Chars originating from the burning or pyrolysis of vegetation may significantly sorb neutral organic contaminants (NOCs). To evaluate the relationship between the char composition and NOC sorption,...

Compositions and sorptive properties of crop residue-derived chars.

http://www.fsl.orst.edu/ltep/Biscuit/Biscuit_files/Refs/Baldock%20OG2002%20fire.pdf

Chemical composition and bioavailability of thermally altered Pinus resinosa (Red pine) wood

Thermochemical processing of biomass produces a solid product containing char (mostly carbon) and ash. This char can be combusted for heat and power, gasified, activated for adsorption applications, or applied to soils as a soil amendment and carbon sequestration agent. The most advantageous use of a given char depends on its physical and chemical characteristics, although the relationship of char properties to these applications is not well understood. Chars from fast pyrolysis and gasification of switchgrass and corn stover were characterized by proximate analysis, CHNS elemental analysis, Brunauer-Emmet-Teller (BET) surface area, particle density, higher heating value (HHV), scanning electron microscopy, X-ray fluorescence ash content analysis, Fourier transform infrared spectroscopy using a photo-acoustic detector (FTIR-PAS), and quantitative 13C nuclear magnetic resonance spectroscopy (NMR) using direct polarization and magic angle spinning. Chars from the same feedstocks produced under slow pyrolysis conditions, and a commercial hardwood charcoal, were also characterized. Switchgrass and corn stover chars were found to have high ash content (32–55 wt %), much of which was silica. BET surface areas were low (7–50 m2/g) and HHVs ranged from 13 to 21 kJ/kg. The aromaticities from NMR, ranging between 81 and 94%, appeared to increase with reaction time. A pronounced decrease in aromatic CH functionality between slow pyrolysis and gasification chars was observed in NMR and FTIR-PAS spectra. NMR estimates of fused aromatic ring cluster size showed fast and slow pyrolysis chars to be similar (∼7–8 rings per cluster), while higher-temperature gasification char was much more condensed (∼17 rings per cluster). © 2009 American Institute of Chemical Engineers Environ Prog, 2009

Characterization of biochar from fast pyrolysis and gasification systems

Soil organic matter (OM) can be stabilized against decomposition by association with minerals, by its inherent recalcitrance and by occlusion in aggregates. However, the relative contribution of these factors to OM stabilization is yet unknown. We analyzed pool size and isotopic composition (14C, 13C) of mineral-protected and recalcitrant OM in 12 subsurface horizons from 10 acidic forest soils. The results were related to properties of the mineral phase and to OM composition as revealed by CPMAS 13C-NMR and CuO oxidation. Stable OM was defined as that material which survived treatment of soils with 6 wt% sodium hypochlorite (NaOCl). Mineral-protected OM was extracted by subsequent dissolution of minerals by 10% hydrofluoric acid (HF). Organic matter resistant against NaOCl and insoluble in HF was considered as recalcitrant OM. Hypochlorite removed primarily 14C-modern OM. Of the stable organic carbon (OC), amounting to 2.4–20.6 g kg−1 soil, mineral dissolution released on average 73%. Poorly crystalline Fe and Al phases (Feo, Alo) and crystalline Fe oxides (Fed−o) explained 86% of the variability of mineral-protected OC. Atomic Cp/(Fe+Al)p ratios of 1.3–6.5 suggest that a portion of stable OM was associated with polymeric Fe and Al species. Recalcitrant OC (0.4–6.5 g kg−1 soil) contributed on average 27% to stable OC and the amount was not correlated with any mineralogical property. Recalcitrant OC had lower Δ14C and δ13C values than mineral-protected OC and was mainly composed of aliphatic (56%) and O-alkyl (13%) C moieties. Lignin phenols were only present in small amounts in either mineral-protected or recalcitrant OM (mean 4.3 and 0.2 g kg−1 OC). The results confirm that stabilization of OM by interaction with poorly crystalline minerals and polymeric metal species is the most important mechanism for preservation of OM in these acid subsoil horizons.

Stabilization of Soil Organic Matter: Association with Minerals or Chemical Recalcitrance?

Spectroscopic characterization of the structural and functional properties of natural organic matter fractions

The compositions of humic acids (HAs) from various Histosols in North America and Europe, of similarly treated plant-extracted materials (PEMs), of coal-extracted humic acids, and of International Humic Substances Society (IHSS) Florida peat were quantified by solid-state 13 C nuclear magnetic resonance (NMR). In order to obtain quantitative intensities, the peak areas in direct-polarization 13-kHz magic-angle spinning (DPMAS) 13 C NMR spectra were corrected for incomplete relaxation by factors measured in cross-polarization spin-lattice relaxation time (CP/T 1 ) experiments with total sideband suppression (TOSS). The elemental compositions (%C, %H, %O + N) of a peat sample, 8 HAs and 2 PEMs were estimated from the NMR results and compared with chemical analyses, as well as solution NMR for two of the HAs. The results are in good agreement, which shows that DPMAS corrected by CP/T 1 -TOSS permits quantitative characterization of HAs and PEMs. The compositions of the PEMs deviate significantly from those of the Histosol HAs. The compositions in terms of nine types of chemical groups were computed. The investigated HAs consist of more than 60% of aromatic and CO carbons (including both carbonyl and carboxyl groups). Previous cross-polarization magic-angle spinning (CPMAS) NMR experiments have significantly underestimated the ratio of sp 2 -to sp 3 -carbons; in particular, the true COO carbon fraction is a factor of two larger than estimated by CPMAS NMR. In spite of their wide range of geographical origins, the compositions of the Histosol HAs appear to be relatively uniform, suggesting that the search for a general model of Histosol HA structure is worthwhile. Eight models proposed in the literature do not reproduce the experimentally determined compositions, but a few models show promising partial agreement.

W. G. Hu

Papers

Quantitative Characterization of Humic Substances by Solid-State Carbon-13 Nuclear Magnetic Resonance

Evaluation of different solid-state 13c nmr techniques for characterizing humic acids