Influence of photolysis on multispectral photoacoustic measurement of nitrogen dioxide concentration

Abstract

Multispectral photoacoustic instruments are commonly used to measure aerosol and nitrogen dioxide (NO₂) light absorption coefficients to determine the radiation budget of the atmosphere. Here a new photoacoustic system is developed to explore the effect of photolysis on the measured signal in a multispectral photoacoustic spectrometer. In this system, a 405-nm laser is used primarily as light source for photolysis. Additionally, a well-overlapped 532-nm laser, modulated at the resonant frequency of the photoacoustic instrument, is used to probe the NO₂ concentration. As a result, the photolysis effect at 405 nm can be observed by the photoacoustic instrument through the 532-nm laser. This work determines an 11% reduction of the photoacoustic signal caused by the photolysis effect for typical conditions, which needs to be taken into account when calibrating multispectral photoacoustic spectrometers with NO₂.

Implications:

Multispectral photoacoustic instruments are commonly used to measure aerosol and nitrogen dioxide (NO₂) light absorption coefficients to determine the radiation budget of the atmosphere. A 405-nm laser is often used in these multispectral photoacoustic instruments. Although NO₂ absorbs strongly at 405 nm, it also has a strong photolysis pathway that is accessible by light of the same wavelength. Photolysis reduces the photoacoustic signal, necessitating special care when interpreting photoacoustic measurements. This paper offers a method for the multispectral photoacoustic instrument user to quantify the influence of the 405-nm NO₂ photolysis effect on the photoacoustic signal.

Acknowledgment

This paper is based upon work supported by NASA EPSCoR under Cooperative Agreement No. NNX10AR89A, by NASA ROSES under grant no. NNX11AB79G, and by the National Science Foundation under grant no. AGS-1040046. Helpful discussions with Dean Venables are gratefully acknowledged.