Validation of a new cavity ring-down spectrometer for measuring tropospheric gaseous hydrogen chloride

Abstract

Reliable, sensitive, and widely available hydrogen chloride (HCl) measurements are important for understanding oxidation in many regions of the troposphere. We configured a commercial HCl cavity ring-down spectrometer (CRDS) for sampling HCl in the ambient atmosphere and developed validation techniques to characterize the measurement uncertainties. The CRDS makes fast, sensitive, and robust measurements of HCl in a high-finesse optical cavity coupled to a laser centred at 5739 cm−1. The accuracy was determined to reside between 5 %–10 %, calculated from laboratory and ambient air intercomparisons with annular denuders. The precision and limit of detection (3σ) in the 0.5 Hz measurement were below 6 and 18 pptv, respectively, for a 30 s integration interval in zero air. The response time of this method is primarily characterized by fitting decay curves to a double exponential equation and is impacted by inlet adsorption/desorption, with these surface effects increasing with relative humidity and decreasing with decreasing HCl mixing ratios. The minimum 90 % response time was 10 s and the equilibrated response time for the tested inlet was 2–6 min under the most and least optimal conditions, respectively. An intercomparison with the EPA compendium method for quantification of acidic atmospheric gases showed good agreement, yielding a linear relationship statistically equivalent to unity (slope of 0.97 ± 0.15). The CRDS from this study can detect HCl at atmospherically relevant mixing ratios, often performing comparably or better in sensitivity, selectivity, and response time than previously reported HCl detection methods.