Modeling nitrous acid and its impact on ozone and hydroxyl radical during the Texas Air Quality Study 2006

Nitrous acid (HONO) mixing ratios for the Houston metropolitan area were simulated with the Community Multiscale Air Quality (CMAQ) Model for an episode during the Texas Air Quality Study (TexAQS) II in August/September 2006 and compared to in-situ MC/IC (mist-chamber/ion chromatograph) and long path DOAS (Differential Optical Absorption Spectroscopy) measurements at three different altitude ranges. Several HONO sources were accounted for in simulations, such as gas phase formation, direct emissions, nitrogen dioxide (NO<sub>2</sub>) hydrolysis, photo-induced formation from excited NO<sub>2</sub> and photo-induced conversion of NO<sub>2</sub> into HONO on surfaces covered with organic materials. Compared to the gas-phase HONO formation there was about a tenfold increase in HONO mixing ratios when additional HONO sources were taken into account, which improved the correlation between modeled and measured values. Concentrations of HONO simulated with only gas phase chemistry did not change with altitude, while measured HONO concentrations decrease with height. A trend of decreasing HONO concentration with altitude was well captured with CMAQ predicted concentrations when heterogeneous chemistry and photolytic sources of HONO were taken into account. Heterogeneous HONO production mainly accelerated morning ozone formation, albeit slightly. Also HONO formation from excited NO<sub>2</sub> only slightly affected HONO and ozone (O<sub>3</sub>) concentrations. Photo-induced conversion of NO<sub>2</sub> into HONO on surfaces covered with organic materials turned out to be a strong source of daytime HONO. Since HONO immediately photo-dissociates during daytime its ambient mixing ratios were only marginally altered (up to 0.5 ppbv), but significant increase in the hydroxyl radical (OH) and ozone concentration was obtained. In contrast to heterogeneous HONO formation that mainly accelerated morning ozone formation, inclusion of photo-induced surface chemistry influenced ozone throughout the day

Tropospheric ozone sources and wave activity over Mexico City and Houston during MILAGRO/Intercontinental Transport Experiment (INTEX-B) Ozonesonde Network Study, 2006 (IONS-06)

During the INTEX-B (Intercontinental Chemical Transport Experiment)/ MILAGRO (Megacities Initiative: Local and Global Research Observations) experiments in March 2006 and the associated IONS-06 (INTEX Ozonesonde Network Study; <a href="http://croc.gsfc.nasa.gov/intexb/ions06.html" target="_blank">http://croc.gsfc.nasa.gov/intexb/ions06.html</a>), regular ozonesonde launches were made over 15 North American sites. The soundings were strategically positioned to study inter-regional flows and meteorological interactions with a mixture of tropospheric O<sub>3</sub> sources: local pollution; O<sub>3</sub> associated with convection and lightning; stratosphere-troposphere exchange. The variability of tropospheric O<sub>3</sub> over the Mexico City Basin (MCB; 19° N, 99° W) and Houston (30° N, 95° W) is reported here. MCB and Houston profiles displayed a double tropopause in most soundings and a subtropical tropopause layer with frequent wave disturbances, identified through O<sub>3</sub> laminae as gravity-wave induced. Ozonesondes launched over both cities in August and September 2006 (IONS-06, Phase 3) displayed a thicker tropospheric column O<sub>3</sub> (~7 DU or 15–20%) than in March 2006; nearly all of the increase was in the free troposphere. In spring and summer, O<sub>3</sub> laminar structure manifested mixed influences from the stratosphere, convective redistribution of O<sub>3</sub> and precursors, and O<sub>3</sub> from lightning NO. Stratospheric O<sub>3</sub> origins were present in 39% (MCB) and 60% (Houston) of the summer sondes. Comparison of summer 2006 O<sub>3</sub> structure with summer 2004 sondes (IONS-04) over Houston showed 7% less tropospheric O<sub>3</sub> in 2006. This may reflect a sampling contrast, August to mid-September 2006 instead of July-mid August 2004

Establishing Lagrangian connections between observations within air masses crossing the Atlantic during the International Consortium for Atmospheric Research on Transport and Transformation experiment

The ITCT-Lagrangian-2K4 (Intercontinental Transport and Chemical Transformation) experiment was conceived with an aim to quantify the effects of photochemistry and mixing on the transformation of air masses in the free troposphere away from emissions. To this end, attempts were made to intercept and sample air masses several times during their journey across the North Atlantic using four aircraft based in New Hampshire (USA), Faial (Azores) and Creil (France). This article begins by describing forecasts from two Lagrangian models that were used to direct the aircraft into target air masses. A novel technique then identifies Lagrangian matches between flight segments. Two independent searches are conducted: for Lagrangian model matches and for pairs of whole air samples with matching hydrocarbon fingerprints. The information is filtered further by searching for matching hydrocarbon samples that are linked by matching trajectories. The quality of these "coincident matches'' is assessed using temperature, humidity and tracer observations. The technique pulls out five clear Lagrangian cases covering a variety of situations and these are examined in detail. The matching trajectories and hydrocarbon fingerprints are shown, and the downwind minus upwind differences in tracers are discussed

MM5 v3.6.1 and WRF v3.5.1 model comparison of standard and surface energy variables in the development of the planetary boundary layer

Air quality forecasting requires atmospheric weather models to generate accurate meteorological conditions, one of which is the development of the planetary boundary layer (PBL). An important contributor to the development of the PBL is the land–air exchange captured in the energy budget as well as turbulence parameters. Standard and surface energy variables were modeled using the fifth-generation Penn State/National Center for Atmospheric Research mesoscale model (MM5), version 3.6.1, and the Weather Research and Forecasting (WRF) model, version 3.5.1, and compared to measurements for a southeastern Texas coastal region. The study period was 28 August–1 September 2006. It also included a frontal passage. The results of the study are ambiguous. Although WRF does not perform as well as MM5 in predicting PBL heights, it better simulates energy budget and most of the general variables. Both models overestimate incoming solar radiation, which implies a surplus of energy that could be redistributed in either the partitioning of the surface energy variables or in some other aspect of the meteorological modeling not examined here. The MM5 model consistently had much drier conditions than the WRF model, which could lead to more energy available to other parts of the meteorological system. On the clearest day of the study period, MM5 had increased latent heat flux, which could lead to higher evaporation rates and lower moisture in the model. However, this latent heat disparity between the two models is not visible during any other part of the study. The observed frontal passage affected the performance of most of the variables, including the radiation, flux, and turbulence variables, at times creating dramatic differences in the r2 values

Influence of Oil and Gas Emissions on Summertime Ozone in the Colorado Northern Front Range

Tropospheric O 3 has been decreasing across much of the eastern U.S. but has remained steady or even increased in some western regions. Recent increases in VOC and NO x emissions associated with the production of oil and natural gas (O&NG) may contribute to this trend in some areas. The Northern Front Range of Colorado has regularly exceeded O 3 air quality standards during summertime in recent years. This region has VOC emissions from a rapidly developing O&NG basin and low concentrations of biogenic VOC in close proximity to urban-Denver NO x emissions. Here VOC OH reactivity (OHR), O 3 production efficiency (OPE), and an observationally constrained box model are used to quantify the influence of O&NG emissions on regional summertime O 3 production. Analyses are based on measurements acquired over two summers at a central location within the Northern Front Range that lies between major regional O&NG and urban emission sectors. Observational analyses suggest that mixing obscures any OPE differences in air primarily influenced by O&NG or urban emission sector. The box model confirms relatively modest OPE differences that are within the uncertainties of the field observations. Box model results also indicate that maximum O 3 at the measurement location is sensitive to changes in NO x mixing ratio but also responsive to O&NGVOC reductions. Combined, these analyses show that O&tp://esrl. noaa.gov/csd, FRAPPNG alkanes contribute over 80% to the observed carbon mixing ratio, roughly 50% to the regional VOC OHR, and approximately 20% to regional photochemical O 3 production

Statistical inference of OH concentrations and air mass dilution rates from successive observations of non-methane hydrocarbons in single air masses

Bayesian inference has been used to determine rigorous estimates of hydroxyl radical concentrations () and air mass dilution rates (K) averaged following air masses between linked observations of nonmethane hydrocarbons (NMHCs) spanning the North Atlantic during the Intercontinental Transport and Chemical Transformation (ITCT)-Lagrangian-2K4 experiment. The Bayesian technique obtains a refined (posterior) distribution of a parameter given data related to the parameter through a model and prior beliefs about the parameter distribution. Here, the model describes hydrocarbon loss through OH reaction and mixing with a background concentration at rate K. The Lagrangian experiment provides direct observations of hydrocarbons at two time points, removing assumptions regarding composition or sources upstream of a single observation. The estimates are sharpened by using many hydrocarbons with different reactivities and accounting for their variability and measurement uncertainty. A novel technique is used to construct prior background distributions of many species, described by variation of a single parameter . This exploits the high correlation of species, related by the first principal component of many NMHC samples. The Bayesian method obtains posterior estimates of , K and following each air mass. Median values are typically between 0.5 and 2.0 × 106 molecules cm−3, but are elevated to between 2.5 and 3.5 × 106 molecules cm−3, in low-level pollution. A comparison of estimates from absolute NMHC concentrations and NMHC ratios assuming zero background (the “photochemical clock” method) shows similar distributions but reveals systematic high bias in the estimates from ratios. Estimates of K are ∼0.1 day−1 but show more sensitivity to the prior distribution assumed

Formaldehyde and its relation to CO, PAN, and SO₂ in the Houston-Galveston airshed

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