Variability in oxidative degradation of charcoal: Influence of production conditions and environmental exposure

Charcoal is a key component of the Black Carbon (BC) continuum, where BC is characterized as a recalcitrant, fire-derived, polyaromatic material. Charcoal is an important source of palaeoenvironmental data, and of great interest as a potential carbon sink, due to its high apparent environmental stability. However, at least some forms of charcoal are clearly susceptible to environmental alteration and degradation over relatively short timescales. Although these processes have importance for the role of charcoal in global biogeochemistry, they remain poorly understood. Here we present results of an investigation into the susceptibility of a range of charcoal samples to oxidative degradation in acidified potassium dichromate. The study examines both freshly-produced charcoal, and charcoal exposed to environmental conditions for up to 50,000 years. We compare the proportion of carbon present in different forms between the samples, specifically with respect to the relative chemical resistance of these forms. This was undertaken in order to improve understanding of the post-depositional diagenetic changes affecting charcoal within environmental deposits. A wide range in chemical compositions are apparent both within and between the sample groups. In freshly-produced charcoal, material produced at 300 degrees C contains carbon with more labile forms than charcoal produced at >= 400 degrees C, signifying a key chemical change over the 300-400 degrees C temperature range. Charcoal exposed to environmental depositional conditions is frequently composed of a highly carboxylated aromatic structure and contains a range of carbon fractions of varying oxidative resistance. These findings suggest that a significant number of the environmental charcoals have undergone post-depositional diagenetic alteration. Further, the data highlight the potential for the use of controlled progressive oxidative degradation as a method to characterize chemical differences between individual charcoal samples. (C) 2011 Elsevier Ltd. All rights reserved.