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Abstract. Fires emit sufficient sulfur to affect local and regional airquality and climate. This study analyzes SO2 emission factors andvariability in smoke plumes from US wildfires and agricultural fires, as well as theirrelationship to sulfate and hydroxymethanesulfonate (HMS) formation.Observed SO2 emission factors for various fuel types show goodagreement with the latest reviews of biomass burning emission factors,producing an emission factor range of 0.47–1.2 g SO2 kg−1 C.These emission factors vary with geographic location in a way that suggeststhat deposition of coal burning emissions and application ofsulfur-containing fertilizers likely play a role in the larger observedvalues, which are primarily associated with agricultural burning. A 0-D boxmodel generally reproduces the observed trends of SO2 and total sulfate(inorganic + organic) in aging wildfire plumes. In many cases, modeled HMSis consistent with the observed organosulfur concentrations. However, acomparison of observed organosulfur and modeled HMS suggests that multipleorganosulfur compounds are likely responsible for the observations but thatthe chemistry of these compounds yields similar production and loss rates asthat of HMS, resulting in good agreement with the modeled results. Weprovide suggestions for constraining the organosulfur compounds observedduring these flights, and we show that the chemistry of HMS can alloworganosulfur to act as an S(IV) reservoir under conditions of pH > 6 andmore »liquid water content>10−7 g sm−3. This canfacilitate long-range transport of sulfur emissions, resulting in increasedSO2 and eventually sulfate in transported smoke.« less

Oceans emit large quantities of dimethyl sulfide (DMS) to the marine atmosphere. The oxidation of DMS leads to the formation and growth of cloud condensation nuclei (CCN) with consequent effects on Earth’s radiation balance and climate. The quantitative assessment of the impact of DMS emissions on CCN concentrations necessitates a detailed description of the oxidation of DMS in the presence of existing aerosol particles and clouds. In the unpolluted marine atmosphere, DMS is efficiently oxidized to hydroperoxymethyl thioformate (HPMTF), a stable intermediate in the chemical trajectory toward sulfur dioxide (SO 2 ) and ultimately sulfate aerosol. Using direct airborne flux measurements, we demonstrate that the irreversible loss of HPMTF to clouds in the marine boundary layer determines the HPMTF lifetime ( τ HPMTF < 2 h) and terminates DMS oxidation to SO 2 . When accounting for HPMTF cloud loss in a global chemical transport model, we show that SO 2 production from DMS is reduced by 35% globally and near-surface (0 to 3 km) SO 2 concentrations over the ocean are lowered by 24%. This large, previously unconsidered loss process for volatile sulfur accelerates the timescale for the conversion of DMS to sulfate while limiting new particle formation inmore »the marine atmosphere and changing the dynamics of aerosol growth. This loss process potentially reduces the spatial scale over which DMS emissions contribute to aerosol production and growth and weakens the link between DMS emission and marine CCN production with subsequent implications for cloud formation, radiative forcing, and climate.« less

Abstract. Formaldehyde (HCHO) has been measured from space for morethan 2 decades. Owing to its short atmospheric lifetime, satellite HCHOdata are used widely as a proxy of volatile organic compounds (VOCs; pleaserefer to Appendix A for abbreviations and acronyms), providing constraintson underlying emissions and chemistry. However, satellite HCHO products fromdifferent satellite sensors using different algorithms have received littlevalidation so far. The accuracy and consistency of HCHO retrievals remainlargely unclear. Here we develop a validation platform for satellite HCHOretrievals using in situ observations from 12 aircraft campaigns with a chemicaltransport model (GEOS-Chem) as the intercomparison method. Application tothe NASA operational OMI HCHO product indicates negative biases (−44.5 %to −21.7 %) under high-HCHO conditions, while it indicates high biases (+66.1 % to+112.1 %) under low-HCHO conditions. Under both conditions, HCHO a priorivertical profiles are likely not the main driver of the biases. By providingquick assessment of systematic biases in satellite products over largedomains, the platform facilitates, in an iterative process, optimization ofretrieval settings and the minimization of retrieval biases. It is alsocomplementary to localized validation efforts based on ground observationsand aircraft spirals.

Abstract. Anthropogenic secondary organic aerosol (ASOA), formed from anthropogenicemissions of organic compounds, constitutes a substantial fraction of themass of submicron aerosol in populated areas around the world andcontributes to poor air quality and premature mortality. However, theprecursor sources of ASOA are poorly understood, and there are largeuncertainties in the health benefits that might accrue from reducinganthropogenic organic emissions. We show that the production of ASOA in 11urban areas on three continents is strongly correlated with the reactivityof specific anthropogenic volatile organic compounds. The differences inASOA production across different cities can be explained by differences inthe emissions of aromatics and intermediate- and semi-volatile organiccompounds, indicating the importance of controlling these ASOA precursors.With an improved model representation of ASOA driven by the observations,we attribute 340 000 PM2.5-related premature deaths per year to ASOA, which isover an order of magnitude higher than prior studies. A sensitivity casewith a more recently proposed model for attributing mortality to PM2.5(the Global Exposure Mortality Model) results in up to 900 000 deaths. Alimitation of this study is the extrapolation from cities with detailedstudies and regions where detailed emission inventories are available toother regions where uncertainties in emissions are larger. In addition tofurther development of institutional air quality management infrastructure,comprehensive airmore »quality campaigns in the countries in South and CentralAmerica, Africa, South Asia, and the Middle East are needed for furtherprogress in this area.« less

Dimethyl sulfide (DMS), emitted from the oceans, is the most abundant biological source of sulfur to the marine atmosphere. Atmospheric DMS is oxidized to condensable products that form secondary aerosols that affect Earth’s radiative balance by scattering solar radiation and serving as cloud condensation nuclei. We report the atmospheric discovery of a previously unquantified DMS oxidation product, hydroperoxymethyl thioformate (HPMTF, HOOCH 2 SCHO), identified through global-scale airborne observations that demonstrate it to be a major reservoir of marine sulfur. Observationally constrained model results show that more than 30% of oceanic DMS emitted to the atmosphere forms HPMTF. Coincident particle measurements suggest a strong link between HPMTF concentration and new particle formation and growth. Analyses of these observations show that HPMTF chemistry must be included in atmospheric models to improve representation of key linkages between the biogeochemistry of the ocean, marine aerosol formation and growth, and their combined effects on climate.

Concentrations of atmospheric trace species in the United States have changed dramatically over the past several decades in response to pollution control strategies, shifts in domestic energy policy and economics, and economic development (and resulting emission changes) elsewhere in the world. Reliable projections of the future atmosphere require models to not only accurately describe current atmospheric concentrations, but to do so by representing chemical, physical and biological processes with conceptual and quantitative fidelity. Only through incorporation of the processes controlling emissions and chemical mechanisms that represent the key transformations among reactive molecules can models reliably project the impacts of future policy, energy and climate scenarios. Efforts to properly identify and implement the fundamental and controlling mechanisms in atmospheric models benefit from intensive observation periods, during which collocated measurements of diverse, speciated chemicals in both the gas and condensed phases are obtained. The Southeast Atmosphere Studies (SAS, including SENEX, SOAS, NOMADSS and SEAC4RS) conducted during the summer of 2013 provided an unprecedented opportunity for the atmospheric modeling community to come together to evaluate, diagnose and improve the representation of fundamental climate and air quality processes in models of varying temporal and spatial scales.

This paper is aimed at discussing progress in evaluating,more »diagnosing and improving air quality and climate modeling using comparisons to SAS observations as a guide to thinking about improvements to mechanisms and parameterizations in models. The effort focused primarily on model representation of fundamental atmospheric processes that are essential to the formation of ozone, secondary organic aerosol (SOA) and other trace species in the troposphere, with the ultimate goal of understanding the radiative impacts of these species in the southeast and elsewhere. Here we address questions surrounding four key themes: gas-phase chemistry, aerosol chemistry, regional climate and chemistry interactions, and natural and anthropogenic emissions. We expect this review to serve as a guidance for future modeling efforts.« less