Development of an Interception Glove Sampler for Skin Exposures to Aromatic Isocyanates

Objectives: Skin is an important exposure route for isocyanate chemicals and contributes to systemic sensitization. Methods for assessing skin exposure are currently limited and generally rely upon removal (e.g. tape-strip) techniques prone to underestimation. The aim of this study is to (i) develop and field test an interception-based hand exposure sampler to monitor potential skin exposure to isocyanates in the workplace, (ii) to develop an analytical method based on ultra-high-performance liquid chromatography-UV absorbance-tandem mass spectrometry (UHPLC-UV-MS/MS) for analyzing glove samples; and (iii) compare it with tape-stripping skin sampling method. Methods: Laboratory investigations assessed different glove materials/fabrics, methods for impregnating with 1-(9-anthracenylmethyl) piperazine (MAP) derivatizing agent, methylene diphenyl diisocyanate (MDI) uptake and recovery, and durability. Following use, gloves were dissected into sections corresponding to different spatial regions (finger, palm) and analyzed using a newly developed UHPLC-UV-MS/MS method capable of differentiating and quantitating different MDI isomers with high sensitivity. Performance of the glove sampler was further assessed in a pilot field study using six workers. Results: A MAP-impregnated thin cotton glove sampler and UHPLC-UV-MS/MS analytical method for detecting MDI were successfully developed in laboratory studies. In subsequent field studies, a total of 384 samples from 14 glove pairs identified full-shift exposures ranged from 0.01 to 306 mu g of 4,4'MDI/worker for each hand. Surface area adjusted MDI values measured with the glove sampler (0.13572 ng MDI cm(-2)) were considerably higher (similar to 400-fold) than values obtained with tape stripping. Conclusion: A glove sampler and a novel UHPLC-UV-MS/MS analytical method were developed to quantitatively measure MDI skin exposure. The novel interception technique overcomes inherent limitations of removal techniques for measuring isocyanate skin exposure and may be useful in exposure surveillance and future research on isocyanate's health risks.