The estuarine geochemical reactivity of Zn isotopes and its relevance for the biomonitoring of anthropogenic Zn and Cd contaminations from metallurgical activities: Example of the Gironde fluvial-estuarine system, France

Zinc stable isotopes measurements by MC-ICP-MS, validated by laboratory intercalibrations, were performed on wild oysters, suspended particles and filtered river/estuarine water samples to provide new constraints for the use of Zn isotopes as environmental tracers. The samples selected were representative of the long range (400 km) transport of metal (Zn, Cd, etc.) contamination from former Zn-refining activities at Decazeville (i.e. δ66Zn > 1 ‰) and its phasing out, recorded during 30 years in wild oysters from the Gironde Estuary mouth (RNO/ROCCH sample bank). The study also addresses additional anthropogenic sources (urban and viticulture) and focuses on geochemical reactivity of Zn in the turbidity gradient and the maximum turbidity zone (MTZ) of the fluvial Gironde Estuary. In this area, dissolved Zn showed a strong removal onto suspended particulate matter (SPM) and progressive enrichment in heavy isotopes with increasing SPM concentrations varying from δ66Zn = -0.02 ‰ at 2 mg/L to +0.90 ‰ at 1310 mg/L. These signatures were attributed to kinetically driven adsorption due to strongly increasing sorption sites in the turbidity gradient and MTZ of the estuary. Oysters from the estuary mouth, contaminated sediments from the Lot River and SPM entering the estuary showed parallel historical evolutions (1979-2010) for Zn/Cd ratios but not for δ66Zn values. Oysters had signatures varying from δ66Zn = 1.43 ‰ in 1983 to 1.18 ‰ in 2010 and were offset by δ66Zn = 0.6 - 0.7 ‰ compared to past (1988) and present SPM from the salinity gradient. Isotopic signatures in river-borne particles entering the Gironde Estuary under contrasting freshwater discharge regimes during 2003-2011 showed similar values (δ66Zn ≈ 0.35 ± 0.03 ‰; 1SD, n=15), i.e. they were neither related to former metal refining activities at least for the past decade nor clearly affected by other anthropogenic sources. Therefore, the Zn isotopic signatures in Gironde oysters reflect the geochemical reactivity of Zn in the estuary rather than signatures of past metallurgical contaminations in the watershed as recorded in contaminated river sediments. The study also shows that the isotopic composition of Zn is strongly fractionated by its geochemical reactivity in the Gironde Estuary, representative of meso-macrotidal estuarine systems.

The pianosa contourite depositional system (northern Tyrrhenian sea): drift morphology and plio-quaternary stratigraphic evolution

The Pianosa Contourite Depositional System (CDS) is located in the Corsica Trough (Northern Tyrrhenian Sea), a confined basin dominated by mass transport and contour currents in the eastern flank and by turbidity currents in the western flank. The morphologic and stratigraphic characterisation of the Pianosa CDS is based on multibeam bathymetry, seismic reflection data (multi-channel high resolution mini GI gun, single-channel sparker and CHIRP), sediment cores and ADCP data. The Pianosa CDS is located at shallow to intermediate water depths (170 to 850 m water depth) and is formed under the influence of the Levantine Intermediate Water (LIW). It is 120 km long, has a maximum width of 10 km and is composed of different types of muddy sediment drifts: plastered drift, separated mounded drift, sigmoid drift and multicrested drift. The reduced tectonic activity in the Corsica Trough since the early Pliocene permits to recover a sedimentary record of the contourite depositional system that is only influenced by climate fluctuations. Contourites started to develop in the Middle-Late Pliocene, but their growth was enhanced since the Middle Pleistocene Transition (0.7–0.9 Ma). Although the general circulation of the LIW, flowing northwards in the Corsica Trough, remained active all along the history of the system, contourite drift formation changed, controlled by sediment influx and bottom current velocity. During periods of sea level fall, fast bottom currents often eroded the drift crest in the middle and upper slope. At that time the proximity of the coast to the shelf edge favoured the formation of bioclastic sand deposits winnowed by bottom currents. Higher sediment accumulation of mud in the drifts occurred during periods of fast bottom currents and high sediment availability (i.e. high activity of turbidity currents), coincident with periods of sea level low-stands. Condensed sections were formed during sea level high-stands, when bottom currents were more sluggish and the turbidite system was disconnected, resulting in a lower sediment influx.

New insights into the transport processes controlling the sulfate-methane-transition-zone near methane vents

Over the past years, several studies have raised concerns about the possible interactions between methane hydrate decomposition and external change. To carry out such an investigation, it is essential to characterize the baseline dynamics of gas hydrate systems related to natural geological and sedimentary processes. This is usually treated through the analysis of sulfate-reduction coupled to anaerobic oxidation of methane (AOM). Here, we model sulfate reduction coupled with AOM as a two-dimensional (2D) problem including, advective and diffusive transport. This is applied to a case study from a deep-water site off Nigeria’s coast where lateral methane advection through turbidite layers was suspected. We show by analyzing the acquired data in combination with computational modeling that a two-dimensional approach is able to accurately describe the recent past dynamics of such a complex natural system. Our results show that the sulfate-methane-transition-zone (SMTZ) is not a vertical barrier for dissolved sulfate and methane. We also show that such a modeling is able to assess short timescale variations in the order of decades to centuries.