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USGS2007

Hydrodynamics of coalbed methane reservoirs in the Black Warrior Basin: Key to understanding reservoir performance and environmental issues

The Black Warrior Basin of the southeastern United States hosts one of the world's most prolific and long-lived coalbed methane plays, and the wealth of experience in this basin provides insight into the relationships among basin hydrology, production performance, and environmental issues. Along the southeast margin of the basin, meteoric recharge of reservoir coal beds exposed in an upturned fold limb exerts a strong control on water chemistry, reservoir pressure, and production performance. Fresh-water plumes containing Na-HCO3 waters with low TDS content extend from the structurally upturned basin margin into the interior of the basin. Northwest of the plumes, coal beds contain Na-Cl waters with moderate to high-TDS content. Carbon isotope data from produced gas and mineral cements suggest that the fresh-water plumes have been the site of significant bacterial activity and that the coalbed methane reservoirs contain a mixture of thermogenic and late-stage biogenic gases. Water produced from the fresh-water plumes may be disposed safely at the surface, whereas underground injection has been used locally to dispose of highly saline water. Wells in areas that had normal hydrostatic reservoir pressure prior to development tend to produce large volumes of water and may take up to 4 a to reach peak gas production. In contrast, wells drilled in naturally underpressured areas distal to the fresh-water plumes typically produce little water and achieve peak gas rates during the first year of production. Environmental debate has focused largely on issues associated with hydrologic communication between deep reservoir coal beds and shallow aquifers. In the coalbed methane fields of the Black Warrior Basin, a broad range of geologic evidence suggests that flow is effectively confined within coal and that the thick intervals of marine shale separating coal zones limit cross-formational flow. ?? 2007 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2007

Organic compounds in produced waters from coalbed natural gas wells in the Powder River Basin, Wyoming, USA

The organic composition of produced water samples from coalbed natural gas (CBNG) wells in the Powder River Basin, WY, sampled in 2001 and 2002 are reported as part of a larger study of the potential health and environmental effects of organic compounds derived from coal. The quality of CBNG produced waters is a potential environmental concern and disposal problem for CBNG producers, and no previous studies of organic compounds in CBNG produced water have been published. Organic compounds identified in the produced water samples included: phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, various non-aromatic compounds, and phthalates. Many of the identified organic compounds (phenols, heterocyclic compounds, PAHs) are probably coal-derived. PAHs represented the group of organic compounds most commonly observed. Concentrations of total PAHs ranged up to 23 ??g/L. Concentrations of individual compounds ranged from about 18 to <0.01 ??g/L. Temporal variability of organic compound concentrations was documented, as two wells with relatively high organic compound contents in produced water in 2001 had much lower concentrations in 2002. In many areas, including the PRB, coal strata provide aquifers for drinking water wells. Organic compounds observed in produced water are also likely present in drinking water supplied from wells in the coal. Some of the organic compounds identified in the produced water samples are potentially toxic, but at the levels measured in these samples are unlikely to have acute health effects. The human health effects of low-level, chronic exposure to coal-derived organic compounds in drinking water are currently unknown. Continuing studies will evaluate possible toxic effects from low level, chronic exposure to coal-derived organic compounds in drinking water supplies.

Applied Geochemistry↗

USGS2007

Composition of pore water in lake sediments, research site "B", Osage County, Oklahoma: Implications for lake water quality and benthic organisms

Shallow ground water at US Geological Survey research site B in northeastern Oklahoma is contaminated with NaCl-rich brine from past and present oil production operations. Contaminated ground water provides a potential source of salts, metals, and hydrocarbons to sediment and water of adjacent Skiatook Lake. A former brine storage pit 10 m in diameter that is now submerged just offshore from site B provides an additional source of contamination. Cores of the upper 16–40 cm of lake sediment were taken at the submerged brine pit, near an offshore saline seep, and at a location containing relatively uncontaminated lake sediment. Pore waters from each 2-cm interval were separated by centrifugation and analyzed for dissolved anions, cations, and trace elements. High concentrations of dissolved Cl − in pore waters (200–5000 mg/L) provide the most direct evidence of contamination, and contrast sharply with an average value of only about 37 mg/L in Skiatook Lake. Chloride/Br − mass ratios of 220–240 in contaminated pore waters are comparable to values in contaminated well waters collected onshore. Dissolved concentrations of Se, Pb, Cu and Ni in Cl − -rich pore waters exceed current US Environmental Protection Agency criteria for probable toxicity to aquatic life. At the submerged brine storage pit, the increase of Cl − concentration with depth is consistent with diffusion-dominant transport from deeper contaminated sediments. Near the offshore saline seep, pore water Cl − concentrations are consistently high and vary irregularly with depth, indicating probable Cl − transport by layer-directed advective flow. Estimated annual contributions of Cl − to the lake from the brine storage pit (∼20 kg) and the offshore seep (∼9 kg) can be applied to any number of similar sources. Generous estimates of the number of such sources at site B indicate minimal impact on water quality in the local inlet of Skiatook Lake. Similar methodologies can be applied at other sites of NaCl contamination surrounding Skiatook Lake and elsewhere.

Oklahoma↗

USGS2007

Mode of occurrence and environmental mobility of oil-field radioactive material at US Geological Survey research site B, Osage-Skiatook Project, northeastern Oklahoma

Two samples of produced-water collected from a storage tank at US Geological Survey research site B, near Skiatook Lake in northeastern Oklahoma, have activity concentrations of dissolved 226 Ra and 228 Ra that are about 1500 disintegrations/min/L (dpm/L). Produced-water also contains minor amounts of small (5–50 μm) suspended grains of Ra-bearing BaSO 4 (barite). Precipitation of radioactive barite scale in the storage tank is probably hindered by low concentrations of dissolved SO 4 (2.5 mg/L) in the produced-water. Sediments in a storage pit used to temporarily collect releases of produced-water have marginally elevated concentrations of “excess” Ra (several dpm/g), that are 15–65% above natural background values. Tank and pit waters are chemically oversaturated with barite, and some small (2–20 μm) barite grains observed in the pit sediments could be transferred from the tank or formed in place. Measurements of the concentrations of Ba and excess Ra isotopes in the pit sediments show variations with depth that are consistent with relatively uniform deposition and progressive burial of an insoluble Ra-bearing host (barite?). The short-lived 228 Ra isotope (half-life = 5.76 a) shows greater reductions with depth than 226 Ra (half-life = 1600 a), that are likely explained by radioactive decay. The 228 Ra/ 226 Ra activity ratio of excess Ra in uppermost pit sediments (1.13–1.17) is close to the ratio measured in the samples of produced-water (0.97, 1.14). Declines in Ra activity ratio (excess) with sediment depth can be used to estimate an average rate of burial of 4 cm/a for the Ra-bearing contaminant. Local shallow ground waters contaminated with NaCl from produced-water have low dissolved Ra (<20 dpm/L) and also are oversaturated with barite. Barite is a highly insoluble Ra host that probably limits the environmental mobility of Ra at site B.

Oklahoma↗

USGS2007

Geologic controls on movement of produced-water releases at US geological survey research Site A, Skiatook lake, Osage county, Oklahoma

Highly saline produced water was released from multiple sources during oil field operations from 1913 to 1973 at the USGS research Site A on Skiatook Lake in northeastern Oklahoma. Two pits, designed to hold produced water and oil, were major sources for release of these fluids at the site. Produced water spills from these and other features moved downslope following topography and downdip by percolating through permeable eolian sand and colluvium, underlying permeable sandstone, and, to a lesser extent, through shales and mudstones. Saline water penetrated progressively deeper units as it moved through the gently dipping bedrock to the north and NW. A large eroded salt scar north of the pits coincides with underlying fine-grained rocks that have retained substantial concentrations of salt, causing slow revegetation. Where not eroded, thick eolian sand or permeable sandstone bedrock is near the surface, and vegetation has been little affected or has reestablished itself after the introduced salt was flushed by precipitation. The extent of salt-contaminated bedrock extends well beyond existing surface salt scars. These results indicate that one of the legacies of surface salt spills can be a volume of subsurface salinization larger than the visible surface disturbance.

Oklahoma↗

USGS2007

Use of dissolved chloride concentrations in tributary streams to support geospatial estimates of Cl contamination potential near Skiatook Lake, northeastern Oklahoma

Releases of NaCl-rich (>100 000 mg/L) water that is co-produced from petroleum wells can adversely affect the quality of ground and surface waters. To evaluate produced water impacts on lakes, rivers and streams, an assessment of the contamination potential must be attainable using reliable and cost-effective methods. This study examines the feasibility of using geographic information system (GIS) analysis to assess the contamination potential of Cl to Skiatook Lake in the Hominy Creek drainage basin in northeastern Oklahoma. GIS-based predictions of affects of Cl within individual subdrainages are supported by measurements of Cl concentration and discharge in 19 tributaries to Skiatook Lake. Dissolved Cl concentrations measured in October, 2004 provide a snapshot of conditions assumed to be reasonably representative of typical inputs to the lake. Chloride concentrations ranged from 5.8 to 2300 mg/L and compare to a value of 34 mg/L in the lake. At the time of sampling, Hominy Creek provided 63% of the surface water entering the lake and 80% of the Cl load. The Cl load from the other tributaries is relatively small (<600 kg/day) compared to Hominy Creek (11 900 kg/day) because their discharges are relatively small (<0.44 m3/s) relative to Hominy Creek (3.1 m3/s). Examination of chemical components other than Cl in stream and lake waters indicates that many species, such as SO4, cannot be used to assess contamination potential because they participate in a number of common biogeochemical processes that alter their concentrations. GIS estimates of well density, well proximity to tributaries (wells within 200 m), and subdrainage area identified tributaries with the most potential for Cl contamination. Tributaries with large measured Cl concentrations (>150 mg/L) were generally in subdrainages with greater well density (>15 wells/km2), relatively large numbers of petroleum wells in close proximity (>2 proximity wells/stream km), and relatively small discharge (<0.005 m3/s). GIS calculations of subdrainage areas can be used to estimate the expected discharge of the tributary for each subdrainage. GIS-based assessment of Cl contamination potential at Skiatook Lake and at other lakes surrounded by oil fields can proceed even when direct measurements of Cl or discharge in tributary streams may be limited or absent.

Oklahoma↗

USGS2007

Centimeter-scale characterization of biogeochemical gradients at a wetland-aquifer interface using capillary electrophoresis

Steep biogeochemical gradients were measured at mixing interfaces in a wetland-aquifer system impacted by landfill leachate in Norman, Oklahoma. The system lies within a reworked alluvial plain and is characterized by layered low hydraulic conductivity wetland sediments interbedded with sandy aquifer material. Using cm-scale passive diffusion samplers, "peepers", water samples were collected in a depth profile to span interfaces between surface water and a sequence of deeper sedimentary layers. Geochemical indicators including electron acceptors, low-molecular-weight organic acids, base cations, and NH4+ were analyzed by capillary electrophoresis (CE) and field techniques to maximize the small sample volumes available from the centimeter-scale peepers. Steep concentration gradients of biogeochemical indicators were observed at various interfaces including those created at sedimentary boundaries and boundaries created by heterogeneities in organic C and available electron acceptors. At the sediment-water interface, chemical profiles with depth suggest that SO42 - and Fe reduction dominate driven by inputs of organic C from the wetland and availability of electron acceptors. Deeper in the sediments (not associated with a lithologic boundary), a steep gradient of organic acids (acetate maximum 8.8 mM) and NH4+ (maximum 36 mM) is observed due to a localized source of organic matter coupled with the lack of electron acceptor inputs. These findings highlight the importance of quantifying the redox reactions occurring in small interface zones and assessing their role on biogeochemical cycling at the system scale.

Oklahoma↗

USGS2007

Evaluation of sulfate reduction at experimentally induced mixing interfaces using small-scale push-pull tests in an aquifer-wetland system

This paper presents small-scale push–pull tests designed to evaluate the kinetic controls on SO 4 2 - "> SO42- reduction in situ at mixing interfaces between a wetland and aquifer impacted by landfill leachate at the Norman Landfill research site, Norman, OK. Quantifying the rates of redox reactions initiated at interfaces is of great interest because interfaces have been shown to be zones of increased biogeochemical transformations and thus may play an important role in natural attenuation. To mimic the aquifer–wetland interface and evaluate reaction rates, SO 4 2 - "> SO42- -rich anaerobic aquifer water ( ∼ 100 mg / L SO 4 2 - ) "> (∼100mg/LSO42-) was introduced into SO 4 2 - "> SO42- -depleted wetland porewater via push–pull tests. Results showed SO 4 2 - "> SO42- reduction was stimulated by the mixing of these waters and first-order rate coefficients were comparable to those measured in other push–pull studies. However, rate data were complex involving either multiple first-order rate coefficients or a more complex rate order. In addition, a lag phase was observed prior to SO 4 2 - "> SO42- reduction that persisted until the mixing interface between test solution and native water was recovered, irrespective of temporal and spatial constraints. The lag phase was not eliminated by the addition of electron donor (acetate) to the injected test solution. Subsequent push–pull tests designed to elucidate the nature of the lag phase support the importance of the mixing interface in controlling terminal electron accepting processes. These data suggest redox reactions may occur rapidly at the mixing interface between injected and native waters but not in the injected bulk water mass. Under these circumstances, push–pull test data should be evaluated to ensure the apparent rate is actually a function of time and that complexities in rate data be considered.

Oklahoma↗

USGS2008

Dissolved metals and associated constituents in abandoned coal-mine discharges, Pennsylvania, USA. Part 2: Geochemical controls on constituent concentrations

Water-quality data for discharges from 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania reveal complex relations among the pH and dissolved solute concentrations that can be explained with geochemical equilibrium models. Observed values of pH ranged from 2.7 to 7.3 in the coal-mine discharges (CMD). Generally, flow rates were smaller and solute concentrations were greater for low-pH CMD samples; pH typically increased with flow rate. Although the frequency distribution of pH was similar for the anthracite and bituminous discharges, the bituminous discharges had smaller median flow rates; greater concentrations of SO4, Fe, Al, As, Cd, Cu, Ni and Sr; comparable concentrations of Mn, Cd, Zn and Se; and smaller concentrations of Ba and Pb than anthracite discharges with the same pH values. The observed relations between the pH and constituent concentrations can be attributed to (1) dilution of acidic water by near-neutral or alkaline ground water; (2) solubility control of Al, Fe, Mn, Ba and Sr by hydroxide, sulfate, and/or carbonate minerals; and (3) aqueous SO4-complexation and surface-complexation (adsorption) reactions. The formation of AlSO4+ and AlHSO42 + complexes adds to the total dissolved Al concentration at equilibrium with Al(OH)3 and/or Al hydroxysulfate phases and can account for 10-20 times greater concentrations of dissolved Al in SO4-laden bituminous discharges compared to anthracite discharges at pH of 5. Sulfate complexation can also account for 10-30 times greater concentrations of dissolved FeIII concentrations at equilibrium with Fe(OH)3 and/or schwertmannite (Fe8O8(OH)4.5(SO4)1.75) at pH of 3-5. In contrast, lower Ba concentrations in bituminous discharges indicate that elevated SO4 concentrations in these CMD sources could limit Ba concentrations by the precipitation of barite (BaSO4). Coprecipitation of Sr with barite could limit concentrations of this element. However, concentrations of dissolved Pb, Cu, Cd, Zn, and most other trace cations in CMD samples were orders of magnitude less than equilibrium with sulfate, carbonate, and/or hydroxide minerals. Surface complexation (adsorption) by hydrous ferric oxides (HFO) could account for the decreased concentrations of these divalent cations with increased pH. In contrast, increased concentrations of As and, to a lesser extent, Se with increased pH could result from the adsorption of these oxyanions by HFO at low pH and desorption at near-neutral pH. Hence, the solute concentrations in CMD and the purity of associated "ochres" formed in CMD settings are expected to vary with pH and aqueous SO4 concentration, with potential for elevated SO4, As and Se in ochres formed at low pH and elevated Cu, Cd, Pb and Zn in ochres formed at near-neutral pH. Elevated SO4 content of ochres could enhance the adsorption of cations at low pH, but decrease the adsorption of anions such as As. Such information on environmental processes that control element concentrations in aqueous samples and associated precipitates could be useful in the design of systems to reduce dissolved contaminant concentrations and/or to recover potentially valuable constituents in mine effluents.

Applied Geochemistry↗

USGS2008

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4 are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe2+ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach-seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7-7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.

Applied Geochemistry↗

USGS2008

Dissolved metals and associated constituents in abandoned coal-mine discharges, Pennsylvania, USA. Part 1: Constituent quantities and correlations

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s-1, with a median of 18.4 L s-1. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-??m pore-size filter) SO4 (34-2000), Fe (0.046-512), Mn (0.019-74), and Al (0.007-108) varied widely. Predominant metalloid elements were Si (2.7-31.3 mg L-1), B (<1-260 ??g L-1), Ge (<0.01-0.57 ??g L-1), and As (<0.03-64 ??g L-1). The most abundant trace metals, in order of median concentrations (range in ??g/L), were Zn (0.6-10,000), Ni (2.6-3200), Co (0.27-3100), Ti (0.65-28), Cu (0.4-190), Cr (<0.5-72), Pb (<0.05-11) and Cd (<0.01-16). Gold was detected at concentrations greater than 0.0005 ??g L-1 in 97% of the samples, with a maximum of 0.0175 ??g L-1. No samples had detectable concentrations of Hg, Os or Pt, and less than half of the samples had detectable Pd, Ag, Ru, Ta, Nb, Re or Sn. Predominant rare-earth elements, in order of median concentrations (range in ??g/L), were Y (0.11-530), Ce (0.01-370), Sc (1.0-36), Nd (0.006-260), La (0.005-140), Gd (0.005-110), Dy (0.002-99) and Sm (<0.005-79). Although dissolved Fe was not correlated with pH, concentrations of Al, Mn, most trace metals, and rare earths were negatively correlated with pH, consistent with solubility or sorption controls. In contrast, As was positively correlated with pH. None of the 140 CMD samples met all US Environmental Protection Agency (USEPA) continuous-concentration criteria for protection of freshwater aquatic organisms; the samples exceeded criteria for Al, Fe, Co, Ni, and/or Zn. Ten percent of the samples exceeded USEPA primary drinking-water standards for As, and 33% exceeded standards for Be. Only one sample met drinking-water standards for inorganic constituents in a public water supply. Except for S, the nonmetal elements (S > C > P = N = Se) were not elevated in the CMD samples compared to average river water or seawater. Compared to seawater, the CMD samples also were poor in halogens (Cl > Br > I > F), alkalies (Na > K > Li > Rb > Cs), most alkaline earths (Ca > Mg > Sr), and most metalloids but were enriched by two to four orders of magnitude with Fe, Al, Mn, Co, Be, Sc, Y and the lanthanide rare-earth elements, and one order of magnitude with Ni and Zn. The ochre samples collected at a subset of 10 sites in 2003 were dominantly goethite with minor ferrihydrite or lepidocrocite. None of the samples for this subset contained schwertmannite or was Al rich, but most contained minor aluminosilicate detritus. Compared to concentrations in global average shale, the ochres were rich in Fe, Ag, As and Au, but were poor in most other metals and rare earths. The ochres were not enriched compared to commercial ore deposits mined for Au or other valuable metals. Although similar to commercial Fe ores in composition, the ochres are dispersed and present in relatively small quantities at most sites. Nevertheless, the ochres could be valuable for use as pigment.

Applied Geochemistry↗

USGS2008

Temporal variation and the effect of rainfall on metals flux from the historic Beatson mine, Prince William Sound, Alaska, USA

Several abandoned Cu mines are located along the shore of Prince William Sound, AK, where the effect of mining-related discharge upon shoreline ecosystems is unknown. To determine the magnitude of this effect at the former Beatson mine, the largest Cu mine in the region and a Besshi-type massive sulfide ore deposit, trace metal concentration and flux were measured in surface run-off from remnant, mineralized workings and waste. Samples were collected from seepage waters; a remnant glory hole which is now a pit lake; a braided stream draining an area of mineralized rock, underground mine workings, and waste piles; and a background location upstream of the mine workings and mineralized rock. In the background stream pH averaged ???7.3, specific conductivity (SC) was ???40 ??S/cm, and the aqueous components indicative of sulfide mineral weathering, SO4 and trace metals, were at detection limits or lower. In the braided stream below the mine workings and waste piles, pH usually varied from 6.7 to 7.1, SC varied from 40 to 120 ??S/cm, SO4 had maximum concentrations of 32 mg/L, and the trace metals Cu, Ni, Pb, and Zn showed maximum total acid extractable concentrations of 186, 5.9, 6.2 and 343 ??g/L, respectively. With an annual rainfall of ???340 cm (estimated from the 2006 water year) it was expected that rain water would have a large effect on the chemistry of the braided stream draining the mine site. A linear mixing model with two end members, seepage water from mineralized rock and background water, estimated that the braided stream contained 10-35% mine drainage. After rain events the braided stream showed a decrease in pH, SC, Ca + Mg, SO4, and alkalinity, due to dilution. The trace metals Ni and Zn followed this same pattern. Sodium + K and Cl did not vary between the background and braided stream, nor did they vary with rainfall. At approximately 2 and 3 mg/L, respectively, these concentrations are similar to concentrations found in rainfall on the coasts of North America. High concentrations of total acid extractable Al and Fe were found at near-neutral pH in most of the waters collected at the site. Equilibrium solubility simulations, performed with PHREEQC, show that the stream waters are saturated with respect to Al, Fe and SiO2 solid phases. Because the "dissolved" sample fractions (acid preserved and filtered to 0.45 ??m) show significant concentrations of Al and Fe it is presumed that these are present as colloids. The relationship between concentrations of Al and Fe, and rainfall was the opposite of that observed for the major ions Ca + Mg, SO4, and alkalinity, in that Al and Fe concentrations increased with increasing rainfall. Concentrations of Cu and Pb followed the same pattern. Adsorption calculations were performed with Visual MINTEQ, using the diffuse double layer electrostatic model and surface complexation constants for the ferrihydrite surface. These results suggest that 30-93% of Cu and 58-97% of Pb was adsorbed to ferrihydrite precipitates in the stream waters. Ni and Zn showed little adsorption in this pH range. Flux calculations show that the total mass of trace metals transported from the mine site, during the 60 day study period, was ranked as Zn (196 kg) > Cu (87 kg) > Pb(1.9 kg) ??? Ni(1.9 kg). Nickel and Zn were transported mostly as dissolved species while Cu and Pb were transported mostly as adsorbed species. pH control on adsorption was evident when Cu and Pb isotherms were normalized by ferrihydrite flux. Decreased stream water pH due to periods of frequent and high volume rain events would cause desorption of Cu and Pb from the ferrihydrite surface, thus changing not only their speciation in solution but also their mechanism of transport. ?? 2007 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2008

Chromium, chromium isotopes and selected trace elements, western Mojave Desert, USA

Chromium(VI) concentrations in excess of the California Maximum Contaminant Level (MCL) of 50 μg/L occur naturally in alkaline, oxic ground-water in alluvial aquifers in the western Mojave Desert, southern California. The highest concentrations were measured in aquifers eroded from mafic rock, but Cr(VI) as high as 27 μg/L was measured in aquifers eroded from granitic rock. Chromium(VI) concentrations did not exceed 5 μg/L at pH < 7.5 regardless of geology. δ 53 Cr values in native ground-water ranged from 0.7 to 5.1‰ and values were fractionated relative to the average δ 53 Cr composition of 0‰ in the earth’s crust. Positive δ 53 Cr values of 1.2 and 2.3‰ were measured in ground-water recharge areas having low Cr concentrations, consistent with the addition of Cr(VI) that was fractionated on mineral surfaces prior to entering solution. δ 53 Cr values, although variable, did not consistently increase or decrease with increasing Cr concentrations as ground-water flowed down gradient through more oxic portions of the aquifer. However, increasing δ 53 Cr values were observed as dissolved O 2 concentrations decreased, and Cr(VI) was reduced to Cr(III), and subsequently removed from solution. As a result, the highest δ 53 Cr values were measured in water from deep wells, and wells in discharge areas near dry lakes at the downgradient end of long flow paths through alluvial aquifers. δ 53 Cr values at an industrial site overlying mafic alluvium having high natural background Cr(VI) concentrations ranged from −0.1 to 3.2‰. Near zero δ 53 Cr values at the site were the result of anthropogenic Cr. However, mixing with native ground-water and fractionation of Cr within the plume increased δ 53 Cr values at the site. Although δ 53 Cr was not necessarily diagnostic of anthropogenic Cr, it was possible to identify the extent of anthropogenic Cr at the site on the basis of the δ 53 Cr values in conjunction with major-ion data, and the δ 18 O and δD composition of water from wells.

Applied Geochemistry↗

USGS2008

A comparison of winter mercury accumulation at forested and no-canopy sites measured with different snow sampling techniques

Atmospheric mercury (Hg) is delivered to ecosystems via rain, snow, cloud/fog, and dry deposition. The importance of snow, especially snow that has passed through the forest canopy (throughfall), in delivering Hg to terrestrial ecosystems has received little attention in the literature. The snowpack is a dynamic system that links atmospheric deposition and ecosystem cycling through deposition and emission of deposited Hg. To examine the magnitude of Hg delivery via snowfall, and to illuminate processes affecting Hg flux to catchments during winter (cold season), Hg in snow in no-canopy areas and under forest canopies measured with four collection methods were compared: (1) Hg in wet precipitation as measured by the Mercury Deposition Network (MDN) for the site in Acadia National Park, Maine, USA, (2) event throughfall (collected after snowfall cessation for accumulations of >8 cm), (3) season-long throughfall collected using the same apparatus for event sampling but deployed for the entire cold season, and (4) snowpack sampling. Estimates (mean ± SE) of Hg deposition using these methods during the 91-day cold season in 2004–2005 at conifer sites showed that season-long throughfall Hg flux (1.80 μg/m 2 ) < snowpack Hg (2.38 ± 0.68 μg/m 2 ) < event throughfall flux (5.63 ± 0.38 μg/m 2 ). Mercury deposition at the MDN site (0.91 μg/m 2 ) was similar to that measured at other no-canopy sites in the area using the other methods, but was 3.4 times less than was measured under conifer canopies using the event sampling regime. This indicates that snow accumulated under the forest canopy received Hg from the overstory or exhibited less re-emission of Hg deposited in snow relative to open areas. The soil surface of field-scale plots were sprayed with a natural rain water sample that contained an Hg tracer ( 202 Hg) just prior to the first snowfall to explore whether some snowpack Hg might be explained from soil emissions. The appearance of the 202 Hg tracer in the snowpack (0–64% of the total Hg mass in the snowpack) suggests that movement of Hg from the soil into the snowpack is possible. However, as with any tracer study the 202 Hg tracer may not precisely represent the reactivity and mobility of natural Hg in soils.

Applied Geochemistry↗

USGS2008

Transport of elemental mercury in the unsaturated zone from a waste disposal site in an arid region

Mercury contained in buried landfill waste may be released via upward emission to the atmosphere or downward leaching to groundwater. Data from the US Geological Survey’s Amargosa Desert Research Site (ADRS) in arid southwestern Nevada reveal another potential pathway of Hg release: long-distance (10 2 m) lateral migration of elemental Hg (Hg 0 ) through the unsaturated zone. Gas collected from multiple depths from two instrumented boreholes that sample the entire 110-m unsaturated zone thickness and are located 100 and 160 m away from the closest waste burial trench exhibit gaseous Hg concentrations of up to 33 and 11 ng m −3 , respectively. The vertical distribution of gaseous Hg in the borehole closest to the disposal site shows distinct subsurface peaks in concentration at depths of 1.5 and 24 m that cannot be explained by radial diffusive transport through a heterogeneous layered unsaturated zone. The inability of current models to explain gaseous Hg distribution at the ADRS highlights the need to advance the understanding of gas-phase contaminant transport in unsaturated zones to attain a comprehensive model of landfill Hg release.

Applied Geochemistry↗

USGS2008

Characterization and cycling of atmospheric mercury along the central US Gulf Coast

Concentrations of atmospheric Hg species, elemental Hg (Hg ∘ ), reactive gaseous Hg (RGM), and fine particulate Hg (Hg-PM 2.5 ) were measured at a coastal site near Weeks Bay, Alabama from April to August, 2005 and January to May, 2006. Mean concentrations of the species were 1.6 ± 0.3 ng m −3 , 4.0 ± 7.5 pg m −3 and 2.7 ± 3.4 pg m −3 , respectively. A strong diel pattern was observed for RGM (midday maximum concentrations were up to 92.7 pg m −3 ), but not for Hg ∘ or Hg-PM 2.5 . Elevated RGM concentrations (>25 pg m −3 ) in April and May of 2005 correlated with elevated average daytime O 3 concentrations (>55 ppbv) and high light intensity (>500 W m −2 ). These conditions generally corresponded with mixed continental-Gulf and exclusively continental air mass trajectories. Generally lower, but still elevated, RGM peaks observed in August, 2005 and January–March, 2006 correlated significantly ( p < 0.05) with peaks in SO 2 concentration and corresponded to periods of high light intensity and lower average daytime O 3 concentrations. During these times air masses were dominated by trajectories that originated over the continent. Elevated RGM concentrations likely resulted from photochemical oxidation of Hg ∘ by atmospheric oxidants. This process may have been enhanced in and by the near-shore environment relative to inland sites. The marine boundary layer itself was not found to be a significant source of RGM. Size segregation determination, using a limited dataset from two different methods, suggested that a significant fraction of particulate Hg was bound to coarse particles (>2.5 μm). A potential source of the large fraction of coarse particulate Hg in the study area is sequestration of RGM within sea salt aerosols. The presence of rapidly depositing RGM and coarse particulate Hg may be important sources of Hg input along the Gulf Coast. However, the impact of these species on deposition rates is yet to be determined.

Applied Geochemistry↗

USGS2008

Influence of sulfate input on freshwater sediments: Insights from incubation experiments

Incubation experiments were carried out under high and low SO42 - conditions to investigate the buffering capacity of lake sediments. Increased SO42 - content in the water column enhanced microbial SO42 - reduction, causing a continuous decrease of SO42 - content from 1086 to 83 mg/L paralleled by an increase of pH in the water column from 3.76 to 7.20. These changes were accompanied by decreased methanogenesis in the incubated sediments. The results demonstrate that the buffering capacity resulted from a variety of biodegradation pathways controlled to a large extent by SO42 - reduction, rather than by direct anaerobic oxidation of CH4. This is documented by distinctly lower ??13C values (from -73.99 to -65.24???) of the CH4 generated under higher SO42 - conditions compared to higher ??13C values (from -68.98 to -61.37???) of the CH4 generated under lower SO42 - conditions. ?? 2008 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2008

In situ arsenic removal in an alkaline clastic aquifer

In situ removal of As from ground water used for water supply has been accomplished elsewhere in circum-neutral ground water containing high dissolved Fe(II) concentrations. The objective of this study was to evaluate in situ As ground-water treatment approaches in alkaline ground-water (pH > 8) that contains low dissolved Fe (<a few tens of μg/L). The low dissolved Fe content limits development of significant Fe-oxide and the high-pH limits As adsorption onto Fe-oxide. The chemistries of ground water in the two aquifers studied are similar except for the inorganic As species. Although total inorganic As concentrations were similar, one aquifer has dominantly aqueous As(III) and the other has mostly As(V). Dissolved O 2 , Fe(II), and HCl were added to water and injected into the two aquifers to form Fe-oxide and lower the pH to remove As. Cycles of injection and withdrawal involved varying Fe(II) concentrations in the injectate. The As concentrations in water withdrawn from the two aquifers were as low as 1 and 6 μg/L, with greater As removal from the aquifer containing As(V). However, Fe and Mn concentrations increased to levels greater than US drinking water standards during some of the withdrawal periods. A balance between As removal and maintenance of low Fe and Mn concentrations may be a design consideration if this approach is used for public-supply systems. The ability to lower As concentrations in situ in high-pH ground water should have broad applicability because similar high-As ground water is present in many parts of the world.

Applied Geochemistry↗