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

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

The validation of a passive sampler for indoor and outdoor concentrations of volatile organic compounds

Volatile organics compounds (VOCs) are ubiquitous in the air we breathe. The use of passive samplers to measure these concentrations can be an effective technique. When exposed for long durations, a passive sampler may be a good tool for investigating chronic exposures to chemicals in the environment. A passive sampler that was designed for occupational exposures can be used as such a tool. Laboratory validation under as many conditions as possible needs to be accomplished so as to characterize the sampler with known parameters. This paper describes the methods and results of an investigation into the validity of using a passive monitor to sample VOCs for a three-week period. Two concentration levels, two relative humidities, and five VOCs were studied. Results indicate that the samplers work best under conditions of high concentration with low relative humidity and low concentration with high relative humidity. For the passive sampler, excluding chloroform, percent deviations from the predicted values varied between -41 and +22 percent; while the values between the passive and the active samplers varied between -27 and +24 percent. Benzene, heptane, and perchloroethylene were sampled with equal precision and accuracy.     

Performance evaluation of a tailor-made passive sampler for monitoring of tropospheric ozone

Introduction

This study presents the performance evaluation of a tailor-made passive sampler developed for the monitoring of tropospheric ozone.

Methods

The performance of the passive sampler was tested in the field conditions in terms of accuracy, precision, blank values, detection limit, effects of some parameters such as sampling site characteristics and sampling period on the field blanks, self-consistency, experimental and theoretical uptake rates, shelf life and comparison with commercial passive samplers.

Results

There was an agreement (R ²?=?0.84) between the responses of passive sampler and the continuous automatic analyser. The accuracy of the sampler, expressed as percent relative error, was obtained lower than 15%. Method precision in terms of coefficient of variance for three simultaneously applied passive samplers was 12%. Sampler detection limit was 2.42???g?m^?3 for an exposure period of 1?week, and the sampler can be stored safely for a period of up to 8?weeks before exposure. Satisfactory self-consistency results showed that extended periods gave the same integrated response as a series of short-term samplers run side by side. The uptake rate of ozone was found to be 10.21?mL?min^?1 in a very good agreement with the theoretical uptake rate (10.32?mL?min^?1). The results of the comparison study conducted against a commercially available diffusion tube (Gradko diffusion tube) showed a good linear relationship (R ²?=?0.93) between two passive samplers.

Conclusions

The sampler seems suitable to be used in large-scale measurements of ozone where no data are available or the number of existing automated monitors is not sufficient.     

The Validation of a Passive Sampler for Indoor and Outdoor Concentrations of Volatile Organic Compounds

Abstract

Volatile organlcs compounds (VOCs) are ubiquitous in the air we breathe. The use of passive samplers to measure these concentrations can be an effective technique. When exposed for long durations, a passive sampler may be a good tool for investigating chronic exposures to chemicals in the environment. A passive sampler that was designed for occupational exposures can be used as such a tool. Laboratory validation under as many conditions as possible needs to be accomplished so as to characterize the sampler with known parameters. This paper describes the methods and results of an investigation into the validity of using a passive monitor to sample VOCs for a three-week period. Two concentration levels, two relative humidities, and five VOCs were studied. Results indicate that the samplers work best under conditions of high concentration with low relative humidity and low concentration with high relative humidity. For the passive sampler, excluding chloroform, percent deviations from the predicted values varied between ?41 and +22 percent; while the values between the passive and the active samplers varied between ?27 and +24 percent. Benzene, heptane, and perchloroethylene were sampled with equal precision and accuracy.     

A second look at the Palmes' diffusive sampler

The Palmes' tube, the first diffusive sampler incorporating a fixed path length, has received wide usage for the sampling of a large number of gaseous pollutants. But despite numerous previous studies, questions remain regarding the accuracy of these inexpensive, simple-to-construct, open-ended samplers. Here the mass transfer resistance in a Palmes' diffusive sampler was measured using the loss of cyclohexane from a Palmes' tube containing liquid cyclohexane at its base. The average loss rates, at factorial combinations of five air incidence angles evenly spaced from 270 degrees to 90 degrees, and five air speeds from 0.5 m/sec to 2.5 m/sec ranged from 46% to 121% higher than rates calculated from the physical dimensions of the sampler, proving the need to calibrate these samplers rather than relying on a theoretical calculation. The mass transfer resistance was nearly constant when the airflow was perpendicular to the sampler and sufficiently high to avoid stagnation, a finding that may explain the widespread acceptance of the results obtained using this sampler.     

Field intercomparison of throughfall measurements performed within the framework of the Pan European intensive monitoring program of EU/ICP Forest

A 6-month field intercomparison study on throughfall measurements was performed at Speulder forest near the west coast in The Netherlands. Twenty throughfall sampling systems were evaluated on accuracy, sampling strategy and performance under field conditions. Throughfall fluxes of NO3-, K+ and Kjeldahl-N generally could be determined with a larger accuracy than fluxes of SO4(2-), NH4+, Na+, Cl-, Mg2+, Ca2+, and alkalinity. Throughfall fluxes of H+ generally had the lowest accuracy. Only 20% of the sampling systems differed more than 20% from the best estimate, whereas 45% of the systems stayed within a 10% range from the best estimate. The difference from the best estimate was mainly caused by aspects related to sampling strategy, like, for example, collecting area, sampler placement. The inaccuracy induced by the sampling system appeared to be much larger than that resulting from the analysis of the samples by different laboratory as determined by ring-tests. The field intercomparison described in this article gave a good insight in the different aspects contributing to the overall accuracy of the measurements. However, performing a future field intercomparison is recommended for throughfall and stemflow in order to also take in account other aspects that might influence the performance of the different measurement systems (e.g. tree species, climate zone, summer/winter period).     

Measurement of Ambient Ground-Level Concentrations of Hydrogen Fluoride

The use of published, accepted methods for measuring ambient levels of gaseous hydrogen fluoride (HF) with a double-tape sampler led to large errors. The major source of error was found to be scrubbing In the stainless steel intake, which was avoided by substituting Teflon for the stainless steel. To avoid this and other problems encountered in the measurement of HF, we revised the double-tape sampler method and modified the double-tape sampler. We designed and constructed an HF calibrator for use in testing the revised method and modified sampler In the field and laboratory.

The results of a round robin indicated that, in the laboratory, the revised method has a single-operator precision of 3 percent at 2.6 μg/m³ and a between-laboratory precision of 4 percent. The average bias at 2.6 μg/m³ was 0.02 μg/m³ and was not significantly different from zero. Comparable precision and accuracy were obtained in the field. The response was linear, at least to 10 μg/m³. The limit of detectability, which appears to be limited by the variability in measurements of blank tapes, is 0.07 μg/m³. The revised method appears both precise and accurate.     

Radial diffusive sampler for the determination of 8-h ambient ozone concentrations

The 8-h ozone radial diffusive sampler was evaluated according to the CEN protocol for the validation of diffusive samplers. All the parameters regarding the sampler characteristics were found to be consistent with the requirements of this protocol apart from the blank value, which must be evaluated and subtracted at each sampling. The nominal uptake rate was determined in laboratory conditions. However, the uptake rate depends on the mass uptake, temperature, humidity and on the combination of temperature and humidity. Based on laboratory experiments, an empirical model has been established which improved the agreement between the radial sampler and the reference method. This improvement was observed under several different meteorological and emission conditions of sampling. By using the model equation of uptake rate, the data quality objective of 30% for the expanded uncertainty included in the O(3) European Directive, is easily attained. Therefore, the sampler represents an appropriate indicative method.     

Evaluation of an intensive sampling and analysis method for carbon monoxide

This paper describes a portable, low-cost whole air sampler capable of collecting 12 1-L samples in tedlar bags and using a single "D" cell for power. The results are presented from two tests of an intensive sampling and analysis method for measuring ambient carbon monoxide (CO) concentrations in urban areas using this sampler. The method is evaluated in comparison with an approved continuous CO analyzer, in intercomparisons of the results of re-analysis of the samples, and by examination of the results from co-located samplers. The precision of the analytical method was found to be +/-0.30 ppmv. The precision of the sampling method was found to be +/-0.73 ppmv and therefore is the limiting factor in the method's overall precision. These values are sufficient to verify attainment of National Ambient Air Quality Standards (NAAQS) levels in urban areas. Improvements in the sampler and analytical procedure are discussed.     

In-vivo passive sampling to measure elimination kinetics in bioaccumulation tests

The application of in-tissue passive sampling to quantify chemical kinetics in fish bioconcentration experiments was investigated. A passive sampler consisting of an acupuncture needle covered with a PDMS tube was developed together with a method for its deployment in rainbow trout. The time to steady state for chemical uptake into the passive sampler was >1 d, so it was employed as a kinetically limited sampler with a deployment time of 2 h. The passive sampler was employed in parallel with the established whole tissue extraction method to study the elimination kinetics of 10 diverse chemicals in rainbow trout. 4-n-nonylphenol and 2,4,6-tri-tert-butylphenol were close to or below the limit of quantification in the sampler. For chlorpyrifos, musk xylene, hexachlorobenzene, 2,5-dichlorobiphenyl and p,p′-DDT, the elimination rate constants determined with the passive sampler method and the established method agreed within 18%. Poorer agreement (35%) was observed for 2,3,4-trichloroanisole and p-diisopropylbenzene because fewer data were obtained with the passive sampling method due to its lower sensitivity. The work shows that in-tissue passive sampling can be employed to measure contaminant elimination kinetics in fish. This opens up the possibility of studying contaminant kinetics in individual fish, thereby reducing the fish requirements and analytical costs for the determination of bioconcentration factors.     

Evaluation of the RAMS continuous monitor for determination of PM2.5 mass including semi-volatile material in Philadelphia,PA

The real-time ambient mass sampler (RAMS) is a continuous monitor based on particle concentrator, denuder, drier, and tapered element oscillating microbalance (TEOM) monitor technology. It is designed to measure PM2.5 mass, including the semi-volatile species NH4NO3 and semi-volatile organic material, but not to measure PM2.5 water content. The performance of the RAMS in an urban environment with high humidity was evaluated during the July 1999 NARSTO-Northeast Oxidant and Particles Study (NEOPS) intensive study at the Baxter water treatment plant in Philadelphia, PA. The results obtained with the RAMS were compared to mass measurements made with a TEOM monitor and to constructed mass obtained with a Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS) sampler designed to determine the chemical composition of fine particles, including the semi-volatile species. An average of 28% of the fine particulate material present during the study was semi-volatile organic material lost from a filter during particle collection, and 1% was NH4NO3 that was also lost from the particles during sampling. The remaining mass was dominantly nonvolatile (NH4)2SO4 (31%) and organic material (37%), with minor amounts of soot, crustal material, and nonvolatile NH4NO3. Comparison of the RAMS and PC-BOSS results indicated that the RAMS correctly monitored for fine particulate mass, including the semivolatile material. In contrast, the heated filter of the TEOM monitor did not measure the semi-volatile material. The comparison of the RAMS and PC-BOSS data had a precision of +/-4.1 microg/m3 (+/-9.6%). The precision of the RAMS data was limited by the uncertainty in the blank correction for the reversible adsorption of water by the charcoal-impregnated cellulose sorbent filter of the RAMS monitor. The precision of the measurement of fine particulate components by the PC-BOSS was +/-6-8%.     

Design and Testing of a New Size Classifying Isokinetic Sequential Aerosol Sampler

Two versions of a size-classifying isokinetic sequential aerosol sampler (SCISAS) have been designed, built, tested, and deployed in a field program in the southwestern United States. The SCISAS units can operate at unattended sites, exposing four or more filter types simultaneously, in two size ranges, for six sampling time Intervals. Design considerations included theoretical estimates of aerosol particle losses in the 0-15 μm size range.

SCISAS prototypes have been tested to evaluate their sampling efficiency as a function of flow rate, the sensitivity of the sampling efficiency to isokinetic matching within the SCISAS sampling stack, the equivalency of their sampling ports, and their passive deposition characteristics. The prototypes were also compared to several other types of aerosol filtration samplers already in common use. These tests show that particle loss mechanisms within the SCISAS usually cause no more than 5 percent losses, and that the SCISAS units agree, within one to two measurement uncertainty intervals, with other types of aerosol samplers.     

A comparative study of the performance of passive samplers

Atmospheric concentrations of benzene, toluene, ethylbenzene, and xylenes (o-xylene and m,p-xylene) were assessed in the Tricity area (Gdańsk-Sopot-Gdynia, Poland) with the use of two types of passive samplers: permeation (homemade passive samplers) and diffusive (Radiello and Orsa 5). Samples were collected during 2008 at selected sites in the Tricity area at monitoring stations belonging to the agency of Regional Air Quality Monitoring Foundation. The field study was conducted to compare the performance of these two different types of passive samplers. A statistical approach was formulated, and the experimental data were evaluated using the paired t test, Wilcoxon signed rank-sum test, and Friedman analysis of variance. All the statistical results confirm the hypothesis that the differences between the performances of the three sampling devices are highly significant. Despite the fact that data obtained with the homemade passive sampler indicated that the results were higher compared with those for the Radiello and Orsa 5 diffusive samplers, the authors note that all differences between the homemade permeation sampler and the Radiello and Orsa 5 diffusive samplers are positive.     

Evaluation of the use of diffusive air samplers for determining temporal and spatial variation of volatile organic compounds in the ambient air of urban communities

The Houston-Galveston metropolitan area has a relatively high density of point and mobile sources of air toxics, and determining and understanding the relationship between emissions and ambient air concentrations of air toxics is important for evaluating potential impacts on public health and formulating effective regulatory policies to control this impact, both in this region and elsewhere. However, conventional ambient air monitoring approaches are limited with regard to expense, siting limitations, and representative sampling necessary for adequate exposure assessment. The overall goal of this multiphase study is to evaluate the use of simple passive air samplers to determine temporal and spatial variability of the ambient air concentrations of selected volatile organic compounds (VOCs) in urban areas. Phase 1 of this study, reported here, was a field evaluation of 3M organic vapor monitors (OVMs) involving limited comparisons with commonly used active sampling methods, an assessment of sampler precision, a determination of optimal sampling duration, and an investigation of the utility of a simple modification of the commercial sampler. The results indicated that a sampling duration of 72 hr exhibited generally low bias relative to automated continuous gas chromatography measurements, good overall precision, and an acceptable number of measurements above detection limits. The modified sampler showed good correlation with the commercial sampler, with higher sampling rates, although lower than expected.     

Field evaluation of two diffusive samplers and two adsorbent media to determine 1,3-butadiene and benzene levels in air

Two types of diffusive samplers, both of which are compatible with thermal desorption, but differ in their geometry—SKC-Ultra (badge-type) and Radiello (radial symmetry-type)—were evaluated indoors and outdoors under varying temperature, humidity and wind speed conditions, using the graphitized adsorbents Carbopack X or Carbograph 5 to measure 1,3-butadiene and benzene in ambient air. The results obtained by diffusive sampling were compared with results obtained using a conventional active sampling method over both long (1 week) and shorter periods (6–24 h). Analysis and detection were performed using an automatic thermal desorber (ATD) connected to a gas chromatograph-flame ionization detector (GC/FID). Results from each sampler and adsorbent combination were examined using ordinary or multiple linear regression analysis. The overall uncertainty (OU) was also determined. In general, the results obtained with both samplers showed good agreement with those obtained by active sampling. Carbopack X appeared to be a more efficient adsorbent than Carbograph 5 for 1,3-butadiene, but the two adsorbents were equivalent for benzene. No effects of either humidity or air velocity were observed. Minor temperature effects were observed for both samplers for 1,3-butadiene. In summary, the results confirmed the accuracy of sampling rates previously determined for the two samplers and adsorbents. We consider the two samplers to be suitable for stationary and personal monitoring for the general population of 1,3-butadiene and benzene in various environments, indoors and outdoors. They are almost independent of meteorological conditions and may be suitable for monitoring industrial atmospheres.     

Evaluation of the Use of Diffusive Air Samplers for Determining Temporal and Spatial Variation of Volatile Organic Compounds in the Ambient Air of Urban Communities

Abstract

The Houston-Galveston metropolitan area has a relatively high density of point and mobile sources of air toxics, and determining and understanding the relationship between emissions and ambient air concentrations of air toxics is important for evaluating potential impacts on public health and formulating effective regulatory policies to control this impact, both in this region and elsewhere. However, conventional ambient air monitoring approaches are limited with regard to expense, siting limitations, and representative sampling necessary for adequate exposure assessment. The overall goal of this multiphase study is to evaluate the use of simple passive air samplers to determine temporal and spatial variability of the ambient air concentrations of selected volatile organic compounds (VOCs) in urban areas. Phase 1 of this study, reported here, was a field evaluation of 3M organic vapor monitors (OVMs) involving limited comparisons with commonly used active sampling methods, an assessment of sampler precision, a determination of optimal sampling duration, and an investigation of the utility of a simple modification of the commercial sampler. The results indicated that a sampling duration of 72 hr exhibited generally low bias relative to automated continuous gas chromatography measurements, good overall precision, and an acceptable number of measurements above detection limits. The modified sampler showed good correlation with the commercial sampler, with higher sampling rates, although lower than expected.     

Monitoring ambient ozone with a network of passive samplers: a feasibility study

Ambient levels of ozone have been measured at 46 mountain forest, desert, Class I Wilderness areas and other remote locations using a network of passive samplers. Typical values were 40-80 ppb (2 week samples) and exhibited temporal variations (studied for up to 1 year) as well as changes with elevation (studied up to 10 500 ft (3 200 m)). The performance of the passive sampler was evaluated with respect to reproducibility, field controls, data capture (>0.95), precision for co-located samples (av. = 11.9%, n = 103), and the role of other atmospheric oxidants as potential interferents (2 locations). Suggestions for additional sampler performance evaluation and network operation are outlined.     

Performance characteristics of PM10 samplers under calm air conditions

The size range of airborne particles that is closely related to specific deposition regions in the human respiratory tract and excess lung burden of these deposited particles is associated with disease. Size-selective sampling, therefore, needs to be performed to assess the related health risks. Performance criteria applied to these samplers must be well characterized in order to provide accurate and reliable results. The PM10 samplers that have been used in place of the total suspended particulate samplers for the collection of ambient air particles are more relevant to potential inhalation hazards. In order to be certified, a PM10 sampler must meet reliable performance specifications, primarily the aerosol penetration test with liquid and solid particles in a wind tunnel (wind speeds of 2, 8, and 24 km/hr). This testing is intended to assure reasonable accuracy in aerosol measurements. However, the sampler performance under calm air conditions has not been well studied. In the present study, the sampling heads of three devices--the Harvard impactor, the Personal Environmental Monitor (PEM), and the Sierra Andersen model 241 dichotomous sampler PM10 inlet head--were tested for aerosol separation efficiency. With the consideration of bias and imprecision of the measurements, five specimens of each type of sampler were chosen for performance testing, repeating the tests 5 times for each specimen. An ultrasonic atomizing nozzle was used to nebulize potassium sodium tartrate tetrahydrate and dioctyl phthalate particles as the solid and liquid challenge aerosols, respectively. The aerosol number concentrations and size distributions upstream and downstream of the samplers were measured by using an aerosizer calibrated against a settling velocity chamber. The results showed that among the samplers tested, the dichotomous sampler PM10 inlet head had the best fit to the PM10 convention, while the other two samplers not only appeared to have a steeper separation-curve slope but also had significant particle bounce when challenged with solid particles. Analysis of variance also confirmed the superiority of the dichotomous samplers. Surface-coating with oil or grease greatly reduced the problem of particle bounce.     

Calibration of polyurethane foam (PUF) disk passive air samplers for quantitative measurement of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs): factors influencing sampling rates

PUF disk passive air samplers are increasingly employed for monitoring of POPs in ambient air. In order to utilize them as quantitative sampling devices, a calibration experiment was conducted. Time integrated indoor air concentrations of PCBs and PBDEs were obtained from a low volume air sampler operated over a 50 d period alongside the PUF disk samplers in the same office microenvironment. Passive sampling rates for the fully-sheltered sampler design employed in our research were determined for the 51 PCB and 7 PBDE congeners detected in all calibration samples. These values varied from 0.57 to 1.55 m3 d(-1) for individual PCBs and from 1.1 to 1.9 m3 d(-1) for PBDEs. These values are appreciably lower than those reported elsewhere for different PUF disk sampler designs (e.g. partially sheltered) employed under different conditions (e.g. in outdoor air), and derived using different calibration experiment configurations. This suggests that sampling rates derived for a specific sampler configuration deployed under specific environmental conditions, should not be extrapolated to different sampler configurations. Furthermore, our observation of variable congener-specific sampling rates (consistent with other studies), implies that more research is required in order to understand fully the factors that influence sampling rates. Analysis of wipe samples taken from the inside of the sampler housing, revealed evidence that the housing surface scavenges particle bound PBDEs.     

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

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