Hydrogen chloride (HCl) at ground sites during CalNex 2010 and insight into its thermodynamic properties

Gas phase hydrogen chloride (HCl) was measured at Pasadena and San Joaquin Valley (SJV) ground sites in California during May and June 2010 as part of the CalNex study. Observed mixing ratios were on average 0.83 ppbv at Pasadena, ranging from below detection limit (0.055 ppbv) to 5.95 ppbv, and were on average 0.084 ppbv at SJV with a maximum value of 0.776 ppbv. At both sites, HCl levels were highest during midday and shared similar diurnal variations with HNO₃. Coupled phase partitioning behavior was found between HCl/Cl^- and HNO₃/NO₃ ^- using thermodynamic modelling and observations. Regional modeling of Cl^- and HCl using CMAQ captures some of the observed relationships but underestimates measurements by a factor of 5 or more. Chloride in the 2.5-10 microm size range in Pasadena was sometimes higher than sea salt abundances, based on co-measured Na⁺, implying that sources other than sea salt are important. The acid-displacement of HCl/Cl^- by HNO₃/NO₃ ^- (phase partitioning of semi-volatile acids) observed at the SJV site can only be explained by aqueous phase reaction despite low RH conditions and suggests the temperature dependence of HCl phase partitioning behavior was strongly impacted by the activity coefficient changes under relevant aerosol conditions (e.g., high ionic strength). Despite the influence from activity coefficients, the gas-particle system was found to be well constrained by other stronger buffers and charge balance so that HCl and Cl^- concentrations were reproduced well by thermodynamic models.