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Evangelos Kakouros

Publications and source records attributed to Evangelos Kakouros.

15 recordsLinked to original sources

Select elements of concern in surface water of three hydrologic basins (Delaware River, Illinois River, and Upper Colorado River)—Data screening for the development of spatial and temporal models

The report focuses on the screening of previously published concentration data associated with 12 elements of concern (aluminum, arsenic, cadmium, chromium, copper, iron, mercury, manganese, lead, selenium, uranium, and zinc) measured in stream surface waters of three hydrologic basins (Delaware River Basin, Illinois River Basin, and the Upper Colorado River Basin). The purpose of this analysis is to determine what subsets of the original dataset (containing more than 1,500,000 observations) may be most suitable for each of two types of modeling efforts. The first type of modeling envisions a machine learning approach to determine which geospatial attributes are most significant in describing the spatial distribution of elemental concentrations within a basin. The second type of modeling envisions a stepwise regression approach to develop multivariable models that can be used to determine high resolution time-series estimates of elemental concentrations or loads at discrete U.S. Geological Survey real-time stream surface water sites. These site-specific temporal models are based on continuous measurements of available discharge and (or) in situ sensor data (temperature, pH, turbidity, dissolved oxygen, specific conductance, and (or) fluorescent dissolved organic matter) as the explanatory variables. The data screening for both model types considered historical trends in analytical methods and detection quantitation limits, the extent of censored data, data density, and environmental relevance with respect to three U.S. Environmental Protection Agency water quality thresholds (drinking water guidelines, human health criteria, and aquatic life criteria). The result of this analysis was the production of a final list of potential models deemed suitable for further development based upon the data exclusion (or inclusion) scheme developed herein for each model type. In both cases, the final models included mostly the three crustal elements (iron, manganese, and aluminum) that are found at comparatively high concentrations in surface water, whereas most of the more pernicious elements were excluded from the final model lists owing to various data limitations. The one exception to this was arsenic, for which the existing data were sufficient at three U.S. Geological Survey real-time sites for potential further development of time-series models.

Colorado, Delaware, Illinois, Indiana, Maryland, N

The relative importance of mercury methylation and demethylation in rice paddy soil varies depending on the presence of rice plants

Neurotoxic methylmercury (MeHg) accumulates in rice grain from paddy soil, where its concentration is controlled by microbial mercury methylation and demethylation. Both up- and down-regulation of methylation is known to occur in the presence of rice plants in comparison to non-vegetated paddy soils; the influence of rice plant presence/absence on demethylation is unknown. To assess the concurrent influence of rice plant presence/absence on methylation and demethylation, and to determine which process was more dominant in controlling soil MeHg concentrations, we maintained six rhizoboxes of paddy soil with and without rice plants. At the peak of plant growth, we simultaneously measured ambient MeHg, ambient inorganic mercury (IHg), and potential rate constants of methylation and demethylation (K meth and K demeth ) in soil using stable isotope tracers and ID-GC-ICPMS. We also measured organic matter content, elemental S, and water-extractable sulfate. We found MeHg concentrations were differentially controlled by MeHg production and degradation processes, depending on whether plants were present. In non-vegetated boxes, MeHg concentration was controlled by K meth , as evidenced by a strong and positive correlation, while K demeth had no relation to MeHg concentration. These results indicate methylation was the dominant driver of MeHg concentration in non-vegetated soil. In vegetated boxes, K demeth strongly and negatively predicted MeHg concentration, indicating that demethylation was the dominant control in soil with plants. MeHg concentration, K meth , and % MeHg all had significantly less variance in vegetated than in non-vegetated soils due to a consistent elimination of greater values. This pattern suggests that reduced MeHg production capacity was a secondary control on MeHg concentrations in vegetated soils. We observed no difference in the magnitude or variance of K demeth between treatments, suggesting that demethylation was robust to soil chemical conditions influenced by the plant, perhaps because of a wider taxonomic diversity of demethylators. Our results suggest that methylation and demethylation processes could both be leveraged to alter MeHg concentrations in rice paddy soil.

Ecotoxicology and Environmental Safety

Geochemical data for water, streambed sediment, and fish tissue from the Sierra Nevada Mercury Impairment Project, 2011–12

This report presents geochemical data for surface water, streambed sediment, and fish tissue samples collected during low-flow conditions in 20 to 24 Sierra Nevada streams during 2011 and 2012. The dataset is part of a larger study designed to assess the factors that control mercury concentrations in fish tissue and to develop a model that predicts mercury concentration in the tissue of selected fish species in Sierra Nevada streams. The ranges of total mercury concentration observed in different matrices of water and sediment from 24 locations were as follows: below detection to 0.86 nanograms per liter in filtered water, below detection to 4.06 nanograms per liter in suspended particulates (greater than 0.3 micrometer in diameter), 1.1 to 381 nanograms per gram in bed sediment less than 2 millimeters, and 28.1 to 1,410 nanograms per gram in bed sediment less than 0.063 millimeters. The ratio of monomethyl mercury to total mercury ranged as follows: below detection to 19.2 percent in filtered water, below detection to 51.7 percent in suspended particles (greater than 0.3 micrometer), and below detection to 7.6 percent in streambed sediment less than 2 millimeters. Fish from 3 species collected at 20 locations had the following range in total mercury concentration (all concentrations wet weight): 10 to 292 nanograms per gram in rainbow trout (293 fish, 19 locations), 13 to 386 nanograms per gram in brown trout (33 fish, 10 locations), and 159 nanograms per gram in hardhead (1 fish). Concentrations of selenium in fish (wet weight) ranged from 60 to 420 nanograms per gram in rainbow trout (66 fish, 19 locations) and from 180 to 240 nanograms per gram in brown trout (6 fish, 2 locations).

Sierra Nevada

A practical method for the determination of total selenium in environmental samples using isotope dilution-hydride generation-inductively coupled plasma-mass spectrometry

A safe, practical, and accurate method for the determination of selenium (Se) in range of environmental samples was developed. Small sample masses, 5–20 mg, were amended with 82 Se enriched isotope for the isotope dilution (ID), preceding a multi-step wet digestion with nitric acid (HNO 3 ) and hydrogen peroxide (H 2 O 2 ). Samples were incubated in an autoclave for 3 h at 20 psi and 126°C. Digestates were subsequently reduced with concentrated hydrochloric acid to Se(IV) the most favorable valence for hydride generation (HG). The solutions were then analyzed on an ICP-MS equipped with Flow Injection system (FIAS-400). Polyatomic, isobaric, and background interferences were removed through the use of HG and ID with an 82 Se enriched isotope spike. Recoveries for certified reference materials were determined and averaged 96% for biological tissues (NRCC DOLT3, DOLT4, DORM2, TORT2, and TORT3, and NIST 2976) and 108% for estuarine sediment (NRCC PACS2) with an average coefficient of variation for replicate measurements of ∼ 3.5%. Limit of detection was 0.13 ng Se g −1 dry weight or 0.19 ng Se L −1 . This method can be broadly applied to biological tissues, sediments, suspended particulates, and water samples with minimal modifications making this method highly useful for assessing the ecotoxicology of total Se in aquatic ecosystems.

Limnology and Oceanography: Methods

Mercury cycling in agricultural and managed wetlands of California: experimental evidence of vegetation-driven changes in sediment biogeochemistry and methylmercury production

The role of live vegetation in sediment methylmercury (MeHg) production and associated biogeochemistry was examined in three types of agricultural wetlands (domesticated or white rice, wild rice, and fallow fields) and adjacent managed natural wetlands (cattail- and bulrush or tule-dominated) in the Yolo Bypass region of California's Central Valley, USA. During the active growing season for each wetland, a vegetated:de-vegetated paired plot experiment demonstrated that the presence of live plants enhanced microbial rates of mercury methylation by 20 to 669% (median = 280%) compared to de-vegetated plots. Labile carbon exudation by roots appeared to be the primary mechanism by which microbial methylation was enhanced in the presence of vegetation. Pore-water acetate (pw[Ac]) decreased significantly with de-vegetation (63 to 99%) among all wetland types, and within cropped fields, pw[Ac] was correlated with both root density (r = 0.92) and microbial Hg(II) methylation (k meth . r = 0.65). Sediment biogeochemical responses to de-vegetation were inconsistent between treatments for “reactive Hg” (Hg(II)R), as were reduced sulfur and sulfate reduction rates. Sediment MeHg concentrations in vegetated plots were double those of de-vegetated plots (median = 205%), due in part to enhanced microbial MeHg production in the rhizosphere, and in part to rhizoconcentration via transpiration-driven pore-water transport. Pore-water concentrations of chloride, a conservative tracer, were elevated (median = 22%) in vegetated plots, suggesting that the higher concentrations of other constituents around roots may also be a function of rhizoconcentration rather than microbial activity alone. Elevated pools of amorphous iron (Fe) in vegetated plots indicate that downward redistribution of oxic surface waters through transpiration acts as a stimulant to Fe(III)-reduction through oxidation of Fe(II)pools. These data suggest that vegetation significantly affected rhizosphere biogeochemistry through organic exudation and transpiration-driven concentration of pore-water constituents and oxidation of reduced compounds. While the relative role of vegetation varied among wetland types, macrophyte activity enhanced MeHg production.

California

Methylmercury production in sediment from agricultural and non-agricultural wetlands in the Yolo Bypass, California, USA

As part of a larger study of mercury (Hg) biogeochemistry and bioaccumulation in agricultural (rice growing) and non-agricultural wetlands in California's Central Valley, USA, seasonal and spatial controls on methylmercury (MeHg) production were examined in surface sediment. Three types of shallowly-flooded agricultural wetlands (white rice, wild rice, and fallow fields) and two types of managed (non-agricultural) wetlands (permanently and seasonally flooded) were sampled monthly-to-seasonally. Dynamic seasonal changes in readily reducible ‘reactive’ mercury (Hg(II) R ), Hg(II)-methylation rate constants (k meth ), and concentrations of electron acceptors (sulfate and ferric iron) and donors (acetate), were all observed in response to field management hydrology, whereas seasonal changes in these parameters were more muted in non-agricultural managed wetlands. Agricultural wetlands exhibited higher sediment MeHg concentrations than did non-agricultural wetlands, particularly during the fall through late-winter (post-harvest) period. Both sulfate- and iron-reducing bacteria have been implicated in MeHg production, and both were demonstrably active in all wetlands studied. Stoichiometric calculations suggest that iron-reducing bacteria dominated carbon flow in agricultural wetlands during the growing season. Sulfate-reducing bacteria were not stimulated by the addition of sulfate-based fertilizer to agricultural wetlands during the growing season, suggesting that labile organic matter, rather than sulfate, limited their activity in these wetlands. Along the continuum of sediment geochemical conditions observed, values of k meth increased approximately 10,000-fold, whereas Hg(II) R decreased 100-fold. This suggests that, with respect to the often opposing trends of Hg(II)-methylating microbial activity and Hg(II) availability for methylation, microbial activity dominated the Hg(II)-methylation process, and that along this biogeochemical continuum, conditions that favored microbial sulfate reduction resulted in the highest calculated MeHg production potential rates. Rice straw management options aimed at limiting labile carbon supplies to surface sediment during the post-harvest fall–winter period may be effective in limiting MeHg production within agricultural wetlands.

California

Mercury cycling in agricultural and managed wetlands of California: seasonal influences of vegetation on mercury methylation, storage, and transport

Plants are a dominant biologic and physical component of many wetland capable of influencing the internal pools and fluxes of methylmercury (MeHg). To investigate their role with respect to the latter, we examined the changing seasonal roles of vegetation biomass and Hg, C and N composition from May 2007-February 2008 in 3 types of agricultural wetlands (domesticated or white rice, wild rice, and fallow fields), and in adjacent managed natural wetlands dominated by cattail and bulrush (tule). We also determined the impact of vegetation on seasonal microbial Hg methylation rates, and Hg and MeHg export via seasonal storage in vegetation, and biotic consumption of rice seed. Despite a compressed growing season of ~ 3 months, annual net primary productivity (NPP) was greatest in white rice fields and carbon more labile (leaf median C:N ratio = 27). Decay of senescent litter (residue) was correlated with microbial MeHg production in winter among all wetlands. As agricultural biomass accumulated from July to August, THg concentrations declined in leaves but MeHg concentrations remained consistent, such that MeHg pools generally increased with growth. Vegetation provided a small, temporary, but significant storage term for MeHg in agricultural fields when compared with hydrologic export. White rice and wild rice seeds reached mean MeHg concentrations of 4.1 and 6.2 ng g dw - 1 , respectively. In white rice and wild rice fields, seed MeHg concentrations were correlated with root MeHg concentrations (r = 0.90, p < 0.001), suggesting transport of MeHg to seeds from belowground tissues. Given the proportionally elevated concentrations of MeHg in rice seeds, white and wild rice crops may act as a conduit of MeHg into biota, especially waterfowl which forage heavily on rice seeds within the Central Valley of California, USA. Thus, while plant tissues and rhizosphere soils provide temporary storage for MeHg during the growing season, export of MeHg is enhanced post-harvest through increased hydrologic and biotic export.

California

Geochemical modeling of changes in shallow groundwater chemistry observed during the MSU-ZERT CO2 injection experiment

A field experiment involving the release of carbon dioxide (CO 2 ) into a shallow aquifer was conducted near Bozeman, Montana, during the summer of 2008, to investigate the potential groundwater quality impacts in the case of leakage of CO 2 from deep geological storage. As an essential part of the Montana State University Zero Emission Research and Technology (MSU-ZERT) field program, food-grade CO 2 was injected over a 30 day period into a horizontal perforated pipe a few feet below the water table of a shallow aquifer. The impact of elevated CO 2 concentrations on groundwater quality was investigated by analyzing water samples taken before, during, and following CO 2 injection, from observation wells located in the vicinity of the injection pipe, and from two distant monitoring wells. Field measurements and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of naturally occurring major and trace element species. The geochemical data were evaluated using principal component analysis (PCA) to (1) understand potential correlations between aqueous species, and (2) to identify minerals controlling the chemical composition of the groundwater prior to CO 2 injection. These evaluations were used to assess possible geochemical processes responsible for the observed increases in the concentrations of dissolved constituents, and to simulate these processes using a multicomponent reaction path model. Reasonable agreement between observed and modeled data suggests that (1) calcite dissolution was the primary pH buffer, yielding increased Ca +2 concentrations in the groundwater, (2) increases in the concentrations of most major and trace metal cations except Fe could be a result of Ca +2 -driven exchange reactions, (3) the release of anions from adsorption sites due to competitive adsorption of carbonate could explain the observed trends of most anions, and (4) the dissolution of reactive Fe minerals (presumed ferrihydrite and fougerite, from thermodynamic analyses) could explain increases in total Fe concentration. Highlights ► Because the possibility of CO 2 leakage cannot be completely ruled out, the potential impact of CO 2 intrusion on the quality of fresh water aquifers overlying CO 2 storage sites needs to be investigated. ► Geochemical data from a field experiment involving the release of carbon dioxide (CO 2 ) into a shallow aquifer were evaluated. ► Geochemical model used to assess possible geochemical processes responsible for the observed increases in the concentrations of dissolved constituents. ► Reasonable agreement between observed and modeled data suggests that increases in the concentrations of most major and trace metal cations except Fe could be a result of Ca +2 -driven exchange reactions and the release of anions from adsorption sites due to competitive adsorption of carbonate could explain the observed trends of most anions.

Montana

Transient changes in shallow groundwater chemistry during the MSU ZERT CO2 injection experiment

Food-grade CO 2 was injected into a shallow aquifer through a perforated pipe placed horizontally 1–2 m below the water table at the Montana State University Zero Emission Research and Technology (MSU-ZERT) field site at Bozeman, Montana. The possible impact of elevated CO 2 levels on groundwater quality was investigated by analyzing 80 water samples taken before, during, and following CO 2 injection. Field determinations and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of trace element species. The geochemical data were first evaluated using principal component analysis (PCA) in order to identify correlations between aqueous species. The PCA findings were then used in formulating a geochemical model to simulate the processes likely to be responsible for the observed increases in the concentrations of dissolved constituents. Modeling was conducted taking into account aqueous and surface complexation, cation exchange, and mineral precipitation and dissolution. Reasonable matches between measured data and model results suggest that: (1) CO 2 dissolution in the groundwater causes calcite to dissolve. (2) Observed increases in the concentration of dissolved trace metals result likely from Ca +2 -driven ion exchange with clays (smectites) and sorption/desorption reactions likely involving Fe (hydr)oxides. (3) Bicarbonate from CO 2 dissolution appears to compete for sorption with anionic species such as HAsO 4 −2 , potentially increasing dissolved As levels in groundwater.

Conference Paper

The effects of sediment and mercury mobilization in the South Yuba River and Humbug Creek confluence area, Nevada County, California: Concentrations, speciation, and environmental fate – Part 1: Field characterization

Millions of pounds of mercury (Hg) were deposited in the river and stream channels of the Sierra Nevada from placer and hard-rock mining operations in the late 1800s and early 1900s. The resulting contaminated sediments are relatively harmless when buried and isolated from the overlying aquatic environment. The entrained Hg in the sediment constitutes a potential risk to human and ecosystem health should it be reintroduced to the actively cycling portion of the aquatic system, where it can become methylated and subsequently bioaccumulated in the food web. Each year, sediment is mobilized within these fluvial systems during high stormflows, transporting hundreds of tons of Hg-laden sediment downstream. The State of California and resource-management agencies, including the Bureau of Land Management (BLM) and the U.S. Forest Service, are concerned about additional disturbances, such as from suction gold dredging activities, which have the potential to mobilize Hg associated with buried sediment layers elevated in Hg that are otherwise likely to remain buried under normal storm conditions. The BLM initiated a study looking at the feasibility of removing Hg-contaminated sediment at the confluence of the South Yuba River and Humbug Creek in the northern Sierra Nevada of California by using standard suction-dredge technology. Additionally, the California State Water Resources Control Board (SWRCB) supported a comprehensive characterization of the intended dredge site. Together, the BLM and SWRCB supported a comprehensive characterization of Hg contamination at the site and the potential effects of sediment disturbance at locations with historical hydraulic mining debris on downstream environments. The comprehensive study consisted of two primary components: field studies and laboratory experiments. The field component, described in this report, had several study elements: 1) a preliminary, smallscale, in-stream dredge test; 2) comprehensive characterization of grain size distribution, Hg speciation, and mineralogy of bed and suspended sediment; 3) a determination of the past and current sources of sediment in the study area; 4) an assessment of Hg bioaccumulation in the local invertebrate population; and 5) a comparison of potential Hg transport caused by natural storm disturbances with potential Hg mobilization caused by suction dredging as a method of Hg removal at the study site. The laboratory component of the study assessed the potential influence of the disturbance of Hg-contaminated sediment through experiments designed to simulate in-stream transport, deposition, and potential methylation of Hg, described in a companion report (see Marvin-DiPasquale and others, 2011). Results of the field studies indicate that the fine-grained fraction (silt-clay, less than 0.063 millimeters) contains the greatest concentration of Hg in contaminated sediment. Because the fine-grained fraction is the most susceptible to longrange fluvial transport, disturbance of Hg-contaminated sediment is likely to increase the concentration and load of Hg in downstream waters. The preliminary, small-scale dredge test showed an increase in the concentration of fine particles and Hg in the water column caused by the dredge activity, despite relatively low concentrations of fine particles and Hg (about 300 nanograms per gram) at the dredge site. Characterization of sediment from two test pits and other sites in the vicinity of the confluence of the South Yuba River and Humbug Creek revealed a highly variable distribution of fine- and coarse-grained sediment. The highest levels of Hg contamination (up to 11,100 ng/g) were associated with the fine-grained fraction of sediment from the bedrock contact zone of Pit 2, a horizon which also yielded grains of gold and gold-Hg amalgam. A closed-circuit tank experiment with a venturi dredge at the base of Pit 1, in a gravel bar within the South Yuba River, resulted in fine-grained suspended sediment remaining in suspension more than 40 hours following the disturbance simulation. Although the volumetric concentration of Hg declined over time as particles settled out, the concentration of Hg on the suspended particles increased over time as the suspended material became finer grained, because Hg is preferentially adsorbed on to clay-sized particles. Mineralogical and chemical analyses indicated that the buried fine-grained material with the greatest Hg contamination was derived from hydraulic mining debris, which consist primarily of Eocene gravels mined in the Malakoff Diggins, North Bloomfield, and Lake City areas within the South Yuba River watershed. Coarse material and more recently deposited sediment were derived primarily from upstream sources on the South Yuba River. The biota assessment indicated that invertebrate taxa collected from all sites on the South Yuba River in 2007, including lower Humbug Creek, had elevated concentrations of total mercury (THg) and methylmercury (MeHg) compared to a reference site on the Bear River, upstream of mining effects. Differences with the reference site were less pronounced in 2008 when a significant reduction in MeHg concentrations was observed in biota across all taxa from concentrations in 2007. It is possible that the inter-annual variation was related to the fact that suction dredging was active in the South Yuba River in 2007 but not in 2008 when a local moratorium was imposed by the BLM. There were significant variations among taxa for both THg and MeHg concentrations, with the water striders (Gerridae) having the highest concentrations of both THg and MeHg; variation among sites was not as strong as between years or among taxa. These results suggest that additional monitoring would be helpful to investigate the possible linkage between variations in MeHg bioaccumulation and levels of suction dredge activity in areas of historical gold mining. Results from the field studies indicate that disturbance of the finegrained Hg-contaminated sediment would likely lead to enhanced mobilization of Hg to downstream environments; therefore, the use of suction dredging to remove Hg at the South Yuba River and Humbug Creek confluence area would likely result in enhanced Hg transport downstream relative to natural conditions.

California

Biogeochemical processes in an urban, restored wetland of San Francisco Bay, California, 2007-2009: Methods and data for plant, sediment and water parameters

The restoration of 18 acres of historic tidal marsh at Crissy Field has had great success in terms of public outreach and visibility, but less success in terms of revegetated marsh sustainability. Native cordgrass (Spartina foliosa) has experienced dieback and has failed to recolonize following extended flooding events during unintended periodic closures of its inlet channel, which inhibits daily tidal flushing. We examined the biogeochemical impacts of these impoundment events on plant physiology and on sulfur and mercury chemistry to help the National Park Service land managers determine the relative influence of these inlet closures on marsh function. In this comparative study, we examined key pools of sulfur, mercury, and carbon compounds both during and between closure events. Further, we estimated the net hydrodynamic flux of methylmercury and total mercury to and from the marsh during a 24-hour diurnal cycle. This report documents the methods used and the data generated during the study.

California

Changes in the chemistry of shallow groundwater related to the 2008 injection of CO2 at the ZERT field site, Bozeman, Montana

Approximately 300 kg/day of food-grade CO 2 was injected through a perforated pipe placed horizontally 2–2.3 m deep during July 9–August 7, 2008 at the MSU-ZERT field test to evaluate atmospheric and near-surface monitoring and detection techniques applicable to the subsurface storage and potential leakage of CO 2 . As part of this multidisciplinary research project, 80 samples of water were collected from 10 shallow monitoring wells (1.5 or 3.0 m deep) installed 1–6 m from the injection pipe, at the southwestern end of the slotted section (zone VI), and from two distant monitoring wells. The samples were collected before, during, and following CO 2 injection. The main objective of study was to investigate changes in the concentrations of major, minor, and trace inorganic and organic compounds during and following CO 2 injection. The ultimate goals were (1) to better understand the potential of groundwater quality impacts related to CO 2 leakage from deep storage operations, (2) to develop geochemical tools that could provide early detection of CO 2 intrusion into underground sources of drinking water (USDW), and (3) to test the predictive capabilities of geochemical codes against field data. Field determinations showed rapid and systematic changes in pH (7.0–5.6), alkalinity (400–1,330 mg/l as HCO 3 ), and electrical conductance (600–1,800 μS/cm) following CO 2 injection in samples collected from the 1.5 m-deep wells. Laboratory results show major increases in the concentrations of Ca (90–240 mg/l), Mg (25–70 mg/l), Fe (5–1,200 ppb), and Mn (5–1,400 ppb) following CO 2 injection. These chemical changes could provide early detection of CO 2 leakage into shallow groundwater from deep storage operations. Dissolution of observed carbonate minerals and desorption-ion exchange resulting from lowered pH values following CO 2 injection are the likely geochemical processes responsible for the observed increases in the concentrations of solutes; concentrations generally decreased temporarily following four significant precipitation events. The DOC values obtained are 5 ± 2 mg/l, and the variations do not correlate with CO 2 injection. CO 2 injection, however, is responsible for detection of BTEX (e.g. benzene, 0–0.8 ppb), mobilization of metals, the lowered pH values, and increases in the concentrations of other solutes in groundwater. The trace metal and BTEX concentrations are all significantly below the maximum contaminant levels (MCLs). Sequential leaching of core samples is being carried out to investigate the source of metals and other solutes.

Montana

Experimental removal of wetland emergent vegetation leads to decreased methylmercury production in surface sediment

We performed plant removal (devegetation) experiments across a suite of ecologically diverse wetland settings (tidal salt marshes, river floodplain, rotational rice fields, and freshwater wetlands with permanent or seasonal flooding) to determine the extent to which the presence (or absence) of actively growing plants influences the activity of the Hg(II)-methylating microbial community and the availability of Hg(II) to those microbes. Vegetated control plots were paired with neighboring devegetated plots in which photosynthetic input was terminated 4–8 months prior to measurements, through clipping aboveground biomass, severing belowground connections, and shading the sediment surface to prevent regrowth. Across all wetlands, devegetation decreased the activity of the Hg(II)-methylating microbial community (k meth ) by 38%, calculated MeHg production potential (MP) rates by 36%, and pore water acetate concentration by 78%. Decreases in MP were associated with decreases in microbial sulfate reduction in salt marsh settings. In freshwater agricultural wetlands, decreases in MP were related to indices of microbial iron reduction. Sediment MeHg concentrations were also significantly lower in devegetated than in vegetated plots in most wetland settings studied. Devegetation effects were correlated with live root density (percent volume) and were most profound in vegetated sites with higher initial pore water acetate concentrations. Densely rooted wetlands had the highest rates of microbial Hg(II)-methylation activity but often the lowest concentrations of bioavailable reactive Hg(II). We conclude that the exudation of labile organic carbon (e.g., acetate) by plants leads to enhanced microbial sulfate and iron reduction activity in the rhizosphere, which results in high rates of microbial Hg(II)-methyation and high MeHg concentrations in wetland sediment.

Journal of Geophysical Research: Biogeosciences

Geochemical data from produced water contamination investigations: Osage-Skiatook Petroleum Environmental Research (OSPER) sites, Osage County, Oklahoma

We report chemical and isotopic analyses of 345 water samples collected from the Osage-Skiatook Petroleum Environmental Research (OSPER) project. Water samples were collected as part of an ongoing multi-year USGS investigation to study the transport, fate, natural attenuation, and ecosystem impacts of inorganic salts and organic compounds present in produced water releases at two oil and gas production sites from an aging petroleum field located in Osage County, in northeast Oklahoma. The water samples were collected primarily from monitoring wells and surface waters at the two research sites, OSPER A (legacy site) and OSPER B (active site), during the period March, 2001 to February, 2005. The data include produced water samples taken from seven active oil wells, one coal-bed methane well and two domestic groundwater wells in the vicinity of the OSPER sites.

Oklahoma

Environmental impacts of petroleum production: Fate of inorganic and organic chemicals in produced water from the Osage-Skiatook Petroleum Environmental Research sites, Osage County, Oklahoma

About 15 scientists from the U. S. Geological Survey, other Federal agencies and academia are involved in a multidisciplinary investigation to study the transport, fate, and natural attenuation of inorganic salts, trace metals, radionuclides and organic compounds present in produced water, and their impacts on soil, surface and ground water and the local ecosystem at the Osage-Skiatook Petroleum Environmental Research (OSPER) A and B sites, located in Osage County, OK. The Branstetter lease, OSPER B site, is typical of many aging petroleum fields in Osage County, which ranks among the top oil and gas producing counties in Oklahoma with close to 40,000 wells. Current production in Osage County is mainly from stripper wells (averaging ~2.8 bbls/d oil and >30 bbls/d brine) that are shallow, mostly 300-700 m in depth, and produce from several sandstones of Pennsylvanian age. About one hectare of land at the OSPER B site is affected by salt scarring, soil salinization and brine and petroleum contamination due to the leakage of produced water and associated hydrocarbons from two brine pits and due to accidental releases from active tank batteries. Eventually, the bulk of inorganic salts and some dissolved organic species in the released brine reach, directly or via the two local streams, the adjacent Skiatook Lake, a 4250-hectare reservoir that provides drinking water to the local communities and is a major recreational fishery. About 40 water samples were obtained from several oil wells at the B site and adjoining areas, the two brine pits, several brine pools and seeps in the impacted area, local streams, Skiatook Lake, and from about 20 boreholes (1-71 m deep), recently drilled and completed with slotted PVC tubing. Water level monitoring and additional sampling is continuing. Results to date show that the produced water is a high-salinity (~150,000 mg/L total dissolved solids) Na-Ca-Cl brine, with relatively high concentrations of Sr, Mg and NH4, but low amounts of SO4 and H2S. With the exception of Fe and Mn, the concentrations of trace metals are low, and the values of dissolved organics are relatively low. As the brine flows from the brine pits through the shallow eolian sand, colluvial and alluvial deposits to the streams and Skiatook Lake, it is diluted by infiltrating water from precipitation. Its chemical composition is modified by sorption, mineral precipitation/dissolution, transpiration, volatilization and oxidation/reduction reactions. Bacteria likely play an important role in many of these reactions.

Oklahoma