Perfluoroalkyl substances (PFAS) occurrence, concentrations and spatial distribution along the French Mediterranean coast and lagoons, based on active biomonitoring.

Tracking PFAS in ecosystems is challenging. In this context, monitoring programs are crucial to fill data gaps, especially in marine environments, which are the ultimate outlets for these forever chemicals. The 2021 chemical contamination monitoring campaign along the French Mediterranean coast established a baseline for PFAS concentrations in mussels, with 90 % of measurements below quantification limits. When detected, long-chain PFCA's were predominant. Spatial distribution patterns suggested continuous PFAS inputs and complex dynamics, shaped by the influence of large watersheds and rivers (Rhône, Aude, Huveaune). Lapeyrade shallow lagoon stood out as the most contaminated site. Similar PFAS profiles in connected sites implied shared sources but raised questions about accumulation processes in mussels. While certain sites had evident sources (e.g., military airbase for Palo lagoon), others remained uncertain (e.g., Toulon bay). Coastal stations (Banyuls, Cap Agde, Brégançon, Pampelonne) showed PFAS contamination without clear onshore sources, possibly due to insufficient transportation process understanding.

The use of copper as plant protection product contributes to environmental contamination and resulting impacts on terrestrial and aquatic biodiversity and ecosystem functions.

Copper-based plant protection products (PPPs) are widely used in both conventional and organic farming, and to a lesser extent for non-agricultural maintenance of gardens, greenspaces, and infrastructures. The use of copper PPPs adds to environmental contamination by this trace element. This paper aims to review the contribution of these PPPs to the contamination of soils and waters by copper in the context of France (which can be extrapolated to most of the European countries), and the resulting impacts on terrestrial and aquatic biodiversity, as well as on ecosystem functions. It was produced in the framework of a collective scientific assessment on the impacts of PPPs on biodiversity and ecosystem services in France. Current science shows that copper, which persists in soils, can partially transfer to adjacent aquatic environments (surface water and sediment) and ultimately to the marine environment. This widespread contamination impacts biodiversity and ecosystem functions, chiefly through its effects on phototrophic and heterotrophic microbial communities, and terrestrial and aquatic invertebrates. Its effects on other biological groups and biotic interactions remain relatively under-documented.

Impacts of neonicotinoids on biodiversity: a critical review.

Neonicotinoids are the most widely used class of insecticides in the world, but they have raised numerous concerns regarding their effects on biodiversity. Thus, the objective of this work was to do a critical review of the contamination of the environment (soil, water, air, biota) by neonicotinoids (acetamiprid, clothianidin, imidacloprid, thiacloprid, thiamethoxam) and of their impacts on terrestrial and aquatic biodiversity. Neonicotinoids are very frequently detected in soils and in freshwater, and they are also found in the air. They have only been recently monitored in coastal and marine environments, but some studies already reported the presence of imidacloprid and thiamethoxam in transitional or semi-enclosed ecosystems (lagoons, bays, and estuaries). The contamination of the environment leads to the exposure and to the contamination of non-target organisms and to negative effects on biodiversity. Direct impacts of neonicotinoids are mainly reported on terrestrial invertebrates (e.g., pollinators, natural enemies, earthworms) and vertebrates (e.g., birds) and on aquatic invertebrates (e.g., arthropods). Impacts on aquatic vertebrate populations and communities, as well as on microorganisms, are less documented. In addition to their toxicity to directly exposed organisms, neonicotinoid induce indirect effects via trophic cascades as demonstrated in several species (terrestrial and aquatic invertebrates). However, more data are needed to reach firmer conclusions and to get a clearer picture of such indirect effects. Finally, we identified specific knowledge gaps that need to be filled to better understand the effects of neonicotinoids on terrestrial, freshwater, and marine organisms, as well as on ecosystem services associated with these biotas.

An integrative perspective on fish health: Environmental and anthropogenic pathways affecting fish stress.

Multifactorial studies assessing the cumulative effects of natural and anthropogenic stressors on individual stress response are crucial to understand how organisms and populations cope with environmental change. We tested direct and indirect causal pathways through which environmental stressors affect the stress response of wild gilthead seabream in Mediterranean costal lagoons using an integrative PLS-PM approach. We integrated information on 10 environmental variables and 36 physiological variables into seven latent variables reflecting lagoons features and fish health. These variables concerned fish lipid reserves, somatic structure, inorganic contaminant loads, and individual trophic and stress response levels. This modelling approach allowed explaining 30 % of the variance within these 46 variables considered. More importantly, 54 % of fish stress response was explained by the dependent lagoon features, fish age, fish diet, fish reserve, fish structure and fish contaminant load latent variables included in our model. This integrative study sheds light on how individuals deal with contrasting environments and multiple ecological pressures.

Linking ecotoxicological effects on biodiversity and ecosystem functions to impairment of ecosystem services is a challenge: an illustration with the case of plant protection products.

There is growing interest in using the ecosystem services framework for environmental risk assessments of chemicals, including plant protection products (PPPs). Although this topic is increasingly discussed in the recent scientific literature, there is still a substantial gap between most ecotoxicological studies and a solid evaluation of potential ecotoxicological consequences on ecosystem services. This was recently highlighted by a collective scientific assessment (CSA) performed by 46 scientific experts who analyzed the international science on the impacts of PPPs on biodiversity, ecosystem functions, and ecosystem services. Here, we first point out the main obstacles to better linking knowledge on the ecotoxicological effects of PPPs on biodiversity and ecological processes with ecosystem functions and services. Then, we go on to propose and discuss possible pathways for related improvements. We describe the main processes governing the relationships between biodiversity, ecological processes, and ecosystem functions in response to effects of PPP, and we define categories of ecosystem functions that could be directly linked with the ecological processes used as functional endpoints in investigations on the ecotoxicology of PPPs. We then explore perceptions on the possible links between these categories of ecosystem functions and ecosystem services among a sub-panel of the scientific experts from various fields of environmental science. We find that these direct and indirect linkages still need clarification. This paper, which reflects the difficulties faced by the multidisciplinary group of researchers involved in the CSA, suggests that the current gap between most ecotoxicological studies and a solid potential evaluation of ecotoxicological consequences on ecosystem services could be partially addressed if concepts and definitions related to ecological processes, ecosystem functions, and ecosystem services were more widely accepted and shared within the ecotoxicology community. Narrowing this gap would help harmonize and extend the science that informs decision-making and policy-making, and ultimately help to better address the trade-off between social benefits and environmental losses caused by the use of PPPs.

Main conclusions and perspectives from the collective scientific assessment of the effects of plant protection products on biodiversity and ecosystem services along the land-sea continuum in France and French overseas territories.

Preservation of biodiversity and ecosystem services is critical for sustainable development and human well-being. However, an unprecedented erosion of biodiversity is observed and the use of plant protection products (PPP) has been identified as one of its main causes. In this context, at the request of the French Ministries responsible for the Environment, for Agriculture and for Research, a panel of 46 scientific experts ran a nearly 2-year-long (2020-2022) collective scientific assessment (CSA) of international scientific knowledge relating to the impacts of PPP on biodiversity and ecosystem services. The scope of this CSA covered the terrestrial, atmospheric, freshwater, and marine environments (with the exception of groundwater) in their continuity from the site of PPP application to the ocean, in France and French overseas territories, based on international knowledge produced on or transposable to this type of context (climate, PPP used, biodiversity present, etc.). Here, we provide a brief summary of the CSA's main conclusions, which were drawn from about 4500 international publications. Our analysis finds that PPP contaminate all environmental matrices, including biota, and cause direct and indirect ecotoxicological effects that unequivocally contribute to the decline of certain biological groups and alter certain ecosystem functions and services. Levers for action to limit PPP-driven pollution and effects on environmental compartments include local measures from plot to landscape scales and regulatory improvements. However, there are still significant gaps in knowledge regarding environmental contamination by PPPs and its effect on biodiversity and ecosystem functions and services. Perspectives and research needs are proposed to address these gaps.

Evaluating pesticide mixture risks in French Mediterranean coastal lagoons waters.

To assess the risk of pesticide mixtures in lagoon waters, this study adopted a multi-step approach using integrative passive samplers (POCIS) and concentration addition (CA) toxicological models. Two French Mediterranean lagoons (Thau and Or) were monitored for a range of 68 pesticides continuously over a period of a year (2015-16). The findings revealed mixtures of dissolved pesticides with varying composition and levels over the year. The Or site contained more pesticides than Thau site (37 vs 28 different substances), at higher concentrations (0.1-58.6 ng.L-1 at Or vs <0.1-9.9 at Thau) and with overall higher detection frequencies. All samples showed a potential chronic toxicity risk, depending on the composition and concentrations of co-occurring pesticides. In 74 % of the samples, this pesticide risk was driven by a few single substances (ametryn, atrazine, azoxystrobin, carbendazim, chlorotoluron, irgarol, diuron and metolachlor) and certain transformation products (e.g. DPMU and metolachlor OA/ESA). Individually, these were a threat for the three taxa studied (phytoplankton, crustaceans and fish). Yet even a drastic reduction of these drivers alone (up to 5 % of their current concentration) would not eliminate the toxicity risks in 56 % of the Or Lagoon samples, due to pesticide mixtures. The two CA-based approaches used to assess the combined effect of these mixtures, determined chronic potential negative impacts for both lagoons, while no acute risk was highlighted. This risk was seasonal, indicating the importance of monitoring in key periods (summer, winter and spring) to get a more realistic picture of the pesticide threat in lagoon waters. These findings suggest that it is crucial to review the current EU Water Framework Directive's risk-assessment method, as it may incorrectly determine pesticide risk in lagoons.

In vivo exposure of marine mussels to venlafaxine: bioconcentration and metabolization.

Pharmaceuticals are present in natural waters, thus contributing to the general exposure of aquatic organisms, but few data are available on the accumulation of these substances in marine organisms. The present study evaluated the in vivo bioconcentration of an antidepressant-venlafaxine (VLF)-in marine mussels (Mytilus galloprovincialis) during 7 days of exposure at nominal 10 µg/L concentration, followed by a 7-day depuration period. The bioconcentration factor (BCF) was 265 mL/g dry weight (dw). VLF accumulation reached an average tissue concentration of 2146 ± 156 ng/g dw within 7 days, showing a first-order kinetics process. N-desmethylvenlafaxine (N-VLF) and O-desmethylvenlafaxine (O-VLF) metabolites were quantified in mussel tissues, whereas N,N-didesmethylvenlafaxine (NN-VLF) was only recorded as being detected. These three metabolites were also quantified in water, indicating an active metabolism and VLF excretion in Mediterranean mussels. Complementary experiments conducted at nominal concentrations of 1, 10, and 100 µg/L for 7 days confirmed the VLF bioconcentration and metabolism and allowed us to quantify a supplementary metabolite, i.e., N,O-didesmethylvenlafaxine (NO-VLF), in mussel tissues. These results encourage further research on a more complete characterization of metabolism and on any disturbances linked to bioconcentration of VLF on bivalves.

Groundwater discharge to coastal streams - A significant pathway for nitrogen inputs to a hypertrophic Mediterranean coastal lagoon.

Near-shore and direct groundwater inputs are frequently omitted from nutrient budgets of coastal lagoons. This study investigated groundwater-driven dissolved inorganic nitrogen (DIN) inputs from an alluvial aquifer to the hypertrophic Or lagoon, with a focus on the Salaison River. Piezometric contours revealed that the Salaison hydrogeological catchment is 42% bigger than the surface watershed and hydraulic gradients suggest significant groundwater discharge all along the stream. Hydrograph separation of the water flow at a gauging station located 3 km upstream from the Or lagoon combined with DIN historical data enabled to estimate that groundwater-driven DIN inputs account for 81-87% of the annual total DIN inputs to the stream upstream from the gauging station. A radon mass balance was performed for the hydrological cycle 2017-2018 to estimate groundwater inflow into the downstream part of the stream. Results showed that (1) DIN fluxes increased by a factor 1.1 to 2.3 between the gauging station and the Salaison outlet, (2) the increase in DIN was due to two groundwater-fed canals and to groundwater discharge along the stream, the latter represented 63-78% of the water flow. This study thus highlights the significance of groundwater driven DIN inputs into the Salaison River, which account for 90% of the annual DIN inputs. This is particularly true in the downstream part of the river, which, on averages, supplies 48% of total DIN inputs to the river. These downstream DIN inputs into the Or lagoon were previously not taken into account in the management of this and other Mediterranean lagoons. The inputs will probably affect restoration processes for many years due to their residence time in the aquifer. This study throws light on a rarely documented source of 'very-nearshore' groundwater discharge to coastal streams in water and nutrient budgets of coastal zone ecosystems.

Reducing PEC uncertainty in coastal zones: a case study on carbamazepine, oxcarbazepine and their metabolites.

Concentrations of the antiepileptic drugs carbamazepine (Cbz), oxcarbazepine (OxCz) and their main metabolites were predicted in a wastewater treatment plant (WTP) and in the vicinity of its submarine outfall located in a Mediterranean coastal zone. Refined predicted environmental concentrations (PECs) were calculated in effluents based on consumption data and human excretion rates. PECs were estimated in the sea using the hydrodynamic MARS 3D model integrating meteorological data, oceanic conditions (wind, tide, atmospheric pressure), freshwater and sewage inputs. Measured environmental concentrations (MECs) were compared to PECs to assess the estimation relevance. In the coastal zone, PEC and MEC were in the same magnitude range. Modeling of Cbz diffusion and advection just above the submarine outfall showed the influence of the thermocline during summer, with low diffusion of Cbz from the bottom to the surface. This work allowed understanding the dispersion of target compounds and deserved further development for a better acknowledgement of vulnerability at local scales.

Organic UV filter concentrations in marine mussels from French coastal regions.

The accumulation of EHMC, OCT and OD-PABA, three common UV filter compounds, was investigated in marine mussels. Wild Mytilus edulis and Mytilus galloprovincialis were sampled in ten sites along the French Atlantic and Mediterranean coasts from June to November. In mussel tissues, 100% of the samples had quantifiable EHMC concentrations ranging from 3 to 256ngg(-1) dry weight, while 55% of the samples had detectable OCT concentrations ranging from under 2 to 7 112ngg(-1) dry weight. These concentrations significantly increased with the rising air temperature in summer, the recreational pressure and the geomorphological structure of the sampling sites (its lack of openness to the wide). This is the first study to report bioaccumulation of UV filters in marine mussels, thus highlighting the need for further monitoring and assessment.

In vitro biomonitoring of contamination by estrogenic compounds in coastal environments: comments on the use of M. galloprovincialis.

The use of mussel extracts in in vitro bioassays which express the estrogen receptor could provide valuable information on the bioavailability of endocrine disruptors in coastal environments. The aim of this study was to assess the temporal variability of the estrogenic responses in bioassays in Mytilus galloprovincialis. A 6-month in situ experiment was conducted in order to follow the estrogenic activity on MELN cell line during the reproduction stages of mussels. Estradiol equivalents (EEQ) determined in mussels using the MELN cell lines ranged from 0.79 to 3.72 ng/g dry weight (d.w.) in males, from 0.42 to 2.33 ng/g d.w. in females and from 3.41 to 4.2 d.w. in undifferentiated bivalves. We observed an increase in EEQ values during the spawning stage for males, not for female. The maximal EEQ values were observed at the indifferent stage. We discuss these results in regards to the actual knowledge on mussels' reproductive cycle and to the possible impact of xeno-estrogens. Variations of E2 levels in mussels must be taken into account for further studies on xeno-estrogens monitoring using hER reporter cell-lines bioassays.

Bioconcentration of two pharmaceuticals (benzodiazepines) and two personal care products (UV filters) in marine mussels (Mytilus galloprovincialis) under controlled laboratory conditions.

Bioaccumulation is essential for gaining insight into the impact of exposure to organic micropollutants in aquatic fauna. Data are currently available on the bioaccumulation of persistent organic pollutants, but there is very little documentation on the bioaccumulation of pharmaceuticals and personal care products (PPCPs). The bioconcentration of selected PPCPs was studied in marine mussels (Mytilus galloprovincialis). The selected PPCPs were two organic UV filters, i.e., 2-ethylhexyl-4-trimethoxycinnamate (EHMC) and octocrylene (OC), and two benzodiazepines (BZP), i.e., diazepam (DZP) and tetrazepam (TZP). Laboratory experiments were performed in which M. galloprovincialis was exposed to these compounds either directly from water, for the less lipophilic substances (BZP) or via spiked food for lipophilic UV filters. M. galloprovincialis uptook and eliminated BZP following first-order kinetics. The biological half-life (t (1/2)) of TZP was 1.4 days, resulting in a bioconcentration factor of 64 and 99 mL g(-1) dry weight (dw), respectively, for 2.3 and 14.5 µg L(-1) of exposure, while the biological half-life (t (1/2)) of DZP was 0.4 days, resulting in a bioconcentration factor of 51 mL g(-1) dw for 13.2 µg L(-1) of exposure. The uptake of UV filter was rapid in mussels, followed by elimination within 24 h. EHMC increased from 15 to 138 ng g(-1) dw in 1 h and decreased to 25 ng g(-1) after 24 h for 11.9 µg L(-1) exposure. OC reached 839 ng g(-1) dw after 1 h and decreased to 33 ng g(-1) after 24 h for 11.6 µg L(-1) exposure. However, EHMC and OC were slightly accumulated in 48 h, i.e., 38 and 60 ng g(-1) dw, respectively.

Temporal study of estrogenic responses of mussel (Mytilus galloprovinciallis) extracts applied to reporter cell lines.

In vitro bioassays would facilitate monitoring of estrogen-like compounds in mussels (Mytilus galloprovincialis) since they tend to accumulate lipophilic compounds in their fat and muscle tissue. However, estradiol (E2) steroid (already identified in mussels) could induce false positive responses. This study focuses on temporal variability in estrogenic responses of mussel extracts and the possible relation of this response with E2 levels. The reproductive cycle and growth were thus monitored for six months in sexed mussels. E2 levels were similar between genders and these levels varied with reproductive stages. human estrogen receptor (hER) activities were similar at all stages except in February. E2 present in male and female extracts accounted for part of the hER activation observed, but no correlation was found between E2 levels and hER activities.