The global distribution of linear and cyclic volatile methyl silxoanes (VMS) was investigated at 20 sites worldwide, including 5 locations in the Arctic, using sorbent-impregnated polyurethane foam (SIP) disk passive air samplers. Cyclic VMS are currently being considered for regulation because they are high production volume chemicals that are potentially persistent, bioaccumulative, and toxic. Linear and cyclic VMS (including L3, L4, L5, D3, D4, D5, and D6) were analyzed for in air at all urban, background, and Arctic sites. Concentrations of D3 and D4 are significantly correlated, as are D5 and D6, which suggests different sources for these two pairs of compounds. Elevated concentrations of D3 and D4 on the West coast of North America and at high elevation sites suggest these sites are influenced by trans-Pacific transport, while D5 and D6 have elevated concentrations in urban areas, which is most likely due to personal care product use. Measured concentrations of D5 were compared to modeled concentrations generated using both the Danish Eulerian Hemispheric Model (DEHM) and the Berkeley-Trent Global Contaminant Fate Model (BETR Global). The correlation coefficients (r) between the measured and modeled results were 0.73 and 0.58 for the DEHM and BETR models, respectively. Agreement between measurements and models indicate that the sources, transport pathways, and sinks of D5 in the global atmosphere are fairly well understood.

Decamethylcyclopentasiloxane (D(5)) is a volatile compound used in personal care products that is released to the atmosphere in large quantities. Although D(5) is currently under consideration for regulation, there have been no field investigations of its atmospheric fate. We employed a recently developed, quality assured method to measure D(5) concentration in ambient air at a rural site in Sweden. The samples were collected with daily resolution between January and June 2009. The D(5) concentration ranged from 0.3 to 9 ng m(-3), which is 1-3 orders of magnitude lower than previous reports. The measured data were compared with D(5) concentrations predicted using an atmospheric circulation model that included both OH radical and D(5) chemistry. The model was parametrized using emissions estimates and physical chemical properties determined in laboratory experiments. There was good agreement between the measured and modeled D(5) concentrations. The results show that D(5) is clearly subject to long-range atmospheric transport, but that it is also effectively removed from the atmosphere via phototransformation. Atmospheric deposition has little influence on the atmospheric fate. The good agreement between the model predictions and the field observations indicates that there is a good understanding of the major factors governing D(5) concentrations in the atmosphere.

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Deriving a parameterisation of ammonia emissions for use in chemistry-transport models (CTMs) is a complex problem as the emission varies locally as a result of local climate and local agricultural management. In current CTMs such factors are generally not taken into account. This paper demonstrates how local climate and local management can be accounted for in CTMs by applying a modular approach for deriving data as input to a dynamic ammonia emission model for Europe. Default data are obtained from information in the RAINS system, and it is demonstrated how this dynamic emission model based on these input data improves the NH₃ calculations in a CTM model when the results are compared with calculations obtained by traditional methods in emission handling. It is also shown how input data can be modified over a specific target region resulting in even further improvement in performance over this domain. The model code and the obtained default values for the modelling experiments are available as supplementary information to this article for use by the modelling community on similar terms as the EMEP CTM model: the GPL licencse v3

Understanding the legacy of persistent organic pollutants requires studying the transition from primary to secondary source control.

Cyclic volatile methyl siloxanes (cVMS) are present in technical applications and personal care products.They are predicted to undergo long-range atmospheric transport, but measurements of cVMS in remote areas remain scarce. An active air sampling method for decamethylcyclopentasiloxane (D5) was further evaluated to include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), and dodecamethylcyclohexasiloxane (D6). Air samples were collected at the Zeppelin observatory in the remote Arctic (79°N, 12°E) with an average sampling time of 81 ± 23 hours in late summer (AugustOctober) and 25 ± 10 hours in early winter (November -December) 2011. The average concentrations of D5 and D6 in late summer were 0.73 ± 0.31 ng/m 3 and 0.23 ± 0.17 ng/m 3 respectively, and 2.94 ± 0.46 ng/m 3 and 0.45 ± 0.18 ng/m 3 in early winter respectively. Detection of D5 and D6 in the Arctic atmosphere 2 confirms their long range atmospheric transport. The D5 measurements agreed well with predictions from an Eulerian atmospheric chemistry-transport model, and seasonal variability was explained by the seasonality in the OH radical concentrations. These results extend our understanding of the atmospheric fate of D5 to high latitudes, but question the levels of D3 and D4 that have previously been measured at Zeppelin with passive air samplers. IntroductionCyclic volatile methyl siloxanes (cVMS) are high-volume production chemicals used in the production of silicone polymers, in personal care products, and in a range of technical applications. cVMS have been found in both the physical environment and in biota, and have lately become subject to increasing scientific scrutiny by environmental scientists and regulators. 1-3The three congeners, and dodecamethylcyclohexasiloxane (D6) have specifically been the focus of the attention.e.g.1-3Hexamethylcyclotrisiloxane (D3) is an additional member of the group of cVMS. The physical-chemical properties of cVMS differ from many known organic pollutants, as they combine high volatility with extreme hydrophobicity and a considerable affinity for organic phases like octanol (Table S1). 4Volatilization to the atmosphere is the main emission pathway of cVMS to the environment. 1-3 Hence the atmosphere is a key compartment for understanding the environmental fate and behavior of cVMS. Once in the atmosphere, cVMS are predicted to be mainly present in the gas phase, and degradation by reaction with hydroxyl radicals is understood to be the main removal mechanism. 5 The atmospheric half-lives due to reaction with hydroxyl radicals are 20.0 days for D3, 10.3 days for D4, 6.7 days for D5, and 5.8 days for D6 (Table S1). The estimated levels of D5 from these models correspond well with observed atmospheric concentrations in the environment. 9, 11 The predicted seasonality of D5 was a consequence of the strong seasonality of the hydroxyl radical concentrations at high latitudes. During the polar night low levels of hydroxyl radicals slow down the atmospheric degradation of D5 and allow it to ...

Abstract. We have developed an integrated model system, EVA (Economic Valuation of Air pollution), based on the impact-pathway chain, to assess the health-related economic externalities of air pollution resulting from specific emission sources or sectors, which can be used to support policy-making with respect to emission control. Central for the system is a newly developed tagging method capable of calculating the contribution from a specific emission source or sector to the overall air pollution levels, taking into account the non-linear atmospheric chemistry. The main objective of this work is to identify the anthropogenic emission sources in Europe and Denmark that contribute the most to human health impacts. In this study, we applied the EVA system to Europe and Denmark, with a detailed analysis of health-related external costs from the ten major emission sectors and their relative contributions. The paper contains a thorough description of the EVA system, the main results from the assessment of the main contributors and a discussion of the most important atmospheric chemical reactions relevant for interpreting the results. The main conclusion from the analysis is that the major contributors to health-related external costs are major power production, agriculture, road traffic, and non-industrial domestic combustion, including wood combustion. We conclude that when regulating the emissions of ammonia from the agricultural sector, both the impacts on nature and on human health should be taken into account. This study confirms that air pollution constitutes a serious problem for human health and that the related external costs are considerable. The results in this work emphasize the importance of defining the right questions in the decision-making process. The results from assessing the impacts from each emission sector depend clearly on the assumption that the other emission sectors are not changed, especially emissions changing concentrations of atmospheric OH and therefore lifetimes of other chemical species.

An integrated model system, EVA (Economic Valuation of Air pollution), based on the impact-pathway chain has been developed to assess the health-related economic externalities of air pollution resulting from specific emission sources or sectors. The model system can be used to support policy-making with respect to emission control. In this study, we apply the EVA system to Europe, and perform a more detailed assessment of past, present, and future health-cost externalities of the total air pollution levels in Europe (including both natural and anthropogenic sources), represented by the years 2000, 2007, 2011, and 2020. We also assess the contribution to the health-related external costs from international ship traffic with special attention to the international ship traffic in the Baltic and North seas, since special regulatory actions on sulfur emissions, called SECA (sulfur emission control area), have been introduced in these areas. We conclude that, despite efficient regulatory actions in Europe in recent decades, air pollution still constitutes a serious problem for human health. Hence the related external costs are considerable. The total health-related external costs for the whole of Europe are estimated at 803 bn euros yr⁻¹ for the year 2000, decreasing to 537 bn euros yr⁻¹ in the year 2020. We estimate the total number of premature deaths in Europe in the year 2000 due to air pollution to be around 680 000 yr⁻¹, decreasing to approximately 450 000 in the year 2020. The contribution from international ship traffic in the Northern Hemisphere was estimated to 7% of the total health-related external costs in Europe in the year 2000, increasing to 12% in the year 2020. In contrast, the contribution from international ship traffic in the Baltic Sea and the North Sea decreases 36% due to the regulatory efforts of reducing sulfur emissions from ship traffic in SECA. Introducing this regulatory instrument for all international ship traffic in the Northern Hemisphere, or at least in areas close to Europe, would have a significant positive impact on human health in Europe