Influence of environmental parameters on the accuracy of nitrogen dioxide passive diffusion tubes for ambient measurement

Two studies at three sites in the UK provided confirmation that systematic positive bias in NO2 diffusion tube measurement occurred because of changes to "within-tube" chemistry, rather than eddy diffusion at the mouth of the tube. In the first study in Cambridge, UK, sampler overestimation for 1 and 2 week exposures was compared to corresponding time-averaged monitor measurements (NO-NO2-NOx, O3) and weather variables. Noninearity between sampler and monitor NO2 measurements was interpreted in terms of spatial and temporal variations in relative and absolute availability of NO, NO2 and O3 at the site. A maximum overestimation occurred for an exposure mean NO2/NOx approximately 0.5. The separate contributions of reduced NO2 photolysis and eddy diffusion were compared in Study II using samplers of two materials, acrylic and quartz, and of different lengths (40, 55, 71 and 120 mm) at three sites: Norwich background, Cambridge intermediate, London kerbside. For compared sites, NO2 measured by acrylic samplers was significantly higher than for equivalent quartz samplers. For quartz samplers [NO2]mean was only just above the monitor at Norwich and London; sampler/monitor NO2 = 1.04 (P = 0.59) and 1.01(P = 0.76), respectively. For acrylic samplers the order of [NO2]mean was 40 mm > 120 mm > 71 mm > or = 55 mm. Excepting 40 mm samplers, this accords with a chemical bias where co-diffusing NO and 03 molecules in longer tubes have more time to react to form excess NO2. Bias in 40 mm samplers is discussed. Eddy diffusion is negligible for standard samplers because [NO2]mean was equivalent for 55 mm and 71 mm acrylic samplers and close to monitor NO2 for 71 mm quartz tubes. Both studies showed that sampler accuracy was dependent on location. Significantly, overestimation was greatest (approximately 3-4 ppb) where the NO2 annual mean was approximately 20 ppb, close to the UK and EU air quality standard of 21 ppb.     

Reliability of nitrogen dioxide passive diffusion tubes for ambient measurement: in situ properties of the triethanolamine absorbent

Factors concerning NO2 uptake by the absorbent triethanolamine (TEA) in NO2 diffusion tubes are examined. Although the nominal freezing point of TEA is 17.9-21.2 degrees C, we show that, for a range of aqueous TEA solutions (0-20%, H2O), no freezing occurs even at -10 degrees C. Therefore NO2 collection efficiency is unlikely to be impaired by low temperature exposure. The recovery of TEA from the meshes of exposed samplers is determined as approximately 98%, even after 42 days, showing that the stability in situ of TEA is unaffected by long-term exposure. A model of a diffusion tube sampling array for simultaneous exposures, with a 0.1 m sampler spacing, shows that NO2 uptake by individual samplers is not affected by the presence of neighbouring tubes in the array. This is confirmed by sampler precision at two Cambridge sites. Four sampler preparation methods are compared for differences in NO2 uptake of exposed samplers. All methods employ TEA as absorbent, transferred by either dipping meshes in a TEA-acetone solution or pipetting aliquots of a TEA-H2O solution onto the meshes. For samplers prepared by three of the methods, no difference in NO2 uptake is found, but for samplers prepared using a 50% v/v TEA-H2O solution, a mean reduction of 18% is found. Student's t-tests show that the difference is highly significant (P < or = 0.001). Reasons for the difference are discussed.     

The effect of absorbent grid preparation method on precision and accuracy of ambient nitrogen dioxide measurements using Palmes passive diffusion tubes

A few studies have suggested that the precision and accuracy of measurement of NO(2) by Palmes-type passive diffusion tube (PDT) are affected by the method of preparation of the triethanolamine (TEA) absorbent coating on the grids. Theses studies have been quite limited in extent and have tended to evaluate PDT accuracy as zero bias between PDT NO(2) value and the exposure-averaged NO(2) determined by co-located chemiluminescence analyser. This ignores the well-documented intrinsic systematic biases on PDT-derived NO(2), such as within-tube chemistry and exposure-duration nitrite loss, which may lead to non-zero bias values irrespective of effects of TEA absorbent preparation method on PDT accuracy. This paper reports on a statistical analysis of a large dataset comprising 680 duplicated PDT exposures spanning 146 separate exposure periods, spread over five urban exposure locations and a number of years. In each exposure period, PDTs prepared by between four and six different grid preparation methods were simultaneously compared. The preparation methods used combinations of the following: acetone or water as the TEA solvent; 20% or 50% as %TEA in the solution; and application of TEA solution by dipping grids for several minutes in the solution before drying and tube assembly, or by pipetting 50 microL of solution directly onto grids already placed in the PDT cap. These represent the range of preparation procedures typically used. Accuracy was evaluated as maximised nitrite capture within an exposure. Data were analysed by general linear modelling including examination of interaction between different aspects of grid preparation method. PDT precision and accuracy were both significantly better, on average, when the PDT grids were prepared by dipping in TEA solution, and neither solvent or %TEA used for the dipping solution were important. Where PDT preparation by pipetting TEA solution onto grids is to be used, better performance was obtained using 20% TEA in water. A systematic positive bias in PDT measure of NO(2), consistent with within-tube oxidation of NO to NO(2) and independent of preparation method, was again evident in this work.     

Measurements of nitrogen dioxide in Greenland using Palmes diffusion tubes

Measurements of nitrogen dioxide using the Palmes diffusion tubes in Uummannaq, Aasiaat, and Nuuk. all located along the west-coast of Greenland, have demonstrated that the levels of pollution at the most heavily impacted sites are comparable to levels in much larger towns in Denmark. The highest concentrations were, in general, observed near sites influenced by car traffic (peak concentrations of up to 16 ppbv), medium concentrations were observed in the residential areas (2 6 ppbv), and very low levels were found at the background locations in the town outskirts (1-2 ppbv). Observations of nitrogen dioxide concentrations less than 0.1 ppbv at a remote site, Akia, 25 km from Nuuk, indicate that, compared to local sources, long-range transport of nitrogen dioxide is not important in western Greenland.     

Performances and application of a passive sampling method for the simultaneous determination of nitrogen dioxide and sulfur dioxide in ambient air

The performances and applicability of a diffusion tubesampler for the simultaneous measurements of NO₂ andSO₂ in ambient air were evaluated. SO₂ andNO₂are collected by the passive sampler using triethanolamine astrapping agent and are determined as sulphate and nitrite withion chromatography. The detection limit (2.3 g m^-3 ofNO₂ and 4.2 g m^-3 of SO₂ for two weekssampling) is adequate for the determination of concentrationsin urban and industrial areas. Precision of the method as RSDis in mean 5% for NO₂ and 12% for SO₂ at theconcentration levels in urban areas. Calibration of the methodwas performed in the field conditions by comparison between theresponses of sampler and the concentrations measured by thecontinuous monitors. High degree of linearity (correlationcoefficients > 0.8) is found between the passive sampler tubeand the continuous monitor data for both NO₂ and SO₂.To reduce the wind velocity influence on passive sampling ofdiffusion tubes, a protective shelter was tested in this study.The overall uncertainty of one measure for the optimised methodis estimated at 5 g m^-3 for NO₂ and 6g m^-3 for SO₂. Suitability of this passivesampling method for air pollution monitoring in urban areas wasdemonstrated by the results shown in this paper on a campaigncarried out in the French agglomeration.     

Evaluation of ogawa passive sampling devices as an alternative measurement method for the nitrogen dioxide annual standard in El Paso, Texas

Nitrogen Dioxide (NO₂) is a common urban air pollutant that results from the combustion of fossil fuels. It causes serious human health effects, is a precursor to the formation of ground level ozone, another serious air pollutant, and is one of the six criteria air pollutants established by the United States (U.S.) Clean Air Act (CAA). Ogawa Passive Sampling Devices (PSDs) for NO₂ were collocated and operated at six NO₂ Federal Reference Method (FRM) monitor locations in the El Paso, Texas area for the 2004 calendar year. Passive samples were taken at 2-week, 3-week, and 4-week intervals and compared against the continuously operating FRM monitors. Results showed that the collective NO₂ annual arithmetic mean for all passive monitors was identical to the NO₂ mean for all FRM monitors. Of the individual locations, three passive annual NO₂ means were identical to their corresponding FRM means, and three passive annual NO₂ means differed from their corresponding FRM means by only one part per billion (ppb). Linear correlation analysis between all readings of the individual NO₂ PSDs and FRM values showed an average absolute difference of 1.2 ppb with an r ² of 0.95. Paired comparison between high and low concentration annual NO₂ sites, seasonal considerations, and interlab quality control comparisons all showed excellent results. The ease of deployment, reliability, and the cost-savings that can be realized with NO₂ PSDs could make them an attractive alternative to FRM monitors for screening purposes, and even possibly an equivalent method for annual NO₂ monitoring. More tests of the Ogawa NO₂ PSD are recommended for different ecosystem and climate regimes.     

A passive sampling method to determine ammonia in ambient air

Ambient ammonia concentrations, mainly originating from agricultural activities, have increased in the last few decades in Europe. As a consequence, critical loads on oligotrophic ecosystems such as forests and mires are greatly exceeded. Monitoring of ambient ammonia concentrations is necessary in order to investigate source-receptor relationships. Measuring ambient ammonia concentrations continuously with high time resolution is very expensive and cost-efficient systems are required. Where time resolution is of minor importance, several cost-effective systems, mainly dry denuder and passive samplers, can be applied. In this paper the Zürcher passive sampler, a diffusive sampling system, is presented. It is a Palmes type sampler with an acidic solution as absorbent and is easy to handle. It was tested at 46 sites in Switzerland over one year. The average concentration in ambient air was 2.5 microg m(-3) +/- 0.4 microg m(-3). The average of the blank values were 0.21 microg m(-3). The detection limit (double the standard deviation of the blank values) was 0.36 microg m(-3). Three passive samplers were exposed at each site and each period. The mean standard deviation of these triplicate measurements was 9.5%. Compared with a discontinuous tubular denuder system and a continuous annular denuder system, the deviation was less than 10%. The Zürcher passive sampler is a useful and cost-efficient tool to determine long-term average ammonia concentrations (one- to four-week periods) in ambient air for mean concentrations above 1 microg m(-3).     

Feasibility study of preparation and certification of reference materials for nitrogen dioxide and sulfur dioxide in diffusive samplers

This paper presents the results of a feasability study for the preparation and certification of reference materials (RMs) for nitrogen dioxide (NO(2)) and sulfur dioxide (SO(2)) in diffusive samplers. RMs for NO(2) were prepared by exposure to gas mixtures in a chamber while the RMs for SO(2) were prepared by liquid spiking. Certification of RMs for NO(2) was found feasible with a certified uncertainty of 5.8% and a proposed shelf life of 5 years. The uncertainty was calculated with contribution from the homogeneity of preparation, stability and transport of the CRMs and from an external verification of the certified value. To reach 5.8% of uncertainty, the contribution of the differences between the results of analysis by ion chromatography and colorimetry must be eliminated. It is proposed to solve this by pre-extracting the samplers with water before analysis. The results of this study indicate that the samplers are stable for at least two years before and after exposure when stored in a refrigerator. By contrast, the certification of RMs for SO(2) was found to not be feasible due to instability problems. This instability was attributed to reaction of sulfate on the walls of the samplers. Alternatively, the preparation of RMs by simultaneous exposure to SO(2) and NO(2) has been tested. Satisfying homogeneities has been reached both for NO(2) and SO(2).     

Laboratory and field comparison of measurements obtained using the available diffusive samplers for ozone and nitrogen dioxide in ambient air

This study presents an evaluation of the extent of differences between measurements performed by O(3) and NO(2) diffusive samplers and by the reference methods for diffusive samplers commercially available. The tests were performed in an exposure chamber under extreme conditions of controlling factors and under field conditions. For NO(2), the results of the laboratory experiments showed that most of the diffusive samplers were affected by extreme exposure conditions. The agreement between the samplers and the reference method was better for the field tests than for the laboratory ones. The estimate of the uptake rate for the exposure conditions using a model equation improved the agreement between the diffusive samplers and the reference methods. The agreement between O(3) measured by the diffusive samplers and by the reference method was satisfactory for 1-week exposure. For 8-hour exposures, the diffusive samplers with high uptake rates quantified better the O(3) concentration than the samplers with low uptake rates. As for NO(2), the results of the O(3) field tests were in better agreement with the reference method than the ones of the laboratory tests. The field tests showed that the majority of diffusive samplers fulfils the 25% uncertainty requirement of the NO(2) European Directive and the 30% uncertainty requirement of the O(3) European Directive for 1-week exposure.     

Evaluation of a fluorometric method for measuring low concentrations of ammonia in ambient air

A fluorometric method developed for measuring low concentrations of ammonium in marine and freshwater ecosystems was adapted for the analysis of ammonia in ambient air. The modified method entails collection of samples on an acid-treated solid adsorbent followed by analysis using a fluorometer. Optimal results were obtained using a commercially available sorbent tube containing 100 mg of acid-treated silica gel for sample collection, and an analytical protocol consisting of sample desorption in DI water, addition of orthopthaldialdehyde (OPA) working reagent, and room temperature incubation. Method accuracy and precision were evaluated by comparing experimentally determined quantities of ammonia to expected levels for sample loadings ranging from 0.16 [micro sign]g to 550 [micro sign]g-accuracy was generally within +/-20%. The estimated LOQ for the method is 0.08 [micro sign]g ammonia per sample which represents a 25-375-fold improvement in sensitivity compared to current NIOSH and OSHA methods for the measurement of ammonia in ambient air. The new method should be useful for applications requiring measurement of low concentrations of ammonia using personal sampling equipment or in the characterization of short-term fluctuations of ammonia concentrations in air.     

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.     

Development of a personal monitoring method for nitrogen dioxide and sulfur dioxide with Sep-Pak C18 cartridge sampling and ion chromatographic determination

Personal monitoring methods for the determination of hourly integrated concentrations of NO2 and SO2 in ambient air have been developed. Triethanolamine (TEA)-impregnated C18 Sep-Pak cartridges were used to collect NO2 and SO2 simultaneously. After sampling, NO2 and SO2 as their nitrite, nitrate, sulfite and sulfate analogues were stripped from the cartridges with a solution of 5% methanol in distilled, deionized water (DDW) and then determined by ion chromatography. Laboratory tests were conducted to evaluate the sampling rate, collection and recovery efficiencies, breakthrough volumes, absorption capacity, interference and sample stability on the cartridge during storage. NO2 and SO2 detection limits of 0.3 and 0.4 ppb respectively for 1 h samples were obtained. Recoveries for both NO2 and SO2 exceeded 85%.     

Long-term measurement of volatile organic compounds in ambient air by canister-based one-week sampling method

A canister-based 1 week sampling method using a mechanical flow controller and a 6 L fused-silica-lined canister was evaluated for the long-term measurement of 47 VOCs in ambient air at pptv (volume/volume) to ppbv levels by use of a three-stage preconcentation method followed by GC-MS analysis. The GC conditions were initially optimized for complete separations of several pptv-level VOCs (e.g. vinyl chloride, 1,3-butadiene, acrylonitrile, 1,2-dichloroethane and chloroform) in ambient air because the selected ions are easily interfered with by coexisting C4-, C5-hydrocarbons and analytes presented at ppbv levels. Thirty-four VOCs determined by the 1 week and 24 h sampling method in December 16-22 (2002) had concentrations of 6.0-15000 pptv per compound. Concentrations of 28 VOCs (including polar VOCs (e.g. methyl isobutyl ketone and butyl acetate)) obtained by the method were approximately equal to the mean values calculated from 24 h sampling (< +/- 10% deviation). Six VOCs that had low concentrations of 6.0-43 pptv showed more than +/- 10% deviation. Thirteen VOCs were not detected during the entire sampling period. The effect of relative humidity or ozone for the specific VOCs (e.g. MIBK, butyl acetate, vinyl chloride, 1,3-butadiene and styrene) was negligible.     

Diode laser system for measurement of gaseous ammonia in ambient air

The use of a second harmonic diode laser system for monitoring gaseous ammonia in tropospheric air is discussed. Using a 96 m White cell operated at 13 torr pressure in flow mode, a minimum detectable concentration lower than 1 ppbv was obtained.The NH₃ mixing ratio was determined by simultaneous spectroscopic analysis of an atmospheric CO₂ line used as a built-in calibration standard.     

Design and laboratory testing of a new flow-through directional passive air sampler for ambient particulate matter

A new type of directional passive air sampler (DPAS) is described for collecting particulate matter (PM) in ambient air. The prototype sampler has a non-rotating circular sampling tray that is divided into covered angular channels, whose ends are open to winds from sectors covering the surrounding 360°. Wind-blown PM from different directions enters relevant wind-facing channels, and is retained there in collecting pools containing various sampling media. Information on source direction and type can be obtained by examining the distribution of PM between channels. Wind tunnel tests show that external wind velocities are at least halved over an extended area of the collecting pools, encouraging PM to settle from the air stream. Internal and external wind velocities are well-correlated over an external velocity range of 2.0-10.0 m s?1, which suggests it may be possible to relate collected amounts of PM simply to ambient concentrations and wind velocities. Measurements of internal wind velocities in different channels show that velocities decrease from the upwind channel round to the downwind channel, so that the sampler effectively resolves wind directions. Computational fluid dynamics (CFD) analyses were performed on a computer-generated model of the sampler for a range of external wind velocities; the results of these analyses were consistent with those from the wind tunnel. Further wind tunnel tests were undertaken using different artificial particulates in order to assess the collection performance of the sampler in practice. These tests confirmed that the sampler can resolve the directions of sources, by collecting particulates preferentially in source-facing channels.     

A field evaluation of a piezo-optical dosimeter for environmental monitoring of nitrogen dioxide

Measurements of 8-hour time-weighted average NO(2) concentrations are reported at 7 different locations in the region of Dunkirk over 5 consecutive days using PiezOptic monitoring badges previously calibrated for the range 0-70 ppb together with data from chemiluminescent analysers in 5 sites (4 fixed and one mobile). The latter facilities also provided data on ozone and NO concentrations and meteorological conditions. Daily averages from the two pairs of badges in different types of sampling cover in each site have been compared with data from the chemiluminescent analysers, and found largely to agree within error margins of +/-30%. Although NO(2) and ozone concentrations were low, rendering detailed discussion impossible, the general features followed expected patterns.     

二氧化硫(高压)气体标准样品的研制

文章对高压气瓶中二氧化硫气体标准样品的制备方法进行了研究 ,对各种可能影响二氧化硫气体标准样品量值准确性的因素进行了分析。所制备的 2 0 .2 μmol/ mol二氧化硫气体标准样品的不确定度仅为 1 .4 % ,且具有良好的压力稳定性并能稳定保存 2 0个月     

Field evaluation of a tailor-made new passive sampler for the determination of NO2 levels in ambient air

This study describes the field evaluation of a tailor-made new glass passive sampler developed for the determination of NO(2), based on the collection on triethanolemine (TEA)-coated fibre filter paper. The sampler has been derived from a Palmes design. The overall uncertainty of the sampler was determined by using Griess-Saltzman ASTM D 1607 standard test method as a reference method. The agreement between the results of the passive sampler and the reference method was +/-7.90% with the correlation coefficient of 0.90. Method precision in terms of coefficient of variance (CV) for three simultaneously applied passive samplers was 8.80%. The uptake rate of NO(2) was found to be 2.49 ml/min in a very good agreement with the value calculated from theory (2.63 ml/min). Sampler detection limit was 1.99 microg/m(3) for an exposure period of 1 week and the sampler can be stored safely for a period of up to 6 weeks before exposure. A comparison of the sampler performance was conducted against a commercially available diffusion tube (Gradko diffusion tube). The results from the applied statistical paired t test indicated that there was no significant difference between the performances of two passive samplers (R (2) > 0.90). Also, another statistical comparison was carried out between the dark and transparent glass passive samplers. The results from the dark-colour sampler were higher than that from the transparent sampler (approximately 25%) during the summer season because of the possible photodegradation of NO(2)-TEA complex.     

Evaluation of a simultaneous sampling method of PAHs, PCDD/Fs and dl-PCBs in ambient air

The Stockholm Convention on Persistent Organic Pollutants (POPs) was signed in May 2001 by 127 countries. Currently, 12 substances are regulated by the convention, and the work on finding new candidate chemicals to the convention has started. Among these 12 substances, dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are the objects of this study. There are no European standard methods for the simultaneous determination of these microorganic compounds, together with polycyclic aromatic hydrocarbons (PAHs) in ambient air--they must be referred to three different methods developed by the U.S. Environmental Protection Agency (EPA). The quali-quantitative analysis of these microorganic pollutants is an important challenge due to the low concentrations at which they may be present. In this study, the development of a simplified, alternative, fast and affordable sampling method for the determination of PAHs, PCDDs, PCDFs and PCBs in ambient air was performed. The sampling time was extended from 24 h to 7 d in order to enrich the sample, to fall within the instrumental limits of detection and to reduce the number of samples to be processed and, therefore, errors that may arise. First of all, experiments with labelled standards were conducted in the research area of Montelibretti (rural station, which is sited about 20 km northeast of Rome), with the purpose of optimizing sampling efficiency. Finally, the method was applied to the analysis of these compounds in the air of a suburban area with small industrial plants in order to evaluate the feasibility of the proposed sampling method system, by comparing concentrations of native compounds acquired during simultaneous daily and weekly sampling.     

Seasonal trends of atmospheric nitrogen dioxide and sulfur dioxide over North Santa Clara, Cuba

Atmospheric nitrogen dioxide (NO₂) and sulfur dioxide (SO₂) levels were monitored simultaneously by means of Radiello passive samplers at six sites of Santa Clara city, Cuba, in the cold and the warm seasons in 2010. The dissolved ionic forms of NO₂ and SO₂ as nitrate and sulfite plus sulfate, respectively, were determined by means of ion chromatography. Analysis of NO₂ as nitrite was also performed by UV–Vis spectrophotometry. For NO₂, significant t tests show good agreement between the results of IC and UV–Vis methods. The NO₂ and SO₂ concentrations peaked in the cold season, while their minimum levels were experienced in the warm season. The pollutant levels do not exceed the maximum allowable limit of the Cuban Standard 39:1999, i.e., 40 μg/m³ and 50 μg/m³ for NO₂ and SO₂, respectively. The lowest pollutant concentrations obtained in the warm season can be attributed to an increase in their removal via precipitation (scavenging) while to the decreased traffic density and industrial emission during the summer holidays (e.g., July and August).