Aging Induced Changes in Biochar's Functionality and Adsorption Behavior for Phosphate and Ammonium.

Biochar, a form of pyrogenic carbon, can contribute to agricultural and environmental sustainability by increasing soil reactivity. In soils, biochar could change its role over time through alterations in its surface chemistry. However, a mechanistic understanding of the aging process and its role in ionic nutrient adsorption and supply remain unclear. Here, we aged a wood biochar (550 °C) by chemical oxidation with 5-15% H2 O2 and investigated the changes in surface chemistry and the adsorption behavior of ammonium and phosphate. Oxidation changed the functionality of biochar with the introduction of carboxylic and phenolic groups, a reduction of oxonium groups and the transformation of pyridine to pyridone. After oxidation, the adsorption of ammonium increased while phosphate adsorption decreased. Ammonium adsorption capacity was nonlinearly related to the biochar's surface charge density (r2 = 0.94) while electrostatic repulsion and loss of positive charge due to destruction of oxonium and pyridine, possibly caused the reduced phosphate adsorption. However, the oxidized biochar substantially adsorbed both ammonium and phosphate when biochar derived organic matter (BDOM) was included. Our results suggest that aging of biochar could reverse its capacity for the adsorption of cationic and anionic species but the inclusion of BDOM could increase ionic nutrient and contaminant retention.