An air sampling method for the determination of isocyanates, aminoisocyanates and amines formed during the thermal degradation of polyurethane (PUR) is presented. The method is based on the collection of air samples using impinger flasks containing di-n-butylamine (DBA) in toluene with a glass fibre filter in series. Isocyanates are derivatized with DBA to urea derivatives, and amines are derivatized in a subsequent work-up procedure with ethyl chloroformate (ET) to carbamate esters. Amine, aminoisocyanate and isocyanate derivatives were characterized using liquid chromatography-time of flight mass spectrometry (LC-TOFMS) and liquid chromatography-chemiluminescent nitrogen detection (LC-CLND). Quantification was performed by LC-MS, monitoring molecular ions [MH]+ in the electrospray mode. The instrumental detection limits for amines, aminoisocyanates and isocyanates were in the ranges 30-40, 2-3 and 3-70 fmol, respectively. Thermal degradation products of PUR were observed in high concentrations during welding in district heating pipes and PUR-coated metal sheets. Eleven isocyanates, three amines and five aminoisocyanates were identified. The concentrations of isocyanates, aminoisocyanates and amines in samples collected in the smoke close to the welding spot were in the ranges 150-650, 4-290 and 1-70 ppb, respectively. In samples collected in the breathing zone, isocyanates and aminoisocyanates were observed in the ranges 9-120 and 4-19 ppb, respectively. The compounds were present in both gas and particle phases. Volatile compounds dominated in the gas phase, whereas less volatile compounds dominated in the particle phase. The method presented makes it possible to sample and determine amines and aminoisocyanates, in addition to isocyanates. The need to monitor these compounds is clearly illustrated by the high concentrations found during the thermal degradation of PUR.
The non-professional use of UV-curing nail polishes poses a risk of sensitization from acrylates and methacrylates.
A method for determination of technical grade isocyanates used in the production of polyurethane (PUR) is presented. The isocyanates in technical grade products were characterised as di-n-butylamine (DBA) derivatives using LC-MS and LC-chemiluminescent nitrogen detection (CLND) and the total isocyanate content was compared to a titration assay. For collection of isocyanates in air, an impinger-filter sampling technique with DBA as derivatisation reagent was used. Characterised DBA and nonadeuterium labelled DBA derivatives of isocyanates in technical products were used as calibration standards and internal standards, respectively, in the analysis of air samples. Three workplaces were studied where PUR products were produced either by spraying or by moulding. In both technical products and in air samples, a number of monomeric, oligomeric and prepolymeric isocyanates of e.g. methylenebisphenyl diisocyanate (MDI) and hexamethylene diisocyanate (HDI) were characterised. Several of these have not previously been described in workplace atmospheres. In the technical isocyanate products, between 69 and 102% of the NCO content determined by titration was accounted for by LC-CLND. Quantifications of a wide range of isocyanates in air samples were performed with correlation coefficients in the range 0.988-0.999 (n= 8) and the instrumental detection limits were 0.7-25 pg. At the two workplaces where MDI- and HDI isocyanurate-based products were sprayed, the isocyanate composition in the air reflected the composition in the technical product. At the workplace where a MDI-based product was used in a moulding process, only the monomeric isocyanates were found in the air. The advantage of using characterised technical grade isocyanates as analytical standards was clearly demonstrated and the possibility of using index compounds when monitoring isocyanate exposure is discussed.
Carvone (l-carvone), a mint flavour in spearmint oil, is considered a mild skin sensitizer. Carvone-sensitization may be linked to oral/perioral signs and oral lichen planus, but studies are sparse. The prevalence of patch test reactions to carvone and relevant findings from the positive group were investigated. Records for patch-tested patients at the Malmö clinic, for the period 1996 to 2016, were studied. Carvone-positive and carvone-negative patients were compared regarding patch test data from baseline series and dental series. Dental series-tested carvone-positive patients were also compared with a matched group. A total of 147 out of 4,221 referred patients had a positive patch test to carvone. Sensitized patients had higher mean age and were primarily women; 73% had oral signs and 57% had oral lichen. Concomitant patch test reactions to gold, nickel and mercury were common. In the matched group-comparison carvone-positive patients had a higher frequency of oral lichen, but no difference was found in sensitization to gold and mercury.
The majority of toothpastes on the Swedish market contain l-carvone, but the concentration hardly relates to the advertised flavour or labelled ingredients. It is hitherto unknown whether the found concentrations are sufficient for induction of contact allergy in individuals with healthy oral mucosa or in those with oral lichenoid lesions or other mucosal disease.
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