Assessment of uncertainty of NO2 measurements by the chemiluminescence method and discussion of the quality objective of the NO2 European Directive

Hereafter, an assessment of the ability of the chemiluminescence method to measure ambient NO2 with an accuracy within 15%, as requested by the data quality objective of European directive 1999/30/CE, is presented. In general, uncertainty is evaluated using the response to reference materials or by means of inter-comparisons used to determine some statistics like repeatability, reproducibility and calibration bias. These are incomplete approaches and the method of the Guide to the Expression of Uncertainty in Measurement, advised by the Directive, should be preferred. In fact, even if it requires a large data set, it allows the relative influence of all possible sources of uncertainty to be studied. The extent of NO2 uncertainty is mainly dependent on the level of NO. It is decreased by NOx and the correlation between NOx and NO. Furthermore, the uncertainty budget reveals that the contribution of accuracy of calibration standard, linearity, converter efficiency and drift of the analyser between calibration checks to the overall uncertainty is less important than the contribution of interference, mainly humidity and PAN in rural areas. The relative expanded uncertainty of the NO2 hourly average exceeds 30% for NO2 concentrations lower than 40 microg m(-3). Nevertheless, the data quality objective of 15% is reached for 200 microg m(-3), the hourly limit value of the European directive. On the contrary, at the limit value on the annual average, 40 microg m(-3), the data quality objective is not met if NO is higher than 100 microg m(-3). However, the data quality objective could be reached by correcting the measurements with the bias due to interference.     

Indoor and outdoor air concentrations of BTEX and NO2: correlation of repeated measurements

Studies on health effects of air pollutants ideally define exposure through the collection of air samples in the participants' homes. Concentrations derived from these samples are then considered as an estimate for the average concentration of air pollutants in the homes. Conclusions drawn from such studies therefore depend very much on the validity of the measured air pollution concentrations. In this paper we analysed repeated BTEX and NO(2) measurements with a time period of several months lying between the two conducted home visits. We investigated the variability of their concentrations over time by determining correlation coefficients and calculating within- and between-home variances. Our population consisted of 631 homes of participants from two cohort studies within the framework of the German study on Indoor Factors and Genetics in Asthma. Air pollutants were measured using passive samplers both indoors and outdoors. The measured BTEX concentrations were poorly correlated, with Pearson's correlation coefficient r ranging from -0.19 to 0.27. Additionally, a considerable seasonal effect could be observed. A higher correlation was found for the NO(2) concentrations with r ranging between 0.24 and 0.55. For the BTEX, the between-home variance was bigger than the within-home variance, for NO(2) both variances were of about the same order. Our results indicate that in a setting of moderate climate like in Germany, the variability of BTEX and NO(2) concentrations over time is high and a single measurement is a poor surrogate for the long-term concentrations of these air pollutants.     

Indoor NO2 pollution and personal exposure to NO2 in two areas with different outdoor NO2 pollution

Indoor NO₂ concentrations were measured in the kitchen, the living room and bedroom of 612 houses in two different areas in the Netherlands. In a group of housewives living in these homes, personal exposure to NO₂ was measured. NO₂ concentrations indoors were dependent on the presence or absence of (un)vented gas appliances. Personal NO₂ exposure was only different between the two areas in the group with the lowest indoor concentrations. In this study, it was determined that gas appliances inside the house are the most important factor with respect to NO₂ exposure and that outside NO₂ concentration played a secondary role, except in situations where gas appliances were absent.     

CO and NO2 pollution in a long two-way traffic road tunnel: investigation of NO2/NOx ratio and modelling of NO2 concentration

The CO, NO and NO2 concentrations, visibility and air flow velocity were measured using continuous analysers in a long Norwegian road tunnel (7.5 km) with traffic in both directions in April 1994 and 1995. The traffic density was monitored at the same time. The NO2 concentration exceeded Norwegian air quality limits for road tunnels 17% of the time in 1994. The traffic through the tunnel decreased from 1994 to 1995, and the mean NO2 concentration was reduced from 0.73 to 0.22 ppm. The ventilation fan control, based on the CO concentration only, was unsatisfactory and the air flow was sometimes low for hours. Models for NO2 concentration based on CO concentration and absolute air flow velocity were developed and tested. The NO2/NOx ratio showed an increase for NOx levels above 2 ppm; a likely explanation for this phenomenon is NO oxidation by O2. Exposure to high NO2 concentrations may represent a health risk for people with respiratory and cardiac diseases. In long road tunnels with two-way traffic, this study indicates that ventilation fan control based on CO concentration should be adjusted for changes in vehicle CO emission and should be supplemented by air flow monitoring to limit the NO2 concentration.     

Validation of a diffusive sampler for NO2

A diffusive sampler for NO2, Willems badge, was validated in laboratory experiments and field tests. The collecting reagent for NO2 in the sampler is triethanolamine, and the analysis is based on a modified colorimetric method, the Saltzman method. The analysis was performed by a flow injection analysis (FIA) technique. The sampling rate for the sampler was determined to be 40.0 ml min-1. There was no effect of NO2 concentration or relative humidity on sampling rate, and the influence of sampling time was found to be small. The detection limit was 4 micrograms m-3 for a 24 h sample. The capacity is high enough to allow sampling of 150 micrograms m-3 for 7 days, which is twice the recommended Swedish short-term (24 h) guideline value as a 98-percentile over 6 months. In field tests, the sampler performed well, even at wind speeds higher than 2 m s-1, and at low temperatures. The overall uncertainty of the method was 24%. The sensitivity and capacity of the method also make it suitable for personal sampling for 2-8 h in working environments.     

Spatial and temporal variation of surface ozone,NO and NO2 at urban,suburban, rural and industrial sites in the southwest of the Iberian Peninsula

Surface ozone is one of the most important photochemical pollutants in the low atmosphere, causing damage to human health, vegetation, materials and climate. The weather (high temperatures and high solar radiation), orography (presence of the Guadalquivir valley) and anthropogenic (the cities of Cádiz, Córdoba, Huelva and Seville and two important industrial complexes) characteristics of the southwestern Iberian Peninsula make this region ideal for the formation and accumulation of ozone. To increase the knowledge of ozone behaviour in this area, the monthly, daily and weekly variations of ozone and its precursors, nitrogen oxides (NO_x?=?NO?+?NO₂), were analysed over a 4-year period (2003 to 2006). Using the k-means cluster technique, 12 representative stations of five different areas with different ozone behaviour were selected from a total of 29 monitoring sites. This is the first time that the analysis of these atmospheric pollutants has been carried out for the whole area, allowing therefore a complete understanding of the dynamics and the relationships of these compounds in this region. The results showed an opposite behaviour among ozone and NO and NO₂ concentrations in urban and suburban zones, marked by maximums of ozone (minimums NO_x) in spring and summer and minimums (maximums) in autumn and winter. A seasonal behaviour, with lower amplitude, was also observed in rural and industrial areas for ozone concentrations, with the NO and NO₂ concentrations remaining at low and similar values during the year in rural zones due to the absence of emission sources in their surroundings. The daily cycles of ozone in urban, suburban and industrial sites registered a maximum value in the early afternoon (14:00–17:00 UTC) while for NO_x two peaks were observed, at 7:00–10:00 UTC and 20:00–22:00. In the case of rural stations, no hourly peak of ozone or NO_x was registered. The weekend effect was studied by using a statistical contrast tests (Student’s t). The results indicated that only areas influenced by important traffic emissions presented a weekend effect for NO and NO₂, whereas an ozone weekend effect was not detected in any case.     

Case studies on summertime measurements of O3, NO2, and SO2 with a DOAS system in an urban semi-industrial region in Athens, Greece

The objective of this study is to analyze the concentrations of SO₂, NO₂, and O₃ measured by a Differential Optical Absorption Spectroscopy (DOAS) system that was operating at the campus of Technological Education Institute of Piraeus during 2008 and 2009 warm periods (July to September) in relation to the prevailing meteorological conditions. The DOAS system was operating in a particularly polluted area of the West part of Attica basin on a continuous basis, measuring the concentration levels of the main pollutants (O₃, NO₂, and SO₂) as well as aromatic hydrocarbon substances (benzene, toluene, and xylene). According to the analysis, the SO₂ concentration levels at this measuring site are rather high and this may be attributed to the characteristics of this measuring site. Proximity of roadways and local circulation are just some of the factors that can affect the concentration levels of monitoring of pollutant concentrations such as NO₂ and surface ozone. The results provide evidence for the occurrence of an atmospheric phenomenon that produces higher ozone concentrations during weekends despite lower concentrations of ozone precursors. This phenomenon is known as the weekend effect.     

Measurements of SO2, NO X and SPM in an industrial area at the Aegean coast of Turkey

Data from continuous measurements of SO₂ NO _x , suspended particulate matter (SPM) and meteorological parameters at seven sites around a highly industrialized region in the Aegean coast of Turkey, between July 15, 1991 to July 31, 1992 were used to evaluate spatial and temporal variations of air quality parameters. Low annual averages and insignificant differences between day and night concentrations were observed at stations far from sources. At stations close to sources, annual average concentrations were high and diurnal patterns were significant. Annual average SO₂ and SPM concentrations in all stations used the Krigging technique to assess the impact of industries on air quality in the surrounding airshed. Results have demonstrated that Turkish air quality standards for SO₂ were exceeded in a circle with a radius of 4 km and which was centered on the petrochemical complex and refinery. Similarly, standards for SPM were exceeded in a circle with a radius of 1.2 km and which was centered on the ironwork plants. Both SO₂ and SPM showed well defined diurnal variations, particularly in stations close to sources. The SO₂ concentrations showed a maximum during day-time, while SPM concentrations peaked after midnight. Although annual average SO₂ and SPM concentrations were highly variable depending on distances between stations and sources, background concentrations of the same pollutants, calculated by stripping episodes from data, did not change significantly from one station to another. Long range transport and resuspension of local soil were suggested as sources of background SO₂ and SPM, respectively. The difference between observed and background concentrations of SO₂ and SPM in each station was related to the impact of industries on air quality at that particular site.     

Correlation between SO2 and NO2 measured in an atmospheric column by a Brewer spectrophotometer and at ground-level by photochemical techniques

An investigation to determine the correlation of atmospheric amounts of SO₂ and NO₂ between columnar measurements from the ground and ground point determinations has been performed. The experimental data have been obtained from a Brewer spectrophotometer for columnar measurements and standard analytical techniques for ground measurements.The results show that the Brewer can give a correct indication of the trend of these pollutants on a monthly averaged basis. The possibility of deducing the mixing layer depth from the measured data has also been investigated but the results obtained are not conclusive due to the lack of an accurate experimental verification.     

Emissions of NO and N2O from soils

Nitric oxide (NO) and nitrous oxide (N₂O) fluxes were measured from agricultural, forest and moorland environments, using chamber techniques. Maximum emissions of NO and N₂O were measured from the agricultural soils shortly after fertiliser application (7 ng NO-N m^–2 s^–1 and 91 ng N₂O-N m^–2 s^–1). For the non-agricultural soils the NO flux ranged from –0.3 to 0.5 ng NO-N m^–2 s^–1 and the N₂O flux ranged from 1 to 2.7 ng N₂O-N m^–2 s^–1. Emissions, however, were increased 2 to 7 fold when N deposition (uplands) and N fixation (alder plantations) contributed to the pool of soil available N. The best predictors of the NO emission were soil NO ₃ ^– and soil temperature, accounting for 60% of the variability observed. The prediction of N₂O was less successful. Only 30% of the variability could be explained by the soil NO ₃ ^– and the soil moisture content, soil temperature did not have a significant effect on the N₂O emission.     

被动采样监测环境空气中SO2和NO2

用自主研制的采样管开展环境空气中SO2和NO2的被动采样监测.结果表明,被动采样监测结果与自动监测结果高度相关,经回归方程修正后,两者的结果没有显著性差异,被动采样的采样和分析产生的误差得以消除.     

Laboratory and field validation of a combined NO2-SO2 Radiello passive sampler

A combined NO2-SO2 Radiello radial-type diffusive sampler was validated under controlled laboratory conditions and compared with NO2-SO2 results of 3 other type of samplers in a field comparison at two locations Ghent-Mariakerke and Borgerhout in Flanders. Laboratory exposures at different temperatures (-5, 10 and 30 degrees C) and relative humidities (0, 50 and 80% RH) in combination with varying concentration levels and exposure times were carried out, with a focus on extreme conditions. Concentration level and exposure time were changed together following suppliers linear working range of samplers and assuring absolute amounts of compounds on the sampler corresponding to those of environmental levels. The average uptake rate for NO2 for 24 hour exposures at 10 degrees C and 50% RH and tested concentration levels (+/-73, 146 and 293 ppb NO2) was 0.076 +/- 0.011 ng ppb(-1) min(-1). Uptake rates during all experiments were lower than the uptake rate given in the instruction manual of the sampler. A significant effect of temperature and relative humidity on NO2 uptake rate was observed. The temperature effect from 10 to 30 degrees C corresponds to the temperature effect given by the supplier of the samplers. High relative humidity (70 to 80%) caused a strong non-reproducible decrease of uptake rate for NO2 at 24 hour experiments but this effect was not observed at longer exposures except for the tests at -5 degrees C. At the tested temperature below zero in combination with high relative humidity the sampler showed anomalous behaviour for NO2. The possible effect of concentration level and exposure time for NO2 needs further research. The average uptake rate for SO2 calculated from all exposures is 0.478 +/- 0.075 ng of sulfate ion each ppb min of SO2 and accords to suppliers uptake rate. No clear effects of temperature, relative humidity or concentration level/exposure time on the uptake rate for SO2 were found, partly due to the large scatter of results. Although NO2 accuracy of Radiello samplers was better during field campaigns than during laboratory validation, IVL and OGAWA samplers gave better results for NO2. In the field, IVL samplers showed best agreement with the continuous analyzers for both NO2 and SO2.     

Effect of Temperature on Absorption Efficiency of NO2 in Arsenite Method

The sodium arsenite method developed by Jacobs andHochheiser is one of the most widely used manualmethods for nitrogen dioxide (NO₂) monitoring inambient air, particularly in developing countries. Asreported, the method gives 82% NO₂ absorptionefficiency (NAE) in the concentration range from 40 to750 g/m³, when only one impinger tube isemployed in the sampling train at a flow rate of 0.2lpm and for 24 h sampling duration. Accordingly,a uniform correction factor (0.82) is used indenominator to calculate the ultimate concentration ofNO₂ in ambient air.In the present investigation, the effect oftemperature on absorption efficiency of NO₂ isstudied employing four impinger tubes in series tocollect the maximum NO₂ generated in the gasstream. The study conducted at 16, 26 and 36 °Ctemperatures shows maximum absorption efficiency(average) of 87.8% at 26°C in 1st impingertube. At lower and higher temperatures, it is foundconsiderably less. A suitable correction factor,therefore, must be applied to estimate actual NO₂concentration in ambient air using arsenite method, intropical countries like India, where atmospherictemperature variations are large (less than 5°Cin winter and more than 45°C in summer).     

惠州市城区NO2污染水平的分析与模拟

分析了2004年惠州市城区各监测站点的NO2数据,结果表明,NO2对城区空气质量影响不大。采用了城市空气质量管理软件模拟了NO2空间分布及日变化情况,且与实测值的比较分析表明,模拟结果在城区内有可比性。但地处城市边缘地带的污染模拟受光化学和区域性污染的影响,有待于进一步研究。所得结论可为惠州市城区优化布点的研究提供一定的参考。     

Field Comparison of two NO2 Passive Samplers to Assess Spatial Variation

Two-week average NO₂ concentrations were measured in Amsterdam (NL), Huddersfield (UK) and Prague (CZ) at 80 sites in each study area, to assess small area spatial variation, using a tube type and a badge type passive sampler. The badges appeared to be less robust than the tubes. The lower detection limit for tubes and badges was 3.7 and 0.91 µg/m³, respectively for fortnightly measurements. Accuracy of the samplers was determined with reference methods (chemiluminescence). The mean ratio of the concentration measured by diffusion tube over that by the reference method was 1.16, 1.03 and 0.77 in Amsterdam, Huddersfield and Prague, respectively. Standardizing the badges for the results obtained in Amsterdam, the relative mean ratio of the concentration measured by the badges over that by the reference method was 0.95 and 0.58 in Huddersfield and Prague, respectively. NO₂ concentrations measured by the two designs did not differ significantly. Mean NO₂ concentrations were 36, 26 and 22 µg/m³ in Amsterdam, Huddersfield and Prague, respectively. The precision of duplicate tubes and badges was 8% and 11%, respectively. Both samplers are suitable for determining real variation in small area NO₂ concentrations in the ranges which occurred. It is concluded that low-cost, simple NO₂ passive samplers can provide reliable information about variation in NO₂ concentrations within urban or rural areas on a small spatial scale. Based on its robustness and its precision, tubes were preferred over badges.     

Growth impact of O3, NO2 and/or SO2 on pinus taeda

Seedlings of two full-sib families of loblolly pine expressing different degrees of sensitivity to O₃ were exposed to 0.05 ppm O₃, 0.10 ppm NO₂, and/or 0.14 ppm SO₂ for 6 hr/day for 28 consecutive days. The treatments were O₃, NO₂, SO₂ (each used alone), O₃+SO₂, O₃+NO₂, and O₃+NO₂+SO₂. Significant growth suppressions were noted with the relatively sensitive family in all but the the NO₂ alone treatments. The O₃+SO₂ treatment had a more significant effect than O₃ alone, but adding NO₂ had an inconsistent effect. Significant growth suppressions were noted for the relatively non-sensitive family only in the O₃+SO₂ and O₃+SO₂+NO₂ combination treatments. Adding NO₂ to O₃+SO₂ had a slightly stimulatory effect. The relatively sensitive pine family suffered a 30% height growth suppression versus a 14% height growth suppression for the relatively insensitive family when exposed to the 3 pollutant combination. Symptoms were noted on less than 4% of the foliage in the most severe treatments. The pollutant concentrations used in this study were below the National Ambient Air Quality Standards (NAAQS) for each pollutant.     

Relating Background NO2 Concentrations in Air to Air Mass History Using Non-Parametric Regression Methods: Application at Two Background Sites in Ireland

The concentration of nitrogen dioxide (NO₂) in background air varies temporally and spatially and is influenced by meteorological and anthropogenic factors. Background concentrations used in local air quality modelling studies have a significant effect on the accuracy of the overall result and when based on short-term monitoring data, variation in concentrations with air mass history is often unaccounted for. The current paper presents a powerful tool for the quantification and separation of local and regional air mass effects on background air quality. The origin of and the regions traversed by an air mass prior to reaching a receptor has been modelled using HYsplit-4. Trajectories (between 12 and 96?h duration) were defined based on the frequency with which they passed into 16 predefined compass quadrants and each represented as a vector. Using this vector as the predictor variable and the background concentration as the response variable, non-parametric regression using a Gaussian kernel function was carried out. A graphical output indicated the trajectory direction of maximum NO₂ concentration, while allowing distinction to be made between spurious and true peaks. In all cases, air mass history was found to have a statistically significant effect on NO₂ concentrations. Incorporating emissions data into the analysis local and regional effects were separated and quantified. It was found that emissions in the UK and Europe have a significant effect on background NO₂ concentrations in Ireland and in some instances supersede domestic emissions. The methods can be used to identify source regions, separate local and regional effects and improve predictions of background concentrations based on limited monitoring data. In particular, the results highlight the importance of considering air mass history when assessing background concentration levels for use in local air quality modelling studies.     

流动注射分光光度法测定天然水中亚硝酸根

采用流动注射分析技术,以N-(1-萘基)乙二胺为显色剂在540nm比色,建立了流动注射分光光度法测定亚硝酸根含量的方法。在30个／h样分析速度下,检测限为0．008mg／L。用于天然水样测定,结果令人满意。     

差分光谱法连续监测空气中SO2、NO2、苯、甲苯方法探讨

差分光谱法(简称DOAS)已广泛用于空气中SO2、NO2、苯、甲苯监测.通过对差分光谱法监测结果与其他传统仪器进行时比,发现用DOAS监测SO2、NO2与点式仪器有较好的一致性,但用DOAS系统监测苯、甲苯与气相色谱法有机物连续监测结果差异较大,相关性较差,运行有一定的局限性.另外,本文对DOAS的最佳运行条件进行了探讨,发现影响光强的氙灯老化和气候条件对DOAS系统运行有较大影响.     

Seasonal characteristics of SO2, NO2, and CO emissions in and around the Indo-Gangetic Plain

Anthropogenic emissions of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and carbon monoxide (CO) exert significant influence on local and regional atmospheric chemistry. Temporal and spatial variability of these gases are investigated using surface measurements by the Central Pollution Control Board (India) during 2005–2009 over six urban locations in and around the Indo-Gangetic Plain (IGP) and supported using the satellite measurements of these gases. The stations chosen are Jodhpur (west of IGP), Delhi (central IGP), Kolkata and Durgapur (eastern IGP), Guwahati (east of IGP), and Nagpur (south of IGP). Among the stations studied, SO₂ concentrations are found to be the highest over Kolkata megacity. Elevated levels of NO₂ occur over the IGP stations of Durgapur, Kolkata, and Delhi. Columnar NO₂ values are also found to be elevated over these regions during winter due to high surface concentrations while columnar SO₂ values show a monsoon maximum. Elevated columnar CO over Guwahati during pre-monsoon are attributed to biomass burning. Statistically significant correlations between columnar NO₂ and surface NO₂ obtained for Delhi, Kolkata, and Durgapur along with very low SO₂ to NO₂ ratios (≤0.2) indicate fossil fuel combustion from mobile sources as major contributors to the ambient air over these regions.