Boutin M, Lesage J, Ostiguy C, Pauluhn J
Institut de recherche Robert-Sauvé en santé et en sécurité du travail, Montréal, Canada.
J Occup Environ Hyg. 2005 Sep;2(9):456-61. doi: 10.1080/15459620500240626.
During the thermal degradation of 1,6-hexamethylenediiso- cyanate-based (HDI) car paint, the eight most abundant isocyanates generated are isocyanic acid, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, and 1,6-hexamethylenediisocyanate. For the first time, a method using solvent-free samplers is proposed and validated for the simultaneous sampling of all these isocyanates. The sampling efficiency during thermal degradation of car paint can be affected by the formation of dust and aerosols and by the emission of many chemicals, such as isocyanic acid, anhydrides, amines, and alcohols that consume the reagent or interfere in the derivatization procedure. Sampling was performed using cassettes containing two 1-(2-methoxyphenyl)piperazine (MOPIP)-coated glass fiber filters (MFs) (approximately 4.9 mg per filter) and compared with bubblers containing 15 mL of MOPIP solution in toluene (1.0 mg/mL(-1)) and with bubblers backed with MFs. A DIN 53436 laboratory scale furnace was used to generate the isocyanates under thermal degradation conditions. For an aliphatic isocyanate concentration of approximately 42 microg(NCO) m(-3), no significant difference in sampling efficiency was observed between the three techniques studied, thus confirming the sampling efficiency of the MFs. The samples were analyzed using high-performance liquid chromatography coupled with electrospray/tandem mass spectrometry. Quantification was performed in daughter mode monitoring (MOPIP+H)(+) fragments. For concentrations between 0.013 microg(NCO) mL(-1) and 0.52 microg(NCO) mL(-1) for the monoisocyanates, and between 0.026 microg(NCO) mL(-1) and 1.04 microg(NCO) mL(-1) for the HDI, the correlation coefficients were in the 0.9974-0.9996 range (n = 18). Analytical reproducibility and precision were better than 95.4% and 94.9%, respectively, for all the isocyanates. The instrumental detection limits, defined as three times the standard deviation measured at the lowest point on the calibration curve were in the 1.8-3.0 ng(NCO) mL(-1) range (n = 8), which corresponds to about 0.37-0.60 microg(NCO) m(-3) for a 15-L air sample when the filters are desorbed in 3 mL.
在基于1,6 - 己二异氰酸酯（HDI）的汽车漆热降解过程中，生成的八种最主要的异氰酸酯为异氰酸、甲基异氰酸酯、乙基异氰酸酯、丙基异氰酸酯、丁基异氰酸酯、戊基异氰酸酯、己基异氰酸酯和1,6 - 己二异氰酸酯。首次提出并验证了一种使用无溶剂采样器同时采集所有这些异氰酸酯的方法。汽车漆热降解过程中的采样效率可能会受到灰尘和气溶胶形成以及许多化学物质排放的影响，例如消耗试剂或干扰衍生化过程的异氰酸、酸酐、胺和醇。采样使用装有两个涂有1 - （2 - 甲氧基苯基）哌嗪（MOPIP）的玻璃纤维滤膜（MF）的采样盒（每个滤膜约4.9 mg），并与装有15 mL甲苯中MOPIP溶液（1.0 mg/mL⁻¹）的鼓泡器以及背后衬有MF的鼓泡器进行比较。使用DIN 53436实验室规模的炉在热降解条件下生成异氰酸酯。对于脂肪族异氰酸酯浓度约为42 μg（NCO）m⁻³的情况，在所研究的三种技术之间未观察到采样效率的显著差异，从而证实了MF的采样效率。使用高效液相色谱 - 电喷雾/串联质谱联用仪对样品进行分析。在子模式监测（MOPIP + H）⁺碎片中进行定量。对于单异氰酸酯浓度在0.013 μg（NCO）mL⁻¹至0.52 μg（NCO）mL⁻¹之间，以及对于HDI浓度在0.026 μg（NCO）mL⁻¹至1.04 μg（NCO）mL⁻¹之间，相关系数在0.9974 - 0.9996范围内（n = 18）。所有异氰酸酯的分析重现性和精密度分别优于95.4%和94.9%。仪器检测限定义为在校准曲线最低点测量的标准偏差的三倍，在1.8 - 3.0 ng（NCO）mL⁻¹范围内（n = 8），当滤膜在3 mL中解吸时，对于15 - L空气样品，这相当于约0.37 - 0.60 μg（NCO）m⁻³。
