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Metal complexation by dissolved organic matter (DOM) is considered to decrease metal bioavailability by lowering the free metal ion concentration, therefore protecting organisms from the deleterious effects of metals (Campbell et al., 2002). In coastal lagoons like Mar Menor, with high terrestrial influence and low exchange with open sea, the levels of both DOM and metals are one or two orders of magnitude higher than in open-waters. In order to verify the free ion activity model (FIAM), copper internalization by Prorocentrum micans, a cosmopolitan dinoflagellate also present in the Mar Menor, was tested in the absence and presence of two types of DOM, commercially available fulvic acids from riverine origin (SRFA) and coastal DOM obtained by ultrafiltration (UF-DOM). The microalgae were exposed to artificial sea water enriched with increasing amounts of Cu65 isotope, at levels from 5 to 100 nM Cu, solely and in combination with DOM. After one-hour exposure, samples were centrifuged and washed and pellets were digested with nitric acid at 90ºC, following Sánchez-Marín et al (2010) and Croteau and Luoma (2005). In parallel, careful measurements of metal complexation by anodic stripping voltammetry (ASV) were performed and total Cu concentrations were measured by ICP-MS. Preliminary results show that copper internalization by the microalgae increases linearly as a function of labile Cu, both in the absence and presence of DOM, in agreement with FIAM and with labile Cu measurements performed by ASV. Future work might include testing the influence of competing metals, such as Pb or Zn, on Cu internalization, and to study Cu bioavailability in natural samples collected in the Mar Menor, in order to shed light into the factors that control Cu bioavailability in coastal lagoons.

Coastal areas are valuable and sensitive environments subjected to great anthropogenic pressure. Among these pressures, metal pollution is of priority concern as these pollutants can reach concentrations that exceed the levels established to protect sensitive organisms in the ecosystem. In coastal lagoons, shallow systems with a reduced exchange with the open sea, metal concentrations are one or two orders of magnitude higher than in open-waters. In addition, these systems are subjected to physicochemical variations that can alter the biogeochemical cycling of the metals. Singular environmental events such as strong winds cause metal resuspension, torrential rain events provoke the entrance of solutes and pollutants, and phytoplankton blooms dramatically increase the concentration of organic matter. These events provoke alterations in the concentration and speciation of metals in the water column. This will have a direct impact in the organisms living in the area, since metal toxicity and bioavailability depends on the chemical speciation. Dissolved organic matter (DOM) is the most important variable influencing metal speciation and bioavailability in seawater. However, the effects of DOM on metal bioavailability have not been yet unravelled and contrasting results have been reported, some showing that DOM protects against metal toxicity and others showing the opposite. The present study was designed to study how the biogeochemical cycling of trace metals in the water column of coastal lagoons is influenced by these singular environmental events and how this affects the incorporation of metals by the primary producers, in this case, microalgae, with particular focus on the effect of dissolved organic matter on metal biouptake. The proposed work combines field sampling and analytical work in the Mar Menor lagoon (SE Spain). This project will substantially contribute to widen our knowledge about the behaviour of metals in coastal areas and to determine how the presence of DOM affects their toxicity., SEEME

The scallop Aequipecten opercularis accumulates high concentrations of lead (Pb) in its tissues, what has led to the ban of its extraction in the Ría de Vigo (Galicia, Spain) for feeding purposes. The Ría de Vigo presents higher levels of Pb than other industrialized Galician Rías, mainly due to a ceramic factory that was operating in the inner part of the Ría from 1961 to 2001 (Álvarez-Iglesias et al., 2003). This study aims at testing the dynamics of bioaccumulation of Pb in this species, its tissue distribution and the subcellular partitioning Pb, with the aim of enhancing our understanding of the mechanisms that provoke the high Pb levels reached in its tissues. Scallops originating from a clean area were exposed in cages in two places in the Ría de Vigo (one harbour and a less impacted location) and 10 individuals were collected every month over a three months period. The bioaccumulation of Pb and other metals was studied including its distribution in several tissues: gills, digestive gland, kidney, muscle, gonad and rest. The results showed that scallops accumulated similar levels of Pb in both locations, and that about 76% of the Pb was found in the kidney. Subcellular partitioning of kidney samples additionally showed that around a 60-70% of Pb in the kidneys was included in metal rich granules, indicating that this is probably the reason of the high levels of Pb observed in this species, as occurs for other bivalves (Darriba and Sánchez-Marín, 2013). Concerning other metals analysed, it was observed that Zn was also mainly accumulated in the kidney, while Cd content was highest in the digestive gland. Cu and Ni were preferentially accumulated in the digestive gland or kidney, depending on the location, and As was mainly found in the muscle. Results will be discussed on the basis of metal pollution in both locations and according to detoxification strategies used by scallops.

Seminario Ibérico de Química Marina (SIQUIMAR), Las Palmas de Gran Canaria (Spain), 6-8th July 2022, Mar Menor coastal lagoon is a shallow system with a reduced exchange with the open sea, that is affected by several anthropogenic pressures, mainly agriculture and mining. The mining sierra of Cartagena-La Unión has been historically discharging mining waste rich in heavy metals in the south area of Mar Menor, resulting in high metal concentrations in sediments (García and Muñoz-Vera., 2015). The nutrients reaching the lagoon, together with the high temperatures, also provoke phytoplankton blooms that lead to high concentrations of dissolved organic matter (DOM). It is well known that total metal concentrations are not good predictors of their bioavailability, and metal speciation should be taken into account. The presence of ligands, such as DOM in the water, may form metal-DOM complexes and protect against the deleterious effects of metals. The present study aims at studying the effect of DOM on the speciation of dissolved metals (Cu and Pb) in Mar Menor waters. With that aim, filtered water was sampled at five sites in Mar Menor lagoon at several sampling periods. Metal concentration was analysed by ICP-MS with Argon gas dilution, DOC was analysed in a carbon-specific infrared gas analyser and optical characterization of DOM was obtained from absorbance and fluorescence spectra. Complexiometric titrations of Cu and Pb were performed by anodic stripping voltammetry following Durán and Nieto (2011). Preliminary results show that Cu and Pb concentrations in Mar Menor waters are higher than in other coastal areas, especially in the south area of the lagoon, reaching concentrations of tens of nanomolar. DOC concentrations are also very high in Mar Menor waters, leading to high complexation capacities for Cu, therefore protecting aquatic biota from the deleterious effects of Cu. Pb, on the contrary, is poorly complexed by DOM, and almost all dissolved Pb is present in inorganic forms, This work has been supported by the Spanish Ministry Science and Innovation and by the European Union through the European Regional Development Fund (ERDF) through ‘SEEME’ PID2019-109355RA-I00) project

Metal concentrations have been quantified in plastic pieces collected from four beaches located in the Mediterranean coast of Spain with different characteristics (i.e. anthropogenic pressures). Several sections of the beach were sampled (i.e. coastline, middle beach and upper dunes). After an acidic extraction, metal levels in the samples were measured for by ICP-MS. In addition to the metal content, plastics have been classified according to their characteristics such as polymer type, color or state of degradation. These characteristics have shown to influence the adsorption capacity of metals by plastics. Some preliminary results have shown that aged and dark colored plastics accumulate higher metal levels probably associated to plastic surface modification. In addition, significative differences in metal accumulation has been observed for each polymer. Finally, the most anthropized beaches (i.e. mining or industry) showed, in general, higher levels of metals such as As, Cd, Pb or Zn. This work shows that metal content in plastics can give an idea about the pollution degree of the area where these plastic pieces have been collected. Therefore, this study is a contribution to the potential use of plastics as pollution monitors.

Microplastics (MPs) are widely distributed in marine environments and have been reported to cause harmful physiological effects in marine bivalves including immune modulation. While Mytilus galloprovincialis is a model species in environmental monitoring studies, little is known regarding the effects of MPs and palladium (Pd), an emerging contaminant, metal on the immune functioning of this species. In this study, gills and gland samples of specimens of M.ytilus galloprovincialis which were exposed to the same particle concentration (2.5 x 10 66 μm3μm /mL) of Control (microalgae), MP (virgin microplastics) and MP-Pd (Pd spiked microplastics) once an hour during 4 hours. Thus, mussels were exposed to 6095 ng of Pd/mussel. Samples analyzed were collected after 4 and 24 hours of exposure and after 24, 48 and 144 hours of depuration. Several innate immune activities (lysozymes, peroxidase, protease, antiprotease, and bactericidal activities) were analyzed. Our data demonstrated that after 24 hours of exposure to MP, a decrease in lysozymes and peroxidase activities occurred, but not in the bactericidal activity which increased. However, when MP-Pd was used, an increase in all these activities was observed compared to MP levels group. These data suggest that when MP are spiked with Pd, the latter compound might induce an inflammatory process that will results in higher levels of most of all the immune activities analyzed. In the gland, however, most of the activity levels were decreased upon MP-Pd treatment compared to MP levels at different time point of exposure depending on the activity. Interestingly, after 24 hours of removing the pollutants from the water, most of the activity levels in both tissues, gills and gland, were recovered to control levels, but not the bactericidal activity. Considering this impairment of the bactericidal activity against possible pathogenic bacteria, a potential threat to mussels population in a polluted scenario is highly plausible.

17 pages, 10 figures, 2 tables, supplementary data https://doi.org/10.1016/j.ecolind.2022.109209, Reconstruction of marine communities in search of baseline (pristine) conditions is a crucial first step for their future restoration. A recent reconstruction (last century) of the sandy-muddy bottom fauna on the continental shelf of a marine protected area (MPA) was performed in the Columbretes Reserve, including periods after and before the Reserve declaration. The dating of sediments and identification of faunal remains (e.g., shells of benthic bivalves and gastropods and pelagic pteropods) were performed in a core (MC2) at a depth of 87 m in 2018. Radiometric data identified sediments older (below 11 cm) and younger (from the top of the core to 11 cm) than ca. 110 years. Mercury analyses validated the 210Pbxs data at 5–7 cm (1967–1989), with a significant Hg peak that coincided with a period of military activities occurring until 1982 in the Columbretes Islands. Both human and climatic variables affected benthic and pelagic communities. Among the human impacts, the cessation of trawling activity after the declaration of the MPA (1980s) influenced the most dominant benthos (bivalves and gastropods) by i) increases in their abundance and ii) changes in the feeding guilds, with a return to baseline conditions by the increase in filter feeders after trawling cessation vs a high abundance of detritus feeders occurring under high trawling activity. Human activities apparently did not affect diversity levels. In parallel, we also identified some recolonization by Octocorallia since the 1980s. Finally, the increase in the pelagic pteropod Creseis acicula since 1995 at the MC2 station probably indicates the result of warming of surface waters in recent decades. Our study based on core reconstructions provides for the first time an historical perspective of the impact of trawling on marine benthos and the positive effect of conservation measures in marine protected areas, The cruise COLVIDEO0518 was financed within the framework of the project MAREMATING (CTM2016-77027-R). The study was also financed by the MICYT project RECOMARES (RTI2018-094066-B-I00), funded by Ministerio de Ciencia e Innovación, MICYIT, With the institutional support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S)

Se presenta la evaluación del estado del Medio Marino y definición del GES en la Demarcación Marina Estrecho y Alborán en relación al Descriptor 8 (Contaminantes químicos en sedimentos, peces y bivalvos y biomarcadores relacionados con la contaminación química en peces y bivalvos)