Photochemical ozone creation potentials (POCPs) for different emission sources of organic compounds under European conditions estimated with a Master Chemical Mechanism

Through the combined application of a speciated VOC emission inventory and an explicit chemical mechanism, a picture has been put together of the different contributions to photochemical ozone formation from 248 VOC emission source categories. The study has shown that the different VOC emission source categories show vastly different propensities for forming photochemical ozone as indexed by their photochemical ozone creation potentials (POCPs). POCPs range from close to zero for numerous processes, including halocarbon solvent usage, through to over 70 for diesel combustion and some reactive solvent and other product usage applications. The consequences of the large range in POCPs are highlighted for cost-effective VOC emission control strategies across north west Europe.     

Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

Seasonal evolutions of ozone (O3) and its nitrogen precursors (NO, NO2) in urban Sfax (Tunisia)

Seasonal evolution of ozone (O3) and its nitrogen precursors (NO, NO2) in downtown Sfax (Tunisia) was monitored. Nitrogen oxides are shown to be closely related to local vehicle sources. Seasonal ozone levels, however, are shown to be dependent on regional meteorological conditions. High ozone levels are due to the effect of anticyclones and stratosphere intrusions (cut-off lows). Low levels are associated with cyclonic conditions of small vertical range of motion. Other than these particular conditions, ozone levels are shown to be relatively higher in fall and winter seasons, characterised by a very steady atmosphere. Overall, the examined meteorological conditions, the ozone concentrations observed in downtown Sfax are characterised by clear day/night cycles, which can be explained by the significant ventilation of the region.     

The Greenhouse effect: impacts of ultraviolet-B (UV-B) radiation, carbon dioxide (CO2), and ozone (O3) on vegetation

There is a fast growing and an extremely serious international scientific, public and political concern regarding man's influence on the global climate. The decrease in stratospheric ozone (O3) and the consequent possible increase in ultraviolet-B (UV-B) is a critical issue. In addition, tropospheric concentrations of 'greenhouse gases' such as carbon dioxide (CO2), nitrous oxide (N2O) and methane (CH4) are increasing. These phenomena, coupled with man's use of chlorofluorocarbons (CFCs), chlorocarbons (CCs), and organo-bromines (OBs) are considered to result in the modification of the earth's O3 column and altered interactions between the stratosphere and the troposphere. A result of such interactions could be the global warming. As opposed to these processes, tropospheric O3 concentrations appear to be increasing in some parts of the world (e.g. North America). Such tropospheric increases in O3 and particulate matter may offset any predicted increases in UV-B at those locations. Presently most general circulation models (GCMs) used to predict climate change are one- or two-dimensional models. Application of satisfactory three-dimensional models is limited by the available computer power. Recent studies on radiative cloud forcing show that clouds may have an excess cooling effect to compensate for a doubling of global CO2 concentrations. There is a great deal of geographic patchiness or variability in climate. Use of global level average values fails to account for this variability. For example, in North America: 1. there may be a decrease in the stratospheric O3 column (1-3%); however, there appears to be an increase in tropospheric O3 concentrations (1-2%/year) to compensate up to 20-30% loss in the total O3 column; 2. there appears to be an increase in tropospheric CO2, N2O and CH4 at the rate of roughly 0.8%, 0.3% and 1-2%, respectively, per year; 3. there is a decrease in erythemal UV-B; and 4. there is a cooling of tropospheric air temperature due to radiative cloud forcing. The effects of UV-B, CO2 and O3 on plants have been studied under growth chamber, greenhouse and field conditions. Few studies, if any, have examined the joint effects of more than one variable on plant response. There are methodological problems associated with many of these experiments. Thus, while results obtained from these studies can assist in our understanding, they must be viewed with caution in the context of the real world and predictions into the future. Biomass responses of plants to enhanced UV-B can be negative (adverse effect); positive (stimulatory effect) or no effect (tolerant). Sensitivity rankings have been developed for both crop and tree species. However, such rankings for UV-B do not consider dose-response curves. There are inconsistencies between the results obtained under controlled conditions versus field observations. Some of these inconsistencies appear due to the differences in responses between cultivars and varieties of a given plant species; and differences in the experimental methodology and protocol used. Nevertheless, based on the available literature, listings of sensitive crop and native plant species to UV-B are provided. Historically, plant biologists have studied the effects of CO2 on plants for many decades. Experiments have been performed under growth chamber, greenhouse and field conditions. Evidence is presented for various plant species in the form of relative yield increases due to CO2 enrichment. Sensitivity rankings (biomass response) are agein provided for crops and native plant species. However, most publications on the numerical analysis of cause-effect relationships do not consider sensitivity analysis of the mode used. Ozone is considered to be the most phytotoxic regional scale air pollutant. In the pre-occupation of loss in the O3 column, any increases in tropospheric O3 concentrations may be undermined relative to vegetation effects. As with the other stress factors, the effects of O3 have been studied both under controlled and field conditions. Thboth under controlled and field conditions. The numerical explanation of cause-effect relationships of O3 is a much debated subject at the present time. Much of the controversy is directed toward the definition of the highly stochastic, O3 exposure dynamics in time and space. Nevertheless, sensitivity rankings (biomass response) are provided for crops and native vegetation. The joint effects of UV-B, CO2 and O3 are poorly understood. Based on the literature of plant response to individual stress factors and chemical and physical climatology of North America, we conclude that nine different crops may be sensitive to the joint effects: three grain and six vegetable crops (sorghum, oat, rice, pea, bean, potato, lettuce, cucumber and tomato). In North America, we consider Ponderosa and loblolly pines as vulnerable among tree species. This conclusion should be moderated by the fact that there are few, if any, data on hardwood species. In conclusion there is much concern for global climate change and its possible effects on vegetation. While this is necessary, such a concern and any predictions must be tempered by the lack of sufficient knowledge. Experiments must be designed on an integrated and realistic basis to answer the question more definitively. This would require very close co-operation and communication among scientists from multiple disciplines. Decision makers must realize this need.     

The radiative efficiency of HCF2OCF2OCF2CF2OCF2H (H-Galden 1040x) revisited

The infrared spectrum of HCF₂OCF₂OCF₂CF₂OCF₂H (CAS# 188690-77-9) has been re-measured. The integrated absorption intensity over the range 1000–1500 cm^?1 measured in the present work is (6.65 ± 0.33) × 10^?17 cm² molecule^?1 cm^?1 in 700 Torr of air at 296 K. The radiative efficiency of HCF₂OCF₂OCF₂CF₂OCF₂H is calculated to be 1.02 W m^?2 ppb^?1. The value reported in the 2007 Intergovernmental Panel on Climate Change (IPCC) report is approximately 35% larger reflecting what we believe to be an erroneously high value for the absorption strength of HCF₂OCF₂OCF₂CF₂OCF₂H adopted by the IPCC.     

Use of passive ambient ozone (O3) samplers in vegetation effects assessment

A stochastistic, Weibull probability model was developed and verified to simulate the underlying frequency distributions of hourly ozone (O3) concentrations (exposure dynamics) using the single, weekly mean values obtained from a passive (sodium nitrite absorbent) sampler. The simulation was based on the data derived from a co-located continuous monitor. Although at the moment the model output may be considered as being specific to the elevation and location of the study site, the results were extremely good. This effort for the approximation of the O3 exposure dynamics can be extended to other sites with similar data sets and in developing a generalized understanding of the stochastic O3 exposure-plant response relationships, conferring measurable benefits to the future use of passive O3 samplers, in the absence of continuous monitoring.     

Comparison of Fe(VI) (FeO4(2-)) and ozone in inactivating Bacillus subtilis spores

The protozoan parasites such as Cryptosporidiumparvum and Giardialamblia have been recognized as a frequent cause of recent waterborne disease outbreaks because of their strong resistance against chlorine disinfection. In this study, ozone and Fe(VI) (i.e., FeO(4)(2-)) were compared in terms of inactivation efficiency for Bacillus subtilis spores which are commonly utilized as an indicator of protozoan pathogens. Both oxidants highly depended on water pH and temperature in the spore inactivation. Since redox potential of Fe(VI) is almost the same as that of ozone, spore inactivation efficiency of Fe(VI) was expected to be similar with that of ozone. However, it was found that ozone was definitely superior over Fe(VI): at pH 7 and 20°C, ozone with the product of concentration×contact time (CˉT) of 10mgL(-1)min inactivate the spores more than 99.9% within 10min, while Fe(VI) with CˉT of 30mgL(-1) min could inactivate 90% spores. The large difference between ozone and Fe(VI) in spore inactivation was attributed mainly to Fe(III) produced from Fe(VI) decomposition at the spore coat layer which might coagulate spores and make it difficult for free Fe(VI) to attack live spores.     

Climate change: potential effects of increased atmospheric carbon dioxide (CO2), ozone (O3), and ultraviolet-B (UV-B) radiation on plant diseases

Continued world population growth results in increased emission of gases from agriculture, combustion of fossil fuels, and industrial processes. This causes changes in the chemical composition of the atmosphere. Evidence is emerging that increased solar ultraviolet-B (UV-B) radiation is reaching the earth's atmosphere, due to stratospheric ozone depletion. Carbon dioxide (CO(2)), ozone (O(3)) and UV-B are individual climate change factors that have direct biological effects on plants. Such effects may directly or indirectly affect the incidence and severity of plant diseases, caused by biotic agents. Carbon dioxide may increase plant canopy size and density, resulting in a greater biomass of high nutritional quality, combined with a much higher microclimate relative humidity. This would be likely to promote plant diseases such as rusts, powdery mildews, leaf spots and blights. Inoculum potential from greater overwintering crop debris would also be increased. Ozone is likely to have adverse effects on plant growth. Necrotrophic pathogens may colonize plants weakened by O(3) at an accelerated rate, while obligate biotroph infections may be lessened. Ozone is unlikely to have direct adverse effects on fungal pathogens. Ozone effects on plant diseases are host plant mediated. The principal effects of increased UV-B on plant diseases would be via alterations in host plants. Increased flavonoids could lead to increased diseased resistance. Reduced net photosynthesis and premature ripening and senescence could result in a decrease in diseases caused by biotrophs and an increase in those caused by necrotrophs. Microbial plant pathogens are less likely to be adversely affected by CO(2), O(3) and UV-B than are their corresponding host plants. Changes in host plants may result in expectable alterations of disease incidence, depending on host plant growth stages and type of pathogen. Given the importance of plant diseases in world food and fiber production, it is essential to begin studying the effects of increased CO(2), O(3) and UV-B (and other climate change factors) on plant diseases. We know very little about the actual impacts of climate change factors on disease epidemiology. Epidemiologists should be encouraged to consider CO(2), O(3) and UV-B as factors in their field studies.     

Ambient ozone (O3) and adverse crop response: a unified view of cause and effect

This paper presents a cohesive view of the dynamics of ambient O(3) exposure and adverse crop response relationships, coupling the properties of photochemical O(3) production, flux of O(3) from the atmosphere into crop canopies and the crop response per se. The results from two independent approaches ((a) statistical and (b) micrometeorological) were analyzed for understanding cause-effect relationships of the foliar injury responses of tobacco cv Bel-W3 to the exposure dynamics of ambient O(3) concentrations. Similarly, other results from two independent approaches were analyzed in: (1) establishing a micrometeorological relationship between hourly ambient O(3) concentrations and their vertical flux from the air into a natural grassland canopy; and (2) establishing a statistical relationship between hourly ambient O(3) concentrations in long-term, chronic exposures and crop yield reductions. Independent of the approach used, atmospheric conditions appeared to be most conducive and the crop response appeared to be best explained statistically by the cumulative frequency of hourly ambient O(3) concentrations between 50 ppb and 90 ppb (100 and 180 microg m(-3)). In general, this concentration range represents intermediate or moderately enhanced hourly O(3) values in a polluted environment. Further, the diurnal occurrence of this concentration range (often approximately between 0900 and 1600 h in a polluted, agricultural environment) coincided with the optimal CO(2) flux from the atmosphere into the crop canopy, thus high uptake. The frequency of occurrence of hourly O(3) concentrations > 90 ppb (180 microg m(-3)) appeared to be of little importance and such concentrations in general appeared to occur during atmospheric conditions which did not facilitate optimal vertical flux into the crop canopy, thus low uptake. Alternatively, when > 90 ppb (180 microg m(-3)) O(3) concentrations occurred during the 0900-1600 h window, their frequency of occurrence was low in comparison to the 50-90 ppb (100-180 microg m(-3)) range. Based on the overall results, we conclude that if the cumulative frequency of hourly ambient O(3) concentrations between 50-62 ppb (100-124 microg m(-3)) occurred during 53% of the growing season and the corresponding cumulative frequency of hourly O(3) concentrations between 50-74 ppb (100-148 microg m(-3)) occurred during 71% of the growing season, then yield reductions in sensitive crops could be expected, if other factors supporting growth, such as adequate soil moisture are not limiting.     

Photochemistry of pesticides, 61). Comparative photochemical studies on methyl 2-benzimidazolecarbamate (Carbendazim) and methyl (1-n-butylcarbamoyl)-2-benzimidazolecarbamate (Benlate) in aqueous hydrochloric acid

The singlet oxygen photolysis of methyl 2-benzimidazolecarbamate (Carbendazim, 1) in aqueous hydrochloric acid has been investigated. 2-Guanidinobenzimidazole 7, benzimidazole 9, 2,4′- (13) and 2,5′-bibenzimidazole 14, were isolated from the reaction products and identified. A comparative study on the singlet oxygen photolysis of Benlate 2 both in MeOH and aqueous hydrochloric acid, was also undertaken.     

The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere

Background, aim, and scope  

Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 ± 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate.     

Investigation of a new approach to decompose two potent greenhouse gases: photoreduction of SF(6) and SF(5)CF(3) in the presence of acetone

In this paper, we addressed the utilization of photochemical method as an innovative technology for the destruction and removal of two potent greenhouse gases, SF(6) and SF(5)CF(3). The destruction and removal efficiency (DRE) of the process was determined as a function of excitation wavelength, irradiation time, initial ratio of acetone to SF(5)X (X represented F or CF(3)), initial SF(5)X concentration, additive oxygen and water vapor concentration. A complete removal was achieved by a radiation period of 55min and 120min for SF(6)-CH(3)COCH(3) system and SF(5)CF(3)-CH(3)COCH(3) system respectively under 184.9nm irradiation. Extra addition of water vapor can enhance DRE by approximately 6% points in both systems. Further studies with GC/MS and FT-IR proved that no hazardous products such as S(2)F(10), SO(2)F(2), SOF(2), SOF(4) were generated in this process.     

Ground-level ozone and ozone vertical profile measurements close to the foothills of the Guadarrama mountain range (Spain)

Continuous measurements of ozone vertical profiles, OVP, in the low troposphere (around 500–2400 m) using an unattended commercial ozone profiler DIAL, were conducted during June–July 2004 in Segovia, SG, a small city in the upper plateau located close to the foothills of the Guadarrama mountain range, Guadarrama, in the Central Massif. The data obtained over almost 37 complete days have enabled us to characterise the ozone vertical exchange, describe the phenomenology of the main ozone peaks, OP, recorded in the city and their relationship with ozone transport/formation from the gas precursor emissions of the greater Madrid area across Guadarrama. To achieve the last objective concurrent measurements of ground-level ozone in SG and a representative monitoring station upwind from Guadarrama, Buitrago de Lozoya, BL, have been used. 72.2% of the concurrent maximum diurnal ozone peaks exceeding the 95 percentile hourly value in SG (OPSG) and BL (OPBL) were linked to ozone transport and formation from the greater Madrid area towards Guadarrama. An estimate of the contribution of the greater Madrid area on OPSG yielded 28 μg m⁻³.The most prominent ozone vertical stratification was linked to the mixing height, MH, and a frequent nocturnal stable layer formed, NSL. Three small ozone enriched-layers were identified at mean heights of 500, 700 and 1000 m, respectively. Ozone tended to decline versus altitude. The hourly patterns of the three layers showed two peak occurrences of similar amplitude in the early morning, 7–8 h, and mid-afternoon, 14–16 h. A minimum was also observed during daytime, 10–11 h, its origin being attributed to a dilution process induced by the “chimney effect” caused by the slopes heating during this period.The comparison between OPSG, and the maximum diurnal ozone peaks in the first layer, OL1P, showed a satisfactory relationship, correlation coefficient, r, of the linear fit 0.77, and comparable mean values, 127 and 130 μg m⁻³, respectively, revealing the presence of an uniform ozone vertical distribution in the 500 m atmospheric layer above ground level during mid-afternoon.     

Biological and photochemical degradation rates of diethylenetriaminepentaacetic acid (DTPA) in the presence and absence of Fe(III)

The environmental fate of ethylenediaminetetraacetic acid (EDTA) has been extensively studied, while much less is known about the environmental behaviour of diethylenetriaminepentaacetic acid (DTPA). In this study, it was confirmed that DTPA is persistent toward biodegradation. The biodegradability of DTPA was investigated in the absence and in the presence of Fe(III) by using CO2 evolution test and Manometric respirometry test. The CO2 evolution and oxygen uptake of iron-free (DTPA was added as free acid) and Fe(III)DTPA were less than in inoculum blank. Possible inhibitor effect was analysed by testing biodegradation of sodium benzoate with and without iron-free or Fe(III)DTPA in the Manometric respirometry test. Only slight inhibition was observed when DTPA was added as free acid. Photodegradation of iron-free DTPA and Fe(III)-DTPA complex was studied by using sunlight and UV radiation at the range 315-400 nm emitted by black light lamps. The results indicate that DTPA added as free acid degrades photochemically in humic lake water. Fe(III)DTPA was shown to be very photolabile in humic lake water in the summer; the photochemical half-life was below one hour. Photodegradation products were identified by the mass spectrometric technique (GC-MS). It was shown that photodegradation of Fe(III)DTPA does not result in total mineralization of the compound. Diethylenetriaminetetraacetic acid, diethylenetriaminetriacetic acid, ethylenediaminetriacetic acid, N,N'- and/or N,N-ethylenediaminediacetic acid, iminodiacetate, ethylenediaminemonoacetic acid and glycine were identified as photodegradation products of Fe(III)DTPA. Based on these observations, we propose a photodegradation pathway for Fe(III)DTPA.     

Effect of ozone on net photosynthesis in oat (Avena sativa) and duckweed (Lemna gibba)

Short exposure to ozone depressed photosynthesis in both oat and duckweed at concentrations above 140 microg m(-3) and 300 microg m(-3), respectively. The effect on exposed oat flag leaves was age-dependent, with maximum susceptibility to ozone 10-20 days after emergence of the panicle. In duckweed, photosynthesis was more sensitive to differences in ozone concentration than to differences in duration of exposure.     

The development and application of a simplified ozone modeling system (SOMS)

This paper describes the development and evaluation of a computationally efficient semi-empirical photochemical model that can be used as a screening tool to obtain quick estimates of the effect of a large number of VOC and NO_x emission control strategies on ozone concentrations. Selected control strategies can subsequently be examined with a more complex model. The model is one component of an ozone management system, the regional ozone decision model (RODM), designed to examine the costs and environmental consequences of alternate ozone abatement strategies.The model was developed by systematic simplification of a detailed photochemical model. At each step of the simplification, the simplified model was tested against observations and against results from the detailed model. The first major simplification was the introduction of a highly parameterized chemistry mechanism, originally developed by Azzi et al. (1992 Proc. 11th Int. Clean Air Conf., 4th Regional IUAPPA Conf.). This modification resulted in a factor of 5 improvement in the computational efficiency of the model. The model with the simplified chemistry was then tested by applying it to a photochemical oxidant episode in the San Joaquin Valley of California. Further improvements in computational speed and efficiency were obtained by uncoupling the chemistry from the transport of VOC and NO_x.