Absolute measurements of total peroxy nitrate mixing ratios by thermal dissociation blue diode laser cavity ring-down spectroscopy.

Peroxycarboxylic nitric anhydrides (PANs) have long been recognized as important trace gas constituents of the troposphere. Here, we describe a blue diode laser thermal dissociation cavity ring-down spectrometer for rapid and absolute measurements of total peroxyacyl nitrate (SigmaPAN) abundances at ambient concentration levels. The PANs are thermally dissociated and detected as NO2, whose mixing ratios are quantified by optical absorption at 405 nm relative to a reference channel kept at ambient temperature. The effective NO2 absorption cross-section at the diode laser emission wavelength was measured to be 6.1 x 10(-19) cm2 molecule(-1), in excellent agreement with a prediction based on a projection of a high-resolution literature absorption spectrum onto the laser line width. The performance, i.e., accuracy and precision of measurement and matrix effects, of the new 405 nm thermal dissociation cavity ring-down spectrometer was evaluated and compared to that of a 532 nm thermal dissociation cavity ring-down spectrometer using laboratory-generated air samples. The new 405 nm spectrometer was considerably more sensitive and compact than the previously constructed version. The key advantage of laser thermal dissociation cavity ring-down spectroscopy is that the measurement can be considered absolute and does not need to rely on external calibration.