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, HOOCH2SCHO), 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.

Most intensive field studies investigating aerosols have been conducted in summer, and thus, wintertime aerosol sources and chemistry are comparatively poorly understood. An aerosol mass spectrometer was flown on the National Science Foundation/National Center for Atmospheric Research C‐130 during the Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) 2015 campaign in the northeast United States. The fraction of boundary layer submicron aerosol that was organic aerosol (OA) was about a factor of 2 smaller than during a 2011 summertime study in a similar region. However, the OA measured in WINTER was almost as oxidized as OA measured in several other studies in warmer months of the year. Fifty‐eight percent of the OA was oxygenated (secondary), and 42% was primary (POA). Biomass burning OA (likely from residential heating) was ubiquitous and accounted for 33% of the OA mass. Using nonvolatile POA, one of two default secondary OA (SOA) formulations in GEOS‐Chem (v10‐01) shows very large underpredictions of SOA and O/C (5×) and overprediction of POA (2×). We strongly recommend against using that formulation in future studies. Semivolatile POA, an alternative default in GEOS‐Chem, or a simplified parameterization (SIMPLE) were closer to the observations, although still with substantial differences. A case study of urban outflow from metropolitan New York City showed a consistent amount and normalized rate of added OA mass (due to SOA formation) compared to summer studies, although proceeding more slowly due to lower OH concentrations. A box model and SIMPLE perform similarly for WINTER as for Los Angeles, with an underprediction at ages <6 hr, suggesting that fast chemistry might be missing from the models.

Wildfires are an important source of nitrous acid (HONO), a photolabile radical precursor, yet in situ measurements and quantification of primary HONO emissions from open wildfires have been scarce. We present airborne observations of HONO within wildfire plumes sampled during the Western Wildfire Experiment for Cloud chemistry, Aerosol absorption and Nitrogen (WE-CAN) campaign. ΔHONO/ΔCO close to the fire locations ranged from 0.7 to 17 pptv ppbv–1 using a maximum enhancement method, with the median similar to previous observations of temperate forest fire plumes. Measured HONO to NO x enhancement ratios were generally factors of 2, or higher, at early plume ages than previous studies. Enhancement ratios scale with modified combustion efficiency and certain nitrogenous trace gases, which may be useful to estimate HONO release when HONO observations are lacking or plumes have photochemical exposures exceeding an hour as emitted HONO is rapidly photolyzed. We find that HONO photolysis is the dominant contributor to hydrogen oxide radicals (HO x = OH + HO2) in early stage (<3 h) wildfire plume evolution. These results highlight the role of HONO as a major component of reactive nitrogen emissions from wildfires and the main driver of initial photochemical oxidation.

[1] Mixing ratios of isoprene, methyl vinyl ketone (MVK), and methacrolein (MACR) were determined continuously during an 8-day period in the summer of 1998 at a rural forested site located within the University of Michigan Biological Station (UMBS). The measurements were obtained as part of the Program for Research on Oxidants: Photochemistry, Emissions, and Transport (PROPHET) study. Fluxes of isoprene were concurrently measured at a nearby tower (AmeriFlux, located 132 m north-northeast of the PROPHET tower). Following the study, 1-kmresolution emission estimates were derived for isoprene within a 60-km radius of the tower using forest density estimates (Biogenic Emissions Inventory System (BEIS3) model). Measured isoprene fluxes at the site compared well with modeled isoprene fluxes when using BEIS3 and a detailed leaf litter-fall data set by tree species from the UMBS site. Mean midday (1000 -1400 LT) mixing ratios for isoprene, MACR, and MVK were 1.90 ± 0.43, 0.07 ± 0.01, and 0.14 ± 0.04 ppbv, respectively. Median midday mixing ratios of these compounds were 1.96 ± 0.26, 0.06 ± 0.02, and 0.10 ± 0.02 ppbv, respectively. Ratios of the isoprene oxidation products to isoprene are understood in the context of previous laboratory and field measurement studies of these compounds and a simple consecutive reaction scheme model. Results of the model indicate that the air masses studied represented relatively fresh emissions with a photochemical age of measured isoprene between 3.6 and 18 min, which is significantly less than the photochemical lifetime of isoprene (t = 45 min at [OH] = 3.35 Â 10 6 molecules cm À3 ). Thus a large portion of the isoprene that reaches the manifold has not had time to react completely with OH, yielding lower than expected ratios based on model calculations that do not explicitly take this into account. A rapid decrease in isoprene mixing ratios was observed soon after sunset, followed by a slower decay throughout the rest of the night. Emission maps were generated indicating that isoprene fluxes are highest in the immediate vicinity of the tower compared to the surrounding area of the site. Thus vertical diffusion and advection from the surrounding region are postulated to cause the observed initial rapid decrease in isoprene at the site. The second isoprene decay may be due to chemistry and/or dynamics, but the effects cannot be separated with the available data.

Abstract. The volatile organic compound (VOC) distribution in the Mexico City Metropolitan Area (MCMA) and its evolution as it is uplifted and transported out of the MCMA basin was studied during the 2006 MILAGRO/MIRAGEMex field campaign. The results show that in the morning hours in the city center, the VOC distribution is dominated by non-methane hydrocarbons (NMHCs) but with a substantial contribution from oxygenated volatile organic compounds (OVOCs), predominantly from primary emissions. Alkanes account for a large part of the NMHC distribution in terms of mixing ratios. In terms of reactivity, NMHCs also dominate overall, especially in the morning hours. However, in the afternoon, as the boundary layer lifts and air is mixed and aged within the basin, the distribution changes as secondary products are formed. The WRF-Chem (Weather Research and Forecasting with Chemistry) model and MOZART (Model for Ozone and Related chemical Tracers) were able to approximate the observed MCMA daytime patterns and abCorrespondence to: E. C. Apel (apel@ucar.edu) solute values of the VOC OH reactivity. The MOZART model is also in agreement with observations showing that NMHCs dominate the reactivity distribution except in the afternoon hours. The WRF-Chem and MOZART models showed higher reactivity than the experimental data during the nighttime cycle, perhaps indicating problems with the modeled nighttime boundary layer height.A northeast transport event was studied in which air originating in the MCMA was intercepted aloft with the Department of Energy (DOE) G1 on 18 March and downwind with the National Center for Atmospheric Research (NCAR) C130 one day later on 19 March. A number of identical species measured aboard each aircraft gave insight into the chemical evolution of the plume as it aged and was transported as far as 1000 km downwind; ozone was shown to be photochemically produced in the plume. The WRF-Chem and MOZART models were used to examine the spatial extent and temporal evolution of the plume and to help interpret the observed OH reactivity. The model results generally showed good agreement with experimental results for the total VOC OH reactivity downwind and gave insight into the distributions of VOC chemical classes. A box model with Published by Copernicus Publications on behalf of the European Geosciences Union. 2354 E. C. Apel et al.: Chemical evolution of volatile organic compounds detailed gas phase chemistry (NCAR Master Mechanism), initialized with concentrations observed at one of the ground sites in the MCMA, was used to examine the expected evolution of specific VOCs over a 1-2 day period. The models clearly supported the experimental evidence for NMHC oxidation leading to the formation of OVOCs downwind, which then become the primary fuel for ozone production far away from the MCMA.