In situ observations of HO2 and OH obtained on the NASA ER‐2 in the high‐ClO conditions of the 1999/2000 Arctic polar vortex

Abstract

Extensive observations of OH and HO2 obtained aboard the NASA ER‐2 inside the Arctic polar vortex during the SAGE III Ozone loss and Validation Experiment (SOLVE) provide the opportunity to identify and test interferences during the measurement of HO2 in the presence of high concentrations of ClO. In‐flight calibrations are consistent with small interferences from CH3O2 (8%) and from ClO (3%) to the total signal on average inside the vortex. Measurements of HO2, OH, ClO, and O3 are used with rate constants derived from laboratory measurements to test the consistency of the reactions that control HO2/OH. Inside the vortex the calculated HO2/OH under predicts the observed HO2/OH by 7% with the JPL‐00 rate constants and over‐predicts the observations by 23% when recent laboratory rates are used. Measurements of HO2 and ClO are used to calculate ozone loss rates and concentrations of HOCl with uncertainties determined from the analysis of HO2/OH. The calculated concentration of HOCl is 52−28+50 pptv, or 0.07 × ClO on average in the vortex. The ozone loss rate from the two cycles controlled by HO2 + ClO is ∼1.5−0.5+1.2 ppbv d−1 in early March.