Mercury oxidation from bromine chemistry in the free troposphere over the southeastern US

Abstract

Abstract. The elevated deposition of atmospheric mercury over the Southeastern United States is currently not well understood. Here we measure partial columns and vertical profiles of bromine monoxide (BrO) radicals, a key component of mercury oxidation chemistry, to better understand the processes and altitudes at which mercury is being oxidized in the atmosphere. We use the data from a ground-based MAX-DOAS instrument located at a coastal site ~ 1 km from the Gulf of Mexico in Gulf Breeze, FL, where we had previously detected tropospheric BrO (Coburn et al., 2011). Our profile retrieval assimilates information about stratospheric BrO from the WACCM chemical transport model, and uses only measurements at moderately low solar zenith angles (SZA) to estimate the BrO slant column density contained in the reference spectrum (SCDRef). The approach has 2.6 degrees of freedom, and avoids spectroscopic complications that arise at high SZA; knowledge about SCDRef helps to maximize sensitivity in the free troposphere (FT). A cloud-free case study day with low aerosol load (9 April 2010) provided optimal conditions for distinguishing marine boundary layer (MBL: 0–1 km) and free tropospheric (FT: 1–15 km) BrO from the ground. The average daytime tropospheric BrO vertical column density (VCD) of ~ 2.3 × 1013 molec cm−2 (SZA < 70°) is consistent with our earlier reports on other days. The vertical profile locates essentially all tropospheric BrO above 4 km, and shows no evidence for BrO inside the MBL (detection limit < 0.5 pptv). BrO increases in the FT. The average FT-BrO mixing ratio was ~ 0.9 pptv between 1–15 km, consistent with recent aircraft observations. We find that the oxidation of gaseous elemental mercury (GEM) by bromine radicals to form gaseous oxidized mercury (GOM) is the dominant pathway for GEM oxidation throughout the troposphere above Gulf Breeze. The column integral oxidation rates range from 3.0–3.4 × 105 molec cm−2 s−1 for bromine, while contributions from ozone (O3) and chlorine (Cl) were 0.9 × 105 and 0.2 × 105 molec cm−2 s−1, respectively. The GOM formation rate is sensitive to recently proposed atmospheric scavenging reactions of the HgBr adduct by nitrogen dioxide (NO2), and to a lesser extent also HO2 radicals. Using a 3-D chemical transport model, we find that surface GOM variations are typical also of other days, and are mainly derived from the free troposphere. Bromine chemistry is active in the FT over Gulf Breeze, where it forms water-soluble GOM that is subsequently available for wet scavenging by thunderstorms or transport to the boundary layer.