Cyano compounds - 577 entries found
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Whittaker S.G., Reeb-Whitaker C.
Characterizing the health and safety needs of the collision repair industry
Production workers in the collision repair shops are potentially exposed to harmful chemicals, including isocyanates, known to cause work-related asthma. The objectives of this study were to gather information on the number of workers potentially exposed to isocyanates and other chemicals, together with health and safety practices for reducing exposure and increasing employer and worker awareness. Data were gathered using a combination of interviews, field investigations and a survey in Washington State. A key finding is that inappropriate selection and insufficient use of respirators and gloves contribute significantly to isocyanate exposures. Possible reasons and implications are discussed.
Journal of Occupational and Environmental Hygiene, May 2009, Vol.6, No.5, p.273-282. 31 ref.
Health and Safety Executive
Field validation of improved sampling methods for airborne cyanoacrylates
The Health and Safety Laboratory has developed revised sampling methods for ethyl-2-cyanoacrylate and methyl-2-cyanoacrylate following the introduction of a 0.3 ppm short-term exposure limit (see RR645, ISN 111549). This report describes a field validation exercise undertaken to assess these improved cyanoacrylate sampling methods. A three-site, four visit field validation exercise has been carried out. The sites visited were a Police scene-of-crime laboratory, an automotive loudspeaker manufacturer and a producer of adhesives which was visited on two occasions. Static sampling was performed using an impinger based reference method together with the two newly developed tubes, based on a commercially-available Tenax tube. Both tubes performed well and the results were generally in good agreement with the reference method over a representative range of concentrations. Both tubes were found to be suitably robust for fieldwork. It is recommended that the tube with steel mesh be used for all measurement of airborne cyanoacrylate concentrations due to better performance in laboratory validation tests.
HSE Books, P.O. Box 1999, Sudbury, Suffolk CO10 2WA, United Kingdom, 2008. vi, 17p. Illus. 2 ref.
RR646.pdf [in English]
Health and Safety Executive
Measurement of alkyl 2-cyanoacrylates at low concentrations: Further work
This report describes research into improved cyanoacrylate sampling methods. The research was an assessment of Automated Thermal Desorption (ATD) as an alternative sampling and analytical technique for the measurement of airborne cyanoacrylate. It involved developing of modified Tenax sampling tubes. Findings are discussed.
HSE Books, P.O. Box 1999, Sudbury, Suffolk CO10 2WA, United Kingdom, 2008. viii, 19p. Illus. 3 ref.
RR645.pdf [in English]
Mingomataj E.Ç., Gjata E., Xhixha F., Hyso E.
A case of isocyanate-induced asthma possibly complicated by food allergy after peanut consumption: A case report
A 50-year male worker employed as vehicle body painter for eight years complained about breathlessness, wheezing, sneezing, nasal obstruction and excessive production of mucus during the use of an acrylic enamel paint. Symptoms occurred 15-20 minutes after workplace exposure and usually persisted until evening, or at times, up to two consecutive days. The symptoms were associated with a decrease in lung function. The use of inhaled adrenergic bronchio-dilatators and steroids relieved the symptoms. Three years earlier, the patient had developed an anaphylactic reaction due to peanut consumption, experiencing urticaria, angioedema and airway obstruction. Both cases gave rise to IgE-mediated symptoms, suggesting an induced Th2 profile.
Journal of Occupational Medicine and Toxicology, Nov. 2008, Vol.3, No.29, 4p. 21 ref.
http://www.occup-med.com/content/pdf/1745-6673-3-29.pdf [in English]
Todd L.A., Mottus K., Mihlan G.J.
A survey of airborne and skin exposures to chemicals in footwear and equipment factories in Thailand
This research reports on an exposure evaluation study at four footwear factories and two equipment factories in Thailand. Workers in these factories were exposed through inhalation and dermal contact to a large number of organic vapors from solvents and adhesives that were applied by hand. In addition, these workers were exposed to highly toxic isocyanates primarily through the dermal route. A total of 286 personal air samples were obtained at the four footwear factories, where 64 samples were also collected from working and tool surfaces. Between 8% and 21% of the workers sampled in each footwear factory were overexposed to mixtures of chemicals from solvents and adhesives. Up to 100% of the workers performing specific job tasks were overexposed to mixtures of chemicals. Between 39% and 69% of the surface samples were positive for unreacted isocyanates. Many of the real-time measurements obtained in the equipment factories exceeded occupational exposure limits. Personal protective equipment and engineering controls were inadequate in all of the factories.
Journal of Occupational and Environmental Hygiene, Mar. 2008, Vol.5, No.3, p.169-181. Illus. 35 ref.
Iranzo García Y.
Internal emergency plans in the chemical industry
Planes de emergencia interior en la industria química [in Spanish]
Contents of this article on internal emergency plans in the chemical industry: example of classification of a dangerous substance (acrylonitrile) used by an enterprise; internal and external emergency plans; categories of accidents in the chemical industry; contents of an internal emergency plan; implementation and updating of the internal emergency plan.
Seguridad y Salud en el Trabajo, May 2008, No.47, p.36-45. Illus. 6 ref.
Got everything covered?
This poster provides practical tips to protect workers from the hazards of isocyanate exposure during spray-on truck bedliner applications. These tips include wearing a supplied-air respirator, using shields with peel-off visors, wearing chemical resistant protective clothing and gloves, ensuring that the ventilation system is operating correctly, washing hands and face after each spraying and consulting a doctor in case of shortness of breath or skin irritation.
Publications Dissemination, National Institute for Occupational Safety and Health (NIOSH), 4676 Columbia Parkway, Cincinnati, OH 45226-2001, USA, Jan. 2008. 1p. Illus.
http://www.cdc.gov/niosh/docs/2008-109/pdfs/2008-109.pdf [in English]
Bello D., Sparer J., Redlich C.A., Ibrahim K., Stowe M.H., Liu Y.
Slow curing of aliphatic polyisocyanate paints in automotive refinishing: A potential source for skin exposure
Polyurethane paints containing aliphatic isocyanates used in automobile body spray painting can cause asthma, and skin exposure may be an important route of sensitization. Automobile body workers are frequently in contact with recently painted and dried auto parts. It is not known how fast the newly-painted car surfaces are fully cured. To address this question, sections of auto bodies were painted and dried by automobile body shop painters following regular practice. It was found that unbound isocyanate species remained present on the majority of painted surfaces for up to 120 hours for typical paint formulations and for one month in some cases. Such surfaces are an under-recognized potential source of skin exposure to automobile body workers.
Journal of Occupational and Environmental Hygiene, June 2007, Vol.4, No.6, p.406-411. Illus. 26 ref.
Robert A., Ducos P., Francin J.M., Marsan P.
Exposure to MDI in 19 French enterprises - Urinary MDA as a biomarker of exposure
Exposition au MDI dans 19 entreprises françaises - La MDA urinaire comme biomarqueur de l'exposition [in French]
Animal experiments have proven that skin exposure to 4,4'- methylenediphenyl diisocyanate (MDI) causes respiratory allergies. It is therefore necessary to take skin exposure into account when evaluating exposure to MDI. Determination of 4,4'-methylenedianiline (MDA) in urine is considered to be a reliable method for evaluating exposure to MDI by all routes of entry. This study was aimed at evaluating the level of skin exposure to MDI in 19 French enterprises in various sectors of activity, my means of measuring the urinary excretion of MDA. Taking the existing technical and analytical capabilities into account, a biological limit of 7µg/L (5µg/g creatinine) for urinary MDA, not to be exceeded at the end of the shift, could be proposed.
Cahiers de notes documentaires - Hygiène et sécurité du travail, 3rd Quarter 2007, No.208, p.7-17. Illus. 55 ref.
Lensen G., Jungbauer F., Gonçalo M., Coenraads P.J.
Airborne irritant contact dermatitis and conjunctivitis after occupational exposure to chlorothalonil in textiles
Chlorothalonil (= 2,4,5,6-tetrachloroisophthalonitrile) is a pesticide that has been on the market for many years. It is used as a fungicide in agriculture, horticulture and floriculture, as a wood preservative, as well as in paint. This article describes an epidemic of airborne irritant contact dermatitis, conjunctivitis and upper airway complaints among seamstresses in a Portuguese trailer tent factory, which was attributed to chlorothalonil. All exposed workers had work-related skin symptoms. After patch testing, it was shown that none of these were of allergic origin. Instead of allergic reactions, a delayed type of irritation was noticed after 72hr to chlorothalonil and to the textile extracts containing high concentrations of chlorothalonil. Although allergic and irritant contact dermatitis from chlorothalonil has been described before, this is the first report of a delayed type of dermatitis, conjunctivitis and upper airway irritation after exposure to chlorothalonil.
Contact Dermatitis, Sep. 2007, Vol.57, No.3, p.181-186. 24 ref.
Lesage J., Stanley J., Karoly W.J., Lichtenberg F.W.
Airborne methlyene diphenyl diisocyanate (MDI) concentrations associated with the application of polyurethane spray foam in residential construction
The objective of this study was to evaluate the exposure to airborne methylene diphenyl diisocyanate (MDI) among spray polyurethane foam applicators. It was conducted during foam application inside five single family homes under construction in the United States and Canada. Spray foam applicators and assistants may be exposed to airborne MDI concentrations above the OSHA permissible exposure limit of 0.20mg/m3, ceiling. At these concentrations, OSHA recommends appropriate respiratory protection. Airborne MDI concentrations decrease rapidly after foam application ceases. The majority of the airborne MDI samples collected in the breathing zones of the spray foam applicators exceeded the OSHA PEL-C. The highest airborne concentrations measured after 15 and 45min were 0.019mg/m3 and 0.003mg/m3, respectively. Other findings are discussed.
Journal of Occupational and Environmental Hygiene, Feb. 2007, Vol.4, No.2, p.145-155. Illus. 14 ref.
Advisory Committee on Existing Chemicals (BUA)
Conclusions of this criteria document which reflects the state of knowledge of April 2006: the toxicity of 2-chlorobenzonitrile and 4-chlorobenzonitrile are low. In rats, the oral LD5l0 for 2-chlorobenzonitrile and 4-chlorobenzonitrile are 396mg and 887mg per kg body weight respectively. For 2-chlorobenzonitrile, the 4h LC50 in rats is more than 440mg/m3 and the dermal LD5l0 in rabbits is between 340 and 600 mg/kg body weight. No corresponding data are available for 4-chlorobenzonitrile. In mutagenicity tests, 2-chlorobenzonitrile is non-mutagenic up to the cytotoxic range. No data on mutagenicity are available for 4-chlorobenzonitrile. No data for either substance are available for an evaluation of the sensitization potential, genotoxicity, carcinogenicity and reproductive toxicity.
S. Hirzel Verlag, Birkenwaldstrasse 44, 70191 Stuttgart, Germany, 2007. xiv, 48p. 121 ref. Price: EUR 00.00. Downloadable version free of charge.
http://www.dav-buchhandlung.de/... [in English]
Advisory Committee on Existing Chemicals (BUA)
Conclusions of this criteria document which reflects the state of knowledge of November 2005: isopropyl isocyanate is highly irritating to the skin, eyes and respiratory tract. In male rats, the 5h LC50 is 499mg/m3 and the oral LD5l0 is 218mg/kg body weight in rats. Animal studies at high concentrations show adverse effects on the respiratory function. In mutagenicity tests, the product is non-mutagenic up to the toxic range. No data are available for an evaluation of the sensitization potential, genotoxicity, carcinogenicity and reproductive toxicity.
S. Hirzel Verlag, Birkenwaldstrasse 44, 70191 Stuttgart, Germany, 2007. xiv, 40p. 79 ref. Price: EUR 00.00. Downloadable version free of charge.
http://www.dav-buchhandlung.de/... [in English]
Pisati G., Baruffini A., Bernabeo F., Cerri S., Mangili A.
Rechallenging subjects with occupational asthma due to toluene diisocyanate (TDI), after long-term removal from exposure
The aims of this study were to determine whether toluene diisocyanate (TDI) bronchial hyperresponsiveness persists in subjects with occupational asthma after long cessation of exposure and whether evolution of specific bronchial TDI sensitization and symptoms and functional abnormalities of asthma were coincident, and to define the determinants at the time of diagnosis of patients' outcome. Twenty-five non-atopic spray painters with occupational asthma due to TDI were re-examined approximately five years after removal from exposure. Tests included spirometry, methacholine challenge and TDI-specific IgE. Seven subjects were still TDI-reactors while 18 had lost reactivity to the substance, among whom however eight still retained some asthma features. This study demonstrates that airway sensitization to TDI and symptoms and functional airway abnormalities of asthma can persist for years after cessation of exposure.
International Archives of Occupational and Environmental Health, Feb. 2007, Vol.80, No.4, p.298-305. Illus. 21 ref.
White J., Coldwell M., Davies T., Helps J., Piney M., Rimmer D., Saunders J., Wake D.
Health and Safety Executive
Isocyanate exposure, emission and control in small motor vehicle repair premises using spray rooms: Phase 1
A mock up spray room was constructed within the Health and Safety Laboratory with dimensions, ventilation conditions and extraction rates set to represent typical car body spray room conditions. A robotic sprayer was used to simulate paint spraying of car parts under a range of conditions; including spray orientation relative to the extraction duct, spray gun type, ventilation set up and extraction rates. Real-time monitors were used in conjunction with standard methods for airborne isocyanate (NCO) concentration monitoring. The main findings were: high NCO levels are present in spray rooms during spraying; airborne NCO levels were homogeneous throughout the spray room; factors affecting the amount of airborne NCO include gun type, gun condition, spray pattern and NCO formulation; airborne NCO took a significant time to clear the spray room. Other findings are discussed.
HSE Books, P.O. Box 1999, Sudbury, Suffolk CO10 2WA, United Kingdom, 2006. x, 111p. Illus. 29 ref.
http://www.hse.gov.uk/research/rrpdf/rr496.pdf [in English]
Pronk A., Yu F., Vlaanderen J., Tielemans E., Preller L., Bobeldijk I., Deddens J.A., Latza U., Baur X., Heederik D.
Dermal, inhalation and internal exposure to 1,6-HDI and its oligomers in car body repair shop workers and industrial spray painters
The objective of this study was to evaluate exposure to hexamethylene diisocyanate (HDI) and its oligomers among car body repair shop workers and industrial spray painters. A total of 95 personal samples were collected from six car body repair shops and five industrial paint shops and analysed using impingers with di-n-butylamine (DBA) in toluene. In parallel, dermal exposure was assessed using nitrile rubber gloves submerged into a solution of DBA in toluene after sampling. Analysis for HDI and its oligomers was performed by liquid chromatography coupled with mass spectrometry. Urine samples collected from 55 workers were analysed for hexamethylene diamine (HDA) by gas chromatography coupled with mass spectrometry. Findings are discussed. HDA was detected in urine of 25% of the spray painters. In addition, HDA was detected in urine of a large proportion of non-spray painters in car body repair shops. Although painting with lacquers containing isocyanates results in the highest external exposures to HDI and oligomers, workers that do not perform paint related tasks are significantly exposed.
Occupational and Environmental Medicine, Sep. 2006, Vol.63, No.9, p.624-631. Illus. 37 ref.
Kakooei H., Shahtaheri S.J., Karbasi H.A.
Evaluation of workers' exposure to methylene diphenyl diisocyanate (MDI) in an automobile manufacturing company, Iran
The objective of this case-control study was to evaluate the inhalation exposure to methylene diphenyl diisocyanate (MDI) among 39 employees working in the window assembly unit of an automobile manufacturing company in Iran. Controls consisted of 117 unexposed workers in other departments of the plant. MDI was determined with a UV-VIS spectrophotometer at 590nm. Lung function was assessed with a digital spirometer. The average concentration of MDI in the window fixation and window glue workplaces were 34.53 and 27.37µg/m3, respectively, which were lower than the threshold limit value recommended by the ACGIH of 51µg/m3. However, there was a significantly higher frequency of respiratory symptoms and a significantly lower lung capacity in the exposed group compared to the unexposed group.
International Journal of Occupational Safety and Ergonomics, 2006, Vol.12, No.4, p.443-449. 22 ref.
Sennbro C.J., Lindh C.H., Mattsson C., Jönsson B.A.G., Tinnerberg H.
Biological monitoring of exposure to 1,5-naphthalene diisocyanate and 4,4'-methylenediphenyl diisocyanate
Biological monitoring of exposure to occupational sensitizers, such as 1,5-naphthalene diisocyanate (NDI) and 4,4'-methylenediphenyl diisocyanate (MDI) is of high importance. In this study, the breathing atmosphere exposure to NDI and MDI was monitored for 30 workers at four different plants. In parallel, urinary as well as blood plasma samples were collected. 1,5-naphthalenediamine (NDA) and 4,4'-methylenedianiline (MDA) in hydrolysed urine and plasma were evaluated as biomarkers of exposure to NDI and MDI, respectively, by means of gas chromatography-mass spectrometry. Air exposure to both MDI and NDI was correlated to their corresponding biomarkers, but with a large individual variation.
International Archives of Occupational and Environmental Health, Sep. 2006, Vol.79, No.8, p.647-653. Illus. 28 ref.
Advisory Committee on Existing Chemicals (BUA)
Conclusions of this criteria document which reflects the state of knowledge of February 2006: 4-chlorophenyl-isocyanate is a colourless to yellowish solid which melts below 30°C. It is highly-reactive chemical intermediate used in the production of certain plant protection chemicals. It hydrolyses in the presence of water, forming 4-chloroaniline. Modes of entry include ingestion, inhalation and skin absorption. The few available animal studies show low toxicity but with inconsistent results. There are no data on chronic ingestion toxicity. In rats, the target organ of chronic inhalation exposure is the lung. It is irritating to the skin and eye. In vitro studies show the product to be non-mutagenic. There are no data on reproductive toxicity and carcinogenicity.
S. Hirzel Verlag, Birkenwaldstrasse 44, 70191 Stuttgart, Germany, 2006. xiv, 58p. 136 ref.
Preventing asthma and death from MDI exposure during spray-on truck bed liner and related applications
Contents of these recommendations for preventing asthma and other respiratory diseases during polyurethane spray-on applications: description of the polyurethane spray-on truck bed lining process; spray applications other than truck bed lining; health effects of isocyanates (lung injury, respiratory sensitization, cancer); current exposure limits; workplace exposure assessments; case reports of isocyanate-induced asthma and other respiratory diseases investigated by NIOSH; recommendations aimed at shop owners and suppliers of chemicals; future research. These recommendations are also summarized on a detachable sheet for display on a notice board. Appendices include: properties and chemical structure of isocyanates; spray enclosure and ventilation design considerations; supplied-air respirators and elements of a respiratory protection programme; surveillance guidelines for work-related asthma.
Publications Dissemination, National Institute for Occupational Safety and Health (NIOSH), 4676 Columbia Parkway, Cincinnati, OH 45226-2001, USA, Sep. 2006. 35p. Illus. 57 ref.
http://www.cdc.gov/niosh/docs/2006-149/pdfs/2006-149.pdf [in English]
Lui Y., et al.
Respiratory protection from isocyanate exposure in the autobody repair and refinishing industry
This study evaluated the effectiveness of respiratory protection against exposure to aliphatic polyisocyanates in automobile body repair shops. A total of 36 shops were assessed for respiratory protection programme completeness. 142 workers were measured for respirator fit factor. In addition, 22 painters from 21 shops were sampled to determine the protection factors of negative pressure, air purifying half-facepiece respirators equipped with organic vapour cartridges and paint pre-filters during spray-painting and priming activities. Findings are discussed. It is concluded half-facepiece respirators equipped with organic vapour cartridges and paint prefilters provide effective protection against isocyanate exposure in spray and priming operations if workers are properly trained and fitted.
Journal of Occupational and Environmental Hygiene, May 2006, Vol.3, No.5, p.234-249. Illus. 58 ref.
Methner M.M., Achutan C.
Case study - Airborne hexamethylene diisocyanate and particulate matter exposures during fire/rescue ladder finishing operations
In 2004, the National Institute for Occupational Safety and Health (NIOSH) received a request from the management of a steel ladder fabrication plant to evaluate employee exposures to hexamethylene diisocyanate (HDI) during spray painting operations. Management representatives were also concerned about exposures to particulate matter and crystalline silica during spray painting and sanding operations. Personal breathing zone and general area samples were collected and analysed. Findings are discussed. All samples were within the NIOSH and ACGIH threshold limit values, although some exceeded the United Kingdom HSE limit values. Particulate matter was well within limits and crystalline silica was not detected. Recommendations were made for further reduction of exposures to HDI.
Journal of Occupational and Environmental Hygiene, Mar. 2006, Vol.3, No.3, p.D28-D32. 11 ref.
Isocyanate exposure in an autobody repair and collision center
This inspection by the Occupational Safety and Health Administration (OSHA) reports on an overexposure to methylene bisphenyl isocyanate (MDI) during the spray application of a protective coating for truck beds. The inspection was conducted at an automobile body repair shop that also operated a spray-on truck bed coating operation. The investigation was initiated as a complaint inspection and was limited to the complaint allegation. The employee alleged that workers were exposed to harmful vapours during application of the truck bed liner. Site visits and sampling confirmed exposures to MDI in excess of the threshold limit value of 0.20mg/m3. A number of recommendations aimed at lowering the level of exposure were made and successfully implemented by the employer.
Journal of Occupational and Environmental Hygiene, Mar. 2006, Vol.3, No.3, p.D24-D27. 3 ref.
Boutin M., Ostiguy C., Dufresne A., Charette M., Lesage J.
Determination of the airborne concentration of isocyanates during the thermal degradation of automobile paint in body repair shops
Détermination de la concentration d'isocyanates aéroportés pendant la dégradation thermique de peinture automobile dans les ateliers de réparation de carrosserie [in French]
Earlier studies showed that the thermal degradation of polyurethane-based car body paints could generate isocyanates, which are potentially harmful substances. An in situ sampling system was devised for the air sampling of isocyanates produced during the thermal degradation process. However under field conditions, various factors can affect the sampling efficiency. The purpose of this study was to validate the sampling technique under actual working conditions and to establish an indicator for evaluating the overall exposure of workers to the isocyanates generated by the thermal degradation of paints. Measurements carried out in three car body repair shops confirmed the reliability of the method.
Institut de recherche Robert-Sauvé en santé et en sécurité du travail du Québec (IRSST), 505 boul. de Maisonneuve Ouest, Montreal (Quebec) H3A 3C2, Canada, 2006. 24p. Illus. 26 ref. Price: CAD 5.30. Downloadable version (PDF format) free of charge.
http://www.irsst.qc.ca/files/documents/PubIRSST/R-456.pdf [in French]
Cyclohexyl isocyanate: Documentation of maximum admissible values for occupational exposure
Izocyjanian cykloheksylu: Dokumentacja proponowanych wartości dopuszczalnych wielkości narżenia zawodowego [in Polish]
Cyclohexyl isocyanate (CHI) is a colourless to pale yellow liquid. It is used as a chemical intermediate in the production of drugs, pesticides, amines, ureas and other carbamoyl compounds. The vapour phases of CHI are strongly irritating to the eyes, skin and mucous membranes. Typical symptoms include breathlessness, dry cough, difficulty in breathing and possibly coughing up blood. Like other isocyanates, CHI may cause skin and respiratory sensitization. Due to the similarity of CHI to other isocyanates, the Expert Group has established the value of 0.04 mg/m3 as a maximum exposure limit (MAC). The notations I (irritation) and A (sensitization) should also be included.
Podstawy i Metody Oceny Środowiska Pracy, 2005, Vol.46, No.4, p.71-82. 21 ref.
Gannon P.F.G., Berg A.S., Gayosso R., Henderson B., Sax S.E., Willems H.M.J.
Occupational asthma prevention and management in industry - An example of a global programme
A global supplier of isocyanate-based automotive coatings developed a programme to address the known potential effects of isocyanates on its workers. The goals of the programme are the prevention, early detection and mitigation of asthma and dermatitis among workers exposed or potentially exposed to isocyanates and products containing isocyanates. The programme includes assessment of exposure, pre-placement questionnaires, spirometry, training of employees, regularly administered questionnaires, medical assessment for abnormal questionnaire responses, process for early reporting and investigation of symptomatic employees and incidents, data review and management reporting. These control measures are relatively inexpensive and can be applied even in small businesses. It is recommended that all employers who manufacture, handle or use isocyanate-containing products consider such a strategy.
Occupational Medicine, Dec. 2005, Vol.55, No.8, p.600-605. Illus. 11 ref.
Sakai T., Morita Y., Roh J., Kim H., Kim Y.
Improvement in the GC-MS method for determining urinary toluene-diamine and its application to the biological monitoring of workers exposed to toluene-diisocyanate
The objective of this study was to develop a simple and sensitive gas chromatography-mass spectrometry (GC-MS) method for determining toluene-diamine (TDA) in urine and to apply the method for biological monitoring of workers exposed to toluene-diisocyanate (TDI). The method involved acid hydrolysis urine followed by the extraction of the free TDA with dichloromethane and the determination of the heptafluorobutyric anhydride derivative by GC-MS. This method was applied to the biological monitoring of 18 workers exposed to an 80:20 mixture of 2,4-TDI and 2,6-TDI. The method was found to be simple and practicable, showing a good correlation with personal TDI exposures.
International Archives of Occupational and Environmental Health, July 2005, Vol.78, No.6, p.459-466. Illus. 22 ref.
Sennbro C.J., Littorin M., Tinnerberg H., Jönsson B.A.G.
Upper reference limits for biomarkers of exposure to aromatic diisocyanates
The objectives of this study were to determine the levels of biomarkers of exposure to several diisocyanates in the urine and blood of occupationally unexposed workers and to calculate their upper reference limits (URLs). Biomarker levels were determined in urinary and plasma samples obtained from 121 occupationally unexposed workers. URLs were then calculated based on these biomarker levels and the levels in an occupationally exposed group of workers. These URLs may be used for screening for occupational exposure, a worker with a biomarker level above the URL being classified as occupationally exposed. Biomarkers of aromatic diisocyanates, especially biomarkers of 4,4'-methylenediphenyl diisocyanate, were present among occupationally unexposed workers, but the source and nature of the exposure is unknown.
International Archives of Occupational and Environmental Health, Aug. 2005, Vol.78, No.7, p.541-546. Illus. 28 ref.
Bonauto D.K., Sumner A.D., Curwick C.C., Whittaker S.G., Lofgren D.J.
Work-related asthma in the spray-on truck bed lining industry
This study examined compensation claims for occupational asthma associated with exposure to methylene diphenyl diisocyanate (MDI) among workers involved in spray-on truck bed lining. A descriptive study of workers' compensation claims was conducted. Eight such claims were identified between 1993 and 2002, resulting in a claims incidence rate of 200 per 10,000 full-time equivalent workers employed. This rate is excessive and suggests a need for significant intervention, including improvements in the clinical assessment provided to MDI-exposed workers.
Journal of Occupational and Environmental Medicine, May 2005, Vol.47, No.5, p.514-517. 12 ref.
Isophorone diisocyanate - determination method
Izocyjanian 3-izocyjanianometylo-3,5,5-trimetylocykloheksylu - metoda oznaczania [in Polish]
A method for the determination of isophorone diisocyanate in air is described. Air samples are collected by drawing a known volume of air through glass fibre filters impregnated with a solution of l-(2-pyridyl)piperazine. The filters are transferred into 4 ml vials and extracted in a shaker with 2 ml of the acetonitrile: dimethylsuloxide (9:1) mixture. The obtained extracts are analyzed by high performance liquid chromatography using ultraviolet or spectrofluorimetric detection. The working range of the analytical method is from 0.1 to 8.0 µg/ml (0.0013 to 0.106 mg/m3 for a 150 l air sample).
Podstawy i Metody Oceny Środowiska Pracy, 2005, Vol.43, No.1, p.13-18.
Cyclohexyl isocyanate - determination method
Izocyjanian cykloheksylu - metoda oznaczania [in Polish]
A method for the determination of cyclohexyl isocyanate in air is described. Air samples are collected by drawing a known volume of air through glass fibre filters impregnated with a solution of l-(2-pyridyl)piperazine. The filters are transferred into 4 ml vials and extracted in a shaker with 2 ml of acetonitrile:dimethylsulfoxide (9:1) mixture. The obtained extracts are analysed by high performance liquid chromatography with ultraviolet or spectrofluorimetric detection. The working range of the analytical method is from 0.1 to 8.0 µg/ml (0.0013 ÷ 0.106 mg/m3 for a 150 l air sample).
Podstawy i Metody Oceny Środowiska Pracy, 2005, Vol.43, No.1, p.5-11.
Ostiguy C., Gagné S., Lesage J., Van Tra H., Cloutier Y.
Development of a highly sensitive analytical method for isocyanates
Développement d'une méthode d'analyse d'isocyanates à très haute sensibilité [in French]
Isocyanates are lung and skin irritants and sensitizers that can cause many diseases, occupational asthma being the most serious. Current methods for determining these substances are often of limited use due to their inadequate sensitivity. This report describes the development of an analytical method to detect low levels of isocyanate in industrial settings. It is based on high-pressure liquid chromatography coupled with mass spectrometry. Sampling is carried out with single-membrane reactive cassettes. The method provides a useful tool for making decisions regarding appropriate personal protective equipment, safer work organization, reassignment of sensitized workers and identification of levels of non-reacted isocyanates in various materials.
Institut de recherche Robert-Sauvé en santé et en sécurité du travail (IRSST), 505 boul. de Maisonneuve Ouest, Montreal (Quebec) H3A 3C2, Canada, 2005. 44p. Illus. 82 ref. Price: CAD 6.42. Downloadable version (PDF format) free of charge.
http://www.irsst.qc.ca/files/documents/PubIRSST/R-419.pdf [in French]
Boutin M., Lesage J., Ostiguy C., Bertrand M.J.
Identification and quantification of isocyanates generated in the thermal degradation of polyurethane-based automobile paint
Identification et quantification des isocyanates générés lors de la dégradation thermique d'une peinture automobile à base de polyuréthane [in French]
Most car paints consist of polyurethanes, polymers obtained by reacting isocyanates with alcohols. During their thermal degradation, polyurethanes may regenerate isocyanates, which can cause asthma, dermatitis, conjunctivitis and acute poisonings. Workers may be exposed to the thermal degradation products of car paints during welding, milling or cutting operations on car body parts. This report presents a systemic approach for studying the thermal degradation process of polyurethanes, in particular the formation of isocyanates and their emission into the air. The results obtained in the laboratory led to the identification of the isocyanates likely to be generated during combustion of the paint. This approach can be used to study the thermal degradation of other polymers such as rubber, polyvinyl chloride and formaldehyde-based polymers.
Institut de recherche Robert-Sauvé en santé et en sécurité du travail (IRSST), 505 boul. de Maisonneuve Ouest, Montreal (Quebec) H3A 3C2, Canada, 2005. 60p. Illus. 115 ref. Price: CAD 6.42. Downloadable version (PDF format) free of charge.
http://www.irsst.qc.ca/files/documents/PubIRSST/R-418.pdf [in French]
Cowie H.A., Hughson G.W., Creely K.S., Graham M.K., Hutchison P.A., Aitken R.J.
Health and Safety Executive
An occupational hygiene assessment of the use and control of isocyanates in the UK
Approximately 6200 motor vehicle repair (MVR) workshops in the United Kingdom use isocyanates, with around 15000 employees directly exposed. In the non-MVR sector, a further 1600 enterprises were estimated to use isocyanates, with around 7000 employees directly exposed. Enterprises carrying out work with the greatest potential for exposure were generally aware of the health hazards and had taken appropriate action to control workers' exposure. Workplace surveys confirmed that exposure levels were generally low and that it was possible to control air concentrations to below the existing exposure limits with basic exposure control measures. These results suggest that isocyanate related asthma cases could be due to momentary lapses in exposure controls rather than prolonged, high level exposure that might be attributed to ignorance of the health risks and the recommended control measures. Alternatively, it is possible that the existing exposure limits do not ensure the adequate protection of exposed workers.
HSE Books, P.O. Box 1999, Sudbury, Suffolk CO10 2WA, United Kingdom, 2005. x, 238p. Illus. 31 ref. Price: GBP 25.00. Downloadable version free of charge.
http://www.hse.gov.uk/research/rrpdf/rr311.pdf [in English]
Karoly W.J., Flatley J.J., Stevenson R.D., Bowers J.D.
Airborne concentrations of methylene diphenyl diisocyanate (MDI) in North American wood mills during the manufacturing of oriented strand board (OSB)
Air samples were taken to determine the effectiveness of control measures used in oriented strand board (OSB) mills to prevent fugitive emissions of wood dust, methylene diphenyl diisocyanate (MDI) and MDI-coated wood dust. Personal sampling results (578 samples covering 11 job categories) ranged from 0.0002 to 0.524mg/m3, and area sampling results (1657 samples covering 14 stationary locutions in the mills) ranged from 0.0002 to 2.5mg/m3. Over 97% of the personal and 92% of the area sampling results were below 0.051mg/m3. Wipe testing was performed to determine the presence of unreacted diisocyanates from various surfaces. Positive results were found in about 13% of the wipe tests on surfaces in process areas.
Journal of Occupational and Environmental Hygiene, Dec. 2004, Vol.1, No.12, p.789-798. Illus. 20 ref.
Liu Y., Berode M., Stowe M.H., Holm C.T., Walsh F.X., Slade M.D., Boeniger M.F., Redlich C.A.
Urinary hexane diamine to assess respiratory exposure to hexamethylene diisocyanate aerosol: A human inhalation study
The use of urinary hexane diamine (HDA) as a biomarker to assess respiratory exposure to hexamethylene diisocyanate (HDI) aerosol was evaluated. Twenty-three auto body shop workers were exposed for two hours to HDI biuret aerosol. HDI exposures were quantified. Urine samples were collected at baseline, immediately post exposure, and every 4-5 hours up to 20 hours and analyzed for HDA using gas chromatography and mass spectrometry. Mean urinary HDA (mgg/g creatinine) increased sharply from the baseline value of 0.7 to 18.1 post exposure and decreased rapidly to 4.7, 1.9 and 1.1, respectively, at 4, 9 and 18 hours post exposure. Considerable individual variability was found. Urinary HDA can assess acute respiratory exposure to HDI aerosol but may however have limited use as a biomarker of exposure in the workplace.
International Journal of Occupational and Environmental Health, July-Sep. 2004, Vol.10, No.3, p.262-271. Illus. 34 ref.
http://www.ijoeh.com/pfds/1003_Liu.pdf [in English]
Maître A., Perdrix A.
Isocyanates [in French]
Isocyanates are characterized by the presence of one or several highly-reactive functional groups, providing them with exceptional industrial properties. This high reactivity also explains why they represent the most important chemical cause of occupational asthma in industrialized countries, and particularly in France. The severity of the pathologies is related to the nature of the induced asthma and bronchiolitis that follow acute exposures. However, there is still a lack of understanding of both the complex physiopathological mechanisms and the mutagenic effects. The requirement for strictly-controlled technical prevention measures, particularly in spray painting, is causing users to consider substitution products.
Encyclopédie médico-chirurgicale, Toxicologie-Pathologie professionnelle, 4th Quarter 2004, No.145, 5p. 64 ref.
Swaen G.M.H., Bloemen L.J.N., Twisk J., Scheffers T., Slangen J.J.M., Collins J.J., ten Berge W.F.J.P.
Mortality update of workers exposed to acrylonitrile in the Netherlands
To study the possible carcinogenic effects of acrylonitrile, the follow up of a cohort of 2842 acrylonitrile workers was updated. The comparison group consisted of 3961 unexposed workers from a fertilizer plant. Industrial hygiene assessments quantified past exposure to acrylonitrile, 8-hour averages as well as peak exposure, the use of personal protective equipment, and exposure to other potential carcinogenic agents. Standardized mortality ratios were calculated to adjust for the effect of age distribution, length of follow-up and temporal changes in background mortality rates. Cumulative dose-effect relations were determined for three exposure categories and three latency periods. The results show that no cancer excess seems related to exposure to acrylonitrile.
Journal of Occupational and Environmental Medicine, July 2004, Vol.46, No.7, p.691-698. 22 ref.
Mutagenic testing of workers exposed to toluene-diisocyanates during plastics production process
This study on the potential mutagenicity of toluene diisocyanates (TDI) involved 26 workers exposed to TDI during the production of plastics, together with 21 non-exposed controls. The concentration of TDI ranged between 0.007mg/3 and 0.016mg/3. Structural chromosome aberrations (SCA) were evaluated in 200 lymphocytes of peripheral blood, with an average occurrence of 2.6. Sister chromatid exchanges (SCE) were examined in 50 cells, the average occurrence being 8.127. Micronuclei (MN) were examined in 500 blocked cytokinesis cells, with an average occurrence of 12.07. The corresponding averages of the control group were 1.89 (SCA), 5.52 (SCE) and 4.38 (MN), respectively. The difference between the groups is of statistical significance, thus confirming the mutagenic activity of toluene diisocyanates or their metabolites.
American Journal of Industrial Medicine, May 2004, Vol.45, No.5, p.468-474. 25 ref.
A summary of health hazard evaluations: Issues related to occupational exposure to isocyanates, 1989 to 2002
Exposure to isocyanates is irritating to the skin, mucous membranes, eyes and respiratory tract. The most common adverse outcome is asthma due to sensitization, followed by contact dermatitis and hypersensitivity pneumonitis. After a background information on the characteristics of isocyanates, this document presents summary reports of 46 isocyanate-related health hazard evaluations (HHEs) carried out between 1989 and 2002, grouped by process type: adhesives; decomposition products; foaming; foundry applications; moulding; other. For each case, a concise description of the results is given, together with the requester's name and the purpose of the HHE.
Publications Dissemination, National Institute for Occupational Safety and Health (NIOSH), 4676 Columbia Parkway, Cincinnati, OH 45226-2002, USA, Jan. 2004. v, 37p. 44 ref.
http://www.cdc.gov/niosh/docs/2004-116/pdfs/2004-116.pdf [in English]
Antonsson A.B., Christensson B., Ancker K.
Do you repair car bodywork?
This booklet is aimed at persons who work in automobile or truck body repair shops and who face the risk of exposure to isocyanates. Among the topics addressed: symptoms of isocyanate exposure (nose and eye irritation, lung function impairment, asthma); limitation of exposure (ventilation, local exhaust, supplied air respirators); safe working methods during sanding, welding and cutting.
Prevent, Box 20133, 104 60 Stockholm, Sweden, 2003. Internet document (pdf format). 22p. Illus. 8 ref.
http://www.prevent.se/doc_pdf/verktyg/pdf/do_you_repair_car.pdf [in English]
Frick M., Björkner B., Hamnerius N., Zimerson E.
Allergic contact dermatitis from dicyclohexylmethane-4,4'-diisocyanate
From August 1999 to April 2001, there was an outbreak of severe eczema at a factory manufacturing medical equipment. A glue, mainly based on the isocyanate dicyclohexylmethane-4,4'-diisocyanate (DMDI), was suspected as being the cause of the problem. 16 workers with recent episodes of eczema were patch tested with a standard series, an isocyanate series and work material. 13 patients reacted to DMDI, nine to 1,6-hexamethylenediisocyanate (HDI) and four to isophoronediisocyanate (IPDI), all of which are aliphatic isocyanates. None reacted to aromatic isocyanates, diphenylmethane-4,4'-diisocyanate (MDI) or toluenediisocyanate (TDI). One explanation for this pattern could be that aromatic diisocyanates are more reactive and therefore inactivated before penetrating the skin. Five patients reacted to dicyclohexylmethane-4,4'-diamine (DMDA) and five to 4,4'-diaminodiphenylmethane (MDA). Concurrent reactions to DMDA and/or MDA with DMDI could be due to cross-reactivity. The positive reactions to MDA could also be a marker of MDI exposure.
Contact Dermatitis, June 2003, Vol.48, No.6, p.305-309. 17 ref.
Lazure L., Abdellaoui H., Lesage J., Charette M.
Evaluation of the confinement of preparation areas during paint spraying
Evaluation du confinement des aires de préparation lors de l'application de peinture [in French]
Automobile body paint shops are a priority target for the prevention of occupational asthma caused by isocyanates. The Occupational Health and Safety Institute of the Canadian Province of Quebec (l'Institut de recherche en santé et en sécurité du travail - IRSST) conducted two earlier studies on the evaluation of isocyanate exposure levels and on the efficiency of paint spray booths. For a full understanding of the levels of exposure to isocyanates in automobile body paint shops, it was also necessary to obtain data on the workstations situated outside the spray booths, in particular in the ventilated preparation area often used for certain types of paint preparation work. This report presents the results of evaluations of the potential exposure levels and the efficiency of systems used for eliminating contaminants present in workplace atmospheres of these preparation areas.
Institut de recherche en santé et en sécurité du travail du Québec (IRSST), 505 boul. de Maisonneuve Ouest, Montreal (Quebec) H3A 3C2, Canada, 2003. 61p. Illus. 11 ref. Price: CAD 6.42. Downloadable version (PDF format) free of charge.
http://www.irsst.qc.ca/files/documents/PubIRSST/R-353.pdf [in French]
Jones M., Cullinan P., Durham S., Newman Taylor A.
Health and Safety Executive
Cellular aspects of occupational asthma: Immunological studies in isocyanate exposed subjects
The cellular and molecular mechanisms that induce asthma due to expsoure to low molecular weight chemicals are not fully understood. The aim of this project was to gain a better understanding of the mechanisms of low molecular weight chemical haptens and in particular isocyanates. The study was carried out among occupational asthma patients in a university hospital, and involved bronchoscopy, specific IgE and T-cell studies. It was found that there was a lack of local IgE and IL-4 production in the lungs following challenge in patients allergic to isocyanates, which parallels the lack of detectable specific IgE in the serum of the majority of patients with isocyanate-induced asthma. There was, however, evidence of local tissue eosinophilia and IL-5 production. These findings suggest that isocyanate induced asthma in humans is a Th2 type response in which IgE does not have an obligatory role.
HSE Books, P.O. Box 1999, Sudbury, Suffolk CO10 2WA, United Kingdom, 2003. ix, 84p. Illus. 44 ref. Price: GBP 15.00.
http://www.hse.gov.uk/research/rrpdf/rr122.pdf [in English]
Frick M., Isaksson M., Björkner B., Hindsén M., Pontén A., Bruze M.
Occupational allergic contact dermatitis in a company manufacturing boards coated with isocyanate lacquer
Following the introduction of a lacquer based on diphenylmethane-4,4'-diisocyanate at a company producing flooring laminate boards, there was an outbreak of work-related skin lesions among workers. In five workers, patch testing was performed with a standard series, an isocyanate series and products present in the work environment. Among workers tested with the lacquer, contact allergy was found with concurrent reactions to 4,4'-diaminodiphenylmethane (MDA). Occupational contact with isocyanates should not be exclusively focused upon respiratory hazards, as this report shows that skin contamination probably increases the risk of developing contact allergy to isocyanates and isocyanate-related substances. When aiming at diagnosing contact allergy to isocyanates, it is desirable to perform a late reading, as positive reactions appear late. MDA appears to be a good marker for isocyanate hypersensitivity.
Contact Dermatitis, May 2003, Vol.48, No.5, p.255-260. 16 ref.
Occupational asthma, lung function decrement, and toluene diisocyanate (TDI) exposure: A critical review of exposure-response relationships
This literature review on the effects of toluene diisocyanate (TDI) exposure on respiratory health focused on bronchial asthma and the accelerated decline in lung function. In the early years of the industry, annual incidence rates of TDI-induced occupational asthma (OA) were as high as 5-6 percent. In settings where mean TDI concentrations have been maintained below 5ppb, OA incidence rates have declined to below 1% annually. Studies from the 1960s and 1970s that examined lung function decrement provided evidence of a decline in forced expiratory volume in one second (FEV1) during periods of ongoing exposure among employees experiencing high rates of work-related symptoms of OA. More recent studies have provided no consistent evidence of accelerated FEV1 loss among employees exposed up to 5ppb TDI (8-hr TWA) even with documented routine short-term TDI concentrations exceeding 20ppb.
Applied Occupational and Environmental Hygiene, Dec. 2002, Vol.17, No.12, p.891-901. 73 ref.
Frequency and trends of occupational asthma due to toluene diisocyanate: A critical review
Reports and statements on the frequency of occupational asthma due to isocyanates are contradictory. In order to clarify the issue, a critical review of the medical literature of the past half-century worldwide has been performed, with special emphasis on toluene diisocyanate (TDI) as the main representative of the isocyanate family. Nine longitudinal workplace studies of 2751 persons under risk allowed the calculation of incidences of occupational asthma due to TDI. Annual incidences were repeatedly above 5% before 1980, and have decreased to between 0 and 0.7% since 1980. Prevalences of occupational asthma due to TDI were estimated from ten cross-sectional studies, based on 788 persons. Prevalences were repeatedly above 10% before 1985, and have been mostly between 0 and 10% in recent years.
Applied Occupational and Environmental Hygiene, Dec. 2002, Vol.17, No.12, p.872-877. Illus. 35 ref.
Daftarian H.S., Lushniak B.D., Reh C.M., Lewis D.M.
Evaluation of self-reported skin problems among workers exposed to toluene diisocyanate (TDI) at a foam manufacturing facility
To investigate the dermal effects of toluene diisocyanate (TDI), a cross-sectional study was carried out at a polyurethane foam manufacturing plant. A totla of 114 workers completed a medical questionnaire and provided blood for antibody testing to TDI and other allergens. A subset of participants reporting skin symptoms underwent skin patch testing to a standard diisocyanate panel. Production line workers were more likely to report skin problems than those working in non-production areas (OR 2.66). Age, sex and duration of employment at the plant were comparable among participants working in production and non-production areas. Specific IgG antibody to TDI was detected in two individuals, while none of the samples demonstrated specific IgE antibody to TDI. Of the 26 workers who underwent skin patch testing, none developed reactions to the diisocyanate allergens. These results suggest that skin symptoms represent an irritant rather than an immunological reaction to TDI, or to an unidentified allergen present in the foam.
Journal of Occupational and Environmental Medicine, Dec. 2002, Vol.44, No.12, p.1197-1202. 30 ref.
Jarand C.W., Akapo S.O., Swenson L.J., Kelman B.J.
Diisocyanate emission from a paint product: A preliminary analysis
The purpose of this study was to evaluate emission of 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), and isophorone diisocyanate (IPDI) from a commercially available two-stage concrete coating. A laboratory model of an outdoor deck coating process was developed and isocyanate concentrations determined by reaction with 1-(2-methoxyphenol)- piperazine and subsequent high performance liquid chromatographic analysis with UV detection. The detection limit for 2,4-TDI and 2,6-TDI urea derivatives was 0.6µg TDI/g wet product, and 0.54µg IPDI/g wet product for the IPDI urea derivative. No 2,4-TDI or IPDI was detected in the mixed product. The 2,6-TDI emission rates per gram of wet product applied per hour after one hour, five hours and 15-hours were 0.32µg, 0.38µg and 0.02µg respectively. These emission rates should allow industrial hygienists to calculate exposures to isocyanates emitted from coating products.
Applied Occupational and Environmental Hygiene, July 2002, Vol.17, No.7, p.491-494. Illus. 14 ref.
Zey J.N., Stewart P.A., Hornung R., Herrick R., McCammon C., Zaebst D., Pottern L.M., Dosemeci M., Bloom T.F.
Evaluation of concurrent personal measurements of acrylonitrile using different sampling techniques
Since the 1980s certain US enterprises engaged in the production of acrylonitrile (AN) monomer, acrylic fibres and resins and other products containing AN have systematically been engaging in monitoring the exposure of their workers to the substance. Each enterprise chose its own method of personal air sampling. The aim of this study was to evaluate these methods in 8 separate locations, in order to establish whether the results can be used in a retrospective epidemiological study. In fact the results show that the plant measurements were sufficiently comparable for purposes of epidemiology.
Applied Occupational and Environmental Hygiene, Feb. 2002, Vol.17, No.2, p.88-95. 19 ref.
Inter-Organization Programme for the Sound Management of Chemicals (IOMC)
Conclusions of this criteria document on acrylonitrile: data from animal studies indicate that the product is a skin, respiratory and severe eye irritant. Acute dermal irritation has been reported in human studies. Animal ingestion and inhalation studies have given rise to the consistent observation of cancers (of the brain and spinal cord, ear canal, gastrointestinal tract and mammary glands), including upon the administration of non-toxic doses. Increases in cancer incidence have not been confirmed in epidemiological studies involving exposed workers, in part due to the limited number of published studies.
World Health Organization, Distribution and Sales Service, 1211 Genève 27, Switzerland, 2002. iv, 51p. Illus. Approx. 220 ref.
http://www.who.int/ipcs/publications/cicad/en/cicad39.pdf [in English]
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