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USGS1996

Geochemical and isotopic composition of ground water with emphasis on sources of sulfate in the upper Floridan Aquifer in parts of Marion, Sumter, and Citrus counties, Florida

In inland areas of northwest central Florida, sulfate concentrations in the Upper Floridan aquifer are extremely variable and sometimes exceed drinking water standards (250 milligrams per liter). This is unusual because the aquifer is unconfined and near the surface, allowing for active recharge. The sources of sulfate and geochemical processes controlling ground-water composition were evaluated in this area. Water was sampled from thirty-three wells in parts of Marion, Sumter, and Citrus Counties, within the Southwest Florida Water Management District; these included at least a shallow and a deep well at fifteen separate locations. Ground water was analyzed for major ions, selected trace constituents, dissolved organic carbon, and stable isotopes (sulfur-34 of sulfate and sulfide, carbon-13 of inorganic carbon, deuterium, and oxygen-18). Sulfate concentrations ranged from less than 0.2 to 1,400 milligrams per liter, with higher sulfate concentrations usually in water from deeper wells. The samples can be categorized into a low sulfate group (less than 30 milligrams per liter) and a high sulfate group (greater than 30 milligrams per liter). For the high sulfate water, concentrations of calcium and magnesium increased concurrently with sulfate. Chemical and isotopic data and mass-balance modeling indicate that the composition of high sulfate waters is controlled by dedolomitization reactions (dolomite dissolution and calcite precipitation, driven by dissolution of gypsum). Gypsum occurs deeper in the aquifer than open intervals of sampled wells. Upward flow has been documented in deeper parts of the aquifer in the study area, which may be driven by localized discharge areas or rapid flow in shallow parts of the aquifer. Mixing between shallow ground water and sulfate-rich water that dissolved gypsum at the base of the aquifer is probably responsible for the range of concentrations observed in the study area. Other solutes that increased with sulfate apparently originate from the gypsum itself, from other mineral assemblages found deeper in the aquifer in association with gypsum, and from residual seawater from less- flushed, deeper parts of the aquifer. These ions are subsequently transported with sulfate to shallower parts of the aquifer where gypsum is not present. The composition of low sulfate ground water is controlled by differences in the extent of microbially mediated reactions, which produce carbon dioxide. This, in turn, influences the extent of calcite dissolution. Ground waters which underwent limited microbial reactions contained dissolved oxygen and were usually in ridge areas where recharge typically is rapid. Anaerobic waters were in lower lying areas of Sumter County, where soils are poorly drained and aquifer recharge is slow. Anaerobic waters had higher concentrations of calcium, bicarbonate, sulfide, dissolved organic carbon, iron, manganese, and silica, and had lower concentrations of nitrate than aerobic ground waters. For low sulfate waters, sulfate generally originates from meteoric sources (atmospheric precipitation), with variable amounts of oxidation of reduced sulfur and sulfate reduction. Sulfide is sometimes removed from solution, probably by precipitation of a sulfide minerals such as pyrite. In areas where deep ground water has low sulfate concentrations, the shallow flow system is apparently deeper than where high sulfate concentrations occur, and upwelling sulfate-rich water is negligible. The range of sulfate concentrations observed in the study areas and differences in sulfate concentrations with depth indicate a complex interaction between shallow and deep ground-water flow systems.

Water-Resources Investigations Report↗

USGS1996

Assessment of intrinsic bioremediation of gasoline contamination in the shallow aquifer, Laurel Bay Exchange, Marine Corps Air Station Beaufort, South Carolina

Laboratory, field, and digital solute-transport- modeling studies demonstrate that microorganisms indigenous to the shallow ground-water system at Laurel Bay Exchange, Marine Corps Air Station Beaufort, South Carolina, can degrade petroleum hydrocarbons in gasoline released at the site. Microorganisms in aquifer sediments incubated in the laboratory under aerobic and anaerobic conditions mineralized radiolabeled carbon 14-toluene to 14 C-carbon dioxide with first-order rate constants of K bio = -0.640 per day and K bio = -0.003 per day, respectively. Digital solute- transport modeling using the numerical code SUTRA revealed that anaerobic biodegradation of benzene occurs with a first-order rate constant near K bio = -0.00025 per day. Sandy aquifer material beneath Laurel Bay Exchange is characterized by relatively high hydraulic conductivities (K aq = 8.9 to 17.3 feet per day), average ground-water flow rate of about 60 feet per year, and a relatively uniform hydraulic gradient of 0.004 feet per foot. The sandy aquifer material also has low adsorptive potentials for toluene and benzene (both about K ad = 2.0 x 10 -9 cubic feet per milligram), because of the lack of natural organic matter in the aquifer. The combination of this ground-water-flow rate and absence of significant adsorptive capacity in the aquifer permits toluene and benzene concentrations to be detected downgradient from the source area in monitoring wells, even though biodegradation of these compounds has been demonstrated. Solute-transport simulations, however, indicate that toluene and benzene will not reach the Broad River, the nearest point of contact with wildlife or human populations, about 3,600 feet west of the site boundary. These simulations also show that contamination will not be transported to the nearest Marine Corps property line about 2,400 feet south of the site. This is primarily because the source of contaminants has essentially been removed, and the low adsorptive capacity of the aquifer sediments has prevented the occurrence of an adsorbed, continuous source of petroleum hydrocarbons. Therefore, digital simulations of toluene and benzene transport at Laurel Bay Exchange indicate that intrinsic bioremediation could be a successful remediation alternative for prohibiting transport of dissolved toluene and benzene to the Broad River.

South Carolina↗

USGS1996

Distribution of petroleum hydrocarbons and toluene biodegradation, Knox Street fire pits, Fort Bragg, North Carolina

An investigation was conducted at the Knox Street fire pits, Fort Bragg, North Carolina, to monitor the distribution of toluene, ethylbenzene, and xylene (TEX) in soil vapor, ground water, and ground-water/vapor to evaluate if total concentrations of TEX at the site are decreasing with time, and to quantify biodegradation rates of toluene in the unsaturated and saturated zones. Soil-vapor and ground-water samples were collected around the fire pits and ground-water/vapor samples were collected along the ground-water discharge zone, Beaver Creek, on a monthly basis from June 1994 through June 1995. Concentrations of TEX compounds in these samples were determined with a field gas chro- matograph. Laboratory experiments were performed on aquifer sediment samples to measure rates of toluene biodegradation by in situ micro- organisms. Based on field gas chromatographic analytical results, contamination levels of TEX compounds in both soil vapor and ground water appear to decrease downgradient of the fire-pit source area. During the 1-year study period, the observed temporal and spatial trends in soil vapor TEX concentrations appear to reflect differences in the distribution of TEX among solid, aqueous, and gaseous phases within fuel-contaminated soils in the unsaturated zone. Soil temperature and soil moisture are two important factors which influence the distribution of TEX com- pounds among the different phases. Because of the short period of data collection, it was not possible to distinguish between seasonal fluc- tuations in soil vapor TEX concentrations and an overall net decrease in TEX concentrations at the study site. No seasonal trend was observed in total TEX concentrations for ground- water samples collected at the study site. Although the analytical results could not be used to determine if ground-water TEX concen- trations decreased during the study at a specific location, the data were used to examine rate constants of toluene biodegradation. Based on ground-water toluene concentration data, a maximum rate constant for anaerobic biodegradation of toluene in the saturated zone was estimated to be as low as 0.002 d-1 or as high as 0.026 d-1. Based on analyses of ground-water/vapor samples, toluene was the prin- cipal TEX compound identified in ground water discharging to Beaver Creek. Observed decreases in ground-water/vapor toluene concentrations during the study period may reflect a decrease in source inputs, an increase in dilution caused by higher ground-water flow, and(or) removal by biological or other physical processes. Rate constants of toluene anaerobic biodegradation determined by laboratory measurements illustrate a typical acclimation response of micro-organisms to hydrocarbon contamination in sediments collected from the site. Toluene biodegradation rate constants derived from laboratory microcosm studies ranged from 0.001 to 0.027 d-1, which is similar to the range of 0.002 to 0.026 d-1 for toluene biodegradation rate constants derived from ground-water analytical data. The close agreement of toluene biodegradation rate constants reported using both approaches offer strong evidence that toluene can be degraded at environmentally significant rates at the study site.

Water-Resources Investigations Report↗

USGS1999

Iron in the aquifer system of Suffolk County, New York, 1990-98

High concentrations of dissolved iron in ground water contribute to the biofouling of public-supply wells, and the treatment and remediation of biofouling are costly. Water companies on Long Island, N.Y., spend several million dollars annually to recondition, redevelop, and replace supply wells and distribution lines; treat dissolved iron with sequestering agents or by filtration; and respond to iron-related complaints by customers. This report summarizes the results of studies done by the U.S. Geological Survey, in cooperation with the Suffolk County Water Authority, to characterize the geochemistry and microbiology of iron in the aquifer system of Suffolk County. This information should be helpful for the siting and operation of supply wells. Concentrations of dissolved iron in Long Island's ground water, and the frequency of iron biofouling of wells, are highest in ground-water-discharge zones, particularly near the south shore. Ground water along a deep north-south flowpath of the Magothy aquifer in southwestern Suffolk County becomes anaerobic (oxygen deficient) and Fe(III) reducing at a distance of 8 to 10 kilometers south of the ground-water divide, and this change coincides with the downgradient increase in dissolved iron concentrations. The distribution of organic carbon, and the distribution and local variations in reactivity of Fe(III), in Magothy aquifer sediments have resulted in localized differences in redox microenvironments. For example, Fe(III)-reducing zones are associated with anaerobic conditions, where relatively large amounts of Fe(III) oxyhydroxide grain coatings are present, whereas sulfate-reducing zones are associated with lignite-rich lenses of silt and clay and appear to have developed in response to the depletion of available Fe(III) oxyhydroxides. The sulfate-reducing zones are characterized by relatively low concentrations of dissolved iron (resulting from iron-disulfide precipitation) and may be large enough to warrant water-supply development. Specific-capacity and water-quality data from wells screened in the Magothy aquifer indicate that water from biofouled wells contains higher median concentrations of total and dissolved iron and manganese, total phosphate, and dissolved sulfate, and lower median concentrations of dissolved oxygen and alkalinity, and lower pH, than does water from unaffected wells. Corresponding data from wells screened in the upper glacial aquifer indicate that water from biofouled wells contains higher median concentrations of total and dissolved manganese and dissolved sulfate, and lower pH, than does water from unaffected wells. Filamentous bacteria were detected in 31 (or 72 percent) of the 43 biofilm samples obtained from biofouled wells during reconditioning. The predominant filamentous organism was Gallionella ferruginea, a major biofouling agent in the upper glacial and Magothy aquifers throughout Suffolk County. Mineral-saturation indices indicate that most of the well-encrusting material is deposited when the wells are shut down. Furthermore, the use of treated water (which has a high pH and sometimes high concentrations of dissolved iron) for pump prelubrication when wells are shut down could greatly increase the rate of iron oxidation.

New York↗

USGS2026

Diverging mineral chemistry of iron and nickel throughout Earth’s changing redox conditions reveals foundation for their evolution as protein cofactors

Iron (Fe) and nickel (Ni) were both foundational to early metabolism, yet their biological trajectories diverged as Earth’s surface redox state changed. Here, we integrate mineral chemistry network analysis, protein metal-site coordination-sphere analysis, and curated redox comparisons to test how geochemistry and metalloprotein architecture co-evolved. Mineral network analyses show broader electronegativity variation and network diversity for Fe-bearing minerals through time relative to Ni-bearing minerals. In structural analyses of protein metal centers in a combined Fe/Ni protein structure set, it is shown that Fe- and Ni-associated environments differ in amino-acid composition, hydropathy structure, and cysteine representation. The greater chemical diversity and electronegativity variation in Fe minerals mirror the higher redox and structural versatility of Fe-binding proteins. The presence of Fe in a broader range of mineral and protein environments demonstrates the chemical adaptability of the metal, from the anoxic Archean to oxidative Earth surface conditions following the Great Oxidation Event. Iron, with its broad redox potential range in Fe-oxidoreductases, has a central role in both anaerobic and aerobic metabolisms. Nickel, by contrast, is less widespread in biology. Today, Ni is predominantly employed in deeply branching anaerobic pathways and by proteins with narrower redox potential ranges. Our results show that evolutionary processes, constrained by metal chemistry, habitually utilize Fe as a redox generalist while retaining Ni in specialized roles. The divergent paths of Ni and Fe, from rocks to proteins, demonstrate the intimate relationship between planetary geochemistry and metabolic origins on Earth and suggest that Fe/Ni geochemistry may inform habitability assessments in extraterrestrial environments when interpreted within specific planetary environmental contexts.

Life↗

USGS2021

Restoration of mangrove forest

Mangrove forests occur worldwide along tropical coasts in inundated soils where primary production and anaerobic conditions contribute to the building of soil organic matter (Also see Mangroves Hot-spot, Volume 2). Note that peat may accumulate in certain coastal mangrove (Middleton and McKee, 2001). The actual amount of soil organic matter stored in these wetlands depends on the balance between primary production and decomposition processes (Middleton and McKee, 2001; Kolka et al., 2018; Middleton, 2020). The restoration of mangroves can increase carbon stocks both in soil and aboveground biomass (Wickland et al., 2013; Chimner et al., 2017; Friess et al., 2019). While tropical inland peatland forests may have higher carbon sequestration rates than mangrove swamps, methane (CH4) emissions are generally lower in mangrove swamp, so that these wetlands have greater carbon sequestration potential (Kolka et al., 2018; Al-Haj and Fulweiler, 2020). Mangroves and forested boreal and temperate peatlands tend to store more carbon than non-forested peatlands (Kolka et al., 2018).

Book chapter↗

USGS2014

Adaptations of indigenous bacteria to fuel contamination in karst aquifers in south-central Kentucky

The karst aquifer systems in southern Kentucky can be dynamic and quick to change. Microorganisms that live in these unpredictable aquifers are constantly faced with environmental changes. Their survival depends upon adaptations to changes in water chemistry, taking advantage of positive stimuli and avoiding negative environmental conditions. The U.S. Geological Survey conducted a study in 2001 to determine the capability of bacteria to adapt in two distinct regions of water quality in a karst aquifer, an area of clean, oxygenated groundwater and an area where the groundwater was oxygen depleted and contaminated by jet fuel. Water samples containing bacteria were collected from one clean well and two jet fuel contaminated wells in a conduit-dominated karst aquifer. Bacterial concentrations, enumerated through direct count, ranged from 500,000 to 2.7 million bacteria per mL in the clean portion of the aquifer, and 200,000 to 3.2 million bacteria per mL in the contaminated portion of the aquifer over a twelve month period. Bacteria from the clean well ranged in size from 0.2 to 2.5 mm, whereas bacteria from one fuel-contaminated well were generally larger, ranging in size from 0.2 to 3.9 mm. Also, bacteria collected from the clean well had a higher density and, consequently, were more inclined to sink than bacteria collected from contaminated wells. Bacteria collected from the clean portion of the karst aquifer were predominantly (,95%) Gram-negative and more likely to have flagella present than bacteria collected from the contaminated wells, which included a substantial fraction (,30%) of Gram-positive varieties. The ability of the bacteria from the clean portion of the karst aquifer to biodegrade benzene and toluene was studied under aerobic and anaerobic conditions in laboratory microcosms. The rate of fuel biodegradation in laboratory studies was approximately 50 times faster under aerobic conditions as compared to anaerobic, sulfur-reducing conditions. The optimum pH for fuel biodegradation ranged from 6 to 7. These findings suggest that bacteria have adapted to water-saturated karst systems with a variety of active and passive transport mechanisms.

Kentucky↗

USGS2003

Big Soda Lake (Nevada). 1. Pelagic bacterial heterotrophy and biomass

Bacterial activities and abundance were measured seasonally in the water column of meromictic Big Soda Lake which is divided into three chemically distinct zones: aerobic mixolimnion, anaerobic mixolimnion, and anaerobic monimolimnion. Bacterial abundance ranged between 5 and 52 x 10 6 cells ml −1 , with highest biomass at the interfaces between these zones: 2–4 mg C liter −1 in the photosynthetic bacterial layer (oxycline) and 0.8–2.0 mg C liter −1 in the chemocline. Bacterial cell size and morphology also varied with depth: small coccoid cells were dominant in the aerobic mixolimnion, whereas the monimolimnion had a more diverse population that included cocci, rods, and large filaments. Heterotrophic activity was measured by [methyl- 3 H]thymidine incorporation and [ 14 C]glutamate uptake. Highest uptake rates were at or just below the photosynthetic bacterial layer and were attributable to small (<1 µ m) heterotrophs rather than the larger photosynthetic bacteria. These high rates of heterotrophic uptake were apparently linked with fermentation; rates of other mineralization processes (e.g. sulfate reduction, methanogenesis, denitrification) in the anoxic mixolimnion were insignificant. Heterotrophic activity in the highly reduced monimolimnion was generally much lower than elsewhere in the water column. Therefore, although the monimolimnion contained most of the bacterial abundance and biomass (&sim;60%), most of the cells there were inactive.

Nevada↗

USGS1999

Phytoremediation of trichloroethene (TCE) using cottonwood trees

Phytoremediation uses the natural ability of plants to degrade contaminants in ground water. A field demonstration designed to remediate aerobic shallow ground water that contains trichloroethene began in April 1996 with the planting of cottonwood trees over an approximately 0.2-hectare area at the Naval Air Station, Fort Worth, Tx. Ground water was sampled in July 1997, November 1997, February 1998, and June 1998. Analyses from samples indicate that tree roots have the potential to create anaerobic conditions in the ground water that will facilitate degradation of trichloroethene by microbially mediated reductive dichlorination. Dissolved oxygen concentrations, which varied across the site, were smallest near a mature cottonwood tree (about-20 years old) 60 meters southwest of the cottonwood plantings. Reduction of dissolved oxygen is the primary microbially mediated reaction occurring in the ground water beneath the planted trees, whereas near the mature cottonwood tree, data indicate that methanogenesis is the most probable reaction occurring. Reductive dichlorination either is not occurring or is not a primary process away from the mature tree. On the basis of isotopic analyses of carbon-13 at locations away from the mature tree, trichloroethene concentration is controlled by volatilization. Phytoremediation uses the natural ability of plants to degrade contaminants in ground water. A field demonstration designed to remediate aerobic shallow ground water that contains trichloroethene began in April 1996 with the planting of cottonwood trees over an approximately 0.2-hectare area at the Naval Air Station, Fort Worth, Tx. Ground water was sampled in July 1997, November 1997, February 1998, and June 1998. Analyses from samples indicate that tree roots have the potential to create anaerobic conditions in the ground water that will facilitate degradation of trichloroethene by microbially mediated reductive dichlorination. Dissolved oxygen concentrations, which varied across the site, were smallest near a mature cottonwood tree (about-20 years old) 60 meters southwest of the cottonwood plantings. Reduction of dissolved oxygen is the primary microbially mediated reaction occurring in the ground water beneath the planted trees, whereas near the mature cottonwood tree, data indicate that methanogenesis is the most probable reaction occurring. Reductive dichlorination either is not occurring or is not a primary process away from the mature tree. On the basis of isotopic analyses of carbon-13 at locations away from the mature tree, trichloroethene concentration is controlled by volatilization.

Conference Paper↗

USGS2002

Microbial ecology of a crude oil contaminated aquifer

Detailed microbial analyses of a glacial outwash aquifer contaminated by crude oil provide insights into the pattern of microbial succession from iron reducing to methanogenic in the anaerobic portion of the contaminant plume. We analysed sediments from this area for populations of aerobes, iron reducers, fermenters and methanogens, using the most probable number method. On the basis of the microbial data the anaerobic area can be divided into distinct physiological zones dominated by either iron-reducers or a consortium of fermenters and methanogens. Chemistry and permeability data show that methanogenic conditions develop first in areas of high hydrocarbon flux. Thus, we find methanogens both in high permeability horizons and also where separate-phase crude oil is present in either the saturated or unsaturated zone. Microbial numbers peak at the top of the separate-phase oil suggesting that growth is most rapid in locations with access to both hydrocarbons and nutrients infiltrating from the surface.

IAHS-AISH Publication↗

USGS2005

Physiological characterization of a broad spectrum reductively dechlorinating consortium

A wetland sediment-derived microbial consortium (WBC-2) was developed by the US Geological Survey and propagated in vitro to large quantities by SiREM Laboratory for potential use in bioaugmentation applications. On the basis of bench-scale tests, the consortium could completely dechlorinate 1,1,2,2-tetrachloroethylene, tetrachloroethylene, trichloroethylene, 1,1,2-trichloroethane, cis- and trans-1,2-dichoroethylene, 1,1-dichloroethylene, 1,2-dichloroethane, and vinyl chloride in culture medium. Batch microcosms were carried out under anaerobic conditions in culture medium with neutral pH and with pH adjusted from acidic (pH 4, 5, and 6) to alkaline (pH 8 and 9). To evaluate oxygen sensitivity of WBC-2, an aliquot was removed from an anaerobic culture vessel and poured into smaller containers on the bench top where a series of oxygen exposures were applied to the culture by bubbling ambient air through the culture at a rate of ??? 100 mL/min. Chlorinated methanes tended to inhibit activity of a wide range of microorganisms. Although toxicity effects from CT addition were observed with WBC-2 in liquid culture at 3 mg/L concentration, WBC-2 in the columns could maintain degradation of CT and chloroform (CF) and of the chlorinated ethanes and ethylenes at CT and CF concentrations of 10 and 20 mg/L, respectively. This is an abstract of a paper presented at the Proceedings of the 8th International In Situ and On-Site Bioremediation Symposium (Baltimore, MD 6/6-9/2005).

Conference Paper↗

USGS1997

Natural attenuation of chlorinated hydrocarbons in a freshwater wetland

Natural attenuation of chlorinated volatile organic compounds (VOC's) occurs as ground water discharges from a sand aquifer to a freshwater wetland at Aberdeen Proving Ground, Md. Field and laboratory results indicate that biotransformation in the anaerobic wetland sediments is an important attenuation process. Relatively high concentrations of the parent compounds trichloroethylene (TCE) and 1,1,2,2-tetrachloroethane (PCA) and low or undetectable concentrations of daughter products were measured in the aquifer. In contrast, relatively high concentrations of the daughter products cis- and trans-1,2-dichloroethylene (12DCE); vinyl chloride (VC); 1,1,2-trichloroethane (112TCA); and 1,2-dichloroethane (12DCA) were measured in ground water in the wetland sediments, although total VOC concentrations decreased upward from about 1 mu mol/L (micromoles per liter) at the base of the wetland sediments to less than 0.2 near the surface. Microcosm experiments showed that 12DCE and VC are produced from anaerobic degradation of both TCE and PCA; PCA degradation also produced 112TCA and 12DCA.

Maryland↗

USGS1978

Reconnaissance for microbial activity in the Magothy aquifer, Bay Park, New York, four years after artificial recharge

Tertiary-treated sewage effluent was injected into the Magothy aquifer at Bay Park, Long Island, N.Y., between 1968 and 1973. In 1977, the microbial flora in water samples from the injection well and from three nearby wells were surveyed. Differences in the composition of the microbial flora among the four wells were found. A bacterial community dominated by facultative and obligate anaerobes, including two Clostridium species and methanogenic bacteria, was found at a well 6.1 m from the injection well. By contrast, except for isolation of Clostridium sphenoides from a well 30 m away, only obligate aerobes and facultative anaerobes were found in water from the injection well and the 30 m well. Only a small number of obligate aerobes were found in samples from a well 61 m away. These results suggest that nutrients in the recharge water formed an organically enriched zone to at least a distance of 6.1 m from the point of injection but not as far as 61 m. Extensive pumping at the end of the injection program apparently removed exogeneous nutrients near the injection well.

New York↗

USGS1998

Ground-water age and atmospheric tracers: Simulation studies and analysis of field data from the Mirror Lake site, New Hampshire

The use of environmental tracers in characterization of ground-water systems is investigated through mathematical modeling of ground-water age and atmospheric tracer transport, and by a field study at the Mirror Lake site, New Hampshire. Theory is presented for modeling ground-water age using the advective-dispersive transport equation. The transport equation includes a zero-order source of unit strength, corresponding to the rate of aging, and can accommodate matrix diffusion and other exchange processes. The effect of temperature fluctuations and layered soils on transport of atmospheric gases to the water table is investigated using a one-dimensional numerical model of chlorofluorocarbon (CFC-11) transport. The nonlinear relation between temperature and Henry's Law coefficient (reflecting air/water phase partitioning) can cause the apparent recharge temperature to be elevated above the annual mean temperature where the water table is shallow. In addition, fine-grained soils can isolate the air phase in the unsaturated zone from the atmosphere. At the USGS' Mirror Lake, New Hampshire fractured-rock research site CFC concentrations near the water table are depleted where dissolved oxygen is low. CFC-11 and CFC-113 are completely absent under anaerobic conditions, while CFC-12 is as low as one-third of modern concentrations. Anaerobic biodegradation apparently consumes CFC's near the water table at this site. One area of active degradation appears to be associated with streamflow loss to ground water. Soil gas concentrations are generally close to atmospheric levels, although some spatial correlation is observed between depleted concentrations of CFC-11 and CFC-113 in soil gas and water-table samples. Results of unsaturated-zone monitoring indicate that recharge occurs throughout the year in the watershed, even during summer evapotranspiration periods, and that seasonal temperature fluctuations occur as much as 5 meters below land surface. Application of ground-water age and CFC-11 transport models to the large-scale ground-water system at Mirror Lake illustrates the similarities between age and chemical transport. Generally, bedrock porosities required to match observed apparent ages from CFC concentrations are high relative to porosities measured on cores. Although matrix diffusion has no effect on steady-state age, it can significantly reduce CFC concentrations in fractured rock in which the effective porosity is low.

New Hampshire↗

USGS1996

The toxicity of selected gasoline components to glucose methanogenesis by aquifer microorganisms

Six model hydrocarbons, representing various classes of chemicals found in gasoline, and methyl ethyl ketone, were assayed for their inhibitory effect on glucose methanogenesis in slurries prepared from aquifer sediments and ground water. Biogas (CH 4 and CO 2 ) production was monitored with an automated pressure transducer system. Benzene, 1-methyl naphthalene, and methyl tert -butyl ether (MTBE) were found to have no inhibitory influence on biogas production rates at concentrations up to 71·7 mg/L. Similarly, octane, cyclohexane, indan, and methyl ethyl ketone (MEK) were found to have only marginal negative effects on the rate of biogas production in aquifer slurries, at concentrations ranging from 51·7 to 72·1 mg/L. Thus, gasoline components had low apparent toxicities to microorganisms responsible for glucose methanogenesis in aquifier slurries. As the concentrations of the assayed hydrocarbons are about 100 times those typically reported after an aquifer has been contaminated with gasoline, it is unlikely that individual hydrocarbons will substantially impact anaerobic metabolic processes.

Anaerobe↗

USGS2014

Runoff sources and flowpaths in a partially burned, upland boreal catchment underlain by permafrost

Boreal soils in permafrost regions contain vast quantities of frozen organic material that is released to terrestrial and aquatic environments via subsurface flowpaths as permafrost thaws. Longer flowpaths may allow chemical reduction of solutes, nutrients, and contaminants, with implications for greenhouse gas emissions and aqueous export. Predicting boreal catchment runoff is complicated by soil heterogeneities related to variability in active layer thickness, soil type, fire history, and preferential flow potential. By coupling measurements of permeability, infiltration potential, and water chemistry with a stream chemistry end member mixing model, we tested the hypothesis that organic soils and burned slopes are the primary sources of runoff, and that runoff from burned soils is greater due to increased hydraulic connectivity. Organic soils were more permeable than mineral soils, and 25% of infiltration moved laterally upon reaching the organic-mineral soil boundary on unburned hillslopes. A large portion of the remaining water infiltrated into deeper, less permeable soils. In contrast, burned hillslopes displayed poorly defined soil horizons, allowing rapid, mineral-rich runoff through preferential pathways at various depths. On the catchment scale, mineral/organic runoff ratios averaged 1.6 and were as high as 5.2 for an individual storm. Our results suggest that burned soils are the dominant source of water and solutes reaching the stream in summer, whereas unburned soils may provide longer term storage and residence times necessary for production of anaerobic compounds. These results are relevant to predicting how boreal catchment drainage networks and stream export will evolve given continued warming and altered fire regimes.

Alaska↗

USGS2016

Basin scale controls on CO 2 and CH 4 emissions from the Upper Mississippi River

The Upper Mississippi River, engineered for river navigation in the 1930s, includes a series of low-head dams and navigation pools receiving elevated sediment and nutrient loads from the mostly agricultural basin. Using high-resolution, spatially resolved water quality sensor measurements along 1385 river kilometers, we show that primary productivity and organic matter accumulation affect river carbon dioxide and methane emissions to the atmosphere. Phytoplankton drive CO 2 to near or below atmospheric equilibrium during the growing season, while anaerobic carbon oxidation supports a large proportion of the CO 2 and CH 4 production. Reductions of suspended sediment load, absent of dramatic reductions in nutrients, will likely further reduce net CO 2 emissions from the river. Large river pools, like Lake Pepin, which removes the majority of upstream sediments, and large agricultural tributaries downstream that deliver significant quantities of sediments and nutrients, are likely to persist as major geographical drivers of greenhouse gas emissions.

Upper Mississippi River↗

USGS2015

Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O 2 and elevated concentrations of Mn 2+ , Fe 2+ , CH 4 , and Ca 2+ over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH 4 and CO 2 gas phases, and sorption of Fe, Mn, and H + . Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH 4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO 2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.

Minnesota↗