M.A. Chappell | USGS Science

USGS2011

Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C nuclear magnetic resonance spectroscopy

Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CH n selection, and recoupled C–H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO 2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO 2 saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%–86.1%), nonpolar alkyl groups (9.0%–28.9%), and aromatic C–O carbons (4.1%–9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO 2 saturation. After exposure to high pressure CO 2 , vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO 2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO 2 –coal interactions at high pressure and the selectivity of lithotypes in response to CO 2 adsorption.

International Journal of Coal Geology↗

USGS2008

Distinguishing black carbon from biogenic humic substances in soil clay fractions

Most models of soil humic substances include a substantial component of aromatic C either as the backbone of humic heteropolymers or as a significant component of supramolecular aggregates of degraded biopolymers. We physically separated coarse (0.2–2.0 μm e.s.d.), medium (0.02–0.2 μm e.s.d.), and fine (> 0.02 μm e.s.d.) clay subfractions from three Midwestern soils and characterized the organic material associated with these subfractions using 13 C-CPMAS-NMR, DTG, SEM-EDX, incubations, and radiocarbon age. Most of the C in the coarse clay subfraction was present as discrete particles (0.2–5 μm as seen in SEM images) of black carbon (BC) and consisted of approximately 60% aromatic C, with the remainder being a mixture of aliphatic, anomeric and carboxylic C. We hypothesize that BC particles were originally charcoal formed during prairie fires. As the BC particles aged in soil their surfaces were oxidized to form carboxylic groups and anomeric and aliphatic C accumulated in the BC particles either by adsorption of dissolved biogenic compounds from the soil solution or by direct deposition of biogenic materials from microbes living within the BC particles. The biogenic soil organic matter was physically separated with the medium and fine clay subfractions and was dominated by aliphatic, anomeric, and carboxylic C. The results indicate that the biogenic humic materials in our soils have little aromatic C, which is inconsistent with the traditional heteropolymer model of humic substances.

Geoderma↗