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.

Site n°5. The Pertuis Breton (Bay of Biscay) France

1.This report presents the results of a field study conducted in the ECASA test site nOS in the Pertuis Breton, France. The site is located on the Atlantic West coasts. It is open to the bay of Biscay, but is slightly protected against westerly winds. The bay has been exploited by intertidal mussels culture for centuries. 2. Within the bay, mussels (Mytilus edulis) are cultivated either by the traditional pole technique, around the bay or on longlines in the centre of the bay. The area occupied by these longline s represents 250 ha, and the resulting annual production is 1 000 tonnes of mussels. The average depth at mid tide is of 13.8 m. The sediment is sandy, with a small fraction of mud. 3. The site is subject to several regular monitoring through the local implementation of national networks aiming at protecting the environment and marine resources, on pollutants (RNO), microbiological quality of the waters (REMI), phytoplanktonic toxic species (REPHY) and growth and mortality of molluscs (REMORA). Benthic macrofauna was studied in 1976. 4. Five sampling sations were chosen along a line, starting under the longlines, and at distances of 50, 100, 200, and 400 metres from the area cultivated. A reference station was chosen in a different direction at 2300 metres of the cultivated area. Sampling methods are described in the text. _Sediments were sampled for different analyses: grain size, content in organic matter, total organic carbon and nitrogen, and phytic pigments (chlorophyll a and phaeopigments). Redox were measured in cores. The macrofauna living into the sediment was also sampled. The water column was sampled for physical (temperature, transparency) and chemical parametres, including oxygen content, salinity, organic matter, dissolved nitrogen forms, phosphates and silicates. Results from benthic macrofauna surveys indicate that there were no significant differences between the different stations and the reference station, all being classified as slightly disturbed. The bay is submitted to freshwater runoffs from two adjacent rivers. 7. The sediment is slightly modified by the culture of bivalves. Total organic carbon, total nitrogen, Eh values and pheopigments were significantly higher under the trestles than in any other stations. Other stations often did not differ from the reference station. 8. The effects of shellfish culture on the water column were. However, it was observed a small decrease of the food available to the molluscs near the rearing 9. The DEB model was able to describe and predict adequately the growth of oysters, both in the Baie des Veys and in the Loch Creran. The parametres for its use in other environment are given, but a tuning of one parametre should be performed with the help of authors. 10. Among the indicators and models for use in are as of intertidal bivalve culture, it is recommended to use the sediment quality index, TOC (Total Organic Carbon), redox and pheopigments, in surficial sediment, AMBI for the macrofauna, chlorophyll a contents and nitrogen forms in the water column, and models describing the carrying capacity, filtration rate of molluscs, and a DEB model to predict the growth of molluscs.

First record of Pagellus bellottii (Teleostei: Sparidae) in the Bay of Biscay, France

The red pandora, Pagellus bellottii Steindachner, 1882, is a tropical and subtropical demersal Sparidae (Porgies) that lives over hard or sandy bottoms in coastal marine waters. It mostly occurs at depths ranging from 10 to 50 metres. It is distributed in the eastern Atlantic, from the Strait of Gibraltar to Angola and the Canary Islands where it is occasionally recorded (Bauchot and Hureau, 1986; Franqueville, 1983). The species is also recorded in the southwestern Mediterranean, in the Alboran Sea, off the Algerian coasts and in the Gulf of Gabes (Oral, 2010). The records of the species in the eastern Mediterranean, Syrian and Israeli waters (Fricke, et al. 2014, Fig. 1) is questioned. We consider these records are misidentification of Pagrus pagrus (Linnaeus, 1758). Pagellus bellottii was also included in the checklist of the fishes from Portugal as a consequence of records coming from the Algarve region, about 36°59′ N, 8° W, the northernmost records in Atlantic waters (de Castro, 1967; Erzini et al., 1996; Carneiro et al., 2014; Carneiro com. pers.). Some specimens were also recorded in Spanish Mediterranean waters, in the Bay of Almería about 36°47′ N, 2°25′ W (Lucena, et al. 1982), the northernmost records for the Mediterranean waters. Herein, the first record of P. bellottii in the Bay of Biscay is reported.

Impacts of high-nitrate freshwater inputs on macrotidal ecosystems. I. Seasonal evolution of nutrient limitation for the diatom-dominated phytoplankton of the Bay of Brest (France)

The chemical factors (inorganic nitrogen, phosphate, silicic acid) that potentially or actually control primary production were determined for the Bay of Brest, France, a macrotidal ecosystem submitted to high-nitrate-loaded freshwater inputs (winter nitrate freshwater concentrations >700 mu M, Si:N molar ratio as low as 0.2, i.e. among the lowest ever published). Intensive data collection and observations were carried out from February 1993 to March 1994 to determine the variations of physical [salinity, temperature, photosynthetically active radiation (PAR), freshwater discharges] and chemical (oxygen and nutrients) parameters and their impacts on the phytoplankton cycle (fluorescence, pigments, primary production). With insufficient PAR the winter stocks of nutrients were almost nonutilized and the nitrate excess was exported to the adjacent ocean, due to rapid tidal exchange. By early April, a diatom-dominated spring bloom developed (chlorophyll a maximum = 7.7 mu g l(-1); primary production maximum = 2.34 g C m(-2) d(-1)) under high initial nutrient concentrations. Silicic acid was rapidly exhausted over the whole water column; it is inferred to be the primary limiting factor responsible for the collapse of the spring bloom by mid-May. Successive phytoplankton developments characterized the period of secondary blooms during summer and fall (successive surface chlorophyll a maxima = 3.5, 1.6, 1.8 and 1.0 mu g l(-1); primary production = 1.24, 1.18 and 0.35 g C m(-2) d(-1)). Those secondary blooms developed under lower nutrient concentrations, mostly originating from nutrient recycling. Until August, Si and P most likely limited primary production, whereas the last stage of the productive period in September seemed to be N limited instead, this being a period of total nitrate depletion in almost the whole water column. Si limitation of spring blooms has become a common feature in coastal ecosystems that receive freshwater inputs with Si:N molar ratios <1. The peculiarity of Si Limitation in the Bay of Brest is its extension through the summer period.