Abstract

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.

Highlights

  • Halogenated compounds that participate in catalytic cycles in the atmosphere have major impacts on atmospheric chemistry

  • The mass emission rate of hydrogen chloride (HCl) from the permeation devices (PDs) was quantified by scrubbing into a 25 mL glass impinger containing 1 mM KOH over 24 h followed by analysis using ion chromatography (IC) with conductivity detection (CD)

  • The suitability of a cavity ring-down spectrometer (CRDS) analyzer for measuring ambient atmospheric HCl was explored through laboratory and ambient air intercomparisons, assessing their inlet and analyzer sampling challenges against established atmospheric sampling techniques for strong acids

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Summary

Introduction

Halogenated compounds that participate in catalytic cycles in the atmosphere have major impacts on atmospheric chemistry. Other methods include scrubbing ambient air using an annular denuder and/or tandem mist chambers to collect HCl, followed by offline analysis such as ion chromatography (IC) (Keene et al, 2007, 2009; United States Environmental Protection Agency, 1999; Young et al, 2013) Online detection methods such as chemical ionization time of flight mass spectrometry (CI-ToFMS) (Crisp et al, 2014), negative ion proton transfer chemical ionization mass spectrometry (NI-PT-CIMS) (Veres et al, 2008), and negative mode atmospheric pressure chemical ionization coupled to triple quadrupole mass spectrometry (APCI-MS-MS) (Karellas et al, 2003) have been shown to be reliable and sensitive methods for HCl detection. We describe and characterize surface effects and recommend inlet configurations for best practices when conducting ambient sampling

Chemicals
In-house HCl permeation device validation
Laboratory intercomparison
Ambient intercomparison
Ion chromatography analysis
Suitability for atmospheric measurements
Instrument performance
Sampling line and instrument response time assessment
Conclusions
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