Analysis of dioxins by gas chromatography/resonance-enhanced multiphoton ionization/mass spectrometry using nanosecond and picosecond lasers.
Dioxins in a soil sample were measured using gas chromatography/resonance-enhanced multiphoton ionization/time-of-flight mass spectrometry coupled with different types of laser sources. The fourth-harmonic emission (266 nm) of a nanosecond Nd:YAG laser (1 ns) provided low ionization efficiency, especially for highly chlorinated dioxins/dibenzofurans (CDDs/CDFs). The ionization efficiency was improved using the fourth-harmonic emission (266 nm) of a picosecond Nd:YAG laser (4 ps), due to shorter singlet excited-state lifetimes. It was, however, difficult to efficiently ionize hepta-CDD and octa-CDD/CDF, because of their shorter lifetimes, which were induced by stronger spin-orbit coupling that led to efficient relaxation of the excited molecule to triplet levels. The ionization efficiency was substantially improved using the fifth-harmonic emission (213 nm) of the picosecond Nd:YAG laser (4 ps), in which the analyte molecule that was relaxed to triplet levels was efficiently ionized using a photon with sufficient energy for ionization, although the pulse energy obtained at 213 nm was only one-third of the pulse energy obtained at 266 nm. The limits of detection achieved for 17 toxic polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDDs/PCDFs) were 0.41-45 pg. The analytical instrument developed in the present study performed sufficiently well for the practical trace analysis of dioxins in soil samples.
Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Motooka, Nishiku, Fukuoka 819-0395, Japan. adan@cstf.kyushuu.ac.jp
Adan
A
Li
Tomohiro
T
Uchimura
Yuka
Y
Watanabe-Ezoe
Totaro
T
Imasaka