Phenanthrene binding and sorption to dissolved and to mineral-associated humic acid

Phenanthrene, a three ring aromatic hydrocarbon, was used as a model substrate to distinguish between binding and sorption to dissolved and to mineral-associated humic acid (HA), with an emphasis on its implication to bioavailability. Binding was analyzed by a fluorescence quenching technique using Aldrich HA and HAs derived from compost, loamy and clay loamy soils. Measurements were made both in buffered water and in a mineral medium to be used later in a bioavailability study. Sorption of phenanthrene to mineral-associated HA was analyzed in batch experiments. Mineral-HA complexes were prepared with goethite, hematite, and Ca²⁺- and Cu²⁺-montmorillonite. Interaction of HA with clay minerals was greater at low pH and was dependent on the mineral type. Sorption of phenanthrene to these complexes was substantially higher at lower pH and higher when the HA was associated with montmorillonite rather than goethite or hematite. Binding coefficients (K_b(oc)) obtained for dissolved HA were at least an order of magnitude higher than sorption coefficients (K_p(oc)) obtained for mineral-associated HA. Both binding and sorption coefficient values were substantially higher for Aldrich HA. This work emphasizes the need for a detailed sorption study before conducting well controlled bioavailability experiments.