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Rare earth element-mineralized carbonatite in the Bear Lodge Alkaline Complex, USA—Ore genesis implications from fluid inclusion characterization

Rare earth element (REE) resources of the Bear Lodge Alkaline Complex, Wyoming, are hosted in variably leached carbonatite spatially related to diatreme breccia pipes. We investigated the genesis of REE and lesser-known gold resources through fluid inclusion analysis of carbonatite, fluorite breccia, and smoky quartz vein samples. Physicochemical characteristics of inclusion-trapped fluids were evaluated using petrography, microthermometry, Raman spectroscopy, decrepitate mound analysis, energy-dispersive spectroscopy, laser ablation inductively coupled plasma mass spectrometry, and noble gas isotope analysis. Microthermometry results reveal three fluid types that affected carbonatite dikes within deeper zones that escaped near-surface, ore-grade REE enrichment: (1) high-temperature (330–432°C) magmatic fluid captured in fine-grained calcite; (2) REE-enriched alkali bicarbonate-sulfate brine; and (3) low-temperature (117–182°C) diluted magmatic or meteoric water. Multiphase brine-like inclusions contain burbankite, nahcolite, strontianite, celestine and alkali sulfate daughter crystals, linking them to early burbankite mineralization. Peripheral smoky quartz and fluorite occurrences at Smith Ridge, 1.5 km from the central carbonatite dike swarm, contain primary inclusions that are Cl-poor and rich in Na-HCO 3 -SO 4 , similar to secondary and pseudosecondary inclusions in carbonatites. Helium isotopes reveal a MORB-like source for carbonatite samples and an older crust signature at Smith Ridge, consistent with the proximal ridge-top exposures of Archean granite. Results from this fluid inclusion study coupled with previous studies of carbonatite mineral paragenesis, show that light REEs (LREEs) were not mobilized great distances. Instead, burbankite crystallized within carbonatite from alkali bicarbonate fluids. With sodium retained in early burbankite, outward-emanating fluids enriched in potassium relative to sodium (higher K:Na) resulted in potassium–ferric iron metasomatism of silicate host rocks. This alkali fractionation was accompanied by fractionation of LREEs and heavy REEs (HREEs), with LREEs dominating the central carbonatite resources. In contrast, areas of peripheral REE mineralization at Bear Lodge are commonly characterized by higher HREE:LREE ratios. The K:Na ratio of associated fenites or alteration assemblages could be indicative of early crystallized burbankite in carbonatites and REE fractionation processes potentially leading to areas of concentrated HREEs with greater supply vulnerabilities.

South Dakota, Wyoming

Microplastics undergo fragmentation during pressurized membrane filtration

Low-micrometer microplastics (<10 μm) have been detected in drinking water, driving growing interest in using pressure-driven membrane filtration to remove these particles and ensure drinking water safety. However, little attention is paid to the fate of microplastics concentrated in the filtration byproduct. In this study, using well-defined polystyrene (PS) and poly(methyl methacrylate) microspheres as model particles, we observed microplastic fragmentation during nanofiltration and the subsequent release of smaller fragments. After operating for 3 h at 20 bar, 67.9 ± 8.0% of the PS spheres in the concentrate, based on particles counted in selected fields of view, were transformed into fractured particles. The characteristic Raman band signals of microplastics were significantly weakened after fragmentation, leading to detection challenges. To address this, a data processing algorithm was developed to identify PS fragments as small as 1 μm. Preliminary statistical analysis reveals that within the tested pressure range, operation time has a stronger influence on fragmentation than pressure magnitude alone and that fragmentation is further governed by the intrinsic mechanical properties of the tested model polymers. This work provides direct evidence that pressure-driven membrane processes induce microplastic fragmentation and highlights the environmental risks associated with the discharge of fragmented microplastics into the concentrate.

Environmental Science & Technology Letters

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

Confocal laser-scanning microscopy (CLSM)-based thermal maturity of Tasmanites and progress in standardization of fluorescence microspectrometry

Evaluation of thermal maturity in vitrinite-free or vitrinite-deficient sediments via fluorescence microspectrometry can provide relevant information related to petroleum exploration and thermal history assessment. However, variation in spectral fluorescence properties of alginite macerals with increasing thermal maturity is largely underexplored. Here, authors of this study have applied confocal laser-scanning microscopy (CLSM) in conjunction with fluorescence microspectrometry to a maturity series of marine Upper Devonian Tasmanites algae from the Ohio Shale (Huron Member) and a single sample from the Marcellus Formation of the Appalachian Basin. Spectral fluorescence properties of Tasmanites were evaluated in relation to orientation, measurement location, and the number of measurements per sample, and were compared to published literature. Emission spectra of Tasmanites from continuous wave laser excitation (405 nm) were acquired from sections perpendicular and parallel to bedding and at different positions within individual Tasmanites bodies. The results showed a progressive red-shift in emission maxima (λ max ) in a large sample sized maturity series ( N = 19), e.g., 493 to 578 nm for the perpendicular section at middle position. Further, blue-shifted apex and mineral-adjacent positions within sections perpendicular to bedding were observed, with the latter being reported here for the first time. While blue-shift at apex positions can be attributed to mechanical deformation-induced reorientation of photoselected fluorophores, the blue-shifted mineral-adjacent positions could result from strain loading and development of a plastic deformation region at the mineral contact zone with Tasmanites . A decrease in standard deviation with increasing number of measured emission maxima is well-observed, and 15 to 20 individual measurements per sample appears sufficient for low standard deviation and coefficient of variance. CLSM-derived thermal maturity parameters indicated that a moderate positive correlation of red/green quotient (Q 650/500 ; R 2 = 0.67) with solid bitumen reflectance (BR o in %) exists. For reproducible results, the determination of λ max and Q 650/500 should be conducted exclusively in the middle position at perpendicular and parallel sections of the polished whole-rock pellets, where the lowest standard deviation in measurement was observed. These results strengthen the suitability and relevance of the CLSM technique in thermal maturity studies of dispersed organic matter (DOM) and contribute to the standardization of fluorescence microspectrometry methods in organic petrology investigation.

Kentucky, Ohio, Virginia, West Virginia

Identifying precursors and tracking pulses of magma ascent in multidisciplinary data during the 2018–2023 phreatomagmatic eruption at Semisopochnoi Island, Alaska

The 2018–2023 phreatomagmatic eruptions at Semisopochnoi Island, Alaska produced abundant long-period (LP) seismicity, harmonic and broadband tremor, and explosion signals over several well-monitored periods of eruption and quiescence. The corresponding dataset provides an excellent opportunity to investigate precursory and syn -eruptive geophysical signals of long-lived phreatomagmatic eruptions using multiparameter observations. We generated explosion and LP event catalogs through novel implementations of the REDPy ( Hotovec-Ellis, 2024 ) repeating event detector in mid-2021 following a network upgrade and the onset of a new phase of the eruption. The hundreds of detected explosions show a high degree of infrasound waveform similarity over more than a year, indicating a repeating source mechanism likely associated with explosive magma-water interaction. The seismic LP catalog shows that events began over a month prior to renewed explosive activity at the beginning of August 2021, and that lower frequency index (FI) LPs were generated in the week prior to the onset of explosions. We applied a recently developed machine learning tool (VOISS-Net, Tan et al., 2024 ) to catalog abundant broadband and harmonic seismic tremor recorded before and during the renewed explosive activity, along with LPs and explosions. The tremor catalogs complement the LP and explosion catalogs by filling out the seismic sequence with the dominant signal types. Together, these catalogs reveal a seismic sequence of renewed unrest that started with several weeks of LP events, followed by LPs with lower FI values and harmonic tremor in the days prior to explosive activity, and finally the onset of discrete explosions and broadband eruption tremor. We interpret this sequence as the ascent of a new pulse of magma that first interacted with the hydrothermal/groundwater system to produce LPs, followed by harmonic tremor, and that ultimately drove explosive magma-water interactions and periods of continuous ash emissions. The 2021 seismic sequence, in combination with long-term records of satellite SO 2 emissions, deformation from interferometric synthetic aperture radar (InSAR) analysis, ash sample analysis, infrasound, and volcano tectonic seismicity, allows us to interpret the entire 9-year period of unrest and eruption that began with an intrusion and earthquake swarm in 2014.

Alaska

Sensitivity of Alabama freshwater gastropod species to nickel exposure

Snails are effective bioindicators due to their prolific distribution, high level of endemism, and capacity to accumulate contaminants. Freshwater snails have unique ecological niches which are imperiled by land‐use change and the introduction of hazardous chemicals. To assess how environmental alterations affect gastropods, lab‐based studies are needed to characterize the toxicity of specific stressors. This can help guide policy decisions and remediation efforts. The aim of this research was to characterize acute toxicity of nickel (Ni) on endemic snails ( Somatogyrus georgianus [Walker, 1904], Elimia cahawbensis [Lea, 1861], and Elimia spp.) and measure the accumulation of Ni and mineral elements including calcium (Ca), magnesium, potassium, and sodium (Na). Snails were exposed to six concentrations (25–800 µg/L) of Ni for 96 h. Among the studied snail species, E. cahawbensis was the most sensitive to Ni, with the lowest lethal concentration where 50% of the organisms died (LC50) at 88.88 µg/L Ni after 96 h. The LC50 at 96 h for S. georgianus was 167.78 µg/L Ni, and 393.13 μg/L Ni for Elimia spp. Except for Elimia spp., mortality of the other two snail species corresponded to the whole‐body uptake of Ni. Nickel exposure also influenced Ca and Na uptake for Elimia spp. All three endemic species are potential candidate species for evaluating localized effects of human activities, and the present study provides a first step in characterizing how snails would be affected by environmental alterations. More research could further characterize potential effects of other human stressors on these endemic snail species. Future research into subindividual responses and routes of exposure can further elucidate variations in species sensitivity.

Alabama

A joint Gaussian process model of geochemistry, geophysics, and temperature for groundwater TDS in the San Ardo Oil Field, California, USA

Decline in availability of fresh groundwater has expanded interest in brackish groundwater resources; however, the distribution of brackish groundwater is poorly understood. Water resources in sedimentary basins across the United States often overlie oil and gas development. Mapping of groundwater total dissolved solids (TDS) using data from oil well geophysical logs has become an important technique for identifying fresh and brackish groundwater. Existing geophysical log analysis methods use porosity and temperature to relate formation resistivity to TDS. Typically, natural geothermal gradients are used to estimate temperature at the location of collected resistivity. However, in thermally enhanced oil fields, steam is injected into the subsurface to mobilize high viscosity oil, creating variable temperature distributions. Furthermore, TDS derived from resistivity also depends on the fractions of dominant ions. Typically, chloride and bicarbonate fractions must be determined. It is also necessary to model TDS across many geologic units with heterogenous porosity distributions. Collectively, each quantity used to estimate TDS (resistivity, porosity, temperature, bicarbonate fraction) varies in space and time, and available data points are rarely collocated. Here, we present a new method of mapping groundwater TDS that continuously models each quantity together with a joint Gaussian process. This method enables mapping fresh and brackish water with practically available data. We apply this method to the San Ardo Oil Field in Monterey County, California, where steam injection occurs. In some areas of the aquifer system overlying the oil zone, the temperature is ∼75 °C, roughly twice the natural background value. Groundwater TDS is typically <1,500 mg/L in the aquifer and increases with depth to ∼9,000 mg/L in the oil-producing zone. A low-permeability clay layer delineates the fresh and brackish water, likely by inhibiting surface recharge from penetrating the deeper zones, allowing higher-TDS connate water to remain in place. Weaker lateral TDS trends may be controlled by recharge patterns associated with the Salinas River. Our model reveals with high certainty that groundwater has freshened in one localized part of the oil-producing zone and suggests with less certainty that more widespread freshening has also occurred. The lowering of TDS was possibly from decades of low-TDS steam injection and the associated fluid production and disposal operations.

California

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

Cotton farming pesticides affect ileal microbiota activity expressions of virulome but not resistome or metabolic pathways in a sedentary wild passerine

The increased use of agrochemicals to enhance crop production has had detrimental environmental effects including implication in the sharp decline of North American farmland-breeding birds. Here, using a combination of deep shotgun metatranscriptomics and pesticide exposure data, we sought to assess whether exposure to cotton ( Gossypium spp.) production had a differential effect on ileum multi-kingdom microbial activity, metabolism, anti-microbial resistance, and virulence factors of sedentary northern mockingbirds ( Mimus polyglottos ) sampled from two cotton-producing areas (16 birds in total) and one uncultivated area (7 birds) in Texas, USA. Both Shannon Index values (Adj. r 2 = 0.174, F (1,21) = 5.633, p = 0.027) and a Mantel test (Spearman ρ = 0.184, p = 0.013) supported a relationship between metabolically active microbiota Bray–Curtis dissimilarities and differences in pesticide mixtures among study areas. Virulence factor richness (Adj. r 2 = 0.182, F (1,21) = 5.890, p = 0.024), Shannon Index (Adj. r 2 = 0.231, F (1,21) = 7.612, p = 0.012), and load (sum of virulence factor abundances; Adj. r 2 = 0.160, F (1,21) = 5.194, p = 0.033) were related to total pesticide load (total quantity of pesticides). We found no pesticide effects on expression of either antimicrobial resistance genes or metabolic pathways.

Texas

Widespread occurrence of former anhydrite phenocrysts in Laramide-age magmas related to porphyry-skarn Cu mineralization at Santa Rita and Hanover-Fierro, New Mexico, USA

Reports of magmatic anhydrite are relatively rare, with only ~30 occurrences documented worldwide so far. However, magmatic anhydrite saturation is difficult to recognize because anhydrite decomposes rapidly in near-surface environments. In most cases, only anhydrite inclusions shielded within other phenocryst phases were able to survive. Alternatively, since anhydrite phenocrysts preserved in fresh volcanic rocks are characteristically intergrown with apatite phenocrysts, the former presence of anhydrite phenocrysts can be recognized based on the occurrence of lath-shaped cavities that show a strong spatial association with apatite phenocrysts. These cavities can be either empty or filled with low-temperature, secondary minerals such as zeolites, carbonates, or microcrystalline silica. A systematic search for the occurrence of such cavities, combined with optical and Raman-spectroscopic identification of anhydrite inclusions preserved within apatite, hornblende and quartz phenocrysts, demonstrates that most of the Laramide-age magmas associated with the Santa Rita and Hanover-Fierro porphyry-skarn Cu (Zn, Mo, Au, Pb) deposits were saturated in magmatic anhydrite. The anhydrite typically coexisted with monosulfide solid solution (MSS), suggesting oxygen fugacities of ~2.0±0.5 log units above the fayalite-magnetite-quartz buffer. The magmas range from andesitic to rhyodacitic in composition, and from shortly pre-mineralization (~61 Ma) to shortly post-mineralization (~57 Ma) in age. In three samples with particularly well-recognizable former anhydrite phenocrysts, their modal abundance could be quantified based on high-resolution scans of polished hand specimens. The observed modal anhydrite abundances of 0.63–1.8 vol% translate into minimum magma sulfur contents of 0.20–0.56 wt% S. The highest sulfur content of 0.56 wt% S is difficult to reconcile with available anhydrite solubility models, but it could be reproduced in an anhydrite solubility experiment performed at 950 °C and 1.15 GPa on a natural latite containing 13.1 wt% dissolved H2O. The sample with the second-highest sulfur content of 0.26 wt% S requires ~10 wt% H2O in the silicate melt, and, consequently, a minimum pressure of ~0.5 GPa. Taken together, the results suggest that the magmas of the Central Mining District were extremely hydrous and thus originated from great depth. Indeed, their major element compositions and reconstructed H2O and S contents agree well with experimentally observed and numerically predicted compositions of residual silicate melts after 50–70 wt% crystallization of ordinary arc basalts at high pressure and high oxygen fugacities.

New Mexico

Mineral chemistry perspective on remobilization of stored magma at Kamakai'a Hills, Southwest Rift Zone of Kilauea, Island of Hawai'i, USA

Differentiated magmas stored in the rift zones of Kīlauea have received more attention in recent years following eruption of andesite during the early phase of 2018 lower East Rift Zone activity. Despite this growing interest, some of the most voluminous eruptions of differentiated rift zone magmas remain poorly studied. One such eruption, and the most voluminous exposed differentiated flow field at Kīlauea, is the Kamakaiʻa Hills. This eruption took place in the Southwest Rift Zone of Kīlauea, a region that is hypothesized to contain a long-lived rift zone reservoir. The Kamakaiʻa Hills flow field encompasses >250 × 10 6 m 3 of basaltic andesite and basalt compositions with a mineral assemblage of orthopyroxene + clinopyroxene + plagioclase during its early ʻaʻā phase and clinopyroxene + plagioclase + olivine during its late pāhoehoe phase. To better understand storage conditions and magma accumulation, this study focuses on major, minor, and trace elements from the mineral assemblage present within the early ʻaʻā and late pāhoehoe phases. The diversity of clinopyroxene and plagioclase compositions within the early ʻaʻā and late pāhoehoe phases, as well as diverse compositions of plagioclase and orthopyroxene within the early ʻaʻā phase, suggest multiple magma bodies and limited pre-eruption magma mixing within the broader Kamakaiʻa Hills reservoir. Oscillatory zoning patterns (particularly in clinopyroxene) imply processes such as recharge events, magma mixing or mingling, or convection within a differentially cooling, chemically stratified reservoir over protracted time intervals, whereas only limited resorbed mineral textures indicate incomplete mixing of heat and chemically distinct magmas during the dike intrusion that triggered the eruption. Mineral-mineral and mineral-melt thermobarometry indicate predominantly shallow (≤2.5 km depth) crustal storage conditions of the cooled, differentiated magma (∼1100 °C and cooler for the basaltic andesites) to hotter temperatures for the basalts (all >1100 °C). Despite the known large standard errors estimated for mineral-melt and mineral-mineral barometry (10s to >100 MPa), the calculated pressures and depths broadly correspond with earthquake swarm depths beneath the Kamakaiʻa Hills, and drill core and fluid inclusion barometry storage depths of differentiated magmas within the lower East Rift Zone. The Kamakaiʻa Hills differentiated magmas have H 2 O contents (∼0.5 wt%, using plagioclase-melt hygrometry) equivalent to typical Kīlauea basalts. Our data and interpretations demonstrate a complex, long-lived rift zone storage system that consisted of multiple magma bodies and was mobilized into eruption through intrusion of a hotter and more primitive summit-derived (uprift) magma.

Hawaii

Simulated mean monthly groundwater-transported nitrogen loads in watersheds on the north shore of Long Island Sound, 1993–2022

Elevated nitrogen loads are pervasive in the Long Island Sound, an estuary that receives freshwater and nutrients from both surface-water and groundwater discharge. Surface-water nitrogen loads to the Long Island Sound are relatively well characterized, but less is known about groundwater-transported nitrogen loads. Prior work on the northern shore of Long Island Sound (Connecticut and areas of New York and Rhode Island) suggested that groundwater travel times are relatively short (median less than 2 years) and that decade-long nutrient legacies are not widespread. Because the travel times are short, groundwater flow and nutrient loads likely vary substantially between months. In the current study, the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency’s Long Island Sound Study and the Connecticut Department of Energy and Environmental Protection, developed a set of models to better characterize spatial and temporal patterns of groundwater-transported nitrogen loading from atmospheric deposition, septic systems, and fertilizers within the study area. The models provide an estimate, with uncertainty, of groundwater-transported nitrogen loads in the study area, filling a key gap in the nitrogen budget for Long Island Sound. The models also highlight the spatial and temporal variation in nitrogen loading throughout the study area. The modeling workflow involved four models. (1) A soil-water-balance model was developed by using the Soil-Water-Balance software to simulate groundwater recharge across the study area for water years 2005 through 2022. The simulated mean monthly recharge from the soil-water-balance model was used as input into a groundwater-flow model. (2) The groundwater-flow model was developed by using the MODFLOW 6 software and data for water years 1993 through 2022 and simulates average monthly hydrologic conditions. The groundwater-flow model was calibrated by using the Iterative Ensemble Smoother method within the PEST++ software. The Iterative Ensemble Smoother method generates an ensemble of sets of parameter values, with each set producing reasonable simulated hydrologic parameter values. (3) An ensemble of MODPATH particle-tracking simulations were run to generate particle flow paths and travel times, with each simulation using a different set of the flow model parameters. (4) A nitrogen load model uses the MODPATH simulation outputs to track nitrogen from the land surface through multiple attenuation zones until it discharges into fresh or saline surface water. As with the groundwater-flow model, the nitrogen model simulated average monthly groundwater-transported nitrogen loads for water years 1993 through 2022. One novel aspect of the nitrogen load model is that the nitrogen attenuation parameters were calibrated to observed nitrogen loads. Across the ensemble of simulated nitrogen loads, the median study-area-wide monthly simulated nitrogen loads from the aquifer to Long Island Sound throughout the year ranged from 900 to 18,600 kilograms of nitrogen per day, with a median load of 5,100 kilograms of nitrogen per day. The simulated loads were based on average monthly conditions for water years 1993 through 2022. Loads were highest during the winter and early spring and lowest during the late summer. However, simulated travel times for groundwater and nitrogen loads discharged to Long Island Sound during summer were longer than travel times for groundwater and loads discharged during the winter, indicating that, on average, groundwater discharged during summer traveled along different, and longer, flow paths, than groundwater discharged during winter. This indicates that summer loads would respond more slowly to changes in nitrogen inputs at the water table than winter loads. Over the entire study area, approximately 15 percent of the simulated load is from atmospheric deposition sources, 30 to 40 percent is from fertilizer, and 50 to 60 percent is from septic systems. The final analysis of the study involved simulating the change in groundwater-transported nitrogen load in response to upgrading septic systems or reducing fertilizing inputs to areas of turf grass. Both management interventions reduced the groundwater-transported nitrogen load, and reductions were greater in areas with greater loads from septic systems or turf-grass fertilizers. The delay between management actions and substantial reductions in groundwater-transported nitrogen loads varied seasonally; loads during the late summer months remained elevated longer than the winter loads.

Connecticut, Rhode Island

Evaluation of daily stream temperature predictions (1979-2021) across the contiguous United States using a spatiotemporal aware machine learning algorithm

Stream temperature controls a variety of physical and biological processes that affect ecosystems, human health, and economic activities. We used 42 years (1979–2021) of data to predict daily summary statistics of stream temperature across >50,000 stream reaches in the contiguous United States using a recurrent graph convolution network. We comprehensively documented the performance – both across all reaches and by stream type (e.g., reservoir or groundwater influence) – as a baseline for future improvement. The model showed reach-level RMSE of <2 °C with 90 % prediction intervals that contain 90.7 % of observations. We also assessed how the model captured variability in ecologically relevant metrics (e.g., R 2 for annual 7-day maximum = 0.76; R 2 for days exceeding 25 °C = 0.75). This model does not outperform state-of-the-art machine learning efforts (e.g., RMSE ≤1.5 °C) due to a limited input set but does provide the most spatially complete modeling to date to support water availability assessments.

contiguous United States

The Sedimentary Geochemistry and Paleoenvironments Project Phase 2 data release: An open data resource for the study of Earth's environmental history

Geochemical data from sedimentary rocks are the primary source of information regarding Earth's surface evolution through time, including its air and water envelopes and interactions with life and deep Earth processes. The Sedimentary Geochemistry and Paleoenvironments Project (SGP) is a scientific consortium centered around open data and community-driven development of cyberinfrastructure tools and resources for sedimentary geochemistry and Earth history. Here we describe the SGP Phase 2 data release, which focused on incorporating Paleoproterozoic and Mesoproterozoic (2500–1000 million years ago) data and better accommodating carbonate data. This data release was built through the involvement of >200 researchers worldwide in academia, government, and industry, and provides the largest available public data resource for our user community in the academic fields of geochemistry, sedimentology, tectonics, paleontology, Earth history, and paleoclimate, as well as the petroleum and minerals industries. The dataset now encompasses 126,006 samples and 4,132,371 geochemical analyses. In addition to direct entry by SGP Team Members, we have ingested and incorporated datasets from the Geoscience Australia OZCHEM database, the Alberta Geological Survey, and the Deep-Time Marine Sedimentary Element Database (DM-SED) compilation. This paper details sampling in the Phase 2 dataset with respect to age, geography, lithology, and other geological characteristics, documents access via our search website and API, discusses possible issues and/or biases in the dataset that could impact analyses, describes plans for governance and stewardship of data from Indigenous lands, and serves as the citable reference paper for the data release.

Chemical Geology

Multiple machine-learning estimation of groundwater levels and trends for the regional Mississippi River Valley alluvial aquifer

The Mississippi River Valley alluvial aquifer provides irrigation, public, and domestic water supplies across the south-central United States. Declining groundwater levels require improved characterization of changing conditions. Traditional potentiometric-surface mapping does not use all available water-level data or quantify uncertainty. To address these limitations, we developed a data-driven multiple machine-learning (MML) framework delivered through two open-source R packages. The covMRVAgen1 software assembles covariates to 155,960 monthly groundwater levels from 57,695 wells; the mmlMRVAgen1 software trains Cubist and Random Forest models, blends them, and makes 1-kilometer gridded predictions of monthly potentiometric surfaces for the period January 1980–December 2022. The MML approach provides a methodological foundation for region-scale spatiotemporal groundwater prediction and uncertainty quantification, generating 90-percent prediction limits with appropriate empirical coverage. Model performance is acceptable, with a root-mean-square error of about 4.2 feet, standard deviation of 24.82 feet, and a normalized Nash–Sutcliffe efficiency of 0.973.

Arkansas, Illinois, Louisiana, Mississippi, Missou

Small-volume tephra deposits of the May 1924 explosions from Halemaʻumaʻu, Kīlauea volcano, and their origin

More than 50 explosive eruptions occurred from Halemaʻumaʻu at Kīlauea volcano over 17 days from May 11 to 27, 1924. Ballistics weighing as much as 14,000 kg were ejected and most landed within 2 km of the vent. Fine ash made up a major component of the tephra and was dispersed tens of kilometers downwind. Draining of the Halemaʻumaʻu lava lake occurred in late February 1924, with the crater floor eventually subsiding by a further ∼70 m (to ∼180 m below the crater rim) by the time the first explosions took place during the night of May 10–11. The largest explosions occurred on May 17–18 and smaller explosions continued until May 27, at which point Halemaʻumaʻu had more than doubled in width and depth. The explosions generated plumes reaching up to ∼10 km high with ballistics ejected up to 2 km from the crater. Almost 100 years later, we investigate and characterize the preserved tephra deposits within ∼3 km of the 1924 crater rim. Grain size and shape analyses were performed on 202 samples collected from 34 tephra profiles using dynamic image analysis, with a subset of layers from nine tephra profiles used for componentry (200 grains per layer in the 0.5–1 mm size fraction). Additionally, we characterize the average diameters (using the five largest clasts) at 216 locations and measure the average diameters of 2291 ballistics (largest per ∼100 m 2 area). Physical descriptions from fieldwork and grain size distributions were used to subdivide the tephra layers into five lithofacies: coarse homogeneous, fine homogenous, red ash, accretionary lapilli-bearing, and finely laminated. Grain size versus shape data show a range of values that demonstrate most grains are dense, smooth, and equant, in alignment with lithic clasts dominating the tephra componentry. The fine grained and accretionary lapilli-bearing nature of some of these lithofacies confirms that water influenced the style of the explosions. However, we also note juvenile clasts within many of the tephra layers, indicating that many of the layers were formed during phreatomagmatic explosions (sensu stricto), despite the eruptive mechanism being dominantly phreatic. Juvenile clasts are more abundant higher in the tephra profiles, suggesting that juvenile magma was more involved later in the explosive sequence. Thermal and hydrologic modeling indicate that groundwater inflow into a short-lived, small-diameter volcanic conduit (10-m to 120-m-diameter used for modeling) during the 78–85 days preceding the first explosion provides a physically plausible mechanism for this eruptive sequence.

Hawaii

Environmental setting and water-quality issues in the lower Tennessee River basin

The goals of the National Water-Quality Assessment Program are to describe current water-quality conditions for a large part of the Nation's water resources, identify water-quality changes over time, and identify the primary natural and human factors that affect water quality. The lower Tennessee River Basin is one of 59 river basins selected for study. The water-quality assessment of the lower Tennessee River Basin study unit began in 1997. The lower Tennessee River Basin study unit encompasses an area of about 19,500 square miles and extends from Chattanooga, Tennessee, to Paducah, Kentucky. The study unit had a population of about 1.5 million people in 1995. The study unit was subdivided into subunits with relatively homogeneous geology and physiography. Subdivision of the study unit creates a framework to assess the effects of natural and cultural settings on water quality. Nine subunits were delineated in the study unit; their boundaries generally coincide with level III and level IV ecoregion boundaries. The nine subunits are the Coastal Plain, Transition, Western Highland Rim, Outer Nashville Basin, Inner Nashville Basin, Eastern Highland Rim, Plateau Escarpment and Valleys, Cumberland Plateau, and Valley and Ridge.The lower Tennessee River Basin consists of predominantly forest (51 percent) and agricultural land (40 percent). Activities related to agricultural land use, therefore, are the primary cultural factors likely to have a widespread effect on surface- and ground-water quality in the study unit. Inputs of total nitrogen and phosphorus from agricultural activities in 1992 were about 161,000 and 37,900 tons, respectively. About 3.7 million pounds (active ingredient) of pesticides was applied to crops in the lower Tennessee River Basin in 1992. State water-quality agencies identified nutrient enrichment and pathogens as water-quality issues affecting both surface and ground water in the lower Tennessee River Basin. Water-quality data collected by State and Federal agencies between 1980 and 1996 were summarized to characterize surface- and ground-water quality of the subunits with respect to these issues. Median concentrations of nitrogen species generally were less than 1 milligram per liter in surface and ground water in all subunits, and were highest throughout the subunits that had the largest percentages of agricultural land use. Median phosphorus concentrations also were less than 1 milligram per liter in all subunits. Phosphatic limestones present in two subunits had a larger effect on phosphorus concentrations in surface and ground water than did the amount of agricultural land use in these subunits. Median counts of fecal coliform were higher in surface water than in ground water in all subunits. The highest median counts in surface water were in the Valley and Ridge (7,500 colonies per 100 milliliters) and the Outer Nashville Basin subunits (5,000 colonies per 100 milliliters). Highest median counts in ground water were in the Inner and Outer Nashville Basin subunit. Natural setting likely has an important effect with respect to fecal contamination of surface and ground water in the lower Tennessee River Basin.

Alabama, Georgia, Kentucky, Mississippi, Tennessee

Climate-driven sulfate export in alpine watersheds may stimulate methylmercury production

Climate change is increasing sulfate export and changing wetland extent in mountain regions. These changes may increase microbially mediated production of the neurotoxic substance methylmercury due to enhanced sulfate metabolism in mountain environments. Here, we assess methylmercury concentrations and formation rates across high-elevation wetlands in the Colorado Rocky Mountains. We also investigate sulfate controls on methylmercury production within subalpine peatlands by amending soils with sulfate to mimic increased stream export of sulfate from the alpine zone and measuring methylmercury formation rates for different sulfate treatments. We found that subalpine peatlands have statistically significant higher methylmercury concentrations and formation rates compared to alpine, mineral-soil wetlands. Methylmercury production in subalpine peatlands also increased significantly ( p < 0.05) following sulfate additions; the highest rates occurred in sediments with intermediate extractable sulfate concentrations (∼0.60–1.4 mg sulfate g −1 dry soil). Our study is the first to identify soil sulfate-related thresholds for methylmercury production and sulfate-limitation of methylmercury production in subalpine peatlands. These findings highlight important linkages between climate-driven mineral weathering and mercury cycling in mountain regions globally.

Colorado