Abstract. Reactive halogen species (RHS), such as X·, X 2 and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols.Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS, released from simulated natural halogen sources like salt pans. Subsequently, the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which results in new functional groups (FTIR spectroscopy), changes UV/VIS absorption, chemical composition (ultrahigh resolution mass spectroscopy (ICR-FT/MS)), or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance.
The pseudo-first-order loss of coniferyl aldehyde, adsorbed on silicon dioxide particles, upon heterogeneous ozonolysis was monitored at various ozone mixing ratios in the absence and presence of simulated sunlight. For the first time we investigated the effect of light on the heterogeneous ozonolysis of coniferyl aldehyde adsorbed on silica particles. We found that UV-VIS light (λ>300 nm) does not impact the degradation of coniferyl aldehyde by ozone but induces an additional, slow photolysis of the aldehyde with a photolytic rate constant of ~10(-5) s(-1). In both cases, that is, in presence and/or absence of light, the heterogeneous ozonation kinetics are well described by an immediate gas-surface reaction formalism with light-independent rate constants of k(2nd)=(7.2±0.9)×10(-19) cm(3) molec(-1) s(-1) and (7.6±1.7)×10(-19) cm(3) molec(-1) s(-1) in the absence and presence of light, respectively. Five oxidation products: glycolic acid, oxalic acid, vanillin, vanillic acid and 3,4-dihydroxybenzoic acid were identified and confirmed by their corresponding standards. Vanillin and vanillic acid absorb light in the region λ>300 nm and thus can further participate in the direct and indirect photolysis processes of atmospheric relevance. A reaction mechanism is proposed in order to elucidate the ozonolysis reaction and to explain the reaction products.
Reactive 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
Reactive halogen species (RHS), such as X·, X<sub>2</sub> and HOX containing X = chlorine and/or bromine, are released by various sources like photo-activated sea-salt aerosol or from salt pans, and salt lakes. Despite many studies of RHS reactions, the potential of RHS reacting with secondary organic aerosol (SOA) and organic aerosol derived from biomass-burning (BBOA) has been neglected. Such reactions can constitute sources of gaseous organohalogen compounds or halogenated organic matter in the tropospheric boundary layer and can influence physicochemical properties of atmospheric aerosols. <br><br> Model SOA from α-pinene, catechol, and guaiacol was used to study heterogeneous interactions with RHS. Particles were exposed to molecular chlorine and bromine in an aerosol smog-chamber in the presence of UV/VIS irradiation and to RHS released from simulated natural halogen sources like salt pans. Subsequently the aerosol was characterized in detail using a variety of physicochemical and spectroscopic methods. Fundamental features were correlated with heterogeneous halogenation, which result in new functional groups, changed UV/VIS absorption, or aerosol size distribution. However, the halogen release mechanisms were also found to be affected by the presence of organic aerosol. Those interaction processes, changing chemical and physical properties of the aerosol are likely to influence e.g. the ability of the aerosol to act as cloud condensation nuclei, its potential to adsorb other gases with low-volatility, or its contribution to radiative forcing and ultimately the Earth's radiation balance
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