ezhe Xu

Ultra-sensitive measurement of peroxy radicals by chemical amplification broadband cavity-enhanced spectroscopy

The PERCA (PEroxy Radical Chemical Amplification) technique, which is based on the catalytic conversion of ambient peroxy radicals (HO2 and RO2, where R stands for any organic chain) to a larger amount of nitrogen dioxide (NO2) amplified by chain reactions by adding high concentrations of NO and CO in the flow reactor, has been widely used for total peroxy radical RO2* (RO2* = HO2 + ΣRO2) measurements. High-sensitivity and accurate measurement of the NO2 concentration plays a key role in accurate measurement of the RO2* concentration. In this paper, we report on the development of a dual-channel chemical amplification instrument, which combined the PERCA method with the incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS), for peroxy radical measurements. The IBBCEAS method is capable of simultaneously measuring multiple species with high spectral identification, and can directly measure NO2 concentrations with high sensitivity and high accuracy and without interference from other absorbers. The detection sensitivity of the developed PERCA-IBBCEAS instrument for HO2 radicals was estimated to be about 0.9 pptv (1σ, 60 s) at a relative humidity (RH) of 10%. Considering the error sources of NO2 detection, CL determination, and the radical partitioning in the air sample, the total uncertainty of RO2* measurements was about 16-20%.

Portable broadband cavity-enhanced spectrometer utilizing Kalman filtering: application to real-time, in situ monitoring of glyoxal and nitrogen dioxide

This article describes the development and field application of a portable broadband cavity enhanced spectrometer (BBCES) operating in the spectral range of 440-480 nm for sensitive, real-time, in situ measurement of ambient glyoxal (CHOCHO) and nitrogen dioxide (NO2). The instrument utilized a custom cage system in which the same SMA collimators were used in the transmitter and receiver units for coupling the LED light into the cavity and collecting the light transmitted through the cavity. This configuration realised a compact and stable optical system that could be easily aligned. The dimensions and mass of the optical layer were 676 × 74 × 86 mm3 and 4.5 kg, respectively. The cavity base length was about 42 cm. The mirror reflectivity at λ = 460 nm was determined to be 0.9998, giving an effective absorption pathlength of 2.26 km. The demonstrated measurement precisions (1σ) over 60 s were 28 and 50 pptv for CHOCHO and NO2 and the respective accuracies were 5% and 4%. By applying a Kalman adaptive filter to the retrieved concentrations, the measurement precisions of CHOCHO and NO2 were improved to 8 pptv and 40 pptv in 21 s.

Removing Water Vapor Interference in Peroxy Radical Chemical Amplification with a Large Diameter Nafion Dryer

The chemical amplification (PERCA) method has been widely used for measuring peroxy radical concentrations in the troposphere. The accuracy and sensitivity of the method is critically dependent on the chain length (CL)-that is, the number of radical amplification cycles. However, CL decreases strongly with higher relative humidity (RH). So far, there does not appear to be a method to overcome this impact. Here we report the development of a Nafion dryer based dual-channel PERCA instrument. The large diameter Nafion dryer efficiently removes water vapor in milliseconds and minimally affects the sample. The low losses of peroxy radicals on the Nafion membrane make it an attractive tool for raising the CL, and thereby the measurement accuracy and sensitivity of PERCA systems. The reported instrument demonstrates this promising and simple method to minimize water vapor interference.

Measurement of aerosol extinction coefficient in the suburb of Beijing by incoherent broadband cavity enhanced absorption spectroscopy

We report on the development of a blue LED based incoherent broadband cavity enhanced spectrometer for aerosol extinction coefficient measurement. Extinction measurement results in the suburb of Beijing during the HOPE-J3A campaign are summarized.

Development of a Cavity-Enhanced Albedometer for Simultaneous Measurement of Aerosol Extinction and Scattering Coefficients

We report on the development of a cavity-enhanced albedometer incorporating broad-band cavity-enhanced spectroscopy approach and an integrating sphere for simultaneous in-situ measurements of aerosol scattering and extinction coefficients on the exact same sample volume.