On the effects of petrographic composition on coalbed methane sorption

The effect of petrographic composition on the methane sorption capacity has been determined for a suite of coals and organic-rich shales. Subbituminous and bituminous coals were separated into bright and dull lithotypes by hand-picking. The methane sorption capacities range between 0.5 and 23.9 cm³/g at a pressure of 6 MPa. The low volatile bituminous Canmore coal and the anthracite sample have the highest capacities with the “natural coke” having the lowest. For low-rank coals there is no significant difference between bright and dull samples except for one coal with the dull sample having a greater sorption capacity than its bright equivalent. For higher-rank coals, the bright samples have a greater methane capacity than the dull samples and the difference between sample pairs increases with rank. The boghead coal samples have the highest sorption capacities in the liptinite-rich coals suite and are higher than subbituminous to medium volatile bituminous samples. Pore size distribution indicates that methane is held as solution gas in liptinite-rich coals and by physical sorption in micropores in liptinite-poor coals. These contrasting processes illustrate that liptinite-rich samples need to be independently assessed. The positive relationship between reactive inertinite content and methane sorption capacity occurs within the subbituminous to medium volatile bituminous coals because the reactive inertinite is structurally similar to vitrinite and have a higher microporosity than non-reactive inertinite. Reactivity of inertinite should be assessed in CBM studies of dull coals to provide a better understanding of petrographic composition effects on methane capacity.     

Hypersaline fluids generated by high-grade metamorphism of evaporites: fluid inclusion study of uranium occurrences in the Western Zambian Copperbelt

In the Pan-African Lufilian belt (Western Zambian Copperbelt), uranium mineralizations, preferentially scattered in kyanite ± talc micaschists (metamorphosed evaporitic sediments) or concentrated along transposed quartz veins provide an opportunity to (1) understand the time/space relationship between the ore minerals and the deformation of the host rocks, (2) identify the different fluid events associated with specific stages of quartz deformation and (3) characterize the ore fluid geochemistry in terms of fluid origin and fluid/rock interactions. In the U occurrences studied in Lolwa and Mitukuluku (Domes region, Western Zambian Copperbelt), two mineralizing stages are described. The first generation of ore fluids (53–59 wt% CaCl₂, 13–15 wt% NaCl; N₂–H₂ in the gas phase of fluid inclusions) circulated during the high-temperature quartz recrystallization, at 500–700 °C. This temperature is in agreement with the P–T conditions recorded during the crustal thickening related to continental collision at ca. 530 Ma. LA-ICPMS analyses show the presence of uranium within this fluid, with a concentration mode around 20 ppm. The second generation of ore fluid (21–32 wt% NaCl, 19–21 wt% CaCl₂; CO₂–CO in the gas phase of fluid inclusions) percolated at lower temperature conditions, at the brittle–ductile transition, between 200 and 300 °C. This temperature could be related to the exhumation of the high-grade metamorphic rocks at ca. 500 Ma. The formation of H₂ and CO is interpreted as the result of radiolysis in the presence of dissolved uranium in the aqueous phase of these fluid inclusions. Finally, a late fluid (14–16 wt% NaCl_equiv) circulated in the brittle domain but seems unrelated to U (re-)mobilization event.     

The origin of shoshonites: new insights from the Tertiary high-potassium intrusions of eastern Tibet

The shoshonitic intrusions of eastern Tibet, which range in age from 33 to 41 Ma and in composition from ultramafic (SiO₂ = 42 %) to felsic (SiO₂ = 74 %), were produced during the collision of India with Eurasia. The mafic and ultramafic members of the suite are characterized by phenocrysts of phlogopite, olivine and clinopyroxene, low SiO₂, high MgO and Mg/Fe ratios, and olivine forsterite contents of Fo₈₇ to Fo₉₃, indicative of equilibrium with mantle olivine and orthopyroxene. Direct melting of the mantle, on the other hand, could not have produced the felsic members. They have a phenocryst assemblage of plagioclase, amphibole and quartz, high SiO₂ and low MgO, with Mg/Fe ratios well below the values expected for a melt in equilibrium with the mantle. Furthermore, the lack of decrease in Cr with increasing SiO₂ and decreasing MgO from ultramafic to felsic rocks precludes the possibility that the felsic members were derived by fractional crystallization from the mafic members. Similarly, magma mixing, crustal contamination and crystal accumulation can be excluded as important processes. Yet all members of the suite share similar incompatible element and radiogenic isotope ratios, which suggests a common origin and source. We propose that melting for all members of the shoshonite suite was initiated in continental crust that was thrust into the upper mantle at various points along the transpressional Red River-Ailao Shan-Batang-Lijiang fault system. The melt formed by high-degree, fluid-absent melting reactions at high-T and high-P and at the expense of biotite and phengite. The melts acquired their high concentrations of incompatible elements as a consequence of the complete dissolution of pre-existing accessory minerals. The melts produced were quartz-saturated and reacted with the overlying mantle to produce garnet and pyroxene during their ascent. The felsic magmas reacted little with the adjacent mantle and preserved the essential features of their original chemistry, including their high SiO₂, low Ni, Cr and MgO contents, and low Mg/Fe ratio, whereas the mafic and ultramafic magmas are the result of extensive reaction with the mantle. Although the mafic magmas preserved the incompatible element and radiogenic isotope ratios of their crustal source, buffering by olivine and orthopyroxene extensively modified their MgO, Ni, Cr, SiO₂ contents and Mg/Fe ratio to values dictated by equilibrium with the mantle.     

Anthropogenic Pb accumulation in forest soils from Lake Clair watershed: Duchesnay experimental forest (Québec, Canada)

Mineral soil horizons (Ae, Bhf1, Bhf2, Bf, BC and C) were carefully collected from two podzolic soil profiles in the Lake Clair watershed (Québec) in order to assess anthropogenic trace metal accumulation. Petrographic and selective analyses were performed to establish the soil mineralogy and properties. Furthermore, a complete sequential extraction procedure has been applied to help understanding the complex chemical speciation of Pb in forest soils. Chemical speciation of Pb showed a strong vertical gradient: 85% of this metal is mainly partitioned in refractory minerals in the C-horizon whereas in the upper Bhf1 and Ae-horizons, less than 50% of Pb is associated with this fraction. In the Ae-horizon, for example, 35%, 30% and 12% of total Pb, respectively, is associated with the exchangeable, labile organic matter and amorphous Fe-Mn oxides fractions. The distribution of Pb and Cr in the studied forest soils mainly reflects progressive contamination of the watershed by anthropogenic atmospheric sources. The anthropogenic source is indicated by elevated Cr and Pb concentrations in the topsoil (Bhf and Ae) horizons and by strong negative correlation between ²⁰⁶Pb/²⁰⁷Pb ratios and total Pb concentrations. According to these isotopic values, penetration of anthropogenic Pb does not exceed 10 cm in both soil profiles. Below this depth, both Pb concentrations and isotopic ratios remain nearly constant and similar to values observed in pre-anthropogenic sediments from Lake Clair. These values are interpreted as the natural geochemical backgrounds of the watershed. Based on that behaviour, calculated anthropogenic Pb net inputs amounted to between 1.24 and 1.8 g/m².     

Sensitivity of the Eastern Mediterranean geomorphic system towards environmental change during the Late Holocene: a chronological perspective

Alluvial and colluvial sediment deposition provide a vital record of environmental change during the Holocene. Firm chronological control on these archives is necessary to enable us to relate sediment dynamics to human activity and climate variability. In the Eastern Mediterranean, such relationships are hard to establish due to the lack of spatially well‐distributed sediment archives with good chronological control. This scarcity is problematic with respect to regional‐scale reconstructions of the temporal variation of sediment dynamics. Here, we present a radiocarbon database (n = 178) of geomorphological activity collected from multiple distinct sediment archives within the territory of Sagalassos in south‐western Turkey. The data were grouped according to their sedimentary facies for analysis using cumulative probability distributions (CPDs) and sedimentation rate (SR) modelling. Two small‐scale colluvial valleys, where chronological information was abundant, were investigated in more detail. Results show that sedimentation chronology differs between individual, nearby cores, as it depends strongly on the local geomorphic situation. A generalizing approach combining multiple core results yields more widely valid conclusions. High sedimentation rates coincided with the initial major anthropogenic disturbance of the landscape and decreased afterwards, probably due to hillslope soil depletion. CPD and SR analysis indicates that in general colluvial sedimentation rates did not change much from 2000 BC onwards. River floodplain sedimentation, in contrast, increased markedly during the first millennium BC and during recent times, and a significant time lag in enhanced sediment deposition between the upper and lower reaches of the river valleys was observed. Copyright © 2012 John Wiley & Sons, Ltd.     

The role of anomalous soil moisture on the inland reintensification of Tropical Storm Erin (2007)

Prior research on tropical storm systems that have made landfall and undergone a period of sustainability or reintensification has been linked to the synoptic environment at the time the storm restrengthened. Tropical Storm (TS) Erin is an interesting case study in that it did not take on hurricane-like structure nor reach hurricane intensity until it moved through west-central Oklahoma on August 19, 2007. This study seeks to examine the possible impact of anomalously wet soils across much of Oklahoma on the reintensification of TS Erin during the early morning hours of August 19, 2007. To determine the degree to which the antecedent soil state impacted TS Erin??s inland evolution and reintensification, analyses of the synoptic environment and the mesoscale environment/boundary layer environment are undertaken using operational and research datasets such as upper air soundings, surface soil moisture and temperature data, and multiple products from the Storm Prediction Center (SPC) mesoanalysis archive. This observational assessment is complemented with numerical experiments using the Weather Research and Forecast Model, Advanced Research Version 3.2 (WRF-ARW) to further study the role of soil moisture availability and surface fluxes that may have led to the boundary layer feedback and inland reintensification. Observational analysis and model results indicate that anomalously wet conditions over the central Oklahoma region may have helped develop a regional boundary layer feedback that appears to have contributed to the inland reintensification of TS Erin. Thus, the anomalously wet land surface had a positive role in TS Erin reintensifying over Oklahoma during the early morning hours of August 19, 2007.     

Arsenic incorporation into FeS2 pyrite and its influence on dissolution: A DFT study

FeS₂ pyrite can incorporate large amounts of arsenic (up to ca. 10 wt%) and hence has a strong impact on the mobility of this toxic metalloid. Focussing on the lowest arsenic concentrations for which the incorporation occurs in solid solution, the substitution mechanisms involved have been investigated by assuming simple incorporation reactions in both oxidising and reducing conditions. The solution energies were calculated by Density Functional Theory (DFT) calculations and we predict that the formation of AsS dianion groups is the most energetically favourable mechanism. The results also suggest that the presence of arsenic will accelerate the dissolution and thus the generation of acid drainage, when the crystal dissolves in oxidising conditions.     

The petrogenesis of volcanics from Mt. Bulusan and Mt. Mayon in the Bicol arc,the Philippines

Pliocene to recent volcanic rocks from the Bulusan volcanic complex in the southern part of the Bicol arc (Philippines) exhibit a wide compositional range (medium- to high-K basaltic-andesites, andesites and a dacite/rhyolite suite), but are characterised by large ion lithophile element enrichments and HFS element depletions typical of subduction-related rocks. Field, petrographic and geochemical data indicate that the more silicic syn- and post-caldera magmas have been influenced by intracrustal processes such as magma mixing and fractional crystallisation. However, the available data indicate that the Bicol rocks as a group exhibit relatively lower and less variable ⁸⁷Sr/⁸⁶Sr ratios (0.7036–0.7039) compared with many of the other subduction-related volcanics from the Philippine archipelago. The Pb isotope ratios of the Bicol volcanics appear to be unlike those of other Philippine arc segments. They typically plot within and below the data field for the Philippine Sea Basin on ²⁰⁷Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb diagrams, implying a pre-subduction mantle wedge similar to that sampled by the Palau Kyushu Ridge, east of the Philippine Trench. ¹⁴³Nd/¹⁴⁴Nd ratios are moderately variable (0.51285–0.51300). Low silica (<55 wt%) samples that have lower ¹⁴³Nd/¹⁴⁴Nd tend to have high Th/Nd, high Th/Nb, and moderately low Ce/Ce* ratios. Unlike some other arc segments in the Philippines (e.g. the Babuyan-Taiwan segment), there is little evidence for the involvement of subducted terrigenous sediment. Instead, the moderately low ¹⁴³Nd/¹⁴⁴Nd ratios in some of the Bicol volcanics may result from subduction of pelagic sediment (low Ce/Ce*, high Th/Nd, and high Th/Nb) and its incorporation into the mantle wedge via a slab-derived partial melt.     

Two‐stage Variscan metamorphism in the Canigou massif: Evidence for crustal thickening in the Pyrenees

The Variscan metamorphism in the Pyrenees is dominantly of the low‐pressure–high‐temperature (LP‐HT) type. The relics of an earlier, Barrovian‐type metamorphism that could be related to orogenic crustal thickening are unclear and insufficiently constrained. A microstructural and petrological study of micaschists underlying an Ordovician augen orthogneiss in the core of the Canigou massif (Eastern Pyrenees, France) reveals the presence of two syntectonic metamorphic stages characterized by the crystallization of staurolite (M1) and andalusite (M2), respectively. Garnet is stable during the two metamorphic stages with a period of resorption between M1 and M2. The metamorphic assemblages M1 and M2 record similar peak temperatures of 580°C at different pressure conditions of 5.5 and 3 kbar, respectively. Using chemical zoning of garnet and calculated P–T pseudosections, a prograde P–T path is constrained with a peak pressure at ~6.5 kbar and 550°C. This P–T path, syntectonic with respect to the first foliation S1, corresponds to a cold gradient (of ~9°C/km), suggestive of crustal thickening. Resorption of garnet between M1 and M2 can be interpreted either in terms of a simple clockwise P–T path or a polymetamorphic two‐stage evolution. We argue in favour of the latter, where the medium‐pressure (Barrovian) metamorphism is followed by a period of significant erosion and crustal thinning leading to decompression and cooling. Subsequent advection of heat, probably from the mantle, leads to a new increase in temperature, coeval with the development of the main regional fabric S2. LA‐ICP‐MS U–Th–Pb dating of monazite yields a well‐defined date at c. 300 Ma. Petrological evidence indicates that monazite crystallization took place close to the M1 peak pressure conditions. However, the similarity between this age and that of the extensive magmatic event well documented in the eastern Pyrenees suggests that it probably corresponds to the age of monazite recrystallization during the M2 LP‐HT event.     

A nonlinear Lagrangian particle model for grains assemblies including grain relative rotations

We formulate a discrete Lagrangian model for a set of interacting grains, which is purely elastic. The considered degrees of freedom for each grain include placement of barycenter and rotation. Further, we limit the study to the case of planar systems. A representative grain radius is introduced to express the deformation energy to be associated to relative displacements and rotations of interacting grains. We distinguish inter-grains elongation/compression energy from inter-grains shear and rotations energies, and we consider an exact finite kinematics in which grain rotations are independent of grain displacements. The equilibrium configurations of the grain assembly are calculated by minimization of deformation energy for selected imposed displacements and rotations at the boundaries. Behaviours of grain assemblies arranged in regular patterns, without and with defects, and similar mechanical properties are simulated. The values of shear, rotation, and compression elastic moduli are varied to investigate the shapes and thicknesses of the layers where deformation energy, relative displacement, and rotations are concentrated. It is found that these concentration bands are close to the boundaries and in correspondence of grain voids. The obtained results question the possibility of introducing a first gradient continuum models for granular media and justify the development of both numerical and theoretical methods for including frictional, plasticity, and damage phenomena in the proposed model.