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USGS2008

Geochemical signatures of thermochemical sulfate reduction in controlled hydrous pyrolysis experiments

A series of gold tube hydrous pyrolysis experiments was conducted in order to investigate the effect of thermochemical sulfate reduction (TSR) on gas generation, residual saturated hydrocarbon compositional alteration, and solid pyrobitumen formation. The intensity of TSR significantly depends on the H 2 O/MgSO 4 mole ratio, the smaller the ratio, the stronger the oxidizing conditions. Under highly oxidizing conditions (MgSO 4 /hydrocarbon wt/wt 20/1 and hydrocarbon/H 2 O wt/wt 1/1), large amounts of H 2 S and CO 2 are generated indicating that hydrocarbon oxidation coupled with sulfate reduction is the dominant reaction. Starting with a mixture of C 21 –C 35 n -alkanes, these hydrocarbons are consumed totally at temperatures below the onset of hydrocarbon thermal cracking in the absence of TSR (400 °C). Moreover, once the longer chain length hydrocarbons are oxidized, secondarily formed hydrocarbons, even methane, are oxidized to CO 2 . Using whole crude oils as the starting reactants, the TSR reaction dramatically lowers the stability of hydrocarbons leading to increases in gas dryness and gas/oil ratio. While their concentrations decrease, the relative distributions of n -alkanes do not change appreciably from the original composition, and consequently, are non-diagnostic for TSR. However, distinct molecular changes related to TSR are observed, Pr/ n -C 17 and Ph/ n -C 18 ratios decrease at a faster rate under TSR compared to thermal chemical alteration (TCA) alone. TSR promotes aromatization and the incorporation of sulfur and oxygen into hydrocarbons leading to a decrease in the saturate to aromatic ratio in the residual oil and in the generation of sulfur and oxygen rich pyrobitumen. These experimental findings could provide useful geochemical signatures to identify TSR in settings where TSR has occurred in natural systems.

Organic Geochemistry↗

USGS2008

Increasing maturity of kerogen type II reflected by alkylbenzene distribution from pyrolysis-gas chromatography-mass spectrometry

A series of Late Devonian to Early Mississippian type II kerogens with vitrinite reflectance values Ro 0.29-2.41% were analyzed using py-GC-MS. In addition, a low maturity kerogen with Ro 0.44% was separated into fractions via density gradient centrifugation, followed by py-GC-MS of the alginite and amorphinite maceral concentrates. Alkylbenzenes and n-alk-1-ene/n-alkane doublets represented the main compound classes identified in all pyrolysates. The pyrolysate from alginite featured 1,2,4-trimethylbenzene and toluene as the two most prominent alkylbenzenes. In contrast, alkylbenzenes in pyrolysates from amorphinite and low maturity bulk kerogens with Ro 0.29-0.63% were dominated by 1,2,3,4-tetramethylbenzene. With increasing thermal maturity, pyrolysates were increasingly dominated by (i) alkylbenzenes with fewer methyl groups, namely by tri- and dimethylbenzenes at medium maturity (Ro 0.69-1.19%), and (ii) by toluene at higher maturity (Ro 1.30-2.41%). With increasing maturity of kerogen type II, the decreasing abundance of highly methyl-substituted alkylbenzenes and the parallel increase in less methyl-substituted alkylbenzenes in flash pyrolysates suggest that demethylation is an important chemical process in the thermal maturation of kerogen type II. ?? 2008 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗

USGS2008

De-convoluting mixed crude oil in Prudhoe Bay Field, North Slope, Alaska

Seventy-four crude oil samples from the Barrow arch on the North Slope of Alaska were studied to assess the relative volumetric contributions from different source rocks to the giant Prudhoe Bay Field. We applied alternating least squares to concentration data (ALS-C) for 46 biomarkers in the range C19-C35 to de-convolute mixtures of oil generated from carbonate rich Triassic Shublik Formation and clay rich Jurassic Kingak Shale and Cretaceous Hue Shale-gamma ray zone (Hue-GRZ) source rocks. ALS-C results for 23 oil samples from the prolific Ivishak Formation reservoir of the Prudhoe Bay Field indicate approximately equal contributions from Shublik Formation and Hue-GRZ source rocks (37% each), less from the Kingak Shale (26%), and little or no contribution from other source rocks. These results differ from published interpretations that most oil in the Prudhoe Bay Field originated from the Shublik Formation source rock. With few exceptions, the relative contribution of oil from the Shublik Formation decreases, while that from the Hue-GRZ increases in reservoirs along the Barrow arch from Point Barrow in the northwest to Point Thomson in the southeast (???250 miles or 400 km). The Shublik contribution also decreases to a lesser degree between fault blocks within the Ivishak pool from west to east across the Prudhoe Bay Field. ALS-C provides a robust means to calculate the relative amounts of two or more oil types in a mixture. Furthermore, ALS-C does not require that pure end member oils be identified prior to analysis or that laboratory mixtures of these oils be prepared to evaluate mixing. ALS-C of biomarkers reliably de-convolutes mixtures because the concentrations of compounds in mixtures vary as linear functions of the amount of each oil type. ALS of biomarker ratios (ALS-R) cannot be used to de-convolute mixtures because compound ratios vary as nonlinear functions of the amount of each oil type.

Organic Geochemistry↗

USGS2008

Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (<3.4 sulfurs per 100 carbons) due to offsetting preservation and H2S elimination reactions. In contrast, TSR solid bitumens are sulfur rich and nitrogen poor solids. These heteroatom distributions are attributed to the ability of TSR to incorporate copious amounts of inorganic sulfur (>3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to distinguish whether solid bitumen, either in situ or removed and concentrated from the rock matrix, was formed via the TCA or TRS process. ?? 2008 Elsevier Ltd.

Organic Geochemistry↗

USGS2008

Assessing the contribution of wetlands and subsided islands to dissolved organic matter and disinfection byproduct precursors in the Sacramento-San Joaquin River Delta: A geochemical approach

This study assesses how rivers, wetlands, island drains and open water habitats within the Sacramento-San Joaquin River Delta affect dissolved organic matter (DOM) content and composition, and disinfection byproduct (DBP) formation. Eleven sites representative of these habitats were sampled on six dates to encompass seasonal variability. Using a suite of qualitative analyses, including specific DBP formation potential, absorbance, fluorescence, lignin content and composition, C and N stable isotopic compositions, and structural groupings determined using CPMAS (cross polarization, magic angle spinning) 13C NMR, we applied a geochemical fingerprinting approach to characterize the DOM from different Delta habitats, and infer DOM and DBP precursor sources and estimate the relative contribution from different sources. Although river input was the predominant source of dissolved organic carbon (DOC), we observed that 13-49% of the DOC exported from the Delta originated from sources within the Delta, depending on season. Interaction with shallow wetlands and subsided islands significantly increased DOC and DBP precursor concentrations and affected DOM composition, while deep open water habitats had little discernable effect. Shallow wetlands contributed the greatest amounts of DOM and DBP precursors in the spring and summer, in contrast to island drains which appeared to be an important source during winter months. The DOM derived from wetlands and island drains had greater haloacetic acid precursor content relative to incoming river water, while two wetlands contributed DOM with greater propensity to form trihalomethanes. These results are pertinent to restoration of the Delta. Large scale introduction of shallow wetlands, a proposed restoration strategy, could alter existing DOC and DBP precursor concentrations, depending on their hydrologic connection to Delta channels. ?? 2008 Elsevier Ltd.

Organic Geochemistry↗

USGS2008

Thermal stability of ladderane lipids as determined by hydrous pyrolysis

Anaerobic ammonium oxidation (anammox) has been recognized as a major process resulting in loss of fixed inorganic nitrogen in the marine environment. Ladderane lipids, membrane lipids unique to anammox bacteria, have been used as markers for the detection of anammox in marine settings. However, the fate of ladderane lipids after sediment burial and maturation is unknown. In this study, anammox bacterial cell material was artificially matured by hydrous pyrolysis at constant temperatures ranging from 120 to 365 ??C for 72 h to study the stability of ladderane lipids during progressive dia- and catagenesis. HPLC-MS/MS analysis revealed that structural alterations of ladderane lipids already occurred at 120 ??C. At temperatures >140 ??C, ladderane lipids were absent and only more thermally stable products could be detected, i.e., ladderane derivatives in which some of the cyclobutane rings were opened. These diagenetic products of ladderane lipids were still detectable up to temperatures of 260 ??C using GC-MS. Thus, ladderane lipids are unlikely to occur in ancient sediments and sedimentary rocks, but specific diagenetic products of ladderane lipids will likely be present in sediments and sedimentary rocks of relatively low maturity (i.e., C31 hopane 22S/(22S + 22R) ratio <0.2 or ????/(???? + ???? + ????) ratio of >0.5). ?? 2008 Elsevier Ltd.

Organic Geochemistry↗

USGS2009

N-15 NMR spectra of naturally abundant nitrogen in soil and aquatic natural organic matter samples of the International Humic Substances Society

The naturally abundant nitrogen in soil and aquatic NOM samples from the International Humic Substances Society has been characterized by solid state CP/MAS 15 N NMR. Soil samples include humic and fulvic acids from the Elliot soil, Minnesota Waskish peat and Florida Pahokee peat, as well as the Summit Hill soil humic acid and the Leonardite humic acid. Aquatic samples include Suwannee River humic, fulvic and reverse osmosis isolates, Nordic humic and fulvic acids and Pony Lake fulvic acid. Additionally, Nordic and Suwannee River XAD-4 acids and Suwannee River hydrophobic neutral fractions were analyzed. Similar to literature reports, amide/aminoquinone nitrogens comprised the major peaks in the solid state spectra of the soil humic and fulvic acids, along with heterocyclic and amino sugar/terminal amino acid nitrogens. Spectra of aquatic samples, including the XAD-4 acids, contain resolved heterocyclic nitrogen peaks in addition to the amide nitrogens. The spectrum of the nitrogen enriched, microbially derived Pony Lake, Antarctica fulvic acid, appeared to contain resonances in the region of pyrazine, imine and/or pyridine nitrogens, which have not been observed previously in soil or aquatic humic substances by 15 N NMR. Liquid state 15 N NMR experiments were also recorded on the Elliot soil humic acid and Pony Lake fulvic acid, both to examine the feasibility of the techniques, and to determine whether improvements in resolution over the solid state could be realized. For both samples, polarization transfer (DEPT) and indirect detection ( 1 H- 15 N gHSQC) spectra revealed greater resolution among nitrogens directly bonded to protons. The amide/aminoquinone nitrogens could also be observed by direct detection experiments.

Organic Geochemistry↗

USGS2009

Comparison of natural gases accumulated in Oligocene strata with hydrous pyrolysis gases from Menilite Shales of the Polish Outer Carpathians

This study examined the molecular and isotopic compositions of gases generated from different kerogen types (i.e., Types I/II, II, IIS and III) in Menilite Shales by sequential hydrous pyrolysis experiments. The experiments were designed to simulate gas generation from source rocks at pre-oil-cracking thermal maturities. Initially, rock samples were heated in the presence of liquid water at 330 ??C for 72 h to simulate early gas generation dominated by the overall reaction of kerogen decomposition to bitumen. Generated gas and oil were quantitatively collected at the completion of the experiments and the reactor with its rock and water was resealed and heated at 355 ??C for 72 h. This condition simulates late petroleum generation in which the dominant overall reaction is bitumen decomposition to oil. This final heating equates to a cumulative thermal maturity of 1.6% R r , which represents pre-oil-cracking conditions. In addition to the generated gases from these two experiments being characterized individually, they are also summed to characterize a cumulative gas product. These results are compared with natural gases produced from sandstone reservoirs within or directly overlying the Menilite Shales. The experimentally generated gases show no molecular compositions that are distinct for the different kerogen types, but on a total organic carbon (TOC) basis, oil prone kerogens (i.e., Types I/II, II and IIS) generate more hydrocarbon gas than gas prone Type III kerogen. Although the proportionality of methane to ethane in the experimental gases is lower than that observed in the natural gases, the proportionality of ethane to propane and i-butane to n-butane are similar to those observed for the natural gases. ?? 13 C values of the experimentally generated methane, ethane and propane show distinctions among the kerogen types. This distinction is related to the ?? 13 C of the original kerogen, with 13 C enriched kerogen generating more 13 C enriched hydrocarbon gases than kerogen less enriched in 13 C. The typically assumed linear trend for ?? 13 C of methane, ethane and propane versus their reciprocal carbon number for a single sourced natural gas is not observed in the experimental gases. Instead, the so-called "dogleg" trend, exemplified by relatively 13 C depleted methane and enriched propane as compared to ethane, is observed for all the kerogen types and at both experimental conditions. Three of the natural gases from the same thrust unit had similar "dogleg" trends indicative of Menilite source rocks with Type III kerogen. These natural gases also contained varying amounts of a microbial gas component that was approximated using the ???? 13 C for methane and propane determined from the experiments. These approximations gave microbial methane components that ranged from 13-84%. The high input of microbial gas was reflected in the higher gas:oil ratios for Outer Carpathian production (115-1568 Nm 3 /t) compared with those determined from the experiments (65-302 Nm 3 /t). Two natural gas samples in the far western part of the study area had more linear trends that suggest a different organic facies of the Menilite Shales or a completely different source. This situation emphasizes the importance of conducting hydrous pyrolysis on samples representing the complete stratigraphic and lateral extent of potential source rocks in determining specific genetic gas correlations. ?? 2009 Elsevier Ltd.

Organic Geochemistry↗

USGS2010

Comparison of XAD with other dissolved lignin isolation techniques and a compilation of analytical improvements for the analysis of lignin in aquatic settings

This manuscript highlights numerous incremental improvements in dissolved lignin measurements over the nearly three decades since CuO oxidation of lignin phenols was first adapted for environmental samples. Intercomparison of the recovery efficiency of three common lignin phenol concentration and isolation techniques, namely XAD, C 18 with both CH 3 OH (C 18 M) and CH 3 CN (C 18 A) used independently for priming and elution steps, and tangential flow filtration (TFF) for a range of aquatic samples including fresh, estuarine and marine waters, was undertaken. With freshwater samples XAD8-1, C 18 M and TFF were all observed to recover ca. 80–90% of the lignin phenols and showed no fractionation effects with respect to diagnostic lignin parameters. With estuarine and marine samples more lignin phenols were recovered with C 18 M and XAD8-1 than TFF because of the increased prevalence of low molecular weight lignin phenols in marine influenced samples. For marine systems, differences were also observed between diagnostic lignin parameters isolated via TFF vs. C 18 M and XAD8-1 as a result of the high molecular weight lignin phenols being less degraded than the bulk. Therefore, it is recommended for future studies of marine systems that only one technique is utilized for ease of intercomparison within studies. It is suggested that for studies solely aimed at recovering bulk dissolved lignin in marine environments that C 18 M and XAD8-1 appear to be more suitable than TFF as they recover more lignin. Our results highlight that, for freshwater samples, all three common lignin phenol concentration and isolation techniques are comparable to whole water concentrated by rotary evaporation (i.e. not isolated) but, that for marine systems, the choice of concentration and isolation techniques needs to be taken into consideration with respect to both lignin concentration and diagnostic parameters. Finally, as the study highlights XAD8-1 to be a suitable method for the isolation of dissolved lignin phenols from aquatic systems (statistically indistinguishable from C 18 M, P < 0.1), lignin data representative of whole waters can be produced for IHSS reference materials or other XAD sample archives.

Organic Geochemistry↗

USGS2010

Organic intermediates in the anaerobic biodegradation of coal to methane under laboratory conditions

Organic intermediates in coal fluids produced by anaerobic biodegradation of geopolymers in coal play a key role in the production of methane in natural gas reservoirs. Laboratory biodegradation experiments on sub-bituminous coal from Texas, USA, were conducted using bioreactors to examine the organic intermediates relevant to methane production. Production of methane in the bioreactors was linked to acetate accumulation in bioreactor fluid. Long chain fatty acids, alkanes (C 19 –C 36 ) and various low molecular weight aromatics, including phenols, also accumulated in the bioreactor fluid and appear to be the primary intermediates in the biodegradation pathway from coal-derived geopolymers to acetate and methane.

Texas↗

USGS2010

Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons

During studies of unconventional natural gas reservoirs of Silurian and Ordovician age in the northern Appalachian basin we observed complete reversal of the normal trend of carbon isotopic composition, such that ??13C methane (C1) >??13C ethane (C2) >??13C propane (C3). In addition, we have observed isotopic reversals in the ??2H in the deepest samples. Isotopic reversals cannot be explained by current models of hydrocarbon gas generation. Previous observations of partial isotopic reversals have been explained by mixing between gases from different sources and thermal maturities. We have constructed a model which, in addition to mixing, requires Rayleigh fractionation of C2 and C3 to cause enrichment in 13C and create reversals. In the deepest samples, the normal trend of increasing enrichment of 13C and 2H in methane with increasing depth reverses and 2H becomes depleted as 13C becomes enriched. We propose that the reactions that drive Rayleigh fractionation of C2 and C3 involve redox reactions with transition metals and water at late stages of catagenesis at temperatures on the order of 250-300??C. Published ab initio calculated fractionation factors for C-C bond breaking in ethane at these temperatures are consistent with our observations. The reversed trend in ??2H in methane appears to be caused by isotopic exchange with formation water at the same temperatures. Our interpretation that Rayleigh fractionation during redox reactions is causing isotopic reversals has important implications for natural gas resources in deeply buried sedimentary basins. ?? 2010.

Organic Geochemistry↗

USGS2011

Role of water in hydrocarbon generation from Type-I kerogen in Mahogany oil shale of the Green River Formation

Hydrous and anhydrous closed-system pyrolysis experiments were conducted on a sample of Mahogany oil shale (Eocene Green River Formation) containing Type-I kerogen to determine whether the role of water had the same effect on petroleum generation as reported for Type-II kerogen in the Woodford Shale. The experiments were conducted at 330 and 350??C for 72h to determine the effects of water during kerogen decomposition to polar-rich bitumen and subsequent bitumen decomposition to hydrocarbon-rich oil. The results showed that the role of water was more significant in bitumen decomposition to oil at 350??C than in kerogen decomposition to bitumen at 330??C. At 350??C, the hydrous experiment generated 29% more total hydrocarbon product and 33% more C15+ hydrocarbons than the anhydrous experiment. This is attributed to water dissolved in the bitumen serving as a source of hydrogen to enhance thermal cracking and facilitate the expulsion of immiscible oil. In the absence of water, cross linking is enhanced in the confines of the rock, resulting in formation of pyrobitumen and molecular hydrogen. These differences are also reflected in the color and texture of the recovered rock. Despite confining liquid-water pressure being 7-9 times greater in the hydrous experiments than the confining vapor pressure in the anhydrous experiments, recovered rock from the former had a lighter color and expansion fractures parallel to the bedding fabric of the rock. The absence of these open tensile fractures in the recovered rock from the anhydrous experiments indicates that water promotes net-volume increase reactions like thermal cracking over net-volume decrease reactions like cross linking, which results in pyrobitumen. The results indicate the role of water in hydrocarbon and petroleum formation from Type-I kerogen is significant, as reported for Type-II kerogen. ?? 2010.

Organic Geochemistry↗

USGS2012

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

A series of methane (CH 4 ) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH 4 pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %R o . In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %R o . For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (P L ) and maximum sorption capacity (Γ max ). The lowest maturity sample (%R o = 0.56) displayed a Langmuir pressure (P L ) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%R o > 2.01) sample at 50 °C. The value of the Langmuir pressure (P L ) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH 4 adsorption on organic rich shales were determined based on the experimental CH 4 isotherms. For the adsorption of CH4 on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs 0 ) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.

Organic Geochemistry↗

USGS2012

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

Organic Geochemistry↗

USGS2013

Multivariate analysis of ATR-FTIR spectra for assessment of oil shale organic geochemical properties

In this study, attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FTIR) was coupled with partial least squares regression (PLSR) analysis to relate spectral data to parameters from total organic carbon (TOC) analysis and programmed pyrolysis to assess the feasibility of developing predictive models to estimate important organic geochemical parameters. The advantage of ATR-FTIR over traditional analytical methods is that source rocks can be analyzed in the laboratory or field in seconds, facilitating more rapid and thorough screening than would be possible using other tools. ATR-FTIR spectra, TOC concentrations and Rock–Eval parameters were measured for a set of oil shales from deposits around the world and several pyrolyzed oil shale samples. PLSR models were developed to predict the measured geochemical parameters from infrared spectra. Application of the resulting models to a set of test spectra excluded from the training set generated accurate predictions of TOC and most Rock–Eval parameters. The critical region of the infrared spectrum for assessing S1, S2, Hydrogen Index and TOC consisted of aliphatic organic moieties (2800–3000 cm −1 ) and the models generated a better correlation with measured values of TOC and S2 than did integrated aliphatic peak areas. The results suggest that combining ATR-FTIR with PLSR is a reliable approach for estimating useful geochemical parameters of oil shales that is faster and requires less sample preparation than current screening methods.

Organic Geochemistry↗

USGS2014

Differentiation of pre-existing trapped methane from thermogenic methane in an igneous-intruded coal by hydrous pyrolysis

So as to better understand how the gas generation potential of coal changes with increasing rank, same-seam samples of bituminous coal from the Illinois Basin that were naturally matured to varying degrees by the intrusion of an igneous dike were subjected to hydrous pyrolysis (HP) conditions of 360 °C for 72 h. The accumulated methane in the reactor headspace was analyzed for δ 13 C and δ2H, and mol percent composition. Maximum methane production (9.7 mg/g TOC) occurred in the most immature samples (0.5 %R o ), waning to minimal methane values at 2.44 %Ro (0.67 mg/g TOC), and rebounding to 3.6 mg/g TOC methane in the most mature sample (6.76 %R o ). Methane from coal with the highest initial thermal maturity (6.76 %R o ) shows no isotopic dependence on the reactor water and has a microbial δ 13 C value of −61‰. However, methane from coal of minimal initial thermal maturity (0.5 %R o ) shows hydrogen isotopic dependence on the reaction water and has a δ 13 C value of −37‰. The gas released from coals under hydrous pyrolysis conditions represents a quantifiable mixture of ancient (270 Ma) methane (likely microbial) that was generated in situ and trapped within the rock during the rapid heating by the dike, and modern (laboratory) thermogenic methane that was generated from the indigenous organic matter due to thermal maturation induced by hydrous pyrolysis conditions. These findings provide an analytical framework for better assessment of natural gas sources and for differentiating generated gas from pre-existing trapped gas in coals of various ranks.

Organic Geochemistry↗

USGS2014

The use of solvent extractions and solubility theory to discern hydrocarbon associations in coal, with application to the coal-supercritical CO 2 system

Samples of three high volatile bituminous coals were subjected to parallel sets of extractions involving solvents dichloromethane (DCM), carbon disulfide (CS 2 ), and supercritical carbon dioxide (CO 2 ) (40 °C, 100 bar) to study processes affecting coal–solvent interactions. Recoveries of perdeuterated surrogate compounds, n-hexadecane-d34 and four polycyclic aromatic hydrocarbons (PAHs), added as a spike prior to extraction, provided further insight into these processes. Soxhlet-DCM and Soxhlet-CS 2 extractions yielded similar amounts of extractable organic matter (EOM) and distributions of individual hydrocarbons. Supercritical CO 2 extractions (40 °C, 100 bar) yielded approximately an order of magnitude less EOM. Hydrocarbon distributions in supercritical CO 2 extracts generally mimicked distributions from the other solvent extracts, albeit at lower concentrations. This disparity increased with increasing molecular weight of target hydrocarbons. Five- and six-ring ring PAHs generally were not detected and no asphaltenes were recovered in supercritical CO 2 extractions conducted at 40 °C and 100 bar. Supercritical CO 2 extraction at elevated temperature (115 °C) enhanced recovery of four-ring and five-ring PAHs, dibenzothiophene (DBT), and perdeuterated PAH surrogate compounds. These results are only partially explained through comparison with previous measurements of hydrocarbon solubility in supercritical CO 2 . Similarly, an evaluation of extraction results in conjunction with solubility theory (Hildebrand and Hansen solubility parameters) does not fully account for the hydrocarbon distributions observed among the solvent extracts. Coal composition (maceral content) did not appear to affect surrogate recovery during CS 2 and DCM extractions but might affect supercritical CO 2 extractions, which revealed substantive uptake (partitioning) of PAH surrogates into the coal samples. This uptake was greatest in the sample (IN-1) with the highest vitrinite content. These findings indicate that hydrocarbon solubility does not exert a strong influence on hydrocarbon behavior in the systems studied. Other factors such as coal composition and maceral content, surface processes (physisorption), or other molecular interactions appear to affect the partitioning of hydrocarbons within the coal–supercritical CO 2 system. Resolving the extent to which these factors might affect hydrocarbon behavior under different geological settings is important to efforts seeking to model petroleum generation, fractionation and expulsion from coal beds and to delineate potential hydrocarbon fate and transport in geologic CO 2 sequestration settings.

Organic Geochemistry↗

USGS2014

Asphaltene content and composition as a measure of Deepwater Horizon oil spill losses within the first 80 days

The composition and content of asphaltenes in spilled and original wellhead oils from the Deepwater Horizon (DWH) incident provide information on the amount of original oil lost and the processes most responsible for the losses within the first 80 days of the active spill. Spilled oils were collected from open waters, coastal waters and coastal sediments during the incident. Asphaltenes are the most refractory component of crude oils but their alteration in the spilled oils during weathering prevents them from being used directly as a conservative component to calculate original oil losses. The alteration is reflected by their increase in oxygen content and depletion in 12 C. Reconnaissance experiments involving evaporation, photo-oxidation, microbial degradation, dissolution, dispersion and burning indicate that the combined effects of photo-oxidation and evaporation are responsible for these compositional changes. Based on measured losses and altered asphaltenes from these experiments, a mean of 61 ± 3 vol% of the original oil was lost from the surface spilled oils during the incident. This mean percentage of original oil loss is considerably larger than previous estimates of evaporative losses based on only gas chromatography (GC) amenable hydrocarbons (32–50 vol%), and highlights the importance of using asphaltenes, as well as GC amenable parameters in evaluating original oil losses and the processes responsible for the losses.

Gulf Of Mexico↗