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USGS2014

Understanding thermodynamic relationships and geochemical mass balances from catchment to coast: A tribute to the life and career of Owen P. Bricker III

This special volume of aquatic geochemistry is dedicated to the memory of Owen Peterson Bricker III (1936–2011) and serves as a tribute to his life and career. Owen had a distinguished and productive research career in both academics at Johns Hopkins University (Fig. 1) and as a public servant with the Maryland Geological Survey, the US Environmental Protection Agency, and the US Geological Survey. He was a pioneer and leader in aqueous geochemistry, who applied a study approach that quantified mineral weathering reactions and equilibrium thermodynamic relations to better understand the chemical evolution of stream water in small watersheds. He will be especially remembered for his efforts to establish rigorous field studies in small catchments around the United States as a means of quantifying the sources of acid-neutralizing capacity that affect the chemical status and biological health of natural waters.

Aquatic Geochemistry↗

USGS2010

The U.S.Geological Survey Energy Resources Program

Energy resources are an essential component of modern society. Adequate, reliable, and affordable energy supplies obtained using environmentally sustainable practices underpin economic prosperity, environmental quality and human health, and political stability. National and global demands for all forms of energy are forecast to increase significantly over the next several decades. Throughout its history, our Nation has faced important, often controversial, decisions regarding the competing uses of public lands, the supply of energy to sustain development and enable growth, and environmental stewardship. The U.S. Geological Survey (USGS) Energy Resources Program (ERP) provides information to address these challenges by supporting scientific investigations of energy resources, such as research on the geology, geochemistry, and geophysics of oil, gas, coal, heavy oil and natural bitumen, oil shale, uranium, and geothermal resources, emerging resources such as gas hydrates, and research on the effects associated with energy resource occurrence, production, and (or) utilization. The results from these investigations provide impartial, robust scientific information about energy resources and support the U.S. Department of the Interior's (DOI's) mission of protecting and responsibly managing the Nation's natural resources. Primary consumers of ERP information and products include the DOI land- and resource-management Bureaus; other Federal, State, and local agencies; the U.S. Congress and the Administration; nongovernmental organizations; the energy industry; academia; international organizations; and the general public.

Fact Sheet↗

USGS2003

Investigation of the possible connection of rock and soil geochemistry to the occurrence of high rates of neurodegenerative diseases on Guam and a hypothesis for the cause of the diseases

High incidences of neurodegenerative diseases, mainly dementia, parkinsonism, and amyotrophic lateral sclerosis, occur on the island of Guam (Koerner, 1952; Kurland and Mulder, 1954). The occurrence and description of the diseases and a summary of the investigations can be found in Perl (1997). The diseases have been more prevalent along the southern coast, particularly the small villages of Umatac, Merizo, and Inarajan (Reed and Brody, 1975; Roman, 1996; and Perl, 1997) (fig. 1), and referred to as the southern villages in this report. Tertiary volcanic rocks underlie most of the southern part of the island, including these villages. The northern part of Guam, with lower incidences of the diseases, consists of carbonate rocks. Epidemiological studies beginning in the early 1950’s failed to show the cause to be genetic etiology (Plato and others, 1986; Zhang and others, 1990). In recent studies, the search for pathogenic mechanisms has shifted to environmental factors. Excesses or deficiencies of various elements from dietary sources including drinking water can have an effect on human health. These deficiencies or excesses can usually be attributed to the geochemical composition of the rocks and derived soils that underlie the area. An example is the high concentration of Se in soil associated with the occurrence of selenosis in adults (Mills, 1996). Yase (1972) suggested that the neurodegenerative diseases on Guam may be related to accumulation of trace elements such as manganese and aluminum, both of which may cause neurodegeneration. It has been suggested that a deficiency in calcium and magnesium in the soil and water along with readily available aluminum could be connected to the occurrence of the diseases (Gajdusek, 1982; Yanagihara and others, 1984; Garruto and others, 1989). Some of the studies investigated metal exposure, particularly aluminum and manganese, and deficiencies in calcium and magnesium (Garruto and others, 1984). Aluminum has been shown to have neurotoxic effects (MacDonald and Martin, 1988), and aluminum has been implicated in the pathogenesis of Alzheimer’s disease and similar dementia by Perl and others (1982). Studies of soils developed on volcanic rocks on Guam and other islands by McLachlan and others (1989) found that soils on Guam averaged 42-fold higher yield of elutable aluminum than soils developed on volcanic rocks on Jamaica or Palau. They did not detect unusually high dietary aluminum or low dietary calcium, but concluded that the soils and possibly the dusts of Guam might be a major source of aluminum entering the body of the inhabitants. This study was conducted to investigate the geochemistry of the soils and rocks of the volcanic southern part of the island of Guam, particularly in the vicinity of the three southern villages (Umatac, Merizo, and Inarajan) with high incidences of the diseases. In addition to total chemical analyses of the soils and rocks, various extractions of soils were carried out. Both excesses and deficiencies of various elements were looked for. Because soluble aluminum in the soil was shown by McLachlan and others (1989) to be unusually high, water-soluble extractions as well as sequential extractions of the soils were carried out. In addition, elements such as aluminum found in dust can traverse the nose-brain barrier in experimental animals (Sunderman, 2000) and respiratory epithelium is known to contain the highest concentration of aluminum in the human body (Tipton and others, 1957). The availability of elements, particularly aluminum from human inhalation of dust, derived from soil, was investigated. The available elements were determined by extractions of soils using a simulated lung-fluid extraction. In order to compare the results of the chemical data of rocks and soils from Guam to other rocks and soils elsewhere, samples of similar rocks and soils were collected in the western United States and similar analyses to those for the Guam samples carried out. The complete chemical analyses of the soils, rocks, and streambed sediments as well as descriptions of the methods used can be found in Miller and others (2002).

Open-File Report↗

USGS2020

Groundwater quality and geochemistry of West Virginia’s southern coal fields

Coal mining has been the dominant industry and land use in West Virginia’s southern coal fields since the mid-1800s. Mortality rates for a variety of serious chronic conditions, such as diabetes, heart disease, and some forms of cancer in Appalachian coal mining regions, are higher than in areas lacking substantial coal mining activity within the Appalachian Region or elsewhere in the United States. Causes of the increased mortality and morbidity are not clear, but poor diet, high rates of smoking, socioeconomic factors, and the quality of groundwater used by area residents are all possible contributing factors. This study was conducted by the U.S. Geological Survey in cooperation with the West Virginia Department of Health and Human Resources and the West Virginia Department of Environmental Protection, with grant support from the Centers for Disease Control and Prevention (CDC) to assess the quality of groundwater in southern West Virginia. The data from this assessment of groundwater quality may be used by the CDC and other agencies to potentially investigate the role or lack thereof of groundwater quality with respect to mortality and morbidity rates in the region. The study was conducted in a region where a high density of current or past coal mining combined with a lack of advanced sewage treatment could affect concentrations of commonly occurring constituents plus contaminants, including nitrate, trace metals, major ions, indicator bacteria, radon, hydrogen sulfide, and dissolved hydrocarbons. Because rural residential wells and mine outfalls are considered private sources of water in the region, and are therefore unregulated and unmonitored, water-quality data are sparse. To fill the data gap and assess the groundwater quality in the region, water-quality samples were collected from 60 sites in a 10-county area. The 60 sites sampled included 46 rural residential homeowner wells and 14 mine outfall discharges used for residential supply. For this study, all samples were collected prior to any filtration or other treatments, typically at the pressure tank, and are indicative of total and dissolved constituents in the untreated water. Generally, data for the 60 sites indicate that most waters sampled do not exceed thresholds for most U.S. Environmental Protection Agency (EPA) drinking-water standards and U.S. Geological Survey (USGS) drinking-water screening criteria. However, there were several notable exceptions. Turbidity exceeded the 5-Nephelometric Turbidity Unit (NTU) EPA treatment technique (TT) drinking-water standard in 14 of 60 (23 percent) sites sampled and exceeded the 1-NTU TT standard in 51 of 60 (85 percent) sites sampled. Turbidity is common in many wells in southern West Virginia and may be attributed to iron oxyhydroxide precipitates, sediment carried into the aquifers from the shallow soil zone due to improperly constructed or cased wells or transported to the aquifer in shallow stress-relief fracture zones or through permeable bedding-plane partings. For the sites sampled, 31 of 60 (52 percent) had pH values at, above, or below the upper and lower range of the EPA Secondary Maximum Contaminant Level (SMCL, 6.5–8.5 standard units). Of those 31 sites, 28 (90 percent) were indicative of acidic corrosive water and 3 (10 percent) were indicative of alkaline water. The Langelier Saturation Index (LSI), which is a measure of the corrosivity of the water, was computed for all sites sampled for the study. Eighty-two percent of the sites sampled had waters that were classified as corrosive, based on a LSI less than −0.5. Corrosive water has the potential to leach lead, copper, and other metals from lead, copper, galvanized, or lead-tin soldered connections in water lines. The chloride to sulfate mass ratio also was assessed with the alkalinity to indicate the potential to promote galvanic corrosion (PPGC) of water lines and plumbing fixtures. Only one of the sites (1.7 percent) classified as a corrosive water site, had a PPGC considered high; the remaining sites were classified as having either a moderate (53.3 percent) or low (45 percent) PPGC. Therefore, the type of plumbing systems sampled for this study may be affected by corrosive water, but the potential for leaching trace metals and other constituents from residential plumbing systems containing older galvanized pipes or lead-tin soldered copper pipes is moderate to low. The indicator bacteria total coliform and Escherichia coli ( E. coli ) also were detected in groundwater samples to varying degrees. Total coliforms, which are a broad class of indicator bacteria, are common in groundwater in southern West Virginia and were detected in 39 of the 60 sites (65 percent) sampled. The presence of total coliform bacteria is a potential indicator of surface contamination, due to improperly constructed or cased wells, or infiltration of soil or other surface contaminants into the aquifer or well bore. E. coli bacteria, however, are much more indicative of fecal contamination of groundwater from either human or animal sources, and 14 of the 60 (23 percent) sites sampled had detections of E. coli . Although only a few strains of E. coli are known pathogens, their presence in groundwater may be an indicator of other related pathogens such as viruses and should be regarded as a serious potential issue. Water treatment such as chlorination, ozonation, or ultraviolet light may be appropriate to kill potential pathogenic bacteria or viruses in the source water. Manganese and iron were prevalent contaminants in the groundwater samples collected for this study, with 30 of 60 (50 percent) sites analyzed for manganese and 25 of 60 (42 percent) sites analyzed for iron exceeding the proposed 50- and 300-micrograms per liter (µg/L) SMCL drinking-water standards, respectively, for aesthetic criteria such as taste, odor, or staining of plumbing fixtures. Fourteen of the 60 sites sampled (23 percent) had concentrations of manganese that exceeded the 300-µg/L USGS health-based screening level, and 1 site exceeded the 1,600-µg/L EPA drinking-water equivalent level, which is based on a lifetime exposure level. Sodium is another common constituent in groundwater within the study area. Sodium has an EPA health-based value (HBV) of 20 milligrams per liter (mg/L) for individuals who are on a sodium-restricted diet for blood pressure or other health reasons. Sodium concentrations exceeded the 20-mg/L EPA HBV in 27 of 60 (45 percent) samples. Radon, a naturally occurring carcinogenic radioactive gas known to cause lung cancer, was detected at concentrations at or exceeding the proposed 300-picocuries per liter (pCi/L) EPA Maximum Contaminant Level (MCL) in 12 of the 60 (20 percent) sites sampled. Sites with radon gas concentrations exceeding the 300-pCi/L proposed MCL have the potential for airborne concentrations of radon to exceed the 4-pCi/L indoor air standard. Inhalation of radon can cause lung cancer, and the 4-pCi/L indoor air standard is based on an inhalation standard. Therefore, homeowners whose wells have radon gas concentrations exceeding 300 pCi/L may be advised to have their indoor air tested to determine if indoor air concentrations exceed the 4-pCi/L indoor air standard established by the EPA. Various factors were analyzed statistically and graphically to determine whether they have an influence on groundwater quality within the study area, including topographic setting, well depth, type of mining (surface or underground), type of site (well or mine outfall), and geologic formation. Only geologic formation and the type of site sampled had strong statistical correlations with one or more of the constituents of concern for this study. The overall chemistry of outfalls (mine outfalls) and wells was significantly different, with a much higher dissolved oxygen content in outfalls than in wells. The dissolved oxygen content is the primary component driving the oxidation and reduction of minerals, and the precipitation of minerals that are saturated or super saturated with respect to various cations and anions. Median dissolved oxygen concentrations for the outfalls sampled was 8.75 mg/L, and only 0.4 mg/L for the wells sampled. Median concentrations of sulfate and selenium were much higher in waters from the outfalls sampled, with median concentrations of 73.75 mg/L and 2.35 µg/L, respectively, compared to the wells sampled, which had median concentrations of 18.3 mg/L and less than (<) the 0.05-µg/L method detection limit, respectively. The maximum selenium concentration was for a well, with a concentration of 16.6 µg/L. The geochemical processes that control sulfate and selenium concentrations in groundwater are similar and are the result of the oxidation of sulfide minerals such as pyrite and ferroselite. Iron and manganese concentrations were elevated in most of the wells sampled, with median concentrations of 269.5 and 124.5 µg/L, respectively, but were rarely detected in the outfalls sampled, with median concentrations of < 4.0 and < 0.4 µg/L, respectively. The difference in iron and manganese between wells and outfalls is indicative of the role of dissolved oxygen on processes controlling groundwater chemistry in the region. Three principal geologic formations were assessed for the study, and the overall chemistry for the Pocahontas, New River, and Kanawha Formations varied substantially with respect to several constituents. Concentrations of calcium, magnesium, and total dissolved solids were highest for sites sampled in the Pocahontas Formation, with median concentrations of 41.9, 18.6, and 312 mg/L, respectively. For constituents that are commonly associated with mining activity, the highest concentrations were for sites sampled in the New River Formation, with median concentrations of iron and manganese of 2,450 µg/L and 482 µg/L, respectively, and a median pH of 6.35 standard units. Concentrations of barium also were elevated in samples collected from sites in the New River Formation, with a median barium concentration of 184 µg/L. The source of the barium is not fully known but may be associated with commingling of shallow groundwater with deeper brines or dissolution of the mineral barite. The highest median sulfate concentrations were from sites sampled in the Pocahontas Formation, with a median concentration of 64.0 mg/L. Of the 12 sites at or exceeding the 300-pCi/L proposed drinking-water standard for radon, 8 (67 percent of MCL exceedances) were for sites deriving water from the Kanawha Formation, 3 (25 percent of MCL exceedances) were for sites deriving water from the New River Formation, and only 1 site was for water from the Pocahontas Formation (8 percent of proposed MCL exceedances). Dissolved hydrocarbons, including methane, ethane, propane, propene, n - and i -butane, 1-butene, n - and i -pentane, pentane, 2- and 3-ethyl pentane, hexane, and benzene were analyzed in samples collected from 59 of the 60 sites to assess the potential occurrence and sources of these trace gases in groundwater within the study area. Results of the analysis indicate that most of the gas is of shallow biogenic origin, possibly associated with coal-bed methane, but a subset of samples has a gas signature and a chloride to bromide ratio indicative of potential mixing with deeper thermogenic gases. Only 2 of the 59 (3.3 percent) sites sampled had concentrations of methane gas, which is a highly combustible and explosive gas, exceeding the 10 milligrams per kilogram level of concern established by the U.S. Office of Surface Mining Reclamation and Enforcement. Principal components analysis was used to assess the primary geochemical processes occurring in the aquifers sampled. The first principal component had significant positive loadings for bromide, chloride, silica, ammonia, barium, iron, manganese, and arsenic, and significant negative loadings for dissolved oxygen, potassium, nitrate, and uranium, and reflects reduction and oxidation (redox) processes occurring in deeper anoxic groundwater or shallow oxic groundwater. The strong positive loadings for iron, manganese, barium, and arsenic are correlated with reducing conditions often found deeper in the aquifer. More oxic water is correlated with oxidation of nitrogen species to nitrate and environmental mobilization of uranium and sulfate in shallow wells and mine outfalls.

West Virginia↗

USGS2009

Geochemistry of soils along a transect from Central Mexico to the Pacific Coast: a pilot study for continental-scale geochemical mapping

The Mexican Geological Survey (SGM), the National Institute of Statistics, Geography and Informatics (INEGI) and the Autonomous University of San Luis Potosi (UASLP) have established a multidisciplinary team with the objective of creating a national program of geochemical mapping of soils in Mexico. This is being done as part of the North American Soil Geochemical Landscapes Project in partnership with the US Geological Survey and the Geological Survey of Canada. As the first step, a pilot study was conducted over a transect that extends from the Mexico–US border near Ciudad Juarez in the north to the Pacific Ocean in the south. This pilot transect was conducted in two phases, and this paper presents results from the first phase, which sampled soils at about a 40-km spacing along a 730-km transect beginning in Central Mexico and ending at the Pacific Coast. Samples were collected from the A and C horizons at each site and 60 elements were analyzed. This pilot study demonstrates that geochemical mapping based on a 40-km spacing is adequate to identify broad-scale geochemical patterns. Geologic influence (i.e., soil parent material) was the most important factor influencing the distribution of elements along the transect, followed by the influence of regional mineralization. The study also showed that influence by human activities over the transect is minimal except possibly in large mining districts. A comparison of element abundance in the A horizon with the environmental soil guidelines in Mexico showed that the natural concentrations of the studied soils were lower than the established threshold for soil restoration with the exception of V and As. The former had a median value (75 mg/kg) approximately equal to the value established in Mexico for soil restoration in agricultural and residential lands (78 mg/kg), and the latter had three values higher than the 22 mg/kg threshold for soil restoration in agricultural and residential lands. These cases demonstrate the importance of knowing the national- and regional-scale geochemistry of Mexican soils as a support for the decision-making process, particularly for the proper formulation and application of soil guidelines designed to protect human and ecosystem health.

Applied Geochemistry↗

USGS2012

Reconnaissance soil geochemistry at the Riverton Uranium Mill Tailings Remedial Action Site, Fremont County, Wyoming

Soil samples were collected and chemically analyzed from the Riverton Uranium Mill Tailings Remedial Action Site, which lies within the Wind River Indian Reservation in Fremont County, Wyoming. Nineteen soil samples from a depth of 0 to 5 centimeters were collected in August 2011 from the site. The samples were sieved to less than 2 millimeters and analyzed for 44 major and trace elements following a near-total multi-acid extraction. Soil pH was also determined. The geochemical data were compared to a background dataset consisting of 160 soil samples previously collected from the same depth throughout the State of Wyoming as part of another ongoing study by the U.S. Geological Survey. Risk from potentially toxic elements in soil from the site to biologic receptors and humans was estimated by comparing the concentration of these elements with soil screening values established by the U.S. Environmental Protection Agency. All 19 samples exceeded the carcinogenic human health screening level for arsenic in residential soils of 0.39 milligrams per kilogram (mg/kg), which represents a one-in-one-million cancer risk (median arsenic concentration in the study area is 2.7 mg/kg). All 19 samples also exceeded the lead and vanadium screening levels for birds. Eighteen of the 19 samples exceeded the manganese screening level for plants, 13 of the 19 samples exceeded the antimony screening level for mammals, and 10 of 19 samples exceeded the zinc screening level for birds. However, these exceedances are also found in soils at most locations in the Wyoming Statewide soil database, and elevated concentrations alone are not necessarily cause for alarm. Uranium and thorium, two other elements of environmental concern, are elevated in soils at the site as compared to the Wyoming dataset, but no human or ecological soil screening levels have been established for these elements.

Wyoming↗

USGS2014

The environmental geochemistry of Arsenic – An overview

Arsenic is one of the most prevalent toxic elements in the environment. The toxicity, mobility, and fate of arsenic in the environment are determined by a complex series of controls dependent on mineralogy, chemical speciation, and biological processes. The element was first described by Theophrastus in 300 B.C. and named arsenikon (also arrhenicon; Caley and Richards 1956 ) referring to its “potent” nature, although it was originally considered an alternative form of sulfur ( Boyle and Jonasson 1973 ). Arsenikon is believed to be derived from the earlier Persian, zarnik (online etymology dictionary, http://www.etymonline.com/index.php?term=arsenic ). It was not until the thirteenth century that an alchemist, Albertus Magnus, was able to isolate the element from orpiment, an arsenic sulfide (As 2 S 3 ). The complex chemistry required to do this led to arsenic being considered a “bastard metal” or what we now call a “metalloid,” having properties of both metals and non-metals. As a chemical element, arsenic is widely distributed in nature and can be concentrated in many different ways. In the Earth’s crust, arsenic is concentrated by magmatic and hydrothermal processes and has been used as a “pathfinder” for metallic ore deposits, particularly gold, tin, copper, and tungsten ( Boyle and Jonasson 1973 ; Cohen and Bowell 2014 ). It has for centuries been considered a potent toxin, is a common poison in actual and fictional crimes, and has led to significant impacts on human health in many areas of the world ( Cullen 2008 ; Wharton 2010 ).

Reviews in Mineralogy and Geochemistry↗

USGS2004

Integrated investigations of environmental effects of historical mining in the Basin and Boulder Mining Districts, Boulder River watershed, Jefferson County, Montana

The Boulder River watershed is one of many watersheds in the western United States where historical mining has left a legacy of acid mine drainage and elevated concentrations of potentially toxic trace elements. Abandoned mine lands commonly are located on or affect Federal land. Cleaning up these Federal lands will require substantial investment of resources. As part of a cooperative effort with Federal land-management agencies, the U.S. Geological Survey implemented an Abandoned Mine Lands Initiative in 1997. The goal of the initiative was to use the watershed approach to develop a strategy for gathering and communicating the scientific information needed to formulate effective and cost-efficient remediation of affected lands in a watershed. The watershed approach is based on the premise that contaminated sites that have the most profound effect on water and ecosystem quality within an entire watershed should be identified, characterized, and ranked for remediation. The watershed approach provides an effective means to evaluate the overall status of affected resources and helps to focus remediation at sites where the most benefit will be gained in the watershed. Such a large-scale approach can result in the collection of extensive information on the geology and geochemistry of rocks and sediment, the hydrology and water chemistry of streams and ground water, and the diversity and health of aquatic and terrestrial organisms. During the assessment of the Boulder River watershed, we inventoried historical mines, defined geological conditions, assessed fish habitat, collected and chemically analyzed hundreds of water and sediment samples, conducted toxicity tests, analyzed fish tissue and indicators of physiological malfunction, examined invertebrates and biofilm, and defined hydrological regimes. Land- and resource-management agencies are faced with evaluating risks associated with thousands of potentially harmful mine sites, and this level of effort is not always feasible for every affected watershed. The detailed work described in this report can help Federal land-management agencies decide which characterization efforts would be most useful in characterization of other affected watersheds.

Montana↗

USGS2022

Groundwater quality and geochemistry of the western wet gas part of the Marcellus Shale Oil and Gas Play in West Virginia

Thirty rural residential water wells in the wet gas region of the Marcellus Shale oil and gas play in northwestern West Virginia were sampled by the U.S. Geological Survey (USGS) in 2018, in cooperation with West Virginia State agencies, to analyze for a range of water-quality constituents, including major ions, trace metals, radionuclides, bacteria, and methane and other dissolved hydrocarbon gases. The groundwater-quality data collected for this study were used to assess the overall quality of groundwater in the study area in relation to public drinking-water standards. The groundwater-quality data were also evaluated with respect to geology, well depth, topographic setting, and proximity to oil and gas wells to identify possible relations to these factors. The presence of total coliform bacteria in groundwater is a potential indicator of surface contamination. The presence of Escherichia coli bacteria is indicative of fecal contamination of groundwater from either human or animal sources and may be considered an indicator of other related pathogens such as viruses. Total coliforms were detected in 26 of the 30 (87 percent) wells sampled. Eleven of the 30 (37 percent) wells sampled had detections of Escherichia coli bacteria. Sodium concentrations in 24 of 30 (80 percent) samples exceeded the U.S. Environmental Protection Agency (EPA) 20-milligram per Liter (mg/L) health-based value (HBV). Manganese, aluminum, and iron concentrations exceeded the EPA 50, 2.0, and 300 micrograms per liter (μg/L) secondary maximum contaminant level (SMCL) drinking-water standards at 14 (47 percent), 7 (23 percent), and 5 (17 percent) of the 30 wells sampled. Two of the 30 (7 percent) wells sampled had concentrations of manganese that exceeded the 300-μg/L USGS health-based screening level (HBSL). Arsenic concentrations at 7 of 30 (23 percent) wells sampled exceeded the 10-μg/L EPA maximum contaminant level (MCL) health-based drinking water standard. The EPA maximum contaminant level goal (MCLG) for arsenic is 0 μg/L and 29 of 30 wells sampled contained detectable concentrations of arsenic. None of the 30 wells sampled exceeded the U.S. Office of Surface Mining Reclamation and Enforcement (OSMRE) 28-mg/L immediate action level (IAL) for methane in groundwater and only 1 of 30 (3 percent) sites exceeded the 10-mg/L OSMRE level of concern (LOC) for methane in groundwater. Of the 28 wells sampled for radon-222 all 28 (100 percent) exceeded the EPA proposed 300-picocuries per liter (pCi/L) MCL for radon. None of the samples exceeded the 4,000-pCi/L alternate maximum contaminant level (AMCL) which is applicable to public drinking water systems that have adopted radon mitigation programs. Wilcoxon Signed Rank Tests indicated statistically significant differences at a 95 percent confidence interval (p less than 0.05) in radium-226, barium, and ethane groundwater concentrations with respect to the density of oil and gas wells present within a 500-meter (m) radius around the rural residential wells sampled for the study. Samples from residential wells that had four or fewer oil and gas wells in the surrounding 500-m radius had statistically lower concentrations of radium-226, bromide, and ethane than samples from residential wells sampled that had five or more oil and gas wells in the surrounding 500-m radius. Given the available data, the relationship between concentrations of radium-226, bromide, and ethane for wells sampled in this study and oil and gas development or natural geochemical processes is not clear. Groundwater-age tracers (chlorofluorocarbons, tritium, and sulfur hexafluoride) were sampled at 17 of the 30 wells. All 17 samples contained a fraction of young, post-1950s groundwater. Many of the groundwater samples collected for this study have high calcium to sodium ratios and low total dissolved solids concentrations, indicating they are dominated by recently recharged water. A subset of samples had chloride to bromide mass ratios between 70 and 200, indicating that deep Appalachian basin brines mixed with the shallow groundwater. For most of the samples in this study, the C 1 through C 6 hydrocarbons have characteristics that reflect a biogenic gas signature that has, to varying degrees, undergone oxidation processes during transport. None of the samples show a characteristic thermogenic cracking pattern among the hydrocarbon ratios.

West Virginia↗

USGS2004

Suwannee river basin and estuary integrated science workshop: September 22-24, 2004 Cedar Key, Florida

In response to the growing number of environmental concerns in the mostly pristine Suwannee River Basin and the Suwannee River Estuary system, the States of Florida and Georgia, the Federal government, and other local organizations have identified the Suwannee River as an ecosystem in need of protection because of its unique biota and important water resources. Organizations with vested interests in the region formed a coalition, the Suwannee Basin Interagency Alliance (SBIA), whose goals are to promote coordination in the identification, management, and scientific knowledge of the natural resources in the basin and estuary. To date, an integrated assessment of the physical, biological, and water resources has not been completed. A holistic, multi-disciplinary approach is being pursued to address the research needs in the basin and estuary and to provide supportive data for meeting management objectives of the entire ecosystem. The USGS is well situated to focus on the larger concerns of the basin and estuary by addressing specific research questions linking water supply and quality to ecosystem function and health across county and state boundaries. A strategic plan is being prepared in cooperation with Federal, State, and local agencies to identify and implement studies to address the most compelling research issues and management questions, and to conduct fundamental environmental monitoring studies. The USGS, Suwannee River Water Management District and the Florida Marine Research Institute are co-sponsoring this scientific workshop on the Suwannee River Basin and Estuary to: Discuss current and past research findings, Identify information gaps and research priorities, and Develop an action plan for coordinated and relevant research activities in the future. This workshop builds on the highly successful basin-wide conference sponsored by the Suwannee Basin Interagency Alliance that was held three years ago in Live Oak, Florida. This years workshop will focus on identifying information needs and priorities and developing partnerships. The USGS is seeking to define the role of the USGS Florida Integrated Science Center (FISC) in conducting integrated research in the Suwannee River Basin, and to establish a cooperative program with other agencies. Participants interested in river, floodplain, springs, estuary, or basin-wide issues are encouraged to attend. Topics for this years workshop include: Water quality and geochemistry: nutrient enrichment, reduction of nutrient loading to ground water, contaminants, and land use, Hydrogeology: interactions among ground water, surface water and ecosystem, modeling, and baseline mapping, Ecosystem dynamics: structure, process, species, and habitats (estuarine, riverine, floodplain, and wetland), and Information management: data sharing, database development, geographic information system (GIS), and basin-wide models.

Open-File Report↗

USGS2019

Alaska Geochemical Database Version 3.0 (AGDB3)—Including “Best Value” Data Compilations for Rock, Sediment, Soil, Mineral, and Concentrate Sample Media

The Alaska Geochemical Database Version 3.0 (AGDB3) contains new geochemical data compilations in which each geologic material sample has one “best value” determination for each analyzed species, greatly improving speed and efficiency of use. Like the Alaska Geochemical Database Version 2.0 before it, the AGDB3 was created and designed to compile and integrate geochemical data from Alaska to facilitate geologic mapping, petrologic studies, mineral resource assessments, definition of geochemical baseline values and statistics, element concentrations and associations, environmental impact assessments, and studies in public health associated with geology. This relational database, created from data-bases and published datasets of the U.S. Geological Survey (USGS), Atomic Energy Commission National Uranium Resource Evaluation (NURE), Alaska Division of Geological & Geophysical Surveys (DGGS), U.S. Bureau of Mines, and U.S. Bureau of Land Management serves as a data archive in support of Alaskan geologic and geochemical projects and contains data tables in several different formats describing historical and new quantitative and qualitative geochemical analyses. The analytical results were determined by 112 laboratory and field analytical methods on 396,343 rock, sediment, soil, mineral, heavy-mineral concentrate, and oxalic acid leachate samples. Most samples were collected by personnel of these agencies and analyzed in agency laboratories or, under contracts, in commercial analytical laboratories. These data represent analyses of samples collected as part of various agency programs and projects from 1938 through 2017. In addition, mineralogical data from 18,138 nonmagnetic heavy-mineral concentrate samples are included in this database. The AGDB3 includes historical geochemical data archived in the USGS National Geochemical Database (NGDB) and NURE National Uranium Resource Evaluation-Hydrogeochemical and Stream Sediment Reconnaissance databases, and in the DGGS Geochemistry database. Retrievals from these data-bases were used to generate most of the AGDB data set. These data were checked for accuracy regarding sample location, sample media type, and analytical methods used. In other words, the data of AGDB3 supersedes data in the AGDB and the AGDB2, but the background about the data in these two earlier versions are needed by users of the current AGDB3 to understand what has been done to amend, clean up, correct and format this data. Corrections were entered, resulting in a significantly improved Alaska geochemical dataset, the AGDB3. Data that were not previously in these databases because the data predate the earliest agency geochemical data-bases, or were once excluded for programmatic reasons, are included here in the AGDB3 and will be added to the NGDB and Alaska Geochemistry. The AGDB3 data provided here are the most accurate and complete to date and should be useful for a wide variety of geochemical studies. The AGDB3 data provided in the online version of the database may be updated or changed periodically.

Alaska↗

USGS2013

The distribution of uranium over Europe: Geological and environmental significance

The variation of baseline levels of uranium in soil and stream sediments over Europe is described, based on new data prepared by the Forum of European Geological Surveys (FOREGS). The samples have been collected and analysed according to the protocols established for the International Union of Geological Sciences/International Association of Geochemistry and Cosmochemistry (IUGS/IAGC) Working Group on Global Geochemical Baselines. The baseline levels of U vary between 0??21 to 53 mg kg-1 in topsoils, 0??19 to 30 mg kg-1 in subsoils and < 1 to 59 mg kg-1 in stream sediments. There is generally good agreement between the levels of U in the three sample types, and the median concentration in all three media is approximately 2 mg kg-1. The most anomalous baseline levels occur over the Variscan orogen, especially areas into which late post-orogenic radiothermal high heat production (HHP) granites were emplaced. Spiderdiagrams based on trace element levels and rare earth element (REE) plots, confirm the association between the highest U anomalies and evolved radiothermal granites. High values are also associated with parts of the Alpine terrain especially in Slovenia, where there are historical U workings, and Southern Italy, where high values of U reflect contemporary volcanism. In contrast, much of the Caledonides of North West Europe and the Precambrian of the Baltic Shield and East European craton and its overlying sedimentary cover have very low values, generally < 4 mg kg-1. The results suggest that the main concern for the environment and human health from U, and the Th and K with which it is generally associated, is the naturally occurring total gamma radiation and radon potential associated with radiothermal granites. This is likely to be especially important where the granites are mineralised and have been worked historically, for example in the North West of the Iberian Peninsula where U and its decay products are likely to be more dispersed in the surface environment. The study also indicates the value of multi-element data in distinguishing between anthropogenic and naturally occurring anomalies.

Transactions of the Institution of Mining and Meta↗

USGS2025

Geochemical processes related to mined, milled, or natural metal deposits in a rapidly changing global environment

The demand for metals and raw materials, such as nickel and copper, has been projected to expand in the coming decades, driven by the global energy transition, the need for green technologies, and expanding infrastructure. Consequently, the increasing extraction and production of mining waste can have adverse impacts on surrounding environments and human health. The aim of this thematic collection is to fill critical knowledge gaps in the present-day cycles of metal(loid)s from source to larger sinks, and the effect of environmental management, anthropogenic development, and climate change. Altogether, the studies have been conducted in different natural settings around the world and comprise investigations in laterites, a soil-medicinal plant system, watersheds, and banded iron formations, among others. The geochemical applications in tracing mineralization, its secondary products, and/or potential impact on the immediate environment are highly diverse with applied tools ranging from isotope tracers to major and trace element systematics. Particularly the use of rare earth elements, their patterns and anomalies are methods employed by several studies in this collection. We summarize the findings to offer a potential future direction for the use of geochemical tracing techniques in resource exploration in the context of climate change and environmental challenges.

Geochemistry: Exploration, Environment, Analysis↗

USGS2007

Processes influencing the transport and fate of contaminated sediments in the coastal ocean– Boston Harbor and Massachusetts Bay

Most of the major urban centers of the United States including Boston, New York, Washington, Chicago, New Orleans, Miami, Los Angeles, San Francisco, and Seattle—are on a coast (fig. 1.1). All of these cities discharge treated sewage effluent into adjacent waters. In 2000, 74 percent of the U.S. population lived within 200 kilometers (km) of the coast. Between 1980 and 2002, the population density in coastal communities increased approximately 4.5 times faster than in noncoastal areas of the U.S. (Perkins, 2004). More people generate larger volumes of wastes, increase the demands on wastewater treatment, expand the area of impervious land surfaces, and use more vehicles that contribute contaminants to street runoff. According to the National Coastal Condition Report II (U.S. Environmental Protection Agency, 2005a), on the basis of coastal habitat, water and sediment quality, benthic index, and fish tissue, the overall national coastal condition is only poor to fair and the overall coastal condition in the highly populated Northeast is poor. Scientific information helps managers to prioritize and regulate coastal-ocean uses that include recreation, commercial fishing, transportation, waste disposal, and critical habitat for marine organisms. These uses are often in conflict with each other and with environmental concerns. Developing a strategy for managing competing uses while maintaining sustainability of coastal resources requires scientific understanding of how the coastal ocean system behaves and how it responds to anthropogenic influences. This report provides a summary of a multidisciplinary research program designed to improve our understanding of the transport and fate of contaminants in Massachusetts coastal waters. Massachusetts Bay and Boston Harbor have been a focus of U.S. Geological Survey (USGS) research because they provide a diverse geographic setting for developing a scientific understanding of the geology, geochemistry, and oceanography of coastal systems in general. Scientific data from this region can also be used to inform decisions about important economic, environmental, and political issues. From the economic viewpoint, the annual value of tourism and shipping in Massachusetts and Cape Cod Bays is about $1.5 billion and $1.9 billion, respectively. Commercial and recreational fishing generates about $240 million per year in the same region (U.S. Environmental Protection Agency, 2005b). The environmental issue is the 300-year history of waste discharge from the Boston metropolitan area into the harbor. This history is punctuated by cycles of environmental degradation, public outcry, and improvements in the sewage treatment system. With each improvement, however, the continuous growth of population in greater Boston (fig. 1.2) and the resulting increase in the volume of waste exceeded the capacity of the treatment system, thereby setting the stage for a new contamination crisis. By the 1980s, the levels of contaminants in sediments of Boston Harbor were among the highest in the nation (National Oceanic and Atmospheric Administration, 1987). Fish were diseased, shellfish beds were closed, and swimming beaches were unsafe after heavy rains; in general, water quality and aesthetics were below acceptable standards. Legal and political issues have always been part of Boston Harbor’s history. The environmental conditions in the 1980s were highlighted in a 1983 legal suit brought by the city of Quincy against the Metropolitan District Commission (MDC, the state agency responsible for sewage treatment) and heads of three state agencies for discharging untreated or poorly treated sewage into the harbor (Dolin, 2004). The suit never went to trial, but through the actions of a Massachusetts Superior Court, the issue of Boston Harbor contamination remained on the political and public agenda. The judge called the harbor “unsafe, unsanitary, indecent, in violation of the law (Clean Water Act), and a danger to the health and welfare of the people” (Forman, 1984). To force the state legislature to implement a plan to improve harbor conditions, the judge threatened to place the MDC in receivership and curtail new sewage hookups for industry. Under intense lobbying by business, the legislature created the Massachusetts Water Resources Authority (MWRA) in December 1984. The independent MWRA was established to manage Boston’s waste treatment system and was given the authority to float bonds to pay for major improvements in the treatment system. In 1985, a Federal court began hearings on a suit brought by the Conservation Law Foundation, the Environmental Protection Agency (USEPA), and towns of Quincy and Winthrop against the MDC and MWRA (as heir to responsibilities of the MDC) for years of violation of the Clean Water Act. The judge ruled against the defendants and required all the parties to submit a construction plan and schedule for a new sewage treatment system. From these submissions, he developed a schedule for treatment system upgrades that would give the “citizens of this commonwealth a public assurance that Boston Harbor will be cleaned up within a defined period of time” (Dolin, 2004). The MWRA’s Boston Harbor cleanup program (Levy and Connor, 1992) has transformed the Boston sewage system. Key improvements were to (1) reduce contaminants at the industrial source; (2) remediate leaks in the sewage-collection system; (3) eliminate sewage sludge discharge to the harbor; (4) upgrade sewage treatment from primary to secondary; (5) construct a new ocean outfall 15.2 km offshore in Massachusetts Bay for discharge of treated effluent (fig. 1.3); and (6) implement improvements in the combined-sewer-overflow system. As part of the harbor cleanup program, the MWRA developed a comprehensive monitoring program (summarized in MWRA, 2004) to assess changes in the harbor and bays that specifically related to the new sewage system. Additional information about conditions and processes in the coastal system on a regional scale and over a long time period was and continues to be important in predicting and interpreting local change. Implementation of the MWRA’s program and the mission of the USGS to understand the geology of the nation’s offshore waters provided an opportunity to conduct a cooperative multidisciplinary research program. This USGS program addresses basic scientific questions as well as concerns raised by management regarding the design, implementation, and assessment of the new sewage treatment system. Already active in Boston Harbor during the late 1970s, the USGS expanded research into Massachusetts Bay with a multidisciplinary program in 1989.

Massachusetts↗

USGS2002

Tracing sources of sulfur in the Florida Everglades

We examined concentrations and sulfur isotopic ratios ( 34 S/ 32 S, expressed as δ 34 S in parts per thousand [‰] units) of sulfate in surface water, ground water, and rain water from sites throughout the northern Everglades to establish the sources of sulfur to the ecosystem. The geochemistry of sulfur is of particular interest in the Everglades because of its link, through processes mediated by sulfate-reducing bacteria, to the production of toxic methylmercury in this wetland ecosystem. Methylmercury, a neurotoxin that is bioaccumulated, has been found in high concentrations in freshwater fish from the Everglades, and poses a potential threat to fish-eating wildlife and to human health through fish consumption. Results show that surface water in large portions of the Everglades is heavily contaminated with sulfate, with the highest concentrations observed in canals and marsh areas receiving canal discharge. Spatial patterns in the range of concentrations and δ 34 S values of sulfate in surface water indicate that the major source of sulfate in sulfur-contaminated marshes is water from canals draining the Everglades Agricultural Area. Shallow ground water underlying the Everglades and rain water samples had much lower sulfate concentrations and δ 34 S values distinct from those found in surface water. The δ 34 S results implicate agricultural fertilizer as a major contributor to the sulfate contaminating the Everglades, but ground water under the Everglades Agricultural Area (EAA) may also be a contributing source. The contamination of the northern Everglades with sulfate from canal discharge may be a key factor in controlling the distribution and extent of methylmercury production in the Everglades.

Florida↗

USGS2020

Occurrence and geochemistry of lead-210 and polonium-210 radionuclides in public-drinking-water supplies from principal aquifers of the United States

On the basis of lifetime cancer risks, lead-210 ( 210 Pb) and polonium-210 ( 210 Po) ≥ 1.0 and 0.7 pCi/L (picocuries per liter), respectively, in drinking-water supplies may pose human-health concerns. 210 Pb and 210 Po were detected at concentrations greater than these thresholds at 3.7 and 1.5%, respectively, of filtered untreated groundwater samples from 1263 public-supply wells in 19 principal aquifers across the United States. Nationally, 72% of samples with radon-222 ( 222 Rn) concentrations > 4000 pCi/L had 210 Pb ≥ 1.0 pCi/L. 210 Pb is mobilized by alpha recoil associated with the decay of 222 Rn and short-lived progeny. 210 Pb concentrations ≥ 1.0 pCi/L occurred most frequently where acidic groundwaters inhibited 210 Pb readsorption (felsic-crystalline rocks) and where reducing alkaline conditions favored dissolution of iron–manganese- (Fe–Mn-) oxyhydroxides (which adsorb 210 Pb) and formation of lead–carbonate complexes (enhancing lead (Pb) mobility). 210 Po concentrations ≥ 0.7 pCi/L occurred almost exclusively in confined Coastal Plain aquifers where old (low percent-modern carbon-14) groundwaters were reducing, with high pH (>7.5) and high sodium/chloride (Na/Cl) ratios resulting from cation exchange. In high-pH environments, aqueous polonium (Po) is poorly sorbed, occurring as dihydrogen polonate (H 2 PoO 3 (aq)) or, under strongly reducing conditions, as a hydrogen-polonide anion (HPo – ). Fe–Mn- and sulfate-reduction and cation-exchange processes may mobilize polonium from mineral surfaces. Po 2+ occurrence in low-to-neutral-pH waters is attenuated by adsorption.

Environmental Science Technology↗

USGS2012

Stable isotope deltas: Tiny, yet robust signatures in nature

Although most of them are relatively small, stable isotope deltas of naturally occurring substances are robust and enable workers in anthropology, atmospheric sciences, biology, chemistry, environmental sciences, food and drug authentication, forensic science, geochemistry, geology, oceanography, and paleoclimatology to study a variety of topics. Two fundamental processes explain the stable isotope deltas measured in most terrestrial systems: isotopic fractionation and isotope mixing. Isotopic fractionation is the result of equilibrium or kinetic physicochemical processes that fractionate isotopes because of small differences in physical or chemical properties of molecular species having different isotopes. It is shown that the mixing of radioactive and stable isotope end members can be modelled to provide information on many natural processes, including 14C abundances in the modern atmosphere and the stable hydrogen and oxygen isotopic compositions of the oceans during glacial and interglacial times. The calculation of mixing fractions using isotope balance equations with isotope deltas can be substantially in error when substances with high concentrations of heavy isotopes (e.g. 13C, 2H, and 18O ) are mixed. In such cases, calculations using mole fractions are preferred as they produce accurate mixing fractions. Isotope deltas are dimensionless quantities. In the International System of Units (SI), these quantities have the unit 1 and the usual list of prefixes is not applicable. To overcome traditional limitations with expressing orders of magnitude differences in isotope deltas, we propose the term urey (symbol Ur), after Harold C. Urey, for the unit 1. In such a manner, an isotope delta value expressed traditionally as−25 per mil can be written as−25 mUr (or−2.5 cUr or−0.25 dUr; the use of any SI prefix is possible). Likewise, very small isotopic differences often expressed in per meg ‘units’ are easily included (e.g. either+0.015 ‰ or+15 per meg can be written as+15 μUr.

Isotopes in Environmental and Health Studies↗

USGS2023

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

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.

California↗