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A natural emissions inventory for the continental United States and surrounding territories is needed in order to use the US Environmental Protection Agency Community Multiscale Air Quality (CMAQ) Model for simulating natural air quality. The CMAQ air modeling system (including the Sparse Matrix Operator Kernel Emissions (SMOKE) emissions processing system) currently estimates non-methane volatile organic compound (NMVOC) emissions from biogenic sources, nitrogen oxide (NO<sub>x</sub>) emissions from soils, ammonia from animals, several types of particulate and reactive gas emissions from fires, as well as sea salt emissions. However, there are several emission categories that are not commonly treated by the standard CMAQ Model system. Most notable among these are nitrogen oxide emissions from lightning, reduced sulfur emissions from oceans, geothermal features and other continental sources, windblown dust particulate, and reactive chlorine gas emissions linked with sea salt chloride. A review of past emissions modeling work and existing global emissions data bases provides information and data necessary for preparing a more complete natural emissions data base for CMAQ applications. A model-ready natural emissions data base is developed to complement the anthropogenic emissions inventory used by the VISTAS Regional Planning Organization in its work analyzing regional haze based on the year 2002. This new data base covers a modeling domain that includes the continental United States plus large portions of Canada, Mexico and surrounding oceans. Comparing July 2002 source data reveals that natural emissions account for 16% of total gaseous sulfur (sulfur dioxide, dimethylsulfide and hydrogen sulfide), 44% of total NO<sub>x</sub>, 80% of reactive carbonaceous gases (NMVOCs and carbon monoxide), 28% of ammonia, 96% of total chlorine (hydrochloric acid, nitryl chloride and sea salt chloride), and 84% of fine particles (i.e., those smaller than 2.5 μm in size) released into the atmosphere. The seasonality and relative importance of the various natural emissions categories are described.
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Multi-year time series records of C<sub>2</sub>-C<sub>6</sub> alkanes, C<sub>2</sub>-C<sub>4</sub> alkenes, ethyne, isoprene, C<sub>6</sub>-C<sub>8</sub> aromatics, trichloroethene (C<sub>2</sub>HCl<sub>3</sub>), and tetrachloroethene (C<sub>2</sub>Cl<sub>4</sub>) from canister samples collected during January 2004–February 2008 at the University of New Hampshire (UNH) AIRMAP Observatory at Thompson Farm (TF) in Durham, NH are presented. The objectives of this work are to identify the sources of nonmethane hydrocarbons (NMHCs) and halocarbons observed at TF, characterize the seasonal and interannual variability in ambient mixing ratios and sources, and estimate regional emission rates of NMHCs. Analysis of correlations and comparisons with emission ratios indicated that a ubiquitous and persistent mix of emissions from several anthropogenic sources is observed throughout the entire year. The highest C<sub>2</sub>-C<sub>8</sub> anthropogenic NMHC mixing ratios were observed in mid to late winter. Following the springtime minimums, the C<sub>3</sub>-C<sub>6</sub> alkanes, C<sub>7</sub>-C<sub>8</sub> aromatics, and C<sub>2</sub>HCl<sub>3</sub> increased in early to mid summer, presumably reflecting enhanced evaporative emissions. Mixing ratios of C<sub>2</sub>Cl<sub>4</sub> and C<sub>2</sub>HCl<sub>3</sub> decreased by 0.7±0.2 and 0.3±0.05 pptv/year, respectively, which is indicative of reduced usage and emissions of these halogenated solvents. Emission rates of C<sub>3</sub>-C<sub>8</sub> NMHCs were estimated to be 10<sup>9</sup> to 10<sup>10</sup> molecules cm<sup>−2</sup> s<sup>−1</sup> in winter 2006. The emission rates extrapolated to the state of New Hampshire and New England were ~2–60 Mg/day and ~12–430 Mg/day, respectively. Emission rates of benzene, toluene, ethylbenzene, xylenes, and ethyne in the 2002 and 2005 EPA National Emissions Inventories were within ±50% of the TF emission rates.
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Simultaneous measurements of gaseous sulfuric acid and particle number size distributions were performed to investigate aerosol nucleation and growth during CAREBeijing-2008. The analysis of the measured aerosols and sulfuric acid with an aerosol dynamic model shows the dominant role of sulfuric acid in new particle formation (NPF) process but also in the subsequent growth in Beijing. Based on the data of twelve NPF events, the average formation rates (2–13 cm<sup>−3</sup> s<sup>−1</sup>) show a linear correlation with the sulfuric acid concentrations (<i>R</i><sup>2</sup>=0.85). Coagulation seems to play a significant role in reducing the number concentration of nucleation mode particles with the ratio of the coagulation loss to formation rate being 0.41±0.16. The apparent growth rates vary from 3 to 11 nm h<sup>−1</sup>. Condensation of sulfuric acid and its subsequent neutralization by ammonia and coagulation contribute to the apparent particle growth on average 45±18% and 34±17%, respectively. The 30% higher concentration of sulfate than organic compounds in particles during the seven sulfur-rich NPF events but 20% lower concentration of sulfate during the five sulfur-poor type suggest that organic compounds are an important contributor to the growth of the freshly nucleated particles, especially during the sulfur-poor cases.
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We have studied the hydration of sulfuric acid – ammonia and sulfuric acid – dimethylamine clusters using quantum chemistry. We calculated the formation energies and thermodynamics for clusters of one ammonia or one dimethylamine molecule together with 1–2 sulfuric acid and 0–5 water molecules. The results indicate that dimethylamine enhances the addition of sulfuric acid to the clusters much more efficiently than ammonia when the number of water molecules in the cluster is either zero, or greater than two. Further hydrate distribution calculations reveal that practically all dimethylamine-containing two-acid clusters will remain unhydrated in tropospherically relevant circumstances, thus strongly suggesting that dimethylamine assists atmospheric sulfuric acid nucleation much more effectively than ammonia.
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The present paper is a preliminary study preparing the introduction of reversible trace gas uptake by ice particles into a 3-D cloud resolving model. For this a 3-D simulation of a tropical deep convection cloud was run with the BRAMS cloud resolving model using a two-moment bulk microphysical parameterization. Trajectories within the convective clouds were computed from these simulation outputs along which the variations of the pristine ice, snow and aggregate mixing ratios and concentrations were extracted. The reversible uptake of 11 trace gases by ice was examined assuming applicability of Langmuir isotherms using recently evaluated (IUPAC) laboratory data. The results show that ice uptake is only significant for HNO<sub>3</sub>, HCl, CH<sub>3</sub>COOH and HCOOH. For H<sub>2</sub>O<sub>2</sub>, using new results for the partition coefficient results in significant partitioning to the ice phase for this trace gas also. It was also shown that the uptake is largely dependent on the temperature for some species. The adsorption saturation at the ice surface for large gas mixing ratios is generally not a limiting factor except for HNO<sub>3</sub> and HCl for gas mixing ratio greater than 1 ppbv. For HNO<sub>3</sub>, results were also obtained using a trapping theory, resulting in a similar order of magnitude of uptake, although the two approaches are based on different assumptions. The results were compared to those obtained using a BRAMS cloud simulation based on a single-moment microphysical scheme instead of the two moment scheme. We found similar results with a slightly more important uptake when using the single-moment scheme which is related to slightly higher ice mixing ratios in this simulation. The way to introduce these results in the 3-D cloud model is discussed.
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The effect of aerosol on clouds poses one of the largest uncertainties in estimating the anthropogenic contribution to climate change. Small human-induced perturbations to cloud characteristics via aerosol pathways can create a change in the top-of-atmosphere radiative forcing of hundreds of Wm<sup>−2</sup>. Here we focus on links between aerosol and deep convective clouds of the Atlantic and Pacific Intertropical Convergence Zones, noting that the aerosol environment in each region is entirely different. The tops of these vertically developed clouds consisting of mostly ice can reach high levels of the atmosphere, overshooting the lower stratosphere and reaching altitudes greater than 16 km. We show a link between aerosol, clouds and the free atmosphere wind profile that can change the magnitude and sign of the overall climate radiative forcing. <br><br> We find that increased aerosol loading is associated with taller cloud towers and anvils. The taller clouds reach levels of enhanced wind speeds that act to spread and thin the anvil clouds, increasing areal coverage and decreasing cloud optical depth. The radiative effect of this transition is to create a positive radiative forcing (warming) at top-of-atmosphere. <br><br> Furthermore we introduce the cloud optical depth (τ), cloud height (<i>Z</i>) forcing space and show that underestimation of radiative forcing is likely to occur in cases of non homogenous clouds. Specifically, the mean radiative forcing of towers and anvils in the same scene can be several times greater than simply calculating the forcing from the mean cloud optical depth in the scene. <br><br> Limitations of the method are discussed, alternative sources of aerosol loading are tested and meteorological variance is restricted, but the trend of taller clouds, increased and thinner anvils associated with increased aerosol loading remains robust through all the different tests and perturbations.
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Cloud condensation nuclei (CCN) concentrations were measured at Egbert, a rural site in Ontario, Canada during the spring of 2007. The CCN concentrations were compared to values predicted from the aerosol chemical composition and size distribution using κ-Köhler theory, with the specific goal of this work being to determine the hygroscopic parameter (κ) of the oxygenated organic component of the aerosol, assuming that oxygenation drives the hygroscopicity for the entire organic fraction of the aerosol. The hygroscopicity of the oxygenated fraction of the organic component, as determined by an Aerodyne aerosol mass spectrometer (AMS), was characterised by two methods. First, positive matrix factorization (PMF) was used to separate oxygenated and unoxygenated organic aerosol factors. By assuming that the unoxygenated factor is completely non-hygroscopic and by varying κ of the oxygenated factor so that the predicted and measured CCN concentrations are internally consistent and in good agreement, κ of the oxygenated organic factor was found to be 0.22±0.04 for the suite of measurements made during this five-week campaign. In a second, equivalent approach, we continue to assume that the unoxygenated component of the aerosol, with a mole ratio of atomic oxygen to atomic carbon (O/C) ≈ 0, is completely non-hygroscopic, and we postulate a simple linear relationship between κ<sub>org</sub> and O/C. Under these assumptions, the κ of the entire organic component for bulk aerosols measured by the AMS can be parameterised as κ<sub>org</sub>=(0.29±0.05)·(O/C), for the range of O/C observed in this study (0.3 to 0.6). These results are averaged over our five-week study at one location using only the AMS for composition analysis. Empirically, our measurements are consistent with κ<sub>org</sub> generally increasing with increasing particle oxygenation, but high uncertainties preclude us from testing this hypothesis. Lastly, we examine select periods of different aerosol composition, corresponding to different air mass histories, to determine the generality of the campaign-wide findings described above.
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Using the Swedish icebreaker Oden as a platform, continuous measurements of airborne mercury (gaseous elemental mercury (Hg<sup>0</sup>), divalent gaseous mercury species Hg<sup>II</sup>X<sub>2</sub>(g) (acronym RGM) and mercury attached to particles (PHg)) and some long-lived trace gases (carbon monoxide CO and ozone O<sub>3</sub>) were performed over the North Atlantic and the Arctic Ocean. The measurements were performed for nearly three months (July–September 2005) during the Beringia 2005 expedition (from Göteborg, Sweden via the proper Northwest Passage to the Beringia region Alaska – Chukchi Penninsula – Wrangel Island and in-turn via a north-polar transect to Longyearbyen, Spitsbergen). The Beringia 2005 expedition was the first time that these species have been measured during summer over the Arctic Ocean going from 60° to 90° N. <br><br> During the North Atlantic transect, concentration levels of Hg<sup>0</sup>, CO and O<sub>3</sub> were measured comparable to typical levels for the ambient mid-hemispheric average. However, a rapid increase of Hg<sup>0</sup> in air and surface water was observed when entering the ice-covered waters of the Canadian Arctic archipelago. Large parts of the measured waters were supersaturated with respect to Hg<sup>0</sup>, reflecting a strong disequilibrium. Heading through the sea ice of the Arctic Ocean, a fraction of the strong Hg<sup>0</sup> pulse in the water was transferred with some time-delay into the air samples collected ~20 m above sea level. Several episodes of elevated Hg<sup>0</sup> in air were encountered along the sea ice route with higher mean concentration (1.81±0.43 ng m<sup>−3</sup>) compared to the marine boundary layer over ice-free Arctic oceanic waters (1.55±0.21 ng m<sup>−3</sup>). In addition, the bulk of the variance in the temporal series of Hg<sup>0</sup> concentrations was observed during July. The Oden Hg<sup>0</sup> observations compare in this aspect very favourably with those at the coastal station Alert. Atmospheric boundary layer O<sub>3</sub> mixing ratios decreased when initially sailing northward. In the Arctic, an O<sub>3</sub> minimum around 15–20 ppbV was observed during summer (July–August). Alongside the polar transect during the beginning of autumn, a steady trend of increasing O<sub>3</sub> mixing ratios was measured returning to initial levels of the expedition (>30 ppbV). Ambient CO was fairly stable (84±12 ppbV) during the expedition. However, from the Beaufort Sea and moving onwards steadily increasing CO mixing ratios were observed (0.3 ppbV day<sup>−1</sup>). On a comparison with coeval archived CO and O<sub>3</sub> data from the Arctic coastal strip monitoring sites Barrow and Alert, the observations from Oden indicate these species to be homogeneously distributed over the Arctic Ocean. Neither correlated low ozone and Hg<sup>0</sup> events nor elevated concentrations of RGM and PHg were at any extent sampled, suggesting that atmospheric mercury deposition to the Arctic basin is low during the Polar summer and autumn.
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Airborne lidar and in-situ measurements of the aerosol properties were conducted between Svalbard Island and Scandinavia in April 2008. Evidence of aerosol transport from Europe and Asia is given. The analysis of the aerosol optical properties based on a multiwavelength lidar (355, 532, 1064 nm) including volume depolarization at 355 nm aims at distinguishing the role of the different aerosol sources (Siberian wild fires, Eastern Asia and European anthropogenic emissions). Combining, first aircraft measurements, second FLEXPART simulations with a calculation of the PBL air fraction originating from the three different mid-latitude source regions, and third level-2 CALIPSO data products (i.e. backscatter coefficient 532 nm,volume depolarization and color ratio between 1064 and 532 nm in aerosol layers) along the transport pathways, appears a valuable approach to identify the role of the different aerosol sources even after a transport time larger than 4 days. Optical depth of the aerosol layers are always rather small (<4%) while transported over the Arctic and ratio of the total attenuated backscatter (i.e. including molecular contribution) provide more stable result than conventional aerosol backscatter ratio. Above Asia, CALIPSO data indicate more depolarization (up to 15%) and largest color ratio (>0.5) for the northeastern Asia emissions (i.e. an expected mixture of Asian pollution and dust), while low depolarization together with smaller and quasi constant color ratio (≈0.3) are observed for the Siberian biomass burning emissions. A similar difference is visible between two layers observed by the aircraft above Scandinavia. The analysis of the time evolution of the aerosol optical properties revealed by CALIPSO between Asia and Scandinavia shows a gradual decrease of the aerosol backscatter, depolarization ratio and color ratio which suggests the removal of the largest particles in the accumulation mode. A similar study conducted for a European plume has shown aerosol optical properties intermediate between the two Asian sources with color ratio never exceeding 0.4 and moderate depolarization ratio being always less than 8%, i.e. less aerosol from the accumulation mode.
