Photochemical ozone and nitric oxide formation in air-nitrogen dioxide mixtures containing sulfur dioxide or chlorine

Experiments were performed to investigate the effects of sulfur dioxide (0–10 ppm) and chlorine (0–15 ppm) on ozone and nitric oxide concentrations in irradiated mixtures of nitrogen dioxide (1–5 ppm) and air. The mixtures were irradiated by ultraviolet fluorescent lamps while flowing at a steady speed through a 9m long, 15.2cm i.d. Pyrex tube. The presence of sulfur dioxide produced no measurable change in the ozone and nitric oxide concentrations. The addition of small quantities of chlorine increased the ozone concentration in much the same manner as the addition of a hydrocarbon. A reaction model was developed for the chlorine-nitrogen dioxide-air mixtures. The observed increase in ozone concentration could only be predicted if the following two reactions were included : ClOO + NO → NO₂ + ClO and ClOO + NO → ClNO + O₂. Significant quantities of unexpected condensation nuclei were also observed in the chlorine-nitrogen dioxide-air mixtures.     

Aircraft measurement of ozone turbulent flux in the atmospheric boundary layer

In May 1995, the “Chimie-Creil 95” experiment was undertaken in the north of France. The field data are first used to validate the methodology for airborne measurement of ozone flux. A certain number of methodological problems due to the location of the fast ozone sensor inside the airplane are, furthermore discussed. The paper describes the instrumentation of the ARAT (Avion de Recherche Atmosphérique et de Télédétection), an atmospheric research and remote-sensing aircraft used to perform the airborne measurements, the area flown over, the meteorological conditions and boundary layer stability conditions. These aircraft measurements are then used to determine ozone deposition velocity and values are proposed for aerodynamic, bulk transfer coefficients (ozone and momentum). The paper also establishes the relationship between the normalised standard deviation and stability parameters (z/L) for ozone, temperature, humidity and vertical velocity. The laws obtained are then presented.     

Particulate and sulfur dioxide concentration measurements in Patras,Greece

The purpose of this study was to obtain a better assessment of the Patras, Greece, air quality, in terms of the primary pollutants total suspended particulates (TSPs) and sulfur dioxide (SO2), because limited and short-duration measurements have been conducted in the past. Installation and operation of a mobile air monitoring station at two different locations in the Patras downtown area and one location in the outskirts of the city was undertaken and covered the periods July 1, 1994-January 30, 1995; March 18-August 23, 1995; and April 19-July 27, 1996, respectively. For both pollutants measured at each location, the monthly average concentrations and typical weekly variation of daily averages, as well as the diurnal variations and frequency concentration distributions in each month of the monitoring periods, were calculated and are presented in bar diagrams. The annual and winter period medians and the annual 98th percentile were also calculated and are compared with the limit and guide values provided by the European Economic Community Council Directive 80/779/EEC. In addition, comparison of SO2 values is made with the limit values adopted by the more recent Directive 1999/30/EC. It was found that the TSP and SO2 levels at all locations were very low and were lower than the levels found in Thessaloniki and Athens, Greece. An attempt to explain what had been measured is also undertaken. The data presented are considered essential for future reference and comparison purposes.     

Lagrangian measurements of sulfur dioxide to sulfate conversion rates

On the basis of Project MISTT data and proposed homogeneous gas phase oxidation mechanisms for sulfur dioxide, it has been suggested that the degree of mixing with background air, the chemical composition of the background air, and the intensity of the sunlight available are key factors determining the rate of sulfur dioxide to sulfate conversion. These hypotheses are examined in light of Lagrangian measurements of conversion rates in power plant plumes made during the Tennessee Plume Study and Project Da Vinci. It is found that the Lagrangian conversion rate measurements are consistent with these hypotheses. It has also been suggested that the concentration of ozone may serve as a workable surrogate for the concentrations of the free radicals involved in the homogeneous gas phase mechanism. The night-time Lagrangian data remind one that the gross difference in mean lifetime of ozone and free radicals can lead to situations in which the ozone concentration is not a good surrogate for the free radical concentrations.     

Tethered balloon measurements of biogenic VOCs in the atmospheric boundary layer

Biogenic volatile organic compounds (BVOCs) were measured on tethered balloon platforms in 11 deployments between 1985 and 1996. A series of balloon sampling packages have been used to describe boundary layer dynamics, BVOC distribution, chemical transformations of BVOCs, and to estimate BVOC emission rates from terrestrial vegetation. Measurements indicated a slow decrease of concentration for BVOCs with altitude in the mixed layer when sampling times were greater than average convective turnover time; surface layer concentrations were more variable because of proximity to various emission sources in the smaller surface layer footprint. Mixed layer concentrations of isoprene remained fairly constant in the middle of the day, in contrast to canopy-level isoprene concentrations, which continued to increase until early evening. Daytime emissions, which increase with temperature and light, appear to be balanced by changes in entrainment and oxidation. Daytime measurements of methacrolein and methyl vinyl ketone, reaction products of the atmospheric oxidation of isoprene, showed fairly constant ratio to each other with altitude throughout the mixed layer. BVOC emission flux estimates using balloon measurements and from the extrapolation of leaf level emissions to the landscape scale were in good agreement.     

Aircraft measurements of the vertical distribution of sulfur dioxide and aerosol scattering coefficient in China

Information on the vertical distribution of air pollution is important for understanding its sources and processes and validating satellite retrievals and chemical transport models. This paper reports the results of the measurements of sulfur dioxide (SO₂) and aerosol scattering coefficient (B_sp) obtained from several aircraft campaigns during summer and autumn 2007 in the north-eastern (NE), north-western (NW), and central-eastern (CE) regions of China. Their vertical profiles over the three regions with contrasting emission characteristics and climates are compared. Very high concentrations/values of SO₂ and B_sp (with a value of up to 51 ppbv and 950 Mm^?1, respectively) were recorded in the lower planetary boundary layer in CE China, indicating high SO₂ emissions in the region. The SO₂ column concentrations determined from the in-situ measurements were compared with Ozone Monitoring Instrument (OMI) SO₂ retrievals. The results show that the OMI data could distinguish the varying levels of SO₂ pollution in the study regions, but appeared to have underestimated the SO₂ column in the highly polluted region of CE China.     

Urban air pollution modelling and measurements of boundary layer height

An urban field trial has been undertaken with the aim of assessing the performance of the boundary layer height (BLH) determination of two models: the Met Office Unified Model (UM) and a Gaussian-type plume model, ADMS. Pulsed Doppler lidar data were used to measure mixing layer height and cloud base heights for a variety of meteorological conditions over a 3 week period in July 2003. In this work, the daily growth and decay of the BLH from the lidar data and model simulations for 5 days are compared. The results show that although the UM can do a good job of reproducing the boundary layer growth, there are occasions where the BLH is overestimated by 30–100%. Within dispersion models it is the BLH that effectively limits the height to which pollution disperses, so these results have very important implications for pollution dispersion modelling. The results show that correct development of the boundary layer in the UM is critically dependant on morning cloud cover. The ADMS model is used routinely by local authorities in the UK for local air-quality forecasting. The ADMS model was run under three settings; an ‘urban’ roughness, a ‘rural’ roughness and a ‘transition’ roughness. In all cases, the ‘urban’ setting over estimated the BLH and is clearly a poor predictor of urban BLH. The ‘transition’ setting, which distinguishes between the meteorological data input site and the dispersion modelling site, gave the best results under the well mixed conditions of the trial.     

Airborne co2 measurements in the Arctic during spring 1983

A set of flask air samples collected from aircraft in March and April 1983 during the Arctic Gas and Aerosol Sampling Program has been analyzed for CO₂ concentration. The results show CO₂ variations of several ppm in the Arctic troposphere, and qualitative agreement with measurements made on air samples collected at the surface. The CO₂ measurements together with air-mass characteristics determined during the flights show that CO₂ concentrations in the Arctic result from mixing of polluted air transported into the Arctic from lower latitudes with cleaner air of maritime and continental origins. The CO₂ concentration is found to increase or decrease with altitude which is probably dependent on the details of transport and the presence or absence of marine sources and/or sinks.     

Qualitative and quantitative effects of ozone and/or sulfur dioxide on field-grown potato plants

Solanum tuberosum L. cv Norchip plants were grown in open-top chambers in the summer of 1986. Plants were treated with charcoal-filtered air, nonfiltered air, or nonfiltered air supplemented with 33, 66, or 99% of the ambient ozone (O3) concentrations from 1000 to 2000 h eastern daylight time daily. In addition, plants received charcoal-filtered air plus 0, 0.15 (393 microg m(-3)), 0.34 (891 microg m(-3)), or 0.61 (1598 microg m(-3)) ppm sulfur dioxide (SO2) from 0900 to 1200 h once every 14 d for a total of four treatments. Ozone induced a linear reduction in number and weight of Grade One (> 6.35-cm diameter) potato tubers and in total weight of tubers. Ozone also induced linear reductions in the percentage of dry matter of tubers and linear decreases in glucose and fructose content of Grade One tubers. Sulfur dioxide induced a stimulation and then decline of the number, percentage of dry matter, and sucrose content of Grade One tubers. The SO2 response best fit a quadratic curve. No O3 x SO2 interactions were detected for any of the yield or quality functions measured.     

The characteristics of ozone and related compounds in the boundary layer of the South China coast: temporal and vertical variations during autumn season

We present measurements of several trace gases made at a subtropical coastal site in Hong Kong in October and November 1997. The gases include O₃, CO, SO₂, and NO_x. The surface measurement data are compared with those from an aircraft study [Kok et al. J. Geophys. Res. 102 (D15) (1997) 19043–19057], and a subset of the latter is used to show the vertical distribution of the trace gases in the boundary layer. During the study period, averaged concentrations at the surface site for O₃, CO, NO_x, and SO₂ were 50, 298, 2.75, and 1.65 ppbv, respectively. Their atmospheric abundance and diurnal pattern are similar to those found in the “polluted” rural areas in North America. The measured trace gases are fairly well mixed in the coastal boundary layer in the warm South China region. Large variability is indicated from the data. Examination of 10-day, isentropic back trajectories shows that the measured trace gases are influenced by maritime air masses, outflow of pollution-laden continental air, and the mixing of the two. The trajectories capture the contrasting chemical features of the large-scale air masses impacting on the study area. CO, NO_x and SO₂ all show higher concentrations in the strong outflow of continental air, as expected, than those in the marine category. Compared with previously reported values for the western Pacific, the much higher levels found in the marine trajectories in our study suggest the impacts of regional and/or sub-regional emissions on the measured trace gases at the study site. The presence of abundant O₃ and other chemically active trace gases in the autumn season, coupled with high solar radiation and warm weather, suggests that the South China Sea is a photochemically active region important for studying the chemical transformation of pollutants emitted from the Asian continent.     

Production of boundary layer ozone from tropical American Savannah biomass burning emissions

Boundary layer ozone and carbon monoxide were measured at a savannah site in the Orinoco river basin, during the dry and wet seasons. CO and O₃ concentrations recorded around noontime show a good linear correlation, suggesting that the higher ozone levels observed during the dry season are photochemically produced during the oxidation of reactive hydrocarbons in the presence of NO_x both emitted by biomass burning. The rate of photochemical ozone production in the boundary layer ozone by biomass burning calculated from the production ratio ΔO₃/ΔCO (0.17±0.01 v : v) and the amount of CO produced by fires (0.26–1.3 mole m⁻² dry season⁻¹), ranges from 0.6 to 2.6 ppbv h⁻¹ for 8 h of daylight. This O₃ production rate is in fairly good agreement with the value derived from RO₂ radical measurements made in the Venezuelan savannah during the dry season. The net boundary layer production of O₃ from all tropical America savannah fires is estimated to range between 0.28 and 0.36 Tmol O₃ per year, which is about 3 times higher than the O₃ produced from pollution sources in the eastern United States during the summer. An extrapolation to all of the world's savannah would indicate a net boundary layer ozone production of about 1.2 Tmol yr⁻¹. This is discussed in the context of the overall global budget of tropospheric ozone.     

The sensitivity of OMI-derived nitrogen dioxide to boundary layer temperature inversions

We assess the sensitivity of tropospheric nitrogen dioxide (NO₂) derived from the Ozone Monitoring Instrument (OMI), to episodes of temperature inversion in the lower boundary layer. Vertical temperature data were obtained from a 91-m meteorological tower located in the study area, which is centered on the Hamilton Census Metropolitan Area, Ontario, Canada. Hamilton is an industrial city with high traffic volumes, and is therefore subjected to high levels of pollution. Pollution buildup is amplified by frequent temperature inversions which are commonly radiative, but are also induced by local physiography, proximity to Lake Ontario, and regional meteorology. The four-year period from January 2005 to December 2008 was investigated. Ground-level data for validation were obtained from in situ air quality monitors located in the study area. The results indicate that OMI is sensitive to changes in the NO₂ levels during temperature inversions, and exhibits changes which roughly parallel those of in situ monitors. Overall, an 11% increase in NO₂ was identified by OMI on inversion days, compared to a 44% increase measured by in situ monitors. The weekend effect was clearly exhibited under both normal and inversion scenarios with OMI. Seasonal and wind direction patterns also correlated fairly well with ground-level data. Temperature inversions have resulted in poor air quality episodes which have severely compromised the health of susceptible populations, sometime leading to premature death. The rationale for this study is to further assess the usefulness of OMI for population exposure studies in areas with sparse resources for ground-level monitoring.     

The development of sulfur dioxide and ozone exposure profiles that mimic ambient conditions in the rural southeastern united states

A design for constructing experimental mixed-pollutant exposure profiles that reflect regional O₃ and SO₂ ambient air quality is described. The profiles were developed using hour-by-hour O₃ and SO₂ concentration data from monitoring sites in the southeastern United States where slash pine is indigenous. Only sites designated rural or remote, with co-monitored O₃ and SO₂, and at least 75% of the hourly values reported for the period April– October, were used. Each site was characterized by concentration, frequency of occurrence and duration of concentration values, length of time between episodes, and frequency of cooccurrence. A base profile, a 30-day hour-by-hour concentration regime, was constructed using averaged air quality characteristics from the selected sites. Using the base profile, additional regimes were constructed by increasing the concentration of all hourly values above a designated minimum, or by increasing the frequency of occurrence of selected hourly concentrations.     

Nitrate reductase activity of needles of Norway spruce fumigated with different mixtures of ozone, sulfur dioxide, and nitrogen dioxide

Four-year-old spruce clones (Picea abies (L.) Karst.) cultivated in sand and provided with a complete nutrient solution, or a solution deficient in magnesium and calcium, were exposed to the pollutant mixtures SO(2)/NO(2), O(3)/NO(2), and O(3)/SO(2)/NO(2), at realistic concentrations for 32 weeks. Fumigation caused a slight increase of total N contents in current year needles, whereas in one-year-old needles N concentrations did not change. The response of nitrate reductase activity to pollutant stress depended on needle age and nutrient supply, respectively. In one-year-old needles fumigation resulted in a significant inhibition of enzyme activity, particularly in Mg and Ca deficient trees. The combination of all three components proved to be most effective in causing a decrease by 60% compared to the control. In contrast, nitrate reductase activity was stimulated in current year needles, especially by O(3)/NO(2) and O(3)/SO(2)/NO(2). Changes in the activity of nitrate and nitrite reductases are considered as a factor contributing to the high phytotoxic potential of pollutant combinations with NO(2).