Diffusive sampling of methyl isocyanate using 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ) as derivatizing agent

A diffusive sampling method for the determination of methyl isocyanate (MIC) in air is introduced. MIC is collected using a glass fiber filter impregnated with 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ). The urea derivative formed is desorbed from the filter with acetonitrile and analyzed by means of high-performance liquid chromatography (HPLC) using fluorescence detection (FLD) with lambdaex = 471 nm and lambdaex = 540 nm. Additionally, a method was developed using tandem mass spectrometric (MS-MS) detection, which was performed as selected reaction monitoring (SRM) on the transition [MIC-NBDPZ + H]+ (m/z 307) to [NBDPZ + H]+ (m/z 250). The diffusive sampler was tested with MIC concentrations between 1 and 35 microg m(-3). The sampling periods varied from 15 min to 8 h, and the relative humidity (RH) was set from 20% up to 80%. The sampling rate for all 15 min experiments was determined to be 15.0 mL min(-1) (using HPLC-FLD) with a relative standard deviation of 9.9% for 56 experiments. At 80% RH, only 15 min sampling gave acceptable results. Further experiments revealed that humidity did not affect the MIC derivative but the reagent on the filter prior to and during sampling. The sampling rate for all experiments (including long term sampling) performed at 20% RH was found to be 15.0 mL min(-1) with a relative standard deviation of 6.3% (N = 42). The limit of quantification was 3 microg m(-3) (LC-MS-MS: 1.3 microg m(-3)) for 15 min sampling periods and 0.2 microg m(-3) (LC-MS-MS: 0.15 microg m(-3)) for 8 h sampling runs applying fluorescence detection.     

A diffusive sampling device for the determination of formaldehyde in air using N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) as reagent

A new method utilizing the diffusive sampling of formaldehyde in air has been developed. Formaldehyde is sampled with the use of a glass fiber filter impregnated with N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH) and phosphoric acid. The formaldehyde hydrazone formed is desorbed from the filter with acetonitrile and determined by high-performance liquid chromatography (HPLC) with UV/visible detection at 474 nm. The sampling rate was determined to be 24.7 mL min-1 with a relative standard deviation of 7% for 48 experiments. The measured sampling rates were not dependent on the formaldehyde concentration (0.1-1.0 mg m-3), sampling time (15-482 min) or relative humidity (20-85%). The detection limit was 70 micrograms m-3 for a 15 min sampling period and 2 micrograms m-3 for an 8 h sampling period.     

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.     

Effects of humidity and filter material on diffusive sampling of isocyanates using reagent-coated filters

Diffusive sampling of methyl isocyanate (MIC) on 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ)-coated glass fibre (GF) filters is strongly affected by high relative humidity (RH) conditions. It is shown that the humidity interference is a physical phenomenon, based on displacement of reagent from the filter surface. In this paper, this drawback has been overcome by changing the filter material to the less polar polystyrene divinyl benzene (SDB). A series of experiments was performed to compare the analyte uptake on the two filter materials for different sampling periods and analyte concentrations at both low and high RH conditions. Additionally, the materials were investigated as well for passive sampling of ethyl (EIC) and phenyl isocyanate (PhIC) with NBDPZ and 1-(2-methoxyphenyl) piperazine (2-MP) as an alternative derivatising agent. Using 2-MP, the mean GF/SDB response ratios were determined to be 1.02 for MIC (RSD: 6.1%) and 1.03 for EIC (RSD: 6.8%), whereas PhIC could only be determined on SDB filters. Using NBDPZ as reagent, the negative influence of high humidity disappeared when SDB filters were used instead of GF filters. Even at low RH conditions, sampling with SDB material generally resulted in a higher analyte uptake than with GF filters. The GF/SDB response ratios were independent of sampling time or analyte concentration and were determined to be 0.70 (RSD: 4.7%) for MIC, 0.84 (RSD: 4.5%) for EIC and 0.95 (RSD 5.4%) for PhIC, meaning that the NBDPZ diffusive sampler based on SDB can be used at all humidity conditions without any restrictions.     

Solvent-free sampling with di-n-butylamine for monitoring of isocyanates in air

The solvent-free sampler for airborne isocyanates consisted of a polypropylene tube with an inner wall coated with a glass fibre filter, coupled in series with a 13 mm glass fibre filter. The filters were impregnated with reagent solution containing equimolar amounts of di-n-butylamine (DBA) and acetic acid. Air sampling was performed with an air flow of 0.2 l min(-1). The formed isocyanate-DBA derivatives were determined using liquid chromatography and tandem mass spectrometry. The sampler was investigated in regard to collection principle and extraction of the formed derivatives with good results. The possibility to store the sampler before sampling and to perform long-term sampling was demonstrated. Field extraction of the sampler was not necessary, as there was no difference between immediately extracted samples and stored ones (2 days). In comparative studies, the sampler was evaluated against a reference method, impinger-filter sampling with DBA as reagent. The ratios between the results obtained with the sampler and the reference in a test chamber at a relative humidity (RH) of 45% was in the range of 83-109% for isocyanates formed during thermal decomposition of PUR. At RH 95%, the range was 72-101% with the exception of isocyanic acid. In two field evaluations, the ratios for fast curing 2,4'- and 4,4'-methylene bisphenyl diisocyanate (MDI) was in the range 81-113% and for the 3-ring MDI the range was 54-70%. For the slower curing 1,6-hexamethylene diisocyanate (HDI) and HDI isocyanurate, the ratios were in the range 78-145%. In conclusion, the solvent-free sampler is a convenient alternative in most applications to the more cumbersome impinger-filter sampler.     

Analysis of indoor gaseous formic and acetic acid, using radial diffusive samplers

A diffusive sampling method for the determination of gaseous acetic and formic acids, using a radial symmetry diffusive sampler, has been optimised for a 7-day exposure time in this study. Sampling rate determinations were performed on data obtained from a dynamic exposure chamber, simulating the indoor conditions of an empty, closed, room, at room temperature and minimal wind speed. Analysis has been performed by means of ion chromatography. The sampling rates for formic acid concentrations of 128 microg m(-3) and 1248 microg m(-3) were determined to be 91.2 +/- 3.9 ml min(-1) and 111.6 +/- 2.8 ml min(-1), respectively. The acetic acid sampling rate was independent of the concentration in the range 160 microg m(-3)-1564 microg m(-3), and amounted to 97.3 +/- 3.1 ml min(-1). Experimentally determined sampling rates showed deviations of 3% for acetic acid, and 3-21% for formic acid, in relation to theoretically derived values. The blank values were as low as 1.69 +/- 0.07 microg for formic acid and 1.21 +/- 0.14 microg for acetic acid, and detection limits lower than 0.5 microg m(-3) could be achieved, which is an improvement of 98-99% compared to previously validated diffusive sampling methods. This study describes the first step of an extended validation program in which the applicability of these types of samplers for the measurement of organic acids will be validated and optimised for the environmental conditions typical for museum showcases.     

Development of active and diffusive sampling methods for determination of 3-methoxybutyl acetate in workplace air

Monitoring of the workplace concentration of 3-methoxybutyl acetate (MBA), which is used in printer's ink and thinner for screen-printing and as an organic solvent to dissolve various resins, is important for health reasons. An active and a diffusive sampling method, using a gas chromatograph equipped with a flame ionization detector, were developed for the determination of MBA in workplace air. For the active sampling method using an activated charcoal tube, the overall desorption efficiency was 101%, the overall recovery was 104%, and the recovery after 8 days of storage in a refrigerator was more than 90%. For the diffusive sampling method using the 3M 3500 organic vapor monitor, the MBA sampling rate was 19.89 cm(3) min(-1). The linear range was from 0.01 to 96.00 microg ml(-1), with a correlation coefficient of 0.999, and the detection limits of the active and diffusive samplers were 0.04 and 0.07 microg sample(-1), respectively. The geometric mean of stationary sampling and personal sampling in a screen-printing factory were 12.61 and 16.52 ppm, respectively, indicating that both methods can be used to measure MBA in workplace air.     

Compact semi-automatic incident sampler for personal monitoring of volatile organic compounds in occupational air

Suddenly occurring and time limited chemical exposures caused by unintended incidents might pose a threat to many workers at various work sites. Monitoring of exposure during such occasional incidents is challenging. In this study a compact, low-weight and personal semi-automatic pumped unit for sampling of organic vapor phase compounds from occupational air during sporadic and suddenly occurring incidents has been developed, providing simple activation by the worker potentially subjected to the sudden occurring exposures when a trained occupational hygienist is not available. The sampler encompasses a tube (glass or stainless steel) containing an adsorbent material in combination with a small membrane pump, where the adsorbent is capped at both ends by gas tight solenoid valves. The sampler is operated by a conventional 9 V battery which tolerates long storage time (at least one year), and is activated by pulling a pin followed by automatic operation and subsequent closing of valves, prior to shipping to a laboratory. The adjustable sampling air flow rate and the sampling time are pre-programmed with a standard setting of 200 mL min(-1) and 30 min, respectively. The average airflow in the time interval 25-30 min compared to average airflow in the interval 2-7 min was 92-95% (n = 6), while the flow rate between-assay precisions (RSD) for six different samplers on three days each were in the range 0.5-3.7%. Incident sampler recoveries of VOCs from a generated VOC atmosphere relative to a validated standard method were between 95 and 102% (+/-4-5%). The valves that seal the sampler adsorbent during storage have been shown to prevent an external VOC atmosphere (500 mg m(-3)) to enter the adsorbent tube, in addition to that the sampler adsorbent is storable for at least one month due to absence of ingress of contaminants from internal parts. The sampler was also suitable for trapping of semi-volatile organophosphates.     

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.     

Diffusive uptake in passive and active adsorbent sampling using thermal desorption tubes

Low flow active sampling techniques collecting vapors and gases using thermally desorbable adsorbents are now feasible and desirable in many applications as they permit long integration times, the potential for miniaturized sampling configurations, and other advantages. At very low air flow rates (< 1 ml min(-1)), diffusive uptake on adsorbents in conventional sorbent tubes may equal or exceed the active (pumped) uptake rate, and even at low flow rates (1-4 ml min(-1)), diffusive uptake may significantly bias measurements. Thus, corrections to account for the diffusive flux or means to limit the diffusive uptake are needed in low flow applications. This paper presents (1) a theoretical analysis of the role of diffusive and advective uptake for several sampling geometries of tube-type samplers; (2) experimental confirmation using both laboratory and field studies; (3) estimates of the tortuosity and porosity of the glass wool packing used to retain the adsorbent, parameters needed to estimate diffusive fluxes in passive and active sampling; (4) a demonstration that orifice-equipped low flow active samplers can reduce diffusive uptake and improve precision, and (5) a model predicting the saturated adsorbent layer that helps to account for the gradual decline in uptake rates seen in passive sampling. Diffusive uptake will depend on the tube configuration and diffusion coefficient of the substance of interest, but for conventional sampling tubes (0.4-0.5 cm id, 1.5 cm air gap), sample flow rates should be maintained above 1 to 4 ml min(-1) to keep errors below 5%. Laboratory experiments showed close agreement with theoretical calculations, and the field study using 1 to 4 d sampling periods and 0.3 ml min(-1) flows demonstrated that the orifice-equipped samplers essentially eliminated diffusive uptake. No significant practical difficulties are encountered using orifices, e.g., pressure drop is minimal. Experimental estimates of tortuosity (0.79 +/- 0.02) and porosity (0.92 +/- 0.10) of the glass wool packing (0.3 cm length) represent relatively little resistance to diffusion; however, variation in the packing and adsorbent placement can degrade the precision achievable by passive samplers. Diffusion barriers, consisting most simply of an orifice, may be used to lower the diffusive uptake. A needle-type orifice permits flows below 0.1 ml min(-1) and is suitable for sampling periods as long as several weeks, and it provided greater precision than conventional open-ended sampling tubes (8% compared to 13%). Finally, the gradual decrease in diffusive fluxes often seen in passive sampling is attributed to additional resistance posed by a saturated adsorbent layer, in agreement with a simple model based on total VOCs and specific adsorptivity of the adsorbent.     

Quantitative determination of hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocyanate (2,6-TDI) monomers at ppt levels in air by alkaline adduct coordination ionspray tandem mass spectrometry

Occupational exposures to isocyanates can lead to occupational asthma. Once sensitized, some workers could react to isocyanate monomers at concentrations below 1% of the Permissible Exposure Limit of 5 ppb in air. Currently available methods are not sufficiently sensitive to adequately evaluate isocyanates present at these levels in workplace air. This article describes a novel method for isocyanate determination allowing the ultratrace quantification in workplace air of hexamethylene diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate monomers. Sampling is performed during a complete workshift at a flow rate of 1 L min(-1) with a cassette containing a 1-(2-methoxyphenyl)piperazine-impregnated 25 mm filter. Analysis is performed using liquid chromatography hyphenated with coordination ionspray tandem mass spectrometry. The analytical method's linearity was measured for a concentration range varying from the limit of detection of 0.04-0.13 ng mL(-1), depending on the monomer, up to approximately 32 ng mL(-1) for every isocyanate monomer, all with correlation coefficients (R(2)) greater than 0.999. The analytical method's lower limit of quantification combined with an adapted sampling strategy allow the quantification of isocyanate monomers down to 0.04 ppt for an 8 h work shift when a lithium adduct is used, which is more than 300 times lower than the most sensitive method currently available. This novel method can be used to confirm the very low level of isocyanate monomers for the safe reassignment of sensitized workers and it is also useful for charting the isocyanate dispersion tail in workplace environments.     

A two-stage cyclone using microcentrifuge tubes for personal bioaerosol sampling

Personal aerosol samplers are widely used to monitor human exposure to airborne materials. For bioaerosols, interest is growing in analyzing samples using molecular and immunological techniques. This paper presents a personal sampler that uses a two-stage cyclone to collect bioaerosols into disposable 1.5 ml Eppendorf-type microcentrifuge tubes. Samples can be processed in the tubes for polymerase chain reaction (PCR) or immunoassays, and the use of multiple stages fractionates aerosol particles by aerodynamic diameter. The sampler was tested using fluorescent microspheres and aerosolized fungal spores. The sampler had first and second stage cut-off diameters of 2.6 microm and 1.6 microm at 2 l min(-1)(geometric standard deviation, GSD = 1.45 and 1.75), and 1.8 microm and 1 microm at 3.5 l min(-1)(GSD = 1.42 and 1.55). The sampler aspiration efficiency was >or=98% at both flow rates for particles with aerodynamic diameters of 3.1 microm or less. For 6.2 microm particles, the aspiration efficiency was 89% at 2 l min(-1) and 96% at 3.5 l min(-1). At 3.5 l min(-1), the sampler collected 92% of aerosolized Aspergillus versicolor and Penicillium chrysogenum spores inside the two microcentrifuge tubes, with less than 0.4% of the spores collecting on the back-up filter. The design and techniques given here are suitable for personal bioaerosol sampling, and could also be adapted to design larger aerosol samplers for longer-term atmospheric and indoor air quality sampling.     

Exposure to airborne isocyanates and other thermal degradation products at polyurethane-processing workplaces

The thermal degradation products of polyurethanes (PURs) and exposure to isocyanates were studied by stationary and personal measurements in five different occupational environments. Isocyanates were collected on glass fibre filters impregnated with 1-(2-methoxyphenyl)piperazine (2MP) and in impingers containing n-dibutylamine (DBA) in toluene. connected to a glass fibre postfilter. The derivatives formed were analysed by liquid chromatography: 2MP derivatives with UV and electrochemical detection and DBA derivatives with mass spectrometric detection. The release of aldehydes and other volatile organic compounds into the air was also studied. In a comparison of the two sampling methods, the 2MP method yielded about 20% lower concentrations for 4,4'-methylenediphenyl diisocyanate (MDI) than did the DBA method. In car repair shops, the median concentration of diisocyanates (given as NCO groups) in the breathing zone was 1.1 microg NCO m(-3) during grinding and 0.3 microg NCO m(-3) during welding, with highest concentrations of 1.7 and 16 pg NCO m(-3), respectively. High concentrations of MDI, up to 25 and 19 microg NCO m(-3), respectively, were also measured in the breathing zone during welding of district heating pipes and turning of a PUR-coated metal cylinder. During installation of PUR-coated floor covering, small amounts of aliphatic diisocyanates were detected in the air. A small-molecular monoisocyanate, methyl isocyanate, and isocyanic acid were detected only during welding and turning operations. The diisocyanate concentrations were in general higher near the emission source than in the workers' breathing zone. A sampling strategy to evaluate the risk of exposure to isocyanates is presented.     

24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).     

Passive sampling of glycol ethers and their acetates in indoor air

This study examined the performances of a thermal desorbable radial diffusive sampler for the weekly measurement of eight glycol ethers in indoor air and described the results of an application of this method carried out as part of HABIT'AIR Nord - Pas de Calais program for the air monitoring of these compounds in sixty homes located in northern France. The target compounds were the four glycol ethers banned from sale to the public in France since the 1990s (i.e. 2-methoxy ethanol, 2-ethoxy ethanol and their acetates) and four other glycol ethers derivatives of which the use have increased considerably (i.e. 1-methoxy-2-propanol, 2-butoxy ethanol and their acetates).A test program was carried out with the aim of validating the passive sampling method. It allowed the estimation of all the parameters of a method for each compound (calibration, analytical precision, desorption efficiency, sampling rate in standard conditions, detection limit and stability of sample before and after exposure), the examination of the influence of environmental factors on the sampling rate by some exposure chamber experiments and the assessment of the uncertainty of the measurements.The results of this evaluation demonstrated that the method has turned out to be suitable for six out of eight glycol ethers tested. The effect of the environmental factors on the sampling rates was the main source of measurement uncertainty. The measurements done in sixty homes revealed a relative abundance of 1-methoxy-2-propanol that was found in more than two thirds of homes at concentration levels of 4.5 microg m(-3) on average (a maximum value of 28 microg m(-3)). 1-methoxy-2-propanol acetate and 2-butoxy ethanol were also detected, but less frequently (in 19% of homes) and with the concentrations below 12 microg m(-3). The highest levels of these glycol ethers appear to be in relation to the emissions occurring at the time of cleaning tasks.     

Validation of diffusive mini-samplers for aldehyde and VOC and its feasibility for measuring the exposure levels of elementary school children

Exposure to various chemicals can cause adverse effects to health, such as asthma and allergies, especially in children. Data on personal exposure levels in children are scarce, thus small lightweight diffusive mini-samplers for aldehydes and volatile organic compounds (VOCs) were designed to measure the exposure level of children to these chemicals. The aim of the study was to validate and examine the applicability of these mini-samplers for measuring daily chemical exposure. The diffusive mini-samplers are 20 mm in length, 11 mm in diameter, and 1.67 g in weight. The devices are cylindrically shaped with polytetrafluoroethylene membrane filters placed at each end. To measure aldehydes and acetone, 20 mg of 2,4-dinitrophenylhydrazine was used as an absorbent. To measure VOCs, a carbon molecular sieve was used. The sampling rate for each chemical was determined by parallel sampling with active samplers in a closed exposure bag. The blank levels of the chemicals and the storage stability of the device were tested. The mini-samplers were compared to commercially available diffusive samplers. To examine the applicability of the samplers, 65 elementary school children carried them for 24 h. The sampling rates for formaldehyde, acetaldehyde, and acetone were 20.9, 22.9, and 19.7 mL min(-1), respectively. The limits of quantification (LOQ) for the 24-hour sampling by high-performance liquid chromatography/ultraviolet (HPLC/UV) analysis were 8.3, 7.6, and 8.8 μg m(-3) for formaldehyde, acetaldehyde, and acetone, respectively. The sampling rates for the 11 VOCs were determined and ranged from 3.3 mL min(-1) for styrene and 2-ethyl-1-hexanol to 11.7 mL min(-1) for benzene. The LOQ for the 24-hour sampling by gas chromatography-mass spectrometry (GC-MS) analysis ranged from 5.9-105.2 μg m(-3), 1.1-24.7 parts per billion. The storage stability after 5 days ranged from 94.8 to 118.2%. Formaldehyde, acetone, benzene, and toluene were detected above the LOQ in more than 90% of the children, and the median concentrations were 21.7, 20.9, 10.1, and 21.5 μg m(-3), respectively. This study shows that the diffusive samplers developed were suitable for children to carry and were capable of measuring the children's daily chemical exposure.     

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.     

扩散法采集个体接触空气中氨

本文采用扩散法将空气中氨采集在磷酸———甘油浸渍的无纺布吸收层上。该法采样速率为１３７６±８４ｍｌ／ｍｉｎ，与动力采样法现场对比测定，总不确定度为±１９３％，。采样器体积小，无噪声，操作方便，适于个体接触量与室内空气污染监测     

Determination of ortho-phthalaldehyde in air and on surfaces

Three sampling and analytical methods have been developed and evaluated for ortho-phthalaldehyde (OPA): (1) an HPLC-UV method for OPA in air, (2) a fluorimetric method for OPA on surfaces, and (3) a colorimetric method for OPA on surfaces. (1) The air sampler contains 350 mg of silica gel coated with 1 mg of acidified 2,4-dinitrophenylhydrazine (DNPH). Air sampling may be conducted at 0.03 to 1.0 L min(-1) for periods up to 8 h. Samples were eluted with ethyl acetate, and the eluents were allowed to stand for 72 h. Analysis was by high performance liquid chromatography (HPLC) with a UV detector set at 369 nm. An unusual phenomenon was the observation that the stability of the sample on a sampler at 3 degrees C tends to decrease as the total quantity of OPA collected on the sampler decreases. Elution of the samples within 24 h of air sampling is required. The detection limit (LOD) is approximately 0.02 microg of OPA per sample. OPA on surfaces may be collected with strips cut from a sheet of polyvinyl alcohol (PVA wipe). (2) In the surface wipe method with analysis by fluorescence measurement, the strips of PVA wipe were placed into dimethyl sulfoxide. An aliquot was treated with aqueous N-acetyl-l-cysteine and ethylenediamine. Analysis was performed with a portable fluorometer (excitation and emission wavelengths = 365 nm and 438 nm, respectively). The LOD is 0.2 microg per sample. (3) In the surface wipe method with visual colorimetric detection, the strips of PVA wipe were placed into 30 : 70 acetonitrile : water. An aliquot was treated with N-(1-naphthyl)ethylenediamine in 0.1 m sulfuric acid. After color development, the LOD is approximately 48 microg per sample. These methods have been field tested in a hospital.     

Development of a sampling method for the simultaneous monitoring of straight-chain alkanes, straight-chain saturated carbonyl compounds and monoterpenes in remote areas

Studies have shown that biogenic compounds, long chain secondary compounds and long lifetime anthropogenic compounds are involved in the formation of organic aerosols in both polluted areas and remote places. This work aims at developing an active sampling method to monitor these compounds (i.e. 6 straight-chain saturated aldehydes from C6 to C11; 8 straight-chain alkanes from C9 to C16; 6 monoterpenes: α-pinene, β-pinene, camphene, limonene, α-terpinene, & γ-terpinene; and 5 aromatic compounds: toluene, ethylbenzene, meta-, para- and ortho-xylenes) in remote areas. Samples are collected onto multi-bed sorbent cartridges at 200 mL min(-1) flow rate, using the automatic sampler SyPAC (TERA-Environnement, Crolles, France). No breakthrough was observed for sampling volumes up to 120 L (standard mixture at ambient temperature, with a relative humidity of 75%). As ozone has been shown to alter the samples (losses of 90% of aldehydes and up to 95% of terpenes were observed), the addition of a conditioned manganese dioxide (MnO(2)) scrubber to the system has been validated (full recovery of the affected compounds for a standard mixture at 50% relative humidity--RH). Samples are first thermodesorbed and then analysed by GC/FID/MS. This method allows suitable detection limits (from 2 ppt for camphene to 13 ppt for octanal--36 L sampled), and reproducibility (from 1% for toluene to 22% for heptanal). It has been successfully used to determine the diurnal variation of the target compounds (six 3 h samples a day) during winter and summer measurement campaigns at a remote site in the south of France.