Isotopic composition of polyhalomethanes from marine macrophytes – systematic effects of the halogen substituents on isotopic composition

Abstract

Environmental context Once released to the atmosphere, halocarbons are involved in key chemical reactions. Stable carbon isotope measurements of halocarbons can provide valuable information on their sources and fate in the atmosphere. Here, we report δ13C values of 13 polyhalomethanes released from brown algae, which may provide a basis for inferring their sources and fate in future studies. Abstract Halocarbons are important vectors of reactive halogens to the atmosphere, where the latter participate in several key chemical processes. An improved understanding of the biogeochemical controls of the production–destruction equilibrium on halocarbons is of vital importance to address potential future changes in their fluxes to the atmosphere. Carbon stable isotope ratios of halocarbons could provide valuable additional information on their sources and fate that cannot be derived from mixing ratios alone. We determined the δ13C values of 13 polyhalomethanes from three brown algae species (Laminaria digitata, Fucus vesiculosus, Fucus serratus) and one seagrass species (Zostera noltii). The δ13C values were determined in laboratory incubations under variable environmental conditions of light, water levels (to simulate tidal events) and addition of hydrogen peroxide (H2O2). The δ13C values of the polyhalomethanes ranged from –42.2 ‰ (±3.5s.d.) for CHCl3 to 6.9 ‰ (±4.5) for CHI2Br and showed a systematic effect of the halogen substituents that could empirically be described in terms of linear free energy relationships. We further observed an enrichment in the δ13C of the polyhalomethanes with decreasing polyhalomethane yield that is attributed to the competing formation of halogenated ketones. Though variable, the isotopic composition of polyhalomethanes may provide useful additional information to discriminate between marine polyhalomethane sources.