title: Exposure to 4,4'-methylenediphenyl diisocyanate (MDI) during moulding of rigid polyurethane foam: determination of airborne MDI and urinary 4,4'-methylenedianiline (MDA).
abstract: Occupational exposure to 4,4'-methylenediphenyl diisocyanate (MDI) was measured during moulding of rigid polyurethane foam. The aim of the study was to find out whether an MDI-derived urinary amine metabolite could be detected in the urine of workers exposed to apparently low levels of MDI. Airborne MDI was sampled on 1-(2-methoxyphenyl)-piperazine (2MP)-impregnated glass fibre filters and determined by high-performance liquid chromatography (HPLC) using ultraviolet (UV) and electrochemical (EC) detection. The limit of detection of MDI was 3 ng ml-1 for a 20 microliters injection. The precision of sample preparation, expressed as relative standard deviation (RSD), was 1.3% with UV detection and 2.1% with EC detection at a concentration of 70 ng MDI ml-1 (n = 6). The 2MP-MDI derivative was stable at +4 degrees C up to eight weeks. The accuracy of the method was validated in an international quality control programme. Workers (n = 57) from three different factories participated in the study. Urinary 4,4'-methylenedianiline (MDA) metabolite was determined after acid hydrolysis as heptafluorobutyric anhydride derivatives by gas chromatography-mass spectrometry using chemical ionisation and monitoring negative ions. The limit of detection in urine was 0.2 nmol l-1. The precision of six analyses for a urine sample spiked to a concentration of 1 nmol l-1 was 29% (RSD). The MDI concentrations were below the limit of detection in most (64%) of the air samples collected in the worker's breathing zone. Still, detectable amounts of MDA were found in 97% of the urine samples. Monitoring of urinary MDA appears to be an appropriate method of assessing MDI exposure in work environments with low or undetectable MDI concentrations in the workplace air.
authors.affiliation: Department of Industrial Hygiene and Toxicology, Finnish Institute of Occupational Health, Topeliuksenkatu 41 a A, FIN-00250 Helsinki, Finland.
authors.forename: K
authors.initials: K
authors.lastname: Kääriä
authors.forename: A
authors.initials: A
authors.lastname: Hirvonen
authors.forename: H
authors.initials: H
authors.lastname: Norppa
authors.forename: P
authors.initials: P
authors.lastname: Piirilä
authors.forename: H
authors.initials: H
authors.lastname: Vainio
authors.forename: C
authors.initials: C
authors.lastname: Rosenberg
mesh_terms: D000328:Adult; D000395:Air Pollutants, Occupational / Q000032:analysis*; D000814:Aniline Compounds / Q000652:urine*; D005260:Female; D006801:Humans; D017953:Isocyanates / Q000032:analysis*; D008297:Male; D008875:Middle Aged; D016273:Occupational Exposure; D011140:Polyurethanes; D001559:Benzhydryl Compounds
chemical_list: D000395:Air Pollutants, Occupational; D000814:Aniline Compounds; D017953:Isocyanates; D011140:Polyurethanes; C005969:4,4'-diphenylmethane diisocyanate; D001559:Benzhydryl Compounds; C009505:4,4'-diaminodiphenylmethane