Influence of temperature changes on ambient air NO<Subscript>x</Subscript> chemiluminescence measurements

Users of automatic air pollution monitors are largely unaware of how certain parameters, like temperature, can affect readings. The present work examines the influence of temperature changes on chemiluminescence NO(x) measurements made with a Thermo Scientific 42i analyzer, a model widely used in air monitoring networks and air pollution studies. These changes are grouped into two categories according to European Standard EN 14211: (1) changes in the air surrounding the analyzers and (2) changes in the sampled air. First, the sensitivity tests described in Standard EN 14211 were performed to determine whether the analyzer performance was adapted to the requirements of the standard. The analyzer met the performance criteria of both tests; however, some differences were detected in readings with temperature changes even though the temperature compensator was on. Sample temperature changes were studied more deeply as they were the most critical (they cannot be controlled and differences of several tens of degrees can be present in a single day). Significant differences in readings were obtained when changing sample temperature; however, maximum deviations were around 3% for temperature ranges of 15°C. If other possible uncertainty contributions are controlled and temperature variations with respect to the calibration temperature are not higher than 15°C, the effect of temperature changes could be acceptable and no data correction should have to be applied.     

Evaluation of short-term Ogawa passive, photolytic, and federal reference method sampling devices for nitrogen oxides in El Paso and Houston, Texas

Passive Sampling Devices (PSDs) have been successfully used by government and academic agencies to monitor common ambient air pollutants such as ozone and nitrogen dioxide (NO(2)). Most PSD studies have involved long-term (e.g. bi-weekly or monthly) sampling. But the Passive Ozone Network of Dallas (POND) studies of 1998 and 1999 showed that high quality 24-hour and 12-hour data using the Ogawa PSD could be collected for ambient ozone concentrations. This paper presents an evaluation of short-term passive sampling results for nitrogen oxides (NO(x)) in El Paso and Houston, Texas, using the Ogawa PSD. The Ogawa NO(x) PSDs were compared to both Federal Reference Method (FRM) monitors and a photolytic converter, with the photolytic converter designed to report closer concentrations to "true" NO(x) by more effectively limiting the interferences of other nitrogen species. Overall, good agreement was noted for all three monitor types in both cities, supporting the potential use of lower cost Ogawa PSDs for large multi-site episodic NO(x)/NO(2)/NO saturation screening studies. This evaluation was conducted during two separate six week periods of the cooler winter months so additional testing of the Ogawa PSDs during different seasons is recommended.     

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.     

Differences between weekend and weekday ozone levels over rural and urban sites in Southern Italy

Air quality data from a network of 11 monitoring stations in the Apulia region of southern Italy during the summer of 2005 reveal a high frequency of ozone law limit violations. Since ozone is a secondary pollutant, air quality control strategies aimed at reducing ozone concentration are not immediate. Herein, we analyse weekly changes in concentration levels of ozone (O(3)), nitrogen oxides (NO(x)), carbon monoxide (CO), and volatile organic compounds (VOCs), and evaluate how the differences in primary emissions cause changes in the production of ozone. The comparison between weekend and weekday levels of O(3) and its precursors are direct evidence for the existence of the "ozone weekend effect." This effect was observed at all stations with a considerable variation in the overall ozone magnitude, including both traffic stations and non-traffic stations. Data from VOC measurements at traffic stations primarily indicated elevated levels of benzene, toluene, and xylenes (BTX); all of these substances showed an overall decrease over the weekend. A single station indicated levels of non-methane hydrocarbon (NMHC) and PM10, both of which did not demonstrate any weekly cycle. Analysis of weekly and diurnal cycles of O(3), NO(x), CO, NMHC, and PM10 indicates that higher weekend ozone levels result from a reduction in the emission of nitrogen oxides on weekends in VOC-sensitive regimes. This indicates that a reduction in VOC and NO(x) levels would be more effective than NO(x) reduction alone. Our results underscore the need for improved and more efficient VOC measurements.     

Harmonization problems in the implemention of the EEC directive on air quality limit values and guide values for sulphur dioxide and suspended particulates

This report deals with the implementation of Article 10 of the Directive on air quality limit values and guide values for sulphur dioxide and suspended particulates (80/779/EEC). For this purpose the Commission, in cooperation with the Member States, has prepared a ‘Common Measurement Programme’ which basically provides for:

1. examination and improvement of the reference measurement methods,
2. examination of the comparability of the measuring procedures and equipment used for monitoring purposes in the Member States,
3. the provision of guidelines and the carrying out of measurements to determine the corresponding stringency of the limit values laid down in Annexes IV and I of the Directive.

     

Evaluation of method of preparation of passive diffusion tubes for measurement of ambient nitrogen dioxide

This study was carried out in response to suggestions that the measurement of NO(2) by Palmes-type passive diffusion tubes (PDT) is affected by the method of preparation of the triethanolamine (TEA) absorbent coating on the grids. The following combinations of factors were investigated: TEA solvent (acetone or water), volume composition of TEA in solvent (50% or 20%), and grid coating method (dipping in solution prior to assembly or pipetting solution on after assembly). Duplicate PDTs prepared by each of the 8 methods were exposed in parallel, in urban air, for a total of 80 separate 1 week exposures. NO(2) concentrations derived from PDTs prepared by pipetting methods were significantly less precise than concentrations from dipping methods, with mean RSDs for duplicate measurements of 13.8% and 8.5%, respectively (n= 316 each category). Pipetting methods using solutions of 50% TEA composition were particularly imprecise (mean RSD 17.2%). Data from PDTs prepared by pipetting methods were systematically more poorly correlated with each other and with data from co-located chemiluminescence analysers, than corresponding data from PDTs prepared by dipping methods, indicating that more consistent accuracy was also obtained by the latter PDTs. The statistical evidence suggested that PDTs prepared by pipetting 50% TEA in water generally gave lower NO(2) concentrations. Although this is in agreement with a previous study, it is also possible that such an observation here may be a statistical artefact given the demonstrably poorer precision of this method. The general tendency of PDTs to show positive bias in NO(2) measurement in urban air in 1 week exposures was again evident in this study (mean biases at roadside and urban centre locations of +35% (n= 475) and +18% (n= 112), respectively) consistent with augmentation of within-tube NO(2) flux by chemical reaction between co-diffusing NO and O(3). Overall, it is recommended that the pipetting method of PDT grid preparation is avoided, or at least investigated further, because of the apparent degradation in precision and accuracy of NO(2) measurement. Potential reasons for the effect are discussed.     

Air quality and ventilation fan control based on aerosol measurement in the bi-directional undersea Bømlafjord tunnel

Aerosol, NO and CO concentration, temperature, air humidity, air flow and number of running ventilation fans were measured by continuous analysers every minute for a whole week for six different one-week periods spread over ten months in 2001 and 2002 at measuring stations in the 7860 m long tunnel. The ventilation control system was mainly based on aerosol measurements taken by optical scatter sensors. The ventilation turned out to be satisfactory according to Norwegian air quality standards for road tunnels; however, there was some uncertainty concerning the NO2 levels. The air humidity and temperature inside the tunnel were highly influenced by the outside metrological conditions. Statistical models for NO concentration were developed and tested; correlations between predicted and measured NO were 0.81 for a partial least squares regression (PLS1) model based on CO and aerosol, and 0.77 for a linear regression model based only on aerosol. Hence, the ventilation control system should not solely be based on aerosol measurements. Since NO2 is the hazardous polluter, modelling NO2 concentration rather than NO should be preferred in any further optimising of the ventilation control.     

环境空气气态污染物(CO、SO2、NO)标准气体质量评估

为了解当前不同来源环境空气气态污染物（CO、SO₂、NO）标气质量状况,选择12家主流气态污染物（CO、SO₂、NO）标气制造商,分别匿名采购3种气态污染物标气,建立2家参考实验室共同测试的模式和计量溯源一致性评价方法,对标气进行测试后,采用En值法评价其定值准确性,同时评估其技术资料完整性。结果显示：12家制造商的72瓶有证标气中,有9瓶标气定值结果准确性评价为不合格,涉及5个制造商来源,其中NO作为反应性气体,不合格标气数量最多,占比达20.8%;12家制造商中8家技术资料完整。鉴于标准气体对气态污染物监测结果的准确性、可比性和可溯源性具有重要意义,建议进一步加强标气质量事中事后监管和行业评估,推动制造商不断提高标气生产水平。标气使用者则应尽量选择质量可靠的有证标气。     

Proximity analysis of air pollution exposure and its potential risk

Proximity analysis and spatial variability of the ambient nitrogen dioxide (NO(2)) concentration in Rayong province, Thailand, were analyzed using geostatistics and spatial modeling techniques. Annual concentrations of nitrogen dioxide were predicted and spatially interpolated using various interpolation techniques (i.e. kriging, IDW and spline). Sensitivity analysis was carried out to assure the accuracy of the predicted results. The GIS-based exposure map was simulated and was assisted to identify high exposure areas. A health risk warning system was set for "action" (exceeds 100% of the annual average NO(2) guideline), for "alert" (between 66-100% of the annual average NO(2) guideline) and for "some concern" (between 33-66% of the annual average NO(2) guideline). Although no areas were exposed to an action level, many locations in the study area could have levels of "some concern". Potential risk to the population was analyzed by spatial interpolation of the nitrogen dioxide concentration with population data. The result indicated the number of people exposed to air pollution, as well as the areas which have a high risk to air pollution. About 88.3% of the total population in the study area live in areas where levels of air pollution are designated as being in the "some concern" zone. About 6.7% of the registered population have their residence in an area where action should be taken for air quality management. The study demonstrates the application of GIS-based prediction for the evaluation of exposure mapping, in order to determine the spatial extent and frequency of areas where pollution levels exceed target values, and their potential health impacts.     

The equivalence of diffusive samplers to reference methods for monitoring O3, benzene and NO2 in ambient air

A study of the equivalence to the reference methods of the Radiello samplers for ozone (O(3)) and benzene as well as the membrane-closed Palmes tube (MCPT) for nitrogen dioxide (NO(2)) is presented. These samplers benefit from new model equations capable of estimating their uptake rate. For O(3), the aim here was to demonstrate the equivalence for the reference period of 8 h and 120 microg m(-3), the target value of the 3rd European Daughter Directive. For benzene, the demonstration of equivalence to the annual limit value of 5 microg m(-3) of the 2nd European Daughter Directive was examined. In the case of NO(2), the equivalence to the annual limit value of the 1st European Daughter Directive (40 microg m(-3)) was considered. Results show that the radial sampler for O(3) fails to meet the Data Quality Objective (DQO) for continuous monitoring. However, with an expanded uncertainty of less than 30%, the O(3) diffusive sampler fulfils the DQO for indicative measurements. For benzene, the Radiello sampler exposed for 7 days gave satisfying results showing the ability of the sampler to meet the DQO of the reference method. Nevertheless, the field tests should be complemented by measurements for a wider range of benzene concentrations. In the case of NO(2), all the results of the laboratory and field experiments respected the requirements necessary for the demonstration of equivalence. Overall, these findings thus show that the Radiello sampler and the MCPT are equivalent to the reference methods only for assessment of benzene and NO(2), respectively.     

Roadside Concentration of Gaseous and Particulate Matter Pollutants and Risk Assessment in Dar-Es-Salaam, Tanzania

This study used manual air sampling method to assess the contribution of road traffic to air pollution level in Dar-es-Salaam City, Tanzania. Samples were collected from 11 different sites. Parameters measured were: sulphur dioxide using pararosaniline method, nitrogen dioxide using saltzman method, particulate matter and particulate lead using filtration method and atomic absorption spectrometric method, respectively. Results showed that hourly average sulphur dioxide concentration range from 127 to 1385 g/m³. The measured values of sulphur dioxide were above the recommended WHO guidelines with an hourly objective value of 350 g/m³ at 87% of the sampling sites. The hourly average nitrogen dioxide concentration ranged from 18 to 53 g/m³. The maximum hourly nitrogen dioxide concentration at 53 g/m³ was below the WHO guideline value of 200 g/m³. The hourly average suspended particulate matter (SPM) ranged from 98 to 1161 g/m³, exceeding the recommended value of 230 g/m³ by WHO at 87% of the sampling sites. The hourly average lead concentration was found to range from 0.60 to 25.6 g/m³, exceeding again the WHO guideline value of 1.5 g/m³at 83% of the sampling sites. Results predicted by Gaussian model when compared with the measured values were found to have a correlation coefficient of 0.8, signifying a good correlation. The risk assessment was undertaken considering the people who spend a significant portion of their time near the roads, such as the Uhuru primary school pupils and the adult population who reside by the roadside. The unit risk realised was 18.2 × 10^–6 for adult population and 2.2 × 10^–6 for pupils, both scenarios showing risk higher than the United Sates of America Environmental Protection Agency (USEPA) acceptable limit of 1× 10^–6. Considering the magnitude of the problem at hand, this study recommends an introduction of mandatory emission tests of SPM, lead and sulphur dioxide (SO₂). The study further recommends the introduction of continuous and/or regular air quality monitoring and the use non-leaded petrol in Tanzania.     

Applicability of hydromorphological monitoring data to locate flood risk reduction measures: Blanice River basin, Czech Republic

This paper presents a new methodological approach, using hydromorphological monitoring data from river networks, to identify stream elements that may negatively influence the course of floods, as well as elements suitable for modifications that will reinforce the natural retention potential of the floodplain. The approach uses data derived from hydromorphological monitoring that conforms to the EN 14614 standard "Water quality--Guidance standard for assessing the hydromorphological features of rivers." Four major aspects of stream modifications that can potentially affect the course and consequences of floods, and that can be derived from hydromorphological monitoring, were identified. These are: (1) modifications that increase the speed of runoff, (2) modifications that restrict the retention potential of the floodplain, (3) potential obstacles to the flood course, and (4) improper alterations of stream route modifications. A GIS is used to identify and locate these critical aspects of stream and floodplain modification. This method was applied in the Blanice River basin, an area in central Europe hit by a severe flood in August 2002. The critical modifications identified were compared with geomorphological mapping to display the different effects of individual types of modifications.     

Estimation of the rate of increase in nitrogen dioxide concentrations from power plant stacks using an imaging-DOAS

The emission of nitrogen compounds from power plants accounts for a significant proportion of the total emissions of nitrogen to the atmosphere. This study seeks to understand the nature of chemical reactions in the atmosphere involving nitrogen, which is important in undertaking quantitative assessments of the contribution of such reactions to local and regional air pollution. The slant column density (SCD) of power-plant-generated NO(2) was derived using imaging differential optical absorption spectroscopy (I-DOAS) with scattered sunlight as a light source. The vertical structure of NO(2) SCD from power plant stacks was simultaneously probed using a pushbroom sensor. Measured SCDs were converted to mixing ratios in calculating the rate of NO(2) increase at the center of the plume. This study presents quantitative measurements of the rate of NO(2) increase in a rising plume. An understanding of the rate of NO(2) increase is important because SO(2) and NO(x) compete for the same oxidizing radicals, and the amount of NO(x) is related to the rates of SO(2) oxidation and sulfate formation. This study is the first to directly obtain the rate of NO(2) increase in power plant plumes using the I-DOAS technique. NO(2) increase rates of 60 and 70 ppb s(-1) were observed at distances of about 45 m from the two stacks of the Pyeongtaek Power Plant, northwest South Korea.     

Analysis of the air pollution climate at a background site in the Po valley

The Po valley in northern Italy is renowned for its high air pollutant concentrations. Measurements of air pollutants from a background site in Modena, a town of 200 thousand inhabitants within the Po valley, are analysed. These comprise hourly data for CO, NO, NO(2), NO(x), and O(3), and daily gravimetric equivalent data for PM(10) from 1998-2010. The data are analysed in terms of long-term trends, annual, weekly and diurnal cycles, and auto-correlation and cross-correlation functions. CO, NO and NO(2) exhibit a strongly traffic-related pattern, with daily peaks at morning and evening rush hour and lower concentrations over the weekend. Ozone shows an annual cycle with a peak in July due to local production; notwithstanding the diurnal cycle dominated by titration by nitrogen oxide, the decreasing long term trend in NO concentration did not affect the long term trend in O(3), whose mean concentration remained steady over the sampling period. PM(10) shows a strong seasonality with higher concentration in winter and lower concentration in summer and spring. Both PM(10) and ozone show a marked weekly cycle in summer and winter respectively. Regressions of PM(10) upon NO(x) show a consistently greater intercept in winter, representing higher secondary PM(10) in the cooler months of the year. There is a seasonal pattern in primary PM(10) to NO(x) ratios, with lower values in winter and higher values in summer, but the reasons are unclear.     

一氧化氮标准气体中二氧化氮杂质FTIR定量方法研究及标气质量分析

一氧化氮标准气体在我国空气质量监测工作中广泛用于氮氧化物分析仪的校准,标准气体的质量对环境空气中氮氧化物的测量结果也有着显著的影响。利用傅里叶变换红外光谱仪建立了一套精确测量低浓度二氧化氮方法,并对一氧化氮标准气体产品中二氧化氮杂质进行了测量。结果显示有少部分样品中存在较高浓度的二氧化氮杂质。进一步讨论了可能导致一氧化氮标准气体中二氧化氮杂质偏高的原因,及此种情况对化学发光法氮氧化物分析仪准确测量空气中氮氧化物可能产生的影响。为了准确校准化学发光法氮氧化物分析仪,应关注一氧化氮标准气体产品中的二氧化氮杂质的含量。     

RELEVANT ASPECTS OF AIR QUALITY IN OPORTO (PORTUGAL): PM10 AND O3

The air quality Framework Directive (FWD) and the correspondent Daughter Directives defined the new strategy for air quality management in Europe. In general, the new standards are more restrictive than those established by the previous legislation. In Portugal, some difficulties can be previewed to achieve those new standards. Thus, this paper aims at evaluating the impact of application of the FWD to Oporto Metropolitan Area in what concerns to the most critical air pollutants in the area (PM₁₀ and O₃). The specific objectives were: i) to analyse the concentration exceedances between 1999 and 2001; ii) to identify the main emission sources; iii) to evaluate the possibility of a new redistribution of the existing monitoring sites; iv) to contribute to the definition of a new strategy for air quality management. The results showed that; i) the standard values for PM₁₀ and O₃ were largely surpassed, possibly concluding that the FWD application implies a strong impact on the air quality management strategies; ii) the main emission sources (road traffic and the neighbour stationary sources localised upwind) affect all the Metropolitan area through intra-region pollutant transport; iii) it is safer maintaining the site localisation to avoid previewing exceedances through mathematical correlations; iv) the reduction of PM₁₀ and of ozone precursors must be performed considering new technologies for cleaner production and gaseous depuration, a rigorous urban and territory planning, the creation of an efficient public transport network and the definition of strict measures for car maintenance.     

Multivariate Statistical Analysis of Meteorological and Air Pollution Data in the ‘Campo De Gibraltar’ Region, Spain

A complete statistical analysis of meteorological and air pollution data was carried out in the ‘Campo de Gibraltar’ region (in the South of Spain) from 1999 to 2002. This is a heavy industrialized area where, up to date, very few air pollution studies have been made. The main objectives of the study presented here have been the characterization of the meteorological and (gaseous and particulate) air pollution conditions in the area, and the relations between them. Multivariate statistical techniques, such as Principal Component Analysis (PCA), have been applied to the data. The results show that air quality in the area is highly dependent on meteorological conditions such as wind persistence and direction, dispersion capability of the atmosphere, and humidity content. On average, sulphur dioxide and nitrogen oxide air pollution, mainly caused by fuel-oil combustion and traffic, respectively, is not very high. However, an important number of exceedences of the limits established by the EU Directive 1999 for PM10 (particulate matter with a diameter less than 10 μm) have been observed in some points of the area. A significant percentage of these exceedences (about 22% on average) are likely caused by African dust intrusions, which usually take place from May to August. From gaseous and particulate air correlations, it seems that anthropogenic activities contribute with about 19% on average.     

Polycyclic aromatic hydrocarbons (PAHs) in atmospheric urban area: monitoring on various types of sites

The air quality over the Toulouse urban area (France) is recorded daily by the regional "Midi-Pyrénées" atmospheric pollution measurements network (ORAMIP). Relevant data is collected from about 100 analysers spread over more than thirty stations. The regulations covering major indicators of atmospheric pollution (ozone, nitrogen dioxide, sulphur dioxide) have been updated in recent years to include additional compounds like polycyclic aromatic hydrocarbons (PAHs). The ORAMIP, in partnership with the ENSIACET has undertaken background PAH average concentration measurements over the urban agglomeration of Toulouse during spring 2006 for various types of sites (traffic, urban, industrial). The sampling was performed using a low volume air sampler equipped with quartz fiber filters and polyurethane foams For the two urban sites, total atmospheric concentrations between 12 and 20 ng/m(3) have been obtained, whereas for the industrial site the values averaged 22 ng/m(3). In addition, and regardless of site, the average concentrations of benzo[a]pyrene, at present the only regulated PAH, were always less than the 1 ng/m(3) limit.     

Effect of sample flow rate and sampling duration on the absorption of NO2 in the sodium arsenite monitoring method

The effect of the two most critical parameters, the sample flow rate and sampling duration, on the absorption efficiency of NO2 in the sodium arsenite method of nitrogen dioxide determination in ambient air was studied. Laboratory experiments showed a high sensitivity to these parameters, which were subjected to variation during actual field monitoring. The reported NO2 absorption efficiency of the method of 82% at a flow rate of 0.2 l min-1 was found to be as low as 33% at a flow rate of 1.0 l min-1 for a sampling duration of 24 h. Similarly, a considerable decrease in absorption efficiency with increasing sampling duration from 2 to 24 h was observed at a particular flow rate. Correction factors for the absorption efficiency were evolved that can be used to update the existing database, as well as future NO2 data generated using this manual monitoring method.     

机场大气污染物高时间分辨率排放清单计算方法研究

通过研究机场大气污染物排放特征,结合我国相关排放政策及规范,以排放因子法为主要方法,设计了可建立机场高时间分辨率大气污染物排放清单的计算方法,以期为机场大气污染物排放实时监管提供研究基础。该方法针对飞机发动机和地面保障设备(GSE),实现了颗粒物、二氧化硫、氮氧化物等大气污染物和温室气体的半小时级别排放量计算。通过收集整理北京首都国际机场日航班计划与GSE运作情况实际数据,计算并建立了高时间分辨率的排放清单,验证了计算方法的可行性。随后,从活动水平误差和排放因子适用性两方面,对清单进行了不确定性分析,并通过计算结果对机场排放特征进行了分析,提出了减排建议。