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Review

Leading Techniques for Per- and Polyfluoroalkyl Substances (PFASs) Remediating in Water and Wastewater

1
State Key Laboratory of Water Engineering Ecology and Environment in Arid Area, Xi’an University of Technology, Xi’an 710048, China
2
Department of Municipal and Environmental Engineering, School of Water Resources and Hydroelectric Engineering, Xi’an University of Technology, Xi’an 710048, China
3
Zhejiang Province Key Laboratory of Recycling and Eco-Treatment of Waste Biomass, Zhejiang University of Science and Technology, Hangzhou 310023, China
*
Author to whom correspondence should be addressed.
Water 2025, 17(9), 1319; https://doi.org/10.3390/w17091319
Submission received: 19 March 2025 / Revised: 23 April 2025 / Accepted: 26 April 2025 / Published: 28 April 2025
(This article belongs to the Special Issue Constructed Wetlands and Emerging Pollutants)

Abstract

:
Per- and polyfluoroalkyl substances (PFASs), a class of synthetic organic compounds since the 1940s, have become widespread and persistent environmental pollutants. Due to their high chemical stability, bioaccumulation potential, and extensive industrial and household applications, PFASs have drawn significant attention from researchers worldwide in recent years, while PFASs have become a hot topic, and the publications are updated very quickly. Various remediation technologies, including adsorption, pyrolysis, biodegradation, and advanced oxidation, have been developed and treated as the leading techniques to mitigate PFAS contamination. Other alternative techniques are foam fractionation, constructed wetland, and piezoelectric ball milling. However, the effectiveness of these methods varies depending on their reaction mechanisms, operational conditions, and environmental factors. This review provides a comprehensive summary of the latest advancements in PFASs removal strategies, highlighting their advantages, limitations, and potential synergies. Furthermore, future research directions and technological developments are discussed to explore more efficient, sustainable, and cost-effective solutions for PFASs remediation.

1. Introduction

Per- and polyfluoroalkyl substances (PFASs) represent a new class of persistent organic pollutants in the environment. Defined as organic compounds containing at least one perfluorinated carbon atom, PFASs encompass compounds such as perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), among others. Their exceptionally strong C–F bonds, with a bond energy of approximately 485 kJ/mol, endow PFASs with remarkable chemical and thermal stability, rendering them persistent in the environment. Therefore, they are called “Forever Chemicals” [1]. PFASs have widespread applications across various industrial and domestic sectors [2], including firefighting to form water-based film-forming foams (AFFFs) [3]. They are prevalent in food packaging materials [4], stain-resistant and waterproof fabrics [5], carpets, leather [6], clothing products [7], non-stick cookware like Teflon [8], polishing agents, lubricants in cleaning products, surfactants, additives in textiles, and construction materials [9]. As such, they are extensively distributed in the natural environment after use. Accordingly, PFASs have been detected in drinking water, wastewater, landfill leachates, rivers, lakes, marine ecosystems, and remote regions, with concentrations ranging from nanograms to milligrams per liter [10]. Furthermore, PFASs are detectable even in various food items, human serum, urine, and cerebrospinal fluid [11].
Indeed, water is an essential substance for human life and one of the most fundamental needs of the human body. However, with the advancement of technology development, many industrial-related compounds were produced while water was inevitably polluted. Thus, studies are continuously conducted along with industrial development and expansion. Various situations are faced while solutions are being explored [12,13]. For example, radioactive contamination has frequently disrupted aquatic ecosystems, posing significant potential risks to human health. The Fukushima nuclear power plant accident in Japan was an example of radioactive isotopes presenting long-term and widespread threats to both marine ecosystems and human health [14]. PFASs are useful materials; however, they constitute a group of pollutants that threaten human health through direct exposure, contaminated water, and ecosystem disruption.
Due to the presence of water-soluble functional groups, PFASs exhibit polarity and are highly soluble in water. Consequently, water bodies have become the primary medium for the migration and accumulation of PFASs. Both groundwater and surface water may be impacted by the discharge of PFASs from surrounding environments. Sources of such discharge include industrial wastewater discharges, the application of firefighting foam, and leaks from landfill sites, etc. When water sources containing PFASs are used for drinking water or food production, individuals may inadvertently ingest PFASs [15]. PFASs do not break down naturally and can accumulate in the human body, where they can be extremely harmful, including developmental impacts. Prenatal exposure to persistent organic pollutants (e.g., PFASs, BFRs, and PCBs) may affect human brain development, potentially leading to learning and memory deficits in children [16]. Potential carcinogenic effects, particularly for specific compounds like PFOA and PFOS [17], have been reported to be associated with increased risks of kidney and testicular cancer [18]. Furthermore, Wu et al. [19] found that co-exposure of PFASs in blood was positively associated with chronic cough risk. Wei et al. [20] suggested that exposure to PFAS during childhood and adolescence could affect future bone health, increasing the risk of osteoporosis in adulthood. Figure 1 illustrates the entry route of PFASs into the human body. Drinking water has been identified as a significant source of human exposure to PFASs.
In 2016, the U.S. Environmental Protection Agency (EPA) proposed health advisory levels for PFOA and PFOS in drinking water, recommending that their combined concentrations should not exceed 70 ng/L [21]. In comparison, the concentration limits for PFOA and PFOS in drinking water set by regulatory authorities in the UK, Germany, Italy, the Netherlands, and Sweden are 10, 300, 30–500, 200–390, and 90 ng/L, respectively. Subsequently, in 2018, the Agency for Toxic Substances and Disease Registry (TSDR) in the United States further lowered the minimum risk levels (MRLs) for PFOA and PFOS by approximately one order of magnitude, compared to the reference doses (RfDs) used by the U.S. EPA to establish the health advisories in 2016 [22]. The Stockholm Convention designated PFOS (along with its salts and related compounds) as a regulated chemical in 2009, followed by PFOA in 2019, perfluorohexanesulfonic acid (PFHxS) in 2022, and perfluorocarboxylic acids (PFCAs), a subgroup of PFAS, in 2024, progressively expanding its list of controlled substances [23].
China has also enacted similar regulations, gradually strengthening controls on PFASs. In 2017, PFHxS was placed under regulation, with a comprehensive ban on its production. Since 2020, the production and use of PFOS, along with its salts and related compounds, have been subjected to strict regulatory oversight [24]. Furthermore, as of March 2023, the use and processing of PFOS, PFOA, and their related substances have been completely prohibited [25].
No doubt, the treatment of PFASs in the water environment is an urgent issue, and extensive studies have been conducted worldwide. Research on PFASs in large shallow lakes conducted by Liu et al. [26] found that the existence of PFASs seriously affected the aquatic ecological environment. More recently, Zeeshan et al. [27] have a comprehensive overview of the occurrence and removal of PFASs through adsorption and biodegradation. Hussain et al. [28] have reviewed the current advances in both destructive and non-destructive methods for removing PFASs from water. These studies collectively highlight the pressing need for effective and sustainable PFASs remediation strategies to mitigate their environmental impact and protect aquatic ecosystems.
This paper focuses on the most recent research and advancements in PFAS remediation techniques. Several leading techniques with principles were presented. It was followed by alternative techniques, which can be promising supplements and can be applied with a combination of leading techniques for PFASs removal. In addition, further research directions are pointed out with the opinion of the authors for further efforts towards PFASs control. The novelty of this review lies in the timely review of the updated literature on PFAS investigations, while future research directions based on the authors’ opinions are presented, considering the massive literature and very fast updating of the global investigations.

2. Leading Treatment Techniques of PFASs

Due to the nature of PFASs, cleaning up contaminated sites is technically challenging and expensive. Traditional water treatment technologies have proven ineffective in removing PFASs, leading to ongoing efforts to develop PFAS removal techniques. Table 1 shows some remediation methods for PFASs in the aquatic environment.

2.1. Adsorption

Adsorption technology utilizes adsorbents to attract PFASs, concentrating them on the surface of the adsorbents and thus reducing the concentration of PFASs in water. Materials such as activated carbon, ion exchange resins, zeolites, and graphene have demonstrated excellent capabilities for removing PFASs in existing research. These adsorbents are cost-effective, easy to operate, and highly efficient in removal, making them widely used in wastewater treatment. Table 2 lists the principles, advantages, and disadvantages of various adsorbents for the treatment of PFASs from wastewater. The adsorption mechanisms of PFASs on various adsorbents include hydrophobic interactions, electrostatic interactions (Positive charge—attraction; negative charge—repulsion), micellation, hydrophobic interactions, complexation, π-π interactions, and hydrogen bonding (Figure 2). Up to now, the literature shows that adsorption is the important leading technique for PFASs remediation.

2.1.1. Activated Carbon

Activated carbon (AC) is widely used for removing pollutants from water due to its low cost and strong adsorption capacity [47]. Previous studies have demonstrated that granular activated carbon (GAC) can effectively remove long-chain PFASs through hydrophobic interactions, but its performance in removing short-chain PFASs is poor [48]. The ozone/biological activated carbon (O3-BAC) process can effectively remove approximately 20.74% of PFASs in drinking water treatment plants through adsorption [49]. The biofilm on BAC provides adsorption sites, allowing for more efficient removal of PFASs from water, with high removal efficiency and long duration.

2.1.2. Resins

Considering the long adsorption equilibrium time and adsorption capacity of AC, utilizing resins for the enrichment of PFASs from solutions has emerged as a promising and efficient removal method [50]. Resins exhibit a wide range of adsorption capacities (200 to 2390 mg PFOS g−1 and 525 to 1500 mg PFOA g−1) [51], with differences in properties among different resins such as the functional groups, porosity, and polymer matrix leading to variations in their adsorption capabilities for PFASs [52]. Generally, anion exchange resins demonstrate better adsorption performance. Studies have shown that a strongly basic anion exchange resin can completely remove PFOA and PFOS from drinking water [53].

2.1.3. Minerals

Minerals are often considered suitable materials for adsorbing PFASs due to their adjustable mesoporous structure or variable layered structure [54]. Electrostatic interactions, hydrophobic interactions, ion exchange, surface complexation, and hydrogen bonding are the mechanisms driving the adsorption of PFAS onto mineral surfaces [40]. Certain mineral materials such as boehmite and alumina may possess positively charged surfaces, making them suitable for adsorbing negatively charged PFASs [55]. Willemsen et al. [56] used molecular dynamics simulations to study the behavior of montmorillonite clay for PFASs. The results showed that hydrophobic interactions are the primary mechanism of adsorption.

2.1.4. Molecularly Imprinted Polymer

MIPs synthesized via precipitation polymerization are employed for the selective adsorption of PFASs. In addition to molecular size, the selectivity of MIPs is influenced by the electrostatic interaction between protonated nitrogen on the polymer surface and PFOS. Compared to other adsorbents, the key advantage of MIPs lies in their high affinity and selectivity [57], as they can generate specific binding sites with particular cavities that complement the target molecules in size, shape, and functionality [41]. MIPs exhibit a wide range of adsorption capacities for PFASs (6.31~1565 mg PFASs g−1), showing significant differences [54].

2.1.5. New-Generation Adsorbents

New-generation adsorbents typically offer advantages over traditional adsorbents due to their larger and more reactive surface area [58]. The adsorption mechanisms of PFASs on novel adsorbents involve electrostatic interfaces, hydrogen bonding, hydrophobic effects, and ion exchange, differing from traditional adsorbents. Among these, hydrophobic and electrostatic interactions are considered the key to PFAS adsorption [59].
Covalent organic frameworks: covalent organic frameworks (COFs) are crystalline covalent porous polymers containing various light elements such as C, H, O, N, Si, and B [60]. Studies have demonstrated that the hydrophobic nature of COFs promotes the adsorption of hydrophobic PFASs, with hydrophobic interactions being the primary driving force [40]. For example, the cationic COF with quaternary ammonium showed a high adsorption capacity for PFOA substitutes, such as hexafluoropropylene oxide dimer acid (GenX) and hexafluoropropylene oxide trimer acid (HFPO-TA), with adsorption capacities of 2.06 mmol/g and 2.16 mmol/g, respectively [61]. Song et al. [62] synthesized an olefin-linked covalent organic framework with NH2 functional groups (COF-NH2) for the solid-phase microextraction of PFASs from fish samples.
Metal–organic frameworks: MOFs are innovative porous crystalline materials composed of organic linkers and metal/metal oxide nodes [44]. The adsorption mechanism of PFASs on MOFs primarily relies on electrostatic and hydrophobic interactions. Researchers have developed an aluminum-based MOF for the laboratory-scale adsorption of PFOA from water; the results demonstrated that the aluminum-based MOF exhibited significantly higher adsorption capacity for PFOA (340 mg/g) compared to AC (120 mg/g) [63]. As a member of the MOF family, ZIF-L has been widely employed in the fabrication of thin-film nanocomposite (TFN) membranes [64]. According to the study by Bi et al. [45], the TFN membrane exhibited outstanding rejection performance for representative PFASs, achieving retention rates of 97.75% and 97.85% for PFOA and PFOS, respectively.
Carbon nanotubes: CNTs are garnering significant attention in the field of environmental remediation due to their unique hollow nanostructure and chemical–physical properties [65]. CNTs possess high surface area and strong hydrophobicity, making them excellent candidates for the adsorption of organic pollutants [66]. Moreover, as the outer diameter increases, the specific surface area of CNTs decreases with smaller diameter CNTs showing higher adsorption potential for PFASs [67]. For example, single-walled carbon nanotubes (SWCNTs) with diameters of 1–2 nm exhibit an adsorption capacity for PFOS exceeding 712 mg/g. In comparison, multi-walled carbon nanotubes (MWCNTs) with diameters of 10 nm and 50 nm have adsorption capacities of 656 mg/g and 514 mg/g, respectively [68].
Organically modified silica: organic-modified silica as adsorbents is a novel class of adsorbents that are effective in removing PFASs. These adsorbents have mesoscopically accessible pores that allow the modifiers to properly cover their surfaces, thus endowing the adsorbents with high adsorption capacity and selectivity [69]. Certain compounds, such as 3-Aminopropyltriethoxysilane, 1,8-Bis(dimethylamine)naphthalene, hexadecyltrimethylammonium bromide, and cross-linked silicate organic esters, have been identified as effective coatings for silica, enhancing its adsorption efficiency for PFASs [70]. The functionalized macroporous silica adsorbents (HSU00107954, HSU00107955, and HSU00107956) developed by Lassen et al. [71] achieved up to 60 times greater PFSAs adsorption capacity than granular activated carbon (GAC). They exhibit outstanding performance, particularly at the sub-nanomolar concentrations typically present in raw and drinking water.
Bio-adsorbents: bio-adsorbents such as biochar, as environmentally friendly and cost-effective adsorbents, have shown tremendous potential in efficiently remedying water pollution. Biochar is prepared using a wide range of raw materials such as plant waste, wood chips, and crop residues [46]. Its adsorption capacity for PFOS and PFOA ranges from 91.6 to 2170 mg/g and from 21.7 to 1350 mg/g, respectively [54]. Due to variations in pyrolysis conditions and raw material composition, the adsorption behavior of biochar varies, and currently, knowledge about PFASs’ adsorption on biochar remains limited.

2.2. Thermal Treatment/Thermal Degradation

Thermal treatment involves utilizing heat energy to initiate the decomposition and degradation processes of pollutants in solid or liquid waste. Thermal decomposition techniques can be applied to remove PFASs from media such as soil or wastewater treatment matrices, such as saturated AC, ion exchange resins, and other contaminated substrates. Additionally, thermal treatment can be used to manage mixed municipal solid waste and hazardous waste-containing PFASs [72].
Evick et al. [73] employed the destructive thermal and nonthermal processes for PFAS treatment; however, the risk of generating additional PFAS compounds due to incomplete degradation remains a concern. The thermal degradation of PFASs adsorbed onto materials can be initiated through two pathways (Figure 3). Firstly, as the solid temperature increases, some PFASs may volatilize and react in the gas phase. Secondly, some less volatile PFASs may undergo thermal degradation within the solid phase [74].
Consequently, the extent and types of byproducts from thermal degradation may vary depending on the volatility of the PFASs. Waterborne PFASs adsorbed onto solids via electrostatic or ion exchange interactions exhibit a lower tendency to volatilize into the gas phase until temperatures rise above 100 °C when water begins to evaporate, weakening their interaction with the solid. For instance, during the regeneration process of media containing PFASs, PFOA does not volatilize below 90 °C, and its surface concentration gradually decreases as the temperature rises from 90 °C to 400 °C [75]. Table 3 gives some compounds of PFASs, which can be decomposed in different thermal conditions [72].
Thermal technologies such as pyrolysis, incineration, and gasification have proven to be effective solutions for degrading PFASs and converting biogenic solids into value-added products such as biochar. These techniques, under specific parameters, can mineralize PFASs and employ unique degradation mechanisms and pathways [76]. For instance, gasification of biogenic solids at 600 °C can degrade PFASs to below detection limits and produce biochar from PFASs. Similarly, the thermal decomposition of biogenic solids at 650 °C has been demonstrated to degrade PFASs of varying chain lengths to below detection limits and produce high-quality biochar with fixed carbon and phosphorus content [77]. Decarboxylated perfluorocarboxylic acids (PFCAs) represent the largest class of PFAS compounds. Under mild conditions (80 to 120 °C), PFCAs of various chain lengths can undergo effective mineralization in a polar aprotic solvent. This process involves a decarboxylation reaction that generates reactive perfluoroalkyl ion intermediates, which further degrade into fluoride ions within 24 h, with a degradation efficiency ranging from 78% to approximately 100% [78].
In a study conducted by Amin et al. [79], thermal treatment of PFAS-contaminated soil in a muffle furnace was found to not only degrade PFAS precursors such as 6:2 fluorotelomer sulfonate but also degrade PFOA and PFOS. The thermal degradation of PFOS involves a three-step random chain scission pathway, beginning with the cleavage of the C-S bond, followed by defluorination of the perfluoroalkyl radical and subsequent radical chain growth reactions and finally the termination of chain growth reactions leading to the formation of short, fluorinated units.

2.3. Biodegradation Processes

Fortunately, nature utilizes biodegradation to address environmental pollutants. It relies on the inherent capabilities of organisms such as bacteria, fungi, plants, and earthworms, along with their enzymes, to degrade chemical bonds in pollutants and convert them into harmless compounds. Compared to physicochemical methods, biodegradation offers the advantage of complete degradation, while also being cost-effective, environmentally friendly, and sustainable [80]. However, pollutants from synthetic chemicals often introduce new chemical constituents, requiring microorganisms to possess the ability to degrade these new compounds. This holds for organochlorines, which are well known for their biodegradation capabilities. However, for organofluorine compounds, especially those with multiple fluorine structures, microbial degradation, while discovered, is not commonly observed in nature [81,82].
Biodegradation through microbes and phytores is the primary pathway for the degradation of fluorinated compounds in the natural environment. Figure 4 illustrates the pathways of PFASs into water and the bioremediation techniques for their remediation. Microalgae such as Scenedesmus, Chlorella, and Chlamydomonas also possess the ability to degrade PFAS and can thrive in extreme environmental conditions, including low light, salt stress, unfavorable temperatures or pH levels, and nutrient limitations [83]. In aquatic systems, the symbiotic relationship between microalgae and bacteria can further enhance PFAS removal efficiency [84]. Additionally, fungi play a crucial role in breaking down complex organic compounds into simpler molecules. Phytoremediation utilizes plant root systems to absorb and degrade PFASs, providing a cost-effective in situ remediation strategy for water and soil environments [32]. Meanwhile, bioelectrochemical systems (BESs) employ electroactive microorganisms to degrade recalcitrant pollutants while simultaneously generating bioelectricity [85].
The biodegradation of PFASs faces a range of unresolved challenges, primarily due to the rarity of defluorination metabolism in nature and the wide chemical diversity of PFASs and their precursors. Due to their stability, the biodegradation capacity of PFASs at low concentrations and under typical environmental conditions is limited. While traditional PFASs such as PFOA and PFOS have been gradually phased out, they remain major classes of PFASs in many contaminated areas due to their inertness and resistance to microbial degradation [80]. These compounds pose serious health hazards to biological health, affecting multiple aspects including the immune system, genetic development, the nervous system, and the endocrine system [18].
For the degradation of perfluorinated compounds, defluorination is the core process, which can be categorized into aerobic and anaerobic defluorination mechanisms based on the microbial transformation of organic matter [86]. Currently, research is increasingly focused on aerobic degradation mechanisms. Studies have shown that activated sludge in wastewater treatment plants can effectively reduce the concentration of short-chain PFASs [80]. Che et al. [87] investigated the structure-specific biotransformation of short-chain fluorinated carboxylic acids under aerobic conditions. Their findings revealed that C–F bonds are susceptible to microbial cleavage only when the α-carbon contains a single C–H bond. Furthermore, substituting one or two hydrogen atoms with fluorine at the α-position significantly inhibit aerobic microbial defluorination.
Although past studies have indicated the difficulty of microbial degradation of PFOA and PFOS, recent experiments suggest that certain microbial species or mixed microbial species can degrade specific PFASs [32]. An experiment showed that after 48 h of cultivation, the HJ4 strain could degrade approximately 67% of PFOS, with the residual concentration of PFOS remaining unchanged [88]. The acidophilic microbial strain A6 has been confirmed to effectively remove 60% of PFOA and PFOS through biodegradation [89]. Under sulfur-limiting conditions, the anaerobic bacterium Pseudomonas strain D2 partially degraded sulfonates, such as H-PFOS and 2,2,2-trifluoroethane, through hydrogen-driven defluorination [90].

2.4. Oxidation Technologies

2.4.1. Photodegradation

Photolysis involves the adsorption of ultraviolet radiation, leading to the cleavage of C–F chemical bonds in PFASs. However, due to the strength of the C–F bond, photolysis exhibits relatively low degradation efficiency for PFASs removal [91]. Vacuum ultraviolet (VUV/UV) processes, as an advanced oxidation process (AOP), have gained increasing attention in the field of water treatment [92]. Studies have found that PFOA can be effectively degraded by VUV radiation, and its effectiveness in degrading PFOA has been demonstrated [93]. Research has shown that compared to 254 nm ultraviolet light, 185 nm VUV radiation can successfully degrade PFOA, leading to the cleavage of C–F bonds [94]. Awoyemi et al. [95] used a hybrid system of ultraviolet light (UV, @185 nm)-assisted ultrasound (600 kHz) to defluorinate PFOS in an air environment. The results achieved 88% synergistic defluorination of PFOS at 10 mg/L, which was 12% more effective than using only a 100 W and 0.2 W/cm2 ultrasound system for 4 h.

2.4.2. Fenton Oxidation

Fenton treatments are advanced oxidation processes (AOPs) that generate reactive oxygen species (ROS) in situ to oxidize organic pollutants in aqueous environments, ultimately mineralizing them into CO2 and water [96]. The key oxidant in the Fenton process, the hydroxyl radical (·OH), is generated through the reaction between ferrous ions (Fe2+) and hydrogen peroxide (H2O2) [34]. Although the Fenton process relies on ·OH as a primary oxidant, the strong stability of C–F bonds in PFASs presents a significant challenge for their degradation. It is widely recognized that individual ·OH radicals alone are not sufficient to effectively break down PFASs. However, in Fenton oxidation, ·OH plays a crucial role by initiating oxidative pathways that may facilitate the partial breakdown of PFASs structures or enhance their susceptibility to further degradation [97].

2.4.3. Sonochemical Degradation

Ultrasound refers to sound waves with frequencies higher than the audible range of the human ear (>16 kHz). Among the various technologies explored for PFASs degradation, sonochemical treatment has shown great promise. Sound waves cause cavitation in the solution, leading to the thermal decomposition of water and PFASs at the bubble–water interface [98]. Sonochemistry is a method that utilizes acoustic fields to induce chemical reactions in solutions, primarily based on cavitation, which involves the formation, growth, and collapse of bubbles [99]. Sonochemical degradation consumes a significant amount of energy when used alone. By adding additives during sonochemical reactions, a large number of free radicals can be generated, reducing energy input and accelerating the degradation rate of PFASs [35]. After 6 h of combined treatment with ultrasound and persulfate, the defluorination rates of PFOA increased from 33.2% to 38.3% [100]. This indicates that adding persulfate to ultrasonic treatment enhances the PFASs degradation.

2.4.4. Electrochemical Oxidation

The mechanism of electrochemical oxidation for PFAS removal involves the direct oxidation at the anode or/and the indirect oxidation mediated by reactive oxygen species [36]. The removal efficiency primarily depends on the electron transfer capability, ·OH generation capability, and oxygen evolution potential (OEP) of the anode material [101], thus requiring the use of electrode materials with high OEP and good stability. Boron-doped diamond (BDD) anodes have been effective in electrochemically oxidizing PFOA and PFOS, mainly through direct anodic oxidation [102]. Liu et al. [103] utilized an oxygen vacancy (Ov)-enhanced cerium dioxide (CeO2) electrode to catalyze PFASs defluorination, enabling adsorption preconcentration and catalytic degradation at low oxidation potentials (1.37 V vs. SHE). This approach achieved a PFOA removal efficiency of 94.0% and a defluorination efficiency of 73.0%.

3. Alternative Treatment Techniques

3.1. Foam Fractionation

In recent years, foam fractionation technology has gained significant attention for removing PFASs from water. Due to the presence of PFASs in water as anions, anion exchange has been proven to be an effective removal method [39,104]. Foam fractionation exploits the surfactant properties of PFASs, allowing them to preferentially partition into foam, which can then be collected as a concentrate for further treatment. This treatment method typically involves two steps: separation/concentration and destruction. Laboratory-scale studies have shown that foam fractionation can effectively recover over 90% of long-chain PFASs. Based on these results, foam fractionation technology has been applied at pilot and commercial scales, successfully treating PFASs in groundwater and landfill leachate [105]. A factory in Australia effectively removed unregulated/short-chain PFASs from contaminated groundwater using surface-active foam fractionation technology [106]. Furthermore, foam separation technology can effectively remove 91% of PFASs from municipal wastewater and 84% of PFASs from industrial wastewater by using aqueous film-forming foams [107,108]. However, this has also led to concerns about increased byproduct formation. FT-based PFASs are a class of PFASs derived from aqueous film-forming foam (AFFF). Among them, a novel FT-based PFAS, namely 6:2 fluorotelomer sulfonamide quaternary ammonium hydroxyl sulfonate (6:2 FTSA-HOPrS, also abbreviated as EtOH-AmPr-PFHxSAPrS), has been detected at high concentrations in wastewater in Tianjin, China [109].

3.2. Constructed Wetland

Constructed wetlands (CWs) are considered an effective method for removing many persistent organic pollutants, including antibiotics, pharmaceuticals, personal care products, pesticides, and PFASs [110]. Previous studies have shown that CWs can effectively remove PFASs from water through the synergistic actions of plants, substrates, and microorganisms [111] (Figure 5). Xiao et al. [112] used CW to treat synthetic wastewater, achieving PFOA removal rates of 49.69% to 73.63% for initial concentrations ranging from 100 to 1000 μg/L. Various scales of CWs have been employed to investigate the removal efficiencies of PFASs. In Singapore, a large-scale CW system was utilized to treat landfill leachate with total PFAS concentrations ranging from 1269 to 7661 ng/L, achieving a removal efficiency of 61% [113]. Medium-sized CWs (<10 m2) have demonstrated the capability to remove PFASs with efficiency rates between 33.6% and 98.0% from wastewater [114,115]. Laboratory-scale CWs have been extensively studied for the removal of PFOA and PFOS with efficiencies of 18.4–72.1% and 13.8–87.4%, respectively [111,116,117]. However, it is noted that wetland plants can accumulate large amounts of PFAS, but when they are harvested, the decaying root system may release PFAS back into the environment.
When a single method is insufficient for PFASs removal, the combination of multiple methods may produce unexpected results [118]. The combination of CWs with a microbial fuel cell (CW-MFC) can efficiently remove PFASs by enhancing the mechanisms of bioelectrochemical processes, substrate adsorption, and plant uptake. Research has found that CW-MFC systems can effectively remove over 96% of PFASs from wastewater under both open-circuit and closed-circuit operations [119]. Qian et al. [120] utilized microbially attached basalt fiber as a CW-MFC substrate, improving PFASs removal by 1.7–3.4% compared to conventional CW-MFC systems. The experimental results of Wang et al. [121] suggest that arbuscular mycorrhizal fungi (AMF)–plant symbiosis enhances plant resilience to PFAS-induced stress while also improving the pollutant removal efficiency of CWs.

3.3. Piezoelectric Ball Milling

Ball milling (BM), as a biomimetic, clean, and straightforward technique, has gained increasing attention due to its broad applications in sample preparation and mechanical redox reactions [122]. Yang et al. [123] developed a piezoelectric-material-assisted ball milling (PZM-BM) process that achieved complete PFOS and PFOA destruction and ~100% defluorination in 2 h, as well as 80% degradation of 21 PFAS in contaminated sediment within 6 h. The PZM-BM process utilizes the collision activation of PZMs during ball milling, generating an electric potential of approximately kV, enabling non-thermal degradation of PFASs without the need for solvents. Yang et al. [124] report a novel piezoelectric ball milling method for treating AFFF with a total organic fluorine concentration of 9.08 mg/L and a total organic carbon content of 234 mg/L. By co-milling with boron nitride, the undiluted AFFF achieved near-complete defluorination, with an organic fluorine-to-fluoride conversion ratio exceeding 95%.

4. Future Research Directions

Although many technical approaches have been made (Figure 6) while adsorption and thermal degradation are well recognized as the major techniques for the moment, the most efficient and cost-effective solution for PFASs control is far from solved. Further efforts and intensive research should be made at the world level/scale toward the entire solution of PFASs curbing. To the best of the authors’ knowledge, these include the following aspects.

4.1. Removal of Short-Chain PFASs

As time progresses, the potential quantity of PFASs detected in aquatic environments continues to change and increase, highlighting the importance of developing an adsorption process capable of effectively adsorbing multiple PFASs. To date, most adsorption studies have focused on long-chain PFASs. Although short-chain PFASs may have lower bioaccumulation potential compared to long-chain PFASs, future removal of short-chain PFASs may pose challenges. In particular, the adsorption capacity of short-chain PFASs is limited, and adsorbents may be saturated and breached within a short period. Once saturation is reached, PFASs may desorb, raising concerns. This issue is crucial because the removal of short-chain PFASs is expected to become mainstream shortly, necessitating the adoption of new technologies to effectively remove these substances from drinking water or wastewater discharges.

4.2. Remediation of PFASs Contamination

The chemical stability of PFASs’ molecular structure leads to their long-term persistence in the environment, necessitating extended periods for remediation. Remediation techniques, such as biological, chemical, and physical methods, are commonly employed to address PFAS contamination. However, due to the complexity of PFASs and their resistance to degradation, remediation processes often require time and continuous monitoring and maintenance to ensure the sustained effectiveness of remediation efforts. These methods encompass various approaches aimed at breaking down or removing PFASs from the environment, each with its advantages and limitations. Table 4 presents some useful information on PFASs remediation techniques. It should be noted and suggested that the combination of the above several approaches should be explored in research and practice for better PFASs removal. This could maximize each approach’s advantages and make the whole system cost-effective.

4.3. Exploring the Degradation Mechanism of Multi-Structured PFAS

The degradation mechanism of complex PFAS structures poses a multifaceted challenge, necessitating the comprehensive application of various resolution methods. Experimental research involving the synthesis of diverse PFASs structures followed by systematic experimentation, alongside simulation studies utilizing computational modeling techniques to simulate the degradation process, is essential. This approach requires extensive research efforts and collaboration to elucidate the degradation mechanisms of complex PFASs [94]. Such insights are crucial for better management and control of the environmental impact of these organic compounds and for optimizing remediation technologies to a certain extent.

4.4. Increased Exploration of Low-Cost Environmental Remediation Technologies for PFASs

PFASs necessitate the development of environmental remediation technologies. Currently, chemical and physical methods are predominantly used for remediating PFAS contamination. Exploring novel PFAS remediation technologies, such as bioremediation, nanomaterials, and electrochemical techniques, can enhance remediation efficiency and reduce costs [30,94], thereby expediting environmental remediation processes. Currently, cost-effectiveness analyses of PFASs removal techniques are extremely limited. Further economic evaluations are highly desirable.

4.5. Development of PFASs Alternatives

In both 2009 and 2019, the Stockholm Convention on Persistent Organic Pollutants expanded to include several PFASs, notably PFOA (Annex A) and PFOS (Annex B). As of February 2023, Denmark, Germany, the Netherlands, Norway, and Sweden have submitted proposals to the European Chemicals Agency (ECHA) to restrict the production and use of PFASs. These proposals are expected to encompass over 10,000 PFASs. Innovation in the development of PFAS substitutes is underway, with many functional alternatives offering sufficient technical performance already developed and implemented in certain usage categories. However, in other usage categories, innovation is scarce due to various factors such as financial or regulatory disincentives to change methods or production, significant technical challenges, lack of awareness of market opportunities, or smaller market sizes.

5. Conclusions

The efficiency of PFAS removal technologies varies due to differences in reaction mechanisms and environmental conditions. Based on the updated literature, it is fair to say that up to now, adsorption, pyrolysis, advanced oxidation, and biodegradation are the leading techniques, while foam fractionation, constructed wetland, and piezoelectric ball milling are the alternative approaches for PFAS curbing in water and wastewater treatment. Although adsorption has been widely studied for its low cost, energy efficiency, ease of operation, and broad applicability across different PFASs concentrations, challenges such as long adsorption times, poor selectivity, limited regeneration capacity, and the need for secondary treatment hinder its large-scale application. Thermal technologies such as pyrolysis, incineration, and gasification have proven to be effective for degrading PFASs, but their high cost under specific parameters control of the facilities as well as the byproducts’ safety need extensive investigation. The high bond energy and strong electronegativity of fluorine make PFASs highly resistant to most chemical oxidation methods, which are further complicated by environmental interferences, necessitating further optimization for practical use. Meanwhile, biotechnology faces significant limitations, including the lack of highly efficient PFAS-degrading microbial strains and prolonged treatment durations, often spanning several months. As a result, its feasibility for large-scale application remains uncertain.
Moving forward, continued research on PFAS remediation is highly desirable to develop more efficient, sustainable, and practical solutions to mitigate PFAS contamination and restore affected environments.

Author Contributions

Z.C. carried out material preparation, literature review, data collection and analysis, and drafted the first version of the manuscript. Y.Z. supervised the process, substantially revised the manuscript and the figures, finalized its content. T.W. and C.S. contributed to discussions and provided critical feedback. All authors have read and agreed to the published version of the manuscript.

Funding

This study was supported by the National Key Research and Development Program of China (No. 2022YFC3702300) and the National Natural Science Foundation of China (No. 42377086, 42407113 and 42403056).

Data Availability Statement

No data were used for the research described in this article.

Conflicts of Interest

The authors state that there are no conflicts of interest.

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Figure 1. The entry route of PFASs into the human body.
Figure 1. The entry route of PFASs into the human body.
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Figure 2. Removal mechanisms for PFASs via adsorbents.
Figure 2. Removal mechanisms for PFASs via adsorbents.
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Figure 3. Proposed thermal decomposition pathways of PFASs.
Figure 3. Proposed thermal decomposition pathways of PFASs.
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Figure 4. Pathways of PFAS into water and bioremediation techniques for remediation.
Figure 4. Pathways of PFAS into water and bioremediation techniques for remediation.
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Figure 5. Removal pathways of PFASs in CWs.
Figure 5. Removal pathways of PFASs in CWs.
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Figure 6. Outlines of PFASs treatment technologies.
Figure 6. Outlines of PFASs treatment technologies.
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Table 1. Remediation methods of PFASs in the aquatic environment.
Table 1. Remediation methods of PFASs in the aquatic environment.
Remediation MethodsPrincipleAdvantagesDisadvantagesReferences
AdsorptionDifferent kinds of adsorbents were selected to adsorb the PFASs to achieve the removal effect.Good removal; low cost; simple operation.Adsorbent regeneration and disposal issues.[29,30]
Thermal
treatment
High-temperature conditions expose PFASs to air or oxygen, breaking the chemical bonds within their molecules.Suitable for different types of PFASs (both long and short chains).Requiring high-temperature conditions; generating harmful gases.[31]
BiodegradationMicroorganisms destroy C–F bonds and defluorinate under aerobic or anaerobic conditions.Good approach for treating unsaturated PFASs.Long degradation cycle; limited degree of mineralization; the degradation efficiency affected by the degree of fluoridation of PFASs.[32]
PhotodegradationPFAS removal using UV or visible light to generate hydrated electrons.Reduced secondary pollution.Low efficiency; high cost;
small-scale application.
[33]
Fenton
oxidation
Production of ·OH by reaction between ferrous ions (Fe2+) and hydrogen peroxide (H2O2).Relatively low cost;
highly maneuverable.
Generating byproducts; requiring long processing time.[34]
Sonochemical
degradation
A type of advanced oxidation treatment that uses ultrasonic irradiation to form high-temperature bubbles with highly oxidizing substances to degrade PFASs.No need to add chemicals; compatible with other degradation technologies.Small-scale application;
high cost;
easily affected by external influences (e.g., solution pH, viscosity coefficient, surface tension coefficient, solution temperature, etc.).
[35]
Electrochemical
oxidation
Adsorption of PFASs onto the electrode by direct/indirect anodic oxidation, degradation by the electrode, or by reaction with other liquids.High removal efficiency; short reaction time.Generation of short-chain PFASs and toxic byproducts;
high maintenance cost.
[36]
Table 2. Principles and advantages and disadvantages of adsorbents for the treatment of PFASs from wastewater.
Table 2. Principles and advantages and disadvantages of adsorbents for the treatment of PFASs from wastewater.
AdsorbentsAdsorption PrinciplesAdvantages and DisadvantagesRemoval EffectsReferences
Activated carbon (AC)High specific surface area and pore structure for effective adsorption of PFASs through hydrophobic interaction.Low cost, simple process;
applicable to many existing treatment plants;
high quality of treated effluent;
ineffective against short-chain PFASs.
Conventional GAC removes 12% of PFOA but does not remove PFOS; powdered AC removes over 90% of PFOS and PFOA within 72 h at 25 °C.[37,38]
Ion exchange resinIt is mainly adsorbed on its surface through ion exchange and electrostatic attraction.Easy to operate and maintain;
regeneration and reuse possibilities;
high removal efficiency;
not very effective at removing short-chain PFASs;
performance is pH-sensitive.
Polystyrene-divinylbenzene (PS-DVB) resins removed >90% of all 35 PFAS compounds in 24 h, while polymethacrylate and polyacrylic resins removed >90% of less than half of the compounds.[39]
Mineral materialsMineral materials with positively charged surfaces adsorb negatively charged compounds (e.g., PFOA, PFOS, etc.) by electrostatic attraction.Economical; large reserves;
variety and wide range of applications, etc.
At concentrations below 1 ppm, the zeolite removes >80% perfluorocarboxylic acid (PFCA) and >60% perfluorosulfonic acid (PFSA) in less than 30 s.[40]
Molecularly imprinted polymers (MIPs)Synthesis of MIPs using precipitation polymerization enables highly selective adsorption of PFASs.High selectivity but high synthesis cost.The binding capacity of MIPs for PFASs varies significantly, ranging from 1.289 to 1455.5 mg⋅g−1 for PFOS and from 5.45 to 12.4 mg⋅g−1 for PFOA.[41,42]
Carbon nanotubes (CNTs)The specific surface area of CNTs decreases with increasing outer diameter, and those with small diameters adsorb more PFASs.With a high specific surface area;
strong hydrophobicity; poor dispersion in water;
good mechanical properties;
chemical and thermal stability;
ineffective against short-chain PFASs.
Polyaniline nanotubes (PANTs) were prepared by chemical oxidation self-assembly. PFOS and PFOA were adsorbed by electrostatic interaction, while the adsorption capacities were as high as 1651 mg g−1 and 1100 mg g−1, respectively.[43]
Metal–organic frameworks (MOFs)Mainly dependent on electrostatic and hydrophobic interactionsHigh surface area; tunable porosity;
higher stability; easy to adapt;
higher synthesis cost;
ineffective against short-chain PFASs.
Thin-film nanocomposite (TFN) membranes achieved retention rates of 97.75% and 97.85% for PFOA and PFOS, respectively.[44,45]
Bio-
adsorbents
Porous structure of biochar, chemical interactions between its surface functional groups and PFASs, and possible π-π stackingEnvironmentally friendly and cost-effective;
wide raw material availability;
good physicochemical properties.
The aminated rice husk adsorbent reached the adsorption equilibrium of PFBA, PFOA, and PFOS within 3 h, 5 h, and 9 h, with the adsorption capacities of 1.70, 2.49 mmol g−1, and 2.65 mmol g−1, respectively.[46]
Table 3. Decomposition of some compounds of PFASs [72].
Table 3. Decomposition of some compounds of PFASs [72].
Chemical CompoundsPyrolysis TemperaturePyrolysis Product
Perfluoro hexane
(n-C6F14)
Does not decompose at <400 °C, requires palladium catalysts.Fluoride and carbide.
Perfluoro pentane
(n-C5F12)
Does not decompose at temperatures below 840 °C.Hydrogen fluoride, fluorocarbons, fluorides, and oxides.
Octafluorocyclobutane
(C4F8)
360~560 °C.Perfluoro propane and hexane.
Perfluoro propane
(n-C3F6)
550~675 °C.Perfluoro-2-butene and PFIB.
2H-heptafluoropropane
(HFP, C3HF7)
Does not decompose at temperatures below 640 °C.Hydrogen fluoride, hexafluoro propane, and trifluoroacetic acid.
Perfluoro ethane
(N-C2F4)
<550 °C;
550~700 °C;
700~750 °C.
Octafluorocyclobutane;
perfluoro propane and butane;
hexafluoroethane and perfluoro isobutene.
Table 4. Principles and methods of common PFAS remediation techniques.
Table 4. Principles and methods of common PFAS remediation techniques.
Remediation TechniquesRemediation PrinciplesMethods
BioremediationUtilization of microbial decomposition of PFASs.Soil biological treatment or biomobilization.
Chemical remediationUtilizes chemicals to break down PFASs.Advanced oxidation treatment.
Physical remediationPhysical mechanics are utilized to separate and remove PFASs.Adsorbents and redox treatments.
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Chen, Z.; Zhao, Y.; Wei, T.; Shen, C. Leading Techniques for Per- and Polyfluoroalkyl Substances (PFASs) Remediating in Water and Wastewater. Water 2025, 17, 1319. https://doi.org/10.3390/w17091319

AMA Style

Chen Z, Zhao Y, Wei T, Shen C. Leading Techniques for Per- and Polyfluoroalkyl Substances (PFASs) Remediating in Water and Wastewater. Water. 2025; 17(9):1319. https://doi.org/10.3390/w17091319

Chicago/Turabian Style

Chen, Zhenzhen, Yaqian Zhao, Ting Wei, and Cheng Shen. 2025. "Leading Techniques for Per- and Polyfluoroalkyl Substances (PFASs) Remediating in Water and Wastewater" Water 17, no. 9: 1319. https://doi.org/10.3390/w17091319

APA Style

Chen, Z., Zhao, Y., Wei, T., & Shen, C. (2025). Leading Techniques for Per- and Polyfluoroalkyl Substances (PFASs) Remediating in Water and Wastewater. Water, 17(9), 1319. https://doi.org/10.3390/w17091319

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