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At least 559 records · Page 31Linked to original sources
USGS2002

Assessment of natural attenuation of ground-water contamination at sites FT03, LF13, and WP14/LF15, Dover Air Force Base, Delaware

Water-quality, aquifer-sediment, and hydrologic data were used to assess the effectiveness of natural attenuation of ground-water contamination at Fire Training Area Three, the Rubble Area Landfill, the Liquid Waste Disposal Landfill, and the Receiver Station Landfill in the East Management Unit of Dover Air Force Base, Delaware. These sites, which are contaminated with chlorinated solvents and fuel hydrocarbons, are undergoing long-term monitoring to determine if natural attenuation continues to sufficiently reduce contaminant concentrations to meet regulatory requirements. This report is the first assessment of the effectiveness of natural attenuation at these sites since long-term monitoring began in 1999, and follows a preliminary investigation done in 1995-96. This assessment was done by the U.S. Geological Survey in cooperation with the U.S. Air Force. Since 1995-96, additional information has been collected and used in the current assessment. The conclusions in this report are based primarily on ground-water samples collected from January through March 2000. Previous analytical results from selected wells, available geologic and geophysical well logs, and newly acquired information such as sediment organic-carbon measurements, hydraulic-conductivity measurements determined from slug tests on wells in the natural attenuation study area, and water-level measurements from surficial-aquifer wells also were used in this assessment. This information was used to: (1) calculate retardation factors and estimate contaminant migration velocities, (2) improve estimates of ground-water flow directions and inferred contaminant migration pathways, (3) better define the areal extent of contamination and the proximity of contaminants to discharge areas and the Base boundary, (4) develop a better understanding of the vertical variability of contaminant concentrations and redox conditions, (5) evaluate the effects of temporal changes on concentrations in the plumes and source areas, and (6) determine whether intrinsic biodegradation is occurring at these sites. The water-quality data indicate that intrinsic biodegradation is occurring at all three sites. The strongest indication of intrinsic biodegradation is the detection of tetrachloroethene and trichloroethene breakdown products within and down-gradient of the source areas. The patterns of electron acceptors and metabolic by-products indicate that contaminant biodegradation has changed the prevailing geochemistry of the surficial aquifer, creating the strongly reducing conditions necessary for chlorinated solvent biodegradation. Geochemical changes include depleted dissolved oxygen and elevated ferrous iron and methane levels relative to concentrations in uncontaminated zones of the surficial aquifer. At Fire Training Area Three and the Rubble Area Landfill sites, natural attenuation appears to be adequate for controlling the migration of the contaminant plumes. At the third site, the Liquid Waste Disposal and Receiver Station Landfills, the plume is larger and the uncertainty about the effectiveness of natural attenuation in reducing contaminant concentrations and controlling plume migration is greater. Ground-water data indicate, however, that U.S. Environmental Protection Agency maximum contaminant levels were not exceeded in any point-of-compliance wells located along the Base boundary. The information presented in this report led to the development of improved conceptual models for these sites, and to the recognition of four issues that are currently unclear and may need further study. These issues include delineating the areal and vertical extent of the contaminant plumes in greater detail, determining the extent of intrinsic biodegradation downgradient of the Liquid Waste Disposal and Receiver Station Landfills, determining the fate of contaminants in the ground-water discharge areas, and determining the effect of temporal variability in source concentrations and ground-water flow patterns on the plume migrating from the Liquid Waste Disposal and Receiver Station Landfills. Some of these issues have been addressed with additional data collection since the January-March 2000 sampling round.

Delaware↗
USGS1996

The effect of using different 0.45 μm filter membranes on 'dissolved' element concentrations in natural waters

The effect of 4 different 0.45 μm pore size filter membrane systems on the ‘dissolved’ concentration of 28 elements in 5 natural water samples of varying matrix is reported. In 3 of the 5 waters, consistently higher concentrations of most elements (minor and trace) are obtained using Nucleopore 47 mm filter and the cellulose acetate/nitrate 47 mm filter than those measured using the 142 mm cellulose nitrate MFS filter or the Gelman capsule 47 mm filter. These distinct and coherent patterns in elemental behaviour disappear for the other 2 samples, an organic-rich peat water of high suspended load and a mineralised sample high in Si and Ca. Thus the nature and degree of filtration artifacts is matrix-dependent. These trends are evident in both data sets produced by 2 independent laboratories using different instrumentation, techniques and calibrating procedures. The average relative standard deviation in elemental concentration across the 4 filter types is in the range 9–21%. The presence of such filtration artifacts must be considered in projects where, for example, seasonal variability of water composition is under examination, data from various sources are being merged or hydrogeochemical surveys are being conducted.

Applied Geochemistry↗
USGS2017

Geochemistry of mercury and other constituents in subsurface sediment—Analyses from 2011 and 2012 coring campaigns, Cache Creek Settling Basin, Yolo County, California

Cache Creek Settling Basin was constructed in 1937 to trap sediment from Cache Creek before delivery to the Yolo Bypass, a flood conveyance for the Sacramento River system that is tributary to the Sacramento–San Joaquin Delta. Sediment management options being considered by stakeholders in the Cache Creek Settling Basin include sediment excavation; however, that could expose sediments containing elevated mercury concentrations from historical mercury mining in the watershed. In cooperation with the California Department of Water Resources, the U.S. Geological Survey undertook sediment coring campaigns in 2011–12 (1) to describe lateral and vertical distributions of mercury concentrations in deposits of sediment in the Cache Creek Settling Basin and (2) to improve constraint of estimates of the rate of sediment deposition in the basin. Sediment cores were collected in the Cache Creek Settling Basin, Yolo County, California, during October 2011 at 10 locations and during August 2012 at 5 other locations. Total core depths ranged from approximately 4.6 to 13.7 meters (15 to 45 feet), with penetration to about 9.1 meters (30 feet) at most locations. Unsplit cores were logged for two geophysical parameters (gamma bulk density and magnetic susceptibility); then, selected cores were split lengthwise. One half of each core was then photographed and archived, and the other half was subsampled. Initial subsamples from the cores (20-centimeter composite samples from five predetermined depths in each profile) were analyzed for total mercury, methylmercury, total reduced sulfur, iron speciation, organic content (as the percentage of weight loss on ignition), and grain-size distribution. Detailed follow-up subsampling (3-centimeter intervals) was done at six locations along an east-west transect in the southern part of the Cache Creek Settling Basin and at one location in the northern part of the basin for analyses of total mercury; organic content; and cesium-137, which was used for dating. This report documents site characteristics; field and laboratory methods; and results of the analyses of each core section and subsample of these sediment cores, including associated quality-assurance and quality-control data.

California↗
USGS2009

The potential of mid- and near-infrared diffuse reflectance spectroscopy for determining major- and trace-element concentrations in soils from a geochemical survey of North America

In 2004, soils were collected at 220 sites along two transects across the USA and Canada as a pilot study for a planned soil geochemical survey of North America (North American Soil Geochemical Landscapes Project). The objective of the current study was to examine the potential of diffuse reflectance (DR) Fourier Transform (FT) mid-infrared (mid-IR) and near-infrared (NIRS) spectroscopy to reduce the need for conventional analysis for the determination of major and trace elements in such continental-scale surveys. Soil samples (n = 720) were collected from two transects (east-west across the USA, and north-south from Manitoba, Canada to El Paso, Texas (USA), n = 453 and 267, respectively). The samples came from 19 USA states and the province of Manitoba in Canada. They represented 31 types of land use (e.g., national forest, rangeland, etc.), and 123 different land covers (e.g., soybeans, oak forest, etc.). The samples represented a combination of depth-based sampling (0-5 cm) and horizon-based sampling (O, A and C horizons) with 123 different depths identified. The set was very diverse with few samples similar in land use, land cover, etc. All samples were analyzed by conventional means for the near-total concentration of 49 analytes (C total , C carbonate and C organic , and 46 major and trace elements). Spectra were obtained using dried, ground samples using a Digilab FTS-7000 FT spectrometer in the mid- (4000-400 cm -1 ) and near-infrared (10,000-4000 cm -1 ) at 4 cm -1 resolution (64 co-added scans per spectrum) using a Pike AutoDIFF DR autosampler. Partial least squares calibrations were develop using: (1) all samples as a calibration set; (2) samples evenly divided into calibration and validation sets based on spectral diversity; and (3) samples divided to have matching analyte concentrations in calibration and validation sets. In general, results supported the conclusion that neither mid-IR nor NIRS would be particularly useful in reducing the need for conventional analysis of soils from this continental-scale geochemical survey. The extreme sample diversity, likely caused by the widely varied parent material, land use at the site of collection (e.g., grazing, recreation, agriculture, etc.), and climate resulted in poor calibrations even for C total , C organic and C carbonate . The results indicated potential for mid-IR and NIRS to differentiate soils containing high concentrations (>100 mg/kg) of some metals (e.g., Co, Cr, Ni) from low-level samples (<50 mg/kg). However, because of the small number of high-level samples, it is possible that differentiation was based on factors other than metal concentration. Results for Mg and Sr were good, but results for other metals examined were fair to poor, at best. In essence, it appears that the great variation in chemical and physical properties seen in soils from this continental-scale survey resulted in each sample being virtually unique. Thus, suitable spectroscopic calibrations were generally not possible.

Applied Geochemistry↗
USGS2026

Understanding the resource potential of natural hydrogen on Earth: Scientific gaps, uncertainties and recommendations

A comprehensive scientific research roadmap is essential to bridge knowledge gaps and deepen the understanding of key geological, geochemical, and geophysical aspects of natural hydrogen (H 2 ) as a potential new energy resource. This paper reviews major scientific uncertainties on natural H 2 , suggesting research priorities, as a guide for defining exploration strategies, techniques, and data interpretation. The uncertainties concern all phases of the natural H 2 cycle, from generation (source rocks) through migration (advection and diffusion) and accumulation (reservoir and cap rocks) to the application and interpretation of subsurface and surface geochemical and geophysical exploration techniques. Understanding H 2 sources and generation rates (the amount of H 2 generated by a given volume of rock over time) is crucial for determining whether a geological H 2 system operates as a short-term dynamic system with rapid H 2 production and release, or as a conventional gas system with long-term accumulations, analogous to petroleum reservoirs. Preliminary estimates for serpentinisation, radiolysis, and organic matter degradation suggest that H 2 generation is not inherently fast, especially for non-hydrothermal continental systems (crystalline basement of shields, ophiolites, peridotite massifs, sedimentary basins), and long-term accumulations, like those of fossil natural gas systems, represent the most likely scenario. The mechanisms of H 2 migration through geological formations require application of fundamental principles of fluid-flow physics, distinguishing advection and diffusion, as well as their forms (from gas-phase, bubble flows to aqueous solutions). Additional studies of H 2 accumulation and retention in subsurface reservoirs could improve understanding of mechanisms of H 2 migration by focusing on the rock fluid-bearing properties and the factors affecting H 2 preservation, such as the presence of cap rocks impermeable to H 2 , pressure conditions, residence times, and microbial or abiotic consumption. Advanced techniques, including reservoir modelling, flow simulations, 3D imaging (micro-CT) of H 2 -bearing rocks, and extraction and analysis of gas occluded in rocks, can provide insights into the stability and potential recoverability of H 2 accumulations. The interpretation of surface exploration techniques, including gas geochemistry, geophysics, and remote sensing, long employed in mineral and energy resource exploration, is now being adapted for natural H 2 studies, but challenges remain in the data interpretation. Distinguishing H 2 seepage due to geological degassing from H 2 produced near the surface by modern microbial processes or artificial sources, such as hammering or drilling for soil-gas sampling, drilling into aquifers, and corrosion in boreholes, is an essential step in exploration. The simple detection of H 2 in soils, even in morphological structures like sub-circular depressions or “fairy circles”, cannot be cursorily interpreted as a signal of natural H 2 seepage from a deep source. A holistic geochemical approach, including isotopic analyses of gases associated with H 2 , is recommended to distinguish among the variety of possible H 2 origins. Observations of H 2 in wells should be interrogated to rule out possible artifacts such as corrosion and drill bit metamorphism. The integration of multiple geophysical methods, including seismic, gravimetric, magnetic, and electro-magnetic surveys, is recommended to mitigate interpretation ambiguities regarding the structure of a subsurface H 2 system (source and reservoir rocks, including fluid and gas storage), due to the non-uniqueness of rock-specific physical properties.

Earth-Science Reviews↗
USGS1994

Ground-water quality and geochemistry, Carson Desert, western Nevada

Aquifers in the Carson Desert are the primary source of drinking water, which is highly variable in chemical composition. In the shallow basin-fill aquifers, water chemistyr varies from a dilute calcium bicarbonate-dominated water beneath the irrigated areas to a saline sodium chloride- dominated water beneath unirrigated areas. Water samples from the shallow aquifers commonly have dissolved solids, chloride, magnesium, sulfate, arsenic, and manganese concentrations that exceed State of Nevada drinking-water standards. Water in the intermediante basin-fill aquifers is a dilute sodium bicarbonate type in the Fallon area and a distinctly more saline sodium chloride type in the Soda Lake-Upsal Hogback area. Dissolved solids, chloride, arsenic, fluoride, and manganese concen- trations commonly exceed drinking-water standards. The basalt aquifer contains a dilute sodium bicarbonate chloride water. Arsenic concentrations exceed standards in all sampled wells. The concen- trations of major constituents in ground water beneath the southern Carson Desert are the result of evapotranspiration and natural geochemical reactions with minerals derived mostly from igneous rocks. Water with higher concentrations of iron and manganese is near thermodynamic equilibrium with siderite and rhodochrosite and indicates that these elements may be limited by the solubility of their respective carbonate minerals. Naturally occurring radionuclides (uranium and radon-222) are present in ground water from the Carson Desert in concen- tratons higher than proposed drinking-water standards. High uranium concentrations in the shallow aquifers may be caused by evaporative concentration and the release of uranium during dissolution of iron and manganese oxides or the oxidation of sedimentary organic matter that typically has elevated uranium concentrations. Ground water in the Carson Desert does not appear to have be contaminated by synthetic organic chemicals.

Open-File Report↗
USGS2008

Natural gas geochemistry of sediments drilled on the 2005 Gulf of Mexico JIP cruise

In April and May 2005, cores were acquired and sub-sampled for gases in lease blocks Atwater Valley 13 and 14 and Keathley Canyon 151 during deep subseafloor drilling conducted as part of the JIP study of gas hydrates in the northern Gulf of Mexico. Sample types included sediment headspace gas, free gas derived from sediment gas exsolution, and gas exsolution from controlled degassing of pressurized cores. The gases measured both onboard and in shore-based labs were nitrogen, oxygen, hydrogen sulfide, carbon dioxide, and the hydrocarbons methane through hexane. The presence of seafloor mounds, seismic anomalies, a shallow sulfate-methane interface, and similar gas compositions and isotopic compositions near the seafloor and at depth suggest an upward flux of methane at both sites. Sediment gases at the Atwater Valley sites, where seafloor mounds and adjacent sediments were cored, strongly suggest a microbial source of methane, with very little thermogenic gas input. Sediment gas from all cores contained from about 96 to 99.9% methane, with the balance composed primarily of carbon dioxide. Methane to ethane ratios were greater than 1000, and often over 10,000. Gases from cores at Keathley Canyon were similar to those at Atwater Valley, however, deeper cores from Keathley Canyon contained more ethane, propane, and butane suggesting mixing with minor concentrations thermogenic gas. The isotopic composition of methane, ethane, and carbon dioxide were measured, and ??13C values range from -84.3 to -71.5???, -65.2 to -46.8???, and -23.5 to -3.0???, respectively, all consistent with microbial gas sources, early diagenesis of organic matter and perhaps biodegradation of petroleum. The presence of deep microbial gas at these sites here and elsewhere highlights a potentially significant, predominantly microbial gas source in the northern Gulf of Mexico.

Marine and Petroleum Geology↗
USGS1988

The association of uranium with organic matter in Holocene peat: An experimental leaching study

Uraniferous peat was sampled from surface layers of a Holocene U deposit in northeastern Washington State. Dried, sized, and homogenized peat that contained5980 ±307 ppm U was subjected to a variety of leaching conditions to determine the nature and strength of U-organic bonding in recently accumulated organic matter. The results complement previous experimental studies of U uptake on peat and suggest some natural or anthropogenic disturbances that are favorable for remobilizing U. The fraction of U leached in 24 h experiments at 25°C ranged from 0 to 95%. The most effective leach solutions contained anions capable of forming stable dissolved complexes with uranyl (UO 2 +2 ) cation. These included H 2 SO 4 ( pH = 1.5) and concentrated (0.01M) solutions of sodium bicarbonate-carbonate ( pH = 7.0–10.0), or sodium pyrophosphate ( pH = 10). Effective leaching by carbonate and pyrophosphate in the absence of added oxidant, and the insignificant effect of added oxidant (as pressurized O 2 ) strongly suggest that U is initially fixed on organic matter as an oxidized U(VI) species. Uranium is more strongly bound than some other polyvalent cations, based on its resistance to exchange in the presence of large excesses of dissolved Ca 2+ and Cu 2+ . Measurements of the rate of U leaching indicate faster rates in acid solution compared to carbonate solution, and are consisten with simultaneous attack of sites with different affinities for U. Sulfuric acid appears a good choice for commercial extraction of U from mined peat. In situ disturbances such as overliming of peat soils, addition of fertilizers containing pyrophosphate, or incursions of natural carbonate-rich waters could produce significant remobilization of U, and possibly compromise the quality of local domestic water supplies.

Applied Geochemistry↗
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↗
USGS1985

Mineralization of breccia pipes in northern Arizona

The Paleozoic sedimentary rocks on the Colorado Plateau of northern Arizona are host to hundreds ofbreccia pipes. The uranium and copper deposits in these breccia pipes transgress formation boundaries from the Mississippian Redwall Limestone to the Triassic Chinle Formation. They are not classic breccia pipes in that there is no volcanic rock associated with them in time or space. They are the result of solution-collapse within the Redwall Limestone and stoping of the overlying strata. The karst development in the Redwall Limestone began in the Mississippian and apparently either continued to the Triassic or was at least once again active during that time. The mineralization apparently occurred shortly thereafter, sometime during the Mesozoic. Mining activity in breccia pipes of the Grand Canyon region began during the nineteenth century and continues today with the operation of the Hack I, II, and III mines, although the exploited commodity has changed from Cu to U. Although small in size, these pipes contain samples with up to 55 percent U 3 O 8 and can yield ore averaging between 0.30 and 0.60 percent U 3 O 8 .Mineralization at the surface commonly occurs within nodules and concretions associated with pyrite and goethite and along fractures, while the primary ore of the unoxidized zones is commonly within a comminuted sandstone matrix surrounding breccia fragments of overlying formations. The ore mineral is uraninite, although associated with it are sphalerite, galena, chalcopyrite, tennantite, millerite, siegenite, and/molybdenite. Some of the surface nodules are encrusted with malachite and are exceptionally enriched in Ag. Pyrite is abundant, and the organic carbon content of some rocks is high enough to suggest that it, along with the pyrite, may be a reductant for uranium. In contrast, it is possible, if uranium were transported as a bicarbonate or carbonate complex, that only a conduit of brecciated rock was necessary to release CO 2 , thus disrupting the equilibrium and allowing uraninite to precipitate. An extensive suite of elements is significantly enriched in the mineralized rock: Ag, As, Ba, Cd, Co, Cr, Cs, Cu, Hg, Mo, Ni, Pb, Sb, Se, Sr, U, V, Zn, and the rare earth elements. Of these, Cu, Pb, Zn, Ag, and particularly As appear to be the best geochemical indicators of mineralized pipes. At present the origin of the mineralizing fluids is not known. The lack of extensive silification within the breccia, along with the 80 degrees to 173 degrees C fluid inclusion-filling temperatures on sphalerite, dolomite, quartz, and calcite, suggests relatively low-temperature mineralizing fluids, although heated in excess of what would be expected from the normal geothermal gradient on the Colorado Plateau. With the exception of the U-mineralized rock, the mineral assemblage and geochemistry is similar to Mississippi Valley-type deposits.

Economic Geology↗
USGS2003

Origin of minerals in joint and cleat systems of the Pottsville Formation, Black Warrior basin, Alabama: Implications for coalbed methane generation and production

Coalbed methane is produced from naturally fractured strata in the lower Pennsylvanian Pottsville Formation in the eastern part of the Black Warrior basin , Alabama . Major fracture systems include orthogonal fractures, which consist of systematic joints in siliciclastic strata and face cleats in coal that strike northeast throughout the basin . Calcite and minor amounts of pyrite commonly fill joints in sandstone and shale and, less commonly, cleats in coal. Joint -fill calcite postdates most pyrite and is a weakly ferroan, coarse-crystalline variety that formed during a period of uplift and erosion late in the burial history. Pyrite forms fine to coarse euhedral crystals that line joint walls or are complexly intergrown with calcite. Stable-isotope data reveal large variations in the carbon isotope composition of joint - and cleat -fill calcite (-10.3 to +24.3 per mil Peedee belemnite [PDB]) but only a relatively narrow range in the oxygen-isotope composition of this calcite (-16.2 to -4.1 per mil PDB). Negative carbon values can be attributed to (super 13) C-depleted CO (sub 2) derived from the oxidation of organic matter, and moderately to highly positive carbon values can be attributed to bacterial methanogenesis. Assuming crystallization temperatures of 20-50 degrees C, most joint- and cleat-fill calcite precipitated from fluids with delta (super 18) O ratios ranging from about -11 to +2 per mil standard mean ocean water (SMOW). Uplift and unroofing since the Mesozoic led to meteoric recharge of Pottsville strata and development of freshwater plumes that were fed by meteoric recharge along the structurally upturned, southeastern margin of the basin. Influxes of fresh water into the basin via faults and coalbeds facilitated late-stage bacterial methanogenesis, which accounts for the high gas content in coal and the carbonate cementation of joints and cleats. Diagenetic and epigenetic minerals can affect the transmissivity and storage capacity of joints and cleats, and they appear to contribute significantly to interwell heterogeneity in the Pottsville Formation. In highly productive coalbed methane fields, joint- and cleat-fill calcite have strongly positive delta (super 13) C values, whereas calcite fill has lower delta (super 13) C values in fields that are shut in or abandoned. Petrographic analysis and stable-isotope geochemistry of joint- and cleat-fill cements provide insight into coalbed methane reservoir quality and the nature and extent of reservoir compartmentalization, which are important factors governing methane production.

American Association of Petroleum Geologists Bulle↗
USGS2009

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies. Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.

Applied Geochemistry↗
USGS2023

Insights into the metamorphic history and origin of flake graphite mineralization at the Graphite Creek graphite deposit, Seward Peninsula, Alaska, USA

Graphite Creek is an unusual flake graphite deposit located on the Seward Peninsula, Alaska, USA. We present field observations, uranium-lead (U–Pb) monazite and titanite geochronology, carbon (C) and sulfur (S) stable isotope geochemistry, and graphite Raman spectroscopy data from this deposit that support a new model of flake graphite ore genesis in high-grade metamorphic environments. The Graphite Creek deposit is within the second sillimanite metamorphic zone of the Kigluaik Mountains gneiss dome. Flake graphite, hosted in sillimanite-gneiss and quartz-biotite paragneiss, occurs as disseminations and in sets of very high grade (up to 50 wt.% graphite), semi-massive to massive graphite lenses 0.2 to 1 m wide containing quartz, sillimanite, inclusions of garnet porphyroblasts, K-feldspar, and tourmaline. Restitic garnet, sillimanite, graphite, and biotite accumulations indicate a high degree of anatexis and melt loss. Strong yttrium depletion in monazite, high europium ratios (Eu/Eu*), and excursions of high strontium and thorium concentrations are consistent with biotite dehydration melting. Monazite and titanite U–Pb ages record peak metamorphism from ~ 97 to 92 million years ago (Ma) and a retrograde event at ~ 85 Ma. Raman spectroscopy confirms the presence of carbonaceous material and highly ordered, crystalline graphite. Graphite δ 13 C VPDB values of − 30 to − 12‰ and pyrrhotite δ 34 S VCDT values of − 14 to 10‰ are consistent with derivation from organic carbon and sulfur in sedimentary rocks, respectively. These data collectively suggest that formation of massive graphite lenses occurred approximately synchronously with high-temperature metamorphism and anatexis of a highly carbonaceous pelitic protolith. Melt extraction and fluid release associated with anatexis were likely crucial for concentrating graphite. High-temperature, graphitic migmatite sequences within high-strain shear zones may be favorable for the occurrence of high-grade flake graphite deposits.

Alaska↗
USGS2007

Geochemistry of rare earth elements in Permian coals from the Huaibei Coalfield, China

The rare earth elements (REEs) in coals are important because of: (a) REE patterns can be an indicator of the nature of source rocks of the mineral matter as well as sedimentary environments; (b) REEs abundance in coal may have industrial-significance. In this study, a total of thirty-four samples of Permian coal, partings, roof, and floor were collected from the Huaibei Coalfield, Anhui Province, China. Abundances of rare earth elements (REEs) and other elements in the samples were determined by inductively coupled-plasma mass spectrometry (ICP-MS) and inductively coupled-plasma atomic emission spectrometry (ICP-AES). The results show that the REEs are enriched in coals in the Huaibei Coalfield as compared with Chinese and U.S. coals and the world coal average. Coals in the Lower Shihezi Formation (No. 7, 5, and 4 Coals) and Upper Shihezi Formation (No. 3) have higher REE abundances than the coals in Shanxi Formation (No. 10). Magmatic intrusion resulted in high enrichment of REEs concentrations in No. 5 and 7 Coals. The REE abundances are positively correlated with the ash content. The mineral matter in these coals is mainly made up of clay minerals and carbonates. The REEs are positively correlated with lithophile elements including Si, Al, Ti, Fe, and Na, which are mainly distributed in clay minerals, indicating that REEs are contained mainly in clay minerals. The REE abundances in coals normalized by the ash are higher than that in partings. REEs abundances of coals cannot be accounted for by the REE content in the mineral matter, and some REEs associated with organic matter in coals. ?? 2007 Elsevier Ltd. All rights reserved.

Journal of Asian Earth Sciences↗
USGS2004

Chapter 11 The phosphoria formation: A model for forecasting global selenium sources to the environment

Mining of the Permian Phosphoria Formation — a marine, oil-generating, phosphatic shale — provided the selenium (Se) source implicated in the recent deaths of livestock in southeast Idaho. Field studies and the geohydrologic balance of Se in southeast Idaho confirm risk to animals from exposure to Se through leaching of mined waste shale into streams, discharge of regional drainage, and impoundment of drainage in wetland areas. Forage grown to stabilize waste rock contoured into hills or used as cross-valley fill provides an additional mechanism of Se exposure for the environment (Mackowiak et al., Chapter 19). The average Se concentration of the Meade Peak Member of the Phosphoria Formation is an order of magnitude higher than those of other exploited marine shales that have been linked to incidences of Se toxicosis via oil refining and irrigation in the western United States. The Phosphoria Formation accumulated in an environment that preserved organic matter and contributed to the formation of economic-grade phosphate and oil deposits. The addition of this phosphate-mining case study enables a comprehensive approach to the identification of marine sedimentary Se sources and a more complete range of ecotoxic field studies on which to establish the conditions and anthropogenic connections that determine uptake, release, and recycling of Se in food webs. A constructed conceptual model of Se pollution indicates that ancient organic-rich depositional marine basins, unre- stricted by age, are linked to the contemporary global distribution of Se source rocks. A global plot shows (a) the areal association of major basins hosting phosphate deposits and petroleum source rocks and (b) the importance of paleo-latitudinal setting in influencing the composition of the deposits. Given the geographic patterns, Se emerges as a contami- nant within specific regions of the globe that may limit phosphate mining, oil refining, and drainage of agricultural lands because of potential ecological risks to vulnerable food webs. Selenium also may serve as a geochemical exploration tool that signals an ancient productive biological environment.

Handbook of Exploration and Environmental Geochemi↗
USGS2010

Distribution, behavior, and transport of inorganic and methylmercury in a high gradient stream

Concentrations of Hg remain elevated in physical and biological media of the South River (Virginia, USA), despite the cessation of the industrial use of Hg in its watershed nearly six decades ago, and physical characteristics that would not seem to favor Hg(II)-methylation. A 3-a study of inorganic Hg (IHg) and methylmercury (MeHg) was conducted in physical media (soil, sediment, surface water, porewater and soil/sediment extracts) to identify non-point sources, transport mechanisms, and potential controls on Hg(II)-methylation. Data collected from surface water and sediment indicate that the majority of the non-point sources of IHg to the South River are within the first 14. km downstream from the historic point source. Partitioning data indicate that particle bound IHg is introduced in this reach, releasing dissolved and colloidal bound IHg, which is transported downstream. Extraction experiments revealed that floodplain soils released a higher fraction of their IHg content in aqueous extractions than fine-grained sediment (FGS). Based on ultrafiltration [<5000 nominal molecular weight cutoff (NMWC)] the majority of soil IHg released was colloidal in nature, providing evidence for the continued evolution of IHg for Hg(II)-methylation from soil. Strong seasonal patterns in MeHg concentrations were observed in surface water and sediment. The highest concentrations of MeHg in surface water were observed at moderate temperatures, suggesting that other factors limit net Hg(II)-methylation. Seasonal changes in sediment organic content and the fraction of 1. N KOH-extractable THg were also observed and may be important factors in controlling net Hg(II)-methylation rates. Sulfate concentrations in surface water are low and the evidence suggests that Fe reduction may be an important Hg(II)-methylation process. The highest sediment MeHg concentrations were observed in habitats with large amounts of FGS, which are more prevalent in the upper half of the study area due to the lower hydrologic gradient and agricultural impacts. Past and present land use practices and other geomorphologic controls contribute to the erosion of banks and accumulation of fine-grained sediment in this section of the river, acting as sources of IHg. ?? 2010 Elsevier Ltd.

Applied Geochemistry↗
USGS1996

Instability of bottom-water redox conditions during accumulation of Quaternary sediment in the Japan Sea

The concentrations of Cd, Cr, Cu, Mo, Ni, Sb, U, V, and Zn were measured in early Quaternary sediment (1.32 to 1.08 Ma) from the Oki Ridge in the Japan Sea. The elements were partitioned between a detrital fraction, composed of terrigenous and volcaniclastic aluminosilicate debris, and a marine fraction, composed of biogenic and hydrogenous debris derived from seawater. The most important factors controlling minor-element accumulation rates in the marine fraction were (1) primary productivity in the photic zone, which largely controlled the flux of particulate organic-matter-bound minor elements settling through the water column and onto the seafloor, and (2) bottom-water redox, which determined the suite of elements that accumulated directly from seawater. This marine fraction of minor elements on Oki Ridge recorded six periods of high minor-element abundance. Assuming a constant bulk sediment accumulation rate, each period lasted roughly 5,000 to 10,000 years with a 41,000-year cycle. Accumulation rates of individual elements such as Cd, Mo, and U suggest sulfate-reducing conditions were established in the bottom water during the 10,000-year periods; accumulation rates of Cr and V during the intervening periods are indicative of less reducing, denitrifying conditions. Interelement ratios, for example, Cu:Mo, V:Cr, and Sb:Mo, further reflect bottom-water instability, such that bottom-water redox actually varied from sulfate reducing to denitrifying during the periods of highest minor-element accumulation rates; it varied from denitrifying to oxidizing during the intervening periods. Sediment lithology supports these interpretations of the minor-element distributions; the sediment is finely laminated for several of the periods represented by Cd, Mo, and U maxima and weakly laminated to bioturbated for the intervening periods. The geochemistry of this sediment demonstrates the unambiguous signal of Mo, principally, but of several other minor elements as well in recording sulfate-reducing conditions in bottom water. The forcing function that altered their accumulation, that is, that altered primary productivity and bottom water redox conditions, is problematic. Currently held opinion suggests that O 2 depletion was most strongly developed during glacial advances. Low sea level during such times is interpreted to have enhanced primary productivity and restricted bottom-water advection.

Paleoceanography and Paleoclimatology↗
USGS1997

Natural or fertilizer-derived uranium in irrigation drainage: A case study in southeastern Colorado, U.S.A.

Drainage from heavily cultivated soils may be contaminated with U that is leached from the soil or added as a trace constituent of PO4-based commercial fertilizer. The effect of decades-long application of U-rich fertilizer on the U concentration of irrigation drainage was investigated in a small (14.2 km2) drainage basin in southeastern Colorado. The basin was chosen because previous reports indicated locally anomalous concentrations of dissolved NO3(6-36 mg l-1) and dissolved U (61 ??g l-1) at the mouth of the only stream. Results of this study indicated minimal impact of fertilizer-U compared to natural U leached from the local soils. Detailed sampling of the stream along a 6 mile (9.7 km) reach through heavily cultivated lands indicated marked decoupling of the buildup of dissolved NO3 and U. Dissolved U increased markedly in the upstream half of the reach and correlated positively with increases in Na, Mg, SO4, B and Li derived from leaching of surrounding shaley soils. In contrast, major increases in dissolved NO3 occurred farther downstream where stream water was heavily impacted by ground water return from extensively fertilized fields. Nitrogen isotopic measurements confirmed that dissolved NO3 originated from fertilizer and soil organic N (crop waste). Uranium isotopic measurements of variably uraniferous waters showed little evidence of contamination with fertilizer-derived U of isotopically distinct 234U/238U alpha activity ratio (A.R. = 1.0). Leaching experiments using local alkaline soil, irrigation water and U-rich fertilizer confirmed the ready leachability of soil-bound U and the comparative immobility of U added with liquid fertilizer. Relatively insoluble precipitates containing Ca-P-U were formed by mixing liquid fertilizer with water containing abundant dissolved Ca. In the local soils soluble Ca is provided by dissolution of abundant gypsum. Similar studies are needed elsewhere because the mobility of fertilizer-derived U is dependent on fertilizer type, porewater chemistry and soil properties (pH, moisture, mineralogy, texture).

Applied Geochemistry↗