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Krishangi D. Groover

Publications and source records attributed to Krishangi D. Groover.

At least 19 recordsLinked to original sources

Status and understanding of groundwater quality in the Mojave Basin Domestic-Supply Aquifer study unit, 2018—California GAMA Priority Basin Project

Groundwater quality in the western part of the Mojave Desert in San Bernardino County, California, was investigated in 2018 as part of the California State Water Resources Control Board Groundwater Ambient Monitoring and Assessment Program Priority Basin Project. The Mojave Basin Domestic-Supply Aquifer study unit (MOBS) region was divided into two study areas—floodplain and regional—to assess differences between the two major aquifers used for drinking water supply in the area. This assessment characterized the quality of ambient groundwater and not the quality of treated drinking water. The study included three components: (1) a status assessment, which characterized the quality of groundwater resources used for domestic drinking-water supply in the floodplain and regional study areas; (2) a brief understanding assessment, which evaluated factors that could potentially affect the quality of groundwater used by domestic wells in the region; and (3) a comparative assessment between the groundwater resources used by domestic wells and public-supply wells in the two study areas. The domestic-well assessment was based on data collected by the U.S. Geological Survey from 48 domestic wells in January–May 2018. The public-supply assessment was based on data for samples from 322 public-supply wells in 2008–18, either collected by the U.S. Geological Survey or compiled from the California State Water Resources Control Boards Division of Drinking Water publicly available database. Concentrations of water-quality constituents in ambient groundwater were compared to regulatory and non-regulatory benchmarks typically used by the State of California and Federal agencies as health-based or aesthetic standards for public drinking water. Relative concentrations, defined as the measured concentration divided by the benchmark concentration, were classified as high (greater than 1.0), moderate (greater than 0.5 for inorganic constituents or 0.1 for organic and special-interest constituents, and not high), or low (concentrations lower than moderate). The floodplain and regional study areas were divided into 15 and 35 grid cells, respectively, and grid-based methods were used to compute the areal proportions of the two study areas with high, moderate, or low relative concentrations of individual constituents and classes of constituents. For the domestic-supply assessment, one or more inorganic constituents with health-based benchmarks were detected at high relative concentrations in 58 percent of the regional study area and 13 percent of the floodplain study area. The inorganic constituents with health-based benchmarks detected at high relative concentrations in the regional study area were arsenic, chromium and hexavalent chromium, fluoride, adjusted gross alpha particle activity, uranium, molybdenum, strontium, and nitrate; only arsenic was detected at high relative concentrations in the floodplain study area. One or more inorganic constituents with secondary maximum contaminant level benchmarks were detected at high concentrations in 15 and 6.7 percent of the regional and floodplain study areas, respectively. The constituents detected at high relative concentrations in the regional study area were total dissolved solids, chloride, sulfate, and iron; only total dissolved solids and sulfate were detected at high relative concentrations in the floodplain study area. Organic constituents were not detected at moderate or high relative concentrations in either the regional or floodplain study areas. Volatile organic compounds were detected at low relative concentrations in 21 and 27 percent of the regional and floodplain study areas, respectively, and pesticides were detected at low relative concentrations in 9.1 and 20 percent of the regional and floodplain study areas, respectively. The only individual organic constituent detected in more than 10 percent of either study area was the trihalomethane trichloromethane. Total coliform bacteria were detected in 15 and 27 percent of the grid wells in the regional and floodplain study areas, respectively. The greater prevalence of high relative concentrations of many inorganic constituents in the regional study area compared to the floodplain area likely indicates the greater diversity of geologic material at depth in aquifer material and generally finer-grained alluvium compared to the floodplain study area combined with generally older groundwater that has had more contact time with aquifer materials. In general, trace element concentrations (1) increased with increasing groundwater age, (2) increased with distance from recharge sources in the mountains, and (3) increased with closer proximity to some types of geological units. In general, groundwater from domestic wells in the floodplain study area is young, with most samples containing a component of modern groundwater based on tritium and unadjusted carbon-14 activities, whereas groundwater from domestic wells in the regional study area generally is old, with most samples having unadjusted carbon-14 ages of 5,000–40,000 years. Public-supply wells in MOBS generally were deeper than domestic wells and presumably are in contact with older, more weathered alluvium that may have more mobile trace elements, such as arsenic or uranium. However, only 26 percent of the public-supply regional study area had high relative concentrations of inorganic constituents, compared to 58 percent for the domestic regional study area. The percentages of the public-supply and domestic floodplain study areas with high relative concentrations of inorganic constituents were 11 and 13 percent, respectively. The ages of groundwater used by public-supply and domestic wells in each study area were similar, which was not expected given the greater depth of the public-supply wells. Three potential factors may contribute to these results: (1) greater spatial footprint of domestic well network, which may result in domestic wells pumping groundwater from fractured bedrock or mineralized areas not used by public-supply wells; (2) greater pumping rates in public-supply wells, resulting in more water being withdrawn from coarse-grained, heterogeneous alluvium than finer-grained layers, which may have higher concentrations of (or more mobile) inorganic constituents; and (3) a greater degree of well management with public-supply wells, which may include pausing use of or decommissioning wells if treating or blending water is not feasible to lower constituent concentrations.

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Nutrient chemistry in the Elizabeth Lake subwatershed—Effects of onsite wastewater treatment systems on groundwater and lake water quality, Los Angeles County, California

Nutrient (nitrogen [N] and phosphorus [P] chemistry) downgradient from onsite wastewater treatment system (OWTS) was evaluated with a groundwater study in the area surrounding Elizabeth Lake, the largest of three sag lakes within the Santa Clara River watershed of Los Angeles County, California. Elizabeth Lake is listed on the “303 (d) Impaired Waters List” for excess nutrients and is downgradient from more than 600 OWTS. The primary objective of this study was to develop a conceptual hydrogeological model to determine if discharge from OWTS is transported into shallow groundwater within the Elizabeth Lake subwatershed and contributes nutrients to Elizabeth Lake in excess of the total maximum daily load limit. An analysis of historical data and data collected for this study provided estimates of aquifer properties, such as hydraulic gradients and other parameters necessary to estimate boundary conditions. Electrical resistivity tomography (ERT) surveys were done to determine the best monitoring well locations and to estimate depth to groundwater. During 4 separate sampling events, 11 wells, 2 imported water tanks, 1 spring (sampled on March 17, 2019), and Elizabeth Lake were sampled, which occurred during February–September 2020. ERT transects and borehole geophysical measurements indicated that there were low to high resistivity materials in the subsurface and potential perched fresh water. Most of the aquifer material was characterized as sandy silt, occasionally with mixed clays and medium gravels, and was estimated to have a hydraulic conductivity from 3.28x10 −3 to 16.4 feet per day, a porosity from 0.34 to 0.42, and a hydraulic gradient from 0.01 to 0.03. Although bedrock was not obvious in ERT transects, all well depths were terminated at depths of an impassible confining layer observed to be a highly consolidated blue-gray clay. Depths to granitic bedrock, based on road outcrops and lithologic driller logs, varied throughout the study area. Depth to the bedrock was estimated to be shallow on the north side of Elizabeth Lake at approximately 30 feet below land surface (ft bls). Depth to bedrock is at 50 ft bls toward the east of the Elizabeth Lake subwatershed, which is at topographic ground surface to the north and south of the residential development. Groundwater levels ranged from approximately 0 to 12 ft bls during this study. Historical water levels ranged from 8 to 16 ft bls in the lower elevation of the study area and increased to depths of as much as 80 ft bls at higher elevations on the north and south boundaries of the Elizabeth Lake subwatershed. Water-quality samples were analyzed for major ions, nutrients, dissolved organic carbon, stable isotopes, and age-dating tracers. A principal component analysis was completed to determine organic matter sources. The proportion of recharge from imported waters, used for domestic consumption, was calculated using stable water isotopes, deuterium (δD) and oxygen (δ 18 O). Recharge from imported waters accounted for approximately 15–71 percent of the total recharge to groundwater within the study area. Total nitrogen concentrations ranged from 0.17 to 30.9 milligrams per liter (mg/L) as N, and phosphorus, measured in the soluble form as orthophosphate, ranged from 0.03 to 0.35 mg/L as P. Nitrate concentrations in groundwater samples ranged from less than the detection limit (0.01 mg/L as N) to approximately 24 mg/L as N. Nitrate was not detected in 3 of the 12 sites sampled during the study (2 wells and Elizabeth Lake). Dissolved organic carbon concentrations ranged from 0.4 to 27 mg/L in groundwater and from 9.9 to 100 mg/L in Elizabeth Lake. Ammonium and orthophosphate concentrations generally were low in groundwater. However, elevated concentrations of ammonium in Elizabeth Lake were assumed to be due to avian waste products or biological nitrogen fixation. Groundwater ages were mostly modern (recharged since 1952), with a median recharge temperature of 13 degrees Celsius. Redox conditions in groundwater indicated the likely occurrence of nitrate attenuation by denitrification downgradient from the wells to the south of Elizabeth Lake before groundwater discharges to the lake. Undetectable nitrate in Elizabeth Lake at the time of sampling was likely due to algal uptake. Most wells contained stable isotopes of nitrogen and oxygen in nitrate (δ 15 N-NO 3 and δ 18 O-NO 3 ) molecules with values consistent with denitrification. However, one monitoring well on the north of Elizabeth Lake (ELLA-8) had no evidence of denitrification, based on elevated concentrations of nitrate and a sufficient amount of dissolved oxygen such that the water was oxic and not favorable for the denitrification reaction. Consequently, this nitrate could be delivered to Elizabeth Lake through groundwater discharge if nitrate is not removed from the system by denitrifying bacteria downgradient from the well before the groundwater discharges into Elizabeth Lake. The principal component analysis demonstrated that dissolved organic matter optical properties track different sources of dissolved organic matter from decayed plants, animals, and animal-derived wastes. Two wells contained strong indicators of OWTS water presence, although geochemical evidence indicated other wells may also be affected by OWTS discharge.

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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.

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Selenium hazards in the Salton Sea environment—Summary of current knowledge to inform future wetland management

Quaternary marine and continental shales in the western United States are sources of selenium that can be loaded into the aquatic environment through mining, agricultural, and energy production processes. The mobilization of selenium from shales through agricultural irrigation has been recognized since the 1930s; however, discovery of deformities in birds and other wildlife using agricultural habitats during the 1980s spurred studies to determine the extent and effects of the contamination. Through these early studies, researchers determined that biota in the Salton Sea drainage basin was at risk from legacy selenium contamination in the Colorado River watershed. The Salton Sea and its surrounding managed and unmanaged wetlands provide vital inland habitat and trophic support for diverse assemblages of resident and migratory wildlife, and understanding regional selenium hazards for these trust species is a priority for many Federal and State agencies. The modern Salton Sea is a shallow, landlocked saline lake in Riverside and Imperial Counties (not shown) of California that is sustained by irrigation return and perennial river inflow. Changes in water transfer agreements under the 2003 Quantification Settlement Agreement (QSA) have resulted in reduced irrigation flow, declining lake levels, and the evolution of unmanaged wetlands in areas where drains and rivers no longer reach the Salton Sea. These wetlands provide additional habitat for some species of concern, but their potential to increase selenium hazards for trust species is largely unknown. From the 1980s to 2020, efforts to document selenium contamination and effects throughout the region have resulted in a considerable amount of selenium data from the Salton Sea and its surrounding drainage basin; however, no long-term (greater than 20 years), consistent sampling program has been established, and all data have been collected by different entities using a variety of protocols and analytical techniques. This lack of coordination has been previously documented in regional management plans and has led to difficulty in reliably assessing selenium hazards in the Salton Sea environment. This report provides a summary of the available disparate selenium information collected from water, sediment, and biota in the Salton Sea region since the 1980s and to identify data gaps that need to be filled to understand the potential effects of selenium on species of concern, including federally endangered desert pupfish ( Cyprinodon macularius ) and Yuma Ridgway’s Rail ( Rallus obsoletus yumanensis; formerly Yuma Clapper Rail, Rallus longirostris yumanensis ). Available data from the Salton Sea drainage basin show that water from the Colorado River has the lowest selenium concentration of all surface water sources. All other surface water flowing into the Salton Sea has elevated selenium concentrations due to evaporation and evapotranspiration that occurs in agricultural fields and associated water delivery infrastructure or leaching of selenium from irrigated farmland soils. The Salton Sea has lower selenium concentrations because of various biogeochemical processes that recycle selenium into the sediment or volatilize it to the atmosphere; however, these mechanisms are not well defined, and it is not clear if selenium cycling will change in response to possible changes in the oxidation state of the Salton Sea bottom waters as water levels decline. Agricultural drains have the highest average selenium concentrations, but few drains have been sampled since changes in irrigation practices have occurred (due to the 2003 QSA). Groundwater selenium concentrations are variable; some wells south of the Salton Sea have selenium concentrations as high as 300 micrograms per liter (µg/L), whereas selenium concentrations are below detection in other wells. Groundwater and surface-water geothermal discharge zones around the margins of the Salton Sea and in unmanaged wetlands have not been studied in detail, and published selenium measurements are not available for these surface features. Selenium concentrations in the sediment of the Salton Sea drainage basin are highest in wetland particulate organic matter and the Salton Sea lakebed, indicating that removal of selenium from the water to the sediment has been a primary mechanism for keeping selenium concentrations low in the water column. Sediment selenium concentrations in wetlands are lower than in the Salton Sea but higher than inflowing drains and rivers, indicating the lentic wetland sites also may be important sinks for selenium because of biogeochemical processes. Sediment selenium data have not been collected in agricultural drains since changes in irrigation practices occurred (due to the 2003 QSA), and it is unknown if selenium sequestration from the water column has changed in these systems. We divided biological data into broad taxonomic categories, including primary producers, invertebrates, herpetofauna, mammals, fishes, and birds to facilitate evaluation of selenium concentrations and spatiotemporal trends observed in the Salton Sea. Overall, selenium concentrations were substantially greater in algae samples compared to all vascular plant samples combined. Median selenium concentrations in several invertebrate taxa (Chironomidae, Formicidae, Corixidae, Corbiculidae and Nereididae, and Decapoda) exceeded the maximum suggested dietary threshold of 3.0–4.0 micrograms per gram (µg/g) dry weight (dw) for predators consuming invertebrates in aquatic food webs. The greatest number of samples were collected from fish, and selenium distributions among species and locations showed that the range for most samples was lower than the U.S. Environmental Protection Agency selenium criterion for aquatic life (8.5 µg/g dw whole body, 11.3 µg/g dw fillets). The median selenium concentrations for whole body fish were below the selenium criterion in most locations, except for bairdiella ( Bairdiella icistia ) from the Salton Sea and irrigation drains, a few individual tilapia spp. (family Cichlidae, including genera Tilapia, Oreochromis , and their hybrids) from the river and river outlets, and several western mosquitofish ( Gambusia affinis ) and sailfin molly ( Poecilia latipinna ) from irrigation drain outlets. For avian samples combined among years and locations, median selenium concentrations in livers from all families except waders and Ibis (family Threskiornithidae) were higher than levels expected to cause selenium toxicosis (10–20 µg/g dw), and all median egg concentrations were above or near 6.0 μg/g dw, which is a conservative threshold value for reproductive impairment. Most knowledge gaps we identified for water, sediment, and biota were interrelated, and the use of integrated approaches to address knowledge gaps can provide greater insight into the drivers behind selenium hazards. Integrated water, sediment, and biota studies could help identify cost-effective management solutions that serve multiple purposes. A comprehensive analysis of the hydrology, biogeochemistry, and food-web processes in wetlands and other habitats can inform predictive models to identify drivers of selenium bioavailability, uptake from the environment and subsequent trophic transfer, ultimately forming the basis for experimental habitat management manipulations to minimize selenium hazards to wildlife. Furthermore, a comprehensive, long-term sampling and analytical laboratory plan would enable comparison of data among different entities that are sampling at the Salton Sea. Such efforts are well suited to help fill knowledge gaps that preclude understanding of selenium hazards and future management options for biota using Salton Sea habitats, including newly formed wetlands throughout the region. All data compiled for this report are available in two U.S. Geological Survey data releases: Groover and others (2022) for water and sediment samples and De La Cruz and others (2022) for biological samples. The data releases include all publicly available data for selenium concentrations in water, sediment, and biological samples collected in and around the Salton Sea, including the Coachella and Imperial Valleys. The data releases also include previously unpublished data.

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Natural and anthropogenic hexavalent chromium, Cr(VI), in groundwater near a mapped plume, Hinkley, California

The Pacific Gas and Electric Company (PG&E) Hinkley compressor station, in the Mojave Desert, 80 miles northeast of Los Angeles, California, is used to compress natural gas as it is transported through a pipeline from Texas to California. Between 1952 and 1964, cooling water was treated with a compound containing hexavalent chromium, Cr(VI), to prevent corrosion of machinery within the compressor station. Cooling wastewater containing Cr(VI) was discharged to unlined ponds and released into groundwater. Since 1964, cooling-water management practices have been used that do not contribute chromium to groundwater.

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Introduction to study area hydrogeology, chromium sources, site history, and purpose of study

Between 1952 and 1964, hexavalent chromium, Cr(VI), was released into groundwater from the Pacific Gas and Electric Company (PG&E) Hinkley compressor station in the Mojave Desert 80 miles (mi) northeast of Los Angeles, California. Remediation began in 1992, and in 2010, site cleanup was projected to require between 10 and 95 years and was expected to cost between $36 and $176 million. A 2007 PG&E study estimated the natural Cr(VI) background in groundwater in Hinkley Valley to be 3.1 micrograms per liter (μg/L). This concentration was used for interim regulatory purposes by the Lahontan Regional Water Quality Control Board (RWQCB). In the fourth quarter (October–December) 2015, the regulatory Cr(VI) plume extended about 3.0 mi downgradient from the release location within the Hinkley compressor station, while groundwater having Cr(VI) concentrations greater than 3.1 μg/L was present more than 8 mi downgradient. Although rocks and minerals in the area are naturally low in chromium, alluvium eroded from the San Gabriel Mountains and transported to Hinkley Valley by the Mojave River, and locally small exposures of mafic rock, including hornblende diorite and basalt, may contribute Cr(VI) to groundwater. In response to limitations of the PG&E 2007 Cr(VI) background study’s methodology, uncertainty in the natural Cr(VI) background concentration, and an increase in the mapped extent of groundwater having Cr(VI) concentrations greater than the interim regulatory background of 3.1 μg/L, the Lahontan RWQCB concluded that the 2007 PG&E background Cr(VI) study should be updated. The purpose of the updated study is to estimate background Cr(VI) concentrations in groundwater within the upper aquifer upgradient, downgradient, near the margins, and within the footprint of the PG&E Cr(VI) plume in Hinkley, California. The scope of the study included eight tasks; results from those tasks are presented in the chapters within this professional paper.

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Survey of chromium and selected element concentrations in rock, alluvium, and core material

Between 1952 and 1964, hexavalent chromium, Cr(VI), was released into groundwater from the Pacific Gas and Electric Company (PG&E) compressor station in Hinkley, California, in the western Mojave Desert 80 miles northeast of Los Angeles, California. In 2015, the extent of anthropogenic Cr(VI) in groundwater in Hinkley and Water Valleys was uncertain, and some Cr(VI) in groundwater may be naturally occurring from rock and aquifer material. On the basis of more than 1,500 portable (handheld) X-ray fluorescence (pXRF) measurements on more than 250 samples of rock, surficial alluvium, and core material from selected wells in Hinkley and Water Valleys, chromium concentrations are commonly low compared to the average bulk continental abundance of 185 milligrams per kilogram (mg/kg). However, chromium concentrations are as high as 530 mg/kg in mafic hornblende diorite that crops out along the western margin of Hinkley Valley in Iron Mountain. Other chromium-containing rocks in the area are either (1) not consistently high in chromium, (2) have limited areal extent, or (3) in the case of basalt, are present only in Water Valley. Chromium concentrations in core material adjacent to the screened intervals of wells sampled for water chemistry and isotopic composition as part of the U.S. Geological Survey Cr(VI) background study ranged from less than the study reporting level (SRL) of 5 mg/kg to 410 mg/kg, with a median concentration of 23 mg/kg. Chromium concentrations in core material were lower in the eastern subarea and higher in the western and the northern subareas of Hinkley Valley and in Water Valley. The highest chromium concentration in core material was in weathered hornblende diorite bedrock. Chromium concentrations in core material adjacent to the screened interval of sampled wells were log-normally distributed below a threshold of 85 mg/kg, and 3 percent of chromium concentrations were greater than 85 mg/kg. Manganese can oxidize trivalent chromium, Cr(III), to Cr(VI). Similar to chromium, manganese concentrations in core material also were log-normally distributed below a threshold of 970 mg/kg, and 5 percent of manganese concentrations were greater than 970 mg/kg. Both chromium and manganese concentrations were higher in fine-textured core material and in visually abundant iron- and manganese-oxide coatings on the surfaces of mineral grains. High concentrations of chromium and manganese in core material commonly co-occurred. Fine-textured core material, chromium concentrations greater than 85 mg/kg, and manganese concentrations greater than 970 mg/kg in core material adjacent to the screened interval of sampled wells were selected for use as metrics (threshold values) within a summative-scale analysis (SSA) developed to identify natural and anthropogenic Cr(VI) in water from wells later within this professional paper (chapter G). Principal component analysis (PCA) of 18 elements within surficial alluvium, rock, and core material measured using pXRF shows distinct elemental assemblages associated with (1) older and more recent “Mojave-type” deposits, including alluvium and lake-margin (beach) deposits sourced from the Mojave River, (2) alluvium eroded from mafic rock, including hornblende diorite that crops out on Iron Mountain, (3) alluvium eroded from felsic volcanic and hydrothermal rock that crops out on Mount General along the eastern margin of Hinkley Valley, (4) playa/mudflat and other fine-textured deposits, and (5) material with visually abundant iron- and manganese-oxide coatings. Most wells sampled as part of this study were completed in Mojave-type deposits. Portable (handheld) X-ray fluorescence data measured on core material from those wells do not appear to be different or unusual compared to the magnitude and range of data from the larger Mojave River groundwater basin, and the core material has a low-chromium, felsic composition consistent with a Mojave River origin. In general, the elemental composition of core material from wells was not measurably altered by admixtures with local mafic, felsic volcanic, or hydrothermal source materials; although, where present, admixtures with basalt may contribute chromium to core material.

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Chromium in minerals and selected aquifer materials

Between 1952 and 1964, hexavalent chromium, Cr(VI), was released into groundwater from a Pacific Gas and Electric Company (PG&E) compressor station in Hinkley, California, in the western Mojave Desert 80 miles northeast of Los Angeles, California. In 2015, the extent of anthropogenic Cr(VI) in groundwater in Hinkley and Water Valleys was uncertain, but some Cr(VI) in groundwater may be naturally occurring from rock and aquifer material. To evaluate potential sources of natural Cr(VI), chromium and other selected trace-element concentrations were measured by inductively coupled plasma-mass spectrometry (ICP-MS), with multi-acid digestion, on 34 samples of surficial alluvium and core material from Hinkley and Water Valleys, California, and on 2 samples of alluvium from the mafic Sheep Creek fan to the southwest. Chromium concentrations in Hinkley and Water Valleys ranged from 2 to 110 milligrams per kilogram (mg/kg), with a median concentration of 14 mg/kg; concentrations were highest in weathered mafic hornblende diorite associated with Iron Mountain. High chromium concentrations also were present within fine-textured materials and visually abundant iron- and manganese-oxide coatings on the surfaces of mineral grains. For comparison, chromium concentrations as high as 170 mg/kg were measured in mafic alluvium from the Sheep Creek fan. In contrast, chromium concentrations were lowest in Mojave-type deposits (Mojave River stream and lake margin deposits), with a median of 6 mg/kg. Chromium concentrations measured by ICP-MS compared favorably with concentrations measured by portable (handheld) X-ray fluorescence (pXRF; chapter B), on the basis of least-squares regression results and a coefficient of determination (R 2 ) of 0.97. Minerals in bulk samples and the heavy (dense) mineral fractions isolated from those samples were identified using optical techniques, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Quartz and feldspar were the most abundant minerals, especially within recent and older Mojave River deposits. Chromium concentrations were as high as 1,250 mg/kg in the heavy-mineral fraction, with specific gravity greater than 3.32. Chromium was not commonly detected in the light-mineral fraction, with specific gravity less than 2.85. Most chromium within the heavy-mineral fraction was substituted within magnetite mineral grains less than 100 micrometers (μm) in diameter, and almost no chromite was present within the heavy-mineral fraction. Although magnetite is resistive to weathering, weathering of magnetite to hematite was identified (1) in Miocene materials underlying unconsolidated deposits in the western subarea of Hinkley Valley and (2) in alluvium within Water Valley that contains weathered minerals eroded from Miocene rock. Less-dense, more easily weathered chromium-containing amphiboles, such as actinolite in older Mojave River alluvium and hornblende in locally derived alluvium from Iron Mountain, were identified optically. Magnetite was not identified in weathered hornblende diorite and was less abundant in locally derived materials and in Miocene materials than in Mojave-type deposits. A comparison of ICP-MS data and sequential extraction data shows that approximately 90 percent of chromium in aquifer material within Hinkley and Water Valleys was not extractable and was interpreted to reside within unweathered mineral grains. Most extractable chromium was within the strong acid extractable fraction. Chromium within the weakly sorbed, and specifically sorbed extractable fractions in oxide accumulations within the regulatory Cr(VI) plume is potentially mobile into groundwater with changes in ionic strength or pH. Although Hinkley and Water Valleys are regionally low in chromium, natural geologic sources of chromium may be present in aquifer materials penetrated by wells completed in (1) weathered hornblende diorite bedrock underlying the western subarea; (2) Miocene deposits underlying the western subarea and unconsolidated material in the northern subarea and Water Valley containing basalt or weathered minerals eroded from Miocene deposits; (3) unconsolidated material containing visually abundant iron- and manganese-oxide coatings on the surfaces of mineral grains that are present near the water table and near lithologic or geologic contacts; and (4) brown clay and mudflat/playa deposits in the northern subarea. Brown clay and mudflat/playa deposits in the eastern subarea near Mount General have a low-chromium, felsic mineralogy similar to Mojave River deposits and do not contain high concentrations of chromium; however, manganese(IV) oxides within these materials may facilitate oxidation of trivalent chromium, Cr(III), to Cr(VI).

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Evaluation of natural and anthropogenic (human-made) hexavalent chromium

Hexavalent chromium, Cr(VI), was released between 1952 and 1964 from the Pacific Gas and Electric Company (PG&E) Hinkley compressor station, in the Mojave Desert about 80 miles northeast of Los Angeles, California. Geologic, geochemical, and hydrologic data from more than 100 wells collected between March 2015 and November 2017 were interpreted using a summative-scale analysis to define the extent of anthropogenic (human-made) Cr(VI) in groundwater. The summative scale consisted of eight questions requiring binary (yes or no) answers for each sampled well. The questions were intended to (1) provide a transparent framework for data interpretation in which all stakeholders participated; (2) provide unbiased interpretation of data traceable to numerical measurements; (3) provide a framework that enabled geologic, geochemical, and hydrologic data to be considered collectively; and (4) consolidate different types of data into a simple, easy-to-understand interpretation. When data from each well are scored using questions and metrics within the summative scale, all stakeholders would score each well the same way and would draw the same summative-scale Cr(VI) plume extent. The areal extent of the summative-scale Cr(VI) plume was 5.5 square miles (mi 2 ); this is larger than the 2.2-mi 2 extent of the October–December 2015 (Q4 2015) regulatory Cr(VI) plume but smaller than the 8.3-mi2 maximum mapped extent of Cr(VI) greater than the interim regulatory Cr(VI) background value of 3.1 micrograms per liter (μg/L). The summative-scale Cr(VI) plume is within the area covered by the PG&E monitoring well network and lies within “Mojave-type” deposits composed of low-chromium stream and near-shore lake deposits sourced from the Mojave River. The summative-scale Cr(VI) plume included all shallow wells within the footprint of the Q4 2015 regulatory Cr(VI) plume, but summative-scale scores indicate that anthropogenic Cr(VI) was not present in several wells within the footprint of the regulatory Cr(VI) plume that were screened within the deep zone of the upper aquifer. The summative-scale Cr(VI) plume extent was consistent with mineralogic and geochemical data collected as part of this study that were not used within the summative-scale analysis. Data from wells outside the summative-scale Cr(VI) plume collected for regulatory purposes from April 2017 through March 2018 were used to estimate Cr(VI) background concentrations as the upper 95-percent tolerance limit (UTL 95 ) in different parts of Hinkley and Water Valleys. The UTL 95 values were calculated using the computer program ProUCL 5.1 and are suitable for use by regulatory agencies in support of (1) updating the regulatory Cr(VI) plume extent and management of Cr(VI) near the plume margins, (2) establishing cleanup goals for Cr(VI) within the updated regulatory Cr(VI) plume, and (3) identifying unusual Cr(VI) concentrations outside the regulatory Cr(VI) plume. The nonparametric UTL 95 values for wells screened in Mojave-type deposits in the eastern, western, and northern subareas of Hinkley Valley were 3.7, 3.9, and 4.0 μg/L, respectively. The normal UTL 95 values for wells screened in undifferentiated, unconsolidated deposits in the eastern and western subareas and the northern subarea upgradient from the Mount General fault were 2.8, 3.8, and 4.8 μg/L, respectively. An overall normal UTL 95 value of 3.8 μg/L was calculated for undifferentiated, unconsolidated deposits in these areas. This value is similar to the overall nonparametric UTL 95 value of 3.9 μg/L calculated for Mojave-type deposits and similar to the maximum Cr(VI) concentration of older groundwater in contact with Mojave-type deposits of 3.6 μg/L. The provenance of most PG&E monitoring wells is not precisely known, and the UTL 95 values for wells screened in undifferentiated, unconsolidated deposits in the different subareas may be more widely applicable for regulatory purposes than the UTL 95 values for Mojave-type deposits. The UTL 95 value of 2.8 μg/L for wells screened in undifferentiated, unconsolidated deposits in the eastern subarea is important for plume management because most of the summative-scale Cr(VI) plume is within the eastern subarea. A UTL 95 value of 5.8 μg/L was calculated for older (pre-1952) groundwater associated with mudflat/playa deposits in the eastern subarea near Mount General. A UTL 95 value of 2.3 μg/L was calculated for Mojave-type deposits within the Cr(VI) plume downgradient from the Hinkley compressor station after regulatory updates. This lower value is consistent with neutral to slightly alkaline, younger (post-1952) groundwater within coarse-textured, low-chromium Mojave-type deposits in this area and may be a suitable metric for Cr(VI) cleanup goals. The UTL 95 value of 4.8 μg/L for wells screened in undifferentiated, unconsolidated deposits in the northern subarea upgradient from the Mount General fault provides for possible increases in Cr(VI) concentrations if water levels continue to decline. Downgradient from the Q4 2015 regulatory Cr(VI) plume and the summative-scale Cr(VI) plume, UTL 95 values of 9.0 and 6.4 μg/L were calculated for wells screened in undifferentiated, unconsolidated deposits in the northern subarea downgradient from the Mount General fault and for Water Valley, respectively, consistent with different geologic and geochemical conditions in these areas. The UTL 95 values calculated as part of this study provide scientifically defensible estimates of background Cr(VI) concentrations that differ with local geologic, geochemical, and hydrologic conditions in Hinkley and Water Valleys. The regulatory Cr(VI) plume extent can be updated on the basis of these values. The summative-scale Cr(VI) plume extent may contain wells having anthropogenic Cr(VI) concentrations less than the UTL 95 values for their respective subareas that may not require regulatory attention, and an updated regulatory Cr(VI) plume extent may be less than the summative-scale Cr(VI) plume extent. The UTL 95 values are not background Cr(VI) concentrations for regulatory purposes, and the authority to establish regulatory values resides solely with the Lahontan Regional Water Quality Control Board.

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Predevelopment water levels, groundwater recharge, and selected hydrologic properties of aquifer materials, Hinkley and Water Valleys, California

Hydrologic and geophysical data were collected to support updates to an existing groundwater-flow model of Hinkley Valley, California, in the Mojave Desert about 80 miles northeast of Los Angeles, California. These data provide information on predevelopment (pre-1930) water levels, groundwater recharge, and selected hydrologic properties of aquifer materials. A predevelopment groundwater-level map, drawn using water-level measurements from 48 wells collected as early as 1918, showed groundwater movement from recharge areas along the Mojave River to evaporative discharge areas near the margin of Harper (dry) Lake in Water Valley. During predevelopment conditions, depth to water ranged from near land surface along the Mojave River to above land surface near Harper (dry) Lake, consistent with flowing wells in Water Valley at that time. Depths to water in much of Hinkley Valley downgradient from the Lockhart fault were less than 20 feet below land surface. By 2017, water-level declines as a result of agricultural pumping, were as much as 60 feet near the Hinkley compressor station. Areal recharge from infiltration of precipitation on the valley floor is negligible. Average annual recharge as infiltration of runoff from upland drainages to Hinkley and Water Valleys averages 64.7 acre-feet per year. In most years recharge does not occur; in years when it occurs, recharge to Hinkley Valley is typically about 296 acre-feet. In contrast, average recharge as infiltration of streamflow from the Mojave River from 1931 to 2015 was between 13,400 and 17,100 acre-feet per year; in some years recharge from the Mojave River exceeded 100,000 acre-ft. Estimates of predevelopment groundwater movement through Hinkley Gap and groundwater discharge to Harper (dry) Lake ranged from 570 to 1,900 and 820 to 2,460 acre-feet per year, respectively; at the time of this study in 2017, groundwater movement through Hinkley Gap was estimated to be about 83 acre-feet per year. Hydraulic-conductivity values estimated from slug-test data for 95 monitoring wells ranged from less than 0.1 to 680 feet per day (ft/d); values generally decreased with depth. Median hydraulic-conductivity values calculated from nuclear magnetic resonance (NMR) data for Mojave River alluvium and near-shore lake deposits were 73 and 11 ft/d, respectively; median hydraulic-conductivity values for locally derived alluvium and weathered bedrock were 6 and 2 ft/d, respectively. Hydraulic-conductivity values, estimated from NMR data for formerly saturated deposits overlying the 2017 water table, were as high as 300 ft/d near the Hinkley compressor station. Downgradient from the Hinkley compressor station, formerly saturated deposits had hydraulic-conductivity values of about 150 ft/d, which were higher than values in saturated material. Coarse-textured, permeable material in formerly saturated deposits above the 2017 water table may have allowed groundwater, released from the Hinkley compressor station that may have contained Cr(VI), to move rapidly downgradient. The Lockhart fault is an impediment to groundwater flow within Hinkley Valley. Groundwater-flow directions from horizontal point-velocity probe data were deflected to the west on the upgradient side of the fault compared to the nominal direction of groundwater flow estimated from water-level data. Younger groundwater was present on the upgradient and downgradient sides of the fault, and older groundwater with unadjusted carbon-14 ages as old as 5,650 years before present was in water from wells within splays of the Lockhart fault, consistent with limited groundwater movement across the fault. As a result, groundwater and Cr(VI) released from the Hinkley compressor station moved to the northwest along the downgradient side of the fault. Coupled well-bore flow and depth-dependent water-quality data show water from wells C-01 and IW-03 within the Q4 2015 (October–December 2015) regulatory Cr(VI) plume was yielded from thin layers within the aquifer that are composed of well-sorted lake-margin (beach) deposits that likely have high lateral and longitudinal connectivity. Collectively, data show highly permeable deposits above the regional water table and thin permeable deposits within saturated portions of the upper aquifer that may have conducted groundwater and Cr(VI) downgradient when releases from the Hinkley compressor station first occurred.

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Sequestration and reoxidation of chromium in experimental microcosms

Groundwater containing hexavalent chromium, Cr(VI), downgradient from the Pacific Gas and Electric Company (PG&E) Hinkley compressor station in the Mojave Desert, 80 miles northeast of Los Angeles, California, is undergoing bioremediation using added ethanol as a reductant in a volume of the aquifer defined as the in situ reactive zone (IRZ). This treatment reduces Cr(VI) to trivalent chromium, Cr(III), which is rapidly sequestered by sorption to aquifer particle surfaces and by co-precipitation within iron (Fe) or manganese (Mn) bearing minerals forming in place as reduction proceeds. Successful mitigation of the Cr(VI) plume is projected to require 10–95 years, at which time bioremediation with ethanol will likely cease. This projection assumes that Cr(VI) removal is permanent and that no Cr(III) will oxidize back to Cr(VI) in the event of changing hydrologic conditions that may cause oxygen-rich water to re-enter the IRZ. Laboratory microcosm experiments were done to explore the process of reductive sequestration of Cr(VI) to Cr(III) and the potential for reoxidation of Cr(III) to Cr(VI). In reductive sequestration experiments, batch microcosms were prepared with aquifer materials collected from sites upgradient of the Cr(VI) regulatory plume. Control microcosms were prepared using Fe- and Mn-coated quartz sand. Unfiltered Mojave River groundwater containing an added tracer of isotopically labeled chromium-50 were reacted with microcosm materials for up to 2 years; during this time, bio-reduction was stimulated by repeated additions of diluted ethanol to maintain reduced conditions within appropriate ranges, avoiding sulfate reducing or methanogenic conditions as much as possible while mimicking field conditions. Analysis of chromium-50, Fe, and Mn obtained by sequential extraction from microcosms harvested (incubation terminated and microcosm contents analyzed) at various times showed that some aqueous chromium (Cr) was sorbed to particle surfaces within hours; reduction to Cr(III) and incorporation into amorphous and crystalline solid phases occurred during the next few months. Amorphous Cr-containing fractions included Fe and Mn hydroxides and organic matter. Ultimately, most of the chromium-50 tracer was present in the less reactive crystalline phase. However, Fe and Mn were broadly distributed at later stages of reduction, and both were spatially co-located with Cr on a micrometer (μm) scale. Solid-phase data collected using scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and X-ray absorption spectroscopy (XAS) indicated that some Cr(III) was associated with mixed valence Fe oxides like magnetite and Fe-Mn oxides like jacobsite. Additionally, Cr(III) was observed within several μm of Fe and Mn embedded in clays and in mineral coatings. To evaluate the potential for reoxidation of Cr(III) to Cr(VI), additional batch microcosms of aquifer materials and mixtures of Fe- and Mn-coated sand were first reduced for more than 1 year and subsequently oxidized for almost 2 years. Hexavalent chromium was formed and was available for release to the aqueous phase during oxidation of all materials; however, the timing and amount of Cr(VI) formed and released varied among substrates. Artificial substrates containing more Mn produced more Cr(VI). Site material characteristic of recent Mojave River deposits contained within the IRZ produced the least Cr(VI) during oxidation, while site materials composed of older Mojave River aquifer material (containing more Mn) produced more Cr(VI). Site material collected from within the IRZ contained more Cr but produced an intermediate amount of Cr(VI) following oxidation. The combined results of microcosm chemistry and solid-phase analyses showed that the nature and locus of Cr(III) sequestration influenced its vulnerability to reoxidation to Cr(VI). It was concluded that co-location of Cr with Mn at later stages of reduction influenced the susceptibility of Cr(III) to reoxidation in microcosms. Reoxidation of Cr(III) to Cr(VI) was observed in experiments with previously reduced material after just 14 days exposure to oxygen. As much as 10 percent of added Cr was oxidized to Cr(VI) in microcosms prepared using recent Mojave River aquifer material, and as much as 20 percent of added Cr was oxidized to Cr(VI) in microcosms prepared using older Mojave River aquifer material. Less Cr(VI) (less than 3 percent of Cr added before reduction) was released to the aqueous phase, and this release occurred following longer oxygen exposure. Site managers may need to plan for long-term monitoring and the possibility of active maintenance of anoxic conditions within the IRZ to ensure permanent sequestration of Cr after bioremediation with ethanol ceases.

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Summary and conclusions

Executive Summary Chromium concentrations in rock and aquifer material in Hinkley and Water Valleys in the Mojave Desert, 80 miles northeast of Los Angeles, California, are generally low compared to the average chromium concentration of 185 milligrams per kilogram (mg/kg) in the average bulk continental crust. Chromium concentrations in felsic, coarse-textured “Mojave-type” deposits, composed of Mojave River stream (alluvium) and lake-margin (beach) deposits sourced from the Mojave River, are as low as 5 mg/kg, with a median concentration of 23 mg/kg in aquifer materials adjacent to the screened intervals of sampled wells. The most abundant chromium-containing mineral within aquifer materials in Hinkley and Water Valleys is magnetite. Magnetite is resistant to weathering, and about 90 percent of chromium remains within unweathered mineral grains. However, chromium-containing hornblende diorite and basalt are present in surrounding uplands, and chromium-containing actinolite is present within some aquifer materials. Although geologic abundance of chromium is clearly important, hexavalent chromium, Cr(VI), concentrations in alkaline oxic groundwater are related to additional factors. Hexavalent chromium concentrations in groundwater are influenced by a combination of processes including (1) mineralogy and the weathering rates of chromium-containing minerals; (2) texture of aquifer deposits; (3) accumulation of chromium weathered from minerals within surface coatings on mineral grains; (4) oxidation of accumulated Cr(III) to Cr(VI) in the presence of manganese oxides (Mn oxides), including the abundance and oxidation states of those Mn oxides; (5) pH-dependent desorption of chromium from coatings on the surfaces of mineral grains into groundwater during appropriate aqueous geochemical conditions; and (6) age (time since recharge) of groundwater. The pH of groundwater increases with groundwater age (time since recharge) as a result of silicate weathering, and desorption of Cr(VI) from aquifer deposits increases with increasing pH as long as groundwater remains oxic. In the absence of the detailed geologic, geochemical, and hydrologic data collected as part of this study, pH-dependent sorption, evaluated as the Cr(VI) occurrence probability at the measured pH, is an effective indicator of natural or anthropogenic Cr(VI). The Pacific Gas and Electric Company (PG&E) Hinkley compressor station is used to compress natural gas as it is transported through a pipeline from Texas to California. Between 1952 and 1964, cooling water containing Cr(VI) was discharged to unlined ponds and released into groundwater in unconsolidated aquifers. The extent of groundwater containing evidence of at least some anthropogenic Cr(VI) was 5.5 square miles (mi 2 ) and was estimated using a summative scale incorporating geologic, geochemical, and hydrologic data collected from more than 100 wells between March 2015 and November 2017. The summative-scale Cr(VI) plume extent is larger than the 2.2 mi 2 extent of the October–December 2015 (Q4 2015) regulatory Cr(VI) plume but is smaller than the 8.3 mi 2 maximum mapped extent of Cr(VI) greater than the interim regulatory Cr(VI) background concentration of 3.1 micrograms per liter (μg/L). The summative-scale Cr(VI) plume is within felsic, low-chromium aquifer material deposited by the Mojave River described as Mojave-type deposits and is within the area covered by the PG&E monitoring well network. Background Cr(VI) concentrations were calculated using the computer program ProUCL 5.1 as the upper 95-percent tolerance limit, UTL 95 , using data from wells outside the summative-scale Cr(VI) plume extent collected between April 2017 and March 2018. The overall UTL 95 for undifferentiated, unconsolidated deposits in the eastern and western subareas and the northern subarea upgradient of the Mount General fault in Hinkley Valley was 3.8 μg/L; this value is similar to the overall UTL 95 value of 3.9 μg/L calculated for Mojave-type deposits in Hinkley and Water Valleys, and is similar to the maximum Cr(VI) concentration of older groundwater in contact with Mojave-type deposits of 3.6 μg/L. In most cases the overall UTL 95 value may be an acceptable Cr(VI) background value near the Cr(VI) plume margin; however, UTL 95 values for the various subareas in Hinkley and Water Valleys provide greater resolution of Cr(VI) background that may be important for some purposes. The UTL 95 values for undifferentiated, unconsolidated deposits in the eastern, western, and northern subareas upgradient of the Mount General fault were 2.8, 3.8, and 4.8 μg/L, respectively. The UTL 95 value of 2.8 μg/L for wells screened in undifferentiated, unconsolidated deposits in the eastern subarea is important for plume management because the Hinkley compressor station and most of the summative-scale Cr(VI) plume are within the eastern subarea. A UTL 95 value of 2.3 μg/L was calculated for Mojave-type deposits downgradient from the Hinkley compressor station. This value represents Cr(VI) concentrations that may have been present in that part of the aquifer had Cr(VI) not been released from the Hinkley compressor station, and it reflects coarser textured deposits in this area and the proximity of those deposits to recharge areas along the Mojave River that results in younger (post-1952), less alkaline groundwater than in wells farther downgradient. This value may be a suitable metric for Cr(VI) cleanup goals within the Cr(VI) plume after regulatory updates. A separate UTL 95 value of 5.8 μg/L was calculated for mudflat/playa deposits and older groundwater near Mount General in the eastern subarea. The UTL 95 values calculated for undifferentiated, unconsolidated deposits in the northern subarea downgradient from the Mount General fault and in Water Valley, including lacustrine (lake) deposits and material eroded from basalt and Miocene deposits, were 9.0 and 6.4 μg/L, respectively. Hexavalent chromium concentrations in more than 70 domestic wells sampled between January 27 and 31, 2016, ranged from less than the study reporting level of 0.1–4.0 μg/L, with a median concentration of 1.2 μg/L. Hexavalent chromium concentrations in water from domestic wells did not exceed UTL 95 values within subareas where the wells were located. Water from 47 percent of domestic wells sampled between January 27 and 31, 2016, had arsenic, uranium, or nitrate concentrations above a maximum contaminant level. Anthropogenic Cr(VI) within groundwater downgradient from the Hinkley compressor station is treated by PG&E using bioremediation by adding ethanol as a reductant within a volume of aquifer known as the in situ reactive zone (IRZ). Laboratory microcosm studies showed that Cr(VI) is rapidly reduced to Cr(III) with additions of ethanol. Reduced Cr(III) is sorbed and is sequestered into crystalline iron and manganese oxides on the surfaces of mineral grains within the microcosms during a period of several months. Trivalent chromium was reoxidized back to Cr(VI) within 2 weeks of return to oxic (oxygen present) conditions within the microcosms. As much as 10 percent of added Cr was oxidized to Cr(VI) in microcosms prepared using recent Mojave River aquifer material, and as much as 20 percent of added Cr was oxidized to Cr(VI) in microcosms prepared using older Mojave River aquifer material. Less Cr(VI) (less than 3 percent of Cr added before reduction) was released to the aqueous phase, and this release occurred following longer time periods of oxygen exposure. Sequestration of chromium with manganese oxides during reduction facilitates reoxidation of Cr(III) to Cr(VI) under oxic conditions. Future maintenance of anoxic (oxygen absent) conditions would ensure continued sequestration of chromium as Cr(III) within IRZ treated portions of the Cr(VI) plume. Although Cr(VI) within the summative-scale Cr(VI) plume may have an anthropogenic history associated with releases from the Hinkley compressor station, Cr(VI) concentrations less than the UTL 95 values for the various subareas may not require regulatory attention. The regulatory Cr(VI) plume can be updated using the UTL 95 values calculated as part of this study. The updated regulatory Cr(VI) plume extent would lie within the summative-scale Cr(VI) plume extent. The authority to establish regulatory Cr(VI) background values, clean-up goals, and future site management practices resides with the Lahontan Regional Water Quality Control Board.

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Characterization of subsurface conditions and recharge at the irrigated four-plex baseball field, Fort Irwin National Training Center, California, 2018–20

The U.S. Geological Survey performed subsurface and geophysical site characterization of the irrigated four-plex baseball field in the Langford Valley–Irwin Groundwater Subbasin, as part of a research study in cooperation with the U.S. Environmental Protection Agency, the Agricultural Research Service, and the Fort Irwin National Training Center, California. To help meet future demands, the Fort Irwin National Training Center is evaluating the efficacy of gravity-fed drywells to enhance storm-water recharge into the Langford Valley–Irwin Groundwater Subbasin by bypassing fine-grained, less permeable deposits between land surface and the water table. The amount, rate, and location of recharge beneath an irrigated baseball field in the groundwater basin at the Fort Irwin National Training Center is not well understood, so data were collected using physical and geophysical techniques to characterize subsurface materials, geologic controls, and the vertical movement of water through the unsaturated zone to the water table near the drywell at the Fort Irwin National Training Center. Based on the data collected and interpreted from these techniques, several fine-grained deposits were identified. Although these deposits appear to impede the downward movement of water through the unsaturated zone locally, they are not laterally continuous, and water appears to continue to move downward when it reaches the edges of the deposits. These data will help managers evaluate recharge at the site and determine if the use of gravity-fed drywells enhances recharge from surface runoff.

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Groundwater quality in shallow aquifers in the western Mojave Desert, California

Groundwater provides more than 40 percent of California’s drinking water. To protect this vital resource, the State of California created the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The Priority Basin Project (PBP) of the GAMA Program provides a comprehensive assessment of the State’s groundwater quality and increases public access to groundwater-quality information. One GAMA-PBP study unit is in the western part of the Mojave Desert, where shallow aquifers provide drinking water for many rural households.

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Selected trace-elements in alluvium and rocks, western Mojave Desert, southern California

Concentrations of twenty-seven elements, including naturally-occurring water-quality contaminants arsenic, chromium, and uranium, were measured in 217 samples of alluvium and rock from the western Mojave Desert, southern California, using portable (pXRF) and laboratory (LXRF) X-ray fluorescence. Comparison of measurements with NIST-traceable standards was good, although pXRF overestimated iron compared to LXRF. Results suggest pXRF survey data are sufficiently accurate to assess regional geochemical differences in geologic-source terrains. Principal component analysis showed rubidium and potassium were associated with alluvium eroded from felsic terrain, while iron, copper, chromium, and to a lesser extent titanium, manganese, and nickel were associated with alluvium eroded from mafic terrain. Zinc, vanadium, and arsenic were associated with alluvium eroded from hydrothermal terrain. Elemental assemblages associated with different source terrains were traced spatially to identify the source and composition of alluvium composing aquifers pumped for water supply. Changes in geologic source terrain to the Mojave River, associated with movement along the San Andreas Fault over the past one to five million years, reduced the mafic fraction and increased the felsic fraction of alluvium deposited to the regionally important floodplain aquifer along the Mojave River—lowering chromium concentrations in alluvium through geologic time. Comparison of pXRF and sequential extraction data from 40 samples showed arsenic and uranium were more abundant on the surfaces of mineral grains, while chromium and vanadium remained mostly within unweathered mineral grains—suggesting arsenic and uranium may be more readily mobilized into groundwater with changes in pH, redox, or ionic strength than chromium or vanadium.

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Natural and man-made hexavalent chromium, Cr(VI), in groundwater near a mapped plume, Hinkley, California—study progress as of May 2017, and a summative-scale approach to estimate background Cr(VI) concentrations

This report describes (1) work done between January 2015 and May 2017 as part of the U.S. Geological Survey (USGS) hexavalent chromium, Cr(VI), background study and (2) the summative-scale approach to be used to estimate the extent of anthropogenic (man-made) Cr(VI) and background Cr(VI) concentrations near the Pacific Gas and Electric Company (PG&E) natural gas compressor station in Hinkley, California. Most of the field work for the study was completed by May 2017. The summative-scale approach and calculation of Cr(VI) background were not well-defined at the time the USGS proposal for the background Cr(VI) study was prepared but have since been refined as a result of data collected as part of this study. The proposed summative scale consists of multiple items, formulated as questions to be answered at each sampled well. Questions that compose the summative scale were developed to address geologic, hydrologic, and geochemical constraints on Cr(VI) within the study area. Each question requires a binary (yes or no) answer. A score of 1 will be assigned for an answer that represents data consistent with anthropogenic Cr(VI); a score of –1 will be assigned for an answer that represents data inconsistent with anthropogenic Cr(VI). The areal extent of anthropogenic Cr(VI) estimated from the summative-scale analyses will be compared with the areal extent of anthropogenic Cr(VI) estimated on the basis of numerical groundwater flow model results, along with particle-tracking analyses. On the basis of these combined results, background Cr(VI) values will be estimated for “Mojave-type” deposits, and other deposits, in different parts of the study area outside the summative-scale mapped extent of anthropogenic Cr(VI).

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Against the current— The Mojave River from sink to source: The 2018 Desert Symposium field trip road log

The Mojave River evolved over the past few million years by “fill and spill” from upper basins near its source in the Transverse Ranges to lower basins. Each newly “spilled into” basin in the series? sustained a long-lived lake but gradually filled with Mojave River sediment, leading to spill to a yet lower elevation? basin. The Mojave River currently terminates at Silver Lake, near Baker, CA, but previously overflowed this terminus onward to Lake Manly in Death Valley during the last glacial cycle. The river’s origin and evolution are intricately interwoven with tectonic, climatic, and geomorphic processes through time, beginning with San Andreas fault interactions that created a mountain range across a former externally draining river. We will see and discuss the Mojave River’s predecessor streams and basins, its evolution as it lengthened to reach the central Mojave Desert, local and regional tectonic controls, groundwater flow, flood history, and support of isolated perennial stream reaches that host endemic species. In association with these subjects are supporting studies such as paleoclimate records, location and timing for groundwater and wetlands in the central Mojave Desert, and effects of modern water usage. The trip introduces new findings for the groundwater basin of Hinkley Valley, including an ongoing remediation project that provides a wealth of information on past and present river flow and associated development of the groundwater system.

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Electrical resistivity investigation of fluvial geomorphology to evaluate potential seepage conduits to agricultural lands along the San Joaquin River, Merced County, California, 2012–13

Increased flows in the San Joaquin River, part of the San Joaquin River Restoration Program, are designed to help restore fish populations. However, increased seepage losses could result from these higher restoration flows, which could exacerbate existing drainage problems in neighboring agricultural lands and potentially damage crops. Channel deposits of abandoned river meanders that are hydraulically connected to the river could act as seepage conduits, allowing rapid and widespread water-table rise during restoration flows. There is a need to identify the geometry and properties of these channel deposits to assess their role in potential increased seepage effects and to evaluate management alternatives for reducing seepage. Electrical and electromagnetic surface geophysical methods have provided a reliable proxy for lithology in studies of fluvial and hyporheic systems where a sufficient electrical contrast exists between deposits of differing grain size. In this study, direct-current (DC) resistivity was used to measure subsurface resistivity to identify channel deposits and to map their subsurface geometry. The efficacy of this method was assessed by using DC resistivity surveys collected along a reach of the San Joaquin River in Merced County, California, during the summers of 2012 and 2013, in conjunction with borings and associated measurements from a hydraulic profiling tool. Modeled DC resistivity data corresponded with data from cores, hand-auger samples, a hydraulic profiling tool, and aerial photographs, confirming that DC resistivity is effective for differentiating between silt and sand deposits in this setting. Modeled DC resistivity data provided detailed two-dimensional cross-sectional resistivity profiles to a depth of about 20 meters. The distribution of high-resistivity units in these profiles was used as a proxy for identifying areas of high hydraulic conductivity. These data were used subsequently to guide the location and depth of wells installed onsite for monitoring flow in the channel deposits. Estimates of the cross-sectional area of channel deposits from DC resistivity pseudosections can provide critical input for groundwater-flow models designed to simulate river seepage and evaluate seepage-management alternatives.

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