Hao Zangabc,
Yingming Feng*bc,
Shengyuan Gao*bc,
Mangmang Sub,
Qiyan Fenga and
Xiangfeng Chend
aSchool of Environment Science and Spatial Informatics, China University of Mining and Technology, Xuzhou 221116, China
bThe First Exploration Team of Shandong Coalfield Geologic Bureau, Qingdao, 266400, Shandong, China
cRizhao Marine Geology Academician Workstation, Rizhao, 276800, Shandong, China
dQilu University of Technology (Shandong Academy of Sciences), Shandong Analysis and Test Center, Key Laboratory for Applied Technology of Sophisticated Analytic Instrument, Jinan, 250014, Shandong, China. E-mail: 15053150182@163.com
First published on 18th September 2025
Per- and polyfluoroalkyl substances (PFASs), emerging contaminants with significant biotoxicity, are widely present in aquatic environments. This review analyzes PFAS removal technologies (including adsorption, oxidation techniques—electrochemical, photocatalytic, and sonolytic—biodegradation, and membrane separation), examining their mechanisms, effectiveness, advantages, disadvantages, and applicability. Adsorption remains the most prevalent method, effectively removing PFASs across various concentration levels. However, limitations include long adsorption cycle, difficulty in removing short-chain PFASs, and less-than-ideal regeneration capabilities, which drives ongoing exploration of novel adsorbent materials. Electrochemical, photocatalytic, and sonolytic degradation technologies offer high removal efficiency, short reaction times, the ability to degrade short-chain PFASs, and mineralization potential. Achieving complete mineralization, however, requires stringent reaction conditions, and high energy demands lead to significant operational costs. For biodegradation technology, the search for microorganisms with high PFAS mineralization capabilities and plant species with high PFAS accumulation capacity remains crucial. Consequently, developing low-cost, highly efficient, and widely applicable PFAS removal technologies is an urgent priority. Combining these technologies with other removal methods may be an important direction for future development.
Environmental significancePerfluoroalkyl and polyfluoroalkyl substances (PFASs) represent an emerging class of contaminants that are ubiquitously present in aquatic environments and exhibit significant biotoxicity. This review analyzes various PFAS removal technologies, including adsorption, oxidation, biodegradation, and membrane separation, examining their treatment mechanisms, effectiveness, advantages, disadvantages, and applicability. The urgent need for cost-effective, efficient, and broadly applicable removal technologies is underscored, with potential future directions for development proposed. |
In the years 2009 and 2019, PFOS along with its salts and PFOA were incorporated into the Stockholm Convention's supplementary list of priority persistent organic pollutants. By 2018, the European Union had established a comprehensive limit of 0.5 μg L−1 for PFASs, with a more stringent threshold of 0.1 μg L−1 for individual compounds in potable water supplies. Echoing this, in 2023, the United States Environmental Protection Agency introduced the “National Primary Drinking Water Regulations,” establishing legally enforceable standards for six PFAS compounds, including a maximum allowable concentration of 4.0 ng L−1 for both PFOA and PFOS.13 Following the implementation of global prohibitions and restrictions on PFASs, the center of gravity for the production and utilization of PFASs has shifted from developed to developing nations. The rapid economic growth in these developing countries has fueled a significant increase in demand for high-performance materials containing perfluorinated compounds.14 China, commencing in the early 2000s, embarked on large-scale production and application of PFASs, emerging as a major producer and consumer of fluoride compounds, and a predominant supplier of short-chain PFASs including PFBS and PFBA.15 PFOS and its associated compounds were also added to China's “List of Key Regulated New Pollutants” in 2023.12 The heightened water solubility and enhanced mobility in aquatic environments of short-chain PFASs have necessitated the advancement of sophisticated and effective treatment methodologies for the elimination of PFAS contaminants.16–19
Despite the hydrophobic nature of the carbon-fluorine chains in conventional PFASs, the presence of functional groups like sulfonates and carboxylates can impart significant water solubility and mobility to these compounds within aquatic systems.20 This enables their entry into water bodies via processes like surface runoff and atmospheric deposition, subsequently leading to their conveyance into marine environments via riverine transport, thereby contributing to global contamination.21,22 Consequently, PFASs are prevalent not only in areas of intense human activity but also in various remote environments, including the world's major oceans,23 polar regions,24–26 glaciers,27 the Qinghai-Tibet Plateau,28 and within the organisms inhabiting these areas.26,29 Pala et al.30 initially identified PFASs in Adélie penguins and their unincubated eggs in the Ross Sea, Antarctica. MacInnis et al.31 observed an exponential increase in PFAS concentrations within Canadian Arctic lakes, a pattern that aligns with historical fluctuations in the market for PFAS production and inventory. Ahrens et al.32 conducted a study on the spatial dissemination and migratory patterns of PFASs from Northern Europe to the South Atlantic. Their findings indicated that the concentration of individual PFAS compounds typically ranged within tens of picograms per liter, with PFOS and PFOA exhibiting the highest concentrations. Muir et al.33 reported that in the Great Lakes of North America, the median concentrations of PFHxA, PFHpA and PFOA increased by factors of 3.0, 16, and 1.4, respectively, between the periods of 2000–2009 and 2015–2019. Additionally, Joerss et al.34 examined the Baltic Sea, discovering that the cyclic compound PFECHS, a substitute for conventional PFAS, constituted the highest proportion of the detected PFAS, underscoring the necessity of monitoring fluorinated alternatives. Yamashita et al.35 discovered that the Tokyo Bay demonstrated substantially augmented concentrations of PFOS, PFHxS, and PFOA, which were approximately three degrees of magnitude greater than the concentrations detected in the marine regions of the Pacific Ocean. This finding suggests a strong association between the high levels of PFASs in Tokyo Bay and the urban and industrial activities in Tokyo. Wang et al.36 reported that in the South China Sea, the concentrations of PFASs in surface seawater and bottom seawater ranged from 125 to 1015 pg L−1, with PFBA and PFOA being the predominant compounds. This study also marked the first detection of PFAS substitutes, such as 6:
2/8
:
2 Cl-PFESA and HFPO-DA in the South China Sea. The spatial distribution of PFASs in this region is influenced by river outflow and oceanic currents, with concentrations decreasing from the estuaries to the coastal areas due to dilution effects. Areas characterized by high population density and advanced industrial development generally exhibit higher PFAS concentrations. Moreover, there is an increasing detection of short-chain and novel PFASs (Table 1), some of which have gradually emerged as substitutes for long-chain PFASs, with their production rates on the rise.
PFAS | Acronym | Chemical formula | Classification | The number of publications | Predominant removal technologies studied |
---|---|---|---|---|---|
Perfluorooctanoic acid | PFOA | C8HF15O2 | Long-chain PFAS | 1350 | Adsorption (48%)/AOPs (27%) |
Perfluorooctanesulfonic acid | PFOS | C8HF17O3S | Long-chain PFAS | 1103 | Adsorption (53%)/AOPs (18%) |
Perfluorobutyric acid | PFBA | C4HF7O2 | Short-chain PFAS | 161 | Adsorption (58%)/AOPs (20%) |
Perfluorobutanesulfonate | PFBS | C4HF9O3S | Short-chain PFAS | 155 | Adsorption (55%)/AOPs (12%) |
Perfluorohexanoic acid | PFHxA | C6HF11O2 | Short-chain PFAS | 113 | Adsorption (37%)/AOPs (27%) |
Perfluorohexanesulfonic acid | PFHxS | C6HF13O3S | Long-chain PFAS | 111 | Adsorption (43%)/AOPs (14%) |
Hexafluoropropylene oxide dimer acid (GenX) | HFPO-DA | C6HF11O3 | Short-chain PFAS | 89 | Adsorption (65%)/membrane (12%) |
Perfluoropentanoic acid | PFPeA | C5HF9O2 | Short-chain PFAS | 66 | Adsorption (30%)/AOPs (24%) |
6![]() ![]() |
6![]() ![]() |
C8H5F13O3S | Long-chain PFAS | 59 | Adsorption (29%)/AOPs (27%) |
Perfluoroheptanoic acid | PFHpA | C7HF13O2 | Long-chain PFAS | 57 | AOPs (35%)/adsorption (26%) |
Perfluorononanoic acid | PFNA | C9HF17O | Long-chain PFAS | 36 | Adsorption (39%)/AOPs (28%) |
6![]() ![]() |
6![]() ![]() |
C8ClF16O4S | Long-chain PFAS | 23 | Adsorption (52%)/AOPs (26%) |
Perfluorodecanoic acid | PFDeA | C10HF19O2 | Long-chain PFAS | 2 | AOPs(photocatalytic)(50%)/biodegradation (50%) |
Perfluoroethylcyclohexane sulfonic acid | PFECHS | C8H2F15O3S | Long-chain PFAS | 1 | Adsorption |
8![]() ![]() |
8![]() ![]() |
C10CIF20O4S | Long-chain PFAS | 1 | Flocculation, anaerobic digestion and aerobic digestion |
A comprehensive topic search was conducted within the Web of Science Core Collection database for publications from 2005 to 2024, focusing on “PFAS” in conjunction with “removal”, “adsorption”, “oxidation”, “bioremediation”, and “membrane separation”. This analysis generated Fig. 1(a), which illustrates the escalating research interest in PFAS removal, particularly post-2016. Keyword co-occurrence analysis (Fig. 1(b)) revealed that prominent research foci within PFAS removal encompass diverse PFAS classes, aqueous environments, adsorption processes, various oxidation technologies, and membrane techniques. Based on the data presented in Fig. 1(a), adsorption is the most extensively investigated removal method. Meanwhile, the proportion of publications concerning mineralization techniques capable of achieving PFAS mineralization in aqueous environments—such as electrochemical oxidation, photocatalysis, and sonolysis—has demonstrated a consistent annual increase. In contrast, the proportion of publications dedicated to other advanced oxidation processes (AOPs) (including ozonation, activated persulfate oxidation, Fenton-like reactions, supercritical water oxidation, electron beam irradiation, and plasma irradiation) as well as other treatment techniques (including hydrothermal processing, advanced reduction processes, and coagulation) remains comparatively low. Subsequently, publications specifically addressing PFAS removal from 2016 to 2024 – a period marked by rapid growth in publication output – were subjected to keyword clustering analysis (Fig. 1(c)). This yielded highly significant and robust clusters, as indicated by a modularity value (Q) of 0.7743 and a weighted mean silhouette score (S) of 0.9154 (where Q > 0.3 signifies a significant cluster structure, and S > 0.7 denotes highly efficient and convincing clustering). The identified significant and robust large clusters (e.g., Cluster #0, #1, and #6) represent mature and persistently active core research directions within this field, commonly addressing PFAS removal from drinking water and removal methods utilizing activated carbon. In contrast, emerging smaller clusters exhibiting high intensity (e.g., Cluster #11) may indicate novel technologies or breakthrough research avenues, such as mineralization techniques. Analysis of the top 17 keywords with the strongest citation bursts further underscores that removal technologies capable of achieving mineralization in aqueous environments represent a current critical research frontier. This finding corroborates the results of the aforementioned keyword burst analysis, which highlighted the recent emergence of sonochemical and photochemical removal techniques. These cluster structures delineate the current knowledge landscape and research priorities within the PFAS removal field. In summary, the bibliometric analysis reveals that (1) research related to adsorption constitutes a substantial and steadily maintained volume. Its focus has evolved from an initial emphasis on activated carbon to include ion-exchange resins and biochar, and more recently, towards metal–organic frameworks (MOFs), covalent organic frameworks (COFs), and molecularly imprinted polymers (MIPs). (2) Research concerning electrochemical oxidation, photocatalysis, and sonolysis within the realm of AOPs exhibits exponential growth, particularly regarding investigations into their mineralization capabilities and mechanisms, representing the most cutting-edge exploratory directions. (3) For the relatively mature membrane separation technology, current research predominantly focuses on its integration with mineralization techniques such as electrochemical and photolytic degradation, signifying a crucial development pathway for practical applications. (4) Publications related to biodegradation show relatively modest growth. Cluster analysis indicates that its research is more concentrated on mechanistic exploration and specific precursors, consistent with the challenges associated with its removal efficiency in actual water treatment. Collectively, these overarching trends establish an essential macroscopic context for the subsequent sections of this review to delve deeply into the principles, efficacy, challenges, and prospects of these four technologies.
This review critically appraises current and emerging technologies for removing persistent PFASs from aquatic environments. It systematically analyzes the mechanisms, efficacy, advantages, limitations, and applicability of adsorption, electrochemical oxidation, photocatalysis, sonolysis, biodegradation, and membrane separation. While adsorption remains widely used, significant gaps persist—including inefficient short-chain PFAS removal, slow kinetics, and poor regeneration—driving the need for novel materials. Advanced oxidation processes offer promising degradation and mineralization potential but face barriers like high energy costs and stringent operational requirements. Biodegradation, though environmentally attractive, is constrained by the limited availability of efficient mineralizing microbes or hyperaccumulating plants. By synthesizing these critical insights and limitations, this review underscores the urgent priority for developing cost-effective, scalable, and universally applicable PFAS treatment solutions. It further highlights the integration of complementary technologies as a pivotal strategy for future advancements in sustainable PFAS remediation.
Adsorbent | PFAS | Initial concentration (mg L−1) | Equilibrium time (h) | Adsorption capacity/removal rate | References |
---|---|---|---|---|---|
Granular activated carbon (GAC) | PFOS | 20–250 | 4 | 0.37 mmol g−1 | 43 |
PFOA | 20–250 | 4 | 0.39 mmol g−1 | ||
Powdered activated carbon (PAC) | PFOS | 20–250 | 168 | 1.04 mmol g−1 | |
PFOA | 20–250 | 168 | 0.67 mmol g−1 | ||
GAC | PFOS | 0.5–10 | 24 | 0.032 mmol g−1 | 44 |
PFOA | 0.5–10 | 120 | 0.031 mmol g−1 | ||
PFHpA | 0.5–10 | 120 | 0.029 mmol g−1 | ||
Activated carbon derived from rice husks | 15 kinds, including PFBA, PFOA, PFHxA, 6![]() ![]() |
0.008 | — | More than 95% | 45 |
BAC | PFHxA | 31.4 | 12.5 | 0.06 mmol g−1 | 46 |
PFHpA | 40 | 12.5 | 0.18 mmol g−1 | ||
PFOA | 120 | 33.5 | 1.03 mmol g−1 | ||
AI400 | PFOS | 20–250 | 168 | 0.42 mmol g−1 | 43 |
PFOA | 20–250 | 168 | 2.92 mmol g−1 | ||
Ion-exchange resin adsorption (IRA)67 | PFOS | 200 | 48 | 5.70 mmol g−1 | 47 |
IRA958 | PFOS | 200 | 48 | 4.68 mmol g−1 | |
IRA96 | PFOS | 200 | 168 | 3.82 mmol g−1 | |
IRA900 | PFOS | 200 | 168 | 4.20 mmol g−1 | |
IRA400 | PFOS | 200 | 168 | 0.53 mmol g−1 | |
IRA410 | PFOS | 200 | 168 | 0.73 mmol g−1 | |
IRA67 | PFHxA | 31.4 | 33.5 | 0.12 mmol g−1 | 46 |
PFHpA | 40 | 33.5 | 0.53 mmol g−1 | ||
PFOA | 120 | 33.5 | 2.82 mmol g−1 | ||
IRA67 | F-53B | 200 | 48 | 4.2 mmol g−1 | 48 |
PFOS | 175 | 20 | 5.5 mmol g−1 | ||
20%[NH2]-COF | GenX | 50 | 0.5 | 0.69 mmol g−1 | 49 |
28%[NH2]-COF | GenX | 50 | 0.5 | 91% | |
GAC | GenX | 50 | — | 0% | |
PAC | GenX | 50 | — | 72% | |
MELEM-COF | PFOA | 1 | 1 | 6.04 mmol g−1 (99.7%) | 50 |
MEL-COF | PFOA | 1 | 1 | 4.83 mmol g−1 (99.3%) | |
MELEM-COF | GenX, PFOA, PFOS, PFDA, PFBA, PFHA | Each 0.02 | 0.5 | More than 97% | |
MOF NU-1000 | Groundwater containing PFCA, PFSA, FTS, etc. | 0.19 ± 0.25 | 0.02 | Anionic PFAS: 58% | 51 |
Non-ionic PFAS: 99% | |||||
MOF UiO-66 | Groundwater containing PFCA, PFSA, FTS, etc. | 0.19 ± 0.25 | 0.17 | Anionic PFAS: 2% | |
Non-ionic PFAS: 95% | |||||
MOF ZIF-8 | Groundwater containing PFCA, PFSA, FTS, etc. | 0.19 ± 0.25 | 0.5 | All less than 10% | |
GAC | Groundwater containing PFCA, PFSA, FTS, etc. | 0.19 ± 0.25 | 48 | Anionic PFAS: 37% | |
Non-ionic PFAS: 44% | |||||
MOF NU-1000 | PFOS, PFHxS, PFBS, PFDA, PFOA, PFHPA, PFPeA, PFBA, and TFA | Each 100 | 0.02–0.17 | 1.16–1.76 mmol g−1 | 52 |
Pre-assembled modified MIL-101(Cr) MOF | PFOA | — | 1 | 1.19 mmol g−1 | 53 |
Synthesized and modified MIL-101(Cr) MOF | PFOA | — | 1 | 1.89 mmol g−1 | |
MIPs | PFOS | 200 | 32 | 0.56 mmol g−1 | 54 |
MWCNTs@MIPs | PFOA | 0.1–20 | 1.33 | 0.03 mmol g−1 | 55 |
While numerous treatment methodologies, particularly oxidation degradation techniques, are under active investigation in laboratory settings,39 the most prevalent technology in practical applications remains adsorption, with a focus on activated carbon and anion exchange resin adsorption processes.40 Furthermore, when compared to other removal techniques, these adsorption technologies exhibit superior economic viability. However, the complex adsorption behavior and mechanisms of PFAS molecules, which possess hydrophilic groups alongside hydrophobic and oleophobic C–F chains, present challenges.41 Despite this, the current adsorption technology, which involves the capture of PFASs without their degradation, necessitates the continuous disposal and regeneration of the adsorbent materials. Future research directions in this field will likely focus on developing adsorbents with high selectivity for PFASs that can be easily desorbed and reused in industrial applications, thereby enhancing the sustainability and efficiency of PFAS removal through adsorption technology.42
In summary, extensive research has consistently demonstrated the effectiveness of PAC and GAC in the removal of PFASs from water systems, particularly in the efficient adsorption of long-chain PFASs.56 However, the current limitations of activated carbon technology lie in its reduced efficacy in adsorbing short-chain PFASs. Long-chain PFASs exhibit strong hydrophobic properties, whereas short-chain PFASs possess a degree of hydrophilicity, which hinders their aggregation on the hydrophobic surfaces of GAC.57 Furthermore, the presence of dissolved organic carbon (DOC) in water can diminish the adsorption capacity of GAC or reduce the overall removal efficiency of PFASs by desorbing previously adsorbed PFASs.58 From a practical standpoint, while activated carbon offers the benefits of low cost and a considerable adsorption capability for long-chain PFASs compared to alternative adsorbents, the regeneration of spent activated carbon remains challenging, even with solvents like methanol or ethanol.59 Consequently, the non-reusability of activated carbon necessitates the safe disposal of the spent material.
In a separate study, Du et al.46 utilized bamboo-derived activated carbon (BAC) for the treatment of actual wastewater. They observed that the dosage of BAC had a pronounced impact on the efficacy of eliminating PFASs. As the BAC dosage increased from 0.1 g L−1 to 0.5 g L−1, the PFOA removal efficiency increased from 33.2% to 96.6%, and remained stable at dosages exceeding 0.7 g L−1. The efficiency of removing PFHxA and PFHpA slightly improved with the increase in the initial dosage. Notably, at a 0.3 g L−1 BAC level, the elimination percentage for PFHxA was merely 8.8%, while that of PFOA reached 88.4%, suggesting preferential adsorption of PFOA at lower adsorbent concentrations. The presence of cations in the wastewater enhanced the adsorption process, whereas anions inhibited it. The coexistence of other organic substances adversely affected the adsorption capacity of BAC. Over a broad pH range, BAC demonstrated high selective adsorption for PFOA while also effectively and consistently removing other PFASs. Consequently, BAC is considered particularly appropriate for the extraction of PFOA from actual wastewater, especially under high pH conditions. However, as it stands, the reusability of BAC is currently less than ideal.
[R4N+]Cl− + PFAS− ⇌ [R4N+]PFAS− + Cl− | (1) |
[R3N] + H+ + PFAS− ⇌ [R3NH+]PFAS− | (2) |
Deng47 found that AERs are effective in the removal of PFOS from wastewater. The efficiency and capacity for PFOS adsorption primarily rely on the polymer structure and porosity. Polyacrylic resins, such as IRA67 and IRA958, can rapidly remove PFOS, reaching adsorption equilibrium in about 48 hours, while polystyrene resins take 168 hours. The adsorption capacity on IRA67 and IRA958 was 4–5 mmol g−1, which exceeded the amount of chloride liberated by the resin, indicating that there were other interactions in addition to anion exchange during the adsorption process. The solution pH had little effect on the adsorption of PFOS by IRA958. However, at a pH greater than 10, the deprotonation of the amine functionality led to the adsorption on IRA67 being significantly affected.
Gao et al.48 undertook an investigation into the removal of F-53B and PFOS from electroplating wastewater using the AER IRA67. Their findings indicated that the adsorption capacities for F-53B and PFOS reached 4.2 and 5.5 mmol g−1 pH was identified as a crucial factor influencing the adsorption process. Under acidic conditions, IRA67 exhibited superior adsorption capabilities for F-53B as well as PFOS. The adsorption capacity significantly decreased at pH levels exceeding 10. In actual wastewater scenarios, IRA67 exhibited the capability to concurrently extract F-53B and PFOS without favoring one compound over the other. However, the removal rate was subject to competitive effects, potentially impacting the overall efficiency of the process. The coexistence of sulfate and chromate in the wastewater collectively diminished the adsorption capacity for both F-53B and PFOS. Du et al.46 found that IRA67 benefits from requiring a low dosage and maintaining consistent removal throughout the adsorption cycle, and that ethanol solution or a mixed solution of NaCl and methanol could successfully regenerate the exhausted IRA67.
AER is currently being employed in actual wastewater treatment plants. A 15-month pilot-scale comparative study by Chow et al.64 on PFAS adsorption revealed that AERs outperformed GAC during long-term operation of a pilot treatment plant. However, both AC and AER technologies face challenges such as competitive adsorption, low adsorption capacity for specific PFASs (like short-chain PFASs), and the high costs associated with them often necessitate regular chemical reactivation to rejuvenate the adsorbent or manage spent adsorbents. For example, spent resins typically undergo chemical reactivation with a blend of salts or alkalis and alcohols like methanol or ethanol, necessitating the treatment of the resulting toxic wastewater.48 Some resins, such as the PS/G/bifunctional resin (A532E),65 can only be directly incinerated after reaching a certain adsorption capacity for PFASs. Between 760 and 980 °C, the PFAS content decreases with the increase in incineration temperature, indicating that PFASs decompose more thoroughly at higher temperatures. However, the emission of gaseous PFASs remains a concern.66 The current methods for regenerating PFAS-loaded resins involve the use of high-concentration alcohol cosolvents, such as 70% methanol, combined with saline. These methods require a separate distillation step to recover the cosolvent. Consequently, future research should focus on developing resins and treatment systems that are not only effective in removing PFASs but are also suitable for regeneration, thereby avoiding potential safety or toxicity issues during the regeneration process.67
Li et al.52 investigated the adsorption of nine PFASs by NU-1000, revealing that this material demonstrates a significant adsorption capacity within an extremely short equilibrium period. NU-1000 stands out as one of the most effective adsorbents, rendering it an exemplary adsorbent for both short-chain and long-chain PFAS compounds. The adsorption capacity for short-chain PFBS was observed to be two orders of magnitude higher than that of activated carbon and resin materials, coupled with excellent regeneration and reusability, with near-complete removal and recovery efficiencies.
In comparison to conventional adsorbents, which are characterized by low adsorption capacities and prolonged equilibrium times, MOF materials exhibit superior capacity and efficiency in the removal of PFASs, thereby representing a novel direction in the research of PFAS removal technologies.
Ji et al.49 developed a COF material with X% amino groups, which interact with the anionic head groups of PFASs, and a substantial hydrophobic surface area, further enhancing its adsorption capabilities. The optimized material, with an amino loading of 20–28%, demonstrated high affinity and rapid kinetics for binding 13 different PFAS compounds. The 20%[NH2]-COF variant exhibited the highest adsorption capacity for GenX at high concentrations, while the 28%[NH2]-COF variant showed the fastest and highest adsorption capacity for GenX and 12 other PFASs under environmental conditions. The COF material's adsorption performance for short-chain PFASs, exemplified by GenX, was significantly superior to that of GAC and PAC, with adsorption levels of 91%, 0%, and 72%, respectively.
Zadehnazari et al.50 synthesized COF nanoparticles, MELEM-COF and MEL-COF, which are highly crystalline and demonstrate excellent affinity for various anionic PFASs through electrostatic interactions. These nanoparticles can simultaneously remove multiple pollutants within 30 minutes, achieving removal efficiencies of 90.0–99.0%, including difficult-to-remove short-chain PFASs like PFBA and PFHA. Cationic MELEM-COF achieves a 2500 mg g−1 adsorption capacity via electrostatic and dipole interactions. Moreover, MELEM-COF demonstrated superior regenerability, allowing for multiple reuses through simple methanol washing at ambient temperature.
Incorporating functional groups within the material framework that enhance hydrogen bonding and electrostatic interactions increases the potential for selective capture and extraction of PFAS species. Precise control of the size and distribution of pores in porous materials can affect the adsorption kinetics of PFASs. In the nascent phase of COF application in PFAS elimination, modifying the COF skeleton with different ionic building blocks or functional groups, using fluorine and oxygen atoms, can significantly enhance the adsorption capacity for PFASs.In summary, COFs are at the cutting edge of research into PFAS removal.75–77
Cao et al.79 discovered that MIPs can effectively remove approximately 90% of PFOA from mixtures, with the advantage of rapid adsorption kinetics being particularly useful for the quick separation and enrichment of PFOA. Yu et al.54 discovered that the adsorption capacity of MIPs is pH-dependent, with a decrease in adsorption capacity observed as the solution pH or ionic strength increases. Cao et al.55 synthesized novel MWCNTs@MIPs using multi-walled carbon nanotubes as the supporting material. Their experiments revealed that PFOA reached adsorption equilibrium on MWCNTs@MIPs within approximately 80 minutes, significantly faster than resin and activated carbon adsorbents. There was no significant loss in adsorption capacity after five consecutive adsorption–desorption–adsorption cycles, and the adsorbent demonstrated a high selective recognition ability for PFOA. Owing to its high selectivity for PFOA and superior regenerative capabilities, the synthesized MWCNTs@MIPs are deemed a promising adsorbent for the extraction of PFOA from aquatic environments.
The rational design of MIPs necessitates ensuring that the structure of PFAS molecules aligns with the material properties, which is a key research direction for future MIP removal technology. Future research will focus on more detailed design based on the characteristics of PFAS molecules.
In conclusion, adsorption technology is widely applied for PFAS removal due to its operational simplicity and low cost. However, its core limitation lies in the selectivity-regeneration conflict. Conventional adsorbents suffer from low regeneration efficiency, and competitive adsorption compromises their practical efficacy. Future breakthroughs in emerging materials should focus on functionalized materials designed for synergistic selective adsorption and mild regeneration. This necessitates a focus on bifunctional material design (e.g., integrating ion-exchange groups with hydrophobic micropores), aiming to enhance selectivity for short-chain PFASs while reducing regeneration energy consumption through weak-bonding mechanisms.
Anode material | PFAS | Current density (mA cm−2) | Initial concentration | Electrolyte | Rate constant | Degradation rate and defluorination rate | References |
---|---|---|---|---|---|---|---|
BDD | PFOA | 50 | 15 mg L−1 | 1500 mg/LNa2SO4 + 167 mg L−1 NaCl | 1.2 ± 0.047 h−1 | 99% & 70% | 90 |
BDD | PFOS | 50 | 10 mg L−1 | 1500 mg/LNa2SO4 + 167 mg L−1 NaCl | 0.37 ± 0.017 h−1 | 95% & 75% | |
Ti/SnO2–Sb–Bi | PFOA | 14 | 50 mg L−1 | 1.4 g L−1 NaClO4 | 1.93 h−1 | 99% & 63.8% | 91 |
Si/BDD | PFOA | 20 | 200 mg L−1 | 0.05 mol L−1 Na2SO4 | 0.444 h−1 | 93.6% & 90.2% | 92 |
Si/BDD | PFBA | 23.24 | 0.114 mmol L−1 | 1.4 g L−1 NaClO4 | 0.0332 min−1 | Not mentioned & ≈80% | 93 |
PFHxA | 0.0335 min−1 | Not mentioned & ≈70% | |||||
PFOA | 0.0428 min−1 | 99% & ≈60% | |||||
PFDeA | 0.0455 min−1 | Not mentioned & ≈50% | |||||
PFBS | 0.0139 min−1 | Not mentioned & ≈50% | |||||
PFHxS | 0.0223 min−1 | Not mentioned & ≈70% | |||||
PFOS | 0.0357 min−1 | Not mentioned & ≈70% | |||||
BDD | F-53B | 30 | 100 mg L−1 | 1 mol L−1 NaCl | 0.0550 min−1 | 80.54% & not mentioned | 94 |
BDD/PbO2 | 0.0742 min−1 | 87.32% & not mentioned | |||||
BDD/SnO2 | 0.0641 min−1 | 90.39% & not mentioned | |||||
BDD/SnO2–F | 0.1097 min−1 | 95.6% & 61.39% |
The efficiency of removal is significantly influenced by the electron transfer capability, OH generation capability, and oxygen evolution potential (OEP) of the anode material. Schaefer et al.90 investigated the effective treatment of PFOA and PFOS in chlorinated water and natural groundwater using boron-doped diamond (BDD) anodes. The use of a radical scavenger, tert-butanol (TBA), revealed no impact on the removal rate and corresponding defluorination rate of PFOA and PFOS, indicating that direct anode oxidation is the primary mechanism. Zhuo91 employed a Ti/SnO2–Sb–Bi electrode for degradation of PFOA. After 2 hours of electrolysis, over 99% of PFOA was degraded, and the F-concentration continued to increase, reaching a defluorination rate of 63.8% after 3 hours. Xiao et al.92 utilized BDD electrodes fabricated on conductive single-crystal silicon substrates, achieving a PFOA removal rate of 93.6% and effective mineralization after 6 hours of degradation. Zhuo et al.93 found that BDD anodes could degrade PFXA and PFXS, and the pseudo-first-order kinetic constants for PFXA and PFXS increased with the elongation of the carbon chain, attributing the rise to enhanced hydrophobicity. Increasing the current density from 0.12 mA cm−2 to 0.59 mA cm−2 resulted in a removal rate of up to 97.48% from 0%. The degradation rate of PFOA in acidic solutions was higher than that in alkaline solutions. Zhuo et al.94 demonstrated that SnO2–F modification could significantly enhance the electrochemical performance of BDD anodes. After fluorination of SnO2 crystals, the SnO2–F particles became smaller, the oxygen evolution potential increased by 0.13 V, and the F-53B degradation efficiency improved by 15.07%. Under optimal operating parameters, the removal rate of F-53B was 95.6% after 30 minutes of electrolysis, and the defluorination rate reached 61.39%.
Electrochemical oxidation is an advanced oxidation technology that can remove or even mineralize PFASs in wastewater, including most short-chain PFASs, in a short period of time. However, challenges persist, including the high cost, low activity, and short lifespan of electrode materials.95 Up to now, most studies have been conducted on relatively pure reaction systems, which centered around using spiked deionized water with specific PFASs, and it is still in the phase of experimentation. Achieving the goal of cleaning up PFASs at extremely low concentrations (ng L−1) remains a significant challenge.96,97
Catalyst | PFAS | Light wavelength | Power | Reaction conditions | Reaction time | Degradation rate and defluorination rate | References |
---|---|---|---|---|---|---|---|
None | PFOA | UV254 nm | 200 W | C0 = 1.35 mmol L−1 pH = 3.0 (O2 0.48 MPa) | 72 h | 89.5% & 33% | 83 |
Phosphotungstic acid | PFOA | UV254 nm | 200 W | C0 = 1.35 mmol L−1 | 24 h | 100% & 70% | |
Ccatalyst = 6.68 mmol L−1 pH = 1.8 (O2 0.48 MPa) | |||||||
None | PFOS | UV254 nm | 14 W | C0 = 0.03 mmol L−1 pH = 10 | 2 h | 5.5% & 0.8% | 101 |
I− | PFOS | UV254 nm | 14 W | C0 = 0.03 mmol L−1 pH = 10 | 2 h | 73.9% & 44.3% | |
I−/humic acid (HA) | PFOS | UV254 nm | 14 W | C0 = 0.03 mmol L−1 pH = 10 | 2 h | 97.9% & 77.0% | |
TiO2 | PFOA | MPUV 250–375 | 600 mW cm−2 | C0 = 5 mmol L−1 | 4 h | 100% | 102 |
TiO2 nanoparticles (1.5–6.0 wt%) | |||||||
Na2SO3 | PFOS | UV254 nm | 250 W | C0 = 0.03 mmol L−1 | 0.5 h | 98% & 70% | 103 |
Ccatalyst = 10 mmol L−1 | |||||||
DO = 5 mg L−1 pH = 9.2 | |||||||
Na2SO3 | F-53B | UV254 nm | 16 × 8.0 mW cm−2 | C0 = 0.16 mmol L−1 | 1 min (removal rate of 99%) | 100% & 85% | 37 |
Ccatalyst = 20 mmol L−1 pH = 10 | |||||||
Na2SO3 | PFOS | UV254 nm | 16 × 8.0 mW cm−2 | C0 = 0.16 mmol L−1 | 2 h | 100% & 70% | |
Ccatalyst = 20 mmol L−1 pH = 10 | |||||||
Na2SO3 | F-53 | UV254 nm | 16 × 8.0 mW cm−2 | C0 = 0.16 mmol L−1 | 3 h | 100% & 70% | |
Ccatalyst = 20 mmol L−1 pH = 10 |
Hori and colleagues83 first investigated the photolytic decomposition of PFOA in water. They found that PFOA underwent complete decomposition in the presence of the catalyst phosphotungstic acid after 24 hours of irradiation with a 200 W xenon mercury lamp. The catalyst remained intact and could be reused in continuous operation. To generate sufficient eaq−, both the power and time of irradiation were significantly increased. Sun et al.101 discovered the UV photodegradation of PFOS in the presence of iodide (I−) and humic acid (HA). Without a catalyst, PFOS exhibited a moderately slow rate of direct photolysis; in the UV/KI process, the degradation velocity was moderate, but there was a significant lag phase in the defluorination process; the inclusion of HA in the UV/KI treatment process significantly enhanced the rate of degradation and defluorination, with the defluorination rate increasing by 11.6 times in 1.5 hours. This acceleration is attributed to HA reducing iodine (I2), hypoiodous acid (HOI), iodate (IO3−), and triiodide (I3−) to iodide (I−), thereby producing more eaq−. These eaq− are capable of cleaving the C–C and C–F bonds in PFOS, resulting in its complete mineralization. Ochiai et al.102 studied the decomposition of PFOA in an aqueous suspension containing a TiO2 photocatalyst. PFOA molecules adhered to the surface of TiO2 following adsorption equilibrium, and the adsorbed PFOA molecules were readily decomposed by the holes and ˙OH produced by TiO2, ultimately producing CO2 and F-. At a TiO2 photocatalyst concentration of 1.5 wt%, almost all 5 mmol L−1 PFOA was decomposed during a 4-hour period of irradiation with a medium-pressure UV lamp at atmospheric pressure. Gu et al.103 significantly enhanced the decomposition of PFOA by employing a high photon flux UV/sulfite system to promote the generation of eaq−. The product of sulfite after the reaction is sulfate, which has a much smaller adverse impact on the environment. In an experiment where the reaction time was increased from 30 minutes (98% of PFOS was decomposed) to 60 minutes, it was observed that the fluoride concentration in the test solution continued to increase, indicating a gradual defluorination. The final defluorination efficiency approached 70%. This suggests that after the complete decomposition of PFOS, other fluorinated intermediates were still undergoing defluorination reactions. Bao et al.37 studied the removal of F-53B, PFOS, and F-53 by UV/sulfite reduction. F-53B was easily decomposed with the help of eaq−, with about 99% decomposition within 1 minute. PFOS disappeared within 2 hours, but about 10% of the remaining F-53 was still observable, requiring an additional hour for complete degradation. This indicates that the incorporation of an oxygen atom in the perfluoroalkyl chain reduces the interaction between F-53 and eaq−, thereby slowing down the molecular decomposition. The rapid degradation kinetics of F-53B suggests that chlorine atoms accelerate the decomposition of the molecule. Moreover, more than 90% of the fluorine from all studied compounds was reclaimed in the form of minerals; however, this process extended over a duration of 8 hours. Prominently, when PFOS was undetectable (2 hours), its defluorination rate reached about 85%, while at the same reaction time, the fluorine recovery rates for F-53B and F-53 were lower (about 70%).
Furtado et al.104 demonstrated that PFOS at concentrations close to environmental levels (100 μg L−1) can indeed be degraded using a TiO2/UV system (25 °C, pH = 4, 1.45 g L−1 TiO2), achieving a substantial removal rate of 83% after 8 hours of treatment. Uwayezu et al.105 employed a 185/254 nm UV, 6 W lamp under the condition of 5 g L−1 persulfate to treat industrial wastewater, groundwater, and landfill leachate for 4 hours. Their findings indicated that the main PFAS degradation rates in industrial wastewater were 57% for PFBA, 80% for PFOA, and 60% for PFOS; the main PFAS degradation rates in groundwater were 94% for 6–2 FTS, 75% for PFOA, 62% for PFOS, and 61% for PFHxS. The removal rates of the main compounds in landfill leachate were as high as 12% for PFHxA, 32% for PFPeA, 56% for PFOA, and 43% for PFOS.
In practical applications, photocatalytic technology gradually degrades high-fluorine PFASs into low-fluorine molecules such as trifluoroacetic acid (CF3COOH), and then completely decomposes them into fluoride ions, achieving complete mineralization.106,107 Nevertheless, the coexistence of other organic substances in wastewater may significantly diminish the effectiveness of PFAS removal processes.108 Moreover, the photocatalytic degradation technology may face secondary pollution issues due to the addition of catalysts, which could limit its practical application. Despite challenges, photocatalytic degradation offers swift elimination and substantial treatment capacity, indicating significant promise for eliminating PFAS pollutants from aquatic environments.109
Dannj et al.114 discovered that in a saturated argon water solution, under ultrasonic irradiation at 640 kHz and 396 W, over 80% of GenX was degraded within 60 minutes, with the primary product being fluoride ions. Wood et al.115 conducted degradation studies on PFOS at frequencies of 44, 400, 500, and 1000 kHz, and found that no degradation of PFOS was observed at 44 kHz. At 400, 500, and 1000 kHz, the degradation rates within 4 hours were 96.9%, 93.8%, and 91.2%, respectively, accompanied by a proportional release of fluoride, signifying the mineralization of PFOS molecules. Awoyemi et al.116 treated aqueous film forming foam (AFFF) and foam fractionation (FF) under the conditions of 187.5 W, 580 kHz, and 3 hours. The total PFAS level in AFFF was reduced from approximately 2200 ppb to approximately 766 ppb, a reduction of about 65%. For FF, the total PFAS level was reduced from approximately 1950 ppb to approximately 60.8 ppb, a reduction of about 97%.
Ultrasonic waves represent a promising degradation technology due to their ease of application, ability to completely mineralize PFASs without producing short-chain PFASs, and requirement for minimal or no chemical additives, along with compatibility with various other technologies.17,117 The key factor influencing the effectiveness of ultrasonic action is the intensity of cavitation, which is dependent on the ultrasonic frequency, power density, and the structure of PFASs. Ultrasonic technology is increasingly gaining attention. However, because of the intricacies of real-world scenarios and the high energy demands, there is still limited understanding of its scalability or field application.118 Despite the high energy requirements and associated costs of ultrasonic irradiation (USI) for water treatment, USI holds promise as a viable method for the complete degradation of PFASs in pre-concentrated or highly concentrated wastewater.119
Microbes and their enzymes represent the primary natural mechanism for degrading fluorinated compounds in contaminated environments, transforming and/or defluorinating organic substances through diverse metabolic pathways to obtain energy and nutrients. For a long time, the biodegradation of the exceptionally stable C–F bonds, particularly within the long-chain perfluoroalkyl moieties of PFASs, has been considered a major obstacle. This has made their complete biodegradation, especially defluorination, extremely challenging and resulted in slow progress. Consequently, PFASs exhibit significant resistance to mineralization. Only a limited number of microbial species can utilize them for growth. Most degradation occurs via co-metabolism, where an additional growth substrate provides the necessary energy and nutrients.121 In contrast, polyfluoroalkyl compounds exhibit somewhat greater biodegradability than their perfluoroalkyl counterparts, as their non-fluorinated sites introduce potential points of enzymatic attack.
Previous research has primarily focused on the transformation of precursor substances: (1) perfluoroalkyl sulfonamide derivatives: these compounds serve as precursors for PFOS. Studies by Benskin et al.122 and Mejia et al.123 elucidated the transformation of N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE). EtFOSE undergoes O-dealkylation to form N-ethyl perfluorooctane sulfonamide (EtFOSA), followed by N-deethylation to yield perfluorooctane sulfonamide (FOSA). FOSA is further oxidized via sulfonamide oxidation (nitrogen atom oxidation) to generate PFOS. Both dealkylation steps are catalyzed by monooxygenases, with no cleavage of C–S bonds occurring throughout the process. (2) Desulfonation of sulfonamide precursors: This process involves cleavage of C–S bonds in compounds such as 6:
2 fluorotelomer sulfonamide (6
:
2 FTSA), generating fluorotelomer intermediates (e.g., 6
:
2 fluorotelomer unsaturated carboxylic acid, 6
:
2 FTUCA). (3) β-Oxidation of hydrogen-containing precursors (e.g., FTOHs): this pathway proceeds stepwise without C–F bond cleavage. Initial oxidation converts FTOHs to fluorotelomer aldehydes (FTALs), which are further oxidized to fluorotelomer carboxylic acids (FTCAs). Subsequent β-oxidation cycles entail dehydration to fluorotelomer unsaturated carboxylic acids (FTUCAs), hydration, and oxidative decarboxylation, yielding progressively shorter-chain perfluoroalkyl carboxylic acids (PFCAs). Kinetic constraints in terminal steps result in predominant accumulation of C4–C6 PFCAs (e.g., PFBA, PFPeA, and PFHxA).Shaw et al.124 demonstrated that the aerobic strain Gordonia sp. NB4-1Y efficiently transformed 6
:
2 FTAB and 6
:
2 FTSA within one week, achieving transformation rates of 85–88%. The primary metabolite was 5
:
3 fluorotelomer carboxylic acid (5
:
3 FTCA), with <2% combined yield of short-chain PFCAs (notably PFBA and PFPeA at detectable levels). Yang et al.125 investigated the desulfonation and defluorination of 6
:
2 FTSA by Rhodococcus jostii RHA1. Their study revealed two major transformation products – 6
:
2 FTUCA and α-OH 5
:
3 FTCA-along with two minor products: 6
:
2 FTCA and PFHpA in RHA1 cultures grown in a sulfur-free medium supplemented with ethanol and 1-butanol, respectively. A substantial body of research has corroborated this process. While current investigations focus predominantly on the aerobic biotransformation of these precursor compounds, studies under anaerobic conditions remain scarce.126–128 Yin et al.129 found that EtFOSA in wetland microcosms was biotransformed aerobically with a half-life of 0.5 days but not biotransformed anaerobically. Yi et al.130 found that under nitrate-reducing conditions with equivalent biomass, the anaerobic biotransformation rate of 6
:
2 fluorotelomer thioether amido sulfonate (FtTAoS) was approximately 10 times slower than that under aerobic conditions. Therefore, continued efforts should be dedicated to investigating anaerobic biotransformation, as these endeavors will facilitate the development of remediation strategies tailored to specific electron-acceptor limiting environments.
While current literature predominantly examines precursor biotransformation to terminal products in environmental samples and microbial consortia, specific bacterial strains with defluorination capabilities for perfluorinated compounds including PFOA and PFOS, have been increasingly identified.131 Yu et al.132 reported C–F bond cleavage in two C6 PFASs through reductive defluorination by an organohalide-respiring microbial community. The major dechlorinating species in the seed culture, Dehalococcoides, was not responsible for the defluorination, as neither its growth nor reductive dehalogenase expression was detected. These findings suggest that minor phylogenetic groups within the community likely mediated the reductive defluorination. Huang et al.133 investigated an acidophilic microorganism, strain A6, which utilizes PFOA/PFOS as electron acceptors under anaerobic conditions. Over 100–120 days, this strain achieved a PFOA removal rate of 46.2% and a PFOS removal rate as high as 40.1%. The detection of short-chain PFAAs (e.g., PFPeA and PFHxA) and F− provided direct evidence for the cleavage of C–F bonds (evidenced by F− release) alongside C–C bond cleavage—a significant breakthrough. These short-chain products are likely transient intermediates.
Constructed wetlands (CWs) represent an eco-friendly ecological remediation technique,134 leveraging the natural functions of wetland plants, soils, and associated microbial networks to facilitate the purification of wastewater.135 Their advantages, including low energy consumption, simple operation, and minimal maintenance, have demonstrated great potential for CWs in remediating PFAS-contaminated water. Gkika et al.136 explored the bioaccumulation of PFASs in macrophytes (Myriophyllum spicatum) and sediment-dwelling invertebrates (Lumbriculus variegatus). Initially, the study identified 18 PFAS compounds at a concentration of 4.06 ng g−1. Following a 56-day exposure involving the aquatic plants, PFAS concentrations had dropped to 32% of their original levels and the number of detectable PFAS compounds was reduced to 8. The coexistence of macrophytes and sediment-dwelling invertebrates resulted in an additional reduction of PFAS levels to 25% of the starting concentration, reaching 1.03 ng g−1. However, the organisms were sensitive to environmental changes and did not achieve complete mineralization. Li et al.137 discovered that constructed wetlands utilizing two typical macrophytes, Potamogeton wrightii and Ceratophyllum demersum, achieved a removal of 33.59–88.99% of PFASs through sediment adsorption, plant extraction, and microbial bioaccumulation. Wang et al.138 found that the symbiotic relationship between arbuscular mycorrhizal fungi and wetland vegetation (Iris pseudacorus L.) not only boosts plant growth and photosynthetic capabilities but also heightens the plants' resilience to oxidative stress caused by PFASs, thereby enhancing the contaminant elimination efficiency of CWs. Ji et al.139 discovered that the CW microbial fuel cell system effectively removed PFOA and PFOS with an efficiency exceeding 96%, indicating a broad application prospect for CWs in removing PFASs. Nevertheless, chronic exposure to PFASs can harm plant growth and microbial diversity,140 which may further affect the stability of CWs and reduce their ability to remove pollutants. Grasping and alleviating the adverse effects of PFAS stress on plant development and microbial community composition is vital for enhancing the enduring efficacy and sustainability of CWs in environmental restoration.
Anthropogenic pollutants often introduce novel chemical structures, demanding that microorganisms possess the capability to degrade these new compounds. While this holds true for organochlorides, which generally exhibit favorable biodegradability, the case for organofluorine compounds—particularly polyfluorinated structures—is distinct. Although microbial degradation of such compounds is documented, it occurs infrequently in natural environments. This scarcity arises because the dominant dechlorinating species within microbial communities are not responsible for reductive defluorination. Consequently, the microorganisms capable of actual defluorination likely represent low-abundance populations. Therefore, it is reasonable to expect that microorganisms enriched or isolated specifically for defluorination will exhibit significantly higher defluorination activity and possess a broader substrate range for fluorinated compounds. Thus, future research must focus on enriching or isolating microorganisms responsible for reductive defluorination, followed by characterizing their physiological properties within highly enriched cultures or pure isolates. Bioremediation, including the study of PFAS removal in constructed wetlands, remains in its infancy and has encountered numerous constraints and obstacles. Identifying microorganisms with high PFAS mineralization capabilities and plant species that can accumulate PFASs effectively, as well as comprehending their absorption mechanisms for various PFAS configurations, and bolstering the synergy between these biological elements to improve the removal rate of PFASs remain significant challenges.141,142
Tang et al.145 investigated the potential of reverse osmosis membranes for the treatment of PFOS-contaminated wastewater, discovering that the retention rate of PFOS exceeded 99% for a broad spectrum of initial concentrations (0.5–1500 mg L−1). No distinct correlation was found between the membrane flux and the initial membrane potential. However, an increase in PFOS concentration was associated with a reduction in membrane flux. Liu et al.146 found that under all operating conditions and in evaluated water matrices, NF membranes exhibited a very high retention rate (about 97%) for the selected 10 PFASs. Ma et al.58 studied the retention or removal effects of commercial RO and NF membranes on PFASs. The study also delved into the impact of surfactants, ionic valence, and solution temperature, which have not been fully explored. The study revealed that cationic surfactants (CTAB) could effectively enhance the filtration efficiency of negatively charged PFASs, while anionic surfactants (SDS) could also improve filtration performance by increasing electrostatic repulsion. Furthermore, the study indicated that the filtration efficiency of PFASs improves with increasing ionic valence, with aluminum (Al3+) and phosphate (PO43−) ions showing outstanding performance. At the same time, it was found that higher temperatures could lead to membrane pore expansion, thereby reducing the filtration efficiency of PFASs. Sadia et al.147 found that reverse osmosis membranes might inherently contain PFASs, which have the potential to leach into the treated drinking water. Leaching tests and direct total oxidizable precursor analysis indicated the presence of PFOS (branched and linear), PFBA, PFHxA, PFNA, and PFOA in five selected commercial reverse osmosis membranes, with leaching potential. This resulted in the release of tens of milligrams of PFASs from each membrane element used for drinking water production.
Membrane separation demonstrates good removal efficiency for both long-chain and short-chain PFASs, but it remains a physical method that does not alter the structure of PFASs. The high-concentration PFAS wastewater produced still necessitates subsequent treatment. Additionally, the composition of real wastewater is exceedingly complex, and the dissolved organic matter present in the wastewater can affect membrane flux due to particle size, which may lead to a decrease in the removal efficiency of PFASs. In practice, pretreatment steps are necessary to mitigate the influence of other organic contaminants on the treatment process. Consequently, the high operating costs and maintenance requirements of membrane separation technologies limit their widespread application in actual water treatment.
Remediation technology | Material | Process | Advantages | Disadvantages | References |
---|---|---|---|---|---|
Adsorption | Carbon adsorption materials (activated carbon and biochar) | Selecting different types of adsorbents for the adsorption and removal of PFASs | Effective removal, simple operation, low cost, and widespread application | Only involves adsorbing PFASs from the liquid phase without degradation and difficult to remove short-chain PFASs, and is greatly affected by organic matter in wastewater. Most carbon adsorption materials cannot be reused, and the subsequent safe disposal remains a problem | 59 and 148 |
Anion exchange resin | Superior removal efficiency to activated carbon, simple operation, and capable of removing some short-chain PFASs | Only involves adsorbing PFASs from the liquid phase without degradation. The adsorption time is long, and it cannot effectively remove non-ionic PFASs, and the recovery and regeneration have certain difficulties | 149 | ||
MOFs and COFs | Superior adsorption kinetics and capacity compared to currently implemented large-scale technologies, particularly for targeted removal of short-chain PFASs, enhancing their potential for ionic contaminant analysis applications | Only involves adsorbing PFASs from the liquid phase without degradation. High cost, still in the laboratory research stage | 74 | ||
MIP | Exhibits selective adsorption and excellent regeneration capacity | Only involves adsorbing PFASs from the liquid phase without degradation. The adsorption capacity is relatively weak, still in the laboratory research stage | 150 | ||
Advanced oxidation technology | Electrodes (BDD, lead dioxide, titanium dioxide, tin dioxide, etc.) | Direct oxidation at the anode or indirect oxidation through active free radicals transforms PFASs into non-toxic, biodegradable byproducts | High removal efficiency(≥80%) and short reaction time | The reaction process will produce short-chain PFASs and toxic byproducts, and the high cost, low activity, and short lifespan of electrode materials make it temporarily difficult to achieve the goal of cleaning up PFASs at extremely low concentrations (ng L−1) | 87, 151 and 152 |
Ultraviolet light | The energy of ultraviolet light causes water molecules to produce hydrated electrons (eaq−), hydroxyl radicals (˙OH), and hydrogen radicals (H˙), which work together with specific catalysts to achieve the decomposition and mineralization of PFASs | Strong removal capacity(≥70%), environmentally friendly, and can reduce secondary pollution | High cost and high energy consumption, currently not suitable for large-scale use | 107, 153 and 154 | |
Ultrasonic waves | Using ultrasonic irradiation to form high-temperature bubbles and highly oxidative substances to degrade PFASs | Easy to apply, capable of complete PFAS mineralization without producing short-chain PFASs, requiring less or no chemicals, and compatible with other technologies | The energy demand is high, and the cost is high, currently not suitable for large-scale use | 17, 113, 117 and 155 | |
Bioremediation | Microorganisms and constructed wetlands | Using microorganisms with high PFAS mineralization capabilities and plant species with high PFAS accumulation capabilities to remove PFASs | Environmental friendliness and economic efficiency, avoiding further damage to the aquatic environment | The reaction time is long, and the removal rate is not high. In the future, it is still necessary to understand their absorption mechanisms for different PFAS structures and enhance the interactions between these biological components to improve the removal rate of PFASs | 141 and 142 |
Membrane separation technology | NF membranes, RO membranes, etc. | Using RO membranes and NF membranes to separate PFASs | Effective removal (≥90%) and simple operation | The replacement of membranes and the treatment of high-concentration retention fluid will increase costs | 146 and 147 |
Considering removal efficiency, treatment time, energy consumption, and cost, adsorption is the most widely used technology for effectively removing PFASs. However, the long adsorption cycle, difficulty in removing short-chain PFASs, and unsatisfactory regeneration capacity are the main challenges. Emerging materials such as MOFs, COFs, and MIPs, with their selective adsorption and excellent regeneration and reusability characteristics, are important research directions for PFAS adsorption technology in the future. Electrochemical, photocatalytic, and ultrasound degradation technologies offer the advantages of high removal efficiency and short reaction time. They can degrade short-chain PFASs and have a mineralizing effect, making them important development directions for PFAS removal. However, the requirements for complete mineralization are high, and so far, most treatment technologies have only reported partial defluorination (i.e., removing fluorine atoms from PFAS molecules). Although the degradation rate (such as the truncation of COOH) can reach 100%, the short-chain intermediates produced, which contain multiple C–F bonds, may be more difficult to degrade and toxic than the precursor molecules. Consequently, the ultimate objective of PFAS remediation should be complete defluorination, where all C–F bonds are decomposed into benign inorganic substances, thereby achieving a zero toxicity level. Biodegradation technology has garnered attention due to its good environmental friendliness, but currently discovered microorganisms and plants exhibit low absorption and mineralization effects on PFASs, and the reaction time is long. Identifying microorganisms with high PFAS mineralization capabilities and plant species with high PFAS accumulation capabilities is a crucial aspect. Membrane separation is a technology for efficient PFAS enrichment, yet the complexity of actual wastewater composition presents challenges. Dissolved organic matter in wastewater can hinder membrane flux due to particle size, which in turn diminishes the removal efficiency of PFASs. Additionally, the cost associated with this technology is comparatively high.
It is worth mentioning that these techniques come with a mix of pros and cons for potential use. In addition, due to the different branching and linear isomers, ionic states, and molecular weights of various PFASs, each with distinct environmental destinies and transformation pathways, it is a great challenge to remediate various PFASs using only a single method. Therefore, it is advisable to tailor the choice of technologies to the properties of PFASs, taking into account the pros and cons of different methods. Future research should concentrate on the following aspects: (a) addressing the issue of extended treatment time and the limited regenerative capabilities of adsorption materials; it is necessary to modify the functional groups of adsorption materials to improve electrostatic interactions and hydrophobicity, thereby increasing the adsorption efficiency and the rate of short-chain PFASs. (b) Innovatively designing short-chain PFAS remediation by altering electrodes and catalysts and developing advanced oxidation technologies with low carbon, low energy consumption, high degradation efficiency, and adaptability to low-concentration PFASs. (c) In light of the escalating issue of short-chain PFAS contamination in potable water, it is essential to develop advanced treatment technologies for real-world groundwater and surface water scenarios, and exploring novel adsorption materials, electrode materials, and catalysts is vital to effectively eliminate low levels of short-chain PFASs amidst the complex compositions found in actual water bodies. (d) Short-chain PFASs exhibit greater resistance to degradation compared to their long-chain homologs. Integrative technologies that leverage concentration and degradation recycling can be devised, including the sequential use of adsorption or membrane separation followed by advanced oxidation and reduction technologies, to effectively remove short-chain PFASs from actual water.
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