Impact of downward-mixing ozone on surface ozone accumulation in southern Taiwan

The ozone that initially presents in the previous day's afternoon mixing layer can remain in the nighttime atmosphere and then be carried over to the next morning. Finally, this ozone can be brought to the ground by downward mixing as mixing depth increases during the daytime, thereby increasing surface ozone concentrations. Variation of ozone concentration during each of these periods is investigated in this work. First, ozone concentrations existing in the daily early morning atmosphere at the altitude range of the daily maximum mixing depth (residual ozone concentrations) were measured using tethered ozonesondes on 52 experimental days during 2004-2005 in southern Taiwan. Daily downward-mixing ozone concentrations were calculated by a box model coupling the measured daily residual ozone concentrations and daily mixing depth variations. The ozone concentrations upwind in the previous day's afternoon mixing layer were estimated by the combination of back air trajectory analysis and known previous day's surface ozone distributions. Additionally, the relationship between daily downward-mixing ozone concentration and daily photochemically produced ozone concentration was examined. The latter was calculated by removing the former from daily surface maximum ozone concentration. The measured daily residual ozone concentrations distributed at 12-74 parts per billion (ppb) with an average of 42 +/- 17 ppb are well correlated with the previous upwind ozone concentration (R2 = 0.54-0.65). Approximately 60% of the previous upwind ozone was estimated to be carried over to the next morning and became the observed residual ozone. The daily downward-mixing ozone contributes 48 +/- 18% of the daily surface maximum ozone concentration, indicating that the downward-mixing ozone is as important as daily photochemically produced ozone to daily surface maximum ozone accumulation. The daily downward-mixing ozone is poorly correlated with the daily photochemically produced ozone and contributes significantly to the daily variation of surface maximum ozone concentrations (R2 = 0.19). However, the contribution of downward-mixing ozone to daily ozone variation is not included in most existing statistical models developed for predicting daily ozone variation. Finally, daily surface maximum ozone concentration is positively correlated with daily afternoon mixing depth, attributable to the downward-mixing ozone.     

Meteorologically adjusted long-term trend of ground-level ozone concentrations in Kaohsiung County,southern Taiwan

Since meteorological changes strongly affect ambient ozone concentrations, trends in concentrations of ozone upon the adjustment of meteorological variations are important of evaluating emission reduction efforts. The goal of this work is to study meteorological effects on the long-term trends of ozone concentration using a multi-variable additive model. Data on the hourly concentrations of ozone were collected from four air-quality stations from 1997 to 2006 in Kaohsiung County to determine the monthly, seasonal and annual average concentrations of ozone. The model incorporates seven meteorological parameters – pressure, temperature, relative humidity, wind speed, wind direction, duration of sunshine and cloud cover. The simulated results show that the long-term ozone concentration increases at 13.84% (or 13.06%) monthly (or annually) after meteorological adjustments, less than at 26.10% (or 23.80%) without meteorological adjustments. Wind speed, duration of sunshine and pressure are the three dominant factors that influence the ground-level ozone levels.     

Effects of reactive hydrocarbons and hydrogen peroxide on antioxidant activity in cherry leaves

One-year-old cherry trees were fumigated with propene and gas-phase hydrogen peroxide, singly and in combination, in controlled-environment chambers for an 8-week period during the summer season. A UV light source was included with the combined propene and hydrogen peroxide regime to provide a source of hydroxyl radicals and ozone, and thus all the constituents of a photochemical smog. Measurements were made of soluble protein concentration and of glutathione reductase activity in leaf extracts from two or three leaf classes in plants from each treatment regime at the end of each fumigation period. Significant increases in soluble protein concentration with respect to the controls were found in plants fumigated with propene and hydrogen peroxide. The occurrence and extent of these differences depended on the leaf class and on the timing of the fumigation period over the summer with respect to bud break. The activity of glutathione reductase was found to be significantly increased in mature lower leaves of plants which had been fumigated with hydrogen peroxide. This effect was independent of the timing of fumigation with respect to bud break. Enzyme activity was also increased in propene and in propene plus hydrogen peroxide treatments, but only when plants were fumigated early in the growth season.     

Effects of open burning of rice straw on concentrations of atmospheric polycyclic aromatic hydrocarbons in central Taiwan

The sizes and concentrations of 21 atmospheric polycyclic aromatic hydrocarbons (PAHs) were measured at Jhu-Shan (a rural site) and Sin-Gang (a town site) in central Taiwan in October and December 2005. Air samples were collected using semi-volatile sampling trains (PS-1 sampler) over 16 days for rice-straw burning and nonburning periods. These samples were then analyzed using a gas chromatograph with a flame-ionization detector (GC/FID). Particle-size distributions in the particulate phase show a bimode, peaking at 0.32-0.56 microm and 3.2-5.6 microm at the two sites during the nonburning period. During the burning period, peaks also appeared at 0.32-0.56 microm and 3.2-5.6 microm at Jhu-Shan, with the accumulation mode (particle size between 0.1 and 3.2 microm) accounting for approximately 74.1% of total particle mass. The peaks at 0.18-0.32 microm and 1.8-3.2 microm at Shin-Gang had an accumulation mode accounting for approximately 70.1% of total particle mass. The mass median diameter (MMD) of 3.99-4.35 microm in the particulate phase suggested that rice-straw burning generated increased numbers of coarse particles. The concentrations of total PAHs (sum of 21 gases + particles) at the Jhu-Shan site (Sin-Gang site) were 522.9 +/- 111.4 ng/ml (572.0 +/- 91.0 ng/ml) and 330.1 +/- 17.0 ng/ml (or 427.5 +/- 108.0 ng/ml) during burning and nonburning periods, respectively, accounting for a roughly 58% (or 34%) increase in the concentrations of total PAHs due to rice-straw burning. On average, low-weight PAHs (about 87.0%) represent the largest proportion of total PAHs, followed by medium-weight PAHs (7.1%), and high-weight PAHs (5.9%). Combustion-related PAHs during burning periods were 1.54-2.57 times higher than those during nonburning periods. The results of principal component analysis (PCA)/absolute principal component scores (APCS) suggest that the primary pollution sources at the two sites are similar and include vehicle exhaust, coal/wood combustion, incense burning, and incineration emissions. Open burning of rice straw was estimated to contribute approximately 5.0-33.5% to the total atmospheric PAHs at the two sites.     

Source profiles and ozone formation potentials of volatile organic compounds in three traffic tunnels in Kaohsiung,Taiwan

Twenty-five volatile organic compounds (VOCs) up to C10 were measured using Carbotrap multibed thermal adsorption tubes during the morning and afternoon rush hours on four different days in all three traffic tunnels in Kaohsiung, Taiwan. A gas chromatograph (GC) equipped with a flame-ionization detector (FID) was then used to analyze the VOCs. The analytical results show that VOC concentrations increase with traffic flow rate, and emission profiles in the three tunnels are mostly in the range C2-C6. In addition to the traffic conditions and vehicle type, the pattern of emissions in each tunnel was also influenced by other factors, such as vehicle age, nearby pollution sources, and the spatial or temporal variation of VOCs in the urban atmosphere. The ozone formation potential (OFP) in each tunnel was assessed based on the maximum incremental reactivities of the organic species, demonstrating that OFP increases with traffic flow rate. Vehicle distribution influences the contributions of organic group to OFP in a tunnel. Meanwhile, when ranked in descending order of contribution to OFP in all tunnels, the organic groups followed the sequence olefins, aromatics, and paraffins.     

Effects of 10% biofuel substitution on ground level ozone formation in Bangkok,Thailand

The Thai Government's search for alternatives to imported petroleum led to the consideration of mandating 10% biofuel blends (biodiesel and gasohol) by 2012. Concerns over the effects of biofuel combustion on ground level ozone formation in relation to their conventional counterparts need addressing. Ozone formation in Bangkok is explored using a trajectory box model. The model is compared against O₃, NO, and NO₂ time concentration data from air monitoring stations operated by the Thai Pollution Control Department. Four high ozone days in 2006 were selected for modeling. Both the traditional trajectory approach and a citywide average approach were used. The model performs well with both approaches but slightly better with the citywide average. Highly uncertain and missing data are derived within realistic bounds using a genetic algorithm optimization. It was found that 10% biofuel substitution will lead to as much as a 16 ppb peak O₃ increase on these four days compared to a 48 ppb increase due to the predicted vehicle fleet size increase between 2006 and 2012. The approach also suggests that when detailed meteorological data is not available to run three dimensional airshed models, and if the air is stagnant or predominately remains over an urban area during the day, that a simple low cost trajectory analysis of O₃ formation may be applicable.     

The southern hemisphere ozone hole split in 2002

Among the most important aspects of the atmospheric pollution problem are the anthropogenic impacts on the stratospheric ozone layer, the related trends of the total ozone content drop and the solar ultraviolet radiation enhancement at the Earth's surface level. During September 2002, the ozone hole over the Antarctic was much smaller than in the previous six years. It has split into two separate holes, due to the appearance of sudden stratospheric warming that has never been observed before in the southern hemisphere. The analysis of this unprecedented event is attempted, regarding both the meteorological and photochemical aspects, in terms of the unusual thermal field patterns and the induced polar vortex disturbances.     

Revised estimates of construction activity and emissions: Effects on ozone and elemental carbon concentrations in southern California

Emissions from diesel-powered construction equipment are an important source of nitrogen oxides (NO_x) and particulate matter (PM). A new emission inventory for construction equipment emissions is developed based on surveys of diesel fuel use; the revised inventory is compared to current emission inventories. California's OFFROAD model estimates are 4.5 and 3.1 times greater, for NO_x and PM respectively, than the fuel-based estimates developed here. The most relevant uncertainties are the overall amount of construction activity/diesel fuel use, exhaust emission factors for PM and NO_x, and the spatial allocation of emissions to county level and finer spatial scales. Construction permit data were used in this study to estimate spatial distributions of emissions; the resulting distribution is well correlated with population growth. An air quality model was used to assess the impacts of revised emission estimates. Increases of up to 15 ppb in predicted peak ozone concentrations were found in southern California. Elemental carbon and fine particle mass concentrations were in better agreement with observations using revised emission estimates, whereas negative bias in predictions of ambient NO_x concentrations increased.     

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.     

Effects of ozone and simulated acid rain on birch seedling growth and formation of ectomycorrhizae

Four-week-old paper birch (Betula papyrifera Marsh.) seedlings, inoculated or non-inoculated with the ectomycorrhizal fungus Pisolithus tinctorius (Pers.) Coker & Couch and grown in steamed or non-steamed soil, were exposed to ozone (O(3)) and/or simulated acid rain (SAR). Plants were exposed to O(3) for 7 h per day on 5 days per week for 12 weeks. O(3) concentrations were maintained between 0.06 and 0.08 ppm. SAR was applied 10 min per day on 2 days per week. O(3), SAR, soil regime and mycorrhizal treatment did not significantly affect any of the measured variables. Interactions between O(3) and SAR, SAR and mycorrhizal treatment, soil regime and mycorrhizal treatment and ozone and soil regime had significant effects. Treatment of seedlings with pH 3.5 SAR caused increases in growth which were more apparent in birch exposed to O(3). Mucorrhizal treatment caused increased growth in non-steamed soil, while growth appeared to decrease in steamed soil. Birch seedlings grew much better in steamed soil. The implications of increased growth in steamed soil may demonstrate the importance of looking at the secondary effects of pollutants on soil-borne organisms.     

Atmospheric ozone: formation and effects on vegetation

Ozone (O(3)) is present both in the troposphere and the stratosphere. Troposphere O(3) is predominantly produced by photochemical reactions involving precursors generated by natural processes and to a much larger extent by man's activities. There is evidence for a trend towards increasing tropospheric O(3) concentrations. However, tropospheric O(3) is known to account for only 10% of the vertical O(3) column above the earth's surface. The stratosphere accounts for an additional 90% of the O(3) column. There is evidence to suggest that there are losses in the stratospheric O(3) due to the updraft of O(3) destroying pollutants generated by both natural processes and by human activity. Such a loss in stratospheric O(3) can result in alterations of incidence in the ultraviolet (UV) radiation to the earth's surface. Tropospheric O(3) is known to be highly phytotoxic. Appropriate exposures to O(3) can result in both acute (symptomatic) and chronic (changes in growth, yield or productivity and quality) effects. Chronic effects are of great concern in terms of both crops and forests. A number of experimental techniques are available to evaluate the chronic effects of O(3) on plants. There are limitations attached to the use of these techniques. However, results obtained, with such techniques are valuable if interpreted in the appropriate context. Among all field evaluation techniques, open-top chambers are the most frequently used method for evaluating the chronic effects of O(3) on crops. The National Crop Loss Assessment Program (NCLAN) of the United States is the largest such effort. However, given the limitations of the open-top chambers and the experimental aspects of NCLAN, its results must be interpreted with caution. On the other hand, acute effects can be evaluated with less complexity through the use of biological indicator plants. The numerical modelling of such effects are also far less complicated than establishing numerical cause and effects relationships for chronic effects. Confounding the acute or chronic responses of plants to O(3), is the presence of other kinds and forms of pollutants in the ambient atmosphere and the incidence of pathogens and pests. The resulting complex interactions and joint effects on plants are poorly understood. Future research must address these issues. In the final analysis we have re-emphasized the fact that plant health is the product of its interaction with the physical and chemical climatology and pathogens and pests. What we have described in this context is the importance of tropospheric O(3) within the chemical climatology of our environment and its effects on vegetation.     

Photochemical ozone formation in the Sydney airshed

The theoretical photostationary state relationship, k₃[O₃][NO]/k₁[NO₂] = 1, was tested in the free atmosphere using data obtained from a series of air mass trajectory experiments which were performed as part of the Sydney Oxidant Study. These data show that in general, the relationship was valid to within a factor of two for the Sydney airshed when three minute averaged concentration measurements were used. The effects of various averaging times upon the experimental photostationary state relationship arc discussed.     

Summertime photochemical ozone formation in Santiago,Chile

The city of Santiago, Chile experiences frequent high pollution episodes and as a consequence very high ozone concentrations, which are associated with health problems including increasing daily mortality and hospital admissions for respiratory illnesses. The development of ozone abatement strategies requires the determination of the potential of each pollutant to produce ozone, taking into account known mechanisms and chemical kinetics in addition to ambient atmospheric conditions. In this study, the photochemical formation of ozone during a summer campaign carried out from March 8–20, 2005 has been investigated using an urban photochemical box model based on the Master Chemical Mechanism (MCMv3.1). The MCM box model has been constrained with 10 min averages of simultaneous measurements of HONO, HCHO, CO, NO, j(O¹D), j(NO₂), 31 volatile organic compounds (VOCs) and meteorological parameters. The O₃–NO_x–VOC sensitivities have been determined by simulating ozone formation at different VOC and NO_x concentrations. Ozone sensitivity analyses showed that photochemical ozone formation is VOC-limited under average summertime conditions in Santiago. The results of the model simulations have been compared with a set of potential empirical indicator relationships including H₂O₂/HNO₃, HCHO/NO_y and O₃/NO_z. The ozone forming potential of each measured VOC has been determined using the MCM box model. The impacts of the above study on possible summertime ozone control strategies in Santiago are discussed.     

The ozone formation potential of 1-bromo-propane

1-Bromo-propane (1-BP) is a replacement for high-end chlorofluorocarbon (HCFC) solvents. Its reaction rate constant with the OH radical is, on a weight basis, significantly less than that of ethane. However, the overall smog formation chemistry of 1-BP appears to be very unusual compared with typical volatile organic compounds (VOCs) and relatively complex because of the presence of bromine. In smog chamber experiments, 1-BP initially shows a faster ozone build-up than what would be expected from ethane, but the secondary products containing bromine tend to destroy ozone such that 1-BP can have a net overall negative reactivity. Alternative sets of reactions are offered to explain this unusual behavior. Follow-up studies are suggested to resolve the chemistry. Using one set of bromine-related reactions in a photochemical grid model shows that 1-BP would be less reactive toward peak ozone formation than ethane with a trend toward even lower ozone impacts in the future.     

Trends in concentration of ground-level ozone and meteorological conditions during high ozone episodes in the Kao-Ping Airshed, Taiwan

This work analyzes the variations in daily maximum 1-hr ozone (O3) concentrations and the long-term trends in annual means of hourly ambient concentrations of O3, nitrogen oxides (nitrous oxide + nitrogen dioxide), and nonmethane hydrocarbons in the three administrative regions of Kao-Ping airshed in southern Taiwan over a recent 8-yr period. The annual or monthly means of all maxima, most 95th percentiles, and some 90th percentiles of the daily maximum 1-hr O3 concentrations exceed the daily limit of 120 parts per billion by volume in all three regions, namely, Kao-hsiung City, Kso-hsiung County, and P'ing-tung County. The monthly means of daily maximum 1-hr O3 concentrations exhibit distinct seasonal variations, with a bimodal form with the maxima in autumn and late winter to the middle of spring and a minimum in summer. The long-term variations in the annual means of hourly O3 concentrations in the three regions exhibit increasing trends. These increases in O3 are associated with the decline in ambient concentrations of nitrogen oxides and nonmethane hydrocarbons. High O3 episodes occur most often in autumn and most rarely in summer. The seasonal mean mixing heights in descending order follow the order of spring, summer, autumn, and winter. Meteorological parameters in autumn and winter indicate that the ground-level O3 tends to accumulate and trigger a high O3 episode on a warm day with sufficient sunlight and low wind in a high-pressure system, consistent with the low mixing heights in these two seasons.     

Photochemical production of ozone and control strategy for Southern Taiwan

An observation-based method (OBM) is developed to evaluate the ozone (O₃) production efficiency (O₃ molecules produced per NO_x molecule consumed) and O₃ production rate (P(O₃)) during a field campaign in southern Taiwan. The method can also provide an estimate of the concentration of OH. A key step in the method is to use observed concentrations of two aromatic hydrocarbons, namely ethylbenzene and m,p-xylene, to estimate the degree of photochemical processing and amounts of photochemically consumed NO_x and NMHCs by OH. In addition, total oxidant (O₃+NO₂) instead of O₃ itself turns out to be very useful for representing ozone production in the OBM approach. The average O₃ production efficiency during the field campaign in Fall (2003) is found to be about 10.2±3.9. The relationship of P(O₃) with NO_x is examined and compared with a one-dimensional (1D) photochemical model. Values of P(O₃) derived from the OBM are slightly lower than those calculated in the 1D model. However, OH concentrations estimated by the OBM are about a factor of 2 lower than the 1D model. Fresh emissions, which affect the degree of photochemical processing appear to be a major cause of the underestimate. We have developed a three-dimensional (3D) OBM O₃ production diagram that resembles the EKMA ozone isopleth diagram to study the relationship of the total oxidant versus O₃ precursors. The 3D OBM O₃ production diagram suggests that reducing emissions of NMHCs are more effective in controlling O₃ than reducing NO_x. However, significant uncertainties remain in the OBM, and considerable more work is required to minimize these uncertainties before a definitive control strategy can be reached. The observation-based approach provides a good alternative to measuring peroxy radicals for evaluating the production of O₃ and formulating O₃ control strategy in urban and suburban environments.     

Meteorologically adjusted trends of daily maximum ozone concentrations in Taipei,Taiwan

The meteorological conditions exert large impacts on ozone concentrations, and may mask the long-term trends in ozone concentrations resulting from precursor emissions. Estimation of long-term trends of ozone concentrations due to the changes in precursor emissions is important for corresponding control strategy. Multiple linear regression (method I), multilayer perceptron (MLP) neural network (method II) and Komogorov-Zurbenko (KZ) filter method plus MLP methodology (method III), are used to estimate the meteorologically adjusted long-term trends of daily maximum ozone concentrations by removing the masking effects of meteorological conditions in this study. The daily maximum ozone concentrations and relative meteorological variables were extracted from six air-monitoring stations in Taipei area from 1994 to 2001. The data collected during 1994–2000 period were used as modeling set and utilized to estimate the meteorologically adjusted trends, and the data of 2001 were used as the validation data. The meteorologically adjusted trends of ozone for these three methods were calculated and compared. The results show that both MLP and KZ filter +MLP models are more suitable than multiple linear regression for estimating the long-term trends of ozone in Taipei, Taiwan. The long-term linear trends of meteorologically adjusted ozone concentrations due to the precursor emissions show an increase trend at all stations, and the percent changes per year range from 1.0% to 2.25% during the modeling period in Taipei area.     

臭氧对活性污泥特性影响研究

探讨了臭氧对于污水生物处理中活性污泥特性的影响。结果显示 ,随着臭氧化的进行 ,促进了活性污泥生物量的减少 ,并有一定量的生物污泥被无机化 ,并且污泥的活性和存活性降低了。其中臭氧投加量低于 0 .1gO3 /gSS时污泥活性即大幅下降 ,而后污泥浓度才随着臭氧量的增加而显著降低。     

Anaerobic degradation of five polycyclic aromatic hydrocarbons from river sediment in Taiwan

This study investigated the anaerobic degradation of five polycyclic aromatic hydrocarbons (PAHs) from Erren River sediment in southern Taiwan. The degradation rates of PAH were in the order: acenaphthene > fluorene > phenanthrene > anthracene > pyrene. The degradation rate was enhanced when the five compounds were present simultaneously in river sediment. Comparison of the PAH degradation rates under three reducing conditions showed the following order: sulfate-reducing conditions > methanogenic conditions > nitrate-reducing conditions. The addition of electron donors (acetate, lactate and pyruvate) enhanced PAH degradation under methanogenic and sulfate-reducing conditions. However, the addition of acetate, lactate or pyruvate inhibited PAH degradation under nitrate-reducing conditions. The addition of heavy metals, nonylphenol and phthalate esters (PAEs) inhibited PAH degradation. Our results show that sulfate-reducing bacteria, methanogen and eubacteria are involved in the degradation of PAH; sulfate-reducing bacteria constitute a major microbial component in PAH degradation. Of the microorganism strains isolated from the sediment samples, we found that strain ER9 expressed the greatest biodegrading ability.