Sorption behavior of three aromatic acids (benzoic acid, 1-naphthoic acid and 9-anthroic acid) on biochar: Cosolvent effect in different liquid phases.

Influence of the cosolvent on the sorption of organic acids on biochar has not been well understood. For this purpose, the sorption (log K _m , L kg ^-1 ) of three aromatic acids (benzoic acid (BA, pK _a  = 4.20), 1-naphthoic acid (1-NAPA, pK _a  = 3.70), and 9-anthroic acid (9-ANTA, pK _a  = 3.65) was evaluated as a function of methanol volume fraction (f _c  = 0.0, 0.25, and 0.5), liquid pH (2.5 and 7.0), ionic composition (CaCl ₂ and KCl) and ionic strength (0.005 M, 0.5 M, and 1 M CaCl ₂ ). A giant Miscanthus-derived biochar (ZPC of 2.86) was used as the sorbent. For all solutes, the sorption coefficients (log K _m ) measured at pH 2.5 (i.e., pH < pK _a ) tended to decrease with increasing f _c , as expected from the cosolvency model, while the result obtained at pH 7.0 was not fully explained by the same model. The log K _m of 1-NAPA in the CaCl ₂ system was always greater than in the KCl system (p < 0.05) and the impact became pronounced at high pH (>pK _a ) with increasing f _c . Increasing the Ca ²⁺ concentration at f _c  = 0.0 (from 0.005 M to 1 M) enhanced the value by 0.32 log unit of K _m . These phenomena indicate a significant role of dissolved Ca ²⁺ in the liquid phase, most likely due to the formation of cation bridges between aromatic carboxylates and the biochar surface (i.e., [R-COO ^- -Ca ²⁺ ]-{Biochar ^- }). A decrease in the dielectric constant of the methanol mixture could fortify the formation of this bridge. Regardless of the degree of cosolvency power (σ), as the number of aromatic rings of solutes increases, K _m decreases in the order BA > 1-NAPA > 9-ANTA, where f _c  = 0.0. In conclusion, the sorption potential of biochar can be significantly weakened by increasing pH and f _c , and in the absence of a divalent cation.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
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