Identifying the Stoichiometry of Metal/Ligand Complex by Coupling Spectroscopy and Modelling: a Comprehensive Study on Two Fluorescent Molecules Specific to Lead.

Two new chemosensors for lead (II) were synthesized based on 5-((anthracen-9-ylmethylene) amino)quinolin-10-ol (ANQ). ANQ was modified in the para position of the imine group via a methoxy link either with methylmethacrylate (ANQ-MMA) or styrene (ANQ-ST). Complexation of those molecules with Pb2+ was studied at room temperature using UV-Visible absorption and fluorescence spectroscopies. Thanks to the UV-visible absorption spectroscopy, it appeared that ANQ-MMA formed 1:1 and 1:2 complexes with lead (II) and ANQ-ST only 1:1 complex. For both molecules, the fluorescence excitation-emission matrices (EEM) signal intensity increased from 0 to 100 µmol.L-1 of lead (II) followed by a saturation for higher concentrations. The decomposition of the obtained EEMs gave a set of empiric fluorescent components that have been directly linked to the distribution of lead complexes obtained with the UV-visible absorption spectroscopy study. This correlation allowed to evidence metal/ligand complex stoichiometry and emerge as a new method to identify empiric components. Moreover, the two ligands showed a promising selectivity for Pb2+, turning them interesting probes for this hazardous metal.

Evidencing the Impact of Coastal Contaminated Sediments on Mussels Through Pb Stable Isotopes Composition.

Heavily contaminated sediments are a serious concern for ecosystem quality, especially in coastal areas, where vulnerability is high due to intense anthropogenic pressure. Surface sediments (54 stations), 50 cm interface cores (five specific stations), river particles, coal and bulk Pb plate from past French Navy activities, seawater and mussels were collected in Toulon Bay (NW Mediterranean Sea). Lead content and Pb stable isotope composition have evidenced the direct impact of sediment pollution stock on both the water column quality and the living organisms, through the specific Pb isotopic signature in these considered compartments. The history of pollution events including past and present contaminant dispersion in Toulon Bay were also demonstrated by historical records of Pb content and Pb isotope ratios in sediment profiles. The sediment resuspension events, as simulated by batch experiments, could be a major factor contributing to the high Pb mobility in the considered ecosystem. A survey of Pb concentrations in surface seawater at 40 stations has revealed poor seawater quality, affecting both the dissolved fraction and suspended particles and points to marina/harbors as additional diffuse sources of dissolved Pb.

Assessing the Plastisphere from Floating Plastics in the Northwestern Mediterranean Sea, with Emphasis on Viruses.

Plastics in the ocean create the "plastisphere", a diverse habitat hosting various life forms. Other than the pollution induced by plastics, the co-occurrence of primary producers, symbiotic organisms, decomposers, and pathogens within the plastisphere raises questions about how they influence the dynamics of marine ecosystems. Here, we used a shotgun DNA-sequencing approach to describe the species thriving on floating plastics collected in two Mediterranean sites. Our findings revealed many species of bacteria, eukaryotes, viruses, and archaea on each plastic. Proteobacteria was dominant (70% of reads in the entire dataset), with other groups such as Ascomycota fungi (11%) and Bacteroidetes (9%) also being represented. The community structure was not affected by the polymeric composition or the plastic shape. Notably, pathogenic Vibrio species, including V. campbelli, V. alginolyticus, and V. coralliilyticus, were among the most abundant species. Viruses, despite showing lower relative abundances, occurred in all samples, especially Herpesvirales, Caudovirales, and Poxviridae groups. A significant finding was the presence of the White Spot Syndrome virus (WSSV). This pathogen, responsible for devastating outbreaks in aquaculture systems, had not been previously reported in the marine plastisphere. Our study emphasizes the need for further investigation into the ecological and economic impacts of plastisphere organisms in the ocean.

Microplastics in the insular marine environment of the Southwest Indian Ocean carry a microbiome including antimicrobial resistant (AMR) bacteria: A case study from Reunion Island.

The increasing threats to ecosystems and humans from marine plastic pollution require a comprehensive assessment. We present a plastisphere case study from Reunion Island, a remote oceanic island located in the Southwest Indian Ocean, polluted by plastics. We characterized the plastic pollution on the island's coastal waters, described the associated microbiome, explored viable bacterial flora and the presence of antimicrobial resistant (AMR) bacteria. Reunion Island faces plastic pollution with up to 10,000 items/km2 in coastal water. These plastics host microbiomes dominated by Proteobacteria (80 %), including dominant genera such as Psychrobacter, Photobacterium, Pseudoalteromonas and Vibrio. Culturable microbiomes reach 107 CFU/g of microplastics, with dominance of Exiguobacterium and Pseudomonas. Plastics also carry AMR bacteria including ß-lactam resistance. Thus, Southwest Indian Ocean islands are facing serious plastic pollution. This pollution requires vigilant monitoring as it harbors a plastisphere including AMR, that threatens pristine ecosystems and potentially human health through the marine food chain.

Bioaccumulation of trace metals in the plastisphere: Awareness of environmental risk from a European perspective.

The term "Plastisphere" refers to the biofilm layer naturally formed by microorganisms attaching to plastic surfaces. This layer possesses the capability to adsorb persistent organic and inorganic pollutants, particularly trace metals, which are the focus of this research study. Immersion experiments were concurrently conducted in five locations spanning four European countries (France, Ireland, Spain, and Italy) utilising eight distinct polymers. These immersions, repeated every three months over a one-year period, aimed to evaluate the baseline bioaccumulation of 12 trace metals. The study underscores the intricate nature of metal bioaccumulation, influenced by both micro-scale factors (such as polymer composition) and macro-scale factors (including geographical site and seasonal variations). Villefranche Bay in France exhibited the lowest metals bioaccumulation, whereas Naples in Italy emerged as the site where bioaccumulation was often the highest for the considered metals. Environmental risk assessment was also conducted in the study. The lightweight nature of certain plastics allows them to be transported across significant distances in the ocean. Consequently, evaluating trace metal concentrations in the plastisphere is imperative for assessing potential environmental repercussions that plastics, along with their associated biota, may exert even in locations distant from their point of emission.

Exploring microplastic contamination in reef-associated fishes of the Tropical Atlantic.

Microplastics (MPs) are ubiquitous in marine compartments, and their transboundary distribution favours the dispersion and accumulation of particles in ecosystems. This study investigated MP contamination in four coastal fish species (Haemulon squamipinna, Chaetodon ocellatus, Syacium micrurum, and Alphestes afer) from the southwestern Tropical Atlantic. An alkaline treatment was applied to extract MPs from the digestive tracts, and a Laser Direct Infrared (LDIR) system was used to identify polymers. All species analysed were contaminated with MPs, with Alphestes afer being the most contaminated (1.45 ± 1.09 MPs individual-1; frequency of occurrence 80 %). No significant differences were found in the number and size of detected particles among species. The most common shapes were fibres and films, and polyethylene was the most abundant polymer. This study provides important baseline data on MP contamination in coastal fish species inhabiting complex habitat areas relevant for conserving marine biodiversity.

From prey to predators: Evidence of microplastic trophic transfer in tuna and large pelagic species in the southwestern Tropical Atlantic.

Plastic pollution is present in most marine environments; however, contamination in pelagic predators, including species of economic interest, is still poorly understood. This study aims to access the macro- and microplastic contamination in tuna and large pelagic species and verify whether a trophic transfer occurs from prey to tunas captured by two fleets in the Southwestern Tropical Atlantic (SWTA). We combined different methodological approaches to analyse the intake of macro- and microplastics. In addition to examining the plastics in the fish' stomachs, we investigated the contamination in the prey retrieved from the guts of predators. A low frequency of occurrence (3%) of macroplastic was detected in the tuna and large pelagic species; conversely, we observed a high frequency of microplastic in the tuna's stomachs (100%) and prey analysed (70%). We evinced the trophic transfer of microplastics by analysing the ingestion rate of particles in prey retrieved from the tuna stomachs. In the 34 analysed prey, we detected 355 microplastic particles. The most contaminated prey were cephalopods and fishes of the Bramidae family. The most frequent microplastic shapes in both prey and tuna stomachs were foams, pellets and fibres (<1 mm). A variety of polymers were identified; the most frequent were styrene-butadiene rubber (SBR), polyamide (PA), polyethylene terephthalate (PET) and polyethylene (PE). Our findings enhance scientific knowledge of how the ecological behaviour of marine species can affect microplastic intake.

Cd transfers during marine sediment resuspension over short and long-term period: Associated risk for coastal water quality.

Cadmium (Cd) is a highly toxic metal, regularly monitored uniformly for water quality across Europe, but scarcely for sediments. This study was designed to compare the kinetics of Cd remobilization and the amplitude of its transfers with different marine sediments. The results showed a highly reproducible transfer kinetics. Dissolved Cd was strongly and quickly removed from the dissolved phase (from 5 min up to 7 h). Then, the dissolved Cd concentration increased progressively to reach a maximal value after two weeks of mixing. The influence of the resuspension intensity representing light wind-induced resuspension up to dredging operations was observed after 2 weeks. The intensity of the sediment resuspension clearly impacted the amplitude of Cd remobilization, dissolved Cd ranging from a few ngL-1 to few hundreds of ngL-1, exceeding the maximal dissolved Cd concentration accepted by the European Union Water Framework Directive (WFD-2008/105 32/EC).

The role of mesopelagic fishes as microplastics vectors across the deep-sea layers from the Southwestern Tropical Atlantic.

Microplastics (MPs; <5 mm) are a macro issue recognised worldwide as a threat to biodiversity and ecosystems. Widely distributed in marine ecosystems, MPs have already been found in the deep-sea environment. However, there is little information on ecological mechanisms driving MP uptake by deep-sea species. For the first time, this study generates data on MP contamination in mesopelagic fishes from the Southwestern Tropical Atlantic (SWTA) to help understand the deep-sea contamination patterns. An alkaline digestion protocol was applied to extract MPs from the digestive tract of four mesopelagic fish species: Argyropelecus sladeni, Sternoptyx diaphana (Sternoptychidae), Diaphus brachycephalus, and Hygophum taaningi (Myctophidae). A total of 213 particles were recovered from 170 specimens, and MPs were found in 67% of the specimens. Fibres were the most common shape found in all species, whereas polyamide, polyethylene, and polyethylene terephthalate were the most frequent polymers. The most contaminated species was A. sladeni (93%), and the least contaminated was S. diaphana (45%). Interestingly, individuals caught in the lower mesopelagic zone (500-1000 m depth) were less contaminated with MPs than those captured in the upper mesopelagic layer (200-500 m). Our results highlight significant contamination levels and reveal the influence of mesopelagic fishes on MPs transport in the deep waters of the SWTA.

Plastic in the inferno: Microplastic contamination in deep-sea cephalopods (Vampyroteuthis infernalis and Abralia veranyi) from the southwestern Atlantic.

Microplastics are a relevant environmental concern in marine ecosystems due to their ubiquity. However, knowledge on their dispersion patterns within the ocean basin and the interaction with biota are scarce and mostly limited to surface waters. This study investigated microplastic contamination in two species of deep-sea cephalopods from the southwestern Atlantic with different ecological behaviour: the vampire squid (Vampyroteuthis infernalis) and the midwater squid (Abralia veranyi). Microplastic contaminated most of the evaluated specimens. V. infernalis showed higher levels of contamination (9.58 ± 8.25 particles individual-1; p < 0.05) than A. veranyi (2.37 ± 2.13 part. ind.-1), likely due to the feeding strategy of V. infernalis as a faecal pellets feeder. The size of extracted microplastics was inversely proportional to the depth of foraging. The microplastics were highly heterogeneous in composition (shape, colour and polymer type). Our results provide information regarding microplastic interaction with deep-sea organisms and evidence of the biological influence in the microplastic sinking mechanism.

Seawater copper content controls biofilm bioaccumulation and microbial community on microplastics.

The adsorption of trace metals on microplastics (MPs) is affected by the presence of surficial biofilms but their interactions are poorly understood. Here, we present the influence of Cu levels in real seawater (Toulon Bay, NW Mediterranean Sea) on microbial communities and Cu content of the resulting biofilms grown during incubation experiments on high density polyethylene. Two sets of incubation experiments were run with seawater supplied with MPs, sampled in two sites with contrasting Cu levels: Pt12 (most contaminated site) and Pt41P (less contaminated site). For each incubation experiment, 5 treatments were considered differing in Cu concentrations, ranging between 30 and 400 nM and between 6 and 60 nM, for Pt12 and Pt41p, respectively. A control experiment (filtered at 0.2 µm) was run in parallel for each incubation experiment. We observed that, at the time scale of the incubation period, both prokaryotic and eukaryotic richness and diversity were higher in the biofilms formed from the most contaminated site. In addition, we showed that Cu levels are shaping biofilm communities, evidencing co-occurrence patterns between prokaryotes and eukaryotes with diatoms playing a central role. These differences in biofilm formation were reflected in the amount of bioaccumulated Cu per dry weight of MPs, exhibiting higher values in the most contaminated site. Within this site, the increase of Cu seawater content enhanced its bioaccumulation onto MPs until reaching saturation. This study strongly suggests a striking link between seawater copper content, biofilm community shaping and the resulting Cu bioaccumulation onto MPs.

Microplastics in a salt-wedge estuary: Vertical structure and tidal dynamics.

The abundance and distribution of microplastics in estuaries have been barely documented, and generally without accounting for the vertical structure in the water column. This study presents the very first data on the occurrence and distribution of microplastics in the Adour Estuary, SW France. The experimental data set was complemented by numerical simulations to gain understanding of the behaviour of suspended microplastics. Microplastics were found throughout the water column with a mean abundance of 1.13 part/m3. Films and fragments were the most abundant types of particles collected. Numerical simulations demonstrated that vertical distribution of microplastics in the water column is highly dependent on particle characteristics and on the local hydrodynamics. The main trend is that neutrally-buoyant microplastics are easily flushed out while heavier microplastics are prone to entrapment in the estuary, in particular under low discharge conditions. The present study suggest that estuaries could be a sink of microplastics.

Have decades of abiotic studies in sediments been misinterpreted?

Sterilization techniques are largely employed to distinguish biotic and abiotic processes in biogeochemical studies as they inhibit microbial activity. Since one century, chemical sterilizers, supposed to preserve original environmental samples, have taken precedence over physical sterilization techniques considered too destructive. Sodium azide (NaN3) is nowadays the most commonly used inorganic chemical sterilizer. It is sufficiently purified to study trace metals, as well. Nevertheless, its (in)activity in physico-chemical processes was never ascertained. Through the investigation of sediment resuspension in seawater, the present work unequivocally demonstrated that NaN3 can impact carbon and trace metals' transfers by altering the redox balance and pH. Unlike decades of blind practice, NaN3 should be used with great care to track abiotic processes from organic matter rich and reductive matrices.

Dissolved organic matter controls of arsenic bioavailability to bacteria.

The presence of arsenic in irrigation and drinking waters is a threat to worldwide human health. Dissolved organic matter (DOM) is a ubiquitous and photoreactive sorbent of arsenic, capable of both suppressing and enhancing its mobility. Microbes can control the mobilization of mineral-bound arsenic, through redox processes thought to occur intracellularly. The role that DOM plays on the bioavailability of arsenic to microbes is often invoked but remains untested experimentally. Here, using a whole-cell biosensor, we tested the role of DOM on As(III) and As(V) bioavailability. Using cation amendments, we explored the nature of As-DOM interactions. We found As bioavailability to be dependent on [As]/[DOM] ratio and on the strength of As binding to DOM which varied as a function of time. We further tested the role of DOM on As(III) photooxidation and showed that As(III) photooxidation rate is limited by the strength of its interactions with DOM and sensitive to ionic competitive desorption. Our study demonstrates the dynamic control that photoreactive DOM poses on the bioavailability and reactivity of As in the environment and highlights the kinetic controls that DOM can possibly exert on As toxicity at various levels in foodwebs.

Evaluation of diffusive gradients in thin films (DGT) technique for speciation of trace metals in estuarine waters - A multimethodological approach.

Understanding the potential bioavailability of trace metals (TM) in marine systems is of prime importance to implement adapted regulations and efficiently protect our coastal and estuarine waters. In this study Diffusive Gradients in Thin films (DGT) technique with two different pore size was used to evaluate the potentially bioavailable fractions (DGT-labile) of Cd, Co, Cu, Ni, Pb and Zn at various depths of a highly stratified estuary (the Krka River estuary, Croatia) both in winter and summer. DGT-labile concentrations were compared to (1) total dissolved concentrations, (2) concentrations of labile species measured by anodic stripping voltammetry (ASV-labile) for Cu and (3) concentrations derived by chemical speciation modelling. High correlation between dissolved and DGT-labile concentrations was found for all metals, except for Zn where contamination problems prevented reliable conclusions. Percentages of DGT-labile fractions over total dissolved concentrations were (AVG ±â€¯SD): 92 ±â€¯3%, 64 ±â€¯2%, 23 ±â€¯5%, 61 ±â€¯3% and 57 ±â€¯6% for Cd, Pb, Cu, Ni and Co, respectively. No significant difference was found between trace metal concentrations measured with an open pore and restricted pore devices, implying the predominance of kinetically labile metal complexes smaller than 1 nm. For Cu, ASV-labile and DGT labile concentrations were highly correlated (0.97) with ASV-labile concentration being around 35% lower than that of the DGT-labile. Modelling of chemical speciation reliably predicted dynamic (free, inorganic and part of organic complexes) concentration of Cd, whereas dynamic concentrations of Cu and Pb were underestimated by 32% and 65%, respectively. In view of the relative simplicity of DGT devices, they are well suited for the monitoring effort of coastal waters, informing on potentially bioavailable concentrations of TM and thereby, helping to achieve good environmental status of coastal waters, as stipulated within the EU Water Framework Directive.

Kinetic processes of copper and lead remobilization during sediment resuspension of marine polluted sediments.

Contaminated sediments could act as a source of contamination to the surrounding environments by several processes (e.g., diffusive flux, sediment resuspension). This study aimed at highlighting the mechanisms of copper and lead mobilization from resuspended particles to the aqueous phase using laboratory experiments and a kinetic model. Three sediments, differed by their compositions and metal partition from Toulon Bay (SE France) were used. In addition, three solid/liquid ratios (0.1, 1 and 10 g L-1) allowed simulating at best natural and anthropogenic scenarios (e.g., storm, nautical traffic, dredging). We monitored metal concentrations, physicochemical parameters (pH, Eh, [O2]) and organic matter concentration along with their optical properties. Experimental results showed successive reactions over short and long terms (hour and day scale, respectively) that controlled Cu and Pb exchanges between particles and the aqueous phase over 4 weeks. The quick Cu removal was attributed to the implications of newly formed oxides while the long-term Cu release in the dissolved fraction from the more refractory solid pool is more likely related to organic complexation. In fact, we observed a transformation of the dissolved organic matter: an increase in molecular weight and in humic fluorescence properties. However, the Pb removal toward the end of the experiment could be explained by a migration toward the exchangeable sites of higher energy, which could correspond to the particulate organic matter or a combination with organic-coating carrier phases. Both kinetic rate and system response times (τi) were coherent despite the variability of parameters intrinsic to sediments (e.g., sediment composition and initial metal repartition) but also extrinsic parameters (solid/liquid ratios). Such a coherence would imply the universality of the obtained constants to be used in a more predictive approach to assess the potential of metal mobility using metal repartition in contaminated sediments when combined with hydrological and sedimentological models.

Long-term monitoring emphasizes impacts of the dredging on dissolved Cu and Pb contamination along with ultraplankton distribution and structure in Toulon Bay (NW Mediterranean Sea, France).

A long-term monitoring during dredging and non-dredging periods was performed. Total and dissolved Cu and Pb concentrations, DGT-labile Pb, ultraphytoplankton abundance and structure were monitored at four sites: dredging site, dumping site (inside/outside of a geotextile bag) and reference site. During the reference period (non-dredging), an increasing contamination in Pb, Cu and a progressive shift from Synechococcus to photosynthetic picoeukaryotes dominance was observed from reference to dumping site. Pb concentrations were significantly higher during dredging period, pointing out sediment resuspension as Pb major source of contamination. Unlike Pb, Cu concentrations were not statistically different during the two periods. Dredging period did not impact on ultraphytoplankton abundance and structure but influence heterotrophic prokaryotes abundance. Sediment resuspension is therefore a major driver of chemical and biological qualities in Toulon Bay. Furthermore, although the geotextile bag reduces particulate transport of the dredged sediment, the transport in the dissolved phase remains a major problem.

Correction to: Microplastics in seawater: sampling strategies, laboratory methodologies, and identification techniques applied to port environment.

The article Microplastics in seawater: sampling strategies, laboratory methodologies, and identification techniques applied to port environment.

Microplastics in seawater: sampling strategies, laboratory methodologies, and identification techniques applied to port environment.

The European Interreg Italy-France 2014-2020 Maritime Project SPlasH! (Stop to Plastics in H2O!) focused on the study of microplastics (MPs) in the marine port environment to evaluate their presence, abundance, and mechanisms of diffusion to the open sea. In the framework of this project, a worldwide review of 74 studies was carried out, providing an overview of MP investigation techniques, focusing on sampling strategies, laboratory methodologies, and identification of MPs collected in seawater, and specifically evaluating their applicability to the marine port environment. Nets were the most commonly used device for MP surface sampling, but their use can be difficult in narrow spaces within the port basins, and they must be coupled to discrete sampling devices to cover all port basins. In the laboratory, density separation (NaCl, ZnCl2, NaI, sodium lauryl sulfate (SLS)), filtration (polycarbonate, polyamide, glass, cellulose, ANOPORE inorganic membrane filters), sieving, visual sorting, and digestion methods (acidic, enzymatic, alkaline, oxidative) were used to separate MPs from seawater. Digestion becomes essential with water samples with great inorganic and organic loads as deriving from a port. Although many studies are based only on visual MP identification under a microscope, analytical identification techniques unequivocally determine the particle nature and the identity of the plastic polymers and are necessary to validate the visual sorting of MPs. Fourier-transform infrared spectroscopy (FTIR) is the most used analytical identification technique.

Characterisation and modelling of marine dissolved organic matter interactions with major and trace cations.

A two-step protocol (nano-filtration and reverse osmosis) was applied for natural organic matter (NOM) preconcentration of a seawater sample. Complexing affinities of the so concentrated marine dissolved NOM (DNOM) towards major and trace cations were studied by potentiometric and voltammetric titration techniques. The potentiometric titration experiments fitted by models describing and characterising the DNOM-cation interactions, revealed four distinct classes of acidic sites (pKa of 3.6, 4.8, 8.6 and 12). A total acidic sites density of 445meq/mol(C) was estimated, with a majority (60%) of carboxylic-like sites. Pseudopolarographic measurements revealed two distinct groups of copper complexes: labile, reducible at about -0.2V; and inert, directly reducible at about -1.4V. Simultaneous competition between copper, calcium and proton highlighted the presence of two classes of binding sites (density of 1.72 and 10.25 meq mol(C)(-1), respectively, corresponding to 3% of total acidic sites). The first class was more specific to copper (logK(CuL) 9.9, logK(CaL) 2.5, pKa 8.6), whereas stronger competition between copper and calcium occurred for the second class (logK(CuL) 6.9, logK(CaL) 5.5, pKa 8.2). The binding sites characterisation was validated by the very good matching of the non-concentrated seawater sample titration data with the simulated curves obtained using the binding parameters from the concentrated sample. Furthermore, this comparison also validated the applied preconcentration protocol, highlighting its negligible influence on organic matter properties when considering copper complexation.