UV Fourier transform measurements of tropospheric O3, NO2, SO2, benzene, and toluene.

Using the differential optical absorption spectroscopy (DOAS) technique and a Fourier transform spectrometer, NO2, SO2, O3, benzene. and toluene were measured during three measurement campaigns held in Brussels in 1995, 1996, and 1997. The O3 concentrations could be explained as the results of the local photochemistry and the dynamical properties of the mixing layer. NO2 concentrations were anti-correlated to the O3 concentrations, as expected. SO2 also showed a pronounced dependence on car traffic. Average benzene and toluene concentrations were, respectively 1.7 ppb and between 4.4 and 6.6 pbb, but high values of toluene up to 98.8 ppb were observed. SO2 concentrations and to a lesser extent, those of NO2 and 03, were dependent on the wind direction. Ozone in Brussels has been found to be influenced by the meteorological conditions prevailing in central Europe. Comparisons with other measurements have shown that 03 and SO2 data are in general in good agreement, but our NO2 concentrations seem to be generally higher.     

Simultaneous DOAS and mist-chamber IC measurements of HONO in Houston,TX

Nitrous acid is an important component of nighttime N-oxide chemistry, and provides a significant source of both OH and NO in polluted urban air masses shortly after sunrise. Several recent studies have called for new sources of HONO to account for daytime levels much higher than are consistent with current understanding. However, measurement of HONO is problematic, with most in-situ techniques reporting higher values than simultaneous optical measurements by long-path DOAS, especially during daytime. The discrepancy has been attributed to positive interference in the in-situ techniques, negative interference in DOAS retrievals, the difficulty of comparing the different air masses sampled by the methods, or combinations of these.During August and September 2006, HONO mixing ratios from collocated long-path DOAS and automated mist-chamber/ion chromatograph (MC/IC) systems ranged from several ppbv during morning rush hour to daytime minima near 100 pptv. Agreement between the two techniques was excellent across this entire range during many days, showing that both instruments accurately measured HONO during this campaign. A small bias towards higher LP-DOAS observations at night can be attributed to slow vertical mixing leading to pronounced HONO profiles. A positive daytime bias of the MC/IC instrument during several days in late August/early September was correlated with photochemically produced compounds such as ozone, HNO₃ and HCHO, but not with NO₂, NO_x, HO₂NO₂, or the NO₂ photolysis rate. While an interferant could not be identified organic nitrites appear a possible explanation for our observations.     

Variations in methane and nitrous oxide mixing ratios at the southern boundary of a Canadian boreal forest

Diurnal and seasonal variations in methane (CH₄) and nitrous oxide (N₂O) mixing ratios were measured above a boreal aspen stand at the southern boundary of the Canadian boreal forest, about 5 km north of agricultural land. The research was conducted between 16 April and 16 September 1994, in the Prince Albert National Park, Saskatchewan, to better understand patterns of CH₄ and N₂O cycling in boreal ecosystems. The research also presents a method for detecting the long-range transport of trace gases using a micrometeorological, laser-based gas monitoring system. Both CH₄ and N₂O featured diurnal cycles consistent with a pattern of net emission for each trace gas. The CH₄ mixing ratio displayed a seasonal variation that was strongly related to soil temperature, with measured values roughly 30 ppb higher in the late summer than in spring. During the latter half of the experiment, the CH₄ mixing ratios varied with wind direction and suggested areas of higher emission to the northeast and east of the measurement tower. The N₂O fluxes also showed favoured directions, although in this case the highest mixing ratios were measured during the springtime in air masses originating south and southwest of the tower. The high springtime values coincided with spring thaw emissions of N₂O from agricultural fields to the south, and the results suggest that the trace gas analysis system detected the long-range transport of N₂O from the agricultural land. Ammonia and ammonium likewise may be transported to the southern boreal forest from agricultural land, and a future investigation at this site could seek to determine the effect of their long-range transport on the southern boreal forest.     

The Estimation of Personal Exposures to Air Pollutants for a Community-Based Study of Health Effects in Asthmatics—Design and Results of Air Monitoring

In order to provide reliable pollutant and meteorological exposure estimates for an epidemiological study of asthmatics residing in two Houston neighborhoods, a dedicated three-tier air monitoring system was established. This consisted of fixed site ambient air monitoring at the center of each study area, a mobile van performing simultaneous indoor and outdoor measurements at selected residences of study participants, and a limited amount of direct personal monitoring for half of the participants. Monitored pollutants Included all criteria pollutant gases, as well as aeroallergens, aldehydes, TSP, and IP. Laboratory analyses provided concentrations of sulfate, nitrate, and trace elements. Continuous measurements of several meteorological parameters also were obtained. Intensive quality assurance and data validation efforts resulted in a high percentage of valid data for most pollutants. Ozone was the only measured pollutant that exceeded the NAAQS during the six-month (May to October) study period. The monitoring scheme allowed important pollutant concentration differences to be detected between day and night, between Indoors and outdoors, and among various indoor environments. The use of these monitoring data in combination with personal activity and household characteristics data to generate estimates of personal exposures for the epidemiological analysis will be described in a subsequent paper.     

Preparing to Measure the Effects of the NOx SIP Call— Methods for Ambient Air Monitoring of NO,NO2, NOy,and Individual NOz Species

Abstract

The capping of stationary source emissions of NO_x in 22 states and the District of Columbia is federally mandated by the NO_x SIP Call legislation with the intended purpose of reducing downwind O₃ concentrations. Monitors for NO, NO₂, and the reactive oxides of nitrogen into which these two compounds are converted will record data to evaluate air quality model (AQM) predictions. Guidelines for testing these models indicate the need for semicontinuous measurements as close to real time as possible but no less frequently than once per hour. The measurement uncertainty required for AQM testing must be less than ±20% (±10% for NO₂) at mixing ratios of 1 ppbv and higher for NO, individual NO_z component compounds, and NO_y. This article is a review and discussion of different monitoring methods, some currently used in research and others used for routine monitoring. The performance of these methods is compared with the monitoring guidelines. Recommendations for advancing speciated and total NO_y monitoring technology and a listing of demonstrated monitoring approaches are also presented.     

Variability of SO2, CO,and light hydrocarbons over a megacity in Eastern India: effects of emissions and transport

The Indo-Gangetic plain (IGP) has received extensive attention of the global scientific community due to higher levels of trace gases and aerosols over this region. Satellite retrievals and model simulations show that, in particular, the eastern part IGP is highly polluted. Despite this attention, in situ measurements of trace gases are very limited over this region. This paper presents measurements of SO₂, CO, CH₄, and C₂–C₅ NMHCs during March 2012–February 2013 over Kolkata, a megacity in the eastern IGP, with a focus on processes impacting their levels. The mean SO₂ and C₂H₆ concentrations during winter and post-monsoon periods were eight and three times higher compared to pre-monsoon and monsoon. Early morning enhancements in SO₂ and several NMHCs during winter connote boundary layer effects. Daytime elevations in SO₂ during pre-monsoon and monsoon suggest impacts of photo-oxidation. Inter-species correlations and trajectory analysis evince transport of SO₂ from regional combustion sources (e.g., coal burning in power plants, industries) along the east of the Indo-Gangetic plain impacting SO₂ levels at the site. However, C₂H₂ to CO ratio over Kolkata, which are comparable to other urban regions in India, show impacts of local biofuel combustions. Further, high levels of C₃H₈ and C₄H₁₀ evince the dominance of LPG/petrochemicals over the study location. The suite of trace gases measured during this study helps to decipher between impacts of local emissions and influence of transport on their levels.     

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.     

Statistical and diagnostic evaluation of a new-generation urban dispersion modelling system against an extensive dataset in the Helsinki area

We have developed a modelling system for predicting the traffic volumes, emissions from stationary and vehicular sources, and atmospheric dispersion of pollution in an urban area. This paper describes a comparison of the NO_x and NO₂ concentrations predicted using this modelling system with the results of an urban air quality monitoring network. We performed a statistical analysis to determine the agreement between predicted and measured hourly time series of concentrations at four permanently located and three mobile monitoring stations in the Helsinki Metropolitan Area in 1996–1997 (at a total of ten urban and suburban measurement locations). At the stations considered, the so-called index of agreement values of the predicted and measured time series of the NO₂ concentrations vary between 0.65 and 0.82, while the fractional bias values range from −0.29 to +0.26. In comparison with corresponding results presented in the literature, the agreement between the measured and predicted datasets is good, as indicated by these statistical parameters. The seasonal variations of the NO₂ concentrations were analysed in terms of the relevant meteorological parameters. We also analysed the difference between model predictions and measured data diagnostically, in terms of meteorological parameters, including wind speed and direction (the latter separately for two wind speed classes), atmospheric stability and ambient temperature, at two monitoring stations in central Helsinki. The modelling system tends to overpredict the measured NO₂ concentrations both at the highest (u⩾6 m s⁻¹) and at the lowest wind speeds (u<2 m s⁻¹). For higher wind speeds, the modelling system overpredicts the measured NO₂ concentrations in certain wind direction intervals; specific ranges were found for both monitoring stations considered. The modelling system tends to underpredict the measured concentrations in convective atmospheric conditions, and overpredict in stable conditions. The possible physico-chemical reasons for these differences are discussed.     

Modelling the photochemical pollution over the metropolitan area of Porto Alegre,Brazil

The main purpose of this study is to evaluate the photochemical pollution over the Metropolitan Area of Porto Alegre (MAPA), Brazil, where high concentrations of ozone have been registered during the past years. Due to the restricted spatial coverage of the monitoring air quality network, a numerical modelling technique was selected and applied to this assessment exercise. Two different chemistry-transport models – CAMx and CALGRID – were applied for a summer period, driven by the MM5 meteorological model. The meteorological model performance was evaluated comparing its results to available monitoring data measured at the Porto Alegre airport. Validation results point out a good model performance. It was not possible to evaluate the chemistry models performance due to the lack of adequate monitoring data. Nevertheless, the model intercomparison between CAMx and CALGRID shows a similar behaviour in what concerns the simulation of nitrogen dioxide, but some discrepancies concerning ozone. Regarding the fulfilment of the Brazilian air quality targets, the simulated ozone concentrations surpass the legislated value in specific periods, mainly outside the urban area of Porto Alegre. The ozone formation is influenced by the emission of pollutants that act as precursors (like the nitrogen oxides emitted at Porto Alegre urban area and coming from a large refinery complex) and by the meteorological conditions.     

Factors Influencing the Variability of SO2 Concentrations in Istanbul

ABSTRACT

The correlation between sulfur dioxide (SO₂) concentrations measured at the European and Asian sides of Istanbul and meteorological parameters is investigated using principal component analysis (PCA) and multiple regression analysis techniques. Several meteorological parameters are selected to represent the atmospheric conditions during two winter periods: 1993–1994 and 1994–1995. Six principal components are found to explain the majority of the observed meteorological variability. Surface pressure, 850-mb temperature, and surface zonal (east-west) and meridional (north-south) winds show high loadings on separate factors identified by PCA. We seek dominant meteorological parameters that control the SO₂ levels at each monitoring station. Several multiple regression analysis models are fitted to the data from each monitoring station using six principal components and previous day SO₂ concentrations as independent variables.

Results suggest that the most important parameters, highly correlated with SO₂ concentrations in the Istanbul metropolitan area, are atmospheric pressure and surface zonal and meridional winds. These components have more influence on the determination of the air pollution levels at the Asian side than at the European side.     

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

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

Estimation of atmospheric trace metal emissions in Vilnius City, Lithuania, using vertical concentration gradient and road tunnel measurement data

A new approach for the estimation of trace metal emissions in Vilnius city was implemented, using vertical concentration profiles in the urban boundary layer and road tunnel measurement data. Heavy metal concentrations were examined in fine and coarse particle fractions using a virtual impactor (cut-off size diameter 2.5 μm). Negative vertical concentration gradients were obtained for all metals (Ba, Pb, V, Sb, Zn) and both fractions. It was estimated that the vertical concentration gradient was formed due to emissions from an area of about 12 km². Road tunnel measurements indicated that trace metal concentrations on fine particles were lower than those on coarse particles, which suggested that re-emitted road dust was highly enriched in trace metal due to historic emissions within the tunnel. Emission rates of different pollutants in the road tunnel were calculated using pollutant concentration differences at the tunnel entrance and exit and traffic flow data. Heavy metal emission rates from the area of Vilnius city were estimated using the vertical gradient of heavy metal concentrations and the coefficient of turbulent mixing, as derived from meteorological measurement data. The emission values calculated by the two different methods coincided reasonably well, which indicated that the main source of airborne trace metals in Vilnius city is traffic. The potential of the vertical concentration gradient method for the direct estimation of urban heavy metal emissions was demonstrated.     

Sulfur dioxide dispersion and source contribution to receptors of downtown Patras, Greece

Background The development of the city of Patras, including harbour relocation, in conjunction with the protection of the regional ecosystems, requires air quality assessment and management. For this reason, a model applicable in the Patras area is necessary and valuable. The goal of this study was to validate a model suitable for predicting the dispersion of sulfur dioxide (SO₂), based on particular activity, topography and weather conditions. Methods We used the US-EPA ISCLT3 integral dispersion model to predict SO₂ concentrations for Patras, Greece. We assumed that the major contribution to Patras air pollution came from central heating, harbour and traffic. We calculated traffic emissions using COPERTIII. Results and Discussion Assigning suitable values of the mixing height, the model predicted the local and spatial distribution of the mean monthly SO₂ concentrations in downtown Patras, as well computed the contribution of the SO₂ emissions originating from each particular source at each receptor location on a seasonal and annual basis. The comparison between predictions and measurements shows that the model performance for estimating the SO₂ concentrations and period pattern is satisfactory. Conclusion The mixing height was the critical parameter for calibrating the model. Model validation promises satisfactory predictions for SO₂ pollution levels on monthly basis. Recommendations and Outlook The model could be used in predicting SO₂ concentrations and source contribution for several downtown Patras receptors using pertinent meteorological and emission information. It could be also extended to predict the dispersion of other primary air pollutants. The calibrated model predictions could be used to fill gaps in monitoring data, saving money and time, and help in assess and manage air quality as Patras develops.     

Investigation of adsorption characteristics of four toxic gases (nitric oxide,nitrogen dioxide,sulfur dioxide,and hydrogen chloride) on the inner surface of nickel-coated manganese steel cylinders and aluminum cylinders

To develop standard toxic gas mixtures, it is essential to identify adsorption characteristics of each toxic gas on the inner surface of a gas cylinder. Thus, this study quantified adsorbed amounts of the four toxic gases (nitric oxide [NO], nitrogen dioxide [NO₂], sulfur dioxide [SO₂], and hydrogen chloride [HCl]) on the inner surface of aluminum cylinders and nickel-coated manganese steel cylinders. After eluting adsorbed gases on the inside of cylinders with ultrapure water, a quantitative analysis was performed on an ion chromatograph. To evaluate the reaction characteristics of the toxic gases with cylinder materials, quantitative analyses of nickel (Ni), iron (Fe), and aluminum (Al) were also performed by inductively coupled plasma optical emission spectrometry (ICP-OES). It was found that the amounts of NO, NO₂, and SO₂ adsorbed on the inner surface of aluminum cylinders were less than 1.0% at the level of 100 μmol/mol mixing ratio, whereas the signal for most heavy metal elements were below their respective detection limits. This study found that the amounts of HCl adsorbed on the inner surface of nickel-coated manganese steel cylinders were less than 5% at the level of 100 μmol/mol mixing ratio, whereas Ni (86 μmol) and Fe (28 μmol) were detected in the same cylinders. It was revealed that the adsorption mainly took place via the reaction of HCl with inner surface material of nickel-coated manganese steel cylinders. On the other hand, in the case of aluminum cylinders, the amounts of the adsorption were determined to be less than 1% at the level of HCl 100 μmol/mol mixing ratio, whereas most of Ni, Fe, and Al were detected at levels similar to their limits of detection. As a result, this study found that aluminum cylinders are more suitable for preparing HCl gas mixtures than nickel-coated manganese steel cylinders.

Implications: To develop a standard toxic gas mixture, it is essential to understand the adsorption characteristics of each toxic gas inside a gas cylinder. It was found that the amounts of NO, NO₂, and SO₂ adsorbed inside aluminum cylinders were less than 1.0% at the level of 100 μmol/mol mixing ratio. The amounts of HCl adsorbed inside nickel-coated manganese steel cylinders were less than 5% at the level of 100 μmol/mol mixing ratio, whereas those inside aluminum cylinders were less than 1%, indicating that aluminum cylinders are more suitable for preparing HCl gas mixtures.     

COS,CS2 and SO2 in aluminium smelter exhaust

Measurements of carbonyl sulfide (COS) and carbondisulfide (CS₂) were carried out on samples drawn from a smoke stack of an aluminium smelter. Volume mixing ratios of 6 ppm COS and 0.1 ppm CS₂ were measured for gases from the electrolysis unit that had previously passed an Al₂O₃ fluid bed reactor and electrostatic precipitators. Specific emissions of 1.6 kg COS and 0.03 kg CS₂ per ton of primary aluminium were found. Extrapolating from this particular smelter’s conditions to a world mix specific COS emissions of about 4 kg/t(Al) are calculated resulting in emissions of annually 0.08 Tg COS into the atmosphere due to electrolytic aluminium production in 1995. Besides the photochemical conversion of anthropogenic CS₂ aluminium production is established to be the second major industrial source of COS probably exceeding automotive tire wear’s and coal combustion’s contributions.     

An observational study of the HONO–NO2 coupling at an urban site in Guangzhou City,South China

The temporal behavior of HONO and NO₂ was investigated at an urban site in Guangzhou city, China, by means of a DOAS system during the Pearl River Delta 2006 intensive campaign from 10 to 24 July 2006. Within the whole measurement period, unexpected high HONO mixing ratios up to 2 ppb were observed even during the day. A nocturnal maximum concentration of about 8.43 ± 0.4 ppb was detected on the night of 24 July 2006. Combining the data simultaneously observed by different instruments, the coupling of HONO–NO₂ and the possible formation sources of HONO are discussed. During the measurement period, concentration ratios of HONO to NO₂ ranged from (0.03 ± 0.1) to (0.37 ± 0.09), which is significantly higher than previously reported values (0.01–0.1). Surprisingly, in most cases a strong daytime correlation between HONO and NO₂ was found, contrary to previous observations in China. Aerosol was found to have a minor impact on HONO formation during the whole measurement period. Using a pseudo steady state approach for interpreting the nocturnal conversion of NO₂ to HONO suggests a non-negligible role of the relative humidity for the heterogeneous HONO formation from NO₂.     

Simultaneous sampling of NH3, HNO3, HC1, SO2 and H2O2 in ambient air by a wet annular denuder system

A new sampling device is described for the simultaneous collection of NH₃, HNO₃, HCl, SO₂ and H₂O₂ in ambient air. The apparatus is based on air sampling by two parallel annular denuder tubes. The gases are collected by absorption in solutions present in the annulus of the denuder tubes. After a sampling time of 30 min at flow rate of 32 ℓ min⁻¹ the solutions are extracted from the denuders and analyzed off-line. The detection limits of NH₃, HNO₃, HCL and SO₂ are in the order of 0.1–0.5 μm⁻³. For H₂O₂ the detection limit is 0.01 μm⁻³. The reproducibility is 5–10% at the level of ambient air concentrations. Comparison of this novel technique with existing methods gives satisfactory results. The compact set-up offers the possibility of field experiments without the need of extensive equipment.     

Heterogeneous reactions of soot aerosols with nitrogen dioxide and nitric acid: atmospheric chamber and Knudsen cell studies

Heterogeneous chemical processes involving trace atmospheric gases with solid particulates, such as carbonaceous aerosol, are not well understood. In an effort to quantify some relevant carbon aerosol systems, the heterogeneous chemistry of NO₂ with both commercial and freshly prepared hexane soot was investigated in an atmospheric reaction chamber. At approximately an atmosphere of total pressure (760 Torr) and under dry conditions (relative humidities⩽1%), kinetic measurements gave an uptake coefficient of (2.4±0.6)×10⁻⁸ for n-hexane soot when referenced to the BET surface area of the sample. Commercial carbon black samples were found to yield a similar uptake coefficient. The reaction of HNO₃ with commercial carbon black was also investigated and gas phase NO₂ was detected as a reaction product. Low-pressure Knudsen cell experiments were carried out to facilitate a quantitative comparison between the two different techniques. The agreement between our current results and previously reported values of the uptake coefficient, with different soot samples and under varied pressure and surface coverage conditions, are discussed along with the possible implications for atmospheric chemistry.     

Temporal Variations of PM2.5, PM10, and Gaseous Precursors during the 1995 Integrated Monitoring Study in Central California

ABSTRACT

The spatial and temporal distributions of particle mass and its chemical constituents are essential for understanding the source-receptor relationships as well as the chemical, physical, and meteorological processes that result in elevated particulate concentrations in California’s San Joaquin Valley (SJV). Fine particulate matter ₍PM_2.5), coarse particulate matter (PM₁₀), and aerosol precursor gases were sampled on a 3-hr time base at two urban (Bakersfield and Fresno) and two non-urban (Kern Wildlife Refuge and Chowchilla) core sites in the SJV during the winter of 1995–1996.

Day-to-day variations of PM_2.5 and PM₁₀ and their chemical constituents were influenced by the synoptic-scale meteorology and were coherent among the four core sites. Under non-rainy conditions, similar diurnal variations of PM_2.5 and coarse aerosol were found at the two urban sites, with concentrations peaking during the nighttime hours. Conversely, PM_2.5 and coarse aerosol peaked during the morning and afternoon hours at the two non-urban sites. Under rainy and foggy conditions, these diurnal patterns were absent or greatly suppressed.

In the urban areas, elevated concentrations of primary pollutants (e.g., organic and elemental carbons) during the late afternoon and nighttime hours reflected the impact from residential wood combustion and motor vehicle exhaust. During the daytime, these concentrations decreased as the mixed layer deepened. Increases of secondary nitrate and sulfate concentrations were found during the daylight hours as a result of photochemical reactions. At the non-urban sites, the same increases in secondary aerosol concentrations occurred during the daylight hours but with a discernable lag time. Concentrations of the primary pollutants also increased at the non-urban sites during the daytime. These observations are attributed to mixing aloft of primary aerosols and secondary precursor gases in urban areas followed by rapid transport aloft to non-urban areas coupled with photochemical conversion.     

Computing surface concentration fluxes of trace gases from a variational method using measured variance and single-level concentration data

Surface fluxes of O₃, CO₂ and SO₂ were estimated from a variational method by using measured concentrations and variances of these trace gases. The measurements were taken over a deciduous forest when it was fully leafed during the summer of 1988 and when it was leafless during the winter of 1990. A flux–variance relation and a flux–gradient relation were employed as constraints in a cost function which is minimized to find the optimal estimate of concentration fluxes of the gases under study. Fluxes of O₃, CO₂ and SO₂ from the variational method were compared with fluxes estimated by the flux–variance relation and measured using an eddy correlation technique. Results show that the variational method improves the estimates of fluxes.