Kuitunen Marja-Leena, Altamirano Jorgelina Cecilia, Siegenthaler Peter, Taure Terhi Hannele, Häkkinen Vesa Antero, Vanninen Paula Sinikka
VERIFIN, Department of Chemistry, University of Helsinki, P.O. Box 55, FIN-00014 Helsinki, Finland.
Laboratorio de Química Ambiental, Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales (IANIGLA, CCT-CONICET), Mendoza 5500, Argentina.
Anal Methods. 2020 May 21;12(19):2527-2535. doi: 10.1039/d0ay00263a.
A simple derivatization technique was developed for the analysis of seven Schedule 3 chemicals and one Schedule 2 chemical listed in the Chemical Weapons Convention (CWC). Phosgene, phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, sulfur monochloride and sulfur dichloride (Schedule 3) as well as arsenic trichloride (Schedule 2) were derivatized using 1-propanol in 40% pyridine solution for analysis with gas chromatography-mass spectrometry (GC-MS). Derivatization temperature and concentration of the derivatization solution were optimized for maximum derivatization recovery. The stabilities of the target analytes and their derivatives in different solvents were studied. The derivatization yield showed a linear response within the analyte concentration range of 0.1-2 mM (10-200 μg ml-1) with correlation coefficients >0.99 (r2), except for AsCl3 which did not show a linear response after derivatization. Good reproducibility with relative standard deviations (RSDs) from 3 to 13% was achieved. The derivatization recovery was 66% for phosgene and 67-80% for the P-containing chemicals phosphorus oxychloride, phosphorus trichloride and phosphorus pentachloride. Recommendations to use the method for screening the presence of these chemicals in organic liquid samples are given. The method is used when CWC-related samples are screened at VERIFIN.
开发了一种简单的衍生化技术，用于分析《化学武器公约》（CWC）中列出的七种附表3化学品和一种附表2化学品。光气、三氯氧磷、三氯化磷、五氯化磷、亚硫酰氯、一氯化硫和二氯化硫（附表3）以及三氯化砷（附表2），使用1-丙醇在40%吡啶溶液中进行衍生化，以用于气相色谱-质谱联用（GC-MS）分析。对衍生化温度和衍生化溶液浓度进行了优化，以实现最大衍生化回收率。研究了目标分析物及其衍生物在不同溶剂中的稳定性。除AsCl3衍生化后未呈现线性响应外，在0.1 - 2 mM（10 - 200 μg ml-1）的分析物浓度范围内，衍生化产率呈现线性响应，相关系数>0.99（r2）。实现了良好的重现性，相对标准偏差（RSD）为3%至13%。光气的衍生化回收率为66%，含磷化学品三氯氧磷、三氯化磷和五氯化磷的衍生化回收率为67%至80%。给出了使用该方法筛选有机液体样品中这些化学品存在情况的建议。VERIFIN在对与《化学武器公约》相关的样品进行筛查时使用该方法。
