Remediation of Wastewater Using Polymeric Materials: Flocculants and Nanofibers

Tuğba Isik
Mineral Research and Exploration General Directorate
Dumlupınar Bulvarı No:33/A, Çukurambar, 06530 Çankaya/Ankara Türkiye
Correspondence to: tugbaisikedu@gmail.com

DOI: https://doi.org/10.70389/PJES.100018

Additional information

• Ethical approval: N/a
• Consent: N/a
• Funding: No industry funding
• Conflicts of interest: N/a
• Author contribution: Tuğba Isik – Conceptualization, Writing – original draft, review and editing
• Guarantor: Tuğba Isik
• Provenance and peer-review:
  Unsolicited and externally peer-reviewed
• Data availability statement: N/a

Keywords: Wastewater remediation, Electrospun fibers, Flocculants, Polymer recycling, Water pollution sources.

Peer Review
Received: 27 March 2025
Accepted: 4 May 2025
Published: 17 May 2025

Introduction

The abundance of water comes to the forefront among other natural sources, but this does not mean that all water sources can be used by humanity. It is known that nearly 97% of water sources are salty, and only 3% of them are freshwater sources, while 69% of this freshwater is trapped in glaciers and 30% is found in groundwaters. Thus, only 1% of fresh water is available for human use, and as we know this little amount is not equally available for the population. According to the WHO and UNICEF report in 2017, approximately 2.1 billion people have serious problems accessing safe and clean water in their homes.¹ With the increasing population in the following years, the water scarcity problem will be more serious if the precautions and required attempts are not considered at the earliest time. Thus, the clean water and sanitation take place as one of the Sustainable Development Goals of United Nations. The water scarcity problem not only causes sanitary and hygiene problems but also has a negative effect on economic development and geopolitics. All the agricultural activities are based on the presence of water and nearly 70% of fresh water is consumed for agricultural activities, which have a huge economic value worldwide. Moreover, conflicts regarding water sources create geopolitical problems between countries and may result in water wars in the future. Therefore, the limited availability of fresh water and the water pollution problem drive humanity into a tight corner, where there are various hazardous chemical contaminations to the water sources and reduced water quality.

Sources of Water Pollution

Due to the universal solvent nature of water, which means that it is capable of dissolving most of the substances than any other liquids, water sources are easily polluted by various pollutants. There are several reasons for water pollution that change its physical and chemical properties in negative manner and result in harmful effects on all living things. Agricultural activity is one of the vital reasons for water pollution. Through agricultural applications, fertilizers and pesticides have been used to  improve crop quality and enhance their grooving. However, these chemicals contaminate the ground and surface waters by increasing nitrogen and phosphate concentrations, resulting in the outstanding growth of algae and eutrophication. On the other hand, industrial wastes are another cause of remarkable water pollution. The wastewater coming from industries contains heavy metals, harmful chemicals, organic pollutants, and oil, and all these pollutants destroy ecosystems by decreasing biodiversity and threatening human health. In a similar way, the pollutants coming out from domestic wastes are also harmful due to the contamination of detergents.²

In recent years, there has been another serious water pollutant: microplastics. Microplastics are the plastic species that are less than 5 mm in size, and there are two major sources for microplastics. The first one is the primary microplastics, which come directly from cosmetic products, synthetic textiles, and pellets used in industrial applications.^3,4 The secondary microplastics arise from the physical, chemical, and biological degradation of large plastics.⁵ All these microplastics contaminate water sources in different ways. The wastewater treatment plants can filter most, but not all, of the microplastics, and some of them mix up with water sources. Also, the microplastics from asphalts surfaces and tires are carried to water sources inevitably.^6,7 Moreover, there is a huge amount of oil spills into the seas each year, and 343,200,000 gallons of oil spill into the sea due to various reasons, such as ship accidents or insufficient waste management strategies. In a similar way, the problems in waste management strategies lead to the pollution of water sources with pathogenic pollutants from medical wastes, heavy metal ions, and dye spills from the textile industry (Figure 1).

Impacts of Water Pollution

Water pollution affects the quality of water sources physically, chemically, and biologically, and correspondingly, it has adverse effects on human health. The accumulation of heavy metals in waters damage both aquatic vegetation and animals, especially in deep waters. The pollutants are adsorbed by aquatic animals, and the accumulated heavy metals are transferred to other living creatures by destroying the food chain, and the balance of the ecosystem is destroyed.⁸ The disruption of the ecosystem has serious results, and human health is related to the balance of the ecosystem. Polluted water sources contain heavy metals and other toxic pollutants, and they can contaminate drinking water in water streams. The water resources are used for irrigation in agricultural activities, and the foods are contaminated in this way. Thus, people who consume these foods are indirectly contaminated by these pollutants.

Historical Index and Change of Pollution

The rise of the water pollution problem dates to the mid-1940s, and the challenges forced the evaluation of water pollution control. Water-borne diseases, degradation of recreational waters, and the outstanding growth in industry and population have sped up water-pollution-related problems, and various precautions have been taken by governments. Municipalities are forced to spend money on funding for water pollution, and laws are enforced to remove any overlapping regulations. In this manner, the Water Quality Index (WQI) was developed in the 1960s to assess river water quality.⁹ The WQI has been revised throughout history, and the most recent one was established in 2017. In this version, water quality is assessed via nine different variables, which are temperature, chemical oxygen demand (COD), dissolved oxygen (DO), suspended solids, total phosphate, total nitrate, detergent, phenol, and choride content.¹⁰ In recent years, governments have taken various precautions to fight water pollution. In May 2021, the European Union adopted the Zero Pollution Action Plan by aiming to reduce air, water, and soil pollution by 2050. The main goals of this plan for water protection are to reduce the plastic litter at sea by 50% and microplastic release by 30%.¹¹

Possible Methods for Wastewater Remediation

When the pollutants in water sources are considered, efficient purification methods are strongly required due to the challenges in water supply coming from organic and inorganic pollutants.¹² Chemical oxidation, coagulation, photocatalysis, and adsorption are widely used techniques for wastewater treatment, but the traditionally used methods are not efficient in the water remediation process due to their several disadvantages, such as high energy consumption, insufficient performance, and the generation of secondary wastes.¹³ At this point, polymers become prominent for wastewater treatment. The polymer-based materials are structurally useful, tailorable, and versatile for various applications, and their tailored structures enhance their adsorption capacities, making the polymers suitable candidates for water treatment applications. Also, recyclable polymers are promising candidates for both waste management and wastewater treatment practices. In this paper, we will focus on the application of electrospun fibers and flocculants in wastewater treatment applications.

Electrospun Fibers

Method Description

The electrospinning method goes back a long way that the first investigations were based on the generation of aerosols from liquid drops under high electrical potential in the 1700s. Then, the developments continued until the 1900s, and the first patented device was developed in 1929 by fabricating artificial silk by Kiyohiko.¹⁴ The first application of polymers in electrospinning was performed by Simm et al. in 1934, and after that date, growing attention has been paid to this method.¹⁵ The fabrication of continuous fibers with ultrathin diameters becomes possible with electrospinning, and solutions, suspensions, or melts from a variety of materials can be applied as precursors. The method allows the control of the surface morphology and topography of resulting materials, and their properties are strongly variable depending on the process parameters.¹⁶ Moreover, not only the polymer precursors but also the ceramic and metal fibers can be fabricated, and the post-modification of fibers with various functionalizing agents is possible.¹⁷ The setup comprises three main components, which are a syringe pump with a small diameter conductive needle to feed the polymer solution, a high voltage supply to apply a direct current potential and create an electrical field, and a grounded collector to gather fibers on itself (Figure 2).

Through the process, the polymer solution is pumped, and the droplet that comes to the capillary nozzle acts as an electrode. When the high voltage is applied to the nozzle, the jet is created, and the polymer is transferred through the electrical field. The electrical field depends on the processing parameters, but it varies between 1.0–5.0 kV cm−1. While the polymer solution is transferred through the electrical field, the solvent evaporates, the polymer solidifies, and the solidified electrospun fibers are collected on the grounded collector.¹⁸ The morphology of collected fibers depends on various parameters, which are the polymer solution properties (concentration, viscosity, surface tension, and vapor pressure of solvent), flow rate of syringe pump, applied electrical field, and environmental conditions (temperature and humidity). Thus, the biggest advantage of electrospinning is its tailorable properties by changing the processing parameters. All these parameters have a strong influence on the fiber morphology. For example, using highly volatile solvents results in porous structures with enhanced hydrophobicity or high concentrations of polymer solutions that have larger fiber diameters with lower surface area at the end, while the low concentrations lead to the formation of beads instead of fibers. Moreover, the viscosity of the solution affects the fiber morphology because the low viscosity results in a lack of chain entanglement and bead formation.

The conductivity of the solution promotes the fiber formation, but higher conductivity than the required levels results in bead formation.¹⁹ Another advantage of this fiber fabrication technique is the ability to use a wide variety of polymer types. In the literature, there are various types of polymers have been used for the fabrication of nanometer to micron scale fibers by using synthetic polymers (polystyrene, polymethylmethacrylate, polyvinyl alcohol, etc.), protein blends (silk, fibrinogen, collagen, etc.) and polysaccharides (cellulose derivatives).²⁰ Alongside its advantages, electrospinning also has some challenges. The major problem faced during the process is the clogging of the nozzle due to the very fast evaporation of solvent on the needle or high viscosity. Also, the polymer and solvent selection is an important step in that there are a limited number of conductive polymers, and it is not possible to process neat, non-conductive polymers. The use of corrosive or harmful solvents might be an environmental issue during the process for synthetic polymers, and sustainable selection of the solvents is required. However, the continuous and fine nanofiber fabrication and bulk production possibilities of the method make electrospinning suitable for various applications.

Literature Examples

Due to urbanization and industrialization all over the world, there are various water pollutants such as oil spills, heavy metals, pathogens, and dyes. The use of electrospun fibers is an emerging trend for water remediation due to their high surface-to-volume ratio, and various studies have been conducted in the literature. Xu et al. utilized polysulfone fibrous mats to remove the suspended particles from bio-polluted water sources²¹ In another study, Gopal et al. fabricated polyvinylidene fluoride electrospun fibers for the pretreatment of wastewater treatment plants before ultrafiltration, and these fibers removed 90% of the microparticles.²² Shi et al. modified the polyacrylonitrile (PAN) nanofibers with silver nanoparticles and investigated their antimicrobial activities against Escherichia coli and Bacillus cereus bacteria.²³ Zhao et al. fabricated PAN electrospun nanofibers with microbial carriers by immobilizing aerobic denitrifying bacteria, and different carbon-to-nitrogen (C/N) ratios were obtained. The optimized parameters were found to be 12% PAN concentration with C/N > 7, and these fibers showed 90% degradation with 200 ppm nitrate-polluted wastewater.²⁴

Proteins have also been used to modify electrospun fibers for wastewater remediation. Xie et al. developed polyvinyl alcohol (PVA) and zein composite nanofibers via electrospinning for the adsorption of copper ions from wastewater. The results showed that a 50% protein addition to the polymer composite improved the Cu(II) ion adsorption capacity up to 26.62 mg/g.²⁵ Chitosan and cellulose composite fibers were fabricated by Phan et al. by using a co-solvent system followed by sodium carbonate treatment for the neutralization of chitosan and deacetylation of cellulose acetate. The mechanical properties reached up to 17 MPa tensile strength for composite fibers with 5.5% elongation in break. The resulting fibers were utilized for the adsorption of heavy metal ions from aqueous solutions, and the results were recorded as 39, 57, and 112 mg/g for arsenic, lead, and copper ions, respectively.²⁶ Janus electrospun fibers have also been used in wastewater treatment applications, and Yan et al. fabricated PAN/carbon nanotube composite electrospun fibers to remove oil from aqueous solutions efficiently. The micro and nanopores through the fibers create channels for the adsorption of oil, and the results showed that 99.8% separation efficiency was recorded with 2188 L/m2.h flux.²⁷ As the latest development, Ahmadijokani et al. reported the use of metal-organic frameworks (MOFs) combined with electrospun fibers by taking advantage of both methods that easy-design, controllable structure and flexibility of electrospun fibers and high permeability, water treatment applicability, and tailored structures of MOFs.²⁸

Recycled Materials

In recent years, recycling plastic waste has become a crucial issue worldwide. The long degradation time and microplastic formation increase the negative impact on the environment, and precautions are required to eliminate the plastic waste problem. At this point, there are various traditional methods in the literature for the recycling of plastics. Electrospinning of waste polymers is one of the latest approaches that can be used for both recycling and reusing waste products for water remediation purposes. Polyethylene terephthalate (PET) is one of the most frequently generated wastes. Disposable water bottles are the main source of PET waste. After their first use, PET bottles run to waste in a quite clean and undeformed way. Thus, recycling and reusing them for further applications is a proper approach to waste management. Siskova et al. recycled PET bottles in binary organic solvents (hexafluoro-2-propanol/dichloromethane), and nano-sized electrospun fibers were fabricated for filtration application of 120 nm particles with 98% efficiency.²⁹

Likewise, Strain et al. processed PET bottles via solution electrospinning for the fabrication of micron-sized electrospun fibers with 62.5 MPa fiber strength. The resulting fibers were utilized for smoke filtration and absorbed smoke 43 times their weight.³⁰ Moreover, polystyrene (PS) is another frequently generated plastic waste, and the main source of this waste is Styrofoam. Esmaeili et al. recycled the PS wastes by varying the processing parameters and investigated their effect on fiber diameter.³¹ Isik et al. recycled Styrofoam wastes via solution electrospinning and investigated the effect of solvent composition and polymer concentration on the surface morphology. By tailoring the solvent composition, interior and exterior porosity were generated, and high adsorption capacity and hydrophobicity were achieved, respectively. Then, the recycled electrospun fibers were used for oil adsorption from wastewaters with up to 124 g/g adsorption capacity and 99% separation efficiency³² (Figure 3). Alongside synthetic polymers, bio-based polymers can be recycled via electrospinning. Keratin extracted from chicken feathers or cellulose has been recycled via electrospinning, and their unique chemical structure makes them available for various filtration applications.^33,34

Flocculants

Method Description

One of the purification methods frequently used in water remediation applications is flocculants. Flocculants are made of polymers, and their working principle is based on the aggregation of suspended solid particles in solution to form large agglomerates, which are called as “flocs.” The formed flocs further aggregate into larger flocs through Van der Waals attractions and they settle out of the solution by separating the clean water and suspended solids (contaminants in water).³⁵ Depending on their chemical structure, flocculants can be synthesized with different surface charges, such as nonionic, anionic, or cationic, and each leads to various applications. Polyacrylamides (PAMs) are among the most commonly used polymers in flocculation applications and can be synthesized with different surface charges through various modifications. Nonionic PAMs stand out due to their hydrophilic nature and can be synthesized through the polymerization of the acrylamide monomer via free radical polymerization with the help of an initiator (Figure 4a).

Since the resulting long-chain continuous polymer structure does not contain any functional groups on its backbone, it is referred to as nonionic PAM, and it is widely used in various water remediation applications.³⁶ Anionic polyacrylamide carries negative charges on its backbone and can be synthesized in different ways. One such method involves the alkaline hydrolysis of amide groups on nonionic polyacrylamide using sodium hydroxide (NaOH). In the presence of heat and NaOH, a portion of the amide groups on the polymer chain undergoes hydrolysis by forming negatively charged functional groups³⁷ (Figure 4b). However, the flocculants synthesized via alkaline hydrolysis result in non-uniform charge distribution along the polymer chain and may limit the separation efficiency during flocculation. Some studies in the literature indicate the effect of negative charge distribution along the polymer chain on flocculation performance. Charge distribution is an important parameter for flocculant synthesis, as well as the molecular weight of the polymer and degree of hydrolysis. As another option, Feng et al. synthesized block copolymers using acrylamide and sodium allyl sulfonate and used them as anionic flocculants for industrial wastewater treatment. They observed that the synthesized polymer formed compact and large flocs while exhibiting a highly efficient flocculation performance.³⁸ For this reason, the use of copolymers synthesized from acrylamide and acrylic acid monomers as anionic flocculants is also frequently reported in the literature (Figure 4c).

Moreover, cationic polyacrylamides carry positive charges along their backbone, and they are synthesized through the reaction of amide groups on formaldehyde with the secondary amine groups on monomers. As a result, a polymer structure with tertiary amine is formed and becomes positively charged under acidic conditions. The presence of hydrophobic groups on the cationic flocculants makes them favorable for the removal of organic substances from the wastewater, such as oils and dyes³⁹ (Figure 4d).

The working principle of flocculants is based on three main mechanisms: charge neutralization, particle adsorption onto the polymer chain, and bridge formation between target particles to create large flocs. In an aqueous system, target particles become destabilized through charge neutralization and interact with the opposite charges on the polymer chain via adsorption. Subsequently, they become trapped within the long polymer chains, agglomerating to form large flocs.³⁸ Both anionic and cationic flocculants work in similar ways during the flocculation process. After the interaction of opposite charges, the target particles are adsorbed on the chain, and the polymer forms a bridge between target particles by forming large flocs and facilitating separation. The only difference between cationic flocculants is that the hydrophobic groups are on their chain because there is minimal interaction with the aqueous solution, and they interact with organic structures present in the system. This results in the formation of larger flocs, making the flocculation process more efficient and faster.⁴⁰ Figure 5 schematically represents the working mechanisms of flocculants in the presence of target molecules.

Literature Examples

The use of flocculation in water remediation occurs in three main steps: the selection of flocculant, its reaction with target contaminants, and the separation of flocs from water through sedimentation. Among the many natural and synthetic polymers available today, polyacrylamide-based flocculants are the most widely used ones in water remediation applications. They function as “thickeners” in municipal wastewater treatment plants by aiding in the removal of suspended solids. Once the polymer is separated from the system, clear and purified water is obtained.

Nonionic flocculants are widely utilized due to their high hydrophilicity and ease of synthesis. Vanotti et al. used synthesized nonionic flocculants in combination with sand drying beds in municipal wastewater treatment and significantly improved treatment performance. This method removed 97% of the total solids from the wastewater while reducing the post-process discharge time of drying beds to just 1 hour.⁴¹ Similarly, Yang et al. achieved wastewater treatment in high-phosphorus hematite flotation effluents using nonionic acrylamide flocculants. These wastewater types are known to be difficult to treat due to their high solid and organic content, but in this study, the turbidity value was successfully reduced to 0.8 NTU using nonionic flocculants.⁴² Subramanian et al. synthesized various copolymer microgels using diallyldimethylammonium chloride (DADMAC) and acrylamide monomers. These copolymers were applied for the treatment of colloidal suspensions containing titanium dioxide, and the copolymers with 30% DADMAC content achieved the highest turbidity removal efficiency.⁴³ Additionally, Amuda and Amoo utilized nonionic polyacrylamides in industrial wastewater treatment, recording a 97% reduction in total solids.⁴⁴

On the other hand, anionic polyacrylamides have been used in wastewater remediation due to the advantage of the interaction between negative charges on the polymer and positive charges on the target particles. In a study by Michaels, anionic polyacrylamide was used to treat clay-containing suspension solutions. It was reported that as the molecular weight of the flocculant increased, the number of hydrolyzed groups also increased, leading to improved flocculation performance in high-molecular-weight polymers.⁴⁵ Kurenkov et al. synthesized anionic flocculants by hydrolyzing high-molecular-weight polyacrylamides at low temperatures and applied them in wastewater treatment. They reported that when the degree of hydrolysis reached 19%, the turbidity values of the solution were minimized.⁴⁶ Amuda et al. used anionic polyacrylamide for the treatment of Abattoir wastewater in Nigeria and reported a 94% reduction in total solids.⁴⁴ Martin et al. applied anionic polyacrylamides in industrial wastewater treatment and achieved a 72% reduction in turbidity.⁴⁷ In another study, Hamza et al. synthesized an anionic polyacrylamide-based copolymer flocculant and reported a 99.42% reduction in turbidity.⁴⁸

Similar to anionic polyacrylamides, cationic polyacrylamides synthesized with positive charges are also used in wastewater treatment, particularly for the separation of organic content and carbon in wastewater. Liu et al. synthesized chitosan-grafted polyacrylamide-itaconic acid flocculants in cationic forms via UV-initiated graft copolymerization and investigated their dye removal performance from wastewater. They reported 81.6% dye removal efficiency with 0.7 mg/mL use of polymer at alkaline pH.⁴⁹ In another application, Irfan et al. used cationic polyacrylamides for the treatment of wastewater from paper mills and reported a 95% reduction in turbidity.⁵⁰ Cheng et al. used cationic polyacrylamide synthesized via inverse emulsion polymerization as a flocculant in kaolin suspensions.⁵¹ Sun et al. compared the performance of a cationic and branched flocculant synthesized through vinyl polymerization using acrylamide and acryloxyethyltrimethylammonium chloride with a nonionic branched polyacrylamide flocculant. They reported that the cationic flocculant performed better.³⁵ In another study, Yang et al. synthesized a cationic flocculant using acrylamide, dimethyl diallyl ammonium chloride, and butyl acrylate monomers through free radical polymerization. The presence of hydrophobic groups on the polymer chain reduced its interaction with the solution, increasing the polymer’s hydrodynamic size and, consequently, the solution’s viscosity. In a study on the separation of oil molecules from aqueous solutions using the synthesized cationic polymer, 93.4% oil separation was achieved with 50 ppm polymer.⁴⁰

Conclusion

In recent years, technological developments have greatly expanded the utilization of polymers in various applications. They have not only been used in the production of consumable products; the wastewater remediation applications have considered the polymeric structures for the removal of pollutants from water sources. The polymeric structures can either be used in membrane or filtration applications via adsorption mechanisms or flocculation applications by taking advantage of electrostatic attractions through the chains. The urgent need for advanced water technologies requires the remediation of polluted wastewater by removing chemical and organic pollutants. The developments in nanotechnology are involved at this stage, although there might be some drawbacks during the fabrication of applications.

Polymer synthesis procedures might require harsh and toxic chemicals to the environment, or nano-sized particles may contaminate the waters during their application. However, the use of natural polymers or recycling the current polymer wastes for new products overcomes these drawbacks and adds a new perspective to water treatment applications. In this review, the two different types of polymeric materials have been investigated and discussed, along with examples from the literature. Firstly, the reasons and possible precautions for wastewater treatment are mentioned. Then, the theoretical background of electrospinning and flocculation mechanisms is explained in detail, and the literature mentions examples of the application of polymeric structures in literature are mentioned.

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Cite this article as:
Isik T. Remediation of Wastewater Using Polymeric Materials: Flocculants and Nanofibers. Premier Journal of Environmental Science 2025;3:100018

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