Oxidation is Key for Black Carbon Surface Functionality and Nutrient Retention in Amazon Anthrosols

Abstract

Aims: Soil black carbon (BC) has been shown to possess large amounts of cation exchange sites and surface charge, and is viewed as a potential soil amendment to improve nutrient retention and for pollutant remediation. This study investigated the nano-scale distribution of reactive functional groups and the binding of cations on the surface of micron-size BC particles, identified the key processes, and explored the sources of surface functionality and their relative contribution to cation exchange capacity (CEC). Materials and Methods: Elemental microprobe and synchrotron-based Scanning Transmission X-ray Spectromicroscopy (STXM) coupled with Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy were used for nano-scale mapping of cations and reactive functional groups, and further distinction of the sources of reactive functional groups generated either by oxidation of BC surfaces or by adsorption of non-BC organic matter onto the BC surfaces. Their respective contribution to cation adsorption was obtained using a depth profile of a BC-rich Anthrosol from the central Amazon, Brazil. Results and Discussion: Adsorption of Non-BC organic matter is more dominant on the surface of BC particle in topsoil as evidenced by a stronger signal of microbial biomass and humic substances extracts. In comparison, a greater level of oxidation was found on the outerlayer of BC particles in subsoil horizons. Organic C in subsoils was found to generate 23-42% more CEC per unit C than topsoil. Based on CEC per unit C, the capacity of BC in creating CEC was 6-7 times higher than Non-BC, and the BC in deeper horizons had up to 20% higher CEC than the topsoil horizon. Near BC surfaces, higher ratios of Ca/C and K/C in subsoil than topsoil horizons reinforce the observation that BC in subsoil horizons had a higher capacity in binding cations and creating CEC than in the topsoil horizon. Conclusions: Oxidation of BC is suggested to be more efficient and important for creating CEC than the adsorption of non-BC onto BC surfaces, thus identified as being key for BC surface functionality and nutrient retention in Amazon Anthrosols.