A new technique using laser flash photolysis in conjunction with laser-induced fluorescence spectroscopy to investigate the reaction kinetics of metastable O(S-1) atom with atmospheric molecules has been demonstrated. The O(S-1) atoms are produced from 193 nm photolysis Of O-3 and detected using a technique of vacuum ultraviolet laser-induced fluorescence (VUV-LIF) at 121.76 nm which is resonant to the O(3s(1)P(1)-2p(1)S) transition. The rate coefficients of the reactions of O(S-1) with O-2, CO2, H2O, O-3 and HCl at room temperature have been determined. (C) 2004 Elsevier B.V. All rights reserved.