Arsenic, chromium, uranium, and vanadium in rock, alluvium, and groundwater, Mojave River and Morongo Areas, western Mojave Desert, southern California

John A. Izbicki, Krishangi D. Groover, Whitney A. Seymour
{"title":"Arsenic, chromium, uranium, and vanadium in rock, alluvium, and groundwater, Mojave River and Morongo Areas, western Mojave Desert, southern California","authors":"John A. Izbicki, Krishangi D. Groover, Whitney A. Seymour","doi":"10.3133/sir20235089","DOIUrl":null,"url":null,"abstract":"First posted October 16, 2023 For additional information, contact: Director,California Water Science CenterU.S. Geological Survey6000 J Street, Placer HallSacramento, California 95819 Trace elements within groundwater that originate from aquifer materials and pose potential public-health hazards if consumed are known as geogenic contaminants. The geogenic contaminants arsenic, chromium, and vanadium can form negatively charged ions with oxygen known as oxyanions. Uranium complexes with bicarbonate and carbonate to form negatively charged ions having aqueous chemistry similar to oxyanions. The concentrations of arsenic, chromium, uranium, and vanadium in groundwater result from the combined effects of (1) geologic abundance within aquifer materials; (2) the fraction of these elements that have weathered from and sorbed to the surfaces of mineral grains and are potentially available to groundwater; and (3) the aqueous chemistry of dissolved oxyanions in groundwater during different redox conditions and pH, both of which are affected by hydrogeology, including the length of time groundwater has been in contact with aquifer materials. Concentrations of arsenic, chromium, uranium, and vanadium were measured in samples of (1) rock, surficial alluvium, and drill cuttings using portable (handheld) X-ray fluorescence (pXRF); (2) operationally defined fractions extractable from these materials; and (3) water from wells sampled between 2000 and 2018 within the 3,500 square mile Mojave River area and Morongo area of the western Mojave Desert, southern California.Regionally, rock and surficial alluvium in the Mojave River and Morongo areas are high in arsenic, low in chromium and uranium, and near the average bulk continental crust concentration for vanadium. Locally, high chromium concentrations are present in mafic rock within the San Gabriel Mountains; high uranium concentrations are present in felsic rock within the San Bernardino Mountains; and high arsenic, uranium, and vanadium concentrations are present in extrusive (volcanic) felsic rock within uplands surrounding groundwater basins along the Mojave River downstream from Barstow, California. Elemental assemblages identified using principal component analyses (PCA) of pXRF data were used to characterize felsic, mafic, and felsic volcanic source terranes in rock, surficial alluvium, and in geologic material penetrated by selected monitoring wells drilled between 1994 and 2018. Highly felsic alluvium associated with recent deposition from the Mojave River was identified along the 90-mile length of the floodplain aquifer along the river. The thickness of these highly felsic alluvial deposits ranged from 200 feet (ft) near Victorville and near Barstow to a thin veneer about 30 ft thick downstream from Victorville and downstream portions of the floodplain aquifer within the Mojave Valley.Groundwater in the Mojave River and Morongo areas was generally oxic and alkaline (pH≥7.5). Maximum concentrations of arsenic, hexavalent chromium [Cr(VI)], uranium, and vanadium in water from as many as 498 wells sampled between 2000 and 2018 were 360, 140, 1,470, and 690 micrograms per liter (μg/L), respectively. Water from 22 percent of sampled wells exceeded the U.S. Environmental Protection Agency (EPA) maximum contaminant level (MCL) for arsenic of 10 μg/L, with arsenic concentrations commonly exceeding the MCL in water from wells east of Barstow, deep wells in the Victorville fan, and in suboxic or reduced groundwater within the floodplain aquifer. Water from about 1 percent of sampled wells had Cr(VI) concentrations greater than the California MCL for total chromium of 50 μg/L, whereas 13 percent of sampled wells had Cr(VI) concentrations greater than the former California MCL of 10 μg/L. Hexavalent chromium concentrations were highest in water from wells in the Sheep Creek alluvial fan, eroded from mafic rock in the San Gabriel Mountains, although Cr(VI) concentrations greater than the former California MCL also were present elsewhere in the study area where mafic materials or older groundwater were present. Water from about 9 percent of sampled wells exceeded the EPA MCL for uranium of 30 μg/L, with concentrations exceeding the MCL commonly associated with irrigation return from agricultural land overlying the floodplain aquifer. Water from about 7 percent of sampled wells had vanadium concentrations greater than the California notification level of 50 μg/L; most of these wells were in the Victorville fan within the Mojave River area. In general, arsenic concentrations were higher in suboxic or reduced water; chromium concentrations were higher in oxic, alkaline (pH≥7.5) water; uranium concentrations were higher in circumneutral to slightly alkaline water (pH≤7.4); and vanadium concentrations were higher in highly alkaline (pH≥8.0) water, independent of redox status.Concentrations within geologic source terranes are not the sole factor controlling the concentrations of geogenic elements in groundwater. Differences in mineral weathering, pH-dependent sorption to surface-exchange sites on mineral grains, and aqueous geochemistry (especially redox status and pH) affect geogenic element concentrations in groundwater. Consequently, the relative abundances of arsenic, Cr(VI), uranium, and vanadium in groundwater differ from their relative abundances in the average bulk continental crust and their regional abundances in rock and surficial alluvium within groundwater basins of the western Mojave Desert. Processes that control the concentrations of arsenic, chromium, uranium, and vanadium in groundwater operate at the mineral-grain and aquifer scale.At the mineral-grain scale, sequential chemical extraction data show arsenic and uranium are more available to groundwater (under specific geochemical conditions) than chromium or vanadium, which largely are unavailable within unweathered mineral grains. Additionally, chromium and vanadium form few aqueous complexes and bind tightly with iron minerals within surface coatings on mineral grains making them less available to groundwater, whereas complexation with other dissolved ions enhances the solubility of uranium and, to a lesser extent, arsenic. Complexation also increases the valence (less negative charge) and increases the size of dissolved oxyanions and uranium complexes with bicarbonate and carbonate making them less readily sorbed to aquifer materials.At the aquifer scale, hydrogeology (including isolation of water in aquifers from surface sources of recharge, older groundwater age, and long contact times between groundwater and aquifer materials) combined with geochemical processes (such as silicate weathering) to produce alkaline groundwater. Desorption from sorption sites on the surfaces of mineral grains with increasing pH increases arsenic, chromium, and vanadium concentrations in water from wells and increases Cr(VI) concentrations as long as water remains oxic.Aqueous geochemistry and concentrations of geogenic contaminants also are affected by anthropogenic activities including (1) discharge of treated municipal wastewater, which may change the redox status of groundwater; (2) return from irrigated agriculture, which may alter the chemistry of groundwater and increase the solubility of trace elements such as uranium; and (3) groundwater pumping and subsequent water-level declines, which may change the source of water yielded by wells. The quality of water imported from northern California and infiltrated from ponds for groundwater recharge may be altered by naturally present trace elements, especially uranium in areas of agricultural land use or chromium within mafic alluvium.","PeriodicalId":478589,"journal":{"name":"Scientific Investigations Report","volume":"73 1","pages":"0"},"PeriodicalIF":0.0000,"publicationDate":"2023-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Scientific Investigations Report","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.3133/sir20235089","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0

Abstract

First posted October 16, 2023 For additional information, contact: Director,California Water Science CenterU.S. Geological Survey6000 J Street, Placer HallSacramento, California 95819 Trace elements within groundwater that originate from aquifer materials and pose potential public-health hazards if consumed are known as geogenic contaminants. The geogenic contaminants arsenic, chromium, and vanadium can form negatively charged ions with oxygen known as oxyanions. Uranium complexes with bicarbonate and carbonate to form negatively charged ions having aqueous chemistry similar to oxyanions. The concentrations of arsenic, chromium, uranium, and vanadium in groundwater result from the combined effects of (1) geologic abundance within aquifer materials; (2) the fraction of these elements that have weathered from and sorbed to the surfaces of mineral grains and are potentially available to groundwater; and (3) the aqueous chemistry of dissolved oxyanions in groundwater during different redox conditions and pH, both of which are affected by hydrogeology, including the length of time groundwater has been in contact with aquifer materials. Concentrations of arsenic, chromium, uranium, and vanadium were measured in samples of (1) rock, surficial alluvium, and drill cuttings using portable (handheld) X-ray fluorescence (pXRF); (2) operationally defined fractions extractable from these materials; and (3) water from wells sampled between 2000 and 2018 within the 3,500 square mile Mojave River area and Morongo area of the western Mojave Desert, southern California.Regionally, rock and surficial alluvium in the Mojave River and Morongo areas are high in arsenic, low in chromium and uranium, and near the average bulk continental crust concentration for vanadium. Locally, high chromium concentrations are present in mafic rock within the San Gabriel Mountains; high uranium concentrations are present in felsic rock within the San Bernardino Mountains; and high arsenic, uranium, and vanadium concentrations are present in extrusive (volcanic) felsic rock within uplands surrounding groundwater basins along the Mojave River downstream from Barstow, California. Elemental assemblages identified using principal component analyses (PCA) of pXRF data were used to characterize felsic, mafic, and felsic volcanic source terranes in rock, surficial alluvium, and in geologic material penetrated by selected monitoring wells drilled between 1994 and 2018. Highly felsic alluvium associated with recent deposition from the Mojave River was identified along the 90-mile length of the floodplain aquifer along the river. The thickness of these highly felsic alluvial deposits ranged from 200 feet (ft) near Victorville and near Barstow to a thin veneer about 30 ft thick downstream from Victorville and downstream portions of the floodplain aquifer within the Mojave Valley.Groundwater in the Mojave River and Morongo areas was generally oxic and alkaline (pH≥7.5). Maximum concentrations of arsenic, hexavalent chromium [Cr(VI)], uranium, and vanadium in water from as many as 498 wells sampled between 2000 and 2018 were 360, 140, 1,470, and 690 micrograms per liter (μg/L), respectively. Water from 22 percent of sampled wells exceeded the U.S. Environmental Protection Agency (EPA) maximum contaminant level (MCL) for arsenic of 10 μg/L, with arsenic concentrations commonly exceeding the MCL in water from wells east of Barstow, deep wells in the Victorville fan, and in suboxic or reduced groundwater within the floodplain aquifer. Water from about 1 percent of sampled wells had Cr(VI) concentrations greater than the California MCL for total chromium of 50 μg/L, whereas 13 percent of sampled wells had Cr(VI) concentrations greater than the former California MCL of 10 μg/L. Hexavalent chromium concentrations were highest in water from wells in the Sheep Creek alluvial fan, eroded from mafic rock in the San Gabriel Mountains, although Cr(VI) concentrations greater than the former California MCL also were present elsewhere in the study area where mafic materials or older groundwater were present. Water from about 9 percent of sampled wells exceeded the EPA MCL for uranium of 30 μg/L, with concentrations exceeding the MCL commonly associated with irrigation return from agricultural land overlying the floodplain aquifer. Water from about 7 percent of sampled wells had vanadium concentrations greater than the California notification level of 50 μg/L; most of these wells were in the Victorville fan within the Mojave River area. In general, arsenic concentrations were higher in suboxic or reduced water; chromium concentrations were higher in oxic, alkaline (pH≥7.5) water; uranium concentrations were higher in circumneutral to slightly alkaline water (pH≤7.4); and vanadium concentrations were higher in highly alkaline (pH≥8.0) water, independent of redox status.Concentrations within geologic source terranes are not the sole factor controlling the concentrations of geogenic elements in groundwater. Differences in mineral weathering, pH-dependent sorption to surface-exchange sites on mineral grains, and aqueous geochemistry (especially redox status and pH) affect geogenic element concentrations in groundwater. Consequently, the relative abundances of arsenic, Cr(VI), uranium, and vanadium in groundwater differ from their relative abundances in the average bulk continental crust and their regional abundances in rock and surficial alluvium within groundwater basins of the western Mojave Desert. Processes that control the concentrations of arsenic, chromium, uranium, and vanadium in groundwater operate at the mineral-grain and aquifer scale.At the mineral-grain scale, sequential chemical extraction data show arsenic and uranium are more available to groundwater (under specific geochemical conditions) than chromium or vanadium, which largely are unavailable within unweathered mineral grains. Additionally, chromium and vanadium form few aqueous complexes and bind tightly with iron minerals within surface coatings on mineral grains making them less available to groundwater, whereas complexation with other dissolved ions enhances the solubility of uranium and, to a lesser extent, arsenic. Complexation also increases the valence (less negative charge) and increases the size of dissolved oxyanions and uranium complexes with bicarbonate and carbonate making them less readily sorbed to aquifer materials.At the aquifer scale, hydrogeology (including isolation of water in aquifers from surface sources of recharge, older groundwater age, and long contact times between groundwater and aquifer materials) combined with geochemical processes (such as silicate weathering) to produce alkaline groundwater. Desorption from sorption sites on the surfaces of mineral grains with increasing pH increases arsenic, chromium, and vanadium concentrations in water from wells and increases Cr(VI) concentrations as long as water remains oxic.Aqueous geochemistry and concentrations of geogenic contaminants also are affected by anthropogenic activities including (1) discharge of treated municipal wastewater, which may change the redox status of groundwater; (2) return from irrigated agriculture, which may alter the chemistry of groundwater and increase the solubility of trace elements such as uranium; and (3) groundwater pumping and subsequent water-level declines, which may change the source of water yielded by wells. The quality of water imported from northern California and infiltrated from ponds for groundwater recharge may be altered by naturally present trace elements, especially uranium in areas of agricultural land use or chromium within mafic alluvium.
岩石、冲积层和地下水中的砷、铬、铀和钒,莫哈韦河和莫洛戈地区,西部莫哈韦沙漠,南加州
欲了解更多信息,请联系:加州水科学中心主任。地下水中的微量元素来源于含水层物质,如果被摄入,会对公众健康造成潜在危害,这些元素被称为地质污染物。地质污染物砷、铬和钒可以与氧形成负电荷离子,即氧阴离子。铀与碳酸氢盐和碳酸盐络合形成带负电荷的离子,其水化学性质与氧阴离子相似。地下水中砷、铬、铀和钒的浓度是由以下因素共同作用的结果:(1)含水层物质的地质丰度;(2)这些元素从矿物颗粒中风化并吸附到表面并可能被地下水利用的部分;(3)不同氧化还原条件和pH下地下水中溶解氧离子的水化学性质,这两者都受到水文地质的影响,包括地下水与含水层物质接触的时间长短。使用便携式(手持式)x射线荧光(pXRF)测量了岩石、地表冲积层和钻屑样品中的砷、铬、铀和钒的浓度;(2)可从这些材料中提取的可操作定义的馏分;(3) 2000年至2018年在加利福尼亚州南部莫哈韦沙漠西部3500平方英里的莫哈韦河地区和莫龙戈地区取样的水井水。从区域上看,莫哈韦河和莫朗戈地区的岩石和地表冲积物砷含量高,铬和铀含量低,接近大陆地壳中钒的平均浓度。在当地,在圣盖博山脉的基性岩石中存在高浓度的铬;在圣贝纳迪诺山脉的长英质岩石中存在高浓度的铀;在加利福尼亚州巴斯托下游的莫哈韦河沿岸的地下水盆地周围的高地上,砷、铀和钒的浓度很高。利用pXRF数据的主成分分析(PCA)确定的元素组合用于表征岩石、地表冲积层和地质物质中的长英质、基性和长英质火山源地体,这些地质物质是1994年至2018年间钻探的选定监测井所穿透的。在沿莫哈韦河90英里长的洪泛区含水层上发现了与莫哈韦河最近沉积有关的高长英质冲积层。这些高度长英质冲积沉积层的厚度从维克托维尔附近和巴斯托附近的200英尺到维克托维尔下游和莫哈韦河谷洪泛区含水层下游部分约30英尺厚的薄层不等。莫哈韦河和Morongo地区的地下水普遍为氧碱性(pH≥7.5)。2000年至2018年期间采样的498口井中,砷、六价铬(Cr(VI))、铀和钒的最大浓度分别为360、140、1470和690微克/升。22%的采样井的水超过了美国环境保护署(EPA)对砷的最大污染物水平(MCL),砷浓度超过了10 μg/L,在Barstow东部的井中,在Victorville扇的深井中,以及在漫滩含水层的缺氧或减少的地下水中,砷浓度通常超过了MCL。大约1%的取样井的水的Cr(VI)浓度高于加州MCL(总铬为50 μg/L),而13%的取样井的Cr(VI)浓度高于前加州MCL (10 μg/L)。绵羊溪冲积扇的井水中六价铬的浓度最高,该井水是从圣盖博山脉的基性岩石中侵蚀而来,尽管在研究区域的其他地方存在基性物质或更古老的地下水,Cr(VI)浓度也高于前加州MCL。大约9%的取样井的水中铀含量超过了EPA的最高浓度限定值(30 μg/L),超过最高浓度通常与洪泛区含水层上农业用地的灌溉回报有关。约7%的采样井中,水的钒浓度高于加州50 μg/L的通报水平;这些井大部分位于莫哈韦河地区的Victorville扇。一般来说,在缺氧或还原水中砷浓度较高;含氧、碱性(pH≥7.5)水中铬浓度较高;环中性至微碱性水(pH≤7.4)中铀浓度较高;在高碱性(pH≥8.0)水中,钒浓度较高,与氧化还原状态无关。 地质源区内的浓度并不是控制地下水中地质元素浓度的唯一因素。矿物风化、矿物颗粒对表面交换点的pH依赖性吸附和水地球化学(特别是氧化还原状态和pH)的差异影响地下水中地质元素的浓度。因此,地下水中砷、铬(VI)、铀和钒的相对丰度不同于它们在平均大块大陆地壳中的相对丰度,也不同于它们在西部莫哈韦沙漠地下水盆地中岩石和浅层冲积物中的区域丰度。控制地下水中砷、铬、铀和钒浓度的过程在矿物颗粒和含水层尺度上起作用。在矿物颗粒尺度上,连续的化学提取数据表明,砷和铀比铬或钒更容易进入地下水(在特定的地球化学条件下),而铬或钒在未风化的矿物颗粒中基本上是不可用的。此外,铬和钒形成很少的水络合物,并与矿物颗粒表面涂层内的铁矿物紧密结合,使它们不容易进入地下水,而与其他溶解离子的络合增强了铀的溶解度,并在较小程度上增强了砷的溶解度。络合作用还增加了价态(减少了负电荷),增加了溶解氧阴离子和与碳酸氢盐和碳酸盐的铀络合物的大小,使它们不容易吸附到含水层物质上。在含水层尺度上,水文地质(包括含水层中的水与地表补给源隔绝、地下水年龄较老、地下水与含水层物质接触时间较长)与地球化学过程(如硅酸盐风化)相结合,产生碱性地下水。随着pH值的增加,矿物颗粒表面吸附部位的解吸会增加井水中砷、铬和钒的浓度,并在水保持含氧状态下增加Cr(VI)的浓度。水地球化学和地质污染物的浓度也受到人为活动的影响,包括:(1)排放处理过的城市废水,这可能会改变地下水的氧化还原状态;(2)灌溉农业的回流,可能改变地下水的化学性质,增加铀等微量元素的溶解度;(3)地下水的抽取和随后的水位下降,这可能会改变井水的来源。从加利福尼亚北部进口的水的质量和从池塘渗透的地下水补给可能会被自然存在的微量元素改变,特别是农业用地地区的铀或基性冲积层中的铬。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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