Emission of volatile halogenated organic compounds over various landforms at the Dead Sea

Abstract

<p><strong>Abstract.</strong> Volatile halogenated organic compounds (VHOCs), such as methyl halides (CH<sub>3</sub>X; X = Br, Cl and I) and very short-lived halogenated substances (VSLS; CHBr<sub>3</sub>, CH<sub>2</sub>Br<sub>2</sub>, CHBrCl<sub>2</sub>, C<sub>2</sub>HCl<sub>3</sub>, CHCl<sub>3</sub> and CHBr<sub>2</sub>Cl) are well known for their significant influence on ozone concentrations and oxidation capacity of the troposphere and stratosphere, and for their key role in aerosol formation. Insufficient characterization of the sources and emission rate of VHOCs limits our present ability to understand and assess their impact in both the troposphere and the stratosphere. Over the last two decades several natural terrestrial sources for VHOCs, including soil and vegetation, have been identified, but our knowledge about emission rates from these sources and their responses to changes in ambient conditions remains limited. Here we report measurements of the mixing ratios and the fluxes of several chlorinated and brominated VHOCs from different landforms and vegetated sites at the Dead Sea during different seasons. Fluxes were highly variable but were generally positive (emissive), corresponding with elevated mixing ratios for all of the VHOCs investigated in the four investigated site types – bare soil, coastal, cultivated and natural vegetated sites – except for fluxes of CH<sub>3</sub>I and C<sub>2</sub>HCl<sub>3</sub> over the vegetated sites. In contrast to previous reports, we also observed emissions of brominated trihalomethanes, with net molar fluxes ordered as follows: CHBr<sub>2</sub>Cl > CHBr<sub>3</sub> > CHBrCl<sub>2</sub> > CHCl<sub>3</sub>. This finding can be explained by the enrichment of soil with Br. Correlation analysis, in agreement with recent studies, indicated common controls for the formation and emission of all the above trihalomethanes but also for CH<sub>2</sub>Br<sub>2</sub>. Also in line with previous reports, we observed elevated emissions of CHCl<sub>3</sub> and C<sub>2</sub>HCl<sub>3</sub> from mixtures of soil and different salt-deposited structures; the high correlations of flux with methyl halides, and particularly with CH<sub>3</sub>I, suggested that at least CH<sub>3</sub>I is also emitted via similar mechanisms or is subjected to similar controls. Overall, our results indicate elevate emission of VHOCs from bare soil under semi-arid conditions. Along with other recent studies, our findings point to the strong emission potential of a suite of VHOCs from saline soils and salt lakes, and call for additional studies of emission rates and mechanisms of VHOCs from saline soils and salt lakes.</p>