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.

Global change and climate-driven invasion of the Pacific oyster (Crassostrea gigas) along European coasts: a bioenergetics modelling approach

Aim The spread of non-indigenous species in marine ecosystems world-wide is one of today's most serious environmental concerns. Using mechanistic modelling, we investigated how global change relates to the invasion of European coasts by a non-native marine invertebrate, the Pacific oyster Crassostrea gigas. Location Bourgneuf Bay on the French Atlantic coast was considered as the northern boundary of C. gigas expansion at the time of its introduction to Europe in the 1970s. From this latitudinal reference, variations in the spatial distribution of the C. gigas reproductive niche were analysed along the north-western European coast from Gibraltar to Norway. Methods The effects of environmental variations on C. gigas physiology and phenology were studied using a bioenergetics model based on Dynamic Energy Budget theory. The model was forced with environmental time series including in situ phytoplankton data, and satellite data of sea surface temperature and suspended particulate matter concentration. Results Simulation outputs were successfully validated against in situ oyster growth data. In Bourgneuf Bay, the rise in seawater temperature and phytoplankton concentration has increased C. gigas reproductive effort and led to precocious spawning periods since the 1960s. At the European scale, seawater temperature increase caused a drastic northward shift (1400 km within 30 years) in the C. gigas reproductive niche and optimal thermal conditions for early life stage development. Main conclusions We demonstrated that the poleward expansion of the invasive species C. gigas is related to global warming and increase in phytoplankton abundance. The combination of mechanistic bioenergetics modelling with in situ and satellite environmental data is a valuable framework for ecosystem studies. It offers a generic approach to analyse historical geographical shifts and to predict the biogeographical changes expected to occur in a climate-changing world.

High alkaline phosphatase activity in phosphate replete waters: The case of two macrotidal estuaries

The occurrence of alkaline phosphatase activity (APA) that hydrolyses organic phosphorus into phosphate (PO4) is commonly related to PO4 deficiency of oceanic, coastal and fresh waters. APA is almost never investigated in PO4-rich estuaries, since very low activities are expected to occur. As a consequence, microbial mineralization of organic phosphorus into PO4 has often been ignored in estuaries. In this study, we examined the importance of potential APA and the associated microbial dynamics in two estuaries, the Aulne and the Elorn (Northwestern France), presenting two different levels of PO4 concentrations. Unexpected high potential APA was observed in both estuaries. Values ranged from 50 to 506 nmol L−1 h−1, which range is usually found in very phosphorus-limited environments. High potential APA values were observed in the oligohaline zone (salinity 5–15) in spring and summer, corresponding to a PO4 peak and a maximum bacterial production of particle-attached bacteria. In all cases, high potential APA was associated with high suspended particulate matter and total particulate phosphorus. The low contribution of the 0.2–1 μm fraction to total APA, the strong correlation between particulate APA and bacterial biomass, and the close relationship between the production of particle-attached bacteria and APA, suggested that high potential APA is mainly due to particle-attached bacteria. These results suggest that the microbial mineralization of organic phosphorus may contribute to an estuarine PO4 production in spring and summer besides physicochemical processes.

Temporal variation of delta C-13 in particulate organic matter and oyster Crassostrea gigas in Marennes-Oleron Bay (France): Effect of freshwater inflow

The temporal variability of delta(13)C in suspended particulate organic matter (POM) and oyster Crassostrea gigas along a salinity gradient was investigated from May 1992 to September 1993 within the estuarine bay of Marennes-Oleron (France). During this period the mean daily discharge of the Charente River exhibited large seasonal variation, with a high discharge from November 1992 to January 1993. Contrary to that at the river mouth and the marine littoral, delta(13)C in POM and in oysters at mid-estuary was affected by the high flood period. The delta(13)C values of POM decreased in mid-estuary and remained at low levels during the high discharge period, indicating an increasing contribution of terrestrial inputs to the estuarine POM pool. At the same site, a remarkable decrease of delta(13)C in oysters occurred between December 1992 and March 1993 (after a time lag compared to the ambient POM), indicating incorporation of terrestrial organic matter in oyster tissues during the high flood discharge. The lag between the delta(13)C decrease in POM and oysters is attributed to the time needed for oyster tissues to incorporate enough newly terrestrial light carbon to be recognized by the delta(13)C measure (about 1 to 2 mo). This time interval depends on tissue turnover time. The delta(13)C POM decrease (i.e. 1.3 parts per thousand) cannot explain entirely the decrease observed in oysters (i.e. 2.3 parts per thousand). In fact, the pattern exhibited by mid-estuarine oysters can be explained by the increasing contribution of terrestrial organic matter to their feeding, and the inability to preferentially utilize specific components of the estuarine POM that are C-13-enriched.

Isotope and fatty acid trends along continental shelf depth gradients: Inshore versus offshore hydrological influences on benthic trophic functioning

Anthropogenic activities and land-based inputs into the sea may influence the trophic structure and functioning of coastal and continental shelf ecosystems, despite the numerous opportunities and services the latter offer to humans and wildlife. In addition, hydrological structures and physical dynamics potentially influence the sources of organic matter (e.g., terrestrial versus marine, or fresh material versus detrital material) entering marine food webs. Understanding the significance of the processes that influence marine food webs and ecosystems (e.g., terrestrial inputs, physical dynamics) is crucially important because trophic dynamics are a vital part of ecosystem integrity. This can be achieved by identifying organic matter sources that enter food webs along inshore–offshore transects. We hypothesised that regional hydrological structures over wide continental shelves directly control the benthic trophic functioning across the shelf. We investigated this issue along two transects in the northern ecosystem of the Bay of Biscay (north-eastern Atlantic). Carbon and nitrogen stable isotope analysis (SIA) and fatty acid analysis (FAA) were conducted on different complementary ecosystem compartments that include suspended particulate organic matter (POM), sedimentary organic matter (SOM), and benthic consumers such as bivalves, large crustaceans and demersal fish. Samples were collected from inshore shallow waters (at ∼1 m in depth) to more than 200 m in depth on the offshore shelf break. Results indicated strong discrepancies in stable isotope (SI) and fatty acid (FA) compositions in the sampled compartments between inshore and offshore areas, although nitrogen SI (δ15N) and FA trends were similar along both transects. Offshore the influence of a permanently stratified area (described previously as a “cold pool”) was evident in both transects. The influence of this hydrological structure on benthic trophic functioning (i.e., on the food sources available for consumers) was especially apparent across the northern transect, due to unusual carbon isotope compositions (δ13C) in the compartments. At stations under the cold pool, SI and FA organism compositions indicated benthic trophic functioning based on a microbial food web, including a significant contribution of heterotrophic planktonic organisms and/or of SOM, notably in stations under the cold pool. On the contrary, inshore and shelf break areas were characterised by a microalgae-based food web (at least in part for the shelf break area, due to slope current and upwelling that can favour fresh primary production sinking on site). SIA and FAA were relevant and complementary tools, and consumers better medium- to long-term system integrators than POM samples, for depicting the trophic functioning and dynamics along inshore–offshore transects over continental shelves.

Stable isotope ratios in bentho-demersal biota along a depth gradient in the bay of biscay: A multitrophic study

Although stable isotope ratios are increasingly used to investigate the trophic ecology of marine organisms, their spatial variations are still poorly understood in the coastal environment. In this study, we measured the stable isotope composition (δ13C, δ15N) of suspended particulate organic matter (SPOM) (primary producer), a suspension feeder, the great scallop Pecten maximus (primary consumer), megabenthic decapods and benthic fishes (secondary consumers) along a depth gradient (from 5m to 155m depth) across the continental shelf of the Bay of Biscay. Although the three trophic levels exhibited similar δ13C patterns along the gradient, the δ15N patterns varied between SPOM, scallops and carnivores. The δ15N difference between SPOM and scallops decreased with increasing depth, suggesting that non trophic factors may affect the stable isotope composition of scallops at deepest sampling stations. An opposed trend was found between scallops and carnivores, suggesting that the trophic level of these carnivores increased at higher depth, possibly as an adaptation to lower prey abundances. Although our results suggest that primary consumers are suitable to establish isotopic baselines in coastal environments, we stress the need for further studies aiming at characterizing the variability of stable isotopes in coastal biota, and the respective effects of baseline, trophic and metabolic factors in their isotopic composition.