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S. F. Diehl

Publications and source records attributed to S. F. Diehl.

14 recordsLinked to original sources

Distribution of arsenic, selenium, and other trace elements in high pyrite Appalachian coals: evidence for multiple episodes of pyrite formation

Pennsylvanian coals in the Appalachian Basin host pyrite that is locally enriched in potentially toxic trace elements such as As, Se, Hg, Pb, and Ni. A comparison of pyrite-rich coals from northwestern Alabama, eastern Kentucky, and West Virginia reveals differences in concentrations and mode of occurrence of trace elements in pyrite. Pyrite occurs as framboids, dendrites, or in massive crystalline form in cell lumens or crosscutting veins. Metal concentrations in pyrite vary over all scales, from microscopic to mine to regional, because trace elements are inhomogeneously distributed in the different morphological forms of pyrite, and in the multiple generations of sulfide mineral precipitates. Early diagenetic framboidal pyrite is usually depleted in As, Se, and Hg, and enriched in Pb and Ni, compared to other pyrite forms. In dendritic pyrite, maps of As distribution show a chemical gradient from As-rich centers to As-poor distal branches, whereas Se concentrations are highest at the distal edges of the branches. Massive crystalline pyrite that fills veins is composed of several generations of sulfide minerals. Pyrite in late-stage veins commonly exhibits As-rich growth zones, indicating a probable epigenetic hydrothermal origin. Selenium is concentrated at the distal edges of veins. A positive correlation of As and Se in pyrite veins from Kentucky coals, and of As and Hg in pyrite-filled veins from Alabama coals, suggests coprecipitation of these elements from the same fluid. In the Kentucky coal samples (n = 18), As and Se contents in pyrite-filled veins average 4200 ppm and 200 ppm, respectively. In Alabama coal samples, As in pyrite-filled veins averages 2700 ppm (n = 34), whereas As in pyrite-filled cellular structures averages 6470 ppm (n = 35). In these same Alabama samples, Se averages 80 ppm in pyrite-filled veins, but was below the detection limit in cell structures. In samples of West Virginia massive pyrite, As averages 1700 ppm, and Se averages 270 ppm (n = 24). The highest concentration of Hg (≤ 102 ppm) is in Alabama pyrite veins. Improved detailed descriptions of sulfide morphology, sulfide mineral paragenesis, and trace-element concentration and distribution allow more informed predictions of: (1) the relative rate of release of trace elements during weathering of pyrite in coals, and (2) the relative effectiveness of various coal-cleaning procedures of removing pyrite. For example, trace element-rich pyrite has been shown to be more soluble than stoichiometric pyrite, and fragile fine-grained pyrite forms such as dendrites and framboids are more susceptible to dissolution and disaggregation but less amenable to removal during coal cleaning.

Alabama;Kentucky;West Virginia

Mineralogic sources of metals in leachates from the weathering of sedex, massive sulfide, and vein deposit mining wastes

Weathered mine waste consists of oxidized primary minerals and chemically unstable secondary phases that can be sources of readily soluble metals and acid rock drainage. Elevated concentrations of metals such as Cd, Cu, Fe, Mn, Ni, Pb, and Zn are observed in deionized water-based leachate solutions derived from complex sedex and Cu-Pb-Zn mine wastes. Leachate (USGS FLT) from the Elizabeth mine, a massive sulfide deposit, has a pH of 3.4 and high concentrations of Al (16700 ug/L), Cu (440 ug/L), and Zn (8620 ug/L). Leachate from the sedex Faro mine has a pH of 3.5 and high concentrations of Al (2040 ug/L), Cu (1930 ug/L), Pb (2080 ug/L), and Zn (52900 ug/L). In contrast, higher-pH leachates produced from tailings of polymetallic vein deposits have order of magnitude lower metal concentrations. These data indicate that highly soluble secondary mineral phases exist at the surface of waste material where the samples were collected. Sulfide minerals from all sites exhibit differential degrees of weathering, from dissolution etched grain rims, to rinds of secondary minerals, to skeletal remnants. These microscale mineral-dissolution textures enhance weathering and metal teachability of waste material. Besides the formation of secondary minerals, sulfide grains from dried tailings samples may be coated by amorphous Fe-Al-Si minerals that also adsorb metals such as Cu, Ni, and Zn.

Conference Paper

Hydrothermal zebra dolomite in the Great Basin, Nevada--attributes and relation to Paleozoic stratigraphy, tectonics, and ore deposits

In other parts of the world, previous workers have shown that sparry dolomite in carbonate rocks may be produced by the generation and movement of hot basinal brines in response to arid paleoclimates and tectonism, and that some of these brines served as the transport medium for metals fixed in Mississippi Valley-type (MVT) and sedimentary exhalative (Sedex) deposits of Zn, Pb, Ag, Au, or barite. Numerous occurrences of hydrothermal zebra dolomite (HZD), comprised of alternating layers of dark replacement and light void-filling sparry or saddle dolomite, are present in Paleozoic platform and slope carbonate rocks on the eastern side of the Great Basin physiographic province. Locally, it is associated with mineral deposits of barite, Ag-Pb-Zn, and Au. In this paper the spatial distribution of HZD occurrences, their stratigraphic position, morphological characteristics, textures and zoning, and chemical and stable isotopic compositions were determined to improve understanding of their age, origin, and relation to dolostone, ore deposits, and the tectonic evolution of the Great Basin. In northern and central Nevada, HZD is coeval and cogenetic with Late Devonian and Early Mississippian Sedex Au, Zn, and barite deposits and may be related to Late Ordovician Sedex barite deposits. In southern Nevada and southwest California, it is cogenetic with small MVT Ag-Pb-Zn deposits in rocks as young as Early Mississippian. Over Paleozoic time, the Great Basin was at equatorial paleolatitudes with episodes of arid paleoclimates. Several occurrences of HZD are crosscut by Mesozoic or Cenozoic intrusions, and some host younger pluton-related polymetallic replacement and Carlin-type gold deposits. The distribution of HZD in space (carbonate platform, margin, and slope) and stratigraphy (Late Neoproterozoic Ediacaran–Mississippian) roughly parallels that of dolostone and both are prevalent in Devonian strata. Stratabound HZD is best developed in Ediacaran and Cambrian units, whereas discordant HZD is proximal to high-angle structures at the carbonate platform margin, such as strike-slip and growth faults and dilational jogs. Fabric-selective replacement and dissolution features (e.g., collapse breccias, voids with geopetal textures) are common, with remaining void space lined with light-colored dolomite crystals that exhibit zoning under cathodoluminescence. Zoned crystals usually contain tiny (<1–3 μm) fluid inclusions with vapor bubbles, requiring Th > ∼70 °C. The oxygen isotopic compositions of HZD are consistent with formation temperatures of 50–150 °C requiring brine circulation to depths of 2–5 km, or more. The few HZD occurrences with the highest concentrations of metals (especially Fe, Mn, and Zn) and the largest isotopic shifts are closely associated with Sedex or MVT deposits known to have formed from hotter brines (e.g., Th > 150–250 °C). These relationships permit that HZD formed at about the same time as dolostone, from brines produced by the evaporation of seawater during arid paleoclimates at equatorial paleolatitudes. Both dolostone and HZD may have formed as basinal brines, which migrated seaward from evaporative pans on the platform, with dolostone forming at low temperatures along shallow migration pathways through permeable limestones, and HZD forming at high temperatures along deeper migration pathways through basal aquifers and dilatant high-angle faults. The small MVT deposits were chemical traps where hot brines encountered rocks or fluids containing reduced sulfur. The abundant Sedex deposits mark sites where hot brine discharged at the seafloor in adjacent basins. Thus the distribution of HZD may map deep migration pathways and upflow zones between eastern shallow marine facies, where evaporative brine could have been generated, and western Sedex deposits, where heated brines discharged along faults into platform margin, slope, and basin facies. The small size and scarcity of Pb-Zn deposits and the abundance of barite deposits in the Great Basin suggests the brines were generally reduced, possibly due to reactions with carbonaceous rocks along deep migration pathways. While this scenario may have occurred at several times, the age and abundance of Sedex deposits suggest that such a hydrology was best developed in the Late Ordovician, Late Devonian, and Early Mississippian, possibly in response to episodes of extension and forebulge faults associated with the Antler orogeny. The improved understanding of HZD may aid future exploration for ore deposits in the Great Basin.

Nevada

What's weathering? Mineralogy and field leach studies in mine waste, Leadville and Montezuma mining districts, Colorado

Weathering is important in the development of rock fabrics that control porosity in mine-waste materials, and in turn, porosity affects metal transport through and from mine-waste piles into watersheds. Mine-waste piles are dynamic physical and chemical systems as evidenced by remnant Fe-oxide boxwork structures after sulfide minerals, development of alteration rinds and etch pits on grains, and precipitation of secondary minerals under low temperature conditions. These microscale changes in the mine-waste materials are the result of partial to total dissolution of sulfide and other minerals. Mine-waste materials from the Dinero, Lower Chatauqua, and Saints John sites, Leadville and Montezuma mining districts, Colorado, exhibit rock fabrics that indicate that weathering products, e.g., Fe oxyhydroxides, jarosite, and clays, have been transported in suspension through the waste piles and deposited in voids and as coatings on rock fragments. Microscale characterization of weathered, partially dissolved minerals lends insight into the source of leachable metals in these mine-waste sites. Mineralogic studies show that galena in the Lower Chatauqua waste is enriched in Ag. Qualitative and semiquantitative microanalysis of weathered, altered galena grains from all three sites show that the Ag-bearing galena is more susceptible to dissolution. It is not surprising, then, that solutions experimentally leached from Lower Chatauqua waste are higher in Pb (2310 ppb) compared to leachates from the Dinero (31 ppb) and Saints John (1360 ppb) wastes. The mobility of metals is increased at acidic pH. Using the USGS Field Leach Test protocol, leachate derived from the Dinero waste has a pH of 3 and high concentrations of Al (443 ppb), Fe (441 ppb), and Zn (7970 ppb). Leachate from Sts. John tailings has a pH about 4 and high concentrations of Mn (1520 ppb), Zn (2240 ppb), and Pb (1360 ppb). Leachate from the Lower Chatauqua waste has an intermediate pH of 5, but in addition to the high Pb level already mentioned, it contains high levels of K (1.9 ppm), Mn (6720 ppb), and Zn (1550 ppb). The high concentration of metals, despite the intermediate pH of the leachate, may be explained by acidic microenvironments that exist at the surfaces of sulfide minerals, where sulfur-and iron-oxidizing microbes may flourish. It is at the reactive mineral-oxygen-water interface where metals are released and low-pH sulfate precipitates such as jarosite-beudantite form.

Colorado

Sources of acid and metals from the weathering of the Dinero waste pile, Lake Fork watershed, Leadville, Colorado

Two trenches were dug into the south Dinero mine-waste pile near Leadville, Colorado, to study the weathering of rock fragments and the mineralogic sources of metal contaminants in the surrounding wetland and Lake Fork Watershed. Water seeping from the base of the south Dinero waste-rock pile was pH 2.9, whereas leachate from a composite sample of the rock waste was pH 3.3. The waste pile was mostly devoid of vegetation, open to infiltration of precipitation, and saturated at the base because of placement in the wetland. The south mine-waste pile is composed of poorly sorted material, ranging from boulder-size to fine-grained rock fragments. The trenches showed both matrix-supported and clast-supported zones, with faint horizontal color banding, suggesting zonation of Fe oxides. Secondary minerals such as jarosite and gypsum occurred throughout the depth of the trenches. Infiltration of water and transport of dissolved material through the pile is evidenced by optically continuous secondary mineral deposits that fill or line voids. Iron-sulfate material exhibits microlaminations with shrinkage cracking and preferential dissolution of microlayers that evidence drying and wetting events. In addition to fluids, submicron-sized to very fine-grained particles such as jarosite are transported through channel ways in the pile. Rock fragments are coated with a mixture of clay, jarosite, and manganese oxides. Dissolution of minerals is a primary source of metals. Skeletal remnants of grains, outlined by Fe-oxide minerals, are common. Potassium jarosite is the most abundant jarosite phase, but Pb-and Ag-bearing jarosite are common. Grain-sized clusters of jarosite suggest that entire sulfide grains were replaced by very fine-grained jarosite crystals. The waste piles were removed from the wetland and reclaimed upslope in 2003. This was an opportunity to test methods to identify sources of acid and metals and metal transport processes within a waste pile. A series of entrapment ponds, lined with limestone rip rap, was created where the mine waste was once situated. A flooded adit discharges low-pH metal-bearing waters into the ponds. A white (Zn, Mn)-sulfate precipitate was observed in 2003 around the edges of the most distal pond.

Colorado

Modes of occurrence of mercury and other trace elements in coals from the warrior field, Black Warrior Basin, Northwestern Alabama

The mineralogic residence and abundance of trace metals is an important environmental issue. Data from the USGS coal quality database show that potentially toxic elements, including Hg, As, Mo, Se, Cu, and Tl are enriched in a subset of coal samples in the Black Warrior Basin of Alabama, USA. Although the coal as-mined typically is low in these elements, localized enrichments occur in high-pyrite coals and near faults. Microscopic analyses demonstrate that the residence of these elements is dominantly in a late-stage pyrite associated with structurally disrupted coal. Further, our data suggest addition of Hg to the coal matrix as well. The source of these trace elements was hydrothermal fluids driven into the Black Warrior Basin by Alleghanian age tectonism. ?? 2004 Published by Elsevier B.V.

International Journal of Coal Geology

Trace-metal sources and their release from mine wastes: examples from humidity cell tests of hardrock mine waste and from Warrior Basin coal

To assess the potential impact of metal and acid contamination from mine-waste piles, it is important to identify the mineralogic source of trace metals and their mode of occurrence. Microscopic analysis of mine-waste samples from both hard-rock and coalmine waste samples demonstrate a microstructural control, as well as mineralogic control, on the source and release of trace metals into local water systems. The samples discussed herein show multiple periods of sulfide mineralization with varying concentrations of trace metals. In the first case study, two proprietary hard-rock mine-waste samples exposed to a series of humidity cell tests (which simulate intense chemical weathering conditions) generated acid and released trace metals. Some trace elements of interest were: arsenic (45-120 ppm), copper (60-320 ppm), and zinc (30-2,500 ppm). Untested and humidity cell-exposed samples were studied by X-ray diffraction, scanning electron microscope with energy dispersive X-ray (SEM/EDX), and electron microprobe analysis. Studies of one sample set revealed arsenic-bearing pyrite in early iron- and magnesium-rich carbonate-filled microveins, and iron-, copper-, arsenic-, antimony-bearing sulfides in later crosscutting silica-filled microveins. Post humidity cell tests indicated that the carbonate minerals were removed by leaching in the humidity cells, exposing pyrite to oxidative conditions. However, sulfides in the silica-filled veins were more protected. Therefore, the trace metals contained in the sulfides within the silica-filled microveins may be released to the surface and (or) ground water system more slowly over a greater time period. In the second case study, trace metal-rich pyrite-bearing coals from the Warrior Basin, Alabama were analyzed. Arsenic-bearing pyrite was observed in a late-stage pyrite phase in microfaults and microveins that crosscut earlier arsenic.

Conference Paper

Structural styles of Paleozoic intracratonic fault reactivation: A case study of the Grays Point fault zone in southeastern Missouri, USA

A pronounced, subparallel set of northeast-striking faults occurs in southeastern Missouri, but little is known about these faults because of poor exposure. The Commerce fault system is the southernmost exposed fault system in this set and has an ancestry related to Reelfoot rift extension. Recent published work indicates that this fault system has a long history of reactivation. The northeast-striking Grays Point fault zone is a segment of the Commerce fault system and is well exposed along the southeast rim of an inactive quarry. Our mapping shows that the Grays Point fault zone also has a complex history of polyphase reactivation, involving three periods of Paleozoic reactivation that occurred in Late Ordovician, Devonian, and post-Mississippian. Each period is characterized by divergent, right-lateral oblique-slip faulting. Petrographic examination of sidwall rip-out clasts in calcite-filled faults associated with the Grays Point fault zone supports a minimum of three periods of right-lateral oblique-slip. The reported observations imply that a genetic link exists between intracratonic fault reactivation and strain produced by Paleozoic orogenies affecting the eastern margin of Laurentia (North America). Interpretation of this link indicate that right-lateral oblique-slip has occurred on all of the northeast-striking faults in southeastern Missouri as a result of strain influenced by the convergence directions of the different Paleozoic orogenies.

Tectonophysics