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.     

Validation of a passive atmospheric deposition sampler for polybrominated diphenyl ethers

An atmospheric deposition sampler was validated with respect to polybrominated diphenyl ethers (PBDEs), a compound group that is widely used as flame retardants in many types of consumer products. The deposition sampler consists of an adsorption cartridge that is connected to a glass funnel. Extraction tests with spiked cartridges using soxhlet extraction with acetone revealed recoveries of >80% for all of the investigated PBDEs. Once adsorbed, PBDEs are stable, as proven by extractions of spiked cartridges that were stored outdoors and collected after different periods of time, up to 84 days. High recoveries indicate that degradation of adsorbed PBDEs does not play a role under realistic field conditions. Bulk deposition rates of PBDEs were determined in a field test with 3 replicates, and a possible breakthrough of target compounds was assessed in the field using a second adsorption cartridge in series. No breakthrough of target compounds could be observed within a sampling period of 61 days, and a bulk deposition rate of approximately 1 ng m(-2) day(-1) for the sum of all analysed PBDEs was measured. The highest deposition rates were measured for octa-brominated congeners, followed by BDEs 99, 183, 153, and 47. Overall, the sampler was successfully validated regarding the atmospheric deposition of PBDEs.     

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.     

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.     

Modelling of the uptake rate of the nitrogen dioxide Palmes diffusive sampler based on the effect of environmental factors

The influence of environmental parameters on the uptake rate of the nitrogen dioxide (NO(2)) Palmes diffusive sampler was investigated. The main factors affecting the uptake rate were found to be wind speed, the preponderant factor, followed by relative humidity and temperature. The NO(2) concentration and exposure time, as well as the interactions among the factors were not found to have a significant influence on the uptake rate of the Palmes sampler. As a result, a model able to predict the uptake rate of the Palmes sampler was established. In addition, by using the model-predicted uptake rate, the agreement between chemiluminescence and the Palmes sampler during the field tests was improved. The NO(2) Palmes diffusive sampler was shown to comply with the requirement on accuracy defined by the European Directive for the indicative methods of measurements.     

Validation of diffusive mini-samplers for aldehyde and VOC and its feasibility for measuring the exposure levels of elementary school children

Exposure to various chemicals can cause adverse effects to health, such as asthma and allergies, especially in children. Data on personal exposure levels in children are scarce, thus small lightweight diffusive mini-samplers for aldehydes and volatile organic compounds (VOCs) were designed to measure the exposure level of children to these chemicals. The aim of the study was to validate and examine the applicability of these mini-samplers for measuring daily chemical exposure. The diffusive mini-samplers are 20 mm in length, 11 mm in diameter, and 1.67 g in weight. The devices are cylindrically shaped with polytetrafluoroethylene membrane filters placed at each end. To measure aldehydes and acetone, 20 mg of 2,4-dinitrophenylhydrazine was used as an absorbent. To measure VOCs, a carbon molecular sieve was used. The sampling rate for each chemical was determined by parallel sampling with active samplers in a closed exposure bag. The blank levels of the chemicals and the storage stability of the device were tested. The mini-samplers were compared to commercially available diffusive samplers. To examine the applicability of the samplers, 65 elementary school children carried them for 24 h. The sampling rates for formaldehyde, acetaldehyde, and acetone were 20.9, 22.9, and 19.7 mL min(-1), respectively. The limits of quantification (LOQ) for the 24-hour sampling by high-performance liquid chromatography/ultraviolet (HPLC/UV) analysis were 8.3, 7.6, and 8.8 μg m(-3) for formaldehyde, acetaldehyde, and acetone, respectively. The sampling rates for the 11 VOCs were determined and ranged from 3.3 mL min(-1) for styrene and 2-ethyl-1-hexanol to 11.7 mL min(-1) for benzene. The LOQ for the 24-hour sampling by gas chromatography-mass spectrometry (GC-MS) analysis ranged from 5.9-105.2 μg m(-3), 1.1-24.7 parts per billion. The storage stability after 5 days ranged from 94.8 to 118.2%. Formaldehyde, acetone, benzene, and toluene were detected above the LOQ in more than 90% of the children, and the median concentrations were 21.7, 20.9, 10.1, and 21.5 μg m(-3), respectively. This study shows that the diffusive samplers developed were suitable for children to carry and were capable of measuring the children's daily chemical exposure.     

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.     

A passive sampler for hydrogen sulfide

The silver nitrate/fluorescein mercuric acetate fluorimetric method for the measurement of atmospheric hydrogen sulfide has been adapted to passive sampling. Standard samplers have been tested and used in both indoor and outdoor environments. Sampler performance was not dependent on construction materials or sunlight intensity and gave similar results to active sampling. Two case studies were carried out, one in the Horniman Museum and its associated storage and study building, London, UK, and the other in the vicinity of a pulp and paper mill and geothermal area North Island, New Zealand. The detection limit of the samplers (50 ppt average for a one-week exposure) provides the opportunity to make measurements in a variety of locations provided exposure times are sufficiently long, i.e., up to one month in areas of low hydrogen sulfide concentration.     

Design and validation of a passive deposition sampler

A new, passive particle deposition air sampler, called the Einstein-Lioy Deposition Sampler (ELDS), has been developed to fill a gap in passive sampling for near-field particle emissions. The sampler can be configured in several ways: with a protective hood for outdoor sampling, without a protective hood, and as a dust plate. In addition, there is an XRF-ready option that allows for direct sampling onto a filter-mounted XRF cartridge which can be used in conjunction with all configurations. A wind tunnel was designed and constructed to test the performance of different sampler configurations using a test dust with a known particle size distribution. The sampler configurations were also tested versus each other to evaluate whether or not the protective hood would affect the collected particle size distribution. A field study was conducted to test the sampler under actual environmental conditions and to evaluate its ability to collect samples for chemical analysis. Individual experiments for each configuration demonstrated precision of the sampler. The field experiment demonstrated the ability of the sampler to both collect mass and allow for the measurement of an environmental contaminant i.e. Cr(6+). The ELDS was demonstrated to be statistically not different for Hooded and Non-Hooded models, compared to each other and the test dust; thus, it can be used indoors and outdoors in a variety of configurations to suit the user's needs.     

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.     

Performance optimisation of a passive sampler for monitoring hydrophobic organic pollutants in water

The performance of an integrative passive sampler that consists of a C18 Empore disk sorbent receiving phase fitted with low density polyethylene membrane was optimised for the measurement of time-weighted average concentrations of hydrophobic micropollutants in water. A substantial improvement of sampling characteristics including the rate of sampling and the sampling precision was achieved by decreasing the internal sampler resistance to mass transfer of hydrophobic organic chemicals. This was achieved by adding a small volume of n-octanol, a solvent with high permeability (solubility [times] diffusivity) for target analytes, to the interstial space between the receiving sorbent phase and the polyethylene diffusion-limiting membrane.     

Development of a diffusive sampling method for determination of methyl isocyanate in air

A diffusive sampling method for determination of methyl isocyanate in air has been developed. A glass fibre filter impregnated with 1-(2-methoxyphenyl)piperazine in a commercially available diffusive sampling device was used to collect methyl isocyanate and the derivative formed was analysed with LC-MS/MS. The sampling rate was determined to be 15.6 ml min(-1), with a relative standard deviation of 7.3%. The sampler was validated for sampling periods from 15 min to 8 h, for relative humidities from 20% to 80% and for concentrations from I to 46 microg m(-3). A field validation was also made and the diffusive sampling results showed no difference compared to a pumped reference method. The impregnated filters have to be stored apart from the diffusive sampler housing and loaded into the sampler prior to each sampling.     

Field intercomparison of diffusive samplers for measuring ammonia

Agricultural production systems are recognised as a major source of atmospheric ammonia. Deposition of ammonia and ammonium may contribute to undesired changes in oligotrophic ecosystems. The continuous measurement of atmospheric ammonia requires expensive and sophisticated techniques and is performed only in a very restrict number of ambient air stations in Europe. Therefore, the application of passive samplers, which have the advantage of being easy to handle and cost-efficient, is useful. In the past the comparability of different passive samplers must be considered as rather scarce. In a joint European project under the leadership of the GSF-Forschungszentrum für Umwelt und Gesundheit, Neuherberg, in 1997 a comparison of different passive ammonia monitoring methods was carried out in a prealpine rural site near Garmisch-Partenkirchen. It was considered valuable to include not only well established systems but also methods still being developed. For the comparative test ten working groups with different methods took part. A wet annular denuder system, which has been developed by the Netherlands Energy Research Foundation for on-line measurement of atmospheric ammonia, served as reference of passive methods. The experiment, which started in June and finished in December, showed that most of the passive samplers fulfil the requirements and can be recommended for further measurements. Additional measurements of meteorological parameters were performed to check the influences of different weather conditions on passive sampling.     

DOAS大气环境质量监测系统与传统点式采样监测法可比性研究

系统比较了DOAS大气监测系统与传统点式采样设备在测定环境空气中二氧化硫的性能。     

Evaluation of the effect of different sampling time periods and ambient air pollutant concentrations on the performance of the Radiello diffusive sampler for the analysis of VOCs by TD-GC/MS

The effect of different sampling exposure times and ambient air pollutant concentrations on the performance of Radiello? samplers for analysis of volatile organic compounds (VOCs) is evaluated. Quadruplicate samples of Radiello? passive tubes were taken for 3, 4, 7 and 14 days. Samples were taken indoors during February and March 2010 and outdoors during July 2010 in La Canonja (Tarragona, Spain). The analysis was performed by automatic thermal desorption (ATD) coupled with capillary gas chromatography (GC)/mass spectrometry detection (MS). The results show significant differences (t-test, p < 0.05) between the amounts of VOCs obtained from the sum of two short sampling periods and a single equivalent longer sampling period for 65% of all the data. 17% of the results show significantly larger amounts of pollutant in the sum of two short sampling periods. Back diffusion due to changes in concentrations together with saturation and competitive effects between the compounds during longer sampling periods could be responsible for these differences. The other 48% of the results that are different show significantly larger amounts in the single equivalent longer sampling period. The remaining 35% of the results do not show significant differences. Although significant differences are observed in the amount of several VOCs collected over two shorter sampling intervals compared to the amount collected during a single equivalent longer sampling period, the ratios obtained are very close to unity (between 0.7 and 1.2 in 75% of cases). We conclude that Radiello? passive samplers are useful tools if their limitations are taken into account and the manufacturer's recommendations are followed.     

Passive aerosol sampler for particle concentrations and size distributions

This research evaluated the UNC passive aerosol sampler as a tool to measure particle mass concentrations and size distributions. The exposure scenario represented high concentrations and exposure periods of a few hours. Mass concentrations measured with the passive sampler were compared to concentrations measured using both a dichotomous sampler and an aerodynamic particle sizer (APS). In addition, the size distributions measured with the passive sampler were compared to those measured using the APS. Mass concentrations measured using the dichotomous sampler and the APS agreed well. The passive sampler tracked, but tended to overestimate, mass concentrations measured by the other two instruments. Size distributions measured with the passive sampler followed the general pattern of those measured using the APS. Overall, the passive sampler demonstrated both its utility and its limitations in these tests. The concentration measurements and size distributions found using passive samplers were more variable than those of the other instruments, but generally followed the data taken using the other methods. The advantages of low cost and ease of use offset the limitations in data quality with the passive sampler; these advantages are particularly welcome for sampling situations where aerosol properties vary over space or time.     

Performance optimization of a membrane assisted passive sampler for monitoring of ionizable organic compounds in water

A thin-walled silicone rubber hollow fibre membrane has been developed as a passive sampler. The inside of the tube is filled with an aqueous solution at an appropriate pH. The tube is sealed at both ends and then immersed in a water sample. In order for the ionizable permeating compounds to be trapped in the aqueous receiving phase, the pH is adjusted such that the compounds are ionized and trapped. The major advantages are its simplicity, low cost and high selectivity, since only ionizable organic compounds are trapped. Additionally, the sampler uses no organic solvent. By adjusting the pH of the acceptor phase, it is possible to control the extraction process and whether the sampler is used in the kinetic or equilibrium regime. Since it is very selective, no further clean-up of the extract is required. The membrane assisted passive sampler has been tested for extraction of chlorophenols under laboratory conditions. The extraction process was found to be linear over a 72 h sampling period. Selectivity of the passive sampler in river water was demonstrated and the extraction process was independent of sample concentration, even at lower concentration levels of analytes. However, the sample matrix in some river water samples led to incomplete trapping, thereby reducing the amount trapped in the acceptor phase. Detection limits (three times signal to noise ratio) were dependant on sample matrix and type of detection system and ranged from 0.05 microg L(-1) to about 1 microg L(-1) with a UV photodiode detector in water samples from one river and 1.0 microg L(-1) to 20 microg L(-1) in another but with an ordinary UV detector. The enrichment factors in river water were 28 for 2-chlorophenol and 44 for 2,4-dichlorophenol over a 72 h sampling period. 4-chlorophenol was poorly extracted and its enrichment factor was 3.     

SAOZ measurements of NO2 at Aberystwyth

We present in this paper fifteen years' measurements, from March 1991 to September 2005, of stratospheric NO2 vertical columns measured by a SAOZ zenith-sky visible spectrometer. The instrument spent most of its time at Aberystwyth, Wales, with occasional excursions to other locations. The data have been analysed with the WinDOAS analysis program with low-temperature high-resolution NO2 cross-sections and fitting a slit function to each spectrum. Because of a change in detector in May 1998 there is some uncertainty about the relative changes before and after this date, which are partially constrained by the results of an intercomparison exercise. However, the effect of the Mt Pinatubo aerosol cloud is very evident in the data from 1991-94, with a decrease of 10% in NO2 in the summer of 1992 (the SAOZ was located in Lerwick, Scotland during the winter of 1991-92 and observed very low NO2 values but these cannot be directly compared to the Aberystwyth data). To focus more on interannual and long-term variations in NO2, a seasonal variation comprising an annual and semi-annual component was fitted to the morning and evening twilight separately from 1995 to the present. This fit yielded average NO2 columns of 4.08 x 10(15) cm(-2) and 2.68 x 10(15) cm(-2) for the evening and morning twilight, respectively, with a corresponding annual amplitude of +/-2.08 x 10(15) cm(-2) and +/-1.50 x 10(15) cm(-2). Departures from the fitted curve show a trend of 6% per decade, consistent with that reported elsewhere, for the period 1998-2003, but in the past two years a distinct interannual variation of amplitude of approximately 8% has emerged.     

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.