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Chemostratigraphy of the Cretaceous Hue Shale in Arctic Alaska: Exploring paleoceanographic controls on trace element enrichment, organic matter accumulation, and source-rock evolution

We document chemostratigraphy in an outcrop of late Albian to early Campanian (∼103–82 Ma) marine source rocks to better understand paleoenvironmental controls on trace element (TE) enrichment and organic matter accumulation in the distal Colville foreland basin of Arctic Alaska and how those drivers are linked to arc volcanism and successions of Cretaceous oceanographic and climatic biogeochemical events. This unique, 113-m-thick section of Cretaceous Hue Shale deposited during a series of previously undocumented Arctic Cretaceous oceanic anoxic events (Lease et al., 2024) is the only known exposure of thermally immature (0.48–0.52% R o , random vitrinite reflectance) Hue Shale in Arctic Alaska. Strata comprise mainly clay-rich mudstone with elevated total organic carbon (TOC) and hydrogen index values reaching 26.3 wt% (mean = 7.5 wt%) and 689 mg hydrocarbon (HC)/g TOC (mean = 385 mg HC/g TOC), respectively. Maceral composition consists predominantly of fluorescent amorphous organic matter, with abundant brightly fluorescent alginite, including Tasmanites , acritarchs, and Leiosphaeridia . Discrete layers of volcanic ash (preserved as bentonite) are present throughout the section and provide quantitative age control based on U–Pb dates. Chemostratigraphic trends are investigated to advance our understanding of local oceanographic conditions and controls on stratigraphic and temporal heterogeneity of Brookian source rocks. Concurrent sedimentary enrichment in Mo, U, V, Pb, and Cu across the Albian–Cenomanian boundary of the exposed basal gamma-ray zone, may reflect anoxic to euxinic benthic redox conditions favoring organic matter accumulation and preservation. Fluctuating degrees of anoxia-euxinia are inferred throughout the overlying Hue Shale succession, reflected by varying patterns of TE enrichment and TE–TOC covariation. Elevated C org /P molar ratios (>250) across most of the section, with several values exceeding 690, signify that enhanced biological productivity is sustained throughout deposition. Enhanced productivity, recorded by both C org /P and excess Ba, also parallels increases in source rock richness (elevated TOC and S 2 values) during the late Albian–early Cenomanian and late Cenomanian – Turonian. Enhanced productivity and variations in oceanic circulation/stratification likely both drove changes in benthic redox conditions that favored organic carbon accumulation and preservation. Increased continental arc volcanism (e.g., Okhotsk–Chukotka volcanic belt) and High Arctic Large Igneous Province magmatic eruptions throughout the Cretaceous, inferred to have influenced nutrient cycling and local aqueous nutrient availability, also have been invoked as potential drivers of organic carbon burial and source-rock development across the sedimentary sequence. Results presented here document the organic-rich and oil-prone source-rock quality of the Hue Shale in the distal part of the Colville foreland basin and bolster the potential for a Cretaceous petroleum system beneath the eastern North Slope.

Alaska

Conventional hydrothermal power-producing systems of the Great Basin, USA

As part of the update to the electric-grade conventional hydrothermal assessment of the Great Basin, USA, Monte Carlo analyses of identified resources within explored regions will be performed to make estimates of discovered resources and associated uncertainty. Analyses use conditional statistics where estimates are conditioned upon a hydrothermal favorability map, allowing for the likelihood that more resources exist in regions of higher hydrothermal favorability. For these analyses, a dataset of identified hydrothermal systems is compiled, and the new compilation is described herein. Recognizing that a single hydrothermal system may be developed with multiple power plants, and that the hydrothermal upflow zone may be several kilometers across with many measurements characterizing a single hydrothermal system, a procedure was developed and employed to create clusters of points (power plants, measurements, etc.) that are associated with a single system, and a new central point was defined as the best estimator of the center of the hydrothermal system. Hydrothermal systems were uniquely identified by grouping electric-grade hydrothermal measurements and operating power plants within a distance of 10 km. Groups that are >10 km apart are assumed to be different electric-grade hydrothermal systems. While 10 km was used as the threshold, most systems were significantly further apart, and most points within groups were typically within 5 km of each other. A well measurement was considered an electric-grade measurement of a hydrothermal system if it had two properties: a measured temperature of >85 °C and evidence of hydrothermal convection. Other points that were added to the dataset are locations of operating powerplants or locations that have been classified as an electric-grade hydrothermal resource by either the U.S Geological Survey (USGS) or the Great Basin Center for Geothermal Energy. After all points are assigned to systems, new points were computed with the goal of identifying the center of the throat of the hydrothermal upflow zone. If operating powerplants exist for a system, then the arithmetic average of all power plant locations is used. Otherwise, if USGS made an estimate, that location is used. In the absence of both powerplants or USGS estimates, the arithmetic average of all electric-grade measurement locations is used. An example is shown of how these newly compiled locations might be ranked for uncertainty analyses, where higher confidence is assumed if measured temperature is higher and there are many supporting measurements indicating an electric-grade resource. In summary, 28 systems have operating power plants, an additional 78 systems are known identified electric-grade hydrothermal resources, and 99 new systems were identified as probable electric-grade systems with varying levels of confidence. These 205 locations are shown as a function of a recent hydrothermal favorability map, conceptually illustrating the conditional statistics that can be used to make estimates of the undiscovered resources of the Great Basin. An accompanying data release provides summaries of developed capacity by system and USGS estimates of likely total capacity and associated uncertainty.

Arizona, California, Idaho, Nevada, Oregon, Utah

Streamflow, ground-water recharge and discharge, and characteristics of surficial deposits in Buzzards Bay Basin, southeastern Massachusetts

Streamflow measurements at 14 low-flow partial-record stations and two discontinued streamflow-gaging stations were related to concurrent streamflows at six long-term streamflow-gaging stations to estimate streamflows at selected flow durations from 50 to 99 percent for water years 1967-91. At low flows, stream discharge per square mile generally increased with increasing percentage of subbasin underlain by stratified-drift deposits. At the 70-, 90-, and 99-percent flow durations, subbasins underlain primarily by stratified-drift deposits had stream discharges per square mile at least 2, 4, and 8 times greater, respectively, than subbasins underlain primarily by till and bedrock deposits. Streamflow measured three times at the Paskamanset River showed that streamflows downstream of municipal pumped wells increased at a lower rate per unit drainage area than streamflows upstream of the pumped wells. When pumpage from wells near the river was added to measured streamflow at the most downstream station, the sum was similar to the potential streamflow at the station if its streamflow per unit area was the same as that upstream from the pumped wells. Mean ground-water recharge and discharge rates were computed from continuous records of daily mean discharge during water years 1967-91 for six streamflow-gaging stations in southeastern Massachusetts and Rhode Island. Estimates of mean ground-water recharge were 19.7 to 22.6 inches per year for stations with drainage areas primarily underlain by till and bedrock deposits, and 23.8 to 25.2 inches per year for stations with drainage areas primarily underlain by stratified-drift deposits. During drought years, annual ground-water recharge can be less than 50 percent of the mean ground-water recharge rate for water years 1967-91. Estimates of ground-water discharge rates generally were 1 to 4 inches per year less than estimates of ground-water recharge rates. Ground-water discharge-duration curves were calculated from hydrograph separation of streamflow records at the six continuous streamflow-gaging stations for water years 1967-91. When streamflows were less than the median streamflow (50-percent duration), ground-water discharges averaged 85.7 percent of the total streamflow at the six streamflow-gaging stations. Ground-water discharges were estimated at the 14 low-flow partial-record stations and two discontinued streamflow-gaging stations by multiplying streamflows at the selected flow durations from 50 to 99 percent for water years 1967-91 by 85.7 percent. Data on surficial deposits in the basin were obtained by drilling 10 wells, by conducting 12 seismic-refraction surveys, and by collecting well log data for 313 wells from consulting firms and the Massachusetts Department of Environmental Management. These data indicated that a few minor corrections could be made to existing saturated thickness maps for stratified-drift deposits in Buzzards Bay Basin. Few well logs were detailed enough to estimate transmissivities; thus existing transmissivity maps were not updated for stratified-drift deposits in the basin.

Massachusetts

Multiple-well monitoring site adjacent to the Midway- Sunset and Buena Vista Oil Fields, Kern County, California

Groundwater quality in and around oil fields in the Southern San Joaquin Valley is of interest to many California residents that rely heavily on groundwater for domestic, commercial, and agricultural use. To help assess the effects of historical oil-field activities and natural geologic sources on groundwater near the southwest margins of the Kern County Groundwater Subbasin, a multiple-well monitoring site was installed near the administrative boundary between the Midway-Sunset and Buena Vista Oil Fields in Kern County, California. The installation of the Midway-Sunset Buena Vista multiple-well monitoring site (MSBV) supports regional analysis of the relations of oil and gas sources to groundwater quality by providing information about the geology, hydrology, geophysical properties, and water quality of the alluvial and upper Tulare aquifers in areas where groundwater data were limited. Data collected from the site included drill cuttings, whole core samples, sidewall core samples, mud-gas analysis, borehole geophysical logs, depth to water measurements, and water quality samples. Whole cores were scanned using dual energy computed tomography. Subsamples of selected cores were analyzed for density, porosity, specific retention, and bulk minerology. Thin sections of the subsamples were prepared, photographed, and examined. Two samples were analyzed using scanning electron microscope technology to examine the microporosity of diatomite laden sediment. Instrumentation installed in the wells collect hourly depth to water measurements. Analysis of the data show there is 355 feet of alluvium overlying the Tulare Formation at the well site. The contact between the two formations is an aquitard resulting in a perched aquifer in the alluvium and unconfined aquifer in the Tulare Formation. The alluvium is more heterogenous and finer grained than the Tulare Formation resulting in markedly higher porosity in the alluvium compared to the Tulare Formation. Higher specific retention observed in the alluvium is attributed to the finer grained sediment and greater abundance of reworked diatomite (as represented by opal-CT [cristobalite-tridymite]) compared to the Tulare Formation. Total dissolved solids (TDS) approached or exceeded 10,000 milligrams per liter (mg/L) in the alluvium from approximately 176 to 242 feet below land surface and at the top of the Amnicola clay at approximately 670 feet below land surface within the Tulare Formation. Elevated TDS, chloride, and boron concentrations in the alluvium and on top of the Amnicola clay likely reflect groundwater that is mixed with oil-field water. Water chemistry and modern-aged groundwater in the alluvial monitoring well (MSBV #3) are consistent with the oil-field water in the alluvium being derived from documented historical surface disposal of oil-field water upslope (northwest) of the site. Water chemistry and pre-modern groundwater age in the deeper Tulare monitoring well (MSBV #1) on top of the Amnicola clay are consistent with oil-field fluids derived from upslope natural geologic sources or old oil wells that leak in the subsurface. Shallow groundwater in the Tulare (MSBV #2) is not affected by mixing with oil-field sources.

EarthArXiv

Hyperspectral (VNIR-SWIR) analysis of roll front uranium host rocks and industrial minerals from Karnes and Live Oak Counties, Texas Coastal Plain

VNIR-SWIR (400–2500 nm) reflectance measurements were made on the surfaces of various cores, cuttings and sample splits of sedimentary rocks from the Tertiary Jackson Group, and Catahoula, Oakville and Goliad Formations. These rocks vary in composition and texture from mudstone and claystone to sandstone and are known host rocks for roll front uranium occurrences in Karnes and Live Oak Counties, Texas. Spectral reflectance profiles, 569 in total, were reduced to 125 representative spectral signatures, which were analyzed using the U.S. Geological Survey's (USGS) Material Identification and Characterization Algorithm (MICA). MICA uses an automated continuum-removal procedure together with a least-squares linear regression to determine the fit of observed sample spectral absorption features to those of reference mineral standards in a spectral library. The reference minerals include various clay, mica, carbonate, ferric and ferrous iron minerals and their mixtures. In addition, absorption feature band-depth analysis was done to identify rock surfaces exhibiting absorption features related to uranium and zeolite minerals, which were not included in the command files used to execute MICA. Rocks from each of the four geologic units produced broadly similar spectral signatures as a result of comparable mineral compositions, but there were some notable differences. For example, Ca- and Na-montmorillonite was matched most frequently to the spectral absorption features in 2-μm (∼2000–2500 nm) wavelengths, while goethite occurred often at 1-μm (∼400–1000 nm) wavelengths. The latter is related to limonitic iron-staining in and around oxidized zones of the uranium roll front as described in previous papers. Rocks of the Jackson Group differed from those of the Catahoula, Oakville and Goliad units in that the former exhibited spectral features we interpret as being due to the presence of lignite-bearing mudstone layers. Goliad rocks exhibit spectral features related to dolomite, gypsum, anhydrite, and an unidentified green clay mineral that is possibly glauconite . Jackson Group rocks also exhibit weak but well-resolved absorption features at 964 and 1157 nm related to either or both zeolite minerals clinoptilolite and heulandite. These zeolite minerals and a few spectra exhibiting hydrous silica absorption features are indicative of alteration of volcanic glass in tuffaceous mudstone and claystone layers. A few sample spectra exhibited strong absorption features at around 1135 nm related to the uranium mineral coffinite. Both the 1135 nm coffinite and 1157 nm zeolite absorption features overlap somewhat, potentially making them difficult to distinguish without additional hyperspectral field, laboratory or remote sensing data. The results of this study were compared to mixtures of minerals described for ore, gangue and alteration minerals in deposit models for sandstone-hosted uranium, sedimentary bentonite and sedimentary zeolite. Use of these spectra can help facilitate mapping of both waste materials from the legacy mining of the above commodities, as well as future exploration and resource assessment activities.

Texas

Three-dimensional temperature maps of the Williston Basin, USA: Implications for deep hot sedimentary and enhanced geothermal resources

As part of U.S. Geological Survey's (USGS) efforts to identify and assess geothermal energy resources of the US, a three-dimensional (3D) geologic and thermal model has been constructed for the Williston Basin, USA. The geologic model consists of all sedimentary units above the Proterozoic and Archean crystalline rock (called basement herein), with a total sedimentary thickness of up to 5 km near the basin center. Twenty-nine geologic units were mapped from interpreted formation tops from 16,465 wells. A 3D temperature model was constructed to a depth of 7 km by constructing a 3D heat flow model for the sedimentary units, followed by estimating underlying temperature using a one-dimensional (1D) analytic solution for heat flow within the underlying crystalline basement. Using the sedimentary basin model, heat flow was simulated in 3D and was calibrated using three temperature datasets: 1) 24 high-confidence static temperature logs (equilibrium thermal profiles), 2) more than15,000 drill stem test (DST) measurements from >7,000 wells, and 3) more than 45,000 bottomhole temperature (BHT) measurements from >14,000 wells. The DST and BHT datasets provide broad spatial coverage, but are lower confidence, primarily because measurements were made prior to attaining thermal equilibrium. DST and BHT measurements were binned regionally to develop representative thermal profiles that generally agree with these lower quality data (hereafter called pseudowell temperature profiles). Layer properties (primarily thermal conductivity and compaction curves) were set to best estimate values, then the heat flow model was calibrated to fit pseudowell and static temperature logs primarily by adjusting basal heat flow to approximate the overall temperature profile. Minor adjustments to thermal conductivity allowed adjusting changes in slope at lithologic contacts. Resulting maps include 3D temperature and basal (bottom of sedimentary units) heat flow estimates, which are used as input for the temperature model of the basement. The crystalline basement temperature model uses an analytic 1D solution to the heat flow equation that requires estimates of heat flow and temperature at the upper boundary (i.e., the sediment/basement contact), radiogenic heat production within the crystalline basement, and reference thermal conductivity (i.e., uncorrected for temperature). Two regions of high heat flow are identified: 1) in western North Dakota along the North American Central Plains Conductivity Anomaly and 2) in eastern Montana near the Poplar dome. Within the sedimentary column in the center of the basin of the basin, an area of approximately 100,000 km2 is predicted to have moderate- to high-temperature geothermal resources (>90 °C) under the thickest sequences of sediments. Where thick insulation and high heat flow coincide, electric-grade resources can be less than 4 km deep. Assuming a maximum feasible drilling depth of 7 km, temperatures are predicted to be as high as 175 °C. The geologic model may be used to identify strata at sufficient temperatures that may have natural permeability or that may have conditions that favor development of enhanced/engineered geothermal systems resources.

Montana, North Dakota, South Dakota

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

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

Coastal barrier resilience and resistance: Analysis and metrics for characterizing coastal state

Barrier islands are shaped by a variety of short- and long-term environmental processes such as storms and relative sea-level rise. These islands, found along the estuarine-marine interface, provide ecosystem services including storm surge and wave attenuation, erosion protection to inland marshes, habitat for fish and wildlife, and recreation. Natural resource managers require actionable information on how barrier island resilience and resistance changes over time to understand how an island’s current state relates to past conditions and to inform restoration prioritization and implementation. The U.S. Geological Survey and The Water Institute collaborated on a study to develop indicators of resilience and resistance for barrier islands in Louisiana. Here, resilience captures island persistence on yearly to decadal time scales, and resistance captures persistence on event time scales of days to weeks. The indicators fall in two categories: Tier 1 Screening Metrics, that can be readily calculated from available data, are easily interpretable as an evaluation of barrier condition, and provide a high-level snapshot of overall barrier resilience and resistance; and Tier 2 Analysis Metrics, which are detailed metrics that required specialized analysis and interpretation and are more applicable to answering specific questions managers may have about barrier state. The research team derived Tier 1 resilience indicators from subaerial land and vegetation cover calculated from publicly available maps and products based on satellite imagery. By benchmarking the total land and vegetation extent against their respective historical maxima, this metric provides a snapshot of an island’s current state in the context of its long-term trajectory. The research team developed Tier 1 resistance indicators based on subaerial island configuration and water level recurrence as a proxy for evaluating island resistance to storms, which are the primary driver of short-term change. These Tier 1 metrics can be analyzed over time to provide a high-level assessment of how an island’s resistance decreases because of elevation loss or sea-level rise or increases due to restoration or natural recovery. The research team developed Tier 2 resilience and resistance indicators and associated analyses to provide detailed information for specific time periods or applications (e.g., wildlife management). These metrics include habitat coverage from high-resolution maps, which show composition changes over time to capture the evolving resilience of specific habitat types; high tide flooding analysis, which evaluate island area relative to specified flooding thresholds to characterize resistance in the short-term or, if analyzed over time, indicate changes in resilience; and hypsometric curve analysis, which allows managers to evaluate island area changes above their own elevation benchmarks of interest and similarly characterize resistance in the short-term or indicate changes in resilience if assessed over time. The research team calculated Tier 1 metrics of the barrier islands and headlands along the coast of Louisiana for the period of 1984 through 2021 and Tier 2 metrics for select times during that period depending on data available and quality. The results were captured in a report card for each barrier, which also includes an overview of the metrics and their interpretation; a restoration and storm history; and Tier 1 and Tier 2 metric analysis, including benchmarking against coastwide and regional values as well as to an island’s pre-restoration trajectory. These report cards provide a readily digestible synthesis of barrier condition and trajectory that coastal managers can use to support restoration prioritization and other decisions.

Louisiana

Hydrogeologic conceptual model of groundwater occurrence and brine discharge to the Dolores River in the Paradox Valley, Montrose County, Colorado

Salinity, or total dissolved solids (TDS), of the Colorado River is a major concern in the southwestern United States where the river provides water to about 40 million people for municipal and industrial use and is used to irrigate about 5.5 million acres of land. Much of the salinity in the Colorado River Basin is derived from natural interactions of surface water and groundwater with various geologic materials (rocks, soils, and alluvial deposits). The Dolores River in southwest Colorado is a major tributary of the Colorado River that historically accounts for about 6 percent of the salinity load to the Upper Colorado River Basin with the Paradox Valley being the primary source of salinity to the Dolores River. The Paradox Valley, one of several salt-anticline valleys in the region, is a fault-bounded topographic basin aligned with and exposing an underlying salt-anticline core. Salt deposits in the Pennsylvanian Paradox Formation of the Hermosa Group form an elongated salt diapir oriented northwest to southeast that is up to 12,000 feet (ft) thick beneath the present valley floor. Surface erosion, groundwater circulation, and weathering during Tertiary and Quaternary valley formation contributed to development of a cap rock, collapse features, breccia, and brine at the top of the exposed salt diapir. Today (2023), brine occurring in the brecciated cap rock and underlying salt deposits is in hydraulic connection with an overlying freshwater alluvial aquifer, and depending on seasonal river stage and hydrologic conditions, the brine discharges to the Dolores River causing the observed increase in salinity as the river crosses the Paradox Valley. To reduce salinity concentrations in the Dolores River, the Bureau of Reclamation (Reclamation) operates the Paradox Valley Unit (PVU). The PVU project consists of nine shallow brine pumping wells near the Dolores River and one deep disposal well where the brine is injected for disposal. When operational, the PVU pumping wells extract brine from the base of the alluvial aquifer that is piped and injected into a deep disposal well about 3 miles southwest of the PVU. The PVU became fully operational July 1, 1996, and by 2015, operation of the PVU had reduced salinity concentrations in the Dolores River by as much as 70 percent compared to pre-PVU conditions. In response to a 4.5 magnitude earthquake, injection operations, and thus PVU pumping, were ceased from March 2019 to June 2022. A trial period of PVU operation began in June 2022 with a reduced injection rate, and thus PVU pumping rate, of about two-thirds capacity to gather additional information and guide future operational decisions. In cooperation with Reclamation, the U.S. Geological Survey (USGS) developed this report to present the current (2023) understanding of groundwater and brine occurrence and discharge to the Dolores River in the Paradox Valley. Results from the compilation of spatial datasets, groundwater sampling and age dating, and aquifer tests are presented to provide improved understanding of the Paradox Valley hydrogeology, to supply datasets for a numerical groundwater-flow and brine-transport model, and to support future operations of the PVU. The hydrogeologic data provided herein, along with the most recent loading analysis for the Dolores River in the Paradox Valley, and a previous conceptual model for brine discharge to the river are used to present a conceptual understanding of groundwater occurrence in the Paradox Valley.

Colorado

Streamflow, base flow, and ground-water recharge in the Housatonic River basin, western Massachusetts and parts of eastern New York and northwestern Connecticut

Streamflows for selected flow durations from 1 to 99 percent and the August median streamflows were estimated for 11 long-term streamflow-gaging stations in and near the study area. Estimates of streamflow and associated standard errors were determined for selected flow durations from 50 to 99 percent and the August median streamflows for 21 low-flow partial-record stations and for selected flow durations from 1 to 99 percent and the August median streamflows for two partial-record stations and seven short-term discontinued streamflow-gaging stations. Median streamflows per square mile for the 10-, 50-, and 90-percent flow durations and the August median streamflows were 3.90, 1.01, 0.185, and 0.248 cubic feet per second per square mile. Streamflows per square mile at selected flow-duration discharges between 1 and 99 percent at the 41 stations were related to basin characteristics to explain differences in streamflow characteristics. Basin characteristics included basin elevations, extent of stratified-drift deposits, land use, aspect, and underlying bedrock geology types. Most streamflow differences were positively correlated to basin elevation differences, most likely because precipitation increases with elevation, and to stratified-drift deposits, which allow more precipitation to recharge the ground water and to discharge later than do till and bedrock deposits. Mean base flow was computed from continuous records of daily mean discharge at 11 long-term streamflow-gaging stations in and near the study area. Mean annual base flow ranged from 13.4 to 24.5 inches per year. Minimum annual base flow ranged from 45 to 72 percent of mean annual rates at the 11 long-term stations, and the ratio of base flow to streamflow (base-flow index) ranged from 0.55 to 0.80. Base-flow durations between 1 and 99 percent were calculated from streamflow records at the 11 long-term streamflow-gaging stations. Base flow accounted for 45.5 to 85.0 percent of total annual streamflow at the 1- and 99-percent flow durations. Ground-water-recharge rates were computed from continuous records of daily mean discharge at 11 long-term streamflow-gaging stations in and near the study area. Mean annual ground-water-recharge rates ranged from 17.5 to 22.4 inches per year at 10 of the 11 long-term stations. Mean annual ground-water-recharge rates ranged from 2 to 7 inches per year higher than base flow. Minimum annual ground-water-recharge rates ranged from 48 to 72 percent of mean annual ground-water-recharge rates. Mean annual potential ground-water recharge was estimated from monthly climatological data collected at six climatological stations in and near the study area. Mean potential ground-water recharge ranged from about 17.9 to 28.9 inches per year, with a median value of 22.6 inches per year. This median value compares well to that calculated by use of streamflow records at the 11 streamflow-gaging stations (20.0 inches per year). Streamflows per square mile for the 10-, 50-, and 90-percent flow durations at stations in and near the study area were similar to those computed for other unregulated long-term continuous streamflow-gaging stations in central and eastern Massachusetts. Base-flow and ground-water-recharge rates in the study area compared closely to results from other studies in southeastern Massachusetts and Rhode Island, which were based on the same computational methods.

Connecticut, Massachusetts, New York

Simulation of groundwater flow and brine discharge to the Dolores River in the Paradox Valley, Montrose County, Colorado

Salinity, or total dissolved solids (TDS), of the Colorado River affects agricultural, municipal, and industrial water users and is an important concern in the Western United States. In the Paradox Valley of southwestern Colorado, natural discharge of sodium-chloride brine to the Dolores River from the underlying core of a salt-valley anticline accounts for about 6 percent of the salinity load to the Colorado River. Formation of the Paradox Valley began during the Miocene, and subsequent erosion exposed the Pennsylvania Paradox Formation in the core of the anticline where a cap rock, collapse features, breccia, and sodium-chloride saturated brine developed at the top of the exposed salt diapir. The discharge of brine to the Dolores River is affected by these dissolution features, along with seasonal hydrologic conditions and density-dependent flow between older dense brine and the younger fresh groundwater in the overlying alluvial aquifer. To reduce TDS concentrations in the Dolores River through the Paradox Valley, the Bureau of Reclamation has pumped brine from a series of shallow wells adjacent to the river since July 1996. The pumped brine is collected and piped to a deep disposal well where it is injected into the Mississippian Leadville Limestone at a depth of about 4,570-meters below land surface. The pumping and injection operation is collectively known as the Paradox Valley Unit (PVU), and by 2015, the PVU had substantially reduced TDS concentrations in the Dolores River by about 70 percent. Since 2019, injection-pressure limits and related seismic activity have constrained deep-well injection and thus brine pumping at the PVU. In cooperation with the Bureau of Reclamation, the U.S. Geological Survey developed a MODFLOW-6 three-dimensional, variable-density groundwater flow and TDS transport model of the Paradox Valley to evaluate the effects of PVU pumping operations on brine discharge to the Dolores River and to guide additional research. The finite-difference model grid consists of 76 rows and 48 columns oriented from northwest to southeast in alignment with valley topography and groundwater-flow directions in the near-surface freshwater alluvial aquifer. A 7-layer hydrogeologic framework was developed from existing datasets to represent the alluvial aquifer, cap rock, collapse breccia, and groundwater flow and TDS transport from the underlying Paradox Formation salt to the Dolores River. The model represents a 33-year transient calibration period from 1987 through 2020 that includes pre-PVU conditions from 1987 through June 1996 and post-PVU conditions from July 1996 through 2020. A 1,000-year simulation of groundwater flow and coupled TDS transport computed the initial conditions for the subsequent 33-year transient simulation. Observations of precipitation, streamflow, evaporation, agricultural land use, and PVU brine pumping rates were used to specify appropriate boundary conditions to the model representing time-varying recharge, tributary streamflow, groundwater underflow, evapotranspiration (ET), and PVU pumping. Values for average monthly streamflow and TDS concentration at the upstream streamgage, the Dolores River at Bedrock (USGS streamgage 09169500), were specified as model input where the Dolores River enters Paradox Valley. Observed pumping from the PVU, water levels and TDS concentrations in groundwater, and streamflow and estimated TDS concentrations at the downstream streamgage, the Dolores River near Bedrock (USGS streamgage 09171100), were calibration targets that constrained the manual calibration of model parameters representing aquifer hydraulic conductivity, storage, streambed conductance, recharge, and (ET). Two primary model-calibration targets were the match between observed and simulated TDS mass flux from PVU pumping wells and the match between estimated and simulated TDS mass flux to the Dolores River. The simulated TDS mass withdrawn by pumping wells is calculated by the model as the product of the assigned pumping rate and simulated groundwater TDS concentrations. Because actual pumping rates were assigned as simulated values, the total simulated PVU pumping for the 33-year calibration is within 0.5 percent of the observed values. However, simulated concentrations and thus mass flux of TDS withdrawn by the PVU pumping wells were consistently about 26 percent less than observed values for all the simulated time periods (33-year simulation, pre-PVU, and post-PVU). The representation of brine inflow was explored through additional modeling to evaluate the effect of the simulated brine source on groundwater TDS concentrations. Results indicated that a saturated-salt constant-flux brine source best replicated the magnitude and transient pattern observed for TDS mass flux from PVU pumping wells. The simulated TDS mass flux to the Dolores River is compared to estimates based on observed streamflow and specific conductance (SC) data for the downstream streamgage. The calibrated model provided a close fit of simulated to measured streamflow at the downstream streamgage, and the calibrated model fit to estimated TDS concentrations at the downstream streamgage was reasonable. The greatest differences between simulated and estimated values occurred during drought periods from June 2000 to March 2003, May 2012 to June 2013, and October 2013 to October 2014, when simulated TDS concentrations in the river were greater than estimated concentrations. In general, simulated TDS mass flux to the river for the pre-PVU period is in good agreement with estimated values (2-percent difference), but the model overestimated TDS mass flux to the river by about 41 percent during the post-PVU period. The model uncertainty with respect to TDS mass flux to the river indicates other processes or model parameters not well represented by the model are affecting the system, especially during drought. During model calibration, the most sensitive parameters were identified as vertical hydraulic conductivity of the alluvial aquifer, conductance of the Dolores River streambed, ET extinction depth and rate, and recharge rate. Five 5-year scenarios of conditions for 2021–25 were simulated to assist evaluation of alternative strategies to manage the discharge of brine into the Dolores River. The first scenario simulates no PVU pumping and serves as a base case for comparison to the other scenarios. Two scenarios simulate the effects of varying withdrawal timing at an annual rate about one-third less than during 2010 through 2018. During high-flow spring snowmelt runoff periods when brine discharge is naturally minimized, PVU pumping does not substantially affect salinity in the Dolores River, and comparison of these two scenarios indicates that scheduling brine withdrawals during times of low river stage is nearly as effective at reducing TDS mass flux to the river as pumping brine year-round. Cessation of pumping during periods of high river stage may be advantageous for system maintenance, brine injection, and seismic-risk reduction. The fourth scenario tested the effect of reducing irrigation-return flow on brine discharge and predicted a slight reduction of TDS mass flux to the Dolores River, but not as great a reduction as that of using the PVU to remove brine. The fifth scenario simulated 5 years of drought conditions without PVU pumping and indicates brine discharge during drought about 15 percent greater than during average hydrologic conditions. Results from scenario 5 are consistent with the calibrated model results and indicate that aquifer properties and ET processes and parameters may be affecting simulation results during drought. The Paradox Valley groundwater model provides a reasonable overall match to observed conditions in the Dolores River. The model is useful for evaluating relative differences between brine management scenarios to inform PVU operational decisions and to identify gaps in data and process understanding. Representation of the brine source, hydraulic-conductivity parameters, and recharge and ET processes were identified as potential areas for additional field and modeling research. Additional research in the Paradox Valley might include field-data collection that provides additional information on the hydrogeologic framework, groundwater levels, groundwater TDS concentrations, stream characteristics, and aquifer properties. Additional modeling efforts could benefit from applying advanced tools for model development, calibration, and visualization including parameter-estimation and sensitivity analysis. Statistical evaluation of known model uncertainties such as hydraulic conductivity, streambed conductance, representations of the brine source, recharge, and ET could improve the match between simulated and estimated TDS mass flux from PVU pumping wells and to the Dolores River further informing model predictions and system understanding for the Paradox Valley.

Colorado

Helium detection as a guide for uranium exploration

Helium, a byproduct of radioactive decay, may prove to be a valuable indicator of the presence and distribution of uranium deposits. Recent technological advances permit the development of instrumentation not previously adapted for this purpose. Commercially available equipment can provide high sensitivity at low cost and allow reasonable mobility for field use. A truck-mounted mass-spectrometer, tuned for helium-4, permits immediate adjustment or modification of sampling patterns in response to accumulating data. The inlet system of the spectrometer has been designed to allow flexibility in gas analyses from various sample types--soil gas, atmosphere, or gases in water. Sensitivity of the instrument is better than 50 parts of helium per 10 9 parts of gas. Replicate samples and standards can be analyzed in only 3 minutes. Helium in soil gas is being used for the initial evaluation of the technique. A hollow probe, as much as 2 m long, is driven into the ground; and a 10-cc syringe is used to purge the probe and extract the gas. This sample is then injected into the inlet system and introduced into the spectrometer at constant pressure. The output signal is displayed on a chart recorder. Investigations can be performed on a qualitative, relative basis, or on a quantitative basis by comparison to calibrated helium standards. Preliminary field testing includes studies of the responses to variations in wind speed, temperature, barometric pressure, moisture, and sampling depth over extended time periods, as well as studies of geologic controls on the helium content in soil gas. Surveys over known uranium occurrences reveal some anomalous helium distributions. This report describes an updated technological approach to an old idea: that of using helium, a byproduct of uranium radioactive decay, as an exploration tool for uranium. Helium is the sixth most abundant gas found in the earth's atmosphere (Table 1). It is an inert gas and very mobile, mixing rapidly. When the alpha particles from the radioactive decay of uranium and thorium pick up two electrons, atoms of the isotope helium-4 are formed. Several helium-4 atoms are produced from each decay series of U-238, U-235, and Th-232 (fig. 1). The half-lives of the parent isotopes are5also shown in figure 1. One gram of uranium will produce ~10 5 atoms of helium-4 per second, and one gram of thorium produces ~2.5 x 10 4 atoms of helium-4 per second (fig. 2). Calculations of the helium produced from the crust and mantle reveal that 1,125 x 10 30 atoms per year are produced, but only 7 x 10 30 atoms per year escape from the earth (Damon and Kulp, 1958). More is being produced than is being lost; in fact, the total atmospheric content of helium could be produced in only 2 million years (MacDonald, 1963)! However, all the crustal and mantle helium-4 does not degas into the atmosphere as it is formed. It is trapped in crystal lattices and in pore spaces within the earth. What this means is that there is excess helium-4 in the earth--excess, that is, compared to the atmospheric concentration in equilibrium with the helium-4 escape rate into space and the helium-4 flux from the crust and mantle (Nicolet, 1957). Near-surface pockets of high helium-4 concentrations are known, and some natural gas fields are so enriched that they are the source for commercial production of helium. Work by Roberts and others (1975) has shown high helium concentration in the soil gas associated with geothermal areas; and work by Clark and Kugler (1973), Dyck (1975), and Goldak (1974), for example, has noted high helium concentrations in soils and waters in the vicinity of uranium deposits. These latter studies certainly indicate the potential of helium detection for use as an exploration tool for uranium.

Open-File Report

Monitoring marine eruptions

Introduction Submarine volcanoes produce much of the same seismicity and eruptive activity as subaerial volcanoes and can pose hazards to society. Although they can be monitored with similar techniques and methods as described in other chapters of this volume, their submerged location brings unique challenges. This chapter addresses these challenges and provides recommendations for monitoring volcanoes fully or partly in marine environments to meet the capabilities described in other chapters of this volume. The United States and its territories host dozens of submarine volcanoes with most (around 60) in the Commonwealth of the Northern Mariana Islands. Approximately 20 of the Northern Mariana Islands submarine volcanoes are known to be hydrothermally active, and 10 have confirmed eruptions since the 1950s (for example, Baker and others, 2008; Tepp and others, 2019a). Nine of those volcanoes were considered by the National Volcanic Threat Assessment (Ewert and others, 2018) to have a combination of eruptive type and summit depth that poses a higher risk of hazardous eruptions, although only one was listed as a moderate (level 3) threat. Other notable submarine volcanoes of interest to the United States that have historically erupted are Axial Seamount off the Washington State coast, Kamaʻehuakanaloa in Hawaiʻi, and Vailuluʻu seamount in American Samoa. All of these, however, have a low risk of hazards because of their depth (greater than 600 meters below sea level) and eruptive type and so are not included in the National Volcanic Threat Assessment. In addition to submarine volcanoes, the submerged flanks of island volcanoes can also be a source of hazardous submarine eruptions—for example, the 1877 eruption of Mauna Loa, Hawai‘i, in Kealakekua Bay (Wanless and others, 2006). The most notable submarine eruption in recent times was the 2022 eruption of Hunga Tonga–Hunga Haʻapai in Tonga, which was one of the largest eruptions on Earth in the past 100 years. It created a massive volcanic plume, unprecedented shock waves, and far-reaching tsunami (Lynett and others, 2022). Other recent submarine eruptions in the Pacific Ocean Basin have produced subaerial plumes that reached aircraft heights (Carey and others, 2014) and large pumice rafts that can affect marine traffic and harbors (for example, Jutzeler and others, 2014; Kornei, 2019). These examples illustrate the potential hazards of major submarine eruptions. Yet, submarine volcanoes are largely unmonitored, and many eruptions occur that are unnoticed or only identified hours or days afterward. Within U.S. territory, submarine volcanoes in the Northern Mariana Islands have been known to produce eruptive activity that can affect society. Reports from fishermen and other marine vessels in the Northern Mariana Islands have noted underwater explosions, sea-surface discoloration, and bubbling water, all of which are known to be signs of submarine volcanic activity. South Sarigan seamount, located about 160 kilometers (km) north of Saipan, erupted in 2010 from greater than 150 meters below the sea surface, resulting in a gas and ash plume that reached more than 11.9 km into the atmosphere (for example, Searcy, 2013; Embley and others, 2014), high enough to affect international air traffic. Precursory and co-eruptive seismicity was detected on the regional Northern Mariana Islands seismic network (Searcy, 2013) and on global monitoring instruments (Green and others, 2013). Monitoring of submarine volcanoes is best accomplished with marine-based instrumentation, which is also useful for monitoring small island volcanoes that may not have the land area necessary for comprehensive subaerial monitoring. The primary marine-based instrumentation used for submarine volcanoes includes ocean-bottom pressure sensors to assess sea-floor deformation, ocean-bottom seismometers (OBSs) to detect seismicity, and both moored and ocean-bottom hydrophones to detect submarine explosions. Other sensors offer important monitoring data, such as turbidity, temperature, and chemistry of hydrothermal emissions. Marine-based instruments are typically deployed in campaign-style networks with no real-time telemetry owing to cost considerations and technical limitations. However, when necessary, marine instruments can be operated in real time using cables to transmit data to land-based facilities; other technologies for this purpose are in use or in development, such as acoustic transmission from the instrument to a moored buoy (Matsumoto and others, 2016) and a winch-based system with a satellite antenna that is part of the instrument mooring (Matsumoto and others, 2019). Emerging technologies for marine-based monitoring may be considered as part of a future monitoring plan. These technologies include ocean gliders and floats with on-board hydrophones that have been used to record earthquakes and submarine eruptions (for example, Matsumoto and others, 2013; Sukhovich and others, 2015) and fiber-optic cables that have been used as strainmeters to detect earthquakes (for example, Marra and others, 2018; Lindsey and others, 2019). Land-based instruments and satellites can also provide some capability for monitoring submarine volcanoes, but they provide more limited observations than marine-based instrumentation.

Scientific Investigations Report

Monthly variability and possible sources of nitrate in ground water beneath mixed agricultural land use, Suwannee and Lafayette Counties, Florida

In an area of mixed agricultural land use in Suwannee and Lafayette Counties of northern Florida, water samples were collected monthly from 14 wells tapping the Upper Floridan aquifer during July 1998 through June 1999 to assess hydrologic and land-use factors affecting the variability in nitrate concentrations in ground water. Unusually high amounts of rainfall in September and October 1998 (43.5 centimeters total for both months) resulted in an increase in water levels in all wells in October 1998. This was followed by unusually low amounts of rainfall during November 1998 through May 1999, when rainfall was 40.7 centimeters below 30-year mean monthly values. The presence of karst features (sinkholes, springs, solution conduits) and the highly permeable sands that overlie the Upper Floridan aquifer provide for rapid movement of water containing elevated nitrate concentrations to the aquifer. Nitrate was the dominant form of nitrogen in ground water collected at all sites and nitrate concentrations ranged from less than 0.02 to 22 milligrams per liter (mg/L), as nitrogen. Water samples from most wells showed substantial monthly or seasonal fluctuations in nitrate concentrations. Generally, water samples from wells with nitrate concentrations higher than 10 mg/L showed the greatest amount of monthly fluctuation. For example, water samples from six of eight wells had monthly nitrate concentrations that varied by at least 5 mg/L during the study period. Water from most wells with lower nitrate concentrations (less than 6 mg/L) also showed large monthly fluctuations. For instance, nitrate concentrations in water from four sites showed monthly variations of more than 50 percent. Large fluctuations in nitrate concentrations likely result from seasonal agricultural practices (fertilizer application and animal waste spreading) at a particular site. For example, an increase in nitrate concentrations observed in water samples from seven sites in February or March 1999 most likely results from application of synthetic fertilizers during the late winter months. Lower nitrate concentrations were detected in water samples from five of eight wells sampled during high-flow conditions for the Suwannee River in March 1998 compared to low-flow conditions in November 1998. Evidence for reduction of nitrate due to denitrification reactions was observed at one site (AC-1), as indicated by elevated concentrations of nitrogen gas and a corresponding increase in nitrogen isotope (d15N-NO3) values with a decrease in nitrate concentrations. Denitrification is unlikely at other sites based on the presence of dissolved oxygen concentrations greater than 2 mg/L in ground water and no observed trend between nitrate concentrations and values d15N-NO3 values. Nitrate was the dominant nitrogen species in most monthly rainfall samples; however, ammonium concentrations were similar or greater than nitrate during November and December 1998. During February through May 1999, both nitrate and ammonium concentrations were substantially higher in monthly rainfall samples collected at the study area compared to mean monthly concentrations at the Bradford Forest site located east of the study area, which is part of the National Atmospheric Deposition Program/National Trends Network. Also, higher nitrogen deposition rates in the study area compared to those at Bradford Forest could indicate that substantial amounts of ammonia are volatilized from fertilizers and animal wastes, released to the atmosphere, and incorporated as nitrate and ammonium in rainfall deposited in the middle Suwannee River Basin. Ground-water samples from most sites had d15N-NO3 values that indicated a mixture of inorganic and organic sources of nitrogen, which corresponded to multiple land uses where both synthetic fertilizers and manure are used on fields near these sites. Distinct d15N-NO3 signatures, however, were observed at some sites. For example, water samples from areas of row-crop farming as the dominant land use had d15N-NO3 values less than 4 per mil, indicating an inorganic nitrogen source such as synthetic fertilizer. In contrast, d15N-NO3 values greater than 9 per mil were found in water samples from three sites where manure from dairy and or poultry operations is spread on fields throughout the year.

Florida

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

New U-Pb geochronology and geochemistry of Paleozoic metaigneous rocks from western Yukon and eastern Alaska, cross-border synthesis, and implications for tectonic models

The tectonic evolution of and relation between the Yukon-Tanana terrane and the Lake George assemblage, as well as other associated tectonic assemblages in western Yukon and eastern Alaska, have been debated for decades. The Yukon-Tanana terrane is widely considered to be an allochthonous rifted fragment derived from the Laurentian continental margin, whereas the Lake George assemblage and associated assemblages are currently interpreted to be part of the parautochthonous continental margin of western North America (Laurentia). To address these topics, we present 40 new U-Pb zircon ages and 20 new whole-rock geochemical analyses. We incorporate these data into a new compilation of available geological mapping for a large area that straddles the Alaska-Yukon border, together with 34 previously published U-Pb age determinations and an extensive geochemical database of metaigneous rocks from Late Devonian to Early Mississippian and middle to late Permian assemblages in this area. Magmatism in the Lake George assemblage and related assemblages occurred in two pulses from about 371 to 360 and from about 358 to 347 million years ago (Ma); geochemical discrimination diagrams indicate a large crustal component, possibly indicative of arc magmatism, for felsic metaigneous rocks and a range of tectonic environments for mafic rocks. Magmatism in the Fortymile River and related assemblages, and parts of the Nasina assemblage—all parts of the Yukon-Tanana terrane—are mainly Early Mississippian and span a crystallization age range from about 361 to 343 Ma; geochemical discrimination diagrams for these rocks indicate primarily arc geochemical signatures for both mafic and felsic rocks. Middle to late Permian crystallization ages (about 261–253 Ma) are indicated for felsic metaigneous rocks in the Klondike assemblage and some of the felsic metaigneous rocks in the Nasina assemblage. Based on our mapping, we propose the existence of a possible unconformity between the Mississippian and Permian felsic metavolcanic rocks within the Nasina assemblage that is marked by sporadic occurrences of stretched-pebble conglomerate. Our combined database supports the well-established model of a magmatic arc comprising the Fortymile River and Finlayson assemblages of the rifted Yukon-Tanana terrane continental fragment on which a middle to late Permian arc (Klondike assemblage) was later built. The assemblages of the Yukon-Tanana terrane were subsequently intruded by Late Triassic to Early Jurassic granitoids, presumably during reaccretion of the Yukon-Tanana terrane to the continental margin. Permian and Late Triassic to Early Jurassic intrusions have not been mapped in the now structurally lower plate Lake George assemblage; their absence is one of the lines of evidence that have been used to support the parautochthonous, rather than allochthonous, origin of the Lake George assemblage and related assemblages. Our new data, together with previously published ranges of igneous crystallization ages and geochemical tectonic signatures of the Late Devonian to Early Mississippian magmatic rocks in the Lake George assemblage and associated assemblages and in the Fortymile River, Nasina, and correlated assemblages of the Yukon-Tanana terrane, indicate that the currently accepted interpretation of the Lake George assemblage and associated rocks being part of parauthochthonous North America is not the only possible interpretation of this tectonic entity. Approximately half of the dated intrusive rocks in the Lake George assemblage are contemporaneous with the metaigneous rocks of the Yukon-Tanana terrane arc (<361 Ma). We speculate that our approximately 361 Ma U-Pb age for quartz syenite in part of the North American continental margin in south-central Yukon defines the beginning of rifting of the Laurentian margin. Although the currently favored model of prolonged middle Paleozoic subduction and extension in both the Yukon-Tanana terrane and parautochthonous North America allows for simultaneous middle Paleozoic magmatism on both sides of the Slide Mountain Ocean, we now propose an alternative hypothesis in which the Lake George assemblage represents a deeper part of the rifted Yukon-Tanana terrane arc. If this is the case, the absence of Permian and Late Triassic to Early Jurassic arc rocks in the Lake George assemblage could be explained either by the arcs of these ages not being wide enough to have affected the Lake George assemblage or by tectonic displacement of these arc rocks away from the Lake George assemblage. Our approximately 259 Ma U-Pb zircon age and geochemical analyses of metarhyolite in the Seventymile terrane in Alaska, which comprises remnants of the back-arc basin that separated the Yukon-Tanana terrane from the Laurentian continental margin, confirm the presence of a late middle Permian volcanic arc component to the terrane. Our approximately 319 Ma U-Pb zircon age from the Chicken assemblage (as redefined in this study) in eastern Alaska, combined with previously reported fossil ages and a U-Pb zircon age from this assemblage, indicate that it is a Late Mississippian to Early Pennsylvanian arc assemblage. We propose several other relatively young, locally developed arc assemblages outboard of the ancient continental margin of Laurentia that may correlate with the Chicken assemblage, but we consider its origin to remain an enigma.

Alaska

Prediction of the probability of elevated nitrate concentrations at groundwater depths used for drinking-water supply in the Puget Sound basin, Washington, 2004–19

The Puget Sound basin encompasses the 13,700-square-mile area that drains to the Puget Sound and the adjacent marine waters of Washington State. Well more than 4 million people live within the basin, with numbers continuing to increase, who rely on the basin’s natural resources including groundwater. The Puget Sound Partnership was created by a Washington State statute to implement a science-based recovery of the Puget Sound to help address impacts to these resources. As part of the recovery, the partnership developed the Puget Sound Vital Signs as measures of ecosystem health that guide the assessment of progress toward Puget Sound recovery goals. The Puget Sound Partnership Leadership Council adopted a Drinking Water Vital Sign associated with human health and quality of life, recognizing certain indicators as integral to the sustainability of Puget Sound recovery efforts. One such Vital Sign indicator was the vulnerability of groundwater throughout the aquifers of the Puget Sound basin to elevated nitrate concentrations as defined by the probability of exceeding 2 milligrams/liter (mg/L) at a specific location and well depth. The U.S. Geological Survey (USGS) led the effort to characterize groundwater vulnerability. For this study, groundwater vulnerability refers to a probability with which a contaminant applied at or near the land surface can migrate to the aquifer of interest for a given set of land-use practices. Nitrate concentration data were selected for evaluation because elevated nitrate concentrations are typically caused by anthropogenic activities and have been associated with deleterious impacts on human health. To identify groundwater vulnerability to elevated nitrate concentrations, logistic regression was used to relate anthropogenic (human associated) and natural variables to the occurrence of elevated nitrate concentrations in untreated groundwater from large public water supply system wells found within the Washington State Department of Health Sentry database. Variables that were analyzed included well depth, soil hydraulic conductivity, precipitation, population density, fertilizer application amounts, and land-use types. Statistically significant models that predicted the probabilities of groundwater nitrate concentrations greater than 2 mg/L based on the predictor variables were created for the time periods 2000–04, 2005–09, 2010–14, and 2015–19. For all time periods, well depth and a measure of the abundance of urban and agricultural land over or near the well consistently helped explain the vulnerability of the well to elevated nitrate concentrations defined as a probability of exceeding 2 mg/L of nitrate. Precipitation and (or) soil hydraulic conductivity were also important predictor variables in the models. The models for each time period were used to create maps of groundwater vulnerability at 150- and 300-foot depths throughout the Puget Sound basin. As expected, the most vulnerable locations were associated with shallower well depths and increased agriculture and urban land cover. Across all four time periods, groundwater vulnerability throughout the Puget Sound was low, with probabilities of exceeding 2 mg/L concentrations of nitrate at depths at 150 and 300 feet typically less than 50 percent. Results also found a slight decrease in probabilities of elevated nitrate concentrations throughout the basin over time. More specifically, additional statistical tests found that groundwater with probabilities of less than about 60 percent declined from 2000 to 2019 and represented more than 75 percent of the modeled Puget Sound basin aquifer. Wells with greater than 60 percent probability increased over the same time period but represented only about 25 percent of the aquifer. The maps and statistical analysis presented in the study provide valuable and informative evaluation of the vulnerability of groundwater in the Puget Sound basin to elevated nitrate concentrations. The probability maps do not represent measured nitrate concentrations in groundwater, but rather they present the probability that nitrate concentrations exceed 2 mg/L. The models and predictions from this study are a viable indicator for the Puget Sound Partnership’s Healthy Human Population—Drinking Water Vital Sign. The logistic regression modeling approach presented here benefits water managers by allowing them to assess temporal trends in a range of probabilities, explore vulnerability changes as new regional land cover and anthropogenic data are generated, and distinguish vulnerabilities at different depths within the aquifer.

Washington