The application of cavity ring -down spectroscopy to atmospheric and physical chemistry

Cavity ring-down spectroscopy (CRDS) is a sensitive form of absorption spectroscopy. Thousands of reflections between two multilayer dielectric mirrors give CRDS an extremely long path-length. The rate of decay of the signal is measured instead of the magnitude of attenuation, so laser intensity fluctuations do not affect the measurement.;At 405.23 nm, NO2 had a detection limit of 150 ppt/10 s (3sigma). Particles were removed by a 0.45 mum filter. Water vapor had a 2.8 ppb NO 2 equivalent interference for 1% water vapor in air, with a simple quadratic dependence on water monomer concentration that might have been due to water dimer. Removing NO2 with an annular denuder coated with guiacol and sodium hydroxide, or reacting the NO2 and NO2 with ozone, allows for an interference measurement. An NOy measurement can be obtained after thermal decomposition of higher oxides and ozone. The interference was easier to accommodate than the quenching found in chemiluminescence.;The water dimer hypothesis was supported by temperature studies resulting in thermodynamics consistent with theory. The oscillator strength at 409 nm was roughly three orders of magnitude stronger than the best available calculations, leading to a serious unanswered question of the possible source of the additional enhancement. Measurements at 532 nm found a similar response, and others have measured a response at 440 nm, suggesting the 6th, 7th and 8th overtones of water dimer occur at ∼532 nm, ∼440 nm and 409 nm with a similar magnitude that is possibly larger than the 3rd and 4th overtones that have not been detectable.;The excellent NO2 detection sensitivity enabled the measurement of NO2 emitted by ambient particles from thermal decomposition. Gas phase interferences were removed with radial aerosol denuders. PANs, ANs, and ammonium nitrate were measured sequentially at 150°C, 215°C and 250°C by the emitted NO2. This technique was applied to ambient air during the Study of Organic Aerosols in Riverside (SOAR) campaign in Riverside during August 2005 and found that PANs were much higher than anticipated. Chamber studies found that PANs were a significant particle phase product from aldehydes.