Bourdin Delphine, Desauziers Valérie
Centre des Matériaux des Mines d'Alès, Ecole des Mines d'Alès, Hélioparc, 2 avenue Pierre Angot, 64053, Pau, Cedex 9, France.
Anal Bioanal Chem. 2014 Jan;406(1):317-28. doi: 10.1007/s00216-013-7460-6. Epub 2013 Nov 20.
Solid-phase microextraction on-fiber derivatization applied to carbonyl compounds is known, but application to indoor air is poorly developed and the methods deserve to be complemented and optimized. In this work, two derivatization reagents, pentafluorophenylhydrazine and o-2,3,4,5,6-(pentaflurobenzyl)hydroxylamine (PFBHA), and three fiber coatings were tested in order to select the best combination. As Carboxen-based coatings were proven to induce the formation of by-products during the thermal desorption step, a polydimethylsiloxane-divinylbenzene fiber in association with PFBHA was finally chosen. The study of the derivatization kinetics showed that the reaction of PFBHA with carbonyl compounds was instantaneous, except for acetone. Analyses were performed by gas chromatography coupled with flame ionization detection and mass spectrometry. For 5 min fiber exposure, the limits of detection are below 0.5 μg m(-3) in selected ion monitoring mode, the reproducibility was 15% on average, and the linearity of the calibration curves was satisfactory. For on-site application, the influence of air humidity and the conditions in which the impregnated fibers were stored were studied. It is possible to store the fibers for 3 days before and for at least 2 days after sampling. The relative humidity of air was shown to have no influence on solid-phase microextraction sampling in the range from 0 to 70%. For formaldehyde, the method was compared with sampling on 2,4-dinitrophenylhydrazine cartridges, and the first results showed good agreement. Finally, the method was applied to three different indoor environments to check its feasibility.
固相微萃取纤维上衍生化技术应用于羰基化合物已有报道，但应用于室内空气方面的研究尚不完善，该方法值得补充和优化。在本研究中，测试了两种衍生化试剂，即五氟苯肼和邻-2,3,4,5,6-（五氟苄基）羟胺（PFBHA），以及三种纤维涂层，以选择最佳组合。由于基于碳分子筛的涂层在热解吸步骤中会诱导副产物的形成，最终选择了聚二甲基硅氧烷-二乙烯基苯纤维与PFBHA联用。衍生化动力学研究表明，除丙酮外，PFBHA与羰基化合物的反应是瞬间的。采用气相色谱-火焰离子化检测和质谱联用进行分析。在选定离子监测模式下，纤维暴露5分钟时，检测限低于0.5 μg m(-3)，平均重现性为15%，校准曲线线性良好。对于现场应用，研究了空气湿度和浸渍纤维储存条件的影响。采样前纤维可保存3天，采样后至少可保存2天。结果表明，在0%至70%的范围内，空气相对湿度对固相微萃取采样没有影响。对于甲醛，将该方法与2,4-二硝基苯肼采样管进行了比较，初步结果显示两者吻合良好。最后，将该方法应用于三种不同的室内环境以检验其可行性。
