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Research about Hinkley, California

Source-linked reports with geographic coverage including Hinkley, California.

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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.

California

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

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.

California

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.

California

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.

California

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).

California

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.

California

Groundwater chemistry and hexavalent chromium

Water samples collected by the U.S. Geological Survey from more than 100 wells between March 2015 and November 2017 in Hinkley and Water Valleys, in the Mojave Desert 80 miles northeast of Los Angeles, California, were analyzed for field parameters, major ions, nutrients, and selected trace elements, including hexavalent chromium, Cr(VI). Water from most wells was alkaline and oxic. The pH ranged from 6.9 in water-table wells near recharge areas along the Mojave River to 9.4 in deeper wells farther downgradient in the northern subarea. Hexavalent chromium concentrations measured by ion chromatography using U.S. Environmental Protection Agency Method 218.6 and a version of that method used for detection of Cr(VI) concentrations as low as 0.06 micrograms per liter (μg/L), produced results comparable to field speciation with subsequent analyses by graphite furnace atomic absorption spectroscopy (coefficient of determination, R 2 , of 0.97). Hexavalent chromium concentrations ranged from less than the study reporting level of 0.10 to 2,500 μg/L. The highest concentrations were within the October–December 2015 (Q4 2015) regulatory Cr(VI) plume downgradient from the Hinkley compressor station. Hexavalent chromium concentrations outside the Q4 2015 regulatory Cr(VI) plume were as high as 11 μg/L. Hexavalent chromium concentrations in water from most wells were distributed in a narrow redox potential and pH band within the overlapping chromate ion, CrO 4 2− (aqueous) , and manganese-3, Mn(III) (solid) , stability fields. The redox potential of water from some wells completed in carbonate-rich mudflat/playa deposits approached the more oxic manganese-4, Mn(IV) (solid) , stability field. However, Cr(VI) concentrations in porewater pressure-extracted from Mn(IV)-containing deposits in the eastern subarea did not exceed 3.3 μg/L, and porewater does not appear to be a source of Cr(VI) concentrations greater than this concentration in water from wells in the eastern subarea. On the basis of comparison with California-wide data, Cr(VI) concentrations at the measured pH were higher than expected for uncontaminated water from wells (1) within the Q4 2015 regulatory Cr(VI) plume, (2) within the eastern subarea nominally crossgradient from the Hinkley compressor station and upgradient from the Q4 2015 regulatory Cr(VI) plume, and (3) from shallow wells in the northern subarea downgradient from the leading edge of the Q4 2015 regulatory Cr(VI) plume. Hexavalent chromium concentrations in alkaline water from wells in the northern subarea of Hinkley Valley and in Water Valley were within ranges expected for uncontaminated water elsewhere in California given their pH and trace-element composition. Hexavalent chromium concentrations were higher than expected on the basis of selected trace-element concentrations that co-occur with Cr(VI) in water from wells within the Q4 2015 regulatory Cr(VI) plume and from wells in the eastern and northern subareas near the plume margins. Hexavalent chromium concentrations did not exceed 4 μg/L in water from domestic wells sampled in Hinkley and Water Valleys and were generally within ranges expected for uncontaminated groundwater given their pH and trace-element composition. Interpretations derived from Cr(VI) and pH, and from Cr(VI) and selected trace-element concentrations collected between March 2015 and November 2017 were used within a summative-scale analysis to determine the Cr(VI) plume extent (chapter G). However, Cr(VI) background concentrations (chapter G) were calculated from regulatory data collected from selected wells between April 2017 and January 2018.

California

Environmental tracers of groundwater source, age, and geochemical evolution

Hexavalent chromium, Cr(VI), was discharged in cooling wastewater to unlined surface ponds from 1952 to 1964 and reached the underlying unconsolidated aquifer at the Pacific Gas and Electric Company (PG&E) Hinkley compressor station in the Mojave Desert, 80 miles northeast of Los Angeles, California. A suite of environmental tracers was analyzed in water samples collected from more than 100 wells to characterize the source, age, and geochemical evolution of groundwater within and near the Cr(VI) plume in Hinkley and Water Valleys. This information was used to help determine the extent of Cr(VI) associated with releases from the Hinkley compressor station and to identify Cr(VI) associated with natural sources. The source of water in most wells, indicated by stable oxygen and hydrogen isotope values for water, delta oxygen-18 and delta deuterium, was recharge by infiltration of intermittent surface flows in the Mojave River. With the exception of small flows in 1958, the Mojave River was largely dry between 1952 and 1969. This dry period spans the period of Cr(VI) releases from the Hinkley compressor station; 1952–69 also spans the period of high tritium levels in precipitation resulting from the atmospheric testing of nuclear weapons and, as a consequence, tritium concentrations in groundwater in Hinkley Valley were comparatively low. Groundwater ages (time since recharge) increased downgradient from the Mojave River and with depth. Tritium, measured by helium ingrowth with a study reporting level of 0.05 tritium unit, was detected in water from 51 percent of wells, with detectable tritium as far as 7 miles downgradient from the Mojave River. Tritium concentrations were higher, and tritium/helium-3 groundwater ages younger, in water from wells near the Mojave River and in water from shallower wells downgradient. Agricultural pumping has decreased groundwater levels as much as 60 feet since 1952. As a result of this pumping, some groundwater containing tritium, and presumably anthropogenic Cr(VI), has been removed from the aquifer. The distribution of wells having carbon-14 activities near or greater than 100-percent modern carbon, consistent with post-1952 recharge water, was similar to the distribution of wells containing detectable tritium. Carbon-14 activities as low as 8.9-percent modern carbon, with carbon-14 ages (unadjusted for reactions with aquifer materials) of almost 20,000 years before present (ybp), were sampled in water from some deep wells. Hexavalent chromium concentrations in older groundwater were as high as 11 micrograms per liter but did not exceed 3.6 micrograms per liter in older water from wells completed in “Mojave-type” deposits (composed of felsic Mojave River stream and near-shore lake deposits sourced from the Mojave River); this value may represent an upper limit on Cr(VI) concentrations in groundwater within Mojave-type deposits that likely approximates background Cr(VI) concentrations in the study area. Chlorofluorocarbons were released to the atmosphere and hydrologic cycle as a result of industrial activity beginning in the 1930s. Chlorofluorocarbon data were not generally suitable for groundwater-age dating in Hinkley and Water Valley because of nonatmospheric contributions from local sources. Strontium-87/86 isotope ratios and stable chromium isotopes, delta chromium-53, provide information on the geochemical evolution of groundwater in the aquifer. Highly radiogenic strontium-87/86 ratios greater than 0.71000 were present in water from wells completed in coarse-textured Mojave-type deposits having low chromium concentrations but were not diagnostic of these materials. Nonradiogenic strontium-87/86 ratios less than 0.70950 were diagnostic of weathered materials in the northern subarea of Hinkley and in Water Valley that were eroded from Miocene (23–5 million ybp) deposits east of the study area. Values for delta chromium-53 ranged from near 0 to 2.8 parts per thousand (‰) difference. The extent of reductive fractionation, mixing with native groundwater, and longitudinal dispersion within the October–December 2015 (Q4 2015) regulatory Cr(VI) plume can be estimated on the basis of the delta chromium-53 isotope composition of groundwater within the plume. Reduction of Cr(VI) to trivalent chromium, Cr(III), can occur in the presence of natural reductants in oxic groundwater. Although not diagnostic of anthropogenic chromium at the concentrations of interest near the Q4 2015 regulatory Cr(VI) plume margin, delta chromium-53 data indicate anthropogenic Cr(VI) within the plume is not conservative and has reacted with aquifer materials; these reactions have removed some anthropogenic Cr(VI) from groundwater. Environmental tracers, and the distribution of modern (post-1952) and premodern (pre-1952) groundwater, inform understanding of the extent of anthropogenic and naturally occurring Cr(VI) near the Q4 2015 regulatory Cr(VI) plume and the understanding of geochemical processes occurring in and near the margins of the Cr(VI) plume. The oxygen and hydrogen isotope compositions of water, tritium/helium-3 groundwater-age data, and carbon-14 data were used with mineralogy and chemistry data as part of a summative-scale analysis to determine the Cr(VI) plume extent later in this professional paper (chapter G).

California

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.

California

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.

California

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.

California

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.

California

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).

California

A plan for study of hexavalent chromium, CR(VI) in groundwater near a mapped plume, Hinkley, California, 2016

The Pacific Gas and Electric Company (PG&E) Hinkley compressor station, in the Mojave Desert 80 miles northeast of Los Angeles, is used to compress natural gas as it is transported through a pipeline from Texas to California. Between 1952 and 1964, cooling water used at the compressor station was treated with a compound containing chromium to prevent corrosion. After cooling, the wastewater was discharged to unlined ponds, resulting in contamination of soil and groundwater in the underlying alluvial aquifer (Lahontan Regional Water Quality Control Board, 2013). Since 1964, cooling-water management practices have been used that do not contribute chromium to groundwater. In 2007, a PG&E study of the natural background concentrations of hexavalent chromium, Cr(VI), in groundwater estimated average concentrations in the Hinkley area to be 1.2 micrograms per liter (μg/L), with a 95-percent upper-confidence limit of 3.1 μg/L (CH2M-Hill, 2007). The 3.1 μg/L upper-confidence limit was adopted by the Lahontan Regional Water Quality Control Board (RWQCB) as the maximum background concentration used to map the plume extent. In response to criticism of the study’s methodology, and an increase in the mapped extent of the plume between 2008 and 2011, the Lahontan RWQCB (Lahontan Regional Water Quality Control Board, 2012) agreed that the 2007 PG&E background-concentration study be updated. The purpose of the updated background study is to evaluate the presence of natural and man-made Cr(VI) near Hinkley, Calif. The study also is to estimate natural background Cr(VI) concentrations in the aquifer upgradient and downgradient from the mapped Cr(VI) contamination plume, as well as in the plume and near its margins. The study was developed by the U.S. Geological Survey (USGS) in collaboration with a technical working group (TWG) composed of community members, the Independent Review Panel (IRP) Manager (Project Navigator, Ltd.), the Lahontan RWQCB, PG&E, and consultants for PG&E.&E.

California