Rayleigh scattering cross-section measurements of nitrogen, argon, oxygen and air

Knowledge about Rayleigh scattering cross sections is relevant to predictions about radiative transfer in the atmosphere, and needed to calibrate the reflectivity of mirrors that are used in high-finesse optical cavities to measure atmospheric trace gases and aerosols. In this work we have measured the absolute Rayleigh scattering cross-section of nitrogen at 405.8 and 532.2 nm using cavity ring-down spectroscopy (CRDS). Further, multi-spectral measurements of the scattering cross-sections of argon, oxygen and air are presented relative to that of nitrogen from 350 to 660 nm using Broadband Cavity Enhanced Spectroscopy (BBCES). The reported measurements agree with refractive index based theory within 0.2 +/- 0.4%, and have an absolute accuracy of better than 13%. Our measurements expand the spectral range over which Rayleigh scattering cross section measurements of argon, oxygen and air are available at near-ultraviolet wavelengths. The expressions used to represent the Rayleigh scattering cross-section in the literature are evaluated to assess how uncertainties affect quantities measured by cavity enhanced absorption spectroscopic (CEAS) techniques. We conclude that Rayleigh scattering cross sections calculated from theory provide accurate data within very low error bounds, and are suited well to calibrate CEAS measurements of atmospheric trace gases and aerosols. (C) 2014 Elsevier Ltd. All rights reserved.