The sediment-to-air fluxes of two polycyclic aromatic hydrocarbons (phenanthrene and pyrene) and a heterocyclic aromatic hydrocarbon (dibenzofuran) from a laboratory-contaminated sediment and those of three polycyclic aromatic hydrocarbons(naphthalene, phenanthrene, and pyrene) from three field sediments were investigated in experimental microcosms. The flux was dependent on the sediment moisture content, air-filled porosity, and the relative humidity of the air flowing over the sedimentsurface. The mathematical model predictions of flux from the laboratory-spiked sediment agreed with observed values. The fluxes of compounds with higher hydrophobicity were more air-side resistance controlled. Conspicuous differences were observed between the fluxes from the laboratory-spiked and two of the three field sediments. Two field sediments showed dramatic increases in mass-transfer resistances with increasing exposure time and had significant fractions of oil and grease. The proposed mathematical model was inadequate for predicting the flux from the latter field sediments. Sediment reworking enhanced the fluxes from the field sediments due to exposure of fresh solids to the air. Variations in flux from the lab-spiked sediment as a result of change in air relative humidity were due to differences in retardation of chemicals on a dry or wet surface sediment. High moisture in the air over the dry sediment increased the competition for sorption sites between water and contaminant and increased thecontaminant flux.
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