Sediment-dissolved organic matter equilibrium partitioning of pentachlorophenol: the role of humic matter.

The dissolved humic matter (HM) has an essential influence on the release of the bound pentachlorophenol (PCP) from the solid sediment. It was studied how the increase of the dissolved HM concentration affects the equilibrium partitioning of PCP between the solid sediment matter and dissolved HM. The lake sedimentary and dissolved HM were isolated and their structural compositions were compared with elemental analyses, solid-sate 13C NMR spectroscopy and degradative analyses by pyrolysis-GC/MS. At the beginning of the equilibrium experiment, the PCP contaminant (200 microg l(-1)) was added into the water-sediment slurry system having an initial dissolved HM concentration. After 35 days, the system has reached an equilibrium and 75.5% of PCP was bound to the total solid sediment, 1.5% to dissolved HM and 23.0% remained free in water. The dissolved HM content was increased by 150% and, at the second equilibrium state after 91 days, only 63.8% of PCP was bound to the total sediment, and even 6.5% to the dissolved HM and 29.7% was free. The structural analyses indicated that the contents of aliphatics, aromatics and carboxylic carbons are lower in sediment than in dissolved HM, the content of carbohydrates in turn is higher in sediment than in dissolved HM, as well as that of different protein descriptors. The closely related partition coefficients for the sediment and dissolved HM, however, implied that the structural dissimilarity of these sorbents does not play so strong roles in the binding affinity of PCP as it would be postulated. The relatively great sorption coefficient of the minor colloid-like particle fraction in water implied its special but quantitatively quite immaterial roles in the partitioning cycle of PCP.