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The flocculation of dyeing wastewater generated a large amount of sludge that was often disposed as refractory hazardous waste. The resource utilization of flocculation sludge was of great significance in terms of low treatment cost of sludge, low environmental risk and high usage efficiency of reactive dyes. Herein, a flocculation sludge-derived (FSD) adsorbent was prepared via cross-linking of flocculation sludge yielding by carboxymethyl chitosan-based flocculants and dyes. FSD adsorbent had excellent selective adsorption performance for methylene blue (MB) treatment. The highest removal rate of MB and adsorption capacity of FSD adsorbent were 96.48 % and 354.7066 mg/g, attributing to its rich functional groups, negative charges and special micropore structure. FSD adsorbent owned the favorable regeneration efficiency and stability. Its removal rate of MB was still above 71.8 % after 6 regeneration-adsorption cycles. Its leaching rate of dyes was only 0.0016 mg/mg that was rather lower than common dried flocculation sludge. The adsorption processes of FSD adsorbent were complex in accordance with its characteristics, adsorption isotherms, adsorption kinetics and theoretical calculation. Multiple adsorption mechanisms were present in the treatment of dyeing wastewater by FSD adsorbent. The resource utilization of flocculation sludge, as adsorbents, was a potential candidate in field application., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

To address the urgent need for efficient removal of lead-containing wastewater and reduce the risk of toxicity associated with heavy-metal wastewater contamination, materials with high removal rates and easy separation must be developed. Herein, a novel organic-inorganic hybrid material based on phosphorylated magnetic chitosan (MSCP) was synthesized and applied for the selective removal of lead (II) from wastewater. From the characterization and the experimental results can be obtained that the magnetic saturation strength of MSCP reaches 14.65 emu/g, which can be separated quickly and regenerated readily, and maintains high adsorption performance even after 5 cycles, indicating that the adsorbent possesses good magnetic separation performance and durability. Also, MSCP showed high selective adsorption performance for lead in the multiple metal ions coexistence solutions at pH 6.0 and room temperature, with an adsorption coefficient S Pb-MSCP of 78.85%, which was much higher than that of MSC (the S Pb-MSC was 11.59%). Additionally, in the single lead system, the sorption characteristics of Pb(II) on MSCP and MCP had obvious pH-responsiveness, and their adsorption capacity increased with the increase of solution pH, reaching the maximal values of 80.19 and 72.68 mg/g, respectively. It is noteworthy that the acid resistance of MSCP with an inert layer coated on the core is significantly improved, with almost no iron leaching from MSCP over the entire acidity range, while MCP has 7.63 mg/g of iron leaching at pH 1.0. Significantly, MSCP exhibited a maximum adsorption capacity of 102.04 mg/g, which matches the Langmuir model at pH 6.0 and 298.15 K, and points to the pseudo-second-order kinetics of the chemisorption process of Pb(II) on MSCP. These findings highlight the great potential of MSCP for Pb(II) removal from aqueous solution, making it a promising solution for Pb(II) contamination in wastewater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Simultaneously removing heavy metal and dye from complex wastewater is of great significance to industrial wastewater treatment. Herein, a novel magnetic adsorbent, DTPA-modified chitosan-coated magnetic silica nanoparticle (FFO@Sil@Chi-DTPA), was successfully prepared and used to enhance the Pb(II) selective adsorption from multi-metal wastewater based on anion-synergism. In the competitive experiment conducted in a multi-ion solution, the type of selective adsorption of metals was changed by the adsorbents before and after amidation, in which FFO@Sil@Chi-DTPA exhibited an excellent selectively for capturing Pb(II), while FFO@Sil@Chi demonstrated highly selective adsorption of silver. More importantly, the selective adsorption of Pb(II)S by FFO@Sil@Chi-DTPA was enhanced from 111.71 to 268.01 mg g -1 when the coexisting MB concentrations ranged from 0 to 100 mg L -1 at pH 6.0. In the Pb(II)-MB binary system, Pb(II) and MB exhibited a synergistic effect, in which the presence of MB strengthened the adsorption effect of Pb(II) due to the sulfonic acid groups in MB molecules that create new specific sites for Pb(II) adsorption, while MB adsorption was also enhanced by the presence of Pb(II). This work provides a new strategy for exploring novel adsorbents that can enhance the selective removal of heavy metal in complex wastewater based on anion-synergism., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Biopolymer-based flocculants have become a potential substitute for inorganic coagulants and synthetic organic flocculants due to their wide natural reserves, environmental friendliness, easy natural degradation, and high material safety. In recent years, with more and more attention to clean technologies, a lot of researches on the modification and application of biopolymer-based flocculants have been carried out. The present paper reviews the latest important information about the base materials of biopolymer-based flocculants, including chitosan, starch, cellulose, and lignin etc. This review also highlights the various modification methods of these base materials according to reaction types in detail. Via the recent researches, the flocculation mechanisms of biopolymer-based flocculants, such as adsorption, bridging, charge neutralization, net trapping, and sweeping, as well as, some other special mechanisms are comprehensively summarized. This paper also focuses on the water treatment conditions, the removal efficiency, and advantages of biopolymer-based flocculants in applications. Further, this review sheds light on the future perspectives of biopolymer-based flocculants, which may make progress in the sources of base materials, modification processes, multi-function, and deepening application researches. We believe that this review can guide the further researches and developments of biopolymer-based flocculants in the future, to develop them with a higher efficiency, a lower cost, more safety, and multi-function for more diversified applications. Graphical abstract., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The fine molecular structure of a flocculant fundamentally determines the internal flocculation mechanism and the final application property. In this work, three series of chitosan-based polymers (CTS-g-PAMD) with divergent charge densities and graft chain distribution were synthesized by graft copolymerization using acrylamide (AM) and acryloyloxyethyltrimethylammonium chloride (DAC). Meanwhile, flocculant with linear chain structure (CTS-CTA) was prepared by etherification using 3-chloro-2-hydroxypropyltrimethylammonium chloride (CTA). The characterization results confirmed that various monomers had been successfully introduced into chitosan. The reaction basically happened on -NH 2 at C 2 of chitosan, and the ring structure of chitosan was destroyed by free radical reaction. The obtained flocculants were used to flocculate bentonite and humic acid solution. Besides dose, the effects of chain structure, charge density and chain distribution on flocculation performance were systematically studied. Based on the fractal theory and flocculation kinetics, the effects of structural factors on floc characteristics were also investigated. The results showed that, flocculant with abundant graft chains exerts better flocculation performance and floc characteristic due to enhanced adsorption electrical neutralization and adsorption bridging effect. The effects of charge density and chain distribution on the flocculation performance were disparate in the range of insufficient and excessive doses. Furthermore, on the basis of the quadratic polynomial model, quantitative structure-effect relationships were established, which has guiding significance for the development and utilization of flocculants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Chitosan-based flocculants are efficient and biodegradable, possessing the potential application in water treatment. A chitosan-based flocculant, CTS-g-PAM, was prepared via grafting copolymerization. Two main structures of CTS-g-PAM were detected by X-ray photoelectron spectroscopy (XPS), and they related to the different performances of CTS-g-PAM in the treatment of model azo dyeing wastewater in terms of removal efficiency, floc size and zeta potential. CTS-g-PAM with the optimal ratio of CN to -NH- owned the best performance. CN reinforced the interaction between CTS-g-PAM and azo dyes and charge neutralization while the flocs formed in the case were large and compacted. However, excessive CN accelerated itself hydrolysis and leaded to the decomposition of CTS-g-PAM, deteriorating the performance of the flocculant., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The chitosan (CTS) characterized with many functional amino and hydroxyl groups has been the research focus on flocculants preparation and synthesis because of the facile grafting and modification to enhance and enlarge its original functions. In this study, a new type of graft modified flocculant CTS-g-PAA and its combination with kaolin have been developed for the treatment of acid blue 83 (AB 83). The CTS-g-PAA prepared by ultrasonic initiation of acrylamide (AM), 3-Acrylamide propyltrimethylammonium chloride (AATPAC) and CTS. The factors affecting CTS-g-PAA molecular weight and CTS graft ratio were examined to have a better understanding and comprehending of the ultrasonic initiated polymerization. The structure and morphological characteristics of CTS-g-PAA were investigated and analyzed by infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy ( 1 H NMR), differential thermal/thermogravimetric (TG/DSC), scanning electron microscopy (SEM) and X-Ray Diffraction (XRD), respectively. The results indicated that the CTS cyclic structure was broken by ultrasonic initiation and the grafting occurred at amino group with C 2 site of CTS. Meanwhile, the CTS-g-PAA coupled with kaolin exhibited superior flocculation performance better than the single removal effect, and the optimum removal rate for AB 83 could achieve 91.9%. The flocculation mechanism was discussed and summarized based on the conduction of zeta potential, FTIR of floc particles and the adsorption ability of the formed kaolin flocs. During the AB 83 flocculation, the CTS-g-PAA adsorption and flocculation contributed much to the AB 83 removal. The added kaolin particles played a crucial role in the enhancement of AB 83 adsorption and flocculation. The kaolin particles and the formed kaolin floc showed an adsorption effect for AB 83, and the kaolin particles also worked as the bridging between the CTS-g-PAA filled with AB 83 to strengthen the flocculation performance. As a result, the flocculation performance for AB 83 removal was greatly improved., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Poly(4-vinyl pyridine) decorated magnetic chitosan biopolymer (VMCP), as an absorbent and reductant, was prepared and used to remove hexavalent chromium (Cr(VI)) from aqueous solution. Compared with undecorated magnetic biopolymer, VMCP exhibited significantly improved removal performance under identical experimental conditions. The kinetics, isotherms, and thermodynamics of Cr(VI) adsorption onto VMCP were investigated. Results demonstrated that the maximum monolayer adsorption capacity of VMCP was 344.83 mg/g, which was considerably higher than most reported adsorbents. The mechanism for Cr(VI) removal was explored based on XPS and FTIR analyses. The main mechanisms were concluded to be Cr(VI) adsorption onto the positively charged VMCP surface and the reduction of Cr(VI) to Cr(III), followed by coordination between Cr(III) and N atoms. The easy regeneration, satisfactory reusability, and remarkable performance in column tests revealed the high potential of VMCP in treating Cr(VI)-contaminated water., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Carboxylated chitosan (CPCTS) is used as substrates in the design and synthesis of CPCTS-based flocculants through UV-initiated polymerization techniques. The synthesized flocculants are applied to remove Cr and Ni ions from chromic acid lotion and electroplating wastewater through two-stage flocculation. This study investigates the effect of flocculant dosage, pH, reaction time, and stirring speed on the removal efficiency of Cr and Ni ions. Results indicated that the total Cr removal ratios by CPCTS-graft-polyacrylamide-co-sodium xanthate (CAC) and CPCTS-graft-poly [acrylamide-2-Acrylamido-2-methylpropane sulfonic acid] (CPCTS-g-P(AM-AMPS)) are 94.7% and 94.6%, respectively. The total Ni removal efficiencies by CAC and CPCTS-g-P(AM-AMPS) are 99.3% and 99.4%, respectively. The two-stage flocculation with CPCTS-based flocculants could reduce the total concentrations of Cr and Ni to 1.0 mg/L and 0.5 mg/L, respectively. The relationship of removal capacity and structural properties between the flocculants with different functional groups is established through Fourier transform infrared spectroscopy, nuclear magnetic resonance, scanning electron microscopy, and X-ray diffraction. The micro-interfacial behavior between the colloidal particles and the solution during the integrated chelation-flocculation are elucidated. Thus, CPCTS-based flocculants could be a potential material for the removal of high amounts of Cr and Ni ions in industrial wastewater., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this study, modified magnetic chitosan microparticles (MCDs) were fabricated and used as adsorbents for the removal of Food Yellow 3 (FY3) and Acid Yellow 23 (AY23) from aqueous solution. The magnetic microparticles were characterized by scanning electronic microscope, Brunauer-Emmett-Teller specific surface area, elemental analysis, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetry analysis, differential scanning calorimetry, and vibrating-sample magnetometer. Then, the effects of pH value, initial dye concentration, and contact time on the adsorption of FY3 and AY23 by MCDs were investigated. Evidently, MCDs showed excellent adsorption performance for both food dyes, and their adsorption capacities (833.33 mg/g for FY3 and 666.67 mg/g for AY23) were considerably higher than those of unmodified adsorbents, which could be attributed to the electrostatic interaction and ion exchange between the grafted cationic polymer and food dyes. Adsorption isotherm and kinetic data of the magnetic microparticles were well fitted by Langmuir isotherm and pseudo-second-order kinetic model, respectively. The regeneration and reusability of MCDs were also explored. Results showed that more than 80% adsorption capacities of MCDs for FY3 and AY23 remained after five adsorption-desorption cycles., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Chitosan (CS)-g-polyacrylamide (PAM) is a highly efficient and environmentally friendly flocculant, which was synthesized through plasma-induced graft copolymerization of CS and acrylamide (AM). The effects of monomer concentration, AM:CS ratio, discharge power, discharge time, post-polymerization temperature, and post-polymerization time on the intrinsic viscosity, grafting ratio, and grafting efficiency of CS-g-PAM were investigated. The optimum conditions of graft copolymerization were as follows: 20% monomer concentration, 7:3 AM:CS ratio, 40 W discharge power, 90 s discharge time, 50°C post-polymerization temperature, and 24 h post-polymerization time. The structural characteristics of CS-g-PAM were characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction. CS-g-PAM exhibited better flocculation efficiency than the commercially available PAM in both diatomite-simulated wastewater and low-turbidity algal water. The optimal turbidity removal efficiency for the diatomite-simulated wastewater was 99.9%, which was obtained with 6 mg L -1 of CS-g-PAM at pH 11.0 and 250 s -1 of velocity gradient. In low-turbidity algal water, the optimal removal efficiencies for chlorophyll-a, turbidity, and COD were 93.6%, 94.5%, and 98.2%, respectively.

Novel adsorbents, poly([2-(methacryloxy)ethyl]trimethylammonium chloride) modified magnetic chitosan particles (DMCPs), were synthesized via free radical polymerization and applied to adsorb Cr(VI) from aqueous solution. The effects of pH (2-11), Cr(VI) concentration (10-200 mg/L) and contact time (0-420 min) on the adsorption performance were evaluated. The results showed that the adsorption capacity of DMCPs was much larger than that of magnetic chitosan particles (MCPs) in the examined pH range and decreased with Cl - concentration increasing, indicating that electrostatic interaction and ion exchange are the governing mechanisms of Cr(VI) adsorption by DMCPs. The Langmuir isotherm model and pseudo-second-order kinetic model fitted the experimental data well. The maximum adsorption capacity of DMCPs is 153.85 mg/g. Besides, Cr(VI)-loaded DMCPs could be easily separated and efficiently regenerated. Therefore, DMCPs are promising candidates for Cr(VI) adsorption owing to their excellent performance in a wide pH range, easy separation and good reusability., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A novel chitosan-based magnetic adsorbent [poly(2-acrylamido-2-methylpropane sulfonic acid) grafted magnetic chitosan microspheres, PMCMs] was successfully fabricated via free radical polymerization for effectively removing the cationic dye methylene blue (MB). The effects of initial solution pH (1.0-10.0), temperature (30-50°C), contact time (0-660min) and initial concentration (50-1600mg/L) were studied. The results indicated that the adsorption capacity increased with the increasing of initial solution pH and temperature. The adsorption kinetic and adsorption equilibrium data fitted closely to the pseudo-second-order kinetic model and Langmuir isotherm model respectively, confirming monolayer adsorption. The maximum adsorption capacity of PMCMs for MB at initial solution 9.0 were 1000, 1250 and 1428mg/g at 30, 40 and 50°C, respectively. Furthermore, the magnetic microspheres could be easily separated using a magnet and effectively regenerated after finishing the treatment process. Therefore, PMCMs are promising candidates for the removal of dye from wastewater., (Copyright © 2018. Published by Elsevier B.V.)

Due to the complexity of contaminants, the effectiveness of traditional flocculants toward water purification is insufficient. To break the limitation, a novel polymer flocculant [chitosan grafted poly (acrylamide-itaconic acid), CS-g-P(AM-IA)] was synthesized via ultraviolet-initiated graft copolymerization reaction. Characterization results revealed that the graft copolymers were successfully synthesized and with rougher surface structure. The solubility of CS-g-P(AM-IA) and chitosan grafted polyacrylamide (CS-g-PAM) were greatly improved and they can dissolve in the wide pH range of 2.0–12.0. CaCl 2 was used as a source of cation bridge to enhance the flocculation of kaolin particles, and its optimum dosage was 150 mg·L −1 . At dosage of 30 mg·L −1 and pH of 5.0, the turbidity removal efficiency of CS-g-P(AM-IA) reached the maximum of 93.8%, whereas those of CS-g-PAM and CS were 96.7% and 76.9%, respectively. The patchwise adsorption of ionic groups embedded in the molecular chain on Ca 2+ -clay complexes took effect to generate flocs with larger particle size. Besides, the decolorization ability of cationic dyes by CS-g-P(AM-IA) was greatly enhanced due to the role of abundant carboxyl groups. In the crystal violet (CV) adsorption experiment, the maximum CV dye removal efficiency for CS-g-P(AM-IA) reached the maximum of 81.6% at dosage of 0.7 mg·mL −1 and pH of 9.0, while those for CS-g-PAM and CS were 51.7% and 36.5%, respectively. [ABSTRACT FROM AUTHOR]

In this work, a novel chitosan-based magnetic adsorbent [poly(2-(dimethylamino)ethyl methacrylate) grafted magnetic chitosan microspheres, GMCMs] was synthesized by graft polymerization of (2-(dimethylamino)ethyl methacrylate on the surface of magnetic chitosan microspheres (MCMs). The as-prepared GMCMs exhibited significantly enhanced adsorption capacity towards anionic dyes (e.g., Acid Green 25 and Reactive Blue 19) compared with MCMs. It is due to the fact that the abundant tertiary amine groups of the grafted polymer protonated at low pH and the polymer chains stretched as a result of electrostatic repulsions and chain-solvent interactions. The stretched polymer chains provided a variety of adsorption sites, which efficiently adsorbed dyes through electrostatic interactions and hydrogen bonding. While, in alkaline conditions, the tertiary amine groups were deprotonated and the polymer chains collapsed due to hydrophobic interactions, which facilitated the regeneration of the dye-loaded GMCMs at high pH. The regenerated GMCMs showed excellent adsorption performance even after five adsorption–desorption cycles. Besides, the GMCMs could be rapidly separated from aqueous solutions under an external magnetic field. Therefore, the GMCMs materials bear great application potentials in water treatment owing to its high adsorption capacity, pH-responsiveness, facile regeneration and good reusability. [ABSTRACT FROM AUTHOR]

Modified natural polymer flocculants has been the focus of research in environmental engineering field. Natural large molecular compound, chitosan (CTS) with many functional amino and hydroxyl groups can be easily modified to enhance its original functions. This work presents an environmentally friendly chitosan-based cationic polyacrylamide flocculants (CTS-g-PAMA) with enhanced function of sterilization and flocculation. CTS-g-PAMA was synthesized through Ultraviolet (UV)-initiated copolymerization. Structure characterization of FTIR, 1 H NMR, XRD and UV spectrum confirmed the successful grafting of AM and MAPTAC. Scanning electron microscopy (SEM) analysis results showed that CTS-g-PAMA exhibited a porous structure with a prodigious surface area. CTS-g-PAMA was then applied to treat a series of simulated waste water containing kaolin or Escherichia coli . Flocculation tests indicated that CTS-g-PAMA not only showed excellent flocculation effect but also showed high sterilization capability. A series of ONP concentration measurement tests through UV spectra analysis and 3D EEM analysis of suspension before and after flocculation were conducted to study sterilization mechanism, and results revealed the sterilization effect of CTS-g-PAMA was essentially bactericidal, not just antibacterial. [ABSTRACT FROM AUTHOR]

Ni2+ rich wastewater has caused critical water contamination, a growing issue of environmental pollution as well as serious threat to aquatic organisms and human health. It is of great significance and urgent to develop a novel and efficient wastewater treatment technology for Ni2+ removal. The efficient removal of Ni2+ by flocculation has always become a hot and focus topic. In this study, a novel chitosan (CS) graft modified flocculants CS-g-P(AM-IA-AATPAC), namely CS-g-PAAI, is prepared by microwave initiation and polymerization, and is applied in the removal of Ni2+. The effects of microwave power, microwave irradiation time, initiator concentration and pH on the CS graft polymerization efficiency and flocculant molecular weight were investigated and optimized, so as to further understand the rules of microwave initiation and CS-g-PAAI graft and polymerization. Various characterization methods indicated the successful grafting and synthesis of CS-g-PAAI. Meanwhile, the structural characteristic results manifested that CS-g-PAAI possessed a good thermal stability, a coarse and porous apparent morphology, and its chemistry and crystal structure was evidently changed and affected after graft polymerization. Compared with CS, PAA and CS-g-PAA, the removal efficiency of Ni2+ by CS-g-PAAI is more exceedingly favorable and desirable. The flocculation effect of Ni2+ by CS-g-PAAI is as high as 86.3% at the optimal condition of pH = 9, flocculant dosage = 4 mg/L, the stirring speed = 400 rpm, and flocculation time = 30 min. Meanwhile, the generated Ni2+ floc size (d 50) and fractal dimension (D f) can reach a high value (d 50 = 339.3 µm, D f = 1.98), which accelerates the sedimentation and separation of the formed Ni2+ flocs. CS-g-PAAI shows excellent flocculation and coordination ability by its powerful coordination groups to strengthen the adsorption and chelating of Ni2+ ions and generate colloidal particles for subsequent flocculation. Then, efficient flocculation was carried out and proceeded through the bridging effect, the concomitant sweeping and netting action. [Display omitted] • CS-g-PAAI with both flocculation and coordination chelating effect was successfully synthesized. • There is a significant synergistic effect between flocculation and coordination chelating. • The introduction of IA can significantly improve the flocculation and removal effect of Ni2+. • 4. The Ni2+ floc particle size and fractal dimension conditioned by CS-g-PAAI are large and desirable. [ABSTRACT FROM AUTHOR]

Natural polymeric flocculants as sludge conditioners have received great attention due to their non-toxic and biodegradable advantages. However, the application of amphiphilic natural flocculants as sludge conditioners is rarely reported. In this work, the novel chitosan-based flocculants (CS-g-PAO) with amphiphilic structure were synthesized by ultraviolet light initiated method for the enhancement of sludge dewatering performance. The solubility of CS-g-PAO was significantly improved in a wide pH range (2.0–10.0). Various characterization methods were used to investigate the structure, thermal stability and surface morphology of copolymers, suggesting the successful synthesis of CS-g-PAO. In dewatering experiments, CS-g-PAO showed superior dewatering performance, and filter cake moisture content could be decreased to 77.98% from 95.14%. Moreover, the results of extracellular polymeric substances (EPS) components indicated that hydrophobic effect of CS-g-PAO was beneficial to remove the protein in S-EPS and TB-EPS, which had the crucial influence on dewatering performance. Furthermore, the dewatering mechanism was discussed based on the effects of zeta potential, apparent viscosity, surface tension and flocs structure on dewaterability. Results revealed that CS-g-PAO had strong hydrophobic association effect and surface activity. In addition, enhanced charge neutralization and hydrophobic interaction played a synergetic role in improving the dewaterability of CS-g-PAO. Image 1 • A novel chitosan-based flocculant with amphiphilic structure was synthesized. • The water solubility of the amphiphilic flocculant was improved in a wide pH range. • The amphiphilic flocculant showed superior dewatering efficiency under low dosage. • All results confirmed the role of charge neutralization and hydrophobic attraction. [ABSTRACT FROM AUTHOR]

The ampholytic chitosan based flocculant carboxylated chitosan graft-(3-chloro-2-hydroxypropyl) trimethylammonium chloride-dimethyl diallyl ammonium chloride (CPCTS-g-P (CTA-DMDAAC)) was synthesized by photo polymerization using carboxylated chitosan (CPCTS), 3-chloro-2-chloropropyltrimethylammonium chloride (CTA) and dimethyldiallylammonium chloride (DMDAAC) as the cationic co-monomers. The effects of monomer concentration, the ratio of CPCTS and cationic monomers, cationic degree, initiator time, photoinitiator concentration, and pH value on the properties of CPCTS-g-P (CTA-DMDAAC) were studied. The microcystis aeruginosa that was cultured in laboratory was used for CPCTS-g-P (CTA-DMDAAC) flocculation tests. The effects of CPCTS-g-P (CTA-DMDAAC) dosage, pH value and G value on flocculation performance were investigated. The maximum removal rate of chlorophyll-a (Chl-a) and chemical oxygen demand (COD) that were obtained by CPCTS-g-P (CTA-DMDAAC) were 98.8% and 96.5% under the conditions of dosage 4 mg/L, pH 7 and G value 200 s−1, respectively. The flocculation experiments showed that chitosan-based flocculant CPCTS-g-P (CTA-DMDAAC) had better flocculation performance than commercially available flocculants cationic polyacrylamide (CPAM), Polyferric Sulfate (PFS), and polymeric aluminium (PAC). [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • A functionalized chitosan-based flocculant (CC-g-PCD) is synthesized by UV initiation. • The concentration of algae decreased as the flocculants dosage increased. • The removal efficiency of CC-g-PCD was higher than that of commercially available coagulant. • CC-g-PCD has high efficiency in the removal of algae and turbidity from raw water. Abstract In this work, carboxylated chitosan modified flocculant (CC-g-PCD) was prepared by graft copolymerization technique to enhance the charge-attracting and adhesion of bridges and net-sweeping capacity of flocculants. The dimethyldiallylammonium chloride (DMDAAC), carboxylated chitosan (CMCS), and 3-chloro-2-chloropropyltrimethylammonium chloride (CTA) were utilized for synthesis of CC-g-PCD via photopolymerization techniques. The synthesized CC-g-PCD was characterized by 1H NMR, SEM, XRD, and FTIR, and the characteristic groups on the main chain and surface morphological structure of CC-g-PCD were investigated. The obtained results indicated that CTA and DMDAAC were successfully grafted into the CPCTS. In ordered to evaluate the flocculation performance of CC-g-PCD at various dosages, stirring intensity (G value), and pH value by detecting Chl a, COD, and turbidity, the actual lake water that contains algae was used for flocculation assessment tests. The experimental results of the water sample with flocculation showed that the maximum flocculation efficiency of turbidity (91.1%), Chl a (97.2%), and COD (97.0%) can be achieved by CC-g-PCD at pH 7, G value 200 s−1, and 4.0 mg/L. The comparison results demonstrated that CC-g-PCD had better flocculation efficiency than commercial flocculants. Finally, based on the analysis of algae removal in combination with Zeta potential measurements, the flocculation mechanisms in actual lake water at various dosages and pH values were adsorption bridging and electrical neutralization. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • A functionalized chitosan-based flocculant (MHCS-g-P(AM-DAC)) is synthesized by UV initiation. • The concentration of algae decreased as the flocculants dosage increased. • The removal efficiency of MHCS-g-P(AM-DAC) was higher than that of commercially available coagulant. • MHCS-g-P(AM-DAC) has high efficiency in the removal of algae and turbidity from raw water. Abstract The graft copolymer flocculant of chitosan namely, maleoyl chitosan-graft-poly(acrylamide–acryloxyethyl trimethyl ammonium chloride) [MHCS-g-P(AM-DAC)], was prepared by UV initiation to improve the solubility and flocculation efficiency of chitosan. Flocculating properties for algae removal were studied systematically. The effects of parameters such as monomer concentration, MHCS content, illumination time, photoinitiator concentration, cationic degree, pH and grafting efficiency over synthesis process of MHCS-g-P(AM-DAC) were studied. The characterization of obtained MHCS-g-P(AM-DAC) were carried out through different analytic techniques. The influences of dosage, pH, and G value on the flocculating properties were also investigated to support that MHCS-g-P(AM-DAC) was more effective than organic flocculant (CPAM) and inorganic coagulant (PFS and PAC) on algae removal. The flocculation mechanisms of MHCS-g-P(AM-DAC) were determinate by obtained zeta values. [ABSTRACT FROM AUTHOR]

In this study, maleyl chitosan- graft -polyacrylamide (MHCS-g-PAM), a novel chitosan-based flocculant, was prepared through UV irradiation, and maleyl chitosan (MHCS) was designed and prepared with maleic anhydride and acrylamide (AM) through maleyl acylation reaction. The effects of monomer concentration, MHCS-to-AM ratio, illumination time, initiator concentration, pH on viscosity, and grafting efficiency were investigated to optimize the synthesis of these substances. MHCS-g-PAM was characterized through Fourier transform infrared spectroscopy, nuclear magnetic resonance hydrogen spectroscopy, scanning electron microscopy, and thermal gravimetric analysis. Flocculation mechanisms in alga-containing wastewater at various pH levels and dosages were examined in detail on the basis of zeta potential measurements. Zeta potential experiments indicated that the adsorption-bridging and charge neutralization mechanisms played an important role in algal removal. Flocculation tests on algal removal demonstrated that the flocculation performance of MHCS-g-PAM was more effective than that of cationic polyacrylamide, polyferric sulfate, and polymeric aluminium. The optimal Chl- a and COD removal rate obtained by MHCS-g-PAM was 98.6% and 94.9% at pH 7 and 4 mg·L − 1 , respectively. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel polymer-functionalized magnetic nanosorbent (PMSC) is synthesized. • PMSC exhibited higher acid resistance than uncoated silica adsorbent (PMC). • PMSC showed excellent selectivity in capturing lead from multi-ion solutions. • It displayed good stability and reusability after five-adsorption–desorption-cycle. • Mechanisms of lead removal by PMSCwere elucidated. Separation and recovery of lead resources from lead-containing wastewater is very important to achieve reuse of lead(II) and environmental protection. Herein, a novel magnetic separation adsorbent, polymer-grafted silica-coated acid-resistant magnetic chitosan composite (PMSC), was facilely constructed and applied for the efficient and selective adsorption of Pb(II) from aqueous solutions. The adsorption results in the Pb(II) mono-contaminated system showed that the adsorption process of PMSC on Pb(II) was significantly pH-responsive and increased with increasing pH, reaching a q max value of 88.03 mg g−1 at pH 6.0, which was more than 6 times of MSC (14.47 mg g−1). More interestingly, the adsorbent with inert silica coated on the core has a higher acid resistance, with almost no iron leaching from PMSC at pH 1.0, while PMC has 3.99 mg L−1 of iron leaching. The results of adsorption isotherms and kinetics of Pb(II) by PMSC showed that Langmuir and pseudo-second-order kinetics can better describe the adsorption behavior, indicating that the adsorption process was mainly controlled by chemisorption and the maximum monolayer adsorption capacity can reach 111.12 mg g−1 at 298.15 K. Furthermore, PMSC maintained about 80 % of the initial adsorption capacity after five cycles of repeated use, demonstrating its good regenerative cycling performance. Also, PMSC showed excellent selective adsorption of Pb(II) in the coexistence solutions of multiple metal ions with the S Pb up to 85.83 %, which was far more than that of MSC (23.55 %), indicating that the polymer grafting had a significant enhancement on the selective performance of the adsorbent. This work could provide design and preparation insights for the development of novel, acid-resistant, recyclable and fast magnetic separation adsorbents for the efficient selective separation of lead ions. [ABSTRACT FROM AUTHOR]

In this work, a highly efficient and environmentally friendly chitosan-based graft flocculant, namely, acrylamide- and dimethyl diallyl ammonium chloride-grafted chitosan [CS-g-P(AM-DMDAAC)], was prepared successfully through plasma initiation. FTIR results confirmed the successful polymerization of CS-g-P(AM-DMDAAC) and P(AM-DMDAAC). P(AM-DMDAAC) was the copolymer of acrylamide- and dimethyl diallyl ammonium chloride. SEM results revealed that a densely cross-linked network structure formed on the surface. XRD results verified that the ordered crystal structure of chitosan in CS-g-P(AM-DMDAAC) was changed into an amorphous structure after plasma-induced polymerization. The flocculation results of low-algal-turbidity water further showed the optimal flocculation efficiency of turbidity removal rate, COD removal rate, and Chl-a removal rate were 99.02%, 96.11%, and 92.20%, respectively. The flocculation efficiency of CS-g-P(AM-DMDAAC) were significantly higher than those obtained by cationic polyacrylamide (CPAM) and Polymeric aluminum and iron (PAFC). This work provided a valuable basis for the design of eco-friendly naturally modified polymeric flocculants to enhance the flocculation of low-algal-turbidity water. [ABSTRACT FROM AUTHOR]

A novel chelating flocculant with branched architectures, polyacrylamide grafted maleoyl chitosan-mercaptoacetic acid (PAM-g-M(CS-MA)), was successfully fabricated using maleic anhydride as the "bridge" between chitosan and polyacrylamide. The functional groups and structural characteristic information of copolymers were obtained via characterization analysis. Flocculation performance was systematically investigated via purifying a series of simulated wastewater containing Cu or Cd. The properties of the flocs were studied to give in-depth evidences for the role of chelation groups and branched architectures in flocculation. Results indicated that PAM-g-M(CS-MA) showed excellent flocculation capacity for heavy metals in high concentrations and was superior to other chelating flocculants. The maximum flocculation efficiency of Cu (93.90%) and Cd (92.47%) was achieved by PAM-g-M(CS-MA) at pH 7, dosage of 100 mg L−1 and stirring speed of 90 rpm. The flocculation mechanisms of PAM-g-M(CS-MA) were deeply explored through the analyses of floc properties. The strong synergistic chelation of mercapto, carboxyl, amide and hydroxyl groups predominated for the capturing of heavy metals; and the branched architectures facilitated the formation of large and stable flocs via adsorption and bridging-furl effect. This study provided a solid foundation for the fabrication of flocculants for heavy metal wastewater treatment. [Display omitted] • A flocculant with branch architectures (PAM-g-M(CS-MA)) was synthesized. • PAM-g-M(CS-MA) showed low-dosage and efficient in heavy metals removal. • The maximum removal rates of Cu (93.90%) and Cd (92.47%) can be achieved by PAM-g-M(CS-MA). • Relationship between the branch architectures and flocculation performance was built. • Flocculation mechanism is composed by synergistic chelation, adsorption and bridging-furl effect. [ABSTRACT FROM AUTHOR]

[Display omitted] • A recyclable flocculant with strong adsorption configuration was prepared simply. • Flocculant can remove Cu(II) and malachite green efficiently and synchronously. • Adsorption by functional groups and sweep flocculation were the mechanism. • Flocculant was easily regenerated and separated. • Flocculant can remove multiple contaminants in single-stage water treatment. Conventional flocculants are difficult to effectively remove dissolved ions and organic matter from water. This work aims to develop an environmentally friendly and renewable core–shell type flocculant (MCHS-g-P(AM-IA)) with octopus tentacle-like strong adsorption structure. The organic shell hydrolyses into molecular chains like octopus tentacles and adsorb dissolved ions/organic macromolecules through suckers-like functional groups, while the magnetic core acts as the growth center of flocs. Configuration and physical/chemical properties of the flocculant were analyzed by a series of characterization methods. Set Cu(II) and malachite green (MG) as models of heavy metal and organic pollutants separately, the removal capacity of MCHS-g-P(AM-IA) for water contaminants was studied in single-contaminant system and binary-contaminant system. The flocculation behavior and mechanism of MCHS-g-P(AM-IA) were deeply investigated by analysis of pH-dependence, background cationic influence and flocculation kinetics and SEM-EDS/XPS analysis of flocs. Furthermore, the flocculation performance in actual water matrix and regeneration tests of MCHS-g-P(AM-IA) were carried out to evaluate the applicable feasibility of flocculants for purification of complex wastewater in single stage water treatment. [ABSTRACT FROM AUTHOR]

[Display omitted] • Chitosan based magnetic composite flocculants are successfully prepared. • The optimal removal rate of Cu(Ⅱ) by MC-g-PAA is over 93.0 %. • MC-g-PAA can effectively increase the floc particle size and fractal dimension of flocs. • The magnetic flocculant has the characteristics of recyclability and recycling. In this study, three magnetic flocculants, namely, MC, MC-g-PAM, and MC-g-PAA, were prepared. The structure characteristics, flocculation performance, and floc characteristics of the three magnetic flocculants were systematically studied and compared. SEM, FT-IR, XPS, XRD, TG–DSC, and VSM characterization results show that MC, MC-g-PAM, and MC-g-PAA are successfully prepared and exhibit good magnetic induction. The removal rates of copper ions by MC, MC-g-PAM, and MC-g-PAA under the optimal coagulation conditions are 93.39 %, 88.64 %, and 61.41 %, respectively. Kinetic fitting shows that the flocculation reaction process of MC and MC-g-PAM conforms to pseudo first-order kinetics, while the flocculation reaction process of MC-g-PAA conforms to pseudo second-order kinetics. The flocs produced by MC-g-PAA have larger particle size and fractal dimension than those by MC and MC-g-PAM. At 80 mg/L dosage and pH 6, the floc size and floc fractal dimension obtained by MC-g-PAA reach the maximum values of 48.28 um and 1.468, respectively. Zeta potential studies show that the flocculation functions of the three flocculants are mainly adsorption bridging, adsorption electric neutralization, and chelating precipitation. Recycling experiments show that MC-g-PAA has good recyclability, and the recovery rate after the fifth use is 77.24 % with the Cu(II) removal rate of 67.53 %. [ABSTRACT FROM AUTHOR]

Separating and recovering lead from heavy metal contaminated wastewater is crucial for the environment remediation and reutilization of lead resources. Herein, a novel adsorbent, the phosphorylated chitosan-coated magnetic silica nanoparticles (Fe 3 O 4 @SiO 2 @CS-P), was successfully fabricated and applied to highly selective adsorption of lead. Competitive experiments were conducted in a multi-ion solution (7 metal ions coexist) at pH 6.0, Fe 3 O 4 @SiO 2 @CS-P exhibited an excellent selectively for capturing lead with the distribution coefficient (0.75 L g−1) more ten times than other metal, while Fe 3 O 4 @SiO 2 @CS demonstrated a highly selective adsorption of silver. These implied that phosphorylation of adsorbent not only improves the sorption performance of lead, but also changes the selective adsorption of metal types. Acidity experiments can draw conclusions that Fe 3 O 4 @SiO 2 @CS-P exhibited better acid resistance (with barely any iron leaching) than silica-uncoated adsorbent (Fe 3 O 4 @CS-P) at pH 1.0. Furthermore, the FTIR and XPS spectra after adsorption suggested that the high adsorption performance and selective capture lead were predominantly controlled by the coordination of the phosphate groups on the surface of the adsorbent. This work shows a broad prospect of developing a series of novel, acid-resistant, good reusable and rapidly separable magnetic materials that can be used to efficiently and selectively capture lead from aqueous solutions. ga1 • A novel phosphorylated chitosan-coated magnetic silica adsorbent was prepared. • FSC-P showed excellent selectivity in capturing lead from multi-ion solutions. • FSC-P exhibited higher acid resistance than uncoated silica adsorbent at pH 1.0. • It displayed good stability and reusability after five-adsorption-desorption-cycle. • Adsorbent binds to lead mainly controlled by the coordination of phosphate groups. [ABSTRACT FROM AUTHOR]