Chemistry Department, Université du Québec à Montréal, Montreal, Canada.
Laboratory Division, Institut de recherche Robert-Sauvé en santé et en sécurité du travail, Montréal, Canada.
Rapid Commun Mass Spectrom. 2022 Aug 30;36(16):e9340. doi: 10.1002/rcm.9340.
Toluene diisocyanate (TDI) is a highly reactive isocyanate commonly used as a mixture of 2,4- and 2,6- isomers in the production of flexible foams. Exposure to TDI occurs primarily through vapour inhalation in workplaces where TDI is produced or used, but dermal exposure is also possible during some tasks. To ensure workplace safety, accurate monitoring of TDI and toluene diamine (TDA) levels is required. Methods of quantifying field effectiveness of gloves in preventing dermal exposure have not been established. Therefore, there is a need to develop a new practical method for assessing glove effectiveness for TDI/TDA.
A new offline SPE UPLC-MS/MS method for the quantitation of TDA isomers from TDI-exposed gloves was developed. Gloves were dipped in a solution of 1% acetic acid leading to a full conversion to TDA. TDA-free amine compounds were derivatized with acetic anhydride to increase chromatographic retention and signal intensity.
2,4-Diaminotoluene-α, α, α-d3 (2,4-d -TDA) was selected as a surrogate standard to minimise the variability in sample preparation and instrumental sensitivity. The choice of UPLC-MS/MS operated in multiple reaction monitoring (MRM) mode allowed to reach much lower limits of detection (LOD). The LOD of the method was 6.86 and 2.83 ng/mL (0.03 and 0.01 μg) for 2,6-TDA and 2,4-TDA, respectively. The limit of quantitation (LOQ) was 22.85 and 9.42 ng/mL (0.11 and 0.05 μg) for 2,6-TDA and 2,4-TDA, respectively.
A new UPLC-MS/MS analytical method has been developed to determine field effectiveness of gloves for preventing dermal exposure to TDI/TDA. The new technique overcomes some limitations for measuring putative dermal exposure to isocyanates and may be useful in exposure monitoring and future research on isocyanate health risks.
甲苯二异氰酸酯（TDI）是一种高反应性异氰酸酯，通常用作 2,4-和 2,6-异构体混合物，用于生产柔性泡沫。TDI 的暴露主要通过在生产或使用 TDI 的工作场所通过蒸气吸入发生，但在某些工作中也可能通过皮肤接触发生。为确保工作场所安全，需要准确监测 TDI 和甲苯二胺（TDA）的水平。尚未建立量化手套在防止皮肤接触方面的现场效果的方法。因此，需要开发一种新的实用方法来评估 TDI/TDA 的手套效果。
开发了一种新的离线 SPE-UPLC-MS/MS 方法，用于定量 TDI 暴露手套中的 TDA 异构体。手套浸入 1%乙酸溶液中，导致完全转化为 TDA。无 TDA 的胺化合物用乙酸酐衍生化，以增加色谱保留和信号强度。
2,4-二氨基甲苯-α，α，α-d3（2,4-d-TDA）被选为替代标准，以最大程度地减少样品制备和仪器灵敏度的可变性。选择 UPLC-MS/MS 以多反应监测（MRM）模式操作，可达到更低的检测限（LOD）。该方法的检测限（LOD）分别为 2,6-TDA 和 2,4-TDA 的 6.86 和 2.83ng/mL（0.03 和 0.01μg）。定量限（LOQ）分别为 22.85 和 9.42ng/mL（0.11 和 0.05μg）。
开发了一种新的 UPLC-MS/MS 分析方法，用于确定手套防止 TDI/TDA 皮肤接触的现场效果。新技术克服了一些用于测量潜在的异氰酸酯皮肤接触的局限性，并且可能对暴露监测和未来的异氰酸酯健康风险研究有用。
