New insight into the adsorption mechanism of PCP by humic substances with different degrees of humification in the presence of Cr(VI).

Humic substances (HSs) have great retention effects on pentachlorophenol (PCP) migration in subsurface environment, but the adsorption mechanism of PCP by HSs with various aromatic/aliphatic moieties and acidic functional groups in the presence of Cr(VI) is still unclear. In this study, the adsorption mechanism of PCP by undissolved humic acid (HA) and humin (HM) extracted from peat, black soil, lignite and coal was investigated under the presence of Cr(VI). According to the results, HA samples had much lower adsorption capacity for hydrophobic PCP than HM samples due to their higher contents of hydrophilic polar oxygen-containing functional groups. In respect to PCP adsorption mechanism, the molecular unsaturation of HSs associated with humification degree was found to be the determinant instead of polarity. Notably, after reacting with Cr(VI), significant decreasing of PCP adsorption quantities occurred on HSs extracted from lignite and coal with higher degrees of unsaturation (H/C < 0.64), while HSs extracted from peat and black soil with lower degrees of unsaturation (H/C > 0.83) kept almost unchanged, which can be attributed to the much higher reactivity of aromatic domains of HSs for Cr(VI) reduction compared with aliphatic moieties. This indicated that the adsorption mechanism of PCP by HSs with higher and lower degrees of unsaturation might be respectively driven by π-π interaction and hydrophobic interaction. This study highlighted the diverse adsorption mechanisms of PCP on HSs with different degrees of humification, and emphasized the coexisting Cr(VI) only have significant effect on PCP adsorption by HSs with higher humification degrees instead of the lower ones.