Innovative biopolyelectrolytes-based technologies for wastewater treatment.

Developing eco-friendly, cost-effective, and efficient methods for treating water pollutants has become paramount in recent years. Biopolyelectrolytes (BPEs), comprising natural polymers like chitosan, alginate, and cellulose, have emerged as versatile tools in this pursuit. This review offers a comprehensive exploration of the diverse roles of BPEs in combating water contamination, spanning coagulation-flocculation, adsorption, and filtration membrane techniques. With ionizable functional groups, BPEs exhibit promise in removing heavy metals, dyes, and various pollutants. Studies showcase the efficacy of chitosan, alginate, and pectin in achieving notable removal rates. BPEs efficiently adsorb heavy metal ions, dyes, and pesticides, leveraging robust adsorption capacity and exceptional mechanical properties. Furthermore, BPEs play a pivotal role in filtration membrane techniques, offering efficient separation systems with high removal rates and low energy consumption. Despite challenges related to production costs and property variability, their environmentally friendly, biodegradable, renewable, and recyclable nature positions BPEs as compelling candidates for sustainable water treatment technologies. This review delves deeper into BPEs' modification and integration with other materials; these natural polymers hold substantial promise in revolutionizing the landscape of water treatment technologies, offering eco-conscious solutions to address the pressing global issue of water pollution.

Self-Assembled Chitosan/Dialdehyde Carboxymethyl Cellulose Hydrogels: Preparation and Application in the Removal of Complex Fungicide Formulations from Aqueous Media.

Environmental contamination with pesticides occurs at a global scale as a result of prolonged usage and, therefore, their removal by low-cost and environmentally friendly systems is actively demanded. In this context, our study was directed to investigate the feasibility of using some self-assembled hydrogels, comprising chitosan (CS) and carboxymethylcellulose (CMC) or dialdehyde (DA)-CMC, for the removal of four complex fungicide formulations, namely Melody Compact (MC), Dithane (Dt), Curzate Manox (CM), and Cabrio®Top (CT). Porous CS/CMC and CS/DA-CMC hydrogels were prepared as discs by combining the semi-dissolution acidification sol-gel transition method with a freeze-drying approach. The obtained CS/CMC and CS/DA-CMC hydrogels were characterized by gel fraction yield, FTIR, SEM, swelling kinetics, and uniaxial compression tests. The batch-sorption studies indicated that the fungicides' removal efficiency (RE%) by the CS/CMC hydrogels was increased significantly with increasing sorbent doses reaching 94%, 93%, 66% and 48% for MC, Dt, CM and CT, respectively, at 0.2 g sorbent dose. The RE values were higher for the hydrogels prepared using DA-CMC than for those prepared using non-oxidized CMC when initial fungicide concentrations of 300 mg/L or 400 mg/L were used. Our results indicated that CS/DA-CMC hydrogels could be promising biosorbents for mitigating pesticide contamination of aqueous environments.

Abatement of some commercial fungicide content from model dispersions by a new thiourea-graft-polyethyleneimine derivative.

A new derivative of polyethyleneimine (PEI) with 9% degree of substitution of its primary and secondary amino groups with thiourea moieties (TU9-PEI) has been synthesized and investigated as flocculant in model suspensions of commercial fungicide formulations Dithane M45, Melody Compact 49 WG, Cabrio®Top, and their mixtures. The structure of TU9-PEI, obtained by an aqueous one-pot strategy involving formaldehyde mediated coupling of PEI and TU, was confirmed by FTIR and 1H NMR spectroscopy as well as the streaming potential measurements. The settling time, polymer dose, and fungicide type and concentration were the parameters used for assessing the flocculation ability of the new polycation sample. The UV-Vis spectroscopy measurements revealed a good removal efficiency of TU9-PEI for all of the fungicides investigated, between 88 and 94%. Slightly higher removal percent was found for greater fungicide concentrations. The charge neutralization was indicated by zeta potential measurements (values close to zero recorded at the optimum polymer dose) as the main mechanism which contributed to the Dithane and Cabrio®Top particle removal and a combined effect of the TU9-PEI/fungicide particle electrostatic attractions and hydrogen bonds between both the amine and thiourea groups of the polycation chains and the hydroxyl ones on the copper oxychloride particles (negative values) in case of the Melody Compact 49 WG particle separation. Particle size and surface morphology analysis data gave supplementary evidences regarding the TU9-PEI ability to separate the fungicides investigated from simulated wastewater.

Cationic Pullulan Derivatives Based Flocculants for Removal of Some Metal Oxides from Simulated Wastewater.

Modified polysaccharides have been increasingly used as flocculants in wastewater treatment due to their non-toxicity, low price, biodegradability, etc. However, the pullulan derivatives are less used in wastewater purification processes. Therefore, this article presents some data regarding FeO and TiO2 particle removal from model suspensions by some pullulan derivatives with pendant quaternary ammonium salt groups, trimethylammonium propyl carbamate chloride (TMAPx-P). The influence of the polymer ionic content, dose, and initial solution concentration as well as of the dispersion pH and composition (metal oxide content, salts, and kaolin) on the separation efficacy were considered. UV-Vis spectroscopy measurements have shown a very good removal efficacy of TMAPx-P for the FeO particles (around 95% and more), irrespective of the polymer and suspension characteristics; a lower clarification of the TiO2 particles suspension (removal efficiency between 68% and 75%) was noticed. Both the zeta potential and the particle aggregates size measurements revealed the charge patch as the main mechanism which governs the metal oxide removal process. The surface morphology analysis/EDX data provided supplementary evidence regarding the separation process. A good removal efficiency (90%) of the pullulan derivatives/FeO flocs for the Bordeaux mixture particles from simulated wastewater was found.

New Quaternary Ammonium Derivatives Based on Citrus Pectin.

New citrus pectin derivatives carrying pendant N,N-dimethyl-N-alkyl-N-(2-hydroxy propyl) ammonium chloride groups were achieved via polysaccharide derivatization with a mixture of N,N-dimethyl-N-alkyl amine (alkyl = ethyl, butyl, benzyl, octyl, dodecyl) and epichlorohydrin in aqueous solution. The structural characteristics of the polymers were examined via elemental analysis, conductometric titration, Fourier Transform Infrared spectroscopy (FTIR) and 1D (1H and 13C) nuclear magnetic resonance (NMR). Capillary viscosity measurements allowed for the study of viscometric behavior as well as the determination of viscosity-average molar mass for pristine polysaccharide and intrinsic viscosity ([η]) values for pectin and its derivatives. Dynamic light scattering measurements (DLS) showed that pectin-based polymers formed aggregates in aqueous solution with a unimodal distribution. Critical aggregation concentration (cac) for the hydrophobic pectin derivatives were determined using fluorescence spectroscopy. Atom force microscopy (AFM) images allowed for the investigation of the morphology of polymeric populations obtained in aqueous solution, consisting of flocs and aggregates for crude pectin and its hydrophilic derivatives and well-organized aggregates for lipophilic pectin derivatives. Antimicrobial activity, examined using the disc diffusion method, proved that all polymers were active against Staphylococcus aureus bacterium and Candida albicans yeast.

Macroporous 3D Chitosan Cryogels for Fastac 10EC Pesticide Adsorption and Antibacterial Applications.

The pesticide pollution of surface water and wastewater has been recognized as a major worldwide concern due to their persistence in the aquatic environment and the potential adverse effects on human, flora, and fauna health. Apart from pesticides, bio-contamination with various bacterial populations leads to waterborne diseases. Hence, it becomes vital to remove the above-mentioned pollutants from water using a suitable process. Consequently, our study emphasized the potential benefits of a highly porous, chemically cross-linked 3D chitosan (CSGA) cryogel in the removal of pesticides and bacteria. The CSGA sponges were prepared using a facile and cost-effective approach that consisted of a three-step cryogenic process: (i) freezing at -18 °C, (ii) storage in a frozen state for a certain period, and (iii) thawing at room temperature. Batch adsorption experiments were performed under different environments, where the effects of several parameters, such as pH, contact time, and initial pollutant concentration were evaluated to identify the appropriate adsorption conditions for maximum pesticide removal. The CSGA-based cryogel sponges exhibited a theoretical maximum adsorption capacity of 160.82 mg g-1 for the Fastac 10EC pesticide and very good recyclability at room temperature. In addition, the antibacterial activities of these sponges were also investigated against various bacterial pathogens. The rates of killing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus were close to 82%, 100%, and 99%, respectively. These results demonstrated that CSGA cryogels could be efficiently used in water remediation and find applications in the removal of pesticides and disinfection.

Grafted Pullulan Derivatives for Reducing the Content of Some Pesticides from Simulated Wastewater.

The goal of the current article was to obtain data regarding the application of a series of grafted pullulan derivatives, as flocculating agents, for removal of some pesticide formulations from model wastewater. The pullulan derivatives are cationic polyelectrolytes, with various content and length of grafted poly[(3-acrylamidopropyl)-trimethylammonium chloride] chains onto the pullulan (P-g-pAPTAC)]. The commercial pesticides are either fungicide (Bordeaux Mixture) (BM) or insecticides (Decis (Dc)-active ingredient Deltamethrin, Confidor Oil (CO)-active ingredient Imidacloprid, Confidor Energy (CE)-active ingredients Deltamethrin and Imidacloprid and Novadim Progress (NP)-active ingredient Dimethoate). The removal efficiency has been assessed by UV-Vis spectroscopy measurements as a function of some parameters, namely polymer dose, grafted chains content and length, pesticides concentration. The P-g-pAPTAC samples showed good removal efficacy at doseop, more than 94% for BM, between 84 and 90% for DC, CO and CE and around 93% for NP. The maximum percentage removal decreased with the pesticides (DC, CO, CE, NP) concentration declining; no effect of BM concentration in suspension on its removal efficiency process has been noted. Differences indicated by zeta potential and particle size distribution measurements regarding the pesticides removal mechanisms by pullulan derivatives (charge neutralization, bridging, etc.) are discussed.

Dextran derivatives application as flocculants.

A large variety of hydrophilic and amphiphilic polyelectrolytes based on dextran have been previously tested as coagulating and flocculating agents in model wastewater treatment and the results are presented in this review article. The dextran derivatives are either cationic, bearing (i) pendent quaternary ammonium groups, N-alkyl-N,N-dimethyl-N-(2-hydroxypropyl)ammonium chloride and (ii)1-(2-hydroxypropyl)-3-methyl imidazolium chloride, randomly distributed along the polymer backbone or anionic, (i) dextran monobasic phosphate with HP(O)(OH) groups and (ii) dextran derivatives with carboxylic groups namely, dextran-g-poly(acrylamide-co-sodium acrylates). This paper will give an overview of the main results obtained in the separation of suspensions and emulsions containing either inorganic (clay, titanium dioxide, zirconium silicate (kreutzonit), zinc oxide and ferric oxide (hematite)) or organic (pesticides: Fastac 10EC, Decis, Dithane M45) contaminants. The investigations considered the influence of some polyelectrolyte characteristics (the charge density, the length of the alkyl substituent, the molecular mass), polyelectrolyte dose and initial concentration, as well as the properties of the model suspensions/emulsions (contaminants concentration, dispersion medium composition and pH) on the separation process. Turbidity/absorbance, zeta potential and particle dimensions measurements allowed to determine the polycation dose where the maximum separation efficiency was obtained, the flocculation mechanism and the floc size and distribution for each peculiar system.

Removal of the commercial pesticides Novadim Progress, Bordeaux mixture and Karate Zeon by pullulan derivatives based flocculants.

Cationic pullulan derivatives have been synthesized and evaluated, for the first time, as flocculants for the separation of the commercial pesticides, Novadim Progress (organophosphoric type), Bordeax mixture and Karate Zeon (pyrethroid type) from synthetic wastewater. The investigated polymer samples contained either pendent tertiary amine or quaternary ammonium salts groups. The separation efficiency was followed by UV-Vis spectroscopy, while the information regarding the mechanism involved in the separation of pesticide particles have been obtained by zeta potential. UV-Vis spectroscopy data showed strong pesticide particles/polycation interactions in case of Novadim Progress and Bordeaux mixture (maximum pesticide removal between 90% and 98%). Good separation efficiency (around 80%) of Karate Zeon emulsion was also noticed. The zeta potential measurements indicated that the charge neutralization was the common flocculation mechanism for the removal of these pesticides. In addition, the hydrogen bondings and chelation of copper ions by amide and/or tertiary amino groups of the polycations had a noteworthy contribution to the pesticide removal.

Cationic polyelectrolyte induced separation of some inorganic contaminants and their mixture (zirconium silicate, kaolin, K-feldspar, zinc oxide) as well as of the paraffin oil from water.

The flocculation efficiency of a cationic polyelectrolyte with quaternary ammonium salt groups in the backbone, namely PCA5 was evaluated on zirconium silicate (kreutzonit), kaolin, K- feldspar and zinc oxide (ZnO) suspensions prepared either with each pollutant or with their mixture. The effect of several parameters such as settling time, polymer dose and the pollutant type on the separation efficacy was evaluated and followed by optical density and zeta potential measurements. Except for ZnO, the interactions between PCA5 and suspended particles led to low residual turbidity values (around 4% for kreutzonit, 5% for kaolin and 8% for K-feldspar) as well as to the reduction of flocs settling time (from 1200 min to 30 min and 120 min in case of kaolinit and K-feldspar, respectively), that meant a high efficiency in their separation. The negative value of the zeta potential and flocs size measurements, at the optimum polymer dose, point to contribution from charge patch mechanism for the particles flocculation. A good efficiency of PCA5 in separation of paraffin oil (a minimum residual turbidity of 9.8%) has been also found.

Ionic dextran derivatives for removal of Fastac 10 EC from its aqueous emulsions.

Separation studies of Fastac 10 EC from model emulsions by cationic polysaccharides were followed by UV-vis spectroscopy and zeta potential measurements. Floc size measurements at the optimum polycation dose were also carried out using laser diffraction technology. The investigated polyelectrolytes contained various amounts of quaternary ammonium salt groups, N-ethyl(octyl)-N,N-dimethyl-2-hydroxypropyl ammonium chloride, attached to a dextran backbone. The effects of polycation dose, its charge density, emulsion pH and pesticide concentration on the flocculation performance were studied. The pesticide removal results (UV-vis spectroscopy) show that the optimum polycation dose decreased with increasing polymer charge density and the emulsion pH and increased with increasing pesticide concentration. The zeta potential values close to zero at the optimum polymer dose point to contribution, mainly, from charge neutralization mechanism for the flocculation process. The flocs size increase with increasing pesticide concentration was also observed.

Separation of TiO2 particles from water and water/methanol mixtures by cationic dextran derivatives.

Cationic polysaccharides with N-alkyl-N,N-dimethyl-N-(2-hydroxypropyl)ammonium chloride pendent groups attached to a dextran backbone were used to flocculate titanium dioxide (TiO2) particles suspended in water as well in water/methanol mixtures (90:10 and 50:50 v/v %). The investigations were performed with respect to the polycation dose, the suspension medium composition and the length of alkyl substituent at the quaternary nitrogen (alkyl=ethyl, octyl, dodecyl). The supernatant residual turbidity values were much lower for TiO2 particles dispersed in solvent mixtures than in water. This finding was explained by the solvent mixtures effect on the charges of both the particle surface and polyelectrolyte chains. The alkyl substituent length did not affect in a dramatic way the separation of TiO2 particles. The supernatant zeta potential dependence on the polycation dose when water/methanol mixtures were used as dispersion medium indicated a charge patch mechanism for the flocculation of TiO2 particles, which was supported by particle aggregates size measurements.

Removal of anionic dyes from aqueous solutions by an ion-exchanger based on pullulan microspheres.

Pullulan-graft-poly(3-acrylamidopropyl trimethylammonium chloride) (P-g-pAPTAC) microspheres were prepared by suspension cross-linking of the pullulan previously grafted with cationic moieties. Adsorption of Azocarmine B by the P-g-pAPTAC microspheres was used as a model to demonstrate the removal of anionic dyes from aqueous solutions. Batch adsorption studies concerning the effect of the contact time, pH, initial dye concentration, temperature, grafting, and the nature of sulfonated anionic dyes on the adsorption kinetics were investigated. Adsorption was shown to be independent of pH. The experimental data best fitted to the pseudo-second order model which provided values of the rate constant k(2) of 1.4×10(-4) g mg(-1) min(-1) for 100 mg L(-1) solution and of 3.7×10(-4) g mg(-1) min(-1) for 500 mg L(-1) solution. From the Langmuir isotherm linear equation, the maximum adsorption capacity determined was 113.63 mg of Azocarmine B per gram of adsorbent; the negative value of the free energy change indicated the spontaneous nature of the adsorption process.

Intrinsic viscosities of polyelectrolytes in the absence and in the presence of extra salt: Consequences of the stepwise conversion of dextran into a polycation.

Viscosities of dilute polymer solutions were measured in capillary viscometers for samples varying in their fraction f of charged units from 0.00 to 0.90. The dependence of the logarithm of the relative viscosity on polymer concentration c is in all cases reproduced quantitatively by three characteristic parameters: [η], the intrinsic viscosity; B, a viscometric interaction parameter (related to the Huggins constant); [η], a parameter required only for polyelectrolytes at low concentrations of extra salt. In pure water [η] increases more than 80 times as the fraction f rises from zero to 0.90 and [η] starts from zero and goes up to ≈71mL/g. Upon the addition of NaCl [η] decreases by at least one order of magnitude (depending on the value of f). The observed dependences of log [η] on logcsalt can be modeled quantitatively by Boltzmann sigmoids.

Novel thermosensitive flocculanting agent based on pullulan.

New thermosensitive polysaccharide (P-g-pNIPAAm) was synthesized by graft-polymerization of p(N-isopropylacrylamide) (pNIPAAm) onto pullulan (P) using Ce(IV) ion as initiator. The grafted polysaccharide was characterized by FT-IR and (1)H NMR spectroscopy and elemental analysis. Its flocculation efficiency was studied in a clay suspension, in comparison with p(NIPAAm) homopolymer, as a function of the polymer dose, temperature and settling time. The thermosensitive polysaccharide could induce clay particle flocculation both below and above the lower critical solution temperature (LCST), but the process was more effective above the LCST. A lower value of the residual turbidity at the optimum polymer dose and a wider flocculation window were recorded at temperature above the LCST. The floc size distribution and surface morphology revealed bigger size flocs when the flocculation was performed above the LCST. The re-dispersion effect was negligible for the flocs obtained in the presence of P-g-pNIPAAm.

Novel biodegradable flocculanting agents based on cationic amphiphilic polysaccharides.

Flocculation properties of a series of cationic polysaccharides, with N-alkyl-N,N-dimethyl-N-(2-hydroxypropyl)ammonium chloride pendent groups attached to a dextran backbone, were evaluated in clay dispersions with respect to length of the alkyl substituent, molar mass, the charge density, and polycation dose. According to turbidimetric results, the alkyl chain length greatly influenced the optimum polymer dose as well as the width of the flocculation window since both increased from an ethyl to a butyl group and decreased for when octyl or dodecyl group was present. The residual turbidity values also varied with the charge density but no dramatic effect was observed with the molar masses investigated. These findings together with the negative value of the zeta potential at the optimum polymer dose and floc size measurements, point to contributions from both patch and bridging mechanisms for the flocculation process.

Novel biodegradable flocculanting agents based on pullulan.

New copolymers with different grafted cationic chain content and length were synthesized by graft-polymerization of (3-acrylamidopropyl)-trimethylammonium chloride onto pullulan in aqueous solution, using potassium persulfate as an initiator. Their flocculation efficiency was studied in a clay suspension as a function of the grafted chains content and length as well as of some flocculation parameters: the polycation dose, the settling time, the parent solution concentration of polycation. All the polysaccharide samples showed flocculation ability: the higher the grafted cationic chain content and length the lower the amount of pullulan derivative was required for reaching the maximum clarity degree (of about 100%). This finding together with the negative value of the zeta potential and floc size measurements, at the optimum polymer dose, point to contributions from both neutralization and bridging mechanisms for flocculation process. The residual turbidity values also varied with the settling time and the parent solution concentration of polymer.

Ionic polymers based on dextran: hydrodynamic properties in aqueous solution and solvent mixtures.

Hydrodynamic properties of a series of ionic polysaccharides with different charge density but the same molecular weight have been evaluated in salt-free aqueous solution and aqueous/organic solvent mixtures by means of capillary viscometry. The polyelectrolytes investigated contain quaternary ammonium salt groups, N-ethyl-N,N-dimethyl-2-hydroxypropylammonium chloride, attached to a dextran backbone. The experimental viscometric data have been plotted in terms of the Wolf method. The results show that the experimental data fit well with this model and allow the calculation of intrinsic viscosities and other hydrodynamic parameters, which provide new information about the dependence of the polyion conformation on its polyion charge density as well as on solvent composition.

Transport properties of some cationic polysaccharides 2. Charge density effect.

The charge density effect on the behavior of some cationic polysaccharides in aqueous and nonaqueous (methanol) solutions was studied by viscometric and conductometric measurements. The polyelectrolytes investigated contain quaternary ammonium salt groups, N-alkyl-N,N-dimethyl-2-hydroxypropylene ammonium chloride, attached to a dextran backbone. This new class of polyelectrolytes has various linear charge density parameters, xi, located below and above the critical threshold value of counterions condensation, xi(c)=1(xi=0.25-3.18). The viscometric data revealed that all copolymers exhibit a polyelectrolyte behavior and were plotted in the terms of Rao equation. The conductometric measurements of solutions of these copolymers were presented as a function of polymer concentration and charge density. The results were analyzed within the Manning's theory and lower experimental values of the equivalent conductivity than the theoretical ones were found. Possible reasons of this discrepancy have been discussed. The interaction parameters were evaluated and these were found to depend on both the polymer concentration and the charge density. The conductometric behavior of these cationic polysaccharides has shown that counterion condensation is not a threshold phenomenon, their association to the charged groups of the polyions taking place for xi>1 as well as xi<1.