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Halogen atoms and oxides are highly reactive and can profoundly affect atmospheric composition. Chlorine atoms can decrease the lifetimes of gaseous elemental mercury (1) and hydrocarbons such as the greenhouse gas methane (2). Chlorine atoms also influence cycles that catalytically destroy or produce tropospheric ozone (3), a greenhouse gas potentially toxic to plant and animal life. Conversion of inorganic chloride into gaseous chlorine atom precursors within the troposphere is generally considered a coastal or marine air phenomenon (4). Here we report mid-continental observations of the chlorine atom precursor nitryl chloride at a distance of 1,400 km from the nearest coastline. We observe persistent and significant nitryl chloride production relative to the consumption of its nitrogen oxide precursors. Comparison of these findings to model predictions based on aerosol and precipitation composition data from long-term monitoring networks suggests nitryl chloride production in the contiguous USA alone is at a level similar to previous global estimates for coastal and marine regions (5). We also suggest that a significant fraction of tropospheric chlorine atoms (6) may arise directly from anthropogenic pollutants., Night-time reactions of nitrogen oxides are known to convert inorganic chloride into chlorine atom ([Cl.sup.*]) precursors (7) (for example, Fig. 1). [N.sub.2][O.sub.5], a nocturnal N[O.sub.x] reservoir (N[O.sub.x] = No 1 [...]

Sulfur dioxide (SO2) is emitted in large quantities from coal‐burning power plants and leads to various harmful health and environmental effects. In this study, we use plume intercepts from the Wintertime INvestigation of Transport, Emission and Reactivity (WINTER) campaign to estimate the oxidation rates of SO2 under wintertime conditions and the factors that determine SO2 removal. Observations suggest that OH governs the rate SO2 oxidation in the eastern United States during winter. The range of mean oxidation rates during the day from power plants were 0.22–0.71%/hr, producing SO2 lifetimes of 13–43 days, if SO2 consumption is assumed to occur during 10.5 hr of daylight in cloudless conditions. Though most nighttime rate measurements were zero within uncertainty, there is some evidence of nighttime removal, which suggests alternate oxidation mechanisms. The fastest nighttime observed SO2 oxidation rate was 0.25±0.07%/hr, producing a combined day/night SO2 lifetime of 8.5–21 days. The upper limit of the oxidation rate (the mean+1σ of the fastest day and night observations) is 16.5%/day, corresponding to a lifetime of 6.1 days. The analysis also quantifies the primary emission of sulfate from power plants. The median mole percentage of SO4‐2 from observed plumes was 1.7% and the mean percentage sulfate was 2.8% for intercepts within 1 hr of transit to power plants. The largest value observed from close intercepts was over 7% sulfate, and the largest extrapolated value was 18%, based on intercepts further from their source and fastest observed oxidation rate. Key Points: The daytime conversion rate of SO2 to SO4‐2 was 0.22‐0.71%/hr in winter under clear‐sky conditions, with lifetimes of 140‐450 hrFor 10.5 hr of daylight, the upper limit of the oxidation rate is 16.5%/day, corresponding to a lifetime of 6.1 daysDirect emissions of SO4‐2 relative to total sulfur (SO2 + SO4‐2) had mean and median values of 1.7% and 2.8%, respectively [ABSTRACT FROM AUTHOR]

United States Environmental Protection Agency guidance on the use of photochemical models for assessing the efficacy of an emissions control strategy for ozone requires that modeling be used in a relative sense. Consequently, testing a modeling system's ability to predict changes in ozone resulting from emission changes is critical. We evaluate model simulations for precursor species (NOx, CO, and volatile organic compounds [VOCs]), radicals (OH and HO2), a secondary pollutant (O3), and the model response of these compounds to weekend/weekday emission changes during California Nexus study in 2010. The modeling system correctly simulated the broad spatial and temporal variation of NOx and O3 in California South Coast. Although the model generally underpredicted the daytime mixing ratios of NO2 at the surface and overpredicted the NO2 column, the simulated weekend to weekday ratios are consistent with each other and match the observed ratios well. The modeling system exhibited reasonable performance in simulating the VOC compounds with fossil fuel origins but has larger bias in simulating certain species associated with noncombustion sources. The modeling system successfully captured the weekend changes of the enhancement ratios for various VOC species to CO and the relative changes of HOx, which are indicators of faster chemical processing on weekends. This work demonstrates satisfactory model performances for O3 and most relevant chemical compounds with more robust performance in simulating weekend versus weekday changes. Improved planetary boundary layer height simulations, a better understanding of OH‐HO2 cycling, continued improvement of emissions, especially urban biogenic emissions and emissions of oxygenated VOCs, are important for future model improvement. Key Points: We evaluate model simulations for O3, NOx, VOCs, and HOx as well as their response to weekend emission changes during CalNex 2010The model results show a robust ability to simulate the weekend effect, for a majority of the relevant chemical speciesFurther understanding is needed for urban biogenic emissions and emissions of oxygenated VOCs such as ethanol, methanol, and acetone [ABSTRACT FROM AUTHOR]

Abstract: Nitric oxide (NO) is emitted in large quantities from coal‐burning power plants. During the day, the plumes from these sources are efficiently mixed into the boundary layer, while at night, they may remain concentrated due to limited vertical mixing during which they undergo horizontal fanning. At night, the degree to which NO is converted to HNO3 and therefore unable to participate in next‐day ozone (O3) formation depends on the mixing rate of the plume, the composition of power plant emissions, and the composition of the background atmosphere. In this study, we use observed plume intercepts from the Wintertime INvestigation of Transport, Emissions and Reactivity campaign to test sensitivity of overnight NOx removal to the N2O5 loss rate constant, plume mixing rate, background O3, and background levels of volatile organic compounds using a 2‐D box model of power plant plume transport and chemistry. The factor that exerted the greatest control over NOx removal was the loss rate constant of N2O5. At the lowest observed N2O5 loss rate constant, no other combination of conditions converts more than 10% of the initial NOx to HNO3. The other factors did not influence NOx removal to the same degree. [ABSTRACT FROM AUTHOR]

Experimental observations from coastal and island wind profilers, aircraft, and other sensors deployed during the California Land-falling Jets Experiment of 1997/98 and the Pacific Land-falling Jets Experiment of 2000/01–2003/04 were combined with observations from operational networks to document the regular occurrence and characteristic structure of shallow (∼400–500 m deep), cold airstreams flowing westward through California’s Petaluma Gap from the Central Valley to the coast during the winter months. The Petaluma Gap, which is the only major air shed outlet from the Central Valley, is ∼35–50 km wide and has walls extending, at most, a modest 600–900 m above the valley floor. Based on this geometry, together with winter meteorological conditions typical of the region (e.g., cold air pooled in the Central Valley and approaching extratropical cyclones), this gap is predisposed to generating westward-directed ageostrophic flows driven by along-gap pressure differences. Two case studies and a five-winter composite analysis of 62 gap-flow cases are presented here to show that flows through the Petaluma Gap significantly impact local distributions of wind, temperature, precipitation, and atmospheric pollutants. These gap flows preferentially occur in pre-cold-frontal conditions, largely because sea level pressure decreases westward along the gap in a stably stratified atmosphere in advance of approaching cold-frontal pressure troughs. Airstreams exiting the Petaluma Gap are only several hundred meters deep and characterized by relatively cold, easterly flow capped by a layer of enhanced static stability and directional vertical wind shear. Airborne air-chemistry observations collected offshore by the NOAA P-3 aircraft illustrate the fact that gap-flow events can transport pollutants from inland to the coast, and that they can contribute to coastally blocked airstreams. The strongest gap-flow cases occur when comparatively deep midtropospheric troughs approach the coast, while the weak cases are tied to anticyclonic conditions aloft. Low-level cold-frontal pressure troughs approaching the coast are stronger and possess a greater along-gap pressure gradient for the strong gap-flow cases. These synoptic characteristics are dynamically consistent with coastal wind profiler observations of stronger low-level gap flow and winds aloft, and greater rainfall, during the strong gap-flow events. However, gap flow, on average, inhibits rainfall at the coast. [ABSTRACT FROM AUTHOR]

Presents a new method of measuring carbon monoxide. Application of principle of gas filter correlation of method; Use of nondispersive infrared absorption.