Absorption of Near UV Light by HNO3/NO3(-) on Sapphire Surfaces.

We have determined absorption of the near UV light (290-345 nm) by nitric acid (HNO3) deposition on sapphire window surfaces as a function of the HNO3 pressure, by using Brewster angle cavity ring-down spectroscopy. Apparent monolayer HNO3 surface absorption cross sections have been obtained; they range between (1.7 ± 1.1) × 10(-19) and (0.29 ± 0.03) × 10(-19) cm(2)/molecule. When nitric acid cross section values on sapphire surfaces were divided by those on fused silica surfaces for which only molecular HNO3 adsorption was reported, a new absorption band appeared in the 320-345 nm region. The shape of this absorption band is similar to that reported for surface nitrate (NO3(-)) at quartz/water interfaces, but is red-shifted by about 10 nm. Our study suggests that a small percentage (<7%) of adsorbed HNO3 formed by HNO3 deposition on sapphire surfaces is dissociated into surface nitrate on the time scale of about 5-7 min. Background transmission changes in the 320-350 nm region after exposing clean sapphire surfaces with many repeated HNO3 deposition/evacuation cycles are consistent with surface nitrate formation. We obtained nitrate surface absorption cross section data over 320-350 nm range. We also modeled photolysis rates of HNO3/NO3(-) on urban grimes. Atmospheric implications of the results are discussed.

Projected ozone trends and changes in the ozone-precursor relationship in the South Coast Air Basin in response to varying reductions of precursor emissions.

UNLABELLED: This study examined the effects of varying future reductions in emissions of oxides of nitrogen (NOx) and volatile organic compounds (VOC) on the location and magnitude of peak ozone levels within California's South Coast Air Basin (SoCAB or Basin). As ozone formation is currently VOC-limited in the Basin, model simulations with 2030 baseline emissions (-61% for NOx and -32% for VOC from 2008) predict 10-20% higher peak ozone levels (i.e., NOx disbenefit) in the western and central SoCAB compared with the 2008 base simulation. With additional NOx reductions of 50% beyond the 2030 baseline emissions (-81% from 2008), the predicted ozone levels are reduced by about 15% in the eastern SoCAB but remain comparable to 2008 levels in the western and central Basin. The Basin maximum ozone site shifts westward to more populated areas of the Basin and will result potentially in greater population-weighted exposure to ozone with even a relatively small shortfall in the required NOx reductions unless accompanied by additional VOC reductions beyond 2030 baseline levels. Once committed to a NOx-focused control strategy, NOx reductions exceeding 90% from 2008 levels will be necessary to attain the ozone National Ambient Air Quality Standards (NAAQS). The findings from this study and other recent work that the current VOC emission estimates are underestimated by about 50% suggest that greater future VOC reductions will be necessary to reach the projected 2030 baseline emissions. Increasing the base year VOC emissions by a factor of 1.5 result in higher 2008 baseline ozone predictions, lower relative response factors, and about 20% lower projected design values. If correct, these findings have important implications for the total and optimum mix of VOC and NOx emission reductions that will be required to attain the ozone NAAQS in the SoCAB. IMPLICATIONS: Results of this study indicate that ozone levels in the western and central SoCAB would remain the same or increase with even a relatively small shortfall in the projected NOx reductions under planned NOx-focused controls. This possibility, therefore, warrants a rigorous analysis of the costs and effects of varying reductions of VOC and NOx on the formation and combined health impacts of ozone and secondary particles. Given the nonlinearity of ozone formation, such analyses should include the implications of gradually increasing global background ozone concentrations and the Basin's topography and meteorology on the practical limits of alternative emission control strategies.

Past and future ozone trends in California's South Coast Air Basin: reconciliation of ambient measurements with past and projected emission inventories.

UNLABELLED: This paper updates the historic trends (1980-2010) in ambient ozone and ozone precursor concentrations in the South Coast Air Basin (SoCAB) and examines the evolution of the ozone-precursor relationship in the Basin. Whereas reductions in NOx (oxide of nitrogen) emissions have decreased nitrate and PM2.5 (particulate matter with an aerodynamic diameter < or = 2.5 microm) concentrations in the Basin during the past decade, ozone levels have increased at the central basin locations since about 2005 following a reversal in the decline of volatile organic compound (VOC)/NOx ratios during the previous two decades. A chemical box model was used to simulate the effects of changes in precursor concentrations on ozone formation using day-of-week-specific initial precursor concentrations that were derived from measurements and'projected to 2020 based on expected emission reductions from 2005 (-10% VOC and -50% NOx). Results show that peak ozone formation rates in 2020 will increase on weekdays by a factor of 3 relative to 2005 and will be comparable to 1995 weekday and 2005 Sunday rates. Ozone production will become precursor limited on Sundays in 2020, but with higher initial rates than 2005. Although a greater NOx reduction scenario in 2020 of -75% will result in even higher initial ozone formation rates, precursor limitation is reached quickly, leading to a further shift westward in the location of peak ozone levels. However ozone levels will likely be lower in downwind areas where transport is more important than local production of ozone. The ambient versus emission inventory reconciliation indicates a factor of 2 underestimation of VOC emissions in 2009 relative to NOx. Other analyses suggest that there is an overall increase in VOC emissions on hot days that is not fully accounted for by emission inventory estimates. Air quality models using emission inventories that underestimate VOC emissions relative to NOx may lead to inaccurate forecasting of the consequence of emission reductions. IMPLICATIONS: The rate and efficiency of ozone formation and accumulation in the SoCAB is more rapid than would be indicated by air quality model simulations based on the current inventory. Projected reductions in NOx emissions without concurrent reductions in VOC emissions will likely cause ozone to increase during the next decade within central regions of the SoCAB compared with a flat or slightly declining trend in far downwind locations. Air quality statistics that are commonly used to track progress toward attainment, such as basin-wide ozone design value and standard exceedances mask these varying trends within the Basin.

Photochemical modeling in California with two chemical mechanisms: model intercomparison and response to emission reductions.

An updated version of the Statewide Air Pollution Research Center (SAPRC) chemical mechanism (SAPRC07C) was implemented into the Community Multiscale Air Quality (CMAQ) version 4.6. CMAQ simulations using SAPRC07C and the previously released version, SAPRC99, were performed and compared for an episode during July-August, 2000. Ozone (O3) predictions of the SAPRC07C simulation are generally lower than those of the SAPRC99 simulation in the key areas of central and southern California, especially in areas where modeled concentrations are greater than the federal 8-hr O3 standard of 75 parts per billion (ppb) and/or when the volatile organic compound (VOC)/nitrogen oxides (NOx) ratio is less than 13. The relative changes of ozone production efficiency (OPE) against the VOC/NOx ratio at 46 sites indicate that the OPE is reduced in SAPRC07C compared with SAPRC99 at most sites by as much as approximately 22%. The SAPRC99 and SAPRC07C mechanisms respond similarly to 20% reductions in anthropogenic VOC emissions. The response of the mechanisms to 20% NOx emissions reductions can be grouped into three cases. In case 1, in which both mechanisms show a decrease in daily maximum 8-hr O3 concentration with decreasing NOx emissions, the O3 decrease in SAPRC07C is smaller. In case 2, in which both mechanisms show an increase in O3 with decreasing NOx emissions, the O3 increase is larger in SAPRC07C. In case 3, SAPRC07C simulates an increase in O3 in response to reduced NOx emissions whereas SAPRC99 simulates a decrease in O3 for the same region. As a result, the areas where NOx controls would be disbeneficial are spatially expanded in SAPRC07C. Although the results presented here are valuable for understanding differences in predictions and model response for SAPRC99 and SAPRC07C, the study did not evaluate the impact of mechanism differences in the context of the U.S. Environmental Protection Agency's guidance for using numerical models in demonstrating air quality attainment. Therefore, additional study is required to evaluate the full regulatory implications of upgrading air quality models to SAPRC07.

A perspective on the development of gas-phase chemical mechanisms for Eulerian air quality models.

An essential component of a three-dimensional air quality model is its gas-phase mechanism. We present an overview of the necessary atmospheric chemistry and a discussion of the types of mechanisms with some specific examples such as the Master Chemical Mechanism, the Carbon Bond, SAPRC and the Regional Atmospheric Chemistry Mechanism (RACM). The first versions of the Carbon Bond and SAPRC mechanisms were developed through a hierarchy of chemical species approach that relied heavily on chemical environmental chamber data. Now a new approach has been proposed where the first step is to develop a highly detailed explicit mechanism such as the Master Chemical Mechanism and the second step is to test the detailed explicit mechanism against laboratory and field data. Finally, the detailed mechanism is condensed for use in a three-dimensional air quality model. Here it is argued that the development of highly detailed explicit mechanisms is very valuable for research, but we suggest that combining the hierarchy of chemical species and the detailed explicit mechanism approaches would be better than either alone.Implication: Many gas-phase mechanisms are available for urban, regional and global air quality modeling. A "hierarchy of chemical species approach," relying heavily on smog-chamber data was used for the development of the early series of mechanisms. Now the development of large, explicit master mechanisms that may be condensed is a significant, trend. However, a continuing problem with air quality mechanism development is due to the high complexity of atmospheric chemistry and the current availability of laboratory measurements. This problem requires a balance between completeness and speculation so that models maintain their utility for policymakers.

Dominant volatile organic compounds (VOCs) measured at four Cannabis growing facilities: Pilot study results.

In recent years, sale of recreational marijuana products has been permitted in several states and countries resulting in rapid growth of the commercial cannabis cultivation and processing industry. As previous research has shown, biogenic volatile organic compounds (BVOCs) emitted from plants can react with other urban air constituents (e.g., NOx, HO radical) and thus negatively affect regional air quality. In this pilot study, BVOC emissions from Cannabis plants were analyzed at four grow facilities. The concentrations of measured BVOCs inside the facilities were between 110 and 5,500 µg m-3. One adult Cannabis plant emits hundreds of micrograms of BVOCs per day and thus can trigger the formation of tropospheric ozone (approximately 2.6 g day-1 plant-1) and other toxic air pollutants. In addition, high concentrations of butane (1,080- 43,000 µg m-3), another reactive VOC, were observed at the facilities equipped with Cannabis oil extraction stations. Implications: High concentrations of VOCs emitted from Cannabis grow facilities can lead to the formation of ozone, secondary VOCs (e.g., formaldehyde and acrolein), and particulate matter. Our results highlight that further assessment of VOC emissions from Cannabis facilities is needed, and this assessment is one of the key factors for developing policies for optimal air pollution control.

Projected changes in particulate matter concentrations in the South Coast Air Basin due to basin-wide reductions in nitrogen oxides, volatile organic compounds, and ammonia emissions.

An ozone abatement strategy for the South Coast Air Basin (SoCAB) has been proposed by the South Coast Air Quality Management District (SCAQMD) and the California Air Resources Board (ARB). The proposed emissions reduction strategy is focused on the reduction of nitrogen oxide (NOx) emissions by the year 2030. Two high PM2.5 concentration episodes with high ammonium nitrate compositions occurring during September and November 2008 were simulated with the Community Multi-scale Air Quality model (CMAQ). All simulations were made with same meteorological files provided by the SCAQMD to allow them to be more directly compared with their previous modeling studies. Although there was an overall under-prediction bias, the CMAQ simulations were within an overall normalized mean error of 50%; a range that is considered acceptable performance for PM modeling. A range of simulations of these episodes were made to evaluate sensitivity to NOx and ammonia emissions inputs for the future year 2030. It was found that the current ozone control strategy will reduce daily average PM2.5 concentrations. However, the targeted NOx reductions for ozone were not found to be optimal for reducing PM2.5 concentrations. Ammonia emission reductions reduced PM2.5 and this might be considered as part of a PM2.5 control strategy. Implications: The SCAQMD and the ARB have proposed an ozone abatement strategy for the SoCAB that focuses on NOx emission reductions. Their strategy will affect both ozone and PM2.5. Two episodes that occurred during September and November 2008 with high PM2.5 concentrations and high ammonium nitrate composition were selected for simulation with different levels of nitrogen oxide and ammonia emissions for the future year 2030. It was found that the ozone control strategy will reduce maximum daily average PM2.5 concentrations but its effect on PM2.5 concentrations is not optimal.

Linking Air Quality and Human Health Effects Models: An Application to the Los Angeles Air Basin.

Proposed emission control strategies for reducing ozone and particulate matter are evaluated better when air quality and health effects models are used together. The Community Multiscale Air Quality (CMAQ) model is the US Environmental Protection Agency's model for determining public policy and forecasting air quality. CMAQ was used to forecast air quality changes due to several emission control strategies that could be implemented between 2008 and 2030 for the South Coast Air Basin that includes Los Angeles. The Environmental Benefits Mapping and Analysis Program-Community Edition (BenMAP-CE) was used to estimate health and economic impacts of the different emission control strategies based on CMAQ simulations. BenMAP-CE is a computer program based on epidemiologic studies that link human health and air quality. This modeling approach is better for determining optimum public policy than approaches that only examine concentration changes.

Evolution of the magnitude and spatial extent of the weekend ozone effect in California's South Coast Air Basin, 1981-2000.

Since the mid-1970s, ozone (O3) levels in portions of California's South Coast Air Basin (SoCAB) on weekends have been as high as or higher than levels on weekdays, even though emissions of O3 precursors are lower on weekends. Analysis of the ambient data indicates that the intensity and spatial extent of the weekend O3 effect are correlated with-day-of-week variations in the extent of O3 inhibition caused by titration with nitric oxide (NO), reaction of hydroxyl radical (OH) with nitrogen dioxide (NO2), and rates of O3 accumulation. Lower NO mixing ratios and higher NO2/oxides of nitrogen (NOx) ratios on weekend mornings allow O3 to begin accumulating approximately an hour earlier on weekends. The weekday/weekend differences in the duration of O3 accumulation remained relatively constant from 1981 to 2000. In contrast, the rate of O3 accumulation decreased by one-third to one-half over the same period; the largest reductions occurred in the central basin on weekdays. Trends in mixing ratios of O3 precursors show a transition to lower volatile organic compound (VOC)/NOx ratios caused by greater reductions in VOC emissions. Reductions in VOC/NOx ratios were greater on weekdays, resulting in higher VOC/NOx ratios on weekends relative to weekdays. Trends in VOC/NOx ratios parallel the downward trend in peak O3 levels, a shift in the location of peak O3 from the central to the eastern portion of the basin, and an increase in the magnitude and spatial extent of the weekend O3 effect.

Diurnal and weekday variations in the source contributions of ozone precursors in California's South Coast Air Basin.

For at least 30 years, ozone (O3) levels on weekends in parts of California's South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O3 precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NOx) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O3 formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NOx associated with black carbon (BC) to NOx associated with carbon monoxide (CO) were approximately 1.25 +/- 0.22 during weekdays and 0.76 +/- 0.07 and 0.52 +/- 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NOx emissions from diesel exhaust can be a major factor causing lower NOx mixing ratios and higher NMHC/NOx ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NOx ratios on weekend mornings.

Sensitivity modeling study for an ozone occurrence during the 1996 Paso Del Norte Ozone Campaign.

Surface ozone pollution has been a persistent environmental problem in the US and Europe as well as the developing countries. A key prerequisite to find effective alternatives to meeting an ozone air quality standard is to understand the importance of local anthropogenic emissions, the significance of biogenic emissions, and the contribution of long-range transport. In this study, an air quality modeling system that includes chemistry and transport, CMAQ, an emission processing model, SMOKE, and a mesoscale numerical meteorological model, WRF, has been applied to investigate an ozone event occurring during the period of the 1996 Paso del Norte Ozone Campaign. The results show that the modeling system exhibits the capability to simulate this high ozone occurrence by providing a comparable temporal variation of surface ozone concentration at one station and to capture the spatial evolution of the event. Several sensitivity tests were also conducted to identify the contributions to high surface ozone concentration from eight VOC subspecies, biogenic VOCs, anthropogenic VOCs and long-range transportation of ozone and its precursors. It is found that the reductions of ETH, ISOP, PAR, OLE and FORM help to mitigate the surface ozone concentration, and like anthropogenic VOCs, biogenic VOC plays a nonnegligible role in ozone formation. But for this case, long-range transport of ozone and its precursors appears to produce an insignificant contribution.