Laboratory Division, Institut de recherche Robert-Sauvé en santé et en sécurité du travail, Montréal, Québec, Canada.
Chemistry Department, Université du Québec à Montréal, Montréal, Québec.
J Occup Environ Hyg. 2020 May;17(5):207-219. doi: 10.1080/15459624.2020.1731518. Epub 2020 Apr 10.
Because of the semi-volatile nature of diisocyanates (being airborne in both physical vapor and particulate phases), their high reactivity and low occupational exposure limits, diisocyanate exposure evaluation has been challenging for industrial hygienists and laboratories. The objective of this study was to compare the toluene diisocyanate (2,4 and 2,6 isomers, TDI) concentration measured by five methods in a flexible polyurethane foam factory using different collection or derivatization approaches. The methods used were: OSHA 42 modified (filter, 1-(2-pyridyl)piperazine) (OSHA), Asset EZ4-NCO (denuder and filter, dibutylamine) (Asset), Iso-Chek (double-filter, 9-(N-methylaminomethyl) anthracene and 1,2-methoxyphenylpiperazine), DAN (filter, 1,8-diaminonaphthalene), and CIP10 (centrifugation, 1,2-methoxyphenylpiperazine). Particle real-time monitoring for concentration and size distribution was performed in parallel to improve the understanding of the potential bias between methods. The comparison study was performed over 3 days, providing 18 replicates for each of the 5 methods. Isocyanate concentrations collected for each sampling method were compared using linear mixed effect modeling. Compared to OSHA, which yielded the highest concentrations overall, the Asset and DAN methods provided the smallest biases (-29% (95% CI [-52;-6]) and -45% (95% CI [-67;-23]), respectively), while the CIP10 and Iso-Chek methods provided the largest biases (-82% (95% CI [-105;-66]) and -96% (95% CI [-118;-75]), respectively). The substantial bias of Iso-Chek and CIP10 seemed to be explained by the predominance of TDI in the form of sub-micron particles that were inadequately captured by these two methods due to their sampling principle, which are particle filtration without derivatizing agent and centrifugation respectively. Asset and DAN performance seemed to decrease as the sampling time increased. While DAN's bias could be related to a reagent deficiency on the filter, the disparities between OSHA and Asset, both considered as reference methods, highlight the fact that the mechanisms of collection, derivation and extraction do not seem to be completely controlled. Finally, an upward trend has been observed between concentrations of particles below 300 nm in size and concentration levels of TDI. It has also been observed that TDI levels increased with the TDI foam index produced at the facility.
由于二异氰酸酯(在物理蒸气和颗粒相两种形态下都为半挥发性物质)具有较高的反应活性和较低的职业暴露限值,因此工业卫生学家和实验室很难对其进行评估。本研究的目的是比较在使用不同收集或衍生方法的柔性聚氨酯泡沫工厂中,五种方法(OSHA42 改良法(滤器,1-(2-吡啶基)哌嗪)(OSHA)、AssetEZ4-NCO(冲击式收集器和滤器,二丁基胺)(Asset)、Iso-Chek(双滤器,9-(N-甲基氨甲基)蒽和 1,2-甲氧基苯并二氮杂卓)、DAN(滤器,1,8-二氨基萘)和 CIP10(离心法,1,2-甲氧基苯并二氮杂卓))测量的甲苯二异氰酸酯(2,4 和 2,6 异构体,TDI)浓度。同时还进行了实时颗粒物浓度和粒径分布的监测,以更好地了解各方法之间可能存在的偏差。比较研究在 3 天内进行,每种方法重复 18 次。使用线性混合效应模型比较每种采样方法收集的异氰酸酯浓度。与 OSHA 相比,OSHA 总体上产生的浓度最高,Asset 和 DAN 方法的偏差最小(分别为-29%(95%CI [-52;-6])和-45%(95%CI [-67;-23])),而 CIP10 和 Iso-Chek 方法的偏差最大(分别为-82%(95%CI [-105;-66])和-96%(95%CI [-118;-75]))。Iso-Chek 和 CIP10 的显著偏差似乎可以用 TDI 以亚微米颗粒形式存在来解释,由于这些方法的采样原理,即分别为无衍生剂的颗粒过滤和离心,这些方法不能充分捕获这些亚微米颗粒。Asset 和 DAN 的性能似乎随着采样时间的增加而下降。虽然 DAN 的偏差可能与滤器上的试剂不足有关,但 OSHA 和 Asset 之间的差异(两者都被认为是参考方法)突显了收集、衍生和提取的机制似乎并未完全受控这一事实。最后,观察到粒径小于 300nm 的颗粒物浓度与 TDI 浓度之间呈上升趋势。还观察到 TDI 水平随工厂生产的 TDI 泡沫指数的增加而增加。