Dynamic of the structural alteration of biochar in ancient Anthrosol over a long timescale by Raman spectroscopy

The presence of biochar with high carbon accumulation capacity and nutrient adsorption is causally associated with archeological soils. Although this type of soil organic matter has been known for a long time, the knowledge of its structure and environmental behavior is still limited. This work used Raman spectroscopy to obtain structural information and identify alterations in biochar particles. To this end, we studied biochar particles found in an archaeological site with a temporal window lasting 12451 to 11080 yr cal BP. The molecular, structural and sp2/sp3 characteristics of the charcoal particles were determined at the time of burning and associated with the temperature, time and characteristics of the burnt material. We propose that the process of oxidation of the biochar occurs during the first 2000 years after its genesis. The oxidation process is a reflection of decreases in the number of defects related to sp2 bonds on amorphous carbons and increases in the number of defects associated with ionic impurities, which clearly indicate the interaction between biochar particles and the soil matrix. The data confirm the hypothesis that the persistence of biochar in the environment is due to its graphite structure and suggest that over a 12000 year timeframe, biochar particles undergo several changes that occur in the disordered phase and are rapidly oxidized.