Abstract. Atmospheric HONO mixing ratios in indoor and outdoor environments span a range of less than a few parts per trillion by volume (pptv) up to tens of parts per billion by volume (ppbv) in combustion plumes. Previous HONO calibration sources have utilized proton transfer acid displacement from nitrite salts or solutions, with output that ranges from tens to thousands of ppbv. Instrument calibrations have thus required large dilution flows to obtain atmospherically relevant mixing ratios. Here we present a simple universal source to reach very low HONO calibration mixing ratios using a nitrite-coated reaction device with the addition of humid air and/or HCl from a permeation device. The calibration source developed in this work can generate HONO across the atmospherically relevant range and has high purity (> 90 %), reproducibility, and tunability. Mixing ratios at the tens of pptv level are easily reached with reasonable dilution flows. The calibration source can be assembled to start producing stable HONO mixing ratios (relative standard error, RSE ≤ 2 %) within 2 h, with output concentrations varying ≤ 25 % following simulated transport or complete disassembly of the instrument and with ≤ 10 % under ideal conditions. The simplicity of this source makes it highly versatile for field and lab experiments. The platform facilitates a new level of accuracy in established instrumentation, as well as intercomparison studies to identify systematic HONO measurement bias and interferences.

Many per- and polyfluoroalkyl substances (PFAS) have been regulated or phased-out of usage due to concerns about persistence, bioaccumulation potential, and toxicity. We investigated the atmospheric fate of a new polyfluorinated alcohol 2-(1,1,2-trifluoro-2-heptafluoropropyloxy-ethylsulfanyl)-ethanol (C3F7OCHFCF2SCH2CH2OH, abbreviated FESOH) by assessing the kinetics and products of the gas-phase reaction of FESOH with chlorine atoms and hydroxyl radicals. Experiments performed in a stainless-steel chamber interfaced to an FTIR were used to determine reaction kinetics and gas-phase products. We report reaction rate constants of k(Cl + FESOH) = (1.5 ± 0.6) × 10–11 cm3 molecule–1 s–1 and k(OH + FESOH) = (4.2 ± 2.0) × 10–12 cm3 molecule–1 s–1. This leads to a calculated FESOH gas-phase lifetime of 2.8 ± 1.3 days with respect to reaction with OH, assuming [OH] = 106 molecule1 cm–3. Gas-phase products of FESOH oxidation included at least two aldehydes, likely C3F7OCHFCF2SCH2C­(O)H and C3F7OCHFCF2SC­(O)­H, and secondary products including COF2, SO2 and C3F7OC­(O)­F. Additional gas-phase experiments performed in a Teflon chamber were used to assess aqueous products by collecting gaseous samples offline into an aqueous sink prior to analysis with ultrahigh performance liquid chromatography-tandem mass spectrometry, resulting in four acidic products: C3F7OCHFCF2SCH2C­(O)­OH, C3F7OCHFCF2S­(O)­(O)­OH, C3F7OCHFC­(O)­OH, and perfluoropropanoic acid (C2F5C­(O)­OH).

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.

Abstract. Atmospheric HONO mixing ratios in indoor and outdoor environments span a range of less than a few parts per trillion by volume (pptv) up to tens of parts per billion by volume (ppbv) in combustion plumes. Previous HONO calibration sources have utilized proton transfer acid displacement from nitrite salts or solutions, with output that ranges from tens to thousands of ppbv. Instrument calibrations have thus required large dilution flows to obtain atmospherically relevant mixing ratios. Here we present a simple universal source to reach very low HONO calibration mixing ratios using a nitrite-coated reaction device with the addition of humid air and/or HCl from a permeation device. The calibration source developed in this work can generate HONO across the atmospherically relevant range and has high purity (90–99 %), reproducibility, and tunability. Mixing ratios at the tens of pptv level are easily reached with reasonable dilution flows. The calibration source can be assembled to start producing stable HONO mixing ratios (RSE ≤ 2 %) within two hours, with output concentrations varying ≤ 25 % following simulated transport or complete disassembly of the instrument, and ≤ 10 % under ideal conditions. The simplicity of this source makes it highly versatile for field and lab experiments. The platform facilitates a new level of accuracy in established instrumentation, as well as intercomparison studies to identify systematic HONO measurement bias and interferences.

Ambient 0.5 Hz hydrogen chloride (HCl) measurements were made in Canadian cities to investigate chlorine activation and constrain the tropospheric chlorine budget. Springtime HCl mixing ratios in a coastal city (St. John’s, NL) were up to 1200 parts per trillion by volume (pptv) with a median of 63 pptv and were consistently elevated during daytime. High time-resolution measurements allowed the attribution of events to general sources, including direct emissions. Most coastal HCl was related to sea-salt aerosol acid displacement (R1) and chlorine activation. Continental urban (Toronto, ON) wintertime HCl mixing ratios reached up to 541 and 172 pptv, with medians of 67 and 11 pptv during two sampling periods characterized by different wind directions. The absence of consistent relationships with NO x , temperature, and wind direction, as well as a lack of diurnal patterns, suggested uncharacterized direct sources of HCl. One period with road salting occurred during sampling, but no relationship to changes in HCl observations was found. The contribution of road salt to the measured HCl may have been masked by larger contributors (such as direct sources of HCl) or perhaps the relationship between HCl and road salt application is not immediate, and thus additional measurements over multiple salting events or between seasons would be required. GEOS-Chem modeled HCl temporal variations in mixing ratios agreed well with coastal measurements only. The measured mixing ratios were underestimated by the model in both locations, but to a greater degree (up to 3 orders of magnitude) in the continental city. The discrepancy between the model and measurements for the continental wintertime city emphasizes the need for a greater understanding of direct sources of HCl and the impact of road salt.