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Plague and trace metals in natural systems

All pathogenic organisms are exposed to abiotic influences such as the microclimates and chemical constituents of their environments. Even those pathogens that exist primarily within their hosts or vectors can be influenced directly or indirectly. Yersinia pestis , the flea-borne bacterium causing plague, is influenced by climate and its survival in soil suggests a potentially strong influence of soil chemistry. We summarize a series of controlled studies conducted over four decades in Russia by Dr. Evgeny Rotshild and his colleagues that investigated correlations between trace metals in soils, plants, and insects, and the detection of plague in free-ranging small mammals. Trace metal concentrations in plots where plague was detected were up to 20-fold higher or lower compared to associated control plots, and these differences were >2-fold in 22 of 38 comparisons. The results were statistically supported in eight studies involving seven host species in three families and two orders of small mammals. Plague tended to be positively associated with manganese and cobalt, and the plague association was negative for copper, zinc, and molybdenum. In additional studies, these investigators detected similar connections between pasturellosis and concentrations of some chemical elements. A One Health narrative should recognize that the chemistry of soil and water may facilitate or impede epidemics in humans and epizootics in non-human animals.

International Journal of Environmental Research an↗

Springs, streams, and gas vent on and near Mount Adams volcano, Washington

Springs and some streams on Mount Adams volcano have been sampled for chemistry and light stable isotopes of water. Spring temperatures are generally cooler than air temperatures from weather stations at the same elevation. Spring chemistry generally reflects weathering of volcanic rock from dissolved carbon dioxide. Water in some springs and streams has either dissolved hydrothermal minerals or has reacted with them to add sulfate to the water. Some samples appear to have obtained their sulfate from dissolution of gypsum while some probably involve reaction with sulfide minerals such as pyrite. Light stable isotope data for water from springs follow a local meteoric water line, and the variation of isotopes with elevation indicate that some springs have very local recharge and others have water from elevations a few hundred meters higher. No evidence was found for thermal or slightly thermal springs on Mount Adams. A sample from a seeping gas vent on Mount Adams was at ambient temperature, but the gas is similar to that found on other Cascade volcanoes. Helium isotopes are 4.4 times the value in air, indicating that there is a significant component of mantle helium. The lack of fumaroles on Mount Adams and the ambient temperature of the gas indicates that the gas is from a hydrothermal system that is no longer active.

Washington↗

Geochemical analyses of ground-water ages, recharge rates, and hydraulic conductivity of the N aquifer, Black Mesa area, Arizona

The Navajo Nation and Hopi Tribe of the Black Mesa area, Arizona, depend on ground water from the N aquifer to meet most tribal and industrial needs. Increasing use of this aquifer is creating concerns about possible adverse effects of increased ground-water withdrawals on the water resources of the region. A thorough understanding of the N aquifer is necessary to assess the aquifer's response to ground-water withdrawals. This study used geochemical techniques as an independent means of improving the conceptual model of ground-water flow in the N aquifer and to estimate recharge rates and hydraulic conductivity. Ground water flows in a south-southeastward direction from the recharge area around Shonto into the confined part of the N aquifer underneath Black Mesa. Ground-water flow paths diverge in the confined part of the aquifer to the northeast and south. The N aquifer thins to extinction south of Black Mesa. This discontinuity could force ground water to diverge along paths of least resistance. Ground water discharges from the confined part of the aquifer into Laguna Creek and Moenkopi Wash and from springs southwest of Kykotsmovi and southeast of Rough Rock after a residence time of about 35,000 years or more. Recent recharge along the periphery of Black Mesa mixes with older ground water that discharges from the confined part of the aquifer and flows away from Black Mesa. Dissolved-ion concentrations, ratios of dissolved ions, dissolved-gas concentrations, tritium, carbon-13, and chlorine-36 data indicate that water in the overlying D aquifer could be leaking into the confined part of the N aquifer in the southeastern part of Black Mesa. The boundary between the leaky and nonleaky zones is defined roughly by a line from Rough Rock to Second Mesa and separates ground waters that have significantly different chemistries. The Dakota Sandstone and Entrada Formation of the D aquifer could be the sources of leakage. Adjusted radiocarbon ground-water ages and data on isotopes of oxygen and hydrogen indicate that more than 90 percent of the water in the confined part of the N aquifer is older than 10,000 years and was recharged during glacial periods. Estimates of recharge rates made on the basis of ground-water ages, aquifer thicknesses, and assumed porosities indicate that the annual average recharge rate in the northwestern part of the study area during the glacial periods was about four times the average annual rate of the past 10,000 years, and that recharge rates for the past 10,000 years are less than modern recharge rates assumed in a previous study. Estimates of horizontal hydraulic conductivity were 0.95 and 1.16 feet per day for the northeast and southwest flow paths, respectively. These values are within the range of hydraulic conductivities calculated from aquifer tests, which ranged from 0.05 to 2.1 feet per day and averaged 0.65 foot per day.

Arizona↗

National Research Program of the Water Resources Division, U.S. Geological Survey: Fiscal Year 1988

The National Research Program (NRP) of the US Geological Survey 's Water Resources Division (WRD) had its beginnings in the late 1950 's when ' core research ' was added as a line item to the Congressional budget. Since that time, the NRP has grown to encompass a broad spectrum of scientific investigations. The sciences of hydrology, mathematics, chemistry, physics, ecology, biology, geology, and engineering are used to gain a fundamental understanding of the processes that affect the availability, movement, and quality of the Nation 's water resources. The NRP is located principally in Reston, VA, Denver, CO, and Menlo Park , CA. The NRP is subdivided into six disciplines as follows: (1) Ecology; (2) Geomorphology and Sediment Transport; (3) Groundwater Chemistry; (4) Groundwater Hydrology; (5) Surface Water Chemistry; and (6) Surface Water Hydrology. The report provides current information about the NRP on an annual basis. Organized by the six research disciplines, the volume contains a summary of the problem, objective, approach, and progress for each project that was active during fiscal year 1988.

Open-File Report↗

Water resources data, North Dakota, water year 1998. Volume 1: Surface water

Water-resources data for the 1998 water year for North Dakota consists of records of discharge, stage, and water quality for streams; contents, stage, and water quality for lakes and reservoirs; and water levels and water quality for ground-water wells. Volume 1 contains records of water discharge for 97 streamflow-gaging stations; stage only for 22 river-stage stations; contents and/or stage for 12 lake or reservoir stations; annual maximum discharge for 32 crest-stage stations; and water-quality for 99 streamflow-gaging stations, 3 river-stage stations, 9 lake or reservoir stations, and several miscellaneous sample sites on streams and lakes. Also included are water-quality data for 2 precipitation-chemistry stations. These data represent that part of the National Water Data System operated by the U.S. Geological Survey and cooperating Federal, State, and local agencies in North Dakota.

North Dakota↗

Effects of historical coal mining and drainage from abandoned mines on streamflow and water quality in Bear Creek, Dauphin County, Pennsylvania — March 1999–December 2002

More than 100 years of anthracite coal mining has changed surface- and ground-water hydrology and contaminated streams draining the Southern Anthracite Coal Field in east-central Pennsylvania. Bear Creek drains the western prong of the Southern Anthracite Coal Field and is affected by metals in drainage from abandoned mines and streamwater losses. Total Maximum Daily Loads (TMDL) developed for dissolved iron of about 5 lb/d (pounds per day) commonly are exceeded in the reach downstream of mine discharges. Restoration of Bear Creek using aerobic ponds to passively remove iron in abandoned mine drainage is under consideration (2004) by the Dauphin County Conservation District. This report, prepared in cooperation with the Dauphin County Conservation District, evaluates chemical and hydrologic data collected in Bear Creek and its receiving waters prior to implementation of mine-drainage treatment. The data collected represent the type of baseline information needed for documentation of water-quality changes following passive treatment of mine drainage in Pennsylvania and in other similar hydrogeologic settings. Seven surface-water sites on Bear Creek and two mine discharges were monitored for nearly three years to characterize the chemistry and hydrology of the following: (1) Bear Creek upstream of the mine discharges (BC-UMD), (2) water draining from the Lykens-Williamstown Mine Pool at the Lykens Water-Level Tunnel (LWLT) and Lykens Drift (LD) discharges, (3) Bear Creek after mixing with the mine discharges (BC-DMD), and (4) Bear Creek prior to mixing with Wiconisco Creek (BCM). Two sites on Wiconisco Creek, upstream and downstream of Bear Creek (WC-UBC and WC-DBC, respectively), were selected to evaluate changes in streamflow and water quality upon mixing with Bear Creek. During periods of below-normal precipitation, streamwater loss was commonly 100 percent upstream of site BC-UMD (streamflow range = 0 to 9.7 ft3/s (cubic feet per second)) but no loss was detected downstream owing to sustained mine water drainage from the Lykens Water-Level Tunnel (range = 0.41 to 3.7 ft3/s), Lykens Drift (range = 0.40 to 6.1 ft3/s), and diffuse zones of seepage. Collectively, mine water inputs contributed about 84 percent of base flow and 53 percent of stormflow measured in the downstream reach. An option under consideration by the Dauphin County Conservation District for treatment of the discharge from the LWLT requires the source of the discharge to be captured and rerouted downstream, bypassing approximately 1,000 feet of stream channel. Because streamwater loss upstream of the tunnel was commonly 100 percent, rerouting the discharge from the LWLT may extend the reach of Bear Creek that is subject to dryness. Differences in the chemistry of water discharging from the LWLT compared to the LD suggest that the flow path through the Lykens-Williamstown Mine Pool to each mine discharge is unique. The LWLT is marginally alkaline (median net acid neutralizing capacity (ANC) = 9 mg/L (milligrams per liter) as CaCO3; median pH = 5.9), commonly becomes acidic (minimum net ANC = -74 mg/L as CaCO3) at low flow, and may benefit from alkaline amendments prior to passive treatment. Water discharging from the LD provides excess ANC (median net ANC = 123 mg/L as CaCO3; median pH = 6.5) to the downstream reach and is nearly anoxic at its source (median dissolved oxygen = 0.5 mg/L). Low dissolved oxygen water with relatively high ANC and metals concentrations discharging from the LD is characteristic of a deeper flow path and longer residence time within the mine pool than the more acidic, oxygenated water discharging from the LWLT. TMDLs for iron have been developed for dissolved species only. Consequently, distinguishing between dissolved and suspended iron in Bear Creek is important for evaluating water-quality improvement through TMDL attainment. Median total iron concentration increased from 550 mg/L (micrograms per liter) at site BC-UM

Pennsylvania↗

Major and trace element composition of copiapite-group minerals and coexisting water from the Richmond mine, Iron Mountain, California

Copiapite-group minerals of the general formula AR 4 (SO 4 ) 6 (OH) 2 · n H 2 O, where A is predominantly Mg, Fe 2+ , or 0.67Al 3+ , R is predominantly Fe 3+ , and n is typically 20, are among several secondary hydrous Fe sulfates occurring in the inactive mine workings of the massive sulfide deposit at Iron Mountain, CA, a USEPA Superfund site that produces extremely acidic drainage. Samples of copiapite-group minerals, some with coexisting water, were collected from the Richmond mine. Approximately 200 mL of brownish pore water with a pH of −0.9 were extracted through centrifugation from a 10-L sample of moist copiapite-group minerals taken from pyritic muck piles. The pore water is extremely rich in ferric iron (Fe 3+ =149 g L −1 , Fe T =162 g L −1 ) and has a density of 1.52 g mL −1 . The composition of the pore water is interpreted in the context of published phase relations in the Fe 2 O 3 –SO 3 –H 2 O system and previous work on the chemistry of extremely acid mine waters and associated minerals in the Richmond mine. Two distinct members of the copiapite mineral group were identified in the samples with coexisting water: (1) abundant magnesiocopiapite consisting of platy crystals 10 to 50 μm and (2) minor aluminocopiapite present as smaller platy crystals that form spheroidal aggregates. The average composition ( n =5) of the magnesiocopiapite is (Mg 0.90 Fe 2+ 0.17 Zn 0.02 Cu 0.01 ) ∑1.10 (Fe 3+ 3.83 Al 0.09 ) ∑3.92 (SO 4 ) 6.00 (OH) 1.96 ·20H 2 O. Bulk compositions determined by digestion and wet-chemical analysis are consistent with the microanalytical results. These results suggest that magnesiocopiapite is the least soluble member of the copiapite group under the prevailing conditions. Micro-PIXE analysis indicates that the copiapite-group minerals in this sample sequester Zn (average 1420 ppm), with lesser amounts of Cu (average 270 ppm) and As (average 64 ppm).

Chemical Geology↗

Reproducibility of geochemical and climatic signals in the Atlantic coral Montastraea faveolata

Monthly resolved, 41-year-long stable isotopic and elemental ratio time series were generated from two separate heads of Montastraea faveolata from Looe Key, Florida, to assess the fidelity of using geochemical variations in Montastraea, the dominant reef-building coral of the Atlantic, to reconstruct sea surface environmental conditions at this site. The stable isotope time series of the two corals replicate well; mean values of ??18O and ??13C are indistinguishable between cores (compare 0.70??? versus 0.68??? for ??13C and -3.90??? versus - 3.94??? for ??18O). Mean values from the Sr/Ca time series differ by 0.037 mmol/mol, which is outside of analytical error and indicates that nonenvironmental factors are influencing the coral Sr/ Ca records at Looe Key. We have generated significant ?? 18O-sea surface temperature (SST) (R = -0.84) and Sr/ Ca-SST (R = -0.86) calibration equations at Looe Key; however, these equations are different from previously published equations for Montastraea. Variations in growth parameters or kinetic effects are not sufficient to explain either the observed differences in the mean offset between Sr/Ca time series or the disagreement between previous calibrations and our calculated ??18O-SST and Sr/Ca-SST relationships. Calibration differences are most likely due to variations in seawater chemistry in the continentally influenced waters at Looe Key. Additional geochemical replication studies of Montastraea are needed and should include multiple coral heads from open ocean localities complemented whenever possible by seawater chemistry determinations. Copyright 2006 by the American Geophysical Union.

Paleoceanography↗

Quality of groundwater in the Denver Basin aquifer system, Colorado, 2003-5

Groundwater resources from alluvial and bedrock aquifers of the Denver Basin are critical for municipal, domestic, and agricultural uses in Colorado along the eastern front of the Rocky Mountains. Rapid and widespread urban development, primarily along the western boundary of the Denver Basin, has approximately doubled the population since about 1970, and much of the population depends on groundwater for water supply. As part of the National Water-Quality Assessment Program, the U.S. Geological Survey conducted groundwater-quality studies during 2003–5 in the Denver Basin aquifer system to characterize water quality of shallow groundwater at the water table and of the bedrock aquifers, which are important drinking-water resources. For the Denver Basin, water-quality constituents of concern for human health or because they might otherwise limit use of water include total dissolved solids, fluoride, sulfate, nitrate, iron, manganese, selenium, radon, uranium, arsenic, pesticides, and volatile organic compounds. For the water-table studies, two monitoring-well networks were installed and sampled beneath agricultural (31 wells) and urban (29 wells) land uses at or just below the water table in either alluvial material or near-surface bedrock. For the bedrock-aquifer studies, domestic- and municipal-supply wells completed in the bedrock aquifers were sampled. The bedrock aquifers, stratigraphically from youngest (shallowest) to oldest (deepest), are the Dawson, Denver, Arapahoe, and Laramie-Fox Hills aquifers. The extensive dataset collected from wells completed in the bedrock aquifers (79 samples) provides the opportunity to evaluate factors and processes affecting water quality and to establish a baseline that can be used to characterize future changes in groundwater quality. Groundwater samples were analyzed for inorganic, organic, isotopic, and age-dating constituents and tracers. This report discusses spatial and statistical distributions of chemical constituents and evaluates natural and human-related processes that affect water quality. Findings are synthesized to assess the vulnerability of the Denver Basin aquifer system to groundwater contamination. The chemistry of groundwater samples collected from the water-table wells was generally different from that of samples collected from the bedrock-aquifer wells. Samples from the water-table wells tended to have higher concentrations of total dissolved solids and most major ions. Concentrations of several constituents with potential human-health concerns, including nitrate, selenium, uranium, and arsenic, decreased with depth and were highest in samples from the water-table wells. Exceedances of drinking-water standards and water-quality benchmarks were more frequently associated with shallow groundwater samples; concentrations of total dissolved solids and sulfate exceeded water-quality benchmarks for about half or more of samples from the water-table wells. The sediments and rocks of the Denver Basin are natural sources of the trace elements selenium, uranium, and arsenic, which affect their concentrations in groundwater. Detections of organic contaminants, which are typically indicative of human sources of contamination to groundwater, were more frequent in samples from the water-table wells. Pesticide compounds and volatile organic compounds were detected in 33 and 62 percent, respectively, of water-table well samples. Detected organic contaminant concentrations were much less than the associated drinking-water standards. Samples collected from the bedrock aquifers had lower concentrations of total dissolved solids than did samples collected from the water-table wells, although within the bedrock-aquifer samples, concentrations increased from the Dawson to Denver to Arapahoe to Laramie-Fox Hills aquifers. Concentrations of total dissolved solids and many constituents varied spatially and with depth in the bedrock aquifers, likely as a result of ion-exchange and oxidation-reduction reactions, which are important processes affecting water quality. Major-ion chemistry generally evolved from a calcium-bicarbonate to calcium-sulfate composition, with some sodium-bicarbonate and sodium-sulfate facies in the deeper bedrock aquifers, likely resulting from longer residence times and more extensive water-rock interaction. Oxidation-reduction conditions generally evolved from oxic at the water table to anoxic with increasing depth in the bedrock aquifers. Most samples from the bedrock aquifers were anoxic. Exceedances of drinking-water standards and water-quality benchmarks for the bedrock aquifers occurred in 1 percent or less of samples for nitrate, selenium, or arsenic; there were no exceedances for uranium. Exceedances for total dissolved solids, sulfate, manganese, and iron were generally between about 10 and 20 percent for the bedrock-aquifer samples. Radon concentrations, which were only measured in samples collected from two of the bedrock aquifers, exceeded the lower proposed drinking-water standard for more than 90 percent of samples but exceeded the higher alternative standard for less than 5 percent of samples. Pesticide compounds and volatile organic compounds were detected in 3 and 22 percent, respectively, of bedrock-aquifer samples, all at concentrations that were that were much less than drinking-water standards. Water-quality data were synthesized to evaluate factors that affect spatial and depth variability in water quality and to assess aquifer vulnerability to contaminants from geologic materials and those of human origin. The quality of shallow groundwater in the alluvial aquifer and shallow bedrock aquifer system has been adversely affected by development of agricultural and urban areas. Land use has altered the pattern and composition of recharge. Increased recharge from irrigation water has mobilized dissolved constituents and increased concentrations in the shallow groundwater. Concentrations of most constituents associated with poor or degraded water quality in shallow groundwater decreased with depth; many of these constituents are not geochemically conservative and are affected by geochemical reactions such as oxidation-reduction reactions. Groundwater age tracers provide additional insight into aquifer vulnerability and help determine if young groundwater of potentially poor quality has migrated to deeper parts of the bedrock aquifers used for drinking-water supply. Age-tracer results were used to group samples into categories of young, mixed, and old groundwater. Groundwater ages transitioned from mostly young in the water-table wells to mostly mixed in the shallowest bedrock aquifer, the Dawson aquifer, to mostly old in the deeper bedrock aquifers. Although the bedrock aquifers are mostly old groundwater of good water quality, several lines of evidence indicate that young, contaminant-bearing recharge has reached shallow to moderate depths in some areas of the bedrock aquifers. The Dawson aquifer is the most vulnerable of the bedrock aquifers to contamination, but results indicate that the older (deeper) bedrock aquifers are also vulnerable to groundwater contamination and that mixing with young recharge has occurred in some areas. Heavy pumping has caused water-level declines in the bedrock aquifers in some parts of the Denver Basin, which has the potential to enhance the transport of contaminants from overlying units. Results of this study are consistent with the existing conceptual understanding of aquifer processes and groundwater issues in the Denver Basin and add new insight into the vulnerability of the bedrock aquifers to groundwater contamination.

Colorado↗

Geochemistry of the Madison and Minnelusa aquifers in the Black Hills area, South Dakota

The Madison and Minnelusa aquifers are two of the most important aquifers in the Black Hills area because of utilization for water supplies and important influences on surface-water resources resulting from large springs and streamflow- loss zones. Examination of geochemical information provides a better understanding of the complex flow systems within these aquifers and interactions between the aquifers. Major-ion chemistry in both aquifers is dominated by calcium and bicarbonate near outcrop areas, with basinward evolution towards various other water types. The most notable differences in major-ion chemistry between the Madison and Minnelusa aquifers are in concentrations of sulfate within the Minnelusa aquifer. Sulfate concentrations increase dramatically near a transition zone where dissolution of anhydrite is actively occurring. Water chemistry for the Madison and Minnelusa aquifers is controlled by reactions among calcite, dolomite, and anhydrite. Saturation indices for gypsum, calcite, and dolomite for most samples in both the Madison and Minnelusa aquifers are indicative of the occurrence of dedolomitization. Because water in the Madison aquifer remains undersaturated with respect to gypsum, even at the highest sulfate concentrations, upward leakage into the overlying Minnelusa aquifer has potential to drive increased dissolution of anhydrite in the Minnelusa Formation. Isotopic information is used to evaluate ground-water flowpaths, ages, and mixing conditions for the Madison and Minnelusa aquifers. Distinctive patterns exist in the distribution of stable isotopes of oxygen and hydrogen in precipitation for the Black Hills area, with isotopically lighter precipitation generally occurring at higher elevations and latitudes. Distributions of 18O in ground water are consistent with spatial patterns in recharge areas, with isotopically lighter 18O values in the Madison aquifer resulting from generally higher elevation recharge sources, relative to the Minnelusa aquifer. Three conceptual models, which are simplifications of lumped-parameter models, are considered for evaluation of mixing conditions and general ground-water ages. For a simple slug-flow model, which assumes no mixing, measured tritium concentrations in ground water can be related through a first-order decay equation to estimated concentrations at the time of recharge. Two simplified mixing models that assume equal proportions of annual recharge over a range of years also are considered. An ?immediate-arrival? model is used to conceptually represent conditions in outcrop areas and a ?time-delay? model is used for locations removed from outcrops, where delay times for earliest arrival of ground water generally would be expected. Because of limitations associated with estimating tritium input and gross simplifying assumptions of equal annual recharge and thorough mixing conditions, the conceptual models are used only for general evaluation of mixing conditions and approximation of age ranges. Headwater springs, which are located in or near outcrop areas, have the highest tritium concentrations, which is consistent with the immediate-arrival mixing model. Tritium concentrations for many wells are very low, or nondetectable, indicating general applicability of the timedelay conceptual model for locations beyond outcrop areas, where artesian conditions generally occur. Concentrations for artesian springs generally are higher than for wells, which indicates generally shorter delay times resulting from preferential flowpaths that typically are associated with artesian springs. In the Rapid City area, a distinct division of isotopic values for the Madison aquifer corresponds with distinguishing 18O signatures for nearby streams, where large streamflow recharge occurs. Previous dye testing in this area documented rapid ground-water flow (timeframe of weeks) from a streamflow loss zone to sites located several miles away. These results are used to ill

Water-Resources Investigations Report↗

Processes affecting δ34S and δ18O values of dissolved sulfate in alluvium along the Canadian River, central Oklahoma, USA

The δ 34 S and δ 18 O values for dissolved sulfate in groundwater are commonly used in aquifer studies to identify sulfate reservoirs and describe biogeochemical processes. The utility of these data, however, often is compromised by mixing of sulfate sources within reservoirs and isotope fractionation during sulfur redox cycling. Our study shows that, after all potential sulfate sources are identified and isotopically characterized, the δ 34 S SO4 and δ 18 O SO4 values differentiate processes such as sulfate-source mixing, sulfide oxidation, barite dissolution, and organosulfur decomposition. During bacterial reduction of sulfate, the values reflect kinetic sulfur isotope fractionation and exchange of oxygen isotopes between sulfate and water. Detailed analysis of the chemistry (Cl and SO 4 concentrations) and isotopic composition (δ 2 H H2O and δ 18 O H2O ) of groundwater in an alluvial aquifer in Central Oklahoma, USA allowed the identification of five distinct end members that supply water to the aquifer (regional groundwater flowing into the study area, river water, leachate from a closed landfill that operated within the site, rain, and surface runoff). The δ 34 S SO4 and δ 18 O SO4 values in each end member differentiated three sources of sulfate: sulfate dissolved from Early to Late Permian rocks within the drainage basin (δ 34 S SO4 = 8–12‰ and δ 18 O SO4 = 10‰), iron sulfides oxidized by molecular oxygen during low water-table levels (δ 34 S SO4 = − 16‰ and δ 18 O SO4 = 10‰), and organosulfur compounds (predominately ester sulfates) from decomposition of vegetation on the surface and from landfill trash buried in the alluvium (δ 34 S SO4 = 8‰ and δ 18 O SO4 = 6‰). During bacterial reduction of these sulfate sources, similar isotope fractionation processes are recorded in the parallel trends of increasing δ 34 S SO4 and δ 18 O SO4 values. When extensive reduction occurs, the kinetic sulfur isotope fractionation (estimated by ε H2S–SO4 = − 23‰) results in the steady increase of δ 34 S SO4 values to greater than 70‰. Equilibrium isotope fractionation during exchange of sulfate oxygen and water oxygen, a process not commonly observed in field-based studies, is documented in δ 18 O SO4 values asymptotically approaching 21‰, the value predicted for conditions at the study site ( ε SO4–H2O = 27‰). These results show that recognition of all potential sulfate sources is a critical first step to resolving complexities in δ 34 S SO4 and δ 18 O SO4 data. The approach taken in this study can be used in other aquifer systems where the identification of multiple sulfate sources and sulfur redox cycling is important to understanding natural processes and anthropogenic influences.

Oklahoma↗

Characterization of dissolved organic materials in surface waters within the blast zone of Mount St Helens, Washington

After the May 18, 1980, eruption of Mount St Helens, the concentration of dissolved organic material in surface waters near the volcano increased significantly as a result of the destruction of the surrounding conifer forest. Low molecular weight organic compounds identified in the blast zone surface waters were derived from pyrolysis of plant and soil organic materials incorporated into pyroclastic flow, mud flow and debris avalanche deposits. A major fraction of the dissolved organic material consisted of high molecular weight, colored, organic acids that are similar in their general properties to aquatic fulvic acids found in more typical surface waters except for greater sulfur contents. The other major fraction of the dissolved organic material consisted of hydrophilic acids, which may include compounds capable of supporting heterotrophic microorganisms, and precursors in the formation of aquatic fulvic acids. The organic chemistry of blast zone surface waters will probably be greatly influenced by the May 18, 1980, eruption for many years.

Washington↗

Limited occurrence of denitrification in four shallow aquifers in agricultural areas of the United States

The ability of natural attenuation to mitigate agricultural nitrate contamination in recharging aquifers was investigated in four important agricultural settings in the United States. The study used laboratory analyses, field measurements, and flow and transport modeling for monitoring well transects (0.5 to 2.5 km in length) in the San Joaquin watershed, California, the Elkhorn watershed, Nebraska, the Yakima watershed, Washington, and the Chester watershed, Maryland. Ground water analyses included major ion chemistry, dissolved gases, nitrogen and oxygen stable isotopes, and estimates of recharge date. Sediment analyses included potential electron donors and stable nitrogen and carbon isotopes. Within each site and among aquifer-based medians, dissolved oxygen decreases with ground water age, and excess N 2 from denitrification increases with age. Stable isotopes and excess N 2 imply minimal denitrifying activity at the Maryland and Washington sites, partial denitrification at the California site, and total denitrification across portions of the Nebraska site. At all sites, recharging electron donor concentrations are not sufficient to account for the losses of dissolved oxygen and nitrate, implying that relict, solid phase electron donors drive redox reactions. Zero-order rates of denitrification range from 0 to 0.14 μmol N L −1 d −1 , comparable to observations of other studies using the same methods. Many values reported in the literature are, however, orders of magnitude higher, which is attributed to a combination of method limitations and bias for selection of sites with rapid denitrification. In the shallow aquifers below these agricultural fields, denitrification is limited in extent and will require residence times of decades or longer to mitigate modern nitrate contamination.

Journal of Environmental Quality↗

The concept of hydrologic landscapes

Hydrologic landscapes are multiples or variations of fundamental hydrologic landscape units. A fundamental hydrologic landscape unit is defined on the basis of land-surface form, geology, and climate. The basic land-surface form of a fundamental hydrologic landscape unit is an upland separated from a lowland by an intervening steeper slope. Fundamental hydrologic landscape units have a complete hydrologic system consisting of surface runoff, ground-water flow, and interaction with atmospheric water. By describing actual landscapes in terms of land-surface slope, hydraulic properties of soils and geologic framework, and the difference between precipitation and evapotranspiration, the hydrologic system of actual landscapes can be conceptualized in a uniform way. This conceptual framework can then be the foundation for design of studies and data networks, syntheses of information on local to national scales, and comparison of process research across small study units in a variety of settings. The Crow Wing River watershed in central Minnesota is used as an example of evaluating stream discharge in the context of hydrologic landscapes. Lake-research watersheds in Wisconsin, Minnesota, North Dakota, and Nebraska are used as an example of using the hydrologic-landscapes concept to evaluate the effect of ground water on the degree of mineralization and major-ion chemistry of lakes that lie within ground-water flow systems.

Minnesota, Nebraska, North Dakota, Wisconsin↗

The geochemistry of water near a surficial organic-rich uranium deposit, northeastern Washington State, U.S.A.

The chemistry of three stream, three spring and six near-surface waters in the vicinity of a Holocene organic-rich uranium deposit is described, with particular emphasis on the chemistry of U. Results characterize the solution behavior of uranium as U-bearing water interacts with relatively undecomposed, surficial organic matter. Of the measured major and trace chemical species, only U is consistently highly enriched (17-318 ppb) relative to reported values for regional waters, or to literature values for waters in largely granitic terrains. R-mode factor analysis of the chemical data suggests that most U is present in a soluble form, but that some U is also associated with fine suspended particulates of clay, organic matter, or hydrous oxides. Calculations that apply thermodynamic data to predict U speciation in solution indicate the relative importance of uranyl carbonate and uranyl phosphate complexes. Analysis of more finely filtered samples (0.05 ??m vs. 0.45 ??m), and direct radiographic observations using fission-track detectors suspended in the waters indicate the presence of some uraniferous particulate matter. Application of existing thermodynamic data for uranous- and uranyl-bearing minerals indicates that all waters are undersaturated with U minerals as long as ambient Eh ??? +0.1 v. If coexisting surface and near-surface waters are sufficiently oxidizing, initial fixation of U in the deposit should be by a mechanism of adsorption. Alternatively, more reducing conditions may prevail in deeper pore waters of the organic-rich host sediments, perhaps leading to direct precipitation or diagenetic formation of U4+ minerals. A 234U 238U alpha activity ratio of 1.08 ?? 0.02 in a spring issuing from a hillslope above the deposit suggests a relatively soluble source of U. In contrast, higher activity ratios of 234U 238U (??? 1.3) in waters in contact with the uraniferous valley-fill sediments suggest differences in the nature of interaction between groundwater and the local, U-rich source rocks. ?? 1987.

Chemical Geology↗

Hydrogeology and water quality at the management systems evaluation area near Piketon, Ohio

This report presents the results of a study by the U.S. Geological Survey, The Ohio State University, and the U.S. Department of Agriculture to describe the hydrology, water quality, and geochemical factors controlling water quality at the Ohio Management Systems Evaluation Area (MSEA). The Ohio MSEA is located on a 650-acre farm in the Scioto River Valley in Pike County, south-central Ohio. The farm is underlain by an incised bedrock valley filled with about 70 feet of sand and gravel outwash deposits that are covered by a veneer of silty clay alluvium and silty loam and sandy loam soils. Outwash sediment are composed predominantly of dolomite, quartz, and calcite, and have a median organic carbon concentration of 0.39 weight percent. Horizontal hydraulic conductivity of the sediment based on results of multiple-well aquifer tests ranges from 400 to 560 feet per day. Ground-water flow is from east to west-southwest at an average velocity of 1.5 to 2.5 feet per day. Ground water and surface water at the site are highly interconnected. Big Beaver Creek recharges the outwash aquifer along the eastern edge of the study area, and ground water discharges to the Scioto River at the western edge of the study area. High-stage events on the Scioto River cause frequent flow reversals in the aquifer that allow streamwater to travel a maximum observed distance of 190 feet inland. A zone of oxidizing waters (characterized by high dissolved oxygen concentration and Eh) is found in shallow ground water for several hundred feet adjacent to Big Beaver Creek and the Scioto River. This zone of oxidizing ground water is caused by the periodic inflow of surface waters to the aquifer. A ground-water budget for the study area indicates that the aquifer received 17.7 inches of recharge during water year 1992; of this amount, 72 percent originated as infiltrating precipitation, 28 percent as infiltration of surface water from Big Beaver Creek, and 0.2 percent as leakage from bedrock. Areal variation in water quality is caused by areal differences in the relative importance of these three recharge sources. The effects of bedrock leakage are evident only in the northeast corner of the study area. Here, deep outwash waters are transitional in composition between the calcium magnesium bicarbonate waters found elsewhere in the outwash aquifer and the calcium sodium chloride waters of the bedrock aquifer. Mixing calculations indicate that these deep outwash waters are composed of as much as 26 percent bedrock water. In the southern part of the MSEA, ground water is diluted by surface water from Big Beaver Creek as it recharges the aquifer through a sand and gravel streambed. At the northeast corner of the MSEA, however, Big Beaver Creek flows across a shale streambed through which no infiltration occurs. Redox reactions in the outwash aquifer control variations in aquifer chemistry with depth. From the water table to about 40 feet below land surface, oxidizing conditions are characterized by the presence of dissolved oxygen and nitrates in ground water, Eh greater than 200 millivolts, ferrihydrite coatings on sediment grains, and the absence of dissolved iron and manganese. From about 40 feet below land surface to the base of the aquifer, reducing conditions are characterized by dissolved oxygen concentrations less than 2 mg/L, Eh less than 200 millivolts, and the presence of dissolved iron and manganese. Denitrification in the reducing zone naturally remediates anthropogenic nitrate contamination of the aquifer while oxidizing pyrite in the aquifer sediment.

Ohio↗

Questa baseline and pre-mining ground-water quality investigation. 25. Summary of results and baseline and pre-mining ground-water geochemistry, Red River Valley, Taos County, New Mexico, 2001-2005

Active and inactive mine sites are challenging to remediate because of their complexity and scale. Regulations meant to achieve environmental restoration at mine sites are equally challenging to apply for the same reasons. The goal of environmental restoration should be to restore contaminated mine sites, as closely as possible, to pre-mining conditions. Metalliferous mine sites in the Western United States are commonly located in hydrothermally altered and mineralized terrain in which pre-mining concentrations of metals were already anomalously high. Typically, those pre-mining concentrations were not measured, but sometimes they can be reconstructed using scientific inference. Molycorp?s Questa molybdenum mine in the Red River Valley, northern New Mexico, is located near the margin of the Questa caldera in a highly mineralized region. The State of New Mexico requires that ground-water quality standards be met on closure unless it can be shown that potential contaminant concentrations were higher than the standards before mining. No ground water at the mine site had been chemically analyzed before mining. The aim of this investigation, in cooperation with the New Mexico Environment Department (NMED), is to infer the pre-mining ground-water quality by an examination of the geologic, hydrologic, and geochemical controls on ground-water quality in a nearby, or proximal, analog site in the Straight Creek drainage basin. Twenty-seven reports contain details of investigations on the geological, hydrological, and geochemical characteristics of the Red River Valley that are summarized in this report. These studies include mapping of surface mineralogy by Airborne Visible-Infrared Imaging Spectrometry (AVIRIS); compilations of historical surface- and ground- water quality data; synoptic/tracer studies with mass loading and temporal water-quality trends of the Red River; reaction-transport modeling of the Red River; environmental geology of the Red River Valley; lake-sediment chemistry; geomorphology and its effect on ground-water flow; geophysical studies on depth to ground-water table and depth to bedrock; bedrock fractures and their potential influence on ground-water flow; leaching studies of scars and waste-rock piles; mineralogy and mineral chemistry and their effect on ground-water quality; debris-flow hazards; hydrology and water balance for the Red River Valley; ground-water geochemistry of selected wells undisturbed by mining in the Red River Valley; and quality assurance and quality control of water analyses. Studies aimed specifically at the Straight Creek natural-analog site include electrical surveys; high-resolution seismic survey; age-dating with tritium/helium; water budget; ground-water hydrology and geochemistry; and comparison of mineralogy and lithology to that of the mine site. The highly mineralized and hydrothermally altered volcanic rocks of the Red River Valley contain several percent pyrite in the quartz-sericite-pyrite (QSP) alteration zone, which weather naturally to acid-sulfate surface and ground waters that discharge to the Red River. Weathering of waste-rock piles containing pyrite also contributes acid water that eventually discharges into the Red River. These acid discharges are neutralized by circumneutral-pH, carbonate-buffered surface and ground waters of the Red River. The buffering capacity of the Red River, however, decreases from the town of Red River to the U.S. Geological Survey (USGS) gaging station near Questa. During short, but intense, storm events, the buffering capacity is exceeded and the river becomes acid from the rapid flushing of acidic materials from natural scar areas. The lithology, mineralogy, elevation, and hydrology of the Straight Creek proximal analog site were found to closely approximate those of the mine site with the exception of the mine site?s Sulphur Gulch catchment. Sulphur Gulch contains three subcatchments?upper Sulphur Gulch, Blind Gulch, and Spring Gulc

New Mexico↗

Geochemical Results of Lysimeter Sampling at the Manning Canyon Repository in the Mercur Mining District, Utah

This report presents chemical characteristics of transient unsaturated-zone water collected by lysimeter from the Manning Canyon repository site in Utah. Data collected by U.S. Geological Survey and U.S. Department of the Interior, Bureau of Land Management scientists under an intragovernmental order comprise the existing body of hydrochemical information on unsaturated-zone conditions at the site and represent the first effort to characterize the chemistry of the soil pore water surrounding the repository. Analyzed samples showed elevated levels of arsenic, barium, chromium, and strontium, which are typical of acidic mine drainage. The range of major-ion concentrations generally showed expected soil values. Although subsequent sampling is necessary to determine long-term effects of the repository, current results provide initial data concerning reactive processes of precipitation on the mine tailings and waste rock stored at the site and provide information on the effectiveness of reclamation operations at the Manning Canyon repository.

Data Series↗