Increasing concentrations of nitrogen dioxide pollution in rural Wales

Monitoring of nitrogen dioxide pollution was carried out in rural environments throughout Wales during a 1-year survey to quantify any changes in background concentrations and distribution of the pollutant since an earlier survey in 1986. There were 23 sites in the present survey of which 16 had been monitored during the 1986 survey. The remaining 7 sites were based on moorland in mid-Wales within map squares for which critical loads for soil acidification are expected to be exceeded by the year 2005. All sites were chosen so as to be remote from major local sources of NO(2) and the values obtained were deemed to be minimum concentrations for the different regions. Measurements were made using diffusion tubes which aimed to provide mean concentrations of NO(2) for 2-week exposure periods. Concentrations of NO(2) were found to be higher in the winter months for most sites and this is probably related to a greater use of fossil fuels for heating buildings at this time of year. The exception was the high concentrations of NO(2) in May and June for several sites in North Wales, and in July and August for a site on Mount Snowdon. These high summer concentrations in North Wales are thought to be related to increased traffic associated with tourism. It is apparent that there has been a substantial increase in rural concentrations of NO(2) throughout Wales since the earlier survey of 1986. As an average of all 16 sites used in both surveys, there was a 53% increase in the annual mean concentration of NO(2). Also, it is evident that, since 1986, there has been a substantial increase in the area of south-eastern Wales which has a background level in excess of 10 ppb NO(2) and a notable reduction in land area with concentrations below 6 ppb NO(2) as an annual mean concentration. The possible future impact of increasing rural concentrations of NO(2) on Welsh vegetation is discussed with references to estimates of critical levels of NO(2) for adverse effects on plants.     

Rural concentrations of nitrogen dioxide pollution throughout Wales

Monitoring of nitrogen dioxide was carried out at over 50 rural sites in Wales throughout 1986. All sites were chosen so as to be remote from any local sources of NO(2) and the values obtained were deemed to be minimum values for the different regions. Measurements were made using a diffusion tube technique which aimed to give mean concentrations of NO(2) for 2-week exposure periods. The results obtained have been used to generate pollution maps to show mean monthly levels of NO(2) for rural environments throughout Wales. It is apparent that levels of NO(2) are generally higher during the winter months. In addition, annual mean concentrations of the pollutant are greatest in the north-eastern and south-eastern parts of Wales with the lowest levels being found along the western coast. The work marks the completion of the first national survey of nitrogen dioxide pollution in Wales. The data are discussed in terms of the potential threat rural concentrations of NO(2) pose to crops and natural vegetation.     

Sensitivity of nitrogen dioxide concentrations to oxides of nitrogen controls in the United Kingdom

There is a possibility of further controls on emissions to the atmosphere of nitrogen oxides to meet air quality objectives in the UK. Data in the National Air Quality Archive were used to calculate the likely sensitivity of hourly concentrations of nitrogen dioxide in ambient urban air to changes in the total oxides of nitrogen. Since the role of atmospheric chemical reactions is to make the response non-linearly dependent on the emissions control, we seek to establish the magnitude and sign of the effects that this non-linearity might cause. We develop a quantitative approach to analysing the non-linearity in the data. Polynomial curve fits have been developed for the empirical ratio NO₂ : NO_x (the ‘yield’). They describe nitrogen dioxide concentrations using total oxides of nitrogen. The new functions have the important feature of increased yield in winter episodes. Simpler functions tend to omit this feature of the yields at the highest hourly concentrations. Based on this study, the hourly nitrogen dioxide objective in the UK may require emissions control of no more than ≈50% on total oxides of nitrogen at the most polluted sites: other sites require less or even no control.     

Detecting and characterising small changes in urban nitrogen dioxide concentrations

Detecting and quantifying abnormal changes in the concentration of urban air pollutants can be difficult due to the influence of meteorology and atmospheric chemistry. This study presents methods to detect and characterise small changes in the concentration of nitrogen dioxide (NO₂) that deviate from expected behaviour. Generalized additive models (GAMs) are used to describe daily mean NO₂ concentrations at roadside monitoring sites to determine how concentrations deviate from measured concentrations. Structural change methods are applied to time series describing this difference to identify change-points, where concentrations of NO₂ deviate significantly from expected behaviour. Methods are also used which quantify the timing and uncertainty associated in the timing of these change-points. For most time series data considered in London, concentrations of NO₂ underwent relatively abrupt changes rather than smoothly varying increases; changes which remain largely undetected in raw time series data. Most change-points occurred in late 2002 or early 2003, and the factors, which may have contributed to them, are discussed. These methods can also identify technical problems with monitoring equipment and are applicable to other instances where detecting sudden atmospheric composition change is important.     

Measurements of personal exposure to nitrogen dioxide in four Mexican cities in 1996

Nitrogen dioxide is a ubiquitous pollutant in urban areas. Indoor NO2 concentrations are influenced by penetration of outdoor concentrations and by indoor sources. The objectives of this study were to evaluate personal exposure to NO2, taking into account human time-activity patterns in four Mexican cities. Passive filter badges were used for indoor, outdoor, and personal NO2 measurements over 48 hr and indoor workplace measurements over 16 hr. Volunteers completed a questionnaire on exposure factors and a time-activity diary during the sample period. An unpaired t test, an analysis of variance (ANOVA), and a linear regression were performed to compare differences among cities and mean personal NO2 concentrations involving housing characteristics, as well as to determine which variables predicted the personal NO2 concentration. Sampling periods were in April, May, and June 1996 in Mexico City, Guadalajara, Cuernavaca, and Monterrey. All 122 volunteers in the study were working adults, with a mean age of 34 (SD +/- 7.38); 64% were female, and the majority worked in public offices and universities. The highest NO2 concentrations were found in Mexico City (36 ppb for outdoor, 57 ppb for indoor, and 39 ppb for personal concentration) and the lowest in Monterrey (19 ppb for outdoor, 24 ppb for indoor, and 24 ppb for personal concentration). Significant differences in NO2 concentrations were found among the cities in different microenvironments. During the sampling period, volunteers spent 85% of their time indoors. The highest personal NO2 concentration was found when volunteers kept their windows closed (p = 0.03). In the regression model adjusted by city and gender, the best predictors of personal NO2 concentration were outdoor levels and time spent outdoors (R2 = 0.68). These findings suggest that outdoor NO2 concentrations were an important influence on the personal exposure to NO2, due to the specific characteristics and personal behavior of the people in these Mexican cities.     

Sources and concentrations of indoor nitrogen dioxide in Barcelona, Spain

Sources and concentrations of indoor nitrogen dioxide (NO2) were examined in Barcelona, Spain, during 1996-1999. A total of 340 dwellings of infants participating in a hospital-based cohort study were selected from different areas of the city. Passive filter badges were used for indoor NO2 measurement over 7-30 days. Dwelling inhabitants completed a questionnaire on housing characteristics and smoking habits. Data on outdoor NO2 concentrations were available for the entire period of the study in the areas of the city where indoor concentrations were determined. Bivariate analysis was performed to investigate relationships between indoor NO2 concentrations on one hand and outdoor NO2 concentrations, housing, and occupant characteristics on the other. Stepwise multiple linear regression was performed with variables that were found to have a significant bivariate relationship. Indoor NO2 mean values ranged between 23.57 ppb in 1996 and 27.02 ppb in 1999, with the highest yearly value of 27.82 ppb in 1997. In the same time period, mean outdoor NO2 concentration ranged between 25.26 and 25.78 ppb with a peak of 30.5 ppb in 1998. Multiple regression analysis showed that principal sources of indoor NO2 concentrations were the use of a gas cooker, the absence of an extractor fan when cooking, and cigarette smoking. The absence of central heating was also associated with higher NO2 concentrations. Finally, each ppb increase in outdoor NO2 was associated with a 1% increase in indoor concentrations.     

Street-level concentrations of nitrogen dioxide and suspended particulate matter in Hong Kong

The concentrations of respirable suspended particulates (PM₁₀), fine suspended particulates (PM_2.5) and nitrogen dioxide (NO₂) were measured in various locations over the territory of Hong Kong. In order to study the contributions of these pollutants from motor vehicles and their characteristics, the attention was focused on the roadside, street-level concentrations. A statistical analysis of the sampling results was conducted to obtain general characteristics of the roadside particulate and nitrogen dioxide pollution and to investigate the effects of traffic volume and meteorological factors on the pollution levels. High correlation coefficients are found between PM₁₀, PM_2.5 and NO₂ concentration.     

Methodological trends in the design of recent microenvironmental studies of personal CO exposure

This paper describes the designs of three recent microenvironmental studies of personal exposure to carbon monoxide (CO) from motor vehicle exhaust. These studies were conducted sequentially, first in four California cities (Los Angeles, Mountain View, Palo Alto, and San Francisco), then in Honolulu, and, most recently, in metropolitan Washington, D.C. Though study purposes differed, each study faced common methodological issues related to personal exposure monitors (PEMs), quality assurance and data collection procedures, and the selection of microenvironments for study.Two major objectives of the California cities study were to determine the CO concentrations typically found in commercial settings and to define and classify microenvironments applicable to such settings: The Honolulu study measured merchant exposure to CO in shopping centers attached to semienclosed parking garages during business hours and commuter exposure to CO in vehicles (passenger cars and buses) on congested roadways during peak periods. The intent of the Washington study was to develop a model of commuter exposure to motor vehicle exhaust using CO as an indicator pollutant.Certain trends are discernible from reviewing the three studies. There are clearly trends in PEM development that have expanded instrument capabilities and automated data collection and storage. There are also trends towards more rigorous quality assurance procedures and more standardized protocols for collecting exposure data. Further, one can see a trend towards more elaborate indicators for identifying microenvironments for study. Finally, there is a trend towards using personal monitors in public policy review and evaluation.     

An empirical model for predicting urban roadside nitrogen dioxide concentrations in the UK

An annual mean concentration of 40 μg m⁻³ has been proposed as a limit value within the European Union Air Quality Directives and as a provisional objective within the UK National Air Quality Strategy for 2010 and 2005, respectively. Emissions reduction measures resulting from current national and international policies are likely to deliver significant reductions in emissions of oxides of nitrogen from road traffic in the near future. It is likely that there will still be exceedances of this target value in 2005 and in 2009 if national measures are considered in isolation, particularly at the roadside. It is envisaged that this `policy gap’ will be addressed by implementing local air quality management to reduce concentrations in locations that are at risk of exceeding the objective. Maps of estimated annual mean NO₂ concentrations in both urban background and roadside locations are a valuable resource for the development of UK air quality policy and for the identification of locations at which local air quality management measures may be required. Maps of annual mean NO₂ concentrations at both background and roadside locations for 1998 have been calculated using modelling methods, which make use of four mathematically straightforward, empirically derived linear relationships. Maps of projected concentrations in 2005 and 2009 have also been calculated using an illustrative emissions scenario. For this emissions scenario, annual mean urban background NO₂ concentrations in 2005 are likely to be below 40 μg m⁻³, in all areas except for inner London, where current national and international policies are expected to lead to concentrations in the range 40–41 μg m⁻³. Reductions in NO_x emissions between 2005 and 2009 are expected to reduce background concentrations to the extent that our modelling results indicate that 40 μg m⁻³ is unlikely to be exceeded in background locations by 2009. Roadside NO₂ concentrations in urban areas in 2005 and 2009 are expected to be significantly higher than in background locations. 21% of urban major road links are expected to have roadside NO₂ greater than or equal to 40 μg m⁻³ in 2005 for our illustrative emissions scenario. The continuing downward trend in traffic emissions is likely to further reduce the number of links exceeding this value by 2009, with about 6% of urban major road links predicted to have concentrations higher than 40 μg m⁻³. The majority of these links are in the London area. The remaining links are generally confined to the most heavily trafficked roads in other big cities.     

An empirical approach for the prediction of annual mean nitrogen dioxide concentrations in London

Annual mean limits for NO₂ concentrations have been set in the European Union, which will be most challenging to meet in large urban conurbations. In this paper, we discuss techniques that have been developed to predict current and future NO₂ concentrations in London, utilising ambient data. Hourly average NO_x (NO+NO₂) and NO₂ concentrations are used to calculate NO_x frequency distributions. By defining relationships between the annual mean NO_x and NO₂ at different sites, it is possible to investigate different NO_x reduction strategies. The application of the frequency distribution approach to monitoring sites in London shows that given the likely change in emissions by 2005, it is unlikely that much of central and inner London will meet the objective. The approaches used suggest that meeting the objective in central London will be the most challenging for policy makers requiring NO_x concentrations as low as 30 ppb, compared with values closer to 36–40 ppb for outer London. Predictions for 2005 indicate that concentrations of NO₂ up to 6 ppb in excess of the objective are likely in central London.     

Measurements of nitrogen dioxide and sulphur dioxide concentrations in urban and rural areas of Poland using a passive sampling method

Measurements of 1-month concentrations of NO(2) and SO(2) were carried out in the period from May 1993 to April 1994 in 147 points in 30 major cities of Poland and in 31 points in rural areas. The measurement points were divided into five classes representing: centres of cities, residential areas, industrial areas, traffic locations and rural areas. Passive samplers were prepared in one laboratory, mailed to local laboratories for sampling and then returned for analysis. The same samplers were used for collecting both NO(2) and SO(2). Analyses for NO(2) absorbed as nitrite were made spectrophotometrically after reaction with Saltzman reagent. Sulphur dioxide was determined as sulphate with ion chromatography. The consistency of data allowed comparison of levels of air pollution in different cities and the production of maps of spatial distribution of NO(2) and SO(2) in rural areas of Poland.     

The influence of highway traffic on ambient nitrogen dioxide concentrations beyond the immediate vicinity of highways

The objective of these analyses was to determine whether highways significantly influence ambient concentrations of NO₂ at distances greater than 200 m. NO₂ was sampled for 14 consecutive days in May 2003 at 67 sites across Montréal, Canada. The association between logarithmic concentrations of NO₂ and land-use variables was assessed using multiple regressions. Locations less than 100 m from the nearest highways were excluded, leaving 61 data points. Then, locations less than 200 m were excluded, leaving 55 data points. Excluding sampling locations located less than 100 or 200 m from the nearest highway did not substantially change the regression parameters. NO₂ was still significantly associated with both the distance from nearest highway and the traffic count on the nearest highway. These findings indicate that the negative association found between distance from highways and NO₂ concentration in several land-use regression studies in Europe and North America was not generated solely by the high concentrations found in the immediate vicinity of highways.     

Measurements of nitrogen dioxide concentrations at rural sites in the United Kingdom using diffusion tubes

Nitrogen dioxide concentrations have been measured at rural sites in the United Kingdom and have revealed a marked spatial variation. The annual mean NO2 concentration varies from approximately 1 microg Nm-3 in Northern Ireland to approximately 7 microg Nm-3 in East Anglia. Though the temporal resolution of the diffusion tube method is limited by exposure periods of 2-4 weeks, it was possible to detect a marked seasonal variation in NO2 concentration at all sites, with higher values in the winter than in the summer. This is in contrast to the small seasonal variation previously observed at sites in London. Sulphur dioxide concentrations were measured daily using a bubbler method and, if expressed in terms of mass of sulphur and nitrogen, the SO2 and NO2 annual mean concentrations were similar. This is in contrast to an S/N ratio of greater than 3 in total UK emissions of SO2 and NOx. It seems likely that this difference is due to a combination of the different spatial distributions and heights of emissions of SO2 and NOx, the influence of local sources of NOx, and the smaller S/N ratio in Continental European emissions.     

A synoptic climatological approach to forecast concentrations of sulfur dioxide and nitrogen oxides in Hong Kong

The objective of this study is to develop an automated synoptic climatological procedure to forecast high air pollution concentrations in the most polluted synoptic categories. The procedure is able to identify air masses historically associated with high air pollution concentrations. The arrival of air mass can be predicted 24 or 48 h in advance with the use of the weather forecast data. The development and statistical basis of the procedure are discussed, and an analysis of the procedure's ability to forecast weather conditions associated with high air pollution concentrations is presented. In addition, the dataset of 24 weather variables from 1993 to 1995 is used to validate the procedure. The procedure predicts that 70.3 and 83.3% of total high and severe SO2 concentration days fall into the identified most polluted categories, and the corresponding figures for NOx are 47.8 and 73.7%. The agreement between observed and predicted values is generally good. The prediction models can explain about 58 and 45% of total variance for NOx and SO2 with RMSEs of 42.5 and 16.5 microg m(-3), respectively. They are smaller than 1 SD of the observations.     

Mercury accumulation in grass and forb species as a function of atmospheric carbon dioxide concentrations and mercury exposures in air and soil

The goal of this study was to investigate the potential for atmospheric Hg degrees uptake by grassland species as a function of different air and soil Hg exposures, and to specifically test how increasing atmospheric CO(2) concentrations may influence foliar Hg concentrations. Four common tallgrass prairie species were germinated and grown for 7 months in environmentally controlled chambers using two different atmospheric elemental mercury (Hg major; 3.7+/-2.0 and 10.2+/-3.5 ng m(-3)), soil Hg (<0.01 and 0.15+/-0.08 micro g g(-1)), and atmospheric carbon dioxide (CO(2)) (390+/-18, 598+/-22 micro mol mol(-1)) exposures. Species used included two C4 grasses and two C3 forbs. Elevated CO(2) concentrations led to lower foliar Hg concentrations in plants exposed to low (i.e., ambient) air Hg degrees concentrations, but no CO(2) effect was apparent at higher air Hg degrees exposure. The observed CO(2) effect suggests that leaf Hg uptake might be controlled by leaf physiological processes such as stomatal conductance which is typically reduced under elevated CO(2). Foliar tissue exposed to elevated air Hg degrees concentrations had higher concentrations than those exposed to low air Hg degrees , but only when also exposed to elevated CO(2). The relationships for foliar Hg concentrations at different atmospheric CO(2) and Hg degrees exposures indicate that these species may have a limited capacity for Hg storage; at ambient CO(2) concentrations all Hg absorption sites in leaves may have been saturated while at elevated CO(2) when stomatal conductance was reduced saturation may have been reached only at higher concentrations of atmospheric Hg degrees . Foliar Hg concentrations were not correlated to soil Hg exposures, except for one of the four species (Rudbeckia hirta). Higher soil Hg concentrations resulted in high root Hg concentrations and considerably increased the percentage of total plant Hg allocated to roots. The large shifts in Hg allocation patterns-notably under soil conditions only slightly above natural background levels-indicate a potentially strong role of plants in belowground Hg transformation and cycling processes.     

Exposure of population and microenvironmental distributions of volatile organic compound concentrations in the EXPOLIS study

Determination of volatile organic compounds (VOCs) formed one part of the EU-EXPOLIS project in which the exposure of European urban populations to particles and gaseous pollutants was studied. The EXPOLIS study concentrated on 30 target VOCs selected on the basis of environmental and health significance and usability of the compounds as markers of pollution sources. In the project, 201 subjects in Helsinki, 50 in Athens, 50 in Basel, 50 in Milan and, 50 in Oxford and 50 in Prague were selected for the final exposure sample. The microenvironmental and personal exposure concentrations of VOCs were the lowest in Helsinki and Basel, while the highest concentrations were measured in Athens and Milan; Oxford and Prague were in between. In all cities, home indoor air was the most significant exposure agent. Workplace indoor air concentrations measured in this study were generally lower than the home indoor concentrations and home outdoor air played a minor role as an exposure agent. When estimating the measured personal exposure concentrations using the measured concentrations and time fractions spent at home indoors, at home outdoors, and at the workplace, it could be concluded that these three microenvironments do not fully explain the personal exposure. Other important sources for personal exposure must be encountered, the most important being traffic/transportation and other indoor environments not measured in this study.     

Effects of sulfur dioxide and oxides of nitrogen emission reductions on fine particulate matter mass concentrations: regional comparisons

Two thermodynamic equilibrium models were applied to estimate changes in mean airborne fine particle (PM2.5) mass concentrations that could result from changes in ambient concentrations of sulfate, nitric acid, or ammonia in the southeastern United States, the midwestern United States, and central California. Pronounced regional differences were found. Southeastern sites exhibited the lowest current mean concentrations of nitrate, and the smallest predicted responses of PM2.5 nitrate and mass concentrations to reductions of nitric acid, which is the principal reaction product of the oxidation of nitrogen dioxide (NO2) and the primary gas-phase precursor of fine particulate nitrate. Weak responses of PM2.5 nitrate and mass concentrations to changes in nitric acid levels occurred even if sulfate concentrations were half of current levels. The midwestern sites showed higher levels of fine particulate nitrate, characterized by cold-season maxima, and were projected to show decreases in overall PM levels following decreases of either sulfate or nitric acid. For some midwestern sites, predicted PM2.5 nitrate concentrations increased as modeled sulfate levels declined, but sulfate reductions always reduced the predicted fine PM mass concentrations; PM2.5 nitrate concentrations became more sensitive to reductions of nitric acid as modeled sulfate concentrations were decreased. The California sites currently have the highest mean concentrations of fine PM nitrate and the lowest mean concentrations of fine PM sulfate. Both the estimated PM2.5 nitrate and fine mass concentrations decreased in response to modeled reductions of nitric acid at all California sites. The results indicate important regional differences in expected PM2.5 mass concentration responses to changes in sulfate and nitrate precursors. Analyses of ambient data, such as described here, can be a key part of weight of evidence (WOE) demonstrations for PM2.5 attainment plans. Acquisition of the data may require special sampling efforts, especially for PM2.5 precursor concentration data.     

Effects of nitrogen dioxide on leaf chlorophyll and nitrogen content of soybean

One-month-old soybean (Glycine max [L.] Merrill), cultivar 'Williams', plants were exposed to nitrogen dioxide (0.1, 0.2, 0.3 and 0.5 ppm) and carbon filtered air (control), 7 h per day, for 5 days, under a controlled environment. Leaf chlorophyll content (Ch a, Ch b, and total Ch content) and foliar nitrogen content (%N) were determined before and after the exposure. The influence of NO(2) treatments up to 0.3 ppm on leaf chlorophyll content was negligible although a stimulatory effect was evident in Ch a and total Ch content with 0.2 ppm NO(2). Marked decline in Ch content was observed with 0.5 ppm treatment; the reductions in Ch a and total Ch were 45% and 47%, respectively. Foliar-N contents of plants treated with 0.2 and 0.3 ppm NO(2) were higher than the control; plants exposed to 0.5 ppm NO(2) showed a 41% reduction in foliar-N compared to pre-exposure values.