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Microbially mediated barite dissolution in anoxic brines

Fluids injected into shale formations during hydraulic fracturing of black shale return with extraordinarily high total-dissolved-solids (TDS) and high concentrations of barium (Ba) and radium (Ra). Barite, BaSO 4 , has been implicated as a possible source of Ba as well as a problematic mineral scale that forms on internal well surfaces, often in close association with radiobarite, (Ba,Ra)SO 4 . The dissolution of barite by abiotic processes is well quantified. However, the identification of microbial communities in flowback and produced water necessitates the need to understand barite dissolution in the presence of bacteria. Therefore, we evaluated the rates and mechanisms of abiotic and microbially-mediated barite dissolution under anoxic and hypersaline conditions in the laboratory. Barite dissolution experiments were conducted with bacterial enrichment cultures established from produced water from Marcellus Shale wells located in northcentral Pennsylvania. These cultures were dominated by anaerobic halophilic bacteria from the genus Halanaerobium . Dissolved Ba was determined by ICP-OES and barite surfaces were investigated by SEM and AFM. Our results reveal that: 1) higher amounts of barium (up to ∼5 × ) are released from barite in the presence of Halanaerobium cultures compared to brine controls after 30 days of reaction, 2) etch pits that develop on the barite (001) surface in the presence of Halanaerobium exhibit a morphology that is distinct from those that form during control experiments without bacteria, 3) etch pits that develop in the presence of Halanaerobium exhibit a morphology that is similar to the morphology of etch pits formed in the presence of strong organic chelators, EDTA and DTPA, and 4) experiments using dialysis membranes to separate barite from bacteria suggest that direct contact between the two is not required in order to promote dissolution. These results suggest that Halanaerobium increase the rate of barite dissolution in anoxic and high ionic strength solutions. Additionally, the increase in rate occurs without direct microbe-mineral contact suggesting that metabolites secreted by the bacteria may be responsible for promotion of dissolution. The findings of this study have implications for understanding barium cycling in marine/hypersaline environments, release of barium (and associated radium) from waste solids generated from energy and mining industries, as well as potential for developing new anti-scaling chemicals.

Applied Geochemistry

Holocene environmental and climatic change in the Northern Great Plains as recorded in the geochemistry of sediments in Pickerel Lake, South Dakota

The sediments in Pickerel Lake, northeastern South Dakota, provide a continuous record of climatic and environmental change for the last 12000 yr. Sediments deposited between 12 and 6 ka (radiocarbon) show extreme variations in composition, oxygen and carbon isotopic composition of bulk carbonate, carbon isotopic composition of organic matter, and magnetic susceptibility. These variations reflect changes in sources of moisture, regional vegetation types, precipitation-evaporation balance, ground- and surface-water influx, water residence time, erosion, lake productivity, water level, and water temperature. The total carbonate content of late Pleistocene sediments steadily increased from <20% at the base of the core to as much as 80% in sediments deposited between 11 and 9 ka. By about 8 ka, the total carbonate content of the sediments had declined to about 40% where it remained with little variation for the past 8 kyr, suggesting relatively stable conditions. There are marked increases in values of ??13C and ??18O in bulk carbonate, and ??13C of organic matter, in sediments deposited between 10 and 6 ka as evaporation increased, and the vegetation in the watershed changed from forest to prairie. This shift toward more 18O-enriched carbonate may also reflect a change in source or seasonality of precipitation. During this early Holocene interval the organic carbon (OC) content of the sediments remained relatively low (2-3%), but then increased rapidly to 4.5% between 7 and 6 ka, reflecting the rapid transition to a prairie lake. The OC content fluctuates slightly between 4 and 6% in sediments deposited over the past 6 kyr. Like OC and total carbonate, most variables measured show little variation in the 13 m of sediment deposited over the past 6 kyr, particularly when compared with early Holocene variations. Although the magnetic susceptibility of this upper 13 m of sediment is generally low (<10 SI units), the upper six meters of the section is marked by striking 1 m cycles (ca. 400-500 yr periodicity) in susceptibility. These cycles are interpreted as being due to variations in the influx of eolian detrital-clastic material. Century-scale cyclic variations in different proxy variables for aridity and eolian activity from sediments deposited over the past 2000 yr in other lakes in the northern Great Plains, as well as in sand dune activity, suggest that aridity cycles were the dominant feature of late Holocene climate of the northern Great Plains. (C) 2000 Elsevier Science Ltd and INQUA. All rights reserved.

Quaternary International

Methylation of Hg downstream from the Bonanza Hg mine, Oregon

Speciation of Hg and conversion to methyl-Hg were evaluated in stream sediment, stream water, and aquatic snails collected downstream from the Bonanza Hg mine, Oregon. Total production from the Bonanza mine was >1360t of Hg, during mining from the late 1800s to 1960, ranking it as an intermediate sized Hg mine on an international scale. The primary objective of this study was to evaluate the distribution, transport, and methylation of Hg downstream from a Hg mine in a coastal temperate climatic zone. Data shown here for methyl-Hg, a neurotoxin hazardous to humans, are the first reported for sediment and water from this area. Stream sediment collected from Foster Creek flowing downstream from the Bonanza mine contained elevated Hg concentrations that ranged from 590 to 71,000ng/g, all of which (except the most distal sample) exceeded the probable effect concentration (PEC) of 1060ng/g, the Hg concentration above which harmful effects are likely to be observed in sediment-dwelling organisms. Concentrations of methyl-Hg in stream sediment collected from Foster Creek varied from 11 to 62ng/g and were highly elevated compared to regional baseline concentrations (0.11-0.82ng/g) established in this study. Methyl-Hg concentrations in stream sediment collected in this study showed a significant correlation with total organic C (TOC, R 2 =0.62), generally indicating increased methyl-Hg formation with increasing TOC in sediment. Isotopic-tracer methods indicated that several samples of Foster Creek sediment exhibited high rates of Hg-methylation. Concentrations of Hg in water collected downstream from the mine varied from 17 to 270ng/L and were also elevated compared to baselines, but all were below the 770ng/L Hg standard recommended by the USEPA to protect against chronic effects to aquatic wildlife. Concentrations of methyl-Hg in the water collected from Foster Creek ranged from 0.17 to 1.8ng/L, which were elevated compared to regional baseline sites upstream and downstream from the mine that varied from <0.02 to 0.22ng/L. Aquatic snails collected downstream from the mine were elevated in Hg indicating significant bioavailability and uptake of Hg by these snails. Results for sediment and water indicated significant methyl-Hg formation in the ecosystem downstream from the Bonanza mine, which is enhanced by the temperate climate, high precipitation in the area, and high organic matter.

Oregon

Petrology, mineralogy and geochemistry of mined coals, western Venezuela

Upper Paleocene to middle Miocene coal samples collected from active mines in the western Venezuelan States of Táchira, Mérida and Zulia have been characterized through an integrated geochemical, mineralogical and petrographic investigation. Proximate, ultimate, calorific and forms of sulfur values, major and trace element, vitrinite reflectance, maceral concentrations and mineral matter content have been determined for 16 channel samples from 14 mines. Ash yield generally is low, ranging from < 1 to 17 wt.% (mean = 5 wt.%) on a dry basis (db). Total sulfur content is low to moderate, ranging from 1 to 6 wt.%, db (average = 1.7 wt.%). Calorific value ranges from 25.21 to 37.21 MJ/kg (10,840–16,000 Btu/lb) on a moist, mineral-matter-free basis (average = 33.25 MJ/kg, 14,300 Btu/lb), placing most of the coal samples in the apparent rank classification of high-volatile bituminous. Most of the coal samples exhibit favorable characteristics on the various indices developed to predict combustion and coking behavior and concentrations of possible environmentally sensitive elements (As, Be, Cd, Cr, Co, Hg, Mn, Ni, Pb, Sb, Se, Th and U) generally are similar to the concentrations of these elements in most coals of the world, with one or two exceptions. Concentrations of the liptinite maceral group range from < 1% to 70 vol.%. Five samples contain > 20 vol.% liptinite, dominated by the macerals bituminite and sporinite. Collotelinite dominates the vitrinite group; telinite was observed in quantities of ≤ 1 vol.% despite efforts to better quantify this maceral by etching the sample pellets in potassium permanganate and also by exposure in an oxygen plasma chamber. Inertinite group macerals typically represent < 10 vol.% of the coal samples and the highest concentrations of inertinite macerals are found in distantly spaced (> 400 km) upper Paleocene coal samples from opposite sides of Lago de Maracaibo, possibly indicating tectonic controls on subsidence related to construction of the Andean orogen. Values of maximum reflectance of vitrinite in oil ( R o max ) range between 0.42% and 0.85% and generally are consistent with the high-volatile bituminous rank classification obtained through ASTM methods. X-ray diffraction analyses of low-temperature ash residues indicate that kaolinite, quartz, illite and pyrite dominate the inorganic fraction of most samples; plagioclase, potassium feldspar, calcite, siderite, ankerite, marcasite, rutile, anatase and apatite are present in minor or trace concentrations. Semiquantitative values of volume percent pyrite content show a strong correlation with pyritic sulfur and some sulfide-hosted trace element concentrations (As and Hg). This work provides a modern quality dataset for the western Venezuela coal deposits currently being exploited and will serve as the foundation for an ongoing coal quality research program in Venezuela.

International Journal of Coal Geology

Legacy of the California Gold Rush: Environmental geochemistry of arsenic in the southern Mother Lode Gold District

Gold mining activity in the Sierra Nevada foothills, both recently and during the California Gold Rush, has exposed arsenic-rich pyritic rocks to weathering and erosion. This study describes arsenic concentration and speciation in three hydrogeologic settings in the southern Mother Lode Gold District: mineralized outcrops and mine waste rock (overburden); mill tailings submerged in a water reservoir; and lake waters in this monomictic reservoir and in a monomictic lake developing within a recent open-pit mine. These environments are characterized by distinct modes of rock-water interaction that influence the local transport and fate of arsenic. Arsenic in outcrops and waste rock occurs in arsenian pyrite containing an average of 2 wt% arsenic. Arsenic is concentrated up to 1300 ppm in fine-grained, friable, iron-rich weathering products of the arsenian pyrite (goethite, jarosite, copiapite), which develop as efflorescences and crusts on weathering outcrops. Arsenic is sorbed as a bidentate complex on goethite, and substitutes for sulfate in jarosite. Submerged mill tailings obtained by gravity core at Don Pedro Reservoir contain arsenic up to 300 ppm in coarse sand layers. Overlying surface muds have less arsenic in the solid fraction but higher concentrations in porewaters (up to 500 μg/L) than the sands. Fine quartz tailings also contain up to 3.5 ppm mercury related to the ore processing. The pH values in sediment porewaters range from 3.7 in buried gypsum-bearing sands and tailings to 7 in the overlying lake sediments. Reservoir waters immediately above the cores contain up to 3.5 μg/L arsenic; lake waters away from the submerged tailings typically contain less than 1 μg/L arsenic. Dewatering during excavation of the Harvard open-pit mine produced a hydrologic cone of depression that has been recovering toward the pre-mining groundwater configuration since mining ended in 1994. Aqueous arsenic concentrations in the 80 m deep pit lake are up to 1000 μg/L. Redistribution of the arsenic occurs during summer stratification, with highest concentrations at middle depths. The total mass of arsenic in the pit lake increases coinciding with early winter rains that erode, partially dissolve, and transport arsenic-bearing salts into the pit lake. Arsenic concentration, speciation, and distribution in the Sierra Nevada foothills depend on many factors, including the lithologic sources of arsenic, climatic influences on weathering of host minerals, and geochemical characteristics of waters with which source and secondary minerals react. Oxidation of arsenian pyrite to goethite, jarosite, and copiapite causes temporary attenuation of arsenic during summer, when these secondary minerals accumulate; subsequent rapid dissemination of arsenic into the aqueous environment is caused by annual winter storms. As the population of the Mother Lode area grows, it is increasingly important to consider these effects during planning and development of land and groundwater resources.

California

Organic petrology and geochemistry of mudrocks from the lacustrine Lucaogou Formation, Santanghu Basin, northwest China: Application to lake basin evolution

Exploration for tight oil in the frontier Santanghu Basin of northwest China has resulted in recent commercial discoveries sourced from the lacustrine Upper Permian Lucaogou Formation, already considered a “world class source rock” in the Junggar Basin to the west. Here we apply an integrated analytical program to carbonate-dominated mudrocks from the Lucaogou Formation in Santanghu Basin to document the nature of organic matter (OM) in the context of an evolving lake system. The organic-rich samples (TOC 2.8–11.4 wt%; n = 10) were widely spaced from an ~ 200 m cored section, interpreted from textural and mineralogical evidence to document transition from a lower under-filled to an overlying balanced-filled lake. Organic matter is dominated by moderate to strongly fluorescent amorphous material with Type I geochemical signature (HI values 510–755; n = 10) occurring in a continuum from lamellar stringers, 10–20 μm thick, some ≥ 1 mm in length (possible microbial mat; preserved only in lower under-filled section) to finely-disseminated amorphous groundmass intimately intermixed with mineral matrix. Biomarkers for methanotrophs and photosynthetic cyanobacteria indicate a complex microbial consortium. A unicellular prasinophyte green alga(?), similar to Tasmanites in marine rocks, is present as discrete flattened discs 50–100 μm in diameter. Type III OM including vitrinite (some fluorescent) and inertinite also is abundant. Solid bitumen, indicating local kerogen conversion, fills voids and occurs throughout the cored section. Vitrinite reflectance values are 0.47–0.58%, consistent with strong OM fluorescence but may be “suppressed”. Other proxies, e.g., biomarker parameters, indicate the Lucaogou Formation is in the early oil window at this location. On average, slightly more amorphous OM and telalginite are present in the lower section, consistent with a shallow, stratified, saline environment with low sediment dilution. More inertinite is present in the upper section, indicating greater terrestrial influx and consistent with higher quartz and plagioclase content (dominantly authigenic chalcedony and albite). Laminated mudstones in the upper section indicate anoxia prevented bioturbation from benthic grazing, also indicating stratified water column conditions. A decrease upsection in authigenic dolomite with reciprocal increase of ankerite/siderite is consistent with decreasing salinity, as is an overall decrease in gammacerane index values. These observations suggest evolution from a shallow, stratified evaporative (saline) setting to a deeper, stratified freshwater basin with higher water input during Lucaogou deposition. The evolution from an under-filled to balance-filled lake in Santanghu Basin is similar to Lucaogou deposition in Junggar Basin, suggesting similar tectonic and climatic controls. Paleoclimate interpretations from other researchers in this area suggested an evolution from semi-arid to humid conditions during the Roadian; we interpret that the evolution from an under-filled to balanced-filled lake seen in our data is in response to climate change, and may represent increased groundwater delivery to the Santanghu Basin.

International Journal of Coal Geology

Mineralogy and geochemistry of boehmite-rich coals: New insights from the Haerwusu Surface Mine, Jungar Coalfield, Inner Mongolia, China

Boehmite-rich coal of Pennsylvanian age was discovered earlier at the Heidaigou Surface Mine, Jungar Coalfield, Inner Mongolia, China. This paper reports new results on 29 bench samples of the no. 6 coal from a drill core from the adjacent Haerwusu Surface Mine, and provides new insights into the origin of the minerals and elements present. The results show that the proportion of inertinite in the no. 6 coal is higher than in other Late Paleozoic coals in northern China. Based on mineral proportions (boehmite to kaolinite ratio) and major element concentrations in the coal benches of the drill core, the no. 6 coal may be divided into five sections (I to V). Major minerals in Sections I and V are kaolinite. Sections II and IV are mainly kaolinite with a trace of boehmite, and Section III is high in boehmite. The boehmite is derived from bauxite in the weathered surface (Benxi Formation) in the sediment-source region. The no. 6 coal is rich in Al2O3 (8.89%), TiO2 (0.47%), Li (116????g/g), F (286????g/g), Ga (18????g/g), Se (6.1????g/g), Sr (350????g/g), Zr (268????g/g), REEs (172????g/g), Pb (30????g/g), and Th (17????g/g). The elements are classified into five associations by cluster analysis, i.e. Groups A, B, C, D, and E. Group A (ash-SiO2-Al2O3-Na2O-Li) and Group B (REE-Sc-In-Y-K2O-Rb-Zr-Hf-Cs-U-P2O5-Sr-Ba-Ge) are strongly correlated with ash yield and mainly have an inorganic affinity. The elements that are negatively or less strongly correlated with ash yield (with exceptions of Fe2O3, Be, V, and Ni) are grouped in the remaining three associations: Group C, Se-Pb-Hg-Th-TiO2-Bi-Nb-Ta-Cd-Sn; Group D, Co-Mo-Tl-Be-Ni-Sb-MgO-Re-Ga-W-Zn-V-Cr-F-Cu; and Group E, S-As-CaO-MnO-Fe2O3. Aluminum is mainly distributed in boehmite, followed by kaolinite. The high correlation coefficients of the Li-ash, Li-Al2O3, and Li-SiO2 pairs indicate that Li is related to the aluminosilicates in the coal. The boehmite-rich coal is high in gallium and F, which occur in boehmite and the organic matter. Selenium and Pb are mainly in epigenetic clausthalite fillings in fractures. The abundant rare earth elements in the coal benches were supplied from two sources: the bauxite on the weathered surface of the Benxi Formation and from adjacent partings by groundwater leaching during diagenesis. The light rare earth elements (LREEs) are more easily leached from the partings and incorporated into the organic matter than the heavy REEs, leading to a higher ratio of LREEs to HREEs in the coal benches than in the overlying partings. ?? 2008 Elsevier B.V. All rights reserved.

International Journal of Coal Geology

Influence of an igneous intrusion on the inorganic geochemistry of a bituminous coal from Pitkin County, Colorado

Although the effects of igneous dikes on the organic matter in coal have been observed at many localities there is virtually no information on the effects of the intrusions of the inorganic constituents in the coal. Such a study may help to elucidate the behavior of trace elements during in situ gasification of coal and may provide insights into the resources potential for coal and coke affected by the intrusion. To determine the effects of an igneous intrusion on the inorganic chemistry of a coal we used a series of 11 samples of coal and natural coke that had been collected at intervals from 3 to 106 cm from a dike that intruded the bituminous Dutch Creek coal in Pitkin, CO. The samples were chemically analyzed for 66 elements. SEM-EDX and X-ray diffraction analysis were performed on selected samples. Volatile elements such as F, Cl, Hg, and Se are not depleted in the samples (coke and coal) nearest the dike that were exposed to the highest temperatures. Their presence in these samples is likely due to secondary enrichment following volatilization of the elements inherent in the coal. Equilibration with ground water may account for the uniform distribution of Na, B, and Cl. High concentrations of Ca, Mg, Fe, Mn, Sr, and CO2 in the coke region are attributed to the reaction of CO and CO2 generated during the coking of the coal with fluids from the intrusion, resulting in the precipitation of carbonates. Similarly, precipitation of sulfide minerals in the coke zone may account for the relatively high concentrations of Ag, Hg, Cu, Zn, and Fe. Most elements are concentrated at the juncture of the fluidized coke and the thermally metamorphosed coal. Many of the elements enriched in this region (for example, Ga, Ge, Mo, Rb, U, La, Ce, Al, K, and Si) may have been adsorbed on either the clays or the organic matter or on both.Although the effects of igneous dikes on the organic matter in coal have been observed at many localities there is virtually no information on the effects of the intrusions on the inorganic constituents in the coal. Such a study may help to elucidate the behavior of trace elements during in situ gasification of coal and may provide insights into the resource potential of coal and coke affected by the intrusion. To determine the effects of an igneous intrusion on the inorganic chemistry of a coal we used a series of 11 samples of coal and natural coke that had been collected at intervals from 3 to 106 cm from a dike that intruded the bituminous Dutch Creek coal in Pitkin, CO. The samples were chemically analyzed for 66 elements. SEM-EDX and X-ray diffraction analysis were performed on selected samples. Volatile elements such as F, Cl, Hg, and Se are not depleted in the samples (coke and coal) nearest the dike that were exposed to the highest temperatures. Their presence in these samples is likely due to secondary enrichment following volatilization of the elements inherent in the coal. Equilibration with ground water may account for the uniform distribution of Na, B, and Cl. High concentrations of Ca, Mg, Fe, Mn, Sr, and CO2 in the coke region are attributed to the reaction of CO and CO2 generated during the coking of the coal with fluids from the intrusion, resulting in the precipitation of carbonates. Similarly, precipitation of sulfide minerals in the coke zone may account for the relatively high concentrations of Ag, Hg, Cu, Zn, and Fe. Most elements are concentrated at the juncture of the fluidized coke and the thermally metamorphosed coal. Many of the elements enriched in this region (for example, Ga, Ge, Mo, Rb, U, La, Ce, Al, K, and Si) may have been adsorbed on either the clays or the organic matter or on both.

International Journal of Coal Geology

The geochemistry of environmentally important trace elements in UK coals, with special reference to the Parkgate coal in the Yorkshire–Nottinghamshire Coalfield, UK

The Parkgate coal of Langsettian age in the Yorkshire–Nottinghamshire coalfield is typical of many coals in the UK in that it has a high sulphur (S) content. Detailed information on the distribution of the forms of S, both laterally and vertically through the seam, was known from previous investigations. In the present work, 38 interval samples from five measured sections of the coal were comprehensively analysed for major, minor and trace elements and the significance of the relationships established using both raw and centered log transformed data. The major elements are used to quantify the variations in the inorganic and organic coal components and determine the trace element associations. Pyrite contains nearly all of the Hg, As, Se, Tl and Pb and is also the major source of the Mo, Ni, Cd and Sb. The clays contain the following elements in decreasing order of association: Rb, Cs, Li, Ga, U, Cr, V, Sc, Y, Bi, Cu, Nb, Sn, Te and Th. Nearly all of the Rb is present in the clay fraction, whereas for elements such as V, Cu and U, a significant amount is thought to be present in the organic matter, based on the K vs trace element regression equations. Only Ge, and possibly Be, would appear to have a dominant organic source. The trace element concentrations are calculated for pyrite, the clay fraction and organic matter. For pyrite it is noted that concentrations agree with published data from the Yorkshire–Nottinghamshire coalfield and also that Tl concentrations (median of 0.33 ppm) in the pyrite are greater than either Hg or Cd. Unlike these elements, Tl has attracted less attention and possibly more information is needed on its anthropogenic distribution and impacts on man and the environment. A seawater source is thought to be responsible for the high concentrations of S, Cl and the non-detrital trace elements in the Parkgate coal. Indicative of the seawater control is the Th/U ratio, which expresses the detrital to non-detrital element contributions. Using other elements, similar ratios can be calculated, which in combination offer greater interpretative value.

Yorkshire–Nottinghamshire coalfield

Petrography, palynology, and paleoecology of the Lower Pennsylvanian Bon Air coal, Franklin County, Cumberland Plateau, southeast Tennessee

Stratigraphy, palynology, petrography, and geochemistry of the Bon Air coal from the Armfield, Dotson, Rutledge, and Shakerag mine sites of Franklin County, Tennessee suggest that Bon Air seams at all sites were small (??? 1.0 mile, 1.6 km), spatially distinct paleomires that evolved from planar to domed within the fluviodeltaic Lower Pennsylvanian Raccoon Mountain Formation. Of observed palynoflora, 88-97% are from lycopsids prevalent in the Westphalian. Densosporites palynomorphs of small lycopsids (e.g., Omphalophloios) dominate at the shale-hosted Armfield site, while Lycospora palynoflora of large arboreous lycopsids (especially Lepidodendron, with lesser Lepidophloios harcourtii and Lepidophloios hallii) dominate where intercalated siltstone/sandstone/shale hosts the coal (all other sites). Palynoflora of other lycopsids (Sigillaria and Paralycopodites), tree ferns, seed ferns, small ferns, calamites, and cordaites are generally minor. Genera of clastic-associated Paralycopodites are most common in Shakerag's coal (??? 10%), yet quite rare in Rutledge or Dotson coals. Overall, the palynomorph assemblages suggest that the Bon Air paleomires were forest swamps, and Early Pennsylvanian in age (Westphalian A, Langsettian). Dominant macerals at all sites are vitrinites, with fine collodetrinite (from strongly decomposed plant debris) more common than coarser collotelinite (from well-preserved plant fragments), and with lesser inertinites (fusinite and semifusinite) and liptinites (dominantly sporinite). Shakerag's coal has greatest abundance (mineral-matter-free) of collotelinite (up to 47%) and total vitrinite (74-79%) of any sites, but lowest liptinite (12-14.5%) and inertinite (7-11%). The Dotson and Rutledge seams contain moderate liptinite (21-23%) and highest inertinite (36-37%), lowest vitrinite (??? 41%), and lowest collotelinite (13-15%). Armfield's seam has relatively high liptinite (26-28%) and vitrinite (56.5-62%), but rather low inertinite (12-15%). Moderately high ash (11.0-20.0%) and low to moderate sulfur (1.24% avg.) are typical, but ash may locally be up to 38% and sulfur up to 2.9%. Volatile matter (32.1-41.3%), calorific value (33.3-34.9 MJ/kg MAF), moisture (2.2-3.4%), and vitrinite reflectance (0.70-0.84% Rmax; 0.64-0.79% Rrandom) place the Bon Air's rank as high-volatile-A bituminous (hvAb). The Armfield coal was probably a channel-distal paleomire, perhaps an oxbow lake or floodplain depression, which domed and then subsided back to planarity prior to burial. Features of its basal and uppermost benches suggest low-lying, often-flooded (but periodically dry) mires marked by fluvial influxes and diverse lycopsid growth. These include variable inertinite, common palynoflora of both small lycopsids (Omphalophloios-like) and large arboreous ones (Lepidophloios and Lepidodendron), minor but significant palynoflora of subaerial levee or levee/mire transition species (especially Paralycopodites), moderate to high ash, variable sulfur, and elevated levels of commonly fluvial trace elements (e.g., Al, Cr, REEs, Rb, Sr, Th, V, Y, and Zr). These benches also contain high total vitrinite, high collotelinite/collodetrinite ratios, and clays with moderate to low kaolinite/quartz ratios, all consistent with the near-neutral pH and limited peat degradation that typify such planar mires. By contrast, middle benches at Armfield reflect mires domed above the land surface, less-often flooded, less-preservational, and of lower pH: coals have lower ash, vitrinite, and collotelinite, less palynoflora of both large arboreous lycopsids and Paralycopodites, and high proportions of kaolinite, liptinite, and Densosporites. Similar data at Shakerag suggest that its mire also grew from planar to domed. However, more abundant Paralycopodites, a kaolinite-poor but quartz-and-illite-rich underclay, benches alternately ash-rich and ash-poor, and an upper bench truncated by channel sandstone, suggest that it was channel-proximal and pron

International Journal of Coal Geology