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.     

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 performance reference compounds in polyethylene-based passive air samplers

Polyethylene-based passive air samplers (PSDs) were loaded with performance reference compounds (PRCs) and deployed in a wind tunnel to examine the effects of wind speed on sampler performance. PRCs could be loaded reproducibly into PSDs, with coefficients of variation only exceeding 20% for the more volatile compounds. When PSDs were exposed to low (0.5-1.5 m s-1) and high (3.5-4.5 m s-1) wind speeds, PRC loss rate constants generally increased with increasing wind speed and decreased with increasing sampler/air partition coefficients. PSD-based air concentrations calculated using PRC loss rate constants and sampler/air partition coefficients and air concentrations measured using active samplers compared closely. PRCs can be used to account for the effect of differences in wind speeds on sampler performance and measure air concentrations with reasonable accuracy.     

Polycyclic aromatic hydrocarbons in ambient air in the Philippines derived from passive sampler with polyurethane foam disk

Passive samplers with polyurethane disks (PUF) were applied in the determination of the concentration of polycyclic aromatic hydrocarbons (PAHs) in ambient air in six residential areas in the Philippines during four simultaneous sampling periods. The uptake profiles of PAHs were determined at one site during one sampling period. Most of the PAHs that were detected in air at concentrations that were significantly higher than their analytical detection limits exhibited a linear uptake trend on the PUF disk. The linear uptake profiles of some high molecular weight (HMW) PAHs were not established and this is attributed to the low concentration of the compounds in air in the gaseous phase. The retention concentrations of phenanthrene-d-10 were determined after depuration in four sampling sites during two sampling periods. The sampling rate for phenanthrene-d-10 was calculated at the linear phase of the uptake using the k_A derived from depuration experiments and the relationship of k_A and sampling rate which was established in a previous passive sampling study. The average sampling rate obtained for phenanthrene d-10 (2.94±0.69 m³ d⁻¹) was applied for derivation of the concentrations of the PAHs in the field samples.The passive sampler with PUF disk and short integration time of 42–56 days is applicable for the derivation of the concentrations of PAHs in ambient air in the Philippines. The concentrations of the organic pollutants derived from the passive sampler showed variability for the six residential areas; reflecting the influence of possible sources of emission of the pollutants at the sites at the different sampling periods. The weather conditions, including the occurrence of a tropical cyclone, increased rainfall and high-relative humidity during the rainy season, had an influence on the concentrations of PAHs derived by the passive sampler.     

Quality control for sampling of PCDD/PCDF emissions from open combustion sources

Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.     

Validation of a flow-through sampler for pesticides and polybrominated diphenyl ethers in air

At locations without access to the electrical grid, a flow-through sampler (FTS) collects large volumes of air for the analysis of semi-volatile organic compounds (SVOCs). To test its performance under field conditions, an FTS and a traditional pumped high volume air sampler, both using polyurethane foam (PUF) as sampling medium, were co-deployed at the campus of the University of Toronto Scarborough from August 2006 to June 2007. Polybrominated diphenyl ethers (PBDEs) and various pesticides were quantified in the samples taken by both samplers to test the FTS's applicability to relatively non-volatile and slightly polar SVOCs. Air concentrations in samples taken with the FTS over five 2-week periods compare favourably with the average of the concentrations in several 24-h active high volume samples taken during the same period. In particular, time trends, temperature dependence relationships, and isomer ratios show a reasonable agreement between the two sampling techniques. An empirical linear solvation energy relationship for predicting the apparent theoretical plate number of the PUF assembly used in the FTS illustrates the effect of chemical properties, as well as temperature and wind speed, on sampling efficiency. In the absence of electrical power, the FTS can collect SVOCs from large air volumes as reliably and quantitatively as traditional HiVol samplers, although without separating gas and particle phase.     

Measurements of selected PCBs in open urban ambient air of Madrid (Spain)

The focus of this study was to characterize the concentration levels of selected PCBs and compare them to compiled data in order to contribute to the international database. The sampling site is located in the outskirts of Madrid and can be considered an open urban area. 32 samples of air were taken from February 1998 to June 1998 by using a high volume air sampler. Glass fiber filters and polyurethane foam (PUF) were used to collect the paniculate and gas phase material, respectively. PUF plugs were Soxhlet extracted and filters were ultrasonically extracted by using pesticide-grade hexane and dichloromethane, respectively. The cleanup procedure was carried out on a florisil column with hexane and hexane/dichloromethane as elution solvents. GC/MS in a selected ion monitoring mode was used for quantification and 29 selected PCBs congeners were analyzed.     

Isokinetic Sampler for Continuous Airborne Aerosol Measurements

For aerosol measurements, especially those concerned with the aerosol particle size distribution, it is important to sample in isokinetic conditions. Most available instrumentation for aerosol measurements is intended for use on the ground under light wind conditions; intake air speeds rarely exceed a few meters per second. If the same instrumentation is used onboard an aircraft, the air must be decelerated 60 or more m/sec before It is sampled by individual instruments.

On The Pennsylvania State University Meteorology research aircraft, the air for all aerosol instruments is decelerated in a single isokinetic sampler located above the roof of the cabin outside the aircraft boundary layer. The air enters the sampler through a carefully designed circular intake. Its velocity is reduced as the cross section increases along a 7° conical diffuser. The expansion cone terminates in a cylindrical chamber in which the air velocity is 1/16 the aircraft speed. Behind the sampling chamber the air is accelerated in a second conical section to an end exhaust port. Exhaust porf "pumping" is used to compensate internal losses and, thus, helps preserve the isokinetic nature of the sampler.

Tubes leading to individual instruments are located in the sampling chamber and may be individually adapted to match the air sampling velocity with the local air speed inside the sampling chamber. The level of turbulence (u_rms/û) in the sampling section is =^0.05.

The sampler has been thoroughly wind tunnel and flight tested and successfully used in August and November, 1974, for field programs in the St. Louis and Tucson metropolitan areas, respectively.     

Further studies on the uptake of persistent organic pollutants (POPs) by polyurethane foam disk passive air samplers

Passive air samplers (PAS) can be used to monitor semi-volatile organic compounds in the atmosphere. Polyurethane foam (PUF) disks are a popular sampling medium because they have a high retention capacity for such compounds. This paper reports a highly time-resolved uptake study, to derive uptake rate data under field conditions, and investigate the effects of using different foam densities on the uptake rate. PUF disks were deployed alongside an active sampler, for periods of up to 12 weeks. The uptake rates were measured for a range of gas- and particle-bound persistent organic pollutants (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)), of different properties, to explore whether gas–particle partitioning affected uptake rate. Uptake rates for two different densities of foam (0.021 and 0.035 g cm^?3) were not statistically significantly different from each other. Uptake rates of light PCBs averaged ～6.5 m³ day^?1, somewhat higher than in previous studies; higher wind speeds and lower temperatures in this study are the likely reason for this difference. The study showed: i) the uptake rate of the compound with lowest K_OA considered in this study (PCB-28/31) declined in the later weeks, indicating an approach to equilibrium; ii) uptake rates of lighter BDEs and heavier PCBs (compounds of intermediate K_OA in this study) remain similar throughout the study period, indicating that they are not approaching equilibrium during the 12-week-study; iii) uptake rates were typically: ～8 m³ day^?1 for PCB-52; ～9.5 m³ day^?1 for PCB-95; ～11 m³ day^?1 for BDE-28 and ～2 m³ day^?1 BDE-99. The latter compound has an important particle-bound component and this lowers the sampling rate compared to predicted uptake rates for compounds which are in the gas phase only. It is shown that knowledge of gas–particle partitioning is needed to correct for this effect, and to improve predicted uptake rates.     

A wind tunnel test of newly developed personal bioaerosol samplers

In this study the performance of two newly developed personal bioaerosol samplers was evaluated. The two test samplers are cyclone-based personal samplers that incorporate a recirculating liquid film. The performance evaluations focused on the physical efficiencies that a personal bioaerosol sampler could provide, including aspiration, collection, and capture efficiencies. The evaluation tests were carried out in a wind tunnel, and the test personal samplers were mounted on the chest of a full-size manikin placed in the test chamber of the wind tunnel. Monodisperse fluorescent aerosols ranging from 0.5 to 20 microm were used to challenge the samplers. Two wind speeds of 0.5 and 2.0 m/sec were employed as the test wind speeds in this study. The test results indicated that the aspiration efficiency of the two test samplers closely agreed with the ACGIH inhalable convention within the size range of the test aerosols. The aspiration efficiency was found to be independent of the sampling orientation. The collection efficiency acquired from these two samplers showed that the 50% cutoff diameters were both around 0.6 microm. However the wall loss of these two test samplers increased as the aerosol size increased, and the wall loss of PAS-4 was considerably higher than that of PAS-5, especially in the aerosol size larger than 5 microm, which resulted in PAS-4 having a relatively lower capture efficiency than PAS-5. Overall, the PAS-5 is considered a better personal bioaerosol sampler than the PAS-4.     

空气中多环芳烃的研究现状

本文比较系统地讨论了空气中多环芳烃（ＰＡＨｓ）的研究现状。重点介绍了空气颗粒物及气相中多环芳烃的采样分析新办法，城市大气及居民室内外空气中多环芳烃的污染状况及其来源，简单介绍了人体接触多环芳烃的水平，指标及空气中多环芳烃的健康风险评价的研究概况。共引文献１２９篇。     

The potential effect of differential ambient and deployment chamber temperatures on PRC derived sampling rates with polyurethane foam (PUF) passive air samplers

Performance reference compound (PRC) derived sampling rates were determined for polyurethane foam (PUF) passive air samplers in both sub-tropical and temperate locations across Australia. These estimates were on average a factor of 2.7 times higher in summer than winter. The known effects of wind speed and temperature on mass transfer coefficients could not account for this observation. Sampling rates are often derived using ambient temperatures, not the actual temperatures within deployment chambers. If deployment chamber temperatures are in fact higher than ambient temperatures, estimated sampler-air partition coefficients would be greater than actual partition coefficients resulting in an overestimation of PRC derived sampling rates. Sampling rates determined under measured ambient temperatures and estimated deployment chamber temperatures in summer ranged from 7.1 to 10 m³ day⁻¹ and 2.2-6.8 m³ day⁻¹ respectively. These results suggest that potential differences between ambient and deployment chamber temperatures should be considered when deriving PRC-based sampling rates.     

The Petroleum Refining Industry—Air Pollution Problems and Control Methods

Polyurethane foam was incorporated as a prefilter on standard hi-volume samplers of the National Air Sampling Network (NASN) in an exploratory study. The foam selectively filtered particles of various sizes. The characteristics of the particles passing through the foam approached the respirable size fraction as defined by reports of the Atomic Energy Commission. The respirable fraction was then collected on a glass-fiber filter. Parameters such as pore size and thickness of the foam, air flow rates, and loadings were studied to determine their effects on the filtration of “respirable” dust. Ambient air was the particulate source, and sizing was accomplished by an Andersen sampler coupled with nephelometric analyses. Some sizing was also done microscopically. The foam was evaluated at several locations to account for possible variations in ambient air over areas of different industrial complexity.     

A directional passive air sampler for monitoring polycyclic aromatic hydrocarbons (PAHs) in air mass

A passive air sampler was developed for collecting polycyclic aromatic hydrocarbons (PAHs) in air mass from various directions. The airflow velocity within the sampler was assessed for its responses to ambient wind speed and direction. The sampler was examined for trapped particles, evaluated quantitatively for influence of airflow velocity and temperature on PAH uptake, examined for PAH uptake kinetics, calibrated against active sampling, and finally tested in the field. The airflow volume passing the sampler was linearly proportional to ambient wind speed and sensitive to wind direction. The uptake rate for an individual PAH was a function of airflow velocity, temperature and the octanol-air partitioning coefficient of the PAH. For all PAHs with more than two rings, the passive sampler operated in a linear uptake phase for three weeks. Different PAH concentrations were obtained in air masses from different directions in the field test.     

Calibration of the Chemcatcher passive sampler for monitoring selected polar and semi-polar pesticides in surface water

Passive sampling is a powerful method for continuous pollution monitoring, but calibration experiments are still needed to generate sampling rates in order to estimate water concentrations for polar compounds. We calibrated the Chemcatcher device with an uncovered SDB-XC Empore disk as receiving phase for 12 polar and semi-polar pesticides in aquatic environments in flow-through tank experiments at two water flow velocities (0.135 m/s and 0.4 m/s). In the 14-day period of exposure the uptake of test substances in the sampler remained linear, and all derived sampling rates R(s) were in the range of 0.1 to 0.5 L/day. By additionally monitoring the release of two preloaded polar pesticides from the SDB-XC disks over time, very high variation in release kinetics was found, which calls into question the applicability of performance reference compounds. Our study expands the applicability of the Chemcatcher for monitoring trace concentrations of pesticides with frequent occurrence in water.     

Per- and polyfluorinated compounds in house dust and indoor air from northern Norway - a pilot study

Polyfluorinated compounds (PFCs) are an extremely versatile class of compounds and are used in a variety of consumer applications and products. Recent studies have suggested that PFCs in indoor air and dust could act as sources of human exposure and outdoor air contamination. This study presents method development and analysis of a wide range of PFCs in dust and air using active sampling techniques with commercially available sampling equipment (forensic nozzles with filter housings for dust collection and polyurethane foam (PUF)-XAD₂-PUF sandwich-tubes for air sampling) using both liquid and gas chromatography mass spectrometry. The developed method was validated and tested for applicability to analyze dust and air samples at both low and high concentrations (0.5 ng and 25 ng per analyte per air sample, respectively). Samples from private households and an office building were analyzed to explore differences in distribution patterns and concentrations. Perfluorooctane sulfonate, perfluorodecane sulfonate, perfluoroheptanoate, perfluorooctanoate and perfluorononanoate were observed in all samples of dust from private households, in the range from 1 to 80.1 ng g⁻¹. Fluorotelomer alcohols (FTOHs) were the predominant PFCs in indoor air samples with ∑FTOHs ranging between 4.7 and 17.9 ng m⁻³. The concentrations found in the present study are generally lower than those previously reported. This variation may be due to differences associated with geographical locations and lifestyles. However, use of different sampling techniques and strategies among studies can introduce large variations in PFC concentration found, making direct comparisons challenging.     

Characterizing perfluorooctanoate in ambient air near the fence line of a manufacturing facility: comparing modeled and monitored values

In order to improve our understanding of the nature, measurement and prediction of salts of perfluorooctanoic acid (PFOA) in air, two studies were performed along the fence line of a fluoropolymer manufacturing facility. First, a six-event, 24-hr monitoring series was performed around the fence line using the OSHA versatile sampler (OVS) system. Perfluorooctanoate concentrations were determined as perfluorooctanoic acid (PFOA) via liquid chromatography and mass spectrometry. Those data indicated that the majority of the PFOA was present as a particulate. No vapor-phase PFOA was detected above a detection limit of approximately 0.07 microg/m3. A follow-up study using a high-volume cascade impactor verified the range of concentrations observed in the OVS data. Both studies aligned with the major transport direction and range of concentrations predicted by an air dispersion model, demonstrating that model predictions agreed with monitoring results. Results from both monitoring methods and predictions from air dispersion modeling showed the primary direction of transport for PFOA was in the prevailing wind direction. The PFOA concentration measured at the site fence over the 10-week sampling period ranged from 0.12 to 0.9 microg/m3. Modeled predictions for the same time period ranged from 0.12 to 3.84 microg/m3. Less than 6% of the particles were larger than 4 microm in size, while almost 60% of the particles were below 0.3 microm. These studies are believed to be the first published ambient air data for PFOA in the environment surrounding a manufacturing facility.     

Passive air monitoring of PCBs and PCNs across East Asia: a comprehensive congener evaluation for source characterization

A comprehensive congener specific evaluation of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in the atmosphere was conducted across East Asia in spring 2008, applying polyurethane foam (PUF) disk passive air sampler (PAS) as monitoring device. Mean concentrations derived for Japan, China and Korea were 184 ± 24, 1100 ± 118, and 156 ± 20 pg m⁻³ for ∑₂₀₂ PCBs, and 9.5 ± 1.5, 61 ± 6, and 16 ± 2.4 pg m⁻³ for ∑₆₃ PCNs, respectively. Relative to reported data from 2004, the present results suggest that air PCBs concentrations have not changed much in Japan and Korea, while it has increased by one order of magnitude in China. From principal component analysis, combustion emerged highly culpable in contemporary emissions of both PCBs and PCNs across the East Asian sub-region. Another factor derived as important to air PCBs was re-emissions/volatilization. Signals from PCBs formulations were also picked, but their general importance was virtually consigned to the re-emissions/volatilization tendencies. On the contrary, counterpart PCNs formulations did not appear to contribute much to air PCNs.     

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.