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At least 415 records · Page 23Linked to original sources

Characterization of Preferential Ground-Water Seepage From a Chlorinated Hydrocarbon-Contaminated Aquifer to West Branch Canal Creek, Aberdeen Proving Ground, Maryland, 2002-04

Wetlands act as natural transition zones between ground water and surface water, characterized by the complex interdependency of hydrology, chemical and physical properties, and biotic effects. Although field and laboratory demonstrations have shown efficient natural attenuation processes in the non-seep wetland areas and stream bottom sediments of West Branch Canal Creek, chlorinated volatile organic compounds are present in a freshwater tidal creek at Aberdeen Proving Ground, Maryland. Volatile organic compound concentrations in surface water indicate that in some areas of the wetland, preferential flow paths or seeps allow transport of organic compounds from the contaminated sand aquifer to the overlying surface water without undergoing natural attenuation. From 2002 through 2004, the U.S. Geological Survey, in cooperation with the Environmental Conservation and Restoration Division of the U.S. Army Garrison, Aberdeen Proving Ground, characterized preferential ground-water seepage as part of an ongoing investigation of contaminant distribution and natural attenuation processes in wetlands at this site. Seep areas were discrete and spatially consistent during thermal infrared surveys in 2002, 2003, and 2004 throughout West Branch Canal Creek wetlands. In these seep areas, temperature measurements in shallow pore water and sediment more closely resembled those in ground water than those in nearby surface water. Generally, pore water in seep areas contaminated with chlorinated volatile organic compounds had lower methane and greater volatile organic compound concentrations than pore water in non-seep wetland sediments. The volatile organic compounds detected in shallow pore water in seeps were spatially similar to the dominant volatile organic compounds in the underlying Canal Creek aquifer, with both parent and anaerobic daughter compounds detected. Seep locations characterized as focused seeps contained the highest concentrations of chlorinated parent compounds, relatively low concentrations of chlorinated daughter compounds, and insignificant concentrations of methane in shallow pore water samples. These seeps were primarily along the creek edge or formed a dendritic-like pattern between the wetland and creek channel. In contrast, seep locations characterized as diffuse seeps contained relatively high concentrations of chlorinated daughter compounds (or a mixture of daughter and parent compounds) and detectable methane concentrations in shallow pore water samples. These seeps were primarily along the wetland boundary. Qualitative thermal infrared surveys coupled with quantitative verification of temperature differences, and screening for volatile organic compound and methane concentrations proved to be effective tools in determining the overall extent of preferential seepage. Hydrologic and physical properties of wetland sediments were characterized at two focused and one diffuse seep location. In the seeps with focused discharge, measured seepage was consistent over the tidal cycle, whereas more variability with tidal fluctuation was measured in the diffuse seep location. At all locations, areas were identified within the general seep boundaries where discharge was minimal. In all cases, the geometric mean of non-zero vertical flux measurements was greater than those previously reported in the non-seep wetland sediments using flow-net analysis. Flux was greater in the focused discharge areas than in the diffuse discharge area, and all fluxes were within the range reported in the literature for wetland discharge. Vertical hydraulic conductivity estimated from seepage flux and a mean vertical gradient at seeps with focused discharge resulted in a minimum hydraulic conductivity two orders of magnitude greater than those estimated in the non-seep sediment. In contrast, vertical conductivity estimates at a diffuse seep were similar to estimates along a nearby line of section through a non-seep area.

Scientific Investigations Report↗

Investigation of ground-water contamination at a drainage ditch, Installation Restoration Site 4, Naval Air Station Corpus Christi, Corpus Christi, Texas, 2005–06

The U.S. Geological Survey, in cooperation with the Naval Facilities Engineering Command Southeast, used newly developed sampling methods to investigate ground-water contamination by chlorobenzenes beneath a drainage ditch on the southwestern side of Installation Restoration Site 4, Naval Air Station Corpus Christi, Corpus Christi, Texas, during 2005-06. The drainage ditch, which is a potential receptor for ground-water contaminants from Installation Restoration Site 4, intermittently discharges water to Corpus Christi Bay. This report uses data from a new type of pore-water sampler developed for this investigation and other methods to examine the subsurface contamination beneath the drainage ditch. Analysis of ground water from the samplers indicated that chlorobenzenes (maximum detected concentration of 160 micrograms per liter) are present in the ground water beneath the ditch. The concentrations of dissolved oxygen in the samples (less than 0.05-0.4 milligram per liter) showed that the ground water beneath and near the ditch is anaerobic, indicating that substantial chlorobenzene biodegradation in the aquifer beneath the ditch is unlikely. Probable alternative mechanisms of chlorobenzene removal in the ground water beneath the drainage ditch include sorption onto the organic-rich sediment and contaminant depletion by cattails through uptake, sorption, and localized soil aeration.

Texas↗

Mercury and methylmercury in water and bottom sediments of wetlands at Lostwood National Wildlife Refuge, North Dakota, 2003-04

Certain ecosystem types, particularly wetlands, have environmental characteristics that can make them particularly sensitive to mercury inputs and that can result in large mercury concentrations in fish or other aquatic biota. To provide information needed to make effective management decisions to decrease human and wildlife exposure to methylmercury in northern prairie pothole wetlands, the U.S. Geological Survey, in cooperation with the North Dakota Department of Health, conducted a study to assess mercury and methylmercury concentrations in wetlands at the Lostwood National Wildlife Refuge (the Refuge) in northwest North Dakota. In April 2003 and 2004, water and bottom-sediment samples were collected from 44 individual wetlands that were classified as one of four wetland types. Many factors that may affect methylmercury production were considered in the study. The prairie pothole wetlands at the Refuge had large ranges in major environmental characteristics. Hydrologic differences, most notably semiannual wetting and drying cycles, that are intrinsic to prairie pothole wetlands affected methylmercury concentrations. This likely resulted from the stimulation of anaerobic microbial activity following reflooding of soils, particularly soils containing substantial organic carbon. Among the four wetland types considered for this study, seasonal and semipermanent wetlands generally had the largest methylmercury concentrations. Regardless of wetland type, however, methylmercury concentrations at the Refuge are large in relation to reported concentrations for natural aquatic systems.

North Dakota↗

Design and Performance of an Enhanced Bioremediation Pilot Test in a Tidal Wetland Seep, West Branch Canal Creek, Aberdeen Proving Ground, Maryland

Because of a lack of available in situ remediation methods for sensitive wetland environments where contaminated groundwater discharges, the U.S. Geological Survey, in cooperation with the U.S. Army Garrison, Aberdeen Proving Ground, Maryland, conceived, designed, and pilot tested a permeable reactive mat that can be placed horizontally at the groundwater/surface-water interface. Development of the reactive mat was part of an enhanced bioremediation study in a tidal wetland area along West Branch Canal Creek at Aberdeen Proving Ground, where localized areas of preferential discharge (seeps) transport groundwater contaminated with carbon tetrachloride, chloroform, tetrachloroethene, trichloroethene, and 1,1,2,2-tetrachloroethane from the Canal Creek aquifer to land surface. The reactive mat consisted of a mixture of commercially available organic- and nutrient-rich peat and compost that was bioaugmented with a dechlorinating microbial consortium, WBC-2, developed for this study. Due to elevated chlorinated methane concentrations in the pilot test site, a layer of zero-valent iron mixed with the peat and compost was added at the base of the reactive mat to promote simultaneous abiotic and biotic degradation. The reactive mat for the pilot test area was designed to optimize chlorinated volatile organic compound degradation efficiency without altering the geotechnical and hydraulic characteristics, or creating undesirable water quality in the surrounding wetland area, which is referred to in this report as achieving geotechnical, hydraulic, and water-quality compatibility. Optimization of degradation efficiency was achieved through the selection of a sustainable organic reactive matrix, electron donor, and bioaugmentation method. Consideration of geotechnical compatibility through design calculations of bearing capacity, settlement, and geotextile selection showed that a 2- to 3-feet tolerable thickness of the mat was possible, with 0.17 feet settlement predicted for unconsolidated sediments between 1.5 and 6 years following installation of the reactive mat. To ensure hydraulic compatibility in the mat design, mat materials that had a hydraulic conductivity greater than the surrounding wetland sediments were selected, and the mixture was optimized to consist of 1.5 parts compost, 1.5 parts peat and 1 part sand as a safeguard against fluidization. Sediment and matrix properties also indicated that a nonwoven geotextile with a cross-plane flow greater than that of the native sediments was suitable as the base of the reactive mat. Another nonwoven geotextile was selected for installation between the iron mix and organic zones of the mat to create more laminar flow conditions within the mat. Total metals and sequential extraction procedure analyses of mat materials, which were conducted to evaluate water-quality compatibility of the mat materials, showed that concentrations of metals in the compost ranged from one-half to one order of magnitude below consensus-based probable effect concentrations in sediment. A 22-inch-thick reactive mat, containing 0.5 percent WBC-2 by volume, was constructed at seep area 3-4W and monitored from October 2004 through October 2005 for the pilot test. No local, immediate failure of the mat or of wetland sediments was observed during mat installation, indicating that design estimates of bearing capacity and geotextile textile selection ensured the integrity of the mat and wetland sediments during and following installation. Measurements of surface elevation of the mat showed an average settlement of the mat surface of approximately 0.25 feet after 10 months, which was near the predicted settlement for unconsolidated sediment. Monitoring showed rapid establishment and sustainment throughout the year of methanogenic conditions conducive to anaerobic biodegradation and efficient dechlorination activity by WBC-2. The median mass removal of chloromethanes and total chloroethenes and ethane during the

Scientific Investigations Report↗

Diel Sampling of Groundwater and Surface Water for Trace Elements and Select Water-Quality Constituents at a Former Zinc Smelter Site near Hegeler, Illinois, August 1-3, 2007

Surface water can exhibit substantial diel variations in the concentration of a number of constituents. Sampling regimens that do not characterize diel variations in water quality can result in an inaccurate understanding of site conditions and of the threat posed by the site to human health and the environment. Surface- and groundwater affected by acid drainage were sampled every 60 to 90 minutes over a 48-hour period at a former zinc smelter known as the Hegeler Zinc Superfund Site, in Hegeler, Ill. Groundwater-quality data from a well at the site indicate stable, low pH, weakly oxidizing geochemical conditions in the aquifer. With the exceptions of temperature and pH, no constituents exhibited diel variations in groundwater. Variations in temperature and pH likely were not representative of conditions in the aquifer. Surface water was sampled at a site on Grape Creek. Diel variations were observed in temperature, dissolved oxygen, pH, and specific conductance, and in the concentrations of nitrite, barium, iron, lead, vanadium, and possibly uranium. Concentrations during the diel cycles varied by about an order of magnitude for nitrite and varied by about a factor of two for barium, iron, lead, vanadium, and uranium. Temperature, dissolved oxygen, specific conductance, nitrite, barium, lead, and uranium generally reached maximum values during the afternoon and minimum values during the night. Iron, vanadium, and pH generally reached minimum values during the afternoon and maximum values during the night. These variations would need to be accounted for during sampling of surface-water quality in similar hydrologic settings. The temperature variations in surface water were affected by variations in air temperature. Concentrations of dissolved oxygen were affected by variations in the intensity of photosynthetic activity and respiration. Nitrite likely was formed by the oxidation of ammonium by dissolved oxygen and degraded by its anaerobic oxidation by ammonium or as part of the decomposition of organic matter. Variations in pH were affected by the photoreduction of Fe3+ to Fe2+ and the precipitation of iron oxyhydroxides. Diel variations in concentrations of iron and vanadium were likely caused by variations in the dissolution and precipitation of iron oxyhydroxides, oxyhydroxysulfates, and hydrous sulfates, which may have been affected by in the intensity of insolation, iron photoreduction, and the concentration of dissolved oxygen. The concentrations of lead, uranium, and perhaps barium in Grape Creek may have been affected by competition for sorption sites on iron oxyhydroxides. Competition for sorption sites was likely affected by variations in pH and the concentration of Fe2+. Constituent concentrations likely also were affected by precipitation and dissolution of minerals that are sensitive to changes in pH, temperature, oxidation-reduction conditions, and biologic activity. The chemical and biologic processes that resulted in the diel variations observed in Grape Creek occurred within the surface-water column or in the underlying sediments.

Scientific Investigations Report↗

Occurrence and sources of Escherichia coli in metropolitan St. Louis streams, October 2004 through September 2007

The occurrence and sources of Escherichia coli (E. coli) , one of several fecal indicator bacteria, in metropolitan St. Louis streams known to receive nonpoint source runoff, occasional discharges from combined and sanitary sewers, and treated wastewater effluent were investigated from October 2004 through September 2007. Three Missouri River sites, five Mississippi River sites, and six small basin tributary stream sites were sampled during base flow and storm events for the presence of E. coli and their sources. E. coli host-source determinations were conducted using local library based genotypic methods. Human fecal contamination in stream samples was additionally confirmed by the presence of Bacteroides thetaiotaomicron , an anaerobic, enteric bacterium with a high occurrence in, and specificity to, humans. Missouri River E. coli densities and loads during base flow were approximately 10 times greater than those in the Mississippi River above its confluence with the Missouri River. Although substantial amounts of E. coli originated from within the study area during base flow and storm events, considerable amounts of E. coli in the Missouri River, as well as in the middle Mississippi River sections downstream from its confluence with the Missouri River, originated in Missouri River reaches upstream from the study area. In lower Mississippi River reaches, bacteria contributions from the numerous combined and sanitary sewer overflows within the study area, as well as contributions from nonpoint source runoff, greatly increased instream E. coli densities. Although other urban factors cannot be discounted, average E. coli densities in streams were strongly correlated with the number of upstream combined and sanitary sewer overflow points, and the percentage of upstream impervious cover. Small basin sites with the greatest number of combined and sanitary sewer overflows (Maline Creek and the River des Peres) had larger E. coli densities, larger loads, and a greater percentage of E. coli attributable to humans than other small basin sites; however, even though small basin E. coli densities typically were much larger than in large river receiving streams, small basins contributed, on average, only a small part (a maximum of 16 percent) of the total E. coli load to larger rivers. On average, approximately one-third of E. coli in metropolitan St. Louis streams was identified as originating from humans. Another one-third of the E. coli was determined to have originated from unidentified sources; dogs and geese contributed lesser amounts, 10 and 20 percent, of the total instream bacteria. Sources of E. coli were largely independent of hydrologic conditions—an indication that sources remained relatively consistent with time.

Missouri↗

Monitoring to assess progress toward meeting the Assabet River, Massachusetts, phosphorus total maximum daily load - Aquatic macrophyte biomass and sediment-phosphorus flux

In 2004, the Total Maximum Daily Load (TMDL) for Total Phosphorus in the Assabet River, Massachusetts, was approved by the U.S. Environmental Protection Agency. The goal of the TMDL was to decrease the concentrations of the nutrient phosphorus to mitigate some of the instream ecological effects of eutrophication on the river; these effects were, for the most part, direct consequences of the excessive growth of aquatic macrophytes. The primary instrument effecting lower concentrations of phosphorus was to be strict control of phosphorus releases from four major wastewatertreatment plants in Westborough, Marlborough, Hudson, and Maynard, Massachusetts. The improvements to be achieved from implementing this control were lower concentrations of total and dissolved phosphorus in the river, a 50-percent reduction in aquatic-plant biomass, a 30-percent reduction in episodes of dissolved oxygen supersaturation, no low-flow dissolved oxygen concentrations less than 5.0 milligrams per liter, and a 90-percent reduction in sediment releases of phosphorus to the overlying water. In 2007, the U.S. Geological Survey, in cooperation with the Massachusetts Department of Environmental Protection, initiated studies to evaluate conditions in the Assabet River prior to the upgrading of wastewater-treatment plants to remove more phosphorus from their effluents. The studies, completed in 2008, implemented a visual monitoring plan to evaluate the extent and biomass of the floating macrophyte Lemna minor (commonly known as lesser duckweed) in five impoundments and evaluated the potential for phosphorus flux from sediments in impounded and free-flowing reaches of the river. Hydrologically, the two study years 2007 and 2008 were quite different. In 2007, summer streamflows, although low, were higher than average, and in 2008, the flows were generally higher than in 2007. Visually, the effects of these streamflow differences on the distribution of Lemna were obvious. In 2007, large amounts of floating macrophytes accumulated behind bridge constrictions and dams; in 2008, high flows during the early part of the growing season carried floating macrophytes past bridges and over dams, minimizing accumulations. Samples of Lemna were collected and weighed to provide an estimate of Lemna biomass based on areal coverage during the summer growing seasons at eight sites in the five impoundments. Average estimated biomass during 2007 was approximately twice the 2008 biomass in each of the areas monitored. In 2007, in situ hyperspectral and high-resolution, multispectral data from the IKONOS satellite were obtained to evaluate the feasibility of using remote sensing to monitor the extent of aquatic plant growth in Assabet River impoundments. Three vegetation indices based on light reflectance were used to develop metrics with which the hyperspectral and satellite data were compared. The results of the comparisons confirmed that the high-resolution satellite imagery could differentiate among the common aquatic-plant associations found in the impoundments. The use of satellite imagery could counterbalance emphasis on the subjective judgment of a human observer, and airborne hyperspectral data can provide higher resolution imagery than multispectral satellite data. In 2007 and 2008, the potential for sediment flux of phosphorus was examined in free-flowing reaches of the river and in the two largest impoundments-Hudson and Ben Smith. These studies were undertaken to determine in situ flux rates prior to the implementation of the Assabet River Total Maximum Daily Load (TMDL) for phosphorus and to compare these rates with those used in the development and evaluation of the TMDL. Water samples collected from a chamber placed on the river bottom were analyzed for total phosphorus and orthophosphorus. Ambient dissolved oxygen concentrations and seasonal temperature differences appeared to affect the rates of sequestration and sediment release of phosphorus. When dissolved oxygen concentrations remained relatively high in the chambers and when the temperature was relatively low, the tendency was for phosphorus concentrations to decrease in the chambers, indicating sediment sequestration of phosphorus; when dissolved oxygen concentrations dropped to near zero and temperatures were warmest, phosphorus concentrations increased in the chambers, indicating phosphorus flux from the sediment. The rates of release and sequestration in the in situ studies were generally comparable with the rates determined in laboratory studies of Assabet River sediment cores for State and Federal agencies. Sediment-core and chamber studies produced substantial sediment fluxes to the water column only under extremely low-DO or anaerobic conditions rarely found in the Assabet River impoundments; thus, sediment is not likely to be a major phosphorus source, especially when compared to the wastewater effluent, which sustains higher ambient concentrations. The regulatory agencies now (2011) have substantial laboratory and field data with which to determine the required 90-percent reduction in phosphorus flux after the completion of upgrades to the wastewater-treatment plants that discharge to the Assabet River.

Massachusetts↗

Effects of a drawdown on plant communities in a freshwater impoundment at Lacassine National Wildlife Refuge, Louisiana

Disturbance is an important natural process in the creation and maintenance of wetlands. Water depth manipulation and prescribed fire are two types of disturbance commonly used by humans to influence vegetation succession and composition in wetlands with the intention of improving wildlife habitat value. A 6,475-hectare (ha) impoundment was constructed in 1943 on Lacassine National Wildlife Refuge in southwest Louisiana to create freshwater wetlands as wintering waterfowl habitat. Ten years after construction of the impoundment, called Lacassine pool, was completed, refuge staff began expressing concerns about increasing emergent vegetation cover, organic matter accumulation, and decreasing area of open water within the pool. Because the presence of permanent standing water impedes actions that can address these concerns, a small impoundment within the pool where it was possible to manipulate water depth was created. The 283-ha subimpoundment called Unit D was constructed in 1989. Water was pumped from Unit D in 1990, and the unit was permanently reflooded about 3 years later. Four prescribed fires were applied during the drawdown. A study was initiated in 1990 to investigate the effect of the experimental drawdown on vegetation and soils in Unit D. Four plant community types were described, and cores were collected to measure the depth of the soil organic layer. A second study of Unit D was conducted in 1997, 4 years after the unit was reflooded, by using the same plots and similar sampling methods. This report presents an analysis and synthesis of the data from the two studies and provides an evaluation of the impact of the management techniques applied. We found that plant community characteristics often differed among the four communities and varied with time. Species richness increased in two of the communities, and total aboveground biomass increased in all four during the drawdown. These changes, however, did not persist when Unit D was reflooded; by 1997, species richness and aboveground biomass were equivalent to values before the drawdown. The change in waterfowl food value of the plant communities during the drawdown varied; it did not change in two communities, increased in one, and decreased in one. A consistent pattern noted was that waterfowl food value was higher in communities that contained open water than in those dominated by emergent plants, both soon after the drawdown was initiated in Unit D and 4 years after reflooding. A reduction in depth of the soil organic layer became apparent 20 months after drawdown was initiated, and this reduction persisted in 1997, 4 years after reflooding. A separate 2003 study on soil characteristics in Lacassine pool found that the depth to the clay layer was lower in Unit D than in the rest of the pool. We were not able to establish a cause-and-effect relation between any changes noted and the fact water levels in the unit were drawn down because the initial study in 1990 did not include control plots. Changes in vegetation and soil organic layer depth identified in Unit D may have occurred in the surrounding Lacassine pool habitat as well. Similarly, we were unable to form any conclusions about the effect of the prescribed fire treatments because there was no information on which plots were burned. Because of the known relation between anaerobic soil conditions and reduced decomposition of organic matter, however, it is likely that the drawdown in Unit D resulted in an increased decomposition rate and a reduction in the depth of the soil organic layer.

Louisiana↗

Chemical and isotopic characteristics of methane in groundwater of Ohio, 2016

In 2016, the U.S. Geological Survey, in cooperation with the Ohio Water Development Authority, investigated the hydrogeologic setting, chemical and isotopic characteristics, and origin of methane in groundwater of Ohio. Understanding the occurrence and distribution of methane in groundwater is important in terms of public safety because methane in water wells can pose a risk of explosion. In addition, documenting the chemical and isotopic characteristics of methane in groundwater can make an important contribution to future stray gas investigations. Water samples were collected from 15 domestic water wells known to produce methane, which were in 12 counties in diverse parts of Ohio. The wells were 75–345 feet deep and tapped a range of aquifer types, including glacial deposits and bedrock of Upper Ordovician, Upper Devonian, Lower Mississippian, and Pennsylvanian ages. Although the hydrogeologic settings were varied, there was a broad similarity among the well sites in that the bedrock was predominantly shale and the glacial deposits were predominantly clay. The wells were sampled for dissolved inorganic constituents; dissolved organic carbon; methane and other dissolved gases; stable isotopes (carbon, hydrogen, and oxygen) of methane, water, and dissolved inorganic carbon; and carbon-14 of methane. Gas composition and stable isotopes of methane were used to differentiate thermogenic and microbial methane. The degree of fractionation of hydrogen and carbon isotopes was used to evaluate the pathway of microbial methanogenesis (carbon dioxide [CO 2 ] reduction or acetate fermentation) and the effects of secondary processes such as oxidation, mixing, and migration. The concentration of carbon-14 of methane was used to evaluate the relative age of the carbon source. The quality of water from the 15 wells differed greatly; water types ranged from CaMgHCO 3 to NaCl, and total dissolved solids concentrations ranged from 318 to 2,940 milligrams per liter (mg/L). Methane concentrations ranged from 1.2 to 120 mg/L. Of the 15 samples, 12 had methane concentrations greater than 28 mg/L, the level that can pose a risk of explosion. Of the 15 samples, 12 had chemical and isotopic characteristics or "signatures" consistent with microbial methane formed by CO 2 reduction. CO 2 reduction is commonly associated with microbial degradation of organic matter in anaerobic aquifers and with the formation of microbial shale gas and coalbed methane along margins of sedimentary basins. Two of 15 samples were interpreted as having a component of thermogenic methane based on the δ 13 C of methane (−50.96 and −47.74 parts per thousand [per mil]) and gas dryness (28 and 5). One of 15 samples (from the shallowest well) had chemical and isotopic characteristics consistent with methane oxidation by sulfate reduction based on light δ 13 C of dissolved inorganic carbon (−31.6 per mil) and evidence of sulfate reduction in terms of the odor and appearance of the water. For the 12 samples interpreted as microbial methane formed by CO 2 reduction, the δ 13 C of methane varied from −75 to −56 per mil. Multiple samples from the same aquifer demonstrated a general trend of increasing δ 13 C of methane with depth. Samples with lighter δ 13 C of methane (−75 to −62 per mil) were from shallower wells (or wells with shallow open intervals), and the isotopic signature of the water was consistent with modern or postglacial groundwater recharge. Three samples with heavier δ 13 C of methane (−61 to −56 per mil) were from deeper wells or more confined aquifers where the isotopic signature of water was consistent with older (glacial) recharge. In addition, δ 13 C of dissolved inorganic carbon was enriched (+12 to +18.9 per mil), and carbon-14 of methane was consistent with carbon associated with Paleozoic bedrock or older glacial deposits. These observations are generally consistent with increased Rayleigh-type fractionation at greater depths; however, other interpretations are possible. Isotopic signatures can be ambiguous, especially in areas with complex geologic histories that include multiple episodes of migration, mixing, and (or) oxidation. Many of the wells were in proximity to multiple potential natural and anthropogenic pathways of methane migration; however, it is not possible to determine if the methane in any of the wells is related to human activities based on the chemical and isotopic data collected for this study.

Ohio↗

Assessment of the presence of sewage in the Mill River under low-flow conditions, Springfield, Massachusetts, 2010–11

The U.S. Geological Survey, in cooperation with the Pioneer Valley Planning Commission, the U.S. Environmental Protection Agency, and the Massachusetts Department of Environmental Protection Senator William X. Wall Experiment Station, assessed the presence of 14 commonly used human-health pharmaceutical compounds, fecal indicator bacteria, and other man-made compounds indicative of the presence of human sewage in the lower reach of the Mill River near its confluence with the Connecticut River in Springfield, Massachusetts. The study was part of the Tri-State Connecticut River Targeted Watershed Initiative and involved the collection and analysis of raw river water at three sites along the reach, extending from Watershops Pond to the mouth, over the course of a low-flow period, July through November 2010. Previous studies in the region indicated that nonpoint or undocumented sources of wastewater contributed a variety of organic contaminants and potentially harmful bacteria to rivers under both high- and low-flow conditions. Additional samples, including a raw sewage sample collected near a Mill River combined sewer overflow during a non-overflow period, were collected in March 2011. The study was designed to determine if city sewage or other domestic sources of wastewater were entering the river within this reach during low-flow conditions. No definitive evidence of sewage was measured in Mill River water samples collected during the study period. Fecal indicator bacteria, including Escherichia coli ( E. coli ) and enterococci bacteria, were detected in all Mill River water samples. In the DNA analysis of enterococci cultures from the Mill River, samples generally tested negative for the Enterococcus faecium ( esp ) human-specific genetic marker, whereas the raw sewage sample tested positive. Samples also generally tested negative in the human-specific rDNA marker assay for the anaerobic bacterium Bacteroidetes . Samples tested negative in 2010 for two Bacteroidetes human-specific genetic markers, HF134 and HF183, except samples from near the mouth of the Mill River, which tested positive. Samples collected in March 2011 from all three measurement sites tested positive for both markers. The results of bacterial analyses suggest that the fecal bacteria in summer and fall months are most likely of animal origin rather than human. Despite the urban setting, long history of development, and many potential sources of man-made contamination in the Mill River, none of the 12 water samples collected during the study contained targeted pharmaceutical compounds at concentrations greater than the analytical reporting levels. Other man-made compounds, like fluorescent whitening agents, were measured and detected in samples at low concentrations 4 out of 5 times the samples were collected; however, the other lines of evidence do not support a sewer source but rather other nonpoint sources upstream in the watershed. The results of this study do not support the hypothesis that aging sewer lines or combined sewer overflow infrastructure leak into the Mill River as tested during the low-flow conditions during sampling for this study. None of the results from Mill River samples offer conclusive evidence of the presence of sewage. Some low-level detections of pharmaceutical compounds, other man-made chemicals, and bacteria suggest an upstream, nonpoint source. A single raw sewage sample was collected, diluted, and examined for comparison with Mill River water samples and to ensure that the analytical methods could detect typical wastewater constituents. High levels of bacteria were measured, and low levels of three anthropogenic pharmaceutical compounds were detected, confirming the effectiveness of the sub-part-per-million method. The concentration of fluorescent whitening agent-1 in the sewage sample was 90,000 times greater than the median concentration in the Mill River samples.

Massachusetts↗

Assessment of potential for natural attenuation of chlorinated ethenes and ethanes in ground water at a petrochemical reclamation site, Harris County, Texas

Redox conditions in the Numerous Sand Channels Zone beneath a petrochemical reclamation site in Harris County, Texas, range from sulfate reducing to methanogenic as indicated by the presence of methane in ground water and the range of molecular hydrogen concentrations. Assessment of the potential for reductive dechlorination using BIOCHLOR as a screening tool indicated conditions favoring anaerobic degradation of chlorinated organic compounds in the Numerous Sand Channels Zone. Evidence supporting reductive dechlorination includes apparently biogenic cis -1,2-dichloroethene; an increased ratio of 1,2-dichloroethane to 1,1,2-trichloroethane downgradient from the assumed contaminant source area; ethene and methane concentrations greater than background concentrations within the area of the contaminant plume; and a positive correlation of the ratio of ethene to vinyl chloride as a function of methane concentrations. The body of evidence presented in this report argues for hydrogenolysis of trichloroethene to cis -1,2-dichloroethene; of 1,1,2-trichloroethane to 1,2-dichloroethane; and of vinyl chloride to ethene within the Numerous Sand Channels Zone. Simulations using BIOCHLOR yielded apparent first-order decay constants for reductive dechlorination in the sequence tetrachloroethene trichloroethene cis -1,2-dichloroethene vinyl chloride ethene within the range of literature values reported for each compound and apparent first-order decay constants for reductive dechlorination in the sequence 1,1,2-trichloroethane 1,2-dichloroethane slightly greater than literature values reported for each compound along the upgradient segment of a simulated ground-water flowpath. Except for vinyl chloride, apparent rates of reductive dechlorination for all simulated species show a marked decrease along the downgradient segment of the simulated ground-water flowpath. Evidence for reductive dechlorination of chlorinated ethenes within the Numerous Sand Channels Zone indicates potential for natural attenuation of chlorinated ethenes. Reductive dechlorination of chlorinated ethanes apparently occurs to a lesser extent, indicating relatively less potential for natural attenuation of chlorinated ethanes. Additional data are needed on the concentrations and distribution of chlorinated ethenes and ethanes in individual fine sand intervals of the Numerous Sand Channels Zone. This information, combined with lower minimum reporting levels for future chloroethane analyses, might enable a more complete and quantitative assessment of the potential for natural attenuation at the site.

Texas↗

Aquifer geochemistry and effects of pumping on ground-water quality at the Green Belt Parkway Well Field, Holbrook, Long Island, New York

Geochemistry, microbiology, and water quality of the Magothy aquifer at a new supply well in Holbrook were studied to help identify factors that contribute to iron-related biofouling of public-supply wells. The organic carbon content of borehole sediments from the screen zone, and the dominant terminal electron-accepting processes (TEAPs), varied by depth. TEAP assays of core sediments indicated that iron reduction, sulfate reduction, and undetermined (possibly oxic) reactions and microbial activity are correlated with organic carbon (lignite) content. The quality of water from this well, therefore, reflects the wide range of aquifer microenvironments at this site. High concentrations of dissolved iron (3.6 to 6.4 micromoles per liter) in water samples from this well indicate that some water is derived from Fe(III)-reducing sediments within the aquifer, but traces of dissolved oxygen indicate inflow of shallow, oxygenated water from shallow units that overlie the local confining units. Water-quality monitoring before and during a 2-day pumping test indicates that continuous pumping from the Magothy aquifer at this site can induce downward flow of shallow, oxygenated water despite the locally confined conditions. Average concentrations of dissolved oxygen are high (5.2 milligrams per liter, or mg/L) in the overlying upper glacial aquifer and at the top of the Magothy aquifer (4.3 mg/L), and low ( < 0.1 mg/L) in the deeper, anaerobic part of the Magothy; average concentrations of phosphate are high (0.4 mg/L) in the upper glacial aquifer and lower (0.008 mg/L) at the top of the Magothy aquifer and in the deeper part of the Magothy (0.013 mg/L). Concentrations of both constituents increased during the 2 days of pumping. The δ 34 S of sulfate in shallow ground water from observation wells (3.8 to 6.4 per mil) was much heavier than that in the supplywell water (-0.1 per mil) and was used to help identify sources of water entering the supply well. The δ 34 S of sulfate in a deep observation well adjacent to the supply well increased from 2.4 per mil before pumping to 3.3 per mil after pumping; this confirms that the pumping induced downward migration of water. The lighter δ 34 S value in the pumped water than in the adjacent observation well probably indicates FeS 2 oxidation (which releases light δ 34 S in adjacent sediments) by the downward flow of oxygenated water.

New York↗

Biodegradation potential of chlorinated solvents in ground water at the Naval Surface Warfare Center, Louisville, Kentucky, July 1999 to February 2000

The U.S. Geological Survey, in cooperation with the U.S. Department of the Navy, Southern Division Naval Facilities Engineering Command, investigated the potential for biodegradation of chlorinated solvents in ground water at the Naval Surface Warfare Center (also known as the Naval Ordnance Station, or the station), Louisville, Kentucky. The subsurface down to at least 100 feet at the station is characterized, from shallowest to deepest, by overburden deposits, a shale layer, and limestone. In general, all of the strata are poorly permeable. The permeable zones of the overburden and the limestone make up the overburden aquifer and the bedrock aquifer, respectively. Observed concentrations of redox-sensitive solutes suggest that the predominant anaerobic terminal electron accepting process in the overburden aquifer can shift between iron reduction and sulfate reduction, possibly as a result of rainfall-induced oxidation events. Daughter-product concentrations and laboratory experiments indicate that a variety of mechanisms, including reductive dechlorination and cometabolic oxidation, appear to be actively

Kentucky↗

Water quality and environmental isotopic analyses of ground-water samples collected from the Wasatch and Fort Union Formations in areas of coalbed methane development — Implications to recharge and ground-water flow, eastern Powder River Basin, Wyoming

Chemical analyses of ground-water samples were evaluated as part of an investigation of lower Tertiary aquifers in the eastern Powder River Basin where coalbed methane is being developed. Ground-water samples were collected from two springs discharging from clinker, eight monitoring wells completed in the Wasatch aquifer, and 13 monitoring or coalbed methane production wells completed in coalbed aquifers. The ground-water samples were analyzed for major ions and environmental isotopes (tritium and stable isotopes of hydrogen and oxygen) to characterize the composition of waters in these aquifers, to relate these characteristics to geochemical processes, and to evaluate recharge and ground-water flow within and between these aquifers. This investigation was conducted in cooperation with the Wyoming State Engineer's Office and the Bureau of Land Management. Water quality in the different aquifers was characterized by major-ion composition. Samples collected from the two springs were classified as calcium-sulfate-type and calcium-bicarbonate-type waters. All ground-water samples from the coalbed aquifers were sodium-bicarbonate-type waters as were five of eight samples collected from the overlying Wasatch aquifer. Potential areal patterns in ionic composition were examined. Ground-water samples collected during this and another investigation suggest that dissolved-solids concentrations in the coalbed aquifers may be lower south of the Belle Fourche River (generally less than 600 milligrams per liter). As ground water in coalbed aquifers flows to the north and northwest away from an inferred source of recharge (clinker in the study area), dissolved-solids concentrations appear to increase. Variation in ionic composition in the vertical dimension was examined qualitatively and statistically within and between aquifers. A relationship between ionic composition and well depth was noted and corroborates similar observations by earlier investigators in the Powder River Basin in both Wyoming and Montana. This relationship results in two different water-quality zones with different characteristics - a shallow zone, comprising the upper part of the Wasatch aquifer, characterized by mixed cation composition and either sulfate or bicarbonate as the dominant anion; and a deeper zone, comprising the lower (deeper) part of the Wasatch aquifer and the underlying coalbed aquifers, characterized by sodium-bicarbonate-type waters. The zonation appears to be related to geochemical processes described by earlier investigators such as dissolution and precipitation of minerals, ion exchange, sulfate reduction, and mixing of waters. Qualitative and statistically significant differences were observed in sulfate concentrations between the coalbed aquifers and the overlying Wasatch aquifer. Ionic composition suggests that bacterially mediated redox processes such as sulfate reduction were probably the dominant geochemical processes in the anaerobic coalbed aquifers. Tritium was used to qualitatively estimate the time of ground-water recharge. Tritium concentrations in both springs suggests that both were recharged after 1952 and contain modern water. Tritium was not detected at concentrations suggestive of modern water in any ground-water samples collected from the coalbed aquifers or in six of eight ground-water samples collected from the overlying Wasatch aquifer. Tritium concentrations in the remaining two wells from the Wasatch aquifer suggest a mixture between submodern (recharged before 1952) and modern water, although the low concentrations suggest that ground water in these two wells have very little modern water. The relative absence of modern water in all aquifers in the study area suggests that recharge processes to these aquifers are probably very slow. Paired d 2 H (deuterium/hydrogen isotopic ratio) and d 18 O (oxygen-18/oxygen-16 isotopic ratio) values for samples collected from the springs and all aquifers are close to the Global Meteoric Water Line, a meteoric water line for North American continental precipitation, and an estimated local meteoric water line, suggesting the water in the aquifers is of meteoric origin. The d 2 H and d 18 O values suggest that the waters were recharged in a colder climate or temperature, mid-latitudes, and mid-continent. In general, the samples do not form separate groups based on aquifer origin; this suggests either intermixing of the waters in the aquifers or that the different aquifers are subject to similar recharge and/or evolutional paths for the water. However, examination of the differences in the values of d 2 H and d 18 O, in combination with major-ion chemistry at three monitoring-well clusters, suggest that changes in the values with depth may represent different timing or sources of recharge to the different aquifers. The areal distribution of d 2 H was examined and an apparent break in the d 2 H along a northwest to southeast trend was observed. In the coalbed aquifers, all but one ground-water sample (collected from the Big George coal bed), show a pattern where the d 2 H values become more negative towards the center of the Powder River Basin and values greater (less negative) than an arbitrary reference value of -140 ‰ (per mil or parts per thousand) were observed near the outcrop area of the Wyodak-Anderson coal zone. In the overlying Wasatch aquifer, the d 2 H values became less negative towards the center of the basin. The values more negative than -140 ‰ are near the outcrop area and the values that are less negative than -140 ‰ are closer to the basin center. It is unclear if this pattern is a result of sample size, different recharge mechanisms, geochemical processes, or if the processes producing these differences are independent or unrecognized. Results of water-quality sampling were compared with selected regulatory and non-regulatory standards as well as commonly-used guidelines for proposed water uses. Dissolved solids was the measure that most frequently exceeded U.S. Environmental Protection Agency public water-supply standards and State of Wyoming domestic-use standards in ground-water samples collected from the Wasatch aquifer and coalbed aquifers. The State of Wyoming agricultural standards (irrigation) for sulfate and dissolved solids were exceeded in some samples collected from the Wasatch aquifer and coalbed aquifers. The State of Wyoming livestock standard for pH was exceeded in some samples collected from the Wasatch aquifer. Water from the Wasatch aquifer ranged from soft to very hard, and water from the coalbed aquifers ranged from moderately hard to very hard. Samples collected from wells completed in both the Wasatch aquifer and coalbed aquifers plotted in a wide range of both sodium- and salinity-hazard classes, but most samples clustered in or near the combined medium-sodium-hazard—high-salinity-hazard classes.

Wyoming↗

Oxidation-reduction processes in ground water at Naval Weapons Industrial Reserve Plant, Dallas, Texas

Concentrations of trichloroethene in ground water at the Naval Weapons Industrial Reserve Plant in Dallas, Texas, indicate three source areas of chlorinated solvents?building 1, building 6, and an off-site source west of the facility. The presence of daughter products of reductive dechlorination of trichloroethene, which were not used at the facility, south and southwest of the source areas are evidence that reductive dechlorination is occurring. In places south of the source areas, dissolved oxygen concentrations indicated that reduction of oxygen could be the dominant process, particularly south of building 6; but elevated dissolved oxygen concentrations south of building 6 might be caused by a leaking water or sewer pipe. The nitrite data indicate that denitrification is occurring in places; however, dissolved hydrogen concentrations indicate that iron reduction is the dominant process south of building 6. The distributions of ferrous iron indicate that iron reduction is occurring in places south-southwest of buildings 6 and 1; dissolved hydrogen concentrations generally support the interpretation that iron reduction is the dominant process in those places. The generally low concentrations of sulfide indicate that sulfate reduction is not a key process in most sampled areas, an interpretation that is supported by dissolved hydrogen concentrations. Ferrous iron and dissolved hydrogen concentrations indicate that ferric iron reduction is the primary oxidation-reduction process. Application of mean first-order decay rates in iron-reducing conditions for trichloroethene, dichloroethene, and vinyl chloride yielded half-lives for those solvents of 231, 347, and 2.67 days, respectively. Decay rates, and thus half-lives, at the facility are expected to be similar to those computed. A weighted scoring method to indicate sites where reductive dechlorination might be likely to occur indicated strong evidence for anaerobic biodegradation of chlorinated solvents at six sites. In general, scores were highest for samples collected on the northeast side of the facility.

Texas↗

Processes affecting the trihalomethane concentrations associated with the third injection, storage, and recovery rest at Lancaster, Antelope Valley, California, March 1998 through April 1999

The formation and fate of trihalomethanes (THM) during the third injection, storage, and recovery test at Lancaster, Antelope Valley, California, were investigated as part of a program to assess the long-term feasibility of using injection, storage, and recovery as a water-supply method and as a way to reduce water-level declines and land-subsidence in the Antelope Valley. The program was conducted by the U.S. Geological Survey in cooperation with the Los Angeles County Department of Public Works and the Antelope Valley-East Kern Water Agency. The water used for injection, storage, and recovery must be disinfected before injection and thus contains THMs and other disinfection by-products. THMs (chloroform, CHCl3, bromodichloromethane, CHCl2Br, dibromochloromethane, CHClBr2, and bromoform, CHBr3) are formed by reaction between natural dissolved organic carbon that is present in water and chlorine that is added during the disinfection step of the drinking water treatment process. THMs are carcinogenic compounds, and their concentrations in drinking water are regulated by the U.S. Environmental Protection Agency. During previous cycles of the Lancaster program, extracted water still contained measurable concentrations of THMs long after continuous pumping had extracted a greater volume of water than had been injected. This raised concerns about the potential long-term effect of injection, storage, and recovery cycles on ground-water quality in Antelope Valley aquifers. The primary objectives of this investigation were to determine (1) what controlled continued THM formation in the aquifer after injection, (2) what caused of the persistence of THMs in the extracted water, even after long periods of pumping, (3) what controlled the decrease of THM concentrations during the extraction period, and (4) the potential for natural attenuation of THMs in the aquifer. Laboratory experiments on biodegradation of THMs in microcosms of aquifer materials indicate that aquifer bacteria did not degrade CHCl3 or CHBr3 under aerobic conditions, but did degrade CHBr3 under anaerobic conditions. However, the aquifer is naturally aerobic and CHCl3 is the dominant THM species; therefore, biodegradation is not considered an important attenuation mechanism for THMs in this aquifer. The alluvial-fan sediments comprising the aquifer have very low contents of organic matter; therefore, sorption is not considered to be an important attenuation mechanism for THMs in this aquifer. Laboratory experiments on formation of THMs in the injection water indicate that continued THM formation in the injection water after injection into the aquifer was limited by the amount of residual chlorine in the injection water at the time of injection. After accounting for THMs formed by reaction of this residual chlorine, THMs behaved as conservative constituents in the aquifer, and the only process affecting the concentration of THMs was mixing of the injection water and the ground water. The mixing process was quantified using mass balances of injected constituents, the sulfur hexafluoride (SF6) tracer that was added to the injected water, and a simple descriptive mathematical mixing model. Mass balance calculations show that only 67 percent of the injected THMs and chloride were recovered by the time that a volume of water equivalent to 132 percent of the injection water volume was extracted. Pumping 250 percent of the injection water volume only increased recovery of injected THMs to 80 percent. THM and SF6 concentrations in the extracted water decreased concomitantly during the extraction period, and THM concentrations predicted from SF6 concentrations closely matched the measured THM concentrations. Because SF6 is a conservative tracer that was initially only present in the injection water, parallel decreases in SF6 and THM concentrations in the extracted water must be due to dilution of injection water with ground water. The simple descriptive mixing mode

Water-Resources Investigations Report↗

Isotope geochemistry and chronology of offshore ground water beneath Indian River Bay, Delaware

Results of geophysical surveys in Indian River Bay, Delaware, indicate a complex pattern of salinity variation in subestuarine ground water. Fresh ground-water plumes up to about 20 meters thick extending hundreds of meters offshore are interspersed with saline ground water, with varying degrees of mixing along the salinity boundaries. It is possible that these features represent pathways for nutrient transport and interaction with estuarine surface water, but the geophysical data do not indicate rates of movement or nutrient sources and reactions. In the current study, samples of subestuarine ground water from temporary wells with short screens placed 3 to 22 meters below the sediment-water interface were analyzed chemically and isotopically to determine the origins, ages, transport pathways, and nutrient contents of the fresh and saline components. Apparent ground-water ages determined from chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), tritium (3H), and helium isotopes (3He and 4He) commonly were discordant, but nevertheless indicate that both fresh and saline ground waters ranged from a few years to at least 50 years in age. Tritium-helium (3H-3He) ages, tentatively judged to be most reliable, indicate that stratified offshore freshwater plumes originating in distant recharge areas on land were bounded by relatively young saline water that was recharged locally from the overlying estuary. Undenitrified and partially denitrified nitrate of agricultural or mixed origin was transported laterally beneath the estuary in oxic and suboxic fresh ground water. Ammonium produced by anaerobic degradation of organic matter in estuarine sediments was transported downward in suboxic saline ground water around the freshwater plumes. Many of the chemical and isotopic characteristics of the subestuarine ground waters are consistent with conservative mixing of the fresh (terrestrial) and saline (estuarine) endmember water types. These data indicate that freshwater plumes detected by geophysical surveys beneath Indian River Bay represent lateral continuations of the active surficial nitrate-contaminated freshwater flow systems originating on land, but they do not indicate directly the magnitude of fresh ground-water discharge or nutrient exchange with the estuary. There is evidence that some of the terrestrial ground-water nitrate is reduced before discharging directly beneath the estuary. Local estuarine sediment-derived ammonium in saline pore water may be a substantial benthic source of nitrogen in offshore areas of the estuary.

Delaware↗

Nitrogen and phosphorus uptake in the Everglades Conservation Areas, Florida, with special reference to the effects of backpumping runoff

In much of the water pumped into the northern Everglades, Florida, concentrations of inorganic nitrogen and phosphorus are relatively high. These nutrients are transported in the canals or into the peripheral marshes. Concentrations decrease sharply within 330 feet or less of the canals, whereas specific conductance remains essentially unchanged within this distance. The sharp decrease in inorganic nitrogen and phosphorus near the canal edge indicates net uptake in these shallow waters. Concentrations of nitrogen and phosphorus also decrease as water moves through the conservation areas in canals. This decrease is due partly to dilution by rainfall and runoff, and partly to net uptake in the canals and their peripheral marsh. The large canals of the northern and eastern parts of the conservation areas often have relatively low concentrations of dissolved oxygen which show little fluctuation within 24 hours. Backpumping 50 percent of the total annual canal runoff in southeast Florida would add from 990 to 6,160 tons of nitrogen and from 10 to 62 tons of phosphorus to the conservation areas. The bottom sediments of the Everglades are a sink for nitrogen and phosphorus. They can, however, be a source of these nutrients when anaerobic conditions exist at the water-sediment interface or when bottom material becomes resuspended. (Woodard-USGS)

Florida↗