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USGS2025

Tracing metal sources and groundwater flow paths in the Upper Animas River watershed using rare earth elements and stable isotopes

Groundwater flow paths and processes that govern metal mobility and transport are difficult to characterize in mountainous bedrock watersheds. Despite the difficulty in holistic characterization, conceptual understanding of subsurface hydrologic and geochemical processes is key to developing remediation plans for locations affected by acid mine drainage, such as the Upper Animas River watershed in southwestern Colorado, USA. Stable isotopes of water and rare earth elements were utilized to evaluate groundwater flow and metal sources within this complex catchment. Stable isotope samples collected from draining mine adits and springs display systematic spatial variation wherein sample sites at higher elevations have greater seasonal variability than sites at lower elevations. The Upper Cement Creek watershed, where multiple draining mines are present, displays the lowest seasonal variation in stable isotopic signatures, potentially indicating the presence of a large, well-mixed volume of groundwater storage or interbasin groundwater flow. Rare earth elements display statistically significant variation between different alteration styles in the catchment. Overprinting of regional propylitic alteration is evident based on enrichment of middle rare earth elements in acidic springs and mines that are not spatially associated with surficial exposures of acid generating alteration styles. Europium anomaly and middle rare earth enrichment signatures from two flooded mine tunnels on opposite sides of a watershed divide indicate connections to the same subsurface flooded mine workings.

Colorado↗

USGS2007

Progressive oxidation of pyrite in five bituminous coal samples: An As XANES and 57 Fe Mössbauer spectroscopic study

Naturally occurring pyrite commonly contains minor substituted metals and metalloids (As, Se, Hg, Cu, Ni, etc.) that can be released to the environment as a result of its weathering. Arsenic, often the most abundant minor constituent in pyrite, is a sensitive monitor of progressive pyrite oxidation in coal. To test the effect of pyrite composition and environmental parameters on the rate and extent of pyrite oxidation in coal, splits of five bituminous coal samples having differing amounts of pyrite and extents of As substitution in the pyrite, were exposed to a range of simulated weathering conditions over a period of 17 months. Samples investigated include a Springfield coal from Indiana (whole coal pyritic S = 2.13 wt.%; As in pyrite = detection limit (d.l.) to 0.06 wt.%), two Pittsburgh coal samples from West Virginia (pyritic S = 1.32–1.58 wt.%; As in pyrite = d.l. to 0.34 wt.%), and two samples from the Warrior Basin, Alabama (pyritic S = 0.26–0.27 wt.%; As in pyrite = d.l. to 2.72 wt.%). Samples were collected from active mine faces, and expected differences in the concentration of As in pyrite were confirmed by electron microprobe analysis. Experimental weathering conditions in test chambers were maintained as follows: (1) dry Ar atmosphere; (2) dry O 2 atmosphere; (3) room atmosphere (relative humidity &sim;20–60%); and (4) room atmosphere with samples wetted periodically with double-distilled water. Sample splits were removed after one month, nine months, and 17 months to monitor the extent of As and Fe oxidation using As X-ray absorption near-edge structure (XANES) spectroscopy and 57 Fe Mössbauer spectroscopy, respectively. Arsenic XANES spectroscopy shows progressive oxidation of pyritic As to arsenate, with wetted samples showing the most rapid oxidation. 57 Fe Mössbauer spectroscopy also shows a much greater proportion of Fe 3+ forms (jarosite, Fe 3+ sulfate, FeOOH) for samples stored under wet conditions, but much less difference among samples stored under dry conditions in different atmospheres. The air-wet experiments show evidence of pyrite re-precipitation from soluble ferric sulfates, with As retention in the jarosite phase. Extents of As and Fe oxidation were similar for samples having differing As substitution in pyrite, suggesting that environmental conditions outweigh the composition and amount of pyrite as factors influencing the oxidation rate of Fe sulfides in coal.

Applied Geochemistry↗

USGS2007

Organic petrology of Paleocene Marcelina Formation coals, Paso Diablo mine, western Venezuela: Tectonic controls on coal type

About 7??Mt of high volatile bituminous coal are produced annually from the four coal zones of the Upper Paleocene Marcelina Formation at the Paso Diablo open-pit mine of western Venezuela. As part of an ongoing coal quality study, we have characterized twenty-two coal channel samples from the mine using organic petrology techniques. Samples also were analyzed for proximate-ultimate parameters, forms of sulfur, free swelling index, ash fusion temperatures, and calorific value. Six of the samples represent incremental benches across the 12-13??m thick No. 4 bed, the stratigraphically lowest mined coal, which is also mined at the 10??km distant Mina Norte open-pit. Organic content of the No. 4 bed indicates an upward increase of woody vegetation and/or greater preservation of organic material throughout the life of the original mire(s). An upward increase in telovitrinite and corresponding decrease in detrovitrinite and inertinite illustrate this trend. In contrast, stratigraphically higher coal groups generally exhibit a 'dulling upward' trend. The generally high inertinite content, and low ash yield and sulfur content, suggest that the Paso Diablo coals were deposited in rain-fed raised mires, protected from clastic input and subjected to frequent oxidation and/or moisture stress. However, the two thinnest coal beds (both 0.7??m thick) are each characterized by lower inertinite and higher telovitrinite content relative to the rest of Paso Diablo coal beds, indicative of less well-established raised mire environments prior to drowning. Foreland basin Paleocene coals of western Venezuela, including the Paso Diablo deposit and time-correlative coal deposits of the Ta??chira and Me??rida Andes, are characterized by high inertinite and consistently lower ash and sulfur relative to Eocene and younger coals of the area. We interpret these age-delimited coal quality characteristics to be due to water availability as a function of the tectonic control of subsidence rate. It is postulated that slower subsidence rates dominated during the Paleocene while greater foreland basin subsidence rates during the Eocene-Miocene resulted from the loading of nappe thrust sheets as part of the main construction phases of the Andean orogen. South-southeastward advance and emplacement of the Lara nappes during the oblique transpressive collision of the Caribbean and South American tectonic plates in the Paleocene was further removed from the sites of peat deposition, resulting in slower subsidence rates. Slower subsidence in the Paleocene may have favored the growth of raised mires, generating higher inertinite concentrations through more frequent moisture stress. Consistently low ash yield and sulfur content would be due to the protection from clastic input in raised mires, in addition to the leaching of mineral matter by rainfall and the development of acidic conditions preventing fixation of sulfur. In contrast, peat mires of Eocene-Miocene age encountered rapid subsidence due to the proximity of nappe emplacement, resulting in lower inertinite content, higher and more variable sulfur content, and higher ash yield.

International Journal of Coal Geology↗

USGS2007

Consumptive Water-Use Coefficients for the Great Lakes Basin and Climatically Similar Areas

Consumptive water use is the portion of water withdrawn (for a particular use) that is evaporated, transpired, incorporated into products or crops, consumed by humans or livestock, or otherwise removed from the immediate water environment. This report, which is organized by water?use categories, includes consumptive?use coefficients for the Great Lakes Basin (including Canada) and for areas climatically similar to the Great Lakes Basin. This report also contains an annotated bibliography of consumptive water?use coefficients. Selected references are listed for consumptive?use data from elsewhere in the world. For the industrial water?use category, the median consumptive?use coefficients were 10 percent for the Great Lakes Basin, climatically similar areas, and the world; the 25th and 75th percentiles for these geographic areas were comparable within 6 percent. The combined domestic and public?supply consumptive?use statistics (median, 25th and 75th percentiles) were between 10 to 20 percent for the various geographic areas. Although summary statistics were similar for coefficients in the livestock and irrigation water?use categories for the Great Lakes Basin and climatically similar areas, statistic values for the world on a whole were substantially lower (15 to 28 percent lower). Commercial and thermoelectric power consumptive?use coefficient statistics (median, 25th, and 75th percentile) also were comparable for the Great Lakes Basin and climatically similar areas, within 2 percent. References for other countries were not found for commercial and thermoelectric power water?use categories. The summary statistics for the mining consumptive?use coefficients varied, likely because of differences in types of mining, processes, or equipment.

Scientific Investigations Report↗

USGS2024

Models no not provide proof: An example of model ambiguity and application of isotopic data in a mine pit lake

Geochemical and hydrologic models of pit lakes are commonly used in environmental regulatory decisions to predict future water quality and hydrologic conditions and to understand existing pit lakes. Models may be used to quantify sulfide oxidation, predict thermal/chemical stratification and mixing, and better understand connections between pit lakes and aquifers. One concern related to the hydrologic character of pit lakes is if they are terminal (a groundwater sink with no outflow) or flowthrough (both receiving groundwater inflow and discharging to groundwater). This question was pertinent to the Liberty pit lake, a small acidic pit lake formed in a former Cu deposit in south-central Nevada where potentiometric and geochemical data potentially indicate pit-lake outflow. Potential discharge to groundwater from the pit lake was evaluated using a water-balance model, but uncertainty in hydraulic parameters led to ambiguity in the hydrologic character. Stable isotopes of water were then sampled from the pit lake and adjacent groundwater wells, which unambiguously indicated the lack of an evaporative signature in downgradient groundwater because the groundwater did not plot on a hypothetical mixing line between evaporated pit lake water and observed meteoric recharge. This methodology provided a more effective and more data-driven approach for understanding pit-lake hydrology. Although predictive models are required to quantify reasonable bounds on future conditions, many models contain substantial uncertainty and are not well suited in some environments. Datasets that provide more clear lines of evidence could be collected from existing pit lakes whenever possible to inform water-rock interaction, limnological behavior, and connectivity to adjacent groundwater.

Nevada↗

USGS2012

Occurrence model for volcanogenic beryllium deposits

Current global and domestic mineral resources of beryllium (Be) for industrial uses are dominated by ores produced from deposits of the volcanogenic Be type. Beryllium deposits of this type can form where hydrothermal fluids interact with fluorine and lithophile-element (uranium, thorium, rubidium, lithium, beryllium, cesium, tantalum, rare earth elements, and tin) enriched volcanic rocks that contain a highly reactive lithic component, such as carbonate clasts. Volcanic and hypabyssal high-silica biotite-bearing topaz rhyolite constitutes the most well-recognized igneous suite associated with such Be deposits. The exemplar setting is an extensional tectonic environment, such as that characterized by the Basin and Range Province, where younger topaz-bearing igneous rock sequences overlie older dolomite, quartzite, shale, and limestone sequences. Mined deposits and related mineralized rocks at Spor Mountain, Utah, make up a unique economic deposit of volcanogenic Be having extensive production and proven and probable reserves. Proven reserves in Utah, as reported by the U.S. Geological Survey National Mineral Information Center, total about 15,900 tons of Be that are present in the mineral bertrandite (Be 4 Si 2 O 7 (OH) 2 ). At the type locality for volcanogenic Be, Spor Mountain, the tuffaceous breccias and stratified tuffs that host the Be ore formed as a result of explosive volcanism that brought carbonate and other lithic fragments to the surface through vent structures that cut the underlying dolomitic Paleozoic sedimentary rock sequences. The tuffaceous sediments and lithic clasts are thought to make up phreatomagmatic base surge deposits. Hydrothermal fluids leached Be from volcanic glass in the tuff and redeposited the Be as bertrandite upon reaction of the hydrothermal fluid with carbonate clasts in lithic-rich sections of tuff. The localization of the deposits in tuff above fluorite-mineralized faults in carbonate rocks, together with isotopic evidence for the involvement of magmatic water in an otherwise meteoric water-dominated hydrothermal system, indicate that magmatic volatiles contributed to mineralization. At the type locality, hydrothermal alteration of dolomite clasts formed layered nodules of calcite, opal, fluorite, and bertrandite, the latter occurring finely intergrown with fluorite. Alteration assemblages and elemental enrichments in the tuff and surrounding volcanic rocks include regional diagenetic clays and potassium feldspar and distinctive hydrothermal halos of anomalous fluorine, lithium, molybdenum, niobium, tin, and tantalum, and intense potassium feldspathization with sericite and lithium-smectite in the immediate vicinity of Be ore. Formation of volcanogenic Be deposits is due to the coincidence of multiple factors that include an appropriate Be-bearing source rock, a subjacent pluton that supplied volatiles and heat to drive convection of meteoric groundwater, a depositional site characterized by the intersection of normal faults with permeable tuff below a less permeable cap rock, a fluorine-rich ore fluid that facilitated Be transport (for example, BeF 4 2- complex), and the existence of a chemical trap that caused fluorite and bertrandite to precipitate at the former site of carbonate lithic clasts in the tuff.

Scientific Investigations Report↗

USGS2002

Rocky Mountain futures: An ecological perspective

The Rocky Mountain West is largely arid and steep, with ecological scars from past human use visible for hundreds of years. Just how damaging were the past 150 years of activity? How do current rates of disturbance compare with past mining, grazing, and water diversion activities? In the face of constant change, what constitutes a "natural" ecosystem? And can a high quality of life be achieved for both human and natural communities in this region. Rocky Mountain Futures presents a comprehensive and wide-ranging examination of the ecological consequences of past, current, and future human activities in the Rocky Mountain region of the United States and Canada. The book brings together 32 leading ecologists, geographers, and other scientists and researchers to present an objective assessment of the cumulative effects of human activity on the region's ecological health and to consider changes wrought by past human use. This combined view of past and present reveals where Rocky Mountain ecosystems are heading, and the authors project what the future holds based upon current economic and social trends and the patterns that emerge from them. The book: examines the biogeographic and paleoenvironmental setting and historical climate that have shaped Rocky Mountain ecosystems traces the direct human influences on landscapes and ecosystems over the past 150 years explores the cumulative effects of past, present, and projected future human activities on tundra, subalpine and montane forests, valleys, grasslands, and waters offers case studies that illustrate specific examples of human influence and current efforts to restore the environment Case studies focus on northern New Mexico; Summit County, Colorado; Flathead Valley, Montana; and Alberta, Canada. Among the contributors are Craig D. Allen, N. Thompson Hobbs, Linda L. Joyce, Robert E. Keane, David Schindler, Timothy R. Seastedt, David Theobald, Diana Tomback, William Travis, Cathy Whitlock, and Jack Stanford. The United Nations has proclaimed 2002 as the International Year of Mountains to increase international awareness of the global importance of mountain ecosystems. The case-based multidisciplinary approach of this book constitutes an important new model for understanding the implications of land-use practices and economic activity on mountains, and will serve a vital role in improving decisionmaking both in the Rocky Mountains and in other parts of the world that face similar challenges.

Book↗

USGS2008

Geochemical controls of elevated arsenic concentrations in groundwater, Ester Dome, Fairbanks district, Alaska

Ester Dome, an upland area near Fairbanks, Alaska, was chosen for a detailed hydrogeochemical study because of the previously reported elevated arsenic in groundwater, and the presence of a large set of wells amenable to detailed sampling. Ester Dome lies within the Fairbanks mining district, where gold-bearing quartz veins, typically containing 2–3 vol.% sulfide minerals (arsenopyrite, stibnite, and pyrite), have been mined both underground and in open cuts. Gold-bearing veins on Ester Dome occur in shear zones and the sulfide minerals in these veins have been crushed to fine-grained material by syn- or post-mineralization movement. Groundwater at Ester Dome is circumneutral, Ca–HCO 3 to Ca–SO 4 type, and ranges from dilute (specific conductance of 48 µS/cm) to more concentrated (specific conductance as high as 2070 µS/cm). In general, solute concentrations increase down hydrologic gradient. Redox species indicate that the groundwaters range from oxic to sub-oxic (low dissolved oxygen, Fe(III) reduction, no SO 4 reduction). Waters with the highest Fe concentrations, as high as 10.7 mg/L, are the most anoxic. Dissolved As concentrations range from < 1 to 1160 µg/L, with a median value of 146 µg/L. Arsenic concentrations are not correlated with specific conductance or Fe concentrations, suggesting that neither groundwater residence time, nor reductive dissolution of iron oxyhydroxides, control the arsenic chemistry. Furthermore, As concentrations do not covary with other constituents that form anions and oxyanions in solution (e.g., HCO 3 , Mo, F, or U) such that desorption of arsenic from clays or oxides also does not control arsenic mobility. Oxidation of arsenopyrite and dissolution of scorodite, in the near-surface environment appears to be the primary control of dissolved As in this upland area. More specifically, the elevated As concentrations are spatially associated with sulfidized shear zones and localities of gold-bearing quartz veins. Consistent with this interpretation, elevated dissolved Sb concentrations (as high as 59 µg/L), also correlated with occurrences of hypogene sulfide minerals, were measured in samples with high dissolved As concentrations.

Chemical Geology↗

USGS2010

Geochemistry of trace elements in coals from the Zhuji Mine, Huainan Coalfield, Anhui, China

The abundances of nine major elements and thirty-eight trace elements in 520 samples of low sulfur coals from the Zhuji Mine, Huainan Coalfield, Anhui, China, were determined. Samples were mainly collected from 10 minable coal seams of 29 boreholes during exploration. The B content in coals shows that the influence of brackish water decreased toward the top of coal seams; marine transgression and regression occurred frequently in the Lower Shihezi Formation. A wide range of elemental abundances is found. Weighted means of Na, K, Fe, P, Be, B, Co, Ni, Cr, Se, Sb, Ba, and Bi abundances in Zhuji coals are higher, and the remainder elements are either lower or equal to the average values of elements in coals of northern China. Compared to the Chinese coals, the Zhuji coals are higher in Na, K, Be, B, Cr, Co, Se, Sn, Sb, and Bi, but lower in Ti, P, Li, V and Zn. The Zhuji coals are lower only in S, P, V and Zn than average U.S. and world coals. Potassium, Mg, Ca, Mn, Sr, As, Se, Sb and light rare earth elements (LREE) had a tendency to be enriched in thicker coal seams, whereas Fe, Ti, P, V, Co, Ni, Y, Mo, Pb and heavy rare earth elements (HREE) were inclined to concentrate in thinner coal seams. The enrichment of some elements in the Shanxi or Upper Shihezi Formations is related to their depositional environments. The elements are classified into three groups based on their stratigraphic distributions from coal seams 3 to 11-2, and the characteristics of each group are discussed. Lateral distributions of selected elements are also investigated. The correlation coefficients of elemental abundances with ash content show that the elements may be classified into four groups related to modes of occurrence of these elements. ?? 2009 Elsevier B.V. All rights reserved.

International Journal of Coal Geology↗

USGS2022

Mine drainage precipitates attenuate and conceal wastewater-derived phosphate pollution in stream water

Hydrous ferric-oxide (HFO) coatings on streambed sediments may attenuate dissolved phosphate (PO 4 ) concentrations at acidic to neutral pH conditions, limiting phosphorus (P) transport and availability in aquatic ecosystems. Mesh-covered tiles on which “natural” HFO from abandoned mine drainage (AMD) had precipitated were exposed to treated municipal wastewater (MWW) effluent or a mixture of stream water and effluent. Between 42 and 99% of the dissolved P in effluent was removed from the water to a thin coating (~2 μm) of HFO on the mesh. Geochemical equilibrium model results predicted the removal of 76 to 99% of PO 4 from the water by adsorption to the HFO, depending on the HFO quantity, initial PO 4 concentration, and pH. The measurements and model results indicated the capacity for P removal decreased as the concentration of P associated with the HFO increased. Continuing accumulation of HFO from upstream AMD sources replenish the in-stream capacity for P attenuation below the MWW discharge. This indicates AMD pollution may conceal P inputs and limit the amount of dissolved P transported to downstream ecosystems. However, HFO-rich sediments also represent a potential source of “legacy” P that could confound management practices intended to decrease nutrient and metal loadings.

Pennsylvania↗

USGS2024

Deep-ocean macrofaunal assemblages on ferromanganese and phosphorite-rich substrates in the Southern California Borderland

Mineral-rich hardgrounds, such as ferromanganese (FeMn) crusts and phosphorites, occur on seamounts and continental margins, gaining attention for their resource potential due to their enrichment in valuable metals in some regions. This study focuses on the Southern California Borderland (SCB), an area characterized by uneven and heterogeneous topography featuring FeMn crusts, phosphorites, basalt, and sedimentary rocks that occur at varying depths and are exposed to a range of oxygen concentrations. Due to its heterogeneity, this region serves as an optimal setting for investigating the relationship between mineral-rich hardgrounds and benthic fauna. This study characterizes the density, diversity, and community composition of macrofauna (>300 μm) on hardgrounds as a function of substrate type and environment (depth and oxygen ranges). Rocks and their macrofauna were sampled quantitatively using remotely operated vehicles (ROVs) during expeditions in 2020 and 2021 at depths above, within, and below the oxygen minimum zone (OMZ). A total of 3,555 macrofauna individuals were counted and 416 different morphospecies (excluding encrusting bryozoans and hydrozoans) were identified from 82 rocks at depths between 231 and 2,688 m. Average density for SCB macrofauna was 11.08 ± 0.87 ind. 200 cm −2 and mean Shannon-Wiener diversity per rock (H′ [loge] ) was 2.22 ± 0.07. A relationship was found between substrate type and macrofaunal communities. Phosphorite rocks had the highest H′ of the four substrates compared on a per-rock basis. However, when samples were pooled by substrate, FeMn crusts had the highest H′ and rarefaction diversity. Of all the environmental variables examined, water depth explained the largest variance in macrofaunal community composition. Macrofaunal density and diversity values were similar at sites within and outside the OMZ. This study is the first to analyze the macrofaunal communities of mineral-rich hardgrounds in the SCB, which support deep-ocean biodiversity by acting as specialized substrates for macrofaunal communities. Understanding the intricate relationships between macrofaunal assemblages and mineral-rich substrates may inform effects from environmental disruptions associated with deep-seabed mining or climate change. The findings contribute baseline information useful for effective conservation and management of the SCB and will support scientists in monitoring changes in these communities due to environmental disturbance or human impact in the future.

California↗

USGS1981

Search for high-calcium limestone in Silurian reefs of northern Indiana

During Silurian time, the Indiana part of the Wabash Platform was a shallow-water area between the proto-lllinois and pro-to-Michigan Basins and a site of growth of hundreds, or perhaps thousands, of reefs. Today, most reefs of northern Indiana are dolomite, but some are dolomitic limestone, and a few are limestone of high purity in deposits that can be mined by open-pit methods. Four of the five generations of reefs of Silurian age in the Great Lakes area have been recognized in northern Indiana. All known oldest-generation reefs in Indiana (second-generation in the Great Lakes area) are dolomitic. A reef in Carroll County containing commercial amounts of high-calcium limestone is the next oldest (third generation), with roots in basal Louisville limestone, and a limestone reef of similar size in Grant County is of a younger (fourth) generation, with its roots in upper Louisville limestone and dolomite. Numerous slightly younger reefs with mostly mixed dolomitic-calcitic compositions are also of this generation, but all known examples are too small to be commercially important. One small limestone reef has been found in the youngest (fifth) generation, with roots in limestone of the Kokomo Limestone Member of the Salina Formation. All known limestone reefs are restricted to an area of six counties in north-central Indiana, although no apparent depositional environment as revealed from study of surrounding inter-reef rocks has been found to account for any restriction. Dolomitization is more likely related to the textures and lithologies of the individual reefs.

Geological Society of America Bulletin↗

USGS2012

Low-level copper exposures increase visibility and vulnerability of juvenile coho salmon to cutthroat trout predators

Copper contamination in surface waters is common in watersheds with mining activities or agricultural, industrial, commercial, and residential human land uses. This widespread pollutant is neurotoxic to the chemosensory systems of fish and other aquatic species. Among Pacific salmonids (Oncorhynchus spp.), copper-induced olfactory impairment has previously been shown to disrupt behaviors reliant on a functioning sense of smell. For juvenile coho salmon (O. kisutch), this includes predator avoidance behaviors triggered by a chemical alarm cue (conspecific skin extract). However, the survival consequences of this sublethal neurobehavioral toxicity have not been explored. In the present study juvenile coho were exposed to low levels of dissolved copper (5-20 microg/L for 3 h) and then presented with cues signaling the proximity of a predator. Unexposed coho showed a sharp reduction in swimming activity in response to both conspecific skin extract and the upstream presence of a cutthroat trout predator (O. clarki clarki) previously fed juvenile coho. This alarm response was absent in prey fish that were exposed to copper. Moreover, cutthroat trout were more effective predators on copper-exposed coho during predation trials, as measured by attack latency, survival time, and capture success rate. The shift in predator-prey dynamics was similar when predators and prey were co-exposed to copper. Overall, we show that copper-exposed coho are unresponsive to their chemosensory environment, unprepared to evade nearby predators, and significantly less likely to survive an attack sequence. Our findings contribute to a growing understanding of how common environmental contaminants alter the chemical ecology of aquatic communities.

Ecological Applications↗

USGS2012

Assessing time-integrated dissolved concentrations and predicting toxicity of metals during diel cycling in streams

Evaluating water quality and the health of aquatic organisms is challenging in systems with systematic diel (24 hour) or less predictable runoff-induced changes in water composition. To advance our understanding of how to evaluate environmental health in these dynamic systems, field studies of diel cycling were conducted in two streams (Silver Bow Creek and High Ore Creek) affected by historical mining activities in southwestern Montana. A combination of sampling and modeling tools were used to assess the toxicity of metals in these systems. Diffusive Gradients in Thin Films (DGT) samplers were deployed at multiple time intervals during diel sampling to confirm that DGT integrates time-varying concentrations of dissolved metals. Thermodynamic speciation calculations using site specific water compositions, including time-integrated dissolved metal concentrations determined from DGT, and a competitive, multiple-metal biotic ligand model incorporated into the Windemere Humic Aqueous Model Version 6.0 (WHAM VI) were used to determine the chemical speciation of dissolved metals and biotic ligands. The model results were combined with previously collected toxicity data on cutthroat trout to derive a relationship that predicts the relative survivability of these fish at a given site. This integrative approach may prove useful for assessing water quality and toxicity of metals to aquatic organisms in dynamic systems and evaluating whether potential changes in environmental health of aquatic systems are due to anthropogenic activities or natural variability.

Science of the Total Environment↗

USGS2017

Microbially mediated barite dissolution in anoxic brines

Fluids injected into shale formations during hydraulic fracturing of black shale return with extraordinarily high total-dissolved-solids (TDS) and high concentrations of barium (Ba) and radium (Ra). Barite, BaSO 4 , has been implicated as a possible source of Ba as well as a problematic mineral scale that forms on internal well surfaces, often in close association with radiobarite, (Ba,Ra)SO 4 . The dissolution of barite by abiotic processes is well quantified. However, the identification of microbial communities in flowback and produced water necessitates the need to understand barite dissolution in the presence of bacteria. Therefore, we evaluated the rates and mechanisms of abiotic and microbially-mediated barite dissolution under anoxic and hypersaline conditions in the laboratory. Barite dissolution experiments were conducted with bacterial enrichment cultures established from produced water from Marcellus Shale wells located in northcentral Pennsylvania. These cultures were dominated by anaerobic halophilic bacteria from the genus Halanaerobium . Dissolved Ba was determined by ICP-OES and barite surfaces were investigated by SEM and AFM. Our results reveal that: 1) higher amounts of barium (up to ∼5 × ) are released from barite in the presence of Halanaerobium cultures compared to brine controls after 30 days of reaction, 2) etch pits that develop on the barite (001) surface in the presence of Halanaerobium exhibit a morphology that is distinct from those that form during control experiments without bacteria, 3) etch pits that develop in the presence of Halanaerobium exhibit a morphology that is similar to the morphology of etch pits formed in the presence of strong organic chelators, EDTA and DTPA, and 4) experiments using dialysis membranes to separate barite from bacteria suggest that direct contact between the two is not required in order to promote dissolution. These results suggest that Halanaerobium increase the rate of barite dissolution in anoxic and high ionic strength solutions. Additionally, the increase in rate occurs without direct microbe-mineral contact suggesting that metabolites secreted by the bacteria may be responsible for promotion of dissolution. The findings of this study have implications for understanding barium cycling in marine/hypersaline environments, release of barium (and associated radium) from waste solids generated from energy and mining industries, as well as potential for developing new anti-scaling chemicals.

Applied Geochemistry↗

USGS2024

Sulphide petrology and ore genesis of the stratabound Sheep Creek sediment-hosted Zn–Pb–Ag–Sn prospect, and U–Pb zircon constraints on the timing of magmatism in the northern Alaska Range

The Sheep Creek prospect is a stratabound Zn–Pb–Ag–Sn massive sulfide occurrence in the Bonnifield mining district, northern Alaska Range. The prospect is within a quartz–sericite–graphite–chlorite schist unit associated with Devonian carbonaceous and siliceous metasedimentary rocks. Volcanogenic massive sulfide (VMS) deposits in the district are hosted in felsic metavolcanic rocks (362 ± 2 Ma) associated with siliciclastic and carbonaceous sedimentary rocks that overlie the stratigraphic sequence hosting the Sheep Creek prospect. Felsic metaigneous rocks in underlying units are 372 ± 4 to 366 ± 4 Ma. Sheep Creek is atypical of the other sulfide deposits in the district in (1) having Sn grades up to 1.2%; (2) being contained in fine-grained, quartz-rich rocks and quartz–pebble conglomerate that likely originated as chert and chert-clast sediment, respectively; and (3) showing minimal evidence of volcanic components in the host rocks. Comparison of immobile trace-element proportions for graphitic and siliceous rocks from the Sheep Creek area with those for argillite associated with the Bonnifield VMS deposits indicates a continental volcanic-arc provenance for the former and a within-plate and passive margin provenance for the latter. In contrast to previously published interpretations, our data analysis supports a clastic-dominated (CD) rather than a VMS affinity for the Sheep Creek prospect. In our model, Zn–Pb–Ag–Sn mineralization formed by syngenetic or early diagenetic processes on or beneath the seafloor, possibly in the shallow-water environment of an outer continental shelf setting. Potential analogues are the Paleozoic CD deposits in the Canadian Selwyn Basin outboard of the Laurentian continental margin.

Alaska↗

USGS2014

Mercury in the nation's streams - Levels, trends, and implications

Mercury is a potent neurotoxin that accumulates in fish to levels of concern for human health and the health of fish-eating wildlife. Mercury contamination of fish is the primary reason for issuing fish consumption advisories, which exist in every State in the Nation. Much of the mercury originates from combustion of coal and can travel long distances in the atmosphere before being deposited. This can result in mercury-contaminated fish in areas with no obvious source of mercury pollution. Three key factors determine the level of mercury contamination in fish - the amount of inorganic mercury available to an ecosystem, the conversion of inorganic mercury to methylmercury, and the bioaccumulation of methylmercury through the food web. Inorganic mercury originates from both natural sources (such as volcanoes, geologic deposits of mercury, geothermal springs, and volatilization from the ocean) and anthropogenic sources (such as coal combustion, mining, and use of mercury in products and industrial processes). Humans have doubled the amount of inorganic mercury in the global atmosphere since pre-industrial times, with substantially greater increases occurring at locations closer to major urban areas. In aquatic ecosystems, some inorganic mercury is converted to methylmercury, the form that ultimately accumulates in fish. The rate of mercury methylation, thus the amount of methylmercury produced, varies greatly in time and space, and depends on numerous environmental factors, including temperature and the amounts of oxygen, organic matter, and sulfate that are present. Methylmercury enters aquatic food webs when it is taken up from water by algae and other microorganisms. Methylmercury concentrations increase with successively higher trophic levels in the food web—a process known as bioaccumulation. In general, fish at the top of the food web consume other fish and tend to accumulate the highest methylmercury concentrations. This report summarizes selected stream studies conducted by the U.S. Geological Survey (USGS) since the late 1990s, while also drawing on scientific literature and datasets from other sources. Previous national mercury assessments by other agencies have focused largely on lakes. Although numerous studies of mercury in streams have been conducted at local and regional scales, recent USGS studies provide the most comprehensive, multimedia assessment of streams across the United States, and yield insights about the importance of watershed characteristics relative to mercury inputs. Information from other environments (lakes, wetlands, soil, atmosphere, glacial ice) also is summarized to help understand how mercury varies in space and time.

Circular↗

USGS1978

Wood River mining district, Idaho - intrusion-related lead-silver deposits derived from country rock source

Lead-silver deposits in the Wood River mining district occur in shear zones in hornfelsed argillite of the Devonian Milligen Formation near granitic plutons and under the Wood River thrust fault. The principal ore minerals are argentiferous galena and sphalerite; siderite is the principal gangue. The δ 34 S values of the sulfide minerals range from +2.2 to +15.0 permil, indicating that the sulfur had a shallow crustal source. Δ 34 S values between sphalerite and galena range from +2.3 to +3.4 permil, corresponding to sulfur isotope temperatures between 280° and 182 °C. Hydrothermal barite has a δ 34 S of +13.2 permil. Lead isotope ratios are radiogenic, also pointing to a shallow crustal source. Quartz gangue has δ 18 O of +16.4 permil and a calculated δ 18 O H20 at 270°C of +8.4 permil. This value is reasonable for a hydrothermal fluid that had reached equilibrium with the argillite country rock. The siderite gangue has δ 18 O and δ 13 C values of +14.0 and -5.5 permil, respectively. Fluid inclusions have homogenization temperatures of 244°-307°C and average 270°C. Freezing-stage measurements ranged from -1.85 to -2.8°C, suggesting salinities of 3.2 to 4.8 weight percent. The δD values of inclusion fluid in ore and gangue minerals are -110 to -120 permil. The geology, isotope, and fluid-inclusion data are consistent with a model of hydrothermal systems of meteoric water in faulted and shattered Paleozoic rocks near plutonic masses. This environment permitted deep circulation of the hydrothermal fluids, which dissolved the metals and sulfur from the Paleozoic host rocks and deposited ore in favorable beds or structures under the regional Wood River thrust fault.

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