Continuous, intermittent and passive sampling of airborne VOCs

Long sampling periods are often advantageous or required for measuring air quality and characterizing exposures. However, sampling periods exceeding 8 to 24 h using thermally desorbable adsorbent tube (TDT) samplers for the measurement of airborne volatile organic compounds (VOCs) face several challenges, including maintaining stable and low flow rates, and avoiding breakthrough of the adsorbent. These problems may be avoided using intermittent sampling; however, the literature contains few if any reports that have evaluated this technique in environmental, occupational or other applications. The purpose of this study is to evaluate continuous, intermittent and passive sampling methods using both laboratory and real-world tests. Laboratory tests compared continuous and intermittent (active) samplers in a controlled dynamic test gas generation system. Field tests used side-by-side active and passive samplers in an office, home workshop and four smokers' homes. All samples were analyzed for a wide range of VOCs by GC-MS. In most instances, intermittent sampling yielded better reproducibility (duplicate precision of 10 +/- 6%) than continuous low-flow sampling (18 +/- 5%), in part due to difficulty maintaining low flows. Concentrations obtained using intermittent sampling agreed with those for continuous sampling, with downward biases resulting primarily from errors in flow rate measurements. In the field, more VOC species were detected using active rather than passive sampling. Passive measurements were 12% lower than continuous measurements, a difference attributed to declining uptake rates at higher concentrations over the 3 to 4 d sampling period. Overall, most measurements obtained using the three sampling methods agreed within 20% for a wide range of concentrations (0.1 to 230 microg m(-3)). Both passive and intermittent sampling approaches are suitable for long sampling periods, but intermittent sampling provides greater flexibility with respect to sampling period, and permits the use of multi-bed adsorbents that can capture a wider range of VOCs.     

Evaluation of VOC measurments in the EXPOLIS study. Air Pollution Exposure Distributions within Adult Urban Urban Populations in Europe

Personal exposures and microenvironment concentrations of 30 target VOCs were measured for 401 participants living in five European cities as a part of the EXPOLIS (Air Pollution Exposure Distributions within Adult Urban Populations in Europe) study. Measurements in Basel used an active charcoal (Carbotech) adsorbent as opposed to the Tenax TA used in the other study centres. In addition, within each centre, personal and microenvironment VOC sampling required different sampling pumps and, because of different sampling durations, different sampling flow rates. Thus, careful testing of the sampling and analysis procedures was required to ensure accuracy and comparability of collected data. Monitor comparison tests using Tenax TA showed a mean VOC concentration ratio of 0.95 between the personal and microenvironment monitors. The LODs for the target VOCs using Tenax TA ranged from 0.7 to 5.2 microg m(-3). The LODs for the 14 target compounds quantifiable using Carbotech ranged from 0.9 to 3.2 microg m(-3). Tenax TA field blanks showed no remarkable contamination with the target VOCs, except benzaldehyde, a known artefact with this adsorbent. Thus, the diffusion barrier system used prevented contamination of Tenax TA samples by passive diffusion during non-sampling periods. Duplicate and parallel evaluations of the Tenax TA and Carbotech showed an average difference of < 17% in VOC concentrations within the sampling methods, but a systematic difference between the methods (Tenax TA: Carbotech concentration ratio = 1.18-2.36). These field evaluations and quality assurance tests showed that interpretation and comparison of the results in any VOC monitoring exercise should be done on a compound by compound basis. It is also apparent that carefully planned and realised QA and QC (QA/QC) procedures are needed in multi-centre studies, where a common sampling method and laboratory analysis technique are not used, to strengthen and simplify the interpretation of observed VOC levels between participating centres.     

Size-selective sampling of particulates using a physiologic sampling pump

Recent laboratory research indicates physiologic sampling of gas and vapor may provide more representative estimates of personal exposures than traditional methods. Modifications to the physiologic sampling pump (PSP) used in that research are described which extend its usefulness to size-selective sampling of particulates. PSPs used in previous research varied motor speed to keep sampling proportional to the subject's inhalation. This caused airflow and particle velocities through the collection device to continually change making those pumps unsuitable for sampling particulates. The modified implementation of the PSP pulls a constant airflow into and through a cyclone, then uses valves to either direct the airflow through, or divert the airflow around, the sampling filter. By using physiologic inputs to regulate the fraction of each second that air flows through the sampling filter, samples may be collected in proportion to inhalation rate. To evaluate the performance of a functional prototype 5 different sizes of monodisperse aerosols of ammonium fluorescein were generated by a vibrating orifice aerosol generator and introduced into a calm air chamber. To simulate different inhalation rates the valves of the PSP were energized using 9 different duty cycles. Efficiency curves are presented and compared to a standard respirable convention by bias mapping. The performance of the modified cyclone used in the PSP sampling head compared favorably with a commercially available cyclone of the same model, operating at a constant airflow (± 10% over almost all the size distributions of concern). The new method makes physiologic sampling of the respirable fraction of particulates feasible.     

Low-flow active and passive sampling of VOCs using thermal desorption tubes: theory and application at an offset printing facility

While air sampling techniques using adsorbent-based collection, thermal desorption and chromatographic analysis have found a niche in ambient air sampling, occupational applications have been more limited. This paper evaluates the use of thermal desorption techniques for low flow active and passive sampling configurations which allow conveniently long duration sampling in occupational settings and other high concentration environments. The use of an orifice enables flows as low as 0.5 ml min(-1) and sampling periods up to several days without significant biases. A model is used to predict sampling rates of a passive sampler encompassing an orifice, a void space, glass wool, and the adsorbent. Laboratory and field tests conducted at a commercial offset printing facility, which contained a variety of volatile organic compounds (primarily aromatic but also a few chlorinated and terpene compounds at levels from 1 to 67,000 microg m(-3)), are used to evaluate the approach. Tenax GR and Carbosieve SIII, both singly and together, were employed as adsorbents. Side-by-side tests comparing high flow, low flow and passive samplers show excellent agreement and high linearity (r = 0.95) for concentrations spanning nearly five orders of magnitude. Active samplers were tested at flows as low as 0.5 ml min(-1), compared to typical flows up to 40 ml min(-1). Passive samplers demonstrated a linear range and agreement with predictions for adsorbate loadings from approximately 1 ng to nearly 10 microg. Using a chemical mass balance receptor model, concentrations in the facility were apportioned to solvents, inks and other indoor and outdoor sources. Overall, the use of low flow active and passive sampling approaches employing thermal desorption techniques provides good performance and tremendous flexibility that facilitates use in many applications, including workplace settings.     

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.     

Occupational exposure to fluorinated hydrocarbons during refrigeration repair work

This study describes refrigeration repair workers' occupational exposures to halogenated refrigerants, focusing on difluorochloromethane (HCFC 22), tetrafluoroethane (HFC 134a) and a mixture of tri-, tetra- and pentafluoroethane (R404A) in 30 work operations. Unlike earlier reported studies, the present study includes working procedures involving welding in order to measure possible occupational exposure to decomposition products. The measurements included hydrogen fluoride (HF), hydrogen chloride (HCl), phosgene (COCl2) and volatile organic compounds (VOC). The exposures were assessed during work operations on small-scale cooling installations like refrigerators and freezers. The repair workers' occupational exposures to refrigerants were moderate, and the major part of the exposures were associated with specific working procedures lasting for relatively short periods of time (<20 min). During these exposure events the concentrations were occasionally high (up to 42434 mg m(-3)). Although welding operations lasted only for short periods of time, HF was detected in 9 out of 15 samples when HCFC 22, HFC 134a or R404A had been used. Hydrogen chloride was detected in 3 out of 5 samples in air polluted with HCFC 22. Phosgene was not detected. A large number of VOCs in various concentrations were found during welding. Except for the applied refrigerants, halogenated compounds were only found in one sample.     

Determination of the dialdehyde glyoxal in workroom air-development of personal sampling methodology

The dialdehyde glyoxal (ethanedial) is an increasingly used industrial chemical with potential occupational health risks. This study describes the development of a personal sampling methodology for the determination of glyoxal in workroom air. Among the compounds evaluated as derivatizing agents; N-methyl-4-hydrazino-7-nitrobenzofurazan (MNBDH), 1,2-phenylenediamine (OPDA), 1-dimethylaminonaphthalene-5-sulfonylhydrazine (dansylhydrazine, DNSH) and 2,4-dinitrophenylhydrazine (DNPH), DNPH was the only reagent that was suitable. Several different samplers were evaluated for sampling efficiency of glyoxal in workroom air using DNPH as derivatizing agent; in-house DNPH coated silica particles packed in two different types of glass tubes, impingers containing acidified DNPH solution, filter cassettes containing glass fibre filters coated with DNPH, a commercially available solid phase cartridge sampler originally developed for formaldehyde sampling (Waters Sep-Pak DNPH-silica cartridge), and the commercially available SKC UMEx 100 passive sampler originally developed for formaldehyde sampling. Aldehyde atmospheres for sampler evaluation were generated with an in-house made vapour atmosphere generator coupled to a sampling unit, with the possibility of parallel sampling. The resulting glyoxal-DNPH derivative was determined using both LC-UV and LC-APCI-MS with negative ionization. By far, the highest recovery of glyoxal was obtained employing one of the in-house DNPH coated silica samplers (93%, RSD = 3.6%, n = 12).     

Development of a diffusive sampling method for determination of methyl isocyanate in air

A diffusive sampling method for determination of methyl isocyanate in air has been developed. A glass fibre filter impregnated with 1-(2-methoxyphenyl)piperazine in a commercially available diffusive sampling device was used to collect methyl isocyanate and the derivative formed was analysed with LC-MS/MS. The sampling rate was determined to be 15.6 ml min(-1), with a relative standard deviation of 7.3%. The sampler was validated for sampling periods from 15 min to 8 h, for relative humidities from 20% to 80% and for concentrations from I to 46 microg m(-3). A field validation was also made and the diffusive sampling results showed no difference compared to a pumped reference method. The impregnated filters have to be stored apart from the diffusive sampler housing and loaded into the sampler prior to each sampling.     

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.     

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.     

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.     

Reliability of nitrogen dioxide passive diffusion tubes for ambient measurement: in situ properties of the triethanolamine absorbent

Factors concerning NO2 uptake by the absorbent triethanolamine (TEA) in NO2 diffusion tubes are examined. Although the nominal freezing point of TEA is 17.9-21.2 degrees C, we show that, for a range of aqueous TEA solutions (0-20%, H2O), no freezing occurs even at -10 degrees C. Therefore NO2 collection efficiency is unlikely to be impaired by low temperature exposure. The recovery of TEA from the meshes of exposed samplers is determined as approximately 98%, even after 42 days, showing that the stability in situ of TEA is unaffected by long-term exposure. A model of a diffusion tube sampling array for simultaneous exposures, with a 0.1 m sampler spacing, shows that NO2 uptake by individual samplers is not affected by the presence of neighbouring tubes in the array. This is confirmed by sampler precision at two Cambridge sites. Four sampler preparation methods are compared for differences in NO2 uptake of exposed samplers. All methods employ TEA as absorbent, transferred by either dipping meshes in a TEA-acetone solution or pipetting aliquots of a TEA-H2O solution onto the meshes. For samplers prepared by three of the methods, no difference in NO2 uptake is found, but for samplers prepared using a 50% v/v TEA-H2O solution, a mean reduction of 18% is found. Student's t-tests show that the difference is highly significant (P < or = 0.001). Reasons for the difference are discussed.     

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.     

Flux of organic compounds from grass measured by relaxed eddy accumulation technique

Fluxes of some Volatile Organic Compounds (VOC) from grass were measured at a golf course in western Sweden, using the Relaxed Eddy Accumulation (REA) technique. The sampling was done by collecting VOC onto adsorbent tubes and the analysis was performed by thermal desorption followed by GC/MS. High emissions were observed after cutting. Transient fluxes of (Z)-3-hexenyl acetate (0.51 microg m(-2) s(-1)), (Z)-3-hexen-1-ol (0.14 microg m(-2) s(-1)) and (Z)-3-hexenal (0.40 microg m(-2) s(-1)) were measured, even at low temperatures. The REA technique requires a relatively large fetch area that is sometimes not available. Therefore, a procedure for correcting measured fluxes from a limited fetch is suggested.     

Systematic Biases in Measurement of Urban Nitrogen Dioxide using Passive Diffusion Samplers

Measurement of nitrogen dioxide using passivediffusion tube over 22 months in Cambridge, U.K. areanalysed as a function of sampler exposure time, andcompared with NO₂ concentrations obtained from aco-located chemiluminescence analyser. The averageratios of passive sampler to analyser NO₂ at acity centre site (mean NO₂ concentration 22 ppb)are 1.27 (n = 22), 1.16 (n = 34) and 1.11 (n = 7) forexposures of 1, 2 and 4-weeks, respectively. Modellingthe generation of extra NO₂ arising from chemicalreaction between co-diffusing NO and O₃ in thetube gave a ratio (modelled/measured) of 1.31 for1-week exposures. Such overestimation is greatest whenNO₂ constitutes, on average, about half of totalNO_x (= NO + NO₂) at the monitoring locality.Although 4-week exposures gave concentrations whichwere not significantly different from analyserNO₂, there was no correlation between thedatasets. At both the city-centre site and anothersemi-rural site (mean NO₂ concentration 11 ppb)the average of the aggregate of four consecutive1-week sampler exposures or of two consecutive 2-weeksampler exposures was systematically greater than fora single 4-week exposure.The results indicate two independent and opposingsystematic biases in measurement of NO₂ bypassive diffusion sampler: an exposure-timeindependent chemical overestimation with magnitudedetermined by local relative concentrations of NO andO₃ to NO₂, and an exposure-time dependentreduction in sampling efficiency. The impact of theseand other potential sources of systematic bias on theapplication of passive diffusion tubes for assessingambient concentrations of NO₂ in short (1-week)or long (4-week) exposures are discussed in detail.     

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.     

Analysis of volatile organic compounds (VOCs) in sediments using in situ SPME sampling

A new method of determining the composition of sediment/soil gases and their volatile organic compound (VOC) content is described. VOCs were collected in situ from intertidal sediments in the Menai Strait and surrounding areas. The sampling was performed using a portable sampler comprising a funnel coupled to a SPME fibre. Gases were extracted from the sediments using a small vacuum pump pulling 100 mL min(-1) at atmospheric pressure. Sixty one different compounds were detected in the samples, and their fluxes and concentrations were determined. The compounds were classified into groups: halogenated, sulfur containing compounds, aldehydes, BTEXs (benzene, toluene, ethyl benzene and xylene) and aliphatic hydrocarbons. Results of principal component analysis (PCA) showed that the chemical composition of extracted gas was influenced primarily by sediment type. Muddy anoxic sediments were dominated by halogenated and sulfur containing compounds and sandy sediments had more aldehydes and BTEXs.     

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.     

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.     

A catalogue of urban hydrocarbons for the city of Leeds: atmospheric monitoring of volatile organic compounds by thermal desorption-gas chromatography

A method has been developed for the speciation and quantitative determination of hydrocarbons in urban air in the city of Leeds. Hydrocarbons were pre-concentrated by adsorbent tube air sampling and analyzed using thermal desorption and gas chromatography with flame ionization detection and structural confirmation by mass spectrometric detection. While automated volatile organic compound (VOC) analyzers produced data for a maximum of about 30 compounds simultaneously, with the method described here, a total of 68 C6-C12 hydrocarbons were measured simultaneously in one analysis at parts per billion (ppb) levels. Several monitoring surveys were performed, one during the winter of 1993 and the other in the summer of 1994, at a number of sites to investigate the levels of VOCs identified in the urban air of Leeds.