Analytical Sciences

Abstract − Analytical Sciences, 31(2), 99 (2015).

Determination of Formaldehyde in Aqueous Samples with a Miniaturized Extraction Capillary Coupled to High-Performance Liquid Chromatography
Ikuo UETA,* Suguru MOCHIZUKI,* Susumu KAWAKUBO,* Tetsuo KUWABARA,* and Yoshihiro SAITO**
*Department of Applied Chemistry, University of Yamanashi, 4-3-11 Takeda, Kofu 400-8511, Japan
**Department of Environmental and Life Sciences, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempakucho, Toyohashi 441-8580, Japan
A novel analytical method for determining formaldehyde (FA) in aqueous samples was developed with a miniaturized extraction capillary in high-performance liquid chromatography (HPLC). The extraction capillary was prepared by packing silica gel particles in a stainless steel capillary of 0.8 mm i.d. and 1.6 mm o.d. A derivatization reagent of 2,4-dinitrophenylhydrazine (DNPH) was impregnated on the silica gel particles by pumping a solution of DNPH to the capillary. Two extraction methods; dynamic extraction and purge-and-trap (PT) methods, were investigated for derivatizing and extracting FA from water samples onto the silica gel in the extraction capillary. The extraction capillary was directly connected to a six-port valve, and then desorption of the derivative from the capillary and injection to conventional HPLC system were simultaneously achieved with a flow of acetonitrile through the capillary. In the dynamic extraction, FA was determined with a simple sample preparation procedure, and the limit of detection (LOD) was 18 μg L−1 at a sample volume of 20 mL, while several limitations were found in the method, such as bleeding of the derivatization reagent and the corresponding derivatized FA from the capillary during the sample load/extraction process. The sensitivity was significantly improved by introducing a PT technique, where the LOD was 6.9 μg L−1 at a sample volume of 20 mL with a sampling time of approximately 20 min. With the PT method, successful recoveries of FA were confirmed for spiked tap water, river water and fruit juice samples.