Measurements of Atmospheric HO₂ Radicals Using Br-CIMS with Elimination of Potential Interferences from Ambient Peroxynitric Acid

As a promising direct measurement method of atmospheric hydroperoxyl radicals (HO2), bromide chemical ionization mass spectrometry (Br-CIMS) has been first demonstrated by Sanchez et al. (Atmos. Meas. Tech. 2016, 9, 3851–3861). However, field application of this method is currently still sparse, and there is still a gap between measured HO2 concentrations and calculated ones derived from the atmospheric equilibrium between HO2 and peroxynitric acid (HO2NO2). In this work, we constructed an improved Br-CIMS with optimizations of custom-built front-end devices, chamber pressures, and instrumental voltages to achieve a 3σ detection limit of 0.5 ppt at an integration time of 60 s and a sensitivity of 1–3 cps ppt–1 under a total reagent ion signal of 0.2 MHz for HO2 detection. HO2NO2, a product from atmospheric reactions between HO2 and NO2, can also be detected by Br-CIMS, whose interference on the HO2 measurement was found but nearly eliminated by regulating key CIMS voltages to minimize the decomposition of (BrHO2NO2)− ions in the MS. In addition, a 2 week field campaign was carried out in urban Shanghai, demonstrating that the interference of HO2 from ambient HO2NO2 was less than 10% of the true HO2 signal under our optimized CIMS voltage setting. Our study suggests that Br-CIMS is a reliable technique for atmospheric HO2 measurements.