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.     

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.     

Nitrogen dioxide distribution in street canyons

Weekly average NO₂ concentrations have been measured at over 40 locations within two canyonlike streets in central London, using passive diffusion tube samplers. A steady decline in concentrations with height is found, levels being close to local background at about 20 m. There is a rapid decline over the first 10–15 m horizontally from the centre of the road and concentrations are close to local background at a distance of 30 m. Concentrations are 10–15% higher close to traffic lights than they are 60 m upstream. Possible reasons for this are discussed. The results provide valuable information to assist in the selection of sites for chemiluminescence monitors, which are required to check compliance with the new European Council air quality standard for NO₂.     

Precision and Accuracy in the Determination of Sulfur Oxides,Fluoride, and Spherical Aluminosilicate Fly Ash Particles in Project MOHAVE

The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO₂ and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m³ and ±2.5 nmol/m³ for the determination of SO₂ and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m³ and ±2.0 nmol/m³ for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m³. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m³. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m³) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m³). The concentrations of SO₂(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SO_x (SO₂(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SO_x and SO₂(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO₂(g) and sulfate results obtained from different types of samplers are given.     

Field Method Comparison between Passive Air Samplers and Continuous Monitors for VOCs and NO2 in El Paso,Texas

Abstract

This study evaluates the performance of Model 3300 Ogawa Passive Nitrogen Dioxide (NO₂) Samplers and 3M 3520 Organic Vapor Monitors (OVMs) by comparing integrated passive sampling concentrations to averaged hourly NO₂ and volatile organic compound (VOC) measurements at two sites in El Paso, TX. Sampling periods were three time intervals (3-day weekend, 4-day weekday, and 7-day weekly) for three consecutive weeks. OVM concentrations were corrected for ambient pressure to account for higher elevation. Precise results (<5% relative standard deviation, RSD) were found for NO₂ measurements from collocated Ogawa samplers. Reproducibility was lower from duplicate OVMs for BTEX (benzene, toluene, ethylbenzene, and xylene isomers) VOCs (≥7% RSD for 2-day samples) with better precision for longer sampling periods. Comparison of Ogawa NO₂ samplers with chemiluminescence measurements averaged over the same time period suggested potential calibration problems with the chemiluminescence analyzer. For BTEX species, generally good agreement was obtained between OVMs and automated-gas chromatograph (auto-GC) measurements. The OVMs successfully tracked increasing levels of VOCs recorded by the auto-GCs.     

A Short-Term Diffusive Sampler for Nitrogen Dioxide Monitoring in Epidemiology

An automated timed exposure diffusive sampler (TEDS) for sampling nitrogen dioxide (NO₂) was developed for use in epidemiological studies. The TEDS sequentially exposes four passive sampling devices (PSD) by microprocessor controlled valves while a pump and air flow guide prevent sampler "starvation." Two TEDS units and two portable, real-time NO₂ monitors were tested for accuracy, precision, sensitivity, and linearity of response. The accuracy of the TEDS was within 10 percent of the calibrated NO₂ values, and precision was within 10 percent of the means of the measured values. The TEDS sensitivity was 20 to 30 ppb-hour for NO₂. Co-location of the TEDS with a chemiluminescent NOX monitor (EPA reference method) showed similar responses to ambient NO₂ (R2 = 0.9991). TEDS allows better time resolution than traditional diffusive samplers (i.e., Palmes tube) while sharing their ability to sample a variety of gases.     

Personal exposures to NO2 in the EXPOLIS-study: relation to residential indoor,outdoor and workplace concentrations in Basel,Helsinki and Prague

Personal exposures, residential indoor, outdoor and workplace levels of nitrogen dioxide (NO₂) were measured for 262 urban adult (25–55 years) participants in three EXPOLIS centres (Basel; Switzerland, Helsinki; Finland, and Prague; Czech Republic) using passive samplers for 48-h sampling periods during 1996–1997. The average residential outdoor and indoor NO₂ levels were lowest in Helsinki (24±12 and 18±11 μg m⁻³, respectively), highest in Prague (61±20 and 43±23 μg m⁻³), with Basel in between (36±13 and 27±13 μg m⁻³). Average workplace NO₂ levels, however, were highest in Basel (36±24 μg m⁻³), lowest in Helsinki (27±15 μg m⁻³), with Prague in between (30±18 μg m⁻³). A time-weighted microenvironmental exposure model explained 74% of the personal NO₂ exposure variation in all centres and in average 88% of the exposures. Log-linear regression models, using residential outdoor measurements (fixed site monitoring) combined with residential and work characteristics (i.e. work location, using gas appliances and keeping windows open), explained 48% (37%) of the personal NO₂ exposure variation. Regression models based on ambient fixed site concentrations alone explained only 11–19% of personal NO₂ exposure variation. Thus, ambient fixed site monitoring alone was a poor predictor for personal NO₂ exposure variation, but adding personal questionnaire information can significantly improve the predicting power.     

Application of passive sorbent tube and canister samplers for volatile organic compounds at refinery fenceline locations in Whiting,Indiana

Select volatile organic compounds (VOCs) in ambient air were measured at four fenceline sites at a petroleum refinery in Whiting, IN, using modified EPA Method 325 A/B with passive tubes and EPA Compendium Method TO-15 with canister samplers. One-week, time-integrated samplers were deployed for 8 weeks with tubes and canister samplers deployed in duplicate. Good precision was obtained from the duplicate tubes (<7%) and duplicate canisters (≤10%) for BTEX, perchloroethylene, and styrene. The tubes yielded statistically significantly higher concentrations than canisters for benzene, toluene, ethylbenzene, and m,p-xylene. However, all differences were estimated to be <0.1 ppbv. No concentration differences among the four Whiting sites were found for any of the VOCs.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at refinery fenceline locations. This pilot study presents VOC data applying a modified version of EPA Method 325 A/B and its comparison to EPA Compendium Method TO-15 canister samplers at four refinery fenceline sites. The findings from this study provide additional confidence in application of the tube method at refineries to ascertain VOC source influence since tube and canister samplers were comparable and good precision was obtained from duplicate sampling for both methods. No overall difference in these reported VOC concentrations was found between Whiting sites for tubes or canisters.     

Gaseous and particulate water-soluble organic and inorganic nitrogen in rural air in southern Scotland

Simultaneous daily measurements of water-soluble organic nitrogen (WSON), ammonium and nitrate were made between July and November 2008 at a rural location in south-east Scotland, using a ‘Cofer’ nebulizing sampler for the gas phase and collection on an open-face PTFE membrane for the particle phase. Average concentrations of NH₃ were 82 ± 17 nmol N m^?3 (error is s.d. of triplicate samples), while oxidised N concentrations in the gas phase (from trapping NO₂ and HNO₃) were smaller, at 2.6 ± 2.2 nmol N m^?3, and gas-phase WSON concentrations were 18 ± 11 nmol N m^?3. The estimated collection efficiency of the nebulizing samplers for the gas phase was 88 (±8) % for NH₃, 37 (±16) % for NO₂ and 57 (±7) % for WSON; reported average concentrations have not been corrected for sampling efficiency. Concentrations in the particle phase were smaller, except for nitrate, at 21 ± 9, 10 ± 6 and 8 ± 9 nmol N m^?3, respectively. The absence of correlation in either phase between WSON and either (NH₃ + NH₄⁺) or NO₃^? concentrations suggests atmospheric WSON has diverse sources. During wet days, concentrations of gas and particle-phase inorganic N were lower than on dry days, whereas the converse was true for WSON. These data represent the first reports of simultaneous measurements of gas and particle phase water-soluble nitrogen compounds in rural air on a daily basis, and show that WSON occurs in both phases, contributing 20–25% of the total water-soluble nitrogen in air, in good agreement with earlier data on the contribution of WSON to total dissolved N in rainfall in the UK.     

Relationship of Indoor N02 Concentrations to Use of Unvented Gas Appliances

In preparation for a prospective study of the relationship of residential nitrogen dioxide exposure and respiratory infections in infants, we conducted a pilot study to assess NO₂ concentrations in a sample of homes in Albuquerque, New Mexico. The methods used to characterize concentrations are described. Three locations in 144 homes were monitored with passive diffusion samplers for two two-week cycles during November and December 1984. Two-week average NO₂ concentrations in the activity room ranged from 2.0 to 168.7 ppb. NO₂ concentrations in the activity room and the infant’s bedroom were fivefold higher in homes with gas stoves than in homes with electric stoves. Sixty-four percent of homes with gas stoves had activity room concentrations that exceeded the highest outdoor concentration. Multiple regression models Indicated that the outdoor concentration, use of a gas stove, particularly one with pilot lights, presence of a gas dryer in the living area, and use of a floor or wall furnace contributed to NO₂ concentrations. Use of a toaster or microwave oven in a house with a gas stove reduced NO₂ concentrations. The results of this study demonstrate a broad range of NO₂ concentrations in Albuquerque. We conclude with suggestions for an exposure assessment strategy that would be valid and feasible in the context of a large epidemiologic study of the health effects of NO₂.     

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.     

Ambient sulfur dioxide,nitrogen dioxide,and ammonia at ten background and rural sites in China during 2007–2008

We present two years (January 2007–December 2008) of atmospheric SO₂, NO₂ and NH₃ measurements from ten background or rural sites in nine provinces in China. The measurements were made on a monthly basis using passive samplers under careful quality control. The results show large geographical and seasonal variations in the concentrations of these gases. The mean SO₂ concentration varied from 0.7 ± 0.4 ppb at Waliguan on Qinghai Plateau to 67.3 ± 31.1 ppb at Kaili in Guizhou province. The mean NO₂ concentration ranged from 0.6 ± 0.4 ppb at Waliguan to 23.9 ± 6.9 ppb at Houma in southern Shanxi. The mean NH₃ concentration ranged from 2.8 ± 3.0 ppb at Shangdianzi in northeastern Beijing to 13.7 ± 8.4 ppb at Houma. At most sites, SO₂ and NO₂ peaked in winter and reached minima in summer, while NH₃ showed maximum values in summer and lower values in cold seasons. On the whole, the geographical distributions of the observed gas concentrations are consistent with those of emissions. The ground measurements of SO₂ and NO₂ are contrasted to the SCIAMACHY SO₂ and OMI NO₂ tropospheric columns, respectively. Although the satellite data can capture the main features of emissions and concentrations of SO₂, they do not reflect the variations of SO₂ in the surface layer. The situation is better for the case of NO₂. The OMI NO₂ columns capture the geographical differences in the ground NO₂ and correlate fairly well with the ground levels of NO₂ at six of the ten sites.     

Assessing Spatial Variability of Ambient Nitrogen Dioxide in Montréal,Canada, with a Land-Use Regression Model

Abstract

The purpose of this study was to derive a land-use regression model to estimate on a geographical basis ambient concentrations of nitrogen dioxide (NO₂) in Montréal, Quebec, Canada. These estimates of concentrations of NO₂ will be subsequently used to assess exposure in epidemiologic studies on the health effects of traffic-related air pollution. In May 2003, NO₂ was measured for 14 consecutive days at 67 sites across the city using Ogawa passive diffusion samplers. Concentrations ranged from 4.9 to 21.2 ppb (median 11.8 ppb). Linear regression analysis was used to assess the association between logarithmic concentrations of NO₂ and land-use variables derived using the ESRI Arc 8 geographic information system. In univariate analyses, NO₂ was negatively associated with the area of open space and positively associated with traffic count on nearest highway, the length of highways within any radius from 100 to 750 m, the length of major roads within 750 m, and population density within 2000 m. Industrial land-use and the length of minor roads showed no association with NO₂. In multiple regression analyses, distance from the nearest highway, traffic count on the nearest highway, length of highways and major roads within 100 m, and population density showed significant associations with NO₂; the best-fitting regression model had a R² of 0.54. These analyses confirm the value of land-use regression modeling to assign exposures in large-scale epidemiologic studies.     

The use of palmes diffusion tubes for measuring NO2 in homes

The results of exposure chamber and field validation tests of NO₂ diffusion tubes are reported. In an exposure chamber about 50 test runs at various relative humidities were performed. The field validation consisted of comparisons between tubes and a chemiluminescence monitor in nine homes during several days in kitchen, living room, bedroom and outdoors. The results indicate a dependency on relative humidity, while the often quoted accuracy of 10% for the diffusion tubes might be too optimistic for the use of the tubes in homes.     

Relating indoor NO2 levels to infant personal exposures

We report here the results of a field survey of personal nitrogen dioxide exposure (PNO₂) of infants and simultaneous indoor NO₂ levels from various points throughout the infants' homes. Personal nitrogen dioxide levels can be predicted by average room NO₂ concentrations when appropriately weighted by infant presence in the room. Bedroom NO₂ concentration alone presents an alternative predictor which is more suitable for use in large scale surveys. Because of the typical infant's peculiar time-location patterns, they receive most of their NO₂ exposures in bedrooms (65 %)and living rooms (32 %), while the kitchen (5 %) and outdoor environments (> 2%)contribute only a small fraction of daily exposure. Average NO₂ exposure during cooking periods can be predicted using passive samplers placed directly over stoves and hours of stove use time.     

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.     

Modeling the intra-urban variability of outdoor traffic pollution in Oslo,Norway—A GA2LEN project

Traffic is a major source of air pollutants in urban environments, and exposure to these pollutants may be associated with adverse health effects. However, inconsistencies in observational epidemiological studies may be caused by differential measurement errors in various approaches in assessing exposure.We aimed to evaluate a simple method for assessing outdoor air pollutant concentrations in Oslo, Norway, through a land-use regression method.Samples of nitrogen oxides (NO_x) were collected in two different weeks using Ogawa passive diffusion samplers simultaneously at 80 locations across Oslo. Independent variables used in subsequent regression models as predictors of the pollutants were derived using the Arc 9 geographic information system (GIS) software. Indicators of land use, traffic, population density, and physical geography were tested.The final regression model yielded an adjusted coefficient of determination (R²) of 0.77 for nitrogen dioxide (NO₂), 0.66 for nitric oxide (NO), and 0.73 for NO_x.The results suggest that a good predictive exposure model can be derived from this approach, which can be used to estimate long-term small-area variation in concentrations for individual exposure assessment in epidemiological studies in a highly cost-effective way. These small-area variations in traffic pollution are important since they may have associations with health effects.     

Major air pollutants in Bursa,Turkey: their levels,temporal changes,interactions, and sources

Bursa is one of the largest cities of Turkey and it hosts 17 organized industrial zones. Parallel to the increase in population, rapidly growing energy consumption, and increased numbers of transport vehicles have impacts on the air quality of the city. In this study, regularly calibrated automatic samplers were employed to get the levels of air pollution in Bursa. The concentrations of CH₄ and N-CH₄ as well as the major air pollutants including PM₁₀, PM_2.5, NO, NO₂, NO_x, SO₂, CO, and O₃, were determined for 2016 and 2017 calendar years. Their levels were 1641.62?±?718.25, 33.11?±?5.45, 42.10?±?10.09, 26.41?±?9.01, 19.47?±?16.51, 46.73?±?16.56, 66.23?±?32.265, 7.60?±?3.43, 659.397?±?192.73, and 51.92?±?25.63 µg/m³ for 2016, respectively. Except for O₃, seasonal concentrations were higher in winter and autumn for both years. O₃, CO, and SO₂ had never exceeded the limit values specified in the regulations yet PM₁₀, PM_2.5, and NO₂ had violated the limits in some days. The ratios of CO/NO_x, SO₂/NO_x, and PM_2.5/PM₁₀ were examined to characterize the emission sources. Generally, domestic and industrial emissions were dominated in the fall and winter seasons, yet traffic emissions were effective in spring and summer seasons. As a result of the correlation process between O_x and NO_x, it was concluded that the most important source of O_x concentrations in winter was NO_x and O₃ was in summer.     

Characterization of the olfactory impact around a wastewater treatment plant: Optimization and validation of a hydrogen sulfide determination procedure based on passive diffusion sampling

A monitoring program based on an indirect method was conducted to assess the approximation of the olfactory impact in several wastewater treatment plants (in the present work, only one is shown). The method uses H₂S passive sampling using Palmes-type diffusion tubes impregnated with silver nitrate and fluorometric analysis employing fluorescein mercuric acetate. The analytical procedure was validated in the exposure chamber. Exposure periods of at least 4 days are recommended. The quantification limit of the procedure is 0.61 ppb for a 5-day sampling, which allows the H₂S immission (ground concentration) level to be measured within its low odor threshold, from 0.5 to 300 ppb. Experimental results suggest an exposure time greater than 4 days, while recovery efficiency of the procedure, 93.0 ± 1.8%, seems not to depend on the amount of H₂S collected by the samplers within their application range. The repeatability, expressed as relative standard deviation, is lower than 7%, which is within the limits normally accepted for this type of sampler. Statistical comparison showed that this procedure and the reference method provide analogous accuracy. The proposed procedure was applied in two experimental campaigns, one intensive and the other extensive, and concentrations within the H₂S low odor threshold were quantified at each sampling point. From these results, it can be concluded that the procedure shows good potential for monitoring the olfactory impact around facilities where H₂S emissions are dominant.

Implications: Passive samplers are very attractive tools to experimentally tackle a number of air pollution problems, especially those related to odor impact. Their small size and cost permit a denser sampling design and thus a more detailed spatial characterization than other techniques. On the other hand, the large inherent variability in passive sampler measures requires an uncertainty analysis of the chemical species and analytical procedures used.