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Intensive air quality measurements made from June 22-25, 2011 in the outflow of the Dallas-Fort Worth (DFW) metropolitan area are used to evaluate nitrous acid (HONO) sources and sinks. A two-layer box model was developed to assess the ability of established and recently identified HONO sources and sinks to reproduce observations of HONO mixing ratios. A baseline model scenario includes sources and sinks established in the literature and is compared to scenarios including three recently identified sources: volatile organic compound-mediated conversion of nitric acid to HONO (S1), biotic emission from the ground (S2), and re-emission from a surface nitrite reservoir (S3). For all mechanisms, ranges of parametric values span lower- and upper-limit values. Model outcomes for 'likely' estimates of sources and sinks generally show under-prediction of HONO observations, implying the need to evaluate additional sources and variability in estimates of parameterizations, particularly during daylight hours. Monte Carlo simulation is applied to model scenarios constructed with sources S1-S3 added independently and in combination, generally showing improved model outcomes. Adding sources S2 and S3 (scenario S2/S3) appears to best replicate observed HONO, as determined by the model coefficient of determination and residual sum of squared errors (r2 = 0.55 ± 0.03, SSE = 4.6 × 106 ± 7.6 × 105 ppt2). In scenario S2/S3, source S2 is shown to account for 25% and 6.7% of the nighttime and daytime budget, respectively, while source S3 accounts for 19% and 11% of the nighttime and daytime budget, respectively. However, despite improved model fit, there remains significant underestimation of daytime HONO; on average, a 0.15 ppt/s unknown daytime HONO source, or 67% of the total daytime source, is needed to bring scenario S2/S3 into agreement with observation. Estimates of 'best fit' parameterizations across lower to upper-limit values results in a moderate reduction of the unknown daytime source, from 0.15 to 0.10 ppt/s.

The air quality in the outflow from Fort Worth, TX was studied in June 2011 at a location surrounded by oil and gas development in the Barnett Shale. The objectives of this study were to understand the major sources of volatile organic compounds (VOCs) and organic aerosols and explore the potential influence each VOC source had on ozone and secondary organic aerosol formation. Measurements of VOCs were apportioned between six factors using Positive Matrix Factorization (PMF): Natural Gas (25 ± 2%; ±99% CL); Fugitive Emissions (15 ± 2%); Internal Combustion Engines (15 ± 2%); Biogenic Emissions (7 ± 1%); Industrial Emissions/Oxidation 1(8 ± 1%); and Oxidation 2 (18 ± 2%). Reactivity calculations suggest the Biogenic and Oxidation 2 factors were the most likely VOC sources to influence local ozone. However, enough OH reactivity was calculated for factors related to the oil and gas development that they could incrementally increase O3. Three organic aerosol (OA) types were identified with PMF applied to high-resolution time-of-flight aerosol mass spectrometry measurements: hydrocarbon-like OA (HOA; 11% of mass) and two classes of oxidized OA (semi- and less-volatile OOA, SV and LV; 45% and 44%, respectively). The HOA correlated with the Internal Combustion Engine VOC factor indicating that a large fraction of the HOA was emitted by gasoline and diesel motors. The SV-OOA correlated with the oxidized VOC factors during most of the study, whereas a correlation between LV-OOA and the oxidized VOC factors was only observed during part of the study. It is hypothesized that SV-OOA and the oxidized VOC factors correlated reasonably well because these factors likely were separated by at most only a few oxidation generations on the oxidation pathway of organic compounds.

We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment.