Determination of technical grade isocyanates used in the production of polyurethane plastics

A method for determination of technical grade isocyanates used in the production of polyurethane (PUR) is presented. The isocyanates in technical grade products were characterised as di-n-butylamine (DBA) derivatives using LC-MS and LC-chemiluminescent nitrogen detection (CLND) and the total isocyanate content was compared to a titration assay. For collection of isocyanates in air, an impinger-filter sampling technique with DBA as derivatisation reagent was used. Characterised DBA and nonadeuterium labelled DBA derivatives of isocyanates in technical products were used as calibration standards and internal standards, respectively, in the analysis of air samples. Three workplaces were studied where PUR products were produced either by spraying or by moulding. In both technical products and in air samples, a number of monomeric, oligomeric and prepolymeric isocyanates of e.g. methylenebisphenyl diisocyanate (MDI) and hexamethylene diisocyanate (HDI) were characterised. Several of these have not previously been described in workplace atmospheres. In the technical isocyanate products, between 69 and 102% of the NCO content determined by titration was accounted for by LC-CLND. Quantifications of a wide range of isocyanates in air samples were performed with correlation coefficients in the range 0.988-0.999 (n= 8) and the instrumental detection limits were 0.7-25 pg. At the two workplaces where MDI- and HDI isocyanurate-based products were sprayed, the isocyanate composition in the air reflected the composition in the technical product. At the workplace where a MDI-based product was used in a moulding process, only the monomeric isocyanates were found in the air. The advantage of using characterised technical grade isocyanates as analytical standards was clearly demonstrated and the possibility of using index compounds when monitoring isocyanate exposure is discussed.     

Penetration patterns of monomeric and polymeric 1,6-hexamethylene diisocyanate monomer in human skin

We investigated penetration patterns of monomeric and polymeric 1,6-hexamethylene diisocyanate (HDI), experimentally and as part of commercial products, in excised full-thickness human skin at 5, 10, 30, or 60 min after exposure. We observed that both monomeric and polymeric HDI were readily absorbed into the skin and that the clearcoat composition affects the penetration rate of the individual isocyanates. The short-term absorption rates for HDI monomer, biuret, and isocyanurate were determined and used to estimate the exposure time required to reach a body burden equal to the American Conference of Governmental Industrial Hygienists (ACGIH) inhalation threshold limit value (TLV) or Oregon State occupational exposure limit (OEL). Oregon is the only government entity in the United States to promulgate a short-term exposure limit (STEL) for HDI-based polyisocyanates biuret and isocyanurate. Based on these absorption rates for a slow-drying clearcoat after 10 min (1.33 μg cm(-2) h(-1)) or 60 min (0.219 μg cm(-2) h(-1)), we calculated that 6.5 and 40 min dermal exposure, respectively, is required to achieve a dose of HDI equivalent to the ACGIH TLV. For biuret, the time to achieve a dose equivalent to the Oregon OEL for slow-drying clearcoat was much shorter (<31 min) than that for fast-drying clearcoat (618 min). Isocyanurate had the shortest skin absorption times regardless of clearcoat formulation (14 s-1.7 min). These results indicate that the dose received through dermal exposure to HDI-containing clearcoats has a significant potential to exceed the dose equivalent to that received through inhalation exposure at established regulatory limits. A critical need exists to monitor dermal exposure quantitatively in exposed workers, to use proper protective equipment to reduce dermal exposure, and to re-evaluate regulatory exposure limits for isocyanates.     

An FTIR investigation of isocyanate skin absorption using in vitro guinea pig skin

Isocyanates may cause contact dermatitis, sensitization and asthma. Dermal exposure to aliphatic and aromatic isocyanates can occur in various exposure settings. The fate of isocyanates on skin is an important unanswered question. Do they react and bind to the outer layer of skin or do they penetrate through the epidermis as unreacted compounds? Knowing the kinetics of these processes is important in developing dermal exposure sampling or decontamination strategies, as well as understanding potential health implications such exposure may have. In this paper the residence time of model isocyanates on hairless guinea pig skin was investigated in vitro using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectrometry. Model isocyanates tested were octyl isocyanate, polymeric hexamethylene diisocyanate isocyanurate (pHDI), polymeric isophorone diisocyanate isocyanurate (pIPDI) and methylenediphenyl diisocyanate (MDI). Isocyanates in ethyl acetate (30 microL) were spiked directly on the skin to give 0.2-1.8 micromol NCO cm(-2) (NCO = -N=C=O), and absorbance of the isocyanate group and other chemical groups of the molecule were monitored over time. The ATR-FTIR findings showed that polymeric isocyanates pHDI and pIPDI may remain on the skin as unreacted species for many hours, with only 15-20% of the total isocyanate group disappearing in one hour, while smaller compounds octyl isocyanate and MDI rapidly disappear from the skin surface (80+% in 30 min). Isocyanates most likely leave the skin surface by diffusion predominantly, with minimal reaction with surface proteins. The significance of these findings and their implications for dermal exposure sampling and isocyanate skin decontamination are discussed.     

Airborne thermal degradation products of polyurethene coatings in car repair shops

A methodology for workplace air monitoring of aromatic and aliphatic, mono- and polyisocyanates by derivatisation with di-n-butylamine (DBA) is presented. Air sampling was performed using midget impinger flasks containing 10 ml of 0.01 mol l(-1) DBA in toluene and a glass-fibre filter in series after the impinger flask, thereby providing the possibility of collecting and derivatising isocyanates in both the gas and particle phases. Quantification was made by LC-MS, monitoring the molecular ions [MH]+. Air samples taken with this method in car repair shops showed that many different isocyanates are formed during thermal decomposition of polyurethane (PUR) coatings. In addition to isocyanates such as hexamethylene (HDI), isophorone (IPDI), toluene (TDI) and methylenediphenyl diisocyanate (MDI), monoisocyanates such as methyl (MIC), ethyl (EIC), propyl (PIC), butyl (BIC) and phenyl isocyanate (PhI) were found. In many air samples the aliphatic monoisocyanates dominated. During cutting and welding operations, the highest levels of isocyanates were observed. In a single air sample from a welding operation in a car repair shop, the highest concentrations found were: MIC, 290; EIC, 60; PIC, 20; BIC, 9; PhI, 27; HDI, 105; IPDI, 39; MDI, 4; and 2,4-TDI and 2,6-TDI 140 microg m(-3). Monitoring the particle size distribution and concentration during grinding, welding and cutting operations showed that ultrafine particles (< 0.1 microm) were formed at high concentrations. Isocyanates with low volatility were mainly found in the particle phase, but isocyanates with a relatively high volatility such as TDI, were found in both the particle and gas phases.     

Quantitative monitoring of dermal and inhalation exposure to 1,6-hexamethylene diisocyanate monomer and oligomers

Respiratory sensitization and occupational asthma are associated with exposure to 1,6-hexamethylene diisocyanate (HDI) in both monomeric and oligomeric forms. The monomer and polymers of diisocyanates differ significantly in their rates of absorption into tissue and their toxicity, and hence may differ in their contribution to sensitization. We have developed and evaluated a liquid chromatography/mass spectrometry (LC-MS) method capable of quantifying HDI and its oligomers (uretidone, biuret, and isocyanurate) in air, tape-stripped skin, and paint samples collected in the automotive refinishing industry. To generate analytical standards, urea derivatives of HDI, biuret, and isocyanurate were synthesized by reaction with 1-(2-methoxyphenyl)piperazine and purified. The urea derivatives were shown to degrade on average by less than 2% per week at -20 degrees C over a 2 month period in occupational samples. The average recovery of HDI and its oligomers from tape was 100% and the limits of detection were 2 and 8 fmol microl(-1), respectively. Exposure assessments were performed on 13 automotive spray painters to evaluate the LC-MS method and the sampling methods under field conditions. Isocyanurate was the most abundant component measured in paint tasks, with median air and skin concentrations of 2.4 mg m(-3) and 4.6 microg mm(-3), respectively. Log-transformed concentrations of HDI (r = 0.79, p < 0.0001) and of isocyanurate (r = 0.71, p < 0.0001) in the skin of workers were correlated with the log-transformed product of air concentration and painting time. The other polyisocyanates were detected on skin for less than 25% of the paint tasks. This LC-MS method provides a valuable tool to investigate inhalation and dermal exposures to specific polyisocyanates and to explore relative differences in the exposure pathways.     

Characterization of thermally generated aerosols from polyurethane foam

Isocyanates constitute a group of highly reactive chemicals used on a large scale for the production of flexible polyurethane (PUR) foam. Exposure to isocyanates is known to produce irritation of the mucous membranes and the eyes. Isocyanates also have strong sensitizing properties and may cause occupational asthma. It is therefore important to monitor isocyanate emissions at workplaces. To obtain information for the improvement of isocyanate samplers and for health risk assessments of exposure, the emitted aerosol from two types of flexible PUR foam subjected to thermal degradation was characterized. Particle size distribution and toluene diisocyanate (TDI) concentration in the emitted aerosols were measured. Thermal degradation of flexible PUR foam at temperatures from 250 to 300 degrees C produced an aerosol with a geometric mean particle diameter of 30-50 nm. Between 5% and 9% of the PUR foam was emitted as TDI, and 2% to 6% of TDI monomers were found in the particle phase under the experimental conditions used. The 2,6-TDI isomer was more abundant in the gas phase than in the particle phase.     

A chemosorptive cylindrical denuder designed for personal exposure measurements of isocyanates-evaluation on generated aerosols of 4,4'-methylenediphenyl diisocyanate

A denuder/filter system constructed for solvent-free personal exposure measurements was evaluated for separation of vapour and particulate 4,4'-methylenediphenyl diisocyanate (4,4'-MDI) generated from heated PUR-foam. The two different phases were collected in the denuder and on the filter, respectively, by chemosorption on a polydimethylsiloxane (SE-30)-dibutylamine (DBA) stationary phase. Both repeatability and the total mass concentration of 4,4'-MDI were similar to that obtained from the reference method, in this case an impinger/filter system. The penetration of particles through the denuder at 300 ml min(-1) was nearly 100% in the particle size range 25 to 700 nm, which fits well with the Gormley-Kennedy equation. Denuder/filter sampling of the 4,4'-MDI aerosol at 500 ml min(-1) yielded a phase distribution that was in accordance with the results from the reference method. The method limit of detection was 6 ng m(-3) and 4 ng m(-3) for the denuder and filter, respectively, when using an air sampling flow rate of 300 ml min(-1) and a sampling period of 15 min. This is well below the Swedish occupational exposure limit (OEL) of 50 and 100 microg m(-3) for an 8-hour working day and a 5-min period, respectively.     

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.     

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 laboratory investigation of the effectiveness of various skin and surface decontaminants for aliphatic polyisocyanates

Isocyanates may cause contact dermatitis and respiratory sensitization leading to asthma. Dermal exposure to aliphatic isocyanates in auto body shops is very common. However, little is known about the effectiveness of available commercial products used for decontaminating aliphatic polyisocyanates. This experimental study evaluated the decontamination effectiveness of aliphatic polyisocyanates for several skin and surface decontaminants available for use in the auto body industry. The efficiency of two major decontamination mechanisms, namely (i) consumption of free isocyanate groups via chemical reactions with active hydrogen components of the decontaminant and (ii) physical removal processes such as dissolution were studied separately for each decontaminant. Considerable differences were observed among surface decontaminants in their rate of isocyanate consumption, of which those containing free amine groups performed the best. Overall, Pine-Sol(R) MEA containing monoethanolamine was the most efficient surface decontaminant, operating primarily via chemical reaction with the isocyanate group. Polypropylene glycol (PPG) had the highest physical removal efficiency and the lowest reaction rate with isocyanates. All tested skin decontaminants performed similarly, accomplishing decontamination primarily via physical processes and removing 70-80% of isocyanates in one wiping. Limitations of these skin decontaminants are discussed and alternatives presented. In vitro testing using animal skins and in vivo testing with field workers are being conducted to further assess the efficiency and identify related determinants.     

Determination of isocyanates, aminoisocyanates and amines in air formed during the thermal degradation of polyurethane

An air sampling method for the determination of isocyanates, aminoisocyanates and amines formed during the thermal degradation of polyurethane (PUR) is presented. The method is based on the collection of air samples using impinger flasks containing di-n-butylamine (DBA) in toluene with a glass fibre filter in series. Isocyanates are derivatized with DBA to urea derivatives, and amines are derivatized in a subsequent work-up procedure with ethyl chloroformate (ET) to carbamate esters. Amine, aminoisocyanate and isocyanate derivatives were characterized using liquid chromatography-time of flight mass spectrometry (LC-TOFMS) and liquid chromatography-chemiluminescent nitrogen detection (LC-CLND). Quantification was performed by LC-MS, monitoring molecular ions [MH]+ in the electrospray mode. The instrumental detection limits for amines, aminoisocyanates and isocyanates were in the ranges 30-40, 2-3 and 3-70 fmol, respectively. Thermal degradation products of PUR were observed in high concentrations during welding in district heating pipes and PUR-coated metal sheets. Eleven isocyanates, three amines and five aminoisocyanates were identified. The concentrations of isocyanates, aminoisocyanates and amines in samples collected in the smoke close to the welding spot were in the ranges 150-650, 4-290 and 1-70 ppb, respectively. In samples collected in the breathing zone, isocyanates and aminoisocyanates were observed in the ranges 9-120 and 4-19 ppb, respectively. The compounds were present in both gas and particle phases. Volatile compounds dominated in the gas phase, whereas less volatile compounds dominated in the particle phase. The method presented makes it possible to sample and determine amines and aminoisocyanates, in addition to isocyanates. The need to monitor these compounds is clearly illustrated by the high concentrations found during the thermal degradation of PUR.     

Protein adducts as biomarkers of exposure to aromatic diisocyanates in workers manufacturing polyurethane (PUR) foam

This work was undertaken to investigate the usefulness of diisocyanate-related protein adducts in blood samples as biomarkers of occupational exposure to toluene diisocyanate (TDI; 2,4- and 2,6-isomers) and 4,4'-methylenediphenyl diisocyanate (MDI). Quantification of adducts as toluene diamines (TDAs) and methylenedianiline (MDA) was performed on perfluoroacylated derivatives by gas chromatography-mass spectrometry (GC-MS/MS) in negative chemical ionisation mode. TDI-derived adducts were found in 77% of plasma and in 59% of globin samples from exposed workers manufacturing flexible polyurethane foam. The plasma levels ranged from 0.003 to 0.58 nmol mL(-1) and those in globin from 0.012 to 0.33 nmol g(-1). The 2,6-isomer amounted to about two-thirds of the sum concentration of TDA isomers. MDI-derived adducts were detected in 3.5% of plasma and in 7% of globin samples from exposed workers manufacturing rigid polyurethane foam. A good correlation was found between the sum of TDA isomers in urine and that in plasma. The relationship between globin adducts and urinary metabolites was ambiguous. Monitoring TDI-derived TDA in plasma thus appears to be an appropriate method for assessing occupational exposure. Contrary to TDI exposure, adducts in plasma or globin were not useful in assessing workers' exposure to MDI. An important outcome of the study was that no amine-related adducts were detected in globin samples from TDI- or MDI-exposed workers, alleviating concerns that TDI or MDI might pose a carcinogenic hazard. Further studies are nevertheless required to judge whether diisocyanates per se could be such a hazard.     

Evaluation of the NIOSH draft method 5525 for determination of the total reactive isocyanate group (TRIG) for aliphatic isocyanates in autobody repair shops. National Institute for Occupational Safety and Health

This paper evaluates the performance of the NIOSH draft method 5525 for analysis of monomeric and TRIG aliphatic isocyanates in autobody repair shops. It was found that an optimized pH gradient enhanced noticeably the resolution and, therefore, identification of aliphatic isocyanates. Samples proved to be very stable for at least a year when stored at -13 degrees C in the freezer, and no major stability problems were found for the MAP reagent. The detector response factor RSD for selected MAP ureas was 40% in the fluorescence (FLD), 3% in the UV at 254 nm (UV254), and 1% in the UV at 370 nm (UV370). The mean FLD/UV254 and UV254/UV370 detector response ratios of standards were 31.7 (RSD = 37.8) and 17.1 (RSD = 5.4), respectively. The FLD/UV254 ratio in bulks varied from 0.41 to 1.97 times the HDI monomer ratio. The mean UV254/UV370 ratio in bulks was 16.1 (range 14.1 to 19.2, N = 38). Mean (range) recovery of 92 (91.2-93.2)% was found for the N3300 (isocyanurate) spiked on 25 mm quartz fiber filters in the range 0.07 to 2.2 microg NCO ml(-1). Mean (range) recovery for impingers was 100.7 (91.7-106.0)% for N3300 in the concentration range of 0.018 to 2.5 microg NCO ml(-1) and 81.0 (76.1-89.1)% for IPDI in the concentration range of 0.016 to 1.87 microg NCO ml(-1). Analytical method precision was 3.4% and mean bias 7.4% (range = 0-25%). The NIOSH draft method 5525 provides flexibility, enhanced sensitivity and specificity, powerful resolution, and very small compound-to-compound variability in the UV254, resulting in a more reliable identification and quantification of aliphatic isocyanates.     

Survey of the occurrence of residues of methyl tertiary butyl ether (MTBE) in Dutch drinking water sources and drinking water

An indicative survey has been carried out in The Netherlands investigating the presence of methyl tertiary butyl ether (MTBE) in drinking water and the corresponding sources. In total, 71 different sites used for the preparation of drinking water in The Netherlands were sampled in two successive seasons in 2001 involving the analysis of 156 samples. (ground water (n = 88), surface water (n = 17), bank filtrate water (n = 6) and drinking water (n = 45)). To combine high sample throughput with high selectivity and sensitivity, off-line purge and trap for sampling and gas chromatography mass spectrometry equipped with an automated thermal desorption sampler (TDS-GC-MS) was selected as the preferred analytical methodology. The developed procedure enabled the analysis of at least 40 samples per day and provided a limit of quantification of 2 ng l(-1). In the first period 63 samples of raw water were analyzed. Concentrations ranged between < 10 ng l(-1) and 420 ng l(-1) with a median concentration below 10 ng l(-1). The second period was focused at the re-sampling of positive locations (MTBE > 10 ng l(-1)) and a few additional drinking water utilities of which both the raw and drinking water of the utilities were analyzed. The median concentration of MTBE in the selected set of drinking water samples was 20 ng l(-1) (n = 45). At one location MTBE was found at a level of 2900 ng l(-1) caused by point source contamination of the ground water (11 900 ng l(-1)). Special attention has been paid to the quality of the results by analyzing all samples in duplicate and the analysis of control samples during each series of analyses.     

Validation of a standardized portable fluorescence method for determining trace beryllium in workplace air and wipe samples

Beryllium is widely used in industry for its unique properties; however, occupational exposure to beryllium particles can cause potentially fatal disease. Consequently, exposure limits for beryllium particles in air and action levels on surfaces have been established to reduce exposure risks for workers. Field-portable monitoring methods for beryllium are desired in order to facilitate on-site measurement of beryllium in the workplace, so that immediate action can be taken to protect human health. In this work, a standardized, portable fluorescence method for the determination of trace beryllium in workplace samples, i.e., air filters and dust wipes, was validated through intra- and inter-laboratory testing. The procedure entails extraction of beryllium in 1% ammonium bifluoride (NH(4)HF(2), aqueous), followed by fluorescence measurement of the complex formed between beryllium ion and hydroxybenzoquinoline sulfonate (HBQS). The method detection limit was estimated to be less than 0.02 microg Be per air filter or wipe sample, with a dynamic range up to greater than 10 microg. The overall method accuracy was shown to satisfy the accuracy criterion (A< or = +/-25%) for analytical methods promulgated by the US National Institute for Occupational Safety and Health (NIOSH). Interferences from numerous metals tested (in >400-fold excess concentration compared to that of beryllium) were negligible or minimal. The procedure was shown to be effective for the dissolution and quantitative detection of beryllium extracted from refractory beryllium oxide particles. An American Society for Testing and Materials (ASTM) International voluntary consensus standard based on the methodology has recently been published.     

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.     

A pilot study on the determination of perfluorooctanesulfonate and other perfluorinated compounds in blood of Canadians

A pilot study was conducted to provide preliminary data on the concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorooctanesulfonamide (PFOSA) in the blood of Canadians. A set of 56 human serum samples was collected from non-occupationally exposed Canadians and analyzed by microbore HPLC-negative ion electrospray tandem mass spectrometry. PFOS was the main component of perfluorinated organic compounds (PFCs) and was detected in all 56 blood specimens at an average concentration of 28.8 ng mL(-1) and a range from 3.7 to 65.1 ng mL(-1). The concentration of PFOA was an order of magnitude lower than that of PFOS and was found only in 16 samples (29%) at concentrations above the limit of quantification (LOQ). PFOSA was not detected at levels above the method detection limit (MDL) in any of the samples. The levels of PFCs observed in the sample group of non-occupationally exposed humans in Canada were similar to the levels reported in a previous US study with a similar sample pool size. Two distinct PFOS isomers in human serum were identified by accurate mass determination.     

Development of a solid phase microextraction (SPME) method for the sampling of VOC traces in indoor air

Solid-phase microextraction (SPME) was studied for the measurement of volatile organic compounds (VOCs) in indoor air. An adsorptive PDMS/Carboxen fibre was used and an analytical methodology was developed in order to overcome competitive adsorption. Kinetics and adsorption isotherms were investigated for different sample volumes and model compounds. In order to evaluate competitive adsorption on the fibre, these compounds were studied alone and in mixture. From the results obtained, the operating conditions allowing co-adsorption of the target compounds were determined: the air sample is enclosed in a 250 mL glass bulb where the SPME fibre is exposed until adsorption equilibrium. This procedure was combined with GC/MS analysis for the identification and quantification of VOCs in indoor air. The performances were determined by using a standard gas containing 10 VOCs representative of indoor environments (acetaldehyde, acetone, BTX, alpha-pinene, trichloroethylene, alkanes). The detection limits were determined in single ion monitoring mode and for a signal to noise ratio of 3. Except acetaldehyde (6 microg m(-3)), they are all below 0.5 microg m(-3). Calibration curves are linear up to 10 micromol m(-3) for all the compounds with good correlation coefficients (above 0.99). The reproducibility ranges from 6 to 12% according to the compound. The methodology was then applied to the comparison of the VOCs content in classrooms of two different schools.     

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.     

Environmental and biological monitoring of methyl ethyl ketone (MEK)

This study was conducted to evaluate the usefulness of various biological parameters for monitoring of workers exposed to methyl ethyl ketone (MEK). Fifty male workers from a large magnetic videotape factory participated in this study. Personal air samples were collected using 3M organic vapor monitors and analysed for MEK by gas chromatography with flame ionisation detector (FID). 10 mL of urine; blood (1 mL) and exhaled air were also collected at the end of an 8-hour workshift. The headspace GC method was applied for measurement of urinary and blood MEK. MEK in expired air was analysed directly by using a GC/FID.The correlation coefficients (r) between environmental MEK and all other biological parameters measured show significant positive relationships. The r for environmental MEK and urine MEK was 0.84; for blood 0.73 and for breath 0.64. The correlation coefficients between blood and urine was 0.72; blood and breath was 0.88 and urine and breath 0.60. These findings suggest that measurements of unmetabolised MEK in blood, exhaled air and urine can be used for biological monitoring of MEK exposure. Nevertheless, laboratory methodological assessment is in favour of measuring urinary MEK as it is non-invasive and does not have to be analysed immediately after collection.