Characterization of n-alkanes in PM2.5 of the Taipei aerosol

Ambient concentrations of n-alkanes with carbon number ranging from 17 to 36 were determined for PM_2.5 samples collected in Taipei city during September 1997–February 1998. The measured concentrations of particulate n-alkanes were in the range of 69–702 ng m⁻³, considerably higher than the concentration levels observed in Los Angeles and Hong Kong. The concentration distributions of n-alkanes homologues obtained in this study exhibited peaks at C₁₉, C₂₄ or C₂₅. This suggests that fossil fuel utilization, such as vehicular exhaust and lubricant residues, was an important contributor to the Taipei aerosol. Source apportionment of PM_2.5 was conducted using carbon preference index (CPI, defined as the ratio of the total concentration of particulate n-alkanes with odd carbon number to that with even carbon number) and U : R ratio (the concentration ratio of unresolved components to resolved components obtained from chromatograms). The low CPI value (0.9–1.9) and high U : R ratio (2.6–6.4) for each sample further confirmed that fossil fuel utilization was the major source of n-alkanes in ambient PM_2.5 of Taipei city. Estimates from these results showed that 69–93% of the n-alkanes in PM_2.5 of the Taipei aerosol originated from vehicular exhaust. The higher concentration level of particulate n-alkanes in the Taipei aerosol was mainly a result of vehicular emissions.     

Laboratory studies on the uptake of aromatic hydrocarbons by ice crystals during vapor depositional crystal growth

Uptake of aromatic hydrocarbons (AH) by ice crystals during vapor deposit growth was investigated in a walk-in cold chamber at temperatures of 242, 251, and 260 K, respectively. Ice crystals were grown from ambient air in the presence of gaseous AH namely: benzene (C₆H₆), toluene (methylbenzene, C₇H₈), the C₈H₁₀ isomers ethylbenzene, o-, m-, p-xylene (dimethylbenzenes), the C₉H₁₂ isomers n-propylbenzene, 4-ethyltoluene, 1,3,5-trimethylbenzene (1,3,5-TMB), 1,2,4-trimethylbenzene (1,2,4-TMB), 1,2,3-trimethylbenzene (1,2,3-TMB), and the C₁₀H₁₄ compound tert.-butylbenzene. Gas-phase concentrations calculated at 295 K were 10.3–20.8 μg m⁻³. Uptake of AH was detected by analyzing vapor deposited ice with a very sensitive method composed of solid-phase micro-extraction (SPME), followed by gas chromatography/mass spectrometry (GC/MS).Ice crystal size was lower than 1 cm. At water vapor extents of 5.8, 6.0 and 8.1 g m⁻³, ice crystal shape changed with decreasing temperatures from a column at a temperature of 260 K, to a plate at 251 K, and to a dendrite at 242 K. Experimentally observed ice growth rates were between 3.3 and 13.3×10⁻³ g s⁻¹ m⁻² and decreased at lower temperatures and lower value of water vapor concentration. Predicted growth rates were mostly slightly higher.Benzene, toluene, ethylbenzene, and xylenes (BTEX) were not detected in ice above their detection limits (DLs) of 25 pg g_ice⁻¹ (toluene, ethylbenzene, xylenes) and 125 pg g_ice⁻¹ (benzene) over the entire temperature range. Median concentrations of n-propylbenzene, 4-ethyltoluene, 1,3,5-TMB, tert.-butylbenzene, 1,2,4-TMB, and 1,2,3-TMB were between 4 and 176 pg g_ice⁻¹ at gas concentrations of 10.3–10.7 μg m⁻³ calculated at 295 K. Uptake coefficients (K) defined as the product of concentration of AH in ice and density of ice related to the product of their concentration in the gas phase and ice mass varied between 0.40 and 10.23. K increased with decreasing temperatures. Values of Gibbs energy (ΔG) were between −4.5 and 2.4 kJ mol⁻¹ and decreased as temperatures were lowered. From the uptake experiments, the uptake enthalpy (ΔH) could be determined between −70.6 and −33.9 kJ mol⁻¹. The uptake entropy (ΔS) was between −281.3 and −126.8 J mol⁻¹ K⁻¹. Values of ΔH and ΔS were rather similar for 4-ethlytoluene, 1,3,5-TMB and tert.-butylbenzene, whereas 1,2,3-TMB showed much higher values.     

The continuous field measurements of soluble aerosol compositions at the Taipei Aerosol Supersite,Taiwan

The characteristics of ambient aerosols, affected by solar radiation, relative humidity, wind speed, wind direction, and gas–aerosol interaction, changed rapidly at different spatial and temporal scales. In Taipei Basin, dense traffic emissions and sufficient solar radiation for typical summer days favored the formation of secondary aerosols. In winter, the air quality in Taipei Basin was usually affected by the Asian continental outflows due to the long-range transport of pollutants carried by the winter monsoon. The conventional filter-based method needs a long time for collecting aerosols and analyzing compositions, which cannot provide high time-resolution data to investigate aerosol sources, atmospheric transformation processes, and health effects. In this work, the in situ ion chromatograph (IC) system was developed to provide 15-min time-resolution data of nine soluble inorganic species (Cl⁻, NO₂⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺). Over 89% of all particles larger than approximately 0.056 μm were collected by the in situ IC system. The in situ IC system is estimated to have a limit of detection lower than 0.3 μg m⁻³ for the various ambient ionic components. Depending on the hourly measurements, the pollutant events with high aerosol concentrations in Taipei Basin were associated with the local traffic emission in rush hour, the accumulation of pollutants in the stagnant atmosphere, the emission of industrial pollutants from the nearby factories, the photochemical secondary aerosol formation, and the long-range transport of pollutants from Asian outflows.     

Volatile organic compound emissions from Siberian larch

We determined hourly emissions of isoprene, monoterpenes and sesquiterpenes from Siberian larch, one of the major tree species in Siberian forests. Summer volatile organic compounds (VOCs) emission from Siberian larch consisted mainly of monoterpenes (about 90%). The monoterpene emission spectrum remained constant during the measurement period, almost half was sabinene and other major monoterpenes were Δ³-carene, β- and α-pinene. During spring and summer, about 10% of the VOCs were sesquiterpenes, mainly α-farnesene. The sesquiterpene emissions declined to 3% in the fall. Isoprene, 2-methyl-3-buten-2-ol (MBO) and 1,8-cineole contributed to less than 3% of the VOC emission during the whole period. The diurnal variation of the emissions could be explained using a temperature-dependent parameterization. Emission potentials normalized to 30 °C were 5.2–21 μg g_dw⁻¹ h⁻¹ (using β-value of 0.09 °C⁻¹) for monoterpenes and 0.4–1.8 μg g_dw⁻¹ h⁻¹ (using β-value of 0.143 °C⁻¹, mean of determined values) for sesquiterpenes. Normalized monoterpene emission potentials were highest in late summer and elevated again in late fall. Sesquiterpene emission potentials were also highest in late summer, but decreased towards fall.     

Comparison of measured and model-calculated real-world traffic emissions

The quality of an emission calculation model based on emission factors measured on roller test stands and statistical traffic data was evaluated using source strengths and emission factors calculated from real-world exhaust gas concentration differences measured upwind and downwind of a motorway in southwest Germany. Gaseous and particulate emissions were taken into account. Detailed traffic census data were taken during the measurements. The results were compared with findings of similar studies.The main conclusion is the underestimation of CO and NO_x source strengths by the model. On the average, it amounts to 23% in case of CO and 17% for NO_x. The latter underestimation results from an undervaluation by 22% of NO_x emission factors of heavy-duty vehicles (HDVs). There are significant differences between source strengths on working days and weekends because of the different traffic split between light-duty vehicles (LDVs) and HDVs. The mean emission factors of all vehicles from measurements are 1.08 g km⁻¹ veh⁻¹ for NO_x and 2.62 g km⁻¹ veh⁻¹ for CO. The model calculations give 0.92 g km⁻¹ veh⁻¹ for NO_x and 2.14 g km⁻¹ veh⁻¹ for CO.The source strengths of 21 non-methane hydrocarbon (NMHC) compounds quantified are underestimated by the model. The ratio between the measured and model-calculated emissions ranges from 1.3 to 2.1 for BTX and up to 21 for 16 other NMHCs. The reason for the differences is the insufficient knowledge of NMHC emissions of road traffic.Particulate matter emissions are dominated by ultra-fine particles in the 10–40 nm range. As far as aerosols larger than 29 nm are concerned, 1.80×10¹⁴ particles km⁻¹ veh⁻¹ are determined for all vehicles, 1.22×10¹⁴ particles km⁻¹ veh⁻¹ and an aerosol volume of 0.03 cm³ km⁻¹ veh⁻¹ are measured for LDVs, and for HDVs 7.79×10¹⁴ particles km⁻¹ veh⁻¹ and 0.41 cm³ km⁻¹ veh⁻¹ are calculated. Traffic-induced turbulence has been identified to have a decisive influence on exhaust gas dispersion near the source.     

Application of circuit model for Taipei City PM10 simulation

This study simulated PM₁₀ concentrations in Taipei City from September 1990 to June 1992, by using a circuit model developed by Tsuang and Chao. Simulation results demonstrated that the scheme performs better than a box model. The correlation coefficient between observed and predicted values was 0.61 with a standard error of 60 μg m^-3. The mean treatment score of successful predictions of high PM₁₀ concentrations (exceeding 125 μg m^-3) was 58%. Fine particulates were found to be the major contributor toward hazardous air quality, under a stable, low wind speed and rainless atmosphere. In addition, the ill-mixed factor was found to be zero. The circuit model is close to a box model equation under an unstable atmosphere where the mixing height is much higher than the surface layer.     

VOC concentration profiles in an ozone non-attainment area: A case study in an urban and industrial complex metroplex in southern Taiwan

VOCs are important precursors of the atmospheric ozone formation species. This study investigated the airborne concentrations of 52 VOCs at two air quality monitoring stations, Daliao and Tzouying, during wintertime in southern Taiwan. Airborne VOCs samples were taken in stainless steel canisters four times per day and analyzed via gas chromatography/mass spectrometry. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential in this ozone non-attainment region. Toluene, propane, isopentane, propene, n-butane, n-pentane and isoprene contributed 78–79% of the 52 VOCs in Daliao. Toluene, 1-butene, isopentane, propene, propane, n-undecane, and n-butane contributed 71–77% of the 52 VOCs in Tzouying. The VOCs concentrations were higher in Daliao due to the high toluene emissions from a paint plant and a solvent plant in the nearby industrial district. The 24-h VOC concentrations averaged 25 ppb higher in Tzouying than in Daliao. The ozone formation potential of airborne VOCs was 1687–2730 and 1717–2261 μg-O₃/g-VOCs in Daliao and Tzouying, respectively. Ozone concentrations in Tzouying were 44 ppb higher than in Daliao during the 1200–1600 sampling period.     

Quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles

There are a number of difficulties associated with the quantitative analysis of volatile organic compounds (VOCs) in atmospheric particles. Therefore, majority of the previous studies on VOCs associated with particles have been qualitative. Air samples were collected in Izmir, Turkey to determine ambient particle and gas phase concentrations of several aromatic, oxygenated and halogenated VOCs. Samples were quantitatively analyzed using thermal desorption–gas chromatography/mass spectrometry. Gas-phase concentrations ranged between 0.02 (bromoform) and 4.65 μg m⁻³ (toluene) and were similar to those previously measured at the same site. Particle-phase concentrations ranged from 1 (1,3-dichlorobenzene) to 933 pg m⁻³ (butanol). VOCs were mostly found in gas-phase (99.9±0.25%). However, the particulate VOCs had comparable concentrations to those reported previously for semivolatile organic compounds. The distribution of particle-phase VOCs between fine (d_p<2.5 μm) and coarse (2.5 μm<d_p<10 μm) fractions was also investigated. It was found that VOCs were mostly associated with fine particles.     

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.     

Secondary aerosol formation through photochemical reactions estimated by using air quality monitoring data in Taipei City from 1994 to 2003

Analyses of diurnal patterns of PM₁₀ in Taipei City have been performed in this study at different daily ozone maximum concentrations (O_3,max) from 1994 to 2003. In order to evaluate secondary aerosol formation at different ozone levels, CO was used as a tracer of primary aerosol, and O_3,max was used as an index of photochemical activity. Results show that when O_3,max exceeds 120 ppb, the highest photochemical formation of secondary aerosol can be found at 15:00 (local time). The produced secondary aerosol is estimated to contribute 30 μg m⁻³ (43%) of PM₁₀ concentration, and about 77% of the estimated secondary PM₁₀ is composed of PM_2.5. The estimated maximum concentration of secondary aerosol occurs 2–3 h later than the maximum ozone concentration. As revealed in an O₃ episode, PM₁₀ and PM_2.5 vary consistently with O₃ at daytime, which suggests that they are mostly secondary aerosols produced from photochemical reactions. Data collected from Taipei aerosol supersite in 2002 indicates that for all O₃ levels, summertime PM_2.5 is composed of 23%, 20%, 9%, and 7% of organic carbon, sulfate, nitrate, and elemental carbon, respectively. Aerosol number and volume size spectra are dominated by submicron particles either from pollution transport or photochemical reactions. Secondary PM₁₀ concentrations show increasing tendencies for the time between 15:00 and 19:00 from 1994–1996 to 2001–2003. This reveals that the abatement of secondary PM₁₀ becomes more important after pronounced primary PM₁₀ reduction in a metropolis.     

Compound specific carbon and hydrogen stable isotope analyses of volatile organic compounds in various emissions of combustion processes

This study presents carbon (δ¹³C) and hydrogen (δD) isotope values of volatile organic compounds (VOCs) in various emission sources using thermal desorption–gas chromatography–isotope ratio mass spectrometry (TD–GC–irMS). The investigated VOCs ranged from C6 to C10. Samples were taken from (i) car exhaust emissions as well as from plant combustion experiments of (ii) various C3 and (iii) various C4 plants. We found significant differences in δ values of analysed VOCs between these sources, e.g. δ¹³C of benzene ranged between (i) −21.7 ± 0.2‰, (ii) −27.6 ± 1.6‰ and (iii) −16.3 ± 2.2‰, respectively and δD of benzene ranged between (i) −73 ± 13‰, (ii) −111 ± 10‰ and (iii) −70 ± 24‰, respectively. Results of VOCs present in investigated emission sources were compared to values from the literature (aluminium refinery emission). All source groups could be clearly distinguished using the dual approach of δ¹³C and δD analysis. The results of this study indicate that the correlation of compound specific carbon and hydrogen isotope analysis provides the potential for future research to trace the fate and to determine the origin of VOCs in the atmosphere using thermal desorption compound specific isotope analysis.     

Trace gas variations at Cape Point,South Africa,during May 1997 following a regional biomass burning episode

During the continuous monitoring of atmospheric parameters at the station Cape Point (34°S, 18°E), a smoke plume originating from a controlled fire of 30-yr-old fynbos was observed on 6 May 1997. For this episode, which was associated with a nocturnal inversion and offshore airflow, atmospheric parameters (solar radiation and meteorological data) were considered and the levels of various trace gases compared with those measured at Cape Point in maritime air. Concentration maxima in the morning of 6 May for CO₂, CO, CH₄ and O₃ amounted to 370.3 ppm, 491 ppb, 1730 ppb and 47 ppb, respectively, whilst the mixing ratios of several halocarbons (F-11, F-12, F-113, CCl₄ and CH₃CCl₃) remained at background levels. In the case of CO, the maritime background level for this period was exceeded by a factor of 9.8. Differences in ozone levels of up to 5 ppb between air intakes at 4 and 30 m above the station (located at 230 m above sea level) indicated stratification of the air advected to Cape Point during the plume event. Aerosols within the smoke plume caused the signal of global solar radiation and UV–A to be attenuated from 52.4 to 13.0 mW cm⁻² and from 2.3 to 1.3 mW cm⁻², respectively, 5 h after the trace gases had reached their maxima. Emission ratios (ERs) calculated for CO and CH₄ relative to CO₂ mixing ratios amounted to 0.042 and 0.0040, respectively, representing one of the first results for fires involving fynbos. The CO ER is somewhat lower than those given in the literature for African savanna fires (average ER=0.048), whilst for CH₄ the ER falls within the range of ERs reported for the flaming (0.0030) and smouldering phases (0.0055) of savanna fires. Non-methane hydrocarbon (NMHC) data obtained from a grab sample collected during the plume event were compared to background levels. The highest ERs (ΔNMHC/ΔCH₄) have been obtained for the C₂–C₃ hydrocarbons (e.g. ethene at 229.3 ppt ppb⁻¹), whilst the C₄–C₇ hydrocarbons were characterised by the lowest ERs (e.g. n-hexane at 1.0 and n-pentane at 0.8 ppt ppb⁻¹).     

Sensitivity of ozone concentrations to diurnal variations of surface emissions in Mexico City: A WRF/Chem modeling study

Sensitivity of ozone (O₃) concentrations in the Mexico City area to diurnal variations of surface air pollutant emissions is investigated using the WRF/Chem model. Our analysis shows that diurnal variations of nitrogen oxides (NO_x = NO + NO₂) and volatile organic compound (VOC) emissions play an important role in controlling the O₃ concentrations in the Mexico City area. The contributions of NO_x and VOC emissions to daytime O₃ concentrations are very sensitive to the morning emissions of NO_x and VOCs. Increase in morning NO_x emissions leads to decrease in daytime O₃ concentrations as well as the afternoon O₃ maximum, while increase in morning VOC emissions tends to increase in O₃ concentrations in late morning and early afternoon, indicating that O₃ production in Mexico City is under VOC-limited regime. It is also found that the nighttime O₃ is independent of VOCs, but is sensitive to NO_x. The emissions of VOCs during other periods (early morning, evening, and night) have only small impacts on O₃ concentrations, while the emissions of NO_x have important impacts on O₃ concentrations in the evening and the early morning.This study suggests that shifting emission pattern, while keeping the total emissions unchanged, has important impacts on air quality. For example, delaying the morning emission peak from 8 am to 10 am significantly reduced the morning peaks of NO_x and VOCs, as well as the afternoon O₃ maxima. It suggests that without reduction of total emission, the daytime O₃ concentrations can be significantly reduced by changing the diurnal variations of the emissions of O₃ precursors.     

Study of the dispersion of VOCs emitted by a municipal solid waste landfill

The dispersion of VOCs emitted by a municipal solid waste landfill was studied for a period of over one year. Sixteen VOCs were monitored: linear alkanes from C₇ to C₁₁, BTEX, trimethylbenzene, trichlorethylene, tetrachlorethylene, α and β-pinenes, limonene. The analytical procedure was first comprised of static long-term sampling of about 2 months using radial diffusion Radiello tubes containing activated carbon, followed by extraction by solvent (i.e. CS₂) and GC/MS analysis. The results were initially analysed on the basis of the total concentration of the quantified VOCs, then by examining the concentrations of certain selected compounds. The influence of different parameters such as operating conditions, meteorological conditions and site morphology was highlighted on the basis of total VOC concentrations. In order to study the VOC's dispersion more closely, 5 compounds were chosen: toluene, benzene, limonene, and the sum trichlorethylene + tetrachlorethylene, as a “marker”, to verify the origin of the VOCs emitted. The results showed that the main source of VOCs is the open cell and lead to different hypotheses on interferences from neighbouring sources and to the proposal of solutions to limit the emission of VOCs and their dispersion. To our knowledge, this type of study has not been accomplished until this day.     

Biomass consumption and CO2, CO and main hydrocarbon gas emissions in an Amazonian forest clearing fire

Biomass consumption and CO₂, CO and hydrocarbon gas emissions in an Amazonian forest clearing fire are presented and discussed. The experiment was conducted in the arc of deforestation, near the city of Alta Floresta, state of Mato Grosso, Brazil. The average carbon content of dry biomass was 48% and the estimated average moisture content of fresh biomass was 42% on wet weight basis. The fresh biomass and the amount of carbon on the ground before burning were estimated as 528 t ha^?1 and 147 t ha^?1, respectively. The overall biomass consumption for the experiment was estimated as 23.9%. A series of experiment in the same region resulted in average efficiency of 40% for areas of same size and 50% for larger areas. The lower efficiency obtained in the burn reported here occurred possibly due to rain before the experiment. Excess mixing ratios were measured for CO₂, CO, CH₄, C₂–C₃ aliphatic hydrocarbons, and PM_2.5. Excess mixing ratios of CH₄ and C₂–C₃ hydrocarbons were linearly correlated with those of CO. The average emission factors of CO₂, CO, CH₄, NMHC, and PM_2.5 were 1,599, 111.3, 9.2, 5.6, and 4.8 g kg^?1 of burned dry biomass, respectively. One hectare of burned forest released about 117,000 kg of CO₂, 8100 kg of CO, 675 kg of CH₄, 407 kg of NMHC and 354 kg of PM_2.5.     

Volatile organic compounds in roadside microenvironments of metropolitan Hong Kong

The characteristics and concentrations of volatile organic compounds (VOCs) in the roadside microenvironments of metropolitan Hong Kong were investigated. The VOC concentrations, especially toluene, benzene and chlorinated VOCs in Hong Kong were high when compared with those in most developed cities. The average and maximum concentration of toluene was 74.9 and 320.0 μg m⁻³, respectively. The respective values for benzene were 25.9 and 128.6 μg m⁻³. The chlorinated VOCs were dominated by trichloroethylene and tetrachloroethylene. The maximum concentrations of these two species reached 248.2 and 144.0 μg m⁻³, respectively. There were strong variations in the spatial fluctuation and characteristic of VOC concentrations. The highest VOC concentrations were found in the industrial district, which were followed by those in the commercial district, the central business district and finally the residential district. The highest concentrations of most VOC species, especially chlorinated VOC were found in the industrial and commercial districts. The average benzene/toluene ratio in Hong Kong was 0.5 suggesting that vehicular emission was the dominant VOC source in most areas of Hong Kong. There were strong deviations in benzene/toluene, benzene/ethylbenzene and benzene/(m+p-xylene) ratios in the commercial district, and highly chlorinated VOC in the industrial and commercial districts. These suggest that there were other benzene and VOC sources overlying on the high background VOC concentrations in these districts. The common usage of organic solvents in the building and construction industries, and in the small industries in the industrial and commercial districts were believed to be important sources of VOC in Hong Kong.     

Receptor modeling of source apportionment of Hong Kong aerosols and the implication of urban and regional contribution

Understanding the spatial–temporal variations of source apportionment of PM_2.5 is critical to the effective control of particulate pollution. In this study, two one-year studies of PM_2.5 composition were conducted at three contrasting sites in Hong Kong from November 2000 to October 2001, and from November 2004 to October 2005, respectively. A receptor model, principal component analysis (PCA) with absolute principal component scores (APCS) technique, was applied to the PM_2.5 data for the identification and quantification of pollution sources at the rural, urban and roadside sites. The receptor modeling results identified that the major sources of PM_2.5 in Hong Kong were vehicular emissions/road erosion, secondary sulfate, residual oil combustion, soil suspension and sea salt regardless of sampling sites and sampling periods. The secondary sulfate aerosols made the most significant contribution to the PM_2.5 composition at the rural (HT) (44 ± 3%, mean ± 1σ standard error) and urban (TW) (28 ± 2%) sites, followed by vehicular emission (20 ± 3% for HT and 23 ± 4% for TW) and residual oil combustion (17 ± 2% for HT and 19 ± 1% for TW). However, at the roadside site (MK), vehicular emissions especially diesel vehicle emissions were the major source of PM_2.5 composition (33 ± 1% for diesel vehicle plus 18 ± 2% for other vehicles), followed by secondary sulfate aerosols (24 ± 1%). We found that the contribution of residual oil combustion at both urban and rural sites was much higher than that at the roadside site (2 ± 0.4%), perhaps due to the marine vessel activities of the container terminal near the urban site and close distance of pathway for the marine vessels to the rural site. The large contribution of secondary sulfate aerosols at all the three sites reflected the wide influence of regional pollution. With regard to the temporal trend, the contributions of vehicular emission and secondary sulfate to PM_2.5 showed higher autumn and winter values and lower summer levels at all the sites, particularly for the background site, suggesting that the seasonal variation of source apportionment in Hong Kong was mainly affected by the synoptic meteorological conditions and the long-range transport. Analysis of annual patterns indicated that the contribution of vehicular emission at the roadside was significantly reduced from 2000/01 to 2004/05 (p < 0.05, two-tail), especially the diesel vehicular emission (p < 0.001, two-tail). This is likely attributed to the implementation of the vehicular emission control programs with the tightening of diesel fuel contents and vehicular emission standards over these years by the Hong Kong government. In contrast, the contribution of secondary sulfate was remarkably increased from 2001 to 2005 (p < 0.001, two-tail), indicating a significant growth in regional sulfate pollution over the years.     

Biogenic VOC emissions from fresh leaf mulch and wood chips of Grevillea robusta (Australian Silky Oak)

The emissions of VOC from freshly cut and shredded Grevillea robusta (Australian Silky Oak) leaves and wood have been measured. The VOC emissions from fresh leaf mulch and wood chips lasted typically for 30 and 20 h respectively, and consisted primarily of ethanol, (E)-2-hexenal, (Z)-3-hexen-1-ol and acetaldehyde. The integrated emissions of the VOCs were 0.38±0.04 g kg⁻¹ from leaf mulch, and 0.022±0.003 g kg⁻¹ from wood chips. These emissions represent a source of VOCs in urban and rural air that has previously been unquantified and is currently unaccounted for. These VOCs from leaf mulch and wood chips will contribute to both urban photochemistry and secondary organic aerosol formation. Any CH₄ emissions from leaf mulch and wood chips were <1×10⁻¹¹ g g dry mass⁻¹ s⁻¹.     

Aircraft measurements of O3, NOx,CO, VOCs,and SO2 in the Yangtze River Delta region

In this study, air pollutants, including ozone (O₃), nitrogen oxides (NO_x = NO + NO₂), carbon monoxides (CO), sulfur dioxide (SO₂), and volatile organic compounds (VOCs) measured in the Yangtze River Delta (YRD) region during several air flights between September/30 and October/11 are analyzed. This measurement provides horizontal and vertical distributions of air pollutants in the YRD region. The analysis of the result shows that the measured O₃ concentrations range from 20 to 60 ppbv. These values are generally below the US national standard (84 ppbv), suggesting that at the present, the O₃ pollutions are modest in this region. The NO_x concentrations have strong spatial and temporal variations, ranging from 3 to 40 ppbv. The SO₂ concentrations also have large spatial and temporal variations, ranging from 1 to 35 ppbv. The high concentrations of CO are measured with small variations, ranging from 3 to 7 ppmv. The concentrations of VOCs are relatively low, with the total VOC concentrations of less than 6 ppbv. The relative small VOC concentrations and the relative large NO_x concentrations suggest that the O₃ chemical formation is under a strong VOC-limited regime in the YRD region. The measured O₃ and NO_x concentrations are strongly anti-correlated, indicating that enhancement in NO_x concentrations leads to decrease in O₃ concentrations. Moreover, the O₃ concentrations are more sensitive to NO_x concentrations in the rural region than in the city region. The ratios of Δ[O₃]/Δ[NO_x] are ?2.3 and ?0.25 in the rural and in the city region, respectively. In addition, the measured NO_x and SO₂ concentrations are strongly correlated, highlighting that the NO_x and SO₂ are probably originated from same emission sources. Because SO₂ emissions are significantly originated from coal burnings, the strong correlation between SO₂ and NO_x concentrations suggests that the NO_x emission sources are mostly from coal burned sources. As a result, the future automobile increases could lead to rapid enhancements in O₃ concentrations in the YRD region.