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.
|Summary and conclusions
|John A. Izbicki, Krishangi D. Groover, Whitney A. Seymour, David M. Miller, John G. Warden, Laurence G. Miller
|USGS Numbered Series
|USGS Publications Warehouse
|California Water Science Center