Acidic herbicides are increasingly monitored in freshwater, since their high solubility favors their rapid transfer to the water phase. Therefore, contaminant levels in the water can vary rapidly and passive sampling would be preferred over spot sampling to integrate all pollution events over a given exposure time. In this work, we propose to compare the conventional pharmaceutical polar organic chemical integrative sampler (POCIS) with modified POCISs containing two different receiving phases: a standard polystyrene divinylbenzene polymer with a higher specific surface area (Chromabond HR-X) and a mixed-mode anion exchange sorbent providing additional strong anion exchange interaction sites (Oasis MAX). Due to its hydrophobic character, Chromabond HR-X had little interaction with water (no sampling of acidic herbicides); whereas Oasis MAX provided acceptable sampling parameters (longer kinetic regime together with higher sampling rates). Additional experiments with POCIS-MAX showed no influence of nitrates on analyte uptakes, and linear isotherms reaching 10 μg L⁻¹, supporting the applicability of this device for the sampling of organic acids in continental water. The performance and reference compound (PRC) approach would be then applicable for POCIS-MAX if no competition is observed with other anions, especially organic acids (e.g., humic acids).
European flounder Platichthys flesus life history patterns were investigated in 3 basins along a latitudinal gradient (Minho, N Portugal; Gironde, SW France; Seine, N France). We used coupled Sr:Ca and Ba:Ca otolith signatures and microstructure to retrospectively determine habitats occupied by flounder during their life, including early larval ontogeny. Flounder exhibited high life history plasticity among and even within basins, apparent by the diversity of habitats used during larval ontogeny and throughout their lives, and by the age at which flounder migrated to freshwater. Egg signatures probably had a strong maternal influence, and our interpretation suggests that flounder spawned and/or hatched predominantly in brackish waters in the Minho, while in the Gironde and Seine, flounder spawned and/or hatched either in coastal, brackish or freshwater environments. The freshwater egg signature was most frequent in the Seine. These interpretations contradict the current general assumption that flounder spawn exclusively in coastal waters. During pre-metamorphosis and metamorphosis, flounder were predominantly in brackish waters in the Minho, while in the Gironde and Seine, they were mainly in coastal and freshwater environments, respectively. The diversity of flounder life histories (LH) (i.e. sequence of habitat residence: freshwater, brackish or coastal) after metamorphosis was similar between the Minho (LH = 13), Gironde (LH = 13) and Seine (LH = 14) basins. The age at which flounder migrated to freshwater also varied among sites, at an earlier age in the Minho and Gironde (< 0.5 yr old) than in the Seine, where flounder migrating from the coast into freshwater reached maximum frequencies at age 1.3 yr old. Thus, catadromy in European flounder may be facultative, and the factors influencing flounder high LH plasticity deserve thorough research.
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Freshwater biofilms have been increasingly used during the last decade in ecotoxicology due to their ecological relevance to assess the effect(s) of environmental stress at the community level. Despite growing knowledge about the effect of various stressors on the structure and the function of these microbial communities, a strong research effort is still required to better understand their response to chemical stress and the influence of environmental stressors in this response. To tackle this challenge, untargeted metabolomics is an approach of choice because of its capacity to give an integrative picture of the exposure to multiple stress and associated effect as well as identifying the molecular pathways involved in these responses. In this context, the present study aimed to explore the use of an untargeted metabolomics approach to unravel at the molecular/ biochemical level the response of the whole biofilm to chemical stress and the influence of various environmental factors in this response. To this end, archived high-resolution mass spectrometry data from previous experiments at our laboratory on the effect of the model photosynthesis inhibitor diuron on freshwater biofilm were investigated by using innovative solutions for OMICs data (e.g., DRomics) and more usual chemometric approaches (multivariate and univariate statistical analyses). The results showed a faster (1 min) and more sensitive response of the metabolome to diuron than usual functional descriptors, including photosynthesis. Also, the metabolomics response to diuron resulted from metabolites following various trends (increasing, decreasing, U/bell shape) along increasing concentration and time. This metabolomics response was influenced by the temperature, photoperiod, and flow. A focus on a plant-specific omega-3 (eicosapentaenoic acid) playing a key role in the trophic chain highlighted the potential relevance of metabolomics approach to establish the link between molecular alteration and ecosystem structure/functioning impairment but also how complex is the response and the influence of all the tested factors on this response at the metabolomics level. Altogether, our results underline that more fundamental researches are needed to decipher the metabolomics response of freshwater biofilm to chemical stress and its link with physiological, structural, and functional responses toward the unraveling of adverse outcome pathways (AOP) for key ecosystem functions (e.g., primary production).
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