SEARCH · USGS Science

Results for “Organic Geochemistry”

Search indexed USGS publications on groundwater, aquifers, geologic maps, mineral resources and earthquakes. Explore source records by subject and place.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 505 records · Page 28Linked to original sources

USGS1997

Hydrogeologic framework and geochemistry of the Edwards aquifer saline-water zone, south-central Texas

The Edwards aquifer supplies drinking water for more than 1 million people in south-central Texas. The saline-water zone of the Edwards aquifer extends from the downdip limit of freshwater to the southern and eastern edge of the Stuart City Formation. Water samples from 16 wells in the Edwards aquifer saline-water zone were collected during July–September 1990 and analyzed for major and minor dissolved constituents, selected stable isotopes, and radioisotopes. These data, supplemental data from an extensive water-quality data base, and data from other previous studies were interpreted to clarify the understanding of the saline-waterzone geochemistry. Most of the isotope and geochemical data indicate at least two distinct hydrological and geochemical regimes in the saline-water zone of the Edwards aquifer. On the basis of hydrogen and oxygen isotopes and radiocarbon data, the shallower updip regime is predominantly meteoric water that has been recharged probably from the freshwater zone within recent geologic time (less than tens of thousands of years). Also, on the basis of hydrogen and oxygen isotope data, water in the hydrologically stagnant regime (downdip) has been thermally altered in reactions with the carbonate rocks of the zone. The deeper water probably is much older than water in the shallow zone and is nearly stagnant relative to that in the shallow zone. The geochemical grouping observed in the wellwater data from well samples in the saline-water zone indicates that the zone is hydrologically compartmentalized, in part because of faults that function as barriers to downdip flow of recharge water. These fault barriers also probably impede updip flow. Flow compartmentalization and the resulting disparity in geochemistry between the two regimes indicate that updip movement of substantial amounts of saline water toward the freshwater zone is unlikely. Estimated in-place temperature of the samples collected indicates an increase with depth and (or) distance from the downdip limit of freshwater. The pH of the samples decreases with increasing distance from the downdip limit of freshwater, but the decrease is caused partly by the increase in temperature. Dissolved major ions and dissolved solids concentrations all indicate a progressive but monotonic increase in salinity from updip to downdip. The alkalinity of the water samples is predominantly bicarbonate because the low-molecular weight aliphatic-acid anion concentrations are small relative to the bicarbonate concentrations. The dissolved organic carbon concentrations also are lower than expected for an aquifer with economic amounts of oil and gas hydrocarbons.

Texas↗

USGS1985

Geologic setting, petrology, and geochemistry of stratiform sphalerite-galena-barite deposits, Red Dog Creek and Drenchwater Creek areas, northwestern Brooks Range, Alaska

Similar stratiform sphalerite-galena-barite deposits occur in the Red Dog Creek area, De Long Mountains quadrangle, and in the Drenchwater Creek area, Howard Pass quadrangle, northwestern Brooks Range, Alaska. The deposits, located approximately 180 km apart, are hosted by Mississippian and Pennsylvanian strata of the Kagvik structural sequence of late Paleozoic and early Mesozoic age. This sequence is situated in the lowermost structural plate of a series of predominantly east-striking, shallow-dipping thrust plates that characterize the regional structure. The deposits occur in shale, tuff, tuffaceous sandstone, altered chert, and quartz exhalite. These units are in places interlayered with or adjacent to bedded or nodular barite or submarine keratophyre flows. Chert and shale commonly contain abundant highly altered, fine-grained feldspar, pumice lapilli, and mafic volcanic rock fragments.The main types of occurrences at Red Dog Creek are: (1) disseminated and stratiform sulfides thinly bedded in organic-rich Mississippian and Pennsylvanian shale and chert, (2) massive sulfide veins and breccia fillings in silicified Mississippian and Pennsylvanian shale, and (3) stratiform sulfide-bearing lenses subdivided into (3a) quartz-exhalite with up to several percent sulfides and barite, (3b) massive sulfide-quartz lenses with up to several percent barite, and (3c) barite-quartz lenses with up to several percent sulfides.At Drenchwater Creek sulfides and barite occur as: (1) disseminations in shale, chert, tuff, and tuffaceous sandstone; (2) disseminations to aggregates in quartz exhalite; and (3) occurrences in veins crosscutting cleavages in brecciated chert and shale.The stratiform sulfides occur in zones up to several thousand meters long and several tens of meters thick. Preliminary grades at Red Dog Creek are 17.1 percent zinc, 5.0 percent lead, and 2.4 oz silver per ton contained in at least 85 million tons.The range of sulfide sulfur isotope values at Red Dog Creek is -16.6 per mil to +3.6 per mil. Sphalerite averages 0.8 per mil. Pyrite is isotopically lighter than coexisting sphalerite in quartz exhalite and massive sulfide lenses. This isotopic relationship is compatible with paragenetic relationships which show pyrite crystallized both earlier and later than other sulfides. Galena is isotopically lighter than coexisting sphalerite. Three groups of geologically and isotopically distinct barites exist including isotopic values appropriate for derivation from late Paleozoic seawater sulfate.Early in the depositional sequence isotopically light pyrite formed from organically reduced seawater sulfate. Sphalerite, galena, late pyrite, and some barite precipitated from two sulfur-bearing solutions that mixed at the mineralization site. Isotopically light barite associated with sulfides precipitated from oxidized H 2 S without seawater sulfate contribution. Lead isotope data from Red Dog and Drenchwater Creeks are compatible with generation of lead in a Phanerozoic mature island-arc setting, a typical orogene, or possibly a back-arc type intracratonic basin.The stratiform sphalerite-galena-barite deposits probably formed in an incipient island-arc environment near a continental margin, containing magmas of keratophyric and andesitic composition, where metal-laden hydrothermal fluids discharged into a deep (?) water, low-energy environment. Later intense deformation, associated with plate docking and thrusting, disrupted and partly remobilized and stratiform deposits.

Alaska↗

USGS1997

Petrography and geochemistry of selected lignite beds in the Gibbons Creek mine (Manning Formation, Jackson Group, Paleocene) of east-central Texas

This study examined the petrographic and geochemical characteristics of two lignite beds (3500 and 4500 beds, Manning Formation, Jackson Group, Eocene) that are mined at the Gibbons Creek mine in east-central Texas. The purpose of the study was to identify the relations among sample ash yield, coal petrography, and trace-element concentrations in lignite and adjoining rock layers of the Gibbons Creek mine. Particular interest was given to the distribution of 12 environmentally sensitive trace elements (As, Be, Cd, Cr, Co, Hg, Mn, Ni, Pb, Sb, Se, and U) that have been identified as potentially hazardous air pollutants (HAPs) in the United States Clean Air Act Amendments of 1990. Eleven lignite, floor, and rock parting samples were collected from incremental channel samples of the 3500 and 4500 beds that were exposed in a highwall of pit A3 at the Gibbons Creek mine. Short proximate and ultimate and forms of sulfur analyses were performed on all lignite samples, and lignite and rock samples were analyzed for 60 major, minor and trace elements. Representative splits of all lignite samples were ground and cast into pellets, and polished for petrographic analyses in blue-light fluorescence and reflected white light to determine liptinite, inertinite, and huminite maceral group percentages. The following observations summarize our results and conclusions about the geochemistry, petrography, and sedimentology of the 3500 and 4500 beds of the Gibbons Creek lignite deposit: (1) Weighted average dry (db) ash yield for the two beds is 29.7%, average total sulfur content is 2.6%, and average calorific value is 7832 Btu (18.22 MJ/kg). Ash yields are greatest in the lower bench (59.33% db) of the 3500 bed and in the upper bench of the 4500 bed (74.61% db). (2) For lignite samples (on a whole-coal basis), the distributions of two of the HAPs (Pb and Sb) are positively related to ash yield, probably indicating an inorganic affinity for these elements. By using cluster analysis we found that Be and Cd were poorly associated with ash yield, indicating a possible organic affinity, and that Ni, Se, Hg, U, and Pb cluster with most of the rare-earth elements. (3) The dominance of the crypto-eugelinite maceral subgroup over the crypto-humotelinite subgroup suggests that all Gibbons Creek lignites were subjected to peat-forming conditions (either biogenic or chemical) conducive to the degradation of wood cellular material into matrix gels, or that original plant material was not very woody and was prone to formation of matrix gels. The latter idea is supported by pollen studies of Gibbons Creek lignite beds; results indicate that the peat was derived in part from marsh plants low in wood tissue. (4) The occurrence of siliceous sponge spicules in the lower benches of the 3500 bed suggests the original peat in this part of the bed was deposited in standing, fresh water. (5) The petrographic data indicate that the upper sample interval of the 3500 bed contains more inertinite (3%) than the other samples studied. Increases in inertinite content in the upper part of the 3500 bed may have been associated with alteration of the peat by acids derived from the volcanic ash or could have been caused by fire, oxidation and drying, or biologic alteration of the peat in the paleo-mire.

International Journal of Coal Geology↗

USGS2026

Estimating paleotemperature using stable isotopes of soil-formed phyllosilicates from paleosols: A review

Fossilized soils, or paleosols, contain soil-formed phyllosilicates whose stable isotopic compositions may be used to calculate paleotemperature and thus reconstruct ancient terrestrial environments. Though paleosols are common in the geologic record, the use of phyllosilicates as paleotemperature proxies is limited in the literature owing to difficulties with selecting optimal paleosols, isolation from non-clay minerals and organic materials, mixtures of phyllosilicates in natural samples, wide variations of chemical compositions for phyllosilicates, and limited to undefined equilibrium fractionation factors between phyllosilicates-water. Here, we address these challenges by examining and comparing methods used for sample selection, mineral isolation, pretreatments, mineral identification, conventional and developing methods for oxygen and hydrogen isotopic analyses, and determination of phyllosilicate-water equilibrium fractionation factors, concluding with recommendations for best approaches for paleotemperature estimation. Additionally, we discuss how to identify and avoid detrital phyllosilicates, the impacts of diagenesis, comparison of stable isotope and non-isotope paleosol paleotemperature proxies, and challenges and opportunities for broadly using paleosols as paleoclimate archives. With ongoing efforts to refine this multi-faceted paleotemperature approach, the stable isotope geochemistry of soil-formed phyllosilicates continues to be an invaluable proxy system, enhancing our understanding of terrestrial paleoenvironments and paleoclimate.

Kansas↗

USGS2002

Geology and geochemistry of Carlin-type gold deposits in China

The Carlin-type gold deposits in China lie mostly near the margins of the Proterozoic Yangtze and Aba cratons. Submicron-sized gold in micron-sized arsenian pyrite is disseminated in fractured Cambrian through Triassic carbonaceous shale and carbonate rocks, and is associated with anomalous Hg, Sb, As, U, and Tl. Alteration typically includes silicification, argilization, and sulfidation. Aqueous fluid inclusions contain CO2, have relatively low temperatures of homogenization (250-150 ??C), and salinities (8-2 wt% equiv. NaCl) that typically decrease from early to later stages. The indicated pressures of 105-330x105 Pa correspond to depths in excess of 1.0 to 3.0 km, assuming hydrostatic conditions. The ??D values of fluid inclusions (-87 to -47%) and the calculated ??18 values for water in ore fluids (-2.1 to 16.2%) reflect interactions between meteoric water and sedimentary rocks. The ??13C values of calcite (-9 to 2%) and ??34S values of sulfides (-24 to 17%) suggest that C and S were derived from marine carbonate (and organic carbon) and diagenetic sulfides (and organic sulfur) in the vicinity of the deposits. Geologic relationships and geochronologic evidence indicate the deposits formed during a late phase of the Yanshanian orogeny (140-75 Ma). These gold deposits share much in common with the Carlin-type gold deposits in Nevada, USA. Both occur in carbonaceous, pyritic, sedimentary rocks deposited on extended margins of Precambrian cratons. The smaller Chinese deposits are generally in more siliceous rocks and the larger Nevada deposits in more calcareous rocks. In both countries, the host rocks prior to mineralization were affected by contractional deformation that produced many of the ore-controlling structures and the deposits do not show consistent spatial or genetic relationships with epizonal plutons. However, the Nevada deposits show broad spatial and temporal relationships with shifting patterns of calc-alkaline magmatism. The ore and alteration mineral assemblages, residence of gold, geochemical signatures, paragenetic sequence, and fluid inclusions are remarkably similar, which indicates that the deposits formed from low salinity, moderately acidic, CO2 and H2S-rich in the crust similar processes at relatively shallow levels in the crust (<5 km). However, the deposits in China are associated with large Hg, Sb, As, U, and Tl deposits, which may reflect higher background abundances of these elements. Stable isotopic data suggest meteoric water evolved to become ore fluids through interactions with sedimentary rocks, although contributions of volatiles or metals from deeper levels are present in some deposits in Nevada. In both countries, the deposits appear to have formed in an area of high paleothermal gradients after a change in stress regime during the later phases of orogenic activity.

Mineralium Deposita↗

USGS2017

Uranium delivery and uptake in a montane wetland, north-central Colorado, USA

Comprehensive sampling of peat, underlying lakebed sediments, and coexisting waters of a naturally uraniferous montane wetland are combined with hydrologic measurements to define the important controls on uranium (U) supply and uptake. The major source of U to the wetland is groundwater flowing through locally fractured and faulted granite gneiss of Proterozoic age. Dissolved U concentrations in four springs and one seep ranged from 20 to 83 ppb (μg/l). Maximum U concentrations are ∼300 ppm (mg/kg) in lakebed sediments and >3000 ppm in peat. Uranium in lakebed sediments is primarily stratabound in the more organic-rich layers, but samples of similar organic content display variable U concentrations. Post-depositional modifications include variable additions of U delivered by groundwater. Uranium distribution in peat is heterogeneous and primarily controlled by proximity to groundwater-fed springs and seeps that act as local point sources of U, and by proximity to groundwater directed along the peat/lakebeds contact. Uranium is initially sorbed on various organic components of peat as oxidized U(VI) present in groundwater. Selective extractions indicate that the majority of sorbed U remains as the oxidized species despite reducing conditions that should favor formation of U(IV). Possible explanations are kinetic hindrances related to strong complex formation between uranyl and humic substances, inhibition of anaerobic bacterial activity by low supply of dissolved iron and sulfate, and by cold temperatures.

Colorado↗

USGS1994

Geochemistry and hydrology of a calcareous fen within the Savage Fen wetlands complex, Minnesota, USA

Savage Fen is a wetlands complex at the base of north-facing bluffs in the Minnesota River Valley. The complex includes 27.8 hectares of calcareous fen that host rare calciphile plants whose populations are declining in Minnesota. Water and sediment compositions in the calcareous fen were studied to gain a better understanding of the hydrologie System that sustains the rare vegetation. Groundwater in the fen is a calcium-magnesium-bicarbonate type with circumneutral pH values. The groundwater composition is the resuit of interactions among water, dissolved and gaseous carbon species, carbonates, and ion exchangers. Shallow groundwater is distinguished from deep groundwater by smaller concentrations of chloride, sulfate, magnesium, and sodium, and larger concentrations of calcium, bicarbonate, hydrogen sulfide, and ammonium. Magnesian calcite is the prevalent carbonate in unconsolidated sedimentary fill beneath the fen and is an important source and sink for dissolved calcium, magnesium, and inorganic carbon. Calcite concentrations just below the water table are small because aerobic and anaerobic oxidation of organic matter increase the partial pressure of carbon dioxide ( P CO 2 ), decrease pH, and cause calcite to dissolve. Thick calcite accumulations just above the water table, in the root zone of calciphile plants, result from water table fluctuations and attendant changes in P CO 2 . Groundwater beneath Savage Fen recharges in lakes and ponds south of the fen and upwells to the surface within the fen. Water at the water table is a mixture of upwelling groundwater and water near the surface that flows downslope from higher elevations in the fen. Changes in oxygen and hydrogen isotope compositions of shallow groundwater indicate that the proportion of upwelling groundwater in shallow groundwater decreases downgradient in the calcareous fen. Encroachment of reed grasses into the calcareous fen may reflect human-caused disturbances in the recharge area.

Minnesota↗

USGS1997

Ground-water geochemistry of Kwajalein Island, Republic of the Marshall Islands, 1991

Ground water on Kwajalein Island is an important source of drinking water, particularly during periods of low rainfall. Fresh ground water is found as a thin lens underlain by saltwater. The concentration of dissolved ions increases with depth below the water table and proximity to the shoreline as high-salinity seawater mixes with fresh ground water. The maximum depth of the freshwater lens is 37 ft. Chloride is assumed to be non-reactive under the range of geochemical conditions on the atoll. The concentration of chloride thus is used as a conservative constituent to evaluate freshwater-saltwater mixing within the aquifer. Concentrations of sodium and for the most part, potassium and sulfate, also appear to be determined by conservative mixing between saltwater and rain. Concentrations of calcium, magnesium, and strontium are higher than expected from conservative mixing; these higher concentrations are a result of the dissolution of carbonate minerals. An excess in dissolved inorganic carbon results from carbonate-mineral dissolution and from the oxidation of organic matter in the aquifer; the stoichiometric difference between excess dissolved inorganic carbon and excess bivalent cations is used as a measure of the amount of organic-matter oxidation. Organic-matter oxidation also is indicated by the low concentration of dissolved oxygen, high concentrations of nutrients, and the presence of hydrogen sulfide in many of the water samples. Low levels of dissolved oxygen indicate oxic respiration, and sulfate reduction is indicated by hydrogen sulfide. The amount of dissolved inorganic carbon released during organic-matter oxidation is nearly equivalent to the amount of carbonate-mineral dissolution. Organic-matter oxidation and carbonate-mineral dissolution seem to be most active either in the unsaturated zone or near the top of the water table. The most plausible explanation is that high amounts of oxic respiration in the unsaturated zone generate carbon dioxide, which causes carbonate minerals to dissolve. Ground water contaminated by petroleum hydrocarbons had the highest levels of mineral dissolution and organic respiration (including sulfate reduction), indicating that bacteria are oxidizing the contaminants.

Kwajalein Island↗

USGS2014

Geochemistry of a marine phosphate deposit: A signpost to phosphogenesis

The Permian age Phosphoria Formation in southeastern Idaho and adjoining states represents possibly the largest marine phosphate deposit in the world. The Meade Peak Member, which contains the highest concentrations and amount of carbonate fluorapatite in the formation, was not significantly altered by mechanical reworking during deposition or subsequently by chemical weathering. Thus, its present composition reflects properties of the Phosphoria Sea that were critical to its accumulation and possibly to the accumulation of most major marine phosphate deposits. These properties included the chemistry of the water column, the hydrography, and the level of primary productivity. Calculated accumulation rates of the PO 4 3− and trace nutrients – Cd, Cu, Ni, and Zn – recorded a dynamic upwelling rate of c. 30 m year −1 that supported primary productivity of 2g C m −2 day −1 . High accumulation rates of the hydrogenous redox-sensitive trace metals – Cr, Mo, U, and V – reflect bottom-water redox conditions that were dominantly suboxic, maintained by a balance between the oxidation of ~ 8% of the organic detritus that settled out of the photic zone and advection of bottom water with a residence time of c .10 years. A limited flux into the basin of siliciclastic lithogenous debris contributed further to elevated concentrations of the seawater-derived sediment fractions.

Book chapter↗

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↗

USGS2016

Geochemistry of the Black Sea during the last 15 kyr: A protracted evolution of its hydrography and ecology

The Black Sea is a 2200 m deep anoxic, marine sea connected to the Mediterranean Sea via the Dardanelles Strait, Marmara Sea, and the 3 km wide, 35 m deep Bosphorus Strait. The biogeochemistry of sediment from the Anatolia slope has recorded changes to the hydrography leading up to and following the input of Mediterranean water at ~9.4 ka (10 3 years B.P.), when global sea level rose to the level of the Bosphorus sill and high-salinity water from the Mediterranean began to spill into the then brackish lake. The water initially mixed little with the lake water but cascaded to the bottom where it remained essentially isolated for ~1.6 kyr, the time required to fill the basin from the bottom up at its present input rate. The accumulation of Mo in the seafloor sediments, a proxy of bottom-water anoxia, increased sharply at ~8.6 ka, when bacterial respiration in the bottom water advanced to SO 4 2− reduction by the oxidation of organic detritus that settled out of the photic zone. Its accumulation remained elevated to ~5.6 ka, when it decreased 60%, only to again increase slightly at ~2.0 ka. The accumulation of C org , a proxy of primary productivity, increased threefold to fourfold at ~7.8 ka, when upward mixing of the high-salinity bottom water replaced the then thin veneer of the brackish photic zone in less than 50 years. From that time onward, the accumulation of C org , Mo, and additional trace metals has reflected the hydrography of the basin and Bosphorus Strait, controlled largely by climate.

Paleoceanography↗

USGS2007

Biogeochemistry of aquifer systems

Many studies have examined the differences in bacterial numbers, composition, and activity between groundwater and sediment samples. The majority of the literature has suggested higher percentages of attached bacteria than of unattached bacteria in aquifer systems, including in pristine aquifers and in aquifers contaminated with petroleum, creosote, sewage, and landfill leachate. In studies of aquifer biogeochemistry, much useful information regarding the microbial ecology of the system can be obtained by looking at organic compound and electron acceptor concentrations. An overview of approaches for identifying the redox characteristics of sediment is given in Christensen et al., and methods specific for determining reactive iron species in aquifers are reviewed by Heron et al. and Tuccillo et al. Other solid-phase electron acceptors that are important in aquifer systems include Mn(IV) oxides and barite. Important biogeochemical reactions catalyzed by indigenous microorganisms also are studied using a variety of experimental approaches including laboratory batch and column experiments as well as field-based in situ microcosms, tracer tests, and push-pull tests. The advantage of using a radiolabeled tracer in a study was that the reaction rates could be determined for the different steps in the denitrification pathway. Historically, researchers trained in geochemistry and hydrology created and tested hypotheses about aquifer biogeochemistry through laboratory assays and field-based geo-chemical measurements and experiments. Jeon et al. extended this research by using push-pull tests combined with stable-isotope probing to identify the specific members of the microbial community actively degrading naphthalene and rates of naphthalene degradation.

Book chapter↗

USGS2020

Geochemistry and age of groundwater in the Williston Basin, USA: Assessing potential effects of shale-oil production on groundwater quality

Thirty water wells were sampled in 2018 to understand the geochemistry and age of groundwater in the Williston Basin and assess potential effects of shale-oil production from the Three Forks-Bakken petroleum system (TBPS) on groundwater quality. Two geochemical groups are identified using hierarchical cluster analysis. Group 1 represents the younger (median 4 He = 21.49 × 10 −8 cm 3 STP/g), less chemically evolved water. Group 2 represents the older (median 4 He = 1389 × 10 −8 cm 3 STP/g), more chemically evolved water. At least two samples from each group contain elevated Cl concentrations (>70 mg/L). Br/Cl, B/Cl, and Li/Cl ratios indicate multiple sources account for the elevated Cl concentrations: septic-system leachate/road deicing salt, lignite beds in the aquifers, Pierre Shale beneath the aquifers, and water associated with the TBPS (one sample). 3 H and 14 C data indicate that 10.8, 21.6, and 67.6% of the samples are modern (post-1952), mixed age, and premodern (pre-1953), respectively. Lumped-parameter modeling of 3 H, SF 6 , 3 He, and 14 C concentrations indicates mean ages of the modern and premodern fractions range from ~1 to 30 years and 1300 to >30,000 years, respectively. Group 2 contains the highest CH 4 concentrations (0.0018–32 mg/L). δ 13 C–CH 4 and C 1 /C 2 +C 3 data in groundwater (−91.7 to −70.0‰ and 1280 to 13,600) indicate groundwater CH 4 is biogenic in origin and not from thermogenic shale gas. Four volatile organic compounds (VOCs) were detected in two samples. One mixed-age sample contains chloroform (0.25 μg/L) and dichloromethane (0.05 μg/L), which are probably associated with septic leachate. One premodern sample contains butane (0.082 μg/L) and n-pentane (0.032 μg/L), which are probably associated with thermogenic gas from a nearby oil well. The data indicate hydrocarbon production activities do not currently (2018) widely affect Cl, CH 4 , and VOC concentrations in groundwater. The predominance of premodern recharge in the aquifers indicates the groundwater moves relatively slowly, which could inhibit widespread chemical movement in groundwater overlying the TBPS. Comparison of groundwater-age data from five major unconventional hydrocarbon-production areas indicates aquifer zones used for water supply in the TBPS area have a lower risk of widespread chemical movement in groundwater than similar aquifer zones in the Fayetteville (Arkansas) and Marcellus (Pennsylvania) Shale production areas, but have a higher risk than similar aquifer zones in the Eagle Ford (Texas) and Haynesville (Texas, Louisiana) Shale production areas.

Montana, North Dakota, South Dakota↗

USGS2021

Exploring the potential of electrospray-Orbitrap for stable isotope analysis using nitrate as a model

Widely used isotope ratio mass spectrometers have limited capabilities to measure metabolites, drugs, or small polyatomic ions without the loss of structural isotopic information. A new approach has recently been introduced that uses electrospray ionization Orbitrap to measure multidimensional isotope signatures of intact polar compounds. Using nitrate as a model compound, this study aims to establish performance metrics for comparisons with conventional IRMS at the natural abundance level. We present a framework on how to convert isotopolog intensities to δ values that are commonly used in the isotope geochemistry community. The quantification of seven nitrate isotopologs provides multiple pathways for obtaining the primary N and O δ values including non-mass-dependent O isotope variations, as well as opportunities to explore nonrandom isotopic distributions (i.e., clumping effects) within molecular nitrate. Using automation and the adaptation of measurement principles that are specific to isotope ratio analysis, nitrate δ15NAIR, δ18OVSMOW, and δ17OVSMOW were measured with a long-term precision of 0.4‰ or better for isotopic reference materials and purified nitrate from environmental samples. In addition, we demonstrate promising results for unpurified environmental samples in liquid form. With these new developments, this study connects the two largely disparate mass spectrometry fields of bioanalytical MS and isotope ratio MS, thus providing a route to measure new isotopic signatures in diverse organic and inorganic solutes.

Analytical Chemistry↗

USGS2006

Mercury methylation influenced by areas of past mercury mining in the Terlingua district, Southwest Texas, USA

Speciation and microbial transformation of Hg was studied in mine waste from abandoned Hg mines in SW Texas to evaluate the potential for methyl-Hg production and degradation in mine wastes. In mine waste samples, total Hg, ionic Hg2+, Hg0, methyl-Hg, organic C, and total S concentrations were measured, various Hg compounds were identified using thermal desorption pyrolysis, and potential rates of Hg methylation and methyl-Hg demethylation were determined using isotopic-tracer methods. These data are the first reported for Hg mines in this region. Total Hg and methyl-Hg concentrations were also determined in stream sediment collected downstream from two of the mines to evaluate transport of Hg and methylation in surrounding ecosystems. Mine waste contains total Hg and methyl-Hg concentrations as high as 19,000 ??g/g and 1500 ng/g, respectively, which are among the highest concentrations reported at Hg mines worldwide. Pyrolysis analyses show that mine waste contains variable amounts of cinnabar, metacinnabar, Hg0, and Hg sorbed onto particles. Methyl-Hg concentrations in mine waste correlate positively with ionic Hg2+, organic C, and total S, which are geochemical parameters that influence processes of Hg cycling and methylation. Net methylation rates were as high as 11,000 ng/g/day, indicating significant microbial Hg methylation at some sites, especially in samples collected inside retorts. Microbially-mediated methyl-Hg demethylation was also observed in many samples, but where both methylation and demethylation were found, the potential rate of methylation was faster. Total Hg concentrations in stream sediment samples were generally below the probable effect concentration of 1.06 ??g/g, the Hg concentration above which harmful effects are likely to be observed in sediment dwelling organisms; whereas total Hg concentrations in mine waste samples were found to exceed this concentration, although this is a sediment quality guideline and is not directly applicable to mine waste. Although total Hg and methyl-Hg concentrations are locally high in some mine waste samples, little Hg appears to be exported from these Hg mines in stream sediment primarily due to the arid climate and lack of precipitation and mine runoff in this region. ?? 2006 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2007

Fate and groundwater impacts of produced water releases at OSPER "B" site, Osage County, Oklahoma

For the last 5 a, the authors have been investigating the transport, fate, natural attenuation and ecosystem impacts of inorganic and organic compounds in releases of produced water and associated hydrocarbons at the Osage-Skiatook Petroleum Environmental Research (OSPER) “A” and “B” sites, located in NE Oklahoma. Approximately 1.0 ha of land at OSPER “B”, located within the active Branstetter lease, is visibly affected by salt scarring, tree kills, soil salinization, and brine and petroleum contamination. Site “B” includes an active production tank battery and adjacent large brine pit, two injection well sites, one with an adjacent small pit, and an abandoned brine pit and tank battery site. Oil production in this lease started in 1938, and currently there are 10 wells that produce 0.2–0.5 m 3 /d (1–3 bbl/d) oil, and 8–16 m 3 /d (50–100 bbl/d) brine. Geochemical data from nearby oil wells show that the produced water source is a Na–Ca–Cl brine (∼150,000 mg/L TDS), with high Mg, but low SO 4 and dissolved organic concentrations. Groundwater impacts are being investigated by detailed chemical analyses of water from repeated sampling of 41 boreholes, 1–71 m deep. The most important results at OSPER “B” are: (1) significant amounts of produced water from the two active brine pits percolate into the surficial rocks and flow towards the adjacent Skiatook reservoir, but only minor amounts of liquid petroleum leave the brine pits; (2) produced-water brine and minor dissolved organics have penetrated the thick (3–7 m) shale and siltstone units resulting in the formation of three interconnected plumes of high-salinity water (5000–30,000 mg/L TDS) that extend towards the Skiatook reservoir from the two active and one abandoned brine pits; and (3) groundwater from the deep section of only one well, BR-01 located 330 m upslope and west of the site, appear not to be impacted by petroleum operations.

Oklahoma↗

USGS2005

Arsenic in ground water of the United States: occurrence and geochemistry

Concentrations of naturally occurring arsenic in ground water vary regionally due to a combination of climate and geology. Although slightly less than half of 30,000 arsenic analyses of ground water in the United States were 1 μg/L, about 10% exceeded 10 μg/L. At a broad regional scale, arsenic concentrations exceeding 10 μg/L appear to be more frequently observed in the western United States than in the eastern half. Arsenic concentrations in ground water of the Appalachian Highlands and the Atlantic Plain generally are very low ( 1 μg/L). Concentrations are somewhat greater in the Interior Plains and the Rocky Mountain System. Investigations of ground water in New England, Michigan, Minnesota, South Dakota, Oklahoma, and Wisconsin within the last decade suggest that arsenic concentrations exceeding 10 μg/L are more widespread and common than previously recognized. Arsenic release from iron oxide appears to be the most common cause of widespread arsenic concentrations exceeding 10 μg/L in ground water. This can occur in response to different geochemical conditions, including release of arsenic to ground water through reaction of iron oxide with either natural or anthropogenic (i.e., petroleum products) organic carbon. Iron oxide also can release arsenic to alkaline ground water, such as that found in some felsic volcanic rocks and alkaline aquifers of the western United States. Sulfide minerals are both a source and sink for arsenic. Geothermal water and high evaporation rates also are associated with arsenic concentrations 10g/L in ground and surface water, particularly in the west. Arsenic release from iron oxide appears to be the most common cause of widespread arsenic concentrations exceeding 10 µg/L a ground water. This can occur in response to different geochemical conditions, including release of arsenic to ground water through reaction of iron oxide with either natural or anthropogenic (i.e., petroleum products) organic carbon. Iron oxide also can release arsenic to alkaline ground water, such as that found in some felsic volcanic rocks and alkaline aquifers of the Western United States. Sulfide minerals are both a source and sink for arsenic. Geothermal water and high evaporation rates also are associated with arsenic concentrations ≥ 10g/L in ground and surface water, particularly in the west.

Ground Water↗

USGS2013

K-Ar dating and delta O-18-delta D characterization of nanometric illite from Ordovician K-bentonites of the Appalachians: illitization and the Acadian-Alleghenian tectonic activity

Nanometric (<0.02, 0.02–0.05, 0.05–0.1, 0.1–0.2 μm) illite fractions were separated from K-bentonite samples from northwestern Georgia, and studied by X-ray diffraction, oxygen and hydrogen isotope geochemistry, and K-Ar dated to more tightly constrain the tectono-thermal history of the Appalachian orogeny. Their XRD patterns are very similar for a given sample with respect to the peak shapes and positions. They are ordered illite-smectite mixed layers with only small variations in the relative proportions of illite and smectite interlayers. The illite crystal thickness distributions also are very homogeneous across the various size fractions of the same sample, but crystallite thickness varies from sample to sample. It can be concluded from the α-β 2 diagram that illitization occurred in all fractions by simultaneous nucleation and crystal growth, except for one sample. In that sample, a period of growth without nucleation was detected on top of the nucleation and growth episode. The K-Ar ages organize into two isochrons, the first at 319.9 ± 2.0 Ma with an initial 40 Ar/ 36 Ar ratio of 271 ± 66 Ma, and the second at 284.9 ± 1.2 Ma with an initial 40 Ar/ 36 Ar ratio of 310 ± 44. One data point above the older isochron and three between the two isochrons suggest a detrital contamination for the former separate and a possible further generation of nanoparticles for the three others. The samples with the older crystallization age consist of illite and illite-rich mixed-layers, and those with the younger age contain smectite-rich mixed-layers without illite, or illite-enriched illite-smectite mixed-layers. The K-Ar ages fit the age trends published previously for similar K-bentonites with regional age patterns between 240 and 270 Ma in the southwestern region, between 270 and 300 Ma in the central zone and the southern Appalachians, and between 315 and 370 Ma in the northernmost. Each of the two generations of illite crystals yields very consistent δ 18 O (V-SMOW) values at 17 ± 1‰ for the older and at 21 ± 1‰ for the younger. If crystallization temperatures of the nanometric illite were between 100 and 200 °C, as suggested by microthermometric determinations, the hydrothermal fluids had δ 18 O values of 4 ± 1‰ in the Dalton district and of 8 ± 1‰ in the Lafayette, Trenton, and Dirtseller districts at 100 °C, and of 11 ± 1 and 15 ± 1‰ in the same locations at 200 °C, probably because the water-rock isotope exchanges at elevated temperature occurred in rock-dominated systems. The δ 18 O of the fluids remained unchanged during local crystal growth, but varied depending on the geographic location of the samples and timing of illitization. The δD (V-SMOW) values of the different size fractions do not provide consistent information; they range from −70 to −45‰ for most nanometric and micrometric fractions (V-SMOW), but with no apparent coherent pattern. Nanometric illite-rich crystals from K-bentonite that underwent tectono-thermal alteration yield constant ages, constant clay mineralogy, constant crystallite size distributions for all of the nucleating and growing illite-type crystals of each sample, as well as constant δ 18 O values implying constant fluid chemistry, all pointing to geologically sudden crystallization.

Georgia↗