Evaluation of Calcium Polysulfide as a Reducing Agent for the Restoration of a Cr(VI)-Contaminated Aquifer.

This study aims at investigating the efficiency of calcium polysulfide (CPS) as a reducing agent for decontamination of a heavily Cr(VI)-contaminated aquifer. Batch experiments were carried out in order to evaluate the effect of time, CPS concentration and the presence of soil on the reductive behavior of CPS. CPS was used at several stoichiometric excesses with respect to Cr(VI) concentration detected in the contaminated groundwater. In addition, the effect of CPS on other groundwater constituents like nitrates, and potential mobilization of soil elements were also evaluated. Finally, column tests were carried out in order to evaluate the efficiency of CPS for the Cr(VI) reduction in flow conditions. The results showed that CPS can be an effective reducing agent for the remediation of the Cr(VI) contaminated aquifer especially at pump and treat methods. The required minimum dose of CPS for reducing Cr(VI) from the initial level of 1000 µg/L below the environmental limit of 50 µg/L was found equivalent to approximately 2.8 mg/L of sulfide anions. Moreover CPS use did not significantly affect soil properties and mobilization of soil elements.

Continuous Flow Process for Cr(VI) Removal from Aqueous Solutions Using Resin Supported Zero-Valent Iron.

The objective of the present study was to evaluate the performance of a nanocomposite material consisting of nano zero valent iron and a cation exchange resin, for the reduction of chromate, by conducting column tests. A cationic resin, Amberlyst 15, was selected as porous host material. The synthesis of the nanocomposite material (R-nFe) was carried out using Green Tea extract to obtain the reduction of adsorbed Fe(III) to the elemental state Fe(0). Three column tests were implemented with different dimensions, corresponding to variable contact times between the aqueous solution and the resin beads loaded with Fe(0), namely 168, 744 and 1260 s respectively for columns I, II and III. The results indicated that the removal of Cr(VI) follows a first order kinetic law with a chemical constant equal to 0.0526 min-1 (8.8 × 10-4 s-1).

An Approach to Electrokinetic Removal of Cr(VI) from Soil and Kaolin Samples.

The present study examines electroremediation's efficiency on Cr(VI) contaminated samples. Electrokinetic experiments were performed applying a DC voltage of 30 V to a cylindrical sample of 30 cm length and 4 cm diameter, using Na2SO4 as background electrolyte solution. The first two experiments, one with kaolin and one with soil, were carried out without applying any pH adjustment in the anode or the cathode compartment, using 0.01 M Na2SO4. Further experiments were carried out increasing the electrolyte's concentration and using Mg(OH)2 to neutralize the generated acidity in the anode. The decrease in Cr(VI) concentration in the soil samples is partly taking place because of its reduction, most likely due to the presence of organic matter. This is indicated by the mass balance calculations which were based on the analyses of treated solid samples and electrolyte solutions. In the kaolin samples electromigration is the main factor resulting in the accumulation of Cr(VI) in the anodic solution.

Comparative evaluation of five plant extracts and juices for nanoiron synthesis and application for hexavalent chromium reduction.

The effectiveness of five plant extracts and juices, i.e. extracts of Camellia sinensis (green tea, GT), Syzygium aromaticum (clove, CL), Mentha spicata (spearmint, SM), Punica granatum juice (pomegranate, PG) and Red Wine (RW), for the production of nanoiron suspensions and their application for Cr(VI) reduction was investigated. Polyphenols contained in extracts act as reducing agents for iron ions in aqueous solutions, forming thus iron nanoparticles, and stabilize the nanoparticles produced from further oxidation and agglomeration. The maximum amount of polyphenols extracted per g of herbs was obtained at herb mass to water volume ratio varying from 10 to 20g/L. Suspensions of nanoparticles with sizes below 60nm were produced by mixing iron chloride solution with the plant extracts and juices investigated. The maximum concentration of nanoiron in suspensions was estimated to 22mM, obtained using RW and PG at a mixing ratio of iron solution to extract equal to 2. Lower concentrations, up to 18mM, were achieved using GT and CL extracts. Therefore, PG juice and RW were considered as more effective for nanoiron production, and, together with GT extracts, they were selected for the production of nanoiron suspensions, which have been proven effective for Cr(VI) reduction, reaching removal capacity as high as 500mg Cr(VI) per g of iron in nanoparticles.

Role of indigenous arsenate and iron(III) respiring microorganisms in controlling the mobilization of arsenic in a contaminated soil sample.

In this study two different treatment options were investigated for the release of arsenic from a contaminated soil sample. The first option was based on the "bioaugmentation" principle and involved addition of a pure Fe(III)-reducing culture, i.e. Desulfuromonas palmitatis. The second option consisted in the "biostimulation" of indigenous bacteria and involved simple addition of nutrients. Due to the strong association of As with soil ferric oxides, the reductive dissolution of soil oxides by D. palmitatis lead to 45 % arsenic release in solution (2.15 mM). When only nutrients were supplied to the soil, the same amounts of Fe and As were dissolved with slower rates and most aqueous As was found to be in the trivalent state, indicating the presence of arsenate reducing species. The arsenate reducing microorganisms were enriched with successive cultures, using Na2HAsO4 as electron acceptor. The phylogenetic analysis revealed that the enriched microbial consortium contained Desulfosporosinus species, which are known arsenate reducers.

Forensic investigation of a chromium(VI) groundwater plume in Thiva, Greece.

A forensic investigation was conducted with the aim of decoupling the contribution of geogenic and anthropogenic Cr(VI) sources in the wider area of Thiva. Groundwater and topsoil samples were collected from two Cr(VI) groundwater plumes of 160 µg/L and 75 µg/L. A series of evidence support the view that the origin of Cr(VI) detected in groundwater is mainly geogenic. These are: (a) the presence of Cr in topsoil of the wider area, (b) the moderate Cr(VI) groundwater concentrations, (c) the high Ni levels within the Cr(VI) plumes, (d) the predominance of Mn(IV), which is a prerequisite for Cr(III) oxidation to Cr(VI), and (e) the absence of co-contaminants. The present study also revealed that, although both Cr(VI) plumes are clearly of geogenic origin, the plume with the elevated Cr(VI) values, in the north of Thiva town, exhibits also an anthropogenic component, which can potentially be attributed to the alkaline environment associated with the old uncontrolled landfill of Thiva and the industrial cluster located in this area.

Column study for the evaluation of the transport properties of polyphenol-coated nanoiron.

Injection of a nano zero valent iron (nZVI) suspension in the subsurface is a remedial option for obtaining the in situ reduction and immobilization of hexavalent chromium in contaminated aquifers. Prerequisite for the successful implementation of this technology is that the nanoparticles form a stable colloidal suspension with good transport properties when delivered in the subsurface. In this study we produced stable suspensions of polyphenol-coated nZVI (GT-nZVI) and we evaluated their transport behavior through representative porous media. Two types of porous materials were tested: (a) silica sand as a typical inert medium and (b) a mixture of calcareous soil and sand. The transport of GT-nZVI through the sand column was effectively described using a classic 1-D convection-dispersion flow equation (CDE) in combination with the colloid filtration theory (CFT). The calculations indicate that nZVI travel distance will be limited in the range 2.5-25cm for low Darcy velocities (0.1-1m/d) and in the order of 2.5m at higher velocities (10m/d). The mobility of GT-nZVI suspension in the soil-sand column is lower and is directly related to the progress of the neutralization reactions between the acidic GT-nZVI suspension and soil calcite.

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.

Synthesis, characterization and stability of Cr(III) and Fe(III) hydroxides.

Chromium is a common contaminant of soils and aquifers and constitutes a major environmental problem. In nature, chromium usually exists in the form of two oxidation states, trivalent, Cr(III), which is relatively innocuous for biota and for the aquatic environment, and hexavalent, Cr(VI) which is toxic, carcinogenic and very soluble. Accordingly, the majority of wastewater and groundwater treatment technologies, include a stage where Cr(VI) is reduced to Cr(III), in order to remove chromium from the aqueous phase and bind the element in the form of environmentally stable solid compounds. In the absence of iron the final product is typically of the form Cr(OH)3·xH2O whereas in the presence of iron the precipitate is a mixed Fe(1-x)Crx(OH)3 phase. In this study, we report on the synthesis, characterisation and stability of mixed (Fex,Cr1-x)(OH)3 hydroxides as compared to the stability of Cr(OH)3. We established that the plain Cr(III) hydroxide, abiding to the approximate molecular formula Cr(OH)3·3H2O, was crystalline, highly soluble, i.e. unstable, with a tendency to transform into the stable amorphous hydroxide Cr(OH)3(am) phase. Mixed Fe0.75Cr0.25(OH)3 hydroxides were found to be of the ferrihydrite structure, Fe(OH)3, and we correlated their solubility to that of a solid solution formed by plain ferrihydrite and the amorphous Cr(III) hydroxide. Both our experimental results and thermodynamic calculations indicated that mixed Fe(III)-Cr(III) hydroxides are more effective enhancers of groundwater quality, in comparison to the plain amorphous or crystalline Cr(III) hydroxides, the latter found to have a solubility typically higher than 50µg/l (maximum EU permitted Cr level in drinking water), while the amorphous Cr(OH)3(am) phase was within the drinking water threshold in the range 5.7

Microbial arsenic reduction in polluted and unpolluted soils from Attica, Greece.

Indigenous soil microorganisms often affect the mobility of heavy metals and metalloids by altering their oxidation state. Under anaerobic conditions, the microbial transformation is usually reduction and may cause the mobilization of contaminants, as happens in the case of arsenic, which is much more stable in the pentavalent state compared to the reduced trivalent form. The aim of this work was to investigate the occurrence of such a microbial activity in representative Greek soils. Five soil samples, with As levels varying between 14 and 259 mg/kg, were examined. The samples were artificially contaminated, by adding 750 mg of As(V) per kg of soil. Initial sorption of As(V) ranged between 70 and 85%. Microbial reduction of arsenic was observed in three of the examined soils, without any obvious correlation with pre-existing levels of contamination. Reduction reached high percentages, i.e. up to 99%, and was accompanied by the corresponding release of reduced As in the aqueous solution. A simultaneous iron reducing activity was also observed in four of the five soil samples.

Removal of contaminant metals from fine grained soils, using agglomeration, chloride solutions and pile leaching techniques.

A leaching process based on the use of a HCl-CaCl2 solution, with total chloride concentration 4M, was investigated for the removal of contaminant metals from fine acidic soils. The possibility to apply this treatment on piles constructed on-site was also examined as a low cost treatment option. The soil sample used in the study was fine in texture, i.e. clay loam, acidic (pH 5.6), and contaminated mainly with Pb, up to 16000mg Pb/kg dry soil, due to past mining activities. The experimental work comprised all the treatment stages, including agglomeration of fine soil particles to increase the permeability of soil, leaching of the agglomerated soil in a laboratory column, removal of metals from the leachate, regeneration and recycling of the leaching solution and final washing of the treated soil. The initial agglomeration treatment resulted in the formation of coarse aggregates and the percolation of leaching solution through the soil column was maintained at high levels, i.e.75ml/cm(2) per day, during the whole treatment. A low amount of HCl acid was required for the removal contaminants from this particular soil, i.e. 0.44mol HCl/kg soil, due to the absence of acid consuming minerals. The extractions achieved were 94% for Pb, 78% for Zn and more than 70% for Cd. The co-dissolution of soil matrix was very limited, with a total weight loss about 3.5%. The final pH of the soil after washing was found to be 5.15, i.e. slightly lower compared to the initial pH of the soil. The results of this study indicate that chloride leaching, in combination with agglomeration and pile leaching techniques, can be a cost effective option for the removal of metal contaminants from fine acidic soils.