E. Kaprara

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.

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.

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.

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.

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.

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.

Environmentally available hexavalent chromium in soils and sediments impacted by dispersed fly ash in Sarigkiol basin (Northern Greece)

Hexavalent chromium is one of the most toxic and carcinogenic species known and can be released into the environment from several sources. In Sarigkiol basin (N Greece) the presence of Cr(VI) in soil, sediments and groundwater may originate from both natural (ophiolitic rocks and their weathering products) and anthropogenic (dispersed fly ash produced from lignite power plants) sources. In this study, the distribution of contents and origin of environmentally available Cr(VI) in soils, sediments, regoliths and fly ash of Sarigkiol basin is presented. Detailed geochemical and mineralogical studies were performed on soil samples (up to 1 m) and regoliths, while leaching tests were also applied to fresh and old fly ash samples. Leachable chromium from soil and sediment samples generally increased with depth and the highest concentrations were observed near to the power plant of Agios Dimitrios. The speciation of chromium in leachates revealed that Cr(VI) concentrations accounted for more than 96% of total Cr. Leaching tests of regoliths established that the natural contribution of Cr(VI) is up to 14 μg kg-1. Therefore, the measurement of higher concentrations (up to 80 μg kg-1) of environmentally available Cr(VI) in soils and sediments can be attributed to the impact/presence of dispersed fly ash in the soils and sediments of the same area. This was also supported by the low correlation recorded between environmentally available chromium and Cr-bearing minerals (mainly serpentine and talc). The influenced zone is located in the eastern part of the basin near the local power plant and surrounds an open conveyor belt that transfers fly ash to an open temporary storage pit. This zone overlies an unconfined porous aquifer thus explaining the elevated concentrations of Cr(VI) in groundwater (up to 120 μg L-1) previously reported in this area.

Potential application of inorganic sulfur reductants for Cr(VI) removal at sub-ppb level

AbstractIn this study, the efficiency of inorganic sulfur reductants (ISRs) for the Cr(VI) removal from drinking water at sub-ppb level was evaluated. Particularly, NaHSO3, Na2S2O3, Na2S2O4, Na2S2O5, and Na2S were examined at doses up to 50 mg S/L, which is equivalent to an increase in sulfate concentration up to 150 mg/L in the treated water. Experimental results showed that the removal efficiency is strongly influenced by solution pH. The optimum pH lies at the range 2–4 for all ISRs tested, whereas their efficiency gradually decreases due to the competition with dissolved oxygen, as reaction pH value increases from 4 to 9. At the typical for natural water pH 7, only Na2S2O4 was found capable to reduce an initial Cr(VI) concentration of 100 μg/L down to the sub-ppb level. The reaction kinetics for this reagent showed that 85% of total Cr(VI) removal was achieved within 2 h. It is important to note that at the equilibrium, reached after 8 h, sulfate concentration was safely below the drinking water regul...

The use of Sn(II) oxy-hydroxides for the effective removal of Cr(VI) from water: Optimization of synthesis parameters

The development of a novel adsorbent based on Sn(II) oxy-hydroxide nanoparticles and the optimization of main synthesis parameters was examined for the efficient removal of hexavalent chromium at low residual concentration levels. The aqueous hydrolysis of Sn(II) salts in a continuous-flow process was evaluated as an effective method to synthesize an appropriate material able to operate both as an electron donor for Cr(VI) reduction, and provide a suitable crystal structure that favors strong complexation with the formed Cr(III) species. Experimental results revealed that the main hydrolysis parameters, such as pH value and tin origin/source, can be used to determine the chemical formula of the produced materials and thereby, eventually improve their uptake capacity for Cr(VI). Among the tested sorbent materials, the synthetic nanostructured hydroromarchite, Sn6O4(OH)4, prepared by the hydrolysis of SnCl2 in a highly acidic environment (pH2), was deemed the best sorbent material and it was further investigated for its Cr(VI) uptake performance under reliable conditions (column experiments) for drinking water treatment. Specifically, Rapid Small-Scale (laboratory) Column Tests indicated that aggregates of the Sn6O4(OH)4 nanomaterial can achieve a maximum uptake capacity of around 19mg/g, keeping the levels of outflow Cr(VI) below 10μg/L during the treatment of natural-like water at pH7. The high efficiency is mainly attributed to the stabilization of Sn(II) content in nanoparticles, as well as the improved surface charge density, reaching 1.0mmol[OH-]/g, whereas the obtained thermodynamic data indicate a combined reduction-sorption process. The latter aspect was further verified by XPS, showing that even in the highly-loaded sorbent materials with adsorbed chromium, its trivalent form is the predominant one. These specific characteristics suggest that the product is a more favorable candidate for wider applications in water treatment units, regarding Cr(VI) removal, compared to other examined sorbent materials.