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.

Sea-level control on the connection between shelf-edge deltas and the Bourcart canyon head (western Mediterranean) during the last glacial/interglacial cycle

A dense grid of high- and very high resolution seismic data, together with piston cores and borehole data providing time constraints, enables us to reconstruct the history of the Bourcart canyon head in the western Mediterranean Sea during the last glacial/interglacial cycle. The canyon fill is composed of confined channel–levee systems fed by a series of successively active shelf fluvial systems, originating from the west and north. Most of the preserved infill corresponds to the interval between Marine Isotope Stage (MIS) 3 and the early deglacial (19 cal ka BP). Its deposition was strongly controlled by a relative sea level that impacted the direct fluvial/canyon connection. During a period of around 100 kyr between MIS 6 and MIS 2, the canyon “prograded” by about 3 km. More precisely, several parasequences can be identified within the canyon fill. They correspond to forced-regressed parasequences (linked to punctuated sea-level falls) topped by a progradational-aggradational parasequence (linked to a hypothetical 19-ka meltwater pulse (MWP)). The bounding surfaces between forced-regressed parasequences are condensed intervals formed during intervals of relative sediment starvation due to flooding episodes. The meandering pattern of the axial incision visible within the canyon head, which can be traced landward up to the Agly paleo-river, is interpreted as the result of hyperpycnal flows initiated in the river mouth in a context of increased rainfall and mountain glacier flushing during the early deglacial.

Sedimentary archives of climate and sea-level changes during the Holocene in the Rhone prodelta (NW Mediterranean Sea)

A 7.38 m-long sediment core was collected from the eastern part of the Rhone prodelta (NW Mediterranean) at 67 m water depth. A multi-proxy study (sedimentary facies, benthic foraminifera and ostracods, clay mineralogy, and major elements from XRF) provides a multi-decadal to century-scale record of climate and sea-level changes during the Holocene. The early Holocene is marked by alternative silt and clay layers interpreted as distal tempestites deposited in a context of rising sea level. This interval contains shallow infra-littoral benthic meiofauna (e.g. Pontocythere elongata, Elphidium spp., Quinqueloculina lata) and formed between ca. 20 and 50 m water depth. The middle Holocene (ca. 8.3 to 4.5 ka cal. BP), is characterized, at the core site, by a period of sediment starvation (accumulation rate of ca. 0.01 cm yr−1) resulting from the maximum landward shift of the shoreline and the Rhone outlet(s). From a sequence stratigraphic point of view, this condensed interval, about 35 cm-thick, is a Maximum Flooding Surface that can be identified on seismic profiles as the transition between delta retrogradation and delta progradation. It is marked by very distinct changes in all proxy records. Following the stabilization of the global sea level, the late Holocene is marked by the establishment of prodeltaic conditions at the core site, as shown by the lithofacies and by the presence of benthic meiofauna typical of the modern Rhone prodelta (e.g. Valvulineria bradyana, Cassidulina carinata, Bulimina marginata). Several periods of increased fluvial discharge are also emphasized by the presence of species commonly found in brackish and shallow water environments (e.g. Leptocythere). Some of these periods correspond to the multi-decadal to centennial late Holocene humid periods recognized in Europe (i.e. the 2.8 ka event and the Little Ice Age). Two other periods of increased runoffs at ca. 1.3 and 1.1 ka cal. BP are recognized, and are likely to reflect periods of regional climate deterioration that are observed in the Rhone watershed.