Chromium in minerals and selected aquifer materials

Abstract

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).