Chemosphere 307 (2022) 135888

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review: Hydrothermal treatment of per- and polyfluoroalkyl

substances (PFAS)
Jianna Li a, b, Brian R. Pinkard a, c, Shuzhong Wang b, Igor V. Novosselov a, *
a
University of Washington, Mechanical Engineering Department, Seattle, WA 98195, USA
b
Key Laboratory of Thermo-Fluid Science and Engineering of MOE, School of Energy and Power Engineering, Xi’an Jiaotong University, 28 Xianning West Road, Xi’an
710049, China
c
Aquagga, Inc., Tacoma, WA 98421, USA

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• State-of-the-art PFAS destruction treat­

ments in hydrothermal conditions are
reviewed.
• Destruction efficiency and reaction
mechanisms of PFAS are presented.
• Environmental impacts of the hydro­
thermal treatments are evaluated.
• Technology research and development
challenges are analyzed.
• Potential directions for future techno­
logical development are proposed.

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

Handling Editor: Y Yeomin Yoon Per: and polyfluoroalkyl substances (PFAS) are a concerning and unique class of environmentally persistent
contaminants with biotoxic effects. Decades of PFAS discharge into water and soil resulted in PFAS bio­
Keywords: accumulation in plants, animals, and humans. PFAS are very stable, and their treatment has become a global
Per- and polyfluoroalkyl substances environmental challenge. Significant efforts have been made to achieve efficient and complete PFAS minerali­
Subcritical hydrothermal treatment
zation using existing and emerging technologies. Hydrothermal treatments in subcritical and supercritical water
Supercritical water oxidation
have emerged as promising end-of-life PFAS destruction technologies, attracting the attention of scholars, in­
PFAS Degradation efficiency
Reaction mechanism dustry, and key stakeholders. This paper reviews the state-of-the-art research on the behavior of PFAS, PFAS
precursors, PFAS alternatives, and PFAS-containing waste in hydrothermal processes, including the destruction
and defluorination efficiency, the proposed reaction mechanisms, and the environmental impact of these
treatments. Scientific literature shows that >99% degradation and >60% defluorination of PFAS can be achieved
through subcritical and supercritical water processing. The limitations of current research are evaluated, special
considerations are given to the challenges of technology maturation and scale-up from laboratory studies to
large-scale industrial application, and potential future technological developments are proposed.

* Corresponding author.
E-mail address: ivn@uw.edu (I.V. Novosselov).

https://doi.org/10.1016/j.chemosphere.2022.135888
Received 23 May 2022; Received in revised form 14 July 2022; Accepted 28 July 2022
Available online 2 August 2022
0045-6535/© 2022 Elsevier Ltd. All rights reserved.
J. Li et al. Chemosphere 307 (2022) 135888

1. Introduction stability of the C–F bond results in environmental persistence of PFAS,

which is especially concerning when combined with the long-distance
Per- and polyfluoroalkyl substances (PFAS) belong to a class of mobility, bioaccumulation, and biotoxic effects. Contamination of the
artificially synthesized fluorine-containing organic compounds, typified airshed, ground and surface waters, and soils have been reported (Lang
by a long hydrophobic aliphatic carbon chain, where the hydrogen et al., 2017; Li et al., 2020a; Garnett et al., 2021; Petre et al., 2021;
atoms are replaced by one or more fluorine atoms, forming at least one Sharma et al., 2022). PFAS from the environment can be transferred into
perfluoroalkyl groups (CnF2n+1). PFAS include both polyfluoroalkyl living organisms, including plants, animals, and humans, gradually
substances (carbon atoms are partly fluorinated) and perfluoroalkyl accumulating up the food chain in increasing concentrations (Olsen
substances (carbon atoms are entirely fluorinated) (Sharma et al., 2022). et al., 2007). PFAS, especially the widely used C8 compounds, such as
In addition, the molecule may be terminated by a functional group, such PFOS and PFOA, have been found in serum (Olsen et al., 2007), blood
as carboxylate in perfluoroalkyl carboxylic acids (PFCAs), sulphonamide (Kannan et al., 2004), urine (Worley et al., 2017), placenta (Blake and
in perfluorooctane sulfonamide (PFOSA), phosphonate in perfluoroalkyl Fenton, 2020), and breast milk (Zheng et al., 2021). A growing body of
phosphonic acids (PFPAs), or sulfonate in perfluoroalkane (or -alkyl) research indicates that PFAS exposure leads to adverse health effects,
sulfonic acids (PFSAs) (Buck et al., 2011; Whitworth et al., 2016; Al posing a severe threat to human reproductive and immune system health
Amin et al., 2020; Dixit et al., 2021). (Bach et al., 2016; Blake et al., 2018; Coperchini et al., 2021; Steenland
According to the number of fluorinated carbon atoms, PFAS are and Winquist, 2021; Sharma et al., 2022), causing liver and kidney
informally classified as “long-chain” or “short-chain”; for instance, long- damage (Roth et al., 2021; Steenland and Winquist, 2021), thyroid
chain PFAS include the PFCAs with eight or more carbons disease (Blake et al., 2018), high cholesterol (Averina et al., 2021),
(CnF2n+1COOH, (n ≥ 8), such as PFOA), and PFSAs with six or more obesity (Averina et al., 2021), decreased fertility (Rickard et al., 2022),
carbons (CnF2n+1SO3H, (n ≥ 6), such as PFOS). In contrast, the short- hormone suppression (Gronnestad et al., 2021), and cancer (Steenland
chain PFAS include PFCAs (n < 8, e.g.: perfluorooctanoic acid, and Winquist, 2021). The widespread presence of PFAS has attracted
PFHxA), PFSAs (n < 6, e.g.: perfluorobutane sulfonate, PFBS) (Buck significant attention worldwide. PFOS and perfluorooctane sulfonyl
et al., 2011; Al Amin et al., 2020; Dixit et al., 2021), fluoride (POSF) have been listed as persistent organic pollutants (POPs)
undecafluoro-2-methyl-3-oxahexanoic acid (HFPO-DA/GenX), under the Stockholm Convention in 2009 (UNEP, 2019). Enforceable
dodecafluoro-3 H-4,8-dioxanonanoate (ADONA), and 9-chlorohexade­ guidelines regulating the allowable concentration of PFAS in drinking
cafluoro-3-oxanonane-1-sulfonate (6:2 Cl-PFESA/F–53B). Fig. 1 shows water have been established in Canada, the EU, Australia, and several US
a classification family tree for non-polymer PFAS. States. The United States Environmental Protection Agency (US EPA)
Due to the presence of the hydrophobic aliphatic carbon chain (Dixit et al., 2021) has established drinking water health advisory levels
(CnF2n+1) and hydrophilic functional group, the strong bonding energies (HALs) for both the individual or total concentration of PFOS and PFOA
(C–F, 485 kJ/mol) and the high redox potential (F to F− , E0 = 3.6 V) (Lu of less than 70 ng/L (EPA, 2016b, a). As of June 2022, the US EPA
et al., 2020), PFAS exhibit unique physicochemical properties. These updated the HAL of PFOA (0.004 ppt) and PFOS (0.02 ppt) and also
include exceptional chemical and thermal stability (i.e., highly issued the updated HALs for perfluorobutane sulfonic acid and its po­
non-flammable and acid/base-resistant) (Lu et al., 2020), low surface tassium salt (PFBS, 2000 ppt) and hexafluoropropylene oxide (HFPO)
tension, and high surface activity. The hydrophobic and oleophobic dimer acid and its ammonium salt (GenX chemicals, 10 ppt).
properties lead to PFAS use in industrial applications and domestic Except for limited exemptions, the import, export, production, and
products, such as textiles, carpets, paper, various coatings, detergent, use of PFOS, PFOA, and other long-chain PFCAs (as well as salts and
lubricants, polymer additives, electronic products, fire-fighting foam, precursors) have been prohibited by the USA (EPA, 2006), EU (EU,
etc. (Munoz et al., 2019; Adamson et al., 2020). On the flip side, the 2021), Canada (2010), Japan (Kawanishi, 2018), and other countries (Li

Fig. 1. An abbreviated, non-polymer PFAS family tree, the data is compiled from the following references (Robert Mueller, 2020; EPA, 2021b; Lee et al., 2021;
Winchell et al., 2021).

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J. Li et al. Chemosphere 307 (2022) 135888

et al.; Government, 2007). PFAS alternatives are being developed to destruction of PFAS and PFAS-containing wastes (EPA, 2021a; Office,
minimize the environmental toxicity and maintain the desirable prop­ 2021). Here we review the state-of-the-art research on the destruction of
erties of PFAS for application as fire extinguishing agents, chrome mist traditional PFAS, PFAS alternatives, and PFAS-containing wastes in
inhibitors, and other applications (Wang et al., 2019; Bao et al., 2020). hydrothermal environments, presenting published data on the destruc­
Since the length of the perfluoroalkyl chain strongly affects bio­ tion efficiency, fluorine transformation pathway, reaction mechanisms,
accumulation (Martin et al., 2019), alternative strategies have been and environmental impact of the hydrothermal treatments. The tech­
focused on using short-chain compounds (Li et al., 2020a) such as per­ nology development challenges and the transitioning from laboratory
fluorobutanesulfonic acid (PFBS), perfluorohexanesulfonic acid (PFHS) studies to large-scale industrial plants are analyzed, and the potential
and perfluorohexanoic acid (PFHA) (Campbell et al., 2009). The fluo­ directions for future technological development are proposed.
roalkylether compounds (ether-PFAS), such as GenX, ADONA, and
F–53B, include oxygen atoms in the molecular backbone, reducing the 2. Technology details
perfluorinated chain length (Munoz et al., 2019). Another proposed
pathway is to switch from perfluorinated to polyfluorinated compounds, Supercritical water (SCW) refers to water at temperatures and pres­
such as 6:2 fluorotelomer sulfonate acid (6:2 FTSA) (Urtiaga et al., sures higher than the critical point (Tc = 374 ◦ C, Pc = 22.1 MPa), while
2018). However, recent studies indicate that these alternatives, such as subcritical water refers to compressed liquid water at temperatures in
6:2 FTSA, GenX, and F–53B, may have similar or even higher toxicity the range from 100 ◦ C to 374 ◦ C and pressures sufficiently elevated to
than conventional PFAS (Munoz et al., 2019; Wang et al., 2019; Olver­ maintain a liquid phase, as shown in Fig. 2 (Savage, 1999). Subcritical
a-Vargas et al., 2022). GenX, F–53B, and hexafluoropropylene oxide and supercritical water physicochemical properties are significantly
trimer acid (HFPO-TA) have been detected in global surface waters, different from liquid water under ambient conditions. For instance, both
wastewater, groundwater, drinking water, and municipal sewage have lower viscosity, high diffusivity, variable density, and low dielec­
sludge, including the United States, Germany, the United Kingdom, the tric constant. Interestingly, SCW behaves like a non-polar solvent, which
Netherlands, Sweden, China, and Korea (Lin et al., 2016; Pan et al., could efficiently dissolve organic substances and gases (Li et al., 2020b);
2018). Moreover, F–53B and HFPO-TA have been exposed to biologicals in some applications, flameless SCWO reactors can be operated in
such as marine organisms, amphibians, as well as marine mammals. distributed reaction regimes, enabling a uniform reaction medium for
ADONA was detected in blood samples of humans, and F–53B was found highly effective destruction of recalcitrant compounds (Moore et al.,
in maternal and cord serum (Wang et al., 2019). 2021; Purohit et al., 2021). The ion product constant of subcritical water
Besides, PFAS precursors, such as fluorotelomer alcohols and fluo­ is roughly three orders of magnitude higher than that of water at
rotelomer sulfonates, are used in industrial and commercial applications ambient conditions resulting in high concentrations of H+ and OH− and
in large quantities. These compounds have been detected in the envi­ making subcritical water an effective acid-base catalytic reaction me­
ronment (Asher et al., 2012), and could also be transformed into the dium (Moller et al., 2011). The ion product constant of SCW is over five
PFCAs and PFSAs that have a longer half-life in the environment, posing orders of magnitude lower than that of water at ambient conditions,
ecological risks and adverse impacts on human health (Zhang et al., facilitating free radical reaction pathways (Savage, 1999) which was
2021b). demonstrated for gasification (Pinkard et al., 2018, 2019a, 2020a),
Therefore, effective PFAS remediation requires efficient and com­ partial oxidation (Pinkard et al., 2019c), and SCWO (Savage et al., 2000;
plete degradation of PFAS, PFAS precursors, and PFAS alternatives, of­ Vogel et al., 2005; Gong et al., 2018) reactions.
fering end-of-life disposal with complete defluorination (cleavage of all The subcritical hydrothermal treatment (HT) utilizes hot compressed
the C–F bonds). Various technologies have been investigated for their water as the reaction medium (Zhang et al., 2021a). It has been used for
application toward PFAS remediation and destruction. These are aimed waste treatment, recycling (Shetty et al., 2022), and energy conversion
at PFAS capture and removal from liquids via granular activated carbon application. HT liquid waste treatment research includes studies on the
(GAC) adsorption (Pauletto and Bandosz, 2022), ion exchange resin decomposition of recalcitrant chemical warfare agents (CWAs) (Pinkard
(IXR) treatment (Maimaiti et al., 2018), nanofiltration (NF), and reverse et al., 2020c), polychlorinated biphenyls (PCBs) (Yamasaki et al., 1980),
osmosis (RO) membrane separation (Wang et al., 2018; Lee et al., 2021). polychlorinated dibenzo-dioxins and polychlorinated dibenzofurans
Physical adsorption methods concentrate PFAS; thus, end-of-life treat­ (PCDD/Fs) (Chen et al., 2012), and PFAS (Hori et al., 2008; Yu et al.,
ment technologies of concentrated feedstocks become necessary. Several 2020; Zhang et al., 2020). Of specific interest to the PFAS environmental
approaches for PFAS degradation or destruction have been proposed, fate topic is hydrothermal liquefaction technology (HTL); HTL has been
including biological treatment (Shahsavari et al., 2021), dual-frequency
ultrasound (DFUS) (Lei et al., 2020), plasma-based technology (Singh
et al., 2019a), sonochemical destruction (Kalra et al., 2021), oxidation
by activated persulfate or peroxymonosulfate oxidation (Wang et al.,
2018; Suhnholz et al., 2021), photocatalytic oxidation (Xu et al., 2020;
Wu et al., 2021), Fenton oxidation (Trojanowicz et al., 2018), electro­
chemical oxidation (Sharma et al., 2022), and incineration (Tsang et al.,
1998). Chemical methods can degrade PFAS by cleaving the C–F bonds;
however, current approaches still require long residence times, high
energy consumption, and expensive chemical additives such as sulfite,
iodide, Fe(III), persulfate, or TiO2 (Trojanowicz et al., 2018; Deng et al.,
2021). Electrochemical methods could achieve a high PFAS degradation
(Sharma et al., 2022); however, the processing becomes rather complex,
and the process economics may not be favorable for large-scale
applications.
Subcritical hydrothermal treatment (HT) and supercritical water
oxidation (SCWO) have been used for the treatment of recalcitrant
organic wastes and recently have attracted attention as promising
technologies for PFAS destruction (Modell, 1980; Hori et al., 2008;
Krause et al., 2022). The US EPA has recommended HT and SCWO as
technologies with significant commercial and industrial potential for the Fig. 2. Phase diagram of water (EPA, 2021a).

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J. Li et al. Chemosphere 307 (2022) 135888

developed to convert biomass such as sewage sludge (Hu et al., 2021), 3. Data analysis
lignocellulosic (Scarsella et al., 2020), kitchen waste (Motavaf et al.,
2021), and microalgae (Biller and Ross, 2011) into energy-dense fuel Here, PFAS removal efficiency is defined as:
precursors (Gollakota et al., 2018).
[PFAS]ini − [PFAS]resi
SCWO process benefits from the high free radical environment to Removal ​ efficiency = × 100%
[PFAS]ini
achieve high organic compounds conversion efficiencies via oxidative
reaction mechanisms. SCWO has also become a promising technology
where [PFAS]ini is the initial measured concentration of PFAS in the
for destroying complex organic compounds and wastes that rapidly
stock solutions, and [PFAS]resi is the residual PFAS concentration in the
dissolve and mix with oxidants in a homogeneous reaction environment,
reaction products.
eventually completely decomposing into harmless small molecules such
The defluorination efficiency indicates the percent of fluorine in
as CO2 and H2O. Heteroatoms are converted to corresponding inorganic
PFAS molecules transformed into fluoride ions:
acids or salts, such as HCl, HF, sulfates, phosphates, etc. (Marrone,
2013). SCWO follows the free radical reaction mechanism (Li et al., CF −
Defluorination ​ efficiency = ∑ × 100%
1991; Boock and Klein, 1993; Croiset et al., 1997), with hydroxyl radi­ Corganic− F
cals (•OH) being the primary oxidizing species owing to their high
reactivity (E0 = 2.33 V). SCWO has been demonstrated to destroy hy­ where C−F is the detected fluoride ions concentration in the products and
drocarbon organics such as methanol (Henrikson et al., 2006), acetic the Corg-F is the concentration of organic fluorine initially bounded in
acid (Lee et al., 1990), phenol (Guan et al., 2011), nitrogenous organics PFAS, which is calculated as the summation of the mole fraction of F in
such as pyridine (Crain et al., 1993), quinoline (Ren et al., 2019), aniline each PFAS multiplied by each PFAS concentration.
(Ma et al., 2012), nitroaniline (Yang et al., 2018), halogenated organics
containing fluorine, chlorine, bromine, or iodine, like PCBs (Kim et al., 4. Degradation of PFAS in subcritical water
2010) and PFAS (Pinkard et al., 2021), and phosphorus-containing or­
ganics such as CWAs (Moore et al., 2021). More than 99% COD/TO­ The scientific literature describes the destruction of pure PFAS
C/organic removal efficiency can be realized at operating T = compounds, PFAS alternatives, and waste containing PFAS in subcritical
500–650 ◦ C, P = 23–28 MPa, and H2O2, O2, or air as the oxidant (Li water. These reports include the effects of reaction parameters such as
et al., 2020b). Some large-scale SCWO facilities have also been devel­ temperature, residence time, additive type and concentrations, Some
oped (with varied success) to treat organic wastewater and sludge, such more recent reports address reaction mechanisms and kinetics. Table 1
as pesticide wastewater (Li et al., 2021), municipal sludge (Xu et al., summarizes the literature related to the degradation and defluorination
2012; Qian et al., 2016), and industrial sludge (Yang et al., 2019). of PFAS in subcritical water reaction environments.
Managing reactor corrosion and salt precipitation has been a significant
challenge in practical applications of SCWO (Vadillo et al., 2013).
4.1. Degradation of PFAS compounds and their precursors

As shown in Table 1, most studies show PFAS removal efficiency

Table 1
The degradation effects of various PFAS and its alternatives in subcritical water without additive.
Substances T P t Additive PFAS Additive Reactor Removal Defluorination Reference
(◦ C) （MPa） (h) concentration concentration type efficiency (%) (%)

GenX 250 – 2 – 20 μg/L – batch ~100 – Zhang et al.

reactor (2021a)
ADONA 300 – 2 – 20 μg/L – batch ~100 – Zhang et al.
reactor (2021a)
F–53B 300 – 2 20 μg/L – batch 12.92 ± 3.39 – Zhang et al.
reactor (2021a)
PFCAs mixture 300 2 – 2000 μg/L – batch ~100 – Zhang et al.
reactor (2020)
PFAA mixture (in 300 2 – – batch ~100 – Zhang et al.
cattail) reactor (2020)
PFOA 350 16.5 1 – – batch 98 12 ± 10 Yu et al.
reactor (2020)
8:2 FTUCA 350 16.5 1 – – batch 98 – Yu et al.
reactor (2020)
7:3 FTCA 350 16.5 1 – – batch 99 ± 0.1% – Yu et al.
reactor (2020)
8:2 FTS 350 16.5 1 – – batch 57 ± 3% – Yu et al.
reactor (2020)
PFOS (in cattail 300 2 – 2352.9 μg/kg – batch 98.4 ± 2.8 – Zhang et al.
roots) reactor (2020)
PFOS (in cattail 300 2 – – batch 49.7 ± 6.3 – Zhang et al.
shoots) reactor (2020)
PFOS 350 23.3 6 118.8 mg/L – batch 9.7 0.16 Hori et al.
reactor (2006)
PFOS 350 16.5 1 – – batch ~0 ~0 Yu et al.
reactor (2020)
AFFF 350 20.7 2 – 3200 mg/L – batch 99.88 – Pinkard (2022)
reactor
PFHS 350 21.2 6 – 5.93 μM – batch 7.6 3.27 Hori et al.
reactor (2008)
PFSAs mixture 300 2 2000 μg/L – batch 10–22 – Zhang et al.
reactor (2020)

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J. Li et al. Chemosphere 307 (2022) 135888

>98% for the temperature range of 250 ◦ C–350 ◦ C and exposure times The defluorination of 8:2 FTUCA, 7:3 FTCA, and 8:2 FTS increased with
from 2 to 6 h. Complete degradation of five PFCAs (PFBA, PFPeA, temperature, indicating the C–F bond’s cleavage.
PFHxA, PFHpA, and PFOA) was achieved after 2 h at 300 ◦ C, while the
removal of PFSAs (PFBS, PFHxS, and PFOS) were <20% at the same 4.2. Degradation of PFAS alternatives
conditions. PFOS destruction may be enhanced by the presence of PFBS
and PFHxS in the mixture (Zhang et al., 2020). During the degradation As mentioned above, the degradation of PFAS alternatives is also
of PFAS in the HT environment, HF is produced due to the cleavage of important and necessary. Hori et al. (2009) have compared the degra­
the C–F bond. Yu et al. (2020) found that 30 ± 6% defluorination was dation of C2F5OC2F4SO−3 , C4F9SO−3 , and C3F7OC2F4SO−3 with the pres­
achieved at 300 ◦ C for PFOA, while almost all PFOS was intact, and no ence of oxygen in subcritical water, reporting that the removal rate of
fluoride was detected in the aqueous phase even at 350 ◦ C. A 35% C3F7OC2F4SO−3 was higher than C2F5OC2F4SO−3 . C4F9SO−3 was more
removal of PFOS was reported in the treatment of a sewage sludge stable than the others at 350 ◦ C, 6 h. This suggests that the presence of an
matrix at 260 ◦ C, although the PFOS yields were stable even when the ether bond and the perfluoroalkyl chain length influence the reactivity
temperature was increased to 350 ◦ C or the residence time was extended of PFAS in subcritical water. In the presence of oxygen, the organic
from 30 to 90 min. Since destruction rates of PFOA and PFOS are very fluorine was converted into F− , minor yields of TFA and CF3H were
different, it was proposed that the initiation steps in the HT environment observed, organic carbon was transformed into CO2, and the sulfur head
take place mainly at, or near, the polar head group rather than in the group was converted to SO2− 4 . When changing the oxygen to argon, the
perfluoroalkyl chain. It has been clearly shown that PFSAs such as PFOS yield of F− , CO2, and SO2−4 decreased, the formation of CF3H and TFA
are much more stable than PFCAs in subcritical water (Yu et al., 2020). increased, and HCF2SO− was produced as a reaction byproduct (Hori
Additional reagents are required to enhance the degradation and et al., 2009).
defluorination of PFSAs. Horia et al. (2012) studied the effect of metals such as Cu, Zn, and Fe
Hori et al. (2006) found that 90.3% PFOS remained in the liquid in the subcritical reaction environment with the presence of O2 and Ar
effluent and with only 0.16% of F− yield after the exposure to 350 ◦ C for on the destruction of cyclic perfluoroalkyl surfactant [CF2(CF2SO2)2N]− .
6 h. The addition of metals enhanced the treatment of PFOS, and Fe has The authors showed that <5% [CF2(CF2SO2)2N]− was removed and
the highest activity, which facilitated near-complete destruction of PFOS <2% F− was released after 6 h at 350 ◦ C and 15.6 MPa even with the
with a corresponding 51.4% yield of F− without any intermediates presence of O2 or Ar. The addition of Fe, Zn, and Cu enhanced the
identified. Zn and Cu also enhanced PFOS destruction, while Al did not mineralization significantly; > 99.9% degradation of [CF2(CF2SO2)2N]−
improve the PFOS degradation. It was found that 42.7% of the PFOS was and 63.5% yield of F− was achieved with 9.6 mmol Fe in the Ar reaction
strongly adsorbed on the surface of Fe in the initial solution, and PFOS in environment. Zn and Cu amendment resulted in 67.85% and 15.1%
the solution was completely degraded after 6 h at 350 ◦ C. The release of degradation of [CF2(CF2SO2)2N]− , 2.02% and 29.7% yield of F− ,
F− continued increasing during the destruction of the PFOS remaining respectively (Horia et al., 2012). Unlike the destruction of PFOS with Fe
on the Fe, and a 61.0% yield of F− was finally obtained after 12 h. (Hori et al., 2006), the cleavage of –(SO2)2N– was more rapid than
Similar improvements were reported when treating shorter chain (C2 to –SO3–. Fe3O4 was produced during the reaction process of
C6) PFSAs with Fe (Hori et al., 2008). [CF2(CF2SO2)2N]− in subcritical water, where the ring-opening reaction
Besides metals, alkalis were also investigated as catalysts in occurred, and HCF2CF2CF2SO−3 was formed as an intermediate (Horia
subcritical water, referred to as hydrothermal alkaline treatment (HALT) et al., 2012).
(Pinkard, 2022). Wu et al. (2019) screened different amendments such Hori et al. (2015) compared the effects of Fe and FeO (with the
as acids, alkalis, oxidants, and reductants for the PFOS degradation in addition of O2) on the decomposition of –O3SC3F6SO−3 and C3F7SO−3 and
hydrothermal conditions. They found that the addition of NaOH, NaBH4, found that in the subcritical water, the Fe was more active than FeO in
and K2FeO4 greatly improved the defluorination (>70%) compared to accelerating the generation of F− . However, in situ disproportionation of
KMnO4, Na2CO3, and Na2S2O3, which only yielded 20% defluorination FeO occurred at higher temperatures (>257 ◦ C), forming Fe and Fe3O4,
under the same reaction environments (350 ◦ C, 16.5 MPa, 90 min). At increasing the degradation of –O3SC3F6SO−3 over Fe addition under su­
the same time, Na2S2O8 showed little enhancement in the PFOS degra­ percritical water conditions. Regardless, the destruction of
dation and F- yields. The authors indicated that the high pH environ­ –O3SC3F6SO−3 was higher than C3F7SO−3 whether Fe or FeO was added.
ment enhanced the PFOS degradation and defluorination rather than the Organic cations or metal ions also affected the degradation and
oxidative or reducing properties of the amendments. Wu et al. (2019) defluorination behavior. Comparative experiments were performed be­
have also performed Zerovalent Iron (ZVI) experiments; however, tween [(C6H5)3S][CF3SO3] and CF3SO3K with the presence of Fe or O2 in
compared to the Hori et al.’s study (Hori et al., 2006), they reported only subcritical water. For [(C6H5)3S][CF3SO3], near 100% removal of
6.3% defluorination was obtained with ZVI powder and only 15.1% CF3SO−3 and 74.4% yield of defluorination were obtained at 373 ◦ C for 6
defluorination with nano-zero-valent iron powder. h with Fe, while only 52.5% degradation of CF3SO−3 and 19.7%
PFOS degradation kinetics depend significantly on the NaOH con­ defluorination were achieved for CF3SO3K under the same conditions.
centration; thus, a second-order rate law was developed to describe the For [(C6H5)3S][CF3SO3], the addition of O2 also enhanced the decom­
PFOS degradation rate. The second-order rate constant was measured as position of CF3SO−3 and inhibited the formation of CHF3 and benzene in
0.052 ± 0.004 M− 1 min− 1 at 350 ◦ C. The defluorination yields were gaseous products (Hori and Yokota, 2015), especially near the critical
lower than the PFOS degradation, indicating that short-chain fluori­ point at 373 ◦ C, where the maximum F− yield (93.6%) was obtained.
nated intermediates may be produced as short-lived intermediates since
the discrepancy between PFOS defluorination and removal decreases at 4.3. Degradation of PFAS-containing waste
higher temperatures, extended residence times, and higher NaOH con­
centrations (Wu et al., 2019). PFAS and its alternatives are present in complex wastewaters,
Currently, only a few papers describe the treatment of PFAS pre­ sludges, and environmental remediation byproducts. It is meaningful to
cursors with HT technology. Yu et al. (2020) reported degradation of study PFAS degradation behavior in realistic sample matrices, which
three PFAA precursors (8:2 FTUCA, 7:3 FTCA, and 8:2 FTS) by HT for 90 could provide more practical guidance for PFAS degradation in large-
min. The authors report >99% destruction of 8:2 FTUCA at 260 ◦ C, > scale plants.
99% of 7:3 FTCA at 350 ◦ C, and only 57 ± 3% destruction of 8:2 FTS at
T = 350 ◦ C. The increase in reaction temperature improved the 4.3.1. Aqueous Film-Forming Foam
decomposition of 7:3 FTCA from 24 ± 10% (260 ◦ C) to 99 ± 0.1% Aqueous film-forming foam (AFFF) is a highly effective fire-fighting
(350 ◦ C); however, no significant differences were observed for 8:2 FTS. foam made of complex mixtures of PFASs and other solvents. AFFF has

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J. Li et al. Chemosphere 307 (2022) 135888

been widely used for extinguishing high-hazard flammable liquid fires at products, most residual PFAS accumulated in the biocrude oil phase,
military bases, oil refineries, and fire departments since the 1960s likely due to greater PFAAs affinity to oil being greater than that for solid
(Moody and Field, 2000; Hao et al., 2021). Fire-fighting training drills and aqueous surfaces. Further separation or destruction of PFAS in
have discharged significant quantities of PFAS into the environment, biocrude oil may be required to allow its subsequent use.
polluting groundwater, drinking water supplies, and soil. In a separate study, different catalysts (Ca(OH)2, GAC, zeolite, red
Hao et al. (2021) studied the treatment of two AFFF blends, based on mud) were added to the sludge to synergistically enhance the degra­
sulfonate and fluorotelomer formulations, respectively, containing over dation of PFAS and improve the biocrude yield and quality. Maximum
109 PFAS species. Compared with PFSAs-based AFFF, the yields of biocrude, carbon conversion efficiency, and energy recovery
fluorotelomer-based AFFF was more reactive under hydrothermal were obtained when adding red mud (including Fe2O3, Al2O3, TiO2,
alkaline conditions, which could achieve complete degradation and CaO2, SiO2, and Na2O). After 2 h exposure of PFAA (PFOA, PFOS, PFBS)
defluorination faster. Rising reaction temperature, extending residence at 300 ◦ C, the concentration of PFOA and PFOS in aqueous products was
time, and increasing NaOH concentration improved the degradation and below the detection limit even without catalyst, but the PFBS concen­
defluorination of PFAS. For example, 98% defluorination for tration was increased when adding zeolite or red mud. For the biocrude
PFSAs-based AFFF was obtained at 350 ◦ C for 90 min with 5 M-NaOH, phase products where most of the residual PFAAs were detected, each
while only 11% defluorination was achieved at 200 ◦ C. All concentra­ catalyst did not affect PFAA degradation, and Ca(OH)2 increased the
tions of PFCAs, FBSA, PFDS, Cl-PFOS, TAmPr-FHxSA, and AmPr-FHxSA concentration of PFBS even further (Zhang and Liang, 2022). Therefore,
were below the detection limit at 350 ◦ C after 30 min with 1 M-NaOH or better approaches are needed to improve the PFSA degradation in both
15 min with 5 M-NaOH. At the same time, the PFSAs (C3 to C8) required aqueous and biocrude phases.
30 min with 5 M-NaOH to be completely degraded, and no fluorinated
gases (such as CHF3 and C2F6) were detected. The degradation kinetics 4.3.3. Typha Latifolia
of PFAS have a higher first-order dependency on NaOH concentration; Typha latifolia is a common cattail species, growing on every
the precise reaction rate constant could not be obtained with 5 M-NaOH. continent except Antarctica (Smith, 1987). It exhibits a strong tolerance
Experiments in continuous reactors with fast heat-up and quenching to pollutants, fast transpiration, and high biomass production potential,
times should be conducted to elucidate reaction kinetics. and it has been recognized as an excellent medium for phytoremediation
Pinkard (2022) also reported the treatment of AFFF containing about to take up environmental contaminants (Demirezen and Aksoy, 2004;
79.8% PFOS, 13.3% PFHxS, and a few other PFSAs and PFCAs under Gobelius et al., 2017). Typha latifolia can accumulate PFAS (such as
alkaline hydrothermal conditions with 5 M-NaOH. Longer residence PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFBS, PFHxS, and PFOS) and PFAS
time and the addition of a heterogeneous catalyst enhanced the degra­ alternatives (such as GenX, ADONA, and F–53B) in both shoots and
dation of AFFF, 99.996% removal of PFAS and complete F− release was roots. The short-chain PFAS are more easily transferred and accumu­
observed at 350 ◦ C, > 20.7 MPa, and 5 M-NaOH after 6 h of exposure. It lated in the shoots (Yin et al., 2017; Zhang et al., 2020, 2021a). Since
was also found that the short-chain PFSAs were slightly more refractory Typha latifolia has a promising potential for taking up PFAS, the plants
than the long-chain PFSAs, with reactivity ordered as PFBS > PFPS > with the sustained accumulation of PFAS should be subsequently treated
PFHxS > PFHpS > PFOS. The PFCAs were suspected to be intermediate to destroy the entrained PFAS.
products during the hydrothermal treatment of PFSAs. Zhang et al. (2020) investigated the removal of perfluoroalkyl acids
(PFAAs) accumulated in the shoots and roots of Typha latifolia. Nearly
4.3.2. Sewage sludge 100% removal efficiency was achieved for all the PFCAs at T > 300 ◦ C
Household and industrial wastewater is a major source of PFAS with 2 h exposure, while 1.6 ± 2.8% and 50.3 ± 6.3% of PFOS remained
emission into the environment, mainly containing PFAAs (long chain in roots and shoots. The residual PFOS concentration in the solid phase
and short chain PFCAs and PFSAs) and PFAA precursors (Arvaniti and was higher than that in the liquid, whether in the roots or shoots. Similar
Stasinakis, 2015). It has been reported that PFAA precursors can be to the PFOS in sewage sludge, the removal of PFOS in Typha latifolia was
converted into PFAAs, increasing the concentration of PFAS during the also higher than that in aqueous PFAA mixtures or aqueous single-PFAS
degradation of wastewater (Schultz et al., 2006). Sewage sludge, a solutions.
byproduct produced during wastewater treatment, has become the PFAS alternatives GenX and ADONA were completely degraded in
major conveyor of PFAS into the environment (Zhang et al., 2010). the aqueous phase, biocrude phase, and solid-phase products at 250 ◦ C
The degradation of PFAAs and transfer of PFAA precursors in sludge after 2 h exposure. However, removing F–53B was more challenging;
after HT were studied by Zhang and Liang (2021). 100% removal effi­ only 76.17% ± 1.67% removal efficiency in roots was obtained at
ciencies of PFOA, PFHpA, and PFHxA were achieved after 2 h of treat­ 300 ◦ C for 2 h. The addition of Ca(OH)2 promoted the degradation of
ment at 250 ◦ C; however, the concentration of PFSAs (including PFOS, F–53B. It was hypothesized that the difference in the chemical structure
PFHxS, and PFBS) was found to increase after the treatment at 300 ◦ C for of the hydrophilic functional group head between GenX, ADONA, and
2 h. On one hand, the thermal process enhanced the desorption and F–53B was responsible for the difference in the destruction rates. For
release of unextracted PFSA, while the PFAA precursors in the sludge instance, GenX and ADONA only have carbon and oxygen and a carboxyl
were converted into PFAAs during the HT process at T < 250 ◦ C. The group, while F–53B also has a stable R–SO-3 functional group, increasing
addition of Ca(OH)2 showed no effect on PFSA degradation and signif­ the stability of the F–53B in the subcritical water and making it more
icantly increased extractable PFSAs (Zhang and Liang, 2021). difficult to destroy (Zhang et al., 2021a).
As mentioned, HTL has been explored as a waste-to-energy process
for sewage sludge, converting organic waste into liquid biocrude oil that 4.4. Reaction mechanism
can be upgraded to transportation fuels (Hu et al., 2021). Therefore, it is
necessary to evaluate the fate of PFAS in each phase produced during the To date, the reaction mechanism studies of PFAS and its alternatives
HTL process. Yu et al. (2020) also treated two PFAAs (PFOA and PFOS) in subcritical water mainly focus on a small number of pure compounds,
and three PFAA precursors (8:2 FTUCA, 7:3 FTCA, and 8:2 FTS) by HTL emphasizing most recalcitrant compounds, such as PFOS and F–53B.
in sludge and found that the PFAS destruction in sludge was significantly
better than that in a pure aqueous solution. While there was almost no 4.4.1. Degradation mechanism of PFOS
PFOS removal in pure water, ~35%–45% removal was observed in In the subcritical hydrothermal alkaline reaction conditions with
sludge at the same reaction conditions. The authors suggested that the NaOH, Wu et al. (2019) found the presence of PFOA and short-chain
improvement may be due to the presence of catalytic metal ions or PFCAs (PFHxA and PFPeA) as intermediates of PFOS degradation. The
mineral solids in the sludge. Comparing HTL liquid and solid-phase authors suggest that the reaction of PFOS is initiated and facilitated by

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J. Li et al. Chemosphere 307 (2022) 135888

OH− with a series of nucleophilic substitution and decarboxylation re­ negative environmental effects, including human health, ecological
actions. They reason that OH− ion replaces the sulfonate group first to quality, and climate change. The emissions of CHF3 contributed to
produce unstable alcohols (the rate-limiting step). Subsequently, F− is global warming to some extent, and the treatment of fluorine-containing
released from the unstable alcohol and ketone intermediates. Due to the liquid products and solid residue impacted terrestrial and aquatic eco­
hydration of ketones, F− is released, and PFOA is formed. Further toxicity. The authors noted that the ecological influence accounted for
decarboxylation of PFOA occurs, and it gradually produces PFHxA and less than 10% compared with human health, climate change, and
PFPeA as intermediates and releases more F- until the fluorocarbon resource allocation.
chain is degraded completely (Wu et al., 2019), as shown in Fig. 3. It is essential to optimize the subcritical HT system to reduce the
Hao et al. (2021) also proposed that OH- can undergo nucleophilic negative impact on the environment. An alkaline amendment can
substitution reactions with PFOS, replacing the F- connected to the C–F eliminate the emission of CHF3 and reduce the reaction residence time.
bond, forming a highly unstable hydroxylated structure, as shown in However, as summarized above, all experiments (so far) have been
Fig. 4. Then the cleavage between C–C bond occurs, generating CO2. carried out in batch reactors. Batch reactors are limited by low pro­
This reaction pathway differs significantly from Wu et al. (2019), cessing capacity, high operation cost, long preheat times, and frequent
showing a clear need for a more detailed understanding of the behavior heating cycles (Xu et al., 2015a). Alternatively, continuous flow reactors
of intermediates in the liquid and gas phase products during the could provide significantly higher throughput, reducing the operation
degradation of PFOS. Additionally, there is a diverse and complex ma­ cost. The continuous flow reactor could also be a better tool for studying
trix of compounds in the PFAS-containing waste, and exploring the the kinetic mechanism (Pinkard et al., 2019c). E.g., Pinkard et al. uti­
interaction mechanism between different PFAS is also required. lized a lab-scale continuous flow reactor with in-situ Raman spectros­
copy to study the decomposition of DMMP (Pinkard et al., 2020b) and
4.4.2. Degradation mechanism of F-53B formic acid (Pinkard et al., 2019b) in sub- and supercritical water. A
The proposed degradation mechanism for ether-PFAS, such as similar approach would benefit PFAS decomposition studies as the un­
F–53B, has a different initiation step from PFOS mechanisms; the certainties with temporal temperature profile during heating and cool­
degradation of F–53B is initiated by substituting terminal Cl with H. ing would be eliminated.
Then, the oxygen bridge (C–O bond) breaks to form ⋅OC2F4SO3- and Lab-scale continuous-flow HT or HALT experiments would simulate
HC6F12. The carboxyl acid is progressively generated by the continuous a more realistic operational scenario and provide the basis for the scale-
defluorination of the terminal carbon, and HC4F8⋅, as well as up of HT or HALT technology. Overall system design can incorporate
HOOC2F2SO3- appear as intermediates in the liquid products. Finally, recuperative heat exchangers, allowing heat recovery and significantly
the F–53B is fully mineralized into F− , CO2, and SO2−
3 , as shown in Fig. 5 decreasing energy demand for PFAS destruction (Strathmann et al.,
(Bao et al., 2019; Zhang et al., 2021a). 2020). Further process optimization efforts should be explored and
implemented as HT and HALT processing approach full-scale
implementation.
4.5. Environmental impact assessment
5. Degradation of PFAS in supercritical water
The destruction and mineralization of PFAS, its alternatives, and
PFAS-containing waste in subcritical water have been successfully To date, only a few publications have reported SCWO treatment of
demonstrated. In order to implement this technology, it is necessary to PFAS and its alternatives to verify the effectiveness, as shown in Table 2.
assess the environmental impact and decrease the reagent consumption As with subcritical water research, most experiments have been per­
of treating PFAS. Zhu et al. (2013) performed a life cycle assessment of formed in batch reactors, with the notable exception of the report by
treating PFOS with iron powder in subcritical water at 350 ◦ C for 6 h in a Krause et al., describing a round-robin study of diluted AFFF destruction
batch reactor. Results show that the fuel consumption for preheating and in three different SCWO reactors (Krause et al., 2022) and a
keeping the reactor at 350 ◦ C, 23.3 MPa, for 6 h contributed >99% of the

Fig. 3. Proposed reaction pathway of PFOS in the HALT conditions (Wu et al., 2019).

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J. Li et al. Chemosphere 307 (2022) 135888

Fig. 4. Additional proposed reaction pathway of PFOS in the HALT conditions (Hao et al., 2021).

380 ◦ C for 6 h exposure. These levels were better than the reactions in
subcritical water—adding Fe powder greatly enhanced the destruction
of PFHS. The fluoride yield was increased by 5.13x, only 5.23% PFHS
remained in the effluent, and the levels of H2, CO2, and CF3H increased
in the gas products. The authors suggested that the H2 was formed due to
the reaction between Fe and SCW, while the CF3H was produced from
the interaction of CF2 and HF. The H2 production, PFHS destruction, and
F− formation all had a positive relationship with the BET surface area of
Fe, indicating that the reaction mainly occurred on the surface of the Fe
particles (Hori et al., 2008). The treatment of [CF2(CF2SO2)2N]- with Ar
at 380 ◦ C, 22.3 MPa for 6 h was also studied. Only 14.4% removal of
[CF2(CF2SO2)2N]- and 16% defluorination were achieved. Substituting
O2 for Ar did not change the results. However, adding Fe into the su­
percritical water with Ar yielded complete degradation of
[CF2(CF2SO2)2N]- and 74.2% yield of F− at 380 ◦ C for 6 h exposure
(Horia et al., 2012). Compared with Fe, the FeO addition enhanced the
degradation of –O3SC3F6 SO3- in supercritical water with Ar, leading to
100% removal of –O3SC3F6 SO3- and 89% yield of F− at 380 ◦ C for 6 h,
while only 77% of F− was produced with Fe under the same conditions.
The difference between Fe or FeO addition was minor for degradation of
C3F7SO−3 , and the overall conversion efficiency of C3F7SO−3 was lower
than that of –O3SC3F6 SO3- (Hori et al., 2015).
Although some PFAS alternatives destruction in supercritical water
has been studied by Hori et al. (Horia et al., 2012; Hori et al., 2015; Hori
and Yokota, 2015), the study was limited to the reaction temperature
just slightly above the critical point and the low oxidant concentration.
As PFOS being one of the most refractory compounds, Pinkard et al.
(2021) studied its destruction in a batch SCWO reactor with higher re­
action temperatures and found that 70% of PFOS was destroyed and
~78% F− was obtained at 500 ◦ C, 1 h exposure with excessive H2O2. The
reason PFOS degradation efficiency was lower than the F− yield might
be due to the adsorption of unreacted PFOS on the reactor walls or losses
of unreacted PFAS during the LCMS sample preparation. Increasing re­
action temperature had a more significant impact on the degradation of
PFOS than extending the residence time, indicating that temperature is
the key reaction parameter for SCWO processing. Pinkard et al. (2021)
proposed that the hydroxyl (•OH) and hydroperoxyl (•HO2) radicals
produced by H2O2 in supercritical water are likely to attack the sulfonate
group first, then break the C–C bonds. HF and CO2 were observed as the
only final products. However, the intermediates and reaction pathways
of PFOS in the SCWO process have not been fully elucidated; this is
illustarted in Fig. 6.
Recently, Krause et al. (2022) analyzed the results of a
proof-of-concept round-robin study that used three similar AFFF feed­
stocks, which mainly contain short-chain and long-chain PFAS,
including PFOS and PFOA. The diluted stock solutions were treated in
three different continuous SCWO reaction systems (Battelle, Aquarden
Technologies, and 374Water) to assess the efficacy of SCWO technology.
Fig. 5. Proposed reaction pathway of F–53B in subcritical water (Zhang Results showed >99.9% chemical oxygen demand (COD) removal effi­
et al., 2021a). ciency and total PFAS degradation, 99% PFOA and PFOS removal were
achieved at T = 590–595 ◦ C, residence times 6–60 s. In the remaining
proof-of-concept case study by McDonough et al. (2022) (see Table 3). PFAS found in the effluent, the PFOS fraction was >70%, and other
compounds like PFHxS, PFBS, PFPeA, or PFOA were also present in
small amounts in the effluent. The alkaline buffer, KOH, was added to
5.1. Degradation effect of PFAS and its alternatives the influent (pH = 12.75), and effluent was measured at pH = 3.26,
suggesting that HF was formed during the SCWO treatment. The fluoride
Hori et al. first studied the degradation of PFAS alternatives in su­ concentration increased ~34x in the liquid products, indicating the
percritical water (Horia et al., 2012; Hori et al., 2015; Hori and Yokota, effective mineralization of organofluorides. Although the destruction
2015), reporting 30.2% PFHS degradation and 9.18% defluorination at

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 J. Li et al.
Table 2
The influence of additives on the degradation of various PFAS in subcritical water compared with the results from the same article.
Substances T P t Additive PFAS Additive Reactor PFAS Removal Defluorination Defluorination Reference
(◦ C) (MPa) (h) concentration concentration type Removal improvements (%) (%) improvement (%)
efficiency (%)

PFSAs mixture 300 2 KOH 2000 μg/L 1 mol batch 85.9 ± 1.2 75.9 – – Zhang et al.
reactor (2020)
F–53B (in cattail 300 – 2 Ca(OH)2 500 ng/L 5 mM batch ~100 87.08 – – Zhang et al.
roots) reactor (2021a)
AFFF 350 1.5 NaOH 5M batch ~100 – 98 ~90 Hao et al. (2021)
reactor
PFOS 350 16.5 1.5 NaOH 50 mg/L 2.5 M batch ~100 ~100 ＞80 ~80 Wu et al. (2019)
reactor
PFOS 350 16.5 1.5 NaOH4 50 mg/L 1M batch ＞80 ~80 ＞70 ~70 Wu et al. (2019)
reactor
AFFF 350 20.7 2 NaOH 3200 mg/L 5M batch 99.95 0.07 120.5 120.5 Pinkard (2022)
reactor
PFOS 350 23.3 6 Fe 118.8 mg/L 9.60 mM batch 99.46 89.76 51.4 51.24 Hori et al. (2006)
reactor
PFHS 350 21.9 6 Fe 1.46 μM 9.61 mM batch 100 82.4 33 29.73 Hori et al. (2008)
reactor
C2F5OC2F4SO−3 350 6 O2 14.6 μM 0.65 MPa batch 40.5 – 36.6 – Hori et al. (2009)
reactor
C2F5OC2F4SO−3 350 6 Ar 14.6 μM 0.65 MPa batch 41.4 – 21.8 – Hori et al. (2009)
reactor
9

C3F7OC2F4SO−3 350 6 O2 14.4 μM 0.65 MPa batch 56.4 – 49.4 – Hori et al. (2009)
reactor
[CF2(CF2SO2)2N]− 350 17.2 6 Ar + Fe 1.46 mM 0.60 MPa/9.60 batch 99.9 96.5 63.5 62.6 Horia et al.
mM reactor (2012)
[CF2(CF2SO2)2N] −
350 15.7 6 Ar + Zn 1.46 mM 0.60 MPa/9.60 batch 67.8 64.4 2.02 1.12 Horia et al.
mM reactor (2012)
[CF2(CF2SO2)2N]− 350 16.6 6 Ar + Cu 1.46 mM 0.60 MPa/9.60 batch 15.1 11.7 29.7 28.8 Horia et al.
mM reactor (2012)
-
O3SC3F6SO−3 350 17.4 6 Ar + Fe 14.7 μM 0.60 MPa/9.60 batch ~100 99 70 ± 3 67 Hori et al. (2015)
mM reactor
C3F7SO−3 350 16.8 6 Ar + Fe 14.7 μM 0.60 MPa/9.60 batch 81 78 23 23 Hori et al. (2015)
mM reactor
-
O3SC3F6SO−3 350 17.5 6 Ar + 14.5 μM 0.60 MPa/9.60 batch 62 ± 1 61 54 ± 3 51 Hori et al. (2015)
FeO mM reactor
C3F7SO−3 350 17.4 6 Ar + 14.9 μM 0.60 MPa/9.60 batch 11 8 14 14 Hori et al. (2015)
FeO mM reactor
[(C6H5)3S][CF3SO3] 373 21.6 6 O2 9.94 μM 4.99 mM batch 100 – 93.6 – Hori and Yokota
reactor (2015)
[(C6H5)3S][CF3SO3] 373 22.8 6 Ar + Fe 9.94 μM 4.99 mM/9.60 batch 100 – 74.4 – Hori and Yokota

Chemosphere 307 (2022) 135888

mM reactor (2015)
CF3SO3K 373 21.6 6 O2 10.1 μM 4.99 mM batch 77.1 – 57.1 – Hori and Yokota
reactor (2015)
CF3SO3K 373 22.1 6 Ar + Fe 10.1 μM 4.99 mM/9.60 batch 52.5 – 19.7 – Hori and Yokota
mM reactor (2015)
J. Li et al. Chemosphere 307 (2022) 135888

Table 3
The degradation of PFAS and its alternatives in supercritical water.
Substances T P t Additive PFAs Additive Reactor type PFAs Removal Defluorination Reference
(◦ C) （MPa） (h) concentration concentration efficiency (%) (%)

[CF2(CF2SO2)2N]− 383 22.7 6 O2 1.46 mM 0.60 MPa/9.60 batch reactor 17.6 10.4 Horia et al.
mM (2012)
[CF2(CF2SO2)2N] −
380 22.3 6 Ar + Fe 14.9 μM 0.60 MPa/9.60 batch reactor 99.9 74.2 Horia et al.
mM (2012)
-
O3SC3F6SO−3 380 22.7 6 Ar + 14.9 μM 0.60 MPa/9.60 batch reactor ~100 89 Hori et al.
FeO mM (2015)
C3H7SO−3 380 22.7 18 Ar + 14.9 μM 0.60 MPa/9.60 batch reactor 70 58 Hori et al.
FeO mM (2015)
PFHS 380 23.8 6 – 5.93 μM – batch reactor 30.2 9.18 Hori et al.
(2008)
PFHS 380 26.4 6 Fe 5.93 μM 9.61 mM batch reactor 94.77 47.1 Hori et al.
(2008)
PFOS 500 ＞22.1 1 H2O2 excessive batch reactor 70 78.2 Pinkard et al.
(2021)
AFFF (PFAS 595 ＞22.1 8s air 243,000 μg/L excessive continuous 99.996 – Krause et al.
mixture) tubular reactor (2022)
AFFF (PFAS 590 24 60s air 38,714.5 μg/L excessive continuous 99.37 – Krause et al.
mixture) tubular reactor (2022)
AFFF (PFAS 590 ＞22.1 10s 40,454 μg/L excessive continuous 99.979 – Krause et al.
mixture) tubular reactor (2022)
AFFF (PFAS 650 22 11s air excess 11% continuous ＞99.999 62.6 McDonough
mixture) tubular reactor et al. (2022)

consideration. The current literature does not provide exact numbers on

the energy required for treatment of PFAS per mass of PFAS treated
basis. The ambiguity hampers comparisons between the costs of
different SCWO reactors and other technologies with PFAS stock con­
centration and composition, different desired levels of destruction or
defluorination, and other boundary conditions required for techno-
economic analysis and comparisons. For example, PFOA treatment
does not require temperatures above 400 ◦ C, while the destruction of a
Fig. 6. Proposed simplified reaction pathway of PFOS by SCWO treatment
more recalcitrant PFOS requires the operation of the SCWO reactor at T
(Pinkard et al., 2021).
> 600 ◦ C. Thus, most authors report overall energy consumption for
reactor operation and do not include defluorination or destruction ef­
efficiency of PFAS was high, additional effluent polishing treatment with
ficiency metrics in the energy consumption analysis. For example,
reverse osmosis (RO) or similar may be needed to remove residual PFAS
Pinkard et al. (2021) calculated that the energy requirements for
from the effluent (Krause et al., 2022), depending on local, state, or
treating PFOS in a batch reactor were ~3060 kJ/kg for heating water
federal discharge guidelines for PFAS-impacted liquids. Some of these
from 20 ◦ C to the supercritical state at 500 ◦ C. In a continuous flow
discharge standards are currently being established. Gaseous reaction
system, the analysis is typically based on the throughput of the system
products should also be studied and verified to meet the emission
basis, e.g., kg/h. McDonough et al. (2022) evaluated the electric energy
standards (Winchell et al., 2021; Krause et al., 2022).
consumption of the pilot-scale SCWO system during the treatment of
Recently, McDonough et al. (2022) reported a proof-of-concept case
AFFF at 1.0 × 105–1.1 × 105 kW h/kg PFAS; the energy consumption
study for a pilot-scale SCWO system at General Atomics, Inc. The feed­
included diesel fuel and energy to operate the air compressor and the
stock was a PFOS-dominant AFFF solution: 94.7% of PFHxS and PFOS
transfer pumps. The cost to operate the pilot scale SCWO was reasonable
and 5.3% of 10 other C4 to C8 PFCAs and C4 to C10 PFSAs. The SCWO
compared to electrochemical oxidation (Soriano et al., 2017), sonolysis
reactor was operated at 650 ◦ C, 22 MPa, with 11% excess oxygen and
(Cheng et al., 2010), and nonthermal plasma (Singh et al., 2019b),
residence times of 10–11 s. Greater than 99.999% destruction effi­
technologies whose electric energy per mass is in the range of (1.9 × 101
ciencies were observed for all 12 PFAAs, while PFOS had the highest
~ 1.5 × 107 kW h/kg); however, these systems may be at lower tech­
removal efficiency of 99.99996%. PFDS showed the lowest removal
nology readiness levels. The energy consumption for the hydrothermal
efficiency of 99.92958%. About 62.6% defluorination was achieved in
alkaline treatment (6.1 × 103 kW h/kg) in a batch reactor in subcritical
the liquid effluent. It was suggested that unrecovered fluorine might be
water (350 ◦ C, ＜ 20 MPa) (Wu et al., 2019) is lower than the General
present in the steam due to the reaction between the added quench/­
Atomics’ pilot-scale SCWO system, which is likely due to the high energy
NaOH with the produced HF. The total fraction of short-chain PFAS
demands for transition across the pseudo-phase change from subcritical
(ΣPFAASC) increased from 3.8% in the influent to 50.8% in the effluent,
water to supercritical water. Operating at high PFAS concentrations can
indicating that long-chain PFAS (ΣPFAALC) that were transformed into
also achieve better system economics.
ΣPFAASC even under aggressive SCWO reaction conditions (McDonough
SCWO is a promising technology for the destruction of complex
et al., 2022). Though the details of the pilot-scale reactor were not
PFAS-containing wastes. To reach commercial large-scale application
disclosed, it is possible that extended residence time and a larger reac­
operation with other organic byproducts such as alcohols, ketones in the
tion zone within the SCWO reactor may further reduce the PFAS levels in
liquid and gas effluents should be considered (Thomas et al., 2020) as
the effluent. A more flexible lab-scale reactor would be advantageous for
the energetic feedstock would affect the reactor temperature and tem­
parametric studies and process optimization.
perature distribution in the reactor, possibly triggering the transition
from flameless SCWO reaction to the onset of hydrothermal flame
5.2. Energy evaluation of SCWO systems (Serikawa et al., 2002; Reddy et al., 2017; Hicks et al., 2019; Moore
et al., 2021). Most practical SCWO systems operate with the liquid hy­
In scaling up SCWO systems, energy consumption is a key drocarbons used as pilot fuels to ignite and sustain the reaction; thus,

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J. Li et al. Chemosphere 307 (2022) 135888

future work should be focused not only on understanding the PFAS ●In the scale-up of SCWO systems, inorganic salt deposition and
degradation mechanisms but also on SCWO kinetics and the interaction material corrosion under high-temperature and high-pressure con­
between hydrocarbon and fluorocarbon chemistries. Additionally, ditions should be considered, which will influence the security and
PFAS-containing wastes such as sludge and industrial wastewater often reliability of the entire SCWO system. Specific to the treatment of
contain inorganic salts, which precipitate in SCWO environments due to concentrated PFAS, high levels of HF in the effluent must be
the non-polar properties of supercritical water leading to corrosion and addressed. To improve the service performance of the reactor ma­
plugging of the reactors (Hodes et al., 2004; Marrone et al., 2004; Xu terial and to reduce the operating cost of the whole system, enhanced
et al., 2015b). It is also known that HF is produced in situ during SCWO SCWO technologies, such as co-oxidation, catalytic oxidation, and
processing of PFAS, which can corrode reactor materials. Therefore, in staged oxidation, can be considered to improve the removal effi­
the reactor design, it is necessary to avoid salt deposition and mitigate ciency of PFAS while reducing the reaction temperature.
material corrosion in the SCWO processing of PFAS. In addition, the ●In the treatment of PFAS-contaminated streams, co-contaminants
economic optimization, including investment and operating costs, must be considered. For example, the reduction of PFAS in bio­
environmental emission impact, and other life cycle analyses of the crude during the HTL treatment of sewage sludge should be studied.
SCWO system also should be studied further to provide evidence and In addition to PFAS and fluoride concentration in the liquid effluents,
support for the commercial application. gas and solid products should satisfy emission standards for
subcritical or supercritical treatment.
6. Conclusion and future outlook ● The PFAS makeup in wastewater or sludge is complex and diverse;
thus, understanding the interaction between multiple PFAS and co-
This review summarizes the state-of-the-art research in the degra­ contaminants is essential for HT or SCWO process.
dation of PFAS, PFAS precursors, PFAS alternatives, and PFAS- ●For both HT and SCWO technology, based on a batch or continuous
containing waste in subcritical and supercritical water, discussing the reaction system, a systematic life-cycle assessment should be
effect of reaction parameters such as temperature, residence time, considered to improve the negative impact on the environment
amendments type and concentration. The PFSAs, PFCAs in the liquid before industrialization, including energy use, resource consump­
effluent degraded completely in subcritical or supercritical water, while tion, pollutant emissions, etc. Here, proper techno-economic analysis
destruction (>99%) and defluorination (>50%) of PFSAs require can guide technology viability.
amendments such as NaOH or Fe powder even at T = 350 ◦ C with
exposure time 1.5–6 h in batch reactor systems. Continuous HT or HALT Credit author statement
systems have not been demonstrated. SCWO processing in batch reactors
is limited to material properties consideration and yielded ~70% PFOS Jianna Li: Conceptualization, Writing - original draft, Writing – re­
destruction at 500 ◦ C; however, continuous flow reactors can operate at view & editing. Brian Pinkard: review & editing. Shuzhong Wang:
high temperatures, operating at 590–650 ◦ C yielded >99% destruction review & editing. Igor Novosselov: Conceptualization, Supervision,
of all PFAS at residence times <60 s. Funding acquisition, Writing - Review & Editing.
Based on the scientific literature at the time of this writing, we can
provide the following comments on the HT and SCWO technologies for Declaration of competing interest
the treatment of PFAS and suggest the directions for future work:
The authors declare the following financial interests/personal re­
● In addition to PFAS, the treatment of PFAS precursors and PFAS al­ lationships which may be considered as potential competing interests:
ternatives by HT, HALT or SCWO technologies should be further BRP is a significant shareholder in Aquagga, Inc., a startup company
studied to understand their stability, degradation rates and routes. commercializing hydrothermal PFAS destruction technology.
●The studies of PFAS degradation in subcritical water are limited to
batch reactors with long residence times (>1.5 h) and aim to eluci­ Data availability
date reaction kinetics and the role of the amendments. Moving to
large-scale implementation, research in continuous HT or HALT No data was used for the research described in the article.
systems should be performed. Future studies should not be limited to
pure PFAS but also include real-world PFAS-containing waste, as the Acknowledgments
matrix effects have been reported in the literature. Opportunities for
heat recovery and process intensification should be considered in Jianna Li is supported by Innovative Leading Talents Scholarship
future research. For example, continuous HT and HALT processes from Xi’an Jiaotong University.
should be explored to reduce energy requirements and optimize
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