Chapter I of Natural and Anthropogenic (Human-Made) Hexavalent Chromium, Cr(VI), in Groundwater near a Mapped Plume, Hinkley, California: Sequestration and Reoxidation of Chromium in Experimental Microcosms

U.S. Geological Survey (USGS) | April 25th, 2023

Documents in this series: Chapter A: Introduction to Study Area Hydrogeology, Chromium Sources, Site History, and Purpose of Study Chapter B: Survey of Chromium and

Documents in this series: Chapter A: Introduction to Study Area Hydrogeology, Chromium Sources, Site History, and Purpose of Study Chapter B: Survey of Chromium and Selected Element Concentrations in Rock, Alluvium, and Core Material Chapter C: Chromium in Minerals and Selected Aquifer Materials Chapter D: Analyses of Regulatory Water-Quality Data Chapter E: Groundwater Chemistry and Hexavalent Chromium Chapter F: Environmental Tracers of Groundwater Source, Age, and Geochemical Evolution Chapter G: Evaluation of Natural and Anthropogenic (Human-Made) Hexavalent Chromium Chapter H: Predevelopment Water Levels, Groundwater Recharge, and Selected Hydrologic Properties of Aquifer Materials, Hinkley and Water Valleys, California Chapter I: Sequestration and Reoxidation of Chromium in Experimental Microcosms Chapter J: Summary and Conclusions 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.

Chapter J of Natural and Anthropogenic (Human-Made) Hexavalent Chromium, Cr(VI), in Groundwater near a Mapped Plume, Hinkley, California: Summary and Conclusions

U.S. Geological Survey (USGS) | April 25th, 2023

Documents in this series: Chapter A: Introduction to Study Area Hydrogeology, Chromium Sources, Site History, and Purpose of Study Chapter B: Survey of Chromium and

Documents in this series: Chapter A: Introduction to Study Area Hydrogeology, Chromium Sources, Site History, and Purpose of Study Chapter B: Survey of Chromium and Selected Element Concentrations in Rock, Alluvium, and Core Material Chapter C: Chromium in Minerals and Selected Aquifer Materials Chapter D: Analyses of Regulatory Water-Quality Data Chapter E: Groundwater Chemistry and Hexavalent Chromium Chapter F: Environmental Tracers of Groundwater Source, Age, and Geochemical Evolution Chapter G: Evaluation of Natural and Anthropogenic (Human-Made) Hexavalent Chromium Chapter H: Predevelopment Water Levels, Groundwater Recharge, and Selected Hydrologic Properties of Aquifer Materials, Hinkley and Water Valleys, California Chapter I: Sequestration and Reoxidation of Chromium in Experimental Microcosms Chapter J: Summary and Conclusions 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 (mi2) 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 mi2 extent of the October–December 2015 (Q4 2015) regulatory Cr(VI) plume but is smaller than the 8.3 mi2 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, UTL95, using data from wells outside the summative-scale Cr(VI) plume extent collected between April 2017 and March 2018. The overall UTL95 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 UTL95 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 UTL95 value may be an acceptable Cr(VI) background value near the Cr(VI) plume margin; however, UTL95 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 UTL95 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 UTL95 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 UTL95 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 UTL95 value of 5.8 μg/L was calculated for mudflat/playa deposits and older groundwater near Mount General in the eastern subarea. The UTL95 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 UTL95 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 UTL95 values for the various subareas may not require regulatory attention. The regulatory Cr(VI) plume can be updated using the UTL95 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. Also see: Natural and Anthropogenic Hexavalent Chromium, Cr(VI), in Groundwater near a Mapped Plume, Hinkley, California

Characterization of Groundwater Recharge and Flow in California's San Joaquin Valley From InSAR-Observed Surface Deformation

American Geophysical Union (AGU) | March 4th, 2021

Surface deformation in California's Central Valley (CV) has long been linked to changes in groundwater storage. Recent advances in remote sensing have enabled the mappin

Surface deformation in California's Central Valley (CV) has long been linked to changes in groundwater storage. Recent advances in remote sensing have enabled the mapping of CV deformation and associated changes in groundwater resources at increasingly higher spatiotemporal resolution. Here, we use interferometric synthetic aperture radar (InSAR) from the Sentinel-1 missions, augmented by continuous Global Positioning System (cGPS) positioning, to characterize the surface deformation of the San Joaquin Valley (SJV, southern two-thirds of the CV) for consecutive dry (2016) and wet (2017) water years. We separate trends and seasonal oscillations in deformation time series and interpret them in the context of surface and groundwater hydrology. We find that subsidence rates in 2016 (mean −42.0 mm/yr; peak −345 mm/yr) are twice that in 2017 (mean −20.4 mm/yr; peak −177 mm/yr), consistent with increased groundwater pumping in 2016 to offset the loss of surface-water deliveries. Locations of greatest subsidence migrated outwards from the valley axis in the wetter 2017 water year, possibly reflecting a surplus of surface-water supplies in the lowest portions of the SJV. Patterns in the amplitude of seasonal deformation and the timing of peak seasonal uplift reveal entry points and potential pathways for groundwater recharge into the SJV and subsequent groundwater flow within the aquifer. This study provides novel insight into the SJV aquifer system that can be used to constrain groundwater flow and subsidence models, which has relevance to groundwater management in the context of California's 2014 Sustainable Groundwater Management Act (SGMA).

Characterizing Nitrates in Central Coast Groundwater

Central Coast Groundwater Coalition (CCGC) | April 1st, 2016

The Central Coast Groundwater Coalition (CCGC) is a third-party cooperative groundwater monitoring program that was established for landowners/operators in the Ce

The Central Coast Groundwater Coalition (CCGC) is a third-party cooperative groundwater monitoring program that was established for landowners/operators in the Central Coast region as an alternative to the individual groundwater monitoring program. The cooperative program collects and synthesizes groundwater monitoring data on behalf of its members to fulfill requirements of the Irrigated Lands Regulatory Program. The Central Coast Regional Water Quality Control Board required that the CCGC characterize groundwater quality in the uppermost aquifer and identify and evaluate groundwater used for drinking water purposes. Specifically, the focus was on evaluating the spatial distribution of nitrate concentrations in ground- water basins used for drinking water and provide statistically-based estimates of where groundwater nitrate concentrations are likely to be above the maximum contaminant level (MCL) for nitrate.

Chino Basin Municipal Water District v. City of Chino et al

Superior Court of California, County of San Bernardino | August 25th, 2014

From "An Evaluation of California's Adjudicated Groundwater Basins" by Langridge et al: "Chino Basin is one of the largest groundwater basins in Southern California. It a

From "An Evaluation of California's Adjudicated Groundwater Basins" by Langridge et al: "Chino Basin is one of the largest groundwater basins in Southern California. It abuts Los Angeles County, Orange County, and Riverside County. Over the past few decades, the basin has experienced rapid growth. The southern area was once notable for containing the heaviest concentration of dairy farms in the United States. There is significant subsidence in areas of the basin due to overpumping. While it is often described as a basin with ongoing conflict, there were also significant collaborative efforts to address basin problems during and after the adjudication process. Three different stakeholder groups—overlying agricultural, overlying non-agricultural, and appropriators—negotiated a management plan prior to adjudication, and it was adopted in a 1978 stipulated judgment. Stakeholders agreed on water rights for each group of users. There were multiple additional amendments over the last twenty years adopted in a 2012 restated judgment." Click here for the Chino basin Department of Water Resources Adjudicated Basin Reporting page.

Chowchilla Subbasin Staff Assessment

California State Water Resources Control Board (SWRCB) | April 1st, 2025

The state intervention process for the Chowchilla Subbasin was triggered in March 2023 when DWR determined the subbasin’s 2022 GSP was inadequate and identified multipl

The state intervention process for the Chowchilla Subbasin was triggered in March 2023 when DWR determined the subbasin’s 2022 GSP was inadequate and identified multiple deficiencies in the GSP. DWR identified issues regarding the local agencies’ plans for managing for the chronic lowering of groundwater levels and land subsidence (land sinking due to groundwater pumping). State Water Board staff reviewed the 2022 GSP and determined that implementing the 2022 GSP would result in additional groundwater level declines, potential impacts to drinking water wells, and damage to subbasin infrastructure, such as canals and levees, through continued land subsidence. The GSAs released a revised draft GSP in August 2024, which they adopted with slight revisions in March 2025 (2025 GSP). State Water Board staff evaluated the 2025 GSP to determine if identified deficiencies were addressed. The GSAs made significant progress through the 2025 GSP and adequately addressed deficiencies. Through the 2025 GSP, the GSAs show a greater commitment to protecting drinking water users and improved groundwater management. State Water Board staff concludes the GSAs amended the GSP such that a probationary designation of the Chowchilla Subbasin is unnecessary and recommends the Board return the Subbasin to DWR’s jurisdiction for continued evaluation of local management under SGMA.

Chowchilla Subbasin Sustainable Groundwater Management Act (SGMA) Groundwater Sustainability Plan (3rd Revision)

Madera County | January 3rd, 2025

In 2024-2025, the GSAs revised the Subbasin GSP to:  Amend the Domestic Well Mitigation Program Refine the Groundwater Level Representative Monitoring Sites (RMS

In 2024-2025, the GSAs revised the Subbasin GSP to:  Amend the Domestic Well Mitigation Program Refine the Groundwater Level Representative Monitoring Sites (RMS) Network Refine Groundwater Level Sustainable Management Criteria (SMC)  Backstop Projects and Management Actions Refine Subsidence SMC and Provide for Subsidence Mitigation

Chowchilla Subbasin Sustainable Groundwater Management Act (SGMA) Groundwater Sustainability Plan (Revised)

Chowchilla Subbasin GSP Advisory Committee | July 27th, 2022

Due to file size, this document has been divided. Part 1, Part 2, Part 3, Part 4, Part 5, Part 6, Part 7, Part 8, Part 9, Part 10, Part 11, Part 12, Part 13, Part 14, Par

Due to file size, this document has been divided. Part 1, Part 2, Part 3, Part 4, Part 5, Part 6, Part 7, Part 8, Part 9, Part 10, Part 11, Part 12, Part 13, Part 14, Part 15, Part 16, Part 17  

Chowchilla Subbasin Sustainable Groundwater Management Act (SGMA) Groundwater Sustainablity Plan

Chowchilla Subbasin GSP Advisory Committee | January 1st, 2020

City of Barstow, et al v. City of Adelanto, el al (Mojave Basin Area cases)

Superior Court of California, County of Riverside | December 5th, 2002

From An Evaluation of California’s Adjudicated Groundwater Basins, Langridge et al, UC Davis (2016): "The Mojave Basin adjudication was initiated by a lawsuit filed

From An Evaluation of California’s Adjudicated Groundwater Basins, Langridge et al, UC Davis (2016): "The Mojave Basin adjudication was initiated by a lawsuit filed May 30, 1990, by the City of Barstow and the Southern California Water Company. The complaint alleged that the cumulative increase in water use in the upper part of the Mojave Basin caused or threatened to cause a reduction in the natural flow of water to the central part of the Mojave Basin. Water users included downstream agriculture (many alfalfa farms), aquaculture, recreational lakes, homeowner associations, and upstream burgeoning municipalities. In the center of the basin is the smaller, low-income town of Barstow, which was concerned about its water supply. A 1993 Stipulated Judgment set forth a proposed physical solution that did not apportion production rights on the basis of preexisting legal water rights, and parties representing over 80 percent of verified water production in the basin agreed to its terms. However, some farmers with overlying rights chose not to stipulate to the judgment. On appeal, the court stated that in considering a stipulated physical solution involving equitable apportionment, the water rights of parties that did not join the stipulation must also be considered. The adjudication set out a complex system to reduce production a producer’s free production allowance (FPA) over time, but withdrawals remain significant in three out of the five subareas. The judgment also contained unique provisions for assuring that the water needs of endangered and other species and their habitat would be protected. One outcome of the adjudication was that many farmers in the western Alto Subarea sold or leased their base annual production (BAP) rights or leased their FPA to municipalities, and population in the Alto Subarea almost doubled. The Barstow Marine Corps Logistics Base east of Barstow is a federal Superfund site."