Roger Lindahl

Diffusive air sampling of reactive compounds. A review

Methods for diffusive sampling of reactive compounds in air are reviewed. Sampler types include sorbent, liquid and filter samplers. The most versatile sampler for reactive compounds is the filter sampler, where reactive compounds are trapped on a reagent-coated filter. Applications are described for the sampling of reactive organics and inorganics. Aldehydes can be sampled using a 2, 4-dinitrophenylhydrazine-coated filter, and amines with a filter coated with 1-naphthyl isothiocyanate. The derivatives formed are determined by high-performance liquid chromatography with ultraviolet detection. Inorganics such as ozone and nitrogen oxides can also be determined with the filter sampler technique.

Analysis of some older Scandinavian formulations of 2,4-dichlorophenoxy acetic acid and 2,4,5-trichlorophenoxy acetic acid for contents of chlorinated dibenzo-p-dioxins and dibenzofurans.

Ten samples of older formulations of 2,4,5-trichlorophenoxy acetic acid and 2,4-dichlorophenoxy acetic acid used in Sweden were analyzed for chlorinated dibenzo-p-dioxins and dibenzofurans. The analyses were performed with gas chromatography/mass spectrometry with a high resolution glass capillary column for maximum isomeric separation and sensitivity. The detection limit was 0.01-0.05 ppm. The amounts of contaminants were of the same order of magnitude as that found earlier in European samples with later production dates (late 1960s and 1970s).

Influence of air humidity on sampling efficiency of some solid adsorbents used for sampling organics from work-room air

Abstract The influence of air humidity on the sampling efficiency of Amberlite XAD porous polymers and activated charcoal was studied by determining the recovery of various organics at 20% and 85% relative humidity. The sampling efficiency of XAD-7 was found to decrease with increasing relative humidity, while the sampling efficiency of XAD-2 and activated charcoal was relatively unaffected for the compounds studied. Activated charcoal had a greater capacity than Amberlite XAD for several types of compounds, however.

Evaluation of a diffusive sampler for air sampling of monoterpenes

A diffusive sampler for the assessment of exposure to terpenes was validated by laboratory experiments and field tests. The uptake rate for α-pinene was calculated to be 11.4 ml min–1. No statistically significant effects of relative humidity, exposure time, concentration of α-pinene or sorbent were found on performing an eight run fractional factorial design. The correlation between pumped sampling and diffusive sampling in a saw mill was good (correlation coefficient = 0.997). No effects of back-diffusion could be shown. The uptake rate was constant over the air speed range 0.05–0.6 m s–1 and the monoterpenes α-pinene, β-pinene and Δ3-carene could be sampled simultaneously. The sampler should be analysed within 14 d after the exposure assessment.

Validation of a diffusive sampler for the determination of acetaldehyde in air

A diffusive sampler for the determination of acetaldehyde in air was evaluated. Acetaldehyde was trapped on a filter impregnated with 2,4-dinitrophenylhydrazine and the hydrazone formed was analysed using HPLC with UV detection. As the capacity of the standard sampler was too low, a modification was made. The capacity of the modified sampler was sufficient for 8 h sampling at 90 mg m–3 and the method was sensitive enough for the measurement of less than 4.5 mg m–3 in a 15 min sampling period. The sampling rate of 17.1 ml min–1(RSD = 6.7%) was not influenced by the sampling time, concentration or relative humidity. The sampler can be used for both personal sampling and area sampling.

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.

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.

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.

Sampling of epichlorohydrin and ethylene chlorohydrin in workroom air using Amberlite XAD-7 resin

Abstract Activated charcoal, Amberlite XAD-2 and Amberlite XAD-7 were evaluated for the adsorption of epichlorohydrin and ethylene chlorohydrin from air followed by desorption with solvent. Ethylene chlorohydrin was found to be unstable on activated charcoal in the presence of carbon disulfide. Recoveries from XAD-2 were low, and XAD-7 was found to be the best adsorbent for the sampling of these compounds from air.

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.