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At least 217 records · Page 12Linked to original sources
USGS2017

Effects of thermal maturation and thermochemical sulfate reduction on compound-specific sulfur isotopic compositions of organosulfur compounds in Phosphoria oils from the Bighorn Basin, USA

Compound-specific sulfur isotope analysis was applied to a suite of 18 crude oils generated from the Permian Phosphoria Formation in the Bighorn Basin, western USA. These oils were generated at various levels of thermal maturity and some experienced thermochemical sulfate reduction (TSR). This is the first study to examine the effects of thermal maturation on stable sulfur isotopic compositions of individual organosulfur compounds (OSCs) in crude oil. A general trend of 34 S enrichment in all of the studied compounds with increasing thermal maturity was observed, with the δ 34 S values of alkyl-benzothiophenes (BTs) tending to be enriched in 34 S relative to those of the alkyl-dibenzothiophenes (DBTs) in lower-maturity oils. As thermal maturity increases, δ 34 S values of both BTs and DBTs become progressively heavier, but the difference in the average δ 34 S value of the BTs and DBTs (Δ 34 S BT-DBT) decreases. Differences in the isotopic response to thermal stress exhibited by these two compound classes are considered to be the result of relative differences in their thermal stabilities. TSR-altered Bighorn Basin oils have OSCs that are generally enriched in 34 S relative to non-TSR-altered oils, with the BTs being enriched in 34 S relative to the DBTs, similar to the findings of previous studies. However, several oils that were previously interpreted to have been exposed to minor TSR have Δ 34 S BT-DBT values that do not support this interpretation. The δ 34 S values of the BTs and DBTs in some of these oils suggest that they did not experience TSR, but were derived from a more thermally mature source. The heaviest δ 34 S values observed in the OSCs are enriched in 34 S by up to 10‰ relative to that of Permian anhydrite in the Bighorn Basin, suggesting that there may be an alternate or additional source of sulfate in some parts of the basin. These results indicate that the sulfur isotopic composition of OSCs in oil provides a sensitive indicator for the extent of TSR, which cannot be determined from other bulk geochemical parameters. Moreover, when combined with additional geochemical and geologic evidence, the sulfur isotopic composition of OSCs in oils can help to identify the source of sulfate for TSR alteration in petroleum reservoirs.

Montana, Wyoming↗
USGS2017

Historical changes in organic matter input to the muddy sediments along the Zhejiang-Fujian Coast, China over the past 160 years

The burial of sedimentary organic matter (SOM) in the large river-influenced estuarine-coastal regions is affected by hydrodynamic sorting, diagenesis and human activities. Typically, the inner shelf region of the East China Sea is a major carbon sink of the Yangtze River-derived fine-grained sediments. Most of the previous work concentrated on the studies of surface sediments or used a single-proxy in this region. In this study, two cores from the Zhejiang-Fujian Coast were analyzed using bulk (TOC, TN and δ 13 C TOC ) and molecular biomarker ( n -alkane, brassicasterol, dinosterol and glycerol dialkyl glycerol tetraether lipids) techniques to clarify the sources, spatiotemporal distribution and fate of SOM in the Yangtze River Estuary and adjacent shelf. Results from this study indicated that the effects of diagenesis and diffusion on different sedimentary biomarkers resulted in overestimation of the relative contribution of terrestrial organic matter (%OM terr ), compared with those based on δ 13 C TOC . The amounts of terrestrial plant organic matter (OM plant ) and%OM terr in sediments decreased offshore. In contrast, the amounts of marine organic matter (OM marine ) increased offshore, but closer to the Yangtze River mouth, the amounts of soil organic matter (OM soil ) increased. Moreover, the amounts of TOC, OM plant and OM marine biomarkers increased, but OM soil and%OM terr decreased over time in recent decades. Our study suggests that spatial organic matter distribution patterns in marine shelf sediments were controlled primarily by hydrodynamic sorting and nutrient concentrations, and temporally diverse patterns were controlled predominantly by anthropogenic influence (e.g., dam construction and soil conservation, reclamation and agricultural plantations, anthropogenic nutrient input, dust storms, eutrophication, etc) and climate events (e.g., interdecadal climatic jump and heavy rain events) in the geological period.

Zhejiang-Fujian Coast↗
USGS2017

Organic petrology and micro-spectroscopy of Tasmanites microfossils: Applications to kerogen transformations in the early oil window

The transformation of kerogen to hydrocarbons in the early stages of oil generation is critical for understanding the resource potential of liquid-rich shale plays. Organic petrology commonly is used for visual evaluation of type, quality, and thermal maturity of organic matter, but the relationship of visual petrographic changes to chemical transformations is not well characterized. To improve understanding of these processes, organic-walled microfossils of the unicellular green alga Tasmanites (composed of algaenan) in Upper Devonian Ohio Shale (Huron Member, Appalachian Basin) were analyzed by micro-spectroscopy techniques including micro-Fourier transform infrared (micro-FTIR), X-ray photoelectron (XPS), electron probe microanalysis (EPMA), and fluorescence. Immature to mid-oil window maturation sequences of core and outcrop samples with solid bitumen reflectance (BR) and vitrinite reflectance (VR) values ranging from 0.45 to 0.80 %Ro were used. Hydrous pyrolysis was applied to low-maturity (BR: 0.25–0.39 %Ro) Huron and time-correlative New Albany shale samples to create similar artificial maturation sequences for comparison. Micro-FTIR spectroscopy revealed a decrease in the CH 2 /CH 3 ratio with increasing maturity, indicating Tasmanites aliphatic chains become shorter and more branched. Oxygenated functional groups decreased relative to aliphatic stretching bands and increased aromaticity was noted at the highest maturities. In samples that were pyrolyzed for 72 h at temperatures of 300–320 °C (BR: 0.56–0.68 %Ro), Tasmanites showed similar trends, whereas at pyrolysis temperatures of 340 °C and higher (BR > 1.0 %Ro), Tasmanites was pseudomorphed by accumulations of solid bitumen, carbonate and sulfide. Replacement of Tasmanites by these phases in hydrous pyrolysis experiments ≥340 °C and its absence at higher maturities (peak oil, VR and BR ≥ 0.9 %Ro) in naturally matured samples, as documented in a previous study, implies that a large fraction of the algaenan component of original organic carbon is converted to petroleum during thermal maturation. XPS analysis indicated the molar proportion of aliphatic carbon increases with increasing thermal maturity, accompanied by decreases in oxygenated functional groups and olefinic carbon. EPMA of Tasmanites showed highest concentrations of S, with concentrations of redox-sensitive trace elements U, Mo, Ni and V generally at or below detection limits. Decrease in organic S with increasing thermal maturity may be related to cleavage of Tasmanites at C S linkages; however, this relationship was inconsistent and presence of adjacent or entrained nanoscale silicate or sulfide phases may impact measured trace element concentrations. Fluorescence microscopy and spectroscopy showed a red shift in spectral maxima and decreased emission intensities with increasing maturity, interpreted as due to non-radiative energy loss possibly because of increased aromaticity. Collectively, these results provide new insights into the in situ chemical transformations that accompany petrographic changes as oil-prone kerogen converts to petroleum with thermal advance from immature conditions into the mid-oil window.

Organic Geochemistry↗
USGS2018

Evidence for major input of riverine organic matter into the ocean

The changes in the structure of XAD-8 isolated dissolved organic matter (DOM) samples along a river (Penobscot River) to estuary (Penobscot Bay) to ocean (across the Gulf of Maine) transect and from the Pacific Ocean were investigated using selective and two dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy coupled with elemental and carbon isotope analysis. The results provide important insights into the nature of relatively stable structures in the river-to-ocean continuum and the enigma of the fate of terrestrial DOM in the marine system. First, lignin and carboxyl-rich alicyclic molecules (CRAMs), which are indistinguishable from mass spectrometry, were clearly differentiated with NMR spectroscopy. NMR unambiguously showed that CRAMs persisted along the river-to-ocean transect and in the Pacific Ocean, while lignin residues dramatically decreased in abundance from the river to the coastal ocean and the Pacific Ocean. The results challenge a previous conclusion that lignin-derived compounds are refractory and can accumulate in the coastal ocean. The loss of terrestrial plant-derived aromatic compounds such as lignin and tannin residues throughout the sequence of riverine, coastal, and open ocean DOM extracts could also partially explain the decreasing organic carbon recovery by XAD-8 isolation and the change in carbon stable isotope composition from riverine DOM (δ 13 C −27.6‰) to ocean DOM (δ 13 C −23.0‰) extracts. The observation, from advanced NMR, of similar CRAM molecules in XAD-8 isolated DOM samples from the Penobscot River to the Penobscot Bay and from the ocean refutes a previous conclusion that XAD-isolated DOM samples from seawater and river are distinctly different. The alicyclic structural features of CRAMs and their presence as the major structural units in DOM extracts from the Penobscot River to Gulf of Maine transect, together with the deduced old 14 C age of CRAMs in the ocean, imply that terrestrial CRAMs may persist on timescales long enough to be transported into the ocean.

Organic Geochemistry↗
USGS2018

Experimental investigation of the role of rock fabric in gas generation and expulsion during thermal maturation: Anhydrous closed-system pyrolysis of a bitumen-rich Eagle Ford Shale

Gold-tube pyrolysis experiments were conducted on miniature core plugs and powdered rock from a bitumen-rich sample of Eagle Ford Shale to investigate the role of rock fabric in gas generation and expulsion during thermal maturation. The samples were isothermally heated at 130, 300, 310, 333, 367, 400, and 425 °C for 72 h under a confining pressure of 68.0 MPa, corresponding to six levels of induced thermal maturity: pre-oil generation (130 °C/72 h), incipient oil/bitumen generation (300 and 310 °C/72 h), early oil generation (333 °C/72 h), peak oil generation (367 °C/72 h), early oil cracking (400 °C/72 h), and late oil cracking (425 °C/72 h). Experimental results show that gas retention coupled with compositional fractionation occurs in the core plug experiments and varies as a function of thermal maturity. During the incipient oil/bitumen generation stage, yields of methane through pentane (C 1 –C 5 ) from core plugs are significantly lower than those from rock powder, and gases from core plugs are enriched in methane. However, the differences in C 1 –C 5 gas yield and composition decrease throughout the oil generation stage, and by the oil cracking stage no obvious compositional difference in C 1 –C 5 gases exists. The decrease in the effect of rock fabric on gas yield and composition with increasing maturity is the result of an increase in gas expulsion efficiency. Pyrolysis of rock powder yields 4–16 times more CO 2 compared to miniature core plugs, with δ 13 C CO2 values ranging from −2.9‰ to −0.6‰, likely due to carbonate decomposition accelerated by reactions with organic acids. Furthermore, lower yields of gaseous alkenes and H 2 from core plug experiments sugge

Organic Geochemistry↗
USGS2018

Suppression of vitrinite reflectance by bitumen generated from liptinite during hydrous pyrolysis of artificial source rock

Mean random vitrinite reflectance (R o ) is the most widely accepted method to determine thermal maturity of coal and other sedimentary rocks. However, oil-immersion R o of polished rock or kerogen samples is commonly lower than R o values measured in samples from adjacent vitrinite-rich coals that have undergone the same level of thermal stress. So-called suppressed R o values have also been observed in hydrous pyrolysis experiments designed to simulate petroleum formation. Various hypotheses to explain R o suppression, such as sorption of products generated from liptinite during maturation, diagenetic formation of perhydrous vitrinite or overpressure, remain controversial. To experimentally test for suppression of vitrinite reflectance, artificial rock was prepared using silica and a calcined blend of limestone and clay with various proportions of thermally immature vitrinite-rich Wyodak-Anderson coal and liptinite-rich kerogen isolated from the oil-prone Parachute Creek Member of the Green River Formation. The samples were subjected to hydrous pyrolysis for 72 h. at isothermal temperatures of 300 °C, 330 °C, and 350 °C to simulate burial maturation. Compared to artificial rock that contains only coal, samples with different proportions of oil-prone kerogen show distinct suppression of calibrated R o at 300 °C and 330 °C. The reflectance of solid bitumen generated during heating of the samples is lower than that of the associated vitrinite and does not interfere with the R o measurements. These results provide the first experimental evidence that R o suppression occurs in vitrinite mixed with liptinite-rich kerogen in a rock matrix. Although the precise chemical mechanism for R o suppression by liptinite remains unclear, free radicals generated from solid bitumen and associated volatile products during maturation of liptinite may contribute to termination reactions that slow the aromatization and rearrangement of polyaromatic sheets in vitrinite, thus suppressing R o . This mechanism does not preclude R o suppression that might result from overpressure or differences in redox conditions during diagenesis.

Organic Geochemistry↗
USGS2019

Hydrous heating experiments at 130°C yield insights into the occurrence of hydrogen sulfide and light alkanes in natural gas reservoirs

Improved understanding of the origin of produced volatiles from conventional reservoirs and unconventional source rocks is critical for petroleum exploration and production. A series of hydrous heating experiments using two immature Type II siliciclastic source rocks, Pennsylvanian Turner Mine shale (TMS) and Devonian New Albany Shale (NAS), at 130 °C over one to two years were conducted to assess gas generation at low temperature. Elemental sulfur (ES) was added to the NAS samples to evaluate the role of sulfur on thermochemical sulfate reduction (TSR). The produced volatile composition was investigated in situ using Raman spectroscopy at the end of the heating experiments. Results show that the two source rocks yield different types and concentrations of volatiles. Only CH 4 and CO 2 were detected following hydrous heating of the TMS source rock in contrast to CH 4 , C 2 H 6 , C 3 H 8 , and CO 2 which were observed in experiments using NAS. Variations in the produced volatiles are likely the result of compositional differences within the respective source rock organic matter. Experiments involving ES show strong H 2 S signals that are likely due to the formation of H 2 S from the reaction of ES with water at 130 °C. H 2 S signals correlate with a greater relative concentration of CH 4 and CO 2 compared to experiments where ES was not added, on a time-normalized basis. The correlation between the presence of H 2 S and an increase in CH 4 and CO 2 concentration could indicate the occurrence of TSR. Here we propose that H 2 S in siliciclastic shale can be generated in the presence of ES at low temperatures via both disproportionation of ES into H 2 S and SO 4 2– , and TSR. Our findings from this study provide experimental evidence that may aid efforts to interpret the origin of H 2 S in low-temperature sedimentary basins.

Pennsylvania↗
USGS2020

Comparability and reproducibility of biomarker ratio values measured by GC-QQQ-MS

The Norwegian Geochemical Standard North Sea Oil-1 was analyzed by gas chromatography triple quadrupole mass spectrometry (GC-QQQ-MS) on two instruments using independently developed analytical methods. Biomarker ratios determined by GC-QQQ-MS were compared to each other and to previously reported values determined by gas chromatography single quadrupole mass spectrometry (GC-Q-MS) or flame ionization detection (GC-FID). Hopane, sterane, and tricyclic ratio values determined by GC-QQQ-MS in multiple reaction monitoring (MRM) mode are comparable to each other, but their comparability to reported values measured by GC-Q-MS in selected ion monitoring (SIM) mode depends in part on whether the compounds in the ratio have similar or dissimilar mass spectral responses. For example, sterane and hopane stereoisomer thermal maturity ratios measured by GC-QQQ-MS in MRM mode agree with previously reported GC-Q-MS SIM values, but an offset is observed for ratios of rearranged hopanes or steranes to their non-rearranged counterparts. Triaromatic steroid, monoaromatic steroid, phenanthrene, and methylphenanthrene ratios measured by GC-QQQ-MS are comparable to each other and to reported GC-Q-MS SIM values. The carbon preference index is comparable across GC-QQQ-MS measurements and reported GC-FID values, while comparability is more variable for other ratios based on pristane, phytane, and/or n -alkanes. Comparability of variably acquired biomarker data could be enhanced in the future by developing instrument- and ratio-specific correction factors or by modifying GC-QQQ-MS parameters and MRM transitions to more closely reproduce previously reported values.

Organic Geochemistry↗
USGS2022

Molecular mechanisms of solid bitumen and vitrinite reflectance suppression explored using hydrous pyrolysis of artificial source rock

The most commonly used parameter for thermal maturity calibration in basin modelling is mean random vitrinite reflectance (R o ). However, R o suppression has been noted in samples containing a high proportion of liptinite macerals. This phenomenon has been demonstrated empirically using hydrous pyrolysis of artificial source rock containing various proportions of thermally immature Wyodak-Anderson coal and liptinite-rich kerogen from the Parachute Creek Member of the Green River Formation. Analysis of samples pyrolyzed at 330 °C for 72 h demonstrates that R o values of both vitrinite and solid bitumen are suppressed in rocks containing liptinite-rich kerogen. Raman and micro-Fourier transform infrared (µ-FTIR) analyses were performed to investigate the mechanisms of suppression. Raman maturity proxies show decreased aromaticity in samples with suppressed R o , particularly in solid bitumen, with aromaticity decreasing as the proportion of liptinite increases. The µ-FTIR proxy for aliphatic chain length and/or branching ratio is static in solid bitumen, yet increases slightly in vitrinite as the liptinite proportion increases. These spectroscopic results suggest slightly different suppression mechanisms for vitrinite and solid bitumen, with reduced C C bond cleavage and marginally reduced aromaticity in vitrinite with suppressed R o , and strongly reduced aromaticity and C C bond cleavage in solid bitumen with suppressed R o . These results support the hypothesis that the generation of free radicals during maturation slows aromatization and highlight the disadvantages of using solid bitumen R o for maturity calibration in liptinite-rich samples. Furthermore, our results indicate that use of Raman data obtained from liptinite-rich samples may also result in suppressed maturity indicators, particularly if the macerals are not identified prior to analysis.

Organic Geochemistry↗
USGS2023

Mapping ancient sedimentary organic matter molecular structure at nanoscales using optical photothermal infrared spectroscopy

Elucidating the molecular structure of sedimentary organic matter (SOM) is key to understanding petroleum generation processes, as well as ancient sedimentary environments. SOM structure is primarily controlled by biogenic source material (e.g., marine vs. terrigenous), depositional conditions, and subsurface thermal history. Additional factors, e.g., strain, may also impact the molecular structure of SOM. Multiple spatially resolved approaches exist for in situ evaluation of SOM, including Raman and infrared spectroscopies, as well as mass spectrometric methods. While these methods have enabled increased understanding of the occurrence and distribution of SOM functional groups, they suffer from disadvantages including low spatial resolution (infrared spectroscopy), limited molecular information (Raman spectroscopy), and sample destruction (mass spectrometric methods). Recent technological advances have resulted in infrared spectrometers capable of breaking the Abbe diffraction limit, greatly increasing the spatial resolutions accessible for an infrared measurement. Here we utilize optical photothermal infrared spectroscopy (O-PTIR) to record maps of functional group distributions at 500 nm spatial resolution in Tasmanites (algal microfossils) from the Upper Devonian Ohio Shale. These data allow for discrimination between Tasmanites , adjacent SOM, and fine-grained minerals. Additionally, functional group distributions within Tasmanites were found to be generally homogenous, although slight variations exist between the body and fold apices (zones of greatest deformation) which may indicate strain-induced chemical reactions. The data presented here represent the first application of O-PTIR to study SOM, highlighting the promise of this analytical approach for future studies evaluating the molecular composition of geologic materials at sub-micron scales.

Organic Geochemistry↗
USGS2025

Validation of the U37K' paleotemperature proxy in the South Brazilian Bight from core-top sediments

The paleothermometer based on the alkenone unsaturation index ( U 37 K ′ "> U37K′ ) is often used to reconstruct past sea surface temperatures (SST). In the SW Atlantic Ocean, however, a limited understanding of the seasonal and depth distribution of coccolithophores, which generates the U 37 K ′ "> U37K′ signal preserved in ocean sediments, hinders accurate estimates of past regional SSTs. We analyzed 45 core-top sediment samples from the continental shelf of the South Brazilian Bight (SBB, 23 °S to 28 °S) to assess regional spatial U 37 K ′ "> U37K′ -SST gradients and improve SST estimates. The U 37 K ′ "> U37K′ data were converted to SST using six published paleotemperature equations and compared to modern observational SST data from the World Ocean Atlas (2018) data set. Data indicate that the U 37 K ′ "> U37K′ signal is produced during the austral summer and autumn when regional episodic upwelling events occur over the inner-shelf and the nutricline shoals at the slope. Our analysis of core-top data shows that SST estimates derived from most calibration equations closely align with modern observed temperatures but are skewed toward warmer months associated with upwelling-derived nutrients. Our findings underscore the importance of considering regional and seasonal biases to improve the accuracy of paleotemperature reconstructions. Understanding the factors influencing the SBB U 37 K ′ "> U37K′ signal enables a more meaningful comparison between regional paleoceanographic studies, improving our understanding of past changes in the SW Atlantic Ocean and our ability to predict regional SST response to ongoing and future warming.

South Brazilian Bight↗
USGS2025

Nanometer-scale relationships between sedimentary organic matter molecular composition, fluorescence, cathodoluminescence, and reflectance: The importance of oxygen content at low thermal maturities

Molecular characterization of sedimentary organic matter (SOM), termed macerals, is a common goal when seeking to understand petroleum generation as well as other geologic processes in deep time. However, unambiguous measurement of discrete macerals is challenging due to the small size of organic particles in sedimentary rocks, the proximity of different organic matter types to one another, mineral-organic matter interactions, and maceral mixing that occurs during SOM isolation prior to ex situ analysis. The recent advent of infrared spectrometers capable of nanometer-scale resolution and the application of these technologies to geologic samples has enabled advances in rapid, in situ molecular characterization of SOM allowing for insights into paleoenvironmental processes, such as organic matter productivity and preservation, among others. Here we employ one such technology, optical photothermal infrared (OPTIR) spectroscopy, to map SOM functional group distributions at 500-nm resolution in a sample from the Lower Cretaceous Sunniland Limestone of the South Florida Basin. Examined fields of view include occurrences of amorphous organic matter (AOM), inertinite, micrinite, solid bitumen, telalginite, and vitrinite. OPTIR data from these macerals are compared against traditional organic petrographic data from the same organic grains including fluorescence intensity and white light reflectance as well as against cathodoluminescence response, an emerging organic petrographic approach. Maceral oxygen content (using carbonyl functional group abundance as a proxy) is observed to vary widely between maceral types but correlates strongly with fluorescence and cathodoluminescence intensity as well as against reflectance. These findings highlight the important role that oxygen content plays in determining the optical properties of SOM and further demonstrate the ability of OPTIR to discriminate subtle molecular differences between SOM types.

Organic Geochemistry↗
USGS2026

Metalloporphyrins in the Eagle Ford Shale

Using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), Zheng et al. (2018, Energy & Fuels 32, 10382) reported abundant iron and vanadyl porphyrins and minor amounts of gallium and nickel porphyrins in asphaltenes extracted from a single lower Eagle Ford Shale sample. This finding is most unusual as iron and gallium porphyrins have been previously found only in coal. In this study, petroporphyrins in samples of the Eagle Ford Shale previously studied by French et al. (2020, Marine Petrol. Geol. 118, 104459), were examined using atmospheric pressure photoionization (APPI) FT-ICR-MS. Vanadyl porphyrins (N4VO) dominated the asphaltenes in thermally immature (VRo < 0.56%) samples decreasing in relative abundance with increasing maturity. Only minor amounts of nickel porphyrins were detected in the immature and early oil samples. The distribution of the vanadyl porphyrins is comparable to those reported for marine oils at varying levels of maturity. Immature samples contained porphyrins that were predominantly deoxophylloerythroetio- (DPEP: DBE = 18) and di- deoxophylloerythroetio (di-DPEP: DBE = 19) porphyrins, while ETIO- (DBE = 17), rhodo- (DBE = 20, 21, and 22) and higher condensed (DBE ≥ 23) porphyrins increased with increasing maturity. The vanadyl porphyrins included species with additional one to three oxygen atoms (N4VOx, x= 1 to 4) and one sulfur atom with one to two oxygen atoms (S1N4VOx, x=1 to 3). The degree of additional oxygen and sulfur atoms is consistent with O/C and Sorg/C of associated kerogen. No iron or gallium porphyrins were detected, showing that they are not a ubiquitous feature of the Eagle Ford. We hypothesize that the previously reported iron and gallium porphyrins (Zheng et al., 2018) were present because the specific sample that was analyzed in detail was from the early onset of the Cenomanian–Turonian oceanic anoxic event (OAE-2) in contrast to the samples investigated in this study that are primarily from the lower part of the Eagle Ford pre-dating OAE-2. Submarine volcanism, associated with eruption of large igneous provinces, occurred pre-OAE-2, injecting iron and other inorganic nutrients, giving rise to algal blooms and the acidification of the seawater. At the onset of OAE-2, boreal water masses flowed into the southern Western Interior Seaway, shifting the water column to more oxygenated conditions. Low pH-high Eh (oxic) conditions enhance the availability of iron and gallium such that these events abruptly changed the seawater chemistry, specifically enriching iron and gallium relative to vanadium and nickel. These pH-Eh conditions are similar to the depositional conditions associated with coals, which are known to contain iron and gallium porphyrins, suggesting similar conditions resulted in iron and gallium metalation of porphyrins in the marine setting of the Western Interior Seaway.

Texas↗
USGS2026

Evidence for a biological origin of uranium-rich carbon masses within the Ediacaran Salt Range Formation of Pakistan

Thucholites are unique organic structures found in igneous and sedimentary rocks composed of a U-C-rich interior enclosed by an organic outer shell. Their formation and occurrence have perplexed scientists for over 100 years. Typically, thucholites are sparse in sedimentary rocks but where found in abundance, they may be the result of rapid paleoecological disruptions, e.g., volcanic ashfall. Here, we evaluated thucholites from the Ediacaran Salt Range Formation of the Indus Basin in Pakistan using field emission scanning electron microscopy (FESEM) and nanoscale secondary ion mass spectroscopy (NanoSIMS) to propose a two-stage mechanism for thucholite development. NanoSIMS results suggest organic matter in thucholite cores formed by biological fractionation (represented by the presence of lighter 13 C/ 12 C and 34 S/ 32 S) while the outer organic mantle formed via radiolysis-induced polymerization. FESEM elemental analysis confirms compositional differences between the two thucholite components (core and mantle), further implying their contrasting origins. Dimensional comparison of thucholite cores and their U-bearing mineral morphologies to ancient and modern U-biomineralized microbes suggests that the thucholite cores formed from metal-biological interactions. The presence of volcanogenic biotite, alkali feldspar, and clay spherules (interpreted as devitrified volcanic glass) with thucholite suggests that the thucholite cores in the Salt Range Formation are biological responses to rapid paleoenvironmental change from volcanic eruption which preserved the fossilized morphologies of Proterozoic microorganisms.

Salt Range↗
USGS2001

Experimental controls on D/H and 13C/12C ratios of kerogen, bitumen and oil during hydrous pyrolysis

Large isotopic transfers between water-derived hydrogen and organic hydrogen occurred during hydrous pyrolysis experiments of immature source rocks, in spite of only small changes in organic 13C/12C. Experiments at 330 ??C over 72 h using chips or powder containing kerogen types I and III identify the rock/water ratio as a main factor affecting ????D for water and organic hydrogen. Our data suggest that larger rock permeability and smaller rock grain size increase the H-isotopic transfer between water-derived hydrogen and thermally maturing organic matter. Increasing hydrostatic pressure may have a similar effect, but the evidence remains inconclusive. ?? 2001 Elsevier Science Ltd. All rights reserved.

Organic Geochemistry↗
USGS2001

Geochemical evidence for mudstone as the possible major oil source rock in the Jurassic Turpan Basin, Northwest China

Geologists and geochemists have debated whether hydrocarbons from Jurassic coal measures are derived from the mudstones or the coals themselves. This paper identifies mudstones as the possible major source rock of hydrocarbons in the Jurassic basins in Northwest China. The Turpan Basin is used as a representative model. Mudstones in the Middle-Lower Jurassic are very well developed in the basin and have an average genetic potential from 2 to 4 mg/g. The vitrinite reflectance of the source rocks ranges from 0.6 to 1.3%, exhibiting sufficient thermal maturity to generate oil and gas. Biomarkers in crude oils from the basin are similar to those in mudstones from the coal-bearing strata, with a low tricyclic terpane (cheilanthane) content, a relatively high content of low carbon number (less than C22) tricyclic terpanes and a low content of high carbon number tricyclic terpanes, relatively high ratios of Ts/Tm, and C29 Ts/17?? (H)-C29 norhopane, and low ratios of Tm/17?? (H)-C30 hopane and 17?? (H)-C31 homohopane/17?? (H)-C30 hopane. These characteristics and the distribution of steranes and terpanes in the crude oil and mudstone differ significantly from those of the Jurassic coals and carbonaceous shales of the basin, indicating mudstone is possibly the major source rock of the oils in the Turpan Basin. ?? 2001 Elsevier Science Ltd. All rights reserved.

Organic Geochemistry↗