Modelling of indoor exposure to nitrogen dioxide in the UK

A dynamic multi-compartment computer model has been developed to describe the physical processes determining indoor pollutant concentrations as a function of outdoor concentrations, indoor emission rates and building characteristics. The model has been parameterised for typical UK homes and workplaces and linked to a time-activity model to calculate exposures for a representative homemaker, schoolchild and office worker, with respect to NO₂. The estimates of population exposures, for selected urban and rural sites, are expressed in terms of annual means and frequency of hours in which air quality standards are exceeded. The annual mean exposures are estimated to fall within the range of 5–21 ppb for homes with no source, and 21–27 ppb for homes with gas cooking, varying across sites and population groups. The contribution of outdoor exposure to annual mean NO₂ exposure varied from 5 to 24%, that of indoor penetration of outdoor air from 17 to 86% and that of gas cooking from 0 to 78%. The frequency of exposure to 1 h mean concentrations above 150 ppb was very low, except for people cooking with gas.     

Personal exposure of children and adults to airborne benzene in four French cities

Atmospheric concentrations of and personal exposure to benzene have been measured in four French metropolitan areas for 210 subjects over two seasons. Half of the volunteers were 6–13-year-old children. The adult subjects were non-smokers, not occupationally exposed and they live and work in the monitored areas. Measurements were performed using diffusive samplers followed by GC-FID analysis. The average values for ambient air concentrations (μg m⁻³) were: Rouen: 1.5; Île de France (Paris area): 1.6; Grenoble: 2.3 and Strasbourg: 2.6, showing that benzene concentrations in the ambient air of the four cities satisfy the requirements of the European Directive 2000/69EC of the European Parliament which stipulates a limit value of 5 μg m⁻³. However, the 48 h exposures measured were found to be between 2.7 and 3.5 times higher than ambient air concentrations. As a consequence, 60% of the subjects investigated, including children, were exposed to concentrations higher than the ambient air limit value. This work confirms that air monitoring data collected by fixed stations should be used with caution when assessing population exposure to benzene, especially given the influence of indoor sources and other polluted microenvironments where people spend part of their time.     

Measurements of nitrogen dioxide on Funen using diffusion tubes

Monitoring of nitrogen dioxide (NO₂) by passive sampling on the Danish island Funen (Fyn) show that the concentration of nitrogen dioxide is low (2–20 ppb). The level of NO₂ in rural and suburban areas is governed by imported airpollution, and elevated NO₂ concentrations due to local traffic are of limited importance. These results are supported by diffusion denuder measurements of nitric acid (HNO₃) and particulate nitrate. Measurements of NO₂ with chemiluminescence and diffusive passive sampling showed good agreement between the methods. The special mounting device for the diffusive samplers used in this work seem to have reduced the turbulence at the open end of the tube. The product from the reaction between nitrogen dioxide and triethanolamine was investigated and tentatively identified as triethanolamine N-oxide, which is in accordance with the observed 1 : 1 stoechiometry in the conversion of NO₂ to nitrite ions.     

Risk factors for increased BTEX exposure in four Australian cities

Benzene, toluene, ethylbenzene and xylenes (BTEX) are common volatile organic compounds (VOCs) found in urban airsheds. Elevated levels of VOCs have been reported in many airsheds at many locations, particularly those associated with industrial activity, wood heater use and heavy traffic. Exposure to some VOCs has been associated with health risks. There have been limited investigations into community exposures to BTEX using personal monitoring to elucidate the concentrations to which members of the community may be exposed and the main contributors to that exposure. In this cross sectional study we investigated BTEX exposure of 204 non-smoking, non-occupationally exposed people from four Australian cities. Each participant wore a passive BTEX sampler over 24h on five consecutive days in both winter and summer and completed an exposure source questionnaire for each season and a diary for each day of monitoring. The geometric mean (GM) and range of daily BTEX concentrations recorded for the study population were benzene 0.80 (0.04-23.8 ppb); toluene 2.83 (0.03-2120 ppb); ethylbenzene 0.49 (0.03-119 ppb); and xylenes 2.36 (0.04-697 ppb). A generalised linear model was used to investigate significant risk factors for increased BTEX exposure. Activities and locations found to increase personal exposure included vehicle repair and machinery use, refuelling of motor vehicles, being in an enclosed car park and time spent undertaking arts and crafts. A highly significant difference was found between the mean exposures in each of the four cities, which may be explained by differences in fuel composition, differences in the mix and density of industry, density of motor vehicles and air pollution meteorology.     

Impact of microenvironmental nitrogen dioxide concentrations on personal exposures in Australia

Indoor and outdoor NO2 concentrations were measured and compared with simultaneously measured personal exposures of 57 office workers in Brisbane, Australia. House characteristics and activity patterns were used to determine the impacts of these factors on personal exposure. Indoor NO2 levels and the presence of a gas range in the home were significantly associated with personal exposure. The time-weighted average of personal exposure was estimated using NO2 measurements in indoor home, indoor workplace, and outdoor home levels. The estimated personal exposures were closely correlated, but they significantly underestimated the measured personal exposures. Multiple regression analysis using other nonmeasured microenvironments indicated the importance of transportation in personal exposure models. The contribution of transportation to the error of prediction of personal exposure was confirmed in the regression analysis using the multinational study database.     

Indoor nitrogen dioxide exposure and children's pulmonary function

Elevated concentrations of nitrogen dioxide (NO2) are produced in the home by the use of unvented gas appliances. In studies on potential health effects of indoor exposure to NO2, exposure has mostly been estimated from the presence or absence of sources like gas cookers in the home. This leads to misclassification of exposure, as NO2 concentrations in the home depend also on source use, ventilation habits, time budgets, etc. The availability of cheap, passive monitoring devices has made it possible to measure indoor concentrations of NO2 directly in health effects studies, albeit with averaging times of one to several days. So far, it has not been evaluated whether this increases the sensitivity of a study to detect health effects of NO2. In this paper, a comparison is made between NO2 sources and weekly average indoor NO2 measurements, as predictors of pulmonary function in a study among children aged 6-12 years. The relationship between exposure and lung functions was found to be generally non-significant in this study. The results further suggested that in this study, measuring indoor NO2 concentrations with passive monitors offered no advantage over the simple use of source presence as exposure variable.     

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.     

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.     

Exposure assessment of air pollutants: a review on spatial heterogeneity and indoor/outdoor/personal exposure to suspended particulate matter,nitrogen dioxide and ozone

This review describes databases of small-scale spatial variations and indoor, outdoor and personal measurements of air pollutants with the main focus on suspended particulate matter, and to a lesser extent, nitrogen dioxide and photochemical pollutants. The basic definitions and concepts of an exposure measurement are introduced as well as some study design considerations and implications of imprecise exposure measurements. Suspended particulate matter is complex with respect to particle size distributions, the chemical composition and its sources. With respect to small-scale spatial variations in urban areas, largest variations occur in the ultrafine (<0.1 μm) and the coarse mode (PM_10–2.5, resuspended dust). Secondary aerosols which contribute to the accumulation mode (0.1–2 μm) show quite homogenous spatial distribution. In general, small-scale spatial variations of PM_2.5 were described to be smaller than the spatial variations of PM₁₀. Recent studies in outdoor air show that ultrafine particle number counts have large spatial variations and that they are not well correlated to mass data. Sources of indoor particles are from outdoors and some specific indoor sources such as smoking and cooking for fine particles or moving of people (resuspension of dust) for coarse particles. The relationships between indoor, outdoor and personal levels are complex. The finer the particle size, the better becomes the correlation between indoor, outdoor and personal levels. Furthermore, correlations between these parameters are better in longitudinal analyses than in cross-sectional analyses. For NO₂ and O₃, the air chemistry is important. Both have considerable small-scale spatial variations within urban areas. In the absence of indoor sources such as gas appliances, NO₂ indoor/outdoor relationships are strong. For ozone, indoor levels are quite small. The study hypothesis largely determines the choice of a specific concept in exposure assessment, i.e. whether personal sampling is needed or if ambient monitoring is sufficient. Careful evaluation of the validity and improvements in precision of an exposure measure reduce error in the measurements and bias in the exposure–effect relationship.     

Personal exposure to PM2.5 and element composition—A comparison between outdoor and indoor workers from two Mexican cities

Many individuals work outdoors in the formal and informal economy of the large urban areas in developing countries, where they are potentially exposed for long periods to high concentrations of ambient airborne particulate matter (PM). This study describes the personal exposures to PM of 2.5 μm aerodynamic diameter and smaller (PM_2.5) for a sample of outdoor and indoor workers in two cities, Mexico City and Puebla, in central Mexico.Thirty-six workers in Mexico City and 17 in Puebla were studied. Thirty were outdoor workers (i.e., taxi and bus drivers, street vendors, and vehicle inspectors) and 23 were indoor (office) workers. Their personal exposures to PM_2.5 were monitored for a mean 19-h period. In Mexico City, the street vendors and taxi drivers overall exposures were significantly higher than indoor workers were. In Puebla, bus drivers had a higher overall exposure than vehicle inspectors or indoor workers. Most of the exposures were above the 65 μg m⁻³ 24-h Mexican standard.In Mexico City, exposures to Si, Ti, Cr, Mn, Fe, Ni, Cu, Mo and Cd were higher for outdoor than for indoor workers. In Puebla, exposures to Si, S, K, Ca, Ti, V, Mn, and Zn also were higher for outdoor workers. In Mexico City outdoor workers exposures to Cu, Pb, Cr, Se and Mo were 4 or more times higher than for Puebla outdoor workers, while Puebla outdoor workers’ exposures to V, Si, Fe and Ca were 3 or more times higher than Mexico City outdoor workers.These results suggest that for these outdoor workers the elevated local ambient air PM concentrations and an extended period spent outside are more important contributors to total exposures than indoor concentrations. These workers could be at particular risk of increased morbidity and mortality associated with ambient PM.     

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.     

Bayesian hierarchical modeling of personal exposure to particulate matter

In the US EPA's 1998 Baltimore Epidemiology-Exposure Panel Study, a group of 16 residents of a single building retirement community wore personal monitors recording personal fine particulate air pollution concentrations (PM_2.5) for 27 days, while other monitors recorded concurrent apartment, central indoor, outdoor and ambient site PM_2.5 concentrations. Using the Baltimore panel study data, we develop a Bayesian hierarchical model to characterize the relationship between personal exposure and concentrations of PM_2.5 indoors and outdoors. Personal exposure is expressed as a linear combination of time spent in microenvironments and associated microenvironmental concentrations. The model incorporates all available monitoring data and accounts for missing data and sources of uncertainty such as measurement error and individual differences in exposure. We discuss the implications of using personal versus ambient PM_2.5 measurements in characterization of personal exposure to PM_2.5.     

The effects of prior exposure to sulphur dioxide and nitrogen dioxide on the water relations of timothy grass (Phleum pratense) under drought conditions

Studies of the growth and water relations of the grass Phleum pratense L. (Timothy) were made after simultaneous exposure to SO(2) and NO(2) at concentrations ranging from 80 + 57.4 microg m(-3) to 240 + 172.2 microg m(-3) (SO(2) + NO(2)). Decreased partitioning to the roots was evident during exposure to the pollutants, but when the plants were returned to clean air restrictions in root growth did not persist. Shoot to root partitioning was, however, complicated by the additional factor of changes in the nutritional status of the soil after additional columns of fresh soil were attached to the original tubes. The rate of use of soil water was nevertheless substantially increased by the pollution treatment and after a period of 23 days in which water was withheld, a clear pollution x water stress interaction was seen. The ability of polluted leaves to conserve water under severe water stress was tested by excising the leaves and measuring their water loss over time. The results from this second experiment showed that conservation of water by the leaves was appreciably affected after exposure to 80 + 57.4 microg m(-3) or 133.3 + 95.6 microg m(-3) SO(2) + NO(2). It seems likely that damage to the cells in the epidermal layer, leading to malfunctioning of stomata, is mainly responsible for the reduced ability to conserve water under conditions of extreme stress.     

Pretreatment with nitrogen dioxide modifies plant response to ozone

Plant growth inhibition by ozone is significantly affected by previous exposure to nitrogen dioxide. Experiments on the early growth of four crop species showed that daily pretreatment with NO₂ (0.08–0.10 ppm for 3 h) immediately prior to exposure to O₃ (0.08–0.10 ppm for 6 h) increased the inhibition of radish and wheat growth, decreased the inhibition of bush bean growth, but had no effect on the growth of mint. The magnitudes of the interactive effects indicate that in regions where relatively high concentrations of O₃ are produced by photochemical processes, for example, downwind from urban centres, assessments of the impact of O₃ on vegetation based on knowledge of response to O₃ alone may be seriously flawed.     

Response of spinach and kidney bean plants to nitrogen dioxide

Different responses of spinach and kidney bean plants to various concentrations of NO(2) in the light and in the dark were shown. Spinach is more resistant than NO(2) than kidney bean. It is not only due to its greater tolerance to NO(2)(-) accumulated in leaves, but also to its stronger ability to metabolize NO(2)(-). The injury of spinach induced by the exposure to high concentration NO(2) in the light was not caused by the accumulation of NO(2)(-), but concerned the large amount of accumulated NH(3). The primary causes of NH(3) accumulation were that the activity of nitrite reductase was not affected by the fumigation on the one hand, and the activities of glutamine synthetase and glutamate synthase were inhibited on the other.     

Effect of acute nitrogen dioxide exposure on the composition of fatty acid associated with phospholipids in alveolar lavage

In vivo exposure of rats to 10 ppm nitrogen dioxide (NO₂) for 12h caused changes in fatty acids composition of alveolar lavage phospholipids. Among the fatty acid species, the relative ratio of palmitic acid, myristic acid and palmitoleic acid increased significantly. While the relative ratio of stearic acid, oleic acid, linoleic acid and arachidonic acid decreased significantly. Both the increase in the incorporation of palmitic acid in phosphatidylcholine which would be released into the alveoli and the increase in the release of phosphatidylcholine into the alveoli may account for the changes in the fatty acid composition of the present findings.     

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.