高效液相色谱法测定环境空气醛酮类化合物
Determination of aldehydes and ketones in ambient air using adsorbent cartridge followed by high performance liquid chromatography
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摘要: 使用涂渍2,4-二硝基苯肼(DNPH)硅胶填充管采集环境空气中醛酮类化合物,通过高效液相色谱法检测其衍生物是一种非常经典的测定醛酮类化合物方法.然而,在此方法的广泛应用过程中,其在定性定量中的诸多问题如吸附管空白值的影响、不饱和醛酮进一步聚合的影响等却常常被忽视.本文主要研究了不同DNPH吸附柱中醛酮化合物的本底值对准确定量的影响,以及选择合适的采样体积减小采样管本底值对定量的影响;重点探讨了丙烯醛和丁烯醛两类不饱和醛的腙类衍生物在DNPH管中的稳定性,以及其腙类衍生物与DNPH进一步生成聚合物对定量的影响.通过对其衍生物在不同吸附管中聚合反应动力学试验,发现使用盐酸催化的吸附管中聚合反应要比使用磷酸催化慢得多.最后确定选择使用盐酸作为催化剂的吸附管,采样后及时解吸,采样至解吸完成时间控制在6 h以内,可有效降低聚合产物对丙烯醛和丁烯醛准确定量的影响.Abstract: The classical method for the determination of carbonyls (aldehydes and ketones) in ambient air was conducted by using 2,4-dinitrophenylhydrazine (DNPH)-coated sorbent cartridge to collect samples. The samples were then analyzed by high performance liquid chromatography. Although this method has been used widely, there are still some drawbacks, eg, the interferences of the background levels of DNPH-cartridges, and the by-products from further reaction on carbonyl-DNP-hydrazone of unsaturated carbonyls with DNPH. This study intends to examine the background levels of three DNPH-cartridges and find an approach to avoid these effects on accurate quantification. The stability of hydrazone derivatives of unsaturated aldehydes, such as acrolein-DNP-hydrazone and crotonaldehyde-DNP-hydrazone, in DNPH-coated cartridge, as well as the effects of their polymerization by-products from the further reaction of hydrazone with DNPH on the quantification. The polymerization of the derivatives in three types of DNPH-coated cartridges purchased from different manufactures was also investigated. It was found that polymerization reaction catalyzed by hydrochloric acid in cartridges was slower than that catalyzed by phosphoric acid. The influence of polymerization products on the accurate quantitation could be reduced, when a hydrochloric acidified DNPH- coated cartridge was used and the sample collection and desorption was conducted within 6 h.
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Key words:
- high performance liquid chromatography (HPLC) /
- ambient air /
- carbonyls
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