Validation and modelling of a novel diffusive sampler for determining concentrations of volatile organic compounds in air

A novel diffusive sampler that combines radial and axial diffusion has been developed that improves upon existing commercially available designs. The POcket Diffusive (POD) sampler has been validated under laboratory and field conditions for the measurements of VOCs in ambient air. Laboratory tests varied sampling conditions of temperature (−30–40 C), humidity (10–80%), wind velocity (0.1–4 m s⁻¹), and concentration (0.5–50 μg m⁻³) for a number of specific VOCs. An overall uncertainty of circa 9% for the measurement of benzene is calculated for the validation tests, in compliance with the data quality objectives of the EU air quality directive 2008/50/EC. A semi-empirical diffusion model has been developed to estimate sampling rates for compounds that were not tested, and for conditions outside of tested ranges during validation. The diffusion model (and validation tests) shows a low influence of environmental conditions on the sampling rate for the POD sampler. Average reproducibility values of circa 3% are reported with overall sampling uncertainties ranging from 9% to 15%, for the whole range of tested conditions, depending on the compound. The adsorbent cartridge is compatible with existing thermal desorption systems in the market. The diffusive sampler can modify the sampling rate by changing the diffusive body within a range of different porosities. Field tests, conducted in parallel with independent quality controlled canister sampling, confirmed the ease of use and quality of VOC measurements with the POD sampler, for compounds that were, and were not, evaluated during laboratory tests.     

Sampling, storage, and analysis of C2-C7 non-methane hydrocarbons from the US National Oceanic and Atmospheric Administration Cooperative Air Sampling Network glass flasks

An analytical technique was developed to analyze light non-methane hydrocarbons (NMHC), including ethane, propane, iso-butane, n-butane, iso-pentane, n-pentane, n-hexane, isoprene, benzene and toluene from whole air samples collected in 2.5l-glass flasks used by the National Oceanic and Atmospheric Administration, Earth System Research Laboratory, Global Monitoring Division (NOAA ESRL GMD, Boulder, CO, USA) Cooperative Air Sampling Network. This method relies on utilizing the remaining air in these flasks (which is at below-ambient pressure at this stage) after the completion of all routine greenhouse gas measurements from these samples. NMHC in sample aliquots extracted from the flasks were preconcentrated with a custom-made, cryogen-free inlet system and analyzed by gas chromatography (GC) with flame ionization detection (FID). C2-C7 NMHC, depending on their ambient air mixing ratios, could be measured with accuracy and repeatability errors of generally < or =10-20%. Larger deviations were found for ethene and propene. Hexane was systematically overestimated due to a chromatographic co-elution problem. Saturated NMHC showed less than 5% changes in their mixing ratios in glass flask samples that were stored for up to 1 year. In the same experiment ethene and propene increased at approximately 30% yr(-1). A series of blank experiments showed negligible contamination from the sampling process and from storage (<10 pptv yr(-1)) of samples in these glass flasks. Results from flask NMHC analyses were compared to in-situ NMHC measurements at the Global Atmospheric Watch station in Hohenpeissenberg, Germany. This 9-months side-by-side comparison showed good agreement between both methods. More than 94% of all data comparisons for C2-C5 alkanes, isoprene, benzene and toluene fell within the combined accuracy and precision objectives of the World Meteorological Organization Global Atmosphere Watch (WMO-GAW) for NMHC measurements.     

Measurements of Pilots’ Occupational Solar UV Exposure

It is known that ultraviolet radiation (UVR) increases by 10–12% every 1000 m altitude; UVR at the 10 000 m of typical cruise altitude for commercial aircraft may be 2–3 times higher than at ground level. Information on the levels of solar UV exposures is essential for the assessment of the occupational risk of pilots developing sun‐related eye disorders and skin cancers. The aim of the study was to investigate how UV hazard exposures can be measured during flights so that the occupational dose can be ascertained and compared with international guidance. This article describes the development of instrumentation for automated time‐stamped spectral measurements which were collected using bespoke automation software. The software enables the advanced acquisition techniques of automated dark signal capture and multiband integration control optimizing the dynamic performance of the spectrometer over the full spectral range. The equipment was successfully tested in a number of aircraft and helicopter flights during 2012–2013 and illustrated in this article on an example of a Gatwick‐Alicante flight.     

An automated monitoring system for VOC ozone precursors in ambient air: development,implementation and data analysis

An automated system for the monitoring of volatile organic compound (VOC) ozone precursors in ambient air is described. The measuring technique consists of subambient preconcentration on a cooled trap followed by thermal desorption and GC/FID analysis. First, the technical development, which permits detection limits below 0.05 ppbv to be reached, proceeded in two steps: (1) the determination of optimum sampling parameters (trap composition and conditioning, outlet split, desorption temperature); (2) the development of a reliable calibration method based on a highly accurate standard. Then, a 4-year field application of the hourly measuring chain was carried out at two urban sites. On the one hand, quality control procedures provided the best VOC identification (peak assignment) and quantification (reproducibility, blank system control). On the other hand, the success and performances of the routine experience (88% of the measurements covered more than 40 target compounds) indicated the high quality and suitability of the instrumentation which is actually applied in several French air quality monitoring networks. Finally, an example of data analysis is presented. Data handling identified important organic compound sources other than vehicle exhaust.     

High-Speed MALDI-TOF Imaging Mass Spectrometry: Rapid Ion Image Acquisition and Considerations for Next Generation Instrumentation

A prototype matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometer has been used for high-speed ion image acquisition. The instrument incorporates a Nd:YLF solid state laser capable of pulse repetition rates up to 5 kHz and continuous laser raster sampling for high-throughput data collection. Lipid ion images of a sagittal rat brain tissue section were collected in 10 min with an effective acquisition rate of roughly 30 pixels/s. These results represent more than a 10-fold increase in throughput compared with current commercially available instrumentation. Experiments aimed at improving conditions for continuous laser raster sampling for imaging are reported, highlighting proper laser repetition rates and stage velocities to avoid signal degradation from significant oversampling. As new high spatial resolution and large sample area applications present themselves, the development of high-speed microprobe MALDI imaging mass spectrometry is essential to meet the needs of those seeking new technologies for rapid molecular imaging.     

Dynamic solid phase microextraction for sampling of airborne sarin with gas chromatography-mass spectrometry for rapid field detection and quantification

A portable dynamic air sampler and solid phase microextraction were used to simultaneously detect, identify, and quantify airborne sarin with immediate analysis of samples using a field portable gas chromatography-mass spectrometry system. A mathematical model was used with knowledge of the mass of sarin trapped, linear air velocity past the exposed sampling fiber, and sample duration allowing calculation of concentration estimates. For organizations with suitable field portable instrumentation, these methods are potentially useful for rapid onsite detection and quantification of high concern analytes, either through direct environmental sampling or through sampling of air collected in bags.     

Instrumental barriers in biological Fourier transform infrared spectroscopy

Biological applications of infrared spectroscopy have pressed for ever greater instrumental capabilities in terms of spectral sensitivity and quantitative exactness. Improved instrumentation has provided measurement of many vibrational modes in biological samples that previously were lost in noise. With highly optimized sampling conditions, useful measurements have been made with a peak-to-peak noise level less than 5 microabsorbance (5×10^–6 absorbance), at 0.5 cm^–1 resolution. However, optical and instrumental instabilities often result in sine waves that are not totally removed by the ratio of sample to reference. These often limit effective spectral sensitivity to 50 or 100 microabsorbance, peak-to-peak, and constitute a non-random noise. Non-atmospheric absorptions, especially one at 1959 cm^–1 with 0.8 cm^–1 band width (FWHM) are reported. The latter is due to a trace impurity in the KBr beam splitter substrate and compensator plate. Improvements in instrumentation and sampling conditions are expected to yield measurements of absorption bands as small as 50 microabsorbance with excellent signal/noise.     

A new certified reference material for benzene measurement in air on a sorbent tube: development and proficiency testing

A certified matrix reference material (CRM) for the measurement of benzene in ambient air has been developed at Laboratoire National de Métrologie et d’Essais. The production of these CRMs was conducted using a gravimetric method fully traceable to the International System of Units. The CRMs were prepared by sampling an accurate mass of a gaseous primary reference material of benzene, using a high-precision laminar flowmeter and a mass flow controller, with a PerkinElmer sampler filled with Carbopack™ X sorbent. The relative standard deviations obtained for the preparation of a batch of 20 tubes loaded with 500 ng of benzene were below 0.2%. Each CRM is considered independent from the others and with its own certified value and an expanded uncertainty estimated to be within 0.5%, lower than the uncertainties of benzene CRMs already available worldwide. The stability of these materials was also established up to 12 months. These CRMs were implemented during proficiency testing, to evaluate the analytical performances of seven French laboratories involved in benzene air monitoring.     

Determination of C1-C3 carboxylic acids in air with diffusion controlled sampling at elevated flow rates

Summary A sampling system for the determination of C₁-C₃ carboxylic acids in air is described. Acids are collected on coated diffusion screens at elevated flow rates (5.6 L/min), and afterwards quantified by ion-chromatography. Collection efficiency, behaviour of the absorbed comounds and the penetration of particles through coated screens are reported. Results of field measurements and their comparison with those obtained with conventional tubular denuder tubes are shown.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Validation of the Willems badge diffusive sampler for nitrogen dioxide determinations in occupational environments

The Willems badge, a diffusive sampler for nitrogen dioxide, has previously been validated for ambient air measurements. This paper describes the laboratory and field validation of the Willems badge for personal sampling under working environment conditions. The mean sampling rate in the laboratory tests was 46 ml min(-1), with an RSD of 12%. No statistically significant effects on sampling rate of the sampling time, concentration of NO2 or relative humidity were found. A slightly decreased sampling rate was observed at low wind velocity. This was also confirmed during static sampling, which makes the sampler less appropriate for static sampling indoors. No back diffusion was observed. Storage of the samplers for two weeks before or after exposure did not affect the sampling rate. Our analysis is based on a modified colorimetric method, performed by FIA (flow injection analysis). This technique was compared to ion chromatography analysis. The use of ion chromatography lowered the detection limit from 11 to 2 microg m(-3) for an 8 h sample, and furthermore enabled the detection of other anions. In conclusion, the diffusive sampler was found to perform well for personal measurements in industrial environments.     

Comparative study of the adsorption performance of a multi-sorbent bed (Carbotrap, Carbopack X, Carboxen 569) and a Tenax TA adsorbent tube for the analysis of volatile organic compounds (VOCs)

A comparison between two types of adsorbent tubes, the commonly used Tenax TA and a multi-sorbent bed (Carbotrap, Carbopack X, Carboxen 569) tube developed in our laboratory, has been done to evaluate their usefulness in the analysis of VOCs in ambient air. Duplicate indoor and outdoor samples of Tenax TA and multi-sorbent tubes of 10, 20, 40, 60 and 90 l were taken in Barcelona city (Spain) on July and October of 2009. Breakthrough values (defined as %VOCs found in the back tube) were determined for all sampling volumes connecting two sampling tubes in series. The analysis was performed by automatic thermal desorption (ATD) coupled with capillary gas chromatography (GC)/mass spectrometry detector (MSD). Significant differences between the concentrations obtained-from multi-sorbent bed and Tenax TA tubes are observed for the very volatile compounds (56 °C < boiling point < 100 °C and 4 kPa < vapour pressure (20 °C) < 47 kPa) (e.g. acetone, isopropanol, n-hexane) and for alcohols and chlorinated compounds (e.g. 1-butanol, carbon disulphide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethylene), being the concentrations found higher in multi-sorbent bed than in Tenax TA tubes. On the other hand, mainly all compounds with boiling points higher than 100 °C (except α-pinene, chlorinated and polar compounds) do not show significant differences between the obtained multi-sorbent bed and Tenax TA tube concentrations. For the concentrations obtained (5 ppt to 100 ppb), Tenax TA present high breakthrough values (from 0 to 77%) for mainly all compounds and sampling volumes studied. On the other hand, multi-sorbent bed tubes do not exhibit important breakthrough values for these compounds, except the VVOCs ethanol (for all sampled volumes), and acetone, dichloromethane and isopropanol (for sampling volumes over 40 l). The concentration differences observed between Tenax TA and multi-sorbent bed tubes are directly related to the high breakthrough values determined for Tenax TA adsorbent.     

热解析-气相色谱法测定印刷品中总挥发性有机化合物释放量

建立用气袋法收集整册印刷品释放的挥发性有机化合物,热解析-气相色谱法检测总挥发性有机化合物(TVOC)的方法。将印刷品样品置入充满高纯氮气的密封PVF采样袋中,在35℃下放置12 h后,用采样器串联Tenax-TA采样管和采样袋,让袋内气体通过采样管,样品释放出的有机化合物被吸附到采样管的吸附剂上。用热解析-气相色谱法测试采样管中挥发性有机化合物的含量,其中苯、甲苯、邻二甲苯、间二甲苯、对二甲苯、乙苯、乙酸丁酯、苯乙烯和正十一烷按外标法定量,其它物质按甲苯标准曲线定量。该方法的加标回收率为74.4%~91.1%,测定结果的相对标准偏差不大于10%(n=9)。该方法的样品采集更贴近印刷品的实际生活场景,可以为评价印刷品挥发性有机物释放对人体健康的影响提供数据基础,为相关评价提供新思路。     

Continuous and real-time bioaerosol monitoring by combined aerosol-to-hydrosol sampling and ATP bioluminescence assay

We present a methodology for continuous and real-time bioaerosol monitoring wherein an aerosol-to-hydrosol sampler is integrated with a bioluminescence detector. Laboratory test was conducted by supplying an air flow with entrained test bacteria (Staphylococcus epidermidis) to the inlet of the sampler. High voltage was applied between the discharge electrode and the ground electrode of the sampler to generate air ions by corona discharge. The bacterial aerosols were charged by the air ions and sampled in a flowing liquid containing both a cell lysis buffer and adenosine triphosphate (ATP) bioluminescence reagents. While the liquid was delivered to the bioluminescence detector, sampled bacteria were dissolved by the cell lysis buffer and ATP was extracted. The ATP was reacted with the ATP bioluminescence reagents, causing light to be emitted. When the concentration of bacteria in the aerosols was varied, the ATP bioluminescence signal in relative light units (RLUs) closely tracked the concentration in particles per unit air volume (# cm⁻³), as measured by an aerosol particle sizer. The total response time required for aerosol sampling and ATP bioluminescence detection increased from 30 s to 2 min for decreasing liquid sampling flow rate from 800 to 200 μLPM, respectively. However, lower concentration of S. epidermidis aerosols was able to be detected with lower liquid sampling flow rate (1 RLU corresponded to 6.5 # cm⁻³ of S. epidermidis aerosols at 200 μLPM and 25.5 # cm⁻³ at 800 μLPM). After obtaining all data sets of concentration of S. epidermidis aerosols and concentration of S. epidermidis particles collected in the flowing liquid, it was found that with our bioluminescence detector, 1 RLU corresponded to 1.8 × 10⁵ (±0.2 × 10⁵) # mL⁻¹ of S. epidermidis in liquid.     

Determination of airborne trialkyl and triaryl organophosphates originating from hydraulic fluids by gas chromatography-mass spectrometry. Development of methodology for combined aerosol and vapor sampling

Methodology for personal occupational exposure assessment of airborne trialkyl and triaryl organophosphates originating from hydraulic fluids by active combined aerosol and vapor sampling at 1.5L/min is presented. Determination of the organophosphates was performed by gas chromatography-mass spectrometry. Combinations of adsorbents (Anasorb 747, Anasorb CSC, Chromosorb 106, XAD-2 and silica gel) with an upstream cassette with glass fiber or PTFE filters and different desorption/extraction solvents (CS(2), CS(2)-dimethylformamide (50:1, v/v), toluene, dichloromethane, methyl-t-butyl ether and methanol) have been evaluated for optimized combined vapor and aerosol air sampling of the organophosphates tri-isobutyl, tri-n-butyl, triphenyl, tri-o-cresyl, tri-m-cresyl and tri-p-cresyl phosphates. The combination of Chromosorb 106 and 37 mm filter cassette with glass fiber filter and dichloromethane as desorption/extraction solvent was the best combination for mixed phase air sampling of the organophosphates originating from hydraulic fluids. The triaryl phosphates were recovered solely from the filter, while the trialkyl phosphates were recovered from both the filter and the adsorbent. The total sampling efficiency on the combined sampler was in the range 92-101% for the studied organophosphates based on spiking experiments followed by pulling air through the sampler. Recoveries after 28 days storage were 98-102% and 99-101% when stored at 5 and -20 degrees C, respectively. The methodology was further evaluated in an exposure chamber with generated oil aerosol atmospheres with both synthetic and mineral base oils with added organophosphates in various concentrations, yielding total sampling efficiencies in close comparison to the spiking experiments. The applicability of the method was demonstrated by exposure measurements in a mechanical workshop where system suitability tests are performed on different aircraft components in a test bench, displaying tricresyl phosphate air concentrations of 0.024 and 0.28 mg/m(3), as well as during aircraft maintenance displaying tri-n-butyl phosphate air concentrations of 0.061 and 0.072 mg/m(3).     

The effect of the wind velocity on the uptake rates of various diffusive samplers

This paper examines the results of experiments carried out in an exposure chamber to determine the wind effects on the performance of various diffusive sampler types commonly used for measuring gaseous pollutants in air. The resistance to wind of six diffusive samplers, two Palmes tubes, a badge with diffusion membrane, the EMD sampler and two radial diffusive samplers for different pollutants was compared in a range of velocities from 0 to 300?cm?s^?1. For all diffusive samplers tested, an increase in uptake rate was observed with increased air velocity usually following a logarithmic function. The consequences are an underestimation in the concentration measured by the diffusive samplers for low wind velocities below 30?cm?s^?1 and conversely an overestimation from 60?cm?s^?1. The magnitude of wind effects depends on diffusive sampler type and exceeds an uptake rate variation of ±20% for the axial diffusion tubes and the EMD sampler. With regard to the characteristics of each diffusive sampler, the dependence of uptake rate on wind velocity was analysed and discussed. The radial diffusive samplers for benzene and particularly the ones having a large and thick porous membrane appear to be the most effective design to minimise the influence of air velocity on passive sampling.     

Evaluation of the novel passive sampler for cyanobacterial toxins microcystins under various conditions including field sampling

In the present study, we have evaluated the effectiveness of a passive sampler for polar organic chemicals to accumulate a group of widespread and hazardous tumor-promoting toxins produced in cyanobacterial water blooms—microcystins (MC). The previously optimized configuration of the sampler based on polycarbonate membrane and Oasis HLB sorbent (2.75 mg/cm²) was validated under various exposure scenarios in laboratory and field. Calibration of the passive sampler conducted under variable conditions and concentrations of MC revealed linearity of the sampling up to 4 weeks. The sampling rates of microcystins for two different exposure scenarios were derived (e.g., MC-LR: R _s = 0.017 L/day under static and 0.087 L/d under turbulent conditions). R _s values were further used for calculations of time-weighted average concentrations in natural water. Improved sensitivity and selectivity of the in-house-made sampler was observed in comparison with the commercially available Polar Organic Compound Integrative Sampler (POCIS). Comparisons of grab and passive sampling methods were performed during cyanobacterial water bloom season in the Brno reservoir, Czech Republic in 2008. Data obtained by passive sampling provided a more relevant picture of the situation and enabled better assessment of potential risks. The present study demonstrated that the modification of POCIS is suitable for monitoring of occurrence and retrospective estimations of microcystin water concentrations, especially with respect to the control of drinking water quality.     

Development of a highly sensitive method for determining atmospheric carbonyl compounds by passive sampling and application of the method to a survey of indoor air

A simple, highly sensitive analytical method for measuring many kinds of carbonyls in air using a passive sampler containing a sorbent (silica gel) coated with 2,4-dinitrophenylhydrazine has been developed. The carbonyls collected by the sampler were extracted with a solvent, and the extracts were subjected to high-performance liquid chromatography (HPLC; UV detection) without first being concentrated. In this method, the volume injection is examined, and is found to have a sensitivity at least 20 times that of ordinary HPLC methods. The air concentrations of nine carbonyls collected by passive sampling over a period of 24?h were estimated by means of conversion equations derived from the results of active sampling;c?=?^{10[log ( y} )^{??? b ] a} , where c is the carbonyl concentration in air (µg/m³); y is the amount of carbonyl collected by the passive sampler (µg); and a and b are constants for each carbonyl compound. The calculated air concentrations were consistent with the concentrations measured by active sampling. This method may be useful in determining personal exposure to ambient carbonyls.     

Collection,storage, and electrophoretic analysis of nanoliter microdialysis samples collected from awake animals in vivo

Microdialysis sampling is an important tool for chemical monitoring in living systems. Temporal resolution is an important figure of merit that is determined by sampling frequency, assay sensitivity, and dispersion of chemical zones during transport from sampling device to fraction collector or analytical system. Temporal resolution has recently been improved by segmenting flow into plugs, so that nanoliter fractions are collected at intervals of 0.1–2 s, thus eliminating temporal distortion associated with dispersion in continuous flow. Such systems, however, have yet to be used with behaving subjects. Furthermore, long-term storage of nanoliter samples created by segmented flow has not been reported. In this work, we have addressed these challenges. A microdialysis probe was integrated to a plug generator that could be stably mounted onto behaving animals. Long-term storage of dialysate plugs was achieved by collecting plugs into high-purity perfluoroalkoxy tubes, placing the tube into hexane and then freezing at −80°C. Slow warming with even temperatures prevented plug coalescence during sample thawing. As a demonstration of the system, plugs were collected from the striatum of behaving rats using a 0.5-mm-long microdialysis probe. Resulting plugs were analyzed 1–4 days later by chip-based electrophoresis. To improve throughput of plug analysis over previous work, the speed of electrophoretic separation was increased by using forced air cooling and 1-butyl-2,3-dimethylimidazolium tetrafluoroborate as a separation buffer additive, allowing resolution of six neuroactive amino acids in 30 s. Concentration changes induced by K⁺ microinjections were monitored with 10 s temporal resolution. The improvements reported in this work make it possible to apply segmented flow microdialysis to the study of behaving animals and enable experiments where the analytical system cannot be placed close to the animal.     

Breath Analysis: Comparison among Methodological Approaches for Breath Sampling

Despite promising results obtained in the early diagnosis of several pathologies, breath analysis still remains an unused technique in clinical practice due to the lack of breath sampling standardized procedures able to guarantee a good repeatability and comparability of results. The most diffuse on an international scale breath sampling method uses polymeric bags, but, recently, devices named Mistral and ReCIVA, able to directly concentrate volatile organic compounds (VOCs) onto sorbent tubes, have been developed and launched on the market. In order to explore performances of these new automatic devices with respect to sampling in the polymeric bag and to study the differences in VOCs profile when whole or alveolar breath is collected and when pulmonary wash out with clean air is done, a tailored experimental design was developed. Three different breath sampling approaches were compared: (a) whole breath sampling by means of Tedlar bags, (b) the end-tidal breath collection using the Mistral sampler, and (c) the simultaneous collection of the whole and alveolar breath by using the ReCIVA. The obtained results showed that alveolar fraction of breath was relatively less affected by ambient air (AA) contaminants (p-values equal to 0.04 for Mistral and 0.002 for ReCIVA Low) with respect to whole breath (p-values equal to 0.97 for ReCIVA Whole). Compared to Tedlar bags, coherent results were obtained by using Mistral while lower VOCs levels were detected for samples (both breath and AA) collected by ReCIVA, likely due to uncorrected and fluctuating flow rates applied by this device. Finally, the analysis of all data also including data obtained by explorative analysis of the unique lung cancer (LC) breath sample showed that a clean air supply might determine a further confounding factor in breath analysis considering that lung wash-out is species-dependent.     

Evaluation of denuder sampling for a mixture of three common gaseous diisocyanates

A denuder sampler has been evaluated for a mixture of three gaseous diisocyanates, i.e. toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI). Sampling was performed at a total concentration of diisocyanates close to the Swedish occupational exposure limit (OEL), which is 10 ppbv (69-92 microg m(-3)), for a 5-min period. The denuder tube was coated with a chemosorptive stationary phase consisting of SE-30 (polydimethylsiloxane) and the derivatising reagent dibutylamine (DBA). It was shown that the denuder has a collection efficiency for HDI and IPDI comparable to that of an impinger method, while sampling of TDI resulted in an 8% lower concentration. Both short-term (15 min) and long-term (8 h) sampling periods were shown to yield reproducible results. For 8-h measurements, a sampling flow rate of 5 mL min(-1) was shown to be suitable for the investigated concentration range, i.e. 10-100 ppbv (69-921 microg m(-3)). A flow rate of 25 mL min(-1) or higher resulted in breakthrough after 8 h due to chromatography of the compounds in the adsorbent. The limit of detection (LOD) for the air sampling method is nearly 500 times lower than the OEL. The denuder tubes can be prepared at least 10 days prior to sampling without degradation of performance. Furthermore, they can be stored up to 6 days in a freezer after sampling without significant loss of analytes.