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At least 361 records · Page 20Linked to original sources

Organic petrography of Leonardian (Wolfcamp A) mudrocks and carbonates, Midland Basin, Texas: The fate of oil-prone sedimentary organic matter in the oil window

To better understand evolution of oil-prone sedimentary organic matter to petroleum and expulsion from source rock, we evaluated organic petrographic features of Leonardian Wolfcamp A repetitive siliceous and calcareous mudrock and fine-grained carbonate lithofacies cycles occurring in the R. Ricker #1 core from Reagan County, Midland Basin, Texas. The objectives of the petrographic investigation were to estimate thermal maturity, identify organic matter types and abundances, and identify the presence or absence of migrated hydrocarbons in organic-lean carbonate layers. An integrated analytical program included geochemical screening [total organic carbon (TOC) content by LECO, programmed pyrolysis by hydrocarbon analyzer with kinetics (HAWK) including analysis of solvent-extracted samples], X-ray diffraction mineralogy, organic petrography, scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) including correlative light and electron microscopy (CLEM), and micro-Fourier transform infrared spectroscopy (μ-FTIR) analyses of solid bitumen. The data indicate all samples are early to middle oil window thermal maturity with solid bitumen reflectance (BR o ) values of 0.55–0.86% and T max of 440–455 °C. Organic matter is predominantly solid bitumen (as identified by optical microscopy) in all lithofacies with minor contributions from inertinite. Solid bitumen abundance decreases from siliceous mudrock (TOC >3.0 wt%) to calcareous mudrock (TOC 1.0 to 3.0 wt%) to fine-grained carbonate (TOC <1.0 wt%) lithofacies. Interpretations of petrographic data suggest siliceous and calcareous mudrocks are source rock lithofacies and contain solid bitumen (with petroleum generation potential) that is residual (what remains) from conversion of an original Type II sedimentary organic matter. In turn, fine-grained carbonates are interpreted as reservoir lithofacies which contained little or no original oil-prone sedimentary organic matter and at present-day contain only a minor component of migrated solid petroleum sourced from adjacent siliceous and calcareous mudrock lithofacies. This work helps to document petroleum generation and migration processes, improve unconventional reservoir characterization and better define areas of oil window thermal maturity in an area critical to United States hydrocarbon production.

Texas↗

Characterization of the unconventional Tuscaloosa marine shale reservoir in southwestern Mississippi, USA: Insights from optical and SEM petrography

This study presents new optical petrography and electron microscopy data, interpreted in the context of previously published petrophysical, geochemical, and mineralogical data, to further characterize the Tuscaloosa marine shale (TMS) as an unconventional reservoir in southwestern Mississippi. The basal high resistivity zone has a higher proportion of Type II sedimentary organic matter than the overlying TMS, indicating it is more prone to oil generation. Optical petrography and electron microscopy reveal a heterogeneous clay matrix with ubiquitous pyrite grains, quartz, feldspar, glaucony, foraminifera, shell fragments, and rarer occurrences of apatite and crinoid fragments as well as liptinite, alginite, inertinite, and vitrinite. Our petrographic observations suggest that higher abundances of detrital quartz grains coupled with minimal authigenic cements result in higher porosity and permeability. However, the TMS is also more clay-rich than other unconventional shale oil and gas plays, which can impair the effectiveness of hydraulic fracture stimulation. Thin section observations reveal alternating clay and calcium carbonate laminae that are interpreted to reflect changes in sediment flux. Planktonic foraminifera indicate an overlying oxygenated water column while benthic inoceramid fragments and pervasive authigenic pyrite suggest anoxic or dysoxic bottom water conditions. Apatite fragments in thin section suggest mixing events and an influx of nutrient-rich sediments. Overall, these observations suggest that a variety of paleodepositional environments occurred in the TMS and the lithofacies diversity resulting from these small-scale depositional cycles makes it difficult to determinatively identify areas conducive to enhanced economic hydrocarbon recovery.

Mississippi, Lousianna↗

The imaging performance of the SRC on Mars Express

The Mars Express spacecraft carries the pushbroom scanner high-resolution stereo camera (HRSC) and its added imaging subsystem super resolution channel (SRC). The SRC is equipped with its own optical system and a 1024×1024 framing sensor. SRC produces snapshots with 2.3 m ground pixel size from the nominal spacecraft pericenter height of 250 km, which are typically embedded in the central part of the large HRSC scenes. The salient features of the SRC are its light-weight optics, a reliable CCD detector, and high-speed read-out electronics. The quality and effective visibility of details in the SRC images unfortunately falls short of what has been expected. In cases where thermal balance cannot be reached, artifacts, such as blurring and “ghost features” are observed in the images. In addition, images show large numbers of blemish pixels and are plagued by electronic noise. As a consequence, we have developed various image improving algorithms, which are discussed in this paper. While results are encouraging, further studies of image restoration by dedicated processing appear worthwhile. The SRC has obtained more than 6940 images at the time of writing (1 September 2007), which often show fascinating details in surface morphology. SRC images are highly useful for a variety of applications in planetary geology, for studies of the Mars atmosphere, and for astrometric observations of the Martian satellites. This paper will give a full account of the design philosophy, technical concept, calibration, operation, integration with HRSC, and performance, as well as science accomplishments of the SRC.

Planetary and Space Science↗

FeS-coated sand for removal of arsenic(III) under anaerobic conditions in permeable reactive barriers

Iron sulfide (as mackinawite, FeS) has shown considerable promise as a material for the removal of As(III) under anoxic conditions. However, as a nanoparticulate material, synthetic FeS is not suitable for use in conventional permeable reactive barriers (PRBs). This study developed a methodology for coating a natural silica sand to produce a material of an appropriate diameter for a PRB. Aging time, pH, rinse time, and volume ratios were varied, with a maximum coating of 4.0 mg FeS/g sand achieved using a pH 5.5 solution at a 1:4 volume ratio (sand: 2 g/L FeS suspension), three days of aging and no rinsing. Comparing the mass deposited on the sand, which had a natural iron-oxide coating, with and without chemical washing showed that the iron-oxide coating was essential to the formation of a stable FeS coating. Scanning electron microscopy images of the FeS-coated sand showed a patchwise FeS surface coating. X-ray photoelectron spectroscopy showed a partial oxidation of the Fe(II) to Fe(III) during the coating process, and some oxidation of S to polysulfides. Removal of As(III) by FeS-coated sand was 30% of that by nanoparticulate FeS at pH 5 and 7. At pH 9, the relative removal was 400%, perhaps due to the natural oxide coating of the sand or a secondary mineral phase from mackinawite oxidation. Although many studies have investigated the coating of sands with iron oxides, little prior work reports coating with iron sulfides. The results suggest that a suitable PRB material for the removal of As(III) under anoxic conditions can be produced through the deposition of a coating of FeS onto natural silica sand with an iron-oxide coating. Iron sulfide (as mackinawite, FeS) has shown considerable promise as a material for the removal of As(III) under anoxic conditions. However, as a nanoparticulate material, synthetic FeS is not suitable for use in conventional permeable reactive barriers (PRBs). This study developed a methodology for coating a natural silica sand to produce a material of an appropriate diameter for a PRB. Aging time, pH, rinse time, and volume ratios were varied, with a maximum coating of 4.0 mg FeS/g sand achieved using a pH 5.5 solution at a 1:4 volume ratio (sand: 2 g/L FeS suspension), three days of aging and no rinsing. Comparing the mass deposited on the sand, which had a natural iron-oxide coating, with and without chemical washing showed that the iron-oxide coating was essential to the formation of a stable FeS coating. Scanning electron microscopy images of the FeS-coated sand showed a patchwise FeS surface coating. X-ray photoelectron spectroscopy showed a partial oxidation of the Fe(II) to Fe(III) during the coating process, and some oxidation of S to polysulfides. Removal of As(III) by FeS-coated sand was 30% of that by nanoparticulate FeS at pH 5 and 7. At pH 9, the relative removal was 400%, perhaps due to the natural oxide coating of the sand or a secondary mineral phase from mackinawite oxidation. Although many studies have investigated the coating of sands with iron oxides, little prior work reports coating with iron sulfides. The results suggest that a suitable PRB material for the removal of As(III) under anoxic conditions can be produced through the deposition of a coating of FeS onto natural silica sand with an iron-oxide coating.

Water Research↗

U-Pb geochronology of zircon and polygenetic titanite from the Glastonbury Complex, Connecticut, USA: An integrated SEM, EMPA, TIMS, and SHRIMP study

U-Pb ages for zircon and titanite from a granodioritic gneiss in the Glastonbury Complex, Connecticut, have been determined using both isotope dilution thermal ionization mass spectrometry (TIMS) and the sensitive high resolution ion microprobe (SHRIMP). Zircons occur in three morphologic populations: (1) equant to stubby, multifaceted, colorless, (2) prismatic, dark brown, with numerous cracks, and (3) elongate, prismatic, light tan to colorless. Cathodoluminescence (CL) imaging of the three populations shows simple concentric oscillatory zoning. The zircon TIMS age [weighted average of 207Pb/206Pb ages from Group 3 grains-450.5 ?? 1.6 Ma (MSWD=1.11)] and SHRIMP age [composite of 206Pb/238 U age data from all three groups-448.2 ?? 2.7 Ma (MSWD = 1.3)], are interpreted to suggest a relatively simple crystallization history. Titanite from the granodioritic gneiss occurs as both brown and colorless varieties. Scanning electron microscope backscatter (BSE) images of brown grains show multiple cross-cutting oscillatory zones of variable brightness and dark overgrowths. Colorless grains are unzoned or contain subtle wispy or very faint oscillatory zoning. Electron microprobe analysis (EMPA) clearly distinguishes the two populations. Brown grains contain relatively high concentrations of Fe2O3, Ce2O3 (up to ~ 1.5 wt.%), Nb2O5, and Zr. Cerium concentration is positively correlated with total REE + Y concentration, which together can exceed 3.5 wt.%. Oscillatory zoning in brown titanite is correlated with variations in REE concentrations. In contrast, colorless titanite (both as discrete grains and overgrowths on brown titanite) contains lower concentrations of Y, REE, Fe2O3, and Zr, but somewhat higher Al2O3 and Nb2O5. Uranium concentrations and Th/U discriminate between brown grains (typically 200-400 ppm U; all analyses but one have Th/U between about 0.8 and 2) and colorless grains (10-60 ppm U; Th/U of 0-0.17). In contrast to the zircon U-Pb age results, SHRIMP U-Pb data from titanite indicate multiple growth episodes. In brown grains, oscillatory zoned cores formed at 443 ?? 6 Ma, whereas white (in BSE) cross-cutting zones are 425 ?? 9 Ma. Colorless grains and overgrowths on brown grains yield an age of 265 ?? 8 Ma (using the Total Pb method) or 265 ?? 5 Ma (using the weighted average of the 206Pb/238U ages). However, EMPA chemical data identify zoning that suggests that this colorless titanite may preserve three growth events. Oscillatory zoned portions of brown titanite grains are igneous in origin; white cross-cutting zones probably formed during a previously unrecognized event that caused partial dissolution of earlier titanite and reprecipitation of a slightly younger generation of brown titanite. Colorless titanite replaced and grew over the magmatic titanite during the Permian Alleghanian orogeny. These isotopic data indicate that titanite, like zircon, can contain multiple age components. Coupling SHRIMP microanalysis with EMPA and SEM results on dated zones as presented in this study is an efficient and effective technique to extract additional chronologic ?? 2002 Elsevier Science B.V. All rights reserved.

Chemical Geology↗

Bacterial dissimilatory reduction of arsenate and sulfate in meromictic Mono Lake, California

The stratified (meromictic) water column of alkaline and hypersaline Mono Lake, California, contains high concentrations of dissolved inorganic arsenic (~200 ??mol/L). Arsenic speciation changes from arsenate [As (V)] to arsenite [As (III)] with the transition from oxic surface waters (misolimnion) to anoxic bottom waters (monimolimnion). A radioassay was devised to measure the reduction of 73As (V) to 73As (III) and tested using cell suspensions of the As (V)-respiring Bacillus selenitireducens, which completely reduced the 73As (V). In field experiments, no significant activity was noted in the aerobic mixolimnion waters, but reduction of 73As (V) to 73As (III) was observed in all the monimolimnion samples. Rate constants ranged from 0.02 to 0.3/day, with the highest values in the samples from the deepest depths (24 and 28 m). The highest activities occurred between 18 and 21 m, where As (V) abundant (rate, ~5.9 ??mol/L per day). In contrast, sulfate reduction occurred at depths below 21 m, with the highest rates attained at 28 m (rate, ~2.3 ??mol/L per day). These results indicate that As (V) ranks second in importance, after sulfate, as an electron acceptor for anaerobic bacterial respiration in the water column. Annual arsenate respiration may mineralize as much as 14.2% of the pelagic photosynthetic carbon fixed during meromixis. When combined with sulfate-reduction data, anaerobic respiration in the water column can mineralize 32-55% of this primary production. As lakes of this type approach salt saturation, As (V) can become the most important electron acceptor for the biogeochemical cycling of carbon.

California↗

An experimental investigation of barite formation in seawater

We report results from time-series decay and sequential leaching experiments of laboratory cultured and coastal plankton to elucidate the mechanisms controlling barite formation in seawater. Batch-cultured diatoms ( Stephanopyxis palmerina ) and coccolithophorids (Emiliania huxleyi) were let to decay in the dark for 8-10 weeks, suspended in aerated seawater. The development of barite crystals was monitored by Scanning Electron Microscopy (SEM). A similar experiment was conducted with plankton collected during the spring-bloom in Vineyard Sound (MA). In addition to SEM, suspended particles were sequentially leached for Ba (distilled water rinse; 10% (v/v) HNO3 rinse at room temperature; 30% (v/v) HCl at 80??C overnight; 50% (v/v) HNO3 at 80??C overnight) immediately after collection, and after 10-week decay in seawater, in seawater poisoned with HgCl2, and in seawater spiked with 135Ba. Both experiments showed an increase in the number of barite crystals during decay. The spring-bloom plankton had initially a large pool of labile Ba, soluble in distilled water and cold dilute HNO3 that was lost from the plankton after 10-week decay in both axenic and nonaxenic conditions. In contrast, Ba in the decayed plankton samples was predominantly in forms extracted by hot HCl and hot HNO3 acids, which were attributed to presence of barite Ba and refractory organic Ba respectively. The increase in barite crystal counts under a Scanning Electron Microscope (SEM), the increase in HCl extractable Ba relative to organic carbon, and the loss of a large fraction of Ba during plankton decay suggest that living plankton consists of a relatively large pool of labile Ba, which is rapidly released during plankton decomposition and acts as the main source of Ba for barite formation in supersaturated microenvironments. Since mass balance indicates that only a small proportion (2 to 4%) of the labile-Ba pool is converted to barite, the availability of microenvironments that could locally concentrate Ba released by plankton decay seems to be the main limiting factor in barite precipitation. ?? 2003 Elsevier Science Ltd.

Geochimica et Cosmochimica Acta↗

Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico: II. Rate and mechanism of biotite weathering

Samples of soil, saprolite, bedrock, and porewater from a lower montane wet forest, the Luquillo Experimental Forest (LEF) in Puerto Rico, were studied to investigate the rates and mechanisms of biotite weathering. The soil profile, at the top of a ridge in the Rio Icacos watershed, consists of a 50–100-cm thick layer of unstructured soil above a 600–800 cm thick saprolite developed on quartz diorite. The only minerals present in significant concentration within the soil and saprolite are biotite, quartz, kaolinite, and iron oxides. Biotite is the only primary silicate releasing significant K and Mg to porewaters. Although biotite in samples of the quartz diorite bedrock is extensively chloritized, chlorite is almost entirely absent in the saprolite phyllosilicates. Phyllosilicate grains are present as 200–1000 μm wide books below about 50 cm depth. X-ray diffraction (XRD) and electron microprobe analyses indicate that the phyllosilicate grains contain a core of biotite surrounded by variable amounts of kaolinite. Lattice fringe images under transmission electron microscope (TEM) show single layers of biotite altering to two layers of kaolinite, suggesting dissolution of biotite and precipitation of kaolinite at discrete boundaries. Some single 14-Å layers are also observed in the biotite under TEM. The degree of kaolinitization of individual phyllosilicate grains as observed by TEM decreases with depth in the saprolite. This TEM work is the first such microstructural evidence of epitaxial growth of kaolinite onto biotite during alteration in low-temperature environments. The rate of release of Mg in the profile, calculated as a flux through the soil normalized per watershed land area, is approximately 500 mol hectare −1 yr −1 (1.6 × 10 −9 mol Mg m soil −2 s −1 ). This rate is similar to the flux estimated from Mg discharge out the Rio Icacos (1000 mol hectare −1 yr −1 , or 3.5 × 10 −9 mol Mg m soil −2 s −1 ), indicating that scaling up from the soil to the watershed is possible for Mg release. The rate of Mg release from biotite, normalized to Brunauer-Emmett-Teller (BET) surface area, is calculated using a mass balance equation which includes the density and volume of phyllosilicate grains, porewater chemistry and flux, and soil porosity. The mean rates of biotite weathering calculated from K and Mg release rates are approximately 6 and 11 × 10 −16 mol biotite m biotite −2 s −1 respectively, significantly slower than laboratory rates (10 −12 to 10 −11 mol biotite m biotite −2 s −1 ). The discrepancy in scaling down from the soil to the laboratory is probably explained by (1) differences in weathering mechanism between the two environments, (2) higher solute concentrations in soil porewaters, (3) loss of reactive surface area of biotite in the saprolite due to kaolinite and iron oxide coatings, and/or (4) unaccounted-for heterogeneities in flow path through the soil.

El Yunque, Luquillo Experimental Forest, Luquillo ↗

The future of scientific communication in the earth sciences: The impact of the internet

Publication on paper of research results following peer-review and editing has been the accepted means of scientific communication for several centuries. Today, the continued growth in the volume of scientific literature, the increased unit costs of archiving paper publications, and the rapidly increasing power and availability of electronic technology are creating tremendous pressures on traditional scientific communication. The earth sciences are not immune from these pressures, and the role of the traditional publication as the primary means of communication is rapidly changing. Electronic publications and network technology are radically altering the relationship between interpretative result and the underlying data. Earth science research institutions, including the Kansas Geological Survey, are experimenting with new forms of on-line publication that assure broad access to research and data and improve application of research results to societal problems. ?? 1997 Elsevier Science Ltd.

Computers & Geosciences↗

Factors controlling the abundance of organic sulfur in flash pyrolyzates of Upper Cretaceous kerogens from Sergipe Basin, Brazil

The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene + dec-1-ene) in the pyrolyzates is variable and may be related to changes in the type of primary organic input and/or to variations in rates of bacterial sulfate reduction. A concomitant increase in S/C and O/C ratios determined in situ using the electron microprobe is observed in AOM and alginites and may be related to a progressive oxidation of the organic matter during sulfurization. The S/C ratio of the AOM is systematically higher than the S C ratio of the alginites. Combined with a thiophene distribution characteristic of pyrolyzates of Type II organic matter, the higher S/C of AOM in Sergipe kerogens suggests that sulfurization and incorporation of low-molecular weight lipids derived from normal marine organic matter into the kerogen structure predominated over direct sulfurization of highly aliphatic algal biomacromolecules.The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene+dec-1-ene) in the pyrolyzates is variable and may be related to changes in the type of primary organic input and/or to variations in rates of bacterial sulfate reduction. A concomitant increase in S/C and O/C ratios determined in situ using the electron microprobe is observed in AOM and alginites and may be related to a progressive oxidation of the organic matter during sulfurization. The S/C ratio of the AOM is systematically higher than the S/C ratio of the alginites. Combined with a thiophene distribution characteristic of pyrolyzates of Type II organic matter, the higher S/C of AOM in Sergipe kerogens suggests that sulfurization and incorporation of low-molecular weight lipids derived from normal marine organic matter into the kerogen structure predominated over direct sulfurization of highly aliphatic algal biomacromolecules.

Conference Paper↗

Analysis of atmospheric paniculate matter; application of optical and selected geochemical techniques

An increase in particulate matter in the atmosphere has been shown to be linked to increased mortality but this relationship is poorly understood. Light microscopy, electron microscopy , electron microprobe , and micro-FTIR techniques have been applied to study atmospheric particulates in Brisbane, Australia as a part of a study on asthma. The particulate matter samples were collected daily from April to August 1992, and the sampling covered the autumn period which is typically a time of high asthma incidence in Brisbane. Volumetrically, most atmospheric particulate matter is less than 2 μ m in size. The microscopic analysis reveals that this material is composed mainly of combusted and incompletely burned hydrocarbons from motor vehicle exhaust emissions, quiescent spores of Mucorales, soil bacteria, and inorganic matter in the form of quartz and other silicates. Elemental and functional group analyses confirm microscope identification, documenting carbon-rich, aromatic exhaust material, more aliphatic pollen and spore material and inorganic matter. Fungal spores dominate bioaerosol and are very abundant from the end of April through May to mid-June. The cytoplasmic content of pollens or fungal spores is commonly regarded as allergenic. Particulates from the exhaust emissions and crustal material in a sub-micrometer size range may act as carriers or dispersive mechanisms for cytoplasmic material from fungal spores and pollens, perhaps causing periods of the highest exhaust emission to be the most allergenic.

International Journal of Coal Geology↗

Lanthanide, yttrium, and zirconium anomalies in the Fire Clay coal bed, Eastern Kentucky

The Fire Clay coal bed in the Central Appalachian basin region contains a laterally-persistent tonstein that is found in the coal throughout most of its areal extent. The tonstein contains an array of minerals, including sanidine, ??-quartz, anatase and euhedral zircon, thhat constitutes strong evidence for a volcanic origin of the parting. For this study, five samples of the tonstein and four sets of coal samples underlying the tonstein were collected from five sites in eastern Kentucky. Inductively coupled plasma-mass spectroscopy (ICP-MS) analysis of the tonstein and underlying coal collected from four sites in eastern Kentucky show that although Zr concentrations are high in the tonstein (570-1820 ppm on a coal-ash basis (cab)), they are highest in the coal directly underlying the tonstein (2870-4540 ppm (cab)). A similar enrichment pattern is observed in the concentration of Y plus the sum of the rare earth elements (Y + ??REE): total Y + ??REE concentrations in the five tonstein samples range from 511 to 565 ppm (cab). However, Y + ??REE contents are highest in the coals directly underlying the tonsteins: values range from 1965 to 4198 ppm (cab). Scanning electron microscopy of samples from coal which directly underlies two of the tonstein samples show that REE-rich phosphate, tentatively identified as monazite, commonly infills cracks in clays and cells in clarain and vitrain. Zircon is rare and commonly subhedral. On the basis of coal chemistry and grain morphology, we suggest that volcanic components in the tonstein were leached by ground water. The leachate, rich in Y and REE precipitated as authigenic mineral phases in the underlying coal.The Fire Clay coal bed in the Central Appalachian basin region contains a laterally-persistent tonstein that is found in the coal throughout most of its areal extent. The tonstein contains an array of minerals, including sanidine, ??-quartz, anatase and euhedral zircon, that constitutes strong evidence for a volcanic origin of the parting. For this study, five samples of the tonstein and four sets of coal samples underlying the tonstein were collected from five sites in eastern Kentucky. Inductively coupled plasma-mass spectroscopy (ICP-MS) analysis of the tonstein and underlying coal collected from four sites in eastern Kentucky show that although Zr concentrations are high in the tonstein (570-1820 ppm on a coal-ash basis (cab)), they are highest in the coal directly underlying the tonstein (2870-4540 ppm (cab)). A similar enrichment pattern is observed in the concentration of Y plus the sum of the rare earth elements (Y+???REE): total Y+???REE concentrations in the five tonstein samples range from 511 to 565 ppm (cab). However, Y+???REE contents are highest in the coals directly underlying the tonsteins: values range from 1965 to 4198 ppm (cab). Scanning electron microscopy of samples from coal which directly underlies two of the tonstein samples show that REE-rich phosphate, tentatively identified as monazite, commonly infills cracks in clays and cells in clarain and vitrain. Zircon is rare and commonly subhedral. On the basis of coal chemistry and grain morphology, we suggest that volcanic components in the tonstein were leached by ground water. The leachate, rich in Y and REE precipitated as authigenic mineral phases in the underlying coal.

International Journal of Coal Geology↗

In-situ analysis of solid bitumen in coal: Examples from the Bowen Basin and the Illinois Basin

Solid bitumen and associated vitrinite from selected coals from the Bowen Basin and the Illinois Basin were studied using electron microprobe and micro-FTIR techniques. The coal studied covers a range of vitrinite reflectance from 0.59% to 1.33%. Carbon content in the bitumen is generally lower than in vitrinite in coals with vitrinite reflectance below 0.67%. In coals with reflectance above 0.67%, carbon content of bitumen is higher than in vitrinite, reflecting higher aromaticity due to hydrocarbon generation. Sulfur and iron content are comparable between vitrinite and bitumen. Functional group distribution suggests the presence of two types of bitumen in the Illinois Basin coals. The more aliphatic variety occurring in veins and cleats is interpreted as pre-gas generation bitumen, and the more aromatic variety filling cells and voids in inertinite as post-gas generation bitumen. (C) 2000 Elsevier Science B.V. All rights reserved.Solid bitumen and associated vitrinite from selected coals from the Bowen Basin and the Illinois Basin were studied using electron microprobe and micro-FTIR techniques. The coal studied covers a range of vitrinite reflectance from 0.59% to 1.33%. Carbon content in the bitumen is generally lower than in vitrinite in coals with vitrinite reflectance below 0.67%. In coals with reflectance above 0.67%, carbon content of bitumen is higher than in vitrinite, reflecting higher aromaticity due to hydrocarbon generation. Sulfur and iron content are comparable between vitrinite and bitumen. Functional group distribution suggests the presence of two types of bitumen in the Illinois Basin coals. The more aliphatic variety occurring in veins and cleats is interpreted as pre-gas generation bitumen, and the more aromatic variety filling cells and voids in inertinite as post-gas generation bitumen.

International Journal of Coal Geology↗

Ion irradiation damage in ilmenite at 100 K

A natural single crystal of ilmenite (FeTiO3) was irradiated at 100 K with 200 keV Ar2+. Rutherford backscattering spectroscopy and ion channeling with 2 MeV He+ ions were used to monitor damage accumulation in the surface region of the implanted crystal. At an irradiation fluence of 1 ?? 1015 Ar2+/cm2, considerable near-surface He+ ion dechanneling was observed, to the extent that ion yield from a portion of the aligned crystal spectrum reached the yield level of a random spectrum. This observation suggests that the near-surface region of the crystal was amorphized by the implantation. Cross-sectional transmission electron microscopy and electron diffraction on this sample confirmed the presence of a 150 nm thick amorphous layer. These results are compared to similar investigations on geikielite (MgTiO3) and spinel (MgAl2O4) to explore factors that may influence radiation damage response in oxides.

Nuclear Instruments and Methods in Physics Researc↗

Dissimilatory arsenate reductase activity and arsenate-respiring bacteria in bovine rumen fluid, hamster feces, and the termite hindgut

Bovine rumen fluid and slurried hamster feces completely reduced millimolar levels of arsenate to arsenite upon incubation under anoxic conditions. This activity was strongly inhibited by autoclaving or aerobic conditions, and partially inhibited by tungstate or chloramphenicol. The rate of arsenate reduction was faster in feces from a population of arsenate-watered (100 ppm) hamsters compared to a control group watered without arsenate. Using radioisotope methods, arsenate reductase activity in hamster feces was also detected at very low concentrations of added arsenate (∼10 μM). Bacterial cultures were isolated from these materials, as well as from the termite hindgut, that grew using H 2 as their electron donor, acetate as their carbon source, and arsenate as their respiratory electron acceptor. The three cultures aligned phylogenetically either with well-established enteric bacteria, or with an organism associated with feedlot fecal wastes. Because arsenite is transported across the gut epithelium more readily than arsenate, microbial dissimilatory reduction of arsenate in the gut may promote the body's absorption of arsenic and hence potentiate its toxicity.

FEMS Microbiology Ecology↗

Geochemical heterogeneity of a gasoline-contaminated aquifer

The scale of biogeochemical reactions was studied in a physically and chemically heterogeneous surficial Coastal Plain aquifer contaminated by a gasoline spill. The physical heterogeneity of the aquifer is manifested in two hydrologic units, a shallow local aquifer of perched water and a regional sandy aquifer. Over the studied vertical interval of 21.3 ft (6.5 m), concentrations of reactive species varied by orders of magnitude, and the impact of biodegradation was expressed to widely varying degrees. A thin (3 ft thick) section of the perched-water zone was the most contaminated; total aromatic hydrocarbons were as high as 19.4 mg/l. Hydrocarbons were degraded by microbially mediated reactions that varied over short vertical distances and time. Anaerobic processes dominated within the low-permeability clay unit, whereas in the more permeable sandy layers nitrate reduction and aerobic degradation occurred. Hydrocarbons were more persistent over time in the low-permeability layer due to the limited availability of electron acceptors for degradation. The microbial degradation of hydrocarbons was linked to sulfate and iron reduction in the clay unit and led to alterations in the aquifer solids; electron microscopy revealed the presence of FeS minerals encrusting primary aquifer grains. High concentrations of Fe 2+ in groundwater, up to 34.5 mg/l, persist in kinetic disequilibrium in the presence of elevated H 2 S levels of 1.0 mg/l. Assessment of aquifer heterogeneities and groundwater contamination was possible due to sample discrimination at a scale of approximately 2 ft (∼0.6 m), a much finer resolution than is attempted in many remedial investigations of polluted aquifers. The information obtained in this type of study is essential to the development of models capable of estimating the fate of hydrocarbons at a site scale.

Journal of Contaminant Hydrology↗

Mode of occurrence of chromium in four US coals

The mode of occurrence of chromium in three US bituminous coals and one US subbituminous has been examined using both X-ray absorption fine structure (XAFS) spectroscopy and a selective leaching protocol supplemented by scanning electron microscopy (SEM) and electron microprobe measurements. A synthesis of results from both methods indicates that chromium occurs principally in two forms in the bituminous coals: the major occurrence of chromium is associated with the macerals and is not readily leached by any reagent, whereas a second, lesser occurrence, which is leachable in hydrofluoric acid (HF), is associated with the clay mineral, illite. The former occurrence is believed to be a small particle oxyhydroxide phase (CrO(OH)). One coal also contained a small fraction (<5%) of the chromium in the form of a chromian magnetite, and the leaching protocol indicated the possibility of a similar small fraction of chromium in sulfide form in all three coals. There was little agreement between the two techniques on the mode of occurrence of chromium in the subbituminous coal; however, only a limited number of subbituminous coals have been analyzed by either technique. The chromium in all four coals was trivalent as no evidence was found for the Cr6+ oxidation state in any coal.

Fuel Processing Technology↗

Spatial patterns of tropospheric ozone in the Mount Rainier region of the Cascade Mountains, USA

Few data exist on tropospheric ozone concentrations in rural and wildland areas of western Washington, U.S.A. We measured tropospheric ozone in Mount Rainier National Park and the Puget Sound region of Washington using electronic analyzers and passive samplers during the summers of 1994 and 1995. Electronic analyzers recorded hourly ozone concentrations from five locations between Seattle and Mount Rainier. Ozone concentrations generally increased with distance from Seattle, with maximum hourly concentrations recorded at Enumclaw (319 m elevation, 50 km SE of Seattle). Paradise (1650 m elevation, 100 km SE of Seattle) had the highest monthly mean concentration of all sites measured with analyzers. Diurnal patterns on high-ozone days indicate that concentrations at Paradise remain near 60 ppbv throughout the day, whereas ozone concentrations closer to Seattle had higher peaks during the afternoon but dropped to near zero at night. Passive ozone samplers were used to measure weekly average ozone exposures in four river drainages within Mount Rainier National Park, across an elevation gradient (420 a??2100 m). In most drainages, ozone levels increased with elevation, with highest average weekly ozone exposure (47 ppbv) recorded at 2100 m. Ozone concentrations are significantly higher in the western portion of the park, indicating that ozone exposure varies considerably over short distances. These data provide a reference point for air quality in western Washington and indicate that intensive sampling is necessary to quantify spatial patterns of tropospheric ozone in mountainous regions.

Washington↗