Electrochemical Characterization of Isolated Nitrogenase Cofactors from Azotobacter vinelandii.

The nitrogenase cofactors are structurally and functionally unique in biological chemistry. Despite a substantial amount of spectroscopic characterization of protein-bound and isolated nitrogenase cofactors, electrochemical characterization of these cofactors and their related species is far from complete. Herein we present voltammetric studies of three isolated nitrogenase cofactor species: the iron-molybdenum cofactor (M-cluster), iron-vanadium cofactor (V-cluster), and a homologue to the iron-iron cofactor (L-cluster). We observe two reductive events in the redox profiles of all three cofactors. Of the three, the V-cluster is the most reducing. The reduction potentials of the isolated cofactors are significantly more negative than previously measured values within the molybdenum-iron and vanadium-iron proteins. The outcome of this study provides insight into the importance of the heterometal identity, the overall ligation of the cluster, and the impact of the protein scaffolds on the overall electronic structures of the cofactors.

Potential use of Bacillus genera for metals removal from spent catalysts.

The aim of the present study was to isolate microorganisms able to tolerate Ni2+ and V5+ from different sites located close to a mineral mine in Guanajuato, Mexico, and then to evaluate their ability to remove metals contained in a spent catalyst. Seventeen isolates were obtained; among them seven presented a minimum inhibitory concentration (MIC) higher than 200 mg/L of Ni2+ and V5+ each. Nickel and Vanadium removal was evaluated in 9 K liquid medium added with spent catalyst at 16% (s/v) pulp density and incubated at 30 °C, 150 rpm for 7 days. Only three isolates which were coded as PRGSd-MS-2, MNSH2-AH-3, and MNSS-AH-4 showed a significant removal at the end of treatment corresponding in mg kg-1 (or percentage metal removal) of 138 (32%), 123 (29%), and 101 (24%) for Ni, respectively; and 557 (26%), 737 (34%), and 456 (21%) mg kg-1 for V, respectively. The same isolates were capable to remove also Al, Fe, As, and Mg at different extent. Cell morphology changes were observed, in comparison to the control system at the end of biological treatment as a higher quantity of spores for MNSH2-AH-3, 2 µm cells in pairs for MNSS-AH-4, also long chain-vegetative cells having inclusions into the cell surface were observed for PRGSd-MS-2. The three isolated microorganisms were identified by sequencing of the 16S gene as Bacillus thuringiensis, Bacillus megaterium, and Bacillus sp, respectively, suggesting its potential use in the treatment of this solid industrial waste.

Recovery of Al, Cr and V from steel slag by bioleaching: Batch and column experiments.

Steel slag is a major by-product of the steel industry and a potential resource of technology critical elements. For this study, a basic oxygen furnace (BOF) steel slag was tested for bacterial leaching and recovery of aluminium (Al), chromium (Cr), and vanadium (V). Mixed acidophilic bacteria were adapted to the steel slag up to 5% (w/v). In the batch tests, Al, Cr, and V were bioleached significantly more from steel slag than in control treatments. No statistical difference was observed arising from the duration of the leaching (3 vs 6 d) in the batch tests. Al and Cr concentrations in the leachate were higher for the smaller particle size of the steel slag (<75 µm), but no difference was observed for V. In the column tests, no statistical difference was found for pH, Al, Cr and V between the live culture (one-step bioleaching) and the supernatant (two-step bioleaching). The results show that the culture supernatant can be effectively used in an upscaled industrial application for metal recovery. If bioleaching is used in the 170-250 million tonnes of steel slag produced per year globally, significant recoveries of metals (100% of Al, 84% of Cr and 8% of V) can be achieved, depending on the slag composition. The removal and recovery percentages of metals from the leachate with Amberlite®IRA-400 are relatively modest (<67% and <5%, respectively), due to the high concentration of competing ions (SO42-, PO43-) in the culture medium. Other ion exchange resins can be better suited for the leachate or methods such as selective precipitation could improve the performance of the resin. Further research is needed to minimise interference and maximise metal recovery.

Airflow-field-induced sandwich-type membrane of block copolymer for selective ion separation.

A simple and effective airflow method to prepare sandwich-type block copolymer films is reported. The films are composed of three layers: vertically oriented nanocylinders align in both upper and bottom layers and irregular nanocylinders exist in the bulk of the film. The vertically oriented nanocylinders in both sides can provide high accessibility to ions and ensures the exchange of chemical species between the membrane and external environment, while the irregularly oriented nanocylinders in the middle part of the film can prolong the pathway of ions transportation and enhance ions selectivity.

An environmentally friendly process for the recovery of valuable metals from spent refinery catalysts.

The present study dealt with the whole valorization process of exhaust refinery catalysts, including metal extraction by ferric iron leaching and metal recovery by precipitation with sodium hydroxide. In the leaching operation the effects on metal recovery of the concentration and kind of acid, the concentration of catalyst and iron (III) were determined. The best operating conditions were 0.05 mol L(-1) sulfuric acid, 40 g L(-1) iron (III), 10% catalyst concentration; almost complete extraction of nickel and vanadium, and 50%extraction efficiency of aluminium and less than 20% for molybdenum. Sequential precipitation on the leach liquor showed that it was not possible to separate metals through such an approach and a recovery operation by means of a single-stage precipitation at pH 6.5 would simplify the procedures and give a product with an average content of iron (68%), aluminium (13%), vanadium (11%), nickel (6%) and molybdenum (1%) which would be potentially of interest in the iron alloy market. The environmental sustainability of the process was also assessed by means of life cycle assessment and yielded an estimate that the highest impact was in the category of global warming potential with 0.42 kg carbon dioxide per kg recovered metal.

Synthesis and characterization of titania hollow fiber and its application to the microextraction of trace metals.

A titania hollow fiber membrane was successfully synthesized in a macro range via a template method coupled with a sol-gel process. Thermal gravimetric and differential thermal analysis (TG-DTA) was employed to study the effect of heat treatment on the synthesized hollow fiber, and the crystal forms of the titania hollow fiber membranes at different temperatures were studied by X-ray diffraction (XRD). The pore structure of the prepared titania hollow fiber was characterized by scanning electron micrograph (SEM) and nitrogen adsorption/desorption measurements. The prepared titania hollow fiber membrane was explored as a new adsorption material for trace metals for the first time and a new method of titania hollow fiber membrane solid phase microextraction (MSPME) online coupled to inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace amount of Cd, Co, V and Ni in human serum samples. In order to validate the developed method, two certified reference materials of NIES.No.10-b rice flour and BCR No.184 bovine muscle were analyzed and the determined values were in good agreement with the certified values.

Development of functional lignin-based spherical particles for the removal of vanadium(V) from an aqueous system.

A new type of functional lignin-based spherical particles (L-CTAB) prepared with the use of hexadecyltrimethylammonium bromide (CTAB) was applied as an effective biosorbent for removing vanadium(V) ions. The porous structure, characteristic functional groups, electrokinetic stability, morphology and size of the L-CTAB particles were examined. The conditions of removal were also investigated, including pH (2-12), sorbent mass (0.1-0.5 g), concentration (10-100 mg/dm3), phase contact time (1-240 min) and temperature (293-333 K). At pH 5.0 the maximum sorption percentage (%S) of V(V) was 45%, while at pH 2.0 it was 32%. The maximum sorption capacity of V(V) for L-CTAB was found to be 10.79 mg/g. The kinetic data indicate that the sorption followed the pseudo-second-order and film diffusion models. Sorption equilibrium for V(V) ions removal by L-CTAB was reached after 60 min at the initial concentrations 10 and 50 mg/dm3. It has been shown that the adsorption of V(V) ions on the surface of L-CTAB is a heterogeneous, endothermic and spontaneous reaction, as evidenced by the calculated values of thermodynamic parameters - free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) - for the tested systems at different temperatures. HCl solutions, used as an L-CTAB regeneration agent, quantitatively eluted V(V) ions.

Factors affecting the performance of microbial fuel cells for sulfide and vanadium (V) treatment.

Sulfide and vanadium (V) are pollutants commonly found in wastewaters. A novel approach has been investigated using microbial fuel cell (MFC) technologies by employing sulfide and V(V) as electron donor and acceptor, respectively. This results in oxidizing sulfide and deoxidizing V(V) simultaneously. A series of operating parameters as initial concentration, conductivity, pH, external resistance were carefully examined. The results showed that these factors greatly affected the performance of the MFCs. The average removal rates of about 82.2 and 26.1% were achieved within 72 h operation for sulfide and V(V), respectively, which were accompanied by the maximum power density of about 614.1 mW m(-2) under all tested conditions. The products generated during MFC operation could be deposited, resulting in removing sulfide and V(V) from wastewaters thoroughly.

Recovery of chromium, copper and vanadium combined with electricity generation in two-chambered microbial fuel cells.

Microbial fuel cells (MFCs) offer a promising solution towards recovery and treatment of heavy metal pollutants. In this study, two-chambered MFCs were employed for recovery of chromium, copper and vanadium (Cr (VI), Cu (II) and V (V)). One g/L concentrations of K2Cr2O7, CuCl2 and NaVO3 served as catholytes, while a mixed culture was used as anolyte. Cr (VI), Cu (II) and V (V) were reduced biologically into less toxic forms of Cr (III), Cu and V (IV) respectively. Power density and cathodic efficiency were calculated for each of the catholytes. Cr (VI) gave the maximum power density and cathodic efficiency due to its high redox potential. Current produced depended on the concentration of the catholyte. Over a period of time, biological reduction of catholytes lead to decrease in the metal concentrations, which demonstrated the application of MFC technology towards heavy metal treatment and recovery in a reasonably cost-effective manner.

Enhanced adsorption properties of zirconium modified chitosan-zeolite nanocomposites for vanadium ion removal.

The novel hybrid adsorbents, which were composed of nanozeolite and nanochitosan (NZ@NCT) and nanozeolite-multi walled carbon nanotube and nanochitosan (CNZ@NCT) were produced by simple method. The adsorption capacity of synthesized nanocomposites towards vanadium (V) was compared with that of a clinoptilolite-nanochitosan nanocomposite (CPL@NCT) obtained from natural zeolite. Zirconium (Zr) was employed to modify prepared nanocomposites because Zr (IV) has a strong affinity towards oxyanions such as V. Zr-modified nanocomposites and their pristine nanocomposites were comparatively characterized by different techniques. Batch experiments were conducted to find out the influence of different experimental factors. The adsorption capacities of all prepared materials towards V ions decreased with temperature increasing from 298 to 348 K. The calculated values of the thermodynamic parameters ΔH and ΔG demonstrated that the adsorption was exothermic and spontaneous. The adsorption process was described by the Freundlich isotherm and pseudo-second order model. The V species loaded nanocomposites could be regenerated by 0.5 M HCl-1.0 M thiourea solution. The adsorption performance was not considerably influenced by the coexistence of the nickel ( Ni2+) but nitrate (NO3-) and sulfate (SO42-) revealed slightly greater negative effects. The as-prepared nanocomposites can be used in three adsorption cycles without specific changing its adsorption efficiency.

Vanadium-basidiomycete fungi interaction and its impact on vanadium biogeochemistry.

Fungi are well known to strongly interact with metals, thereby influencing metal biogeochemistry in the terrestrial environment. To assess and quantify potential fungi-vanadium (V) interactions, Amanita muscaria, Armillaria cepistipes, Xerocomus badius and Bjerkandera adusta were cultured in media containing soluble V (VOSO4 or NaVO3) or solid-phase V of different chemical forms and oxidation state (V2O3, VO2, V2O5, or V-Ti magnetite slag). All fungi underwent physiological and structural changes, as revealed by alterations in FT-IR peak positions and intensities relative to the control, and morphological changes of mycelia, as observed by scanning electron microscopy. The diametric growth size generally decreased with decreasing oxidation state of V and with increasing concentrations of VOSO4 and NaVO3, implying that V toxicity is dependent on V speciation. The tolerance index, the ratio of treated and control mycelium (dry weight), shows different tendencies, suggesting additional factors influencing fungi weight, such as the formation of extrahyphal crystals. Vanadium accumulation from VOSO4 and NaVO3 medium in all fungi (up to 51.3 mg g-1) shows the potential of fungi to immobilise soluble V, thereby reducing its impacts on environmental and human health. Uptake and accumulation of V in slag was insignificant, reflecting the association of slag V with insoluble crystalline materials. The fungal accumulation of V in medium amended with V-oxides demonstrates the ability of fungi to solubilise solid-phase V compounds, thereby introducing previously immobile V into the V biogeochemical cycle and into the food chain where it may impact ecological and human health. A.muscaria lowered the pH of the medium substantially during cultivation, indicating acidolysis and complexolysis via excretion of organic acids (e.g. oxalic acid). Oxidation of VOSO4 was observed by a colour change of the medium to yellow during B. adusta cultivation, revealing the role of fungally-mediated redox transformation in V (im)mobilisation. The calculated removal efficiencies of soluble V were 40-90% for A. cepistipes and X. badius, but a much lower recovery (0-20%) was observed from V oxides and slag (0-20%) by all fungi. This suggests the probable application of fungi for bio-remediation of mobile/soluble V in contaminated soils but not of V incorporated in the lattice of soil minerals.

Multi-step column leaching using low-molecular-weight organic acids for remediating vanadium- and chromium-contaminated soil.

In soil, vanadium (V) contamination is commonly concomitant with chromium (Cr) contamination, which poses potential risks to humans, animals, and plants due to the transfer of toxic metals and the increase in their concentrations via the food chain or through direct exposure. This study applied a multi-step column leaching process using low-molecular-weight organic acids (LMWOAs) to treat V-contaminated soil from a smelter site that contains 2015.1 mg V kg-1 and 1060.3 mg Cr kg-1. After leaching three times with an equivalent solution/soil ratio of 0.3 mL/g using 1.0 M oxalic acid solution, the total removal rates reached 77.2% and 7.2% for V and Cr, respectively, while the removal rates of the extractable fractions reached 118.6% and 99.2% due to the reduction in residual fraction (F4) of toxic metals. Simultaneously, the distribution and redistribution of geochemical fractions of V and Cr were determined with a sequential extraction technique, and the greater proportion of potential mobile fractions of V (65.1%) may increase its leaching from soil relative to Cr (7.1%). In addition, a lower pH of the leaching agent increased the efficiency of the leaching process to an extent. Compared with batch extraction with a typical solution to soil ratio of 10 mL/g, multi-step column leaching used less agent and hence produced less wastewater. This strategy could reduce the mobilization and bioavailability of toxic metals, and potentially enhance in situ soil flushing for the remediation of V- and Cr- contaminated soil.

Recovery of V(V) from complex vanadium solution using capacitive deionization (CDI) with resin/carbon composite electrode.

The resin-activated carbon composite (RAC) electrodes were fabricated and applied in capacitive deionization for recovery of V(V) from complex vanadium solution. The adsorption capacity of the RAC electrode for V(V) is extremely low and the reduction of V(V) is significant in low pH solution, but the adsorbed V(V) on the electrode increases obviously and the reduction of V(V) gradually diminishes with the rise of pH. However, as the pH is increased to 10, the adsorbed V(V) on the RAC electrode declines. The higher applied potential is beneficial to the adsorption of V(V) and 1.0 V is appropriate for the adsorption. The impurities ions (Al, P and Si) are mainly adsorbed in the electric double layers on the RAC electrode and V(V) is dominantly adsorbed by the resins in the electrode. The adsorbed impurity ions can be easily removed by diluted H2SO4 and V(V) can be effectively eluted by 10% NaOH solution. The vanadium-bearing eluent can be recycled to recover and enrich vanadium from the complex solution. The performance of the RAC electrode keeps stable during the cyclic operation. This study may provide a promising and novel method for the recovery and separation of metals from aqueous solution.

Adsorption characteristics of vanadium on different resin-active carbon composite electrodes in capacitive deionization.

Three kinds of anion exchange resins (AERs) (D201, D301, D314) and one kind of cation exchange resin (D860) were used with activated carbon (AC) to fabricated the ion exchange resin-AC (IER/AC) composite electrodes in capacitive deionization (CDI) for selective adsorption of V(V). The characteristics of four kinds of composite electrodes, such as wettability, pore distribution and electrochemical properties, indicates IER/AC composite has great potential as electrode materials for the electro-adsorption in CDI. The pH of solution has apparent influence on the adsorption capacity of the composite electrodes for V(V) because of the various V(V) species in the solution with different pH. The reduction rate of V(V) on IER/AC electrodes mainly relates to the amount of VO2+ in solution. The adsorption capacity of AER/AC electrodes for V(V) is slightly affected by the applied voltage may be due to that the adsorption of V(V) is mainly dependent on ion exchange with AERs and only a minority of V(V) is adsorbed by electrostatic adsorption. The adsorbed V(V) on D860/AC electrode decreases with the rising applied voltage because the pH increases with the increase of voltage. The separation of V(V) from V(V), Al and P indicates that the selective adsorption capability of IER/AC composite electrode is related to the migration rate of V(V), Al, P at different voltages and the selectivity of resins. This study may provide reference for recovering and separating metal ions from aqueous solution with CDI.

Removal of vanadium from wastewater using surface-modified lignocellulosic material.

Palm fruit husk, a lignocellulosic material, is an agricultural solid waste. Since raw palm fruit husk does not adsorb V (V), it was subjected to surface modification with a cationic surfactant cetyl trimethyl ammonium bromide (CTAB). The surface-modified palm fruit husk showed adsorption capability for V (V). The maximum adsorption of V (V) takes place at pH 4. Adsorption equilibrium data were fitted to Langmuir, Freundlich, and Dubinin Radushkevich (D-R) isotherm models. Kinetic studies showed that the adsorption data fit second-order kinetic model better than first order. Desorption of V (V) proved that it is feasible to recover V (V) from the spent adsorbent. Effect of coexisting anions like Molybdate, sulfate, nitrate, phosphate, and thiocyanate on the adsorption of V (V) was also studied and the foreign ions compete for the adsorption sites with V (V) anionic species. Quantitative removal of V (V) was achieved from synthetic wastewater.

Toxicological Evaluation of Brassica napus Extract Containing Vanadium, Nutricultured in Jeju Water.

This study evaluated the mutagenicity and acute toxicity of the juice extract of nutricultured Brassica napus containing vanadium (BECV). The BECV was prepared by nutriculture for 7 days in Jeju water containing vanadium. The mutagenic effects of BECV were investigated using the bacterial reverse mutation test, chromosome aberration test, and micronucleus test. Based on the results of the mutagenicity test, we propose that BECV is not a mutagenicity-inducing agent. In the acute oral toxicity study, male and female Sprague-Dawley rats were administered a single limiting dose of 0.014, 0.14, or 1.4 µg BECV/kg body weight; the rats were then observed for 7 days. No acute lethal effect was observed at the maximal dose of 1.4 µg BECV/kg body weight. In the subacute study, male and female rats were administered once daily, by oral gavage, a dose of 0.028, 0.14, and 0.7 µg/kg body weight of BECV for 28 days. No significant toxicity was observed not only hematological, biochemical, and pathological parameters but also the body and organ weights when compared to controls. The level of BECV with no observed adverse effects in male and female rats was 0.7 µg/kg body weight (concentration of vanadium in BECV) in the subacute toxicity study.

Removal of vanadium and palladium ions by adsorption onto magnetic chitosan nanoparticles.

Chitosan (CS), synthesized from chitin chemically extracted from shrimp shells, was used for the synthesis of magnetic chitosan nanoparticles (Fe3O4-CSN), which makes the adsorbent easier to separate. Fe3O4-CSN was used for the removal of toxic metals such as vanadium (V(V)) and palladium (Pd(II)) ions from aqueous solutions. Influencing factors on the adsorption process such as pH, contact time, adsorbent dosage, and agitation speed were investigated. A competitive adsorption of V(V) and Pd(II) ions for the active sites was also studied. The monolayer maximum adsorption capacities (Qm) of 186.6 and 192.3 mg/g were obtained for V(V) and Pd(II) ions, respectively. The pseudo-second-order equation gave the best fit for the kinetic data, implying that chemisorption was the determining step. Freundlich model yielded a much better fit than the other adsorption models assessed (Langmuir, Temkin and Dubinin-Radushkevich). Thus, the adsorption of V(V) and Pd(II) ions onto Fe3O4-CSN is a combination of physical and chemical adsorption, as based on the kinetics and equilibrium study. Generally, physical adsorption is the mechanism that governs the system, while chemical adsorption is the slowest adsorption step that takes place. Thermodynamic studies displayed that the adsorption process was exothermic and spontaneous. Removal efficiencies of 99.9% for V(V) and 92.3% for Pd(II) ions were achieved, implying that Fe3O4-CSN adsorbent had an excellent ability for the removal of the metal ions from real industrial wastewaters without remarkable matrix effect. Graphical abstract ᅟ.

Recovery of gallium and vanadium from gasification fly ash.

The Puertollano Integrated Coal Gasification Combined Cycle (IGCC) Power Plant (Spain) fly ash is characterized by a relatively high content of Ga and V, which occurs mainly as Ga2O3 and as Ga3+ and V3+ substituting for Al3+ in the Al-Si fly ash glass matrix. Investigations focused on evaluating the potential recovery of Ga and V from these fly ashes. Several NaOH based extraction tests were performed on the IGCC fly ash, at different temperatures, NaOH/fly ash (NaOH/FA) ratios, NaOH concentrations and extraction times. The optimal Ga extraction conditions was determined as 25 degrees C, NaOH 0.7-1 M, NaOH/FA ratio of 5 L/kg and 6 h, attaining Ga extraction yields of 60-86%, equivalent to 197-275 mg of Ga/kg of fly ash. Re-circulation of leachates increased initial Ga concentrations (25-38 mg/L) to 188-215 mg/L, while reducing both content of impurities and NaOH consumption. Carbonation of concentrated Ga leachate demonstrated that 99% of the bulk Ga content in the leachate precipitates at pH 7.4. At pH 10.5 significant proportions of impurities, mainly Al (91%), co-precipitate while >98% of the bulk Ga remains in solution. A second carbonation of the remaining solution (at pH 7.5) recovers the 98.8% of the bulk Ga. Re-dissolution (at pH 0) of the precipitate increases Ga purity from 7 to 30%, this being a suitable Ga end product for further purification by electrolysis. This method produces higher recovery efficiency than currently applied for Ga on an industrial scale. In contrast, low V extraction yields (<64%) were obtained even when using extreme alkaline extraction conditions, which given the current marked price of this element, limits considerably the feasibility of V recovery from IGCC fly ash.

Vanadium recovery from oil fly ash by leaching, precipitation and solvent extraction processes.

In order to reduce the environmental impact due to land disposal of oil fly ash from power plants and to valorize this waste material, the removal of vanadium was investigated using leaching processes (acidic and alkaline treatments), followed by a second step of metal recovery from leachates involving either solvent extraction or selective precipitation. Despite a lower leaching efficiency (compared to sulfuric acid), sodium hydroxide was selected for vanadium leaching since it is more selective for vanadium (versus other transition metals). Precipitation was preferred to solvent extraction for the second step in the treatment since: (a) it is more selective; enabling complete recovery of vanadate from the leachate in the form of pure ammonium vanadate; and (b) stripping of the loaded organic phase (in the solvent extraction process) was not efficient. Precipitation was performed in a two-step procedure: (a) aluminum was first precipitated at pH 8; (b) then ammonium chloride was added at pH 5 to bring about vanadium precipitation.

Selective recovery of vanadium and scandium by ion exchange with D201 and solvent extraction using P507 from hydrochloric acid leaching solution of red mud.

D201 resin and P507 extractant diluted with sulfonated kerosene were used to respectively separate vanadium and scandium, and impurity ions from hydrochloric acid leaching solution of red mud. More than 99% of vanadium was selectively adsorbed from the hydrochloric acid leaching solution under the conditions of pH value of 1.8, volume ratio of leaching solution to resin of 10, and flow rate of 3.33 mL/min. Maximum extraction and separation of scandium was observed from the acid leaching solution at an aqueous pH value of 0.2. More than 99% of scandium can be selectively extracted using 15% P507, 5% TBP at the aqueous solution/organic phase (A/O) ratio of 10:1 for 6 min. The loaded organic phase was washed with 0.3 mol/L sulfuric acid, wherein most impurities were removed. After the process of desorption or stripping, precipitation, and roasting, high-purity V2O5 and Sc2O3 were obtained. Finally, a conceptual flow sheet was established to separate and recover vanadium and scandium from red mud hydrochloric acid leaching solution.