Methylene diphenyl diisocyanate occupational exposure data in industry (1998-2020): A descriptive summary from an industrial hygiene perspective.

This paper provides an overview of airborne methylene diphenyl diisocyanate (MDI) concentrations in workplaces across North America and Europe. A total of 7649 samples were collected between 1998 and 2020 by producers of MDI during product stewardship activities at customer sites, primarily using validated OSHA or ISO sampling and analysis techniques. As would be expected from the low vapor pressure of MDI, 80% of the concentrations were less than 0.01 mg/m3 (1 ppb) and 93% were less than 0.05 mg/m3 (5 ppb). Respiratory protection is an integral part of Industrial Hygiene practices; therefore, its use was studied and summarized. While covering a variety of MDI applications, a large number of samples was obtained from composite wood manufacturing facilities, offering specific insight into potential exposures associated with different process sections and job types in this industry sector. Given the potential presence in industrial processes of MDI-containing dust or aerosols, future work should place increased emphasis on also investigating dermal exposure. The data reported in this paper provide valuable information for product stewardship and industrial hygiene purposes throughout the MDI-processing industry.

Development of a new SPE UPLC-MS/MS method for extraction and quantitation of toluene diamine on gloves following toluene diisocyanate exposure.

RATIONALE: Toluene diisocyanate (TDI) is a highly reactive isocyanate commonly used as a mixture of 2,4- and 2,6- isomers in the production of flexible foams. Exposure to TDI occurs primarily through vapour inhalation in workplaces where TDI is produced or used, but dermal exposure is also possible during some tasks. To ensure workplace safety, accurate monitoring of TDI and toluene diamine (TDA) levels is required. Methods of quantifying field effectiveness of gloves in preventing dermal exposure have not been established. Therefore, there is a need to develop a new practical method for assessing glove effectiveness for TDI/TDA. METHOD: A new offline SPE UPLC-MS/MS method for the quantitation of TDA isomers from TDI-exposed gloves was developed. Gloves were dipped in a solution of 1% acetic acid leading to a full conversion to TDA. TDA-free amine compounds were derivatized with acetic anhydride to increase chromatographic retention and signal intensity. RESULTS: 2,4-Diaminotoluene-α, α, α-d3 (2,4-d3 -TDA) was selected as a surrogate standard to minimise the variability in sample preparation and instrumental sensitivity. The choice of UPLC-MS/MS operated in multiple reaction monitoring (MRM) mode allowed to reach much lower limits of detection (LOD). The LOD of the method was 6.86 and 2.83 ng/mL (0.03 and 0.01 µg) for 2,6-TDA and 2,4-TDA, respectively. The limit of quantitation (LOQ) was 22.85 and 9.42 ng/mL (0.11 and 0.05 µg) for 2,6-TDA and 2,4-TDA, respectively. CONCLUSION: A new UPLC-MS/MS analytical method has been developed to determine field effectiveness of gloves for preventing dermal exposure to TDI/TDA. The new technique overcomes some limitations for measuring putative dermal exposure to isocyanates and may be useful in exposure monitoring and future research on isocyanate health risks.

Health effects of exposure to isocyanates in a car factory.

OBJECTIVES: Isocyanates are known to induce occupational diseases. The aim of this work was to assess the health effects of exposure to isocyanates and to test the sensitivity of selected parameters for early detection of isocyanate-related allergic diseases. METHODS: In total, 35 employees from one factory were tested: 26 workers exposed to isocyanates (exposed group) and nine office workers (control group). All subjects filled in a questionnaire regarding possible health problems. Fractional exhaled nitric oxide (FeNO) and spirometry were measured for each subject at the same time during two consecutive working days. A urine sample was taken for a biological exposure test (BET). RESULTS: No significant difference was found between the exposed and control groups for spirometry parameters and FeNO. However, in the exposed group, FeNO was highly elevated (> 50 ppb) in five subjects (all reporting health problems at the workplace, all with normal spirometry and non-smokers). The BET revealed a significant difference (p < 0.001) between the exposed and control groups for 4,4´-methylenediphenyl diamine (MDA) in the urine. CONCLUSIONS: Our examination showed the usefulness of the BET in monitoring of workplace exposure to isocyanates and the importance of FeNO in monitoring of allergic inflammation of airways in non-smoking employees with normal spirometry.

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.

Isocyanates and hydrogen cyanide in fumes from heated proteins and protein-rich foods.

Toxic compounds in cooking fumes could cause respiratory problems. In the present study, the formation of isocyanic acid (ICA), methyl isocyanate (MIC), and hydrogen cyanide (HCN) was studied during the heating of proteins or frying of protein-rich foods. Heating was performed in an experimental setup using a tube oven set at 200-500°C and in a kitchen when foods with different protein content were fried at a temperature around 300°C. ICA, MIC, and HCN were all generated when protein or meat was heated. Individual amino acids were also heated, and there was a significant positive correlation between their respective nitrogen content and the formation of the measured compounds. Gas from heated protein or meat also caused carbamylation in albumin. ICA, MIC, and HCN were also present in fumes generated when meat, egg, and halloumi were fried in a kitchen pan. The levels of ICA were here twice that of the Swedish occupational exposure limit. If ICA, MIC, and HCN in fumes from heated protein-rich foods could contribute to the risk of airway dysfunction among those exposed is not clear, but it is important to avoid inhaling frying and grilling fumes and to equip kitchens with good exhaust ventilation.

[Determination of diphenylmethane diisocyanate in workplace air by HPLC with impregnated filter membrane].

Objective: To develop a method for determining diphenylmethane diisocyanate in workplace air by HPLC with impregnated filter membrane. Methods: MDI in workplace air reacted with 1- (2-pyridyl) piperazine on impregnated filter membrane to form MDI-urea derivatives, after elution and filtration, it was detected by HPLC-UV. Results: Limit of detection was 0.003 8 µg/ml and limit of quantification was 0.013 µg/ml. Good linearity was obtained in the range of 0.013~2.000 µg/ml (r=0.999 7) . The precision was 3.10%~8.03% (n=6) , while the recovery was 96.3%~101.9%. Asorption capacity of the membrane was 40.8 µg MDI, and could be stored for 14 days in the light-proof environment of 2~8 ℃. Conclusion: The method optimized testing steps for MDI's standard curve, and provided good guidance for determination of MDI in workplace air with impregnated fiter membrane.

Analysis of isocyanates in indoor dust.

Isocyanates are harmful semi-volatile organic compounds that are emitted from various consumer products like polyurethane foam-based mattresses. Although it is a concern that isocyanates might accumulate in indoor dust, causing infants and toddlers, in particular, to be exposed to them, little information is available on the levels of isocyanates in the indoor environment. In this study, we investigated the suitability of an analytical method for determining the presence and level of isocyanates in the indoor dust. The method we developed displayed acceptable linearity, accuracy, and precision in the analysis of eleven different isocyanates. By using this analytical method, we could detect five isocyanates (ICA, MIC, EIC, PIC, and PHI) and quantify three isocyanates (MIC, EIC, and PHI) in indoor dust collected in different houses. This study is the first to focus on the pollution of indoor dust by isocyanates, and the tested method is suitable for the estimation of the level of isocyanate exposure. Graphical abstract ᅟ.

Wasabia koreana Nakai: A Preliminary Study on Nutrients and Chemical Compounds That May Impact Sensory Properties.

In this study, the nutritional, functional, and chemical measurements of sensory attributes of different parts of wasabi, namely, leaf, petiole, and rhizome, were investigated. Proximate composition analysis showed the presence of high amounts of carbohydrates in the rhizome and amino acid composition analysis confirmed high proportions of glutamic acid and aspartic acid in all three parts. While proximate composition showed low lipid content in wasabi, ω-3 fatty acids accounted for a high proportion (>44%) of the total lipids. Wasabi leaves had high vitamin C and total phenolic contents, and thus demonstrated antioxidant capacity. Allyl isothiocyanate, which gives wasabi its characteristic pungent taste, was identified by gas chromatography/mass spectrometry and an electronic nose. On an electronic tongue, wasabi leaves showed compounds associated with sourness and saltiness while the petiole had high content of compounds associated with sweetness and bitterness. This study provides basic data for the utilization of wasabi parts as food materials based on their nutritional, functional, and chemical measure of sensory attributes.

Effect of ventilation velocity on hexavalent chromium and isocyanate exposures in aircraft paint spraying.

Exposure control system performance was evaluated during aircraft paint spraying at a military facility. Computational fluid dynamics (CFD) modeling, tracer gas testing, and exposure monitoring examined contaminant exposure vs. crossflow ventilation velocity. CFD modeling using the RNG k-ϵ turbulence model showed exposures to simulated methyl isobutyl ketone of 294 and 83.6 ppm, as a spatial average of five worker locations, for velocities of 0.508 and 0.381 m/s (100 and 75 fpm), respectively. In tracer gas experiments, observed supply/exhaust velocities of 0.706/0.503 m/s (136/99 fpm) were termed full-flow, and reduced velocities were termed 3/4-flow and half-flow. Half-flow showed higher tracer gas concentrations than 3/4-flow, which had the lowest time-averaged concentration, with difference in log means significant at the 95% confidence level. Half-flow compared to full-flow and 3/4-flow compared to full-flow showed no statistically significant difference. CFD modeling using these ventilation conditions agreed closely with the tracer results for the full-flow and 3/4-flow comparison, yet not for the 3/4-flow and half-flow comparison. Full-flow conditions at the painting facility produced a velocity of 0.528 m/s (104 fpm) midway between supply and exhaust locations, with the supply rate of 94.4 m3/s (200,000 cfm) exceeding the exhaust rate of 68.7 m3/s (146,000 cfm). Ventilation modifications to correct this imbalance created a midhangar velocity of 0.406 m/s (80.0 fpm). Personal exposure monitoring for two worker groups-sprayers and sprayer helpers ("hosemen")-compared process duration means for the two velocities. Hexavalent chromium (Cr[VI]) exposures were 500 vs. 360 µg/m3 for sprayers and 120 vs. 170 µg/m3 for hosemen, for 0.528 m/s (104 fpm) and 0.406 m/s (80.0 fpm), respectively. Hexamethylene diisocyanate (HDI) monomer means were 32.2 vs. 13.3 µg/m3 for sprayers and 3.99 vs. 8.42 µg/m3 for hosemen. Crossflow velocities affected exposures inconsistently, and local work zone velocities were much lower. Aircraft painting contaminant control is accomplished better with the unidirectional crossflow ventilation presented here than with other observed configurations. Exposure limit exceedances for this ideal condition reinforce continued use of personal protective equipment.

An indoor air quality evaluation in a residential retrofit project using spray polyurethane foam.

Understanding of indoor air quality (IAQ) during and after spray polyurethane foam (SPF) application is essential to protect the health of both workers and building occupants. Previous efforts such as field monitoring, micro-chamber/spray booth emission studies, and fate/transport modeling have been conducted to understand the chemical exposure of SPF and guide risk mitigation strategies. However, each type of research has its limitation and can only reveal partial information on the relationship between SPF and IAQ. A comprehensive study is truly needed to integrate the experimental design and analytical testing methods in the field/chamber studies with the mathematical tools employed in the modeling studies. This study aims to bridge this gap and provide a more comprehensive understanding on the impact of SPF to IAQ. The field sampling plan of this research aims to evaluate the airborne concentrations of methylene diphenyl diisocyanate (MDI), formaldehyde, acetaldehyde, propionaldehyde, tris(1-chlor-2-propyl)phosphate (TCPP), trans-1-chloro-3,3,3-trifluoropropene (SolsticeTM), and airborne particles. Modifications to existing MDI sampling and analytical methods were made so that level of quantification was improved. In addition, key fate and transport modeling input parameters such as air changes per hour and airborne particle size distribution were measured. More importantly, TCPP accumulation onto materials was evaluated, which is important to study the fate and transport of semi-volatile organic compounds. The IAQ results showed that after spray application was completed in the entire building, airborne concentrations decreased for all chemicals monitored. However, it is our recommendation that during SPF application, no one should return to the application site without proper personal protection equipment as long as there are active spray activities in the building. The comparison between this field study and a recent chamber study proved surface sorption and particle deposition is an important factor in determining the fate of airborne TCPP. The study also suggests the need for further evaluation by employing mathematical models, proving the data generated in this work as informative to industry and the broader scientific community.

Methemoglobinemia resulting from exposure in a confined space: Exothermic self-polymerization of 4,4'-methylene diphenyl diisocyanate (MDI) material.

A worker attempting to remove solidified material inside a confined space (storage tank) suffered severe methemoglobinemia and almost died. The tank contained liquid 4,4'-methylene diphenyl diisocyanate monomer that had solidified after an equipment power failure caused excessive heating. Wearing a full-face elastomeric air-purifying respirator and Tyvek® coveralls, the worker used pneumatic air hammers to break up the solid material. After two tank entries totaling slightly less than one hour, the worker complained of headache and dizziness and within two hours of exiting the tank, he was admitted to the hospital in severe respiratory distress. During his eight-week hospital course, he suffered a cardiac arrest among other complications. An investigation into the cause of the worker's illness used onsite gas chromatography-mass spectrometry which identified aniline and p-toluidine vapor within the tank, attributable to overheating that led to formation of the solid material. Both are well-known causes of methemoglobinemia, and had the initial characterization of the confined space atmosphere adequately identified the hazards present appropriate engineering controls and personal protective equipment could have allowed the tank entrant to work safely in the space.

Center for the Polyurethanes Industry summary of unpublished industrial hygiene studies related to the evaluation of emissions of spray polyurethane foam insulation.

Spray polyurethane foam (SPF) insulation is used as thermal insulation for residential and commercial buildings. It has many advantages over other forms insulation; however, concerns have been raised related to chemical emissions during and after application. The American Chemistry Council's (ACC's) Center for the Polyurethanes Industry (CPI) has gathered previously unpublished industrial hygiene air sampling studies submitted by member companies that were completed during an eight-year period from 2007-2014. These studies address emissions from medium density closed cell and low density open cell formulations. This article summarizes the results of personal and area air samples collected during application and post application of SPF to interior building surfaces in both laboratory and field environments. Chemicals of interest included: Volatile Organic Compounds (VOCs), methylene diphenyl diisocyanate (MDI), flame retardants, amine catalysts, blowing agents, and aldehydes. Overall, the results indicate that SPF applicators and workers in close proximity to the application are potentially exposed to MDI in excess of recommended and governmental occupational exposure limits and should use personal protective equipment (PPE) consisting of air supplied respirators and full-body protective clothing to reduce exposure. Catalyst emissions can be reduced by using reactive catalysts in SPF formulations, and mechanical ventilation is important in controlling emissions during and after application.

Isocyanate Exposure Below Analytical Detection When a Paint Brush and Roller Are Used to Apply Moisture-Cure Polyurethane Paint.

Isocyanate exposure is known to be hazardous when polyurethane paints are applied with a spray gun, but less is known of exposure when paint is applied with a paint brush and roller. Concentrations of 1,6-hexamethylene diisocyanate (HDI) monomer and three HDI polymers were assessed when two moisture-cure polyurethane paints containing 31-35% isocyanates were applied with a paint roller and brush. Short-term 15-min samples were taken during paint application in an indoor test environment with no ventilation (n= 12); in an outdoor test environment (n= 11); and in an outdoor in-situ assessment (n= 22). The outdoor in-situ assessment involved the painting of a bus shelter and light poles at a public transit station over two night shifts. All isocyanate samples were below analytical detection. The analytical limits of detection for HDI monomer, HDI biuret, HDI isocyanurate, and HDI uretdione were 0.005, 0.84, 0.87, and 0.88 µg, respectively. The finding that isocyanate concentrations were below detection is attributed to the use of paint roller and brush which minimize paint aerosolization and the paint formulation itself which contained <1% of volatile HDI monomer.

Development of an Interception Glove Sampler for Skin Exposures to Aromatic Isocyanates.

OBJECTIVES: Skin is an important exposure route for isocyanate chemicals and contributes to systemic sensitization. Methods for assessing skin exposure are currently limited and generally rely upon removal (e.g. tape-strip) techniques prone to underestimation. The aim of this study is to (i) develop and field test an interception-based hand exposure sampler to monitor potential skin exposure to isocyanates in the workplace, (ii) to develop an analytical method based on ultra-high-performance liquid chromatography-UV absorbance-tandem mass spectrometry (UHPLC-UV-MS/MS) for analyzing glove samples; and (iii) compare it with tape-stripping skin sampling method. METHODS: Laboratory investigations assessed different glove materials/fabrics, methods for impregnating with 1-(9-anthracenylmethyl)piperazine (MAP) derivatizing agent, methylene diphenyl diisocyanate (MDI) uptake and recovery, and durability. Following use, gloves were dissected into sections corresponding to different spatial regions (finger, palm) and analyzed using a newly developed UHPLC-UV-MS/MS method capable of differentiating and quantitating different MDI isomers with high sensitivity. Performance of the glove sampler was further assessed in a pilot field study using six workers. RESULTS: A MAP-impregnated thin cotton glove sampler and UHPLC-UV-MS/MS analytical method for detecting MDI were successfully developed in laboratory studies. In subsequent field studies, a total of 384 samples from 14 glove pairs identified full-shift exposures ranged from 0.01 to 306 µg of 4,4'-MDI/worker for each hand. Surface area adjusted MDI values measured with the glove sampler (0.13-572ng MDI cm-2) were considerably higher (~400-fold) than values obtained with tape stripping. CONCLUSION: A glove sampler and a novel UHPLC-UV-MS/MS analytical method were developed to quantitatively measure MDI skin exposure. The novel interception technique overcomes inherent limitations of removal techniques for measuring isocyanate skin exposure and may be useful in exposure surveillance and future research on isocyanate's health risks.

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.

Identification of methylene diphenyl diisocyanate thermal degradation products in a generation chamber by liquid chromatography coupled with tandem mass spectrometry.

Isocyanate thermal degradation characterization by liquid chromatography coupled with electrospray tandem mass spectrometry has been performed to elucidate the methylene diphenyl diisocyanate (MDI) thermal degradation structure emitted in a generation chamber using a temperature between 50°C and 180°C to produce MDI vapors. [M+H](+) ions containing an isocyanate functional group were studied by tandem mass spectrometry. The [M+H](+) ion analyses based on the combination of full scans and precursor ion scans were useful for identifying all structures. The compounds emitted were identified and validated as a mixture of compounds containing amine and isocyanate functions. Residual MDI, methylene diphenyl amino-isocyanate, and methylene diphenyl diamine were identified. Polymerized forms of these structures were also observed because amine and isocyanate chemical functions react rapidly to polymerize. These results must be used with special care by scientists establishing sensitization diagnostics and developing sampling devices using generation chambers as they must be related to MDI behavior in workplaces. Even if pure MDI is introduced in the generation chamber, several different compounds are generated when the MDI is heated at a high temperature. This can result in some misleading interpretations for non-specific isocyanate sampling device development and sensitization diagnostics as MDI is present in the chamber with other compounds with known adverse effects.

Hexavalent chromium and isocyanate exposures during military aircraft painting under crossflow ventilation.

Exposure control systems performance was investigated in an aircraft painting hangar. The ability of the ventilation system and respiratory protection program to limit worker exposures was examined through air sampling during painting of F/A-18C/D strike fighter aircraft, in four field surveys. Air velocities were measured across the supply filter, exhaust filter, and hangar midplane under crossflow ventilation. Air sampling conducted during painting process phases (wipe-down, primer spraying, and topcoat spraying) encompassed volatile organic compounds, total particulate matter, Cr[VI], metals, nitroethane, and hexamethylene diisocyanate, for two worker groups: sprayers and sprayer helpers ("hosemen"). One of six methyl ethyl ketone and two of six methyl isobutyl ketone samples exceeded the short term exposure limits of 300 and 75 ppm, with means 57 ppm and 63 ppm, respectively. All 12 Cr[VI] 8-hr time-weighted averages exceeded the recommended exposure limit of 1 µg/m3, 11 out of 12 exceeded the permissible exposure limit of 5 µg/m3, and 7 out of 12 exceeded the threshold limit value of 10 µg/m3, with means 38 µg/m3 for sprayers and 8.3 µg/m3 for hosemen. Hexamethylene diisocyanate means were 5.95 µg/m3 for sprayers and 0.645 µg/m3 for hosemen. Total reactive isocyanate group--the total of monomer and oligomer as NCO group mass--showed 6 of 15 personal samples exceeded the United Kingdom Health and Safety Executive workplace exposure limit of 20 µg/m3, with means 50.9 µg/m3 for sprayers and 7.29 µg/m3 for hosemen. Several exposure limits were exceeded, reinforcing continued use of personal protective equipment. The supply rate, 94.4 m3/s (200,000 cfm), produced a velocity of 8.58 m/s (157 fpm) at the supply filter, while the exhaust rate, 68.7 m3/s (146,000 cfm), drew 1.34 m/s (264 fpm) at the exhaust filter. Midway between supply and exhaust locations, the velocity was 0.528 m/s (104 fpm). Supply rate exceeding exhaust rate created re-circulations, turbulence, and fugitive emissions, while wasting energy. Smoke releases showing more effective ventilation here than in other aircraft painting facilities carries technical feasibility relevance.

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.

Air-Fed Visors Used for Isocyanate Paint Spraying--Potential Exposure When the Visor Is Lifted.

Continuous-flow air-supplied breathing apparatus with a visor is the respiratory protective equipment (RPE) of choice within the motor vehicle repair trade for protection against exposure to isocyanate paints. Whilst these devices are capable of providing adequate protection, a common workplace practice of sprayers lifting up the visor of their RPE immediately after spraying when checking the quality of the paint finish is thought to have an impact on the protection afforded. While the visor lift may be only for a few seconds, this action, especially if repeated numerous times during a work shift, could potentially result in a significant increase in exposure.Informal interviews with paint sprayers were conducted to understand the reasons for this behaviour followed by a series of laboratory tests to quantify the potential degree of exposure as a result of a visor lift.The majority of the paint sprayers interviewed explained their reasons for lifting their visors immediately after spraying and before the spray booth had been adequately cleared by ventilation. The main reasons given for a visor lift included a combination of habit, poor visibility due to poor visual clarity of the visor screen material, over spray, scratched visor screens, internal visor reflections, and poor booth lighting.The findings of the tests showed that the degree of protection provided by the visor when in the lifted position is in the approximate range of 1-3.7 (mean 1.7) and over the whole of the exposure period (from start of the lift to recovery of protection after refitting) is in the approximate range of 1.4-9.0 (mean 2.7). This is a significant reduction when compared to the assigned protection factor of 40 for this class of device and the measured protection factors of 5000-10 000 when worn correctly.These results clearly demonstrate that lifting the visor whilst still within a contaminated atmosphere considerably increases the wearer's exposure and that this is an example where improvements in RPE design can contribute to lower exposure.