Measurement-based modeling of bromine-induced oxidation of mercury above the Dead Sea
1The Institute of Earth Sciences, The Hebrew University, Jerusalem, Israel
2Department of Environmental Sciences and Energy, The Weizmann Institute of Science, Israel
3Division of Atmospheric Sciences, Desert Research Institute, 2215 Raggio Parkway, Reno, Nevada, 89512, USA
Abstract. Atmospheric mercury depletion events (AMDEs) outside the polar regions – driven by high levels of reactive bromine species (RBS) – were observed recently in the warm Dead Sea boundary layer. Efficient oxidation of gaseous elemental mercury (GEM) under temperate conditions by RBS was unexpected considering that the thermal back dissociation reaction of HgBr, a proposed key mechanism, is more than 2.5 orders of magnitude higher under Dead Sea temperatures compared with polar temperatures. The goal of this study was to improve understanding of RBS-mercury interactions using numerical simulations based on a comprehensive measurement campaign performed at the Dead Sea during summer 2009.
Results demonstrate a high efficiency and central role of BrOx (i.e., Br + BrO) for AMDEs at the Dead Sea, with relative contributions for GEM depletion of more than ~90 %. BrO was found to be the dominant oxidant with relative contribution above 80 %. Best agreement between simulations and observations was achieved by applying rate constants for kHg+Br and kHg+BrO of 2.7×10−13 cm3 molecule−1 s−1 and 1.5 × 10−13 cm3 molecule−1 s−1, respectively – indicating that kHg+BrO is higher than most reported values and that BrO is a more efficient oxidant than Br in the ozone-rich atmosphere (i.e., for [BrO]/[Br] >2). This further explains why the efficiency of GEM oxidation by reactive bromine species at the Dead Sea doesn't critically depend on Br and, therefore, is comparable to the efficiency in polar regions even under much higher temperatures. These findings also support the hypothesis identified in a previous study, that Br-induced GEM depletion can be important above oceans in the mid-latitudes and tropics. In the presence of anthropogenic NO2, RBS activity can lead to enhanced NO3 formation, which then causes significant nighttime GEM depletion.