Surface Partitioning in Organic-Inorganic Mixtures Contributes to the Size-Dependence of the Phase-State of Atmospheric Nanoparticles.

Atmospheric particulate matter is one of the main factors governing the Earth's radiative budget, but its exact effects on the global climate are still uncertain. Knowledge on the molecular-scale surface phenomena as well as interactions between atmospheric organic and inorganic compounds is necessary for understanding the role of airborne nanoparticles in the Earth system. In this work, surface composition of aqueous model systems containing succinic acid and sodium chloride or ammonium sulfate is determined using a novel approach combining X-ray photoelectron spectroscopy, surface tension measurements and thermodynamic modeling. It is shown that succinic acid molecules are accumulated in the surface, yielding a 10-fold surface concentration as compared with the bulk for saturated succinic acid solutions. Inorganic salts further enhance this enrichment due to competition for hydration in the bulk. The surface compositions for various mixtures are parametrized to yield generalizable results and used to explain changes in surface tension. The enhanced surface partitioning implies an increased maximum solubility of organic compounds in atmospheric nanoparticles. The results can explain observations of size-dependent phase-state of atmospheric nanoparticles, suggesting that these particles can display drastically different behavior than predicted by bulk properties only.

Extensive organohalogen contamination in wildlife from a site in the Yangtze River Delta.

The environmental and human health concerns for organohalogen contaminants (OHCs) extend beyond the 23 persistent organic pollutants (POPs) regulated by the Stockholm Convention. The current, intense industrial production and use of chemicals in China and their bioaccumulation makes Chinese wildlife highly suitable for the assessment of legacy, novel and emerging environmental pollutants. In the present study, six species of amphibians, fish and birds were sampled from paddy fields in the Yangtze River Delta (YRD) were screened for OHCs. Some extensive contamination was found, both regarding number and concentrations of the analytes, among the species assessed. High concentrations of chlorinated paraffins were found in the snake, Short-tailed mamushi (range of 200-340 µg g(-)(1)lw), Peregrine falcon (8-59 µg g(-1)lw) and Asiatic toad (97 µg g(-)(1)lw). Novel contaminants and patterns were observed; octaCBs to decaCB made up 20% of the total polychlorinated biphenyls (PCBs) content in the samples and new OHCs, substituted with 5-8 chlorines, were found but are not yet structurally confirmed. In addition, Dechlorane 602 (DDC-DBF) and numerous other OHCs (DDTs, hexachlorocyclohexanes (HCHs), polybrominated diphenyl ethers (PBDEs), hexbromocyclododecane (HBCDD), chlordane, heptachlor, endosulfan and Mirex) were found in all species analyzed. These data show extensive chemical contamination of wildlife in the YRD with a suite of OHCs with both known and unknown toxicities, calling for further in-depth studies.

Polychlorinated naphthalenes in Swedish background air.

Polychlorinated naphthalenes (PCNs) with four to eight chlorines were studied in air collected at two background stations in Sweden, one southerly and one northerly. Air was sampled with a high-volume sampler, and gas-phase adsorbents and filters were analyzed separately. The sum of TeCNs to HxCNs in the gaseous phase ranged between 1 and 10 pg/m3 with significantly higher concentrations at the southern location Hoburgen. HpCNs and OCN were below the detection limit. The highest concentrations were found in two samples from Hoburgen with the air masses coming from SW and W and during warm weather (+11 degrees C). The lowest concentration was found in a sample from the northern location Ammarnäs at cold weather (-22 degrees C) when the air came from the east. A correlation was found between logP and 1/T indicating that temperature has a larger effect than location on the concentration in the gas phase. The TeCNs constituted 50-75% in the gaseous phase. In most filter samples TeCNs and PeCNs were below the limit of quantitation. PUF samples with air trajectories from W to NE had relatively higher concentrations of late eluting TeCNs and PeCNs, while in samples with winds from SE to S the early eluting congeners dominated. Samples with early eluting congeners were mainly collected at lower temperature. TriCNs constituted the dominant homologue group both in the gaseous and particulate phase of air samples as well as in bulk deposition from a rural monitoring station south of Stockholm. The octanol-air partition coefficient described the gas/particle interaction well for samples collected at temperatures down to -8 degrees C.