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We used a diagenetic model to test the hypothesis that manganese-rich layers in gas hydrate-bearing Arctic Ocean sediments are reliable time markers for interglacial periods. In the model, diagenesis is fuelled by two sources of reactive carbon: particulate organic carbon settling to the sediment surface, and methane diffusing up from deep gas hydrate deposits. The model includes oxidation of organic carbon and soluble reduced manganese by oxygen supplied continuously from an invariant bottom-water oxygen reservoir; reduction of particulate manganese by hydrogen sulfide generated through anaerobic methane oxidation; transport of dissolved oxygen and manganese by diffusion; and advective transport of particulate components by burial. Particulate organic matter and particulate manganese are only supplied to the sediment during interglacials. Sulfate reduction is not modeled explicitly; instead, the effect of anaerobic methane oxidation on Mn reduction is simulated at the lower boundary of the model by prescribing that particulate manganese is reduced there to soluble Mn(II). The soluble reduced Mn then diffuses upward and is oxidatively precipitated to Mn(IV) by downward diffusing oxygen. The upward flux of soluble Mn(II) is thus a function of the rate at which particulate manganese is advected into the Mn-reduction layer at the bottom of the model; it is not synchronous with events at the sediment–water interface. Model runs reveal that, under idealized but realistic conditions for the Arctic Ocean, oxidation of upward-diffusing Mn(II) generates post-depositional manganese enrichments that cannot readily be distinguished from the manganese-rich sediment layers that accumulate during interglacials. This compromises the use of manganese-rich layers as proxies for interglacial periods. In contrast, manganese-rich layers may be used as first-order markers of interglacial periods in sediments where gas hydrates or other forms of reactive carbon are absent. [ABSTRACT FROM AUTHOR]

Abstract: Sandy sediments of tidal beaches are poor in reactive substances because they are regularly flushed by significant flow caused by tidal forcing. This transport process may significantly affect the flux of reactive solutes to the ocean. A two dimensional model coupling the Richards equation that describes the flow in permeable sediments and the conservation equation of the silicic acid was developed to simulate the evolution of the silicic acid concentration into a variably saturated porous media submitted to tidal forcing. A detailed algorithm of drainage zone under tidal forcing and numerical methods needed to solve it are properly presented. Flux to the ocean has been estimated. The silicic acid concentration displays a permanent lens with low silicic acid concentration at the top of the tidal zone. This lens that results from the tidal forcing, presents weak variations of area during the tidal cycle. Silicic outflux to the ocean increases with increasing beach slope, hydraulic conductivity and tidal range. Simulations reveal that the total silicic acid flux to the ocean from the coastal marine sands can be considered as significant compared to the flux supplied by the rivers. These results may alter the previously published global budget of the silicic acid to the ocean. [Copyright &y& Elsevier]

Abstract: Bioturbation refers to the mixing of sediment particles resulting from benthic faunal activity. It is the dominant particle mixing process in most marine sediments and exerts an important control on diagenetic processes. In models, bioturbation is usually treated as a diffusive process where the biodiffusion coefficient (Db) characterizes the biological mixing intensity. Biodiffusion coefficients are classically computed by fitting a diffusive model to vertical profiles of particle-bound radioisotopes. One peculiar observation is tracer-dependence: Db values from short-lived tracers tend to be larger than those obtained from long-lived tracers from the same site. Recent theoretical work, based on random walk theory and Lattice Automaton Bioturbation Simulations (LABS), has suggested that this tracer-dependence is simply a model artifact and has concluded that the biodiffusion model is not applicable to the short observational time scales associated with short-lived radioisotopes. Here we have compiled a global dataset of Db values obtained from different radiotracers to assess tracer-dependence from a data perspective. Tracer-dependence is significant in low-mixing environments like slope and deep-sea sediments, but is not present in intensely mixed coastal areas. Tracer-dependence is absent when the number of mixing events is larger than 20, or the potential length scale is greater than 0.5cm. Roughly this comes down to tracer-derived Db values greater than 2cm2 yr−1. This condition is met for 68%, 50%, and 8% of published Db values obtained from coastal, continental slope, and abyssal environments, respectively. These results show that short-lived radioisotopes are suitable to quantify biodiffusion mixing in sedimentary environments featuring intense bioturbation. [ABSTRACT FROM AUTHOR]

Manganese is a major redox reactive element of benthic metabolism. We have built a database of existing knowledge on the benthic geochemistry of Mn in the Bay of Biscay, in order to comprehensively assess the behaviour of Mn in a variety of environments during early diagenesis. The database contains vertical profiles of particulate and dissolved Mn species of 59 cores collected during 17 cruises between 1997 and 2006 at nine stations positioned between 140 and 4,800 m water depths. At all studied stations, Mn species follow the conventional distribution, where Mn(III,IV) species are enriched in the oxic layer, and dissolved Mn is present in the anoxic sediments. A minor part of Mn-oxides originates from sedimenting particles. The major part is of diagenetic origin, and derives from the oxidation of upward-diffusing dissolved Mn(II). Mn-oxide inventories are higher at the deeper stations than at the shallower ones. This difference cannot be attributed to different sources of sedimenting particles, but it must depend on sedimentation rate and diagenetic processes. At depth, dissolved Mn(II) concentrations are constant. This probably reflects equilibrium with an authigenic Mn(II) phase, which is the ultimate phase into which Mn is fossilized. The Mn content of deeper anoxic sediments is similarly low in all the cores studied, associated with corresponding trends of Mn content in sedimenting particles of the Bay of Biscay. Bioturbation, rather than redox oscillations, can convey Mn(III,IV) species downwards into the anoxic sediments where they are reduced, associated with a peak of dissolved Mn. Because dissolved Mn(II) is re-oxidized when it diffuses towards the oxic layer, the inventory of the diagenetic Mn(III,IV) phase remains at steady state, especially at stations where the oxic layer is thick. It then becomes possible to calculate the residence time of diagenetic Mn(III,IV) particles within the oxic layer, using the upward-directed flux of pore water Mn(II). By applying this residence time to the accumulation of sediments within the oxic layer, we obtain the sediment mass accumulation rate. The values calculated for the sediments of the Bay of Biscay fit well with accumulation rates obtained from radionuclides or sediment traps. The method has also been validated with data collected in other marine sedimentary environments. [ABSTRACT FROM AUTHOR]

Precise indices based on n -alkane signatures were developed in order to determine the sources and composition of sedimentary organic matter (SOM) in coastal systems. The Arcachon Bay (France), a well-studied temperate lagoon, was used as an example of a complex coastal system sheltering a wide diversity of OM sources. Three main groups of sources were well discriminated from their n -alkane signatures: seagrass ( Zostera sp.) produced mainly n -C 17 , n -C 19 , n -C 21 , n -C 23 and n -C 25 alkanes, algae (Rhodophyta, Chlorophyta) produced n -C 15 and n -C 17 and the terrigenous input [ Quercus sp., Spartina sp. and river suspended particulate OM (SPOM)] was characterized by n -C 25 , n -C 27 , n -C 29 , n -C 31 and n -C 33 . From the above and literature n -alkane fingerprints, we developed a set of indices ( n -alkane ratios) to quantify the contribution of these three major sources of the SOM. At the Arcachon Bay scale, they indicated that SOM was composed mainly of seagrass (ca. 53 ± 19%) and terrestrial (ca. 41 ± 17%) material, followed by algae (ca. 6 ± 9%). Moreover, the new n -alkane indices exhibited more relevant spatial patterns than classical ones – the TAR (C 27 + C 29 + C 31 /C 15 + C 17 + C 19 ; terrestrial to aquatic ratio) and the P aq (C 23 + C 25 /C 23 + C 25 + C 29 + C 31 ; aquatic plant %) – with a greater contribution from marine sources in the central part of the lagoon where a high density of Zostera seagrass was observed. Therefore, the development of precise indices adapted to the local diversity of OM sources is needed when using n -alkanes for quantifying the source composition of SOM in complex coastal systems. [ABSTRACT FROM AUTHOR]

Abstract: Sandy sediments of continental shelves and most beaches are often thought of as geochemical deserts because they are usually poor in organic matter and other reactive substances. The present study focuses on analyses of dissolved biogenic compounds of surface seawater and pore waters of Aquitanian coastal beach sediments. To quantitatively assess the biogeochemical reactions, we collected pore waters at low tide on tidal cross-shore transects unaffected by freshwater inputs. We recorded temperature, salinity, oxygen saturation state, and nutrient concentrations. These parameters were compared to the values recorded in the seawater entering the interstitial environment during floods. Cross-shore topography and position of piezometric level at low tide were obtained from kinematics GPS records. Residence time of pore waters was estimated by a tracer approach, using dissolved silica concentration and kinetics estimate of quartz dissolution with seawater. Kinetics parameters were based on dissolved silica concentration monitoring during 20-day incubations of sediment with seawater. We found that seawater that entered the sediment during flood tides remained up to seven tidal cycles within the interstitial environment. Oxygen saturation of seawater was close to 100%, whereas it was as low as 80% in pore waters. Concentrations of dissolved nutrients were higher in pore waters than in seawater. These results suggest that aerobic respiration occurred in the sands. We propose that mineralised organic matter originated from planktonic material that infiltrated the sediment with water during flood tides. Therefore, the sandy tidal sediment of the Aquitanian coast is a biogeochemical reactor that promotes or accelerates remineralisation of coastal pelagic primary production. Mass balance calculations suggest that this single process supplies about 37kmol of nitrate and 1.9kmol of dissolved inorganic phosphorus (DIP) to the 250-km long Aquitanian coast during each semi-diurnal tidal cycle. It represents about 1.5% of nitrate and 5% of DIP supplied by the nearest estuary. [Copyright &y& Elsevier]