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  • Isocyanates

1982

CIS 82-1950 Malo J.L., Zeiss C.R.
Occupational hypersensitivity pneumonitis after exposure to diphenylmethane diisocyanate
A foundry worker developed dyspnoea and a restrictive breathing defect after exposure to diphenylmethane diisocyanate (MDI). His symptoms and lung function impairment subsided after he left foundry work. Specific inhalation challenges with MDI induced general malaise, a significant increase in body temperature and leukocyte count, and a decrease in forced vital capacity and transfer factor. Total antibody activity to a MDI human serum albumin conjugate was detected by ammonium sulfate precipitation and specific IgG antibodies were demonstrated by the enzyme-linked immunoabsorbent technique.
American Review of Respiratory Disease, Jan. 1982, Vol.125, No.1, p.113-116. Illus. 29 ref.

CIS 82-1378 Pacheco Y., Vergnon J.M., Grosclaude M., Biot N., Perrin-Fayolle M.
Case study of bronchoalveolitis due to isocyanate
A propos d'un cas de bronchoalvéolite à l'isocyanate [en francés]
Case study of mixed bronchial and alveolar disease in a worker exposed to isocyanate, with considerations on the aetio-pathogenic mechanisms of poisoning by this substance. Results of analysis of clinical signs and tests showed bronchial reactions due to a twofold mechanism (irritant and immunological), with parieto-alveolar reactions due to type-III hypersensitivity reaction.
Revue française d'allergologie, 1982, Vol.22, No.1, p.15-17. 11 ref.

CIS 82-1050 Woolrich P.F.
Toxicology, industrial hygiene and medical control of TDI, MDI, and PMPPI
The isocyanates used in the manufacture of polyurethanes cause sensitisation responses and also causes fire and explosion hazards. This review covers: chemical identifiers; chemical and physical properties; toxicological effects on animals; industrial hygiene and medical controls; first aid.
American Industrial Hygiene Association Journal, Feb. 1982, Vol.43, No.2, p.89-97. Illus. 33 ref.

CIS 82-443 Morel C., Gendre M., Cavigneaux A., Protois J.C.
Isophorone diisocyanate
Diisocyanate d'isophorone [en francés]
Synonyms, uses, physical and chemical properties, methods of detection and determination in air, fire hazards, pathology and toxicology (irritation of skin, mucous membranes of the eyes and respiratory tract; release of toxic substances in the event of fire; ACGIH TLV: 0.01ppm or 0.09mg/m3). References to relevant French safety and health regulations, and the French and international transport safety regulations. Technical and medical recommendations.
Cahiers de notes documentaires - Sécurité et hygiène du travail, 1st quarter 1982, No.106, p.151-154. 12 ref.

CIS 82-440 Mur J.M., Meyer-Bisch C., Cavelier C., Pham Q.T., Lacube P.
Isocyanates and lung function. A study of workers exposed to isocyanates on a polyurethane foam injection station
Isocyanates et fonction respiratoire. Etude d'ouvriers exposés à un poste d'injection de mousse polyuréthanne [en francés]
Study carried out in an automobile plant on 51 workers exposed to isocyanates and on 14 workers subsequently removed from exposure as a result of pathological findings. The study included an interview, a clinical examination and a series of lung function tests. The sensitising effect of isocyanates on the respiratory system was confirmed. Since many of those who had been withdrawn from exposure continue to present lung function anomalies, it is not possible to exclude the hypothesis that prolonged exposure to isocyanates may, over the long term, induce pulmonary fibrosis.
Cahiers de notes documentaires - Sécurité et hygiène du travail, 1st quarter 1982, No.106, Note No.1366-106-82, p.83-88. 17 ref.

1981

CIS 82-1915 Warwick C.J., Bagon D.A., Purnell C.J.
Application of electrochemical detection to the measurement of free monomeric aromatic and aliphatic isocyanates in air by high-performance liquid chromatography
1-(2-Methoxyphenyl)piperazine is used as the electrogenic reagent in the determination. It forms electrochemically active derivatives with all of the isocyanates of occupational hygiene interest that are readily oxidised at carbon electrodes. These derivatives are strongly absorbing in the ultraviolet region, enabling a combination of electrochemical and ultraviolet detectors to be employed to provide additional qualitative information if required. Comparison is made between the electrochemical detection method and high-performance liquid chromatography - ultraviolet detection methods for isocyanate analysis. The electrochemical detection method was significantly more sensitive than UV detection methods for the determination of phenyl isocyanate, toluene diisocyanate, hexamethylene diisocyanate and (4,4'-diisocyanatodiphenyl)methane in air.
Analyst, June 1981, Vol.106, p.676-685. Illus. 19 ref.

CIS 82-1703 Gallagher J.S., Ted Tse C.S., Brooks S.M., Bernstein I.L.
Diverse profiles of immunoreactivity in toluene diisocyanate (TDI) asthma
Possible immunoreactivity to mono- and diisocyanate protein conjugates was evaluated in 15 workers with TDI asthma and 17 normal (non-exposed) volunteers. Leucocyte migration tests and measurement of specific IgE by RAST suggest that isocyanates have the potential for eliciting heterogeneous immune responses in certain subpopulations of exposed workers. Continued contact with isocyanates may be necessary for maintenance of specific immunity.
Journal of Occupational Medicine, Sep. 1981, Vol.23, No.9, p.610-616. Illus. 40 ref.

CIS 82-1609 Purnell C.J., Walker R.F.
Methods for the determination of atmospheric isocyanates
Reported methods for the determination of aliphatic and aromatic isocyanates are discussed. Spectrophotometric methods provide a total isocyanate figure, but for mixtures of the monomer and prepolymer a calibration graph using similar standard mixtures is required. These methods are simple and inexpensive. Chromatographic methods are necessary to resolve the concentrations of individual isocyanates present in a mixture. High-performance thin-layer chromatography and high-performance liquid chromatography are the preferred techniques.
Analytical Proceedings, Nov. 1981, p.472-478. 35 ref.

CIS 82-1598 Karol M.H.
Survey of industrial workers for antibodies to toluene diisocyanate
Screening programme of 103 workers exposed 6-24 months to tolylene diisocyanate (TDI) concentrations <0.02ppm; 20 of the workers had acute exposures to TDI as a result of spills or splashes. Antibody responses by radioallergosorbent (RAST) test were observed only in some of the workers with an acute exposure history, and particularly in those whose acute exposure was accompanied by immediate respiratory symptoms and a decrease in FEV1 of 20% or greater. RAST test may be of value in routine serologic screening as an early warning of developing TDI hypersensitivity.
Journal of Occupational Medicine, Nov. 1981, Vol.23, No.11, p.741-747. Illus. 22 ref.

CIS 82-1363 Arslanian G.
Pathogenicity of isocyanates: Cross-sectional study of 38 workers exposed to diphenylmethane diisocyanate
Pathogénicité des isocyanates à propos d'une enquête transversale sur trente huit personnes exposées au diisocyanate de diphénylméthane (M.D.I.) [en francés]
This MD thesis gives the results of an investigation carried out following the occurrence of 3 cases of occupational asthma due to isocyanates, comparing the results of clinical examinations and spirographic tests in 38 exposed workers and 38 worker controls from a nearby workshop, with considerations on the state of the art concerning the harmful effects of isocyanates, especially as regards lung disease. Stress is on OSH rules (wearing of personal protective equipment, periodic monitoring of diphenylmethane diisocyanate concentration in air), and the necessity to screen predisposed workers by pre-employment medical examinations, with regular medical examinations (clinical, lung function tests) of exposed workers.
Université de Paris VI, Faculté de médecine Broussais Hôtel-Dieu, Paris, France, 1981. 55p. 31 ref.

CIS 82-1350 Weill H., Butcher B., Dharmarajan V., Glindmeyer H., Jones R., Carr J., O'Neil C., Salvaggio J.
Respiratory and immunologic evaluation if isocyanate exposure in a new manufacturing plant
Report of a study in which 168 wokers were examined prior to the start of work in a new toluene diisocyanate (TDI) plant and followed up together with newly recruited workers for a 5.5 years; the final study population was 277. TDI exposure was determined by personal monitors using the paper tape stain method for 8h measurement. Exposure levels were above current US TLV of 0.02ppm for 3% of exposure time. Detailed job histories gave cumulative exposure as a product of time and concentration. Pulmonary function changes for spirometric measurements, lung volumes and diffusing capacities were computed. Average annual FEV1 decline was 24ml/year. The effect of TDI exposure on FEV1 annual change was manifest in those who never smoked cigarettes. Clinically important bronchial hypersensitivity to TDI developed in 4.3% of the study population. TDI acts as a partial agonist on lymphocytes to stimulate adenosine monophosphate (AMP) levels; lymphocytes of TDI sensitive individuals have decreased ability to respond to cyclic AMP stimuli.
National Institute for Occupational Safety and Health, 4676 Columbia Parkway, Cincinnati, Ohio 45226, USA, 1981. 152p. Illus. 40 ref.

CIS 82-1004 Hosein H.R., Farkas S.
Risk associated with the spray application of polyurethane foam
Exposure to isocyanate vapour and to dust and overspray of polyurethane foam was evaluated using personal and area sampling at sites where insulating foam was applied by spraying in confined spaces. Exposure to tolylene diisocyanate vapour was frequently ≥ 0.08ppm for personal samples and 0.148ppm for area samples. Organic vapour cartridge respirators used by the sprayers were covered with overspray. Helpers used protective plastic bags over the head which posed an oxygen-starvation hazard. Workers' necks, faces, hair and clothing were contaminated with polyurethane particles and dust. Recommendations are made for reductions of significant health hazards existing at these work sites.
American Industrial Hygiene Association Journal, Sep. 1981, Vol.42, No.9, p.663-665. 14 ref.

CIS 82-734 Goldberg P.A., Walker R.F., Ellwood P.A., Hardy H.L.
Determination of trace atmospheric isocyanate concentrations by reversed-phase high-performance liquid chromatography using 1-(2-pyridyl)piperazine reagent
Aliphatic and aromatic isocyanates are determined in air by drawing a test atmosphere through a 2x10-4M solution of 1-(2-pyridyl)piperazine in toluene at a rate of 1l/min for 5-20min. The sample solution, in which the isocyanates form urea derivatives, is evaporated to dryness and an acetonitrile solutin of the residue is chromatographed using a column packed with ODS-Hypersil 5µm silica gel and eluted with an acetonitrile-0.1M ammonium acetae mobile phase at 2.0ml/minflow rate. The lower limit of detection for MDI and TDI is 0.5µg/m3 for a 10l air sample.
Journal of Chromatography, 1981, Vol.212, p.93-104. Illus. 38 ref.

CIS 82-791 Israeli R., Smirnov V., Sculsky M.
Symptoms of intoxication due to dicyclohexyl-methane-4,4'-diisocyanate exposure
Vergiftungserscheinungen bei Dicyclohexyl-Methan-4,4'-Diisocyanat-Exposition [en alemán]
Dicyclohexylmethane 4,4'-diisocyanate (DMDI) is used for coating glass bottles to prevent injuries among bottle users. The production process is described and 3 cases of poisoning are studied. Eleven of 15 workers who were first exposed to DMDI showed allergic and non-allergic skin reactions. Six suffered from vertigo with or without headaches and 4 showed obstructive ventilatory disorders, tachycardia, and hypotension (ECG normal). All were treated with oral antihistamines and local steroid application. The signs of the intoxication disappeared after 10-14 days from the beginning of the treatment. There was no difference in the clinical syndrome between the atopic and the non-atopic workers. It seems that DMDI does not affect the respiratory tract as strongly as TDI. The chronic effects of DMDI and the organic isocyanates are discussed. The difficulties of measuring DMDI in air are explained (TLV = 0.003ppm).
International Archives of Occupational and Environmental Health, 1981, Vol.48, No.2, p.179-184. Illus. 19 ref.

CIS 82-748 Innocenti A., Franzinelli A., Sartorelli E.
Longitudinal study of workers suffering from polyurethane asthma
Studio longitudinale in lavoratori affetti da asma da resine poliuretaniche [en italiano]
In 37 polyurethane production workers with isocyanate asthma, examinations carried out 40 months after exposure had ceased showed that asthmatic symptoms had disappeared in 32 workers but that chronic bronchitis had developed in 6. The progressive impairment of ventilatory function was evaluated by measuring the decrease in forced vital capacity (FVC) and FEV1 after exposure had ceased. Mean annual decreases of 86.3 and 67.7ml, respectively, were observed. Tolylene diisocyanate induces chronic and irreversible lung damage even after exposure is discontinued and impairment of FVC is greater than that of FEV1.
Medicina del lavoro, May-June 1981, Vol.72, No.3, p.231-237. 43 ref.

CIS 82-439 Walker R.F., Pinches M.A.
Chemical interference effects in the measurement of atmospheric toluene diisocyanate concentrations when sampling with an impregnated paper tape
The effect of toluenediamine (TDA), and a range of solvents and catalysts, on the measurement of tolylene diisocyanate (TDI) concentrations using a commercially available impregnated paper tape was evaluated. Low concentrations of TDA occurs as a hydrolysis product of TDI in polyurethane-producing factory atmospheres, produced a significant attenuation in the stain intensity formed by a given TDI concentration on MCM 4000 TDI paper tape. No interference effects were observed for the solvents and catalysts studied.
American Industrial Hygiene Association Journal, May 1981, Vol.42, No.5, p.392-397. Illus. 34 ref.

CIS 82-434
National Board for Occupational Safety and Health (Arbetarskyddsstyrelsen)
Isocyanates
Isocyanater [en sueco]
Amended version of the directive AFS 1980:10 (CIS 80-1980). The amendments relate to the scope (does not apply to quantities of ≤250g isocyanates per year and per person), medical supervision (workers with pulmonary disorders and with an allergic predisposition should not be given work involving exposure to isocyanates). An appendix contains a medical questionnaire about the worker's lungs and smoking habits. A subsequent amendment (AFS 1981:20 of 10 Dec. 1981) limits the scope: the provisions do not apply where exposure to the isocyanate-containing substance does not exceed 1h per week, provided the product contains no gaseous propellant and is not under pressure, that mixing takes place in a sealed container and that operators wear disposable gloves. Duplicate of CIS 80-1940.
Publikationsservice, Fack, 171 84 Solna, Sweden, 19 Feb. 1981. 20 + 5p. Gratis.

CIS 82-416 Hobara T., Kobayashi H., Higashihara E., Hirota H., Sakai T.
Health hazards due to exposure to low levels of toluene diisocyanate
Tolylene diisocyanate (TDI) concentrations in the workplace air of a plant producing polyurethane foam were measured. The serum IgE of 39 workers, and leucograms and pulmonary function tests in 20 workers showed: TDI workplace air concentrations were 0.017-0.021ppm, which was lower than the TLV. Serum IgE was significantly higher in TDI workers than in controls. Some of the workers with less than 1 year exposure to TDI showed significantly high serum IgE values. All these TDI-exposed workers with high serum IgE levels had symptoms of eosinophilia and obstructive ventilatory impairment. Summary and wording of all tables (serum IgE levels, leukograms, pulmonary function tests by flow-volume curve) in English.
Yamaguchi Igaku (Yamaguchi Medical Journal), Mar. 1981, Vol.30, No.1, p.87-91. Illus. 13 ref.

CIS 82-412 Morel C., Gendre M., Cavigneaux A., Protois J.C.
French National Research and Safety Institute (Institut national de recherche et de sécurité
Hexamethylene-1,6-diisocyanate
1,6-diisocyanate d'hexaméthylène [en francés]
Uses, physical and chemical properties, methods of detection and determination in air, fire hazards (low flammability, open-cup flashpoint: 135°C) and extinguishing agents, pathology and toxicology (inflammatory skin reaction, eye irritation, respiratory disorders, NIOSH TLV: 0.035mg/m3). Reference to the French occupational safety and health legislation and French and international transport regulations. Technical and medical recommendations.
Cahiers de notes documentaires - Sécurité et hygiène du travail, 4th quarter 1981, No.105, p.633-636. 13 ref.

CIS 81-1933 Morel C., Gendre M., Limasset J.C., Cavigneaux A., Protois J.C.
French National Research and Safety Institute (Institut National de recherche et de sécurité)
Methyl isocyanate
Isocyanate de méthyle [en francés]
Uses, physical and chemical properties, methods of detection and determination in air, fire hazards (open-cup flashpoint: -7°C), pathology and toxicology (strongly irritant to skin, conjunctival tissue, respiratory tract; U.S. TLV: 0.05mg/m3). French OSH regulations; French and international regulations concerning transport. Recommendations for technical and medical prevention.
Cahiers de notes documentaires - Sécurité et hygiène du travail, 3rd quarter 1981, No.104, p.451-454. 11 ref.

CIS 81-1327 Mahieu J.C.
Production and use of polyurethane foams
Mise en oeuvre des mousses polyuréthanes. [en francés]
This fact sheet gives a summary of basic information: succinct data on properties, uses and production methods; table of hazards and safety measures (poisoning, fire, chemical and thermal burns, explosions); relevant French legislation.
Cahiers de notes documentaires - Sécurité et hygiène du travail, 1st quarter 1981, No.102, Note No.1304-102-81, p.69-72.

CIS 81-1088 Lob M., Boillat M.A.
Delayed asthma due to diphenylmethane diisocyanate
Asthme retardé au diphénylméthane-diisocyanate (MDI). [en francés]
See CIS 72-2260 for a case study (Lob M.) on delayed asthma with fever due to this substance. The present article gives a more recent similar case study (following exposure while welding polyurethane belts) and 3 others which turned up in the course of an investigation in the various plants where these belts were used. In all these cases the workers concerned had been exposed to fumes given off during welding of the belts, using a hot plate. The fumes did not contain tolylene diisocyanate. Follows a review of the pyrolysis of polyurethanes and theories on the mechanism of respiratory disorders due to diisocyanates, emphasing the hazards of inhalation tests and the importance of occupational anamnesis in the case studies described.
Schweizerische medizinische Wochenschrift - Journal suisse de médecine, 31 Jan. 1981, Vol.111, No.5, p.150-154. Illus. 23 ref.

1980

CIS 86-429 Toluene diisocyanate (TDI)
Diisocianato de tolueno (TDI) [en portugués]
Data sheet on toluene diisocyanate (TDI), containing information on: chemical composition, properties, main hazards, emergency measures, first-aid measures, handling and storage, and treatment of residues. The TLV in Brazil is: 0.016ppm (0.11mg/m3).
Fundacentro, C.P. 11484, CEP 05499 São Paulo, SP, Brazil, 1980. 2p. Bibl.

CIS 84-773 Mazzella di Bosco M., Tarducci G., Esposito Iacenna V.
Health effects of hydrocyanic acid, cyanides, cyano compounds, cyanic acid and its esters
Contributo alla conoscenza della patologia da acido cianidrico, cianuri, composti del cianogeno, acido cianico e suoi esteri [en italiano]
Aspects reviewed are: pathogenesis (toxicological profiles of hydrocyanic acid; organic compounds such as nitriles; isocyanates), symptoms of acute poisoning, long-term exposure, first aid, prevention and biological monitoring. Conclusions: knowledge of the occupational pathology is relatively sparse, especially as regards the clinical picture of prolonged exposure; medical supervision of exposed subjects is not without difficulties even when methods of biological monitoring are available.
Rivista degli infortuni e delle malattie professionali, Sept.-Dec. 1980, Vol.6, Nos.5-6, p.685-700. 60 ref.

CIS 81-1349 Baur X., Dorsch W., Fruhmann G., Römmelt H., Roth P., Diller W.
Clinical symptoms and results of a RAST test and an inhalation provocation test
Klinische Symptomatik und Ergebnisse von RAST und inhalativem Provokationstest [en alemán]
Report on research to determine the indicative value of the RAST test for clinical diagnosis of asthma due to isocyanate. Description of preparation of test discs, methods used for carrying out the RAST test and TDI exposure test. Technical data concerning exposure, symptoms and results of x-ray examinations, lung function tests and RAST tests in 9 workers with symptoms of respiratory sensitivity are set out in tabular form, with comments. The results show a specific sensitisation with IgE antibodies in several patients with asthma due to exposure to isocyanates. The results of the RAST and the exposure test did not always agree. Tranfer to other work did not always result in immediate disappearance of respiratory disorder.
Zentralblatt für Arbeitsmedizin, Arbeitsschutz, Prophylaxe und Ergonomie, Apr. 1980, No.4, p.104-109. 22 ref.

CIS 81-1348 Diller W., Alt E., Bauer X., Fruhmann G.
Mass screening using specific radioallergosorbent tests (RAST) of workers exposed to isocyanate
Feldstudie mit spezifischen Radio-Allergo-Sorbens-Testen (RAST) bei Isocyanat-Exponierten (TDI) [en alemán]
Results of RAST tests of serum samples from 117 workers exposed to tolylene diisocyanate. The tests were negative in 83 exposed but symptomless workers; in 34 exposed workers with respiratory symptoms 5 had positive RAST test findings. Apparently, isocyanates have a low degree of antigenic potential, but in the case of exposure to isocyanates together with respiratory symptoms, a positive RAST test shows an allergic condition, in which case the worker should be transferred immediately to another post.
Zentralblatt für Arbeitsmedizin, Arbeitsschutz, Prophylaxe und Ergonomie, Apr. 1980, No.4, p.100-103. 18 ref.

CIS 81-1302 Determination of isocyanates in air - Liquid chromatography method
Bestämming av isocyanater i luft - Vätskekromatografisk metod (HPLC) [en sueco]
Description of a liquid chromatography method (high performance) which overcomes some of the disadvantages of spectrophotometric methods (high separation sensitivity for isocyanate adducts). The air to be analysed is passed through a solution of 9-(N-methylaminomethyl)anthracene in toluene. Reaction times vary between 20min and 2h according to the type of isocyanate. The sample is eluted with an acetonitrile/triethylammonium phosphate buffer solution. Detection is by measuring UV absorbance (254nm).
Arbetarskyddsstyrelsen, Arbetsmedicinska avdelningen, 171 84 Solna, Sweden, 1980. 13p. Illus. 2 ref.

CIS 81-1089 Durand G., Linglin P.
Isocyanates and respiratory function - Use of respiratory function tests with a "vitalograph" apparatus in occupational medicine
Isocyanates et fonction respiratoire - Apports du vitalograph en médecine du travail [en francés]
MD thesis. General considerations on isocyanates (properties, industrial uses, poisoning symptoms, mode of toxicity, TLVs). Report on an investigation in 25 workers employed in a plant using diphenylmethane diisocyanate to protect a rigid polyurethane foam used in the manufacture of skis. The major part of the thesis is devoted to a presentation and detailed analysis of the results of spirometric tests with a "vitalograph" (technical data on this apparatus are given); VC, FEV1, mean mid-expiratory flow rate. Out of 20 subjects whose spirometric tracings could be used, 6 showed a significant reduction in one or more parameters during the daily hours of work. The influence of smoking is considered, and the limitations of the results obtained are emphasised.
Université scientifique et médicale de Grenoble, Domaine de la Merci, La Tronche, France, 1980. 75p. Illus. 40 ref.

CIS 81-731 Dharmarajan V., Rando R.J.
Critical evaluation of continuous monitors for toluene diisocyanate.
The modalities and results of an exhaustive and critical laboratory study to evaluate the performance of continuous area and personal monitors are described. The studies consisted of dynamic calibrations, the effect of humidity and temperature on the measurements, and the interferences due to commonly encountered contaminants in a TDI manufacturing plant. The response and resolution of the personal monitor for short-term fluctuations of TDI concentration in time and space are reported.
American Industrial Hygiene Association Journal, Dec. 1980, Vol.41, No.12, p.869-878. Illus. 14 réf.

CIS 81-488 Nava C., Briatico-Vangosa G.
Isocyanate pathology: Methods of immunological diagnosis
La patologia da isocianati: metodi di diagnosi immunologica [en italiano]
250 workers exposed to diisocyanates were studied. Skin tests were done with conjugates of tolylene diisocyanate (TDI) or methylene diisocyanate (MDI) and human or egg albumin. There were reactions due to the presence of IgE and IgG immunoglobins, and cross reactions between the isocyanates. Exposure tests were also done in 45 cases: there were immediate and/or diphasic reactions in 55.6% and late reactions in 22.2%. The immunogenic and allergogenic properties of TDI and MDI were established.
Medicina del lavoro, July-Aug. 1980, Vol.71, No.4, p.305-311. Illus. 13 ref.

CIS 81-171 Andersen M., Binderup M.L., Kiel P., Larsen H., Maxild J.
Mutagenic action of isocyanates used in the production of polyurethanes.
Toluene diisocyanate (TDI), 4-4'-methylenediphenyl isocyanate (MDI), 1,6-hexane diisocyanate (HDI), phenyl isocyanate, and 1-naphthyl isocyanate, were tested for mutagenicity in Salmonella. TDI, 1-naphthyl isocyanate, and MDI were mutagenic after metabolic activation. The effect is ascribed to the amine analogues formed during hydrolysis. Isocyanates are thus potentially mutagenic and carcinogenic to man.
Scandinavian Journal of Work, Environment and Health, Sep. 1980, Vol.6, No.3, p.221-226. Illus. 20 ref.

CIS 81-117 Ascher R.
Hazards of organic isocyanates and their prevention
Risques et prévention lors de l'utilisation des isocyanates organiques. [en francés]
Communication to the Joint Technical Regional Committee for the Textile Industry (Comité technique régional des industries textiles), Lille, France. Contents: health disorders and health damage due to commercially available polyurethanes (PU); statistics of compensated disease due to PU in France; properties of isocyanates used in industry; principal uses (paints and varnishes, expanded plastics for moulding; foaming); hazards; preventive medicine; safety engineering (integrated safety; collective protection; storage and distribution; work on storage tanks; leakage; liquid transfer of isocyanates; risk of inhalation); methods of analysis in the atmosphere; fire hazards and their prevention.
Caisse régionale d'assurance maladie du Nord de la France, 11 boulevard Vauban, BP 3008, 59024 Lille Cedex, 12 June 1980. 34p. Illus. 15 ref. Gratis.

CIS 80-1940 Isocyanates
Isocyanater [en sueco]
This directive (effective 1 Jan. 1981) applies to all activities involved in the production and indusrial use of isocyanates. Contents: general rules (substitution of less harmful substances; use wherever possible of prepolymerised isocyanates; personnel information); medical supervision; marking and labelling; workplaces and workplace layout and equipment (ventilation); elimination of spills; personal protection and personal hygiene. Appended: detailed commentaries (properties of 8 isocyanates, health hazards, reference to other directives and standards).
AFS 1980:10, Arbetarskyddsstyrelsen, Fack, 171 84 Solna, Sweden, 19 Aug. 1980. 20p. Gratis.

CIS 80-1669 Prügger F.
Health damage due to diisocyanates
Erkrankung durch Diisocyanate [en alemán]
Tolylene, diphenylmethane, naphthylene and hexamethylene diisocyanates are the most important as regards volume of production and number of workers exposed. Disorders of the respiratory tract (including a recent case of allergic asthma) were observed in 5% of the exposed workers. Roundup of the state of the art concerning toxic concentrations in animals and man, symptoms and health damage. In comparison with the lung disorders due to these substances, toxic and allergic skin disorders are relatively insignificant. Review of the symptoms and clinical course of allergic asthma; results of immunological research.
Sichere Arbeit, 1980, Vol.33, No.2, p.23-25.

CIS 80-1336 Smith A.B., Brooks S.M., Blanchard J., Bernstein I.L., Gallagher J.
Absence of airway hyperreactivity to methacholine in a worker sensitized to toluene diisocyanate (TDI).
A woman exposed to TDI working in a plant producing polyester-resin/fibrous reinforced plastic fixtures reacted negatively to tests for p-tolyl isocyanate IgE antibodies and leukocyte inhibition factor for isocyanate antigen. Methacholine challenges were negative even when symptoms were at a maximum. Airway response to TDI may not always be accompanied by methacholine hyperreactivity.
Journal of Occupational Medicine, May 1980, Vol.22, No.5, p.327-331. 42 ref.

CIS 80-1097 White W.G., Morris M.J., Sugden E., Zapata E.
Isocyanate-induced asthma in a car factory
Respiratory symptoms occurred in women machinists making seat covers from nylon backed with flame-bonded polyurethane foam. A study of 192 women showed an increase in asthmatic symptoms associated with this fabric. Results are given of lung function and environmental studies. Concentrations of 0.0003-0.003ppm tolylene diisocyanate (TDI) were found in the air around the fabric. 4 of 9 women with symptoms had IgE antibodies to TDI.
Lancet, 5 Apr. 1980, Vol.1, No.8171, p.756-760. 10 ref.

1979

CIS 80-1646 Cavelier C., Mereau P., Mur J.M.
Results of two epidemiological surveys with workers producing polyurethane foam mouldings.
Résultats de deux enquêtes épidémiologiques chez des ouvriers fabriquant des pièces en mousse de polyuréthane. [en francés]
One study comprised 318 people working in factories manufacturing car trimmings and seats. The mean atmospheric concentration of isocyanates (TDI and MDI) was generally below the threshold limit value of 0.02ppm. There was no excessive incidence of bronchitic or asthmatic disorders or allergic reactions, especially in TDI exposed workers. Reduction in VC and in factor K (CO transfer/alveolar volume) was observed in the most highly exposed subjects. The second study involved 125 people working in a factory using massive quantities of TDI. Atmospheric concentrations of isocyanates were higher than the TLV on average, with peaks up to 100 times the TLV. There was an excessive incidence of subacute symptoms and syndromes of the restrictive type. Results are compared with those of other authors. A reduction of the TLV is recommended, and MDI should replace TDI.
Edition INRS No.1103, Institut national de recherche et de sécurité, 30 rue Oliver-Noyer, 75680 Paris Cedex 14, France, Dec. 1979, p.103-151. Illus. 33 ref.

CIS 80-1329 Diisocyanates
Diisocyanater [en noruego]
Revision of the previous rules (CIS 77-1342). The TLVs for 2,4-tolylene, 2,6-tolylene and diphenylmethane diisocyanates are now fixed at 0.01ppm.
Bestillingsnr. 313, Directorate of Labour Inspection (Direktoratet for arbeidstilsynet), Postboks 8103 Dep., Oslo 1, Norway, May 1979. 8p. Gratis.

CIS 80-1345 Chester E.H., Martinez-Catinchi F.L., Schwartz H.J., Horowitz J., Fleming G.M., Gerblich A.A., McDonald E.W., Brethauer R.
Patterns of airway reactivity to asthma produced by exposure to toluene diisocyanate.
Bronchial inhalation challenge tests were done in 20 symptomatic workers exposed to toluene diisocyanate (TDI) and 10 asthmatic and 10 healthy controls. The presence of immediate, dual and late reactions in symptomatic workers suggested the presence of specific sensitivity to TDI. TDI may cause asthma by both specific and non-specific (irritant) mechanisms.
Chest, Feb. 1979, Vol.75, No.2, Supplement, p.229-231. Illus. 9 ref.

CIS 80-1110 Alexandersson R., Kolmodin-Hedman B., Hedenstierna G., Magnusson M.
Diisocyanates - HDI: Lung physiology studies in car painters
Diisocyanater - HDI: Lungfysiologiska undersökningar av billackerare [en sueco]
The effects of isocyanates, especially hexamethylene diisocyanate (HDI), were studied in car painters, sheet-metal workers (exposed to solvents, but not HDI), and car mechanics (no exposures). The results of lung function studies (spirometry and nitrogen washout) on Monday morning were compared with those on Friday afternoon. Closing volume was increased in HDI-exposed workers, and tended to increase over the working week. The nitrogen washout method indicates small airways effects before they are discernible by spirometry.
Arbete och hälsa - Vetenskaplig skriftserie 1980:5, Arbetarskyddsverket, Stockholm, Sweden, 1979. 22p. 37 ref.

CIS 80-1005 Nordic Group of Experts for TLV Documentation - 9. Diisocyanates
Nordiska expertgruppen för gränsvärdesdokumentation - 9. Diisocyanater [en sueco]
Literature survey of diisocyanate toxicity: physicochemical properties; toxicology, organic effects (irritation, sensitisation, lung function, skin, conjunctiva, blood and haematopoietic organs, gastrointestinal tract); pathogenic mechanism; exposure indices; dose-response relation (acute and chronic effects); research needs; evaluation of data. Appended: TLVs adopted in 18 countries; sampling and analysis methods.
Arbete och hälsa - Vetenskaplig skriftserie 1979:34, Arbetarskyddsverket, Stockholm, Sweden, Aug. 1979, 54p. 106 ref.

CIS 80-998 Lipina T.G., Tubina A.Ja., Kunilova L.V.
Determination of tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate in air
Opredelenie toluilendiizocianata i 4,4'-difenilmetandiizocianata v vozduhe [en ruso]
2 photocolorimetric methods are described. 4,4'-Diphenylmethane diisocyanate reacts by condensation with p-dimethylaminobenzaldehyde (DABA) in the presence of acetic acid. Sensitivity is 0.25µg/4ml solution. Detection limit is 0.04mg/m3. 2,4-Tolylene diisocyanate also reacts with DABA. Sensitivity is 0.5µg/4ml; detection limit 0.025mg/m3. Chlorobenzene, phosgene, ammonia and biphenyl vapours do not interfere. The diisocyanates can be determined separately.
Gigiena truda i professional'nye zabolevanija, Aug. 1979, No.8, p.55-56. 7 ref.

CIS 80-735 Hardy H.L., Devine J.M.
Use of organic isocyanates in industry - Some industrial hygiene aspects.
The health hazards (skin contact, eye splash, ingestion, inhalation) of isocyanate monomers and prepolymers are set out, and recent papers dealing with acute and chronic effects of isocyanate inhalation and their relevance to hygiene standards are reviewed. Methods of process control (substitution, total enclosure, partial enclosure under local exhaust extraction) are presented.
Annals of Occupational Hygiene, 1979, Vol.22, No.4, p.421-427. 14 ref.

CIS 80-435 Tse C.S.T., Chen S.E., Bernstein I.L.
Induction of murine reaginic antibodies by toluene diisocyanate - An animal model of immediate hypersensitivity reactions to isocyanates.
Investigation to establish an analogous homocytotropic antibody model in mice immunised with isocyanate-protein conjugates. Tolylene diisocyanate (TDI) was conjugated to serum albumins; the amount of ligand was determined spectrophotometrically. Mice were immunised and boosted 28 days later with 100µg TDI conjugated proteins or unconjugated proteins plus 1mg alum. Sera were assessed for 48h passive cutaneous anaphylaxis; sera from mice immunised with conjugated serum albumin demonstrated passive cutaneous anaphylaxis titers of 1:57 or higher when challenged with homologous conjugates and somewhat lower titers after reactions with heterologous conjugates. Mice immunised with carrier proteins alone produced homocytotropic antibody (1:40) to corresponding unconjugated proteins and homologous TDI-conjugates (1:5 to 1:10) but not to heterologous carrier proteins or TDI-conjugates. Findings are shown in tabular form.
American Review of Respiratory Disease, Oct. 1979, Vol.120, No.4, p.829-835. 17 ref.

CIS 80-433 Bjurström R.
Determination of isocyanates in workplace air by liquid chromatography
Mätning av isocyanater i arbetsmiljön med vätskekromatografisk metodik [en sueco]
Testing of a new method, more sensitive than those currently used to determine concentrations of isocyanates in workplace air. The concentration of isocyanates is determined by combining them with an anthracene derivative when sampling. After separation in the laboratory the isocyanates are determined individually by high-pressure liquid chromatography. The method has been used in industry with good results (manufacture of polyurethane cushions). English version may be obtained from Health and Safety Executive, Translation Services, Explosion and Flame Laboratory, Harpur Hill, Buxton, Derbyshire, United Kingdom.
Undersökningsrapport 1979:23, Arbetarskyddsstyrelsen, 17184 Solna, Sweden, 1979. 42p. Illus. 5 ref. Price: Swe-cr.10.00.

CIS 80-466 Harries M.G., Burge P.S., Samson M., Taylor A.J.N., Pepys J.
Isocyanate asthma: respiratory symptoms due to 1,5-naphthylene diisocyanate.
Occupational asthma is reported in 3 workers exposed to 1,5-naphthylene diisocyanate (NDI), a hot curing agent used in manufacturing rubber. NDI was thought to be safer than tolylene or diphenylmethane diisocyanate on account of its higher melting point. Provocation tests indicated sensitisation to NDI. After 3 years, airways narrowing persisted in the 2 workers who remained exposed.
Thorax, Dec. 1979, Vol.34, No.6, p.762-766. 12 ref.

CIS 79-1916 Kryńska A., Pośniak M.
Method for determining tolylene diisocyanate in air
Metoda oznaczania toluilenodwuizocyjanianu w powietrzu [en polonés]
A review of the industrial uses and toxicity of 2,4-tolylene diisocyanate (TDI) and various methods for its determination in air is followed by a description of a colorimetric method by which 0.06mg TDI can be determined in 1m3 air. The TDI is converted into diamine by hydrolysis; the diamine is caused to react with sodium carbonate, and then with salt R, used as a passive component in the coupling reaction which produces an azo dye. Maximum absorption of the compound thus obtained occurs at 490nm wavelength, and the variation coefficient is within ±6%. Salt R effectively replaces N-(1-naphtlyl)ethylenediamine which is difficult to obtain; thus the sensitivity and accuracy of this method are comparable with those of Marcali's method.
Prace Centralnego instytutu ochrony pracy, 1979, Vol.29, No.100, p.35-43. 20 ref.

CIS 79-1631
Health and Safety Executive, London.
Isocyanates: Toxic hazards and precautions
This guidance note gives information on: properties; chemical formulae; TLVs (0.02ppm for toluene diisocyanate and diphenylmethane diisocyanate, and other aromatic isocyanates, 0.01ppm for isophorone diisocyanate, in the United Kingdom); determination of environmental levels; toxic effects; handling of isocyanates; protective clothing; medical supervision of workers and first aid; statutory requirements; descriptive list of 5 types of isocyanate compounds and of 5 other isocyanates; industrial uses; toxic hazards and precautions to be taken in manufacturing processes for foam block, flexible foam (flame bonding), moulded articles, polyurethane foam, etc.) and use of urethane rubbers, polyurethane paints and lacquers, printing inks, adhesives, and foundry core binders.
Guidance Note EH 16, H.M. Stationery Office, P.O. Box 569, London SE1 9NH, United Kingdom, Feb. 1979. 7p. Price: £0.30.

CIS 79-1424 Karol M.H., Sandberg T., Riley E.J., Alarie Y.
Longitudinal study of tolyl-reactive IgE antibodies in workers hypersensitive to TDI.
3 workers with tolylene diisocyanate (TDI) sensitivity were evaluated for IgE antibodies over 13 months, using a radioallergosorbent test system. Antibody titres were elevated in 2 who experienced several bronchial hypersensitivity responses to TDI with or without cutaneous reactions during the study period. Antibody titres were low in a third subject who showed no such reactions during the study. In the absence of renewed TDI exposure, sensitive workers may have titres indistinguishable from those of non-sensitive TDI-workers.
Journal of Occupational Medicine, May 1979, Vol.21, No.5, p.354-358. 10 ref.

CIS 79-730 Tyrer F.H.
Hazards of spraying with two-pack paints containing isocyanates.
The spray from these paints consists partly of isocyanate in liquid form, and partly of particles of the prepolymer, with isocyanate droplets adhering to them. 6 case histories of paint sprayers allergic to isocyanates are given, illustrating the lack of information provided by manufacturers and of precautions taken. Recommendations made included: spraying only in booths or enclosures with effective exhaust ventilation; use of airline breathing apparatus; exclusion of workers with a history of respiratory allergy; mention of the isocyanate ingredient on the label.
Journal of the Society of Occupational Medicine, Jan. 1979, Vol.29, No.1, p.22-24.

1978

CIS 84-1645
British Cast Iron Research Association
Handling, storage and disposal of hazardous materials in the foundry - materials for isocyanate-based processes
This data sheet describes the hazard from isocyanate-based processes for mould and core making in foundries and recommends measures to prevent accidental exposure.
BCIRA, Alvenchurch, Birmingham B48 7QB, United Kingdom, 1978. 3p. 7 ref.

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