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USGS2013

Tracing groundwater with low-level detections of halogenated VOCs in a fractured carbonate-rock aquifer, Leetown Science Center, West Virginia, USA

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from 3 H/ 3 He and SF 6 data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC–ECD) exceeded that possible for air–water equilibrium in 34 of the 47 samples (median TDVOC of 24,800 pg kg −1 ), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20 a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The 3 H/ 3 He groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2 a in 2004 following a wet climatic period (2003–2004), and ages in the range of 4–7 a in periods of more average precipitation (2008–2009). The SF 6 and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg Formation located to the west of the LSC. A two-a record of specific conductance, water temperature, and discharge recorded at 30-min intervals demonstrated an approximately 3-month lag in discharge at Gray Spring. The low groundwater ages of waters from the carbonate rocks support rapid advective transport of contaminants from the LSC vicinity, yet the nearly ubiquitous occurrence of low-level concentrations of halogenated VOCs at the LSC suggests the presence of long-term persistent sources, such as seepage from the closed and sealed landfill, infiltration of VOCs that may persist locally in the epikarst, exchange with low-permeability zones in fractured rock, and upward leakage of older water that may contain elevated concentrations of halogenated VOCs from earlier land use activities.

West Virginia↗

USGS2013

Links between climate change, water-table depth, and water chemistry in a mineralized mountain watershed

Recent studies suggest that climate change is causing rising solute concentrations in mountain lakes and streams. These changes may be more pronounced in mineralized watersheds due to the sensitivity of sulfide weathering to changes in subsurface oxygen transport. Specific causal mechanisms linking climate change and accelerated weathering rates have been proposed, but in general remain entirely hypothetical. For mineralized watersheds, a favored hypothesis is that falling water tables caused by declining recharge rates allow an increasing volume of sulfide-bearing rock to become exposed to air, thus oxygen. Here, we test the hypothesis that falling water tables are the primary cause of an increase in metals and SO4 (100-400%) observed since 1980 in the Upper Snake River (USR), Colorado. The USR drains an alpine watershed geologically and climatologically representative of many others in mineralized areas of the western U.S. Hydrologic and chemical data collected from 2005 to 2011 in a deep monitoring well (WP1) at the top of the USR watershed are utilized. During this period, both water table depths and groundwater SO4 concentrations have generally increased in the well. A numerical model was constructed using TOUGHREACT that simulates pyrite oxidation near WP1, including groundwater flow and oxygen transport in both saturated and unsaturated zones. The modeling suggests that a falling water table could produce an increase in metals and SO4 of a magnitude similar to that observed in the USR (up to 300%). Future water table declines may produce limited increases in sulfide weathering high in the watershed because of the water table dropping below the depth of oxygen penetration, but may continue to enhance sulfide weathering lower in the watershed where water tables are shallower. Advective air (oxygen) transport in the unsaturated zone caused by seasonally variable recharge and associated water table fluctuations was found to have little influence on pyrite oxidation rates near WP1. However, this mechanism could be important in the case of a shallow dynamic water table and more abundant/reactive sulfides in the shallow subsurface. Data from WP1 and numerical modeling results are thus consistent with the falling water table hypothesis, and illustrate fundamental processes linking climate and sulfide weathering in mineralized watersheds.

Applied Geochemistry↗

USGS2013

234U/238U and δ87Sr in peat as tracers of paleosalinity in the Sacramento-San Joaquin Delta of California, USA

The purpose of this study was to determine the history of paleosalinity over the past 6000+ years in the Sacramento-San Joaquin Delta (the Delta), which is the innermost part of the San Francisco Estuary. We used a combination of Sr and U concentrations, d87Sr values, and 234U/238U activity ratios (AR) in peat as proxies for tracking paleosalinity. Peat cores were collected in marshes on Browns Island, Franks Wetland, and Bacon Channel Island in the Delta. Cores were dated using 137Cs, the onset of Pb and Hg contamination from hydraulic gold mining, and 14C. A proof of concept study showed that the dominant emergent macrophyte and major component of peat in the Delta, Schoenoplectus spp., incorporates Sr and U and that the isotopic composition of these elements tracks the ambient water salinity across the Estuary. Concentrations and isotopic compositions of Sr and U in the three main water sources contributing to the Delta (seawater, Sacramento River water, and San Joaquin River water) were used to construct a three-end-member mixing model. Delta paleosalinity was determined by examining variations in the distribution of peat samples through time within the area delineated by the mixing model. The Delta has long been considered a tidal freshwater marsh region, but only peat samples from Franks Wetland and Bacon Channel Island have shown a consistently fresh signal (<0.5 ppt) through time. Therefore, the eastern Delta, which occurs upstream from Bacon Channel Island along the San Joaquin River and its tributaries, has also been fresh for this time period. Over the past 6000+ years, the salinity regime at the western boundary of the Delta (Browns Island) has alternated between fresh and oligohaline (0.5-5 ppt).

California↗

USGS2014

Investigation of off-site airborne transport of lead from a superfund removal action site using lead isotope ratios and concentrations

Lead (Pb) concentration and Pb isotopic composition of surface and subsurface soil samples were used to investigate the potential for off-site air transport of Pb from a former white Pb processing facility to neighboring residential homes in a six block area on Staten Island, NY. Surface and subsurface soil samples collected on the Jewett White Pb site were found to range from 1.122 to 1.138 for 206 Pb/ 207 Pb and 2.393 to 2.411 for 208 Pb/ 207 Pb. The off-site surface soil samples collected from residential backyards, train trestle, near site grass patches and background areas varied from 1.144 to 1.196 for 206 Pb/ 207 Pb and 2.427 to 2.464 for 208 Pb/ 207 Pb. Two soil samples collected along Richmond Terrace, where Jewett site soils accumulated after major rain events, varied from 1.136 to 1.147 for 206 Pb/ 207 Pb and 2.407 to 2.419 for 208 Pb/ 207 Pb. Lead concentration for on-site surface soil samples ranged from 450 to 8000 ug/g, on-site subsurface soil samples ranged from 90,000 to 240,000 ug/g and off-site samples varied from 380 to 3500 ug/g. Lead concentration and isotopic composition for the Staten Island off-site samples were similar to previously published data for other northeastern US cities and reflect re-suspension and re-mobilization of local accumulated Pb. The considerable differences in both the Pb isotopic composition and Pb concentration of on-site and off-site samples resulted in the ability to geochemically trace the transport of particulate Pb. Data in this study indicate minimal off-site surface transport of Pb from the Jewett site into the neighboring residential area.

New York↗

USGS2014

Contaminants from Cretaceous black shale: I. Natural weathering processes controlling contaminant cycling in Mancos Shale, southwestern United States, with emphasis on salinity and selenium

Soils derived from black shale can accumulate high concentrations of elements of environmental concern, especially in regions with semiarid to arid climates. One such region is the Colorado River basin in the southwestern United States where contaminants pose a threat to agriculture, municipal water supplies, endangered aquatic species, and water-quality commitments to Mexico. Exposures of Cretaceous Mancos Shale (MS) in the upper basin are a major contributor of salinity and selenium in the Colorado River. Here, we examine the roles of geology, climate, and alluviation on contaminant cycling (emphasis on salinity and Se) during weathering of MS in a Colorado River tributary watershed. Stage I (incipient weathering) began perhaps as long ago as 20 ka when lowering of groundwater resulted in oxidation of pyrite and organic matter. This process formed gypsum and soluble organic matter that persist in the unsaturated, weathered shale today. Enrichment of Se observed in laterally persistent ferric oxide layers likely is due to selenite adsorption onto the oxides that formed during fluctuating redox conditions at the water table. Stage II weathering (pedogenesis) is marked by a significant decrease in bulk density and increase in porosity as shale disaggregates to soil. Rainfall dissolves calcite and thenardite (Na 2 SO 4 ) at the surface, infiltrates to about 1 m, and precipitates gypsum during evaporation. Gypsum formation (estimated 390 kg m −2 ) enriches soil moisture in Na and residual SO 4 . Transpiration of this moisture to the surface or exposure of subsurface soil (slumping) produces more thenardite. Most Se remains in the soil as selenite adsorbed to ferric oxides, however, some oxidizes to selenate and, during wetter conditions is transported with soil moisture to depths below 3 m. Coupled with little rainfall, relatively insoluble gypsum, and the translocation of soluble Se downward, MS landscapes will be a significant nonpoint source of salinity and Se to the Colorado River well into the future. Other trace elements weathering from MS that are often of environmental concern include U and Mo, which mimic Se in their behavior; As, Co, Cr, Cu, Ni, and Pb, which show little redistribution; and Cd, Sb, V, and Zn, which accumulate in Stage I shale, but are lost to varying degrees from upper soil intervals. None of these trace elements have been reported previously as contaminants in the study area.

Colorado↗

USGS2014

Contaminants from Cretaceous black shale: II. Effect of geology, weathering, climate, and land use on salinity and selenium cycling, Mancos Shale landscapes, southwestern United States

The Cretaceous Mancos Shale (MS) is a known nonpoint source for a significant portion of the salinity and selenium (Se) loads in the Colorado River in the southwestern United States and northwestern corner of Mexico. These two contaminants pose a serious threat to rivers in these arid regions where water supplies are especially critical. Tuttle et al. (companion paper) investigates the cycling of contaminants in a Colorado River tributary watershed (Uncompahgre River, southwestern Colorado) where the MS weathers under natural conditions. This paper builds on those results and uses regional soil data in the same watershed to investigate the impact of MS geology, weathering intensity, land use, and climate on salt and Se storage in and flux from soils on the natural landscape, irrigated agriculture fields, areas undergoing urban development, and wetlands. The size of salinity and Se reservoirs in the MS soils is quantified. Flux calculations show that during modern weathering, natural landscapes cycle salt and Se; however, little of it is released for transport to the Uncompahgre River (10% of the annual salinity and 6% of the annual Se river loads). When irrigated, salinity and Se loads from the MS soil increase (26% and 57% of the river load, respectively), causing the river to be out of compliance with Federal and State Se standards. During 100 years of irrigation, seven times more Se has been removed from agricultural soil than what was lost from natural landscapes during the entire period of pedogenesis. Under more arid conditions, even less salt and Se are expected to be transported from the natural landscape. However, if wetter climates prevail, transport could increase dramatically due to storage of soluble phases in the non-irrigated soil. These results are critical input for water-resource and land-use managers who must decide whether or not the salinity and Se in a watershed can be managed, what sustainable mitigation strategies are possible, and what landscapes should be targeted. The broader implications include providing a reliable approach for quantifying nonpoint-source contamination from MS and other rock units elsewhere that weather under similar conditions and, together with results from our companion paper, address the complex interplay of geology, weathering, climate, and land use on contaminant cycling in the arid Southwest.

Colorado↗

USGS2014

Biochar application to hardrock mine tailings: Soil quality, microbial activity, and toxic element sorption

Waste rock piles from historic mining activities remain unvegetated as a result of metal toxicity and high acidity. Biochar has been proposed as a low-cost remediation strategy to increase soil pH and reduce leaching of toxic elements, and improve plant establishment. In this laboratory column study, biochar made from beetle-killed pine wood was assessed for utility as a soil amendment by mixing soil material from two mine sites collected near Silverton, Colorado, USA with four application rates of biochar (0%, 10%, 20%, 30% vol:vol). Columns were leached seven times over 65 days and leachate pH and concentration of toxic elements and base cations were measured at each leaching. Nutrient availability and soil physical and biological parameters were determined following the incubation period. We investigated the hypotheses that biochar incorporation into acidic mine materials will (1) reduce toxic element concentrations in leaching solution, (2) improve soil parameters (i.e. increase nutrient and water holding capacity and pH, and decrease compaction), and (3) increase microbial populations and activity. Biochar directly increased soil pH (from 3.33 to 3.63 and from 4.07 to 4.77 in the two materials) and organic matter content, and decreased bulk density and extractable salt content in both mine materials, and increased nitrate availability in one material. No changes in microbial population or activity were detected in either mine material upon biochar application. In leachate solution, biochar increased base cations from both materials and reduced the concentrations of Al, Cd, Cu, Pb, and Zn in leachate solution from one material. However, in the material with greater toxic element content, biochar did not reduce concentrations of any measured dissolved toxic elements in leachate and resulted in a potentially detrimental release of Cd and Zn into solution at concentrations above that of the pure mine material. The length of time of effectiveness and specific sorption by biochar is variable by element and the toxic element concentration and acidity of the initial mine material.

Applied Geochemistry↗

USGS2014

A multiple-tracer approach to understanding regional groundwaterflow in the Snake Valley area of the eastern Great Basin, USA

Groundwater in Snake Valley and surrounding basins in the eastern Great Basin province of the western United States is being targeted for large-scale groundwater extraction and export. Concern about declining groundwater levels and spring flows in western Utah as a result of the proposed groundwater withdrawals has led to efforts that have improved the understanding of this regional groundwater flow system. In this study, environmental tracers (del2H, del18O, 3H, 14C, 3He, 4He, 20Ne, 40Ar, 84Kr, and 129Xe) and major ions from 142 sites were evaluated to investigate groundwater recharge and flow-path characteristics. With few exceptions, del2H and del18O show that most valley groundwater has similar ratios to mountain springs, indicating recharge is dominated by relatively high-altitude precipitation. The spatial distribution of 3H, terrigenic helium (4Heterr), and 3H/3He ages shows that modern groundwater (<60 yr) in valley aquifers is found only in the western third of the study area. Pleistocene and late-Holocene groundwater is found in the eastern parts of the study area. The age of Pleistocene groundwater is supported by minimum adjusted radiocarbon ages of up to 32 ka. Noble gas recharge temperatures (NGTs) are generally 1–11 degrees C in Snake and southern Spring Valleys and >11 degrees C to the east of Snake Valley and indicate a hydraulic discontinuity between Snake and Tule Valleys across the northern Confusion Range. The combination of NGTs and 4Heterr shows that the majority of Snake Valley groundwater discharges as springs, evapotranspiration, and well withdrawals within Snake Valley rather than continuing northeastward to discharge at either Fish Springs or the Great Salt Lake Playa. The refined understanding of groundwater recharge and flow paths acquired from this multi-tracer investigation has broad implications for interbasin subsurface flow estimates and future groundwater development.

Nevada, Utah↗

USGS2015

Characteristics and environmental aspects of slag: a review

Slag is a waste product from the pyrometallurgical processing of various ores. Based on over 150 published studies, this paper provides an overview of mineralogical and geochemical characteristics of different types of slag and their environmental consequences, particularly from the release of potentially toxic elements to water. This chapter reviews the characteristics of both ferrous (steel and blast furnace Fe) and non-ferrous (Ag, Cu, Ni, Pb, Sn, Zn) slag. Interest in slag has been increasing steadily as large volumes, on the order of hundreds of millions of tonnes, are produced annually worldwide. Research on slag generally focuses on potential environmental issues related to the weathering of slag dumps or on its utility as a construction material or reprocessing for secondary metal recovery. The chemistry and mineralogy of slag depend on the metallurgical processes that create the material and will influence its fate as waste or as a reusable product. The composition of ferrous slag is dominated by Ca and Si. Steel slag may contain significant Fe, whereas Mg and Al may be significant in Fe slag. Calcium-rich olivine-group silicates, melilite-group silicates that contain Al or Mg, Ca-rich glass, and oxides are the most commonly reported major phases in ferrous slag. Calcite and trace amounts of a variety of sulfides, intermetallic compounds, and pure metals are typically also present. The composition of non-ferrous slag, most commonly from base-metal production, is dominated by Fe and Si with significant but lesser amounts of Al and Ca. Silicates in the olivine, pyroxene, and melilite groups, as well as glass, spinels, and SiO 2 (i.e., quartz and other polymorphs) are commonly found in non-ferrous slag. Sulfides and intermetallic compounds are less abundant than the silicates and oxides. The concentrations of some elements exceed generic USEPA soil screening levels for human contact based on multiple exposure pathways; these elements include Al, Cr, Cu, Fe, Mn, Pb, and Zn based on bulk chemical composition. Each slag type usually contains a specific suite of elements that may be of environmental concern. In general, non-ferrous slag may have a higher potential to negatively impact the environment compared to ferrous slag, and is thus a less attractive material for reuse, based on trace element chemistry, principally for base metals. However, the amount of elements released into the environment is not always consistent with bulk chemical composition. Many types of leaching tests have been used to help predict slag’s long-term environmental behavior. Overall, ferrous slags produce an alkaline leachate due to the dissolution of Ca oxides and silicates derived from compounds originally added as fluxing agents, such as lime. Ferrous slag leachate is commonly less metal-rich than leachate from non-ferrous slag generated during base metal extraction; the latter leachate may even be acidic due to the oxidation of sulfides. Because of its characteristics, ferrous slag is commonly used for construction and environmental applications, whereas both non-ferrous and ferrous slag may be reprocessed for secondary metal recovery. Both types of slag have been a source of some environmental contamination. Research into the environmental aspects of slag will continue to be an important topic whether the goal is its reuse, recycling, or remediation.

Applied Geochemistry↗

USGS2015

Diel cycling of trace elements in streams draining mineralized areas: a review

Many trace elements exhibit persistent diel, or 24-h, concentration cycles in streams draining mineralized areas. These cycles can be caused by various physical and biogeochemical mechanisms including streamflow variation, photosynthesis and respiration, as well as reactions involving photochemistry, adsorption and desorption, mineral precipitation and dissolution, and plant assimilation. Iron is the primary trace element that exhibits diel cycling in acidic streams. In contrast, many cationic and anionic trace elements exhibit diel cycling in near-neutral and alkaline streams. Maximum reported changes in concentration for these diel cycles have been as much as a factor of 10 (988% change in Zn concentration over a 24-h period). Thus, monitoring and scientific studies must account for diel trace-element cycling to ensure that water-quality data collected in streams appropriately represent the conditions intended to be studied.

Applied Geochemistry↗

USGS2015

Characterizing toxicity of metal-contaminated sediments from mining areas

This paper reviews methods for testing the toxicity of metals associated with freshwater sediments, linking toxic effects with metal exposure and bioavailability, and developing sediment quality guidelines. The most broadly applicable approach for characterizing metal toxicity is whole-sediment toxicity testing, which attempts to simulate natural exposure conditions in the laboratory. Standard methods for whole-sediment testing can be adapted to test a wide variety of taxa. Chronic sediment tests that characterize effects on multiple endpoints (e.g., survival, growth, and reproduction) can be highly sensitive indicators of adverse effects on resident invertebrate taxa. Methods for testing of aqueous phases (pore water, overlying water, or elutriates) are used less frequently. Analysis of sediment toxicity data focuses on statistical comparisons between responses in sediments from the study area and responses in one or more uncontaminated reference sediments. For large or complex study areas, a greater number of reference sediments is recommended to reliably define the normal range of responses in uncontaminated sediments – the ‘reference envelope’. Data on metal concentrations and effects on test organisms across a gradient of contamination may allow development of concentration-response models, which estimate metal concentrations associated with specified levels of toxic effects (e.g. 20% effect concentration or EC20). Comparisons of toxic effects in laboratory tests with measures of impacts on resident benthic invertebrate communities can help document causal relationships between metal contamination and biological effects. Total or total-recoverable metal concentrations in sediments are the most common measure of metal contamination in sediments, but metal concentrations in labile sediment fractions (e.g., determined as part of selective sediment extraction protocols) may better represent metal bioavailability. Metals released by the weak-acid extraction of acid-volatile sulfide (AVS), termed simultaneously-extracted metals (SEM), are widely used to estimate the ‘potentially-bioavailable’ fraction of metals that is not bound to sulfides (i.e., SEM-AVS). Metal concentrations in pore water are widely considered to be direct measures of metal bioavailability, and predictions of toxicity based on pore-water metal concentrations may be further improved by modeling interactions of metals with other pore-water constituents using Biotic Ligand Models. Data from sediment toxicity tests and metal analyses has provided the basis for development of sediment quality guidelines, which estimate thresholds for toxicity of metals in sediments. Empirical guidelines such as Probable Effects Concentrations or (PECs) are based on associations between sediment metal concentrations and occurrence of toxic effects in large datasets. PECs do not model bioavailable metals, but they can be used to estimate the toxicity of metal mixtures using by calculation of probable effect quotients (PEQ = sediment metal concentration/PEC). In contrast, mechanistic guidelines, such as Equilibrium Partitioning Sediment Benchmarks (ESBs) attempt to predict both bioavailability and mixture toxicity. Application of these simple bioavailability models requires more extensive chemical characterization of sediments or pore water, compared to empirical guidelines, but may provide more reliable estimates of metal toxicity across a wide range of sediment types.

Applied Geochemistry↗

USGS2015

The fate of cyanide in leach wastes at gold mines: an environmental perspective

This paper reviews the basic chemistry of cyanide, methods by which cyanide can be analyzed, and aspects of cyanide behavior that are most relevant to environmental considerations at mineral processing operations associated with gold mines. The emphasis is on research results reported since 1999 and on data gathered for a series of U.S. Geological Survey studies that began in the late 1990s. Cyanide is added to process solutions as the CN − anion, but ore leaching produces numerous other cyanide-containing and cyanide-related species in addition to the desired cyanocomplex of gold. These can include hydrogen cyanide (HCN); cyanometallic complexes of iron, copper, zinc, nickel, and many other metals; cyanate (CNO − ); and thiocyanate (SCN − ). The fate of these species in solid wastes and residual process solutions that remain once gold recovery activities are terminated and in any water that moves beyond the ore processing facility dictates the degree to which cyanide poses a risk to aquatic organisms and aquatic-dependent organisms in the local environment. Cyanide-containing and cyanide-related species are subject to attenuation mechanisms that lead to dispersal to the atmosphere, chemical transformation to other carbon and nitrogen species, or sequestration as cyanometallic precipitates or adsorbed species on mineral surfaces. Dispersal to the atmosphere and chemical transformation amount to permanent elimination of cyanide, whereas sequestration amounts to storage of cyanide in locations from which it can potentially be remobilized by infiltrating waters if conditions change. From an environmental perspective, the most significant cyanide releases from gold leach operations involve catastrophic spills of process solutions or leakage of effluent to the unsaturated or saturated zones. These release pathways are unfavorable for two important cyanide attenuation mechanisms that tend to occur naturally: dispersal of free cyanide to the atmosphere and sunlight-catalyzed dissociation of strong cyanometallic complexes, which produces free cyanide that can then disperse to the atmosphere. The widest margins of environmental safety will be achieved where mineral processing operations are designed so that time for offgassing, aeration, and sunlight exposure are maximized in the event that cyanide-bearing solutions are released inadvertently.

Applied Geochemistry↗

USGS2015

Effects and quantification of acid runoff from sulfide-bearing rock deposited during construction of Highway E18, Norway

The Highway E18 between the cities of Grimstad and Kristiansand, southern Norway, constructed in the period 2006–2009, cuts through sulfide-bearing rock. The geology of this area is dominated by slowly-weathering gneiss and granites, and oxidation of fresh rock surfaces can result in acidification of surface water. Sulfide-containing rock waste from excavations during construction work was therefore deposited in three waste rock deposits off-site. The deposits consist of 630,000–2,360,000 metric tons of waste rock material. Shell sand and limestone gravel were added in layers in adequate amounts to mitigate initial acid runoff in one of the deposits. The shell sand addition was not adequate in the two others. The pH in the effluents from these two was reduced from 4.9–6.5 to 4.0–4.6, and Al concentrations increased from below 0.4 mg/L to 10–20 mg/L. Stream concentrations of trace metals increased by a factor of 25–400, highest for Ni, and then in decreasing order for Co, Mn, Cd, Zn and Cu. Concentrations of As, Cr and Fe remained unchanged. Ratios of Co/Ni and Cd/Zn indicate that the metal sources for these pair of metals are sphalerite and pyrite, respectively. Based on surveys and established critical limits for Al, surface waters downstream became toxic to fish and invertebrates. The sulfur release rates were remarkably stable in the monitoring period at all three sites. Annual sulfur release was 0.1–0.4% of the total amount of sulfur in the deposit, indicating release periods of 250–800 years. Precipitates of Al-hydroxysulfates, well-known from mining sites, were found at the base of the deposits, in streams and also along the ocean shore-line. The effects of added neutralization agents in the deposits and in treatment areas downstream gradually decreased, as indicated by reduced stream pH over time. Active measures are needed to avoid harmful ecological effects in the future.

Applied Geochemistry↗

USGS2014

Mobilization of selenium from the Mancos Shale and associated soils in the lower Uncompahgre River Basin, Colorado

This study investigates processes controlling mobilization of selenium in the lower part of the Uncompahgre River Basin in western Colorado. Selenium occurs naturally in the underlying Mancos Shale and is leached to groundwater and surface water by limited natural runoff, agricultural and domestic irrigation, and leakage from irrigation canals. Soil and sediment samples from the study area were tested using sequential extractions to identify the forms of selenium present in solid phases. Selenium speciation was characterized for nonirrigated and irrigated soils from an agricultural site and sediments from a wetland formed by a leaking canal. In nonirrigated areas, selenium was present in highly soluble sodium salts and gypsum. In irrigated soils, soluble forms of selenium were depleted and most selenium was associated with organic matter that was stable under near-surface weathering conditions. Laboratory leaching experiments and geochemical modeling confirm that selenium primarily is released to groundwater and surface water by dissolution of highly soluble selenium-bearing salts and gypsum present in soils and bedrock. Rates of selenium dissolution determined from column leachate experiments indicate that selenium is released most rapidly when water is applied to previously nonirrigated soils and sediment. High concentrations of extractable nitrate also were found in nonirrigated soils and bedrock that appear to be partially derived from weathered organic matter from the shale rather than from agricultural sources. Once selenium is mobilized, dissolved nitrate derived from natural sources appears to inhibit the reduction of dissolved selenium leading to elevated concentrations of selenium in groundwater. A conceptual model of selenium weathering is presented and used to explain seasonal variations in the surface-water chemistry of Loutzenhizer Arroyo, a major tributary contributor of selenium to the lower Uncompahgre River.

Colorado↗

USGS2014

Assessing the solubility controls on vanadium in groundwater, northeastern San Joaquin Valley, CA

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from <3 μg/L to 70 μg/L with a median of 21 μg/L. Concentrations of V were highest in samples collected from oxic groundwater (49% > 25 μg/L) and lowest in samples collected from anoxic groundwater (70% < 0.8 μg/L). In oxic groundwater, speciation modeling (SM) using PHREEQC predicted that V exists primarily as the oxyanion H 2 VO 4 − . Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V 5+ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH) 3 + ]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH) 3 molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V 3+ - or mixed V 3+ /Fe 3+ -oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions. Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO 3 ) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO 3 extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.

California↗

USGS2015

Using biotic ligand models to predict metal toxicity in mineralized systems

The biotic ligand model (BLM) is a numerical approach that couples chemical speciation calculations with toxicological information to predict the toxicity of aquatic metals. This approach was proposed as an alternative to expensive toxicological testing, and the U.S. Environmental Protection Agency incorporated the BLM into the 2007 revised aquatic life ambient freshwater quality criteria for Cu. Research BLMs for Ag, Ni, Pb, and Zn are also available, and many other BLMs are under development. Current BLMs are limited to ‘one metal, one organism’ considerations. Although the BLM generally is an improvement over previous approaches to determining water quality criteria, there are several challenges in implementing the BLM, particularly at mined and mineralized sites. These challenges include: (1) historically incomplete datasets for BLM input parameters, especially dissolved organic carbon (DOC), (2) several concerns about DOC, such as DOC fractionation in Fe- and Al-rich systems and differences in DOC quality that result in variations in metal-binding affinities, (3) water-quality parameters and resulting metal-toxicity predictions that are temporally and spatially dependent, (4) additional influences on metal bioavailability, such as multiple metal toxicity, dietary metal toxicity, and competition among organisms or metals, (5) potential importance of metal interactions with solid or gas phases and/or kinetically controlled reactions, and (6) tolerance to metal toxicity observed for aquatic organisms living in areas with elevated metal concentrations.

Applied Geochemistry↗

USGS2015

Biogeochemical aspects of uranium mineralization, mining, milling, and remediation

Natural uranium (U) occurs as a mixture of three radioactive isotopes: 238 U, 235 U, and 234 U. Only 235 U is fissionable and makes up about 0.7% of natural U, while 238 U is overwhelmingly the most abundant at greater than 99% of the total mass of U. Prior to the 1940s, U was predominantly used as a coloring agent, and U-bearing ores were mined mainly for their radium (Ra) and/or vanadium (V) content; the bulk of the U was discarded with the tailings (Finch et al., 1972). Once nuclear fission was discovered, the economic importance of U increased greatly. The mining and milling of U-bearing ores is the first step in the nuclear fuel cycle, and the contact of residual waste with natural water is a potential source of contamination of U and associated elements to the environment. Uranium is mined by three basic methods: surface (open pit), underground, and solution mining (in situ leaching or in situ recovery), depending on the deposit grade, size, location, geology and economic considerations (Abdelouas, 2006). Solid wastes at U mill tailings (UMT) sites can include both standard tailings (i.e., leached ore rock residues) and solids generated on site by waste treatment processes. The latter can include sludge or “mud” from neutralization of acidic mine/mill effluents, containing Fe and a range of coprecipitated constituents, or barium sulfate precipitates that selectively remove Ra (e.g., Carvalho et al., 2007). In this chapter, we review the hydrometallurgical processes by which U is extracted from ore, the biogeochemical processes that can affect the fate and transport of U and associated elements in the environment, and possible remediation strategies for site closure and aquifer restoration. This paper represents the fourth in a series of review papers from the U.S. Geological Survey (USGS) on geochemical aspects of UMT management that span more than three decades. The first paper (Landa, 1980) in this series is a primer on the nature of tailings and radionuclide mobilization from them. The second paper (Landa, 1999) includes coverage of research carried out under the U.S. Department of Energy’s Uranium Mill Tailings Remedial Action Program (UMTRA). The third paper (Landa, 2004) reflects the increased focus of researchers on biotic effects in UMT environs. This paper expands the focus to U mining, milling, and remedial actions, and includes extensive coverage of the increasingly important alkaline in situ recovery and groundwater restoration.

Applied Geochemistry↗

USGS2014

Mercury deposition and methylmercury formation in Narraguinnep Reservoir, southwestern Colorado, USA

Narraguinnep Reservoir in southwestern Colorado is one of several water bodies in Colorado with a mercury (Hg) advisory as Hg in fish tissue exceed the 0.3 μg/g guideline to protect human health recommended by the State of Colorado. Concentrations of Hg and methyl-Hg were measured in reservoir bottom sediment and pore water extracted from this sediment. Rates of Hg methylation and methyl-Hg demethylation were also measured in reservoir bottom sediment. The objective of this study was to evaluate potential sources of Hg in the region and evaluate the potential of reservoir sediment to generate methyl-Hg, a human neurotoxin and the dominant form of Hg in fish. Concentrations of Hg (ranged from 1.1 to 5.8 ng/L, n = 15) and methyl-Hg (ranged from 0.05 to 0.14 ng/L, n = 15) in pore water generally were highest at the sediment/water interface, and overall, Hg correlated with methyl-Hg in pore water (R 2 = 0.60, p = 0007, n = 15). Net Hg methylation flux in the top 3 cm of reservoir bottom sediment varied from 0.08 to 0.56 ng/m 2 /day (mean = 0.28 ng/m 2 /day, n = 5), which corresponded to an overall methyl-Hg production for the entire reservoir of 0.53 g/year. No significant point sources of Hg contamination are known to this reservoir or its supply waters, although several coal-fired power plants in the region emit Hg-bearing particulates. Narraguinnep Reservoir is located about 80 km downwind from two of the largest power plants, which together emit about 950 kg-Hg/year. Magnetic minerals separated from reservoir sediment contained spherical magnetite-bearing particles characteristic of coal-fired electric power plant fly ash. The presence of fly-ash magnetite in post-1970 sediment from Narraguinnep Reservoir indicates that the likely source of Hg to the catchment basin for this reservoir has been from airborne emissions from power plants, most of which began operation in the late-1960s and early 1970s in this region.

Colorado↗