Source characterization of ozone precursors by complementary approaches of vehicular indicator and principal component analysis

Measurements of speciated non-methane hydrocarbons (NMHCs) were conducted in an ozone non-attainment metropolis with pronounced industrial emissions in addition to traffic ones. Highly variable and complex natures of industrial sources make their composition profiles difficult to determine. In the circumstances of no reliable source profiles, two simple complementary approaches were attempted to characterize sources of NMHCs. First, a robust vehicular indicator, 3-methylpentane (3MC5A), which is an intrinsic component of gasoline, was used to estimate contributions of traffic versus non-traffic sources for major NMHCs with high ozone-forming potentials (OFPs), such as ethene, toluene, xylene, isoprene, etc. Second, the method of principal component analysis (PCA) was employed to further discern non-traffic emissions into various source groups. A total of 454 ambient samples were sampled in the urban-industrial complex metropolis (Kaohsiung, Taiwan) to build up a large dataset to be tested by the two complementary approaches. It was found that four types of emissions, i.e., traffic, household fuel leakage, industrial, and biogenic, were responsible for the observed ambient NMHCs. The industrial contribution was significant for ethene and toluene (with 48–67% and 33–62%, respectively), whereas xylene was found to be mainly vehicular. In addition, isoprene revealed its biogenic nature. OFPs arising from vehicular, industrial and biogenic contributions could be further assessed for the purpose of emission control of NMHCs in the ozone non-attainment area.     

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.     

Emissions of isoprene,monoterpene and short-chained carbonyl compounds from Eucalyptus spp. in southern Australia

Eucalypts are among the highest emitters of biogenic volatile organic compounds, yet there is relatively little data available from field studies of this genus. Emissions of isoprene, monoterpenes and the short-chained carbonyls formaldehyde, acetaldehyde and acetone were determined from four species (Eucalyptus camaldulensis, Eucalyptus globulus, Eucalyptus grandis, and Eucalytpus viminalis) in Australia. A smaller comparative study was conducted on E. camaldulensis in south-eastern Australia. Carbonyl emissions, reported here for the first time from eucalypts, were generally comparable with rates reported for other species, with diurnal emissions peaking at about 4, 75 and 34 nmol m^?2 min^?1 for acetone, formaldehyde and acetaldehyde respectively. There was wide variation in diurnal isoprene and monoterpene emissions between species, but under standard conditions, isoprene emissions were much lower than previous reports. Conversely, standard emission rates of monoterpenes were as much as six times greater than previous reports for some species. Emission of each carbonyl was correlated with its ambient concentration across different species, but more weakly related to temperature. Acetaldehyde emission in particular was significantly correlated with transpiration, but not with sap flow or with ethanol concentrations in xylem sap, suggesting fermentation within the leaf and stomatal conductance are primary controlling processes. Differences in acetaldehyde exchange velocities between sites, in addition to transpiration differences, suggest stomata may indeed exert long term emission regulation, in contrast to compounds for which no biological sink exists.     

Characteristics of ambient C2–C11 non-methane hydrocarbons in metropolitan Nagoya,Japan

To understand the characteristics of non-methane hydrocarbon (NMHC) abundance in an urban air of Nagoya, one of the metropolitan areas of Japan, 48 species of C₂–C₁₁ NMHCs were measured with a measurement system, developed in this study, by using gas chromatography with flame ionization detection (GC/FID) continuously for one year from December 2003 to November 2004.Annual mean concentration of NMHCs in normal and propylene equivalent (PE) in Nagoya was compared with those in four urban areas of Seoul, London, Lille, and Dallas to extract characteristics of urban air. While the absolute values of the normal and PE concentrations of alkanes, alkenes, alkyne, and aromatics were significantly different among these urban areas, the proportions of each chemical group to the total NMHC were not so different.In Nagoya, the total normal concentration was high from November to February and low from June to August. The pattern of the seasonal variation was influenced mainly by that of alkanes. On the other hand, the total PE concentration was high from July to December and low from January to June. The pattern of the seasonal variation was influenced mainly by those of alkenes and aromatics. Particularly the normal concentration of isoprene was high from May to September because of large emission associated with activity of plants. As the results, in summer, the PE concentration of isoprene was especially high, and its contribution to the total NMHCs measured in this study was approximately 40%. The total PE concentrations were high in summer when the concentration of OH radicals is also high, suggesting that the productions of ozone and secondary organic aerosol (SOA) are likely to be promoted in summer of Nagoya.     

Improved land cover and emission factors for modeling biogenic volatile organic compounds emissions from Hong Kong

This paper describes a study of local biogenic volatile organic compounds (BVOC) emissions from the Hong Kong Special Administrative Region (HKSAR). An improved land cover and emission factor database was developed to estimate Hong Kong emissions using MEGAN, a BVOC emission model developed by Guenther et al. (2006). Field surveys of plant species composition and laboratory measurements of emission factors were combined with other data to improve existing land cover and emission factor data. The BVOC emissions from Hong Kong were calculated for 12 consecutive years from 1995 to 2006. For the year 2006, the total annual BVOC emissions were determined to be 12,400 metric tons or 9.82 × 10⁹ g C (BVOC carbon). Isoprene emission accounts for 72%, monoterpene emissions account for 8%, and other VOCs emissions account for the remaining 20%. As expected, seasonal variation results in a higher emission in the summer and a lower emission in the winter, with emission predominantly in day time. A high emission of isoprene occurs for regions, such as Lowest Forest-NT North, dominated by broadleaf trees. The spatial variation of total BVOC is similar to the isoprene spatial variation due to its high contribution. The year to year variability in emissions due to weather was small over the twelve-year period (?1.4%, 2006 to 1995 trendline), but an increasing trend in the annual variation due to an increase in forest land cover can be observed (+7%, 2006 to 1995 trendline). The results of this study demonstrate the importance of accurate land cover inputs for biogenic emission models and indicate that land cover change should be considered for these models.     

Daily, weekly, and seasonal time courses of VOC concentrations in a semi-urban area near Barcelona

In order to study the daily, weekly, and seasonal patterns and possible origins of air concentrations of volatile organic compounds (VOCs), measurements were taken on a minute-by-minute basis with a PTR-MS in the vicinity of a highway in a semi-urban site near Barcelona. Four periods of the year were chosen and samples were taken under different meteorological conditions and at different phenological stages of the surrounding vegetation. None of the measured VOCs concentrations exceeded air-quality guidelines. The results showed that diurnal, weekly, and seasonal fluctuations in measured VOC concentrations depended on variations in the strength of sources, as well as on photochemical activity and meteorological conditions. There was a decrease in concentrations in most VOCs when mixing depth, photochemical destruction, and wind speed increased at midday. On the other hand, high values of some VOCs occurred at night when the strength of their sinks and the mixing layer decreased. Interestingly, in June, night emissions and concentration peaks of methanol and acetone occurred in periods with dew formation and no wind. VOCs related to anthropogenic emissions presented a weekly pattern of variation with a clear distinction being found between working days and the weekend. The seasonal variation showed higher levels in December for all VOCs, except for isoprene. The thinning of the mixing layer leading to greater concentrations of volatiles and lower wind speeds in winter could account for those higher VOC levels. Benzene and toluene originated mainly from anthropogenic emissions. The sources of acetaldehyde, methanol, and acetone appeared to be mainly biogenic and these compounds were the most abundant of all the measured VOCs. Isoprene concentration patterns suggest a predominantly anthropogenic origin in December and March and a mainly biogenic origin in June and October. All these data provide useful information on the dynamics of VOCs in an area where ozone levels in summer exceed quite often the standard protection thresholds for O₃.     

NMOC,ozone, and organic aerosol in the southeastern United States, 1999–2007: 1. Spatial and temporal variations of NMOC concentrations and composition in Atlanta,Georgia

Volatile organic compounds (VOCs) are emitted from anthropogenic and natural (biogenic) sources into the atmosphere. Characterizing their ambient mixing ratios or concentrations is a challenge because VOCs comprise hundreds of species, and accurate measurements are difficult. Long-term hourly and daily-resolution data have been collected in the metropolitan area of Atlanta, Georgia, a major city dominated by motor vehicle emissions. A series of observations of daily, speciated C₂–C₁₀ non-methane organic compounds (NMOC) and oxygenated hydrocarbons (OVOC) in mid-town Atlanta (Jefferson Street, JST) are compared with data from three urban-suburban sites and a nearby non-urban site. Annual-average mixing ratios of NMOC and OVOC at JST declined from 1999 through 2007. Downward trends in NMOC, CO, and NO_y corroborate expected emission changes as reflected in emission inventories for Atlanta’s Fulton County. Comparison of the JST NMOC composition with data from roadside and tunnel sampling reveals similarities to motor vehicle dominated samples. The JST annual average VOC-OH reactivities from 1999 to 2007 were relatively constant compared with the decline in annual-average NMOC mixing ratios. Mean reactivity at JST, in terms of concentration*k_OH, was approximately 40% alkenes, 22% aromatics, 16% isoprene and 6% other biogenics, 13% C₇–C₁₀ alkanes and 3% C₂-C₆ alkanes, indicating that biogenic NMOCs are important but not dominant contributors to the urban reactive NMOC mix. In contrast, isoprene constituted ～50% of the VOC-OH reactivities at two non-urban sites. Ratios of 24-hour average CO/benzene, CO/isopentane, and CO/acetylene concentrations indicate that such species are relatively conserved, consistent with their low reactivity. Ratios of more-reactive to less-reactive species show diurnal variability largely consistent with expected emission patterns, transport and mixing of air, and chemical processing.     

Modeling speciated terpenoid emissions from the European boreal forest

We present the first estimates of speciated monoterpene emissions from the North European coniferous forests. Measured emission factors and emission profiles of boreal tree species (Picea abies, Pinus sylvestris, Betula pendula, Salix phylicifolia, Populus tremula, and Alnus incana) were used together with detailed satellite land cover information and meteorological data in an emission model based on the Guenther emission algorithms. The variation of the coniferous biomass within the boreal region (60°N to 70°N) was obtained from forest inventory data, and the seasonal variability of the deciduous biomass was taken into account through simple boreal climatology parameterisation. The annual biogenic emissions in the boreal zone are dominated by coniferous species, but in the summer months, the deciduous contribution to the monoterpene and isoprene emissions is considerable. Norway spruce (Picea abies) is the most important isoprene emitter in the north European boreal forests. The biogenic emission fluxes in the South boreal zone are approximately twice as high as fluxes in the North boreal zone. α- and β-pinene, carene, and cineole are the most abundant emitted terpenes, with a strong contribution of isoprene and linalool during the summer months.     

Characterising sources and sinks of rural VOC in eastern France

Fifty non-methane hydrocarbons (NMHC) and seventeen carbonyl compounds were measured at a French rural site from 1997 to 2001, as part of the EMEP programme. Data handling was based on an original source-receptor approach. First, the examination of the levels and trends was completed by the comparison of the seasonal distribution of rural and urban VOC/acetylene ambient ratios. This analysis has shown that most of the compounds derived from mixing and photochemical transformation of mid-range transported urban pollutants from the downwind urban area. Then, identified sources and sinks were temporally apportioned. Urban air masses mixing explains, at least, 80% of the wintertime levels of anthropogenic NMHC and isoprene. In summer, photochemistry dominates the day-to-day distribution of anthropogenic NMHC whilst summertime isoprene is also controlled by in-situ biogenic emissions. Then, the results of C(1)-C(3) carbonyls were discussed with respect to their direct biogenic and anthropogenic emissions and photochemical production through the [carbonyl/auto-exhaust tracers] emission ratio. Diluted vehicle exhaust emissions mainly contribute to the total content of lower aldehydes in winter while other processes control lower ketones. Secondary production is predominant in summer with at least a 50% high intensity. Its dependence upon temperature and radiation is also demonstrated. Finally, the importance of the primary and secondary biogenic production of acetone and formaldehyde is assessed. In particular, biogenic contribution would explain 37 +/- 25% of acetone levels in summer.     

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.     

Estimating Taiwan biogenic VOC emission: Leaf energy balance consideration

The goal of the present study is to provide a comprehensive model to estimate biogenic volatile organic compounds (BVOCs) in Taiwan. In addition to metrological data, the model consists of (1) 83 land-use patterns, (2) emission factors for various vegetations, (3) energy balance equation to account for leaf temperature, and (4) correction terms for photosynthetically active radiation. The model output includes 4 categories of 33 BVOCs [isoprene, methylbutenol (MBO), 14 species of monoterpenes and 17 other BVOCs]. The results of model verification based on several approaches include: (1) predicted isoprene emission flux correlates relatively good with the observed isoprene concentration (R² = 0.66); (2) correlation between leaf temperature and observed isoprene levels is better than that between ambient temperature and isoprene concentrations (R² = 0.63 vs. 0.58); (3) model-predicted isoprene fluxes match well with observed 3-day diurnal isoprene concentration variations; and (4) subsequent model-predicted O₃ concentrations with the BVOC input obtained in the present study match well than that with previous estimated BVOC data with the observed 6-day diurnal O₃ levels in 8 air quality monitoring stations.Based on the meteorological data in 2000, the total emission of BVOCs in Taiwan was simulated to be about 433,000 ton (33% of total VOCs) of which both isoprene and 14 species of monoterpenes account for about 34%, with 17 species of other BVOCs being 31% and <2% contribution from MBO. Total emissions of BVOCs are higher in lower and medium altitude (300–1000 m) mountain areas with an average of around 15–30 ton km⁻² y⁻¹. The implication of the other results is also discussed.     

Effects of temperature and land use on predictions of biogenic emissions in Eastern Texas,USA

Accurate estimates of biogenic volatile organic compound emissions are critical for air quality planning in areas such as Eastern Texas where biogenic emissions comprise a significant fraction of the total volatile organic compound inventory. Uncertainties in biogenic volatile organic chemical emission estimates associated with different land use databases, surface temperature databases, and temperature interpolation methods were quantified and compared. The sensitivity of isoprene emissions to land use classification was investigated by comparing predictions based on land use data recently compiled for Eastern Texas to those based on the Biogenic Emissions Landcover Database version 3.1 (BELD3). Previous studies have only made these comparisons with the previous BELD version 2 database. Isoprene emission increased throughout much of Eastern Texas because areas classified as agricultural or savannah in BELD3 were more accurately classified as Post Oak, Live Oak, mesquite, and juniper in the new database. These results indicate the need for land use studies in areas poorly characterized in the BELD3. The sensitivity of isoprene emission estimates to uncertainties in surface temperatures were investigated by comparing predictions based on two different temperature databases and three different interpolation techniques. Spatial interpolations of surface temperatures collected at available Automated Surface Observing System (ASOS) stations in Houston, Austin, and Dallas were similar to the spatial interpolations of surface temperatures obtained from the ETA Data Assimilation System (EDAS). As a result, substantial variations in isoprene emissions were not observed over the majority of the modeling domain; however, differences of 4 F over localized regions produced a 35% difference in isoprene emissions. Comparisons between the isoprene emissions of the three interpolation methods sometimes revealed large variations, with maximum temperature differences of 4 F resulting in 60% differences in isoprene emissions in areas with the highest isoprene emissions. It was noted that the ASOS stations were clustered in urban areas and not in areas with the highest biogenic emissions. More ambient temperature monitors need to be located in rural locations to provide robust estimates of biogenic emissions and facilitate validation of interpolated temperature fields.     

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.     

Biogenic volatile organic compound emissions from a lowland tropical wet forest in Costa Rica

Twenty common plant species were screened for emissions of biogenic volatile organic compounds (BVOCs) at a lowland tropical wet forest site in Costa Rica. Ten of the species examined emitted substantial quantities of isoprene. These species accounted for 35–50% of the total basal area of old-growth forest on the major edaphic site types, indicating that a high proportion of the canopy leaf area is a source of isoprene. A limited number of canopy-level BVOC flux measurements were also collected by relaxed eddy accumulation (REA). These measurements verify that the forest canopy in this region is indeed a significant source of isoprene. In addition, REA fluxes of methanol and especially acetone were also significant, exceeding model estimates and warranting future investigation at this site. Leaf monoterpene emissions were non-detectable or very low from the species surveyed, and ambient concentrations and REA fluxes likewise were very low. Although the isoprene emission rates reported here are largely consistent with phylogenetic relations found in other studies (at the family, genus, and species levels), two species in the family Mimosaceae, a group previously found to consist largely of non-isoprene emitters, emitted significant quantities of isoprene. One of these, Pentaclethra macroloba (Willd.) Kuntze, is by far the most abundant canopy tree species in the forests of this area, composing 30–40% of the total basal area. The other, Zygia longifolia (Humb. & Bonpl.) Britton & Rose is a common riparian species. Our results suggest that the source strength of BVOCs is important not only to tropical atmospheric chemistry, but also may be important in determining net ecosystem carbon exchange.     

Characteristic behavior of peroxyacetyl nitrate (PAN) in Seoul megacity, Korea

We measured the concentrations of peroxyacetyl nitrate (PAN) and other photochemically reactive species, including O(3), NO(2), and non-methane hydrocarbons (NMHCs), in the Seoul Metropolitan area (SMA) during May through June in 2004 and 2005. PAN was determined using a fast chromatograph with luminol-based chemiluminescence detection. Mixing ratios of PAN ranged from below the detection limit (0.1ppbv) to 10.4ppbv with an average of 0.8ppbv. O(3) concentrations ranged from 0 to 141ppbv. The average PAN/O(3) ratio of 0.07 was higher than that observed in cities of Europe and North America (0.02) where control strategies have been enforced to reduce hydrocarbon emissions through extensively reformulated gasoline programs. Strong positive correlations between daily PAN and O(3) maxima during the day demonstrate that similar photochemical factors controlled the production of these two chemicals. However, relationships between PAN and its precursors, NO(2) and NMHCs, suggest that PAN production was more sensitive to NO(2) than NMHCs levels whereas O(3) production was limited by the overall availability of NMHCs. It is likely that the compositions of NMHCs in SMA were favorable for PAN production because of the low fractions of oxygenated compounds in automobile fuels. PAN maxima were observed around noon, which was 2-3h earlier than the much broader O(3) maxima that occurred in the midafternoon. After reaching the maximum, PAN concentrations rapidly dropped within a few hours, which could be largely due to thermal destruction and to limited production under the typically low NO(2) levels that occurred in the early afternoon. The heterogeneous destruction of particulate matter could be an additional sink for PAN in SMA.     

Isoprene emission from tropical tree species

Foliar emission of isoprene was measured in nine commonly growing tree species of Delhi, India. Dynamic flow enclosure technique was used and gas samples were collected onto Tenax-GC/Carboseive cartridges, which were then attached to the sample injection system in the gas chromatograph (GC). Eluting compounds were analysed using a flame ionisation detector (FID). Out of the nine tree species, isoprene emission was found in six species (Eucalyptus sp., Ficus benghalensis, Ficus religiosa, Mangifera indica, Melia azedarach, and Syzygium jambolanum), whereas, in the remaining three tree species (Alstonia scholaris, Azadirachta indica, and Cassia fistula) no isoprene emission was detected or the levels of emission were negligible or below the detection limit (BDL). Among six tree species, the highest hourly emission (10.2 +/- 6.8 microg g(-1) leaf dry weight, average of five seasons) was observed in Ficus religiosa, while minimum emission was from Melia azedarach (2.2 +/- 4.9 microg g(-1) leaf dry weight, average of five seasons). Isoprene emission (average of six species), over five seasons, was found to vary between 3.9 and 8.5 microg g(-1) leaf dry weight during the rainy season. In addition, significant diurnal variation in isoprene emission was observed in each species. The preliminary estimate made in this study on the annual biogenic VOC emission from India may probably be the first of its kind from this part of the world.     

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.     

VOC source–receptor relationships in Houston during TexAQS-II

During the TRAMP field campaign in August–September 2006, C₂–C₁₀ volatile organic compounds (VOCs) were measured continuously and online at the urban Moody Tower (MT) site. This dataset was compared to corresponding VOC data sets obtained at six sites located in the highly industrialized Houston Ship Channel area (HSC). Receptor modeling was performed by positive matrix factorization (PMF) at all sites. Conditional probability functions (CPF) were used to determine the origin of the polluted air masses in the Houston area. A subdivision into daytime and nighttime was carried out to discriminate photochemical influences. Eight main source categories of industrial, mobile, and biogenic emissions were identified at the urban receptor site, seven and six, respectively, at the different HSC sites. At MT natural gas/crude oil contributed most to the VOC mass (27.4%), followed by liquefied petroleum gas (16.7%), vehicular exhaust (15.3%), fuel evaporation (14.3%), and aromatics (13.4%). Also petrochemical sources from ethylene (4.7%) and propylene (3.6%) play an important role. A minor fraction of the VOC mass can be attributed to biogenic sources mainly from isoprene (4.4%). Based on PMF analyses of different wind sectors, the total VOC mass was estimated to be twofold at MT with wind directions from HSC compared to air from a typical urban sector, for petrochemical compounds more than threefold. Despite the strong impact of air masses influenced by industrial sources at HSC, still about a third of the total mass contributions at MT can be apportioned to other sources, mainly motor vehicles and aromatic solvents. The investigation of diurnal variation in combination with wind directional frequencies revealed the greatest HSC impact at the urban site during the morning, and the least during the evening.     

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.     

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.