Supercritical gas sorption on moist coals

The effect of moisture on the CO₂ and CH₄ sorption capacity of three bituminous coals from Australia and China was investigated at 55 °C and at pressures up to 20 MPa. A gravimetric apparatus was used to measure the gas adsorption isotherms of coal with moisture contents ranging from 0 to about 8%. A modified Dubinin–Radushkevich (DR) adsorption model was found to fit the experimental data under all conditions. Moisture adsorption isotherms of these coals were measured at 21 °C. The Guggenheim–Anderson–de Boer (GAB) model was capable of accurately representing the moisture isotherms over the full range of relative pressures.Moist coal had a significantly lower maximum sorption capacity for both CO₂ and CH₄ than dry coal. However, the extent to which the capacity was reduced was dependent upon the rank of the coal. Higher rank coals were less affected by the presence of moisture than low rank coals. All coals exhibited a certain moisture content beyond which further moisture did not affect the sorption capacity. This limiting moisture content was dependent on the rank of the coal and the sorbate gas and, for these coals, corresponded approximately to the equilibrium moisture content that would be attained by exposing the coal to about 40–80% relative humidity. The experimental results indicate that the loss of sorption capacity by the coal in the presence of water can be simply explained by volumetric displacement of the CO₂ and CH₄ by the water. Below the limiting moisture content, the CO₂ sorption capacity reduced by about 7.3 kg t^− 1 for each 1% increase in moisture. For CH₄, sorption capacity was reduced by about 1.8 kg t^− 1 for each 1% increase in moisture.The heat of sorption calculated from the DR model decreased slightly on addition of moisture. One explanation is that water is preferentially attracted to high energy adsorption sites (that have high energy by virtue of their electrostatic nature), expelling CO₂ and CH₄ molecules.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

The present day formation of apatite in Mexican continental margin sediments

Results of pore water and sediment analyses from the western Mexican continental margin strongly suggest the present day formation of apatite. The interstitial water phosphate and fluoride profiles indicate chemical removal at a depth which corresponds to a large maximum in the phosphorus content of the sediments. Apatite is identified within this maximum via X-ray diffraction but is elsewhere undetectable in the core. Radioisotopic thorium, uranium, and radium data support the conclusion that this deposit is modern. The present day depositional environment is consistent with those reported by other workers for phosphorite formation with the exception that pore water magnesium is not depleted below its seawater value.     

Chemical models of vitrinite reflectance evolution

A global kinetic model of vitrinite reflectance evolution is developed to illustrate a new approach to vitrinite reflectance modelling. The method utilizes quantitative pyrolysisgas Chromatographic data from isolated vitrinite kerogens to derive the concentrations of structurally specific moieties (alkylphenol precursors) in vitrinite kerogens as a function of rank. This data set is used to calibrate a gaussian distributed activation energy model for phenol-precursor loss from vitrinites using published burial histories. Phenol yield is then correlated with vitrinite reflectance. The predictive vitrinite reflectance model based on this phenol system is tested against a well from the US Gulf Coast area, the results being compared with a Lopatin model of the same well. This type of vitrinite reflectance model is numerically compatible with current generation kinetic models of hydrocarbon production from source rock kerogens, and has a better heating rate independence than Lopatin's method.

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Zusammenfassung Um eine neue Annäherung an das Modellieren der Vitrinit-Reflexion zu demonstrieren, wurde ein global-kinetisches Modell der Entwicklung der Vitrinit-Reflexion erstellt. Die Methode verwendet Daten von quantitativer Pyrolyse-Gas Chromatographie isolierten Vitrinitkerogens, um die Konzentration von strukturspezifischen Moieten (Alkylophenol-Vorläufer) in Vitrinitkerogen als Funktion der Reihenfolge zu erhalten. Verwendet werden diese Daten, um ein nach Gauss verteiltes Aktivierungsenergiemodell zu kalibrieren, das mit Hilfe von veröffentlichten Ablagerungsgeschichten den Phenol-Vorläuferverlust von Vitriniten beschreibt. Die Phenol-Ausbeute wird dann mit der Vitrinit-Reflexion korreliert. Das auf dem Phenolsystem basierende Vitrinit-Reflexionsmodell wird in einem Test einem Bohrloch an der amerikanischen Golfküste gegenübergestellt. Die Ergebnisse werden mit dem Lopatinmodell des selben Bohrlochs verglichen. Diese Art eines Vitrinit-Reflexionsmodells ist numerisch wettbewerbsfähig mit der heutigen Generation kinetischer Modelle der Kohlenwasserstofferzeugung aus Trägergesteinskerogenen. Außerdem ist seine Unabhängigkeit von der Erhitzungsrate größer als mit der Lopatin-Methode.

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Résumé L'auteur présente un modèle cinétique global de l'évaluation du pouvoir réflecteur de la vitrinite, afin d'illuster une approche nouvelle dans la modélisation de ce pourvoir réflecteur. Cette méthode utilise des données quantitatives fournies par la pyrolyse combinée à la Chromatographie en phase gazeuse et relatives à des kérogènes de vitrinite. A partir de ces données, on exprime les concentrations des fractions à structure spécifique dans les kérogènes vitrinitiques en fonction du degré d'évolution. A partir de cet ensemble de données, on établit un modèle de l'énergie d'activation selon une distribution gaussienne, applicable à la perte de phénol-précurseur dans les vitrinites, en se référant à cet effet aux déroulements historiques de l'enfouissement fournis par la littérature. La production de phénol est alors mise en relation avec le pourvoir réflecteur de la vitrinite. Le modèle du pouvoir réflecteur prévisible, basé sur ce système des phénols a été contrôlé dans un forage de la côte du golfe du Mexique (USA), et les résultats comparés à ceux du modèle de Lopatin appliqué au même forage. Le modèle présenté est numériquement compatible avec les modèles cinétiques habituels qui rendent compte de la production d'hydrocarbure à partir des kérogènes des roches-mères; il présente une meilleure indépendance que la méthode de Lopatin par rapport au taux d'échauffement.

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Large-strain deformation and strain partitioning in polyphase rocks: Dislocation creep of olivine–magnesiowüstite aggregates

Aggregates composed of olivine and magnesiowüstite have been deformed to large strains at high pressure and temperature to investigate stress and strain partitioning, phase segregation and possible localization of deformation in a polyphase material. Samples with 20 vol.% of natural olivine and 80 vol.% of (Mg_0.7Fe_0.3)O were synthesized and deformed in a gas-medium torsion apparatus at temperatures of 1127 °C and 1250 °C, a confining pressure of 300 MPa and constant angular displacement rates equivalent to constant shear strain rates of 1–3.3 × 10^− 4 s^− 1. The samples deformed homogeneously to total shear strains of up to γ  15. During constant strain rate measurements the flow stress remained approximately stable at 1250 °C while it progressively decreased after the initial yield stress at the lower temperature. Mechanical data, microstructures and textures indicate that both phases were deforming in the dislocation creep regime. The weaker component, magnesiowüstite, controlled the rheological behavior of the bulk material and accommodated most of the strain. Deformation and dynamic recrystallization lead to grain refinement and to textures that were not previously observed in pure magnesiowüstite and may have developed due to the presence of the second phase. At 1127 °C, olivine grains behaved as semi-rigid inclusions rotating in a viscous matrix. At 1250 °C, some olivine grains remained largely undeformed while deformation and recrystallization of other grains oriented for a-slip on (010) resulted in a weak foliation and a texture typical for pure dry olivine aggregates. Both a-slip and c-slip on (010) were activated in olivine even though the nominal stresses were up to 2 orders of magnitude lower than those needed to activate these slip systems in pure olivine at the same conditions.     

Cripple Creek and other alkaline-related gold deposits in the southern Rocky Mountains, USA: influence of regional tectonics

Alkaline-related epithermal vein, breccia, disseminated, skarn, and porphyry gold deposits form a belt in the southern Rocky Mountains along the eastern edge of the North American Cordillera. Alkaline igneous rocks and associated hydrothermal deposits formed at two times. The first was during the Laramide orogeny (about 70-40 Ma), with deposits restricted spatially to the Colorado mineral belt (CMB). Other alkaline igneous rocks and associated gold deposits formed later, during the transition from a compressional to an extensional regime (about 35-27 Ma). These younger rocks and associated deposits are more widespread, following the Rocky Mountain front southward, from Cripple Creek in Colorado through New Mexico. All of these deposits are on the eastern margin of the Cordillera, with voluminous calc-alkaline rocks to the west. The largest deposits in the belt include Cripple Creek and those in the CMB. The most important factor in the formation of all of the gold deposits was the near-surface emplacement of relatively oxidized volatile-rich alkaline magmas. Strontium and lead isotope compositions suggest that the source of the magmas was subduction-modified subcontinental lithosphere. However, Cripple Creek alkaline rocks and older Laramide alkaline rocks in the CMB that were emplaced through hydrously altered LREE-enriched rocks of the Colorado (Yavapai) province have ²⁰⁸Pb/²⁰⁴Pb ratios that suggest these magmas assimilated and mixed with significant amounts of lower crust. The anomalously hot, thick, and light crust beneath Colorado may have been a catalyst for large-scale transfer of volatiles and crustal melting. Increased dissolved H₂O (and CO₂, F, Cl) of these magmas may have resulted in more productive gold deposits due to more efficient magmatic-hydrothermal systems. High volatile contents may also have promoted Te and V enrichment, explaining the presence of fluorite, roscoelite (vanadium-rich mica) and tellurides in the CMB deposits and Cripple Creek as opposed to deposits to the south. Deep-seated structures of regional extent that formed during the Proterozoic allowed the magmas to rise to shallow crustal levels. Proterozoic sites of intrusions at 1.65, 1.4, and 1.1 Ga were also important precursors to alkaline-related gold deposits. Many of the larger gold deposits are located at sites of Proterozoic intrusions, and are localized at the intersection of northeast-trending ductile shear zones formed during Mesoproterozoic deformation, and an important north-trending fault formed during 1.1 Ga rifting.     

Symphurus civitatium (Pleuronectiformes: Cynoglossidae), a second estuarine-occurring tonguefish off the Southeastern United States and Northern Gulf of Mexico

Two species of tonguefishes,Symphurus plagiusa (Linnaeus 1766) andSymphurus civitatium Ginsburg 1951, occur sympatrically and sometimes syntopically in shallow water habitats in North Carolina and Louisiana estuaries. In North Carolina, approximately 2% of 430 small (<75 mm SL) tonguefishes collected wereS. civitatium, while in Barataria Bay, Louisiana, this species was more abundant and cosmopolitan in distribution than wasS. plagiusa, comprising over 82% of 3,564 tonguefishes collected with a small beam trawl over a 2-yr period. Historical literature has regardedS. plagiusa as the only tonguefish species inhabiting inshore waters in both regions. Presence of a secondSymphurus species in shallow estuaries has been overlooked, most probably due to difficulties in identifying early post-settlement juveniles because both species have similar morphologies and overlapping dorsal-fin and anal-fin ray counts. Juveniles can be readily recognized by differences in number of caudal-fin rays (10 inS. plagiusa versus 12 inS. civitatium), especially when used in combination with pigmentation patterns and posterior extent of the jaws relative to the posterior margin of the lower eye. The most distinctive pigmentation difference between juveniles of these two species (allowing for accurate identifications of over 98% of juveniles) is the absence inS. civitatium (12–61 mm SL) of a series of melanophores overlying pterygiophore regions of the dorsal and anal fins on the blind side. This feature contrasts markedly with that of juvenileS. plagiusa (12–65 mm SL), which are characterized by two interrupted, diagonal series of dark chromatophores converging, but not merging, with posterior tapering of the body. Occurrence of two sympatric species of tonguefishes in estuarine environments in the northcentral Gulf of Mexico and southeastern U.S. potentially compromises results of earlier ecological and distributional studies that assumed presence of only a single tonguefish species in these regions.     

Contact angles in CO2-water-coal systems at elevated pressures

Injection of carbon dioxide into coal seams is considered to be a potential method for its sequestration away from the atmosphere. However, water present in coals may retard injection: especially if carbon dioxide does not wet the coal as well as water. Thus contact angles in the coal-water-CO₂ system were measured using CO₂ bubbles in water/coal systems at 40 °C and pressures up to 15 MPa using five bituminous coals. At low pressures, in this CO₂/water/coal system, receding contact angles for the coals ranged between 80° to 100°; except for one coal that had both high ash yield and low rank, with a contact angle of 115°, indicating that it was hydrophilic. With increasing pressure, the receding contact angles for the different coals decreased, indicating that they became more CO₂-wetting. The relationship between contact angle and pressure was approximately linear. For low ash or high rank coals, at high pressure the contact angle was reduced to 30-50°, indicating the coals became strongly CO₂-wetting; that is CO₂ fluids will spontaneously penetrate these wet coals. In the case of the coal that was both high ash and hydrophilic, the contact angle did not drop to 90° even at the highest pressures used. These results suggest that CO₂ will not be efficiently adsorbed by all wet coals equally well, even at high pressure. It was found that at high pressures (> 2 MPa) the rate of penetration of carbon dioxide into the coals increased rapidly with decreasing contact angle, independently of pressure. Injecting CO₂ into wet coals that have both low rank and high ash will not trap CO₂ as well as injecting it into high rank or low ash coals.     

Elucidation of the Alum Shale kerogen structure using a multi-disciplinary approach

The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (¹³C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. ¹³C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CH_xO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (f_a), O/C and relative proportions of various carbon types estimated by ¹³C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.     

Ludlow (Silurian) stromatoporoid biostromes from Gotland, Sweden: facies, depositional models and modern analogues

Stacked stromatoporoid‐dominated biostromes of the Ludlow‐age Hemse Group (Silurian) in eastern Gotland, Sweden, are 0·5–5 m thick and a few tens of metres to >1 km in lateral extent. They form one of the world's richest Palaeozoic stromatoporoid deposits. This study compiles published and new data to provide an overall facies model for these biostromes, which is assessed in relation to possible modern analogues. Some biostromes have predominantly in‐place fossils and are regarded as reefs, but lack rigid frameworks because of abundant low‐profile non‐framebuilding stromatoporoids; other biostromes consist of stromatoporoid‐rich rudstones interpreted here as storm deposits. Variation between these two `end‐members' occurs both between interlayered biostromes and also vertically and laterally within individual biostromes. Such variation produces problems of applying established reef classification terms and demonstrates the need for the development of terminology that recognizes taphonomic destruction of reef fabrics. An approach to such terminology is found in all four categories of a recent biostrome classification scheme that are easily recognized in the Hemse biostrome facies: autobiostromes (>60% in place); autoparabiostromes (a mixture of in‐place and overturned reef‐building organisms, 20–60% in place); parabiostromes (builders are overturned and damaged, <20% in place); and allobiostromes (transported and detrital reef material, nothing in place). These categories provide a broad taphofacies scheme for the Hemse biostromes, which are mostly autoparabiostrome to allobiostrome. The biostromes developed on crinoidal grainstone sheets and expanded laterally across relatively flat substrates in a marine setting of low siliciclastic input. Planar erosion surfaces commonly terminate biostrome tops. Three broadly similar modern analogues are identified, each of which has elements in common with the Hemse biostromes, but none of which is an exact equivalent: (a) laterally expanded and coalesced back‐barrier patch reefs behind the Belize barrier, an area influenced by limited accommodation space; (b) a hurricane‐influenced shelf, interpreted for Grand Cayman, where reef cores consist of rubble and lack substantial framework; the wide distribution of rounded pebbles and cobbles of stromatoporoids in the Hemse biostromes most probably resulted from hurricanes; (c) coral carpets in 5–15 m water depth of the northern Red Sea, where lateral expansion of low‐diversity frames dominated by Porites coral has produced low‐profile biostromes up to 8 m thick and several km long. Such carpets accumulated large amounts of carbonate, with little export, as in the Hemse biostromes, although the latter did not build frameworks because of the nature of growth of the stromatoporoids. The notable lack of algae in the Hemse biostrome facies is also a feature of Red Sea coral carpets; nevertheless, coral carpets are ecologically different. Hemse biostromes lack evidence of a barrier reef system, although this may not be exposed; the facies assemblage is consistent with either a storm/hurricane‐influenced mid‐ to upper ramp or back‐barrier system.