Organic-rich Sedimentary Rocks Research Articles

Artificial intelligence-based prediction of hydrogen adsorption in various kerogen types: Implications for underground hydrogen storage and cleaner production

Hydrogen offers significant potential as a sustainable energy source. However, its storage and transportation pose challenges due to its volatility and low density. Subsurface geological formations, such as shale, sandstone, and coal, have been investigated as potential storage sites for hydrogen. Precise estimation of hydrogen adsorption in these formations necessitates a thorough understanding of kerogens, organic-rich sedimentary rocks prevalent in unconventional formations. In this study, we introduce a novel approach employing Extreme Gradient Boosting (XGBoost), Random forest (RF), Light gradient Boosting (LGBM), and Natural gradient boosting (NGBM) algorithms to intelligently predict hydrogen adsorption in various kerogen types. Among these, the NGBM algorithm, utilizing three input features (temperature, pressure, and kerogen types), demonstrated the highest predictive accuracy, achieving an R2 value of 0.989, RMSE of 0.062, and MAE of 0.037 for all data samples. SHAP diagram analysis identified kerogen types as the most influential parameter within the NGBM model. The presented approach has implications beyond energy storage, highlighting the significance of advanced technologies in addressing complex energy challenges. Precise hydrogen adsorption estimation in subsurface formations is vital for developing sustainable energy solutions, and our approach has the potential to expedite progress in this field. Interdisciplinary collaboration among geologists, chemists, and data scientists is crucial for devising innovative solutions for sustainable energy.

Uranium isotopes in non-euxinic shale and carbonate reveal dynamic Katian marine redox conditions accompanying a decrease in biodiversity prior to the Late Ordovician Mass Extinction

The Late Ordovician mass extinction (LOME) is the first major mass extinction event in the Phanerozoic. However, global biodiversity started to decline during the Katian (prior to the LOME) and coeval global ocean redox conditions are not well understood. The deposition of Katian organic-rich sedimentary rocks, namely the calcareous Collingwood Member and overlying siliciclastic Rouge River Member, was triggered by the concurrent Taconic Orogeny in southern Ontario (Canada) near the interface between the epicratonic Appalachian and Michigan basins. In this study, we used geochemical elemental proxies and uranium isotope compositions (δ238U) to reconstruct local and global ocean redox states during deposition of both units at seven drill core localities throughout southern Ontario. Local redox conditions are revealed by several proxies (redox sensitive trace metals, Fe speciation, and Corg:P ratios). Collectively, these proxies suggest spatiotemporal redox variations for the Collingwood Member: O2-deficient conditions (non-euxinic) for the deep waters of the Appalachian and Michigan basins and mostly oxic-suboxic conditions for the shallow waters. In contrast, predominantly oxic-suboxic conditions are suggested for the Rouge River Member.Global ocean redox conditions are inferred from the δ238U of both units. The coeval seawater δ238U value during Collingwood Member deposition is estimated to be from ∼−0.87‰ to ∼−0.64‰, based on both carbonate δ238U (samples leached with 1 N HCl) and δ238Ubulk-non-detrital data (corrected from the bulk δ238U). Particularly, the δ238Ubulk-non-detrital data of the Collingwood Member from multiple cores (both shallow and deep waters) are positively correlated with elemental redox proxies, suggesting a local redox control on δ238U offsets between sediments and water columns. In contrast, the δ238Ubulk-non-detrital of the suboxic Rouge River Member (average = −0.32 ± 0.12‰) from several cores do not correlate with local redox proxies. The coeval seawater δ238U during Rouge River Member deposition is estimated between −0.62 ± 0.12‰ and −0.42 ± 0.12‰ assuming a δ238U offset of 0.1–0.3‰ as observed between modern suboxic sediments and seawater. For this range of seawater δ238U, a three-sink U isotope mass balance model suggests a contraction of global euxinic seafloor area from deposition of the Collingwood Member (0.5–31.6%; median = 1.0–14.2%) to the Rouge River Member (0.2–2.0%; median = 0.3–1.0%), which could have been associated with the concurrent Taconic Orogeny. Collectively, global marine redox proxy data (i.e., δ98Mo, δ238U) from this and previous studies imply dynamic Katian ocean redox conditions during the decrease of metazoan biodiversity prior to the LOME. As a similar extent of global ocean euxinia during the LOME2 also occurred episodically during the Katian but did not result in LOME2-like mass extinctions, it is suggested that other factors (e.g., climate), besides expanded ocean euxinia, could have contributed to the second phase of the LOME.

Mercury isotope constraints on the timing and pattern of magmatism during the end-Triassic mass extinction

The End-Triassic Mass Extinction (ETME) was broadly coincident with the emplacement of the Central Atlantic Magmatic Province (CAMP). However, the relationship between evolutionary phases of CAMP (i.e. prolonged shallow intrusive pulses and later extrusives) and the ETME is not clear. Here, a high-resolution record of changing magmatic activity is established using mercury (Hg) isotopes through a Triassic-Jurassic sedimentary succession deposited on the northern flank of CAMP. Successive negative and positive mass independent fractionation (MIF) of odd Hg isotopes through the end-Triassic interval in this succession suggest dominantly thermogenic Hg release from intrusive heating of organic-rich sedimentary rocks, followed by mainly volcanogenic input of mantle-sourced Hg. This inferred pattern is also supported by correlations to available CAMP ages. Minimum calculated volumes of thermogenic and volcanogenic Hg needed to drive the observed shifts at the basin-scale are plausible based on likely CAMP Hg release volumes, and biotic turnover in the studied region was unlikely to have occurred before the onset of volcanogenic Hg release.

Basaltic sills emplaced in organic-rich sedimentary rocks: Consequences for organic matter maturation and Cretaceous paleo-climate

Many continental large igneous provinces coincide with climate perturbations and mass extinctions. When basaltic plumbing systems traverse carbon-rich sedimentary rocks, large volumes of greenhouse gases may be generated. We document how intrusive sills of the Mesozoic High Arctic Large Igneous Province affected surrounding fine-grained, organic-rich siliciclastic rocks of the Sverdrup Basin in the Canadian Arctic Archipelago. Petrographic and X-ray diffraction data from samples located near sills show the presence of high-temperature metamorphic phases (diopside, andalusite, garnet, and cordierite). Raman thermometry on organic matter yields peak temperatures of 385−400 °C near sill contacts, tailing off to far-field temperatures of ≤230 °C. Samples located >20 m from sills show no systematic change in vitrinite reflectance and have a VRo eq% value of ∼2.5%, which indicates a temperature of ∼210 °C. The finite element thermal modeling tool SUTRAHEAT was applied to the 17-m-thick Hare Sill, emplaced at 3 km depth at 1105 °C. SUTRAHEAT results show that contact-proximal rocks attain temperatures of >700 °C for a brief period (∼1 year). By 5 years, the Hare Sill is completely solidified (<730 °C), and the temperature anomaly collapses rapidly thereafter as the thermal pulse propagates outward. By 10 years, all rocks within 10 m of the Hare Sill are between 450 °C and 400 °C, rocks at 20 m from the contact attain 200 °C, yet far-field temperatures (>50 m) have barely changed. When multiple sills are emplaced between 4 km and 6 km depth, all rocks between sills reach ∼250 °C after 100 years, showing that it is possible to raise regional-scale background temperatures by ∼150 °C for the observed High Arctic Large Igneous Province sill density. Vitrinite reflectance data and pyrolysis results, together with SILLi thermal modeling, indicate that much of the hydrocarbon-generating potential was eliminated by High Arctic Large Igneous Province intrusions. The SILLi model yields ∼20 tonnes/m2 of organic equivalent CO2 (all carbon gas is reported as CO2) from the Hare Sill alone when emplaced into Murray Harbour Formation rocks with 5.7 wt% organic carbon, and ∼226 tonnes/m2 by emplacement of multiple sills throughout the 2-km-thick Blaa Mountain Group with 3 wt% organic carbon. On a basin scale, this yields a total of ∼2550 Gt CO2 from the Hare Sill, with ∼13,000 Gt CO2 being generated by the multiple sill scenario, similar to estimates from other large igneous provinces. Much of the Blaa Mountain Group rocks now have organic carbon contents of <1 wt%, which is consistent with large volumes of carbon-species gas having been generated, likely a mixture of CO2, CH4, and other species. However, organic-rich Murray Harbour Formation rocks show no obvious reduction in organic carbon content toward the Hare Sill intrusive contacts, which suggests that not all of the carbon was lost from the sedimentary package hosting High Arctic Large Igneous Province magmas. We suggest that some of the gas generated by contact metamorphism failed to drain out for lack of high-permeability conduits, and then back-reacted to form calcite cements and pyrobitumen during cooling.

Release of mercury during contact metamorphism of shale: Implications for understanding the impacts of large igneous province volcanism

Elevated mercury (Hg) in sedimentary strata are a widely used tracer for assessing the relationship between large igneous province (LIP) activity and global environmental change. A key unknown in applying this proxy is the extent to which Hg was sourced from contact metamorphism of sedimentary rocks during sill intrusions versus gaseous emissions of the magmas themselves. Here, we investigate Hg behaviour during contact metamorphism of shales. We show loss of 80–99% of the sedimentary Hg in contact aureoles in four case studies covering the interactions around dykes, sills and plutons associated the High Arctic LIP (Sverdrup Basin, Canada), the Karoo LIP (South Africa) and the Skagerrak-centred LIP (Oslo Rift, Norway). A combination of geochemical data and thermal modelling around a dyke from the High Arctic LIP shows 33% Hg volatilization in the aureole at 265–300°C. The other cases show similar behaviours with significant lowering of organic-bound Hg, more significantly in the innermost 60% of the contact aureoles. We hypothesize that gaseous Hg is transported out of aureoles during metamorphism, together with CH4 and CO2. Furthermore, we estimate the thermogenic Hg mobilization from Karoo LIP aureoles as 72–192 t per km3 of aureole, which is between 1–3 times the estimated volumetric Hg release from Karoo magmas. When scaling our results to the size of the shale portions of the Karoo Basin affected by the LIP and a timescale of 100 kyr of sill emplacement, the average Hg flux is calculated to have been 78–207 t/y with maximum values up to ∼300 t/y. The pulsed nature of intrusive volcanism suggests that this thermogenic Hg flux could have dominated LIP Hg emissions during periods of their life span. Our results demonstrate that the global Hg cycle can be significantly perturbed following LIP-scale sill emplacement into organic-rich sedimentary rocks and our quantification of the emissions based on source-rock analysis provides important information for independent interpretation of the sedimentary Hg record.

Impact of permeability evolution in igneous sills on hydrothermal flow and hydrocarbon transport in volcanic sedimentary basins

Abstract. Sills emplaced in organic-rich sedimentary rocks trigger the generation and migration of hydrocarbons in volcanic sedimentary basins. Based on seismic and geological observations, numerical modeling studies of hydrothermal flow around sills show that thermogenic methane is channeled below the intrusion towards its tip, where hydrothermal vents nucleate and transport methane to the surface. However, these models typically assume impermeable sills and ignore potential effects of permeability evolution in cooling sills, e.g., due to fracturing. Here, we combine a geological field study of a volcanic basin (Neuquén Basin, Argentina) with a hybrid finite-element–finite-volume method (FEM–FVM) of numerical modeling of hydrothermal flow around a sill, including hydrocarbon generation and transport. Our field observations show widespread veins within sills composed of graphitized bitumen and cooling joints filled with solid bitumen or fluidized shale. Raman spectroscopy indicates graphitization at temperatures between 350 and 500 ∘C, suggesting fluid flow within the intrusions during cooling. This finding motivates our modeling setup, which investigates flow patterns around and through intrusions that become porous and permeable upon solidification. The results show three flow phases affecting the transport of hydrocarbons generated in the contact aureole: (1) contact-parallel flow toward the sill tip prior to solidification, (2) upon complete solidification, sudden vertical “flushing” of overpressured hydrocarbon-rich fluids from the lower contact aureole towards and into the hot sill along its entire length, and (3) stabilization of hydrocarbon distribution and fading hydrothermal flow. In low-permeability host rocks, hydraulic fracturing facilitates flow and hydrocarbon migration toward the sill by temporarily elevating porosity and permeability. Up to 7.5 % of the generated methane is exposed to temperatures >400 ∘C in the simulations and may thus be permanently stored as graphite in or near the sill. Porosity and permeability creation within cooling sills may impact hydrothermal flow, hydrocarbon transport, and venting in volcanic basins, as it considerably alters the fluid pressure configuration, provides vertical flow paths, and helps to dissipate overpressure below the sills.

Paralava and clinker from the Canadian Arctic: a record of combustion metamorphism dating back to the late Miocene

Outcrops with conspicuous reddish to yellow-colored clinker, blackish paralava, and blends of both with a breccia-like appearance occur across the Canadian Arctic. We examined such rocks on Ellesmere Island, Banks Island, and the Mackenzie Delta area. These rocks are a product from natural combustion of bituminous shale and low-rank coal seams in Cretaceous and Paleogene host sedimentary rocks, respectively. The main mineral phases of clinker and silicate paralava samples are comprised of quartz + hematite ± feldspars ± cristobalite (or tridymite) ± cordierite–sekaninaite ± clinopyroxene ± sillimanite ± glass. Slag-like iron oxide paralava (74–95 wt.% total Fe2O3) consisting of hematite ± magnetite ± clinopyroxene occur in Paleogene host sedimentary rocks, rich in siderite concretions. The whole-rock geochemical composition of clinker and silicate paralava shows similarities for samples from the same outcrop. Regional and local specific elemental enrichments are mainly inherited from the sedimentary protoliths, which are characterized by volcanogenic input (Paleocene sedimentary rocks) or oxygen-depleted depositional conditions (Upper Cretaceous bituminous sedimentary rocks). Spontaneous combustion could take place when the organic-rich sedimentary rocks become exposed to atmospheric oxygen. This process has occurred at least since the Messinian stage (Miocene) on Ellesmere Island (6.1 ± 0.2 Ma; 40Ar/39Ar incremental heating dating on whole-rock paralava) and continues until now. An active combustion process on scree from a coal seam and clastic Eureka Sound Group sedimentary rocks was observed on Ellesmere Island.

Coupled reduction of structural Fe(III) in nontronite and oxidation of petroleum hydrocarbons

Fe-bearing clay minerals are frequently present in oil reservoirs as potential electron acceptor. Compounds in crude oil may mediate microbial reduction of structural Fe(III) in clay minerals through their roles as electron donor and shuttle. However, there is limited knowledge about these roles and resulting transformation of oil compounds. In this study, bio-reduction of structural Fe(III) in nontronite (NAu-2, Fe-rich smectite) by the dissimilatory iron-reducing bacterium (DIRB) Shewanella putrefaciens CN32 was investigated in the presence of either crude oil or specific fractions of oil. Lactate was added in some experiments as extra electron donor. The fractions of saturates (nC14-nC20 alkanes and nC8-nC14-alkyl cyclohexanes), aromatics (with two/three benzene rings), and polar compounds (carboxylic acids) of crude oil were adsorbed to NAu-2 surface. Without CN32, crude oil was able to slightly reduce structural Fe(III) in NAu-2. In the presence of CN32, reduction of Fe(III) in NAu-2 was coupled with oxidation of bulk oil and saturated/aromatic fractions. The reduction extent (21.5 ± 0.3%) and rate (0.04 ± 0.00 mM/h) by the saturated oil fraction (nC17-nC30 alkanes and nC10-nC23-alkyl cyclohexanes as electron donors) were slightly lower than those by bulk oil (22.8 ± 0.4% and 0.05 ± 0.00 mM/h, respectively), but those by the aromatic fraction with two benzene rings were much higher (30.8 ± 0.2% and 0.15 ± 0.00 mM/h, respectively). Fe(III) bio-reduction was coupled with oxidative transformation of oil compounds. Specifically, n-alkanes and alkyl cyclohexanes with shorter carbon chains and aromatic isomers with fewer methyl groups were more easily degraded (i.e., dibenzothiophene series) and/or desorbed (i.e., phenanthrene series) than n-alkanes and alkyl cyclohexanes with longer carbon chains and aromatic isomers with more methyl groups. These hydrocarbons were degraded to oxygen-containing compounds, mainly saturated fatty acids, monocyclic naphthenic acids, and phenols. In the presence of lactate as extra electron donor, the aromatic fraction significantly promoted the Fe(III) bio-reduction extent and rate, suggesting its role as electron shuttle. The oxidative transformation of oil compounds driven by bio-reduction of clay minerals has broad implications for the coupled biogeochemical cycles of carbon and iron in oil reservoirs and organic-rich sedimentary rocks.

Carbon isotopic composition and organic petrography of thermally metamorphosed Antarctic coal: Implications for evaluation of δ13Corg excursions in paleo-atmospheric reconstruction

Large, globally documented negative δ13C excursions that occur across the Permian-Triassic transition are thought to represent the isotopic fingerprint of considerable releases of isotopically light carbon into the atmosphere, with the largest of these excursions (as much as −22.2‰) measured in bulk organic matter in coals and carbonaceous shales from Antarctica. Previous studies have attributed the carbon isotopic excursion (CIE) at the Permian–Triassic boundary to the release of CH4 from organic-rich rocks intruded by dikes and sills associated with the Siberian Traps flood basalts (Russia) and Longwood-Bluff (New Zealand) intrusions. However, any assessment of paleoatmospheric conditions based on this or other δ13Corg excursions must consider the multiple controls on isotopic composition, including maceral content and post-depositional diagenetic and maturation processes. Permian-age coal seams and associated sediments in Antarctica were extensively altered after burial by localized high heat flow and, in some cases, by contact metamorphism associated with Jurassic dikes and sills. Levels of organic maturation reach anthracite, meta-anthracite, and even graphite; such intense thermal alteration had the potential to change the carbon isotopic composition of the bulk organic matter (δ13Corg). To evaluate the Permian–Triassic isotopic excursion in Antarctica, it is important to understand the inherent variability in δ13Corg in Permian-age coal and organic-rich sedimentary rocks prior to the CIE; thus, 128 samples representing pre-boundary coals and shales were selected from the United States Polar Rock Repository for analysis. Petrographic (maceral analysis and vitrinite reflectance), geochemical (C, H, N), and carbon isotopic analyses were performed. Based on the presence of coarse-grained circular and fine-grained lenticular mosaic in the anisotropic cokes found in samples in close proximity to intrusions, the rank of the samples prior to intrusion is estimated to have been medium volatile bituminous (∼1.2% Rmax). These highly altered coals and cokes can have random vitrinite reflectances (Rr) exceeding 6%. Subsequent to intrusion, alteration beyond the contact aureoles continued due to high heat flow, producing high rank coals with Rr > 2%. Values of δ13Corg range between −26.5 and –21.1‰ (5.4‰ difference). Significant relationships (at the 1 and 5% levels) exist between δ13Corg and the level of organic maturity, organic carbon (Corg) content (i.e., size of the carbon reservoir), and total inertinite content, suggesting variability due to these factors should be considered when assessing isotopic excursions and interpretation of Permian-Triassic atmospheric conditions. These findings highlight the importance of incorporating organic petrography into δ13Corg studies.

New U-Pb baddeleyite ID-TIMS ages from the intrusive high-Ti-Sr rocks of the Southern Paraná LIP, Brazil: Implications for correlations with environmental disturbances during the Early Cretaceous

Large volumes of mafic igneous rocks are commonly emplaced during Large Igneous Province (LIP) eruptions, and these mafic rocks are often contemporaneous with periods of environmental disturbances, such as global ocean anoxia, and as a result, mass extinctions. The Paraná-Etendeka LIP is no exception, and has been previously correlated with, and interpreted to be the cause of the Valanginian oceanic anoxic event (OAE), a small global environmental disturbance. Here, we present new U-Pb ID-TIMS baddeleyite ages from high-Ti-Sr mafic intrusive rocks from the Paraná LIP, in Brazil. While these data are potentially complicated by the presence of Pb-loss and inheritance, it is possible to interpret geologically meaningful ages from them. The first high-precision age is reported for the type-locality of the Florianópolis Dyke Swarm, in North Santa Catarina Island, which yields an age of 132.53 ± 0.40/0.40/0.42 Ma. We also report an age of 132.07 ± 0.27/0.30/0.33 Ma for a dolerite sill, which intrudes organic-rich sedimentary rocks of the Paraná Basin. The emplacement of high-Ti-Sr magmas at ca. 132 Ma suggests that there was up to 2 Myr of intrusive magmatism in the southern part of the Paraná LIP. Further investigation on the mafic intrusive magmatism from the Paraná LIP through robust high-precision geochronology is required to elucidate the proposed linkage more clearly with environmental changes during the Early Cretaceous.

Influencing factors and significance of organic and inorganic nitrogen isotopic compositions in lacustrine sedimentary rocks

Comprehensive nitrogen biogeochemical cycle has been reconstructed for representative lacustrine organic-rich sedimentary rock in China, namely the Triassic Yanchang Formation (YF, 199–230 Ma) in Ordos and the Cretaceous Qingshankou Formation (QF, 86–92 Ma) in Songliao basins, by evaluating the organic and inorganic nitrogen isotopic compositions rather than only organic or bulk nitrogen isotopic compositions. The results indicate that the nitrogen isotope values of bulk rock (δ15Nbulk) in the non-metamorphic stage are significantly different from that of kerogen, which challenge the conceptual framework of sedimentary nitrogen isotope interpretation. The δ15Nbulk from the YF and QF were lower than their respective the nitrogen isotope values of kerogen (δ15Nker), with offsets up to ∼5.1‰, which have the inverse relationship for the metamorphosed rock. Thermal evolution did not significantly modify the δ15N of bulk rock and kerogen. The δ15N of sediments from the YF (δ15Nbulk, 1.6‰–5.6‰) were lower than that of rock from the QF (δ15Nbulk, 10.2‰–15.3‰). The nitrogen isotope values of silicate incorporated nitrogen (δ15Nsil) were slightly lower than those of the δ15Nker in the YF and obviously lower for the QF. The fact that different nitrogen cycles occur in the YF and QF due to the different depositional redox conditions leads to different isotopic results. The YF water environment dominated by oxic conditions is not conducive to the occurrence of denitrification and anammox, and no abundant N2 loss leads to the relatively light δ15Nbulk. In the stratified water for the QF, redox transition zone promotes denitrification and anammox, resulting in the heavy δ15Nbulk of rock and promotes the DNRA, resulting in heavy δ15Nker and low δ15Nsil.

Genesis of the Loma Galena Pb-Ag Deposit, Navidad District, Patagonia, Argentina: A Unique Epithermal System Capped by an Anoxic Lake

Abstract Loma Galena (978,852 t Pb, 206 Moz Ag) is one of eight epithermal deposits in the world-class Navidad Pb + Ag ± (Zn, Cu) district located in the Cañadón Asfalto continental foreland basin, northern Patagonia, Argentina. This basin formed during the Jurassic in an extensional tectonic regime during the breakup of Gondwana. Host rocks comprise major listric faulted and tilted blocks of K-rich andesite to dacite lava flows (173.9–170.8 Ma; U-Pb ages for zircon) unconformably overlain by mudstone interbedded with stromatolitic and pisolitic limestones, sandstone, coal, and an Sr-rich evaporite layer deposited in a lacustrine environment. The mineralization occurs as disseminations in the organic-rich sedimentary rocks, in veins and hydrothermal breccia dikes in the hanging walls and footwalls of NW- and NE-striking normal faults, in volcanic autobreccias, and in a phreatic breccia at the contact of volcanic and sedimentary rocks. The earliest hydrothermal minerals consist of veins of colloform, crustiform, and cockade calcite 1 (δ13Cfluid –4.7 to 0.8‰; δ18Ofluid 4.8–11.6‰) and siderite. The precipitating fluids were likely basement-exchanged basinal brines having salinities of 9.5 to 16.4 wt % NaCl equiv and temperatures of 154.7° to 212°C. The interaction of these fluids with the host volcanic rocks formed calcite, albite, adularia, and celadonite-glauconite-group minerals followed by chlorite and siderite as fO2 decreased. Fluids intermittently boiled, as evidenced by bladed (platy) texture in calcite 1. Subsequent mineralizing stages contributed to the metal endowment of Loma Galena. The abundance of organic-rich mudstone and δ34S from –15.4 to 12.9‰ for sulfides suggests that the bottom waters of the lake were anoxic and the loci of microbial sulfate reduction (evaporites have δ34S 35‰). Mixing of upflowing metal-rich basinal fluids carrying some S from depth with this H2S-rich connate water efficiently precipitated Ag-bearing framboidal pyrite, colloform pyrite-marcasite, chalcopyrite, bornite, tennantite-tetrahedrite, sphalerite, and galena as veins, breccias, and disseminations in host rocks. The highest grade and tonnage of the ores are found in autobreccias at the junction of the uppermost lava flow and in the overlying mudstone, where the addition of a strong microbial signature is recorded in sulfides. This event also led to partial dissolution of magmatic and hydrothermal feldspar and calcite 1 in the altered volcanic rocks. Mineralization was followed by hydrothermal brecciation and successive precipitation of chalcedony (δ18Ofluid 2.6–4.8‰), barite (δ34S 15.7–22‰; 160.9°–183.8°C; 7.7–9.7 wt % NaCl equiv), calcite 2 (δ18Ofluid –10.2 to –3.7‰, 58°–95°C; 1.9–7.0 wt % NaCl equiv), strontianite, and quartz in brecciated veins and breccias; kaolinite (δ18Ofluid 2–6.2‰), illite-smectite, smectite, and carbonates with minor chalcedony and barite in the volcanic rocks; and calcite, chalcedony, and barite in the sedimentary rocks. A trend of decreasing salinity with decreasing temperature and lowering δ18O of the fluids with time suggests dilution of the basinal fluids by mixing with Jurassic meteoric water (δ18O −9 to −5.2‰). Loma Galena is a unique example of a polymetallic epithermal system formed in a sublacustrine anoxic environment that promoted the efficient deposition and preservation of Ag-bearing sulfides, thereby contributing to the large size and relatively high grade of the deposit.

Geochemistry of dolerite intrusions of the southeastern Main Karoo Basin, South Africa: Magma evolution, evidence for thermogenic gas sequestration, and potential implications for the early Toarcian Oceanic Anoxic Event

The igneous intrusions of the Karoo Large Igneous Province (LIP) provide critical information on the magma plumbing system, which served as source rock maturation agent for organic-rich sedimentary rocks of the Main Karoo Basin as well as pathway and barrier to subsurface fluid flow. Here, we present results from the research borehole KWV-01 drilled in the Eastern Cape Province of South Africa. The intersected succession, spanning the Dwyka to the lower Beaufort Group, provides representative samples of the Karoo LIP magma plumbing system.Using whole-rock and Sr-Nd isotope analyses, our data suggest that primary melts were derived from a sub-lithospheric mantle source and acquired a subduction signature through interaction with a metasomatised lithospheric mantle. Three magma types identified within this study show a geochemical overlap with previously reported data from the Golden Valley Sill Complex, ca. 220 km to the NW of the analysed borehole. The results of MELTS and EC-RAFC modelling on the three magma types reveal that their compositional differences are related to variable degrees of fractional crystallisation and contamination by lower crustal rocks and/or the sedimentary host rocks of the Main Karoo Basin.Our results indicate that at least one of the sills acted as fractured reservoir, thereby providing evidence that igneous intrusions are important for CO2 sequestration. We quantified the implications of this process for the Karoo LIP-related Toarcian Oceanic Anoxic Event using the thermogenic gas budget produced by state-of-the-art computer simulations and tested various end-member scenarios for partial thermogenic gas sequestration. In agreement with recent studies, we show that all the flat parts of the Karoo sills acted as sequestration reservoirs. Our results have general implications for LIP volcanism in organic-rich basins, suggesting that a good first-order approximation of thermogenic gas emission is half the amount mobilised in the contact aureoles of LIP plumbing systems.

Mercury loss and isotope fractionation during thermal maturation of organic-rich mudrocks

Mercury (Hg) concentration and isotopic composition of organic-rich sedimentary rocks have been widely used as proxies to track ancient volcanism and associated environmental perturbations. However, interpretation of the Hg data is based on the assumption that the thermal maturity of the sedimentary rocks has limited effects on Hg abundance and isotopic composition, which is yet to be evaluated. Here we conduct closed-system anhydrous pyrolysis experiments to investigate the changes of Hg concentration and isotope composition during the thermal mature process, using both marine and lacustrine mudrocks. A siliceous shale section (Luocun, China) with heterogeneous thermal maturity caused by dike intrusion was also analyzed for Hg. Significant Hg loss (over 80%), with variations of δ202Hg (by 0.3 to 0.7‰) but small variations of Δ199Hg (by <0.1 to 0.36‰), were observed during the experiment. The Hg isotopic variation may be caused by the release of isotopically distinct Hg in different mineral phases at different temperatures. Samples from the Luocun section have anomalously low Hg and Hg/TOC values, due to thermal maturity. These findings suggest that (1) thermal maturation of organic-rich shales may be an important factor in distribution of Hg in sediments, and (2) the use of Hg, Hg/TOC and Hg isotopes proxies for paleoclimate and paleoceanography reconstruction should be applied in caution in substrates that may have experienced significant thermal alteration, especially if sill/dike intrusions were present that may cause large varieties of thermal maturity within sedimentary sections.

Diagnostic biosignature transformation under simulated martian radiation in organic-rich sedimentary rocks

As we look for traces of ancient life on Mars, we need to consider the impact of ionizing radiation in the biosignature preservation process. Here, we irradiated two organic rich terrestrial samples (Enspel and Messel shales) that have Martian analog mineralogies, with simulated cosmic rays to a dose of 0.9 MGy, equivalent of 15 million years of radiation exposure on the Martian surface. We compared a range of biosignatures before and after exposure, including total organic carbon, bulk stable carbon isotope ratios, diagnostic lipid biomarkers (hopanes and steranes), and Raman signatures akin to those collected by the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument on Perseverance. While we did not observe a significant difference in total organic carbon, bulk stable carbon isotopes, or Raman G-band signatures, we found that five lipid biomarkers decreased by a factor of two to three in the Enspel shale. This degree of degradation exceeds current predictions by existing models or experimental studies in organic rich samples and challenges our current understanding of complex biosignatures under ionizing irradiation.

Optimization of two-dimensional T1*–T2* relaxation correlation measurements in shale

Shale reservoirs, composed of fine-grained and organic-rich sedimentary rock, are common unconventional oil and gas reservoirs. Magnetic resonance (MR) relaxometry, a non-destructive and non-invasive method, is a key technique for shale evaluation. The T1*–T2* relaxation correlation, a rapid two-dimensional MR measurement, is a newly emerging and powerful tool to study the structure of materials with short transverse relaxation times. T1* and T2* are the effective longitudinal and transverse relaxation times. T1*–T2* measurement is a promising laboratory method to analyze fluid and organic matter components in shale, but it is very sensitive to the acquisition parameters. In this paper, the effects of acquisition parameters, including flip angle α, initial interval τ1, α pulse interval τ, and scan number, on T1*–T2* relaxation correlation of shale were analyzed by numerical simulations and core plug experiments. The optimized T1*–T2* measurement can be two orders of magnitude faster than a simple T1–T2* measurement. This work provides a theoretical and practical guide for undertaking T1*–T2* measurements, which should be helpful for further laboratory study of shale.

Biomarkers and PAH chemostratigraphy in the study of the Frasnian anoxic event in the Pimenteiras Formation outcrop of the Parnaíba Basin, Brazil

The Late Devonian is characterized by episodes of sea-level rise and expansion of dysoxic to anoxic paleoenvironments, resulting in a global abundance of organic-rich sedimentary rocks. These changes have been well documented in biostratigraphic studies of Euroamerica basins. However, the relationship between sea-level rise and marine anoxia in Western Gondwana sedimentary rocks is not completely understood. Here, biomarker and PAH diagnostic ratios were applied to investigate changing depositional paleoenvironment and organic matter inputs of the Pimenteiras Formation along the western edge of the Parnaíba Basin. First, 24 shale samples collected from 16 regionally distributed outcrops were analysed, revealing variability in depositional paleoenvironment conditions. Secondly, for detailed study a 15-m thick outcrop was chosen, from which 11 shale samples were collected. These samples were submitted to chemostratigraphic and palynostratigraphic analyses and their records were highlighted. Two sample groups were identified, one sample group containing mixed organic matter, predominantly terrigenous and with fresh-brackish water organisms, deposited under dysoxic conditions. The other sample group comprised mixed organic matter containing a high contribution of marine organisms, preserved under anoxic conditions. Results indicated a marine flooding surface in the Pimenteiras Formation Outcrop 1, associated with a Devonian transgressive event related to sea-level rise and probably to global anoxic conditions during the Frasnian in the Parnaíba Basin. In addition, it was possible to correlate the abundance of miospores Verrucosisporites genus with high Retene/Chrysene values, suggesting that these miospores can be associated with a biological precursor of retene.

Re-Os systematics and chronology of graphite

Natural graphite forms in a range of metamorphic and hydrothermal environments across timelines spanning from the birth of the solar system, to the evolution of early Precambrian life, and the development of contemporary geotectonic cycles. A precise timeline of these and other graphite-forming events, however, has hitherto been obscured by a lack of radiometric ages and as such, chronologies are inferred from host-rock or hydrothermal mineral ages. Herein we examine the Re-Os systematics and chronology of graphite formed in a suite of terrestrial and extraterrestrial environments (n = 17) with the principal aim of establishing the viability of Re-Os geochronology of natural graphite.Graphite Re and Os contents and isotopic ratios exhibit a wide range of values that extend up to 1520 ppb Re, 19,577 ppt Os, and 4101 and 42.18 for 187Re/188Os and 187Os/188Os ratios, respectively. These values are broadly comparable to those reported for crustal sulfides, organic-rich sedimentary rocks, and hydrocarbons. X-ray diffraction crystallinity data reveals that graphite Re abundances show a broadly inverse correlation with graphite formation temperature and crystallinity (d002 and Lc(002)) with interplanar spacing (d002) having the strongest anti-correlation with graphite Re contents.Graphite Re-Os geochronology is demonstrated with two independent case studies (Wollaston-Mudjatik Transition shear zones, Saskatchewan, Canada and Merelani Hills, Tanzania) yielding precise (<1%) Re-Os isochron dates of 1731.52 ± 7.43 Ma (2σ; MSWD = 1.3) and 586.89 ± 2.39 Ma (2σ; MSWD = 1.2) that are consistent, within uncertainty, to their mineralization ages constrained by other radiometric methods. These data confirm that graphite mineralization was synchronous with Trans-Hudsonian exhumation and tsavorite-tanzanite gemstone mineralization, respectively. Method accuracy, however, appears contingent on the analytical protocols used to isolate graphite, e.g. handpicking vs. heavy liquids (SPT) and water, with the latter perturbing graphite Re-Os systematics by as much as 20%. We, therefore, recommend handpicking paired with magnetic separation and grain mount examination.Our Re-Os age results are then coupled with new SIMS carbon isotope data (Wollaston-Mudjatik Transition graphite: δ13C = −21.64 to −15.28‰; Merelani Hills graphite: δ13C = −25.90 to −24.36‰) and 187Os/188Osi isotope data (Wollaston-Mudjatik Transition graphite = 0.3119 ± 0.0037; Merelani Hills graphite = 1.680 ± 0.038) to constrain graphitic carbon to sedimentary carbonate/organic (Wollaston-Mudjatik Transition graphite) and organic (Merelani Hills graphite) carbon sources. This unique pairing of isotope systems in graphite provides the first detailed chronology of localized carbon mobility in the Earth’s crust.Re-Os graphite geochronology likely has wide applications in ore-deposit and metamorphic geology with the potential to reshape our understanding of carbon cycling in the crust-mantle system, and for graphite exploration initiatives that are critical for a global transition to a green economy.

High temperature generation and equilibration of methane in terrestrial geothermal systems: Evidence from clumped isotopologues

Fluids emanating from geothermal areas contain trace quantities of methane and other simple hydrocarbons. These hydrocarbons are thought to derive from thermal cracking of organic matter dissolved in circulating meteoric or seawater or found in pre-existing organic-rich sedimentary rocks, but an abiotic origin has also been proposed. We measured the relative abundances of four CH4 isotopologues (12CH4, 13CH4, 12CH3D, and 13CH3D) in hydrothermal gases discharged by steam vents and geothermal wells from Iceland and Nisyros island (Greece) in order to investigate the origin of methane. Measured methane samples yielded consistently low Δ13CH3D values (13CH3D abundance relative to stochastic) of 0.82–1.77‰, which correspond to high apparent temperatures of isotopologue equilibrium (TΔ13CH3D = 278–490 °C). Hydrothermal well fluids from the Krafla and Námafjall geothermal fields in Iceland yielded the lowest Δ13CH3D values, and thus the highest Δ13CH3D-based temperatures averaging 438-45+55 °C. Those samples also show the most pronounced departures in δDCH4 and δ13CCH4 values expected for isotopic equilibrium with respect to δDH2O and δ13CCO2. In contrast, CH4 samples from natural steam vents in other Iceland locations and in Nisyros have slightly higher Δ13CH3D values (with TΔ13CH3D=351-35+42 °C) and have δDCH4 and δ13CCH4 values that are consistent with those expected for isotopic equilibrium with both H2O and CO2. The short fluid residence times (1–50 years) in systems that are exploited for geothermal energy, such as Krafla and Námafjall, combined with the proximity of a hot magma chamber, favor the preservation of kinetic signals. The initial disequilibrium δDCH4 and δ13CCH4 values are consistent with a thermogenic origin from immature organics dissolved in hydrothermally heated groundwater, but an abiotic origin cannot be excluded. The high apparent Δ13CH3D-based temperatures at Krafla and Námafjall could therefore represent nonequilibrium signals associated with either pyrolysis or abiotic generation of CH4 in a superheated vapor or supercritical water phase (>374 °C), considered to exist in the roots of the system above the magmatic heat source. Isotopologue equilibration calculations demonstrate that under such conditions (e.g. > 400 °C) kinetic signals would be erased in days to months, implying rapid migration and quenching of CH4 into the overlying subcritical (<300 °C) hydrothermal reservoir fluids. In systems with longer fluid residence times such as Nisyros, equilibrium isotopologue distributions at temperatures of ~ 350 °C are consistent with long fluid residence times on the order of > 100 years. Our calculations further reveal that CO2–CH4 isotopic equilibration requires unreasonably long fluid residence times, suggesting that any apparent 13C equilibrium may be coincidental.

Hydrothermal recycling of sedimentary ammonium into oceanic crust and the Archean ocean at 3.24 Ga

Abstract The Archean ocean supported a diverse microbial ecosystem, yet studies suggest that seawater was largely depleted in many essential nutrients, including fixed nitrogen. This depletion was in part a consequence of inefficient nutrient recycling under anoxic conditions. Here, we show how hydrothermal fluids acted as a recycling mechanism for ammonium (NH4+) in the Archean ocean. We present elemental and stable isotope data for carbon, nitrogen, and sulfur from shales and hydrothermally altered volcanic rocks from the 3.24 Ga Panorama district in Western Australia. This suite documents the transfer of NH4+ from organic-rich sedimentary rocks into underlying sericitized dacite, similar to what is seen in hydrothermal systems today. On modern Earth, hydrothermal fluids that circulate through sediment packages are enriched in NH4+ to millimolar concentrations because they efficiently recycle organic-bound N. Our data show that a similar hydrothermal recycling process dates back to at least 3.24 Ga, and it may have resulted in localized centers of enhanced biological productivity around hydrothermal vents. Last, our data provide evidence that altered oceanic crust at 3.24 Ga was enriched in nitrogen, and, when subducted, it satisfies the elemental and isotopic source requirements for a low-N, but 15N-enriched, deep mantle nitrogen reservoir as sampled by mantle plumes.