Effect of heavy metals on the sorption of hydrophobic organic compounds to wood charcoal

Black carbon (BC) is believed to be an important adsorbent of organic pollutants. A complex suite of heavy metals and organic pollutants is commonly present in many situations. An issue that has received little direct attention is the effect of heavy metals on sorption of organic compounds to BC. We found that coadsorption of Cu2+ at an environmentally relevant, comparable concentration (50 mg L-1) decreases sorption of both the polar compound, 2,4-dichlorophenol (DCP), and nonpolar compounds, 1,2-dichlorobenzene (DCB) and naphthalene (NAP), by 30-60%, as measured by the change in the distribution coefficient (K-d). This was attributed to surface complexation of Cu2+ to form hydration shells of dense water that directly compete with organics for adsorption surface area. In contrast, coadsorption of Ag+ increases sorption of the organic solutes, which was accounted for by the decline in hydrophilicity of the local region around Ag+-complexed functionalities due to softness of the cation, leading to mitigated competitive sorption of water. Coadsorption of heavy metal ions to nonporous graphite, a model of the BC graphene (polycyclic aromatic) structure that has no O-containing groups, however, only slightly inhibits organic adsorption due to the low affinities of metal ions to graphite surface. The results of the present study showed that the presence of coexisting heavy metals greatly affects sorption of organic pollutants on BC and thereby their fate and transport.