Groundwater quality is often affected by anthropogenic activities in urban settings. This study examines groundwater quality in and around the Santa Fe Springs Oil Field in Los Angeles County, California, where oil and gas production commonly intersects with high density industrial, commercial and residential land uses. Utilizing a combination of new and historical data, we evaluated potential pathways that would allow for oil field formation fluids to migrate into groundwater and whether mixing may have occurred based on the distribution of groundwater and oil field formation fluid tracers in samples. Samples were analyzed for a wide array of constituents including volatile organic compounds, light hydrocarbons, major ions, and various isotopic compositions. Despite evidence of oil field infrastructure providing potential pathways of migration via uncemented annular spaces, casing breaches and historical disposal of oil field formation water in surface ponds, the distribution and occurrence of stable isotopes of water, chloride, boron, and total dissolved solids do not indicate mixing of oil field formation water and groundwater. However, methane isotopic signatures and the presence of heavier alkanes suggest gas from oil-bearing formations have migrated from depth via oil field well infrastructure. Volatile organic compound detections were mainly from manufactured compounds unrelated to oil and gas production, with a relatively limited number of petroleum hydrocarbons also detected. Volatile organic compounds were generally found in wells tapping shallow, modern aged groundwater, indicating anthropogenic activities occurring at or near land surface as the source. Study results suggest that while oil field infrastructure provides migration pathways for oil field formation fluids to be introduced into groundwater, urban land uses not related to oil and gas production are the primary drivers of groundwater quality degradation.

The fumigant pesticide 1,2-dibromo-3-chloropropane (DBCP) was widely used in California agriculture during the 1960s and 1970s before being banned in 1979. Despite this ban, DBCP continues to contaminate groundwater due to its persistence and mobility. This study evaluates the distribution, historical trends, and projected persistence of DBCP in California using data from over 13,000 public supply wells and additional domestic, irrigation, and observation wells (1980–2022). Since 2010, DBCP has been detected in 9% of public-supply wells statewide, with higher frequencies in the San Joaquin Valley (21%) and upper Santa Ana River watershed (13%), where DBCP use was most prevalent. Approximately 70% of wells had decreasing concentration trends, whereas increases were more common in deeper wells, indicating downward vertical migration of the DBCP front. Groundwater-age estimates show that recharge timing aligns with the 1960s–1970s loading period, enabling reconstruction of peak inputs and providing a basis for age-based modeling. To estimate future persistence, we applied a one-dimensional advection–dispersion model that simulates long-term declines in peak concentrations based on groundwater age, historical loading, and a 38-year degradation half-life. Model projections suggest that concentrations above the maximum contaminant level may persist in a declining number of wells until approximately 2080 (range: 2048–2109), with longer persistence in the San Joaquin Valley. The simplified modeling framework, based on age distributions typical of wells capturing peak concentrations, can provide practical regional-scale assessment of non-point source contaminants where long-term monitoring exists. This study highlights how the legacy of DBCP contamination will likely affect California's groundwater resources throughout the 21st century.

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 micrograms 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 (S2-) concentrations (maximum concentration 29 milligrams 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.

This article is a joint statement of recommendations for HIV prevention in industrialized countries targeting men who have sex with men. The statement was issued at an international symposium of HIV prevention practitioners and theorists organized in 1996 by the Deutsche AIDS-Hilfe, the national German AIDS organization. The objectives of the symposium were: (1) To identify and critically examine current paradigms; (2) To promote a deeper and more intensive debate; (3) To create a basis for new international collaborative ventures; and, (4) To consolidate and advance international discussion. The meeting focused on three topics: (1) New and neglected factors influencing people to engage in sexual acts which increase or decrease risk; (2) The meaning of sexuality/sexual acts and identity; and, (3) The factors fostering or impeding the implementation of prevention strategies, present and future. Among the recommendations made by the participants are: placing a greater focus on protective factors as opposed to risk factors; examining the meaning and context of sexual acts more closely; moving beyond prescriptive advice on sexual safety; and expanding beyond an ex-2 elusive focus on HIV so as to include other health issues. [Article copies available for a fee from The Haworth Document Delivery Seivice: 1-800-342-9678. E-mail address: getinfo@haworthpressinc.com ]

Noble gases record fluid interactions in multiphase subsurface environments through fractionation processes during fluid equilibration. Water in the presence of hydrocarbons at the subsurface acquires a distinct elemental signature due to the difference in solubility between these two fluids. We find the atmospheric noble gas signature in produced water is partially preserved after hydrocarbons production and water disposal to unlined ponds at the surface. This signature is distinct from meteoric water and can be used to trace oil-field water seepage into groundwater aquifers. We analyse groundwater (n = 30) and fluid disposal pond (n = 2) samples from areas overlying or adjacent to the Fruitvale, Lost Hills, and South Belridge Oil Fields in the San Joaquin Basin, California, USA. Methane (2.8 x 10(-7) to 3 x 10(-2) cm(3) STP/cm(3)) was detected in 27 of 30 groundwater samples. Using atmospheric noble gas signatures, the presence of oil-field water was identified in 3 samples, which had equilibrated with thermogenic hydrocarbons in the reservoir. Two (of the three) samples also had a shallow microbial methane component, acquired when produced water was deposited in a disposal pond at the surface. An additional 6 samples contained benzene and toluene, indicative of interaction with oil-field water; however, the noble gas signatures of these samples are not anomalous. Based on low tritium and C-14 contents (<= 0.3 TU and 0.87-6.9 pcm, respectively), the source of oil-field water is likely deep, which could include both anthropogenic and natural processes. Incorporating noble gas analytical techniques into the groundwater monitoring programme allows us to 1) differentiate between thermogenic and microbial hydrocarbon gas sources in instances when methane isotope data are unavailable, 2) identify the carrier phase of oil-field constituents in the aquifer (gas, oil-field water, or a combination), and 3) differentiate between leakage from a surface source (disposal ponds) and from the hydrocarbon reservoir (either along natural or anthropogenic pathways such as faulty wells).

The purpose of this study is to determine the occurrence, movement, and sources of perchlorate in groundwater using a comprehensive set of environmental tracers coupled with discrete borehole data. Potential sources of perchlorate to groundwater at the study site have been attributed to waste disposal and industrial activities as well as to past agricultural operations. Perchlorate concentrations in samples ranged from <1 to 40 mu g/l, with a median of 6.1 mu g/l. Concentrations were relativity consistent with depth except at one site where dilution may be occurring due to the infiltration of surface water from Pyrite Creek. Well-bore flow profiles indicated that perchlorate redistribution was occurring via intra-well bore flow at one site where up to 14,000 mg/year of perchlorate could be moving from the shallower to the deeper zones of the alluvial aquifer. Natural attenuation processes of perchlorate do not appear to be widespread in groundwater but do occur in portions of the aquifer adjacent to the Santa Ana River, likely limiting the mobility of perchlorate from the southernmost extent of the mapped plume to areas farther down-gradient. Age dating tracers indicate that the advective transport of perchlorate originating from the waste disposal ponds has largely moved through the zones of the aquifer sampled. Age distributions, noble gas temperature, delta neon values and stable isotopes of water indicate that a substantial fraction of perchlorate in groundwater may have been mobilized from the unsaturated zone and/or is from the infiltration of storm water runoff originating from Pyrite Canyon.

Relative risks of groundwater-quality degradation near selected California oil fields are estimated by examining spatial and temporal patterns in chemical and isotopic data in the context of groundwater-age categories defined by tritium and carbon-14. In the Coastal basins, western San Joaquin Valley (SJV), and eastern SJV; 82, 76, and 0% of samples are premodern (pre-1953 recharge), respectively; and 3, 0, and 31% are modern (recharged during or after 1953), respectively. Carbon-14 and helium-4 data indicate most premodern samples are 1000 to 10,000 (33%) or >10,000 (50%) years old. Organic chemicals that could be associated with deeper hydrocarbon reservoirs (e.g. thermogenic gases and benzene) occur most frequently in premodern groundwater, suggesting premodern groundwater has a higher risk of degradation from upward migration of hydrocarbons than modern and mixed-age groundwater. Low sulfate concentrations in some premodern groundwater containing high thermogenic-methane concentrations (>28 mg/L) indicate methane attenuation associated with sulfate reduction can be limited in premodern groundwater. The more common occurrence of manufactured compounds, like tetrachloroethene, in modern and mixed-age groundwater than in premodern groundwater indicates modern and mixed-age groundwater has a higher risk of degradation from land-surface sources than premodern groundwater. Time-series data for chloride in groundwater affected by disposal of oil-field water in unlined ponds indicate some modern and mixed-age groundwater are susceptible to chemical migration within 2-3 km of surface sources. Timescales for diluting chloride concentrations in groundwater with fresh recharge once disposal ponds are decommissioned are shorter in mixed-age groundwater with large fractions of modern water (9-14 years in one example) than in mixed-age groundwater with large fractions of premodern water (no evidence of dilution after 12 years of monitoring in one example). The presence of predominantly premodern groundwater in the Coastal basins and western SJV indicates these areas have relatively high risk from upward migration of hydrocarbons, reduced methane attenuation capacity, and long dilution times, whereas predominantly modernand mixed-age groundwater in the eastern SJV indicates this area has relatively high risk from chemical migration from land-surface sources and subsequent extensive spreading. Age-based characterizations of relative risk could inform the design of groundwater-monitoring programs near oil fields in terms of the spatial distribution of monitoring points relative to source areas and monitoring frequency and duration.

Due to concerns over the effects of oil production activities on groundwater quality in California, chemical, isotopic, dissolved gas and age-dating tracers were analyzed in samples collected from public-supply wells and produced-water sites in the Fruitvale oil field (FVOF). A combination of newly collected and historical data was used to determine whether oil formation fluids have mixed with groundwater used for public supply and what the potential pathways for the migration of oil formation fluids into groundwater may be. Stable isotopes of water (delta H-2 and delta O-18) and age dating (H-3, He-3(tr)it, SF6 and C-14) tracers in groundwater samples were consistent with the Kern River being the main source of recharge to aquifers. The distribution of major ion concentrations and pH with distance from the Kern River indicate that natural processes were the primary controls on groundwater salinity. Two of 14 groundwater samples had delta(13) C-DIC values (- 2.4 to + 1.9 per mil) consistent with mixtures of < 1 to about 9 percent oil-field water. Concentrations of TDS in groundwater samples were generally much lower (129-1,200 milligrams per liter (mg/l), median 216 mg/l) than produced water samples (586-24,930 mg/l, median 2,717 mg/l), suggesting that any mixing of oil-field water with groundwater has not significantly affected groundwater salinity. Trace concentrations of thermogenic methane were detected in three groundwater samples that did not have dissolved inorganic or isotopic indicators consistent with mixing of oilfield water, suggesting that stray gases may have migrated from the subsurface via preferential pathways such as leaky well bores into groundwater aquifers. Low concentrations of petroleum hydrocarbons were detected in samples that also contained anthropogenic VOCs and components of post- and pre-1950s recharge, indicating that petroleum hydrocarbons could have come from subsurface and/or surface sources. Overall, the results of this study indicated that groundwater currently used for public supply in the FVOF was of good quality with little, if any, effects from oil production activities. This may be due in part to the relatively rapid flushing of the aquifer system by recharge from the Kern River.

Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range = 0.010-0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p < 0.001, ρ = 0.90, range = 145-15,900 mg/L), Mn + Fe concentrations (p < 0.001, ρ = 0.82, range = <0.005-18.5 mg/L), and pH (p < 0.001, ρ = -0.67, range = 6.2-9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median = 3.1) differed from those in oil-field water (median = 0.51). PHREEQC mixing calculations and spatial geochemical variations suggest that the Ra in the oil-field water was removed by coprecipitation with secondary barite and adsorption on Mn-Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

In 2014, samples from 37 monitoring wells at 17 locations, within or near oil fields, and one site >5km from oil fields, in the Los Angeles Basin, California, were analyzed for dissolved hydrocarbon gas isotopes and abundances. The wells sample a variety of depths of an aquifer system composed of unconsolidated and semiconsolidated sediments under various conditions of confinement. Concentrations of methane in groundwater samples ranged from 0.002 to 150mg/Lsome of the highest concentrations reported in a densely populated urban area. The C-13 and H-2 of the methane ranged from -80.8 to -45.5 per mil () and -249.8 to -134.9, respectively, and, along with oxidation-reduction processes, helped to identify the origin of methane as microbial methanogenesis and CO2 reduction as its main formation pathway. The distribution of methane concentrations and isotopes is consistent with the high concentrations of methane in Los Angeles Basin groundwater originating from relatively shallow microbial production in anoxic or suboxic conditions. Source of the methane is the aquifer sediments rather than the upward migration or leakage of thermogenic methane associated with oil fields in the basin. Plain Language Summary High dissolved methane gas concentrations were measured in 37 groundwater samples collected in the Los Angeles Basin, California. The origin of the methane was identified as microbial activity rather than from the burial and heating of organic material. The source of the methane was microbial production in shallow, oxygen-depleted aquifers rather than the upward migration or leakage of methane associated with oil fields in the basin.

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First posted August 3, 2016 Revised January 31, 2017 For additional information, contact: Director, California Water Science CenterU.S. Geological Survey6000 J Street, Placer HallSacramento, California 95819http://ca.water.usgs.gov In 2014 and 2015, the U.S. Geological Survey (USGS) sampled water wells in the Los Angeles Basin and southern San Joaquin Valley, California, and oil wells in the San Joaquin Valley for analysis of multiple chemical, isotopic, and groundwater-age tracers. The purpose of this reconnaissance sampling was to evaluate the utility of tracers for assessing the effects of oil and gas production activities on groundwater quality in California. The study was done in cooperation with the California State Water Resources Control Board. Results of the study are intended to help design a regional groundwater-monitoring program to be implemented as part of California Senate Bill 4 (SB 4 statutes of 2013). The regional monitoring program plans to assess the effects of oil and gas production activities on groundwater quality and to provide a regional context for local monitoring of the groundwater-quality effects from well-stimulation treatments, which are techniques used to improve oil and gas production by increasing their rate of flow to the well. California SB 4 mandates that this local monitoring is to be done by oil-well operators in accordance with monitoring criteria established by the State Water Board. This report evaluates the utility of the chemical, isotopic, and groundwater-age tracers for assessing sources of salinity, methane, and petroleum hydrocarbons in groundwater overlying or near several California oil fields. Tracers of dissolved organic carbon inoil-field-formation water are also discussed. Tracer data for samples collected from 51 water wells and 4 oil wells are examined.

First posted December 9, 2016 Revised November 21, 2017 For additional information, contact: Director, California Water Science CenterU.S. Geological Survey 6000 J Street, Placer Hall Sacramento, California 95819 Exploratory sampling of groundwater in coastal Los Angeles County and Kern and Kings Counties of the southern San Joaquin Valley was done by the U.S. Geological Survey from September 2014 through January 2015 as part of the California State Water Resources Control Board's Water Quality in Areas of Oil and Gas Production Regional Groundwater Monitoring Program. The Regional Groundwater Monitoring Program was established in response to the California Senate Bill 4 of 2013 mandating that the California State Water Resources Control Board design and implement a groundwater-monitoring program to assess potential effects of well-stimulation treatments on groundwater resources in California. The U.S. Geological Survey is in cooperation with the California State Water Resources Control Board to collaboratively implement the Regional Groundwater Monitoring Program through the California Oil, Gas, and Groundwater Project. Many researchers have documented the utility of different suites of chemical tracers for evaluating the effects of oil and gas development on groundwater quality. The purpose of this exploratory sampling effort was to determine whether tracers reported in the literature could be used effectively in California. This reconnaissance effort was not designed to assess the effects of oil and gas on groundwater quality in the sampled areas. A suite of water-quality indicators and geochemical tracers were sampled at groundwater sites in selected areas that have extensive oil and gas development. Groundwater samples were collected from a total of 51 wells, including 37 monitoring wells at 17 multiple-well monitoring sites in coastal Los Angeles County and 5 monitoring wells and 9 water-production wells in southern San Joaquin Valley, primarily in Kern and Kings Counties. Groundwater samples were analyzed for field waterquality indicators; organic constituents, including volatile and semi-volatile organic compounds and dissolved organic carbon indicators; naturally present inorganic constituents, including trace elements, nutrients, major and minor ions, and iron species; naturally present stable and radioactive isotopes; dissolved noble gases; dissolved standard and hydrocarbon gases, δ13C of methane, ethane, and δ2 H of methane. In total, 249 constituents and water-quality indicators were measured. Four types of quality-control samples (blanks, replicates, matrix spikes, and surrogates spiked in environmental and blank samples) were collected at approximately 10 percent of the wells. The quality-control data were used to determine whether the groundwater-sample data were of sufficient quality for the measured analytes to be used as potential indicators of oil and gas effects. The data from the 51 groundwater samples and from the quality-control samples are presented in this report.

The geochemical conditions, occurrence of selected trace elements, and processes controlling the occurrence of selected trace elements in groundwater were investigated in groundwater basins of the Desert and Basin and Range (DBR) hydrogeologic provinces in southeastern California as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA PBP is designed to provide an assessment of the quality of untreated (raw) groundwater in the aquifer systems that are used for public drinking-water supply. The GAMA PBP is being conducted by the California State Water Resources Control Board in collaboration with the U.S. Geological Survey and the Lawrence Livermore National Laboratory. The DBR hydrogeologic provinces consist of 141 defined groundwater basins separated by mountain ranges, faults, and other features. This report presents analyses of data collected from nine study areas within the DBR hydrogeologic provinces: Antelope Valley, Borrego Valley, the Central Desert area, Coachella Valley, Colorado River, Indian Wells Valley, Low-Use Basins of the Mojave and Sonoran Deserts, the Mojave, and Owens Valley. Collectively, these nine study areas are referred to as the DBR study unit. The study unit covers approximately 7,000 square miles and includes the 63 groundwater basins in the DBR hydrogeologic provinces in which groundwater is used for public drinking-water supply. The vast majority of the 223 wells sampled for this study were long-screened production wells used primarily for public supply. Uncorrected carbon-14 (14C) groundwater ages for samples collected in the DBR study unit ranged from less than (<) 100 to 33,700 years before present (BP). Sixty-six percent of sample ages were greater than (>) 100 years BP, and 40 percent were >3,800 years BP. Samples collected from wells located adjacent to mountain-front recharge areas or major surface-water features generally had younger groundwater ages than did samples collected from wells located away from mountain fronts or towards the distal ends of basin groundwater flow paths. Most groundwater sampled in the DBR study unit had alkaline pH: 89 percent of sample pH values ranged from 7.1 to 9.8, with 37 percent greater than or equal to (≥) 7.9. Groundwater age was significantly correlated (positively) with pH, likely because silicate weathering is a primary control on groundwater pH and is a slow process. The oxidation-reduction (redox) condition of the groundwater sampled in the DBR study unit was predominantly oxic (71 percent), except in the Colorado River study area where organic-rich fluvial aquifers provide the electron donors necessary to support iron-reducing (anoxic-Fe) redox processes. The cation type of 78 percent of the samples was either sodium- or mixed-type, and the anion type of 83 percent of the samples was either bicarbonate- or mixed-type. Sodium-type groundwaters generally were older and more alkaline than calcium-type groundwaters, consistent with the change in water chemistry expected from cation exchange between groundwater and aquifer sediments over long periods of time. Because of the correlation with young groundwater, calcium-type groundwater was predominantly from wells located adjacent to mountain-front recharge areas. Arsenic (As), boron (B), fluoride (F), molybdenum (Mo), strontium (Sr), uranium (U), and vanadium (V) were selected for assessment in this study because they occurred at concentrations greater than California Department of Public Health or U.S. Environmental Protection Agency regulatory or non-regulatory drinking-water-quality benchmarks in more than 2 percent of the 223 samples collected in the DBR study unit. As and F were detected most commonly (18 and 13 percent, respectively) at concentrations above associated water-quality benchmarks and Sr and V least frequently (both at 3 percent). Given that 14C groundwater ages are predominantly >100 years BP, land use in the study unit is primarily undeveloped, and chemicals derived from anthropogenic sources, such as volatile organic compounds, were infrequently detected, high concentrations of these trace elements in groundwater were most likely the result of natural factors and not anthropogenic factors. As, F, Mo, and V concentrations showed significant positive correlations to groundwater age and to pH. This relation is partly due to the sources of trace elements likely being the weathering of primary minerals, such as silicate minerals, which is a slow process that takes place over hundreds to thousands of years. This relation also reflects the positive correlation between groundwater age and pH. Geochemical modeling predicted that the dominant species of As, Mo, and V in solution were oxyanions (HAsO42–, MoO42–, and H2VO4–), which are likely to be mobile in alkaline groundwater because mineral surfaces composing aquifer matrices have a predominantly negative surface charge under alkaline conditions. F also exists predominantly as a negatively charged ion (F–). At pH values >7.5, saturation indices generated by the geochemical modeling program PHREEQC indicated that F solubility may be somewhat limited by the precipitation of the mineral fluorapatite [Ca5(PO4)3F]. Speciation modeling of As in anoxic-Fe groundwater (iron-reducing conditions) showed that samples were supersaturated with orpiment (As2S3), indicating that mineral precipitation may be responsible for low As concentrations observed in reducing groundwater. In contrast, U concentrations showed significant negative correlations to groundwater age and to pH. Higher U concentrations generally occurred in samples for which geochemical modeling indicated that the uncharged ternary complex Ca2UO2(CO3)3 was the dominant aqueous U species. This uncharged complex is not attracted to the charged surfaces of minerals and thus increases U solubility. Formation of Ca2UO2(CO3)3 was greater in younger groundwaters because calcium and uranium concentrations generally were lower in older groundwaters, likely due to cation-exchange processes and precipitation of the mineral calcite as groundwater pH increased. Co-precipitation of U with the calcite (CaCO3) may remove U from the aqueous phase. Saturation indices indicated that the anoxic-Fe groundwaters from the Colorado River study area were supersaturated with the mineral uraninite (UO2), suggesting that UO2 precipitation may be responsible for the low concentrations of U observed in these samples. Concentrations of strontium, which exists primarily in a cationic form (Sr2+), were not significantly correlated with either groundwater age or pH. Strontium concentrations showed a strong positive correlation with total dissolved solids (TDS). Dissolved constituents, such as Sr, that interact with mineral surfaces through outer-sphere complexation become increasingly soluble with increasing TDS concentrations of groundwater. Boron concentrations also showed a significant positive correlation with TDS, indicating the B may interact to a large degree with mineral surfaces through outer-sphere complexation.

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment-Priority Basin Project (GAMA-PBP) ranged from less than the study reporting limit of 1 microgram per liter (mg/L) to 32 mg/L. Statewide, Cr(VI) was reported in 31 percent of wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 mg/L in 4 percent of wells. Cr(VI) data collected for regulatory purposes overestimated Cr(VI) occurrence compared to spatially-distributed GAMA-PBP data. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and at higher concentrations in alkaline (pH >= 8), oxic water; and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that can mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return. Published by Elsevier Ltd.

First posted November 24, 2015 For additional information, contact: Director, California Water Science Center U.S. Geological Survey 6000 J Street, Placer Hall Sacramento, CA 95819 http://ca.water.usgs.gov The Borrego Valley is a small valley (110 square miles) in the northeastern part of San Diego County, California. Although the valley is about 60 miles northeast of city of San Diego, it is separated from the Pacific Ocean coast by the mountains to the west and is mostly within the boundaries of Anza-Borrego Desert State Park. From the time the basin was first settled, groundwater has been the only source of water to the valley. Groundwater is used for agricultural, recreational, and municipal purposes. Over time, groundwater withdrawal through pumping has exceeded the amount of water that has been replenished, causing groundwater-level declines of more than 100 feet in some parts of the basin. Continued pumping has resulted in an increase in pumping lifts, reduced well efficiency, dry wells, changes in water quality, and loss of natural groundwater discharge. As a result, the U.S. Geological Survey began a cooperative study of the Borrego Valley with the Borrego Water District (BWD) in 2009. The purpose of the study was to develop a greater understanding of the hydrogeology of the Borrego Valley Groundwater Basin (BVGB) and to provide tools to help evaluate the potential hydrologic effects of future development. The objectives of the study were to (1) improve the understanding of groundwater conditions and land subsidence, (2) incorporate this improved understanding into a model that would assist in the management of the groundwater resources in the Borrego Valley, and (3) use this model to test several management scenarios. This model provides the capability for the BWD and regional stakeholders to quantify the relative benefits of various options for increasing groundwater storage. The study focuses on the period 1945–2010, with scenarios 50 years into the future. This report documents and presents (1) an analysis of the conceptual model, (2) a description of the hydrologic features, (3) a compilation and analysis of water-quality data, (4) the measurement and analysis of land subsidence by using geophysical and remote sensing techniques, (5) the development and calibration of a two-dimensional borehole-groundwater-flow model to estimate aquifer hydraulic conductivities, (6) the development and calibration of a three-dimensional (3-D) integrated hydrologic flow model, (7) a water-availability analysis with respect to current climate variability and land use, and (8) potential future management scenarios. The integrated hydrologic model, referred to here as the “Borrego Valley Hydrologic Model” (BVHM), is a tool that can provide results with the accuracy needed for making water-management decisions, although potential future refinements and enhancements could further improve the level of spatial and temporal resolution and model accuracy. Because the model incorporates time-varying inflows and outflows, this tool can be used to evaluate the effects of temporal changes in recharge and pumping and to compare the relative effects of different water-management scenarios on the aquifer system. Overall, the development of the hydrogeologic and hydrologic models, data networks, and hydrologic analysis provides a basis for assessing surface and groundwater availability and potential water-resource management guidelines.

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from <3 mu g/L to 70 mu g/L with a median of 21 mu g/L. Concentrations of V were highest in samples collected from oxic groundwater (49% > 25 mu g/L) and lowest in samples collected from anoxic groundwater (70% < 0.8 mu g/L). In oxic groundwater, speciation modeling (SM) using PHREEQC predicted that V exists primarily as the oxyanion H2VO4. Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V5+ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4-8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH)(3)(+)]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH)(3) molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V3+ - or mixed V3+/Fe3+-oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions.Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO3) extract (37-71%), followed by the oxalate-ascorbic acid extract (19-60%) and the oxalate extract (3-14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO3 extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system. Published by Elsevier Ltd.

: The receding Arctic ice cap illustrates the impacts, both positive and negative, of a changing global climate. Environmental changes have brought new challenges and opportunities including transportation, tourism, exploration, and access to previously inaccessible natural resources. These new opportunities will result in increased human activity in the region from tourism to mineral extraction. Chances for military conflict remain low, however an array of potential large scale man-made crises are increasing with the opening Arctic. Potential Search and Rescue (SAR) and environmental crises include oil spills, airline emergencies, and foundering cruise ships. Currently, the Arctic has little infrastructure or resources to provide any substantial response to these events and the demand will only grow in a busier Arctic. This paper will explore the issue of emergency logistics shortfalls throughout the region. Specific points include analysis of the supporting participants and requirements driving them, the resource gap, approaches to bridging that gap, storage and deployment options. The assessment concludes with a conceptual model for addressing the resource gap across the region within a budget-constrained environment and the impacts of inaction.