Effects of reactive hydrocarbons on ozone formation in southern Taiwan

Ambient air samples were collected at 13 air quality monitoring stations in Kaohsiung city, Kaohsiung county, and Pingtung county (KKP) to investigate the composition and spatial distribution of C₂–C₁₀ non-methane hydrocarbons (NMHCs) in southern Taiwan. Ozone formation potentials (OFPs) of NMHCs were estimated using maximum incremental reactivity (MIR) and k_OH method (reactivity of NMHC with OH radical) to assess the relative effects of hydrocarbons on ozone formation. The measurements showed that mixing ratios of toluene, ethene, ethyne, ethane, isopantane and propane were the highest among all measured species at most of the sampling sites. Nevertheless, considering both the photochemical reactivities and mixing ratios of all the measured species, toluene, xylene, ethene and propene were calculated to have the highest OFPs and reactivities. The OFPs and reactivities assessed by the MIR and k_OH methods for the four compounds accounted for 54.5% and 39.3% of all the measured species. Larger benefit margin of ozone abatement may be obtained by reducing emissions of a group of key species with high OFPs.2,2-dimethylbutane (22DMC4) was used as an indicator of traffic emissions to distinguish traffic from non-traffic contributions of key species in Kaohsiung metropolitan area. It revealed that the contribution of non-traffic source was significant for toluene, whereas xylene was found to be primarily from the traffic source in Kaohsiung metropolitan area during the sampling periods.     

Characteristics and diurnal variations of NMHCs at urban,suburban, and rural sites in the Pearl River Delta and a remote site in South China

The Pearl River Delta (PRD) is one of the most industrialized and urbanized regions in China. With rapid growth of the economy, it is suffering from deteriorating air quality. Non-methane hydrocarbons (NMHCs) were investigated at urban and suburban sites in Guangzhou (GZ), a rural site in PRD and a clean remote site in South China, in April 2005. Additional roadside samples in GZ and Qingxi (QX, a small industrial town in PRD), ambient air samples at the rooftop of a printing factory in QX and exhaust samples from liquefied petroleum gas (LPG)—fueled taxis in GZ were collected to help identify the source signatures of NMHCs. A large fraction of propane (47%) was found in exhaust samples from LPG-fueled taxis in GZ and extremely high levels of toluene (2.0–3.1 ppmv) were found at the rooftop of the printing factory in QX. Vehicular and industrial emissions were the main sources of NMHCs. The effect of vehicular emission on the ambient air varied among the three PRD sites. The impact of industrial emissions was widespread and they contributed greatly to the high levels of aromatic hydrocarbons, especially toluene, at the three PRD sites investigated. Leakage from vehicles fueled by LPG contributed mainly to the high levels of propane and n-butane at the urban GZ site. Ethane and ethyne from long-range transport and isoprene from local biogenic emission were the main contributors to the total hydrocarbons at the remote site. Diurnal variations of NMHCs showed that the contribution from vehicular emissions varied with traffic conditions and were more influenced by fresh emissions at the urban site and by aged air at the suburban and rural sites. Isoprene from biogenic emission contributed largely to the ozone formation potential (OFP) at the remote site. Ethene, toluene and m/p-xylene were the main contributors to the OFP at the three PRD sites.     

Diurnal and seasonal cycles of ozone precursors observed from continuous measurement at an urban site in Taiwan

Hourly measurement of 56 ozone precursors was conducted by a monitoring station located in a metropolitan area in central Taiwan. After nearly a year of continuous operation at this urban site, both diurnal and seasonal cycles of nonmethane hydrocarbons (NMHCs) were clearly observed, which was caused by the interplay between source, chemical loss, and meteorology. Selected species representing three different types of major sources namely the household fuel leakage, vehicular exhaust and gasoline evaporation, as well as biogenic emissions exhibit dramatic diurnal or seasonal cycles with each displaying its own unique characteristics.Ethane and propane, largely originated from leakage of natural gas or liquefied petroleum gases (LPG), showed concentrations elevating throughout the night and early morning, but began to decrease towards noon as the nocturnal temperature inversion elevated. Because of the lower chemical reactivity and somewhat more constant emissions than other measured target compounds, their diurnal cycles were presumably the direct reflection of the mixing height over the metropolitan area.For compounds originating from vehicular plus evaporative emissions such as benzene, which accounts for most of the monitored compounds, their diurnal cycles were also largely controlled by the variation in the height of temperature inversion.Of all the 56 species monitored, isoprene, an abundant biogenic species largely released by plants, showed distinct diurnal and seasonal cycles different from the other measured NMHCs. Its concentration usually peaked at noon in summer and fall when temperature and solar radiation reached their maximum level, demonstrating the close relationship of isoprene with photosynthesis.Seasonal variation was also clearly observed for the other NMHCs quantified. With the exception of isoprene, most species show higher average concentration in winter and lower in summer with the fall values being the intermediate, which presumably is caused by both the seasonal variation in HO abundance and the height of the temperature inversion.     

Estimate of initial isoprene contribution to ozone formation potential in Beijing, China

Volatile organic compounds (VOCs) are important precursors of tropospheric ozone formation. Isoprene contributions to ozone formation by using ambient mixing ratios are generally underestimated because of rapid chemical losses. In this study, ambient mixing ratios of major VOC species were continuously measured at Peking university (PKU) and YUFA, urban and sub-urban sites in Beijing, the city that will host 2008 Olympic Games. The observed mixing ratios of methyl vinyl ketone (MVK), methacrolein (MACR) and isoprene were used to derive the mixing ratios of initial isoprene, which means the ambient isoprene level before it undergoes any photochemical reaction with OH radicals. The average mixing ratios of initial isoprene were 3.3±1.6 and 2.9±1.5 ppbv at PKU and YUFA sites, respectively. The percentages of initial isoprene in total initial VOCs were 10.8% at PKU site and 11.4% at YUFA site, in reasonable agreement with the isoprene contribution in total VOC emissions as derived from source inventories. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential (OFP) for major VOC species. The OFP for initial isoprene accounted for 23% of the total OFPs for all measured species, compared to 11% using ambient mixing ratios of isoprene at PKU site. Similarly, at YUFA site, the ambient measured isoprene and initial isoprene contributed 10% and 22%, respectively, to the OFPs for total measured VOCs. It seems that isoprene has similar contribution to ozone formation at both sites in Beijing city.     

Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong

Ambient air quality measurements of 156 species including 39 alkanes, 32 alkenes, 2 alkynes, 24 aromatic hydrocarbons, 43 halocarbons and 16 carbonyls, were carried out for 120 air samples collected at two sampling stations (CW and TW) in 2001 throughout Hong Kong. Spatial variations of volatile organic compounds (VOCs) in the atmosphere were investigated. Levels of most alkanes and alkenes at TW site were higher than that at the CW site, while the BTEX concentrations at the two sites were close. The BTEX ratios at CW and TW were 1.6:10.1:1.0:1.6 and 2.1:10.8:1.0:2.0, respectively. For major halogenated hydrocarbons, the mean concentrations of chloromethane, CFCs 12 and 22 did not show spatial variations at the two sites. However, site-specific differences were observed for trichloroethene and tetrachloroethene. Furthermore, there were no significant differences for carbonyls such as formaldehyde, acetaldehyde and acetone between the two sites. The levels of selected hydrocarbons in winter were 1-5 times that in summer. There were no common seasonal trends for carbonyls in Hong Kong. The ambient level of formaldehyde, the most abundant carbonyl, was higher in summer. However, levels of acetaldehyde, acetone and benzaldehyde in winter were 1.6-3.8 times that in summer. The levels of CFCs 11 and 12, and chloromethane in summer were higher than that in winter. Strong correlation of most hydrocarbons with propene and n-butane suggested that the primary contributors of hydrocarbons were vehicular emissions in Hong Kong. In addition, gasoline evaporation, use of solvents, leakage of liquefied petroleum gas (LPG), natural gas leakage and other industrial emissions, and even biogenic emissions affected the ambient levels of hydrocarbons. The sources of halocarbons were mainly materials used in industrial processes and as solvents. Correlation analysis suggested that photochemical reactions made significant contributions to the ambient levels of carbonyls in summer whereas in winter motor vehicle emissions would be the major sources of the carbonyls. The photochemical reactivity of selected VOCs was estimated in this study. The largest contributors to ozone formation were formaldehyde, toluene, propene, m,p-xylene, acetaldehyde, 1-butene/i-butene, isoprene and n-butane, suggesting that motor vehicles, gasoline evaporation, use of solvents, leakage of LPG, photochemical processes and biogenic emission are sources in the production of ozone. On the other hand, VOCs from vehicles and gasoline evaporation were predominant with respect to reactions with OH radical.     

Source apportionment of ambient non-methane hydrocarbons in Hong Kong: application of a principal component analysis/absolute principal component scores (PCA/APCS) receptor model

Receptor-oriented source apportionment models are often used to identify sources of ambient air pollutants and to estimate source contributions to air pollutant concentrations. In this study, a PCA/APCS model was applied to the data on non-methane hydrocarbons (NMHCs) measured from January to December 2001 at two sampling sites: Tsuen Wan (TW) and Central & Western (CW) Toxic Air Pollutants Monitoring Stations in Hong Kong. This multivariate method enables the identification of major air pollution sources along with the quantitative apportionment of each source to pollutant species. The PCA analysis identified four major pollution sources at TW site and five major sources at CW site. The extracted pollution sources included vehicular internal engine combustion with unburned fuel emissions, use of solvent particularly paints, liquefied petroleum gas (LPG) or natural gas leakage, and industrial, commercial and domestic sources such as solvents, decoration, fuel combustion, chemical factories and power plants. The results of APCS receptor model indicated that 39% and 48% of the total NMHCs mass concentrations measured at CW and TW were originated from vehicle emissions, respectively. 32% and 36.4% of the total NMHCs were emitted from the use of solvent and 11% and 19.4% were apportioned to the LPG or natural gas leakage, respectively. 5.2% and 9% of the total NMHCs mass concentrations were attributed to other industrial, commercial and domestic sources, respectively. It was also found that vehicle emissions and LPG or natural gas leakage were the main sources of C(3)-C(5) alkanes and C(3)-C(5) alkenes while aromatics were predominantly released from paints. Comparison of source contributions to ambient NMHCs at the two sites indicated that the contribution of LPG or natural gas at CW site was almost twice that at TW site. High correlation coefficients (R(2) > 0.8) between the measured and predicted values suggested that the PCA/APCS model was applicable for estimation of sources of NMHCs in ambient air.     

Revealing source signatures in ambient BTEX concentrations

Management of ambient concentrations of Volatile Organic Compounds (VOCs) is essential for maintaining low ozone levels in urban areas where its formation is under a VOC-limited regime. The significant decrease in traffic-induced VOC emissions in many developed countries resulted in relatively comparable shares of traffic and non-traffic VOC emissions in urban airsheds. A key step for urban air quality management is allocating ambient VOC concentrations to their pertinent sources. This study presents an approach that can aid in identifying sources that contribute to observed BTEX concentrations in areas characterized by low BTEX concentrations, where traditional source apportionment techniques are not useful. Analysis of seasonal and diurnal variations of ambient BTEX concentrations from two monitoring stations located in distinct areas reveal the possibility to identify source categories. Specifically, the varying oxidation rates of airborne BTEX compounds are used to allocate contributions of traffic emissions and evaporative sources to observed BTEX concentrations.     

C2–C10 nonmethane hydrocarbons measured in Dallas,USA—Seasonal trends and diurnal characteristics

Nonmethane hydrocarbons (NMHCs) are important precursors of ozone and other photo oxidants. We presented continuous hourly average concentrations of 45 C₂–C₁₀ NMHCs measured in urban area of Dallas, USA from 1996 to 2004. Most of the selected compounds are good variables with less noise. The top 10 species with high ozone-generating potential were identified according to their concentrations and reactivities. The ambient concentrations of abundant anthropogenic emission hydrocarbons measured in Dallas were about 2–4 times of the background values measured in the remote areas with adjacent latitude. The time series for anthropogenic emission hydrocarbons showed an obvious seasonal cycle with relatively high concentration in winter and low concentration in summer. The sinusoidal function with a linearly decreasing factor could well fit the time series of NMHCs. The phase of seasonal cycle for the aromatic hydrocarbons of toluene, m/p xylene and o-xylene that might come from both vehicle emission and solvent utilities evaporation was about 1 month earlier than that for alkanes and alkenes that mainly came from vehicle emission. Ambient NMHCs in Dallas decreased with a stable rate during 1996–2004. For most of compounds with high ozone-generating potential, the rate of ambient concentration decrease was higher or much higher than the rate of volatile organic compounds (VOCs) source emission reduction estimated by EPA's National Emission Inventory. On weekdays, the morning hydrocarbon concentration peak was coincident with morning traffic rush time in Dallas. Another concentration peak was delayed to afternoon traffic rush time. The characteristics of VOCs sources, photochemical removal processes and atmospheric dilution could be interpreted by the diurnal variations of benzene/ethylbenzene (B/E), toluene/ethylbenzene (T/E) and xylene/ethylbenzene (X/E). The ratio of VOC/NO_x measured in Dallas was substantially smaller than that calculated for USA cities. Ozone formation in Dallas was VOC sensitive.     

Pollution characteristics of ambient volatile organic compounds (VOCs) in the southeast coastal cities of China

With the rapid urbanization, the southeast coastal cities of China are facing increasing air pollution in the past decades. Large emissions of VOCs from vehicles and petrochemical factories have contributed greatly to the local air quality deterioration. Investigating the pollution characteristics of VOCs is of great significance to the environmental risk assessment and air quality improvement. Ambient VOC samples were collected simultaneously from nine coastal cities of southeast China using the Tedlar bags, and were subsequently preprocessed and analyzed using a cryogenic preconcentrator and a gas chromatography–mass spectrometry system, respectively. VOC compositions, spatial distributions, seasonal variations and ozone formation potentials (OPFs) were discussed. Results showed that methylene chloride, toluene, isopropyl alcohol and n-hexane were most abundant species, and oxygenated compounds, aromatics and halogenated hydrocarbons were most abundant chemical classes (62.5–95.6 % of TVOCs). Both industrial and vehicular exhausts might contribute greatly to the VOC emissions. The VOC levels in the southeast coastal cities of China were sufficiently high (e.g., 6.5 μg?m^?3 for benzene) to pose a health risk to local people. A more serious pollution state was found in the southern cities of the study region, while higher VOC levels were usually observed in winter. The B/T ratio (0.26?±?0.09) was lower than the typical ratio (ca. 0.6) for roadside samples, while the B/E (1.6–7.6) and T/E (7.2–26.8) ratios were higher than other cities around the world, which indicated a unique emission profile in the study region. Besides, analysis on ozone formation potentials (OFPs) indicated that toluene was the most important species in ozone production with the accountabilities for total OFPs of 22.6 to 59.6 %.     

Contribution of isoprene to formaldehyde and ozone formation based on its oxidation products measurement in Beijing,China

The atmospheric mixing ratios of methacrolein (MACR) and methyl vinyl ketone (MVK), the two specific products from isoprene oxidation in the atmosphere, were measured in Beijing from March to November, 2006. Distinct amounts of MACR and MVK were detected during vegetable growing seasons from April to October with ambient levels of 0.11–0.67 ppbv and 0.19–1.36 ppbv, respectively. The reacted isoprene and its ozone formation potentials (OFPs) in Beijing were evaluated in the range of 0.49–3.46 ppbv and 6.4–44.7 ppbv, respectively, from April to October. OFP of the reacted isoprene accounted for 10.6–23.6% of the total OFPs of VOCs (including carbonyls and isoprene) and 6.38–29.9% of the photo-chemically produced ozone. The maximum OFP of the original emitted isoprene prior to its photo-oxidation was calculated as 56.0 ppbv in August. The contribution from the reacted isoprene in Beijing to HCHO formation was also estimated to be in the range of 0.35–2.45 ppbv from April to October, which accounted for 4.6–11.5% of ambient HCHO.     

Sources of ambient volatile organic compounds and their contributions to photochemical ozone formation at a site in the Pearl River Delta, southern China

The Positive Matrix Factorization (PMF) receptor model and the Observation Based Model (OBM) were combined to analyze volatile organic compound (VOC) data collected at a suburban site (WQS) in the PRD region. The purposes are to estimate the VOC source apportionment and investigate the contributions of these sources and species of these sources to the O₃ formation in PRD. Ten VOC sources were identified. We further applied the PMF-extracted concentrations of these 10 sources into the OBM and found "solvent usage 1", "diesel vehicular emissions" and "biomass/biofuel burning" contributed most to the O₃ formation at WQS. Among these three sources, higher Relative Incremental Reactivity (RIR)-weighted values of ethene, toluene and m/p-xylene indicated that they were mainly responsible for local O₃ formation in the region. Sensitivity analysis revealed that the sources of "diesel vehicular emissions", "biomass/biofuel burning" and "solvent usage 1" had low uncertainties whereas "gasoline evaporation" showed the highest uncertainty.     

A combined approach for the evaluation of a volatile organic compound emissions inventory

Emissions inventories significantly affect photochemical air quality model performance and the development of effective control strategies. However, there have been very few studies to evaluate their accuracy. Here, to evaluate a volatile organic compound (VOC) emissions inventory, we implemented a combined approach: comparing the ratios of carbon bond (CB)-IV VOC groups to nitrogen oxides (NOx) or carbon monoxide (CO) using an emission preprocessing model, comparing the ratios of VOC source contributions from a source apportionment technique to NOx or CO, and comparing ratios of CB-IV VOC groups to NOx or CO and the absolute concentrations of CB-IV VOC groups using an air quality model, with the corresponding ratios and concentrations observed at three sites (Maryland, Washington, DC, and New Jersey). The comparisons of the ethene/NOx ratio, the xylene group (XYL)/NOx ratio, and ethene and XYL concentrations between estimates and measurements showed some differences, depending on the comparison approach, at the Maryland and Washington, DC sites. On the other hand, consistent results at the New Jersey site were observed, implying a possible overestimation of vehicle exhaust. However, in the case of the toluene group (TOL), which is emitted mainly from surface coating and printing sources in the solvent utilization category, the ratios of TOL/ NOx or CO, as well as the absolute concentrations revealed an overestimate of these solvent sources by a factor of 1.5 to 3 at all three sites. In addition, the overestimate of these solvent sources agreed with the comparisons of surface coating and printing source contributions relative to NOx from a source apportionment technique to the corresponding value of estimates at the Maryland site. Other studies have also suggested an overestimate of solvent sources, implying a possibility of inaccurate emission factors in estimating VOC emissions from surface coating and printing sources. We tested the impact of these overestimates with a chemical transport model and found little change in ozone but substantial changes in calculated secondary organic aerosol concentrations.     

A land use database and examples of biogenic isoprene emission estimates for the state of Texas, USA

Using data from a variety of sources, land use and vegetation in Texas were mapped with a spatial resolution of approximately 1 km. Over 600 classifications were used to characterize the land use and land cover throughout the state and field surveys were performed to assign leaf biomass densities, by species, to the land cover classifications. The total leaf biomass densities associated with these land use classifications ranged from 0 to 556 g/m², with the highest assigned total and oak leaf biomass densities located in central and eastern Texas. The land cover data were used as input to a biogenic emissions model, GLOBEIS2. Estimates of biogenic emissions of isoprene based on GLOBEIS2 and the new land cover data showed significant differences when compared to biogenic isoprene emissions estimated using previous land cover data and emission estimation procedures. For example, for one typical domain in eastern Texas, total daily isoprene emissions increased by 38% with the new modeling tools. These results may ultimately affect the way in which ozone and other photochemical pollutants are modeled and evaluated in the state of Texas.     

Application of OMI observations to a space-based indicator of NOx and VOC controls on surface ozone formation

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NO_x) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the “Ratio”) from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios <1 and NO_x at Ratios >2; both NO_x and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria, the OMI data indicate that ozone formation became: 1. more sensitive to NO_x over most of the United States from 2005 to 2007 because of the substantial decrease in NO_x emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO₂, and 2. more sensitive to NO_x with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g., Chicago), the data clearly indicate that ozone formation became more sensitive to NO_x from 2005 to 2007. In cities with relatively high isoprene emissions (e.g., Atlanta), we found that the increase in the Ratio due to decreasing NO_x emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.     

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.     

Comparison of regional and global land cover products and the implications for biogenic emission modeling

Accurate estimates of biogenic emissions are required for air quality models that support the development of air quality management plans and attainment demonstrations. Land cover characterization is an essential driving input for most biogenic emissions models. This work contrasted the global Moderate Resolution Imaging Spectroradiometer (MODIS) land cover product against a regional land cover product developed for the Texas Commissions on Environmental Quality (TCEQ) over four climate regions in eastern Texas, where biogenic emissions comprise a large fraction of the total inventory of volatile organic compounds (VOCs) and land cover is highly diverse. The Model of Emissions of Gases and Aerosols from Nature (MEGAN) was utilized to investigate the influences of land cover characterization on modeled isoprene and monoterpene emissions through changes in the standard emission potential and emission activity factor, both separately and simultaneously. In Central Texas, forest coverage was significantly lower in the MODIS land cover product relative to the TCEQ data, which resulted in substantially lower estimates of isoprene and monoterpene emissions by as much as 90%. Differences in predicted isoprene and monoterpene emissions associated with variability in land cover characterization were primarily caused by differences in the standard emission potential, which is dependent on plant functional type. Photochemical modeling was conducted to investigate the effects of differences in estimated biogenic emissions associated with land cover characterization on predicted ozone concentrations using the Comprehensive Air Quality Model with Extensions (CAMx). Mean differences in maximum daily average 8-hour (MDA8) ozone concentrations were 2 to 6 ppb with maximum differences exceeding 20 ppb. Continued focus should be on reducing uncertainties in the representation of land cover through field validation.

Implications: Uncertainties in the estimation of biogenic emissions associated with the characterization of land cover in global and regional data products were examined in eastern Texas. Misclassification between trees and low-growing vegetation in central Texas resulted in substantial differences in isoprene and monoterpene emission estimates and predicted ground-level ozone concentrations. Results from this study indicate the importance of land cover validation at regional scales.     

Impact of biogenic emission uncertainties on the simulated response of ozone and fine particulate matter to anthropogenic emission reductions

The role of emissions of volatile organic compounds and nitric oxide from biogenic sources is becoming increasingly important in regulatory air quality modeling as levels of anthropogenic emissions continue to decrease and stricter health-based air quality standards are being adopted. However, considerable uncertainties still exist in the current estimation methodologies for biogenic emissions. The impact of these uncertainties on ozone and fine particulate matter (PM2.5) levels for the eastern United States was studied, focusing on biogenic emissions estimates from two commonly used biogenic emission models, the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the Biogenic Emissions Inventory System (BEIS). Photochemical grid modeling simulations were performed for two scenarios: one reflecting present day conditions and the other reflecting a hypothetical future year with reductions in emissions of anthropogenic oxides of nitrogen (NOx). For ozone, the use of MEGAN emissions resulted in a higher ozone response to hypothetical anthropogenic NOx emission reductions compared with BEIS. Applying the current U.S. Environmental Protection Agency guidance on regulatory air quality modeling in conjunction with typical maximum ozone concentrations, the differences in estimated future year ozone design values (DVF) stemming from differences in biogenic emissions estimates were on the order of 4 parts per billion (ppb), corresponding to approximately 5% of the daily maximum 8-hr ozone National Ambient Air Quality Standard (NAAQS) of 75 ppb. For PM2.5, the differences were 0.1-0.25 microg/m3 in the summer total organic mass component of DVFs, corresponding to approximately 1-2% of the value of the annual PM2.5 NAAQS of 15 microg/m3. Spatial variations in the ozone and PM2.5 differences also reveal that the impacts of different biogenic emission estimates on ozone and PM2.5 levels are dependent on ambient levels of anthropogenic emissions.     

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.