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USGS2001

Standard reference water samples for rare earth element determinations

Standard reference water samples (SRWS) were collected from two mine sites, one near Ophir, CO, USA and the other near Redding, CA, USA. The samples were filtered, preserved, and analyzed for rare earth element (REE) concentrations (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) by inductively coupled plasma-mass spectrometry (ICP-MS). These two samples were acid mine waters with elevated concentrations of REEs (0.45–161 μg/l). Seventeen international laboratories participated in a ‘round-robin’ chemical analysis program, which made it possible to evaluate the data by robust statistical procedures that are insensitive to outliers. The resulting most probable values are reported. Ten to 15 of the participants also reported values for Ba, Y, and Sc. Field parameters, major ion, and other trace element concentrations, not subject to statistical evaluation, are provided.

Applied Geochemistry↗
USGS2001

Composition and origin of coalbed gases in the Lower Silesian basin, southwest Poland

Coalbed gases in the Lower Silesian Coal Basin (LSCB) of Poland are highly variable in both their molecular and stable isotope compositions. Geochemical indices and stable isotope ratios vary within the following ranges: hydrocarbon (CHC) index CHC = CH4/(C2H6+C3H8) from 1.1 to 5825, wet gas (C2+) index C2+ = (C2H6+ C3H8+ C4H10+ C5H12) / (CH4+ C2H6+ C3H8+ C4H10+ C5H12) 100 (%) from 0.0 to 48.3%, CO2-CH4 (CDMI) index CDMI = CO2/ (CO2+ CH4) 100 (%) from 0.1 to 99.9%, ??13C(CH4) from -66.1 to -24.6%o, ??D(CH4) from -266 to -117%o, ??13C(C2H6) from -27.8 to -22.8%o, and ??13C(CO2) from -26.6 to 16.8%o. Isotopic studies reveal the presence of 3 genetic types of natural gases: thermogenic (CH4, higher gaseous hydrocarbons, and CO2), endogenic CO2, and microbial CH4 and CO2. Thermogenic gases resulted from coalification processes, which were probably completed by Late Carboniferous and Early Permian time. Endogenic CO2 migrated along the deep-seated faults from upper mantle and/or magma chambers. Minor volumes of microbial CH4 and CO2 occur at shallow depths close to the abandoned mine workings. "Late-stage" microbial processes have commenced in the Upper Cretaceous and are probably active at present. However, depth-related isotopic fractionation which has resulted from physical and physicochemical (e.g. diffusion and adsorption/desorption) processes during gas migration cannot be neglected. The strongest rock and gas outbursts occur only in those parts of coal deposits of the LSCB which are dominated by large amounts of endogenic CO2. ?? 2001 Elsevier Science Ltd.

Applied Geochemistry↗
USGS2001

Geochemical and mineralogical controls on trace element release from the Penn Mine base-metal slag dump, California

Base-metal slag deposits at the Penn Mine in Calaveras County, California, are a source of environmental contamination through leaching of potentially toxic elements. Historical Cu smelting at Penn Mine (1865-1919) generated approximately 200,000 m3 of slag. The slag deposits, which are flooded annually by a reservoir used for drinking water and irrigation, also may be in contact with acidic ground waters (pH < 4) from the adjacent mine area. Slags vary from grey to black, are glassy to crystalline, and range in size from coarse sand to large (0.6 ?? 0.7 ?? 1.5 m), tub-shaped casts. Metals are hosted by a variety of minerals and two glass phases. On the basis of mineralogy, slags are characterized by 4 main types: fayalite-rich, glassy, willemite-rich, and sulfide-rich. The ranges in metal and metalloid concentrations of 17 slag samples are: As, 0.0004-0.92; Ba, 0.13-2.9; Cd, 0.0014-1.4; Cu, 0.18-6.4; Pb, 0.02-11; and Zn, 3.2-28 wt.%. Leachates from Toxicity Characteristic Leaching Procedure tests (acetic acid buffered at pH 4.93) on two wiltemite-rich slags contained Cd and Pb concentrations (up to 2.5 and 30 mg/l, respectively) in excess of US Environmental Protection Agency (USEPA) regulatory limits. Analyses of filtered (0.45 ??m) water, collected within the flooded slag dump during reservoir drawdown, reveal concentrations of Cd (1.7 ??g/l), Cu (35 ??g/l), and Zn (250 ??g/l) that exceed USEPA chronic toxicity guidelines for the protection of aquatic life. Data from field and laboratory studies were used to develop geochemical models with the program EQ3/6 that simulate irreversible mass-transfer between slag deposits and reservoir waters. These models include kinetic rate laws for abiotic sulfide oxidation and surface-controlled dissolution of silicates, oxides, and glass. Calculations demonstrate that the main processes controlling dissolved metal concentrations are (1) dissolution of fayalite, willemite, and glass; (2) sulfide oxidation; and (3) secondary phase precipitation. Close agreement between model results and measured concentrations of Al, Ba, Cu, Fe, SiO2, and SO4 in the slag dump pore waters suggests that the dissolved concentrations of these elements are controlled by solubility equilibrium with secondary phases. Differences between predicted and measured Cd and Pb concentrations imply that field weathering rates of glass and sulfides are approximately two orders of magnitude lower than laboratory rates. Overprediction of Pb release may also reflect other attenuation processes in the natural system, such as sorption or coprecipitation. ?? 2001 Elsevier Science Ltd. All rights reserved.

Applied Geochemistry↗
USGS2001

Mercury and methylmercury in water and sediment of the Sacramento River Basin, California

Mercury (Hg) and methylmercury (CH3Hg+) concentrations in streambed sediment and water were determined at 27 locations throughout the Sacramento River Basin, CA. Mercury in sediment was elevated at locations downstream of either Hg mining or Au mining activities where Hg was used in the recovery of Au. Methylmercury in sediment was highest (2.84 ng/g) at a location with the greatest wetland land cover, in spite of lower total Hg at that site relative to other river sites. Mercury in unfiltered water was measured at 4 locations on the Sacramento River and at tributaries draining the mining regions, as well as agricultural regions. The highest levels of Hg in unfiltered water (2248 ng/l) were measured at a site downstream of a historic Hg mining area, and the highest levels at all sites were measured in samples collected during high streamflow when the levels of suspended sediment were also elevated. Mercury in unfiltered water exceeded the current federal and state recommended criterion for protection of aquatic life (50 ng/l as total Hg in unfiltered water) only during high streamflow conditions. The highest loading of Hg to the San Francisco Bay system was attributed to sources within the Cache Creek watershed, which are downstream of historic Hg mines, and to an unknown source or sources to the mainstem of the Sacramento River upstream of historic Au mining regions. That unknown source is possibly associated with a volcanic deposit. Methylmercury concentrations also were dependent on season and hydrologic conditions. The highest levels (1.98 ng/l) in the Sacramento River, during the period of study, were measured during a major flood event. The reactivity of Hg in unfiltered water was assessed by measuring the amount available for reaction by a strong reducing agent. Although most Hg was found to be nonreactive, the highest reactivity (7.8% of the total Hg in water) was measured in the sample collected from the same site with high CH3Hg+ in sediment, and during the time of year when that site was under continual flooded conditions. Although Hg concentrations in water downstream of the Hg mining operations were measured as high as 2248 ng/l during stormwater runoff events, the transported Hg was found to have a low potential for geochemical transformations, as indicated by the low reactivity to the reducing agent (0.0001% of the total), probably because most of the Hg in the unfiltered water sample was in the mercury sulfide form.

Applied Geochemistry↗
USGS2002

Spatial and temporal variability of trace element concentrations in an urban subtropical watershed, Honolulu, Hawaii

Trace metal concentrations in soils and in stream and estuarine sediments from a subtropical urban watershed in Hawaii are presented. The results are placed in the context of historical studies of environmental quality (water, soils, and sediment) in Hawaii to elucidate sources of trace elements and the processes responsible for their distribution. This work builds on earlier studies on sediments of Ala Wai Canal of urban Honolulu by examining spatial and temporal variations in the trace elements throughout the watershed. Natural processes and anthropogenic activity in urban Honolulu contribute to spatial and temporal variations of trace element concentrations throughout the watershed. Enrichment of trace elements in watershed soils result, in some cases, from contributions attributed to the weathering of volcanic rocks, as well as to a more variable anthropogenic input that reflects changes in land use in Honolulu. Varying concentrations of As, Cd, Cu, Pb and Zn in sediments reflect about 60 a of anthropogenic activity in Honolulu. Land use has a strong impact on the spatial distribution and abundance of selected trace elements in soils and stream sediments. As noted in continental US settings, the phasing out of Pb-alkyl fuel additives has decreased Pb inputs to recently deposited estuarine sediments. Yet, a substantial historical anthropogenic Pb inventory remains in soils of the watershed and erosion of surface soils continues to contribute to its enrichment in estuarine sediments. Concentrations of other elements (e.g., Cu, Zn, Cd), however, have not decreased with time, suggesting continued active inputs. Concentrations of Ba, Co, Cr, Ni, V and U, although elevated in some cases, typically reflect greater proportions attributed to natural sources rather than anthropogenic input. ?? 2002 Elsevier Science Ltd. All rights reserved.

Applied Geochemistry↗
USGS2002

Assessment of metal loads in watersheds affected by acid mine drainage by using tracer injection and synoptic sampling: Cement Creek, Colorado, USA

Watersheds in mineralized zones may contain many mines, each of which can contribute to acidity and the metal load of a stream. In this study the authors delineate hydrogeologic characteristics determining the transport of metals from the watershed to the stream in the watershed of Cement Creek, Colorado. Combining the injection of a chemical tracer, to determine a discharge, with synoptic sampling, to obtain chemistry of major ions and metals, spatially detailed load profiles are quantified. Using the discharge and load profiles, the authors (1) identified sampled inflow sources which emanate from undisturbed as well as previously mined areas; (2) demonstrate, based on simple hydrologic balance, that unsampled, likely dispersed subsurface, inflows are significant; and (3) estimate attenuation. For example, along the 12-km study reach, 108 kg per day of Zn were added to Cement Creek. Almost half of this load came from 10 well-defined areas that included both mined and non-mined parts of the watershed. However, the combined effect of many smaller inflows also contributed a substantial load that could limit the effectiveness of remediation. Of the total Zn load, 58.3 kg/day came from stream segments with no visible inflow, indicating the importance of contributions from dispersed subsurface inflow. The subsurface inflow mostly occurred in areas with substantial fracturing of the bedrock or in areas downstream from tributaries with large alluvial fans. Despite a pH generally less than 4.5, there was 58.4 kg/day of Zn attenuation that occurred in mixing zones downstream from inflows with high pH. Mixing zones can have local areas of pH that are high enough for sorption and precipitation reactions to have an effect. Principal component analysis classified inflows into 7 groups with distinct chemical signatures that represent water-rock interaction with different mineral-alteration suites in the watershed. The present approach provides a detailed snapshot of metal load for the watershed to support remediation decisions, and quantifies processes affecting metal transport.

Colorado↗
USGS2002

Assessing mine drainage pH from the color and spectral reflectance of chemical precipitates

The pH of mine impacted waters was estimated from the spectral reflectance of resident sediments composed mostly of chemical precipitates. Mine drainage sediments were collected from sites in the Anthracite Region of eastern Pennsylvania, representing acid to near neutral pH. Sediments occurring in acidic waters contained primarily schwertmannite and goethite while near neutral waters produced ferrihydrite. The minerals comprising the sediments occurring at each pH mode were spectrally separable. Spectral angle difference mapping was used to correlate sediment color with stream water pH (r2=0.76). Band-center and band-depth analysis of spectral absorption features were also used to discriminate ferrihydrite and goethite and/or schwertmannite by analyzing the 4T1??? 6A1 crystal field transition (900-1000 nm). The presence of these minerals accurately predicted stream water pH (r2=0.87) and provided a qualitative estimate of dissolved SO4 concentrations. Spectral analysis results were used to analyze airborne digital multispectral video (DMSV) imagery for several sites in the region. The high spatial resolution of the DMSV sensor allowed for precise mapping of the mine drainage sediments. The results from this study indicate that airborne and space-borne imaging spectrometers may be used to accurately classify streams impacted by acid vs. neutral-to-alkaline mine drainage after appropriate spectral libraries are developed.

Pennsylvania↗
USGS2002

The geohydrologic setting of Yucca Mountain, Nevada

This paper provides a geologic and hydrologic framework of the Yucca Mountain region for the geochemical papers in this volume. The regional geologic units, which range in age from late Precambrian through Holocene, are briefly described. Yucca Mountain is composed of dominantly pyroclastic units that range in age from 11.4 to 15.2 Ma. The principal focus of study has been on the Paintbrush Group, which includes two major zoned and welded ash-flow tuffs separated by an important hydrogeologic unit referred to as the Paintbrush non-welded (PTn). The regional structural setting is currently one of extension, and the major local tectonic domains are presented together with a tectonic model that is consistent with the known structures at Yucca Mountain. Streamflow in this arid to semi-arid region occurs principally in intermittent or ephemeral channels. Near Yucca Mountain, the channels of Fortymile Wash and Amargosa River collect infrequent runoff from tributary basins, ultimately draining to Death Valley. Beneath the surface, large-scale interbasin flow of groundwater from one valley to another occurs commonly in the region. Regional groundwater flow beneath Yucca Mountain originates in the high mesas to the north and returns to the surface either in southern Amargosa Desert or in Death Valley, where it is consumed by evapotranspiration. The water table is very deep beneath the upland areas such as Yucca Mountain, where it is 500-750 m below the land surface, providing a large thickness of unsaturated rocks that are potentially suitable to host a nuclear-waste repository. The nature of unsaturated flow processes, which are important for assessing radionuclide migration, are inferred mainly from hydrochemical or isotopic evidence, from pneumatic tests of the fracture systems, and from the results of in situ experiments. Water seeping down through the unsaturated zone flows rapidly through fractures and more slowly through the pores of the rock matrix. Although capillary forces are expected to divert much of the flow around repository openings, some may drip onto waste packages, ultimately causing release of radionuclides, followed by transport down to the water table. ?? 2002 Elsevier Science Ltd. All rights reserved.

Applied Geochemistry↗
USGS2002

U-Pb ages of secondary silica at Yucca Mountain, Nevada: Implications for the paleohydrology of the unsaturated zone

Uranium, Th and Pb isotopes were analyzed in layers of opal and chalcedony from individual mm- to cm-thick calcite and silica coatings at Yucca Mountain, Nevada, USA, a site that is being evaluated for a potential high-level nuclear waste repository. These calcite and silica coatings on fractures and in lithophysal cavities in Miocene-age tuffs in the unsaturated zone (UZ) precipitated from descending water and record a long history of percolation through the UZ. Opal and chalcedony have high concentrations of U (10 to 780 ppm) and low concentrations of common Pb as indicated by large values of 206Pb/204Pb (up to 53,806), thus making them suitable for U-Pb age determinations. Interpretations of U-Pb isotope systems in opal samples at Yucca Mountain are complicated by the incorporation of excess 234U at the time of mineral formation, resulting in reverse discordance of U-Pb ages. However, the 207PB/235U ages are much less affected by deviation from initial secular equilibrium and provide reliable ages of most silica deposits between 0.6 and 9.8 Ma. For chalcedony subsamples showing normal age discordance, these ages may represent minimum times of deposition. Typically, 207Pb/235U ages are consistent with the microstratigraphy in the mineral coating samples, such that the youngest ages are for subsamples from outer layers, intermediate ages are from inner layers, and oldest ages are from innermost layers. 234U and 230Th in most silica layers deeper in the coatings are in secular equilibrium with 238U, which is consistent with their old age and closed system behavior during the past -0.5 Ma. The ages for subsamples of silica layers from different microstratigraphic positions in individual calcite and silica coating samples collected from lithophysal cavities in the welded part of the Topopah Spring Tuff yield slow long-term average growth rates of 1 to 5 mm/Ma. These data imply that the deeper parts of the UZ at Yucca Mountain maintained long-term hydrologic stability over the past 10 Ma. despite significant climate variations. U-Pb ages for subsamples of silica layers from different microstratigraphic positions in individual calcite and silica coating samples collected from fractures in the shallower part of the UZ (welded part of the overlying Tiva Canyon Tuff) indicate larger long-term average growth rates up to 23 mm/Ma and an absence of recently deposited materials (ages of outermost layers are 3-5 Ma.). These differences between the characteristics of the coatings for samples from the shallower and deeper parts of the UZ may indicate that the nonwelded tuffs (PTn), located between the welded parts of the Tiva Canyon and Topopah Spring Tuffs, play an important role in moderating UZ flow.

Applied Geochemistry↗
USGS2002

Physical and stable-isotope evidence for formation of secondary calcite and silica in the unsaturated zone, Yucca Mountain, Nevada

Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite??fluorite??zeolites that is frequently capped by chalcedony??quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (??? 3 mm) with low-relief outer surfaces whereas shallow-dipping fractures and lithophysal cavities typically contain thicker, more coarsely crystalline deposits characterized by unusual thin, tabular calcite blades up to several cms in length. These blades may be capped with knobby or corniced overgrowths of late-stage calcite intergrown with opal. The observed textures in the fracture and cavity deposits are consistent with deposition from films of water fingering down fracture footwalls or drawn up faces of growing crystals by surface tension and evaporated at the crystal tips. Fluid inclusion studies have shown that most early-stage and some intermediate-stage calcite formed at temperatures of 35 to 85??C. Calcite deposition during the past several million years appears to have been at temperatures < 30??C. The elevated temperatures indicated by the fluid inclusions are consistent with temperatures estimated from calcite ??18O values. Although others have interpreted the elevated temperatures as evidence of hydrothermal activity and flooding of the tuffs of the potential repository, the authors conclude that the temperatures and fluid-inclusion assemblages are consistent with deposition in a UZ environment that experienced prolonged heat input from gradual cooling of nearby plutons. The physical restriction of the deposits (and, therefore, fluid flow) to fracture footwalls and cavity floors and the heterogeneous and limited distribution of the deposits provides compelling evidence that they do not reflect flooding of the thick UZ at Yucca Mountain. The textures and isotopic and chemical compositions of these mineral deposits are consistent with deposition in a UZ setting from meteoric waters percolating downward along fracture flow paths.

Applied Geochemistry↗
USGS2002

234U/238U evidence for local recharge and patterns of groundwater flow in the vicinity of Yucca Mountain, Nevada, USA

Uranium concentrations and 234U/238U ratios in saturated-zone and perched ground water were used to investigate hydrologic flow and downgradient dilution and dispersion in the vicinity of Yucca Mountain, a potential high-level radioactive waste disposal site. The U data were obtained by thermal ionization mass spectrometry on more than 280 samples from the Death Valley regional flow system. Large variations in both U concentrations (commonly 0.6-10 ??g 1-1) and 234U/238U activity ratios (commonly 1.5-6) are present on both local and regional scales; however, ground water with 234U/238U activity ratios from 7 up to 8.06 is restricted largely to samples from Yucca Mountain. Data from ground water in the Tertiary volcanic and Quaternary alluvial aquifers at and adjacent to Yucca Mountain plot in 3 distinct fields of reciprocal U concentration versus 234U/238U activity ratio correlated to different geographic areas. Ground water to the west of Yucca Mountain has large U concentrations and moderate 234U/238U whereas ground water to the east in the Fortymile flow system has similar 234U/238U, but distinctly smaller U concentrations. Ground water beneath the central part of Yucca Mountain has intermediate U concentrations but distinctive 234U/238U activity ratios of about 7-8. Perched water from the lower part of the unsaturated zone at Yucca Mountain has similarly large values of 234U/238U. These U data imply that the Tertiary volcanic aquifer beneath the central part of Yucca Mountain is isolated from north-south regional flow. The similarity of 234U/238U in both saturated- and unsaturated-zone ground water at Yucca Mountain further indicates that saturated-zone ground water beneath Yucca Mountain is dominated by local recharge rather than regional flow. The distinctive 234U/238U signatures also provide a natural tracer of downgradient flow. Elevated 234U/238U in ground water from two water-supply wells east of Yucca Mountain are interpreted as the result of induced flow from 40 a of ground-water withdrawal. Elevated 234U/238U in a borehole south of Yucca Mountain is interpreted as evidence that natural downgradient flow is more likely to follow southerly paths in the structurally anisotropic Tertiary volcanic aquifer where it becomes diluted by regional flow in the Fortymile system.

Applied Geochemistry↗
USGS2002

Uranium-series disequilibrium in tuffs from Yucca Mountain, Nevada, as evidence of pore-fluid flow over the last million years

Samples of tuff from boreholes drilled into fault zones in the Exploratory Studies Facility (ESF) and relatively unfractured rock of the Cross Drift tunnels, at Yucca Mountain, Nevada, have been analysed by U-series methods. This work is part of a project to verify the finding of fast flow-paths through the tuff to ESF level, indicated by the presence of 'bomb' 36Cl in pore fluids. Secular radioactive equilibrium in the U decay series, (i.e. when the radioactivity ratios 234U/238U, 230Th/234U and 226Ra/230Th all equal 1.00) might be expected if the tuff samples have not experienced radionuclide loss due to rock-water interaction occurring within the last million years. However, most fractured and unfractured samples were found to have a small deficiency of 234U (weighted mean 234U/238U=0.95??0.01) and a small excess of 230Th (weighted mean 230Th/234U 1.10??0.02). The 226Ra/230Th ratios are close to secular equilibrium (weighted mean = 0.94??0.07). These data indicate that 234U has been removed from the rock samples in the last ???350 ka, probably by pore fluids. Within the precision of the measurement, it would appear that 226Ra has not been mobilized and removed from the tuff, although there may be some localised 226Ra redistribution as suggested by a few ratio values that are significantly different from 1.0. Because both fractured and unfractured tuffs show approximately the same deficiency of 234U, this indicates that pore fluids are moving equally through fractured and unfractured rock, More importantly, fractured rock appears not to be a dominant pathway for groundwater flow (otherwise the ratio would be more strongly affected and the Th and Ra isotopic ratios would likely also show disequilibrium). Application of a simple mass-balance model suggests that surface infiltration rate is over an order of magnitude greater than the rate indicated by other infiltration models and that residence time of pore fluids at ESF level is about 400 a. Processes of U sorption, precipitation and re-solution are believed to be occurring and would account for these anomalous results but have not been included in the model. Despite the difficulties, the U-series data suggest that fractured rock, specifically the Sundance and Drill Hole Wash faults, are not preferred flow paths for groundwater flowing through the Topopah Spring tuff and, by implication, rapid-flow, within 50 a, from the surface to the level of the ESF is improbable. ?? 2002 Elsevier Science Ltd. All rights reserved.

Applied Geochemistry↗
USGS2002

Percolation flux and Transport velocity in the unsaturated zone, Yucca Mountain, Nevada

The percolation flux for borehole USW UZ-14 was calculated from 14C residence times of pore water and water content of cores measured in the laboratory. Transport velocity is calculated from the depth interval between two points divided by the difference in 14C residence times. Two methods were used to calculate the flux and velocity. The first method uses the 14C data and cumulative water content data directly in the incremental intervals in the Paintbrush nonwelded unit and the Topopah Spring welded unit. The second method uses the regression relation for 14C data and cumulative water content data for the entire Paintbrush nonwelded unit and the Topopah Spring Tuff/Topopah Spring welded unit. Using the first method, for the Paintbrush nonwelded unit in boreholeUSW UZ-14 percolation flux ranges from 2.3 to 41.0 mm/a. Transport velocity ranges from 1.2 to 40.6 cm/a. For the Topopah Spring welded unit percolation flux ranges from 0.9 to 5.8 mm/a in the 8 incremental intervals calculated. Transport velocity ranges from 1.4 to 7.3 cm/a in the 8 incremental intervals. Using the second method, average percolation flux in the Paintbrush nonwelded unit for 6 boreholes ranges from 0.9 to 4.0 mm/a at the 95% confidence level. Average transport velocity ranges from 0.6 to 2.6 cm/a. For the Topopah Spring welded unit and Topopah Spring Tuff, average percolation flux in 5 boreholes ranges from 1.3 to 3.2 mm/a. Average transport velocity ranges from 1.6 to 4.0 cm/a. Both the average percolation flux and average transport velocity in the PTn are smaller than in the TS/TSw. However, the average minimum and average maximum values for the percolation flux in the TS/TSw are within the PTn average range. Therefore, differences in the percolation flux in the two units are not significant. On the other hand, average, average minimum, and average maximum transport velocities in the TS/TSw unit are all larger than the PTn values, implying a larger transport velocity for the TS/TSw although there is a small overlap.

Applied Geochemistry↗
USGS2003

Characterization and diagenesis of strong-acid carboxyl groups in humic substances

A small fraction of carboxylic acid functional groups in humic substances are exceptionally acidic with pKa values as low as 0.5. A review of acid-group theory eliminated most models and explanations for these exceptionally acidic carboxyl groups. These acidic carboxyl groups in Suwannee River fulvic acid were enriched by a 2-stage fractionation process and the fractions were characterized by elemental, molecular-weight, and titrimetric analyses, and by infrared and 13C- and 1H-nuclear magnetic resonance spectrometry. An average structural model of the most acidic fraction derived from the characterization data indicated a high density of carboxyl groups clustered on oxygen-heterocycle alicyclic rings. Intramolecular H-bonding between adjacent carboxyl groups in these ring structures enhanced stabilization of the carboxylate anion which results in low pKa1 values. The standard, tetrahydrofuran tetracarboxylic acid, was shown to have similar acidity characteristics to the highly acidic fulvic acid fraction. The end products of 3 known diagenetic pathways for the formation of humic substances were shown to result in carboxyl groups clustered on oxygen-heterocycle alicyclic rings.

Applied Geochemistry↗
USGS2003

Baseflow and stormflow metal fluxes from two small agricultural catchments in the Coastal Plain of the Chesapeake Bay Basin, United States

Annual yields (fluxes per unit area) of Al, Mn, Fe, Ni, Cd, Pb, Zn, Cu, Cr, Co, As and Se were estimated for two small non-tidal stream catchments on the Eastern Shore of the Chesapeake Bay, United States - a poorly drained dissected-upland watershed in the Nanticoke River Basin, and a well-drained feeder tributary in the lower reaches of the Chester River Basin. Both watersheds are dominated by agriculture. A hydrograph-separation technique was used to determine the baseflow and stormflow components of metal yields, thus providing important insights into the effects of hydrology and climate on the transport of metals. Concentrations of suspended-sediment were used as a less-costly proxy of metal concentrations which are generally associated with particles. Results were compared to other studies in Chesapeake Bay and to general trends in metal concentrations across the United States. The study documented a larger than background yield of Zn and Co from the upper Nanticoke River Basin and possibly enriched concentrations of As, Cd and Se from both the upper Nanticoke River and the Chesterville Branch (a tributary of the lower Chester River). The annual yield of total Zn from the Nanticoke River Basin in 1998 was 18,000 g/km2/a, and was two to three times higher than yields reported from comparable river basins in the region. Concentrations of Cd also were high in both basins when compared to crustal concentrations and to other national data, but were within reasonable agreement with other Chesapeake Bay studies. Thus, Cd may be enriched locally either in natural materials or from agriculture.

Applied Geochemistry↗
USGS2003

A rapid procedure for the determination of thorium, uranium, cadmium and molybdenum in small sediment samples by inductively coupled plasma-mass spectrometry: Application in Chesapeake Bay

This paper describes a rapid procedure that allows precise analysis of Mo, Cd, U and Th in sediment samples as small as 10 mg by using a novel approach that utilizes a "pseudo" isotope dilution for Th and conventional isotope dilution for Mo, Cd and U by ICP-MS. Long-term reproducibility of the method is between 2.5 and 5% with an advantage of rapid analysis on a single digestion of sediment sample and the potential of adding other elements of interest if so desired. Application of this method to two piston cores collected near the mouth of the Patuxent River in Chesapeake Bay showed that the accumulation of authigenic Mo and Cd varied in response to the changing bottom water redox conditions, with anoxia showing consistent oscillations throughout both pre-industrial and industrial times. Accumulation of authigenic U shows consistent oscillations as well, without any apparent increase in productivity related to anoxic trends. Degrees of Mo and Cd enrichment also inversely correlate to halophilic microfaunal assemblages already established as paleoclimate proxies within the bay indicating that bottom water anoxia is driven in part by the amount of freshwater discharge that the area receives. ?? 2002 Elsevier Science Ltd. All rights reserved.

Applied Geochemistry↗
USGS2003

Evidence for chlorine recycling - Hydrosphere, biosphere, atmosphere - In a forested wet zone on the Canadian Shield

The ability to measure environmental levels of 36Cl by Accelerator Mass Spectrometry and 3H by 3He-ingrowth Mass Spectrometry has made it possible to use the pulses of these two isotopes released into the atmosphere during nuclear weapons testing as tracers of Cl and water movement in soils and groundwater. The authors have investigated the movement of these tracers below a forested wet zone, and have found that both are retarded to a differing extent in the near surface because of vegetative uptake and recycling. Adsorption by clay particles, followed by slow release to the groundwater, may also be significant. The data accumulated in this region of near vertical recharge have gone a considerable distance towards explaining the anomalously low concentrations of 36Cl measured in the 5 Laurentian Great Lakes, as well as indicating possible mechanisms for large scale Cl- recycling in the atmosphere and biosphere. Identification of the near-term non-conservative behaviour of the Cl- is significant, since such a phenomenon could introduce errors in many watershed calculations, e.g. water residence times, evaporation rates, and mixing calculations. Published by Elsevier Science Ltd.

Applied Geochemistry↗
USGS2003

Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

Applied Geochemistry↗