A novel approach to calibrating a photoacoustic absorption spectrometer using polydisperse absorbing aerosol

Abstract

Abstract. A new technique for calibrating photoacoustic aerosol absorption spectrometers with multiple laser passes in the acoustic cavity (multi-pass PAS) has been developed utilizing polydisperse and highly absorbing aerosol. This is the first calibration technique for multi-pass PAS instruments that utilizes particles instead of reactive gases and does not require knowledge of the exact size or refractive index of the absorbing aerosol. In this new method, highly absorbing materials are aerosolized into a polydisperse distribution and measured simultaneously with a multi-pass PAS and a cavity-attenuated phase shift particulate matter single-scattering albedo (CAPS PMSSA, Aerodyne Inc.) instrument. The CAPS PMSSA measures the bulk absorption coefficient through the subtraction of the scattering coefficient from the extinction coefficient. While this approach can have significant errors in ambient aerosol, the accuracy and precision of the CAPS PMSSA are high when the measured aerosol has a low single-scattering albedo (SSA) and particles are less than 300 nm in size, in which case truncation errors are small. To confirm the precision and accuracy of the new calibration approach, a range of aerosol concentrations were sent to the multi-pass PAS and CAPS PMSSA instruments using three different absorbing substances: Aquadag, Regal Black, and Nigrosin. Six repetitions with each of the three substances produced stable calibrations, with the standard deviation of the calibration slopes being less than 2 % at 660 nm and less than 5 % at 405 nm for a given calibration substance. Calibrations were also consistent across the different calibration substances (standard deviation of 2 % at 660 nm and 10 % at 405 nm) except for Nigrosin at 405 nm. The accuracy of the calibration approach is dependent on the SSA of the calibration substance but is roughly 6 % for the calibration substances used here, which all have an SSA near 0.4 at 405 nm. This calibration technique is easily deployed in the field as it involves no toxic or reactive gases and it does not require generation of a monodisperse aerosol. Advantages to this particle-based calibration technique versus techniques based on ozone or nitrogen dioxide absorption include no reactive losses or impact from carrier gases and the broad absorption characteristics of the particles, which eliminate potentially significant errors in calibration that come with small errors in the peak wavelength of the laser light when utilizing gas-phase standards.