Bromination of marine particulate organic matter through oxidative mechanisms
Bruce D. Ravel, Alessandra C. Leri, Kathleen Thornton, Lawrence M. Mayer
Although bromine is considered conservative in seawater, it exhibits a well established correlation with organic carbon in marine sediments. This carbon-bromine association was recently attributed to covalent bonding, with organobromine in sinking particulates providing a putative link between sedimentary organobromine and organic matter cycling in surface waters. Here, we demonstrate incorporation of bromine into algal particulate detritus through peroxidative and photochemical mechanisms. Peroxidative bromination was enhanced by addition of exogenous bromoperoxidase, but the enzyme was not required for the reaction. Fenton-like reaction conditions also promoted bromination, especially under solar irradiation, implicating radical mechanisms in the euphotic zone as another abiotic source of brominated particulates. These reactions produced aliphatic and aromatic forms of organobromine, consistent with the lipid- and protein-rich nature of membrane substrates. Native biogenic organobromines also appeared in both forms. Experimental evidence and samples from oceanic midwater sediment traps imply that the aromatic fraction is more stable than the aliphatic. These experiments establish Br as a versatile oxidant in the transformation of planktonic organic matter, perhaps accounting for the apparent chemical heterogeneity of sedimentary Br7. Organobromine may serve as a marker of oxidative breakdown of marine organic detritus, with the metastable component providing a short-lived indicator of early-stage oxidation.