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Dissolved arsenic concentrations in surface waters within the upper portions of the Klamath River Basin, Oregon and California

Arsenic toxicity is an environmental health problem. Levels of arsenic in surface waters at some locations in the Klamath River Basin in southern Oregon and northern California can exceed the U.S. Environmental Protection Agency (EPA) standard for drinking water. There are both anthropogenic and natural sources of arsenic. The Klamath River Basin consists primarily of volcanic deposits and contains an underground geothermal system with hot springs and warm water wells, all known natural sources of arsenic. Anthropogenic sources of arsenic are related to the agricultural use of herbicides, fungicides, and insecticides. Surface water arsenic levels can also be affected by fertilizer amendments, evaporative concentration, oxygen-level depletion, and various geochemical transformations that can increase arsenic mobilization. In this study by the U.S. Geological Survey and the Bureau of Reclamation, dissolved concentrations of arsenic, copper, and lead were measured in surface waters at 39 unique sites within the upper portions of the Klamath River Basin between 2018 and 2022. In every year, except 2022, sites were sampled four times between April and November. Surface-water arsenic concentrations varied up to four-orders of magnitude among sites. Median arsenic concentration was lowest at Cherry Creek (0.03 micrograms per liter [μg/L]) and highest at Wood Kimball Spring (36.7 μg/L), two sites located north of Upper Klamath Lake. The highest arsenic concentrations (17.4±4.9 μg/L, n =3) were found in drain sites (defined here as a waterbody returning used irrigation water) while the lowest arsenic concentrations were found in an artesian well (0.8 μg/L, n =1). The elevated arsenic concentrations of the drain sites suggest that arsenic might be concentrated or mobilized by agricultural activities, water re-use practices, and (or) by geochemical processes occurring around water stored in drains (that is, in the water column and across sediment water boundaries). A source of arsenic in drain water in the Klamath Strait Drain area includes water used for irrigation originating from Ady Canal. Other potential sources include groundwater, geothermal water, and local soils and sediments. Seasonal differences in surface-water arsenic concentrations were detected at 13 sites, 10 of which had higher arsenic concentrations in summer than in either spring or fall. The sites sampled around Upper Klamath Lake, the impounded rivers, one of the two canal sites, and 5 of the 14 river sites had higher surface-water arsenic concentrations in the summer than in either spring or fall. Surface-water arsenic concentrations from groundwater sources (that is, springs and in the artesian well) did not vary significantly among seasons (p-values greater than 0.1). Median surface-water concentrations of copper and lead ranged from 0.03 to 3.7 μg/L, and from 0.013 to 0.175 μg/L ( n =2–18), respectively. Dissolved concentrations of both metals were below acute toxicity endpoints reported by the EPA for freshwater animals. Surface-water arsenic concentrations varied independently from corresponding changes in surface-water lead or copper concentrations. However, arsenic concentrations measured in bed-sediment samples collected from a subset of sites located north of Upper Klamath Lake correlated strongly and significantly with the corresponding sedimentary lead concentrations ( p =0.015). Aqueous arsenic speciation measured in a subset of sites in 2019 and 2022 showed that all the arsenic existed as arsenic (V), the most oxidized arsenic species, and presumably, the least toxic. The highest proportions of arsenite (As(III)), the presumably most toxic arsenic species, relative to total arsenic concentrations were found at drain sites. Our assessment of dissolved arsenic concentrations in various surface-water bodies in the Upper Klamath River Basin reveals geographical areas of consistently low (below 2.1 μg/L), moderate (below 10 μg/L) and high (above 10 μg/L) surface-water arsenic concentrations. South of Upper Klamath Lake, surface-water arsenic concentrations were consistently higher than 20 μg/L at two drain sites located in an area of predominant agricultural land use with extensive water re-use practices. North of Upper Klamath Lake, surface-water arsenic concentrations greater than 20 μg/L were consistently measured at sites with limited nearby agricultural activities, suggesting a geogenic source. The consistently high arsenic levels from the Wood River at Jackson F. Kimball State Park, Fort Creek, and Crooked Creek, which are sites located at or near headwater spring sources, suggest a natural background source of arsenic. Water flowing downstream from this area could be a potential source of arsenic to Upper Klamath Lake and the Upper Klamath River.

California, Oregon

A review of abrupt permafrost thaw: Definitions, usage, and a proposed conceptual framework

Purpose of Review We review how ‘abrupt thaw’ has been used in published studies, compare these definitions to abrupt processes in other Earth science disciplines, and provide a definitive framework for how abrupt thaw should be used in the context of permafrost science. Recent Findings We address several aspects of permafrost systems necessary for abrupt thaw to occur and propose a framework for classifying permafrost processes as abrupt thaw in the future. Based on a literature review and our collective expertise, we propose that abrupt thaw refers to thaw processes that lead to a substantial persistent environmental change within a few decades. Abrupt thaw typically occurs in ice-rich permafrost but may be initiated in ice-poor permafrost by external factors such as hydrologic change (i.e., increased streamflow, soil moisture fluctuations, altered groundwater recharge) or wildfire. Summary Permafrost thaw alters greenhouse gas emissions, soil and vegetation properties, and hydrologic flow, threatening infrastructure and the cultures and livelihoods of northern communities. The term ‘abrupt thaw’ has emerged in scientific discourse over the past two decades to differentiate processes that rapidly impact large depths of permafrost, such as thermokarst, from more gradual, top-down thaw processes that impact centimeters of near-surface permafrost over years to decades. However, there has been no formal definition for abrupt thaw and its use in the scientific literature has varied considerably. Our standardized definition of abrupt thaw offers a path forward to better understand drivers and patterns of abrupt thaw and its consequences for global greenhouse gas budgets, impacts to infrastructure and land-use, and Arctic policy- and decision-making.

Current Climate Change Reports

A practical decision tool for marine bird mortality assessments

Given the rise in anthropogenic, environmental, and disease events contributing to marine bird mortality, there is a critical need to improve the rigor of mortality assessments. Deficits in data collection and mortality estimation can hinder a manager’s ability to document the scale of events and assess population level impacts. Therefore, to inform decisions required during activities, such as conservation status assessments or harvest management, organizations may choose to incorporate mortality assessments into response plans. Resources, capacity, and assets to assess mortality vary across jurisdictions (federal, state, Indigenous, local, etc.), and clear guidance to support mortality assessments is often unavailable or not clearly addressed. Here, we present a decision support tool to help managers identify and evaluate survey options to assess bird mortality in a diverse array of scenarios. The objective of the decision tool is to improve data collection and availability, which will increase the ability to estimate mortality robustly, given situation-specific attributes and constraints. This decision tool is designed to guide the response when a mortality event is initially encountered and offers suggestions for assessment and reporting procedures in the absence of other guidance or to complement existing protocols. The decision tool is also meant to inform decision making for response determination and resource allocation. The tool facilitates examination of options for further assessment and monitoring, which users determine by examining questions pertaining to species prioritization, determination of mortality minimum spatial extent, and the potential magnitude of impacts on affected species. Finally, identification of appropriate survey methods that address imperfect detection when a complete census is not possible are determined by exploring location, spatial and temporal extent, and the type of species affected. Ultimately, this decision tool aims to facilitate and improve the standardization of mortality assessments, equipping managers with a practical resource to navigate the decision-making process for marine bird mortality estimation.

Ornithological Applications

Produced water geochemistry from hydraulically stimulated Niobrara Formation petroleum wells: Origin of salinity and temporal perspectives on treatment and reuse

Produced water (i.e., a mixture of returned injection fluids and geologic formation brines) represents the largest volumetric waste stream associated with petroleum production in the United States. As such, produced water has been the focus of intense study with emphasis on understanding the geologic origin of the fluids, environmental impacts of unintended or intentional release, disposal concerns, and their commodity (e.g., lithium) potential. However, produced water geochemistry from many active petroleum plays remain poorly constrained leading to knowledge gaps associated with the origin of brine salinity and parameters (e.g., radium levels) that can impact treatment, disposal, and possible reuse. Here we evaluate the major ion geochemistry, radium concentrations, and stable water isotope composition of ~120 produced water samples collected from 17 producing unconventional petroleum wells in Weld County, Colorado from the Late Cretaceous Niobrara Formation. This sample set encompasses eight produced water time series from four new wells across production days 0 to ~365 and from four established wells across production days ~1000 to ~1700. Additionally, produced water from nine other established Niobrara Formation wells were sampled at discrete time points ranging from day 458 to day 2256, as well as hydraulic fracturing input fluids. These results expand the available Niobrara Formation produced water geochemical data, previously limited to few wells sampled within the first year of production, allowing for the heterogeneity of major ions and radium to be evaluated. Furthermore, we explore the geochemical relationships between major ion ratios and stable water isotope composition to understand the origin of salinity in Niobrara Formation brines from the Denver-Julesburg Basin. These findings are discussed with perspective toward potential treatment and reuse of Niobrara produced water prior to disposal.

Colorado, Nebraska, Wyoming

Vulnerability assessment of groundwater influenced ecosystems in the Northeastern United States

Groundwater-influenced ecosystems (GIEs) are increasingly vulnerable due to groundwater extraction, land-use practices, and climate change. These ecosystems receive groundwater inflow as a portion of their baseflow or water budget, which can maintain water levels, water temperature, and chemistry necessary to sustain the biodiversity that they support. In some systems (e.g., springs, seeps, fens), this connection with groundwater is central to the system’s integrity and persistence. Groundwater management decisions for human use often do not consider the ecological effects of those actions on GIEs. This disparity can be attributed, in part, to a lack of information regarding the physical relationships these systems have with the surrounding landscape and climate, which may influence the environmental conditions and associated biodiversity. We estimate the vulnerability of areas predicted to be highly suitable for the presence of GIEs based on watershed (U.S. Geological Survey Hydrologic Unit Code 12 watersheds: 24–100 km 2 ) and pixel (30 m × 30 m pixels) resolution in the Atlantic Highlands and Mixed Wood Plains EPA Level II Ecoregions in the northeastern United States. We represent vulnerability with variables describing adaptive capacity (topographic wetness index, hydric soil, physiographic diversity), exposure (climatic niche), and sensitivity (aquatic barriers, proportion urbanized or agriculture). Vulnerability scores indicate that ~26% of GIEs were within 30 m of areas with moderate vulnerability. Within these GIEs, climate exposure is an important contributor to vulnerability of 40% of the areas, followed by land use (19%, agriculture or urbanized). There are few areas predicted to be suitable for GIEs that are also predicted to be highly vulnerable, and of those, climate exposure is the most important contributor to their vulnerability. Persistence of GIEs in the northeastern United States may be challenged as changes in the amount and timing of precipitation and increasing air temperatures attributed to climate change affect the groundwater that sustains these systems.

Connecticut, Delaware, District of Columbia, Maine

Evaluating machine learning approaches to identify and predict oil and gas produced water lithium concentrations

Recently, the demand for battery-grade lithium has substantially increased, largely due to electrification of the transportation sector. The search for new lithium sources has turned to produced waters (frequently brines), a large-volume wastewater by-product of oil and gas extraction. Geochemical analysis indicates the presence of varying concentrations of lithium from produced water samples collected across the United States and represented in the U.S. Geological Survey’s National Produced Water Geochemical Database, as well as mixtures of Marcellus Shale produced water included in the Pennsylvania Department of Environmental Protection’s Oil and Gas Well Waste Reports. We first examined whether the geochemical signature of the lithium-bearing produced waters is sufficiently distinct so that machine learning (ML) can be used to correctly classify samples to the formation of origin. The produced water sample data used to assess classification accuracy were from the Marcellus Shale, Utica Shale and Point Pleasant Formation (Utica), and Smackover Formation oil and gas wells. Further, we evaluated the potential for ML to accurately classify Marcellus Shale produced water spatially (i.e., northeast versus southwest Pennsylvania). We then investigated whether ML algorithms applied to a suite of geochemical concentration data (i.e. Ba, Br, Cl, K, Mg, Sr) may be used to predict the lithium concentration of an unknown sample. Finally, we applied an estimated economic lithium grade cutoff of 150 milligrams per liter (mg/l) and assessed the utility of ML to predict whether a produced water sample would fall above or below the grade cutoff based on the suite of geochemical parameters. Four machine learning algorithms—Random Forest (RF), Gradient Boosting Trees (GBT), Extreme Boosting (XGBoost), and Deep Neural Networks (DNN) were assessed. This study successfully demonstrates that all four machine learning methods can precisely and accurately estimate lithium concentrations and geologic formation classification. The products of this study contribute to the growing body of knowledge aimed at expanding the lithium resource base within the United States.

Alabama, Arkansas, Florida, Georgia, Louisiana, Mi

Groundwater quality near the Placerita Oil Field, California, 2018

Groundwater-quality data and potential fluid-migration pathways near the Placerita Oil Field in Los Angeles County, California, were examined by the U.S. Geological Survey to determine if oil-field fluids (water and gas from oil-producing and non-producing zones) have mixed with groundwater resources. Six of the 13 new groundwater samples collected for this study contained petroleum hydrocarbons, thermogenic gas, inorganic chemical signatures, and (or) isotopic values consistent with potential mixing with fluids from hydrocarbon-bearing formations. For historical groundwater samples, benzene was the most detected petroleum hydrocarbon. The historical groundwater samples with a benzene concentration greater than 0.5 micrograms per liter were from environmental monitoring wells at industrial or commercial facilities unrelated to oil and gas development that, in many cases, have identified soil or groundwater contamination and were not typically analyzed for other constituents that could provide additional lines of evidence for potential mixing with oil-field fluids. Methane was not detected in any of the 12 historical samples with a reported measurement. Reviewing historical data revealed factors that could potentially adversely affect groundwater quality in the study area. These factors include modified hydraulic gradients caused by large volumes of water extracted from the main production area and reinjected downgradient into nonproducing zones, well-barrier failures in wells constructed in the northern part of the oil field before the 1970s, well-barrier failures in produced-water disposal wells downgradient from the main production area, and naturally occurring hydrocarbons at shallow intervals. The groundwater samples most geochemically similar to samples from hydrocarbon-bearing formations were in areas where hydrocarbons are naturally occurring at shallow intervals and where oil development is at shallow depths. Additional data for hydraulic heads, water quality, and formation temperatures at multiple depths in areas with large injection volumes and well-integrity issues are needed to evaluate whether those factors have contributed to mixing between fluids from oil-producing or injection formations and groundwater resources.

California

Cancer risk and estimated lithium exposure in drinking groundwater in the US

Importance Lithium is a naturally occurring element in drinking water and is commonly used as a mood-stabilizing medication. Although clinical studies have reported associations between receiving lithium treatment and reduced cancer risk among patients with bipolar disorder, to our knowledge, the association between environmental lithium exposure and cancer risk has never been studied in the general population. Objectives To evaluate the association between exposure to lithium in drinking groundwater and cancer risk in the general population. Design, Setting, and Participants This cohort study included participants with electronic health record and residential address information but without cancer history at baseline from the All of Us Research Program between May 31, 2017, and June 30, 2022. Participants were followed up until February 15, 2023. Statistical analysis was performed from September 2023 through October 2024. Exposure Lithium concentration in groundwater, based on kriging interpolation of publicly available US Geological Survey data on lithium concentration for 4700 wells across the contiguous US between May 12, 1999, and November 6, 2018. Main Outcome and Measures The main outcome was cancer diagnosis or condition, obtained from electronic health records. Stratified Cox proportional hazards regression models were used to estimate the hazard ratios (HRs) and 95% CIs for risk of cancer overall and individual cancer types for increasing quintiles of the estimated lithium exposure in drinking groundwater, adjusting for socioeconomic, behavioral, and neighborhood-level variables. The analysis was further conducted in the western and eastern halves of the US and restricted to long-term residents living at their current address for at least 3 years. Results A total of 252 178 participants were included (median age, 52 years [IQR, 36-64 years]; 60.1% female). The median follow-up time was 3.6 years (IQR, 3.0-4.3 years), and 7573 incident cancer cases were identified. Higher estimated lithium exposure was consistently associated with reduced cancer risk. Compared with the first (lowest) quintile of lithium exposure, the HR for all cancers was 0.49 (95% CI, 0.31-0.78) for the fourth quintile and 0.29 (95% CI, 0.15-0.55) for the fifth quintile. These associations were found for all cancer types investigated in both females and males, among long-term residents, and in both western and eastern states. For example, for the fifth vs first quintile of lithium exposure for all cancers, the HR was 0.17 (95% CI, 0.07-0.42) in females and 0.13 (95% CI, 0.04-0.38) in males; for long-term residents, the HR was 0.32 (95% CI, 0.15-0.66) in females and 0.24 (95% CI, 0.11-0.52) in males; and the HR was 0.01 (95% CI, 0.00-0.09) in western states and 0.34 (95% CI, 0.21-0.57) in eastern states. Conclusions and Relevance In this cohort study of 252 178 participants, estimated lithium exposure in drinking groundwater was associated with reduced cancer risk. Given the sparse evidence and unknown mechanisms of this association, follow-up investigation is warranted.

contiguous United States

Determination of per- and polyfluoroalkyl substances in water by direct injection of matrix-modified centrifuge supernatant and liquid chromatography/tandem mass spectrometry with isotope dilution

A direct-injection liquid chromatography/tandem mass spectrometry method was developed to determine 34 per- and polyfluoroalkyl substances (PFAS), including selected branched isomers, in centrifuge supernatant of matrix-modified (amended with approximately 50 percent methanol) water samples. The method has been validated in reagent water, surface water, groundwater, and wastewater effluent. Other water types (for example, drinking water, untreated wastewater, and landfill leachate) have been analyzed by the method but not systematically validated. Recovery of isotope-dilution standards, added to each sample, may be used to assess method performance in nonvalidated matrices on a sample-by-sample basis. Using this method, PFAS concentrations were determined in the range of 2–2,000 nanograms per liter in water samples. This range can be extended by diluting concentrated samples. At circumneutral pH, most compounds are present in the environment in their ionized form, and data are reported as such (for example, perfluorooctanoic acid is referred to as “perfluorooctanoate” [PFOA], perfluorooctane sulfonic acid is referred to as “perfluorooctane sulfonate” [PFOS]). Sample preparation procedures were designed without the use of filtration and with minimum sample handling steps to mitigate procedural losses of target compounds due to sorption to surfaces. Further, isotope-dilution quantification allowed for the correction of bias that may result from procedural losses, matrix-induced signal suppression or enhancement, and other factors. Validation experiments to characterize bias and variability, method detection level, and holding time were done in four distinct water matrices—reagent water, surface water, treated wastewater effluent, and groundwater—at multiple concentration levels. Mean PFAS recoveries met data quality objectives of bias and variability studies in all four validation matrices except for two compounds with low and variable recovery in the reagent water matrix only. Isotope-dilution standards, treated as surrogate compounds, were analyzed in more than 1,500 customer-submitted environmental samples with aggregate recovery of 102.5±6.5 percent (mean±standard deviation). Maximum holding times for all target compounds in the four validation matrices were 28 days for refrigerated samples and 90 days for frozen samples.

Techniques and Methods

Characterization of the hydrogeologic framework, groundwater-flow system, geochemistry, and aquifer hydraulic properties of the shallow groundwater system in the Wilcox and Lorraine process areas of the Wilcox Oil Company Superfund site near Bristow, Oklahoma, 2022

The Wilcox Oil Company Superfund site (hereinafter referred to as “the site”) was formerly an oil refinery northeast of Bristow in Creek County, Oklahoma. Historical refinery operations contaminated the soil, surface water, streambed sediments, alluvium, and groundwater with refined and stored products at the site. The Wilcox and Lorraine process areas are where the highest concentrations of volatile organic compounds, semivolatile organic compounds, polycyclic aromatic hydrocarbons, and trace elements (including metals) (collectively hereinafter referred to as “contaminants”) were measured in a local shallow perched groundwater system within the alluvium (hereinafter referred to as the “alluvial aquifer”) at the site during previous site assessments. In order to understand the potential migration of contaminants through the soil and groundwater in these areas, the U.S. Geological Survey, in cooperation with the U.S. Environmental Protection Agency, investigated aquifer characteristics of the alluvial aquifer in the Wilcox and Lorraine process areas of the site to (1) document hydraulic conductivity and other aquifer characteristics of the alluvial aquifer that govern contaminant fate and transport, (2) describe the geospatial extent and concentration of the contaminants in the alluvial aquifer in the Wilcox and Lorraine process areas, and (3) describe the geochemical controls pertaining to oxidation and reduction governing the fate and transport and the degradation potential of contaminants in the groundwater. Various data were compiled and collected to evaluate the aquifer characteristics at the site including the hydrogeologic framework, groundwater-flow system, geochemistry, and hydraulic properties of the aquifer. A total of 20 new (2022) groundwater monitoring wells were installed at the site to collect data used to supplement groundwater-level altitude and groundwater-quality data collected from older, existing groundwater monitoring wells and piezometers. Data compiled and collected for the study were used to evaluate the characteristics of the alluvial aquifer at the site. These aquifer characteristics are defined by the hydrogeologic framework, groundwater-flow system, geochemistry, and hydraulic properties of the aquifer.

Oklahoma

Water quality of the Boca Raton canal system and effects of the Hillsboro Canal inflow, southeastern Florida, 1990-91

The City of Boca Raton in southeastern Palm Beach County, Florida, is an urban residential area that has sustained a constant population growth with subsequent increase in water use. The Boca Raton network of canals is controlled to provide for drainage of excess water, to maintain proper coastal ground-water levels to prevent saltwater intrusion, and to recharge the surficial aquifer system from which the city withdraws potable water. Most of the water supplied to the Boca Raton canal system and the surficial aquifer system, other than rainfall and runoff, is pumped from the Hillsboro Canal. The Biscayne aquifer, principal hydrogeologic unit of the surficial aquifer system, is highly permeable and there is a close relation between water levels in the canals and the aquifer. The amount of water supplied by seepage from the conservation areas is unknown. Because the Hillsboro Canal flows from Lake Okeechobee and Water Conservation Areas 1 and 2, which are places of more highly mineralized ground water and surface water, the canal is a possible source of contamination. Water samples were collected at 10 canal sites during wet and dry seasons and analyzed for major inorganic ions and related characteristics, nutrients, and trace elements. All concentrations were generally within or less than the drinking-water standards established by the Florida Department of Environmental Protection. The high concentrations of sodium and chloride that were detected in samples from the Boca Raton canal system are probably from the more mineralized water of the Hillsboro Canal. Other water-quality data, gathered from various sources from 1982 through 1991, did not indicate any significant changes nor trends. The data include pesticide and metal analyses of water samples and bottom sediments collected at four canal sites in the Boca Raton study area by the U.S. Geological Survey during 1982-84. The effects of the Hillsboro Canal on the water quality of the Boca Raton canal system are indicated by increased concentrations of sodium, chloride, dissolved solids, and total organic carbon. Concentrations of the constituents in the canal water generally decrease with distance from the Hillsboro Canal pumping station and are the result of dilution by receiving canal waters.

Florida

Overstorey mortality promotes juvenile piñon pine growth during favourable weather at cooler, wetter sites

Hotter droughts have resulted in widespread tree die-off events globally, frequently leading to regeneration failure. Dry forest recovery often depends on the growth and survival of extant juvenile trees. However, it is unclear how microenvironmental changes following overstorey tree die-off affect juvenile trees, particularly in dryland systems where tree recruitment is typically limited by water availability and heat stress. We simulated an overstorey tree die-off event by girdling trees in piñon-juniper woodlands across the south-western United States. We sampled juvenile piñon pine growth from live and dead overstorey treatments across six study sites spanning a regional latitudinal gradient and local elevational gradients. We examined how juvenile branch and needle growth differed between live and dead overstorey treatments, and whether responses varied with weather conditions and juvenile tree size following overstorey mortality. We found greater juvenile branch and needle growth under dead compared with live overstorey trees for 2 years following overstorey mortality at mid- and high-elevation sites which are typically cooler and wetter than the other sites. These observed growth releases were contingent on favourable post-mortality weather conditions. Higher growth under dead overstorey occurred at sites experiencing near-average climatic water deficits compared with sites experiencing above-average climatic water deficits. Growth at all sites increased from the first to second year after overstorey mortality. Across sites, growth was unrelated to juvenile tree size. Synthesis . Our results underscore differentiation in juvenile responses to overstorey tree die-off driven by local site conditions and weather across the range of Pinus edulis . Overstorey mortality resulted in consistently higher juvenile growth only at climatically favourable sites and during favourable weather, while unmeasured microsite differences could help account for variation observed at the hottest and driest site. Results from less climatically favourable sites suggest that overstorey trees neither directly limit nor facilitate juvenile growth, though further study over longer timeframes is needed to resolve the pace and magnitude of potential recovery or decline. Overall, juvenile vigour may be promoted following overstorey mortality only in a narrow spatial (site) and temporal (weather) environmental context, suggesting additional vulnerabilities for piñon populations under more arid conditions.

Arizona, Colorado

Reconstruction of Holocene and Last Interglacial vegetation dynamics and wildfire activity in Southern Siberia

Wildfires are a rapidly increasing threat to boreal forests. While our understanding of the drivers behind wildfires and their environmental impact is growing, it is mostly limited to the observational period. Here we focus on the boreal forests of southern Siberia and exploit a U–Th-dated stalagmite from Botovskaya Cave, located in the upper Lena region of southern Siberia, to document wildfire activity and vegetation dynamics during parts of two warm periods: the Last Interglacial (LIG; specifically part of the Last Interglacial maximum between 124.1 and 118.8 ka) and the Holocene (10–0 ka). Our record is based on levoglucosan (Lev), a biomarker sensitive to biomass burning, and on lignin oxidation products (LOPs) that discriminate between open and closed forest and hard- or softwood vegetation. In addition, we used carbonate carbon stable isotope ratios ( δ 13 C ), which reflect a dominant control of the host rock, to evaluate soil respiration and local infiltration changes. Our LOP data suggest that, during the Last Interglacial, the region around Botovskaya Cave was characterised by open forest, which by ca. 121.5 ka underwent a transition from fire-resistant hardwood to fire-prone softwood. The Lev record indicates that fire activity was high and increased towards the end of Last Interglacial just before 119 ka. In contrast, the Holocene was characterised by a closed-forest environment with mixed hard- and softwood vegetation. Holocene fire activity varied but at a much lower level than during the Last Interglacial. We attribute the changes in wildfire activity during the intervals of interest to the interplay between vegetation and climate. The open forests of the Last Interglacial were more likely to ignite than their closed Holocene equivalents, and their flammability was aided by warmer and drier summers and a stronger seasonal temperature contrast due to the increase in seasonal insolation difference compared to the Holocene. Our comparison of the last two interglacial intervals suggests that, with increasing global temperatures, the boreal forest of southern Siberia may become progressively more vulnerable to higher wildfire activity.

Botovskaya Cave, Siberia

Rare earth element potential in coal and coal ash in the U.S. Gulf Coast

United States heavy reliance on imports of critical minerals (CMs), including rare earth elements (REEs), underscores the importance of development of domestic sources. The study objective was to quantify CM and REE concentrations in coal and coal ash in the US Gulf Coast region. CM and REE concentrations were measured for 118 samples from outcrops and 14 mines in the Gulf Coast. Results show that total REE + Yttrium (REY) concentrations (dry coal basis) are comparable to those of the upper continental crust (UCC) with localized hot spots, such as the Texas Gibbons Creek mine (REY ≤ ~ 2860 ppm). When normalized to UCC REY concentration (169 ppm, dry coal basis), REY to UCC ratios for Gulf Coast coal samples range from 0.1 to 17 (median ratio 0.6). REE extractability from lignites is high (median: 63%–93%) using environmentally benign weak acid. In addition to raw coal, coal ash from power plants could also serve as an REE source with a median ratio of REY in ash relative to coal of 4; however, extractability from coal ash is generally much lower (≤ 5% using the same weak acid as in coal). The median basket price for extracted REY as oxides from coal, assuming 70% extractability, is $3.2 per tonne of coal and $186 billion based on 58 billion metric tonnes of dry coal in the Gulf Coast. REEs important for magnets (Pr + Nd + Tb + Dy) account for ~ 80% of the total value. The corresponding median basket price for extracted REY as oxides from coal ash, assuming ~ 30% extractability, is ~$4.4 per tonne of ash and $1.2 billion based on 258 million tonnes of ash. REE production from coal would likely require co-products, such as activated carbon or humic acids, to attain economic viability. Production of REEs from coal ash could offset remediation costs related to potential water contamination. This reconnaissance study shows the potential for REE production from coal and coal ash in the Gulf Coast; however, carbon coproducts and/or societal benefits would likely be required for socioeconomic viability.

Alabama, Florida, Louisiana, Mississippi, Texas

Geological context and significance of the clay-sulfate transition region in Mount Sharp, Gale crater, Mars: An integrated assessment based on orbiter and rover data

On Mars, phyllosilicate (“clay”) minerals are often associated with older terrains, and sulfate minerals are associated with younger terrains, and this dichotomy is taken as evidence that Mars’ surface dried up over time. Therefore, in situ investigation of the Mount Sharp strata in Gale crater, which record a shift from dominantly clay-bearing to sulfate-bearing minerals, as seen in visible−near-infrared orbital reflectance spectra, is a key science objective for the Mars Science Laboratory (MSL) Curiosity rover mission. Here, we present regional (orbiter-based) and in situ (rover-based) evidence for a low-angle erosional unconformity that separates the lacustrine and marginal lacustrine deposits of the Carolyn Shoemaker formation from the dominantly eolian deposits of the lower Mirador formation within the orbitally defined clay-sulfate transition region. The up-section record of wetter (Carolyn Shoemaker formation) to drier (lower Mirador formation) depositional conditions is accompanied by distinct changes in diagenesis. Clay minerals occur preferentially within the Carolyn Shoemaker formation and are absent within the lower members of the Mirador formation. At and above the proposed unconformity, strata are characterized by an increase in diagenetic nodules enriched in X-ray amorphous Mg-sulfate. Early clay formation in the Carolyn Shoemaker formation may have created a hydraulic barrier such that later migrating magnesium- and sulfur-rich fluids accumulated preferentially within the lower members of the Mirador formation. The proposed unconformity may have also acted as a fluid conduit to further promote Mg-sulfate nodule formation at the Carolyn Shoemaker−Mirador formation boundary. These results confirm an association of the clay-sulfate transition with the drying of depositional environments, but they also suggest that at least some orbital sulfate signatures within the region are not time-congruent with the environmental signals extracted from primary sedimentology. Our findings highlight that complex interactions among primary depositional environment, erosion, and diagenesis contribute to the transition in clay-sulfate orbital signatures observed in the stratigraphy of Mount Sharp.

GSA Bulletin

Evaluation of solid bitumen created from marine oil shale bituminite under hydrous and anhydrous pyrolysis conditions

To test the influence of environmental conditions on aromaticity of solid bitumen generated during petroleum generation, four organic-rich (26–36 wt% total organic carbon) oil shale samples collected from the Neoproterozoic–Lower Cambrian restricted marine Salt Range Formation in the upper Indus Basin, Pakistan, were pyrolyzed under hydrous and anhydrous conditions. Experiments used closed system batch reactors at subcritical water temperatures between 300 and 370°C for 72 h. Thermal conversion of bituminite in the Salt Range oil shales created a newly formed solid bitumen, similar to previous observations from experiments on the Eocene lacustrine Green River Formation Mahogany zone oil shale. Newly formed solid bitumen in the Salt Range Formation oil shales generally has higher reflectance (R o ) in hydrous residues compared to anhydrous experiments subjected to the same time-temperature conditions, also similar to prior observations. This finding supports the hypothesis that radical disproportionation is favored in the presence of hydrogen contributed by water, promoting aromatization in the solid bitumen residue with concomitant increased expulsion of saturated hydrocarbons. Indigenous solid bitumen (and vitrinite in a comparison sample) also shows higher reflectance values in hydrous versus anhydrous residues, indicating that additional aromatization in the presence of exogenous hydrogen occurs both in newly formed organic matter and in organic matter that is present throughout the experiment. Despite similarities in their bulk rock geochemical screening parameters, R o evolution shows different trajectories amongst the four Salt Range oil shales, suggesting as-yet undetermined differences in kinetic properties which are probably related to differences in a priori chemical composition. These results have implications for the use of solid bitumen reflectance (BR o ) as a thermal proxy, suggesting BR o values and appearance could vary as a function of the concentration of water. Variation in water concentration may be present at the reservoir or formation scale, but may also be present at a much finer scale in tight oil shales where permeability is several orders of magnitude lower than conventional reservoirs. Therefore, local variations in the presence of water potentially could explain substantial variation in BR o values and appearance in closely spaced source rock samples and even within an individual microscope field.

Journal of Analytical and Applied Pyrolysis

Investigation of land cover within wetland complexes at Dixie Meadows, Churchill County, Nevada, from October 2015 to January 2022

The U.S. Geological Survey investigated land cover at subannual time steps within six wetland areas in Dixie Valley, Churchill County, Nevada, from October 2015 to January 2022. As requested by the U.S. Fish and Wildlife Service, we used aerial photography and satellite remote sensing data to map surface water and other land cover types within the wetland complexes. We identified five land cover classes using the green normalized difference vegetation index (gNDVI) and its inverse relationship to the normalized difference water index (NDWI) within three U.S. Department of Agriculture National Agriculture Imagery Program aerial images (acquired in 2015, 2017, and 2019) and 110 European Space Agency Sentinel-2 satellite images (acquired 2015–2022). The relative wetness of soil conditions within each land cover class is estimated by comparison to previously published observations of relative conductivity measured by 79 field-based sensors within the wetlands from 2019 to 2021. We mapped the areal coverage of the five land cover classes for approximately 385 acres (1,559,000 square meters [m²]) comprising six individual wetland complexes as well as a larger 1,298- acre (5,254,000-m 2 ) area of interest inclusive of the wetland complexes and adjacent landscape. Land cover of open water (Class 5) primarily within ponds at one of the wetland complexes comprised 8,333 m 2 , on average, of the wetland complexes. Land cover of mixed shallow surface water, saturated soil, and vegetation (Class 4) comprised 111,723 m 2 on average of the wetland complexes. Land cover of dense green vegetation canopy cover (Class 3) that often (46 percent of observations) had underlying surface water or saturated soil conditions comprised 592,522 m 2 on average of the wetland complexes. The remaining areas of the wetland complexes not mapped as these three land cover types (Classes 2 and 1) had sparse vegetation or bare soil cover and commonly (greater than or equal to 67 percent of observations) had dry soil conditions. The investigation of land cover detailed in this report could inform future efforts to map land cover more precisely via higher resolution remote sensing or ground-based surveying or could be incorporated with other environmental monitoring data to characterize habitat and hydrology of the wetland complexes at Dixie Meadows.

Nevada

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