Geology topics

Whitney A. Seymour

Publications and source records attributed to Whitney A. Seymour.

10 recordsLinked to original sources

USGS2024

Groundwater sustainability and land subsidence in California’s Central Valley

The Central Valley of California is one of the most prolific agricultural regions in the world. Agriculture is reliant on the conjunctive use of surface-water and groundwater. The lack of available surface-water and land-use changes have led to pumping-induced groundwater-level and storage declines, land subsidence, changes to streamflow and the environment, and the degradation of water quality. As a result, in part, the Sustainable Groundwater Management Act (SGMA) was developed. An examination of the components of SGMA and contextualizing regional model applications within the SGMA framework was undertaken to better understand and quantify many of the components of SGMA. Specifically, the U.S. Geological Survey (USGS) updated the Central Valley Hydrologic Model (CVHM) to assess hydrologic system responses to climatic variation, surface-water availability, land-use changes, and groundwater pumping. MODFLOW-OWHM has been enhanced to simulate the timing of land subsidence and attribute its inelastic and elastic portions. In addition to extending CVHM through 2019, the new version, CVHM2, includes several enhancements as follows: managed aquifer recharge (MAR), pumping with multi-aquifer wells, inflows from ungauged watersheds, and more detailed water-balance subregions, streamflow network, diversions, tile drains, land use, aquifer properties, and groundwater level and land subsidence observations. Combined with historical approximations, CVHM2 estimates approximately 158 km 3 of storage loss in the Central Valley from pre-development to 2019. About 15% of the total storage loss is permanent loss of storage from subsidence that has caused damage to infrastructure. Climate extremes will likely complicate the efforts of water managers to store more water in the ground. CVHM2 can provide data in the form of aggregated input datasets, simulate climatic variations and changes, land-use changes or water management scenarios, and resulting changes in groundwater levels, storage, and land subsidence to assist decision-makers in the conjunctive management of water supplies.

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USGS2023

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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USGS2023

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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USGS2023

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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USGS2023

Analyses of regulatory water-quality data

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 northeast of Los Angeles, California. The Pacific Gas and Electric Company has monitored groundwater near Hinkley, California, for Cr(VI) and other constituents since the late 1980s. By June 2017, more than 20,000 samples had been collected and analyzed for Cr(VI) for regulatory purposes. Most Cr(VI) samples were analyzed using the U.S. Environmental Protection Agency (EPA) Method 218.6 with a laboratory reporting level (LRL) of 0.2 micrograms per liter (μg/L). Between July 2012 and June 2017, selected samples were analyzed for low-level Cr(VI) concentrations using a modified version of EPA Method 218.6 with an LRL of 0.06 μg/L. Field-blank data and duplicate samples collected during this period indicate a study reporting level (SRL) of 0.2 μg/L for most analyses and a SRL of 0.12 μg/L for low-level Cr(VI) analyses. The overall precision for Cr(VI) data analyzed by both methods at the interim regulatory Cr(VI) background concentration of 3.1 μg/L was 0.09 μg/L, or about 3 percent. Hexavalent chromium concentration trends were calculated for 564 monitoring wells for the period from July 2012 through June 2017. Upward Cr(VI) concentration trends were present in water from 102 monitoring wells throughout Hinkley and Water Valleys. Upward Cr(VI) concentration trends in water from wells near the margins of the October–December 2015 (Q4 2015) regulatory Cr(VI) plume (1) within strands of the Lockhart fault east and southeast of the Hinkley compressor station and (2) in water from shallow wells within the northern subarea were consistent with expansion of the Cr(VI) plume in these areas between 2012 and 2017. Upward Cr(VI) concentration trends were widely distributed elsewhere in Hinkley and Water Valleys outside the Q4 2015 regulatory Cr(VI) plume and were commonly associated with declining water levels. These upward trends may result from natural Cr(VI) sources, including movement of Cr(VI) containing groundwater from (1) weathered bedrock, (2) fine-textured deposits, or (3) secondarily oxidized material distributed throughout aquifer deposits. Downward Cr(VI) concentration trends were observed in 146 monitoring wells. Downward trends were largely within the Q4 2015 regulatory Cr(VI) plume and can be attributed to remediation activities downgradient from the Hinkley compressor station. Hexavalent chromium concentration trends also were calculated for 219 domestic wells from July 2012 through June 2017. Upward Cr(VI) concentration trends in 8 domestic wells and downward trends in 23 domestic wells were clustered largely within former residential areas west of the Q4 2015 regulatory Cr(VI) plume. Results of Cr(VI) trend analyses (including upward, downward, and no trend) were used with other data as part of a summative-scale analysis (chapter G) to define the extent of anthropogenic Cr(VI) and natural Cr(VI) within Hinkley and Water Valleys.

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USGS2023

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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USGS2023

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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USGS2023

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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USGS2022

Hydrogeologic characterization of the San Antonio Creek Valley watershed, Santa Barbara County, California

The San Antonio Creek Valley watershed (SACVW) is located in western Santa Barbara County, about 15 miles south of Santa Maria and 55 miles north of Santa Barbara, California. The SACVW is about 135 square miles and encompasses the San Antonio Creek Valley groundwater basin; the SACVW is separated from adjacent groundwater basins by the Casmalia and Solomon Hills to the north, and the Purisima Hills to the south. At the western, downstream part of the valley, uplifted, consolidated rocks cause groundwater to discharge at land surface at Barka Slough. Since the late 1800s, groundwater has been the primary source of water for agricultural, military, municipal, and domestic uses. Groundwater withdrawal by pumping exceeded the amount of water replenishing the aquifer system during water years 1948–2018, causing groundwater-level declines of more than 150 feet in parts of the valley and reducing base flow at Barka Slough. Reliance on groundwater for agricultural water use (primarily for the irrigation and frost protection of vineyards, and fruit and berry crops) continues to strain the sustainability of the groundwater system. Through a cooperative agreement, the Santa Barbara County Water Agency and Vandenberg Space Force Base invited the U.S. Geological Survey to address declines in groundwater levels, develop a better understanding of the hydrogeologic system, and provide tools to help evaluate and manage the effects of future development of the San Antonio Creek Valley groundwater basin within the encompassing San Antonio Creek Valley watershed (SACVW). The objectives of this study were to (1) refine the hydrogeologic framework of the San Antonio Creek Valley watershed, (2) quantify the hydrologic budget of the valley, and (3) develop hydrologic modeling tools to evaluate and aid in managing the groundwater resource. This report focuses on the first and second objectives to construct a hydrogeologic framework and characterize the historical and present-day hydrologic conditions of the SACVW during water years 1948–2018. As part of the second objective, work included quantifying the hydrologic budget and evaluating the hydrogeologic system using a combination of existing data and geologic and hydrologic data collected for this study. The groundwater-flow system in the SACVW consists of five hydrogeologic units. These separate water-bearing units were identified based on hydrogeologic properties, such as sediment grain size, vertical-head differences in multiple-depth, monitoring-well sites, long-term groundwater level responses to pumping and climate, and the chemical character of groundwater and groundwater age in the mostly semi-consolidated to unconsolidated basin-fill sediments. The hydrogeologic units that comprise the different aquifers vary in their lithologic composition. The upper and lower aquifers (upper Paso Robles Formation, and lower Paso Robles Formation and Careaga Sandstone, respectively) are relatively coarse grained and are comprised of sand, gravel, and clay; the middle confining unit (the middle Paso Robles Formation) is relatively fine grained and is comprised of primarily clay, silt, and sand. The Pezzoni-Casmalia and Los Alamos faults, which are inferred to transect the SACVW between the western and eastern areas of the valley floor, do not appear to substantially affect the groundwater system. Present-day recharge to the study area occurs primarily as infiltration from precipitation and streams in the upland areas of the Casmalia Hills and Solomon Hills, and along the main channel of San Antonio Creek. Reported estimates of annual natural recharge during water years 1948–2018 generally ranged from about 5,000 acre-feet to more than about 30,000 acre-feet. Stable and radioactive isotopes show that groundwater from the lower aquifer is old and probably was recharged as infiltration from precipitation and streams in the eastern upland areas of the Solomon Hills; however, the infiltration and recharge from these sources probably does not occur under present-day climatic conditions. Anthropogenic recharge, from sources such as return flow from agricultural irrigation, municipal water systems, and wastewater effluent, was estimated to range from about 600 acre-feet in 1948 to about 6,600 acre-feet in 2018. The average annual amount of groundwater removed from the SACVW by pumping during 1948–2018 was estimated to be about 17,200 acre-feet per year, increasing from about 3,000 acre-feet in 1948 to about 32,600 acre-feet in 2018. Estimates of annual pumpage generally exceeded estimates of annual recharge beginning in the mid-1970s and continuing through 2018. The predominant direction of groundwater flow under historical and present-day conditions was from the eastern uplands in the Solomon Hills to the west along San Antonio Creek to the discharge area in Barka Slough, and from the northern uplands in the Casmalia Hills south to San Antonio Creek. Pumpage since the early 1900s and the subsequent groundwater-level declines have substantially reduced the amount of natural groundwater discharge at Barka Slough. Estimates of base flow to San Antonio Creek at the western, downstream extent of the SACVW have varied over time in response to changes in groundwater pumpage and climate; however, there was an overall decline in base flow during water years 1956–2018, decreasing from an average of about 1,700 acre-feet per year during 1956–69, to about 300 acre-feet per year during 2016–18. The long-term extraction of groundwater correlates with a decrease in groundwater levels by more than about 150 feet since the early 1940s in the eastern part of the basin near Los Alamos, and as much as about 50 feet in the upland areas and in the western part of the basin. At Barka Slough, groundwater levels have declined below land surface in some places, altering native riparian vegetation in and around the slough. Surface-water quality in the SACVW varied depending on location and the time of year the samples were collected and on the amount of annual precipitation Most groundwater in the SACVW was calcium-bicarbonate-type water with total dissolved-solids concentrations of about 500–800 milligrams per liter generally representing water naturally recharged as infiltration from precipitation and streams. Total dissolved-solids concentrations in some wells ranged from 800 to 8,000 milligrams per liter, suggesting mixing of naturally recharged infiltrated water with water associated with oil-bearing geologic formations, agricultural products, or the evaporation of shallow groundwater. Concentrations of total dissolved solids and the chemical constituents chloride, nitrate plus nitrite (as nitrogen), calcium, and magnesium at selected wells generally increased during water years 1980–2018; increasing concentrations of these constituents may be associated with the expansion of agriculture in the watershed over time and the corresponding increase in the use of nitrates and calcium- and magnesium-based fertilizers and soil additives in modern agricultural practices. The predominant direction of groundwater flow during historical and present-day conditions was from the eastern uplands in the Solomon Hills to the west along San Antonio Creek toward Barka Slough, and from the western uplands in the Casmalia Hills south to San Antonio Creek. The age of groundwater in the SACVW was evaluated using radioactive isotopes, and the flow of groundwater within the SACVW was evaluated using radioactive and stable isotopes. Modern groundwater (recharged after 1952) was generally found adjacent to San Antonio Creek and its tributaries in wells with perforated depths that averaged about 270 feet below land surface. Pre-modern groundwater (recharged before 1952) was found in wells that had average perforation depths of about 540 ft below land surface. Pre-modern groundwater identified in wells in the eastern upland area is interpreted to have had long, slow travel times to the western part of the SACVW where it was eventually discharged as base flow at Barka Slough or extracted as groundwater pumpage.

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USGS2015

Cr(VI) occurrence and geochemistry in water from public-supply wells in California

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 (μg/L) to 32 μg/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 μg/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.

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