Using a reduced Common Representative Intermediates (CRIv2-R5) mechanism to simulate tropospheric ozone in a 3-D Lagrangian chemistry transport model

A reduced chemical scheme (CRIv2-R5) which describes ozone formation from the tropospheric degradation of methane and 22 emitted non-methane hydrocarbons and oxygenated volatile organic compounds has been applied in a global-3D chemistry transport model (STOCHEM). The scheme, which contains 220 species in 609 reactions, has been used to simulate ozone and its precursors for the meteorological year of 1998 and the results have been compared with those from STOCHEM runs with its original chemistry. Compared with the original chemistry scheme, the degradation of a larger number of more reactive VOCs in the CRI scheme results in the formation (and their consequent transportation) of more NO_x active reservoirs thus leading to formation of more ozone away from land-based sources. Conversely, the more reactive VOCs also lead to greater removal of OH in continental areas and greater formation of OH in marine environments. STOCHEM run with the CRI scheme simulates more ozone (by up to 10 ppb), which results in better agreement with observed vertical ozone profiles. The CRI scheme transforms the globally and annually integrated ozone budget for the considered year in STOCHEM from a net loss of ?55 Tg yr^?1 to a net gain of +50 Tg yr^?1.     

Surface ozone and NOx concentrations at a high altitude Mediterranean site,Greece

Ozone was measured in six- and NO_x in five sampling periods in 1996–97, mostly during summer, at a 1070 m altitude site in northern Peloponnese. Mean values in each sampling period ranged from 43–48 ppb exceeding the European Union 24 h plant protection standard. The background ozone concentration of 43 ppb derived from the correlation of ozone with NO^′_x also exceeded the EU plant protection standard. Ozone exhibited maxima in the afternoon and minima during the night; in certain 24–48 h periods, however, the ozone concentrations remained practically constant; in these short periods air mass back trajectories indicated air masses which originated in north Africa. NO^′_x concentrations had maximum of 24 h around noon. Their mean concentrations ranged from 0.5–0.7 ppb, smaller than respective concentrations in north-central Europe.     

The influence of south foehn on the ozone mixing ratios at the high alpine site Arosa

Within 2 years of trace gas measurements performed at Arosa (Switzerland, 2030 m above sea level), enhanced ozone mixing ratios were observed during south foehn events during summer and spring (5–10 ppb above the median value). The enhancements can be traced back to ozone produced in the strongly industrialized Po basin as confirmed by various analyses. Backward trajectories clearly show advection from this region during foehn. NO_y versus O₃ correlation and comparison of O₃ mixing ratios between Arosa and Mt. Cimone (Italy, 2165 m asl) suggest that ozone is the result of recent photochemical production (+5.6 ppb on average), either directly formed during the transport or via mixing of air processed in the Po basin boundary layer. The absence of a correlation between air parcel residence times over Europe and ozone mixing ratios at Arosa during foehn events is in contrast to a previous analysis, which suggested such correlation without reference to the origin of the air. In the case of south foehn, the continental scale influence of pollutants emission on ozone at Arosa appears to be far less important than the direct influence of the Po basin emissions. In contrast, winter time displays a different situation, with mean ozone reductions of about 4 ppb for air parcels passing the Po basin, probably caused by mixing with ozone-poor air from the Po basin boundary layer.     

Improving ozone modeling in complex terrain at a fine grid resolution – Part II: Influence of schemes in MM5 on daily maximum 8-h ozone concentrations and RRFs (Relative Reduction Factors) for SIPs in the non-attainment areas

Part II presents a comprehensive evaluation of CMAQ for August of 2002 on twenty-one sensitivity simulations (detailed in Part I) in MM5 to investigate the model performance for O₃ SIPs (State Implementation Plans) in the complex terrain. CMAQ performance was quite consistent with the results of MM5, meaning that accurate meteorological fields predicted in MM5 as an input resulted in good model performance of CMAQ. In this study, PBL scheme plays a more important role than its land surface models (LSMs) for the model performance of CMAQ. Our results have shown that the outputs of CMAQ on eighteen sensitivity simulations using two different nudging coefficients for winds (2.5 and 4.5 × 10^?4 s^?1, respectively) tend to under predict daily maximum 8-h ozone concentrations at valley areas except the TKE PBL sensitivity simulations (ETA M-Y PBL scheme with Noah LSMs and 5-layer soil model and Gayno-Seaman PBL) using 6.0 × 10^?4 s^?1 with positive MB (Mean Bias). At mountain areas, none of the sensitivity simulations has presented over predictions for 8-h O₃, due to relatively poor meteorological model performance. When comparing 12-km and 4-km grid resolutions for the PX simulation in CMAQ statistics analysis, the CMAQ results at 12-km grid resolution consistently show under predictions of 8-h O₃ at both of valley and mountain areas and particularly, it shows relatively poor model performance with a 15.1% of NMB (Normalized Mean Bias). Based on our sensitivity simulations, the TKE PBL sensitivity simulations using a maximum value (6 × 10^?4) among other sensitivity simulations yielded better model performance of CMAQ at all areas in the complex terrain. As a result, the sensitivity of RRFs to the PBL scheme may be considerably significant with about 1–3 ppb in difference in determining whether the attainment test is passed or failed. Furthermore, we found that the result of CMAQ model performance depending on meteorological variations is affected on estimating RRFs for attainment demonstration, indicating that it is necessary to improve model performance. Overall, G_c (Gayo-Seaman PBL scheme) using the coefficient for winds, 6 × 10^?4 s^?1, sensitivity simulation predicts daily maximum 8-h ozone concentration closer to observations during a typical summer period from May to September and provides generally low future design values (DVFs) at valley and mountain areas compared to other simulations.     

Chemical transport models

Background, aim, and scope  Improving the parameterization of processes in the atmospheric boundary layer (ABL) and surface layer, in air quality and chemical transport models. To do so, an asymmetrical, convective, non-local scheme, with varying upward mixing rates is combined with the non-local, turbulent, kinetic energy scheme for vertical diffusion (COM). For designing it, a function depending on the dimensionless height to the power four in the ABL is suggested, which is empirically derived. Also, we suggested a new method for calculating the in-canopy resistance for dry deposition over a vegetated surface. Materials and methods  The upward mixing rate forming the surface layer is parameterized using the sensible heat flux and the friction and convective velocities. Upward mixing rates varying with height are scaled with an amount of turbulent kinetic energy in layer, while the downward mixing rates are derived from mass conservation. The vertical eddy diffusivity is parameterized using the mean turbulent velocity scale that is obtained by the vertical integration within the ABL. In-canopy resistance is calculated by integration of inverse turbulent transfer coefficient inside the canopy from the effective ground roughness length to the canopy source height and, further, from its the canopy height. Results  This combination of schemes provides a less rapid mass transport out of surface layer into other layers, during convective and non-convective periods, than other local and non-local schemes parameterizing mixing processes in the ABL. The suggested method for calculating the in-canopy resistance for calculating the dry deposition over a vegetated surface differs remarkably from the commonly used one, particularly over forest vegetation. Discussion  In this paper, we studied the performance of a non-local, turbulent, kinetic energy scheme for vertical diffusion combined with a non-local, convective mixing scheme with varying upward mixing in the atmospheric boundary layer (COM) and its impact on the concentration of pollutants calculated with chemical and air-quality models. In addition, this scheme was also compared with a commonly used, local, eddy-diffusivity scheme. Simulated concentrations of NO₂ by the COM scheme and new parameterization of the in-canopy resistance are closer to the observations when compared to those obtained from using the local eddy-diffusivity scheme. Conclusions  Concentrations calculated with the COM scheme and new parameterization of in-canopy resistance, are in general higher and closer to the observations than those obtained by the local, eddy-diffusivity scheme (on the order of 15–22%). Recommendations and perspectives  To examine the performance of the scheme, simulated and measured concentrations of a pollutant (NO₂) were compared for the years 1999 and 2002. The comparison was made for the entire domain used in simulations performed by the chemical European Monitoring and Evaluation Program Unified model (version UNI-ACID, rv2.0) where schemes were incorporated.     

Improving ozone modeling in complex terrain at a fine grid resolution: Part I – examination of analysis nudging and all PBL schemes associated with LSMs in meteorological model

Meteorological variables such as temperature, wind speed, wind directions, and Planetary Boundary Layer (PBL) heights have critical implications for air quality simulations. Sensitivity simulations with five different PBL schemes associated with three different Land Surface Models (LSMs) were conducted to examine the impact of meteorological variables on the predicted ozone concentrations using the Community Multiscale Air Quality (CMAQ) version 4.5 with local perspective. Additionally, the nudging analysis for winds was adopted with three different coefficients to improve the wind fields in the complex terrain at 4-km grid resolution. The simulations focus on complex terrain having valley and mountain areas at 4-km grid resolution. The ETA M–Y (Mellor–Yamada) and G–S (Gayno–Seaman) PBL schemes are identified as favorite options and promote O₃ formation causing the higher temperature, slower winds, and lower mixing height among sensitivity simulations in the area of study. It is found that PX (Pleim–Xiu) simulation does not always give optimal meteorological model performance. We also note that the PBL scheme plays a more important role in predicting daily maximum 8-h O₃ than land surface models. The results of nudging analysis for winds with three different increased coefficients' values (2.5, 4.5, and 6.0 × 10^?4 s^?1) over seven sensitivity simulations show that the meteorological model performance was enhanced due to improved wind fields, indicating the FDDA nudging analysis can improve model performance considerably at 4-km grid resolution. Specifically, the sensitivity simulations with the coefficient value (6.0 × 10^?4) yielded more substantial improvements than with the other values (2.5 and 4.5 × 10^?4). Hence, choosing the nudging coefficient of 6.0 × 10^?4 s^?1 for winds in MM5 may be the best choice to improve wind fields as an input, as well as, better model performance of CMAQ in the complex terrain area. As a result, a finer grid resolution is necessary to evaluate and access of CMAQ results for giving a detailed representation of meteorological and chemical processes in the regulatory modeling. A recommendation of optimal scheme options for simulating meteorological variables in the complex terrain area is made.     

Ozone and meteorological boundary-layer conditions at Summit,Greenland, during 3–21 June 2000

The temporal and spatial distributions of boundary-layer ozone were studied during June 2000 at Summit, Greenland, using surface-level measurements and vertical profiling from a tethered balloon platform. Three weeks of continuous ozone surface data, 133 meteorological vertical profile data and 82 ozone vertical profile data sets were collected from the surface to a maximum altitude of 1400 m above ground.The lower atmosphere at Summit was characterized by the prevalence of strong stable conditions with strong surface temperature inversions. These inversions reversed to neutral to slightly unstable conditions between ∼9.00 and 18.00 h local time with the formation of shallow mixing heights of ∼70–250 m above the surface.The surface ozone mixing ratio ranged from 39 to 68 ppbv and occasionally had rapid changes of up to 20 ppb in 12 h. The diurnal mean ozone mixing ratio showed diurnal trends indicating meteorological and photochemical controls of surface ozone. Vertical profiles were within the range of 37–76 ppb and showed strong stratification in the lower troposphere. A high correlation of high ozone/low water vapor air masses indicated the transport of high tropospheric/low stratospheric air into the lower boundary layer. A ∼0.1–3 ppb decline of the ozone mixing ratio towards the surface was frequently observed within the neutrally stable mixed layer during midday hours. These data suggest that the boundary-layer ozone mixing ratio and ozone depletion and deposition to the snowpack are influenced by photochemical processes and/or transport phenomena that follow diurnal dependencies. With 37 ppb of ozone being the lowest mixing ratio measured in all data no evidence was seen for the occurrence of ozone depletion episodes similar to those that have been reported within the boundary layer at coastal Arctic sites during springtime.     

Increasing interannual and altitudinal ozone mixing ratios in the Catalan Pyrenees

Interannual, seasonal, daily and altitudinal patterns of tropospheric ozone mixing ratios, as well as ozone phytotoxicity and the relationship with NO_x precursors and meteorological variables were monitored in the Central Catalan Pyrenees (Meranges valley and Forest of Guils) over a period of 5 years (2004–2008). Biweekly measurements using Radiello passive samplers were taken along two altitudinal transects comprised of thirteen stations ranging from 1040 to 2300 m a.s.l. Visual symptoms of ozone damage in Bel-W3 tobacco cultivars were evaluated biweekly for the first three years (2004–2006). High ozone mixing ratios, always above forest and vegetation protection AOT40 thresholds, were monitored every year. In the last 14 years, the AOT40 (Apr–Sept.) has increased significantly by 1047 μg m^?3 h per year. Annual means of ozone mixing ratios ranged between 38 and 67 ppb_v (38 and 74 ppb_v during the warm period) at the highest site (2300 m) and increased at a rate of 5.1 ppb_v year^?1. The ozone mixing ratios were also on average 35–38% greater during the warm period and had a characteristic daily pattern with minimum values in the early morning, a rise during the morning and a decline overnight, that was less marked the higher the altitude. Whereas ozone mixing ratios increased significantly with altitude from 35 ppb_v at 1040 m–56 ppb_v at 2300 m (on average for 2004–2007 period), NO₂ mixing ratios decreased with altitude from 5.5 ppb_v at 1040 m–1 ppb_v at 2300 m. The analysis of meteorological variables and NO_x values suggests that the ozone mainly originated from urban areas and was transported to high-mountain sites, remaining aloft in absence of NO. Ozone damage rates increased with altitude in response to increasing O₃ mixing ratios and a possible increase in O₃ uptake due to more favorable microclimatic conditions found at higher altitude, which confirms Bel-W3 as a suitable biomonitor for ozone concentrations during summer time. Compared to the valley-bottom site the annual means of ozone mixing ratios are 37% larger in the higher sites. Thus the AOT40 for the forest and vegetation protection threshold is greatly exceeded at higher sites. This could have substantial effects on plant life at high altitudes in the Pyrenees.     

Tropical tropospheric ozone observed in Thailand

The mixing ratios of surface ozone at two rural/remote sites in Thailand, Inthanon and Srinakarin, have been measured continuously for the first time. Almost identical seasonal variations of O₃ with dry season maximum and a wet season minimum with a large seasonal amplitude are observed at both sites during 1996–1998. At Inthanon, the monthly averaged O₃ mixing ratios range 9–55 ppb, with the annual average of 27 ppb. The ozone mixing ratios at Srinakarin are in the similar range, 9–45 ppb with annual average of 28 ppb. Based on trajectory analysis of O₃ data at Inthanon, the long-range transport of O₃ under Asian monsoon regime could primarily explain the low O₃ mixing ratios of 13 ppb in clean marine air mass from Indian Ocean during wet season but only partly explain the relatively low O₃ mixing ratios, 26 ppb or less, in continental air mass from northeast Asia either in wet or dry season. The highest O₃ mixing ratios are found in air masses transported within southeast Asia, averaged 46 ppb in dry season. The high O₃ mixing ratios during the dry season are suggested to be significantly due to the local/sub-regional scale O₃ production triggered by biomass burning in southeast Asia rather than long-range transport effect.     

Ozone response to precursor controls: comparison of data analysis methods with the predictions of photochemical air quality simulation models

Comparisons were made between the predictions of six photochemical air quality simulation models (PAQSMs) and three indicators of ozone response to emission reductions: the ratios of O₃/NO_z and O₃/NO_y and the extent of reaction. The values of the two indicator ratios and the extent of reaction were computed from the model-predicted mixing ratios of ozone and oxidized nitrogen species and were compared to the changes in peak 1 and 8 h ozone mixing ratios predicted by the PAQSMs. The ozone changes were determined from the ozone levels predicted for base-case emission levels and for reduced emissions of volatile organic compounds (VOCs) and oxides of nitrogen (NO_x). For all simulations, the model-predicted responses of peak 1 and 8 h ozone mixing ratios to VOC or NO_x emission reductions were correlated with the base-case extent of reaction and ratios of O₃/NO_z and O₃/NO_y. Peak ozone values increased following NO_x control in 95% (median over all simulations) of the high-ozone (>80 ppbv hourly mixing ratio in the base-case) grid cells having mean afternoon O₃/NO_z ratios less than 5 : 1, O₃/NO_y less than 4 : 1, or extent less than 0.6. Peak ozone levels decreased in response to NO_x reductions in 95% (median over all simulations) of the grid cells having peak hourly ozone mixing ratios greater than 80 ppbv and where mean afternoon O₃/NO_z exceeded 10 : 1, O₃/NO_y was greater than 8 : 1, or extent exceeded 0.8. Ozone responses varied in grid cells where O₃/NO_z was between 5 : 1 and 10 : 1, O₃/NO_y was between 4 : 1 and 8 : 1, or extent was between 0.6 and 0.8. The responses in such grid cells were affected by ozone responses in upwind grid cells and by the changes in ozone levels along the upwind boundaries of the modeling domains.     

Synoptic weather patterns and their relationship to high ozone concentrations in the Taichung Basin

Frequent high ozone days (defined as daily maximum ozone concentration ⩾80 ppb) during recent years in the Taichung Basin have caused much concern. High ozone days occur mainly during autumn and spring. Statistically, there is no clear linear relationship between a single meteorological variable and ozone concentration. In this study, data from 1996–2000 has shown that high ozone concentrations occur during two types of synoptic weather patterns. The first type is a continental cyclone emanating from mainland China, the southern part of it swept towards Taiwan by easterly winds. The second pattern is a tropical depression moving northwards toward the region, the northern part of it affecting Taiwan via easterly winds. Both types cover Taiwan with easterly winds, which are blocked by the Central Mountain Ranges (altitude of 2000–3000 m). The ranges create lee cyclogenesis to the west, which is unfavorable for pollutant dispersion and leads to serious air pollution episodes.The statistical results of the synoptic weather patterns in relation to ozone concentrations are based on the 5 yr data (1996–2000). This was obtained from a network of air-pollution monitoring sites in the study area, while the vertical data come from two 3-day tethersonde experimental campaigns conducted during March and October 2000, measuring air pressure, air temperature, relative humidity, wind speed and direction, non-methane hydrocarbons, NO_x and O₃.     

Measurements of primary trace gases and NOY composition in Houston,Texas

Concentrations of CO, SO₂, NO, NO₂, and NO_Y were measured atop the University of Houston's Moody Tower supersite during the 2006 TexAQS-II Radical and Aerosol Measurement Project (TRAMP). The lowest concentrations of all primary and secondary species were observed in clean marine air in southerly flow. SO₂ concentrations were usually low, but increased dramatically in sporadic midday plumes advected from sources in the Houston Ship Channel (HSC), located NE of the site. Concentrations of CO and NO_x displayed large diurnal variations in keeping with their co-emission by mobile sources in the Houston Metropolitan Area (HMA). CO/NO_x emission ratios of 5.81 ± 0.94 were observed in the morning rush hour. Nighttime concentrations of NO_x (NO_x = NO + NO₂) and NO_Y (NO_Y = NO + NO₂ + NO₃ + HNO₃ + HONO + 21N₂O₅ + HO₂NO₂ + PANs + RONO₂ + p-NO₃^? + …) were highest in winds from the NNW-NE due to emission from mobile sources. Median ratios of NO_x/NO_Y were approximately 0.9 overnight, reflecting the persistence and/or generation of NO_Z (NO_Z = NO_Y ? NO_x) species in the nighttime Houston boundary layer, and approached unity in the morning rush hour. Daytime concentrations of NO_x and NO_Y were highest in winds from the HSC. NO_x/NO_Y ratios reached their minimum values (median ca 0.63) from 1300 to 1500 CST, near local solar noon, and air masses often retained enough NO_x to sustain additional O₃ formation farther downwind. HNO₃ and PANs comprised the dominant NO_Z species in the HMA, and on a median basis represented 17–20% and 12–15% of NO_Y, respectively, at midday. Concentrations of HNO₃, PANs, and NO_Z, and fractional contributions of these species to NO_Y, were at a maximum in NE flow, reflecting the source strength and reactivity of precursor emissions in the HSC. As a result, daytime O₃ concentrations were highest in air masses with HSC influence. Overall, our findings confirm the impact of the HSC as a dominant source region within the HMA. A comparison of total NO_Y measurements with the sum of measured NO_Y species (NO_Yi = NO_x + HNO₃ + PANs + HONO + p-NO₃^?) yielded excellent overall agreement during both day ([NO_Y](ppb) = ([NO_Yi](ppb)11.03 ± 0.16) ? 0.42; r² = 0.9933) and night ([NO_Y](ppb) = ([NO_Yi](ppb)11.01 ± 0.16) + 0.18; r² = 0.9975). A similar comparison between NO_Y–NO_x concentrations and the sum of NO_Zi (NO_Zi = HNO₃ + PANs + HONO + p-NO₃^?) yielded good overall agreement during the day ([NO_Z](ppb) = ([NO_Zi](ppb)11.01 ± 0.30) + 0.044 ppb; r² = 0.8527) and at night ([NO_Z](ppb) = ([NO_Zi](ppb)11.12 ± 0.69) + 0.16 ppb; r² = 0.6899). Median ratios of NO_Z/NO_Zi were near unity during daylight hours but increased to approximately 1.2 overnight, a difference of 0.15–0.50 ppb. Differences between NO_Z and NO_Zi rarely exceeded combined measurement uncertainties, and variations in NO_Z/NO_Zi ratios may have resulted solely from errors in conversion efficiencies of NO_Y species and changes in NO_Y composition. However, nighttime NO_Z/NO_Zi ratios and the magnitude of NO_Z ? NO_Zi differences were generally consistent with recent observations of ClNO₂ in the nocturnal Houston boundary layer.     

Estimating the effects of increased urbanization on surface meteorology and ozone concentrations in the New York City metropolitan region

Land use and pollutant emission changes can have significant impacts on air quality, regional climate, and human health. Here we describe a modeling study aimed at quantifying the potential effects of extensive changes in urban land cover in the New York City (NYC), USA metropolitan region on surface meteorology and ozone (O₃) concentrations. The SLEUTH land-use change model was used to extrapolate urban land cover over this region from “present-day” (ca. 1990) conditions to a future year (ca. 2050), and these projections were subsequently integrated into meteorological and air quality simulations. The development of the future-year land-use scenario followed the narrative of the “A2” scenario described by the Intergovernmental Panel on Climate Change (IPCC), but was restricted to the greater NYC area. The modeling system consists of the Penn State/NCAR MM5 mesoscale meteorological model; the Sparse Matrix Operator Kernal Emissions processing system; and the US EPA Community Multiscale Air Quality model, and simulations were performed for two 18-day episodes, one near-past and one future. Our results suggest that extensive urban growth in the NYC metropolitan area has the potential to increase afternoon near-surface temperatures by more than 0.6 °C and planetary boundary layer (PBL) heights by more than 150 m, as well as decrease water vapor mixing ratio by more than 0.6 g kg⁻¹, across the NYC metropolitan area, with the areal extent of all of these changes generally coinciding with the area of increased urbanization. On the other hand, the impacts of these land use changes on ozone concentrations are more complex. Simulation results indicate that future changes in urbanization, with emissions held constant, may lead to increases in episode-average O₃ levels by about 1–5 ppb, and episode-maximum 8 h O₃ levels by more than 6 ppb across much of the NYC area. However, spatial patterns of ozone changes are heterogeneous and also indicate the presence of areas with decreasing ozone concentrations. When anthropogenic emissions were increased to be consistent with the extensive urbanization in the greater NYC area, the O₃ levels increased in outer counties of the metropolitan region but decreased in others, including coastal Connecticut and the Long Island Sound area.     

Variations of the increasing trend of tropospheric NO2 over central east China during the past decade

A numerical analysis using a regional chemical transport model (CTM) is presented in comparison with Global Ozone Monitoring Experiment (GOME) and SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) satellite NO₂ measurements over East Asia from 1996 to 2005 from a climatological perspective. Modeling results agree well with satellite retrievals in geographical distribution patterns, with systematic underestimation of the absolute values. The sharp increase in NO₂ vertical column densities (VCDs) over central east China (CEC) after the year 2000 (14.1–20.5% yr⁻¹ for the satellite observations and 10.8% yr⁻¹ for model simulations) is analyzed quantitatively over different megacity clusters. The distinct emission increase patterns are responsible for the different increase trends observed over the Beijing megacity cluster (BJ), the Yangtze Delta (YD) and other CEC regions. The growth rate of satellite measured and CMAQ-modeled NO₂ VCDs for the YD is much higher than that in other regions, with no clear seasonal variation. Apart from BJ and YD, NO₂ emissions from other regions in CEC also expand considerably.     

Mesoscale modelling of vertical atmospheric transport in the Alps associated with the advection of a tropopause fold – a winter ozone episode

The role of vertical atmospheric transport (VAT) for a winter ozone episode (January 1988) in the Alps, observed both on the mountain crest (3580 m asl) and in the lee of the Alps (209 m asl), is investigated. Numerical simulations were carried out with a doubly nested mesoscale model (14 km horizontal resolution), characterised by a refined orography scheme. A comparison between the modelled vertical profiles with features observed in the aerological soundings over Payerne indicated that the model is able to reproduce the fold in the Alps down to 650 hPa. Frictional processes are found to be responsible for the fragmentation of the lower parts of the fold when it is advected over the mountains, thus enhancing ozone concentrations at the mountain crest with likely cross-tropopause mixing. Vertically propagating gravity waves and strong mesoscale vertical winds (nordfoehn) are responsible for the further downward transport of ozone-rich air to the lower troposphere. This mechanism leads to ozone concentrations up to 70 ppb(v) in the leeside. The study is important because tropospheric ozone trends in the lee of the Alps have been inferred, in the past, from ozone peaks associated with such nordfoehn conditions. It is now shown that nordfoehn may entrain air which has been recently exchanged across the tropopause.     

Impact of biogenic VOC emissions on a tropical cyclone-related ozone episode in the Pearl River Delta region,China

For quantitative estimate of biogenic volatile organic compound emissions (BVOCs) in South China and their impact on the regional atmospheric chemistry, a 3-day tropical cyclone-related ozone episode was modeled using chemical transport model CMAQ, which was driven by the mesoscale meteorological model MM5. Hourly biogenic emission inventories were constructed using the Sparse Matrix Operator Kernel Emissions (SMOKE) model. The simulation results show good agreement with observation data in air temperature, ozone and NO_x levels. The estimated biogenic emissions of isoprene, terpene, and other reactive VOCs (ORVOCs) during this tropical cyclone-related episode are 8500, 3400, and 11 300 ton day⁻¹, respectively. The ratio of isoprene to the total BVOCs was 36.4%. Two test runs were carried out with one incorporated biogenic emissions and the other without. The simulations show that Guangdong province, particularly the Pearl River Delta (PRD) region, was the area most reactive to biogenic emissions in South China. More ozone was produced in all layers under 1500 m when biogenic emissions were included in comparison to that without BVOCs. The net formation of ozone from 9:00 to 15:00 h was the highest near the surface and could reach 38 ppb, which include 4 ppb attributed to biogenic impact. The enhanced ozone due to biogenic emissions first appeared in the PRD region and slowly spread to a greater area in South China. Process analysis indicated that the surface ozone budget was dominated by the vertical transport and dry deposition. The horizontal transport and gas-phase chemical production were relatively small in the surface layer. Presumably, ozone was produced in upper layers within the atmospheric boundary layer and convected down to surface where it is destroyed. When BVOCs was included, apart from the enhancement of gas-phase chemical production of ozone, both the surface deposition and vertical transport were also augmented.     

Expected ozone benefits of reducing nitrogen oxide (NOx) emissions from coal-fired electricity generating units in the eastern United States

On hot summer days in the eastern United States, electricity demand rises, mainly because of increased use of air conditioning. Power plants must provide this additional energy, emitting additional pollutants when meteorological conditions are primed for poor air quality. To evaluate the impact of summertime NO_x emissions from coal-fired electricity generating units (EGUs) on surface ozone formation, we performed a series of sensitivity modeling forecast scenarios utilizing EPA 2018 version 6.0 emissions (2011 base year) and CMAQ v5.0.2. Coal-fired EGU NO_x emissions were adjusted to match the lowest NO_x rates observed during the ozone seasons (April 1–October 31) of 2005–2012 (Scenario A), where ozone decreased by 3–4 ppb in affected areas. When compared to the highest emissions rates during the same time period (Scenario B), ozone increased ～4–7 ppb. NO_x emission rates adjusted to match the observed rates from 2011 (Scenario C) increased ozone by ～4–5 ppb. Finally in Scenario D, the impact of additional NO_x reductions was determined by assuming installation of selective catalytic reduction (SCR) controls on all units lacking postcombustion controls; this decreased ozone by an additional 2–4 ppb relative to Scenario A. Following the announcement of a stricter 8-hour ozone standard, this analysis outlines a strategy that would help bring coastal areas in the mid-Atlantic region closer to attainment, and would also provide profound benefits for upwind states where most of the regional EGU NO_x originates, even if additional capital investments are not made (Scenario A).

Implications: With the 8-hr maximum ozone National Ambient Air Quality Standard (NAAQS) decreasing from 75 to 70 ppb, modeling results indicate that use of postcombustion controls on coal-fired power plants in 2018 could help keep regions in attainment. By operating already existing nitrogen oxide (NO_x) removal devices to their full potential, ozone could be significantly curtailed, achieving ozone reductions by up to 5 ppb in areas around the source of emission and immediately downwind. Ozone improvements are also significant (1–2 ppb) for areas affected by cross-state transport, especially Mid-Atlantic coast regions that had struggled to meet the 75 ppb standard.     

Ozone uptake by citrus trees exposed to a range of ozone concentrations

The Citrus genus includes a large number of species and varieties widely cultivated in the Central Valley of California and in many other countries having similar Mediterranean climates. In the summer, orchards in California experience high levels of tropospheric ozone, formed by reactions of volatile organic compounds (VOC) with oxides of nitrogen (NO_x). Citrus trees may improve air quality in the orchard environment by taking up ozone through stomatal and non-stomatal mechanisms, but they may ultimately be detrimental to regional air quality by emitting biogenic VOC (BVOC) that oxidize to form ozone and secondary organic aerosol downwind of the site of emission. BVOC also play a key role in removing ozone through gas-phase chemical reactions in the intercellular spaces of the leaves and in ambient air outside the plants. Ozone is known to oxidize leaf tissues after entering stomata, resulting in decreased carbon assimilation and crop yield. To characterize ozone deposition and BVOC emissions for lemon (Citrus limon), mandarin (Citrus reticulata), and orange (Citrus sinensis), we designed branch enclosures that allowed direct measurement of fluxes under different physiological conditions in a controlled greenhouse environment. Average ozone uptake was up to 11 nmol s^?1 m^?2 of leaf. At low concentrations of ozone (40 ppb), measured ozone deposition was higher than expected ozone deposition modeled on the basis of stomatal aperture and ozone concentration. Our results were in better agreement with modeled values when we included non-stomatal ozone loss by reaction with gas-phase BVOC emitted from the citrus plants. At high ozone concentrations (160 ppb), the measured ozone deposition was lower than modeled, and we speculate that this indicates ozone accumulation in the leaf mesophyll.     

Peroxyacetyl nitrate and peroxypropionyl nitrate in Porto Alegre,Brazil

For 41 days between 25 May 1996 and 27 March 1997, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) have been measured by electron capture gas chromatography at Santa Rita near Porto Alegre, RS, Brazil, where light-duty vehicles used either ethanol or a gasoline–MTBE blend. Daily maximum concentrations ranged from 0.19 to 6.67 ppb for PAN and 0.06 to 0.72 ppb for PPN. Linear regression of maximum PPN vs. maximum PAN yielded a slope of 0.105±0.004 (R²=0.974). Diurnal variations of ambient PAN often followed those of ozone with respect to time of day but not with respect to amplitude. This was reflected in the large relative standard deviations associated with the study-averaged PAN/ozone concentration ratio, 0.037±0.105 (ppb/ppb, n=789) and the maximum PAN/maximum ozone concentration ratio, 0.028±0.015 (ppb/ppb, range 0.005–0.078, n=41). On several days PAN accounted for large fractions of the total ambient NO_x in the late morning and afternoon hours, e.g., PAN/NO_x⩽0.58 and PAN/(NO_x–NO) ⩽0.76 on 27 March 1997. The amount of PAN lost by thermal decomposition (TPAN) was comparable in magnitude to that present in ambient air. The ratios TPAN/(PAN+TPAN) were up to 0.53, 0.67 and 0.64 during the warm afternoons of 25, 26 and 27 March 1997, respectively. The highest calculated value of TPAN was 5.6 ppb on 27 March 1997. On that day the 24 h-averaged value of TPAN (1.01 ppb) was nearly the same as that of PAN (1.09 ppb). Using computer kinetic modeling (SAPRC 97 chemical mechanism) and sensitivity analysis of VOC incremental reactivity, we ranked VOC present in Porto Alegre ambient air for their importance as precursors to PAN and to PPN. Using as input data the averages of VOC concentrations measured in downtown Porto Alegre during the ca. 1 yr period March 1996–April 1997, we calculated that the most important precursors to PAN and PPN were the SAPRC 97 model species ARO2 (which includes the aromatics xylenes, trimethylbenzenes, ethyltoluenes, etc.), which accounted for ca. 17% of the total PAN and total PPN formation potentials. Overall, the results indicate a major role for aromatics and alkenes and a minor role for acetaldehyde and ethanol as precursors to peroxyacyl nitrates in the Porto Alegre urban area.     

Quantification of nitrate leaching from German forest ecosystems by use of a process oriented biogeochemical model

Simulations with the process oriented Forest-DNDC model showed reasonable to good agreement with observations of soil water contents of different soil layers, annual amounts of seepage water and approximated rates of nitrate leaching at 79 sites across Germany. Following site evaluation, Forest-DNDC was coupled to a GIS to assess nitrate leaching from German forest ecosystems for the year 2000. At national scale leaching rates varied in a range of 0–>80 kg NO₃–N ha⁻¹ yr⁻¹ (mean 5.5 kg NO₃–N ha⁻¹ yr⁻¹). A comparison of regional simulations with the results of a nitrate inventory study for Bavaria showed that measured and simulated percentages for different nitrate leaching classes (0–5 kg N ha⁻¹ yr⁻¹:66% vs. 74%, 5–15 kg N ha⁻¹ yr⁻¹:20% vs. 20%, >15 kg N ha⁻¹ yr⁻¹:14% vs. 6%) were in good agreement. Mean nitrate concentrations in seepage water ranged between 0 and 23 mg NO₃–N l⁻¹.