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G. N. Breit

Publications and source records attributed to G. N. Breit.

15 recordsLinked to original sources

Vulnerability of deep groundwater in the Bengal Aquifer System to contamination by arsenic

Shallow groundwater, the primary water source in the Bengal Basin, contains up to 100 times the World Health Organization (WHO) drinking-water guideline of 10g l 1 arsenic (As), threatening the health of 70 million people. Groundwater from a depth greater than 150m, which almost uniformly meets the WHO guideline, has become the preferred alternative source. The vulnerability of deep wells to contamination by As is governed by the geometry of induced groundwater flow paths and the geochemical conditions encountered between the shallow and deep regions of the aquifer. Stratification of flow separates deep groundwater from shallow sources of As in some areas. Oxidized sediments also protect deep groundwater through the ability of ferric oxyhydroxides to adsorb As. Basin-scale groundwater flow modelling suggests that, over large regions, deep hand-pumped wells for domestic supply may be secure against As invasion for hundreds of years. By contrast, widespread deep irrigation pumping might effectively eliminate deep groundwater as an As-free resource within decades. Finer-scale models, incorporating spatial heterogeneity, are needed to investigate the security of deep municipal abstraction at specific urban locations. ?? 2010 Macmillan Publishers Limited. All rights reserved.

Nature Geoscience

Weathering of the New Albany Shale, Kentucky, USA: I. Weathering zones defined by mineralogy and major-element composition

Comprehensive understanding of chemical and mineralogical changes induced by weathering is valuable information when considering the supply of nutrients and toxic elements from rocks. Here minerals that release and fix major elements during progressive weathering of a bed of Devonian New Albany Shale in eastern Kentucky are documented. Samples were collected from unweathered core (parent shale) and across an outcrop excavated into a hillside 40 year prior to sampling. Quantitative X-ray diffraction mineralogical data record progressive shale alteration across the outcrop. Mineral compositional changes reflect subtle alteration processes such as incongruent dissolution and cation exchange. Altered primary minerals include K-feldspars, plagioclase, calcite, pyrite, and chlorite. Secondary minerals include jarosite, gypsum, goethite, amorphous Fe(III) oxides and Fe(II)-Al sulfate salt (efflorescence). The mineralogy in weathered shale defines four weathered intervals on the outcrop-Zones A-C and soil. Alteration of the weakly weathered shale (Zone A) is attributed to the 40-a exposure of the shale. In this zone, pyrite oxidization produces acid that dissolves calcite and attacks chlorite, forming gypsum, jarosite, and minor efflorescent salt. The pre-excavation, active weathering front (Zone B) is where complete pyrite oxidation and alteration of feldspar and organic matter result in increased permeability. Acidic weathering solutions seep through the permeable shale and evaporate on the surface forming abundant efflorescent salt, jarosite and minor goethite. Intensely weathered shale (Zone C) is depleted in feldspars, chlorite, gypsum, jarosite and efflorescent salts, but has retained much of its primary quartz, illite and illite-smectite. Goethite and amorphous FE(III) oxides increase due to hydrolysis of jarosite. Enhanced permeability in this zone is due to a 14% loss of the original mass in parent shale. Denudation rates suggest that characteristics of Zone C were acquired over 1 Ma. Compositional differences between soil and Zone C are largely attributed to illuvial processes, formation of additional Fe(III) oxides and incorporation of modern organic matter.

Applied Geochemistry

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies. Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.

Applied Geochemistry

Characteristics, extent and origin of hydrothermal alteration at Mount Rainier Volcano, Cascades Arc, USA: Implications for debris-flow hazards and mineral deposits

Hydrothermal alteration at Mount Rainier waxed and waned over the 500,000-year episodic growth of the edifice. Hydrothermal minerals and their stable-isotope compositions in samples collected from outcrop and as clasts from Holocene debris-flow deposits identify three distinct hypogene argillic/advanced argillic hydrothermal environments: magmatic-hydrothermal, steam-heated, and magmatic steam (fumarolic), with minor superimposed supergene alteration. The 3.8 km 3 Osceola Mudflow (5600 y BP) and coeval phreatomagmatic F tephra contain the highest temperature and most deeply formed hydrothermal minerals. Relatively deeply formed magmatic-hydrothermal alteration minerals and associations in clasts include quartz (residual silica), quartz–alunite, quartz–topaz, quartz–pyrophyllite, quartz–dickite/kaolinite, and quartz–illite (all with pyrite). Clasts of smectite–pyrite and steam-heated opal–alunite–kaolinite are also common in the Osceola Mudflow. In contrast, the Paradise lahar, formed by collapse of the summit or near-summit of the edifice at about the same time, contains only smectite–pyrite and near-surface steam-heated and fumarolic alteration minerals. Younger debris-flow deposits on the west side of the volcano (Round Pass and distal Electron Mudflows) contain only low-temperature smectite–pyrite assemblages, whereas the proximal Electron Mudflow and a < 100 y BP rock avalanche on Tahoma Glacier also contain magmatic-hydrothermal alteration minerals that are exposed in the avalanche headwall of Sunset Amphitheater, reflecting progressive incision into deeper near-conduit alteration products that formed at higher temperatures. The pre-Osceola Mudflow alteration geometry is inferred to have consisted of a narrow feeder zone of intense magmatic-hydrothermal alteration limited to near the conduit of the volcano, which graded outward to more widely distributed, but weak, smectite–pyrite alteration within 1 km of the edifice axis, developed chiefly in porous breccias. The edifice was capped by a steam-heated alteration zone, most of which resulted from condensation of fumarolic vapor and oxidation of H 2 S in the unsaturated zone above the water table. Weakly developed smectite–pyrite alteration extended into the west and east flanks of the edifice, spatially associated with dikes that are localized in those sectors; other edifice flanks lack dikes and associated alteration. The Osceola collapse removed most of the altered core and upper east flank of the volcano, but intensely altered rocks remain on the uppermost west flank. Major conclusions of this study are that: (1) Hydrothermal–mineral assemblages and distributions at Mount Rainier can be understood in the framework of hydrothermal processes and environments developed from studies of ore deposits formed in analogous settings. (2) Frequent eruptions supplied sufficient hot magmatic fluid to alter the upper interior of the volcano hydrothermally, despite the consistently deep (≥ 8 km) magma reservoir which may have precluded formation of economic mineral deposits within or at shallow depths beneath Mount Rainier. The absence of indicator equilibrium alteration-mineral assemblages in the debris flows that effectively expose the volcano to a depth of 1–1.5 km also suggests a low potential for significant high-sulfidation epithermal or porphyry-type mineral deposits at depth. (3) Despite the long and complex history of the volcano, intensely altered collapse-prone rocks were spatially restricted to near the volcano's conduit system and summit, and short distances onto the upper east and west flanks, due to the necessary supply of reactive components carried by ascending magmatic fluids. (4) Intensely altered rocks were removed from the summit, east flank, and edifice interior by the Osceola collapse, but remain on the upper west flank in the Sunset Amphitheater area and present a continuing collapse hazard. (5) Visually conspicuous rocks on the lower east and mid-to-lower west flanks are not intensely altered and probably have not significantly weakened the rock, and thus do not present significant collapse hazards. (6) Alteration developed most intensely within breccia units, because of their high permeability and porosity. Volcanoes with abundant near-conduit upper-edifice breccias are prone to alteration increasing the possibility of collapse, whereas those that are breccia-poor (e.g., massive domes) are less prone to alteration.

Journal of Volcanology and Geothermal Research

Origin of secondary sulfate minerals on active andesitic stratovolcanoes

Sulfate minerals in altered rocks on the upper flanks and summits of active andesitic stratovolcanoes result from multiple processes. The origin of these sulfates at five active volcanoes, Citlalte??petl (Mexico), and Mount Adams, Hood, Rainier, and Shasta (Cascade Range, USA), was investigated using field observations, petrography, mineralogy, chemical modeling, and stable-isotope data. The four general groups of sulfate minerals identified are: (1) alunite group, (2) jarosite group, (3) readily soluble Fe- and Al-hydroxysulfates, and (4) simple alkaline-earth sulfates such as anhydrite, gypsum, and barite. Generalized assemblages of spatially associated secondary minerals were recognized: (1) alunite+silica??pyrite??kaolinite?? gypsum??sulfur, (2) jarosite+alunite+silica; (3) jarosite+smectite+silica??pyrite, (4) Fe- and Al-hydroxysulfates+silica, and (5) simple sulfates+silica??Al-hydroxysulfates??alunite. Isotopic data verify that all sulfate and sulfide minerals and their associated alteration assemblages result largely from the introduction of sulfur-bearing magmatic gases into meteoric water in the upper levels of the volcanoes. The sulfur and oxygen isotopic data for all minerals indicate the general mixing of aqueous sulfate derived from deep (largely disproportionation of SO2 in magmatic vapor) and shallow (oxidation of pyrite or H2S) sources. The hydrogen and oxygen isotopic data of alunite indicate the mixing of magmatic and meteoric fluids. Some alunite-group minerals, along with kaolinite, formed from sulfuric acid created by the disproportionation of SO2 in a condensing magmatic vapor. Such alunite, observed only in those volcanoes whose interiors are exposed by erosion or edifice collapse, may have ??34S values that reflect equilibrium (350??50 ??C) between aqueous sulfate and H2S. Alunite with ??34S values indicating disequilibrium between parent aqueous sulfate and H2S may form from aqueous sulfate created in higher level low-temperature environments in which SO2 is scrubbed out by groundwater or where H2S is oxidized. Jarosite-group minerals associated with smectite in only slightly altered volcanic rock are formed largely from aqueous sulfate derived from supergene oxidation of hydrothermal pyrite above the water table. Soluble Al- and Fehydroxysulfates form in low-pH surface environments, especially around fumaroles, and from the oxidation of hydrothermal pyrite. Anhydrite/gypsum, often associated with native sulfur and occasionally with small amounts of barite, also commonly form around fumaroles. Some occurrences of anhydrite/gypsum may be secondary, derived from the dissolution and reprecipitation of soluble sulfate. Edifice collapse may also reveal deep veins of anhydrite/gypsum??barite that formed from the mixing of saline fluids with magmatic sulfate and dilute meteoric water. Alteration along structures associated with both hydrothermal and supergene sulfates, as well as the position of paleo-water tables, may be important factors in edifice collapse and resulting debris flows at some volcanoes. ?? 2004 Elsevier B.V. All rights reserved.

Chemical Geology

Stratovolcano stability assessment methods and results from Citlaltepetl, Mexico

Citlalt&eacute;petl volcano is the easternmost stratovolcano in the Trans-Mexican Volcanic Belt. Situated within 110 km of Veracruz, it has experienced two major collapse events and, subsequent to its last collapse, rebuilt a massive, symmetrical summit cone. To enhance hazard mitigation efforts we assess the stability of Citlalt&eacute;petl's summit cone, the area thought most likely to fail during a potential massive collapse event. Through geologic mapping, alteration mineralogy, geotechnical studies, and stability modeling we provide important constraints on the likelihood, location, and size of a potential collapse event. The volcano's summit cone is young, highly fractured, and hydrothermally altered. Fractures are most abundant within 5&ndash;20-m wide zones defined by multiple parallel to subparallel fractures. Alteration is most pervasive within the fracture systems and includes acid sulfate, advanced argillic, argillic, and silicification ranks. Fractured and altered rocks both have significantly reduced rock strengths, representing likely bounding surfaces for future collapse events. The fracture systems and altered rock masses occur non-uniformly, as an orthogonal set with N&ndash;S and E&ndash;W trends. Because these surfaces occur non-uniformly, hazards associated with collapse are unevenly distributed about the volcano. Depending on uncertainties in bounding surfaces, but constrained by detailed field studies, potential failure volumes are estimated to range between 0.04&ndash;0.5 km 3 . Stability modeling was used to assess potential edifice failure events. Modeled failure of the outer portion of the cone initially occurs as an "intact block" bounded by steeply dipping joints and outwardly dipping flow contacts. As collapse progresses, more of the inner cone fails and the outer "intact" block transforms into a collection of smaller blocks. Eventually, a steep face develops in the uppermost and central portion of the cone. This modeled failure morphology mimics collapse amphitheaters

Bulletin of Volcanology

Sources of sulfate supporting anaerobic metabolism in a contaminated aquifer

Field and laboratory techniques were used to identify the biogeochemical factors affecting sulfate reduction in a shallow, unconsolidated alluvial aquifer contaminated with landfill leachate. Depth profiles of 35 S-sulfate reduction rates in aquifer sediments were positively correlated with the concentration of dissolved sulfate. Manipulation of the sulfate concentration in samples revealed a Michaelis−Menten-like relationship with an apparent K m and V max of approximately 80 and 0.83 μM SO 4 - 2 ·day - 1 , respectively. The concentration of sulfate in the core of the leachate plume was well below 20 μM and coincided with very low reduction rates. Thus, the concentration and availability of this anion could limit in situ sulfate-reducing activity. Three sulfate sources were identified, including iron sulfide oxidation, barite dissolution, and advective flux of sulfate. The relative importance of these sources varied with depth in the alluvium. The relatively high concentration of dissolved sulfate at the water table is attributed to the microbial oxidation of iron sulfides in response to fluctuations of the water table. At intermediate depths, barite dissolves in undersaturated pore water containing relatively high concentrations of dissolved barium (∼100 μM) and low concentrations of sulfate. Dissolution is consistent with the surface texture of detrital barite grains in contact with leachate. Laboratory incubations of unamended and barite-amended aquifer slurries supported the field observation of increasing concentrations of barium in solution when sulfate reached low levels. At a deeper highly permeable interval just above the confining bottom layer of the aquifer, sulfate reduction rates were markedly higher than rates at intermediate depths. Sulfate is supplied to this deeper zone by advection of uncontaminated groundwater beneath the landfill. The measured rates of sulfate reduction in the aquifer also correlated with the abundance of accumulated iron sulfide in this zone. This suggests that the current and past distributions of sulfate-reducing activity are similar and that the supply of sulfate has been sustained at these sites.

Environmental Science & Technology

Sulfur-bearing coatings on fly ash from a coal-fired power plant: Composition, origin, and influence on ash alteration

Fly ash samples collected from two locations in the exhaust stream of a coal-fired power plant differ markedly with respect to the abundance of thin (≈0.1 μm) sulfur-rich surface coatings that are observable by scanning electron microscopy. The coatings, tentatively identified as an aluminum-potassium-sulfate phase, probably form upon reaction between condensed sulfuric acid aerosols and glass surfaces, and are preferentially concentrated on ash exposed to exhaust stream gases for longer. The coatings are highly soluble and if sufficiently abundant, can impart an acidic pH to solutions initially in contact with ash. These observations suggest that proposals for ash use and predictions of ash behavior during disposal should consider the transient, acid-generating potential of some ash fractions and the possible effects on initial ash leachability and alteration.

Fuel

Environmental issues associated with fossil fuel resources; an evaluation of research opportunities for the U.S. Geological Survey's Energy Resources Program

Fossil fuel consumption in the United States has nearly tripled within the last 50 years (fig. 1), and is expected to continue increasing. As our knowledge and awareness of environmental consequences related to fossil fuel extraction and use grow, we as a nation, face the challenge of balancing our energy requirements with a desire for environmentally cleaner fuel. To help meet this challenge, the Energy Resources Program (ERP) of the Geologic Division (GD), U.S. Geological Survey (USGS) sponsored three internal workshops and a World Wide Web (WWW) workshop. The primary goal of these workshops was to identify those environmental issues that are related to fossil fuels, are national in scope, and are within the purview of the USGS as an earth-science government agency. Those issues so identified will be prioritized according to ERP's future research plan and according to the extent they provide an environmental framework for ERP's petroleum and coal assessments. The purpose of this paper is to provide the results of the internal and WWW workshops as proposed topics of research for future ERP work, delineate studies to answer the questions related to each proposed research area, and link the studies to the seven science goals of the Geologic Division. The information provided herein will be used in preparing the USGS Geologic Division's FY2000 prospectus and ERP's next five-year strategic plan. Acknowledgements. The authors wish to acknowledge information on ERP environmental projects provided by Les Magoon, Paul Lillis, Keith Kvenvolden, Tom Lorenson, and Bob Rosenbauer. Peter Schweitzer was instrumental in providing the software for the WWW workshop, Cheryl Adkisson for constructing the workshop web pages, and Laura Friedrich for constructing the web pages summarizing the internal workshops. Stan Mroczkowski, Jim Otton, Donna Read, and Dorothy Tanti provided notes of or logistical assistance for the internal workshops. This report reflects the collective input of numerous USGS managers and scientists their participation in the workshops is greatly appreciated.

Open-File Report

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

Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87 Sr 86 Sr "> 87Sr86Sr ratios by less than 0.00001 at 1.95θ of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87 Sr 86 Sr "> 87Sr86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material.

Chemical Geology: Isotope Geoscience Section