Origin of hexavalent chromium in groundwater: The example of Sarigkiol Basin, Northern Greece.

Hexavalent chromium constitutes a serious deterioration factor for the groundwater quality of several regions around the world. High concentrations of this contaminant have been also reported in the groundwater of the Sarigkiol hydrological basin (near Kozani city, NW Greece). Specific interest was paid to this particular study area due to the co-existence here of two important factors both expected to contribute to Cr(VI) presence and groundwater pollution; namely the area's exposed ophiolitic rocks and its substantial fly ash deposits originating from the local lignite burning power plant. Accordingly, detailed geochemical, mineralogical, hydro-chemical, geophysical and hydrogeological studies were performed on the rocks, soils, sediments and water resources of this basin. Cr(VI) concentrations varied in the different aquifers, with the highest concentration (up to 120µgL-1) recorded in the groundwater of the unconfined porous aquifer situated near the temporary fly ash disposal site. Recharge of the porous aquifer is related mainly to precipitation infiltration and occasional surface run-off. Nevertheless, a hydraulic connection between the porous and neighboring karst aquifers could not be delineated. Therefore, the presence of Cr(VI) in the groundwater of this area is thought to originate from both the ophiolitic rock weathering products in the soils, and the local leaching of Cr(VI) from the diffused fly ash located in the area surrounding the lignite power plant. This conclusion was corroborated by factor analysis, and the strongly positively fractionated Cr isotopes (δ53Cr up to 0.83‰) recorded in groundwater, an ash leachate, and the bulk fly ash. An anthropogenic source of Cr(VI) that possibly influences groundwater quality is especially apparent in the eastern part of the Sarigkiol basin.

Estimation of hydraulic parameters in a complex porous aquifer system using geoelectrical methods.

Geoelectrical methods have been widely used for the estimation of aquifer hydraulic properties. In this study, geoelectrical methods were applied in a lithologically and hydrochemically complex porous aquifer to estimate its porosity, hydraulic conductivity and transmissivity. For this purpose, the electrical resistivity of the aquifer as well as the electrical conductivity of the groundwater was measured in 37 sites and wells. Initially, the Archie's law was used to generate sets of cementation factor (m) and alpha (α) parameter from which the mode values of α=0.98 and m=1.75 are representative of the studied aquifer. The transmissivity of the aquifer varies from 5.1×10(-3) to 3.1×10(-5)m(2)/s, whereas the mean value of its porosity is 0.45. The hydraulic conductivity of the aquifer which was calculated according to Archie's law varies from 2.08×10(-6) to 6.84×10(-5)m/s and is strongly correlated with the pumping test's hydraulic conductivity. In contrast, the hydraulic conductivity which was calculated using Dar-Zarrouk parameters presents lower correlation with the pumping test's hydraulic conductivity. Furthermore, a relation between aquifer resistivity and hydraulic conductivity was established for the studied aquifer to enable the estimation of these parameters in sites lacking data.

Seawater intrusion mapping using electrical resistivity tomography and hydrochemical data. An application in the coastal area of eastern Thermaikos Gulf, Greece.

The aim of this study was to determine the extent and geometrical characteristics of seawater intrusion in the coastal aquifer of the eastern Thermaikos Gulf, Greece. Hydrochemical data and geoelectrical measurements were combined and supplemented to determine the hydrochemical regime of the study site in regard to seawater phenomena. Chemical analysis of groundwater was performed in 126 boreholes and fifteen electrical resistivity tomographies (ERT) were measured, whereas in two sites the ERT measurements were repeated following the wet season. The Cl(-) concentrations recorded reached 2240 mg/L indicating seawater intrusion which was also verified by ionic ratios. The ionic ratios were overlapped and a seawater intrusion map (SWIM) was produced. A significant part of the coastal aquifer (up to 150 km(2)) is influenced by seawater intrusion. The areas with the most intensive salinization are located between Nea Kallikratia-Epanomi and Aggelochori-Peraia. According to the ERTs, in the influenced areas the salinization of the aquifer exceeds 1 km toward the mainland and its depth reaches 200 m. In the area surrounding Thessaloniki airport, the ERTs revealed salinization of the upper aquifer to depths of up to 40 m, whereas the lower aquifer is uninfluenced. This abnormal distribution of seawater intrusion demonstrates the value of geoelectrical methods in the study of seawater intrusion especially in areas with limited available hydrochemical data.

Radon and radioactivity at a town overlying Uranium ores in northern Greece.

Extensive measurements of (222)Rn in the town of Xanthi in N Greece show that the part of the town overlying granite deposits and the outcrop of a uranium ore has exceptionally high indoor radon levels, with monthly means up to 1500 Bq m(-3). A large number of houses (40%) in this part of the town exhibit radon levels above 200 Bq m(-3) while 11% of the houses had radon levels above 400 Bq m(-3). Substantial interannual variability as well as the highest in Europe winter/summer ratios (up to 12) were observed in this part of the town, which consist of traditional stone masonry buildings of the late 19th-early 20th century. Measurements of (238)U and (232)Th content of building materials from these houses as well as radionuclide measurements in different floors show that the high levels of indoor radon measured in these buildings are not due to high radon emanation rates from the building materials themselves but rather due to high radon flux from the soil because of the underlying geology, high radon penetration rates into the buildings from underground due to the lack of solid concrete foundations in these buildings, or a combination thereof. From the meteorological variables studied, highest correlation with indoor (222)Rn was found with temperature (r(2) = 0.65). An indoor radon prognostic regression model using temperature, pressure and precipitation as input was developed, that reproduced indoor radon with r(2) = 0.69. Hence, meteorology is the main driving factor of indoor radon, with temperature being the most important determinant. Preliminary flux measurements indicate that the soil-atmosphere (222)Rn flux should be in the range 150-250 Bq m(-2) h(-1), which is in the upper 10% of flux values for Europe.

Geogenic Cr oxidation on the surface of mafic minerals and the hydrogeological conditions influencing hexavalent chromium concentrations in groundwater.

This study aims to specify the source minerals of geogenic chromium in soils and sediments and groundwater and to determine the favorable hydrogeological environment for high concentrations of Cr(VI) in groundwaters. For this reason, chromium origin and the relevant minerals were identified, the groundwater velocity was calculated and the concentrations of Cr(VI) in different aquifer types were determined. Geochemical and mineralogical analyses showed that chromium concentrations in soils and sediments range from 115 to 959 mg/kg and that serpentine prevails among the phyllosilicates. The high correlation between chromium and serpentine, amphibole and pyroxene minerals verifies the geogenic origin of chromium in soils and sediments and, therefore, in groundwater. Manganese also originates from serpentine, amphibole and pyroxene, and is strongly correlated with chromium, indicating that the oxidation of Cr(III) to Cr(VI) is performed by manganese-iron oxides located on the surface of Cr-Mn-rich minerals. Backscattered SEM images of the soils revealed the unweathered form of chromite grains and the presence of Fe-Mn-rich oxide on the outer surface of serpentine grains. Chemical analyses revealed that the highest Cr(VI) concentrations were found in shallow porous aquifers with low water velocities and their values vary from 5 to 70 µg/L. Cr(VI) concentrations in ophiolitic complex aquifers ranged between 3 and 17 µg/L, while in surface water, karst and deeper porous aquifers, Cr(VI) concentrations were lower than the detection limit of 1.4 µg/L.

Occurrence of Cr(VI) in drinking water of Greece and relation to the geological background.

This study provides a survey on potential Cr(VI) exposure attributed to drinking water in Greece. For this reason, a wide sampling and chemical analysis of tap waters from around 600 sites, supplied by groundwater resources, was conducted focusing on areas in which the geological substrate is predominated by ultramafic minerals. Results indicate that although violations of the current chromium regulation limit in tap water are very rare, 25% of cases showed Cr(VI) concentrations above 10 µg/L, whereas Cr(VI) was detectable in 70% of the samples (>2 µg/L). Mineralogy and conditions of groundwater reservoirs were correlated to suggest a possible Cr(VI) leaching mechanism. Higher Cr(VI) values are observed in aquifers in alluvial and neogene sediments of serpentine and amphibolite, originating from the erosion of ophiolithic and metamorphic rocks. In contrast, Cr(VI) concentration in samples from ophiolithic and metamorphic rocks was always below 10 µg/L due to both low contact time and surface area, as verified by low conductivity and salt concentration values. These findings indicate that under specific conditions, pollution of water by Cr(VI) is favorable by a slow MnO2-catalyzed oxidation of soluble Cr(III) to Cr(VI) in which manganese products [Mn(III)/Mn(II)] are probably re-oxidized by oxygen.