Program at the Oak Ridge National Laboratory has been to examine end-member shales to develop a data base that will aid in evaluations if shales are ever considered as a repository host rock. Five end-member shales were selected for comprehensive characterization: the Chattanooga Shale from Fentress County, Tennessee; the Pierre Shale from Gregory County, South Dakota; the Green River Formation from Garfield County, Colorado; and the Nolichucky Shale and Pumpkin Valley Shale from Roane County, Tennessee. Detailed micromorphological and mineralogical characterizations of the shales were completed by Lee et al. (1987) in ORNL/TM-10567. Thismore » report is a supplemental characterization study that was necessary because second batches of the shale samples were needed for additional studies. Selected physical, chemical, and mineralogical properties were determined for the second batches; and their properties were compared with the results from the first batches. Physical characterization indicated that the second-batch and first-batch samples had a noticeable difference in apparent-size distributions but had similar primary-particle-size distributions. There were some differences in chemical composition between the batches, but these differences were not considered important in comparison with the differences among the end-member shales. The results of x-ray diffraction analyses showed that the second batches had mineralogical compositions very similar to the first batches. 9 refs., 9 figs., 4 tabs.« less

Measurements of Methane Emissions and Volatile Organic Compounds from Shale Gas Operations in the Marcellus Shale

NASA Astrophysics Data System (ADS)

Omara, M.; Subramanian, R.; Sullivan, M.; Robinson, A. L.; Presto, A. A.

2014-12-01

The Marcellus Shale is the most expansive shale gas reserve in play in the United States, representing an estimated 17 to 29 % of the total domestic shale gas reserves. The rapid and extensive development of this shale gas reserve in the past decade has stimulated significant interest and debate over the climate and environmental impacts associated with fugitive releases of methane and other pollutants, including volatile organic compounds. However, the nature and magnitude of these pollutant emissions remain poorly characterized. This study utilizes the tracer release technique to characterize total fugitive methane release rates from natural gas facilities in southwestern Pennsylvania and West Virginia that are at different stages of development, including well completion flowbacks and active production. Real-time downwind concentrations of methane and two tracer gases (acetylene and nitrous oxide) released onsite at known flow rates were measured using a quantum cascade tunable infrared laser differential absorption spectrometer (QC-TILDAS, Aerodyne, Billerica, MA) and a cavity ring down spectrometer (Model G2203, Picarro, Santa Clara, CA). Evacuated Silonite canisters were used to sample ambient air during downwind transects of methane and tracer plumes to assess volatile organic compounds (VOCs). A gas chromatograph with a flame ionization detector was used to quantify VOCs following the EPA Method TO-14A. A preliminary assessment of fugitive emissions from actively producing sites indicated that methane leak rates ranged from approximately 1.8 to 6.2 SCFM, possibly reflecting differences in facility age and installed emissions control technology. A detailed comparison of methane leak rates and VOCs emissions with recent published literature for other US shale gas plays will also be discussed.

Nanoscale Experimental Characterization and 3D Mechanistic Modeling of Shale with Quantified Heterogeneity

NASA Astrophysics Data System (ADS)

Bennett, K. C.; Borja, R. I.

2014-12-01

Shale is a fine-grained sedimentary rock consisting primarily of clay and silt, and is of particular interest with respect to hydrocarbon production as both a source and seal rock. The deformation and fracture properties of shale depend on the mechanical properties of its basic constituents, including solid clay particles, inclusions such as silt and organics, and multiscale porosity. This paper presents the results of a combined experimental/numerical investigation into the mechanical behavior of shale at the nanoscale. Large grids of nanoindentation tests, spanning various length scales ranging from 200-20000 nanometers deep, were performed on a sample of Woodford shale in both the bedding plane normal (BPN) and bedding plane parallel (BPP) directions. The nanoindentions were performed in order to determine the mechanical properties of the constituent materials in situ as well as those of the highly heterogeneous composite material at this scale. Focused ion beam (FIB) milling and scanning electron microscopy (SEM) were used in conjunction (FIB-SEM) to obtain 2D and 3D images characterizing the heterogeneity of the shale at this scale. The constituent materials were found to be best described as consisting of near micrometer size clay and silt particles embedded in a mixed organic/clay matrix, with some larger (near 10 micrometers in diameter) pockets of organic material evident. Indented regions were identified through SEM, allowing the 200-1000 nanometer deep indentations to be classified according to the constituent materials which they engaged. We use nonlinear finite element modeling to capture results of low-load (on the order of milliNewtons) and high-load (on the order of a few Newtons) nanoindentation tests. Experimental results are used to develop a 3D mechanistic model that interprets the results of nanoindentation tests on specimens of Woodford shale with quantified heterogeneity.

Origin of dolomite in Miocene Monterey Shale and related formations in the Temblor Range, California

USGS Publications Warehouse

Friedman, I.; Murata, K.J.

1979-01-01

Dolomites in thick sections of Miocene Monterey Shale and related formations in the Temblor Range of California acquired their isotopic compositions as they formed at shallow depth in the original sediment rich in organic matter, and retained the composition against the vicissitudes of burial diagenesis. The oxygen isotopes of dolomites of successive beds record changes in temperature of bottom water while the carbon isotopes of the same samples indicate changes in the kind of microbial activity (sulfate reduction vs carbohydrate fermentation) that prevailed at shallow depths in the sediment. In an auxiliary study, two samples of dolomite from sediments of Cariaco Basin off Venezuela (DSDP site 147) were found to have ??5C13 of -14.1 and -9.8 per ml PDB, although they occur in a heavy-carbon zone containing bicarbonate as heavy as +8.4 per ml. These dolomites probably originated at shallow depth in the light-carbon zone of microbial sulfate reducers and were buried under later sediments down into the heavy-carbon zone of microbial fermenters of carbohydrates without losing their original light-carbon composition. ?? 1979.

Vertical hydraulic conductivity measurements in the Denver Basin, Colorado

USGS Publications Warehouse

Barkmann, P.E.

2004-01-01

The Denver Basin is a structural basin on the eastern flank of the Rocky Mountain Front Range, Colorado, containing approximately 3000 ft of sediments that hold a critical groundwater resource supplying many thousands of households with water. Managing this groundwater resource requires understanding how water gets into and moves through water-bearing layers in a complex multiple-layered sedimentary sequence. The Denver Basin aquifer system consists of permeable sandstone interbedded with impermeable shale that has been subdivided into four principle aquifers named, in ascending order, the Laramie-Fox Hills, Arapahoe, Denver, and Dawson aquifers. Although shale can dominate the stratigraphic interval containing the aquifers, there is very little empirical data regarding the hydrogeologic properties of the shale layers that control groundwater flow in the basin. The amount of water that flows vertically within the basin is limited by the vertical hydraulic conductivity through the confining shale layers. Low vertical flow volumes translate to low natural recharge rates and can have a profound negative impact on long-term well yields and the economic viability of utilizing the resource. To date, direct measurements of vertical hydraulic conductivity from cores of fine-grained sediments have been published from only five locations; and the data span a wide range from 1??10-3 to 1??10-11 cm/sec. This range may be attributable, in part, to differences in sample handling and analytical methods; however, it may also reflect subtle differences in the lithologic characteristics of the fine-grained sediments such as grain-size, clay mineralogy, and compaction that relate to position in the basin. These limited data certainly call for the collection of additional data.

Petrographic maturity parameters of a Devonian shale maturation series, Appalachian Basin, USA. ICCP Thermal Indices Working Group interlaboratory exercise

USGS Publications Warehouse

Araujo, Carla Viviane; Borrego, Angeles G.; Cardott, Brian; das Chagas, Renata Brenand A.; Flores, Deolinda; Goncalves, Paula; Hackley, Paul C.; Hower, James C.; Kern, Marcio Luciano; Kus, Jolanta; Mastalerz, Maria; Filho, João Graciano Mendonça; de Oliveira Mendonça, Joalice; Rego Menezes, Taissa; Newman, Jane; Suarez-Ruiz, Isabel; Sobrinho da Silva, Frederico; Viegas de Souza, Igor

2014-01-01

This paper presents results of an interlaboratory exercise on organic matter optical maturity parameters using a natural maturation series comprised by three Devonian shale samples (Huron Member, Ohio Shale) from the Appalachian Basin, USA. This work was conducted by the Thermal Indices Working Group of the International Committee for Coal and Organic Petrology (ICCP) Commission II (Geological Applications of Organic Petrology). This study aimed to compare: 1. maturation predicted by different types of petrographic parameters (vitrinite reflectance and spectral fluorescence of telalginite), 2. reproducibility of the results for these maturation parameters obtained by different laboratories, and 3. improvements in the spectral fluorescence measurement obtained using modern detection systems in comparison with the results from historical round robin exercises.Mean random vitrinite reflectance measurements presented the highest level of reproducibility (group standard deviation 0.05) for low maturity and reproducibility diminished with increasing maturation (group standard deviation 0.12).Corrected fluorescence spectra, provided by 14 participants, showed a fair to good correspondence. Standard deviation of the mean values for spectral parameters was lowest for the low maturity sample but was also fairly low for higher maturity samples.A significant improvement in the reproducibility of corrected spectral fluorescence curves was obtained in the current exercise compared to a previous investigation of Toarcian organic matter spectra in a maturation series from the Paris Basin. This improvement is demonstrated by lower values of standard deviation and is interpreted to reflect better performance of newer photo-optical measuring systems.Fluorescence parameters measured here are in good agreement with vitrinite reflectance values for the least mature shale but indicate higher maturity than shown by vitrinite reflectance for the two more mature shales. This red shift in λmax beyond 0.65% vitrinite reflectance was also observed in studies of Devonian shale in other basins, suggesting that the accepted correlation for these two petrographic thermal maturity parameters needs to be re-evaluated.A good linear correlation between λmax and Tmax for this maturation series was observed and λmax 600 nm corresponds to Tmax of 440 °C. Nevertheless if a larger set of Devonian samples is included, the correlation is polynomial with a jump in λmax ranging from 540 to 570 nm. Up to 440 °C of Tmax, the λmax, mostly, reaches up to 500 nm; beyond a Tmax of 440 °C, λmax is in the range of 580–600 nm. This relationship places the “red shift” when the onset of the oil window is reached at Tmax of 440 °C. Moreover, the correlation between HI and λmax (r2 = 0.70) shows a striking inflection and decrease in HI above a λmax of 600 nm, coincident with the approximate onset of hydrocarbon generation in these rocks.

Leaching of polycyclic aromatic hydrocarbons from oil shale processing waste deposit: a long-term field study.

PubMed

Jefimova, Jekaterina; Irha, Natalya; Reinik, Janek; Kirso, Uuve; Steinnes, Eiliv

2014-05-15

The leaching behavior of selected polycyclic aromatic hydrocarbons (PAHs) from an oil shale processing waste deposit was monitored during 2005-2009. Samples were collected from the deposit using a special device for leachate sampling at field conditions without disturbance of the upper layers. Contents of 16 priority PAHs in leachate samples collected from aged and fresh parts of the deposit were determined by GC-MS. The sum of the detected PAHs in leachates varied significantly throughout the study period: 19-315 μg/l from aged spent shale, and 36-151 μg/l from fresh spent shale. Among the studied PAHs the low-molecular weight compounds phenanthrene, naphthalene, acenaphthylene, and anthracene predominated. Among the high-molecular weight PAHs benzo[a]anthracene and pyrene leached in the highest concentrations. A spent shale deposit is a source of PAHs that could infiltrate into the surrounding environment for a long period of time. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation of Controlling Factors Impacting Water Quality in Shale Gas Produced Brine

NASA Astrophysics Data System (ADS)

Fan, W.; Hayes, K. F.; Ellis, B. R.

2014-12-01

The recent boom in production of natural gas from unconventional reservoirs has generated a substantial increase in the volume of produced brine that must be properly managed to prevent contamination of fresh water resources. Produced brine, which includes both flowback and formation water, is often highly saline and may contain elevated concentrations of naturally occurring radioactive material and other toxic elements. These characteristics present many challenges with regard to designing effective treatment and disposal strategies for shale gas produced brine. We will present results from a series of batch experiments where crushed samples from two shale formations in the Michigan Basin, the Antrim and Utica-Collingwood shales, were brought into contact with synthetic hydraulic fracturing fluids under in situ temperature and pressure conditions. The Antrim has been an active shale gas play for over three decades, while the Utica-Collingwood formation (a grouped reservoir consisting of the Utica shale and Collingwood limestone) is an emerging shale gas play. The goal of this study is to investigate the influence of water-rock interactions in controlling produced water quality. We evaluate toxic element leaching from shale samples in contact with model hydraulic fracturing fluids under system conditions corresponding to reservoir depths up to 1.5 km. Experimental results have begun to elucidate the relative importance of shale mineralogy, system conditions, and chemical additives in driving changes in produced water quality. Initial results indicate that hydraulic fracturing chemical additives have a strong influence on the extent of leaching of toxic elements from the shale. In particular, pH was a key factor in the release of uranium (U) and divalent metals, highlighting the importance of the mineral buffering capacity of the shale. Low pH values persisted in the Antrim and Utica shale experiments and resulted in higher U extraction efficiencies than that observed in the presence of the carbonate-rich Collingwood limestone. In addition to assessing U leaching, we also measured the activity of 226Ra and 228Ra via high-resolution gamma ray spectroscopy. Laboratory results will be compared to observations from a complimentary field sampling campaign of Antrim produced brine.

Investigation of water-soluble organic matter extracted from shales during leaching experiments

NASA Astrophysics Data System (ADS)

Zhu, Yaling; Vieth-Hillebrand, Andrea; Wilke, Franziska D. H.; Horsfield, Brian

2017-04-01

The huge volumes and unknown composition of flowback and produced waters cause major public concerns about the environmental and social compatibility of hydraulic fracturing and the exploitation of gas from unconventional reservoirs. Flowback and produced waters contain not only residues of fracking additives but also chemical species that are dissolved from the shales themselves during fluid-rock interaction. Knowledge of the composition, size and structure of dissolved organic carbon (DOC) as well as the main controls on the release of DOC are a prerequisite for a better understanding of these interactions and its effects on composition of flowback and produced water. Black shales from four different geological settings and covering a maturity range Ro = 0.3-2.6% were extracted with deionized water. The DOC yields were found to decrease rapidly with increasing diagenesis and remain low throughout catagenesis. Four DOC fractions have been qualitatively and quantitatively characterized using size-exclusion chromatography. The concentrations of individual low molecular weight organic acids (LMWOA) decrease with increasing maturity of the samples except for acetate extracted from the overmature Posidonia shale, which was influenced by hydrothermal brines. The oxygen content of the shale organic matter also shows a significant influence on the release of organic acids, which is indicated by the positive trend between oxygen index (OI) and the concentrations of formate and acetate. Based on our experiments, both the properties of the organic matter source and the thermal maturation progress of the shale organic matter significantly influence the amount and quality of extracted organic compounds during the leaching experiments.

Assessment of hydrocarbon source rock potential of Polish bituminous coals and carbonaceous shales

USGS Publications Warehouse

Kotarba, M.J.; Clayton, J.L.; Rice, D.D.; Wagner, M.

2002-01-01

We analyzed 40 coal samples and 45 carbonaceous shale samples of varying thermal maturity (vitrinite reflectance 0.59% to 4.28%) from the Upper Carboniferous coal-bearing strata of the Upper Silesian, Lower Silesian, and Lublin basins, Poland, to evaluate their potential for generation and expulsion of gaseous and liquid hydrocarbons. We evaluated source rock potential based on Rock-Eval pyrolysis yield, elemental composition (atomic H/C and O/C), and solvent extraction yields of bitumen. An attempt was made to relate maceral composition to these source rock parameters and to composition of the organic matter and likely biological precursors. A few carbonaceous shale samples contain sufficient generation potential (pyrolysis assay and elemental composition) to be considered potential source rocks, although the extractable hydrocarbon and bitumen yields are lower than those reported in previous studies for effective Type III source rocks. Most samples analysed contain insufficient capacity for generation of hydrocarbons to reach thresholds required for expulsion (primary migration) to occur. In view of these findings, it is improbable that any of the coals or carbonaceous shales at the sites sampled in our study would be capable of expelling commercial amounts of oil. Inasmuch as a few samples contained sufficient generation capacity to be considered potential source rocks, it is possible that some locations or stratigraphic zones within the coals and shales could have favourable potential, but could not be clearly delimited with the number of samples analysed in our study. Because of their high heteroatomic content and high amount of asphaltenes, the bitumens contained in the coals are less capable of generating hydrocarbons even under optimal thermal conditions than their counterpart bitumens in the shales which have a lower heteroatomic content. Published by Elsevier Science B.V.

Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

USGS Publications Warehouse

Horan, M.F.; Morgan, J.W.; Grauch, R.I.; Coveney, R.M.; Murowchick, J.B.; Hulbert, L.J.

1994-01-01

Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/192Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/192Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively. ?? 1994.

Multivariate analysis relating oil shale geochemical properties to NMR relaxometry

USGS Publications Warehouse

Birdwell, Justin E.; Washburn, Kathryn E.

2015-01-01

Low-field nuclear magnetic resonance (NMR) relaxometry has been used to provide insight into shale composition by separating relaxation responses from the various hydrogen-bearing phases present in shales in a noninvasive way. Previous low-field NMR work using solid-echo methods provided qualitative information on organic constituents associated with raw and pyrolyzed oil shale samples, but uncertainty in the interpretation of longitudinal-transverse (T1–T2) relaxometry correlation results indicated further study was required. Qualitative confirmation of peaks attributed to kerogen in oil shale was achieved by comparing T1–T2 correlation measurements made on oil shale samples to measurements made on kerogen isolated from those shales. Quantitative relationships between T1–T2 correlation data and organic geochemical properties of raw and pyrolyzed oil shales were determined using partial least-squares regression (PLSR). Relaxometry results were also compared to infrared spectra, and the results not only provided further confidence in the organic matter peak interpretations but also confirmed attribution of T1–T2 peaks to clay hydroxyls. In addition, PLSR analysis was applied to correlate relaxometry data to trace element concentrations with good success. The results of this work show that NMR relaxometry measurements using the solid-echo approach produce T1–T2 peak distributions that correlate well with geochemical properties of raw and pyrolyzed oil shales.

Determination of maximal amount of minor gases adsorbed in a shale sample by headspace gas chromatography.

PubMed

Zhang, Chun-Yun; Hu, Hui-Chao; Chai, Xin-Sheng; Pan, Lei; Xiao, Xian-Ming

2014-02-07

In this paper, we present a novel method for determining the maximal amount of ethane, a minor gas species, adsorbed in a shale sample. The method is based on the time-dependent release of ethane from shale samples measured by headspace gas chromatography (HS-GC). The study includes a mathematical model for fitting the experimental data, calculating the maximal amount gas adsorbed, and predicting results at other temperatures. The method is a more efficient alternative to the isothermal adsorption method that is in widespread use today. Copyright © 2013 Elsevier B.V. All rights reserved.

43 CFR 3900.40 - Multiple use development of leased or licensed lands.

Code of Federal Regulations, 2011 CFR

2011-10-01

... (Continued) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Oil Shale Management-Introduction § 3900.40 Multiple use development of leased or licensed... production of deposits of oil shale does not preclude the BLM from issuing other exploration licenses or...

43 CFR 3930.13 - Performance standards for surface mines.

Code of Federal Regulations, 2011 CFR

2011-10-01

... OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) MANAGEMENT OF OIL SHALE EXPLORATION AND LEASES Management of Oil Shale Exploration Licenses and Leases § 3930.13 Performance standards for surface mines. (a) Pit widths for each oil shale seam must be engineered and designed to eliminate...

Heterogeneity of shales in different scales and its implications to laboratory analyses - examples from sedimentology and organic geochemistry study of the Lower Paleozoic shales from shale gas exploration well located in the Baltic Basin, Poland.

NASA Astrophysics Data System (ADS)

Roszkowska-Remin, Joanna; Janas, Marcin

2017-04-01

We present the litho-sedimentological, organic geochemical results and organic porosity estimation of the Ordovician and Silurian shales in the SeqWell (shale gas exploration well located in the Pomerania region, Poland). The most perspective black and bituminous shales of the Upper Ordovician and the Lower Silurian may seem to be homogeneous. However, our results reveal that these shales show heterogeneity at different scales (m to mm). For example, in most cases the decrease of TOC content in the m scale is related to pyroclastic rock intercalations and "dark bioturbations" with no color difference when compared with surrounding sediments. While in cm scale heterogeneity is related to bioturbations, density of organic-rich laminas, or abundance of carbonates and pyrite. Without a detailed sedimentological study of polished core surfaces and Rock-Eval analyses those observations are rather invisible. The correct interpretation of results requires the understanding of rock's heterogeneity in different scales. It has a critical importance for laboratory tests applied on few cm long samples, especially if the results are to be extrapolated to wider intervals. Therefore in ShaleSeq project, a detailed sedimentological core logging and analysis of geochemical parameters of perspective formations in m to mm scale was performed for the first time. The results show good correlation between bioturbation index (BI) and organic geochemical indicators like organic carbon content (TOC) or oxic deposition conditions indicator (oxygen index - OI) leading to the assumption that environmental conditions may have played a crucial role in organic carbon preservation. The geochemical analyses of 12 samples showed that even within the few cm long sections shale can be really diversified. Eight out of twelve analyzed samples were considered geochemically mostly homogeneous, whilst four of them showed evident heterogeneity. Concluding, the sampling should be preceded by detailed sedimentological study, as it allows to control if the chosen samples are representative for wider intervals and give opportunity to place the laboratory results in the wider context. An attempt to estimate organic porosity using Rock-Eval data was based on Marathon Oil company study of the Polish Lower Paleozoic shales. The results of this study and suggested equations were used to calculate hypothetical organic porosity of the most perspective shales in the SeqWell. Calculated organic porosities in % bulk volume of rock suggested that organic porosity for Upper Ordovician and Lower Silurian shales in SeqWell may be at the level of 0,1-2,9% in bulk volume of rock. These results would suggest that organic porosity doesn't play a major role in total porosity system in these shales at the certain thermal maturity level. The hypothetical organic porosity values were not validated by the microscopic study though. Our study are part of the ShaleSeq Project co-funded by Norway Grants of the Polish-Norwegian Research Programme operated by the National Centre for Research and Development.

Organic Substances from Unconventional Oil and Gas Production in Shale

NASA Astrophysics Data System (ADS)

Orem, W. H.; Varonka, M.; Crosby, L.; Schell, T.; Bates, A.; Engle, M.

2014-12-01

Unconventional oil and gas (UOG) production has emerged as an important element in the US and world energy mix. Technological innovations in the oil and gas industry, especially horizontal drilling and hydraulic fracturing, allow for the enhanced release of oil and natural gas from shale compared to conventional oil and gas production. This has made commercial exploitation possible on a large scale. Although UOG is enormously successful, there is surprisingly little known about the effects of this technology on the targeted shale formation and on environmental impacts of oil and gas production at the surface. We examined water samples from both conventional and UOG shale wells to determine the composition, source and fate of organic substances present. Extraction of hydrocarbon from shale plays involves the creation and expansion of fractures through the hydraulic fracturing process. This process involves the injection of large volumes of a water-sand mix treated with organic and inorganic chemicals to assist the process and prop open the fractures created. Formation water from a well in the New Albany Shale that was not hydraulically fractured (no injected chemicals) had total organic carbon (TOC) levels that averaged 8 mg/L, and organic substances that included: long-chain fatty acids, alkanes, polycyclic aromatic hydrocarbons, heterocyclic compounds, alkyl benzenes, and alkyl phenols. In contrast, water from UOG production in the Marcellus Shale had TOC levels as high as 5,500 mg/L, and contained a range of organic chemicals including, solvents, biocides, scale inhibitors, and other organic chemicals at thousands of μg/L for individual compounds. These chemicals and TOC decreased rapidly over the first 20 days of water recovery as injected fluids were recovered, but residual organic compounds (some naturally-occurring) remained up to 250 days after the start of water recovery (TOC 10-30 mg/L). Results show how hydraulic fracturing changes the organic composition of shale formation water, and that some injected organic substances are retained on the shale and slowly released. Thus, appropriate safe disposal of produced water is needed long into production. Changes in organic substances in formation water may impact microbial communities. Current work is focused on UOG production in the Permian Basin, Texas.

Micro Mechanics and Microstructures of Major Subsurface Hydraulic Barriers: Shale Caprock vs Wellbore Cement

NASA Astrophysics Data System (ADS)

Radonjic, M.; Du, H.

2015-12-01

Shale caprocks and wellbore cements are two of the most common subsurface impermeable barriers in the oil and gas industry. More than 60% of effective seals for geologic hydrocarbon bearing formations as natural hydraulic barriers constitute of shale rocks. Wellbore cements provide zonal isolation as an engineered hydraulic barrier to ensure controlled fluid flow from the reservoir to the production facilities. Shale caprocks were deposited and formed by squeezing excess formation water and mineralogical transformations at different temperatures and pressures. In a similar process, wellbore cements are subjected to compression during expandable tubular operations, which lead to a rapid pore water propagation and secondary mineral precipitation within the cement. The focus of this research was to investigate the effect of wellbore cement compression on its microstructure and mechanical properties, as well as a preliminary comparison of shale caprocks and hydrated cement. The purpose of comparative evaluation of engineered vs natural hydraulic barrier materials is to further improve wellbore cement durability when in contact with geofluids. The micro-indentation was utilized to evaluate the change in cement mechanical properties caused by compression. Indentation experiments showed an overall increase in hardness and Young's modulus of compressed cement. Furthermore, SEM imaging and Electron Probe Microanalysis showed mineralogical alterations and decrease in porosity. These can be correlated with the cement rehydration caused by microstructure changes as a result of compression. The mechanical properties were also quantitatively compared to shale caprock samples in order to investigate the similarities of hydraulic barrier features that could help to improve the subsurface application of cement in zonal isolation. The comparison results showed that the poro-mechanical characteristics of wellbore cement appear to be improved when inherent pore sizes are shifted to predominantly nano-scale range as characteristic of pore-size distribution typical for shale rocks. The effect of compression on cement appears to petrophysically alter cement towards the properties of shale caprocks, although the process is achieved much faster than in the case of shale diagenesis over geological times.

Germanium and uranium in coalified wood bom upper Devonian black shale

USGS Publications Warehouse

Breger, I.A.; Schopf, J.M.

1955-01-01

Microscopic study of black, vitreous, carbonaceous material occurring in the Chattanooga shale in Tennessee and in the Cleveland member of the Ohio shale in Ohio has revealed coalified woody plant tissue. Some samples have shown sufficient detail to be identified with the genus Cauixylon. Similar material has been reported in the literature as "bituminous" or "asphaltic" stringers. Spectrographic analyses of the ash from the coalified wood have shown unusually high percentages of germanium, uranium, vanadium, and nickel. The inverse relationship between uranium and germanium in the ash and the ash content of various samples shows an association of these elements with the organic constituents of the coal. On the basis of geochemical considerations, it seems most probable that the wood or coalified wood was germanium-bearing at the time logs or woody fragmenta were floated into the basins of deposition of the Chattanooga shale and the Cleveland member of the Ohio shale. Once within the marine environment, the material probably absorbed uranium with the formation of organo-uranium compounds such as exist in coals. It is suggested that a more systematic search for germaniferous coals in the vicinity of the Chattanooga shale and the Cleveland member of the Ohio shale might be rewarding. ?? 1955.

Thermal maturity of northern Appalachian Basin Devonian shales: Insights from sterane and terpane biomarkers

USGS Publications Warehouse

Hackley, Paul C.; Ryder, Robert T.; Trippi, Michael H.; Alimi, Hossein

2013-01-01

To better estimate thermal maturity of Devonian shales in the northern Appalachian Basin, eleven samples of Marcellus and Huron Shale were characterized via multiple analytical techniques. Vitrinite reflectance, Rock–Eval pyrolysis, gas chromatography (GC) of whole rock extracts, and GC–mass spectrometry (GCMS) of extract saturate fractions were evaluated on three transects that lie across previously documented regional thermal maturity isolines. Results from vitrinite reflectance suggest that most samples are immature with respect to hydrocarbon generation. However, bulk geochemical data and sterane and terpane biomarker ratios from GCMS suggest that almost all samples are in the oil window. This observation is consistent with the presence of thermogenic gas in the study area and higher vitrinite reflectance values recorded from overlying Pennsylvanian coals. These results suggest that vitrinite reflectance is a poor predictor of thermal maturity in early mature areas of Devonian shale, perhaps because reported measurements often include determinations of solid bitumen reflectance. Vitrinite reflectance interpretations in areas of early mature Devonian shale should be supplanted by evaluation of thermal maturity information from biomarker ratios and bulk geochemical data.

Estimating Emissions of Toxic Hydrocarbons from Natural Gas Production Sites in the Barnett Shale Region of Northern Texas.

PubMed

Marrero, Josette E; Townsend-Small, Amy; Lyon, David R; Tsai, Tracy R; Meinardi, Simone; Blake, Donald R

2016-10-04

Oil and natural gas operations have continued to expand and move closer to densely populated areas, contributing to growing public concerns regarding exposure to hazardous air pollutants. During the Barnett Shale Coordinated Campaign in October, 2013, ground-based whole air samples collected downwind of oil and gas sites revealed enhancements in several potentially toxic volatile organic compounds (VOCs) when compared to background values. Molar emissions ratios relative to methane were determined for hexane, benzene, toluene, ethylbenzene, and xylene (BTEX compounds). Using methane leak rates measured from the Picarro mobile flux plane (MFP) system and a Barnett Shale regional methane emissions inventory, the rates of emission of these toxic gases were calculated. Benzene emissions ranged between 51 ± 4 and 60 ± 4 kg h -1 . Hexane, the most abundantly emitted pollutant, ranged from 642 ± 45 to 1070 ± 340 kg h -1 . While observed hydrocarbon enhancements fall below federal workplace standards, results may indicate a link between emissions from oil and natural gas operations and concerns about exposure to hazardous air pollutants. The larger public health risks associated with the production and distribution of natural gas are of particular importance and warrant further investigation, particularly as the use of natural gas increases in the United States and internationally.

Organic / inorganic carbon content and isotope analysis of 3.1Ga Cleaverville Formation in Pilbara, Australia: Result of DXCL project

NASA Astrophysics Data System (ADS)

Miki, T.; Kiyokawa, S.; Ito, T.; Yamaguchi, K. E.; Ikehara, M.

2014-12-01

DXCL project was targeted for 3.2-3.1 Ga hydrothermal chert-black shale (Dixon Island Formation) and black shale-banded iron formation (Cleaverville Formation). CL3 core (200m long) was drilled from 1) upper part of Black Shale Member (35m thick) to 2) lower part of BIF Member (165m thick) of the Cleaverville Formation. Here, the BIF Member can be divided into three submembers; Greenish shale-siderite (50m thick), Magnetite-siderite (55m thick) and Black shale-siderite (60m) submembers. In this study, we used bulk samples and samples treated by hot hydrochloric acid in order to extract organic carbon. 　The Black shale Member consists of black carbonaceous　matter and fine grain quartz (< 100μm). Organic carbon content (Corg) of black shale is 1.2% in average and organic carbon isotope ratio (δ13Corg) is -31.4 to -28.7‰. On the other hand, inorganic carbon isotope ratio of siderite (δ13Ccarb) was -5.2 to +12.6‰. 　In the BIF Member, the Greenish shale-siderite submember is composed of well laminated greenish sideritic shale and white chert (<7mm thick), which is gradually increase from black shale of the Black shale Member through about 10m. Magnetite-siderite submember contains very fine magnetite lamination with inter-bedded greenish sideritic shale and siderite lamination. Hematite is identified near fractured part. The Black shale-siderite submember is composed of black shale, siderite and chert bands. 　1) Siderite layers of these three submembers showedδ13Ccarb value of -14.6 to -3.8‰. Corg and δ13Corg content are 0.2% and -18.3 to -0.3‰. 2) Siderite grains within greenish sideritic shales showedδ13Ccarb value of -12.9 to +15.0‰. 3) Black shale of Corg and δ13Corg content in the BIF Member are 0.1% and -36.3 to -17.1‰ respectively. 　We found great difference in values of δ13Ccarb of siderite. One is Corg-rich shale (up to +15.0‰) and the other is Corg-poor siderite layers (up to -3.8‰). The lighter value of siderite layers may be originated from precursor organic carbon which is strongly affected by biological activity.

Validation Results for Core-Scale Oil Shale Pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Staten, Josh; Tiwari, Pankaj

2015-03-01

This report summarizes a study of oil shale pyrolysis at various scales and the subsequent development a model for in situ production of oil from oil shale. Oil shale from the Mahogany zone of the Green River formation was used in all experiments. Pyrolysis experiments were conducted at four scales, powdered samples (100 mesh) and core samples of 0.75”, 1” and 2.5” diameters. The batch, semibatch and continuous flow pyrolysis experiments were designed to study the effect of temperature (300°C to 500°C), heating rate (1°C/min to 10°C/min), pressure (ambient and 500 psig) and size of the sample on product formation.more » Comprehensive analyses were performed on reactants and products - liquid, gas and spent shale. These experimental studies were designed to understand the relevant coupled phenomena (reaction kinetics, heat transfer, mass transfer, thermodynamics) at multiple scales. A model for oil shale pyrolysis was developed in the COMSOL multiphysics platform. A general kinetic model was integrated with important physical and chemical phenomena that occur during pyrolysis. The secondary reactions of coking and cracking in the product phase were addressed. The multiscale experimental data generated and the models developed provide an understanding of the simultaneous effects of chemical kinetics, and heat and mass transfer on oil quality and yield. The comprehensive data collected in this study will help advance the move to large-scale in situ oil production from the pyrolysis of oil shale.« less

Calorimetric determination of the heat of combustion of spent Green River shale at 978 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mraw, S.C.; Keweshan, C.F.

1987-08-01

A Calvet-type calorimeter was used to measure heats of combustion of spent Colorado oil shales. For Green River shale, the samples were members of a sink-float series spanning oil yields from 87 to 340 L . tonne/sup -1/. Shale samples (30-200 mg) are dropped into the calorimeter at high temperature, and a peak in the thermopile signal records the total enthalpy change of the sample between room temperature and the final temperature. Duplicate samples from the above sink-float series were first retorted at 773 K and then dropped separately into nitrogen and oxygen at 978 K. The resulting heats aremore » subtracted to give the heat of combustion, and the results are compared to values from classical bomb calorimetry. The agreement shows that the heats of combustion of the organic component are well understood but that question remain on the reactions of the mineral components.« less

Effects of Salinity and Confining Pressure on Hydration-Induced Fracture Propagation and Permeability of Mancos Shale

NASA Astrophysics Data System (ADS)

Zhang, Shifeng; Sheng, James J.

2017-11-01

Low-salinity water imbibition was considered an enhanced recovery method in shale oil/gas reservoirs due to the resulting hydration-induced fractures, as observed at ambient conditions. To study the effect of confining pressure and salinity on hydration-induced fractures, time-elapsed computerized tomography (CT) was used to obtain cross-sectional images of shale cores. Based on the CT data of these cross-sectional images, cut faces parallel to the core axial in the middle of the core and 3D fracture images were also reconstructed. To study the effects of confining pressure and salinity on shale pore fluid flowing, shale permeability was measured with Nitrogen (N2), distilled water, 4% KCl solution, and 8% KCl solution. With confining pressures increased to 2 MPa or more, either in distilled water or in KCl solutions of different salinities, fractures were observed to close instead to propagate at the end of the tests. The intrinsic permeabilities of #1 and #2 Mancos shale cores were 60.0 and 7000 nD, respectively. When tested with distilled water, the permeability of #1 shale sample with 20.0 MPa confining pressure loaded, and #2 shale sample with 2.5 MPa confining pressure loaded, decreased to 0.45 and 15 nD, respectively. Using KCl can partly mitigate shale permeability degradation. Compared to 4% KCl, 8% KCl can decrease more permeability damage. From this point of view, high salinity KCl solution should be required for the water-based fracturing fluid.

Shale gas characterization based on geochemical and geophysical analysis: Case study of Brown shale, Pematang formation, Central Sumatra Basin

NASA Astrophysics Data System (ADS)

Haris, A.; Nastria, N.; Soebandrio, D.; Riyanto, A.

2017-07-01

Geochemical and geophysical analyses of shale gas have been carried out in Brown Shale, Middle Pematang Formation, Central Sumatra Basin. The paper is aimed at delineating the sweet spot distribution of potential shale gas reservoir, which is based on Total Organic Carbon (TOC), Maturity level data, and combined with TOC modeling that refers to Passey and Regression Multi Linear method. We used 4 well data, side wall core and 3D pre-stack seismic data. Our analysis of geochemical properties is based on well log and core data and its distribution are constrained by a framework of 3D seismic data, which is transformed into acoustic impedance. Further, the sweet spot of organic-rich shale is delineated by mapping TOC, which is extracted from inverted acoustic impedance. Our experiment analysis shows that organic materials contained in the formation of Middle Pematang Brown Shale members have TOC range from 0.15 to 2.71 wt.%, which is classified in the quality of poor to very good. In addition, the maturity level of organic material is ranging from 373°C to 432°C, which is indicated by vitrinite reflectance (Ro) of 0.58. In term of kerogen type, this Brown shale formation is categorized as kerogen type of II I III, which has the potential to generate a mixture of gasIoil on the environment.

Effects of organic wastes on water quality from processing of oil shale from the Green River Formation, Colorado, Utah, and Wyoming

USGS Publications Warehouse

Leenheer, J.A.; Noyes, T.I.

1986-01-01

A series of investigations were conducted during a 6-year research project to determine the nature and effects of organic wastes from processing of Green River Formation oil shale on water quality. Fifty percent of the organic compounds in two retort wastewaters were identified as various aromatic amines, mono- and dicarboxylic acids phenols, amides, alcohols, ketones, nitriles, and hydroxypyridines. Spent shales with carbonaceous coatings were found to have good sorbent properties for organic constituents of retort wastewaters. However, soils sampled adjacent to an in situ retort had only fair sorbent properties for organic constituents or retort wastewater, and application of retort wastewater caused disruption of soil structure characteristics and extracted soil organic matter constituents. Microbiological degradation of organic solutes in retort wastewaters was found to occur preferentially in hydrocarbons and fatty acid groups of compounds. Aromatic amines did not degrade and they inhibited bacterial growth where their concentrations were significant. Ammonia, aromatic amines, and thiocyanate persisted in groundwater contaminated by in situ oil shale retorting, but thiosulfate was quantitatively degraded one year after the burn. Thiocyanate was found to be the best conservative tracer for retort water discharged into groundwater. Natural organic solutes, isolated from groundwater in contact with Green River Formation oil shale and from the White River near Rangely, Colorado, were readily distinguished from organic constituents in retort wastewaters by molecular weight and chemical characteristic differences. (USGS)

Bentonite deposits of the northern Black Hills district, Wyoming, Montana, and South Dakota

USGS Publications Warehouse

Knechtel, Maxwell M.; Patterson, Sam H.

1962-01-01

The northern Black Hills bentonite mining district includes parts of Crook County, Wyo., Carter County, Mont., and Butte County, S. Dak. Within this district, many beds of bentonite occur interspersed with sedimentary strata of Cretaceous age that have an average total thickness of about 3,000 feet and consist chiefly of marine shale, marl, and argillaceous sandstone. The bentonite beds occur in formations ranging upward from the Newcastle sandstone to the lower part of the Mitten black shale member of the Pierre shale. Tertiary (?) and Quaternary deposits of gravel, sand, and silt are present on extensive terraces, and deposits of such materials also extend along stream courses in all parts of the district. The overall geologic structure of the district is that of a broad northwestward- plunging anticline, in which the strata dip gently toward the northeast, north, and northwest. The overall structure is interrupted, however, by several subordinate folds which bring the bentonite beds to the surface repeatedly, so that large resources of bentonite are present under light overburden. The northern Black Hills district is an important source of commercial gel-forming sodium-type bentonite. During the period 1941-56 more than 5 million tons of raw bentonite was mined, most of which came from the Clay Spur bed near the top of the Mowry shale; a few thousand tons was mined from bed A in the Newcastle sandstone. Calcium-type bentonite occurs in bed B in the Mowry shale and in bed I at the base of the Mitten black shale member. Seven other beds are sufficiently thick and continuous to warrant consideration as prospective sources of bentonite for industrial use. Most of the bentonite produced is sold for use (a) as an ingredient of drilling mud; (b) for preparing metallurgical molding sand of superior dry strength; and (c) for the bonding material used in pelletizing taconite iron ore of the Lake Superior region. The results of drilling-mud and foundry-sand bonding-clay tests of several hundred samples, as well as analyses of selected samples, chiefly by X-ray, differential thermal, base exchange and spectrographic methods, are included in this report.

Organic pi-stacking Semiconducting Material: Design, Synthesis and the Analysis of Structure and Properties

NASA Astrophysics Data System (ADS)

Wilkinson, Taylor Marie

Oil shales are naturally occurring heterogeneous composites with micro-scale, micro-structural variations. They may be found throughout the world, with large deposits located in the United States; shales are composed of organic matter known as kerogen, clays, calcite, quartz, and other minerals. Typically their microstructure consists of a composite network where the organic matter is housed in open and closed pores between different mineral phases that range in size from sub-micron to several microns. Currently, it is unknown how the micro-scale heterogeneity of the shale will impact hydraulic fracture, which is the key extraction technique used for these materials. In this thesis, high-resolution topographic and modulus maps were collected from oil shales with the use of new nanoindentation techniques in order to characterize the micro-scale, micro-structural variations that are typical for these materials. Dynamic modulus mapping allows for substantially higher spatial resolution of properties across grains and intragranular regions of kerogen than has previously been produced with standard quasistatic indentation methods. For accurate scanning, surface variations were minimized to maintain uniform contact of the tip and appropriate quasi-static and dynamic forces were used to maintain displacement amplitudes that avoid plastic deformation of the sample. Sample preparation to minimize surface roughness was completed with the use of focused ion beam milling, however, some variation was still noted. Due to the large changes in modulus values between the constituents of the shale, there were variations in the recorded displacement amplitude values as well. In order to distinguish biased data due to surface topography or a lack of displacement amplitude, filtering techniques were developed, optimization and implemented. Variations in surface topography, which resulted in the indenter tip not being able to accurately resolve surface features, and inadequate displacement amplitude values that prohibit differentiation between material changes and the noise floor of the machine, were removed. These filters resulted in a more valid interpretation of the micro-scale, micro-structural features and arrangement, as well as the mechanical properties, that are common to oil shales.

The Eastern Gas Shales Project (EGSP) Data System: A case study in data base design, development, and application

USGS Publications Warehouse

Dyman, T.S.; Wilcox, L.A.

1983-01-01

The U.S. Geological Survey and Petroleum Information Corporation in Denver, Colorado, developed the Eastern Gas Shale Project (EGSP)Data System for the U.S. Department of Energy, Morgantown, West Virginia. Geological, geochemical, geophysical, and engineering data from Devonian shale samples from more than 5800 wells and outcrops in the Appalachian basin were edited and converted to a Petroleum Information Corporation data base. Well and sample data may be retrieved from this data system to produce (1)production-test summaries by formation and well location; (2)contoured isopach, structure, and trendsurface maps of Devonian shale units; (3)sample summary reports for samples by location, well, contractor, and sample number; (4)cross sections displaying digitized log traces, geochemical, and lithologic data by depth for wells; and (5)frequency distributions and bivariate plots. Although part of the EGSP Data System is proprietary, and distribution of complete well histories is prohibited by contract, maps and aggregated well-data listings are being made available to the public through published reports. ?? 1983 Plenum Publishing Corporation.

A Comparative Study of T1 and T2 Relaxation in Shale

NASA Astrophysics Data System (ADS)

Keating, K.; Obasi, C. C.; Pashin, J. C.

2015-12-01

Nuclear magnetic resonance (NMR) relaxation measurement have been used extensively in petroleum and, more recently, in groundwater resource evaluation to estimate the porosity, pore-size distributions, permeability, fluid saturation, and fluid mobility. In shale, the transverse decay rate of NMR signal is sensitive to the microporosity, but is also affected by the paramagnetic contributions of clay and other iron-bearing minerals. Furthermore, contrasts in the magnetic susceptibility of the mineral matrix and pore fluids that result in an inhomogeneous magnetic field within the pore space results in an extra term in transverse relaxation. These issues can cause errors in NMR-based estimates of pore-size distribution and permeability. In this study we compare T1 and T2 relaxation time distributions in order to study the molecular mechanism of relaxation in brine-saturated mixtures of clay and other common minerals. We collected measurements on a range of mixtures of clay minerals common in shale (illite, glauconite, celadonite, chamosite, montmorillonite and kaolinite) and pyrite. To constrain the interpretation of the NMR data, we measured the magnetic susceptibility and surface area of all samples. We are confident that by accounting for the presence and variations of clay and pyrite in shale, we can substantially improve both the NMR estimate of pore-size distribution and permeability.

Feasibility Assessment of CO2 Sequestration and Enhanced Recovery in Gas Shale Reservoirs

NASA Astrophysics Data System (ADS)

Vermylen, J. P.; Hagin, P. N.; Zoback, M. D.

2008-12-01

CO2 sequestration and enhanced methane recovery may be feasible in unconventional, organic-rich, gas shale reservoirs in which the methane is stored as an adsorbed phase. Previous studies have shown that organic-rich, Appalachian Devonian shales adsorb approximately five times more carbon dioxide than methane at reservoir conditions. However, the enhanced recovery and sequestration concept has not yet been tested for gas shale reservoirs under realistic flow and production conditions. Using the lessons learned from previous studies on enhanced coalbed methane (ECBM) as a starting point, we are conducting laboratory experiments, reservoir modeling, and fluid flow simulations to test the feasibility of sequestration and enhanced recovery in gas shales. Our laboratory work investigates both adsorption and mechanical properties of shale samples to use as inputs for fluid flow simulation. Static and dynamic mechanical properties of shale samples are measured using a triaxial press under realistic reservoir conditions with varying gas saturations and compositions. Adsorption is simultaneously measured using standard, static, volumetric techniques. Permeability is measured using pulse decay methods calibrated to standard Darcy flow measurements. Fluid flow simulations are conducted using the reservoir simulator GEM that has successfully modeled enhanced recovery in coal. The results of the flow simulation are combined with the laboratory results to determine if enhanced recovery and CO2 sequestration is feasible in gas shale reservoirs.

Implications of contact metamorphism of Mancos Shale for critical zone processes

NASA Astrophysics Data System (ADS)

Navarre-Sitchler, A.

2016-12-01

Bedrock lithology imparts control on some critical zone processes, for example rates and extent of chemical weathering, solute release though mineral dissolution, and water flow. Bedrock can be very heterogeneous resulting in spatial variability of these processes throughout a catchment. In the East River watershed outside of Crested Butte, Colorado, bedrock is dominantly comprised of the Mancos Shale; a Cretaceous aged, organic carbon rich marine shale. However, in some areas the Mancos Shale appears contact metamorphosed by nearby igneous intrusions resulting in a potential gradient in lithologic change in part of the watershed where impacts of lithology on critical zone processes can be evaluated. Samples were collected in the East River valley along a transect from the contact between the Tertiary Gothic Mountain laccolith of the Mount Carbon igneous system and the underlying Manocs shale. Porosity of these samples was analyzed by small-angle and ultra small-angle neutron scattering. Results indicate contact metamorphism decreases porosity of the shale and changes the pore shape from slightly anisotropic pores aligned with bedding in the unmetamorphosed shale to isotropic pores with no bedding alignment in the metamorphosed shales. The porosity analysis combined with clay mineralogy, surface area, carbon content and oxidation state, and solute release rates determined from column experiments will be used to develop a full understanding of the impact of contact metamorphism on critical zone processes in the East River.

Comparison of Pore Fractal Characteristics Between Marine and Continental Shales

NASA Astrophysics Data System (ADS)

Liu, Jun; Yao, Yanbin; Liu, Dameng; Cai, Yidong; Cai, Jianchao

Fractal characterization offers a quantitative evaluation on the heterogeneity of pore structure which greatly affects gas adsorption and transportation in shales. To compare the fractal characteristics between marine and continental shales, nine samples from the Lower Silurian Longmaxi formation in the Sichuan basin and nine from the Middle Jurassic Dameigou formation in the Qaidam basin were collected. Reservoir properties and fractal dimensions were characterized for all the collected samples. In this study, fractal dimensions were originated from the Frenkel-Halsey-Hill (FHH) model with N2 adsorption data. Compared to continental shale, marine shale has greater values of quartz content, porosity, specific surface area and total pore volume but lower level of clay minerals content, permeability, average pore diameter and methane adsorption capacity. The quartz in marine shale is mostly associated with biogenic origin, while that in continental shale is mainly due to terrigenous debris. The N2 adsorption-desorption isotherms exhibit that marine shale has fewer inkbottle-shaped pores but more plate-like and slit-shaped pores than continental shale. Two fractal dimensions (D1 and D2) were obtained at P/Po of 0-0.5 and 0.5-1. The dimension D2 is commonly greater than D1, suggesting that larger pores (diameter >˜ 4nm) have more complex structures than small pores (diameter <˜ 4nm). The fractal dimensions (both D1 and D2) positively correlate to clay minerals content, specific surface area and methane adsorption capacity, but have negative relationships with porosity, permeability and average pore diameter. The fractal dimensions increase proportionally with the increasing quartz content in marine shale but have no obvious correlation with that in continental shale. The dimension D1 is correlative to the TOC content and permeability of marine shale at a similar degree with dimension D2, while the dimension D1 is more sensitive to those of continental shale than dimension D2. Compared with dimension D2, for two shales, dimension D1 is better associated with the content of clay minerals but has worse correlations with the specific surface area and average pore diameter.

An evaluation of water quality in private drinking water wells near natural gas extraction sites in the Barnett Shale formation.

PubMed

Fontenot, Brian E; Hunt, Laura R; Hildenbrand, Zacariah L; Carlton, Doug D; Oka, Hyppolite; Walton, Jayme L; Hopkins, Dan; Osorio, Alexandra; Bjorndal, Bryan; Hu, Qinhong H; Schug, Kevin A

2013-09-03

Natural gas has become a leading source of alternative energy with the advent of techniques to economically extract gas reserves from deep shale formations. Here, we present an assessment of private well water quality in aquifers overlying the Barnett Shale formation of North Texas. We evaluated samples from 100 private drinking water wells using analytical chemistry techniques. Analyses revealed that arsenic, selenium, strontium and total dissolved solids (TDS) exceeded the Environmental Protection Agency's Drinking Water Maximum Contaminant Limit (MCL) in some samples from private water wells located within 3 km of active natural gas wells. Lower levels of arsenic, selenium, strontium, and barium were detected at reference sites outside the Barnett Shale region as well as sites within the Barnett Shale region located more than 3 km from active natural gas wells. Methanol and ethanol were also detected in 29% of samples. Samples exceeding MCL levels were randomly distributed within areas of active natural gas extraction, and the spatial patterns in our data suggest that elevated constituent levels could be due to a variety of factors including mobilization of natural constituents, hydrogeochemical changes from lowering of the water table, or industrial accidents such as faulty gas well casings.

Experimental Determination of the Fracture Toughness and Brittleness of the Mancos Shale, Utah.

NASA Astrophysics Data System (ADS)

Chandler, Mike; Meredith, Phil; Crawford, Brian

2013-04-01

The hydraulic fracturing of Gas-Shales has become a topic of interest since the US Shale Gas Revolution, and is increasingly being investigated across Europe. A significant issue during hydraulic fracturing is the risk of fractures propagating further than desired into aquifers or faults. This occured at Preese Hall, UK in April and May 2011 when hydraulic fractures propagated into an adjacent fault causing 2.3ML and 1.7ML earthquakes [1]. A rigorous understanding of how hydraulic fractures propagate under in-situ conditions is therefore important for treatment design, both to maximise gas accessed, and to minimise risks due to fracture overextension. Fractures will always propagate along the path of least resistance, but the direction and extent of this path is a complex relationship between the in-situ stress-field, the anisotropic mechanical properties of the rock, and the pore and fracturing pressures [2]. It is possible to estimate the anisotropic in-situ stress field using an isolated-section hydraulic fracture test, and the pore-pressure using well logs. However, the anisotropic mechanical properties of gas-shales remain poorly constrained, with a wide range of reported values. In particular, there is an extreme paucity of published data on the Fracture Toughness of soft sediments such as shales. Mode-I Fracture Toughness is a measure of a material's resistance to dynamic tensile fracture propagation. Defects such as pre-existing microcracks and pores in a material can induce high local stress concentrations, causing fracture propagation and material failure under substantially lower stress than its bulk strength. The mode-I stress intensity factor, KI, quantifies the concentration of stress at the crack tip. For linear elastic materials the Fracture Toughness is defined by the critical value of this stress intensity factor; KIc, beyond which rapid catastrophic crack growth occurs. However, rocks such as shales are relatively ductile and display significant non-linearity. This produces hysteresis during cyclic loading, allowing for the calculation of a brittleness coefficient using the residual displacement after successive loading cycles. This can then be used to define a brittleness corrected Fracture Toughness, KIcc. We report anisotropic KIcc values and a variety of supporting measurements made on the Mancos Shale in the three principle Mode-I crack orientations (Arrester, Divider and Short-Transverse) using a modified Short-Rod sample geometry. The Mancos is an Upper Cretaceous shale from western Colorado and eastern Utah with a relatively high siliclastic content for a gas target formation. The Short-Rod methodology involves the propagation of a crack through a triangular ligament in a chevron-notched cylindrical sample [3]. A very substantial anisotropy is observed in the loading curves and KIcc values for the three crack orientations, with the Divider orientation having KIcc values 25% higher than the other orientations. The measured brittleness for these Mancos shales is in the range 1.5-2.1; higher than for any other rocks we have found in the literature. This implies that the material is extremely non-linear. Increases in KIcc with increasing confining pressure are also investigated, as Shale Gas reservoirs occur at depths where confining pressure may be as high as 35MPa and temperature as high as 100oC. References [1] C.A. Green, P. Styles & B.J. Baptie, "Preese Hall Shale Gas Fracturing", Review & Recommendations for Induced Seismic Mitigation, 2012. [2] N.R. Warpinski & M.B. Smith, "Rock Mechanics and Fracture Geometry", Recent advances in Hydraulic Fracturing, SPE Monograms, Vol. 12, pp. 57-80, 1990. [3] F. Ouchterlony, "International Society for Rock Mechanics Commision on Testing Methods: Suggested Methods for Determining the Fracture Toughness of Rock", International Journal of Rock Mechanics and Mining Science & Geomechanics Abstracts, Vol. 25, 1988.

Shale: an overlooked option for US nuclear waste disposal

USGS Publications Warehouse

Neuzil, Christopher E.

2014-01-01

Toss a dart at a map of the United States and, more often than not, it will land where shale can be found underground. A drab, relatively featureless sedimentary rock that historically attracted little interest, shale (as used here, the term includes clay and a range of clay-rich rocks) is entering Americans’ consciousness as a new source of gas and oil. But shale may also offer something entirely different—the ability to safely and permanently house high-level nuclear waste.

Effect of thermal maturity on remobilization of molybdenum in black shales

NASA Astrophysics Data System (ADS)

Ardakani, Omid H.; Chappaz, Anthony; Sanei, Hamed; Mayer, Bernhard

2016-09-01

Molybdenum (Mo) concentrations in sedimentary records have been widely used as a method to assess paleo-redox conditions prevailing in the ancient oceans. However, the potential effects of post-depositional processes, such as thermal maturity and burial diagenesis, on Mo concentrations in organic-rich shales have not been addressed, compromising its use as a redox proxy. This study investigates the distribution and speciation of Mo at various thermal maturities in the Upper Ordovician Utica Shale from southern Quebec, Canada. Samples display maturities ranging from the peak oil window (VRo ∼ 1%) to the dry gas zone (VRo ∼ 2%). While our data show a significant correlation between total organic carbon (TOC) and Mo (R2 = 0.40, n = 28, P < 0.0003) at lower thermal maturity, this correlation gradually deteriorates with increasing thermal maturity. Intervals within the thermally overmature section of the Utica Shale that contain elevated Mo levels (20-81 ppm) show petrographic and sulfur isotopic evidence of thermochemical sulfate reduction (TSR) along with formation of recrystallized pyrite. X-ray Absorption Fine Structure spectroscopy (XAFS) was used to determine Mo speciation in samples from intervals with elevated Mo contents (>30 ppm). Our results show the presence of two Mo species: molybdenite Mo(IV)S2 (39 ± 5%) and Mo(VI)-Organic Matter (61 ± 5%). This new evidence suggests that at higher thermal maturities, TSR causes sulfate reduction coupled with oxidation of organic matter (OM). This process is associated with H2S generation and pyrite formation and recrystallization. This in turn leads to the remobilization of Mo and co-precipitation of molybdenite with TSR-derived carbonates in the porous intervals. This could lead to alteration of the initial sedimentary signature of Mo in the affected intervals, hence challenging its use as a paleo-redox proxy in overmature black shales.

43 CFR 3926.10 - Conversion of an R, D and D lease to a commercial lease.

Code of Federal Regulations, 2011 CFR

2011-10-01

... (Continued) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE LEASING...) Documentation that there have been commercial quantities of oil shale produced from the lease, including the... application, in whole or in part, if it determines that: (1) There have been commercial quantities of shale...

Water use competition scenarios during the upcoming development of shale gas reserves across the Mexican Eagle Ford play Image already added

NASA Astrophysics Data System (ADS)

Arciniega, S.; Breña-Naranjo, J. A.; Hernaández Espriú, A.; Pedrozo-Acuña, A.

2017-12-01

Mexico has significant shale oil and gas resources mainly contained within the Mexican part of the Eagle Ford play (Mex-EF), in the Burgos Basin located in northern Mexico. Over the last years, concerns about the water use associated to shale gas development using hydraulic fracturing (HF) have been increasing in the United States and Canada. In Mexico, the recent approval of a new energy bill allows the exploration, development and production of shale gas reserves. However, several of the Mexican shale gas resources are located in water-limited environments, such as the Mex-EF. The lack of climate and hydrological gauging stations across this region constrains information about how much freshwater from surface and groundwater sources is available and whether its interannual water availability is sufficient to satisfy the water demand by other users (agricultural, urban) of the region This work projects the water availability across the Mex-EF and its water use derived from the expansion of unconventional gas developments over the next 15 years. Water availability is estimated using a water balance approach, where the irrigation's groundwater withdrawals time series were reconstructed using remote sensing products (vegetation index and hydrological outputs from LSMs) and validated with in situ observed water use at three different irrigation districts of the region. Water use for HF is inferred using type curves of gas production, flowback and produced (FP) water and curves of drilled wells per year from the US experience, mainly from the Texas-EF play. Scenarios that combine freshwater use and FP water use for HF are developed and the spatial distribution of HF well pads is projected using random samples with a range of wells' horizontal length. This proposed methodology can be applied in other shale formations of the world under water stress and it also helps to determine whether water scarcity can be a limiting factor for the shale gas industry over the next decades. Image already added

Naphthenic acids in groundwater overlying undeveloped shale gas and tight oil reservoirs.

PubMed

Ahad, Jason M E; Pakdel, Hooshang; Lavoie, Denis; Lefebvre, René; Peru, Kerry M; Headley, John V

2018-01-01

The acid extractable organics (AEOs) containing naphthenic acids (NAs) in groundwater overlying undeveloped shale gas (Saint-Édouard region) and tight oil (Haldimand sector, Gaspé) reservoirs in Québec, Canada, were analysed using high resolution Orbitrap mass spectrometry and thermal conversion/elemental analysis - isotope ratio mass spectrometry. As classically defined by C n H 2n+Z O 2 , the most abundant NAs detected in the majority of groundwater samples were straight-chain (Z = 0) or monounsaturated (Z = -2) C 16 and C 18 fatty acids. Several groundwater samples from both study areas, however, contained significant proportions of presumably alicyclic bicyclic NAs (i.e., Z = -4) in the C 10 -C 18 range. These compounds may have originated from migrated waters containing a different distribution of NAs, or are the product of in situ microbial alteration of shale organic matter and petroleum. In most groundwater samples, intramolecular carbon isotope values generated by pyrolysis (δ 13 C pyr ) of AEOs were on average around 2-3‰ heavier than those generated by bulk combustion (δ 13 C) of AEOs, providing further support for microbial reworking of subsurface organic carbon. Although concentrations of AEOs were very low (<2.0 mg/L), the detection of potentially toxic bicyclic acids in groundwater overlying unconventional hydrocarbon reservoirs points to a natural background source of organic contaminants prior to any large-scale commercial hydrocarbon development. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

Experimental Investigation of Mechanical Properties of Black Shales after CO2-Water-Rock Interaction

PubMed Central

Lyu, Qiao; Ranjith, Pathegama Gamage; Long, Xinping; Ji, Bin

2016-01-01

The effects of CO2-water-rock interactions on the mechanical properties of shale are essential for estimating the possibility of sequestrating CO2 in shale reservoirs. In this study, uniaxial compressive strength (UCS) tests together with an acoustic emission (AE) system and SEM and EDS analysis were performed to investigate the mechanical properties and microstructural changes of black shales with different saturation times (10 days, 20 days and 30 days) in water dissoluted with gaseous/super-critical CO2. According to the experimental results, the values of UCS, Young’s modulus and brittleness index decrease gradually with increasing saturation time in water with gaseous/super-critical CO2. Compared to samples without saturation, 30-day saturation causes reductions of 56.43% in UCS and 54.21% in Young’s modulus for gaseous saturated samples, and 66.05% in UCS and 56.32% in Young’s modulus for super-critical saturated samples, respectively. The brittleness index also decreases drastically from 84.3% for samples without saturation to 50.9% for samples saturated in water with gaseous CO2, to 47.9% for samples saturated in water with super-critical carbon dioxide (SC-CO2). SC-CO2 causes a greater reduction of shale’s mechanical properties. The crack propagation results obtained from the AE system show that longer saturation time produces higher peak cumulative AE energy. SEM images show that many pores occur when shale samples are saturated in water with gaseous/super-critical CO2. The EDS results show that CO2-water-rock interactions increase the percentages of C and Fe and decrease the percentages of Al and K on the surface of saturated samples when compared to samples without saturation. PMID:28773784

Organoporosity Evaluation of Shale: A Case Study of the Lower Silurian Longmaxi Shale in Southeast Chongqing, China

PubMed Central

Chen, Fangwen; Lu, Shuangfang; Ding, Xue

2014-01-01

The organopores play an important role in determining total volume of hydrocarbons in shale gas reservoir. The Lower Silurian Longmaxi Shale in southeast Chongqing was selected as a case to confirm the contribution of organopores (microscale and nanoscale pores within organic matters in shale) formed by hydrocarbon generation to total volume of hydrocarbons in shale gas reservoir. Using the material balance principle combined with chemical kinetics methods, an evaluation model of organoporosity for shale gas reservoirs was established. The results indicate that there are four important model parameters to consider when evaluating organoporosity in shale: the original organic carbon (w(TOC0)), the original hydrogen index (I H0), the transformation ratio of generated hydrocarbon (F(R o)), and the organopore correction coefficient (C). The organoporosity of the Lower Silurian Longmaxi Shale in the Py1 well is from 0.20 to 2.76%, and the average value is 1.25%. The organoporosity variation trends and the residual organic carbon of Longmaxi Shale are consistent in section. The residual organic carbon is indicative of the relative levels of organoporosity, while the samples are in the same shale reservoirs with similar buried depths. PMID:25184155

Germanium and uranium in coalified wood from Upper Devonian black shale

USGS Publications Warehouse

Breger, Irving A.; Schopf, James M.

1954-01-01

Microscopic study of black, vitreous, carbonaceous material occurring in the Chattanooga shale in Tennessee and in the Cleveland member of the Ohio shale in Ohio has revealed coalified woody plant tissue. Some samples have shown sufficient detail to be identified with the genus Callixylon. Similar material has been reported in the literature as "bituminous" or "asphaltic" stringers. Spectrographic analyses of the ash from the coalified wood have shown unusually high percentages of germanium, uranium, vanadium, and nickel. The inverse relationship between uranium and germanium in the ash and the ash content of various samples shows an association of these elements with the organic constituents of the coal. On the basis of geochemical considerations, it seems most probable that the wood or coalified wood was germanium-bearing at the time logs or woody fragments were floated into the basins of deposition of the Chattanooga shale and the Cleveland member of the Ohio shale. Once within the marine environment, the material probably absorbed uranium with the formation of organo-uranium compounds such as have been found to exist in coals. It is suggested that a more systematic search for germaniferous coals in the vicinity of the Chattanooga shale and the Cleveland member of the Ohio shale might be rewarding.

How microfracture roughness can be used to distinguish between exhumed cracks and in-situ flow paths in shales

NASA Astrophysics Data System (ADS)

Pluymakers, Anne; Kobchenko, Maya; Renard, François

2017-01-01

Flow through fractures in shales is of importance to many geoengineering purposes. Shales are not only caprocks to hydrocarbon reservoirs and nuclear waste or CO2 storage sites, but also potential source and reservoir rocks for hydrocarbons. The presence of microfractures in shales controls their permeability and transport properties. Using X-ray micro-tomography and white light interferometry we scanned borehole samples obtained from 4 km depth in the Pomeranian shales in Poland. These samples contain open exhumation/drying cracks as well as intact vein-rock interfaces plus one striated slip surface. At micron resolution and above tensile drying cracks exhibit a power-law roughness with a scaling exponent, called the Hurst exponent H, of 0.3. At sub-micron resolution we capture the properties of the clay interface only, with H = 0.6. In contrast, the in-situ formed veins and slip surface exhibit H = 0.4-0.5, which is deemed representative for in-situ fractures. These results are discussed in relation to the shale microstructure and linear elastic fracture mechanics theory. The data imply that the Hurst roughness exponent can be used as a microstructural criterion to distinguish between exhumation and in-situ fractures, providing a step forward towards the characterization of potential flow paths at depth in shales.

Screening for Dissolved Methane in Groundwater Across Texas Shale Plays

NASA Astrophysics Data System (ADS)

Nicot, J. P.; Mickler, P. J.; Hildenbrand, Z.; Larson, T.; Darvari, R.; Uhlman, K.; Smyth, R. C.; Scanlon, B. R.

2014-12-01

There is considerable interest in methane concentrations in groundwater, particularly as they relate to hydraulic fracturing in shale plays. Recent studies of aquifers in the footprint of several gas plays across the US have shown that (1) dissolved thermogenic methane may or may not be present in the shallow groundwater and (2) shallow thermogenic methane may be naturally occurring and emplaced through mostly vertical migration over geologic time and not necessarily a consequence of recent unconventional gas production. We are currently conducting a large sampling campaign across the state of Texas to characterize shallow methane in fresh-water aquifers overlying shale plays and other tight formations. We collected a total of ~800 water samples, ~500 in the Barnett, ~150 in the Eagle Ford, ~80 in the Haynesville shale plays as well as ~50 in the Delaware Basin of West Texas. Preliminary analytical results suggest that dissolved methane is not widespread in shallow groundwater and that, when present at concentrations exceeding 10 mg/L, it is often of thermogenic origin according to the isotopic signature and to the presence of other light hydrocarbons. The Barnett Shale contains a large methane hotspot (~ 2 miles wide) along the Hood-Parker county line which is likely of natural origin whereas the Eagle Ford and Haynesville shales, neglecting microbial methane, show more distributed methane occurrences. Samples from the Delaware Basin show no methane except close to blowouts.

The Kingak shale of northern Alaska-regional variations in organic geochemical properties and petroleum source rock quality

USGS Publications Warehouse

Magoon, L.B.; Claypool, G.E.

1984-01-01

The Kingak Shale, a thick widespread rock unit in northern Alaska that ranges in age from Early Jurassic through Early Cretaceous, has adequate to good oil source rock potential. This lenticular-shaped rock unit is as much as 1200 m thick near the Jurassic shelf edge, where its present-day burial depth is about 5000 m. Kingak sediment, transported in a southerly direction, was deposited on the then marine continental shelf. The rock unit is predominantly dark gray Shale with some interbeds of thick sandstone and siltstone. The thermal maturity of organic matter in the Kingak Shale ranges from immature (2.0%R0) in the Colville basin toward the south. Its organic carbon and hydrogen contents are highest in the eastern part of northern Alaska south of and around the Kuparuk and Prudhoe Bay oil fields. Carbon isotope data of oils and rock extracts indicate that the Kingak Shale is a source of some North Slope oil, but is probably not the major source. ?? 1984.

Sea Level and Paleoenvironment Control on Late Ordovician Source Rocks, Hudson Bay Basin, Canada

NASA Astrophysics Data System (ADS)

Zhang, S.; Hefter, J.

2009-05-01

Hudson Bay Basin is one of the largest Paleozoic sedimentary basins in North America, with Southampton Island on its north margin. The lower part of the basin succession comprises approximately 180 to 300 m of Upper Ordovician strata including Bad Cache Rapids and Churchill River groups and Red Head Rapids Formation. These units mainly comprise carbonate rocks consisting of alternating fossiliferous limestone, evaporitic and reefal dolostone, and minor shale. Shale units containing extremely high TOC, and interpreted to have potential as petroleum source rocks, were found at three levels in the lower Red Head Rapids Formation on Southampton Island, and were also recognized in exploration wells from the Hudson Bay offshore area. A study of conodonts from 390 conodont-bearing samples from continuous cores and well cuttings from six exploration wells in the Hudson Bay Lowlands and offshore area (Comeault Province No. 1, Kaskattama Province No. 1, Pen Island No. 1, Walrus A-71, Polar Bear C-11 and Narwhal South O-58), and about 250 conodont-bearing samples collected from outcrops on Southampton Island allows recognition of three conodont zones in the Upper Ordovician sequence, namely (in ascendant sequence) Belodina confluens, Amorphognathus ordovicicus, and Rhipidognathus symmetricus zones. The three conodont zones suggest a cycle of sea level changes of rising, reaching the highest level, and then falling during the Late Ordovician. Three intervals of petroleum potential source rock are within the Rhipidognathus symmetricus Zone in Red Head Rapids Formation, and formed in a restricted anoxic and hypersaline condition during a period of sea level falling. This is supported by the following data: 1) The conodont Rhipidognathus symmetricus represents the shallowest Late Ordovician conodont biofacies and very shallow subtidal to intertidal and hypersaline condition. This species has the greatest richness within the three oil shale intervals to compare other parts of Red Head Rapids Formation. 2) Type I kerogen is normally formed in quiet, oxygen-deficient, shallow water environment. Rock-Eval6 data from 40 samples of the three oil shale intervals, collected from outcrops on Southampton Island, demonstrate that the proportion of Type I kerogen gradually increases in the mixed Type I-Type II kerogen from the lower to upper oil shale intervals. 3) Pristane/phytane ratio can be used as a paleoenvironment indicator. The low ratios in the three oil shale intervals range from 0.5 to 0.9 and indicate anoxic and hypersaline conditions. In addition, the presence of isorenieratene derivatives from green phototrophic sulfur bacteria (Chlorobiaceae), with highest relative concentrations in the lower oil shale intervals, points to anoxia reaching into the photic zone of the water column.

43 CFR 3922.10 - Application processing fee.

Code of Federal Regulations, 2011 CFR

2011-10-01

... MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE LEASING Application Processing... process for a competitive oil shale lease is as follows: (1) The applicant nominating the tract for...

Major and trace elements in Mahogany zone oil shale in two cores from the Green River Formation, piceance basin, Colorado

USGS Publications Warehouse

Tuttle, M.L.; Dean, W.E.; Parduhn, N.L.

1983-01-01

The Parachute Creek Member of the lacustrine Green River Formation contains thick sequences of rich oil-shale. The richest sequence and the richest oil-shale bed occurring in the member are called the Mahogany zone and the Mahogany bed, respectively, and were deposited in ancient Lake Uinta. The name "Mahogany" is derived from the red-brown color imparted to the rock by its rich-kerogen content. Geochemical abundance and distribution of eight major and 18 trace elements were determined in the Mahogany zone sampled from two cores, U. S. Geological Survey core hole CR-2 and U. S. Bureau of Mines core hole O1-A (Figure 1). The oil shale from core hole CR-2 was deposited nearer the margin of Lake Uinta than oil shale from core hole O1-A. The major- and trace-element chemistry of the Mahogany zone from each of these two cores is compared using elemental abundances and Q-mode factor modeling. The results of chemical analyses of 44 CR-2 Mahogany samples and 76 O1-A Mahogany samples are summarized in Figure 2. The average geochemical abundances for shale (1) and black shale (2) are also plotted on Figure 2 for comparison. The elemental abundances in the samples from the two cores are similar for the majority of elements. Differences at the 95% probability level are higher concentrations of Ca, Cu, La, Ni, Sc and Zr in the samples from core hole CR-2 compared to samples from core hole O1-A and higher concentrations of As and Sr in samples from core hole O1-A compared to samples from core hole CR-2. These differences presumably reflect slight differences in depositional conditions or source material at the two sites. The Mahogany oil shale from the two cores has lower concentrations of most trace metals and higher concentrations of carbonate-related elements (Ca, Mg, Sr and Na) compared to the average shale and black shale. During deposition of the Mahogany oil shale, large quantities of carbonates were precipitated resulting in the enrichment of carbonate-related elements and dilution of most trace elements as pointed out in several previous studies. Q-mode factor modeling is a statistical method used to group samples on the basis of compositional similarities. Factor end-member samples are chosen by the model. All other sample compositions are represented by varying proportions of the factor end-members and grouped as to their highest proportion. The compositional similarities defined by the Q-mode model are helpful in understanding processes controlling multi-element distributions. The models for each core are essentially identical. A four-factor model explains 70% of the variance in the CR-2 data and 64% of the O1-A data (the average correlation coefficients are 0. 84 and 0. 80, respectively). Increasing the number of factors above 4 results in the addition of unique instead of common factors. Table I groups the elements based on high factor-loading scores (the amount of influence each element has in defining the model factors). Similar elemental associations are found in both cores. Elemental abundances are plotted as a function of core depth using a five-point weighted moving average of the original data to smooth the curve (Figure 3 and 4). The plots are grouped according to the four factors defined by the Q-mode models and show similar distributions for elements within the same factor. Factor 1 samples are rich in most trace metals. High oil yield and the presence of illite characterize the end-member samples for this factor (3, 4) suggesting that adsorption of metals onto clay particles or organic matter is controlling the distribution of the metals. Precipitation of some metals as sulfides is possible (5). Factor 2 samples are high in elements commonly associated with minerals of detrital or volcanogenic origin. Altered tuff beds and lenses are prevalent within the Mahogany zone. The CR-2 end-member samples for this factor contain analcime (3) which is an alteration product within the tuff beds of the Green River Formation. Th

The source rock potential of the Karroo coals of the south western Rift Basin of Tanzania

NASA Astrophysics Data System (ADS)

Mpanju, F.; Ntomola, S.; Kagya, M.

For many years geoscientists believed that coals (Type III Kerogen) generate gas only. The geochemical study of Durand and Parrante ( Petrolum Geochemistry and Exploration of Europe, pp. 255-265, 1983) revealed that coals have reasonable potential for oil generation. On this basis forty outcrop samples of Lower and Upper Permian age, i.e. coals and carbonaceous shales, were collected from the south western Rift Basin of Tanzania. The aim of the study was to determine the richness, type, maturity and hydrocarbon potential of the above samples. These samples were subjected to both geochemical and petrological analyses. Geochemical analyses included solvent extraction, TOC, GC, GC-MS and pyrolysis. The petrological analysis included vitrinite reflectance, spore fluorescence and maceral content. The geochemical analyses showed all samples to be rich in organic matter of Types II and III and samples from Songwe Kiwira, Namwele, Mbamba Bay, Njuga and Mhukuru coalfields were in an early mature-mature stage of hydrocarbon generation. Whereas samples from Ketewaka and Ngaka coalfields showed a GC-trace of early generated waxy oil. All samples contained organic matter derived from terrestrial material which was deposited under oxic environment. The Hydrogen Index of most coals and carbonaceous shales was greater than 200 indicating that they can generate oil or light oil. Petrological observations showed all samples to be in the range of 0.47-0.67% Ro and some of them were rich in both liptinite and vitrinite macerals. From both geochemical and petrological observations it was concluded that the Lower and Upper Permian coals and carbonaceous shales under study are probably capable of generating oil. The oil generated has the same characteristics as that generated by Cretaceous and Tertiary coals discovered from other parts of the world, i.e. Adjuna and Kutei Basins in Indonesia and the Gippsland Basin in Australia (Kirkland et al., AAPG Bull.71, 577, 1987).

Appraisal of transport and deformation in shale reservoirs using natural noble gas tracers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heath, Jason E.; Kuhlman, Kristopher L.; Robinson, David G.

2015-09-01

This report presents efforts to develop the use of in situ naturally-occurring noble gas tracers to evaluate transport mechanisms and deformation in shale hydrocarbon reservoirs. Noble gases are promising as shale reservoir diagnostic tools due to their sensitivity of transport to: shale pore structure; phase partitioning between groundwater, liquid, and gaseous hydrocarbons; and deformation from hydraulic fracturing. Approximately 1.5-year time-series of wellhead fluid samples were collected from two hydraulically-fractured wells. The noble gas compositions and isotopes suggest a strong signature of atmospheric contribution to the noble gases that mix with deep, old reservoir fluids. Complex mixing and transport of fracturingmore » fluid and reservoir fluids occurs during production. Real-time laboratory measurements were performed on triaxially-deforming shale samples to link deformation behavior, transport, and gas tracer signatures. Finally, we present improved methods for production forecasts that borrow statistical strength from production data of nearby wells to reduce uncertainty in the forecasts.« less

Hydrologic-information needs for oil-shale development, northwestern Colorado

USGS Publications Warehouse

Taylor, O.J.

1982-01-01

Hydrologic information is not adequate for proper development of the large oil-shale reserves of Piceance basin in northwestern Colorado. Exploratory drilling and aquifer testing are needed to define the hydrologic system, to provide wells for aquifer testing, to design mine-drainage techniques, and to explore for additional water supplies. Sampling networks are needed to supply hydrologic data on the quantity and quality of surface water, ground water, and springs. A detailed sampling network is proposed for the White River basin because of expected impacts related to water supplies and waste disposal. Emissions from oil-shale retorts to the atmosphere need additional study because of possible resulting corrosion problems and the destruction of fisheries. Studies of the leachate materials and the stability of disposed retorted shale piles are needed to insure that these materials will not cause problems. Hazards related to in-situ retorts, and the wastes related to oil-shale development in general also need further investigation. (USGS)

Synthesis and analysis of jet fuel from shale oil and coal syncrudes

NASA Technical Reports Server (NTRS)

Gallagher, J. P.; Collins, T. A.; Nelson, T. J.; Pedersen, M. J.; Robison, M. G.; Wisinski, L. J.

1976-01-01

Thirty-two jet fuel samples of varying properties were produced from shale oil and coal syncrudes, and analyzed to assess their suitability for use. TOSCO II shale oil and H-COAL and COED syncrudes were used as starting materials. The processes used were among those commonly in use in petroleum processing-distillation, hydrogenation and catalytic hydrocracking. The processing conditions required to meet two levels of specifications regarding aromatic, hydrogen, sulfur and nitrogen contents at two yield levels were determined and found to be more demanding than normally required in petroleum processing. Analysis of the samples produced indicated that if the more stringent specifications of 13.5% hydrogen (min.) and 0.02% nitrogen (max.) were met, products similar in properties to conventional jet fuels were obtained. In general, shale oil was easier to process (catalyst deactivation was seen when processing coal syncrudes), consumed less hydrogen and yielded superior products. Based on these considerations, shale oil appears to be preferred to coal as a petroleum substitute for jet fuel production.

Metal speciation in Julia Creek oil shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hirner, A.V.

1989-03-01

The concentrations of 19 elements were determined in organic and inorganic phases of the Julia Creek Oil Shale (Queensland/Australia). The phases were obtained by solvent and alkaline extractions as well as by stepwise demineralization with strong acids. Together with the results of other groups, a consistent model concerning the partition of trace elements in the various sedimentary components could be achieved. Whereas V, Ni and Ag show distributions comparable to the abundances of the correspondent phases in the sample, Ca, Mn and Co are concentrated in the mineral components, and B, As and Pb are enriched in kerogen. Al, Cr,more » Fe, Cu, Zn, Mo, Cd and Sb range between these extremes, while Au and Hg are contained in the humic substances only.« less

43 CFR 3900.50 - Land use plans and environmental considerations.

Code of Federal Regulations, 2011 CFR

2011-10-01

...) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Oil Shale Management-Introduction § 3900.50 Land use plans and environmental considerations. (a...

Fractal Characteristics of Continental Shale Pores and its Significance to the Occurrence of Shale Oil in China: a Case Study of Biyang Depression

NASA Astrophysics Data System (ADS)

Li, Jijun; Liu, Zhao; Li, Junqian; Lu, Shuangfang; Zhang, Tongqian; Zhang, Xinwen; Yu, Zhiyuan; Huang, Kaizhan; Shen, Bojian; Ma, Yan; Liu, Jiewen

Samples from seven major exploration wells in Biyang Depression of Henan Oilfield were compared using low-temperature nitrogen adsorption and shale oil adsorption experiments. Comprehensive analysis of pore development, oiliness and shale oil flowability was conducted by combining fractal dimension. The results show that the fractal dimension of shale in Biyang Depression of Henan Oilfield was negatively correlated with the average pore size and positively correlated with the specific surface area. Compared with the large pore, the small pore has great fractal dimension, indicating the pore structure is more complicated. Using S1 and chloroform bitumen A to evaluate the relationship between shale oiliness and pore structure, it was found that the more heterogeneous the shale pore structure, the higher the complexity and the poorer the oiliness. Clay minerals are the main carriers involved in crude oil adsorption, affecting the mobility of shale oil. When the pore complexity of shale was high, the content of micro- and mesopores was high, and the high specific surface area could enhance the adsorption and reduce the mobility of shale oil.

Seismic based characterization of total organic content from the marine Sembar shale, Lower Indus Basin, Pakistan

NASA Astrophysics Data System (ADS)

Aziz, Omer; Hussain, Tahir; Ullah, Matee; Bhatti, Asher Samuel; Ali, Aamir

2018-02-01

The exploration and production of unconventional resources has increased significantly over the past few years around the globe to fulfill growing energy demands. Hydrocarbon potential of these unconventional petroleum systems depends on the presence of significant organic matter; their thermal maturity and the quality of present hydrocarbons i.e. gas or oil shale. In this work, we present a workflow for estimating Total Organic Content (TOC) from seismic reflection data. To achieve the objective of this study, we have chosen a classic potential candidate for exploration of unconventional reserves, the shale of the Sembar Formation, Lower Indus Basin, Pakistan. Our method includes the estimation of TOC from the well data using the Passey's ΔlogR and Schwarzkofp's methods. From seismic data, maps of Relative Acoustic Impedance (RAI) are extracted at maximum and minimum TOC zones within the Sembar Formation. A geostatistical trend with good correlation coefficient (R2) for cross-plots between TOC and RAI at well locations is used for estimation of seismic based TOC at the reservoir scale. Our results suggest a good calibration of TOC values from seismic at well locations. The estimated TOC values range from 1 to 4% showing that the shale of the Sembar Formation lies in the range of good to excellent unconventional oil/gas play within the context of TOC. This methodology of source rock evaluation provides a spatial distribution of TOC at the reservoir scale as compared to the conventional distribution generated from samples collected over sparse wells. The approach presented in this work has wider applications for source rock evaluation in other similar petroliferous basins worldwide.

The Hydrocarbon Fingerprints of Organic-rich Shales

NASA Astrophysics Data System (ADS)

Davies, S. J.; Sommariva, R.; Blake, R.; Ortega, M.; Cuss, R. J.; Harrington, J.; Emmings, J.; Lovell, M.; Monks, P.

2016-12-01

Geological characterization of key source rocks and potential unconventional reservoirs from the UK Mississippian has shed new light on the heterogeneous character of shales (mudstones) and also on the mechanisms for preserving organic matter of different types and abundances. Sedimentological studies of these mudstones suggest that systematic variations in total organic carbon (TOC) content are related to the dominant sediment delivery process (hemipelagic suspension settling vs. sediment gravity flows). Questions remain, however, as to how the physical character and chemical composition (e.g. lithology, mineralogy, organic matter type, maturity and abundance) of a mudstone relates to the volume and type of hydrocarbon gas that could be released. Using novel proof-of-principle laboratory experiments, we demonstrate that it is possible to quantify, in real-time (second by second), methane and a wide range of non-methane hydrocarbons (NMHC) gases as they are released from a crushed mudstone sample. Real time measurements are undertaken using proton-transfer-reaction time-of-flight mass spectrometry (PTR- TOF- MS). The PTR technique is not sensitive to some classes of NHMC and the whole range of hydrocarbons is analyzed using thermal desorption gas chromatography mass spectrometry (TD- GC- MS). Our data indicate that NMHC gases (mostly alkanes and aromatics) are released with temperature and humidity-dependent release rates, which depend on the physio-chemical characteristics of the different hydrocarbons classes and on the mode of storage within the shale. Knowledge of the abundance of methane and the speciated NMHC, and how that relates to geological characteristics of a mudstone is important to understand both the source rock potential and the potential pollutants. Ultimately, we aim to link these results to the geomechanical properties of shales. We discuss the implications of our findings for the environment and for the industrial and commercial exploitation of source rocks and unconventional reservoirs.

The influence of total suction on the brittle failure characteristics of clay shales

NASA Astrophysics Data System (ADS)

Amann, F.; Linda, W.; Zimmer, S.; Thoeny, R.

2013-12-01

Clay shale testing is challenging and the results obtained from standard laboratory tests may not always reflect the strength of the clay shale in-situ. This is to a certain extend associated with the sensitivity of these rock types to desaturation processes during drilling, sample storage, and sample preparation. In this study the relationship between total suction, uniaxial compressive strength and Brazilian tensile (BTS) strength of cylindrical samples of Opalinus Clay was established in a systematic manner. Unconfined uniaxial compression and BTS tests were performed utilizing a servo-controlled testing procedure. Total suctions in the specimens was generated in air tight desiccators using supersaturated saline solutions which establish a relative humidity ranging from 20% to 99%. For unconfined compressive strength tests loading of the specimens occurred parallel to bedding. For BTS tests loading was either oriented normal or perpendicular to bedding. Both, the crack initiation and volumetric strain reversal threshold values were determined using volumetric and radial stress-strain methods. The results of BTS tests show that the tensile strength normal and perpendicular to bedding increases by a factor of approximately 3 when total suction is increased from 0 to 90 MPa (i.e. saturation decreases from 1.0 to 0.7) . Beyond 90 MPa total suction no further increase in tensile strength was observed, most probably due to shrinkage cracks which alter the tensile strength of the clay shale. Results obtained from UCS tests suggest that higher total suctions result in higher UCS values. Between total suctions of 0 to 90 MPa, the strength increase is almost linear (i.e. the UCS increases by a factor of 1.5 MPa). Beyond 90 MPa total suction no further strength increase was observed. A similar trend can be observed for crack initiation and crack damage values. In the same range of total suction the crack initiation stress increases by a factor of 5 (from 2 MPa to 10 MPa), and the crack damage stress increases by a factor of 2 (from 6 to 12 MPa). In addition to UCS tests, the water retention curve of intact and disturbed specimens was established. Here, results indicate that the drying path remains nearly unaffected by mechanical damage. However, the wetting path is considerably affected by mechanical damage.

Shallow groundwater quality and geochemistry in the Fayetteville Shale gas-production area, north-central Arkansas, 2011

USGS Publications Warehouse

Kresse, Timothy M.; Warner, Nathaniel R.; Hays, Phillip D.; Down, Adrian; Vengosh, Avner; Jackson, Robert B.

2012-01-01

The Mississippian Fayetteville Shale serves as an unconventional gas reservoir across north-central Arkansas, ranging in thickness from approximately 50 to 550 feet and varying in depth from approximately 1,500 to 6,500 feet below the ground surface. Primary permeability in the Fayetteville Shale is severely limited, and successful extraction of the gas reservoir is the result of advances in horizontal drilling techniques and hydraulic fracturing to enhance and develop secondary fracture porosity and permeability. Drilling and production of gas wells began in 2004, with a steady increase in production thereafter. As of April 2012, approximately 4,000 producing wells had been completed in the Fayetteville Shale. In Van Buren and Faulkner Counties, 127 domestic water wells were sampled and analyzed for major ions and trace metals, with a subset of the samples analyzed for methane and carbon isotopes to describe general water quality and geochemistry and to investigate the potential effects of gas-production activities on shallow groundwater in the study area. Water-quality analyses from this study were compared to historical (pregas development) shallow groundwater quality collected in the gas-production area. An additional comparison was made using analyses from this study of groundwater quality in similar geologic and topographic areas for well sites less than and greater than 2 miles from active gas-production wells. Chloride concentrations for the 127 groundwater samples collected for this study ranged from approximately 1.0 milligram per liter (mg/L) to 70 mg/L, with a median concentration of 3.7 mg/L, as compared to maximum and median concentrations for the historical data of 378 mg/L and 20 mg/L, respectively. Statistical analysis of the data sets revealed statistically larger chloride concentrations (p-value <0.001) in the historical data compared to data collected for this study. Chloride serves as an important indicator parameter based on its conservative transport characteristics and relatively elevated concentrations in production waters associated with gas extraction activities. Major ions and trace metals additionally had lower concentrations in data gathered for this study than in the historical analyses. Additionally, no statistical difference existed between chloride concentrations from water-quality data collected for this study from 94 wells located less than 2 miles from a gas-production well and 33 wells located 2 miles or more from a gas-production well; a Wilcoxon rank-sum test showed a p-value of 0.71. Major ion chemistry was investigated to understand the effects of geochemical and reduction-oxidation (redox) processes on the shallow groundwater in the study area along a continuum of increased rock-water interaction represented by increases in dissolved solids concentration. Groundwater in sandstone formations is represented by a low dissolved solids concentration (less than 30 mg/L) and slightly acidic water type. Shallow shale aquifers were represented by dissolved solids concentrations ranging upward to 686 mg/L, and water types evolving from a dominantly mixed-bicarbonate and calcium-bicarbonate to a strongly sodium-bicarbonate water type. Methane concentration and carbon isotopic composition were analyzed in 51 of the 127 samples collected for this study. Methane occurred above a detection limit of 0.0002 mg/L in 32 of the 51 samples, with concentrations ranging upward to 28.5 mg/L. Seven samples had methane concentrations greater than or equal to 0.5 mg/L. The carbon isotopic composition of these higher concentration samples, including the highest concentration of 28.5 mg/L, shows the methane was likely biogenic in origin with carbon isotope ratio values ranging from -57.6 to -74.7 per mil. Methane concentrations increased with increases in dissolved solids concentrations, indicating more strongly reducing conditions with increasing rock-water interaction in the aquifer. As such, groundwater-quality data collected for this study indicate that groundwater chemistry in the shallow aquifer system in the study area is a result of natural processes, beginning with recharge of dilute atmospheric precipitation and evolution of observed groundwater chemistry through rock-water interaction and redox processes.

Time-dependent deformation of gas shales - role of rock framework versus reservoir fluids

NASA Astrophysics Data System (ADS)

Hol, Sander; Zoback, Mark

2013-04-01

Hydraulic fracturing operations are generally performed to achieve a fast, drastic increase of permeability and production rates. Although modeling of the underlying short-term mechanical response has proven successful via conventional geomechanical approaches, predicting long-term behavior is still challenging as the formation interacts physically and chemically with the fluids present in-situ. Recent experimental work has shown that shale samples subjected to a change in effective stress deform in a time-dependent manner ("creep"). Although the magnitude and nature of this behavior is strongly related to the composition and texture of the sample, also the choice of fluid used in the experiments affects the total strain response - strongly adsorbing fluids result in more, recoverable creep. The processes underlying time-dependent deformation of shales under in-situ stresses, and the long-term impact on reservoir performance, are at present poorly understood. In this contribution, we report triaxial mechanical tests, and theoretical/thermodynamic modeling work with the aim to identify and describe the main mechanisms that control time-dependent deformation of gas shales. In particular, we focus on the role of the shale solid framework versus the type and pressure of the present pore fluid. Our experiments were mainly performed on Eagle Ford Shale samples. The samples were subjected to cycles of loading and unloading, first in the dry state, and then again after equilibrating them with (adsorbing) CO2 and (non-adsorbing) He at fluid pressures of 4 MPa. Stresses were chosen close to those persisting under in-situ conditions. The results of our tests demonstrate that likely two main types of deformation mechanisms operate that relate to a) the presence of microfractures as a dominating feature in the solid framework of the shale, and b) the adsorbing potential of fluids present in the nanoscale voids of the shale. To explain the role of adsorption in the observed compaction creep, we postulate a serial coupling between 1) stress-driven desorption of the fluid species, 2) diffusion of the desorbed species out of the solid, and 3) consequent shrinkage. We propose a model in which the total shrinkage of the solid (Step 3) that is measured as bulk compaction, is driven by a change in stress state (Step 1), and evolves in time controlled by the diffusion characteristics of the system (Step 2). Our experimental and modeling study shows that both the nature of the solid framework of the shale, as well as the type and pressure of pore fluids affect the long-term in-situ mechanical behavior of gas shale reservoirs.

Influence of the Kingak Shale ultimate shelf margin on frontal structures of the Brooks Range in the National Petroleum Reserve in Alaska

USGS Publications Warehouse

Stier, Natalie E.; Connors, Christopher D.; Houseknecht, David W.

2014-01-01

The Jurassic–Lower Cretaceous Kingak Shale in the National Petroleum Reserve in Alaska (NPRA) includes several southward-offlapping depositional sequences that culminate in an ultimate shelf margin, which preserves the depositional profile in southern NPRA. The Kingak Shale thins abruptly southward across the ultimate shelf margin and grades into condensed shale, which is intercalated with underlying condensed shale and chert of the Upper Triassic Shublik Formation and overlying condensed shale of the Lower Cretaceous pebble shale unit and the gamma-ray zone (GRZ) of the Hue Shale. This composite of condensed shale forms a thin (≈300-meter) and mechanically weak section between much thicker and mechanically stronger units, including the Sadlerochit and Lisburne Groups below and the sandstone-prone foredeep wedge of the Torok Formation above. Seismic interpretation indicates that the composite condensed section acted as the major detachment during an Early Tertiary phase of deformation in the northern foothills of the Brooks Range and that thrust faults step up northward to the top of the Kingak, or to other surfaces within the Kingak or the overlying Torok. The main structural style is imbricate fault-bend folding, although fault-propagation folding is evident locally, and large-displacement thrust faults incorporate backthrusting to form structural wedges. The Kingak ultimate shelf margin served as a ramp to localize several thrust faults, and the spatial relationship between the ultimate shelf margin and thrust vergence is inferred to have controlled many structures in southern NPRA. For example, the obliqueness of the Carbon Creek anticline relative to other structures in the foothills is the result of northward-verging thrust faults impinging obliquely on the Kingak ultimate shelf margin in southwestern NPRA.

Comparison of organic geochemistry and metal enrichment in two black shales: Cambrian Alum Shale of Sweden and Devonian Chattanooga Shale of United States

USGS Publications Warehouse

Leventhal, J.S.

1991-01-01

In most black shales, such as the Chattanooga Shale and related shales of the eastern interior United States, increased metal and metalloid contents are generally related to increased organic carbon content, decreased sedimentation rate, organic matter type, or position in the basin. In areas where the stratigraphic equivalents of the Chattanooga Shale are deeply buried and and the organic material is thermally mature, metal contents are essentially the same as in unheated areas and correlate with organic C or S contents. This paradigm does not hold for the Cambrian Alum Shale Formation of Sweden where increased metal content does not necessarily correlate with organic matter content nor is metal enrichment necessarily related to land derived humic material because this organic matter is all of marine source. In southcentral Sweden the elements U, Mo, V, Ni, Zn, Cd and Pb are all enriched relative to average black shales but only U and Mo correlate to organic matter content. Tectonically disturbed and metamorphosed allochthonous samples of Alum Shale on the Caledonian front in western Sweden have even higher amounts for some metals (V, Ni, Zn and Ba) relative to the autochthonous shales in this area and those in southern Sweden. ?? 1991 Springer-Verlag.

Comparative acute toxicity of shale and petroleum derived distillates.

PubMed

Clark, C R; Ferguson, P W; Katchen, M A; Dennis, M W; Craig, D K

1989-12-01

In anticipation of the commercialization of its shale oil retorting and upgrading process, Unocal Corp. conducted a testing program aimed at better defining potential health impacts of a shale industry. Acute toxicity studies using rats and rabbits compared the effects of naphtha, Jet-A, JP-4, diesel and "residual" distillate fractions of both petroleum derived crude oils and hydrotreated shale oil. No differences in the acute oral (greater than 5 g/kg LD50) and dermal (greater than 2 g/kg LD50) toxicities were noted between the shale and petroleum derived distillates and none of the samples were more than mildly irritating to the eyes. Shale and petroleum products caused similar degrees of mild to moderate skin irritation. None of the materials produced sensitization reactions. The LC50 after acute inhalation exposure to Jet-A, shale naphtha, (greater than 5 mg/L) and JP-4 distillate fractions of petroleum and shale oils was greater than 5 mg/L. The LC50 of petroleum naphtha (greater than 4.8 mg/L) and raw shale oil (greater than 3.95 mg/L) also indicated low toxicity. Results demonstrate that shale oil products are of low acute toxicity, mild to moderately irritating and similar to their petroleum counterparts. The results further demonstrate that hydrotreatment reduces the irritancy of raw shale oil.

Sedimentary provenance of Maastrichtian oil shales, Central Eastern Desert, Egypt

NASA Astrophysics Data System (ADS)

Fathy, Douaa; Wagreich, Michael; Mohamed, Ramadan S.; Zaki, Rafat

2017-04-01

Maastrichtian oil shales are distributed within the Central Eastern Desert in Egypt. In this study elemental geochemical data have been applied to investigate the probable provenance of the sedimentary detrital material of the Maastrichtian oil shale beds within the Duwi and the Dakhla formations. The Maastrichtian oil shales are characterized by the enrichment in Ca, P, Mo, Ni, Zn, U, Cr and Sr versus post-Archean Australian shales (PAAS). The chondrite-normalized patterns of the Maastrichtian oil shale samples are showing LREE enrichment, HREE depletion, slightly negative Eu anomaly, no obvious Ce anomaly and typical shale-like PAAS-normalized patterns. The total REE well correlated with Si, Al, Fe, K and Ti, suggesting that the REE of the Maastrichtian oil shales are derived from terrigenous source. Chemical weathering indices such as Chemical Index of Alteration (CIA), Chemical Proxy of Alteration (CPA) and Plagioclase Index of Alteration (PIA) indicate moderate to strong chemical weathering. We suggest that the Maastrichtian oil shale is mainly derived from first cycle rocks especially intermediate rocks without any significant inputs from recycled or mature sources. The proposed data illustrated the impact of the parent material composition on evolution of oil shale chemistry. Furthermore, the paleo-tectonic setting of the detrital source rocks for the Maastrichtian oil shale is probably related to Proterozoic continental island arcs

43 CFR 3930.40 - Assessments for missing diligence milestones.

Code of Federal Regulations, 2011 CFR

2011-10-01

...) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) MANAGEMENT OF OIL SHALE EXPLORATION AND LEASES Management of Oil Shale Exploration Licenses and Leases § 3930.40 Assessments for...

43 CFR 3922.40 - Tract delineation.

Code of Federal Regulations, 2011 CFR

2011-10-01

..., DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE LEASING Application Processing § 3922.40 Tract... the oil shale resource. (b) The BLM may delineate more or less lands than were covered by an...

Maps showing thermal maturity of Upper Cretaceous marine shales in the Wind River Basin, Wyoming

USGS Publications Warehouse

Finn, Thomas M.; Pawlewicz, Mark J.

2013-01-01

The Wind River Basin is a large Laramide (Late Cretaceous through Eocene) structural and sedimentary basin that encompasses about 7,400 square miles in central Wyoming. The basin is bounded by the Washakie Range, Owl Creek, and southern Bighorn Mountains on the north, the Casper arch on the east and northeast, the Granite Mountains on the south, and the Wind River Range on the west. Important conventional and unconventional oil and gas resources have been discovered and produced from reservoirs ranging in age from Mississippian through Tertiary. It has been suggested that various Upper Cretaceous marine shales are the principal hydrocarbon source rocks for many of these accumulations. Numerous source rock studies of various Upper Cretaceous marine shales throughout the Rocky Mountain region have led to the conclusion that these rocks have generated, or are capable of generating, oil and (or) gas. With recent advances and success in horizontal drilling and multistage fracture stimulation there has been an increase in exploration and completion of wells in these marine shales in other Rocky Mountain Laramide basins that were traditionally thought of only as hydrocarbon source rocks. Important parameters that control hydrocarbon production from shales include: reservoir thickness, amount and type of organic matter, and thermal maturity. The purpose of this report is to present maps and a structural cross section showing levels of thermal maturity, based on vitrinite reflectance (Ro), for Upper Cretaceous marine shales in the Wind River Basin.

Strength anisotropy of shales deformed under uppermost crustal conditions

NASA Astrophysics Data System (ADS)

Bonnelye, Audrey; Schubnel, Alexandre; David, Christian; Henry, Pierre; Guglielmi, Yves; Gout, Claude; Fauchille, Anne-Laure; Dick, Pierre

2017-01-01

Conventional triaxial tests were performed on three sets of samples of Tournemire shale along different orientations relative to bedding (0°, 45°, and 90°). Experiments were carried out up to failure at increasing confining pressures ranging from 2.5 to 160 MPa, at strain rates ranging between 3 × 10-7s-1 and 3 × 10-5s-1. This allowed us to determine the entire anisotropic elastic compliance matrix as a function of confining pressure. Results show that the orientation of principal stress relative to bedding plays an important role on the brittle strength, with 45° orientation being the weakest. We fit our results with a wing crack micromechanical model and an anisotropic fracture toughness. We found low values of internal friction coefficient and apparent friction coefficient in agreement with friction coefficient of clay minerals (between 0.2 and 0.3) and values of KIc comparable to that already published in the literature. We also showed that strain rate has a strong impact on peak stress and that dilatancy appears right before failure and hence highlighting the importance of plasticity mechanisms. Although brittle failure was systematically observed, stress drops and associated slips were slow and deformation always remained aseismic (no acoustic emission were detected). This confirms that shales are good lithological candidates for shallow crust aseismic creep and slow slip events.

Thermal maturity and organic composition of Pennsylvanian coals and carbonaceous shales, north-central Texas: Implications for coalbed gas potential

USGS Publications Warehouse

Hackley, P.C.; Guevara, E.H.; Hentz, T.F.; Hook, R.W.

2009-01-01

Thermal maturity was determined for about 120 core, cuttings, and outcrop samples to investigate the potential for coalbed gas resources in Pennsylvanian strata of north-central Texas. Shallow (< 600??m; 2000??ft) coal and carbonaceous shale cuttings samples from the Middle-Upper Pennsylvanian Strawn, Canyon, and Cisco Groups in Archer and Young Counties on the Eastern Shelf of the Midland basin (northwest and downdip from the outcrop) yielded mean random vitrinite reflectance (Ro) values between about 0.4 and 0.8%. This range of Ro values indicates rank from subbituminous C to high volatile A bituminous in the shallow subsurface, which may be sufficient for early thermogenic gas generation. Near-surface (< 100??m; 300??ft) core and outcrop samples of coal from areas of historical underground coal mining in the region yielded similar Ro values of 0.5 to 0.8%. Carbonaceous shale core samples of Lower Pennsylvanian strata (lower Atoka Group) from two deeper wells (samples from ~ 1650??m; 5400??ft) in Jack and western Wise Counties in the western part of the Fort Worth basin yielded higher Ro values of about 1.0%. Pyrolysis and petrographic data for the lower Atoka samples indicate mixed Type II/Type III organic matter, suggesting generated hydrocarbons may be both gas- and oil-prone. In all other samples, organic material is dominated by Type III organic matter (vitrinite), indicating that generated hydrocarbons should be gas-prone. Individual coal beds are thin at outcrop (< 1??m; 3.3??ft), laterally discontinuous, and moderately high in ash yield and sulfur content. A possible analog for coalbed gas potential in the Pennsylvanian section of north-central Texas occurs on the northeast Oklahoma shelf and in the Cherokee basin of southeastern Kansas, where contemporaneous gas-producing coal beds are similar in thickness, quality, and rank.

Experimental Determination of P-V-T-X Properties and Adsorption Kinetics in the CO2-CH4 System under Shale Gas Reservoir Conditions

NASA Astrophysics Data System (ADS)

Xiong, Y.; Wang, Y.

2014-12-01

Shale gas production via hydrofracturing has profoundly changed the energy portfolio in the USA and other parts of the world. Under the shale gas reservior conditions, CO2 and H2O, either in residence or being injected during hydrofracturing or both, co-exist with CH4. One important feature characteristic of shale is the presence of nanometer-scale (1-100 nm) pores in shale or mudstone. The interactions among CH4, CO2 and H2O in those nano-sized pores directly impact shale gas storage and gas release from the shale matrix. Therefore, a fundamental understanding of interactions among CH4, CO2 and H2O in nanopore confinement would provide guidance in addressing a number of problems such as rapid decline in production after a few years and low recovery rates. We are systematically investigating the P-V-T-X properties and adsorption kinetics in the CH4-CO2-H2O system under the reservior conditions. We have designed and constructed a unique high temperature and pressure experimental system that can measure both of the P-V-T-X properties and adsorption kinetics sequentially. We measure the P-V-T-X properties of CH4-CO2 mixtures with CH4 up to 95 vol. %, and adsorption kinetics of various materials, under the conditions relevant to shale gas reservoir. We use three types of materials: (I) model materials, (II) single solid phases separated from shale samples, and (III) crushed shale samples from both the known shale gas producing formations and the shale gas barren formations. The model materials are well characterized in terms of pore sizes. Therefore, the results associated with the model material serve as benchmarks for our model development. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This research is supported by a Geoscience Foundation LDRD.

Structure, Mechanics and Flow Properties of Fractured Shale: Core-Scale Experimentation and In-situ Imaging

NASA Astrophysics Data System (ADS)

Abdelmalek, B. F.; Karpyn, Z.; Liu, S.

2014-12-01

Over the last several years, hydrocarbon exploitation and development in North America has been heavily centered on shale gas plays. However, the physical attributes of shales and their manifestation on transport properties and storage capacity remain poorly understood. Therefore, more experimentally based data are needed to fill the gaps in understanding both transport and storage of fluids in shale. The proposed work includes installation and testing of an experimental system which is capable of monitoring the dynamic evolution of shale core permeability under variable loading conditions and in coordination with X-ray microCT imaging. The goal of this study is to better understand and quantify fluid flow patterns and associated transport dynamics of fractured shale samples. The independent variables considered in this study are: mechanical loading and pore pressure. The mechanical response of shale core is captured for different loading paths. To best replicate the in-situ production scenario, the pore pressure is progressively depleted to mimic pressure decline. During the course of experimentation, permeability is estimated using the pulse-decay method under tri-axial stress boundary conditions. Simultaneously, X-ray microCT imaging is used with a tracer gas that is allowed to flow through the sample as an illuminating agent. In the presence of an illuminating agent, either Xenon or Krypton, the X-ray CT scanner can image fractures, global pathways and diffusional fronts in the matrix, as well as sorption sites that reflect heterogeneities in the sample and localized deformation. Anticipated results from these experiments will help quantify permeability evolution as a function of different loading conditions and pore pressure depletion. Also, the X-ray images will help visualize the change of flow patterns and the intensity of sorption as a function of mechanical loading and pore pressure.

Effects of acid-volatile sulfide on metal bioavailability and toxicity to midge (Chironomus tentans) larvae in black shale sediments

USGS Publications Warehouse

Ogendi, G.M.; Brumbaugh, W.G.; Hannigan, R.E.; Farris, J.L.

2007-01-01

Metal bioavailability and toxicity to aquatic organisms are greatly affected by variables such as pH, hardness, organic matter, and sediment acid-volatile sulfide (AVS). Sediment AVS, which reduces metal bioavailability and toxicity by binding and immobilizing metals as insoluble sulfides, has been studied intensely in recent years. Few studies, however, have determined the spatial variability of AVS and its interaction with simultaneously extracted metals (SEM) in sediments containing elevated concentrations of metals resulting from natural geochemical processes, such as weathering of black shales. We collected four sediment samples from each of four headwater bedrock streams in northcentral Arkansa (USA; three black shale-draining streams and one limestone-draining stream). We conducted 10-d acute whole-sediment toxicity tests using the midge Chironomus tentans and performed analyses for AVS, total metals, SEMs, and organic carbon. Most of the sediments from shale-draining streams had similar total metal and SEM concentrations but considerable differences in organic carbon and AVS. Zinc was the leading contributor to the SEM molar sum, averaging between 68 and 74%, whereas lead and cadmium contributed less than 3%. The AVS concentration was very low in all but two samples from one of the shale streams, and the sum of the SEM concentrations was in molar excess of AVS for all shale stream sediments. No significant differences in mean AVS concentrations between sediments collected from shale-draining or limestone-draining sites were noted (p > 0.05). Midge survival and growth in black shale-derived sediments were significantly less (p < 0.001) than that of limestone-derived sediments. On the whole, either SEM alone or SEM-AVS explained the total variation in midge survival and growth about equally well. However, survival and growth were significantly greater (p < 0.05) in the two sediment samples that contained measurable AVS compared with the two sediments from the same stream that contained negligible AVS. ?? 2007 SETAC.

Geology of the Devonian black shales of the Appalachian Basin

USGS Publications Warehouse

Roen, J.B.

1984-01-01

Black shales of Devonian age in the Appalachian Basin are a unique rock sequence. The high content of organic matter, which imparts the characteristic lithology, has for years attracted considerable interest in the shales as a possible source of energy. The recent energy shortage prompted the U.S. Department of Energy through the Eastern Gas Shales Project of the Morgantown Energy Technology Center to underwrite a research program to determine the geologic, geochemical, and structural characteristics of the Devonian black shales in order to enhance the recovery of gas from the shales. Geologic studies by Federal and State agencies and academic institutions produced a regional stratigraphic network that correlates the 15 ft black shale sequence in Tennessee with 3000 ft of interbedded black and gray shales in central New York. These studies correlate the classic Devonian black shale sequence in New York with the Ohio Shale of Ohio and Kentucky and the Chattanooga Shale of Tennessee and southwestern Virginia. Biostratigraphic and lithostratigraphic markers in conjunction with gamma-ray logs facilitated long-range correlations within the Appalachian Basin. Basinwide correlations, including the subsurface rocks, provided a basis for determining the areal distribution and thickness of the important black shale units. The organic carbon content of the dark shales generally increases from east to west across the basin and is sufficient to qualify as a hydrocarbon source rock. Significant structural features that involve the black shale and their hydrocarbon potential are the Rome trough, Kentucky River and Irvine-Paint Creek fault zone, and regional decollements and ramp zones. ?? 1984.

The role of fluid mobility in the development of shale weathering profiles: Direct observations from a vadose zone monitoring system

NASA Astrophysics Data System (ADS)

Druhan, J. L.; Wang, J.; Cargill, S.; Murphy, C.; Tune, A. K.; Dietrich, W. E.; Rempe, D.

2017-12-01

Extensive effort has focused on resolving the contribution of weathering reactions to the transfer of mass over scales ranging from individual hillslope weathering profiles, across local watersheds, to continental drainage networks. A persistent limitation in quantifying these fluxes is the variability in fluid flowpaths through the subsurface, which may alter the extent of chemical weathering relative to that expected from idealized homogenous conditions. In the past decade, the consequence of fluid travel time on solute flux has been recognized as a key complexity in the interpretation of solute concentrations, particularly in upland watersheds characterized by fracture flowpaths, as is typical of shale-dominated landscapes. Though recent studies have suggested a variety of models for solute generation in such dual (matrix and fracture flow) domain systems, a central impediment to advancing prediction is the lack of direct observations. Here, we report solute chemistry as a function of depth across an 18 m thick vadose zone of weathered argillite (shale) in the Eel River Critical Zone Observatory (ERCZO) using novel sub-horizontal distributed samplers (Vadose Zone Monitoring System). We contrast a year of major and trace ion chemistry obtained from water samples collected approximately biweekly using two complementary sampling systems, one applying active pressure to extract matrix-bound pore fluid, and the other using a passive collection method to extract freely draining water. Precipitation falling during the winter rainy season passes through this vadose zone, causing increased rock moisture that is subsequently depleted by transpiring trees. Solute concentrations reflect these seasonal changes, and, surprisingly, normalized ion ratios span the full range of values reported for the world's largest rivers. Notably, for some major cations, freely draining water is consistently less concentrated than matrix-bound water, and the composition of vadose zone water is consistently more variable than the underlying groundwater. Dual domain 1D reactive transport simulations demonstrate that even a simplified scoping model for solute concentrations across fractured shale systems requires a non-uniform fluid travel time to reasonably reproduce observations.

Detection of early changes in lung cell cytology by flow-systems analysis techniques. Progress report, January 1--December 31, 1978. [Resulting from exposure to toxic agents associated with production and use of synthetic fuels from oil shale and coal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steinkamp, J.A.; Wilson, J.S.; Svitra, Z.V.

1979-02-01

This report summarizes ongoing experiments to develop cytological and biochemical indicators for measuring damage to respiratory tract cells of experimental animals exposed by inhalation to environmental toxic agents. The specific goal is to apply flow cytometric methods to analyze and detect changes in lung epithelium as a function of exposure to toxic agents associated with the production and utilization of synthetic fuels from oil shale and coal. During the past 6 months, hamsters were exposed to raw and spent oil shale particulates, silica dust, and ozone, and DNA content measurements were performed on lung cell samples. Although initial shale exposuresmore » did not yield the expected results, recent data show atypical changes in DNA content per cell distributions. Ozone exposures also were expanded to include DNA measurements and cytology, ranging up to 72 h postexposure. Progress was achieved in developing a new method for quantitating pulmonary macrophage phagocytosis in rats using micron-sized fluorescent spheres. New methods for determining alkaline phosphatase, DNA content, and protein also were under development. Plans are to continue developing cytological and biochemical markers for measuring atypical cellular changes, including macrophage function, and to emphasize exposing experimental animals to particulates and gaseous agents for studying dose-damage relationships.« less

New Advances in Re-Os Geochronology of Organic-rich Sedimentary Rocks.

NASA Astrophysics Data System (ADS)

Creaser, R. A.; Selby, D.; Kendall, B. S.

2003-12-01

Geochronology using 187Re-187Os is applicable to limited rock and mineral matrices, but one valuable application is the determination of depositional ages for organic-rich clastic sedimentary rocks like black shales. Clastic sedimentary rocks, in most cases, do not yield depositional ages using other radioactive isotope methods, but host much of Earth's fossil record upon which the relative geological timescale is based. As such, Re-Os dating of black shales has potentially wide application in timescale calibration studies and basin analysis, if sufficiently high precision and accuracy could be achieved. This goal requires detailed, systematic studies and evaluation of factors like standard compound stoichiometry, geologic effects, and the 187Re decay constant. Ongoing studies have resulted in an improved understanding of the abilities, limitations and systematics of the Re-Os geochronometer in black shales. First-order knowledge of the effects of processes like hydrocarbon maturation and low-grade metamorphism is now established. Hydrocarbon maturation does not impact the ability of the Re-Os geochronometer to determine depositional ages from black shales. The Re-Os age determined for the Exshaw Fm of western Canada is accurate within 2σ analytical uncertainty of the known age of the unit (U-Pb monazite from ash, conodont biostratigraphy). This suggests that the large improvement in precision attained for Re-Os dating of black shales by Cohen et al (ESPL 1999) over the pioneering work of Ravizza & Turekian (GCA 1989), relates to advances in analytical methodologies and sampling strategies, rather than a lack of disturbance by hydrocarbon maturation. We have found that a significant reduction in isochron scatter can be achieved by using an alternate dissolution medium, which preferentially attacks organic matter in which Re and Os are largely concentrated. This likely results from a more limited release of detrital Os and Re held in silicate materials during dissolution, compared with the inverse aqua regia medium used for Carius tube analysis. Using these "organic-selective" dissolution techniques, precise depositional ages have now been obtained from samples with very low TOC contents ( ˜0.5%), meaning that a greater range of clastic sedimentary rocks is amenable for Re-Os age dating. Well-fitted Re-Os isochrons of plausible geological age have also been determined from low-TOC shales subjected to chlorite-grade regional metamorphism. These results further illustrate the wide, but currently underutilized, potential of the Re-Os geochronometer in shales. The precision of age data attainable by the Re-Os system directly from black shales can be better than +/- 1% uncertainty (2σ , derived from isochron regression analysis), and the derived ages are demonstrably accurate.

43 CFR 3900.62 - Special requirements to protect the lands and resources.

Code of Federal Regulations, 2011 CFR

2011-10-01

... (Continued) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Oil Shale Management-Introduction § 3900.62 Special requirements to protect the lands and...

Elevated Atmospheric Levels of Benzene and Benzene-Related Compounds from Unconventional Shale Extraction and Processing: Human Health Concern for Residential Communities.

PubMed

Rich, Alisa L; Orimoloye, Helen T

2016-01-01

The advancement of natural gas (NG) extraction across the United States (U.S.) raises concern for potential exposure to hazardous air pollutants (HAPs). Benzene, a HAP and a primary chemical of concern due to its classification as a known human carcinogen, is present in petroleum-rich geologic formations and is formed during the combustion of bypass NG. It is a component in solvents, paraffin breakers, and fuels used in NG extraction and processing (E&P). The objectives of this study are to confirm the presence of benzene and benzene-related compounds (benzene[s]) in residential areas, where unconventional shale E&P is occurring, and to determine if benzene[s] exists in elevated atmospheric concentrations when compared to national background levels. Ambient air sampling was conducted in six counties in the Dallas/Fort Worth Metroplex with passive samples collected in evacuated 6-L Summa canisters. Samples were analyzed by gas chromatography/mass spectrometry, with sampling performed at variable distances from the facility fence line. Elevated concentrations of benzene[s] in the atmosphere were identified when compared to U.S. Environmental Protection Agency's Urban Air Toxics Monitoring Program. The 24-hour benzene concentrations ranged from 0.6 parts per billion by volume (ppbv) to 592 ppbv, with 1-hour concentrations from 2.94 ppbv to 2,900.20 ppbv. Benzene is a known human carcinogen capable of multisystem health effects. Exposure to benzene is correlated with bone marrow and blood-forming organ damage and immune system depression. Sensitive populations (children, pregnant women, elderly, immunocompromised) and occupational workers are at increased risk for adverse health effects from elevated atmospheric levels of benzene[s] in residential areas with unconventional shale E&P.

Assessing Radium Activity in Shale Gas Produced Brine

NASA Astrophysics Data System (ADS)

Fan, W.; Hayes, K. F.; Ellis, B. R.

2015-12-01

The high volumes and salinity associated with shale gas produced water can make finding suitable storage or disposal options a challenge, especially when deep well brine disposal or recycling for additional well completions is not an option. In such cases, recovery of commodity salts from the high total dissolved solids (TDS) of the brine wastewater may be desirable, yet the elevated concentrations of the naturally occurring radionuclides such as Ra-226 and Ra-228 in produced waters (sometimes substantially greater than the EPA limit of 5 pCi/L) may concentrate during these steps and limit salt recovery options. Therefore, assessing the potential presence of these Ra radionuclides in produced water from shale gas reservoir properties is desirable. In this study, we seek to link U and Th content within a given shale reservoir to the expected Ra content of produced brine by accounting for secular equilibrium within the rock and subsequent release to Ra to native brines. Produced brine from a series of Antrim shale wells and flowback from a single Utica-Collingwood shale well in Michigan were sampled and analyzed via ICP-MS to measure Ra content. Gamma spectroscopy was used to verify the robustness of this new Ra analytical method. Ra concentrations were observed to be up to an order of magnitude higher in the Antrim flowback water samples compared to those collected from the Utica-Collingwood well. The higher Ra content in Antrim produced brines correlates well with higher U content in the Antrim (19 ppm) relative to the Utica-Collingwood (3.5 ppm). We also observed an increase in Ra activity with increasing TDS in the Antrim samples. This Ra-TDS relationship demonstrates the influence of competing divalent cations in controlling Ra mobility in these clay-rich reservoirs. In addition, we will present a survey of geochemical data from other shale gas plays in the U.S. correlating shale U, Th content with produced brine Ra content. A goal of this study is to develop a method to predict the expected Ra activity in shale gas produced brines on a regional or play-specific basis in an effort to guide wastewater management practices or optimize regional treatment strategies.

Re-assessing the Molybdenum Isotope Composition of Pre-GOE Seawater: Evidence for Dynamic Ocean Redox

NASA Astrophysics Data System (ADS)

Ostrander, C. M.; Kendall, B.; Roy, M.; Romaniello, S. J.; Nunn, S. J.; Gordon, G. W.; Olson, S. L.; Lyons, T. W.; Zheng, W.; Anbar, A. D.

2016-12-01

Molybdenum (Mo) isotope compositions of Archean shales can provide important insights into ocean and atmosphere redox dynamics prior to the Great Oxidation Event (GOE). Unfortunately, the relatively limited Mo isotope database and small number of sample sets for Archean shales do not allow for in-depth reconstructions and specifically make it difficult to differentiate global from local effects. To accurately estimate the Mo isotope composition of Archean seawater and better investigate the systematics of local and global redox, more complete sample sets are needed. We carried out a Mo isotope analysis of the euxinic 2.65 Ga Roy Hill Shale sampled in two stratigraphically correlated cores, and revisited the well-studied euxinic 2.5 Ga Mt. McRae Shale in higher resolution. Our data show contrasting Mo isotope values in the 2.65 Ga Roy Hill Shale between near- and offshore depositional environments, with systematically heavier isotope values in the near-shore environment. High-resolution analysis of the Mt. McRae Shale yields oscillating Mo concentrations and isotope values at the cm- to dm-scale during the well-characterized "whiff of O2" interval, with the heaviest isotope values measured during euxinic deposition. Variations in the measured isotope values within each section are primarily associated with redox changes in the local depositional environment and amount of detrital content. Both non-quantitative removal of Mo associated with incorporation into non-euxinic sediments and large detrital Mo contributions shift some measured isotopic compositions toward lighter values. This is readily apparent in the near-shore Roy Hill Shale section and the Mt. McRae Shale, but may not fully explain variations observed in the offshore Roy Hill Shale deposit. Here, euxinic deposition is not accompanied by Mo enrichments or isotopic compositions as heavy as the near-shore equivalent, even after detrital correction. This disparity between the near- and offshore environment could signify spatial variation in the Mo isotope composition of 2.65 Ga seawater and highlights the need for multi-site and high-resolution studies in order to best assess paleoenvironmental conditions.

Experimental investigation of changes in methane adsorption of bitumen-free Woodford Shale with thermal maturation induced by hydrous pyrolysis

USGS Publications Warehouse

Hu, Haiyan; Zhang, Tongwei; Wiggins-Camacho, Jaclyn D.; Ellis, Geoffrey S.; Lewan, Michael D.; Zhang, Xiayong

2014-01-01

This study quantifies the effects of organic-matter (OM) thermal maturity on methane (CH4) sorption, on the basis of five samples that were artificially matured through hydrous pyrolysis achieved by heating samples of immature Woodford Shale under five different time–temperature conditions. CH4-sorption isotherms at 35 °C, 50 °C, and 65 °C, and pressures up to 14 MPa on dry, solvent-extracted samples of the artificially matured Woodford Shale were measured. The results showed that CH4-sorption capacity, normalized to TOC, varied with thermal maturity, following the trend: maximum oil (367 °C) > oil cracking (400 °C) > maximum bitumen/early oil (333 °C) > early bitumen (300 °C) > immature stage (130 °C). The Langmuir constants for the samples at maximum-oil and oil-cracking stages are larger than the values for the bitumen-forming stages. The total pore volume, determined by N2 physisorption at 77 K, increases with increased maturation: mesopores, 2–50 nm in width, were created during the thermal conversion of organic-matter and a dramatic increase in porosity appeared when maximum-bitumen and maximum-oil generation stages were reached. A linear relationship between thermal maturity and Brunauer–Emmett–Teller (BET) surface area suggests that the observed increase in CH4-sorption capacity may be the result of mesopores produced during OM conversion. No obvious difference is observed in pore-size distribution and pore volume for samples with pores 2 physisorption at 273 K. The isosteric heat of adsorption and the standard entropy for artificially matured samples ranged from 17.9 kJ mol−1 to 21.9 kJ mol−1 and from −85.4 J mol−1 K−1 to −101.8 J mol−1 K−1, respectively. These values are similar to the values of immature Woodford kerogen concentrate previously observed, but are larger than naturally matured organic-rich shales. High-temperature hydrous pyrolysis might have induced Lewis acid sites on both organic and mineral surfaces, resulting to some extent, in chemical interactions between the adsorption site and the methane C–H bonds. The formation of abundant mesopores (2–50 nm) within organic matter during organic-matter thermal maturation makes a great contribution to the increase in both BET surface area and pore volume, and a significant increase in 2–6 nm pores occurs at maximum-oil-generation and oil-cracking to gas, ultimately controlling the methane-adsorption capacity. Therefore, consideration of pore-size effects and thermal maturity is very important for gas in place (GIP) prediction in organic-rich shales.

Standardization of reflectance measurements in dispersed organic matter: results of an exercise to improve interlaboratory agreement

USGS Publications Warehouse

Hackley, Paul C.; Araujo, Carla Viviane; Borrego, Angeles G.; Bouzinos, Antonis; Cardott, Brian; Cook, Alan C.; Eble, Cortland; Flores, Deolinda; Gentzis, Thomas; Gonçalves, Paula Alexandra; Filho, João Graciano Mendonça; Hámor-Vidó, Mária; Jelonek, Iwona; Kommeren, Kees; Knowles, Wayne; Kus, Jolanta; Mastalerz, Maria; Menezes, Taíssa Rêgo; Newman, Jane; Pawlewicz, Mark; Pickel, Walter; Potter, Judith; Ranasinghe, Paddy; Read, Harold; Reyes, Julito; Rodriguez, Genaro De La Rosa; de Souza, Igor Viegas Alves Fernandes; Suarez-Ruiz, Isabel; Sýkorová, Ivana; Valentine, Brett J.

2015-01-01

Vitrinite reflectance generally is considered the most robust thermal maturity parameter available for application to hydrocarbon exploration and petroleum system evaluation. However, until 2011 there was no standardized methodology available to provide guidelines for vitrinite reflectance measurements in shale. Efforts to correct this deficiency resulted in publication of ASTM D7708: Standard test method for microscopical determination of the reflectance of vitrinite dispersed in sedimentary rocks. In 2012-2013, an interlaboratory exercise was conducted to establish precision limits for the D7708 measurement technique. Six samples, representing a wide variety of shale, were tested in duplicate by 28 analysts in 22 laboratories from 14 countries. Samples ranged from immature to overmature (0.31-1.53% Ro), from organic-lean to organic-rich (1-22 wt.% total organic carbon), and contained Type I (lacustrine), Type II (marine), and Type III (terrestrial) kerogens. Repeatability limits (maximum difference between valid repetitive results from same operator, same conditions) ranged from 0.03-0.11% absolute reflectance, whereas reproducibility limits (maximum difference between valid results obtained on same test material by different operators, different laboratories) ranged from 0.12-0.54% absolute reflectance. Repeatability and reproducibility limits degraded consistently with increasing maturity and decreasing organic content. However, samples with terrestrial kerogens (Type III) fell off this trend, showing improved levels of reproducibility due to higher vitrinite content and improved ease of identification. Operators did not consistently meet the reporting requirements of the test method, indicating that a common reporting template is required to improve data quality. The most difficult problem encountered was the petrographic distinction of solid bitumens and low-reflecting inert macerals from vitrinite when vitrinite occurred with reflectance ranges overlapping the other components. Discussion among participants suggested this problem could not be easily corrected via kerogen concentration or solvent extraction and is related to operator training and background. No statistical difference in mean reflectance was identified between participants reporting bitumen reflectance vs. vitrinite reflectance vs. a mixture of bitumen and vitrinite reflectance values, suggesting empirical conversion schemes should be treated with caution. Analysis of reproducibility limits obtained during this exercise in comparison to reproducibility limits from historical interlaboratory exercises suggests use of a common methodology (D7708) improves interlaboratory precision. Future work will investigate opportunities to improve reproducibility in high maturity, organic-lean shale varieties.

Organic compounds in produced waters from shale gas wells.

PubMed

Maguire-Boyle, Samuel J; Barron, Andrew R

2014-01-01

A detailed analysis is reported of the organic composition of produced water samples from typical shale gas wells in the Marcellus (PA), Eagle Ford (TX), and Barnett (NM) formations. The quality of shale gas produced (and frac flowback) waters is a current environmental concern and disposal problem for producers. Re-use of produced water for hydraulic fracturing is being encouraged; however, knowledge of the organic impurities is important in determining the method of treatment. The metal content was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Mineral elements are expected depending on the reservoir geology and salts used in hydraulic fracturing; however, significant levels of other transition metals and heavier main group elements are observed. The presence of scaling elements (Ca and Ba) is related to the pH of the water rather than total dissolved solids (TDS). Using gas chromatography mass spectrometry (GC/MS) analysis of the chloroform extracts of the produced water samples, a plethora of organic compounds were identified. In each water sample, the majority of organics are saturated (aliphatic), and only a small fraction comes under aromatic, resin, and asphaltene categories. Unlike coalbed methane produced water it appears that shale oil/gas produced water does not contain significant quantities of polyaromatic hydrocarbons reducing the potential health hazard. Marcellus and Barnett produced waters contain predominantly C6-C16 hydrocarbons, while the Eagle Ford produced water shows the highest concentration in the C17-C30 range. The structures of the saturated hydrocarbons identified generally follows the trend of linear > branched > cyclic. Heterocyclic compounds are identified with the largest fraction being fatty alcohols, esters, and ethers. However, the presence of various fatty acid phthalate esters in the Barnett and Marcellus produced waters can be related to their use in drilling fluids and breaker additives rather than their presence in connate fluids. Halogen containing compounds are found in each of the water samples, and although the fluorocarbon compounds identified are used as tracers, the presence of chlorocarbons and organobromides formed as a consequence of using chlorine containing oxidants (to remove bacteria from source water), suggests that industry should concentrate on non-chemical treatments of frac and produced waters.

Geology of the Devonian black shales of the Appalachian basin

USGS Publications Warehouse

Roen, J.B.

1983-01-01

Black shales of Devonian age in the Appalachian basin are a unique rock sequence. The high content of organic matter, which imparts the characteristic lithology, has for years attracted considerable interest in the shales as a possible source of energy. Concurrent with periodic and varied economic exploitations of the black shales are geologic studies. The recent energy shortage prompted the U.S. Department of Energy through the Eastern Gas Shales Project of the Morgantown Energy Technology Center to underwrite a research program to determine the geologic, geochemical, and structural characteristics of the Devonian black shales in order to enhance the recovery of gas from the shales. Geologic studies produced a regional stratigraphic network that correlates the 15-foot sequence in Tennessee with 3,000 feet of interbedded black and gray shales in central New York. The classic Devonian black-shale sequence in New York has been correlated with the Ohio Shale of Ohio and Kentucky and the Chattanooga Shale of Tennessee and southwestern Virginia. Biostratigraphic and lithostratigraphic markers in conjunction with gamma-ray logs facilitated long range correlations within the Appalachian basin and provided a basis for correlations with the black shales of the Illinois and Michigan basins. Areal distribution of selected shale units along with paleocurrent studies, clay mineralogy, and geochemistry suggests variations in the sediment source and transport directions. Current structures, faunal evidence, lithologic variations, and geochemical studies provide evidence to support interpretation of depositional environments. In addition, organic geochemical data combined with stratigraphic and structural characteristics of the shale within the basin allow an evaluation of the resource potential of natural gas in the Devonian shale sequence.

Stress-dependent elastic properties of shales—laboratory experiments at seismic and ultrasonic frequencies

NASA Astrophysics Data System (ADS)

Szewczyk, Dawid; Bauer, Andreas; Holt, Rune M.

2018-01-01

Knowledge about the stress sensitivity of elastic properties and velocities of shales is important for the interpretation of seismic time-lapse data taken as part of reservoir and caprock surveillance of both unconventional and conventional oil and gas fields (e.g. during 4-D monitoring of CO2 storage). Rock physics models are often developed based on laboratory measurements at ultrasonic frequencies. However, as shown previously, shales exhibit large seismic dispersion, and it is possible that stress sensitivities of velocities are also frequency dependent. In this work, we report on a series of seismic and ultrasonic laboratory tests in which the stress sensitivity of elastic properties of Mancos shale and Pierre shale I were investigated. The shales were tested at different water saturations. Dynamic rock engineering parameters and elastic wave velocities were examined on core plugs exposed to isotropic loading. Experiments were carried out in an apparatus allowing for static-compaction and dynamic measurements at seismic and ultrasonic frequencies within single test. For both shale types, we present and discuss experimental results that demonstrate dispersion and stress sensitivity of the rock stiffness, as well as P- and S-wave velocities, and stiffness anisotropy. Our experimental results show that the stress-sensitivity of shales is different at seismic and ultrasonic frequencies, which can be linked with simultaneously occurring changes in the dispersion with applied stress. Measured stress sensitivity of elastic properties for relatively dry samples was higher at seismic frequencies however, the increasing saturation of shales decreases the difference between seismic and ultrasonic stress-sensitivities, and for moist samples stress-sensitivity is higher at ultrasonic frequencies. Simultaneously, the increased saturation highly increases the dispersion in shales. We have also found that the stress-sensitivity is highly anisotropic in both shales and that in some of the cases higher stress-sensitivity of elastic properties can be seen in the direction parallel to the bedding plane.

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

USGS Publications Warehouse

Tuttle, M.L.W.; Breit, G.N.

2009-01-01

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.

delta 15N and non-carbonate delta 13C values for two petroleum source rock reference materials and a marine sediment reference material

USGS Publications Warehouse

Dennen, Kristin O.; Johnson, Craig A.; Otter, Marshall L.; Silva, Steven R.; Wandless, Gregory A.

2006-01-01

Samples of United States Geological Survey (USGS) Certified Reference Materials USGS Devonian Ohio Shale (SDO-1), and USGS Eocene Green River Shale (SGR-1), and National Research Council Canada (NRCC) Certified Marine Sediment Reference Material (PACS-2), were sent for analysis to four separate analytical laboratories as blind controls for organic rich sedimentary rock samples being analyzed from the Red Dog mine area in Alaska. The samples were analyzed for stable isotopes of carbon (delta13Cncc) and nitrogen (delta15N), percent non-carbonate carbon (Wt % Cncc) and percent nitrogen (Wt % N). SDO-1, collected from the Huron Member of the Ohio Shale, near Morehead, Kentucky, and SGR-1, collected from the Mahogany zone of the Green River Formation are petroleum source rocks used as reference materials for chemical analyses of sedimentary rocks. PACS-2 is modern marine sediment collected from the Esquimalt, British Columbia harbor. The results presented in this study are, with the exceptions noted below, the first published for these reference materials. There are published information values for the elemental concentrations of 'organic' carbon (Wt % Corg measured range is 8.98 - 10.4) and nitrogen (Wt % Ntot 0.347 with SD 0.043) only for SDO-1. The suggested values presented here should be considered 'information values' as defined by the NRCC Institute for National Measurement Reference Materials and should be useful for the analysis of 13C, 15N, C and N in organic material in sedimentary rocks.

Development of Porosity Measurement Method in Shale Gas Reservoir Rock

NASA Astrophysics Data System (ADS)

Siswandani, Alita; Nurhandoko, BagusEndar B.

2016-08-01

The pore scales have impacts on transport mechanisms in shale gas reservoirs. In this research, digital helium porosity meter is used for porosity measurement by considering real condition. Accordingly it is necessary to obtain a good approximation for gas filled porosity. Shale has the typical effective porosity that is changing as a function of time. Effective porosity values for three different shale rocks are analyzed by this proposed measurement. We develop the new measurement method for characterizing porosity phenomena in shale gas as a time function by measuring porosity in a range of minutes using digital helium porosity meter. The porosity of shale rock measured in this experiment are free gas and adsorbed gas porosoty. The pressure change in time shows that porosity of shale contains at least two type porosities: macro scale porosity (fracture porosity) and fine scale porosity (nano scale porosity). We present the estimation of effective porosity values by considering Boyle-Gay Lussaac approximation and Van der Waals approximation.

Deliberating the perceived risks, benefits, and societal implications of shale gas and oil extraction by hydraulic fracturing in the US and UK

NASA Astrophysics Data System (ADS)

Thomas, Merryn; Partridge, Tristan; Harthorn, Barbara Herr; Pidgeon, Nick

2017-04-01

Shale gas and oil production in the US has increased rapidly in the past decade, while interest in prospective development has also arisen in the UK. In both countries, shale resources and the method of their extraction (hydraulic fracturing, or 'fracking') have been met with opposition amid concerns about impacts on water, greenhouse gas emissions, and health effects. Here we report the findings of a qualitative, cross-national deliberation study of public perceptions of shale development in UK and US locations not yet subject to extensive shale development. When presented with a carefully calibrated range of risks and benefits, participants' discourse focused on risks or doubts about benefits, and potential impacts were viewed as inequitably distributed. Participants drew on direct, place-based experiences as well as national contexts in deliberating shale development. These findings suggest that shale gas development already evokes a similar 'signature' of risk across the US and UK.

Determination of interstitial chloride in shales and consolidated rocks by a precision leaching technique

USGS Publications Warehouse

Manheim, Frank T.; Peck, E.E.; Lane, Candice M.

1985-01-01

The authors have devised a technique for determining chloride in interstitial water of consolidated rocks. Samples of rocks ranging from 5 to 10 g are crushed and sieved under controlled conditions and then ground with distilled water to submicron size in a closed mechanical mill. The chloride concentrations and total pore-water concentrations, obtained earlier from the same samples by low-temperature vacuum desiccation, are used to arrive at the 'original' pore-water chloride concentrations by a simple iteration procedure. Interstitial chlorinity results obtained from Cretaceous and Jurassic strata in the Gulf of Mexico coastal areas ranged from 20 to 100 g/kg Cl with reproducibility approaching plus or minus 1%.

Organic geochemistry: Effects of organic components of shales on adsorption: Progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, P.C.

1988-11-01

The Sedimentary Rock Program at the Oak Ridge National Laboratory is investigating shale to determine its potential suitability as a host rock for the disposal of high-level radioactive wastes (HLW). The selected shales are Upper Dowelltown, Pierre, Green River Formation, and two Conasauga (Nolichucky and Pumpkin Valley) Shales, which represent mineralogical and compositional extremes of shales in the United States. According to mineralogical studies, the first three shales contain 5 to 13 wt % of organic matter, and the two Conasauga Shales only contain trace amounts (2 wt %) of organic matter. Soxhlet extraction with chloroform and a mixture ofmore » chloroform and methanol can remove 0.07 to 5.9 wt % of the total organic matter from these shales. Preliminary analysis if these organic extracts reveals the existence of organic carboxylic acids and hydrocarbons in these samples. Adsorption of elements such as Cs(I), Sr(II) and Tc(VII) on the organic-extracted Upper Dowelltown, Pierre, green River Formation and Pumpkin Valley Shales in synthetic groundwaters (simulating groundwaters in the Conasauga Shales) and in 0.03-M NaHCO/sub 3/ solution indicates interaction between each of the three elements and the organic-extractable bitumen. 28 refs., 8 figs., 10 tabs.« less

43 CFR 3903.51 - Minimum production and payments in lieu of production.

Code of Federal Regulations, 2011 CFR

2011-10-01

...) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT...) Each lease must meet its minimum annual production amount of shale oil or make a payment in lieu of...

Lidar-based fracture characterization: An outcrop-scale study of the Woodford Shale, McAlister Shale Pit, Oklahoma

NASA Astrophysics Data System (ADS)

Hanzel, Jason

The use of lidar (light detection and ranging), a remote sensing tool based on principles of laser optometry, in mapping complex, multi-scale fracture networks had not been rigorously tested prior to this study despite its foreseeable utility in interpreting rock fabric with imprints of complex tectonic evolution. This thesis demonstrates lidar-based characterization of the Woodford Shale where intense fracturing could be due to both tectonism and mineralogy. The study area is the McAlister Shale Pit in south-central Oklahoma where both the upper and middle sections of the Woodford Shale are exposed and can be lidar-mapped. Lidar results are validated using hand-measured strike and dips of fracture planes, thin sections and mineral chemistry of selected samples using X-ray diffraction (XRD). Complexity of the fracture patterns as well as inaccessibility of multiple locations within the shale pit makes hand-measurement prone to errors and biases; lidar provides an opportunity for less biased and more efficient field mapping. Fracture mapping with lidar is a multi-step process. The lidar data are converted from point clouds into a mesh through triangulation. User-defined parameters such as size and orientation of the individual triangular elements are then used to group similar elements into surfaces. The strike and dip attribute of the simulated surfaces are visualized in an equal area lower hemisphere projection stereonet. Three fracture sets were identified in the upper and middle sections with common orientation but substantially different spatial density. Measured surface attributes and spatial density relations from lidar were validated using their hand-measured counterparts. Thin section analysis suggests that high fracture density in the upper Woodford measured by both the lidar and the hand-measured data could be due to high quartz. A significant finding of this study is the reciprocal relation between lidar intensity and gamma-ray (GR), which is generally used to infer outcrop mineralogy. XRD analysis of representative samples along the common profiles show that both GR and lidar intensity were influenced by the same minerals in essentially opposite ways. Results strongly suggest that the lidar cannot only remotely map the geomorphology, but also the relative mineralogical variations to the first order of approximation.

Multidimensional and comprehensive two-dimensional gas chromatography of dichloromethane soluble products from a high sulfur Jordanian oil shale.

PubMed

Amer, Mohammad W; Mitrevski, Blagoj; Jackson, W Roy; Chaffee, Alan L; Marriott, Philip J

2014-03-01

A high sulfur Jordanian oil shale was converted into liquid hydrocarbons by reaction at 390 °C under N2, and the dichloromethane soluble fraction of the products was isolated then analyzed by using gas chromatography (GC). Comprehensive two-dimensional GC (GC×GC) and multidimensional GC (MDGC) were applied for component separation on a polar - non-polar column set. Flame-ionization detection (FID) was used with GC×GC for general sample profiling, and mass spectrometry (MS) for component identification in MDGC. Multidimensional GC revealed a range of thiophenes (th), benzothiophenes (bth) and small amounts of dibenzothiophenes (dbth) and benzonaphthothiophenes (bnth). In addition, a range of aliphatic alkanes and cycloalkanes, ethers, polar single ring aromatic compounds and small amounts of polycyclic aromatics were also identified. Some of these compound classes were not uniquely observable by conventional 1D GC, and certainly this is true for many of their minor constituent members. The total number of distinct compounds was very large (ca.>1000). GC×GC was shown to be appropriate for general sample profiling, and MDGC-MS proved to be a powerful technique for the separation and identification of sulfur-containing components and other polar compounds. © 2013 Published by Elsevier B.V.

Geochemical variations of rare earth elements in Marcellus shale flowback waters and multiple-source cores in the Appalachian Basin

NASA Astrophysics Data System (ADS)

Noack, C.; Jain, J.; Hakala, A.; Schroeder, K.; Dzombak, D. A.; Karamalidis, A.

2013-12-01

Rare earth elements (REE) - encompassing the naturally occurring lanthanides, yttrium, and scandium - are potential tracers for subsurface groundwater-brine flows and geochemical processes. Application of these elements as naturally occurring tracers during shale gas development is reliant on accurate quantitation of trace metals in hypersaline brines. We have modified and validated a liquid-liquid technique for extraction and pre-concentration of REE from saline produced waters from shale gas extraction wells with quantitative analysis by ICP-MS. This method was used to analyze time-series samples of Marcellus shale flowback and produced waters. Additionally, the total REE content of core samples of various strata throughout the Appalachian Basin were determined using HF/HNO3 digestion and ICP-MS analysis. A primary goal of the study is to elucidate systematic geochemical variations as a function of location or shale characteristics. Statistical testing will be performed to study temporal variability of inter-element relationships and explore associations between REE abundance and major solution chemistry. The results of these analyses and discussion of their significance will be presented.

Visual classification of very fine-grained sediments: Evaluation through univariate and multivariate statistics

USGS Publications Warehouse

Hohn, M. Ed; Nuhfer, E.B.; Vinopal, R.J.; Klanderman, D.S.

1980-01-01

Classifying very fine-grained rocks through fabric elements provides information about depositional environments, but is subject to the biases of visual taxonomy. To evaluate the statistical significance of an empirical classification of very fine-grained rocks, samples from Devonian shales in four cored wells in West Virginia and Virginia were measured for 15 variables: quartz, illite, pyrite and expandable clays determined by X-ray diffraction; total sulfur, organic content, inorganic carbon, matrix density, bulk density, porosity, silt, as well as density, sonic travel time, resistivity, and ??-ray response measured from well logs. The four lithologic types comprised: (1) sharply banded shale, (2) thinly laminated shale, (3) lenticularly laminated shale, and (4) nonbanded shale. Univariate and multivariate analyses of variance showed that the lithologic classification reflects significant differences for the variables measured, difference that can be detected independently of stratigraphic effects. Little-known statistical methods found useful in this work included: the multivariate analysis of variance with more than one effect, simultaneous plotting of samples and variables on canonical variates, and the use of parametric ANOVA and MANOVA on ranked data. ?? 1980 Plenum Publishing Corporation.

Limited fluid in carbonate-shale hosted thrust faults of the Rocky Mountain Fold-and-Thrust Belt (Sun River Canyon, Montana)

NASA Astrophysics Data System (ADS)

OBrien, V. J.; Kirschner, D. L.

2001-12-01

It is widely accepted that fluids play a fundamental role in the movement of thrust faults in foreland fold-and-thrust belts. We have begun a combined structure-geochemistry study of faults in the Rocky Mountain fold-and-thrust belt in order to provide more insight into the occurrence and role(s) of fluid in the deformation of thrust faults. We focus on faults exposed in the Sun River Canyon of Montana, an area that contains some of the best exposures of the Rocky Mountain fold-and-thrust belt in the U.S. Samples were collected from two well exposed thrusts in the Canyon -- the Diversion and French thrusts. Both faults have thrust Mississippian dolostones over Cretaceous shales. Displacement exceeds several kilometers. Numerous small-displacement, subsidiary faults characterize the deformation in the hanging wall carbonates. The footwall shales accommodated more penetrative deformation, resulting in well developed foliation and small-scale folds. Stable isotope data have been obtained from host rock samples and veins from these faults. The data delimit an arcuate trend in oxygen-carbon isotope space. Approximately 50 host rock carbonate samples from the hanging walls have carbon and oxygen isotope values ranging from +3 to 0 and 28 to 19 per mil, respectively. There is no apparent correlation between isotopic values and distance from thrust fault at either locality. Fifteen samples of fibrous slickensides on small-displacement faults in the hanging walls have similar carbon and lower oxygen isotope values (down to 16 per mil). And 15 veins that either post-date thrusting or are of indeterminate origin have carbon and oxygen isotope values down to -3 and12 per mil, respectively. The isotopic data collected during the initial stages of this project are similar to some results obtained several hundred kilometers north in the Front Ranges of the Canadian Rockies (Kirschner and Kennedy, JGR 2000) and in carbonate fold-thrust belts of the Swiss Helvetic Alps and Italian Apennines. These data are consistent with limited infiltration of fluid through fractures and minor faults into hanging walls of large-displacement thrust faults.

Mechanical Properties of Gas Shale During Drilling Operations

NASA Astrophysics Data System (ADS)

Yan, Chuanliang; Deng, Jingen; Cheng, Yuanfang; Li, Menglai; Feng, Yongcun; Li, Xiaorong

2017-07-01

The mechanical properties of gas shale significantly affect the designs of drilling, completion, and hydraulic fracturing treatments. In this paper, the microstructure characteristics of gas shale from southern China containing up to 45.1% clay were analyzed using a scanning electron microscope. The gas shale samples feature strongly anisotropic characteristics and well-developed bedding planes. Their strength is controlled by the strength of both the matrix and the bedding planes. Conventional triaxial tests and direct shear tests are further used to study the chemical effects of drilling fluids on the strength of shale matrix and bedding planes, respectively. The results show that the drilling fluid has a much larger impact on the strength of the bedding plane than that of the shale matrix. The impact of water-based mud (WBM) is much larger compared with oil-based mud. Furthermore, the borehole collapse pressure of shale gas wells considering the effects of drilling fluids are analyzed. The results show that the collapse pressure increases gradually with the increase of drilling time, especially for WBM.

Oil/source rock correlations in the Polish Flysch Carpathians and Mesozoic basement and organic facies of the Oligocene Menilite Shales: Insights from hydrous pyrolysis experiments

USGS Publications Warehouse

Curtis, John B.; Kotarba, M.J.; Lewan, M.D.; Wieclaw, D.

2004-01-01

The Oligocene Menilite Shales in the study area in the Polish Flysch Carpathians are organic-rich and contain varying mixtures of Type-II, Type-IIS and Type-III kerogen. The kerogens are thermally immature to marginally mature based on atomic H/C ratios and Rock-Eval data. This study defined three organic facies, i.e., sedimentary strata with differing hydrocarbon-generation potentials due to varying types and concentrations of organic matter. These facies correspond to the Silesian Unit and the eastern and western portions of the Skole Unit. Analysis of oils generated by hydrous pyrolysis of outcrop samples of Menilite Shales demonstrates that natural crude oils reservoired in the flysch sediments appear to have been generated from the Menilite Shales. Natural oils reservoired in the Mesozoic basement of the Carpathian Foredeep appear to be predominantly derived and migrated from Menilite Shales, with a minor contribution from at least one other source rock most probably within Middle Jurassic strata. Definition of organic facies may have been influenced by the heterogeneous distribution of suitable Menilite Shales outcrops and producing wells, and subsequent sample selection during the analytical phases of the study. ?? 2004 Elsevier Ltd. All rights reserved.

Exposure to dust and particle-associated 1-nitropyrene of drivers of diesel-powered equipment in underground mining.

PubMed

Scheepers, P T J; Micka, V; Muzyka, V; Anzion, R; Dahmann, D; Poole, J; Bos, R P

2003-07-01

A field study was conducted in two mines in order to determine the most suitable strategy for ambient exposure assessment in the framework of a European study aimed at validation of biological monitoring approaches for diesel exhaust (BIOMODEM). Exposure to dust and particle-associated 1-nitropyrene (1-NP) was studied in 20 miners of black coal by the long wall method (Czech Republic) and in 20 workers in oil shale mining by the room and pillar method (Estonia). The study in the oil shale mine was extended to include 100 workers in a second phase (main study). In each mine half of the study population worked underground as drivers of diesel-powered trains (black coal) and excavators (oil shale). The other half consisted of workers occupied in various non-diesel production assignments. Exposure to diesel exhaust was studied by measurement of inhalable and respirable dust at fixed locations and by personal air sampling of respirable dust. The ratio of geometric mean inhalable to respirable dust concentration was approximately two to one. The underground/surface ratio of respirable dust concentrations measured at fixed locations and in the breathing zones of the workers was 2-fold or greater. Respirable dust was 2- to 3-fold higher in the breathing zone than at fixed sampling locations. The 1-NP content in these dust fractions was determined by gas chromatography-mass spectrometry/mass spectrometry and ranged from 0.003 to 42.2 ng/m(3) in the breathing zones of the workers. In mine dust no 1-NP was detected. In both mines 1-NP was observed to be primarily associated with respirable particles. The 1-NP concentrations were also higher underground than on the surface (2- to 3-fold in the coal mine and 10-fold or more in the oil shale mine). Concentrations of 1-NP in the breathing zones were also higher than at fixed sites (2.5-fold in the coal mine and 10-fold in the oil shale mine). For individual exposure assessment personal air sampling is preferred over air sampling at fixed sites. This study also suggests that particle-associated 1-NP much better reflects the ambient exposure to diesel exhaust particles than dust concentrations. Therefore, measurement of particle-associated 1-NP is preferred over measurement of dust concentrations by gravimetry, when linking ambient exposure to biomonitoring outcomes such as protein and DNA adducts and excretion of urinary metabolites of genotoxic substances.

The atmospheric inventory of Xenon and noble cases in shales The plastic bag experiment

NASA Technical Reports Server (NTRS)

Bernatowicz, T. J.; Podosek, F. A.; Honda, M.; Kramer, F. E.

1984-01-01

A novel trapped gas analysis protocol is applied to five shales in which the samples are sealed in air to eliminate the possibility of gas loss in the preanalysis laboratory vacuum exposure of a conventional protocol. The test is aimed at a determination concerning the hypothesis that atmospheric noble gases occur in the same proportion as planetary gases in meteorites, and that the factor-of-23 deficiency of air Xe relative to planetary Xe is made up by Xe stored in shales or other sedimentary rocks. The results obtained do not support the shale hypothesis.

Characterization of the Marcellus Shale based on computer-assisted correlation of wireline logs in Virginia and West Virginia

USGS Publications Warehouse

Enomoto, Catherine B.; Olea, Ricardo A.; Coleman, James L.

2014-01-01

The Middle Devonian Marcellus Shale in the Appalachian basin extends from central Ohio on the west to eastern New York on the east, and from north-central New York on the north to northern Tennessee on the south. Its thickness ranges from 0 feet (ft) where it pinches out to the west to as much as 700 ft in its eastern extent. Within the Broadtop synclinorium, the thickness of the Marcellus Shale ranges from 250 to 565 ft. Although stratigraphic complexities have been documented, a significant range in thickness most likely is because of tectonic thickening from folds and thrust faults. Outcrop studies in the Valley and Ridge and Appalachian Plateaus provinces illustrate the challenges of interpreting the relation of third-order faults, folds, and “disturbed” zones to the regional tectonic framework. Recent field work within the Valley and Ridge province determined that significant faulting and intraformational deformation are present within the Marcellus Shale at the outcrop scale. In an attempt to determine if this scale of deformation is detectable with conventional wireline logs, petrophysical properties (primarily mineralogy and porosity) were measured by interpretation of gamma-ray and bulk-density logs. The results of performing a statistical correlation of wireline logs from nine wells indicated that there are discontinuities within the Millboro Shale (undifferentiated Marcellus Shale and Mahantango Formation) where there are significant thickness differences between wells. Also, some intervals likely contain mineralogy that makes these zones more prone to layer-shortening cleavage duplexes. The Correlator program proved to be a useful tool in a region of contractional deformation.

Chemical and mineralogical analysis of devonian black-shale samples from Martin County, Kentucky; Carroll and Washington counties, Ohio; Wise County, Virginia; and Overton County, Tennessee, U.S.A.

USGS Publications Warehouse

Leventhal, J.S.; Hosterman, J.W.

1982-01-01

Core samples of Devonian shales from five localities in the Appalachian basin have been analyzed chemically and mineralogically. The amounts of major elements are similar; however, the minor constituents, organic C, S, phosphate and carbonate show ten-fold variations in amounts. Trace elements Mo, Ni, Cu, V, Co, U, Zn, Hg, As and Mn show variations in amounts that can be related to the minor constituents. All samples contain major amounts of quartz, illite, two types of mixed-layer clays, and chlorite in differing quantities. Pyrite, calcite, feldspar and kaolinite are also present in many samples in minor amounts. Dolomite, apatite, gypsum, barite, biotite and marcasite are present in a few samples in trace amounts. Trace elements listed above are strongly controlled by organic C with the exception of Mn which is associated with carbonate minerals. Amounts of organic C generally range from 3 to 6%, and S is in the range of 2-5%. Amounts of trace elements show the following general ranges in ppm (parts per million): Co, 20-40; Cu, 40-70; U, 10-40; As, 20-40; V, 150-300; Ni, 80-150; high values are as much as twice these values. The organic C was probably the concentrating agent, and the organic C and sulfide S together created an environment that immobilized and preserved these trace elements. Closely spaced samples showing an abrupt transition in color also show changes in organic C, S and trace-element contents. Several associations exist between mineral and chemical content. Pyrite and marcasite are the only minerals found to contain sulfide-S. In general, the illite-chlorite mixed-layer clay mineral shows covariation with organic C if calcite is not present. The enriched trace elements are not related to the clay types, although the clay and organic matter are intimately associated as the bulk fabric of the rock. ?? 1982.

Characterization and growth mechanism of a peculiar nodular structure in shale: Comprehensive study over the Sitakund anticline, Bengal basin.

NASA Astrophysics Data System (ADS)

Gazi, M. Y.; Kabir, S. M. M.; Imam, M. B.

2017-12-01

Nodular shales commonly occur in comparatively older and silty shales near the axial (proximity to core) region of Sitakund Anticline (Study area), Sitapahar Anticline, Patharia Structure, Sylhet Anticline and Mirinja Anticline as observed. Stratigraphically, they are pronounced in the Surma group of Neogene succession. They are less abundant in limb portion. In many outcrop, they are found in the incompetent bed with the obliterated bedding bounded by well bedded competent beds. Their occurrence are sporadic rather than continuous along and across the strike of the bed. At some places huge number cluster of small and big nodular shales occur while in the other places, they occur as isolated mass in the highly disturbed or obliterated beds. The Surma group is the prime startigraphic unit in Bangladesh with major economic and academic importance. Yet there is a lack of comprehensive characterization of mudrocks of Surma group. This has prompted the present research to be undertaken. An initial field based study has been followed by detail textural, mineralogical, petrological and geochemical by using upscale laboratory techniques that include Thin Section Microscopy, Laser Particle Size Analyses, X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and X-ray Florescence (XRF). From laser diffraction analysis, it is evident that nodular shales are silty in nature containing approximately 60% silt (Mainly quartz). XRD pattern shows that Nodular shale contains clay minerals, predominantly illite, Kaolinite, Chlorite and expandable mixed layer clay mineral. Detail geochemical analysis of some nodular shale samples shows that there are no significant variation from other samples in major and trace element concentration. Microcrack's within the quartz grains were observed in nodular shale. Projection of 15 nodular shale long axes in outcrop shows their orientation in NNW-SSE that is parallel to the fold axis. The study suggests a new name of conventionally called nodular shales. The proposed name is "Clay Cabbage". A new model naming as "Tectono-Diagenetic (TD) Model" is proposed in this study concerning the origin of nodular shale.

Local CO2-induced swelling of shales

NASA Astrophysics Data System (ADS)

Pluymakers, Anne; Dysthe, Dag Kristian

2017-04-01

In heterogeneous shale rocks, CO2 adsorbs more strongly to organic matter than to the other components. CO2-induced swelling of organic matter has been shown in coal, which is pure carbon. The heterogeneity of the shale matrix makes an interesting case study. Can local swelling through adsorption of CO2 to organic matter induce strain in the surrounding shale matrix? Can fractures close due to CO2-induced swelling of clays and organic matter? We have developed a new generation of microfluidic high pressure cells (up to 100 bar), which can be used to study flow and adsorption phenomena at the microscale in natural geo-materials. The devices contain one transparent side and a shale sample on the other side. The shale used is the Pomeranian shale, extracted from 4 km depth in Poland. This formation is a potential target of a combined CO2-storage and gas extraction project. To answer the first question, we place the pressure cell under a Veeco NT1100 Interferometer, operated in Vertical Scanning Interferometry mode and equipped with a Through Transmissive Media objective. This allows for observation of local swelling or organic matter with nanometer vertical resolution and micrometer lateral resolution. We expose the sample to CO2 atmospheres at different pressures. Comparison of the interferometry data and using SEM-EDS maps plus optical microscopy delivers local swelling maps where we can distinguish swelling of different mineralogies. Preliminary results indicate minor local swelling of organic matter, where the total amount is both time- and pressure-dependent.

Correlation between electron spin resonance spectra and oil yield in eastern oil shales

USGS Publications Warehouse

Choudhury, M.; Rheams, K.F.; Harrell, J.W.

1986-01-01

Organic free radical spin concentrations were measured in 60 raw oil shale samples from north Alabama and south Tennessee and compared with Fischer assays and uranium concentrations. No correlation was found between spin concentration and oil yield for the complete set of samples. However, for a 13 sample set taken from a single core hole, a linear correlation was obtained. No correlation between spin concentration and uranium concentration was found. ?? 1986.

Monitoring concentration and isotopic composition of methane in groundwater in the Utica Shale hydraulic fracturing region of Ohio.

PubMed

Claire Botner, E; Townsend-Small, Amy; Nash, David B; Xu, Xiaomei; Schimmelmann, Arndt; Miller, Joshua H

2018-05-03

Degradation of groundwater quality is a primary public concern in rural hydraulic fracturing areas. Previous studies have shown that natural gas methane (CH 4 ) is present in groundwater near shale gas wells in the Marcellus Shale of Pennsylvania, but did not have pre-drilling baseline measurements. Here, we present the results of a free public water testing program in the Utica Shale of Ohio, where we measured CH 4 concentration, CH 4 stable isotopic composition, and pH and conductivity along temporal and spatial gradients of hydraulic fracturing activity. Dissolved CH 4 ranged from 0.2 μg/L to 25 mg/L, and stable isotopic measurements indicated a predominantly biogenic carbonate reduction CH 4 source. Radiocarbon dating of CH 4 in combination with stable isotopic analysis of CH 4 in three samples indicated that fossil C substrates are the source of CH 4 in groundwater, with one 14 C date indicative of modern biogenic carbonate reduction. We found no relationship between CH 4 concentration or source in groundwater and proximity to active gas well sites. No significant changes in CH 4 concentration, CH 4 isotopic composition, pH, or conductivity in water wells were observed during the study period. These data indicate that high levels of biogenic CH 4 can be present in groundwater wells independent of hydraulic fracturing activity and affirm the need for isotopic or other fingerprinting techniques for CH 4 source identification. Continued monitoring of private drinking water wells is critical to ensure that groundwater quality is not altered as hydraulic fracturing activity continues in the region. Graphical abstract A shale gas well in rural Appalachian Ohio. Photo credit: Claire Botner.

Oil and gas geochemistry and petroleum systems of the Fort Worth Basin

USGS Publications Warehouse

Hill, R.J.; Jarvie, D.M.; Zumberge, J.; Henry, M.; Pollastro, R.M.

2007-01-01

Detailed biomarker and light hydrocarbon geochemistry confirm that the marine Mississippian Barnett Shale is the primary source rock for petroleum in the Fort Worth Basin, north-central Texas, although contributions from other sources are possible. Biomarker data indicate that the main oil-generating Barnett Shale facies is marine and was deposited under dysoxic, strong upwelling, normal salinity conditions. The analysis of two outcrop samples and cuttings from seven wells indicates variability in the Barnett Shale organic facies and a possibility of other oil subfamilies being present. Light hydrocarbon analyses reveal significant terrigenous-sourced condensate input to some reservoirs, resulting in terrigenous and mixed marine-terrigenous light hydrocarbon signatures for many oils. The light hydrocarbon data suggest a secondary, condensate-generating source facies containing terrigenous or mixed terrigenous-marine organic matter. This indication of a secondary source rock that is not revealed by biomarker analysis emphasizes the importance of integrating biomarker and light hydrocarbon data to define petroleum source rocks. Gases in the Fort Worth Basin are thermogenic in origin and appear to be cogenerated with oil from the Barnett Shale, although some gas may also originate by oil cracking. Isotope data indicate minor contribution of biogenic gas. Except for reservoirs in the Pennsylvanian Bend Group, which contain gases spanning the complete range of observed maturities, the gases appear to be stratigraphically segregated, younger reservoirs contain less mature gas, and older reservoirs contain more mature gas. We cannot rule out the possibility that other source units within the Fort Worth Basin, such as the Smithwick Shale, are locally important petroleum sources. Copyright ?? 2007. The American Association of Petroleum Geologists. All rights reserved.

Water and mineral relations of Atriplex canescens and A. cuneata on saline processed oil shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richardson, S.G.

1979-01-01

Growth, mineral uptake and water relations of Atriplex canescens and A. cuneata, both native to the arid oil shale region of northeastern Utah, were studied in the greenhouse and laboratory as affected by various salinity levels and specific ions in processed oil shale. Salinity of the shale was manipulated by moistening leached processed oil shale to near field capacity (20% H/sub 2/O by weight) with solutions of shale leachate, sodium sulfate, magnesium sulfate or sodium chloride at equiosmotic concentrations ranging from 0 to -30 bars. Although shale salinity did not affect osmotic adjustment, zero turgor points of A. canescens becamemore » more negative with reductions in shale moisture percentage. Differences in plant growth due to differet ions in the soil solution could not be explained by effects on osmotic adjustment. However, greater growth of A. canescens in Na/sub 2/SO/sub 4/ treated than MgSO/sub 4/ treated leached shale was associated with greater leaf succulence, greater lamina lengths and lamina widths and lower diffusive leaf resistances. Potassium added to leached and unleached processed oil shale increased shoot and root biomass production, shoot/root ratio, leaf K content, and water use efficiency of a sodium-excluding Atriplex canescens biotype but did not increase growth of a sodium-accumulating biotype.« less

Spectroscopic geochemical study of vanadiferous marine sediments of the Gibellini claims, southern Fish Creek Range, Eureka County, Nevada

USGS Publications Warehouse

Böhlke, J.K.; Radtke, A.S.; Heropoulos, Chris; Lamothe, P.J.

1981-01-01

Samples of cuttings from three drill holes in the Gibellini claims were analyzed by emission spectroscopic techniques for a large suite of major and trace elements. Unoxidized siliceous "black shale" from drill hole NGA 7 is strongly enriched in Cd, Mo, Sb, Se, V, and Zn, and also contains relatively high concentrations of As, Ba, Cu, Ni, and Tl compared with nonmetalliferous shales. Analyses of 103 samples plotted against depth in drill holes NGA, NG31, and NGA7, and selected XRD data, show the following: 1. Groups of elements with distinct distribution patterns define most of major mineralogic components of the rocks. The "normal shale" component, which includes several detrital and authigenic phases, is indicated by covariations among Ti, Al, Fe, Na, Mg, K, B, Be, Co, Cr, Ga, La, Sc, Sr, and Zr. The shale component is diluted by varying amounts of the following minerals (and associated elements): silica (Si); dolomite (Mg, Ca, Mn, Sr); apatite (Ca, Be, Cr, La, Sr, Y); barite (Ba, Sr); sphalerite (Zn, Cd, Fe?); smithsonite (Cd, Co, Mn, Ni, Zn); bianchite (Cd, Ni, Zn) ; and bokite (V). Pyrite, gypsum, and jarosite were also identified.2. The highly siliceous kerogenous metalliferous Gibellini facies is underlain by argillaceous and (or) dolomitic rocks. The transition zone deduced from the chemical data is not well defined in all instances, but probably represents the bottom of the black shale deposit. 3. Oxidation has reached to variable depths up to at least 150 ft, and has caused profound changes in the distributions of the enriched metals. Molybdenum, Se, and V have been partially removed from the upper parts of the sections and are concentrated near or slightly above the base of the Gibellini facies. Cadmium, Ni, and Zn have been strongly leached and now occur at or below the base of the Gibellini facies. The variable depth of oxidation, the redistribution and separation of the metals, and the complex mineralogy of the deposit may make development of the claim complicated.

Thermal stability of some aircraft turbine fuels derived from oil shale and coal

NASA Technical Reports Server (NTRS)

Reynolds, T. W.

1977-01-01

Thermal stability breakpoint temperatures are shown for 32 jet fuels prepared from oil shale and coal syncrudes by various degrees of hydrogenation. Low severity hydrotreated shale oils, with nitrogen contents of 0.1 to 0.24 weight percent, had breakpoint temperatures in the 477 to 505 K (400 to 450 F) range. Higher severity treatment, lowering nitrogen levels to 0.008 to 0.017 weight percent, resulted in breakpoint temperatures in the 505 to 533 K (450 to 500 F) range. Coal derived fuels showed generally increasing breakpoint temperatures with increasing weight percent hydrogen, fuels below 13 weight percent hydrogen having breakpoints below 533 K (500 F). Comparisons are shown with similar literature data.

Carbon Dioxide Sealing Capacity: Textural or Compositional Controls?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cranganu, Constantin; Soleymani, Hamidreza; Sadiqua, Soleymani

2013-11-30

This research project is aiming to assess the carbon dioxide sealing capacity of most common seal-rocks, such as shales and non-fractured limestones, by analyzing the role of textural and compositional parameters of those rocks. We hypothesize that sealing capacity is controlled by textural and/or compositional pa-rameters of caprocks. In this research, we seek to evaluate the importance of textural and compositional parameters affecting the sealing capacity of caprocks. The conceptu-al framework involves two testable end-member hypotheses concerning the sealing ca-pacity of carbon dioxide reservoir caprocks. Better understanding of the elements controlling sealing quality will advance our knowledge regarding the sealingmore » capacity of shales and carbonates. Due to relatively low permeability, shale and non-fractured carbonate units are considered relatively imper-meable formations which can retard reservoir fluid flow by forming high capillary pres-sure. Similarly, these unites can constitute reliable seals for carbon dioxide capture and sequestration purposes. This project is a part of the comprehensive project with the final aim of studying the caprock sealing properties and the relationship between microscopic and macroscopic characteristics of seal rocks in depleted gas fields of Oklahoma Pan-handle. Through this study we examined various seal rock characteristics to infer about their respective effects on sealing capacity in special case of replacing reservoir fluid with super critical carbon dioxide (scCO{sub 2}). To assess the effect of textural and compositional properties on scCO{sub 2} maximum reten-tion column height we collected 30 representative core samples in caprock formations in three counties (Cimarron, Texas, Beaver) in Oklahoma Panhandle. Core samples were collected from various seal formations (e.g., Cherokee, Keys, Morrowan) at different depths. We studied the compositional and textural properties of the core samples using several techniques. Mercury Injection Porosimetry (MIP), Scanning Electron Microsco-py SEM, and Sedigraph measurements are used to assess the pore-throat-size distribu-tion, sorting, texture, and grain size of the samples. Also, displacement pressure at 10% mercury saturation (Pd) and graphically derived threshold pressure (Pc) were deter-mined by MIP technique. SEM images were used for qualitative study of the minerals and pores texture of the core samples. Moreover, EDS (Energy Dispersive X-Ray Spec-trometer), BET specific surface area, and Total Organic Carbon (TOC) measurements were performed to study various parameters and their possible effects on sealing capaci-ty of the samples. We found that shales have the relatively higher average sealing threshold pressure (Pc) than carbonate and sandstone samples. Based on these observations, shale formations could be considered as a promising caprock in terms of retarding scCO{sub 2} flow and leak-age into above formations. We hypothesized that certain characteristics of shales (e.g., 3 fine pore size, pore size distribution, high specific surface area, and strong physical chemical interaction between wetting phase and mineral surface) make them an effi-cient caprock for sealing super critical CO{sub 2}. We found that the displacement pressure at 10% mercury saturation could not be the ultimate representative of the sealing capacity of the rock sample. On the other hand, we believe that graphical method, introduced by Cranganu (2004) is a better indicator of the true sealing capacity. Based on statistical analysis of our samples from Oklahoma Panhandle we assessed the effects of each group of properties (textural and compositional) on maximum supercriti-cal CO{sub 2} height that can be hold by the caprock. We conclude that there is a relatively strong positive relationship (+.40 to +.69) between supercritical CO{sub 2} column height based on Pc and hard/ soft mineral content index (ratio of minerals with Mohs hardness more than 5 over minerals with Mohs hardness less than 5) in both shales and limestone samples. Average median pore radius and porosity display a strong negative correlation with supercritical CO{sub 2} retention column height. Also, increasing bulk density is positive-ly correlated with the supercritical CO{sub 2} retention column height. One of the most im-portant factors affecting sealing capacity and consequently the height of supercritical CO{sub 2} column is sorting of the pore throats. We observed a strong positive correlation be-tween pore throat sorting and height of CO{sub 2} retention column, especially in shales. This correlation could not be observed in limestone samples. It suggests that the pore throat sorting is more controlling the sealing capacity in shales and shales with well sorted pore throats are the most reliable lithology as seal. We observed that Brunauer–Emmett–Teller (BET) surface area shows a very strong correlation with CO{sub 2} retention column height in limestone samples while BET surface area did not display significant correlation in shales. Pore structure based on SEM mi-crographs exhibits strong correlation with CO{sub 2} retention column height in limestones. Both intercrystalline and vuggy structures have negative correlations while intergranu-lar texture has positive correlation in limestone with respect to CO{sub 2} retention column height. Textural effects observed on SEM micrographs did not show statistically signifi-cant correlation with supercritical CO{sub 2} retention column height in shale samples. Finally, we showed that increasing hard/soft mineral index is strongly correlated with the displacement pressure in limestone samples. Vuggy texture displays a relatively strong and negative correlation with displacement pressure values at 10% mercury satu-ration in shale samples.« less

Methanogenic archaea in marcellus shale: a possible mechanism for enhanced gas recovery in unconventional shale resources.

PubMed

Tucker, Yael Tarlovsky; Kotcon, James; Mroz, Thomas

2015-06-02

Marcellus Shale occurs at depths of 1.5-2.5 km (5000 to 8000 feet) where most geologists generally assume that thermogenic processes are the only source of natural gas. However, methanogens in produced fluids and isotopic signatures of biogenic methane in this deep shale have recently been discovered. This study explores whether those methanogens are indigenous to the shale or are introduced during drilling and hydraulic fracturing. DNA was extracted from Marcellus Shale core samples, preinjected fluids, and produced fluids and was analyzed using Miseq sequencing of 16s rRNA genes. Methanogens present in shale cores were similar to methanogens in produced fluids. No methanogens were detected in injected fluids, suggesting that this is an unlikely source and that they may be native to the shale itself. Bench-top methane production tests of shale core and produced fluids suggest that these organisms are alive and active under simulated reservoir conditions. Growth conditions designed to simulate the hydrofracture processes indicated somewhat increased methane production; however, fluids alone produced relatively little methane. Together, these results suggest that some biogenic methane may be produced in these wells and that hydrofracture fluids currently used to stimulate gas recovery could stimulate methanogens and their rate of producing methane.

Shale characterization in mass transport complex as a potential source rock: An example from onshore West Java Basin, Indonesia

NASA Astrophysics Data System (ADS)

Nugraha, A. M. S.; Widiarti, R.; Kusumah, E. P.

2017-12-01

This study describes a deep-water slump facies shale of the Early Miocene Jatiluhur/Cibulakan Formation to understand its potential as a source rock in an active tectonic region, the onshore West Java. The formation is equivalent with the Gumai Formation, which has been well-known as another prolific source rock besides the Oligocene Talang Akar Formation in North West Java Basin, Indonesia. The equivalent shale formation is expected to have same potential source rock towards the onshore of Central Java. The shale samples were taken onshore, 150 km away from the basin. The shale must be rich of organic matter, have good quality of kerogen, and thermally matured to be categorized as a potential source rock. Investigations from petrography, X-Ray diffractions (XRD), and backscattered electron show heterogeneous mineralogy in the shales. The mineralogy consists of clay minerals, minor quartz, muscovite, calcite, chlorite, clinopyroxene, and other weathered minerals. This composition makes the shale more brittle. Scanning Electron Microscope (SEM) analysis indicate secondary porosities and microstructures. Total Organic Carbon (TOC) shows 0.8-1.1 wt%, compared to the basinal shale 1.5-8 wt%. The shale properties from this outcropped formation indicate a good potential source rock that can be found in the subsurface area with better quality and maturity.

Quantification of Organic Porosity and Water Accessibility in Marcellus Shale Using Neutron Scattering

DOE PAGES

Gu, Xin; Mildner, David F. R.; Cole, David R.; ...

2016-04-28

Pores within organic matter (OM) are a significant contributor to the total pore system in gas shales. These pores contribute most of the storage capacity in gas shales. Here we present a novel approach to characterize the OM pore structure (including the porosity, specific surface area, pore size distribution, and water accessibility) in Marcellus shale. By using ultrasmall and small-angle neutron scattering, and by exploiting the contrast matching of the shale matrix with suitable mixtures of deuterated and protonated water, both total and water-accessible porosity were measured on centimeter-sized samples from two boreholes from the nanometer to micrometer scale withmore » good statistical coverage. Samples were also measured after combustion at 450 °C. Analysis of scattering data from these procedures allowed quantification of OM porosity and water accessibility. OM hosts 24–47% of the total porosity for both organic-rich and -poor samples. This porosity occupies as much as 29% of the OM volume. In contrast to the current paradigm in the literature that OM porosity is organophilic and therefore not likely to contain water, our results demonstrate that OM pores with widths >20 nm exhibit the characteristics of water accessibility. In conclusion, our approach reveals the complex structure and wetting behavior of the OM porosity at scales that are hard to interrogate using other techniques.« less

Quantification of Organic Porosity and Water Accessibility in Marcellus Shale Using Neutron Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, Xin; Mildner, David F. R.; Cole, David R.

Pores within organic matter (OM) are a significant contributor to the total pore system in gas shales. These pores contribute most of the storage capacity in gas shales. Here we present a novel approach to characterize the OM pore structure (including the porosity, specific surface area, pore size distribution, and water accessibility) in Marcellus shale. By using ultrasmall and small-angle neutron scattering, and by exploiting the contrast matching of the shale matrix with suitable mixtures of deuterated and protonated water, both total and water-accessible porosity were measured on centimeter-sized samples from two boreholes from the nanometer to micrometer scale withmore » good statistical coverage. Samples were also measured after combustion at 450 °C. Analysis of scattering data from these procedures allowed quantification of OM porosity and water accessibility. OM hosts 24–47% of the total porosity for both organic-rich and -poor samples. This porosity occupies as much as 29% of the OM volume. In contrast to the current paradigm in the literature that OM porosity is organophilic and therefore not likely to contain water, our results demonstrate that OM pores with widths >20 nm exhibit the characteristics of water accessibility. In conclusion, our approach reveals the complex structure and wetting behavior of the OM porosity at scales that are hard to interrogate using other techniques.« less

The Description of Shale Reservoir Pore Structure Based on Method of Moments Estimation

PubMed Central

Li, Wenjie; Wang, Changcheng; Shi, Zejin; Wei, Yi; Zhou, Huailai; Deng, Kun

2016-01-01

Shale has been considered as good gas reservoir due to its abundant interior nanoscale pores. Thus, the study of the pore structure of shale is of great significance for the evaluation and development of shale oil and gas. To date, the most widely used approaches for studying the shale pore structure include image analysis, radiation and fluid invasion methods. The detailed pore structures can be studied intuitively by image analysis and radiation methods, but the results obtained are quite sensitive to sample preparation, equipment performance and experimental operation. In contrast, the fluid invasion method can be used to obtain information on pore size distribution and pore structure, but the relative simple parameters derived cannot be used to evaluate the pore structure of shale comprehensively and quantitatively. To characterize the nanoscale pore structure of shale reservoir more effectively and expand the current research techniques, we proposed a new method based on gas adsorption experimental data and the method of moments to describe the pore structure parameters of shale reservoir. Combined with the geological mixture empirical distribution and the method of moments estimation principle, the new method calculates the characteristic parameters of shale, including the mean pore size (x¯), standard deviation (σ), skewness (Sk) and variation coefficient (c). These values are found by reconstructing the grouping intervals of observation values and optimizing algorithms for eigenvalues. This approach assures a more effective description of the characteristics of nanoscale pore structures. Finally, the new method has been applied to analyze the Yanchang shale in the Ordos Basin (China) and Longmaxi shale from the Sichuan Basin (China). The results obtained well reveal the pore characteristics of shale, indicating the feasibility of this new method in the study of the pore structure of shale reservoir. PMID:26992168

The Description of Shale Reservoir Pore Structure Based on Method of Moments Estimation.

PubMed

Li, Wenjie; Wang, Changcheng; Shi, Zejin; Wei, Yi; Zhou, Huailai; Deng, Kun

2016-01-01

Shale has been considered as good gas reservoir due to its abundant interior nanoscale pores. Thus, the study of the pore structure of shale is of great significance for the evaluation and development of shale oil and gas. To date, the most widely used approaches for studying the shale pore structure include image analysis, radiation and fluid invasion methods. The detailed pore structures can be studied intuitively by image analysis and radiation methods, but the results obtained are quite sensitive to sample preparation, equipment performance and experimental operation. In contrast, the fluid invasion method can be used to obtain information on pore size distribution and pore structure, but the relative simple parameters derived cannot be used to evaluate the pore structure of shale comprehensively and quantitatively. To characterize the nanoscale pore structure of shale reservoir more effectively and expand the current research techniques, we proposed a new method based on gas adsorption experimental data and the method of moments to describe the pore structure parameters of shale reservoir. Combined with the geological mixture empirical distribution and the method of moments estimation principle, the new method calculates the characteristic parameters of shale, including the mean pore size (mean), standard deviation (σ), skewness (Sk) and variation coefficient (c). These values are found by reconstructing the grouping intervals of observation values and optimizing algorithms for eigenvalues. This approach assures a more effective description of the characteristics of nanoscale pore structures. Finally, the new method has been applied to analyze the Yanchang shale in the Ordos Basin (China) and Longmaxi shale from the Sichuan Basin (China). The results obtained well reveal the pore characteristics of shale, indicating the feasibility of this new method in the study of the pore structure of shale reservoir.

Molecular characterization and comparison of shale oils generated by different pyrolysis methods using FT-ICR mass spectrometry

USGS Publications Warehouse

Jin, J.M.; Kim, S.; Birdwell, J.E.

2011-01-01

Fourier transform ion cyclotron resonance mass spectrometry (FT ICR-MS) was applied in the analysis of shale oils generated using two different pyrolysis systems under laboratory conditions meant to simulate surface and in situ oil shale retorting. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules. Comparison of FT ICR-MS results to standard oil characterization methods (API gravity, SARA fractionation, gas chromatography-flame ionization detection) indicated correspondence between the average Double Bond Equivalence (DBE) and asphaltene content. The results show that, based on the average DBE values and DBE distributions of the shale oils examined, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions and in the presence of water.

Impact of Shale Gas Development on Water Resources: A Case Study in Northern Poland

NASA Astrophysics Data System (ADS)

Vandecasteele, Ine; Marí Rivero, Inés; Sala, Serenella; Baranzelli, Claudia; Barranco, Ricardo; Batelaan, Okke; Lavalle, Carlo

2015-06-01

Shale gas is currently being explored in Europe as an alternative energy source to conventional oil and gas. There is, however, increasing concern about the potential environmental impacts of shale gas extraction by hydraulic fracturing (fracking). In this study, we focussed on the potential impacts on regional water resources within the Baltic Basin in Poland, both in terms of quantity and quality. The future development of the shale play was modeled for the time period 2015-2030 using the LUISA modeling framework. We formulated two scenarios which took into account the large range in technology and resource requirements, as well as two additional scenarios based on the current legislation and the potential restrictions which could be put in place. According to these scenarios, between 0.03 and 0.86 % of the total water withdrawals for all sectors could be attributed to shale gas exploitation within the study area. A screening-level assessment of the potential impact of the chemicals commonly used in fracking was carried out and showed that due to their wide range of physicochemical properties, these chemicals may pose additional pressure on freshwater ecosystems. The legislation put in place also influenced the resulting environmental impacts of shale gas extraction. Especially important are the protection of vulnerable ground and surface water resources and the promotion of more water-efficient technologies.

Impact of shale gas development on water resources: a case study in northern poland.

PubMed

Vandecasteele, Ine; Marí Rivero, Inés; Sala, Serenella; Baranzelli, Claudia; Barranco, Ricardo; Batelaan, Okke; Lavalle, Carlo

2015-06-01

Shale gas is currently being explored in Europe as an alternative energy source to conventional oil and gas. There is, however, increasing concern about the potential environmental impacts of shale gas extraction by hydraulic fracturing (fracking). In this study, we focussed on the potential impacts on regional water resources within the Baltic Basin in Poland, both in terms of quantity and quality. The future development of the shale play was modeled for the time period 2015-2030 using the LUISA modeling framework. We formulated two scenarios which took into account the large range in technology and resource requirements, as well as two additional scenarios based on the current legislation and the potential restrictions which could be put in place. According to these scenarios, between 0.03 and 0.86% of the total water withdrawals for all sectors could be attributed to shale gas exploitation within the study area. A screening-level assessment of the potential impact of the chemicals commonly used in fracking was carried out and showed that due to their wide range of physicochemical properties, these chemicals may pose additional pressure on freshwater ecosystems. The legislation put in place also influenced the resulting environmental impacts of shale gas extraction. Especially important are the protection of vulnerable ground and surface water resources and the promotion of more water-efficient technologies.

43 CFR 3900.61 - Federal minerals where the surface is owned or administered by other Federal agencies, by state...

Code of Federal Regulations, 2011 CFR

2011-10-01

... (Continued) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Oil Shale Management-Introduction § 3900.61 Federal minerals where the surface is owned or...

Influence of sintering temperature on the characteristics of shale brick containing oil well-derived drilling waste.

PubMed

Li, Xiang-Guo; Lv, Yang; Ma, Bao-Guo; Jian, Shou-Wei; Tan, Hong-Bo

2011-11-01

The influence of sintering temperature on the physico-mechanical characteristics (such as water absorption, apparent porosity, bulk density, weight loss on ignition, firing shrinkage, and compressive strength), leachability, and microstructure of shale brick containing oil well-derived drilling waste (DW) was investigated. The experiments were conducted at a temperature ranging from 950°C to 1,050°C with 30% DW addition. The results indicate that increasing the sintering temperature decreases the water absorption and apparent porosity and increases the shrinkage, density, and compressive strength of sintered specimens. Moreover, the physico-mechanical properties of samples sintered at 1,050°C meet the requirements of the MU20 according to GB/T 5101-2003 (in China). The heavy metal concentrations of the leachate are much lower than the current regulatory limits according to GB16889-2008. The results from XRD and SEM show that increasing sintering temperature results in an increase of the high temperature liquid phase, which may have a significant effect on the densification process of the samples.

Well-construction, water-level, geophysical, and water-quality data for ground-water monitoring wells for Arnold Air Force Base, Tennessee

USGS Publications Warehouse

Hough, C.J.; Mahoney, E.N.; Robinson, J.A.

1992-01-01

Sixty-five wells were installed at 39 sites in the Arnold Air Force Base area in Coffee and Franklin Counties, Tennessee. The wells were installed to provide information on subsurface lithology, aquifer characteristics, ground-water levels, and ground-water quality. Well depths ranged from 11 to 384 feet. Water-quality samples were collected from 60 wells and analyzed for common inorganic ions, trace metals, and volatile organic compounds. The median dissolved-solids concentrations were 60 milligrams per liter in the shallow aquifer, 48 million gallons per liter in the Manchester aquifer, 1,235 milligrams per liter in the Fort Payne aquifer, and 1,712 milligrams per liter in the upper Central Basin aquifer. Caliper, temperature, natural gamma, electric, neutron porosity, gamma-gamma density, and acoustic velocity borehole-geophysical logs were obtained for the six deep wells completed below the Chattanooga Shale. Petrographic and modal analysis were performed on rock samples from each deep well. These six deep wells provide the first information in the study area on hydraulic head and water quality from below the Chattanooga Shale.

Life-cycle analysis of shale gas and natural gas.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, C.E.; Han, J.; Burnham, A.

2012-01-27

The technologies and practices that have enabled the recent boom in shale gas production have also brought attention to the environmental impacts of its use. Using the current state of knowledge of the recovery, processing, and distribution of shale gas and conventional natural gas, we have estimated up-to-date, life-cycle greenhouse gas emissions. In addition, we have developed distribution functions for key parameters in each pathway to examine uncertainty and identify data gaps - such as methane emissions from shale gas well completions and conventional natural gas liquid unloadings - that need to be addressed further. Our base case results showmore » that shale gas life-cycle emissions are 6% lower than those of conventional natural gas. However, the range in values for shale and conventional gas overlap, so there is a statistical uncertainty regarding whether shale gas emissions are indeed lower than conventional gas emissions. This life-cycle analysis provides insight into the critical stages in the natural gas industry where emissions occur and where opportunities exist to reduce the greenhouse gas footprint of natural gas.« less

Carbon, nitrogen, and sulfur geochemistry of Archean and Proterozoic shales from the Kaapvaal Craton, South Africa

NASA Astrophysics Data System (ADS)

Watanabe, Yumiko; Naraoka, Hiroshi; Wronkiewicz, David J.; Condie, Kent C.; Ohmoto, Hiroshi

1997-08-01

The C, N, and S contents and VC and δ 13Cδ 34S values were analyzed for 100 shale samples from ten formations, 3.0 to 2.1 Ga in age, in the central and eastern regions of the Kaapvaal Craton, South Africa. The Kaapvaal shales are characterized by generally low contents of organic C (range 0.06-2.79 wt%, average 0.47 wt%), N (range <0.01-0.09 wt%, average 0.1 wt%), and S (range <0.01-1.63 wt%, average 0.1 wt%). The low N/C (<0.005) and H/C (mostly ˜0.2) atomic ratios in kerogens from the shales indicated that the Kaapvaal shales lost considerable amounts of N, C, S, and H during diagenesis and regional metamorphism (up to the greenschist facies). From the theoretical relationships between the H/C ratios of kerogen and organic C contents of shales, the original C contents of the Archean and Proterozoic shales from the Kaapvaal Craton are estimated to be on average ˜2 wt%. These values are similar to the average organic C content of modern marine sediments. This suggests that the primary organic productivity and the preservation of organic matter in the ocean during the period of 3.0 to 2.1 Ga were similar to those in the Phanerozoic era, provided the flux of clastic sediments to the ocean was similar. This would also imply that the rate of O 2 accumulation in the atmosphere-ocean system, which has equaled the burial rate of organic matter in sediments, has been the same since ˜3.0 Ga. The δ 34S values of bulk-rock sulfides (mostly pyrite) range from +2.7 to +7.4%‰ for seven sulfide-rich samples of ˜2.9 Ga to ˜2.6 Ga. These values are consistent with a suggestion by Ohmoto (1992) and Ohmoto et al. (1993) that most pyrite crystals in Archean shales were formed by bacterial reduction of seawater sulfate with δ 34S values between +2 and +10‰, and that the Archean seawater was sulfate rich. Changes in the δ 13C org values during maturation of kerogen were evaluated with theoretical calculations from the experimental data of Peters et al. (1981) and Lewan (1983), and from the observations by Simoneit et al. (1981) on natural samples. These evaluations suggest that the magnitudes of δ 13C org increase are much less than those estimated by Hayes et al. (1983) and Des Marais et al. (1992), and only about 2 to 3%‰ for the kerogens that decreased their H/C ratios from 1.5 to less than 0.3. Based on the relationships among sulfide-S contents, organic-C contents, and δ 13C org values, four different types of depositional environments are identified for the Archean and early Proterozoic shales in the Kaapvaal Craton: (I) euxinic marine basins, characterized by normal marine organisms with δ 13C org= -33 ± 3%‰ (II) near-shore, oxic marine environment, characterized by normal marine organisms with δ 13C org = -31 ± 3%‰; (III) hypersaline, low-sulfate lakes, characterized by organisms with δ 13C org= -2 ± 3%‰; and (IV) euxinic, marine basins which supported the activity of methanogenic and methanotrophic bacteria and accumulated organic matter with δ 13C org= -43 ± 3%‰. In contrast to the currently popular model positing a global anoxic ocean prior to ˜2.2 Ga (e.g., Des Marais et al, 1992; Hayes, 1994; Logan et al., 1995), this study suggests that the development of anoxic basins, which accumulated Group II and IV sediments, occurred only regionally and episodically during the period between 3.0 Ga and 2.1 Ga. This further suggests that the normal ocean has been oxic since at least ˜3.0 Ga. Diversifications of environments, as well as of biological species, had already occurred ˜3.0 Ga. The carbon isotope mass balance calculation suggests that the removal rates of organic C and carbonate C from the ocean and the weathering rates of organic C and carbonate C on the continents during the 3.0-2.1 Ga period were basically the same as those in the Phanerozoic era. This would have been possible only if the atmospheric P O 2 level had been basically constant since at least 3.0 Ga. The results of this study, therefore, add to a growing list of evidence that the atmosphere has been oxic (i.e., P O 2 > 1%PAL) since at least 3.0 Ga. The list of evidence includes the sulfur isotope data on Archean sedimentary rocks ( Ohmoto and Felder, 1987; Ohmoto et al., 1993), the Fe 3+Ti ratios of paleosols ( Ohmoto, 1996), and the paragenesis of minerals in the "detrital" gold-uranium ores in pre-2.0 Ga quartz pebble beds that suggests nondetrital origins for uraninite and pyrite in these deposits ( Barnicoat et al., 1997).

Investigating GHGs and VOCs emissions from a shale gas industry in Germany and the UK

NASA Astrophysics Data System (ADS)

Cremonese, L.; Weger, L.; Denier Van Der Gon, H.; Bartels, M. P.; Butler, T. M.

2017-12-01

The shale gas and shale oil production boom experienced in the US led the country to a significant reduction of foreign fuel imports and an increase in domestic energy security. Several European countries are considering to extract domestic shale gas reserves that might serve as a bridge in the transition to renewables. Nevertheless, the generation of shale gas leads to emissions of CH4 and pollutants such as PM, NOx and VOCs, which in turn impact local and regional air quality and climate. Results from numerous studies investigating greenhouse gas and pollutant emissions from shale oil and shale gas extraction in North America can help in estimating the impact of such industrial activity elsewhere, when local regulations are taken into consideration. In order to investigate the extent of emissions and their distribution from a potential shale gas industry in Germany and the United Kingdom, we develop three drilling scenarios compatible with desired national gas outputs based on available geological information on potential productivity ranges of the reservoirs. Subsequently we assign activity data and emissions factors to wells under development, as well as to producing wells (from activities at the well site up until processing plants) to enable emissions quantification. We then define emissions scenarios to explore different shale gas development pathways: 1) implementation of "high-technology" devices and recovery practices (low emissions); 2) implementation of "low-technology" devices and recovery practices (high emissions), and 3) intermediate scenarios reflecting assumptions on local and national settings, or extremely high emission events (e.g. super-emitters); all with high and low boundaries of confidence driven by uncertainties. A comparison of these unconventional gas production scenarios to conventional natural gas production in Germany and the United Kingdom is also planned. The aim of this work is to highlight important variables and their ranges, to promote discussion and communication of potential impacts, and to construct possible visions for a future shale gas development in the two study countries. In a follow-up study, the impact of pollutant emissions from these scenarios on air quality will be explored using the Weather Research and Forecasting model with chemistry (WRF-Chem) model.

Organic and inorganic composition and microbiology of produced waters from Pennsylvania shale gas wells

USGS Publications Warehouse

Akob, Denise M.; Cozzarelli, Isabelle M.; Dunlap, Darren S.; Rowan, Elisabeth L.; Lorah, Michelle M.

2015-01-01

Hydraulically fractured shales are becoming an increasingly important source of natural gas production in the United States. This process has been known to create up to 420 gallons of produced water (PW) per day, but the volume varies depending on the formation, and the characteristics of individual hydraulic fracture. PW from hydraulic fracturing of shales are comprised of injected fracturing fluids and natural formation waters in proportions that change over time. Across the state of Pennsylvania, shale gas production is booming; therefore, it is important to assess the variability in PW chemistry and microbiology across this geographical span. We quantified the inorganic and organic chemical composition and microbial communities in PW samples from 13 shale gas wells in north central Pennsylvania. Microbial abundance was generally low (66–9400 cells/mL). Non-volatile dissolved organic carbon (NVDOC) was high (7–31 mg/L) relative to typical shallow groundwater, and the presence of organic acid anions (e.g., acetate, formate, and pyruvate) indicated microbial activity. Volatile organic compounds (VOCs) were detected in four samples (∼1 to 11.7 μg/L): benzene and toluene in the Burket sample, toluene in two Marcellus samples, and tetrachloroethylene (PCE) in one Marcellus sample. VOCs can be either naturally occurring or from industrial activity, making the source of VOCs unclear. Despite the addition of biocides during hydraulic fracturing, H2S-producing, fermenting, and methanogenic bacteria were cultured from PW samples. The presence of culturable bacteria was not associated with salinity or location; although organic compound concentrations and time in production were correlated with microbial activity. Interestingly, we found that unlike the inorganic chemistry, PW organic chemistry and microbial viability were highly variable across the 13 wells sampled, which can have important implications for the reuse and handling of these fluids

An in situ estimation of anisotropic elastic moduli for a submarine shale

NASA Astrophysics Data System (ADS)

Miller, Douglas E.; Leaney, Scott; Borland, William H.

1994-11-01

Direct arrival times and slownesses from wide-aperture walkaway vertical seismic profile data acquired in a layered anisotropic medium can be processed to give direct estimate of the phase slowness surface associated with the medium at the depth of the receivers. This slowness surface can, in turn, be fit by an estimated transversely isotropic medium with a vertical symmetry axis (a 'TIV' medium). While the method requires that the medium between the receivers and the surface be horizontally stratified, no further measurement or knowledge of that medium is required. When applied to data acquired in a compacting shale sequence (here termed the 'Petronas shale') encountered by a well in the South China Sea, the method yields an estimated TIV medium that fits the data extremely well over 180 deg of propagation angles sampled by 201 source positions. The medium is strongly anisotropic. The anisotropy is significantly anelliptic and implies that the quasi-shear mode should be triplicated for off-axis propagation. Estimated density-normalized moduli (in units of sq km/sq s) for the Petronas shale are A(sub 11) = 6.99 +/- 0.21, A(sub 33) = 5.53 +/- 0.17, A(sub 55) = 0.91 +/- 0.05, and A(sub 13) = 2.64 +/- 0.26. Densities in the logged zone just below the survey lie in the range between 2200 and 2400 kg/cu m with an average value close to 2300 kg/cu m.

Stratigraphy and depositional environments of the Lower Mississippian Joana Limestone in southern White Pine and northern Lincoln Counties, Nevada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gilmore, T.J.

1990-04-01

The Lower Mississippian Joana Limestone in the southern Schell Creek and Egan ranges of east-central Nevada is composed of three depositional facies: the unbedded wackestone with grainstone/packstone facies or Facies 1; the bedded wackestone with mudstone facies or Facies 2; and the restricted wackestone, mudstone/shale facies, or Facies 3. Facies 1 is characterized by Waulsortian-type carbonate buildups with massive unbedded wackestone cores, grainstone flanking beds and grainstone/packstone capping units. Facies 2 is characterized by an upward progression of sedimentary bedding types from thinly laminated to large scale trough cross-bedding that indicates a shoaling upward of this facies. Facies 3 ismore » characterized by sparse wackestones, mudstones, and shale which show a decrease in both faunal types and diversity and an increase in fine clastics. The restricted wackestone, mudstone/shale facies grades upward into the Mississippian Chainman Shale. The age of the Joana Limestone is confirmed as late Kinderhookian to early Osagean based primarily on conodonts and foraminifera. In the middle beds of the Joana Limestone, the previously unreported upper Siphonodella crenulata conodont zone occurs which helps correlate the Joana Limestone with regional transgressive/regressive sea level events. Color alteration indices of these conodonts are 1.5 to 2, and occur in the oil generation window. Additionally, oil staining was observed in numerous samples located primarily in the lower half of the formation, represented by Facies 3, the unbedded wackestone with grainstone/packstone facies.« less

United States Air Force Shale Oil to Fuels. Phase II.

DTIC Science & Technology

1981-11-01

and modified so that any off-gas from the LPS, stripper column, product drums, spent caustic drums, and sample ports would be sent to the caustic ...product, or in the spent caustic . After the desalted Paraho shale oil was processed in Production Run No. 2, the catalyst bed was flushed with light cycle...58 20 First-Stage Hydrotreating of Occidental Shale Oil -- Spent Catalyst Analysis - Run 1 ....... 59 21 First-Stage Hydrotreating of Occidental

Understanding public perception of hydraulic fracturing: a case study in Spain.

PubMed

Costa, D; Pereira, V; Góis, J; Danko, A; Fiúza, A

2017-12-15

Public acceptance is crucial for the implementation of energy technologies. Hydraulic fracturing is a technology widely used in the USA for natural gas production from shale formations, but currently finds strong public opposition worldwide, especially in Europe. Shale gas exploitation and exploration have the potential to significantly reduce import dependency in several countries, including Spain. To better understand public opinion on this issue, this article reports a survey targeting both the entire Spanish population and the inhabitants of the province of Burgos, the location where shale gas exploration permits have already been issued. Results demonstrate that half of the Spanish population opposes shale gas, and this opposition increases in autonomous communities that are closer to possible exploration sites. The results also show that socio-demographic aspects are not strong predictors of opposition. In addition, Burgos' population show different behaviours toward shale gas that demonstrates that proximity and prospect of shale gas development affects opinion. Finally, there is still a great level of unfamiliarity with high volume hydraulic fracturing and shale gas in both populations sampled. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reconnaissance for uranium in black shale, Northern Rocky Mountains and Great Plains, 1953

USGS Publications Warehouse

Mapel, W.J.

1954-01-01

Reconnaissance examinations for uranium in 22 formations containing black shale were conducted in parts of Montana, North Dakota, Utah, Idaho, and Oregon during 1953. About 150 samples from 80 outcrop localities and 5 oil and gas wells were submitted for uranium determinations. Most of the black shale deposits examined contain less than 0.003 percent uranium; however, thin beds of black shale at the base of the Mississippian system contain 0.005 percent uranium at 2 outcrop localities in southwestern Montana and as much as 0.007 percent uranium in a well in northeastern Montana. An eight-foot bed of phosphatic black shale at the base of the Brazer limestone of Late Mississippian age in Rich County, Utah, contains as much as 0.009 percent uranium. Commercial gamma ray logs of oil and gas wells drilled in Montana and adjacent parts of the Dakotas indicate that locally the Heath shale of Late Mississippian age contains as much as 0.01 percent equivalent uranium, and black shales of Late Cretaceous age contain as much as 0.008 percent equivalent uranium.

Fracturing and brittleness index analyses of shales

NASA Astrophysics Data System (ADS)

Barnhoorn, Auke; Primarini, Mutia; Houben, Maartje

2016-04-01

The formation of a fracture network in rocks has a crucial control on the flow behaviour of fluids. In addition, an existing network of fractures , influences the propagation of new fractures during e.g. hydraulic fracturing or during a seismic event. Understanding of the type and characteristics of the fracture network that will be formed during e.g. hydraulic fracturing is thus crucial to better predict the outcome of a hydraulic fracturing job. For this, knowledge of the rock properties is crucial. The brittleness index is often used as a rock property that can be used to predict the fracturing behaviour of a rock for e.g. hydraulic fracturing of shales. Various terminologies of the brittleness index (BI1, BI2 and BI3) exist based on mineralogy, elastic constants and stress-strain behaviour (Jin et al., 2014, Jarvie et al., 2007 and Holt et al., 2011). A maximum brittleness index of 1 predicts very good and efficient fracturing behaviour while a minimum brittleness index of 0 predicts a much more ductile shale behaviour. Here, we have performed systematic petrophysical, acoustic and geomechanical analyses on a set of shale samples from Whitby (UK) and we have determined the three different brittleness indices on each sample by performing all the analyses on each of the samples. We show that each of the three brittleness indices are very different for the same sample and as such it can be concluded that the brittleness index is not a good predictor of the fracturing behaviour of shales. The brittleness index based on the acoustic data (BI1) all lie around values of 0.5, while the brittleness index based on the stress strain data (BI2) give an average brittleness index around 0.75, whereas the mineralogy brittleness index (BI3) predict values below 0.2. This shows that by using different estimates of the brittleness index different decisions can be made for hydraulic fracturing. If we would rely on the mineralogy (BI3), the Whitby mudstone is not a suitable candidate for hydraulic fracturing while if we would rely on stress-strain data (BI2) the Whitby mudstone would be a very good candidate. We are aiming to perform these kind of measurements on a wide variety of shales with varying compositions and origins etc. and compare all results and come up with a better brittleness index, as well as link the brittleness indices to the fracturing behaviour seen in the samples. References: Holt, R., Fjaer, E., Nes, O. & Alassi, H., 2011. A shaly look at brittleness. 45th U.S. Rock Mechanics / Geomechanics Symposium, ARMA-11-366 Jarvie, D., Hill, J., Ruble, T. & Pollastro, R., 2007. Unconventional shale-gas system: The Mississippian Barnett Shale of North-Central Texas as one model for thermogenic shale-gas assessment. AAPG, 91(doi: 10.1306/12190606068), pp. 475-499. Jin, X., Shah, S. N., Rogiers, J.-C. & Zhang, B., 2014. Fraccability Evaluation in Shale Reservoirs - An Integrated Petrophysics and Geomechanics Approach. Woodlands, Texas, SPE.

Diagenetic variation at the lamina scale in lacustrine organic-rich shales: Implications for hydrocarbon migration and accumulation

NASA Astrophysics Data System (ADS)

Liang, Chao; Cao, Yingchang; Liu, Keyu; Jiang, Zaixing; Wu, Jing; Hao, Fang

2018-05-01

Lacustrine carbonate-rich shales are well developed within the Mesozoic-Cenozoic strata of the Bohai Bay Basin (BBB) of eastern China and across southeast Asia. Developing an understanding of the diagenesis of these shales is essential to research on mass balance, diagenetic fluid transport and exchange, and organic-inorganic interactions in black shales. This study investigates the origin and distribution of authigenic minerals and their diagenetic characteristics, processes, and pathways at the scale of lacustrine laminae within the Es4s-Es3x shale sequence of the BBB. The research presented in this study is based on thin sections, field emission scanning electron microscope (FESEM) and SEM-catholuminescence (CL) observations of well core samples combined with the use of X-ray diffraction (XRD), energy dispersive spectroscopy, electron microprobe analysis, and carbon and oxygen isotope analyses performed using a laser microprobe mass spectrometer. The dominant lithofacies within the Es4s-Es3x sequence are a laminated calcareous shale (LCS-1) and a laminated clay shale (LCS-2). The results of this study show that calcite recrystallization1 is the overarching diagenetic process affecting the LCS-1, related to acid generation from organic matter (OM) thermal evolution. This evolutionary transition is the key factor driving the diagenesis of this lithofacies, while the transformation of clay minerals is the main diagenetic attribute of the LCS-2. Diagenetic differences occur within different laminae and at variable locations within the same lamina level, controlled by variations in mineral composition and the properties of laminae interfaces. The diagenetic fluid migration scale is vertical and responses (dissolution and replacement) are limited to individual laminae, between zero and 100 μm in width. In contrast, the dominant migration pathway for diagenetic fluid is lateral, along the abrupt interfaces between laminae boundaries, which leads to the vertical transmission of diagenetic responses. The recrystallization boundaries between calcite laminae act as the main migration pathways for the expulsion of hydrocarbons from these carbonate-rich lacustrine shales. However, because the interaction between diagenetic fluids and the shales themselves is limited to the scale of individual lamina, this system is normally closed. The occurrence of abnormal pressure fractures can open the diagenetic system, however, and cause interactions to occur throughout laminae; in particular, the closed-open (C-O) diagenetic process at this scale is critical to this shale interval. Multi-scale C-O systems are ubiquitous and episodic ranging from the scale of laminae to the whole basin. Observations show that such small-scale systems are often superimposed onto larger ones to constitute the complex diagenetic system seen within the BBB combining fluid transport, material and energy exchange, and solid-liquid and organic-inorganic interactions.

43 CFR 3900.30 - Filing documents.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 43 Public Lands: Interior 2 2011-10-01 2011-10-01 false Filing documents. 3900.30 Section 3900.30 Public Lands: Interior Regulations Relating to Public Lands (Continued) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Oil Shale Management...

Organic content of Devonian shale in western Appalachian basin.

USGS Publications Warehouse

Schmoker, J.W.

1980-01-01

In the organic-rich facies of the Devonian shale in the western part of the Appalachian basin, the distribution of organic matter provides an indirect measure of both gas in place and the capacity of the shale to supply gas to permeable pathways.The boundary between organic-rich ('black') and organic-poor ('gray') facies is defined here as 2% organic content by volume. The thickness of organic-rich facies ranges from 200ft in central Kentucky to 1000ft along the Kentucky-West Virginia border. The average content of the organic-rich facies increases from 5% by volume on the edge to 16% in central Kentucky. The net thickness of organic matter in the organic-rich facies shows the amount of organic material in the shale, and is the most fundamental of the organic-content characterizations. Net thickness of organic matter ranges between 20 and 80ft (6.1 and 24.4m) within the mapped area.-from Author

Empirical test of an illite/muscovite 40Ar/39Ar thermochronometer

NASA Astrophysics Data System (ADS)

Verdel, C.; van der Pluijm, B. A.; Niemi, N. A.; Hall, C. M.

2010-12-01

Minerals which both preserve age information and indicate metamorphic conditions are particularly useful in thermochronology. Variations in sub-greenschist facies metamorphism have traditionally been quantified in terms of the illite to muscovite transition, a transformation which involves the growth of crystallites of increasing thickness at higher metamorphic temperatures. Thickness variations may influence Ar retention within these K-rich minerals, both in nature and during neutron irradiation. Along a transect in the southwestern US from the Grand Canyon to Death Valley, metamorphic conditions of a stratigraphic interval (the Middle Cambrian Bright Angel Shale and laterally equivalent Carrara Fm.) range from zeolite facies in the east to greenschist facies in the west, as determined by estimating illite crystallite thickness with X-ray diffraction. 40Ar/39Ar step-heating experiments were conducted on illite/muscovite-rich, micron to submicron grain sizes of these shales that were encapsulated in quartz tubes prior to irradiation. The proportion of 39Ar expelled during irradiation decreases in these samples as both crystallite thickness and grain size increases. Spectra from the least metamorphosed samples (diagenetic zone) are staircase-shaped and reach maximum ages that appear to reflect the age of detrital muscovite. Spectra from the highest grade samples (epizone) display partial plateaus and yield much younger maximum ages. Based on these findings we conclude that Ar can escape from illite via two processes: loss from low retention sites on crystallite edges and c-axis perpendicular volume diffusion. Based on our empirical data, the closure temperature of illite appears to lie at or near the anchizone-epizone bounday, or roughly 200-300 °C. Illite/muscovite thickness and 40Ar/39Ar data may therefore be useful for studies of detrital muscovite geochronology in very low grade shales and as a thermochronometer for higher grade pelites.

The silicon isotope composition of the upper continental crust

NASA Astrophysics Data System (ADS)

Savage, Paul S.; Georg, R. Bastian; Williams, Helen M.; Halliday, Alex N.

2013-05-01

The upper continental crust (UCC) is the major source of silicon (Si) to the oceans and yet its isotopic composition is not well constrained. In an effort to investigate the degree of heterogeneity and provide a robust estimate for the average Si isotopic composition of the UCC, a representative selection of well-characterised, continentally-derived clastic sediments have been analysed using high-precision MC-ICPMS. Analyses of loess samples define a narrow range of Si isotopic compositions (δ30Si = -0.28‰ to -0.15‰). This is thought to reflect the primary igneous mineralogy and predominance of mechanical weathering in the formation of such samples. The average loess δ30Si is -0.22 ± 0.07‰ (2 s.d.), identical to average granite and felsic igneous compositions. Therefore, minor chemical weathering does not resolvably affect bulk rock δ30Si, and loess is a good proxy for the Si isotopic composition of unweathered, crystalline, continental crust. The Si isotopic compositions of shales display much more variability (δ30Si = -0.82‰ to 0.00‰). Shale Si isotope compositions do not correlate well with canonical proxies for chemical weathering, such as CIA values, but do correlate negatively with insoluble element concentrations and Al/Si ratios. This implies that more intensive or prolonged chemical weathering of a sedimentary source, with attendant desilicification, is required before resolvable negative Si isotopic fractionation occurs. Shale δ30Si values that are more positive than those of felsic igneous rocks most likely indicate the presence of marine-derived silica in such samples. Using the data gathered in this study, combined with already published granite Si isotope analyses, a weighted average composition of δ30Si = -0.25 ± 0.16‰ (2 s.d.) for the UCC has been calculated.

Discussion on upper limit of maturity for marine shale gas accumulation

NASA Astrophysics Data System (ADS)

Huang, Jinliang; Dong, Dazhong; Zhang, Chenchen; Wang, Yuman; Li, Xinjing; Wang, Shufang

2017-04-01

The sedimentary formations of marine shale in China are widely distributed and are characterized by old age, early hydrocarbon-generation and high thermal evolution degree, strong tectonic deformation and reformation and poor preservation conditions. Therefore whether commercial shale gas reservoirs can be formed is a critical issue to be studied. The previous studies showed that the upper threshold of maturity (Ro%) for the gas generation of marine source rocks is 3.0%. Based on comparative studies of marine shale gas exploration practices at home and abroad and reservoir experimental analysis results, we proposed in this paper that the upper threshold of maturity (Ro%) for marine shale gas accumulation is 3.5%. And the main proofs are as follows: (1) There is still certain commercial production in the area with the higher than 3.0% in Marcellus and Woodford marine shale gas plays in North America; (2) The Ro of the Silurian Longmaxi shale in the Sichuan Basin in China is between 2.5% and 3.3%. However, the significant breakthrough has been made in shale gas exploration and the production exceeds 7 billion m3 in 2016; (3) The TOC of the Cambrian Qiongzhusi organic-rich shale in Changning Region in the Sichuan Basin ranges 2% to 7.1% and the Ro is greater than 3.5%. And the resistivity logging of organic-rich shale appears low-ultra low resistivity and inversion of Rt curve. It's suggested that the organic matters in Qiongzhusi organic-rich shale occurs partial carbonization which leads to stronger conductivity; (4) Thermal simulation experiments showed that the specific surface of shale increases with Ro. And the specific surface and adsorptive capacity both reach maximum when the Ro is 3.5%; (5) The analysis of physical properties and SEM images of shale reservoirs indicated that when Ro is higher than 3.5%, the dominant pores of Qiongzhusi shale are micro-pores while the organic pores are relatively poor-developed, and the average porosity is less than 2%.

Characterization of Unconventional Reservoirs: CO2 Induced Petrophysics

NASA Astrophysics Data System (ADS)

Verba, C.; Goral, J.; Washburn, A.; Crandall, D.; Moore, J.

2017-12-01

As concerns about human-driven CO2 emissions grow, it is critical to develop economically and environmentally effective strategies to mitigate impacts associated with fossil energy. Geologic carbon storage (GCS) is a potentially promising technique which involves the injection of captured CO2 into subsurface formations. Unconventional shale formations are attractive targets for GCS while concurrently improving gas recovery. However, shales are inherently heterogeneous, and minor differences can impact the ability of the shale to effectively adsorb and store CO2. Understanding GCS capacity from such endemic heterogeneities is further complicated by the complex geochemical processes which can dynamically alter shale petrophysics. We investigated the size distribution, connectivity, and type (intraparticle, interparticle, and organic) of pores in shale; the mineralogy of cores from unconventional shale (e.g. Bakken); and the changes to these properties under simulated GCS conditions. Electron microscopy and dual beam focused ion beam scanning electron microscopy were used to reconstruct 2D/3D digital matrix and pore structures. Comparison of pre and post-reacted samples gives insights into CO2-shale interactions - such as the mechanism of CO2 sorption in shales- intended for enhanced oil recovery and GCS initiatives. These comparisons also show how geochemical processes proceed differently across shales based on their initial diagenesis. Results show that most shale pore sizes fall within meso-macro pore classification (> 2 nm), but have variable porosity and organic content. The formation of secondary minerals (calcite, gypsum, and halite) may play a role in the infilling of fractures and pore spaces in the shale, which may reduce permeability and inhibit the flow of fluids.

Black shale - Its deposition and diagenesis.

USGS Publications Warehouse

Tourtelot, H.A.

1979-01-01

Black shale is a dark-colored mudrock containing organic matter that may have generated hydrocarbons in the subsurface or that may yield hydrocarbons by pyrolysis. Many black shale units are enriched in metals severalfold above expected amounts in ordinary shale. Some black shale units have served as host rocks for syngenetic metal deposits.Black shales have formed throughout the Earth's history and in all parts of the world. This suggests that geologic processes and not geologic settings are the controlling factors in the accumulation of black shale. Geologic processes are those of deposition by which the raw materials of black shale are accumulated and those of diagenesis in response to increasing depth of burial.Depositional processes involve a range of relationships among such factors as organic productivity, clastic sedimentation rate, and the intensity of oxidation by which organic matter is destroyed. If enough organic material is present to exhaust the oxygen in the environment, black shale results.Diagenetic processes involve chemical reactions controlled by the nature of the components and by the pressure and temperature regimens that continuing burial imposes. For a thickness of a few meters beneath the surface, sulfate is reduced and sulfide minerals may be deposited. Fermentation reactions in the next several hundred meters result in biogenic methane, followed successively at greater depths by decarboxylation reactions and thermal maturation that form additional hydrocarbons. Suites of newly formed minerals are characteristic for each of the zones of diagenesis.

Stress dependence of permeability of intact and fractured shale cores.

NASA Astrophysics Data System (ADS)

van Noort, Reinier; Yarushina, Viktoriya

2016-04-01

Whether a shale acts as a caprock, source rock, or reservoir, understanding fluid flow through shale is of major importance for understanding fluid flow in geological systems. Because of the low permeability of shale, flow is thought to be largely confined to fractures and similar features. In fracking operations, fractures are induced specifically to allow for hydrocarbon exploration. We have constructed an experimental setup to measure core permeabilities, using constant flow or a transient pulse. In this setup, we have measured the permeability of intact and fractured shale core samples, using either water or supercritical CO2 as the transporting fluid. Our measurements show decreasing permeability with increasing confining pressure, mainly due to time-dependent creep. Furthermore, our measurements show that for a simple splitting fracture, time-dependent creep will also eliminate any significant effect of this fracture on permeability. This effect of confinement on fracture permeability can have important implications regarding the effects of fracturing on shale permeability, and hence for operations depending on that.

USAF shale oil program status

NASA Technical Reports Server (NTRS)

Delaney, C. L.

1984-01-01

The test and evaluation program on shale derived fuel being conducted by the Air Force is intended to accomplish the minimum amount of testing necessary to assure both the safe use of shale oil derived turbine fuels in operational USAF aircraft and its compatibility with USAF handling systems. This program, which was designed to take advantage of existing R&D testing programs, began in 1981. However, due to a problem in acquiring the necessary fuel, the testing program was suspended until July 1983 when an additional sample of shale derived fuel was received. Tentatively, the Air Force is planning to make three relatively minor revisions to the procurement specifications requirements for the production shale derived fuel. These are: (1) Aromatic Contest (min) - 9% (by volume); (2) Nitrogen (max - 20 ppm by weight); and (3) Antioxidants - 9.1 g/100 gal (U.S.)

Total arsenic and selenium analysis in Marcellus shale, high-salinity water, and hydrofracture flowback wastewater.

PubMed

Balaba, Ronald S; Smart, Ronald B

2012-11-01

Trace levels of arsenic and selenium can be toxic to living organisms yet their quantitation in high ionic strength or high salinity aqueous media is difficult due to the matrix interferences which can either suppress or enhance the analyte signal. A modified thiol cotton fiber (TCF) method employing lower flow rates and centrifugation has been used to remove the analyte from complex aqueous media and minimize the matrix interferences. This method has been tested using a USGS (SGR-1b) certified reference shale. It has been used to analyze Marcellus shale samples following microwave digestion as well as spiked samples of high salinity water (HSW) and flow back wastewater (WRF6) obtained from an actual gas well drilling operation. Quantitation of arsenic and selenium is carried out by graphite furnace atomic spectroscopy (GFAAS). Extraction of arsenic and selenium from Marcellus shale exposed to HSW and WRF6 for varying lengths of time is also reported. Copyright © 2012 Elsevier Ltd. All rights reserved.

Characterization of coal-derived hydrocarbons and source-rock potential of coal beds, San Juan Basin, New Mexico and Colorado, U.S.A.

USGS Publications Warehouse

Rice, D.D.; Clayton, J.L.; Pawlewicz, M.J.

1989-01-01

Coal beds are considered to be a major source of nonassociated gas in the Rocky Mountain basins of the United States. In the San Juan basin of northwestern New Mexico and southwestern Colorado, significant quantities of natural gas are being produced from coal beds of the Upper Cretaceous Fruitland Formation and from adjacent sandstone reservoirs. Analysis of gas samples from the various gas-producing intervals provided a means of determining their origin and of evaluating coal beds as source rocks. The rank of coal beds in the Fruitland Formation in the central part of the San Juan basin, where major gas production occurs, increases to the northeast and ranges from high-volatile B bituminous coal to medium-volatile bituminous coal (Rm values range from 0.70 to 1.45%). On the basis of chemical, isotopic and coal-rank data, the gases are interpreted to be thermogenic. Gases from the coal beds show little isotopic variation (??13C1 values range -43.6 to -40.5 ppt), are chemically dry (C1/C1-5 values are > 0.99), and contain significant amounts of CO2 (as much as 6%). These gases are interpreted to have resulted from devolatilization of the humic-type bituminous coal that is composed mainly of vitrinite. The primary products of this process are CH4, CO2 and H2O. The coal-generated, methane-rich gas is usually contained in the coal beds of the Fruitland Formation, and has not been expelled and has not migrated into the adjacent sandstone reservoirs. In addition, the coal-bed reservoirs produce a distinctive bicarbonate-type connate water and have higher reservoir pressures than adjacent sandstones. The combination of these factors indicates that coal beds are a closed reservoir system created by the gases, waters, and associated pressures in the micropore coal structure. In contrast, gases produced from overlying sandstones in the Fruitland Formation and underlying Pictured Cliffs Sandstone have a wider range of isotopic values (??13C1 values range from -43.5 to -38.5 ppt), are chemically wetter (C1/C1-5 values range from 0.85 to 0.95), and contain less CO2 (< 2%). These gases are interpreted to have been derived from type III kerogen dispersed in marine shales of the underlying Lewis Shale and nonmarine shales of the Fruitland Formation. In the underlying Upper Cretaceous Dakota Sandstone and Tocito Sandstone Lentil of the Mancos Shale, another gas type is produced. This gas is associated with oil at intermediate stages of thermal maturity and is isotopically lighter and chemically wetter at the intermediate stage of thermal maturity as compared with gases derived from dispersed type III kerogen and coal; this gas type is interpreted to have been generated from type II kerogen. Organic matter contained in coal beds and carbonaceous shales of the Fruitland Formation has hydrogen indexes from Rock-Eval pyrolysis between 100 and 350, and atomic H:C ratios between 0.8 and 1.2. Oxygen indexes and atomic O:C values are less than 24 and 0.3, respectively. Extractable hydrocarbon yields are as high as 7,000 ppm. These values indicate that the coal beds and carbonaceous shales have good potential for the generation of liquid hydrocarbons. Voids in the coal filled with a fluorescent material that is probably bitumen is evidence that liquid hydrocarbon generation has taken place. Preliminary oil-source rock correlations based on gas chromatography and stable carbon isotope ratios of C15+ hydrocarbons indicate that the coals and (or) carbonaceous shales in the Fruitland Formation may be the source of minor amounts of condensate produced from the coal beds at relatively low levelsof thermal maturity (Rm=0.7). ?? 1989.

Refining of Military Jet Fuels from Shale Oil. Volume I. Part II. Preparation of Laboratory-Scale Fuel Samples.

DTIC Science & Technology

1982-03-01

ON SPEC Meeting Specifications *1 OXY Test Series on In Situ Shale Oil P Pressure (P + N) Paraffins and Naphthenes PHO Test Series on Above-Ground...material, the crude shale is heated and processed through caustic desalt- ing similar to conventional technology. The desalted oil is mixed with recycle...with hot regenerated catalyst. Spent catalyst and oil vapors are disengaqed by -.eans of high temperature cyclones. The spent catalyst first passes

43 CFR 3900.20 - Appealing the BLM's decision.

Code of Federal Regulations, 2011 CFR

2011-10-01

... 43 Public Lands: Interior 2 2011-10-01 2011-10-01 false Appealing the BLM's decision. 3900.20 Section 3900.20 Public Lands: Interior Regulations Relating to Public Lands (Continued) BUREAU OF LAND MANAGEMENT, DEPARTMENT OF THE INTERIOR RANGE MANAGEMENT (4000) OIL SHALE MANAGEMENT-GENERAL Oil Shale...

Composition of the Rex Chert and associated rocks of the Permian Phosphoria Formation: Soda Springs area, SE Idaho

USGS Publications Warehouse

Hein, James R.; McIntyre, Brandie; Perkins, Robert B.; Piper, David Z.; Evans, James

2002-01-01

This study, one in a series, reports bulk chemical and mineralogical compositions, as well as petrographic and outcrop descriptions of rocks collected from three measured outcrop sections of the Rex Chert member of the Phosphoria Formation in SE Idaho. The three measured sections were chosen from ten outcrops of Rex Chert that were described in the field. The Rex Chert overlies the Meade Peak Phosphatic Shale Member of the Phosphoria Formation, the source of phosphate ore in the region. Rex Chert removed as overburden comprises part of the material disposed in waste-rock piles during phosphate mining. It has been proposed that the chert be used to cap and isolate waste piles, thereby inhibiting the leaching of potentially toxic elements into the environment. It is also used to surface roads in the mining district. The rock samples studied here constitute a set of individual chert beds that are representative of each stratigraphic section sampled. The informally named cherty shale member that overlies the Rex Chert in measured section 1 was also described and sampled. The upper Meade Peak and the transition zone to the Rex Chert were described and sampled in section 7. The cherts are predominantly spicularite composed of granular and mosaic quartz, and sponge spicules, with various but minor amounts of other fossils and detrital grains. The cherty shale member and transition rocks between the Meade Peak and Rex Chert are siliceous siltstones and argillaceous cherts with ghosts of sponge spicules and somewhat more detrital grains than the chert. The overwhelmingly dominant mineral is quartz, although carbonate beds are rare in each section and are composed predominantly of calcite and dolomite in addition to quartz. Feldspar, mica, clay minerals, calcite, dolomite, and carbonate fluorapatite are minor to trace minerals in the chert. The mean concentrations of oxides and elements in the Rex Chert and the cherty shale member are dominated by SiO2, which averages 94.6%. Organic-carbon contents are generally very low in the chert, but are up to 1.8 wt. % in cherty shale member samples and up to 3.3% in samples from the transition between the Meade Peak and Rex Chert. Likewise, phosphate (P2O5) is generally low in the chert, but can be up to 3.1% in individual beds. Selenium concentrations in Rex Chert and cherty shale member samples vary from Q-mode factors are interpreted to represent the following rock and mineral components: chert-silica component consisting of Si (± Ba); phosphorite-phosphate component composed of P, Ca, As, Y, V, Cr, Sr, and La (± Fe, Zn, Cu, Ni, Li, Se, Nd, Hg); shale component composed of Al, Na, Zr, K, Ba, Li, and organic C (± Ti, Mg, Se, Ni, Fe, Sr, V, Mn, Zn); carbonate component (dolomite, calcite, silicified carbonates) composed of carbonate C, Mg, Ca, and Si (± Mn); tentatively organic matter-hosted elements (and/or sulfide-sulfate phases) composed of Cu (± organic C, Zn, Mn Si, Ni, Hg, and Li). Selenium shows a dominant association with the shale component, but correlations and Qmode factors also indicate that organic matter (within the shale component) and carbonate fluorapatite may host a portion of the Se. Consideration of larger numbers of factors in Qmode analysis indicates that native Se (a factor containing Se (± Ba)) may also comprise a minor component of the Se compliment.

Modelling the deployment of CO₂ storage in U.S. gas-bearing shales

DOE PAGES

Davidson, Casie L.; Dahowski, Robert T.; Dooley, James J.; ...

2014-12-31

The proliferation of commercial development in U.S. gas-bearing shales helped to drive a twelve-fold increase in domestic gas production between 2000 and 2010, and the nation's gas production rates continue to grow. While shales have long been regarded as a desirable caprock for CCS operations because of their low permeability and porosity, there is increasing interest in the feasibility of injecting CO₂ into shales to enhance methane recovery and augment CO₂ storage. Laboratory work published in recent years observes that shales with adsorbed methane appear to exhibit a stronger affinity for CO₂ adsorption, offering the potential to drive additional CH₄more » recovery beyond primary production and perhaps the potential to store a larger volume of CO₂ than the volume of methane displaced. Recent research by the authors on the revenues associated with CO₂-enhanced gas recovery (CO₂-EGR) in gas-bearing shales estimates that, based on a range of EGR response rates, the average revenue per ton of CO₂ for projects managed over both EGR and subsequent storage-only phases could range from $0.50 to $18/tCO₂. While perhaps not as profitable as EOR, for regions where lower-cost storage options may be limited, shales could represent another “early opportunity” storage option if proven feasible for reliable EGR and CO₂ storage. Significant storage potential exists in gas shales, with theoretical CO₂ storage resources estimated at approximately 30-50 GtCO₂. However, an analysis of the comprehensive cost competitiveness of these various options is necessary to understand the degree to which they might meaningfully impact U.S. CCS deployment or costs. This preliminary analysis shows that the degree to which EGR-based CO₂ storage could play a role in commercial-scale deployment is heavily dependent upon the offsetting revenues associated with incremental recovery; modeling the low revenue case resulted in only five shale-based projects, while under the high revenue case, shales accounted for as much as 20 percent of total U.S. storage in the first 20 years of deployment. Interestingly, even in this highest revenue case, there appear to be no negative-cost projects that would be profitable in a no-policy environment as modeled under the assumptions employed. While this reflects a very first look at the potential for shales, it is clear that more laboratory and experimental work are needed to reduce uncertainty in key variables and begin to differentiate and identify high-potential shales for early pilot study.« less

Munsell color value as related to organic carbon in Devonian shale of Appalachian basin

USGS Publications Warehouse

Hosterman, J.W.; Whitlow, S.I.

1981-01-01

Comparison of Munsell color value with organic carbon content of 880 samples from 50 drill holes in Appalachian basin shows that a power curve is the best fit for the data. A color value below 3 to 3.5 indicates the presence of organic carbon but is meaningless in determining the organic carbon content because a large increase in amount of organic carbon causes only a minor decrease in color value. Above 4, the color value is one of the factors that can be used in calculating the organic content. For samples containing equal amounts of organic carbon, calcareous shale containing more than 5% calcite is darker than shale containing less than 5% calcite.-Authors

The use of shale ash in dry mix construction materials

NASA Astrophysics Data System (ADS)

Gulbe, L.; Setina, J.; Juhnevica, I.

2017-10-01

The research was made to determine the use of shale ash usage in dry mix construction materials by replacing part of cement amount. Cement mortar ZM produced by SIA Sakret and two types of shale ashes from Narva Power plant (cyclone ash and electrostatic precipitator ash) were used. Fresh mortar properties, hardened mortar bulk density, thermal conductivity (λ10, dry) (table value) were tested in mortar ZM samples and mortar samples in which 20% of the amount of cement was replaced by ash. Compressive strenght, frost resistance and resistance to sulphate salt solutions were checked. It was stated that the use of electrostatic precipitator ash had a little change of the material properties, but the cyclone ash significantly reduced the mechanical strength of the material.

Environmental research on a modified in situ oil shale task process. Progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1980-05-01

This report summarizes the progress of the US Department of Energy's Oil Shale Task Force in its research program at the Occidental Oil Shale, Inc. facility at Logan Wash, Colorado. More specifically, the Task Force obtained samples from Retort 3E and Retort 6 and submitted these samples to a variety of analyses. The samples collected included: crude oil (Retort 6); light oil (Retort 6); product water (Retort 6); boiler blowdown (Retort 6); makeup water (Retort 6); mine sump water; groundwater; water from Retorts 1 through 5; retort gas (Retort 6); mine air; mine dust; and spent shale core (Retort 3E).more » The locations of the sampling points and methods used for collection and storage are discussed in Chapter 2 (Characterization). These samples were then distributed to the various laboratories and universities participating in the Task Force. For convenience in organizing the data, it is useful to group the work into three categories: Characterization, Leaching, and Health Effects. While many samples still have not been analyzed and much of the data remains to be interpreted, there are some preliminary conclusions the Task Force feels will be helpful in defining future needs and establishing priorities. It is important to note that drilling agents other than water were used in the recovery of the core from Retort 3E. These agents have been analyzed (see Table 12 in Chapter 2) for several constituents of interest. As a result some of the analyses of this core sample and leachates must be considered tentative.« less

Refining of Military Jet Fuels from Shale Oil. Part II. Volume III. Above Ground Shale Oil Process Data.

DTIC Science & Technology

1982-03-01

system. Regenerator flue gas composi- tion, spent catalyst carbon content and regenerated cata- lyst content are monitored for material balance purposes...and good material balance closures obtained. During each run pro- duct gas samples, regenerator flue gas samples, spent and -85- regenerated...TEMPERATURE DEPENDENCE OF DENITROGENATION AT 2 LHSV ON CO/MO ......................... 26 111-2 TEMPERATURE DEPENDENCE OF DESULFURIZATION AT 2 LHSV ON

Methane occurrence in groundwater of south-central New York State, 2012: summary of findings

USGS Publications Warehouse

Heisig, Paul M.; Scott, Tia-Marie

2013-01-01

A survey of methane in groundwater was undertaken to document methane occurrence on the basis of hydrogeologic setting within a glaciated 1,810-square-mile area of south-central New York that has not seen shale-gas resource development. The adjacent region in northeastern Pennsylvania has undergone shale-gas resource development from the Marcellus Shale. Well construction and subsurface data were required for each well sampled so that the local hydrogeologic setting could be classified. All wells were also at least 1 mile from any known gas well (active, exploratory, or abandoned). Sixty-six domestic wells and similar purposed supply wells were sampled during summer 2012. Field water-quality characteristics (pH, specific conductance, dissolved oxygen, and temperature) were measured at each well, and samples were collected and analyzed for dissolved gases, including methane and short-chain hydrocarbons. Carbon and hydrogen isotopic ratios of methane were measured in 21 samples that had at least 0.3 milligram per liter (mg/L) methane.

Dual pore-connectivity and flow-paths affect shale hydrocarbon production

NASA Astrophysics Data System (ADS)

Hayman, N. W.; Daigle, H.; Kelly, E. D.; Milliken, K. L.; Jiang, H.

2016-12-01

Aided with integrated characterization approaches of droplet contact angle measurement, mercury intrusion capillary pressure, low-pressure gas physisorption, scanning electron microscopy, and small angle neutron scattering, we have systematically studied how pore connectivity and wettability are associated with mineral and organic matter phases of shales (Barnett, Bakken, Eagle Ford), as well as their influence on macroscopic fluid flow and hydrocarbon movement, from the following complementary tests: vacuum saturation with vacuum-pulling on dry shale followed with tracer introduction and high-pressure intrusion, tracer diffusion into fluid-saturated shale, fluid and tracer imbibition into partially-saturated shale, and Wood's metal intrusion followed with imaging and elemental mapping. The first three tests use tracer-bearing fluids (hydrophilic API brine and hydrophobic n-decane) fluids with a suite of wettability tracers of different sizes and reactivities developed in our laboratory. These innovative and integrated approaches indicate a Dalmatian wettability behavior at a scale of microns, limited connectivity (<500 microns from shale sample edge) shale pores, and disparity of well-connected hydrophobic pore network ( 10 nm) and sparsely connected hydrophilic pore systems (>50-100 nm), which is linked to the steep initial decline and low overall recovery because of the limited connection of hydrocarbon molecules in the shale matrix to the stimulated fracture network.

Dual pore-connectivity and flow-paths affect shale hydrocarbon production

NASA Astrophysics Data System (ADS)

Hu, Q.; Barber, T.; Zhang, Y.; Md Golam, K.

2017-12-01

Aided with integrated characterization approaches of droplet contact angle measurement, mercury intrusion capillary pressure, low-pressure gas physisorption, scanning electron microscopy, and small angle neutron scattering, we have systematically studied how pore connectivity and wettability are associated with mineral and organic matter phases of shales (Barnett, Bakken, Eagle Ford), as well as their influence on macroscopic fluid flow and hydrocarbon movement, from the following complementary tests: vacuum saturation with vacuum-pulling on dry shale followed with tracer introduction and high-pressure intrusion, tracer diffusion into fluid-saturated shale, fluid and tracer imbibition into partially-saturated shale, and Wood's metal intrusion followed with imaging and elemental mapping. The first three tests use tracer-bearing fluids (hydrophilic API brine and hydrophobic n-decane) fluids with a suite of wettability tracers of different sizes and reactivities developed in our laboratory. These innovative and integrated approaches indicate a Dalmatian wettability behavior at a scale of microns, limited connectivity (<500 microns from shale sample edge) shale pores, and disparity of well-connected hydrophobic pore network ( 10 nm) and sparsely connected hydrophilic pore systems (>50-100 nm), which is linked to the steep initial decline and low overall recovery because of the limited connection of hydrocarbon molecules in the shale matrix to the stimulated fracture network.

77 FR 62253 - Agency Information Collection Activities: Comment Request

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-12

... digital geologic information related to coal, coalbed gas, shale gas and other energy resources and... assessments concerning coal and coal bed gas occurrences. Requesting external cooperation is the best way for... organic-rich shale, and obtain other information (including geophysical or seismic data, sample collection...

The Impact of a Potential Shale Gas Development in Germany and the United Kingdom on Pollutant and Greenhouse Gas Emissions

NASA Astrophysics Data System (ADS)

Weger, L.; Cremonese, L.; Bartels, M. P.; Butler, T. M.

2016-12-01

Several European countries with domestic shale gas reserves are considering extracting this natural gas resource to complement their energy transition agenda. Natural gas, which produces lower CO2 emissions upon combustion compared to coal or oil, has the potential to serve as a bridge in the transition from fossil fuels to renewables. However, the generation of shale gas leads to emissions of CH4 and pollutants such as PM, NOx and VOCs, which in turn impact climate as well as local and regional air quality. In this study, we explore the impact of a potential shale gas development in Europe, specifically in Germany and the United Kingdom, on emissions of greenhouse gases and pollutants. In order to investigate the effect on emissions, we first estimate a range of wells drilled per year and production volume for the two countries under examination based on available geological information and on regional infrastructural and economic limitations. Subsequently we assign activity data and emissions factors to the well development, gas production and processing stages of shale gas generation to enable emissions quantification. We then define emissions scenarios to explore different storylines of potential shale gas development, including low emissions (high level of regulation), high emissions (low level of regulation) and middle emissions scenarios, which influence fleet make-up, emission factor and activity data choices for emissions quantification. The aim of this work is to highlight important variables and their ranges, to promote discussion and communication of potential impacts, and to construct possible visions for a future shale gas development in the two study countries. In a follow-up study, the impact of pollutant emissions from these scenarios on air quality will be explored using the Weather Research and Forecasting model with chemistry (WRF-Chem) model.

Modified Lipid Extraction Methods for Deep Subsurface Shale

PubMed Central

Akondi, Rawlings N.; Trexler, Ryan V.; Pfiffner, Susan M.; Mouser, Paula J.; Sharma, Shikha

2017-01-01

Growing interest in the utilization of black shales for hydrocarbon development and environmental applications has spurred investigations of microbial functional diversity in the deep subsurface shale ecosystem. Lipid biomarker analyses including phospholipid fatty acids (PLFAs) and diglyceride fatty acids (DGFAs) represent sensitive tools for estimating biomass and characterizing the diversity of microbial communities. However, complex shale matrix properties create immense challenges for microbial lipid extraction procedures. Here, we test three different lipid extraction methods: modified Bligh and Dyer (mBD), Folch (FOL), and microwave assisted extraction (MAE), to examine their ability in the recovery and reproducibility of lipid biomarkers in deeply buried shales. The lipid biomarkers were analyzed as fatty acid methyl esters (FAMEs) with the GC-MS, and the average PL-FAME yield ranged from 67 to 400 pmol/g, while the average DG-FAME yield ranged from 600 to 3,000 pmol/g. The biomarker yields in the intact phospholipid Bligh and Dyer treatment (mBD + Phos + POPC), the Folch, the Bligh and Dyer citrate buffer (mBD-Cit), and the MAE treatments were all relatively higher and statistically similar compared to the other extraction treatments for both PLFAs and DGFAs. The biomarker yields were however highly variable within replicates for most extraction treatments, although the mBD + Phos + POPC treatment had relatively better reproducibility in the consistent fatty acid profiles. This variability across treatments which is associated with the highly complex nature of deeply buried shale matrix, further necessitates customized methodological developments for the improvement of lipid biomarker recovery. PMID:28790998

Impacts of Marcellus Shale Natural Gas Production on Regional Air Quality

NASA Astrophysics Data System (ADS)

Swarthout, R.; Russo, R. S.; Zhou, Y.; Mitchell, B.; Miller, B.; Lipsky, E. M.; Sive, B. C.

2012-12-01

Natural gas is a clean burning alternative to other fossil fuels, producing lower carbon dioxide (CO2) emissions during combustion. Gas deposits located within shale rock or tight sand formations are difficult to access using conventional drilling techniques. However, horizontal drilling coupled with hydraulic fracturing is now widely used to enhance natural gas extraction. Potential environmental impacts of these practices are currently being assessed because of the rapid expansion of natural gas production in the U.S. Natural gas production has contributed to the deterioration of air quality in several regions, such as in Wyoming and Utah, that were near or downwind of natural gas basins. We conducted a field campaign in southwestern Pennsylvania on 16-18 June 2012 to investigate the impact of gas production operations in the Marcellus Shale on regional air quality. A total of 235 whole air samples were collected in 2-liter electropolished stainless- steel canisters throughout southwestern Pennsylvania in a regular grid pattern that covered an area of approximately 8500 square km. Day and night samples were collected at each grid point and additional samples were collected near active wells, flaring wells, fluid retention reservoirs, transmission pipelines, and a processing plant to assess the influence of different stages of the gas production operation on emissions. The samples were analyzed at Appalachian State University for methane (CH4), CO2, C2-C10 nonmethane hydrocarbons (NMHCs), C1-C2 halocarbons, C1-C5 alkyl nitrates and selected reduced sulfur compounds. In-situ measurements of ozone (O3), CH4, CO2, nitric oxide (NO), total reactive nitrogen (NOy), formaldehyde (HCHO), and a range of volatile organic compounds (VOCs) were carried out at an upwind site and a site near active gas wells using a mobile lab. Emissions associated with gas production were observed throughout the study region. Elevated mixing ratios of CH4 and CO2 were observed in the southwest and northeast portions of the study area indicating multiple emission sources. We also present comparisons of VOC fingerprints observed in the Marcellus Shale to our previous observations of natural gas emissions from the Denver-Julesburg Basin in northeast Colorado to identify tracers for these different natural gas sources.

AFRRI (Armed Forces Radiobiology Research Institute) Annual Research Report 1 October 1980-30 September 1981.

DTIC Science & Technology

1981-09-30

weight of either petroleum-derived jet propulsion fuel number 5 (JP5) or one of three samples of shale-derived JP5 (1). The surviving rats were...sacrificed at 14 days after dosing. In another study, rats were gavaged with one of the four fuel samples at the rate of 24 mI/kg body weight and sacrificed...at 1, 2, or 3 days postdosing. A significant difference was seen in the lethality of the three shale-derived samples , even though all originated from

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, J.M.; Sheppard, M.C.; Houwen, O.H.

Previous work on shale mechanical properties has focused on the slow deformation rates appropriate to wellbore deformation. Deformation of shale under a drill bit occurs at a very high rate, and the failure properties of the rock under these conditions are crucial in determining bit performance and in extracting lithology and pore-pressure information from drilling parameters. Triaxial tests were performed on two nonswelling shales under a wide range of strain rates and confining and pore pressures. At low strain rates, when fluid is relatively free to move within the shale, shale deformation and failure are governed by effective stress ormore » pressure (i.e., total confining pressure minus pore pressure), as is the case for ordinary rock. If the pore pressure in the shale is high, increasing the strain rate beyond about 0.1%/sec causes large increases in the strength and ductility of the shale. Total pressure begins to influence the strength. At high stain rates, the influence of effective pressure decreases, except when it is very low (i.e., when pore pressure is very high); ductility then rises rapidly. This behavior is opposite that expected in ordinary rocks. This paper briefly discusses the reasons for these phenomena and their impact on wellbore and drilling problems.« less

Lateral fluid flow in a compacting sand-shale sequence: South Caspian basin.

USGS Publications Warehouse

Bredehoeft, J.D.; Djevanshir, R.D.; Belitz, K.R.

1988-01-01

The South Caspian basin contains both sands and shales that have pore-fluid pressures substantially in excess of hydrostatic fluid pressure. Pore-pressure data from the South Caspian basin demonstrate that large differences in excess hydraulic head exist between sand and shale. The data indicate that sands are acting as drains for overlying and underlying compacting shales and that fluid flows laterally through the sand on a regional scale from the basin interior northward to points of discharge. The major driving force for the fluid movement is shale compaction. We present a first- order mathematical analysis in an effort to test if the permeability of the sands required to support a regional flow system is reasonable. The results of the analysis suggest regional sand permeabilities ranging from 1 to 30 md; a range that seems reasonable. This result supports the thesis that lateral fluid flow is occurring on a regional scale within the South Caspian basin. If vertical conduits for flow exist within the basin, they are sufficiently impermeable and do not provide a major outlet for the regional flow system. The lateral fluid flow within the sands implies that the stratigraphic sequence is divided into horizontal units that are hydraulically isolated from one another, a conclusion that has important implications for oil and gas migration.-Authors

Projecting the Water Footprint Associated with Shale Resource Production: Eagle Ford Shale Case Study.

PubMed

Ikonnikova, Svetlana A; Male, Frank; Scanlon, Bridget R; Reedy, Robert C; McDaid, Guinevere

2017-12-19

Production of oil from shale and tight reservoirs accounted for almost 50% of 2016 total U.S. production and is projected to continue growing. The objective of our analysis was to quantify the water outlook for future shale oil development using the Eagle Ford Shale as a case study. We developed a water outlook model that projects water use for hydraulic fracturing (HF) and flowback and produced water (FP) volumes based on expected energy prices; historical oil, natural gas, and water-production decline data per well; projected well spacing; and well economics. The number of wells projected to be drilled in the Eagle Ford through 2045 is almost linearly related to oil price, ranging from 20 000 wells at $30/barrel (bbl) oil to 97 000 wells at $100/bbl oil. Projected FP water volumes range from 20% to 40% of HF across the play. Our base reference oil price of $50/bbl would result in 40 000 additional wells and related HF of 265 × 10 9 gal and FP of 85 × 10 9 gal. The presented water outlooks for HF and FP water volumes can be used to assess future water sourcing and wastewater disposal or reuse, and to inform policy discussions.

Lithologic Controls on Critical Zone Processes in a Variably Metamorphosed Shale-Hosted Watershed

NASA Astrophysics Data System (ADS)

Eldam Pommer, R.; Navarre-Sitchler, A.

2017-12-01

Local and regional shifts in thermal maturity within sedimentary shale systems impart significant variation in chemical and physical rock properties, such as pore-network morphology, mineralogy, organic carbon content, and solute release potential. Even slight variations in these properties on a watershed scale can strongly impact surface and shallow subsurface processes that drive soil formation, landscape evolution, and bioavailability of nutrients. Our ability to map and quantify the effects of this heterogeneity on critical zone processes is hindered by the complex coupling of the multi-scale nature of rock properties, geochemical signatures, and hydrological processes. This study addresses each of these complexities by synthesizing chemical and physical characteristics of variably metamorphosed shales in order to link rock heterogeneity with modern earth surface and shallow subsurface processes. More than 80 samples of variably metamorphosed Mancos Shale were collected in the East River Valley, Colorado, a headwater catchment of the Upper Colorado River Basin. Chemical and physical analyses of the samples show that metamorphism decreases overall rock porosity, pore anisotropy, and surface area, and introduces unique chemical signatures. All of these changes result in lower overall solute release from the Mancos Shale in laboratory dissolution experiments and a change in rock-derived solute chemistry with decreasing organic carbon and cation exchange capacity (Ca, Na, Mg, and K). The increase in rock competency and decrease in reactivity of the more thermally mature shales appear to subsequently control river morphology, with lower channel sinuosity associated with areas of the catchment underlain by metamorphosed Mancos Shale. This work illustrates the formative role of the geologic template on critical zone processes and landscape development within and across watersheds.

Ecological risks of shale oil and gas development to wildlife, aquatic resources and their habitats

USGS Publications Warehouse

Brittingham, Margaret C.; Maloney, Kelly O.; Farag, Aïda M.; Harper, David D.; Bowen, Zachary H.

2014-01-01

Technological advances in hydraulic fracturing and horizontal drilling have led to the exploration and exploitation of shale oil and gas both nationally and internationally. Extensive development of shale resources has occurred within the United States over the past decade, yet full build out is not expected to occur for years. Moreover, countries across the globe have large shale resources and are beginning to explore extraction of these resources. Extraction of shale resources is a multistep process that includes site identification, well pad and infrastructure development, well drilling, high-volume hydraulic fracturing and production; each with its own propensity to affect associated ecosystems. Some potential effects, for example from well pad, road and pipeline development, will likely be similar to other anthropogenic activities like conventional gas drilling, land clearing, exurban and agricultural development and surface mining (e.g., habitat fragmentation and sedimentation). Therefore, we can use the large body of literature available on the ecological effects of these activities to estimate potential effects from shale development on nearby ecosystems. However, other effects, such as accidental release of wastewaters, are novel to the shale gas extraction process making it harder to predict potential outcomes. Here, we review current knowledge of the effects of high-volume hydraulic fracturing coupled with horizontal drilling on terrestrial and aquatic ecosystems in the contiguous United States, an area that includes 20 shale plays many of which have experienced extensive development over the past decade. We conclude that species and habitats most at risk are ones where there is an extensive overlap between a species range or habitat type and one of the shale plays (leading to high vulnerability) coupled with intrinsic characteristics such as limited range, small population size, specialized habitat requirements, and high sensitivity to disturbance. Examples include core forest habitat and forest specialists, sagebrush habitat and specialists, vernal pond inhabitants and stream biota. We suggest five general areas of research and monitoring that could aid in development of effective guidelines and policies to minimize negative impacts and protect vulnerable species and ecosystems: (1) spatial analyses, (2) species-based modeling, (3) vulnerability assessments, (4) ecoregional assessments, and (5) threshold and toxicity evaluations.

Ecological risks of shale oil and gas development to wildlife, aquatic resources and their habitats.

PubMed

Brittingham, Margaret C; Maloney, Kelly O; Farag, Aïda M; Harper, David D; Bowen, Zachary H

2014-10-07

Technological advances in hydraulic fracturing and horizontal drilling have led to the exploration and exploitation of shale oil and gas both nationally and internationally. Extensive development of shale resources has occurred within the United States over the past decade, yet full build out is not expected to occur for years. Moreover, countries across the globe have large shale resources and are beginning to explore extraction of these resources. Extraction of shale resources is a multistep process that includes site identification, well pad and infrastructure development, well drilling, high-volume hydraulic fracturing and production; each with its own propensity to affect associated ecosystems. Some potential effects, for example from well pad, road and pipeline development, will likely be similar to other anthropogenic activities like conventional gas drilling, land clearing, exurban and agricultural development and surface mining (e.g., habitat fragmentation and sedimentation). Therefore, we can use the large body of literature available on the ecological effects of these activities to estimate potential effects from shale development on nearby ecosystems. However, other effects, such as accidental release of wastewaters, are novel to the shale gas extraction process making it harder to predict potential outcomes. Here, we review current knowledge of the effects of high-volume hydraulic fracturing coupled with horizontal drilling on terrestrial and aquatic ecosystems in the contiguous United States, an area that includes 20 shale plays many of which have experienced extensive development over the past decade. We conclude that species and habitats most at risk are ones where there is an extensive overlap between a species range or habitat type and one of the shale plays (leading to high vulnerability) coupled with intrinsic characteristics such as limited range, small population size, specialized habitat requirements, and high sensitivity to disturbance. Examples include core forest habitat and forest specialists, sagebrush habitat and specialists, vernal pond inhabitants and stream biota. We suggest five general areas of research and monitoring that could aid in development of effective guidelines and policies to minimize negative impacts and protect vulnerable species and ecosystems: (1) spatial analyses, (2) species-based modeling, (3) vulnerability assessments, (4) ecoregional assessments, and (5) threshold and toxicity evaluations.

Laboratory characterization of shale pores

NASA Astrophysics Data System (ADS)

Nur Listiyowati, Lina

2018-02-01

To estimate the potential of shale gas reservoir, one needs to understand the characteristics of pore structures. Characterization of shale gas reservoir microstructure is still a challenge due to ultra-fine grained micro-fabric and micro level heterogeneity of these sedimentary rocks. The sample used in the analysis is a small portion of any reservoir. Thus, each measurement technique has a different result. It raises the question which methods are suitable for characterizing pore shale. The goal of this paper is to summarize some of the microstructure analysis tools of shale rock to get near-real results. The two analyzing pore structure methods are indirect measurement (MIP, He, NMR, LTNA) and direct observation (SEM, TEM, Xray CT). Shale rocks have a high heterogeneity; thus, it needs multiscale quantification techniques to understand their pore structures. To describe the complex pore system of shale, several measurement techniques are needed to characterize the surface area and pore size distribution (LTNA, MIP), shapes, size and distribution of pore (FIB-SEM, TEM, Xray CT), and total porosity (He pycnometer, NMR). The choice of techniques and methods should take into account the purpose of the analysis and also the time and budget.

Experimental investigations of the wettability of clays and shales

NASA Astrophysics Data System (ADS)

Borysenko, Artem; Clennell, Ben; Sedev, Rossen; Burgar, Iko; Ralston, John; Raven, Mark; Dewhurst, David; Liu, Keyu

2009-07-01

Wettability in argillaceous materials is poorly understood, yet it is critical to hydrocarbon recovery in clay-rich reservoirs and capillary seal capacity in both caprocks and fault gouges. The hydrophobic or hydrophilic nature of clay-bearing soils and sediments also controls to a large degree the movement of spilled nonaqueous phase liquids in the subsurface and the options available for remediation of these pollutants. In this paper the wettability of hydrocarbons contacting shales in their natural state and the tendencies for wettability alteration were examined. Water-wet, oil-wet, and mixed-wet shales from wells in Australia were investigated and were compared with simplified model shales (single and mixed minerals) artificially treated in crude oil. The intact natural shale samples (preserved with their original water content) were characterized petrophysically by dielectric spectroscopy and nuclear magnetic resonance, plus scanning electron, optical and fluorescence microscopy. Wettability alteration was studied using spontaneous imbibition, pigment extraction, and the sessile drop method for contact angle measurement. The mineralogy and chemical compositions of the shales were determined by standard methods. By studying pure minerals and natural shales in parallel, a correlation between the petrophysical properties, and wetting behavior was observed. These correlations may potentially be used to assess wettability in downhole measurements.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalyoncu, R.S.; Boyer, J.P.; Snyder, M.J.

Partial data on the characterization of Well 0-1 (Christian County, Kentucky) shales were first reported in the Fifth Quarterly Technical Progress Report on January 1978. This report presents all the characterization data and its analysis on the 0-1 shales. Coring of Well 0-1 was accomplished in October 1976. A total of 17 samples were obtained, 13 for Battelle and 4 for other DOE Contractors. Methane is almost the sole hydrocarbon gas present in these shales, with higher chain hydrocarbon gases nearly nonexistent. An apparent increase in hydrocarbon gas contents with shale depth is observed. Other organic contents (in the formmore » of carbon and hydrogen) also show an increase with increasing shale depth. An increase in hydrocarbon gas contents with carbon and hydrogen contents is also noticeable. Natural gas, carbon and hydrogen contents all vary inversely with bulk densities. 0-1 shales show low mercury intrusion porosities and very low to negligible gas permeabilities. Lithology of these shales is very similar to those previously reported, quartz being the most abundant single mineral. Illite and kaolin are the major clay minerals with a number of carbonates (nahcolite, sortite, siderite) present in moderate quantities. Pyrite is also observed in significant quantities.« less

Ultraviolet laser-induced lateral photovoltaic response in anisotropic black shale

NASA Astrophysics Data System (ADS)

Miao, Xinyang; Zhu, Jing; Zhao, Kun; Yue, Wenzheng

2017-12-01

The anisotropy of shale has significant impact on oil and gas exploration and engineering. In this paper, a-248 nm ultraviolet laser was employed to assess the anisotropic lateral photovoltaic (LPV) response of shale. Anisotropic angle-depending voltage signals were observed with different peak amplitudes ( V p) and decay times. We employed exponential models to explain the charge carrier transport in horizontal and vertical directions. Dependences of the laser-induced LPV on the laser spot position were observed. Owing to the Dember effect and the layered structure of shale, V p shows an approximately linear dependence with the laser-irradiated position for the 0° shale sample but nonlinearity for the 45° and 90° ones. The results demonstrate that the laser-induced voltage method is very sensitive to the structure of materials, and thus has a great potential in oil and gas reservoir characterization.

VEGETATIVE REHABILITATION OF ARID LAND DISTURBED IN THE DEVELOPMENT OF OIL SHALE AND COAL

EPA Science Inventory

Field experiments were established on sites disturbed by exploratory drilling in the oil shale region of northeastern Utah and on disturbed sites on a potential coal mine in south central Utah. Concurrently, greenhouse studies were carried out using soil samples from disturbed si...

Modeling of gas generation from the Barnett Shale, Fort Worth Basin, Texas

USGS Publications Warehouse

Hill, R.J.; Zhang, E.; Katz, B.J.; Tang, Y.

2007-01-01

The generative gas potential of the Mississippian Barnett Shale in the Fort Worth Basin, Texas, was quantitatively evaluated by sealed gold-tube pyrolysis. Kinetic parameters for gas generation and vitrinite reflectance (Ro) changes were calculated from pyrolysis data and the results used to estimate the amount of gas generated from the Barnett Shale at geologic heating rates. Using derived kinetics for Ro evolution and gas generation, quantities of hydrocarbon gas generated at Ro ??? 1.1% are about 230 L/t (7.4 scf/t) and increase to more that 5800 L/t (186 scf/t) at Ro ??? 2.0% for a sample with an initial total organic carbon content of 5.5% and Ro = 0.44%. The volume of shale gas generated will depend on the organic richness, thickness, and thermal maturity of the shale and also the amount of petroleum that is retained in the shale during migration. Gas that is reservoired in shales appears to be generated from the cracking of kerogen and petroleum that is retained in shales, and that cracking of the retained petroleum starts by Ro ??? 1.1%. This result suggests that the cracking of petroleum retained in source rocks occurs at rates that are faster than what is predicted for conventional siliciclastic and carbonate reservoirs, and that contact of retained petroleum with kerogen and shale mineralogy may be a critical factor in shale-gas generation. Shale-gas systems, together with overburden, can be considered complete petroleum systems, although the processes of petroleum migration, accumulation, and trap formation are different from what is defined for conventional petroleum systems. Copyright ?? 2007. The American Association of Petroleum Geologists. All rights reserved.

Petroleum source rock evaluation of the Alum and Dictyonema Shales (Upper Cambrian-Lower Ordovician) in the Baltic Basin and Podlasie Depression (eastern Poland)

NASA Astrophysics Data System (ADS)

Kosakowski, Paweł; Kotarba, Maciej J.; Piestrzyński, Adam; Shogenova, Alla; Więcław, Dariusz

2017-03-01

We present geochemical characteristics of the Lower Palaeozoic shales deposited in the Baltic Basin and Podlasie Depression. In the study area, this strata are represented by the Upper Cambrian-Lower Ordovician Alum Shale recognized in southern Scandinavia and Polish offshore and a equivalent the Lower Tremadocian Dictyonema Shale from the northern Estonia and the Podlasie Depression in Poland. Geochemical analyses reveal that the Alum Shale and Dictyonema Shale present high contents of organic carbon. These deposits have the best source quality among the Lower Palaeozoic strata, and they are the best source rocks in the Baltic region. The bituminous shales complex has TOC contents up to ca. 22 wt%. The analysed rocks contain low-sulphur, oil-prone Type-II kerogen deposited in anoxic or sub-oxic conditions. The maturity of the Alum and Dictyonema Shales changes gradually, from the east and north-east to the west and south-west, i.e. in the direction of the Tornquist-Teisseyre Zone. Samples, located in the seashore of Estonia and in the Podlasie region, are immature and in the initial phase of "oil window". The mature shales were found in the central offshore part of the Polish Baltic Basin, and the late mature and overmature are located in the western part of the Baltic Basin. The Alum and Dictyonema Shales are characterized by a high grade of radioactive elements, especially uranium. The enrichment has a syngenetic or early diagenetic origin. The measured content of uranium reached up to 750 ppm and thorium up to 37 ppm.

Water resources of Hot Springs County, Wyoming

USGS Publications Warehouse

Plafcan, Maria; Ogle, Kathy Muller

1994-01-01

The wells and springs inventoried in Hot Springs County most commonly had been completed in or issued from the Quaternary alluvium, Quaternary terrace deposits, Fort Union and Mesaverde Formations, Cody Shale, and the Frontier and Chugwater Formations. The largest discharges measured were from the Quaternary terrace deposits (400 gallons per minute) and the Phosphoria Formation (1,000 gallons per minute). Discharges from all other geologic units varied, but most wells and springs yielded 50 gallons per minute or less.Water-quality samples collected from springs that issued from the Absaroka Volcanic Supergroup, the Bighorn Dolomite, and the Flathead Sandstone had the lowest dissolved-solids concentrations, which ranged from 58 to 265 milligrams per liter, and the least variable water types. Water from the volcanic rocks was a sodium bicarbonate type; whereas, water from the Flathead Sandstone was a calcium bicarbonate type. Water types for all the other aquifers varied from sampling site to sampling site; however, water samples from the Fort Union Formation and the Cody Shale were consistently of the sodium sulfate type. The effect of oil- and gas-development at Hamilton Dome on thermal spring discharges at Hot Springs State Park near Thermopolis was studied. The estimated drawdown from 1918, when the Hamilton Dome oil field was discovered, to 1988 was made using drill-stem data from previous studies. Drawdown at Big Spring in the Park was estimated to be less than 3 feet on the basis of recent oil- and water-production data, previous modeling studies, and the estimated water-level drawdown of 330 feet in wells at the Hamilton Dome oil field.Streams originating in the Plains region of the county, such as Middle Fork Owl Creek, are ephemeral or intermittent; whereas, streams originating in the mountains, such as Gooseberry Creek, are perennial. Average annual runoff across the county ranges from 0.26 inches at a representative streamflow-gaging station near Worland in the plains region to 5.4 inches in the Owl Creek Mountains and southeastern Absaroka Range.

Speciation and weathering of selenium in upper cretaceous chalk and shale from South Dakota and Wyoming, USA

NASA Astrophysics Data System (ADS)

Kulp, Thomas R.; Pratt, Lisa M.

2004-09-01

In geologic materials, petroleum, and the environment, selenium occurs in various oxidation states (VI, IV, 0, -II), mineralized forms, and organo-Se complexes. Each of these forms is characterized by specific chemical and biochemical properties that control the element's solubility, toxicity, and environmental behavior. The organic rich chalks and shales of the Upper Cretaceous Niobrara Formation and the Pierre Shale in South Dakota and Wyoming are bentoniferous stratigraphic intervals characterized by anomalously high concentrations of naturally occurring Se. Numerous environmental problems have been associated with Se derived from these geological units, including the development of seleniferous soils and vegetation that are toxic to livestock and the contamination of drinking water supplies by Se mobilized in groundwater. This study describes a sequential extraction protocol followed by speciation treatments and quantitative analysis by Hydride Generation-Atomic Absorption Spectroscopy. This protocol was utilized to investigate the geochemical forms and the oxidation states in which Se occurs in these geologic units. Organic Se and di-selenide minerals are the predominant forms of Se present in the chalks, shales, and bentonites, but distinctive variations in these forms were observed between different sample types. Chalks contain significantly greater proportions of Se in the form of di-selenide minerals (including Se associated with pyrite) than the shales where base-soluble, humic, organo-Se complexes are more prevalent. A comparison between unweathered samples collected from lithologic drill cores and weathered samples collected from outcrop suggest that the humic, organic-Se compounds in shale are formed during oxidative weathering and that Se oxidized by weathering is more likely to be retained by shale than by chalk. Selenium enrichment in bentonites is inferred to result from secondary processes including the adsorption of Se mobilized by groundwater from surrounding organic rich sediments to clay mineral and iron hydroxide surfaces, as well as microbial reduction of Se within the bentonitic intervals. Distinct differences are inferred for the biogeochemical pathways that affected sedimentary Se sequestration during periods of chalk accumulation compared to shale deposition in the Cretaceous seaway. Mineralogy of sediment and the nature of the organic matter associated with each of these rock types have important implications for the environmental chemistry and release of Se to the environment during weathering.

Baseline well inventory and groundwater-quality data from a potential shale gas resource area in parts of Lee and Chatham Counties, North Carolina, October 2011-August 2012

USGS Publications Warehouse

Chapman, Melinda J.; Gurley, Laura N.; Fitzgerald, Sharon A.

2014-01-01

Records were obtained for 305 wells and 1 spring in northwestern Lee and southeastern Chatham counties, North Carolina. Well depths ranged from 26 to 720 feet and yields ranged from 0.25 to 100 gallons per minute. A subset of 56 wells and 1 spring were sampled for baseline groundwaterquality constituents including the following: major ions; dissolved metals; nutrients; dissolved gases (including methane); volatile and semivolatile organic compounds; glycols; isotopes of strontium, radium, methane (if sufficient concentration), and water; and dissolved organic and inorganic carbon. Dissolved methane gas concentrations were low, ranging from less than 0.00007 (lowest reporting level) to 0.48 milligrams per liter. Concentrations of nitrate, boron, iron, manganese, sulfate, chloride, total dissolved solids, and measurements of pH exceeded federal and state drinking water standards in a few samples. Iron and manganese concentrations exceeded the secondary (aesthetic) drinking water standard in approximately 35 to 37 percent of the samples.

Shale gas characteristics of the Lower Toarcian Posidonia Shale in Germany: from basin to nanometre scale

NASA Astrophysics Data System (ADS)

Schulz, Hans-Martin; Bernard, Sylvain; Horsfield, Brian; Krüger, Martin; Littke, Ralf; di primio, Rolando

2013-04-01

The Early Toarcian Posidonia Shale is a proven hydrocarbon source rock which was deposited in a shallow epicontinental basin. In southern Germany, Tethyan warm-water influences from the south led to carbonate sedimentation, whereas cold-water influxes from the north controlled siliciclastic sedimentation in the northwestern parts of Germany and the Netherlands. Restricted sea-floor circulation and organic matter preservation are considered to be the consequence of an oceanic anoxic event. In contrast, non-marine conditions led to sedimentation of coarser grained sediments under progressively terrestrial conditions in northeastern Germany The present-day distribution of Posidonia Shale in northern Germany is restricted to the centres of rift basins that formed in the Late Jurassic (e.g., Lower Saxony Basin and Dogger Troughs like the West and East Holstein Troughs) as a result of erosion on the basin margins and bounding highs. The source rock characteristics are in part dependent on grain size as the Posidonia Shale in eastern Germany is referred to as a mixed to non-source rock facies. In the study area, the TOC content and the organic matter quality vary vertically and laterally, likely as a consequence of a rising sea level during the Toarcian. Here we present and compare data of whole Posidonia Shale sections, investigating these variations and highlighting the variability of Posidonia Shale depositional system. During all phases of burial, gas was generated in the Posidonia Shale. Low sedimentation rates led to diffusion of early diagenetically formed biogenic methane. Isochronously formed diagenetic carbonates tightened the matrix and increased brittleness. Thermogenic gas generation occurred in wide areas of Lower Saxony as well as in Schleswig Holstein. Biogenic methane gas can still be formed today in Posidonia Shale at shallow depth in areas which were covered by Pleistocene glaciers. Submicrometric interparticle pores predominate in immature samples. At thermal maturities beyond the oil window, intra-mineral and intra-organic pores develop. In such overmature samples, nanopores occur within pyrobitumen masses. Important for gas storage and transport, they likely result from exsolution of gaseous hydrocarbon. References Bernard S., Wirth R., Schreiber A., Bowen L., Aplin A.C., Mathia E.J., Schulz H-M., & Horsfield B.: FIB-SEM and TEM investigations of an organic-rich shale maturation series (Lower Toarcian Posidonia Shale): Nanoscale pore system and fluid-rock interactions. AAPG Bulletin Special Issue "Electron Microscopy of Shale Hydrocarbon Reservoirs" (in press). Bernard, S., Horsfield, B., Schulz, H-M., Wirth, R., Schreiber, A., & Sherwood, N., 2012, Geochemical evolution of organic-rich shales with increasing maturity: A STXM and TEM study of the Posidonia Shale (Lower Toarcian, northern Germany): Marine and Petroleum Geology 31 (1) 70-89. Lott, G.K., Wong, T.E., Dusar, M., Andsbjerg, J., Mönnig, E., Feldman-Olszewska, A. & Verreussel, R.M.C.H., 2010. Jurassic. In: Doornenbal, J.C. and Stevenson, A.G. (editors): Petroleum Geological Atlas of the Southern Permian Basin Area. EAGE Publications b.v. (Houten): 175-193.

Provenance analysis of the Oligocene turbidites (Andaman Flysch), South Andaman Island: A geochemical approach

NASA Astrophysics Data System (ADS)

Bandopadhyay, P. C.; Ghosh, Biswajit

2015-07-01

The Oligocene-aged sandstone-shale turbidites of the Andaman Flysch are best exposed along the east coast of the South Andaman Island. Previously undocumented sandstone-shale geochemistry, investigated here, provides important geochemical constraints on turbidite provenance. The average 70.75 wt% SiO2, 14.52 wt% Al2O3, 8.2 wt% FeMgO and average 0.20 Al2O3/SiO2 and 1.08 K2O/Na2O ratios in sandstones, compare with quartzwackes. The shale samples have average 59.63 wt% SiO2, 20.29 wt% Al2O3, 12.63 wt% FeMgO and average 2.42 K2O/Na2O and 0.34 Al2O3/SiO2 ratios. Geochemical data on CaO-Na2O-K2O diagram fall close to a granite field and on K2O/Na2O-SiO2 diagram within an active continental margin tectonic setting. The range and average values of Rb and Rb/Sr ratios are consistent with acid-intermediate igneous source rocks, while the values and ratios for Cr and Ni are with mafic rocks. Combined geochemical, petrographic and palaeocurrent data indicate a dominantly plutonic-metamorphic provenance with a lesser contribution from sedimentary and volcanic source, which is possibly the Shan-Thai continental block and volcanic arc of the north-eastern and eastern Myanmar. Chemical index of alteration (CIA) values suggests a moderate range of weathering of a moderate relief terrane under warm and humid climate.

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development, north-central Arkansas

USGS Publications Warehouse

Warner, Nathaniel R.; Kresse, Timothy M.; Hays, Phillip D.; Down, Adrian; Karr, Jonathan D.; Jackson, R.B.; Vengosh, Avner

2013-01-01

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH4 gas content and its C isotopes (δ13CCH4), and select isotope tracers (δ11B, 87Sr/86Sr, δ2H, δ18O, δ13CDIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH4 was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH4/L. The δ13CCH4 of dissolved CH4 ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH4 concentrations, with a possible minor contribution of trace amounts of thermogenic CH4. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ13CCH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO3 dominated, (3) TDS > 100 mg/L and Na–HCO3dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (87Sr/86Sr = 0.7097–0.7166), C (δ13CDIC = −21.3‰ to −4.7‰), and B (δ11B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO3, and higher-mineralized Na–HCO3 composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH4 and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.

Synchrotron-based transmission x-ray microscopy for improved extraction in shale during hydraulic fracturing

NASA Astrophysics Data System (ADS)

Kiss, Andrew M.; Jew, Adam D.; Joe-Wong, Claresta; Maher, Kate M.; Liu, Yijin; Brown, Gordon E.; Bargar, John

2015-09-01

Engineering topics which span a range of length and time scales present a unique challenge to researchers. Hydraulic fracturing (fracking) of oil shales is one of these challenges and provides an opportunity to use multiple research tools to thoroughly investigate a topic. Currently, the extraction efficiency from the shale is low but can be improved by carefully studying the processes at the micro- and nano-scale. Fracking fluid induces chemical changes in the shale which can have significant effects on the microstructure morphology, permeability, and chemical composition. These phenomena occur at different length and time scales which require different instrumentation to properly study. Using synchrotron-based techniques such as fluorescence tomography provide high sensitivity elemental mapping and an in situ micro-tomography system records morphological changes with time. In addition, the transmission X-ray microscope (TXM) at the Stanford Synchrotron Radiation Lightsource (SSRL) beamline 6-2 is utilized to collect a nano-scale three-dimensional representation of the sample morphology with elemental and chemical sensitivity. We present the study of a simplified model system, in which pyrite and quartz particles are mixed and exposed to oxidizing solution, to establish the basic understanding of the more complex geology-relevant oxidation reaction. The spatial distribution of the production of the oxidation reaction, ferrihydrite, is retrieved via full-field XANES tomography showing the reaction pathway. Further correlation between the high resolution TXM data and the high sensitivity micro-probe data provides insight into potential morphology changes which can decrease permeability and limit hydrocarbon recovery.

Shallow Aquifer Methane Gas Source Assessment

NASA Astrophysics Data System (ADS)

Coffin, R. B.; Murgulet, D.; Rose, P. S.; Hay, R.

2014-12-01

Shale gas can contribute significantly to the world's energy demand. Hydraulic fracturing (fracking) on horizontal drill lines developed over the last 15 years makes formerly inaccessible hydrocarbons economically available. From 2000 to 2035 shale gas is predicted to rise from 1% to 46% of the total natural gas for the US. A vast energy resource is available in the United States. While there is a strong financial advantage to the application of fracking there is emerging concern about environmental impacts to groundwater and air quality from improper shale fracking operations. Elevated methane (CH4) concentrations have been observed in drinking water throughout the United States where there is active horizontal drilling. Horizontal drilling and hydraulic-fracturing can increase CH4 transport to aquifers, soil and the vadose zone. Seepage can also result from casing failure in older wells. However, there is strong evidence that elevated CH4 concentrations can be associated with topographic and hydrogeologic features, rather than shale-gas extraction processes. Carbon isotope geochemistry can be applied to study CH4source(s) in shallow vadose zone and groundwater systems. A preliminary TAMU-CC isotope data set from samples taken at different locations in southern Texas shows a wide range of CH4 signatures suggesting multiple sources of methane and carbon dioxide. These data are interpreted to distinguish regions with methane contributions from deep-sourced horizontal drilling versus shallow system microbial production. Development of a thorough environmental assessment using light isotope analysis can provide understanding of shallow anthropogenic versus natural CH4sources and assist in identifying regions that require remedial actions.

Understanding Shale Gas: Recent Progress and Remaining Challenges

DOE PAGES

Striolo, Alberto; Cole, David R.

2017-08-27

Because of a number of technological advancements, unconventional hydrocarbons, and in particular shale gas, have transformed the US economy. Much is being learned, as demonstrated by the reduced cost of extracting shale gas in the US over the past five years. However, a number of challenges still need to be addressed. Many of these challenges represent grand scientific and technological tasks, overcoming which will have a number of positive impacts, ranging from the reduction of the environmental footprint of shale gas production to improvements and leaps forward in diverse sectors, including chemical manufacturing and catalytic transformations. This review addresses recentmore » advancements in computational and experimental approaches, which led to improved understanding of, in particular, structure and transport of fluids, including hydrocarbons, electrolytes, water, and CO 2 in heterogeneous subsurface rocks such as those typically found in shale formations. Finally, the narrative is concluded with a suggestion of a few research directions that, by synergistically combining computational and experimental advances, could allow us to overcome some of the hurdles that currently hinder the production of hydrocarbons from shale formations.« less

Integrated geostatistics for modeling fluid contacts and shales in Prudhoe Bay

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perez, G.; Chopra, A.K.; Severson, C.D.

1997-12-01

Geostatistics techniques are being used increasingly to model reservoir heterogeneity at a wide range of scales. A variety of techniques is now available with differing underlying assumptions, complexity, and applications. This paper introduces a novel method of geostatistics to model dynamic gas-oil contacts and shales in the Prudhoe Bay reservoir. The method integrates reservoir description and surveillance data within the same geostatistical framework. Surveillance logs and shale data are transformed to indicator variables. These variables are used to evaluate vertical and horizontal spatial correlation and cross-correlation of gas and shale at different times and to develop variogram models. Conditional simulationmore » techniques are used to generate multiple three-dimensional (3D) descriptions of gas and shales that provide a measure of uncertainty. These techniques capture the complex 3D distribution of gas-oil contacts through time. The authors compare results of the geostatistical method with conventional techniques as well as with infill wells drilled after the study. Predicted gas-oil contacts and shale distributions are in close agreement with gas-oil contacts observed at infill wells.« less

Distribution of Hydroxyl Groups in Kukersite Shale Oil: Quantitative Determination Using Fourier Transform Infrared (FT-IR) Spectroscopy.

PubMed

Baird, Zachariah Steven; Oja, Vahur; Järvik, Oliver

2015-05-01

This article describes the use of Fourier transform infrared (FT-IR) spectroscopy to quantitatively measure the hydroxyl concentrations among narrow boiling shale oil cuts. Shale oil samples were from an industrial solid heat carrier retort. Reference values were measured by titration and were used to create a partial least squares regression model from FT-IR data. The model had a root mean squared error (RMSE) of 0.44 wt% OH. This method was then used to study the distribution of hydroxyl groups among more than 100 shale oil cuts, which showed that hydroxyl content increased with the average boiling point of the cut up to about 350 °C and then leveled off and decreased.

Synchrotron X-ray Applications Toward an Understanding of Elastic Anisotropy

NASA Astrophysics Data System (ADS)

Kanitpanyacharoen, Waruntorn

The contribution of this dissertation is to expand the current knowledge of factors and mechanisms that influence the development of preferred orientation of minerlas and pores in different materials, ranging from rocks in Earth's crust to minerals in the deep Earth. Preferred orientation--a main contributing component to elastic anisotropy--is however very challenging to quantify. The overall focus of this thesis thus aims to (1) apply the capabilities of synchrotron X-ray techniques to determine preferred orientations of hexagonal metals and shales under different conditions and (2) enhance our understanding of their relationships to the elastic properties. Lattice preferred orientation (LPO) or 'texture' of hexagonal close-packed iron (hcp- Fe) crystals during deformation has been suggested as the cause of the elastic anisotropy observed in Earth's inner core. However, relatively little is known about LPO of other hcp metals. An investigation of a wide range of hcp metals (Cd, Zn, Os, and Hf) as analogs to hcp-Fe was thus undertaken to better understand deformation mechanisms at high pressure and temperature in Chapter 2. Results show that all hcp metals preferentially align their c-axes near the compression axis during deformation but with considerable differences. The gradual texture evolution in Cd and Zn is mainly controlled by basal slip systems while a rapid texture development in Os and Hf at ambient temperature is due to a dominant role of tensile twinning, with some degree of basal slip. At elevated temperature, tensile twinning is suppressed and texturing is governed by combined basal and prismatic slip. Under all conditions, basal slip appears to be the main deformation mechanism in hcp metals at high pressure and temperature. These findings are similar to those of hcp-Fe and useful to better understand the deformation mechanisms of hcp metals and their implications for elastic anisotropy. In Chapter 3, a high-energy synchrotron X-ray diffraction technique was applied to characterize LPO and phase proportions of Posidonia Shale collected in the Hils Syncline from Germany, in order to examine the influence of clay content, burial depth, and thermal history. The samples used in this study had experienced different local temperatures during burial and uplifting, as established by the maturity of kerogen (0.68-1.45% vitrinite reflectance, Ro), but their constituent clay minerals, including kaolinite, illite-mica, and illite-smectite, show similar degrees of LPO in all samples, ranging between 3.7 and 6.3 multiple of random distribution (m.r.d.). These observations imply that the difference in local thermal history, which significantly affects the maturity of kerogen, at most marginally influences LPO of clays, as the alignment of clays was established early in the history. In Chapter 4, the SPO of constituents phases in Kimmeridge Shale (North Sea, UK) and Barnett Shale (Gulf of Mexico, USA) was quantified to a resolution of ˜1 mum by using synchrotron X-ray microtomography (SXMT) technique. Measurements were done at different facilities (ALS, APS, and SLS) to characterize 3D microstructures, explore resolution limitations, and develop satisfactory procedures for data quantification. Segmentation images show that the SPO of low density features, including pores, fractures, and kerogen, is mostly anisotropic and oriented parallel to the bedding plane. Small pores are generally dispersed, whereas some large fractures and kerogen have irregular shapes and remain aligned horizontally. In contrast, pyrite exhibits no SPO. The volume fractions and aspect ratios of low density features extracted from three synchrotron sources show excellent agreement with 6.3(6)% for Kimmeridge Shale and 4.5(4)% for Barnett Shale. A small variation is mainly due to differences of optical instruments and technical setups. The SXMT is proven to be a crucial technique to investigate 3D internal structures of fine-grained materials at high-resolution. A relationship between LPO, SPO, and elastic anisotropy of the Qusaiba Shale from the Rub'al-Khali basin in Saudi Arabia is established in Chapter 5. The Qusaiba samples exhibit strong LPO of clay minerals (2.4-6.8 m.r.d.) due to their high total clay content and high degree of compaction. The SPO of pores, fractures, and kerogen here are also anisotropic and organized mainly parallel to bedding, with little connectivity of the flat pores normal to the bedding. The microscopic information (LPO) extracted from different synchrotron X-ray techniques is then applied in different averaging approaches (Voigt, Reuss, Hill, and Geometric mean) to calculate macroscopic properties of shales. (Abstract shortened by UMI.)

Organic petrology of selected oil shale samples from lower Carboniferous Albert Formation, New Brunswick, Canada

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalkreuth, W.; Macauley, G.

1984-04-01

Incident light microscopy was used to describe maturation and composition of organic material in oil shale samples from the Lower Carboniferous Albert Formation of New Brunswick. The maturation level was determined in normal (white) light by measuring vitrinite reflectance and in fluorescent light by measuring fluorescence spectral of alginite B. Results indicate low to intermediate maturation for all of the samples. Composition was determined by maceral analysis. Alginite B is the major organic component in all samples having significant oil potential. Oil yields obtained from the Fischer Assay process, and oil and gas potentials from Rock-Eval analyses correlate to themore » amounts of alginite B and bituminite determined in the samples. In some of the samples characterized by similar high concentrations of alginite B, decrease in Fischer Assay yields and oil and gas potentials is related to an increase in maturation, as expected by increase in the fluorescence parameter lambda/sub max/ and red/green quotient of alginite B. Incident light microscopy, particularly with fluorescent light, offers a valuable tool for the identification of the organic matter in oil shales and for the evaluation of their oil and gas potentials.« less

The Valley and Ridge Province of eastern Pennsylvania - stratigraphic and sedimentologic contributions and problems ( USA).

USGS Publications Warehouse

Epstein, J.B.

1986-01-01

The rocks in the area, which range from Middle Ordovician to Late Devonian in age, are more than 7620 m thick. This diversified group of sedimentary rocks was deposited in many different environments, ranging from deep sea, through neritic and tidal, to alluvial. In general, the Middle Ordovician through Lower Devonian strata are a sedimentary cycle related to the waxing and waning of Taconic tectonism. The sequence began with a greywacke-argillite suite (Martinsburg Formation) representing synorogenic basin deepening. This was followed by basin filling and progradation of a sandstone-shale clastic wedge (Shawangunk Formation and Bloomsburg Red Beds) derived from the erosion of the mountains that were uplifted during the Taconic orogeny. The sequence ended with deposition of many thin units of carbonate, sandstone, and shale on a shelf marginal to a land area of low relief. Another tectonic-sedimentary cycle, related to the Acadian orogeny, began with deposition of Middle Devonian rocks. Deep-water shales (Marcellus Shale) preceded shoaling (Mahantango Formation) and turbidite sedimentation (Trimmers Rock Formation) followed by another molasse (Catskill Formation). -from Author

Experimental Study and Numerical Modeling of Fracture Propagation in Shale Rocks During Brazilian Disk Test

NASA Astrophysics Data System (ADS)

Mousavi Nezhad, Mohaddeseh; Fisher, Quentin J.; Gironacci, Elia; Rezania, Mohammad

2018-06-01

Reliable prediction of fracture process in shale-gas rocks remains one of the most significant challenges for establishing sustained economic oil and gas production. This paper presents a modeling framework for simulation of crack propagation in heterogeneous shale rocks. The framework is on the basis of a variational approach, consistent with Griffith's theory. The modeling framework is used to reproduce the fracture propagation process in shale rock samples under standard Brazilian disk test conditions. Data collected from the experiments are employed to determine the testing specimens' tensile strength and fracture toughness. To incorporate the effects of shale formation heterogeneity in the simulation of crack paths, fracture properties of the specimens are defined as spatially random fields. A computational strategy on the basis of stochastic finite element theory is developed that allows to incorporate the effects of heterogeneity of shale rocks on the fracture evolution. A parametric study has been carried out to better understand how anisotropy and heterogeneity of the mechanical properties affect both direction of cracks and rock strength.

Assessment and longitudinal analysis of health impacts and stressors perceived to result from unconventional shale gas development in the Marcellus Shale region.

PubMed

Ferrar, Kyle J; Kriesky, Jill; Christen, Charles L; Marshall, Lynne P; Malone, Samantha L; Sharma, Ravi K; Michanowicz, Drew R; Goldstein, Bernard D

2013-01-01

Concerns for health and social impacts have arisen as a result of Marcellus Shale unconventional natural gas development. Our goal was to document the self-reported health impacts and mental and physical health stressors perceived to result from Marcellus Shale development. Two sets of interviews were conducted with a convenience sample of community members living proximal to Marcellus Shale development, session 1 March-September 2010 (n = 33) and session 2 January-April 2012 (n = 20). Symptoms of health impacts and sources of psychological stress were coded. Symptom and stressor counts were quantified for each interview. The counts for each participant were compared longitudinally. Participants attributed 59 unique health impacts and 13 stressors to Marcellus Shale development. Stress was the most frequently-reported symptom. Over time, perceived health impacts increased (P = 0·042), while stressors remained constant (P = 0·855). Exposure-based epidemiological studies are needed to address identified health impacts and those that may develop as unconventional natural gas extraction continues. Many of the stressors can be addressed immediately.

Methane and CO2 Adsorption Capacities of Kerogen in the Eagle Ford Shale from Molecular Simulation.

PubMed

Psarras, Peter; Holmes, Randall; Vishal, Vikram; Wilcox, Jennifer

2017-08-15

Over the past decade, the United States has become a world leader in natural gas production, thanks in part to a large-fold increase in recovery from unconventional resources, i.e., shale rock and tight oil reservoirs. In an attempt to help mitigate climate change, these depleted formations are being considered for their long-term CO 2 storage potential. Because of the variability in mineral and structural composition from one formation to the next (even within the same region), it is imperative to understand the adsorption behavior of CH 4 and CO 2 in the context of specific conditions and pore surface chemistry, i.e., relative total organic content (TOC), clay, and surface functionality. This study examines two Eagle Ford shale samples, both recovered from shale that was extracted at depths of approximately 3800 m and having low clay content (i.e., less than 5%) and similar mineral compositions but distinct TOCs (i.e., 2% and 5%, respectively). Experimentally validated models of kerogen were used to the estimate CH 4 and CO 2 adsorption capacities. The pore size distributions modeled were derived from low-pressure adsorption isotherm data using CO 2 and N 2 as probe gases for micropores and mesopores, respectively. Given the presence of water in these natural systems, the role of surface chemistry on modeled kerogen pore surfaces was investigated. Several functional groups associated with surface-dissociated water were considered. Pressure conditions from 10 to 50 bar were investigated using grand canonical Monte Carlo simulations along with typical outgassing temperatures used in many shale characterization and adsorption studies (i.e., 60 and 250 °C). Both CO 2 and N 2 were used as probe gases to determine the total pore volume available for gas adsorption spanning pore diameters ranging from 0.3 to 30 nm. The impacts of surface chemistry, outgassing temperature, and the inclusion of nanopores with diameters of less than 1.5 nm were determined for applications of CH 4 and CO 2 storage from samples of the gas-producing region of the Eagle Ford Shale. At 50 bar and temperatures of 60 and 250 °C, CH 4 adsorption increased across all surface chemistries considered by 60% and 2-fold, respectively. In the case of CO 2 , the surface chemistry played a role at both 10 and 50 bar. For instance, at temperatures of 60 and 250 °C, CO 2 adsorption increased across all surface chemistries by 6-fold and just over 2-fold, respectively. It was also found that at both 10 and 50 bar, if too low an outgassing temperature is used, this may lead to a 2-fold underestimation of gas in place. Finally, neglecting to include pores with diameters of less than 1.5 nm has the potential to underestimate pore volume by up to 28%. Taking into consideration these aspects of kerogen and shale characterization in general will lead to improvements in estimating the CH 4 and CO 2 storage potential of gas shales.

Detachments in Shale: Controlling Characteristics on Fold-Thrust Belt Style

NASA Astrophysics Data System (ADS)

Hansberry, Rowan; King, Ros; Collins, Alan; Morley, Chris

2013-04-01

Fold-thrust belts occur across multiple tectonic settings where thin-skinned deformation is accommodated by one or more detachment zones, both basal and within the fold-thrust belt. These fold-thrust belts exhibit considerable variation in structural style and vergence depending on the characteristics (e.g. strength, thickness, and lithology) and number of detachment zones. Shale as a detachment lithology is intrinsically weaker than more competent silts and sands; however, it can be further weakened by high pore pressures, reducing resistance to sliding and; high temperatures, altering the rheology of the detachment. Despite the implications for petroleum exploration and natural hazard assessment the precise nature by which detachments in shale control and are involved in deformation in fold-thrust belts is poorly understood. Present-day active basal detachment zones are usually located in inaccessible submarine regions. Therefore, this project employs field observations and sample analysis of ancient, exhumed analogues to document the nature of shale detachments (e.g. thickness, lithology, dip and dip direction, deformational temperature and thrust propagation rates) at field sites in Thailand, Norway and New Zealand. X-ray diffraction analysis of illite crystallinity and oxygen stable isotopes analysis are used as a proxy for deformational temperature whilst electron-backscatter diffraction analysis is used to constrain microstructural deformational patterns. K-Ar dating of synkinematic clay fault gouges is being applied to date the final stages of activity on individual faults with a view to constraining thrust activation sequences. It is not possible to directly measure palaeo-data for some key detachment parameters, such as pore pressure and coefficients of friction. However, the use of critical taper wedge theory has been used to successfully infer internal and basal coefficients of friction and depth-normalized pore pressure within a wedge and at its base (e.g. Platt, 1986; Bilotti and Shaw, 2005; Morley, 2007). Therefore, through a mixture of field observations, sample analysis and theoretical analysis it will be possible to determine a full range of shale detachment parameters and their impact on the structural style of fold-thrust belts across a variety of settings. Recent work in Muak Lek, central Thailand has focused on a structural investigation of fold-thrust belt deformation of a passive margin sequence as a result of continent-continent collision during the Triassic Indosinian Orogeny. Exceptional outcropping of the detachment lithology is accessible in the Siam City Cement quarry allowing construction of sections detailing the deformational style across the detachment itself. The detachment forms complex, 3-dimensional duplex-like structures creating egg-carton geometries enveloping foliation surfaces in the zones of most intense strain. Up section strain decreases to discrete thrust imbricates of decametre scale. Samples of limestone and secondary calcite were collected through the sections for oxygen stable isotopes analysis which show a distinct pattern of isotopic fractionation across the main thrust and into the detachment. Results from this study give insights into the nature of shale detachments and the control on fold-thrust belt development.

Sulfur-, oxygen-, and carbon-isotope studies of Ag-Pb-Zn vein-breccia occurrences, sulfide-bearing concretions, and barite deposits in the north-central Brooks Range, with comparisons to shale-hosted stratiform massive sulfide deposits: A section in Geologic studies in Alaska by the U.S. Geological Survey, 1998

USGS Publications Warehouse

Kelley, Karen D.; Leach, David L.; Johnson, Craig A.

2000-01-01

Stratiform shale-hosted massive sulfide deposits, sulfidebearing concretions and vein breccias, and barite deposits are widespread in sedimentary rocks of Late Devonian to Permian age in the northern Brooks Range. All of the sulfide-bearing concretions and vein breccias are hosted in mixed continental-marine clastic rocks of the Upper Devonian to Lower Mississippian Endicott Group. The clastic rocks and associated sulfide occurrences underlie chert and shale of Mississippian-Pennsylvanian(?) age that contain large stratiform massive sulfide deposits like that at Red Dog. The relative stratigraphic position of the vein breccias, as well as previously published mineralogical, geochemical, and lead-isotope data, suggest that the vein breccias formed coevally with overlying shale-hosted massive sulfide deposits and that they may represent pathways of oreforming hydrothermal fluids. Barite deposits are hosted either in Mississippian chert and limestone (at essentially the same stratigraphic position as the shale-hosted massive sulfide deposits) or Permian chert and shale. Although most barite deposits have no associated base-metal mineralization, barite occurs with massive sulfide deposits at the Red Dog deposit.Galena and sphalerite from most vein breccias have δ34S values from –7.3 to –0.7‰ (per mil) and –5.1 to 3.6‰, respectively; sphalerite from sulfide-bearing concretions have δ34S values of 0.7 and 4.7‰. This overall range in δ34S values largely overlaps with the range previously determined for galena and sphalerite from shale-hosted massive sulfide deposits at Red Dog and Drenchwater. The Kady vein-breccia occurrence is unusual in having higher δ34S values for sphalerite (12.1 to 12.9‰) and pyrite (11.3‰), consistent with previously published values for the shale-hosted Lik deposit. The correspondence in sulfur isotopic compositions between the stratiform and vein-breccia deposits suggests that they share a common source of reduced sulfur, or derived reduced sulfur by similar geochemical processes. Most likely, the reduced sulfur was derived by biogenic sulfate reduction (BSR) or thermochemical sulfate reduction (TSR) of seawater sulfate during Devonian-Mississippian time.The δ18O values of quartz from the vein breccias are between 16.6 and 19.9‰. Using the sphalerite-galena sulfur isotopic temperature of 188°±25°C, the calulated hydrothermal fluids had δ18O values of 4.2 to 7.5‰. The calculated range of δ18O values of the fluids is similar to that of pore fluids in equilibrium with sedimentary rocks during diagenesis at 100°– 190°C.

78 FR 6829 - Agency Information Collection Activities: Submitted for Office of Management and Budget (OMB...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-01-31

... information related to coal, coal bed gas, shale gas and other energy resources and related information..., coal bed gas, and other solid fuel occurrences. Requesting external cooperation is the best way for... organic-rich shale, and obtain other information (including geophysical or seismic data, sample collection...

Aptian ‘Shale Gas’ Prospectivity in the Downdip Mississippi Interior Salt Basin, Gulf Coast, USA

USGS Publications Warehouse

Hackley, Paul C.; Valentine, Brett J.; Enomoto, Catherine B.; Lohr, Celeste D.; Scott, Krystina R.; Dulong, Frank T.; Bove, Alana M.

2016-01-01

This study evaluates regional ‘shale gas’ prospectivity of the Aptian section (primarily Pine Island Shale) in the downdip Mississippi Salt Basin (MSB). Previous work by the U.S. Geological Survey estimated a mean undiscovered gas resource of 8.8 trillion cubic feet (TCF) in the chronostratigraphic-equivalent Pearsall Formation in the Maverick Basin of south Texas, where industry has established a moderately successful horizontal gas and liquids play. Wells penetrating the downdip MSB Aptian section at depths of 12,000-15,000 ft were used to correlate formation tops in a 15-well cross-section extending about 200 miles (mi) east-southeastward from Adams Co. to Jackson Co. Legacy cuttings from these wells were analyzed for thermal maturity and source rock quality. Bitumen reflectance (n=53) increases with increasing present-day burial depth in the east-central study area from 1.0% to 1.7%. As the Aptian section shallows in Adams Co. to the west, bitumen Ro values are higher (1.7-2.0%), either from relatively greater heat flux or greater mid-Cenomanian uplift and erosion in this area. Total organic carbon (TOC) content ranges 0.01-1.21 and averages 0.5 wt.% (n=51); pyrolysis output (S2; n=51) averages 0.40 mg HC/g rock, indicating little present-day hydrocarbon-generative potential. Bitumen reflectance is preferred as a thermal maturity parameter as Tmax values are unreliable. Normalized X-ray diffraction (XRD) mineral analyses (n=26) indicate high average clay abundance (53 wt.%) relative to quartz (29%) and carbonate (18%). Mineral content shows a spatial relationship to an Appalachian orogen clastic sediment source, with proximal high clay and quartz and distal high carbonate content. Clastic influx from the Appalachian orogen is confirmed by detrital zircon U-Pb ages with dominant Grenville and Paleozoic components [105 ages from a Rodessa sandstone and 112 ages from a Paluxy (Albian) sandstone]. Preliminary information from fluid inclusion microthermometry (41 aqueous measurements from calcite cements in one argillaceous James Limestone sample) indicates homogenization temperatures (Th) of 120-135°C, consistent with present-day bottom-hole conditions and measured bitumen Ro values towards the western end of the MSB. Downdip in the central MSB, microthermometry (26 aqueous measurements from quartz dust rims in one Paluxy sandstone sample) and measured bitumen Ro values indicate maximum temperatures may have been significantly higher (~25°C) than present-day conditions. High inclusion salinities (15-25 wt.% salt) at both locations suggest interaction of pore fluids with evaporites. Mercury injection capillary pressure (MICP) analyses (n=3) indicate porosity ranges 1.3-2.1% and permeability 0.006-0.02 µD for Pine Island and Rodessa shales. Overall, results from this work indicate generally poor ‘shale gas’ prospectivity compared to other shale reservoirs based primarily on depth, low organic content, low porosity, and high clay content. However, thickness and thermal maturity are appropriate, moderate reservoir pressures are present, and petroleum systems modelling by others has indicated high undiscovered gas potential for the basin as a whole.

The Impact of a Potential Shale Gas Development in Germany and the United Kingdom on Local and Regional Air Quality

NASA Astrophysics Data System (ADS)

Weger, L.; Lupascu, A.; Cremonese, L.; Butler, T. M.

2017-12-01

Numerous countries in Europe that possess domestic shale gas reserves are considering exploiting this unconventional gas resource as part of their energy transition agenda. While natural gas generates less CO2 emissions upon combustion compared to coal or oil, making it attractive as a bridge in the transition from fossil fuels to renewables, production of shale gas leads to emissions of CH4 and air pollutants such as NOx, VOCs and PM. These gases in turn influence the climate as well as air quality. In this study, we investigate the impact of a potential shale gas development in Germany and the United Kingdom on local and regional air quality. This work builds on our previous study in which we constructed emissions scenarios based on shale gas utilization in these counties. In order to explore the influence of shale gas production on air quality, we investigate emissions predicted from our shale gas scenarios with the Weather Research and Forecasting model with chemistry (WRF-Chem) model. In order to do this, we first design a model set-up over Europe and evaluate its performance for the meteorological and chemical parameters. Subsequently we add shale gas emissions fluxes based on the scenarios over the area of the grid in which the shale gas activities are predicted to occur. Finally, we model these emissions and analyze the impact on air quality on both a local and regional scale. The aims of this work are to predict the range of adverse effects on air quality, highlight the importance of emissions control strategies in reducing air pollution, to promote further discussion, and to provide policy makers with information for decision making on a potential shale gas development in the two study countries.

Compaction bands in shale revealed through digital volume correlation of time-resolved X-ray tomography scans

NASA Astrophysics Data System (ADS)

McBeck, J.; Kobchenko, M.; Hall, S.; Tudisco, E.; Cordonnier, B.; Renard, F.

2017-12-01

Previous studies have identified compaction bands primarily within sandstones, and in fewer instances, within other porous rocks and sediments. Using Digital Volume Correlation (DVC) of X-ray microtomography scans, we find evidence of localized zones of high axial contraction that form tabular structures sub-perpendicular to maximum compression, σ1, in Green River shale. To capture in situ strain localization throughout loading, two shale cores were deformed in the HADES triaxial deformation apparatus installed on the X-ray microtomography beamline ID19 at the European Synchrotron Radiation Facility. In these experiments, we increase σ1 in increments of two MPa, with constant confining pressure (20 MPa), until the sample fails in macroscopic shear. After each stress step, a 3D image of the sample inside the rig is acquired at a voxel resolution of 6.5 μm. The evolution of lower density regions within 3D reconstructions of linear attenuation coefficients reveal the development of fractures that fail with some opening. If a fracture produces negligible dilation, it may remain undetected in image segmentation of the reconstructions. We use the DVC software TomoWarp2 to identify undetected fractures and capture the 3D incremental displacement field between each successive pair of microtomography scans acquired in each experiment. The corresponding strain fields reveal localized bands of high axial contraction that host minimal shear strain, and thus match the kinematic definition of compaction bands. The bands develop sub-perpendicular to σ1 in the two samples in which pre-existing bedding laminations were oriented parallel and perpendicular to σ1. As the shales deform plastically toward macroscopic shear failure, the number of bands and axial contraction within the bands increase, while the spacing between the bands decreases. Compaction band development accelerates the rate of overall axial contraction, increasing the mean axial contraction throughout the sample, and strengthens the shale sufficiently to localize shear faults. These results are critical to robust assessment of deformation patterns in shale rocks in contexts such as nuclear waste storage, hydrocarbon recovery and groundwater access.

Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China

PubMed Central

Wang, Lingqing; Liang, Tao

2015-01-01

Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China’s largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 104 mg·kg−1 with an average value of 4.67 × 103 mg·kg−1, which was significantly higher than the average value in China (181 mg·kg−1). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (LaN/YbN, LaN/SmN and GdN/YbN). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind. PMID:26198417

Geochemical fractions of rare earth elements in soil around a mine tailing in Baotou, China.

PubMed

Wang, Lingqing; Liang, Tao

2015-07-22

Rare earth mine tailing dumps are environmental hazards because tailing easily leaches and erodes by water and wind. To assess the influence of mine tailing on the geochemical behavior of rare earth elements (REEs) in soil, sixty-seven surface soil samples and three soil profile samples were collected from different locations near China's largest rare earth mine tailing. The total concentration of REEs in surface soils ranged from 156 to 5.65 × 10(4) mg·kg(-1) with an average value of 4.67 × 10(3) mg·kg(-1), which was significantly higher than the average value in China (181 mg·kg(-1)). We found obvious fractionation of both light and heavy REEs, which was supported by the North American Shale Composite (NASC) and the Post-Archean Average Australian Shale (PAAS) normalized concentration ratios calculated for selected elements (La(N)/Yb(N), La(N)/Sm(N) and Gd(N)/Yb(N)). A slightly positive Ce anomaly and a negative Eu anomaly were also found. For all 14 REEs in soils, enrichment was intensified by the mine tailing sources and influenced by the prevailing wind.

Iron isotope biogeochemistry of Neoproterozoic marine shales

NASA Astrophysics Data System (ADS)

Kunzmann, Marcus; Gibson, Timothy M.; Halverson, Galen P.; Hodgskiss, Malcolm S. W.; Bui, Thi Hao; Carozza, David A.; Sperling, Erik A.; Poirier, André; Cox, Grant M.; Wing, Boswell A.

2017-07-01

Iron isotopes have been widely applied to investigate the redox evolution of Earth's surface environments. However, it is still unclear whether iron cycling in the water column or during diagenesis represents the major control on the iron isotope composition of sediments and sedimentary rocks. Interpretation of isotopic data in terms of oceanic redox conditions is only possible if water column processes dominate the isotopic composition, whereas redox interpretations are less straightforward if diagenetic iron cycling controls the isotopic composition. In the latter scenario, iron isotope data is more directly related to microbial processes such as dissimilatory iron reduction. Here we present bulk rock iron isotope data from late Proterozoic marine shales from Svalbard, northwestern Canada, and Siberia, to better understand the controls on iron isotope fractionation in late Proterozoic marine environments. Bulk shales span a δ 56Fe range from -0.45 ‰ to +1.04 ‰ . Although δ 56Fe values show significant variation within individual stratigraphic units, their mean value is closer to that of bulk crust and hydrothermal iron in samples post-dating the ca. 717-660 Ma Sturtian glaciation compared to older samples. After correcting for the highly reactive iron content in our samples based on iron speciation data, more than 90% of the calculated δ 56Fe compositions of highly reactive iron falls in the range from ca. -0.8 ‰ to +3 ‰ . An isotope mass-balance model indicates that diagenetic iron cycling can only change the isotopic composition of highly reactive iron by < 1 ‰ , suggesting that water column processes, namely the degree of oxidation of the ferrous seawater iron reservoir, control the isotopic composition of highly reactive iron. Considering a long-term decrease in the isotopic composition of the iron source to the dissolved seawater Fe(II) reservoir to be unlikely, we offer two possible explanations for the Neoproterozoic δ 56Fe trend. First, a decreasing supply of Fe(II) to the ferrous seawater iron reservoir could have caused the reservoir to decrease in size, allowing a higher degree of partial oxidation, irrespective of increasing environmental oxygen levels. Alternatively, increasing oxygen levels would have led to a higher proportion of Fe(II) being oxidized, without decreasing the initial size of the ferrous seawater iron pool. We consider the latter explanation as the most likely. According to this hypothesis, the δ 56Fe record reflects the redox evolution of Earth's surface environments. δ 56Fe values in pre-Sturtian samples significantly heavier than bulk crust and hydrothermal iron imply partial oxidation of a ferrous seawater iron reservoir. In contrast, mean δ 56Fe values closer to that of hydrothermal iron in post-Sturtian shales reflects oxidation of a larger proportion of the ferrous seawater iron reservoir, and by inference, higher environmental oxygen levels. Nevertheless, significant iron isotopic variation in post-Sturtian shales suggest redox heterogeneity and possibly a dominantly anoxic deep ocean, consistent with results from recent studies using iron speciation and redox sensitive trace metals. However, the interpretation of generally increasing environmental oxygen levels after the Sturtian glaciation highlights the need to better understand the sensitivity of different redox proxies to incremental changes in oxygen levels to enable us to reconcile results from different paleoredox proxies.

Ultra-small-angle neutron scattering with azimuthal asymmetry

DOE PAGES

Gu, X.; Mildner, D. F. R.

2016-05-16

Small-angle neutron scattering (SANS) measurements from thin sections of rock samples such as shales demand as great a scattering vector range as possible because the pores cover a wide range of sizes. The limitation of the scattering vector range for pinhole SANS requires slit-smeared ultra-SANS (USANS) measurements that need to be converted to pinhole geometry. The desmearing algorithm is only successful for azimuthally symmetric data. Scattering from samples cut parallel to the plane of bedding is symmetric, exhibiting circular contours on a two-dimensional detector. Samples cut perpendicular to the bedding show elliptically dependent contours with the long axis corresponding tomore » the normal to the bedding plane. A method is given for converting such asymmetric data collected on a double-crystal diffractometer for concatenation with the usual pinhole-geometry SANS data. Furthermore, the aspect ratio from the SANS data is used to modify the slit-smeared USANS data to produce quasi-symmetric contours. Rotation of the sample about the incident beam may result in symmetric data but cannot extract the same information as obtained from pinhole geometry.« less

Ultra-small-angle neutron scattering with azimuthal asymmetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, X.; Mildner, D. F. R.

Small-angle neutron scattering (SANS) measurements from thin sections of rock samples such as shales demand as great a scattering vector range as possible because the pores cover a wide range of sizes. The limitation of the scattering vector range for pinhole SANS requires slit-smeared ultra-SANS (USANS) measurements that need to be converted to pinhole geometry. The desmearing algorithm is only successful for azimuthally symmetric data. Scattering from samples cut parallel to the plane of bedding is symmetric, exhibiting circular contours on a two-dimensional detector. Samples cut perpendicular to the bedding show elliptically dependent contours with the long axis corresponding tomore » the normal to the bedding plane. A method is given for converting such asymmetric data collected on a double-crystal diffractometer for concatenation with the usual pinhole-geometry SANS data. Furthermore, the aspect ratio from the SANS data is used to modify the slit-smeared USANS data to produce quasi-symmetric contours. Rotation of the sample about the incident beam may result in symmetric data but cannot extract the same information as obtained from pinhole geometry.« less

Petrophysical Properties of Cody, Mowry, Shell Creek, and Thermopolis Shales, Bighorn Basin, Wyoming

NASA Astrophysics Data System (ADS)

Nelson, P. H.

2013-12-01

The petrophysical properties of four shale formations are documented from well-log responses in 23 wells in the Bighorn Basin in Wyoming. Depths of the examined shales range from 4,771 to 20,594 ft. The four formations are the Thermopolis Shale (T), the Shell Creek Shale (SC), the Mowry Shale (M), and the lower part of the Cody Shale (C), all of Cretaceous age. These four shales lie within a 4,000-ft, moderately overpressured, gas-rich vertical interval in which the sonic velocity of most rocks is less than that of an interpolated trendline representing a normal increase of velocity with depth. Sonic velocity, resistivity, neutron, caliper, and gamma-ray values were determined from well logs at discrete intervals in each of the four shales in 23 wells. Sonic velocity in all four shales increases with depth to a present-day depth of about 10,000 ft; below this depth, sonic velocity remains relatively unchanged. Velocity (V), resistivity (R), neutron porosity (N), and hole diameter (D) in the four shales vary such that: VM > VC > VSC > VT, RM > RC > RSC > RT, NT > NSC ≈ NC > NM, and DT > DC ≈ DSC > DM. These orderings can be partially understood on the basis of rock compositions. The Mowry Shale is highly siliceous and by inference comparatively low in clay content, resulting in high sonic velocity, high resistivity, low neutron porosity, and minimal borehole enlargement. The Thermopolis Shale, by contrast, is a black fissile shale with very little silt--its high clay content causes low velocity, low resistivity, high neutron response, and results in the greatest borehole enlargement. The properties of the Shell Creek and lower Cody Shales are intermediate to the Mowry and Thermopolis Shales. The sonic velocities of all four shales are less than that of an interpolated trendline that is tied to velocities in shales above and below the interval of moderate overpressure. The reduction in velocity varies among the four shales, such that the amount of offset (O) from the trendline is OT > OSC > OC > OM, that is, the velocity in the Mowry Shale is reduced the least and the velocity in the Thermopolis Shale is reduced the most. Velocity reductions are attributed to increases in pore pressure during burial, caused by the generation and retention of gas, with lithology playing a key role in the amount of reduction. Sonic velocity in the four shale units remains low to the present day, after uplift and erosion of as much as 6,500 ft in the deeper part of the basin and consequent possible reduction from maximum pore pressures reached when strata were more deeply buried. A model combining burial history, the decrease of effective stress with increasing pore pressure, and Bower's model for the dependence of sonic velocity on effective stress is proposed to explain the persistence of low velocity in shale units. Interruptions to compaction gradients associated with gas occurrences and overpressure are observed in correlative strata in other basins in Wyoming, so the general results for shales in the Bighorn Basin established in this paper should be applicable elsewhere.

Imbibition of hydraulic fracturing fluids into partially saturated shale

NASA Astrophysics Data System (ADS)

Birdsell, Daniel T.; Rajaram, Harihar; Lackey, Greg

2015-08-01

Recent studies suggest that imbibition of hydraulic fracturing fluids into partially saturated shale is an important mechanism that restricts their migration, thus reducing the risk of groundwater contamination. We present computations of imbibition based on an exact semianalytical solution for spontaneous imbibition. These computations lead to quantitative estimates of an imbibition rate parameter (A) with units of LT-1/2 for shale, which is related to porous medium and fluid properties, and the initial water saturation. Our calculations suggest that significant fractions of injected fluid volumes (15-95%) can be imbibed in shale gas systems, whereas imbibition volumes in shale oil systems is much lower (3-27%). We present a nondimensionalization of A, which provides insights into the critical factors controlling imbibition, and facilitates the estimation of A based on readily measured porous medium and fluid properties. For a given set of medium and fluid properties, A varies by less than factors of ˜1.8 (gas nonwetting phase) and ˜3.4 (oil nonwetting phase) over the range of initial water saturations reported for the Marcellus shale (0.05-0.6). However, for higher initial water saturations, A decreases significantly. The intrinsic permeability of the shale and the viscosity of the fluids are the most important properties controlling the imbibition rate.

Multiparameter Analysis of Gas Transport Phenomena in Shale Gas Reservoirs: Apparent Permeability Characterization.

PubMed

Shen, Yinghao; Pang, Yu; Shen, Ziqi; Tian, Yuanyuan; Ge, Hongkui

2018-02-08

The large amount of nanoscale pores in shale results in the inability to apply Darcy's law. Moreover, the gas adsorption of shale increases the complexity of pore size characterization and thus decreases the accuracy of flow regime estimation. In this study, an apparent permeability model, which describes the adsorptive gas flow behavior in shale by considering the effects of gas adsorption, stress dependence, and non-Darcy flow, is proposed. The pore size distribution, methane adsorption capacity, pore compressibility, and matrix permeability of the Barnett and Eagle Ford shales are measured in the laboratory to determine the critical parameters of gas transport phenomena. The slip coefficients, tortuosity, and surface diffusivity are predicted via the regression analysis of the permeability data. The results indicate that the apparent permeability model, which considers second-order gas slippage, Knudsen diffusion, and surface diffusion, could describe the gas flow behavior in the transition flow regime for nanoporous shale. Second-order gas slippage and surface diffusion play key roles in the gas flow in nanopores for Knudsen numbers ranging from 0.18 to 0.5. Therefore, the gas adsorption and non-Darcy flow effects, which involve gas slippage, Knudsen diffusion, and surface diffusion, are indispensable parameters of the permeability model for shale.

Life-cycle greenhouse gas emissions of shale gas, natural gas, coal, and petroleum.

PubMed

Burnham, Andrew; Han, Jeongwoo; Clark, Corrie E; Wang, Michael; Dunn, Jennifer B; Palou-Rivera, Ignasi

2012-01-17

The technologies and practices that have enabled the recent boom in shale gas production have also brought attention to the environmental impacts of its use. It has been debated whether the fugitive methane emissions during natural gas production and transmission outweigh the lower carbon dioxide emissions during combustion when compared to coal and petroleum. Using the current state of knowledge of methane emissions from shale gas, conventional natural gas, coal, and petroleum, we estimated up-to-date life-cycle greenhouse gas emissions. In addition, we developed distribution functions for key parameters in each pathway to examine uncertainty and identify data gaps such as methane emissions from shale gas well completions and conventional natural gas liquid unloadings that need to be further addressed. Our base case results show that shale gas life-cycle emissions are 6% lower than conventional natural gas, 23% lower than gasoline, and 33% lower than coal. However, the range in values for shale and conventional gas overlap, so there is a statistical uncertainty whether shale gas emissions are indeed lower than conventional gas. Moreover, this life-cycle analysis, among other work in this area, provides insight on critical stages that the natural gas industry and government agencies can work together on to reduce the greenhouse gas footprint of natural gas.

Shale Gas Geomechanics for Development and Performance of Unconventional Reservoirs

NASA Astrophysics Data System (ADS)

Domonik, Andrzej; Łukaszewski, Paweł; Wilczyński, Przemysław; Dziedzic, Artur; Łukasiak, Dominik; Bobrowska, Alicja

2017-04-01

Mechanical properties of individual shale formations are predominantly determined by their lithology, which reflects sedimentary facies distribution, and subsequent diagenetic and tectonic alterations. Shale rocks may exhibit complex elasto-viscoplastic deformation mechanisms depending on the rate of deformation and the amount of clay minerals, also bearing implications for subcritical crack growth and heterogeneous fracture network development. Thus, geomechanics for unconventional resources differs from conventional reservoirs due to inelastic matrix behavior, stress sensitivity, rock anisotropy and low matrix permeability. Effective horizontal drilling and hydraulic fracturing technologies are required to obtain and maintain high performance. Success of these techniques strongly depends on the geomechanical investigations of shales. An inelastic behavior of shales draws increasing attention of investigators [1], due to its role in stress relaxation between fracturing phases. A strong mechanical anisotropy in the vertical plane and a lower and more variable one in the horizontal plane are characteristic for shale rocks. The horizontal anisotropy plays an important role in determining the direction and effectiveness of propagation of technological hydraulic fractures. Non-standard rock mechanics laboratory experiments are being applied in order to obtain the mechanical properties of shales that have not been previously studied in Poland. Novel laboratory investigations were carried out to assess the creep parameters and to determine time-dependent viscoplastic deformation of shale samples, which can provide a limiting factor to tectonic stresses and control stress change caused by hydraulic fracturing. The study was supported by grant no.: 13-03-00-501-90-472946 "An integrated geomechanical investigation to enhance gas extraction from the Pomeranian shale formations", funded by the National Centre for Research and Development (NCBiR). References: Ch. Chang M. D. Zoback. 2009. Viscous creep in room-dried unconsolidated Gulf of Mexico shale (I): Experimental results. Journal of Petroleum Science and Engineering 69: 239-246.

The influence of nitrate on selenium in irrigated agricultural groundwater systems.

PubMed

Bailey, Ryan T; Hunter, William J; Gates, Timothy K

2012-01-01

Selenium (Se) contamination of groundwater is an environmental concern especially in areas where aquifer systems are underlain by Se-bearing geologic formations such as marine shale. This study examined the influence of nitrate (NO₃) on Se species in irrigated soil and groundwater systems and presents results from field and laboratory studies that further clarify this influence. Inhibition of selenate (SeO₄) reduction in the presence of NO₃ and the oxidation of reduced Se from shale by autotrophic denitrification were investigated. Groundwater sampling from piezometers near an alluvium-shale interface suggests that SeO₄ present in the groundwater was due in part to autotrophic denitrification. Laboratory shale oxidation batch studies indicate that autotrophic denitrification is a major driver in the release of SeO₄ and sulfate. Similar findings occurred for a shale oxidation flow-through column study, with 70 and 31% more reduced Se and S mass, respectively, removed from the shale material in the presence of NO₃ than in its absence. A final laboratory flow-through column test was performed with shallow soil samples to assess the inhibition of SeO₄ reduction in the presence of NO₃, with results suggesting that a concentration of NO₃ of approximately 5 mg L or greater will diminish the reduction of SeO₄. The inclusion of the fate and transport of NO₃ and dissolved oxygen is imperative when studying or simulating the fate and transport of Se species in soil and groundwater systems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Characterization and Analysis of Liquid Waste from Marcellus Shale Gas Development.

PubMed

Shih, Jhih-Shyang; Saiers, James E; Anisfeld, Shimon C; Chu, Ziyan; Muehlenbachs, Lucija A; Olmstead, Sheila M

2015-08-18

Hydraulic fracturing of shale for gas production in Pennsylvania generates large quantities of wastewater, the composition of which has been inadequately characterized. We compiled a unique data set from state-required wastewater generator reports filed in 2009-2011. The resulting data set, comprising 160 samples of flowback, produced water, and drilling wastes, analyzed for 84 different chemicals, is the most comprehensive available to date for Marcellus Shale wastewater. We analyzed the data set using the Kaplan-Meier method to deal with the high prevalence of nondetects for some analytes, and compared wastewater characteristics with permitted effluent limits and ambient monitoring limits and capacity. Major-ion concentrations suggested that most wastewater samples originated from dilution of brines, although some of our samples were more concentrated than any Marcellus brines previously reported. One problematic aspect of this wastewater was the very high concentrations of soluble constituents such as chloride, which are poorly removed by wastewater treatment plants; the vast majority of samples exceeded relevant water quality thresholds, generally by 2-3 orders of magnitude. We also examine the capacity of regional regulatory monitoring to assess and control these risks.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bazillian, Morgan; Pedersen, Ascha Lychett; Pless, Jacuelyn

Shale gas resource potential in China is assessed to be large, and its development could have wide-ranging economic, environmental, and energy security implications. Although commercial scale shale gas development has not yet begun in China, it holds the potential to change the global energy landscape. Chinese decision-makers are wrestling with the challenges associated with bringing the potential to reality: geologic complexity; infrastructure and logistical difficulties; technological, institutional, social and market development issues; and environmental impacts, including greenhouse gas emissions, impacts on water availability and quality, and air pollution. This paper briefly examines the current situation and outlook for shale gasmore » in China, and explores existing and potential avenues for international cooperation. We find that despite some barriers to large-scale development, Chinese shale gas production has the potential to grow rapidly over the medium-term.« less

Characterizing porosity of selected Early Palaeozoic shales from the Baltic Basin: organic petrology, gas adsorption and WIP and KIP approach.

NASA Astrophysics Data System (ADS)

Słomski, Piotr; Mastalerz, Maria; Szczepański, Jacek; Derkowski, Arkadiusz; Topór, Tomasz

2017-04-01

The porosity in the selected Ordovician and Silurian mudstones from the Baltic Basin collected from three wells (W1, M1, B1 and O3) was examined in a suite of 78 samples representing the Kopalino, Sasino, Prabuty, Pasłęk (including Jantar Member) and Pelplin Formations. Organic petrology, mineral composition along with N2 low-pressure adsorption (NLPA), water and kerosene immersion porosimetry (WIP and KIP, respectively) as well as image analysis techniques were used to determine pore volumes, pore sizes and pore-size distributions and to evaluate factors controlling porosity. The majority of the investigated samples represent argillaceous mudstones. Only a few samples from O3 and W1 are different lithologically and represent siliceous-argillaceous, calcareous, or calcareous-argillicaous mudstones. The samples are characterized by total organic carbon (TOC) content ranging from 0.13 to 7.20 wt. % and vitrinite reflectance (Ro) ranging from 1.02 to 1.22%, indicating late mature rocks within condensate - wet gas window. Total porosity measured using WIP is in the range from 4.6 % to 10 %, while KIP gave values from 1.5 % to 8.9 %. NLPA technique on the 75 µm size fraction revealed that mesopores area is in the range from 10.59 to 34.34 m2/g, while mesopores volume ranges from 0.024 to 0.062 cm3/g. Correlation between mesopores surface area and Ro is weak, but in general the surface area of mesopores is the largest in the least mature samples. Moreover, as indicated by gas adsorption data, both pores greater than 30 nm and smaller than 4 nm are important contributors to the total mesoporess surface area. In general, rather weak correlation between different mudstone constituents (including kerogen types) and porosity measured by means of various techniques (WIP, KIP and NLPA) reveal that there is no single factor controlling porosity in the investigated suite of samples. This conclusion is also confirmed by image analysis performed on large-scale high-resolution BSE images for selected representative samples. However, for mesopores, the dominant contribution comes from organic matter for the Jantar, Prabuty and Sasino Formations, as indicated by NLPA technique. Furthermore, importance of clay minerals for macropore volume is indicated by WIP and KIP technique. Acknowledgments: the study was supported from grant SHALESEQ (No PL12-0109) and SHALEMECH (No BG2/ShaleMech/14) funded by the National Centre for Research and Development.

Use of Digital Volume Correlation to Measure Deformation of Shale Using Natural Markers

NASA Astrophysics Data System (ADS)

Dewers, T. A.; Quintana, E.; Ingraham, M. D.; Jacques, C. L.

2016-12-01

We apply digital volume correlation (DVC) to interpreting deformation as influenced by shale heterogeneity. An extension of digital image correlation, DVC uses 3D images (CT Scans) of a sample before, during and after loading to determine deformation in terms of a 3D strain map. The technology tracks the deformation of high and low density regions within the sample to determine full field 3D strains within the sample. High pyrite shales (Woodford and Marcellus in this study) are being used as the high density pyrite serves as an excellent point to track in the volume correlation. Preliminary results indicate that this technology is promising for measuring true volume strains, strain localization, and strain portioning by microlithofacies within specimens during testing. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Estimation of brittleness indices for pay zone determination in a shale-gas reservoir by using elastic properties obtained from micromechanics

NASA Astrophysics Data System (ADS)

Lizcano-Hernández, Edgar G.; Nicolás-López, Rubén; Valdiviezo-Mijangos, Oscar C.; Meléndez-Martínez, Jaime

2018-04-01

The brittleness indices (BI) of gas-shales are computed by using their effective mechanical properties obtained from micromechanical self-consistent modeling with the purpose of assisting in the identification of the more-brittle regions in shale-gas reservoirs, i.e., the so-called ‘pay zone’. The obtained BI are plotted in lambda-rho versus mu-rho λ ρ -μ ρ and Young’s modulus versus Poisson’s ratio E-ν ternary diagrams along with the estimated elastic properties from log data of three productive shale-gas wells where the pay zone is already known. A quantitative comparison between the obtained BI and the well log data allows for the delimitation of regions where BI values could indicate the best reservoir target in regions with the highest shale-gas exploitation potential. Therefore, a range of values for elastic properties and brittleness indexes that can be used as a data source to support the well placement procedure is obtained.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Striolo, Alberto; Cole, David R.

Because of a number of technological advancements, unconventional hydrocarbons, and in particular shale gas, have transformed the US economy. Much is being learned, as demonstrated by the reduced cost of extracting shale gas in the US over the past five years. However, a number of challenges still need to be addressed. Many of these challenges represent grand scientific and technological tasks, overcoming which will have a number of positive impacts, ranging from the reduction of the environmental footprint of shale gas production to improvements and leaps forward in diverse sectors, including chemical manufacturing and catalytic transformations. This review addresses recentmore » advancements in computational and experimental approaches, which led to improved understanding of, in particular, structure and transport of fluids, including hydrocarbons, electrolytes, water, and CO 2 in heterogeneous subsurface rocks such as those typically found in shale formations. Finally, the narrative is concluded with a suggestion of a few research directions that, by synergistically combining computational and experimental advances, could allow us to overcome some of the hurdles that currently hinder the production of hydrocarbons from shale formations.« less

Hydrocarbon source potential of the Tanezzuft Formation, Murzuq Basin, south-west Libya: An organic geochemical approach

NASA Astrophysics Data System (ADS)

El Diasty, W. Sh.; El Beialy, S. Y.; Anwari, T. A.; Batten, D. J.

2017-06-01

A detailed organic geochemical study of 20 core and cuttings samples collected from the Silurian Tanezzuft Formation, Murzuq Basin, in the south-western part of Libya has demonstrated the advantages of pyrolysis geochemical methods for evaluating the source-rock potential of this geological unit. Rock-Eval pyrolysis results indicate a wide variation in source richness and quality. The basal Hot Shale samples proved to contain abundant immature to early mature kerogen type II/III (oil-gas prone) that had been deposited in a marine environment under terrigenous influence, implying good to excellent source rocks. Strata above the Hot Shale yielded a mixture of terrigenous and marine type III/II kerogen (gas-oil prone) at the same maturity level as the Hot Shale, indicating the presence of only poor to fair source rocks.

Mason’s equation application for prediction of voltage of oil shale treeing breakdown

NASA Astrophysics Data System (ADS)

Martemyanov, S. M.

2017-05-01

The application of the formula, which is used to calculate the maximum field at the tip of the pin-plane electrode system was proposed to describe the process of electrical treeing and treeing breakdown in an oil shale. An analytical expression for the calculation of the treeing breakdown voltage in the oil shale, as a function of the inter-electrode distance, was taken. A high accuracy of the correspondence of the model to the experimental data in the range of inter-electrode distances from 0.03 to 0.5 m was taken.

Integrity of production wells and confining unit at the Naval Weapons Industrial Reserve Plant, Dallas, Texas, 1995

USGS Publications Warehouse

Jones, Sonya A.; Paillet, Frederick L.

1997-01-01

The results of borehole geophysical log analysis indicate that two of the production wells could have vertically connected intervals where cement bonding in the well annulus is poor. The other production wells have overall good bonding. Temperature logs do not indicate flow behind casing except in the screened interval of one well. Geophysical logs show the Eagle Ford Shale ranges from 147 to 185 feet thick at the site. The Eagle Ford Shale has low permeability and a high plasticity index. These physical characteristics make the Eagle Ford Shale an excellent confining unit.

Molecular characterization and comparison of shale oils generated by different pyrolysis methods

USGS Publications Warehouse

Birdwell, Justin E.; Jin, Jang Mi; Kim, Sunghwan

2012-01-01

Shale oils generated using different laboratory pyrolysis methods have been studied using standard oil characterization methods as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI) and atmospheric photoionization (APPI) to assess differences in molecular composition. The pyrolysis oils were generated from samples of the Mahogany zone oil shale of the Eocene Green River Formation collected from outcrops in the Piceance Basin, Colorado, using three pyrolysis systems under conditions relevant to surface and in situ retorting approaches. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules and the distribution of nitrogen-containing compound classes. Comparison of FT-ICR MS results to other oil characteristics, such as specific gravity; saturate, aromatic, resin, asphaltene (SARA) distribution; and carbon number distribution determined by gas chromatography, indicated correspondence between higher average double bond equivalence (DBE) values and increasing asphaltene content. The results show that, based on the shale oil DBE distributions, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions, and under high pressure, moderate temperature conditions in the presence of water. We also report, for the first time in any petroleum-like substance, the presence of N4 class compounds based on FT-ICR MS data. Using double bond equivalence and carbon number distributions, structures for the N4 class and other nitrogen-containing compounds are proposed.

Sustainability of UK shale gas in comparison with other electricity options: Current situation and future scenarios.

PubMed

Cooper, Jasmin; Stamford, Laurence; Azapagic, Adisa

2018-04-01

Many countries are considering exploitation of shale gas but its overall sustainability is currently unclear. Previous studies focused mainly on environmental aspects of shale gas, largely in the US, with scant information on socio-economic aspects. To address this knowledge gap, this paper integrates for the first time environmental, economic and social aspects of shale gas to evaluate its overall sustainability. The focus is on the UK which is on the cusp of developing a shale gas industry. Shale gas is compared to other electricity options for the current situation and future scenarios up to the year 2030 to investigate whether it can contribute towards a more sustainable electricity mix in the UK. The results obtained through multi-criteria decision analysis suggest that, when equal importance is assumed for each of the three sustainability aspects shale gas ranks seventh out of nine electricity options, with wind and solar PV being the best and coal the worst options. However, it outranks biomass and hydropower. Changing the importance of the sustainability aspects widely, the ranking of shale gas ranges between fourth and eighth. For shale gas to become the most sustainable option of those assessed, large improvements would be needed, including a 329-fold reduction in environmental impacts and 16 times higher employment, along with simultaneous large changes (up to 10,000 times) in the importance assigned to each criterion. Similar changes would be needed if it were to be comparable to conventional or liquefied natural gas, biomass, nuclear or hydropower. The results also suggest that a future electricity mix (2030) would be more sustainable with a lower rather than a higher share of shale gas. These results serve to inform UK policy makers, industry and non-governmental organisations. They will also be of interest to other countries considering exploitation of shale gas. Copyright © 2017 Elsevier B.V. All rights reserved.

Thick sequences of silicate and carbonate rocks of sedimentary origin in North America an interim report

USGS Publications Warehouse

Love, John David

1956-01-01

Thick sequences of silicate and carbonate rocks of sedimentary origin have been investigated in 64 areas in North America. The areas containing the thickest and most homogeneous stratigraphic sections more than 1,000 feet thick, buried at depths greater than 10,000 feet are: 1. Uinta Basin, Utah, where the Mancos shale is 1,300 to 5,000 feet thick, the Weber sandstone is 1,000 to 1,600 feet thick, and Mississippian limestones are 1,000 to 1,500 feet thick. 2. Washakie Basin, Wyoming, and Sand Wash Ba.sin, Colorado, where the Lewis shale is 1,000 to 2,000 feet thick and the Cody-Mancos shale is 4,500 to 5,500 feet thick. 3. Green River Basin, Wyoming, where the Cody-Hilliard-Baxter-Mancos shale sequence averages more than 3,000 feet, the siltstone and shale of the Chugwater formation totals 1,000 feet, and the Madison limestone ranges from 1,000 to 1,400 feet thick. 4. Red Desert (Great Divide) Basin, Wyoming, where the Cody shale is 4,000 feet thick. 5. Hanna Basin, Wyoming, where the Steele shale is 4,500 feet thick. 6. Wind River Basin, Wyoming, where the Cody shale is 3,600 to 5,000 feet thick. Geochemical characteristics of these rocks in these areas are poorly known but are being investigated. A summary of the most pertinent recent ana1yses is presented.

Helium release during shale deformation: Experimental validation

DOE PAGES

Bauer, Stephen J.; Gardner, W. Payton; Heath, Jason E.

2016-07-01

This paper describes initial experimental results of helium tracer release monitoring during deformation of shale. Naturally occurring radiogenic 4He is present in high concentration in most shales. During rock deformation, accumulated helium could be released as fractures are created and new transport pathways are created. We present the results of an experimental study in which confined reservoir shale samples, cored parallel and perpendicular to bedding, which were initially saturated with helium to simulate reservoir conditions, are subjected to triaxial compressive deformation. During the deformation experiment, differential stress, axial, and radial strains are systematically tracked. Release of helium is dynamically measuredmore » using a helium mass spectrometer leak detector. Helium released during deformation is observable at the laboratory scale and the release is tightly coupled to the shale deformation. These first measurements of dynamic helium release from rocks undergoing deformation show that helium provides information on the evolution of microstructure as a function of changes in stress and strain.« less

Predominance and Metabolic Potential of Halanaerobium spp. in Produced Water from Hydraulically Fractured Marcellus Shale Wells.

PubMed

Lipus, Daniel; Vikram, Amit; Ross, Daniel; Bain, Daniel; Gulliver, Djuna; Hammack, Richard; Bibby, Kyle

2017-04-15

Microbial activity in the produced water from hydraulically fractured oil and gas wells may potentially interfere with hydrocarbon production and cause damage to the well and surface infrastructure via corrosion, sulfide release, and fouling. In this study, we surveyed the microbial abundance and community structure of produced water sampled from 42 Marcellus Shale wells in southwestern Pennsylvania (well age ranged from 150 to 1,846 days) to better understand the microbial diversity of produced water. We sequenced the V4 region of the 16S rRNA gene to assess taxonomy and utilized quantitative PCR (qPCR) to evaluate the microbial abundance across all 42 produced water samples. Bacteria of the order Halanaerobiales were found to be the most abundant organisms in the majority of the produced water samples, emphasizing their previously suggested role in hydraulic fracturing-related microbial activity. Statistical analyses identified correlations between well age and biocide formulation and the microbial community, in particular, the relative abundance of Halanaerobiales We further investigated the role of members of the order Halanaerobiales in produced water by reconstructing and annotating a Halanaerobium draft genome (named MDAL1), using shotgun metagenomic sequencing and metagenomic binning. The recovered draft genome was found to be closely related to the species H. congolense , an oil field isolate, and Halanaerobium sp. strain T82-1, also recovered from hydraulic fracturing produced water. Reconstruction of metabolic pathways revealed Halanaerobium sp. strain MDAL1 to have the potential for acid production, thiosulfate reduction, and biofilm formation, suggesting it to have the ability to contribute to corrosion, souring, and biofouling events in the hydraulic fracturing infrastructure. IMPORTANCE There are an estimated 15,000 unconventional gas wells in the Marcellus Shale region, each generating up to 8,000 liters of hypersaline produced water per day throughout its lifetime (K. Gregory, R. Vidic, and D. Dzombak, Elements 7:181-186, 2011, https://doi.org/10.2113/gselements.7.3.181; J. Arthur, B. Bohm, and M. Layne, Gulf Coast Assoc Geol Soc Trans 59:49-59, 2009; https://www.marcellusgas.org/index.php). Microbial activity in produced waters could lead to issues with corrosion, fouling, and souring, potentially interfering with hydraulic fracturing operations. Previous studies have found microorganisms contributing to corrosion, fouling, and souring to be abundant across produced water samples from hydraulically fractured wells; however, these findings were based on a limited number of samples and well sites. In this study, we investigated the microbial community structure in produced water samples from 42 unconventional Marcellus Shale wells, confirming the dominance of the genus Halanaerobium in produced water and its metabolic potential for acid and sulfide production and biofilm formation. Copyright © 2017 American Society for Microbiology.

Predominance and Metabolic Potential of Halanaerobium spp. in Produced Water from Hydraulically Fractured Marcellus Shale Wells

PubMed Central

Lipus, Daniel; Vikram, Amit; Ross, Daniel; Bain, Daniel; Gulliver, Djuna; Hammack, Richard

2017-01-01

ABSTRACT Microbial activity in the produced water from hydraulically fractured oil and gas wells may potentially interfere with hydrocarbon production and cause damage to the well and surface infrastructure via corrosion, sulfide release, and fouling. In this study, we surveyed the microbial abundance and community structure of produced water sampled from 42 Marcellus Shale wells in southwestern Pennsylvania (well age ranged from 150 to 1,846 days) to better understand the microbial diversity of produced water. We sequenced the V4 region of the 16S rRNA gene to assess taxonomy and utilized quantitative PCR (qPCR) to evaluate the microbial abundance across all 42 produced water samples. Bacteria of the order Halanaerobiales were found to be the most abundant organisms in the majority of the produced water samples, emphasizing their previously suggested role in hydraulic fracturing-related microbial activity. Statistical analyses identified correlations between well age and biocide formulation and the microbial community, in particular, the relative abundance of Halanaerobiales. We further investigated the role of members of the order Halanaerobiales in produced water by reconstructing and annotating a Halanaerobium draft genome (named MDAL1), using shotgun metagenomic sequencing and metagenomic binning. The recovered draft genome was found to be closely related to the species H. congolense, an oil field isolate, and Halanaerobium sp. strain T82-1, also recovered from hydraulic fracturing produced water. Reconstruction of metabolic pathways revealed Halanaerobium sp. strain MDAL1 to have the potential for acid production, thiosulfate reduction, and biofilm formation, suggesting it to have the ability to contribute to corrosion, souring, and biofouling events in the hydraulic fracturing infrastructure. IMPORTANCE There are an estimated 15,000 unconventional gas wells in the Marcellus Shale region, each generating up to 8,000 liters of hypersaline produced water per day throughout its lifetime (K. Gregory, R. Vidic, and D. Dzombak, Elements 7:181–186, 2011, https://doi.org/10.2113/gselements.7.3.181; J. Arthur, B. Bohm, and M. Layne, Gulf Coast Assoc Geol Soc Trans 59:49–59, 2009; https://www.marcellusgas.org/index.php). Microbial activity in produced waters could lead to issues with corrosion, fouling, and souring, potentially interfering with hydraulic fracturing operations. Previous studies have found microorganisms contributing to corrosion, fouling, and souring to be abundant across produced water samples from hydraulically fractured wells; however, these findings were based on a limited number of samples and well sites. In this study, we investigated the microbial community structure in produced water samples from 42 unconventional Marcellus Shale wells, confirming the dominance of the genus Halanaerobium in produced water and its metabolic potential for acid and sulfide production and biofilm formation. PMID:28159795

Marketable transport fuels made from Julia Creek shale oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1987-03-01

CSR Limited and the CSIRO Division of Energy Chemistry have been working on the problem of producing refined products from the Julia Creek deposit in Queensland, Australia. Two samples of shale oil, retorted at different temperatures from Julia Creek oil shale, were found to differ markedly in aromaticity. Using conventional hydrotreating technology, high quality jet and diesel fuels could be made from the less aromatic oil. Naphtha suitable for isomerization and reforming to gasoline could be produced from both oils. This paper discusses oil properties, stabilization of topped crudes, second stage hydrotreatment, and naphtha hydrotreating. 1 figure, 4 tables.

Mass and heat transfer in crushed oil shale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Carley, J.F.; Ott, L.L.; Swecker, J.L.

1995-03-01

Studies of heat and mass transfer in packed beds, which disagree substantially in their findings, have nearly all been done with beds of regular particles of uniform size, whereas oil-shale retorting involves particles of diverse irregular shapes and sizes. The authors, in 349 runs, measured mass-transfer rates front naphthalene particles buried in packed beds by passing through air at room temperature. An exact catalog between convection of heat and mass makes it possible to infer heat-transfer coefficients from measured mass-transfer coefficients and fluid properties. Some beds consisted of spheres, naphthalene and inert, of the same, contrasting or distributed sizes. Inmore » some runs, naphthalene spheres were buried in beds of crushed shale, some in narrow screen ranges and others with a wide size range. In others, naphthalene lozenges of different shapes were buried in beds of crushed shale in various bed axis orientations. This technique permits calculation of the mass-transfer coefficient for each active particle in the bed rather than, as in most past studies, for the bed as a whole. The data are analyzed by the traditional correlation of Colburn j{sub D} vs. Reynolds number and by multiple regression of the mass-transfer coefficient on air rate, sizes of active and inert particles, void fraction, and temperature. Principal findings are: local Reynolds number should be based on the active-particle size, not the average for the whole bed; differences between shallow and deep beds are not appreciable; mass transfer is 26% faster for spheres and lozenges buried in shale than in all-sphere beds; orientation of lozenges in shale beds has little or no effect on mass-transfer rate; and for mass or heat transfer in shale beds, log(j{center_dot}{epsilon}) = {minus}0.0747 - 0.6344 log N{sub Re} + 0. 0592 log {sup 2} N{sub Re}.« less

Water Saturation Relations and Their Diffusion-Limited Equilibration in Gas Shale: Implications for Gas Flow in Unconventional Reservoirs

NASA Astrophysics Data System (ADS)

Tokunaga, Tetsu K.; Shen, Weijun; Wan, Jiamin; Kim, Yongman; Cihan, Abdullah; Zhang, Yingqi; Finsterle, Stefan

2017-11-01

Large volumes of water are used for hydraulic fracturing of low permeability shale reservoirs to stimulate gas production, with most of the water remaining unrecovered and distributed in a poorly understood manner within stimulated regions. Because water partitioning into shale pores controls gas release, we measured the water saturation dependence on relative humidity (rh) and capillary pressure (Pc) for imbibition (adsorption) as well as drainage (desorption) on samples of Woodford Shale. Experiments and modeling of water vapor adsorption into shale laminae at rh = 0.31 demonstrated that long times are needed to characterize equilibrium in larger (5 mm thick) pieces of shales, and yielded effective diffusion coefficients from 9 × 10-9 to 3 × 10-8 m2 s-1, similar in magnitude to the literature values for typical low porosity and low permeability rocks. Most of the experiments, conducted at 50°C on crushed shale grains in order to facilitate rapid equilibration, showed significant saturation hysteresis, and that very large Pc (˜1 MPa) are required to drain the shales. These results quantify the severity of the water blocking problem, and suggest that gas production from unconventional reservoirs is largely associated with stimulated regions that have had little or no exposure to injected water. Gravity drainage of water from fractures residing above horizontal wells reconciles gas production in the presence of largely unrecovered injected water, and is discussed in the broader context of unsaturated flow in fractures.

A multi-scale micromechanics framework for shale using the nano-tools

NASA Astrophysics Data System (ADS)

Ortega, J.; Ulm, F.; Abousleiman, Y.

2009-12-01

The successful prediction of poroelastic properties of fine-grained rocks such as shale continues to be a formidable challenge for the geophysics community. The highly heterogeneous nature of shale in terms of its compositional and microstructural features translates into a complex anisotropic behavior observed at macroscopic length scales. The recent application of instrumented indentation for the mechanical characterization of shale has revealed the granular response and intrinsic anisotropy of its porous clay phase at nanometer length scales [1-2]. This discovered mechanical behavior at the grain scale has been incorporated into the development of a multi-scale, micromechanics model for shale poroelasticity [3]. The only inputs to the model are two volumetric parameters synthesizing the mineralogy and porosity information of a shale sample. The model is meticulously calibrated and validated, as displayed in Fig. 1, with independent data sets of anisotropic elasticity obtained from nanoindentation experiments and standard laboratory acoustic measurements for shale specimens with and without organic content. The treatment of the elastic anisotropy corresponding to the porous clay fabric, as sensed by nanoindentation, delineates the contribution of the intrinsic anisotropy in shale to its overall anisotropy observed at macroscales. Furthermore, the proposed poroelastic formulation provides access to intrinsic rock parameters such as Biot pore pressure coefficients that are of importance for problems of flow in porous media. In addition, the model becomes a useful tool in geophysics applications for the prediction of shale acoustic properties from material-specific information such as porosity, mineralogy, and density measurements. References: [1] Ulm, F.-J., Abousleiman, Y. (2006) ‘The nanogranular nature of shale.’ Acta Geot. 1(2), 77-88. [2] Bobko, C., Ulm, F.-J. (2008) ‘The nano-mechanical morphology of shale.’ Mech. Mat. 40(4-5), 318-337. [3] Ortega, J. A., Ulm, F.-J., Abousleiman, Y. (2009) ‘The nanogranular acoustic signature of shale.’ Geophysics 74(3), D65-D84. Fig. 1. Comparisons between predicted and experimental elasticity obtained from nanoindentation experiments (left) and acoustic measurements (right) for shale with and without organic content (hollow and solid data points). Nanoindentation elasticity of the porous clay in shale is presented as a function of the clay packing density (one minus the nanoporosity). The x-1, x-3 directions correspond to parallel and normal-to-bedding plane properties, respectively. All nanoindentation data and acoustic measurements for organic-rich shale from [2-3]. Acoustic measurements for organic-free shale were gathered from literature sources compiled in [3].

Pyrolysis gas chromatography-mass spectrometry to characterize organic matter and its relationship to uranium content of Appalachian Devonian black shales

USGS Publications Warehouse

Leventhal, J.S.

1981-01-01

Gas Chromatographic analysis of volatile products formed by stepwise pyrolysis of black shales can be used to characterize the kerogen by relating it to separated, identified precursors such as land-derived vitrinite and marine-source Tasmanites. Analysis of a Tasmanites sample shows exclusively n-alkane and -alkene pyrolysis products, whereas a vitrinite sample shows a predominance of one- and two-ring substituted aromatics. For core samples from northern Tennessee and for a suite of outcrop samples from eastern Kentucky, the organic matter type and the U content (<10-120ppm) show variations that are related to precursor organic materials. The samples that show a high vitrinite component in their pyrolysis products are also those samples with high contents of U. ?? 1981.

On the changing petroleum generation properties of Alum Shale over geological time caused by uranium irradiation

NASA Astrophysics Data System (ADS)

Yang, Shengyu; Schulz, Hans-Martin; Horsfield, Brian; Schovsbo, Niels H.; Noah, Mareike; Panova, Elena; Rothe, Heike; Hahne, Knut

2018-05-01

An interdisciplinary study was carried out to unravel organic-inorganic interactions caused by the radiogenic decay of uranium in the immature organic-rich Alum Shale (Middle Cambrian-Lower Ordovician). Based on pyrolysis experiments, uranium content is positively correlated with the gas-oil ratios and the aromaticities of both the free hydrocarbons residing in the rock and the pyrolysis products from its kerogen, indicating that irradiation has had a strong influence on organic matter composition overall and hence on petroleum potential. The Fourier Transform Ion Cyclotron Resonance mass spectrometry data reveal that macro-molecules in the uranium-rich Alum Shale samples are less alkylated than less irradiated counterparts, providing further evidence for structural alteration by α-particle bombardment. In addition, oxygen containing-compounds are enriched in the uranium-rich samples but are not easily degradable into low-molecular-weight products due to irradiation-induced crosslinking. Irradiation has induced changes in organic matter composition throughout the shale's entire ca. 500 Ma history, irrespective of thermal history. This factor has to be taken into account when reconstructing petroleum generation history. The Alum Shale's kerogen underwent catagenesis in the main petroleum kitchen area 420-340 Ma bp. Our calculations suggest the kerogen was much more aliphatic and oil-prone after deposition than that after extensive exposure to radiation. In addition, the gas sorption capacity of the organic matter in the Alum Shale can be assumed to have been less developed during Palaeozoic times, in contrast to results gained by sorption experiments performed at the present day, for the same reason. The kerogen reconstruction method developed here precludes overestimations of gas generation and gas retention in the Alum Shale by taking irradiation exposure into account and can thus significantly mitigate charge risk when applied in the explorations for both conventional and unconventional hydrocarbons.

Four dimensional X-ray imaging of deformation modes in organic-rich Green River Shale retorted under uniaxial compression

NASA Astrophysics Data System (ADS)

Kobchenko, M.; Pluymakers, A.; Cordonnier, B.; Tairova, A.; Renard, F.

2017-12-01

Time-lapse imaging of fracture network development in organic-rich shales at elevated temperatures while kerogen is retorted allows characterizing the development of microfractures and the onset of primary migration. When the solid organic matter is transformed to hydrocarbons with lower molecular weight, the local pore-pressure increases and drives the propagation of hydro-fractures sub-parallel to the shale lamination. On the scale of samples of several mm size, these fractures can be described as mode I opening, where fracture walls dilate in the direction of minimal compression. However, so far experiments coupled to microtomography in situ imaging have been performed on samples where no load was imposed. Here, an external load was applied perpendicular to the sample laminations and we show that this stress state slows down, but does not stop, the propagation of fracture along bedding. Conversely, microfractures also propagate sub-perpendicular to the shale lamination, creating a percolating network in three dimensions. To monitor this process we have used a uniaxial compaction rig combined with in-situ heating from 50 to 500 deg C, while capturing three-dimensional X-ray microtomography scans at a voxel resolution of 2.2 μm; Data were acquired at beamline ID19 at the European Synchrotron Radiation Facility. In total ten time-resolved experiments were performed at different vertical loading conditions, with and without lateral passive confinement and different heating rates. At high external load the sample fails by symmetric bulging, while at lower external load the reaction-induced fracture network develops with the presence of microfractures both sub-parallel and sub-perpendicular to the bedding direction. In addition, the variation of experimental conditions allows the decoupling of the effects of the hydrocarbon decomposition reaction on the deformation process from the influence of thermal stress heating on the weakening and failure mode of immature shale.

Transient pressure-pulse decay permeability measurements in the Barnett shale

NASA Astrophysics Data System (ADS)

Bhandari, A. R.; Reece, J.; Cronin, M. B.; Flemings, P. B.; Polito, P. J.

2012-12-01

We conducted transient pressure-pulse decay permeability measurements on core plugs of the Barnett shale using a hydrostatic pressure cell. Core plugs, 3.8 cm in diameter and less than 2.5 cm in length, were prepared from a core obtained at a depth of approximately 2330 m from the Mitchel Energy 2 T. P. Sims well in the Mississippian Barnett Formation (Loucks and Ruppel, 2007). We performed permeability measurements of the core plugs using argon at varying confining pressures in two different directions (perpendicular and parallel to bedding planes). We calculate gas permeability from changes in pressure with time using the analytical solution of the pressure diffusion equation with appropriate boundary conditions for our test setup (Dicker and Smits, 1988). Based on our limited results, we interpret 2 × 10-18 m2 for vertical permeability and 156 × 10-18 m2 for horizontal permeability. We demonstrate an extreme stress dependence of the horizontal flow permeability where permeability decreases from 156 × 10-18 m2 to 2.5 × 10-18 m2 as the confining stress is increased from 3.5 to 35 MPa. These permeability measurements are at the high side of other pulsed permeability measurements in the Barnett shale (Bustin et al. 2008; Vermylen, 2011). Permeabilities calculated from mercury injection capillary pressure curves, using theoretically derived permeability-capillary pressure models based on parallel tubes assumption, are orders of magnitude less than our transient pressure-pulse decay permeability measurements (for example, 3.7×10-21 m2 (this study), 10-21 -10-20 m2 (Sigal, 2007), 10-20 -10-17 m2 (Prince et al., 2010)). We interpret that the high measured permeabilities are due to microfractures in the sample. At this point, we do not know if the microfractures are due to sampling disturbance (stress-relief induced) or represent an in-situ fracture network. Our study illustrates the importance of characterization of microfractures at the core scale to understand better the transport behavior in shale matrix and sealing efficiency of cap rocks. References Bustin et al. (2008), Impact of shale properties on pore structure and storage characteristics, SPE 119892. Dicker and Smits (1988), A practical method for determining permeability from laboratory pressure-pulse decay measurements, SPE 17578. Loucks and Ruppel (2007), Mississippian Barnett Shale: Lithofacies and depositional setting of a deep-water shale gas succession in the Fort Worth Basin, Texas, AAPG 2007. Sigal (2007), Mercury capillary pressure measurements on Barnett core. (http://shale.ou.edu/Home/Publication) Prince et al. (2010), Shale diagenesis and permeability: examples from the Barnett shale and the Marcellus formation, AAPG 2010. Vermylen, J.P. (2011), Geomechanical studies of the Barnett Shale, Texas, USA, PhD thesis, Stanford University.

Magnetic anisotropy of Silurian organic-rich shale rocks and calcareous concretions from Northern Poland

NASA Astrophysics Data System (ADS)

Niezabitowska, Dominika; Szaniawski, Rafał

2017-04-01

The research has been performed on Wenlockian shales of Pelplin formation from the Pomerania region located in Northern Poland. These organic-rich marine shales were deposited on the western shelf of the Baltica paleo-continent and currently they constitute the cover of East European Platform. The studied shales lie almost completely flat without signs of tectonic deformations. Rock magnetic studies were carried out with the aim of recognizing ferro- and paramagnetic minerals in shales and thus fully understanding the origin of the magnetic anisotropy. The typical dark shales and spherical calcareous concretions from two boreholes were sampled. Based on deflection of shales beds bordered with a concretions, we deduce that such concretions were formed in the early stage of diagenesis, before the final compaction and lithification of surrounding shales. We obtained similar rockmagnetic results for both of rock types. The results of thermal variation of magnetic susceptibility and hysteresis loops show that the magnetic susceptibility is mainly controlled by paramagnetic minerals, due to domination of phyllosilicate minerals, with a smaller impact of ferromagnetic phase. The results of the hysteresis studies documented the domination of low coercivity ferromagnetic minerals, that is magnetite and pyrrhotite. The deposition alignment of flocculated phyllosilicates and further compaction determine distinct bedding parallel foliation of the AMS (Anisotropy of Magnetic Susceptibility) in the both drill cores. In one of the drill core the maximal AMS axes are almost randomly distributed in the bedding plane and show only a weak tendency for grouping. In the second drill core the magnetic lineation is better defined. In the case of concretions the bedding parallel magnetic foliation is also evident but it is much weaker than in shales. In turn, the magnetic lineation in the both drill cores is well developed and the maximal AMS axes are well grouped. In both of the cores the orientation of lineation from concretions complies with site mean lineation from shale rocks. To summarize, the results imply that the phyllosilicate minerals from shales are typically well aligned in the bedding plane by compaction processes. In the case of calcareous concretions the foliation is less developed due to their earlier cementation of flocculated phyllosicates in the calcareous matrix, which occurred before the end of sediments compaction. A good grouping of the maximal AMS axes within the early cemented concretions suggest that the magnetic lineation is rather sedimentary than tectonic in origin. We suggest that the magnetic lineation is probably related to the orientation of flocculated phyllosilicates due to transportation. This work has been funded by the Polish National Centre for Research and Development within the Blue Gas project (No BG2/SHALEMECH/14). Samples were provided by the PGNiG SA.

Viscous Creep in Dry Unconsolidated Gulf of Mexico Shale

NASA Astrophysics Data System (ADS)

Chang, C.; Zoback, M. D.

2002-12-01

We conducted laboratory experiments to investigate creep characteristics of dry unconsolidated shale recovered from the pathfinder well, Gulf of Mexico (GOM). We subjected jacketed cylindrical specimens (25.4 mm diameter) to hydrostatic pressure that increased from 10 to 50 MPa in steps of 5 MPa. We kept the pressure constant in each step for at least 6 hours and measured axial and lateral strains (provided by LVDTs) and ultrasonic velocities (provided by seismic-wave transducers). The dry shale exhibited pronounced creep strain at all pressure levels, indicating that the dry frame of the shale possesses an intrinsic viscous property. Interestingly, the creep behavior of the shale is different above and below 30 MPa confining pressure. Above 30 MPa, the amount of creep strain in 6 hours is nearly constant with equal pressurization steps, indicating a linear viscous rheology. Below 30 MPa, the amount of creep increases linearly as pressure is raised in constant incremental steps, suggesting that the creep deformation accelerates as pressure increases within this pressure range. Thus, the general creep behavior of the GOM shale is characterized by a bilinear dependence on pressure magnitude. This creep characteristic is quite different from that observed in unconsolidated reservoir sands (Hagin and Zoback, 2002), which exhibited nearly constant amount of creep regardless of the pressure magnitude for equal increasing steps of pressure. The shale exhibits a lack of creep (and nearly negligible strain recovery) when unloaded, suggesting that the creep strain is irrecoverable and can be considered viscoplastic deformation. SEM observations show that the major mechanism of compaction of the dry shale appears to be packing of clay and a progressive collapse of pore (void) spaces. Creep compaction is considerably more significant than compaction that occurs instantaneously, indicating that the process of shale compaction is largely time-dependent.

Assessment of Appalachian basin oil and gas resources: Devonian gas shales of the Devonian Shale-Middle and Upper Paleozoic Total Petroleum System: Chapter G.9 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

USGS Publications Warehouse

Milici, Robert C.; Swezey, Christopher S.; Ruppert, Leslie F.; Ryder, Robert T.

2014-01-01

This report presents the results of a U.S. Geological Survey (USGS) assessment of the technically recoverable undiscovered natural gas resources in Devonian shale in the Appalachian Basin Petroleum Province of the eastern United States. These results are part of the USGS assessment in 2002 of the technically recoverable undiscovered oil and gas resources of the province. This report does not use the results of a 2011 USGS assessment of the Devonian Marcellus Shale because the area considered in the 2011 assessment is much greater than the area of the Marcellus Shale described in this report. The USGS assessment in 2002 was based on the identification of six total petroleum systems, which include strata that range in age from Cambrian to Pennsylvanian. The Devonian gas shales described in this report are within the Devonian Shale-Middle and Upper Paleozoic Total Petroleum System, which extends generally from New York to Tennessee. This total petroleum system is divided into ten assessment units (plays), four of which are classified as conventional and six as continuous. The Devonian shales described in this report make up four of these continuous assessment units. The assessment results are reported as fully risked fractiles (F95, F50, F5, and the mean); the fractiles indicate the probability of recovery of the assessment amount. The products reported are oil, gas, and natural gas liquids. The mean estimates for technically recoverable undiscovered hydrocarbons in the four gas shale assessment units are 12,195.53 billion cubic feet (12.20 trillion cubic feet) of gas and 158.91 million barrels of natural gas liquids

Chemical Degradation of Polyacrylamide during Hydraulic Fracturing

NASA Astrophysics Data System (ADS)

Xiong, B.; Tasker, T.; Miller, Z.; Roman-White, S.; Farina, B.; Piechowicz, B.; Burgos, W.; Joshi, P.; Zhu, L.; Gorski, C.; Zydney, A.; Kumar, M.

2017-12-01

Polyacrylamide (PAM) based friction reducers are a primary ingredient of slickwater hydraulic fracturing fluids. Little is known regarding the fate of these polymers under downhole conditions, which could have important environmental impacts including strategies for reuse or treatment of flowback water. The objective of this study was to evaluate the chemical degradation of high molecular weight PAM, including the effects of shale, oxygen, temperature, pressure, and salinity. Data were obtained with a slickwater fracturing fluid exposed to both a shale sample collected from a Marcellus shale outcrop and to Marcellus core samples at high pressures/temperatures (HPT) simulating downhole conditions. Based on size exclusion chromatography analyses, the peak molecular weight of the PAM was reduced by two orders of magnitude, from roughly 10 MDa to 200 kDa under typical HPT fracturing conditions. The rate of degradation was independent of pressure and salinity but increased significantly at high temperatures and in the presence of oxygen dissolved in fracturing fluid. Results were consistent with a free radical chain scission mechanism, supported by measurements of sub-M hydroxyl radical concentrations. The shale sample adsorbed some PAM ( 30%), but importantly it catalyzed the chemical degradation of PAM, likely due to dissolution of Fe2+ at low pH. These results provide the first evidence of radical-induced degradation of PAM under HPT hydraulic fracturing conditions without additional oxidative breaker.

Controls on Methane Occurrences in Shallow Aquifers Overlying the Haynesville Shale Gas Field, East Texas.

PubMed

Nicot, Jean-Philippe; Larson, Toti; Darvari, Roxana; Mickler, Patrick; Slotten, Michael; Aldridge, Jordan; Uhlman, Kristine; Costley, Ruth

2017-07-01

Understanding the source of dissolved methane in drinking-water aquifers is critical for assessing potential contributions from hydraulic fracturing in shale plays. Shallow groundwater in the Texas portion of the Haynesville Shale area (13,000 km 2 ) was sampled (70 samples) for methane and other dissolved light alkanes. Most samples were derived from the fresh water bearing Wilcox formations and show little methane except in a localized cluster of 12 water wells (17% of total) in a approximately 30 × 30 km 2 area in Southern Panola County with dissolved methane concentrations less than 10 mg/L. This zone of elevated methane is spatially associated with the termination of an active fault system affecting the entire sedimentary section, including the Haynesville Shale at a depth more than 3.5 km, and with shallow lignite seams of Lower Wilcox age at a depth of 100 to 230 m. The lignite spatial extension overlaps with the cluster. Gas wetness and methane isotope compositions suggest a mixed microbial and thermogenic origin with contribution from lignite beds and from deep thermogenic reservoirs that produce condensate in most of the cluster area. The pathway for methane from the lignite and deeper reservoirs is then provided by the fault system. © 2017, National Ground Water Association.

The impact of shale gas on the cost and feasibility of meeting climate targets—A global energy system model analysis and an exploration of uncertainties

DOE PAGES

Few, Sheridan; Gambhir, Ajay; Napp, Tamaryn; ...

2017-01-27

There exists considerable uncertainty over both shale and conventional gas resource availability and extraction costs, as well as the fugitive methane emissions associated with shale gas extraction and its possible role in mitigating climate change. This study uses a multi-region energy system model, TIAM (TIMES integrated assessment model), to consider the impact of a range of conventional and shale gas cost and availability assessments on mitigation scenarios aimed at achieving a limit to global warming of below 2 °C in 2100, with a 50% likelihood. When adding shale gas to the global energy mix, the reduction to the global energymore » system cost is relatively small (up to 0.4%), and the mitigation cost increases by 1%–3% under all cost assumptions. The impact of a “dash for shale gas”, of unavailability of carbon capture and storage, of increased barriers to investment in low carbon technologies, and of higher than expected leakage rates, are also considered; and are each found to have the potential to increase the cost and reduce feasibility of meeting global temperature goals. Finally, we conclude that the extraction of shale gas is not likely to significantly reduce the effort required to mitigate climate change under globally coordinated action, but could increase required mitigation effort if not handled sufficiently carefully.« less

The impact of shale gas on the cost and feasibility of meeting climate targets—A global energy system model analysis and an exploration of uncertainties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Few, Sheridan; Gambhir, Ajay; Napp, Tamaryn

There exists considerable uncertainty over both shale and conventional gas resource availability and extraction costs, as well as the fugitive methane emissions associated with shale gas extraction and its possible role in mitigating climate change. This study uses a multi-region energy system model, TIAM (TIMES integrated assessment model), to consider the impact of a range of conventional and shale gas cost and availability assessments on mitigation scenarios aimed at achieving a limit to global warming of below 2 °C in 2100, with a 50% likelihood. When adding shale gas to the global energy mix, the reduction to the global energymore » system cost is relatively small (up to 0.4%), and the mitigation cost increases by 1%–3% under all cost assumptions. The impact of a “dash for shale gas”, of unavailability of carbon capture and storage, of increased barriers to investment in low carbon technologies, and of higher than expected leakage rates, are also considered; and are each found to have the potential to increase the cost and reduce feasibility of meeting global temperature goals. Finally, we conclude that the extraction of shale gas is not likely to significantly reduce the effort required to mitigate climate change under globally coordinated action, but could increase required mitigation effort if not handled sufficiently carefully.« less

Environmental consequences of shale gas exploitation and the crucial role of rock microfracturing

NASA Astrophysics Data System (ADS)

Renard, Francois

2015-04-01

The growing exploitation of unconventional gas and oil resources has dramatically changed the international market of hydrocarbons in the past ten years. However, several environmental concerns have also been identified such as the increased microseismicity, the leakage of gas into freshwater aquifers, and the enhanced water-rock interactions inducing the release of heavy metals and other toxic elements in the produced water. In all these processes, fluids are transported into a network of fracture, ranging from nanoscale microcracks at the interface between minerals and the kerogen of the source rock, to well-developed fractures at the meter scale. Characterizing the fracture network and the mechanisms of its formation remains a crucial goal. A major difficulty when analyzing fractures from core samples drilled at depth is that some of them are produced by the coring process, while some other are produced naturally at depth by the coupling between geochemical and mechanical forces. Here, I present new results of high resolution synchrotron 3D X-ray microtomography imaging of shale samples, at different resolutions, to characterize their microfractures and their mechanisms of formation. The heterogeneities of rock microstructure are also imaged, as they create local stress concentrations where cracks may nucleate or along which they propagate. The main results are that microcracks form preferentially along kerogen-mineral interfaces and propagate along initial heterogeneities according to the local stress direction, connecting to increase the total volume of fractured rock. Their lifetime is also an important parameter because they may seal by fluid circulation, fluid-rock interactions, and precipitation of a cement. Understanding the multi-scale processes of fracture network development in shales and the coupling with fluid circulation represents a key challenge for future research directions.

Comparison of caprock pore networks which potentially will be impacted by carbon sequestration projects.

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCray, John; Navarre-Sitchler, Alexis; Mouzakis, Katherine

Injection of CO2 into underground rock formations can reduce atmospheric CO2 emissions. Caprocks present above potential storage formations are the main structural trap inhibiting CO2 from leaking into overlying aquifers or back to the Earth's surface. Dissolution and precipitation of caprock minerals resulting from reaction with CO2 may alter the pore network where many pores are of the micrometer to nanometer scale, thus altering the structural trapping potential of the caprock. However, the distribution, geometry and volume of pores at these scales are poorly characterized. In order to evaluate the overall risk of leakage of CO2 from storage formations, amore » first critical step is understanding the distribution and shape of pores in a variety of different caprocks. As the caprock is often comprised of mudstones, we analyzed samples from several mudstone formations with small angle neutron scattering (SANS) and high-resolution transmission electron microscopy (TEM) imaging to compare the pore networks. Mudstones were chosen from current or potential sites for carbon sequestration projects including the Marine Tuscaloosa Group, the Lower Tuscaloosa Group, the upper and lower shale members of the Kirtland Formation, and the Pennsylvanian Gothic shale. Expandable clay contents ranged from 10% to approximately 40% in the Gothic shale and Kirtland Formation, respectively. During SANS, neutrons effectively scatter from interfaces between materials with differing scattering length density (i.e., minerals and pores). The intensity of scattered neutrons, I(Q), where Q is the scattering vector, gives information about the volume and arrangement of pores in the sample. The slope of the scattering data when plotted as log I(Q) vs. log Q provides information about the fractality or geometry of the pore network. On such plots slopes from -2 to -3 represent mass fractals while slopes from -3 to -4 represent surface fractals. Scattering data showed surface fractal dimensions for the Kirtland formation and one sample from the Tuscaloosa formation close to 3, indicating very rough surfaces. In contrast, scattering data for the Gothic shale formation exhibited mass fractal behavior. In one sample of the Tuscaloosa formation the data are described by a surface fractal at low Q (larger pores) and a mass fractal at high Q (smaller pores), indicating two pore populations contributing to the scattering behavior. These small angle neutron scattering results, combined with high-resolution TEM imaging, provided a means for both qualitative and quantitative analysis of the differences in pore networks between these various mudstones.« less

Creep Behavior of Posidonia Shale at Elevated Pressure and Temperature

NASA Astrophysics Data System (ADS)

Rybacki, E.; Herrmann, J.; Wirth, R.; Dresen, G.

2017-12-01

Unconventional reservoir rocks are usually stimulated by repeated hydraulic fracturing operations. However, the production rate often decays with time that may arise from creep-induced fracture closure by proppant embedment. To examine experimentally the creep behavior of shales, we deformed immature carbonate-rich Posidonia shale at constant stress conditions and elevated temperatures between 50° and 200°C and confining pressures of 50 to 200 MPa. Samples showed transient creep in the semibrittle regime with high deformation rates at high differential stress, high temperature, and low confinement. Strain was mainly accommodated by deformation of the weak organic matter and phyllosilicates and by pore space reduction. At relatively low stress the samples deformed in the primary creep regime with continuously decelerating strain rate. The relation between strain and time can be described by an empirical power law equation, where the fitted parameters vary with temperature, pressure and stress. Our results suggest that healing of hydraulic fractures at low stresses by creep-induced proppant embedment is unlikely within a creep period of several years. At high differential stress (85-90% of the triaxial strength), as may be expected in situ at contact areas due to stress concentrations, the shale showed secondary creep, followed by tertiary creep until failure. In this regime, stress corrosion may induce microcrack propagation and coalescence. Secondary creep rates were also described by a power law that predicts faster fracture closure rates than for primary creep and likely contributes to production rate decline. Comparison of our data with published primary creep data on other shales suggest that the long-term creep behavior of shales can be correlated to their brittleness estimated from composition. Low creep strain is supported by a high fraction of strong minerals that can build up a load-bearing framework.

Soil properties of crocker formation and its influence on slope instability along the Ranau-Tambunan highway, Sabah

NASA Astrophysics Data System (ADS)

Azlan, Noran Nabilla Nor; Simon, Norbert; Hussin, Azimah; Roslee, Rodeano

2016-11-01

The Crocker formation on the study area consists of an inter-bedded shale and sandstone. The intense deformation and discontinuity on sandstone and shale beds of the arenaceous Crocker Formation makes them easily exposed to weathering and instability. In this study, a total of 15 selected slopes representing highly weathered material of stable and unstable conditions were studied to identify the characteristics of soil material on both conditions and how these characteristics will lead to instability. Physical properties analysis of soil material were conducted on 5 samples from stable slopes and 10 samples from failed slopes collected along the Ranau-Tambunan highway (RTM), Sabah. The analysis shows that the Crocker Formation consists mainly of poorly graded materials of sandy SILT with low plasticity (MLS) and PI value ranges from 1%-14. The failures materials are largely consist of low water content (0.94%-2.03%), higher finer texture material (11%-71%), intermediate liquid limit (21%-44%) and low plastic limit (20%-30%) while stable material consist of low water content (1.25%-1.80%), higher coarser texture material (43%-78%), low liquid limit (25%-28%) and low plastic limit (22%-25%). Specific gravity shows a ranges value of 2.24-2.60 for both slope conditions. The clay content in failed slope samples exhibit a slightly higher percentage of clay indicating a higher plasticity value compared to stable slopes. Statistical analysis was carried out to examine the association between landslide occurrences with soil physical properties in both stable and unstable slopes. The significant of both slope condition properties association to landslide occurrences was determined by mean rank differences. The study reveals that the grain size and plasticity of soil have contributed largely to slope instability in the study area.

Radioactivity in wastes generated from shale gas exploration and production - North-Eastern Poland.

PubMed

Jodłowski, Paweł; Macuda, Jan; Nowak, Jakub; Nguyen Dinh, Chau

2017-09-01

In the present study, the K-40, U-238, Ra-226, Pb-210, Ra-228 and Th-228 activity concentrations were measured in 64 samples of wastes generated from shale gas exploration in North-Eastern Poland. The measured samples consist of drill cuttings, solid phase of waste drilling muds, fracking fluids, return fracking fluids and waste proppants. The measured activity concentrations in solid samples vary in a wide range from 116 to around 1100 Bq/kg for K-40, from 14 to 393 Bq/kg for U-238, from 15 to 415 Bq/kg for Ra-226, from 12 to 391 Bq/kg for Pb-210, from a few Bq/kg to 516 Bq/kg for Ra-228 and from a few Bq/kg to 515 Bq/kg for Th-228. Excluding the waste proppants, the measured activity concentrations in solid samples oscillate around their worldwide average values in soil. In the case of the waste proppants, the activity concentrations of radionuclides from uranium and thorium decay series are significantly elevated and equal to several hundreds of Bq/kg but it is connected with the mineralogical composition of proppants. The significant enhancement of Ra-226 and Ra-228 activity concentrations after fracking process was observed in the case of return fracking fluids, but the radium isotopes content in these fluids is comparable with that in waste waters from copper and coal mines in Poland. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of Mineralogy, Pressure, Temperature and Stress on Mechanical roperties of shale Rocks

NASA Astrophysics Data System (ADS)

Herrmann, J.; Rybacki, E.; Sone, H.; Dresen, G. H.

2017-12-01

The production of hydrocarbons from unconventional reservoirs, like tight shale plays increased tremendously over the past decade. Hydraulic fracturing is a common method to increase the productivity of a well drilled in these reservoirs. Unfortunately, the production rate decreases over time presumably due to fracture healing. The healing rate induced by proppant embedment depends on pressure (p), temperature (T), stress (σ) - conditions and on shale composition. To improve understanding of the influence of these parameters on fracture healing, we conducted constant strain rate experiments (p = 50 - 100 MPa, T = 50 - 125 °C, ɛ/t = 5 * 10-4 - 5 * 10-6 s-1) on porous ( 8 %), quartz - rich ( 72 vol %) Bowland shale (UK) and on low porosity ( 3 %), clay - rich ( 33 vol %) Posidonia shale (GER), deformed perpendicular to bedding and with as-is water content. Bowland shale showed mainly brittle behaviour with predominantly elastic deformation before failure and a high strength (280 - 350 MPa). In contrast, Posidonia shale deformed semibrittle with pronounced inelastic deformation and low peak strength (165 - 220 MPa). For both shale rocks, static Young's moduli vary between 12 - 18 GPa. In addition, we performed a series of constant stress tests on both shales at p = 30 - 115 MPa, T = 75 - 150 °C and σ = 160 - 450 MPa. Samples showed transient (primary) creep with increasing strain rates for increasing temperature and stress and decreasing pressure. An empirical power law in the form of ɛ = A*tm is used to describe the observed relation between inelastic strain (ɛ) and time (t), where the constant A is mainly affected by temperature and stress and the exponent m accounts for the influence of pressure. Compared to quartz - rich, strong Bowland shale, the creep behaviour of clay - rich, weak Posidonia shale is much more sensitive to changes in pressure, temperature and stress. Electron microscopy suggests that creep was mainly accommodated by deformation of weak phases (TOC, clay, mica). Our results suggest a low fracture healing rate of Bowland shale, whereas fractures within the Posidonia formation tend to close faster.

Community-based risk assessment of water contamination from high-volume horizontal hydraulic fracturing.

PubMed

Penningroth, Stephen M; Yarrow, Matthew M; Figueroa, Abner X; Bowen, Rebecca J; Delgado, Soraya

2013-01-01

The risk of contaminating surface and groundwater as a result of shale gas extraction using high-volume horizontal hydraulic fracturing (fracking) has not been assessed using conventional risk assessment methodologies. Baseline (pre-fracking) data on relevant water quality indicators, needed for meaningful risk assessment, are largely lacking. To fill this gap, the nonprofit Community Science Institute (CSI) partners with community volunteers who perform regular sampling of more than 50 streams in the Marcellus and Utica Shale regions of upstate New York; samples are analyzed for parameters associated with HVHHF. Similar baseline data on regional groundwater comes from CSI's testing of private drinking water wells. Analytic results for groundwater (with permission) and surface water are made publicly available in an interactive, searchable database. Baseline concentrations of potential contaminants from shale gas operations are found to be low, suggesting that early community-based monitoring is an effective foundation for assessing later contamination due to fracking.

Ecology and distribution of large branchiopods (Crustacea, Branchiopoda, Anostraca, Notostraca, Laevicaudata, Spinicaudata) of the Eastern Cape Karoo, South Africa

PubMed Central

Mabidi, Annah; Bird, Matthew S.; Perissinotto, Renzo; Rogers, D. Christopher

2016-01-01

Abstract A survey of the large branchiopod fauna of the Eastern Cape Karoo region of South Africa was undertaken to provide baseline biodiversity information in light of impending shale gas development activities in the region. Twenty-two waterbodies, including nine dams and thirteen natural depression wetlands, were sampled during November 2014 and April 2015. A total of 13 species belonging to four orders were collected, comprising five anostracans, one notostracan, six spinicaudatans and one laevicaudatan. Cyzicus australis was most common, occurring in 46% of the waterbodies. Species co-occurred in 87% of the waterbodies, with a maximum number of six species recorded from the same waterbody. Our new distribution records for Lynceus truncatus, Streptocephalus spinicaudatus and Streptocephalus indistinctus represent substantial expansions of the previously known ranges for these species. Tarkastad is now the westernmost record for Streptocephalus spinicaudatus, while Jansenville now constitutes the southernmost record for Streptocephalus indistinctus. Large branchiopod distribution data from previous Eastern Cape records were combined with our current data, demonstrating that a total of 23 large branchiopod species have been recorded from the region to date. As the Karoo is one of the few major shale basins in the world where the natural baseline is still largely intact, this survey forms a basis for future reference and surface water quality monitoring during the process of shale gas exploration/extraction. PMID:27853398

Theoretical modeling of rhenium isotope fractionation, natural variations across a black shale weathering profile, and potential as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Miller, Christian A.; Peucker-Ehrenbrink, Bernhard; Schauble, Edwin A.

2015-11-01

We present the first data documenting environmental variations in the isotope composition of Re, and the first theoretical models of equilibrium Re isotope fractionation factors. Variations of δ187Re at modern surface temperatures are predicted to be ‰ level for redox (ReVII ⇌ ReIV) and perrhenate thiolation reactions (ReVIIO4- ⇌ReVIIOXS4-X- ⇌ReVII S4-). Nuclear volume fractionations are calculated to be smaller than mass dependent effects. Values of δ187Re from New Albany Shale samples presented in this work and in a previous study show a range of 0.8‰ over a stratigraphic interval of ∼20 m. The magnitude of variation is consistent with theoretical predictions and may provide evidence for changing δ187Re of seawater in the geologic past. A -0.3‰ change in δ187Re across a 14 m horizontal black shale weathering profile is accompanied by a hundred-fold decrease in Re concentration and a 75% decrease in organic carbon associated with the transition from reducing to oxic weathering environment. We attribute decreasing δ187Re to the loss of organically bound Re component (δ187Re = -0.28‰). The Re isotope composition of the complementary detrital silicate fraction varies from -0.59 to -1.5‰, depending on the choice of silicate Re concentration.

Anisotropic Failure Strength of Shale with Increasing Confinement: Behaviors, Factors and Mechanism.

PubMed

Cheng, Cheng; Li, Xiao; Qian, Haitao

2017-11-15

Some studies reported that the anisotropic failure strength of shale will be weakened by increasing confinement. In this paper, it is found that there are various types of anisotropic strength behaviors. Four types of anisotropic strength ratio ( S A 1 ) behaviors and three types of anisotropic strength difference ( S A 2 ) behaviors have been classified based on laboratory experiments on nine groups of different shale samples. The cohesion c w and friction angle ϕ w of the weak planes are proven to be two dominant factors according to a series of bonded-particle discrete element modelling analyses. It is observed that shale is more prone to a slight increase of S A 1 and significant increase of S A 2 with increasing confinement for higher cohesion c w and lower to medium friction angle ϕ w . This study also investigated the mechanism of the anisotropic strength behaviors with increasing confinement. Owing to different contributions of c w and ϕ w under different confinements, different combinations of c w and ϕ w may have various types of influences on the minimum failure strength with the increasing confinement; therefore, different types of anisotropic behaviors occur for different shale specimens as the confinement increases. These findings are very important to understand the stability of wellbore and underground tunneling in the shale rock mass, and should be helpful for further studies on hydraulic fracture propagations in the shale reservoir.

Empirically assessing the potential release of rare earth elements from black shale under simulated hydraulic fracturing conditions

DOE PAGES

Yang, Jon; Verba, Circe; Torres, Marta; ...

2018-02-01

Rare earth elements (REEs) are economically important to modern society and the rapid growth of technologies dependent on REEs has placed considerable economic pressure on their sourcing. This study addresses whether REEs could be released as a byproduct of natural gas extraction from a series of experiments that were designed to simulate hydraulic fracturing of black shale under various pressure (25 and 27.5 MPa) and temperature (50, 90, 130 °C) conditions. The dissolved REEs in the reacted fluids displayed no propensity for the REEs to be released from black shale under high pressure and temperature conditions, a result that ismore » consistent across the different types of fluids investigated. Overall, there was a net loss of REEs from the fluid. These changes in dissolved REEs were greatest at the moment the fluids first contacted the shale and before the high temperature and high pressure conditions were imposed, although the magnitude of these changes (10 -4 μg/g) were small compared to the magnitude of the total REE content present in the solid shale samples (10 2 μg/g). These results highlight the variability and complexity of hydraulic fracturing systems and indicate that REE may not serve as robust tracers for fracturing fluid-shale reactions. Additionally, the results suggest that significant quantities of REEs may not be byproducts of hydraulically fractured shales.« less

Empirically assessing the potential release of rare earth elements from black shale under simulated hydraulic fracturing conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jon; Verba, Circe; Torres, Marta

Rare earth elements (REEs) are economically important to modern society and the rapid growth of technologies dependent on REEs has placed considerable economic pressure on their sourcing. This study addresses whether REEs could be released as a byproduct of natural gas extraction from a series of experiments that were designed to simulate hydraulic fracturing of black shale under various pressure (25 and 27.5 MPa) and temperature (50, 90, 130 °C) conditions. The dissolved REEs in the reacted fluids displayed no propensity for the REEs to be released from black shale under high pressure and temperature conditions, a result that ismore » consistent across the different types of fluids investigated. Overall, there was a net loss of REEs from the fluid. These changes in dissolved REEs were greatest at the moment the fluids first contacted the shale and before the high temperature and high pressure conditions were imposed, although the magnitude of these changes (10 -4 μg/g) were small compared to the magnitude of the total REE content present in the solid shale samples (10 2 μg/g). These results highlight the variability and complexity of hydraulic fracturing systems and indicate that REE may not serve as robust tracers for fracturing fluid-shale reactions. Additionally, the results suggest that significant quantities of REEs may not be byproducts of hydraulically fractured shales.« less

Anisotropic Failure Strength of Shale with Increasing Confinement: Behaviors, Factors and Mechanism

PubMed Central

Cheng, Cheng; Li, Xiao; Qian, Haitao

2017-01-01

Some studies reported that the anisotropic failure strength of shale will be weakened by increasing confinement. In this paper, it is found that there are various types of anisotropic strength behaviors. Four types of anisotropic strength ratio (SA1) behaviors and three types of anisotropic strength difference (SA2) behaviors have been classified based on laboratory experiments on nine groups of different shale samples. The cohesion cw and friction angle ϕw of the weak planes are proven to be two dominant factors according to a series of bonded-particle discrete element modelling analyses. It is observed that shale is more prone to a slight increase of SA1 and significant increase of SA2 with increasing confinement for higher cohesion cw and lower to medium friction angle ϕw. This study also investigated the mechanism of the anisotropic strength behaviors with increasing confinement. Owing to different contributions of cw and ϕw under different confinements, different combinations of cw and ϕw may have various types of influences on the minimum failure strength with the increasing confinement; therefore, different types of anisotropic behaviors occur for different shale specimens as the confinement increases. These findings are very important to understand the stability of wellbore and underground tunneling in the shale rock mass, and should be helpful for further studies on hydraulic fracture propagations in the shale reservoir. PMID:29140292

Stratigraphy of the Silurian outcrop belt on the east side of the Cincinnati Arch in Kentucky, with revisions in the nomenclature

USGS Publications Warehouse

McDowell, Robert C.

1983-01-01

Silurian rocks form a narrow arcuate outcrop belt about 100 mi long on the east side of the Cincinnati Arch in Kentucky. They range from as much as 300 ft thick in the north to a pinchout edge in the south. The nomenclature of this sequence is revised to reflect mappability and lithologic uniformity on the basis of detailed mapping at a scale of 1:24,000 by the U.S. Geological Survey in cooperation with the Kentucky Geological Survey. The Silurian rocks are divided into two parts: the Crab Orchard Group, raised in rank from Crab Orchard Formation and redefined, in the lower part of the Silurian section, and Bisher Dolomite in the upper part of the section. The Crab Orchard Group is subdivided into the Drowning Creek Formation (new name) at the base of the Silurian, overlain by the Alger Shale (adopted herein) south of Fleming County and by the Estill Shale (elevated to formational rank) north of Bath County. The Brassfield Member (reduced in rank from Brassfield Dolomite or Formation) and the Plum Creek Shale and Oldham Members of the former Crab Orchard Formation are included as members of the Drowning Creek; the Lulbegrud Shale, Waco, and Estill Shale Members of the former Crab Orchard Formation are now included in the Alger. The Drowning Creek Formation, 20 to 50 ft thick, is composed mainly of gray fine to coarse-grained dolomite with shale interbeds. The dolomite beds average several inches thick, with bedding surfaces that are locally smooth but generally irregular and are fossiliferous in many places; fossils include brachiopods, crinoid columnals, horn corals, colonial corals, trilobites, pelecypods, and bryozoans. The shale interbeds average several inches thick, except for its Plum Creek Shale Member which is entirely shale and as much as 12 ft thick, and are most abundant in the upper half of the formation. The members of the Drowning Creek intergrade and are indistinguishable in the northern part of the area. The Alger Shale, as much as 170 feet thick, is predominantly grayish-green clay shale with a thin (0.5-3 ft) dolomite member (the Waco, or its northern equivalent, the Dayton Dolomite Member, reduced in rank from Dayton Limestone) near the base. North of Bath County, the Lulbegrud Shale and Dayton Dolomite Members are reassigned to the underlying Drowning Creek Formation, the Estill Shale Member is elevated to formational status, and the Alger is dropped. The Bisher Dolomite, which overlies the Estill Shale in the northernmost part of the Silurian belt, ranges from 0 to 300 ft in thickness and is composed of medium-to coarse-grained, gray, fossiliferous dolomite. The Silurian section overlies Upper Ordovician rocks in apparent conformity, although faunal studies suggest a minor hiatus, and is overlain by Middle to Upper Devonian rocks in a regional angular unconformity that truncates the entire Silurian section at the southwest end of the outcrop belt, where it is nearest the axis of the Cincinnati Arch. All of the units recognized in the Silurian appear to thicken eastward, away from the axis of the arch and towards the Appalachian basin. This, with the presence of isolated remnants of the Brassfield near the axis, suggest that formation of the arch was initiated in Early Silurian time by subsidence of its eastern flank.

Initial characterization of mudstone nanoporosity with small angle neutron scattering using caprocks from carbon sequestration sites.

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCray, John; Navarre-Sitchler, Alexis; Mouzakis, Katherine

Geological carbon sequestration relies on the principle that CO{sub 2} injected deep into the subsurface is unable to leak to the atmosphere. Structural trapping by a relatively impermeable caprock (often mudstone such as a shale) is the main trapping mechanism that is currently relied on for the first hundreds of years. Many of the pores of the caprock are of micrometer to nanometer scale. However, the distribution, geometry and volume of porosity at these scales are poorly characterized. Differences in pore shape and size can cause variation in capillary properties and fluid transport resulting in fluid pathways with different capillarymore » entry pressures in the same sample. Prediction of pore network properties for distinct geologic environments would result in significant advancement in our ability to model subsurface fluid flow. Specifically, prediction of fluid flow through caprocks of geologic CO{sub 2} sequestration reservoirs is a critical step in evaluating the risk of leakage to overlying aquifers. The micro- and nanoporosity was analyzed in four mudstones using small angle neutron scattering (SANS). These mudstones are caprocks of formations that are currently under study or being used for carbon sequestration projects and include the Marine Tuscaloosa Group, the Lower Tuscaloosa Group, the upper and lower shale members of the Kirtland Formation, and the Pennsylvanian Gothic shale. Total organic carbon varies from <0.3% to 4% by weight. Expandable clay contents range from 10% to {approx}40% in the Gothic shale and Kirtland Formation, respectively. Neutrons effectively scatter from interfaces between materials with differing scattering length density (i.e. minerals and pores). The intensity of scattered neutrons, I(Q), where Q is the scattering vector, gives information about the volume of pores and their arrangement in the sample. The slope of the scattering data when plotted as log I(Q) vs. log Q provides information about the fractality or geometry of the pore network. Results from this study, combined with high-resolution TEM imaging, provide insight into the differences in volume and geometry of porosity between these various mudstones.« less

Iridium contents in the Late Cretaceous-Early Tertiary clays in relation to the K/T boundary, North Jordan

NASA Astrophysics Data System (ADS)

Abboud, Iyad Ahmed

2016-06-01

The mineralogy, lithology, and geochemistry of five discrete laminations across the K/T boundary of clayey shale at the Yarmouk River area, Jordan, were examined. There were no marked changes in the mineralogy of the clayey shale within the K/T boundary. This outcrop consists of more than 100 m of Maastrichtian oil shale overlying about 20 m limestone. Marly limestone included many clay laminations from organic and volcanic origins, which are considered an evidence of the K/T boundary through detected iridium anomalies. Any of these particular lamellae range from 2 mm to 5 mm in thickness. Smectite was the predominant clay mineral in smectitic shale laminations. It was located at eight meters above the K/T boundary and includes some anomalous concentrations of iridium and traces of other elements. The analysis of geochemical platinum group at the K/T boundary clays showed anomalous enrichments of iridium, compared with other carbonate rocks as a result of weathering processes of oil shale, or through concentration from weathering of basalt flows, but not pointing to an impact process. The clays in late Maastrichtian have Ir-Sc prevailed anomalies and synchronize with increasing of terrigenous and volcanogenic traced elements. Kaolin, smectite, and volkonskoite were the dominant clay minerals at the K/T boundary with high concentrations of iridium. The concentration levels of iridium in some laminations of the Yarmouk sediments ranged between 1.6 and 7.8 ppb.

The Shale Gas potential of Lower Carboniferous Sediments in Germany

NASA Astrophysics Data System (ADS)

Kerschke, D.; Mihailovic, A.; Schulz, H., -M.; Horsfield, B.

2012-04-01

Organic-rich Carboniferous sediments are proven source rocks for conventional gas systems in NW Europe and are likely gas shale candidates. Within the framework of GeoEnergie, an initiative to strengthen scientific excellence, funded by the German Ministry of Education and Research (BMBF), the influence of palaeogeography and basin dynamics on sedimentology and diagenesis is being investigated. Our aim is to unravel the evolution of shale gas-relevant properties which control gas prospectivity and production parameters like porosity, brittleness, etc. for the Lower Carboniferous in Germany. Northern Germany is underlain by thick, mudstone-bearing Carboniferous successions with a wide range of thermal maturities. Some of these mudstone horizons are rich in organic carbon which is either of marine and/or terrigenous origin. During the Carboniferous deposition of fine-grained, TOC-rich basinal sediments changed into shallow marine to paralic siliciclastic sediments (carbonates during the Lower Carboniferous) in the north, and grade into coarse-grained sediments close to the uprising Variscan mountains in the south. As a result different architectural elements including TOC-rich fine-grained sediments like basinal shales, fine-grained parts of turbidites, and shallow marine mudstones occur in both the Lower and the Upper Carboniferous section. A high shale gas potential occurs in basinal shales of Namurian age with marine organic material and TOC contents of up to 8 % (Rhenish Alum Shales). Such sediments with thermal maturities between 1.3 to 3.0 % vitrinite reflectance and sufficient quartz contents occur in wide areas of present-day Central European Basins System (CEBS), and are at favourable depth for shale gas exploration predominantly along the southern CEBS margin.

Fracture patterns and their origin in the upper Devonian Antrim Shale gas reservoir of the Michigan basin; a review

USGS Publications Warehouse

Ryder, Robert T.

1996-01-01

INTRODUCTION: Black shale members of the Upper Devonian Antrim Shale are both the source and reservoir for a regional gas accumulation that presently extends across parts of six counties in the northern part of the Michigan basin (fig. 1). Natural fractures are considered by most petroleum geologists and oil and gas operators who work the Michigan basin to be a necessary condition for commercial gas production in the Antrim Shale. Fractures provide the conduits for free gas and associated water to flow to the borehole through the black shale which, otherwise, has a low matrix permeability. Moreover, the fractures assist in the release of gas adsorbed on mineral and(or) organic matter in the shale (Curtis, 1992). Depths to the gas-producing intervals (Norwood and Lachine Members) generally range from 1,200 to 1,800 ft (Oil and Gas Journal, 1994). Locally, wells that produce gas from the accumulation are as deep as 2,200 (Oil and Gas Journal, 1994). Even though natural fractures are an important control on Antrim Shale gas production, most wells require stimulation by hydraulic fracturing to attain commercial production rates (Kelly, 1992). In the U.S. Geological Survey's National Assessment of United States oil and gas, Dolton (1995) estimates that, at a mean value, 4.45 trillion cubic feet (TCF) of gas are recoverable as additions to already discovered quantities from the Antrim Shale in the productive area of the northern Michigan trend. Dolton (1995) also suggests that undiscovered Antrim Shale gas accumulations exist in other parts of the Michigan basin. The character, distribution, and origin of natural fractures in the Antrim Shale gas accumulation have been studied recently by academia and industry. The intent of these investigations is to: 1) predict 'sweet spots', prior to drilling, in the existing gas-producing trend, 2) improve production practices in the existing trend, 3) predict analogous fracture-controlled gas accumulations in other parts of the Michigan basin, and 4) improve estimates of the recoverable gas in the Antrim Shale gas plays (Dolton, 1995). This review of published literature on the characteristics of Antrim Shale fractures, their origin, and their controls on gas production will help to define objectives and goals in future U.S. Geological Survey studies of Antrim Shale gas resources.

Variability of oil and gas well productivities for continuous (unconventional) petroleum accumulations

USGS Publications Warehouse

Charpentier, Ronald R.; Cook, Troy A.

2013-01-01

Over the last decade, oil and gas well productivities were estimated using decline-curve analysis for thousands of wells as part of U.S. Geological Survey (USGS) studies of continuous (unconventional) oil and gas resources in the United States. The estimated ultimate recoveries (EURs) of these wells show great variability that was analyzed at three scales: within an assessment unit (AU), among AUs of similar reservoir type, and among groups of AUs with different reservoir types. Within a particular oil or gas AU (such as the Barnett Shale), EURs vary by about two orders of magnitude between the most productive wells and the least productive ones (excluding those that are dry and abandoned). The distributions of EURs are highly skewed, with most of the wells in the lower part of the range. Continuous AUs were divided into four categories based on reservoir type and major commodity (oil or gas): coalbed gas, shale gas, other low-permeability gas AUs (such as tight sands), and low-permeability oil AUs. Within each of these categories, there is great variability from AU to AU, as shown by plots of multiple EUR distributions. Comparing the means of each distribution within a category shows that the means themselves have a skewed distribution, with a range of approximately one to two orders of magnitude. A comparison of the three gas categories (coalbed gas, shale gas, and other low-permeability gas AUs) shows large overlap in the ranges of EUR distributions. Generally, coalbed gas AUs have lower EUR distributions, shale gas AUs have intermediate sizes, and the other low-permeability gas AUs have higher EUR distributions. The plot of EUR distributions for each category shows the range of variation among developed AUs in an appropriate context for viewing the historical development within a particular AU. The Barnett Shale is used as an example to demonstrate that dividing wells into groups by time allows one to see the changes in EUR distribution. Subdivision into groups can also be done by vertical versus horizontal wells, by length of horizontal completion, by distance to closest previously drilled well, by thickness of reservoir interval, or by any other variable for which one has or can calculate values for each well. The resulting plots show how one can subdivide the total range of productivity in shale-gas wells into smaller subsets that are more appropriate for use as analogs.

Undiscovered petroleum resources for the Woodford Shale and Thirteen Finger Limestone-Atoka Shale assessment units, Anadarko Basin

USGS Publications Warehouse

Higley, Debra K.

2011-01-01

In 2010 the U.S. Geological Survey assessed undiscovered oil and gas resources for the Anadarko Basin Province of Colorado, Kansas, Oklahoma, and Texas. The assessment included three continuous (unconventional) assessment units (AU). Mean undiscovered resources for the (1) Devonian Woodford Shale Gas AU are about 16 trillion cubic feet of gas (TCFG) and 192 million barrels of natural gas liquids (MMBNGL), (2) Woodford Shale Oil AU are 393 million barrels of oil (MMBO), 2 TCFG, and 59 MMBNGL, and (3) Pennsylvanian Thirteen Finger Limestone-Atoka Shale Gas AU are 6.8 TCFG and 82 MMBNGL. The continuous gas AUs are mature for gas generation within the deep basin of Oklahoma and Texas. Gas generation from the Woodford Shale source rock started about 335 Ma, and from the Thirteen Finger Limestone-Atoka Shale AU about 300 Ma. Maturation results are based on vitrinite reflectance data, and on 1D and 4D petroleum system models that calculated vitrinite reflectance (Ro), and Rock-Eval and hydrous pyrolysis transformation (HP) ratios through time for petroleum source rocks. The Woodford Shale Gas AU boundary and sweet spot were defined mainly on (1) isopach thickness from well-log analysis and published sources; (2) estimated ultimate recoverable production from existing, mainly horizontal, wells; and (3) levels of thermal maturation. Measured and modeled Ro ranges from about 1.2% to 5% in the AU, which represents marginally mature to overmature for gas generation. The sweet spot included most of the Woodford that was deposited within eroded channels in the unconformably underlying Hunton Group. The Thirteen Finger Limestone-Atoka Shale Gas AU has no known production in the deep basin. This AU boundary is based primarily on the gas generation window, and on thickness and distribution of organic-rich facies from these mainly thin shale and limestone beds. Estimates of organic richness were based on well-log signatures and published data.

Reconnaissance for uranium in the coal of Sao Paulo, Santa Catarina, and Rio Grande do Sul, Brazil

USGS Publications Warehouse

Haynes, Donald D.; Pierson, Charles T.; White, Max G.

1958-01-01

Uranium-bearing coal and carbonaceous shale of the Rio Bonito formation of Pennsylvanian age have been found in the States of Sao Paulo, Santa Catarlna and Rio Grande do Sul, Brazil. The uranium oxide content of the samples collected in the State of Sao Paulo ranges from 0.001 percent to 0.082 percent. The samples collected in Santa Catarina averaged about 0.002 percent uranium oxide; those collected in Rio Grande do Sul, about 0.003 percent uranium oxide. Since the field and laboratory investigations are still in their initial stages, only raw data on the radioactivity and uranium content of Brazilian coals are given in this report.

Radionuclide concentration variations in the fuel and residues of oil shale-fired power plants: Estimations of the radiological characteristics over a 2-year period.

PubMed

Vaasma, Taavi; Loosaar, Jüri; Kiisk, Madis; Tkaczyk, Alan Henry

2017-07-01

Several multi-day samplings were conducted over a 2-year period from an oil shale-fired power plant operating with pulverized fuel type of boilers that were equipped with either novel integrated desulphurization system and bag filters or with electrostatic precipitators. Oil shale, bottom ash and fly ash samples were collected and radionuclides from the 238 U and 232 Th series as well as 40 K were determined. The work aimed at determining possible variations in the concentrations of naturally occurring radionuclides within the collected samples and detect the sources of these fluctuations. During the continuous multi-day samplings, various boiler parameters were recorded as well. With couple of exceptions, no statistically significant differences were detected (significance level 0.05) between the measured radionuclide mean values in various ash samples within the same sampling. When comparing the results between multiple years and samplings, no statistically significant variations were observed between 238 U and 226 Ra values. However, there were significant differences between the values in the fly ashes when comparing 210 Pb, 40 K, 228 Ra and 232 Th values between the various samplings. In all cases the radionuclide activity concentrations in the specific fly ash remained under 100 Bq kg -1 , posing no radiological concerns when using this material as an additive in construction or building materials. Correlation analysis between the registered boiler parameters and measured radionuclide activity concentrations showed weak or no correlation. The obtained results suggest that the main sources of variations are due to the characteristics of the used fuel. The changes in the radionuclide activity concentrations between multiple years were in general rather modest. The radionuclide activity concentrations varied dominantly between 4% and 15% from the measured mean within the same sampling. The relative standard deviation was however within the same range as the relative measurement uncertainty, suggesting that the main component of fluctuations is derived from the measurement method and approach. The obtained results indicate that representativeness of the data over a longer time period is valid only when a fuel with a similar composition is used and when the combustion boilers operate with a uniform setup (same boiler type and purification system). The results and the accompanying statistical analysis clearly demonstrated that in order to obtain data with higher reliability, a repeated multi-day sampling should be organized and combined with the registered boiler technical and operational parameters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quantification of Organic richness through wireline logs: a case study of Roseneath shale formation, Cooper basin, Australia

NASA Astrophysics Data System (ADS)

Ahmad, Maqsood; Iqbal, Omer; Kadir, Askury Abd

2017-10-01

The late Carboniferous-Middle Triassic, intracratonic Cooper basin in northeastern South Australia and southwestern Queensland is Australia's foremost onshore hydrocarbon producing region. The basin compromises Permian carbonaceous shale like lacustrine Roseneath and Murteree shale formation which is acting as source and reservoir rock. The source rock can be distinguished from non-source intervals by lower density, higher transit time, higher gamma ray values, higher porosity and resistivity with increasing organic content. In current dissertation we have attempted to compare the different empirical approaches based on density relation and Δ LogR method through three overlays of sonic/resistivity, neutron/resistivity and density/resistivity to quantify Total organic content (TOC) of Permian lacustrine Roseneath shale formation using open hole wireline log data (DEN, GR, CNL, LLD) of Encounter 1 well. The TOC calculated from fourteen density relations at depth interval between 3174.5-3369 meters is averaged 0.56% while TOC from sonic/resistivity, neutron/resistivity and density/resistivity yielded an average value of 3.84%, 3.68%, 4.40%. The TOC from average of three overlay method is yielded to 3.98%. According to geochemical report in PIRSA the Roseneath shale formation has TOC from 1 - 5 wt %.There is unpromising correlations observed for calculated TOC from fourteen density relations and measured TOC on samples. The TOC from average value of three overlays using Δ LogR method showed good correlation with measured TOC on samples.

A comprehensive method for the fracability evaluation of shale combined with brittleness and stress sensitivity

NASA Astrophysics Data System (ADS)

Wang, Xiaoqiong; Ge, Hongkui; Wang, Daobing; Wang, Jianbo; Chen, Hao

2017-12-01

An effective fracability evaluation on the fracture network is key to the whole process of shale gas exploitation. At present, neither a standard criteria nor a generally accepted evaluation method exist. Well log and laboratory results have shown that the commonly used brittleness index calculated from the mineralogy composition is not entirely consistent with that obtained from the elastic modulus of the rock, and is sometimes even contradictory. The brittle mineral reflects the brittleness of the rock matrix, and the stress sensitivity of the wave velocity reflects the development degree of the natural fracture system. They are both key factors in controlling the propagating fracture morphology. Thus, in this study, a novel fracability evaluation method of shale was developed combining brittleness and stress sensitivity. Based on this method, the fracability of three shale gas plays were evaluated. The cored cylindrical samples were loaded under uniaxial stress up to 30 MPa and the compressional wave velocities were obtained along the axis stress direction at each MPa stress. From the stress velocity evolution, the stress sensitivity coefficients could be obtained. Our results showed that the fracability of Niutitang shale is better than that of Lujiaping shale, and the fracability of Lujiaping shale is better than Longmaxi shale. This result is in good agreement with acoustic emission activity measurements. The new fracability evaluation method enables a comprehensive reflection of the characteristics of rock matrix brittleness and the natural fracture system. This work is valuable for the evaluation of hydraulic fracturing effects in unconventional oil and gas reservoirs in the future.

Water Saturation Relations and Their Diffusion-Limited Equilibration in Gas Shale: Implications for Gas Flow in Unconventional Reservoirs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tokunaga, Tetsu K.; Shen, Weijun; Wan, Jiamin

Large volumes of water are used for hydraulic fracturing of low permeability shale reservoirs to stimulate gas production, with most of the water remaining unrecovered and distributed in a poorly understood manner within stimulated regions. Because water partitioning into shale pores controls gas release, we measured the water saturation dependence on relative humidity (rh) and capillary pressure (P c) for imbibition (adsorption) as well as drainage (desorption) on samples of Woodford Shale. Experiments and modeling of water vapor adsorption into shale laminae at rh = 0.31 demonstrated that long times are needed to characterize equilibrium in larger (5 mm thick)more » pieces of shales, and yielded effective diffusion coefficients from 9 × 10 -9 to 3 × 10 -8 m 2 s -1, similar in magnitude to the literature values for typical low porosity and low permeability rocks. Most of the experiments, conducted at 50°C on crushed shale grains in order to facilitate rapid equilibration, showed significant saturation hysteresis, and that very large P c (~1 MPa) are required to drain the shales. These results quantify the severity of the water blocking problem, and suggest that gas production from unconventional reservoirs is largely associated with stimulated regions that have had little or no exposure to injected water. Finally, gravity drainage of water from fractures residing above horizontal wells reconciles gas production in the presence of largely unrecovered injected water, and is discussed in the broader context of unsaturated flow in fractures.« less

Water Saturation Relations and Their Diffusion-Limited Equilibration in Gas Shale: Implications for Gas Flow in Unconventional Reservoirs

DOE PAGES

Tokunaga, Tetsu K.; Shen, Weijun; Wan, Jiamin; ...

2017-11-15

Large volumes of water are used for hydraulic fracturing of low permeability shale reservoirs to stimulate gas production, with most of the water remaining unrecovered and distributed in a poorly understood manner within stimulated regions. Because water partitioning into shale pores controls gas release, we measured the water saturation dependence on relative humidity (rh) and capillary pressure (P c) for imbibition (adsorption) as well as drainage (desorption) on samples of Woodford Shale. Experiments and modeling of water vapor adsorption into shale laminae at rh = 0.31 demonstrated that long times are needed to characterize equilibrium in larger (5 mm thick)more » pieces of shales, and yielded effective diffusion coefficients from 9 × 10 -9 to 3 × 10 -8 m 2 s -1, similar in magnitude to the literature values for typical low porosity and low permeability rocks. Most of the experiments, conducted at 50°C on crushed shale grains in order to facilitate rapid equilibration, showed significant saturation hysteresis, and that very large P c (~1 MPa) are required to drain the shales. These results quantify the severity of the water blocking problem, and suggest that gas production from unconventional reservoirs is largely associated with stimulated regions that have had little or no exposure to injected water. Finally, gravity drainage of water from fractures residing above horizontal wells reconciles gas production in the presence of largely unrecovered injected water, and is discussed in the broader context of unsaturated flow in fractures.« less

Oil-source correlations between the Mississippian Heath Shales and the reservoired oils in the Pennsylvanian Tyler Sands, Montana

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cole, G.A.; Drozd, R.J.; Daniel, J.A.

The Mississippi Heath Formation exposed in Fergus County, central Montana, is comprised predominantly of nearshore, marine, black, calcareous shales and carbonates with minor anhydrite and coal beds. The black shales and limestones have been considered as sources for shale oil via Fischer Assay and pyrolysis analysis. These shales are potential source units for the oils reservoired in the overlying Pennsylvanian Tyler Formation sands located 50 mi (80 km) to the east of the Fergus County Heath sediment studied. Heath Formation rocks from core holes were selectively sampled in 2-ft increments and analyzed for their source rock characteristics. Analyses include percentmore » total organic carbon (%TOC), Rock-Eval pyrolysis, pyrolysis-gas chromatography, and characterization of the total soluble extracts using carbon isotopes and gas chromatography-mass Spectrometry. Results indicated that the Heath was an excellent potential source unit that contained oil-prone, organic-rich (maximum of 17.6% TOC), calcareous, black shale intervals. The Heath and Tyler formations also contained intervals dominated by gas-prone, organic-rich shales of terrestrial origin. Three oils from the Tyler Formation sands in Musselshell and Rosebud counties were characterized by similar methods as the extracts. The oils were normally mature, moderate API gravity, moderate sulfur, low asphaltene crudes. Oil to source correlations between the Heath shale extracts and the oils indicated the Heath was an excellent candidate source rock for the Tyler reservoired oils. Conclusions were based on excellent matches between the carbon isotopes of the oils and the kerogen-kerogen pyrolyzates, and from the biomarkers.« less

Continuously increasing δ98Mo values in Neoarchean black shales and iron formations from the Hamersley Basin

NASA Astrophysics Data System (ADS)

Kurzweil, Florian; Wille, Martin; Schoenberg, Ronny; Taubald, Heinrich; Van Kranendonk, Martin J.

2015-09-01

We present Mo-, C- and O-isotope data from black shales, carbonate- and oxide facies iron formations from the Hamersley Group, Western Australia, that range in age from 2.6 to 2.5 billion years. The data show a continuous increase from near crustal δ98Mo values of around 0.50‰ for the oldest Marra Mamba and Wittenoom formations towards higher values of up to 1.51‰ for the youngest sample of the Brockman Iron Formation. Thereby, the trend in increasing δ98Mo values is portrayed by both carbonate facies iron formations and black shales. Considering the positive correlation between Mo concentration and total organic carbon, we argue that this uniformity is best explained by molybdate adsorption onto organic matter in carbonate iron formations and scavenging of thiomolybdate onto sulfurized organic matter in black shales. A temporal increase in the seawater δ98Mo over the period 2.6-2.5 Ga is observed assuming an overall low Mo isotope fractionation during both Mo removal processes. Oxide facies iron formations show lowest Mo concentrations, lowest total organic carbon and slightly lower δ98Mo compared to nearly contemporaneous black shales. This may indicate that in iron formation settings with very low organic matter burial rates, the preferential adsorption of light Mo isotopes onto Fe-(oxyhydr)oxides becomes more relevant. A similar Mo-isotope pattern was previously found in contemporaneous black shales and carbonates of the Griqualand West Basin, South Africa. The consistent and concomitant increase in δ98Mo after 2.54 billion years ago suggests a more homogenous distribution of seawater molybdate with uniform isotopic composition in various depositional settings within the Hamersley Basin and the Griqualand West Basin. The modeling of the oceanic Mo inventory in relation to the Mo in- and outflux suggests that the long-term build-up of an isotopically heavy seawater Mo reservoir requires a sedimentary sink for isotopically light Mo. The search for this sink (i.e. adsorption onto Mn-oxides in well oxygenated surface oceans and/or subaerial environments or incomplete thiomolybdate formation in weakly sulfidic settings) remains debated, but its relevance becomes more important closer to the Great Oxidation Event and is probably related to already weakly oxidizing conditions even prior to the 2.5 Ga "whiff of oxygen".

Methane and benzene in drinking-water wells overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas

USGS Publications Warehouse

McMahon, Peter B.; Barlow, Jeannie R.; Engle, Mark A.; Belitz, Kenneth; Ging, Patricia B.; Hunt, Andrew G.; Jurgens, Bryant; Kharaka, Yousif K.; Tollett, Roland W.; Kresse, Timothy M.

2017-01-01

Water wells (n = 116) overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas were sampled for chemical, isotopic, and groundwater-age tracers to investigate the occurrence and sources of selected hydrocarbons in groundwater. Methane isotopes and hydrocarbon gas compositions indicate most of the methane in the wells was biogenic and produced by the CO2 reduction pathway, not from thermogenic shale gas. Two samples contained methane from the fermentation pathway that could be associated with hydrocarbon degradation based on their co-occurrence with hydrocarbons such as ethylbenzene and butane. Benzene was detected at low concentrations (<0.15 μg/L), but relatively high frequencies (2.4–13.3% of samples), in the study areas. Eight of nine samples containing benzene had groundwater ages >2500 years, indicating the benzene was from subsurface sources such as natural hydrocarbon migration or leaking hydrocarbon wells. One sample contained benzene that could be from a surface release associated with hydrocarbon production activities based on its age (10 ± 2.4 years) and proximity to hydrocarbon wells. Groundwater travel times inferred from the age-data indicate decades or longer may be needed to fully assess the effects of potential subsurface and surface releases of hydrocarbons on the wells.

Methane and Benzene in Drinking-Water Wells Overlying the Eagle Ford, Fayetteville, and Haynesville Shale Hydrocarbon Production Areas.

PubMed

McMahon, Peter B; Barlow, Jeannie R B; Engle, Mark A; Belitz, Kenneth; Ging, Patricia B; Hunt, Andrew G; Jurgens, Bryant C; Kharaka, Yousif K; Tollett, Roland W; Kresse, Timothy M

2017-06-20

Water wells (n = 116) overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas were sampled for chemical, isotopic, and groundwater-age tracers to investigate the occurrence and sources of selected hydrocarbons in groundwater. Methane isotopes and hydrocarbon gas compositions indicate most of the methane in the wells was biogenic and produced by the CO 2 reduction pathway, not from thermogenic shale gas. Two samples contained methane from the fermentation pathway that could be associated with hydrocarbon degradation based on their co-occurrence with hydrocarbons such as ethylbenzene and butane. Benzene was detected at low concentrations (<0.15 μg/L), but relatively high frequencies (2.4-13.3% of samples), in the study areas. Eight of nine samples containing benzene had groundwater ages >2500 years, indicating the benzene was from subsurface sources such as natural hydrocarbon migration or leaking hydrocarbon wells. One sample contained benzene that could be from a surface release associated with hydrocarbon production activities based on its age (10 ± 2.4 years) and proximity to hydrocarbon wells. Groundwater travel times inferred from the age-data indicate decades or longer may be needed to fully assess the effects of potential subsurface and surface releases of hydrocarbons on the wells.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barber, A.J.; Tjokrosapoetro, S.; Charlton, T.R.

In Timor, eastern Indonesia, where the northern margin of the Australian continent is colliding with the Banda Arc, Australian continental margin sediments are being incorporated into an imbricate wedge, which passes northward into a foreland fold and thrust belt. Field mapping in Timor has shown that scale clays, containing irregularly shaped or phacoidal blocks (up to several meters long) and composed of a wide range of lithologies derived from local stratigraphic units, occur in three environments: along wrench faults, as crosscutting shale diapirs, and associated with mud volcanoes. A model is proposed linking these phenomena. Shales become overpressured as amore » result of overthrusting; this overpressure is released along vertical wrench faults, which cut through the overthrust units; overpressured shales containing blocks of consolidated units rise along the fault zones as shale diapirs; and escaping water, oil, and gas construct mud volcanoes at the surface. 6 figures, 1 table.« less

Fracking in Tight Shales: What Is It, What Does It Accomplish, and What Are Its Consequences?

NASA Astrophysics Data System (ADS)

Norris, J. Quinn; Turcotte, Donald L.; Moores, Eldridge M.; Brodsky, Emily E.; Rundle, John B.

2016-06-01

Fracking is a popular term referring to hydraulic fracturing when it is used to extract hydrocarbons. We distinguish between low-volume traditional fracking and the high-volume modern fracking used to recover large volumes of hydrocarbons from shales. Shales are fine-grained rocks with low granular permeabilities. During the formation of oil and gas, large fluid pressures are generated. These pressures result in natural fracking, and the resulting fracture permeability allows oil and gas to escape, reducing the fluid pressures. These fractures may subsequently be sealed by mineral deposition, resulting in tight shale formations. The objective of modern fracking is to reopen these fractures and/or create new fractures on a wide range of scales. Modern fracking has had a major impact on the availability of oil and gas globally; however, there are serious environmental objections to modern fracking, which should be weighed carefully against its benefits.

Hydrogeology and results of aquifer tests in the vicinity of a hazardous-waste disposal site near Byron, Illinois

USGS Publications Warehouse

Kay, Robert T.; Olson, David N.; Ryan, Barbara J.

1989-01-01

The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, conducted an investigation of a Superfund Site near Byron, Illinois. The purpose of the investigation was to determine the hydrogeologic properties of the Galena-Platteville and St. Peter aquifers, the primary water-supply aquifers for domestic supply in the area. The Galena and Platteville Groups and older St. Peter Sandstone are separated by the Harmony Hill Shale Member of the Glenwood Formation. The Harmony Hill Shale Member is a semiconfining unit. Groundwater flow in the study area is from the site northwestward to the Rock River. Movement of groundwater in the dolomites is mainly through joints, fractures, and solution openings. Analysis of the Galena-Platteville aquifer-test data indicates that the calculated aquifer transmissivity ranges from 490 to 670 sq ft/day, and the calculated specific yield ranges from 0.017 to 0.140. Aquifer test data also indicate that the Galena-Platteville aquifer is heterogeneous and anisotropic. Analysis of the St. Peter aquifer-test data indicates that the calculated transmissivity of the aquifer ranges from 1,200 to 1 ,305 sq ft/day, storativity ranges from 0.000528 to 0.00128, horizontal hydraulic conductivity ranges from 2.9 to 3.1 ft/day, and leakage through the Harmony Hill Shale Member ranges from .000123 to .000217 ft/day/ft. (USGS)

Pacific Enewetak Atoll Crater Exploration (PEACE) program, Enewetak Atoll, Republic of the Marshall Islands; Part 1, Drilling operations and descriptions of boreholes in vicinity of KOA and OAK craters

USGS Publications Warehouse

Henry, T.W.; Wardlaw, B.R.; Skipp, Betty; Major, R. P.; Tracey, J.I.

1986-01-01

Evidence of a post-Cretaceous uplift of the Sioux Quartzite ridge in southeastern South Dakota consists of deformation of the Dakota Formation, Graneros Shale, Greenhorn Limestone, Carlile Shale, and Niobrara Formation of Cretaceous age. The Greenhorn is warped upward about 400 ft on the Sioux Quartzite with a formation dip ranging from 30-50 ft/mi. Elsewhere in eastern South Dakota the dip of the Greenhorn ranges from 3-8 ft/mi. (Author 's abstract)

Life cycle carbon footprint of shale gas: review of evidence and implications.

PubMed

Weber, Christopher L; Clavin, Christopher

2012-06-05

The recent increase in the production of natural gas from shale deposits has significantly changed energy outlooks in both the US and world. Shale gas may have important climate benefits if it displaces more carbon-intensive oil or coal, but recent attention has discussed the potential for upstream methane emissions to counteract this reduced combustion greenhouse gas emissions. We examine six recent studies to produce a Monte Carlo uncertainty analysis of the carbon footprint of both shale and conventional natural gas production. The results show that the most likely upstream carbon footprints of these types of natural gas production are largely similar, with overlapping 95% uncertainty ranges of 11.0-21.0 g CO(2)e/MJ(LHV) for shale gas and 12.4-19.5 g CO(2)e/MJ(LHV) for conventional gas. However, because this upstream footprint represents less than 25% of the total carbon footprint of gas, the efficiency of producing heat, electricity, transportation services, or other function is of equal or greater importance when identifying emission reduction opportunities. Better data are needed to reduce the uncertainty in natural gas's carbon footprint, but understanding system-level climate impacts of shale gas, through shifts in national and global energy markets, may be more important and requires more detailed energy and economic systems assessments.

Release of Particulate Iron Sulfide during Shale-Fluid Interaction.

PubMed

Kreisserman, Yevgeny; Emmanuel, Simon

2018-01-16

During hydraulic fracturing, a technique often used to extract hydrocarbons from shales, large volumes of water are injected into the subsurface. Although the injected fluid typically contains various reagents, it can become further contaminated by interaction with minerals present in the rocks. Pyrite, which is common in organic-rich shales, is a potential source of toxic elements, including arsenic and lead, and it is generally thought that for these elements to become mobilized, pyrite must first dissolve. Here, we use atomic force microscopy and environmental scanning electron microscopy to show that during fluid-rock interaction, the dissolution of carbonate minerals in Eagle Ford shale leads to the physical detachment, and mobilization, of embedded pyrite grains. In experiments carried out over a range of pH, salinity, and temperature we found that in all cases pyrite particles became detached from the shale surfaces. On average, the amount of pyrite detached was equivalent to 6.5 × 10 -11 mol m -2 s -1 , which is over an order of magnitude greater than the rate of pyrite oxidation expected under similar conditions. This result suggests that mechanical detachment of pyrite grains could be an important pathway for the mobilization of arsenic in hydraulic fracturing operations and in groundwater systems containing shales.

Converting oil shale to liquid fuels: energy inputs and greenhouse gas emissions of the Shell in situ conversion process.

PubMed

Brandt, Adam R

2008-10-01

Oil shale is a sedimentary rock that contains kerogen, a fossil organic material. Kerogen can be heated to produce oil and gas (retorted). This has traditionally been a CO2-intensive process. In this paper, the Shell in situ conversion process (ICP), which is a novel method of retorting oil shale in place, is analyzed. The ICP utilizes electricity to heat the underground shale over a period of 2 years. Hydrocarbons are produced using conventional oil production techniques, leaving shale oil coke within the formation. The energy inputs and outputs from the ICP, as applied to oil shales of the Green River formation, are modeled. Using these energy inputs, the greenhouse gas (GHG) emissions from the ICP are calculated and are compared to emissions from conventional petroleum. Energy outputs (as refined liquid fuel) are 1.2-1.6 times greater than the total primary energy inputs to the process. In the absence of capturing CO2 generated from electricity produced to fuel the process, well-to-pump GHG emissions are in the range of 30.6-37.1 grams of carbon equivalent per megajoule of liquid fuel produced. These full-fuel-cycle emissions are 21%-47% larger than those from conventionally produced petroleum-based fuels.

Using SEM Analysis on Ion-Milled Shale Surface to Determine Shale-Fracturing Fluid Interaction

NASA Astrophysics Data System (ADS)

Lu, J.; Mickler, P. J.; Nicot, J. P.

2014-12-01

It is important to document and assess shale-fluid interaction during hydraulic fracturing (HF) in order to understand its impact on flowback water chemistry and rock property. A series of autoclave experiments were conducted to react shale samples from major oil and gas shales with synthetic HF containing various additives. To better determine mineral dissolution and precipitation at the rock-fluid interface, ion-milling technique was applied to create extremely flat rock surfaces that were examined before and after the autoclave experiments using a scanning electron microscope (SEM) coupled with energy dispersive spectroscopy (EDS) detectors. This method is able to reveal a level of detail not observable on broken surface or mechanically polished surface. It allows direct comparison of the same mineral and organic matter particles before and after the reaction experiments. Minerals undergone dissolution and newly precipitated materials are readily determined by comparing to the exact locations before reaction. The dissolution porosity and the thickness of precipitates can be quantified by tracing and measuring the geometry of the pores and precipitates. Changes in porosity and permeability were confirmed by mercury intrusion capillary tests.

The first data on the porous space structure of the Domanik shales as a potential object for EOR applying

NASA Astrophysics Data System (ADS)

Kadyrov, R.; Statsenko, E.

2018-05-01

The resources of shale oil, contained in the organic matter of the wood deposits, can be considered as a source of profitable production of hydrocarbons, when modern EOR technologies are used. As a result of the primary studies of the pore space structure, it is revealed that two types of porous space are prevailing in the studied samples of the Domanik oil shales. The most prevailing is intrakerogen porosity with pore volumes of 5 × 10-8 1 × 10-6 mm3. The volumetric reconstruction of the structure of this pore space shows that the voids are confined directly to micro lenses of organic matter. The second type of the found void is represented by leaching cracks. It is characteristic of more carbonate varieties of the Dominik oil shale with spotted structure. It is the oil shale intervals with such cracks that are of greatest interest to the EOR, since they consist of a large area with smaller pores and through which pressurization and spread of various agents are possible to occur in order to increase the oil recovery.

Quality of ground water in Routt County, northwestern Colorado

USGS Publications Warehouse

Covay, Kenneth J.; Tobin, R.L.

1980-01-01

Chemical and bacteriological data were collected to describe the quality of water from selected geologic units in Routt County, Colo. Calcium bicarbonate was the dominant water-chemistry type; magnesium, sodium, and sulfate frequently occurred as codominant ions. Specific conductance values ranged from 50 to 6,000 micromhos. Mean values of specific conductance, dissolved solids , and hardness from the sampled aquifers were generally greatest in waters from the older sedimentary rocks of the Lance Formation, Lewis Shale, Mesaverde Group, and Mancos Shale, and least in the ground waters from the alluvial deposits, Browns Park Formation, and the basement complex. Correlations of specific conductance with dissolved solids and specific conductance with hardness were found within specified concentration ranges. On the basis of water-quality analyses, water from the alluvial desposits, Browns Park Formation, and the basement complex generally is the most suitable for domestic uses. Chemical constituents in water from wells or springs exceeded State and Federal standards for public-water supplies or State criteria for agricultural uses were pH, arsenic, boron, chloride, iron, fluoride, manganese, nitrite plus nitrate, selenium, sulfate, or dissolved solids. Total-coliform bacteria were detected in water from 29 sites and fecal-coliform bacteria were detected in water from 6 of the 29 sites. (USGS)

Subcritical fracturing of shales under chemically reactive conditions

NASA Astrophysics Data System (ADS)

Chen, X.; Callahan, O. A.; Eichhubl, P.; Olson, J. E.

2016-12-01

Growth of opening-mode fractures under chemically reactive subsurface conditions is potentially relevant for seal integrity in subsurface CO2 storage and hazardous waste disposal. Using double-torsion load relaxation tests we determine mode-I fracture toughness (KIC), subcritical index (SCI), and the stress-intensity factor vs fracture velocity (K-V) behavior of Marcellus, Woodford, and Mancos shales. Samples are tested under ambient air and aqueous conditions with variable NaCl and KCl concentrations, variable pH, and temperatures of up to 70. Under ambient air condition, KIC determined from double torsion tests is 1.3, 0.6, and 1.1 MPam1/2 for Marcellus, Woodford, and Mancos shales, respectively. SCI under ambient air condition is between 55 and 90 for the shales tested. Tests in aqueous solutions show a significant drop of KIC compared to ambient air condition. For tests in deionized water, KIC reduction is 18.5% for Marcellus and 47.0% for Woodford. The presence of aqueous fluids also results in a reduction of the SCI up to 85% compared to ambient condition. K-V curves generally obey a power-law relation throughout the load-relaxation period. However, aqueous-based tests on samples result in K-V curves deviating from the power-law relation, with the SCI values gradually decreasing with time during the relaxation period. This non-power-law behavior is obvious in Woodford and Mancos, but negligible in Marcellus. We find that the shales interact with the aqueous solution both at the fracture tip and within the rock matrix during subcritical fracturing. For Marcellus shale, water mainly interacts with the fracture tip on both tests due to low matrix permeability and less reactive mineral composition. However, Woodford and Mancos react strongly with water causing significant sample degradation. The competition between degradation and fracture growth results in the time-dependent SCI: at lower fracture velocities, the tip interacts longer with the chemically altered area around the tip; at higher fracture velocities, the fracture propagates through the altered area before significant degradation. Our results display strong weakening effects of chemically reactive fluids on subcritical fracture properties with implications on subsurface storage seal performance.

Applying Data Mining Techniques to Chemical Analyses of Pre-drill Groundwater Samples within the Marcellus Formation Shale Play in Bradford County, Pennsylvania

NASA Astrophysics Data System (ADS)

Wen, T.; Niu, X.; Gonzales, M. S.; Li, Z.; Brantley, S.

2017-12-01

Groundwater samples are collected for chemical analyses by shale gas industry consultants in the vicinity of proposed gas wells in Pennsylvania. These data sets are archived so that the chemistry of water from homeowner wells can be compared to chemistry after gas-well drilling. Improved public awareness of groundwater quality issues will contribute to designing strategies for both water resource management and hydrocarbon exploration. We have received water analyses for 11,000 groundwater samples from PA Department of Environmental Protection (PA DEP) in the Marcellus Shale footprint in Bradford County, PA for the years ranging from 2010 to 2016. The PA DEP has investigated these analyses to determine whether gas well drilling or other activities affected water quality. We are currently investigating these analyses to look for patterns in chemistry throughout the study area (related or unrelated to gas drilling activities) and to look for evidence of analytes that may be present at concentrations higher than the advised standards for drinking water. Our preliminary results reveal that dissolved methane concentrations tend to be higher along fault lines in Bradford County [1]. Lead (Pb), arsenic (As), and barium (Ba) are sometimes present at levels above the EPA maximum contaminant level (MCL). Iron (Fe) and manganese (Mn) more frequently violate the EPA standard. We find that concentrations of some chemical analytes (e.g., Ba and Mn) are dependent on bedrock formations (i.e., Catskill vs. Lock Haven) while concentrations of other analytes (e.g., Pb) are not statistically significantly distinct between different bedrock formations. Our investigations are also focused on looking for correlations that might explain water quality patterns with respect to human activities such as gas drilling. However, percentages of water samples failing EPA MCL with respect to Pb, As, and Ba have decreased from previous USGS and PSU studies in the 1990s and 2000s. Public access to pre-drill datasets such as the one we are investigating will allow better understanding of the controls on ground water chemistry, i.e., natural and anthropogenic impacts. [1] Li et al. (2016) Journal of Contaminant Hydrology 195, 23-30.

Shale Gas characteristics of Permian black shales (Ecca group, Eastern Cape, South Africa)

NASA Astrophysics Data System (ADS)

Geel, Claire; Booth, Peter; Schulz, Hans-Martin; Horsfield, Brian; de Wit, Maarten

2013-04-01

This study involves a comprehensive and detailed lithological, sedimentalogical, structural and geochemical description of the lower Ecca Group in the Eastern Cape, South Africa. The Ecca group hosts a ~ 245 million year old organic-rich black shale, which has recently been the focus of interest of petroleum companies worldwide. The shale was deposited under anoxic conditions in a setting which formed as a consequence of retro-arc foreland basin development related to the Cape Fold Belt. This sedimentary/tectonic environment provided the conditions for deeply buried black shales to reach maturity levels for development in the gas window. The investigation site is called the Greystone Area and is situated north of Wolwefontein en route to Jansenville. The area has outcrops of the Dwyka, the Ecca and the lower Beaufort Groups. The outcrops were mapped extensively and the data was used in conjunction with GIS software to produce a detailed geological map. North-south cross sections were drawn to give indication of bed thicknesses and formation depths. Using the field work, data two boreholes were accurately sited on the northern limb of a shallow easterly plunging syncline. The first borehole reached 100m and the second was drilled to 292m depth (100m percussion and 192m core). The second borehole was drilled 200m south of the first, to penetrate the formations at a greater depth and to avoid surface weathering. Fresh core from the upper Dwyka Group, the Prince Albert Formation, the Whitehill Formation, Collingham Formation and part of the Ripon Formation were successfully extracted and a detailed stratigraphic log has been drawn up. The core was sampled during extraction and the samples were immediately sent to the GFZ in Potsdam, Germany, for geochemical analyses. As suspected the black shales of the the Whitehill Formation are high in organic carbon and have an average TOC value of 4.5%, whereas the Prince Albert and Collingham Formation are below 1%. Tmax values and the evolution of organic material to bitumen characterise these sediments as overmature. The HI and OI results reveal that the Collingham and Whitehill sediments are type II kerogen and the Prince Albert is type III kerogen sediment. XRD data shows major rock forming minerals of the black shales to be quartz, illite, muscovite and chlorite with some plagioclase and large amounts of accessory pyrite. Average meso-and macro-porosity of these black shales is 1.5% and SEM images confirm that these sediments are tightly packed. The samples are highly affected by the Cape Fold Belt due to its location so far south and is unlikely to hold gas at this position, however this ongoing investigation will give greater insight to the gas potential of these black shales which are found more north of the region. At the GFZ open system pyrolyses and thermovaporization analyses are still underway.

Thermal maturity patterns (conodont color alteration index and vitrinite reflectance) in Upper Ordovician and Devonian rocks of the Appalachian basin: a major revision of USGS Map I-917-E using new subsurface collections: Chapter F.1 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

USGS Publications Warehouse

Repetski, John E.; Ryder, Robert T.; Weary, David J.; Harris, Anita G.; Trippi, Michael H.; Ruppert, Leslie F.; Ryder, Robert T.

2014-01-01

The conodont color alteration index (CAI) introduced by Epstein and others (1977) and Harris and others (1978) is an important criterion for estimating the thermal maturity of Ordovician to Mississippian rocks in the Appalachian basin. Consequently, the CAI isograd maps of Harris and others (1978) are commonly used by geologists to characterize the thermal and burial history of the Appalachian basin and to better understand the origin and distribution of oil and gas resources in the basin. The main objectives of this report are to present revised CAI isograd maps for Ordovician and Devonian rocks in the Appalachian basin and to interpret the geologic and petroleum resource implications of these maps. The CAI isograd maps presented herein complement, and in some areas replace, the CAI-based isograd maps of Harris and others (1978) for the Appalachian basin. The CAI data presented in this report were derived almost entirely from subsurface samples, whereas the CAI data used by Harris and others (1978) were derived almost entirely from outcrop samples. Because of the different sampling methods, there is little geographic overlap of the two data sets. The new data set is mostly from the Allegheny Plateau structural province and most of the data set of Harris and others (1978) is from the Valley and Ridge structural province, east of the Allegheny structural front (fig. 1). Vitrinite reflectance, based on dispersed vitrinite in Devonian black shale, is another important parameter for estimating the thermal maturity in pre-Pennsylvanian-age rocks of the Appalachian basin (Streib, 1981; Cole and others, 1987; Gerlach and Cercone, 1993; Rimmer and others, 1993; Curtis and Faure, 1997). This chapter also presents a revised percent vitrinite reflectance (%R0) isograd map based on dispersed vitrinite recovered from selected Devonian black shales. The Devonian black shales used for the vitrinite studies reported herein also were analyzed by RockEval pyrolysis and total organic carbon (TOC) content in weight percent. Although the RockEval and TOC data are included in this chapter (table 1), they are not shown on the maps. The revised CAI isograd and percent vitrinite reflectance isograd maps cover all or parts of Kentucky, New York, Ohio, Pennsylvania, Virginia, and West Virginia (fig. 1), and the following three stratigraphic intervals: Upper Ordovician carbonate rocks, Lower and Middle Devonian carbonate rocks, and Middle and Upper Devonian black shales. These stratigraphic intervals were chosen for the following reasons: (1) they represent target reservoirs for much of the oil and gas exploration in the Appalachian basin; (2) they are stratigraphically near probable source rocks for most of the oil and gas; (3) they include geologic formations that are nearly continuous across the basin; (4) they contain abundant carbonate grainstone-packstone intervals, which give a reasonable to good probability of recovery of conodont elements from small samples of drill cuttings; and (5) the Middle and Upper Devonian black shale contains large amounts of organic matter for RockEval, TOC, and dispersed vitrinite analyses. Thermal maturity patterns of the Upper Ordovician Trenton Limestone are of particular interest here, because they closely approximate the thermal maturity patterns in the overlying Upper Ordovician Utica Shale, which is the probable source rock for oil and gas in the Upper Cambrian Rose Run Sandstone (sandstone), Upper Cambrian and Lower Ordovician Knox Group (Dolomite), Lower and Middle Ordovician Beekmantown Group (dolomite or Dolomite), Upper Ordovician Trenton and Black River Limestones, and Lower Silurian Clinton/Medina sandstone (Cole and others, 1987; Jenden and others, 1993; Laughrey and Baldassare, 1998; Ryder and others, 1998; Ryder and Zagorski, 2003). The thermal maturity patterns of the Lower Devonian Helderberg Limestone (Group), Middle Devonian Onondaga Limestone, and Middle Devonian Marcellus Shale-Upper Devonian Rhine street Shale Member-Upper Devonian Ohio Shale are of interest, because they closely approximate the thermal maturity patterns in the Marcellus Shale, Upper Devonian Rhinestreet Shale Member, and Upper Devonian Huron Member of the Ohio Shale, which are the most important source rocks for oil and gas in the Appalachian basin (de Witt and Milici, 1989; Klemme and Ulmishek, 1991). The Marcellus, Rhinestreet, and Huron units are black-shale source rocks for oil and (or) gas in the Lower Devonian Oriskany Sandstone, the Upper Devonian sandstones, the Middle and Upper Devonian black shales, and the Upper Devonian-Lower Mississippian(?) Berea Sandstone (Patchen and others, 1992; Roen and Kepferle, 1993; Laughrey and Baldassare, 1998).

Elemental composition of airborne dust in the Shale Shaker House during an offshore drilling operation.

PubMed

Hansen, A B; Larsen, E; Hansen, L V; Lyngsaae, M; Kunze, H

1991-12-01

During 2 days of an offshore drilling operation in the North Sea, 16 airborne dust samples from the atmosphere of the Shale Shaker House were collected onto filters. During this operation, drilling mud composed of a water slurry of barite (BaSO4) together with minor amounts of additives, among them chrome lignosulphonate and chrome lignite, was circulated between the borehole and the Shale Shaker House. The concentration of airborne dust in the atmosphere was determined and the elemental composition of the particles analysed by both PIXE (proton-induced X-ray emission) and ICP-MS (inductively coupled plasma-mass spectrometry). The total amount of dust collected varied from 0.04 to 1.41 mg m-3 with barium (Ba) as the single most abundant element. The open shale shakers turned out to be the major cause of generation of dust from the solid components of the drilling mud.

Permeability Evolution of Slowly Slipping Faults in Shale Reservoirs

NASA Astrophysics Data System (ADS)

Wu, Wei; Reece, Julia S.; Gensterblum, Yves; Zoback, Mark D.

2017-11-01

Slow slip on preexisting faults during hydraulic fracturing is a process that significantly influences shale gas production in extremely low permeability "shale" (unconventional) reservoirs. We experimentally examined the impacts of mineralogy, surface roughness, and effective stress on permeability evolution of slowly slipping faults in Eagle Ford shale samples. Our results show that fault permeability decreases with slip at higher effective stress but increases with slip at lower effective stress. The permeabilities of saw cut faults fully recover after cycling effective stress from 2.5 to 17.5 to 2.5 MPa and increase with slip at constant effective stress due to asperity damage and dilation associated with slip. However, the permeabilities of natural faults only partially recover after cycling effective stress returns to 2.5 MPa and decrease with slip due to produced gouge blocking fluid flow pathways. Our results suggest that slowly slipping faults have the potential to enhance reservoir stimulation in extremely low permeability reservoirs.

Stratigraphy and vertical hydraulic conductivity of the St. Francois Confining Unit in the Viburnum Trend and evaluation of the Unit in the Viburnum Trend and exploration areas, southeastern Missouri

USGS Publications Warehouse

Kleeschulte, Michael J.; Seeger, Cheryl M.

2003-01-01

The confining ability of the St. Francois confining unit (Derby-Doerun Dolomite and Davis Formation) was evaluated in ten townships (T. 31?35 N. and R. 01?02 W.) along the Viburnum Trend of southeastern Missouri. Vertical hydraulic conductivity data were compared to similar data collected during two previous studies 20 miles south of the Viburnum Trend, in two lead-zinc exploration areas that may be a southern extension of the Viburnum Trend. The surficial Ozark aquifer is the primary source of water for domestic and public-water supplies and major springs in southern Missouri. The St. Francois confining unit lies beneath the Ozark aquifer and impedes the movement of water between the Ozark aquifer and the underlying St. Francois aquifer (composed of the Bonneterre Formation and Lamotte Sandstone). The Bonneterre Formation is the primary host formation for lead-zinc ore deposits of the Viburnum Trend and potential host formation in the exploration areas. For most of the more than 40 years the mines have been in operation along the Viburnum Trend, about 27 million gallons per day were being pumped from the St. Francois aquifer for mine dewatering. Previous studies conducted along the Viburnum Trend have concluded that no large cones of depression have developed in the potentiometric surface of the Ozark aquifer as a result of mining activity. Because of similar geology, stratigraphy, and depositional environment between the Viburnum Trend and the exploration areas, the Viburnum Trend may be used as a pertinent, full-scale model to study and assess how mining may affect the exploration areas. Along the Viburnum Trend, the St. Francois confining unit is a complex series of dolostones, limestones, and shales that generally is 230 to 280 feet thick with a net shale thickness ranging from less than 25 to greater than 100 feet with the thickness increasing toward the west. Vertical hydraulic conductivity values determined from laboratory permeability tests were used to represent the St. Francois confining unit along the Viburnum Trend. The Derby-Doerun Dolomite and Davis Formation are statistically similar, but the Davis Formation would be the more hydraulically restrictive medium. The shale and carbonate values were statistically different. The median vertical hydraulic conductivity value for the shale samples was 62 times less than the carbonate samples. Consequently, the net shale thickness of the confining unit along the Viburnum Trend significantly affects the effective vertical hydraulic conductivity. As the percent of shale increases in a given horizon, the vertical hydraulic conductivity decreases. The range of effective vertical hydraulic conductivity for the confining unit in the Viburnum Trend was estimated to be a minimum of 2 x 10-13 ft/s (foot per second) and a maximum of 3 x 10-12 ft/s. These vertical hydraulic conductivity values are considered small and verify conclusions of previous studies that the confining unit effectively impedes the flow of ground water between the Ozark aquifer and the St. Francois aquifer along the Viburnum Trend. Previously-collected vertical hydraulic conductivity data for the two exploration areas from two earlier studies were combined with the data collected along the Viburnum Trend. The nonparametric Kruskal-Wallis statistical test shows the vertical hydraulic conductivity of the St. Francois confining unit along the Viburnum Trend, and west and east exploration areas are statistically different. The vertical hydraulic conductivity values generally are the largest in the Viburnum Trend and are smallest in the west exploration area. The statistical differences in these values do not appear to be attributed strictly to either the Derby-Doerun Dolomite or Davis Formation, but instead they are caused by the differences in the carbonate vertical hydraulic conductivity values at the three locations. The calculated effective vertical hydraulic conductivity range for the St. Franc

Effect of drilling fluid systems and temperature on oil mist and vapour levels generated from shale shaker.

PubMed

Steinsvåg, Kjersti; Galea, Karen S; Krüger, Kirsti; Peikli, Vegard; Sánchez-Jiménez, Araceli; Sætvedt, Esther; Searl, Alison; Cherrie, John W; van Tongeren, Martie

2011-05-01

Workers in the drilling section of the offshore petroleum industry are exposed to air pollutants generated by drilling fluids. Oil mist and oil vapour concentrations have been measured in the drilling fluid processing areas for decades; however, little work has been carried out to investigate exposure determinants such as drilling fluid viscosity and temperature. A study was undertaken to investigate the effect of two different oil-based drilling fluid systems and their temperature on oil mist, oil vapour, and total volatile organic compounds (TVOC) levels in a simulated shale shaker room at a purpose-built test centre. Oil mist and oil vapour concentrations were sampled simultaneously using a sampling arrangement consisting of a Millipore closed cassette loaded with glass fibre and cellulose acetate filters attached to a backup charcoal tube. TVOCs were measured by a PhoCheck photo-ionization detector direct reading instrument. Concentrations of oil mist, oil vapour, and TVOC in the atmosphere surrounding the shale shaker were assessed during three separate test periods. Two oil-based drilling fluids, denoted 'System 2.0' and 'System 3.5', containing base oils with a viscosity of 2.0 and 3.3-3.7 mm(2) s(-1) at 40°C, respectively, were used at temperatures ranging from 40 to 75°C. In general, the System 2.0 yielded low oil mist levels, but high oil vapour concentrations, while the opposite was found for the System 3.5. Statistical significant differences between the drilling fluid systems were found for oil mist (P = 0.025),vapour (P < 0.001), and TVOC (P = 0.011). Increasing temperature increased the oil mist, oil vapour, and TVOC levels. Oil vapour levels at the test facility exceeded the Norwegian oil vapour occupational exposure limit (OEL) of 30 mg m(-3) when the drilling fluid temperature was ≥50°C. The practice of testing compliance of oil vapour exposure from drilling fluids systems containing base oils with viscosity of ≤2.0 mm(2) s(-1) at 40°C against the Norwegian oil vapour OEL is questioned since these base oils are very similar to white spirit. To reduce exposures, relevant technical control measures in this area are to cool the drilling fluid <50°C before it enters the shale shaker units, enclose shale shakers and related equipment, in addition to careful consideration of which fluid system to use.

Total selenium and selenium species in irrigation drain inflows to the Salton Sea, California, April and July 2007

USGS Publications Warehouse

May, Thomas W.; Walther, Michael J.; Saiki, Michael K.; Brumbaugh, William G.

2007-01-01

This report presents the results for two sampling periods during a 4-year monitoring survey to provide a characterization of selenium concentrations in selected irrigation drains flowing into the Salton Sea, California. Total selenium, selenium species, and total suspended solids were determined in water samples, and total selenium was determined in sediment, detritus, and biota that included algae, plankton, midge larvae (family, Chironomidae), and two fish species-western mosquitofish (Gambusia affinis), and sailfin molly (Poecilia latipinna). In addition, sediments were analyzed for percent total organic carbon and particle size. Total selenium concentrations in water for both sampling periods ranged from 1.43 to 47.1 micrograms per liter, predominately as selenate, which is typical of waters leached out of selenium-contaminated marine shales under alkaline and oxidizing conditions. Total selenium concentrations ranged from 0.88 to 20.2 micrograms per gram in biota, and from 0.15 to 28.9 micrograms per gram in detritus and sediment.

Stratigraphic cross sections of the Niobrara interval of the Cody Shale and associated rocks in the Wind River Basin, central Wyoming

USGS Publications Warehouse

Finn, Thomas M.

2017-02-07

The Wind River Basin in Wyoming is one of many structural and sedimentary basins that formed in the Rocky Mountain foreland during the Laramide orogeny. The basin is nearly 200 miles long, 70 miles wide, and encompasses about 7,400 square miles in central Wyoming. The basin is bounded by the Washakie Range, Owl Creek uplift, and southern Bighorn Mountains on the north, the Casper arch on the east, the Granite Mountains on the south, and Wind River Range on the west.Many important conventional oil and gas fields producing from reservoirs ranging in age from Mississippian through Tertiary have been discovered in this basin. In addition, an extensive unconventional overpressured basin-centered gas accumulation has been identified in Cretaceous and Tertiary strata in the deeper parts of the basin. It has long been suggested that various Upper Cretaceous marine shales, including the Cody Shale, are the principal hydrocarbon source rocks for many of these accumulations. With recent advances and success in horizontal drilling and multistage fracture stimulation, there has been an increase in exploration and completion of wells in these marine shales in other Rocky Mountain Laramide basins that were traditionally thought of only as hydrocarbon source rocks.The two stratigraphic cross sections presented in this report were constructed as part of a project carried out by the U.S. Geological Survey to characterize and evaluate the undiscovered continuous (unconventional) oil and gas resources of the Niobrara interval of the Upper Cretaceous Cody Shale in the Wind River Basin in central Wyoming. The primary purpose of the cross sections is to show the stratigraphic relationship of the Niobrara equivalent strata and associated rocks in the lower part of the Cody Shale in the Wind River Basin. These two cross sections were constructed using borehole geophysical logs from 37 wells drilled for oil and gas exploration and production, and one surface section along East Sheep Creek near Shotgun Butte in the northwestern part of the basin. Both lines originate at the East Sheep Creek surface section and end near Clarkson Hill in the extreme southeastern part of the basin. The stratigraphic interval extends from the upper part of the Frontier Formation to the middle part of the Cody Shale. The datum is the base of the “chalk kick” marker bed, a distinctive resistivity peak or zone in the lower part of the Cody Shale. A gamma ray and (or) spontaneous potential (SP) log was used in combination with a resistivity log to identify and correlate units. Marine molluscan index fossils collected from nearby outcrop sections were projected into the subsurface to help determine the relative ages of the strata and aid in correlation.

Reservoir capacity estimates in shale plays based on experimental adsorption data

NASA Astrophysics Data System (ADS)

Ngo, Tan

Fine-grained sedimentary rocks are characterized by a complex porous framework containing pores in the nanometer range that can store a significant amount of natural gas (or any other fluids) through adsorption processes. Although the adsorbed gas can take up to a major fraction of the total gas-in-place in these reservoirs, the ability to produce it is limited, and the current technology focuses primarily on the free gas in the fractures. A better understanding and quantification of adsorption/desorption mechanisms in these rocks is therefore required, in order to allow for a more efficient and sustainable use of these resources. Additionally, while water is still predominantly used to fracture the rock, other fluids, such as supercritical CO2 are being considered; here, the idea is to reproduce a similar strategy as for the enhanced recovery of methane in deep coal seams (ECBM). Also in this case, the feasibility of CO2 injection and storage in hydrocarbon shale reservoirs requires a thorough understanding of the rock behavior when exposed to CO2, thus including its adsorption characteristics. The main objectives of this Master's Thesis are as follows: (1) to identify the main controls on gas adsorption in mudrocks (TOC, thermal maturity, clay content, etc.); (2) to create a library of adsorption data measured on shale samples at relevant conditions and to use them for estimating GIP and gas storage in shale reservoirs; (3) to build an experimental apparatus to measure adsorption properties of supercritical fluids (such as CO2 or CH 4) in microporous materials; (4) to measure adsorption isotherms on microporous samples at various temperatures and pressures. The main outcomes of this Master's Thesis are summarized as follows. A review of the literature has been carried out to create a library of methane and CO2 adsorption isotherms on shale samples from various formations worldwide. Large discrepancies have been found between estimates of the adsorbed gas density from different measurement techniques using representative fluids (such as CH4 and CO2) at elevated pressures, and the adsorbed density can range anywhere between the liquid and the solid state of the adsorbate. Whether these discrepancies are associated with the inherent heterogeneity of mudrocks and/or with poor data quality requires more experiments under well-controlled conditions. Nevertheless, it has been found in this study that methane GIP estimates can vary between 10-45% and 10-30%, respectively, depending on whether the free or the total amount of gas is considered. Accordingly, CO2 storage estimates range between 30-90% and 15-50%, due to the larger adsorption capacity and gas density at similar pressure and temperature conditions. A manometric system has been designed and built that allows measuring the adsorption of supercritical fluids in microporous materials. Preliminary adsorption tests have been performed using a microporous 13X zeolite and CO 2 as an adsorbing gas at a temperature of 25oC and 35oC and at pressures up to 500 psi. Under these conditions, adsorption is quantified with a precision of +/- 3%. However, relative differences up to 15-20% have been observed with respect to data published in the literature on the same adsorbent and at similar experimental conditions. While it cannot be fully explained with uncertainty analysis, this discrepancy can be reduced by improving experiment practice, thus including the application of a higher adsorbent's regeneration temperature, of longer equilibrium times and of a careful flushing of the system between the various experimental steps. Based on the results on 13X zeolite, virtual tests have been conducted to predict the performance of the manometric system to measure adsorption on less adsorbing materials, such as mudrocks. The results show that uncertainties in the estimated adsorbed amount are much more significant in shale material and they increase with increasing pressure. In fact, relative uncertainties in the adsorbed amount can reach up to 80 and 200% at 500 and 1600 psia, respectively. The latter can be reduced (i) by increasing the mass of adsorbent material (15.2% and 42.3% when the mass of adsorbent is doubled as compared to the experiment with 13X zeolite) and/or (ii) by increasing the precision of the pressure transducers (uncertainty is further reduced to 3% and 8.4% from case (i) when the transducers with 0.05% accuracy are used. These experiments are justified by the need of extending the current data set on gas adsorption of mudrocks, thus enabling a more reliable estimate on the available gas reserves in shale reservoir and the potential of carbon dioxide storage. (Abstract shortened by UMI.).

Composition, diagenetic transformation and alkalinity potential of oil shale ash sediments.

PubMed

Mõtlep, Riho; Sild, Terje; Puura, Erik; Kirsimäe, Kalle

2010-12-15

Oil shale is a primary fuel in the Estonian energy sector. After combustion 45-48% of the oil shale is left over as ash, producing about 5-7 Mt of ash, which is deposited on ash plateaus annually almost without any reuse. This study focuses on oil shale ash plateau sediment mineralogy, its hydration and diagenetic transformations, a study that has not been addressed. Oil shale ash wastes are considered as the biggest pollution sources in Estonia and thus determining the composition and properties of oil shale ash sediment are important to assess its environmental implications and also its possible reusability. A study of fresh ash and drillcore samples from ash plateau sediment was conducted by X-ray diffractometry and scanning electron microscopy. The oil shale is highly calcareous, and the ash that remains after combustion is derived from the decomposition of carbonate minerals. It is rich in lime and anhydrite that are unstable phases under hydrous conditions. These processes and the diagenetic alteration of other phases determine the composition of the plateau sediment. Dominant phases in the ash are hydration and associated transformation products: calcite, ettringite, portlandite and hydrocalumite. The prevailing mineral phases (portlandite, ettringite) cause highly alkaline leachates, pH 12-13. Neutralization of these leachates under natural conditions, by rainwater leaching/neutralization and slow transformation (e.g. carbonation) of the aforementioned unstable phases into more stable forms, takes, at best, hundreds or even hundreds of thousands of years. Copyright © 2010 Elsevier B.V. All rights reserved.

Tectonic setting of Jurassic basins in Central Mongolia: Insights from the geochemistry of Tsagaan-Ovoo oil shale

NASA Astrophysics Data System (ADS)

Erdenetsogt, B. O.; Hong, S. K.; Choi, J.; Odgerel, N.; Lee, I.; Ichinnorov, N.; Tsolmon, G.; Munkhnasan, B.

2017-12-01

Tsagaan-Ovoo syncline hosting Lower-Middle Jurassic oil shale is a part of Saikhan-Ovoo the largest Jurassic sedimentary basin in Central Mongolia. It is generally accepted that early Mesozoic basins are foreland basins. In total, 18 oil shale samples were collected from an open-pit mine. The contents of organic carbon, and total nitrogen and their isotopic compositions as well as major element concentrations were analyzed. The average TOC content is 12.4±1.2 %, indicating excellent source rock potential. C/N ratios show an average of 30.0±1.2, suggesting terrestrial OM. The average value of δ15N is +3.9±0.2‰, while that of δ13Corg is -25.7±0.1‰. The isotopic compositions argue for OM derived dominantly from land plant. Moreover, changes in δ15N values of analyzed samples reflect variations in algal OM concentration of oil shale. The lowest δ15N value (+2.5‰) was obtained from base section, representing the highest amount of terrestrial OM, whereas higher δ15N values (up to +5.2‰) are recorded at top section, reflecting increased amount of algal OM. On the other hand, changes in δ15N value may also represent changes in redox state of water column in paleolake. The oil shale at bottom of section with low δ15N value was accumulated under oxic condition, when the delivery of land plant OM was high. With increase in subsidence rate through time, lake was deepened and water column was depleted in oxygen probably due to extensive phytoplankton growth, which results increase in algae derived OM contents as well as bulk δ15N of oil shale. The average value of CAI for Tsagan-Ovoo oil shale is 81.6±1.3, reflecting intensive weathering in the source area. The plotted data on A-CN-K diagram displays that oil shale was sourced mainly from Early Permian granodiorite and diorite, which are widely distributed around Tsagaan-Ovoo syncline. To infer tectonic setting, two multi-dimensional discrimination diagrams were used. The results suggest that the tectonic setting of Tsagaan-Ovoo syncline, in which the studied oil shale was deposited, was continental rift. This finding contradicts with generally accepted contractile deformation during early Mesozoic in Mongolia and China. Further detailed study is required to decipher the tectonic settings of central Mongolian Jurassic basins.

The geological and microbiological controls on the enrichment of Se and Te in sedimentary rocks

NASA Astrophysics Data System (ADS)

Bullock, Liam; Parnell, John; Armstrong, Joseph; Boyce, Adrian; Perez, Magali

2017-04-01

Selenium (Se) and tellurium (Te) have become elements of high interest, mainly due to their photovoltaic and photoconductive properties, and can contaminate local soils and groundwater systems during mobilisation. Due to their economic and environmental significance, it is important to understand the processes that lead to Se- and Te-enrichment in sediments. The distribution of Se and Te in sedimentary environments is primarily a function of redox conditions, and may be transported and concentrated by the movement of reduced fluids through oxidised strata. Se and Te concentrations have been measured in a suite of late Neoproterozoic Gwna Group black shales (UK) and uranium red bed (roll-front) samples (USA). Due to the chemical affinity of Se and sulphur (S), variations in the S isotopic composition of pyrite have also been measured in order to provide insights into their origin. Scanning electron microscopy of pyrite in the black shales shows abundant inclusions of the lead selenide mineral clausthalite. The data for the black shale samples show marked enrichment in Te and Se relative to crustal mean and several hundreds of other samples processed through our laboratory. While Se levels in sulphidic black shales are typically below 5 ppm, the measured values of up to 116 ppm are remarkable. The Se enrichment in roll-fronts (up to 168 ppm) is restricted to a narrow band of alteration at the interface between the barren oxidised core, and the highly mineralised reduced nose of the front. Te is depleted in roll-fronts with respect to the continental crust and other geological settings and deposits. S isotope compositions for pyrite in both the black shales and roll-fronts are very light and indicate precipitation by microbial sulphate reduction, suggesting that Se was microbially sequestered. Results show that Gwna Group black shales and U.S roll-front deposits contain marked elemental enrichments (particularly Se content). In Gwna Group black shales, Se and Te were sequestered out of seawater into pyritic shales at a higher rate than into crusts. Se enrichment in roll-fronts relates to the initial mobilisation of trace elements in oxidised conditions, and later precipitation downgradient in reduced conditions. Results highlight the potential for sedimentary types of Se- and Te-bearing deposits. The enrichment of elements of high value for future technologies in sedimentary rocks deserve careful assessment for potential future resources, and should be monitored during exploration and mobilisation due to the potential contamination effects. This work forms part of the NERC-funded 'Security of Supply of Mineral Resources' project, which aims to detail the science needed to sustain the security of supply of strategic minerals in a changing environment.

Geohydrology and ground-water quality at the Pueblo Depot activity landfill near Pueblo, Colorado

USGS Publications Warehouse

Watts, Kenneth R.; Ortiz, Roderick F.

1990-01-01

Groundwater samples were collected from the shallow unconfined aquifer at the Pueblo Depot Activity (Colorado) landfill and downstream from the landfill. The Pueblo Depot Activity is a U.S. Department of the Army facility in southeastern Colorado about 15 miles east of Pueblo, Colorado. The land-fill is underlain by upland alluvial terrace deposits that overlie a thick and almost impermeable shale. Saturated thickness of the aquifer generally is from 5 to 10 feet. Groundwater flow at the landfill is to the south-southeast toward the Arkansas River valley. Though not hydraulically connected to the upland terrace deposits, the alluvium underlying the Arkansas River valley may be recharged by groundwater that is discharged from seeps at the contact of the upland terrace deposits and the Pierre Shale. The water is classified as a mixed-cation mixed-anion type water that has concentrations of dissolved solids of 710 to 1,810 mg/L. Dissolved-solids concentrations increase downgradient. Chemical analysis, done to determine possible contamination of the groundwater, indicated that concentrations of trichloroethylene ranged from 5.2 to 2,900 microg/L and of trans-1,2-dichloroethylene ranged from 5 to 720 microg/L. The areal distribution of these volatile organic compounds indicate that there possibly are two sources of contamination of groundwater at the landfill, one upgradient from the landfill and the other within the landfill. Analysis of water samples from wells and seeps offsite and downgradient from the landfill did not indicate either contaminant in groundwater from the alluvial aquifer underlying the Arkansas River valley. (USGS)

Volatile-organic molecular characterization of shale-oil produced water from the Permian Basin

USGS Publications Warehouse

Khan, Naima A.; Engle, Mark A.; Dungan, Barry; Holguin, F. Omar; Xu, Pei; Carroll, Kenneth C.

2016-01-01

Growth in unconventional oil and gas has spurred concerns on environmental impact and interest in beneficial uses of produced water (PW), especially in arid regions such as the Permian Basin, the largest U.S. tight-oil producer. To evaluate environmental impact, treatment, and reuse potential, there is a need to characterize the compositional variability of PW. Although hydraulic fracturing has caused a significant increase in shale-oil production, there are no high-resolution organic composition data for the shale-oil PW from the Permian Basin or other shale-oil plays (Eagle Ford, Bakken, etc.). PW was collected from shale-oil wells in the Midland sub-basin of the Permian Basin. Molecular characterization was conducted using high-resolution solid phase micro extraction gas chromatography time-of-flight mass spectrometry. Approximately 1400 compounds were identified, and 327 compounds had a >70% library match. PW contained alkane, cyclohexane, cyclopentane, BTEX (benzene, toluene, ethylbenzene, and xylene), alkyl benzenes, propyl-benzene, and naphthalene. PW also contained heteroatomic compounds containing nitrogen, oxygen, and sulfur. 3D van Krevelen and double bond equivalence versus carbon number analyses were used to evaluate molecular variability. Source composition, as well as solubility, controlled the distribution of volatile compounds found in shale-oil PW. The salinity also increased with depth, ranging from 105 to 162 g/L total dissolved solids. These data fill a gap for shale-oil PW composition, the associated petroleomics plots provide a fingerprinting framework, and the results for the Permian shale-oil PW suggest that partial treatment of suspended solids and organics would support some beneficial uses such as onsite reuse and bio-energy production.

Hydrothermal Liquefaction Biocrude Compositions Compared to Petroleum Crude and Shale Oil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jarvis, Jacqueline M.; Billing, Justin M.; Hallen, Richard T.

We provide a direct and detailed comparison of the chemical composition of petroleum crude oil (from the Gulf of Mexico), shale oil, and three biocrudes (i.e., clean pine, microalgae Chlorella sp., and sewage sludge feedstocks) generated by hydrothermal liquefaction (HTL). Ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) reveals that HTL biocrudes are compositionally more similar to shale oil than petroleum crude oil and that only a few heteroatom classes (e.g., N1, N2, N1O1, and O1) are common to organic sediment- and biomass-derived oils. All HTL biocrudes contain a diverse range of oxygen-containing compounds when compared tomore » either petroleum crude or shale oil. Overall, petroleum crude and shale oil are compositionally dissimilar to HTL oils, and >85% of the elemental compositions identified within the positive-ion electrospray (ESI) mass spectra of the HTL biocrudes were not present in either the petroleum crude or shale oil (>43% for negative-ion ESI). Direct comparison of the heteroatom classes that are common to both organic sedimentand biomass-derived oils shows that HTL biocrudes generally contain species with both smaller core structures and a lower degree of alkylation relative to either the petroleum crude or the shale oil. Three-dimensional plots of carbon number versus molecular double bond equivalents (with observed abundance as the third dimension) for abundant molecular classes reveal the specific relationship of the composition of HTL biocrudes to petroleum and shale oils to inform the possible incorporation of these oils into refinery operations as a partial amendment to conventional petroleum feeds.« less

Volatile-organic molecular characterization of shale-oil produced water from the Permian Basin.

PubMed

Khan, Naima A; Engle, Mark; Dungan, Barry; Holguin, F Omar; Xu, Pei; Carroll, Kenneth C

2016-04-01

Growth in unconventional oil and gas has spurred concerns on environmental impact and interest in beneficial uses of produced water (PW), especially in arid regions such as the Permian Basin, the largest U.S. tight-oil producer. To evaluate environmental impact, treatment, and reuse potential, there is a need to characterize the compositional variability of PW. Although hydraulic fracturing has caused a significant increase in shale-oil production, there are no high-resolution organic composition data for the shale-oil PW from the Permian Basin or other shale-oil plays (Eagle Ford, Bakken, etc.). PW was collected from shale-oil wells in the Midland sub-basin of the Permian Basin. Molecular characterization was conducted using high-resolution solid phase micro extraction gas chromatography time-of-flight mass spectrometry. Approximately 1400 compounds were identified, and 327 compounds had a >70% library match. PW contained alkane, cyclohexane, cyclopentane, BTEX (benzene, toluene, ethylbenzene, and xylene), alkyl benzenes, propyl-benzene, and naphthalene. PW also contained heteroatomic compounds containing nitrogen, oxygen, and sulfur. 3D van Krevelen and double bond equivalence versus carbon number analyses were used to evaluate molecular variability. Source composition, as well as solubility, controlled the distribution of volatile compounds found in shale-oil PW. The salinity also increased with depth, ranging from 105 to 162 g/L total dissolved solids. These data fill a gap for shale-oil PW composition, the associated petroleomics plots provide a fingerprinting framework, and the results for the Permian shale-oil PW suggest that partial treatment of suspended solids and organics would support some beneficial uses such as onsite reuse and bio-energy production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Double torsion fracture mechanics testing of shales under chemically reactive conditions

NASA Astrophysics Data System (ADS)

Chen, X.; Callahan, O. A.; Holder, J. T.; Olson, J. E.; Eichhubl, P.

2015-12-01

Fracture properties of shales is vital for applications such as shale and tight gas development, and seal performance of carbon storage reservoirs. We analyze the fracture behavior from samples of Marcellus, Woodford, and Mancos shales using double-torsion (DT) load relaxation fracture tests. The DT test allows the determination of mode-I fracture toughness (KIC), subcritical crack growth index (SCI), and the stress-intensity factor vs crack velocity (K-V) curves. Samples are tested at ambient air and aqueous conditions with variable ionic concentrations of NaCl and CaCl2, and temperatures up to 70 to determine the effects of chemical/environmental conditions on fracture. Under ambient air condition, KIC determined from DT tests is 1.51±0.32, 0.85±0.25, 1.08±0.17 MPam1/2 for Marcellus, Woodford, and Mancos shales, respectively. Tests under water showed considerable change of KIC compared to ambient condition, with 10.6% increase for Marcellus, 36.5% decrease for Woodford, and 6.7% decrease for Mancos shales. SCI under ambient air condition is between 56 and 80 for the shales tested. The presence of water results in a significant reduction of the SCI from 70% to 85% compared to air condition. Tests under chemically reactive solutions are currently being performed with temperature control. K-V curves under ambient air conditions are linear with stable SCI throughout the load-relaxation period. However, tests conducted under water result in an initial cracking period with SCI values comparable to ambient air tests, which then gradually transition into stable but significantly lower SCI values of 10-20. The non-linear K-V curves reveal that crack propagation in shales is initially limited by the transport of chemical agents due to their low permeability. Only after the initial cracking do interactions at the crack tip lead to cracking controlled by faster stress corrosion reactions. The decrease of SCI in water indicates higher crack propagation velocity due to faster stress corrosion rate in water than in ambient air. The experimental results are applicable for the prediction of fracture initiation based on KIC, modeling fracture pattern based on SCI, and the estimation of dynamic fracture propagation such as crack growth velocity and crack re-initiation.

Prediction of total organic carbon content in shale reservoir based on a new integrated hybrid neural network and conventional well logging curves

NASA Astrophysics Data System (ADS)

Zhu, Linqi; Zhang, Chong; Zhang, Chaomo; Wei, Yang; Zhou, Xueqing; Cheng, Yuan; Huang, Yuyang; Zhang, Le

2018-06-01

There is increasing interest in shale gas reservoirs due to their abundant reserves. As a key evaluation criterion, the total organic carbon content (TOC) of the reservoirs can reflect its hydrocarbon generation potential. The existing TOC calculation model is not very accurate and there is still the possibility for improvement. In this paper, an integrated hybrid neural network (IHNN) model is proposed for predicting the TOC. This is based on the fact that the TOC information on the low TOC reservoir, where the TOC is easy to evaluate, comes from a prediction problem, which is the inherent problem of the existing algorithm. By comparing the prediction models established in 132 rock samples in the shale gas reservoir within the Jiaoshiba area, it can be seen that the accuracy of the proposed IHNN model is much higher than that of the other prediction models. The mean square error of the samples, which were not joined to the established models, was reduced from 0.586 to 0.442. The results show that TOC prediction is easier after logging prediction has been improved. Furthermore, this paper puts forward the next research direction of the prediction model. The IHNN algorithm can help evaluate the TOC of a shale gas reservoir.

A Collection of Chemical, Mineralogical, and Stable Isotopic Compositional Data for Green River Oil Shale from Depositional Center Cores in Colorado, Utah, and Wyoming

USGS Publications Warehouse

Tuttle, Michele L.W.

2009-01-01

For over half a century, the U.S. Geological Survey and collaborators have conducted stratigraphic and geochemical studies on the Eocene Green River Formation, which is known to contain large oil shale resources. Many of the studies were undertaken in the 1970s during the last oil shale boom. One such study analyzed the chemistry, mineralogy, and stable isotopy of the Green River Formation in the three major depositional basins: Piceance basin, Colo.; Uinta basin, Utah; and the Green River basin, Wyo. One depositional-center core from each basin was sampled and analyzed for major, minor, and trace chemistry; mineral composition and sulfide-mineral morphology; sulfur, nitrogen, and carbon forms; and stable isotopic composition (delta34S, delta15N, delta13C, and delta18O). Many of these data were published and used to support interpretative papers (see references herein). Some bulk-chemical and carbonate-isotopic data were never published and may be useful to studies that are currently exploring topics such as future oil shale development and the climate, geography, and weathering in the Eocene Epoch. These unpublished data, together with most of the U.S. Geological Survey data already published on these samples, are tabulated in this report.

Mapping thermal maturity in the Chainman shale, near Eureka, Nevada, with Landsat Thematic Mapper images

USGS Publications Warehouse

Rowan, L.C.; Pawlewicz, M.J.; Jones, O.D.

1992-01-01

The purpose of this study was to determine if there is a correlation between measurements of organic matter (OM) maturity and laboratory measurements of visible and near-infrared spectral reflectance, and if Landsat Thematic Mapper (TM) images could be used to map maturity. The maturity of Mississippian Chainman Shale samples collected in east-central Nevada and west-central Utah was determined by using vitrinite reflectance and Rock-Eval pyrolysis. TM 4/TM 5 values correspond well to vitrinite reflectance and hydrogen index variations, and therefore this ratio was used to evaluate a TM image of the Eureka, Nevada, area for mapping thermal maturity differences in the Chainman Shale. -from Authors

The Search for Biosignatures on Mars: Using Predictive Geology to Optimize Exploration Targets

NASA Technical Reports Server (NTRS)

Oehler, Dorothy Z.; Allen, Carlton C.

2011-01-01

Predicting geologic context from satellite data is a method used on Earth for exploration in areas with limited ground truth. The method can be used to predict facies likely to contain organic-rich shales. Such shales concentrate and preserve organics and are major repositories of organic biosignatures on Earth [1]. Since current surface conditions on Mars are unfavorable for development of abundant life or for preservation of organic remains of past life, the chances are low of encountering organics in surface samples. Thus, focusing martian exploration on sites predicted to contain organic-rich shales would optimize the chances of discovering evidence of life, if it ever existed on that planet.

Shale Gas and Oil in Germany - Resources and Environmental Impacts

NASA Astrophysics Data System (ADS)

Ladage, Stefan; Blumenberg, Martin; Houben, Georg; Pfunt, Helena; Gestermann, Nicolai; Franke, Dieter; Erbacher, Jochen

2017-04-01

In light of the controversial debate on "unconventional" oil and gas resources and the environmental impacts of "fracking", the Federal Institute for Geosciences and Natural Resources (BGR) conducted a comprehensive resource assessment of shale gas and light tight oil in Germany and studied the potential environmental impacts of shale gas development and hydraulic fracturing from a geoscientific perspective. Here, we present our final results (BGR 2016), incorporating the majority of potential shale source rock formations in Germany. Besides shale gas, light tight oil has been assessed. According to our set of criteria - i.e. thermal maturity 0.6-1.2 %vitrinite reflectance (VR; oil) and >1.2 % VR (gas) respectively, organic carbon content > 2%, depth between 500/1000 m and 5000 m as well as a net thickness >20 m - seven potentially generative shale formations were indentified, the most important of them being the Lower Jurassic (Toarcian) Posidonia shale with both shale gas and tight oil potential. The North German basin is by far the most prolific basin. The resource assessment was carried out using a volumetric in-place approach. Variability inherent in the input parameters was accounted for using Monte-Carlo simulations. Technically recoverable resources (TRR) were estimated using recent, production-based recovery factors of North American shale plays and also employing Monte-Carlo simulations. In total, shale gas TRR range between 320 and 2030 bcm and tight oil TRR between 13 and 164 Mio. t in Germany. Tight oil potential is therefore considered minor, whereas the shale gas potential exceeds that of conventional resources by far. Furthermore an overview of numerical transport modelling approaches concerning environmental impacts of the hydraulic fracturing is given. These simulations are based on a representative lithostratigraphy model of the North-German basin, where major shale plays can be expected. Numerical hydrogeological modelling of frac fluid migration in the subsurface has been conducted, as well as stress modelling to estimate frac dimension magnitudes and the potential frequency of induced seismity. The results of these simulations reveal that the probabiltiy of impacts on shallow groundwater by the upward migration of fracking fluids from a deep shale formation through the geological underground in the North German basin is small. BGR 2016 - Schieferöl und Schiefergas in Deutschland - Potenziale und Umweltaspekte, 197p, Hannover, 2016: http://www.bgr.bund.de/DE/Themen/Energie/Downloads/Abschlussbericht_13MB_Schieferoelgaspotenzial_Deutschland_2016.pdf?__blob=publicationFile&v=5.

On the possibility of magnetic nano-markers use for hydraulic fracturing in shale gas mining

NASA Astrophysics Data System (ADS)

Zawadzki, Jaroslaw; Bogacki, Jan

2016-04-01

Recently shale gas production became essential for the global economy, thanks to fast advances in shale fracturing technology. Shale gas extraction can be achieved by drilling techniques coupled with hydraulic fracturing. Further increasing of shale gas production is possible by improving the efficiency of hydraulic fracturing and assessing the spatial distribution of fractures in shale deposits. The latter can be achieved by adding magnetic markers to fracturing fluid or directly to proppant, which keeps the fracture pathways open. After that, the range of hydraulic fracturing can be assessed by measurement of vertical and horizontal component of earth's magnetic field before and after fracturing. The difference in these components caused by the presence of magnetic marker particles may allow to delineate spatial distribution of fractures. Due to the fact, that subterranean geological formations may contain minerals with significant magnetic properties, it is important to provide to the markers excellent magnetic properties which should be also, independent of harsh chemical and geological conditions. On the other hand it is of great significance to produce magnetic markers at an affordable price because of the large quantities of fracturing fluids or proppants used during shale fracturing. Examining the properties of nano-materials, it was found, that they possess clearly superior magnetic properties, as compared to the same structure but having a larger particle size. It should be then possible, to use lower amount of magnetic marker, to obtain the same effect. Although a research on properties of new magnetic nano-materials is very intensive, cheap magnetic nano-materials are not yet produced on a scale appropriate for shale gas mining. In this work we overview, in detail, geological, technological and economic aspects of using magnetic nano-markers in shale gas mining. Acknowledgment This work was supported by the NCBiR under Grant "Electromagnetic method to estimate penetration of proppant in the fracturing process".

Chemical and physical characteristics of coal and carbonaceous shale samples from the Salt Range coal field, Punjab Province, Pakistan

USGS Publications Warehouse

Warwick, Peter D.; Shakoor, T.; Javed, Shahid; Mashhadi, S.T.A.; Hussain, H.; Anwar, M.; Ghaznavi, M.I.

1990-01-01

Sixty coal and carbonaceous shale samples collected from the Paleocene Patala Formation in the Salt Range coal field, Punjab Province, Pakistan, were analyzed to examine the relationships between coal bed chemical and physical characteristics and depositional environments. Results of proximate and ultimate analyses, reported on an as received basis, indicate that coal beds have an average ash yield of 24.23 percent, average sulfur content of 5.32 percent, average pyritic sulfur content of 4.07 percent, and average calorific value of 8943 Btu (4972 kcal/kg). Thirty five coal samples, analyzed on a whole coal, dry basis for selected trace elements and oxides, have anomalously high average concentrations of Ti, at O.3& percent; Zr, at 382 ppm; and Se, at 11.4 ppm, compared to world wide averages for these elements in coal.Some positive correlation coefficients, significant at a 0.01 level, are those between total sulfur and As, pyritic sulfur and As, total sulfur and sample location, organic sulfur and Se, calorific value (Btu) and sample location, and coal bed thickness and Se. Calorific values -for the samples, calculated on a moist, mineral matter free basis, indicate that the apparent rank of the coal is high volatile C bituminous.Variations observed in the chemical and physical characteristics of the coal beds may be related to depositional environments. Total ash yields and concentrations of Se and organic sulfur increase toward more landward depositional environments and may be related to an increase of fluvial influence on peat deposition. Variations in pyritic sulfur concentrations may be related to post-peat pyrite filled burrows commonly observed in the upper part of the coal bed. The thickest coal beds that have the lowest ash content, and highest calorific values, formed from peats deposited in back barrier, tidal flat environments of the central and western parts of the coal field. The reasons for correlations between Se and coal bed thickness and Se and ash content are not clear and may be a product of averaging.

Microfractures in bed-parallel veins (beef) as predictors of vertical macrofractures in shale: Vaca Muerta Formation, Agrio Fold-and-Thrust Belt, Argentina

NASA Astrophysics Data System (ADS)

Ukar, Estibalitz; Lopez, Ramiro G.; Laubach, Stephen E.; Gale, Julia F. W.; Manceda, René; Marrett, Randall

2017-11-01

Shales of the Upper Jurassic-Lower Cretaceous Vaca Muerta Formation are the main source rock for petroleum in the Neuquén Basin, Argentina and an important unconventional exploration target. Folded Vaca Muerta Formation is well exposed in the Agrio Fold-and-Thrust belt where an arid climate and rapid erosion reveal relatively unweathered shale strata accessible along creek beds at Arroyo Mulichinco and in 10+ m-tall cliffs at Puesto. Widespread within these organic-rich shales are several cm-thick, prominent bed-parallel veins (BPVs) of fibrous calcite (beef) that are cut by multiple sets of vertical calcite lined or filled fractures having apertures unaffected by near-surface stress release. Similar, and probably contemporaneous fractures are present within horizons of interbedded dolomitic rock. Evidence that vertical fractures in BPVs and dolomitic horizons continue into shale beds suggests that in-depth analysis of vertical fractures within BPVs and dolomitic horizons allows fracture set and orientation identification and size population measurements-primarily aperture distributions-that circumvent some of the limitations of shale outcrops. At Arroyo Mulichinco, four main fracture sets are present separable by orientation and crosscutting relations. An E-W set is oldest, followed by successively younger NE-SW, NW-SE, and N-S sets. At Puesto, the E-W and N-S sets are the most prominent and show opposite cross-cutting relationships (E-W set is youngest) indicating a possible episode of younger E-W fractures. The E-W set shows the highest micro-and macrofracture intensity at both localities. The intensity of N-S micro- and macrofractures is similar at both outcrops away from faults, but macrofracture intensity increases closer to faults. While macrofracture abundance is similar in BPVs and in shale, microfractures having apertures smaller than ∼0.1 mm are mostly absent in shale and dolomitic layers but are abundant cutting BPVs. Thus, microfractures are BPV-bounded and only fractures wider than ∼0.05 mm are tall enough to cut into shale. Nevertheless, using size distributions of microfractures in BPVs that are absent in shale accurately predicts the abundance of macrofractures in nearby shale, either because microfractures in organic shale have annealed, or because of only small differences in fracture strain for fractures of different sizes across different rocks types. Microfractures in readily sampled BPVs may be a practical way to diagnose or predict attributes of macrofractures in adjacent shale.

Sedimentology and stratigraphy of the Kanayut Conglomerate, central and western Brooks Range, Alaska; report of 1981 field season

USGS Publications Warehouse

Nilsen, T.H.; Moore, T.E.

1982-01-01

The Upper Devonian and Lower Mississippian(?) Kanayut Conglomerate forms a major stratigraphic unit along the crest of the Brooks Range of northern Alaska. It crops out for an east-west distance of about 900 km and a north-south distance of about 65 km. The Kanayut is wholly allochthonous and has probably been transported northward on a series of thrust plates. The Kanayut is as thick as 2,600 m in the east-central Brooks Range. It thins and fines to the south and west. The Kanayut forms the middle part of the allochthonous sequence of the Endicott Group, an Upper Devonian and Mississippian clastic sequence underlain by platform limestones of the Baird Group and overlain by platform limestone, carbonaceous shale, and black chert of the Lisburne Group. The Kanayut overlies the marine Upper Devonian Noatak Sandstone or, where it is missing, the marine Upper Devonian Hunt Fork Shale. It is overlain by the marine Mississippian Kayak Shale. The Kanayut Conglomerate forms the fluvial part of a large, coarse-grained delta that prograded to the southwest in Late Devonian time and retreated in Early Mississippian time. Four sections of the Kanayut Conglomerate in the central Brooks Range and five in the western Brooks Range were measured in 1981. The sections from the western Brooks Range document the presence of fluvial cycles in the Kanayut as far west as the shores of the Chukchi Sea. The Kanayut in this area is generally finer grained than it is in the central and eastern Brooks Range, having a maximum clast size of 3 cm. It is probably about 300 m thick. The upper and lower contacts of the Kanayut are gradational. The lower Kanayut contains calcareous, marine-influenced sandstone within channel deposits, and the upper Kanayut contains probable marine interdistributary-bay shale sequences. The members of the Kanayut Conglomerate cannot be differentiated in this region. In the central Brooks Range, sections of the Kanayut Conglomerate at Siavlat Mountain and Kakivilak Creek are typically organized into fining-upward fluvial cycles. The maximum clast size is about 3 cm in this area. The Kanayut in this region is 200-500 m thick and can be divided into the Ear Peak, Shainin Lake, and Stuver Members. The upper contact of the Kanayut with the Kayak Shale is very gradational at Kakivilak Creek and very abrupt at Siavlat Mountain. Paleocurrents from fluvial strata of the Kanayut indicate sediment transport toward the west and south in both the western and central Brooks Range. The maximum clast size distribution generally indicates westward fining from the Shainin Lake region.

Towards Characterization, Modeling, and Uncertainty Quantification in Multi-scale Mechanics of Oragnic-rich Shales

NASA Astrophysics Data System (ADS)

Abedi, S.; Mashhadian, M.; Noshadravan, A.

2015-12-01

Increasing the efficiency and sustainability in operation of hydrocarbon recovery from organic-rich shales requires a fundamental understanding of chemomechanical properties of organic-rich shales. This understanding is manifested in form of physics-bases predictive models capable of capturing highly heterogeneous and multi-scale structure of organic-rich shale materials. In this work we present a framework of experimental characterization, micromechanical modeling, and uncertainty quantification that spans from nanoscale to macroscale. Application of experiments such as coupled grid nano-indentation and energy dispersive x-ray spectroscopy and micromechanical modeling attributing the role of organic maturity to the texture of the material, allow us to identify unique clay mechanical properties among different samples that are independent of maturity of shale formations and total organic content. The results can then be used to inform the physically-based multiscale model for organic rich shales consisting of three levels that spans from the scale of elementary building blocks (e.g. clay minerals in clay-dominated formations) of organic rich shales to the scale of the macroscopic inorganic/organic hard/soft inclusion composite. Although this approach is powerful in capturing the effective properties of organic-rich shale in an average sense, it does not account for the uncertainty in compositional and mechanical model parameters. Thus, we take this model one step forward by systematically incorporating the main sources of uncertainty in modeling multiscale behavior of organic-rich shales. In particular we account for the uncertainty in main model parameters at different scales such as porosity, elastic properties and mineralogy mass percent. To that end, we use Maximum Entropy Principle and random matrix theory to construct probabilistic descriptions of model inputs based on available information. The Monte Carlo simulation is then carried out to propagate the uncertainty and consequently construct probabilistic descriptions of properties at multiple length-scales. The combination of experimental characterization and stochastic multi-scale modeling presented in this work improves the robustness in the prediction of essential subsurface parameters in engineering scale.

Improved Characterization and Modeling of Tight Oil Formations for CO 2 Enhanced Oil Recovery Potential and Storage Capacity Estimation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sorensen, James; Smith, Steven; Kurz, Bethany

Tight oil formations such as those in the Bakken petroleum system are known to hold hundreds of billions of barrels of oil in place; however, the primary recovery factor for these plays is typically less than 10%. Tight oil formations, including the Bakken Formation, therefore, may be attractive candidates for enhanced oil recovery (EOR) using CO 2. Multiphase fluid behavior and flow in fluid-rich shales can vary substantially depending on the size of pore throats, and properties such as fluid viscosity and density are much different in nanoscale pores than in macroscale pores. Thus it is critical to understand themore » nature and distribution of nano-, micro-, and macroscale pores and fracture networks. To address these issues, the Energy & Environmental Research Center (EERC) has been conducting a research program entitled “Improved Characterization and Modeling of Tight Oil Formations for CO 2 Enhanced Oil Recovery Potential and Storage Capacity Estimation.” The objectives of the project are 1) the use of advanced characterization methods to better understand and quantify the petrophysical and geomechanical factors that control CO 2 and oil mobility within tight oil formation samples, 2) the determination of CO 2 permeation and oil extraction rates in tight reservoir rocks and organic-rich shales of the Bakken, and 3) the integration of the laboratory-based CO 2 permeation and oil extraction data and the characterization data into geologic models and dynamic simulations to develop predictions of CO 2 storage resource and EOR in the Bakken tight oil formation. A combination of standard and advanced petrophysical characterization techniques were applied to characterize samples of Bakken Formation tight reservoir rock and shales from multiple wells. Techniques included advanced computer tomography (CT) imaging, scanning electron microscopy (SEM) techniques, whole-core and micro x-ray CT imaging, field emission (FE) SEM, and focused ion beam (FIB) SEM. Selected samples were also analyzed for geomechanical properties. X-ray CT imaging yielded information on the occurrence of fractures, bedding planes, fossils, and bioturbation in core, as well as data on bulk density and photoelectric factor logs, which were used to interpret porosity, organic content, and mineralogy. FESEM was used for characterization of nano- and microscale features, including nanoscale pore visualization and micropore and pore throat mineralogy. FIBSEM yielded micro- to nanoscale visualization of fracture networks, porosity and pore-size distribution, connected versus isolated porosity, and distribution of organics. Results from the characterization activities provide insight on nanoscale fracture properties, pore throat mineralogy and connectivity, rock matrix characteristics, mineralogy, and organic content. Laboratory experiments demonstrated that CO 2 can permeate the tight matrix of Bakken shale and nonshale reservoir samples and mobilize oil from those samples. Geologic models were created at scales ranging from the core plug to the reservoir, and dynamic simulations were conducted. The data from the characterization and laboratory-based activities were integrated into modeling research activities to determine the fundamental mechanisms controlling fluid transport in the Bakken, which support EOR scheme design and estimation of CO 2 storage potential in tight oil formations. Simulation results suggest a CO 2 storage resource estimate range of 169 million to 1.5 billion tonnes for the Bakken in North Dakota, possibly resulting in 1.8 billion to 16 billion barrels of incremental oil.« less

Maps showing thermal maturity of Upper Cretaceous marine shales in the Bighorn Basin, Wyoming and Montana

USGS Publications Warehouse

Finn, Thomas M.; Pawlewicz, Mark J.

2014-01-01

The Bighorn Basin is one of many structural and sedimentary basins that formed in the Rocky Mountain foreland during the Laramide orogeny, a period of crustal instability and compressional tectonics that began in latest Cretaceous time and ended in the Eocene. The basin is nearly 180 mi long, 100 mi wide, and encompasses about 10,400 mi2 in north-central Wyoming and south-central Montana. The basin is bounded on the northeast by the Pryor Mountains, on the east by the Bighorn Mountains, and on the south by the Owl Creek Mountains). The north boundary includes a zone of faulting and folding referred to as the Nye-Bowler lineament. The northwest and west margins are formed by the Beartooth Mountains and Absaroka Range, respectively. Important conventional oil and gas resources have been discovered and produced from reservoirs ranging in age from Cambrian through Tertiary. In addition, a potential unconventional basin-centered gas accumulation may be present in Cretaceous reservoirs in the deeper parts of the basin. It has been suggested by numerous authors that various Cretaceous marine shales are the principal source rock for these accumulations. Numerous studies of various Upper Cretaceous marine shales in the Rocky Mountain region have led to the general conclusion that these rocks have generated or are capable of generating oil and (or) gas. In recent years, advances in horizontal drilling and multistage fracture stimulation have resulted in increased exploration and completion of wells in Cretaceous marine shales in other Rocky Mountain Laramide basins that were previously thought of only as hydrocarbon source rocks. Important parameters controlling hydrocarbon production from these shale reservoirs include: reservoir thickness, amount and type of organic matter, and thermal maturity. The purpose of this report is to present maps and a cross section showing levels of thermal maturity, based on vitrinite reflectance (Ro), for selected Upper Cretaceous marine shales in the Bighorn Basin.

Evaluation of PAH contamination in soil treated with solid by-products from shale pyrolysis.

PubMed

Nicolini, Jaqueline; Khan, Muhammad Y; Matsui, M; Côcco, Lílian C; Yamamoto, Carlos I; Lopes, Wilson A; de Andrade, Jailson B; Pillon, Clenio N; Arizaga, Gregorio G Carbajal; Mangrich, Antonio S

2015-01-01

The aim of this work was to evaluate the concentrations of polycyclic aromatic hydrocarbons (PAHs) in soils to which solid shale materials (SSMs) were added as soil conditioners. The SSMs were derived from the Petrosix pyrolysis process developed by Petrobras (Brazil). An improved ultrasonic agitation method was used to extract the PAHs from the solid samples (soils amended with SSMs), and the concentrations of the compounds were determined by gas chromatography coupled to mass spectrometry (GC-MS). The procedure provided satisfactory recoveries, detection limits, and quantification limits. The two-, three-, and four-ring PAHs were most prevalent, and the highest concentration was obtained for phenanthrene (978 ± 19 μg kg(-1) in a pyrolyzed shale sample). The use of phenanthrene/anthracene and fluoranthene/pyrene ratios revealed that the PAHs were derived from petrogenic rather than pyrogenic sources. The measured PAH concentrations did not exceed national or international limit values, suggesting that the use of SSMs as soil conditioners should not cause environmental damage.

A novel method for the determination of adsorption partition coefficients of minor gases in a shale sample by headspace gas chromatography.

PubMed

Zhang, Chun-Yun; Hu, Hui-Chao; Chai, Xin-Sheng; Pan, Lei; Xiao, Xian-Ming

2013-10-04

A novel method has been developed for the determination of adsorption partition coefficient (Kd) of minor gases in shale. The method uses samples of two different sizes (masses) of the same material, from which the partition coefficient of the gas can be determined from two independent headspace gas chromatographic (HS-GC) measurements. The equilibrium for the model gas (ethane) was achieved in 5h at 120°C. The method also involves establishing an equation based on the Kd at higher equilibrium temperature, from which the Kd at lower temperature can be calculated. Although the HS-GC method requires some time and effort, it is simpler and quicker than the isothermal adsorption method that is in widespread use today. As a result, the method is simple and practical and can be a valuable tool for shale gas-related research and applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Understanding fluid transport through the multiscale pore network of a natural shale

NASA Astrophysics Data System (ADS)

Davy, Catherine A.; Nguyen Kim, Thang; Song, Yang; Troadec, David; Blanchenet, Anne-Marie; Adler, Pierre M.

2017-06-01

The pore structure of a natural shale is obtained by three imaging means. Micro-tomography results are extended to provide the spatial arrangement of the minerals and pores present at a voxel size of 700 nm (the macroscopic scale). FIB/SEM provides a 3D representation of the porous clay matrix on the so-called mesoscopic scale (10-20 nm); a connected pore network, devoid of cracks, is obtained for two samples out of five, while the pore network is connected through cracks for two other samples out of five. Transmission Electron Microscopy (TEM) is used to visualize the pore space with a typical pixel size of less than 1 nm and a porosity ranging from 0.12 to 0.25. On this scale, in the absence of 3D images, the pore structure is reconstructed by using a classical technique, which is based on truncated Gaussian fields. Permeability calculations are performed with the Lattice Boltzmann Method on the nanoscale, on the mesoscale, and on the combination of the two. Upscaling is finally done (by a finite volume approach) on the bigger macroscopic scale. Calculations show that, in the absence of cracks, the contribution of the nanoscale pore structure on the overall permeability is similar to that of the mesoscale. Complementarily, the macroscopic permeability is measured on a centimetric sample with a neutral fluid (ethanol). The upscaled permeability on the macroscopic scale is in good agreement with the experimental results.

The Drenchwater deposit, Alaska: An example of a natural low pH environment resulting from weathering of an undisturbed shale-hosted Zn-Pb-Ag deposit

USGS Publications Warehouse

Graham, G.E.; Kelley, K.D.

2009-01-01

The Drenchwater shale-hosted Zn-Pb-Ag deposit and the immediate vicinity, on the northern flank of the Brooks Range in north-central Alaska, is an ideal example of a naturally low pH system. The two drainages, Drenchwater and False Wager Creeks, which bound the deposit, differ in their acidity and metal contents. Moderately acidic waters with elevated concentrations of metals (pH ??? 4.3, Zn ??? 1400 ??g/L) in the Drenchwater Creek drainage basin are attributed to weathering of an exposed base-metal-rich massive sulfide occurrence. Stream sediment and water chemistry data collected from False Wager Creek suggest that an unexposed base-metal sulfide occurrence may account for the lower pH (2.7-3.1) and very metal-rich waters (up to 2600 ??g/L Zn, ??? 260 ??g/L Cu and ???89 ??g/L Tl) collected at least 2 km upstream of known mineralized exposures. These more acidic conditions produce jarosite, schwertmannite and Fe-hydroxides commonly associated with acid-mine drainage. The high metal concentrations in some water samples from both streams naturally exceed Alaska state regulatory limits for freshwater aquatic life, affirming the importance of establishing base-line conditions in the event of human land development. The studies at the Drenchwater deposit demonstrate that poor water quality can be generated through entirely natural weathering of base-metal occurrences, and, possibly unmineralized black shale.

Characteristics and geological significance of Re-Os isotopic system of evaporites in Mboukoumassi deposit, the Republic of Congo

NASA Astrophysics Data System (ADS)

Zhao, Xianfu; Wang, Zongqi; Liu, Chenglin; Li, Chao; Jiao, Pengcheng; Zhao, Yanjun; Zhang, Fan

2018-02-01

Evaporite dating has been an open problem. The study investigates the Re-Os isotopic system in the organic-rich sedimentary rocks to constrain the infilling of sedimentary basin and related geological events. In the Mboukoumassi potash deposit in the Republic of Congo (Congo-Brazzaville) in West Africa, several layers of organic-rich dark shale were found in the evaporite series. Through drilling core, the dark shale in the evaporite is found to satisfy the requirements of Re-Os isotope test. The result shows that the Re-Os isochron age of the dark shale in the study area ranges from 78.7 ± 1.1 to 96 ± 7 Ma, which is the first precise age of the Mboukoumassi potash deposit in the Republic of Congo (Congo-Brazzaville), West Africa. Therefore, the age of deposition of this set of evaporite may be Cenomanian-Turonian, which is younger than the age previously thought (around 113-125Ma, Aptian). The Re-Os isotopic dating technique used for the pioneering study on the precise dating of the Mboukoumassi potash deposit provides a new approach to the study of the sedimentary age of ancient evaporite deposits. The initial 187Os/188Os value decreasing from 2.02 ± 0.21 to 0.982 ± 0.03 for the core sample reflects the source rock chang along the core, and this is consistent with the geological evolution of the basin.

Geochemical and multi-isotopic ( 87Sr/ 86Sr, 143Nd/ 144Nd, 238U/ 235U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

DOE PAGES

Phan, Thai T.; Gardiner, James B.; Capo, Rosemary C.; ...

2017-10-25

Here, we investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from –7.8 to –6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from amore » well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns.« less

Geochemical and multi-isotopic ( 87Sr/ 86Sr, 143Nd/ 144Nd, 238U/ 235U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phan, Thai T.; Gardiner, James B.; Capo, Rosemary C.

Here, we investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from –7.8 to –6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from amore » well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns.« less

Multiple Approaches to Characterizing Nano-Pore Structure of Barnett Shale

NASA Astrophysics Data System (ADS)

Hu, Q.; Gao, Z.; Ewing, R. P.; Dultz, S.; Kaufmann, J.; Hamamoto, S.; Webber, B.; Ding, M.

2013-12-01

Microscopic characteristics of porous media - pore shape, pore-size distribution, and pore connectivity - control fluid flow and mass transport. This presentation discusses various approaches to investigating nano-pore structure of Barnett shale, with its implications in gas production behavior. The innovative approaches include imbibition, tracer diffusion, edge-accessible porosity, porosimetry (mercury intrusion porosimetry, nitrogen and water vapor sorption isotherms, and nuclear magnetic resonance cyroporometry), and imaging (Wood's metal impregnation followed with laser ablation-inductively coupled plasma-mass spectrometry, focused ion beam/scanning electron microscopy, and small angle neutron scattering). Results show that the shale pores are predominantly in the nm size range, with measured median pore-throat diameters about 5 nm. But small pore size is not the major contributor to low gas recovery; rather, the low mass diffusivity appears to be caused by low pore connectivity of Barnett shale. Chemical diffusion in sparsely-connected pore spaces is not well described by classical Fickian behavior; anomalous behavior is suggested by percolation theory, and confirmed by results of imbibition and diffusion tests. Our evolving complementary approaches, with their several advantages and disadvantages, provide a rich toolbox for tackling the nano-pore structure characteristics of shales and other natural rocks.

Benthic foraminiferal fauna as a tool to indicate the Toarcian Oceanic Anoxic Event in homogeneous Ammonitico Rosso series of Bakonycsernye (Transdanubian Hungary)

NASA Astrophysics Data System (ADS)

Zsiborás, Gábor; Görög, Ágnes

2017-04-01

In the last decades, since the Toarcian Oceanic Anoxic Event (T-OAE, ˜182 Ma) recognized, several studies was dealing with the effect of it on the foraminiferal faunas from black shales and marls of the epicontinental region. Only a few work was made from the Tethyan oceanic basin region (Monaco et al., 1994; Nini et al., 1995; Pettinelli et al., 1997) characterized by occurrence of black shales between the "Lower Posidonia Shale" and the Ammonitico Rosso. However, the black shale is absent in some Tehyan sections substituted by red or grey marls. Only Reolid et al. (2015) focused on foraminifera from this kind of successions, from the Betic Cordillera, where the T-OAE was not detected. From the section of Tű zkövesárok of Bakonycsernye, Transdanubian Central Range, Hungary, Monostori in Galácz et al. (2008) based on the Bairdidae dominated ostracod fauna indicated suboxic environment at the Pliensbachian/Toarcian boundary. Thus the aim of our study was to give paleoecological interpretation of the foraminiferal fauna of this 2 m thick Ammonitico Rosso sequence. Foraminifers were extracted from six red nodular, slightly argillaceous limestone (Tű zkövesárok Limestone) samples from the Pliensbachian part (Emaciatum Zone) and one sample from the Toarcian part (Tenuicostatum Zone) which begins with a hardground and following by red marl (Kisgerecse Marl). The washing residues of the lower four samples contains foraminifers, sponge spicules, radiolarians and echinodermata parts (crinoids and holothurians). The upper two Pliensbachian samples include more foraminifers, however, other groups are absent. The Toarcian sample contains crinoids and less foraminifers (30%). Overall 68 taxa were identified, 54 on species, 14 on generic level. The most of the specimens have calcitic tests, in the Pliensbachian, agglutinated forms are 7-24% of the fauna, however, they are absent in the Toarcian. Upwards to the Pliensbachian/Toarcian boundary, the diversity of the fauna rapidly increased. Above the boundary, the number of species decreased to the 40% of the Pliensbachian maximum diversity. Sorting the specimens by morphological features is a tool for the paleoecological evaluation. In the Pliensbachian assemblages, the biconvex groups (Lenticulina) are dominant, however, elongated (Nodosaria and Eoguttulina) and flattened (Planularia) groups are dominant in the Toarcian. This morphological changing indicates the decreasing of seawater oxygen level and current energy in the lowermost Toarcian. It does not show anoxia but can be suboxia caused by abrupt deepening. The previous results of the ostracod studies indicated the same events. The Pliensbachian/Toarcian boundary section of Tű zkövesárok include a similar foraminiferal fauna to other Tethyan successions Spoleto and Umbria-Marche Apennines (Central Italy), Ionian Basin (Greece); and epicontinental sequences e. g., Lusitanian Basin (Portugal) which all have black shale layers in the Early Toarcian. In contrast, the Betic section with very similar lithology to Bakonycsernye provided a totally different fauna with dominance of agglutinated forms and without significant diversity changes at the boundary. The studied boundary section is the first Ammonitico Rosso sequence which foraminiferal fauna indicated the environmental changes caused by the T-OAE in the deep basin of the Tethyan Realm. The Research was supported by the Hantken Foundation.

Recovery and fractionation of phosphorus retained by lightweight expanded shale and masonry sand used as media in subsurface flow treatment wetlands.

PubMed

Forbes, Margaret G; Dickson, Kenneth L; Saleh, Farida; Waller, William T; Doyle, Robert D; Hudak, Paul

2005-06-15

Most subsurface flow treatment wetlands, also known as reed bed or root zone systems, use sand or gravel substrates to reduce organics, solids, and nutrients in septic tank effluents. Phosphorus (P) retention in these systems is highly variable and few studies have identified the fate of retained P. In this study, two substrates, expanded shale and masonry sand, were used as filter media in five subsurface flow pilot-scale wetlands (2.7 m3). After 1 year of operation, we estimated the annual rate of P sorption by taking the difference between total P (TP) of substrate in the pilot cells and TP of substrate not exposed to wastewater (control). Means and standard deviations of TP retained by expanded shale were 349 +/- 171 mg kg(-1), respectively. For a substrate depth of 0.9 m, aerial P retention by shale was 201 +/- 98.6 g of P m(-2) year(-1), respectively. Masonry sand retained an insignificant quantity of wastewater P (11.9 +/- 21.8 mg kg(-1)) and on occasion exported P. Substrate samples were also sequentially fractionated into labile P, microbial P, (Fe + Al) P, humic P, (Ca + Mg) P, and residual P. In expanded shale samples, the greatest increase in P was in the relatively permanent form of (Fe + Al) P (108 mg kg(-1)), followed by labile P (46.7 mg kg(-1)) and humic P (39.8 mg kg(-1)). In masonry sand, there was an increase in labile P (9.71 mg kg(-1)). Results suggest that sand is a poor candidate for long-term P storage, but its efficiency is similar to that reported for many sand, gravel, and rock systems. By contrast, expanded shale and similar products with high hydraulic conductivity and P sorption capacity could greatly improve performance of P retention in constructed wetlands.

Fischer Assays of Oil Shale Drill Cores and Rotary Cuttings from the Piceance Basin, Colorado - 2009 Update

USGS Publications Warehouse

Mercier, Tracey J.; Brownfield, Michael E.; Johnson, Ronald C.; Self, Jesse G.

1998-01-01

This CD-ROM includes updated files containing Fischer assays of samples of core holes and cuttings from exploration drill holes drilled in the Eocene Green River Formation in the Piceance Basin of northwestern Colorado. A database was compiled that includes more than 321,380 Fischer assays from 782 boreholes. Most of the oil yield data were analyzed by the former U.S. Bureau of Mines oil shale laboratory in Laramie, Wyoming, and some analyses were made by private laboratories. Location data for 1,042 core and rotary holes, oil and gas tests, as well as a few surface sections are listed in a spreadsheet and included in the CD-ROM. These assays are part of a larger collection of subsurface information held by the U.S. Geological Survey, including geophysical and lithologic logs, water data, and chemical and X-ray diffraction analyses having to do with the Green River oil shale deposits in Colorado, Wyoming, and Utah. Because of an increased interest in oil shale, this CD-ROM disc containing updated Fischer assay data for the Piceance Basin oil shale deposits in northwestern Colorado is being released to the public.

Identification of crude oil source facies in Railroad Valley, Nevada, using multivariate analysis of crude oil and hydrous pyrolysis data from the Meridian Spencer Federal 32-29 well

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conlan, L.M.; Francis, R.D.

Comparison of biological markers of a hydrous pyrolyzate of Mississippian-Chainman Shale from the Meridian Spencer Federal 32-29 well with two crude oils produced from the same well and crude oils produced from Trap Springs, Grant Canyon, Bacon Flats, and Eagle Springs fields indicate the possibility of three distinct crude oil source facies within Railroad Valley, Nevada. The two crude oil samples produced in the Meridian Spencer Federal 32-29 well are from the Eocene Sheep Pass Formation (MSF-SP) at 10,570 ft and the Joana Limestone (MSF-J) at 13,943 ft; the pyrolyzate is from the Chainman Shale at 10,700 ft. The Chainmanmore » Shale pyrolyzate has a similar composition to oils produced in Trap Springs and Grant Canyon fields. Applying multivariate statistical analysis to biological marker data shows that the Chainman Shale is a possible source for oil produced at Trap Springs because of the similarities between Trap Springs oils and the Chainman Shale pyrolyzate. It is also apparent that MSF-SP and oils produced in the Eagle Springs field have been generated from a different source (probably the Sheep Pass Formation) because of the presence of gammacerane (C{sub 30}). MSF-J and Bacon Flats appear to be either sourced from a pre-Mississippian unit or from a different facies within the Chainman Shale because of the apparent differences between MSF-J and Chainman Shale pyrolyzate.« less

Carbon-13 and proton nuclear magnetic resonance analysis of shale-derived refinery products and jet fuels and of experimental referee broadened-specification jet fuels

NASA Technical Reports Server (NTRS)

Dalling, D. K.; Bailey, B. K.; Pugmire, R. J.

1984-01-01

A proton and carbon-13 nuclear magnetic resonance (NMR) study was conducted of Ashland shale oil refinery products, experimental referee broadened-specification jet fuels, and of related isoprenoid model compounds. Supercritical fluid chromatography techniques using carbon dioxide were developed on a preparative scale, so that samples could be quantitatively separated into saturates and aromatic fractions for study by NMR. An optimized average parameter treatment was developed, and the NMR results were analyzed in terms of the resulting average parameters; formulation of model mixtures was demonstrated. Application of novel spectroscopic techniques to fuel samples was investigated.

The geochemistry of naturally occurring methane and saline groundwater in an area of unconventional shale gas development

NASA Astrophysics Data System (ADS)

Harkness, Jennifer S.; Darrah, Thomas H.; Warner, Nathaniel R.; Whyte, Colin J.; Moore, Myles T.; Millot, Romain; Kloppmann, Wolfram; Jackson, Robert B.; Vengosh, Avner

2017-07-01

Since naturally occurring methane and saline groundwater are nearly ubiquitous in many sedimentary basins, delineating the effects of anthropogenic contamination sources is a major challenge for evaluating the impact of unconventional shale gas development on water quality. This study investigates the geochemical variations of groundwater and surface water before, during, and after hydraulic fracturing and in relation to various geospatial parameters in an area of shale gas development in northwestern West Virginia, United States. To our knowledge, we are the first to report a broadly integrated study of various geochemical techniques designed to distinguish natural from anthropogenic sources of natural gas and salt contaminants both before and after drilling. These measurements include inorganic geochemistry (major cations and anions), stable isotopes of select inorganic constituents including strontium (87Sr/86Sr), boron (δ11B), lithium (δ7Li), and carbon (δ13C-DIC), select hydrocarbon molecular (methane, ethane, propane, butane, and pentane) and isotopic tracers (δ13C-CH4, δ13C-C2H6), tritium (3H), and noble gas elemental and isotopic composition (helium, neon, argon) in 105 drinking-water wells, with repeat testing in 33 of the wells (total samples = 145). In a subset of wells (n = 20), we investigated the variations in water quality before and after the installation of nearby (<1 km) shale-gas wells. Methane occurred above 1 ccSTP/L in 37% of the groundwater samples and in 79% of the samples with elevated salinity (chloride > 50 mg/L). The integrated geochemical data indicate that the saline groundwater originated via naturally occurring processes, presumably from the migration of deeper methane-rich brines that have interacted extensively with coal lithologies. These observations were consistent with the lack of changes in water quality observed in drinking-water wells following the installation of nearby shale-gas wells. In contrast to groundwater samples that showed no evidence of anthropogenic contamination, the chemistry and isotope ratios of surface waters (n = 8) near known spills or leaks occurring at disposal sites mimicked the composition of Marcellus flowback fluids, and show direct evidence for impact on surface water by fluids accidentally released from nearby shale-gas well pads and oil and gas wastewater disposal sites. Overall this study presents a comprehensive geochemical framework that can be used as a template for assessing the sources of elevated hydrocarbons and salts to water resources in areas potentially impacted by oil and gas development.

Preliminary report on the clay mineralogy of the Upper Devonian Shales in the southern and middle Appalachian Basin

USGS Publications Warehouse

Hosterman, John W.; Loferski, Patricia J.

1978-01-01

The distribution of kaolinite in parts of the Devonian shale section is the most significant finding of this work. These shales are composed predominately of 2M illite and illitic mixed-layer clay with minor amounts of chlorite and kaolinite. Preliminary data indicate that kaolinite, the only allogenic clay mineral, is present in successively older beds of the Ohio Shale from south to north in the southern and middle parts of the Appalachian basin. This trend in the distribution of kaolinite shows a paleocurrent direction to the southwest. Three well-known methods of preparing the clay fraction for X-ray diffraction analysis were tested and evaluated. Kaolinite was not identified in two of the methods because of layering due to differing settling rates of the clay minerals. It is suggested that if one of the two settling methods of sample preparation is used, the clay film be thin enough for the X-ray beam to penetrate the entire thickness of clay.

Lung Cancer Risk from Radon in Marcellus Shale Gas in Northeast U.S. Homes.

PubMed

Mitchell, Austin L; Griffin, W Michael; Casman, Elizabeth A

2016-11-01

The amount of radon in natural gas varies with its source. Little has been published about the radon from shale gas to date, making estimates of its impact on radon-induced lung cancer speculative. We measured radon in natural gas pipelines carrying gas from the Marcellus Shale in Pennsylvania and West Virginia. Radon concentrations ranged from 1,520 to 2,750 Bq/m 3 (41-74 pCi/L), and the throughput-weighted average was 1,983 Bq/m 3 (54 pCi/L). Potential radon exposure due to the use of Marcellus Shale gas for cooking and space heating using vent-free heaters or gas ranges in northeastern U.S. homes and apartments was assessed. Though the measured radon concentrations are higher than what has been previously reported, it is unlikely that exposure from natural gas cooking would exceed 1.2 Bq/m 3 (<1% of the U.S. Environmental Protection Agency's action level). Using worst-case assumptions, we estimate the excess lifetime (70 years) lung cancer risk associated with cooking to be 1.8×10 -4 (interval spanning 95% of simulation results: 8.5×10 -5 , 3.4×10 -4 ). The risk profile for supplemental heating with unvented gas appliances is similar. Individuals using unvented gas appliances to provide primary heating may face lifetime risks as high as 3.9×10 -3 . Under current housing stock and gas consumption assumptions, expected levels of residential radon exposure due to unvented combustion of Marcellus Shale natural gas in the Northeast United States do not result in a detectable change in the lung cancer death rates. © 2016 Society for Risk Analysis.

Characterization of Radium and Radon Isotopes in Hydraulic Fracturing Flowback Fluid and Gas from the Marcellus Shale

NASA Astrophysics Data System (ADS)

Bardsley, A.

2015-12-01

High volume hydraulic fracturing of unconventional deposits has expanded rapidly over the past decade in the US, with much attention focused on the Marcellus Shale gas reservoir in the northeastern US. We use naturally occurring radium isotopes and 222Rn to explore changes in formation characteristics as a result of hydraulic fracturing. Gas and produced waters were analyzed from time series samples collected soon after hydraulic fracturing at three Marcellus Shale well sites in the Appalachian Basin, USA. Analyses of δ18O, Cl- , and 226Ra in flowback fluid are consistent with two end member mixing between injected slick water and formation brine. All three tracers indicate that the ratio of injected water to formation brine declines with time across both time series. Cl- concentration (max ~1.5-2.2 M) and 226Ra activity (max ~165-250 Bq/Kg) in flowback fluid are comparable at all three sites. There are differences evident in the stable isotopic composition (δ18O & δD) of injected slick water across the three sites, but all appear to mix with formation brine of similar isotopic composition. On a plot of water isotopes, δ18O in formation brine-dominated fluid is enriched by ~3-4 permille relative to the Global Meteoric Water Line, indicating oxygen exchange with shale. The ratio of 223Ra/226Ra and 228Ra/226Ra in produced waters is quite low relative to shale samples analyzed. This indicates that most of the 226Ra in the formation brine must be sourced from shale weathering or dissolution rather than emanation due to alpha recoil from the rock surface. During the first week of flowback, ratios of short lived isotopes 223Ra and 224Ra to longer lived radium isotopes change modestly, suggesting rock surface area per unit of produced water volume did not change substantially. For one well, longer term gas samples were collected. The 222Rn/methane ratio in produced gas from this site declines with time and may represent a decrease in the brine to gas ratio in the reservoir over the course of six months after initial fracturing. Naturally occurring radium and radon isotopes show promise in elucidating sub-surface dynamics following hydraulic fracturing plays.

Noble gases in gas shales : Implications for gas retention and circulating fluids.

NASA Astrophysics Data System (ADS)

Basu, Sudeshna; Jones, Adrian; Verchovsky, Alexander

2016-04-01

Gas shales from three cores of Haynesville-Bossier formation have been analysed simultaneously for carbon, nitrogen and noble gases (He, Ne, Ar, Xe) to constrain their source compositions and identify signatures associated with high gas retention. Ten samples from varying depths of 11785 to 12223 feet from each core, retrieved from their centres, have been combusted from 200-1200°C in incremental steps of 100°C, using 5 - 10 mg of each sample. Typically, Xe is released at 200°C and is largely adsorbed, observed in two of the three cores. The third core lacked any measureable Xe. High 40Ar/36Ar ratio up to 8000, is associated with peak release of nitrogen with distinctive isotopic signature, related to breakdown of clay minerals at 500°C. He and Ne are also mostly released at the same temperature step and predominantly hosted in the pore spaces of the organic matter associated with the clay. He may be produced from the uranium related to the organic matter. The enrichment factors of noble gases defined as (iX/36Ar)sample/(iX/36Ar)air where iX denotes any noble gas isotope, show Ne and Xe enrichment observed commonly in sedimentary rocks including shales (Podosek et al., 1980; Bernatowicz et al., 1984). This can be related to interaction of the shales with circulating fluids and diffusive separation of gases (Torgersen and Kennedy, 1999), implying the possibility of loss of gases from these shales. Interaction with circulating fluids (e.g. crustal fluids) have been further confirmed using 20Ne/N2, 36Ar/N2 and 4He/N2 ratios. Deviations of measured 4He/40Ar* (where 40Ar* represents radiogenic 40Ar after correcting for contribution from atmospheric Ar) from expected values has been used to monitor gas loss by degassing. Bernatowicz, T., Podosek, F.A., Honda, M., Kramer, F.E., 1984. The Atmospheric Inventory of Xenon and Noble Gases in Shales: The Plastic Bag Experiment. Journal of Geophysical Research 89, 4597-4611. Podosek, F.A., Honda, M., Ozima, M., 1980. Sedimentary noble gases. Geochimica Cosmochimica Acta 44, 1875-1884. Torgersen, T., Kennedy, B.M., 1999. Air-Xe enrichments in Oil Field Gases and the Influence of Water during Oil Migration and Storage. Earth and Planetary Science Letters167, 239-253.

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

USGS Publications Warehouse

Tuttle, M.L.W.; Breit, G.N.; Goldhaber, M.B.

2009-01-01

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies. Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.

Performance Assessments of Generic Nuclear Waste Repositories in Shale

NASA Astrophysics Data System (ADS)

Stein, E. R.; Sevougian, S. D.; Mariner, P. E.; Hammond, G. E.; Frederick, J.

2017-12-01

Simulations of deep geologic disposal of nuclear waste in a generic shale formation showcase Geologic Disposal Safety Assessment (GDSA) Framework, a toolkit for repository performance assessment (PA) whose capabilities include domain discretization (Cubit), multiphysics simulations (PFLOTRAN), uncertainty and sensitivity analysis (Dakota), and visualization (Paraview). GDSA Framework is used to conduct PAs of two generic repositories in shale. The first considers the disposal of 22,000 metric tons heavy metal of commercial spent nuclear fuel. The second considers disposal of defense-related spent nuclear fuel and high level waste. Each PA accounts for the thermal load and radionuclide inventory of applicable waste types, components of the engineered barrier system, and components of the natural barrier system including the host rock shale and underlying and overlying stratigraphic units. Model domains are half-symmetry, gridded with Cubit, and contain between 7 and 22 million grid cells. Grid refinement captures the detail of individual waste packages, emplacement drifts, access drifts, and shafts. Simulations are run in a high performance computing environment on as many as 2048 processes. Equations describing coupled heat and fluid flow and reactive transport are solved with PFLOTRAN, an open-source, massively parallel multiphase flow and reactive transport code. Additional simulated processes include waste package degradation, waste form dissolution, radioactive decay and ingrowth, sorption, solubility, advection, dispersion, and diffusion. Simulations are run to 106 y, and radionuclide concentrations are observed within aquifers at a point approximately 5 km downgradient of the repository. Dakota is used to sample likely ranges of input parameters including waste form and waste package degradation rates and properties of engineered and natural materials to quantify uncertainty in predicted concentrations and sensitivity to input parameters. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525. SAND2017- 8305 A

Rehabilitation potential and practices of Colorado oil shale lands. Progress report, June 1, 1978--May 31, 1979

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, C.W.

The following document is a third-year progress report for the period June 1, 1978 to May 31, 1979. The overall objective of the project is to study the effects of seeding techniques, species mixtures, fertilizer, ecotypes, improved plant materials, mycorrhizal fungi, and soil microorganisms on the initial and final stages of reclamation obtained through seeding and subsequent succession on disturbed oil shale lands. Plant growth medias that are being used in field-established test plots include retorted shale, soil over retorted shale, subsoil materials, and surface disturbed topsoils. Because of the long-term nature of successional and ecologically oriented studies the projectmore » is just beginning to generate significant publications. Several of the studies associated with the project have some phases being conducted principally in the laboratories and greenhouses at Colorado State Univerisity. The majority of the research, however, is being conducted on a 20 hectare Intensive Study Site located near the focal points of oil shale activity in the Piceance Basin. The site is at an elevation of 2,042 m, receives approximately 30 to 55 cm of precipitation annually, and encompasses the plant communities most typical of the Piceance Basin. Most of the information contained in this report originated from the monitoring and sampling of research plots established in either the fall of 1976 or 1977. Therefore, data that have been obtained from the Intensive Study Site represent only first- or second-year results. However, many trends have been identified in thesuccessional process and the soil microorganisms and mycorrhizal studies continue to contribute significant information to the overall results. The phytosociological study has progressed to a point where field sampling is complete and the application and publication of this materials will be forthcoming in 1979.« less

“Multi-temperature” method for high-pressure sorption measurements on moist shales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gasparik, Matus; Ghanizadeh, Amin; Gensterblum, Yves

2013-08-15

A simple and effective experimental approach has been developed and tested to study the temperature dependence of high-pressure methane sorption in moist organic-rich shales. This method, denoted as “multi-temperature” (short “multi-T”) method, enables measuring multiple isotherms at varying temperatures in a single run. The measurement of individual sorption isotherms at different temperatures takes place in a closed system ensuring that the moisture content remains constant. The multi-T method was successfully tested for methane sorption on an organic-rich shale sample. Excess sorption isotherms for methane were measured at pressures of up to 25 MPa and at temperatures of 318.1 K, 338.1more » K, and 348.1 K on dry and moisture-equilibrated samples. The measured isotherms were parameterized with a 3-parameter Langmuir-based excess sorption function, from which thermodynamic sorption parameters (enthalpy and entropy of adsorption) were obtained. Using these, we show that by taking explicitly into account water vapor as molecular species in the gas phase with temperature-dependent water vapor pressure during the experiment, more meaningful results are obtained with respect to thermodynamical considerations. The proposed method can be applied to any adsorbent system (coals, shales, industrial adsorbents) and any supercritical gas (e.g., CH{sub 4}, CO{sub 2}) and is particularly suitable for sorption measurements using the manometric (volumetric) method.« less

Geochemistry of Archean shales from the Pilbara Supergroup, Western Australia

NASA Astrophysics Data System (ADS)

McLennan, Scott M.; Taylor, S. R.; Eriksson, K. A.

1983-07-01

Archean clastic sedimentary rocks are well exposed in the Pilbara Block of Western Australia. Shales from turbidites in the Gorge Creek Group ( ca. 3.4 Ae) and shales from the Whim Creek Group ( ca. 2.7 Ae) have been examined. The Gorge Creek Group samples, characterized by muscovite-quartzchlorite mineralogy, are enriched in incompatible elements (K, Th, U, LREE) by factors of about two, when compared to younger Archean shales from the Yilgarn Block. Alkali and alkaline earth elements are depleted in a systematic fashion, according to size, when compared with an estimate of Archean upper crust abundances. This depletion is less notable in the Whim Creek Group. Such a pattern indicates the source of these rocks underwent a rather severe episode of weathering. The Gorge Creek Group also has fairly high B content (85 ± 29 ppm) which may indicate normal marine conditions during deposition. Rare earth element (REE) patterns for the Pilbara samples are characterized by light REE enrichment ( La N/Yb N ≥ 7.5 ) and no or very slight Eu depletion ( Eu/Eu ∗ = 0.82 - 0.99 ). A source comprised of about 80% felsic igneous rocks without large negative Eu-anomalies (felsic volcanics, tonalites, trondhjemites) and 20% mafic-ultramafic volcanics is indicated by the trace element data. Very high abundances of Cr and Ni cannot be explained by any reasonable provenance model and a secondary enrichment process is called for.

Stream measurements locate thermogenic methane fluxes in groundwater discharge in an area of shale-gas development.

PubMed

Heilweil, Victor M; Grieve, Paul L; Hynek, Scott A; Brantley, Susan L; Solomon, D Kip; Risser, Dennis W

2015-04-07

The environmental impacts of shale-gas development on water resources, including methane migration to shallow groundwater, have been difficult to assess. Monitoring around gas wells is generally limited to domestic water-supply wells, which often are not situated along predominant groundwater flow paths. A new concept is tested here: combining stream hydrocarbon and noble-gas measurements with reach mass-balance modeling to estimate thermogenic methane concentrations and fluxes in groundwater discharging to streams and to constrain methane sources. In the Marcellus Formation shale-gas play of northern Pennsylvania (U.S.A.), we sampled methane in 15 streams as a reconnaissance tool to locate methane-laden groundwater discharge: concentrations up to 69 μg L(-1) were observed, with four streams ≥ 5 μg L(-1). Geochemical analyses of water from one stream with high methane (Sugar Run, Lycoming County) were consistent with Middle Devonian gases. After sampling was completed, we learned of a state regulator investigation of stray-gas migration from a nearby Marcellus Formation gas well. Modeling indicates a groundwater thermogenic methane flux of about 0.5 kg d(-1) discharging into Sugar Run, possibly from this fugitive gas source. Since flow paths often coalesce into gaining streams, stream methane monitoring provides the first watershed-scale method to assess groundwater contamination from shale-gas development.

The variation of molybdenum isotopes within the weathering system of the black shales

NASA Astrophysics Data System (ADS)

Jianming, Z.

2016-12-01

Jian-Ming Zhu 1,2, De-Can Tan 2, Liang Liang 2, Wang Jing21 State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing, 100083, China 2 State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, 550002, China Molybdenum (Mo) stable isotopes have been developed as a tracer to indicate the evolution of the atmospheric and oceanic oxygenation related with continent weathering, and to reveal the extent of ancient oceanic euxinia. Molybdenum isotopic variation within the weathering system of basalts has been studied, and was presented the whole trend with heavier isotopes preferentially removed during weathering processes. However, there are few researches to study the variation of Mo isotopes during black shale weathering, especiall on the behavoir of Mo isotopes within the perfect shales' profiles. Here, the weathering profiles of Mo and selenium(Se)-rich carbonaceous rocks in Enshi southwest Hubei Province were selected. The Mo isotopes was measured on Nu Plasma II's MC-ICP-MS using 97Mo-100Mo double spike, and δ98/95Mo was reported relative to NIST 3134. A comprehensive set of Mo isotopic composition and concentration data from the unweathered, weakly and intensely weathered rocks were collected. The δ98/95Mo in fresh shales (220±248 mg/kg Mo, 1SD, n=41) from Shadi and Yutangba drill cores varies from 0.41‰ to 0.99‰ with an average of 0.67±0.16‰, while the strongly weathered shales (19.9±5.8 mg/kg Mo, 1SD, n=5) from Shadi profiles are isotopically heavier with average δ98/95Mo values of 1.03±0.10‰ (1SD, n=5). The Locally altered shales exposed in a quarry at Yutangba are highly enriched in Mo, varing from 31 to 2377 mg/kg with an average of 428 ±605mg/kg (1SD, n=24), approximately 2 times greater than that in fresh shales samples. These rocks are presented a significant variation in δ98/95Mo values varing from -0.24 ‰ to -3.99 ‰ with average -1.67±1.57‰, showing the extremely negative δ98/95Mo values existed in natural samples. This suggested that Mo isotopes can be fractionated during shales weathering processes, with lighter isotopes preferentially removed. This finding is in contrast to the previous knowledge from basalt weathering, and requires further study.

Pore Characterization of Shale Rock and Shale Interaction with Fluids at Reservoir Pressure-Temperature Conditions Using Small-Angle Neutron Scattering

NASA Astrophysics Data System (ADS)

Ding, M.; Hjelm, R.; Watkins, E.; Xu, H.; Pawar, R.

2015-12-01

Oil/gas produced from unconventional reservoirs has become strategically important for the US domestic energy independence. In unconventional realm, hydrocarbons are generated and stored in nanopores media ranging from a few to hundreds of nanometers. Fundamental knowledge of coupled thermo-hydro-mechanical-chemical (THMC) processes that control fluid flow and propagation within nano-pore confinement is critical for maximizing unconventional oil/gas production. The size and confinement of the nanometer pores creates many complex rock-fluid interface interactions. It is imperative to promote innovative experimental studies to decipher physical and chemical processes at the nanopore scale that govern hydrocarbon generation and mass transport of hydrocarbon mixtures in tight shale and other low permeability formations at reservoir pressure-temperature conditions. We have carried out laboratory investigations exploring quantitative relationship between pore characteristics of the Wolfcamp shale from Western Texas and the shale interaction with fluids at reservoir P-T conditions using small-angle neutron scattering (SANS). We have performed SANS measurements of the shale rock in single fluid (e.g., H2O and D2O) and multifluid (CH4/(30% H2O+70% D2O)) systems at various pressures up to 20000 psi and temperature up to 150 oF. Figure 1 shows our SANS data at different pressures with H2O as the pressure medium. Our data analysis using IRENA software suggests that the principal changes of pore volume in the shale occurred on smaller than 50 nm pores and pressure at 5000 psi (Figure 2). Our results also suggest that with increasing P, more water flows into pores; with decreasing P, water is retained in the pores.

Fundamentals of gas flow in shale; What the unconventional reservoir industry can learn from the radioactive waste industry

NASA Astrophysics Data System (ADS)

Cuss, Robert; Harrington, Jon; Graham, Caroline

2013-04-01

Tight formations, such as shale, have a wide range of potential usage; this includes shale gas exploitation, hydrocarbon sealing, carbon capture & storage and radioactive waste disposal. Considerable research effort has been conducted over the last 20 years on the fundamental controls on gas flow in a range of clay-rich materials at the British Geological Survey (BGS) mainly focused on radioactive waste disposal; including French Callovo-Oxfordian claystone, Belgian Boom Clay, Swiss Opalinus Clay, British Oxford Clay, as well as engineered barrier material such as bentonite and concrete. Recent work has concentrated on the underlying physics governing fluid flow, with evidence of dilatancy controlled advective flow demonstrated in Callovo-Oxfordian claystone. This has resulted in a review of how advective gas flow is dealt with in Performance Assessment and the applicability of numerical codes. Dilatancy flow has been shown in Boom clay using nano-particles and is seen in bentonite by the strong hydro-mechanical coupling displayed at the onset of gas flow. As well as observations made at BGS, dilatancy flow has been shown by other workers on shale (Cuss et al., 2012; Angeli et al. 2009). As well as experimental studies using cores of intact material, fractured material has been investigated in bespoke shear apparatus. Experimental results have shown that the transmission of gas by fractures is highly localised, dependent on normal stress, varies with shear, is strongly linked with stress history, is highly temporal in nature, and shows a clear correlation with fracture angle. Several orders of magnitude variation in fracture transmissivity is seen during individual tests. Flow experiments have been conducted using gas and water, showing remarkably different behaviour. The radioactive waste industry has also noted a number of important features related to sample preservation. Differences in gas entry pressure have been shown across many laboratories and these may be attributed to different core preparation techniques. Careful re-stressing of core barrels and sealing techniques also ensure that experiments are conducted on near in situ condition. The construction of tunnels within shale clearly aids our understanding of the interaction of engineered operations (borehole drilling or tunnelling) on the behaviour of the rock. References: Angeli, M., Soldal, M., Skurtveit, E. and Aker, E., (2009) Experimental percolation of supercritical CO2 through a caprock. Energy Procedia 1, 3351-3358 Cuss, R.J., Harrington, J.F., Giot, R., and Auvray, C. (2012) Experimental observations of mechanical dilation at the onset of gas flow in Callovo-Oxfordian Claystone. Poster Presentation 5th International Meeting Clays in Natural and Engineered Barriers for Radioactive Waste Confinement, Montpellier, France October 22nd - 25th 2012.

Characterization of Early Stage Marcellus Shale Development Atmospheric Emissions and Regional Air Quality Impacts using Fast Mobile Measurements

NASA Astrophysics Data System (ADS)

Goetz, J. D.; Floerchinger, C. R.; Fortner, E.; Wormhoult, J.; Massoli, P.; Herndon, S. C.; Kolb, C. E., Jr.; Knighton, W. B.; Shaw, S. L.; Knipping, E. M.; DeCarlo, P. F.

2014-12-01

The Marcellus shale is the largest shale gas resource in the United States and is found in the Appalachian region. Rapid large-scale development, and the scarcity of direct air measurements make the impact of Marcellus shale development on local and regional air quality and the global climate highly uncertain. Air pollutant and greenhouse gas emission sources include transitory emission from well pad development as well as persistent sources including the processing and distribution of natural gas. In 2012, the Aerodyne Inc. Mobile Laboratory was equipped with a suite of real-time (~ 1 Hz) instrumentation to measure source emissions associated with Marcellus shale development and to characterize regional air quality in the Marcellus basin. The Aerodyne Inc. Mobile Laboratory was equipped to measure methane, ethane, N2O (tracer gas), C2H2 (tracer gas), CO2, CO, NOx, aerosols (number, mass, and composition), and VOC including light aromatic compounds and constituents of natural gas. Site-specific emissions from Marcellus shale development were quantified using tracer release ratio methods. Emissions of sub-micron aerosol mass and VOC were generally not observed at any tracer release site, although particle number concentrations were often enhanced. Compressor stations were found to have the largest emission rates of combustion products with NOx emissions ranging from 0.01 to 1.6 tons per day (tpd) and CO emissions ranging from 0.03 to 0.42 tpd. Transient sources, including a well site in the drill phase, were observed to be large emitters of natural gas. The largest methane emissions observed in the study were at a flowback well completion with a value of 7.7 tpd. Production well pads were observed to have the lowest emissions of natural gas and the emission of combustion products was only observed at one of three well pads investigated. Regional background measurements of all measured species were made while driving between tracer release sites and while stationary at night. Median background mixing ratios of methane in Pennsylvania were observed to be 19.7 ppmv in the Southwestern part of the state and 20.5 ppmv in Northeast. The atmospheric background measurements provide information about the temporal and spatial characteristics of the Marcellus basin during the early stages of shale gas development.

Geochemical and multi-isotopic (87Sr/86Sr, 143Nd/144Nd, 238U/235U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

NASA Astrophysics Data System (ADS)

Phan, Thai T.; Gardiner, James B.; Capo, Rosemary C.; Stewart, Brian W.

2018-02-01

We investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from -7.8 to -6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from a well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns. Limestone units thought to have formed under open ocean (oxic) conditions have δ238U values and REE patterns consistent with modern seawater. The δ238U values in whole rock shale and authigenic phases are greater than those of modern seawater and the upper crust. The δ238U values of reduced phases (the oxidizable fraction consisting of organics and sulfide minerals) are ∼0.6‰ greater than that of modern seawater. Bulk shale and carbonate cement extracted from the shale have similar δ238U values, and are greater than δ238U values of adjacent limestone units. We suggest these trends are due to the accumulation of chemically and, more likely, biologically reduced U from anoxic to euxinic bottom water as well as the influence of diagenetic reactions between pore fluids and surrounding sediment and organic matter during diagenesis and catagenesis.

Shale Gas Boom or Bust? Estimating US and Global Economically Recoverable Resources

NASA Astrophysics Data System (ADS)

Brecha, R. J.; Hilaire, J.; Bauer, N.

2014-12-01

One of the most disruptive energy system technological developments of the past few decades is the rapid expansion of shale gas production in the United States. Because the changes have been so rapid there are great uncertainties as to the impacts of shale production for medium- and long-term energy and climate change mitigation policies. A necessary starting point for incorporating shale resources into modeling efforts is to understand the size of the resource, how much is technically recoverable (TRR), and finally, how much is economically recoverable (ERR) at a given cost. To assess production costs of shale gas, we combine top-down data with detailed bottom-up information. Studies solely based on top-down approaches do not adequately account for the heterogeneity of shale gas deposits and are unlikely to appropriately estimate extraction costs. We design an expedient bottom-up method based on publicly available US data to compute the levelized costs of shale gas extraction. Our results indicate the existence of economically attractive areas but also reveal a dramatic cost increase as lower-quality reservoirs are exploited. Extrapolating results for the US to the global level, our best estimate suggests that, at a cost of 6 US$/GJ, only 39% of the technically recoverable resources reported in top-down studies should be considered economically recoverable. This estimate increases to about 77% when considering optimistic TRR and estimated ultimate recovery parameters but could be lower than 12% for more pessimistic parameters. The current lack of information on the heterogeneity of shale gas deposits as well as on the development of future production technologies leads to significant uncertainties regarding recovery rates and production costs. Much of this uncertainty may be inherent, but for energy system planning purposes, with or without climate change mitigation policies, it is crucial to recognize the full ranges of recoverable quantities and costs.

On the origin of a phosphate enriched interval in the Chattanooga Shale (Upper Devonian) of Tennessee-A combined sedimentologic, petrographic, and geochemical study

NASA Astrophysics Data System (ADS)

Li, Yifan; Schieber, Juergen

2015-11-01

The Devonian Chattanooga Shale contains an uppermost black shale interval with dispersed phosphate nodules. This interval extends from Tennessee to correlative strata in Kentucky, Indiana, and Ohio and represents a significant period of marine phosphate fixation during the Late Devonian of North America. It overlies black shales that lack phosphate nodules but otherwise look very similar in outcrop. The purpose of this study is to examine what sets these two shales apart and what this difference tells us about the sedimentary history of the uppermost Chattanooga Shale. In thin section, the lower black shales (PBS) show pyrite enriched laminae and compositional banding. The overlying phosphatic black shales (PhBS) are characterized by phosbioclasts, have a general banded to homogenized texture with reworked layers, and show well defined horizons of phosphate nodules that are reworked and transported. In the PhBS, up to 8000 particles of P-debris per cm2 occur in reworked beds, whereas the background black shale shows between 37-88 particles per cm2. In the PBS, the shale matrix contains between 8-16 phosphatic particles per cm2. The shale matrix in the PhBS contains 5.6% inertinite, whereas just 1% inertinite occurs in the PBS. The shale matrix in both units is characterized by flat REE patterns (shale-normalized), whereas Phosbioclast-rich layers in the PhBS show high concentrations of REEs and enrichment of MREEs. Negative Ce-anomalies are common to all samples, but are best developed in association with Phosbioclasts. Redox-sensitive elements (Co, U, Mo) are more strongly enriched in the PBS when compared to the PhBS. Trace elements associated with organic matter (Cu, Zn, Cd, Ni) show an inverse trend of enrichment. Deposited atop a sequence boundary that separates the two shale units, the PhBS unit represents a transgressive systems tract and probably was deposited in shallower water than the underlying PBS interval. The higher phosphate content in the PhBS is interpreted as the result of a combination of lower sedimentation rates with reworking/winnowing episodes. Three types of phosphatic beds that reflect different degrees of reworking intensity are observed. Strong negative Ce anomalies and abundant secondary marcasite formation in the PhBS suggests improved aeration of the water column, and improved downward diffusion of oxygen into the sediment. The associated oxidation of previously formed pyrite resulted in a lowering of pore water pH and forced dissolution of biogenic phosphate. Phosphate dissolution was followed by formation of secondary marcasite and phosphate. Repeated, episodic reworking caused repetitive cycles of phosphatic dissolution and reprecipitation, enriching MREEs in reprecipitated apatite. A generally "deeper" seated redox boundary favored P-remineralization within the sediment matrix, and multiple repeats of this process in combination with wave and current reworking at the seabed led to the formation of larger phosphatic aggregates and concentration of phosphate nodules in discrete horizons.

Fungal diversity in major oil-shale mines in China.

PubMed

Jiang, Shaoyan; Wang, Wenxing; Xue, Xiangxin; Cao, Chengyou; Zhang, Ying

2016-03-01

As an insufficiently utilized energy resource, oil shale is conducive to the formation of characteristic microbial communities due to its special geological origins. However, little is known about fungal diversity in oil shale. Polymerase chain reaction cloning was used to construct the fungal ribosomal deoxyribonucleic acid internal transcribed spacer (rDNA ITS) clone libraries of Huadian Mine in Jilin Province, Maoming Mine in Guangdong Province, and Fushun Mine in Liaoning Province. Pure culture and molecular identification were applied for the isolation of cultivable fungi in fresh oil shale of each mine. Results of clone libraries indicated that each mine had over 50% Ascomycota (58.4%-98.9%) and 1.1%-13.5% unidentified fungi. Fushun Mine and Huadian Mine had 5.9% and 28.1% Basidiomycota, respectively. Huadian Mine showed the highest fungal diversity, followed by Fushun Mine and Maoming Mine. Jaccard indexes showed that the similarities between any two of three fungal communities at the genus level were very low, indicating that fungi in each mine developed independently during the long geological adaptation and formed a community composition fitting the environment. In the fresh oil-shale samples of the three mines, cultivable fungal phyla were consistent with the results of clone libraries. Fifteen genera and several unidentified fungi were identified as Ascomycota and Basidiomycota using pure culture. Penicillium was the only genus found in all three mines. These findings contributed to gaining a clear understanding of current fungal resources in major oil-shale mines in China and provided useful information for relevant studies on isolation of indigenous fungi carrying functional genes from oil shale. Copyright © 2015. Published by Elsevier B.V.

Influence of Composition and Deformation Conditions on the Strength and Brittleness of Shale Rock

NASA Astrophysics Data System (ADS)

Rybacki, E.; Reinicke, A.; Meier, T.; Makasi, M.; Dresen, G. H.

2015-12-01

Stimulation of shale gas reservoirs by hydraulic fracturing operations aims to increase the production rate by increasing the rock surface connected to the borehole. Prospective shales are often believed to display high strength and brittleness to decrease the breakdown pressure required to (re-) initiate a fracture as well as slow healing of natural and hydraulically induced fractures to increase the lifetime of the fracture network. Laboratory deformation tests were performed on several, mainly European black shales with different mineralogical composition, porosity and maturity at ambient and elevated pressures and temperatures. Mechanical properties such as compressive strength and elastic moduli strongly depend on shale composition, porosity, water content, structural anisotropy, and on pressure (P) and temperature (T) conditions, but less on strain rate. We observed a transition from brittle to semibrittle deformation at high P-T conditions, in particular for high porosity shales. At given P-T conditions, the variation of compressive strength and Young's modulus with composition can be roughly estimated from the volumetric proportion of all components including organic matter and pores. We determined also brittleness index values based on pre-failure deformation behavior, Young's modulus and bulk composition. At low P-T conditions, where samples showed pronounced post-failure weakening, brittleness may be empirically estimated from bulk composition or Young's modulus. Similar to strength, at given P-T conditions, brittleness depends on the fraction of all components and not the amount of a specific component, e.g. clays, alone. Beside strength and brittleness, knowledge of the long term creep properties of shales is required to estimate in-situ stress anisotropy and the healing of (propped) hydraulic fractures.

Multi-scale Multi-dimensional Imaging and Characterization of Oil Shale Pyrolysis

NASA Astrophysics Data System (ADS)

Gao, Y.; Saif, T.; Lin, Q.; Al-Khulaifi, Y.; Blunt, M. J.; Bijeljic, B.

2017-12-01

The microstructural evaluation of fine grained rocks is challenging which demands the use of several complementary methods. Oil shale, a fine-grained organic-rich sedimentary rock, represents a large and mostly untapped unconventional hydrocarbon resource with global reserves estimated at 4.8 trillion barrels. The largest known deposit is the Eocene Green River Formation in Western Colorado, Eastern Utah, and Southern Wyoming. An improved insight into the mineralogy, organic matter distribution and pore network structure before, during and after oil shale pyrolysis is critical to understanding hydrocarbon flow behaviour and improving recovery. In this study, we image Mahogany zone oil shale samples in two dimensions (2-D) using scanning electron microscopy (SEM), and in three dimensions (3-D) using focused ion beam scanning electron microscopy (FIB-SEM), laboratory-based X-ray micro-tomography (µCT) and synchrotron X-ray µCT to reveal a complex and variable fine grained microstructure dominated by organic-rich parallel laminations which are tightly bound in a highly calcareous and heterogeneous mineral matrix. We report the results of a detailed µCT study of the Mahogany oil shale with increasing pyrolysis temperature. The physical transformation of the internal microstructure and evolution of pore space during the thermal conversion of kerogen in oil shale to produce hydrocarbon products was characterized. The 3-D volumes of pyrolyzed oil shale were reconstructed and image processed to visualize and quantify the volume and connectivity of the pore space. The results show a significant increase in anisotropic porosity associated with pyrolysis between 300-500°C with the formation of micron-scale connected pore channels developing principally along the kerogen-rich lamellar structures.

Trace elements reconnaissance investigations in New Mexico and adjoining states in 1951

USGS Publications Warehouse

Bachman, George O.; Read, Charles B.

1952-01-01

In the summer and fall of 1951, a reconnaissance search was made in New Mexico and adjacent states for uranium in coal and carbonaceous shale, chiefly of Mesozoic age, and black marine shale of Paleozoic age. Tertiary volcanic rocks, considered to be a possible source for uranium in the coal and associated rocks, were examined where the volcanic rocks were near coal-bearing strata. Uranium in possibly commercial amounts was found at La Ventana Mesa, Sandoval County, New Mexico. Slightly uranifeous coal and carbonaceous shale were found near San Ysidro, Sandoval County, and on Beautiful Mountain, San Juan County, all in New Mexico, and at Keams Canyon, Navajo County, and near Tuba City, Coconino County, in Arizona. Except for La Ventana deposit, none appeared to be of economic importance at the time this report was written, but additional reconnaissance investigations have been underway this field season, in the area where the deposits occur. Marine black shale of Sevonian age was examined in Otero and Socorro Counties, New Mexico and Gila County, Arizona. Mississippian black shale in Socorro County and Pennsylvanian black shale in Taos County, New Mexico were also tested. Equivalent uranium content of samples of these shales did not exceed 0.004 percent. Rhyolitic tuff from the Mount Taylor region is slightly radioactive as is the Bandelier tuff in the Nacimiento region and in the Jemez Plateau. Volcanic rocks in plugs and dikes in the northern Chuska Mountains and to the north in New Mexico as well as in northeastern Arizona and southeastern Utah are slightly radioactive. Coal and carbonaceous rocks in the vicinity of these and similar intrusions are being examined.

Wellsite, laboratory, and mathematical techniques for determining sorbed gas content of coals and gas shales utilizing well cuttings

USGS Publications Warehouse

Newell, K.D.

2007-01-01

Drill cuttings can be used for desorption analyses but with more uncertainty than desorption analyses done with cores. Drill cuttings are not recommended to take the place of core, but in some circumstances, desorption work with cuttings can provide a timely and economic supplement to that of cores. The mixed lithologic nature of drill cuttings is primarily the source of uncertainty in their analysis for gas content, for it is unclear how to apportion the gas generated from both the coal and the dark-colored shale that is mixed in usually with the coal. In the Western Interior Basin Coal Basin in eastern Kansas (Pennsylvanian-age coals), dark-colored shales with normal (??? 100 API units) gamma-ray levels seem to give off minimal amounts of gas on the order of less than five standard cubic feet per ton (scf/ton). In some cuttings analyses this rule of thumb for gas content of the shale is adequate for inferring the gas content of coals, but shales with high-gamma-ray values (>150 API units) may yield several times this amount of gas. The uncertainty in desorption analysis of drill cuttings can be depicted graphically on a diagram identified as a "lithologic component sensitivity analysis diagram." Comparison of cuttings desorption results from nearby wells on this diagram, can sometimes yield an unique solution for the gas content of both a dark shale and coal mixed in a cuttings sample. A mathematical solution, based on equating the dry, ash-free gas-contents of the admixed coal and dark-colored shale, also yields results that are correlative to data from nearby cores. ?? 2007 International Association for Mathematical Geology.

4D petroleum system model of the Mississippian System in the Anadarko Basin Province, Oklahoma, Kansas, Texas, and Colorado, U.S.A.

USGS Publications Warehouse

Higley, Debra K.

2013-01-01

The Upper Devonian and Lower Mississippian Woodford Shale is an important petroleum source rock for Mississippian reservoirs in the Anadarko Basin Province of Oklahoma, Kansas, Texas, and Colorado, based on results from a 4D petroleum system model of the basin. The Woodford Shale underlies Mississippian strata over most of the Anadarko Basin portions of Oklahoma and northeastern Texas. The Kansas and Colorado portions of the province are almost entirely thermally immature for oil generation from the Woodford Shale or potential Mississippian source rocks, based mainly on measured vitrinite reflectance and modeled thermal maturation. Thermal maturities of the Woodford Shale range from mature for oil to overmature for gas generation at present-day depths of about 5,000 to 20,000 ft. Oil generation began at burial depths of about 6,000 to 6,500 ft. Modeled onset of Woodford Shale oil generation was about 330 million years ago (Ma); peak oil generation was from 300 to 220 Ma.Mississippian production, including horizontal wells of the informal Mississippi limestone, is concentrated within and north of the Sooner Trend area in the northeast Oklahoma portion of the basin. This large pod of oil and gas production is within the area modeled as thermally mature for oil generation from the Woodford Shale. The southern boundary of the trend approximates the 99% transformation ratio of the Woodford Shale, which marks the end of oil generation. Because most of the Sooner Trend area is thermally mature for oil generation from the Woodford Shale, the trend probably includes short- and longer-distance vertical and lateral migration. The Woodford Shale is absent in the Mocane-Laverne Field area of the eastern Oklahoma panhandle; because of this, associated oil migrated from the south into the field. If the Springer Formation or deeper Mississippian strata generated oil, then the southern field area is within the oil window for associated petroleum source rocks. Mississippian fields along the western boundary of the study area were supplied by oil that flowed northward from the Panhandle Field area and westward from the deep basin.

Thorium/U systematics of Precambrian deep-sea pelagic balck shales: implications for redox state of the early atmosphere

NASA Astrophysics Data System (ADS)

Jia, Y.; McCulloch, M.; Charlotte, A.

2003-12-01

To address the question of the redox state of the Precambrian atmosphere-hydrosphere system via sediments requires measurement of redox sensitive trace elements, and inter-element ratios, in deep water black shales with a chemical sedimentary "hydrogenic" component. This approach is endorsed by recent progress in research of redox-sensitive trace metals records in late Proterozoic and Phanerozoic sedimentary rocks, which has provided important clues to how the redox state of depositional environments has changed over time. Many conventional studies, in contrast, have been on first cycle volcanogenic turbidites with a minimal hydrogenic input (Taylor and McLennan, 1995). Accordingly, we have analyzed the redox-sensitive, trace element compositions of the 2.1 Ga black shales in Birimian Blet, West Africa, and the 2.7 Ga Archean counterparts in Timmins, Canada, Tati Belt, Botswana, and Kanowna District, Western Australia. These pyrite-bearing black shales, which were originally argillaceous sediments containing organic matter and low in thermal maturity, were primarily deposited in the deep-sea pelagic environments. Th/U ratios are lower in the Proterozoic shales (0.38-0.82, average 0.67), and Archean shales (0.47-3.65, average 2.43) relative to "conventional" Archean upper crust (3.8), PAAS (4.7), or average upper continental crust (3.8). Calculated U concentrations from hydrogenic component are between 0.90 and 2.45 in the Proterozoic shales, and range from 0.06 to 0.96 for the Archean black shales. Given the conservative behavior of Th in the sedimentary cycle, variably low Th/U ratios in these Precambrian black shales signify that U6+, soluble in oxidized surface waters, was reduced to insoluble U4+ in reducing bottom waters, as in the contemporary Black Sea. The results are consistent with a locally to globally oxidized atmosphere-shallow hydrosphere pre-2.0 Ga. Taylor, S.R., and McLennan, S.C., 1995. The geochemical evolution of the continental crust: Reviews of Geophysics, v. 33. p. 241-265.

Geology and sequence stratigraphy of undiscovered oil and gas resources in conventional and continuous petroleum systems in the Upper Cretaceous Eagle Ford Group and related strata, U.S. Gulf Coast Region

USGS Publications Warehouse

Dubiel, Russell F.; Pearson, Ofori N.; Pitman, Janet K.; Pearson, Krystal M.; Kinney, Scott A.

2012-01-01

The U.S. Geological Survey (USGS) recently assessed the technically recoverable undiscovered oil and gas onshore and in State waters of the Gulf Coast region of the United States. The USGS defined three assessment units (AUs) with potential undiscovered conventional and continuous oil and gas resources in Upper Cretaceous (Cenomanian to Turonian) strata of the Eagle Ford Group and correlative rocks. The assessment is based on geologic elements of a total petroleum system, including hydrocarbon source rocks (source rock maturation, hydrocarbon generation and migration), reservoir rocks (sequence stratigraphy and petrophysical properties), and traps (formation, timing, and seals). Conventional oil and gas undiscovered resources are in updip sandstone reservoirs in the Upper Cretaceous Tuscaloosa and Woodbine Formations (or Groups) in Louisiana and Texas, respectively, whereas continuous oil and continuous gas undiscovered resources reside in the middip and downdip Upper Cretaceous Eagle Ford Shale in Texas and the Tuscaloosa marine shale in Louisiana. Conventional resources in the Tuscaloosa and Woodbine are included in the Eagle Ford Updip Sandstone Oil and Gas AU, in an area where the Eagle Ford Shale and Tuscaloosa marine shale display vitrinite reflectance (Ro) values less than 0.6%. The continuous Eagle Ford Shale Oil AU lies generally south of the conventional AU, is primarily updip of the Lower Cretaceous shelf edge, and is defined by thermal maturity values within shales of the Eagle Ford and Tuscaloosa that range from 0.6 to 1.2% Ro. Similarly, the Eagle Ford Shale Gas AU is defined downdip of the shelf edge where source rocks have Ro values greater than 1.2%. For undiscovered oil and gas resources, the USGS assessed means of: 1) 141 million barrels of oil (MMBO), 502 billion cubic feet of natural gas (BCFG), and 4 million barrels of natural gas liquids (MMBNGL) in the Eagle Ford Updip Sandstone Oil and Gas AU; 2) 853 MMBO, 1707 BCFG, and 34 MMBNGL in the Eagle Ford Shale Oil AU; and 3) 50,219 BCFG and 2009 MMBNGL in the Eagle Ford Shale Gas AU.

Deposition of sedimentary organic matter in black shale facies indicated by the geochemistry and petrography of high-resolution samples, blake nose, western North Atlantic

USGS Publications Warehouse

Barker, C.E.; Pawlewicz, M.; Cobabe, E.A.

2001-01-01

A transect of three holes drilled across the Blake Nose, western North Atlantic Ocean, retrieved cores of black shale facies related to the Albian Oceanic Anoxic Events (OAE) lb and ld. Sedimentary organic matter (SOM) recovered from Ocean Drilling Program Hole 1049A from the eastern end of the transect showed that before black shale facies deposition organic matter preservation was a Type III-IV SOM. Petrography reveals that this SOM is composed mostly of degraded algal debris, amorphous SOM and a minor component of Type III-IV terrestrial SOM, mostly detroinertinite. When black shale facies deposition commenced, the geochemical character of the SOM changed from a relatively oxygen-rich Type III-IV to relatively hydrogen-rich Type II. Petrography, biomarker and organic carbon isotopic data indicate marine and terrestrial SOM sources that do not appear to change during the transition from light-grey calcareous ooze to the black shale facies. Black shale subfacies layers alternate from laminated to homogeneous. Some of the laminated and the poorly laminated to homogeneous layers are organic carbon and hydrogen rich as well, suggesting that at least two SOM depositional processes are influencing the black shale facies. The laminated beds reflect deposition in a low sedimentation rate (6m Ma-1) environment with SOM derived mostly from gravity settling from the overlying water into sometimes dysoxic bottom water. The source of this high hydrogen content SOM is problematic because before black shale deposition, the marine SOM supplied to the site is geochemically a Type III-IV. A clue to the source of the H-rich SOM may be the interlayering of relatively homogeneous ooze layers that have a widely variable SOM content and quality. These relatively thick, sometimes subtly graded, sediment layers are thought to be deposited from a Type II SOM-enriched sediment suspension generated by turbidities or direct turbidite deposition.

Evaluating the oxidation of shale during hydraulic fracturing using SEM-EDS and spectrocolorimetry

NASA Astrophysics Data System (ADS)

Tan, X. Y.; Nakashima, S.

2017-12-01

During hydraulic fracturing (fracking) for shale gas/oil extraction, oxygen is introduced into deep oxygen-poor environments, and Fe2+-bearing minerals in rocks can be oxidized thus leading to the degradation of rock quality. Akita diatomaceous shale is considered to be one of the source rocks for oil and gas fields in northwestern Japan. Outcrops of Akita shale often show presence of jarosite (Fe sulfate: yellow) and/or goethite (Fe hydroxide: brown to orange) as oxidation products of pyrite (FeS2). Several series of oxidation experiments of Akita shale under dry, humid, and wet conditions were conducted at temperatures of around 30 oC and 50oC for 30-40 days. Portable color spectro-colorimeters were used to monitor color changes of the rock surfaces every hour. SEM-EDS, UV-Vis, and Raman spectroscopic analyses were performed on the rock sample surface to examine the chemical and mineralogical compositions of Akita shale before and after the dry, humid, and wet experiments. In SEM-EDS analyses before the humid experiment, Fe and S containing phases show their atomic ratio close to 1:2 indicating that this is pyrite (FeS2). After the experiment, the ratio changed to around 1:1 suggesting a conversion from pyrite (FeS2) to mackinawite-like mineral (FeS). In addition, the formation of Ca sulfate (possibly gypsum: CaSO4.2H2O) and goethite-like Fe hydroxide were identified which were not present initially. Therefore, oxidation pathways of iron sulfide (pyrite: FeS2) via FeS to sulfate is confirmed by our humid experiments around 30oC on Akita shale. These oxidation processes might occur during the fracking of shale within relatively short time periods associated with precipitation of sulfates and hydroxides. Therefore, further studies are needed for their effects on rock properties and gas/oil production.

Malignant human cell transformation of Marcellus shale gas drilling flow back water

PubMed Central

Yao, Yixin; Chen, Tingting; Shen, Steven S.; Niu, Yingmei; DesMarais, Thomas L; Linn, Reka; Saunders, Eric; Fan, Zhihua; Lioy, Paul; Kluz, Thomas; Chen, Lung-Chi; Wu, Zhuangchun; Costa, Max

2015-01-01

The rapid development of high-volume horizontal hydraulic fracturing for mining natural gas from shale has posed potential impacts on human health and biodiversity. The produced flow back waters after hydraulic stimulation is known to carry high levels of saline and total dissolved solids. To understand the toxicity and potential carcinogenic effects of these waste waters, flow back water from five Marcellus hydraulic fracturing oil and gas wells were analyzed. The physicochemical nature of these samples was analyzed by inductively coupled plasma mass spectrometry and scanning electron microscopy / energy dispersive X-ray spectroscopy. A cytotoxicity study using colony formation as the endpoint was carried out to define the LC50 values of test samples using human bronchial epithelial cells (BEAS-2B). The BEAS-2B cell transformation assay was employed to assess the carcinogenic potential of the samples. Barium and strontium were among the most abundant metals in these samples and the same metals were found elevated in BEAS-2B cells after long-term treatment. BEAS-2B cells treated for 6 weeks with flow back waters produced colony formation in soft agar that was concentration dependant. In addition, flow back water-transformed BEAS-2B cells show a better migration capability when compared to control cells. This study provides information needed to assess the potential health impact of post-hydraulic fracturing flow back waters from Marcellus Shale natural gas mining. PMID:26210350

Oil shale combustor model developed by Greek researchers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1986-09-01

Work carried out in the Department of Chemical Engineering at the University of Thessaloniki, Thessaloniki, Greece has resulted in a model for the combustion of retorted oil shale in a fluidized bed combustor. The model is generally applicable to any hot-solids retorting process, whereby raw oil shale is retorted by mixing with a hot solids stream (usually combusted spent shale), and then the residual carbon is burned off the spent shale in a fluidized bed. Based on their modelling work, the following conclusions were drawn by the researchers. (1) For the retorted particle size distribution selected (average particle diameter 1600more » microns) complete carbon conversion is feasible at high pressures (2.7 atmosphere) and over the entire temperature range studied (894 to 978 K). (2) Bubble size was found to have an important effect, especially at conditions where reaction rates are high (high temperature and pressure). (3) Carbonate decomposition increases with combustor temperature and residence time. Complete carbon conversion is feasible at high pressures (2.7 atmosphere) with less than 20 percent carbonate decomposition. (4) At the preferred combustor operating conditions (high pressure, low temperature) the main reaction is dolomite decomposition while calcite decomposition is negligible. (5) Recombination of CO/sub 2/ with MgO occurs at low temperatures, high pressures, and long particle residence times.« less

Reconstruction of paleoenvironment recorded in the Ediacaran Lantain black shales

NASA Astrophysics Data System (ADS)

Liu, Y. H.; Lee, D. C.; You, C. F.; Zhou, C.

2016-12-01

The Ediacaran period (635-542 Ma) was a critical time in the history of life and Earth, during which profound changes in complex megascopic life and probably ocean oxygenation occurred. A growing evidence demonstrates that the Early Ediacaran ocean was not simply a largely anoxic basin as previous thought. Pulsed oxidation or a multilayered water column had been proposed to explain the presence of Lantain macrofossils. To verify these models, in-situ isotopic analysis becomes critical in identifying the isotopic signatures of authigenic minerals, and to avoid mixing in the signals from detrital and diagenetic phases. In this study, samples from Lantain Member II, a 40 m thick black shale unit containing macrofossils and overlaying the cap carbonate, were analyzed, including one sample from the lower part of Member II and six samples from upper part of Member II. Abundant xenotimes were overgrown on the detrital zircon grains during early diagenesis in all the samples. This authigenic phosphate mineral provides the best constraint of depositional age. In addition, framboidal pyrites and microbial mats are alternatively present on the top of Member II, where layered barites are found in one sample, supporting the model of frequent changes of redox conditions. Preliminary results show that the depositional age of barite-bearing black shale is > 520 Ma. In this study, we will combine the in-situ U-Pb xenotime dating and sulfur isotopes in barite and pyrite to discuss the evolution of redox conditions in the Ediacaran ocean.