Abstract
This Thesis focuses on the evaluation of the present status regarding the concentrations of potentially toxic elements in surface geochemical media of dispersion and the transport mechanisms from the geosphere to biosphere at the metalliferous region of NE Chalkidiki peninsula, including the wider mining area of Stratoni village. Stratoni comprises the only case of mining and processing of sulphide ore in Greece. Currently, the Mavres Petres sulfide ore deposit is mined whereas one of the future mine development plans is the Skouries project. The aim of the present Thesis is the development of a methodology that will contribute to the environmental risk assessment by determining the origin, concentration, mobility and fate of potentially toxic elements, according to the model: source – pathway – target.Geologically, the studied area consists of the metamorphic rocks of Kerdylia and Vertiskos geotectonic units which have been intruded by Tertiary magmatic rocks. Various ore deposits are ...
This Thesis focuses on the evaluation of the present status regarding the concentrations of potentially toxic elements in surface geochemical media of dispersion and the transport mechanisms from the geosphere to biosphere at the metalliferous region of NE Chalkidiki peninsula, including the wider mining area of Stratoni village. Stratoni comprises the only case of mining and processing of sulphide ore in Greece. Currently, the Mavres Petres sulfide ore deposit is mined whereas one of the future mine development plans is the Skouries project. The aim of the present Thesis is the development of a methodology that will contribute to the environmental risk assessment by determining the origin, concentration, mobility and fate of potentially toxic elements, according to the model: source – pathway – target.Geologically, the studied area consists of the metamorphic rocks of Kerdylia and Vertiskos geotectonic units which have been intruded by Tertiary magmatic rocks. Various ore deposits are strongly related to the Tertiary intrusive bodies including the Madem Lakkos and Mavres Petres Pb-Zn-Ag orebodies, Piavitsa mixed sulphide and manganese ore deposits and the porphyry Cu-Au deposits in Skouries and Fisoka areas.Streams are originating from the Stratonikon Mountain, which is located northwards of the Stratoni village and follow a general N-S direction. The three main streams that are investigated are flowing within the sub-basins of Piavitsa, Kerasia and Kokkinolakkas (named from west to east). They all discharge their water in Asprolakkas stream which has an E-W direction flowing towards the north part of Ierissos Gulf.The methodology that was followed included the selection of 13 sampling stations covering the three catchment basins. In each sampling station, surface waters and stream sediments were collected while aquatic organisms were also collected from specific sites.The chemical analyses of water samples showed that each of the studied basin presents its own hydrogeochemical features as a result of separate geological and mineralogical characteristics, as well as geochemical processes. In particular, Kokkinolakkas stream water is characterised by elevated concentrations of Ca, Mg and SO4, and metals and metalloids such as Pb (4-64 κg/l), Zn (290-1350 κg/l), Mn (1680-7899 κg/l), Ni (12-50 κg/l), Cd (2-8 κg/l), As (8-45 κg/l) and Sb (9-16 κg/l), as a result of the dissolution of gangue and sulphide minerals of the Madem Lakkos and Mavres Petres ore deposits, occurring upstream of the sampling points. Concentrations of these chemical parameters usually exceed the parametric values set by the European Union for the quality of water intended to be used for human consumption. Additionally, Mn levels are higher than the permissible environmental limit of 2 mg/l for surface waters intended to be used for irrigation, set for Chalkidiki Prefecture.As far as Kokkinolakkas stream water is concerned, colloids and suspended matter represent an important transportation pathway for Pb, and to a lesser extent for other potentially toxic elements like As, Cu, Zn and Sb. On the contrary, Mn, Ni, Mo, Co as well as Zn and Sb are mainly transported as free ions, presenting the highest correlation coefficients with the electrical conductivity of the water samples.Surface waters from Piavitsa present a significantly better chemical qualitative status with specific water samples being characterised by concentrations higher than the European Union limits for K (1-13 mg/l), Sb (0,5-9 κg/l), as well as Pb (2-45 κg/l), Mn (5-106 κg/l) and As (4-141 κg/l) for various sampling locations. Surface water from Tsarkia Lakkos, located upstream in Piavitsa basin, systematically show the highest As values among all the samples of the studied area. Downstream of this basin, concentrations of As have beenVdiluted but are still maintained to high levels. Water samples from Kerasia catchment area present lower concentrations of major ions in relation to Piavitsa basin, and only Pb (2-33 κg/l) and As (7-42 κg/l) show elevated values. Arsenic seems to be the most important environmental problem, regarding the surface water chemistry of Kerasia and Piavitsa. The elevated concentrations of As can be attributed to the competitive behaviour between this metalloid and bicarbonate ions for filling in available absorption space on Fe(III) oxides. Furthermore, As is well known for its higher mobility compared to metals under the near neutral – slightly alkaline pH conditions prevailing in Kerasia and Piavitsa stream waters.The collection of water samples during all the seasons of a hydrologic year revealed that major ion content is lower in the wet period as a result of dilution caused by the heavy rainfall during those months. On the other hand, heavy metal and metalloid concentrations of Kokkinolakkas surface water reach maximum values at the same period due to the enhanced dissolution of sulphide minerals associated with the primary mineralization, resulting to a "flush" of contamination downstream.The collected stream sediment samples were characterised mineralogically by XRD and SEM-EDS methods. According to the XRD results, all collected stream sediment samples show similar mineralogical composition consisting of quartz, feldspar (albite/anorthite) and amphibole (actinolite) as the main silicate minerals, and clinochlore, illite and montmorillonite as minor clay minerals. Calcite was only detected in one sample from Kokkinolakkas stream. Additionally, SEM-EDS results for representative samples revealed the presence of various manganiferous and sulfide minerals at Tsarkia Lakkos sediments, whereas sediments in Kokkinolakkas stream are dominated by metallic sulfide grains of the primary mineralization occurring at Madem Lakkos and Mavres Petres areas. Also, retained filters from surface water samples of Kokkinolakkas and Kerasia basins were examined under the scanning electron microscope. Results showed that particulate material from both basins is characterized by grains of Fe and S, enriched in Pb, As and Zn, whereas filters from Kokkinolakkas stream comprise oxidized particles of Pb (size <3 κm) and to al lesser extent of Fe and S, often containing traces of Zn, Cu, As and Sb.Regarding the chemical analyses of stream sediments, samples from Kokkinolakkas and Tsarkia Lakkos sites are characterised by Pb (1165-3439 mg/kg), Zn (1368-4538 mg/kg), Mn (6811 up to >10000 mg/kg), Cd (3,8-21,6 mg/kg), As (964-2714 mg/kg) and Sb (30-70 mg/kg) concentrations higher than both the world average range in soil composition and the median values reported for soils of the wider Stratoni area. Stream sediments from the other locations present lower metal levels in comparison with the previously mentioned sites, but Pb (68-320 mg/kg), Zn (73-476 mg/kg), As (42-220 mg/kg) and Sb (up to 10 mg/kg) values are usually higher than the world average range in soil composition, reflecting the elevated geochemical background of the studied area. In contrast, Cu (30-349 mg/kg), Co (9-36 mg/kg), Ni (47-242 mg/kg) and Cr (38-319 mg/kg) levels for all the collected sediments do not present significant spatial variation and are similar to the world average range, indicating that there are no significant sources of contamination for these elements. The only exception is Karatza Lakkos stream sediment which has a notable Cu concentration (349 mg/kg) higher than both the average range in soils and the median value of 104 mg/kg reported for the Stratoni area, being influenced by the porphyry copper mineralization occurring in nearby Skouries.Despite the high total metal content of stream sediments, the results of sequential extraction procedure for representative stream sediment samples revealed that the majority of the analyzed chemical elements (Pb, Zn, Mn, Cu, Ni, Cr) are mainly bound to the operationally defined geochemical phase of amorphous – poorly crystalline Fe and Mn oxides and the residual fraction. The exchangeable and the carbonate/specifically adsorbed phases, which are considered to be the most bioavailable, are of minor importance for all the metals apart from Cd which is characterized by high bioaccesibility. However, elevated concentrations of Pb, Zn and Mn were measured in the carbonate form at Kokkinolakkas stream sediments, indicating the potential release of these metals under acidic conditions.VIThe results of chemical analyses of tadpoles that live in the aquatic environment of Piavitsa and Kerasia basins showed that these organisms significantly accumulate elevated levels of metals, but they tend to concentrate Zn and Cd to a greater extent than the other metals i.e. Pb, Mn, Cu, Ni, Cr and As, in relation to the concentrations present in the sediments. Tadpoles that live in the studied area show considerably higher concentrations of Pb, Zn, Mn and As in comparison to those that live in a stream located at Varvara, which were considered as reference samples. It is remarkable that concentrations of Zn (494-2029 mg/kg), Mn (1621-13306 mg/kg), As (56-659 mg/kg), Cr (38-118 mg/kg) and Cd (3,8-6,6 mg/kg) in the tissue of tadpoles increase with increasing concentrations in the stream sediments. The highest measured levels of Pb (103-554 mg/kg) in tadpoles are also in accordance with the highest concentrations of this element in sediments between the sites where organisms were collected.The methodology that was applied and was based on the determination of concentrations of potentially toxic elements in surface waters, sediments and tissue of tadpoles represents a reliable and effective approach for the environmental risk assessment of the examined mining area. The results from this research are considered very significant providing valid scientific data for the present qualitative status of Asprolakkas hydrological basin and are available for any future comparison.Bearing in mind the future mine developments at Skouries area, the results of chemical analyses of surface waters and stream sediments of Piavitsa basin are proposed to be used for the application of a model related to the prediction of water quality downstream of this catchment basin. Finally, the continuous monitoring of the qualitative status of Asprolakkas stream, according to the applied methodology of this thesis, is strongly recommended
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