Preprints
https://doi.org/10.5194/amt-2021-105
https://doi.org/10.5194/amt-2021-105

  27 Apr 2021

27 Apr 2021

Review status: this preprint is currently under review for the journal AMT.

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

Teles C. Furlani1, Patrick R. Veres2, Kathryn E. R. Dawe3,a, J. Andrew Neuman2,4, Steven S. Brown2,5, Trevor C. VandenBoer1, and Cora J. Young1 Teles C. Furlani et al.
  • 1Department of Chemistry, York University, Toronto, ON, Canada
  • 2NOAA Chemical Sciences Laboratory, Boulder, CO, USA
  • 3Department of Chemistry, Memorial University of Newfoundland, St. John's, NL, Canada
  • 4Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, USA
  • 5Department of Chemistry, University of Colorado, Boulder, CO, USA
  • anow at: SEM Ltd., St. John’s, NL, Canada

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 calibration and 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 centered at 5739 cm−1. The accuracy was determined to reside between 5–10 %, calculated from laboratory calibrations and an ambient air intercomparison with annular denuders. The precision and limit of detection (3σ) in the 0.5 Hz measurement were below 6 pptv and 18 pptv, respectively for a 30 second 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 RH and decreasing with decreasing HCl mixing ratios. The response time for the tested inlet was 2–6 minutes 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 comparable or better in sensitivity, selectivity, and response-time from previously reported HCl detection methods.

Teles C. Furlani et al.

Status: open (until 22 Jun 2021)

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Teles C. Furlani et al.

Teles C. Furlani et al.

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Short summary
This study characterized and validated a commercial spectroscopic instrument for measurement of hydrogen chloride (HCl) in the atmosphere. Near the Earth’s surface, HCl acts as the dominant reservoir for other chlorine-containing reactive chemicals that play an important role in atmospheric chemistry. The properties of HCl make it challenging to measure. The instrument we investigated can overcome many of these challenges, enabling reliable HCl measurements.