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Lipid tracers including fatty acids, hydroxyacids, n-alkanols, sterols and triterpenoids were used to determine the origin and fate of suspended particulate organic matter (POM) collected in the Rhône River (France). This seasonal survey (April 2011 to May 2013) revealed a year-round strong terrestrial higher-plant contribution to the particulate organic matter (POM), with significant algal inputs observed in March and attributed to phytoplanktonic blooms likely dominated by diatoms. Major terrigenous contributors to our samples are gymnosperms, and more precisely their roots and stems, as evidenced by the presence of high proportions of ω-hydroxydocosanoic acid (a suberin biomarker). The high amounts of coprostanol detected clearly show that the Rhône River is significantly affected by sewage waters. Specific sterol degradation products were quantified and used to assess the part of biotic and abiotic degradation of POM within the river. Higher-plant-derived organic matter appears to be mainly affected by photo-oxidation and autoxidation (free radical oxidation), while organic matter of mammal or human origin, evidenced by the presence of coprostanol, is clearly more prone to bacterial degradation. Despite the involvement of an intense autoxidation-inducing homolytic cleavage of peroxy bonds, a significant proportion of hydroperoxides is still intact in higher plant debris. These compounds could affect the degradation of terrestrial material by inducing an intense autoxidation upon its arrival at sea.

The lipid content of seven samples of sinking particles collected with sediment traps moored at ~ 100 m depth in summer and fall across the Canadian Beaufort Shelf (Arctic Ocean) was investigated. Our main goal was to quantify and characterize the biotic and abiotic degradation processes that acted on sinking material during these periods. Diatoms, which dominated the phytoplanktonic assemblage in every trap sample, appeared to be remarkably sensitive to Type II (i.e. involving singlet oxygen) photodegradation processes in summer, but seemed to be relatively unaffected by biotic degradation at the same time. Hence, the relative recalcitrance of phytodetritus towards biodegradation processes during the Arctic midnight sun period was attributed to the strong photodegradation state of heterotrophic bacteria, which likely resulted from the efficient transfer of singlet oxygen from photodegraded phytoplanktonic cells to attached bacteria. In addition, the detection in trap samples of photoproducts specific to wax ester components found in herbivorous copepods demonstrated that zooplanktonic faecal material exported out of the euphotic zone in summer were affected by Type II photodegradation processes as well. By contrast, sinking particles collected during the autumn were not influenced by any light-driven stress. Further chemical analyses showed that photodegraded sinking particles contained an important amount of intact hydroperoxides, which could then induce a strong oxidative stress in underlying sediments.

For the next decades significant climatic changes should occur in the Arctic zone. The expected destabilisation of permafrost and its consequences for hydrology and plant cover should increase the input of terrigenous carbon to coastal seas. Consequently, the relative importance of the fluxes of terrestrial and marine organic carbon to the seafloor will likely change, strongly impacting the preservation of organic carbon in Arctic marine sediments. Here, we investigated the lipid content of surface sediments collected on the Mackenzie basin in the Beaufort Sea. Particular attention was given to biotic and abiotic degradation products of sterols and monounsaturated fatty acids. By using sitosterol and campesterol degradation products as tracers of the degradation of terrestrial higher plant inputs and brassicasterol degradation products as tracers of degradation of phytoplanktonic organisms, it could be observed that autoxidation, photooxidation and biodegradation processes act much more intensively on higher plant debris than on phytoplanktonic organisms. Examination of oxidation products of monounsaturated fatty acids showed that photo- and autoxidation processes act more intensively on bacteria than on phytodetritus. Enhanced damages induced by singlet oxygen (transferred from senescent phytoplanktonic cells) in bacteria were attributed to the lack of an adapted antioxidant system in these microorganisms. The strong oxidative stress observed in the sampled sediments resulted in the production of significant amounts of epoxy acids and unusually high proportions of monounsaturated fatty acids with a trans double bond. The formation of epoxy acids was attributed to peroxygenases (enzymes playing a protective role against the deleterious effects of fatty acid hydroperoxides in vivo), while cis/trans isomerisation was probably induced by thiyl radicals produced during the reaction of thiols with hydroperoxides. Our results confirm the important role played by abiotic oxidative processes in the degradation of marine bacteria and do not support the generally expected refractory character of terrigenous material deposited in deltaic systems.

Surface waters from the Beaufort Sea in the Arctic Ocean were evaluated for dissolved organic carbon (DOC), and optical characteristics including UV (ultraviolet) radiation and PAR (photosynthetically active radiation) diffuse attenuation (Kd), and chromophoric and fluorescent dissolved organic matter (CDOM and FDOM) as part of the MALINA field campaign (30 July to 27 August). Spectral absorption coefficients (aCDOM (350 nm) (m−1)) were significantly correlated to both diffuse attenuation coefficients (Kd) in the UV-A and UV-B and to DOC concentrations. This indicates CDOM as the dominant attenuator of both UV and PAR solar radiation and suggests its use as an optical proxy for DOC concentrations in this region. While the Mackenzie input is the main driver of CDOM dynamics in low salinity waters, locally, primary production can create significant increases in CDOM. Extrapolating CDOM to DOC relationships, we estimate that ∼16% of the DOC in the Mackenzie River does not absorb radiation at 350 nm. The discharges of DOC and its chromophoric subset (CDOM) by the Mackenzie River during the MALINA cruise are estimated as ∼0.22 TgC and 0.18 TgC, respectively. Three dissolved fluorescent components (C1–C3) were identified by fluorescence excitation/emission matrix spectroscopy (EEMS) and parallel factor (PARAFAC) analysis. Our results showed an aquatic dissolved organic matter (DOM) component (C1), probably produced in the numerous lakes of the watershed, that co-dominated with a terrestrial humic-like component (C2) in the Mackenzie Delta Sector. This aquatic DOM could partially explain the high CDOM spectral slopes observed in the Beaufort Sea.