Oxidative ageing induces change in the functionality of biochar and hydrochar: Mechanistic insights from sorption of atrazine

Abstract One attraction of using hydrochar (HC) and biochar (BC) in soil is their intrinsic affinity for organic contaminants. Oxidative ageing is likely to induce changes in physicochemical properties and functionality. To explore the long-term potential trajectories for corn stalk HC and BC to adsorb organic pollutants, we employed HC and BC exposure in 5% H 2 O 2 to simulate oxidative ageing and get insights into mechanisms of atrazine adsorption on fresh and artificially aged materials. The physicochemical properties of fresh and aged materials were systematically compared using elemental analysis, SSA, FTIR, XPS and SEM-EDS, alongside K 2 Cr 2 O 7 /H 2 SO 4 treatment to assess chemical oxidation stability. Atrazine is a typical herbicide chemical and hydrophobic organic pollutant. Adsorption isotherms of atrazine were used to reveal differences in mechanisms of sorption to BC and HC, by assessment before and ageing. BC freshly produced at 650 °C displayed higher capacity for atrazine sorption than BC produced at 500 °C, with a dominant role for π-π EDA interactions. The sorption capacity of HC freshly produced at 250 °C was higher than for HC produced at 200 °C HC, owing to higher C content and atrazine partitioning into the organic phase. Ageing increased the surface abundance of oxygenated functional groups for BC and HC and diminished bulk aromaticity. After ageing, atrazine sorption by high temperature BC was lower, but for HC it was increased. Such divergent effects must be considered when developing strategies to co-manage contaminants and carbon through the addition of carbonized materials to land.