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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]

Abstract: Hydrographic structure of the water column, dissolved nutrient concentrations and the distribution of suspended particulate matter were recorded from CDT measurements and Niskin bottles sampling on the continental slope of the Bay of Biscay and on the axis of Capbreton canyon. Ascorbate extraction was applied here for the first time on marine suspended particles to determine the content of reactive Fe- and Mn-oxides, and P associated with Fe-oxides. Hydrographic structure of the south-eastern part of the Bay of Biscay did not change during the last three decades. Particulate organic carbon (POC) contents dropped strongly with depth, showing that organic matter mineralization was efficient in the water column. Organic matter mineralized in the water column had a Redfield N:P ratio. POC percent of particles collected at depth were higher during a bloom period, suggesting that some new organic matter reached the bottom. Contents of Fe and Mn extracted with the ascorbate leaching solution showed that suspended particles originated from the Gironde estuary, one of the major sources of particles in the Bay of Biscay. Intermediate and deeper nepheloid layers occurred in the Capbreton canyon. Particles of nepheloid layers were enriched in Mn- and Fe-oxides because they originated from resuspension of surface sediment. [Copyright &y& Elsevier]

Abstract: Particulate rare earth elements (REEs) were measured in modern sediment from the Bay of Biscay. Vertical profiles of total and reactive (ascorbate reducible) REEs have been studied in four contrasted sites ranging at water depth from 150 to 2800 m. The focus is on the coupling between the diagenetic conditions and the behavior of particulate REE. Total REEs fraction appears to be affected by the presence of metal sulphides that may act as an important carrier phase for solid REEs. In sediments where sulphate reduction is weak, the transfer from an unknown previous phase, stable in oxic conditions, to another one associated with sulphides seems to be direct, without mobilization in porewaters. In sediments where greater sulphate reduction occurs, we note the formation of an additional “authigenic” phase. Consequently, a threshold level of dissolved sulphide is a prerequisite for the formation of an additional “authigenic” REEs fraction. No direct relationship between the REEasc profiles and authigenic metal oxides have been observed, indicating that authigenic Fe and Mn oxides do not act as an efficient traps in the sediment. Despite particulate REE are mobile in these sediments, no fractionation of the lanthanide series is observed in relation to the redox conditions. [Copyright &y& Elsevier]

Abstract: The relationship between particulate organic carbon (POC) concentrations measured in modern sediment and fluxes of exported POC to the sediment surface needs to be understood in order to use POC content as a proxy of paleo-environmental conditions. The objective of our study was to compare POC concentrations, POC mineralization rates calculated from O2 consumption and POC burial rates. Benthic O2 distributions were determined in 58 fine-grained sediment cores collected at different periods at 14 stations in the southeastern part of the Bay of Biscay with depths ranging from 140 to 2800m. Depth-dependent volume-specific oxygen consumption rates were used to assess rates of aerobic oxidation of organic matter (OM), assuming that O2 consumption solely was related to heterotrophic activity at the sediment–water interface. Heterogeneity of benthic O2 fluxes denoted changes in time and space of fresh organic material sedimentation. The most labile fraction of exported POC engendered a steep decrease in concentration in the upper 5mm of vertical O2 profiles. The rupture in the gradient of O2 microprofile may be related to the bioturbation-induced mixing depth of fast-decaying carbon. Average diffusive O2 fluxes showed that this fast-decaying OM flux was much higher than buried POC, although diffusive O2 fluxes underestimated the total sediment oxygen demand, and thus the fast-decaying OM flux to the sediment surface. Sedimentary POC burial was calculated from sediment mass accumulation rate and the organic carbon content measured at the top of the sediment. The proportion of buried POC relative to total exported POC ranged at the most between 50% and 10%, depending on station location. Therefore, for a narrow geographic area like the Bay of Biscay, burial efficiency of POC was variable. A fraction of buried POC consisted of slow-decaying OM that was mineralized within the upper decimetres of sediment through oxic and anoxic processes. This fraction was deduced from the decrease with depth in POC concentration. At sites located below 500m water depth, where the fast-decaying carbon did not reach the anoxic sediment, the slow-decaying pool may control the O2 penetration depth. Only refractory organic material was fossilized in sedimentary records at locations where labile OM did not reach the anoxic portion of the sediment. [Copyright &y& Elsevier]

Abstract: Vertical profiles from the water column, including the maximum turbidity zone (MTZ) to the consolidated sediment were sampled in September 2000 in the freshwater reaches of the Gironde Estuary during a complete neap tide-spring tide cycle. The vertical distributions of dissolved major redox parameters and metals (Mn, Fe, Cd, Cu, V, Co, Ni, Mo, and U) were determined. Reactive particulate metal fractions were also determined from selective leaching. The studied system is characterized by density layers functioning at different time-scales, consisting of two mobile layers, i.e., the liquid (LM) and the soft mud (SM), overlying consolidated sediments (CS). This results in a three-zone diagenetic regime where (1) O2 dynamics are fast enough to show depletion in the rapidly mixed LM sequence (tidal time-scale), (2) denitrification occurs on the weekly time-scale mixing SM sequence, and (3) the Mn, Fe, and sulfate cycling occurs in the CS layer (annual time-scale). The studied trace metals show differential behavior during early diagenesis: (1) Cd, Cu, and V are released into pore water preferentially from organic matter in the SM, (2) Co, Ni, and U are released in the CS from Mn and Fe oxides during reductive dissolution, and (3) Mo from both processes. Transient conditions (i.e., oscillations of redox fronts and reoxidation processes), due to the dynamics of the mobile layers, strongly influence the trace metal distributions as inducing resolubilization (Cd, Cu, and Mo). In the CS, authigenic metal phases accumulate, either by direct precipitation with sulfides (Cu, Cd) or co-precipitation with Fe-sulfides (Mo). Microbially mediated reduction of Fe oxides is proposed to control U removal from pore water by reduction of U(VI) to U(IV) at depth. However, a significant fraction of the trace metals is trapped in the sediment in exchangeable forms, and therefore is susceptible to be mobilized due to resuspension of estuarine sediment during strong river flood periods and/or dredging activities. [Copyright &y& Elsevier]