Field testing passive air samplers for current use pesticides in a tropical environment

Air was sampled for one year in the central valley of Costa Rica using an active high-volume sampler as well as passive samplers (PAS) based on polyurethane foam (PUF) disks and XAD-resin filled mesh cylinders. Extracts were analyzed for pesticides that are either banned or currently used in Costa Rican agriculture. Sampling rates for PUF-based passive air samplers, determined from the loss of depuration compounds spiked on the disks prior to deployment averaged 5.9 +/- 0.9 m3 x d(-1) and were higher during the windier dry season than during the rainy season. Sampling rates for the XAD-based passive sampler were determined from the slopes of linear relationships that were observed between the amount of pesticide sequestered in the resin and the length of deployment, which varied from 4 months to 1 year. Those sampling rates increased with decreasing molecular size of a pesticide, and their average of 2.1 +/- 1.5 m3 x d(-1) is higher than rates previously reported for temperate and polar sampling sites. Even though the trends of the sampling rate with molecular size and temperature are consistent with the hypothesis that molecular diffusion controls uptake in passive samplers, the trends are much more pronounced than a direct proportionality between sampling rate and molecular diffusivity would suggest. Air concentrations derived by the three sampling methods are within a factor of 2 of each other, suggesting that properly calibrated PAS can be effective tools for monitoring levels of pesticides in the tropical atmosphere. In particular, HiVol samplers, PUF-disk samplers, and XAD-based passive samplers are suitable for obtaining information on air concentration variability on the time scale of days, seasons and years, respectively. This study represents the first calibration study for the uptake of current use pesticides by passive air samplers.     

In situ measurement of PCB pore water concentration profiles in activated carbon-amended sediment using passive samplers

Vertical pore water profiles of in situ PCBs were determined in a contaminated mudflat in San Francisco Bay, CA, 30 months after treatment using an activated carbon amendment in the upper layer of the sediment. Pore water concentrations were derived from concentrations of PCBs measured in two passive samplers; polyethylene (PE, 51 μm thick) and polyoxymethylene (POM, 17 μm thick) at different sediment depths. To calculate pore water concentrations from PCB contents in the passive samplers, an equilibrium approach and a first-order uptake model were applied, using five performance reference compounds to estimate pore water sampling rates. Vertical pore water profiles showed good agreement among the measurement and calculation methods with variations within a factor of 2, which seems reasonable for in situ measurements. The close agreements of pore water estimates for the two sampler materials (PE and POM) and the two methods used to translate uptake in samplers to pore water concentrations demonstrate the robustness and suitability of the passive sampling approach. The application of passive samplers in the sediment presents a promising method for site monitoring and remedial treatment evaluation of sorbent amendment or capping techniques that result in changes of pore water concentrations in the sediment subsurface.     

Calibration of a passive sampler for both gaseous and particulate phase polycyclic aromatic hydrocarbons

A novel passive air sampler was designed and tested that individually collects the gaseous and particulate phase polycyclic aromatic hydrocarbons (PAHs) in air. The sampler was calibrated against a conventional active sampler in an indoor environment. A PUF (polyurethane foam) disk and a piece of GFF (glass fiber filter) were installed in a sampling shelter for collecting gaseous and particulate phase PAHs, respectively. The passive samplers were deployed in seven indoor locations for 86 days. Six times during this period, 24-h conventional active sampling was conducted for calibration at an average interval of 17-days. Principle component analysis showed that the measured congener profile compositions were totally different between the gaseous and particulate phase PAHs, but similar between the passive and the active samples. This suggested that gaseous and particulate phase PAHs were primarily trapped by the PUF disk and GFF, respectively. Linear relationships between the passively and the actively measured and log-transformed concentrations were derived for calibration of both gaseous and particulate phase PAHs. The uptake rates of the sampler were 0.10 +/- 0.014 m3/d and 0.007 +/- 0.001 m3/d for gaseous and particulate phase PAHs, respectively. The rates were significantly lower than those reported in the literature using similar PUF samplers, mainly because of the special design with limited air circulation.     

Time-weighted average water sampling in Lake Ontario with solid-phase microextraction passive samplers

In this study, three types of solid-phase microextraction (SPME) passive samplers, including a fiber-retracted device, a polydimethylsiloxane (PDMS)-rod and a PDMS-membrane, were evaluated to determine the time weighted average (TWA) concentrations of polycyclic aromatic hydrocarbons (PAHs) in Hamilton Harbor (the western tip of Lake Ontario, ON, Canada). Field trials demonstrated that these types of SPME samplers are suitable for the long-term monitoring of organic pollutants in water. These samplers possess all of the advantages of SPME: they are solvent-free, sampling, extraction and concentration are combined into one step, and they can be directly injected into a gas chromatograph (GC) for analysis without further treatment. These samplers also address the additional needs of a passive sampling technique: they are economical, easy to deploy, and the TWA concentrations of target analytes can be obtained with one sampler. Moreover, the mass uptake of these samplers is independent of the face velocity, or the effect can be calibrated, which is desirable for long-term field sampling, especially when the convection conditions of the sampling environment are difficult to measure and calibrate. Among the three types of SPME samplers that were tested, the PDMS-membrane possesses the highest surface-to-volume ratio, which results in the highest sensitivity and mass uptake and the lowest detection level.     

Passive air sampling using semipermeable membrane devices at different wind-speeds in situ calibrated by performance reference compounds

Semipermeable membrane devices (SPMDs) are passive samplers used to measure the vapor phase of organic pollutants in air. This study tested whether extremely high wind-speeds during a 21-day sampling increased the sampling rates of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), and whether the release of performance reference compounds (PRCs) was related to the uptakes at different wind-speeds. Five samplers were deployed in an indoor, unheated, and dark wind tunnel with different wind-speeds at each site (6-50 m s(-1)). In addition, one sampler was deployed outside the wind tunnel and one outside the building. To test whether a sampler, designed to reduce the wind-speeds, decreased the uptake and release rates, each sampler in the wind tunnel included two SPMDs positioned inside a protective device and one unprotected SPMD outside the device. The highest amounts of PAHs and PCBs were found in the SPMDs exposed to the assumed highest wind-speeds. Thus, the SPMD sampling rates increased with increasing wind-speeds, indicating that the uptake was largely controlled by the boundary layer at the membrane-air interface. The coefficient of variance (introduced by the 21-day sampling and the chemical analysis) for the air concentrations of three PAHs and three PCBs, calculated using the PRC data, was 28-46%. Thus, the PRCs had a high ability to predict site effects of wind and assess the actual sampling situation. Comparison between protected and unprotected SPMDs showed that the sampler design reduced the wind-speed inside the devices and thereby the uptake and release rates.     

A passive sampler for the determination of airborne ammonia concentrations near large-scale animal facilities

Few data are available on the ammonia emissions of large-scale outdoor animal facilities in arid climates such as those found in California's San Joaquin Valley. Passive samplers provide an ideal tool for studying such large and heterogeneous area sources, because they are inexpensive, portable, and fully self-contained. UC Davis passive ammonia samplers incorporate modifications on a previous design, the Willems Badge, for ease of analysis. Citric acid was chosen as a coating medium though it performed as well as oxalic, sulfuric, and tartaric acids. Zefluor PTFE prefilters were used instead of Teflo though both showed the same resistance to diffusion. Citric acid-coated filters were stable for up to 10 weeks, though more so if stored in Petri dishes rather than in the sampling cassettes themselves. The most effective sampler position was found to be in a face-down configuration fixed into the wind to avoid debris and sensitivity to wind shifts. A new method of rinsing the filters within the cassettes by dropwise elution proved highly effective, with 85% of the ammonium being removed in the first 3 mL of the 10-mL rinse volume. Application of the sampler at a dairy in the Joaquin Valley revealed large variations in concentrations at different locations along the downwind fenceline, which correlated with animal populations and activities directly upwind. In addition, large variations in ammonia concentrations were observed in relation to time of day and animal activity. Field blank loadings were of 1.40 microg NH4-N/filter (SD = 0.74 microg NH4-N/filter). Replicate passive samplers placed side-by-side during sampling episodes agreed with a slope of 1.010 (standard error = 0.028). Impingers were used as a reference method to obtain the correlation between filter loadings and air concentrations, yielding an "effective sampling rate" for the passive samplers of 6.18 L/h (error = 0.23 L/h). Using a theoretical calculation, that "effective flow rate" was calculated to be 6.29 L/h. The method's limit of detection was found to be 82.5 microg NH4-N/m3. Wind speed was found to theoretically affect linearity of sampler response only for speeds less than 0.92 m/s.     

Automated sampler for the measurement of non-methane organic compounds

An automated sampler has been constructed for the unattended collection of whole-air samples in Summa passivated stainless steel canisters. The sampler consists of a Viton diaphragm pump; a differential-pressure flow controller; a 2-position, 3-port valve; a 10-port multiposition valve; and a digital valve sequence programmer that controls the sequence and timing of the electrically actuated valves. All connecting tubing was constructed from Silcosteel tubing. Two configurations of the automated sampler and a passive collection system were evaluated by comparing the combined sampling precisions of the three systems with the analytic precision, derived from replicate analyses of an ambient air sample. The analytic precision was generally < +/- 5%, with higher values observed for analytes with mixing ratios in the tens of pptv. However, analytic precision values for methanol and ethanol were poor, greater than +/- 20%. Values for sampling precision were greater by about a factor of 2 than the analytic precision. The poor results for the light oxygenated hydrocarbons could be caused by sorption of the analytes in the preconcentration and sampling systems and difficulties in peak integration.     

A flow-through sampler for semivolatile organic compounds in air

A widely acknowledged limitation of current passive air sampling designs for semivolatile organic chemicals is their relatively low sampling rate, severely constraining the temporal resolution that can be achieved. Addressing the need for an improved sampling design which achieves significantly faster uptake while maintaining the capability of providing quantitative information, a new sampler has been developed that provides greatly increased sampling rates by forcing the wind to blow through the sampling medium. The sampler consists of a horizontally oriented, aerodynamically shaped, stainless steel flow tube mounted on a post with ball bearings, which turns into the wind with the help of vanes. A series of polyurethane foam (PUF) discs with relatively large porosity mounted inside the flow tube serve as the sampling medium. The sampled air volume is calculated from wind speed, which is measured outside the sampler and after passage through the sampling medium using precalibrated vortex rotor and turbine anemometers mounted on top of the sampler and at the exit of the flow tube, respectively. Small battery-operated data loggers are used for data storage. Under typical wind speed conditions, the sampler can collect 100 m(3)/ day, which is approaching the sampling rates of conventional high volume samplers. Controlled experiments in the laboratory and frontal chromatography theory yield the theoretical plate number and breakthrough volumes for polychlorinated biphenyls and polycyclic aromatic hydrocarbons in the PUF plugs and allow for the estimation of breakthrough levels for relatively volatile organic chemicals. After correction for breakthrough, the air concentration obtained with the new flow-through sampler are independent of sampling length and volume and compare favorably with those obtained from conventional pumped high volume samples.     

Levels and sources of personal inhalation exposure to volatile organic compounds

Personal exposures to VOCs of 12 urban dwellers were measured directly via personal monitoring and indirectly via static monitoring combined with personal activity diaries. Over 5-10 days, day-to-day variations in personal exposures of individuals were substantial, with statistically significant (p<0.05) deviation from the normal distribution observed for daily exposures to one or more VOCs for several subjects. Daytime concentrations generally exceeded night time, with day:night mean concentration ratios for each sampling day >1 for most VOCs, with the maximum (3.85) occurring for 1,3-butadiene. Exposure in the home contributed 50-80% of overall individual exposure to 1,3-butadiene and benzene. For most VOCs, while absolute values of direct and indirect exposure estimates were significantly different (p<0.05), linear regression of direct and indirect exposure estimates revealed statistically significant correlation (p<0.01), confirming previous observations that indirect monitoring can provide satisfactory estimates of personal inhalation exposure to VOCs. ETS, the use of vehicles, and heating (but not cooking) all made appreciable contributions to personal exposure to all target VOCs.     

Rapidly equilibrating micrometer film sampler for priority pollutants in air

Modified polymer-coated glass samplers (POGs), termed EVA samplers, consist of micrometer-thin layers of ethylene vinyl acetate (EVA) coated onto a glass fiber filter or aluminum foil substrate. These samplers were designed to equilibrate rapidly with priority pollutants in air, making them ideal for short-term spatial studies in ambient or indoor air. The EVA sampler was calibrated by measuring the uptake of polychlorinated biphenyls (PCBs) over 8 weeks in an indoor environment, and four different film thicknesses were monitored that ranged from 0.1 to 30 μm. The results were used to calculate the average mass transfer coefficient (50.5 m/day) and generate contour maps that provide guidance in choosing an appropriate EVA sampler for a particular study based on film thickness, deployment time, and the log K(OA) of the anlayte. A range of air pollutant classes was also added to the EVA sampler prior to deployment to assess depuration rates. These included polychlorinated biphenyls (PCBs), current-use pesticides (CUPs), perfluorinated compounds (PFCs), and polybrominated diphenyl ethers (PBDEs). On the basis of the depuration profiles, the EVA sampler was a suitable equilibrium sampler for several CUPs and PCBs; however, for the high molecular weight PCBs and PBDEs, the EVA sampler operates as a linear uptake sampler. Samplers were also evaluated for their use as a rapid screening tool for assessing concentrations of siloxanes in indoor air. The EVA sampler was used to estimate air concentrations for D4 and D5 in laboratory air to be 118 and 89 ng/m(3), respectively. Analyses were performed directly using thermal desorption gas chromatography/mass spectrometry (TDS-GC-MS). EVA samplers show promise due to their relatively low cost and ease of deployment and applicability to a wide range of priority chemicals. The ability to alter the film thickness, and hence the sorption capacity and performance of the EVA sampler, allows for a versatile sampler that can be used under varying sampling conditions and deployment times.     

Method for the in situ calibration of a passive phosphate sampler in estuarine and marine waters

Passive samplers for phosphate were calibrated in the laboratory over a range of flow velocities (0-27 cm s(-1)) and ionic strengths (0-0.62 mol kg(-1)). The observed sampling rates were between 0.006 and 0.20 L d(-1). An empirical model allowed the estimation of these sampling rates with a precision of 8.5%. Passive flow monitors (PFMs), based on gypsum dissolution rates, were calibrated for the same range of flow velocities and ionic strength. Mass loss rates of the PFMs increased with increasing ionic strength. We demonstrate that this increase is quantitatively accounted for by the increased gypsum solubility at higher ionic strengths. We provide a calculation scheme for these solubilities for an environmentally relevant range of temperatures and salinities. The results imply that co-deployed PFMs can be used for estimating the flow effect on the in situ sampling rates of the phosphate samplers, and we expect that the same may hold for other passive samplers.     

Aquatic passive sampling of herbicides on naked particle loaded membranes: accelerated measurement and empirical estimation of kinetic parameters

Water-sampler equilibrium partitioning coefficients and aqueous boundary layer mass transfer coefficients for atrazine, diuron, hexazionone and fluometuron onto C18 and SDB-RPS Empore disk-based aquatic passive samplers have been determined experimentally under a laminar flow regime (Re = 5400). The method involved accelerating the time to equilibrium of the samplers by exposing them to three water concentrations, decreasing stepwise to 50% and then 25% of the original concentration. Assuming first-order Fickian kinetics across a rate-limiting aqueous boundary layer, both parameters are determined computationally by unconstrained nonlinear optimization. In addition, a method of estimation of mass transfer coefficients--therefore sampling rates--using the dimension-less Sherwood correlation developed for laminar flow over a flat plate is applied. For each of the herbicides, this correlation is validated to within 40% of the experimental data.The study demonstrates that for trace concentrations (sub 0.1 microg/L) and these flow conditions, a naked Empore disk performs well as an integrative sampler over short deployments (up to 7 days) for the range of polar herbicides investigated. The SDB-RPS disk allows a longer integrative period than the C18 disk due to its higher sorbent mass and/or its more polar sorbent chemistry. This work also suggests that for certain passive sampler designs, empirical estimation of sampling rates may be possible using correlations that have been available in the chemical engineering literature for some time.     

Development and calibration of a passive sampler for perfluorinated alkyl carboxylates and sulfonates in water

Perfluorinated chemicals (PFCs) are emerging environmental contaminants with a global distribution. Due to their moderate water solubility, the majority of the environmental burden is assumed to be in the water phase. This work describes the application of the first passive sampler for the quantitative assessment of concentrations of perfluorinated alkylcarboxylates (PFCAs) and sulfonates (PFSAs) in water. The sampler is based on a modified Polar Organic Chemical Integrative Sampler (POCIS) with a weak anion exchange sorbent as a receiving phase. Sampling rates were between 0.16 and 0.37 L d(-1), and the duration of the kinetic sampling stage was between 2.2 and 13 d. A field deployment in the most urbanized estuary in Australia (Sydney Harbour) showed trace level concentrations from passive samplers (0.1-12 ng L(-1)), in good agreement with parallel grab sampling (0.2-16 ng L(-1)). A separate field comparison of the modified POCIS with standard POCIS suggests the latter may have application for PFC sampling, but with a more limited range of analytes than the modified POCIS which contains a sorbent with a mixed mode of action.     

Passive monitoring method for 3-ethenylpyridine: a marker for environmental tobacco smoke

A new method was developed to assess environmental tobacco smoke in air. The method is based on passive sampling and subsequent measurement of the concentration of 3-ethenylpyridine, a vapor-phase compound specific to tobacco smoke. Air samples were collected using a 3M organic vapor monitor. Tests were carried out in a dynamic chamber to determine the sampling rate (25.7 cm3/min). 3-Ethenylpyridine was desorbed from the sampler with 1 mL of pyridine/toluene mixture. 3-Ethenylpyridine was quantified by gas chromatography/mass spectrometry. The limit of detection was 0.01 microgram/sample, corresponding to a concentration of 0.27 microgram/m3 air calculated for a sampling period of 24 h. Field measurements were carried out to test the performance of the method. Mean concentrations ranging from 1.3 to 5.3 micrograms/m3 were measured for 3-ethenylpyridine in smoking environments, but no 3-ethenylpyridine was detected in nonsmoking environments. Active sampling using charcoal tubes was used as a reference method in the chamber tests and field measurements. Individual exposures can be easily and accurately measured by means of the passive sampler. Because of simple sample treatment, the method is also well-suited for large-scale monitoring of environmental tobacco smoke.     

Application of sorbent impregnated polyurethane foam (SIP) disk passive air samplers for investigating organochlorine pesticides and polybrominated diphenyl ethers at the global scale

As part of continued efforts under the Global Atmospheric Passive Sampling (GAPS) Network to develop passive air samplers applicable to a wide-range of compounds, sorbent-impregnated polyurethane foam (SIP) disk samplers were codeployed and tested against conventional polyurethane foam (PUF) disk samplers. The SIP disk sampler has a higher sorptive capacity compared to the PUF disk sampler, due to its impregnation with ground XAD resin. The two sampler types were codeployed at 20 sites during the 2009, 3-month long spring sampling period of the GAPS Network. Air concentrations for chlordanes (trans-chlordane, cis-chlordane, and trans-nonachlor) and endosulfans (endosulfan I, endosulfan II, and endosulfan sulfate) derived from PUF disk and SIP disk samplers showed near 1:1 agreement and confirmed previous results for polychlorinated biphenyls (PCBs). Discrepancies observed for α-HCH and γ-HCH in PUF disk versus SIP disk are attributed to lack of "comparability" of the PUF and SIP data sets, due to differences in effective air sampled by the two devices caused by saturation of these higher volatility compounds in the lower capacity PUF disk samplers. Analysis of PBDEs in PUF and SIP disks showed relatively good agreement but highlighted challenges associated with high blanks levels for PBDEs. The higher capacity SIP disk samplers allowed for the analysis of pentachlorobenzene (PeCBz) and hexachlorobenzene (HCBz) and revealed a relatively uniform global distribution of these compounds. The results of this study further validate the SIP disk sampler as a complement to the PUF disk sampler, with capabilities for a broad range of POPs targeted under international POPs treaties such as the Stockholm Convention on POPs and its Global Monitoring Plan.     

Influence of sampler configuration on the uptake kinetics of a passive air sampler

Passive air samplers (PAS) are simple and cost-effective tools to monitor semivolatile organic compounds in air. Chemical uptake occurs by molecular diffusion from ambient air to a passive sampling medium (PSM). Previous calibration studies indicate that even for the same type of PAS, passive air sampling rates (R, m(3)(air)/d) can be highly variable due to the influence of a number of factors. Earlier studies mainly focused on factors (e.g., wind speed and temperature) influencing R via the kinetic resistance posed by the air boundary layer surrounding the PSM because that layer was deemed to be the main factor determining the uptake kinetics. Whereas recent calibration studies suggest that the PAS configuration can influence R, so far few studies have specifically focused on this factor. In this study, with the objective to understand the effect of PAS configurations on R, we applied a gravimetrical approach to study the kinetics of water vapor uptake from indoor air by silica gel placed inside cylindrical PAS of various configurations. We also conducted an indoor calibration for polychlorinated biphenyls on the same type of PAS using XAD-resin as the PSM. R was found to be proportional to the interfacial transfer area of the PSM but not the amount of the PSM because chemicals mainly accumulated in the outer layer of the PSM during the deployment time of the PAS. The sampler housing and the PSM can introduce kinetic resistance to chemical uptake as indicated by changes in R caused by positioning the PSM at different distances from the opening of the sampler housing and by using PSM of different diameters. Information gained from this study is useful for optimizing the PAS design with the objective to reduce the material and shipping costs without sacrificing sampling efficiency.     

Assessing the influence of meteorological parameters on the performance of polyurethane foam-based passive air samplers

Polyurethane foam (PUF) disk passive air samplers were evaluated under field conditionsto assessthe effect of temperature and wind speed on the sampling rate for polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs). Passive samples integrated over 28-day periods were compared to high-volume air samples collected for 24 h, every 7 days. This provided a large data set of 42 passive sampling events and 168 high-volume samples over a 3-year period, starting in October 2003. Average PUF disk sampling rates for gas-phase chemicals was approximately 7 m3 d(-1) and comparable to previous reports. The high molecular weight PAHs, which are mainly particle-bound, experienced much lower sampling rates of approximately 0.7 m3 d(-1). This small rate was attributed to the ability of the sampling chamber to filter out coarse particles with only the fine/ultrafine fraction capable of penetration and collection on the PUF disk. Passive sampler-derived data were converted to equivalent air volumes (V(EQ), m3) using the high-volume air measurement results. Correlations of V(EQ) against meteorological data collected on-site yielded different behavior for gas- and particle-associated compounds. For gas-phase chemicals, sampling rates varied by about a factor of 2 with temperature and wind speed. The higher sampling rates at colder temperatures were explained bythe wind effecton sampling rates. Temperature and wind were strongly correlated with the greatest winds at coldertemperatures. Mainly particle-phase compounds (namely, the high molecular weight PAHs) had more variable sampling rates. Sampling rates increased greatly atwarmertemperatures as the high molecular weight PAH burden was shifted toward the gas phase and subject to higher gas-phase sampling rates. At colder temperatures, sampling rates were reduced as the partitioning of the high molecular weight PAHs was shifted toward the particle phase. The observed wind effect on sampling for the particle-phase compounds is believed to be tied to this strong temperature dependence on phase partitioning and hence sampling rate. For purposes of comparing passive sampler derived data for persistent organic pollutants, the factor of 2 variability observed for mainly gas-phase compounds is deemed to be acceptable in many instances for semiquantitative analysis. Depuration compounds may be used to improve accuracy and provide site-specific sampling rates, although this adds a level of complexity to the analysis. More research is needed to develop and test passive air samplers for particle-associated chemicals.     

Development of a flow controller for long-term sampling of gases and vapors using evacuated canisters

Anthropogenic activities contribute to the release of a wide variety of volatile organic compounds (VOC) into microenvironments. Developing and implementing new air sampling technologies that allow for the characterization of exposures to VOC can be useful for evaluating environmental and health concerns arising from such occurrences. A novel air sampler based on the use of a capillary flow controller connected to evacuated canisters (300 mL, 1 and 6 L) was designed and tested. The capillary tube, used to control the flow of air, is a variation on a sharp-edge orifice flow controller. It essentially controls the velocity of the fluid (air) as a function of the properties of the fluid, tube diameter and length. A model to predict flow rate in this dynamic system was developed. The mathematical model presented here was developed using the Hagen-Poiseuille equation and the ideal gas law to predict flow into the canisters used to sample for long periods of time. The Hagen-Poiseuille equation shows the relationship between flow rate, pressure gradient, capillary resistance, fluid viscosity, capillary length and diameter. The flow rates evaluated were extremely low, ranging from 0.05 to 1 mL min(-1). The model was compared with experimental results and was shown to overestimate the flow rate. Empirical equations were developed to more accurately predict flow for the 300 mL, 1 and 6 L canisters used for sampling periods ranging from several hours to one month. The theoretical and observed flow rates for different capillary geometries were evaluated. Each capillary flow controller geometry that was tested was found to generate very reproducible results, RSD < 2%. Also, the empirical formulas developed to predict flow rate given a specified diameter and capillary length were found to predict flow rate within 6% of the experimental data. The samplers were exposed to a variety of airborne vapors that allowed for comparison of the effectiveness of capillary flow controllers to sorbent samplers and to an online gas chromatograph. The capillary flow controller was found to exceed the performance of the sorbent samplers in this comparison.     

Field calibration of rapidly equilibrating thin-film passive air samplers and their potential application for low-volume air sampling studies

This paper reports on a field calibration and ambient deployment study with rapidly equilibrating thin-film passive air samplers. POlymer-coated Glass (POG) samplers have a coating of ethylene vinyl acetate (EVA) less than 1 microm thick coated on to glass, which can be dissolved off after exposure and prepared for quantification of persistent organic pollutants (POPs) that have partitioned into the film during field exposure. In this study, POGs were exposed for up to 18 d, in a study to assess compound uptake rates and their time to approach equilibrium. Results confirmed theoretical predictions, with time to equilibrium varying between a few hours to ca. 20 d for PCB-18 and PCB-138, respectively. Performance reference compounds and contaminated POGs were used to investigate depuration kinetics, confirming that lighter congeners behave extremely dynamically with substantial losses from the films over periods of a few hours. Repeated deployments of the samplers for different3-d periods yielded detectable levels of a range of PCB congeners, which had partitioned from as little as approximately 2 to 10 m3 air. This highlights the potential utility of POGs for extremely sensitive and dynamic passive air sampling in the future to help improve understanding of sources, environmental fate, and behavior of POPs. Recommendations are made for future improvements/refinements in POG sampling and handling procedures.     

New device and method for flux-proportional sampling of mobile solutes in soil and groundwater

The importance of monitoring the transport of organic contaminants in soil and groundwater, and the pros and cons of existing sampling methods, are outlined. A new, alternative sampling method is proposed, using a passive sampler that functions as a water-permeable, semi-infinite sink for passing solutes of interest. Tracers integrated in the device store information on the volume of water passing through the sampler during the installation period. The conceptual basis of the sampling method is described. This device enables flux-proportional monitoring of the concentrations of mobile contaminants in the soil and groundwater. 14C-labeled phenanthrene (PHEN) and glyphosate (GLY) are used as case study compounds in laboratory experiments. The sorption capacities and uptake kinetics of 13 adsorbents are screened and compared, as well as the dissolution kinetics of three tracer salts: calcium citrate, calcium fluoride (CaF2), and calcium hydrogen phosphate (CaHPO4). The application of the passive sampler is then demonstrated in long-term laboratory experiments, using large soil columns under steady-state hydraulic conditions. The accumulated flux of PHEN was sampled with an accuracy of 3.6%-17.8%, using graphitized carbon, hexagonal mesoporous silica, and cross-linked polymers as adsorbents. The accumulated flux of GLY was sampled with an accuracy of 12.4%, using gamma-alumina as an adsorbent. The advantages and limitations of this new environmental monitoring method are discussed.