Characterization and evaluation of magnesite ore mining by-products of Gerakini mines (Chalkidiki, N. Greece).

The qualitative and quantitative characterization of several mining by-product samples, were collected from the magnesite mine of "Grecian Magnesite SA" company (Gerakini, Chalkidiki, North Greece), was aiming to evaluate the possibility of upgrading their refractory properties by applying thermal treatment. The concentration range of main components for the selected best qualified samples was 38.7-43 wt% for MgO, 37.5-44.1 wt% for SiO2 and 6.5-7.3 wt% for FeO. The mineralogical characterization revealed the presence of olivine, pyroxenes and serpentine, with the concentration of the latter positively correlated to LOI. Microprobe analyses clarified the presence of olivine [(Mg1.79Fe0.19Ni0.01)SiO4], consisting mainly of 90 wt% of forsterite (Mg2SiO4) and 10 wt% of fayalite (Fe2SiO4), as well as of pyroxene group minerals [(Mg0.87Fe0.08Ca0.01Cr0.01)(Si0.98Al0.04)O3], consisting mainly of 91 wt% enstatite (MgSiO3) and 9 wt% of ferrosilite (FeSiO3), respectively. The thermal treatment of the qualified samples demonstrated that at the temperature of 650-680 °C serpentine is almost totally decomposed and at the temperature of 850 °C it has been totally recrystallized to olivine and pyroxenes. At higher temperature treatment (1300 °C), it seems that there is a recrystallization process that favors the deformation of olivine and the further formation of pyroxenes, due to the excess of Si available from the initial decomposition of serpentine, while the presence of magnesite resulted to the restriction of olivine deformation through the partial capture of available Si. For increasing the olivine percentage and, subsequently, the improvement of refractory properties of this material, at temperature > 1300°C, the ideal theoretical addition dose of wt% MgO for optimizing the formation of olivine was calculated, ranging from 7.4 to 17.5 wt%. The latter calculations are reported for the first time in the literature regarding this kind of materials.

Application of powdered activated carbon (PAC) for membrane fouling control in a pilot-scale MBR system.

Membrane fouling is considered to be the most serious drawback in wastewater treatment when using membrane bioreactors (MBRs), leading to membrane permeability decrease and efficiency deterioration. This work aims to develop an integrated methodology for membrane fouling control, using powdered activated carbon (PAC), which will enhance the adsorption of soluble microbial products (SMP) and improve membrane filterability, by altering the mixed liquor's characteristics. Reversible fouling was assessed in terms of sludge filterability measurements, according to the standard time-to-filter (TTF) method, while irreversible fouling was assessed in terms of SMP removal. Results showed that the addition of PAC at the concentration of 3 g/L in the mixed liquor reduced SMP concentration and enhanced substantially the sludge filterability. Furthermore, the TTFPAC/TTFno PAC ratios were lower, than the corresponding SMPPAC./SMPno PAC ratios, indicating that the batch-mode, short-term addition of PAC promotes the reversible, rather than the irreversible fouling mitigation.

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.

Stabilization of tannery sludge by co-treatment with aluminum anodizing sludge and phytotoxicity of end-products.

A global demand for efficient re-utilization of produced solid wastes, which is based on the principles of re-use and recycling, results to a circular economy, where one industry's waste becomes another's raw material and it can be used in a more efficient and sustainable way. In this study, the influence of a by-product addition, such as aluminum anodizing sludge, on tannery waste (air-dried sludge) stabilization was examined. The chemical characterization of tannery waste leachate, using the EN 12457-2 standard leaching test, reveals that tannery waste cannot be accepted even in landfills for hazardous wastes, according to the EU Decision 2003/33/EC. The stabilization of tannery waste was studied applying different ratios of tannery waste and aluminum anodizing sludge, i.e. 50:50, 60:40, 70:30 and 80:20 ratios respectively. Subsequently, the stabilization rate of the qualified as optimum homogenized mixture of 50:50 ratio was also tested during time (7, 15 and 30days). Moreover, this stabilized product was subjected to phytotoxicity tests using the Lepidium sativum, Sinapis alba and Sorghum saccharatum seeds. The experimental results showed that aluminum anodizing sludge managed to stabilize effectively chromium and organic content of tannery waste, which are the most problematic parameters influencing its subsequent disposal. As a result, tannery waste stabilized with the addition of aluminum anodizing sludge at 50:50 ratio can be accepted in non-hazardous waste landfills, as chromium and dissolved organic carbon concentrations in the respective leachate are below the relevant regulation limits, while the stabilized waste shows decreased phytotoxicity.

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.

Monitoring the role of Mn and Fe in the As-removal efficiency of tetravalent manganese feroxyhyte nanoparticles from drinking water: An X-ray absorption spectroscopy study.

The implementation of amorphous tetravalent manganese feroxyhyte (TMFx) nanoparticles, prepared via co-precipitation synthesis, as an efficient As(V)-removal material is investigated using X-ray absorption fine structure (XAFS) spectroscopy at the Fe-, Mn- and As-K-edges. The optimum synthesis conditions and chemical composition of the TMFx adsorbent were determined by the degree of polymerization in the adsorbents' microstructure. Under synthesis into mildly acidic conditions, the change in the polymerization of the metal-oxyhydroxyl chains (metal=Fe, Mn) provides more adsorption sites at edges and corner sites in the bonding environment of Fe and Mn, respectively, thereby enhancing As uptake. After exposure to As-polluted water, similar microstructural changes related to As-bidentate and monodentate geometries are generated: As(V) preferentially occupies the high energy adsorption sites ((2)C complexes) available in the Mn-oxyhydroxyl groups and the low energy edge sites offered by Fe ((2)E complexes). It is revealed that optimum arsenic-removal by TMFx occurs into mildly acidic synthesis pH and for iron to manganese molar ratio equal to 3.

Kinetic modeling of AS(III) and AS(V) adsorption by a novel tetravalent manganese feroxyhyte.

HYPOTHESIS: The purpose of the present work is the development of a kinetic model for the adsorption of As(III) and As(V) onto tetravalent manganese feroxyhyte (δ-Fe0.75Mn0.25OOH), which have been recently proved to be very efficient adsorbent for the particular species. EXPERIMENTS: In this respect equilibrium and adsorption kinetic experiments onto this type of adsorbent for As(III) and As(V) were performed. Two sizes of adsorbate particles are tested in order to acquire better insight to the adsorption process. RESULTS: The adsorption kinetic curves cannot be described by the well-known adsorption kinetic models so a detailed model that takes into account the structure of the adsorbent particle is developed. The model parameters were extracted by the requirement of agreement between model and experimental results. The batch model developed here is necessary for the development of models for fixed bed adsorption devices in order to exploit the commercial prospects of the particular adsorbent. This work constitutes the first attempt of kinetic study and adsorption model development for the specific very promising adsorbent.

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).

Optimizing magnetic nanoparticles for drinking water technology: The case of Cr(VI).

The potential of magnetite nanoparticles to be applied in drinking water treatment for the removal of hexavalent chromium is discussed. In this study, a method for their preparation which combines the use of low-cost iron sources (FeSO4 and Fe2(SO4)3) and a continuous flow mode, was developed. The produced magnetite nanoparticles with a size of around 20 nm, appeared relatively stable to passivation providing a removal capacity of 1.8 µg Cr(VI)/mg for a residual concentration of 50 µg/L when tested in natural water at pH7. Such efficiency is explained by the reducing ability of magnetite which turns Cr(VI) to an insoluble Cr(OH)3 form. The successful operation of a small-scale system consisting of a contact reactor and a magnetic separator demonstrates a way for the practical introduction and recovery of magnetite nanoparticles in water treatment technology.

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.

Incineration of tannery sludge under oxic and anoxic conditions: study of chromium speciation.

A tannery sludge, produced from physico-chemical treatment of tannery wastewaters, was incinerated without any pre-treatment process under oxic and anoxic conditions, by controlling the abundance of oxygen. Incineration in oxic conditions was performed at the temperature range from 300°C to 1200°C for duration of 2h, while in anoxic conditions at the temperature range from 400°C to 600°C and varying durations. Incineration under oxic conditions at 500°C resulted in almost total oxidation of Cr(III) to Cr(VI), with CaCrO4 to be the crystalline phase containing Cr(VI). At higher temperatures a part of Cr(VI) was reduced, mainly due to the formation of MgCr2O4. At 1200°C approximately 30% of Cr(VI) was reduced to Cr(III). Incineration under anoxic conditions substantially reduced the extent of oxidation of Cr(III) to Cr(VI). Increase of temperature and duration of incineration lead to increase of Cr(VI) content, while no chromium containing crystalline phase was detected.

Utilization of phosphogypsum in tannery sludge stabilization and evaluation of the radiological impact.

The current global trend towards increasingly stringent environmental standards and efforts for efficient utilization and re-use of available by-products and/or wastes, favors the use of low-cost sorbent materials for the treatment of heavy metal-contaminated solid wastes. In this study, the stabilization of tannery sludge, produced from the physicochemical and biological treatment of tannery wastewaters, was examined by the addition of phosphogypsum (PG) at a ratio of 1:1. Characterization of the tannery sludge leachates showed high amounts of chromium which exceeded the acceptable level for disposal in non-hazardous waste landfills, while the dissolved organic carbon (DOC) concentrations exceeded the limits for disposal in landfills for hazardous wastes, according to the EU Decision 2003/33/EC. Leachates of the waste stabilized with PG presented chromium and DOC concentrations below the regulation limits for disposal in landfills for non-hazardous wastes. Moreover, mixing PG with tannery sludge resulted in a stabilized waste with reduced radioactivity.

Cu-Zn powders as potential Cr(VI) adsorbents for drinking water.

This work examines the possibility of applying CuZn alloys as a reducing medium for the efficient removal of hexavalent chromium from drinking water. In an effort to develop a route for producing powders of CuZn alloys under mild conditions and investigate the optimum composition for such application, a series of alloys in the form of powders were prepared, by a sequence of Cu and Zn ball-milling and low temperature annealing. Batch Cr(VI) removal tests, performed to evaluate and compare the efficiency of the products under typical natural water parameters (pH 7 and natural-like water), indicated that the best performing material have a composition around 50 wt% Cu. The dominant reduction mechanisms are both the corrosion of the alloy surface and the electron transfer to the solution. The behavior of granulated CuZn media was tested in rapid-scale column tests using the commercial KDF which verified the high potential of CuZn alloys in Cr(VI) removal. Nevertheless, Cu and Zn leaching problems should be also considered.

Equilibrium, thermodynamic and kinetic studies on biosorption of Mn(II) from aqueous solution by Pseudomonas sp., Staphylococcus xylosus and Blakeslea trispora cells.

Biosorption of Mn(II) from aqueous solutions using Pseudomonas sp., Staphylococcus xylosus and Blakeslea trispora cells was investigated under various experimental conditions of pH, biomass concentration, contact time and temperature. The optimum pH value was determined to 6.0 and the optimum biomass concentration to 1.0 g L(-1) for all types of cells. Mn(II) biosorption was found to fit better to the Langmuir model for Pseudomonas sp. and B. trispora and to Freundlich model for S. xylosus. Langmuir model gave maximum Mn(II) uptake capacity 109 mg g(-1) for Pseudomonas sp. and much lower, 59 mg g(-1) and 40 mg g(-1) for S. xylosus and B. trispora, respectively. Pseudo-second-order kinetic model was also found to be in good agreement with the experimental results. Thermodynamic parameters of the adsorption confirmed the endothermic nature of sorption process with positive heat of enthalpy, accompanied by a positive value of entropy change. Interestingly, desorption experiments by treating biomass with 0.1 M HNO(3) solution resulted to more than 88% recovery of the adsorbed Mn(II) from Pseudomonas sp. and almost 95% and 99% from S. xylosus and B. trispora cells respectively, thus indicating that Mn(II) can be easily and quantitatively recovered from biomass.