Regional Variations in Sulfate and Nitrate on Annual,Seasonal, and Synoptic Time Scales

ABSTRACT

Ambient data from Interagency Monitoring of Protected Visual Environments (IMPROVE) monitors are analyzed to evaluate the spatial structure of SO₄ and NO₃ aerosols in the mid-Atlantic region. Sub-weekly, seasonal, and annual data values are compared between the IMPROVE Washington, DC, site and three rural sites. Synoptic perturbations are compared between sites to quantify similarities in short-term temporal perturbations of SO₄ and NO₃. Based on these comparisons between the rural and urban IMPROVE monitors, the spatial structure of SO₄ shows broad regional homogeneity that is recognizable from both the long-term average values and the short-term variations.

NO₃ data on a seasonal and annual basis show much larger spatial gradients between the urban Washington monitor and the three rural monitors than do SO₄ data. Short-term NO₃ perturbations at the three rural monitors also differ significantly from those at the Washington site. These dissimilarities in NO₃ levels between the rural and urban IMPROVE monitors on both short-term and longer-term time scales indicate little homogeneity of NO₃ aerosols in the mid-Atlantic region considered here. The volatility of NO₃ aerosols and the removal rate of HNO₃ via dry deposition could contribute to the spatial variability differences shown here between SO₄ and NO₃.     

Geostatistical characterization of nitrogen dioxide concentration in an urban area: Part II: Time component of the estimation error

The temporal component of the estimation error is usually neglected in calculation of the variance of the error associated with the mapping of annual nitrogen dioxide (NO₂) concentration. However, under realistic hypotheses, adding a temporal term to the spatial estimation variance is convenient enough. In a survey using passive diffusion samplers, which was carried out in 2001 on the Mulhouse area, the two measurement phases do not allow calculation of variance of the temporal error. But this error is accessible by means of the few fixed analyzers that continuously measure NO₂ concentrations. The statistics of the experimental temporal error are examined and the temporal variogram is calculated. Experimental quadratic error is then compared to the theoretical estimation variance, deduced from the temporal variogram.The fixed analyzers available in Alsace are then used to “optimize” empirically the duration and the date of the beginning of the temporary measurement phases.Without increasing the cost of the temporary survey, it is then possible to improve the precision of the maps of annual NO₂ concentration, by combining the spatial optimization presented in Part I of the paper, and the temporal optimization presented here.     

Validation of nitrogen dioxide diffusion tube methodology in the UK

Measurement of ambient NO₂ concentrations using diffusion tube samplers is widespread in many countries, particularly in the UK. A National Network of NO₂ diffusion tube samplers has been operational at over 1200 sites in the UK for over 5 years. Some previous studies have indicated that NO₂ diffusion tube samplers may overestimate NO₂ concentrations by up to 30%, whereas others have shown an underestimation. Hence, the UK Department of Environment, Transport and the Regions commissioned this large-scale validation study. In this study diffusion tubes were exposed at 17 urban background monitoring sites equipped with chemiluminescent NO₂ monitors within the UK Automatic Urban Monitoring Network. Over a one year period, diffusion tubes were exposed for 2- and 4-week periods, blacked out or clear and sheltered (from the wind) or unsheltered, in order to investigate the effect of a number of possible variables. The results of the study show that overall average NO₂ concentrations calculated from diffusion tube measurements are likely to be within 10% of chemiluminescent measurement data. The uncertainty on this average difference is ±24–38% for individual diffusion tube measurements, but reduces to ±10–18% for annual averages. Differences due to the exposure period and exposure procedure were found, but these were not large.     

A study of surface ozone and the relation to complex wind flow in Hong Kong

Ozone measurements made from 5 sites in Hong Kong have been analyzed, including those from one upwind, one downwind, and three urban locales. The data are analyzed in terms of the seasonal and diurnal trends. A subset of data in autumn is further analyzed to study the relationship between the ozone spatial pattern and wind flow as well as other meteorological parameters. The results show that averaged ozone levels at most sites exhibit maxima in autumn, which appears to be a unique feature for eastern Asia. On average the daily maximum 1-h concentrations are found to be higher in the western (normally downwind) site than those on the eastern side and in urban areas. Examination of surface wind patterns and other meteorological parameters suggest that elevated ozone concentrations on the western side occur during the days with intense solar radiation, light winds, and in the presence of a unique wind circulation. The wind reversal in the western parts under the “convergence” flow is believed to be an important cause of the high-ozone events observed there. Such wind flow may re-circulate/transport nearby urban plumes (in this case the Hong Kong–Shenzhen urban complex). Examination of chemical data from the western site has shown that averaged afternoon SO₂ to NO_x ratios on days with wind reversal are larger than those of typical urban Hong Kong and that a significant SO₂ enhancement was clearly indicated on several occasions. The SO₂ enhancement may be interpreted as being the evidence to suggest the contribution of regional sources and/or Hong Kong’s power plants (both containing high SO₂). A case study has shown that when moderately strong northwesterly wind prevails, elevated ozone and SO₂ can be transported to western Hong Kong from the inner Pearl Delta region. This study has also indicated that under the impact of ENE winds the eastern side of Hong Kong is not frequently affected by the re-circulating ozone plumes present in the western side.     

Neural modelling of the spatial distribution of air pollutants

In this paper, a new method to calculate the average spatial distribution of air pollutants based on diffusive sampling measurements and artificial neural networks evaluation is presented. Most established methods like interpolation algorithms are inflexible or limited in considering important distribution parameters such as emission sources or land use. Of special interest are air quality measurements since they provide a direct view on the actual pollutant level. With diffusive samplers, the average concentration of many gaseous species over a large area can be determined simultaneously. During a project in Cyprus, NO₂ diffusive samplers were exposed at 270 sites in six month-long campaigns throughout one year providing the database for the model described in this paper. A multilayer perceptron was trained with the NO₂ measurement data and distribution parameters like population density and meteorological parameters using a 1 × 1 km grid covering Cyprus. The best fit could be achieved with an emissions inventory including previously simulated concentration plumes and population density data as input nodes for the neural network, resulting in realistic maps of the annual average distribution of NO₂ in Cyprus.     

Trend analysis of urban NO2 concentrations and the importance of direct NO2 emissions versus ozone/NOx equilibrium

The annual air quality standard of NO₂ is often exceeded in urban areas near heavy traffic locations. Despite significant decrease of NO_x emissions in 1986–2005 in the industrial and harbour area near Rotterdam, NO₂ concentrations at the urban background remain at the same level since the end of the nineties. Trend analysis of monitoring data revealed that the ozone/NO_x equilibrium is a more important factor than increasing direct NO₂ emissions by traffic. The latter has recently been identified as an additional NO₂ source due to the introduction of oxy-catalytic converters in diesel vehicles and the growing number of diesel vehicles. However, in Rotterdam over the period 1986–2005 direct NO₂ emissions by road traffic only increased 3–4%. Due to the importance of the ozone/NO_x equilibrium, it is concluded that local NO_x emissions in Rotterdam need substantial reduction to achieve lower NO₂ urban background levels. This is a relatively costly abatement strategy and, therefore, a “hotspot” approach aiming at reducing NO_x emissions by local traffic measures is more effective to meet European air quality standards.     

Distribution of reactive nitrogen species in the remote free troposphere: data and model comparisons

The available reactive nitrogen measurements from the global free troposphere obtained during the period of 1985–1995 have been compiled and analyzed. The species of interest are NO, NO_x (NO+NO₂), NO_y, PAN, HNO₃ and O₃. Data extending to 13 km have been gridded with a 5°×5° horizontal and 1 km vertical resolution. The data have been divided into two seasons, namely “Winter” and “Summer” depending upon the time and location of the observations. Data described here as well as additional analysis have also been archived and are accessible on-line through the World Wide Web at: http://george.arc.nasa.gov/∼athakur. Global maps of the reactive nitrogen species distribution are produced in a form that would be most useful for the test and evaluation of models of tropospheric transport and chemistry. Limited comparisons of the observed reactive nitrogen species data with predictions by 3-D global models were performed using three selected models. Significant model to model as well as data to model differences were frequently observed. During summer, models tended to underpredict NO (−25 to −60%) while significantly overpredicting HNO₃ (+250 to +400%) especially in the upper troposphere. Similarly, the seasonal HNO₃ variations predicted by some models were opposite to those observed. PAN was generally overpredicted, especially in the upper troposphere, while NO_y was underpredicted. Ozone on average was better simulated but significant deviations at specific locations were evident. By comparing model predictions with observations, an overall quantitative assessment of the accuracy with which these three models describe the global distribution of measured reactive nitrogen species is provided. No reliable trend information for any of the reactive nitrogen species was possible based on the presently available data set. The reactive nitrogen data currently offer only a limited spatial and temporal coverage for the validation of global models.     

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

Estimation of Ambient PM2.5 Concentrations in Maryland and Verification by Measured Values

Abstract

In 1997, Maryland had no available ambient Federal Reference Method data on particulate matter less than 2.5 μm in aerodynamic diameter (PM_2.5), but did have annual ambient data for PM smaller than 10 μm (PM₁₀) at 24 sites. The PM₁₀ data were analyzed in conjunction with local annual and seasonal zip-code-level emission inventories and with speciated PM_2.5 data from four nearby monitors in the IMPROVE network (located in the national parks, wildlife refuges, and wilderness areas) in an effort to estimate annual average and seasonal high PM_2.5 concentrations at the 24 PM₁₀ monitor sites operating from 1992 to 1996. All seasonal high concentrations were estimated to be below the 24-hr PM_2.5 National Ambient Air Quality Standards (NAAQS) at the sites operating in Maryland between 1992 and 1996. The estimates also indicated that 12 monitor sites might exceed the 3-year annual average PM_2.5 NAAQS of 15 ug/m³, but Maryland’s air quality shows signs that it has been improving since 1992. The estimates also were compared with actual measurements after the PM_2.5 monitor network was installed. The estimates were adequate for describing the chemical composition of the PM_2.5, forecasting compliance status with the 24-hr and annual standards, and determining the spatial variations in PM_2.5 across central Maryland.     

Seasonal variation in atmospheric aerosol concentration and composition at urban and rural sites in northern England

Seasonal variations in atmospheric aerosol concentration and composition have been determined at two nearby sites, one urban and one rural, near Leeds, W. Yorkshire. Aerosols, sampled on a daily basis and collected in the size ranges < 2.5 μm and 2.5−15 μm, were analysed for total mass, SO²⁻₄, NO⁻₃, Cl⁻ and NH⁺₄. Dark smoke and SO₂ were also measured at both sites. Results are given covering the period October 1982–September 1983. The average concentration of particles was higher at the urban site. The urban-rural difference in coarse particle concentration, which was about a factor of 2, was more significant than the difference in the fine particle concentration, which was only 1.3. Smoke and SO₂ concentrations showed strong wintertime maxima and summertime minima. Fine NO⁻₃ and Cl⁻ concentrations also had pronounced wintertime maxima and summertime minima attributed to the variation in volatility of their ammonium salts. Total mass, SO²⁻₄ and NH⁺₄ did not show any clear seasonal variations. Anti-cyclonic conditions in summer resulted in elevated mass concentrations of secondary pollutants, e.g. SO²⁻₄. The fine fraction contained ca 50% water-soluble inorganic ions at Leeds and slightly more at the rural site. These proportions showed little seasonal variation.     

PM10 Levels in the Lower Fraser Valley,British Columbia,Canada: An Overview of Spatiotemporal Variations and Meteorological Controls

ABSTRACT

Three years of hourly averaged PM₁₀ (particulate matter less than 10 Lrm in diameter) tapered element oscillating microbalance (TEOM) data from 10 sites in the large coastal valley incorporating Greater Vancouver were used to investigate the spatiotemporal dimensions and air pollution meteorology of particulate pollution. During the period studied, the provincial “acceptable” objective daily concentration of 50 μg m^-3 was exceeded at 7 of the 10 sites. The highest annual, seasonal, and maximum hourly concentrations were recorded at Abbotsford in the central valley. Mean seasonal PM₁₀ concentrations were highest in the wintertime in the western Lower Fraser Valley (LFV) and in the summertime at the central and eastern valley locations. Within the network, interstation correlations of daily average concentrations exceed 0.8 at interstation distances less than 20 km and decrease thereafter. For daily maximum concentrations (hourly), interstation correlations decrease sharply with distance. Meteorological conditions responsible for elevated par-ticulate concentrations in the LFV are associated with (1) short periods (1- to 3-hr duration) of reduced dispersion during summer nights at sites close to primary sources, (2) summer anticyclonic conditions when photochemical pollutant concentrations build up across the entire valley, and (3) occasional wintertime “gap wind” events in the eastern valley.     

Overestimation of urban nitrogen dioxide by passive diffusion tubes: a comparative exposure and model study

A detailed comparative trial of passive diffusion tubes (PDT) for measurement of NO₂ in urban air has been undertaken in Edinburgh, UK. Acrylic, foil-wrapped and quartz tubes were exposed in parallel for 1-week and 4-week periods at three urban sites equipped with continuous analysers for NO, NO_x and O₃. Standard acrylic PDTs significantly overestimated NO₂ concentrations relative to chemiluminescence analysers, by an average of 27% over all sites for 1-week exposures. No significant difference was observed between standard and foil-wrapped acrylic tubes (both UV blocking). The mean ratio between quartz (UV transmitting) tubes and chemiluminescence analysers was 1.06. Quartz PDT data suggest a tendency for in situ photolysis to offset (but in a non-quantifiable way) the effect of chemical overestimation. The 4-week exposures yielded systematically lower NO₂ concentration than average NO₂ from four sequential 1-week exposures over the same period. The reduction in the apparent NO₂ sampling rate with time mostlikely arises from in situ photolysis of trapped NO₂. Hourly NO₂, NO and O₃ data for 20 1-week exposures were used as input to a numerical model of diffusion tube operation incorporating chemical reaction between co-diffusing NO and O₃ within the tube. The mean calculated overestimation of 22% for NO₂ from the PDT model simulations is close to the average difference between acrylic PDT and analyser NO₂ concentrations (24% for the same exposure periods), showing that within-tube chemistry can account for observed discrepancies in NO₂ measurement between the two techniques. Overestimation by PDT generally increased as average NO₂/NO_x ratios decreased. Accurate quantitative correction of PDT measurements is not possible. Nevertheless, PDT NO₂ concentrations were correlated with both analyser NO₂ and NO_x suggesting that acrylic PDTs retain a qualitative measure of NO₂ and NO_x variation at a particular urban location.     

Origin and variability of upper tropospheric nitrogen oxides and ozone at northern mid-latitudes

Year-long measurements of NO_x and ozone performed during the NOXAR project are compared to results from the ECHAM4.L39(DLR)/CHEM (E39/C) and GISS coupled chemistry–climate models. The measurements were taken on flights between Europe and the eastern United States and between Europe and the Far East in the latitude range 40–65°N. Our comparison concentrates on the upper troposphere and reveals strong longitudinal variations in seasonal mean NO_x of more than 200 pptv, which both models are able to reproduce qualitatively. Vertical profiles show maximum NO_x values 2–3 km below the tropopause (“E-shape”) with a strong seasonal cycle. E39/C simulates a maximum located at the tropopause and with a reasonable seasonal cycle. The GISS model reproduces the seasonal cycle but not the profile's shape due to its coarser vertical resolution. A comparison of NO_x frequency distributions reveals that both models are capable of reproducing the observed variability, except that E39/C shows no very high NO_x mixing ratios.Both models show that lightning and surface NO_x emissions contribute the most to the seasonal cycle of NO_x at tropopause altitudes. The impact of lightning in the upper troposphere does not vary strongly with altitude, whereas the impact of surface emissions decreases with altitude. Among all sources, lightning contributes the most to the variability of NO_x in the upper troposphere in northern mid-latitudes during summer.     

A prediction-based approach to modelling temporal and spatial variability of traffic-related air pollution in Montreal, Canada

Concentrations of traffic-related air pollution can be highly variable at the local scale and can have substantial seasonal variability. This study was designed to provide estimates of intra-urban concentrations of ambient nitrogen dioxide (NO₂) in Montreal, Canada, that would be used subsequently in health studies of chronic diseases and long-term exposures to traffic-related air pollution. We measured concentrations of NO₂ at 133 locations in Montreal with passive diffusion samplers in three seasons during 2005 and 2006. We then used land use regression, a proven statistical prediction method for describing spatial patterns of air pollution, to develop separate estimates of spatial variability across the city by regressing NO₂ against available land-use variables in each of these three periods. We also developed a “pooled” model across these sampling periods to provide an estimate of an annual average. Our modelling strategy was to develop a predictive model that maximized the model R². This strategy is different from other strategies whose goal is to identify causal relationships between predictors and concentrations of NO₂.Observed concentrations of NO₂ ranged from 2.6 ppb to 31.5 ppb, with mean values of 12.6 ppb in December 2005, 14.0 ppb in May 2006, and 8.9 ppb in August 2006. The greatest variability was observed during May. Concentrations of NO₂ were highest downtown and near major highways, and they were lowest in the western part of the city. Our pooled model explained approximately 80% of the variability in concentrations of NO₂. Although there were differences in concentrations of NO₂ between the three sampling periods, we found that the spatial variability did not vary significantly across the three sampling periods and that the pooled model was representative of mean annual spatial patterns.     

Rural ozone in the southeastern United States

Ozone measurements are reported for five rural sites in the Tennessee Valley region of the southeastern U.S. for periods ranging from 18 to 83 months during the years 1977 through 1984. Rural ozone (O₃) levels were found to equal or exceed urban values for the same region. The daily maximum 1-h average concentration was found to peak during the summer months, while the 24-h average concentrations were greatest in the spring. The annual cycle of daily maximum concentrations is related to the seasonal photochemical cycle. The annual cycle in 24-h average concentrations is best explained by the combined effects of the annual cycles in solar intensity and noctural O₃ depletion. There was no indication that stratospheric intrusions exhibited a significant influence on the annual O₃ cycles. Evidence was found for elevated O₃ levels during touchdown of plumes from large power plants. No long-term trend in rural O₃ concentrations, either daily maxima or means, was discernible.     

Analysis of the relationship between ambient levels of O3, NO2 and NO as a function of NOx in the UK

Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO_x, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O₃ and NO₂) varies with the level of NO_x, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NO_x-independent and NO_x-dependent contributions. The former is effectively a regional contribution which equates to the regional background O₃ level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO₂ emissions, (ii) the thermal reaction of NO with O₂ at high NO_x, and (iii) common-source emission of species which promote NO to NO₂ conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HO_x radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NO_x, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO₂ and O₃, are used to define expressions which describe the likely variation of annual mean NO₂ as a function of NO_x at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O₃.     

Seasonal variation of atmospheric ammonia and particulate ammonium concentrations in the urban atmosphere of yokohama over a 5-year period

Measurements of ammonia and particulate ammonium were made in the daytime (1200–1500) at a urban site in Yokohama during the 5-year period, 1982–1986. Diurnal NH₃ concentrations showed a distinct seasonal trend with a maximum in summer. The diurnal monthly average concentrations were above 10 ppb during the late spring and summer months, while the concentrations during the winter months were between 1 and 5 ppb. The seasonal variation was found to be very similar to that of the average air temperature and showed a periodic pattern over 1 year. A good correlation was observed between diurnal NH₃ concentrations and average air temperatures during the 5-year period. The annual mean concentrations were in the range of 6.6–7.6 ppb with only a minor deviation. The diurnal monthly average concentrations of particulate NH₄⁺ were between 1 and 4 μg m⁻³ and no significant seasonal variations were seen. As a short-term study, simultaneous measurements of NH₃, HNO₃ and particulate NO₃⁻ were made. The diurnal mean concentrations of NH₃ and HNO₃ were 7.6 and 0.8 ppb, respectively. The concentration of particulate NO₃⁻ ranged from 0.3 to 6μg⁻³. Both HNO₃ and particulate NO₃⁻ concentrations were relatively low and constant. Thus, NH₃ and HNO₃ levels did not agree with the concentrations predicted from the NH₄NO₃ equilibrium constant.     

Modeling the long-term frequency distribution of regional ozone concentrations

Efficient methods are developed for modeling emissions – air quality relationships that govern ozone and NO₂ concentrations over very long periods of time. A baseline model evaluation study is conducted to assess the accuracy and speed with which the relationship between pollutant emissions and the frequency distribution of O₃ concentrations throughout the year can be computed along with annual average NO₂ values using a deterministic photochemical airshed model driven by automated objective analysis of measured meteorological parameters. Methods developed are illustrated by application to the air quality situation that exists in Southern California. Model performance statistics for O₃ are similar to the results obtained in previous short-term episodic model evaluation studies that were based on hand-crafted meteorological inputs that are supplemented by expensive field measurement campaigns. Model predictions at one of the highest NO₂ concentration sites in the US indicate that measured violation of the US annual average NO₂ air quality standard at that site occurs because other species such as HNO₃ and PAN are measured as if they were NO₂ by the chemiluminescent NO_x monitors in current use.     

A Statistical Assessment of Saturation and Mobile Sampling Strategies to Estimate Long-Term Average Concentrations across Urban Areast

Abstract

The objectives of this study were: (1) to quantify the errors associated with saturation air quality monitoring in estimating the long-term (i.e., annual and 5 yr) mean at a given site from four 2-week measurements, once per season; and (2) to develop a sampling strategy to guide the deployment of mobile air quality facilities for characterizing intraurban gradients of air pollutants, that is, to determine how often a given location should be visited to obtain relatively accurate estimates of the mean air pollutant concentrations. Computer simulations were conducted by randomly sampling ambient monitoring data collected in six Canadian cities at a variety of settings (e.g., population-based sites, near-roadway sites). The 5-yr (1998–2002) dataset consisted of hourly measurements of nitric oxide (NO), nitrogen dioxide (NO₂), oxides of nitrogen (NO_x), sulfur dioxide (SO₂), coarse particulate matter (PM₁₀), fine particulate matter (PM_2.5)_, and CO. The strategy of randomly selecting one 2-week measurement per season to determine the annual or long-term average concentration yields estimates within 30% of the true value 95% of the time for NO₂, PM₁₀ and NO_x. Larger errors, up to 50%, are expected for NO, SO₂, PM_2.5, and CO. Combining concentrations from 85 random 1-hr visits per season provides annual and 5-yr average estimates within 30% of the true value with good confidence. Overall, the magnitude of error in the estimates was strongly correlated with the variability of the pollutant. A better estimation can be expected for pollutants known to be less temporally variable and/or over geographic areas where concentrations are less variable. By using multiple sites located in different settings, the relationships determined for estimation error versus number of measurement periods used to determine long-term average are expected to realistically portray the true distribution. Thus, the results should be a good indication of the potential errors one could expect in a variety of different cities, particularly in more northern latitudes.     

Comparative evaluation of nitrogen oxides and ozone passive diffusion tubes for exposure studies

Passive diffusion tubes are recognised as a cost-effective sampling method for characterising the spatial variability, as well as the seasonal and annual trends, of NO₂ concentrations in urban areas. In addition, NO_X and O₃ passive diffusion tubes have been developed and deployed in urban and rural areas. Despite their many advantages (e.g. low operational and analysis cost, small size and no need for power supply), they have certain limitations mainly related to their accuracy and precision. In particular, the absorbent solution used, the length of the exposure period, the exact location and use of protective devices, and other environmental conditions (e.g. wind, ambient temperature and relative humidity) may have a significant impact on the performance of passive diffusion tubes. The aim of this study is to evaluate the performance of co-located NO₂, NO_X and O₃ diffusion tubes in an urban environment.A one-year passive sampling campaign was carried out in Birmingham (UK) for this purpose. NO₂, NO_X and O₃ diffusion tubes (including triplicate sets of each) were co-located at one urban background and two roadside permanent air quality monitoring stations equipped with standard gas analysers. In addition, meteorological data, such as wind speed and direction, ambient temperature and relative humidity, were obtained during the same period of time. A thorough QA/QC procedure, including storage and laboratory blanks was followed throughout the campaign. The analysis of results showed a very good agreement of NO₂ passive samplers with co-located chemiluminescence analysers, but substantial underestimations of total NO_X levels by the diffusion tubes. The O₃ diffusion sampler appeared to marginally overestimate the automatic UV analyser results, especially during warm weather periods.