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USGS2003

Characterization of limestone reacted with acid-mine drainage in a pulsed limestone bed treatment system at the Friendship Hill National Historical Site, Pennsylvania, USA

Armoring of limestone is a common cause of failure in limestone-based acid-mine drainage (AMD) treatment systems. Limestone is the least expensive material available for acid neutralization, but is not typically recommended for highly acidic, Fe-rich waters due to armoring with Fe(III) oxyhydroxide coatings. A new AMD treatment technology that uses CO 2 in a pulsed limestone bed reactor minimizes armor formation and enhances limestone reaction with AMD. Limestone was characterized before and after treatment with constant flow and with the new pulsed limestone bed process using AMD from an inactive coal mine in Pennsylvania (pH=2.9, Fe =150 mg/l, acidity =1000 mg/l CaCO 3 ). In constant flow experiments, limestone is completely armored with reddish-colored ochre within 48 h of contact in a fluidized bed reactor. Effluent pH initially increased from the inflow pH of 2.9 to over 7, but then decreased to <4 during the 48 h of contact. Limestone grains developed a rind of gypsum encapsulated by a 10- to 30-μm thick, Fe-Al hydroxysulfate coating. Armoring slowed the reaction and prevented the limestone from generating any additional alkalinity in the system. With the pulsed flow limestone bed process, armor formation is largely suppressed and most limestone grains completely dissolve resulting in an effluent pH of >6 during operation. Limestone removed from a pulsed bed pilot plant is a mixture of unarmored, rounded and etched limestone grains and partially armored limestone and refractory mineral grains (dolomite, pyrite). The ∼30% of the residual grains in the pulsed flow reactor that are armored have thicker (50- to 100-μm), more aluminous coatings and lack the gypsum rind that develops in the constant flow experiment. Aluminium-rich zones developed in the interior parts of armor rims in both the constant flow and pulsed limestone bed experiments in response to pH changes at the solid/solution interface.

Applied Geochemistry↗

USGS2004

Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and δ-MnO 2 . A specific surface area of 746 m 2 g −1 and a surface site density of 2.1 mmol g −1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH IEP value of 2.2. Two site types (≡XOH and ≡YOH) were used. The fraction of total sites attributed to ≡XOH ( α ) and p K a2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. p K a2 values of 2.35±0.077 (≡XOH) and 6.06±0.040 (≡YOH) were determined at the 95% confidence level. The calculated average α value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. p K a2 and α values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba 2+ , Ca 2+ , Cd 2+ , Co 2+ , Cu 2+ , Mg 2+ , Mn 2+ , Ni 2+ , Pb 2+ , Sr 2+ and Zn 2+ . In addition, average model parameters were used to predict additional sorption data for which complementary titration data were not available. The two-site model accounts for variability in the titration data and most metal sorption data are fit well using the p K a2 and α values reported above. A linear free energy relationship (LFER) appears to exist for some of the metals; however, redox and cation exchange reactions may limit the prediction of surface complexation constants for additional metals using the LFER.

Applied Geochemistry↗

USGS2004

Geological and anthropogenic factors influencing mercury speciation in mine wastes: An EXAFS spectroscopy study

The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600??C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345??C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500-2000 ??m and <45 ??m size fractions (e.g., from 97-810 mg/kg Hg in calcines from the Sulphur Bank Mine, CA). The proportion of Hg-sulfides present also increased by 8-18% as particle size decreased over the same size range. This finding suggests that insoluble yet soft Hg-sulfides are subject to preferential mechanical weathering and become enriched in the fine-grained fraction, while soluble Hg phases are leached out more readily as particle size decreases. The speciation of Hg in mine wastes is similar to that in distributed sediments located downstream from the same waste piles, indicating that the transport of Hg from mine waste piles does not significantly impact Hg speciation. Hg LIII-EXAFS analysis of samples from Au mining regions, where elemental Hg(0) was introduced to aid in the Au recovery process, identified the presence of Hg-sulfides and schuetteite (Hg3O2SO4), which may have formed as a result of long-term Hg(0) burial in reducing high-sulfide sediments. ?? 2003 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

USGS2004

The origin of high sulfate concentrations in a coastal plain aquifer, Long Island, New York

Ion-exchange batch experiments were run on Cretaceous (Magothy aquifer) clay cores from a nearshore borehole and an inland borehole on Long Island, NY, to determine the origin of high SO42- concentrations in ground water. Desorption batch tests indicate that the amounts of SO 42- released from the core samples are much greater (980-4700 ??g/g of sediment) than the concentrations in ground-water samples. The locally high SO42- concentrations in pore water extracted from cores are consistent with the overall increase in SO 42- concentrations in ground water along Magothy flow paths. Results of the sorption batch tests indicate that SO42- sorption onto clay is small but significant (40-120 ??g/g of sediment) in the low-pH (<5) pore water of clays, and a significant part of the SO42- in Magothy pore water may result from the oxidation of FeS2 by dissolved Fe(III). The acidic conditions that result from FeS2 oxidation in acidic pore water should result in greater sorption of SO42- and other anions onto protonated surfaces than in neutral-pH pore water. Comparison of the amounts of Cl- released from a clay core sample in desorption batch tests (4 ??g/g of sediment) with the amounts of Cl- sorbed to the same clay in sorption tests (3.7-5 ??g/g) indicates that the high concentrations of Cl- in pore water did not originate from connate seawater but were desorbed from sediment that was previously in contact with seawater. Furthermore, a hypothetical seawater transgression in the past is consistent with the observed pattern of sorbed cation complexes in the Magothy cores and could be a significant source of high SO42- concentrations in Magothy ground water.

Applied Geochemistry↗

USGS1996

Removal of selenium from contaminated agricultural drainage water by nanofiltration membranes

Seleniferous agricultural drainage wastewater has become a new major source of pollution in the world. In the USA, large areas of farmland in 17 western states, generate contaminated salinized drainage with Se concentrations much higher than 5 ??g/l, the US Environmental Protection Agency water-quality criterion for the protection of aquatic life; Se values locally reach 4200 ??g/l in western San Joaquin Valley, California. Wetland habitats receiving this drainage have generally shown Se toxicosis in aquatic birds causing high rates of embryonic deformity and mortality, or have indicated potential ecological damage. Results of our laboratory flow experiments indicate that nanofiltration, the latest membrane separation technology, can selectively remove > 95% of Se and other multivalent anions from > 90% of highly contaminated water from the San Joaquin Valley, California. Such membranes yield greater water output and require lower pressures and less pretreatment, and therefore, are more cost effective than traditional reverse osmosis membranes. Nanofiltration membranes offer a potential breakthrough for the management of Se contaminated wastes not only from agricultural drainage, but from other sources also.

Applied Geochemistry↗

USGS1997

Natural or fertilizer-derived uranium in irrigation drainage: A case study in southeastern Colorado, U.S.A.

Drainage from heavily cultivated soils may be contaminated with U that is leached from the soil or added as a trace constituent of PO4-based commercial fertilizer. The effect of decades-long application of U-rich fertilizer on the U concentration of irrigation drainage was investigated in a small (14.2 km2) drainage basin in southeastern Colorado. The basin was chosen because previous reports indicated locally anomalous concentrations of dissolved NO3(6-36 mg l-1) and dissolved U (61 ??g l-1) at the mouth of the only stream. Results of this study indicated minimal impact of fertilizer-U compared to natural U leached from the local soils. Detailed sampling of the stream along a 6 mile (9.7 km) reach through heavily cultivated lands indicated marked decoupling of the buildup of dissolved NO3 and U. Dissolved U increased markedly in the upstream half of the reach and correlated positively with increases in Na, Mg, SO4, B and Li derived from leaching of surrounding shaley soils. In contrast, major increases in dissolved NO3 occurred farther downstream where stream water was heavily impacted by ground water return from extensively fertilized fields. Nitrogen isotopic measurements confirmed that dissolved NO3 originated from fertilizer and soil organic N (crop waste). Uranium isotopic measurements of variably uraniferous waters showed little evidence of contamination with fertilizer-derived U of isotopically distinct 234U/238U alpha activity ratio (A.R. = 1.0). Leaching experiments using local alkaline soil, irrigation water and U-rich fertilizer confirmed the ready leachability of soil-bound U and the comparative immobility of U added with liquid fertilizer. Relatively insoluble precipitates containing Ca-P-U were formed by mixing liquid fertilizer with water containing abundant dissolved Ca. In the local soils soluble Ca is provided by dissolution of abundant gypsum. Similar studies are needed elsewhere because the mobility of fertilizer-derived U is dependent on fertilizer type, porewater chemistry and soil properties (pH, moisture, mineralogy, texture).

Applied Geochemistry↗

USGS1997

Iron deposition as acidic groundwater encounters carbonates in the alluvium of Pinal Creek, Arizona, U.S.A.

In a column experiment, acidic groundwater from Pinal Creek Arizona, a Cu mining area, was eluted through a composited alluvial sample obtained from a core that had been removed from a well downgradient of the acidic groundwater. The minerals present in typical grains and flakes in the alluvium before and after the elution were determined by X-ray diffraction (XRD), scanning electron microscopy, and energy dispersive multichannel analyses (EDX). The concentrations of Fe, Ti, Mn, Si, Al, Na, Ca, K, Mg and S in these grains and flakes and in their microcrystalline surface coatings were measured by EDX. In addition to magnetite, hematite, and Fe-Ti oxides, Fe was most concentrated in micas (especially biotite-like flakes) and in the microcrystalline coatings. The measured elements in these microcrystalline coatings were primarily K, Fe, Al, and Si. The microcrystalline coatings on the mica flakes also contained Mg. The approximate 1:3 Mg:Si atomic ratios (ARs) of the biotite-like flakes both before and after the elution would suggest that the Fe deposited during the elution had not substituted for Mg in these flakes. As a result of the elution, assuming no loss of Si, the averaged recorded Fe:Si AR of the microcrystalline coatings increased from (0,46 to 0.58):3.00. Iron deposition on the typical grains and flakes may relate to the presence of Fe in the particle on which it is deposited or to the presence of Fe in the microcrystalline surface coatings before elution. The data here are not sufficient for a statistical evaluation, but elution caused the following trends: (1) The Fe:Si A R increased in the (K,Fe,Al,Si)-microcrystalline surface coatings; (2) For the mica flakes, there was more than a 2-fold increase in the Fe:Si AR for the microcrystalline surface coatings of the Fe-rich biotite-like flakes but no measurable increase of the Fe:Si AR for the microcrystalline surface coatings of the muscovite-like flakes that contained 3-5 times less Fe; (3) Also for the biotite-like flakes, the increase in Fe:Si AR was greater in the flakes that had a higher Fe:Si AR; (4) The Fe deposition on the Fe-rich microcrystalline surface coatings of the feldspar was much greater than on the Fe-poor, beige quartz and feldspar grains that, prior to elution, had only CaSO4 microcrystalline coatings; and (5) No Fe was deposited on Fe-poor grains with no microcrystalline surface coating.

Arizona↗

USGS1997

Arsenic and lead concentrations in the Pond Creek and Fire Clay coal beds, eastern Kentucky coal field

The Middle Pennsylvanian Breathitt Formation (Westphalian B) Pond Creek and Fire Clay coal beds are the 2 largest producing coal beds in eastern Kentucky. Single channel samples from 22 localities in the Pond Creek coal bed were obtained from active coal mines in Pike and Martin Countries, Kentucky, and a total of 18 Fire Clay coal bed channel samples were collected from localities in the central portion of the coal field. The overall objective of this study was to investigate the concentration and distribution of potentially hazardous elements in the Fire Clay and Pond Creek coal beds, with particular emphasis on As and Pb, 2 elements that are included in the 1990 Clean Air Act Amendments as potential air toxics. The 2 coals are discussed individually as the depositional histories are distinct, the Fire Clay coal bed having more sites where relatively high-S lithologies are encountered. In an effort to characterize these coals, 40 whole channel samples, excluding 1-cm partings, were analyzed for major, minor and trace elements by X-ray fluorescence and proton-induced X-ray emission spectroscopy. Previously analyzed samples were added to provide additional geographic coverage and lithotype samples from one site were analyzed in order to provide detail of vertical elemental trends. The As and Pb levels in the Fire Clay coal bed tend to be higher than in the Pond Creek coal bed. One whole channel sample of the Fire Clay coal bed contains 1156 ppm As (ash basis), with a single lithotype containing 4000 ppm As (ash basis). Most of the As and Pb appears to be associated with pyrite, which potentially can be removed in beneficiation (particularly coarser pyrite). Disseminated finer pyrite may not be completely removable by cleaning. In the examination of pyrite conducted in this study, it does not appear that significant concentration of As or Pb occurs in the finer pyrite forms. The biggest potential problem of As- or Pb-enriched pyrite is, therefore, one of refuse disposal.

Applied Geochemistry↗

USGS1997

Effects of carbon dioxide variations in the unsaturated zone on water chemistry in a glacial-outwash aquifer

The research site at Otis Air Base, Cape Cod, Massachusetts, has been developed for hydrogeological and geochemical studies of sewage-effluent contaminated groundwater since 1982. Research of hydrologic properties, transport, and chemical and biological processes is ongoing, but the origin of background water chemistry has not been determined. The principal geochemical process giving rise to the observed background water chemistry is CO2-controlled hydrolysis of Na feldspar. Geochemical modeling demonstrated that CO2 sources could vary over the project area. Analyses of unsaturated zone gases showed variations in CO2 which were dependent on land use and vegetative cover in the area of groundwater recharge. Measurements of CO2 in unsaturated-zone gases showed that concentrations of total inorganic C in recharge water should range from about 0.035 to 1.0 mmoles/L in the vicinity of Otis Air Base. Flux of CO2 from the unsaturated zone varied for a principal land uses, ranging from 86 gC/m2/yr for low vegetated areas to 1630 gC/m2/yr for a golf course. Carbon dioxide flux from woodlands was 220 gC/m2/yr, lower than reported fluxes of 500 to 600 gC/m2/yr for woodlands in a similar climate. Carbon dioxide flux from grassy areas was 540 gC/m2/yr, higher than reported fluxes of 230 to 490 gC/m2/yr for grasslands in a similar climate.

Applied Geochemistry↗

USGS1997

Distribution of terminal electron-accepting processes in an aquifer having multiple contaminant sources

Concentrations of electron acceptors, electron donors, and H2 in groundwater were measured to determine the distribution of terminal electron-accepting processes (TEAPs) in an alluvial aquifer having multiple contaminant sources. Upgradient contaminant sources included two separate hydrocarbon point sources, one of which contained the fuel oxygenate methyl tertbutyl ether (MTBE). Infiltrating river water was a source of dissolved NO31 SO4 and organic carbon (DOC) to the downgradient part of the aquifer. Groundwater downgradient from the MTBE source had larger concentrations of electron acceptors (dissolved O2 and SO4) and smaller concentrations of TEAP end products (dissolved inorganic C, Fe2+ and CH4) than groundwater downgradient from the other hydrocarbon source, suggesting that MTBE was not as suitable for supporting TEAPs as the other hydrocarbons. Measurements of dissolved H2 indicated that SO4 reduction predominated in the aquifer during a period of high water levels in the aquifer and river. The predominant TEAP shifted to Fe3+ reduction in upgradient areas after water levels receded but remained SO4 reducing downgradient near the river. This distribution of TEAPs is the opposite of what is commonly observed in aquifers having a single contaminant point source and probably reflects the input of Dec and SO4 to the aquifer from the river. Results of this study indicate that the distribution of TEAPs in aquifers having multiple contaminant sources depends on the composition and location of the contaminants and on the availability of electron acceptors.

Applied Geochemistry↗

USGS1998

Factors controlling As and U in shallow ground water, southern Carson Desert, Nevada

Unusually high As and U concentrations (> 100 ??g/L) are widespread in shallow ground water beneath the southern Carson Desert. The high concentrations, which locally exceed 1000 ??g/L, are of concern from a human health standpoint because the shallow ground water is used for domestic supply. Possible affects on wildlife are also of concern because the ground water flows into shallow lakes and marshes within wildlife refuges. Arsenic and U concentrations in ground water of the southern Carson Desert appear to be affected by evaporative concentration, redox reactions, and adsorption. The relation of these elements with Cl suggest that most of the high concentrations can be attributed to evaporative concentration of Carson River water, the primary source of recharge. Some ground water contains higher As and U concentrations that cannot be explained by evaporative concentration alone. Oxidation-reduction reactions, involving metal oxides and sedimentary-organic matter, appear to contribute As, U, inorganic C, Fe and Mn to the ground water. Arsenic in Fe-oxide was confirmed by chemical extraction and is consistent with laboratory adsorption studies. Uranium in both sedimentary-organic C and Fe-oxide coatings has been confirmed by fission tracks and petrographic examination. Arsenic concentrations in the ground water and chemical extracts of aquifer sediments are broadly consistent with adsorption as a control on some dissolved As concentrations. An apparent loss of As from some ground water as evaporative concentration proceeds is consistent with adsorption as a control on As. However, evidence for adsorption should be viewed with caution, because the adsorption model used values for the adsorbent that have not been shown to be valid for the aquifer sediments throughout the southern Carson Desert. Hydrologic and geochemical conditions in the Carson Desert are similar to other areas with high As and U concentrations in ground water, including the Salton Sea basin and southern San Joaquin Valley of California. Hydrologic and geochemical conditions that produced some sandstone-tyPe U-ore deposits, including those in the non-marine, closed-basin sediments of the Morrison Formation near Grants, New Mexico, suggest that the Carson Desert may be a modern analog for those systems.

Applied Geochemistry↗

USGS1998

The chemical evolution of Kurnub Group palcowater in the Sinai-Negev province - A mass balance approach

The chemical evolution of the Kurnub Group paleowater was studied starting from rainwater in recharge areas of the Sinai and along groundwater flowpaths leading to the natural outlets of this regional aquifer. This was achieved by investigating the chemical composition of groundwater, ionic ratios, degrees of saturation with common mineral species, normative analysis of dissolved salts and by modeling of rock/water interaction and mixing processes occurring along groundwater flow paths. The initial groundwater composition used is from the Nakhel well in Sinai. It evolves from desert rainwater percolating through typical Kurnub Group lithology in Sinai. This rainwater dissolves mainly gypsum, halite and dolomite together with smaller amounts of marine aerosol and K-feldspar. At the same time it precipitates calcite, SiO2, smectite and degasses CO2. Between the area of Nakhel and the northern Negev the chemistry of Kurnub Group waters is influenced by dissolution of halite and lesser amounts of gypsum of surficial origin in recharge areas, small amounts of feldspars and of dolomite cement in sandstones eroded from the Arabo-Nubian igneous massif of Sinai and organic degradation-derived CO2. Concomitantly, there is precipitation of calcite, smectite, SiO2 and probably analcime characteristic of sediments in continental closed basins. North of the Negev, the Kurnub Group fluids are diluted and altered by mixing with Judea Group aquifer groundwaters. On the E there is mixing with residual brines from the water body ancestral to the Dead Sea, prior to discharge into the Arava valley. Rock/water interaction indicated by NETPATH and PHREEQC modeling is in agreement with lithology and facies changes previously observed in the Kurnub Group sequence.

Applied Geochemistry↗

USGS1998

Flow of river water into a Karstic limestone aquifer. 1. Tracing the young fraction in groundwater mixtures in the Upper Floridan Aquifer near Valdosta, Georgia

The quality of water in the Upper Floridan aquifer near Valdosta, Georgia is affected locally by discharge of Withlacoochee River water through sinkholes in the river bed. Data on transient tracers and other dissolved substances, including Cl − , 3 H, tritiogenic helium-3 ( 3 He), chlorofluorocarbons (CFC-11, CFC-12, CFC-113), organic C (DOC), O 2 (DO), H 2 S, CH 4 , δ 18 O, δD, and 14 C were investigated as tracers of Withlacoochee River water in the Upper Floridan aquifer. The concentrations of all tracers were affected by dilution and mixing. Dissolved Cl − , δ 18 O, δD, CFC-12, and the quantity ( 3 H+ 3 He) are stable in water from the Upper Floridan aquifer, whereas DOC, DO, H 2 S, CH 4 , 14 C, CFC-11, and CFC-113 are affected by microbial degradation and other geochemical processes occurring within the aquifer. Groundwater mixing fractions were determined by using dissolved Cl − and δ 18 O data, recognizing 3 end-member water types in the groundwater mixtures: (1) Withlacoochee River water (δ 18 O=−2.5±0.3‰, Cl − =12.2±2 mg/l), (2) regional infiltration water (δ 18 O=−4.2±0.1‰, Cl − =2.3±0.1 mg/l), and (3) regional paleowater resident in the Upper Floridan aquifer (δ 18 O=−3.4±0.1‰, Cl − =2.6±0.1 mg/l) (uncertainties are ±1σ). Error simulation procedures were used to define uncertainties in mixing fractions. Fractions of river water in groundwater range from 0 to 72% and average 10%. The influence of river-water discharge on the quality of water in the Upper Floridan aquifer was traced from the sinkhole area on the Withlacoochee River 25 km SE in the direction of regional groundwater flow. Infiltration of water is most significant to the N and NW of Valdosta, but becomes negligible to the S and SE in the direction of general thickening of post-Eocene confining beds overlying the Upper Floridan aquifer.

Georgia↗

USGS1998

Flow of river water into a karstic limestone aquifer: 2. Dating the young fraction in groundwater mixtures in the Upper Floridan aquifer near Valdosta, Georgia

Tritium/helium-3 ( 3 H/ 3 He) and chlorofluorocarbon (CFCs, CFC–11, CFC–12, CFC–113) data are used to date the young fraction in groundwater mixtures from a karstic limestone aquifer near Valdosta, Georgia, where regional paleowater in the Upper Floridan aquifer receives recharge from two young sources—the flow of Withlacoochee River water through sinkholes in the river bed, and leakage of infiltration water through post-Eocene semi-confining beds above the Upper Floridan aquifer. In dating the young fraction of mixtures using CFCs, it is necessary to reconstruct the CFC concentration that was in the young fraction prior to mixing. The 3 H/ 3 He age is independent of the extent of dilution with older ( 3 H-free and 3 He trit -free) water. The groundwater mixtures are designated as Type-1 for mixtures of regional paleowater and regional infiltration water and Type-2 for mixtures containing more than approximately 4% of river water. The fractions of regional paleowater, regional infiltration water, and Withlacoochee River water in the groundwater mixtures were determined from Cl − and δ 18 O data for water from the Upper Floridan aquifer at Valdosta, Georgia. The chlorofluorocarbons CFC–11 and CFC–113 are removed by microbial degradation and/or sorption processes in most anaerobic (Type-2) groundwater at Valdosta, but are present in some aerobic Type-1 water. CFC–12 persists in both SO 4 -reducing and methanogenic water. The very low detection limits for CFCs (approximately 0.3 pg kg −1 ) permitted CFC–11 and CFC–12 dating of the fraction of regional infiltration water in Type-1 mixtures, and CFC-12 dating of the river-water fraction in Type-2 mixtures. Overall, approximately 50% of the 85 water samples obtained from the Upper Floridan aquifer have CFC–12-based ages of the young fraction that are consistent with the 3 H concentration of the groundwater. Because of uncertainties associated with very low 3 H and 3 He content in dilute mixtures, 3 H/ 3 He dating is limited to the river-water fraction in Type-2 mixtures containing more than about 10% river water. Of the 41 water samples measured for 3 H/ 3 He dating, dilution of 3 H and low 3 He concentration limited 3 H/ 3 He dating to 16 mixtures in which 3 H/ 3 He ages are defined with errors ranging from ±2 to ±7.5 a (1 σ). After correction for dilution with (assumed) CFC-free regional infiltration water and regional paleowater in the Upper Floridan aquifer, adjusted CFC–12 ages agree with 3 H/ 3 He ages within 5 a or less in 7 of the 9 co-dated Type-2 mixtures. Tritium data and dating based on both CFC–11 and CFC–12 in Type-1 mixtures indicate that travel times of infiltration water through the overlying Post-Eocene semi-confining beds exceed 35 a. The CFC and 3 H/ 3 He dating indicate that the river fraction in most groundwater entered the groundwater reservoir in the past 20 to 30 a. Few domestic and municipal supply wells sampled intercept water younger than 5 a. Calculated velocities of river water in the Upper Floridan aquifer downgradient of the sinkhole area range from 0.4 to 8.2 m/d. Radiocarbon data indicate that ages of the regional paleowater are on the 10 000-a time scale. An average lag time of approximately 10 to 25 a is determined for discharge of groundwater from the surficial and intermediate aquifers above the Upper Floridan aquifer to the Withlacoochee River.

Georgia↗

USGS1999

Isotopic identification of the source of methane in subsurface sediments of an area surrounded by waste disposal facilities

The major source of methane (CH4) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH4 and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH4 up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH4 included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments. Isotopic analyses included ??13C, ??D, 14C, and 3H on select CH4 samples and ??D and ??18O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had ??13C values from -79 to -82???, typical of natural 'drift gas' generated by microbial CO2-reduction. The CH4 from the shallow lacustrine deposits had ??13C values from -63 to -76???, interpreted as a mixture between CH4 generated by microbial fermentation and the CO2-reduction processes within the subsurface sediments. The ??D values of all the CH4 samples were quite negative ranging from -272 to -299???. Groundwater sampled from the deeper zones also showed quite negative ??D values that explained the light ??D observed for the CH4. Radiocarbon analyses of the CH4 showed decreasing 14C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH4 detected in the fill deposits of this site was microbial CH4 generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH4 from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH4 could not be completely ruled out.

Applied Geochemistry↗

USGS1999

Geomorphological assessment of sediment contamination in an urban stream system

Little is known about the influence of fluvial-geomorphological features on the dispersal of sediment-related contaminants in urban drainage systems. This study investigates the relation between reach-scale geomorphological conditions and network-scale patterns of trace-element concentrations in a partially urbanized stream system in East-Central Illinois, USA Robust statistical analysis of bulk sediment samples reveals levels of Cr, Cu, Pb, Ni, and Zn exceed contamination thresholds in the portion of the watershed in close proximity to potential sources of pollution-in this case storm-sewer outfalls. Although trace-element concentrations decrease rapidly downstream from these sources, substantial local variability in metal levels exists within contaminated reaches. This local variability is related to reach-scale variation in fluvial-geomorphic conditions, which in turn produces variation in the degree of sorting and organic-matter content of bed material. Metal concentrations at contaminated sites also exhibit considerable variability over time. Analytical tests on specific size fractions of material collected at a highly contaminated site indicate that Cr and Ni are concentrated in the 0.063 to 0.250 mm fraction of the sediment. This fraction also has elevated concentration of Zr. SEM analysis shows that the fine sand fraction contains shards of stainless steel within a matrix of zircon sand, an industrial material associated with a nearby alloy casting operation. Samples of suspended load and bedload at the contaminated site also have elevated amounts of trace metals, but concentrations of Ni and Cr in the bedload are less than concentrations in the bed material, suggesting that these trace elements are relatively immobile. Off the other hand, amounts of CU and Zn in the bedload exceed concentrations in the bed material, implying that these trace metals are preferentially mobilized during transport events.

Applied Geochemistry↗

USGS1999

Hydrocarbon gases associated with permafrost in the Mackenzie Delta, Northwest Territories, Canada

Molecular and isotopic analyses of core gas samples from 3 permafrost research core holes (92GSCTAGLU, 92GSCKUMAK, 92GSCUNIPKAT; sample core depths ranging from 0.36 to 413.82 m) in the Mackenzie Delta of the Northwest Territories of Canada reveal the presence of hydrocarbon gases from both microbial and thermogenic sources. Analyses of most headspace and blended gas samples from the ice-bonded permafrost portion of the core holes yielded C1/(C2 + C3) hydrocarbon gas ratios and CH4-C isotopic compositions (??13C CH4) indicative of microbially sourced CH4 gas. However, near the base of ice-bonded permafrost and into the underlying non-frozen stratigraphic section, an increase in ethane (C2) concentrations, decreases in C1/(C2 + C3) hydrocarbon gas ratios, and CH4-C isotopic (??13C CH4) data indicate the presence of hydrocarbon gases derived from a thermogenic source. The thermogenic gas below permafrost in the Mackenzie Delta likely migrated from deeper hydrocarbon accumulations and/or directly from thermally mature hydrocarbon source rocks.

Applied Geochemistry↗

USGS1999

Iron reduction in the sediments of a hydrocarbon-contaminated aquifer

Sediments sampled at a hydrocarbon-contaminated, glacial-outwash, sandy aquifer near Bemidji, Minnesota, were analyzed for sediment-associated Fe with several techniques. Extraction with 0.5 M HCl dissolved poorly crystalline Fe oxides and small amounts of Fe in crystalline Fe oxides, and extracted Fe from phyllosilicates. Use of Ti-citrate-EDTA-bicarbonate results in more complete removal of crystalline Fe oxides. The average HCl-extractable Fe(III) concentration in the sediments closest to the crude-oil contamination (16.2 μmol/g) has been reduced by up to 30% from background values (23.8 μmol/g) as a result of Fe(III) reduction in contaminated anoxic groundwater. Iron(II) concentrations are elevated in sediments within an anoxic plume in the aquifer. Iron(II) values under the oil body (19.2 μmol/g) are as much as 4 times those in the background sediments (4.6 μmol/g), indicating incorporation of reduced Fe in the contaminated sediments. A 70% increase in total extractable Fe at the anoxic/oxic transition zone indicates reoxidation and precipitation of Fe mobilized from sediment in the anoxic plume. Scanning electron microscopy detected authigenic ferroan calcite in the anoxic sediments and confirmed abundant Fe(III) oxyhydroxides at the anoxic/oxic boundary. The redox biogeochemistry of Fe in this system is coupled to contaminant degradation and is important in predicting processes of hydrocarbon degradation.

Applied Geochemistry↗