Abstract. Total gaseous chlorine (TClg) measurements can improve our
understanding of unknown sources of Cl in 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 processes. We describe high-time-resolution in situ measurements
of TClg by thermolyzing 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 previously 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 s, respectively. Complete conversion was observed for six
organochlorine compounds, including alkyl, allyl, and aryl C–Cl bonds, which
are amongst the strongest Cl-containing bonds. The quantitative conversion
of these strong C–Cl bonds suggests complete conversion of similar or weaker
bonds that characterize all other TClg. We applied this technique to
both outdoor and indoor environments and found reasonable agreements in
ambient background mixing ratios with the sum of expected HCl from known
long-lived 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 potential applications.