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Sulfidization and magnetization above hydrocarbon reservoirs

Post-depositional iron-sulfide (Fe-S) minerals that are related to hydrocarbon seepage have changed the original magnetizations at Cement oil field (Anadarko basin, Oklahoma), at Simpson oil field (North Slope basin, Alaska), and above deep Cretaceous oil and gas reservoirs, south Texas coastal plain. At Cement, ferrimagnetic pyrrhotite (Fe 7 S 8 ) formed with pyrite and marcasite in Permian red beds. The Fe-S minerals contain sulfur from two sources: (1) abiogenic sulfide, which has positive δ 34 S values, derived from thermochemical reduction of sulfate in deep reservoirs; and (2) biogenic sulfide, which has negative δ 34 S values, produced by reactions mediated by sulfate-reducing bacteria fed by leaking hydrocarbons. At Simpson, ferrimagnetic greigite (Fe 3 S 4 ) dominates magnetizations in nonmarine Upper Cretaceous clastic beds that contain epigenetic sulfide (δ 34 S > +20 per mil) and seeping biodegraded oil. In this setting, the authigenic magnetic sulfide mineral apparently incorporated sulfide produced by bacterial sulfate reduction under limited sulfate conditions. An inferred hydrocarbon food source for the sulfate-reducing bacteria links the hydrocarbon seepage to the greigite. The greigite is perhaps forming today. In middle Tertiary sandstones of southeast Texas, pyrite and marcasite formed when abiogenic H 2 S (enriched in 34 S) migrated upward from deep reservoirs, or when H 2 S (depleted in 34 S) was produced at shallow depths by bacteria that used organic material dissolved in migrating water from depth. The pyrite and marcasite replaced detrital magnetic iron-titanium oxide minerals. The degree of such replacement appears to increase toward faults that connect deep petroleum reservoirs to shallow sandstone. Our results show that abiologic and biologic mechanisms can generate different magnetic sulfide minerals in some sulfidic zones of hydrocarbon seepage. More commonly the magnetizations in such zones would be diminished as a result of the replacement of detrital magnetic minerals by the common nonmagnetic sulfide minerals, or would remain unchanged if such detrital minerals were originally absent.

Book chapter

Microbial transformations of azaarenes in creosite-contaminated soil and ground water: Laboratory and field studies

Azaarenes or aromatic nitrogen heterocycles are a class of compounds found in wood-preservative wastes containing creosote. The fate and movement of these compounds in contaminated aquifers is not well understood. Water-quality studies in an aquifer contaminated with creosote near Pensacola, Florida, indicated that ground water was contaminated with several azaarenes and their oxygenated and alkylated derivatives, suggesting that these oxygenated compounds may be products of microbial transformation reactions. Accordingly, laboratory studies were designed to investigate the fate of these compounds. Under aerobic conditions, soil pseudomonads isolated from creosote-contaminated soil converted quinoline to 2(1H)quinoline that subsequently was degraded to unknown products. A methanogenic consortium isolated from an anaerobic sewage digestor, in presence of ground-water and creosote-contaminated soil, converted quinoline, isoquinoline, and 4-methylquinoline to their respective oxygenated analogs. In addition, N-, C-, and O-methylated analogs of oxygenated azaarenes were identified by gas chromatography-mass spectrometry (GC-MS) in aerobic cultures. Under the experimental conditions, 2-methylquinoline was biorefractory. Presence of similar biotransformation products in anaerobic cultures and contaminated ground water from the Pensacola site provided further evidence that these compounds indeed were mivrobial transformation products. Stable isotope labeling studies indicated that the source of the oxygen atom for this hydroxylation reaction under aerobic and anaerobic conditions was water. A mechanism was proposed for this hydroxylation reaction. Whereas parent azaarenes are biodegradable in both anaerobic and aerobic zones, oxygenated and alkylated analogs are more biorefractory and, hence, persistent in anaerobic zones of contaminated aquifers.

Water Science and Technology

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2011

Previous investigations indicate that concentrations of chlorinated volatile organic compounds are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington. Phytoremediation combined with ongoing natural attenuation processes was the preferred remedy selected by the U.S. Navy, as specified in the Record of Decision for the site. The U.S. Navy planted two hybrid poplar plantations on the landfill in spring 1999 to remove and to control the migration of chlorinated volatile organic compounds in shallow groundwater. The U.S. Geological Survey has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision. This report presents groundwater geochemical and selected volatile organic compound data collected at Operable Unit 1 by the U.S. Geological Survey during June 20-22, 2011, in support of long-term monitoring for natural attenuation. In 2011, groundwater samples were collected from 13 wells and 9 piezometers. Samples from all wells and piezometers were analyzed for redox sensitive constituents and dissolved gases, and samples from 5 of 13 wells and all piezometers also were analyzed for chlorinated volatile organic compounds. Concentrations of redox sensitive constituents measured in 2011 were consistent with previous years, with dissolved oxygen concentrations all at 0.4 milligram per liter or less; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. The reductive declorination byproducts - methane, ethane, and ethene - were either not detected in samples collected from the upgradient wells in the landfill and the upper aquifer beneath the northern phytoremediation plantation or were detected at concentrations less than those measured in 2010. Chlorinated volatile organic compound concentrations in 2011 at most piezometers were similar to or slightly less than chlorinated volatile organic compound concentrations measured in previous years. For the upper aquifer beneath the southern phytoremediation plantation, chlorinated volatile organic compound concentrations in 2011 in groundwater from the piezometers were extremely high and continued to vary considerably over space and between years. At piezometer P1-9, the total chlorinated volatile organic compound concentrations increased from 9,500 micrograms per liter in 2010 to more than 44,000 micrograms per liter in 2011. Total chlorinated volatile organic compound concentrations decreased at piezometers P1-6, P1-7, and P1-10 compared to the concentrations measured in 2010. One or both of the reductive dechlorination byproducts ethane and ethene were detected at all piezometers and three of the four wells in the southern plantation. For the intermediate aquifer, concentrations of redox sensitive constituents and chlorinated volatile organic compounds in 2011 were consistent with concentrations measured in previous years, with the exception of notable decreases in sulfate and chloride concentrations at well MW1-28. Concentrations of the reductive dechlorination byproducts ethane and ethene decreased at wells MW1-25 and MW1-28 compared to previously measured concentrations.

Washington

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June and October 2012

Previous investigations indicate that concentrations of chlorinated volatile organic compounds are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington. The U.S. Geological Survey has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision for the site. This report presents groundwater geochemical and selected chlorinated volatile organic compound data collected at Operable Unit 1 by the U.S. Geological Survey during June and October 2012, in support of long-term monitoring for natural attenuation. Groundwater samples were collected from 13 wells and 9 piezometers, as well as from 10 shallow groundwater passive-diffusion sampling sites in the nearby marsh. Samples from all wells and piezometers were analyzed for oxidation-reduction (redox) sensitive constituents and dissolved gases. Samples from all piezometers also were analyzed for chlorinated volatile organic compounds, as were all samples from the passive-diffusion sampling sites. In 2012, concentrations of redox-sensitive constituents measured at all wells and piezometers were consistent with those measured in previous years, with dissolved oxygen concentrations all at 0.4 milligram per liter or less; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. In the upper aquifer of the northern plantation in 2012, chlorinated volatile organic compound (CVOC) concentrations at all piezometers were similar to those measured in previous years, and concentrations of the reductive dechlorination byproducts ethane and ethene were slightly higher or the same as concentrations measured in 2011. In the upper aquifer of the southern plantation, CVOC concentrations measured in piezometers during 2012 continued to be extremely variable as in previous years, and often very high, and reductive dechlorination byproducts were detected in two of the four wells and in all piezometers. Beneath the marsh adjacent to the southern plantation, chloroethene concentrations measured in 2012 continued to vary spatially and temporarily, and also were very high. Additionally, CVOC concentrations measured in samplers deployed in access tubes were about two to four times less than those measured in the two samplers buried nearby, beneath the marsh stream. Total CVOC concentration, at what has been historically the most contaminated passive-diffusion sampler site (S-4), continued an increasing trend. For the intermediate aquifer in 2012, concentrations of reductive dechlorination byproducts ethane and ethene were consistent with those measured in previous years.

Washington

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, July 2013

Previous investigations indicate that concentrations of chlorinated volatile organic compounds (CVOCs) are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington. The U.S. Geological Survey has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision for the site. This report presents groundwater geochemical and selected CVOC data collected at Operable Unit 1 by the U.S. Geological Survey during July 9–18, 2013, in support of longterm monitoring for natural attenuation. Groundwater samples were collected from 13 wells and 9 piezometers, as well as from 10 shallow groundwater passive-diffusion sampling sites in the nearby marsh. Samples from all wells and piezometers were analyzed for oxidation-reduction (redox) sensitive constituents and dissolved gases. Samples from all piezometers and four wells also were analyzed for CVOCs, as were all samples from the passive-diffusion sampling sites. In 2013, concentrations of redox-sensitive constituents measured at all wells and piezometers were consistent with those measured in previous years, with dissolved oxygen concentrations at all except an upgradient well 0.2 milligrams per liter or less; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. In the upper aquifer of the northern plantation in 2013, CVOC concentrations at all piezometers were similar to those measured in previous years, and concentrations of the reductive dechlorination byproducts ethane and ethene were slightly lower or the same as concentrations measured in 2012. In the upper aquifer of the southern plantation, CVOC concentrations measured in piezometers during 2013 continued to be variable as in previous years, and often very high, and reductive dechlorination byproducts were detected in two of the three wells and in all but one piezometer. Beneath the marsh adjacent to the southern plantation, chloroethene concentrations measured in 2013 continued to vary spatially and temporaly, and also were very high. Total CVOC concentrations, at what have been historically the most contaminated passive-diffusion sampler sites (S-4, S-4B, S-5, and S-5B) remained elevated. For the intermediate aquifer in 2013, concentrations of reductive dechlorination byproducts ethane and ethene and CVOCs were consistent with those measured in previous years.

Washington

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June and September 2014

Previous investigations indicate that concentrations of chlorinated volatile organic compounds (CVOCs) are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington. The U.S. Geological Survey has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation at the site. This report presents groundwater geochemical and selected CVOC data collected at Operable Unit 1 by the U.S. Geological Survey during June 23–25 and September 4, 2014, in support of long-term monitoring for natural attenuation. Groundwater samples were collected from 13 wells and 9 piezometers, as well as from 10 shallow groundwater passive-diffusion sampling sites in the nearby marsh. Samples from all wells and piezometers were analyzed for oxidation-reduction (redox) sensitive constituents and dissolved gases. Samples from all piezometers and four wells also were analyzed for CVOCs, as were all samples from the passive-diffusion sampling sites. In 2014, concentrations of redox-sensitive constituents measured at all wells and piezometers were consistent with those measured in previous years, with dissolved oxygen concentrations all less than 1 milligram per liter; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. In the upper aquifer of the northern plantation in 2014, CVOC concentrations at all piezometers were similar to those measured in previous years, and concentrations of the reductive dechlorination byproducts ethane and ethene were slightly lower or the same as concentrations measured in 2013. In the upper aquifer of the southern plantation, CVOC concentrations measured in piezometers during 2014 continued to be variable as in previous years, often high, and reductive dechlorination byproducts were detected in one of the three wells and in all but two piezometers. Beneath the marsh adjacent to the southern plantation, chloroethene concentrations measured in 2014 continued to vary spatially and temporally, and were high. Trends for total CVOC concentration continued to increase at the historically most contaminated passive‑diffusion sampler sites (S-4, S-4B, and S-5). For the intermediate aquifer in 2014, concentrations of reductive dechlorination byproducts ethane and ethene and CVOCs were consistent with those measured in previous years.

Washington

Groundwater geochemical and selected volatile organic compound data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, July 2015

Previous investigations indicate that concentrations of chlorinated volatile organic compounds (CVOCs) are substantial in groundwater beneath the 9-acre former landfill at Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington. The U.S. Geological Survey has continued to monitor groundwater geochemistry to ensure that conditions remain favorable for contaminant biodegradation as specified in the Record of Decision for the site. This report presents groundwater geochemical and selected CVOC data collected at Operable Unit 1 by the U.S. Geological Survey during July 6–8 and July 31, 2015 in support of long-term monitoring for natural attenuation. Water samples were collected from 13 wells, 9 piezometers, and 13 shallow groundwater passive-diffusion sampling sites in the nearby marsh. Samples from all wells and piezometers were analyzed for oxidation-reduction (redox) sensitive constituents. Samples from all piezometers and four wells also were analyzed for CVOCs and dissolved gases, as were all samples from the passive-diffusion sampling sites. In 2015, concentrations of redox-sensitive constituents measured at all wells and piezometers were consistent with those measured in previous years, with dissolved oxygen concentrations all less than 1 milligram per liter; little to no detectable nitrate; abundant dissolved manganese, iron, and methane; and commonly detected sulfide. In the upper aquifer of the northern plantation in 2015, CVOC concentrations at all piezometers were similar to those measured in previous years, and concentrations of the reductive dechlorination byproducts ethane and ethene were equivalent to the concentrations measured in 2014. In the upper aquifer of the southern plantation, CVOC concentrations measured in piezometers during 2015 continued to be variable as in previous years, and often very high, and reductive dechlorination byproducts were detected in one of the three wells and in piezometers. Beneath the marsh adjacent to the southern plantation, CVOC concentrations measured in 2015 continued to vary spatially and temporally, and were high. The total CVOC concentration, at what have been historically the most contaminated passive-diffusion sampler sites (S-4 T, S-4B T, and S-5 T), continued elevated trends, as did one of the new sampler sites (S-9 T) installed in 2015. For the intermediate aquifer in 2015, concentrations of reductive dechlorination byproducts ethane and ethene and CVOCs were consistent with those measured in previous years.

Washington

PFAS sampling activities in the U.S. Geological Survey national networks

Per- and polyfluoroalkyl substances (PFAS), frequently called “forever chemicals,” are used for a wide variety of industrial purposes and are often found in common household and industrial items such as firefighting foams, non-stick cookware, and water-resistant materials. The contamination of water, air, and soil by PFAS is a national and global issue due to their widespread occurrence in multiple applications and resistance to biodegradation and other traditional treatment processes. Research indicates that many PFAS can be emitted to the atmosphere and transported and deposited long distances from the source. The U.S. Geological Survey (USGS) Water Resources Mission Area received funding to implement a national-scale sampling effort to assess PFAS occurrence. To follow agency directives, the National Water Quality Network (NWQN) added PFAS sample monitoring for both surface water and groundwater, and also added PFAS monitoring to selected sites in the National Atmospheric Deposition Program (NADP).

General Information Product

Assessment of volatile organic compounds in surface water at Canal Creek, Aberdeen Proving Ground, Maryland, November 1999–September 2000

The purpose of this report is to describe the occurrence and distribution of volatile organic compounds in surface-water samples collected by the U.S. Geological Survey in the Canal Creek area of Aberdeen Proving Ground, Maryland, from November 1999 through September 2000. The report describes the differences between years with below normal and normal precipitation, the effects of seasons, tide stages, and location on volatile organic compound concentrations in surface water, and provides estimates of volatile organic concentration loads to the tidal Gunpowder River. Eighty-four environmental samples from 20 surface-water sites were analyzed. As many as 13 different volatile organic compounds were detected in the samples. Concentrations of volatile organic compounds in surface-water samples ranged from below the reporting limit of 0.5 micrograms per liter to a maximum of 50.2 micrograms per liter for chloroform. Chloroform was detected most frequently, and was found in 55 percent of the environmental samples that were analyzed for volatile organic compounds (46 of 84 samples). Carbon tetrachloride was detected in 56 percent of the surface-water samples in the tidal part of the creek (34 of 61 samples), but was only detected in 3 of 23 samples in the nontidal part of the creek. 1,1,2,2-Tetrachloroethane was detected in 43 percent of the tidal samples (26 of 61 samples), but was detected at only two nontidal sites and only during November 1999. Three samples were collected from the tidal Gunpowder River about 300 feet from the mouth of Canal Creek in May 2000, and none of the samples contained volatile organic compound concentrations above detection levels. Volatile organic compound concentrations in surface water were highest in the reaches of the creek adjacent to the areas with the highest known levels of ground-water contamination. The load of total volatile organic compounds from Canal Creek to the Gunpowder River is approximately 1.85 pounds per day (0.84 kilograms per day), or 674 pounds per year. Volatile organic compounds that reach the Gunpowder River become substantially diluted. Although natural-attenuation processes in the study area such as biodegradation are highly effective at reducing contaminant concentration in ground water before it discharges to the creek, natural attenuation is not 100 percent effective at all locations or under all tidal, seasonal, and climatic conditions as indicated by detection of volatile organic compounds in Canal Creek.

Maryland

Water-quality monitoring and studies of the formation and fate of trihalomethanes during the third injection, storage and recovery test at Lancaster, Antelope Valley, California, March 1998 through April 1999

The U.S. Geological Survey, in cooperation with the Los Angeles County Department of Public Works and the Antelope Valley-East Kern Water Agency, conducted three cycles of injection, storage, and recovery tests to evaluate the feasibility of artificially recharging ground water in the Lancaster area of Antelope Valley, California. During the third cycle (March 1998 through April 1999), the tests included investigations of the formation and fate of trihalomethanes in the aquifer. Trihalomethanes are disinfection by-products formed by reaction between natural dissolved organic carbon that is present in water and chlorine that is added during the drinking-water-treatment process. This report includes a discussion of the design of the investigation; descriptions of the sampling, analytical, and experimental methods used in the investigation; and a presentation of the data collected. During the third cycle, 60 million gallons of chlorinated water was injected into the aquifer through well 7N/12W-27P2 in the Los Angeles County Department of Public Works well field in Lancaster between April 15 and June 16, 1998. One hundred fifty million gallons of water was extracted from the same well between June 30, 1998, and April 29, 1999. Water-quality samples were collected during the entire cycle from the well and from a nearby set of nested piezometers, and were analyzed for residual chlorine, dissolved organic carbon, trihalomethane, major anion, and dissolved solid concentrations; ultraviolet absorbance spectra; and a number of field water-quality parameters. A statistical analysis was done to evaluate the analytical precision of the residual chlorine, dissolved organic carbon, trihalomethane, and ultraviolet absorbance measurements on these samples. The formation of trihalomethanes in the injection water was examined in laboratory experiments: Trihalomethane concentrations in samples of injection water were monitored during a storage period, and trihalomethane formation potential in the presence of excess chlorine was measured. The role of mixing between injection water and ground water and the conservative or non-conservative behavior of trihalomethanes was studied by adding a conservative tracer, sulfur hexafluoride, to the injection water and monitoring its concentration in the extraction water. The potential for biodegradation of trihalomethanes by aquifer bacteria was assessed in laboratory experiments: Microcosms containing ground water or extraction water and sediment or concentrated bacteria were spiked with trihalomethanes, and the amount of trihalomethanes was monitored during an incubation period. The potential for sorption of trihalomethanes to aquifer sediments was assessed in laboratory experiments: Mixtures of sediment and water were spiked with trihalomethanes, and then the trihalomethane concentrations were measured after an equilibration period.

Open-File Report

Estimated minimum discharge rates of the Deepwater Horizon spill— Interim report to the flow rate technical group from the Mass Balance Team

All of the calculations and results in this report are preliminary and intended for the purpose, and only for the purpose, of aiding the incident team in assessing the extent of the spilled oil for ongoing response efforts. Other applications of this report are not authorized and are not considered valid. Because of time constraints and limitations of data available to the experts, many of their estimates are approximate, are subject to revision, and certainly should not be used as the Federal Government's final values for assessing volume of the spill or its impact to the environment or to coastal communities. Each expert that contributed to this report reserves the right to alter his conclusions based upon further analysis or additional information. An estimated minimum total oil discharge was determined by calculations of oil volumes measured as of May 17, 2010. This included oil on the ocean surface measured with satellite and airborne images and with spectroscopic data (129,000 barrels to 246,000 barrels using less and more aggressive assumptions, respectively), oil skimmed off the surface (23,500 barrels from U.S. Coast Guard [USCG] estimates), oil burned off the surface (11,500 barrels from USCG estimates), dispersed subsea oil (67,000 to 114,000 barrels), and oil evaporated or dissolved (109,000 to 185,000 barrels). Sedimentation (oil captured from Mississippi River silt and deposited on the ocean bottom), biodegradation, and other processes may indicate significant oil volumes beyond our analyses, as will any subsurface volumes such as suspended tar balls or other emulsions that are not included in our estimates. The lower bounds of total measured volumes are estimated to be within the range of 340,000 to 580,000 barrels as of May 17, 2010, for an estimated average minimum discharge rate of 12,500 to 21,500 barrels per day for 27 days from April 20 to May 17, 2010.

Louisiana

Geochemical analysis of potash mine seep oils, collapsed breccia pipe oil shows and selected crude oils, Eddy County, New Mexico

Oil shows, in the form of oil stains and bleeding oil, in core samples from two breccia pipes, Hills A and C, Eddy County, New Mexico, and seepage oils in a potash mine near Hill C breccia pipe are geochemically similar. The geochemical similarities strongly suggest that they belong to the same family of oils and were derived from similar sources. The oils are relatively high in sulfur (0.89 to 1.23 percent), rich in hydrocarbons (average 82 percent), relatively high in saturated hydrocarbon/aromatic hydrocarbon ratios (average 2.9), and based on analysis of seep oils alone, have a low API gravity (average 19.4?). The oils are for the most part severely biodegraded as attested by the loss of n-paraffin molecules. Geochemical comparison of seven crude oils collected in the vicinity of the breccia pipes indicates that the Yates oils are the likely source of the above family of oils. Six barrels of crude oil that were dumped into a potash exploration borehole near Hill C breccia pipe, to release stuck casing, are considered an unlikely source of the breccia pipe and mine seep oils. Volumetric and hydrodynamic constraints make it highly improbable that such a small volume of 'dumped' oil could migrate over distances ranging from about 600 feet to 2.5 miles to the sites of the oil shows.

Open-File Report

Movement and fate of creosote waste in ground water, Pensacola, Florida; U.S. Geological Survey toxic waste--ground-water contamination program

In 1983, the U.S. Geological Survey, Office of Hazardous Waste Hydrology, selected the former American Creosote Works site near Pensacola, Florida as a national research demonstration area. Seventy-nine years (1902-81) of seepage from unlined discharge impoundments had released creosote, diesel fuel, and pentachlorophenol (since 1950) wastes into the ground-water system. A cluster of from 2 to 5 wells constructed at different depths at 9 sites yielded water which revealed contamination 600 feet downgradient and to a depth of 100 feet below land surface near the site. The best cross-sectional representation of the contaminant plume was obtained from samples collected and analyzed for oxidation-reduction sensitive inorganic chemical constituents. Energy dispersive x-ray fluorescence detected recently formed iron carbonate in soil samples from highly reducing ground-water zones. Approximately eighty specific organic contaminants were isolated from ground-water samples by gas-chromotography/mass spectrometry. Column studies indicate the dimethyl phenols are not sorbed or degraded by the sand-and-gravel aquifer materials. Five of nineteen individual phenolic and related compounds are biodegradable based on anaerobic digestor experiments with ACW site bacterial populations. The potential impacts in the nearby Pensacola Bay biotic community are being evaluated. (USGS)

Open-File Report

Manmade organic compounds in the surface waters of the United States: a review of current understanding

This report reviews the occurrence and distribution of manmade organic compounds in the surface waters of the United States. On the basis of their aqueous solubilities, nonionic organic compounds partition themselves between water, dissolved organic matter, particulate organic matter, and the lipid reservoirs of aquatic organisms. Ionized organic compounds can be absorbed to sediments, thereby reducing their aqueous concentrations. Transformation processes of photolysis, hydrolysis, biodegradation, and volatilization can attenuate organic compounds, and attenuation rate commonly follow a first-order kinetic process. Eight groups of manmade organic compounds are discussed: 1. Polychlorinated biphenyls and organochlorine insecticides, 2. Carbamate and organophosphorus insecticides, 3. Herbicides, 4. Phenols, 5. Halogenated aliphatic and monocyclic aromatic hydrocarbons, 6. Phthalate esters, 7. Polychlorinated dibenzo-p-dioxins, and 8. Polycyclic aromatic hydrocarbons. For each compound group, data pertaining to use, production, and properties are presented and discussed. Processes that influence that the environmental fate of each group, as determined primarily through laboratory studies, are reviewed, and important fate processes are identified. Environmental concentrations of compounds from each group in water, biota, and sediment are given to demonstrate representative values for comparison to concentrations determined during ongoing research. Finally, where sufficient data exist, regional and temporal contamination trends in the United States are discussed.

Open-File Report

Water-quality and hydrologic conditions at a site of ground-water contamination by volatile organic compounds, South Grafton, Massachusetts, September and October 1994

Ground-water quality and hydrologic data were collected at a site contaminated by volatile organic compounds (VOCs) in South Grafton, Massachusetts, during September and October 1994. The VOCs have formed a plume of contaminated ground water at an abandoned textile mill adjacent to the Blackstone River. Concentrations of total VOCs in the plume ranged from less than 1 to more than 40,000 micrograms per liter. Trichloroethylene (TCE) was the primary chlorinated contaminant, comprising as much as 98 percent of the total VOCs. The highest concentration, 43,000 micrograms per liter, was higher than any previously measured concentration at the site; however, the maximum extent and distribution of concentrations in the VOC plume in September 1994 was similar to that found in July 1993 and in earlier rounds of sampling. In addition to TCE, 1,2-dichloroethene (1,2-DCE) and vinyl chloride were detected at most sites. Spatial and temporal changes in concentrations of TCE, 1,2-DCE, and vinyl chloride are consistent with the hypothesis that TCE biodegradation was the source of 1,2-DCE and vinyl chloride. Ground water at the site contained low to moderately high concentrations of dissolved solids (44 to 406 milligrams per liter), had a moderately high specific conductance (155 to 670 microsiemens per centimeter at 25 degrees Celsius), and was slightly acidic (pH=5.9 to 7.0). Concentrations of the major ions-calcium, sodium, chloride, and sulfate-were not related to VOC concentrations. Dissolved-oxygen concentrations were low (0 to 2 milligrams per liter) throughout most of the aquifer. Distribution of nitrogen species, iron, and manganese indicates that zones of varying oxidation-reduction potential were present in the aquifer. Concentrations of trace metals other than iron or manganese, including arsenic, cadmium, chromium, and copper, generally were less than analytical detection limits. Stream stage in the Blackstone River at the site during September and October 1994 fluctuated by about 1 to 2 feet within 24-hour periods. These rapid fluctuations resulted from sudden release of impounded water at a hydroelectric-generating facility downstream from the site. In addition to the daily fluctuations, rapid small changes in stream stage also occurred that were related to storms. Fluctuations in ground-water levels in four observation wells at the site were similar in amplitude and timing to the rapid fluctuations in stream stage; the daily fluctuations of ground-water levels were greatest in an observation well within 100 feet of the river and least in an observation well about 300 feet from the river. Because ground- water levels at the study site seem to be affected by fluctuations in stage of the Blackstone River, transport of the VOC plume in ground water also is likely to be affected by the fluctuations in stage.

Open-File Report

Petroleum systems of the San Joaquin Basin Province -- geochemical characteristics of gas types: Chapter 10 in Petroleum systems and geologic assessment of oil and gas in the San Joaquin Basin Province, California

The San Joaquin Basin Province is a petroliferous basin filled with predominantly Late Cretaceous to Pliocene-aged sediments, with organic-rich marine rocks of Late Cretaceous, Eocene, and Miocene age providing the source of most of the oil and gas. Previous geochemical studies have focused on the origin of the oil in the province, but the origin of the natural gas has received little attention. To identify and characterize natural gas types in the San Joaquin Basin, 66 gas samples were analyzed and combined with analyses of 15 gas samples from previous studies. For the purpose of this resource assessment, each gas type was assigned to the most likely petroleum system. Three general gas types are identified on the basis of bulk and stable carbon isotopic composition—thermogenic dry (TD), thermogenic wet (TW) and biogenic (B). The thermogenic gas types are further subdivided on the basis of the δ 13 C values of methane and ethane and nitrogen content into TD-1, TD-2, TD-Mixed, TW-1, TW-2, and TW-Mixed. Gas types TD-1 and TD-Mixed, a mixture of biogenic and TD-1 gases, are produced from gas fields in the northern San Joaquin Basin. Type TD-1 gas most likely originated from the Late Cretaceous to Paleocene Moreno Formation, a gas-prone source rock. The biogenic component of the TD-Mixed gas existed in the trap prior to the influx of thermogenic gas. For the assessment, these gas types were assigned to the Winters- Domengine Total Petroleum System, but subsequent to the assessment were reclassified as part of the Moreno-Nortonville gas system. Dry thermogenic gas produced from oil fields in the southern San Joaquin Basin (TD-2 gas) most likely originated from the oil-prone source rock of Miocene age. These samples have low wetness values due to migration fractionation or biodegradation. The thermogenic wet gas types (TW-1, TW-2, TW-Mixed) are predominantly associated gas produced from oil fields in the southern and central San Joaquin Basin. Type TW-1 gas most likely originates from source rocks within the Eocene Kreyenhagen Formation or the Eocene Tumey formation of Atwill (1935). Type TW-2 gas most likely originates from the Miocene Monterey Formation and equivalents. TW-Mixed gas is likely a mixture of biogenic and wet thermogenic gas (TW-1 or TW-2) derived from source rocks mentioned above. The thermogenic wet gas types are included in the corresponding Eocene or Miocene total petroleum systems. Type B gas is a dry, nonassociated gas produced from the Pliocene San Joaquin Formation in the central and southern San Joaquin Basin. This gas type most likely originated from Pliocene marine source rocks as a product of methanogenesis, and defines the Neogene Nonassociated Gas Total Petroleum System.

California

Recharge processes in an alluvial aquifer riparian zone, Norman Landfill, Norman, Oklahoma, 1998-2000

Analyses of stable isotope profiles (d2H and d18O) in the saturated zone, combined with water-table fluctuations, gave a comprehensive picture of recharge processes in an alluvial aquifer riparian zone. At the Norman Landfill U.S. Geological Survey Toxic Substances Hydrology research site in Norman, Oklahoma, recharge to the aquifer appears to drive biodegradation, contributing fresh supplies of electron acceptors for the attenuation of leachate compounds from the landfill. Quantifying recharge is a first step in studying this process in detail. Both chemical and physical methods were used to estimate recharge. Chemical methods included measuring the increase in recharge water in the saturated zone, as defined by isotopic signature, specific conductance or chloride measurements; and infiltration rate estimates using storm event isotopic signatures. Physical methods included measurement of water-table rise after individual rain events and on an approximately monthly time scale. Evapotranspiration rates were estimated using diurnal watertable fluctuations; outflux of water from the alluvial aquifer during the growing season had a large effect on net recharge at the site. Evaporation and methanogenesis gave unique isotopic signatures to different sources of water at the site, allowing the distinction of recharge using the offset of the isotopic signature from the local meteoric water line. The downward movement of water from large, isotopically depleted rain events in the saturated zone yielded recharge rate estimates (2.2 - 3.3 mm/day), and rates also were determined by observing changes in thickness of the layer of infiltrated recharge water at the top of the saturated zone (1.5 - 1.6 mm/day). Recharge measured over 2 years (1998-2000) in two locations at the site averaged 37 percent of rainfall, however, part of this water had only a short residence time in the aquifer. Isotopes showed recharge water entering the ground-water system in winter and spring, then being removed during the growing season by phreatophyte transpiration. Recharge timing was variable over the course of the study; July and August were the only months that had no recharge in both years. Recharge to the aquifer from the slough (wetland pond) was estimated at one location using the isotopic signature of water affected by evaporation. Recharge was correlated with the rainfall amount over the period of estimation, suggesting that recharge from the slough to the downgradient aquifer was an episodic process, corresponding to elevated water levels in the slough after large rain events.

Oklahoma

Monitoring the natural attenuation of petroleum in ground water at the former naval complex, Operable Unit A, Adak Island, Alaska, May and June 2003

During May and June 2003, the U.S. Geological Survey installed monitoring wells and collected data to characterize the effectiveness of natural attenuation processes for remediating petroleum-contaminated ground water at Operable Unit A of the former Naval complex on Adak Island, Alaska. In addition, the evidence for petroleum biodegradation in ground water was evaluated at selected petroleum sites, plans for future natural attenuation monitoring were suggested for the selected petroleum sites, and the natural attenuation monitoring strategy for the Downtown area of Adak Island was reviewed and refinements were suggested. U.S. Geological Survey personnel measured water levels and collected ground-water samples from about 100 temporary boreholes and 50 monitoring wells. Most samples were analyzed on-site for concentrations of selected petroleum compounds and natural attenuation parameters such as dissolved oxygen, ferrous iron, and carbon dioxide. The U.S. Geological Survey evaluated the data on-site, selected new monitoring well locations, and installed, developed, and sampled 10 monitoring wells. The review and suggestions for the natural attenuation monitoring strategy focused on how to better achieve monitoring objectives specified in the Record of Decision for Adak Island petroleum sites. To achieve the monitoring objective of verifying that natural attenuation is occurring, the monitoring plans for each monitored natural attenuation site need to include sampling of at least one strategically placed well at the downgradient margin of the contaminant plume margin, preferably where contaminant concentrations are detectable but less than the cleanup level. Collection of natural attenuation parameter data and sampling background wells is no longer needed to achieve the monitoring objective of demonstrating the occurrence of natural attenuation. To achieve the objective of monitoring locations where chemical concentrations exceed specified cleanup levels, at least one natural attenuation well within or immediately downgradient from the contaminant source area at each site needs to be monitored. Achieving the Record of Decision-specified final monitoring objective of estimating the rate of natural attenuation to demonstrate achievement of cleanup levels within 75 years will be problematic. Demonstrating (predicting) achievement of cleanup levels within any timeframe in a technically defensible manner will be difficult to achieve using any type of short-term monitoring and evaluation, and will be particularly difficult to achieve through monitoring and evaluation of dissolved-phase petroleum only. Overall, natural attenuation processes appear to have greatly limited the extent of ground-water contamination at most sites investigated and have limited the risk that petroleum contaminants pose to downgradient receptors. Clarification or refinement of the monitoring objective to demonstrate cleanup within 75 years would be a reasonable prelude to developing a monitoring and data evaluation strategy to meet the objective.

Scientific Investigations Report