Environmental Pollution 348 (2024) 123782

Contents lists available at ScienceDirect

Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Formation of volatile chlorinated and brominated products during low

temperature thermal decomposition of the representative PFAS
perfluorohexane sulfonate (PFHxS) in the presence of NaCl and NaBr☆
Yuwei Zhao *, Paul G. Koster van Groos 1, Nikita Thakur , Mark E. Fuller , Anthony Soto ,
Paul B. Hatzinger
Biotechnology Development and Applications Group, APTIM, 17 Princess Rd. Lawrenceville, NJ, 08648, USA

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

Keywords: Per- and polyfluoroalkyl substances (PFAS) are synthetic organofluorine compounds known for their chemical
PFAS and physical stability as well as their wide range of uses. Some PFAS are widely distributed in the environment,
Perhaloalkane leading to concerns related to both environmental and human health. High temperature thermal treatment (i.e.,
Volatile organofluorine compounds
incineration) has been utilized for PFAS treatment, but this requires significant infrastructure and energy,
Pyrolysis
prompting interest in lower temperature approaches that may still lead to efficient destruction. Lower treatment
temperatures, however, increase the potential for incomplete PFAS mineralization and formation of volatile
organofluorine (VOF) products. Herein, we report the formation of novel VOF products that include chlorinated
and brominated compounds during the thermal treatment of potassium perfluorohexane sulfonate (PFHxS), a
representative perfluoroalkyl acid (PFAA). By comparing the gas chromatography-mass spectrometry (GC-MS)
results of known VOF stocks to evolved VOF during thermal treatment of PFAS, the formation of perfluorohexyl
chloride and perfluorohexyl bromide was observed when PFHxS was heated at temperatures between 275 and
475 ◦ C in the presence of NaCl and NaBr, respectively. To our knowledge, this is the first report of chlorinated or
brominated VOF products during thermal treatment of a PFAA. These findings suggest that a range of mixed
halogenated VOF may form during thermal treatment of PFAS at relatively low temperature (e.g., 500 ◦ C) and
that these can be a function of salts present in the matrix.

1. Introduction and laboratory-scale studies generally indicate that PFAS mineralization

Per- and polyfluoroalkyl substances (PFAS) are synthetic chemicals
known for their heat resistance and repellency properties (Buck et al.,
2011). The persistence of PFAS in the environment and their potential
human health impacts make treatment challenging (Cordner et al.,
2019; Sznajder-Katarzyń et al., 2019; Bell et al., 2021; Garg et al., 2021;
Shahsavari et al., 2021). Thermal treatment approaches have been uti­
lized for many difficult to treat contaminants and thought capable of
removing PFAS in aqueous film-forming foam (AFFF), sewage sludge,
contaminated soils, and municipal waste (Vecitis et al., 2009a; Roth
et al., 2020; Kundu et al., 2021; Verma et al., 2023). While questions
regarding the formation and/or persistence of very short chain fluoro­
carbon products (e.g., CF4) currently remain, preliminary conceptual
can be achieved at temperatures exceeding 1000 ◦ C, albeit with high
energy consumption (Vecitis et al., 2009a; Maga et al., 2021).
In addition to high temperature approaches, lower temperature and
more energy efficient approaches are actively being explored, but
challenges associated with possible by-products, such as short-chain
perfluoroalkyl acids (PFAAs) need to be considered (Watanabe et al.,
2018; Wang et al.; Xiao et al., 2020; Krusic and Roe, 2004). For more
comprehensive evaluation of thermal treatment methods, a better un­
derstanding of the relevant intermediate species and products, as well as
possible transformation mechanisms, is critical (Zhang et al., 2023).
Difficulties associated with sample collection and analysis pose a
significant obstacle for the observation of volatile products resulting
from incomplete PFAS destruction (Longendyke et al., 2022). To date,

☆
This paper has been recommended for acceptance by Jiayin Dai.
* Corresponding author.
E-mail address: yuwei.zhao@aptim.com (Y. Zhao).
1
Current address: ExxonMobil Biomedical Sciences Inc., Annandale, NJ, USA

https://doi.org/10.1016/j.envpol.2024.123782
Received 20 December 2023; Received in revised form 26 February 2024; Accepted 11 March 2024
Available online 12 March 2024
0269-7491/© 2024 Elsevier Ltd. All rights reserved.
Y. Zhao et al.
standardized methods (e.g., USEPA OTM-45) that primarily focus on a
limited set of targeted PFAS are inadequate for fully tracing the fate of
all PFAS throughout thermal processes (Al Amin et al., 2020; Jahnke and
Berger, 2009; Liang and Su, 2009; Wang et al., 2022). The low con­
centrations and vast diversity of potential by-products pose significant
challenges to their detection, differentiation, and quantification using
traditional analytical approaches (Al Amin et al., 2020; Arana Juve
et al., 2023). Additionally, the lack of reference materials for many
possible PFAS degradation by-products further complicates the process.
Despite these challenges, previous research has identified some long
and short chain fluorinated products formed during thermal treatment
of perfluorocarboxylic acids (PFCAs), including 1H-perfluoroheptane
and perfluoro-1-heptene (Krusic and Roe, 2004; LaZerte et al., 1953).
Short-chain products and intermediates resulting from thermal treat­
ment including tetrafluoroethene (C2F4), difluorocarbene (CF2), tri­
fluoromethyl radicals (CF3), and tetrafluoromethane (CF4) have also
been observed or inferred (Wang et al.; Vecitis et al., 2009b; West et al.,
2023; Krug et al., 2022). When oxygen is present, these may be further
transformed into carbon dioxide, carbon monoxide, and hydrogen
fluoride (Altarawneh et al., 2022; Aleksandrov et al., 2019). Much
research has focused on PFAS alone, or PFAS in combination with a solid
matrix, such as activated carbon (Wang et al.; Sonmez Baghirzade et al.,
2021; DiStefano et al., 2022), but these results may not fully reflect the
complexity of real-world applications. For example, PFAS-laden soils,
sludge, or drill spoils from well installation often contain other organic
(e.g., natural organic matter, hydrocarbons, solvents) and inorganic (e.
g., major anions Cl− , NO−3 , SO−4 ) compounds. It is crucial to extend PFAS
research efforts to consider the effects of such compounds on potential
products resulting from PFAS treatment. Previous research demon­
strated that perfluoroalkyl halides can result from reactions between
perfluoroalkyl salts and chlorine or bromine gas at temperatures below
70 ◦ C (Hauptschein et al., 1952; Hauptschein and Grosse, 1951).
This work explored the possibility that inorganic chloride and bro­
mide salts commonly present in solid media might result in similar
perfluoroalkyl halide compounds after thermal treatment. The products
formed during the low temperature treatment of PFHxS in the presence
of NaCl and NaBr, based on gas chromatography-mass spectrometry
(GC-MS), were compared to known mixed halogen VOF. To the best of
our knowledge, this effort is among the first describing mixed halogen
VOF formation resulting from thermal treatment of PFAS in presence of
halide salts. This highlights a critical area for further investigation,
aimed at understanding the potential for such interactions and their
implications for PFAS remediation efforts.
2. Materials and methods
Materials. Eight volatile organofluorine (VOF) compounds and two
volatile perfluoroalkyl halides were purchased from SynQuest Labora­
tories (Alachua, FL): tetrafluoromethane, 1H-perfluorohexane, 1H-per­
fluoroheptane, hexafluoropropylene, perfluorohexene-1, perfluoro
hepetene-1, perfluorooctene-1, 1H-perfluorooctane, perfluorohexyl
chloride, and perfluorohexyl bromide. Potassium perfluorohexane sul­
fonate (PFHxS) was purchased from Sigma Aldrich (Milwaukee, WI).
Additional information about PFAS, VOF, and other chemicals used in
this research is available in Table S1.
Sample preparation. QUIKRETE® all-purpose sand (Atlanta, GA)
was sieved to <600 μm and used as a loading matrix for PFAS. PFHxS
was dissolved in methanol (concentration ~ 10 g/L), and aliquots were
then mixed with the sand (nominal loading of 2.4 mg PFHxS/g). The
methanol was evaporated under a stream of nitrogen until the weight of
the sand was constant. The sand was then homogenized in a glass jar
using a rotary tumbler. NaCl and NaBr were separately pulverized to a
fine powder using a mortar and pestle, and 10 mg/g was mixed with the
PFAS-loaded sand for selected experiments.
Thermal decomposition experiments. Fig. S1a presents the sche­
matic of the thermal system used in this study. Thermal experiments
2
Environmental Pollution 348 (2024) 123782
were conducted in a tube furnace (Lindberg/MPH, Riverside, MI),
equipped with a stainless-steel process tube that has a 1.9-cm inner
diameter and 50-cm length. All transfer line tubing was polyvinyl
chloride (PVC), and fittings were stainless steel, glass, polypropylene,
and polystyrene. PFHxS-loaded sand (3 g) was placed in a heavy-gauge
nickel combustion boat (Fisherbrand, Canada) within the steel tube in
the furnace. Nitrogen gas (99.999%) was purged through the system at
25 mL/min overnight to remove oxygen and trace gases from the system,
and the same flow rate was used during experiments. The temperature
both inside and outside the steel tube within the furnace was logged by a
K-type thermocouple. Two 25 mL glass midget impingers with 20 mL of
carbonate buffer solution (10 mM each of Na2CO3 and NaHCO3) were
placed in series to absorb water-soluble or water-reactive PFAS, HF, and
sulfur oxide species from the off gas exiting the steel tube. After passing
through the impinger traps, the gas was collected in Flex Foil gas sam­
pling bags (SKC, Inc., Eighty Four, PA) for later VOF analysis by GC-MS.
During heating of the furnace, the temperature was maintained for a
minimum of 30 min at 200 ◦ C, 275 ◦ C, 325 ◦ C, 375 ◦ C, 425 ◦ C, and
550 ◦ C to allow for gas collection (Fig. S1b). The carbonate solution in
the impingers and the gas sampling bags were changed for each tem­
perature plateau.
VOF characterization by GC-MS. Analysis of known VOF and the
gaseous by-products from thermal decomposition of PFAS collected in
gas sampling bags was accomplished using a Hewlett Packard 6890 Gas
Chromatograph system, coupled to a Hewlett Packard 5973 Mass Se­
lective Detector (MSD), equipped with a DB-624 GC column (60 m ×
0.25 mm, i. d., 1.4 μm film thickness; J&W, Santa Clara, CA). The
following temperature program was used: initial oven temperature was
45 ◦ C for 5 min; this was then raised to 250 ◦ C at 15 ◦ C/min, with a final
bake out temperature of 275 ◦ C for 4 min. Helium was used as carrier gas
with a flow rate of 1 mL/min (constant flow). The sample injection
volume was 100 μL. Known VOF were prepared in the same type of gas
sample bags in nitrogen at (nominal) concentrations of 40 ppmv.
The Mass Selective Detector (MSD) was operated in the electron
impact (EI) mode. The ion source temperature was 230 ◦ C and the
electron energy was 70 eV. The mass ranges from m/z 45 to 550 was
scanned. The key ion fragments produced from the known VOF com­
pounds, especially those suggestive of halogen-containing compounds,
were compared to those observed in the gas samples collected during the
thermal decomposition experiments.
Due to the unavailability of reference standards for VOF compounds,
chemical identification within this study was qualitative rather than
quantitative. Details regarding the calibration of the GC-MS equipment
are provided in the supporting information. Furthermore, given the
absence of the detected VOF compounds in standard mass spectrometry
(MS) libraries, identification of these compounds was facilitated through
comparison with known VOF stock compounds, employing a dot prod­
uct calculation to measure the similarity in the overall pattern (Equation
(1)) (Tsugawa et al., 2015).
∑( )
wi Iunknown,i wi Istock,i
Dot Product = √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ Equation 1
∑( )2 ∑ ( )2
wi Iunknown,i wi Istock,i
where Iunknown,I is the intensity of peak i in the unknown spectrum and
Istock,i is the intensity of peak i in the VOF stock spectrum. The coefficient
wi is the weight value to reduce the effect of high abundance intensities.
Dot product value of unity suggests perfect agreement between two
spectra.
3. RESULTS and DISCUSSION
GC-MS chromatograms of a mixture of eight known VOF stocks
(Fig. S3), the ion fragment mass-to-charge (m/z) spectra for each VOF
stock (Fig. S4), and two volatile perfluoroalkyl halides (Fig. S5) are
presented in Supporting Information. GC-MS chromatograms
Y. Zhao et al.
incorporating ion fragment m/z signals were more clearly visualized
using a heat map, where the y-axis represents the GC retention time, the
x-axis represents the m/z of relevant ion fragments, and the color in­
tensity reflects the abundance of each fragment. Fig. 1a displays the heat
map for a mixture of select VOF, illustrating the dominant ion fragments
of each.
Thermal decomposition of PFHxS. The VOF collected during
thermal decomposition of PFHxS in sand were identified by comparing
the ion fragments obtained to those from the known VOF stocks
(Fig. 1a). Fig. 1b shows the sum of ion fragment abundance from all the
gas samples collected during PFHxS pyrolysis. The comparison of 1H-
perfluorohexane and perfluorohexene-1 that were readily apparent
after thermal decomposition with their corresponding VOF stocks
resulted in calculated dot product values of 0.98 and 0.97, respectively,
verifying the identity of these two VOF products. In the analysis of 1H-
perfluorohexane and perflurohexene-1, common fragments identified in
both the thermally generated VOF and known VOF included CF2H+ (m/z
51), CF+3 (m/z 69), and C3F5 (m/z 131). As noted above, the limited
+
availability of VOF standards precluded absolute quantification of the
VOF compounds produced during thermal decomposition, but VOF
identity was determined based on the characteristic fragmentation
pattern of the purchased VOF compounds.
Thermal decomposition of PFHxS in the presence of NaCl. When
PFHxS-loaded sand was heated in the presence of solid NaCl, in addition
to potential known VOF (Fig. S6b), the collected VOF also contained two
unique ion fragments (m/z 85 and m/z 87) at a retention time of 6.1 min
(Fig. 2d). These fragments were only detected in thermal decomposition
gas samples and were not found in any purchased VOF stocks except
purchased perfluorohexyl chloride. Fig. S7 compares the abundance of
m/z 85, and m/z 87 in the spectrum gas samples collected at 275, 325,
375, and 425 ◦ C. (Results from temperatures 200 and 550 ◦ C were
excluded due to the lack of identifiable peaks). The observed ratios of
ion fragments 85 and 87 at different temperature varied from 2.8 to 3.2,
which closely aligns with the natural abundance ratio of 3.1 of chlorine
isotopes 35Cl and 37Cl. Based on these observations, it was hypothesized
that fragment m/z 85 and m/z 87 correspond to CF35 37 +
2 Cl and CF2 Cl ,
+
respectively.
Evidence supporting identification of the unknown compound
described above was achieved by comparing its fragment pattern with
that of commercially available perfluorohexyl chloride. The GC-MS ion
fragment pattern of purchased perfluorohexyl chloride (C6F13Cl) stock
was observed at a retention time of 6.1 min (Fig. 1c). Fig. 2a compares
the total relative abundance of main ion fragments at 6.1 min with the
relative abundance of those from the perfluorohexyl chloride stock. The
compound detected at 6.1 min exhibited similar fragmentation and
relative abundance patterns as the perfluorohexyl chloride stock.
Additionally, the m/z 85 to m/z 87 ratios observed during analyses from
the thermal experiment and the perfluorohexyl chloride stock were
nearly identical, 3.1 and 3.0, respectively. The dot product values for the
VOF compound generated at 275, 325, 375, and 425 ◦ C in comparison to
the perfluorohexyl chloride stock were 0.989, 0.994, 0.990, and 0.990,
respectively. However, the dot product values of the same VOF calcu­
lated in comparison with 1H-perfluorohexane, chosen for its similar
retention time of 6.0 min, were significantly lower, e.g., 0.672, 0.686,
0.672, and 0.672, which indicated the new VOF was not 1H-perfluoro­
hexane with a shifted GC retention time. These findings strongly sup­
port the conclusion that the chemical detected at 6.1 min was
perfluorohexyl chloride (C6F13Cl) generated during the pyrolysis of
PFHxS in the presence of NaCl.
Thermal decomposition of PFHxS in the presence of NaBr. When
PFHxS pyrolysis was performed in the presence of NaBr, along with the
potential known VOF (Fig. S6d), perfluorohexyl bromide (C6F13Br) was
detected, with the GC ion fragments obtained at a retention time 6.8 min
(Fig. 1e). A distinctive ion fragment for perfluorohexyl bromide is m/z
129, CF79 2 Br . The corresponding compound with heavier
+ 81
Br
81 +
(CF2 Br ) has the same molecular weight as C3F5 and, without the
+
3
Environmental Pollution 348 (2024) 123782
advantage of high-resolution mass spectrometry, the abundance of m/z
131 must be assumed to represent the total abundance of both fragments
(Fig. 1f). Analogous to the observation of perfluorohexyl chloride above,
perfluorohexyl bromide was detected in VOF produced in the presence
of NaBr, with the GC retention time of 6.8 min, and exhibiting charac­
teristic ion fragmentation and relative abundance patterns to the per­
fluorohexyl bromide stock (Fig. 2b). The dot product values for the
compound generated at 275, 325, 375, and 425 ◦ C were 0.995, 0.999,
0.908, and 0.997, respectively, when compared with perfluorohexyl
bromide stock. Additionally, comparisons were made with 1H-perfluor­
ooctane stock, selected for its similar retention time of 6.8 min to tar­
geted compound, yielding dot product values of 0.646, 0.662, 0.599,
and 0.662, respectively. The pronounced difference in dot product
values strongly supports the identification of the targeted compound as
perfluorohexyl bromide. It should be noted that m/z 129 and m/z 131
indicative of CF2Br fragments were also detected at additional retention
times, indicating the potential production of other perfluoroalkyl bro­
mide compounds, which may warrant further investigation.
Perfluoroalkyl halides can be synthesized by heating the corre­
sponding perfluoroalkyl salt in presence of chlorine or bromine gas
under low temperature (less than 70 ◦ C) (Hauptschein et al., 1952;
Hauptschein and Grosse, 1951). In this study, NaCl and NaBr served as
sources for chlorine and bromine, respectively, both of which are rela­
tively stable/inert at such low temperatures. The mechanism for the
formation of perfluoroalkyl halides during the pyrolysis of PFHxS in this
study is not fully elucidated. It is not known if the process is affected by
the parent PFAS carbon chain length or functional head group (e.g.,
PFCA), or if PFAA precursor compounds are also susceptible to this re­
action. In the experiments described here, the apparent yield of 1H-per­
fluorohexane observed in GC-MS chromatograms was reduced when
perfluorohexyl chloride or perfluorohexyl bromide were produced.
Alkyl halides can be synthesized through the substitution of hydrogen
atoms by halogens under varying experimental conditions (Gu et al.,
2013; Sugiyama et al., 1999). This observation raises the possibility that
1H-perfluorohexane may serve as a precursor to perfluorohexyl chlo­
ride, but other mechanisms and intermediates may also occur. Never­
theless, a competitive reaction pathway may exist between the
formation of these two compounds.
The occurrence of chlorinated organic compound formation during
thermal processes is not unprecedented. Previous studies have docu­
mented the formation of dioxins during the gasification of municipal
solid waste, and the impact of temperature has been well investigated
(McKay, 2002a). Notably, it has been demonstrated that de novo syn­
thesis of dioxin can be achieved in the presence of CuCl2 or FeCl3, which
both act as chlorine sources and catalysts, at temperatures below 600 ◦ C
(Cai et al., 2022; Bei et al., 2022; Mckay, 2002b). NaCl, although not
directly causing dioxin formation, may enter the gas phase at lower
temperatures and catalyze dioxin synthesis by exchanging ions with
metals like Fe/Cu (Bei et al., 2022). In our experiment setup, NaCl was
mixed with the sand and placed within a stainless-steel furnace tube.
Both the sand and the stainless-steel tube could potentially serve as
sources of iron for the formation of FeCl3, the sand due to the presence of
iron minerals, and the stainless-steel tube due to the presence of triva­
lent iron on its surface due to repeated use and exposure to HF. Further
experimental validation is required to substantiate such hypotheses
regarding the exact mechanistic understanding of mixed-halogen per­
haloalkane production.
One challenge in utilizing thermal treatment approaches for PFAS
treatment concerns the generation of unknown VOF. Given the number
of VOF that may result from low temperature thermal treatment, more
information regarding these compounds is needed, and analytical
methods are still under development (Yao et al., 2022; Baker et al.,
2023; Watanabe et al., 2016). While it is uncertain whether chlorinated
perfluoroalkyl compounds beyond perfluorohexyl chloride were gener­
ated in our studies, the observation of m/z 129 (and m/z 131) ion
fragments at multiple retention times is interesting and provides
Y. Zhao et al. Environmental Pollution 348 (2024) 123782

Fig. 1. Ion fragment comparison of known VOF compounds and VOF generated during thermal decomposition experiments. a) Ion fragment abundance for the
mixture of seven VOF stocks; b) Total ion fragment abundance of VOF from PFHxS pyrolysis; c) Ion fragment abundance for perfluorohexyl chloride; d) Total ion
fragment abundance of VOF from PFHxS pyrolysis in the presence of NaCl; e) Ion fragment abundance for the perfluorohexyl bromide; f) Total ion fragment
abundance of VOF from PFHxS pyrolysis in the presence of NaBr.

4
Y. Zhao et al.
Fig. 2. a) Abundance of selected ion fragments relative to CF+
3 for perfluorohexyl chloride stock and in the peak detected at 6.1 min in the gas collected during PFHxS
pyrolysis in presence of NaCl; b) Abundance of selected ion fragments relative to CF+
3 for perfluorohexyl bromide stock and in the peak detected at 6.8 min in the gas
collected during PFHxS pyrolysis in presence of NaBr.
preliminary evidence of additional perfluoroalkyl bromide compounds
beyond perfluorohexyl bromide. This might further extend the list of
VOF that should be considered during thermal treatment of
PFAS-contaminated wastes. The formation of mixed halogenated
by-products illustrates challenges associated with characterizing and
quantifying performance of thermal PFAS treatment approaches utiliz­
ing lower temperature processes – both ex situ and in situ (Wang et al.,
2022). Whether higher temperature processes are sensitive to similar
effects may also warrant consideration.
These initial studies, conducted with a single representative PFAA
(PFHxS) and two simple halogen salts, raise several questions. For
example, which PFAS or structural components of PFAS are susceptible
to formation of mixed halogen VOF during thermal processes, and can
the resulting products be predicted? Can other possible co-occurring
halogenated compounds (e.g., chlorinated solvents) beyond the simple
salts studied during this effort serve as Cl or Br sources that also lead to
mixed halogenated VOF during thermal treatment? How do matrix
conditions (e.g., different salt concentrations) impact formation of the
mixed halogen VOF, and can better understanding of such variations be
utilized to yield more favorable products? Finally, what is the ultimate
fate of mixed halogenated VOF, and do they warrant health and/or
regulatory concerns? Further research is required to improve mecha­
nistic understanding of the formation of these mixed halogen VOF
during thermal PFAS decomposition, and to better define the extent of
this issue, including implications for both ex situ and in situ thermal
treatment of PFAS.
4. Conclusion
In this study, we experimentally identified perhaloalkanes with
mixed halogens generated during the low temperature pyrolysis of
PFHxS. Our thermal experiments with PFHxS in the presence of solid
NaCl and NaBr resulted in perfluorohexyl chloride and perfluorohexyl
bromide products, respectively. These studies demonstrate that mixed
halogenated products may occur as PFAS pyrolysis by-products at
5
Environmental Pollution 348 (2024) 123782
relatively low temperatures and further illustrate the challenge of fully
accounting for all fluorine during thermal decomposition of PFAS.
Because chlorine is ubiquitous in soil, water, and many industrial and
municipal waste streams, it is likely to be present with PFAS during any
type of thermal treatment, potentially yielding chlorinated VOF. During
the envisioned thermal treatment approaches for PFAS contaminated
media, the elimination of chlorine and bromine may not be practical or
feasible. Therefore, a more comprehensive understanding of the thermal
decomposition of PFAS, the formation of mixed halogen VOF products,
and their destruction, will be essential in developing effective strategies
for managing PFAS and minimizing potential environmental and human
health risks.
CRediT authorship contribution statement
Yuwei Zhao: Writing – review & editing, Writing – original draft,
Visualization, Validation, Software, Project administration, Investiga­
tion, Data curation, Conceptualization. Paul G. Koster van Groos:
Writing – review & editing, Visualization, Funding acquisition, Data
curation, Conceptualization. Nikita Thakur: Investigation. Mark E.
Fuller: Writing – review & editing, Supervision, Conceptualization.
Anthony Soto: Formal analysis. Paul B. Hatzinger: Writing – review &
editing, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Y. Zhao et al.
Acknowledgments
The investigators acknowledge and thank the Strategic Environ­
mental Research and Development Program for support of this research
under project ER21-1135 (grant W912HQ21C0046). Views, opinions,
and/or findings contained herein are those of the authors and should not
be construed as an official Department of Defense position or decision
unless so designated by other official documentation.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.envpol.2024.123782.
References
Al Amin, M., et al., 2020. Recent advances in the analysis of per- and polyfluoroalkyl
substances (PFAS)—a review. Environ. Technol. Innovat. 19 https://doi.org/
10.1016/j.eti.2020.100879. Preprint at.
Aleksandrov, K., et al., 2019. Waste Incineration of Polytetrafluoroethylene (PTFE) to
Evaluate Potential Formation of Per-And Poly-Fluorinated Alkyl Substances (PFAS)
in Flue Gas. https://doi.org/10.1016/j.chemosphere.2019.03.191.
Altarawneh, M., Almatarneh, M.H., Dlugogorski, B.Z., 2022. Thermal decomposition of
perfluorinated carboxylic acids: kinetic model and theoretical requirements for PFAS
incineration. Chemosphere 286, 131685.
Arana Juve, J.-M., Wang, B., Wong, M.S., Ateia, M., Wei, Z., 2023. Complete
defluorination of per- and polyfluoroalkyl substances — dream or reality? Curr Opin
Chem Eng 41, 100943.
Baker, T.J., et al., 2023. An infrared spectral database for gas-phase quantitation of
volatile per-and polyfluoroalkyl substances (PFAS). J. Quant. Spectrosc. Radiat.
Transf. 295, 108420.
Bei, J., et al., 2022. Revealing the mechanism of dioxin formation from municipal solid
waste gasification in a reducing atmosphere. Environ. Sci. Technol. 56,
14539–14549.
Bell, E.M., et al., 2021. Exposure, health effects, sensing, and remediation of the
emerging PFAS contaminants – scientific challenges and potential research
directions. Sci. Total Environ. 780. https://doi.org/10.1016/j.
scitotenv.2021.146399. Preprint at.
Buck, R.C., et al., 2011. Perfluoroalkyl and polyfluoroalkyl substances in the
environment: terminology, classification, and origins. Integrated Environ. Assess.
Manag. 7, 513–541.
Cai, P., et al., 2022. Formation mechanism and influencing factors of dioxins during
incineration of mineralized refuse. J. Clean. Prod. 342.
Cordner, A., et al., 2019. Guideline levels for PFOA and PFOS in drinking water: the role
of scientific uncertainty, risk assessment decisions, and social factors. J. Expo. Sci.
Environ. Epidemiol. 29, 157–171.
DiStefano, R., Feliciano, T., Mimna, R.A., Redding, A.M., Matthis, J., 2022. Thermal
destruction of PFAS during full-scale reactivation of PFAS-laden granular activated
carbon. Remediation 32, 231–238.
Garg, S., et al., 2021. Remediation of water from per-/poly-fluoroalkyl substances (PFAS)
- challenges and perspectives. J. Environ. Chem. Eng. 9.
Gu, L., Lu, T., Zhang, M., Tou, L., Zhang, Y., 2013. Efficient oxidative chlorination of
aromatics on saturated sodium chloride solution. Adv. Synth. Catal. 355,
1077–1082.
Hauptschein, M., Grosse, A.V., 1951. Perfluoroalkyl halides prepared from silver
perfluoro-fatty acid salts. I. Perfluoroalkyl iodides. J. Am. Chem. Soc. 73,
2461–2463.
Hauptschein, M., Nodiff, E.A., Grosse, A.V., 1952. Perfluoroalkyl halides prepared from
silver perfluoro-fatty acid salts. II. Perfluoroalkyl bromides and chlorides. J. Am.
Chem. Soc. 74, 1347–1350.
Jahnke, A., Berger, U., 2009. Trace analysis of per- and polyfluorinated alkyl substances
in various matrices—how do current methods perform? J. Chromatogr. A 1216,
410–421.
Krug, J.D., et al., 2022. Combustion of C1 and C2 PFAS: kinetic modeling and
experiments. J. Air Waste Manage. Assoc. 72, 256–270.
Krusic, P.J., Roe, D.C., 2004. Gas-phase NMR technique for studying the thermolysis of
materials: thermal decomposition of ammonium perfluorooctanoate. Anal. Chem.
76, 3800–3803.
Environmental Pollution 348 (2024) 123782
Kundu, S., et al., 2021. Removal of PFASs from biosolids using a semi-pilot scale
pyrolysis reactor and the application of biosolids derived biochar for the removal of
PFASs from contaminated water. Environ. Sci. 7, 638–649.
LaZerte, J.D., Hals, L.J., Reid, T.S., Smith, G.H., 1953. Pyrolyses of the salts of the
perfluoro carboxylic acids. J. Am. Chem. Soc. 75, 4525–4528.
Liang, C., Su, H.W., 2009. Identification of sulfate and hydroxyl radicals in thermally
activated persulfate. Ind. Eng. Chem. Res. 48, 5558–5562.
Longendyke, G.K., Katel, S., Wang, Y., 2022. PFAS fate and destruction mechanisms
during thermal treatment: a comprehensive review. Environ. Sci. J. Integr. Environ.
Res.: Process. Impacts 24 196–208. https://doi.org/10.1039/d1em00465d. Preprint
at.
Maga, D., Aryan, V., Bruzzano, S., 2021. Environmental assessment of various end-of-life
pathways for treating per- and polyfluoroalkyl substances in spent fire-extinguishing
waters. Environ. Toxicol. Chem. 40, 947–957.
McKay, G., 2002a. Dioxin characterisation, formation and minimisation during
municipal solid waste (MSW) incineration: review. Chem. Eng. J. 86, 343–368.
Mckay, G., 2002b. Dioxin characterisation, formation and minimisation during
municipal solid waste (MSW) incineration: review. Chem. Eng. J. 86.
Roth, J., et al., 2020. Release of volatile per-and polyfluoroalkyl substances from aqueous
film-forming foam. Environ. Sci. Technol. Lett. 7, 164–170.
Shahsavari, E., et al., 2021. Challenges and current status of the biological treatment of
PFAS-contaminated soils. Front. Bioeng. Biotechnol. 8 https://doi.org/10.3389/
fbioe.2020.602040. Preprint at.
Sonmez Baghirzade, B., et al., 2021. Thermal regeneration of spent granular activated
carbon presents an opportunity to break the forever PFAS cycle. Environ. Sci.
Technol. 55, 5608–5619.
Sugiyama, H., Katagiri, Y., Kaneko, M., Watanabe~and, T., Hirayama, T., 1999.
Chlorination of pyrene in soil components with sodium chloride under xenon
irradiation. Chemosphere 38.
Sznajder-Katarzyńska, K., Surma, M., Cieślik, I., 2019. A review of perfluoroalkyl acids
(PFAAs) in terms of sources, applications, human exposure, dietary intake, toxicity,
legal regulation, and methods of determination. J. Chem. 2019.
Tsugawa, H., et al., 2015. MS-DIAL: data-independent MS/MS deconvolution for
comprehensive metabolome analysis. Nat. Methods 12, 523–526.
Vecitis, C.D., Park, H., Cheng, J., Mader, B.T., Hoffmann, M.R., 2009a. Treatment
technologies for aqueous perfluorooctanesulfonate (PFOS) and perfluorooctanoate
(PFOA). Front. Environ. Sci. Eng. China 3, 129–151.
Vecitis, C.D., Park, H., Cheng, J., Mader, B.T., Hoffmann, M.R., 2009b. Treatment
technologies for aqueous perfluorooctanesulfonate (PFOS) and perfluorooctanoate
(PFOA). Front. Environ. Sci. Eng. China 3, 129–151.
Verma, S., Lee, T., Sahle-Demessie, E., Ateia, M., Nadagouda, M.N., 2023. Recent
advances on PFAS degradation via thermal and nonthermal methods. Chemical
Engineering Journal Advances 13. https://doi.org/10.1016/j.ceja.2022.100421.
Preprint at.
Wang, J., Song, M., Abusallout, I. & Hanigan, D. Thermal Decomposition of Two Gaseous
Perfluorocarboxylic Acids: Products and Mechanisms. doi:10.1021/acs.est.2c08210.
Wang, J., et al., 2022. Critical review of thermal decomposition of per-and
polyfluoroalkyl substances: mechanisms and implications for thermal treatment
processes. Cite This: Environ. Sci. Technol. 2022, 5370.
Watanabe, N., Takemine, S., Yamamoto, K., Haga, Y., Takata, M., 2016. Residual organic
fluorinated compounds from thermal treatment of PFOA, PFHxA and PFOS adsorbed
onto granular activated carbon (GAC). J. Mater. Cycles Waste Manag. 18, 625–630.
Watanabe, N., Takata, M., Takemine, S., Yamamoto, K., 2018. Thermal mineralization
behavior of PFOA, PFHxA, and PFOS during reactivation of granular activated
carbon (GAC) in nitrogen atmosphere. Environ. Sci. Pollut. Control Ser. 25,
7200–7205.
West, C.P., Brown, H.M., Fedick, P.W., 2023. Molecular characterization of the thermal
degradation of per- and polyfluoroalkyl substances in aqueous film-forming foams
via temperature-programmed thermal desorption–pyrolysis–direct analysis in real
time–mass spectrometry. Environ. Sci. Technol. Lett. https://doi.org/10.1021/acs.
estlett.3c00064.
Xiao, F., et al., 2020. Thermal stability and decomposition of perfluoroalkyl substances
on spent granular activated carbon. Environ. Sci. Technol. Lett. 7, 343–350.
Yao, B., et al., 2022. The First Quantitative Investigation of Compounds Generated from
PFAS, PFAS-Containing Aqueous Film-Forming Foams and Commercial
Fluorosurfactants in Pyrolytic Processes. https://doi.org/10.1016/j.
jhazmat.2022.129313.
Zhang, J., et al., 2023. Review of influence of critical operation conditions on by-
product/intermediate formation during thermal destruction of PFAS in solid/
biosolids. Sci. Total Environ. 854.