Validation of a passive atmospheric deposition sampler for polybrominated diphenyl ethers

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

Laboratory and field validation of a combined NO2-SO2 Radiello passive sampler

A combined NO2-SO2 Radiello radial-type diffusive sampler was validated under controlled laboratory conditions and compared with NO2-SO2 results of 3 other type of samplers in a field comparison at two locations Ghent-Mariakerke and Borgerhout in Flanders. Laboratory exposures at different temperatures (-5, 10 and 30 degrees C) and relative humidities (0, 50 and 80% RH) in combination with varying concentration levels and exposure times were carried out, with a focus on extreme conditions. Concentration level and exposure time were changed together following suppliers linear working range of samplers and assuring absolute amounts of compounds on the sampler corresponding to those of environmental levels. The average uptake rate for NO2 for 24 hour exposures at 10 degrees C and 50% RH and tested concentration levels (+/-73, 146 and 293 ppb NO2) was 0.076 +/- 0.011 ng ppb(-1) min(-1). Uptake rates during all experiments were lower than the uptake rate given in the instruction manual of the sampler. A significant effect of temperature and relative humidity on NO2 uptake rate was observed. The temperature effect from 10 to 30 degrees C corresponds to the temperature effect given by the supplier of the samplers. High relative humidity (70 to 80%) caused a strong non-reproducible decrease of uptake rate for NO2 at 24 hour experiments but this effect was not observed at longer exposures except for the tests at -5 degrees C. At the tested temperature below zero in combination with high relative humidity the sampler showed anomalous behaviour for NO2. The possible effect of concentration level and exposure time for NO2 needs further research. The average uptake rate for SO2 calculated from all exposures is 0.478 +/- 0.075 ng of sulfate ion each ppb min of SO2 and accords to suppliers uptake rate. No clear effects of temperature, relative humidity or concentration level/exposure time on the uptake rate for SO2 were found, partly due to the large scatter of results. Although NO2 accuracy of Radiello samplers was better during field campaigns than during laboratory validation, IVL and OGAWA samplers gave better results for NO2. In the field, IVL samplers showed best agreement with the continuous analyzers for both NO2 and SO2.     

Design and laboratory testing of a new flow-through directional passive air sampler for ambient particulate matter

A new type of directional passive air sampler (DPAS) is described for collecting particulate matter (PM) in ambient air. The prototype sampler has a non-rotating circular sampling tray that is divided into covered angular channels, whose ends are open to winds from sectors covering the surrounding 360°. Wind-blown PM from different directions enters relevant wind-facing channels, and is retained there in collecting pools containing various sampling media. Information on source direction and type can be obtained by examining the distribution of PM between channels. Wind tunnel tests show that external wind velocities are at least halved over an extended area of the collecting pools, encouraging PM to settle from the air stream. Internal and external wind velocities are well-correlated over an external velocity range of 2.0-10.0 m s?1, which suggests it may be possible to relate collected amounts of PM simply to ambient concentrations and wind velocities. Measurements of internal wind velocities in different channels show that velocities decrease from the upwind channel round to the downwind channel, so that the sampler effectively resolves wind directions. Computational fluid dynamics (CFD) analyses were performed on a computer-generated model of the sampler for a range of external wind velocities; the results of these analyses were consistent with those from the wind tunnel. Further wind tunnel tests were undertaken using different artificial particulates in order to assess the collection performance of the sampler in practice. These tests confirmed that the sampler can resolve the directions of sources, by collecting particulates preferentially in source-facing channels.     

A passive sampler for hydrogen sulfide

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

被动式个体采样器在环境监测中的应用

本文报道了用被动式个体采样器监测空气小常见污染物ＮＯ２,ＳＯ２．提出了样品测定之前对每种污染物的具体实验要求。对济南市有关场所空气进行了监测。总结了个体采样器的优点。     

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

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

Metal diffusion properties of a Nafion-coated porous membrane in an aquatic passive sampler system

A cellulose acetate membrane, positioned in a passive sampler system, was coated with the perfluorinated polymer Nafion. Aqueous metal transport through the membrane and the Nafion film was investigated. The Nafion-coated membrane prevents the transport of metals bound to natural organic material to the receiving phase in the passive sampler, while copper associated with small synthetic ligands pass through the Nafion film. Increasing thickness of the Nafion film decreases the metal uptake rate to the receiving phase in the passive sampler and increases the response time. A decreased response time for the passive sampler would provide a better estimation of rapid changes in concentration, particularly for dynamic aquatic systems such as urban runoff. Limited biofouling protection with the Nafion coating was demonstrated by growth inhibition of natural periphyton communities on glass surfaces.     

A novel passive water sampler for in situ sampling of antibiotics

Passive water sampling has several advantages over active methods; it provides time-integrated data, can save on time and cost compared to active methods, and yield high spatial resolution data through co-deployment of simple, cheap units. However, one problem with many sampler designs in current use is that their uptake rates for trace substances of interest are flow-rate dependent, thereby requiring calibration data and other information to enable water concentrations to be derived from the mass per sampler. However, the 'family' of samplers employing the principle of diffusive gradients in thin films (DGT) provides an in situ means of quantitatively measuring labile species in aquatic systems without field calibration. So far, this technique has only been tested and applied in inorganic substances: metals, radionuclides, nutrients, etc. Design and applications of DGT to trace organic contaminants ('o-DGT') would be of widespread interest. This study describes the laboratory testing and performance characteristics of o-DGT, with the antibiotic sulfamethoxazole (SMX) as a model compound and XAD18 as the novel binding agent. o-DGT uptake of SMX increased with time and decreased with diffusion layer thickness, confirming the principle for SMX. XAD18 showed sufficiently high capacity for SMX for routine field applications. o-DGT measurement of SMX was independent of pH (6-9) and ionic strength (0.001-0.1 M) and not affected by flow rate once above static conditions. The diffusion coefficient of SMX in the sampler was measured using an independent diffusion cell and information is presented to allow temperature correction and derivation of aqueous concentrations from deployed samplers. The potential use of o-DGT for in situ measurement of pharmaceutical antibiotics is confirmed by this study and applications are briefly discussed.     

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

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

Dry deposition study by using dry deposition plate and water surface sampler in Shalu, central Taiwan

This study presents the chemical composition of dry deposition by using dry deposition plate and water surfaces sampler during daytime and nighttime sampling periods at a near highway traffic sampling site. In addition, the characterization for mass and water soluble species of total suspended particulate (TSP), PM2.5 and PM10 were also studied at this sampling site during August 22 to October 31 of 2006 around central Taiwan. The samples collected were analyzed by using Ion Chromatography (DIONEX 100) for the ionic species analysis. Results of the particulate dry deposition fluxes are higher in the water surfaces sampler than that of the dry deposition plate. In other words, the results also indicated that water surface can absorb more ambient dry deposition inorganic pollutants than that of dry deposition plate in this study. The results obtained in this study indicated that the ionic species of Cl(-), NO3(-) and SO4(2-) occupied about average 60-70% downward flux out of total ionic species for either dry deposition plate or water surfaces sampler during August to October of 2006 at this near highway traffic sampling site.     

Development of an integrative passive sampler for the monitoring of organic water pollutants

The development of convenient and competitive devices and methods for monitoring of organic pollutants in the aquatic environment is of increasing interest. An integrative passive sampling system has been developed which consists of a solid poly(dimethylsiloxane) (PDMS) material (tube or rod), acting as hydrophobic organic receiving phase, enclosed in a water-filled or an air-filled low-density polyethylene (LDPE) membrane tubing. These samplers enable the direct analysis of the pollutants accumulated during exposure in the receiving phase by thermodesorption-GC/MS, avoiding expensive sample preparation and cleanups. The capabilities of these sampling devices were studied for the sampling of 20 persistent organic pollutants (chlorobenzenes, hexachlorocyclohexanes, p,p'-DDE, PAHs, and PCBs) in laboratory exposure experiments. For the three sampler designs investigated the uptake of all target analytes was integrative over exposure periods up to 9 days (except PCB 101). The determined sampling rates range from 4 to 1340 microl h(-1) for the water-filled samplers and from 20 to 6360 microl h(-1) for the air-filled ones, respectively. The sampling rate of the analytes is dependent on their molecular weight, partition between water and sampler media (PDMS, polyethylene, water, air) and also of the sampler design. The passive samplers enable the estimation of time-weighted average (TWA) concentration of water pollutants in the lower ng l(-1) to pg l(-1) range.     

Field evaluation of a tailor-made new passive sampler for the determination of NO2 levels in ambient air

This study describes the field evaluation of a tailor-made new glass passive sampler developed for the determination of NO(2), based on the collection on triethanolemine (TEA)-coated fibre filter paper. The sampler has been derived from a Palmes design. The overall uncertainty of the sampler was determined by using Griess-Saltzman ASTM D 1607 standard test method as a reference method. The agreement between the results of the passive sampler and the reference method was +/-7.90% with the correlation coefficient of 0.90. Method precision in terms of coefficient of variance (CV) for three simultaneously applied passive samplers was 8.80%. The uptake rate of NO(2) was found to be 2.49 ml/min in a very good agreement with the value calculated from theory (2.63 ml/min). Sampler detection limit was 1.99 microg/m(3) for an exposure period of 1 week and the sampler can be stored safely for a period of up to 6 weeks before exposure. A comparison of the sampler performance was conducted against a commercially available diffusion tube (Gradko diffusion tube). The results from the applied statistical paired t test indicated that there was no significant difference between the performances of two passive samplers (R (2) > 0.90). Also, another statistical comparison was carried out between the dark and transparent glass passive samplers. The results from the dark-colour sampler were higher than that from the transparent sampler (approximately 25%) during the summer season because of the possible photodegradation of NO(2)-TEA complex.     

Calibration of two passive air sampler configurations for monitoring concentrations of hexabromocyclododecanes in indoor air

While polyurethane foam (PUF) disk passive air samplers are employed increasingly to monitor persistent organic pollutants in indoor air, they essentially sample only the vapour phase. As a previous investigation of the vapour : particle phase partitioning of hexabromocyclododecanes HBCDs in (outdoor) air reported them to be present largely in the particulate phase, we monitored three offices using active air samplers. In each, approximately 65% of HBCDs were present in the vapour phase, suggesting PUF disk passive samplers are suitable for monitoring HBCDs in indoor air. Concentrations in the three offices (239-359 pg Sigma HBCD m(-3)) exceed substantially those reported in outdoor air from the United States (2.1-11 pg Sigma HBCD m(-3)), but are in line with outdoor air from Stockholm. The relative abundance of the three principal diastereomers in office air was closer to that found in technical HBCD formulations (i.e. predominantly gamma-HBCD) than in most US outdoor air samples. Time integrated air concentrations of alpha-, beta-, and gamma-HBCD were obtained for an office using a low volume sampler operated over a 50 d period alongside PUF disk samplers. This calibration exercise yielded the following passive air sampling rates for both a fully- and part-sheltered PUF disk sampler design: for alpha-, beta-, and gamma-HBCD, 0.87, 0.89, and 0.91 m3 d(-1) respectively (fully-sheltered) and 1.38, 1.54, and 1.55 m3 d(-1) respectively (part-sheltered). Deployment of the part-sheltered configuration yielded concentrations approximately 35% lower than those obtained using a high volume sampler, consistent with PUF disk samplers measuring primarily the vapour phase.     

Simplification and validation of a large volume polyurethane foam sampler for the analysis of persistent hydrophobic compounds in drinking water

The use of a large volume polyurethane foam (PUF) sampler was validated for rapid extraction of persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in raw water and treated water from drinking water plants. To validate the recovery of target compounds in the sampling process, a (37)Cl-labeled standard was spiked into the 1st PUF plug prior to filtration. An accelerated solvent extraction method, as a pressurized liquid extractor (PLE), was optimized to extract the PUF plug. For sample preparation, tandem column chromatography (TCC) clean-up was used for rapid analysis. The recoveries of labeled compounds in the analytical method were 80-110% (n = 9). The optimized PUF-PLE-TCC method was applied in the analysis of raw water and treated potable water from seven drinking water plants in South Korea. The sample volume used was between 18 and 102 L for raw water at a flow rate of 0.4-2 L min(-1), 95 and 107 L for treated water at a flow rate of 1.5-2.2 L min(-1). Limit of quantitation (LOQ) was a function of sample volume and it decreased with increasing sample volume. The LOQ of PCDD/Fs in raw waters analyzed by this method was 3-11 times lower than that described using large-size disk-type solid phase extraction (SPE) method. The LOQ of PCDD/F congeners in raw water and treated water were 0.022-3.9 ng L(-1) and 0.018-0.74 ng L(-1), respectively. Octachlorinated dibenzo-p-dioxin (OCDD) was found in some raw water samples, while their concentrations were well below the tentative criterion set by the Japanese Environmental Ministry for drinking water. OCDD was below the LOQ in the treated drinking water.     

Determining the agricultural ammonia immission using bark bio-monitoring: comparison with passive sampler measurements

Bark samples of spruce, pine and oak trees were collected at two sites in southern Bavaria which are characterized by high agricultural ammonia emissions. The samples were taken using a recently developed bark sampling device which removes a defined layer of the bark. The bark was then analysed for ammonium concentration in order to reflect the environmental ammonia immission. The measured bark concentrations decreased with rising distance between the sample trees and the ammonia source. This applied (i) to measurements inside a closed forest stand ranging from forest edge with high immission to forest interior with much lower immission, and (ii) to the open field where single-standing trees were sampled. Comparing the ammonium concentrations among the three different tree species revealed significant correlations. Thus, it could be shown that old spruce trees are as usable for bark bio-monitoring as the traditionally used pine and oak trees. The ammonium concentrations of the bark were significantly correlated to measurements taken by ammonia passive samplers at the same locations. These results indicate that bark samples may be used for a standardised monitoring of airborne ammonia load. A major advantage of the technique is the determination of the long-term accumulative ammonia load using a single measurement.     

A low-tech, low-cost passive sampler for the long-term monitoring of phosphate loads in rivers and streams

The concentration of dissolved reactive phosphorus (DRP) in rivers can change intermittently within minutes depending on the weather and water discharge (Q), or activities in the watershed. Accordingly, accurate estimation of the annual DRP load requires frequent sampling or even continuous monitoring, which is laborious and cost-intensive. We present the design and laboratory evaluation of a new, robust, low-cost, low-tech device based on passive samplers (P-traps). The traps use Fe-(oxy)hydroxide coated quartz sand as an adsorbent enclosed in a vertical grid of individual cells separated from the river water by filter membranes. They are inexpensive, easy to handle, resistant to repeated desiccation and immersion and exposable for several months. They permit estimation of discharge dependent time weighted average DRP concentrations (C-Q relationships) and annual P loads of rivers characterized by highly variable DRP concentrations with a relative accuracy of +/- 3%.     

环境水体中油的采样工具的设计及其可行性研究

由于油在水中呈不均匀分布的特性,所以有关环境水体中油的采样工具,一直是环保部门关注的焦点。为此提出了“理想（或称假想）水柱”的概念,并依此设计出一种在环境监测工作中使用的便携式测水中油用采样器,适用于工业废水、生活污水及污染的地表水的采取。其特点是,一个底部可开闭的采样器,采样器中的采样瓶（包括瓶底衬盖、瓶底盖）与内拉杆、外套管通过螺纹联接,移动内拉杆、外套管,便可以方便地采取一定面积下的含油水柱。采样瓶装卸简单,运输方便,在实验室中可将其直接用作操作瓶。用这种采样器,计算结果将更接近真实情况。本装置已于９２ 年１２ 月３０日获国家发明专利,专利号：８９１０２４７１．９,证书号：１６３８１。     

Field evaluation of a passive sampler of polycyclic aromatic hydrocarbons (PAHs) in an urban atmosphere (Bologna, Italy)

A simple device consisting of a Petri dish containing cellulose paper soaked with paraffin oil (hereinafter defined "artificial leaf", AL) was deployed in a typical urban site and partitioning of a set of PAHs between the atmosphere and AL was investigated. Gas-phase PAHs rapidly equilibrate with AL, thus rendering it a promising cost-effective tool for spatial and temporal trends studies of air quality.     

Validation of a diffusive sampler for NO2

A diffusive sampler for NO2, Willems badge, was validated in laboratory experiments and field tests. The collecting reagent for NO2 in the sampler is triethanolamine, and the analysis is based on a modified colorimetric method, the Saltzman method. The analysis was performed by a flow injection analysis (FIA) technique. The sampling rate for the sampler was determined to be 40.0 ml min-1. There was no effect of NO2 concentration or relative humidity on sampling rate, and the influence of sampling time was found to be small. The detection limit was 4 micrograms m-3 for a 24 h sample. The capacity is high enough to allow sampling of 150 micrograms m-3 for 7 days, which is twice the recommended Swedish short-term (24 h) guideline value as a 98-percentile over 6 months. In field tests, the sampler performed well, even at wind speeds higher than 2 m s-1, and at low temperatures. The overall uncertainty of the method was 24%. The sensitivity and capacity of the method also make it suitable for personal sampling for 2-8 h in working environments.     

Design and field application of an automated cartridge sampler for VOC concentration and flux measurements

One of the major limitations in advancing the understanding of tropospheric ozone and aerosol generation and developing strategies for their control is the technical ability to accurately measure volatile organic compounds (VOCs). This paper describes the design of a constant flow VOC sampler. The versatile sampler can be used for fully automated concentration and flux measurements of VOCs. The sampler incorporates a microprocessor control unit and provides highly accurate mass flow control and significant ease of operation. Sampling sequences can be programmed directly or by remote control through a PC. All important operational parameters necessary for a complete sampling audit trail are logged. Compact weatherproof housings and low power consumption allow operation at remote sites and locations which are sensitive to disturbances or have restricted access. Inner wetted surfaces of the sampler are constructed from non-contaminating materials that do not sorb or emit VOC, and thus permit the collection of representative samples even in environments with very low VOC concentrations. The cartridge magazine provides a maximum of 20 sequential cartridge samples, which allows for long-term air quality assessments. In the dual channel mode, two samples can be collected simultaneously through two independent sample loops, providing ten sequential sample pairs. This design allows the parallel collection of (a) quality assurance backup samples, (b) samples on two different types of cartridges/sorbents to allow a variety of analyses, or (c) differential samples for flux measurements using enclosure, aerodynamic profile, or relaxed eddy accumulation (REA) methods. Field applications including airplane profile measurements above a tropical rainforest area, as well as gradient and REA measurements over a mid-latitude mixed forest stand are described, and demonstrate the validity and flexibility of the system. In particular, the application of the VOC sampler as an integrated part of a REA system is emphasized.