Accurate physical-chemical properties ͑aqueous solubility S W , octanol-water partition coefficient K OW , vapor pressure P, Henry's law constant H, octanol-air partition coefficient K OA , octanol solubility S O ) are of fundamental importance for modeling the transport and fate of organic pollutants in the environment. Energies of phase transfer are used to describe the temperature dependence of these properties. When trying to quantify the behavior of contaminant mixtures such as the polychlorinated biphenyls, consistent physical-chemical properties are required for each individual congener. A complete set of temperature dependent property data for sixteen polychlorinated biphenyls 8,15,28,29,31,52,61, 101, 105, 118, 138, 153, 155, 180, 194͒ was derived, based on all experimentally obtained values reported for these congeners in the literature. Log mean values derived from the experimental data were adjusted to yield an internally consistent set of data for each congener. These adjusted data also show a greater degree of interhomologue consistency, which can be illustrated with the help of simple quantitative structure-property relationships that use molar mass and the number of chlorine substitutions in ortho-positions as descriptors. The extent of the required adjustment gives an indication of the uncertainty of the averaged measured values and is typically lower than might be expected from the range of the reported measured values.
The study of organic contaminants at high altitudes is motivated by the potential risk that they pose to humans living in, or depending on resources derived from, mountains and to terrestrial and aquatic ecosystems in alpine areas. Mountains are also ideal settings to study contaminant transport and behavior along gradients of climate and surface cover. Information on organic contaminants in mountains is compiled from the literature and synthesized, with a focus on atmospheric transport and deposition, contaminant dynamics in alpine lakes and aquatic organisms, and concentration differences with altitude. Diurnal mountain winds, in connection with enhanced deposition at higher elevations caused by low temperatures and high precipitation rates, conspire to make mid-latitude mountains become convergence zones for selected persistent organic chemicals. In particular, the more volatile constituents of contaminant mixtures seem to become enriched, relative to the less volatile constituents at higher altitudes. For selected contaminants, concentration inversions (i.e., concentrations that increase with elevation) have been observed. A notable difference between cold trapping in high latitudes and high altitudes is the likely importance of precipitation. High rates of snow deposition in mid- and high-latitude mountains may lead to a large contaminant release during snowmelt. Regions above the tree line often have little capacity to retain the released contaminants, suggesting the potential for a highly dynamic contaminant fate situation during the snow-free season with significant revolatilization and runoff. The chemical and environmental factors that control the orographic cold trapping of organic contaminants should be examined further by measuring and comparatively interpreting concentration gradients along several mountain slopes with widely different characteristics. Future efforts should further focus on the bioaccumulation and potential effects of contaminants in the upper trophic levels of alpine food chains, on measuring more water-soluble, persistent organic contaminants, and on studying how climate change may affect contaminant dynamics in mountain settings.
Snow scavenging, a seasonal snowpack, and a dynamic water balance are incorporated in a non-steady-state generic multimedia fate model in order to investigate the effect of snow on the magnitude and temporal variability of organic contaminant concentrations in various environmental media. Efficient scavenging of large nonpolar organic vapors and particle-bound organic chemicals by snow can lead to reduced wintertime air concentrations and incorporation in the snowpack. The snow cover functions as a temporary storage reservoir that releases contaminants accumulating over the winter during a short melt period, resulting in temporarily elevated concentrations in air, water, and soil. The intensity of these peaks increases with the length of the snow accumulation period. Organic chemicals of sufficient volatility (log KOA < 9; e.g., light polychlorinated biphenyls) can volatilize from the snowpack, resulting in springtime concentration maxima in the atmosphere. The behavior of fairly water-soluble chemicals during snowmelt depends on their relative affinity for the newly formed liquid water phase and the rapidly diminishing ice surface-quantitatively expressed by their interface-water partition coefficient (KIW). Chemicals with a preference for the dissolved phase (low KIW; e.g., pentachlorophenol) can become enriched in the first meltwater fractions and experience a temporary concentration peak in lakes and rivers. Organic chemicals that are neither volatile enough to evaporate from the snowpack nor sufficiently water soluble to dissolve in the meltwater (e.g., polybrominated diphenyl ethers) sorb to the particles in the snowpack. These particles may be sufficiently contaminated to constitute the major input route to the terrestrial environment upon release during snowmelt. Because wintertime deposition to the snowpack may be higher than to a non-snow covered surface, this can result in higher soil concentrations of persistent organic contaminants in the long term. The potential ecotoxicological significance of peak exposures demands a better understanding of the role of snow in the fate of organic contaminants.
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