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Deformation by pressure solution and grain boundary sliding in a retrograde shear zone in southern New England, USA

Alleghanian phyllonites in a shear zone in southern New England were formed by the retrogression and hydration of a high-grade Acadian pelitic schist. The retrogression was locally incomplete, resulting in both heterogeneous mineralogy and mineral compositions, and in many arrested reaction textures. These features, documented by backscattered electron and element map imaging, and by 40 Ar/ 39 Ar dating, provide a record of the processes active as the schist was converted to a phyllonite. On the margins of the shear zone relic biotite and garnet grains survive but are partially replaced by chlorite. Relic high-grade muscovite flakes containing up to 35 % paragonite (pg) also persist but are entrained in swarms of pg-poor muscovite flakes producing folia with an anastomosing network of muscovite grains of variable composition. Single crystals of pg-rich muscovite are truncated by muscovite in successively younger cross-cutting folia that contain decreasing pg contents, falling to <5% pg in the youngest folia. In the core of the shear zone all high-grade minerals are destroyed, but recrystallization continues with earlier greenschist facies folia replaced by lower grade and pg-poorer muscovite in younger folia. Muscovite grains in truncated folia are commonly kinked and selective recrystallization of muscovite in kink bands to pg-poor-compositions demonstrates that strain energy helped drive recrystallization. The boundaries of these new pg-poor muscovite folia are sharp, and truncations indicate that grain boundary sliding (GBS) involved dissolution. GBS also enabled folding by flexural slip along muscovite grain boundaries. Fold amplitudes increased as chlorite dissolved from fold limbs precipitated in fold hinges producing crescent-shaped saddle-reef-like structures. Together these observations of truncation and replacement by dissolution and precipitation demonstrate that pressure solution and GBS facilitated both the formation of the phyllonitic shear zone and slip along it.

Connecticut

Updating and recalibrating the integrated Santa Rosa Plain Hydrologic Model to assess stream depletion and to simulate future climate and management scenarios in Santa Rosa, Sonoma County, California

The Santa Rosa Plain Hydrologic Model (SRPHM) was developed and published in 2014 through a collaboration between the U.S. Geological Survey (USGS) and Sonoma Water to analyze the hydrologic system in the Santa Rosa Plain watershed, help meet the increasing demand for fresh water, and prepare for future uncertainties in water resources. The original model simulated hydrological conditions and water use from water years 1975 to 2010. Recently (2023), the USGS, in cooperation with Sonoma Water and the California State Water Resources Control Board, updated the SRPHM model to extend its simulation period to the end of the 2018 calendar year, incorporate new estimates of rural and agricultural water use, and use efficient input format for climate variables. The updated model was recalibrated, and evaluation of the new model calibration is included in this report. This report presents the results of comparing the hydraulic heads, streamflow, and groundwater budget simulated by the updated model with those generated by the original model and observed data. The main difference in the simulated budget between the original and updated SRPHM is the estimates of agricultural pumping, rural domestic pumping, and return flow generated from rural water use that was not simulated in the original model. The revised agricultural pumping is simulated using the agricultural package, which constrains pumping to available groundwater. The use of the agricultural package leads to a more realistic estimation of agricultural water use, with revised agricultural pumping being one-third less than that in the original model. The revised rural pumping is about half of the pumping in the original model because of using detailed parcel data to estimate population density in rural areas instead of coarse census tracts. Overall, average total inflows for water years 2006–10 simulated by the updated model were about 2 percent less than the original model, and the average total updated outflows were nearly 5 percent less than the original model. The updated model was then used to generate stream depletion maps, simulate climate change scenarios during 2019–99, and simulate water rights allocation using the Model for Decision Support in Integrated River Basin Management (MODSIM). The results from simulating eight future climate scenarios indicated either an increase in groundwater storage or no significant change in the next 80 years, along with an increase in recharge, an increase in actual evapotranspiration in six out of eight climate projections, and an increase in surface runoff. The increases in the simulated future groundwater storage, recharge, evapotranspiration, and runoff in most climate projections are mainly driven by the projected increase in precipitation in most of the future climate scenarios. The updated model also was used to test a pilot case study demonstrating water-resource allocation among different users with different water rights using the integrated MODSIM-Groundwater and Surface-Water Flow Model (GSFLOW) platform. The updated SRPHM serves as a valuable tool for analyzing historical and future hydrologic conditions in the Santa Rosa Plain watershed and preparing for future uncertainties.

California

Peak streamflow trends in Montana and northern Wyoming and their relation to changes in climate, water years 1921–2020

Frequency analysis on annual peak streamflow (hereinafter, peak flow) is essential to water-resources management applications, including critical structure design (for example, bridges and culverts) and floodplain mapping. Nonstationarity is a statistical property of a peak-flow series such that the distributional properties (the mean, variance, or skew) change either gradually (monotonic trend) or abruptly (shift, step change or change point) through time. Not incorporating or accounting for observed nonstationarity into peak-flow frequency analysis might result in a poor representation of the true probability of large floods and thus misrepresent the actual flood risks to life and property. This report summarizes how hydroclimatic variability might affect the temporal and spatial distributions of peak-flow data in the State of Montana (and northern Wyoming) and is part of a larger study to document peak-flow nonstationarity and hydroclimatic changes across a nine-State region consisting of Illinois, Iowa, Michigan, Minnesota, Missouri, Montana, North Dakota, South Dakota, and Wisconsin. A wide range of analyses and statistical approaches are applied to document the primary mechanisms controlling floods and characterize temporal changes in hydroclimatic variables and peak flows. This study was completed in cooperation with the Montana Department of Natural Resources and Conservation. The purpose of this report is to characterize temporal and spatial patterns of nonstationarity in peak flows and hydroclimatology in Montana and northern Wyoming. In this evaluation, peak-flow, daily streamflow, and model-simulated gridded climatic data were examined for monotonic trends, change points, and other statistical properties that might indicate changing climatic and environmental conditions. This report includes background information on the study area, the history of U.S. Geological Survey peak-flow data collection and frequency analysis in Montana, and the review of research relating to hydroclimatic variability and change in Montana. This study might help provide a framework for addressing potential nonstationarity issues in peak-flow frequency updates that commonly are completed by the U.S. Geological Survey in cooperation with other agencies throughout the Nation. The analytical structure of this study includes analyses of monotonic trends and change points in numerous hydroclimatic variables in assigned 30-, 50-, 75-, and 100-year analysis periods. For Montana and part of Wyoming, the 30-, 50-, 75, and 100-year analyses included 157, 70, 48, and 12 streamgages, respectively. For those streamgages, nonstationarities were analyzed in the following variables: (1) climatic variables, including annual and seasonal (winter, spring, summer, and fall) temperature and precipitation; (2) daily streamflow variables, including the annual center of volume duration, annual center of volume median, and peaks over threshold with a mean of four events per year; and (3) annual peak-flow variables, including peak-flow timing and magnitude. A likelihood approach was used to express statistical confidence and assign the nonstationarity results as likely upward or downward (highest statistical confidence), somewhat likely upward or downward (less statistical confidence), or about as likely as not (little statistical confidence; hereinafter, neutral). For the nonstationarity analyses of the climatic, daily streamflow, and peak-flow variables, the results are presented in detail and discussed with respect to statewide patterns and geographic variability. For each of the 30-, 50-, and 75-year analyses, peak-flow change-point and monotonic trend analyses were compiled for streamgages classified with likely downward or likely upward trends. For those streamgages, the associated basin characteristics and nonstationarity results for peak-flow timing, daily streamflow, and climatic variables were investigated and statistically compared to discern associations among other variables that might contribute to the peak-flow nonstationarity results. The 50- and 75-year peak-flow nonstationarities identified in this study are mostly downward, in association with mostly upward temperature and potential evapotranspiration:precipitation monotonic trends. For the 50-, 75-, and 100-year analyses, the peak-flow change points are predominantly downward and are concentrated in the 1970s and 1980s, which indicates general consistency among the longer trend periods. These findings are in association with substantial research documenting globally rising temperature and atmospheric greenhouse gas concentrations that might be largely attributed to anthropogenic activities. Anthropogenic effects might represent long-term (on the order of several decades to more than a century) climate changes that might happen within highly variable natural climate fluctuations. Several paleo studies in the north-central United States have indicated that hydroclimatic extremes (that is, low- and high-streamflow conditions) before European settlement have been outside of extremes since the 1900s. Depending on the interactions of anthropogenic effects and natural climate variability, extreme high-streamflow conditions might occur in the future, even in the presence of long-term downward peak-flow trends.

Montana, Wyoming

Comparative crop yield forecasting using satellite-derived biophysical and agro-climatic predictors in Sub-Saharan Africa

Timely and accurate crop yield forecasting is central to food security early warning systems, particularly in climate-vulnerable regions. While operational forecasting frameworks commonly rely on precipitation and vegetation indices such as NDVI, their ability to provide actionable lead time remains limited. Here, we evaluate the added value of satellite-derived biophysical Essential Climate Variables (ECVs): Leaf Area Index (LAI) and Fraction of Photosynthetically Active Radiation (FAPAR), for forecasting millet yield in Burkina Faso (BF) and maize yield in South Africa (ZA) and Malawi (MW). Using Random Forest models, we quantify forecast skill across the growing season at both national and sub-national scales. Results show that LAI and FAPAR provide effective forecast lead times of approximately 4 months in BF, 2 months in ZA, and up to 6 months in MW relative to harvest. At peak performance, Mean Absolute Percentage Error (MAPE) reaches 19.8% (LAI) and 23.8% (FAPAR) in BF, 12.0% and 9.8% in ZA, and 21.8% and 20.8% in MW, respectively. Across countries, biophysical parameters often outperform NDVI and precipitation, particularly in arid and semi-arid regions. At the sub-national level, LAI and FAPAR enable classification of administrative units into high and moderate-skill forecast units, revealing strong spatial heterogeneity linked to crop dominance. However, forecast skill declines where the target crop is not the dominant type, highlighting an important limitation for operational deployment. Overall, the findings suggest that satellite-derived biophysical parameters can provide earlier and more spatially resolved yield signals than commonly used predictors, with potential to improve the timeliness and effectiveness of food security early warning systems.

Remote Sensing Applications: Society and Environme

Navigating uncertainty and competing objectives: Spring chinook salmon recovery in the upper Willamette river

Globally, anadromous fish populations are threatened with extinction due to multiple factors, including river impoundments that block migration, widespread alteration of physical habitat, temperature, and flow regimes, commercial and recreational harvest, changes in biological communities, and long-term climate trends. In this synthesis, we describe how physical and biological factors, policy and law, and public resource allocation affect management of spring-run Chinook Salmon ( Oncorhynchus tshawytscha ) in the Upper Willamette River (UWR), Oregon, USA. Efforts to restore salmon populations often involve trade-offs, for example, water management decisions must account for flood control, agricultural and municipal water use, and management of other species. UWR Chinook Salmon recovery efforts are also governed by multiple laws, policies, and action agencies that in some cases have incongruent objectives. Competing and conflicting objectives, combined with uncertainty regarding the outcomes of proposed management actions, create significant challenges for decision makers. Resource limitations, regulatory constraints, and incongruent objectives have created challenges for managers in the UWR, but opportunities exist for improved adaptive management and collaboration, which could build trust and engagement among stakeholders and ultimately support the successful implementation of decision tools. A suite of decision support tools that have been used in the Willamette River basin and elsewhere across the range of Pacific salmon have the potential to enhance decision processes. These tools can be effective when decision makers and stakeholders commit to long-term, collaborative utilization of the tools for decision making, and when available resources and regulatory environments are conducive to implementation and adaptive refinement of both the decision-support tools and management plans. The general biological and institutional principles discussed for UWR Chinook Salmon in this work apply more generally to populations of anadromous fishes across their range, especially to populations in highly regulated river systems.

Oregon

Trace elements in streambed sediment and fish liver at selected sites in the Upper Colorado River Basin, Colorado 1995-96

Trace elements were analyzed in streambed-sediment samples collected from 16 sites and in fish-liver samples collected from 14 sites in the Upper Colorado River Basin in Colorado as part of the National Water-Quality Assessment program. Sites sampled represented agricultural, mining, mixed, and urban/recreation land uses and background conditions. The results for 15 trace elements in streambed-sediment and in fish-liver samples are presented in this report. Fourteen of the selected trace elements were detected in streambed-sediment samples collected at all sites. Twelve of the selected trace elements were detected in fish liver at more than 50 percent of the sites. Cadmium, copper, selenium, and zinc were selected for a more detailed analysis. Cadmium, copper, and zinc concentrations in streambed sediment were highest at mining land-use sites in the Southern Rocky Mountains physiographic province. Selenium concentrations in streambed sediment were highest at an agricultural land-use site in the Colorado Plateau physiographic province. The concentration of trace elements in streambed sediment generally increased as particle size decreased. Concentrations of trace elements in fish liver generally did not follow the same relation to land use as concentrations in streambed sediment; however, cadmium concentrations in fish liver were highest at a mining land-use site in the Southern Rocky Mountains physiographic province, and selenium concentrations in fish liver were highest at an agricultural land-use site in the Colorado Plateau physiographic province. Copper and zinc concentrations in fish liver were highest at mixed land-use sites. Comparison of streambed-sediment and fish-liver concentrations to two other similar NAWQA studies in the Rocky Mountain region generally indicated similar patterns in relation to land use for streambed sediment, but not for fish liver. Cadmium, copper, and zinc concentrations in streambed sediment were highest at sites affected by mining in all three study units. Selenium concentrations in streambed sediment did not indicate relations among the three study units when compared to land use. Cadmium in fish liver was highest at sites affected by mining in all three study units. Copper, selenium, and zinc in fish liver did not indicate relations among the three study units when compared to land use.

Colorado

High-resolution landscape-scale maps of nutrients, phytoplankton, and related water-quality constituents in Suisun Bay and the Sacramento–San Joaquin Delta, California, during 2018—Results from high-resolution underway surveys

We examined the abundance and distribution of nutrients and phytoplankton in the tidal aquatic environments of the Sacramento–San Joaquin Delta (Delta) and Suisun, Grizzly, and Honker Bays in California by completing three spatial surveys that used continuous underway high frequency (1 hertz) measurements and sampling onboard a high-speed boat. Surveys were conducted in May, July, and October 2018. Water was sampled continuously during surveys to simultaneously collect information about the concentration and spatial distribution of all major nutrient forms together with information about the major classes of phytoplankton and associated standard field measurements of water quality, such as dissolved oxygen, dissolved organic matter, pH, salinity, specific conductance, turbidity, and water temperature. The results show a greater than 50-fold variation in nutrient and phytoplankton concentrations across space and time, providing evidence of the dynamic environmental processes that shape the ways nutrients interact with and affect Delta aquatic habitats.

Data Report

Decadal trends and occurrence of geogenic constituents and mixtures in groundwater across the continental United States

Worldwide, about 50% of the population is served by groundwater-sourced drinking water. Numerous groundwater quality assessments have found that geogenic constituents are among the most common contaminants in drinking-water aquifers. Documenting changing groundwater quality is a crucial aspect of water availability assessments. We assess trends and occurrence of geogenic constituent concentrations in groundwater across the continental United States using 3 decades of data from the U.S. Geological Survey’s National Water Quality Network. Thousands of groundwater wells were grouped into agricultural, urban, or domestic supply network types. Although most networks and constituents had no statistically significant change in concentration, many had increasing concentration trends, elevated concentrations, or both. Lithium, sodium, radium, sulfate, and uranium had increasing trends in more than 10% of the study networks. Urban and domestic well networks had increasing lithium and sodium trends more often than agricultural networks. Manganese most commonly increased in domestic well networks; uranium more commonly increased in agricultural and urban networks. Elevated concentration mixtures were widespread, and mixture complexities appeared to increase over time. Our results indicate that more than 2.3 million domestic-well users may be affected by elevated concentrations of one or more geogenic constituents.

continental United States

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

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

British Columbia, Washington

Hydrogeologic framework and extent of saltwater intrusion in Kings, Queens, and Nassau Counties, Long Island, New York

In 2016, the U.S. Geological Survey began a multiyear cooperative study with the New York State Department of Environmental Conservation to evaluate the sustainability of Long Island’s sole-source aquifer system through hydrogeologic mapping, compilation of groundwater chloride concentrations, and groundwater flow modeling. In the initial phase of the islandwide study, the hydrogeologic framework and extent of saltwater intrusion in aquifers in Kings, Queens, and Nassau Counties on western Long Island, N.Y., were investigated. The aquifer system underlying western Long Island has been under stress from pumping of public, irrigation (golf course), and industrial supply wells. Saltwater intrusion has occurred from surrounding embayments (East River, Long Island Sound, Jamaica Bay, and the Atlantic Ocean) due to pumping. Eighteen boreholes were drilled and cores taken during 2019–21 to collect hydrogeologic, geochemical, and geophysical data to delineate the complex subsurface hydrogeology and extent of saltwater intrusion within the study area. Evaluation of the new cores, reexamination of legacy core descriptions, and analysis of borehole geophysical logs was used to refine the previously published hydrogeologic framework of Pleistocene and Cretaceous unconsolidated sediments in the area, including delineation of a previously undefined hydrogeologic unit between the Magothy aquifer and the Raritan confining unit, herein named the “upper Raritan aquifer.” The upper Raritan aquifer was first recognized in southeastern Nassau County from an analysis of about 50 closely spaced boreholes with high-resolution core descriptions and gamma-ray (gamma) logs. Further analysis of borehole logs across the study area indicated that the upper Raritan aquifer was also present in Kings and Queens Counties. Nuclear magnetic resonance (NMR) logging was used for the first time on Long Island to provide estimates of the hydraulic properties of the major aquifer and confining units. Unlike other geophysical logs that record responses to the rock matrix and fluid properties and are strongly dependent on mineralogy, NMR logs record responses to the presence of hydrogen protons in the formation fluid to determine water fraction and pore-size distribution. NMR log analysis provided estimates of the clay-bound, capillary-bound, and mobile water fractions and hydraulic conductivity of aquifers and confining units penetrated by five wells in Nassau County. Pumpage for public-supply and industrial wells on Long Island began in the 1870s with small, localized suppliers of populated areas in Kings and Queens Counties. By 1904–16, pumpage for public water supply in Kings County averaged 21 million gallons per day, and averaged 37 million gallons per day in Queens County, mostly from the upper glacial aquifer. Saltwater intrusion was reported as early as the beginning of the 20th century and included the upper glacial-Jameco-Magothy and Lloyd-North Shore aquifer systems. By 1936, pumping in central Kings County created a major cone of depression in the water table extending to the south shore of much of Kings County and into southwestern Queens County. Saltwater intrusion has caused the shutdown of public-supply wells in Kings, Queens, and Nassau Counties. A large saltwater intrusion wedge in the Lloyd aquifer was indicated in southern Queens County in the early part of the 20th century, and the saltwater interface may have been onshore predevelopment. Most of Kings and Queens Counties are intruded with saltwater in both the upper glacial-Jameco-Magothy and Lloyd-North Shore aquifers systems. Saltwater increased during the 20th century and continues to increase to the present (2023) in the Lloyd-North Shore aquifer system in Great Neck and Manhasset Neck in northern Nassau County. A major wedge of saltwater intrusion in the upper glacial-Jameco-Magothy aquifer in southwestern Nassau County appears to be increasing.

New York

Land-use interactions, Oil-Field infrastructure, and natural processes control hydrocarbon and arsenic concentrations in groundwater, Poso Creek Oil Field, California, USA

Like many hydrocarbon production areas in the U.S., the Poso Creek Oil Field in California includes and is adjacent to other land uses (agricultural and other developed lands) that affect the hydrology and geochemistry of the aquifer overlying and adjacent to oil development. We hypothesize that the distributions of hydrocarbons and arsenic in groundwater in such areas will be controlled by complex interactions between mixed land uses, oil-field infrastructure, and natural processes. In 2020–2021, samples of groundwater and surface water were collected and analyzed for a large suite of inorganic and organic chemicals and isotope and gas tracers to test this hypothesis. Those data are supplemented with ancillary data on historical geochemistry, hydrology, geology, and oil-field infrastructure. Hydrocarbons in groundwater (e.g., methane through pentane gases and benzene) are associated with natural processes (e.g., fault offsets or transition in sediment depositional environment) and oil-field infrastructure (e.g., fluid-migration pathways associated with uncemented annulus in oil wells or unlined pits). Arsenic concentrations >10 μg per liter (μg/L; maximum concentration 12.9 μg/L) are associated with natural processes in old, high-pH groundwater, and more recent recharge of water from natural and/or engineered recharge processes. Along the southwest margin of the oil field, pumping for drinking-water and irrigation supplies in combination with engineered groundwater recharge produce a depression in groundwater elevations where groundwater with elevated sulfate concentrations from agricultural areas and groundwater with hydrocarbons from the oil field mix to produce a zone of sulfate reduction that removes hydrocarbons and arsenic from groundwater but produces elevated sulfide (S 2- ) concentrations (maximum concentration 29 mg per liter, mg/L). In this study, multiple approaches were required to resolve the overlapping effects of land uses, oil-field infrastructure, and natural processes on the distributions of hydrocarbons and arsenic in groundwater. The combined use of geographic, historical, physical, chemical, isotopic, and other information to constrain processes could be a useful approach for studies in other hydrocarbon-production areas. This is particularly important where land uses affect aquifer hydrology to an extent that causes mixing of groundwaters with different chemical compositions.

California

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

Integrating detrital magnetite geochemistry and (U-Th)/He chronometry as a sediment provenance tool in geologic and metallogenic terranes

Magnetite is ubiquitous in porphyry Cu systems and in sediment sourcing both barren and mineralized regions, with potential as an indicator mineral in concealed and coarsely-mapped terranes. We develop and test a workflow for integrated geochemistry and (U–Th)/He (He) dating for inferring detrital magnetite (DMt) provenance in these settings. The ca. 70 Ma Taurus porphyry Cu–Mo(–Au) district in eastern interior Alaska serves as a test case. DMt from streams draining porphyry-related mineralization was characterized by geochemistry and mineral inclusion and microstructure observations, complemented by similar data for potential porphyry and host rock sources. Principal component analysis and clustering of DMt geochemical data resolve multiple populations in our samples geochemically and texturally compatible with derivation from metamorphic, porphyry-related hydrothermal, and igneous sources. Hydrothermal magnetite comprises ∼16–50% of DMt nearest porphyry mineralization but diminishes to ∼4% ∼15 km downstream. Subsampled grains within populations yield ∼160–110 Ma, ∼70 Ma, ∼55 Ma, and ∼20 Ma magnetite He date modes. Combined with provenance, He dates capture Early Cretaceous regional exhumation of metamorphic host rock and Late Cretaceous porphyry Cu mineralization. DMt grains showing partial hematite replacement yield ca. 55–20 Ma dates regardless of source, overlapping regional warm/wet climatic intervals. We interpret Cenozoic dates to reflect exhumation to near-surface oxidizing conditions and(or) supergene weathering. Magnetite is thus a promising target phase for (1) tracking the spatiotemporal distribution of porphyry systems, and (2) linking the formation and exhumation of these systems to a regional geologic history, both in Alaska and globally.

Alaska, Yukon

Critical review of mercury methylation and methylmercury demethylation rate constants in aquatic sediments for biogeochemical modeling

Mercury is a toxin that causes neurological impairments in adults, is particularly harmful for fetuses and children, and is deadly in severe cases, making it a worldwide health concern. Methylmercury (MeHg) is the environmentally relevant form of mercury (Hg) because it biomagnifies along the food chain. Methylmercury is mainly produced in aquatic sediments via methylation of inorganic Hg (Hg(II)) and transformed back via demethylation. Because transformation rates determine MeHg concentrations, quantification of methylation and demethylation rates is needed to inform management of MeHg. Published rate constants for Hg(II) methylation ( 𝑘 𝑚 ) and MeHg demethylation ( 𝑘 𝑑 ) vary greatly, stemming partly from differences in experimental methods. We conducted a comprehensive review of rate laws, evaluated published rate constants, and performed biogeochemical simulations to assess variability in reported 𝑘 𝑚 and 𝑘 𝑑 . Based on selected studies employing the same pseudo-first-order rate law and similar experimental methods, we found that 𝑘 𝑚 = 0.04 ± 0.03 d −1 is a reasonable range for wetland sediments. Over a number of environments, maximum 𝑘 𝑑 was smaller at sites without Hg source ( 𝑘 𝑑 = 0.5 d −1 ) than at sites with identified Hg source ( 𝑘 𝑑 = 1.8 d −1 ). Larger variability and higher uncertainty in 𝑘 𝑑 compared to 𝑘 𝑚 highlight the need for more research on MeHg demethylation rates. This critical review: (a) aids the design of future experimental studies of 𝑘 𝑚 and 𝑘 𝑑 ; (b) provides guidance for comparing rate constants from different studies; (c) presents a biogeochemical reaction model to assess rate constants; and (d) informs selection of 𝑘 𝑚 and 𝑘 𝑑 values from the literature for use in model simulations.

Critical Reviews in Environmental Science and Tech