Intercomparison of OH radical measurement in a complex atmosphere in Chengdu, China

Atmospheric oxidation is a driving force of complex air pollution, and accurate hydroxyl radical (OH) measurement is helpful in investigating the radical-cored photooxidation mechanism in the troposphere. A self-developed laser-induced fluorescence instrument by the Anhui Institute of Optics Fine Mechanics, Chinese Academy of Sciences (AIOFM-LIF), was able to measure OH concentration with high sensitivity and good time resolution, and a detection limit of 1.7 × 10⁵ cm^-3 (1σ, 30 s). A long-period, multi-level intercomparison of hydroxyl radical (OH) measurements between AIOFM-LIF and PKU-LIF (the Peking University laser-induced fluorescence system) was conducted in Chengdu, China. The measurement between two instruments was in excellent agreement in the 5-min time resolution. Linear regression analysis reported a linear slope of 0.96 with a 0.68 × 10⁶ cm^-3 offset, and the correlation coefficient R² was 0.85. The overall linearity with only a slight offset indicated a negligible influence on OH measurement. No noticeable artifacts from ozonolysis were observed under the condition of high ozone and ozonolysis-related compound concentrations. In addition to the subtraction of background signal through wavelength modulation, the dynamic correction on ozone photolysis interference ensured high intercomparison quality in both relatively constant and rapidly varying periods. Based on the reliability of OH_AIOFM and OH_PKU, comparisons under different oxidation-related species (NOx, VOCs, O₃, PM_2.5) levels and typical scenarios (rich-BVOC and high-reactivity) were carried out to evaluate the performance under complex atmospheres. A slightly higher drift was observed in a certain scenario, but the general data variability due to environmental changes did not affect the measurement accuracy. The intercomparison demonstrated that both systems are able to achieve reliable OH data under typical conditions of complex atmospheric pollution in China. Additional improvements are necessary for future intercomparisons in order to enhance the confidence in OH detection accuracy.