Bioinspired Neuron-like Adsorptive Networks for Heavy Metal Capture and Tunable Electrochemically Mediated Recovery.

Electrochemical techniques have garnered increasing attention as a heavy metal remediation platform for pollutant mitigation and sustainable recycling. Inspired by the biological signal-transfer mode, biomimic neuron-like hierarchical adsorptive networks were constructed by interweaving one-dimensional manganese oxide nanowires into polyaniline-decorated hollow structural metal-organic frameworks (MOFs). The prepared biomimic neuron adsorbent exhibits good adsorption capacity toward cations (Pb2+) and oxyanions (Cr2O72-) at the neutral state; tunable cation/oxyanion desorption can be electrochemically switched at the oxidized and reduced states, respectively, where the biomimic neuron-like hierarchical adsorptive networks facilitated electron transfer and benefited substantial redox reactions. The combination of simulations and calculations demonstrates that the curvature-induced polarization in a hollow MOF structure enhances the desorption efficiencies by improving the redox processes at the electrode-electrolyte interface, which facilitate the promising implementation in terms of water economy and downstream waste sustainability.

A mesoporous cationic metal-organic framework with a high density of positive charge for enhanced removal of dichromate from water.

An imidazolium-functionalized mesoporous cationic Cr-based metal-organic framework (MOF) with high densities of positive charges was synthesized for the first time via a mixed-solvent strategy. The cationic mesoporous Cr-based MOF showed excellent adsorption performances in the removal of dichromate Cr2O72- from water with a large uptake of 321 mg g-1 and good regeneration ability.

Competition in chromate adsorption onto micro-sized granular ferric hydroxide.

Hexavalent chromium is highly toxic and elaborate technology is necessary for ensured removal during drinking water production. The present study aimed at estimating the potential of a micro-sized iron hydroxide (µGFH] adsorbent for chromate removal in competition to ions presents in drinking water. Freundlich and Langmuir models were applied to describe the adsorption behaviour. The results show a high dependency on the pH value with increasing adsorption for decreasing pH values. The adsorption capacity in deionized water (DI) at pH 7 was 5.8 mg/g Cr(VI) while it decreased to 1.9 mg/g Cr(VI) in Berlin drinking water (DW) at initial concentrations of 1.2 mg/L. Desorption experiments showed reversible adsorption indicating ion exchange and outer sphere complexes as main removal mechanisms. Competing ions present in DW were tested for interfering effects on chromate adsorption. Bicarbonate was identified as main inhibitor of chromate adsorption. Sulfate, silicate and phosphate also decreased chromate loadings, while calcium enhanced chromate adsorption. Adsorption kinetics were highly dependent on particle size and adsorbent dose. Adsorption equilibrium was reached after 60 min for particles smaller than 63 µm, while 240 min were required for particles from 125 µm to 300 µm. Adsorption kinetics in single solute systems could be modelled using the homogeneous surface diffusion model (HSDM) with a surface diffusion coefficient of 4∙10 -14 m2/s. Competitive adsorption could be modelled using simple equations dependent on time, adsorption capacity and concentrations only.

Dynamic interactions between sulfidated zerovalent iron and dissolved oxygen: Mechanistic insights for enhanced chromate removal.

Recent research on contaminant removal by zerovalent iron (ZVI) has evolved from investigating simple model systems to systems that encompass increased dimensions of complexity. Sulfidation and aerobic conditions are two of the most broadly relevant complications. Combining these two, this study investigated the dynamic interactions between sulfidated microscale ZVI and dissolved O2, for removal of Cr(VI), a model contaminant for metals and metalloids. The results show that the coupling of sulfidation and oxygenation significantly improves Cr removal, which is attributed to enhanced Fe(II) production that resulted from accelerated corrosion of Fe(0). The Cr(VI) removal rate increased with increasing O2 saturation from 0% to 100% but showed a bimodal dependence on the S/Fe ratio. At the optimal S/Fe ratio, the ZVI exhibits a highly porous surface morphology, which, according to prior literature on sulfur induced corrosion, promotes corrosion. In addition, a novel time series correlation was developed between aqueous Fe(II) and Cr(VI) based on data collected in the presence and absence of 1,10-phenanthroline, to probe for changes of reductants during the reaction time course. The analysis indicated that Fe(0) was responsible for the initial small amount of Cr(VI) removal, which then transitioned to a phase controlled by surface Fe(II). The slopes of the time series correlations during the latter phase of the reaction vary with experimental conditions but are mostly much higher than the theoretical stoichiometric ratio between Cr(VI) and Fe(II) (i.e., 0.33), indicating that Fe(II) regeneration contributes significantly to Cr removal.

Reductive solidification/stabilization of chromate in municipal solid waste incineration fly ash by ascorbic acid and blast furnace slag.

Fly ash is a hazardous byproduct of municipal solid waste incineration (MSWI). Cementitious material that is based on ground-granulated blast furnace slag (GGBFS) has been tested and proposed as a binder to stabilize Pb, Cd, and Zn in MSWI fly ash (FA). Cr, however, still easily leaches from MSWI FA. Different reagents, such as ascorbic acid (VC), NaAlO2, and trisodium salt nonahydrate, were investigated as potential Cr stabilizers. The results of the toxicity characteristic leaching procedure (TCLP) showed that VC significantly improved the stabilization of Cr via the reduction of Cr(VI) to Cr(III). VC, however, could interfere with the hydration process. Most available Cr was transformed into stable Cr forms at the optimum VC content of 2 wt%. Cr leaching was strongly pH dependent and could be represented by a quintic polynomial model. The results of X-ray diffraction and scanning electron microscopy-energy dispersive analysis revealed that hollow spheres in raw FA were partially filled with hydration products, resulting in the dense and homogeneous microstructure of the solidified samples. The crystal structures of C-S-H and ettringite retained Zn and Cr ions. In summary, GGBFS-based cementitious material with the low addition of 2 wt% VC effectively immobilizes Cr-bearing MSWI FA.

Simultaneous removal of nitrate and chromate in groundwater by a spiral fiber based biofilm reactor.

A spiral fiber based biofilm reactor was developed to remove nitrate and chromate simultaneously. The denitrification and Cr(VI) removal efficiency was evaluated with synthetic groundwater (NO3--N=50mg/L) under different Cr(VI) concentrations (0-1.0mg/L), carbon nitrogen ratios (C/N) (0.8-1.2), hydraulic retention times (HRT) (2-16h) and initial pHs (4-10). Nitrate and Cr(VI) were completely removed without nitrite accumulation when the Cr(VI) concentration was lower than 0.4mg/L. As Cr(VI) up to 1.0mg/L, the system was obviously inhibited, but it recovered rapidly within 6days due to the strong adaption and domestication of microorganisms in the biofilm reactor. The results demonstrated that high removal efficiency of nitrate (≥99%) and Cr(VI) (≥95%) were achieved at lower C/N=0.9, HRT=8h, initial pH=7, and Cr(VI)=1.0mg/L. The technology proposed in present study can be alternative for simultaneous removal of co-contaminants in groundwater.

A Water-Stable Cationic Metal-Organic Framework as a Dual Adsorbent of Oxoanion Pollutants.

A three-dimensional water-stable cationic metal-organic framework (MOF) pillared by a neutral ligand and with Ni(II)  metal nodes has been synthesized employing a rational design approach. Owing to the ordered arrangement of the uncoordinated tetrahedral sulfate (SO4 (2-) ) ions in the channels, the compound has been employed for aqueous-phase ion-exchange applications. The compound exhibits rapid and colorimetric aqueous-phase capture of environmentally toxic oxoanions (with similar geometries) in a selective manner. This system is the first example of a MOF-based system which absorbs both dichromate (Cr2 O7 (2-) ) and permanganate (MnO4 (-) ) ions, with the latter acting as a model for the radioactive contaminant pertechnetate (TcO4 (-) ).

Mechanisms of Chromate, Selenate, and Sulfate Adsorption on Al-Substituted Ferrihydrite: Implications for Ferrihydrite Surface Structure and Reactivity.

Ferrihydrite is a nanocrystalline Fe (hydr)oxide and important sink for environmental contaminants. Although Fe (hydr)oxides are rarely pure in natural systems, little is known about the effects of structural impurities such as Al on the surface properties and reactivity of ferrihydrite. In this study, we characterized the adsorption mechanisms of chromate, selenate, and sulfate on Al-substituted ferrihydrite (0, 6, 12, 18, and 24 mol % Al) using in situ attenuated total reflection Fourier transform infrared spectroscopy. Spectral data sets recorded as a function of pH were processed using a multivariate curve resolution technique to identify which types of surface species form and to generate their concentration profiles as a function of pH and Al content. Results show a significant increase in relative fraction of outer-sphere complexes for all three oxyanions with increasing Al substitution. In addition, the effect of Al substitution is found to be mechanism-specific in the case of chromate, with bidentate complexes disproportionately suppressed over monodentate complexes at higher Al contents. Overall, our findings have important implications for the fate of chromate, selenate, and sulfate in subsurface environments and offer new insight into the surface reactivity of Al-ferrihydrite.

Simultaneous removal of chromate and nitrate in a packed-bed bioreactor using biodegradable meal box as carbon source and biofilm carriers.

An up-flow packed-bed bioreactor was constructed to investigate the simultaneous removal of chromate and nitrate using biodegradable meal box as carbon source and biofilm carriers. The bioreactor was operated for 164days with varying influent Cr(VI) concentrations (2.0-50.0mg/L) and hydraulic retention times (HRT, 10-24h). It was shown that complete denitrification and Cr(VI) reduction could be achieved when influent Cr(VI) concentrations were lower than 20mg/L with a HRT of 17h. Shortening the HRT could significantly reduce the effluent CODcr. It was also observed that Cr(III) was mainly immobilized on the biofilm. Further investigation on Cr distribution in the biofilm compartments indicated that Cr(VI) reduction occurred in all compartments and the intercellular Cr was dominant. High-throughput sequencing analysis showed that Proteobacteria, Bacteroidetes and Firmicutes were the dominant phyla in the biofilm and Cr(VI) stress had a negative effect on the abundance of most bacteria.

Synthesis and optimization of Fe2O3 nanofibers for chromate adsorption from contaminated water sources.

In this work, α-Fe2O3 nanofibers were synthesized via electrospinning and characterized to observe optimal morphological and dimensional properties towards chromate removal. The Fe2O3 nanofiber samples were tested in aqueous solutions containing chromate (CrO4(2-)) to analyze their adsorption capabilities and compare them with commercially-available Fe2O3 nanoparticles. Synthesized Fe2O3 nanofibers were observed with a variety of different average diameters, ranging from 23 to 63 nm, while having a constant average grain size at 34 nm, point zero charge at pH 7.1, and band gap at 2.2 eV. BET analysis showed an increase in specific surface area with decreasing average diameter, from 7.2 to 59.2 m(2)/g, due to the increased surface area-to-volume ratio with decreasing nanofiber size. Based on CrO4(2-) adsorption isotherms at pH 6, adsorption capacity of the Fe2O3 nanofibers increased with decreasing diameter, with the 23 nm sized nanofibers having an adsorption capacity of 90.9 mg/g, outperforming the commercially-available Fe2O3 nanoparticles by nearly 2-fold. Additionally, adsorption kinetics was also analyzed, increasing with decreasing nanofiber diameter. The enhanced performance of the nanofiber is suggested to be caused solely due to the increased surface area, in part by its size and morphology. Electrospun Fe2O3 nanofibers provide a promising solution for effective heavy metal removal through nanotechnology-integrated treatment systems.

Studies of anions sorption on natural zeolites.

This work presents results of FT-IR spectroscopic studies of anions-chromate, phosphate and arsenate - sorbed from aqueous solutions (different concentrations of anions) on zeolites. The sorption has been conducted on natural zeolites from different structural groups, i.e. chabazite, mordenite, ferrierite and clinoptilolite. The Na-forms of sorbents were exchanged with hexadecyltrimethylammonium cations (HDTMA(+)) and organo-zeolites were obtained. External cation exchange capacities (ECEC) of organo-zeolites were measured. Their values are 17mmol/100g for chabazite, 4mmol/100g for mordenite and ferrierite and 10mmol/100g for clinoptilolite. The used initial inputs of HDTMA correspond to 100% and 200% ECEC of the minerals. Organo-modificated sorbents were subsequently used for immobilization of mentioned anions. It was proven that aforementioned anions' sorption causes changes in IR spectra of the HDTMA-zeolites. These alterations are dependent on the kind of anions that were sorbed. In all cases, variations are due to bands corresponding to the characteristic Si-O(Si,Al) vibrations (occurring in alumino- and silicooxygen tetrahedra building spatial framework of zeolites). Alkylammonium surfactant vibrations have also been observed. Systematic changes in the spectra connected with the anion concentration in the initial solution have been revealed. The amounts of sorbed CrO4(2-), AsO4(3-) and PO4(3-) ions were calculated from the difference between their concentrations in solutions before (initial concentration) and after (equilibrium concentration) sorption experiments. Concentrations of anions were determined by spectrophotometric method.

Adsorption of chromate and cupric ions onto chitosan-coated cotton gauze.

A chitosan-coated cotton gauze was prepared by UV-curing and tested as adsorbent to remove copper (II) and chromium (VI) ions from water solutions. The adsorbent characterization was carried out by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX) and Fourier Transform Infrared Spectroscopy in Attenuated Total Reflection (FTIR-ATR). Adsorption of copper and chromium ions onto the gauze was tested in batch process at different experimental conditions. The effects of pH, temperature, contact time and metal ion concentration were investigated. The optimum adsorption took place at pH 3 for Cr(VI) and pH 5 for Cu(II) ions respectively, while the temperature did not affect the adsorption process. Pseudo-first and pseudo-second order models were used to investigate the adsorption kinetics which was found very fast and better described by the pseudo-second order model for both metal ions. The adsorption of Cr(VI) ions was satisfactory described by the Langmuir isotherm, while that of Cu(II) ions showed a better agreement with the Freundlich model.

Modeling oxyanion adsorption on ferralic soil, part 2: chromate, selenate, molybdate, and arsenate adsorption.

High levels of oxyanions are found in the soil environment, often as a result of human activity. At high concentrations, oxyanions can be harmful to both humans and wildlife. Information about the interactions between oxyanions and natural samples is essential for understanding the bioavailability, toxicity, and transport of these compounds in the environment. In the present study, the authors investigated the reactivity of different oxyanions (AsO4 , MoO4 , SeO4 , and CrO4 ) at different pH values in 2 horizons of a ferralic soil. By combining available microscopic data on iron oxides with the macroscopic data obtained, the authors were able to use the charge distribution model to accurately describe the adsorption of these 4 oxyanions and thus to determine the surface speciation. The charge distribution model was previously calibrated and evaluated using phosphate adsorption/desorption data. The adsorption behavior on ferralic soil is controlled mainly by the natural iron oxides present, and it is qualitatively analogous to that exhibited by synthetic iron oxides. The highest adsorption was found for arsenate ions, whereas the lowest was found for selenate, with chromate and molybdate ions showing an intermediate behavior.

Immobilization of chromate in hyperalkaline waste streams by green rusts and zero-valent iron.

Zero-valent iron (ZVI) and green rusts can be used as reductants to convert chromium from soluble, highly toxic Cr(VI) to insoluble Cr(III). This study compared the reduction rates of Cr(VI) by ZVI and two carbonate green rust phases in alkaline/hyperalkaline solutions. Batch experiments were carried out with synthetic chromate solutions at pH 7.7-12.3 and a chromite ore processing residue (COPR) leachate (pH approximately 12.2). Green rust removes chromate from high pH solutions (pH 10-12.5) very rapidly (<400 s). Chromate reduction rates for both green rust phases were consistently higher than for ZVI throughout the pH range studied; the surface area normalized rate constants were two orders of magnitude higher in the COPR leachate solution at pH 12.2. The performances of both green rusts were unaffected by changes in pH. In contrast, ZVI exhibited a marked decline in reduction rate with increasing pH to become almost ineffective above pH12.

Comparative evaluations on bio-treatment of hexavalent chromate by resting cells of Pseudochrobactrum sp. and Proteus sp. in wastewater.

Two marine bacterial strains, B5 and H24, were isolated from long-term Cr(VI) contaminated seawater and identified as Pseudochrobactrum and Proteus, respectively, based on 16S rRNA gene sequence analyses. Both strains were examined for their tolerance to Cr(VI) and other metal salts and their abilities to reduce Cr(VI) to trivalent chromium [Cr(III)]. Growing cells of Pseudochrobactrum sp. B5 and Proteus sp. H24 could tolerate Cr(VI) at a concentration of 2000 and 1500 mg/l and completely reduce 1000 mg/l Cr(VI) in LB medium within 96 and 144 h, respectively. Resting cells of the two strains were able to reduce 200mg/l Cr(VI) in Tris-HCl buffer within 16 and 24h, respectively. Furthermore, resting cells of both strains were able to reduce Cr(VI) in industrial wastewaters three times consecutively. Overall, this study provides evidence of the potential for application of chromate-reducing bacteria to direct Cr(VI) decontamination of industrial effluents.

Bifunctional calix[4]arene sensor for Pb(II) and Cr2O7(2-) ions.

A readily available chromionophore 5,11,17,23-tetra-tert-butyl-25,27-bis(hydrazidecarbonylmethoxy)-26,28-dihydroxycalix[4]arene (HCC4) was employed as a chromogenic sensing probe selective for Pb(II) and Cr2O7(2-) ions among a series of various ions such as Li(I), Na(I), K(I), Rb(I), Ba(II), Sr(II), Al(III), Cd(II), Co(II), Cu(II), Hg(II), Ni(II), Pb(II) and Zn(II) as well as Cr2O7(2-), CH3CO2(-), Br(-), Cl(-), F(-), I(-), ClO4(-) and NO3(-) that have been examined by UV-visible and fluorescence spectroscopic techniques. The HCC4 in DCM-MeCN system forms 2:1 (ligand-metal) complex with Pb(II). It also shows 2:1 stoichiometry with Cr2O7(2-). The complexation phenomenon has been confirmed by FTIR spectroscopy that favors the selective nature of HCC4 with Pb(II) and Cr2O7(2-). Thermal gravimetric analysis (TGA) also supports its utility in drastic conditions.

Highly sensitive, highly specific whole-cell bioreporters for the detection of chromate in environmental samples.

Microbial bioreporters offer excellent potentialities for the detection of the bioavailable portion of pollutants in contaminated environments, which currently cannot be easily measured. This paper describes the construction and evaluation of two microbial bioreporters designed to detect the bioavailable chromate in contaminated water samples. The developed bioreporters are based on the expression of gfp under the control of the chr promoter and the chrB regulator gene of TnOtChr determinant from Ochrobactrum tritici 5bvl1. pCHRGFP1 Escherichia coli reporter proved to be specific and sensitive, with minimum detectable concentration of 100 nM chromate and did not react with other heavy metals or chemical compounds analysed. In order to have a bioreporter able to be used under different environmental toxics, O. tritici type strain was also engineered to fluoresce in the presence of micromolar levels of chromate and showed to be as specific as the first reporter. Their applicability on environmental samples (spiked Portuguese river water) was also demonstrated using either freshly grown or cryo-preserved cells, a treatment which constitutes an operational advantage. These reporter strains can provide on-demand usability in the field and in a near future may become a powerful tool in identification of chromate-contaminated sites.

Synergistic effect of coupling zero-valent iron with iron oxide-coated sand in columns for chromate and arsenate removal from groundwater: Influences of humic acid and the reactive media configuration.

A column study was conducted using a combination of zero-valent iron (Fe(0)) and iron oxide-coated sand (IOCS) for removing Cr(VI) and As(V) from groundwater. The removal efficiency and mechanism of Cr(VI) and As(V), the effects of humic acid (HA), and the various configurations of Fe(0) and IOCS were investigated. The results showed that the use of an Fe(0) and IOCS mixture in a completely mixed configuration can achieve the highest removal of both Cr(VI) and As(V), whilst the effects of HA were marginal in using these reactive materials. The solid phase analysis revealed the occurrence of the synergistic effect in these reactive materials as Fe(2+) can be adsorbed onto the IOCS and transform the iron oxides to magnetite, providing more reactive surface area for Cr(VI) reduction and reducing the passivation on the Fe(0). As(V) can then be removed by adsorption onto these iron corrosion products. HA can be adsorbed onto the IOCS so that the impacts of the deposition of HA aggregates on the Fe(0) surface can be reduced, thus enhancing the Fe(0) corrosion.

Efficient removal of chromate and arsenate from individual and mixed system by malachite nanoparticles.

Malachite nanoparticles of 100-150 nm have been efficiently and for the first time used as an adsorbent for the removal of toxic arsenate and chromate. We report a high adsorption capacity for chromate and arsenate on malachite nanoparticle from both individual and mixed solution in pH ∼4-5. However, the adsorption efficiency decreases with the increase of solution pH. Batch studies revealed that initial pH, temperature, malachite nanoparticles dose and initial concentration of chromate and arsenate were important parameters for the adsorption process. Thermodynamic analysis showed that adsorption of chromate and arsenate on malachite nanoparticles is endothermic and spontaneous. The adsorption of these anions has also been investigated quantitatively with the help of adsorption kinetics, isotherm, and selectivity coefficient (K) analysis. The adsorption data for both chromate and arsenate were fitted well in Langmuir isotherm and preferentially followed the second order kinetics. The binding affinity of chromate is found to be slightly higher than arsenate in a competitive adsorption process which leads to the comparatively higher adsorption of chromate on malachite nanoparticles surface.

Properties and applications of zeolites.

Zeolites are aluminosilicate solids bearing a negatively charged honeycomb framework of micropores into which molecules may be adsorbed for environmental decontamination, and to catalyse chemical reactions. They are central to green-chemistry since the necessity for organic solvents is minimised. Proton-exchanged (H) zeolites are extensively employed in the petrochemical industry for cracking crude oil fractions into fuels and chemical feedstocks for other industrial processes. Due to their ability to perform cation-exchange, in which the cations that are originally present to counterbalance the framework negative charge may be exchanged out of the zeolite by cations present in aqueous solution, zeolites are useful as industrial water-softeners, in the removal of radioactive Cs+ and Sr2+ cations from liquid nuclear waste and in the removal of toxic heavy metal cations from groundwaters and run-off waters. Surfactant-modified zeolites (SMZ) find particular application in the co-removal of both toxic anions and organic pollutants. Toxic anions such as arsenite, arsenate, chromate, cyanide and radioactive iodide can also be removed by adsorption into zeolites that have been previously loaded with co-precipitating metal cations such as Ag+ and Pb2+ which form practically insoluble complexes that are contained within the zeolite matrix.