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Fate and transport of petroleum hydrocarbons in soil and ground water at Big South Fork National River and Recreation Area, Tennessee and Kentucky, 2002-2003

In 2002 and 2003, the U.S. Geological Survey (USGS), by agreement with the National Park Service (NPS), investigated the effects of oil and gas production operations on ground-water quality at Big South Fork National River and Recreation Area (BISO) with particular emphasis on the fate and transport of petroleum hydrocarbons in soils and ground water. During a reconnaissance of ground-water-quality conditions, samples were collected from 24 different locations (17 springs, 5 water-supply wells, 1 small stream, and 1 spring-fed pond) in and near BISO. Benzene, toluene, ethylbenzene, and xylene (BTEX) compounds were not detected in any of the water samples, indicating that no widespread contamination of ground-water resources by dissolved petroleum hydrocarbons probably exists at BISO. Additional water-quality samples were collected from three springs and two wells for more detailed analyses to obtain additional information on ambient water-quality conditions at BISO. Soil gas, soil, water, and crude oil samples were collected at three study sites in or near BISO where crude oil had been spilled or released (before 1993). Diesel range organics (DRO) were detected in soil samples from all three of the sites at concentrations greater than 2,000 milligrams per kilogram. Low concentrations (less than 10 micrograms per kilogram) of BTEX compounds were detected in lab-analyzed soil samples from two of the sites. Hydrocarbon-degrading bacteria counts in soil samples from the most contaminated areas of the sites were not greater than counts for soil samples from uncontaminated (background) sites. The elevated DRO concentrations, the presence of BTEX compounds, and the low number of -hydrocarbon-degrading bacteria in contaminated soils indicate that biodegradation of petroleum hydrocarbons in soils at these sites is incomplete. Water samples collected from the three study sites were analyzed for BTEX and DRO. Ground-water samples were collected from three small springs at the two sites located on ridge tops. BTEX and DRO were not detected in any of the water samples, and petroleum hydrocarbons do not appear to have leached into ground water at these sites. Ground-water samples were collected from a small spring and from three auger holes at the third site, which is located in a stream valley. BTEX and DRO were not detected in these ground-water samples, and currently, petroleum hydrocarbons do not appear to be leaching into ground water at this site. Weathered crude oil, however, was detected at the water surface in one of the auger holes, indicating that soluble petroleum hydrocarbons may have leached into the ground water and may have migrated downgradient from the site in the past. The concentration of soluble petroleum hydrocarbons present in the ground water would depend on the concentration of the hydrocarbons in the crude oil at the site. A laboratory study was conducted to examine the dissolution of petroleum hydrocarbons from a fresh crude oil sample collected from one of the study sites. The effective solubility of benzene, toluene, ethylbenzene, and total xylenes for the crude oil sample was determined to be 1,900, 1,800, 220, and 580 micrograms per liter (?g/L), respectively. These results indicate that benzene and toluene could be present at concentrations greater than maximum contaminant levels (5 ?g/L for benzene and 1,000 ?g/L for toluene for drinking water) in ground water that comes into contact with fresh crude oil from the study area.

Scientific Investigations Report

Borehole geophysical monitoring of amendment emplacement and geochemical changes during vegetable oil biostimulation, Anoka County Riverfront Park, Fridley, Minnesota

The U.S. Geological Survey ( USGS ) conducted a series of geophysical investigations to monitor a field-scale biostimulation pilot project at the Anoka County Riverfront Park ( ACP ), downgradient from the Naval Industrial Reserve Ordnance Plant, in Fridley, Minnesota. The pilot project was undertaken by the U.S. Naval Facilities Engineering Command, Southern Division, for the purpose of evaluating biostimulation using emulsified vegetable oil to treat ground water contaminated with chlorinated hydrocarbons. Vegetable oil was introduced to the subsurface to serve as substrate for naturally occurring microbes, which ultimately break down chlorinated hydrocarbons into chloride, carbon dioxide, and water through oxidation-reduction reactions. In support of this effort, the USGS collected cross-borehole radar data and conventional borehole geophysical data in five site visits over 1.5 years to evaluate the effectiveness of geophysical methods for monitoring emplacement of the vegetable oil emulsion and for tracking changes in water chemistry. Radar zero-offset profile ( ZOP ) data, radar traveltime tomograms, electromagnetic ( EM ) induction logs, natural gamma logs, neutron porosity logs, and magnetic susceptibility logs were collected and analyzed. In order to facilitate data interpretation and to test the effectiveness of radar for monitoring oil-emulsion placement and movement, three injection mixtures with different radar signatures were used: (1) vegetable oil emulsion, (2) vegetable oil emulsion with a colloidal iron tracer, and (3) vegetable oil emulsion with a magnetite tracer. Based on petrophysical modeling, mixture (1) was expected to increase radar velocity and decrease radar attenuation relative to background—a water-saturated porous medium; mixtures (2) and (3) were expected to increase radar velocity and increase radar attenuation because of their greater electrical conductivity compared to background ground water. Radar ZOP data and tomograms show increased EM velocity in the vicinity of injection wells. Comparison of pre- and post-injection datasets shows that velocity anomalies are observed only in planes connected to injection wells, indicating that the emulsified vegetable oil does not migrate far after injection. In contrast to the localization of velocity anomalies, radar attenuation anomalies are observed in all zero-offset profiles, particularly those downgradient from the injection wells. Despite the expected signatures of different tracers, increases in attenuation are observed downgradient from all three injection wells; thus, we infer that the attenuation changes do not result from the iron tracers alone. Over the period of data collection, the slowness (reciprocal velocity) anomalies are relatively stable, whereas the attenuation anomalies generally increase in magnitude and extent. One explanation for the attenuation changes is that products of vegetable oil-enhanced biodegradation (for example, chloride) increase the specific conductance of ground water and thus bulk electrical conductivity and radar attenuation. This interpretation is supported by the results of EM-induction and magnetic susceptibility logs, which indicate increases in electrical conductivity in the absence of magnetic anomalies that might result from the iron and magnetite. Based on the geophysical data, conceptual models of the distributions of emulsified vegetable oil and ground water with altered chemistry were developed. The field data indicate that, in several cases, the plume of ground water with altered chemistry would not be detected by direct chemical sampling given the construction of monitoring wells; hence the geophysical data provide valuable site-specific insights for the interpretation of water samples and monitoring of biostimulation projects. Application of geophysical methods to data from the ACP demonstrated the utility of radar for monitoring biostimulation injections.

Minnesota

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

Davis Pond freshwater prediversion biomonitoring study: freshwater fisheries and eagles

In January 2001, the construction of the Davis Pond freshwater diversion structure was completed by the U.S. Army Corps of Engineers. The diversion of freshwater from the Mississippi River is intended to mitigate saltwater intrusion from the Gulf of Mexico and to lessen the concomitant loss of wetland areas. In addition to the freshwater inflow, Barataria Bay basin would receive nutrients, increased flows of sediments, and water-borne and sediment-bound compounds. The purpose of this biomonitoring study was, therefore, to serve as a baseline for prediversion concentrations of selected contaminants in bald eagle ( Haliaeetus leucocephalus ) nestlings (hereafter referred to as eaglets), representative freshwater fish, and bivalves. Samples were collected from January through June 2001. Two similarly designed postdiversion studies, as described in the biological monitoring program, are planned. Active bald eagle nests targeted for sampling eaglet blood (n = 6) were generally located southwest and south of the diversion structure. The designated sites for aquatic animal sampling were at Lake Salvador, at Lake Cataouatche, at Bayou Couba, and along the Mississippi River. Aquatic animals representative of eagle prey were collected. Fish were from three different trophic levels and have varying feeding strategies and life histories. These included herbivorous striped mullet ( Mugil cephalus ), omnivorous blue catfish ( Ictalurus furcatus ), and carnivorous largemouth bass ( Micropterus salmoides ). Three individuals per species were collected at each of the four sampling sites. Freshwater Atlantic rangia clams ( Rangia cuneata ) were collected at the downstream marsh sites, and zebra mussels ( Dreissena spp.) were collected on the Mississippi River. The U.S. Geological Survey (USGS) Biomonitoring of Environmental Status and Trends (BEST) protocols served as guides for fish sampling and health assessments. Fish are useful for monitoring aquatic ecosystems because they accumulate pesticides and other contaminants. Biomarker data on individual fish, generated at the USGS National Wetlands Research Center (Lafayette, La.), included percent white blood cells in whole blood, spleen weight to body weight ratio, liver weight to body weight ratio, condition factor, splenic macrophage aggregates, and liver microsomal 7-ethoxyresorufin-o-deethylase (EROD) activity. Fish age was estimated by comparing total lengths with values from the same species in the Southeast United States as determined from the literature. Contaminant analyses were coordinated by the U.S. Fish and Wildlife Service (USFWS) Analytical Control Facility (Laurel, Md.), where residues of organochlorine (OC) pesticides, total polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (AHs), and trace elements were determined. The organic contaminant data were generated at the Mississippi State University Chemical Lab (Mississippi State, Miss.), and the inorganic contaminant data were generated by the Texas A&M University Geochemical and Environmental Research Group (College Station, Tex.). Statistical tests were performed to assess relationships among contaminants, fish age, fish species, and collection sites. Trends in interspecific differences among fish in concentrations of contaminants were noted. Striped mullet (hereafter mullet) frequently displayed the highest chemical concentrations. Levels of contaminants were generally higher in samples obtained from the Mississippi River than in those collected from the diversion area and were higher in mussels and clams (hereafter bivalves) than in fish. Because the Mississippi River sampling site for mullet and largemouth bass was downriver of the structure and south of New Orleans and the catfish site was upriver, the downriver data may not be directly reflective of the results from the receiving waters at the Davis Pond structure. Compared to the Caernarvon freshwater prediversion study in 1990 that assessed possible influx of contaminants with the freshwater diversion, contaminant levels in fishes and bivalves in this study were generally lower, yet three nontoxic inorganic elements in Davis Pond fish samples exhibited ranges of concentrations that were more than two times higher than did those from Caernarvon. Levels in bivalves were different between diversions but about equal in the numbers of trace elements showing high levels per location. Contaminant values were compared to those listed in various literature and agency sources, both regional and national, including the National Contaminant Biomonitoring Program (NCBP), in which the 85th percentile and above represents what is considered to be an elevated contaminant concentration and cause for concern. Generally, bivalves were at the high end of their ranges for both organic and inorganic contaminants. In this study, OCs were detectable in 67 percent of fish from the Mississippi River site, ranging from 0.15 to 1.09 μg/g wet weight (ww) or fresh weight (fw), and in 11 percent of the fish from the marsh sites, ranging from 0.06 to 0.612 μg/g ww. Bivalves from the Mississippi River had OC levels of 0.096 μg/g ww, whereas none were detectable in bivalves at the marsh sites. In this study, p,p ’-dichlorodiphenyldichloroethylene ( p,p’ -DDE) (a biodegradation product of DDT [dichlorodiphenyl trichloroethane]) and total PCBs were the most frequently detected OCs and were primarily from the Mississippi River. For total OC content, using adjusted least squares means, some significant interactions were noted between fish species and sites. PAHs were detected in aquatic animals at all sites (range of 0.017–17.534 μg/g ww), as were AHs (range of 0.423–4.549 μg/g ww); the highest levels of PAHs and AHs were found in bivalves from the Mississippi River. When analysis of variance (α = 0.05) was performed with data from aquatic animals, there were only two significant relationships between PAHs, AHs, and OCs between species, site, and age or the interaction among these variables. There was an interaction between fish species and n-decane (an AH) in that mullet and largemouth bass had significantly higher levels than did catfish ( P = 0.0175). When general linear means were used to investigate associations of inorganic contaminants among fish species, site, and age or any interactions among these variables, no significant results were noted for arsenic, cadmium, lead, beryllium, boron, molybdenum, or nickel. The range of mercury in fish in this study was 0.04–0.14 μg/g ww (0.14– 0.48 μg/g dry weight [dw]), with the most elevated levels detected in predatory largemouth bass at the sampling point farthest downstream from the structure and within the marsh area. Mercury was positively correlated with fish age ( P = 0.0152), where levels were estimated to increase 0.0253 parts per million (ppm) dw per year. In the Mississippi River, catfish showed significantly higher levels of mercury than did mullet or largemouth bass ( P = 0.00167). Among fish species, mullet displayed the highest levels in fish of aluminum, barium, manganese, and iron, all considered to have low toxicity in hydrologic systems. An interaction between fish and site was seen with aluminum ( P = 0.0031), where concentrations in mullet were significantly higher in the Mississippi River than at the other sites, as was also seen with barium ( P = 0.0009), chromium ( P = <0.0001), manganese ( P = 0.0004), strontium ( P = 0.0074), vanadium ( P = 0.0156), and zinc ( P = 0.0059). For iron ( P = 0.0.0001), mullet and largemouth bass at both the Mississippi River and Lake Salvador showed higher levels than did catfish, and these two species showed higher levels at two of the four sites. An interaction between fish and site was also seen with chromium ( P = <0.0001) in that concentrations in mullet were significantly higher in the Mississippi River than at the other sites, as was also seen with strontium ( P = 0.0074), vanadium ( P = 0.0156), and zinc ( P = 0.0059), metals for which deleterious effects have been demonstrated in other ecosystems. The NCBP program lists the 85th percentile for zinc at 34.2 μg/g fw (117.9 μg/g dw). In the Davis Pond prediversion biomonitoring study (hereafter the current study), one fish (MUL31RIVER, fish ID 8) showed values higher than that (125.4 μg/g dw or 37.54 μg/g ww), and the Mississippi River bivalve sample (MUSSRIVER) had a value of 140 μg/g dw (41.2 μg/g ww). In the current study, approximately 86 percent of the fish had measurable selenium levels, yet none reached the 85th percentile. The 85th percentile for selenium from the NCBP was 0.73 μg/g ww. Significantly higher levels of selenium were seen in mullet than in largemouth bass and catfish ( P = 0.0023). The NCBP 85th percentile for lead is 0.22 μg/g ww (0.76 μg/g dw). In the current study, the range of concentrations of lead was as much as 18.3 ppm dw (MUL31RIVER, fish ID 8), with the three most elevated values (range of 3.46–5.31 μg/g ww) coming from mullet from the Mississippi River. Biomarker data are measurable and directly reflect the condition of the animal, and measuring more than one biomarker in an individual increases confidence in health assessments. In the current study, biomarkers included macrophage aggregates (MAs), liver (hepatosomatic index [HSI]) and spleen (splenosomatic index [SSI]) weight to body weight ratios, percent white blood cells (WBCs) in whole blood, and condition factor. Few significant differences were noted with any of the biomarkers between sites, and there were no relationships between species and sites. For improved use of biomarker assessments, an increase in fish sample size would be useful for postdiversion sampling, as would comparisons of fish of the same sex and reproductive condition. During the current study, success for eagle nests in the diversion area and reference sites was similar as determined by numbers of nestlings fledged. When temperatures were below average during winter 2000, nests in both regions similarly failed. At each nest, the primary evidence of food items was small mammals. Eaglets (n = 6) generally appeared healthy, and whole blood concentrations of organic contaminants exceeded detection limits with three incidences of p,p’ -DDE (0.002–0.006 μg/L ww) and one incidence of oxychlordane (0.002 μg/L ww). The levels of p,p’ -DDE were well below those that have been inversely correlated with productivity and success rates of nesting bald eagles on a regional scale. The low values found in the whole blood samples for OC pesticides and PCBs were even lower when corrected for plasma volume. Aluminum values were 3.66 and 5.75 μg/L in two samples, zinc ranged from 5.21 to 6.77 μg/L ww in six samples, and silicon ranged from 1.7 to 4.6 μg/L in four samples. Selenium was detectable in each bird with the range at 0.332–0.566 μg/L ww, and strontium ranged from 0.0581 to 0.0975 μg/L ww. Mercury was detectable in blood samples from each bird and ranged from 0.0254 to 0.0845 μg/L ww, whereas lead was detectable in four samples and ranged from 0.0042 to 0.0136 μg/L ww. Although no detectable levels of total PCBs were found (also correlated with decreased reproductive productivity), 70 percent of the aquatic animals from the Mississippi River contained total PCBs (range 0.13–0.79 μg/L), whereas only about 7 percent of the aquatic animals sampled from the marsh area contained PCBs. Suggestions for postdiversion sampling include lowering the analytical detection limit for some metals, sampling aquatic animals over the course of a single season, obtaining a higher sample number of mature fish of one species (for example, blue catfish) within a range of total lengths for biomarker analyses, obtaining otoliths for estimating fish ages, assessing dioxins in eaglet blood, examining triazines in water, and obtaining all Mississippi River fish samples as close to the Davis Pond structure intake as possible. Because contaminants found in blood of eaglets reflect their prey species and because of the contaminant levels found in fish in the current study, eaglets may not be consuming primarily these species; therefore, obtaining juvenile nutria ( Myocastor coypus ) or turtle species for contaminant analyses might be considered, as well as collecting greater blood volume and using plasma to measure OCs and PCBs. Data obtained postdiversion will be compared with prediversion data to monitor changes.

Louisiana

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

Contamination movement around a permeable reactive barrier at Solid Waste Management Unit 12, Naval Weapons Station Charleston, North Charleston, South Carolina, 2009

The U.S. Geological Survey and the Naval Facilities Engineering Command Southeast investigated natural and engineered remediation of chlorinated volatile organic compound groundwater contamination at Solid Waste Management Unit 12 at the Naval Weapons Station Charleston, North Charleston, South Carolina, beginning in 2000. In early 2004, groundwater contaminants began moving around the southern end of a permeable reactive barrier (PRB) installed by a consultant in December 2002. The PRB is a 130-foot-long and 3-foot-wide barrier consisting of varying amounts of zero-valent iron with or without sand mixture. Contamination moving around the PRB probably has been transported at least 75 feet downgradient from the PRB at a rate of about 15 to 29 feet per year. The diversion of contamination around the southern end of the PRB may be due to construction difficulties associated with the PRB installation or to reduced permeability in the PRB. An event that took place during installation of the PRB, which may have caused permeability loss, was the collapse and subsequent abandonment of a 110-foot-long trench originally designed to be the PRB on November 11, 2002, approximately 25 feet upgradient (west) from the final PRB. Guar gum with antimicrobial preservative in a polymer slurry had been used to stabilize the abandoned trench prior to collapse and was only partially recovered. Residual guar gum can cause permeability reduction in a PRB. It also is possible that permeability reduction took place within the PRB by slow degradation of the guar gum slurry or mineral precipitation. Despite the likely permeability reduction in and near the PRB immediately following installation, there is evidence that contaminants moved through the PRB and were degraded, consistent with the planned purpose of the PRB. Volatile organic compound contamination in groundwater downgradient from the PRB is subject to attenuation by phytovolatilization, sorption, and biodegradation. Pulses of contamination increases have been observed in some monitoring wells downgradient from the PRB. The pulses may reflect downgradient transport of contaminant pulses; however, lateral shifting of the plume is a more likely explanation for the concentration changes at well 12MW-12S. The ability to monitor the fate and behavior of the plume in the forest is severely limited because the present axis of maximum contamination in that area bypasses all but one of the existing monitoring wells (12MW-12S). Moreover, the 2009 data indicate that there are no optimally placed sentinel wells in the probable path of contaminant transport. Thus the monitoring network is no longer adequate to monitor the groundwater contamination downgradient from the PRB.

South Carolina

Status and understanding of groundwater quality in the South Coast Range-Coastal study unit, 2008: California GAMA Priority Basin Project

Groundwater quality in the South Coast Range–Coastal (SCRC) study unit was investigated from May through November 2008 as part of the Priority Basin Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The study unit is located in the Southern Coast Range hydrologic province and includes parts of Santa Barbara and San Luis Obispo Counties. The GAMA Priority Basin Project is conducted by the U.S. Geological Survey (USGS) in collaboration with the California State Water Resources Control Board and the Lawrence Livermore National Laboratory. The GAMA Priority Basin Project was designed to provide a statistically unbiased, spatially distributed assessment of untreated groundwater quality within the primary aquifer system. The primary aquifer system is defined as that part of the aquifer corresponding to the perforation interval of wells listed in the California Department of Public Health (CDPH) database for the SCRC study unit. The assessments for the SCRC study unit were based on water-quality and ancillary data collected in 2008 by the USGS from 55 wells on a spatially distributed grid, and water-quality data from the CDPH database. Two types of assessments were made: (1) status, assessment of the current quality of the groundwater resource, and (2) understanding, identification of the natural and human factors affecting groundwater quality. Water-quality and ancillary data were collected from an additional 15 wells for the understanding assessment. The assessments characterize untreated groundwater quality, not the quality of treated drinking water delivered to consumers by water purveyors. The first component of this study, the status assessment of groundwater quality, used data from samples analyzed for anthropogenic constituents such as volatile organic compounds (VOCs) and pesticides, as well as naturally occurring inorganic constituents such as major ions and trace elements. Although the status assessment applies to untreated groundwater, Federal and California regulatory and non-regulatory water-quality benchmarks that apply to drinking water are used to provide context for the results. Relative-concentrations (sample concentration divided by benchmark concentration) were used for evaluating groundwater. A relative-concentration greater than (>) 1.0 indicates a concentration greater than the benchmark and is classified as high. Inorganic constituents are classified as moderate if relative-concentrations are >0.5 and less than or equal to (≤) 1.0, or low if relative-concentrations are ≤0.5. For organic constituents, the boundary between moderate and low relative-concentrations was set at 0.1. Aquifer-scale proportion was used in the status assessment as the primary metric for evaluating regional-scale groundwater quality. High aquifer-scale proportion is defined as the areal percentage of the primary aquifer system with a high relative-concentration for a particular constituent or class of constituents. Moderate and low aquifer-scale proportions were defined as the areal percentage of the primary aquifer system with moderate and low relative-concentrations, respectively. Two statistical approaches—grid-based and spatially weighted—were used to evaluate aquifer-scale proportions for individual constituents and classes of constituents. Grid-based and spatially weighted estimates were comparable for the study (within 90 percent confidence intervals). For inorganic constituents with human-health benchmarks, relative-concentrations were high for at least one constituent for 33 percent of the primary aquifer system in the SCRC study unit. Arsenic, molybdenum, and nitrate were the primary inorganic constituents with human-health benchmarks that were detected at high relative-concentrations. Inorganic constituents with aesthetic benchmarks, referred to as secondary maximum contaminant levels (SMCLs), had high relative-concentrations for 35 percent of the primary aquifer system. Iron, manganese, total dissolved solids (TDS), and sulfate were the inorganic constituents with SMCLs detected at high relative-concentrations. In contrast to inorganic constituents, organic constituents with human-health benchmarks were not detected at high relative-concentrations in the primary aquifer system in the SCRC study unit. Of the 205 organic constituents analyzed, 21 were detected—13 with human-health benchmarks. Perchloroethene (PCE) was the only VOC detected at moderate relative-concentrations. PCE, dichlorodifluoromethane (CFC-12), and chloroform were detected in more than 10 percent of the primary aquifer system. Of the two special-interest constituents, one was detected; perchlorate, which has a human-health benchmark, was detected at moderate relative-concentrations in 29 percent of the primary aquifer system and had a detection frequency of 60 percent in the SCRC study unit. The second component of this study, the understanding assessment, identified the natural and human factors that may have affected groundwater quality in the SCRC study unit by evaluating statistical correlations between water-quality constituents and potential explanatory factors. The potential explanatory factors evaluated were land use, septic tank density, well depth and depth to top-of-perforations, groundwater age, density and distance to the nearest formerly leaking underground fuel tank (LUFT), pH, and dissolved oxygen (DO) concentration. Results of the statistical evaluations were used to explain the occurrence and distribution of constituents in the study unit. DO was the primary explanatory factor influencing the concentrations of many inorganic constituents. Arsenic, iron, and manganese concentrations increased as DO concentrations decreased, consistent with patterns expected as a result of reductive dissolution of iron and (or) manganese oxides in aquifer sediments. Molybdenum concentrations increased in anoxic conditions and in oxic conditions with high pH, reflecting two mechanisms for the mobilization of molybdenum—reductive dissolution and pH-dependent desorption under oxic conditions from aquifer sediments. Nitrate concentrations decreased as DO concentrations decreased which would be consistent with degradation of nitrate under anoxic conditions (denitrification). It also is possible that nitrate concentrations decreased in relation to increasing depth and groundwater age and not as a result of denitrification. Groundwater age was another explanatory factor frequently correlated to several inorganic constituents. Iron and manganese concentrations were higher in pre-modern (water recharged before 1952) or mixed-age groundwater. This correlation is one indication that iron and manganese are from natural sources. Nitrate, TDS, and sulfate concentrations were higher in modern groundwater (water recharged since 1952) and may indicate that human activities increase concentrations of nitrate, TDS, and sulfate. Land use was a third explanatory factor frequently correlated with inorganic constituents. Nitrate, TDS, and sulfate concentrations were higher in agricultural land-use areas than in natural land-use areas, indicating that increased concentrations may be a result of agricultural practices. Organic constituents usually were detected at low relative-concentrations; therefore, statistical analyses of relations to explanatory factors usually were done for classes of constituents (for example, pesticides or solvents) as well as for selected constituents. The number of VOCs detected in a well was not correlated to any of the explanatory factors evaluated. The number of pesticide and solvent detections and PCE and CFC-12 concentrations were higher in modern groundwater than in pre-modern groundwater. PCE and CFC-12 also were positively correlated to the density of LUFTs. PCE was negatively correlated to natural land use. Chloroform concentrations were positively correlated to the density of septic systems. Perchlorate concentrations were greater in agricultural areas than in urban or natural areas. Correlation of perchlorate with DO may indicate that perchlorate biodegradation under anoxic conditions may occur. Anthropogenic sources have contributed perchlorate to groundwater in the SCRC study unit, although low levels of perchlorate may occur naturally.

California

Variable-density groundwater flow and contaminant transport, Operable Unit 1, Naval Base Kitsap, Keyport, Washington

Chlorinated volatile organic compounds (CVOCs) have migrated to groundwater beneath a former 9-acre landfill at Operable Unit 1 (OU-1) on Naval Base Kitsap, which was active from the 1930s through 1973 on the Keyport Peninsula, in Kitsap County, Washington. Biodegradation of CVOCs at OU-1 limits the mass of dissolved-phase CVOCs in groundwater that discharges to surface water, but contaminant concentrations up to 630 milligrams per liter persist in localized areas, likely from the dissolution of residual, non-aqueous phase liquids. Variable-density groundwater-flow and contaminant-transport models were developed using the SEAWAT-Version 4 computer program to simulate the direction and rate of groundwater flow in a 5.9 square-mile (mi 2 ) - area surrounding the Keyport Peninsula, to estimate the CVOC mass in groundwater and the rate of mass loading, and to assess possible remedial activities at OU-1. The study area is underlain by Quaternary deposits consisting of alternating glacial and interglacial sediments ranging from 500 to 1,500 feet (ft) thick. A hydrogeologic model delineated a sequence of 10 units including a relatively thin package (less than 100 ft) of recent sediments (Vashon Stade and younger) beneath the Keyport Peninsula that are underlain by the much thicker (more than 300 ft) Clover Park Aquitard, which overlies a confined, sea-level aquifer.

Washington

Geologic assessment of undiscovered oil and gas resources in the Cherokee Platform area of Kansas, Oklahoma, and Missouri

In 2015, the U.S. Geological Survey completed a geology-based assessment to estimate the volumes of undiscovered, technically recoverable petroleum resources in the Cherokee Platform Province area of southeastern Kansas, northeastern Oklahoma, and southwestern Missouri. The U.S. Geological Survey identified four stratigraphic intervals that contain petroleum source rocks: (1) thin shales in the Middle to Upper Ordovician Simpson Group, (2) shales within the Upper Devonian to Lower Mississippian Woodford Shale and stratigraphically equivalent Chattanooga Shale, (3) coals and coal-associated shales and mudstones in the Middle Pennsylvanian (Desmoinesian) Cherokee and Marmaton Groups, and (4) thin marine shales within the Marmaton Group and the Upper Pennsylvanian (Missourian) Kansas City and Lansing Groups. Based on the nature of the petroleum accumulations, the characterization of the compositions and thermal maturity of the organic matter in the rocks, and the compositions of the produced petroleum, the U.S. Geological Survey identified three total petroleum systems (TPS) containing four assessment units (AU): the Paleozoic Composite TPS with the Paleozoic Conventional Assessment Unit (AU), the Woodford/Chattanooga TPS with the Woodford Shale Oil AU and the Woodford Biogenic Gas AU, and the Desmoinesian Coal TPS with the Desmoinesian Coalbed Gas AU. Assessment unit summaries follow 1. Three source rock intervals have contributed geochemically distinct oils to reservoirs within the Paleozoic Conventional AU. These intervals are the Simpson Group; the Woodford and Chattanooga Shales; and the Marmaton, Kansas City, and Lansing Groups. The major petroleum source rocks are the Woodford and Chattanooga Shales. The Paleozoic Conventional AU includes reservoirs that range in age from the Upper Cambrian Arbuckle Group to the lower Permian Chase Group. Most oil production in the province has been from Pennsylvanian sandstone reservoirs. Estimated undiscovered petroleum resources for this AU are a mean of 3 million barrels of oil (MMBO), 140 billion cubic feet of gas (BCFG), and 4 million barrels of natural gas liquids (MMBNGL). 2. The Woodford Shale Oil AU contains undiscovered continuous petroleum resources within the Woodford Shale and Chattanooga Shale. The geologic model for the AU assumes that petroleum resources remain trapped within the shale following petroleum migration. For most of the AU, organic matter within the Woodford Shale and Chattanooga Shale is thermally mature with respect to petroleum generation as shown by vitrinite reflectance values between 0.6 and 1 percent. Petroleum has been produced from the Woodford Shale and Chattanooga Shale. Estimated undiscovered petroleum resources for this AU are means of 460 MMBO, 640 BCFG, and 7 MMBNGL. 3. The Woodford Shale Biogenic Gas AU contains undiscovered continuous petroleum resources in the east-central portion of the Cherokee Platform Province near the Ozark uplift where the Woodford Shale and Chattanooga Shale are at depths of 1,250 ft or shallower. At those depths, methanogenesis and(or) biodegradation of thermogenic natural gases can be found where the shale may be more fractured and more susceptible to groundwater penetrations. The mean assessed volume of undiscovered gas for this assessment unit is 416 BCFG and 1 MMBNGL. 4. The Desmoinesian Coalbed Gas AU contains undiscovered continuous petroleum resources within the Middle Pennsylvanian coals and coal-associated shales and mudstones. The boundaries for the Desmoinesian Coalbed Gas AU are, in part, defined by the extent, depth, and thickness of the coals. Within the Desmoinesian Coalbed Gas AU, a sweet spot area was delineated based on a 10 foot or greater net coal thickness. Gas analytical data show that natural gas produced from the coals has a mixed biogenic and thermogenic origin and that there is significant migration of natural gas into the coals from adjacent conventional sandstone reservoirs. The estimated mean volume of undiscovered gas is 10.0 trillion cubic ft of gas (TCFG), and 23 MMBNGL. For the three continuous (unconventional) assessment units and one conventional assessment unit in the Cherokee Platform Province, total mean volumes of undiscovered petroleum resources are estimated to be 463 MMBO, 11.2 TCFG and 35 MMBNGL.

Kansas, Missouri, Oklahoma

Groundwater chemistry, hydrogeologic properties, bioremediation potential, and three-dimensional numerical simulation of the sand and gravel aquifer at Naval Air Station Whiting Field, near Milton, Florida, 2015–20

The U.S. Geological Survey completed a study between 2015 and 2020 of groundwater contamination in the sand and gravel aquifer at a Superfund site in northwestern Florida. Groundwater-quality samples were collected from representative monitoring wells located along a groundwater-flow pathway and analyzed in the field and laboratory. In general, ambient groundwater in the sand and gravel aquifer is acidic, dilute, and oxic. Groundwater age-dating results indicate recharge to the contaminated parts of the aquifer occurred between the 1970s and 1980s. Natural gamma, electromagnetic induction, and borehole nuclear magnetic resonance logs indicated that aquifer hydraulic conductivities generally increased with depth as the aquifer formation material became coarser, characteristic of a prograding marginal-marine delta depositional environment. Aquifer formation material incubated with radiocarbon (carbon-14) cis -1,2-Dichloroethylene demonstrated biodegradation directly to carbon dioxide in contaminated and uncontaminated parts of the aquifer. A three-dimensional, numerical groundwater-flow MODFLOW model of the sand and gravel aquifer in the study area was constructed. The calibrated model reasonably reproduced measured groundwater heads and streamflows. Moreover, the model can be used to run simulations of outcomes of potential remedial strategies, such as monitored natural attenuation, as part of future feasibility studies in the area.

Florida

Determination of stream reaeration coefficients by use of tracers

Stream reaeration is the physical absorption of oxygen from the atmosphere by a flowing stream. This is the primary process by which a stream replenishes the oxygen consumed in the biodegradation of organic wastes. Prior to 1965, reaeration rate coefficients could be estimated only by indirect methods. In 1965, a direct method of measuring stream reaeration coefficients was developed whereby a radioactive tracer gas was injected into a stream-the principle being that the tracer gas would be desorbed from the stream inversely to how oxygen would be absorbed. The technique has since been modified by substituting hydrocarbon gases for the radioactive tracer gas. This manual describes the slug-injection and constant-rate-injection methods of measuring gas-tracer desorption. Emphasis is on the use of rhodamine WT dye as a relatively conservative tracer and propane as the nonconservative gas tracer, on planning field tests, on methods of injection, sampling, and analysis, and on techniques for computing desorption and reaeration coefficients.

Techniques of Water-Resources Investigations

Field tests of polyethylene-membrane diffusion samplers for characterizing volatile organic compounds in stream-bottom sediments, Nyanza Chemical Waste Dump Superfund site, Ashland, Massachusetts

A plume of volatile organic compounds (VOCs) in ground water extends from the Nyanza Chemical Waste Dump Superfund site in Ashland, Massachusetts, northward toward a mill pond on the Sudbury River and eastward toward the Sudbury River and former mill raceway downstream from the mill pond. Polyethylene-membrane water-to-vapor (vapor) and water-to-water (water) diffusion samplers were installed January 1999 in bottom sediments along the Sudbury River and former mill raceway in a pilot study to determine if vapor samplers would be useful in this setting for delineating a plume of contaminants in ground water near the river and raceway, to evaluate equilibration time for vapor-diffusion samplers, and to determine if diffusion samplers might be an alternative to seepage meters (inverted steel drums) and sediment sampling for evaluating concentrations of VOCs in bottom sediments. Of five tested compounds (benzene, trichloroethene, toluene, tetrachloroethene, and chlorobenzene), chlorobenzene and trichloroethene were most frequently detected in vapor from vapor-diffusion samplers. The distribution of VOCs was generally consistent with a previously mapped plume of contaminants in ground water. The field evaluation of equilibration times for vapor-diffusion samplers was inconclusive because of changing hydrologic conditions that may have affected concentrations of VOCs, possible variations in concentrations ofVOCs over short distances, and imprecise sampling and analytical methods. The limited data, however, indicated that equilibration may require 3 weeks or more in some settings. VOCs detected in samples from water-diffusion samplers and their concentrations were comparable to results from seepage meters, and VOCs detected in vapor-diffusion samplers correlated with VOCs detected in water-diffusion samplers. These results indicate that either vapor-or water-diffusion samplers would serve as an economical alternative to seepage meters for sampling of VOCs in pore water from stream-bottom sediments. Results from diffusion samplers correlated poorly with results from sediment samples, partly because of high quantitation limits for chemical analyses of sediments. In general, results from the diffusion samplers better represented the distribution of VOCs than the results from the sediment samples. This pilot study indicates that diffusion samplers are an economical means of identifying 'hotspots' for contaminants in bottom sediments and can provide insights on transport pathways for contaminants near surface-water bodies. After establishing equilibration times for a particular site, diffusion samplers also may be useful for studying variations in concentrations of VOCs over short distances, variations with time and changing hydrologic conditions, and processes such as chemical transformations by biodegradation and exchanges between surface water and ground water in the hyporheic zone.

Water-Resources Investigations Report

Methodology for applying monitored natural attenuation to petroleum hydrocarbon-contaminated ground-water systems with examples from South Carolina

Natural attenuation processes such as dispersion, advection, and biogradation serve to decrease concentrations of disssolved contaminants as they are transported in all ground-water systems. However, the efficiency of these natural attenuation processes and the degree to which they help attain remediation goals, varies considerably from site to site. This report provides a methodology for quantifying various natural attenuation mechanisms. This methodology incorporates information on (1) concentrations of contaminants in space and/or time; (2) ambient reduction/oxidation (redox) conditions; (3) rates and directions of ground-water flow; (4) rates of contaminant biodegradation; and (5) demographic considerations, such as the presence of nearby receptor exposure points or property boundaries. This document outlines the hydrologic, geochemical, and biologic data needed to assess the efficiency of natural attenuation, provides a screening tool for making preliminary assessments, and provides examples of how to determine when natural attenuation can be a useful component of site remediation at leaking underground storage tank sites. At a site in the Piedmont Physiographic Province (Laurens, South Carolina), hydrologic and water-chemistry data indicate that the natural attenuation capacity for benzene is approximately 5 percent per foot of flowpath. As a result, benzene concentrations would decrease from about 28,000 micrograms per liter in ground water at the source area to less than 5 micrograms per liter 200 feet downgradient and prior to discharging to a stream. Because of this rapid attenuation, contaminants do not presently impact the stream downgradient of the site. In contrast, at a site in the coastal Plain Physiographic Province (Charleston, South Carolina), hydrologic and water-chemistry data indicate that, even thought the site has a substantial natural attenuation capacity, it may not be sufficient to fully protect a nearby point of ground-water discharge. These two sites illustrate how the efficiency of natural attenuation processes acting on petroleum hydrocarbons can be systematically evaluated using hydrologic, geochemical, and microbiologic methods. These methods, in turn, can be used to assess the role that the natural attenuation of petroleum hydrocarbons can play in achieving overall site remediation.

South Carolina

Occurrence and temporal variability of methyl tert -butyl ether (MTBE) and other volatile organic compounds in select sources of drinking water : results of the focused survey

The large-scale use of the gasoline oxygenate methyl tert -butyl ether (MTBE), and its high solubility, low soil adsorption, and low biodegradability, has resulted in its detection in ground water and surface water in many places throughout the United States. Studies by numerous researchers, as well as many State and local environmental agencies, have discovered high levels of MTBE in soils and ground water at leaking underground gasoline-storage-tank sites and frequent occurrence of low to intermediate levels of MTBE in reservoirs used for both public water supply and recreational boating. In response to these findings, the American Water Works Association Research Foundation sponsored an investigation of MTBE and other volatile organic compounds (VOCs) in the Nation's sources of drinking water. The goal of the investigation was to provide additional information on the frequency of occurrence, concentration, and temporal variability of MTBE and other VOCs in source water used by community water systems (CWSs). The investigation was completed in two stages: (1) reviews of available literature and (2) the collection of new data. Two surveys were associated with the collection of new data. The first, termed the Random Survey, employed a statistically stratified design for sampling source water from 954 randomly selected CWSs. The second, which is the focus of this report, is termed the Focused Survey, which included samples collected from 134 CWS source waters, including ground water, reservoirs, lakes, rivers, and streams, that were suspected or known to contain MTBE. The general intent of the Focused Survey was to compare results with the Random Survey and provide an improved understanding of the occurrence, concentration, temporal variability, and anthropogenic factors associated with frequently detected VOCs. Each sample collected was analyzed for 66 VOCs, including MTBE and three other ether gasoline oxygenates (hereafter termed gasoline oxygenates). As part of the Focused Survey, 451 source-water samples and 744 field quality-control (QC) samples were collected from 78 ground-water, 39 reservoir and (or) lake, and 17 river and (or) stream source waters at fixed intervals for a period of 1 year. Using a common assessment level of 0.2 μg/L (micrograms per liter) (2.0 μg/L for methyl ethyl ketone), 37 of the 66 VOCs analyzed were detected in both surveys. However, VOCs, especially MTBE and other gasoline oxygenates, were detected more frequently in the Focused Survey than in the Random Survey. MTBE was detected in 55.5 percent of the CWSs sampled in the Focused Survey and in 8.7 percent of those sampled in the Random Survey. Little difference in occurrence, however, was observed for trihalomethanes (THMs), which were detected in 16.4 and 14.8 percent of Focused Survey and Random Survey CWSs, respectively. This may indicate a pervasive occurrence of THMs in several source-water types, regardless of CWS size or geographic location. Using data at or above the method detection limit to assess temporal variability and anthropogenic factors associated with frequent detection of select VOCs, concentrations in the Focused Survey in ground-water, reservoir, and river source waters were typically less than 1 μg/L. Also, at a 95-percent confidence interval, no statistically significant differences were observed in comparing concentrations in the first and second ground-water sample. A weak seasonal pattern was observed in samples collected from reservoirs and lakes where gasoline oxygenates and other gasoline compounds were detected more frequently during spring and summer, presumedly a result of increased use of motorized watercraft during these seasons. In contrast, seasonal patterns were not observed in samples collected from rivers and streams. The lack of seasonal differences in river and stream source waters sampled may indicate a common and continuous source of contamination. The most frequently detected VOC (MTBE) and the two most frequently occurring subgroups of VOCs (gasoline oxygenates and THMs) detected in CWS source waters were further characterized to evaluate some anthropogenic factors that may better explain their frequent occurrence. Gasoline oxygenates were detected in 73.9 percent of all CWSs sampled. The concentration of gasoline oxygenates was slightly correlated with watercraft use on reservoirs inside MTBE high-use areas (r2=0.3783) but not outside of these areas (r2=0.0242). In general, the concentration of gasoline oxygenates increased as watercraft use increased. THMs were detected in 47.8 percent of the CWSs supplied by surface water. The frequent occurrence of THMs in reservoir source waters was determined to be an artifact of disinfection and the recycling of chlorinated water to these reservoirs. All CWSs with frequent occurrence of THMs served by a reservoir indicated that chlorine was added to waters for various reasons and that the chlorinated water was then released back to, or upstream of, the reservoir or lake that was sampled.

Water-Resources Investigations Report

Distribution and mass loss of volatile organic compounds in the surficial aquifer at sites FT03, LF13, and WP14/LF15, Dover Air Force Base, Delaware, November 2000–February 2001

Ground-water and surface-water sampling was conducted in the natural attenuation study area in the East Management Unit of Dover Air Force Base, Delaware to determine the distributions of volatile organic compounds in the vicinity of four sites?Fire Training Area Three, the Rubble Area Landfill, the Receiver Station Landfill, and the Liquid Waste Disposal Landfill. This work was done by the U.S. Geological Survey, in cooperation with the U.S. Air Force, as part of an ongoing assessment of the effectiveness of natural attenuation at these sites. The specific objectives of the study were to (1) determine the areal and vertical extent of the contaminant plumes and source areas, (2) measure volatile organic compound concentrations in ground-water discharge areas and in surface water under base-flow conditions, (3) evaluate the potential for off-site migration of the mapped plumes, and (4) estimate the amount of mass loss downgradient of the Liquid Waste Disposal and Receiver Station Landfills. A direct-push drill rig and previously installed multi-level piezometers were used to determine the three-dimensional distributions of volatile organic compounds in the 30?60-foot-thick surficial aquifer underlying the natural attenuation study area. A hand -driven mini-piezometer was used to collect ground-water samples in ground-water discharge areas. A total of 319 ground-water and 4 surface-water samples were collected from November 2000 to February 2001 and analyzed for chlorinated solvents and fuel hydrocarbons. The contaminant plumes migrating from Fire Training Area Three and the Rubble Area Landfill are approximately 500 feet and 800 feet, respectively, in length. These plumes consist predominantly of cis-1,2-dichloroethene, a daughter product, indicating that extensive dechlorination of tetrachloroethene and trichloroethene has occurred at these sites. With an approximate length of 2,200 feet, the plume migrating from the Receiver Station and Liquid Waste Disposal Landfills is the largest of the three plumes in the East Management Unit. In this plume, the parent compounds, tetrachloroethene and trichloroethene, as well as cis-1,2-dichloroethene, are present downgradient of the source. Vinyl chloride was not detected in the natural attenuation study area. Vertical water-quality profiles indicate that volatile organic compounds are present mainly in the upper part of the surficial aquifer. Plumes of fuel hydrocarbon constituents were not detected in the natural attenuation study area. Volatile organic compounds were present at concentrations above detection limits in 6 of 14 samples collected from the aquifer underlying the bed of Pipe Elm Branch and the drainage ditch adjacent to Fire Training Area Three, indicating that the plumes migrating from Fire Training Area Three and the Receiver Station and Liquid Waste Disposal Landfills are reaching these ground-water discharge areas. In contrast, sampling results indicated that the plume from the Rubble Area Landfill does not reach these ground-water discharge areas. Trichloroethene was present above detection limits in one of four surface-water samples collected from Pipe Elm Branch and the drainage ditch adjacent to Fire Training Area Three. The trichloroethene concentration is below applicable Delaware Department of Natural Resources and Environmental Control surface-water-quality standards for human health. An assessment of chlorinated-solvent mass loss in the plume migrating from the Receiver Station and Liquid Waste Disposal Landfills indicates that tetrachloroethene and trichloroethene mass loss downgradient of the source is negligible. Cis-1,2-dichloroethene, however, appears to biodegrade by an unidentified reaction in the plume. Plan-view maps of the plume migrating from the Receiver Station and Liquid Waste Disposal Landfills indicate that tetrachloroethene, trichloroethene, and cis-1,2-dichloroethene may migrate off Dover Air Force Base property approximately 1,500 f

Delaware

Evaluation of passive diffusion bag and dialysis samplers in selected wells at Hickam Air Force Base, Hawaii, July 2001

Field comparisons of chemical concentrations obtained from dialysis samplers, passive diffusion bag samplers, and low-flow samplers showed generally close agreement in most of the 13 wells tested during July 2001 at Hickam Air Force Base, Hawaii. The data for chloride, sulfate, iron, alkalinity, arsenic, and methane appear to show that the dialysis samplers are capable of accurately collecting a passive sample for these constituents. In general, the comparisons of volatile organic compound concentrations showed a relatively close correspondence between the two different types of diffusion samples and between the diffusion samples and the low-flow samples collected in most wells. Divergence appears to have resulted primarily from the pumping method, either producing a mixed sample or water not characteristic of aquifer water moving through the borehole under ambient conditions. The fact that alkalinity was not detected in the passive diffusion bag samplers, highly alkaline waters without volatilization loss from effervescence, which can occur when a sample is acidified for preservation. Both dialysis and passive diffusion bag samplers are relatively inexpensive and can be deployed rapidly and easily. Passive diffusion bag samplers are intended for sampling volatile organic compounds only, but dialysis samplers can be used to sample both volatile organic compounds and inorganic solutes. Regenerated cellulose dialysis samplers, however, are subject to biodegradation and probably should be deployed no sooner than 2 weeks prior to recovery. 1 U.S. Geological Survey, Columbia, South Carolina. 2 Air Florce Center for Environmental Excellence, San Antionio, Texas.

Hawaii

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

Geohydrologic reconnaissance of a ground-water contamination problem in the Argonne Road area near Spokane, Washington

Three domestic wells that withdraw groundwater from an alluvium-filled trough cut into granite were found to be contaminated with the organic solvents tetrachloroethene, trichloroethene, 1,1,1-trichloroethane, and 1 ,2-trans-dichloroethene. The suspected source of contamination is a nearby septic-tank sludge disposal area. There is concern that the affected aquifer is tributary to the Spokane aquifer, which has been accorded ' sole source ' status by the U.S. Environmental Protection Agency. Preliminary estimates suggest that groundwater in the area is moving toward the Spokane aquifer and that the transit time may range from 2.5 to 25 years. Because of longitudinal dispersion, however, the plume of contaminants may move at a faster rate than the ambient groundwater and may arrive at given destinations more quickly than calculated above. A literature search has indicated that the dissolved solute phase of the contaminants will not be significantly affected by sorption, volatilization, chemical activity, or biodegradation. Because of the preliminary nature of the investigation, many questions relating to the extent of contamination remain unanswered. A list of suggested additional studies to answer those questions and to refine and confirm the findings of this investigation is presented. (Author 's abstract)

Water-Resources Investigations Report