Can biochar and hydrochar stability be assessed with chemical methods?

•Acid dichromate oxidation distinguishes reactivity of biochars and hydrochars .•Feedstocks may significantly influence biochar reactivity.•Holocene charcoal is not suited as standard material due to low reactivity. Field application of biochar is intended to increase soil carbon (C) storage. The assessment of C storage potential of biochars lacks methods and standard materials. The reactivity of biochars and hydrochars may be one possible means of evaluating their environmental stability. The aim of this study was to evaluate the reactivity of biochar produced by gasification (GS) and hydrochar produced by hydrothermal carbonisation (HTC). The approach included analysis of the two different char types produced from the same three feedstocks. Moreover, we analysed the reactivity of Holocene charcoal (150 and 2000yr old) to evaluate whether or not their use as standard materials to represent stable biochar is meaningful. We assessed carbon loss following oxidation with acid dichromate as well as hydrolysis with HCl. Our results showed that chemical reactivity is not a straightforward approach for characterising the stability of biochar and hydrochar. Acid hydrolysis showed little difference between HTCs and GSs, despite the contrasting elemental composition. Using acid dichromate oxidation, we determined that GSs contained ca. 70% of oxidation resistant C while the proportion for HTCs was2000yr old charcoal>HTCs>feedstock and was related to elemental composition. This shows that acid dichromate oxidation may allow differentiation of the reactivity of modern biochars but that there is not necessarily a relationship between reactivity and age of Holocene charcoals. As the chemical reactivity of biochars may change with exposure time in soil, it is poorly suited for assessing their environmental residence time.