In situ carbothermal synthesis of carbonized bacterial cellulose embedded with nano zero-valent iron for removal of Cr(VI).

Carbonized bacterial cellulose embedded with highly dispersed nano zero-valent iron (nZVI), denoted as nZVI@CBC, was prepared through one-step in situ carbothermal treatment of bacterial cellulose adsorbing iron(III) nitrate. The structure characteristics of nZVI@CBC and its performance in removing hexavalent chromium Cr(VI) were investigated. Results showed the formation of nZVI@CBC with a surface area of 409.61 m2/g at 800 °C, with nZVI particles of mean size 28.2 nm well distributed within the fibrous network of CBC. The stability of nZVI was enhanced by its carbon coating, despite some inevitable oxidation of exposed nZVI. Batch experiments demonstrated that nZVI@CBC exhibited superior removal efficiency compared to bare nZVI and CBC. Under optimal conditions, nZVI@CBC exhibited a high Cr(VI) adsorption capacity of up to 372.42 mg/g. Therefore, nZVI@CBC shows promise as an effective adsorbent for remediating Cr(VI) pollution in water.

Immature persimmon residue as a novel biosorbent for efficient removal of Pb(II) and Cr(VI) from wastewater: Performance and mechanisms.

Owing to the powerful affinity of tannin toward heavy metal ions, it is frequently immobilized on adsorbents to enhance their adsorption properties. However, natural adsorbents containing tannin have been overlooked owing to its water solubility. Herein, a novel natural adsorbent based on the immature persimmon residue (IPR) with soluble tannin removed was fabricated to eliminate Pb(II) and Cr(VI) in aquatic environments. The insoluble tannin in IPR endowed it with prosperous properties for eliminating Pb(II) and Cr(VI), and the IPR achieved maximum Pb(II) and Cr(VI) adsorption quantities of 68.79 mg/g and 139.40 mg/g, respectively. Kinetics and isothermal adsorption analysis demonstrated that the removal behavior was controlled by monolayer chemical adsorption. Moreover, the IPR exhibited satisfactory Pb(II) and Cr(VI) removal efficiencies even in the presence of multiple coexisting ions and showed promising regeneration potential after undergoing five consecutive cycles. Additionally, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) analysis unveiled that the elimination mechanisms were primarily electrostatic attraction, chelation and reduction. Overall, the IPR, as a tannin-containing biosorbent, was verified to possess substantial potential for heavy metal removal, which can provide new insights into the development of novel natural adsorbents from the perspective of waste resource utilization.

Amyloid-Templated Palladium Nanoparticles for Water Purification by Electroreduction.

Electrocatalysis offers great promise for water purification but is limited by low active area and high uncontrollability of electrocatalysts. To overcome these constraints, we propose hybrid bulk electrodes by synthesizing and binding a Pd nanocatalyst (nano-Pd) to the electrodes via amyloid fibrils (AFs). The AFs template is effective for controlling the nucleation, growth, and assembly of nano-Pd on the electrode. In addition, the three-dimensional hierarchically porous nanostructure of AFs is beneficial for loading high-density nano-Pd with a large active area. The novel hybrid cathodes exhibit superior electroreduction performance for the detoxification of hexavalent chromium (Cr6+ ), 4-chlorophenol, and trichloroacetic acid in wastewater and drinking water. This study provides a proof-of-concept design of an AFs-templated nano-Pd-based hybrid electrode, which constitutes a paradigm shift in electrocatalytic water purification, and broadens the horizon of its potential engineered applications.

Cationic surface-modified regenerated nanocellulose hydrogel for efficient Cr(VI) remediation.

Because nanocellulose has a large specific surface area and abundant hydroxyl functional groups due to its unique nanomorphology, interest increases as an eco-friendly water treatment material. However, the distinctive properties of nanocellulose, which exists in a dispersion state, strongly hamper its usage in practical water treatment processes. Additionally, nanocellulose shows low performance in removing anionic pollutants because of its anionic characteristics. In an effort to address this challenge, regenerated cellulose (RC) hydrogel was fabricated through cellulose's dissolution and regeneration process using an eco-friendly aqueous solvent system. Subsequently, a crosslinking process was carried out to introduce the cationic functional groups to the RC surface PEI coating (P/RC). As a result, the PEI surface cationization process improved the mechanical rigidity of RC and showed an excellent Cr(VI) removal capacity of 578 mg/g. In addition, the prepared P/RC maintained more than 90% removal efficiency even after seven reuses.

Pseudomonas putida APRRJVITS11 as a potent tool in chromium (VI) removal from effluent wastewater.

Bioremediation is an essential feature of microorganisms concerning contaminations in soil and water. The use of microorganisms has been proved to be an effective treatment of industrially released effluents comprising of heavy metals, such as chromium (VI). In the current study, seasonal variations were observed in the concentrations of chromium(VI) as the samples from selected locations showed an increase in mean concentration during the summer compared to the low mean during winter, suggesting excessive evaporation in the summer leading to the heavy metal accumulation. Among the 35 isolates obtained from tannery effluent contaminated wastewater sources the 3 unique strains identified as Streptococcus pyogenes strain APRRJVITS10, Pseudomonas putida strain APRRJVITS11, and Bacillus thuringiensis strain APRRJVITS15, showed tolerance toward chromium(VI) and the maximum tolerance for each strain was 1250 ppm. The media optimization through shake flask methods showed chromium(VI) (in 100 ml LB broth) removal of 47.82%, 48.11%, and 49.93% by S. pyogenes, P. putida, and B. thuringiensis respectively. Further, Pseudomonas putida showed chromium(VI) (in 1500 ml LB broth) removal of 50.48% in optimized conditions, proving to be highly potential for treating effluent wastewater for chromium(VI) removal.

Combined Application of MMT K10 Supported Copper Oxide Nanoparticles for Complete Removal of Cr(VI) from Aqueous Solution and Their Antibacterial Potential.

Montmorillonite K10 (MMT K10) supported copper oxide nanoparticles (CuONPs) were synthesized by incorporating CuONPs onto the surface of MMT K10 by reducing the metal precursor with the help of hydrazine hydrate. Effects of various factors on the efficiency of composite to remove hexavalent chromium were studied to find out the optimum conditions for maximum removal. Under optimum conditions 15 mg of the synthesized nanocomposite was found capable to almost completely remove (99.9 %) hexavalent chromium in 30 min from a 10 ppm aqueous chromium solution and that too in a wide range of pH from 2.88 to 5.56. The synthesized MMT K10 supported CuONPs were characterized by UV, SEM-EDX, FTIR and XRD studies. The average particle size of supported CuONPs was found to be 22.9 nm. Antibacterial potential of the prepared composite was also studied for one Gram-positive bacterium Staphylococcus aureus (ATCC 25323) and one Gram-negative bacterium Pseudomonas aeruginosa (ATCC 27853). The prepared nanocomposite was found to have excellent bactericidal potential and its statistical analysis was performed using t-test which indicates both bacterial strains of Pseudomonas aeruginosa and Staphylococcus aureus show different zone of inhibition for different concentrations.

Mechanistic study of Cr (VI) removal by modified alginate/GO composite via synergistic adsorption and photocatalytic reduction.

A novel composite material was prepared by blending graphene oxide into polyethyleneimine grafted sodium alginate. The synthesized material was investigated as adsorbent and photocatalyst for the removal of hexavalent chromium (Cr (VI)) from aqueous solutions. The composite material has shown remarkable removal efficiency for Cr (VI) in high initial concentration solutions as the removal rate reached 86.16% and 99.92% for adsorption and photoreduction, respectively. We discovered experimentally that the adsorption was dominated via electrostatic interaction while the blending of GO could contribute in stimulating electrons for the photoreduction process. Moreover, the photoreduction can alter the surface charge of chromium species, thus electrostatic repulsion could regenerating the active sites of composite spontaneously. The conduction band energy was calculated as -2.04 eV, which proved that blending GO can narrow the bandgap of the composite material, thus enhance the light response and the photoreduction ability towards Cr (VI).

Rapid removal of Cr(III) from high-salinity wastewater by cellulose-g-poly-(acrylamide-co-sulfonic acid) polymeric bio-adsorbent.

A cellulose-g-poly-(acrylamide-co-sulfonic acid) polymeric bio-adsorbent (CASA) was prepared by grafting copolymerization, and used to adsorb Cr(III) from leather wastewater. The SEM, XRD, FTIR, and XPS results showed that CASA contains many spherical particles and functional groups such as NH2, CO, and HSO3. The adsorption experiments revealed that CASA presented excellent adsorption performance for Cr(III) (274.69 mg/g of max adsorption capacity) from high-salinity wastewater, which was much better than other reported adsorbents with different structures. Meanwhile, adsorption equilibrium could be reached within 10 min due to the introduction of abundant sulfonic acid groups on its surface. In addition, the adsorption process followed the Langmuir adsorption isotherm, and the experimental data conformed to the pseudo-second-order kinetics model. Moreover, the main adsorption mechanisms include chelation, electrostatic interactions, and cation exchange, which provide an important theoretical basis for the removal of toxic inorganic pollutants from leather wastewater.

Polysaccharide-based (nano)materials for Cr(VI) removal.

Chromium is a potentially poisonous and carcinogenic species, which originates from human activities and various industries such as leather, steel, iron, and electroplating industries. Chromium is present in various oxidation states, among which hexavalent chromium (Cr(VI)) is highly toxic as a natural contaminant. Therefore, chromium, particularly Cr(VI), must be eliminated from the environment, soil, and water to overcome significant problems due to its accumulation in the environment. There are different approaches such as adsorption, ion exchange, photocatalytic reduction, etc. for removing Cr(VI) from the environment. By converting Cr(VI) to Cr(III), its toxicity is reduced. Cr(III) is essential for the human diet, even in small amounts. Today, biopolymers such as alginate, cellulose, gum, pectin, starch, chitin, and chitosan have received much attention for the removal of environmental pollutants. Biopolymers, particularly polysaccharides, are very useful compounds due to their OH and NH2 functional groups and some advantages such as biodegradability, biocompatibility, and accessibility. Therefore, they can be widely applied in catalytic applications and as efficient adsorbents for the removal of toxic compounds from the environment. This review briefly investigates the application of polysaccharide-based (nano)materials for efficient Cr(VI) removal from the environment using adsorption/reduction, photocatalytic, and chemical reduction mechanisms.

Effective removal of levofloxacin drug and Cr(VI) from water by a composed nanobiosorbent of vanadium pentoxide@chitosan@MOFs.

Wastewaters is generally polluted with various inorganic and organic contaminants which require effective multipurpose purification technology. In this respect, a novel V2O5@Ch/Cu-TMA nanobiosorbent was constructed via encapsulation of nanoscale metal organic frameworks (Cu-TMA) into vanadium pentoxide-imbedded-chitosan matrix to comprehensively investigate its efficiency in removal of levofloxacin drug (LEVO) (e.g., organic pollutant) and chromium (VI) (e.g., inorganic pollutant) from water. Both LEVO drug and Cr(VI) adsorptions were correlated to pseudo-second order (R2 = 1) and Langmuir isotherm (R2 = 0.9924 for LEVO and R2 = 0.9815 for Cr(VI)). Adsorption of Cr(VI) was confirmed to be spontaneous and endothermic reactions, while LEVO was found to proceed via spontaneous and exothermic reactions based on the thermodynamic parameters. The emerged V2O5@Ch/Cu-TMA is regarded as an excellent nanobiosorbent for removal of inorganic contaminant as Cr(VI) from all natural water samples (tap, sea and wastewater) with percentages range 92.43%-96.95% and organic contaminant as LEVO drug from tap and wastewater (91.99%-97.20%).

Removal performance and mechanisms of toxic hexavalent chromium (Cr(VI)) with ZnCl2 enhanced acidic vinegar residue biochar.

Acidic vinegar residue (VR) and toxic hexavalent chromium (Cr(VI)) are unfavorable substances due to their toxicity against the environment. In this study, modified biochar was prepared to investigate the removal mechanisms of Cr(VI). The results showed that ZnCl2 could yield highly aromatic products with improved pore structures. The adsorption capacity of modified biochar reached the highest efficiency (236.81 mg g-1) when the mass ratio of ZnCl2/VR was 1, which is higher than the control (9.96 mg g-1). In addition, Cr(VI) adsorption coexisted with physical and chemical adsorption. The mechanisms of modified biochar to Cr(VI) removal included electrostatic attraction, pore filing, reduction and surface complexation. Notably, as a fermented product, VR biochar was a nitrogen-rich product; the formation of the amino group could provide a direct solid site for Cr(VI) adsorption. Subsequently, amorphous silica could be converted into silanol to provide additional adsorption sites. This work establishes the theoretical basis for efficient Cr(VI) removal and VR reuse.

Facile fabrication of novel magnetic ZIF-67 MOF@aminated chitosan composite beads for the adsorptive removal of Cr(VI) from aqueous solutions.

Metal organic frameworks (MOFs) have become premium candidates for the removal of hazardous contaminants from wastewater. However, MOFs have a vast obstacle which is their poor recyclability. In this study, ZIF-67 was decorated with magnetic Fe3O4 nanoparticles, and then embedded into aminated chitosan (AmCs) matrix to form core-dual shell Fe3O4/ZIF-67@AmCs composite beads. Diverse analysis tools were utilized to ensure the successful fabrication of the magnetic composite beads. The fabricated magnetic composite beads were examined their adsorptive removal aptitude towards toxic Cr(VI) ions. The gained results refereed that a maximum adsorption capacity of 119.05 mg/g was attained by magnetic Fe3O4/ZIF-67@AmCs composite beads at 25 °C. The process obeyed both of Langmuir and Freundlich isotherm models, and the pseudo 2nd order was more suitable kinetic model to represent the adsorption process. Besides, Fe3O4/ZIF-67@AmCs composite showed an excellent recyclability for the removal of Cr(VI) ions from their aqueous solutions for seven consecutive cycles.

Biological treatment of hazardous heavy metals by Streptomyces rochei ANH for sustainable water management in agriculture.

Microbial bioremediation of heavy metals-polluted industrial effluents has been adopted as one of the most effective eco-friendly tool to cope up with the harmful effects of metals. This study was designed to investigate the biosorption potential of marine actinomycetes isolated from the Alexandrian Mediterranean Seacoast, Egypt, with their potential use in metal remediation of industrial effluents. Among the nine marine actinomycetes isolates, Streptomyces rochei ANH showed the highest versatile metal resistance capability with MIC values of 125 mg/l for Cr6+ and 60 mg/l for both Cd2+ and Pb2+. Additionally, scanning electron micrographs showed complete disintegration of Cr6+-treated biomass compared with the control ones where spores remained intact and connected in long chains. The study also aimed to improve the percentage of Cr6+ biosorption by S. rochei ANH biomass using the statistical designs of Plackett-Burman and Box-Behnken where up to 85% of Cr6+ removal was recorded under the following conditions: pH (5), incubation temperature (30 °C), contact time (3 h), agitation speed (90 rpm), initial Cr6+ concentration (50 mg/l) and living biomass concentration (10 mg/ml). The results also showed that the percentage of Cr6+ biosorption by S. rochei ANH decreased gradually beyond these values. Moreover, the results revealed that the use of the biomass of S. rochei ANH is an effective biotechnological agent for the biological treatment of heavy metal-contaminated tannery effluent where the percentages of metal removal were in the following order: Ni2+ (100%) ≥ Cu2+ ≥ Mn2+ ≥ Fe2+ > Pb2+ (95%) ≥ Cd2+ > Cr6+ (86%). Furthermore, the treated effluent exhibited a stimulating effect on the germination process of Lepidium sativum seeds. Therefore, the present study implies that S. rochei ANH can be considered a powerful candidate to mitigate hazardous heavy metals pollution from industrial effluents and improve the water quality for agricultural purposes.

Microbial Sensing and Removal of Heavy Metals: Bioelectrochemical Detection and Removal of Chromium(VI) and Cadmium(II).

The presence of inorganic pollutants such as Cadmium(II) and Chromium(VI) could destroy our environment and ecosystem. To overcome this problem, much attention was directed to microbial technology, whereas some microorganisms could resist the toxic effects and decrease pollutants concentration while the microbial viability is sustained. Therefore, we built up a complementary strategy to study the biofilm formation of isolated strains under the stress of heavy metals. As target resistive organisms, Rhizobium-MAP7 and Rhodotorula ALT72 were identified. However, Pontoea agglumerans strains were exploited as the susceptible organism to the heavy metal exposure. Among the methods of sensing and analysis, bioelectrochemical measurements showed the most effective tools to study the susceptibility and resistivity to the heavy metals. The tested Rhizobium strain showed higher ability of removal of heavy metals and more resistive to metals ions since its cell viability was not strongly inhibited by the toxic metal ions over various concentrations. On the other hand, electrochemically active biofilm exhibited higher bioelectrochemical signals in presence of heavy metals ions. So by using the two strains, especially Rhizobium-MAP7, the detection and removal of heavy metals Cr(VI) and Cd(II) is highly supported and recommended.

Facial Synthesis of Adsorbent from Hemicelluloses for Cr(VI) Adsorption.

It is challenging work to develop a low-cost, efficient, and environmentally friendly Cr(VI) adsorbent for waste water treatment. In this paper, we used hemicelluloses from chemical fiber factory waste as the raw material, and prepared two kinds of carbon materials by the green hydrothermal method as adsorbent for Cr(VI). The results showed that hemicelluloses hydrothermally treated with citric acid (HTC) presented spherical shapes, and hemicelluloses hydrothermally treated with ammonia solution (HTC-NH2) provided spongy structures. The adsorption capacity of the samples can be obtained by the Langmuir model, and the adsorption kinetics could be described by the pseudo-second-order model at pH 1.0. The maximum adsorption capacity of HTC-NH2 in the Langmuir model is 74.60 mg/g, much higher than that of HTC (61.25 mg/g). The green hydrothermal treatment of biomass with ammonia solution will provide a simple and feasible way to prepare adsorbent for Cr(VI) in waste water treatment.

Identification of metal binding motifs in protein frameworks to develop novel remediation strategies for Hg2+ and Cr(VI).

Amino acid sequences in metal-binding proteins with chelating properties offer exciting applications in biotechnology and medical research. To enhance their application in bioremediation studies, we explicitly aimed to identify specific metal-binding chelating motifs in protein structures for two significant pollutants, such as mercury (Hg2+) and chromium Cr(V1). For this purpose, we have performed an extensive coordination chemistry approach by retrieving Hg2+ and Cr(V1) binding protein structures from the protein database and validated using the B-factor, a term defining uncertainty of the atoms and with occupancy to obtain the best binding motifs. Our analysis revealed that acidic amino acids like aspartic acid, glutamic acid, and basic amino acids such as cysteine and histidine are predominant in coordinating with these metals. The order of preference in Hg2+-bound structures is predicted to be Cys > His > Asp > Glu, and for Cr(V1) is His > Asp > Glu. Examination of the atomic coordinates and their distance from each metal revealed that the sulfur atoms of cysteine showing more preference towards Hg2+coordination with an atomic distance ranging from 1.5 to 2.9 Å. Likewise, oxygen atoms of aspartic acid, glutamic acid and nitrogen atoms of histidine are within 2 Å of Cr(V1) coordination. Based on these observations, we obtained C-C-C, C-X(2)-C-C-(X)2-C, H-C-H motifs for Hg2+, and D-X(1)-D, H-X(3)-E motif for Cr(V1) to be shared within the coordination space of 3 Å. As a future scope, we propose that the identified metal-binding chelating motifs are oligopeptides and can display on the surface of microorganisms such as Escherichia coli and Saccharomyces cerevisiae for effective removal of natural Hg2+ and Cr(V1) through biosorption. Hence, our results will provide the basis for futuristic bioremediation.

Biodegradable gelatin composite hydrogels filled with cellulose for chromium (VI) adsorption from contaminated water.

Biopolymers are promising materials for water treatment applications due to their abundance, low cost, expandability, and chemical structure. In this work, gelatin hydrogels filled with cellulose in the form of pristine eucalyptus residues (PER) or treated eucalyptus residues (TER) were prepared for adsorption and chromium removal in contaminated water. PER is a lignocellulosic compound, with cellulose, hemicellulose, and lignin, while TER has cellulose as a major component. FT-Raman Spectroscopy and FTIR analysis confirmed the crosslink reaction with glutaraldehyde and indicated that fillers altered the gelatin molecular vibrations and formed new hydrogen bonds, impacting the hydrogels' crystalline structure. The hydrogen bond energy was altered by the cellulosic fillers' addition and resulted in higher thermal stability (~10 °C). Hydrogels presented a Fickian diffusion, where gelatin hydrogel showed the highest swelling ability (466%), and composites showed lower values with the filler content increase. The chromium adsorption capacity presented values between 12 and 13 mg/g, i.e., featuring an excellent removal capacity which is related with hydrogel crosslinked structure and fibers surface hydroxyl groups, highlighting gelatin hydrogel TER 5% with better removal capacity. The developed hydrogels were produced from biomacromolecules with low-cost and potential application in contaminated water.

Study on detoxification and removal mechanisms of hexavalent chromium by microorganisms.

Extensive industrial activities have led to an increase of the content of chromium in the environment, which causes serious pollution to the surrounding water, soil and atmosphere. The enrichment of chromium in the environment through the food chain ultimately affects human health. Therefore, the remediation of chromium pollution is crucial to development of human society. A lot of scholars have paid attention to bioremediation technology owing to its environmentally friendly and low-cost. Previous reviews mostly involved pure culture of microorganisms and rarely discussed the optimization of bioreduction conditions. To make up for these shortcomings, we not only introduced in detail the conditions that affect microbial reduction but also innovatively introduced consortium which may be the cornerstone for future treatment of complex field environments. The aim of this study is to summary chromium toxicity, factors affecting microbial remediation, and methods for enhancing bioremediation. However, the actual application of bioremediation technology is still facing a major challenge. This study also put forward the current research problems and proposed future research directions, providing theoretical guidance and scientific basis for the application of bioremediation technology.

Iron oxides decorated graphene oxide/chitosan composite beads for enhanced Cr(VI) removal from aqueous solution.

This study is the first to evaluate the effects of Iron oxides (FeOx) species and their decoration on graphene oxide/chitosan (GO/CS) composites for Cr(VI) removal and the possibility of Fe secondary pollution. Results show that Fe(III) is a better decoration material than Fe(II) and decoration through immersion-evaporation shows a higher adsorption capacity of Cr(VI) (Qe) than co-precipitation. Fe2O3-GO/CS as the only eco-friendly composite for enhanced Cr(VI) removal is further used for batch adsorption experiments, characterization, kinetics, isotherms, and thermodynamic studies. It is found that Cr(VI) removal mainly includes electrostatic attraction between Cr(VI) oxyanions and surface -NH3+ and -OH2+, and the adsorbed Cr(VI) partially reduces to Cr(III). Qe increases with the increasing initial Cr(VI) concentration, contact time, and temperature, while decreases with the increasing pH and mass and volume ratio (m/v). The coexisting ions (Cl-, NO3-, SO42-, PO43-, As, Fe, and Pb) can cause an obvious decrease of Qe. The removal efficiency (Re) and Qe are 94.3% and 83.8 mg/g, respectively under the optimal conditions. After five times of regeneration, Re is still as high as 84% and Qe drops about 2.6%. Cr(VI) adsorption is spontaneous and endothermic, which is best fitted with the Sips model, and the fitted maximum Qe is 131.33 mg/g.

Hydroxypropyl chitosan-based dual self-healing hydrogel for adsorption of chromium ions.

A facile, environmentally benign approach had been developed for the preparation of dual self-healing and adsorption hydrogel through hydroxypropyl chitosan (HPCS), polyacrylamide (PAM) and polyvinyl alcohol (PVA). The self-healing capability of the hydrogels without any external stimulus was ascribed to dynamic Schiff-base bonds, borate bonds and hydrogen bonds, while the adsorption capacity of hydrogels came from the protonated amino group effect at a specific pH. It was demonstrated that the HPP DN hydrogel had a maximum equilibrium swelling ratio of 643% and a maximum compressive strength of 267 kPa. The weight loss of HPP DN hydrogel was 14.26% lower than that of HPCS/PAM single network hydrogel, furthermore, HPP DN hydrogel could achieve self-healing within 10 h. Due to the large number of active groups, the adsorption capacity of Cr6+ reached 95.31 mg/g. It could adsorb in a wide pH range of 1 to 6, and could describe by pseudo-first-order kinetic model and Langmuir adsorption isotherm model, which would provide a new idea for the adsorption and removal of heavy metal ions. In short, the prepared HPP hydrogel had dual self-healing ability, adsorption capacity and mechanical strength, which would make it a promising candidate for long-life adsorbent.