Biochar-derived organic carbon promoting the dehydrochlorination of 1,1,2,2-tetrachloroethane and its molecular size effects: Synergies of dipole-dipole and conjugate bases.

The environmental effects of biochar-derived organic carbon (BDOC) have attracted increasing attention. Nevertheless, it is unknown how BDOC might affect the natural attenuation of widely distributed chloroalkanes (e.g., 1,1,2,2-tetrachloroethane (TeCA)) in aqueous environments. We firstly observed that the kinetic constants (ke) of TeCA dehydrochlorination in the presence of BDOC samples or their different molecular size fractions (<1 kDa, 1∼10 kDa, and >10 kDa) ranged from 9.16×103 to 26.63×103 M-1h-1, which was significantly greater than the ke (3.53×103 M-1h-1) of TeCA dehydrochlorination in the aqueous solution at pH 8.0, indicating that BDOC samples and their different molecular size fractions all could promote TeCA dehydrochlorination. For a given BDOC sample, the kinetic constants (ke) of TeCA dehydrochlorination in the initial pH 9.0 solution was 2∼3 times greater than that in the initial pH 8.0 solution due to more formation of conjugate bases. Interestingly, their DOC concentration normalized kinetic constants (ke/[DOC]) were negatively correlated with SUVA254, and positively correlated with A220/A254 and the abundance of aromatic protein-like/polyphenol-like matters. A novel mechanism was proposed that the CH dipole of BDOC aliphatic structure first bound with the CCl dipole of TeCA to capture the TeCA molecule, then the conjugate bases (-NH-/-NH2 and deprotonated phenol-OH of BDOC) could attack the H atom attached to the β-C atom of bound TeCA, causing a CCl bond breaking and the trichloroethylene formation. Furthermore, a fraction of >1 kDa had significantly greater ke/[DOC] values of TeCA dehydrochlorination than the fraction of <1 kDa because >1 kDa fraction had higher aliphiticity (more dipole-dipole sites) as well as more N-containing species and aromatic protein-like/polyphenol-like matters (more conjugate bases). The results are helpful for profoundly understanding the BDOC-mediated natural attenuation and fate change of chloroalkanes in the environment.