Efficient removal of chromate from wastewater using a one-pot synthesis of chitosan cross-linked ceria incorporated hydrous copper oxide bio-polymeric composite.

Remediating hexavalent chromium [Cr(VI)] from contaminated water systems is a significant concern due to its harmful effects on human health, aquatic life, and plants. To tackle this issue, scientists have created a chitosan cross-linked hydrous ceria incorporated cupric oxide bio-polymeric composite (CHCCO) by combining chitosan biopolymer with corresponding metal ions using glutaraldehyde as a cross-linker. The composite was characterized using advanced analytical instruments such as FTIR, p-XRD, SEM, XPS, etc. The synthesized composite (CHCCO) was then tested for its efficiency in removing Cr(VI) from synthetic Cr(VI) aqueous samples. The parameters examined included pH, material dose, contact time, concentration, temperature, and co-existing ions. The experimental data showed that the kinetics and equilibrium data fit well with the pseudo-second-order and the Freundlich isotherm models, respectively. Thermodynamic analysis demonstrated that the investigated surface adsorption process is spontaneous and endothermic. Except for the SO42- ion, no other species imparts adverse influence significantly on the reaction. The CHCCO bio-composite surfaces were refreshed using a dilute NaOH (1.0 M) solution and effectively recycled five times for Cr(VI) adsorption, indicating no significant surface activity deterioration. This study highlights the high effectiveness of CHCCO bio-polymeric composites in Cr(VI) remediation and the potential for this technology as an easy-to-use technique for environmental restoration.

Au nanoparticles decorated graphitic carbon nitride nanosheets as a sensitive and selective fluorescence probe for Fe3+ and dichromate ions in aqueous medium.

Graphitic carbon nitride mutated with metal nanoparticles has captivated great interest as an effective fluorescent sensor for the detection of harmful ions present in water. In the present work, bulk-gCN was synthesized using melamine as precursor, and further Au-gCN nanocomposite were fabricated via in-situ direct reduction deposition method. The structural, morphological, compositional, stability and optical properties of bulk gCN and Au-gCN nanocomposite were examined using various scattering and spectroscopic techniques such as HRTEM, XPS, XRD and SEM. The synthesized bulk gCN straggles during selectivity studies with different cations and anions because of its uneven surface morphology, however in Au-gCN gold nanoparticles are uniformly distributed on the gCN sheets which results in its enhanced selectivity over bulk gCN. This leads to the fabrication of an optical sensor for Fe3+ and Cr2O72- ions with limit of detection of 4.62 and 2.77 µM, respectively. The sensing of Fe3+ ions corresponds to the photoinduced electron transfer (PET) mechanism, while the detection of chromate species is associated with an inner filter effect (IFE). The practical applicability of the sensor was also evaluated for different environmental water samples. The high stability, sensitivity, and specificity of Au-gCN nanocomposite make it a potential fluorescent probe for Fe3+ and Cr2O72- ions in water samples.

Effect of biochar-derived DOM on contrasting redistribution of chromate during Schwertmannite dissolution and recrystallization.

Biochar-derived dissolved organic matter (BDOM), is extensively involved in the recrystallization of minerals and the speciation alteration of associated toxic metals. This study investigates how BDOM extracted from tobacco petiole (TP) or tobacco stalk (TS) biochar influences the speciation repartitioning of Cr(VI) in environments impacted by acid mine drainage (AMD), focusing on interactions with secondary minerals during Schwertmannite (Sch) dissolution and recrystallization. TP-BDOM, rich in lignin-like substances, slowed down the Cr-Sch dissolution and Cr release under acidic conditions compared to TS-BDOM. TP-BDOM's higher O/C component exerts a delayed impact on Cr-Sch stability and Cr(VI) reduction. In-situ ATR-FTIR and 2D-COS analysis showed that carboxylic and aromatic N-OH groups in BDOM could interact with Cr-Sch surfaces, affecting sulfate and Cr(VI) release. It was also observed that slight recrystallization occurred from Cr-Sch to goethite, along with increased Cr incorporation into secondary minerals within TS-BDOM. This enhances our understanding of BDOM's role in Cr(VI) speciation changes in AMD-contaminated sites.

Simultaneous adsorption of chromate and arsenate onto ferrihydrite/alginate composite beads: Competition and mechanism.

Ferrihydrite is an effective adsorbent of chromate and arsenate. In order to gain insight into the application of ferrihydrite in water treatment, macroporous alginate/ferrihydrite beads, synthesized using two different methods (internal and encapsulation processes), were used in this work. The properties of the ferrihydrite were assessed using various techniques, including X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) theory, and zetametry. The results showed that the specific surface area of the ferrihydrite was 242 m2/g, and the PZC was pH8. The kinetic and isotherm adsorption properties of the ferrihydrite were evaluated in this study. The results indicate that the pseudo second-order and Freundlich models accurately describe the kinetic and isotherm adsorption properties of chromates and arsenates. For chromate removal, ferrihydrite exhibited a relatively high adsorption capacity (40.7 mgCr/g) compared to other adsorbents. However, the arsenate adsorption capacity of MFHB-SI (140.8 mgAs/g) was shown to be the most optimal. The internal synthesis process was suitable for arsenate retention due to the resulting arsenate precipitation. The competitive adsorption analyses indicated that the presence of chromate does not limit the adsorption of arsenate. However, the presence of arsenate almost completely inhibits the adsorption of chromate when the arsenate concentration is above 50 mg/L, due to the precipitation reaction of arsenate.

Modeling the Role in pH on Contaminant Sequestration by Zerovalent Metals: Chromate Reduction by Zerovalent Magnesium.

The role of pH in sequestration of Cr(VI) by zerovalent magnesium (ZVMg) was characterized by global fitting of a kinetic model to time-series data from unbuffered batch experiments with varying initial pH values. At initial pH values ranging from 2.0 to 6.8, ZVMg (0.5 g/L) completely reduced Cr(VI) (18.1 µM) within 24 h, during which time pH rapidly increased to a plateau value of ∼10. Time-series correlation analysis of the pH and aqueous Cr(VI), Cr(III), and Mg(II) concentration data suggested that these conditions are controlled by combinations of reactions (involving Mg0 oxidative dissolution and Cr(VI) sequestration) that evolve over the time course of each experiment. Since this is also likely to occur during any engineering applications of ZVMg for remediation, we developed a kinetic model for dynamic pH changes coupled with ZVMg corrosion processes. Using this model, the synchronous changes in Cr(VI) and Mg(II) concentrations were fully predicted based on the Langmuir-Hinshelwood kinetics and transition-state theory, respectively. The reactivity of ZVMg was different in two pH regimes that were pH-dependent at pH < 4 and pH-independent at the higher pH. This contrasting pH effect could be ascribed to the shift of the primary oxidant of ZVMg from H+ to H2O at the lower and higher pH regimes, respectively.

Rapid formation of uniformly layered materials by coupling reaction-diffusion processes with mechanical responsiveness.

Straightforward manufacturing pathways toward large-scale, uniformly layered composites may enable the next generation of materials with advanced optical, thermal, and mechanical properties. Reaction-diffusion systems are attractive candidates to this aim, but while layered composites theoretically could spontaneously arise from reaction-diffusion, in practice randomly oriented patches separated by defects form, yielding nonuniformly patterned materials. A propagating reaction front can prevent such nonuniform patterning, as is the case for Liesegang processes, in which diffusion drives a reaction front to produce layered precipitation patterns. However, while diffusion is crucial to control patterning, it slows down transport of reactants to the front and results in a steady increase of the band spacing as the front advances. Here, we circumvent these diffusive limitations by embedding the Liesegang process in mechanically responsive hydrogels. The coupling between a moving reaction front and hydrogel contraction induces the formation of a self-regulated transport channel that ballistically carries reactants toward the area where patterning occurs. This ensures rapid and uniform patterning. Specifically, large-scale ([Formula: see text]5-cm) uniform banding patterns are produced with tunable band distance (d = 60 to 160 µm) of silver dichromate crystals inside responsive gelatin-alginate hydrogels. The generality and applicability of our mechanoreaction-diffusion strategy are demonstrated by forming patterns of precipitates in significantly smaller microscopic banding patterns (d = 10 to 30 µm) that act as self-organized diffraction gratings. By circumventing the inherent limitations of diffusion, our strategy unlocks the potential of reaction-diffusion processes for the manufacturing of uniformly layered materials.

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.

Jointed Synchronous Photocatalytic Oxidation and Chromate Reduction Enabled by the Defect Distribution upon BiVO4: Mechanism Insight and Toxicity Assessment.

Exploring active and ecological materials for the restoration of complex pollution system is highly desired. This study presents a facile defect-tailoring strategy for combined pollutants purification with BiVO4 photocatalysis in which the jointed synchronous reaction of oxidation and reduction is integrated instead of the sequential reaction in two individual systems. XPS and EPR reveal that BiVO4 with a suitable oxygen vacancies (OVs) concentration and distribution exhibits superior photocatalytic activity under the coexistence of TC-HCl and Cr(VI) with Cr(VI) reduction efficiency increased by 71 times compared with the individual Cr(VI) system along with TC-HCl removal efficiency comparable to a single TC-HCl system. The mechanism of synchronous redox reactions mediated by surface OVs is revealed by comprehensive characterization together with reaction kinetic analysis, and the electronic band structure adjustment induced by the OVs variation is confirmed. Active species identification tests and intermediate product analysis confirm that singlet oxygen (1O2) accounts for the selective oxidation of TC-HCl, while electrons dominate the reduction of Cr(VI), under a coexistent environment. The influence of water quality parameters (e.g., pH, cations, anions, and organic substances) on the photocatalytic activity is investigated considering the complexity of the real aquatic environment. Importantly, toxicity assessment with Gram-negative strain E. coli as a model bacterium validates that the toxicity of the intermediates can be reduced to low or even ultralow levels. This work is dedicated to the mechanistic study of defect photocatalysis over BiVO4 and provides a jointed synchronous reaction system for combined pollutant purification.

Chromate fate and effect in bioelectrochemical systems for remediation of chlorinated solvents.

A continuous-flow bioelectrochemical reactor was developed in a previous study to address the bioremediation of groundwater contaminated by trichloroethene (TCE). The present report investigated the applicability of the same system in the presence of Cr(VI) and its possible inhibitory effect on dehalorespiring bacterial populations. Preliminary batch tests were performed at the optimal cathodic reducing potential for the reductive dechlorination (RD) of TCE (-0.65 V vs. the standard hydrogen electrode) with two different dechlorinating microorganism consortia. The results demonstrated that Cr(VI) removal efficacy was increased by microorganisms that had been previously acclimatised to Cr(VI). Specifically, Cr(VI) was completely reduced only in the presence of acclimated microorganisms. The presence of chromate negatively affected RD performance, by either (i) limiting the TCE transformation to cis-dichloroethene at lower concentrations, or (ii) completely inhibiting RD at higher concentrations. In contrast, after the acclimation period, RD was extended down to vinyl chloride, which is the main TCE daughter product. Finally, the continuous flow reactor was fed by synthetic groundwater contaminated with TCE (50 µM) and Cr(VI) (45 µM), and the experimental results showed that Cr(VI) was completely reduced under RD conditions. Moreover, TCE removal was complete, with vinyl chloride and ethene as the main intermediates, thus indicating that chromate inhibition was decreased by Cr(VI) removal.

Connections between the internal and the external capsules and the globus pallidus in the sheep: A dichromate stain X-ray microtomographic study.

Sheep are recognized as useful species for translational neurodegeneration research, in particular for the study of Huntington disease. There is a lack of information regarding the detailed anatomy and connections of the basal ganglia of sheep, in normal myeloarchitectonics and in tract-tracing studies. In this work, the organization of the corticostriatal projections at the level of the putamen and globus pallidus (GP) are explored. For the first time, the myeloarchitectonic pattern of connections between the internal (IC) and the external (EC) capsules with the GP have been investigated in the sheep. Formaldehyde-fixed blocks of the striatum were treated with a metallic stain containing potassium dichromate and visualized using micro-CT (µ-CT). The trivalent chromium (Cr3+), attached to myelin phospholipids, imparts a differential contrast to the grey and white matter compartments, which allows the visualization of myelinated fascicles in µ-CT images. The fascicles were classified according to their topographical location in dorsal supreme fascicles (X, Y, apex) arising from the IC and EC; pre-commissurally, basal fascicles connecting the ventral part of the EC with the lateral zone of the ventral pallidum (VP) and, post-commissurally, superior (Z1 ), middle (Z2 ) and lower (Z3 ) fascicles, connecting at different levels the EC with the GP. The results suggest that the presumptive cortical efferent and afferent fibres to the pallidum could be organized according to a dorsal to ventrolateral topography in the sheep, similar to that seen in other mammals. The proposed methodology has the potential to delineate the myeloarchitectonic patterns of nervous systems and tracts.

Upcycling of groundwater treatment sludge to magnetic Fe/Mn-bearing nanorod for chromate adsorption from wastewater treatment.

Groundwater treatment sludge is a Fe/Mn-bearing waste that is mass produced in groundwater treatment plant. In this study, sludge was converted to a magnetic adsorbent (MA) by adding ascorbate. The sludge was weakly magnetised in the amorphous form with Fe and Mn contents of 28.8% and 8.1%, respectively. After hydrothermal treatment, Fe/Mn oxides in the sludge was recrystallised to siderite and rhodochrosite, with jacobsite as the intermediate in the presence of ascorbate. With an increment in ascorbate dosage, the obtained magnetic adsorbent had a significant increase in chromate adsorption but a decrease in magnetisation. When the Mascorbate/MFe molar ratio was 10, the produced MA-10 was a dumbbell-shaped nanorod with a length of 2-5 µm and a diameter of 0.5-1 µm. This MA-10 showed 183.2 mg/g of chromate adsorption capacity and 2.81 emu/g of magnetisation. The mechanism of chromate adsorption was surface coprecipitation of the generated Cr3+ and Fe3+/Mn4+ from redox reaction between chromate and siderite/rhodochrosite on MA-10, separately. This study demonstrated an efficient recycling route of waste sludge from groundwater treatment to produce MA for treating chromate-bearing wastewater.

Degradation and mechanism of microcystin-LR by PbCrO4 nanorods driven by visible light.

This work focuses on the photocatalytic removal of recalcitrant organic pollutants in water treatment. Based on facile precipitation reaction, we fabricated a photocatalyst (PbCrO4) in single crystals that present evident response to visible light and employed the catalyst in the photocatalytic decomposition of microcystin-LR (MC-LR). In the degradation test using the nanorods with prepared PbCrO4 photocatalyst, a 100% removal efficiency (27 min reaction) and a kinetics constant of 0.1356 min-1 were achieved. Such a high performance of PbCrO4 in photocatalytic conversion of MC-LR was ascribed to its high carrier separation efficiency, positive valence band (VB) position, and good delocalization of VB and conduction band (CB). The test of electron spin-resonance resonance (ESR) demonstrated that excessive free OH radicals were produced during the PbCrO4 photocatalysis of MC-LR. The density functional theory (DFT) and LC/MS/MS technology were employed to ascertain the intermediates during the MC-LR photocatalytic degradation. The major intermediates were resulted from the attack of hydroxyl radicals to the ADDA side chains of MC-LR structure. This study provides a proof-of-concept strategy to develop effective photocatalysts to efficiently produce OH radicals for the visible-light induced photocatalytic degradation of MC-LR in water.

Effects of accelerated aging on characteristics, leaching, and toxicity of commercial lead chromate pigmented microplastics.

It is of environmental significance to study the leaching performance of additives from microplastics (MPs) and further evaluate the toxicity of leachate to microalgae. Here, we investigated the effects of accelerated aging on characteristics, leaching, and toxicity of commercial lead chromate pigmented MPs. Results show that aging of MPs caused surface cracks and fragmentation, increased their surface area and carbonyl contents, and promoted the release of lead chromate pigment. Chromium (Cr) and lead (Pb) tend to leach under acidic condition, rather than neutral and alkali environment. Aging treatment facilitates the leaching performance and a high concentration of NaCl solution also favors the leaching process. Toxicology experiments demonstrate that only high concentration of leachate (>10 µg L-1) exerted significant inhibitory influence (p < 0.005) on cell photosynthesis of Microcystis aeruginosa. The growth inhibition of algal cells remarkably increased with increasing leachate concentrations. We observed more inhibiting effects on cell growth and photosynthesis using the leachates of aged MPs. Longer aging time leads to more release of Cr and Pb, rendering higher toxicity to microalgae. These novel findings will benefit us from assessing the leaching behavior of additives in MPs and their toxicological risks to aquatic organisms.

Chitosan-grafted tetrapolymer using two monomers: pH-responsive high-performance removals of Cu(II), Cd(II), Pb(II), dichromate, and biphosphate and analyses of adsorbed microstructures.

For circumventing the cumbersome and expensive multifunctional and multipolymer adsorbents for high-performance removals of hazardous water-contaminant(s), chitosan-g-[2-acrylamido-2-methyl-1-propanoic acid (AMPS)-co-2-(3-acrylamidopropanamido)-2-methylpropane-1-sulfonic acid (APAMPS)-co-2-(N-(3-amino-3-oxopropyl)acrylamido)-2-methylpropane-1-sulfonic acid (NAOPAMPS)-co-acrylamide (AM)] (i.e., chitosan-g-tetrapolymer), a multifunctional scalable and reusable hydrogel, was synthesized by grafting of chitosan and in situ attachments of N-H functionalized NAOPAMPS and APAMPS hydrophilic acrylamido-monomers during free-radical solution-polymerization of the two ex situ added AMPS and AM monomers in water. The response surface methodology was employed to synthesize one hydrogel envisaging the optimum balance between swelling and stability for the superadsorption of Cu(II), Cd(II), Pb(II), Cr2O72-, and HPO42-. The in situ attachments of NAOPAMPS and APAMPS, grafting of chitosan into tetrapolymer, structures and properties, pH-responsive abilities, superadsorption mechanism, and reusability were understood via in depth microstructural analyses of adsorbed and/or unadsorbed chitosan-g-tetrapolymer(s) through 1H/13C NMR, FTIR, XPS, TGA, XRD, DLS, and pHPZC. The maximum adsorption capacities of Cd(II), Cu(II), Pb(II), Cr2O72-, and HPO42- were 1374.41, 1521.08, 1554.08, 47.76, and 32.76 mg g-1, respectively.

A paper-based length of stain analytical device for naked eye (readout-free) detection of cystic fibrosis.

The test of sweat chloride is routinely performed as a worldwide newborn screening (NBS) to the diagnosis of cystic fibrosis (CF) in infants. However, the available methods for measurement of chloride in sweat suffer from such limitations as either low selectivity and/or requiring relatively large sample size. In this work, we have designed an analytical ruler that can measure chloride ion in sweat and hence can be used for the diagnosis of cystic fibrosis. This micro-pad (µ-PAD) device is fabricated by making hydrophilic micro-channel on a filter paper impregnated with silver dichromate. After addition of chloride ion-containing sweat sample, it moves through the channel, leading to the formation of an AgCl sediment, which deposits as a white color stain, the length of which in the channel being proportional to the amount of chloride ion in sweat. A well-defined linear relation was observed between the length of white color stain and the concentration of chloride ion in the sample solutions with a relative standard deviation of 3.6% (n = 3) for an artificial sweat sample containing 100 mM chloride ion. The possible interfering effects of several different cations and anions on the detection of chloride ion were investigated and the results well-confirmed the selectivity of the proposed method. With the use of only 2.0 µL of the sample solution, the µPAD was able to measure the chloride content of sweat over a concentration range of 20.0-100.0 mM, which covers both the healthy range (˂ 40 mM) and the risky range (˃60 mM) of chloride ion. Analysis of chloride content of sweat samples by the µPAD agreed well with those obtained by a standard electrochemical method (with relative errors of lower than 10%).

Anaerobic methane oxidation coupled to chromate reduction in a methane-based membrane biofilm batch reactor.

Chromate can be reduced by methanotrophs in a membrane biofilm reactor (MBfR). In this study, we cultivated a Cr(VI)-reducing biofilm in a methane (CH4)-based membrane biofilm batch reactor (MBBR) under anaerobic conditions. The Cr(VI) reduction rate increased to 0.28 mg/L day when the chromate concentration was ≤ 2.2 mg/L but declined sharply to 0.01 mg/L day when the Cr(VI) concentration increased to 6 mg/L. Isotope tracing experiments showed that part of the 13C-labeled CH4 was transformed to 13CO2, suggesting that the biofilm may reduce Cr(VI) by anaerobic methane oxidation (AnMO). Microbial community analysis showed that a methanogen, i.e., Methanobacterium, dominated in the biofilm, suggesting that this genus is probably capable of carrying out AnMO. The abundance of Methylomonas, an aerobic methanotroph, decreased significantly, while Meiothermus, a potential chromate-reducing bacterium, was enriched in the biofilm. Overall, the results showed that the anaerobic environment inhibited the activity of aerobic methanotrophs while promoting AnMO bacterial enrichment, and high Cr(VI) loading reduced Cr(VI) flux by inhibiting the methane oxidation process.

Arsenic removal by copper-impregnated natural mineral tufa part II: a kinetics and column adsorption study.

This batch and column kinetics study of arsenic removal utilized copper-impregnated natural mineral tufa (T-Cu(A-C)) under three ranges of particle size. Non-competitive kinetic data fitted by the Weber-Morris model and the single resistance mass transfer model, i.e., mass transfer coefficient kfa and diffusion coefficient (Deff) determination, defined intra-particle diffusion as the dominating rate controlling step. Kinetic activation parameters, derived from pseudo-second-order rate constants, showed low dependence on adsorbent geometry/morphology and porosity, while the diffusivity of the pores was significant to removal efficacy. The results of competitive arsenic adsorption in a multi-component system of phosphate, chromate, or silicate showed effective arsenic removal using T-Cu adsorbents. The high adsorption rate-pseudo-second-order constants in the range 0.509-0.789 g mg-1 min-1 for As(V) and 0.304-0.532 g mg1 min1 for As(III)-justified further application T-Cu(A-C) in a flow system. The fixed-bed column adsorption data was fitted using empirical Bohart-Adams, Yoon-Nelson, Thomas, and dose-response models to indicate capacities and breakthrough time dependence on arsenic influent concentration and the flow rate. Pore surface diffusion modeling (PSDM), following bed-column testing, further determined adsorbent capacities and mass transport under applied hydraulic loading rates.

Insights into the mode of flavin mononucleotide binding and catalytic mechanism of bacterial chromate reductases: A molecular dynamics simulation study.

Enzymes from natural sources protect the environment via complex biological mechanisms, which aid in reductive immobilization of toxic metals including chromium. Nevertheless, progress was being made in elucidating high-resolution crystal structures of reductases and their binding with flavin mononucleotide (FMN) to understand the underlying mechanism of chromate reduction. Therefore, herein, we employed molecular dynamics (MD) simulations, principal component analysis (PCA), and binding free energy calculations to understand the dynamics behavior of these enzymes with FMN. Six representative chromate reductases in monomeric and dimeric forms were selected to study the mode, dynamics, and energetic component that drive the FMN binding process. As evidenced by MD simulation, FMN prefers to bind the cervix formed between the catalytic domain surrounded by strong conserved hydrogen bonding, electrostatic, and hydrophobic contacts. The slight movement and reorientation of FMN resulted in breakage of some crucial H-bonds and other nonbonded contacts, which were well compensated with newly formed H-bonds, electrostatic, and hydrophobic interactions. The critical residues aiding in tight anchoring of FMN within dimer were found to be strongly conserved in the bacterial system. The molecular mechanics combined with the Poisson-Boltzmann surface area binding free energy of the monomer portrayed that the van der Waals and electrostatic energy contribute significantly to the total free energy, where, the polar solvation energy opposes the binding of FMN. The proposed proximity relationships between enzyme and FMN binding site presented in this study will open up better avenues to engineer enzymes with optimized chromate reductase activity for sustainable bioremediation of heavy metals.

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.

Adsorption mechanisms of chromate and phosphate on hydrotalcite: A combination of macroscopic and spectroscopic studies.

Hydrotalcite (HT) is a layered double hydroxide (LDH), which is considered as a potential adsorbent to remove anion contaminants. In this study, adsorption of chromate (CrO4) and phosphate (PO4) on HT was conducted at various pH and temperatures. Related adsorption mechanisms were determined via the isotherm, kinetic, and competitive adsorption studies as well as the Cr K-edge X-ray absorption fine-structure (XAFS) spectroscopy. The maximum adsorption capacities for CrO4 and PO4 on HT were 0.16 and 0.23 mmol g-1. Regarding adsorption kinetics, CrO4 and PO4 adsorption on HT could be well described by the second order model, and the rate coefficient of CrO4 and PO4 on HT decreased significantly with the increasing pH from 5 to 9. The adsorption kinetics for CrO4 and PO4 were divided into fast and slow stages with the boundary at 15 min. This biphasic adsorption behavior might be partially attributed to multiple reactive pathways including anion exchange and surface complexation. Fitting results of Cr K-edge EXAFS analysis showed a direct bonding between CrO4 and Al on HT surfaces. Such a surface complexation appeared to be the rate-limiting step for CrO4 adsorption on HT. By contrast, the diffusion through the hydrated interlayer space of HT was the major rate-limiting step for PO4. This study determined the adsorption behaviors of CrO4 and PO4 on HT, including the initial transfer process and the subsequent adsorption mechanisms. Such information could improve the strategy to use HT as the potential adsorbent for the remediation of anionic pollutants.