Fluid migration pathways to groundwater in mature oil fields: Exploring the roles of water injection/production and oil-well integrity in California, USA.

Mature oil fields potentially contain multiple fluid migration pathways toward protected groundwater (total dissolved solids, TDS, in nonexempted aquifer <10,000 mg/L) because of their extensive development histories. Time-series data for water use, fluid pressures, oil-well construction, and geochemistry from the South Belridge and Lost Hills mature oil fields in California are used to explore the roles of injection/production of oil-field water and well-integrity issues in fluid migration. Injection/production of oil-field water modified hydraulic gradients in both oil fields, resulting in chemical transport from deeper groundwater and hydrocarbon-reservoir systems to aquifers in the oil fields. Those aquifers are used for water supply outside the oil-field boundaries. Oil wells drilled before 1976 can be fluid migration pathways because a relatively large percentage of them have >10 m of uncemented annulus that straddles oil-well casing damage and/or the base of groundwater with TDS <10,000 mg/L. The risk of groundwater-quality degradation is higher when wells with those risk factors occur in areas with upward hydraulic gradients created by positive net injection, groundwater withdrawals, or combinations of these variables. The complex changes in hydrologic conditions and groundwater chemistry likely would not have been discovered in the absence of years to decades of monitoring data for groundwater elevations and chemistry, and installation of monitoring wells in areas with overlapping risk factors. Important monitoring concepts based on results from this and other studies include monitoring hydrocarbon-reservoir and groundwater systems at multiple spatiotemporal scales and maintaining transparency and accessibility of data and analyses. This analysis focuses on two California oil fields, but the methods used and processes affecting fluid migration could be relevant in other oil fields where substantial injection/production of oil-field water occurs and oil-well integrity is of concern.

Perfluoroalkyl and Polyfluoroalkyl Substances in Groundwater Used as a Source of Drinking Water in the Eastern United States.

In 2019, 254 samples were collected from five aquifer systems to evaluate perfluoroalkyl and polyfluoroalkyl substance (PFAS) occurrence in groundwater used as a source of drinking water in the eastern United States. The samples were analyzed for 24 PFAS, major ions, nutrients, trace elements, dissolved organic carbon (DOC), volatile organic compounds (VOCs), pharmaceuticals, and tritium. Fourteen of the 24 PFAS were detected in groundwater, with 60 and 20% of public-supply and domestic wells, respectively, containing at least one PFAS detection. Concentrations of tritium, chloride, sulfate, DOC, and manganese + iron; percent urban land use within 500 m of the wells; and VOC and pharmaceutical detection frequencies were significantly higher in samples containing PFAS detections than in samples with no detections. Boosted regression tree models that consider 57 chemical and land-use variables show that tritium concentration, distance to the nearest fire-training area, percentage of urban land use, and DOC and VOC concentrations are the top five predictors of PFAS detections, consistent with the hydrologic position, geochemistry, and land use being important controls on PFAS occurrence in groundwater. Model results indicate that it may be possible to predict PFAS detections in groundwater using existing data sources.

Predicting regional fluoride concentrations at public and domestic supply depths in basin-fill aquifers of the western United States using a random forest model.

A random forest regression (RFR) model was applied to over 12,000 wells with measured fluoride (F) concentrations in untreated groundwater to predict F concentrations at depths used for domestic and public supply in basin-fill aquifers of the western United States. The model relied on twenty-two regional-scale environmental and surficial predictor variables selected to represent factors known to control F concentrations in groundwater. The testing model fit R2 and RMSE were 0.52 and 0.78 mg/L. Comparisons of measured to predicted proportions of four F-concentrations categories (<0.7 mg/L, 0.7-2 mg/L, >2 mg/L - 4 mg/L, and > 4 mg/L) indicate that the model performed well at making regional-scale predictions. Differences between measured and predicted proportions indicate underprediction of measured F at values by between 4 and 20 mg/L, representing less than 1% of the regional scale predicted values. These residuals most often map to geographic regions where local-scale processes including evaporative discharge in closed basins or intermittent streams concentrate fluoride in shallow groundwater. Despite this, the RFR model provides spatially continuous F predictions across the basin-fill aquifers where discrete samples are missing. Further, the predictions capture documented areas that exceed the F maximum contaminant level for drinking water of 4 mg/L and areas that are below the oral-health benchmark of 0.7 mg/L. These predictions can be used to estimate fluoride concentrations in unmonitored areas and to aid in identifying geographic areas that may require further investigation at localized scales.

Groundwater Quality of Aquifers Overlying the Oxnard Oil Field, Ventura County, California.

Groundwater samples collected from irrigation, monitoring, and municipal supply wells near the Oxnard Oil Field were analyzed for chemical and isotopic tracers to evaluate if thermogenic gas or water from hydrocarbon-bearing formations have mixed with surrounding groundwater. New and historical data show no evidence of water from hydrocarbon-bearing formations in groundwater overlying the field. However, thermogenic gas mixed with microbial methane was detected in 5 wells at concentrations ranging from 0.011-9.1 mg/L. The presence of these gases at concentrations <10 mg/L do not indicate degraded water quality posing a known health risk. Analysis of carbon isotopes (δ13C-CH4) and hydrogen isotopes (δ2H-CH4) of methane and ratios of methane to heavier hydrocarbon gases were used to differentiate sources of methane between a) microbial, b) thermogenic or c) mixed sources. Results indicate that microbial-sourced methane is widespread in the study area, and concentrations overlap with those from thermogenic sources. The highest concentrations of thermogenic gas were observed in proximity to relatively high density of oil wells, large injection volumes of water disposal and cyclic steam, shallow oil development, and hydrocarbon shows in sediments overlying the producing oil reservoirs. Depths of water wells containing thermogenic gas were within approximately 200 m of the top of the Vaca Tar Sand production zone (approximately 600 m below land surface). Due to the limited sampling density, the source and pathways of thermogenic gas detected in groundwater could not be conclusively determined. Thermogenic gas detected in the absence of co-occurring water from hydrocarbon-bearing formations may result from natural gas migration over geologic time from the Vaca Tar Sand or deeper formations, hydrocarbon shows in sediments overlying producing zones, and/or gas leaking from oil-field infrastructure. Denser sampling of groundwater, potential end-members, and pressure monitoring could help better distinguish pathways of thermogenic gases.

Fluoride occurrence in United States groundwater.

Data from 38,105 wells were used to characterize fluoride (F) occurrence in untreated United States (U.S.) groundwater. For domestic wells (n = 11,032), water from which is generally not purposely fluoridated or monitored for quality, 10.9% of the samples have F concentrations >0.7 mg/L (U.S. Public Health Service recommended optimal F concentration in drinking water for preventing tooth decay) (87% are <0.7 mg/L); 2.6% have F > 2 mg/L (EPA Secondary Maximum Contaminant Level, SMCL); and 0.6% have F > 4 mg/L (EPA MCL). The data indicate the biggest concern with F in domestic wells at the national scale could be one of under consumption of F with respect to the oral-health benchmark (0.7 mg/L). Elevated F concentrations relative to the SMCL and MCL are regionally important, particularly in the western U.S. Statistical comparisons of potentially important controlling factors in four F-concentration categories (<0.1-0.7 mg/L; >0.7-2 mg/L; >2-4 mg/L; >4 mg/L) at the national scale indicate the highest F-concentration category is associated with groundwater that has significantly greater pH values, TDS and alkalinity concentrations, and well depths, and lower Ca/Na ratios and mean annual precipitation, than the lowest F-concentration category. The relative importance of the controlling factors appears to be regionally variable. Three case studies illustrate the spatial variability in controlling factors using groundwater-age (groundwater residence time), water-isotope (evaporative concentration), and water-temperature (geothermal processes) data. Populations potentially served by domestic wells with F concentrations <0.7, >0.7, >2, and >4 mg/L are estimated to be ~28,200,000, ~3,110,000; ~522,000; and ~172,000 people, respectively, in 40 principal aquifers with at least 25 F analyses per aquifer.

Occurrence and Sources of Radium in Groundwater Associated with Oil Fields in the Southern San Joaquin Valley, California.

Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range = 0.010-0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p < 0.001, ρ = 0.90, range = 145-15,900 mg/L), Mn + Fe concentrations (p < 0.001, ρ = 0.82, range = <0.005-18.5 mg/L), and pH (p < 0.001, ρ = -0.67, range = 6.2-9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median = 3.1) differed from those in oil-field water (median = 0.51). PHREEQC mixing calculations and spatial geochemical variations suggest that the Ra in the oil-field water was removed by coprecipitation with secondary barite and adsorption on Mn-Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

Hydrocarbons in Upland Groundwater, Marcellus Shale Region, Northeastern Pennsylvania and Southern New York, U.S.A.

Water samples from 50 domestic wells located <1 km (proximal) and >1 km (distal) from shale-gas wells in upland areas of the Marcellus Shale region were analyzed for chemical, isotopic, and groundwater-age tracers. Uplands were targeted because natural mixing with brine and hydrocarbons from deep formations is less common in those areas compared to valleys. CH4-isotope, predrill CH4-concentration, and other data indicate that one proximal sample (5% of proximal samples) contains thermogenic CH4 (2.6 mg/L) from a relatively shallow source (Catskill/Lock Haven Formations) that appears to have been mobilized by shale-gas production activities. Another proximal sample contains five other volatile hydrocarbons (0.03-0.4 µg/L), including benzene, more hydrocarbons than in any other sample. Modeled groundwater-age distributions, calibrated to 3H, SF6, and 14C concentrations, indicate that water in that sample recharged prior to shale-gas development, suggesting that land-surface releases associated with shale-gas production were not the source of those hydrocarbons, although subsurface leakage from a nearby gas well directly into the groundwater cannot be ruled out. Age distributions in the samples span ∼20 to >10000 years and have implications for relating occurrences of hydrocarbons in groundwater to land-surface releases associated with recent shale-gas production and for the time required to flush contaminants from the system.

Elevated Manganese Concentrations in United States Groundwater, Role of Land Surface-Soil-Aquifer Connections.

Chemical data from 43 334 wells were used to examine the role of land surface-soil-aquifer connections in producing elevated manganese concentrations (>300 µg/L) in United States (U.S.) groundwater. Elevated concentrations of manganese and dissolved organic carbon (DOC) in groundwater are associated with shallow, anoxic water tables and soils enriched in organic carbon, suggesting soil-derived DOC supports manganese reduction and mobilization in shallow groundwater. Manganese and DOC concentrations are higher near rivers than farther from rivers, suggesting river-derived DOC also supports manganese mobilization. Anthropogenic nitrogen may also affect manganese concentrations in groundwater. In parts of the northeastern U.S. containing poorly buffered soils, ∼40% of the samples with elevated manganese concentrations have pH values < 6 and elevated concentrations of nitrate relative to samples with pH ≥ 6, suggesting acidic recharge produced by the oxidation of ammonium in fertilizer helps mobilize manganese. An estimated 2.6 million people potentially consume groundwater with elevated manganese concentrations, the highest densities of which occur near rivers and in areas with organic carbon rich soil. Results from this study indicate land surface-soil-aquifer connections play an important role in producing elevated manganese concentrations in groundwater used for human consumption.

Methane in groundwater from a leaking gas well, Piceance Basin, Colorado, USA.

Site-specific and regional analysis of time-series hydrologic and geochemical data collected from 15 monitoring wells in the Piceance Basin indicated that a leaking gas well contaminated shallow groundwater with thermogenic methane. The gas well was drilled in 1956 and plugged and abandoned in 1990. Chemical and isotopic data showed the thermogenic methane was not from mixing of gas-rich formation water with shallow groundwater or natural migration of a free-gas phase. Water-level and methane-isotopic data, and video logs from a deep monitoring well, indicated that a shale confining layer ~125m below the zone of contamination was an effective barrier to upward migration of water and gas. The gas well, located 27m from the contaminated monitoring well, had ~1000m of uncemented annular space behind production casing that was the likely pathway through which deep gas migrated into the shallow aquifer. Measurements of soil gas near the gas well showed no evidence of methane emissions from the soil to the atmosphere even though methane concentrations in shallow groundwater (16 to 20mg/L) were above air-saturation levels. Methane degassing from the water table was likely oxidized in the relatively thick unsaturated zone (~18m), thus rendering the leak undetectable at land surface. Drilling and plugging records for oil and gas wells in Colorado and proxies for depth to groundwater indicated thousands of oil and gas wells were drilled and plugged in the same timeframe as the implicated gas well, and the majority of those wells were in areas with relatively large depths to groundwater. This study represents one of the few detailed subsurface investigations of methane leakage from a plugged and abandoned gas well. As such, it could provide a useful template for prioritizing and assessing potentially leaking wells, particularly in cases where the leakage does not manifest itself at land surface.

Methane and Benzene in Drinking-Water Wells Overlying the Eagle Ford, Fayetteville, and Haynesville Shale Hydrocarbon Production Areas.

Water wells (n = 116) overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas were sampled for chemical, isotopic, and groundwater-age tracers to investigate the occurrence and sources of selected hydrocarbons in groundwater. Methane isotopes and hydrocarbon gas compositions indicate most of the methane in the wells was biogenic and produced by the CO2 reduction pathway, not from thermogenic shale gas. Two samples contained methane from the fermentation pathway that could be associated with hydrocarbon degradation based on their co-occurrence with hydrocarbons such as ethylbenzene and butane. Benzene was detected at low concentrations (<0.15 µg/L), but relatively high frequencies (2.4-13.3% of samples), in the study areas. Eight of nine samples containing benzene had groundwater ages >2500 years, indicating the benzene was from subsurface sources such as natural hydrocarbon migration or leaking hydrocarbon wells. One sample contained benzene that could be from a surface release associated with hydrocarbon production activities based on its age (10 ± 2.4 years) and proximity to hydrocarbon wells. Groundwater travel times inferred from the age-data indicate decades or longer may be needed to fully assess the effects of potential subsurface and surface releases of hydrocarbons on the wells.

Groundwater ages and mixing in the Piceance Basin natural gas province, Colorado.

Reliably identifying the effects of energy development on groundwater quality can be difficult because baseline assessments of water quality completed before the onset of energy development are rare and because interactions between hydrocarbon reservoirs and aquifers can be complex, involving both natural and human processes. Groundwater age and mixing data can strengthen interpretations of monitoring data from those areas by providing better understanding of the groundwater flow systems. Chemical, isotopic, and age tracers were used to characterize groundwater ages and mixing with deeper saline water in three areas of the Piceance Basin natural gas province. The data revealed a complex array of groundwater ages (<10 to >50,000 years) and mixing patterns in the basin that helped explain concentrations and sources of methane in groundwater. Age and mixing data also can strengthen the design of monitoring programs by providing information on time scales at which water quality changes in aquifers might be expected to occur. This information could be used to establish maximum allowable distances of monitoring wells from energy development activity and the appropriate duration of monitoring.

Assessing the relative bioavailability of DOC in regional groundwater systems.

It has been hypothesized that the degree to which a hyperbolic relationship exists between concentrations of dissolved organic carbon (DOC) and dissolved oxygen (DO) in groundwater may indicate the relative bioavailability of DOC. This hypothesis was examined for 73 different regional aquifers of the United States using 7745 analyses of groundwater compiled by the National Water Assessment (NAWQA) program of the U.S. Geological Survey. The relative reaction quotient (RRQ), a measure of the curvature of DOC concentrations plotted versus DO concentrations and regressed to a decaying hyperbolic equation, was used to assess the relative bioavailability of DOC. For the basalt aquifer of Oahu, Hawaii, RRQ values were low (0.0013 mM(-2)), reflecting a nearly random relationship between DOC and DO concentrations. In contrast, on the island of Maui, treated sewage effluent injected into a portion of the basalt aquifer resulted in pronounced hyperbolic DOC-DO behavior and a higher RRQ (142 mM(-2)). RRQ values for the 73 aquifers correlated positively with mean concentrations of ammonia, dissolved iron, and manganese, and correlated negatively with mean pH. This indicates that greater RRQ values are associated with greater concentrations of the final products of microbial reduction reactions. RRQ values and DOC concentrations were negatively correlated with the thickness of the unsaturated zone (UNST) and depth to the top of the screened interval. Finally, RRQ values were positively correlated with mean annual precipitation (MAP), and the highest observed RRQ values were associated with aquifers receiving MAP rates ranging between 900 and 1300 mm/year. These results are uniformly consistent with the hypothesis that the hyperbolic behavior of DOC-DO plots, as quantified by the RRQ metric, can be an indicator of relative DOC bioavailability in groundwater systems.

Groundwater depletion and sustainability of irrigation in the US High Plains and Central Valley.

Aquifer overexploitation could significantly impact crop production in the United States because 60% of irrigation relies on groundwater. Groundwater depletion in the irrigated High Plains and California Central Valley accounts for ~50% of groundwater depletion in the United States since 1900. A newly developed High Plains recharge map shows that high recharge in the northern High Plains results in sustainable pumpage, whereas lower recharge in the central and southern High Plains has resulted in focused depletion of 330 km(3) of fossil groundwater, mostly recharged during the past 13,000 y. Depletion is highly localized with about a third of depletion occurring in 4% of the High Plains land area. Extrapolation of the current depletion rate suggests that 35% of the southern High Plains will be unable to support irrigation within the next 30 y. Reducing irrigation withdrawals could extend the lifespan of the aquifer but would not result in sustainable management of this fossil groundwater. The Central Valley is a more dynamic, engineered system, with north/south diversions of surface water since the 1950s contributing to ~7× higher recharge. However, these diversions are regulated because of impacts on endangered species. A newly developed Central Valley Hydrologic Model shows that groundwater depletion since the 1960s, totaling 80 km(3), occurs mostly in the south (Tulare Basin) and primarily during droughts. Increasing water storage through artificial recharge of excess surface water in aquifers by up to 3 km(3) shows promise for coping with droughts and improving sustainability of groundwater resources in the Central Valley.

Dissolved oxygen as an indicator of bioavailable dissolved organic carbon in groundwater.

Concentrations of dissolved oxygen (DO) plotted vs. dissolved organic carbon (DOC) in groundwater samples taken from a coastal plain aquifer of South Carolina (SC) showed a statistically significant hyperbolic relationship. In contrast, DO-DOC plots of groundwater samples taken from the eastern San Joaquin Valley of California (CA) showed a random scatter. It was hypothesized that differences in the bioavailability of naturally occurring DOC might contribute to these observations. This hypothesis was examined by comparing nine different biochemical indicators of DOC bioavailability in groundwater sampled from these two systems. Concentrations of DOC, total hydrolysable neutral sugars (THNS), total hydrolysable amino acids (THAA), mole% glycine of THAA, initial bacterial cell counts, bacterial growth rates, and carbon dioxide production/consumption were greater in SC samples relative to CA samples. In contrast, the mole% glucose of THNS and the aromaticity (SUVA(254)) of DOC was greater in CA samples. Each of these indicator parameters were observed to change with depth in the SC system in a manner consistent with active biodegradation. These results are uniformly consistent with the hypothesis that the bioavailability of DOC is greater in SC relative to CA groundwater samples. This, in turn, suggests that the presence/absence of a hyperbolic DO-DOC relationship may be a qualitative indicator of relative DOC bioavailability in groundwater systems.

Fate of effluent-borne contaminants beneath septic tank drainfields overlying a Karst aquifer.

Groundwater quality effects from septic tanks were investigated in the Woodville Karst Plain, an area that contains numerous sinkholes and a thin veneer of sands and clays overlying the Upper Floridan aquifer (UFA). Concerns have emerged about elevated nitrate concentrations in the UFA, which is the source of water supply in this area of northern Florida. At three sites during dry and wet periods in 2007-2008, water samples were collected from the septic tank, shallow and deep lysimeters, and drainfield and background wells in the UFA and analyzed for multiple chemical indicators including nutrients, nitrate isotopes, organic wastewater compounds (OWCs), pharmaceutical compounds, and microbiological indicators (bacteria and viruses). Median NO3-N concentration in groundwater beneath the septic tank drainfields was 20 mg L(-1) (8.0-26 mg L(-1)). After adjusting for dilution, about 25 to 40% N loss (from denitrification, ammonium sorption, and ammonia volatilization) occurs as septic tank effluent moves through the unsaturated zone to the water table. Nitrogen loading rates to groundwater were highly variable at each site (3.9-12 kg N yr(-1)), as were N and chloride depth profiles in the unsaturated zone. Most OWCs and pharmaceutical compounds were highly attenuated beneath the drainfields; however, five Cs (caffeine, 1,7-dimethylxanthine, phenol, galaxolide, and tris(dichloroisotopropyl)phosphate) and two pharmaceutical compounds (acetaminophen and sulfamethoxazole) were detected in groundwater samples. Indicator bacteria and human enteric viruses were detected in septic tank effluent samples but only intermittently in soil water and groundwater. Contaminant movement to groundwater beneath each septic tank system also was related to water use and differences in lithology at each site.

Biodegradation of 17beta-estradiol, estrone and testosterone in stream sediments.

Biodegradation of 17beta-estradiol (E2), estrone (E1), and testosterone (T) was investigated in three wastewater treatment plant (WWTP) affected streams in the United States. Relative differences in the mineralization of [4-(14)C] substrates were assessed in oxic microcosms containing saturated sediment or water-only from locations upstream and downstream of the WWTP outfall in each system. Upstream sediment demonstrated significant mineralization of the "A" ring of E2, E1, and T, with biodegradation of T consistently greater than that of E2 and no systematic difference in E2 and E1 biodegradation. "A" ring mineralization also was observed in downstream sediment, with E1 and T mineralization being substantially depressed relative to upstream samples. In marked contrast, E2 mineralization in sediment immediately downstream from the WWTP outfalls was more than double that in upstream sediment. E2 mineralization was observed in water, albeit at insufficient rate to prevent substantial downstream transport. The results indicate that, in combination with sediment sorption processes which effectively scavenge hydrophobic contaminants from the water column and immobilize them in the vicinity of the WWTP outfall, aerobic biodegradation of reproductive hormones can be an environmentally important mechanism for noncon-servative (destructive) attenuation of hormonal endocrine disruptors in effluent-affected streams.

Distinguishing iron-reducing from sulfate-reducing conditions.

Ground water systems dominated by iron- or sulfate-reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe(2+)) and sulfide (sum of H(2)S, HS(-), and S(=) species and denoted here as "H(2)S"). This approach is based on the observation that concentrations of Fe(2+) and H(2)S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe(2+) concentrations are high, H(2)S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe(2+) with H(2)S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron- and the sulfate-reducing microorganisms that catalyze the production of Fe(2+) and H(2)S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe(2+) and H(2)S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H(2)) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe(2+)/H(2)S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H(2) approximately 0.2 to 0.8 nM). Conversely, if the Fe(2+)/H(2)S ratio was less than 0.30, consistent sulfate-reducing (H(2) approximately 1 to 5 nM) conditions were observed over time. Concomitantly high Fe(2+) and H(2)S concentrations were associated with H(2) concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron- and sulfate-reducing zones or concomitant iron and sulfate reduction under nonelectron donor-limited conditions. These observations suggest that Fe(2+)/H(2)S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems.

Potential for 4-n-nonylphenol biodegradation in stream sediments.

The potential for in situ biodegradation of 4-nonylphenol (4-NP) was investigated in three hydrologically distinct streams impacted by wastewater treatment plants (WWTPs) in the United States. Microcosms were prepared with sediments from each site and amended with [U-ring-(14)C]4-n-nonylphenol (4-n-NP) as a model test substrate. Microcosms prepared with sediment collected upstream of the WWTP outfalls and incubated under oxic conditions showed rapid and complete mineralization of [U-ring-(14)C]4-n-NP to (14)CO(2) in all three systems. In contrast, no mineralization of [U-ring-(14)C]4-n-NP was observed in these sediments under anoxic (methanogenic) conditions. The initial linear rate of [U-ring-(14)C]4-n-NP mineralization in sediments from upstream and downstream of the respective WWTP outfalls was inversely correlated with the biochemical oxygen demand (BOD) of the streambed sediments. These results suggest that the net supply of dissolved oxygen to streambed sediments is a key determinant of the rate and extent of 4-NP biodegradation in stream systems. In the stream systems considered by the present study, dissolved oxygen concentrations in the overlying water column (8-10 mg/L) and in the bed sediment pore water (1-3 mg/L at a depth of 10 cm below the sediment-water interface) were consistent with active in situ 4-NP biodegradation. These results suggest WWTP procedures that maximize the delivery of dissolved oxygen while minimizing the release of BOD to stream receptors favor efficient biodegradation of 4-NP contaminants in wastewater-impacted stream environments.

Biotransformation of caffeine, cotinine, and nicotine in stream sediments: implications for use as wastewater indicators.

Microbially catalyzed cleavage of the imadazole ring of caffeine was observed in stream sediments collected upstream and downstream of municipal wastewater treatment plants (WWTP) in three geographically separate stream systems. Microbial demethylation of the N-methyl component of cotinine and its metabolic precursor, nicotine, also was observed in these sediments. These findings indicate that stream sediment microorganisms are able to substantially alter the chemical structure and thus the analytical signatures of these candidate waste indicator compounds. The potential for in situ biotransformation must be considered if these compounds are employed as markers to identify the sources and track the fate of wastewater compounds in surface-water systems.