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Volcanic gas monitoring

Introduction As magma rises through the crust, decreasing pressure conditions allow volatiles to exsolve from the magma. These volatiles then migrate upward through the crust, where they can be stored at shallower levels or escape to the atmosphere. Rising magma also heats rock masses beneath volcanic centers, causing water in shallow aquifers and hydrothermal systems to boil and release additional gases and steam (see chapter F , this volume; Ingebritsen and Hurwitz, 2024). The chemistry and quantity of gases that reach the surface during periods of quiescence or volcanic unrest can reveal that gas-rich magma is ascending, crystallizing, or alternatively stalling, with important implications for volcanic hazard (for example, Sutton and others, 1992; Aiuppa and others, 2007, 2021; Werner and others, 2009, 2011, 2012; Moretti and others, 2013; de Moor and others, 2016; Lewicki and others, 2019; Edmonds and others, 2022; Kern and others, 2022; Kunrat and others, 2022). Most volcanoes in Alaska and the western United States are characterized by weak degassing, with one or more low-temperature fumaroles (typically near the local boiling temperature of water) and connect to a deeper and sometimes extensive hydrothermal system (for example, McGee and others, 2001; Symonds and others, 2003a, b). Hydrothermal systems will affect the chemistry of rising gases exsolved from deeper magma (Symonds and others, 2001), including sulfur dioxide (SO 2 ), hydrogen chloride (HCl), and water vapor (for example, Doukas and Gerlach, 1995; Gerlach and others, 1998, 2008; Symonds and others, 2001; Werner and others, 2013). As an example, depending on factors such as temperature, pressure, and oxidation state, rising SO 2 will react with groundwater to form hydrogen sulfide (H 2 S) gas, dissolved sulfate (SO 4 2− ), or elemental sulfur (Christenson, 2000; Symonds and others, 2001; Werner and others, 2008). The reaction and dissolution of SO 2 into shallow groundwater is commonly referred to as scrubbing, and can reduce the likelihood that ascending, degassing magma can be detected. Carbon dioxide, however, in addition to exsolving from magma early in the ascent process, is not easily removed by hydrothermal fluids (Lowenstern, 2001). As scrubbing and other processes take place, the SO 2 /H 2 S, CO 2 /SO 2 , and CO 2 /H 2 S ratios may change. High rates of SO 2 emission indicate that magma has moved to relatively shallow levels in the volcano and that the system has heated up enough to establish dry pathways from depth to the surface. Monitoring multiple gas species and the total output of those species is thereby useful for volcano monitoring during both periods of quiescence, to establish background degassing conditions, and during unrest, when gas geochemistry and emission rates can provide information on changing conditions, such as magma ascent. To provide context for multidisciplinary volcano forecasts, we focus on the following two key required capabilities: (1) characterizing baseline geochemistry and gas discharge from volcanoes and volcanic regions and (2) monitoring changes in gas geochemistry and discharge to inform forecasts of volcanic eruptions and their effects. Sufficient baseline data must be collected to identify and interpret anomalous degassing associated with volcanic unrest (for example, Sorey and others, 1998; Rouwet and others, 2014). Differences in volcano type, baseline degassing rates, local hydrology, and geography (for example, high versus low latitude) will result in a different baseline for each volcano. Volcanoes of any threat level that exhibit one or more degassing phenomena would ideally be monitored by techniques needed to establish baseline degassing data, with the sampling frequency of baseline data dictated by the threat level (table E1). Additional monitoring techniques become necessary during periods of unrest. In general, three of the most important techniques for gas monitoring are (1) direct sampling of fumarole, spring, and soil gases for laboratory geochemical measurements, (2) measurements of the chemical composition of the volcanic plume and emission rates of major gas species (for example, H 2 O, CO 2 , SO 2 , and H 2 S) by satellite, airborne, or ground-based techniques, and (3) measurements of diffuse emissions of CO 2 and other gases through soils. Various methods and instruments may be useful both for baseline studies and during unrest.

Scientific Investigations Report

Invasion of perennial sagebrush steppe by shallow-rooted exotic cheatgrass reduces stable forms of soil carbon in a warmer but not cooler ecoregion

Soil organic carbon ('SOC') in drylands comprises nearly a third of the global SOC pool and has relatively rapid turnover and thus is a key driver of variability in the global carbon cycle. SOC is also a sensitive indicator of longer-term directional change and disturbance-responses of ecosystem C storage. Biome-scale disruption of the dryland carbon cycle by exotic annual grass invasions (mainly Bromus tectorum, 'Cheatgrass') threatens carbon storage and corresponding benefits to soil hydrology and nutrient retention. Past studies on cheatgrass impacts mainly focused on total C, and of the few that evaluated SOC, none compared the very different fractions of SOC, such as relatively unstable particulate organic carbon (POC) or relatively stable, mineral-associated organic carbon (MAOC). We measured SOC and its POC and MAOC constituents in the surface soils of sites that had sagebrush canopies but differed in whether their understories had been invaded by cheatgrass or not, in both warm and relatively colder ecoregions of the western USA. MAOC stocks were 36.1% less in the 0–10 cm depth and 46.1% less in the 10–20 cm depth in the cheatgrass-invaded stands compared to the uninvaded stands of the warmer Colorado Plateau, but not in the cooler and more carbon-rich Wyoming Basin ecoregion. In plots where cheatgrass increased SOC, it was via unstable POC. These findings indicate that cheatgrass effects on the distribution of soil carbon among POC and MAOC fractions may vary among ecoregions, and that cheatgrass can reduce forms of carbon that are otherwise considered stable and 'secure', i.e. sequestered.

Environmental Research Communications

The Hardscrabble Creek complex: A newly discovered, mostly buried, Mesoproterozoic mafic-ultramafic pluton in the Wet Mountains, Colorado, USA

The origin of prolific ca. 1.4 Ga ferroan magmatism between the southwestern USA and eastern Canada is enigmatic and has been explained by various models, including extensional, mantle plume, and convergent plate-margin models. Rare mafic plutons are associated with the ferroan plutons, which may help constrain their mantle source and tectonic setting. In the southwestern USA, only two such mafic plutons are known to exist. We present the first evidence for a third, mostly buried, potentially layered, mafic-ultramafic Mesoproterozoic pluton, informally referred to as the Hardscrabble Creek complex, in the central Wet Mountains of Colorado, USA. Recent geophysical data show an elliptical magnetic and gravity high spatially coincident with local gabbroic outcrops. New field and petrographic analyses of these exposed rocks reveal that they consist of ultramafic to mafic cumulates, including orthopyroxenite, olivine norite, norite, and anorthosite. High-precision U-Pb dating of zircon from orthopyroxenite and norite yield weighted mean 206 Pb/ 238 U dates of 1352.36 ± 1.60 Ma and 1352.37 ± 1.71 Ma, respectively. These dates indicate that the complex formed over a narrow timeframe, after the adjacent 1362 ± 7 Ma ferroan San Isabel Granite, and during the waning stages of the regional ca. 1.4 Ga ferroan magmatism. Whole-rock geochemistry and Nd-Sr-Pb isotope compositions of samples from the Hardscrabble Creek complex are similar to those of the San Isabel Granite, suggesting that they were derived from the same or a similar mantle source. The mineral chemistry of the samples is comparable to Proterozoic massif-type anorthosites and related mafic intrusions, indicating that the Hardscrabble Creek complex and San Isabel Granite together represent a rare anorthosite-mangerite-charnockite-granite (AMCG) suite in the southwestern USA. The Hardscrabble Creek complex is unique because it formed ~80 m.y. after the other few mafic plutons in the southwestern USA, and it contains an ultramafic section that is absent from these plutons and rare to the AMCG suite in general. A combination of arc-like whole-rock geochemistry, chondrite uniform reservoir-like Nd-Sr-Pb isotopes, and ocean island basalt (OIB)-like zircon trace element chemistry suggests that the complex was derived from a partial melt of OIB-like mantle and interacted with metasomatically enriched lithospheric mantle. The enriched lithospheric mantle signature, combined with the long ~160 m.y. duration of magmatism in the region, is consistent with a period of protracted convergent tectonism.

Colorado

The Long Island Sound and Watershed Metadata map application

The Long Island Sound and its watershed encompass an area of about 17,000 square miles and include the Connecticut, Housatonic, and Thames Rivers, which all drain to the sound. Dozens of organizations from government agencies, nonprofits, and Tribal Nations have developed projects and monitoring programs to analyze and protect the water resources of the watershed and sound. The abundance of data and lack of an existing searchable index require a centralized metadata repository to allow users to find water resources data more efficiently. The U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency and the Long Island Sound Study, has created an interactive map application to visualize and search for metadata information across organizations working to monitor and protect the Long Island Sound.

Connecticut, Massachusetts, New Hampshire, New Yor

Evidence of mineral alteration in a salt marsh subterranean estuary: Implications for carbon and trace element cycling

Subterranean estuaries (STE) in salt marshes are biogeochemically active zones where interactions between terrestrial groundwater and seawater drive complex cycling of carbon and trace elements, influenced by mineral dissolution. These systems, characterized by fine-grained organic-rich peat overlying permeable coastal aquifers, play a crucial role as a blue carbon sink, yet their geochemical dynamics remain poorly understood. We investigated dissolved trace elements, carbon, silica, and radium isotopes in a salt marsh STE (Sage Lot Pond, Waquoit Bay, MA) over seasonal and annual cycles. Our results reveal that groundwater and estuarine water circulation through marsh peat and aquifer sediments leads to enrichments of dissolved organic and inorganic carbon (DOC and DIC), Si, Ba, and Mn, with variable source/sink behavior of Fe and net removal of U. Submarine groundwater discharge dominated Ba fluxes, whereas pore water drainage from marsh peat acted as the main sink for U and source of Si. Fe cycling was variable, with terrestrial Fe largely removed as groundwater passed through the STE, consistent with Fe-sulfide and amorphous phase formation. Radium isotope ratios identified two distinct subsurface flow pathways, influenced by metal-oxide cycling and organic matter breakdown. Si production was decoupled from DIC, suggesting Si originates from mineral alteration, whereas DIC results from both mineral weathering and microbial respiration. Silicate mineral alteration, coupled with marsh pore water drainage, accounts for up to 16% of annual DIC exports (66 g C m −2 y −1 ), highlighting the importance of STEs in coastal carbon and trace element cycling, especially as marshes face environmental change.

Massachusetts

Assessing environmental drivers of denitrification in restored riverine floodplains

Restoration of impaired floodplains is an increasingly prevalent strategy for alleviating water quality concerns and reducing downstream flooding at watershed scales. Floodplains temporarily store water and slow flow velocity to promote sedimentation during overbank flooding and remove inorganic nitrogen from floodwater and groundwater via denitrification. Evaluating the impacts of different restoration strategies on denitrification can inform more strategic investments into floodplain modifications that improve water quality outcomes. Our research investigates how denitrification rates in floodplains respond to environmental factors that are actionable from an engineering perspective through design and water resources management. We seasonally measured soil denitrification enzyme activity and various environmental characteristics in 4 floodplains with different restoration design and management approaches at the confluence of the Wabash and Tippecanoe Rivers in Indiana, United States. Our results showed that denitrification rates in an agricultural floodplain were significantly lower than in restored floodplains with native vegetation. Certain soil conditions characteristic of floodplain wetlands were associated with higher denitrification, particularly elevated total nitrogen, moisture, silt, and organic matter contents. Vegetation species composition was correlated with denitrification rates. This link may reflect the direct effects of vegetation on soil conditions, such as supplying labile organic carbon, or indirect effects, such as vegetation acting as an indicator of hydrologic regime and land use. Denitrification seasonally varied, peaking in winter when nitrate supply from rivers draining agricultural watersheds in the region is also high. Substrate limitation of soil denitrification enzyme activity was most significant during the summer when overbank flooding, which replenishes soil nitrogen stocks, rarely occurs. Our findings indicate that denitrification capacity will likely be maximized in riverine floodplains that are restored as wetlands with diverse native vegetation and enhanced hydrologic connectivity. Such restoration activities promote higher denitrification rates via elevated moisture, fine sediment deposition, and soil organic matter.

Tippecanoe River, Wabash River

Sensitivity of benthic biota and toxicity of cadmium, cobalt, copper, nickel, lead, and zinc mixtures in Washington, United States, and British Columbia, Canada

Relative sensitivities and responses of juvenile white sturgeon ( Acipenser transmontanus ), Hyalella azteca , two families of mayfly (Ephemerellidae, Heptageniidae), one family of caddisfly (Brachycentridae), and a natural community of benthic macroinvertebrates (BMI) to multiple metals are predicted using previously collected laboratory and field samples and a metal mixture model. Biological responses in single metal exposures are used to parameterize toxicity functions, which include accumulations of hydrogen and selected metals on biological receptors, intrinsic potencies of hydrogen and metals, sensitivities of organisms, and times of exposure. The model then is used to predict responses in multiple metal laboratory exposures and field-collected porewater. The following sensitivity sequence in porewater was determined based on endpoints of survival or total abundance: juvenile white sturgeon greater than (>) Ephemerellidae family > Hyalella azteca > Heptageniidae family about equal to (~) benthic macroinvertebrate community > Brachycentridae family. The fraction of porewater samples that are predicted to have adverse impacts on benthic biota (20-percent or greater negative response) depends on organism sensitivities and metal toxicities, and ranges from 44 to 48 percent for juvenile white sturgeon, 23 to 26 percent for the Ephemerellidae family, 16 to 22 percent for Hyalella azteca , 5 to 8 percent for the Heptageniidae family and BMI community, and 0 percent for the caddisfly family. The most toxic porewater in the upper Columbia River Basin (UCR) is at the backwater bar site at Deadmans Eddy and China Bend. The model also indicates that the element responsible for the most toxic conditions in UCR porewater is copper for all organisms, except Hyalella azteca and the metal-insensitive Brachycentridae family. Copper and lead result in the most toxic conditions for Hyalella azteca . This approach and results can aid in assessing metal toxicity and its potential risk to aquatic biota in ecosystems impacted by historical mining activities.

British Columbia, Washington

Recent scientific contributions by the U.S. Geological Survey in the San Francisco Bay and Sacramento–San Joaquin Delta Estuary

Introduction The San Francisco Bay and Sacramento–San Joaquin Delta Estuary (hereafter, Bay-Delta) is the largest estuary on the West Coast of the United States. The Bay-Delta covers more than 1,600 square miles and drains a watershed of more than 75,000 square miles, which is greater than 40 percent of California. The region surrounding the Bay-Delta is home to about 10 million people, and its habitats (fig. 1) support more than 800 plant and animal species. The waterways of the Bay-Delta are the central hub of California’s extensive freshwater delivery system, supplying water to more than 27 million Californians and 4 million acres of farmland in the Central Valley. The U.S. Geological Survey (USGS) is the primary science agency of the U.S. Department of the Interior, providing a broad range of Earth, water, biological, and mapping data and expertise to inform natural resource management across the country. This fact sheet focuses on research conducted by the USGS in the Bay-Delta region, mostly within the past 5 years. The fact sheet is organized across five major themes: water flow and water quality, fish and wildlife, wetland restoration, invasive species, and hazards. In each of these areas, the USGS works closely with Federal, State, and local agencies; academia; and non-governmental organizations to provide objective, evidence-based science. The data and knowledge gained from USGS research and monitoring are publicly available and are routinely used by agencies, including the U.S. Bureau of Reclamation, U.S. Army Corps of Engineers, U.S. Fish and Wildlife Service, California Department of Water Resources, California Department of Fish and Wildlife, California State Water Resources Control Board, Delta Stewardship Council, and many additional organizations and stakeholders to inform management of the Bay-Delta region and its resources.

California

Evaluating groundwater quality influences from oil field operations and other anthropogenic activities in an urban setting, Santa Fe Springs, California

Groundwater quality is often affected by anthropogenic activities in urban settings. This study examines groundwater quality in and around the Santa Fe Springs Oil Field in Los Angeles County, California, where oil and gas production commonly intersects with high density industrial, commercial and residential land uses. Utilizing a combination of new and historical data, we evaluated potential pathways that would allow for oil field formation fluids to migrate into groundwater and whether mixing may have occurred based on the distribution of groundwater and oil field formation fluid tracers in samples. Samples were analyzed for a wide array of constituents including volatile organic compounds, light hydrocarbons, major ions, and various isotopic compositions. Despite evidence of oil field infrastructure providing potential pathways of migration via uncemented annular spaces, casing breaches and historical disposal of oil field formation water in surface ponds, the distribution and occurrence of stable isotopes of water, chloride, boron, and total dissolved solids do not indicate mixing of oil field formation water and groundwater. However, methane isotopic signatures and the presence of heavier alkanes suggest gas from oil-bearing formations have migrated from depth via oil field well infrastructure. Volatile organic compound detections were mainly from manufactured compounds unrelated to oil and gas production, with a relatively limited number of petroleum hydrocarbons also detected. Volatile organic compounds were generally found in wells tapping shallow, modern aged groundwater, indicating anthropogenic activities occurring at or near land surface as the source. Study results suggest that while oil field infrastructure provides migration pathways for oil field formation fluids to be introduced into groundwater, urban land uses not related to oil and gas production are the primary drivers of groundwater quality degradation.

California

Geophysical identification of potential groundwater – surface water interactions in the Bonita Peak Mining District, San Juan County, Colorado

This report includes the results and interpretation of geophysical investigations to aid in the location, identification, and conceptual site model (CSM) development of the near surface groundwater and surface water hydrology of the Upper Cement Creek and California Gulch of the Animas Rivers within the Bonita Peak Mining Districts (BPMD). Mine influenced water (MIW) from numerous mine adits within the BPMD has altered the geochemistry and ecology of these ground and surface waters. Many studies of varying scales have investigated the geology, hydrogeology, geochemistry, and aqueous chemistry of these adits and impacted areas. Field investigations using non-invasive geophysical methods were conducted in the summer of 2019 to aid in identifying potential groundwater inputs to these streams and further the CSM of the near surface within and along these streams. Two field deployments were completed in August and September of 2019. In August 2019, Phase 1 was completed using multifrequency electromagnetic induction (EMI) and thermal infrared imaging (TIR) to measure the bulk electrical conductivity, magnetic susceptibility, and the temperature response at known and suspected groundwater seeps into the Upper Cement Creek and California Gulch stretches of these alpine streams. Results and interpretation from Phase 1 were used to co-locate stretches of these streams for further detailed fiber optic distributed temperature system (FODTS) monitoring of the temperature dynamics for submeter identification of potential groundwater seeps during Phase 2. Phase 2 included additional EMI measurements, FODTS measurements, and repeated some Phase 1 measurements for improved data quality. All these data were used for the combined qualitative interpretation identifying seep locations. The data from both Phase 1 and Phase 2 are available in the USGS data release at: https://www.sciencebase.gov/catalog/item/5f18a30082cef313ed84879b. These data include detailed near-surface electrical conductivity and magnetic susceptibility mapping, discrete TIR imaging, and several kilometers of FODTS data. These data were georeferenced and used to identify potential groundwater seeps into these streams. The results indicate a complex near surface geophysical and hydrogeologic regime. Seeps are classified and spatially correlated to the EMI, TIR, and geochemical sampling results. This report is a thorough compilation of the geophysical field efforts in the summer of 2019, the data processing, and interpretations of these data. These data alone should not be used for final interpretations of the complex hydrogeology within these alpine systems. Rather, these data should be combined with other known data from various investigations to further refine the CSM and guide decisions for future investigations, watershed protective measures, and other site decisions. Geographical information system (GIS) layers of these results are available to project managers for such integration and combined interpretations.

Colorado

Generating geochemical and mineralogy distributions of soil in the conterminous United States using Bayesian hierarchical spatial models

Characterizing geochemical and mineralogical soil distributions across large spatial extents is essential for understanding mineral resources, ecosystem processes, and environmental risks. Rasters of soil geochemical distributions for the conterminous United States, however, are limited. We present a Bayesian modeling workflow and tool for generating predictive geochemical and mineralogy distribution maps for the conterminous United States using integrated nested Laplace approximation (INLA) with the stochastic partial differential equation approach. By modeling soil geostatistical data with environmental covariates (soil properties, topography, climate, and land cover), we generate predictive distributions of soil geochemistry that can be mapped or extracted for further analyses. As an example, we model the spatial distribution of trace elements in soil relevant to vertebrate health (cobalt, copper, iron, manganese, selenium, and zinc) and provide a workflow that can be used to generate and visualize predictive distributions of 39 other major and trace elements and 21 minerals of the soil survey, supporting a variety of ecological, environmental, and agricultural applications.

MethodsX

Zircon as a pathfinder to REE mineralization

Carbonatites and alkaline silicate rocks are major primary sources of the rare earth elements (REE) and other critical metals, such as Nb. Despite the economic significance of these rocks, their formation and the processes of REE enrichment are poorly understood. Here, statistical analysis of a global dataset demonstrates that zircon geochemistry is a powerful recorder of REE metallogenesis and a potential pathfinder for REE deposits. Zircons from REE and Nb fertile intrusions lack Eu anomalies and have elevated Gd/Yb and Th/Yb, indicating they crystallised from magmas that originated from deep, oxidised and enriched mantle sources. Complexes with Nb enrichment have low U/Nb, reflecting an enriched mantle source, whereas high U/Nb in REE-only fertile intrusions suggest a subduction-metasomatised mantle source. Machine learning models demonstrate high accuracy in classifying zircon from barren and fertile deposits. Classification of detrital zircons shows that REE-enriched deposits correlate with supercontinent assembly, whereas Nb fertile complexes are associated with supercontinent breakup. This approach offers a new, mineral to global scale, petrologic and exploration tool that enhances understanding of REE metallogenesis.

Geochemical Perspectives Letters

Relating systematic molecular and textural properties of graptolite pyrolyzed via gold tube hydrous pyrolysis: Implications for thermal proxies in lower Paleozoic marine shales

A series of gold tube pyrolysis experiments (72 h, 300–550 °C, 50 MPa) conducted on a graptolite-rich lower Paleozoic marine shale generated pyrolysis residues for a comprehensive evaluation of the molecular and structural variability of three types of graptolite periderm. Organic petrology, Raman spectroscopy, and field emission scanning electron microscopy (FE-SEM) with energy dispersive spectroscopy (EDS) were combined to evaluate the thermal evolution process. The three types of graptolite periderm, namely granular, non-granular, and nodular graptolite, were analyzed by Raman spectroscopy wherein point measurements were obtained after the maceral was identified and the location verified by organic petrology. Distinct thermal evolution pathways among non-granular, granular, and nodular graptolite periderms were recorded. The evolution patterns of the Raman parameters, particularly D1 and G bands, highlight the differences in geochemical composition of the graptolite periderm types and the alteration of molecular structure with increasing thermal maturity. Raman parameters D1 (position of the D1 peak), G-FWHM (full width at half maximum of the G peak), and ratios D1-FWHM/G-FWHM (full width at half maximum of the D1 peak ratioed to G-FWHM) and A D1 /A G (ratio of D1 and G peak intensities) showed effectiveness in assessing thermal maturity. Bireflectance with increasing gold tube pyrolysis temperature followed a hierarchy: non-granular > granular > nodular, reflecting different molecular alignment intensities. Qualitative FE-SEM evaluation showed that fine-grained mineral inclusions (primarily Fe-sulfide as determined via EDS) were associated with the graptolite populations, with granular graptolite containing greater amounts of coarser-grained (e.g., ∼300–1400 nm) mineral inclusions relative to non-granular and nodular graptolite, which contain finer-grained (e.g., ∼100–200 nm) inclusions difficult to resolve with optical microscopy. These findings are investigated to highlight the mechanisms that drive organic matter evolution within graptolite during thermal maturation, as well as to explore some of the limitations of using spectroscopic parameters as thermal maturity proxies.

International Journal of Coal Geology

Quality of groundwater used for domestic supply in the eastern Sacramento Valley and adjacent foothills, California

Summary More than 2 million Californians rely on groundwater from privately owned domestic wells for drinking-water supply. This report summarizes a water-quality survey of domestic and small-system drinking-water supply wells in the eastern Sacramento Valley and adjacent foothills where more than 25,000 residents are estimated to use privately owned domestic wells. Study results show that inorganic and organic constituents in groundwater were present above regulatory (maximum contaminant level, MCL) benchmarks for public drinking-water quality in 8 and 3 percent, respectively, of the aquifer area used for domestic drinking-water supply (herein, “domestic groundwater resources”; fig. 1). The only inorganic constituent detected above regulatory benchmarks was arsenic. The only organic constituent exceeding regulatory benchmarks was the fumigant 1,2,3-trichloropropane (1,2,3-TCP). Three additional organic constituents—the disinfection by-product chloroform, the gasoline oxygenate methyl tert -butyl ether (MTBE), and the solvent tetrachloroethene (PCE)—were detected at low concentrations below one-tenth of regulatory benchmarks in 34, 10, and 10 percent of domestic groundwater resources, respectively. Total dissolved solids (TDS), iron, and manganese exceeded non-regulatory aesthetic guidelines for drinking water in 5, 10, and 26 percent of domestic groundwater resources, respectively. Per- and polyfluoroalkyl substances (PFASs) were detected in 29 percent of domestic groundwater resources,with 5 percent exceeding the recently enacted (April 2024) U.S. Environmental Protection Agency MCLs. Total coliform and enterococci bacteria were detected in 13 and 8 percent of domestic groundwater resources, respectively. Redox sensitive constituents in this study included arsenic, manganese, nitrate, and iron. In the lower elevation portions of the eastern Sacramento Valley study area, reducing conditions in groundwater aquifers promote elevated arsenic, iron, and manganese, and conversely lower concentrations of nitrate. The presence of the volatile organic compound (VOC) 1,2,3-TCP was related to its past history in select agricultural land uses (on orchards or vineyards) in the Sacramento Valley; however, unlike in the San Joaquin Valley where orchards and vineyards are more common, its detection frequency was low (only detected in one well in this study). Chloroform was frequently detected in this study at low levels. Chloroform is a disinfection byproduct commonly found in domestic wells treated by shock chlorination. The solvent PCE is among the most frequently detected VOCs in groundwater, which is primarily related to its long history of use and its persistence in groundwater in oxic conditions. The gasoline oxygenate MTBE was a contaminant introduced to groundwater through atmospheric exchange when it was used as a fuel additive to decrease smog inducing emissions from vehicles. Its occurrence in groundwater at low levels is expected and makes it a potentially useful tracer of relatively recent recharge water being withdrawn from wells. The PFASs are anthropogenic chemicals with hundreds of uses, and they have been incorporated into many different products, processes, and applications worldwide. Like MTBE, the occurrence of PFASs in groundwater may be in part due to atmospheric exchange, but there are several other pathways that contribute PFASs to the environment.

California

Tapwater exposures, residential risk, and mitigation in a PFAS-impacted-groundwater community

Tapwater (TW) safety and sustainability are priorities in the United States. Per/polyfluoroalkyl substance(s) (PFAS) contamination is a growing public-health concern due to prolific use, widespread TW exposures, and mounting human-health concerns. Historically-rural, actively-urbanizing communities that rely on surficial-aquifer private wells incur elevated risks of unrecognized TW exposures, including PFAS, due to limited private-well monitoring and contaminant-source proliferation in urbanizing landscapes. Here, a broad-analytical-scope TW-assessment was conducted in a hydrologically-vulnerable, Mississippi River alluvial-island community, where PFAS contamination of the shallow-alluvial drinking-water aquifer has been documented, but more comprehensive contaminant characterization to inform decision-making is currently lacking. In 2021, we analyzed 510 organics, 34 inorganics, and 3 microbial groups in 11 residential and community locations to assess (1) TW risks beyond recognized PFAS issues, (2) day-to-day and year-to-year risk variability, and (3) suitability of the underlying sandstone aquifer as an alternative source to mitigate TW-PFAS exposures. Seventy-six organics and 25 inorganics were detected. Potential human-health risks of detected TW exposures were explored based on cumulative benchmark-based toxicity quotients ( ∑ TQ ). Elevated risks ( ∑ TQ ≥ 1) from organic and inorganic contaminants were observed in all alluvial-aquifer-sourced synoptic samples but not in sandstone-aquifer-sourced samples. Repeated sampling at 3 sites over 52–55 h indicated limited variability in risk over the short-term. Comparable PFAS-specific ∑ TQ for spatial-synoptic, short-term (3 days) temporal, and long-term (3 years quarterly) temporal samples indicated that synoptic results provided useful insight into the risks of TW-PFAS exposures at French Island over the long-term. No PFAS detections in sandstone-aquifer-sourced samples over a 3 year period indicated no PFAS-associated risk and supported the sandstone aquifer as an alternative drinking-water source to mitigate community TW-PFAS exposures. This study illustrated the importance of expanded contaminant monitoring of private-well TW, beyond known concerns (in this case, PFAS), to reduce the risks of a range of unrecognized contaminant exposures.

Wisconsin

Dietary bioavailability of uranium to a model freshwater invertebrate

Uranium (U) mining increases environmental exposures. Understanding how U is taken up by organisms can aid in evaluating the potential for bioaccumulation and toxicity. Although the importance of aqueous geochemical speciation is well recognized for U bioavailability after dissolved exposures, far less is known about the processes controlling U bioavailability after dietary exposures. This study characterizes the biogeochemical drivers of dietary U uptake in the freshwater snail Lymnaea stagnalis in laboratory experiments. Solids tested included benthic diatoms pre-exposed to dissolved U(VI), soils from contaminated U mine sites, and colloidal hydrous ferric oxide (HFO) synthesized in the presence of dissolved U(VI) or with U complexed by natural organic matter (NOM). Results showed that U was bioavailable from all solids. Uranium assimilation efficiency (AE), a proxy for dietary U bioavailability, varied among solids. AE was lowest for the U-contaminated soils (25 ± 17%) and highest for the U-laden diatoms (71 ± 13%). AE varied slightly among HFO preparations, suggesting modest influences of NOM and iron on U bioavailability. Increases in dietary U exposures reduced feeding rates, and the extent of feeding inhibition appeared inversely related to U bioavailability. The high U assimilation and range of bioavailability have implications for toxicity risks inferred without considering dietary uptake.

Environmental Science and Technology

A time-space model of graphite mineral systems

Increasing demand for graphite in energy storage systems warrants review of graphite ore genesis in a mineral systems framework. Orogenic graphite encompasses the metamorphic and orogenic mineral systems that produce flake graphite and hydrothermal vein (lump and chip) graphite deposits, respectively. A common feature of orogenic graphite deposits is an association with upper amphibolite- to granulite-facies metasedimentary rocks in continent-continent or continent-island arc collisional orogens. Orogenic flake graphite deposits form primarily through graphitization of organic carbon during regional metamorphism, but strain localization and partial melting of pelitic protoliths are likely important processes for graphite grade and quality enrichment. Orogenic vein graphite deposits precipitate from hydrothermal fluids, possibly derived from metamorphism or anatexis at depth. Decarbonation reactions in mixed calcareous-carbonaceous metasedimentary sequences are the most likely carbon sources for the veins. In contrast, intrusion-related graphite includes magmatic-hydrothermal and metamorphic mineral systems that form primarily in continental arc settings via the interaction of magmas with carbonaceous sedimentary packages. Magmatic-hydrothermal flake graphite deposits are hosted in plutonic and volcanic rocks, and result from the exsolution of CO 2 -CH 4 -rich fluids from melts contaminated by such packages. Contact metamorphism of carbonaceous sedimentary rocks by plutons produces some microcrystalline (amorphous) graphite deposits, including many in China. Compilation of geologic data from known graphite deposits globally suggests that pulses of carbon deposition in the Paleoproterozoic, Mesoproterozoic, and Neoproterozoic provided source carbon material. Subsequent supercontinent orogenesis at ca. 2,100 to 1,700 Ma (Columbia), ca. 1,300 to 1,000 Ma (Rodinia), and ca. 650 to 500 Ma (Gondwana) resulted in the genesis of orogenic flake and vein graphite deposits, where favorable geologic components overlapped with organic ± carbonate carbon-rich strata. Cryogenian deposition of graphite protoliths and Cryogenian – Cambrian metamorphic mineralization account for nearly 75% of all known resources globally and coincide with profound carbon isotope excursions and climate variability, implying a link with the global carbon budget. Comparatively few graphite deposits are associated with Pangea-forming orogens, attributed to less exhumation and/or denudation. High-temperature metasedimentary belts containing organic carbon-rich protoliths are most favorable for hosting orogenic flake graphite deposits, whereas sequences that also contain carbonate protoliths are favorable for orogenic graphite veins. Continent-scale orogenic belts may host both deposit types along with vanadium deposits. Use of a time-space mineral systems framework for graphite deposits can improve exploration models needed to ensure future supply of this critical mineral and provide insights into Earth’s long-term carbon cycle.

Mineralium Deposita

Triple-oxygen isotopic evidence of prolonged direct bioleaching of pyrite with O2

Sulfate is often touted as containing atmospheric oxygen whose isotopic signature can constrain redox, environmental conditions, and biological activity. Yet, the amount and isotopic fractionation associated with air-O 2 incorporation during sulfate formation is still debated, making its verification difficult. In this study, we identify a distinct, microbially dominated environment with the potential to preserve maximum signals of air-O 2 in sulfate. We report triple-oxygen isotope data for sulfate produced from pyrite oxidation in microbial and abiotic experiments, and from natural dissolved sulfate from the Rio Tinto, Spain, an acid mine drainage site. The oxygen isotope systematics of sulfate in these environments define a unique kinetic isotope effect associated with initial stage pyrite oxidation by Acidithiobacillus ferrooxidans that preserves >80 % oxygen from air-O 2 in sulfate. Unlike experiments, which evolve toward water-oxygen dominated sulfate on short time scales, Rio Tinto, Spain hosts a microbe rich environment with distinct geochemistry that maintains high O 2 -oxygen in sulfate. Therefore, in addition to containing isotopic records from water and air, sulfates can also contain a biosignature that is promising for understanding conditions on Mars and early Earth.

Earth and Planetary Science Letters