Observations of bromine explosions in smog chamber experiments above a model salt pan

Abstract

AbstractReactive halogen species (RHS), such as Cl, Br, or BrO, can have significant influence on chemical processes in the troposphere, including the destruction of ozone, change in the chemical balance of OH and HO2, and increased deposition of toxic compounds (like mercury), with potential consequences for the global climate. Previous studies have shown that salt lakes can provide a significant source for gaseous RHS. Environmental conditions, such as salt composition, relative humidity (RH), pH, and temperature (T), might have a strong influence on reactive bromine levels. In our laboratory experiments, NaCl salt containing 0.33% NaBr by weight was exposed to simulated sunlight in a Teflon smog chamber under various conditions of RH and ozone concentrations. BrO levels were observed by a differential optical absorption spectrometer in combination with a multireflection cell (White cell). The concentrations of OH and Cl radicals were quantified by the radical clock method. We present the first direct observation of BrO from the “bromine explosion” (autocatalytic release of reactive bromine from salt surfaces—key to ozone destruction) in the laboratory above a simulated salt pan. The maximum BrO mixing ratio of 6419 ± 71 ppt at 60% RH was observed to be one order of magnitude higher than at 37% RH and 2% RH. The release of RHS from the salt pan is possibly controlled by the thickness of the quasi‐liquid layer, covering the reactive surface of the halide crystals, as the layer thickness strongly depends on RH. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 312–326, 2012