Manos Dassenakis

The importance of natural organic material for environmental processes in waters and soils (Technical Report)

The role and function of natural organic material (NOM) for the terrestrial and aquatic environment is strongly related to nutrient availability for plants, relevant for crop production, as well as to be a source of energy for macroand microorganisms, to influence physico-chemical conditions of soil and sediments and to buffering and exchange capacity, relevant for the immobilization and mobilization of environmental pollutants. This article will review the available information about the importance of natural organic material for environmental processes in water and soil. After explaining general terms regarding natural organic material and its chemical structure and presenting the actual state of analytical methods, interactions between environmental variables and the natural organic material as regards its formation and behaviour, as well as interactions between natural organic material and the fate of pollutants in the terrestrial and aquatic environment are discussed emphasizing some relevant processes such as sorption, mobility and bioavailability. Finally some aspects on modeling such processes are presented.

Effects of multiple source pollution on a small Mediterranean river

Abstract The small Mediterranean riverine system of the Litheos river, which flows through the city of Trikala, and its drainage area are subjected to pollution from point and non point sources,which results in poor quality of surface waters. The pollution sources include urban activities, agriculture, industrial activities, handicrafts and traffic. The concentration levels and the geochemical behaviour of nutrients, trace metals and organic pollutants were studied during the period 1991–1992, in a project supported by the Municipality of Trikala. The simultaneous existence of several polluting sources leads to significant variations in the concentrations and distributions of main pollutants, which are elevated in the neighbourhood of polluting activities in various parts of the river (NO3− above the city, NH3, NO2− and detergents near central rainwater collector, into the city, P04 below the city, near the waste water treatment plant, PAI-Is and metals in another river branch in the ‘industrial’ zone of the city). The appearance of concentration maxima of various pollutants in various parts of the river indicates environmental problems in the whole length of the river. The water quality is significantly influenced and in most cases is unsuitable for human consumption. The mean values of the main pollutants in Litheos (NO3− 4.0 mg N/1, NH3 0.23 mg N/1, NO2− 0.10 mg N/1, P 0.37 mg P/1, Cu 7.1 μg/l, Pb 4.8 μg/l, Zn 3.9 μg/l, Ni 12.8 μg/l, Cr 3.5 μg/l) characterize Litheos as a moderately polluted river, but the observation of eutrophication phenomena and the appearance of some high concentrations of heavy metals and/or organic pollutants in certain parts of the river reveal that a serious effort must be made in order to avoid further deterioration of Litheos water quality.

Trace metals transport and behaviour in the Mediterranean estuary of Acheloos river

Abstract The concentration levels and the chemical behaviour of trace metals during their transport, were studied in the estuary of the Acheloos river, in western Greece. It is a typical, non tidal and stratified Mediterranean estuary which, although is not heavily polluted, is affected by a lot of human activities (dams, agriculture, fishing, etc.) that, in combination with its hydrological and morphological characteristics, affect also the distribution of trace metals. The concentration levels of metals in the estuary are lower than in polluted Greek gulfs and rivers. In the Acheloos case, in contrast to polluted estuaries, the dissolved metal concentrations are increased seawards whereas the particulate metal concentrations and the metal content of the particles are decreased. Suspended particulate matter and especially particles having diameter

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.

The use of various methods for the study of metal pollution in marine sediments, the case of Euvoikos Gulf, Greece

This study presents the results on heavy metal (Mn, Fe, Cu, Zn) analyses of sediments taken from Euvoikos Gulf, Greece, which is a semi-enclosed system receiving pollution loads from several urban and industrial sources and is affected by a strong tidal current. A sequential extraction schema and two single-step methods were used for the determination of trace metals. The data of the 1997 period are compared with data from previous studies carried out in the authors’ laboratory in the area (1980, 1993) using various analytical techniques, in an attempt to evaluate both the evolution of pollution in the area and the effectiveness of analytical methods. It has been confirmed that a significant part of the pollution load remains in coastal localities in the vicinity of the land based pollution sources, whereas there are also some more remote sites where small polluted particles are transported, deposited and accumulated. The sedimentology regime of the area affects the concentration of metals in a rather complex way depending also on its content of carbonates, organic C and clay minerals. The study of sediment cores has indicated elevated metal concentrations in recent surface sediments. On the other hand, some environmentally positive trends were also observed (i.e. the reduction of mobile metals). A systematic monitoring is needed in the marine environment coupled with some reduction in pollution inputs and integrated management on the coastal zone because the overall hydrological characteristics of the area favour its rapid self-restoration. # 2002 Elsevier Science Ltd. All rights reserved.

Trace metals in sediments of a Mediterranean estuary affected by human activities (Acheloos river estuary, Greece)

Trace metals were studied in the sediments of the ecologically, economically and scientifically important estuary of the Acheloos river, in western Greece. Human activities (dams, agriculture, traffic, etc.) influence the estuarine system of Acheloos and in combination with the hydrological, mineralogical and morphological characteristics of the estuary affect the chemical behaviour and the distribution patterns of trace metals in its sediments. The large scale disturbance of the system is imminent in the near future as it is planned to divert approximately 50% of the river water. A study of the distribution patterns of trace metals revealed that in the estuary there are zones with different metal levels. The concentrations of most metals (Al, Fe, Cu, Ni, Zn) are elevated in three of these zones (upstream, sill, seawards). A different behaviour was observed for Mn due to its association with carbonates that were observed in significant concentrations throughout the estuarine zone. A sequential extraction procedure, applied to the sediments, indicated low percentages of easily exchangeable metals, increased mobility of Cu and Zn and increased association of Ni, Cr and Fe with the aluminosilicate lattice. Although the river is not considered to be heavily polluted, some metals have shown an enrichment in the surface sediments as a result of general anthropogenic activities not derived from point sources.

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.

Levels of perfluorinated compounds in raw and cooked Mediterranean finfish and shellfish

Perfluorinated compounds (PFCs) were analyzed in several species of small Mediterranean fish and shellfish, all of which are popular in Greek diet. Analysis was conducted in raw samples and in samples cooked by the two ways preferred in Greek cuisine, i.e. fried in olive oil and grilled. PFCs above the detection limit were found in all raw samples except sardine, mussel and squid. The predominant PFC was PFOS (perfluorooctane sulfonate), the highest concentration of which was measured in picarel (20.4 ng g(-1) fresh weight). The PFOS values for the rest of the samples were between <LOD and 5.66 ng g(-1) fw. The concentrations of the detected PFCs were in most cases higher after frying or grilling, this increase being statistically significant. Based on these results, the Tolerable Daily Intake for PFOS and PFOA (perfluorooctanoic acid) through consumption of fish and seafood was well below the values proposed by EFSA.

Chemical Characteristics of Aetoliko Lagoon, Greece, after an Ecological Shock

Abstract A series of chemical parameters were studied in the water, particulate matter and sediments of Aetoliko lagoon, a wetland in western Greece, after an ecological impact at the end of November 1990, which resulted in massive death of fish. The permanent anoxic conditions in the deeper water layer of the lagoon, with the simultaneous formation of hydrogen sulfide, are the main characteristics of the system. The dramatic reduction of the dissolved oxygen in the surface water which was substituted by the hydrogen sulfide of the near bottom water layer caused the sudden death of organisms. This phenomenon also affected the nutrients. Ammonia was the main nitrogen form; phosphates and silicates were concentrated in near bottom waters, and the concentrations of nitrates and nitrites were much lower in December than 3 months later in the surface waters. The behaviour of trace metals also indicated that in the extraordinary conditions studied, the main mechanisms of transport of metals among the main phases of the system (dissolved-particulate-sediments) were severely disturbed.

Trace metals in a tidal Mediterranean embayment

Abstract The Euvoikos gulf, and the strait of Euripos therein, is a restricted embayment on the eastern coast of Greece having a significant, unusual tidal phenomenon and receiving some domestic, trade and industrial wastes from the town of Chalkis and several coastal industries. The purpose of the present work was to study the influence of the tidal current and the anthropogenic inputs on the distributions of several trace elements (namely, Pb, Cu, Zn, Cr, Fe, Mn and Ni) in the seawaters (as dissolved and particulate species) and the sea-bottom sediments. Thorough mixing, resuspension and transport of fine particles and direct discharges are the major mechanisms affecting the distribution patterns.