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At least 145 records · Page 8Linked to original sources

Stable carbon isotopes of HCO3- in oil-field waters-implications for the origin of CO2

The δ 13 C values of dissolved HCO 3 − in 75 water samples from 15 oil and gas fields (San Joaquin Valley, Calif., and the Houston-Galveston and Corpus Christi areas of Texas) were determined to study the sources of CO 2 of the dissolved species and carbonate cements that modify the porosity and permeability of many petroleum reservoir rocks. The reservoir rocks are sandstones which range in age from Eocene through Miocene. The δ 13 C values of total HCO 3 − indicate that the carbon in the dissolved carbonate species and carbonate cements is mainly of organic origin. The range of δ 13 C values for the HCO 3 − of these waters is −20–28 per mil relative to PDB. This wide range of δ 13 C values is explained by three mechanisms. Microbiological degradation of organic matter appears to be the dominant process controlling the extremely low and high δ 13 C values of HCO 3 − in the shallow production zones where the subsurface temperatures are less than 80°C. The extremely low δ 13 C values (< −10 per mil) are obtained in waters where concentrations of SO 4 2− are more than 25 mg/l and probably result from the degradation of organic acid anions by sulfate-reducing bacteria ( SO 4 2− + CH 3 COO − → 2 HCO 3 − + HS − ). The high δ 13 C values probably result from the degradation of these anions by methanogenic bacteria ( CH 3 COO − + H 2 O ai HCO 3 − + CH 4 ). Thermal decarboxylation of short-chain aliphatic acid anions (principally acetate) to produce CO 2 and CH 4 is probably the major source of CO 2 for production zones with subsurface temperatures greater than 80°C. The δ 13 C values of HCO 3 − for waters from zones with temperatures greater than 100°C result from isotopic equilibration between CO 2 and CH 4 . At these high temperatures, δ 13 C values of HCO 3 − decrease with increasing temperatures and decreasing concentrations of these acid anions.

Geochimica et Cosmochimica Acta

Sources and flux of natural gases from Mono Lake, California

The ability to identify a formation mechanism for natural gas in a particular environment requires consideration of several geochemical factors when there are multiple sources present. Four primary sources of methane have been identified in Mono Lake. Two of these sources were associated with numerous natural gas seeps which occur at various locations in the lake and extend beyond its present boundary; the two other gas sources result from current microbiological processes. In the natural gas seeps, we observed flow rates as high as 160 moles CH 4 day −1 , and estimate total lakewide annual seep flux to be 2.1 × 10 6 moles CH 4 . Geochemical parameters ( δ 13 CH 4 , δDCH 4 , CH 4 /[ C 2 H 6 + C 3 H 8 ]) and δ 14 CH 4 measurements revealed that most of the seeps originate from a paleo-biogenic ( δ 13 CH 4 = about −70%.). natural gas deposit of Pleistocene age which underlies the current and former lakebed. Gas seeps in the vicinity of hot springs had, in combination with the biogenic gas, a prominent thermogenic gas component resulting from hydrothermal alteration of buried organic matter.

California

The organic geochemistry of black sedimentary barite: Significance and implications of trapped fatty acids

Fatty acids isolated in sedimentary black barite (BaSO 4 ) from Arkansas and Nevada were identified by gas chromatography-mass spectroscopy. The dominant or major fatty acids found in these beds of barite are C 16:0 , C 18:0 , and C 18:1 . The occurrence and distribution of these acids in this type of rock may serve as “molecular fingerprints” of microbial biogeochemical processes. The organic matter and associated microorganisms are shown to be trapped within the finely crystalline barite, thus forming a closed system for microbial diagenesis. Important differences that occur in the distribution of the lesser or minor fatty acids probably result from: (1) the nature of the progenitor organic detritus in the environment of barite deposition: and (2) the subsequent degree of microbiological alteration of the parent organic debris swept into and trapped in the depositional environment. Three general models of sedimentary environments are proposed in which anoxic conditions may prevail and where barium sulfate (BaSO 4 ) may precipitate: (1) in a silled basin with semi-restricted circulation; (2) on an outer continental shelf where the slope is encroached upon by water of the oxygen minimum layer; (3) on a low-energy, inner shelf or semi-restricted embayment impinged by a wedge of anoxic water. The major geochemical and geological parameters which are believed to be the significant factors controlling the formation and high grade of these organic-rich, black bedded barites are: (1) a unique source of barium-rich fluid that only contains trace amounts of other elements; (2) the presence of an anoxic bottom environment within the depositional basin; (3) a reflux source of sulfate ion; (4) an adequate source of organic matter. The results of this study may serve as guidelines for future exploration in similar, untested sedimentary basins, especially those with rocks of middle Paleozoic age.

Arkansas, Nevada

Biological measurements and related chemical features in Soviet and United States regions of the Bering Sea

The U.S. results of a joint U.S.-U.S.S.R. expedition to the Bering Sea in 1984 investigated the chemical and biological interactions in the south, east, north and west regions. The nutrients, phytoplankton biomass and primary productivity were enhanced near the ends of a north-south transect of stations. The southern end of the transect had characteristics of the North Pacific Ocean with high nutrient and low phytoplankton concentrations and an elevated concentration of peridinin indicative of dinoflagellates. The middle station of the transect, near the shelf break, had low nutrients and phytoplankton in the upper euphotic zone, but a submerged chlorophyll b maximum indicated green algae was located on the upper boundary of high ammonium concentration and pycnocline. The north end of the transect over the shelf at mid-depth on the boundary of high nitrate and ammonium concentrations produced the highest primary production. Pigment analysis (chlorophyll a , diadinoxanthin and fucoxanthin) indicated the dominance of diatoms and was coincidental to oxygen saturation values as large as 150%. The highest phaeophorbide a concentrations were also observed in this area, suggesting relatively high grazing stress. Measurements of low molecular weight hydrocarbons also suggest high microbiological degradation rates of organic matter in the sediments in the north region. Overall, this research strongly relates nutrient, oxygen and pigment concentrations to the production, decomposition and recycling processes in the open ocean and shelf areas of the Bering Sea.

Bering Sea

Crude oil in a shallow sand and gravel aquifer-II. Organic geochemistry

Crude oil spilled from a pipeline break in a remote area of north-central Minnesota has contaminated a shallow glacial outwash aquifer. Part of the oil was sprayed over a large area to the west of the pipeline and part of it accumulated in an oil body that floats at the water table to the east of the point of discharge. Total dissolved organic carbon (TDOC) concentrations in shallow groundwater collected in the oil spray area reach 16 mg/l. This is nearly an order of magnitude higher than the TDOC concentrations of native groundwater (∼2–3mg/l). The additional TDOC derives from the partial degradation of petroleum residues deposited at the land surface and transported to the aquifer by vertical recharge. In the vicinity of the oil body, TDOC concentrations in groundwater are 48 mg/l, 58% of the TDOC being composed of non-volatile organic C. The majority of the volatile DOC (63%) is a mixture of low-molecular-weight saturated, aromatic and alicyclic hydrocarbons derived from the oil. Downgradient from the oil body along the direction of groundwater flow, concentrations of all measured constituents of the TDOC pool decrease. Concentrations begin to decline most rapidly, however, in the zone where dissolved O 2 concentrations begin to increase, ∼50m downgradient from the leading edge of the oil. Within the anoxic zone near the oil body, removal rates of isometric monoaromatic hydrocarbons vary widely. This indicates that the removal processes are mediated mainly by microbiological activity. Molecular and spectroscopic characterization of the TDOC and its spatial and temporal variation provide evidence of the importance of biogeochemical processes in attenuating petroleum contaminants in this perturbed subsurface environment.

Applied Geochemistry

A new sampler for the collection and retrieval of dry dust deposition

Atmospheric dust can influence biogeochemical cycles, accelerate snowmelt, and affect air, water quality, and human health. Yet, the bulk of atmospherically transported material remains poorly quantified in terms of total mass fluxes and composition. This lack of information stems in part from the challenges associated with measuring dust deposition. Here we report on the design and efficacy of a new dry deposition sampler (Dry Deposition Sampling Unit (DSU)) and method that quantifies the gravitational flux of dust particles. The sampler can be used alone or within existing networks such as those employed by the National Atmospheric Deposition Program (NADP). Because the samplers are deployed sterile and the use of water to remove trapped dust is not required, this method allows for the recovery of unaltered dry material suitable for subsequent chemical and microbiological analyses. The samplers were tested in the laboratory and at 15 field sites in the western United States. With respect to material retention, sampler performance far exceeded commonly used methods. Retrieval efficiency was >97% in all trials and the sampler effectively preserved grain size distributions during wind exposure experiments. Field tests indicated favorable comparisons to dust-on-snow measurement across sites ( r 2 0.70, p < 0.05) and within sites to co-located aerosol data ( r 2 0.57–0.99, p < 0.05). The inclusion of dust deposition and composition monitoring into existing networks increases spatial and temporal understanding of the atmospheric transport on materials and substantively furthers knowledge of the effects of dust on terrestrial ecosystems and human exposure to dust and associated deleterious compounds.

Arizona, California, Colorado, Idaho, Nevada, Utah

Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters

The formation of acid mine drainage from metals extraction or natural acid rock drainage and its mixing with surface waters is a complex process that depends on petrology and mineralogy, structural geology, geomorphology, surface-water hydrology, hydrogeology, climatology, microbiology, chemistry, and mining and mineral processing history. The concentrations of metals, metalloids, acidity, alkalinity, Cl - , F - and SO 4 2- found in receiving streams, rivers, and lakes are affected by all of these factors and their interactions. Remediation of mine sites is an engineering concern but to design a remediation plan without understanding the hydrogeochemical processes of contaminant mobilization can lead to ineffective and excessively costly remediation. Furthermore, remediation needs a goal commensurate with natural background conditions rather than water-quality standards that might bear little relation to conditions of a highly mineralized terrain. This paper reviews hydrogeochemical generalizations, primarily from US Geological Survey research, that enhance our understanding of the origin, transport, and fate of contaminants released from mined and mineralized areas. Mobility of potential or actual contaminants from mining and mineral processing activities depends on (1) occurrence : is the mineral source of the contaminant actually present? (2) abundance : is the mineral present in sufficient quantity to make a difference? (3) reactivity : what are the energetics, rates, and mechanisms of sorption and mineral dissolution and precipitation relative to the flow rate of the water? and (4) hydrology : what are the main flow paths for contaminated water? Estimates of relative proportions of minerals dissolved and precipitated can be made with mass-balance calculations if minerals and water compositions along a flow path are known. Combined with discharge, these mass-balance estimates quantify the actual weathering rate of pyrite mineralization in the environment and compare reasonably well with laboratory rates of pyrite oxidation except when large quantities of soluble salts and evaporated mine waters have accumulated underground. Quantitative mineralogy with trace-element compositions can substantially improve the identification of source minerals for specific trace elements through mass balances. Post-dissolution sorption and precipitation (attenuation) reactions depend on the chemical behavior of each element, solution composition and pH, aqueous speciation, temperature, and contact-time with mineral surfaces. For example, little metal attenuation occurs in waters of low pH (<3.5) and metals tend to maintain element ratios indicative of the main mineral or group of minerals from which they dissolved, except Fe, SiO 2 , and redox-sensitive oxyanions (As, Sb, Se, Mo, Cr, V). Once dissolved, metal and metalloid concentrations are strongly affected by redox conditions and pH. Iron is the most reactive because it is rapidly oxidized by bacteria and archaea and Fe(III) hydrolyzes and precipitates at low pH (1&ndash;3) which is related directly to its first hydrolysis constant, pK 1 = 2.2. Several insoluble sulfate minerals precipitate at low pH including anglesite, barite, jarosite, alunite and basaluminite. Aluminum hydrolyzes near pH 5 (pK 1 = 5.0) and provides buffering and removal of Al by mineral precipitation from pH 4&ndash;5.5. Dissolved sulfate behaves conservatively because the amount removed from solution by precipitation is usually too small relative to the high concentrations in the water column and relative to the flow rate of the water.

Applied Geochemistry

Formation and prevention of pipe scale from acid mine drainage at Iron Mountain and Leviathan Mines, California, USA

Pipelines carrying acid mine drainage (AMD) to treatment plants commonly form pipe scale, an Fe(III)-rich precipitate that forms inside the pipelines and requires periodic and costly cleanout and maintenance. Pipelines at Iron Mountain Mine (IMM) and Leviathan Mine (LM) in California carry acidic water from mine sources to a treatment plant and have developed pipe scale. Samples of scale and AMD were collected from both mine sites for mineralogical, microbiological, and chemical analysis. The scale mineralogy was primarily schwertmannite with minor amounts of poorly crystalline goethite. Although the bulk composition of the scale was similar along the length of the pipeline at IMM, the number of iron-oxidizing bacteria and concentrations of associated trace elements decreased along the flow-path inside the pipeline. Laboratory batch experiments with unfiltered AMD from IMM and LM showed that Fe(II) oxidation was driven by microbial activity when the pH was <5. A remediation strategy of decreasing the pH to <2.2 was tested through geochemical modeling and laboratory experiments. These experiments indicated that scale formation could be prevented by decreasing the pH, which could be achieved at IMM by mixing source waters. However, the presence of Fe(III)-rich scale in a pipeline buffers the pH to higher values that may affect the efficacy of this remedial approach.

California

Hydrogeochemistry and coal-associated bacterial populations from a methanogenic coal bed

Biogenic coalbed methane (CBM), a microbially-generated source of natural gas trapped within coal beds, is an important energy resource in many countries. Specific bacterial populations and enzymes involved in coal degradation, the potential rate-limiting step of CBM formation, are relatively unknown. The U.S. Geological Survey (USGS) has established a field site, (Birney test site), in an undeveloped area of the Powder River Basin (PRB), with four wells completed in the Flowers-Goodale coal bed, one in the overlying sandstone formation, and four in overlying and underlying coal beds (Knoblach, Nance, and Terret). The nine wells were positioned to characterize the hydraulic conductivity of the Flowers-Goodale coal bed and were selectively cored to investigate the hydrogeochemistry and microbiology associated with CBM production at the Birney test site. Aquifer-test results indicated the Flowers-Goodale coal bed, in a zone from about 112 to 120 m below land surface at the test site, had very low hydraulic conductivity (0.005 m/d) compared to other PRB coal beds examined. Consistent with microbial methanogenesis, groundwater in the coal bed and overlying sandstone contain dissolved methane (46 mg/L average) with low &delta; 13 C values (&minus;67&permil; average), high alkalinity values (22 meq/kg average), relatively positive &delta; 13 C-DIC values (4&permil; average), and no detectable higher chain hydrocarbons, NO 3 &minus; , or SO 4 2&minus; . Bioassay methane production was greatest at the upper interface of the Flowers-Goodale coal bed near the overlying sandstone. Pyrotag analysis identified Aeribacillus as a dominant in situ bacterial community member in the coal near the sandstone and statistical analysis indicated Actinobacteria predominated coal core samples compared to claystone or sandstone cores. These bacteria, which previously have been correlated with hydrocarbon-containing environments such as oil reservoirs, have demonstrated the ability to produce biosurfactants to break down hydrocarbons. Identifying microorganisms involved in coal degradation and the hydrogeochemical conditions that promote their activity is crucial to understanding and improving in situ CBM production.

Montana, Wyoming

Water quality and ecological risk assessment of intermittent streamflow through mining and urban areas of San Marcos River sub-basin, Mexico

Intermittent rivers are becoming more ecologically stressed worldwide. Flow cessation occurs naturally and spatiotemporally in these systems and anthropogenic activities such as wastewater discharges can have considerable impacts. Public entities mostly monitor water quality in permanent streams, leading to insufficient monitoring of intermittent streams and consequently to their potentially inadequate management.. This study analyzed spatiotemporal patterns of water quality and associated ecological risk through the quantification of physicochemical and microbiological pollutants in the intermittent river system of El Novillo and San Marcos in Northeast Mexico. Results showed that water quality varied geographically and seasonally. Based on national and international criteria, annual averages of water quality parameters analyzed suggested that streamflow in these river systems is of poor quality and poses high ecological risk to aquatic life. In the urban area, annual mean concentrations of Cd and Pb (0.14 and 0.4 mg/L) were 77- and 10-fold higher than their respective water quality criteria (<0.0018 and 0.04 mg/L). Statistically significant (q < 0.05) correlations were identified in concentrations of cyanide, Cd, Cu and Pb between wastewater seeping into the river and streamflow within the urban area. These observations highlight the unique sensitivity of intermittent urban streams to anthropogenic activities and may provide useful information to enhance current water management plans for the El Novillo-San Marcos River system for the protection of ecosystem integrity and human health.

El Novillo Canyon

Changes in microbial communities and associated water and gas geochemistry across a sulfate gradient in coal beds: Powder River Basin, USA

Competition between microbial sulfate reduction and methanogenesis drives cycling of fossil carbon and generation of CH 4 in sedimentary basins. However, little is understood about the fundamental relationship between subsurface aqueous geochemistry and microbiology that drives these processes. Here we relate elemental and isotopic geochemistry of coal-associated water and gas to the microbial community composition from wells in two different coal beds across CH 4 and SO 4 2− gradients (Powder River Basin, Montana, USA). Areas with high CH 4 concentrations generally have higher alkalinity and δ 13 C-DIC values, little to no SO 4 2− , and greater conversion of coal-biodegradable organics to CH 4 (based on δ 13 C-CH 4 and δ 13 C-CO 2 values). Wells with SO 4 2− concentrations from 2 to 10 mM had bacterial populations dominated by several different sulfate-reducing bacteria and archaea that were mostly novel and unclassified. In contrast, in wells with SO 4 2− concentrations <1 mM, the sequences were dominated by presumptive syntrophic bacteria as well as archaeal Methanosarcinales and Methanomicrobiales . The presence of sequences indicative of these bacteria in low SO 4 2− methanogenic wells may suggest a syntrophic role in coal biodegradation and/or the generation of methanogenic substrates from intermediate organic compounds. Archaeal sequences were observed in all sampled zones, with an enrichment of sequences indicative of methanogens in low SO 4 2− zones and unclassified sequences in high SO 4 2− zones. However, sequences indicative of Methanomassiliicoccales were enriched in intermediate SO 4 2− zones and suggest tolerance to SO 4 2− and/or alternative metabolisms in the presence of SO 4 2− . Moreover, sequences indicative of methylotrophic methanogens were more prevalent in an intermediate SO 4 2− and CH 4 well and results suggest an important role for methylotrophic methanogens in critical zone transitions. The presented results demonstrate in situ changes in bacterial and archaeal population distributions along a SO 4 2− gradient associated with recalcitrant, organic carbon that is biodegraded and converted to CO 2 and/or CH 4 .

Powder River Basin

The dynamic influence of subsurface geological processes on the assembly and diversification of thermophilic microbial communities in continental hydrothermal systems

An accepted paradigm of hydrothermal systems is the process of phase separation, or boiling, of a deep, homogeneous hydrothermal fluid as it ascends through the subsurface resulting in gas rich and gas poor fluids. While phase separation helps to explain first-order patterns in the chemistry and biology of a hot spring’s surficial expression, we know little about the subsurface architecture beneath “phase-separated” pools and the timescales over which phase separation processes occur. Essentially, we have a two-dimensional understanding of a four-dimensional process. By combining geophysical, geochemical, isotopic, and microbiological measurements of two adjacent phase-separated hot springs in Norris Geyser Basin, Yellowstone National Park, we provide a four-dimensional assessment of phase separation processes and their biological manifestation. We uniquely show that Yellowstone’s hydrothermal waters originate from a deep sedimentary aquifer and that both meteoric recharge and shallow reactive transport processes are required to establish the geobiological feedbacks that drive bimodal distributions in the geochemical and microbial composition of hot springs. Specifically, over periods of tens of years, gas-enriched fluids containing volcanic sulfide mix with meteoric waters resulting in microbially-mediated production of sulfuric acid by thermoacidophilic Archaea in the near subsurface. In contrast, over periods of hundreds of years, anoxic residual liquid rises to the surface where it is infused with atmospheric gas fostering Archaea and Bacteria that are largely dependent on oxygen. As such, our results provide formative insight into the causative links between subsurface geological processes, the development of geochemical fluids, and the assembly and diversification of thermophilic microbial communities in hydrothermal systems.

Wyoming

Using Cl/Br ratios and other indicators to assess potential impacts on groundwater quality from septic systems: A review and examples from principal aquifers in the United States

A detailed review was made of chemical indicators used to identify impacts from septic tanks on groundwater quality. Potential impacts from septic tank leachate on groundwater quality were assessed using the mass ratio of chloride–bromide (Cl/Br), concentrations of selected chemical constituents, and ancillary information (land use, census data, well depth, soil characteristics) for wells in principal aquifers of the United States. Chemical data were evaluated from 1848 domestic wells in 19 aquifers, 121 public-supply wells in 6 aquifers, and associated monitoring wells in four aquifers and their overlying hydrogeologic units. Based on previously reported Cl/Br ratios, statistical comparisons between targeted wells (where Cl/Br ratios range from 400 to 1100 and Cl concentrations range from 20 to 100 mg/L) and non-targeted wells indicated that shallow targeted monitoring and domestic wells (<20 m depth below land surface) had a significantly ( p < 0.05) higher median percentage of houses with septic tanks (1990 census data) than non-targeted wells. Higher ( p = 0.08) median nitrate–N concentration (3.1 mg/L) in oxic (dissolved oxygen concentrations >0.5 mg/L) shallow groundwater from target domestic wells, relative to non-target wells (1.5 mg/L), corresponded to significantly higher potassium, boron, chloride, dissolved organic carbon, and sulfate concentrations, which may also indicate the influence of septic-tank effluent. Impacts on groundwater quality from septic systems were most evident for the Eastern Glacial Deposits aquifer and the Northern High Plains aquifer that were associated with the number of housing units using septic tanks, high permeability of overlying sediments, mostly oxic conditions, and shallow wells. Overall, little or no influence from septic systems were found for water samples from the deeper public-supply wells. The Cl/Br ratio is a useful first-level screening tool for assessing possible septic tank influence in water from shallow wells (<20 m) with the range of 400–1100. The use of this ratio would be enhanced with information on other chloride sources, temporal variability of chloride and bromide concentrations in shallow groundwater, knowledge of septic-system age and maintenance, and the use of multiple tracers (combination of additional chemical and microbiological indicators).

Journal of Hydrology

Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Coring operations, core sedimentology, and lithostratigraphy

In February 2007, BP Exploration (Alaska), the U.S. Department of Energy, and the U.S. Geological Survey completed the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well (Mount Elbert well) in the Milne Point Unit on the Alaska North Slope. The program achieved its primary goals of validating the pre-drill estimates of gas hydrate occurrence and thickness based on 3-D seismic interpretations and wireline log correlations and collecting a comprehensive suite of logging, coring, and pressure testing data. The upper section of the Mount Elbert well was drilled through the base of ice-bearing permafrost to a casing point of 594 m (1950 ft), approximately 15 m (50 ft) above the top of the targeted reservoir interval. The lower portion of the well was continuously cored from 606 m (1987 ft) to 760 m (2494 ft) and drilled to a total depth of 914 m. Ice-bearing permafrost extends to a depth of roughly 536 m and the base of gas hydrate stability is interpreted to extend to a depth of 870 m. Coring through the targeted gas hydrate bearing reservoirs was completed using a wireline-retrievable system. The coring program achieved 85% recovery of 7.6 cm (3 in) diameter core through 154 m (504 ft) of the hole. An onsite team processed the cores, collecting and preserving approximately 250 sub-samples for analyses of pore water geochemistry, microbiology, gas chemistry, petrophysical analysis, and thermal and physical properties. Eleven samples were immediately transferred to either methane-charged pressure vessels or liquid nitrogen for future study of the preserved gas hydrate. Additional offsite sampling, analyses, and detailed description of the cores were also conducted. Based on this work, one lithostratigraphic unit with eight subunits was identified across the cored interval. Subunits II and Va comprise the majority of the reservoir facies and are dominantly very fine to fine, moderately sorted, quartz, feldspar, and lithic fragment-bearing to -rich sands. Lithostratigraphic and palynologic data indicate that this section is most likely early Eocene to late Paleocene in age. The examined units contain evidence for both marine and non-marine lithofacies, and indications that the depositional environment for the reservoir facies may have been shallower marine than originally interpreted based on pre-drill wireline log interpretations. There is also evidence of reduced salinity marine conditions during deposition that may be related to the paleo-climate and depositional conditions during the early Eocene.

Alaska

Processes affecting transport of uranium in a suboxic aquifer

At the Naturita site in Colorado, USA, groundwaters were sampled and analyzed for chemical composition and by culture and culture-independent microbiological techniques. In addition, sediments were extracted with a dilute sodium carbonate solution to determine quantities of labile uranium within the sediments. Samples from the upgradient portion of the contaminated aquifer , where very little dissolved Fe(II) is found in the groundwater, have uranium content that is controlled by U(VI) adsorption and few metal-reducing bacteria are observed. In the extreme downgradient portion of the aquifer, where dissolved Fe(II) is observed, uranium content of the sediments includes significant quantities of reduced U(IV) and diverse populations of Fe(III)-reducing bacteria were present in the subsurface with the potential of reducing U(VI) to U(IV).

Physics and Chemistry of the Earth

Total- and methyl-mercury concentrations and methylation rates across the freshwater to hypersaline continuum of the Great Salt Lake, Utah, USA

We examined mercury (Hg) speciation in water and sediment of the Great Salt Lake and surrounding wetlands, a locale spanning fresh to hypersaline and oxic to anoxic conditions, in order to test the hypothesis that spatial and temporal variations in Hg concentration and methylation rates correspond to observed spatial and temporal trends in Hg burdens previously reported in biota. Water column, sediment, and pore water concentrations of methylmercury (MeHg) and total mercury (THg), as well as related aquatic chemical parameters were examined. Inorganic Hg(II)-methylation rates were determined in selected water column and sediment subsamples spiked with inorganic divalent mercury ( 204 Hg(II)). Net production of Me 204 Hg was expressed as apparent first-order rate constants for methylation ( k meth ), which were also expanded to MeHg production potential (MPP) rates via combination with tin reducible &lsquo;reactive&rsquo; Hg(II) (Hg(II) R ) as a proxy for bioavailable Hg(II). Notable findings include: 1) elevated Hg concentrations previously reported in birds and brine flies were spatially proximal to the measured highest MeHg concentrations, the latter occurring in the anoxic deep brine layer (DBL) of the Great Salt Lake; 2) timing of reduced Hg(II)-methylation rates in the DBL (according to both k meth and MPP) coincides with reduced Hg burdens among aquatic invertebrates (brine shrimp and brine flies) that act as potential vectors of Hg propagation to the terrestrial ecosystem; 3) values of k meth were found to fall within the range reported by other studies; and 4) MPP rates were on the lower end of the range reported in methodologically comparable studies, suggesting the possibility that elevated MeHg in the anoxic deep brine layer results from its accumulation and persistence in this quasi-isolated environment, due to the absence of light (restricting abiotic photo demethylation) and/or minimal microbiological demethylation.

Utah

Pilot-scale expanded assessment of inorganic and organic tapwater exposures and predicted effects in Puerto Rico, USA

A pilot-scale expanded target assessment of mixtures of inorganic and organic contaminants in point-of-consumption drinking water (tapwater, TW) was conducted in Puerto Rico (PR) to continue to inform TW exposures and corresponding estimations of cumulative human-health risks across the US. In August 2018, a spatial synoptic pilot assessment of than 524 organic, 37 inorganic, and select microbiological contaminant indicators was conducted in 14 locations (7 home; 7 commercial) across PR. A follow-up 3-day temporal assessment of TW variability was conducted in December 2018 at two of the synoptic locations (1 home, 1 commercial) and included daily pre- and post-flush samples. Concentrations of regulated and unregulated TW contaminants were used to calculate cumulative in vitro bioactivity ratios and Hazard Indices (HI) based on existing human-health benchmarks. Synoptic results confirmed that human exposures to inorganic and organic contaminant mixtures, which are rarely monitored together in drinking water at the point of consumption, occurred across PR and consisted of elevated concentrations of inorganic contaminants (e.g., lead, copper), disinfection byproducts (DBP), and to a lesser extent per/polyfluoroalkyl substances (PFAS) and phthalates. Exceedances of human-health benchmarks in every synoptic TW sample support further investigation of the potential cumulative risk to vulnerable populations in PR and emphasize the importance of continued broad characterization of drinking-water exposures at the tap with analytical capabilities that better represent the complexity of both inorganic and organic contaminant mixtures known to occur in ambient source waters. Such health-based monitoring data are essential to support public engagement in source water sustainability and treatment and to inform consumer point-of-use treatment decision making in PR and throughout the US.

Puerto Rico

Temporally dense monitoring of pathogen occurrence at four drinking-water well sites – Insights and Implications

Yearlong, event based, microbiological and chemical sampling was conducted at four public water supply well sites spanning a range of geologic settings and well depths to look for correlation between precipitation events and microbial occurrence. Near-continuous monitoring using autosamplers occurred just before, during, and after 5–7 sampling events triggered by rainfall and/or snowmelt. Microbial genetic material was noted at all four locations during all but one sampling event, but was exceedingly variable in time, where one sample would have no detections and the next sample could be a relatively high concentration. The highest microbial sums (microbial concentrations summed over an event) were observed during months in which precipitation exceeded historical averages. Extended wet conditions through the spring thaw resulted in the highest percentage of microbial positive samples, though at relatively low concentrations. Sampling events that followed drier than normal periods showed longer lag times between the onset of precipitation and microbial occurrence, as well as lower microbial detection rates. Although a general lag time pattern was observed at each site, the largest offset in time was observed at the site with the greatest depth to water. The study's temporally dense representation of drinking water pathogen characterization suggests that single event or infrequent periodic sampling of a drinking water supply cannot provide a representative characterization of the probability that pathogens are present, which likely has ramifications for calculating health risk assessments.

Minnesota