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R. B. Wanty

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

At least 19 recordsLinked to original sources

Influence of sulfur-bearing polyatomic species on high precision measurements of Cu isotopic composition

An increased interest in high precision Cu isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has developed recently for various natural geologic systems and environmental applications, these typically contain high concentrations of sulfur, particularly in the form of sulfate (SO 4 2- ) and sulfide (S). For example, Cu, Fe, and Zn concentrations in acid mine drainage (AMD) can range from 100??g/L to greater than 50mg/L with sulfur species concentrations reaching greater than 1000mg/L. Routine separation of Cu, Fe and Zn from AMD, Cu-sulfide minerals and other geological matrices usually incorporates single anion exchange resin column chromatography for metal separation. During chromatographic separation, variable breakthrough of SO 4 2- during anion exchange resin column chromatography into the Cu fractions was observed as a function of the initial sulfur to Cu ratio, column properties, and the sample matrix. SO 4 2- present in the Cu fraction can form a polyatomic 32 S- 14 N- 16 O- 1 H species causing a direct mass interference with 63 Cu and producing artificially light ?? 65 Cu values. Here we report the extent of the mass interference caused by SO 4 2- breakthrough when measuring ?? 65 Cu on natural samples and NIST SRM 976 Cu isotope spiked with SO 4 2- after both single anion column chromatography and double anion column chromatography. A set of five 100??g/L Cu SRM 976 samples spiked with 500mg/L SO 4 2- resulted in an average ?? 65 Cu of -3.50?????5.42??? following single anion column separation with variable SO 4 2- breakthrough but an average concentration of 770??g/L. Following double anion column separation, the average SO 4 2- concentration of 13??g/L resulted in better precision and accuracy for the measured ?? 65 Cu value of 0.01?????0.02??? relative to the expected 0??? for SRM 976. We conclude that attention to SO 4 2- breakthrough on sulfur-rich samples is necessary for accurate and precise measurements of ?? 65 Cu and may require the use of a double ion exchange column procedure. ?? 2010.

Chemical Geology

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, δ 56 Fe and δ 66 Zn isotopic signatures of filtered stream water samples varied by ∼3.5‰ and 0.4‰, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in δ 56 Fe were linked to redox and precipitation reactions occurring in the stream, while changes in δ 66 Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<−2.0‰) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4‰). Acidic drainage from mine wastes contributed heavier dissolved Fe (∼+0.5‰) and lighter Zn (∼+0.2‰) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe ( δ 56 Fe ∼ 0‰) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds.

Applied Geochemistry

A regional soil and sediment geochemical study in northern California

Regional-scale variations in soil geochemistry were investigated in a 20,000-km 2 study area in northern California that includes the western slope of the Sierra Nevada, the southern Sacramento Valley and the northern Coast Ranges. Over 1300 archival soil samples collected from the late 1970s to 1980 in El Dorado, Placer, Sutter, Sacramento, Yolo and Solano counties were analyzed for 42 elements by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry following a near-total dissolution. These data were supplemented by analysis of more than 500 stream-sediment samples from higher elevations in the Sierra Nevada from the same study site. The relatively high-density data (1 sample per 15 km 2 for much of the study area) allows the delineation of regional geochemical patterns and the identification of processes that produced these patterns. The geochemical results segregate broadly into distinct element groupings whose distribution reflects the interplay of geologic, hydrologic, geomorphic and anthropogenic factors. One such group includes elements associated with mafic and ultramafic rocks including Cr, Ni, V, Co, Cu and Mg. Using Cr as an example, elevated concentrations occur in soils overlying ultramafic rocks in the foothills of the Sierra Nevada (median Cr = 160 mg/kg) as well as in the northern Coast Ranges. Low concentrations of these elements occur in soils located further upslope in the Sierra Nevada overlying Tertiary volcanic, metasedimentary and plutonic rocks (granodiorite and diorite). Eastern Sacramento Valley soil samples, defined as those located east of the Sacramento River, are lower in Cr (median Cr = 84 mg/kg), and are systematically lower in this suite compared to soils from the west side of the Sacramento Valley (median Cr = 130 mg/kg). A second group of elements showing a coherent pattern, including Ca, K, Sr and REE, is derived from relatively silicic rocks types. This group occurs at elevated concentrations in soils overlying volcanic and plutonic rocks at higher elevations in the Sierras (e.g. median La = 28 mg/kg) and the east side of the Sacramento Valley (median 20 mg/kg) compared to soils overlying ultramafic rocks in the Sierra Nevada foothills (median 15 mg/kg) and the western Sacramento Valley (median 14 mg/kg). The segregation of soil geochemistry into distinctive groupings across the Sacramento River arises from the former presence of a natural levee (now replaced by an artificial one) along the banks of the river. This levee has been a barrier to sediment transport. Sediment transport to the Valley by glacial outwash from higher elevations in the Sierra Nevada and, more recently, debris from placer Au mining has dominated sediment transport to the eastern Valley. High content of mafic elements (and low content of silicic elements) in surface soil in the west side of the valley is due to a combination of lack of silicic source rocks, transport of ultramafic rock material from the Coast Ranges, and input of sediment from the late Mesozoic Great Valley Group, which is itself enriched in mafic elements. A third group of elements (Zn, Cd, As and Cu) reflect the impact of mining activity. Soil with elevated content of these elements occurs along the Sacramento River in both levee and adjacent flood basin settings. It is interpreted that transport of sediment down the Sacramento River from massive sulfide mines in the Klamath Mountains to the north has caused this pattern. The Pb, and to some extent Zn, distribution patterns are strongly impacted by anthropogenic inputs. Elevated Pb content is localized in major cites and along major highways due to inputs from leaded gasoline. Zinc has a similar distribution pattern but the source is tire wear.

Applied Geochemistry

Regional variations in water quality and relationships to soil and bedrock weathering in the southern Sacramento Valley, California, USA

Regional patterns in ground- and surface-water chemistry of the southern Sacramento Valley in California were evaluated using publicly available geochemical data from the US Geological Survey's National Water Information System (NWIS). Within the boundaries of the study area, more than 2300 ground-water analyses and more than 20,000 surface-water analyses were available. Ground-waters from the west side of the Sacramento Valley contain greater concentrations of Na, Ca, Mg, B, Cl and SO 4 , while the east-side ground-waters contain greater concentrations of silica and K. These differences result from variations in surface-water chemistry as well as from chemical reactions between water and aquifer materials. Sediments that fill the Sacramento Valley were derived from highlands to the west (the Coast Ranges) and east (the Sierra Nevada Mountains), the former having an oceanic provenance and the latter continental. These geologic differences are at least in part responsible for the observed patterns in ground-water chemistry. Thermal springs that are common along the west side of the Sacramento Valley appear to have an effect on surface-water chemistry, which in turn may affect the ground-water chemistry.

Applied Geochemistry

A regional-scale study of chromium and nickel in soils of northern California, USA

A soil geochemical survey was conducted in a 27,000-km 2 study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700-10,000 mg/kg Cr and 1300-3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80-1420 mg/kg Cr and 65-224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30-370 mg/kg Cr and 16-110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada. Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO 3 , HCl, HF, HClO 4 ), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO 3 ) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 ??g L -1 and averaging 16.4 ??g L -1 . This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.

Applied Geochemistry

Environmental effects of hydrothermal alteration and historical mining on water and sediment quality in Central Colorado

The U.S. Geological Survey conducted an environmental assessment of 198 catchments in a 54,000-km2 area of central Colorado, much of which is on Federal land. The Colorado Mineral Belt, a northeast-trending zone of historical base- and precious-metal mining, cuts diagonally across the study area. The investigation was intended to test the hypothesis that degraded water and sediment quality are restricted to catchments in which historical mining has occurred. Water, streambed sediment, and aquatic insects were collected from (1) catchments underlain by single lithogeochemical units, some of which were hydrothermally altered, that had not been prospected or mined; (2) catchments that contained evidence of prospecting, most of which contain hydrothermally altered rock, but no historical mining; and (3) catchments, all of which contain hydrothermally altered rock, where historical but now inactive mines occur. Geochemical data determined from catchments that did not contain hydrothermal alteration or historical mines met water quality criteria and sediment quality guidelines. Base-metal concentrations from these types of catchments showed small geochemical variations that reflect host lithology. Hydrothermal alteration and mineralization typically are associated with igneous rocks that have intruded older bedrock in a catchment. This alteration was regionally mapped and characterized primarily through the analysis of remote sensing data acquired by the ASTER satellite sensor. Base-metal concentrations among unaltered rock types showed small geochemical variations that reflect host lithology. Base-metal concentrations were elevated in sediment from catchments underlain by hydrothermally altered rock. Classification of catchments on the basis of mineral deposit types proved to be an efficient and accurate method for discriminating catchments that have degraded water and sediment quality. Only about 4.5 percent of the study area has been affected by historical mining, whereas a larger part of the study area is underlain by hydrothermally altered rock that has weathered to produce water and sediment with naturally elevated geochemical baselines.

Colorado

Aquatic ecosystems in Central Colorado are influenced by mineral forming processes and historical mining

Stream water and sediment toxicity to aquatic insects were quantified from central Colorado catchments to distinguish the effect of geologic processes which result in high background metals concentrations from historical mining. Our sampling design targeted small catchments underlain by rocks of a single lithology, which allowed the development of biological and geochemical baselines without the complication of multiple rock types exposed in the catchment. By accounting for geologic sources of metals to the environment, we were able to distinguish between the environmental effects caused by mining and the weathering of different mineralized areas. Elevated metal concentrations in water and sediment were not restricted to mined catchments. Impairment of aquatic communities also occurred in unmined catchments influenced by hydrothermal alteration. Hydrothermal alteration style, deposit type, and mining were important determinants of water and sediment quality and aquatic community structure. Weathering of unmined porphyry Cu-Mo occurrences resulted in water (median toxic unit (TU) = 108) and sediment quality (TU = 1.9) that exceeded concentrations thought to be safe for aquatic ecosystems (TU = 1). Metalsensitive aquatic insects were virtually absent from streams draining catchments with porphyry Cu-Mo occurrences (1.1 individuals/0.1 m2 ). However, water and sediment quality (TU = 0.1, 0.5 water and sediment, respectively) and presence of metalsensitive aquatic insects (204 individuals/0.1 m2 ) for unmined polymetallic vein occurrences were indistinguishable from that for unmined and unaltered streams (TU = 0.1, 0.5 water and sediment, respectively; 201 individuals/0.1 m2 ). In catchments with mined quartz-sericite-pyrite altered polymetallic vein deposits, water (TU = 8.4) and sediment quality (TU = 3.1) were degraded and more toxic to aquatic insects (36 individuals/0.1 m2 ) than water (TU = 0.4) and sediment quality (TU = 1.7) from mined propylitically altered polymetallic vein deposits. The sampling approach taken in this study distinguishes the effects of different mineral deposits on ecosystems and can be used to more accurately quantify the effect of mining on the environment.

Conference Paper

Regional Geochemical Results from Analyses of Stream-Water, Stream-Sediment, Soil, Soil-Water, Bedrock, and Vegetation Samples, Tangle Lakes District, Alaska

We report chemical analyses of stream-water, stream-sediment, soil, soil-water, bedrock, and vegetation samples collected from the headwaters of the Delta River (Tangle Lakes District, Mount Hayes 1:250,000-scale quadrangle) in east-central Alaska for the period June 20-25, 2006. Additionally, we present mineralogic analyses of stream sediment, concentrated by panning. The study area includes the southwestward extent of the Bureau of Land Management (BLM) Delta River Mining District (Bittenbender and others, 2007), including parts of the Delta River Archeological District, and encompasses an area of about 500 km2(approximately bordered by the Denali Highway to the south, near Round Tangle Lake, northward to the foothills of the Alaska Range (fig. 1). The primary focus of this study was the chemical characterization of native materials, especially surface-water and sediment samples, of first-order streams from the headwaters of the Delta River. The impetus for this work was the need, expressed by the Alaska Department of Natural Resources (ADNR), for an inventory of geochemical and hydrogeochemical baseline information about the Delta River Mining District. This information is needed because of a major upturn in exploration, drilling, and general mineral-resources assessments in the region since the late 1990s. Currently, the study area, called the 'MAN Project' area is being explored by Pure Nickel, Inc. (http://www.purenickel.com/s/MAN_Alaska.asp), and includes both Cu-Au-Ag and Ni-Cu-PGE (Pt-Pd-Au-Ag) mining claims. Geochemical data on surface-water, stream-sediment, soil, soil-water, grayleaf willow (Salix glauca L.), and limited bedrock samples are provided along with the analytical methodologies used and panned-concentrate mineralogy. We are releasing the data at this time with only minimal interpretation.

Open-File Report

Stability of low levels of perchlorate in drinking water and natural water samples

Perchlorate ion (ClO4-) is an environmental contaminant of growing concern due to its potential human health effects, impact on aquatic and land animals, and widespread occurrence throughout the United States. The determination of perchlorate cannot normally be carried out in the field. As such, water samples for perchlorate analysis are often shipped to a central laboratory, where they may be stored for a significant period before analysis. The stability of perchlorate ion in various types of commonly encountered water samples has not been generally examined-the effect of such storage is thus not known. In the present study, the long-term stability of perchlorate ion in deionized water, tap water, ground water, and surface water was examined. Sample sets containing approximately 1000, 100, 1.0, and 0.5 ??g l-1 perchlorate ion in deionized water and also in local tap water were formulated. These samples were analyzed by ion chromatography for perchlorate ion concentration against freshly prepared standards every 24 h for the first 7 days, biweekly for the next 4 weeks, and periodically after that for a total of 400 or 610 days for the two lowest concentrations and a total of 428 or 638 days for the high concentrations. Ground and surface water samples containing perchlorate were collected, held and analyzed for perchlorate concentration periodically over at least 360 days. All samples except for the surface water samples were found to be stable for the duration of the study, allowing for holding times of at least 300 days for ground water samples and at least 90 days for surface water samples. ?? 2006 Elsevier B.V. All rights reserved.

Analytica Chimica Acta

Geologic, hydrologic, and geochemical interpretations of mineral deposits as analogs for understanding transport of environmental contaminants

Base- and precious-metal mineral deposits comprise anomalous concentrations of metals and associated elements, which may be useful subjects for study as analogs for migration of environmental contaminants. In the geologic past, hydrothermal mineral deposits formed at the intersection of favorable geologic, hydrologic and geochemical gradients. In the present, weathering of these sulfide-rich deposits occurs as a result of the interplay between rates of oxygen supply versus rates of ground or surface-water flow. Transport and spatial dispersion of elements from a mineral deposit occurs as a function of competing rates of water flow versus rates of attenuation mechanisms such as adsorption, dilution, or (co)precipitation. In this paper we present several case studies from mineralized and altered sedimentary and crystalline aquifers in the western United States to illustrate the geologic control of ground-water flow and solute transport, and to demonstrate how this combined approach leads to a more complete understanding of the systems under study as well as facilitating some capability to predict major flow directions in aquifers.

Journal of Geochemical Exploration

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

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