Fast Fourier transform analysis in cavity ring-down spectroscopy: Application to an optical detector for atmospheric NO₂

A fast Fourier transform (FFT) method for analysis of ring-down decays from a cavity ring-down (CRD) spectrometer has been tested and compared with alternative fitting methods. The ring-down times derived from the FFT method are obtained with a precision close to that of the Levenberg-Marquardt non-linear least-squares method, but the fitting algorithm is ~100 times faster, allowing real-time fitting of individual ring-down traces on a personal computer. Advantages of the FFT method are discussed, and the method is demonstrated for the measurement of NO₂ partial pressures equivalent to mixing ratios of 150 pptv and above in laboratory air, using a CRD spectrometer based on an external cavity diode laser operating at wavelengths around 410 nm. The absorption by NO₂ is distinguished from other cavity losses either by using synthetic (zero) air reference samples, or by diverting the sampled laboratory airflow through an NO₂ chemical scrubber consisting of hydroxyapatite on a TiO₂ substrate. Typical mixing ratios of NO ₂ in the laboratory air are ~25 ppbv.