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Arsenic, chromium, uranium, and vanadium in rock, alluvium, and groundwater, Mojave River and Morongo Areas, western Mojave Desert, southern California

Trace elements within groundwater that originate from aquifer materials and pose potential public-health hazards if consumed are known as geogenic contaminants. The geogenic contaminants arsenic, chromium, and vanadium can form negatively charged ions with oxygen known as oxyanions. Uranium complexes with bicarbonate and carbonate to form negatively charged ions having aqueous chemistry similar to oxyanions. The concentrations of arsenic, chromium, uranium, and vanadium in groundwater result from the combined effects of (1) geologic abundance within aquifer materials; (2) the fraction of these elements that have weathered from and sorbed to the surfaces of mineral grains and are potentially available to groundwater; and (3) the aqueous chemistry of dissolved oxyanions in groundwater during different redox conditions and pH, both of which are affected by hydrogeology, including the length of time groundwater has been in contact with aquifer materials. Concentrations of arsenic, chromium, uranium, and vanadium were measured in samples of (1) rock, surficial alluvium, and drill cuttings using portable (handheld) X-ray fluorescence (pXRF); (2) operationally defined fractions extractable from these materials; and (3) water from wells sampled between 2000 and 2018 within the 3,500 square mile Mojave River area and Morongo area of the western Mojave Desert, southern California. Regionally, rock and surficial alluvium in the Mojave River and Morongo areas are high in arsenic, low in chromium and uranium, and near the average bulk continental crust concentration for vanadium. Locally, high chromium concentrations are present in mafic rock within the San Gabriel Mountains; high uranium concentrations are present in felsic rock within the San Bernardino Mountains; and high arsenic, uranium, and vanadium concentrations are present in extrusive (volcanic) felsic rock within uplands surrounding groundwater basins along the Mojave River downstream from Barstow, California. Elemental assemblages identified using principal component analyses (PCA) of pXRF data were used to characterize felsic, mafic, and felsic volcanic source terranes in rock, surficial alluvium, and in geologic material penetrated by selected monitoring wells drilled between 1994 and 2018. Highly felsic alluvium associated with recent deposition from the Mojave River was identified along the 90-mile length of the floodplain aquifer along the river. The thickness of these highly felsic alluvial deposits ranged from 200 feet (ft) near Victorville and near Barstow to a thin veneer about 30 ft thick downstream from Victorville and downstream portions of the floodplain aquifer within the Mojave Valley. Groundwater in the Mojave River and Morongo areas was generally oxic and alkaline (pH≥7.5). Maximum concentrations of arsenic, hexavalent chromium [Cr(VI)], uranium, and vanadium in water from as many as 498 wells sampled between 2000 and 2018 were 360, 140, 1,470, and 690 micrograms per liter (μg/L), respectively. Water from 22 percent of sampled wells exceeded the U.S. Environmental Protection Agency (EPA) maximum contaminant level (MCL) for arsenic of 10 μg/L, with arsenic concentrations commonly exceeding the MCL in water from wells east of Barstow, deep wells in the Victorville fan, and in suboxic or reduced groundwater within the floodplain aquifer. Water from about 1 percent of sampled wells had Cr(VI) concentrations greater than the California MCL for total chromium of 50 μg/L, whereas 13 percent of sampled wells had Cr(VI) concentrations greater than the former California MCL of 10 μg/L. Hexavalent chromium concentrations were highest in water from wells in the Sheep Creek alluvial fan, eroded from mafic rock in the San Gabriel Mountains, although Cr(VI) concentrations greater than the former California MCL also were present elsewhere in the study area where mafic materials or older groundwater were present. Water from about 9 percent of sampled wells exceeded the EPA MCL for uranium of 30 μg/L, with concentrations exceeding the MCL commonly associated with irrigation return from agricultural land overlying the floodplain aquifer. Water from about 7 percent of sampled wells had vanadium concentrations greater than the California notification level of 50 μg/L; most of these wells were in the Victorville fan within the Mojave River area. In general, arsenic concentrations were higher in suboxic or reduced water; chromium concentrations were higher in oxic, alkaline (pH≥7.5) water; uranium concentrations were higher in circumneutral to slightly alkaline water (pH≤7.4); and vanadium concentrations were higher in highly alkaline (pH≥8.0) water, independent of redox status. Concentrations within geologic source terranes are not the sole factor controlling the concentrations of geogenic elements in groundwater. Differences in mineral weathering, pH-dependent sorption to surface-exchange sites on mineral grains, and aqueous geochemistry (especially redox status and pH) affect geogenic element concentrations in groundwater. Consequently, the relative abundances of arsenic, Cr(VI), uranium, and vanadium in groundwater differ from their relative abundances in the average bulk continental crust and their regional abundances in rock and surficial alluvium within groundwater basins of the western Mojave Desert. Processes that control the concentrations of arsenic, chromium, uranium, and vanadium in groundwater operate at the mineral-grain and aquifer scale. At the mineral-grain scale, sequential chemical extraction data show arsenic and uranium are more available to groundwater (under specific geochemical conditions) than chromium or vanadium, which largely are unavailable within unweathered mineral grains. Additionally, chromium and vanadium form few aqueous complexes and bind tightly with iron minerals within surface coatings on mineral grains making them less available to groundwater, whereas complexation with other dissolved ions enhances the solubility of uranium and, to a lesser extent, arsenic. Complexation also increases the valence (less negative charge) and increases the size of dissolved oxyanions and uranium complexes with bicarbonate and carbonate making them less readily sorbed to aquifer materials. At the aquifer scale, hydrogeology (including isolation of water in aquifers from surface sources of recharge, older groundwater age, and long contact times between groundwater and aquifer materials) combined with geochemical processes (such as silicate weathering) to produce alkaline groundwater. Desorption from sorption sites on the surfaces of mineral grains with increasing pH increases arsenic, chromium, and vanadium concentrations in water from wells and increases Cr(VI) concentrations as long as water remains oxic. Aqueous geochemistry and concentrations of geogenic contaminants also are affected by anthropogenic activities including (1) discharge of treated municipal wastewater, which may change the redox status of groundwater; (2) return from irrigated agriculture, which may alter the chemistry of groundwater and increase the solubility of trace elements such as uranium; and (3) groundwater pumping and subsequent water-level declines, which may change the source of water yielded by wells. The quality of water imported from northern California and infiltrated from ponds for groundwater recharge may be altered by naturally present trace elements, especially uranium in areas of agricultural land use or chromium within mafic alluvium.

California↗

Atrazine and its metabolites as indicators of stream-aquifer interaction in Kansas, USA

A survey of atrazine and its metabolites in Kansas ground water indicated that ground-water quality was impacted by stream-aquifer interaction between rivers in the Kansas River basin and their adjacent alluvial aquifers. Atrazine was detected in 19 of the 78 samples. The most common metabolite, deethylatrazine, was detected in 25 samples, 18 of which also had atrazine. The deethylatrazine/atrazine ratio (DAR) of < 1.0 indicates rapid movement of agricultural chemicals to ground water. In this study, 12 of 18 samples had DAR values < 1.0, suggesting rapid recharge to the aquifers. Hydroxyatrazine is seldom detected in ground water. In this study hydroxyatrazine was detected primarily in wells sited in alluvium of rivers. These rivers contain atrazine in varying concentrations. Results of the study suggest that stream-aquifer interaction is a process contributing to the presence of both atrazine and its metabolites in ground water in these areas.A survey of atrazine and its metabolites in Kansas ground water indicated that ground water quality was impacted by stream-aquifer interaction between rivers in the Kansas River basin and their adjacent alluvial aquifers. Atrazine was detected in 19 of the 78 samples. The most common metabolite, deethylatrazine, was detected in 25 samples, 18 of which also had atrazine. The deethylatrazine/attrazine ratio (DAR) of < 1.0 indicates rapid movement of agricultural chemicals to ground water. In this study, 12 of 18 samples had DAR values < 1.0, suggesting rapid recharge to the aquifers. Hydroxyatrazine is seldom detected in ground water. In this study hydroxyatrazine was detected primarily in wells sited in alluvium of rivers. These rivers contain atrazine in varying concentration. Results of the study suggest that stream-aquifer interaction is a process contributing to the presence of both attrazine and its metabolites in ground water in these areas.

Kansas↗

Effect of urban runoff on the quality of lakes in Eagan, Minnesota

Sixteen lakes in the city of Eagan, Minnesota, were sampled during 1982-83 to detect water-quality changes that might have occurred because of urbanization since a previous study conducted during 1972-78. Each of the lakes was sampled five times to determine pH, specific conductance, dissolved oxygen, water temperature, transparency, and concentration of dissolved chloride. Three determinations of chlorophyll were made for each of the lakes near the end of the study, and additional determinations were made for a few lakes of particular interest. Most of the lakes have been incorporated into the city's storm-runoff system for use as retention basins during large storms. The chemistry of the lakes appears to be degraded by urban runoff. Chloride concentrations were significantly higher in six lakes than during the previous study, and remained elevated (about 30 milligrams per liter) in four other lakes. The association between increased chloride and specific conductance with runoff from urban areas suggests that the lakes are subject to contamination by chloride commonly present in urban runoff, and chloride concentrations harmful to aquatic life may have been associated with high specific conductance measured in one of the lakes. Analysis of the data collected for this study indicate that the chemistry of the lakes changes, adjusting to a variety of influences including (1) alternate loading and flushing by runoff, (2) excessive average-annual precipitation, (3) changing ground-water and lake interactions, and (4) changing land use in the lake watersheds. Some lakes affected by urban runoff had reduced concentrations of total phosphorus; however, other lakes unaffected by urban runoff also had significantly lower phosphorus, suggesting that increased precipitation may have diluted the lake water. Ten phosphorus-loading models tested or developed during the previous study generally were found to be inadequate for describing the results of this study. The trophic status of 12 lakes improved but declined in the other 4 lakes, and productivity increased 38 percent in what had been the least-eutrophic lake.

Minnesota↗

Petrogenesis and geological history of a uranium source rock: a case study in northeastern Washington, U.S.A.

A small (4 km 2 ) drainage basin in northeastern Washington contains highly uraniferous groundwater and highly uraniferous peaty sediments of Holocene age. The U is derived from granitic bedrock that underlies the entire drainage basin and that contains 9–16 ppm U. This local bedrock was studied by petrographic, chemical and isotopic methods to determine conditions of its petrogenesis and post-emplacement history that may have contributed to its present high U content and source-rock capability. The original magma was derived by anatexis of Precambrian continental crust of probable mixed metaigneous and metasedimentary character. Mineral-melt partitioning controlled the enrichment of U in chemically evolved phases of the crystallizing melt. Following emplacement in the upper crust at ∼100Ma, the pluton interacted with meteoric-hydrothermal water at ambient temperatures 300°C. Locally intense fracturing promoted alteration, and fracturing and alteration probably continued during later regional uplift in the Eocene. Regional uplift was followed by low-temperature alteration and weathering in the middle to late Tertiary. The combined result of hydrothermal alteration and low-temperature alteration and weathering was the redistribution of U from primary mineral hosts such as allanite to new sites on fracture surfaces and in secondary minerals such as hematite. Zones of highly fractured and altered rock show the most obvious evidence of this process. A model is proposed in which high-angle fractures beneath the drainage basin were the sites of Tertiary supergene enrichments of U. Recent glacio-isostatic uplift has elevated these older enriched zones to shallow levels where they are now being leached by oxidizing groundwater. The chemistry, mineralogy, texture and geological history of this U source-rock suggest criteria for locating other granitic terrane that may contain uraniferous waters and associated young surficial U deposits. The details of U distribution and mobility at this site also apply to the general topic of U mobility in granitic rocks.

Washington↗

Comprehensive inter-laboratory calibration of reference materials for δ18O versus VSMOW using various on-line high-temperature conversion techniques

Internationally distributed organic and inorganic oxygen isotopic reference materials have been calibrated by six laboratories carrying out more than 5300 measurements using a variety of high-temperature conversion techniques (HTC) in an evaluation sponsored by the International Union of Pure and Applied Chemistry (IUPAC). To aid in the calibration of these reference materials, which span more than 125‰, an artificially enriched reference water ( δ 18 O of +78.91‰) and two barium sulfates (one depleted and one enriched in 18 O) were prepared and calibrated relative to VSMOW2 and SLAP reference waters. These materials were used to calibrate the other isotopic reference materials in this study, which yielded: Reference material δ 18 O and estimated combined uncertainty IAEA-602 benzoic acid +71.28 ± 0.36‰ USGS35 sodium nitrate +56.81 ± 0.31‰ IAEA-NO-3 potassium nitrate +25.32 ± 0.29‰ IAEA-601 benzoic acid +23.14 ± 0.19‰ IAEA-SO-5 barium sulfate +12.13 ± 0.33‰ NBS 127 barium sulfate +8.59 ± 0.26‰ VSMOW2 water 0‰ IAEA-600 caffeine −3.48 ± 0.53‰ IAEA-SO-6 barium sulfate −11.35 ± 0.31‰ USGS34 potassium nitrate −27.78 ± 0.37‰ SLAP water −55.5‰ The seemingly large estimated combined uncertainties arise from differences in instrumentation and methodology and difficulty in accounting for all measurement bias. They are composed of the 3-fold standard errors directly calculated from the measurements and provision for systematic errors discussed in this paper. A primary conclusion of this study is that nitrate samples analyzed for δ 18 O should be analyzed with internationally distributed isotopic nitrates, and likewise for sulfates and organics. Authors reporting relative differences of oxygen-isotope ratios ( δ 18 O) of nitrates, sulfates, or organic material should explicitly state in their reports the δ 18 O values of two or more internationally distributed nitrates (USGS34, IAEA-NO-3, and USGS35), sulfates (IAEA-SO-5, IAEA-SO-6, and NBS 127), or organic material (IAEA-601 benzoic acid, IAEA-602 benzoic acid, and IAEA-600 caffeine), as appropriate to the material being analyzed, had these reference materials been analyzed with unknowns. This procedure ensures that readers will be able to normalize the δ 18 O values at a later time should it become necessary. The high-temperature reduction technique for analyzing δ 18 O and δ 2 H is not as widely applicable as the well-established combustion technique for carbon and nitrogen stable isotope determination. To obtain the most reliable stable isotope data, materials should be treated in an identical fashion; within the same sequence of analyses, samples should be compared with working reference materials that are as similar in nature and in isotopic composition as feasible.

Rapid Communications in Mass Spectrometry↗

Techniques for restoration of disturbed coastal wetlands of the Great Lakes

A long history of human-induced degradation of Great Lakes wetlands has made restoration a necessity, but the practice of wetland restoration is relatively new, especially in large lake systems. Therefore, we compiled tested methods and developed additional potential methods based on scientific understanding of Great Lakes wetland ecosytems to providc an overview of approaches for restoration. We addressed this challenge by focusing on four general fields of science: hydrology, sedimentology, chemistry, and biology. Hydrologic remediation methods include restoring hydrologic connections between diked and hydrologically altered wetlands and the lakes, restoring water tables lowered by ditching, and restoring natural variation in lake levels of regulated lakes Superior and Ontario. Sedimentological remediation methods include management of sediment input from uplands, removal or proper management of dams on tributary rivers, and restoration of protective barrier beaches and sand spits. Chemical remediation methods include reducing or eliminating inputs of contaminants from point and non-pont sources, natural sediment remediation by biodegradation and chemical degradation, and active sediment remediation by removal or by in situ treatment Biological remediation methods include control of non-target organisms, enhancing populations of target organisms, and enhancing habitat for target organisms. Some of these method were used in three major restoration projects (Metzger Marsh on Lake Erie and Cootes Paradise and Oshawa Second Marsh on Lake Ontario), which are described as case studies to show practical applications of wetland restoration in the Great Lakes. Successful restoration techniques that do not require continued manipulation must be founded in the basic tenets of ecology and should mimic natural processes. Success is demonstrated by the sustainability, productivity, nutrient-retention ability, invasibility, and biotic interactions within a restored wetland.

Wetlands↗

Reactive solute transport in streams: A surface complexation approach for trace metal sorption

A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron- oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

Water Resources Research↗

Lithologic descriptions of two cores and ground-water-quality data from five counties in the northeastern part of the coastal plain of South Carolina, 1988 and 1991

This report presents data collected as part of a hydrologic investigation of Darlington, Dillon, Florence, Marion, and Marlboro Counties in the northeastern part of the Coastal Plain of South Carolina. These data include lithologic descriptions of sediment recovered from two continuously cored boreholes and water-quality results for samples collected from 17 existing wells. One continuously cored borehole was drilled near Lake Darpo in the northern part of Darlington County to a total depth of 447 feet below land surface. The other borehole was drilled in Lake City in the south-central part of Florence County to a total depth of 1,090 feet below land surface. Water-quality results presented in this report include specific conductance, dissolved oxygen, temperature, pH, alkalinity, major- and minor-ion chemistry, and hydrogen sulfide.

South Carolina↗

The future of nearshore processes research

The nearshore is the transition region between land and the continental shelf including (from onshore to offshore) coastal plains, wetlands, estuaries, coastal cliffs, dunes, beaches, surf zones (regions of wave breaking), and the inner shelf (Figure ES-1). Nearshore regions are vital to the national economy, security, commerce, and recreation. The nearshore is dynamically evolving, is often densely populated, and is under increasing threat from sea level rise, long-term erosion, extreme storms, and anthropogenic influences. Worldwide, almost one billion people live at elevations within 10 m of present sea level. Long-term erosion threatens communities, infrastructure, ecosystems, and habitat. Extreme storms can cause billions of dollars of damage. Degraded water quality impacts ecosystem and human health. Nearshore processes, the complex interactions between water, sediment, biota, and humans, must be understood and predicted to manage this often highly developed yet vulnerable nearshore environment. Over the past three decades, the understanding of nearshore processes has improved. However, societal needs are growing with increased coastal urbanization and threats of future climate change, and significant scientific challenges remain. To address these challenges, members of academia, industry, and federal agencies (USGS, USACE, NPS, NOAA, FEMA, ONR) met at the “The Past and Future of Nearshore Processes Research: Reflections on the Sallenger Years and a New Vision for the Future” workshop to develop a nearshore processes research vision where societal needs and science challenges intersect. The resulting vision is comprised of three broad research themes: Long-term coastal evolution due to natural and anthropogenic processes: As global climate change alters the rates of sea level rise and potentially storm patterns and coastal urbanization increases over the coming decades, an understanding of coastal evolution is critical. Improved knowledge of long-term morphological, ecological, and societal processes and their interactions will result in an improved ability to simulate coastal change. This will enable proactive solutions for resilient coasts and better guidance for reducing coastal vulnerability. Extreme Events: Flooding, erosion, and the subsequent recovery: Hurricane Sandy caused flooding and erosion along hundreds of miles of shoreline, flooded New York City, and impacted communities and infrastructure. Overall U.S. coastal extreme event related economic losses have increased substantially. Furthermore, climate change may cause an increase in coastal extreme events and rising sea levels could increase the occurrence of extreme events. Addressing this research theme will result in an improved understanding of the physical processes during extreme events, leading to improved models of flooding, erosion, and recovery. The resulting societal benefit will be more resilient coastal communities. The physical, biological and chemical processes impacting human and ecosystem health: Nearshore regions are used for recreation, tourism, and human habitation, and provide habitat and valuable ecosystem services. These areas must be sustained for future generations, however overall coastal water quality is declining due to microbial pathogens, fertilizers, pesticides, and heavy metal contamination, threatening ecosystem and human health. To ensure sustainable nearshore regions, predictive real-time water- and sediment-based based pollutant modeling capabilities must be developed, which requires expanding our knowledge of the physics, chemistry, and biology of the nearshore. The resulting societal benefits will include better beach safety, healthier ecosystems, and improved mitigation and regulatory policies. The scientists and engineers of the U.S. nearshore community are poised to make significant progress on these research themes, which have significant societal impact. The U.S. nearshore community, including academic, government, and industry colleagues, recommends multi-agency investment into a coordinated development of observational and modeling research infrastructure to address these themes, as discussed in the whitepaper. The observational infrastructure should include development of new sensors and methods, focused observational programs, and expanded nearshore observing systems. The modeling infrastructure should include improved process representation, better model coupling, incorporation of data assimilation techniques, and testing of real-time models. The observations will provide test beds to compare and improve models.

Report↗

Comparison of two estrogen chemically activated luciferase expression cell bioassays to liquid chromatography–mass spectrometry for quantifying estrone in water samples

Chemically activated luciferase expression (CALUX) cell bioassays are popular tools for assessing endocrine activity of chemicals such as certain environmental contaminants. Although activity equivalents can be obtained from CALUX analysis, directly comparing these equivalents to those obtained from analytical chemistry methods can be problematic because of the complexity of endocrine active pathways. We explored the suitability of two estrogen CALUX bioassays (the Organisation for Economic Co-operation and Development–approved VM7Luc4E2 cell bioassay and the VM7LucERβc9 cell bioassay) for quantitation of estrogen. Quadrupole-time of flight ultraperformance liquid chromatography–mass spectrometry (LC/MS) was selected as a comparative method. Regression analysis of measured estrone (E1) calibration samples showed all three methods to be highly predictive of nominal concentrations ( p ≤ 7.5 × 10 –51 ). Extracts of water sampled from laboratory dilutor tanks containing E1 at 0, 20, and 200 ng/L alone and in combination with atrazine were selected to test the quantitative capabilities of the CALUX assays. Process controls (0 and 100 ng E1/L) and a separate E1 standard (10 ng/ml, used to prepare the E1 process control) were also tested. Levels of E1 determined by LC/MS analysis and bioanalytical equivalents (ng E1/L) determined by CALUX analyses were comparable except in certain instances where the samples required dilution prior to CALUX analyses (e.g., the E1 process control and E1 standard). In those instances, measurements by CALUX were slightly but significantly decreased relative to LC/MS. Atrazine had no effect on the ability of either LC/MS or the CALUX bioassays to quantify E1. The present study illustrates the CALUX bioassays as successful in quantifying an estrogen in simple water samples and further characterizes their utility for screening. Environ Toxicol Chem 2023;42:333–339. Published 2022. This article is a U.S. Government work and is in the public domain in the USA.

Environmental Toxicology and Chemistry↗

Simulated flow of groundwater and brine from a flooded salt mine in Livingston County, New York, and effects of remedial pumping on an overlying aquifer

Two ceiling collapses in the Retsof salt mine near Geneseo in upstate New York in spring 1994 resulted in the upward propagation of two columns of rubble through 600 feet of overlying shale and carbonate bedrock. This upward propagation formed a hydraulic connection between the lower confined aquifer (LCA) and the mine and allowed water from the aquifer and bedrock fracture zones that intersected the rubble columns to flow into the mine at a rate of 18,000 gallons per minute (gal/min) . All salt mining ceased in September 1995, and the mine was completely flooded by January 1996. The flow of water from the lower confined aquifer into the mine caused widespread drawdowns, and water levels in the aquifer declined by as much as 400 feet near the collapse area and by more than 50 feet at wells 7 miles to the north and south. Within 3 to 4 weeks of the collapses, water levels in about a dozen domestic and industrial wells had declined severely, and some wells went dry. Water levels in at least 58 wells in the lower and middle confined aquifers were affected by mine flooding. Groundwater in the upper unconfined aquifer and surface water in streams were unaffected by water-level drawdown, but channels of the Genesee River and Beards Creek were altered by land subsidence related to the mine collapse. Water levels recovered from 1996 through 2006, but the mine is now filled with about 15 billion gallons of saturated halite brine. The weight of the overlying rock and sediment is expected to cause the salt beds to deform and fill the mine cavity during the next several hundred years; this in turn could displace as much as 80 percent of the brine and cause it to move upward through the rubble chimneys, rendering the LCA unusable as a source of water supply. Saline water was detected in the LCA in 2002 but was found to be derived primarily from fractures in the limestone and shale units between the mine and the LCA, rather than from the mine. In September 2006, the mine company began a brine-mitigation project that entailed pumping five wells finished in limestone and shale units within the collapse areas to alter the flow gradient and thereby prevent further movement of brine and saline water into the LCA. The pumped brine was routed to an onsite desalination plant. At the same time, the U.S. Geological Survey (USGS) began a study in cooperation with the New York State Office of the Attorney General to construct numerical models to analyze the groundwater chemistry and delineate the directions of flow. Specific objectives of the study were to: * Assess the sources of salinity within the collapse area and identify the factors that control the movement and mixing of freshwater, saline waters from fracture zones, and brine; * Evaluate the likelihood that the pumping will induce anhydrite dissolution and lead to continued land subsidence; * Construct variable-density groundwater flow models to predict the effect of remedial pumping on salinity within the LCA; * Evaluate the effectiveness of remedial pumping in preventing the movement of saline water into the LCA; and * Predict the extent of brine migration 8 years after a hypothetical shutdown of all pumping in 2008. This report (1) summarizes the hydrogeologic setting and effects of mine flooding, (2) describes the geochemical and variable-density model simulations and their principal results, (3) discusses the implications of (a) continued pumping and desalination to protect the LCA and (b) a full shutdown of pumping after 2008, and (4) suggests further research that could lead to refinement of model predictions. Additional information may be found in Yager and others (2001 and 2009). These reports can be accessed at http://pubs.usgs.gov/pp/pp1611/ and http://pubs.usgs.gov/pp/pp1767/, respectively. A summary of simulation results can be accessed at http://ny.water.usgs.gov/projects/Coram/seawat/seawat.html.

New York↗

Hydrogeologic setting and simulation of pesticide fate and transport in the unsaturated zone of a regolith-mantled, carbonate-rock terrain near Newville, Pennsylvania

Physical and chemical data were collected from May 1991 through April 1993 at a 4.5 hectare field site in Cumberland County, Pa., about 5 kilometers southeast of Newville. These data were used to define the hydrogeologic setting of a field site representative of the intensively farmed carbonate valleys of southeastern and south-central Pennsylvania. The environmental processing of commonly used pesticides (herbicides, fungicides, and insecticides) in the unsaturated zone was simulated with a process- oriented digital model to evaluate the environmental fate and transport of pesticides to ground water. Site data and modelling results provide a basis for a discussion of water-quality implications of agricultural best-management practices. The carbonate valleys of Pennsylvania comprise regolith-mantled carbonate-rock terrains that consist of broad undulating upland areas dissected by mostly dry valleys and widely spaced spring-fed creeks. The upland areas are farmed and exhibit possess a doline karst topography with many closed depressions, sinkholes, and bedrock outcrops. Unsaturated materials at the field site consist of an almost continuous soil cover composed of fine-grained residuum underlain by an intermediate vadose zone composed of karstified limestone. Soils are absent on scattered bedrock outcrops and are more than 12 meters thick in other areas of the site. The soil profile stores appreciable quantities of water with a volumetric average of about 36 percent water at field capacity. Organic carbon content of soil materials is about 1.7 percent in the Ap-horizon and from 0.1 to 0.3 percent throughout the full thickness of the B- and C-horizons. Atrazine, metolachlor, simazine, and the atrazine soil metabolites deethylatrazine and deisopropylatrazine were detected at concentrations above 0.05 mg/L in just the upper 0.6 meters of soil materials. However, detectable concentrations of atrazine, simazine, and atrazine soil metabolites were measured in water samples from lysimeters installed in soil materials at depths of 1.2, 2.1, and 3.7 meters and from monitor wells completed in the saturated zone to depths of 122 meters. Data collected from the field site were used to configure a pesticide screening model based on the pesticide version of the leaching estimation and chemistry model (LEACHP) developed by Wagenet and Hutson (1987). Model simulations show that most field-applied pesticides volatilize to the atmosphere, accumulate in soils, degrade in the subsurface environment, or leach to ground water. Model results were used to rank the leaching potentials of 66 pesticides. Eighteen of 32 herbicides, 4 of 9 fungicides, and 10 of 25 insecticides have moderate to large potential for leaching to ground water. A review of available pesticide monitoring data suggests that many compounds given moderate or high leaching potentials have not been tested for in ground water and the presence of pesticides in Pennsylvania's ground water may be underreported. Monitoring data do not exist for more than two-thirds of the pesticide compounds currently used in agricultural, carbonate areas of Pennsylvania. Knowledge of processes that govern fate and transport of pesticides is needed to facilitate development of effective pesticide best-management practices. In addition to comprehensive monitoring for pesticides and pesticide degradation products in ground water downgradient of areas of pesticide use, improved (1) characterization of unsaturated flow and transport through regolith mantled carbonate rocks, (2) estimates of pesticide degradation rates, (3) understanding of soil-property controls on pesticide movement, and (4) management models developed from process-oriented research would aid in understanding the processes.

Water-Resources Investigations Report↗

Arsenic in ground-water under oxidizing conditions, south-west United States

Concentrations of dissolved arsenic in ground-water in alluvial basins of Arizona commonly exceed 50 μg L −1 and reach values as large as 1,300 μg L −1 . Arsenic speciation analyses show that arsenic occurs in the fully oxidized state of plus 5 (As+5), most likely in the form of HAsO4 ∼2 , under existing oxidizing and pH conditions. Arsenic in source areas presumably is oxidized to soluble As before transport into the basin or, if after transport, before burial. Probable sources of arsenic are the sulphide and arsenide deposits in the mineralized areas of the mountains surrounding the basins. Arsenic content of alluvial material ranged from 2 to 88 ppm. Occurrence and removal of arsenic in ground-water are related to the pH and the redox condition of the ground-water, the oxidation state of arsenic, and sorption or exchange. Within basins, dissolved arsenic correlates (P<0.01) with dissolved molybdenum, selenium, vanadium, and fluoride and with pH, suggesting sorption of negative ions. The sorption hypothesis is further supported by enrichment of teachable arsenic in the basin-fill sediments by about tenfold relative to the crustal abundance and by as much as a thousandfold relative to concentrations found in ground-water. Silicate hydrolysis reactions, as defined within the alluvial basins, under closed conditions cause increases in pH basinward and would promote desorption. Within the region, large concentrations of arsenic are commonly associated with the central parts of basins whose chemistries evolve under closed conditions. Arsenic does not correlate with dissolved iron (r = 0.09) but may be partly controlled by iron in the solid phase. High solid-phase arsenic contents were found in red clay beds. Large concentrations of arsenic also were found in water associated with red clay beds. Basins that contain the larger concentrations are bounded primarily by basalt and andesite, suggesting that the iron content as well as the arsenic content of the basin fill may play a role in the occurrence of arsenic in ground-water. Under oxidizing conditions in Arizona, arsenic in ground-water appears to be controlled in part by sorption or desorption of HAsO4 ∼2 on active ferric oxyhydroxide surfaces.

Arizona, California, Nevada, New Mexico↗

Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

Florida↗

Influence of bromide on the performance of the amphipod Hyalella azteca in reconstituted waters

Poor performance of the amphipod Hyalella azteca has been observed in exposures using reconstituted waters. Previous studies have reported success in H. azteca water-only exposures with the addition of relatively high concentrations of bromide. The present study evaluated the influence of lower environmentally representative concentrations of bromide on the response of H. azteca in 42-d water-only exposures. Improved performance of H. azteca was observed in reconstituted waters with >0.02 mg Br/L.

Environmental Toxicology and Chemistry↗

The origin of the Cerro Prieto geothermal brine

The Cerro Prieto geothermal brine may have originated from mixing of Colorado River water with seawater evaporated to about six times its normal salinity. This mixture circulated deeply and was heated by magmatic processes. During deep circulation, Li, K, Ca, B, SiO 2 and rare alkalis were transferred from rock minerals to the water, and Mg, SO 4 , and a minor quantity of Na were transferred to the rock. Similar alteration of seawater salt chemistry has been observed in coastal geothermal systems and produced in laboratory experiments. After heating and alteration the brine was further diluted to its present range of composition. Oxygen isotopes in the fluid are in equilibrium with reservoir calcite and have been affected by exploitation-induced boiling and dilution.

Geothermics↗

Stability of inorganic and methylated arsenic species in laboratory standards, surface water and groundwater under three different preservation regimes

Geogenic arsenic (As) adversely affects drinking water quality in geologically diverse aquifers across the globe. Although the species of As significantly affects its fate, transport, toxicity, and As treatment technology efficacy, reported effectiveness of As species preservation methods varies widely with preservation methods and natural water geochemistry. Our study 1) evaluates the shelf life of As(III), As(V), dimethylarsinate (DMA), and monomethylarsonate (MMA) in standards prepared with ultrapure water; 2) establishes a hold time for these As species in low-iron (Fe) groundwater and surface water samples preserved with a concentration of EDTA that exceeded the sum of the molar concentrations of Al, Fe, Mn, Ca, Mg, and Sr (molar excess of EDTA); and 3) evaluates As(III) species stability in groundwater samples with detectable SO 4 and up to 6.5 mg/L Fe concentrations preserved in 3 ways: less than molar excess EDTA, molar excess EDTA, and Vacuette® tubes with an unknown (proprietary) amount of EDTA. Arsenic species standards prepared with 2.5 mM EDTA in ultrapure water and stored at 4 °C had a shelf life of at least 180 days. As(III) was stable for at least 15 days and DMA and MMA were stable for at least 90 days in environmental samples with Fe less than 1 mg/L that were preserved with a molar excess of EDTA and stored in opaque containers at 4 °C. As(III) species were not stable for any holding time in samples with Fe greater than 1 mg/L and detectable SO 4 when preserved with a molar excess of EDTA and stored in white high density polyethylene bottles at room temperature, or when preserved by storage in EDTA containing Vacuette® tubes at 4 °C. For geochemical or water quality studies where the distribution of As(III) and As(V) is a critical factor, an understanding of the sample chemistry, rapid As speciation analysis after sample collection, and collecting a field spike with the sample can be helpful for collecting accurate inorganic As species data.

Applied Geochemistry↗