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The rate of ocean uptake of anthropogenic CO2 has declined over the past decade, so a critical question for science and policy is whether the ocean will continue to act as a sink. Large areas of the ocean remain without observations for carbonate system variables, and oceanic CO2 observations have declined since 2017. The Mediterranean Sea is one such an area, especially its eastern part, where there is a paucity of carbonate system data, with large areas not sampled or only sampled by ship-based discrete measurements as opposed to high frequency, sensor-equipped time-series fixed stations. The aim of this study was to analyze a multi-year time-series of high-frequency (hourly) partial pressure CO2 (pCO2) and pH measurements in the Eastern Mediterranean, along with low-frequency (monthly) measurements of total dissolved inorganic carbon and total alkalinity. The pCO2 time-series was the first obtained in the Eastern Mediterranean. The study was conducted at a fixed platform of the POSEIDON system (Heraklion Coastal Buoy) located near Crete Island. Temperature was the dominant factor controlling the temporal variability of pCO2 and pH, while the remaining non-thermal variability appeared to be related to evaporation, water mixing, and biological remineralization-production. The air-sea CO2 fluxes indicated a transition from a winter-spring sink period to a summer-autumn source period. The annual air-sea CO2 flux was too low (-0.16 ± 0.02 mol m-2 yr-1) and variable to conclusively characterize the area as a net source or sink of CO2, highlighting the need for additional high frequency observation sites. Algorithms were developed using temperature, chlorophyll and salinity data to estimate pCO2 and total alkalinity, in an effort to provide tools for estimates in poorly observed areas/periods from remotely sensed products. The applicability of the algorithms was tested using Surface Ocean CO2 Atlas (SOCAT) data from the Eastern Mediterranean Sea (1999 to 2020) which showed that the algorithm pCO2 estimates were generally within ±20 μatm of the pCO2 values reported by SOCAT. Finally, the integration and analysis of the data provided directions on how to optimize the observing strategy, by readapting sensor location and using estimation algorithms with remote sensing data.

There is a general scarcity of oceanic observations that concurrently examine air–sea interactions, coastal–open-ocean processes and physical–biogeochemical processes, in appropriate spatiotemporal scales and under continuous, long-term data acquisition schemes. In the Mediterranean Sea, the resulting knowledge gaps and observing challenges increase due to its oligotrophic character, especially in the eastern part of the basin. The oligotrophic open Cretan Sea's biogeochemistry is considered to be representative of a greater Mediterranean area up to 106 km2, and understanding its features may be useful on even larger oceanic scales, since the Mediterranean Sea has been considered a miniature model of the global ocean. The spatiotemporal coverage of biogeochemical (BGC) observations in the Cretan Sea has progressively increased over the last decades, especially since the creation of the POSEIDON observing system, which has adopted a multiplatform, multivariable approach, supporting BGC data acquisition. The current POSEIDON system's status includes open and coastal sea fixed platforms, a Ferrybox (FB) system and Bio-Argo autonomous floats that remotely deliver fluorescence as a proxy of chlorophyll-a (Chl-a), O2, pH and pCO2 data, as well as BGC-related physical variables. Since 2010, the list has been further expanded to other BGC (nutrients, vertical particulate matter fluxes), ecosystem and biodiversity (from viruses up to zooplankton) variables, thanks to the addition of sediment traps, frequent research vessel (R/V) visits for seawater–plankton sampling and an acoustic Doppler current profiler (ADCP) delivering information on macrozooplankton–micronekton vertical migration (in the epipelagic to mesopelagic layer). Gliders and drifters are the new (currently under integration to the existing system) platforms, supporting BGC monitoring. Land-based facilities, such as data centres, technical support infrastructure, calibration laboratory and mesocosms, support and give added value to the observatory. The data gathered from these platforms are used to improve the quality of the BGC-ecosystem model predictions, which have recently incorporated atmospheric nutrient deposition processes and assimilation of satellite Chl-a data. Besides addressing open scientific questions at regional and international levels, examples of which are presented, the observatory provides user-oriented services to marine policy makers and the society, and is a technological test bed for new and/or cost-efficient BGC sensor technology and marine equipment. It is part of European and international observing programs, playing a key role in regional data handling and participating in harmonization and best practices procedures. Future expansion plans consider the evolving scientific and society priorities, balanced with sustainable management.

The Surface Ocean CO2 Atlas (SOCAT) is a synthesis of quality-controlled fCO2 (fugacity of carbon dioxide) values for the global surface oceans and coastal seas with regular updates. Version 3 of SOCAT has 14.7 million fCO2 values from 3646 data sets covering the years 1957 to 2014. This latest version has an additional 4.6 million fCO2 values relative to version 2 and extends the record from 2011 to 2014. Version 3 also significantly increases the data availability for 2005 to 2013. SOCAT has an average of approximately 1.2 million surface water fCO2 values per year for the years 2006 to 2012. Quality and documentation of the data has improved. A new feature is the data set quality control (QC) flag of E for data from alternative sensors and platforms. The accuracy of surface water fCO2 has been defined for all data set QC flags. Automated range checking has been carried out for all data sets during their upload into SOCAT. The upgrade of the interactive Data Set Viewer (previously known as the Cruise Data Viewer) allows better interrogation of the SOCAT data collection and rapid creation of high-quality figures for scientific presentations. Automated data upload has been launched for version 4 and will enable more frequent SOCAT releases in the future. High-profile scientific applications of SOCAT include quantification of the ocean sink for atmospheric carbon dioxide and its long-term variation, detection of ocean acidification, as well as evaluation of coupled-climate and ocean-only biogeochemical models. Users of SOCAT data products are urged to acknowledge the contribution of data providers, as stated in the SOCAT Fair Data Use Statement. This ESSD (Earth System Science Data) "living data" publication documents the methods and data sets used for the assembly of this new version of the SOCAT data collection and compares these with those used for earlier versions of the data collection (Pfeil et al., 2013; Sabine et al., 2013; Bakker et al., 2014). Individual data set files, included in the synthesis product, can be downloaded here: doi:10.1594/PANGAEA.849770. The gridded products are available here: doi:10.3334/CDIAC/OTG.SOCAT_V3_GRID.

A compilation of data from several cruises between 1998 and 2013 was used to derive polynomial fits that estimate total alkalinity (AT) and total dissolved inorganic carbon (CT) from measurements of salinity and temperature in the Mediterranean Sea surface waters. The optimal equations were chosen based on the 10-fold cross-validation results and revealed that second- and third-order polynomials fit the AT and CT data respectively. The AT surface fit yielded a root mean square error (RMSE) of ± 10.6 μmol kg−1, and salinity and temperature contribute to 96 % of the variability. Furthermore, we present the first annual mean CT parameterization for the Mediterranean Sea surface waters with a RMSE of ± 14.3 μmol kg−1. Excluding the marginal seas of the Adriatic and the Aegean, these equations can be used to estimate AT and CT in case of the lack of measurements. The identified empirical equations were applied on the 0.25° climatologies of temperature and salinity, available from the World Ocean Atlas 2013. The 7-year averages (2005–2012) showed that AT and CT have similar patterns with an increasing eastward gradient. The variability is influenced by the inflow of cold Atlantic waters through the Strait of Gibraltar and by the oligotrophic and thermohaline gradient that characterize the Mediterranean Sea. The summer–winter seasonality was also mapped and showed different patterns for AT and CT. During the winter, the AT and CT concentrations were higher in the western than in the eastern basin. The opposite was observed in the summer where the eastern basin was marked by higher AT and CT concentrations than in winter. The strong evaporation that takes place in this season along with the ultra-oligotrophy of the eastern basin determines the increase of both AT and CT concentrations.

In order to assess seasonal and interannual variability in the export of particulate matter and its main constituents, sediment traps were deployed at five successive depths from February 2006 to March 2010 in the deepest basin of the Mediterranean (SE Ionian Sea, NESTOR site). The average total mass fluxes were 66, 58, 54, 34, and 52 mg m−2 d−1, at 700, 1200, 2000, 3200, and 4300 m, respectively. The temporal variations of the mass flux showed similar seasonal signal at all sampling depths with higher values in spring–summer and lower in autumn–winter. Changes in the main constituents of the mass flux (organic carbon, carbonates, opal, and lithogenic matter) largely followed the same temporal variability with total mass flux, revealing mechanisms of rapid vertical (top-down) transport from 700 m down to 4300 m depth. Lateral inputs at the deepest trap are probably of importance, attributed to the influence of the deep Adriatic water, characterized by relatively higher turbidity than overlying water masses. Two major processes seem to control the seasonal mass flux variability: (a) primary productivity at the euphotic zone; and (b) episodic dust input events. Primary productivity shows two maxima during late winter/early spring and late spring/summer, as witnessed by the organic carbon, carbonate, and opal fluxes in the mesopelagic and bathypelagic layers, whereas the influence of dust inputs is evidenced by enhanced lithogenic fluxes occurring during spring and summer. The interannual variability generally shows a gradual increase of fluxes during the time frame of the experiment. Both seasonal and interannual variability of mass flux are associated with variations in the intensity and position of the neighboring Pelops anticyclonic gyre, which appears to affect the upwelling of intermediate, nutrient-rich waters and subsequently the surface productivity. Combination of estimated satellite and algorithm-generated primary production data for the Ionian Sea, calculated POC fluxes out of the euphotic layer and POC fluxes measured by sediment traps at the mesopelagic and bathypelagic layers of NESTOR site during our 4 yr experiment, reveal that only a small portion of primary production (0.46%) reaches at 3200 m, corresponding to a mean annual carbon export of 1.12 g C m−2 yr−1.

Distribution, production and grazing of the copepod community were investigated in the northern Aegean Sea, which is characterized by a permanent thermohaline front. Cruises were conducted along a transect crossing the frontal area during spring and late summer. Biomass and production of autotrophs were measured by size fractionation and heterotrophic nanoflagellates and ciliates were also studied. Copepod biomass, production and grazing impact on the phytoplankton and ciliate populations were estimated. The copepod community was sampled with a 45 μm net to include the smallest species and their developmental stages. The size, structure and distribution of the phytoplankton imply that most carbon was fixed by picoplankton during both seasons and throughout the study area. The partitioning of carbon among the different plankton compartments was not a broad-based pyramid and the biomass of heterotrophs was higher than that of autotrophs, except in the non-frontal region during spring. Copepod biomass was substantially higher in the frontal area. Our results showed that the small-sized copepods (calanoids and cyclopoids) dominated in terms of biomass and production, but also had a greater influence on the efficiency of the trophic coupling between the primary producers and the protozooplankton than the larger species, stressing their importance in the northern Aegean Sea and the Eastern Mediterranean in general. [ABSTRACT FROM AUTHOR]

The Mediterranean Sea has been sampled irregularly by research vessels in the past, mostly by national expeditions in regional waters. To monitor the hydrographic, biogeochemical and circulation changes in the Mediterranean Sea, a systematic repeat oceanographic survey programme called Med-SHIP was recommended by the Mediterranean Science Commission (CIESM) in 2011, as part of the Global Ocean Ship-based Hydrographic Investigations Program (GO-SHIP). Med-SHIP consists of zonal and meridional surveys with different frequencies, where comprehensive physical and biogeochemical properties are measured with the highest international standards. The first zonal survey was done in 2011 and repeated in 2018. In addition, a network of meridional (and other key) hydrographic sections were designed: the first cycle of these sections was completed in 2016, with three cruises funded by the EU project EUROFLEETS2. This paper presents the physical and chemical data of the meridional and key transects in the Western and Eastern Mediterranean Sea collected during those cruises., (© 2024. The Author(s).)

In the period 1987-2017, a series of physical and chemical measurements related to oxygen variability at a trough area with a maximum depth of ~420 m in the West Saronikos Gulf, reveal the following: In the early 90s, deep winter mixing occurred resulting in an oxygenation down to ~420 m followed by an oxygen decline. This decline reached near-bottom hypoxic conditions (O 2  < ~62 μM (μmol/L)) after 1998, while a denitrification phase occurred after 2000 and a complete bottom anoxia in 2005. In June 2012, an oxygenation down to ~350 m was detected that most likely occurred in winter 2012. The 2012 oxygenation raised the until-then anoxic bottom concentrations to hypoxic ones in the years towards 2017 via vertical diffusive oxygen transfer. Observations of the benthic communities during the hypoxia, severe hypoxia (O 2  < ~15 μM) and oxygen recovery phases showed a peak of opportunists in the hypoxia and a long faunal depletion in the severe hypoxia phases. A reversal in the benthic community structure appeared after the oxygenation of 2012 with the (re)appearance of opportunists while, in 2017, the community showed signs of retreat to earlier stages. The main anthropogenic pressure that could tentatively affect the oxygen concentration in the study area is posed by the Athens treated-sewage outfall at ~40 km away from the trough, which inputs organic matter into the Saronikos Gulf through effluent water of reduced salinity that, in addition, may alter the stratification opposing the vertical mixing. We show that the treated sewage output had no influence on a) the stratification, b) the particulate and dissolved organic carbon and c) the sewage-derived organic matter. Instead, the long-term dissolved oxygen variability with the deep renewal events was mostly driven by the large-scale atmosphere-ocean conditions (heat exchange and evaporation-minus-precipitation budget) that determine the hydrographic characteristics and the winter mixing., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Microplastics (MPs) are recognized as an increasing threat to the marine environment, but little is known about their effects on benthic organisms, including sea urchins, when ingested. For this purpose, wild sea urchins (P. lividus) and seafloor sediment samples were investigated across three coastal areas of Zakynthos Island (Ionian Sea), each exposed to different anthropogenic pressures, revealing a consistent pattern in MP abundance, shape, and color. Biomarkers related to oxidative stress, neurotoxicity, and genotoxicity showed no significant effects of MP ingestion in the sea urchins, except for a positive correlation between GST activity and ingested MPs, suggesting a possible activation of their detoxification system in response to MP ingestion. While MP concentrations in sea urchins and sediments were within the low range reported in the global literature, it remains crucial to conduct further investigations in areas with MP pollution approaching predicted levels to fully comprehend the potential effects of MP pollution on marine organisms., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Climate change driven by human activities encompasses the increase in atmospheric CO 2 concentration and sea-surface temperature. Little is known regarding the synergistic effects of these phenomena on bacterial communities in oligotrophic marine ecosystems that are expected to be particularly vulnerable. Here, we studied bacterial community composition changes based on 16S rRNA sequencing at two fractions (0.1-0.2 and >0.2 μm) during a 10- day fully factorial mesocosm experiment in the eastern Mediterranean where the pH decreased by ~0.3 units and temperature increased by ~3 °C to project possible future changes in surface waters. The bacterial community experienced significant taxonomic differences driven by the combined effect of time and treatment; a community shift one day after the manipulations was noticed, followed by a similar state between all mesocosms at the third day, and mild shifts later on, which were remarkable mainly under sole acidification. The abundance of Synechococcus increased in response to warming, while the SAR11 clade immediately benefited from the combined acidification and warming. The effect of the acidification itself had a more persistent impact on community composition. This study highlights the importance of studying climate change consequences on ecosystem functioning both separately and simultaneously, considering the ambient environmental parameters.

The last decade increasing attention to litter accumulation in the marine environment revealed the issue of the terrestrial fluxes of plastic pollution into the oceans. However, limited studies investigate the macro-litter abundance and composition particularly in freshwater ecosystems and the adjusted coastal environment. In this study, we conducted an empirical analysis of anthropogenic litter (AL) in two freshwater streams and their estuaries of Lesvos island (Greece), strongly affected by the waste mismanagement in the Moria refugee camp. A total of 1,622 litter items were collected from five sites during the field campaign between the 3rd and 6th of June 2019. Among these, artificial polymer items (mainly drink bottles, single-use plastic bags, cutlery, and trays) irrespective of the site location constituted the major part ranging from 46 to 91% of total AL by mass. Drink bottles and plastic cutlery are found in higher percentage at Moria camp river and its estuary, while packaging and bag litter are more abundant at upstream sites. The operation of the camp has increased the AL abundance 13 times more than the reference site, causing severe threat to human health and to freshwater and marine environment. It is therefore important to improve the waste management system at (inter)national (change in production and packaging policy) and local scale (introducing sustainable solutions to refugee camp design) by promoting recycling and circular economy projects to diminish AL pollution., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

A medium resolution underwater gamma ray spectrometer was deployed in the submarine groundwater spring of Anavalos and was combined with conductivity and temperature sensors for continuous measurements of natural radioactivity, salinity and water temperature, respectively. The activity concentrations of radon progenies varied from (5-40) kBq m -3 , exhibited reverse dependence with salinity and were found above the guideline proposed by Environmental Protection Agency (11 kBq m -3 ). Their ratio was above unity indicating radon gas escape to the atmosphere. Time-series of the activity concentration together with their ratios were provided enabling the system configuration for long term monitoring applications. The in-situ method proved to be an effective tool to study the radioactivity levels of the spring and the groundwater - seawater interaction process. Furthermore, the proposed tool provides cost-effective measurements in terms of real-time and long-term requirements and, it is characterized by flexibility in terms of sensor integration in different platforms to perform submarine groundwater studies in a temporal and spatial manner., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Metal and metallothionein (MT) in mixed zooplankton were investigated as means of monitoring metal availability regarding environmental exposure. Spatial and temporal variability of Cd, Cu, Ni, Zn, Fe, Mn and Pb in zooplankton and seawater were studied in Saronikos Gulf (Aegean Sea, Eastern Mediterranean), once every second month during an annual cycle (2011-2012). Particulate organic carbon and chlorophyll α were also measured in seawater samples. Median zooplankton metal concentrations were 0.65, 32.4, 7.1, 864, 1420, 40.2 and 26.8 μg g -1 dw for Cd, Cu, Ni, Zn, Fe, Mn and Pb, respectively, and 109 μg g -1 ww for MTs. Metal levels in zooplankton and MTs were higher at sites influenced by human-derived pressures. Additionally, metal concentrations in pelagic fish flesh from the Greek MED-POL data base were used for bioconcentration and biomagnification factors calculation. Bioconcentration from water to zooplankton was higher than metal transfer from either seston to zooplankton or zooplankton to fish.

Mesocosm experiments have been fundamental to investigate the effects of elevated CO 2 and ocean acidification (OA) on planktic communities. However, few of these experiments have been conducted using naturally nutrient-limited waters and/or considering the combined effects of OA and ocean warming (OW). Coccolithophores are a group of calcifying phytoplankton that can reach high abundances in the Mediterranean Sea, and whose responses to OA are modulated by temperature and nutrients. We present the results of the first land-based mesocosm experiment testing the effects of combined OA and OW on an oligotrophic Eastern Mediterranean coccolithophore community. Coccolithophore cell abundance drastically decreased under OW and combined OA and OW (greenhouse, GH) conditions. Emiliania huxleyi calcite mass decreased consistently only in the GH treatment; moreover, anomalous calcifications (i.e. coccolith malformations) were particularly common in the perturbed treatments, especially under OA. Overall, these data suggest that the projected increase in sea surface temperatures, including marine heatwaves, will cause rapid changes in Eastern Mediterranean coccolithophore communities, and that these effects will be exacerbated by OA.

In recent years, the Mediterranean Sea has become an accumulation zone for waste generated by the 22 countries bordering its shores. Although the effects of plastic litter on the marine environment and on organisms have recently been studied in other areas, further information is needed for the Mediterranean Sea and, in particular, about plastics additives inputs and interactions with the biota and the trophic network, such as phthalates and bisphenol A. Plastic material production, use and disposal contribute also to the release of heavy metals into the environment, such as mercury (Hg), often used during the production of chlorine, the primary ingredient in PVC, lead (Pb) and cadmium (Cd), which are used as stabilizers in PVC and leach out of products during use and disposal. Our research aims to evaluate phthalates, bisphenol A and heavy metals contamination in Lepidopus caudatus (Pisces, Trichiuridae), which could be considered as a potential sentinel species. For the evaluation of toxicological effects, we evaluated the expression of vitellogenin and metallothioneins 1. In all samples analyzed, we have not found microplastics in the gastrointestinal tract but chemical analysis revealed the presence of high content of phthalates, and in particular high quantities of DIDP, DEHP, bis-benzylester phthalate, bis-butyl ester phthalate and mono-N-butyl ester phthalate in different organs. Instead, trace elements detected in tissue revealed a trend of concentrations generally higher in liver and intestine than gill and muscle tissues. Immunohistochemical analysis for anti-metallothionein 1 antibody showed a strong positivity of liver cells, both in females and males. Analysis for the anti-vitellogenin antibody showed in females a strong positivity both in the liver cells and in the gonads, in male specimens was found to be always negative except for a specimen, in which it was highlighted a positivity in some areas of the liver and of the gonad.

A natural pH gradient caused by marine CO2 seeps off the Methana peninsula (Saronikos Gulf, eastern Peloponnese peninsula) was used as a natural laboratory to assess potential effects of ocean acidification on coccolithophores. Coccolithophore communities were therefore investigated in plankton samples collected during September 2011, September 2016 and March 2017. The recorded cell concentrations were up to ~50 x103 cells/l, with a high Shannon index of up to 2.8, along a pH gradient from 7.61 to 8.18, with values being occasionally <7. Numerous holococcolithophore species represented 60-90% of the surface water assemblages in most samples during September samplings. Emiliania huxleyi was present only in low relative abundances in September samples, but it dominated in March assemblages. Neither malformed nor corroded coccolithophores were documented. Changes in the community structure can possibly be related to increased temperatures, while the overall trend associates low pH values with high cell densities. Our preliminary results indicate that in long-termed acidified, warm and stratified conditions, the study of the total coccolithophore assemblage may prove useful to recognize the intercommunity variability, which favors the increment of lightly calcified species such as holococcolithophores., Competing Interests: The authors have declared that no competing interests exist.

The aim of this work is to assess trace metal pollution status (Cd, Cu, Ni, Pb, Zn) in the waters of Saronikos Gulf, Greece, in line with the WFD and MSFD European Directives, based on data collected over a decade (2000-2010). Dissolved metal background levels are estimated for the first time for Greek marine waters and the upper limits are: Cd: 0.574 nmol L(-1); Cu: 8.26 nmol L(-1); Ni: 7.94 nmol L(-1); Pb: 2.60 nmol L(-1); Zn: 115 nmol L(-1). The variability of dissolved and particulate metals reflected the presence of several point sources and revealed the importance of natural mechanisms acting as non-point sources. The status of Saronikos Gulf is classified as 'High' for most metals studied. An exception to this is the enclosed Elefsis Bay where Cu, Ni and Zn concentrations are found above background. Our work will assist the implementation of WFD and MSFD directives in Greece., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Ocean acidification is expected to alter marine systems, but there is uncertainty about its effects due to the logistical difficulties of testing its large-scale and long-term effects. Responses of biological communities to increases in carbon dioxide can be assessed at CO2 seeps that cause chronic exposure to lower seawater pH over localised areas of seabed. Shifts in macroalgal communities have been described at temperate and tropical pCO2 seeps, but temporal and spatial replication of these observations is needed to strengthen confidence our predictions, especially because very few studies have been replicated between seasons. Here we describe the seawater chemistry and seasonal variability of macroalgal communities at CO2 seeps off Methana (Aegean Sea). Monitoring from 2011 to 2013 showed that seawater pH decreased to levels predicted for the end of this century at the seep site with no confounding gradients in Total Alkalinity, salinity, temperature or wave exposure. Most nutrient levels were similar along the pH gradient; silicate increased significantly with decreasing pH, but it was not limiting for algal growth at all sites. Metal concentrations in seaweed tissues varied between sites but did not consistently increase with pCO2. Our data on the flora are consistent with results from laboratory experiments and observations at Mediterranean CO2 seep sites in that benthic communities decreased in calcifying algal cover and increased in brown algal cover with increasing pCO2. This differs from the typical macroalgal community response to stress, which is a decrease in perennial brown algae and proliferation of opportunistic green algae. Cystoseira corniculata was more abundant in autumn and Sargassum vulgare in spring, whereas the articulated coralline alga Jania rubens was more abundant at reference sites in autumn. Diversity decreased with increasing CO2 regardless of season. Our results show that benthic community responses to ocean acidification are strongly affected by season.