Chemosphere 286 (2022) 131685

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Thermal decomposition of perfluorinated carboxylic acids: Kinetic model

and theoretical requirements for PFAS incineration
Mohammednoor Altarawneh a, *, Mansour H. Almatarneh b, Bogdan Z. Dlugogorski c, *
a
United Arab Emirates University, Department of Chemical and Petroleum Engineering, Al-Ain, 15551, United Arab Emirates
b
University of Jordan, Department of Chemistry, Amman, 11942, Jordan
c
Charles Darwin University, Energy and Resources Institute, Darwin, NT, 0909, Australia

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

• The study presents a kinetic model on

thermal decomposition of a PFOA model
compound.
• Major initiation routes include subse­
quent elimination of HF/CO and direct
ejection of HF/CO2.
• Profiles of decomposition products
illustrate formation of several CnFm
species.
• Perfluorinated cyclic compounds arise
from ring-closure of singlet-diradical
structures.

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

Handling editor: Derek Muir Thermal decomposition of high-fluorine content PFAS streams for the disposal of old generations of concentrates
of firefighting foams, exhausted ion-exchanged resins and granular activated carbon, constitutes the preferred
Keywords: method for destruction of these materials. This contribution studies the thermal transformation of per­
Fluorotelomer carboxylic acids fluoropentanoic acid (C4F9C(O)OH, PFPA), as a model PFAS species, in gas-phase reactions over broad ranges of
Reaction mechanisms
temperature and residence time, which characterise incinerators and cement kilns. Our focus is only on gas-phase
Pyrolysis
reactions, to formulate a gas-phase submodel that, in future, could be used in comprehensive simulation of
thermal destruction of PFAS; such comprehensive models will need to comprise fluorine mineralisation on flyash
and in clinker material. Our submodel consists of 56 reactions and 45 species, and includes new pathways that
cover the initial decomposition channels of PFPA, including those that lead to the formation of the n-C4F9 radical,
the abstraction of hydroxyl H by O/H radicals, the fragmentation of the n-C4F9 radical, reactions between HF and
perfluoropentanoic acid, as well as between HF and heptafluorobutanoyl fluoride (C3F7COF), and the cyclisation
reactions. The model illustrates the formation of a wide spectrum of small CnFm and CnHFm compounds in the
temperature window of 800–1500 K, 2 and 25 s residence time in a plug flow reactor, providing theoretical
estimates for the operating conditions of PFAS thermal destruction systems. The initiation reactions involve the
loss of HF and formation of the transition α-lactone species that converts to C3F7COF, with C4F9C(O)OH
completely decomposed at 1020 K for 2 s residence time. At 1500 K, we predict the emission of ꞉CF2 (biradical
difluorocarbene), HF, CO2, CO, CF4, C2F6, and C2F4, but at < 1400 K, we note the formation of 1H-nonafluoro­
butane (C4HF9), phosgene (COF2), and heptafluorobutanoyl fluoride (C3F7COF), with 1-C4F8, 2-C4F8 and C3HF7
persisting to 1500 K. We demonstrate that, the gas-phase pyrolysis processes by themselves convert PFAS to HF

* Corresponding authors.
E-mail addresses: mn.altarawneh@uaeu.ac.ae (M. Altarawneh), bogdan.dlugogorski@cdu.edu.au (B.Z. Dlugogorski).

https://doi.org/10.1016/j.chemosphere.2021.131685
Received 27 March 2021; Received in revised form 21 July 2021; Accepted 25 July 2021
Available online 29 July 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
M. Altarawneh et al. Chemosphere 286 (2022) 131685

and short-chain fluorocarbons, with similar product distribution for short (2 s) and long (25 s) residence times, as
long as the treatment temperature exceeds 1500 K. These residence times reflect those encountered in in­
cinerators and cement kilns, respectively. Thermokinetic and mechanistic insights revealed herein shall assist to
innovate PFAS thermal disposal technologies, and, from a fundamental perspective, to accelerate research
progress in modelling of gas/solid reactions that mineralise PFAS-derived fluorine.

1. Introduction
The most common scenarios of remediation of PFAS (per and poly­
fluoroalkyl substances) include the destruction of concentrates of PFAS-
based firefighting foams and sewage sludge as well as ion-exchange
resins (IER), granulated activated carbon (GAC) and similar materials
loaded with adsorbed PFAS extracted from contaminated water (Garg
et al., 2021; Horst et al., 2021; Winchell et al., 2021). The destruction
technologies used for this purpose must be versatile and non-specific to
decompose a large variety of PFAS chemicals and mineralise their
fluorine content, such as in CaF2 or as F‾ in aqueous phase (Wang et al.,
2015; Hori et al., 2021; Riedel et al., 2021). For example, the so-called
Light Water formulations of firefighting foams, produced by the 3M
Company until 2002, accounted for 55% of the total amount of the
stored concentrates in 2004 in the USA (Darwin, 2004). Light Water
typically contained two classes of fluorosurfactants: (i) filmers that in
post-1970 formulations consisted mainly of potassium PFOS (per­
fluorooctane sulfonate) added to the so-called 3% concentrates at levels
of between 1 and 1.84 %, as active matter; and, (ii) foamers, based on
the two species illustrated in Scheme 1, at levels of between 2.56 and
2.74% (active matter) (Alm and Stern, 1992).
In practice, the formulations produced by the 3M Company
comprised many impurities and byproduct chemicals because of the
non-selective operation of the Simons electrofluorination cell and the
subsequent synthesis steps that included no purification of target species
(Dlugogorski and Schaefer, 2021). Hundreds of fluorosurfactant species
detected both in the environment and in the concentrates represent the
legacy of the Light Water concentrates (Backe et al., 2013; Barzen-­
Hanson et al., 2017). One such group of byproducts, from the Simons
cell and the subsequent hydrolysis, comprises potassium PFOA (per­
fluorooctanoate) and its homologues. (In this article, PFOA denotes both
perfluorooctanoate and perfluorooctanoic acid and, similarly, for other
acidic PFAS.) While not added on purpose to the post-1970 formulations
of Light Water, these species represented about 2% of the entire PFAS
load in the concentrates (Dlugogorski and Schaefer, 2021). PFOA also
appeared in fluorotelomer-based concentrates of the pre-2015 fire­
fighting foams, with fluorotelomer technology used by the competitors
of the 3M Company. The fluorotelomer based formulations accounted
for the remaining 45% of the stored concentrates (Darwin, 2004).
Apparently, PFOA was used as a synthesis aid in the production of flu­
orotelomer surfactants. Thus, destruction of concentrates of firefighting
foams involves treatment of significant amounts of PFOA and its ho­
mologues, making one of these species a convenient molecule to
investigate in mechanistic studies, as we do in the present work. The
same reasoning applies to the thermal disposal of IER and GAC that may
contain high loads of PFOA, say from the clean-up of ground water
contaminated with products of decomposition of ammonium per­
fluorooctanoate used in manufacturing of fluoropolymers (Schroeder
et al., 2021).
The total organic fluorine (TOF) of the most common concentrates of
defence-grade Light Water corresponded to between 1.8 and 2.1%. This
can be compared with 0.8–1.2% of TOF present in the concentrates
based on fluorotelomer surfactants, produced by the competitors of the
3M Company for the military market (Snow et al., 2017). Concentrates
of PFAS foams prepared for the civilian applications, to pass UL 162 and
EN 1568:3 standards, typically comprise around 0.3–0.4% TOF (Dubocq
et al., 2020; Dlugogorski and Schaefer, 2021). Treatment processes to
handle concentrates of firefighting foams must, therefore, be capable of
destruction and mineralisation of the very high abundance of organic
fluorine in these materials. At present, only the combustion-based
destruction processes, especially cement kilns, can effectively reme­
diate such concentrated streams of PFAS (Holmes and Klein, 2020;
Winchell et al., 2021). Cement kilns provide long gas residence time that
typically exceed 10 s at temperatures above 1700 K, with clinker min­
eralising the fluorine (Meystre and Silva, 2015; Holmes and Klein,
2020). The latter authors also reported the destruction and removal
efficiency of PFOS, PFOA and PFHxS (perfluorohexanesulfonic aicd/­
sulfonate) in cement kilns to be better than 99.9993%. In comparison,
incinerators operate under a range of conditions that depend on the
application and technology, with multiple hearth furnaces and fluidised
bed furnaces used in sewage sludge incineration, and moving grate,
rotary kiln and liquid injection incinerators more common for handling
municipal and hazardous waste (Winchell et al., 2021). Except for rotary
kilns and liquid injection, these systems do not operate at temperatures
higher than 1300 K, typically below 1150 K, with the residence time of 2
s for moving grade and several seconds for multiple hearts and fluidised
bed installations (Winchell et al., 2021). This comparison of the vari­
ability in the operating conditions of incinerators has prompted us to

Scheme 1. Examples of foamers used by the 3M Company in its formulations of PFOS foams (Dlugogorski and Schaefer, 2021); Light Water contained hundreds of
congeners of these chemicals.

2
M. Altarawneh et al.
develop the first comprehensive submodel of the gas-phase reactions
that occur in incinerators to provide the theoretical estimates of PFAS
destruction and mineralisation as function of the operating conditions.
While, in this work, we execute the submodel under the pyrolysis con­
ditions, the submodel can accept concentrations of moisture and oxygen
typically encountered in practical systems (Taylor et al., 2014).
Detailed mechanistic studies on degradation of PFAS compounds
have generally focused on catalysed reactions in which calcium hy­
droxide (Wang et al., 2015), alumina (Wang et al., 2019) and hematite
(Gao and Chorover, 2012) effectively destroy the pollutants at temper­
atures as low as 670 K. The merits of the catalyst-assisted process are the
subsequent capture of HF, leading to fluorination of the metal oxide, and
the release of water. Unfortunately, at this temperature, the capture
operates only at about 80% efficiency, with the thermal treatment
emitting short-chair fluorocarbons (Wang et al., 2015). Measured XRD
patterns confirm the generation of CaF2 phases upon reaction of PFOS
with Ca(OH)2 across the temperature window of 570–1170 K (Wang
et al., 2015). Conversion of metal oxides into their metal fluorides was
suggested to take place via the interaction of the metal oxide (or hy­
droxide) with the degradation fragments of PFAS rather than with the
PFAS molecule itself; namely, with a wide array of CnFm radicals.
Depending on the operational temperature, partial or full mineralisation
of fluorine follows the initial decomposition of the parent PFAS molecule
(Wang et al., 2012, 2015, 2019).
Along the same line of enquiry, other investigations addressed the
thermal decomposition of PFOA. A recent study by Xiao et al. (2020)
investigated thermal decomposition of different PFAS compounds with a
varying chain length of the CF2 groups over spent granular activated
carbon (GAC). The mass spectra revealed both the sublimation of PFOA
from GAC and its partial decomposition at temperatures as low as 473 K.
Stockenhuber et al. (2019) reported the formation of
perfluoro-1-heptene (1-C7F14), 1H-perfluorohexane (C6HF13, 1H-tride­
cafluorohexane) and 1H-perfluoroheptane (C7HF15, 1H-pentadecafluor­
oheptane) from the thermal degradation of PFOA under an inert N2
atmosphere in a gas-phase process between 300 and 750 ◦ C for long
residence time of up to 46 s. The FT-IR spectra highlighted the formation
of HF, CO, CO2. Production of HF was shown to be sensitive to the
applied residence time, in which longer residence time suppressed the
generation of HF, presumably due to its consumption in the hydro­
fluorination reaction: HF + alkene → fluoroalkane. The temperature for
the onset of the decomposition of PFOA, reported by Stockenhuber et al.
(2019), fall below the expected temperature for the gas-phase initiation
reaction. This indicates promotion of the decomposition process on the
walls of their reactor. Krusic et al. (2005) studied the kinetics of the
thermolysis of PFOA in quartz ampoules, reporting 1H-perfluoroheptane
and perfluoro-1-heptene as major and minor products, respectively.
Adding crushed quartz significantly accelerated the decomposition of
PFOA, indicating a strong catalytic effect, although the nature of this
effect was different for quartz and borosilicate surfaces. Finally, within a
different context of the thermal degradation of PFOA in aqueous solu­
tions, as function of temperature and pH, Liu et al. (2017) also identified
perfluoro-1-heptene, as the only species that formed under their
experimental conditions. In summary, all experimental results on the
decomposition of PFOA suggest that the process starts with the emission
of HF from the head group and leads to the initial formation of 1H-per­
fluoroheptane and perfluoro-1-heptene (Krusic et al., 2005; Liu et al.,
2017; Stockenhuber et al., 2019; Xiao et al., 2020). However, the
mechanistic details of the process remain unknown, and there is no
comprehensive kinetic model to predict the yields of the decomposition
products.
In a previous theoretical density functional theory (DFT) study, we
illustrated reaction and activation energies for pathways operating in
the initial decomposition of perfluorobutanoic acid (C3F7C(O)OH), as a
representative model compound for the degradation of PFOA (Altar­
awneh, 2012). Among several opening channels, we found the elimi­
nation of HF leading to a α-lactone intermediate to dominate the initial
3
Chemosphere 286 (2022) 131685
decomposition of the perfluorobutanoic acid, similarly to the formation
of a transitional species of α-sultone that may arise in the pyrolysis of
PFOS (Altarawneh, 2021; Weber et al., 2021), but is too unstable to be
observed experimentally. Computed reaction rate constants established
the fate of the initially-formed α-lactone intermediate to be dominated
by two temperature-dependent competing channels affording penta­
fluoropropanoyl fluoride (and CO), and a closed-shell singlet CF3CF2CF꞉
species (and CO2). A significant hyperconjugation across the carbon
alkyl chain, induced by fluorine atoms elevated the barrier height for a
channel directly eliminating CO2 to produce 1H-perfluorobutane
(C4HF9, 1H-nonafluorobutane).
Our previous study has only focused on the initial decomposition
pathways without attempting to construct a comprehensive kinetic
model that considers channels leading to smaller CnFm-type fragments
from subsequent decomposition reactions. Crucially, the previous DFT
study (Altarawneh, 2012) did not include important parallel bimolec­
ular reactions involving HF and the H/O radical pool. These reactions
significantly contribute to the PFAS decomposition process, especially at
elevated temperatures. Likewise, the recent detection of novel per­
fluorinated cyclic compounds (Singh et al., 2019) warrants mapping out
relevant reaction pathways that were not addressed in previous in­
vestigations. In a recent study (Altarawneh, 2021), we investigated
pathways that operate in the thermal decomposition of
perfluoro-1-butanesulfonic acid (C4F9SO2OH), as a model compound of
PFOS. Our kinetic modelling (Altarawneh, 2021) demonstrated SO2 as
the major sulfur species with a noticeable contribution by SO3. The
investigated reaction pathways included hydrofluorination, hydrolysis,
and fragmentation of the alkyl chain.
To this end, this study revisits reactions operating in the initial
thermal decomposition of perfluoropentanoic acid (as a model com­
pound for PFOA and, in general, for PFAS) in light of the recent exper­
imental findings. As reported by Khan et al. (2020) for PFOS, the length
of the perfluoroalkyl chain exerts a rather minor influence on the re­
action and activation energies for the initial decomposition channels.
Similarly, the findings of Bentel et al. (2019), albeit gained in the context
of PFAS reduction by solvated electrons, demonstrated very similar
decomposition trends among perfluoroalkyl carboxylic acids (n = 2-10;
where n denotes the number of CF3 and CF2 segments that form a single
perfluoroalkyl chain). These authors also described defluorination effi­
ciency of PFCA (perfluoroalkyl carboxylic acids) in a UV-irradiated
environment to reside in the very narrow range of 49.1-59.5%
(n=2-10). As such, we anticipate that the kinetic model of the thermal
decomposition of the perfluoropentanoic acid (n = 4) will represent well
the decomposition behaviour of longer-chain PFCA (e.g., n = 7). From
these perspectives, the current investigation has four aims: i) to
construct a kinetic model that describes the decay of PFPA and forma­
tion of most important products reported in experiments; ii) to elucidate
the role of the essential bimolecular reactions induced by the abundant
HF species that form in the initial stages of the degradation of PFPA; iii)
to address the reactions that contribute to the formation of cyclic per­
fluorinated species; and, iv) to establish the theoretical (modelled) re­
quirements for destruction and mineralisation of PFAS in gas reactions
under conditions corresponding to those encountered in incinerators. It
is expected that, the mechanism developed in this contribution will
provide much improved and much more detailed understanding of the
transformation chemistry of PFAS compounds under a pyrolytic envi­
ronment, including profiles of degradation products of PFAS species,
with direct application to modelling of the remediation of these con­
taminants in practical thermal processes.
2. Computational detail
Gaussian 09 (Frisch et al., 2009) suite of programs afforded all
structural optimisations and energy calculations based on the M062X
DFT method at the polarised basis set of 6-311 + G(d,p) (Montgomery
et al., 2000). Given the size of the C7F15C(O)OH molecule, we have
M. Altarawneh et al. Chemosphere 286 (2022) 131685

found it computationally prohibitive to perform all calculations for the Table 1

PFOA molecule itself, and hence selected the perfluoropentanoic acid as Modified Arrhenius parameters fitted in the temperature range of 500–2000 K.
a model compound. Nonetheless, we report trends in bond dissociation Several of these reactions also appear in our presented kinetic model on the
enthalpies and activation enthalpies for several classes of reactions pyrolysis of a PFOS model compound (Altarawneh, 2021).
involving a varying length of perfluorinated alkyl chain of between 2 Reaction A (s− 1, cm3, n Ea Method
and 7. The meta-hybrid M062X functional performs well in attaining molecule) (kcal/
mol)
thermokinetic values for a broad spectrum of applications in organic
chemistry (Zhao and Truhlar, 2008). Our quantum chemical studies on 1 M0 (Perfluoropentanoic 1.39 × 1012 0.40 61.0 TST
halogenated (i.e., chlorinated/brominated) compounds established a acid) → M1 + HF
9
2 M0 → CO2 + HF + M6 3.59 × 10 0.97 68.8 TST
satisfactory performance of the adopted methodology in computing (Perfluoro-1-butene)
thermochemical and kinetic parameters (Altarawneh et al., 2009; 3 M0 → CO2 + M5 (1H- 6.27 × 1011 0.82 71.2 VTST
Altarawneh and Dlugogorski, 2014a, b; Altarawneh et al., 2019; Lee perfluorobutane)
et al., 2020). Likewise, Table S1 in the Supplementary Material (SM) 4 M0 → H + M4 1.29 × 1013 0.96 89.0 TST
5 M0 → COOH + M7 (n-C4F9) 1.30 × 1013 0.65 86.5 VTST
contrasts computed reaction enthalpies for a few reactions involving
6 M0 + H → H2 + M4 1.87 × 1013 0.0 16.4 TST
fluorinated species with analogous experimental values, calculated 7 M4 → M7 (n-C4F9) + CO2 1.00 × 1013 0.0 0.0 TST
based on standard enthalpies of formation (ΔfHo298.) of involved species 8 M1 → CO2 + M3 (n-C4F8) 3.11 × 1012 0.59 34.0 TST
(Afeefy et al., 2005). The average of deviations between calculated and 9 M3 → M6 1.59 × 109 1.48 43.9 TST
experimentally-based values only amounts to 1.9 kcal/mol. In their 10 M1 → CO + M2 6.88 × 1011 0.49 19.0 TST
(Heptafluorobutanoyl
study on the thermal decomposition of PFOS, Khan et al. (2020) found
fluoride)
that, values calculated by the M062X method generally reproduce 11 M5 → M6 + HF 6.18 × 109 1.2 89.0 TST
analogous figures obtained by the chemistry model G3X. Stability of 12 M7 → M6 + F 1.22 × 1012 0.54 58.3 VTST
wavefunctions of singlet-diradical species was verified. 13 M7 → CF2 + M8 (n-C3F7) 7.47 × 1013 0.86 53.7 VTST
14 M8 → F + M9 1.22 × 1012 0.54 58.3 VTST
Calculations of the intrinsic reaction coordinate (IRC) (Hratchian
15 C2F4 + C2F4 ⇆ cyc-C4F8 5.0 × 1011 0.0 23.0 TST
and Schlegel, 2005) confirmed the atomic connection between transi­ 16 C2F5 → CF3 + CF2 4.13 × 1015 0.0 60.0 TST
tion states and their associated reactants and products. We computed all 18 M7 → C2F4 + C2F5 5.10 × 1011 0.9 42.6 TST
reaction and activation enthalpies at 298.15 K. The KiSThelP package 19 M8 ⇆ C2F4 + CF3 8.66 × 1011 0.9 43.9 TST
(Canneaux et al., 2014) served to obtain the reaction rate constants 20 M17 → M9 + HF 6.18 × 109 1.2 89.0 TST
21 M0 + HF → M10 3.00 × 104 5.13 13.2 TST
based on the conventional transition state (TST). Modified Arrhenius
22 M10 → M12 + HF 3.10 × 1011 0.71 80.2 TST
parameters, k(T) = A Tn e− (Ea/(RT)), were fitted between 500 and 2000 K. 23 M10 → M6 + HF + FC(O)OH 3.17 × 1010 0.73 75.2 TST
Plausible contributions from quantum tunnelling effects on k(T) values 24 M10 → M5 + FC(O)OH 5.70 × 1012 0.40 80.9 TST
were accounted for via the inclusion of a one-dimensional Eckart bar­ 25 M2 + HF → M14 1.56 × 1014 0.0 33.6 TST
26 M14 → M9 3.61 × 1010 0.82 78.3 TST
rier. In order to set a benchmark of accuracy for the computed reaction
(Perfluoropropene) + HF +
rate constants, Figure S1 (SM) portrays a close agreement, in terms of COF2
the comparison of Arrhenius plots, between our results and the corre­ 27 M14 → M17 (1H- 9.19 × 1013 0.90 88.2 TST
sponding literature values (Ainagos, 1991), for the important dissocia­ perfluoropropane) + COF2
tion reaction n-C4F9 → C2F4 + C2F5. The two sets of values are within a 28 M12 → M13 + HF 9.54 × 1010 0.66 55.4 TST
29 M2 + HF → M14 8.56 × 1014 0.00 33.6 TST
factor of 2–5 between 800 and 1200 K. Reaction rate constants for a few
30 C2F4 + HF → C2F5H 6.98 × 1010 0.00 48.0 TST
barrierless reactions were calculated based on the variational transition 31 M2 → COF + M8 5.00 × 1012 0.00 87.0 VTST
state theory (VTST) (Garrett and Truhlar, 2005). This method minimises 32 CHF3 → CF2 + HF 3.95 × 1010 1.11 76.9 TST
the rate constants as function of temperature and reaction coordinates (i.
e., bond stretching). Minimum energy points required in the VTST cal­
culations were attained by varying the relevant C–C and C–F bonds by an 3. Results and discussion
increment of 0.1 Å, until the structure no longer retains a single imag­
inary frequency along the designated reaction coordinate. Table 1 as­ Herein, we update the previously suggested mechanism (Altar­
sembles all estimated constants for the reaction rates introduced in this awneh, 2012) for the decomposition of perfluorobutanoic acid, consid­
study or by (Altarawneh, 2021). ering four new sets of important reactions: namely, (i) pathways leading
The CHEMKIN-RRO software (Reaction Design, 2013) performed to formation of a n-C4F9 radical and its further decomposition into
kinetic modelling based on a plug-flow reactor model (PFR); thereby, smaller CnFm fragments; (ii) the abstraction of the hydroxyl H by O/H
providing simultaneous solution to the governing ordinary differential radicals; (iii) bimolecular reactions involving HF molecules; and, (iv)
equations that describe the change of species concentrations as function cyclisation reactions. We commence the discussion by considering the
of the reactor coordinate. Section 3.6 describes details of the modelled initial decomposition channels of C4F9C(O)OH, including those that lead
reactor, flow conditions, temperature and residence time. While our to the formation of the n-C4F9 radical. Then we proceed to cover the
submodel can admit atmospheres that are typical of incinerators, here, abstraction of hydroxyl H by O/H radicals, before addressing the frag­
we include the results of pyrolysis of PFPA, as a model PFAS species, in mentation of the n-C4F9 radical. We then cover the reactions between HF
N2 bath gas. NASA polynomials were obtained with the aid of the and perfluoropentanoic acid, as well as between HF and hepta­
CHEMRATE software (Mokrushin et al., 2002) using the computed fluorobutanoyl fluoride, and then describe the cyclisation reactions.
vibrational frequencies, rotational constants, and values of ΔfHo298.
Literature provides no account on the value of ΔfHo298 for the per­ 3.1. Initial decomposition of the perfluoropentanoic acid
fluoropentanoic acid. Thus, we computed ΔfHo298 from the isodesmic
reaction given in Scheme S1 of the SM. Other ΔfHo298 values, for initially Our previous DFT study (Altarawneh, 2012) presents ten plausible
formed perfluorinated products and intermediates, followed from the initiation channels operating in the thermal decomposition of the per­
figure of ΔfHo298 for the perfluoropentanoic acid (− 533.2 kcal/mol) and fluorobutanoic acid. Direct dissociation of the C–C bonds at α, β and γ
the estimated enthalpies of the relevant reactions. NASA polynomials for locations away from the carboxylic group and the fission of the hydroxyl
all species are provided in the SM. O–H bond proceed via sizable endothermic reactions of 87.5, 85.3, 93.7
and 89.0 kcal/mol, respectively. The CO2 expulsion reactions require
the activation enthalpy of between 77.3 and 96.2 kcal/mol. For this

4
M. Altarawneh et al.
reason, these reactions contribute rather minimally to the initial
degradation of PFPA and its homologues. By examining the relevant
activation enthalpies, the HF elimination, requiring 54.2 and 35.1
kcal/mol of activation and reaction enthalpies, in this order, and leading
to the formation of a α-lactone intermediate, appears to be far more
important than the other reactions. Further decomposition of the
α-lactone intermediate branches into two channels forming penta­
fluoropropanoyl fluoride molecule and a singlet CF3CF2CF꞉ species.
While literature reports no detection of the perfluoroalkyl α-lactones
and perfluoroalkylacyl fluorides as intermediates in the thermal
decomposition of PFCA (but note that, Weber et al. have recently proved
the formation of pentafluoropropanoyl fluoride in the pyrolysis of
PFOS), the channels similar to those shown in Scheme 2 for PFPA
dominate the initial decomposition of fluoroacetic (Blake and Tomlin­
son, 1971) and trifluoroacetic (David and Philip, 1997) acids.
Fig. 1 depicts the augmented reactions pathways that prevail at the
initial stages of the degradation of the PFPA, M0 (to simplify the nota­
tion, chemical species are termed as Mx in the subsequent discussion).
The computed enthalpies, presented in the lowermost part of Fig. 1,
depart only by small values from their analogous estimates calculated
using the G3MP2B3 composite chemistry model and reported in our
previous study (Altarawneh, 2012). The direct formation of 1H-perfluor­
obutane (M5) and perfluoro-1-butene (M6, 1-C4F8), which are analo­
gous to the experimentally observed 1H-perfluoroheptane and
perfluoro-1-heptene from the decomposition of PFOA (Krusic et al.,
2005; Stockenhuber et al., 2019), proceeds via sizable activation en­
thalpies of 72.4 kcal/mol and 69.3 kcal/mol, respectively. The calcu­
lated barrier for the elimination of a CO2 molecule along the reaction M0
→ M5 + CO2 matches the corresponding barrier encountered in the
decarboxylation of acetic acid into methane and CO2 of 71.2 kcal/mol
(Nguyen et al., 1995). As suggested by Stockenhuber et al. (2019), direct
formation of perfluoro-1-heptene (along with HF and CO2) may occur
through a six-centred transition state. Our calculated enthalpic barrier
for this new pathway amounts to 69.3 kcal/mol through the transition
structure TS3. The high barrier of TS3 arises because of the strength of
secondary C–F bonds (115.4 kcal/mol). Scheme 3 portrays the
geometrical features of TS3.
The channel of M0 → M6 + HF + CO2 is endothermic by 13.3 kcal/
mol. Nonetheless, elimination of HF in the reaction M0 → M1 + HF
remains the leading channel with an activation enthalpy of 60.7 kcal/
mol. The formed α-lactone intermediate (M1) is unstable because it only
needs to climb a facile barrier of 18.6 kcal/mol to dissociate into hep­
tafluorobutanoyl fluoride (M2) and CO (TS4). In a competing minor
pathway, the diradical species CF3CF2CF2CF꞉꞉ (M3) forms through an
enthalpic barrier of 33.4 kcal/mol (TS5). A 1,2-F shift transforms M3
into the thermodynamically more stable perfluoro-1-butene (M6)
molecule via an accessible enthalpic barrier of 44.4 kcal/mol.
The two considered bond fission channels characterise the rupture of
Scheme 2. Previously presented initialisation channels.
5
Chemosphere 286 (2022) 131685
the O–H bond in the hydroxyl group (M0 → M4 + H) and the α C–C bond
(M0 → M7 + C(O)OH). The former is endothermic by 111.8 kcal/mol
while the latter by 86.2 kcal/mol. Our calculated bond dissociation free
energy for the fission of the C–C(O)OH bond (90.5 kcal/mol) clearly
overshoots a corresponding value of 63.9 kcal/mol calculated by Liu
et al. (2017) at the B3LYP/6-31G(d) level of theory. It is well-established
that, the commonly deployed B3LYP functional significantly un­
derestimates reaction enthalpies when compared with meta-hybrid DFT
methods (Zhao and Truhlar, 2008), deployed in the present study. The
scission of the O–H bond most likely proceeds via bimolecular reactions
with H/OH/F radicals in the pyrolytic andoxidative environments.
3.2. Abstraction of the hydroxyl by O/H radicals
Fig. 2 shows reaction and activation enthalpies for abstraction of the
hydroxyl H atom by H/OH/F radicals, providing estimates for the facile
barriers. Despite the best efforts, our attempts were unsuccessful in
finding an activation enthalpy for the thermally-neutral H abstraction by
F atoms. Likewise, literature values of the kinetic rate constants for the
abstraction of the hydroxyl H by F atoms often feature a temperature-
independent behaviour; i.e., the reaction does not encounter a genuine
reaction barrier (Assaf et al., 2018). In our kinetic modelling, we
adapted rate parameters for the reaction F + methanol → HF + methoxy
(Dóbé et al., 1994) to account for the H abstraction from the per­
fluoropentanoic acid by fluorine atoms.
A decarboxylation reaction along the channel M4 → M7 + CO2
(CF3CF2CF2CF2., n-C4F9) releases 5.3 kcal/mol of enthalpy without
climbing a reaction barrier. When the decomposition process of per­
fluorinated carboxylic acids proceeds in an environment with estab­
lished H/O/F radical pools, long-chain fluoroalkyl radicals constitute
the prominent initial intermediates. For example, such scenarios prevail
in recent experiments that investigated the decomposition of PFOA to
radical species in non-equilibrium plasma that included hot and solvated
electrons (Singh et al., 2019). Thus, it is of interest to address in details
the subsequent decomposition pathways of long-chain fluoroalkyl rad­
icals, also for applications in non-thermal systems.
3.3. Fragmentation of the n-C4F9 radical
The formation of the major products of 1H-perfluoroheptane and
perfluoro-1-heptene from the pyrolysis of PFOA (Krusic et al., 2005)
may take place via a direct loss of a fluorine atom from the n-C7F15
radical (producing the perfluoro-1-heptene molecule) and by HF addi­
tion (producing C4HF9). We envisage that fluorine mineralisation (i.e.,
capturing the fluorine content of PFAS by Ca(OH)2 (Wang et al., 2015),
or as F− in aqueous solutions (Hori et al., 2021), is not limited to the
parent PFAS species, but could also encompass active CnFm radicals and
intermediates that form from the degradation of PFAS compounds. Thus,
M. Altarawneh et al. Chemosphere 286 (2022) 131685

Fig. 1. Reaction pathways operating in the unimolecular decomposition of perfluoropentanoic acid (M0). Values in bold and italic fonts denote reaction and
activation enthalpies, respectively. All values were calculated at 298.15 K and are presented kcal/mol.

As shown in Fig. 1, the n-C4F9 radical (M7) branches into three

Scheme 3. Structure of TS.
in a future contribution, it will be insightful to theoretically address the
sequential conversion of potent metal hydroxides into their fluorides
through dissociative adsorption of PFAS compounds, and their derived
products.
plausible channels. Expulsion of a difluorocarbene (꞉CF2) molecule takes
place in a barrierless endothermic reaction of 55.2 kcal/mol. This route
affords the n-CF3CF2CF2 radical (M8). Unlike methylidene (꞉꞉CH2, dihy­
dridocarbon), the singlet-state of the ꞉ CF2 molecule is more stable than
its triplet configuration. Our calculated energy gap between the triplet
and singlet difluorocarbenes corresponds to 52.5 kcal/mol, in a close
agreement with the experimental figure of 55.6 kcal/mol of Brahms and
Dailey (1996). In a more energy demanding pathway, departure of a
fluorine atom to produce perfluoro-1-butene is noticeably endothermic
by 58.6 kcal/mol. Nonetheless, this value is significantly lower than
bond dissociation enthalpies for secondary C–F in alkanes (115.4
kcal/mol).
The most plausible channel signifies fragmentation of M7 into C2F4
and C2F5. through an accessible reaction enthalpy of 40.1 kcal/mol
(TS22). Fig. 3 plots the branching ratios for two most probable exit
channels of the n-C4F9 radical (M7), based on their reaction rate con­
stants listed in Table 1. Higher entropy of activation for the channel ꞉CF2
+ n-C3F7. renders it to be competitive with the degradation reaction
C2F4 + n-C2F5. across the entire temperature window explored in Fig. 3,
albeit with the change in the dominant reaction that occurs around
1200 K. Thus, both channels assume comparable importance during the

Fig. 2. Reaction (in bold) and activation (in italic) enthalpies for H abstraction from the hydroxyl H in the perfluoropentanoic (M0) molecule by H and OH radicals.
All values are in kcal/mol at 298.15 K.

6
M. Altarawneh et al.
Fig. 3. Branching ratios for the two competing channels in the unimolecular
decomposition of the n-C4F9 radical.
decomposition of PFAS compounds with long perfluoroalkyl chains.
Next, we turn our attention to elucidate the effect of the length of the
perfluoroalkyl chain on the energy requirements for the expulsion of
꞉CF2 and C2F4 molecules. Figure S2a (SM) depicts enthalpic values for
the sequential loss of CF2 groups, commencing from a n-C7F15 radical.
The five considered C–C fissions in Figure S2 essentially exhibit similar
bond dissociation enthalpies in the very narrow range of 54.9–55.9 kcal/
mol. Similarly, Figure S2b illustrates the loss of C2F4 molecules from
perfluorinated n-C4-7F7-15 radicals arising via enthalpy barriers of
38.2–40.8 kcal/mol. However, the very shallow reverse barriers (1–3
kcal/mol) plausibly diminish the overall contribution of these reactions
in a practical pyrolytic environment. Nonetheless, fission of the
F3C–C2F4 bond requires a slightly higher barrier of 44.2 kcal/mol. In a
nutshell, we infer that, the length of the perfluorinated alkyl n-CnFm
radicals induces a rather minor influence on energies pertinent to their
gas-phase fragmentation, i.e., via the ꞉CF2 and C2F4 routes. We note the
recent B3LYP/6-311 + G(2 d, 2p) calculations of Bentel at al (Bentel
et al., 2019) that reveal a somehow noticeable variations (within 3
kcal/mol) in bond dissociation enthalpies of C–F in ionic
CF3(CF2)n-COO- and CF3(CF2)n-SO2O− species. With a very strong bond
dissociation enthalpy (~110 kcal/mol), fission of secondary C–F bonds
is unlikely to contribute significantly in the homogenous gas phase
decomposition of PFCA.
3.4. Hydrofluorination of perfluoropentanoic acid and
heptafluorobutanoyl fluoride
Hydrogen halides (HCl and HBr) are by far the most important
halogen carriers during the thermal decomposition of halogenated
compounds (Altarawneh et al., 2009, 2019). For instance, it has been
consistently found that approximately between 50 and 60% of the initial
bromine present in brominated flame retardants transfers into HBr
during their pyrolysis. The noticeable absence of the C6F13COF homo­
logue of heptafluorobutanoyl fluoride (M2) from the products of
degradation of PFOA as evident in the work of Stockenhuber et al.
(2019), coupled with the disappearance of H–F vibrations (i.e.,
3700–4200 cm− 1), suggest a potential hydrofluorination route that
consumes both molecules. It should also be noted that, Weber et al.
(2021) detected the formation of C7F15COF from the pyrolysis of PFOS.
Likewise, abundant HF molecules appearing at the onset of the pyrolysis
of PFOA may induce the degradation of PFOA via bimolecular reactions.
However, literature presents no account on a direct homogenous
7
Chemosphere 286 (2022) 131685
hydrofluorination of the terminal carbonyl groups (C– – O) in carboxylic
acids, –C(O)OH, and acyl fluorides, –COF.
Very recently Altarawneh (2021) investigated a series of hydrolysis
and hydrofluorination reactions involving the transformation of hepta­
fluorobutanoyl fluoride and subsequently-formed molecules. Kinetics of
these reactions were discussed to establish the competitive nature of
three pathways, namely, HF addition, hydrolysis, and C–C bond fission.
Herein, we limit our analysis to HF addition reactions to simulate the
effect of purely pyrolytic environment. We emphasise the importance of
these reactions, HF + perfluoropentanoic acid/heptafluorobutanoyl
fluoride, for the formation of experimentally observed products from the
decomposition of PFOA. Fig. 4 presents the potential energy surfaces
(PES) of the bimolecular reactions of HF with PFPA and C3F7COF. In
Fig. 4a, the fission of the H–F bond across the aldehydic C–O bond in the
M0 structure demands a low barrier of only 14.1 kcal/mol. This reaction
results in the formation of the double hydroxylated adduct of M10 that
exists in a well-depth of 25.0 kcal/mol, in reference to the initially
separated reactants.
The M10 intermediate branches into three channels, all with sizable
enthalpic barriers in the range of 75.9–81.7 kcal/mol. The transition
TS11 signifies the formation of carbonofluoridic acid (FC(O)OH) and the
1H-perfluorobutane molecule. An unimolecular elimination of HF from
C4HF9 generates 1-C4F8 through a high enthalpic barrier of 90.2 kcal/
mol in a reaction that is endothermic by 26.6 kcal/mol. In a parallel
pathway, the six-centred transition state TS12 marks the direct forma­
tion of 1-C4F8, HF, and FC(O)OH molecules. In the third pathway, for­
mation of the epoxy intermediate M12 takes place via TS13 (80.0 kcal/
mol). The relative importance of the pathways shown in Fig. 4a rests on
a competition between the reverse reaction M10 → M0 + HF and frag­
mentation of M10 via the three pathways. The enthalpic barriers for
these pathways (75.9–81.7 kcal/mol) significantly surpass that of M10
→ M0 + HF (39.2 kcal/mol). The shallow enthalpic barrier for the HF
removal from the M10 intermediate diminishes the importance of the
HF-assisted decomposition pathways depicted in Fig. 4a. Overall, the
length of the carbon chain (4 in this study versus 5 in (Altarawneh,
2021) exerts a minor influence on values of the activation energies
pertinent to HF addition.
Fig. 4b illustrates the dissociation of the HF molecule over the C– –O
bond in the heptafluorobutanoyl fluoride via an accessible reaction
enthalpy of 34.9 kcal/mol, generating the M14 adduct in a noticeably
exothermic reaction of − 132 kcal/mol. Decomposition of the M14 in­
termediate proceeds via three pathways similar to those operating in the
fragmentation of M10. The three corridors produce perfluoropropene,
1H-perfluoropropane, carbonyl difluoride (COF2), in addition to the
epoxy intermediate M16. The enthalpic barrier for the back dissociation
corresponds to 66.4 kcal/mol, lower than the barrier for transition state
TS16 (78.6 kcal/mol). However, at high temperatures both reaction
routes may be competitive affording the corridors in Fig. 4b to consume
heptafluorobutanoyl fluoride.
Preliminary kinetic modelling of pathways shown in Fig. 1 discloses
that, ꞉CF2 and HF constitute the ultimate fluorine carriers at high tem­
peratures. For this reason, it is vital to include the bimolecular ꞉CF2 + HF
reaction (and subsequent steps) in the kinetic model for the thermal
degradation of PFAS. Pyrolysis of CHF3 is dominated by its fragmenta­
tion into ꞉CF2 and HF (Hidaka et al., 1991; Han et al., 2010). Several
experimental studies (mainly behind shock waves) report reaction rate
parameters for dissociation of CHF3 into ꞉CF2 and HF with apparent
activation energies in the range of 58.3–72.3 kcal/mol. We are unaware
of any theoretically obtained values. Our calculated activation en­
thalpies for the reaction ꞉CF2 + HF ⇆ CHF3 entail values of 18.6 and
78.0 kcal/mol in the forward and reverse direction, respectively. The
shallow forward barrier indicates a rapid and facile consumption of ꞉CF2
and HF into CHF3. Fig. 5 contrasts the computed rate constants for the
backward dissociation reaction CHF3 → CF2 + HF with the analogous
experimental values of Schug et al. (1979), and the recommended values
of Han et al. (2010). The agreement is rather satisfactory, especially at
M. Altarawneh et al. Chemosphere 286 (2022) 131685

Fig. 4. Reaction pathways operating in the bimolecular reaction of HF with perfluoropentanoic acid (a) and heptafluorobutanoyl fluoride (b). Values in bold and
italic fonts denote reaction and activation enthalpies, respectively. All values are in kcal/mol.

high temperatures relevant to the temperature window for the formation
of ꞉CF2 and HF (Han et al., 2010).
3.5. Formation of perfluorinated cyclic compounds
Oxidation and pyrolysis of halogenated alkanes and alkenes often
result in the formation of cyclic halogenated compounds. For example,
pyrolysis of hexachloropropene (C3Cl6) above ~1200 K generated a
wide array of cyclic chlorinated compounds, including C6Cl6 (hexa­
chlorobenzene), C6Cl8 (1,3,5-octachlorohexatriene), and C8Cl8 (octa­
chlorostyrene) (Dellinger et al., 1989). DFT calculations established
reaction pathways for the formation of chlorinated (Altarawneh et al.,
2009) and brominated (Altarawneh et al., 2019) cyclic compounds. A
minor amount of cyc-C4F8 was detected during pyrolysis of n-C4F10 (Yu
et al., 2008). In comparison, Ellis et al. (2001) reported the appearance
of cyc-C4F8 as one of the main products in the oxidative thermolysis of
fluorinated polymers, and so did many others, starting from the pio­
neering work of Lewis and Naylor (1947). The Diels-Alder cyclo-addi­
tion of small halogenated chains, followed by successive addition of
halogen atoms at high temperature, constitutes a key step in these
mechanisms (Ahubelem et al., 2015).
While cyclic perfluorinated compounds have not yet been observed
in the pyrolysis of PFOA, several gaseous cyclic perfluorinated com­
pounds (C4F8, C5F10, C6F12, C7F14, and C8F16) formed in the non-
equilibrium plasma generated above solutions of PFAS (Singh et al.,
2019), including that of PFOA. The mechanism proposed by Singh et al.
(2019) entails the generation of singlet diradical species (where the
radical character appears at the two ends of the carbon chain),
ring-closure of these radicals, and conversion into stable cyclic com­
pounds via loss of a fluorine atom. However, our calculations discovered

8
M. Altarawneh et al.
Fig. 5. Comparison between computed and literature values for the dissocia­
tion reaction CHF3 → CF2 + HF. aRef (Schug et al., 1979), bRef (Han
et al., 2010).
that, for instance, a CF3(CF2)5CF꞉꞉ diradical (a singlet diradical, where
the two radical characters appear on a terminal carbon atom) is more
stable than its counterpart .CF2(CF2)5CF2. (the two carbon atoms at the
two ends of the chain bear a radical character) by 72.1 kcal/mol
(Scheme 4).
Furthermore, we were not able to locate a transition state that results
in the formation of cyclic CnF2n from their corresponding .CF2(CF2)2n-
.
2CF2 diradical intermediates. The formation of the cyclic perfluorinated
compounds in Singh’s et al. (Singh et al., 2019) experiments indicates
the direct cyclisation routes from corresponding unsaturated aliphatic
chains. Fig. 6 presents the reaction and activation enthalpies for the
cyclisation of CF3(CF2)3–5CF꞉ into perfluorinated cyclic cyc-C5F10,
cyc-C6F12, cyc-C7F14, and cyc-C8F16 compounds. The transition states,
TS18-21, signify shifts of fluorine atoms between the two terminal car­
bon atoms, accompanied with a ring closure. Note that, cyc-C4F8 arises
from two C2F4 molecules rather than from the singlet diradical, and
significant strain arises in the 4-membered ring to allow this cyclisation
to occur.
A ring strain in transition state leading to cyc-C5F10 (TS18)
Scheme 4. Thermodynamic stability of CF2(CF2)5CF2 versus CF3(CF2)5.
9
Chemosphere 286 (2022) 131685
noticeably increases the activation enthalpy, compared with transition
states leading to formation of cyc-C6F12, cyc-C7F14, and cyc-C8F16 (53.9
versus 43.5–44.4 kcal/mol). No analogous transition state could be
found for the formation of cyc-C4F8 from CF3(CF2)2CF꞉꞉. As shown in
Fig. 6, the cyclic perfluorinated compounds are more stable than their
parent CF2(CF2)mCF2 di-radicals.
The sequential build-up from shorter building blocks signifies the
second pathway in the formation of cyclic perfluorinated compounds. In
this regard, ꞉CF2 and C2F4 molecules represent potent precursors. Yu
et al. (2008) located a transition state with a modest barrier of only 8.9
kcal/mol for the cyclo-addition of these two moieties leading to
cyc-C3F6. This reaction has been included in our kinetic analysis. (Note
that Table 1 only includes the reactions that we compute in the present
contribution.). Likewise, we found that, the self-condensation of two
C2F4 molecules, yielding cyc-C4F8, passes via a reaction enthalpy of 25.0
kcal/mol (TS23, shown in Scheme S2) in a highly exothermic reaction of
49.6 kcal/mol. Experimental evidence for the formation of cyc-C4F8
comes from the studies of Simon and Kaminsky (1998), who found the
pyrolysis of polytetrafluoroethylene (PTFE) to produce up to 9.9 wt%
cyc-C4F8, and by Mięsowicz (1987) who reported 29–34 wt% cyc-C4F8. It
is anticipated that, further cyclo-addition of CF2/C2F4 (and their radical
forms) will grow the size of cyclic perfluorinated compounds. Proposed
mechanisms follow the well-documented channels for the synthesis of
polyaromatic hydrocarbons (PAHs) (Richter and Howard, 2000).
Finally, we are now in a position to elucidate plausible reasonings for
the absence of C6F13COF (the major predicted product herein at low and
intermediates temperatures) from the degradation products of PFOA in
Stockenhuber et al. (2019) study. Decomposition of the trideca­
fluoroheptanoyl fluoride is likely to commence via fission of the C–COF
bond (i.e., 87.0 kcal/mol). Thus, C6F13COF should be thermally stable at
relatively high temperatures. However, the non-detection of trideca­
fluoroheptanoyl fluoride could be attributed to several factors. In
addition to its removal via the hydrofluorination pathway, similar to
that shown in Fig. 4b for heptafluorobutanoyl fluoride, the catalytic
nature of alumina surfaces deployed in Stockenhuber’s et al. experi­
ments may provide a surface-assisted degradation channel (Hou et al.,
2013). Aldehydic O presents a site in a molecule of C6F13COF that may
engender the dissociative adsorption of C6F13COF over the noticeably
catalytic alumina and/or AlF3 surfaces.
More importantly, Stockenhuber et al. (2019) introduced gaseous
PFOA into the reactor through slow evaporation of its powdered form. It
is not clear if a thermal decomposition in the condensed medium
occurred prior to vaporisation, especially if the vaporiser was operated
close to the boiling point of PFOA (462–465 K). Likewise, Xiao et al.
(2020) decomposed PFOA in a thermal desorption-pyrolysis unit but did
not mention the heating ramp; pyrolysers from CDS Analytical can be
operated between 20 K/ms and 1000 K/min, followed by a period of a
constant temperature reaction, which Xiao et al. set at 30 s for tem­
peratures higher than the boiling point of PFOA. This makes it impos­
sible to estimate the contribution of the solid-phase reactions to the
overall decomposition of PFOA. Thermal decomposition processes of
polymeric materials in the condensed phase are mainly triggered by
bimolecular reactions that lead to elimination of stable molecules (i.e.,
H2O, CO, CO2, HX), followed by C–C bridging (Starnes, 2002). As such,
these reactions may promote expulsion of CO2 molecules from the
structure of PFOA, prior to evaporation into the gas phase. For instance,
we have shown previously (Altarawneh and Altarawneh, 2012), that
major products from thermal decomposition of acetamide originate
from a series of complex bimolecular reaction that take place in the
condensed medium. Similarly, it was demonstrated (Clark et al., 2015)
that bimolecular reactions of carboxylic acids (acetic, vinylacetic
(3-butenoic acid), butanoic, crotonic ((2E)-but-2-enoic acid), iso­
crotonic ((2Z)-but-2-enoic acid)) significantly reduce activation bar­
riers, and alter the products branching ratios (decarboxylation versus
dehydration), in reference to unimolecular pathways. In summary,
experimental identification of C6F13COF, as a key intermediate as
M. Altarawneh et al.
Fig. 6. Pathways for the formation of perfluorinated cyclic compounds from ring closure of their corresponding closed-shell singlet intermediates. All enthalpy
values are in kcal/mol computed at 298.15 K.
predicted by the quantum chemical calculations, during the pyrolysis of
PFOA (and, more general, any perfluoroalkylacyl fluoride in pyrolysis of
PFCA) remains an outstanding research problem.
Hydrolysis may constitute another potent pathway for the removal of
CnF2n+1-containing species in a reaction that sequentially produces
shorter perfluorinated carboxylic acids:
CF3(CF2)mCOF + H2O → HF + CF3(CF2)mC(O)OH → CF3(CF2)mCOF + HF
+ CO
CF3(CF2)mCOF + H2O → HF + CF3(CF2)mC(O)OH
Singh et al. (2019) suggested the appearance of the hydrolysis re­
action in their plasma-induced water treatment of PFAS to decompose
CF3(CF2)mCOF. The unavoidable presence of moisture in real combus­
tion environments is expected to reduce the yield of perfluorinated al­
dehydes. For this reason, we plan to investigate the hydrolysis reaction
in combustion systems in future work, both experimentally and
quantum-chemically, to refine further the present model.
3.6. Kinetic modelling
The developed model consists of 56 reactions and 45 species. Table 1
presents the reaction rate constants computed in this study or by
Altarawneh (2021) and incorporated in the model. Additional
10
Chemosphere 286 (2022) 131685
fragmentation and bimolecular reactions of CnFm species were adopted
from the n-C4F10 combustion subset of Yu et al. (2008). Kinetic param­
eters for important reactions involving CHF3/CHF2 were extracted from
a kinetic model of Han et al. (2010) on co-pyrolysis of methane and
trifluoromethane. These reactions were also included in our recent study
on thermal decomposition of a PFOS model compound (Altarawneh,
2021). Arrhenius coefficients for termination reactions of COF were
adopted from literature: 2COF → CO + COF2 (Ninomiya et al., 2001),
COF → F + CO (Knyazev et al., 1997), and COF + F → COF2 (Cobos et al.,
1995). Kinetic modelling deploys a PFR model (reactor length of 10 cm
and an internal diameter of 0.5 cm) operated under 1 atm, at tempera­
ture between 500 and 1500 K, and a residence time of 25 s. The inlet
stream consists of 2% mol of perfluoropentanoic acid (M0) in N2 (i.e.,
purely pyrolytic conditions). These conditions cover typical gas resi­
dence time and temperature in cement kiln systems, albeit without ac­
counting for O2, H2O and additional radical pools, which are present in
the process gases. The gas residence time in kiln systems correspond to
(all values are averages) 9.3 s at 1475 K in the kiln itself, 3.9 s at 1290 K
in precalciner and 8.9 s at 1045 K in the heating cyclones (Meystre and
Silva, 2015). Thermochemical and kinetic parameters that comprise the
model are enclosed in the SM.
While the relevant experimental investigations point out to the for­
mation of several products, these studies do not provide temperature-
dependent profiles of the species emerging from the reactor.
M. Altarawneh et al.
Nonetheless, simulated yields of products, obtained in the present study,
should provide a valuable insight into mechanistic trends governing the
decomposition of PFOA, and other PFCA homologues, in general, and
provide the theoretical requirements for the operating conditions for
burning of PFAS in incinerators. Our mechanistic analysis provides
accessible pathways, that potentially underpin the generation of major
experimental products such as HF, perfluorinated alkenes, CnHFm spe­
cies, and cyclic compounds. The model is expected to satisfactorily ac­
count for evolution of products from the decomposition of the
perfluorinated alkyl chain. This is affirmed by the close agreement be­
tween experimental and product profiles in case of n-C4F10 as demon­
strated by Yu et al. (2008). As an accuracy benchmark of the adopted
simulation framework, our computed thermokinetic parameters were
successfully contrasted with representative experimental measure­
ments, please refer to discussion in Section 2 and the values provided in
Table S1 and Figure S1. This indicates that, the calculated activation
barriers for the initiation steps in the decomposition of the of per­
fluoropentanoic acid should exhibit an acceptable accuracy margin, i.e.,
within 1–3 kcal/mol.
The model predicts an onset temperature at ~780 K for the decom­
position of the perfluoropentanoic acid with a full degradation at ~950
K, for the residence time of 25 s, following a steep decomposition profile
(Fig. 7a). Our predicted onset temperature exceeds the analogous values
determined experimentally of above 723 K. The difference (by ~60 K) in
modelled and measured onset temperature can be rationalised consid­
ering the construction material of the reactor in Stockenhuber’s et al.
(2019) experiments. It is well-documented that minute concentration of
transition metal oxides in alumina substantially catalyse the decompo­
sition of halogenated compounds, as does AlF3 that replaces Al2O3 on
Fig. 7. Decay profile of perfluoropentanoic acid (a), mole fraction of major (b), and minor (c and d) species from pyrolysis of a perfluoropentanoic acid at a residence
time of 25 s.
11
Chemosphere 286 (2022) 131685
the reactor walls early in the pyrolysis process and is known for its
strong acidic sites (Fang et al., 2019). Our previous work on oxidative
decomposition of 4-chlorobiphenyl (Hou et al., 2013) reported a
remarkably lower onset temperature for its decomposition when
compared with the analogous value measured in reactors made out of
high purity quartz and high purity quartz coated with boric oxide to
minimise catalytic wall effects (i.e, 573 versus 773 K). Overall, following
the loss of SO3/SO2 versus CO2/CO, the decomposition of our
PFCA-model compound proceeds via similar degradation pathways to
these presented in our recent study for PFOS surrogate (Altarawneh,
2021).
Fig. 7b depicts profiles of major products while Fig. 7c and d shows
mole fractions of minor CnFm and CnFmH species. Analysis of reaction
pathways are presented in Fig. 8. Minor species include carbonyl
difluoride (COF2), C2F4, CF4, C2F6, C3F6 and CHF3, in addition to minute
concentrations of cyc-C4F8, C2HF3 and C2H2F4. At low decomposition
temperature (i.e., 800–850 K), decay of the perfluoropentanoic acid
solely occurs via the two-step reaction sequence M0 → HF + M1 → CO +
heptafluorobutanoyl fluoride (M2). Between 800 and 1100 K, mole
fraction of CO closely matches that of M2 (Fig. 7b). As the temperature
increases, direct formation of perfluoro-1-butene (CO2 + HF + M6), and
to a lesser extent C4HF9 (CO2 + M5), become gradually the important
decomposition channels. At 1200 K, the generation of hepta­
fluorobutanoyl fluoride, perfluoro-1-butene, and 1H-perfluorobutane
accounts for 58.0%, 34.3% and 7.8%, of the initial decomposition of
the perfluoropentanoic acid (Fig. 8a), respectively. Departure of the CO
profile from that of heptafluorobutanoyl fluoride in Fig. 7b tracks the
consumption of C3F7COF by the hydrofluorination sequence illustated in
Fig. 4b as well as by fission of its C–COF bond (46.5%). The yield of
M. Altarawneh et al. Chemosphere 286 (2022) 131685

Fig. 8. Analysis of initiation reaction pathways at different temperatures (a), and subsequent fragmentation pathways at 1200 K (b).

perfluoro-1-butene peaks at ~1300 K accounting for the mole fraction of mainly in CF3. → ꞉CF2 + F and C3F7COF ⇆ COF. + n-C3F7. reactions
17% of the product gases, as illustrated in Fig. 7b. between 900 and 1300 K. The model predicts a key role of F atoms in
The addition of HF consumes 53.5% of formed heptafluorobutanoyl
fluoride at 1200 K (Fig. 8b). The hydrofluorination reaction accounts for
chain shortening reactions, which eventually lead to the formation of
perfluoropropene (58.6%) and of 1H-perfluoropropane (41.4%). None­
theless, perfluoropropene (C3F6) readily degrades into ꞉CF2 and C2F4
(99%, Fig. 8b) with a maximum yield of only 0.005 (based on mole
fraction of products, Fig. 7d) around 1300 K. Formation of 1H-perfluor­
opropane mimics the synthesis of the experimentally detected product
1H-perfluorohexane in the experiment of Stockenhuber et al. (2019). As
shown in Fig. 7a, HF remains the leading product at all temperatures,
despite of its significant depletion via the hydrofluorination reaction:
heptafluorobutanoyl fluoride + HF. Hydrofluorination of per­
fluoropropene into 1H-perfluoropropane is rather limited, consuming
only 2% of the formed perfluoropropene. As pictured in Fig. 7c, the yield
of 1H-perflurobutane attains its maximum value at 0.03 at around 1200
K.
Formation of smaller CnFm fragments commences via fission of the
C–C(O)OH in perfluoropentanoic acid. The fluoropropyl radical (n-C3F7)
decomposes into ꞉CF2 + C2F5. (21.6%) and CF3. + C2F4 (78.4%). Frag­
mentation of CF3. produces a fluorine atom and ꞉CF2. Kinetic parameters
of this important reaction were adopted from a shock-tube study of
Cobos et al. (2010). Computed coefficients from the sensitivity analysis
on the production of F atoms (shown in Fig. 9) reveal that F atoms arise Fig. 9. Normalised sensitivity analysis for production of F atoms at the middle
of the reactor. The equal signs in the legend denote reversible kinetic reactions.

12
M. Altarawneh et al.
driving decomposition of the perfluoropentanoic acid at elevated tem­
peratures. The major consumption route of perfluoro-1-butene stems
from its reaction with F atom to produce the n-C4F9 radical. Abstraction
of the hydroxyl H atom via the reaction F + M0 → M4 + HF accounts for
25.6% of the total consumption of the perfluoropentanoic acid at 1500
K. A direct loss of CO2 marks the sole fate of the M4 radical and
significantly contributes to the formation of CO2 molecules at high
temperatures as documented in Fig. 7b. At low and intermediate tem­
peratures, n-C4F9. forms via addition of a fluorine atom to the n-C4F8
molecule (Fig. 8b, right-hand side). The importance of the channel
leading to heptafluorobutanoyl fluoride diminishes with temperature.
At 1200 K, the n-C4F9 radical fractures into C2F4/C2F5. (91.2%) and
꞉CF2/n-C3F7. (8.8%). Decomposition of C2F5 radical gives ꞉CF2 and CF3..
At 1200 K, nearly 50% of the formed C2F4 molecules (from degradation
of n-C3F7 and n-C4F7 radicals) decompose to produce ꞉CF2 molecules.
The addition of HF to ꞉CF2 to generate CHF3 consumes 12.7% of
difluorocarbene. Fragmentation of all CnFm species at high temperatures
produces ꞉CF2 as the major fluorine carrier, beyond 1400 K.
Self-addition of CF3 radicals to form C2F6 represents a minor contribu­
tion to the flux of fluorine between 1100 and 1300 K.
Due to the negligible formation of H/OH radicals in the current
model, their contribution in decomposition of the perfluoropentanoic
acid remains limited. However, in an environment rich with O/H radical
pool (as in co-oxidation of perfluorinated carboxylic acids with hydro­
carbons and other fuels), abstraction of the hydroxyl group leading to
CO2 and n-CnF2n+1 radical will most likely constitute a dominant chan­
nel. Such reactions may prevail under real scenarios; i.e., when, per­
fluorinated carboxylic acids (and PFAS in general) are treated in thermal
destruction systems. For this reason, it is of a practical importance to
investigate transformation chemistry that dictates interaction of small
perfluorinated species with commonly deployed catalysts in the capture
and treatments of PFAS streams, i.e., alumina and Ca(OH)2, for PFAS
decomposition and fluorine mineralisation in cement kilns or with other
metal oxides that predominate in fly ash in the incinerators.
Formation of 1H-perfluropropane from hydrofluorination of per­
fluoropropene consumes only 2.0% of C3F6; not shown in the figures. To
further address the hydrofluorination capacity of perfluorinated al­
kenes, in Fig. 10, we plot the temperature-dependent mole fraction of
C2HF5 that results from the reaction of an equimolar mixture of HF and
C2F4. Formation of C2HF5 appears to be minimal, even when allowing a
longer residence time of 60 s for the occurrence of this bimolecular
Fig. 10. Effect of residence time on the formation of C2HF5 from the reaction
HF + C2F4 ⇆ C2HF5 starting from an equimolar concentration of the
two reactants.
13
Chemosphere 286 (2022) 131685
reaction. The yield of C2F4 from pyrolysis of polytetrafluoroethylene
(PTFE) reached 76 wt% at 823 K (Simon and Kaminsky, 1998). Per­
fluoropropene accounted for 7.1 wt% of the initial mass of PTFE (Simon
and Kaminsky, 1998). Similarly, the yield of cyc-C4F8 approached 8%
from the pyrolysis of PTFE, rising to 29–34% at 923–973 K (Mięsowicz,
1987). The predicted low yield of cyc-C4F8 (2 × 10− 5 at 1200 K) herein
can be understood in view of the rapid degradation of its main building
block (C2F4) into ꞉CF2 at temperatures higher than 1200 K. In other
words, formation temperature of C2F4 (from decomposition of
n-C3F7./n-C4F9.) coincides with its fragmentation into ꞉CF2 molecules.
Overall, in the absence of gas-solid reactions, at > 1500 K, we predict
the emission of ꞉CF2 (biradical difluorocarbene), HF, CO2, CO, CF4, C2F6,
and C2F4, as the terminal products of decomposition of PFAS, but at <
1400 K, we note the formation of C4HF9, COF2, and C3F7COF, with 1-
C4F8, 2-C4F8 and C3HF7 persisting to 1500 K. These predictions have
great significance to the remediation of PFAS in incinerators, but we
wish to stress that our study has not considered the role of flyash in these
systems, and did not include gas composition (moisture, oxygen, fuel)
typically encountered in incinerators. For instance, municipal waste
combustors display 10% O2 and 15% moisture at the exhaust (Taylor
et al., 2014). In addition, pyrolysing or oxidising waste itself provides a
hydrogen source to mineralise fluorine to HF. We expect these consid­
erations to improve the mineralisation of PFAS in real combustion sys­
tems. Thus, our model needs to be executed by future users under their
target conditions. Short residence time of 2.0 s (a value that typically
applies in waste incinerators) slightly alters the predicted yield of major
fluorine-bearing species at elevated temperatures and delays the com­
plete elimination of PFPA to around 1020 K, as illustrated in Fig. 7a.
Figure S3 contrasts mole fractions of ꞉CF2, C2F4, C2F6 and HF attained
with 2 and 25 residence times. A lower yield of HF in case of a longer
residence time coincides with its consumption through the illustrated
bimolecular addition reactions.
We conclude our discussion with two comments. Firstly, we note that
while PFPA (or any PFCA in general) disappears by 1020 K, C–C bonds in
the product molecules start to show significant fission only at temper­
atures above 1200 K, with the transitional species disappearing by 1500
K. These are the theoretical requirements for handling PFAS in thermal
systems, based solely on the gas-phase reactions, in the absence of
moisture and oxygen in the gas phase, and heterogenous processes in the
modelling. We expect that these theoretical limits can be further refined
(i.e., decreased) in subsequent calculations, in which our model will
serve as a submodel in comprehensive computations. Secondly, the ef­
ficiency of practical incineration systems is defined by temperature,
residence time and turbulence (mixing). It is well known that, highly
turbulent conditions in incinerators provide uniform temperature and
minimise the emissions of products of incomplete combustion (e.g.
(Winchell et al., 2021),). The plug flow reactor model deployed in this
study assumes perfect mixing but only in the direction perpedicular to
flow, and no mixing in the axial direction. From this perspective, future
investigations should also include calculations of PFAS destruction and
mineralisation in stirred reactors.
4. Conclusions
This contribution reports thermokinetic parameters for a wide range
of reactions that govern the initial decomposition of the per­
fluoropentanoic acid, a model PFAS species, and the subsequent evo­
lution of the composition of reaction gases as function of residence time.
Modelled profiles of product species and the analysis of reaction path­
ways reveal the competitive importance of two routes; namely, the
formation of heptafluorobutanoyl fluoride + HF + CO (at low and in­
termediates temperatures) and production of perfluro-1-butene + CO2
+ HF (at high temperatures). Decomposition of HF over the C– – O bond
in heptafluorobutanoyl fluoride initiates an important pathway that
transforms C3F7COF into 1H-perfluoropropane. Fission of C–COF bond
in the heptafluorobutanoyl fluoride affords the generation of ꞉CF2
M. Altarawneh et al.
molecules at high temperatures. Hydrofluorination of perfluorinated
alkenes into their respective hydrofluoroalkanes constitutes a minor
corridor at all investigated temperatures. Formation of cyclic per­
fluorinated compounds via ring-closure reactions of their corresponding
diradical adducts arises via accessible activation enthalpies. The tem­
perature window for the formation of C2F4 favours its degradation into
꞉CF2 molecules, rather than its self-addition to produce cyc-C4F8. The
presence of H/O/F radical in combustion medium is anticipated to shift
the product profiles toward formation of n-CnF2n+1 radicals, that readily
degrade into F, ꞉CF2, and C2F4, and eventually to HF in the presence of a
hydrogen source.
The analysis of reaction pathways provided an important insight into
the relative importance of plausible initial decomposition channels. The
formation of a fluorine atom via the radical reactions such as CF3 ⇆ F +
CF2 drives a facile degradation route of the parent perfluoropentanoic
acid that results in the generation of short perfluorinated species. As
PFAS are generally deployed in formulations with hydrocarbon and
carbohydrate materials (e.g., hydrocarbon surfactants and gums present
in concentrates of PFAS foams) future work should focus on developing
reaction mechanisms and chemical kinetic models for the co-pyrolysis/
oxidation of PFAS with these materials or with typical fuels.
While this study considered H and OH to arise only from the
decomposition of perfluoropentanoic acid itself, in incinerators and
other practical combustion systems, these radical pools will increase in
size, prompting the formation of F, CF2 and C2F4 at lower temperatures
and shorter residence time, and enhanced mineralisation of fluorine.
Our work provides a suitable submodel to be incorporated into future
comprehensive mechanisms that will also include heterogenous pro­
cesses. Such models should also comprise coupling between fluorine
reservoirs in the gas and solid phases. Evidently, attempts to destroy
PFAS in systems, which are operated at too low temperature or at too
low residence time and do not include a means to bind the fluorine, may
convert PFAS to short-chain perfluoro- and hydrofluorocarbons, and
other species such as COF2, known for its toxicity. From this perspective,
further calculations are needed to gain understanding of the role of
oxygen, moisture and fuel (as source of hydrogen) on the mineralisation
of fluorine to HF in gas phase reactions and on the destruction of tran­
sitional species. We have demonstrated that the gas phase conditions, in
the absence of reactions with solid phase species (such as clinker), in
both incinerators and cement kilns, lead to similar product distribution,
provided that the gas phase temperature exceeds 1200 K. Note that we
also predict the emission of the toxic COF2 for the operating temperature
of up to 1400 K, as a minor product, and a range C3–C4 fluorocarbons up
to 1500 K. Thus, our model predicts 1020 K and 1500 K as the theo­
retical temperatures for destruction of PFAS species and evolution of HF,
respectively, in incinerators operated at the residence time of 2 s.
Careful field studies are also needed to investigate the role of flyash in
mineralisation of fluorine from PFAS in incinerators, in conjunction with
measurements of emissions of PFC and HFC, to determine whether such
systems do indeed discharge these species. It is important to emphasise
that we predict no formation of the highly toxic perfluoroisobutene,
even as a minor species, under all temperatures and residence times
considered in this study.
Credit author statement
Mohammednoor Altarawneh: Conceptualisation, Methodology,
Writing - Original Draft, Formal Analysis, Mansour H. Almatarneh:
Formal analysis, Bogdan Z. Dlugogorski: Conceptualisation, Writing –
Review & Editing, Data Curation.
Declaration of competing interest
Authors declare no conflict of interest.
14
Chemosphere 286 (2022) 131685
Acknowledgments
This study has been supported by a UPAR grant from the United Arab
Emirates University (grant number: 31N451) and a computational time
allocation from Compute Canada.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.chemosphere.2021.131685.
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