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.     

Passive sampling of ambient, gaseous air pollutants: an assessment from an ecological perspective

During some past two decades there has been a growing interest among air pollution-vegetation effects-scientists to use passive sampling systems for quantifying ambient, gaseous air pollutant concentrations, particularly in remote and wilderness areas. On the positive side, excluding the laboratory analysis costs, passive samplers are inexpensive, easy to use and do not require electricity to operate. Therefore, they are very attractive for use in regional-scale air quality assessments. Passive samplers allow the quantification of cumulative air pollutant exposures, as total or average pollutant concentrations over a sampling duration. Such systems function either by chemical absorption or by physical adsorption of the gaseous pollutant of interest onto the sampling medium. Selection of a passive sampler must be based on its known or tested characteristics of specificity and linearity of response to the chemical constituent being collected. In addition, the effects of wind velocity, radiation, temperature and relative humidity must be addressed in the context of absorbent/adsorbent performance and sampling rate. Because of all these considerations, passive samplers may provide under- or overestimations of the cumulative exposures, compared to the corresponding data from co-located continuous monitors or active samplers, although such statistical variance can be minimized by taking necessary precautions. On the negative side, cumulative exposures cannot identify short-term (相似文献   

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.     

Intercalibration of a passive wind-vane flux sampler against a continuous-flow denuder for the measurements of atmospheric ammonia concentrations and surface exchange fluxes

A passive wind-vane flux sampler is a simple low-cost device used to estimate long-term vertical fluxes of ammonia in the atmospheric surface boundary layer. The passive flux sampler measures the horizontal flux of ammonia. A vertical gradient of the horizontal flux, combined with micro-meteorological measurements of wind speed and temperature, is used to estimated the vertical flux of ammonia using a modified aerodynamic gradient technique. The passive wind-vane flux sampler gradient was calibrated against a gradient measured with fast response (6 min) continuous-flow denuders. The measurements were carried out at a heathland located in an intensive farming area in the centre of the Netherlands. A field campaign took place over 70 day period in the summer of 1996, during which the sampling periods of the passive wind-vane flux sampler varied between 3 and 9 days. The comparison clearly showed that the long-term measurements with the passive wind-vane flux samplers gave accurate average ammonia deposition values for the field campaign as a whole which deviated by only 18% from the reference flux. However, there was no significant correlation between the fluxes from the passive samplers and the reference method for the individual 10 periods which were compared. Possible explanations found for the lacking correlation were (I) a high percentage number of half-hour emission events within each period resulted in a significant large relative deviation between the fluxes, and (II) uncertainties in the reference method might also explain the lacking correlation. The passive wind-vane flux samplers proved to be a stable method for long-term measurements (months to years) due to a close to 100% optimal functioning during the field campaign.     

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.     

Passive sampler for PM10-2.5 aerosol

This study investigates the use of a small passive sampler for aerosol particles to determine particulate matter (PM)10-2.5 concentrations in outdoor air. The passive sampler collects particles by gravity, diffusion, and convective diffusion onto a glass coverslip that is then examined with an optical microscope; digital images are processed with free software and the resultant PM10-2.5 concentrations determined. Both the samplers and the analyses are relatively inexpensive. Passive samplers were collocated with Federal Reference Method (FRM) samplers in Chapel Hill, NC; Phoenix, AZ; and Birmingham, AL; for periods from 5 to 15 days. Particles consisted primarily of inorganic dusts at some sites and a mix of industrial and inorganic materials at other sites. Measured concentrations ranged from < 10 microg/m3 to approximately 40 microg/m3. Overall, PM10-2.5 concentrations measured with the passive samplers were within approximately 1 standard deviation of concentrations measured with the FRM samplers. Concentrations determined with passive samplers depend on assumptions about particle density and shape factors and may also depend somewhat on local wind speed and turbulence; accurate values for these parameters may not be known. The degree of agreement between passive and FRM concentrations measured here suggests that passive measurements may not be overly dependent on accurate knowledge of these parameters.     

Volatile organic compounds at two oil and natural gas production well pads in Colorado and Texas using passive samplers

A pilot study was conducted in application of the U.S. Environmental Protection Agency (EPA) Methods 325A/B variant for monitoring volatile organic compounds (VOCs) near two oil and natural gas (ONG) production well pads in the Texas Barnett Shale formation and Colorado Denver–Julesburg Basin (DJB), along with a traffic-dominated site in downtown Denver, CO. As indicated in the EPA method, VOC concentrations were measured for 14-day sampling periods using passive-diffusive tube samplers with Carbopack X sorbent at fenceline perimeter and other locations. VOCs were significantly higher at the DJB well pad versus the Barnett well pad and were likely due to higher production levels at the DJB well pad during the study. Benzene and toluene were significantly higher at the DJB well pad versus downtown Denver. Except for perchloroethylene, VOCs measured at passive sampler locations (PSs) along the perimeter of the Barnett well pad were significantly higher than PSs farther away. At the DJB well pad, most VOC concentrations, except perchloroethylene, were significantly higher prior to operational changes than after these changes were made. Though limited, the results suggest passive samplers are precise (duplicate precision usually ≤10%) and that they can be useful to assess spatial gradients and operational conditions at well pad locations over time-integrated periods.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at multiple fenceline locations at petrochemical refineries. This pilot study presents initial data demonstrating the utility of Methods 325A/B for monitoring at ONG facilities. Measurements revealed elevated concentrations reflective of production levels and spatial gradients of VOCs relative to source proximity at the Barnett well pad, as well as operational changes at the DJB well pad. Though limited, these findings indicate that Methods 325A/B can be useful in application to characterize VOCs at well pad boundaries.     

Computational fluid dynamic modeling of two passive samplers

To effectively use a passive sampler for monitoring trace contaminants in the gas-phase, its sampling characteristics as a function of ambient wind conditions must be known. In this study two commonly used passive samplers were evaluated using computational fluid dynamics. Contaminant uptake by the polyurethane foam (PUF) was modeled using a species transport model. The external-internal flow interactions in the sampler were characterized, and the uptake rates of contaminant species were quantified. The simulations show that flow fields in the samplers have strong velocity gradients, and single-point velocity measurements do not capture flow interactions accurately. Sampling rates calculated for a PUF in freestream are in good agreement with sampling rates for PUFs in the passive samplers studied for the same average velocity over the PUF. The calculated sampling rates are in general agreement with those obtained experimentally by other researchers.     

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.     

Verification of diffusive and pumped samplers for volatile organic compounds using a controlled atmosphere test facility

There is a requirement to verify the performance of sorbent-based passive or active samplers and to extend their use, where possible, to monitor volatile organic compounds (VOCs) that are known to be photochemical ozone pre-cursors or are relevant to the activities of the petrochemical industry. We report measurements of the 14-day diffusive uptake rates for the VOCs: i-butane (2-methyl propane), n-butane, i-pentane (2-methyl butane), n-pentane, n-hexane, benzene, toluene, and m-xylene (at environmental level concentrations) for industry standard axial samplers (Perkin–Elmer-type samplers) containing the sorbents Carbopack-X, -Z, -B or Tenax-TA. We also present data on back-diffusion, blank levels, and storage for the above sorbents, and describe the simultaneous use of the sorbent Carbopack-X for pumped sampling of certain VOCs. The results were obtained by dosing samplers in a controlled atmosphere test facility (CATFAC) operating under well-defined conditions of concentration, nominal temperature of 20 °C, wind speed of 0.5 m s^?1, and relative humidities of 0% and 80%. Field measurements were also obtained to provide supplementary data to support the laboratory study. Results are compared to existing published data, where these are available.     

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.     

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.     

A multi-variate statistical model integrating passive sampler and meteorology data to predict the frequency distributions of hourly ambient ozone (O3) concentrations

A multi-variate, non-linear statistical model is described to simulate passive O3 sampler data to mimic the hourly frequency distributions of continuous measurements using climatologic O3 indicators and passive sampler measurements. The main meteorological parameters identified by the model were, air temperature, relative humidity, solar radiation and wind speed, although other parameters were also considered. Together, air temperature, relative humidity and passive sampler data by themselves could explain 62.5-67.5% (R(2)) of the corresponding variability of the continuously measured O3 data. The final correlation coefficients (r) between the predicted hourly O3 concentrations from the passive sampler data and the true, continuous measurements were 0.819-0.854, with an accuracy of 92-94% for the predictive capability. With the addition of soil moisture data, the model can lead to the first order approximation of atmospheric O3 flux and plant stomatal uptake. Additionally, if such data are coupled to multi-point plant response measurements, meaningful cause-effect relationships can be derived in the future.     

Comparison of real-time instruments used to monitor airborne particulate matter

Measurements collected using five real-time continuous airborne particle monitors were compared to measurements made using reference filter-based samplers at Bakersfield, CA, between December 2, 1998, and January 31, 1999. The purpose of this analysis was to evaluate the suitability of each instrument for use in a real-time continuous monitoring network designed to measure the mass of airborne particles with an aerodynamic diam less than 2.5 microns (PM2.5) under wintertime conditions in the southern San Joaquin Valley. Measurements of airborne particulate mass made with a beta attenuation monitor (BAM), an integrating nephelometer, and a continuous aerosol mass monitor (CAMM) were found to correlate well with reference measurements made with a filter-based sampler. A Dusttrak aerosol sampler overestimated airborne particle concentrations by a factor of approximately 3 throughout the study. Measurements of airborne particulate matter made with a tapered element oscillating microbalance (TEOM) were found to be lower than the reference filter-based measurements by an amount approximately equal to the concentration of NH4NO3 observed to be present in the airborne particles. The performance of the Dusttrak sampler and the integrating nephelometer was affected by the size distribution of airborne particulate matter. The performance of the BAM, the integrating nephelometer, the CAMM, the Dusttrak sampler, and the TEOM was not strongly affected by temperature, relative humidity, wind speed, or wind direction within the range of conditions encountered in the current study. Based on instrument performance, the BAM, the integrating nephelometer, and the CAMM appear to be suitable candidates for deployment in a real-time continuous PM2.5 monitoring network in central California for the range of winter conditions and aerosol composition encountered during the study.     

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.     

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.     

Systematic biases in measured PM10 values with U.S. Environmental Protection Agency-approved samplers at Owens Lake, California

From 1993 through 1998, Wedding or Graseby high-volume PM10 samplers were collocated with tapered element oscillating microbalance (TEOM) samplers at three sites at Owens Lake, CA. The study area is heavily impacted by windblown dust from the dry Owens Lake bed, which was exposed as a result of water diversions to the city of Los Angeles. A dichotomous (dichot) sampler and three collocated Partisol samplers were added in 1995 and 1999, respectively. U.S. Environmental Protection Agency (EPA) operating procedures were followed for all samplers, except for a Wedding sampler that was not cleaned for the purpose of this study. On average, the TEOM and Partisol samplers agreed to within 6%, and the dichot, Graseby, and Wedding samplers measured lower PM10 concentrations by about 10, 25, and 35%, respectively. Surprisingly, the "clean" Wedding sampler consistently measured the same concentration as the "dirty" Wedding sampler through 85 runs without cleaning. The finding that the Graseby and Wedding high-volume PM10 samplers read consistently lower than the TEOM, Partisol, and dichot samplers at Owens Lake is consistent with PM10 sampler comparisons done in other fugitive dust areas, and with wind tunnel tests showing that sampler cut points can be significantly lower than 10 microns under certain conditions. However, these results are opposite of the bias found for TEOM samplers in areas that have significant amounts of volatile particles, where the TEOM reads low due to the vaporization of particles on the TEOM's heated filter. Coarse particles like fugitive dust are relatively unaffected by the filter temperature. This study shows that in the absence of volatile particles and in the presence of fugitive dust, a different systematic bias of up to 35% exists between samplers using dichot inlets and high-volume samplers, which may cause the Graseby and Wedding PM10 samplers to undermeasure PM10 by up to 35% when the PM10 is predominantly from coarse particulate sources.     

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.     

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.     

Systematic Biases in Measured PM10 Values with U.S. Environmental Protection Agency-Approved Samplers at Owens Lake,California

ABSTRACT

From 1993 through 1998, Wedding or Graseby high-volume PM₁₀ samplers were collocated with tapered element oscillating microbalance (TEOM) samplers at three sites at Owens Lake, CA. The study area is heavily impacted by windblown dust from the dry Owens Lake bed, which was exposed as a result of water diversions to the city of Los Angeles. A dichotomous (dichot) sampler and three collocated Partisol samplers were added in 1995 and 1999, respectively. U.S. Environmental Protection Agency (EPA) operating procedures were followed for all samplers, except for a Wedding sampler that was not cleaned for the purpose of this study. On average, the TEOM and Partisol samplers agreed to within 6%, and the dichot, Graseby, and Wedding samplers measured lower PM₁₀ concentrations by about 10, 25, and 35%, respectively. Surprisingly, the “clean” Wedding sampler consistently measured the same concentration as the “dirty” Wedding sampler through 85 runs without cleaning. The finding that the Graseby and Wedding high-volume PM₁₀ samplers read consistently lower than the TEOM, Partisol, and dichot samplers at Owens Lake is consistent with PM₁₀ sampler comparisons done in other fugitive dust areas, and with wind tunnel tests showing that sampler cut points can be significantly lower than 10 um under certain conditions. However, these results are opposite of the bias found for TEOM samplers in areas that have significant amounts of volatile particles, where the TEOM reads low due to the vaporization of particles on the TEOM's heated filter. Coarse particles like fugitive dust are relatively unaffected by the filter temperature. This study shows that in the absence of volatile particles and in the presence of fugitive dust, a different systematic bias of up to 35% exists between samplers using dichot inlets and high-volume samplers, which may cause the Graseby and Wedding PM₁₀ samplers to undermeasure PM₁₀ by up to 35% when the PM₁₀ is predominantly from coarse particulate sources.