Measurement and analysis of atmospheric concentrations of isoprene and its reaction products in central Texas

A field experiment was conducted in August 1998 to investigate the concentrations of isoprene and isoprene reaction products in the surface and mixed layers of the atmosphere in Central Texas. Measured near ground-level concentrations of isoprene ranged from 0.3 (lower limit of detection – LLD) to 10.2 ppbv in rural regions and from 0.3 to 6.0 ppbv in the Austin urban area. Rural ambient formaldehyde levels ranged from 0.4 ppbv (LLD) to 20.0 ppbv for 160 rural samples collected, while the observed range was smaller at Austin (0.4–3.4 ppbv) for a smaller set of samples (37 urban samples collected). Methacrolein levels did not vary as widely, with rural measurements from 0.1 ppbv (LLD) to 3.7 ppbv and urban concentrations varying between 0.2 and 5.7 ppbv. Isoprene flux measurements, calculated using a simple box model and measured mixed-layer isoprene concentrations, were in reasonable agreement with emission estimates based on local ground cover data. Ozone formation attributable to biogenic hydrocarbon oxidation was also calculated. The calculations indicated that if the ozone formation occurred at low VOC/NO_x ratios, up to 20 ppbv of ozone formed could be attributable to biogenic photooxidation. In contrast, if the biogenic hydrocarbon reaction products were formed under low NO_x conditions, ozone production attributable to biogenics oxidation would be as low as 1 ppbv. This variability in ozone formation potentials implies that biogenic emissions in rural areas will not lead to peak ozone levels in the absence of transport of NO_x from urban centers or large rural NO_x sources.     

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.     

A review of surface ozone in the polar regions

Surface ozone records from ten polar research stations were investigated for the dependencies of ozone on radiative processes, snow-photochemisty, and synoptic and stratospheric transport. A total of 146 annual data records for the Arctic sites Barrow, Alaska; Summit, Greenland; Alert, Canada; Zeppelinfjellet, Norway; and the Antarctic stations Halley, McMurdo, Neumayer, Sanae, Syowa, and South Pole were analyzed. Mean ozone at the Northern Hemisphere (NH) stations (excluding Summit) is ∼5 ppbv higher than in Antarctica. Statistical analysis yielded best estimates for the projected year 2005 median annual ozone mixing ratios, which for the Arctic stations were 33.5 ppbv at Alert, 28.6 ppbv at Barrow, 46.3 ppbv ppb at Summit and 33.7 ppbv at Zeppelinfjellet. For the Antarctic stations the corresponding ozone mixing ratios were 21.6 ppbv at Halley, 27.0 ppbv at McMurdo, 24.9 ppbv at Neumayer, 27.2 ppbv at Sanae, 29.4 ppbv at South Pole, and 25.8 ppbv at Syowa. At both Summit (3212 m asl) and South Pole (2830 m asl), annual mean ozone is higher than at the lower elevation and coastal stations. A trend analysis revealed that all sites in recent years have experienced low to moderate increases in surface ozone ranging from 0.02 to 0.26 ppbv yr⁻¹, albeit none of these changes were found to be statistically significant trends. A seasonal trend analysis showed above-average increases in ozone during the spring and early summer periods for both Arctic (Alert, Zeppelinfjellet) and Antarctic (McMurdo, Neumayer, South Pole) sites. In contrast, at Barrow, springtime ozone has been declining. All coastal stations experience springtime episodes with rapid depletion of ozone in the boundary layer, attributable to photochemically catalyzed ozone depletion from halogen chemistry. This effect is most obvious at Barrow, followed by Alert. Springtime depletion episodes are less pronounced at Antarctic stations. At South Pole, during the Antarctic spring and summer, photochemical ozone production yields frequent episodes with enhanced surface ozone. Other Antarctic stations show similar, though less frequent spring and summertime periods with enhanced ozone. The Antarctic data provide evidence that austral spring and summertime ozone production in Antarctica is widespread, respectively, affects all stations at least through transport events. This ozone production contributes to a several ppbv enhancement in the annual mean ozone over the Antarctic plateau; however, it is not the determining process in the Antarctic seasonal ozone cycle. Although Summit and South Pole have many similarities in their environmental conditions, this ozone production does not appear to be of equal importance at Summit. Amplitudes of diurnal, summertime ozone cycles at these polar sites are weaker than at lower latitude locations. Amplitudes of seasonal ozone changes are larger in the Southern Hemisphere (by ∼5 ppbv), most likely due to less summertime photochemical ozone loss and more transport of ozone-rich air to the Arctic during the NH spring and summer months.     

Increase in springtime tropospheric ozone at a mountainous site in Japan for the period 1998–2006

The trend of tropospheric ozone from 1998 to 2006 was examined based on continuous measurements made at a site on Mt. Happo, Japan. We focused our study on springtime ozone, to coincide with the East Asian continental outflow that dominates the lower tropospheric ozone over Japan during this season. The observed increase of ～1 ppbv yr^?1 in the mean ozone level was statistically significant. We also found that the probability distribution of the springtime ozone mixing ratios was substantially modified, with the ozone mixing ratios greatly increasing at the upper end of the probability distribution. This increase has been particularly large since 2003, with larger increases occurring at the higher percentiles. The number of high-ozone days doubled during 2003–2006 compared to 1999–2002. One of the very likely explanations is the enhancement of regional ozone pollution due to rapidly increasing anthropogenic emissions from East Asia.     

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.     

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.     

Effect of climate change on air quality

Air quality is strongly dependent on weather and is therefore sensitive to climate change. Recent studies have provided estimates of this climate effect through correlations of air quality with meteorological variables, perturbation analyses in chemical transport models (CTMs), and CTM simulations driven by general circulation model (GCM) simulations of 21st-century climate change. We review these different approaches and their results. The future climate is expected to be more stagnant, due to a weaker global circulation and a decreasing frequency of mid-latitude cyclones. The observed correlation between surface ozone and temperature in polluted regions points to a detrimental effect of warming. Coupled GCM–CTM studies find that climate change alone will increase summertime surface ozone in polluted regions by 1–10 ppb over the coming decades, with the largest effects in urban areas and during pollution episodes. This climate penalty means that stronger emission controls will be needed to meet a given air quality standard. Higher water vapor in the future climate is expected to decrease the ozone background, so that pollution and background ozone have opposite sensitivities to climate change. The effect of climate change on particulate matter (PM) is more complicated and uncertain than for ozone. Precipitation frequency and mixing depth are important driving factors but projections for these variables are often unreliable. GCM–CTM studies find that climate change will affect PM concentrations in polluted environments by ±0.1–1 μg m^?3 over the coming decades. Wildfires fueled by climate change could become an increasingly important PM source. Major issues that should be addressed in future research include the ability of GCMs to simulate regional air pollution meteorology and its sensitivity to climate change, the response of natural emissions to climate change, and the atmospheric chemistry of isoprene. Research needs to be undertaken on the effect of climate change on mercury, particularly in view of the potential for a large increase in mercury soil emissions driven by increased respiration in boreal ecosystems.     

On springtime high ozone events in the lower troposphere from Southeast Asian biomass burning

Ozone peaks with mixing ratios as high as 138 ppbv were observed in the lower troposphere (2.5–4.5 km) over Hong Kong in spring. Simultaneously observed high humidity suggests that this enhanced ozone was not the result of transport from the upper troposphere. Back trajectory analysis suggests that these enhancements resulted from lateral transport. Air masses arriving at the altitude of the ozone peaks appear to have passed over continental Southeast Asia where the bulk of biomass burning occurs at this time of the year (February–April). We hypothesize that biomass burning in this region provided the necessary precursors for the observed ozone enhancement. As far as we know this is the first observation of highly enhanced ozone layers associated with biomass burning in continental Southeast Asia.     

Hydrocarbon emissions from industrial release events in the Houston-Galveston area and their impact on ozone formation

Ambient measurements have shown that ozone formation in the Houston-Galveston area of Texas is frequently much more rapid than in other urban areas. One of the contributing factors is believed to be short-term episodic or “event” emissions from industrial facilities, particularly releases that contain significant mass fractions of highly reactive volatile organic compounds (HRVOCs). In this work, time series analyses are used to compare average annual flow rates for air pollutant emissions with those released during reported emission events. The results indicate that the magnitude and frequency of HRVOC event emissions are an important element in accurately reflecting ozone precursor emission patterns in the Houston-Galveston area, particularly in Harris, Brazoria, Galveston, and Chambers counties. More than 50% of the reported episodic (event) emissions of HRVOCs are ethene and approximately a third are propene; the remainders are isomers of butene and 1,3-butadiene. Most events last less than 24 h. The mass released in an event can vary from a few hundred to more than 100,000 lb, and the dominant type of industrial source is chemical manufacturers (SIC 2869). Daily emissions from a single facility can vary from annual average emissions by multiple orders of magnitude at a frequency of several times a year. Because there are so many facilities in the Houston-Galveston area, HRVOC emission variability of this magnitude can be expected daily, at some time and some location in the Houston-Galveston area. If the emission variability occurs at times and locations where atmospheric conditions are conducive to ozone formation, both ambient data and photochemical modeling indicate that industrial emission events can lead to elevated concentrations of ozone. Specifically, peak, area-wide ozone concentration can be increased by as much as 100 ppb for large HRVOC emission events.     

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.     

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.     

Aromatic hydrocarbons at urban,sub-urban,rural (8°52′N; 67°19′W) and remote sites in Venezuela

Using the novel on-line proton transfer reaction mass spectrometry (PTR-MS) technique, atmospheric concentrations of benzene, toluene, xylenes, and C₉-benzenes were measured in Caracas (urban), Altos de Pipe (sub-urban), Calabozo (rural) and Parupa (remote), during various campaigns in 1999 and 2000.Average daytime mixing ratios measured in Caracas are 1.1, 3.2, 3.7, and 2.7 nmol/mol for benzene, toluene, xylenes, and C₉-benzenes. At the sub-urban site, located only few km from Caracas, relatively low levels (∼20% of the levels measured in Caracas) of these aromatic hydrocarbons were observed.At the rural site during the dry season, higher concentrations of benzene (0.15 nmol/mol) were recorded, whereas those of toluene (0.08 nmol/mol) were lower during that time. The aromatic hydrocarbon ratios in the wet season (benzene: 0.08 nmol/mol; toluene: 0.09 nmol/mol) are consistent with an aged urban plume, whereas biomass burning emissions dominate during the dry season. From rural and urban [benzene]/[toluene] ratios a mean HO concentration of 2.6×10⁶ molecules/cm³ was estimated during the wet season. This value must be considered an overestimate because it does not account for background concentrations which are likely for benzene and toluene.At the remote “La Gran Sabana” region (Parupa) very low mixing ratios (0.031 and 0.015 nmol/mol for benzene and toluene) are showing the pristine region to be unaffected by local sources. From the [benzene]/[toluene] ratio we deduced, that “urban” air arriving from the coastline (350 km) is likely mixed with air containing some background of benzene and toluene.Urban emissions (automobiles) should be the major source of aromatic compounds, however, during the dry season biomass burning seems to make an important contribution.     

Ozone production from Grenoble city during the August 2003 heat wave

The heat wave from 1 to 16 August 2003 is considered in the city of Grenoble (French Alps). The modelling system (PREVALP) is based on several models operating on nested domains: MM5 for dynamics, CHIMERE for chemistry (18 km and 6 km grid size) and METPHOMOD for both dynamics and chemistry (2 km grid size). The analysis of the results shows that during the heat wave, the mixing layer is thicker, up to 3500 m agl, hence inducing transport of ozone to high altitude. Two regimes were diagnosed: (1) a freely developing convective layer, (2) a layer trapped under south wind which makes ozone precursors accumulate in the city. Local ozone production is estimated to be 40% of the plume maximum in case (2) and only 30% in case (1). Sensitivity analysis by step increase for temperature at the boundary of the inner domain shows the non-linearity of the response; in this case most of the effect comes from chemistry. By changing biogenic emission significant changes are observed in restricted areas.     

Pollution influences on atmospheric composition and chemistry at high northern latitudes: Boreal and California forest fire emissions

We analyze detailed atmospheric gas/aerosol composition data acquired during the 2008 NASA ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) airborne campaign performed at high northern latitudes in spring (ARCTAS-A) and summer (ARCTAS-B) and in California in summer (ARCTAS-CARB). Biomass burning influences were widespread throughout the ARCTAS campaign. MODIS data from 2000 to 2009 indicated that 2008 had the second largest fire counts over Siberia and a more normal Canadian boreal forest fire season. Near surface arctic air in spring contained strong anthropogenic signatures indicated by high sulfate. In both spring and summer most of the pollution plumes transported to the Arctic region were from Europe and Asia and were present in the mid to upper troposphere and contained a mix of forest fire and urban influences. The gas/aerosol composition of the high latitude troposphere was strongly perturbed at all altitudes in both spring and summer. The reactive nitrogen budget was balanced with PAN as the dominant component. Mean ozone concentrations in the high latitude troposphere were only minimally perturbed (<5 ppb), although many individual pollution plumes sampled in the mid to upper troposphere, and mixed with urban influences, contained elevated ozone (ΔO₃/ΔCO = 0.11 ± 0.09 v/v). Emission and optical characteristics of boreal and California wild fires were quantified and found to be broadly comparable. Greenhouse gas emission estimates derived from ARCTAS-CARB data for the South Coast Air Basin of California show good agreement with state inventories for CO₂ and N₂O but indicate substantially larger emissions of CH₄. Simulations by multiple models of transport and chemistry were found to be broadly consistent with observations with a tendency towards under prediction at high latitudes.     

Methanol measurements in the lower troposphere near Innsbruck (047°16′N; 011°24′E), Austria

Diurnal variations on a time scale of minutes of the mixing ratios of methanol were measured using proton transfer reaction mass spectrometry (PTR-MS) technique during 67 days throughout the time span from November 1996 to July 1998 together with benzene and other volatile organic compounds at the western outskirts of Innsbruck, Austria. Comparison with the course of the mixing ratio of benzene, which served as marker for traffic emissions, as well as the observation of a seasonal variation allowed to distinguish between different sources for methanol release into the troposphere. Strong evidence for methanol removal via deposition on dew-wetted surfaces is obtained from the comparison of meteorological data with methanol mixing ratios. The mean volume mixing ratio of total methanol was 7.5 nmol mol⁻¹. Mixing ratios ranged from 0.03 up to 45 nmol mol⁻¹.     

Reactions between ozone and building products: Impact on primary and secondary emissions

Reactions of ozone on common building products were studied in a dedicated emission test chamber system. Fourteen new and unused products were exposed to 100–160 ppb of ozone at 23 °C and 50% RH during 48 h experiments. Ozone deposition velocities calculated at steady state were between 0.003 cm s⁻¹ (alkyd paint on polyester film) and 0.108 cm s⁻¹ (pine wood board). All tested product showed modified emissions when exposed to ozone and secondary emissions of several aldehydes were identified. Carpets and wall coverings emitted mainly C₅–C₁₀ n-aldehydes, typical by-products of surface reactions. Linoleum, polystyrene tiles and pine wood boards also showed increased emissions of formaldehyde, benzaldehyde and hexanal associated with reduced emissions of unsaturated compounds suggesting the occurrence of gas-phase reactions. The ozone removal on the different tested products was primarily associated with surface reactions. The relative contribution of gas-phase reactions to the total ozone removal was estimated to be between 5% and 30% for pine wood boards depending on relative humidity (RH) and on the incoming ozone concentration and 2% for polystyrene tiles. On pine wood board, decreasing ozone deposition velocities were measured with increasing ozone concentrations and with RH increasing in the range 30–50%.     

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.     

Measurement of total site mercury emissions from a chlor-alkali plant using ultraviolet differential optical absorption spectroscopy and cell room roof-vent monitoring

This technical note describes a United States Environmental Protection Agency (U.S. EPA) measurement project to determine elemental mercury (Hg⁰) emissions from a mercury cell chlor-alkali (MCCA) facility in the southeastern U.S. during a 53-day monitoring campaign in the fall of 2006. The optical remote sensing (ORS) area source measurement method EPA OTM 10 was used to provide Hg⁰ flux data for the site. These results are reported and compared with cell room roof-vent monitoring data acquired by the facility for similar time periods. The 24-h extrapolated mercury emission rate estimates determined by the two monitoring approaches are shown to be similar with overall averages in the 400 g day^?1 range with maximum values around 1200 g day^?1. Results from the OTM 10 measurements, which include both cell room emissions and potential fugitive sources outside the cell room, are shown to be approximately 10% higher than cell room monitoring results indicating that fugitive emissions from outside the cell room produce a small but measurable effect for this site.     

Secondary organic aerosol importance in the future atmosphere

In order to investigate the secondary organic aerosol (SOA) response to changes in biogenic volatile organic compounds (VOC) emissions in the future atmosphere and how important will SOA be relative to the major anthropogenic aerosol component (sulfate), the global three-dimensional chemistry/transport model TM3 has been used. Emission estimates of biogenic VOC (BVOC) and anthropogenic gases and particles from the literature for the year 2100 have been adopted.According to our present-day model simulations, isoprene oxidation produces 4.6 Tg SOA yr⁻¹, that is less than half of the 12.2 Tg SOA yr⁻¹ formed by the oxidation of other BVOC. In the future, nitrate radicals and ozone become more important than nowadays, but remain minor oxidants for both isoprene and aromatics. SOA produced by isoprene is estimated to almost triple, whereas the production from other BVOC more than triples. The calculated future SOA burden change, from 0.8 Tg at present to 2.0 Tg in the future, is driven by changes in emissions, oxidant levels and pre-existing particles. The non-linearity in SOA formation and the involved chemical and physical feedbacks prohibit the quantitative attribution of the computed changes to the above-mentioned individual factors. In 2100, SOA burden is calculated to exceed that of sulfate, indicating that SOA might become more important than nowadays. These results critically depend on the biogenic emissions and thus are subject to the high uncertainty associated with these emissions estimated due to the insufficient knowledge on plant response to carbon dioxide changes. Nevertheless, they clearly indicate that the change in oxidants and primary aerosol caused by human activities can contribute as much as the change in BVOC emissions to the increase of the biogenic SOA production in the future atmosphere.     

Applications of satellite remote sensing data for estimating biogenic emissions in southeastern Texas

The sensitivity of biogenic emission estimates and air quality model predictions to the characterization of land use/land cover (LULC) in southeastern Texas was examined using the Global Biosphere Emissions and Interactions System (GloBEIS) and the Comprehensive Air Quality Model with extensions (CAMx). A LULC database was recently developed for the region based on source imagery collected by the Landsat 7 Enhanced Thematic Mapper-Plus sensor between 1999 and 2003, and field data for land cover classification, species identification and quantification of biomass densities.  Biogenic emissions estimated from the new LULC data set showed good general agreement in their spatial distribution, but were approximately 40% lower than emissions from the LULC data set currently used by the State of Texas, primarily because of differences in the biomass estimates of key species such as Quercus. Predicted ozone mixing ratios using the biogenic emissions produced from the new LULC data set were as much as 26 ppb lower in some areas on some days, depending on meteorological conditions. Satellite data and image classification techniques provide useful tools for mapping and monitoring changes in LULC. However, field validation is necessary to link species and biomass densities to the classification system used for accurate biogenic emissions estimates, especially in areas such as riparian corridors that contain dense spatial coverage of key species.