Use of Unmanned Surface Vehicles (USVs) in Water Chemistry Studies.

Unmanned surface vehicles (USVs) equipped with integrated sensors are a tool valuable to several monitoring strategies, offering enhanced temporal and spatial coverage over specific timeframes, allowing for targeted examination of sites or events of interest. The elaboration of environmental monitoring programs has relied so far on periodic spot sampling at specific locations, followed by laboratory analysis, aiming at the evaluation of water quality at a catchment scale. For this purpose, automatic telemetric stations for specific parameters have been installed by the Institute of Marine Biological Resources and Inland Waters of Hellenic Centre for Marine Research (IMBRIW-HCMR) within several Greek rivers and lakes, providing continuous and temporal monitoring possibilities. In the present work, USVs were deployed by the Athens Water and Sewerage Company (EYDAP) as a cost-effective tool for the environmental monitoring of surface water bodies of interest, with emphasis on the spatial fluctuations of chlorophyll α, electrical conductivity, dissolved oxygen and pH, observed in Koumoundourou Lake and the rivers Acheloos, Asopos and Kifissos. The effectiveness of an innovative heavy metal (HM) system installed in the USV for the in situ measurements of copper and lead was also evaluated herewith. The results obtained demonstrate the advantages of USVs, setting the base for their application in real-time monitoring of chemical parameters including metals. Simultaneously, the requirements for accuracy and sensitivity improvement of HM sensors were noted, in order to permit full exploitation of USVs' capacities.

Assessing marine macrolitter on the coastline of the Asterousia Biosphere Reserve: Insights from a community-based study.

Even in pristine and remote environments of the Mediterranean, marine litter is building up threatening habitats and species and inhibiting sustainable development. The present study reports the findings of beach litter surveys carried out by 250 local community members in nine sites along the coastline of the Asterousia Biosphere Reserve, situated in the southernmost end of Europe. The average recorded litter density along these sites amounted to 125 items per 100 meters of coastline (range: 22-510) and to 0.05 items per square meter of beach (range: 0.01-0.13). Only two of the nine surveyed beaches were found to be in good environmental status, in compliance with the European threshold value for beach litter. The other seven studied beaches surpassed the European threshold value. The primary sources of the litter identified in the study can be attributed to unsustainable practices and inadequate waste management by individuals, communities and municipalities using the coastal and marine environment. Additionally, unsustainable waste management practices within the agricultural sector were also found to be a significant contributor to marine litter pollution.

Chromium speciation, mobility, and Cr(VI) retention-release processes in ultramafic rocks and Fe-Ni lateritic deposits of Greece.

Water contamination by geogenic hexavalent chromium is an emerging issue in areas developed on ultramafic rocks and their weathering products. In this study, samples of serpentinites, soil, and laterites were collected and analyzed for the levels of Cr species, distribution into phases of different mobility, mineralogy, Cr oxidation capacity, and leaching of Cr(VI). Total chromium (2176-21,929 mg kg-1) was mainly found in Cr spinels (~ 50% wt as Cr2O3) and Fe (hydr)oxides (2.5% wt). Total Cr(VI) contents (0.49-11.5 mg kg-1) increased from the serpentinites to the soil and lateritic deposit, i.e., during the advanced stages of weathering, which were accompanied by increased Cr mobility. Batch experiments of 500-h duration showed that Cr(VI) released in water at rates of 0.25-1.20 nM h-1. Rates were higher in water of pH 5.7 rather than pH 8.5, because more Cr(VI) was formed during the experimental period. Asbolane-type Mn oxides and Mn-bearing crystalline Fe oxides were responsible for Cr(III) oxidation. Most of the generated Cr(VI) (52-79% of total Cr(VI)) remained solid-bound by adsorption and/or precipitation processes. Because all samples had a self-capacity to oxidize Cr(III), it seems that retention processes will ultimately define the extent of geogenic Cr(VI) contamination of aquatic systems.

Plastic pollution on the Mediterranean coastline: Generating fit-for-purpose data to support decision-making via a participatory-science initiative.

Plastic pollution is a global problem and reliable, coherent and comparable data are essential for targeted mitigation strategies. Throughout the years Mediterranean NGOs have significantly contributed to providing data and information on the temporal and spatial distribution of marine litter found stranded on beaches; thus participatory-science campaigns are an essential tool to fill in the marine litter knowledge gaps. The present study reports the findings of beach litter surveys carried out by 7 NGOs in 23 sites along the coastline of the Mediterranean. The average litter density per site varied from 53 items/100 m to 6,660 items/100 m, with a median of 451 items/100 m. The majority of litter items were made of artificial/anthropogenic polymer materials accounting for 90% of all litter collected. Litter from shoreline sources accounted for 38%. Single-use plastics (SUPs) accounted for 38% of all items recorded ranging from 18.6% to 66.9% for the different beaches. 30% of the investigated beaches had more than 50% of SUPs of the total items recorded, thus providing baseline information and supporting evidence for the Single-Use Plastics Directive.

Marine litter on the beaches of the Adriatic and Ionian Seas: An assessment of their abundance, composition and sources.

The abundance, composition and sources of marine litter were determined on beaches located in the seven countries of the Adriatic-Ionian macroregion, namely Albania, Bosnia and Herzegovina, Croatia, Greece, Italy, Montenegro and Slovenia. A total of 70,581 marine litter items were classified and recorded through one-year long surveys carried out in 31 sites. The average litter density of 0.67 items/m2 found within this study is considered to be relatively high. The beaches investigated differed in terms of human-induced pressures; their majority is classified either as semi-urban or semi-rural, while very few beaches could be characterized as urban or remote/natural. The majority of litter items were made of artificial/anthropogenic polymer materials accounting for 91.1% of all litter. Litter from shoreline sources accounted for 33.4% of all litter collected. The amount of litter from sea-based sources ranged in the different countries from 1.54% to 14.84%, with an average of 6.30% at regional level.

Characterization of PM2.5 chemical composition at the Demokritos suburban station, in Athens Greece. The influence of Saharan dust.

The aim of this work is to study the atmospheric concentrations of selected major and trace elements and ions found in PM2.5, at a suburban site in Athens, Greece, and discuss on the impact of the different sources. Special focus is given to the influence of Saharan dust episodes. The seasonal variability in the metal and ion concentrations is also examined. The results show that PM2.5 mass concentrations are significantly influenced by Saharan dust events; it is observed that when the PM2.5 concentration is higher than 25 µg/m3, five out of six times, the air mass crossed North Africa at an altitude within the boundary layer. Fe is found to be the element with the more significant seasonal variability, displaying much higher concentrations during cold period. The frequent Saharan dust intrusions in the cold period of this dataset may explain this result. Mineral dust and secondary aerosol are the main PM2.5 components (29 and 34%, respectively). During Saharan dust events, the concentration of mineral dust is increased by 35% compared to the days without dust intrusions, while an increase of 68% of the sea salt is also observed. During event days, PM2.5 concentrations are also increased by 14%. Anthropogenic components do not decrease during those days, while sulfate displays even a slight increase, suggesting enrichment of mineral dust with secondary sulfates. The results indicate that African dust intrusions add a rather significant PM pollution load even in the PM2.5 fraction, with implication to population exposure and human health.

Organic complexation of copper in throughfall and open field bulk deposition: Influence of the tree canopy of Mediterranean forest ecosystems.

The complexing capacity for Cu ions (LT) and the apparent stability constant values (logKapp) were measured in throughfall (TF) and open field bulk deposition (BD), at two Mediterranean forest ecosystems of western Greece. LT was measured for the first time in the TF of natural forests. Concentrations of LT were three-to-four-fold higher in TF (mean ± st.dev: 2014 ± 769 nM for Varetada and 1565 ± 595 nM for Karpenissi) compared to those in BD (531 ± 517 nM and 468 ± 321 nM, respectively). In all TF and BD samples, LT concentrations were significantly higher than the corresponding total Cu concentrations, indicating that Cu was fully complexed. The LT/TOC ratios in TF were found comparable between the two study sites (235 ± 149 nM mg-1 C for Varetada and 256 ± 233 nM mg-1 C for Karpenissi) and with those of BD (226 ± 257 and 163 ± 163 nM mg-1 C, respectively). The determined mean logKapp values were almost identical in TF (6.8 ± 0.7 at Varetada; 6.8 ± 0.6 at Karpenissi) and BD (6.5 ± 0.6 at Varetada; 6.8 ± 0.3 at Karpenissi), pointing to the fact that regardless of the enrichment of TF in ligands (LT(TF) > LT(BD)) the type of binding sites remain the same. The logKapp values which were obtained herewith are similar to those obtained for humic-like substances (HULIS), indicating them as the most widespread type of ligands in BD and TF.

Predictors of cadmium and lead concentrations in the blood of residents from the metropolitan area of Athens (Greece).

The Cd and Pb blood contents of healthy adult subjects who are non-occupationally exposed and living in the metropolitan area of Athens (Greece) have not been assessed thus far. Additionally, Greeks rank first among EU27 in terms of smoking habits. To fill the existing gap, we aimed to evaluate the predictors and propose reference values (RVs) of the Cd (CdB) and Pb (PbB) blood concentrations in residents of the metropolitan area of Athens (Greece). Age, sex, smoking, alcohol drinking, educational status and nutritional habits were used as variables, with an emphasis on smoking. CdB and PbB determinations were performed directly by graphite furnace atomic absorption spectrometry (GFAAS) following the appropriate dilution of the samples with Triton-X-100. The RVs of CdB and PbB proposed for the general adult population of the Metropolitan area of Athens, Greece (upper limit of the 95% CI of the 95th percentile of the distribution of values), were 2.3 and 88µgL(-1) (P95: 1.8 and 77µgL(-1); 95% CI (P95): 1.5-2.3 and 70-88µgL(-1)), respectively. Males had a higher median CdB (0.69µgL(-1)) than females (0.55µgL(-1)). Subjects aged <40years had a lower median CdB (0.51µgL(-1)) than the elderly (≥60years; 0.60µgL(-1)). The CdB in smokers (1.2µgL(-1)) was almost threefold higher than in non-smokers (0.46µgL(-1)). The PbB levels were higher in males (31µgL(-1)) than females (20µgL(-1)). Subjects aged <40years had a lower median PbB (17µgL(-1)) than the elderly (≥60years; 32µgL(-1)). A multiple linear regression analysis demonstrated that the predictor variables for the CdB levels were the standardized beta weight, smoking, age, alcohol consumption, and intake of leafy vegetables, whereas for the PbB levels they were sex and age.

Copper complexing properties and physico-chemical characterisation of the organic matter in Greek herbal infusions.

Complex formation is among the mechanisms affecting metals' bioaccessibility. Evaluating the extent of interactions between trace elements and several constituents of food items is of great interest. This paper examines the release of copper-complexing ligands in herbal infusions of 13 aromatic plants commonly used in Greece. The concentration of ligands (LT) and the copper-binding strength (logKapp) of herbal infusions were determined with Differential Pulse Anodic Stripping Voltammetry (DPASV). All herbal infusions were found to release Cu complexing ligands, at concentrations ranging from 8.8 to 112.5 µM in rosemary and marjoram, respectively. In all infusions the total copper concentrations were lower than the corresponding LT values, indicating that Cu is fully complexed. Aiming to partially characterise the physico-chemical properties of the released organic material, the surface active substances (SAS), reduced sulphur species (RS) and catalytically active compounds (CAC) were measured, for the first time, in herbal infusions by sensitive electrochemical techniques.

New insights into hydrothermal vent processes in the unique shallow-submarine arc-volcano, Kolumbo (Santorini), Greece.

We report on integrated geomorphological, mineralogical, geochemical and biological investigations of the hydrothermal vent field located on the floor of the density-stratified acidic (pH ~ 5) crater of the Kolumbo shallow-submarine arc-volcano, near Santorini. Kolumbo features rare geodynamic setting at convergent boundaries, where arc-volcanism and seafloor hydrothermal activity are occurring in thinned continental crust. Special focus is given to unique enrichments of polymetallic spires in Sb and Tl (±Hg, As, Au, Ag, Zn) indicating a new hybrid seafloor analogue of epithermal-to-volcanic-hosted-massive-sulphide deposits. Iron microbial-mat analyses reveal dominating ferrihydrite-type phases, and high-proportion of microbial sequences akin to "Nitrosopumilus maritimus", a mesophilic Thaumarchaeota strain capable of chemoautotrophic growth on hydrothermal ammonia and CO2. Our findings highlight that acidic shallow-submarine hydrothermal vents nourish marine ecosystems in which nitrifying Archaea are important and suggest ferrihydrite-type Fe(3+)-(hydrated)-oxyhydroxides in associated low-temperature iron mats are formed by anaerobic Fe(2+)-oxidation, dependent on microbially produced nitrate.

Copper complexing properties of exudates and metabolites of macroalgae from the Aegean Sea.

Macroalgae are a significant source of extracellular organic material in the coastal areas of the Mediterranean, including organic ligands which serve as modulators of metal complexing capacity. This paper examines the release of copper-complexing ligands by 24 macroalgal species, including chlorophyta, rhodophyta, ochrophyta as well as Posidonia oceanica, common throughout the Mediterranean. Metabolites isolated from the algae Dictyota dichotoma and Pterocladiella capillacea were examined for the first time regarding their Cu-complexing properties. The concentration of ligands (LT) and the copper-binding strength (logKapp) of exudates and metabolites were determined by electrochemical methods. All algal species released ligands giving LT concentrations ranging from 109 to 744 nM in unfiltered samples. An increase in the concentration of ligands up to 15 times in comparison to the blank was observed after 48 h of culturing macroalgae in artificial seawater. The binding strength (log Kapp) varied among species from 7.0 to 8.6, except for the metabolites for which it was lower (log Kapp=6). Most of the ligands released were in the dissolved phase, with the contribution of particulate and/or colloidal organic matter (up to 46% of total ligands) appearing to be important only in specific macroalgal species.

Bioaccumulation of metals (Cd, Cu, Zn) by the marine bivalves M. galloprovincialis, P. radiata, V. verrucosa and C. chione in Mediterranean coastal microenvironments: association with metal bioavailability.

The concentrations of Cd, Cu and Zn in both the whole soft tissue and separate organs (gills, mantle, muscle and digestive gland) of wild bivalves (Mytilus galloprovincialis, Pinctada radiata, Venus verrucosa and Callista chione) from three different coastal microenvironments of Greece were monitored from 2003 to 2004. In parallel, by employing appropriate analytical protocols for metal partitioning, the labile fraction of the metals was determined in the dissolved phase, suspended particulate matter and sediments. Differences in the metal levels were detected both among the study areas as well as among the bivalves examined. Significant bioaccumulation was demonstrated regarding Zn in M. galloprovincialis specimens from the highly industrialized Gulf of Elefsis and Cd in P. radiata and V. verrucosa from the Maliakos Gulf, which is influenced by extended agricultural activity occurring at the neighbouring area and a river outflow. Data of the metal levels in the various environmental phases were correlated with their concentrations in bivalves' tissues. The clear relationships obtained in many cases among the labile metal concentrations and the bioaccumulated concentrations in bivalves point out that the labile fraction of a metal is the most bioavailable. The lack of positive correlation for C. chione confirms the occurrence of effective mechanisms of internal regulation of metal concentrations.

Heavy metals in raw, fried and grilled Mediterranean finfish and shellfish.

The effect of domestic pan-frying and grilling on Cd, Cr, Cu, Fe, Hg, Ni, Pb and Zn content of popular small Mediterranean finfish and shellfish was studied. The species selected -namely anchovy, bogue, hake, picarel, sardine, sand smelt, stripped mullet, Mediterranean mussel, shrimp and squid- are among the most commonly marketed and consumed in Greece and most of the Mediterranean countries. Both culinary practices examined resulted in increased metals concentrations compared to those of raw samples, the increment being inversely related to fish size and -in most cases- being more extended in pan-frying. The consumption of cooked seafood is expected to provide significant amounts of Fe and Zn followed, in decreasing order, by Cr, Cu and Ni. In addition, the estimation of (a) weekly intakes and (b) target hazard quotients for the toxic elements Cd, Hg and Pb revealed that the cooked fish and shellfish do not pose any health risk for the consumers.

Comparison of ISO-GUM and Monte Carlo methods for the evaluation of measurement uncertainty: application to direct cadmium measurement in water by GFAAS.

The propagation stage of uncertainty evaluation, known as the propagation of distributions, is in most cases approached by the GUM (Guide to the Expression of Uncertainty in Measurement) uncertainty framework which is based on the law of propagation of uncertainty assigned to various input quantities and the characterization of the measurand (output quantity) by a Gaussian or a t-distribution. Recently, a Supplement to the ISO-GUM was prepared by the JCGM (Joint Committee for Guides in Metrology). This Guide gives guidance on propagating probability distributions assigned to various input quantities through a numerical simulation (Monte Carlo Method) and determining a probability distribution for the measurand. In the present work the two approaches were used to estimate the uncertainty of the direct determination of cadmium in water by graphite furnace atomic absorption spectrometry (GFAAS). The expanded uncertainty results (at 95% confidence levels) obtained with the GUM Uncertainty Framework and the Monte Carlo Method at the concentration level of 3.01 µg/L were ±0.20 µg/L and ±0.18 µg/L, respectively. Thus, the GUM Uncertainty Framework slightly overestimates the overall uncertainty by 10%. Even after taking into account additional sources of uncertainty that the GUM Uncertainty Framework considers as negligible, the Monte Carlo gives again the same uncertainty result (±0.18 µg/L). The main source of this difference is the approximation used by the GUM Uncertainty Framework in estimating the standard uncertainty of the calibration curve produced by least squares regression. Although the GUM Uncertainty Framework proves to be adequate in this particular case, generally the Monte Carlo Method has features that avoid the assumptions and the limitations of the GUM Uncertainty Framework.

Integrated use of biomarkers (superoxide dismutase, catalase and lipid peroxidation) in mussels Mytilus galloprovincialis for assessing heavy metals' pollution in coastal areas from the Saronikos Gulf of Greece.

Mussels are used as sentinel organisms and bioindicators to evaluate the toxic effects of chemical pollutants in marine organisms, especially heavy metals, representing an important tool for biomonitoring environmental pollution in coastal areas. Antioxidant defence enzymes play an important role in cellular antioxidant defence systems and protect from oxidative damage by reactive oxygen species (ROS). Indigenous mussels Mytilus galloprovincialis of the Saronikos Gulf of Greece were used for monitoring heavy metal pollution in three polluted sites in the area and in one unpolluted site. Seasonal variations of the activity of antioxidant defence enzymes, superoxide dismutase (SOD) and catalase (CAT), as well as lipid peroxidation (LP) were measured as biomarkers in a period of three years in relation to concentrations of trace metals in their gills and mantle and compared to mussels from an unpolluted sampling site. SOD activity increased at least 2 fold at the polluted sites when compared to the control site (the high activity was recorded in the spring time). CAT activity was increased 2-3 times at the polluted sites, with high activity in the winter and spring time, compared to the control site. LP concentration was twice higher at the polluted sites, following the same seasonal pattern. Trace metals contents in mussels collected at polluted sites were 3-4 fold higher compared to the control site and showed moderate variations along the months, with a winter maximum followed by a summer pre-spawning minimum matching the seasonal trends of temperature and salinity. Our results showed that metal pollution in the Elefsis Bay (the most polluted coastal area) causes relatively medium levels of oxidative stress in tissues of mussels due to cellular oxy-radical generation. This study, which is the first in the area, showed that seasonal variations of the activity of antioxidant defence enzymes and LP concentrations in mussels can be used as potential biomarkers of toxicity for long-term monitoring in marine coastal ecosystems.

Molecular biomarkers of oxidative stress in aquatic organisms in relation to toxic environmental pollutants.

The potential of oxygen free radicals and other reactive oxygen species (ROS) to damage tissues and cellular components, called oxidative stress, in biological systems has become a topic of significant interest for environmental toxicology studies. The balance between prooxidant endogenous and exogenous factors (i.e., environmental pollutants) and antioxidant defenses (enzymatic and nonenzymatic) in biological systems can be used to assess toxic effects under stressful environmental conditions, especially oxidative damage induced by different classes of chemical pollutants. The role of these antioxidant systems and their sensitivity can be of great importance in environmental toxicology studies. In the past decade, numerous studies on the effects of oxidative stress caused by some environmental pollutants in terrestrial and aquatic species were published. Increased numbers of agricultural and industrial chemicals are entering the aquatic environment and being taken up into tissues of aquatic organisms. Transition metals, polycyclic aromatic hydrocarbons, organochlorine and organophosphate pesticides, polychlorinated biphenyls, dioxins, and other xenobiotics play important roles in the mechanistic aspects of oxidative damage. Such a diverse array of pollutants stimulate a variety of toxicity mechanisms, such as oxidative damage to membrane lipids, DNA, and proteins and changes to antioxidant enzymes. Although there are considerable gaps in our knowledge of cellular damage, response mechanisms, repair processes, and disease etiology in biological systems, free radical reactions and the production of toxic ROS are known to be responsible for a variety of oxidative damages leading to adverse health effects and diseases. In the past decade, mammalian species were used as models for the study of molecular biomarkers of oxidative stress caused by environmental pollutants to elucidate the mechanisms underlying cellular oxidative damage and to study the adverse effects of some environmental pollutants with oxidative potential in chronic exposure and/or sublethal concentrations. This review summarizes current knowledge and advances in the understanding of such oxidative processes in biological systems. This knowledge is extended to specific applications in aquatic organisms because of their sensitivity to oxidative pollutants, their filtration capacity, and their potential for environmental toxicology studies.

Environmental impacts of coastal aquaculture in eastern Mediterranean bays: the case of Astakos Gulf, Greece.

GOAL, SCOPE AND BACKGROUND: Over the last decade Greece has become a leading country in the EU as concerns the cage farming of seabream and seabass. A strong debate has risen, however, about the environmental impacts of aquacultures in the coastal areas. The present paper deals with this problem and it is based on measurements of physico-chemical parameters in the water column, particulate matter and sediments in the area of Astakos Gulf, a coastal embayment in western Greece where three big fish farms are currently operating. METHODS: Water samples were collected by using Hydro-Bios sampling bottles, whereas a prototype sediment trap was installed under a fish cage for the collection of particulate matter. Temperature, dissolved oxygen, pH and salinity were measured in situ using portable equipment. Nutrients were determined by standard spectrophotometric methods. Trace metals were determined by Atomic Absorption Spectrometry. Dissolved organic carbon was determined by a Shimadzu 5000A carbon analyzer, whereas organic carbon in sediments was determined titrimetrically. RESULTS AND DISCUSSION: No clear eutrophication incidents have been identified, although the water column near the fish farms was enriched in nutrients and organic carbon. A sludge 'blanket' covers considerable parts of the seabed and is enriched in colloidal organic carbon and trace metals (Cd, Cu, Fe and Zn) that come from unused fish food. The biodegradation of this sludge leads to the development of anoxic conditions followed by the formation of undesirable gases, precipitation or remobilization of metals and the extinction of benthic fauna. CONCLUSION: The operation of fish farms at the coastal area of Astakos Gulf, and probably in similar Mediterranean gulfs, affects the marine environment, particularly in the vicinity of the cages. The most significant influence concerns the near-bottom water layer. The environmental impacts depend on the amount of food given to fishes, the mode of feeding, the fish density in cages, the annual production and the years of unit operation. The hydrology and the geomorphology of the area are also critical factors for its environmental quality. RECOMMENDATION AND OUTLOOK: The success of the fish-farming sector in the Mediterranean is accompanied by environmental and, in some extents, by social and marketing problems. These problems, derived from the rapid development of fish farming, can be solved only through an integrated management, using methods such as environmental impact assessment, risk assessment, economic evaluation, vulnerability assessments, resource accounting, cost-benefit analysis and outcome-based monitoring.