Journal of Environmental Chemical Engineering 9 (2021) 105784

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Remediation of water from per-/poly-fluoroalkyl substances (PFAS) –

Challenges and perspectives
Shafali Garg a, Jingshi Wang b, Pankaj Kumar a, Vandana Mishra a, c, Hassan Arafat d, e,
Radhey Shyam Sharma a, c, *, Ludovic F. Dumée d, e, f, **
a
Bioresources and Environmental Biotechnology Laboratory, Department of Environmental Studies, University of Delhi, Delhi 110007, India
b
Deakin University, Geelong, Institute for Frontier Materials, Waurn Ponds, Victoria, Australia
c
Delhi School of Climate Change & Sustainability, Institute of Eminence, University of Delhi, Delhi 110007, India
d
Khalifa University, Department of Chemical Engineering, Abu Dhabi, United Arab Emirates
e
Center for Membrane and Advanced Water Technology, Khalifa University, Abu Dhabi, United Arab Emirates
f
Research and Innovation Center on CO2 and Hydrogen, Khalifa University, Abu Dhabi, United Arab Emirates

A R T I C L E I N F O A B S T R A C T

Keywords: Per-/poly-fluoroalkyl substances (PFAS) are an emerging class of environmental contaminants used as additives
PFAS to either enhance the thermo-chemical stability of products or alter the properties of surfaces. PFAS are
Treatment train amphiphilic molecules, composed of fluoro-alkyl chains terminated by specialized functional groups such as
Removal
carboxylic, sulphonic acids, phosphates, sulphonamides, and betaines; offering surfactant-like behavior, and
Degradation
Remediation, tandem technologies
making them highly persistent and mobile across all environmental compartments. The treatment of PFAS
contaminated water remains very complex due to the typically low concentrations and because of the complexity
of the wastewater matrix in which PFAS are present. Exposure to trace amounts of PFAS can cause severe health
impacts across all life forms. Trains of treatment or removal techniques must be employed to achieve higher
removal rates. This review assesses existing methods for PFAS capture, concentration, and degradation from
wastewaters. The performance and selectivity, as well as scalability and cost-effectiveness, of these techniques
are critically compared while operating limitations, as well as emerging solutions, are presented to evaluate the
combinatorial benefits of tandem operations for successful PFAS remediation. The discussion is then focused on

Abbreviations: ACs, Activated Carbons; AFFF, Aqueous Film-Forming Foams; AFPO, Ammonium Perfluorooctanoate; ASH, Air Sparged Hydrocyclon; BCF, Bio­
accumulation Factor; BDD, Boron-Doped Diamond; BiFeO3, Bismuth Ferrite; BiOCl, Bismuth Oxychloride; C.D., Current Density; CaCl2, Calcium Chloride; CaF2,
Calcium Fluoride; CBCs, Coconut-Based Carbons; CNTs, Carbon Nanotubes; DCMD, Direct Contact Membrane Distillation; DMAPAA-Q, (N-[3-(Dimethylamino)
Propyl]Acrylamide Methyl Chloride Quaternary;; EO, Electro-Oxidation; FTCAs, Fluorotelomer Carboxylic Acid; FTOH, Fluorotelomer Alcohol; FTS, Fluorotelomer
sulfonate; Ga2O3, Gallium Trioxide; GAC, Granular Activated Carbon; GO, Graphene Oxide; H2O2, Hydrogen Peroxide; HCl, Hydrochloric acid; HF, Hydrogen
fluoride; In2O3, Indium Trioxide; IrO2, Iridium Dioxide; KOC, Organic-Carbon Partition Coefficient; KOW, Octanol-Water Partition Coefficient; LCMS, Liquid Chro­
matography Mass Spectroscopy; LDH, Layered Double Hydroxides; LOQ, Limit of Quantification; MF, Microfiltration; MIPs, Molecularly Imprinted Polymers; MnOx,
Manganese Oxides; MQL, Method Quantification Limit; MWCNTs, Multi-Walled Carbon Nanotubes; Na2SO4, Sodium Sulfate; NaCl, Sodium Chloride; NaOH, Sodium
hydroxide; NF, Nanofiltration; O3, Ozone; OEP, Oxygen Evolution Potential; OH–, Hydroxyl Ion; PAC, Powdered Activated Carbon; PbO2, Lead Oxide; PC, Photo-
Catalysis; PDFA, Perfluorodecanoic Acid; PEC, Photo-Electrocatalytic; PFAAs, Perfluoroalkyl Acids; PFAS, Per-/Poly-Fluoroalkyl Substances; PFBA C3F7COOH,
Perfluorobutanoic Acid; PFBS, Perfluorobutane Sulfonate; PFCAs, Perfluoro Carboxylic Acids; PFCs, Perfluorinated Compounds; PFDA, Perfluorodecanoic acid;
PFDoDA, Perfluorododecanate; PFHpA C6F13COOH, Perfluoroheptanoic Acid; PFHpS, Perfluoroheptanesulfonic Acid; PFHxA C5F11COOH, Perfluorohexanoic Acid;
PFHxS, Perfluorohexane sulfonate; PFNA, Perfluorononanoic Acid; PFOA C7F15COOH, Perfluorooctanoic Acid; PFOS, Perfluorooctane Sulphonic Acid; PFOSA,
Perfluorooctane Sulfonamide; PFPeA C4F9COOH, Perfluoropentanoic Acid; PFPrA C2F5COOH, Perfluoropropionic Acid; PFSAs, Perfluoro Sulphonic Acids; PFTDA
PFTeDA, Perfluorotetradecanoic Acid; PFTrDA, Perfluorotridecanoic Acid; PFUnDA, Perfluoroundecanoic Acid; polyDADMAC, Polydiallyldimethyl Ammonium
Chloride; POPs, Persistent Organic Pollutants; POSA, Perfluorooctane sulfonamide; POSF, Perfluorooctane Sulfonyl Fluoride; rGO, Reduced Graphene Oxide; RO,
Reverse Osmosis; RuO2, Ruthenium oxide; S2O2– 8 , Persulfate; SnO2, Tin dioxide; SWCNTs, Single Walled Carbon Nanotubes; TFA CF3COOH, Trifluoroacetic Acid;
TiO2, Titanium dioxide; UF, Ultrafiltration; U.S. EPA, United States Environmental Protection Agency; WTPs, Water Treatment Plants; WWTPs, Wastewater
Treatment Plants; ZVI, Zero Valent Iron.
* Corresponding author at: Bioresources and Environmental Biotechnology Laboratory, Department of Environmental Studies, University of Delhi, Delhi 110007,
India.
** Corresponding author at: Khalifa University, Department of Chemical Engineering, Abu Dhabi, United Arab Emirates.
E-mail addresses: rssharma@es.du.ac.in (R.S. Sharma), ludovic.dumee@ku.ac.ae (L.F. Dumée).

https://doi.org/10.1016/j.jece.2021.105784
Received 26 April 2021; Received in revised form 15 May 2021; Accepted 29 May 2021
Available online 2 June 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
S. Garg et al.
prospects for more cost-effective and scalable PFAS remediation solutions enabling the treatment of dilute and
complex water matrices, required to deal with these extremely persistent pollutants.
1. Introduction
Per- or poly-fluoroalkyl substances (PFAS) represent a class of
manmade organo-fluorine compounds composed of fully or partially
fluorinated alkyl chains terminated by polar acid groups such as
carboxylate, sulphonate, or phosphonate [1]. The very stable C-F bond
provides PFAS with both tremendous thermal and chemical stabilities,
unique wettability, and friction properties, supporting their role as ad­
ditives in the manufacturing of flame retardants such as aqueous
film-forming foams, flame-resistant materials, across the
semi-electronic, packaging, anti-adhesive, and metal finishing areas [2].
The very stable C‒F bond provides PFAS with both tremendous thermal
and chemical stabilities, unique wettability, and friction properties,
supporting their role as additives in the manufacturing of flame-resistant
materials, across the semi-electronic, packaging, anti-adhesive, and
metal finishing areas [2]. The high bioaccumulation factor (BCF) of
PFAS owing to its strong protein-affinity coupled with its tremendous
persistence has resulted in PFAS toxicity in organisms across the biomes
globally [3].
The fate and transport of PFAS in various environmental compart­
ments remain unclear. Although long-chained PFAS (>11) were found
to adhere firmly to soil particles, shorter precursors tend to enter porous
substrates and infiltrate groundwater runoffs, polluting both agricul­
tural soil and freshwater sources, from where it might enter food chain
[4–6]. Multiple GenX PFAS and PFAS precursors are known to be vol­
atile and tend to escape into the atmosphere [7–9]. The partitioning
coefficients of all PFAS compounds are not extensively known yet, but
values of the octanol-water partition coefficient log Kow for Per­
fluorooctane sulfonate (PFOS) and Perfluorooctanoic acid (PFOA) were
reported at 4.49 and 4.81, respectively, while the organic-carbon
partition coefficient (KOC) of these two compounds was reported at
2.57 and 2.06 respectively, indicating high PFAS mobility both in water
and soil systems [10].
A maximum permissible limit of 400 and 200 ng L–1 for PFOA and
PFOS, respectively, in drinking water has been set by U.S. EPA, however,
the industrial water samples often reveal much higher concentrations
[11]. Thus, there is an urgent need to develop cost-effective solutions to
manage PFAS containing-effluents, in order to reduce their health haz­
ards towards exposed populations and ecosystems [12]. Treatment
technologies for PFAS were previously partly reviewed with a specific
focus on either the source of the PFAS, such as groundwater [13] and soil
[14], or on the type of the treatment technologies used. Advanced oxi­
dation/reduction processes (AOPs/ARPs) [15,16], adsorption [17],
nanotechnological solutions with photocatalysis, electrochemical
degradation, and adsorption [18], have been reviewed separately.
Degradation pathways by biological agents [19], for short and
ultra-short PFAS precursors [20], and by chemical and physical methods
[21] have been summarized in different studies. The treatment train
approaches or the combinatorial processes have been suggested as a way
forward for the future PFAS treatment research for the effective and
efficient removal of these compounds from complex water systems [22].
The importance of wastewater-based treatment techniques for PFAS
have been assessed and highlighted in multiple previous studies
[23–26]. However, a critical opinion discussing the different capture
and degradation technologies available, taking in consideration their
efficiencies and challenges is missing, to link scalability to technological
implementation towards the development of best remediation guide­
lines and practices for PFAS treatment.
The purpose of this review is not only to guide on factors that affect
treatment and review performance but also to develop a high-level
analysis of the recurring challenges arising from PFAS contaminated
2
Journal of Environmental Chemical Engineering 9 (2021) 105784
wastewater treatment from both processes and operational points of
view. First, general PFAS capture techniques will be discussed in terms
of their respective operability and overall performance, and limitations.
Second, PFAS degradation techniques will be critically presented with
the associated degradation pathways (See SI, Annexure 1). A focus on
their ability to remediate low PFAS levels in complex water matrices will
be provided to develop a critical discussion on the techniques’ current
limitations. The discussion will then develop aspects related to the long-
term efficiency and cost-effectiveness of specific trains of combinatorial
solutions investigated to date to provide holistic PFAS removal strate­
gies. The need for novel processes and materials solutions will be
highlighted as the likely primary way forward to develop rapidly rele­
vant approaches for the global remediation of PFAS-contaminated
wastewaters.
2. PFAS capture/concentration technologies
This section assesses the capture/concentration technologies of PFAS
with a focus on their efficacy to remediate both model and real effluents,
their applicability in Wastewater Treatment Plants (WWTPs), and pro­
vide solutions to overcome the challenges in their selectivity to capture
PFAS.
2.1. Adsorption technologies
Adsorption remains a widely used PFAS removal method, offering
extremely high sorption rates of 2390 mg PFOS g-1 for IRA67/pH > 10
(IERs) [27]. PFAS adsorption onto solid adsorbate is dictated by elec­
trostatic, hydrogen bonding, and hydrophobic interactions, depending
on the water matrix composition and overall adsorbate properties. Ad­
sorbates can be modified with a superficial monomolecular layer to
impart specific properties facilitating binding of the target PFAS mole­
cules. PFAS, usually have negatively charged terminal groups at
environmentally-relevant pHs, enabling its binding with positively
charged adsorbates [28]. The hydrophobic fluorinated alkyl chains
render PFAS extremely electronegative while the hydrophilic polar head
group typically a carboxylic, sulphonic, or phosphonic acid, enables
improved adhesion to adsorbates. Owing to these properties, PFAS form
micelle, acting as surfactants in solution, which is often exploited for
their successful removal [29]. Key materials used for PFAS adsorption
include activated carbons (ACs), granular activated carbon (GAC)[13],
and powdered activated carbon (PAC); both of which offer high surface
area, as well as organo-clay materials, minerals, bio-sorbents, molecu­
larly imprinted polymers (MIPs), nanomaterials such as carbon nano­
tubes (CNTs), and ion-exchange resins (IERs) [30].
2.1.1. Activated carbon
Capture by adsorption with carbon-based materials is the most
common practice for the treatment of PFOS or PFOA in contaminated
water. PFAS adsorption efficiency of over 99% was reported with acti­
vated carbons [31]. Surface modification plays an important role in
achieving higher removal rates. Out of two types of commercial GACs,
charcoal-based (F400) and coconut-based (CBC), modification with a
strong acid such as HCl increased the positive charge onto the surface of
the materials offering better adsorption efficiencies (7–8% for F400 and
6–9% for CBC) for negatively-charged PFAS, while treatment with
NaOH yielded no such benefits. The addition of heat-activated persulfate
(22–25% for F400 and 27–35% for CBC) and H2O2 and Fe (4–8% for
F400 and 12–13% for CBC) reduced the adsorption of PFAS on both
types of GACs [32] (Table 1, Entries 1–6). The addition of a sulfur
polymer- polysulfide to PAC increased the capacity of the adsorption
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 1
Case studies on adsorption and coagulation of PFAS.
Entry Treatment Substance Reaction kinetics Removal (%) Time Scale Reference
(qe) (mmol g–1)

Adsorption
1 Granular activated carbon (GAC) (pH= PFOS, PFOA 0.51 n.d 160,120 h Bench [35]
3.08, 3.0) 0.38
2 Powdered activated carbon (PAC) PFOS 0.69 56 4h Bench [35]
(pH= 3.0, 3.01) PFOA 0.79 34
3 GAC (1250 t, 24 filters, Chemviron F- PFOS Not studied 64 ± 11 n.d. Field- DWTP [71]
400 (Density 440 kg m-3; 12 filters), PFOA 45 ± 19
Norit ROW 0.8 (Density 381 kg m-3; 2
filters) and Norit 1240 EN (Density
485 kg m-3, 6 filters)
4 GAC+R.O. PFOS Not studied 86 ± 7 n.d. Field- DWTP [71]
PFOA 89 ± 22
5 GAC (Filtrasorb® 400, SA= 1050 m2 g- PFBA, PFPeA, Total PFAS PFOS (C6), PFTeDA (C13) 140 days Field- WTP [194]
1
) PFHxA, PFHpA, sorption= 25 µg g–1 and FOSA (C8)- ~80%,
PFOA, PFNA, PFDA, PFUnDA
PFUnDA, PFDoDA, (C10), PFDoDA (C11), PFDA
PFTeDA, PFBS, (C9), PFNA (C8)- 70–80%,
PFHxS, PFHxS (C6), PFOA (C7)-
PFOS, FOSA 60–70%, PFPeA (C4) and
PFBA (C3)- 14− 32%
6 Bamboo-derived AC (BAC) and resin PFHxA, PFHpA, PFOA: 2.82 (IRA67), 65–90 48 h Pilot- washing [195]
IRA67 PFOA 1.03 (BAC) wastewater
7 Anion exchange resin (Purolite® PFBA, PFPeA, Total PFAS PFUnDA (C10), 165 days Field- WTP [194]
A600, average diameter= 610 ± 90 PFHxA, PFHpA, sorption= 44 µg g–1 PFDoDA (C11), FOSA (C8),
mm) PFOA, PFNA, PFDA, and PFDA (C9)- 80–90%
PFUnDA, PFDoDA, and PFNA (C8) and PFTeDA
PFTeDA, PFBS, (C13)- 70–80%, PFBA (C3)
PFHxS, and PFPeA (C4)- 10–23%
PFOS, FOSA
8 IER- AI400 (pH=3.10, 3.02) PFOS, PFOA 0.36 n.d. 120 h Bench [35]
3.39
9 IER (Purolite®A520E, A600E, and PFOA, PFOS, PFBA, 0.006–0.093 100% up to a certain bed 70–80 h Bench [37]
A532E) and PFBS 0.009–0.105 volume (A600E,
0.016–0.130 A520E)
50–60 h
(A532E)
10 IER (Purolite® A592 and A860) PFAS including 45 ± 2 >98 (<10 ng L–1) PFSA = 25 Pilot- River [196]
Gen-X 62 ± 4 min (A592), water
69 ± 3 70 min (A860)
106 ± 3 Precursor
98 ± 5 PFAS = 50
84 ± 3 min (A592),
32 ± 3 100 min
(A860)
11 CNTs- 20 wt% graphene composite PFOA 2.415 × 10-3 96.9 4h Bench [41]
electrodes (BET SA=126.8 m2 g-1, pore
diameter=17.1 Ǻ, V=0.6)
12 MWNTs (Anode= Pt foil (20 mm × 40 PFOA 8.2 × 10-3 n.d. 3h Bench [42]
mm, cathode= Ti sheet (20 mm × 40 PFOS 6.5 × 10-3 2h
mm × 0.5 mm, SA= 6 cm2,
thickness=15 µm, V=0.6)
13 Polyaniline nanotubes (PANTs) (outer PFOS, 3.301 80, 40 h Bench [81]
diameter= 200 nm, inner diameter= PFOA 2.657 64
100 nm)
14 3-(trimethoxysily)propyl- PFOS 0.071 n.d. 0.083 Bench [47]
octadecyldimethyl-ammonium PFHxS 0.065
chloride (TPODAC) in a Si-O-Si PFBuS 0.065
framework (SA=140.6 ± 2.5 m2 g–1)
15 Chitosan crosslinked with PFOS 5.5 n.d. 100 h Bench [46]
epichlorohydrin (SA=14.2 m2 g–1, pore
volume= 9.11 cm3 g-1, pH=3.0)
16 Molecularly imprinted polymers PFOA (template), 0.016 90 0.83 Bench [197]
(MIPs) PFOS 0.013
Two functional monomers- 2-
(trifluoromethyl) acrylic acid (TFMAA)
and 4-vinyl pyridine (4-Vpy) and
ethylene glycol dimethacrylate
(EGDMA) as cross-linker in the
presence of azobisisobutyronitrile
(AIBN) (pH=2.0–5.0)
17 GO (SA= 434.6 m2 g–1) PFOA 0.039 × 10-3 60 48 h Bench and [48]
field- airport
2 -3
18 GO modified with FeO (SA=242.4 m PFOA 0.064 × 10 ~90 3–4 h Bench and [48]
g–1) field- airport
(continued on next page)

3
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 1 (continued )
Entry Treatment Substance Reaction kinetics Removal (%) Time Scale Reference
(qe) (mmol g–1)

19 AC-alumina composite- RemB PFOA 0.062 × 10-3 90 3–4 h Bench and [48]
(SA=123.4 m2 g–1) field- airport
20 Organo-clay: PFOA, PFHxS (0.782 – hematite > 0.5 Bench [198]
Hematite (SA=9.9 m2 g–1, pH=5.9), PFOS, 0.927) × 10-3 > kaolinite >
kaolinite (SA= 23.11 m2 g-1, pH= 3.6), PFHxA, PFOS (0.588–0.624) montmorillonite
montmorillonite (SA= 67.52 m2 g-1, PFHxS × 10–3 ≫ PFOA
pH= 7.2) (0.251–2.707) ×
10–3 ≫ PFHxA
(0.108–0.188) ×
10–3
Coagulation
21 GO (adsorbent) + PFOS + Fulvic acid PFOS 0.061 ± 0.003 day–1 45.8 ± 1.8% 6 h (11.4 ± Bench- [199]
(flocculating agent) 0.5 days half- Organismic-
life in carp carp
intestine)
22 Alum (>60 mg L–1) PFOS, PFOA n.d. < 30 1.5 Bench [53]
23 Alum PFOA n.d. 42 1.5 Bench [57]
24 Ferric chloride (3–5 mg L–1) PFOA, PFOS n.d. 0 1.5 Bench [53]
25 FeCl3 PFOA n.d 4 1.5 Bench [57]
26 FeCl3 + FA (Conc.=50 mg L-1, pH=4) PFOA n.d. 47.6 (9.6) 0.5 Bench and [51]
PFOS 94.7 (14.3) Field
27 FeCl3 PFOS/PFOA n.d. 8/6 0.917 Bench [52]
Alum 23/18
PACl 35/27
(Conc.=5.0 mg L–1, pH=7.2) 65/72
Moringa oleifera (Conc.=30.0 mg L–1, 98/94
pH= 7.2)
M. oleifera + PAC (contact time=10
min)
Electro-coagulation
28 Iron electrode (C.D.=37.5 m cm–2, pH PFOA n.d. 93 1.5 Bench [57]
3.77, and mixing speed=180 rpm)
29 Iron electrode + H2O2 (C.D.=37.5 m PFOA n.d. >99 0.67 Bench [57]
cm–2, pH 3.77, and mixing speed=180
rpm)
30 Periodically reversed Al-Zn electrodes PFOS n.d. 100 0.167 Bench, Field- [58]
(Dimensions=60 × 40 × 2 mm, C. PFHxS 95.6 Groundwater
D.=12 V, pH 7.0, and mixing speed= PFBS 87.4
400 rpm (Reaction by-products O, Al,
C, N, Zn, and F elements)
31 Zn electrode+NaCl (SA= 200 cm2, PFOA 5.74 ± 0.08 96.7 0.167 Bench [200]
width 1 mm) (C.D.= 0.18 Wh L-1) PFOS 7.69 ± 0.04 3.6
Mg electrode+NaCl PFDA 11.3
Al electrode+NaCl PFNA 10.6
Fe electrode+NaCl PFHpA (PFDA > PFNA > PFOS >
PFBA PFOA >
PFHpA ≫PFBA)

process of PFOA reducing its concentration in the sample from 5000 µg
L-1 to 30 µg L-1 within 1 h while stirring. In contrast with PAC, GAC
adsorbed only 200 µg L-1 PFOA due to the lower specific surface area
offered by these materials. The use of PAC also significantly reduced the
generation of dust from the adsorbent degradation, which may block the
pores on the membranes. PAC materials were found to generate dust
concentrations of up to 11,146 µg m–3 for PFOA which was lowered to
only 159 µg m–3 upon addition of polysulfide, which helps prevent less
frequent filter clogging, demonstrating the role and impact of surface
modifiers [33].
2.1.2. Ion-exchange resins
Ion exchange resins (IER) show higher adsorption capacity
(210–2575 mg PFOS g–1 and 1206 mg PFOA g–1) as compared with non-
ionic resins (37–41 mg PFOS g–1 and 38–46 mg PFOA g–1) [34,35].
Different functional groups, polymer matrices of the resins, and porosity
levels dictate the suitability of resins for adsorbing PFAS [17]. Poly
(styrene) resins with type I quaternary ammonium functional groups
showed higher adsorption capacities than poly(acrylic) resins exhibiting
similar functional groups for most PFAS (Perfluorobutanoic Acid
(PFBA), Perfluorohexanoic Acid (PFHxA), PFOA, Perfluorobutane
Sulfonate (PFBS), and Perfluorohexane sulfonate (PFHxS)) except PFOS.
Sulfate as the mobile counter ion, worked more favorably for both types
of resins [36] (Table 1, Entries 6–10). Increased hydrophobicity of the
resins was found to play a major role in the adsorption of PFAS. Van der
Waal forces also play a role in the adsorption process and on assessment
with resins of varied hydrophobicity, the highest hydrophobic resin
displayed the highest adsorption capacity, i.e., in the range of
52.3–260.5 mg g–1. For scale-up operations, the volume of regeneration
of effluents requiring incineration after adsorption can be reduced by up
to 96.5% by using reverse osmosis technologies. Thin poly(amide)
membrane from GE Osmonics designed for brackish water operated at
20–22 bar pressure, gave an average water recovery rate of 65%. This
was followed by vacuum evaporation between 35 and 38 ◦ C. This
reduced the overall operational costs [37]. Cationic polymer-based
hydrogels such as DMAPAA-Q (N-[3-(dimethylamino)propyl]acryl­
amide, methyl chloride quaternary) were also efficient (80–100%
removal) in supporting the adsorption of legacy as well as Gen-X PFAS
and regeneration for up to 10 cycles resulted in no loss of efficiency [38].
2.1.3. Carbon nanotubes
The ability to alter the design of sorbents at the nanoscale has also led

4
S. Garg et al.
to the development of more efficient adsorption materials offering larger
surface areas and enthalpies of adsorption, consistently limiting hys­
teresis of adsorption and greater cyclic performance recovery rates [18].
The presence of nano-sized bubbles increases the surface area onto
which the PFAS adsorbed allowing for more hydrophobic interactions
and subsequently, more adsorption capacity [39]. In a study conducted
to understand the importance of surface roughness and nano-cavities,
under vacuum-degassing, 74–79% of the initial PFOS removal was
compromised with adsorption carried out with CNTs and graphite [40].
Single-walled CNTs (SWCNTs) showed better sorption capacity (556 mg
PFOS g–1, and 492 mg PFOA g–1) [41] than Multi-walled CNTs (MWNTs)
(2.69 mg PFOA g–1) [42]. This higher sorption capacity is facilitated by
hydrophobic interactions, therefore, adsorbents functionalized with
hydrophilic hydroxyl or carboxyl groups are added for aiding such
adsorption processes [43]. However, the electrostatic repulsion between
negatively charged CNTs and anionic PFAS could act against the
adsorption process. Generally, with a decrease in carbon chain length
(<6C), adsorption decreases [44]. 28% amine-functionalized organic
frameworks carried out >90% PFAS adsorption [45]. Thus, surface area,
functional groups, and hydrophobicity are the most important de­
terminants of adsorbent performance. These studies are further sum­
marized in Table 1, Entries 11–13.
By the application of an electric field, the adsorption capacity of the
nanotubes, i.e., electrosorption to MWNTs sheets, increased. Following
pseudo-second-order kinetics, an increase of 41–60 folds for PFOS
(3.251 mg g–1) and PFOA (3.395 mg g–1) was observed when using
continuous sheets supplied with electric field compared to discrete
MWNT powders (PFOS: 1.6 mg g–1 and PFOA: 0.911 mg g–1). This was
attributed to the improved electrostatic attraction between positively
charged electrodes and negatively charged PFOS– and PFO– [42].
2.1.4. Other adsorbents
Bio-sorbents such as chitosan, biochar, husks of rice and wheat, and
quaternized cellulose, extracted from cotton fibers, offer a promising
waste-to-resource approach that is both scalable and cost-effective,
aligning well with circular economy strategies. Chitosan provided
good adsorption capacities of 645–2710 mg g− 1 for PFOS [46]. In a
combined process, MIPs prepared with chitosan crosslinked with
epichlorohydrin was used to permanently confine micelle arrays,
demonstrating the role of electrostatic interactions for PFAS capture,
with adsorption capacities of 105 mg g–1 for PFOS, 95 mg g–1 for PFHxS,
and 65 mg g–1 perfluorobutane sulfonate (PFBS), reached equilibria
within 5 min. In terms of stability, the MIPs showed over 90% recovery
in subsequent adsorption trials for up to 5 cycles with adsorption not
going below 85% for all three types of PFAS [47].
PFOS are known to adsorb well onto carbon materials, such as gra­
phene oxide (GO) (580 ± 205 mg g–1 or mg L–1 measured in terms of
Freundlich affinity coefficient) [29,48]. Graphene oxide (GO) is a
unique monomolecular layer of graphene which can be functionalized
with various functional groups. The use of Mg2+ and Ca2+ cations in­
creases the strength of binding between GO and PFOS by the bridging
effect [49]. Aluminium- and iron-based minerals such as alumina, he­
matite, goethite are able to bind to POPs by hydrophobic and π-π in­
teractions [50]. The use of a commercial material, RemBind™ (RemB),
an activated carbon/clay/alumina-based adsorbent, offered over 90% of
PFOS removal, which comparable to iron oxide modified GO composites
(FeG), but much greater removal than pristine GO (~60%) tested under
the same conditions. The pH and ionic strength of the solution also had
limited impact on the behavior of most of these adsorbents but for GO,
and electrostatic interactions were not found to affect extensively the
binding capacity of the adsorbents. Hence, Ligand exchange mecha­
nisms driven by Fe- and Al-minerals of FeG and RemB as well as hy­
drophobic interactions were found to drive these alumina-minerals
interactions and the functionalization of the GO with metal oxides hel­
ped to enhance the adsorption capacity of GO [48]. These studies are
summarized in Table 1, Entries 14–20.
5
Journal of Environmental Chemical Engineering 9 (2021) 105784
2.2. Coagulation
Coagulation is a conventional treatment method, used widely in
WWTPs. The search for selecting coagulating agents for PFAS capture is
directed around either primary coagulation strategies, whereby chem­
icals directly lead to PFAS coagulation, or secondary coagulation stra­
tegies, whereby PFAS is adsorbed onto discrete powder-like adsorbents,
which are thereafter coagulated. In addition, electro-coagulation, floc­
culation, and sedimentation have also been demonstrated as potential
treatment routes to selectively capture PFAS. Charge neutralization
resulting in separation via. settlement, floatation, or precipitation is
basically the working principle behind the four mechanisms discussed in
this section [51].
2.2.1. Conventional coagulants
Synthetic (alum, ferric chloride, and polyaluminum chloride) and
natural (Moringa oleifera) coagulants were tested for their performance.
Conventional coagulants such as polyaluminum chloride or ferric chlo­
ride effectively neutralized between 0.1 and 1 mg L–1 of PFOS or PFOA
within 30 min of mixing in synthetic wastewater. These strategies are,
however, often ineffective with industrial level concentrations of PFAS
(above 10 mg L–1). PFOA or PFOS removal for the concentration of ~60
mg L–1 with alum only reached 20% efficiency in laboratory-scale con­
ditions. At 5 mg L–1, the efficiency of PFOS/PFOA removal was found to
vary for different coagulant materials from polyaluminium chloride
(PaC) (35/27%) to alum (23/18%) and ferric chloride (8/6%).
M. oleifera @[C0] = 30 mg L–1, coagulated 65% of PFOS and 72% of
PFOA, and conjugated with PaC in 10 min, the removal efficiencies
increased to 98% PFOS and 94% PFOA [52]. pH, non-organic matter,
and stirring time are deciding operating conditions for coagulants per­
formance, and further works on more complex and realistic water
matrices are required [51,53].
Commercial coagulants such as cationic polymers polydiallyl
dimethyl ammonium chloride (polyDADMAC) and polyamine, a co-
polymer of epichlorohydrin and dimethylamine also increase the sorp­
tion of PFAS to Aqueous film-forming foams (AFFF)-impacted grounds
by a factor of 2.0–6.1 [54]. Conventional coagulants such as alum or
ferric chloride were ineffective in treating PFAS from WWTPs [55].
Studies found that flocculation at WWTPs increased PFAS concentration
observed over a three days period. PFHxS increased by 300% by day 3,
Perfluoroheptanoic acid (PFHpA) by 2% by day 2, PFBA, Per­
fluoropentanoic acid (PFPeA), and Perfluorodecanoic acid (PFDA)
decreased by 5–25% by day 2. This could be attributed to the effects of
filtration and precursor degradation [56]. These studies are summarized
in Table 1, Entries 21–27.
2.2.2. Electrocoagulation
Electrocoagulation was found to facilitate the coagulation of PFOS or
PFOA rapidly by promoting sol-gel formation by neutralizing the
negative charge of PFAS by means of a sacrificial anode of iron/
aluminum. These are means to generate hydrous ferric oxide/aluminum
hydroxides, which neutralizes the electrostatic charge across the ad­
sorbates, facilitating the coagulation. However, H+ generation at the
cathode caused the floatation of the adsorbents, eventually requiring
regeneration or replacement. The iron electrode charged at a current
density of 37.5 mA cm–2 was used to coagulate 93% of PFOA within 90
min @3.77 initial pH and 180 rpm of mixing speed. The addition of
H2O2 to this reaction resulted in the oxidative transformation of ferrous
to ferric ions, which increased the removal to >99% within 40 min [57]
(Table 1, Entries 28–31). Using the same electrode over many cycles,
generates a passivation effect, which can be negated by periodic
reversing of electrode polarity. The use of switching polarity was
demonstrated for Zn-Al electrodes with reversing cycles every 10 min @
12.0 V, 7.0 pH, stirring speed of 400 rpm, and initial concentration of 1
mg L–1. The removal of various PFAS compounds was demonstrated
using this set-up, with 87.4% removal of PFBS, 95.6% of PFHxS, and
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 2
Case studies using high-pressure membranes for PFAS concentration.
Entry Process Membrane code Compounds Treatment conditions Feed Efficiency (%) Scale Reference
concentration
(mg.L-1)

1 RO BW30, ESPA3, PFOS Cross-flow 0.5–1600 >99 Bench [65]

LFC3, and SG semiconductor
wastewater
pH 4
2 RO BW30, LFC1, PFOS Crossflow 10 >99 Bench [68]
LFC3, ESPA3, and synthetic
SG semiconductor
wastewater
pH 4
3 RO BW30, XLE, and PFHxA Crossflow 100 BW30, XLE, Bench [69]
SW30XLE synthetic industrial SW30XLE >99 at
effluents pH 7.1
pH 3.5 and 7.1
4 UF-RO n.d. PFOA and PFOS Crossflow 15–26 > 99 Bench [71]
Surface water quality 61–86 and Field
5 NF NF90, NF270, DK PFOS Crossflow 10 90–99 Bench [68]
synthetic
semiconductor
wastewater
pH 4
6 NF NF270, NF200, PFPnA, PFBS, PFHxA, PFHpA, PFHxS, Crossflow 1 For all PFAs Bench [74]
DK, DL PFOA, 6:2 FtS, PFNA, PFOS, FOSA, synthetic tertiary- >95
PFDA, PFUnA, PFDS, PFDoA, PFTeA treated wastewater 5> pH > 6;
pH 3 – 10 60–80
at pH 3
7 NF NF27, NTR-7450 PFHxA Cross-flow 100 70–99 Bench [76]
Synthetic water
pH 3.3, 7, and 10
8 NF NF270 PFOA Cross-flow 1 85–90 Bench [80]
Synthetic water
pH 7
9 NF NF90, NF270 PFHxA Crossflow 100 NF90 Bench [69]
synthetic industrial >97 at pH 3.5
effluents >99 at pH 7.1
pH 3.5 and 7.1 NF270
>80 at pH 3.5
>95 at pH 7.1

Notes: XLE: extra-low filtration, LFC: low fouling composite, SG: Singapore membrane, ESPA: energy saving polyamide, NF: nanofiltration, DL: dual-layer, ACM:
Actively Cool Membrane.

100% of PFOS within 10 min of operation from real groundwater [58].
2.3. Membrane filtration
Membrane filtration is a process whereby a semipermeable or porous
membrane is used to selectively separate a solvent from solutes [59].
Membrane filtration allows the opportunity to concentrate PFAS, which
offers the potential of PFAS reuse in industrial processes. The membrane
separation process is driven by a pressure, electrical or temperature
gradient, leading to specific solvent permeation through the membrane
and solutes’ rejection capabilities. The solutes rejection mechanisms in
membranes may, in fact, occur due to a combination of sieving and
charge attraction/repulsion mechanisms. The former mechanism is
typically applicable to particulate matter while the latter dominates the
rejection of ions and small organic molecules [60].
Although low-pressure membranes, such as microfiltration (MF) and
ultrafiltration (UF) membranes with large pore size distributions
centered around 100–400 and ~10 nm, respectively, are unsuitable for
rejecting low molecular weight compounds such as PFAS [61], they
remain useful during pre-treatment processes for concentrating PFAS
and to mitigate fouling at subsequent treatment processes. The appli­
cation of MF membranes in the direct contact membrane distillation
process (DCMD) was reported as a pre-treatment for concentrating
PFPeA compounds from synthetic wastewater [62]. Since the DCMD
processes are driven by vapor pressure differences, the filtration trials
were conducted at different temperatures. At a feed temperature of
50 ◦ C, the rejection of PFPeA reached the highest value of 85%. The
rejection of PFPeA was found to drop from 85% to 58% when the feed
temperature was increased from 50 to 70 ◦ C, which was correlated with
an increase in the evaporation rate of the feed solution.
However, high-pressure membrane processes, including nano­
filtration (NF) and reverse osmosis (RO) have been widely applied at
bench and pilot scale for sequestering PFAS from wastewater. Few full-
scale trials were performed to increase the rate of evaporation of the feed
solution over the past two decades since the pore size/molecular weight
cut-off (MWCO) of these membranes is sufficient for the PFAS retention
[63,64]. The applications of RO and NF processes for PFAS treatment are
summarized in Table 2.
2.3.1. Application of RO processes for PFAS treatment
The first study on concentrating PFAS using four commercial RO
membranes showed efficacy to remove >99% of PFOS (538 g mol− 1)
across a concentration range of 0.5–1600 mg L− 1 from semiconductor
wastewater [65]. Although the rejection performance was enhanced
with increasing concentration of PFOS in the feed. The PFOS rejection by
commercially available membranes such as brackish water (BW30), low
fouling composite (LFC3), and Singapore membrane (SG) all reached
>99.9% PFOS concentration, while a less significant enhancement of the
PFOS rejection was observed for the Energy-Saving Poly(amide)
(ESPA3) membranes. The PFOS rejection performance was reconciled
with NaCl solutions’ rejection for these RO membranes, suggesting size
exclusion as the controlling factor for rejecting PFOS and that the tighter
RO membranes can effectively reject more PFOS molecules, which are
governed by solubility and diffusivity of the solute and solvent. Similar

6
S. Garg et al.
Osmosis, FL: Filtration, NF: Nanofiltration, OR: Oxidation/reduction, SC: Sonochemical, PT: Photo/Thermal, BT: Biological treatment, ET: Enzymatic treatment, UV:
Ultraviolet, AF: Air-fractionation, OZ: Ozonation, RP: Reduction processes, AR: Aeration, EO: Electro-oxidation, PC: Photocatalysis, UF: Ultrafiltration, TP: Water
treatment plant, OP: Oxidation processes, ZI: Zero-valent iron, BC: Biological activated carbon.
mechanism has also been reported for pharmaceuticals [66]. Theoreti­
cally, negatively charged membranes shall reject negatively charged
organic compounds more effectively owing to electrostatic repulsions
[67]. The ESPA3 exhibited a more negative streaming potential charge
at pH 4, while both BW30 and LFC3 were similar to each other and
exhibited a less negative absolute charge at the same pH. The results
suggest that the impact of electrostatic repulsions on PFOS rejection is
not as significant as size exclusion mechanisms when using RO mem­
branes for PFAS removal. Using RO membranes for treating PFOS mol­
ecules at lower concentrations (10 mg L− 1) [68] and for treating PFAS
with shorter-chain such as PFHxA also confirmed similar behaviors [69]
(Table 2, Entries 1–5).
Another series of studies evaluated the normalized initial RO fluxes
to differentiate the effect of initial flux from that of the membrane ma­
terials properties showed superior removal efficiencies of >99% for
PFOS with SG, LFC1, LFC3, BW30, and ESPA3 RO membranes [68].
From an operation point of view, the filtration conducted at higher
applied pressures led to a severe degree of fouling, hindering the passage
of both water and PFOS molecules, and subsequently rejecting more
PFOS molecules over time. Furthermore, LFC1, LFC3, and ESPA3 with a
surface roughness of 135.8 ± 12.8, 108.4 ± 12.4, and 181.9 ± 26.1 nm,
respectively were found to be more easily and rapidly fouled than SG
and BW30 with a surface roughness of 17.3 ± 3.0 and 68.3 ± 12.5 nm,
respectively. The results imply that RO membranes with rougher sur­
faces were more susceptible to PFOS adsorption than those with smooth
surfaces by providing more surface areas, in line with silica colloidal
matter fouling, a relevant comparison point to PFAS given molecular
weights and native compounds charge [70].
RO membranes were also often applied in combination with other
techniques, improved PFAS removal process efficiencies across several
pilot plants and a drinking water treatment plant (DWTP). UF pre-
treatment prior to RO units was tested to remove PFOS and PFOA
molecules. The UF-RO treatment trains were able to reject >99% of
PFOS and PFOA owing to the RO barriers [71]. In both pilot and
full-scale operations similarly, tertiary effluents containing per­
fluoroalkyl acids (PFAAs) were treated by RO followed with
7
Journal of Environmental Chemical Engineering 9 (2021) 105784
Fig. 1. Comparison of technology performance
in terms of removal efficiency achieved to
capture or degrade PFAS, with the treatment
trains or hybrid systems both in the lab- and at
field-scale. Data recorded in Tables 1–6.
Missing bars represent lack of data in the
respective research articles. From the box-plots,
it is observable that there is consistently high
removal shown by treatment train approaches,
affirming their usefulness for upscalability and
achieving high efficiency. Notes: AC: Activated
carbon, IR: Ion-exchange resin, NA: Nano­
adsorbent, OT: Others, CC: Conventional coag­
ulant, EC: Electrocoagulant, RO: Reverse
Ultraviolet-advanced oxidation processes (RO-UV/AOPs) showing
complete mineralization of the PFAA substances, though the content
within the post-treatment RO concentrates [72] was not explicitly
mentioned in the study, but it highlights the usefulness of hybrid tech­
nologies (Table 6).
2.3.2. Application of NF processes for PFAS treatment
The retention performance of NF membranes, semipermeable
membranes with looser microstructures compared to RO membranes, is
also governed by size exclusion of compounds. NF270 membranes were
used to reject nine PFAS, including PFBA, PFPeA, PFHxA, PFOA, per­
fluorononanoic acid (PFNA), PFDA, PFBS, PFHxS, and PFOS [73].
Retention by the NF270 membranes was achieved for PFBS and PFHxS,
exhibiting a molecular weight of 300 and 314 g mol–1, for which the
rejection dropped to 93% and 97%, respectively [73]. For lower mo­
lecular weight PFAS compounds, only 70% of PFPeA (264 g mol–1) was
rejected by NF270 in a separate study [74]. Based on the size exclusion
mechanisms, the MWCO of NF membranes, defined for rejection at or
above 80%, therefore appears to lay around 300 g mol–1.
The performance of NF membranes to reject PFAS compounds may
be enhanced further by controlling electrostatic repulsions between the
contaminants and the membrane surface [67,75]. The impact of the pH
on the retention of anionic Perfluorooctane sulfonamide (POSA) [74],
and PFHxA molecules [69,76] by negatively charged NF membranes
were reported for several bench-scale studies. In these studies, PFOA,
POSA, and PFHxA dissociated into negative ions at the pH range of 3–10.
At lower pH range, for the NF270 membranes, exhibiting an isoelectric
point at around pH 4, the surface charge of the membranes became less
negative to neutral, which led to the reduction of solute rejection and
hence adsorption of PFAS compounds. As the solution pH increased
toward the alkaline range (pH 6–10), the membrane surface with
dissociated carboxylic functional groups became strongly negatively
charged, which increased PFAS rejection from electrostatic repulsion
between anionic PFAS molecules and the membrane surface [69, 74, 76,
77]. Furthermore, the membrane materials can be engineered to
enhance the fouling resistance against PFAS compounds. The BW30
Fig. 2. Comparison of technology performance
in terms of time taken to capture or degrade
PFAS, with the treatment trains or hybrid sys­
tems both in the lab- and at field-scale. Data
recorded in Tables 1–6. Missing bars represent
lack of data in the respective research articles.
From the box-plots, it is observable that some of
the adsorption, aeration and biological tech­
nologies show extremely high removal times
and with the exception of field studies with
water treatment plants (WTPs), most of the
treatment train studies bring down the removal
time significantly.
S. Garg et al.
membranes with amine enriched surfaces would be more negatively
charged under alkaline conditions, thus attributing to a stronger repul­
sive interaction with the dissociated PFAS ions and subsequently resist
PFAS adsorption [78] (Table 2, Entries 6–9).
Membrane fouling caused by the adsorption of PFAS is also
inevitable during NF filtration processes, which subsequently in­
fluences rejection and permeation. A significant 35% permeation
reduction was observed during the filtration experiments using 9
PFAS compounds [73]. Smaller PFAS molecules, such as PFHxS and
PFBS, remained undetected at the end of filtration tests in the
permeate solution, indicating that the fouling layer hindered the
passage of PFAS molecules and likely concentrated them in the cake
layer onto the membrane surface. Such rejection enhancements were
caused by the entrapment of PFAS within the selective poly(amide)
layer of the membrane material [68,79]. The cake layer formation,
however, led to a decline in the PFAS rejection capability over time, i.
e., membrane fouling.
The selective layer of NF membranes could also be tailored to feature
nanoscale surface pores across the material surface to minimize inor­
ganic fouling [80]. The water flux of such NF membranes declined by
18% at the end of 20 h scaling tests with a mixture of the PFOA and salt
solutions containing sodium chloride (NaCl), calcium chloride (CaCl2),
and sodium sulfate (Na2SO4). The virgin NF270 experienced a much
higher flux decline by 28% compared to the modified membranes
(Table 2). The operating parameters in terms of removal and time taken
are compared in Figs. 1 and 2.
2.4. Limitations and directions for PFAS capture technologies
Adsorption is one of the most commonly applied techniques for PFAS
capture since performing at low operating costs, and offering high
removal efficiencies up to 2710 mg PFOS g–1 for chitosan [46],
2390 mg PFOS g–1 for IERs [27], and 1651 mg PFOS g–1 for CNTs [81],
respectively. The simplicity of the design and both the modulation and
regeneration potential (especially MIPs and CNTs) of the process also
favor the implementation of these materials. However, low adsorption
and coagulation rates may detrimentally extend the operating times, up
to 240 h for GAC, 168 h for IERs, 10 h for CNTs, MIPs, and bio-sorbents,
thus requiring thermal regeneration of adsorbent such as GAC with
temperatures above 600 ◦ C, creates waste residuals to dispose off
exhausted carbon, process optimization is necessary in terms of pH,
temperature, and contact time [17]. Different absorption chemistry is
observed for varied conditions of pH. Sorbents, such as activated carbon
materials, are expensive and regeneration is not always feasible [82].
The nature of the performance achieved ranged widely based on the
different types and expected interaction mechanisms between the sur­
face of the adsorbents and coagulants and the PFAS solutes. Initial
concentration of the PFAS solute also plays a critical role in determining
the removal efficiency. A direct comparison of the performance of the
two main types of adsorbates is not entirely valid but specific isotherms
of adsorption as well as reaction kinetics should be standard methods to
evaluate interplays and link operating conditions to capture outputs.
Resins and bio-sorbents were found to be much better adsorbents
compared to AC, which are nevertheless the most reported materials in
literature due to their low cost and accessibility. PAC has 100 times more
surface area than GAC but they are not reusable whereas GAC, even
though more expensive can undergo regeneration, a couple of times
[83]. However, the regeneration costs of ACs hinder their application in
daily-use processes and new regeneration strategies, specific to PFAS
contaminations, must be developed.
Conventional coagulation, flocculation, and sedimentation tech­
niques are not able to achieve more than 20% removal with real
wastewater. Pollutants are transferred to another phase without being
degraded, regeneration is neither practiced nor feasible with floccula­
tion. Spent coagulants are often removed after usage and chemicals
added each time while changing wastewater load. Sacrificial electrodes
8
Journal of Environmental Chemical Engineering 9 (2021) 105784
add to the cost of the process and make electrocoagulation an energy-
intensive process [84]. Sedimentation, however, has no effect on the
concentration of PFAS in WWTPs [85,86]. Hence, ineffective for treat­
ment of PFAS.
Although novel adsorbent materials and especially nanomaterials
are promising adsorbent materials, limitations of their scalability, and
potentially toxic side effects from the bare adsorbents if released in
decontaminated waters, represent a major hindrance to their develop­
ment. Furthermore, adsorption and coagulation are often coupled with
other concentration techniques such as membrane filtration to maximize
removal.
NF membranes with looser microstructures may be more energy-
efficient towards PFAS rejection, compared to RO membranes. How­
ever, the MWCO of NF membranes is larger than that of RO limiting
their applicability to reject low molecular weight PFAS compounds.
Furthermore, unlike RO membranes of which rejection mechanisms
are governed predominantly by size exclusion, the performance of NF
membranes are under significant influence of the chemistry of PFAS
contaminated feed such as pH, ionic strength, and the content of dis­
solved organic matters [68,74]. Although the retention performance of
RO at a large scale remained at the same level as bench-scale studies,
as a non-destructive method for PFAS treatment, disposal of the PFAS
concentrated brine has always been an issue [87]. At the pilot scale,
the retention performance of the NF membrane, especially in combi­
nation with other treatment processes such as electro-oxidation (EO)
and photocatalysis, cannot match the hybrid approaches conducted at
the bench scale (>93–99%) [73,88,89]. These challenges and research
needs are summarized in Table 7. Most of the current studies are done
on a laboratory scale and lack the field application studies. Systematic
studies to develop ultra-selective PFAS capture pathways or materials
are therefore required.
3. PFAS degradation technologies
This section focuses on recent advances in degradation, decomposi­
tion or mineralization of PFAS, mostly achieved by oxidation/reduction
of PFAS, covered as the physicochemical processes of catalysis, wet
oxidation-reduction, sonochemical, photo/thermal as well as the
biochemical processes, which involve biologically derived catalysts or
biological systems leading to PFAS degradation. The mechanism of
degradation of PFOA and the various reaction intermediaries have also
been discussed.
3.1. Catalysis
The catalytic degradation of PFOA compounds has been studied
using both photocatalytic and electrocatalytic approaches. The strong
bond dissociation energy of the C‒F bonds (<544 kJ mol–1) represents a
key challenge to mineralize PFOA efficiently. This section provides links
to the properties of materials and kinetics of reactions and the primary
catalytic degradation pathways of PFOA compounds are discussed. Po­
tential new materials that can be used in this application as well as
scalable routes towards energy-efficient PFOA treatment will be
introduced.
3.1.1. Photocatalysis
Photolysis was initially considered as a potential option since used
extensively for the degradation of a variety of toxic agrochemicals,
pharmaceuticals, and other industrial compounds [60,90]. However,
direct photolysis of different PFOA compounds in water with UV-C
(254 nm) even up to 300 min of exposure showed very low degrada­
tion [91]. The photon energy of UV-C of 254 nm (471 kJ mol–1) remains
insufficient to split the C-F bond [21]. Although shorter wavelength,
below 200 nm, would yield photon energies of >600 kJ mol–1, the
operating costs involved with such UV sources, and yet low efficacy, are
typically considered prohibitive for scale-up applications. Thus, the
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 3
Photo-, electro- and photoelectro- catalytic performance towards the degradation of PFOA materials. All kinetic degradation rates reported were normalized for
comparison purposes. Most of the tests done to date reported data on perfluorooctanoic acid compounds [55]. However, [136,201] can be referred to for better
understanding.
Entry PFOA Materials details and Catalytic operation Major by-products Kinetic degradation Comments on performance Reference
properties conditions besides H+ and F- rate (min-1)

Photocatalysis
1 PFOA Titanium dioxide 254 nm @ 400 W and 25 oC; PFHpA, PFHxA, F- 2 and 5 Limited impact of the TNTs on [95]
nanotubes (TNTs), 9 nm 50 mg L− 1 PFOA ions the rate
inner diameter dispersed
in solution
2 PFOA Cu and Fe doped 254 nm @ 400 W and 25 oC, PFHpA, PFHeA, 1 and 3.1 Increased rate with metal [202]
titanium dioxide thin 0.5 g L− 1 catalyst, varied pH; PFPeA, PFBA, doping but no significant
films dispersed in 50 mg L− 1 PFOA PFPrA, TFA changes
solution
3 PFOA Titanium dioxide Pb 254 nm @ 400 W and 25 oC; PFHpA with a 2 and 85 Pd doping more efficient than [99]
doped thin films catalyst concentration from reduced number previous metal doping
dispersed in solution 0.1 to 3 g L− 1; 50 mg L− 1 of the CF2 units;
PFOA PFHpA, PFHeA,
PFPeA, PFBA,
PFPrA, and TFA
4 PFOA TiO2-rGO 200 and 600 nm wavelength Not assessed but 0.2 and 1.9 TiO2 alone was worse than [93]
@ 150 W, catalyst theorized photolytic reference. The level
concentration from 0.05 to of TiO2 doping on the graphene
0.5 g L− 1. 50 mg L− 1 PFOA was not evaluated
5 PFOA Pt, Pd, Ag modified TiO2 125 W at 365 nm, 5.3 Not assessed 20 and 121 Doping levels were not assessed. [96]
mWcm-2; catalyst 0.5 g L− 1; Unclear if Pt had the same
PFOA 60 mg L− 1 atomic level of doping as others
6 PFOA In2O3 nanostructures 15 W @ 254 nm; catalyst Not assessed 5 and 1323; best The geometry and size of the [92]
concentration 0. 5 g L− 1; performance for the particles were varied by
PFOA concentration of porous spheres adjusting the co-solvent addition
30 mg L− 1 compared to dense during hydrothermal synthesis.
cubes Variations attributed to the level
of O vacancies
7 PFOA In2O3 and Titanium 23 W @ 254 nm; PFOA 100 Not assessed 4 and 25 Tests were done with model [203]
oxide μmol L− 1 mixed with 0.05 g secondary effluents showed
L− 1 of much less degradation
photocatalyst capability; reduction by ~ 6
times
8 PFOA ZnO/rGO nanocomposite 1 g L− 1 of ZnO/rGO; PFOA PFPrA, PFBA, 33–100 Strong adsorption component [204]
concentration 100 mg L− 1; PFHpA, (LCMS (up to 35% of initial PFOA
irradiation density 1464.6 data) concentration after 1 h) not
Wm− 2 deducted; (values corrected I
rate column)
9 PFOA Pb-BiFeO3/rGO 5 W irradiation @ 254 nm; Not assessed 1–13 The density of nanoparticles on [205]
10–100 mg L–1 PFOA; the rGO was not evaluated. Best
50–400 mg L–1 performance achieved for mid-
range rGO doping amount
(0.5 %)
10 PFOA TiO2–MWCNT 300 W @ 365 nm; PFOA at PFPA, PFBA, 3–17 Very large loadings of catalysts. [206]
30 mg L–1 and 1.6 g L–1 of PFPeA, PFHxA, Limited evaluation of titania
TiO–2MWCNT catalysts PFHpA (LCMS) loadings
11 PFOA Bismuth oxychloride 254 nm @ 10 W; 1 g L− 1 of Not assessed 21–78 The level of vacancies and zeta [186]
nanosheets catalyst; 20 μmol L− 1 potential directly impact
performance. Radicals
quenchers affect the stability of
the reaction and reduction
kinetics
12 PFOA surface defective BiOCl 300 W with broad sunlight- Not assessed 4–17 Catalyst is unstable and [185]
like spectrum with an dissolves over time
intensity of 105 mW cm-2;
PFOA 50 μmol L− 1; 1 g L− 1 of
catalyst
13 PFOA Titania 23 W, emitting 254 nm; TFA, PFPrA, 5–50 Radicals quenchers affect the [207]
6 mW. cm− 2; PFBA, PFPeA, rate of degradation dramatically
PFHxA, PFHpA,
PFOA
14 PFOA Phosphotungstic acid PFOA 5–40 mg⋅L− 1; PFOA, PFHpA, 5–56 Kinetics offers a lower pH [208]
(H3PW12O40) 8 W @ 254 nm; PFHxA, PFPeA, dependence to pH compared to
PFBA other materials.
PFPrA, TFA
15 PFOA Ga2O3 PFOA 75 PFOA, PFHpA, 8–30 Nitrogen bubbling supports the [97]
μmol L− 1 with 0.5 g L− 1
PFHxA, PFPeA, kinetics while O2 bubbling
β-Ga2O3 powder; PFBA slowed it down
254 nm @ 15 W; PFPrA, TFA
16 PFOA MnOx vacancies rich PFHpA; PFHxA; 135–220 at pH 3.8 Synergistic •OH and H+ [184]
doped In2O3 PFPeA; PFBA degradation pathway.
(continued on next page)

9
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 3 (continued )
Entry PFOA Materials details and Catalytic operation Major by-products Kinetic degradation Comments on performance Reference
properties conditions besides H+ and F- rate (min-1)

1 g L− 1 catalyst PFOA
50 mg L–1; 100 mW cm–2
(500 W nominal) @ 254 nm
17 PFOA Photocatalyst- UV–vis irradiation with CO2, F– 1.63 µmol h–1 No consumption of catalyst [102]
heteropolyacid tungstic Xe-Hg lamp (200 W) takes place
Electrocatalysis
18 PFOA Mixed composite thin 100 mg L− 1 Not assessed 10–64 [209]
film materials with Ti/ PFOA concentration at a
SnO2-Sb, Ti/SnO2-Sb/ constant current density of
PbO2 and Ti/SnO2-Sb/ 10 mA cm-2 with a
MnO2 10 mmol L− 1 NaClO4
supporting electrolyte
solution; Current densities
ranging from 5,
10, 20, 30 and 40
10 mA cm–2
19 PFOA Boron-doped diamond pH 3; − 0.5 to − 0.6 V PFOA, PFHpA, 46–103 Changes in Fe and Mn oxidation [108]
anode; FeMn-doped PFHxA, PFPeA, states and densities visible after
carbon aerogel cathode PFBA reaction
PFPrA, TFA
20 PFHxS, Titanium suboxide 5 mA cm− 2; 1–15 mA cm–2; Not assessed Individual (5×10–6 A systematic study looking at [210]
PFBA, electrodes SA of 468.05 cm2 to 3.5×10–8 m s–1) the impact of mixing various
PFBS, Mixture (1 × 10-5 to PFOA and PFOS compounds
PFPeA, 8 × 10–8 m s–1) together on selective
PFHpA, degradation
PFHxA
21 PFOA Ti/SnO2-Sb/PbO2-Zr 5–30 mA PFOA, PFHpA, 110–410 Impact of magnetic stirring [211]
electrode cm− 2; 30–75 ◦ C; 100 mg L− 1
PFHxA, PFPeA, beneficial to the
PFOA; 7.5–16 V applied PFBA homogenization and
voltage PFPrA, TFA defluorination process
22 PFOS F and Sb co-doped Ti/ PFOA 100 mg L–1; pH 3; PFOA, PFHpA, 150–350 Enhanced affinity through [212]
SnO2 electrode with Sn- 3–5 V; 1–17 mA cm–2; PFHxA, PFPeA, fluoride doping
Sb interlayer stirring PFBA
PFPrA, TFA
Photo-electro catalysis
23 PFOA rGO/BiOCl composite 14 W @ 254 nm; bias Not assessed 0.9 (EC), 7.9 (PC), 6.7 times increase in [107]
powders/assemblies voltage 40.1 (PEC ozone), performance with combinatorial
of + 2.0 V; 72.8 (PEC with processes; 15% loss in 4 cycles
1
Ozone dosage of 25 mg h− Ozone)
bubbled in oxygen at
10 mg L− 1 in PFOA
solution at pH 3

photolytic degradation kinetics of model PFOA and PFOS solutions, with
reported chain lengths of 6–10 carbons, was poor (10–7 to 10–5 min–1)
(Table 5, Entries 12–14). However, the photocatalytic degradation ki­
netics of PFOA in either complex model solutions, with mixed PFOA
sources and other contaminants mimicking wastewaters, or real efflu­
ents were also low on the order of 10–9 to 10–8 min–1, demonstrating the
need for more efficient and sustainable radicals generation pathways
[92,93].
Photo-catalysis (PC), however, involving heterogeneous photo­
catalysts was found to decompose PFOA compounds at longer light
wavelength than photolysis and to provide greater yields and thus much
faster kinetics (Table 3, Entries 1–17). During heterogeneous PC, the
photocatalyst will absorb light and generate electron transfers towards
the surface of the semiconductor. The energy input will either split
water, generating radicals, or directly degrade absorbed contaminants
onto the catalyst surface. The first studies on PC of PFOA compounds
were carried out in the early 1990 s with titania macroparticles slurry
reactors, generated by sol-gel, and led to rates of reactions in the order of
10–5 to 10–6 min–1 much slower compared to rates reported for other
contaminants, such as pharmaceuticals, dyes or other persistent organic
pollutants (POPs) [90,94]. Stemming from this study, nanoscale single
semiconductors, such as titanium dioxide (TiO2) nanoparticles and
nanotubes, gallium oxide (Ga2O3) nanosheets, and indium trioxide
(In2O3) nanoparticles were developed for slurry reactor applications and
found to be up to 1000 times more effective for PFOA treatment than
direct photolysis due to the larger surface area offered for photo-electron
generation and radical formation [95–97].
Generating vacancies across single metal oxides leading to electron-
holes into the surface microstructure of the photocatalyst was also
demonstrated to lead to enhanced reactivities with titanium sub-oxide
as well as In2O3 materials [98]. Oxygen vacancies generation was
found to increase the reactivity towards PFOA by 20–100 folds for both
titanium oxide and indium oxide photocatalysts [96,99]. The highest
reported catalytic rate, to-date, was achieved for hollow indium oxide
spheres with a few percent of oxygen vacancies which reached
1323 min-1 for PFOA. Other ways of improving photocatalysis have been
discussed in Section 6.
Under environmental conditions, PFOS is not known to undergo
photolysis, and the half-life of PFOA was estimated to be 349 days [100].
In lab-scale studies, direct photolysis with H2O2 and UV–visible irradi­
ation produced CO2, F– (~27–57%), and shorter-chained PFAS,
degrading 42–56% PFAS [101]. The use of heteropolyacid photocatalyst
under tungstic irradiation of 200 W xenon-mercury lamp resulted in the
complete mineralization of PFOA (≈100%) into CO2 and F–. No photo­
catalyst was used in this process, leaving behind the entire photocatalyst
for reuse [102]. Calcium (Ca2+) present across calcium gluconate can be
used, in reactions where fluoride is generated as a reaction metabolite,
to form CaF2 to capture F–, which is environmentally benign [103].
Within 60 min, ≈100% PFOA was degraded to SO4 and O2 anions, e–,
and shorter chained intermediates when irradiated with UV with Ga2O3
and peroxymonosulfate as co-catalysts [104].

10
S. Garg et al.
Fig. 3. Comparison of photocatalytic or electrocatalytic performance in terms of wavelength of light and power consumption linking it with the corresponding
degradation rate has been shown. Data recorded in Table 3. Power of approximately 250 W and wavelength of visible light range between 380 and 600 nm are
effective in photoelectrocatalytic removal.
3.1.2. Electro-catalysis
Electrocatalysis (EC), an effective advanced oxidation process, has
been successfully used for the degradation of micropollutants in
wastewater including dyes, other POPs, and more recently PFOA com­
pounds [105]. Electrochemical treatment of aqueous pollutants allows
for fast oxidation performance in relatively mild operating conditions
and does not require extensive chemical pre-treatments, limiting the
environmental footprint of the technology [106].
The cost-effectiveness of the EC process, however, remains low due
to the high energy requirements, relatively unstable electrode materials
over time due to pitting and corrosion issues [105, 106]. Several side
reactions will occur simultaneously during any EC process, including a
hydrogen evolution reaction (HER) at the cathode and an oxygen evo­
lution reaction at the anode. Although the rate of hydroxyl radicals
generation increases semi-linearly with respect to the current density, or
applied voltage across the electrode stack, while the system’s power
consumption will increase as the square of the voltage, making the EC
process often limited to low operating voltages [107]. A strategy to
overcome this energy loss at high voltages, while still benefiting from
the high yield of radical generation from EC, is to develop combinatorial
processes where EC operated at low current densities is used in parallel
to either hydrothermal or ultrasonic processes.
To date, the focus of PFOA treatment with EC has however been on
the development of more stable materials, able to operate over a larger
range of current densities without undergoing either dramatic integrity
failures or surface passivation/oxidation (Table 3, Entries 18–22). PFOA
was degraded in a system composed of boron-doped diamond (BDD)
anodes and Ti/SnO2-Sb-Bi cathodes [108]. The reaction mechanism was
linked to favorable electron transfer from PFOA to BDD anode while
other anode materials, such as Pt, Ti/IrO2, Ti/RuO2, and Ti/IrO2-RuO2
were found to be inefficient to eliminate PFOA. Although BDD elec­
trodes offer better performance and well-established chemical and
electrochemical stabilities, long life, and high oxygen evolution poten­
tial (OEP), its manufacturing costs are redibitory to its scalable appli­
cation. Conductive materials were therefore, considered as substrates for
BDD deposition, including various metals and semiconductors. Although
titanium metal offers advantages in terms of cost and scalability, issues
related to interface delamination and compatibility between the BDD
and the TiO2 native oxide layer have limited their development. It is also
difficult to grow in-situ BDD on titanium due to the strong H2 uptake
observed by titanium metal during plasma-growth of BDD, leading to
fracture and degradation of the titanium matrix. Several metal oxides
such as PbO2, SnO2, RuO2, and TiO2 have been demonstrated as active
anode surface materials for EC because they exhibit high oxygen evo­
lution potential leading to larger densities of hydroxyl radical genera­
tion as well as relatively high electron transfer capabilities.
Electro-Fenton reactions, relying on H2O2 generation and subsequent
11
Journal of Environmental Chemical Engineering 9 (2021) 105784
split in the presence of Fe2+ ions, have been demonstrated with porous
carbon electrodes, offering excellent pore interconnectivity and
conductive properties for the reactions [109]. However, adding Fe to
porous carbons was found to largely alter the 2-electron oxygen reduc­
tion pathway into a 4-electron pathway, resulting in much slower H2O2
yield rates. Other metals, including Mn, have been used in such reactions
but still await their use for PFOA treatment.
3.1.3. Photo-electro catalysis
Recently, the development of photo-electrocatalytic (PEC) reactors,
combining the benefits and reactivities of both photo and electro­
catalytic processes have emerged as efficient alternatives to AOP for
POPs remediation. PEC is particularly promising since offering a de-
multiplied rate of degradation compared to single catalytic process
(Table 3, Entry 23).
The application of PEC was demonstrated for the degradation of
PFOA with reduced graphene oxide (rGO)-BiOCl composites. The com­
bination of PC and EC into a PEC system led to a significant increase in
the catalytic performance by up to 6.7 times [107]. The direct rate for EC
was 0.9 min–1, while this increased to 7.9 min–1 for PC. PEC reached a
promising value of 40.1 min–1 while the addition of O3 to the process
doped the reaction up to 72.8 min–1. No measurable degradation of the
materials was reported confirming that although the density of radicals
generated was strongly increased, this did not come at the expense of
surface damage or poisoning of the materials. A challenge with BiOCl is,
however, its dissolution over time limiting long-term performance and
leading to Bi3+ ions release in the solution [110]. The comparison on the
performance parameters of the EC and PC processes in terms of current
density and light wavelength employed has been shown in Fig. 3.
3.2. Wet Oxidation-reduction reactions
Oxidation-reduction reactions involve electron transfer from an
electron donor (reductant) to an electron acceptor (oxidant), which re­
sults in either partial to complete mineralization of the target contami­
nant directly or through the formation of free radicals that degrade the
target contaminants indirectly [16]. PFAS are highly stable molecules,
thus degradation via free radicals is typically more efficient, rather than
the direct electron transfer. Fenton agents, heat-activated persulfate,
bimetals, sub-critical water, and reduction with elemental iron- Zero
Valent Iron (ZVI) are the most commonly used reagents [111]. Fluorine
has a reduction potential of 3.6 V, making it the most potent inorganic
oxidant; thus, mere one-electron oxidants are ineffective in defluori­
nating PFAS [112]. This is also, why hydroxyl-based (•OH) oxidation
technologies are mildly effective for PFAS oxidation. AOP with UV
irradiation and use of catalyst- H2O2 or S2O2-8 resulted in < 10% of
PFOA and PFNA and 10–50% of PFOS removal, tested with PFAS
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 4
Case studies on Physicochemical degradation of PFAS.
Entry Treatment Substance Conditions Removal (%) Time Degradation by-products Scale Reference
(Initial
concentrations)

Wet oxidation-reduction processes

1 Heat-activated PFOS pH ≤ 3, activation No effect 6h C4-C7 homologs of PFOA Bench [119]
persulphate PFOA temperatures of up to 60 ◦ C, 86–98
oxidation S2O2–
8 concentrations of up
to 84 mM
2 UV-activated GenX – <5, 3h –CF2 removal at every step Bench [121]
persulfate PFOA 27 with the generation of SO2–4
and OH–
-
3 UV-sulfite GenX – >90 2h F , PFPrA, TPA Bench [121]
4 Ozonation PFOS, Flow rate= 2 mg L–1 81.08, n.d. All were detectable. Field- WTP [56]
(H2O2 + UV) PFOA 25 Ozonation is ineffective in
+ WTP PFAS degradation
processes
(Adsorption +
filtration)
5 ZVI + biochar PFOA, PFHpA, Hardwood-oak based 17–94 120 days F–, removal efficiencies Bench [213]
PFHxA, biochar, pH= 8.5 depend on carbon chain
PFPeA, PFOS, length, 0–17% removal for
PFBA, PFHpS, short-chained PFCAs (C6-
PFHxS, PFBS C7), 20–70% for short-
chained PFSAs
6 γ-ray irradiation PFOA 50 kGy, Ar saturated 100 2–3 h C6F13-CF(H)-COOH Bench [164]
with a 60Co (10 mg L− 1) atmosphere, pH 6.7, 50 PFOA substituted with alkyl
source, Catalysts- t-butanol/H2O2 groups
Electron beam EB: 100 kGy, pH 12.5 C7F13-COOH,
(EB) CF3CHCH2COH
irradiations (CH3)2COOH
PFOA substituted
with different
alkyl groups
7 γ-ray irradiation PFOA 96 Gy/min, pH 13, N2 Degradation 12 h PFBA, PFPeA, PFHxA Bench [214]
with a60Co (20 mg L− 1) saturated atmosphere, rate- 0.67 h–1,
source Catalysts- t-butanol/H2O2 > 99
8 Plasma-based PFOS, PFOA with Ni-Cr and Al ring as 96–98 1h PFHpA, PFHxA, PFPeA, Bench [215]
reactor electrodes PFBA
PFHxS and PFBS (from PFOS
only)
Sonochemical degradation
9 Sonochemical AFFF (ANSUL 500 kHz or 1 MHz PFSA- 90.5, 13 h F– and SO2–
4 Bench [130]
reactor with 12 and 3 M) PFCA- 26.6,
transducers (P. FTS- 38.4
D.=12 kW,
Initial pH=
<4.0)
10 Sonochemical K-PFOS 400 kHz 96.9 Up to 4 h PFOA, PFHpA, PFHxA Bench [134]
500 93.8
1000 91.2
11 Sonochemical PFOA (240 nM) 358 kHz Not calculated 14 min Not studied Bench [127]
(A 20 kHz PFOS (200 nM) 358 17 min
horned PFBA (470 nM) 610 33 min
transducer PFBS (300 nM) 610 33 min
placed PFHA (320 nM) 610 19 min
perpendicular to PFHS (230 nM) 610 26 min
an Allied Signal
– Elac Nautik
ultrasonic
transducer, P.
D.=250 W L-1,
T = 10 ◦ C)
12 Sonochemical PFBS (300 nM) 358 KHz 66 42.3 min Not studied Bench [128]
(An allied Signal PFBA (470 nM) 57 57.2 min
– Elac Nautik PFHS (250 nM) 86 23.2 min
ultrasonic PFHA (320 nM) 90 16.8 min
transducer, P.
D.=250 W L-1,
T = 10 ◦ C)
13 Sonochemical PFOA 358 kHz 99 16.9 min CO, CO2, formaldehyde, Bench [135]
(An allied Signal (10,000 nM) 87 25.7 min carbonyl fluoride, HF
– Elac Nautik PFOS
ultrasonic (10,000 nM)
transducer, P.
(continued on next page)

12
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 4 (continued )
Entry Treatment Substance Conditions Removal (%) Time Degradation by-products Scale Reference
(Initial
concentrations)

D.= 250 W L-1,

T = 10 ◦ C)
14 Sonolysis + O3 PFOS, 354 or 612 kHz 61, Up to 2 h Pseudo-first-order rate Field- Landfill [133]
PFOA 56 kinetics if followed, not groundwater
studied
Photo/Thermal
15 UV irradiation AFFF feed water UV intensity= 210–280 nm 16.8 20 min Limitedly studied, Bench [124]
PFHxA
17 UV–vis PFOA No photo or chemical 89.5 72 h CO2, F–, and short-chain Bench [102]
irradiation with catalyst perfluorocarboxylic acids
tungstic Xe-Hg
lamp (200 W)
18 UV–vis with PFOA Chemical catalyst- H2O2 35.5 24 h CO2, F– Bench [102]
tungstic Xe-Hg
lamp
19 Heat AFPO 196–234 ◦ C > 99 2.2–43.8 min, 1-H-perfluoroheptane Bench [138]
350–400 ◦ C, follows first- 0.2 s (90–95%)
order kinetics
20 Heat PFOA 355–385 ◦ C, follows first- ~100 2 s, T1/2 1-H-perfluoroheptane, SiF4 Bench [137]
order kinetics = 26 min
@ 385 ◦ C
21 Heat PFAS 350 ◦ C 99.91 10–14 days Volatile PFAS captured with PFAS- [140]
400 ◦ C 99.998 scrubber impacted soil,
in-situ thermal
treatment
22 Heat PFOS 726.85 ◦ C >99 0.2 s PFOA and SO2 Bench [136]
∑
23 Heat 9PFAS- 350 ◦ C 43 (fortified), 75 min Not studied Bench and [216]
fortified and field 450 ◦ C 71 (fortified field
contaminated 550 ◦ C clay), 87
(fortified sand),
79 (field)
> 99 (field and
fortified)
71–99 (field)
24 Heat PFOS 350 ◦ C > 99 (with 1–30 min Defluorination, CaF2 Bench [217]
425 ◦ C lime)
> 99 (without
lime)
25 Heat+ Ca(OH)2 PFOS 300 − 600 ◦ C, 70–71, 15 min CaF2 and Ca5(PO4)3F Field- Sludge [165]
700 − 900 ◦ C 68
26 Heat+ Ca PFOS 300–900 ◦ C >90 (PFOS) 15 min CaF2, –CF, –CF3, –C3F3, PFAS waste [142]
(OH)2/CaCO3/ PFOA 450 ◦ C with Ca(OH)2 >80 (PFHxS) –C3F5
CaO PFHxS >50 (PFOA)
>45 (FOSA)
∑
27 Heat+GAC+N2/ PFCAs 200–700 ◦ C, follows first- >99.99 (at n.d. Volatile organofluorine Bench [141]
∑7
O2/CO2/air 3PFSAs order kinetics 700 ◦ C) species, F–
atmosphere PFECA
28 Smoldering PFAS-impacted >900 ◦ C 16 <140 min Altered, shortened, or, Bench and [139]
column + GAC soil 44 volatile perfluorinated field
PFAS on GAC compounds

contaminated surface and groundwater [113] (Table 4, entries 1–8).
H2O2 [102], Na2S2O8 [114], O3 [115], Na/KMnO4 [116] were shown
to successfully decompose PFOA into F– and CO2. OH– ions were also
generated, which helps in further oxidation. Na2S2O8 degrades PFOS
into PFOA with the help of SO•– 4 and (•OH) which further decomposes
with the loss of ‒CF2 at every step until full degradation (defluorination)
[117]. H2O2 and humic acid were used as catalysts in such reactions.
PFOA was oxidized with heat-activated persulfate at
T = 50 ◦ C/pH = 2/t = 100 h, whereas PFOS did not oxidize even at
90 ◦ C. PFOA, likely, breaks down as follows with persulfate: PFOA,
PFHpA, PFHxA, PFPeA, PFBA, Perfluoropropionic Acid (PFPrA), Tri­
fluoroacetic Acid (TFA), and so on [118]. By-products have not been
consistently studied in these studies. In a bench-scale study, testing the
efficiency of heat-activated persulfate towards the decomposition of
PFOA and PFOS, PFOS remained unaffected, whereas PFOA showed
98% removal within 6 h. Undesirable shorter-chained intermediates,
chlorates, and metals were also flocculated in the process [119]. In
another field study, oxidative conversion resulted in an increase of
PFCAs in the urban run-off by a median of 69% between 2.8 and
56 ng L–1 [120].
PFOS and PFOA underwent reductive dehalogenation by zero-valent
metals, such as iron with sub- and super-critical water at a temperature
of over >250 ◦ C, and pressurized between 0.78 and 0.81 MPa, forming
fluorine and sulfate [114]. Aqueous electrons (e–aq) have emerged as the
promising and powerful reductive agents produced in UV/sulfite [121]
or UV/iodide [122] systems to decompose PFAS especially PFOS, PFOA,
and PFHxA. TiO2 due to its strong catalytic ability, hydrophilicity,
chemical, structural stability, durability, nontoxicity, and economic
considerations coupled with morphological purposiveness, is another
promising catalyzing agent [99]. Defluorination of PFOS occurs with
vitamin B12 as a catalyst and Ti(III) as a reducing agent measured in
terms of F– released with branched PFOS releasing much higher F–
(71%) as compared to linear (18%). This occurs because of the
defluorination reaction in which radical intermediates are formed
around the carbons, breaking the C‒C bond [123].
During ozonation processes, O3 is injected directly into the waste
stream [124]. O3 failed to degrade PFOS or PFOA in a peroxone process
at 4–5 pH. Although alkaline ozonation removed 71% of PFOA and 76%

13
S. Garg et al.
of PFOS in a peroxone-assisted process increasing the removal to 99%
for PFOA and 89% for PFOS within 4 h of operation [115]. Similarly, a
process called ozofractionation with O3 injected into a foaming frac­
tionator instead of directly in air exploits the surfactant properties and
foaming ability of PFAS towards water remediation. The hydrophilic
polar head and hydrophobic carbon tail helped in micelle formation. On
sparging O3, a PFAS foam was formed which was separated from the
water stream. Ozofractionation achieved a 99.99% reduction of PFAS
from 28.8 to <0.002 ng L–1, in this manner [125].
3.3. Sonochemical degradation
Upon application of an ultrasonic field (>16 kHz), the soundwaves
cause the bubbles present in the solution to reach their maximal radial
expansion and undergo a quasi-adiabatic compression. This energy is
converted into kinetic energy of the molecule, which is released when
the bubble collapses to burst. This phenomenon is called cavitation.
Temperatures close to 5000 K are generated in this process, resulting in
the pyrolysis of any chemicals, such as PFAS, present in the solution
[126]. In this reaction, PFAS is mineralized by two processes, including,
the cleavage of ionic functional groups by pyrolytic action followed by
the defluorination resulting in smaller molecular weight PFAS com­
pounds formation. The frequencies used range from 202 to 1500 kHz
with power densities of 83–333 W L–1 [127–132]. The cavitating bub­
ble’s number, radius, temperature, pressure, dynamics, and symmetry
are determined by the applied frequency [128]. The number of active
bubbles per unit time and the mass transfer to the bubble surface of the
PFAS species determine the rate of degradation of PFAS.
In a lab-scale study conducted, at 400 kHz, 96.9% of degradation
was observed over 4 h. The hydrated electron release mechanism has
been suggested for such a reaction resulting in defluorination of PFOS,
accompanied by sulfate release. CO and CO2 were also produced during
this degradation mechanism [133] (Table 4, Entries 9–14). To enhance
degradation, in an experiment, dual-frequency exposure of
20 + 202 kHz and 20 + 610 kHz was studied. Enhancements of 12%
and 23% were achieved for PFOS and PFOA degradation respectively at
20 + 202 kHz. However, there was relatively no enhancement at a fre­
quency of 20 + 610 kHz. On single frequency exposure for up to 4 h,
tested at various frequencies of 400, 500, and 1000 kHz, 96.9%, 93.8%,
and 91.2% respectively of PFOS was degraded. At higher frequencies up
to 1000 kHz, the degradation efficiency decreases to ~91% because of
the overall reduction in the intensity of cavitation frequency collapse
[134]. At 500 kHz, 90.5% of Perfluoro Sulphonic Acids (PFSAs), 26.6%
of Perfluoro Carboxylic Acids (PFCAs), and 38.4% of Fluorotelomer
sulfonate (FTS) were degraded with 12 transducers in 13 h [129]. At
higher initial concentrations of 10,000 nM, up to 99% of PFOA and 87%
of PFOS were degraded at 358 kHz [135]. In a field-scale study of
groundwater impacted with PFAS, PFOS and PFOA were reduced by
61% and 56% respectively by sonolysis, carried out in the presence of
other organic contaminants at a frequency of 354/612 kHz and power
density of 250 W L–1 [133].
3.4. Photo/Thermal degradation
Thermolysis involves using high temperatures to break the C‒C or C‒
F bonds of the PFAS chain to form shorter chained moieties which will
eventually be degraded like the photolytic degradation products.
Incineration remains the most commonly applied thermal degradation
technique [136]. Other pathways utilize chemicals and
critical/sub-critical ions to support thermal dissociation of PFAS, and
the most efficient studies are discussed in Table 4, Entries 15–28.
Incineration of PFAS such as PFOA, PFOS, and Ammonium Per­
fluorooctanoate (AFPO) takes place successfully at temperatures as high
as 600–1000 ◦ C. The estimated half-life of PFOA was 26 min at 385 ◦ C,
while ~99% was degraded within 9 h leaving 1-H-perfluoroheptane as
the major by-product and Perfluoro-1-heptene as the minor by-product
14
Journal of Environmental Chemical Engineering 9 (2021) 105784
[137,138]. The remediation of PFAS-impacted soils by smoldering with
and without GAC-mixed soil was evaluated. Up to 44% of degradation of
PFAS was achieved with GAC compared to only 16%, without GAC. The
total organic fluoride analysis confirmed that GAC-application enhanced
the rate of PFAS volatilization from soils and water, which supported the
decomposition of PFOA at low operating temperatures (down to
200 ◦ C). Only sub-1% levels of PFAS were emitted as quantifiable PFAS
after treatment [139]. PFSAs (400–450 ◦ C) require higher temperatures
than PFCAs (350 ◦ C) to completely volatilize [140]. In an N2 atmosphere
and at 700 ◦ C, >99.99% of PFOA and PFOS were decomposed to yield
fluoride ions as major quantifiable by-product [141].
PFOS decomposition takes place by hydrogen fluoride (HF) loss
resulting in an α-sultone formation that decomposes spontaneously to
form PFOA and SO2. The PFOS decomposition did not begin with C‒S
bond fission. The terminal functional groups (‒SO3H, ‒COOH, ‒
SO2NH2, etc.) detach entirely during PFAS incineration. The acid head
group of PFOS was destroyed at 1000 K, and PFOS degraded following
first-order kinetics with a half-life of 0.2 s [136]. The lime treatment of
PFOS between 350 and 900 ◦ C, resulted in the formation of CaF2, ‒CF, ‒
CF3, ‒C3F3, ‒C3F5 [142]. Shorter, altered, or more volatile forms of PFAS
were hypothesized to be formed in the process with the potential of
long-range transport [139]. To minimize the spread of volatile pre­
cursors of PFAS, a scrubber is recommended to be used at thermal
mineralization sites. Toxic greenhouse gases such as dioxins, furans, CF4,
and C2F6 were produced alongside CO2 during this operation in the field
[143,144].
3.5. Biological degradation
WWTPs may serve as the largest target sites for large-scale opera­
tions for the treatment of PFAS via microbial- or phyto-degradation.
Wetlands are known to represent physicochemical conditions of
WWTPs, therefore, also serve as a repository of microbes and plants
useful in bioremediation of targeted contaminants. This section dis­
cusses the potential of microbes and wetland plants, besides enzymes
and protein to treat PFAS from wastewaters.
3.5.1. Wetlands plants and microbes for bioremediation
Though initially microbial degradation was suggested to be of
limited importance for PFAS degradation [19,145], recent evidence
suggests enrichment of different bacterial phyla in the order of Proteo­
bacteria > Actinobacteria > Verrucomicrobia > Bacteroidetes > Cyano­
bacteria > Firmicutes in water-soil-plant systems fortified with varying
concentrations of eight PFAS, indicating their relevance in biodegra­
dation [146]. Acidimicrobium A6, an Actinobacteria, follows reductive
defluorination and removes ~60% of PFOA/PFOS (100 mg L–1) within
100 days [147]. In aerobic conditions, the presence of N-ethyl per­
fluorooctane sulfonamide (N-EtFOSA)-enriched Methylocaldum in wet­
lands as potential N-EtFOSA-degrader, whereas under anaerobic
conditions showed a dominance of Methanomethylovorans [148].
Both aerobic and anaerobic degradation pathways of 8:2 Fluo­
rotelomer Alcohol (FTOH) have been elucidated [149]. Acidimicrobium
Gordonia, Desulfococcus, Pseudomonas, and some other lineages of bac­
teria use fluorotelomers such as 6:2 FTS as sulfur sources [150]. PFAS
show resistance to anaerobic bacteria and anaerobic bacteria are im­
mune to PFAS toxicity and thus, they continue their methanogenic ac­
tivity in PFAS contaminated sites [151]. AFFF/PFAS mixture also failed
to inhibit microbial methane generation, and most PFAS sorbed onto the
microbes and did not undergo any decomposition [152].
Plants with varying capabilities of uptake, translocation, and
biotransformation of PFAS from industrial effluent, contaminated irri­
gation water, and landfill leachates have been reported. The fate of PFAS
in plants remains a net outcome of complex interactions between
physicochemical properties of PFAS, the physiological capability of the
plant species, and abiotic factors. The PFAS concentration ratio in the
plant to environmental matrices (wastewater, surface water, lake, and
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 5
Case studies on biological/biochemical degradation of PFAS.
Entry Treatment Substance Conditions Removal Time Degradation by-products Scale Reference
(%)

Organismic
1 Phanaerochete 6:2 FTOH, Lab-cultured 50, 28 F–, 5:3 polyfluorinated acid (40%), Bench [218]
chrysosporium 8:2 FTOH 70 days 5:2 sFTOH (10%), PFHxA (4%), and
others
(about 1% each). Fewer metabolites
were produced after 8:2 FTOH
degradation, such as 7:2
sFTOH (6%), PFOA (5%), 7:2 Ft
ketone (3%), and others (<1%
each).
2 Ti(III)-citrate with Branched An aqueous solution with pH 9.0 71 7 F- Bench [123]
vitamin B12 as a catalyst PFOS and at 70 ◦ C days
from cyanocobalamin
3 Acidimicrobium sp. strain PFOS, PFOA The initial concentration of <60 100 F–, shorter PFAS, acetate, Fe (III) Bench [147]
(A6) 0.1 mg L–1 and 100 mg L–1, ferric days
ions as the catalyst, hydrogen as an
electron donor
4 2 strains of Pseudomonas PFHxS, 8:2 Field-isolated strains, 40 ± 3 10 Bioaccumulation, F–, shorter PFAS Bench [219]
sp. FTOH Alkanotrophic conditions using days
octanol
Enzymatic
5 Laccase-mediated PFOA Batch-reactions ~50 157 pseudo-first-order with rate Bench [159]
oxidative humification days constant of 0.0044 day–1, No PFCAs,
F–, shorter-chained aliphatic
compounds
6 Horseradish peroxidase PFOA Batch reactions 68 6h F–, and shorter-chained aliphatic Bench [158]
+ 4-methoxy phenol compounds
7 Hemp protein (Cannabis PFOS+PFHxS Pump and treat batch reactions 97.9 1h Not studied Bench [161]
∑
sativa) PFAS 95.2
8 Soy and pea protein 97
82
9 Egg protein 48
30
10 Lupin protein 85
73
11 Whey protein 29
9

agriculture fields) in yam roots (0.53–0.59) and sugarcane stems
(0.65–0.67) confirmed significant uptake of PFBS and PFHpA, respec­
tively [153]. Bioaccumulation and translocation in roots and shoots of
Juncus effusus varied with the carbon chain length in a greenhouse study.
J. effusus-soil interfaces together accumulated 82.8% of PFAAs (C4 to
C8) from aqueous solution in 21 days [154]. Wheat, soybean, and
pumpkin; grown in hydroponics; effectively metabolized N-EtFOSA into
FOSA, Perfluorooctane sulfonamide (PFOSA), PFOS, and other
shorter-chain PFAS, PFHxS, and PFBS in roots and shoots with
biotransformation pathways different from animals and microbes [155].
Different wetland plants, Alisma orientale, Arundo donax, Canna indica,
Cyperus alternifoliusm, C. papyrus, Thalia dealbata, Phragmites australis,
Pontederia cordata, show potential to accumulate PFOS mainly in roots
(48.8− 95.8%), while PFOA mostly in shoots (29.3− 77.4%). Localiza­
tion of PFAS confirmed that uptake and translocation of PFAS occur both
across cell walls and/or intercellular spaces, and across plasma mem­
branes [156]. Another study from riparian wetland showed high affinity
of Cyperus congestus, Eichhornia crassipes, Persicaria amphibia, Phragmites
australis, Polygonum salicifolium, Ruppia maritime, and Schoenoplectus
corymbosus to PFOA accumulation in the range 11.7–38 ng g–1, with a
BCF range of 0.05–0.37 [157].
Taking clues from emerging reports of wetland plants and microbes
as PFAS accumulators and degraders, a constructed wetland may serve
as an integrated system relying on physicochemical and biological
processes for large-scale, eco-friendly treatment of PFAS, combining
benefits from different types of treatment methods.
3.5.2. Enzymes and proteins for bioremediation
Both enzymes and proteins have shown promise in PFAS degradation
or removal. Horseradish peroxidases co-polymerize phenol and PFOA in
the presence of H2O2 from an aqueous solution and about 68% removal
of PFOA was achieved [158]. Laccase also reduces 50% PFOA in 157
days. Both peroxidases and laccase are humification enzymes, which
degraded PFAS following either radical abstraction of double bonds or
Kolbe’s decarboxylation in a stepwise conversion of ‒CF2 moiety
generating CO2 and F– [159]. Enzymatic degradation yields partially
fluorinated shorter-chained alcohols and aldehydes, lacking
shorter-chained PFCAs. Peroxidase/laccase-catalyzed oxidative humifi­
cation reactions are prevalent in the environment, therefore, serve as
environmentally benign methods for PFAS treatment [160].
Protein powder of hemp (Cannabis sativa) has shown >98% removal
of PFOS and PFHxS from real contaminated groundwater in a pump and
treat system in a contact time of 1 h/pH 4–6, where salinity exerted a
positive impact on removal rate [161]. Hemp protein adsorbs PFAS
comparable to a GAC: Norit® (<1% difference for total PFAS) but re­
mains ~2.7 times cheaper than GAC (hemp protein: US$45 kg–1 vs GAC:
US$125 kg–1) [162]. Thus, the combinatorial or tandemly applied
technologies have come up as a solution to the problems of applicability
and scalability (Table 5, Entries 1–11).
3.6. Limitations and directions for PFAS degradation technologies
Chemical degradation technologies are mainly hindered by in­
terferences by ions and their untargeted actions. The need to maintain
conditions of pH and temperature, slow reaction rates, as well as the
addition of chemicals further add to the composition load of the water
are however limiting the extension of these technologies. Additionally,
the reaction intermediates and metabolites produced could be more

15
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 6
Case studies on treatment train approach for PFAS treatment.
Entry Treatment Substance Conditions Removal (%) Time Degradation Scale Reference
by-products

1 UV-Air fractionation AFFF feed water UV intensity = 210–280 nm, 81.3% PFAS in total, 20 min A limited study, Bench [124]
airflow and 80% PFHxS, PFHxA
rate of 30 L min− 1 and feed 100% PFHpS, 87.0%
flow rate of 1.4 L min− 1 PFOS, 16.7% PFHxA,
50.0% PFHpA, and
91% PFOA
2 UV/O3 AFFF feed water UV intensity = 210–280 nm, 73 20 min A limited study, Bench [124]
Ozone generator PFHxA
wavelength = 185 nm
3 UV-O3 - air AFFF feed water UV intensity = 210–280 nm, > 95 20 min A limited study, Bench [124]
fractionation Ozone generator PFHxA
wavelength= 185 nm, air
flow
rate= 30 L min− 1 and feed
flow= 1.4 L min− 1
4 WTP + RO + advanced PFOS, PFOA UF= 0.04 nm pore size, <MQL n.d. Could not be Field- [56]
oxidation RO= >300 MW substances detected, hence WTP
rejected not studied
5 GAC + ZVI + V-UV + PFOA [GAC]= 12.5 mg L–1/[Fe0]= 50 5–7 h C7, C6, C5, C4, Bench [176]
Fenton 7.5 gL-1/[H2O2]= and C3
22.8 mmol L–1, UV @ 185 nm
6 UV + iodide + Humic PFOS pH= 10, [HA]= 1 mg L–1, 55.6 1.5 I2, I–, I–3, IO–3, Bench [220]
acid [PFOS]= 0.03 mM HOI
7 GAC + AER + NF PFAS 270 Da cut-off of N.F. >99 35 weeks Not studied Pilot [221]
8 Aeration + duckweed PFAS The initial concentration of >95 (80% of PFOS 7 h +2 weeks Not studied Bench [178]
200 ng L–1, pH 2.3, aeration with aeration)
of 7 h
9 O3 + GAC+ PFAS such as Regenerated GAC with 10–99 90 days Not studied Pilot [222]
biodegradation PFBS, PFHpA, 0.65 O3
PFNA, and
PFOA and flame
retardants
10 GAC vs. Superfine Contaminated The SPAC has a mean particle For 77, 57, 200, 42 Concentration Pilot [223]
powder activated groundwater, diameter of 0.88 µm groundwater = GAC (h) study,
carbon (SPAC) + AFFF feed water and it was delivered as slurry = 6.2 Not studied
ceramic microfiltration having a density of 100 g- SPAC = 11
(CMF), SA of SPAC SPAC L–1, membrane flux For fire training
= 927 ± 40 m2 g–1, 60–65 LMH with a crossflow grounds =
dosage = 500 mg L–1 velocity of 0.18 m s–1 SPAC = 2990
(µg PFAA g–1 AC)
11 Adsorption + PC Iron hydr Initial PFOA conc.= 200 µgL- 95.2% 1h C7, C6, C5, C4, Bench [224]
1
(oxide) & , Adsorbent conc.= 1 gL-1 in photodegraded, C3, and so on,
carbon spheres 1:1 ratio, pH= 7, t = 4 h, 57.2% defluorinated OH–
solar light through quartz
photo-reactor while stirring
at 200 rpm
Entry Process Membrane code Compounds Treatment Feed Efficiency (%) Scale Reference
conditions concentration
(mg L–1)
12 NF + GAC NF270 PFBA, PFPeA, PFHxA, PFOA, Crossflow 0.001 93–99 in 8–33 Bench [73]
PFNA, PFBS, PFHxS, and synthetic days
PFOS, and PFDA groundwater
pH 3.5 and 7.1
13 NF + EO NF270 PFHxA Crossflow 64 and 204 89.1/88.7 in Bench [88]
Synthetic water 0.9–4.4 h and
pH 2–11 field
14 NF + 2540-ACM5- TSF PFOA Crossflow 0.005 and 0.1 66.9 in 1 min Field [89]
photocatalysis 2.5 in. (6.4 cm) in Synthetic water
+ UF diameter pH 2–11
15 RO-UV + AOP n.d. PFPnA, PFBS, PFHxA, PFHpA, Crossflow 52–227 >99 (Time = n. Bench [72]
PFHxS, PFOA, 6:2 FtS, PFNA, Tertiary effluent d.) and
PFOS, PFDA field
16 O3 + PFPnA, PFHxA, PFHpA, and 53, 30, 53, and
Biologically PFOA 24 respectively
activated for 25–35 min
carbon (BAC) +
GAC

Notes: WTP processes include coagulation/flocculation and sedimentation, then ultra-filtration (UF), reverse osmosis (RO), advanced oxidation, and finally
stabilization.

16
S. Garg et al.
toxic than the primary PFAS target [19].
The slow kinetics of PFOA degradation was found to be largely
dependent on the light wavelength used as well as on the overall energy
input provided to the system, due to the very high C-F bond energy of the
system. Although the range of non-terminal by-products produced was
found to be typically limited, their stability and typical low concentra­
tions, make their degradation extremely challenging. In addition, the
release of fluoride ions, leading to HF formation is a major hazard and no
study to date looked at synergistic degradation/recovery strategies to
remove fluoride acids while they form. Further materials development,
particularly regarding the surface area and oxygen vacancy control
should also be considered with stabilization strategies involving metal
doping or nano-texturation.
Advanced oxidation and reduction processes are able to achieve
partial or complete degradation with efficiencies between 55% and
100% [163]. The oxidation of F– is thermodynamically unfavorable due
to the high electronegativity of the element. PFOA or PFOS have no
hydrogen that can be acted upon by hydroxyl radicals to form less
thermodynamically stable hydrogen ions, thus simple oxidation
methods are ineffective on PFAS. However, AOPs with persulfate and
ionization radiations have been proven to be effective in degrading PFAS
[164]. Similarly, ARPs with activated persulfate and aqueous electrons
have proven to be more useful for PFAS degradation.
Incineration is a common and well-studied PFAS remediation
method, which can guarantee the complete decomposition of a large
range of PFAS compounds. However, extremely high-temperature gen­
eration also entails heavy capital investment on the equipment. The
generation and potential release of toxic fluorinated and greenhouse
gases such as hexafluoroethane and tetrafluoromethane with warming
potential of 5700 and 11,900 and half-lives of 50,000 and 10,000 years
respectively require further cleaning technologies such as scrubbing and
electrostatic precipitation, which might concur additional input costs.
However, the use of Ca(OH)2 or persulfate can bring down the release of
toxic gases from both sludge and solid waste to produce environmental-
friendly CaF2 [118, 142, 165].
Sonochemical degradation enables the generation of temperatures
above 500 ◦ C that are sufficient to degrade a broad range of PFAS
compounds, which reaction pathways are sustained for nano-seconds. In
dilute concentrations of about 1 µM, sonochemical degradation works
well but it is rendered unsuitable for real wastewater samples, where the
water mixture is complex. The interferences in real wastewater bring
down the efficiency of such degradation processes. Sonochemical
degradation must be coupled with other processes such as ozonation and
filtration to make it self-sustaining or achieve higher removal rates.
Bioremediation is a promising field as it is an environmentally
benign and economically cheap method. However, biodegradation
processes for PFAS treatment are underdeveloped and understudied
currently. It is hampered by extremely long reaction times (2 days to 2
years), a very slow decomposition rate (36–60 years for reaction yield of
25% for PFCAs) [166], low removal rates (0–68%) [167,168]. The
half-life of precursors (1200–1700 years for poly(acrylate) and 24–281
years for poly(urethane)) [167], degradation rates, and mass balance
differ greatly because of environmental conditions. An estimate of the
PFOA half-lives in these conditions was predicted to range between 10
and 17 years and 870–1400 years [169,170] thus hindering the scal­
ability of such processes (Summarized in Table 7, also Figs. 1 and 2).
4. Treatment train approaches
Tandem use of the aforementioned technologies has proven to be
more effective in the case of treatment of POPs such as PFAS given its
unique stability and recalcitrance [171–173]. To solve the limitations of
capital investment, time consumption, and efficacy of removal, treat­
ment train approaches play a significant role in achieving higher
removal rates with wide-field applicability. The use of capture tech­
niques such as adsorption, filtration, and coagulation coupled with
17
Journal of Environmental Chemical Engineering 9 (2021) 105784
degradation techniques such as EC, AOP, advanced reduction processes
(ARPs), and sonochemical has proven to radically improve the rate of
PFAS treatment. These are known as treatment train processes and are
used to achieve high in-situ treatment efficiency [174]. In a pilot-scale
study, a waste disposal site was used as a source of PFAS. GAC was
used to adsorb PFOA, PFOS, and PFHxA followed by thermolysis to
obtain fluorine recoveries of 51%, 70%, and 74% respectively, up from
30%, 72%, and 46% without GAC. The use of a catalyst- NaOH further
improved the recovery by 74%, 90%, and 91% respectively for PFOA,
PFOS, and PFHxA [175]. These studies are summarized in Table 6, En­
tries 1–16.
The use of bimetals and zero-valent metals along with adsorption
techniques for capture are often recommended. The use of membranes is
often also desirable to achieve higher removal efficiencies followed by
PFAS degradation techniques [13]. Oxidation by ZVI and adsorption by
GAC were combined with photocatalytic degradation by a vacuum
UV-Fenton system at 185 nm to degrade PFOA. Generation of aqueous
electrons helps in oxidation of iodide, which drives defluorination of
PFOA. From an initial concentration of 10 mg L–1, PFOA was effectively
defluorinated to a final concentration of 3.23 mg L–1 with [GAC] =
12.5 mg L–1/[Fe0] = 7.5 gL-1/[H2O2] = 22.8 mmol L–1. Intermediates
such as C7, C6, C5, C4, and C3 were generated in the process by the
photochemical activity of H2O2 generated OH– [176]. The addition of
KOH and removal of the water from sand resulted in complete
defluorination in a ball milling experiment with AFFF-impacted soils.
98% of PFOS and 99% of PFOA were removed in 4 h. Up to 96% removal
was also achieved on-site at a firefighting training area with this tech­
nique [162]. The continuous application of a mechano-chemical and a
hydrothermal process resulted in the adsorption of PFOA in a fixed bed
reactor. Mg-Al-layered double hydroxides- LDH-1 and LDH-2 were able
to remove 90% and 98% of PFOA within 2 h and 40 min respectively
with an initial concentration of 20 mg L–1 of PFOA, volume of 20 mL,
and 0.05 g of adsorbent. This increased its potential for field application
[177].
Phytoremediation efficiency of 14.4% with duckweed was also
achieved by adding an aeration step with more than 95% PFAS removal
from deionized water with 7 h of aeration [178]. In a patented tech­
nology, coagulation combined with air-sparging and hydrocyclone was
used to report 80–97% removal from AFFF-contaminated groundwater.
The water was chemically treated with a metal coagulant and a polymer
and then it was sent to an air-sparged hydrocyclone (ASH) chamber
where air and water fall at a tangential angle to form bubbles or foam.
This foam is then clarified of water in the subsequent steps [179]. The
performance comparison of different capture, degradation, and combi­
natorial technologies is represented in Figs. 1–3.
The limitations of the different treatment processes are coupled in
the treatment train approaches. ASH is desirable and patented because it
can handle large volumes and other kinds of wastewater, with short
retention times [180]. However, mass balance loss in the form of volatile
precursors occurred during the thermal treatment of the PFAS foam
[175]. High capital investment is guaranteed, however, without a 100%
guarantee of PFAS removal. High removal rates are achieved with
filtration during which sludge and oil-based wastes are generated in the
ASH treatment process [180]. Energy- and cost-intensive incinerators,
sonicators, and electrochemical equipment, and loss of adsorbents are
other shortcomings of such kind of processes [175].
5. Future perspectives
Capture technologies are dominated by activated carbons, which
despite efficiently capturing PFAS compounds, were found to suffer
high-cost penalties with respect to their regeneration, due to very robust
PFAS materials interactions. The cost of the adsorbents also remains a
hindrance, and significant cost-reductions could be achieved through
more sustainable materials development. Cost-analysis of the technol­
ogies should also be evaluated systematically to understand the
S. Garg et al. Journal of Environmental Chemical Engineering 9 (2021) 105784

Table 7
The major limitations, advantages, and removals of various PFAS capture, concentration, and degradation technologies as concluded from the present study.
Type Technology Governing parameters Advantages Challenges Common Challenges Additional
References

Capture Adsorption Geometrical: Pore shape, GAC adsorb longer-chained Regeneration is difficult (ACs, Charge of the material
size, and surface area PFAS better biomaterials, and minerals) Transient charge on
Chemical: Molecular Adsorption capacities (g-1 of Regeneration process power- or PFAS molecules [17]
weight, charge, and PFOS/PFOA) pressure-driven (MIPs, CNTs and Effluent properties such
functional group PAC: 1.2–375 mg, IER: IERs) as pH, temperature,
2.5–3067 mg, electrical conductivity,
Chitosan: 645–2580 mg, CNTs: organic matter,
140–1651 mg inorganic
Removal efficiencies of 23% for Frequent replacement of ions [225]
bio-adsorbents and minerals to adsorbents
>99% for IERs, CNTs and ACs
Coagulation Stirring duration Ease of WWTP implementation Dose (~60 mg L–1 alum
remediates only 20% PFOS/
PFOA)
Coagulant dose Swift action in 0.167–1.5 h Corroding of electrodes (H+)
Electrode configuration 99% removal efficiency with Disposing-off used coagulants [192]
electrocoagulation Sludge management
Concentration Membrane Electrostatic repulsion NF (MWCO of 200–1000 Da), Pore size changes due to [88]
filtration more powerful than size Flux >95% changing pH
exclusion
High-pressure driven Effect of functional groups and
membranes (RO, NF), electrostatic repulsion
more effective
Pore-size RO (MWCO <100 Da), Flux Handling and disposal of [75]
Surface roughness >99% concentrates
Surface zeta potential Ease of membrane tuning and
Isoelectric point fabrication
Degradation Catalysis Oxygen vacancies Degradation rate- Poisoning of the catalytic system Formation of shorter-
0.2–1323 min–1 over time chained
Zeta potential Presence of oxygen holes and Doping or stress of degraded precursors and by-
porous structural design helps products/ions products
Radicals quenchers Removal of 80 to >99% Formation of GHGs and [108]
dependent on metal-oxide HF
doping Need of pre-filtration of
In2O3 better than TiO2 effluent (except for
Sonochemical Reactor configuration Up to 98% removals Presence of contaminants in incineration and in [133]
water such as bicarbonates and wetlands
VOCs hinder acoustic waves
propagation
Sonication time Additives, e.g., persulfate ups Energy consumption
removal
Irradiation density Dual frequencies ups removal Upscaling
Ultrasonic frequencies Treatment trains with ozonation Noise pollution
or UV
Power densities Useful for in-situ groundwater Aging of the ultrasound
Atmospheric conditions remediation sonicators
Initial [PFAS]
Operating pH
Temperature
Additives
Photo/ Temperature Low operating times of 0.02 s to Low thermalization potential of [165,175]
Thermal 75 min Volatile PFAS
Irradiation frequency Addition of Ca(OH)2 prevents High operation cost
CO2 leaching into the
atmosphere
Exposure time Supercritical water (94.8% Production of CF3H (Global
PFHxA) remediates more than warming potential:14,800)
subcritical water (83.6% PFHxS)
High mineralization rates
High removal efficiency
Oxidation/ Additive concentration Supercritical water (94.8% OH- less effective in PFAS [16]
reduction Reaction duration PFHxA) remediates > subcritical reduction
water (83.6% PFHxS)
PFAS functional group Highly reductive hydrated e– Presence of Cl- and solids in
water reduces mineralization by
25%
Reaction duration ZVI, fenton agents and electron Variable degradation rate:
Solution chemistry: pH, beams increase removals 0.041 min–1 with persulfate to
T, DO, and TDS 0.00023 s–1 with heat-activated
Organic and inorganic persulfate
constituents: HA, nitrate,
and sulfate
Biological Environment friendly [171]
(continued on next page)

18
S. Garg et al.
Table 7 (continued )
Type Technology Governing parameters Advantages
Seeding density of
culture
Effluents toxicity Cost-effective
Bioaccumulation Upscalable via. Economical
potential options such as constructed
wetlands
Initial [PFAS] Removal efficiencies of 18–96%
Enzymatic removal >>
Organismic removal
Time of enzymatic degradation:
1–6 h
scalability of the approach as well as the feasibility of scaled-up opera­
tions and reactor design. The use of biomaterials (US$246 ton–1 for
activated biochar) over synthetic ($1500 ton-1 for activated carbon)
could help in cost-cutting [181]. Hemp protein powder shows not only
high efficacy to remove PFAS but also remains cost-effective comparing
with commercial adsorbents such as GAC.
Most membrane separation systems have emerged as promising al­
ternatives on model solutions (Figs. 1–3) yet remain largely non-
competitive on large scales since only allowing for several factors of
concentrations. RO still proves to be more cost-effective ($2 m–3),
calculated with the average price of electricity at 8.14 cents KW h–1.
Conventional water treatment methods are still a mere $0.25 m–3,
making it the most wide-reaching treatment practice [127]. The inte­
gration of membranes with catalysts however represents a promising
alternative to generate PFAS lean streams in a single step.
Future degradation-focused research directions should focus on of­
fering greater yields of radical generation through more resilient and
efficient catalysts engineering while reducing the sensitivity of the cat­
alysts to specific adsorption of radical scavengers. Strategies to develop
high surface area photo-electrocatalytic reactors (PECRs) and photo-
electrocatalytic membrane reactors (PECMRs) should also be further
investigated to allow for developing sustainable and cost-effective con­
centration/degradation processes. The development of advanced photo,
electrocatalytic materials, and membrane reactors has a great potential
to play, beyond the sole scope of PFAS, across a range of POPs.
The presence of oxygen vacancies will deeply affect the local atomic
microstructure and electronic properties along the surface of the mate­
rial, therefore allowing for direct fine-tuning of their intrinsic physico­
chemical properties in PEC processes [182,183]. The charge generation
and separation, as well as subsequent surface reactions, may be
controlled through precise defect engineering. Particularly, the presence
of vacancies will (i) extend the light absorption range of the material,
enabling its operation across a wider range of wavelength and poten­
tially within the visible range, (ii) promote charge-carrier separation,
critical to reducing the probability of electron-hole recombination, as
well as (iii) improve surface reactions in terms of yield and selectivity by
affecting the specific adsorption of contaminants across the surface of
the materials [182]. The dependence of the rate of reaction on the level
of oxygen vacancies was found to be clear for several vacancy-induced
materials for PFOA degradation [184–186]. A challenge with
oxygen-vacancy engineering however lies with the relatively short span
stability of these defects. Oxidation reactions may occur over time and
routes to stabilize the vacancies were demonstrated through specific
metal doping of the microstructure of the semiconductors [187,188].
The development of composite nano-structured photocatalysts for
both slurry reactors and surface reactors has allowed for a further in­
crease in photo-electron generation and recombination. Graphene oxide
and its derivatives were used on several occasions as support for
19
Journal of Environmental Chemical Engineering 9 (2021) 105784
Challenges Common Challenges Additional
References
Toxicity or inactivation of
microbes due to harmful PFAS
metabolites
Disposal issues and trophic
transfer of bio-concentrated and
bio-accumulated PFAS in plants
Extremely slow degradation
rates
(0.003 min–1 for HRP,
0.0044 day–1 for laccase)
Enzymatic degradation: 1–6 h [158]
faster than
Organismic accumulation/
breakdown: Up to 100 days
semiconductor decoration [93, 189–191]. The presence of graphene was
found to support electron conduction and therefore results in increased
yields of reaction. Key factors such as light source and wavelength, re­
action temperature, solution pH, dissolved oxygen, and dissolved
organic matter present in the solution, as well as the presence of radical
scavengers will also affect the rate of PFOA compounds degradation. The
control of the process conditions is therefore as critical as the design of
proper photo-catalysts.
Electrocoagulation [58], AOPs, and ARPs [16] have proven to be
effective in remediation of waters from PFAS such as electrocoagulation
removes 65% of fluorine from water but also offer the additional benefit
of treating other water quality parameters such as 60% of total organic
carbons (TOC) is treated with electrocoagulation which is of major
concern for water quality keepers [192]. Fe2+ as the activation agent has
proven to be most economical compared to other activation agents
[117]. The research on cost-effectiveness of oxidation-reduction tech­
nologies is highly limited and more research is required to make these
methods scalable. Similarly, sono-chemistry and biological methods for
PFAS treatment, although promising, are yet in their nascent stages and
further demonstrations are required to establish the conversion mech­
anisms and the applicability of these methods to real wastewaters. These
limitations may be overcome by implementing combinatorial processes
such as dual-frequency systems for sono-chemistry are known to reduce
the cost by 23% to $7.5 m–3 from $10 m–3.
Given the highly localized nature of PFAS contamination and varied
source water compositions, it appears unlikely that a single technology
will emerge as a universal solution for PFAS contaminated source wa­
ters. Further combinations of technologies, including coagulation/floc­
culation or air scouring with adsorbent or membrane materials, may
equally offer technical advances supporting lower operating costs and
selective recovery of PFAS [54]. It is also important not to downplay the
role played by other compounds present and mixed with PFAS com­
pounds [193]. Water recovery as an obvious point represents a first
critical milestone, but other compounds mixed with PFAS should also be
valorized towards a zero-liquid discharge (ZLD) approach. At this
expense only, would such technologies, applied to PFAS or other POPs,
may allow for a truly circular economy strategy.
6. Conclusions
This review critically analyzed the core challenges such as efficiency,
time consumption, influence of effluent and technical properties and
their limitations thereof, related to the development of some of the most
important water remediation techniques related to PFAS compounds’
capture, concentration, and degradation (Table 7). The efficiency of
these remediation strategies is primarily hampered by the low concen­
tration of PFAS compounds, the complexity of the source waters matrix,
and new technologies to selectively concentrate PFAS are required as
S. Garg et al.
pretreatment steps prior to PFAS degradation. Tandem, combinatorial,
or hybrid technologies, developed as trains of sequential treatment ap­
proaches are very likely one of the most promising ways forward to
increase the efficiency of the remediation steps by reducing the need of
pretreatment, operational durations and costs, and to limit the release of
toxic by-products into the environment.
CRediT authorship contribution statement
Shafali Garg: Conceptualization, Methodology, Writing - original
draft. Jingshi Wang: Data curation, Writing - review & editing. Pankaj
Kumar: Visualization, Data curation. Hassan Arafat: Visualization,
Data curation. Vandana Mishra: Supervision, Writing - review & edit­
ing. Radhey Sharma: Supervision, Writing - review & editing. Ludovic
Dumee: Supervision, Validation, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
A/Prof. Ludovic Dumee acknowledges the Australian Research
Council (ARC) for his Discovery Early Career Research Award (DECRA)
2018. LFD acknowledges the support from Khalifa University through
project RC2-2019-007. The authors acknowledge the support of Deakin
University and the Micro-Nano Group (Prof. Lingxue Kong). The support
extended by the Ministry of Education, Government of India to the Delhi
School of Climate Change & Sustainability, Institute of Eminence, Uni­
versity of Delhi is duly acknowledged by RSS and VM. SG and PK extend
thanks to University Grants Commission for Junior Research Fellowship
and University of Delhi.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jece.2021.105784.
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