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PubMedDate not supplied

Development and application of a dichotomous vapor/aerosol sampler for HDI-derived total reactive isocyanate group.

A dichotomous vapor/aerosol sampler was developed for measurement of HDI (1,6-hexamethylene diisocyanate)-derived total reactive isocyanate group (TRIG). The sampler consisted of an impactor or cyclone inlet, followed by an annular diffusional denuder, and a glass-fiber filter backup. The denuder walls and backup filter were each coated with 20 mg tributylphosphate and 1 mg MAMA reagent (9-N-methylamino-methylanthracene). After collection, MAMA-derivatized isocyanates were desorbed from the sampler and determined by high-performance liquid chromatography with dual-wavelength ultraviolet absorbance and fluorescence detection. Test atmospheres of HDI vapor and of HDI/HDI-biuret aerosols were generated in the laboratory and sampled with the optimized dichotomous sampler. Vapor phase HDI was completely collected by the diffusional denuder. When a mixture of HDI-biuret and HDI (approximately 30 ppb) was nebulized and collected with the dichotomous sampler, approximately 78% of the HDI was in the vapor phase, whereas about 22% was associated with the aerosol fraction. The dichotomous sampler was then used to measure vapor and condensed phase TRIG in a paint spray booth during application of a polyurethane paint. Measured levels of TRIG during the spraying operation averaged 391 +/- 154 micrograms/m3. Concentrations of HDI monomer averaged only 14 +/- 6.5 micrograms/m3. HDI-biuret was the largest component of TRIG found in these samples and was completely in the condensed aerosol phase. In contrast, the majority of the HDI was in the vapor phase, but significant (15-26%) amounts were measured in the aerosol fraction of the paint overspray. Thus, significant partitioning of HDI between vapor and condensed phases was demonstrated in both the laboratory and field, even when its concentration was well below the vapor saturation point.

Aerosols↗
PubMedDate not supplied

An outbreak of naphthalene di-isocyanate-induced asthma in a plastics factory.

Seven cases of possible naphthalene di-isocyanate-related occupational asthma occurred in 1987 and 1988. These cases were reported to the National Institute for Occupational Safety and Health by personnel at a Midwest factory that manufactured plastic wheels for fork-lift trucks. The reporting of cases prompted (a) an evaluation of the workplace, including a medical screening of workers, to detect additional cases; and (b) an industrial-hygiene survey to determine the level of exposure to isocyanates.

Adult↗
PubMed1987

Methyl isocyanate liquid and vapor permeation through selected respirator diaphragms and chemical protective clothing.

Initially, a study was undertaken to evaluate selected chemical protective clothing suitable for use by emergency response personnel confronted with methyl isocyanate (MIC). Twenty-two chemical protective clothing materials were tested against liquid methyl isocyanate. Chemical permeation breakthrough times for these clothing materials demonstrate that only one of these garments can be considered as a candidate material against liquid MIC. In a subsequent study, three chemical protective clothing materials were evaluated against approximately 800 ppm MIC vapor. Chemical permeation breakthrough times demonstrate that these materials can be considered candidate materials. A final study tested self-contained breathing apparatus (SCBA) diaphragms. Four SCBA diaphragms were tested and all experienced rapid breakthrough when exposed to liquid MIC. Next, three SCBA diaphragms were exposed to approximately 800 ppm MIC vapor. The data demonstrate that the SCBA should be worn inside a total encapsulating suit.

Cyanates↗
PubMedDate not supplied

Field comparison of impingers and treated filters for sampling of total aliphatic isocyanates with the MAP reagent.

Results of a comparative field study on the performance of 25-mm inhalable samplers (Institute of Occupational Medicine [IOM]) and midget impingers for the collection of total isocyanates in air using the 1-(9-anthracenylmethyl)piperazine (MAP) reagent are presented. Air sampling and analysis was performed according to the National Institute for Occupational Safety and Health MAP draft method 5525. Midget impingers filled with 15 mL of 1 x 10(-4) M MAP in butyl benzoate were operated at 1 L/min. IOM cassettes loaded with 25-mm quartz fiber filters impregnated with 500 microg MAP, were operated at 2 L/min. Filters were field extracted with 10 mL of 1 x 10(-4) M MAP in acetonitrile. Thirty-four impinger-IOM pairs were collected in three autobody shops during spray painting tasks. Regression analysis [Ln (IOM) = 1.0 Ln (impinger), R2 = 0.98] and a paired t-test (Pr > 0.9) demonstrated that impingers and IOMs perform equally in their collection efficiency for the monomer and total oligomeric hexamethylene diisocyanate (HDI). IOM performance did not deteriorate at longer sampling times compared with the impinger performance. Within-sampler variability was calculated from the individual coefficients of variation (CV) of the 17 pairs of like samplers. The mean of CVs (SD)% for the monomer and total oligomeric HDI was approximately 12 (12)% and 15 (13)% for the IOM and the impinger sampler, respectively. Poor correlation (Pearson correlation coefficient < 0.3) and statistically nonsignificant differences (P > 0.74 two-sided) were found for the between-sampler CVs. Factors that might have influenced the observed sampler agreement are also discussed. It is concluded that MAP impregnated filters can be successfully used for sampling of slow curing total aliphatic isocyanates in air.

Air Pollutants, Occupational↗
PubMed2006

Respiratory protection from isocyanate exposure in the autobody repair and refinishing industry.

This study, part of the Survey of Painters and Repairers of Auto bodies by Yale (SPRAY), evaluated the effectiveness of respiratory protection against exposure to aliphatic polyisocyanates. A total of 36 shops were assessed for respiratory protection program completeness; 142 workers were measured for respirator fit factor (FF) using PortaCount Plus respirator fit tester. Twenty-two painters from 21 shops were sampled using NIOSH method 5525 to determine the workplace protection factor (WPF) of negative pressure, air-purifying half-facepiece respirators equipped with organic vapor cartridges and paint prefilters during spray-painting and priming activities. Only 11 shops (30%) had written respiratory protection programs. Eighty percent of all fit tested workers passed the test on the first try with FF >or= 100, and 92% passed the second test after respirator use training. Overall geometric mean (GM) FF was 1012 for all fit tested workers. Significant differences on pass rate (92% vs. 72%) and on FF (1990 vs. 736) were found between previously fit tested workers vs. nontested workers. Twenty-nine WPF samples were collected. The outside facepiece GM concentration of total isocyanate group (NCO) was 378.4 micro g NCO/m(3) with 96% concentrations exceeding the U.K. short-term exposure limit, 70 micro g NCO/m(3), but no in-facepiece concentrations exceeded the limit. The GM WPF of total NCO was 319 (GSD 4) and the 5th percentile was 54. WPF of total NCO was positively correlated with the duration of painting task. FF positively correlated with WPF when FF was 450. We conclude that negative pressure, air-purifying half-facepiece respirators equipped with organic vapor cartridges and paint prefilters provide effective protection against isocyanate exposure in spray and priming operations if workers are properly trained and fitted.

Adult↗
PubMed1992

Carbamoylation reactions of N-methyl-N'-aryl-N-nitrosoureas and corresponding phenyl isocyanates to 5'-amino-5'-deoxythymidine: importance of carbamoylation in mouse skin carcinogenic processes.

Carbamoylation reactions of N-methyl-N'-aryl-N-nitrosoureas (I-X: X = -OCH3, -CH3, -H, -Cl, and -COCH3) and of their corresponding phenyl isocyanates (II-X: X = -OCH3, -CH3, -H, -Cl and -COCH3) to the amino group of 5'-amino-5'-deoxythymidine have been kinetically studied in a PBS. The pseudo-first-order rate constants (kc x 10(4) s-1, 37 degrees C) are 9.21 for I-OCH3, 5.11 for I-CH3, 20.1 for I-H, 3.45 for I-Cl and 5.75 for I-COCH3. These rate constants correlated well with the tumorigenic potency of I-X to mouse skin (r = 0.761), but did not correlate with the other factors [solvolytic reactivity, alkylating activity to 4-(p-nitrobenzyl)pyridine, and mutagenicity on Salmonella typhimurium TA1535]. When the rate ratio (kc/ks) of the carbamoylation (kc) with the solvolysis (ks) was compared with the tumorigenic potency, a much better correlation was found between them (r = 0.876). Since II-X were too reactive to measure their kinetic data, the extent of their reactions at the 60 min time point was compared with the reactions of I-X. The reactivity of II-X (II-OCH3 greater than II-CH3 greater than II-H greater than II-Cl greater than II-COCH3) did not correlate with that of I-X (I-H greater than I-OCH3 greater than I-CH3 greater than I-Cl greater than I-COCH3), but both I-X and II-X gave the same carbamoylated and solvolysis products. The present results suggest that carbamoylation of amino groups in cellular constituents by N-nitrosoureas is a critical factor in inducing mouse skin tumors by the agents and that the generated isocyanates may not be the key intermediates for the carbamoylation reactions.

Animals↗
PubMed1981

Toluene-diisocyanate induced asthma: evaluation of antibodies in the serum of affected workers against a tolyl mono-isocyanate protein conjugate.

Radioallergosorbent testing was used to look for the presence of specific IgE antibody against a para-tolyl-mono-isocyanate human serum albumin conjugate in sera from five groups of subjects. The first three groups consisted of individuals exposed to toluene diisocyanate (TDI) who had been shown by bronchial provocation testing with levels of TDI below the threshold limit value of 0.02 parts/10(6), to have immediate asthmatic reactions, late asthmatic reactions or no respiratory changes at all. The two control groups consisted of atopic and non-atopic individuals who had no respiratory symptoms and no known exposure to TDI. Although RAST showed high ct/min in some of the sera from patients with proven TDI-induced respiratory disease, these levels were not significantly different from controls and appeared to reflect the presence in these sera of high levels of total IgE (greater than 100 mu ml--1). There is no evidence from this study for the presence of specific IgE antibody against a para-tolyl mono isocyanate human serum albumin conjugate in patients with TDI-induced respiratory disease. This finding may reflect absence of antibodies, or that the techniques for their detection are not always effective even when performed by experienced persons, and there is a potential source of error in the interpretation of results when sera contain large amounts of IgE.

Antibody Formation↗
PubMed1994

Sputum eosinophilia after asthmatic responses induced by isocyanates in sensitized subjects.

To assess the nature and the time-course of the cellular component of airway inflammation induced by isocyanates, we examined nine subjects with occupational asthma induced by toluene- or methylene diphenyl-diisocyanate (TDI, MDI) and four control subjects never exposed to isocyanates. Sputum was induced by inhalation of ultrasonically nebulized hypertonic saline (3-4% NaCl) before and 8, 24, 48 h after inhalation challenge with TDI or MDI. Expectorated samples were incubated with dithiothreitol, washed and cytocentrifuged. Differential cell counts were obtained on slides stained with May-Grünwald-Giemsa. Metachromatic cells (mast cells and basophils) were counted on slides stained with toluidine blue at pH 0.1. One occupational asthmatic exhibited a dual reaction to TDI, two exhibited a single early asthmatic reaction to MDI, six exhibited a late asthmatic reaction to TDI (n = 5) or MDI (n = 1), whereas no reactions were observed in control subjects after TDI challenge. In sensitized subjects eosinophils increased from a median value (interquartile range) of 5 (15)% before challenge to 29 (29)% (P = 0.014) and to 30 (31)% (P = 0.031) 8 and 24 h after TDI/MDI challenges, respectively. Sputum eosinophilia was observed both in early and late reactors and declined to near to baseline values 48 hr after challenge. Percentages of eosinophils in control subjects did not exceed 7% during the study.(ABSTRACT TRUNCATED AT 250 WORDS)

Adult↗
PubMed1996

Reactive airways dysfunction syndrome induced by exposure to a mixture containing isocyanate: functional and histopathologic behaviour.

A 31-year-old machinist experienced acute symptoms of rhinoconjunctivitis, coughing, shortness of breath, and wheezing after sudden exposure to fumes containing isocyanates and solvents. Lung function tests carried out 11 days after the event showed reduced flow rates. Forty days after the acute inhalational injury, expiratory flows improved, and the PC20 was 0.8 mg/ml, showing moderate bronchial hyperresponsiveness. Six days later, the subject underwent bronchoscopy. Bronchial biopsies showed a marked loss of epithelial cells, severe subepithelial oedema, and inflammatory cells infiltrate (mainly lymphocytes). The subject was given inhaled steroids. The PC20 was back to normal 42 days later. Bronchial biopsies then showed incomplete regeneration of the epithelial layer with few ciliated cells and persistence of inflammation (lymphocyte infiltrate) in epithelia and connective tissue. We conclude that irritant exposure to a mixture of isocyanates and solvents can cause occupational asthma without a latency period, i.e., reactive airways dysfunction syndrome.

Adult↗
PubMed1985

Effects of methyl isocyanate on the respiratory tract of rats.

Static exposure of rats to methyl isocyanate, for one hour, led to respiratory impairment during and after exposure. The resultant changes in breathing pattern suggest that this compound is both a sensory and a pulmonary irritant. Low concentrations resulted in extensive necrosis and loss of epithelial cells in the proximal airways but widespread alveolar damage was found only after exposure to high, lethal concentrations. At high concentrations methyl isocyanate probably caused peracute death through reflex inhibition of breathing. Animals surviving the exposure exhibited signs of airway narrowing and development of (haemorrhagic) pulmonary oedema. The epithelial lesions were repaired rapidly, but residual peribronchial fibrosis and signs of renewed injury/inflammation were apparent.

Animals↗
PubMed1990

Delayed eye and other consequences from exposure to methyl isocyanate: 93% follow up of exposed and unexposed cohorts in Bhopal.

A follow up study three years after exposure to methyl isocyanate in 93% of exposed survivors and "control" residents in 10 Bhopali communities showed an excess of eye irritation, eyelid infection, cataract, and a decrease in visual acuity among the exposed people. Breathlessness was twice as common in the heavily exposed clusters as those with lower exposure, a trend that could not be explained by different age or smoking patterns (OR 2.05, 95% CI 1.36-3.08). Case referent analysis of outpatient attendances at Bhopal Eye Hospital, considering patients with severe refractive errors and astigmatism as "controls," showed a 40% increased risk of trachoma, 36% increased risk of other lid infections, and 45% increased risk of irritant symptoms among previously exposed people. "Bhopal eye syndrome" may thus include full resolution of the initial interpalpebral superficial erosion, a subsequent increased risk of eye infections, hyperresponsive phenomena (irritation, watering, and phlyctens), and possibly cataracts. It remains to be confirmed whether this reflects a more generalised disease as a consequence of previous exposure to methyl isocyanate or whether it is only the eye that is affected.

Accidents, Occupational↗
PubMed1999

Biological monitoring to assess exposure from use of isocyanates in motor vehicle repair.

OBJECTIVES: To develop a method for the measurement of a metabolite of hexamethylene diisocyanate (HDI), an isocyanate, and use it to assess the exposure of sprayers employed in motor vehicle repair shops. METHODS: Urine samples were taken from sprayers wearing personal protective equipment and spraying in booths or with local exhaust ventilation, from bystanders, and from unexposed subjects. Samples were analyzed for a metabolite of HDI, hexamethylene diamine (HDA), by gas chromatography-mass spectrometry (GC-MS). RESULTS: HDA was detected in four sprayers and one bystander out of 22 workers. No HDA was detected in the urine of unexposed subjects. CONCLUSIONS: Exposure to isocyanates still occurs despite the use of personal protective equipment and the use of a booth or extracted space. Health surveillance is likely to be required to provide feedback on the adequacy of controls even if such precautions are used and to identify cases of early asthma. Biological monitoring can provide a useful additional tool to assess exposure and the adequacy of controls in this group of exposed workers.

Automobiles↗
PubMed1994

Inhibition of mouse embryonic, yolk sac, and limb-bud functions by the methyl isocyanate metabolite S-(N-methylcarbamoyl)glutathione.

We previously reported that S-(N-methylcarbamoyl)glutathione (SMG), a conjugate formed by the reversible reaction between methyl isocyanate and glutathione, inhibited the development of mouse embryos in culture. The present study was done to determine whether SMG produced embryotoxicity by inhibiting yolk sac functions. For this purpose we determined the effects of an embryotoxic concentration of SMG on mouse yolk sac uptake mechanisms and lysosomal proteolysis as well as on the incorporation of [3H]leucine in mouse embryonic and limb-bud proteins. After 5 h of culture, SMG inhibited the uptake of [14C]sucrose and 125I-labelled bovine serum albumin in isolated day 15 yolk sacs to 62 and 77% of control, respectively. Lysosomal proteolysis was not inhibited, as judged by the release of trichloroacetic acid soluble radioactivity into the culture media. Uptake and incorporation of [3H]leucine from free [3H]leucine or from [3H]leucine-labelled protein in SMG-treated day 9 embryos were inhibited, respectively, to 61 and 25% of the control uptake during a 16-h labelling period. SMG also inhibited the incorporation of free [3H]leucine into limb-bud proteins. SMG-induced inhibition of 125I-labelled bovine serum albumin uptake by yolk sacs was partially prevented by the thiol donors N-acetylcysteine and glutathione but not by acivicin (gamma-glutamyl transpeptidase inhibitor) and aminooxyacetic acid (cysteine conjugate beta-lyase inhibitor). These data suggest that SMG suppresses embryonic growth primarily by an inhibition of nutrient uptake by the yolk sac. We postulate that this inhibition is due to tissue carbamoylation by methyl isocyanate released from SMG.

Aminooxyacetic Acid↗
PubMed1994

Reaction of 6-hydroxytetrahydro-beta-carboline-3-carboxylic acids with isocyanates and isothiocyanates.

The reaction of (-)-(3,S)-6-hydroxy-1,2,3,4-tetrahydro-beta-carboline-3-carboxylic acid (3a) with isocyanates and isothiocyanates gave the (+/-)-beta-carboline-hydantoin (4a-d) and -thiohydantoin systems (5a-d). The treatment of (-)-(1S,3S)-6-hydroxy-1-methyl-1,2,3,4-tetrahydro-beta-carboline-3-ca rbo xylic acid (3b) with isocyanates yielded the (+/-)-cis diastereomer of the beta-carboline-hydantoin rings (4e-h). However, the reaction of 3b with isothiocyanates provided the corresponding trans isomer (5e-h). These results have been confirmed by 13C-NMR data and nuclear Overhauser effect (NOE) experiments. The new compounds were tested for in vitro binding affinity to the central-type benzodiazepine receptors.

Animals↗
PubMed1987

Effect of methyl isocyanate (MIC) gas on the eyes of Fischer 344 rats.

The accidental release of methyl isocyanate gas in Bhopal, India, was reported to cause temporary blindness and other eye injuries in many of the exposed people. Methyl isocyanate (MIC) is known to be corrosive and to irritate intact skin and mucous membranes, but little is known about the extent of ocular damage incurred during exposure to its vapors. The eyes of male and female Fischer 344 rats were evaluated immediately after a 2-hr exposure to 0, 3, 10, or 30 ppm of MIC, and periodically thereafter during a 91-day recovery period. During exposure to 10 ppm and higher concentrations, rats kept their eyes partially closed. Copious lacrimation and occasional frothy nasal discharge were evident. Eyes were examined under ultraviolet light after topical application of sodium fluorescein, and histopathologic examination included lids, cornea, lens, retina, optic nerve, and Harderian gland. There was no significant gross or microscopic evidence of epithelial erosion or ulceration of the cornea, or of adjacent tissues immediately after, or at any time following exposures. No skin irritation was noted. It would appear that the natural protective mechanisms of the eye of rats were adequate to prevent ocular damage at these exposure levels.

Animals↗
PubMed1987

Two-hour methyl isocyanate inhalation and 90-day recovery study in B6C3F1 mice.

B6C3F1 mice were exposed by inhalation to 0, 3, 10, and 30 ppm methyl isocyanate for 2 hr followed by a 90-day recovery period. Sixteen of eighty (20%) male mice in the 30 ppm group died following exposure. There were no other unscheduled deaths in the mice. Five mice/sex/group were examined at 2 hr or at 1, 3, 7, 14, 28, 49, or 91 days following exposure. Chemical-related changes were restricted to the respiratory system. At 30 ppm there were extensive necrosis and erosion of the respiratory and olfactory epithelium in the nasal cavity. Severe necrosis and epithelial erosion were also found in the trachea and main bronchi. Regeneration of the mucosal epithelium occurred rapidly in the nasal cavity and airways. In the turbinates, mild incomplete olfactory epithelial regeneration persisted to day 91 in the male mice. Intraluminal fibrotic projections covered by respiratory epithelium and bronchial fibrosis were found in the major airways of the 30 ppm male and female mice by day 7. The intraluminal fibrosis persisted to day 91. In males with severe bronchial fibrosis, chronic alveolitis and atelectasis were found. In mice exposed to 3 or 10 ppm, persistent pulmonary changes were not found. These studies indicate that methyl isocyanate inhalation at or near lethal concentrations can cause persistent fibrosis of the major bronchi in mice.

Animals↗
PubMed1996

Bronchoprovocation tests in the diagnosis of isocyanate-induced asthma.

Over the past 25 years, investigators have continued to improve on the approach to providing nonirritant exposures for the accurate diagnosis of isocyanate-induced asthma. Although the technology used in testing has become more sophisticated and may be fairly considered the domain of the bioengineer, the chemist, and the industrial hygienist, the requirements of the physician have remained unchanged. The physician must observe the level of exposure closely and monitor the worker's symptoms and lung function. Direct physician involvement in the testing procedure remains critical to the worker's safety and for the accurate diagnosis of isocyanate-induced asthma.

Asthma↗
PubMed2004

Allergic contact dermatitis from isocyanates among sculptors.

Allergic contact dermatitis from isocyanates is rare. We present the cases of two sculptors who developed a dermatitis from polyurethane sculpting materials. The patients reacted to diphenylmethane diisocyanate and isophorone diisocyanate. One of the patients had positive patch-test reactions to 1,6-hexamethylene diisocyanate and toluene diisocyanate as well. The patients also exhibited a sensitivity to diaminodiphenylmethane, an amine that has been reported in other cases of isocyanate sensitivity.

Adult↗