Frédéric Vaultier

Autoxidative and Photooxidative Reactivity of Highly Branched Isoprenoid (HBI) Alkenes

Autoxidation of several mono-, di-, tri- and tetra-unsaturated highly branched isoprenoid (HBI) alkenes was induced in organic solvents using a radical initiator and enhancer, and their degradation rates were compared to those of classical phytoplanktonic lipids (mono-unsaturated fatty acids, sterols and chlorophyll phytyl side-chain). Autoxidation of two HBI trienes was also investigated in senescent and highly photodegraded diatom cells, collected in the Antarctic, using Fe2+ ions as radical inducers. Autoxidation rates of HBI alkenes were found to increase with the number of tri-substituted double bonds, as expected. Further, HBI trienes possessing one bis-allylic position (where hydrogen abstraction is highly favoured) were found to be particularly reactive towards autoxidation and degraded at similar rates compared to polyunsaturated fatty acids in diatom cells. By comparison of the autoxidation products of the most reactive tri-unsaturated HBI with the corresponding photooxidation products, some specific tracers of these two types of abiotic degradation processes were identified. The lack of reactivity of the mono-unsaturated HBI IP25 and a structurally similar di-unsaturated HBI towards autoxidative degradation supports the good preservation of these biomarkers in marine sediments.

Photochemical Production and Behavior of Hydroperoxyacids in Heterotrophic Bacteria Attached to Senescent Phytoplanktonic Cells

The photooxidation of cellular monounsaturated fatty acids was investigated in senescent phytoplanktonic cells (Emiliania huxleyi) and in their attached bacteria under laboratory controlled conditions. Our results indicated that UV-visible irradiation of phytodetritus induced the photooxidation of oleic (produced by phytoplankton and bacteria) and cis-vaccenic (specifically produced by bacteria) acids. These experiments confirmed the involvement of a substantial singlet oxygen transfer from senescent phytoplanktonic cells to attached bacteria, and revealed a significant correlation between the concentration of chlorophyll, a photosensitizer, in the phytodetritus and the photodegradation state of bacteria. Hydroperoxyacids (fatty acid photoproducts) appeared to be quickly degraded to ketoacids and hydroxyacids in bacteria and in phytoplanktonic cells. This degradation involves homolytic cleavage (most likely induced by UV and/or transition metal ions) and peroxygenase activity (yielding epoxy acids).

Autoxidation as a major player in the fate of terrestrial particulate organic matter in seawater

The Rhone River plays a major role in the Mediterranean Sea, being both its main freshwater source and its major particulate matter provider. This survey of the fate of terrestrial particulate organic matter (POM) was conducted along the salinity gradient of the Rhone River plume, between 2012 and 2014. It revealed that autoxidation acts rapidly and intensely upon the POMs arrival at sea, with α-amyrin and β-amyrin autoxidation rates going from 12.9 ± 2.9% to 45.0 ± 6.4% and 10.7 ± 4.0% to 50.3 ± 4.4%, respectively, between fresh water (salinity 0) and seawater (salinity 38). These compounds, being unambiguous markers of the terrestrial origin of POM, allow us to unequivocally characterize the POM as terrestrial. While it was originally believed that a desorption of redox-active trace metal ions was the favoring factor that kick-started this intense autoxidation, this study evidences no trace metal desorption in the Rhone River mixing zone and hence no correlation between high autoxidation rates and the presence of trace metal ions. Autoxidation rates however were very well correlated with salinity levels within the river plume, with r 2 reaching 0.801, 0.962, and 0.943 for sitosterol, α-amyrin, and β-amyrin, respectively, in November 2014.