Sorption of anthracene (C14H10) and 9-anthroic acid (C15H10O2) onto biochar-amended soils as affected by field aging treatments

Abstract

There is a lack of information on how aging affects the sorption of ionizable organic compounds on biochar-amended soils. To that end, this study investigates the sorption of two hydrophobic solutes (anthracene (ANT) and 9-anthroic acid (9-ANCA)) onto biochar-amended (5%, w/w) soils as a function of aging period (0, 6, and 12 months), electrolyte (5 mM CaCl₂ and 10 mM KCl), and aqueous pH. The isotherm plot of both solutes was fairly linear (r² > 0.998) and the linear sorption coefficient (K_d, L kg^-1) was obtained from this. In CaCl₂ solution at pH 5, the log K_d of ANT tended to decrease (from 3.90 to 3.72) with an increasing aging period, which was attributed to clogged pore surface, whereas the differences in 9-ANCA sorption (from 2.56 to 2.51) were not significant (α = 0.05). The increased ANT sorption at acidic pH (<4) could be attributed to π-π interaction. Aqueous Ca²⁺ ions played an important role in 9-ANCA sorption by forming a Ca-bridge between anionic solute and negatively charged adsorbent surface, thus accounting for up to 35% of its sorption at alkaline pH (>8). The spectroscopic data and isoelectric point measurement results indicated that the number of oxygen-containing functional groups and the content of elemental oxygen were both higher in aged samples, resulting in a more polar (negatively charged) surface. The formation of surface polar groups and the associated deformation altered the adsorbent nature of the tested biochar, thereby fortifying the hydrophilic retention propensity for ionizable organic solutes.

Keywords: Biochar aging; Ca-bridge; Field weathering; Functional group; Ionizable organic solute.