02 May 2022
02 May 2022
Status: a revised version of this preprint was accepted for the journal AMT.

Development and Validation of a New In-Situ Technique to Measure Total Gaseous Chlorine in Ambient Air

Teles C. Furlani1, Peter M. Edwards2, Tara F. Kahan3, and Cora J. Young1 Teles C. Furlani et al.
  • 1Department of Chemistry, York University, Toronto, Canada
  • 2Department of Chemistry, University of York, York, UK
  • 3Department of Chemistry, University of Saskatchewan, Saskatoon, Canada

Abstract. Total gaseous chlorine (TClg) measurements can improve our understanding of unknown sources of Cl to the atmosphere. Existing techniques for measuring TClg have been limited to offline analysis of extracted filters and do not provide suitable temporal information on fast atmospheric process. We describe high time-resolution in-situ measurements of TClg by combusting ambient air over a heated platinum (Pt) substrate coupled to a cavity ring-down spectrometer (CRDS). The method relies on the complete decomposition of TClg to release Cl atoms that react to form HCl, for which detection by CRDS has been shown to be fast and reliable. The method was validated using custom organochlorine permeation devices (PDs) that generated gas-phase dichloromethane (DCM), 1-chlorobutane (CB), and 1,3-dichloropropene (DCP). The optimal conversion temperature and residence time through the high-temperature furnace was 825 °C and 1.5 seconds, respectively. Complete conversion was indicated by the near unity orthogonal distance regression analysis slope (±σ) of 0.996 ± 0.012, 1.048 ± 0.006, and 1.027 ± 0.061 for DCM, CB, and DCP, respectively. Breaking these strong C-Cl bonds represents a proof of concept for complete conversion of all similar or weaker bonds that characterize all other TClg. We applied this technique to both outdoor and indoor environments and found reasonable comparisons in ambient background mixing ratios with the sum of expected HCl from known Cl species. We measured the converted TClg in an indoor environment during cleaning activities and observed varying levels of TClg comparable to previous studies. The method validated here is capable of measuring in-situ TClg and has a broad range of applications to make routine TClg measurements in a variety of applications.

Teles C. Furlani et al.

Status: final response (author comments only)

Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor | : Report abuse
  • RC1: 'Comment on amt-2022-130', Anonymous Referee #1, 12 Jun 2022
  • RC2: 'Comment on amt-2022-130', Anonymous Referee #2, 13 Jun 2022

Teles C. Furlani et al.

Teles C. Furlani et al.


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Short summary
This study describes a new technique to measure the sum of gas phase chlorine-containing chemicals in the atmosphere. The method converts any chlorine-containing molecule to hydrogen chloride, which can be detected in real time using a cavity ring-down spectrometer. The new method was validated through laboratory experiments, as well as by making measurements outdoors and indoors during cleaning with a chlorine-based cleaner.