Manassis Mitrakas

Kilogram-scale synthesis of iron oxy-hydroxides with improved arsenic removal capacity: Study of Fe(II) oxidation–precipitation parameters

Various iron oxy-hydroxides were synthesized in a continuous flow kilogram-scale production reactor through the precipitation of FeSO(4) and FeCl(2) in the pH range 3-12 under intense oxidative conditions to serve as arsenic adsorbents. The selection of the optimum adsorbent and the corresponding conditions of the synthesis was based not only on its maximum As(III) and As(V) adsorption capacity but also on its potential efficiency to achieve the arsenic health regulation limit in NSF challenge water. As a result, the adsorbent prepared at pH 4, which consists of schwertmannite, was selected because it exhibited the highest adsorption capacity of 13 μg As(V)/mg, while maintaining a residual arsenic concentration of 10 μg/L at an equilibrium pH 7. The high surface charge and the activation of an ion-exchange mechanism between SO(4)(2-) adsorbed in the Stern layer and arsenate ions were found to significantly contribute to the increased adsorption capacity. Adsorption capacity values observed in rapid scale column experiments illustrate the improved efficiency of the qualified adsorbent compared to the common commercial arsenic adsorbents.

Inorganic engineered nanoparticles in drinking water treatment: a critical review

This review summarizes the recent research in the field of inorganic engineered nanoparticle development with direct or potential interest for drinking water treatment. The incorporation of engineered nanoparticles into drinking water treatment technologies against the removal of heavy metals, microorganisms and organic pollutants appears as a very dynamic branch of nanotechnology. Nanoparticles owe their potential to the high specific surface area and surface reactivity compared to conventional bulk materials. Depending on the mechanism of uptake, nanoparticles can be designed to establish high selectivity against specific pollutants and provide the required efficiency for application. However, despite early encouraging results, nanoparticles meet a number of limitations to get promoted and become part of large-scale water treatment plants. The most important is their availability in the required large quantities and their efficiency to fulfil the strict regulations for drinking water consumption and environmental safety. Both deal with the particle preparation cost and the cost of treatment operation with respect to the increase in supplied water price for the consumers. Under this view, this work attempts to evaluate reported studies according to their possibility to meet the reliable requirements of water technology and also suggests an experimental approach to allow validation of tested nanoparticles.

A novel approach for arsenic adsorbents regeneration using MgO

An integrated procedure for the regeneration of iron oxy-hydroxide arsenic adsorbents by granulated MgO is proposed in this study. A continuous recirculation configuration, with a NaOH solution flowing sequentially through the saturated adsorbent (leaching step) and the MgO (adsorption step) column beds, was optimized by utilizing the high arsenic adsorption efficiency of MgO at strong alkaline environments. Experimental results indicated that the total amount of leached arsenic was captured by MgO whereas the regenerated iron oxy-hydroxide recovered around 80% of its removal capacity upon reuse. The improved adsorption capacity of MgO for As(V), which is maximized at pH 10, is explained by the intermediate hydration to Mg(OH)2 and the following As(V) oxy-anions adsorption on its surface through the formation of monodentate inner sphere complexes, as it is deduced from the AsK-edge X-ray absorption fine structure (EXAFS) analysis. In addition to the economical-benefits, corresponding tests proved that the solid wastes of this process, namely spent MgO/Mg(OH)2, can be environmentally safely disposed as stable additives in cement products, while the alkaline solution is completely detoxified and can be recycled to the regeneration task.

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.

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.

Fe-based nanoparticles as tunable magnetic particle hyperthermia agents

Magnetic hyperthermia, an alternative anticancer modality, is influenced by the composition, size, magnetic properties, and degree of aggregation of the corresponding nanoparticle heating agents. Here, we attempt to evaluate the AC magnetic field heating response of Fe-based nanoparticles prepared by solar physical vapor deposition, a facile, high-yield methodology. Nanoparticle systems were grown by evaporating targets of Fe and Fe3O4 with different stoichiometry. It is observed that Fe3O4 nanoparticles residing in the magnetic monodomain region exhibit increased heating efficiency together with high specific loss power values above 0.9 kW/g at 765 kHz and 24 kA/m, compared with that of 0.1 kW/g for zero-valent Fe nanoparticles under the same conditions. The enhanced performance of Fe3O4 nanoparticles under the range of field explored (12–24 kA/m) may be attributed to the activation of a magnetic hysteresis loss mechanism when the applied AC field surpasses the particle anisotropy field at H ≥ 0.5HA. Thi...

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.

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.

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.

Comparative study of As(V) removal by ferric coagulation and oxy-hydroxides adsorption: laboratory and full-scale case studies

ABSTRACT This research attempts to evaluate the efficiency of the two main arsenic removal processes, i.e. Fe(III) coagulation and iron oxy-hydroxides adsorption, by combining laboratory-scale experiments and results from operating full-scale water treatment units, located in several places of Greece. The proposed experimental procedure showed that the removal ability of Fe(III) coagulation is proportional to the added iron salt dose and appears to be much more efficient than the adsorption process applied in columns filled with iron oxy-hydroxide solid media. Furthermore, the comparison with the results obtained from large-scale water treatment plants indicated the possibility to predict the required quantities of chemicals’ addition, or adsorbents in scaling-up the laboratory or pilot-scale systems, respectively. However, apart from the effectiveness of each method, the variation in water flow rates, the residual arsenic concentrations, and the specific requirements for operation and maintenance should ...