F. Pinakidou

Tetravalent manganese feroxyhyte: a novel nanoadsorbent equally selective for As(III) and As(V) removal from drinking water.

The development of a single-phase Fe/Mn oxy-hydroxide (δ-Fe0.76Mn0.24OOH), highly efficient at adsorbing both As(III) and As(V), is reported. Its synthesis involves the coprecipitation of FeSO4 and KMnO4 in a kilogram-scale continuous process, in acidic and strongly oxidizing environments. The produced material was identified as a manganese feroxyhyte in which tetravalent manganese is homogeneously distributed into the crystal unit, whereas a second-order hollow spherical morphology is favored. According to this structuration, the oxy-hydroxide maintains the high adsorption capacity for As(V) of a single Fe oxy-hydroxide combined with enhanced As(III) removal based on the oxidizing mediation of Mn(IV). Ion-exchange between arsenic species and sulfates as well as the strongly positive surface charge further facilitate arsenic adsorption. Batch adsorption tests performed in natural-like water indicate that Mn(IV)-feroxyhyte can remove 11.7 μg As(V)/mg and 6.7 μg As(III)/mg at equilibrium pH 7, before residual concentration overcomes the regulation limit of 10 μg As/L for drinking water. The improved efficiency of this material, its low cost, and the possibility for scaling-up its production to industry indicate the high practical impact and environmental importance of this novel adsorbent.

Identification of implantation-induced defects in GaN: A near-edge x-ray absorption fine structure study

We apply near-edge x-ray absorption fine structure spectroscopy, at the N K edge, in order to identify the signature of implantation-induced defects in the partial density of empty states in GaN implanted with O, Mg, and Si ions. The dose range was 1014–1018 cm−2. It is found that two of the implantation-induced defects introduce characteristic resonances (hereafter called RL1 and RL2) in the near-edge x-ray absorption fine structure spectra. RL1 appears 1.7 eV below the absorption edge, its formation is independent of the projectile and the implantation dose, and is attributed to nitrogen interstitials. RL2, which appears at about 1.0 eV above the absorption edge, is generated when the dose exceeds 1016 cm−2 and is attributed to nitrogen dangling bonds.

Optimization of tetravalent manganese feroxyhyte's negative charge density: A high-performing mercury adsorbent from drinking water

This study demonstrates an optimization procedure for the development of an Hg-specified adsorbent able to comply with the regulation limit for drinking water of 1μg/L. On this purpose, the synthesis of Mn(IV)-feroxyhyte was modified to achieve high negative charge density by combining alkaline and extreme oxidizing conditions. In particular, precipitation of FeSO4 at pH9 and excess of KMnO4 follows a very fast nucleation step providing a product with very small nanocrystal size (1-2nm), high specific surface area (300m2/g) and maximum negative charge density (1.8mmol H+/g). The adsorbent was validated for Hg removal in batch experiments and column tests using natural-like water indicating an adsorption capacity as high as 2.5μg/mg at equilibrium concentration 1μg/L under reliable conditions of application. Importantly, the adsorption is an exothermic spontaneous process, resulting in the formation of inner sphere complexes by sharing both A-type and B-type oxygen atoms with the metal surface octahedral as revealed by the X-ray absorption fine structure results.

An X-ray absorption study of synthesis- and As adsorption-induced microstructural modifications in Fe oxy-hydroxides.

Synthetic adsorbents based on Fe oxy-hydroxides (FeOOH) prepared under a wide range of pH-values via intense oxidation conditions of FeSO4 as well as the As(III) and As(V) adsorption mechanism are investigated using X-ray absorption fine structure (XAFS) spectroscopies at the Fe- and As-K-edges. Synthesis in an alkaline environment promotes the face-connectivity of the Fe(O,OH)6 chains at the expense of edge- and corner-sharing linkage, which is consistent with the lower surface charge density and in turn with the lower arsenic adsorption capacity. Microstructural changes are also detected after As(V) adsorption onto FeOOH synthesized at pH 5.5: the ratio of face-/edge-sharing sites increases from approximately 0.4-0.7 as a function of the As(V)-loading. This modification of the polymeric Fe(O,OH)6 structure at higher As/Fe ratios is attributed to strong As(V) bidentate mononuclear ((2)E) and binuclear ((2)C) adsorption. In contrast, no alterations in the FeOOH microstructure were observed, possibly due to the weaker (2)E linkage of As(III).

A XAFS study of plain and composite iron(III) and chromium(III) hydroxides

Reduction of hexavalent Cr(VI) to the trivalent state is the common strategy for remediation of Cr(VI) contaminated waters and soils. In the presence of Fe the resulting compounds are usually mixed Fe(III)-Cr(III) phases, while, under iron-free conditions, reduction leads to formation of plain Cr(III) hydroxides. Environmental stability of these compounds depends on their structure and is important to understand how different precipitation conditions affect the local atomic order of resulting compounds and thus their long term stability. In current study, typical Cr(VI) environmental remediation products, i.e. plain and mixed Fe(III)-Cr(III) hydroxides, were synthesized by hydrolysis and redox reactions and their structure was studied by X ray diffraction and X ray absorption fine structure techniques. Plain Cr(III) hydroxide was found to correspond to the molecular formula Cr(OH)3·3H2O and was identified as crystalline in XRD. However, the same compound when examined by EXAFS did not exhibit any clear local order in the range of EXAFS detectable distances, i.e. between 0 and 5Å. Namely, EXAFS spectroscopy detected only contribution from the first nearest neighboring (Cr-O) shell, suggesting that CrO6 octahedra interconnection is loose, in accordance with the suggested anti-bayerite structure of this compound. Mixed Fe(III)-Cr(III) systems resembled 2-line ferrihydrite irrespective of the synthesis route. Analysis of Fe-K-EXAFS and Cr-K-EXAFS spectra indicated that FeO6 octahedra are bonded by sharing both edges and corners, while CrO6 octahedra seem to prefer edge sharing linkage. EXAFS data also suggest that Fe-Cr hydroxide produced by hydrolysis presents a better arrangement of CrO6 octahedra compared to the redox product.

XAFS characterization of buried SixNyOz samples

The microstructure and the near edge X-ray absorption fine structure (NEXAFS) signature of defect states in buried silicon oxynitrides is studied, as a function of the film composition, using extended X-ray absorption fine structure (EXAFS) and NEXAFS measurements at the N- and O-K edges. The films were fabricated by ion implantation of N2O+ into Si substrates. The NEXAFS spectra are characterized by two resonance lines, which appear 1.2 eV below and 0.5 eV above the N-K absorption edge, respectively. Based on the NEXAFS analysis results we propose that the first resonance line is attributed to the N pair defect while the second one, which is characteristic of N-rich samples, to N-dangling bonds. The EXAFS measurements reveal that the Si–O distance is constant and independent of the N concentration while the Si–N distance decreases with increasing oxygen content. In addition to that, regions of partially reacted Si (designated a-Si:N) are detected in samples were the (N/O) ratio exceeds the value of 2. Contrary to that, the mechanism of formation of the a-Si:N islands is inhibited as the oxygen concentration increases and the corresponding (N/O) ratio is less than 2.

Sn(II) oxy-hydroxides as potential adsorbents for Cr(VI)-uptake from drinking water: An X-ray absorption study

The feasibility of implementing a Sn(II) oxy-hydroxide (Sn6O4(OH)4) for the reduction and adsorption of Cr(VI) in drinking water treatment was investigated using XAFS spectroscopies at the Cr-K-edge. The analysis of the Cr-K-edge XANES and EXAFS spectra verified the effective use of Sn6O4(OH)4 for successful Cr(VI) removal. Adsorption isotherms, as well as dynamic Rapid Small Scale Test (RSSCT) in NSF water matrix showed that Sn6O4(OH)4 can decrease Cr(VI) concentration below the upcoming regulation limit of 10μg/L for drinking water. Moreover, an uptake capacity of 7.2μg/mg at breakthrough concentration of 10μg/L was estimated from the RSSCT, while the residual Cr(VI) concentration ranged at sub-ppb level for a significant period of the experiment. Furthermore, no evidence for the formation of Cr(OH)3 precipitates was found. On the contrary, Cr(III)-oxyanions were chemisorbed onto SnO2, which was formed after Sn(II)-oxidation during Cr(VI)-reduction. Nevertheless, changes in the type of Cr(III)-inner sphere complexes were observed after increasing surface coverage: Cr(III)-oxyanions preferentially sorb in a geometry which combines both bidentate binuclear ((2)C) and monodentate ((1)V) geometries, at the expense of the present bidentate mononuclear ((2)E) contributions. On the other hand, the pH during sorption does not affect the adsorption mechanism of Cr(III)-species. The implementation of Sn6O4(OH)4 in water treatment technology combines the advantage of rapidly reducing a large amount of Cr(VI) due to donation of two electrons by Sn(II) and also the strong chemisorption of Cr(III) in a combination of the (2)C and (1)V configurations, which enhances the safe disposal of spent adsorbents.

Study of fossil bones by synchrotron radiation micro-spectroscopic techniques and scanning electron microscopy

Earlymost Villafranchian fossil bones of an artiodactyl and a perissodactyl from the Milia excavation site in Grevena, Greece, were studied in order to evaluate diagenetic effects. Optical microscopy revealed the different bone types (fibro-lamellar and Haversian, respectively) of the two fragments and their good preservation state. The spatial distribution of bone apatite and soil-originating elements was studied using micro-X-ray fluorescence (µ-XRF) mapping and scanning electron microscopy. The approximate value of the Ca/P ratio was 2.2, as determined from scanning electron microscopy measurements. Bacterial boring was detected close to the periosteal region and Fe bearing oxides were found to fill bone cavities, e.g. Haversian canals and osteocyte lacunae. In the perissodactyl bone considerable amounts of Mn were detected close to cracks (the Mn/Fe weight ratio takes values up to 3.5). Goethite and pyrite were detected in both samples by means of metallographic microscopy. The local Ca/P ratio determined with µ-XRF varied significantly in metal-poor spots indicating spatial inhomogeneities in the ionic substitutions. XRF line scans that span the bone cross sections revealed that Fe and Mn contaminate the bones from both the periosteum and medullar cavity and aggregate around local maxima. The formation of goethite, irrespective of the local Fe concentration, was verified by the Fe K-edge X-ray absorption fine structure (XAFS) spectra. Finally, Sr K-edge extended XAFS (EXAFS) revealed that Sr substitutes for Ca in bone apatite without obvious preference to the Ca1 or Ca2 unit-cell site occupation.

On the Nanostructure of Cu in TixCu1-x and TiN/Cu Films: A XAFS Study

The effect of chemical composition on the bonding environment of Cu, in a series of Ti1-x Cux and TiN/Cu films, is studied using X-Ray Absorption Spectroscopies (XAFS) at the Cu-K-edge. The EXAFS analysis reveals that in all studied samples Cu is amorphous. However, its bonding environment depends on the chemical composition. More specifically, in the Ti1-xCux films, Cu is coordinated with Ti and Cu and belongs both to intermetallic TiCu and to an amorphous Cu matrix. The coordination number of Cu, i.e., the sum of Ti and Cu first neighbours, increases systematically from 6.3 ± 0.7 to 10.6 ± 0.9 when the Cu content increases from 24.1 to 52.7 at%. On the contrary, in the TiN/Cu films, the type of atoms that consists the 1st nearest neighbour shell of Cu varies as a function of the Cu concentration. More specifically, in the TiN/Cu film with the lowest Cu content (27.3 at%), intermetallic TiCu is detected. At intermediate Cu concentration (37.8 at%), Cu is bonded to both Ti and Cu atoms. Finally, in the TiN/Cu film with the highest Cu content (67.7 at%), Cu is metallic.

Modification of the N bonding environment in GaN after high-dose Si implantation: An x-ray absorption study

The microstructure and electronic structure of epitaxially grown GaN, that has been subjected to high-dose Si implantation, is studied using x-ray absorption fine structure (XAFS) spectroscopy. More specifically, XAFS is used to probe the formation of N–Si bonds and to study the implantation induced distortions in the lattice. The analysis of the extended XAFS spectra reveals that implantation with 100keV Si ions with a fluence equal to 1×1018cm−2 renders the material amorphous and promotes the formation of Si–N bonds with a bond length equal to that corresponding in Si3N4. In addition to that, the N–Ga distances increase by ∼5% due to the lattice expansion caused by the incorporation of the Si ions and the formation of point and extended defects. The absence of long or midrange order is also verified by the near edge XAFS (NEXAFS) spectra where the characteristic peaks are smeared out. However, a characteristic sharp resonance line, that appears about 1eV above the absorption edge, indicates the existenc...