Nitryl chloride (ClNO2) is a chlorine atom source and reactive nitrogen reservoir formed during the night by heterogeneous reactions of dinitrogen pentoxide on chloride‐containing aerosol particles. The main factors that influence ClNO2 production include nitrogen oxides, ozone, aerosol surface area, soluble chloride, and ambient relative humidity. Regions with strong anthropogenic activity therefore have large ClNO2 formation potential even inland of coastal regions due to transport or local emissions of soluble chloride. As part of the Nitrogen, Aerosol Composition, and Halogens on a Tall Tower field study, we report wintertime vertically resolved ClNO2 and molecular chlorine (Cl2) measurements taken on a 300 m tall tower located at NOAA's Boulder Atmospheric Observatory in Weld County, CO, during February and March of 2011. Gas and particle phase measurements aboard the tower carriage allowed for a detailed description of the chemical state of the nocturnal atmosphere as a function of height. These observations show significant vertical structure in ClNO2 and Cl2 mixing ratios that undergo dynamic changes over the course of a night. Using these measurements, we focus on two distinct combustion plume events where ClNO2 mixing ratios reached 600 and 1300 parts per trillion by volume, respectively, aloft of the nocturnal surface layer. We infer ClNO2 yields from N2O5‐aerosol reactions using both observational constraints and box modeling. The derived yields in these plumes suggest efficient ClNO2 production compared to the campaign average, where in‐plume yields range from 0.3 to 1; the campaign average yield in the boundary layer is 0.05 ± 0.15, with substantial night‐to‐night and within night variability similar to previous measurements in this region.

[1] Heterogeneous N 2 O 5 uptake onto aerosol is the primary nocturnal path for removal of NO x (= NO + NO 2 ) from the atmosphere and can also result in halogen activation through production of ClNO 2 . The N 2 O 5 uptake coefficient has been the subject of numerous laboratory studies; however, only a few studies have determined the uptake coefficient from ambient measurements, and none has been focused on winter conditions, when the portion of NO x removed by N 2 O 5 uptake is the largest. In this work, N 2 O 5 uptake coefficients are determined from ambient wintertime measurements of N 2 O 5 and related species at the Boulder Atmospheric Observatory in Weld County, CO, a location that is highly impacted by urban pollution from Denver, as well as emissions from agricultural activities and oil and gas extraction. A box model is used to analyze the nocturnal nitrate radical chemistry and predict the N 2 O 5 concentration. The uptake coefficient in the model is iterated until the predicted N 2 O 5 concentration matches the measured concentration. The results suggest that during winter, the most important influence that might suppress N 2 O 5 uptake is aerosol nitrate but that this effect does not suppress uptake coefficients enough to limit the rate of NO x loss through N 2 O 5 hydrolysis. N 2 O 5 hydrolysis was found to dominate the nocturnal chemistry during this study consuming~80% of nocturnal gas phase nitrate radical production. Typically, less than 15% of the total nitrate radical production remained in the form of nocturnal species at sunrise when they are photolyzed and reform NO 2 . , et al. (2013), N 2 O 5 uptake coefficients and nocturnal NO 2 removal rates determined from ambient wintertime measurements, J. Geophys. Res. Atmos., 118,[9331][9332][9333][9334][9335][9336][9337][9338][9339][9340][9341][9342][9343][9344][9345][9346][9347][9348][9349][9350]

[1] A negative-ion proton-transfer chemical ionization mass spectrometer was deployed on a mobile tower-mounted platform during Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) to measure nitrous acid (HONO) in the winter of 2011. High resolution vertical profiles revealed (i) HONO gradients in nocturnal boundary layers, (ii) ground surface dominates HONO production by heterogeneous uptake of NO 2 , (iii) significant quantities of HONO may be deposited to the ground surface at night, (iv) daytime gradients indicative of ground HONO production or emission, and (v) an estimated surface HONO reservoir comparable or larger than integrated daytime HONO surface production. Nocturnal integrated column observations of HONO and NO 2 allowed direct evaluation of nocturnal ground surface uptake coefficients for these species (γ NO2, surf = 2 × 10 À6 to 1.6 × 10 À5 and γ HONO, surf = 2 × 10 À5 to 2 × 10 À4 ). The quantity of surface-deposited HONO was also modeled, showing that HONO deposited to the surface at night was at least 25%, and likely in excess of 100%, of the calculated unknown daytime HONO source. These results suggest that if nocturnally deposited HONO forms a conservative surface reservoir, which can be released the following day, a significant fraction of the daytime HONO source can be explained for the NACHTT observations. Citation: VandenBoer, T. C., et al. (2013), Understanding the role of the ground surface in HONO vertical structure: High resolution vertical profiles during

Isocyanic acid (HNCO) has only recently been measured in the ambient atmosphere, and many aspects of its atmospheric chemistry are still uncertain. HNCO was measured during three diverse field campaigns: California Nexus-Research at the Nexus of Air Quality and Climate Change (CalNex 2010) at the Pasadena ground site, Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT 2011) at the Boulder Atmospheric Observatory (BAO) in Weld County, CO, and Biofuel Crops emission of Ozone precursors intensive (BioCORN 2011), in a cornfield NW of Fort Collins, CO. Mixing ratios varied from below detection limit (~0.003 ppbv) to over 1.2 ppbv during a period when agricultural burning impacted the BAO Tower site. Urban areas, such as the CalNex 2010 Pasadena site, appear to have both primary (combustion) and secondary (photochemical) sources of HNCO, 50 ± 9%, and 33 ± 12%, respectively, while primary sources were responsible for the large mixing ratios of HNCO observed during the wintertime NACHTT study in suburban Colorado. Isocyanic acid during the BioCORN study in rural NE Colorado was closely correlated to ozone and therefore likely photochemically produced as a secondary product from amines or formamide. The removal of HNCO from the lower atmosphere is thought to be due to deposition, as common gas phase loss processes of photolysis and reactions with hydroxyl radicals, are slow. These ambient measurements are consistent with some HNCO deposition, which was evident at night at these surface sites.

[1] The Nitrogen, Aerosol Composition, and Halogens on a Tall Tower (NACHTT) field experiment took place during late winter, 2011, at a site 33 km north of Denver, Colorado. The study included fixed-height measurements of aerosols, soluble trace gases, and volatile organic compounds near surface level, as well as vertically resolved measurements of nitrogen oxides, aerosol composition, soluble gas-phase acids, and halogen species from 3 to 270 m above ground level. There were 1928 individual profiles during the three-week campaign to characterize trace gas and aerosol distributions in the lower levels of the boundary layer. Nitrate and ammonium dominated the ionic composition of aerosols and originated primarily from local or regional sources. Sulfate and organic matter were also significant and were associated primarily with longer-range transport to the region. Aerosol chloride was associated primarily with supermicron size fractions and was always present in excess of gas-phase chlorine compounds. The nighttime radical reservoirs, nitryl chloride, ClNO 2 , and nitrous acid, HONO, were both consistently present in nighttime urban air. Nitryl chloride was especially pronounced in plumes from large point sources sampled aloft at night. Nitrous acid was typically most concentrated near the ground surface and was the dominant contributor (80%) to diurnally averaged primary OH radical production in near-surface air. Large observed mixing ratios of light alkanes, both in near-surface air and aloft, were attributable to local emissions from oil and gas activities.

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Cancer has become the primary reason of deaths in Dilovasi probably due to its location with unique topography under the influence of heavy industrialization and traffic. In this study, possible sources and carcinogenic health risks of PAHs and PCBs were investigated in Dilovasi region by Positive Matrix Factorization (PMF) and the USEPA approach, respectively. PAHs and PCBs were measured monthly for a whole year at 23 sampling sites using PUF disk passive samplers. Average ambient air concentrations were found as 285±431ng/m and 4152±6072pg/m, for ΣPAH and ΣPCB, respectively. PAH concentrations increased with decreasing temperature especially at urban sites, indicating the impact of residential heating in addition to industrial activities and traffic. On the other hand, PCB concentrations mostly increased with temperature probably due to enhanced volatilization from their sources. Possible sources of PAHs were found as emissions of diesel and gasoline vehicles, biomass and coal combustion, iron and steel industry, and unburned petroleum/petroleum products, whereas iron-steel production, coal and biomass burning, technical PCB mixtures, and industrial emissions were identified for PCBs. The mean carcinogenic risk associated with inhalation exposure to PAHs and PCBs were estimated to be >10 and >10, respectively, at all sampling points, while the 95th percentile was >10 at 15 of 23 and >10 at 8 of 23 sampling locations, respectively. Probabilistic assessment showed, especially for PCBs, that a majority of Dilovasi population face significant health risks. The higher risks due to PCBs further indicated that PCBs and possibly other pollutants originating from the same sources such as PBDEs and PCNs may be an important issue for the region.

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