Methylenediphenyl diisocyanate lysine conjugates in the urine of workers exposed to methylenediphenyl diisocyanate.

Diisocyanates have long been a leading cause of occupational asthma. As control often relies on personal protective equipment and there is the potential for skin uptake, biological monitoring is often used to assess worker exposure. Current routine biological monitoring methods do not distinguish between a diisocyanate and the corresponding diamine exposure in urine samples; therefore, a specific urinary biomarker is desirable. Urine samples were obtained from a group of workers exposed to methylenediphenyl diisocyanate (MDI) where aerosol generation was unlikely. Lysine conjugates of MDI were extracted from urine by solid phase extraction; analysis was performed by liquid chromatography tandem mass spectrometry. Acetylated MDI-lysine (acMDI-Lys) conjugates were detected in 73% of samples tested from persons with exposure to MDI compared to 93% of samples that were positive for methylene dianiline (MDA) in hydrolysed urine. There was a weak but significant positive correlation between the two biomarkers (r = 0.377). This is the first report detecting and quantifying acMDI-Lys in the urine of workers exposed to MDI, and acMDI-Lys may be a useful non-invasive biomarker in discriminating between MDI and MDA exposures.