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Silicones are an important class of hydrophobic compounds in widespread use. To evaluate their fate in the environment, an accurate value of the air-water partition (Henry's law) constant is necessary, which, unfortunately, is lacking at present. A static head space and a newly developed dynamic vapor entry loop method were used to obtain the air-water partition constant for six volatile methyl siloxanes. Internally consistent data were obtained. The value of Henry's constant, as calculated from pure component vapor pressure and aqueous solubility, was 10- to 170-fold greater than the experimental values. A correction to the Henry's constant that involves the ratio of the thermodynamic activity coefficient for a methyl siloxane at infinite dilution to that at saturation solubility in the aqueous phase is proposed.

The desorption-resistant fraction of laboratory-spiked phenanthrene in two Louisiana (USA) sediments was not observed to be significantly different, but the two sediments exhibited different condensed-phase organic carbon contents, as defined operationally by the organic carbon remaining after combustion of the sediment at 375 degrees C. Only 3% of the original saturated phenanthrene in the sediments was not readily removed by exposure to a nonpolar polymeric resin and sorbent XAD-2. Allowing the laboratory-spiked contaminants to age for periods of up to three years yielded little difference in the desorption-resistant characteristics of the sediments. Field-contaminated sediments from Utica Harbor (Utica, NY, U.S.A.) and Rouge River (Detroit, MI, USA) that had a lengthy (decades to a century) period of contamination, however, exhibited significantly different desorption-resistant contaminant fractions, consistent with the fractions of condensed-phase organic carbon in the sediments. Measurements of the fraction that could be rapidly desorbed using the XAD-2 sorbent also accounted for essentially all desorption to pore water and, thus, provided a good prediction of effective bulk partition coefficients. It was concluded that the condensed-phase organic carbon was a good indicator of the potential for desorption resistance in field-contaminated sediments and that the rapidly desorbing fraction provided a quantitative indicator of its significance.

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A model was developed to predict biphasic sorption and desorption of hydrophobic organic compounds in contaminated sediments. The model was based on relatively rapid porous diffusion in amorphous organic carbon and slow solid-phase diffusion in condensed-phase organic carbon. The model was used to simulate measured solid-fluid phase desorption (rates and pore-water concentrations) for four polycyclic aromatic hydrocarbons exhibiting a range of hydrophobicities (phenanthrene, anthracene, pyrene, and benzo[a]pyrene) in two field-contaminated sediments from Utica Harbor (Utica, NY, USA) and Rouge River (Detroit, MI, USA). Pore-water concentrations have been related to bioavailability, indicating the potential usefulness of the model to predict bioavailability. Key model parameters included the fraction of condensed-phase carbon (estimated by combustion at 375 degrees C), partition coefficient to the condensed-phase carbon (estimated by desorption measurements on coal-like particles physically separated from Utica Harbor sediments), and diffusivity and ratio of volume to surface area of the condensed-phase organic matter (fitted to measured desorption data on both sediments and for the measured polycyclic aromatic hydrocarbons). Best fit for the diffusion coefficient in the condensed-phase organic matter was 8.5 x 10(-20) m2/s, and ratio of volume to surface area was 2 microm. These parameters estimated measured pore-water concentrations of all polycyclic aromatic hydrocarbons in both sediments with an average error of 46% and a correlation coefficient of 0.76 and the fast-desorbing fractions (as measured by the fraction removed with a nonpolar polymeric sorbent XAD-2) with an average error of approximately 30% and a correlation coefficient of 0.54 (14% and 0.76, respectively, for all but benzo[a]pyrene). Modeling results were relatively insensitive to the two fitted parameters, with changes of an order of magnitude or more being required to affect the correlation between the model and observations significantly.