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R. B. Wanty

Publications and source records attributed to R. B. Wanty.

At least 37 records · Page 2Linked to original sources

Development of a solenoid pumped in situ zinc analyzer for environmental monitoring

A battery powered submersible chemical analyzer, the Zn-DigiScan (Zn Digital Submersible Chemical Analyzer), has been developed for near real-time, in situ monitoring of zinc in aquatic systems. Microprocessor controlled solenoid pumps propel sample and carrier through an anion exchange column to separate zinc from interferences, add colorimetric reagents, and propel the reaction complex through a simple photometric detector. The Zn-DigiScan is capable of self-calibration with periodic injections of standards and blanks. The detection limit with this approach was 30 μg L −1 . Precision was 5–10% relative standard deviation (R.S.D.) below 100 μg L −1 , improving to 1% R.S.D. at 1000 μg L −1 . The linear range extended from 30 to 3000 μg L −1 . In situ field results were in agreement with samples analyzed by inductively coupled plasma mass spectrometry (ICPMS). This pump technology is quite versatile and colorimetric methods with complex online manipulations such as column reduction, preconcentration, and dilution can be performed with the DigiScan. However, long-term field deployments in shallow high altitude streams were hampered by air bubble formation in the photometric detector.

Analytica Chimica Acta↗

Engelmann Spruce (Picea engelmannii) as a biological monitor of changes in soil metal loading related to past mining activity

Engelmann spruce (Picea engelmannii) is the dominant tree species in many abandoned mine areas of the Rocky Mountains. It is long-lived, and therefore, may act as a long term biological monitor of changes in soil chemistry caused by past mining activity. In this study, laser ablation inductively coupled mass spectrometry (LA-ICPMS) was used to analyze individual tree rings of Engelmann spruce for Fe, Zn, Cu, Cd, Mn, Pb and Sr concentrations. Cores were obtained from trees growing in tailings-impacted and control (non-tailings impacted) sites near the Waldorf mine (Waldorf, CO, USA). Zinc, Cu, Fe, Cd, Pb and Sr concentrations remained low and consistent over time in the control tree rings. However, in the tailings impacted cores, concentrations of Zn, Cu, Fe and Cd increase significantly in post-mining rings. In addition, Zn, Cu, Fe, and Cd concentrations in pre-mining rings of both the control and tailings impacted cores are similar, indicating that present day soil concentrations of these elements in the control area are a reasonable estimation of background for this area. Lead and Sr concentrations in control and tailings-impacted rings remained similar and relatively constant through time and are not useful in determining changes in soil chemistry due to past mining activity. ?? 2004 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

Environmental behavior of two molybdenum porphyry systems

Our study focuses on the geology, hydrology, and geochemistry of a variety of molybdenum (Mo) porphyry systems. The systems are either high fluorine, granite, Climax-type, systems (e.g. Mount Emmons/ Redwell Mo deposit, Colorado and Questa Mo deposit, New Mexico) or low fluorine granodiorite systems (e.g. Buckingham Stockwork Mo deposit, Battle Mountain, Nevada and Cannivan Gulch Mo deposit, Montana). The water quality of streams, natural springs, mine discharge, and ground water from drill holes were assessed in the region of these deposits. The ultimate goal of our study is to understand the environmental behavior of these Mo porphyry systems in the context of geologic setting, hydrologic regime, and climate.

Conference Paper↗

Mobilization and attenuation of metals downstream from a base-metal mining site in the Matra Mountains, northeastern Hungary

Regional geochemical baseline values have been established for Hungary by the use of low-density stream-sediment surveys of flood-plain deposits of large drainage basins and of the fine fraction of stream sediments. The baseline values and anomaly thresholds thus produced helped to evaluate the importance of high toxic element concentrations found in soils in a valley downstream of a polymetallic vein-type base-metal mine. Erosion of the mine dumps and flotation dump, losses of metals during filtering, storage and transportation, human neglects, and operational breakdowns, have all contributed to the contamination of a small catchment basin in a procession of releases of solid waste. The sulfide-rich waste material weathers to a yellow color; this layer of 'yellow sand' blankets a narrow strip of the floodplain of Toka Creek in the valley near the town of Gyongyosoroszi. Contamination was spread out in the valley by floods. Metals present in the yellow sand include Pb, As, Cd, Cu, Zn, and Sb. Exposure of the local population to these metals may occur through inhalation of airborne particulates or by ingestion of these metals that are taken up by crops grown in the valley. To evaluate the areal extent and depth of the contamination, active stream sediment, flood-plain deposits, lake or reservoir sediments, soils, and surface water were sampled along the erosion pathways downstream of the mine and dumps. The flood-plain profile was sampled in detail to see the vertical distribution of elements and to relate the metal concentrations to the sedimentation and contamination histories of the flood plain. Downward migration of mobile Zn and Cd from the contaminated upper layers under supergene conditions is observed, while vertical migration of Pb, As, Hg and Sb appears to be insignificant. Soil profiles of 137Cs which originated from above-ground atomic bomb tests and the Chernobyl accident, provide good evidence that the upper 30-40 cm of the flood-plain sections, which includes the yellow sand contamination, were deposited in the last 30-40 years.The regional geochemical baseline values are established for Hungary using low-density stream-sediment surveys of flood-plain deposits of large drainage basins and of the fine fraction of stream sediments. The baseline values and anomaly thresholds allowed the evaluation of the importance of high toxic element concentrations in soils in a valley, downstream of a polymetallic vein-type base-metal mine. The metals present in the yellow sand include Pb, As, Cd, Cu, Zn and Sb. To evaluate the areal extent and depth of the contamination, active stream sediment, flood-plain deposits, lake or reservoir sediments, the soils and surface water were sampled along the erosion pathways downstream of the mine and dumps.

Journal of Geochemical Exploration↗

222Rn transport in a fractured crystalline rock aquifer: Results from numerical simulations

Dissolved 222Rn concentrations in ground water from a small wellfield underlain by fractured Middle Proterozoic Pikes Peak Granite southwest of Denver, Colorado range from 124 to 840 kBq m-3 (3360-22700 pCi L-1). Numerical simulations of flow and transport between two wells show that differences in equivalent hydraulic aperture of transmissive fractures, assuming a simplified two-fracture system and the parallel-plate model, can account for the different 222Rn concentrations in each well under steady-state conditions. Transient flow and transport simulations show that 222Rn concentrations along the fracture profile are influenced by 222Rn concentrations in the adjoining fracture and depend on boundary conditions, proximity of the pumping well to the fracture intersection, transmissivity of the conductive fractures, and pumping rate. Non-homogeneous distribution (point sources) of 222Rn parent radionuclides, uranium and 226Ra, can strongly perturb the dissolved 222Rn concentrations in a fracture system. Without detailed information on the geometry and hydraulic properties of the connected fracture system, it may be impossible to distinguish the influence of factors controlling 222Rn distribution or to determine location of 222Rn point sources in the field in areas where ground water exhibits moderate 222Rn concentrations. Flow and transport simulations of a hypothetical multifracture system consisting of ten connected fractures, each 10 m in length with fracture apertures ranging from 0.1 to 1.0 mm, show that 222Rn concentrations at the pumping well can vary significantly over time. Assuming parallel-plate flow, transmissivities of the hypothetical system vary over four orders of magnitude because transmissivity varies with the cube of fracture aperture. The extreme hydraulic heterogeneity of the simple hypothetical system leads to widely ranging 222Rn values, even assuming homogeneous distribution of uranium and 226Ra along fracture walls. Consequently, it is concluded that 222Rn concentrations vary, not only with the geometric and stress factors noted above, but also according to local fracture aperture distribution, local groundwater residence time, and flux of 222Rn from parent radionuclides along fracture walls.

Journal of Hydrology↗

Hydrogeologic and water-quality data used to evaluate the effects of focused recharge on ground-water quality near Princeton, Minnesota, 1991-95

This study was part of the Management Systems Evaluation Area (MSEA) Program, a multi-scale, inter-agency initiative to evaluate the effects of agricultural systems on water quality in the midwest corn belt. The research was part of the U.S. Geological Survey Toxics Substances Hydrology Program. The research area was located in the Anoka Sand Plain about 5 kilometers southwest of Princeton, Minnesota. This report presents temperature, precipitation, soil-moisture, water-quality, and other data collected during 1991-95 to evaluate the effects of focused recharge on ground-water quality at the Princeton MSEA.

Minnesota↗

Relationships between 222Rn dissolved in ground water supplies and indoor 222Rn concentrations in some Colorado front range houses

Indoor 222Rn concentrations were measured in 37 houses with alpha track detectors placed in water-use rooms near water sources (bathrooms, laundry rooms, and kitchens) and in non-water-use living rooms, dining rooms, and bedrooms away from water sources. Results show that relative contributions of 222Rn to indoor air from water use are insignificant when soil-gas concentrations are high but become increasingly important as the ratio of 222Rn-in-water:222Rn-in-soil gas increases. High soil-gas 222Rn concentrations may mask 222Rn contributions from water even when waterborne 222Rn concentrations are as high as 750 kBq m-3. Ground water in Precambrian Pikes Peak granite averages 340 kBq m-3222Rn, vs. 170 kBq m-3 in Precambrian migmatite, but average 222Rn concentrations in soil gas are also lower in migmatite. Because the ratio of 222Rn-in- water:222Rn-in-soil gas may be consistently higher for houses in migmatite than in Pikes Peak granite, indoor air in houses built on migmatite may have a greater relative contribution from water use even though average 222Rn concentrations in the water are lower. Continuous monitoring of 222Rn concentrations in air on 15-min intervals also indicates that additions to indoor concentrations from water use are significant and measurable only when soil-gas concentrations are low and concentrations in water are high. When soil-gas concentrations were mitigated to less than 150 Bq m-3 in one house, water contributes 20-40% of the annual indoor 222Rn concentration in the laundry room (222Rn concentration in water of 670 kBq m-3). Conversely, when the mitigation system is inactive, diurnal fluctuations and other variations in the soil-gas 222Rn contribution swamp the variability due to water use in the house. Measurable variations in indoor concentrations from water use were not detected in one house despite a low soil-gas contribution of approximately 150 Bq m-3 because waterborne 222Rn concentrations also are low (80 kBq m-3). This result suggests that 222Rn concentrations in water near the recommended EPA limit in drinking water of 11 kBq m-3 may not contribute measurable amounts of 222Rn to indoor air in most houses.

Health Physics↗

Thermodynamics and kinetics of reactions involving vanadium in natural systems: Accumulation of vanadium in sedimentary rocks

A critical review of thermodynamic data for aqueous and solid V species is presented to evaluate dissolution, transport, and precipitation of V under natural conditions. Emphasis is given to results of experimental studies of V chemistry, especially those for which the experimental conditions are near those found in nature. Where possible, data are obtained for or corrected to the reference conditions of 298.15K, 1 atm (1.01325 bar) and zero ionic strength. Vanadium [IV] (V IV ) and vanadium[V] (V V ) are the most soluble forms of V in nature, and their complexes with fluoride, sulfate, and oxalate may act to increase V solubility under oxidizing conditions. Because redox behavior is of fundamental importance to understanding natural V chemistry, the kinetics of reduction of V IV to V III H 2 S were studied. Although H 2 S is predicted from thermodynamic data to be capable of reducing V IV to V III , this reaction has not been demonstrated experimentally. Experiments were carried out under conditions of temperature (45°C), pH (3.6–6.8), ionic strength (0.05–0.1 m), and V concentrations (9.8–240 μmolar) likely to be found in nature. Because the reaction is very slow, H 2 S concentrations in excess of natural conditions were used (8.1 × 10 −4 to 0.41 atm). The results show that V IV is reduced to V III under a variety of conditions. The rate increases with increasing pH, but is not appreciably affected by ionic strength (as represented by the concentration of KCl, which was used as the supporting electrolyte in all cases). Prior to initiation of the reaction, there is an induction period, the length of which increases with increasing KCl concentration or decreasing pH. Attempts to model the reaction mechanism by numerical methods have failed to produce a satisfying fit of the results, indicating partial reaction orders, a complex mechanism, or involvement of a variety of intermediate species. The results of the thermodynamic and kinetic studies were applied to understanding the genesis of V deposits such as those commonly found on the Colorado Plateau. Vanadium in these sandstone-hosted deposits is present mostly in the reduced oxidation state, V III . Because of the insolubility of V III oxyhydroxides, it is likely that a more oxidized form of V (either [IV] or [V]) was transported to the site of mineralization, and that the V was reduced in situ and subsequently precipitated. A probable reductant is hydrogen sulfide; the presence of pyrite cogenetic with the V minerals documents the presence of H 2 S during mineralization. The experiments described here show that H 2 S could have reduced V IV to V III , and thus led to the formation of these deposits.

Geochimica et Cosmochimica Acta↗

Contribution of 222Rn in domestic water supplies to 222Rn in indoor air in Colorado homes

The contribution of 222Rn from domestic water wells to indoor air was investigated in a study of 28 houses near Conifer, CO. Air concentrations determined by alpha-track detectors (ATDs) and continuous radon monitors were compared with the predictions of a single-cell model. In many of the houses, the water supply was shown to contribute significantly to levels of indoor 222Rn. The data from the ATD study were augmented with a continuous monitoring study of a house near Lyons, CO. The well water in that house has the highest known concentration of 222Rn in water yet reported (93 MBq m-3). The temporal pattern in the indoor 222Rn concentration corresponds to water-use records. In general, it is difficult to quantify the proportion of indoor radon attributable to water use. Several lines of evidence suggest that the single-cell model underestimates this proportion. Continuous- monitoring data, although useful, are impractical due to the cost of the equipment. We propose a protocol for 222Rn measurement based on three simultaneous integrating radon detectors that may help estimate the proportion of indoor 222Rn derived from the water supply.

Health Physics↗

Vanadium accumulation in carbonaceous rocks: A review of geochemical controls during deposition and diagenesis

Published data relevant to the geochemistry of vanadium were used to evaluate processes and conditions that control vanadium accumulation in carbonaceous rocks. Reduction, adsorption, and complexation of dissolved vanadium favor addition of vanadium to sediments rich in organic carbon. Dissolved vanadate (V(V)) species predominate in oxic seawater and are reduced to vanadyl ion (V(IV)) by organic compounds or H2S. Vanadyl ion readily adsorbs to particle surfaces and is added to the sediment as the particles settle. The large vanadium concentrations of rocks deposited in marine as compared to lacustrine environments are the result of the relatively large amount of vanadium provided by circulating ocean water compared to terrestrial runoff. Vanadium-rich carbonaceous rocks typically have high contents of organically bound sulfur and are stratigraphically associated with phosphate-rich units. A correspondence between vanadium content and organically bound sulfur is consistent with high activities of H2S during sediment deposition. Excess H2S exited the sediment into bottom waters and favored reduction of dissolved V(V) to V(IV) or possibly V(III). The stratigraphic association of vanadiferous and phosphatic rocks reflects temporal and spatial shifts in bottom water chemistry from suboxic (phosphate concentrated) to more reducing (euxinic?) conditions that favor vanadium accumulation. During diagenesis some vanadium-organic complexes migrate with petroleum out of carbonaceous rocks, but significant amounts of vanadium are retained in refractory organic matter or clay minerals. As carbon in the rock evolves toward graphite during metamorphism, vanadium is incorporated into silicate minerals. ?? 1991.

Chemical Geology↗

Radon-222 and its parent radionuclides in groundwater from two study areas in New Jersey and Maryland, U.S.A.

A study of groundwater chemistry and radionuclide mobility in New Jersey and Maryland was conducted to investigate natural processes that control the mobility of radionuclides in the water-rock system. Groundwater was sampled from two geological units in New Jersey and from six in Maryland. The water sampled was from aquifiers in fractured metamorphic rocks of varying composition and metamorphic grade. In both areas, groundwater chemistry was affected most by aquifier mineralogy and lithology; concentrations of total dissolved U, 226Ra and 222Rn were similarly affected. In evey sample for which measurements were made, dissolved Utotal and 226Ra were present in much lower concentrations than 222Rn when expressed in terms of their radioactivity. On the other hand, the total amount of 222Rn that could be produced in these rocks, given their U contents, is much higher than the concentrations observed in groundwater. Thus, the emanating efficiencies of the aquifer rocks studied must be near 10% or less. Such low emanating efficiencies require that a fraction of the 226Ra in the rock be located close to the water-rock interface so that 222Rn, when produced, can be rapidly and efficiently transferred to the aqueous phase. This condition is established when a similar fraction of the U is in a readily leachable position. No known U or Ra solids were supersaturated in any of the samples. Thus, adsorption processes probably play a role in limiting mobilities of Utotal and 226Ra. Concentrations of Utotal and 226Ra found in the water samples are comparable to those found in experimental studies of adsorption onto mineral surfaces. ?? 1991.

Maryland, New Jersey↗

Geochemistry of vanadium in an epigenetic, sandstone-hosted vanadium-uranium deposit, Henry Basin, Utah

The epigenetic Tony M vanadium-uranium orebody in south-central Utah is hosted in fluvial sandstones of the Morrison Formation (Upper Jurassic). Although the deposit is mined for uranium, vanadium has a higher average abundance in the ore. Thus, the geochemistry of vanadium in the orebody was studied to characterize ore-forming processes within the inferred ground-water flow regime. Measurements of the relative amounts of V (super +3) and V (super +4) in ore minerals show that V (super +3) is more abundant. Thermodynamic calculations show that vanadium was more likely transported to the site of mineralization as V (super +4) . The ore formed as V (super +4) was reduced by hydrogen sulfide, followed by hydrolysis and precipitation of V (super +3) in oxide minerals (e.g., montroseitc or paramontroseite) or chlorite. Uranium was transported as uranyl ion (U (super +6) ), or some complex thereof, and reduced by hydrogen sulfide, forming coffinite. Detrital organic matter in the rocks served as the carbon source for sulfate-reducing bacteria. It was this bacteriogenic H 2 S that reduced the metals in the mineralization process.Possible sources for the V and U in this deposit have been identified previously. Vanadium most likely was derived from the dissolution of iron-titanium oxides, which liberated Fe as well as V. A zone of titanium-rich remnants is observed updip and up the hydrologic gradient from the deposit (M. Goldhaber and R. L. Reynolds, unpub. data). Uranium probably was derived from the overlying Brushy Basin Member of the Morrison Formation (Northrop, 1982). A preliminary age date for the deposit of 115 Ma (K. Ludwig, 1986, pers. commun.) indicates that the ore formed after deposition of the Brushy Basin Member.Previous studies have shown that the ore formed at the density-stratified interface between a basinal brine and dilute meteoric water. The mineralization processes described above occurred within the mixing zone between these two fluids. Stable isotope analyses of ore-stage dolomite show a progressively heavier carbon and oxygen isotope signature with increasing depth through an ore horizon, consistent with the two-solution interface model.

Economic Geology↗

Geochemical controls of vanadium accumulation in fossil fuels

High vanadium contents in petroleum and other fossil fuels have been attributed to organic-matter type, organisms, volcanic emanations, diffusion of sea water, and epigenetic enrichment. However, these factors are inadequate to account for the high abundance of vanadium in some fossil fuels and the paucity in others. By examining vanadium deposits in sedimentary rocks with sparse organic matter, constraints are placed on processes controlling vanadium accumulation in organic-rich sediments. Vanadium, as vanadate (V(V)), entered some depositional basins in oxidizing waters from dry, subaerial environments. Upon contact with organic matter in anoxic waters, V(V) is reduced to vanadyl (V(IV)), which can be removed from the water column by adsorption. H2S reduces V(IV) to V(III), which hydrolyzes and precipitates. The lack of V(III) in petroleum suggests that reduction of V(IV) to V(III) is inhibited by organic complexes. In the absence of strong complexing agents, V(III) forms and is incorporated in clay minerals.

Conference Paper↗