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USGS2003

Selected natural attenuation monitoring data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2001

Previous investigations have shown that natural attenuation and biodegradation of chlorinated volatile organic compounds (CVOCs) are substantial in shallow ground water beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center (NUWC), Division Keyport, Washington. The U.S. Geological Survey (USGS) has continued to monitor ground-water geochemistry to assure that conditions remain favorable for contaminant biodegradation. This report presents the ground-water geochemical and selected CVOC data collected at OU 1 by the USGS during June 11-14, 2001 in support of the long-term monitoring for natural attenuation. Overall, the June 2001 data indicate that redox conditions in the upper aquifer remain favorable for reductive dechlorination of CVOCs because strongly reducing conditions persisted beneath much of the former landfill. Redox conditions in the intermediate aquifer down gradient of the landfill appear to have become more favorable for reductive dechlorination because June 2001 dissolved hydrogen concentrations indicated strongly reducing conditions there for the first time. Although changes in redox conditions were observed at certain wells during 2001, a longer monitoring period is needed to ascertain if phytoremediation activities are affecting the ground-water chemistry. A minor change to future monitoring is proposed. Filtered organic carbon (previously referred to as dissolved, and defined as that which passes through a 0.45-micrometer membrane filter) should be analyzed in the future rather than unfiltered (previously referred to as total) organic carbon because the filtered analysis may be a better measure of bioavailable organic carbon. Unfiltered and filtered organic carbon data were collected during June 2001 for comparison. Filtered organic carbon data collected in the future could be reasonably compared with historical unfiltered organic carbon data by multiplying the historical data by a factor of about 0.9.

Open-File Report↗

USGS1997

Responses of sediment geochemistry to climate change in Owens Lake sediment: An 800-k.y. record of saline/fresh cycles in core OL-92

Geochemical parameters of sediments from drill hole OL-92 indicate that Owens Lake was saline, alkaline, and highly productive during interglacial periods, and was hydrologically open and relatively unproductive during glacial periods. Abundance of CaCO 3 , organic carbon, and cation-exchange capacity of the clay fraction show cyclic variation down the core. Six minima in these components during the past 500 k.y. are interpreted as caused by intensive overflow that occurred during Sierran glacial advances. Maxima in these components indicate closed-lake conditions, reflecting warmer and more arid interglacial climates. The pattern of CaCO 3 abundance suggests that closed lake conditions predominated over the past 500 k.y. The absence of gaylussite and gypsum in the sediments, however, indicates lake salinity never exceeded about 15 wt %, a limit which requires flushing of accumulated salts every 10 k.y. Oscillations of CaCO 3 generally indicate a 100-k.y. dominant cycle, a characteristic of the marine δ 18 O record. Four of the last five marine isotope terminations are clearly shown in the Owens Lake record. The last interglacial at Owens Lake appears to have occurred between 120 ka and 50 ka. The roughly 10-k.y. offset between this interval and marine oxygen-isotope stage 5 reflects either error in the age-depth model, or alternatively, a time lag between changes in Northern Hemisphere ice volumes and the manifestation of local climate change in lake geochemistry and sedimentology.

California↗

USGS2014

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↗

USGS2015

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↗

USGS2016

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↗

USGS1997

Natural attenuation of chlorinated volatile organic compounds in a freshwater tidal wetland, Aberdeen Proving Ground, Maryland

Ground-water contaminant plumes that are flowing toward or currently discharging to wetland areas present unique remediation problems because of the hydrologic connections between ground water and surface water and the sensitive habitats in wetlands. Because wetlands typically have a large diversity of microorganisms and redox conditions that could enhance biodegradation, they are ideal environments for natural attenuation of organic contaminants, which is a treatment method that would leave the ecosystem largely undisturbed and be cost effective. During 1992-97, the U.S. Geological Survey investigated the natural attenuation of chlorinated volatile organic compounds (VOC's) in a contaminant plume that discharges from a sand aquifer to a freshwater tidal wetland along the West Branch Canal Creek at Aberdeen Proving Ground, Maryland. Characterization of the hydrogeology and geochemistry along flowpaths in the wetland area and determination of the occurrence and rates of biodegradation and sorption show that natural attenuation could be a feasible remediation method for the contaminant plume that extends along the West Branch Canal Creek. The aquifer, which received contaminants in the past from sources that were located upgradient of the current eastern boundary of the wetland, is about 40 to 45 feet thick in the study area. The overlying wetland sediments consist of two distinct layers that have a combined thickness of about 6 to 12 feet--an upper unit of peat and a lower unit of silty to sandy clay or clayey sand. Head distributions show strong vertical gradients, and flow directions are predominantly upward through the wetland sediments. Tidal fluctuations, however, cause some reversals in ground-water-flow directions and changes in discharge locations, which affect the distribution and transport of contaminants. The average linear velocity of ground water is estimated to be about 2 to 3 feet per year along vertical flow lines in the wetland area, and the total ground-water discharge along a 1-foot-wide strip of the wetland extending from the eastern wetland boundary to the creek is in the range of 0.13 to 0.25 feet squared per day. The major parent contaminants in the aquifer were trichloroethylene (TCE); 1,1,2,2-tetrachloroethane (PCA); carbon tetrachloride (CT); and chloroform (CF). The aquifer was typically aerobic, but ground water in the wetland sediments became increasingly anaerobic along the upward flow direction. Iron-reducing conditions were predominant in the lower wetland sediment unit composed of clayey sand and silt, and methanogenesis was predominant in an upper unit composed of peat. Total concentrations of VOC's and the relative proportions of parent compounds to anaerobic daughter products changed substantially as the contaminants were transported upward through these changing redox environments. Concentrations of the parent compounds TCE and PCA ranged from about 100 to 2,000 micrograms per liter in the aquifer beneath the wetland, whereas concentrations of daughter products were low or undetectable. In contrast, the parent compounds commonly were not detected in ground water in the wetland sediments, but the daughter compounds 1,2- dichloro-ethylene (12DCE), vinyl chloride (VC), 1,1,2-trichloroethane (112TCA), and 1,2-dichloroethane (12DCA) were observed. 12DCE and VC were the dominant daughter products in the wetland sediments, even where PCA was the primary parent contaminant discharging to the wetland. The presence of these daughter products in water in the wetland sediments indicates that TCE and PCA are degraded by reductive dechlorination reactions in the naturally anaerobic wetland sediments. Although production of daughter products was observed, total concentrations of the VOC's decreased upward through the 6- to 12-feet-thick wetland sediments and were less than 5 micrograms per liter near the surface. The daughter products are apparently further degraded by these anaerobic processes to non-chlorinated, non-toxic endproducts, or are removed by other attenuation processes such as aerobic degradation or volatilization. Several sets of anaerobic microcosms, some amended with TCE concentrations of 400 or 990 micrograms per liter (3.0 or 7.5 micromoles per liter) and one amended with PCA concentration of 480 micrograms per liter (2.9 micromoles per liter), were constructed in the laboratory using wetland sediment and ground water from the study area. These microcosm experiments confirmed field observations that 12DCE and VC are the dominant daughter products from anaerobic biodegradation of both TCE and PCA. Production of 112TCA and 12DCA also was observed in the PCA-amended microcosms, but concentrations were lower than those of 12DCE and VC. These results indicate that degradation of PCA occurs through both hydrogenolysis and dichloroelimination pathways under anaerobic conditions. Daughter products were not observed in sterile controls, except for relatively low concentrations of 12DCE in the PCA-amended controls, suggesting that the reactions were predominantly microbially mediated. Parent and daughter concentrations in the microcosms decreased to less than 5 micrograms per liter in less than 34 days under methanogenic conditions, thus showing extremely rapid biodegradation rates in these organic-rich wetland sediments. Maximum potential rate constants for biodegradation of TCE and PCA, which were calculated from the microcosm exper-iments assuming first-order degradation rates, ranged from 0.10 to 0.31 per day under methanogenic conditions, corresponding to half-lives of 2 to 7 days. The rate constant for TCE biodegradation under sulfate-reducing conditions was 0.045 West Branch, Aberdeen Proving Ground, Maryland 3 per day (half-life of 15 days), which is lower than under methanogenic conditions. These estimated rate constants for the wetland sediments are two to three orders of magnitude higher than those reported in the literature for TCE biodegradation in microcosms constructed with sandy aquifer sediments. Aerobic biodegradation rates for cis-12DCE, trans-12DCE, and VC were in the same range as those measured for TCE and PCA under anaerobic conditions in microcosm experiments. Thus, production of these daughter products by anaerobic biodegradation of TCE and PCA could be balanced by their consumption where oxygen is available in the wetland sediment, such as near roots and land surface. In the aerobic microcosm experiments, biodegradation of cis-12DCE, trans-12DCE, and VC occurred only if methane consumption occurred, indicating that methanotrophs were involved in the process. Aerobic biodegradation was fastest for vinyl chloride and slowest for TCE in the microcosm experiments. These results agree with other laboratory and field studies that have shown faster degradation by methane-utilizing cultures when the compounds are less halogenated. Equilibrium sorption isotherms were measured in 24-hour batch tests and used to estimate distribution coefficients ( K d 's) to describe the ratios of sorbed to aqueous concentrations of PCA and the daughter products cis-12DCE, trans-12DCE, and VC. The estimated K d's for PCA, cis-12DCE, trans-12DCE, and VC were about 2.3, 1.8, 2.4, and 1.3 liters per kilogram of sediment, respectively. Sorbed concentrations of PCA, cis-12DCE, and trans-12DCE in the wetland sediments, therefore, would be expected to be about twice the concentration measured in the water, whereas sorbed concentrations of VC would not be much greater than the aqueous concentrations. Coefficients of retardation, which were calculated using the K d 's and an advective flow velocity of about 2 feet per year, indicate that sorption alone would cause the movement of the contaminants in the wetland sediments to be 6 to 10 times slower than the advective ground-water flow. Biodegradation and sorption, therefore, are significant natural attenuation mechanisms for chlorinated hydrocarbons in these wetland sediments. The relatively thin layers of wetland sediments are critical in reducing contaminant concentrations and toxicity of the ground water before it discharges to the wetland surface and the creek, and natural attenuation in the wetland sediments could be an effective remediation method for the ground-water contaminants.

Maryland↗

USGS2004

Selected natural attenuation monitoring data, Operable Unit 1, Naval Undersea Warfare Center, Division Keyport, Washington, June 2002

Previous investigations indicated that natural attenuation and biodegradation of chlorinated volatile organic compounds (CVOCs) are substantial in shallow ground water beneath the 9-acre former landfill at Operable Unit 1 (OU 1), Naval Undersea Warfare Center (NUWC), Division Keyport, Washington. The U.S. Geological Survey (USGS) has continued to monitor ground-water geochemistry to assure that conditions remain favorable for contaminant biodegradation. This report presents the geochemical and selected CVOC data for ground water at OU 1, collected by the USGS during June 10-14, 2002, in support of long-term monitoring for natural attenuation. Overall, the geochemical data for June 2002 indicate that redox conditions in the upper-aquifer water remain favorable for reductive dechlorination of chlorinated VOCs because strongly reducing conditions persisted beneath much of the former landfill. Redox conditions in the intermediate aquifer downgradient of the landfill also remained favorable for reductive dechlorination, although the 2002 dissolved hydrogen (H2) concentration from well MW1-28 is questionable. Changes in redox conditions were observed at certain wells during 2002, but a longer monitoring period and more thorough interpretation are needed to ascertain if phytoremediation activities are affecting redox conditions and if biodegradation processes are changing over time. The Navy intends to complete a more thorough interpretation in preparation for the 5-year review of OU 1 scheduled for 2004. There were a few substantial differences between the 2002 concentrations and previously observed concentrations of volatile organic compounds. Total CVOC concentrations in 2002 samples decreased substantially in all piezometers sampled in the northern plantation, and the largest percentages of decrease were for the compounds trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE). Changes in total CVOC concentrations in the southern plantation were less consistent. Historically high concentrations were observed in samples from three piezometers, with particularly substantial increases in TCE and cis-DCE concentrations, and historically low concentrations were observed in two piezometers, with particularly substantial decreases in TCE and cis-DCE concentrations. Similarly to the redox chemistry, a longer monitoring period and more thorough interpretation are needed to ascertain if phytoremediation activities are affecting CVOC concentrations and if biodegradation processes are changing over time. No changes in monitoring plans are proposed for June 2003, although the practice of deploying a data sonde downhole while purging the wells will be discontinued. Downhole monitoring added uncertainty to selected measured dissolved H2 concentrations because of the possibility that the sonde and cable created a bridge that resulted in non-equilibrium dissolved H2 concentrations at the wells.

Open-File Report↗

USGS1991

Geochemistry of dissolved inorganic carbon in a Coastal Plain aquifer. 1. Sulfate from confining beds as an oxidant in microbial CO2 production

A primary source of dissolved inorganic carbon (DIC) in the Black Creek aquifer of South Carolina is carbon dioxide produced by microbially mediated oxidation of sedimentary organic matter. Groundwater chemistry data indicate, however, that the available mass of inorganic electron acceptors (oxygen, Fe(III), and sulfate) and observed methane production is inadequate to account for observed CO 2 production. Although sulfate concentrations are low (approximately 0.05–0.10 mM) in aquifer water throughout the flow system, sulfate concentrations are greater in confining-bed pore water (0.4–20 mM). The distribution of culturable sulfate-reducing bacteria in these sediments suggests that this concentration gradient is maintained by greater sulfate-reducing activity in sands than in clays. Calculations based on Fick's Law indicate that possible rates of sulfate diffusion to aquifer sediments are sufficient to explain observed rates of CO 2 production (about 10 −5 mmoll −1 year −1 ), thus eliminating the apparent electron-acceptor deficit. Furthermore, concentrations of dissolved hydrogen in aquifer water are in the range characteristic of sulfate reduction (2–6 nM), which provides independent evidence that sulfate reduction is the predominant terminal electron-accepting process in this system. The observed accumulation of pyrite- and calcite-cemented sandstones at sand-clay interfaces is direct physical evidence that these processes have been continuing over the history of these sediments.

Journal of Hydrology↗

USGS2005

Palaeohydrology of the Southwest Yukon Territory, Canada, based on multiproxy analyses of lake sediment cores from a depth transect

Lake-level variations at Marcella Lake, a small, hydrologically closed lake in the southwestern Yukon Territory, document changes in effective moisture since the early Holocene. Former water levels, driven by regional palaeohydrology, were reconstructed by multiproxy analyses of sediment cores from four sites spanning shallow to deep water. Marcella Lake today is thermally stratified, being protected from wind by its position in a depression. It is alkaline and undergoes bio-induced calcification. Relative accumulations of calcium carbonate and organic matter at the sediment-water interface depend on the location of the depositional site relative to the thermocline. We relate lake-level fluctuations to down-core stratigraphic variations in composition, geochemistry, sedimentary structures and to the occurrence of unconformities in four cores based on observations of modern limnology and sedimentation processes. Twenty-four AMS radiocarbon dates on macrofossils and pollen provide the lake-level chronology. Prior to 10 000 cal. BP water levels were low, but then they rose to 3 to 4 m below modern levels. Between 7500 and 5000 cal. BP water levels were 5 to 6 m below modern but rose by 4000 cal. BP. Between 4000 and 2000 cal. BP they were higher than modern. During the last 2000 years, water levels were either near or 1 to 2 m below modern levels. Marcella Lake water-level fluctuations correspond with previously documented palaeoenvironmental and palaeoclimatic changes and provide new, independent effective moisture information. The improved geochronology and quantitative water-level estimates are a framework for more detailed studies in the southwest Yukon. ?? 2005 Edward Arnold (Publishers) Ltd.

Holocene↗

USGS1997

Mercury accumulation in Devils Lake, North Dakota effects of environmental variation in closed-basin lakes on mercury chronologies

Sediment cores were collected from lakes in the Devils Lake Basin in North Dakota to determine if mercury (Hg) accumulation chronologies from sediment-core data are good indicators of variations in Hg accumulation rates in saline lakes. Sediment cores from Creel Bay and Main Bay, Devils Lake were selected for detailed analysis and interpretation. The maximum Hg concentration in the Creel Bay core was 0.15 micrograms per gram at 8 to 9 centimeters. The maximum Hg concentration in the Main Bay core was 0.07 micrograms per gram at 5 to 7 centimeters. The general decreases in Hg concentrations with depth are attributed to historic variations in atmospheric Hg deposition rate. Hg stratigraphies combined with 210Pb and 137Cs dating analyses yield Hg chronologies that indicate a general increase in Hg accumulation rates in Devils Lake since the middle of the 19th century. Mean modern Hg accumulation rates in Creel Bay were 4.9 nanograms per square centimeter per year, and rates in Main Bay were 1.8 nanograms per square centimeter per year. Mean preindustrial Hg accumulation rates in Creel Bay were 1.2 nanograms per square centimeter per year, and rates in Main Bay were 1.6 nanograms per square centimeter per year. Relatively low Hg concentrations in recent sediments in the Devils Lake Basin, along with similarities in Hg accumulation rates between lakes in the Devils Lake Basin and other lakes in the northern interior of North America, indicate that local sources of Hg are not important sources of Hg. Results of the study indicate that accurate Hg chronologies are discernible in sediment cores collected from saline lakes. However, spatial and temporal variations in lake level and water chemistry common to saline lakes make interpretation of radioisotopic and geochemical chronologies difficult. Hg geochemistry in Devils Lake, and presumably in other saline lakes, is dynamic. The results of this study indicate that the absolute amount of sediment transported to Devils Lake, along with the associated Hg and total organic carbon, and the distribution of sedimentation patterns in Devils Lake may be affected by changing lake levels.

Water, Air, & Soil Pollution↗

USGS2002

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

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

New York↗

USGS1980

Plan of study for the Northern Atlantic Coastal Plain Regional Aquifer System Analysis

Sediments of Cretaceous to Holocene age compose the Northern Atlantic Coastal Plain aquifer system in an area of 50,000 square miles in parts of New York, New Jersey, Delaware, Maryland, Virginia, and North Carolina. The aquifer system is a major source of water supply in the area. About 1.4 billion gallons is withdrawn from its aquifers each day. Increasing withdrawal of ground water has created or intensified several problems such as declining water levels, development of large cones of depression, saltwater intrusion, spreading of ground-water contamination, and land subsidence. The U.S. Geological Survey has begun a comprehensive study that will define the geology, hydrology, and geochemistry of the aquifer system. The effects of future utilization of the aquifer system will be determined and alternative plans for water withdrawal will be evaluated through computer simulation modeling. This report describes the objectives, organization, and work plans of the study, and describes the work to be accomplished in each U.S. Geological Survey District of the study area.

Delaware;Maryl;New Jersey;North Carolina;Virginia↗

USGS1985

Paleoclimate controls on late paleozoic sedimentation and peat formation in the central appalachian basin (U.S.A.)

In the central Appalachian basin, at least two major climate changes affected sedimentation during the late Paleozoic. Stratigraphically, these two changes are indicated by the distribution of coal beds, the variation in coal quality, and the variation in rock lithologies. In latest Mississippian or earliest Pennsylvanian time, the climate changed from dry-seasonal tropical to ever-wet (equable) tropical. The equable climate prevailed into the Middle Pennsylvanian, influencing the morphology and geochemistry in peat-forming environments. Many of the peat deposits, which formed under the equable climate, were probably domed (raised bogs); low concentrations of dissolved solids in peat formation water resulted in low buffering capacity. Organic acids caused acidic (pH < 4), antiseptic conditions that resulted in intense leaching of mineral matter, minimal degradation of organic matter, and low-ash and low-sulfur peat deposits; the resulting coal beds are also low in ash and sulfur. Associated rocks are noncalcareous and consist of sequences of interbedded shale, siltstone, and sandstone including quartz arenite. Another climate change occurred in late Middle Pennsylvanian time when evapopation periodically exceeded rainfall resulting in an increase of both dissolved solids and pH (4 to ∼ 7) in surface and near-surface water. Throughout the remainder of the Pennsylvanian, the surfaces of peat deposits were probably planar (not domed); water in peat-forming and other depositional environments became more nearly neutral. The coal beds derived from these peats are highly variable in both ash and sulfur contents. Drier or more seasonal climates are also indicated by sequences of (1) calcareous sandstone and shale, (2) nonmarine limestone that shows shallow-water and subaerial exposure features, and (3) calcareous paleosols that have caliche characteristics. Our data and observations indicate that physical depositional environment models for the origin of coal do not adequately explain variations in mineral matter content and composition in commercial quality coal beds in the central Appalachian basin. Stratigraphic variation in mineral matter in coal beds, and in syngenetic and early diagenetic minerals in rocks associated with the coal beds, appears to be better explained by changes in geochemical conditions of nonmarine sedimentation. Paleoclimate was a principle control on these geochemical conditions.

International Journal of Coal Geology↗

USGS1994

Environmental conditions affecting concentrations of He, CO2, O2 and N2 in soil gases

The measurement of concentrations of volatile species in soil gases has potential for use in geochemical exploration for concealed ore deposits and for monitoring of subsurface contaminants. However, the interpretation of anomalies in surficial gases can be difficult because soil-gas concentrations are dependent on both meteorological and environmental conditions. For this study, concentrations of He, CO 2 , O 2 and N 2 and meteorological conditions were monitored for 10–14 months at eight nonmineralized sites in both humid and dry environments. Gases were collected at 0.6–0.7-m depth at seven sites. At one site, gases were collected from 0.3-, 0.6-, 1.2-, and 2.0-m depths; diurnal monitoring studies were conducted at this site also. Rain and snowfall, soil and air temperatures, barometric pressure, and relative humidity were monitored at all the sites. The sand, silt and clay content, and the organic carbon content of surficial soil were measured at each site. Meteorological conditions generally affected He and CO 2 concentrations in the same way at all the sites; however, these effects were modified by local environmental conditions. Both seasonal and diurnal concentration changes occurred. The most important seasonal concentration changes were related to rain and snowfall and soil and air temperatures. Seasonal changes tended to be larger then the diurnal changes, but both could be related to the same processes. Local conditions of soil type and organic content affected the amount of pore space and moisture present in the soil and therefore the soil-gas concentrations.

Applied Geochemistry↗

USGS2013

Characterization of mercury contamination in the Androscoggin River, Coos County, New Hampshire

The former chloralkali facility in Berlin, New Hampshire, was designated a Superfund site in 2005. Historic paper mill activities resulted in the contamination of groundwater, surface water, and sediments with many organic compounds and mercury (Hg). Hg continues to seep into the Androscoggin River in elemental form through bedrock fractures. The objective of this study was to spatially characterize (1) the extent of Hg contamination in water, sediment, and biota; (2) Hg speciation and methylmercury (MeHg) production potential rates in sediment; (3) the availability of inorganic divalent Hg (Hg(II)) for Hg(II)-methylation (MeHg production); and (4) ancillary sediment geochemistry necessary to better understand Hg speciation and MeHg production potential rates in this system. Concentrations of total mercury (THg) and MeHg in sediment, pore water, and biota in the Androscoggin River were elevated downstream from the former chloralkali facility compared with those upstream from reference sites. Sequential extraction of surface sediment showed a distinct difference in Hg speciation upstream compared with downstream from the contamination site. An upstream site was dominated by potassium hydroxide-extractable forms (for example, organic-Hg or particle-bound Hg(II)), whereas sites downstream from the point source were dominated by more chemically recalcitrant forms (largely concentrated nitric acid-extractable), indicative of elemental mercury or mercurous chloride. At all sites, only a minor fraction (less than 0.1 percent) of THg existed in chemically labile forms (for example, water extractable or weak acid extractable). All metrics indicated that a greater percentage of mercury at an upstream site was available for Hg(II)-methylation compared with sites downstream from the point source, but the absolute concentration of bioavailable Hg(II) was greater downstream from the point source. In addition, the concentration of tin-reducible inorganic reactive mercury, a surrogate measure of bioavailable Hg(II) generally increased with distance downstream from the point source. Whereas concentrations of mercury species on a sediment-dry-weight basis generally reflected the relative location of the sample to the point source, river-reach integrated mercury-species inventories and MeHg production potential (MPP) rates reflected the amount of fine-grained sediment in a given reach. THg concentrations in biota were significantly higher downstream from the point source compared with upstream reference sites for smallmouth bass, white sucker, crayfish, oligochaetes, bat fur, nestling tree swallow blood and feathers, adult tree swallow blood, and tree swallow eggs. As with tin-reducible inorganic reactive mercury, THg in smallmouth bass also increased with distance downstream from the point source. Toxicity tests and invertebrate community assessments suggested that invertebrates were not impaired at the current (2009 and 2010) levels of mercury contamination downstream from the point source. Concentrations of THg and MeHg in most water and sediment samples from the Androscoggin River were below U.S. Environmental Protection Agency (USEPA), the Canadian Council of Ministers of the Environment, and probable effects level guidelines. Surface-water and sediment samples from the Androscoggin River had similar THg concentrations but lower MeHg concentrations compared with other rivers in the region. Concentrations of THg in fish tissue were all above regional and U.S. Environmental Protection Agency guidelines. Moreover, median THg concentrations in smallmouth bass from the Androscoggin River were significantly higher than those reported in regional surveys of river and streams nationwide and in the Northeastern United States and Canada. The higher concentrations of mercury in smallmouth bass suggest conditions may be more favorable for Hg(II)-methylation and bioaccumulation in the Androscoggin River compared with many other rivers in the United States and Canada.

New Hampshire↗

USGS1991

Selectivity and effectiveness of extractants used to release metals associated with organic matter

Partial extraction procedures can be used to release metals associated with organic matter in natural materials. Reagents commonly employed for this purpose include hydrogen peroxide, Na hypochlorite and Na pyrophosphate. This study tested the selectivity of these reagents by comparing the amount of Fe, Mn, Zn and Cu they released from sulfide and oxide minerals and determined the ability of these reagents to release the same metals from peat. Sodium hypochlorite and Na pyrophosphate released between 0.2 and 8.7% of the total metal content of the Fe, Cu and Zn minerals. In contrast, three commonly used hydrogen peroxide reagents released significantly more metals from the oxides and sulfides. Percentages of Zn and Mn released from the peat samples were comparable for all extractions tested. Per cent Cu released from peat by Na pyrophosphate was very low compared to that released by hydrogen peroxide/HNO 3 or na hypochlorite. A smaller fraction of Fe was released from peat by Na hypochlorite than by the other reagents. Iron release by Na hypochlorite correlates with the organic carbon content of the peat samples. A universal extractant for metals associated with organic matter in all types of samples has not been identified. Sodium hypochlorite and Na pyrophosphate are better than hydrogen peroxide in selectively releasing metals bound to organic matter because they do not release significant amounts of metals from oxide and sulfide minerals.

Applied Geochemistry↗

USGS2011

Carbon and nitrogen biogeochemistry of a Prairie Pothole Wetland, Stutsman County, North Dakota, USA

The concentration and form of dissolved organic C (DOC) and N species (NH 4 + and NO 3 - ) were investigated as part of a larger hydrogeochemical study of the Cottonwood Lake Study Area within the Prairie Potholes region. Groundwater, pore water and surface wetland water data were used to help characterize the relationships between surface and groundwater with respect to nutrient dynamics. Photosynthesis and subsequent decomposition of vegetation in these hydrologically dynamic wetlands generates a large amount of dissolved C and N, although the subsurface till, derived in part from organic matter rich Pierre Shale, is a likely secondary source of nutrients in deeper groundwater. While surface water DOC concentrations ranged from 2.2 to 4.6 mM, groundwater values were 0.15 mM to 3.7 mM. Greater specific UV absorbance (SUVA 254 ) in the wetland water column and in soil pore waters relative to groundwater indicate more reactive DOC in the surface to near-surface waters. Circumneutral wetlands had greater SUVA254, possibly because of variations in vegetation communities. The dominant inorganic nitrogen species was NH 4 + in both wetland water and most ground water samples. The exceptions were 3 wells with NO 3 - ranging from 38 to 115 μM. Shallow groundwater wells (Well 28 and Well 13S) with greater connection to wetland surface water had greater NH 4 + concentrations (1.1 mM and 120 μM) than other well samples (3–90 μM). Pore water nutrient chemistry was more similar to surface water than ground water. Nitrogen results suggest reducing conditions in both groundwater and surface water, possibly due to the microbial uptake of O 2 by decaying vegetation in the wetland water column, labile organic C available in shallow groundwater, or the oxidation of pyrite associated with the subsurface.

North Dakota↗

USGS2002

Geochemistry of surface and pore water at USGS coring sites in wetlands of South Florida, 1994 and 1995

In this report, we present preliminary data on surface and pore water geochemistry from 22 sites in south Florida sampled during 1994 and 1995. These results are part of a larger study designed to evaluate the role of biogeochemical processes in sediments in the cycling of carbon, nitrogen, phosphorus, and sulfur in the south Florida ecosystem. The data are briefly discussed in regard to regional trends in the concentrations of chemical species, and general diagenetic processes in sediments. These results are part of a larger study designed to evaluate the role of biogeochemical processes in sediments in the cycling of carbon, nitrogen, phosphorus, and sulfur in the south Florida ecosystem. These elements play a crucial role in regulating organic sedimentation, nutrient dynamics, redox conditions, and the biogeochemistry of mercury in the threatened wetlands of south Florida. Pore water samples for chemical analyis were obtained using a piston corer/squeezer designed to avoid compression of the sediment and avoid oxidation and contamination of the pore water samples. Results show distinct regional trends in both surface water and pore water geochemistry. Most chemical species in surface and pore water show peak concentrations in Water Conservation Area 2A, with diminishing concentrations to the south and west into Water Conservation Area 3A, and Everglades National Park. The largest differences observed were for phosphate and sulfide, with concentrations in pore waters in Water Conservation Area 2A up to 500x higher than concentrations observed in freshwater marsh areas of Water Conservation Area 3A and Everglades National Park. Sites near the Hillsboro Canal in Water Conservation Area 2A are heavily contaminated with both phosphorus and sulfur. Pore water profiles for dissolved reactive phosphate suggest that recycling of phosphorus at these contaminated sites occurs primarily in the upper 20 cm of sediment. High levels of sulfide in pore water in Water Conservation Area 2A may inhibit mercury methylation here. At sites in Water Conservation Area 3A south of Alligator Alley, sulfide levels are much lower and sulfate reduction in the sediments here may be conducive to methyl mercury formation. Concentration versus depth profiles of biogeochemically important chemical species in pore water at most sites are smoth curves amenable to modelling using standard diagenetic equations. This should allow prediction of rates of biogeochemical processes in these sediments for incorporation in ecosystem models.

Florida↗