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Polyurethane foam (PUF) disk passive air samplers were evaluated under field conditionsto assessthe effect of temperature and wind speed on the sampling rate for polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs). Passive samples integrated over 28-day periods were compared to high-volume air samples collected for 24 h, every 7 days. This provided a large data set of 42 passive sampling events and 168 high-volume samples over a 3-year period, starting in October 2003. Average PUF disk sampling rates for gas-phase chemicals was approximately 7 m3 d(-1) and comparable to previous reports. The high molecular weight PAHs, which are mainly particle-bound, experienced much lower sampling rates of approximately 0.7 m3 d(-1). This small rate was attributed to the ability of the sampling chamber to filter out coarse particles with only the fine/ultrafine fraction capable of penetration and collection on the PUF disk. Passive sampler-derived data were converted to equivalent air volumes (V(EQ), m3) using the high-volume air measurement results. Correlations of V(EQ) against meteorological data collected on-site yielded different behavior for gas- and particle-associated compounds. For gas-phase chemicals, sampling rates varied by about a factor of 2 with temperature and wind speed. The higher sampling rates at colder temperatures were explained bythe wind effecton sampling rates. Temperature and wind were strongly correlated with the greatest winds at coldertemperatures. Mainly particle-phase compounds (namely, the high molecular weight PAHs) had more variable sampling rates. Sampling rates increased greatly atwarmertemperatures as the high molecular weight PAH burden was shifted toward the gas phase and subject to higher gas-phase sampling rates. At colder temperatures, sampling rates were reduced as the partitioning of the high molecular weight PAHs was shifted toward the particle phase. The observed wind effect on sampling for the particle-phase compounds is believed to be tied to this strong temperature dependence on phase partitioning and hence sampling rate. For purposes of comparing passive sampler derived data for persistent organic pollutants, the factor of 2 variability observed for mainly gas-phase compounds is deemed to be acceptable in many instances for semiquantitative analysis. Depuration compounds may be used to improve accuracy and provide site-specific sampling rates, although this adds a level of complexity to the analysis. More research is needed to develop and test passive air samplers for particle-associated chemicals.

Diffusion coefficients (D) of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were determined by film-stacking technique in low-density polyethylene (LDPE) and two types of polydimethylsiloxane (PDMS) (also known as silicone rubber, SR) with the trade names AlteSil TM and SilasticThe estimated values of D for PCBs and PAHs over a wide range of hydrophobicity were 2-2.5 orders of magnitude lower in LDPE than in SR polymers. Log D (m 2 s À1 ) of PCBs ranged from À10.1 to À10.9 for SRs and from À12.4 to À13.7 for LDPE. For PAHs these ranges were À9.8 to À11.4 for SRs and À11.9 to À13.7 for LDPE. Compared with the D values calculated in water, D were 1-2 and 3-4 orders of magnitude lower in SR and LDPE, respectively. For PAH molecules, D was lower than for PCBs with a similar molecular weight, probably because of their more rigid structure. The range of log D for PCBs in SR was only 0.5 log units (factor of 3.2) versus 1.2 log units (factor of 16) in LDPE. Although compound classes showed different relations, a linear relation of D with total surface area was the most universal. This relation may be used for prediction of D values in SR and LDPE polymers for other organic compounds.

Sampling rates (Rs) for silicone rubber (SR) passive samplers were measured under two different hydrodynamic conditions. Concentrations were maintained in the aqueous phase by continuous equilibration with SR sheets of a large total surface area which had been spiked with polycyclic aromatic hydrocarbons and/or polychlorinated biphenyls. Test sheets made of the same SR but of much smaller surface area were used to measure the uptake rate. Measured Rs values decreased with increasing passive sampler-water partition coefficient (Kpw) according to Rs approximately Kpw(-0.08) under both hydrodynamic conditions. This decrease is not significantly different from modeled values if the uncertainty of the diffusion coefficients in water is included. Modeling also confirmed that uptake of the test compounds under the experimental conditions was entirely controlled by diffusion in the water phase. A model using Rs approximately M(-0.47) is suggested for extrapolation of Rs estimated from the dissipation of performance reference compounds to target compounds in a higher hydrophobicity range.

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Photolysis of 2- and 4-chlorophenol samples in water ice of the initial concentrations 10(-7) to 10(-2) mol L(-1) is reported. Major phototransformations appeared to be based on the coupling reactions due to chlorophenol aggregation at the grain boundaries of the polycrystalline state. The main products, chlorobiphenyldiols, belong to the family of phenolic halogenated compounds (such as hydroxylated polychlorobiphenyls) that are known xenobiotics found in nature. No photosolvolysis products, that is products from intermolecular reactions between organic and water molecules, were observed at temperatures below -10 degrees C. Raising the temperature to -5 degrees C caused a moderate photosolvolytic activity in the case of 4-chlorophenol (formation of hydroquinone), in contrast to 2-chlorophenol which was almost exclusively transformed into pyrocatechol. It is suggested that photosolvolysis above this temperature occurs in a liquid or quasi-liquid layer that covers the ice crystal surfaces. The results support our model in which significant amounts of some persistent, bioaccumulative, and toxic compounds may be generated by photochemistry of primary pollutants in cold ecosystems and in the upper atmosphere, and may be subsequently released to the environment.

The protonation degree of cresol red (CR) in frozen aqueous solutions at 253 or 77 K, containing various acids (HF, HCl, HNO3, H2SO4, and p-toluenesulfonic acid), sodium hydroxide, NaCl, or NH4Cl, was examined using UV/Vis absorption spectroscopy. CR, a weak organic diacid, has been selected as a model system to study the acid-base interactions at the grain boundaries of ice. The multivariate curve resolution alternating least-squares method was used to determine the number and abundances of chemical species responsible for the overlaying absorption visible spectra measured. The results showed that the extent of CR protonation, enhanced in the solid state by 2-4 orders of magnitude in contrast to the liquid solution, is principally connected to an increase in the local concentration of acids. It was found that this enhancement was not very sensitive to either the freezing rate or the type of acid used and that CR apparently established an acid-base equilibrium prior to solidification. In addition, the presence of inorganic salts, such as NaCl or NH4Cl, is reported to cause a more efficient deprotonation of CR in the former case and an enhanced protonation in the latter case, being well explained by the theory of Bronshteyn and Chernov. CR thus served as an acid-base indicator at the grain boundaries of ice samples. Structural changes in the CR molecule induced by lowering the temperature and a presence of the constraining ice environment were studied by the absorption and 1H NMR spectroscopies. Cryospheric and atmospheric implications concerning the influence of acids and bases on composition and reactivity of ice or snow contaminants were examined.

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