Optimization of the design of air quality monitoring networks and its application to NO2 and O3 in Jaen,Spain

The assessment of air quality is necessary in order to control and reduce pollution to levels which minimise harmful effects on human health and the environment. This paper describes a method to design air quality monitoring networks for nitrogen dioxide and ozone and its application in Jaen (southern Spain). A fibre-glass filter impregnated with triethanolamine was used in diffusive sampling badges for NO₂ determination. For O₃ analysis, sodium nitrite was selected and nitrate, a product of the reaction of ozone and nitrite, was used to assess the ozone concentrations. Sampling campaigns with passive diffusion samplers at 62 sites were then carried out to obtain information on the pollution emissions in Jaen. The sampling campaigns in 2001–2002 revealed an average concentration of 10.4 μg/m³ NO₂ with maximum values up to 22.5 μg/m³ in Jaen City centre. The average ozone concentrations were recorded downwind from the emission source, reaching 96.2 μg/m³; the average ozone value in Jaen was 72.0 μg/m³. After spatial interpolation of the obtained values with Geographical Information Systems, a selection of the best locations for the monitoring stations was made, in line with the macro- and microscale siting requirements of the European Directive 2008/50/EC on ambient air quality and cleaner air for Europe. A second sampling campaign with diffusive samplers was carried out in 2005–2006 to control if the locations of the air quality assessment stations were still representative for their zone.     

Design of air quality monitoring networks and its application to NO2 and O3 in Cordova, Spain

Air monitoring networks are necessary to assess air quality in order to reduce pollution to levels which minimise harmful effects on human health and the environment. This paper describes a method to design air quality monitoring networks for nitrogen dioxide and ozone and its application in Cordova, Andalusia, southern Spain. The city has a population of 325,453 inhabitants and traffic is its main source of air pollution. The first step of this method made it possible to determine from historical data that two control stations for NO₂ and one control stations for O₃ are necessary according to the legislation. Sampling campaigns with passive diffusion samplers at 81 sites were then carried out to obtain information on the pollution distribution in Cordova. The sampling campaigns in 2001–2002 revealed an average concentration of 19.5 μg/m³ for NO₂ with maximum values up to 28.6 μg/m³ in Cordova city centre. The average ozone concentrations were recorded downwind from the emission source, reaching 91.8 μg/m³; the average ozone value in Cordova was 65.3 μg/m³. After spatial interpolation of the obtained values with Geographical Information Systems, a selection of the best locations for the monitoring stations was made, in line with the macro- and microscale siting requirements of the European Directive 2008/50/EC on ambient air quality and cleaner air for Europe. A second sampling campaign with diffusive samplers was carried out in 2007 to control if the locations of the air quality assessment stations were still representative for their zone.     

Direct observation of spin-forbidden formation of O(D) in the near-UV photolysis of ozone

Time-of-flight measurements have been made of the O(¹D) fragment following the photolysis of ozone in the near-UV. At 321.9 nm fragments are seen with kinetic energies the values of which are those expected from spin-forbidden dissociation with ground state O₂(X³Σ_g⁻) molecules as the co-product. Spin-allowed dissociation of internally excited ozone molecules is also seen to produce translationally cold O(¹D) and O₂(a¹Δ_g) products. The implications for the dissociation of tropospheric ozone are briefly discussed.     

Analysis of ambient ozone and precursor monitoring data in a densely populated residential area of Kuwait

Analysis of ozone (O₃) pollution in the Salmiyah residential area of Kuwait was conducted over a period of 12 months, from March 2008 to February 2009. Salmiyah is a densely populated area, mainly by expatriates. Apartment buildings are the dominant type of dwellings available in Salmiyah. The area is surrounded by major highways that get congested with traffic at peak hours of the day. The objectives of this work were: to monitor ambient tropospheric levels of O₃ and its precursors both for test comparing such levels to international standard limits and for assessing their health effects, to understand their diurnal behaviors, and to study their seasonal trends. The results of this study indicated that O₃, nitrogen dioxide (NO₂), and non-methane hydrocarbons (NMHC) exceeded the ambient air quality standards during specific times of the year. The diurnal patterns for NO₂ and NMHC showed three peaks which were directly dependent on high traffic density, while only two daily maxima were observed in the case of O₃. Finally, O₃ compared to its precursors exhibited a completely opposite monthly mean distribution with the highest concentration levels detected during the summer season (July and August).     

Kinetics of Active Oxygen Species with Implications for Atmospheric Ozone Chemistry

Photochemical processes involving singlet oxygen (O₂(a¹Δ)), oxygen atoms_, and ozone are critical in determining atmospheric ozone concentrations. Here we report on kinetic measurements and modeling that examine the importance of the reactions of vibrationally excited ozone. Oxygen atoms and O₂(a¹Δ) were produced by UV laser photolysis of ozone. Time‐resolved absorption spectroscopy was used for O₃ concentration measurements. It was found that vibrationally excited ozone formed by O + O₂ + M → O₃(ν) + M recombination reacts effectively with O₂(a¹Δ) and O atoms. The reaction O₃(υ) + O₂(a¹Δ) → O + 2O₂ results in a reduction of the ozone recovery rate due to O atom regeneration, whereas the reaction O₃(υ) + O → 2O₂ removes two odd oxygen species, resulting in incomplete ozone recovery. The possible impact of these reactions on the atmospheric O₂(a¹Δ) and O₃ budgets at altitudes in the range of 80–100 km is considered.     

Air quality monitoring network design to control nitrogen dioxide and ozone, applied in Malaga, Spain

Air monitoring networks are necessary to assess air quality in order to reduce pollution to levels which minimize harmful effects on human health and the environment. This paper describes a method to design or optimize air quality monitoring networks for nitrogen dioxide and ozone and its application in Malaga, a medium large city located in Andalusia, southern Spain, with traffic being the main source of air pollution. The completion of this method revealed that the old assessment network in Malaga was badly designed and made it possible to determine that one traffic-orientated and one background control station were necessary for NO₂ assessment in Malaga, as well as two control stations for O₃. First the number of stations necessary is obtained from historical data. Sampling campaigns with passive diffusion samplers at 74 sites were then carried out to obtain information on the pollution distribution in Malaga. The average concentrations found for NO₂ and O₃ were 22.8 μg/m³ and 64.3 μg/m³ respectively. Maximum values of up to 42.2 μg/m³ NO₂ were found in Malaga city centre and O₃ reached 91.5 μg/m³ downwind from the emission source. After spatial interpolation of the obtained values with Geographical Information Systems, a selection of the best locations for the monitoring stations was made, in line with the macro- and microscale siting requirements of the European Directive 2008/50/EC on ambient air quality and cleaner air for Europe.     

Deactivation of vibrationally excited ozone by O(3P) atoms

Using laser-induced fluorescence of ozone (to measure the rate of disappearance of O₃²) and NO₂ titration (to determine O atom concentrations), we have determined bimolecular rate constants for the deactivation by O(³P atoms) of ozone in excited stretching and bending modes. These experiments do not distinguish between deactivation by (a) the exchange of vibrational and translational energy or (b) the chemical reaction O₃ + O → 2O₂. If the non-reactive pathway (a) is assumed to dominate, then O(³P) is 150 times more effective than O₂ in deactivating O²₃. If chemical reaction (b) is dominant, the bimolecular rate constant for O²₃ + O(³P) is larger by a factor of 150–1500 than that for ground-state ozone.     

Ozone monitoring in a Mediterranean forest using diffusive and continuous sampling

Ambient ozone was measured in a forest in Castelporziano (Italy) characterised by the prevailing presence of Holm-oak trees (Quercus ilex L.) from June to November 2003. Two methods for measuring ozone were used: long-term monitoring using diffusive samplers at three heights within the canopy, and continuous monitoring at two heights using the UV method. Results for one week mean ozone levels above and below the canopy from the diffusive samplers were compared to those obtained using the automatic analyser at the same levels. A good correlation between the two sampling techniques was found. Continuous monitoring showed a daily cycle with a midday maximum and a nocturnal minimum. While the forest floor consistently had the lowest ozone concentration, there were no differences during most daytime hours. The midday maximum is clearly due to downward mixing with O₃-rich air from above. The night-time ozone decay within the canopy is the result of dry deposition of O₃ and most likely due to reaction with biogenically produced NO. AOT40 within and above the canopy mostly exceeded the critical levels.     

Ground level ozone (O3) associated with radon (222Rn) and particulate matter (PM) concentrations in Bucharest metropolitan area and adverse health effects

The aim of this paper is to contribute with new information in the application of ground based radon (²²²Rn) observations to atmospheric research, namely its relation with air pollution due to ground-level ozone (O₃) and particle matter in two size fractions (PM10 and PM2.5) for Bucharest metropolitan area in Romania. During January 1–December 31, 2011, ground levels of radon, ozone and particulate matter (PM) have been continuously monitored in synergy with the main meteorological parameters (air temperature, humidity and pressure), and daily global air quality indices. A systematic analysis of surface ozone observations of ground level radon, ozone and PM is presented. Observational results indicate the following yearly daily mean ground level concentrations: 40.26 ± 7.54 Bq/m³ for radon, 90.51 μg/m³ for ozone, 35.96 μg/m³ for PM2.5, and 40.91 μg/m³ for PM10. The assessment of the results showed the influence of local and meteorological conditions on the daily mean radon, ozone and PM concentrations. However, in densely populated metropolitan area of Bucharest the mean daily values of ozone, PM2.5, PM10, and attached ²²²Rn are sometimes higher than European Community limit values leading to serious public concern during the last years. Due to the high risk of increased levels of O₃, PM2.5, PM10, and attached ²²²Rn on human health respiratory function (especially for children and older persons), and urban green, the results are very useful for atmospheric, radiological protection, epidemiological and environmental studies.     

THE STIMULATING EFFECT OF A COLD, DARK PRETREATMENT ON THE ETIOPLAST/CHLOROPLAST TRANSFORMATION OF ANGIOSPERMS–II. SYNERGISM BETWEEN RED-LIGHT and COLD PRETREATMENT ON THE CO2- and O2-GAS-EXCHANGE OF WHEAT LEAVES

Abstract— Recently we reported on the stimulating effect of a cold, dark pretreatment on the processes of greening of dark-grown angiosperms under continuous white light (Schönbohm et al., 1988; Physiol. Plant. 72 ,541–546). These effects could be nullified by a subsequent second dark phase (25°C) which precedes the white light period. Our analysis was now focused on the effect of cold, dark pretreatments (with or without red-preirradiation) on the gas exchange (O₂; CO₂) of etiolated primary leaves of wheat during a subsequent white light period. The following results were obtained: (1) The net-O₂-consumption under continuous white light decreased much more quickly after a cold than after a warm pretreatment. (2) This effect was enhanced by red-preirradiation. (3) The O₂-compensation point was reached more quickly during the de-etiolation period when the leaves had been subjected to a cold instead to a warm pretreatment. (4) The “cold-effect” could be nullified by a subsequent warm, dark pretreatment (in this material the compensation point could not be reached within 8 h). (5) Cold treated material which had also been exposed to red light showed during the first 30 min of de-etiolation an extremely strong ^“out-burst” of CO₂. No correlation was apparent between the O₂-uptake and this high CO₂-release. (6) A cold, dark pretreatment induces a decrease of CO₂-release during the second half of the de-etiolation period. This effect could be nullified by a secondary warm, dark treatment given after the cold, dark pretreatment. Our experiments indicate that red-preirradiation and cold, dark pretreatment stimulate chlorophyll synthesis (Schonbohm et al., 1988) and also photosynthetic O₂-evolution and CO₂-uptake. We also assume that this pretreatment causes CO₂ release that is neither directly related to the respiratory electron transport chain nor to the photorespiration.     

Semiconductor Sensors for Studying the Heterogeneous Destruction of Ozone at Low Concentrations

Prospects for the use of semiconductor resistive sensors in studies of the heterogeneous destruction of ozone at low concentrations (5–400 μg/m³) were shown. The influence of various factors (sensor temperature, gas flow rate, ozone concentration) on the results of ozone concentration measurements with sensors of various types was studied. Methods for forming a sensitive layer of In₂O₃(3% Fe₂O₃) sensors with specified parameters of calibration curves were proposed. The optimum conditions for the operation of sensors in a flow mode were formulated. The results of the study of heterogeneous destruction of ozone on microfiber polymer and natural disperse (sand, coals) materials obtained by the developed method were presented.     

Spectroscopic measurement of the free radicals NO3, BRO,IO, and OH in the troposphere

Free radicals are the driving force for most chemical processes in the atmosphere. In particular OH- and nitrate radicals (NO₃) play a central role in the troposphere. However, recent investigations indicate an important influence of the halogen-oxide radicals BrO, IO, and possibly ClO on tropospheric chemistry. Therefore, the knowledge of the concentration of those species in the atmosphere is a key requirement for the investigation of atmospheric chemistry. Unfortunately the low concentration of free radicals makes measurements particularly difficult. Among several techniques applied to the problem UV/visible differential absorption spectroscopy (also known as DOAS) appears to be the most successful for the observation of the above species. Detection limits of the order of 10⁶ to 10⁷ molec/cm³ have been reached, which are sufficiently low to resolve the diurnal variation profiles of the observed radicals. As examples tropospheric DOAS measurements of NO₃- and OH radicals at mid latitudes are presented, as well as observations of BrO in the Canadian Arctic. The latter measurements are discussed with a scenario combining BrO catalyzed ozone loss and atmospheric dispersion to explain the observed rapid changes in ozone with the measured levels of BrO.     

Effect of atmospheric pressure on ozone cracking of rubber

Ozone chamber testing of rubbers occupies a prominent place in the field of polymeric degradation testing. In such testing the rate of ozone cracking of rubber vulcanizates is a function of the rate of collision of ozone molecules with the rubber surface, all other factors constant. However, the conventional mode of expression of the ozone concentration in chamber testing is on a volume O₃ per volume air basis, i.e. parts O₃ per hundred million (10⁸) air by volume, abbreviated by pphm.In this paper we show that at equal ozone concentrations expressed as pphm, cracking rate is a function of the ambient atmospheric pressure (in the chamber). Thus variations in ozone test results may occur in intra- or inter-laboratory testing if ambient atmospheric pressure at the time or place of test is sufficiently different. A mode of expression that avoids this is recommended, i.e. the partial pressure of O₃ in mPa.     

Oxidative decomposition of oxalate ion with ozone in aqueous solution

The oxidation of oxalate ions with ozone in aqueous solution has been studied, and the effects of pH, temperature, and reactant concentrations on the reaction rate and efficiency have been estimated. The oxidative decomposition is most effective in alkaline medium (pH ≥ 10) at 50°C. Under these conditions, the consumption of ozone is 0.6±0.1 g per gram of oxalate or 1.1±0.1 mol per mole of oxalate, which corresponds to the stoichiometry (COO^–)₂ + O₃ + H₂O → 2CO₃^2– + O₂ + 2H⁺.     

Photolysis of ozone in the ultraviolet region. Reactions of O(1D), O2(1Δg) and O≠2

Reactions of O(¹D) and O₂(¹Δ_g) with ozone have been observed time resolved by the detection of the product O³P) and their rate constants have been determined. It is found that vibrationally excited molecular oxygen, O^≠₂, also produces O(³P) in reaction with ozone. These observations are supported by the results of quantum yield determinations of the ozone decomposition in UV-photolysis.     

Mechanism and kinetics of the reaction of ozone with sodium chloride in aqueous solutions

It is shown experimentally that Cl⁻ appreciably accelerates ozone decomposition in water (τ_1/2 = 1.5 h versus 6 h in pure water). The decomposition of ozone in NaCl solutions includes the reversible reaction of ozone with the chloride ion (O₃ + Cl⁻ → O₃⁻ + Cl) as the key step, which is followed by the development of a chain reaction in which chain propagation is performed alternately by the chlorine atom Cl and its monoxide ClO. The current concentrations of the chlorine atom are rather low ([Cl] ∼ 10⁻¹⁴ mol/l). The overall process is satisfactorily described by a first-order rate law with respect to ozone. The decomposition of ozone in aqueous solutions of NaCl is not accompanied by the formation of products other than oxygen. In particular, no noticeable amounts of hypochlorites and chlorates are observed. This is particularly significant for medicinal applications of ozonized isotonic solutions.     

Determination of total and non-water soluble iodine in atmospheric aerosols by thermal extraction and spectrometric detection (TESI)

Iodine has recently been of interest in atmospheric chemistry due to its role in tropospheric ozone depletion, modification of the HO/HO₂ ratio and aerosol nucleation. Gas-phase iodine chemistry is tightly coupled to the aerosol phase through heterogeneous reactions, which are dependent on iodine concentrations and speciation in the aerosol. To date, the only method available for total iodine determination in aerosols is collection on filters by impaction and quantification by neutron activation analysis (NAA). NAA is not widely available to all working groups and is costly to commission. Here, we present a method to determine total iodine concentrations in aerosol impact filter samples by combustion of filter sub-samples (∼5 cm²) at 1,000 °C, trapping in deionised water and quantification by UV/Vis spectroscopy. Both quartz and cellulose filters were analysed from four separate sampling campaigns. The method proved to be sensitive (3σ = 6 ng absolute iodine ≈ 3 pmol m⁻³) precise (RSD ∼ 5%) and accurate, as determined by external and standard addition calibrations. Total iodine concentrations ranged from 10 pmol m⁻³ over the Southern Ocean to 100 pmol m⁻³ over the tropical Atlantic, in agreement with previous estimates. The soluble iodine concentration (extracted with water and measured by ICP-MS) was then subtracted from the total iodine to yield non-water-soluble iodine (NSI). The NSI fraction ranged from 20% to 53% of total iodine, and thus can be significant in some cases.     

Rate coefficient for the reaction of CCl3 radicals with ozone

The rate coefficient for the reaction of CCl₃ radicals with ozone has been measured at 303 ± 2 K. The CCl₃ radicals were generated by the pulsed laser photolysis of carbon tetrachloride at 193 nm. The time profile of CCl₃ concentration was monitored with a photoionization mass spectrometer. Addition of the O₃–O₂ mixture to this system caused a decay of the CCl₃ concentration because of the reactions of CCl₃ + O₃ → products (5) and CCl₃ + O₂ → products (4). The decay of signals from the CCl₃ radical was measured in the presence and absence of ozone. In the absence of ozone, the O₃–O₂ mixture was passed through a heated quartz tube to convert the ozone to molecular oxygen. Since the rate coefficient for the reaction of CCl₃ + O₂ could be determined separately, the absolute rate coefficient for reaction ( 5 ) was obtained from the competition among these reactions. The rate coefficient determined for reaction ( 5 ) was (8.6 ± 0.5) × 10^?13 cm³ molecule^?1 s^?1 and was also found to be independent of the total pressure (253–880 Pa of N₂). This result shows that the reaction of CCl₃ with O₃ cannot compete with its reaction with O₂ in the ozone layer. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 310–316, 2003     

An Ozone Generator of Miniaturization and Modularization with the Narrow Discharge Gap

The method of ionization discharge has a key action on the process of the ionization and decomposition of O₂ molecule as well as the re-decomposition of O₃ molecule. In this paper, an ozone generation of miniaturization which was fabricated by stacking discharge modules with rectangle is introduced, only volume of 23.0×53.0×42.0 cm³ for ozone production capacity of 1 kg/hr. In addition, the ozone concentration and its production efficiency are significantly improved in comparison with a conventional ozone generator, which have the highest ozone concentration of 308 g/Nm³ and the production efficiency of 118 g/kWh at ozone concentration of 200 g/Nm³.     

Mercury in atmospheric aerosols: A preliminary case study for the city of Krakow,Poland

The level of contamination by mercury associated with airborne particulate matter in Krakow was determined. Samples of PM10 were collected on quartz filters using low-volume samplers. The total particulate mercury (TPM) concentrations in collected samples were determined by mercury analyser MA-3000 (Nippon Instruments Corporation). The reported results include also data on the carbonaceous aerosol and inorganic ions concentrations during the reported sampling campaign. The average concentration of the Total Particulate Mercury (TPM) in Krakow (Poland) was 0.22 ng·m⁻³ (during the period from 22 February to 2 March) and 0.49 ng·m⁻³ (on 3 March). A marked correlation between TPM and elemental carbon (EC) as well as with Cl^– was found. No significant association of the TPM with NO₃^– and SO₄^2– could be shown. The dry deposition flux of mercury was calculated as an average over the sampling period and was 47.3 ng·m⁻²·d⁻¹.