The benzene polycarboxylic acid (BPCA) pattern of wood pyrolyzed between 200°C and 1000°C

Environmental charcoals represent a poorly defined part of the black carbon (BC) combustion continuum and may differ widely in their chemical and physical properties, depending on combustion conditions and source material. The benzene polycarboxylic acid (BPCA) molecular marker method is well established to quantify the BC component in charcoal, soil and sediment, although observed variations between labs could stem from subtle differences in methods. The objectives of this study were to identify and improve potential sources of analytical uncertainty. The improved method was then used to qualitatively characterize wood charred at 200–1000 °C. One significant improvement of the BPCA method was to replace citric acid with phthalic acid as an internal standard, which is more stable in acidic solution and more similar to the target compounds. Also, including a soil reference material as a quality control in each analysis proved to be a robust tool to detect for variations in reproducibility. For the thermosequence, elemental O/C and H/C ratios typically decreased with temperature to 60.03 at 1000 °C, whereas BPCA concentrations peaked at 700 °C. With temperature B6CA proportions increased consistently (6–98%), except for a plateau at 250–500 °C. Thus, relative contributions of B6CA reflected the pyrolysis temperature and probably also the degree of condensation of the charcoals we investigated. Future work will show if our results can be directly related to charcoal produced under oxygen limited conditions, including charcoal formed at wildfires or so called biochar for agricultural use

Rapid molecular screening of black carbon (biochar) thermosequences obtained from chestnut wood and rice straw: A pyrolysis-GC/MS study

Rice straw and chestnut wood were heated between 200 and 1000 °C (T CHAR) to produce Black C 'thermosequences'. The molecular properties of the charred residues were assessed by pyrolysis-GC/MS to investigate the relation between charring intensity and pyrolysis fingerprint. Samples obtained at T CHAR > 500 °C (wood) or >700 °C (straw) gave low quality pyrograms and poor reproducibility because of high thermal stability, but pyrolysis-GC/MS allowed to track the thermal degradation of the main biocomponents (polysaccharides, lignin, methylene chain-based aliphatics, triterpenoids, chlorophyll and proteins) in the lower temperature range, mostly occurring between T CHAR 250 and 500 °C. With increasing T CHAR, the charred residues of these biocomponents lose characteristic functional groups, aromatise and finally condense into non-pyrolysable biomass. The proportions of the pyrolysis products of unspecific origin (benzene, toluene, PAHs, etc.), increase with charring intensity, while the ratios that reflect the abundance of alkyl cross-linkages between aromatic moieties (e.g. benzene/toluene, naphthalene/alkylnaphthalene) decrease. These results provide the guidelines to using pyrolysis-GC/MS for the molecular characterisation of different components in Black C and biochar, which is an important parameter for predicting Black C/biochar behaviour in soil. Results are consistent with earlier studies of these samples using the BPCA (benzenepolycarboxylic acid) method and the ring current-induced 13C benzene chemical shift NMR (Nuclear Magnetic Resonance) approach. Pyrolysis-GC/MS provides more information on molecular structures in the low temperature range (T CHAR ≤ 500 °C) while the BPCA and NMR ring current methods provide more reliable estimations of charring intensity, especially at higher temperatures (T CHAR ≥ 500 °C). © 2012 Elsevier Ltd.This study was partly funded by the Spanish Ministry of Science and Education under the framework of the CONSOLIDER-INGENIO 2010 program TCP (CSD2007-00058).Peer Reviewe