Methoxyl stable isotopic constraints on the origins and limits of coal-bed methane.

Microbial coal-bed methane is an important economic resource and source of a potent greenhouse gas, but controls on its formation are poorly understood. To test whether the microbial degradability of coal limits microbial methane, we monitored methoxyl group demethylation­a reaction that feeds methanogenesis­in a global sample suite ranging in maturity from wood to bituminous coal. Carbon isotopic compositions of residual methoxyl groups were inconsistent with a thermal reaction, instead implying a substrate-limited biologic process. This suggests that deep biosphere communities participated in transforming plant matter to coal on geologic time scales and that methoxyl abundance influences coal-bed methane yield. Carbon isotopic enrichments resulting from microbial methylotrophy also explain an enigmatic offset in the carbon-13 content of microbial methane from coals and conventional hydrocarbon deposits.

Application of micro-FTIR mapping and SEM to study compositional heterogeneity of siltstones: Example from the Late Devonian-Early Mississippian Middle Bakken Member.

This paper explores the applicability of micro-FTIR mapping to study heterogeneity of organic matter-lean siltstones. Closely spaced samples of Late Devonian dolomitic siltstones of the Middle Bakken Member were analysed with micro-FTIR, powder X-ray diffraction, and scanning electron microscopy (SEM) to explore the distribution and chemical properties of organic matter (OM), muscovite/feldspar/clay group, carbonates, and quartz, and their influence on porosity and permeability of these rocks. Our results show that quartz is the dominant component of the samples, and the main mineralogical differences between the samples are reflected in the abundance of carbonate minerals. Organic matter content is usually far below 1 wt. % and dominantly represented by terrestrially derived vitrinite and inertinite. Micro-FTIR mapping demonstrates that the more spatially connected quartz and muscovite/feldspar/clays become, the larger permeability in the rock develops, and these correlations are especially strong for planes parallel to bedding. In contrast, carbonate connectivity shows a strong negative correlation with permeability. No correlations between connectivity of components and porosity have been detected. These observations suggest that micro-FTIR not only can document compositional heterogeneity of siltstones, but also has potential to help understanding their permeability systems.

Mapping the chemistry of resinite, funginite and associated vitrinite in coal with micro-FTIR.

Micro-FTIR mapping is a powerful tool for nondestructive, in situ chemical characterization of coal macerals at high resolution. In this study, the chemistry of resinite, funginite and associated vitrinite is characterized via reflectance micro-FTIR for Cenozoic high volatile C bituminous coals from Colombia. In comparison with the micro-FTIR spectra of vitrinite and inertinite, the corresponding spectra of liptinite macerals in the same coals are characterized by stronger aliphatic CH(x) absorbance at 3000-2800 and 1460-1450 cm⁻¹, but less intense aromatic C=C ring stretching vibration and aromatic CH(x) out-of-plane deformation at 700-900 cm⁻¹. The aliphatic components in resinite have the longest carbon chains and are least branched, bestowing the highest hydrocarbon generation potential on resinite among the three macerals studied. In contrast, funginite exhibits the strongest aromatic character, the highest aromaticity, the lowest 'A' factor values and the lowest C=O/C=C ratios among the three maceral groups. Vitrinite generally displays intermediate chemical characteristics. Reflectance micro-FTIR mapping of coal samples further confirms the aliphatic character of resinite and the aromatic nature of funginite. In addition, chemical mapping of resinite and adjacent vitrinite shows that vitrinite immediately adjacent to resinite displays higher aliphatic CH(x) stretching intensity than more distant vitrinite, suggesting that chemical components from resinite can diffuse over short distances into adjacent vitrinite, specifically causing hydrogen enrichment. It needs to be pointed out, however, that the region of influence is localized and limited to a narrow zone, whose extent likely depends on resinite's properties, such as its size and aliphatic material content. This way, the chemical map of resinite and associated vitrinite provides direct evidence of the intermaceral effects occurring during the peat forming stage or during later coalification. No influence of funginite (primarily fungal spores and sclerotia) on the chemistry of adjacent vitrinite has been demonstrated, which is likely due to the highly aromatic structure of this type of funginite.

Chemical fractionation of metals in wetland sediments: Indiana Dunes National Lakeshore.

Tessier-type (1979) sequential extractions for heavy metals (Cd, Cr, Cu, Fe, Mn, Pb, and Zn) were conducted on sediments from two wetland sites, one inundated and the other drained, within the Indiana Dunes National Lakeshore (IDNL), NW Indiana, with the objective of (i) evaluating extraction techniques on organic-rich sediments, (ii) determining the geochemistry and mobility of potentially biotoxic trace metals in a contaminated environment, and (iii) considering the implications of different restoration strategies on the potential for heavy metal remobilization. Long and repeated extractions were needed to effectively degrade the organic-rich sediments (up to 75% of the sediment by mass). Analysis of sulfur fractionation revealed that it was predominantly sequestered along with the organically bound fraction (renamed oxidizable). Metal recovery was good with the sum of the extractant steps typically within 20% of the total metal concentration determined after total microwave digestion. Results showed metal fractionation to be both metal- and site-specific, The oxidizable fraction is dominant for Cu, Cr, and Fe (>65% of the nonresidual fraction for almost all samples) and overall is most important also for Cd and Pb. The iron/manganese oxide fraction is important for Pb, Mn, and Zn, particularly at the drained site. The carbonate bound fraction is relatively insignificant at both sites, except for Cd and Mn, although it is more important at the drained site. The exchangeable fraction is significant in the uppermost sediments at the drained site, particularly for Cd (3-24%), Pb (3-14%), and Zn (36-45%); whereas, for the inundated site, it ranged only from 0 to 1% Zn, with no detectable Cd or Pb. Chromium, Cu, and Fe exist in forms not likely to be remobilized, whereas Cd, Mn, Pb, and Zn are potentially mobile if drained wetland sites are reflooded (and pH and redox potential altered). Simple mass balance calculations illustrate the potential for the removal of approximately 84,375 kg of exchangeable Zn if currently drained sites across the IDNL are reflooded, with concentrations in water draining into Lake Michigan as high as 5 ppm.