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Metaproteomics and metagenomics reveal microbial pathways of organic matter degradation and methanogenesis in a marginally producing natural gas well

The expansion of natural gas production and utilization worldwide has led to the decline of many once-productive wells, eventually resulting in costly well-plugging and unused infrastructure. However, in areas like the Michigan basin, MI, where the majority of natural gas is biogenically produced, microbial communities could potentially be stimulated to generate additional methane, increasing gas supply and reducing the need to drill new wells. In this study, we performed metaproteomic, metagenomic, and geochemical analyses of Antrim Shale formation water from a marginally producing natural gas well to evaluate resident microbial community functions in the context of potential bioenergy production. Functional proteins involved in methanogenesis, degradation/catabolism (including organic matter degradation), biosynthesis, energy utilization, transmembrane transport, and stress response were among the most commonly identified groups. Three metagenome-assembled genomes (MAGs) were characterized, including Methanomicrobiaceae, Methanothrix , and Smithella . For each, the identified proteins involved in methanogenesis and the degradation of diverse organic compounds, strongly suggest their role in utilizing shale-derived organic matter. These findings provide an increased understanding of the microorganisms and their metabolisms generating natural gas in the Antrim Shale and establish a foundation for future stimulation efforts aimed at enhancing biogenic methane production in marginal gas wells.

Michigan

Deep subsurface organic-rich shale supports abundant, diverse, and novel fungi

As Earth’s principal reservoir of organic carbon and microbial biomass, the deep subsurface hosts microorganisms capable of mobilizing this once-sequestered carbon. Contrary to standard assumptions of eukaryotic scarcity, this study documents abundant fungal communities, ranging from 4.2 × 10 3 to 6.8 × 10 3 fungal cells mL −1 , across a methane-producing organic-rich shale 247–556 meters below the surface. Although fungal:bacterial cell ratios ranged from 1:7028 to 1:713, application of biomass conversion factors developed for oceanic systems yielded a median fungal:bacterial biomass ratio of 1:4.7. 16S rRNA gene amplicons revealed bacterial and archaeal communities mirroring those found in well-characterized extremophilic, carbon-degrading environments, while sequencing of 18S rRNA gene and ITS rRNA spacer amplicons collectively identified a eukaryotic hotspot with 689 fungal OTUs across six phyla. The dominant fungal classes, Agaricomycetes and Dothideomycetes, are well-established degraders of recalcitrant carbon compounds at the surface, suggesting they may similarly contribute to organic matter degradation and ecosystem maintenance in the subsurface. Cultivation and isolation efforts yielded 205 fungal strains, including 13 candidate novel taxa, underscoring the deep subsurface as an underexplored eukaryotic habitat. Stable carbon isotopes indicate methane is predominantly generated via microbial conversion of the fossil carbon, while water isotopes suggest in situ geochemical conditions have been relatively stable since the Late Pleistocene, with subglacial recharge as a plausible mechanism for microbial introduction. Collectively, these findings suggest that fungi are underrecognized contributors to organic matter transformation and functional diversity in the deep biosphere, revealing a critical gap in our understanding of deep subsurface ecosystem processes.

Indiana, Michigan, Ohio

The δ13C signature of dissolved organic and inorganic carbon reveals complex carbon transformations within a salt marsh

Coastal wetlands have high rates of atmospheric CO 2 uptake, which is subsequently respired back to the atmosphere, stored as organic matter within flooded, anoxic soils, or exported to the coastal ocean. Transformation of fixed carbon occurs through a variety of subsurface aerobic and anaerobic microbial processes, and results in a large inventory of dissolved carbon. Carbon source and the roles of aerobic respiration, sulfate reduction, and methane cycling were evaluated within salt marsh peat and the underlying sandy subterranean estuary. There is a large increase in dissolved inorganic carbon (DIC, 7,350 ± 3,900 μmol L −1 ), dissolved organic carbon (DOC, 1,040 ± 1,480 μmol L −1 ) and CH 4 (14.5 ± 33.3 μmol L −1 ) within the marsh porewaters compared to creek waters. Alkalinity production (5,730 ± 2,170 μeq L −1 ) and sulfate removal (1,810 ± 1,970 μmol L −1 ) indicate anaerobic respiration, however, relative contributions from the various decomposition pathways cannot be identified due to overlapping geochemical signatures. The δ 13 C of the DOC (−29.0 ± 3.7‰) and DIC (−11.2 ± 1.1‰) produced within the marsh differed from the bulk soil organic matter δ 13 C (−14.5 ± 0.2‰). We explore a variety of mechanisms that could result in co-occurring depleted δ 13 C-DOC and enriched δ 13 C-DIC compared to the bulk soil organic carbon pool and salt marsh vegetation, including selective mineralization, production of δ 13 C-depleted bacterial biomass, and methane-derived DOC. While important questions remain about carbon cycling pathways, we found evidence of a cryptic methane cycle. Alteration of the δ 13 C of carbon species complicates source attribution in solid and dissolved phases and careful consideration should be used when carbon is partitioned between in situ salt marsh production and external marine and terrestrial sources.

Massachusetts

Diverging mineral chemistry of iron and nickel throughout Earth’s changing redox conditions reveals foundation for their evolution as protein cofactors

Iron (Fe) and nickel (Ni) were both foundational to early metabolism, yet their biological trajectories diverged as Earth’s surface redox state changed. Here, we integrate mineral chemistry network analysis, protein metal-site coordination-sphere analysis, and curated redox comparisons to test how geochemistry and metalloprotein architecture co-evolved. Mineral network analyses show broader electronegativity variation and network diversity for Fe-bearing minerals through time relative to Ni-bearing minerals. In structural analyses of protein metal centers in a combined Fe/Ni protein structure set, it is shown that Fe- and Ni-associated environments differ in amino-acid composition, hydropathy structure, and cysteine representation. The greater chemical diversity and electronegativity variation in Fe minerals mirror the higher redox and structural versatility of Fe-binding proteins. The presence of Fe in a broader range of mineral and protein environments demonstrates the chemical adaptability of the metal, from the anoxic Archean to oxidative Earth surface conditions following the Great Oxidation Event. Iron, with its broad redox potential range in Fe-oxidoreductases, has a central role in both anaerobic and aerobic metabolisms. Nickel, by contrast, is less widespread in biology. Today, Ni is predominantly employed in deeply branching anaerobic pathways and by proteins with narrower redox potential ranges. Our results show that evolutionary processes, constrained by metal chemistry, habitually utilize Fe as a redox generalist while retaining Ni in specialized roles. The divergent paths of Ni and Fe, from rocks to proteins, demonstrate the intimate relationship between planetary geochemistry and metabolic origins on Earth and suggest that Fe/Ni geochemistry may inform habitability assessments in extraterrestrial environments when interpreted within specific planetary environmental contexts.

Life

Emerging investigator series: Post-wildfire sediment geochemical characterization reveals manganese reactivity and a potential link to water quality impairment in the Gallinas Creek watershed, New Mexico

Water quality post-wildfire is often impaired by increased turbidity and elevated concentrations of elements such as manganese (Mn) and iron (Fe). Precipitation events exacerbate these issues, due in part to increased erosion and transport of sediment from hillslopes to surface water. Both Mn and Fe are major redox-active elements in sediments that drive a variety of biogeochemical cycles, precipitate adsorptive phases, and can themselves be drinking water contaminants. By investigating Mn and Fe sediment geochemistry in post-wildfire sediment deposits, related water quality hazards can be assessed. To establish and strengthen this connection, we analyzed the geochemistry of sediment deposits and surface water in the Gallinas Creek watershed, New Mexico over 1.5 years post-wildfire. Analyses included particle size analysis, water extractions, sequential extractions and aqua regia extractions to determine metal partitioning in sediment deposits. Data demonstrate Mn concentrations were distributed across labile and reactive fractions, such as the exchangeable and oxyhydroxide fractions, while Fe concentrations were mainly associated with the residual fraction. Manganese concentrations in aqua regia extractions and several fractions of sequential extractions were also strongly and significantly correlated with fine-grained sediment while the same pools of Fe concentrations were not. Dissolved Mn concentrations in surface water were elevated (>50 μg L −1 ) multiple times over the 1.5 years post-wildfire, highlighting a relationship between sediment geochemistry and water quality. This work shows Mn in sediments mobilized post-wildfire has an influence on water quality and highlights how further investigation into Mn sediment redox processes and mineralogy post-wildfire can inform risk assessments and resource management.

New Mexico

Season and antecedent conditions impact concentration-discharge relationships for dissolved organic carbon and alkalinity in southeast Alaskan watershed

Fluvial export of dissolved carbon plays an important role in watershed-scale biogeochemistry. Predicted changes in climate are expected to impact watershed hydrologic regimes, and in turn, the sources and export of dissolved carbon from watersheds. Here, we utilize high resolution measurements of discharge and dissolved carbon concentration to examine how concentration-discharge (CQ) relationships vary seasonally and during high flow events over the main runoff season (May–October) in a temperate forested watershed in Southeast Alaska. Concentration-discharge relationships for dissolved organic carbon (DOC) and alkalinity demonstrated strong seasonal patterns, with more linear relationships in May and June versus other months. Changing power law model slopes ( b values; the exponent in a power law regression between runoff and carbon yields) indicated potentially shifting watershed sources (biogenic vs. geologic) and contrasting dominant flowpaths (shallow vs. deeper groundwater) for DOC and alkalinity over the sampling period. During the largest storm event of the study, DOC and alkalinity b values shifted from an overall pattern of transport (mean b = 1.58 values >1.0 indicate transport limitation) and source limitation (mean b = 0.48, values <1.0 indicate source limitation) to chemostatic (DOC, b = 0.99; alkalinity, b = 1.019). In June through August, patterns in hysteresis index suggest that CQ relationships were altered when storms followed in close succession to each other. Together, these findings indicate that seasonal and antecedent flow conditions play a role in dissolved carbon export from forested watersheds. Understanding these dynamics, particularly during winter months, will become increasingly important as changes to hydroclimate impact riverine carbon export.

Alaska

Evidence for organic and igneous carbon sources in the Mesoproterozoic Adirondack Highlands graphite district, New York

This study examined the origin of graphite mineralization in the Mesoproterozoic Adirondack Highlands. Flake graphite was mined from the historic mining district around Ticonderoga, New York, USA, from the 1850s to the 1920s. Most of the production and reserves from the district are disseminated graphite from feldspathic quartz schists (e.g., Dixon-American Graphite Co. mine, Faxon property, Flake Graphite Company). Protolith sediments of the schists were deposited in the Trans-Adirondack backarc basin at ca. 1.25 Ga and were metamorphosed to high grade at 1.18–1.15 Ga during the accretionary Shawinigan orogeny and at 1.09–1.02 Ga during the Ottawan phase of the Grenvillian orogeny. Major elements and carbon isotopes of graphite from schists (δ 13 C = −28.1‰ to −5.4‰ relative to Vienna Peedee belemnite) are consistent with derivation from organic carbon in protolith sandstones that devolatilized during metamorphism. Some small mines and prospects in the district mined graphitic calcite marbles and clinopyroxene ± scapolite skarns associated with a pegmatite suite dated by U-Pb in zircon to 1.04–1.01 Ga (e.g., Lead Hill and Crown Point deposits), and rare graphite veins are observed at several deposits. Hydrothermal flake graphite from pegmatites, skarns, and veins are distinct from graphite in schist-hosted deposits and have δ 13 C values that cluster around −7‰ to −5‰, consistent with deposition from igneous CO 2 . Covariation of carbon and oxygen stable isotopes and U-Pb zircon geochronology are not compatible with precipitation from fluids derived from country rock metapelites or marbles. Some graphite districts elsewhere show compelling evidence for remobilization and redeposition of sedimentary-derived carbon as hydrothermal graphite, sometimes as thick veins producing world-class, high-grade deposits. In the Adirondacks, there is evidence for two generations of graphite mineralization with distinct carbon sources: syngenetic graphite with an organic origin in Shawinigan quartz schists and epigenetic graphite with an igneous origin in Ottawan skarns and pegmatites.

New York

Perchlorate, metals, organic compounds, and lead isotopes in groundwater, surface water, shallow groundwater, and soil within and near the Middleton Municipal Airport–Morey Field (C29), Middleton, Wisconsin, 2022

The Middleton Municipal Airport–Morey Field (C29) is in the City of Middleton and adjacent to the towns of Middleton and Springfield, Wisconsin. Nearby homes in the towns rely on private drinking water wells, and residents are concerned about the potential contamination of groundwater and surface water by airport activities, including flights by small aircraft that use leaded aviation fuel and a fireworks display in July 2021. The U.S. Geological Survey, in cooperation with the Town of Middleton, completed a study in 2022 to characterize the occurrence and sources of perchlorate, metals (including lead), and organic compounds in samples of groundwater, surface water, shallow groundwater, and soils within and near the airport. Lead isotopes were also measured to determine sources of lead by comparing samples to environmental references. Magnitudes of concentrations from samples of water and soil collected in 2022, and their spatial patterns across site locations, indicate the fireworks display in July 2021 was a likely source of perchlorate and metals in the airport study area. The highest perchlorate concentration was measured in surface water at the southeastern corner of the airport near the fireworks launch site; the highest concentrations of fireworks-associated metals were measured in shallow groundwater near the same location. Fireworks were not the only possible source of perchlorate and metals in the airport study area because both were also detected upgradient and away from the fireworks launch site. Ratios of lead isotopes indicate that lead measured in water and soil within the airport study area was primarily sourced from background atmospheric lead deposition or Wisconsin galena lead ore. However, two groundwater samples (one upgradient and one downgradient from the airport; both with concentrations less than 1 microgram per liter) had isotopic signatures matching leaded aviation fuel sold at the airport.

Wisconsin

Water-quality assessment of the Ozark Plateaus study unit, Arkansas, Kansas, Missouri, and Oklahoma — Nutrients, bacteria, organic carbon, and suspended sediment in surface water, 1993-95

Nutrient, bacteria, organic carbon, and suspended- sediment samples were collected from 1993-95 at 43 surface-water-quality sampling sites within the Ozark Plateaus National Water- Quality Assessment Program study unit. Most surface-water-quality sites have small or medium drainage basins, near-homogenous land uses (primarily agricultural or forest), and are located predominantly in the Springfield and Salem Plateaus. The water-quality data were analyzed using selected descriptive and statistical methods to determine factors affecting occurrence in streams in the study unit. Nitrogen and phosphorus fertilizer use increased in the Ozark Plateaus study unit for the period 1965-85, but the application rates are well below the national median. Fertilizer use differed substantially among the major river basins and physiographic areas in the study unit. Livestock and poultry waste is a major source of nutrient loading in parts of the study unit. The quantity of nitrogen and phosphorus from livestock and poultry wastes differed substantially among the river basins of the study unit's sampling network. Eighty six municipal sewage-treatment plants in the study unit have effluents of 0.5 million gallons per day or more (for the years 1985-91). Statistically significant differences existed in surface-water quality that can be attributed to land use, physiography, and drainage basin size. Dissolved nitrite plus nitrate, total phosphorus, fecal coliform bacteria, and dissolved organic carbon concentrations generally were larger at sites associated with agricultural basins than at sites associated with forested basins. A large difference in dissolved nitrite plus nitrate concentrations occurred between streams draining basins with agricultural land use in the Springfield and Salem Plateaus. Streams draining both small and medium agricultural basins in the Springfield Plateau had much larger concentrations than their counterparts in the Salem Plateau. Drainage basin size was not a significant factor in affecting total phosphorus, fecal coliform bacteria, or dissolved organic carbon concentrations. Suspended-sediment concentrations generally were small and indicative of the clear water in streams in the Ozark Plateaus. A comparison of the dissolved nitrite plus nitrate, total phosphorus, and fecal coliform data collected at the fixed and synoptic sites indicates that generally the data for streams draining basins of similar physiography, land-use setting, and drainage basin size group together. Many of the variations are most likely the result of differences in percent agricultural land use between the sites being compared or are discharge related. The relation of dissolved nitrite plus nitrate, total phosphorus, and fecal coliform concentration to percent agricultural land use has a strong positive 2 Water-Quality Assessment-Nutrients, Bacteria, Organic Carbon, and Suspended Sediment in Surface Water, 1993-95 correlation, with percent agricultural land use accounting for between 42 and 60 percent of the variation in the observed concentrations.

Arkansas, Kansas, Missouri, Oklahoma

Water-quality assessment of south-central Texas — Descriptions and comparisons of nutrients, pesticides, and volatile organic compounds at three intensive fixed sites, 1996-98

Water-quality samples were collected during April 1996-April 1998 at three intensive fixed sites in the San Antonio region of the South-Central Texas study unit as part of the U.S. Geological Survey National Water-Quality Assessment Program. The sampling strategy for the intensive fixed-site assessment is centered on obtaining information about the occurrence and seasonal patterns of selected constituents including nutrients, pesticides, and volatile organic compounds. The three sites selected to determine the effects of agriculture and urbanization on surface-water quality in the study unit are Medina River at LaCoste (agriculture indicator site), Salado Creek (lower station) at San Antonio (urban indicator site), and San Antonio River near Elmendorf (integrator site). Concentrations of two nutrients, dissolved nitrite plus nitrate nitrogen and total phosphorus, were largest at the integrator site, which is downstream of municipal wastewater treatment plants. Nitrite plus nitrate nitrogen concentrations at this site often exceeded the U.S. Environmental Protection Agency (EPA) maximum contaminant level (MCL) for drinking water. All total phosphorus concentrations at the site exceeded the EPA recommended maximum concentration for streams not discharging directly into reservoirs. Nitrite plus nitrate nitrogen concentrations at the integrator site tended to be smaller, and total phosphorus concentrations at the urban site tended to be larger in samples collected during stormflow than during base flow. The most detections and largest concentrations of three pesticides (atrazine, diazinon, and prometon) were in samples collected at the urban site. Some pesticide concentrations at the agriculture site showed a seasonal pattern of increasing concentrations during spring, the peak application season. Four pesticides (atrazine, deethylatrazine, diazinon, and prometon) were detected in at least 38 percent of samples collected at all three sites. The concentrations of all detected pesticides that have an MCL were less than the MCL at the three sites. More volatile organic compounds (VOC) were detected at the urban indicator site than at the agriculture indicator site, mostly likely because more sources are located in urbanized areas. The most VOCs detected and the largest concentrations of two VOCs (chloroform and tetrahydrofuran) were in samples from the integrator site. More VOCs were detected in samples collected at the integrator site during stormflow than during base flow. The concentrations of all detected VOCs that have an MCL were less than the MCL at the three sites.

Texas

Concentrations and distribution of manmade organic compounds in the Lake Tahoe Basin, Nevada and California, 1997-99

The U.S. Geological Survey, in cooperation with the Tahoe Regional Planning Agency and the Lahontan Regional Water-Quality Control Board, sampled Lake Tahoe, major tributary streams to Lake Tahoe, and several other lakes in the Lake Tahoe Basin for manmade organic compounds during 1997-99. Gasoline components were found in all samples collected from Lake Tahoe during the summer boating season. Methyl tert -butyl ether (MTBE), benzene, toluene, ethylbenzene, and xylenes (BTEX) were the commonly detected compounds in these samples. Most samples from tributary streams and lakes with no motorized boating had no detectable concentrations of gasoline components. Motorized boating activity appears to be directly linked in space and time to the occurrence of these gasoline components. Other sources of gasoline components to Lake Tahoe, such as the atmosphere, surface runoff, and subsurface flow, are minor compared to the input by motorized boating. Water sampled from Lake Tahoe during mid-winter, when motorized boating activity is low, had no MTBE and only one sample had any detectable BTEX compounds. Soluble pesticides rarely were detected in water samples from the Lake Tahoe Basin. The only detectable concentrations of these compounds were in samples from Blackwood and Taylor Creeks collected during spring runoff. Concentrations found in these samples were low, in the 1 to 4 nanograms per liter range. Organochlorine compounds were detected in samples collected from semipermeable membrane devices (SPMD's) collected from Lake Tahoe, tributary streams, and Upper Angora Lake. In Lake Tahoe, SPMD samples collected offshore from urbanized areas contained the largest number and highest concentrations of organochlorine compounds. The most commonly detected organochlorine compounds were cis- and trans-chlordane, p , p' -DDE, and hexachlorobenzene. In tributary streams, SPMD samples collected during spring runoff generally had higher combined concentrations of organochlorine compounds than those collected during baseflow conditions. Upper Angora Lake had the fewest number of organochlorine compounds detected of all lake samples. Dioxins and furans were not detected in SPMD samples from two sites in Lake Tahoe or from two tributary streams. The number of polycyclic aromatic hydrocarbon (PAH) compounds and their combined concentrations generally were higher in samples from Lake Tahoe than those from tributary streams. Areas of high-motorized boating activity at Lake Tahoe had the largest number and highest concentrations of PAH's. PAH compounds were detected in samples from SPMD's in four of six tributary streams during spring runoff, all tributary streams during baseflow conditions, and at all lake sites. The most commonly detected PAH's in tributary streams during spring runoff were phenanthrene, fluoranthene, pyrene, and chrysene, and during baseflow conditions were phenanthrene, 1-methylphenanthrene, diethylnaphthalene, and pyrene. Upper Truckee River, which has an urban area in its drainage basin, had the largest number and highest combined concentration of PAH's of all stream samples. Bottom-sediment from Lake Tahoe had detectable concentrations of p-cresol, a phenol, in all but one sample. A sample collected near Chambers Lodge contained phenol at an estimated concentration of 4 micrograms per kilogram (µg/kg). Bottom-sediment samples from tributary streams had no detectable concentrations of organochlorine or PAH compounds. Several compounds were detected in bottom sediment from Upper Angora Lake at high concentrations. These compounds and their concentrations were p , p' -DDD (10 µg/kg), p , p' -DDE (7.4 µg/kg), 2,6-dimethylnaphthalene (estimated at 190 µg/kg), pentachlorophenol (3,000 µg/kg), and p-cresol (4,400 µg/kg).

California, Nevada

Sedimentological and geochemical characterization of lacustrine deposits of the Babouri-Figuil basin, northern Cameroon: Implications for source rocks distribution and petroleum exploration

The West and Central African Rift System (WCARS) refers to the series of Cretaceous rift basins where commercial hydrocarbon accumulations have been discovered. Some of the WCARS frontier basins are currently being investigated to increase our understanding of these basins in light of new commercial discoveries. The present study was performed in the Babouri-Figuil Basin (BFB), which is genetically related to the WCARS and constitutes an area of interest in terms of petroleum prospecting, where the distribution of petroleum source rocks and potential targets for petroleum exploration across the entire basin is poorly understood. For the current study, an integrated facies analysis along with organic and inorganic geochemical techniques were applied to the basin's Cretaceous deposits with the aim of reconstructing the paleodepositional environment, assessing factors that triggered the input of organic matter, and providing a spatial overview of the organic matter accumulation in the basin based on outcrop samples. An alluvial fan-lacustrine-braided river system is inferred from the facies analysis of the stratigraphic sequence consisting of conglomerate, sandstone, siltstone, limestone, marlstone, and claystone. Bulk analysis of organic matter reveals that black shale and massive claystone are the main prospective petroleum source rocks in the basin. Inorganic geochemical analyses reveal the influence of anoxic conditions, moderate to high primary productivity, and low terrigenous inputs in organic matter enrichment. The formations rich in organic matter are predominantly concentrated in the western and eastern parts of the basin which may represent areas with depressions, characterized by high accommodation space. In terms of the regional context of the WCARS rift basins, typical hydrocarbon exploration in the BFB may target basal-conglomerate, sandstone beds situated directly above or/and interbedded with the Lower Cretaceous source rocks, and the Upper Cretaceous sandstone beds. Basement rocks (granite, granodiorite, and gneisses) and oil shale deposits may represent potential unconventional hydrocarbon exploration. The current integrated study provides an insight that should guide future hydrocarbon exploration campaigns in the basin.

Babouri-Figuil basin

Natural attenuation of chlorinated volatile organic compounds in ground water at Area 6, Naval Air Station Whidbey Island, Washington

Natural attenuation is a viable alternative to pump and treat for meeting remediation objectives in the vicinity of the southern contaminant plume. The combination of historically low contaminant concentrations in ground water, a landfill cap that limits source area contributions, favorable conditions for degradation of VC, and a relatively long downgradient distance to potential receptors are all favorable for natural attenuation as a remediation alternative. Natural attenuation could effectively meet all but one remediation goal that extraction wells PW- 2, PW-4, PW-6, PW-7, PW-8 and PW-9 are currently being employed to meet. The goal of preventing migration of all VC across the site boundary could not be met by natural attenuation. Some VC would migrate south of the Navy boundary, but the potential for subsequent VC mineralization downgradient of the base and the existing institutional controls would result in minimal additional risk from using natural attenuation. In the western contaminant plume natural attenuation is not currently a viable alternative to pump and treat for meeting remediation objectives. There is a possibility that rates for reductive dechlorination of TCE and TCA could increase substantially if the plume was allowed to migrate beneath the Oak Harbor landfill, but there are not enough data to be certain of such an increase. TCA and TCE concentrations at the leading edge of the western plume need to be reduced to at least 25 and 40 µg/L, respectively, to be protective of potential downgradient receptors. Source area TCA and TCE concentrations have decreased substantially over the past ten years, and the extraction wells PW-3 and PW-5 in particular are removing a significant mass of contaminants from ground water, so natural attenuation may be a viable alternative for the western plume in the future. There would be some possible side benefits of using natural attenuation as an alternative to pump and treat in the southern contaminant plume. The first would be that the resulting decrease in the amount of treated water that would need to be recharged in the swale north of the landfill would result in less off-base migration of contamination across the western site boundary. The second benefit would be a substantial reduction in the amount of dissolved iron and manganese being extracted from the shallow aquifer and run through the treatment system. Removing that source of operation and maintenance problems would result in more effective containment and removal of contamination in the western contaminant plume. The most critical data gap identified in this evaluation is the paucity of contaminant chemistry information downgradient of the Navy boundary in the vicinity of the southern contaminant plume. Without such data, the behavior of the plume and the protectiveness of natural attenuation to downgradient receptors cannot be verified, and field attenuation rates for VC cannot be determined directly. The existing long-term monitoring plan would need to be reviewed and revised if natural attenuation is selected as a remedy for the contamination in the southern plume. In particular, additional performance monitoring wells may be required downgradient of the property.

Washington

Petrogenesis and mineralization potential of spinifex komatiitic basalts in the Bradley Peak greenstone terrane, Wyoming Province

Komatiitic volcanic rocks are important hosts of Ni sulfide mineralization and record early Earth evolution; however, those in the well-studied Archean Wyoming Province have received little attention. Here, we elucidate the timing and petrogenesis of the Bradley Peak komatiitic volcanic rocks using field and textural observations, geochronology, and geochemistry. Detrital and igneous zircon U-Pb ages for two samples from previously undated units support published age determinations, placing the eruption age at 2.72 Ga. Stratigraphy of the volcanic flows was mapped and 36 samples including cumulates, greenschists, and spinifex-textured rocks were collected. Whole-rock geochemistry was used to classify the spinifex-textured samples as Al-undepleted komatiitic basalts (11–17 wt% MgO). Platinum-group element concentrations (n = 25) are like those in global Al-undepleted komatiitic basalts, and PGE/Ti ratios do not indicate the volcanic flows likely host sulfide mineralization. Initial ε Nd values of −0.5 to +4.7 (n = 16), indicate that these lavas were derived from a depleted mantle source and have negligible evolved crust contamination. The primary magma to the komatiitic basalt flows is estimated to have had 19 wt% MgO and be derived from ∼15 to 25 % mantle partial melting at 3–4 GPa. Trace element chemistry and thermodynamic modeling suggest the primary melt assimilated local banded iron formation. Although the Bradley Peak komatiitic basalts do not contain positive evidence of magmatic sulfide deposits, depleted Au in the flows suggests they could be source rocks for nearby orogenic gold deposits.

Wyoming

Reaction kinetics and accelerant effects of sulfides in early mature hydrocarbon generation using hydrous pyrolysis

Hydrocarbon generation in organic-rich sediments is influenced by the molecular organic composition and relative abundance of associated minerals. Certain mineral-derived elements act as catalysts and reaction intermediaries, facilitating early-stage hydrocarbon formation in potential source rocks. This study investigated the role of sulfur contributed from pyrite as an accelerant in thermal reaction, focusing on its effects on early maturation and consequent hydrocarbon generation from gilsonite (low-sulfur solid petroleum). Hydrous pyrolysis (HP) experiments were conducted on mixtures of gilsonite and pyrite in varying ratios (1:0.1, 1:0.5, 1:1, 1:2, and 1:10 w/w gilsonite:pyrite) at 320, 350, and 370 °C for 72 h. Untreated and thermally altered residues were analyzed using solid bitumen reflectance (BR o , %), total organic carbon (TOC) content, programmed temperature pyrolysis, scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) to evaluate the potential accelerant role of pyritic sulfur in hydrocarbon formation. The results show HP residues at 320 and 350 °C with greater pyrite concentrations had higher BR o , while reflectance values were similar in the 370 °C residues, regardless of pyrite concentration, suggesting enhanced reaction at lower thermal conditions. Increasing pyrite content systematically decreased hydrogen index (HI) values while increasing the transformation ratio (TR) and production index (PI), indicating enhanced conversion of organic matter to hydrocarbons with increasing pyrite concentrations. Gas yields increased with pyrite addition, particularly at 350 °C, confirming secondary cracking effects. However, gas production stabilized or declined at higher pyrite loadings (1:10), suggesting alternative reaction pathways such as coke formation. Our data indicate the presence of pyrite lowers the activation energy for thermal cracking, shifting peak experimental hydrocarbon generation temperatures downward by 20–30 °C, with the most pronounced accelerant effects observed at moderate pyrite concentrations (1:0.5 and 1:1). The thermodynamic framework reveals that pyrite stability is influenced by experimental conditions, with pyrrhotite formation favored in the presence of gilsonite due to reduced oxygen fugacity. Pyrite transformation to pyrrhotite, as observed through XRD, SEM-EDS, and predicted by thermodynamic data, further supports the accelerant role of S, as pyrrhotite exhibits a higher hydrogen transfer potential, promoting early oil generation. These findings highlight the importance of pyrite in modulating hydrocarbon generation pathways in organic-rich systems.

Journal of Analytical and Applied Pyrolysis

Understanding the resource potential of natural hydrogen on Earth: Scientific gaps, uncertainties and recommendations

A comprehensive scientific research roadmap is essential to bridge knowledge gaps and deepen the understanding of key geological, geochemical, and geophysical aspects of natural hydrogen (H 2 ) as a potential new energy resource. This paper reviews major scientific uncertainties on natural H 2 , suggesting research priorities, as a guide for defining exploration strategies, techniques, and data interpretation. The uncertainties concern all phases of the natural H 2 cycle, from generation (source rocks) through migration (advection and diffusion) and accumulation (reservoir and cap rocks) to the application and interpretation of subsurface and surface geochemical and geophysical exploration techniques. Understanding H 2 sources and generation rates (the amount of H 2 generated by a given volume of rock over time) is crucial for determining whether a geological H 2 system operates as a short-term dynamic system with rapid H 2 production and release, or as a conventional gas system with long-term accumulations, analogous to petroleum reservoirs. Preliminary estimates for serpentinisation, radiolysis, and organic matter degradation suggest that H 2 generation is not inherently fast, especially for non-hydrothermal continental systems (crystalline basement of shields, ophiolites, peridotite massifs, sedimentary basins), and long-term accumulations, like those of fossil natural gas systems, represent the most likely scenario. The mechanisms of H 2 migration through geological formations require application of fundamental principles of fluid-flow physics, distinguishing advection and diffusion, as well as their forms (from gas-phase, bubble flows to aqueous solutions). Additional studies of H 2 accumulation and retention in subsurface reservoirs could improve understanding of mechanisms of H 2 migration by focusing on the rock fluid-bearing properties and the factors affecting H 2 preservation, such as the presence of cap rocks impermeable to H 2 , pressure conditions, residence times, and microbial or abiotic consumption. Advanced techniques, including reservoir modelling, flow simulations, 3D imaging (micro-CT) of H 2 -bearing rocks, and extraction and analysis of gas occluded in rocks, can provide insights into the stability and potential recoverability of H 2 accumulations. The interpretation of surface exploration techniques, including gas geochemistry, geophysics, and remote sensing, long employed in mineral and energy resource exploration, is now being adapted for natural H 2 studies, but challenges remain in the data interpretation. Distinguishing H 2 seepage due to geological degassing from H 2 produced near the surface by modern microbial processes or artificial sources, such as hammering or drilling for soil-gas sampling, drilling into aquifers, and corrosion in boreholes, is an essential step in exploration. The simple detection of H 2 in soils, even in morphological structures like sub-circular depressions or “fairy circles”, cannot be cursorily interpreted as a signal of natural H 2 seepage from a deep source. A holistic geochemical approach, including isotopic analyses of gases associated with H 2 , is recommended to distinguish among the variety of possible H 2 origins. Observations of H 2 in wells should be interrogated to rule out possible artifacts such as corrosion and drill bit metamorphism. The integration of multiple geophysical methods, including seismic, gravimetric, magnetic, and electro-magnetic surveys, is recommended to mitigate interpretation ambiguities regarding the structure of a subsurface H 2 system (source and reservoir rocks, including fluid and gas storage), due to the non-uniqueness of rock-specific physical properties.

Earth-Science Reviews

2023 Earthquake Ground-Motion Workshop for the Central and Eastern United States, with a focus on the Gulf and Atlantic Coastal Plains—Agenda and abstracts

The U.S. Geological Survey held a virtual workshop December 7–8, 2023, to share research and ideas about earthquake ground motions in the Central and Eastern United States, with a focus on the Atlantic and Gulf Coastal Plains. The workshop was organized to learn about potential regionalization of ground-motion characteristics (source, path, and site), consider new explanatory variables for site response, and hear and discuss updates on ground-motion research on the Atlantic and Gulf Coastal Plains. The workshop was organized into a series of contributed presentations and three panel discussions held during 2 days. This report documents the agenda, contributed abstracts, and panel summaries.

Scientific Investigations Report

Widespread terrestrial ecosystem disruption at the onset of the Paleocene–Eocene Thermal Maximum

The Paleocene–Eocene Thermal Maximum (PETM, ~56 Mya) interval was marked by massive 13 C-depleted carbon emissions into the ocean/atmosphere system, manifested as a negative carbon isotope excursion (CIE) in sedimentary components, and ~5 °C global average warming. Episodes of hydrological perturbations and soil-erosion have been widely documented for the PETM but their link with vegetation- and carbon cycle changes remain poorly constrained. Here, we present organic microfossil evidence showing a strong increase in fern-dominated pioneer vegetation that replaced coniferous forests on the margin of the Norwegian Sea during the first millennia of the CIE. With the present stratigraphic constraints, the “fern spike” occurred simultaneously in terrestrial settings along the North Sea, Arctic Ocean, the US east coast and in southern Australia, indicating that pioneer vegetation persisted for several millennia following a partial collapse of previously stable terrestrial ecosystems. Both the ferns and influx of microcharcoal imply recurrent physical disturbance, including soil destabilization and erosion, potentially linked to droughts, wildfires, and strong hydrological forcing resulting from extreme climate change. Together with evidence for reworked clay minerals and ancient organic matter (kerogen), these findings show that highly disturbed terrestrial ecosystems were widespread across mid- and high-latitude regions globally. Carbon cycle model simulations suggest that a substantial loss of standing and buried biomass, along with oxidation of soil organic matter, acted as important positive feedbacks during the onset of the CIE. Additionally, enhanced kerogen weathering likely contributed as another major positive feedback throughout both the onset and main phase of the CIE.

Proceedings of the National Academy of Sciences