Comprehensive methylene diphenyl diisocyanate (MDI) evaluation method comparison using a laboratory generation system.

Isocyanates are reactive semivolatile contaminants that must be assessed in occupational environments, and specific evaluation methods are required to address the challenges related to isocyanate emission characteristics. Several standard methods exist, but significant differences remain regarding the diversity of industrial isocyanate emissions. This study presents a method to establish a baseline comparison of three sampling principles. A fine aerosol (mass median aerodynamic diameter of 250 nm) of pure methylene diphenyl diisocyanate (MDI) was produced (5-60 µg m-3) using a laboratory generation system (n = 31 generation experiments). Airborne MDI was measured with the following four methods, with an emphasis on the spatial distribution of the collected MDI within the sampler: (1) Swinnex cassette 13 mm, glass fibre filter (GFF), 9-(N-methylaminomethyl) anthracene (MAMA-Swin); (2) closed-face cassette (CFC) 37 mm, GFF (end filter and inner walls), MAMA-37; (3) impinger and backup GGF, 1,2-methoxyphenylpiperazine (MP) (ISO 16702/MDHS 25); and (4) denuder and GFF (Asset EZ4-NCO), dibutylamine (DBA) (ISO 17334-1). Bland and Altman analyses determined that there were no significant bias between the methods although Asset was not in agreement with MAMA-Swin (95% confidence interval above the ±20% criteria). Significant correlations (P < 0.05) were observed between airborne MDI concentration levels and their distribution within the Asset (denuder vs. end filter) and impinger (collecting solution vs. backup filter) subsections. The presence of impregnated inner walls in the CFC did not increase collection efficiency for the generated MDI aerosol. Non-uniform MAMA impregnation on GFF was demonstrated, whereas the collected MDI was evenly distributed in the air samples. These results provided the basis of comparison for other studies involving more complex isocyanate emissions.

Development and characterization of an adaptable aerosolized methylene diphenyl diisocyanate generation system.

Reactive semivolatile contaminants, such as isocyanates, can be particularly difficult to assess in occupational environments. While standard methods exist for isocyanates, there are still significant differences between the results they provide for various occupational environments or processes. This study presents the validation of a laboratory system for the generation of controlled atmospheres of isocyanates. A system consisting of different modules generated airborne methylene diphenyl diisocyanate (MDI) by nebulizing a solution into mixing and exposure chambers with control of flow rate, temperature, and relative humidity. Sampling was performed through an eight-port flow splitter that allowed only very slight within-test variability. MDI was measured using the Asset EZ4-NCO® and a modified version of the Iso-Chek® sampling system. MDI specific particle-size distribution was measured by a Marple Sierra cascade. Aerosol real-time monitoring was performed using a condensation particle counter, an electrical low-pressure impactor (ELPI+), and an aerosol optical spectrometer, providing additional information on system stability and particle-size distribution of the generated aerosol. The system was able to generate MDI concentration levels ranging from 4 to 233 µg m-3, with a steady-state level reached within 5 minutes, and with well-documented intra-test and inter-test variability (RSD of 4% and 15%, respectively). Accuracy and representativeness of MDI data were confirmed by the agreement between MAMA and Asset EZ4-NCO (used as reference), with a mean bias of 3%. Using the Asset EZ4-NCO capability, the vapor-particle partitioning of MDI was evaluated to be 8% and 92%, respectively, at a concentration ranging from 20 to 25 µg m-3. The system may therefore be used for exhaustive method intercomparison studies and could also be adapted to generate other emission types of semivolatile compounds.

On-site comparison of the OSHA 47, Asset EZ4-NCO, Iso-Chek, DAN, and CIP10 methods for measuring methylene diphenyl diisocyanate (MDI) at an oriented-strand board (OSB) factory.

Diisocyanates are occupational contaminants and known sensitizers causing irritation (skin and respiratory tract) as well as occupational asthma. Because of their physicochemical properties (semi-volatile and high reactivity) and low occupational limits, diisocyanate exposure evaluation is still a challenge nowadays for industrial hygienists and laboratories. The objective of this study was to compare the methylene diphenyl diisocyanate (MDI) concentrations measured by five methods using different collection or derivatization approaches in an oriented-strand board (OSB) factory. The methods used were: OSHA 47 (filter, 1-(2-pyridyl)piperazine) (OSHA), Asset EZ4-NCO (denuder and filter, dibutylamine) (Asset), Iso-Chek (double-filter, 9-(N-methylaminomethyl) anthracene and 1,2-methoxyphenylpiperazine), DAN (filter, 1,8-diaminonaphthalene), and CIP10 (centrifugation, 1,2-methoxyphenylpiperazine). Real-time monitoring of particle concentration and size distribution was performed to explain the potential bias between methods. The comparison study was performed over 3 consecutive days, generating at least 18 replicates for each of the 5 methods. The results of each methods were compared using linear mixed effect modeling. Compared to Asset, which yielded the highest concentrations overall, the OSHA method provided the smallest bias with -18% (95% CI [-61;24]) (not significant) for MDI monomer and the DAN method provided the smallest bias with -30 (95% CI [-70;9]) (not significant) for Total Reactive Isocyanate Group (TRIG). The CIP10 and Iso-Chek methods provided the largest biases for MDI monomer (-83% (95% CI [-115;-51]) and -78% (95% CI [-110;-46]), respectively) as well as for TRIG (-87% (95% CI [-120;-55]) and -75% (95% CI [-107;-44]), respectively). The underestimations of the CIP10 and Iso-Chek were explained by its inefficient sampling principle for fines particles and the use of a non-impregnated filter to collect aerosol MDI, respectively. This study confirms that impregnated filter, including denuding device such as the Asset EZ4-NCO sampler, collects the MDI-coated wood particles and MDI vapor with similar efficiency. It also demonstrates for the first time in this type of MDI emission a significant agreement for TRIG concentration between the DAN method in the impregnated filter configuration and an international standard one such as Asset.

On site comparison of the OSHA 42, Asset EZ4-NCO, Iso-Chek, DAN and CIP10 methods for measuring toluene diisocyanate (TDI) at a polyurethane foam factory.

Because of the semi-volatile nature of diisocyanates (being airborne in both physical vapor and particulate phases), their high reactivity and low occupational exposure limits, diisocyanate exposure evaluation has been challenging for industrial hygienists and laboratories. The objective of this study was to compare the toluene diisocyanate (2,4 and 2,6 isomers, TDI) concentration measured by five methods in a flexible polyurethane foam factory using different collection or derivatization approaches. The methods used were: OSHA 42 modified (filter, 1-(2-pyridyl)piperazine) (OSHA), Asset EZ4-NCO (denuder and filter, dibutylamine) (Asset), Iso-Chek (double-filter, 9-(N-methylaminomethyl) anthracene and 1,2-methoxyphenylpiperazine), DAN (filter, 1,8-diaminonaphthalene), and CIP10 (centrifugation, 1,2-methoxyphenylpiperazine). Particle real-time monitoring for concentration and size distribution was performed in parallel to improve the understanding of the potential bias between methods. The comparison study was performed over 3 days, providing 18 replicates for each of the 5 methods. Isocyanate concentrations collected for each sampling method were compared using linear mixed effect modeling. Compared to OSHA, which yielded the highest concentrations overall, the Asset and DAN methods provided the smallest biases (-29% (95% CI [-52;-6]) and -45% (95% CI [-67;-23]), respectively), while the CIP10 and Iso-Chek methods provided the largest biases (-82% (95% CI [-105;-66]) and -96% (95% CI [-118;-75]), respectively). The substantial bias of Iso-Chek and CIP10 seemed to be explained by the predominance of TDI in the form of sub-micron particles that were inadequately captured by these two methods due to their sampling principle, which are particle filtration without derivatizing agent and centrifugation respectively. Asset and DAN performance seemed to decrease as the sampling time increased. While DAN's bias could be related to a reagent deficiency on the filter, the disparities between OSHA and Asset, both considered as reference methods, highlight the fact that the mechanisms of collection, derivation and extraction do not seem to be completely controlled. Finally, an upward trend has been observed between concentrations of particles below 300 nm in size and concentration levels of TDI. It has also been observed that TDI levels increased with the TDI foam index produced at the facility.

Development of a method for quantification of toluene diisocyanate and methylenediphenyl diisocyanate migration from polyurethane foam sample surface to artificial sweat by HPLC-UV-MS.

The US Environmental protection agency (EPA) has published guidance that includes test procedures for evaluating indoor exposure to chemicals from products. One of the test procedures represents the migration test for evaluating potential dermal exposure from home furniture. Such an evaluation involves the chemical measurement of the sweat which is currently unavailable in the literature. The objective of this project was to develop and validate an analytical method for quantification of migration of 4,4'-methylenediphenyl diisocyanate (MDI), 2,6-toluene diisocyanate (2,6-TDI) and 2,4-toluene diisocyanate (2,4-TDI) from a polyurethane (PU) flexible foam to artificial sweat that meets the recommendations of the EPA test protocol. Following the EPA protocol, six synthetic sweat solutions were prepared and used in evaluation of isocyanate recovery performance. The migration tests were conducted using five foam types that were chosen and supplied by PU foam manufacturers to represent the types most commonly found in commercial products, and with formulations anticipated to have the highest potential residual TDI or MDI. Migration tests were conducted using glass fiber filters (GFF) coated with 1-(2-methoxyphenyl)piperazine (1,2-MP) and analyzed using HPLC equipped with a UV detector for quantification and a MS detector to qualify peaks. The detection limits of the method were 0.002 µg/mL for 2,6-TDI, 0.011 µg/mL for 2,4-TDI, and 0.003 µg/mL for MDI. Quantification limits were 0.006 µg/mL, 0.037 µg/mL, and 0.010 µg/mL, respectively. The recovery tests on a Teflon surface for 5 of the 6 EPA-recommended synthetic sweat solutions indicate the recovery percentage was approximately 80% for diisocyanates. Recovery for the sixth sweat solution was low, approximately 30%. TDI and MDI migration was not observed when testing was conducted on foam samples.

Assessment of Occupational Exposure to Organic Flame Retardants: A Systematic Review.

BACKGROUND: Flame retardants (FRs) are widespread in common goods, and workers in some industries can be exposed to high concentrations. Numerous studies describe occupational exposure to FRs, but the diversity of methods and of reported results renders their interpretation difficult for researchers, occupational hygienists, and decision makers. OBJECTIVES: The objectives of this paper are to compile and summarize the scientific knowledge on occupational exposure to FRs as well as to identify research gaps and to formulate recommendations. METHODS: Five databases were consulted for this systematic literature review (Embase, Medline [Pubmed], Global health, Web of Science, and Google Scholar), with terms related to occupational exposure and to FRs. Selected studies report quantitative measurements of exposure to organic FRs in a workplace, either in air, dust, or in workers' biological fluids. The Preferred Reporting Items for Systematic reviews and Meta-Analyses statement guidelines were followed. RESULTS: The search yielded 1540 published articles, of which 58 were retained. The most frequently sampled FRs were polybrominated diphenyl ethers and novel brominated FRs. Offices and electronic waste recycling facilities were the most studied occupational settings, and the highest reported exposures were found in the latter, as well as in manufacturing of printed circuit boards, in aircrafts, and in firefighters. There were recurrent methodological issues, such as unstandardized and ill-described air and dust sampling, as well as deficient statistical analyses. CONCLUSIONS: This review offers several recommendations. Workplaces such as electronic waste recycling or manufacturing of electronics as well as firefighters and aircraft personnel should be granted more attention from researchers and industrial hygienists. Methodical and standardized occupational exposure assessment approaches should be employed, and data analysis and reporting should be more systematic. Finally, more research is needed on newer chemical classes of FRs, on occupational exposure pathways, and on airborne FR particle distribution.

Diesel engine exhaust exposure in underground mines: Comparison between different surrogates of particulate exposure.

Exposure to diesel particulate matter (DPM) is frequently assessed by measuring indicators of carbon speciation, but these measurements may be affected by organic carbon (OC) interference. Furthermore, there are still questions regarding the reliability of direct-reading instruments (DRI) for measuring DPM, since these instruments are not specific and may be interfered by other aerosol sources. This study aimed to assess DPM exposure in 2 underground mines by filter-based methods and DRI and to assess the relationship between the measures of elemental carbon (EC) and the DRI to verify the association of these instruments to DPM. Filter-based methods of respirable combustible dust (RCD), EC, and total carbon (TC) were used to measure levels of personal and ambient DPM. For ambient measurements, DRI were used to monitor particle number concentration (PNC; PTrak), particle mass concentration (DustTrak DRX and DustTrak 8520), and the submicron fraction of EC (EC1;Airtec). The association between ambient EC and the DRI was assessed by Spearman correlation. Geometric mean concentrations of RCD, respirable TC (TCR) and respirable elemental EC (ECR) were 170 µg/m3, 148 µg/m3, and 83 µg/m3 for personal samples, and 197 µg/m3, 151 µg/m3, and 100 µg/m3 for ambient samples. Personal measurements had higher TCR:ECR ratios compared to ambient samples (1.8 vs. 1.50) and weaker association between ECR and TCR. Among the DRI, the measures of EC1 by the Airtec (ρ = 0.86; P < 0.001) and the respirable particles by the DustTrak 8520 (ρ = 0.74; P < 0.001) showed the strongest association with EC, while PNC showed a weak and non-significant association with EC. In conclusion, this study provided important information about the concentrations of DPM in underground mines by measuring several indicators using filter-based methods and DRI. Among the DRI, the Airtec proved to be a good tool for estimating EC concentrations and, although the DustTrak showed good association with EC, interferences from other aerosol sources should be considered when using this instrument to assess DPM.

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.

Determination of triglycidyl isocyanurate from air samples by ultra-performance liquid chromatography coupled with coordination ion spray mass spectrometry.

RATIONALE: Ultra-performance liquid chromatography (UPLC) coupled with coordination ion spray tandem mass spectrometry was used for the analysis of air samples containing triglycidyl isocyanurate. The method is not affected by any chromatographic interference and the filter extract is compatible with the UPLC system, as opposed to approaches using high-performance liquid chromatography coupled with ultraviolet detection and gas chromatography coupled with mass spectrometry. METHODS: Accu-cap™ filters that had sampled triglycidyl isocyanurate were extracted using a mixture of acetonitrile/acetone (95/5) diluted with 3 volumes of water and were then analyzed. The mass spectrometry method uses sodium as the alkali adduct complexing with the triglycidyl isocyanurate in positive mode, and this complex is then analyzed using the survivor mode where the same ion is monitored in the first and third quadrupoles of a triple quadrupole mass spectrometer. RESULTS: The method has a limit of detection and limit of quantitation of 50 and 170 ng/filter, respectively. The dynamic range was between 480 and 24,000 ng/sample, which is equivalent to 2 µg/m(3) and 100 µg/m(3) based on a sampling volume of 240 L. The intra- and inter-day precisions were both <4% and the overall accuracy was 97 ± 3%. The method was tested with personal breathing zone random samples collected from workers using triglycidyl isocyanurate in their tasks, and all the random samples were easily quantified. CONCLUSIONS: A new method by UPLC coupled with coordination ion spray tandem mass spectrometry using sodium as the alkali adduct is now available for industrial hygienists who want to evaluate exposures of workers to triglycidyl isocyanurate in workplaces.

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.