Use of the Novel Derivatizing Agent 1,8-Diaminonapthalene With the CIP10 Sampler to Measure 4,4'-Methylene Diphenyl Diisocyanate Atmospheres.

DAN is a novel derivatizing agent for isocyanate sampling which targets total reactive isocyanate group (TRIG). Field evaluations have been conducted for 4,4'-Methylene diphenyl diisocyanate (MDI) sampling using DAN as the derivatizing agent in a CIP10. The perimidone formed, selective of TRIG, was analyzed in laboratory by liquid chromatography coupled to tandem mass spectrometry. Workplaces using MDI-based polyurethane spray foam and MDI wood product binder were studied. Each study compared the data obtained between the CIP10/DAN, the CIP10/MP, and a reference method. As a first evaluation, the CIP10/DAN sampled simulated MDI spray foam atmosphere in parallel with impingers (reference method) and CIP10/MP. The mean of the TRIG concentration values measured was 16% (95% confidence interval [CI], [1, 31]) higher for the CIP10/MP samples as compared to the impinger samples, while the mean TRIG concentrations found were 98% (95% CI [63, 133]) higher for the CIP10/DAN samples as compared to the impinger samples. For sampling done in a real workplace using MDI-based spray foam, the CIP10/DAN method showed lower results than the CIP10/MP method. The presence of hygroscopic DMSO used in the DAN approach is a limitation and may prevent obtaining accurate results in the spray foam atmosphere. CIP10/DAN was also studied in MDI wood product binder atmosphere. Mean TRIG concentrations found were 80% (95% CI [51, 110]) and 79% (95% CI [50, 108]) lower for the CIP10/MP and CIP10/DAN method, respectively, as compared to the reference method (a 13-mm filter coated with MP). In this case, the CIP10 may have reached its limit in this last evaluation where vapors and particles below 1 µm were not collected as efficiently as they were with the reference method.

Implementation and evaluation of an analytical method for a novel derivatizing agent to measure 4,4'-methylene diphenyl diisocyanate atmospheres.

Accurate measurement of 4,4'-methylene diphenyl diisocyanate (MDI) atmospheres is a challenge since the molecule is both chemically reactive and likely to be present in aerosol form when heated and sprayed because of its low vapor pressure. Meeting this challenge requires optimizing both the sampling device used and the derivatization agent employed to stabilize the isocyanate functional group. This study describes the use of a novel derivatization reagent for isocyanate sampling to address the challenge of MDI aerosol exposure sampling. Like most conventional derivatizing agents for isocyanates, 1,8-diaminonapthalene (DAN) reacts with isocyanate functional groups to form a urea. However, unlike other isocyanate derivatizing agents, the sample workup procedure with DAN includes a second step which yields a single analyte molecule, perimidone, for each isocyanate group. This feature gives DAN the unique ability to assess exposure to "total reactive isocyanate group" (TRIG). The analytical method implemented to quantitate the perimidone uses liquid chromatography coupled with tandem mass spectrometry. Positive mode ionization led to LOD and LOQ of 10 ng/mL and 34 ng/mL, respectively. The dynamic range was from 50-2000 ng/mL (with R(2) ≥ 0.990), which corresponds to TRIG concentrations in air from 0.07-3.04 µg/m(3), assuming 60 min of sampling at 10 L/min (based on use of the CIP-10M sampler). The intra-day and inter-day analytical precisions were <4% for all of the concentration levels tested, and the accuracy was within an appropriate range of 98 ± 2%. Minimal matrix effect was observed, and a total recovery of 109% was obtained. The approach seems to be promising for TRIG measurements and further work is planned to establish DAN method behavior in samplers used for workplace monitoring.

Comparison between the ASSET EZ4 NCO and Impinger Sampling Devices for Aerosol Sampling of 4,4'-Methylene Diphenyl Diisocyanate in Spray Foam Application.

4,4'-methylene diphenyl diisocyanate (MDI) aerosol exposure evaluation in spray foam insulation application is known to be a challenge. Current available techniques are either not user-friendly or are inaccurate or are not validated for this application. A new sampler has recently been developed to address the user-friendliness issues with other samplers: the ASSET EZ4-NCO, but the use of this sampler in spray foam insulation applications has not been demonstrated or validated. Because of this, the current work was undertaken to provide a comparison of the ASSET sampler with an impinger method, considered to be the best available method in the context of spray foam insulation, and hence the pertinence of comparing this sampler to an impinger method, considered to be the best available method for measuring MDI monomer and oligomers for this particular application. Liquid chromatography coupled with tandem mass spectrometry method for MDI monomer and oligomer analysis was implemented based on the Supelco literature. It allows the analysis of MDI-dibutylamine (DBA) and MDI 3-ring-DBA with a minimum reported value of 5ng ml(-1), a dynamic range of 5-140ng ml(-1), precision <15% and accuracy >80%. This method was used to quantify MDI aerosols collected with the ASSET sampler in an MDI spray foam environment in parallel with the toluene/MOPIP impinger reference method. The ASSET sampler significantly underestimated the levels of MDI monomer and oligomers when compared to the reference method. The estimated bias was 72% (95% confidence interval [CI] 54-89%) for the monomer and 96% (95% CI 76-115%) for the oligomers. These results demonstrate the importance of evaluating each new sampler for each isocyanate application prior to a formal worker exposure evaluation.

CIP10 optimization for 4,4-methylene diphenyl diisocyanate aerosol sampling and field comparison with impinger method.

4,4-methylene diphenyl diisocyanate (MDI) aerosol exposure evaluation in spray foam insulation application is known as being a challenge because the spray foam application actually involves a fast-curing process. Available techniques are either not user-friendly or are inaccurate or not validated for this application. To address these issues, a new approach using a CIP10M was developed to appropriately collect MDI aerosol in spray foam insulation while being suitable for personal sampling. The CIP10M is a commercially available personal aerosol sampler that has been validated for the collection of microbial spores into a liquid medium. Tributylphosphate with 1-(2-methoxyphenyl)piperazine (MOPIP) was introduced into the CIP10M to collect and stabilize the MDI aerosols. The limit of detection and limit of quantification of the method were 0.007 and 0.024 µg ml(-1), respectively. The dynamic range was from 0.024 to 0.787 µg ml(-1) (with R (2) ≥ 0.990), which corresponds to concentrations in the air from 0.04 to 1.3 µg m(-3), assuming 60 min of sampling at 10 l min(-1). The intraday and interday analytical precisions were <2% for all of the concentration levels tested, and the accuracy was within an appropriate range of 98 ± 1%. No matrix effect was observed, and a total recovery of 99% was obtained. Parallel sampling was performed in a real MDI foam spraying environment with a CIP10M and impingers containing toluene/MOPIP (reference method). The results obtained show that the CIP10M provides levels of MDI monomer in the same range as the impingers, and higher levels of MDI oligomers. The negative bias observed for MDI monomer was between 2 and 26%, whereas the positive bias observed for MDI oligomers was between 76 and 113%, with both biases calculated with a confidence level of 95%. The CIP10M seems to be a promising approach for MDI aerosol exposure evaluation in spray foam applications.