Nikolaos Kantiranis

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.

Effect of in vitro aging on the flexural strength and probability to fracture of Y-TZP zirconia ceramics for all-ceramic restorations.

OBJECTIVES Dental zirconia restorations should present long-term clinical survival and be in service within the oral environment for many years. However, low temperature degradation could affect their mechanical properties and survival. The aim of this study was to investigate the effect of in vitro aging on the flexural strength of yttrium-stabilized (Y-TZP) zirconia ceramics for ceramic restorations. METHODS One hundred twenty bar-shaped specimens were prepared from two ceramics (ZENO Zr (WI) and IPS e.max(®) ZirCAD (IV)), and loaded until fracture according to ISO 6872. The specimens from each ceramic (nx=60) were divided in three groups (control, aged for 5h, aged for 10h). One-way ANOVA was used to assess statistically significant differences among flexural strength values (P<0.05). The variability of the flexural strength values was analyzed using the two-parameter Weibull distribution function, which was applied for the estimation of Weibull modulus (m) and characteristic strength (σ0). The crystalline phase polymorphs of the materials (tetragonal, t, and monoclinic, m, zirconia) were investigated by X-ray diffraction (XRD) analysis, Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. RESULTS A slight increase of the flexural strength after 5h, and a decrease after 10h of aging, was recorded for both ceramics, however statistically significant was for the WI group (P<0.05). Both ceramics presented a t→m phase transformation, with the m-phase increasing from 4 to 5% at 5h to around 15% after 10h. SIGNIFICANCE The significant reduction of the flexural strength after 10h of in vitro aging, suggests high fracture probability for one of the zirconia ceramics tested.

Spatial and seasonal variations of the chemical, mineralogical and morphological features of quasi-ultrafine particles (PM 0.49) at urban sites.

Combining chemical and physical-structural information of particles is a key issue in PM investigations. Chemical, mineralogical, and morphological characterization of quasi-ultrafine particles (PM 0.49) was carried out at two urban sites of varying traffic-influence (roadside and urban background) in Thessaloniki, northern Greece, during the cold and the warm period of 2013. Bulk analyses of chemical species included organic and elemental carbon (OC, EC), water soluble organic carbon (WSOC), ionic species (NO3(-), SO4(2-), Cl(-), Na(+), NH4(+), K(+), Mg(2+), Ca(2+)) and trace elements (As, Ba, Cd, Cr, Cu, Fe, Pb, Mn, Ni, Zn, Pt, Pd, Rh, Ru, and Ir). X-ray diffractometry (XRD) was employed for the mineralogical analysis of PM 0.49 in order to identify and quantify amorphous and crystalline phases. In addition, scanning electron microscopy coupled with energy dispersive spectrometry (SEM-EDS) was employed for morphological characterization and elemental microanalysis of individual particles. Findings of this work could provide the basis for designing epidemiological and toxicity studies to mitigate population exposure to UFPs.

Extra-framework cation release from heulandite-type rich tuffs on exchange with NH4+

The outgoing cations of Greek heulandite-rich tuff samples (heulandite type-III, 91wt.%, mica 4wt.%, feldspar 5wt. %, CEC 2.22meq/g) were analysed upon exchange with ammonium acetate using atomic absorption spectrometry (AAS). The kinetic curves of each cation were investigated over a total time of contact of 720h with sampling at frequent intervals. The materials were examined by powder X-ray diffraction, SEM-EDS, and AAS. The sorption ability was measured using the ammonium acetate saturation method. It was found that Ca(2+) presents an unexpected extra-framework release and a surprisingly high degree of exchange (90%). The exchange of Mg (57%) is also worthy of note whereas the behavior of K(+) showed an expected rapid initial release. The behavior of Na(+) must be similar. However, its lower concentration in the zeolitic material minimizes its overall significance somewhat. On the other hand, Ca(2+) and Mg(2+) release is kinetically much slower, compared to that of alkali metal ions, and this phenomenon indicates that different exchange energies are needed till final equilibrium.

Separation of Uranium from Aqueous Solutions Using Al3+‐ and Fe3+‐modified Titanium‐ and Zirconium Phosphates

Abstract The ability of four amorphous Al3+‐ and Fe3+‐doped titanium and zirconium sorbents to separate U(VI) from acidic aqueous solutions (pHinit=3, ionic strength 0.1 M established by NaNO3) was investigated using a batch technique and instrumental neutron activation analysis. All investigated sorbents were found to be chemically stable and remove considerable amounts of uranium from acidic aqueous solutions (pHinit=3). The scanning electron microscopic and powder‐X‐ray diffraction examination of the grains of the two investigated titanium phosphates after contacting the uranium solutions revealed the formation of sodium autunite (Na2(UO2)2(PO4)2 · 6‐8H2O) accompanied, in the case of the Fe3+‐doped titanium phosphate, by iron uranyl phosphate hydroxide hydrate (Fe(UO2)2(PO4)2(OH) · 7H2O). No crystal formation was observed in the cases of uranium sorbed by zirconium phosphates indicating the different sorption mechanism involved.

Effect of heat treatment and in vitro aging on the microstructure and mechanical properties of cold isostatic-pressed zirconia ceramics for dental restorations

OBJECTIVES The temperature variations during the veneering firing cycles of a zirconia dental ceramic can negatively affect its mechanical properties. A possible synergistic effect of both heat-treatment and aging while exposed to the oral environment could result to catastrophic failure. The aim of the present study was to investigate the effect of heat treatment followed during veneering and in vitro aging on the mechanical and microstructural properties of zirconia dental ceramics. METHODS Three specimens from each of two zirconia blocks (Ivoclar IPS e.max ZirCAD (IV) and Wieland ZENO Zr (WI)) were cut by CAD/CAM technology, fully sintered and polished. Each one was cut in four equal parts. One part was used as control (C), one was heat-treated (H), one was aged (A) (134°C, 2bar, 10h) and one was heat-treated and subsequently aged (HA). The mechanical properties (nano-hardness (H) and elastic modulus (E*)) were investigated by nano-indentation tests while the surface characterization was carried out with XRD, FTIR and SEM. RESULTS Different treatments on IV and WI samples resulted in a reduction of both H and E* values, however the differences were not statistically significant (p>0.05). The combination of treatments imposes an overall effect (p<0.001), enhancing the influence on both H and E* values. This reduction in mechanical properties was followed by an increase of monoclinic content. Greater variations in both H and E* values were recorded for WI samples. SIGNIFICANCE The clinical performance of zirconia dental ceramics may be affected during firing and aging resulting in increased probability of failure.

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 areas 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.

Sol-Gel Derived Mg-Based Ceramic Scaffolds Doped with Zinc or Copper Ions: Preliminary Results on Their Synthesis, Characterization, and Biocompatibility

Glass-ceramic scaffolds containing Mg have shown recently the potential to enhance the proliferation, differentiation, and biomineralization of stem cells in vitro, property that makes them promising candidates for dental tissue regeneration. An additional property of a scaffold aimed at dental tissue regeneration is to protect the regeneration process against oral bacteria penetration. In this respect, novel bioactive scaffolds containing Mg2+ and Cu2+ or Zn2+, ions known for their antimicrobial properties, were synthesized by the foam replica technique and tested regarding their bioactive response in SBF, mechanical properties, degradation, and porosity. Finally their ability to support the attachment and long-term proliferation of Dental Pulp Stem Cells (DPSCs) was also evaluated. The results showed that conversely to their bioactive response in SBF solution, Zn-doped scaffolds proved to respond adequately regarding their mechanical strength and to be efficient regarding their biological response, in comparison to Cu-doped scaffolds, which makes them promising candidates for targeted dental stem cell odontogenic differentiation and calcified dental tissue engineering.

Thermal distinction of HEU-type mineral phases contained in Greek zeolite-rich volcaniclastic tuffs

Ten zeolite-bearing rocks rich in HEU-type zeolites from Evros District and Samos island were studied. The samples were heated at 450°C for 8 h and the reductions in the intensity and the peak area of the (020) reflection was measured. Electron microscope and thermal analyses were used, as well. The results of the above methods gave an explicit picture for the HEU-type phases that exist in each sample and they led to their regrouping in three different groups: group I where the main phase of deter- mined HEU-type zeolite was clinoptilolite, group II, presenting mediate characteristics between groups I and III, where the contained main phase of HEU-type zeolite is intermediate heulandite, and group III, where heulandite is the main HEU-type zeolite phase. The combined study of the XRD results in initial and thermally treated samples, compared with the SEM-EDS results and the thermal study of the mass recovery during the cooling stage of the thermal analysis constitute a useful tool for the classification of the HEU-type zeolites in their different phases.

Study of the Bioactive Behavior of Thermally Treated Modified 58S Bioactive Glass

Thermal treatment of bioactive glasses can affect their microstructure and thus their bioactivity. The aim of this study was the characterization of the thermally treated sol-gel-derived bioactive glass 58S at characteristic temperatures and the dependence of its bioactive behavior on the specific thermal treatment. The thermal behavior of the bioactive glass was studied by thermal analysis (TG/DTA). Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Diffractometry (XRD) were used for the characterization of the bioactive glass. The bioactive behavior in Simulated Body Fluid (SBF) was examined by Scanning Electron Microscopy (SEM-EDS) and FTIR. The major crystal phases after thermal treatment were Calcium Silicates, Wollastonite and Pseudowollastonite, while all thermally treated samples developed apatite after 48 hours in SBF. A slight enhancement of bioactivity was observed for the samples heated at the temperature range 910-970oC.