Implementing magnetically-active Sn-based nanocomposites in hexavalent chromium removal from drinking water.

A novel nanocomposite consisting of Fe3O4-loaded tin oxyhydroxy-chloride is demonstrated as an efficient adsorbent for the removal of hexavalent chromium in compliance to the new drinking water regulation. This study introduces a continuous-flow production of the nanocomposite through the separate synthesis of (i) 40 nm Fe3O4 nanoparticles and (ii) multilayered spherical arrangements of a tin hydroxy-chloride identified as abhurite, before the application of a wet-blending process. The homogeneous distribution of Fe3O4 nanoparticles on the abhurite's morphology, features nanocomposite with magnetic response whereas the 10 % loaded nanocomposite preserves a Cr(VI) uptake capacity of 7.2 mg/g for residual concentrations below 25 µg/L. Kinetic and thermodynamic examination of the uptake evolution indicates a relative rapid Cr(VI) capture dominated by interparticle diffusion and a spontaneous endothermic process mediated by reduction to Cr(III). The efficiency of the optimized nanocomposite was validated in a pilot unit operating in a sequence of a stirring reactor and a rotary magnetic separator showing an alternative and competitive application path than typical fixed-bed filtration, which is supported by the absence of any acute cellular toxicity according to human kidney cell viability tests.

Anaerobic digestion biogas upgrading using a two-stage membrane system under pilot-scale conditions.

In the present work, the construction, and operation of a pilot-scale biogas upgrading system is presented, employing 2 commercial polyimide (PI) membranes. The Upgrading system treats biogas produced via anaerobic digestion of the sludge, produced from the treatment of municipal wastewater in the facilities of Thessaloniki's Wastewater Treatment Plant. The goal of the separation unit is the production of high purity biomethane (>95%) for potential reuse in terms of energy. The fabrication of the pilot scale system includes the scale up of a laboratory setup separating CO2 from binary CH4-CO2 gas mixture. After the stability tests of the process, for the operation of 5 months (February to June 2023) the purity and recovery of CH4 in the final gas product. The experimental results showed an average recovery of CH4 of 95.7% for an average 55% feed composition, whereas the average purity in the final product was equal to 82.4%. The purity results were lower because of the N2 presence in the product stream (average 17.5%). After normalization with the help of the lab-scale binary results, the expected results assuming N2 absence would be 99.8% CH4 purity and 67% CH4 recovery. Finally, 3 different membrane configurations are compared in terms of their energy production, concluding to the efficiency of 2-stage configuration with recycling stream for the optimal combination of theoretical stage cut fractions.

Evaluation of polymeric membranes' performance during laboratory-scale experiments, regarding the CO2 separation from CH4.

The present study evaluates the separation performance of a commercially available polymeric membrane, when employed for the upgrade of biogas to enrich CH4 from a simulated binary gas mixture. For this purpose, a laboratory-scale membrane set-up device has been designed and assembled, aiming to achieve the production of high purity biomethane (>95%) with simultaneous recycling and utilization of the (considered as) waste CO2 stream. The examined membrane is a polysulfone (PSF) hollow fiber (HF) one, applied in counter-current flow. The feed concentration of gases consisted between 55-70 vol% and 45-30 vol%, regarding CH4 and CO2 respectively, whereas the effect of retentate pressure was studied in the range between 0.7 and 1.5 bars. The experimental results reveal that the concentration of CH4 in the retentate stream can exceed the target value of 95%, when the applied pressure values are above the limit of 1 bar. Any increase in the feed pressure can lead also to higher CH4 purity on the retentate side, however the retentate mass flow decreases, leading to smaller recovery values of CH4. A significant increase in the CH4 purity is observed, when the CH4 recovery drops below 40%, suggesting the need for the application of multiple membrane modules, operating in series. Regarding the CO2 concentration in the permeate stream, its percentages range between 30 and 50%, which are not considered as sufficient to permit immediate reuse, whereas the need of extra membrane modules to improve the purity of gas streams is confirmed.

The origin of Uranium in groundwater of the eastern Halkidiki region, northern Greece.

Uranium (U) pollution in groundwater has become a serious problem worldwide. Even in low concentrations, U has both radiological and toxicological impacts on human health. In this study an integrated hydrogeological approach was applied to conceptualize an aquifer system, and determine the origin of U detected in the aquifer of the eastern Halkidiki region in northern Greece. Data from measurements of groundwater level and hydrochemical and stable isotope analyses of groundwater samples were applied to perform geochemical modeling and multivariate statistical analysis. The modeling and statistical analysis identified three hydrogeochemical groups within the studied hydro-system, and U(VI) as the dominant U species. The first group is linked to the deeper aquifer which is characterized by water-rock interactions with weathering products of granodiorite. In this group the dominant U species is uranyl phosphate and U concentration is 3.7 µg/L. The upper aquifer corresponds to the second hydrogeochemical group where U concentrations are mainly influenced by high concentrations of nitrogen species (NO3- and NO2-). Factor analysis further discriminated the upper aquifer into a saline coastal zone and an inland zone impacted by agricultural activities. The third hydrogeochemical group presents the highest concentration of U (up to 15 µg/L) in groundwater and corresponds to the internal aquifer system. The U within this system is triggered by the presence of Mn2+, while the long residence time of the groundwater contributes synergistically to the hydrogeochemical process. Manganese triggers U oxidation in parallel with Fe2+ precipitation that acts as a regulator of U concentration. Groundwater depletion of the upper aquifers promotes the up-coning of geothermal fluids from fault zones leading to increased concentrations of U in the mid-depth aquifers.

Membrane Fouling Controlled by Adjustment of Biological Treatment Parameters in Step-Aerating MBR.

A promising solution for membrane fouling reduction in membrane bioreactors (MBRs) could be the adjustment of operating parameters of the MBR, such as hydraulic retention time (HRT), food/microorganisms (F/M) loading and dissolved oxygen (DO) concentration, aiming to modify the sludge morphology to the direction of improvement of the membrane filtration. In this work, these parameters were investigated in a step-aerating pilot MBR that treated municipal wastewater, in order to control the filamentous population. When F/M loading in the first aeration tank (AT1) was ≤0.65 ± 0.2 g COD/g MLSS/d at 20 ± 3 °C, DO = 2.5 ± 0.1 mg/L and HRT = 1.6 h, the filamentous bacteria were controlled effectively at a moderate filament index of 1.5-3. The moderate population of filamentous bacteria improved the membrane performance, leading to low transmembrane pressure (TMP) at values ≤ 2 kPa for a great period, while at the control MBR the TMP gradually increased reaching 14 kPa. Soluble microbial products (SMP), were also maintained at low concentrations, contributing additionally to the reduction of ΤΜP. Finally, the step-aerating MBR process and the selected imposed operating conditions of HRT, F/M and DO improved the MBR performance in terms of fouling control, facilitating its future wider application.

Effect of Operating Conditions on Membrane Fouling in Pilot-Scale MBRs; Filaments Growth, Diminishing Dissolved Oxygen and Recirculation Rate of the Activated Sludge.

This is the first study that examines the effect of operating conditions on fouling of Membrane Bio-Reactors (MBRs), which treat municipal wastewater in field conditions, with specific regard to the controlled development of filamentous microorganisms (or filaments). The novelty of the present work is extended to minimize the dissolved oxygen (DO) in recirculated activated sludge for improving the process of denitrification. For this purpose, two pilot-scale MBRs were constructed and operated in parallel: i) Filament-MBR, where an attempt was made to regulate the growth of filaments by adjustment of DO, the Food-to-Microorganisms (F/M) ratio and temperature, and ii) Control-MBR, where a gentle stirring tank was employed for the purpose of zeroing the DO in the recycled sludge. Results showed that low temperature (< 15 °C) slightly increased the number of filaments in the Filament-MBR which, in turn, decreased the Trans-Membrane Pressure (TMP). As the Soluble Microbial Products (SMP) and the colloids are considered to be the basic foulants of membranes in MBR systems, specific attention was directed to keep their concentration at low values in the mixed liquor. The low F/M ratio in the aeration tanks which preceded the membrane tank was achieved to keep the SMP proteins and carbohydrates at very low values in the mixed liquor, i.e., less than 6 mg/L. Moreover, as a result of the low recirculation rate (2.6∙Qin), good aggregation of the produced excess sludge was achieved, and low concentration of colloids with a size ≤50 nm (nearly the membranes' pore size used for filtration/separation) was measured, accounted for maximum 15% of the total colloids. Additionally, the increase in filamentous population at the Filament-MBR contributed to the further reduction of colloids in the mixed liquor at 7.9%, contributing beneficially to the reduction of TMP and of membrane fouling. The diminishing of DO in the recirculated sludge improved denitrification, and resulted in lower concentrations of Ν-NO3- and TN in the effluent of the Control-MBR. Furthermore, the recirculation rate of Qr = 2.6∙Qin, in comparison with Qr = 4.3∙Qin, resulted in improved performance regarding the removal of N-NH4+. Finally, high organics removal and ammonium nitrification was observed in the effluent of both pilots, since COD and Ν-ΝΗ4+ concentrations were generally in the range of 10-25 mg/L and < 0.1 mg/L, respectively.

Chemical and ecotoxicological assessment of sludge-based biosolids used for corn field fertilization.

Sludge-based biosolids can be used for crop fertilization and for soil enrichment with organic matter. The prerequisites for their application are laid out in 86/278/EEC which sets limits for metals of toxicological concern in the biosolid and in the recipient soil. In this context, three kinds of sludge-based biosolids from a municipal wastewater treatment plant were submitted to the leaching tests EN 12457-2 and ΝΕΝ 7341. The leachates were examined for their physicochemical, chemical, and ecotoxicological characteristics four times within a year. Even in the more aggressive metal leaching method (ΝΕΝ 7341), results were much lower than the limits set in Council Directive 86/278/EEC. Correlations were noted between numerous parameters and principal component analysis grouped them in 3 components explaining 76% of total variation. These leaching tests were also performed on soil-biosolid samples from another investigative research in which two of the three kinds of biosolids had been incorporated in corn fields at doses 0, 20, and 40 tn/ha. EN 12457-2 leaching tests indicated that Ni and Cd leaching was affected by biosolid incorporation in soil, in relation to the type of the receiving soil (clay or sand). The leachates from the soil-biosolid mixtures were practically not toxic for the organisms tested (D. magna, V. fischeri, higher plants). In summary the biosolids were considered of low environmental risk when utilized in the field. A detailed risk assessment encompassing both chemical and ecotoxicological analysis is necessary for integrated evaluation of biosolids.

Combined Effect of Colloids and SMP on Membrane Fouling in MBRs.

Membrane fouling investigations in membrane bioreactors (MBRs) are a top research issue. The aim of this work is to study the combined effect of colloids and soluble microbial products (SMPs) on membrane fouling. Two lab-pilot MBRs were investigated for treating two types of wastewater (wwt), synthetic and domestic. Transmembrane pressure (TMP), SMP, particle size distribution and treatment efficiency were evaluated. Chemical Oxygen Demand (COD) removal and nitrification were successful for both kinds of sewage reaching up to 95-97% and 100%, respectively. Domestic wwt presented 5.5 times more SMP proteins and 11 times more SMP carbohydrates compared to the synthetic one. In contrast, synthetic wwt had around 20% more colloids in the mixed liquor with a size lower than membrane pore size (<400 nm) than domestic. Finally, the TMP at 36 days reached 16 kPa for synthetic wwt and 11 kPa for domestic. Therefore, synthetic wwt, despite its low concentration of SMPs, caused severe membrane fouling compared to domestic, a result that is attributed to the increased concentration of colloids. Consequently, the quantity of colloids and possibly their special characteristics play decisive and more important roles in membrane fouling compared to the SMP-a novel conclusion that can be used to mitigate membranes fouling.

Origin, implications and management strategies for nitrate pollution in surface and ground waters of Anthemountas basin based on a δ15N-NO3- and δ18O-NO3- isotope approach.

Nitrate pollution of surface and groundwater resources is a major worldwide environmental problem. In this study nitrogen isotopes of water, soil, fertilizer and manure were analyzed to determine the pollution sources of nitrate in the groundwater and surface waters of Anthemountas basin. The SIAR model and multivariate statistical analysis were used to determine and quantify the contribution of different NO3̄ sources in groundwater and surface water. Additionally, a detailed literature overview was carried out to identify the origin of nitrate pollution in surface and ground waters based on ΝΟ3- isotopes. The Piper diagram identified the dominant water types as Mg-Ca-HCO3 and Ca-Mg-HCO3. Nitrate concentrations reached 162.0 mg/L in groundwater and 39.0 mg/L in surface waters. The main source of nitrate in groundwater was mainly nitrified ammonium-based synthetic urea and less nitrate-based synthetic fertilizers. The correlation of SIAR results with other trace elements revealed a negative correlation between hexavalent chromium and a) nitrate-based synthetic fertilizers, and b) nitrification of urea synthetic fertilizers. However, a positive correlation was observed between hexavalent chromium and anthropogenic organic matter. The literature overview provided the basis to design a novel management protocol for nitrate pollution that includes three steps: a) fundamental research, b) management tools, c) monitoring and preservation actions. However, an integrated management protocol for nitrate pollution requires a deeper understanding of the hydro-system and the full participation of local farmers and stakeholders.

Improvement of Manganese Feroxyhyte's Surface Charge with Exchangeable Ca Ions to Maximize Cd and Pb Uptake from Water.

The surface configuration of tetravalent manganese feroxyhyte (TMFx) was appropriately modified to achieve higher negative surface charge density and, hence, to improve its efficiency for the removal of dissolved Cd and Pb mostly cationic species from water at pH values commonly found in surface or ground waters. This was succeeded by the favorable engagement of Ca2+ cations onto the surface of a mixed Mn-Fe oxy-hydroxide adsorbent during the preparation step, imitating an ion-exchange mechanism between H+ and Ca2+; therefore, the number of available negatively-charged adsorption sites was increased. Particularly, the calcium coverage can increase the deprotonated surface oxygen atoms, which can act as adsorption centers, as well as maintain them during the subsequent drying procedure. The developed Ca-modified adsorbent (denoted as TMFx-Ca) showed around 10% increase of negative surface charge density, reaching 2.0 mmol [H+]/g and enabling higher adsorption capacities for both Cd and Pb aquatic species, as was proved also by carrying out specific rapid small-scale column tests, and it complied with the corresponding strict drinking water regulation limits. The adsorption capacity values were found 6.8 µg·Cd/mg and 35.0 µg·Pb/mg, when the restructured TMFx-Ca adsorbent was used, i.e., higher than those recorded for the unmodified material.

Using Additives for Fouling Control in a Lab-Scale MBR; Comparing the Anti-Fouling Potential of Coagulants, PAC and Bio-Film Carriers.

This study investigates the effect of different additives, such as coagulants/flocculants, adsorption agents (powdered activated carbon, PAC), and bio-film carriers, on the fouling propensity of a lab-scale membrane bio-reactor (MBR) treating synthetic municipal wastewater. The coagulation agents FO 4350 SSH, Adifloc KD 451, and PAC1 A9-M at concentrations of 10 mg/L, 10 mg/L, and 100 mg Al/L, respectively, and PAC at a concentration of 3.6 ± 0.1 g/L, exhibited the best results during their batch-mode addition to biomass samples. The optimal additives FO 4350 SSH and Adifloc KD 451 were continuously added to the bioreactor at continuous-flow addition experiments and resulted in increased membrane lifetime by 16% and 13%, respectively, suggesting that the decrease of SMPc concentration and the increase of sludge filterability is the dominant fouling reduction mechanism. On the contrary, fouling reduction was low when PAC1 A9-M and PAC were continuously added, as the membrane lifetime was increased by approximately 6%. Interestingly, the addition of bio-film carriers (at filling ratios of 40%, 50%, and 60%) did not affect SMPc concentration, sludge filterability, and trans-membrane pressure (TMP). Finally, the effluent quality was satisfactory in terms of organics and ammonia removal, as chemical oxygen demand (COD), biochemical oxygen demand (BOD)5, and ΝΗ-N concentrations were consistently below the permissible discharge limits and rarely exceeded 30, 15, and 0.9 mg/L, respectively.

Adsorption of Se(IV) and Se(VI) species by iron oxy-hydroxides: Effect of positive surface charge density.

Batch and continuous mode experiments were used to determine the influence of physic-chemicals characteristics of iron oxy-hydroxides (FeOOHs) on selenium adsorption. Batch experiments and continuous flow rapid small-scale column tests (RSSCTs) at pH 7 and NSF (National Sanitation Foundation) water matrix, showed that the adsorption capacity of FeOOHs for Se(IV) is strongly related to positive surface charge density (PSCD), and gradually increases when synthesis pH is lowered. The highest PSCD value of 3.25 mmol [OH-]/g was observed at synthesis pH 2.5 (FeOOH/2.5) and the lowest, 0.45 mmol [OH-]/g, was observed at synthesis pH 9 (FeOOH/9). A thermodynamic study verified the endothermic (ΔΗ° 21.4 kJ/mol) chemisorption of Se(IV) by the qualified FeOOH/2.5. EXAFS data showed that Se(IV) is involved in three types of surface complexes: bidentate mononuclear edge-sharing (1E) and two types of binuclear inner-sphere (2C) linkage between the SeO32- pyramids, and Fe(O,OH)6 octahedra. The FeOOHs were evaluated by their adsorption capacity (Q10) at residual concentrations equal to the EU drinking water regulation limit of 10 µg/L, e.g. in conditions implemented in full-scale water treatment plants. The qualified FeOOH/2.5 was found to be the most effective for Se(IV) adsorption with a Q10 value 4.3 mg Se(IV)/g. In contrast, the Q10 value for Se(VI) was almost three orders of magnitude lower (10 µg Se(VI)/g) than that for Se(IV). Finally, regeneration experiments showed that FeOOHs reuse for Se(IV) removal is economically feasible and the recovery of selenium by precipitation as elemental Se contributes to green chemistry.

Fluoride removal from water by composite Al/Fe/Si/Mg pre-polymerized coagulants: Characterization and application.

Fluoride, an anionic pollutant, is possibly to be found in excessive concentrations especially in groundwaters and can show detrimental effects on human health, in concentrations higher than the commonly applied legislation limit of 1.5 mg/L The most commonly applied method for water de-fluoridation is performed by Al-based coagulants, which however presents some important limitations, such as the applied relatively high dosage, producing rather excessive amounts of chemical sludge. In this study, the use of novel pre-polymerized Al-based coagulants was examined, regarding their efficiency towards fluoride removal, as compared with the conventionally applied AlCl3. The novel coagulants were characterized by measuring the main physico-chemical properties, the aluminum species distribution, the zeta potential, the particles' size distribution and the produced flocs' sizes. The results showed that the Mg-containing coagulant (PSiFAC-Mg30-10-15) was the most efficient, when applied in pH values relevant to fluoride-containing groundwaters; it was also the only coagulant, which increases its efficiency at pH values > 7. The uptake capacity of coagulants, regarding fluoride, to reach the residual/equilibrium concentration limit of 1.5 mg F/L (Q1.5-value) at the pH value 7.0 ±â€¯0.1 were found 170, 134 and 94 mg F/g Al for the cases of PSiFAC-Mg30-10-15, AlCl3·6H2O and PSiFAC-Na1.5-10-15, respectively. Accordingly, at the pH value 7.8 ±â€¯0.2 the Q1.5-values were found 189, 118 and 41 mg F/g Al for the same coagulants; whereas considering the residual aluminum concentration this was ranged at 15 ±â€¯5, 25 ±â€¯5 and 30 ±â€¯5 µg Al/L, respectively. In addition, (beneficial) increase of residual magnesium concentration, when applying the coagulant PSiFAC-Mg30-10-15 was 15 ±â€¯5 mg/L.

Application of a ceramic membrane contacting process for ozone and peroxone treatment of micropollutant contaminated surface water.

This study investigates the performance of membrane-based ozonation and peroxone processes, regarding the transformation of carbamazepine (CBZ), benzotriazole (BZT), p-chlorobenzoic acid (pCBA) and atrazine (ATZ) in natural surface waters, as well as the formation of bromates. Ozonation, performed with the use of ceramic membrane contactor, was able to diminish CBZ concentration below 0.1 µM at 0.4 mg O3/mg DOC, i.e. presenting >90% removal rate, whereas the transformation of BZT, pCBA and ATZ was not exceeded 70%, 57% and 49%, respectively, under the same experimental conditions. The addition of H2O2 reduced the removal efficiency of CBZ, since up to -8% transformation values were observed at 0.1 mg O3/mg DOC. In contrast, the transformation of ozone-resistant compounds pCBA and ATZ was slightly improved by approximately 5-10%, at 0.8 mg O3/mg DOC. Membrane-based oxidative treatment of surface water resulted to high bromate concentrations (49 µg/L and 28 µg/L for ozone and peroxone process, respectively, at 0.8 mg O3/mg DOC). The results obtained by using the membrane contactor were also compared with the corresponding from conventional batch experiments. These results suggest that the implementation of membrane contactors with the highest possible inner surface per volume along with the use of low ozone gas concentration are required to improve the removal of micropollutants and diminish bromate formation.

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.

Cadmium, mercury, and nickel adsorption by tetravalent manganese feroxyhyte: selectivity, kinetic modeling, and thermodynamic study.

This study is aiming to investigate tetravalent manganese feroxyhyte (TMFx) adsorption efficiency in removing heavy metals. The motivation of this study was the fact that TMFx is a highly negatively charged nanostructure material and that the metals Cd, Hg, and Ni were characterized as priority pollutants for drinking water. TMFx was evaluated through batch and continuous flow experiments in National Sanitation Foundation (NSF) water matrix which simulated the physicochemical characteristics of natural water. Water's pH significantly influences Cd and Ni adsorption efficiency which gradually increases when pH value rises from 5 to 9, while the corresponding one for Hg remains almost constant. Thermodynamic data showed a spontaneous and an exothermic nature weak-chemisorption (ΔΗ° = -17.5 ± 2 kJ/mol) of Cd, Ni, and Hg by TMFx. The determined ranking of adsorption affinity and selectivity (Cd > Ni > Hg) seems to be governed by the metals' speciation, as well as by hydration free energy, which is influenced, however, by their atomic radius. The lower adsorption capacity and selectivity of TMFx for Hg should be attributed both to uncharged species and to higher atomic radius. The similar Cd and Ni speciation in the NSF water matrix leads to the conclusion that the better affinity, selectivity, and adsorption kinetic of Cd versus Ni should be attributed to the lower hydration free energy of Cd which is in turn related to its higher atomic radius. The faster adsorption kinetic (Hg > Cd > Ni) of Hg may be attributed to the lower radius of its anhydrate species. Furthermore, TMFx showed high removal efficiency under continuous flow application in an adsorption bed setup. The determined uptake capacity (q RL) at equilibrium-breakthrough concentration equal to the drinking water regulation limit (RL) of each metal were q 1 = 2.5 µg Hg/mg TMFx, q 5 = 5.2 µg Cd/mg TMFx, and q 20 = 7.1 µg Ni/mg TMFx. Leaching tests of spent TMFx samples from the rapid small-scale column tests (RSSCTs) could be treated either as inert wastes after Cd and Ni adsorption or as non-hazardous waste after Hg adsorption.

Reductive precipitation and removal of Cr(VI) from groundwaters by pipe flocculation-microfiltration.

Chromium (Cr(VI)) is a very toxic and carcinogenic element, which is widely present in groundwaters, mainly due to geogenic conditions. The limit of Cr(VI) in drinking water is expected to be reduced to 10 µg/L in both the USA and the European Union. Recent literature findings indicated that the most efficient process in reducing Cr(VI) levels to below 10 µg/L proved to be Cr(VI) reduction by Fe(II), by applying a molar ratio Fe(II)/Cr(VI) of around 9. In the present work, we investigated the reduction of Cr(VI) by Fe(II) in pipe flocculation reactors followed by filtration of insoluble products by microfiltration. The proposed technology involves re-circulation of a part of the sludge in the pipe reactors, in order to improve kinetics and efficiency of the process. The obtained results showed that with a Fe(II) dose of around 1 mg/L, Cr(VI) was reduced to below 10 µg/L, by even an initial concentration as high as 300 µg/L of Cr(VI), corresponding to a molar ratio Fe(II)/Cr(VI) of around 3, thus reducing the overall quantity of reductive reagents and of the produced sludge. This ratio was also confirmed by the XPS analysis, which also showed that Cr(VI) was reduced to Cr(III) and then precipitated either as Cr(OH)3 or associated with the produced iron oxides.

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.

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.

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.