Water Research 198 (2021) 117121

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Water Research
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Microwave regeneration of granular activated carbon saturated with

PFAS
Erica Gagliano a, Pietro P. Falciglia a, Yeakub Zaker b, Tanju Karanfil b,∗, Paolo Roccaro a,∗
a
Department of Civil Engineering and Architecture, University of Catania, Catania, 95125, Italy
b
Department of Environmental Engineering and Earth Science, Clemson University, Clemson (SC), 29634, United States of America

a r t i c l e i n f o a b s t r a c t

Article history: This study investigated the regeneration of PFAS-saturated granular activated carbons (GACs) by mi-
Received 18 January 2021 crowave (MW) irradiation. Two commercially available GACs (bituminous coal based GAC [BCGAC] and
Revised 29 March 2021
lignite coal based GAC [LCGAC]) were saturated with perfluorooctanoic acid (PFOA) and perfluorooctane
Accepted 3 April 2021
sulfonic acid (PFOS) and then irradiated at different MW conditions (applied power = 125 - 500 W, irra-
Available online 5 April 2021
diation time = 3 - 12 min). The performance of MW regeneration for PFOS- or PFOA-saturated GACs was
Keywords: assessed by evaluating the variation of GAC adsorption capacity (regeneration efficiency, RE) and weight
GAC adsorption loss percentage (WL). Moreover, the effect of MW irradiation on GAC textural properties (e.g., surface
Contaminants of emerging concern (CEC) area and pore volume) was examined through N2 adsorption isotherms. Additionally, five successive ad-
Microwave (MW) irradiation sorption/regeneration cycles were carried out at the MW operational condition that allowed to reach the
Poly- and perfluoroalkyl substances (PFAS) target temperature (T>600°C) while minimizing the WL.
Regeneration.
Both GACs exhibited a strong ability to convert MW irradiation into a rapid temperature increase (~150°C
min−1 at 500 W). The highest values of RE (>90%) for both PFOA- and PFOS-saturated GACs were ob-
tained at MW irradiation conditions that employed short regeneration time (3 min) and optimal tem-
perature. Indeed, the highest RE did not occur at the highest temperatures (>750°C) due to the damage
of GAC porous structure, particularly for LCGAC. After five cycles, the observed values of RE (~65%) and
a moderate weight loss (<7%) demonstrated the good performance of MW irradiation for regenerating
PFOA- and PFOS-saturated BCGAC. The obtained findings pointed out that MW irradiation is a promising
alternative regeneration technique for PFAS-saturated GAC.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction sequently, PFAS are categorized into long-chain and short-chain,

Poly- and perfluoroalkyl substances (PFAS) are a class of an-
thropogenic compounds that attracted attention worldwide as con-
taminants of high concern (Ateia et al., 2019; ITRC, 2020). Over
several decades, they have been used in an array of formulations
for the manufacture of several commercial products such as fire-
fighting foams, food packing, stain repellents, and non-stick cook-
ware (Buck et al., 2011; Rahman et al., 2014). The widespread
use of PFAS is certainly ascribable to their unique properties such
as chemical-thermal stability and hydrophilic-lipophilic nature im-
parted by chemical composition (Gagliano et al., 2020; ITRC, 2017).
PFAS structure is made up of a C-F chain of varying length, and it
also includes a charged functional group attached at one end (e.g.,
carboxylic or sulfonic acid) (Buck et al., 2011; Du et al., 2014). Con-
∗
Corresponding authors:
E-mail addresses: tkaranf@clemson.edu (T. Karanfil), paolo.roccaro@unict.it (P.
Roccaro).
according to C-F chain length, and into perfluoroalkyl carboxylic
acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs), according
to the type of functional group (Buck et al., 2011; ITRC, 2017).
Recently, PFAS have been called “forever chemicals” due to their
persistence and mobility in environment as well as their toxicity
for human and wildlife (Crawford et al., 2017; Hölzer et al., 2009;
Sorlini et al., 2019). Their occurrence in water bodies is the re-
sult of consumer-product degradation, firefighting activities, and
discharges of fluorochemical manufacturing facilities (Ateia et al.,
2019; Hu et al., 2016). Consequently, PFAS have been detected
worldwide from ng L−1 to μg L−1 or even mg L−1 levels at some
contaminated sites (Gagliano et al., 2020; Rahman et al., 2014).
Amongst long-chain PFAS, perfluorooctanoic acid (PFOA) and per-
fluorooctane sulfonic acid (PFOS) has been the most widely used
and, although their production has been banned, they have been
detected in groundwater, surface water, wastewater, and tap wa-
ter around the world (Gagliano et al., 2020; Takagi et al., 2008).
The need for efficient PFAS removal from water is a growing need

https://doi.org/10.1016/j.watres.2021.117121
0043-1354/© 2021 Elsevier Ltd. All rights reserved.
E. Gagliano, P.P. Falciglia, Y. Zaker et al.
as a result of increasing regulatory attention and general concern
regarding the exposure effects (Kucharzyk et al., 2017; Park et al.,
2020; Sorlini et al., 2019). In recent years, a significant progress has
been made to investigate the application of innovative advanced
technologies such as plasma treatment, electrochemical and pho-
tocatalysis (Ji et al., 2020; Ross et al., 2018). Nevertheless, at pilot-
and full-scale operations, adsorption using granular activated car-
bon (GAC) has been the most widely used approach for treatment
of PFAS-contaminated water (Du et al., 2014; Gagliano et al., 2020;
Shivakoti et al., 2010). However, periodic GAC replacement is re-
quired.
From an environmental and sustainability standpoint, the re-
generation of exhausted AC is a more attractive alternative then
landfill disposal, which could lead to a secondary contamination
pathway. The regeneration should allow an increase in GAC life-
time, restoring its adsorption capacity by removing the adsorbed
PFAS (Gagliano et al., 2020; Yuen and Hameed, 2009). However, the
regeneration of PFAS-exhausted GAC is a challenging task for both
water utilities and activated carbon manufactures. Among different
regeneration techniques, chemical regeneration, using a solution of
sodium salts and organic alcohol, allows the desorption of PFAS
molecules out of carbon pores (Wang et al., 2014; Woodard et al.,
2017). However, the use of organic alcohol has negative impacts
for full-scale applications and, consequently, on-site regeneration
is not feasible (Gagliano et al., 2020). Furthermore, the manage-
ment of eluate having high PFAS concentration is another limiting
factor of chemical regeneration. Over the years, the thermal regen-
eration of exhausted GAC has been extensively performed at 800
- 10 0 0°C under mildly oxidizing atmospheric conditions (usually
carbon dioxide and steam) (Guo and Du, 2012; Zanella et al., 2014).
However, these conditions lead to a considerable amount of carbon
lost (5 - 15%) by attrition, burn-off and washout, and, subsequent
decline in the adsorption capacity (Zanella et al., 2014). Further-
more, thermal regeneration under oxidative gases negatively af-
fects carbon porous structure (e.g., a decrease in micropore volume
and a shift to pores of narrower sizes) and it may lead to changes
in carbon functional groups. The carbonization of adsorbates may
also result in pore blockage due to coke formation (Ania et al.,
2005).
Therefore, the development of alternative regeneration tech-
niques for PFAS-exhausted GAC is highly desirable in order to: (i)
avoid the harmful secondary pollution after landfill disposal, (ii)
save costs related to GAC replacement, (iii) restore GAC adsorption
capacity while ensuring the preservation of its porous structure
(Gagliano et al., 2020; Yuen and Hameed, 2009).
Developed for radar and communication purposes, microwave
(MW) irradiation is a well-established technology alternative to
conventional heating. It has also been recently proposed as a po-
tentially viable approach for regenerating GAC saturated with both
organic and inorganic compounds (Ania et al., 2007; Ao et al.,
2018; Falciglia et al., 2020b; Foo and Hameed, 2012). Compared
to conventional thermal heating, MW irradiation offers several ad-
vantages: interior heating, higher heating rates, selective heating,
greater control of the heating process, no direct contact between
the heating source and heated materials, and reduced equipment
size and waste (Falciglia et al., 2018; Kim et al., 2014). Previous
studies have pointed out the outperformance of the MW over
conventional thermal regeneration for saturated activated carbons
(Ania et al., 2005; Durán-Jiménez et al., 2019).
The major driving force of the treatment is the dielectric na-
ture of the irradiated material (e.g., activated carbon), which al-
lows the conversion of low power irradiation energy into a rapid
temperature increase (Ania et al., 2007; Falciglia et al., 2020a).
Its dielectric heating capacity leads to a large reduction in treat-
ment time and energy consumption, making the application cost-
effective (Ao et al., 2018; Falciglia et al., 2018). Jointly with high
2
Water Research 198 (2021) 117121
GAC dielectric features, high mechanical strength and a good re-
sistance towards heat and radiation are other essential features for
promoting GAC regeneration by MW irradiation (Ania et al., 2007;
Biniak et al., 1997; Durán-Jiménez et al., 2019; Gagliano et al.,
2019). To the best of our knowledge, the applicability of MW ir-
radiation for regenerating PFAS-saturated GACs has not been re-
ported in the literature. Therefore, the aim of the present study
was to systematically examine the regeneration of two com-
mercially available GACs saturated with selected long-chain PFAS
(i.e., PFOA and PFOS) by MW irradiation for multiple adsorp-
tion/regeneration cycles. MW regeneration was performed at dif-
ferent operational conditions (MW power levels and irradiation
times) in order to examine the variation in GAC adsorption ca-
pacity (in terms of regeneration efficiency) and GAC weight loss
percentage. Afterwards, the optimum temperature for MW regen-
eration with the lowest GAC weight loss was selected to carry out
five successive PFAS adsorption/regeneration cycles. The changes in
GAC textural properties (e.g., surface area and pore volume) after
MW irradiation were assessed through N2 adsorption isotherms in
order to evaluate the MW effect on GAC porous structure.
2. Materials and methods
2.1. Materials
The two commercial GACs selected for the experiments are ob-
tained from steam activation of bituminous coal (BCGAC) and lig-
nite coal (LCGAC), and they were purchased from Calgon Carbon
Corporation and Norit, respectively (Table 1). Both GACs have been
extensively tested in PFAS removal studies, and they are currently
employed at water treatment facilities (Kothawala et al., 2017;
Liu et al., 2019; Ochoa-Herrera and Sierra-Alvarez, 2008; Park et al.,
2020). As-received GACs were washed in distilled and deionized
water (DDW) several times, dried at 100°C overnight and then
stored in a desiccator until use. The dried GACs were sieved at 10
- 20 mesh size in order to obtain a fraction from 0.85 to 2 mm.
PFOS (CAS n. 1763-23-1, ≥ 96% purity) and PFOA (CAS n. 335-
67-1, ≥ 96% purity) were obtained from Sigma Aldrich. Liquid chro-
matography (LC) - grade ammonium acetate, acetonitrile and wa-
ter were purchased from Fischer Scientific. Table S1 (Supplemen-
tary materials) reports the physicochemical properties of PFOA and
PFOS investigated in this study.
2.2. Adsorption and MW regeneration experiments
In order to obtain GACs (both BCGAC and LCGAC) fully satu-
rated with PFOA and PFOS, GAC samples were saturated with high
concentrated (500 mg L−1 ) solution of PFOA or PFOS in DDW, to
ensure that the active sites on GAC inner surface were fully oc-
cupied (Foo, 2018; Sun et al., 2017). Five grams of GAC (BCGAC
or LCGAC) were added to 200 mL of solution (PFOA or PFOS in
DDW), the mixture was kept stirred (180 rpm) at room tempera-
ture (25 ±1°C) for 24 h to ensure that the equilibrium was estab-
lished, as also confirmed with the preliminary tests which was in
agreement with previous experimental studies (Ochoa-Herrera and
Sierra-Alvarez, 2008; Yao et al., 2014). After saturation, aqueous
Table 1
Features of GACs used for the experiments.
LCGAC BCGAC
Base material (-) Lignite coal Bituminous coal
Iodine number (mg g-1 ) 500 1000
Abrasion resistance (AWWA) (%) min. 70 min. 75
Moisture (as packed) (%) max. 8 max. 2
Apparent density, vibrating feed (g mL-1 ) 0.38 0.49
Uniformity coefficient (-) 2.1 1.9
E. Gagliano, P.P. Falciglia, Y. Zaker et al.
samples were centrifugated to separate the activated carbons be-
fore analysis through Liquid Chromatography/Mass Spectrometry
(LC/MS-MS) (as described in “Analytical methods” section) in order
to measure the remaining concentration of compounds in solution.
The amount of PFOA and PFOS adsorbed by BCGAC and LCGAC was
calculated as follows:
V(C0 −Cf )
q= (1)
m
where, q is the adsorption capacity (mg g−1 ), C0 (mg L−1 ) and Cf
(mg L−1 ) are the initial and final concentrations of each compound
in the solution, respectively, and V (L) is the volume of the solu-
tion and m (g) is the GAC mass. PFOA- or PFOS-saturated BCGAC
and LCGAC were separated from liquid solution through vacuum
filtration and transferred into ceramic crucible for the regeneration
experiments.
A modified domestic 2.45 GHz - MW oven equipped with cy-
clonic inverter owing a maximum power of 1.25 kW was employed
for the saturated GAC - regeneration purpose. The temperature
(T,°C) reached by GACs after MW irradiation was recorded through
a k-type thermocouple (Omega Engineering Inc., U.S.A.).
Before performing MW regeneration of PFAS-saturated GAC, 5
g of BCGAC or LCGAC, separately, were subjected to MW irradia-
tion at different power levels (from 125 to 500 W) and irradiation
times (from 3 to 12 min) to develop the temperature profiles. Con-
sequently, based on temperature reached by GACs, several MW ir-
radiation conditions (combinations of power and irradiation time)
were selected and applied for the regeneration of PFOA- and PFOS-
saturated GACs.
The dried regenerated GAC was employed in the subsequent ad-
sorption test and a small amount (~20 mg) was used for GAC char-
acterization (as reported in section 2.3). Adsorption tests were car-
ried out as reported above. The efficiency of MW regeneration was
evaluated by means of the regeneration efficiency (RE, %) and the
single-step desorption efficiency (SSDE, %). Specifically, SSDE allows
the understanding of PFOA and PFOS desorption among different
cycles, whereas RE enables to study the evolution of the overall
yield of MW regeneration. The RE was calculated as followed:
qi
RE = · 100 (2)
q0
Where qi is the adsorption capacity of the MW regenerated GAC
and q0 is the adsorption capacity of the virgin GAC. Whereas, the
SSDE was determined by:
qn
SSDE = · 100 (3)
qn−1
Where qn and qn-1 are the adsorption capacities of the MW re-
generated GAC in a given cycle n and in the previous regeneration
cycle (n-1), respectively.
Besides the RE and SSDE, GAC weight loss percentage (WL, %)
represents another important parameter could affect the applica-
bility of MW for the regeneration of PFOA- and PFOS-saturated
GAC. It was calculated as:
w0 −wt
WL = · 100 (4)
w0
Where w0 and wt are the mass of GAC (g) before and after MW
irradiation, respectively.
The operating conditions (i.e., irradiation power and irradiation
time), which allow the achievement of the highest RE and the low-
est WL values, were selected for the successive five adsorption-
regeneration cycles.
In order to verify the potential leaching of PFOS or PFOA and
their related shorter chain compounds (as degradation products)
from MW-regenerated GACs, 5 g of PFOA- or PFOS-saturated BC-
GAC after MW regeneration (irradiated at T>600°C) were added
3
Water Research 198 (2021) 117121
to 200 mL of DDW (PFAS free solution) or to 200 mL of MeOH
with NaOH (100 mmol L−1 ) (MeOH+NaOH solution). The two
mixtures were kept stirred (180 rpm) at room temperature (25
±1°C) for 48 h. Then, liquid samples from the two mixtures were
withdrawn and analysed through LC/MS-MS (as described below)
in order to determine the residual concentrations of PFAS (both
long- and short-chain compounds) potentially released from MW-
regenerated BCGAC in DDW or MeOH+NaOH solution. Specifically,
MeOH+NaOH solution was selected due to its high PFAS recovery
from GAC (~90-100%), in agreement with Xiao et al. (2020).
2.3. GAC characterization
The surface areas, pore volumes and pore size distributions
of GAC samples (before and after MW irradiation) were mea-
sured by nitrogen physisorption data at 77 °K after degassing
the samples at 298 °K for 10 h with ASAP 2020 analyzer (Mi-
cromeritics Instrument Corp. U.S.). Brunauer-Emmett-Teller (BET)
equation was used to calculate the specific surface area, whereas
the pore size distribution of GAC samples were determined from
the nitrogen isotherms using the Density Functional Theory (DFT)
(Dastgheib et al., 2004; Lowell et al., 1985). The reproducibility of
measurements was assessed from triplicate data of randomly se-
lected samples and the relative standard deviation (RSD) of BET
surface area, micropore volume, and total pore volume resulted
less than 4 %.
2.4. Analytical method
The determination of PFOA and PFOS was conducted using the
method described by Park et al. (2020), with few modifications.
Specifically, the high-volume direct injection was performed using
a Liquid Chromatography coupled to ESI-triple Quadrupole Mass
Spectrometer (Agilent 6470 LC/TQ) operated in the negative ion-
ization mode. The mobile phase (in LC grade solvents) was: A) 100
mM ammonium acetate in water (pH 10) B) acetonitrile. A combi-
nation of 50% of A and 50% of B was delivered at a flow rate of 0.4
mL min−1 by the binary pump.
An Agilent ZORBAX RRHD Eclipse Plus C18 column (2.1 × 100
mm, 1.8 μm particle size) was installed at the Binary pump. More-
over, polytetrafluoroethylene-free vials, caps, and septa were used
to reduce PFAS background. Data acquisition was performed in
Multiple Reaction Monitoring (MRM) mode. For each compound,
two MRM transitions (PFOS: 499/80, 499/99; PFOA: 413/169,
413/369) were used for quantification and confirmation, respec-
tively.
Due to the high concentrations used in the present study, sam-
ples were diluted with LC grade water to obtain concentrations
ranging between 5 - 500 μg L−1 . Afterwards, calibration curves
were constructed and the correlation coefficients (R2 ) of the cali-
bration curves for PFOS and PFOA were >0.98. Based on the lowest
acceptable calibration standard, the detection limit of both PFOA
and PFOS measurements was 1 μg L−1 . For selected experiments
carried out to monitor the potential release of PFAS from MW re-
generated GAC, the analytical determination of other PFAS (listed
in Table S2) was conducted using the method described above with
few modifications. In these measurements the detection limit was
0.4 μg L−1 .
3. Results and discussion
3.1. GAC temperature profiles and weight loss during MW irradiation
The variation of GACs temperature with irradiation times at
different power levels is shown in Fig. 1. The comparison of the
temperature profiles reveals that both BCGAC and LCGAC have the
E. Gagliano, P.P. Falciglia, Y. Zaker et al. Water Research 198 (2021) 117121

Fig. 1. Temperature profiles of BCGAC [a] and LCGAC [b] at 3 different power levels (250, 375 and 500 W). (Red dashed line indicates Ttarget =600 °C).

same trend, where temperature increases with increasing the ir- Table 2
Experimental conditions of MW irradiation for PFOA- and PFOS-saturated GACs
radiation time and power. However, LCGAC reached higher tem-
(both BCGAC and LCGAC).
perature than BCGAC when the MW power was 375 W for irra-
diation time longer than 3 min. Moreover, at the highest power Experimental Power Irradiation Total consumed Temperature
conditions (Watt) time (min) energy (kWh) reached ≥ 600 °C
investigated (500 W), the increase in temperature (°C) with ir-
radiation time (min) was faster for LCGAC than BCGAC (156 and 1 125 12 0.025 NO
146°C min−1 , respectively). Overall, among the operational condi- 2 250 6 0.025 YES
3 250 8 0.033 YES
tions investigated, the irradiation at 500 W for 5 min resulted in
4 375 4 0.025 YES
the highest GAC temperatures, which were 730 and 780°C for BC- 5 375 6 0.038 YES
GAC and on LCGAC, respectively. However, temperatures ≥ 600°C 6 500 3 0.025 YES
were also attained at a lower MW power (250 W) applied for 6
min and above, demonstrating the ability of GACs to convert a low
adsorbed MW power into a rapid temperature increase. Regardless placement, as previously demonstrated by Falciglia et al. (2020a).
of power applied, both GACs reached the minimal value of 250°C WL – T relationship may also be useful in the selection of commer-
after 1 min of irradiation, which correspond to a T increase ratio cially available GACs. At a comparable value of adsorption capacity
of 250°C min−1 . This sharp rise of GAC temperature within short for a target compound, GAC characterized by lower WL and sharp
irradiation times is the key factor in the MW regeneration process. T rise should be preferred since it is more prone to MW irradiation
The difference in temperature profiles observed for the BC- or thermal regeneration.
GAC and LCGAC samples may be ascribed to difference in their Among the different experimental conditions investigated in the
chemical composition. The oxygen content in LCGAC is higher than present study to develop temperature profiles, six combinations of
that of BCGAC, 8.7% and 5.9% respectively (Cheng et al., 2005; power (W) and irradiation time (t, min) were selected for the re-
Dastgheib et al., 2004). Indeed, most of oxygen functionalities are generation of PFAS-saturated GAC (Table 2). These combinations of
polar functional groups, which are more prone to absorb MW en- power and irradiation time correspond to a total consumed en-
ergy than nonpolar ones (Pi et al., 2017), providing a plausible ex- ergy (E) in the 0.025 - 0.038 kWh range (Remya and Lin, 2011).
planation for the highest temperature reached in LCGAC during the Specifically, the highest E is achievable applying a power of 375
MW irradiation. W for an irradiation time of 6 min, whereas the lowest one is at-
The variation of weight loss with temperature increase on BC- tained when GAC samples were irradiated at 125 W for 12 min,
GAC and LCGAC samples (irradiated at several power levels and ir- 250 W for 6 min, or 500 W for 3 min. The MW irradiation con-
radiation times) is shown in Fig. 2. ditions employed in the present study were selected based on the
The GAC weight loss (WL, %) increased linearly with the in- criterion of maintaining the GAC (both BCGAC and LCGAC) temper-
crease in temperature (R2 >0.98), and the highest WLs were 6.1% ature over 600°C, which would allow the PFOA and PFOS thermal
and 6.9% for BCGAC and LCGAC, respectively. desorption from GACs. This value can be referred to the thermo-
Weight loss is one of the main factors affecting the scaling-up gravimetric (TGA) analysis of PFOA and PFOS chemical compounds,
of the MW technology, especially to calculate the cost of GAC re- as reported elsewhere (Wang et al., 2011; Xiao et al., 2020). The

Fig. 2. Variation of weight loss with GAC temperature ([a] BCGAC, [b] LCGAC). (Red dashed line indicates the highest WL obtained for BCGAC and LCGAC).

4
E. Gagliano, P.P. Falciglia, Y. Zaker et al.
Fig. 3. [a] Temperature, weight loss and [b] regeneration efficiency of PFOA-saturated GAC (BCGAC and LCGAC) for the different MW irradiation conditions investigated.
TGA analysis conducted under N2 atmosphere revealed a single-
step degradation of PFOS at ~425 – 500°C, while PFOA degradation
started at lower temperature (~300°C). Moreover, it was demon-
strated that the total thermal decomposition of a wide group of
PFAS (including PFOA and PFOS) occurred at 600°C (or above)
(Wang et al., 2011; Watanabe et al., 2018, 2016; Xiao et al., 2020).
Indeed, PFAS molecules thermally destabilized are transferred from
GAC to gas phase with the potential generation of organofluorine
compounds (Xiao et al., 2020). Whereas, PFAS thermal destruc-
tion requires temperatures higher than 900°C which are commonly
employed at carbon manufacture plants for GAC reactivation pro-
cess (ITRC, 2018; Xiao et al., 2020). Consequently, for the regenera-
tion purpose, the MW irradiation conditions (power and irradiation
time) applied in the present study were set to ensure the achieve-
ment of temperature needed for PFOA and PFOS thermal decom-
position, avoiding the damage of GAC.
It should be highlighted that when BCGAC and LCGAC were ir-
radiated at 125 W for 12 min, the GAC temperatures were much
lower than 60 0°C (~30 0°C). However, this combination of power
and time (125 W for 12 min) was selected as control experiment
to further understand the PFAS desorption process.
3.2. MW regeneration of PFOA-saturated GACs
The results from batch adsorption experiments showed that the
adsorption capacity of PFOA was 20.0 mg g−1 and 21.9 mg g−1 on
virgin BCGAC and LCGAC, respectively. PFOA-saturated BCGAC and
LCGAC samples were irradiated at several MW operational con-
ditions (Table 2). Temperature, weight loss and regeneration effi-
ciency of PFOA-saturated GACs observed are depicted in Fig. 3. As
expected, PFOA-saturated GAC samples irradiated at 125 W for 12
min reached temperature of 268 and 340°C, respectively, far from
the target temperature of 600°C (Fig. 3a), which also corresponded
to the lowest WLs (< 2% for the BCGAC sample and ~6.5% for the
LCGAC). Overall, PFOA-saturated LCGAC samples exhibited higher
WL than PFOA-saturated BCGAC samples, although in some cases
the temperatures reached by GAC samples were almost the same
(e.g., MW irradiation at 250 W for 6 and 8 min). Moreover, the
highest temperatures were reached for both PFOA-saturated LCGAC
and BCGAC samples (753 and 685°C, respectively) at the power of
375 W applied for 6 min.
The temperatures recorded at the end of the MW regeneration
process (for both BCGAC and LCGAC) were almost similar to that
reached by the virgin GACs when irradiated at the same conditions
(Fig. 1). This suggests that GAC acts as the major MW-absorbing
phase (Durán-Jiménez et al., 2019; Mao et al., 2015), and the pres-
ence of adsorbed PFOA had small influence on the conversion of
electromagnetic energy into heat during MW irradiation.
The regeneration efficiency (RE) calculated according to
Eq. 2 for PFOA-saturated BCGAC and LCGAC as a function of differ-
ent MW powers and irradiation times is shown in Fig. 3b. Barring
5
Water Research 198 (2021) 117121
two conditions (obtained for 125 W - 12 min and 375 W - 6 min,
separately discussed), the RE values were in the range of 75-94%
for both the PFOA-saturated BCGAC and LCGAC.
The lowest values of RE (< 30%) were obtained when PFOA-
saturated GAC samples (BCGAC and H30 0 0) were irradiated at 125
W for 12 min. This combination of MW power and irradiation
time, which corresponds to a total consumed energy of 0.025 kWh,
seems to be insufficient for regenerating PFOA-saturated GAC due
to the low temperatures reached (Fig. 3a). The unsatisfactory re-
generation at 125 W for 12 min was also supported by GAC textu-
ral characterization after MW irradiation, as detailed below. Based
on RE values obtained, it can be argued that the highest MW re-
generation efficiency did not occur at the highest total power con-
sumed (0.038 kWh), which was obtained for a MW irradiation of
375 W for 6 min. At this irradiation condition, the highest temper-
atures have been reached by PFOA-BCGAC and PFOA-LCGAC (685
and 753°C, respectively). Nevertheless, RE for PFOA-BCGAC was
74.3% and RE for PFOA-LCGAC was 60.3% (Fig. 3b).
The RE values of MW irradiation for regenerating PFOA-
saturated GAC are similar to that obtained in previous experimen-
tal studies after one adsorption/regeneration cycle, in which MW
irradiation was investigated for the regeneration of AC samples sat-
urated with organic (e.g., methylene blue, phenol, chlorampheni-
col) (Ania et al., 2005; Foo, 2018; Sun et al., 2017) and inorganic
compounds (e.g., cesium) (Falciglia et al., 2020b).
These findings demonstrate that MW irradiation could effec-
tively regenerate PFOA-saturated GAC. It could be assumed that
adsorbed PFOA was thermally destabilized by MW heating, des-
orbed from GAC and transferred to the gas phase. Indeed, it was
demonstrated that spent GAC (Filtrasorb 200, Calgon Corporation)
saturated with PFOA heated in a quartz tube furnace for 30 min at
temperature higher than 300°C lead to PFOA thermal degradation
to gaseous productions (Xiao et al., 2020). While the highest min-
eralization of PFOA (92.4 mol%) occurred at 700°C. Comparing to
conventional thermal heating, MW irradiation allowed the lower-
ing of treatment time since temperatures higher than 600°C were
obtained in less than 8 min. Moreover, the potential release of
PFOA and its degradation compounds (shorter chain compounds)
from MW regenerated BCGAC (MW irradiated at T>600°C) was
evaluated both in DDW and MeOH+NaOH solution. The results
revealed that PFOA concentrations were 3.5 μg L−1 and 316 μg
L−1 in DDW and MeOH+NaOH solution, respectively. The concen-
trations of other shorter PFCAs (i.e., PFHpA, PFHxA, PFPeA, PFBA)
were under the detection limit (<0.4 μg L−1 ) in DDW, whereas
in MeOH+NaOH solution the concentration of each compound was
lower than 60 μg L−1 . These results pointed out that: (i) PFOA is
removed (>99%) from PFOA-exhausted GAC by the MW regenera-
tion; (ii) negligible amounts of shorter PFCAs were released from
MW-regenerated BCGAC in both DDW and MeOH+NaOH solution.
Temperatures higher than 600°C might have a detrimental ef-
fect on the porous structure of GAC (Ania et al., 2005). Therefore,
E. Gagliano, P.P. Falciglia, Y. Zaker et al.
Fig. 4. [a] BET area variation of GAC samples (PFOA-BCGAC and PFOA-LCGAC) due to MW regeneration at different irradiation conditions; [b] Variation of total pore volume
(Vtot) and micropore volume (Vmicro) on the MW regenerated GACs (PFOA-BCGAC and PFOA-LCGAC).
the effect of MW regeneration, performed at different irradia-
tion conditions, on GAC physical characteristics (PFOA-BCGAC and
PFOA-LCGAC) was evaluated by means of nitrogen adsorption
isotherms. The change in BET areas and pore volumes of both BC-
GAC and LCGAC as a result of MW irradiation are shown in Fig. 4.
The positive values represent the increase over the virgin condi-
tion, while a decrease in BET area and pore volume is depicted
with negative values.
The results reveal that the variations in both BET area and to-
tal pore volume of PFOA-saturated BCGAC were within 15%, even
though the micropore volume increased more than 20% after MW
regeneration performed at 250 W - 6 min and 250 W - 8 min
(Fig. 4). Such changes seem do not affect significantly the MW re-
generation efficiency for PFOA-saturated BCGAC (Fig. 3b).
In contrast, a decrease in BET area and pore volumes were ob-
served for LCGAC after MW irradiation (Fig. 4). The negative impact
of MW irradiation on LCGAC was attributed to the higher pres-
ence of functional oxygen groups (Cheng et al., 2005). As reported
elsewhere (Ania et al., 2007; Pi et al., 2017; Zhang et al., 2012),
upon heating, a large amount of gases (coming from desorption of
volatiles and the decomposition of oxygen-containing groups) are
evolved. As a result, the LCGAC porous structure was more nega-
tively affected than BCGAC, depending on the extent of MW irradi-
ation.
The highest decrease of BET area in PFOA-saturated LCGAC oc-
curred when MW irradiation was performed at 375 W for 6 min (a
18% decrease compared to virgin LCGAC) (Fig. 4a). The decrease in
BET area observed for LCGAC regenerated samples was also found
for total pore volume (Fig. 4b). This suggests that the MW irra-
diation created a residual deposit in LCGAC pores, which blocked
the porosity and reduced both BET area and total pore volume
(Wang et al., 2010). The harsh regeneration condition applied, at
which the temperature of 753°C was reached, also contributed to
Fig. 5. Temperature reached by PFOS-saturated GACs (BCGAC and LCGAC) and the percentage of weight loss at several MW irradiation conditions [a]; Regeneration efficiency
for PFOS-saturated BCGAC and LCGAC samples after MW regeneration [b].
6
Water Research 198 (2021) 117121
the damage of LCGAC porous structure. This deterioration of LCGAC
sample, irradiated at 375 W for 6 min, negatively affected the ad-
sorption capacity of regenerated LCGAC, as demonstrated by a low
value of RE obtained (~60%, Fig. 3b). Overall, it seems that the re-
duction in total pore volumes affects negatively the adsorption ca-
pacity of MW regenerated LCGAC, as observed for data obtained at
375 W - 4 min and 375 W - 6 min MW (Fig. 3b and Fig. 4b).
3.3. MW regeneration of PFOS-saturated GACs
From batch adsorption experiments, similar PFOS adsorption
capacities were obtained on virgin BCGAC and LCGAC, 19.8 and
20.0 mg g−1 , respectively. Temperature, weight loss percentage and
regeneration efficiency for PFOS-saturated GACs are reported in
Fig. 5. Similar to PFOA-saturated GAC samples, LCGAC saturated
with PFOS reached higher temperature than BCGAC when both
GACs were irradiated at the same MW power and irradiation time
(Fig. 5a).
While the power of 125 W and irradiation time of 12 min
yielded temperatures much lower than 600°C (T=240°C in PFOS-
saturated BCGAC, T=370°C in PFOS-saturated LCGAC), the lowest
REs were obtained for both BCGAC and LCGAC (Fig. 5b).
Despite the higher temperatures reached, the RE values for
PFOS-saturated LCGAC were slightly lower than those obtained for
BCGAC. Specifically, the RE values for PFOS-saturated BCGAC were
equal or greater than 80% (expect for MW irradiation at 125 W
for 12 min due to the low temperature reached). At the highest
power (500 W) applied for the shortest irradiation time (3 min),
the RE values were higher than 90% for both PFOS-saturated GAC
samples (Fig. 5b). However, the lowest WL of BCGAC samples (4%
vs. 10.5% in LCGAC) encouraged its application for the investigation
of the five successive adsorption/regeneration cycles (section 3.4).
As previously pointed out for PFOA, the potential release of PFOS
E. Gagliano, P.P. Falciglia, Y. Zaker et al. Water Research 198 (2021) 117121

Fig. 6. BET area variation in GACs (PFOS-BCGAC and PFOS-LCGAC) with MW regeneration performed at different irradiation conditions [a]; Variation of total pore volume
(Vtot) and micropore volume (Vmicro) for MW regenerated GACs (PFOS-BCGAC and PFOS-LCGAC) [b].

and its related degradation products (shorter chain compounds)

from MW regenerated GAC (MW irradiated at T>600°C) was also
assessed in both DDW and MeOH+NaOH solution. The results re-
vealed that PFOS concentrations were 58 μg L−1 and 2.4 mg L−1 in
DDW and MeOH+NaOH solution, respectively. Shorter PFSAs (i.e.,
PFHpS, PFHxS, PFPeS, PFBS) were under the detection limit (<0.4
μg L−1 ) in DDW, whereas higher concentrations were observed
in MeOH+NaOH solution (PFBS=8 μg L−1 ; PFHxS=215 μg L−1 ;
PFHpS=62 μg L−1 ; PFPeS= 27 μg L−1 ). These results corroborate
that PFOS is removed from the GAC by the MW regeneration and
negligible PFSAs desorption occurs during the following adsorption
cycle.
The RE values after one adsorption/regeneration cycle for PFOS-
saturated GACs were in good agreement with those of previ-
ous studies carried out on AC saturated with both organic and
inorganic compounds (Ania et al., 2005; Falciglia et al., 2020b;
Foo, 2018; Sun et al., 2017).
The variation of RE across MW regeneration performed at dif- Fig. 7. Regeneration efficiency (RE), Single-step desorption efficiency (SSDE) and
ferent power and irradiation time reflects the change in BET weight loss (WL) for PFOA- and PFOS-saturated BCGAC throughout MW regener-
area and total pore volume of irradiated GAC samples compared ation cycles (MW Power=500 W, MW irradiation time=3 min).
to virgin ones. GAC porous structure after MW regeneration de-
pends on PFOS removal rate and the deposition of regeneration
residues, which might block carbon pores (Durán-Jiménez et al., (Deng et al., 2015; Du et al., 2016, 2015; Punyapalakul et al., 2013).
2019; Wang et al., 2010). This is shown in Fig. 6 with the BET area The regeneration percentages higher than 80% were achieved
and pore volume percentage variations in PFOS-saturated BCGAC when PFOS saturated AC samples (e.g., bamboo derived AC and
and LCGAC. coconut shell based GAC) using a solution of ethanol or methanol
Similar to PFOA-saturated BCGAC, the BET area variations in (>50%). Indeed, a solution of organic alcohol was required to
PFOS-saturated BCGAC were lower than 15% (Fig. 6a). The changes desorb the hydrophobic C-F chain. However, chemical regeneration
in pore volume were also limited to a maximum of 20%. This data using an organic solvent is not suitable for the full-scale drinking
demonstrates that MW irradiation has a slight effect on BCGAC water applications (Gagliano et al., 2020).
porous structure (Fig. 6b). On the other hand, a more noticeable
decrease (up to 30%) in BET area for PFOS-saturated LCGAC was 3.4. Investigation of adsorption-regeneration cycles for PFOA- and
obtained after MW irradiation, demonstrating the negative impact PFOS-saturated BCGAC
of MW on LCGAC as previously pointed out for PFOA-saturated
LCGAC. For instance, the MW regeneration performed at 375 W To further assess the performance of MW irradiation for the re-
for 6 min resulted in damages to the pore structure of carbon, as generation of GAC saturated with PFOA and PFOS, five successive
demonstrated by the decrease in BET area (20%) and in pore vol- adsorption-regeneration cycles were carried out. BCGAC was se-
ume (30% and 44% of total pore volume and microporous volume, lected for these experiments owing to its lower WL than LCGAC,
respectively). Those variations in LCGAC porous structure led to a which encourages its applicability for MW regeneration.
reduction in the adsorption capacity (RE < 60%). Among irradiation conditions investigated in the present study
The efficiency of MW regeneration obtained in the (Table 2), a MW power of 500 W and irradiation time of 3 min
present study was compared with the findings reported by were selected since this combination yielded a temperature higher
Xiao et al. (2020). The authors reported that the thermal treat- than 600°C. Moreover, it allowed a better preservation of BCGAC
ment of spent GAC (Filtrasorb 200, Calgon Corporation) at 500°C porous structure, ensuring a good thermal desorption of PFOS and
for 30 min allowed the decomposition of PFAS (i.e., 99% for PFOS), PFOA (RE > 90%) with the lowest carbon weight loss (WL < 4.3%).
although the recovery of GAC adsorption capacity was not eval- The trends observed in RE, SSDE and WL values for both
uated, and a significant mineralization of PFOS (86.8 mol %) was PFOA- and PFOS-saturated BCGAC throughout five successive ad-
reached at 800°C (treatment time = 30 min). To further highlight sorption/regeneration cycles are depicted in Fig. 7. The RE values of
the potential of MW regeneration, a comparison was also made PFOA- and PFOS-saturated BCGAC followed different trends. Specif-
with the chemical regeneration results for PFOS-saturated AC ically, the RE values of PFOA-saturated BCGAC increased until the

7
E. Gagliano, P.P. Falciglia, Y. Zaker et al.
Table 3
Textural properties variation of PFOA- and PFOS-saturated BCGAC with regeneration cycles performed at 500 W for 3 min.
Virgin BCGAC
BET area (m2 g-1 ) 894
Total pore volume, Vtot (cm3 g-1 ) 0.51
Micropore volume, Vmicro (cm3 g-1 ) 0.33
Mesopore volume, Vmeso (cm3 g-1 ) 0.18
Average pore size (nm) 4.0
R1: after 1 adsorption/regeneration cycle
R3: after 3 adsorption/regeneration cycles
R5: after 5 adsorption/regeneration cycles
3rd cycle (~95%), further adsorption/regeneration cycles led to a
gradual decrease in RE, which was ~65% after the 5th cycle. In
comparison, PFOS-saturated BCGAC irradiated at 500 W for 3 min
reached the highest RE after the 1st cycle, then RE gradually de-
creased to 63.5% after the 5th adsorption/regeneration cycle.
The single-step desorption efficiency (SSDE) provides the per-
centage of PFOA and PFOS desorption in each cycle, allowing to
evaluate the desorption yield in the different cycles (Ania et al.,
2007; Çalişkan et al., 2012) (Fig. 7). For the PFOS-saturated BCGAC,
the SSDE was ~90% and it remained almost constant throughout
successive cycles, demonstrating a high rate of PFOS desorption.
Conversely, a gradual increase followed by a sharp decrease can be
observed in SSDE for PFOA-saturated BCGAC samples (Fig. 7). This
suggests that PFOA desorption from regenerated BCGAC was easier
until the 3rd cycle at which the highest RE was also obtained.
WL increased almost linearly with MW regeneration cycles in
both PFOS- and PFOA-saturated BCGAC samples (Fig. 7). Although
the greater loss of mass carbon occurred after the 1st cycle (WL
~4%), total WL remained was <7% after 5 successive cycles of PFOS-
and PFOA-saturated BCGAC. This percentage is lower than that at-
tributed to conventional thermal regeneration of GAC, which is in
the range of 5 - 15% at each regeneration cycle (Zanella et al.,
2014). Moreover, the obtained values of WL corroborate the ad-
vantage of MW regeneration over the conventional thermal re-
generation and they are in good agreement with previous find-
ings reported in literature (Falciglia et al., 2020b; Liu et al., 2004;
Sun et al., 2017; Wei et al., 2012).
Textural properties of PFOA- and PFOS-saturated BCGAC af-
ter several adsorption/regeneration cycles are reported in Table 3.
The physical features of the regenerated carbons (i.e., BET area
and pore volume) did not differ noticeably from the virgin sam-
ples as demonstrated by the percentage variation remaining lower
than 20% (Table 3). This demonstrates that the application of
short MW irradiation times (i.e., 3 min) could preserve the porous
structure of the regenerated carbons throughout several adsorp-
tion/regeneration cycles. After the 3rd cycle, the lack in mesoporos-
ity (Vmeso <0.05 cm3 g−1 ) may delay the migration of the PFOS
molecules desorbed from BCGAC. This is also true for the PFOA-
saturated BCGAC after the 5th adsorption/regeneration cycle. In-
deed, a fall in mesopore volume (Vmeso = 0.08 cm3 g−1 ) and
a decrease in average pore size (~3.8 nm) occurred (Table 3). A
gradual blockage of the porous structure seemed to occur due to
the fraction of adsorbed PFOA or PFOS molecules which did not
evolve from the carbon surface during the regeneration after suc-
cessive cycles. These molecules may remain inside the pore net-
work of BCGAC and give rise to carbonaceous residues (Ania et al.,
2005; Foo and Hameed, 2012). Consequently, the formation of coke
deposits and damage to porosity may cause the decrease in the
adsorption capacity of regenerated BCGAC, as demonstrated by
the decrease in RE throughout several cycles (Ania et al., 2005;
Falciglia et al., 2020b).
It is noteworthy that when water-saturated GACs are irradi-
ated with MW, GAC grains could act as “hotspots” and their in-
ternal temperature is higher than the recorded temperature on
Water Research 198 (2021) 117121
PFOA R1 PFOA R3 PFOA R5 PFOS R1 PFOS R3 PFOS R5
901 894 1099 865 1018 1052
0.49 0.54 0.47 0.53 0.43 0.52
0.32 0.3 0.39 0.25 0.38 0.43
0.17 0.24 0.08 0.28 0.05 0.09
4.5 4.8 3.8 5.0 3.6 3.8
the external surface due to a cooling down effect (T~ 400°C)
(Falciglia et al., 2020b; Yang et al., 2017). The thermal gradient
from the interior of the grain to its surface allows the MW-induced
reaction to proceed more quickly and effectively at a lower bulk
temperature, thus saving energy and shortening the processing
time. In addition, the “hotspots” favour heterogenous reactions be-
tween GAC and the gases taking part in the reaction, which might
contribute to PFAS desorption through stripping mechanism of in-
terstitial water (Falciglia et al., 2018; Sun et al., 2016).
4. Conclusion and future perspectives
The applicability of MW irradiation for the regeneration of
PFOA- and PFOS-saturated GAC was investigated in terms of regen-
eration efficiency, carbon weight loss and variation of GAC textural
properties. The key findings were summarized as follow:
• During MW irradiation, fast temperature increases were ob-
tained on both GACs (~150°C min−1 at power of 500 W). Fur-
thermore, temperatures higher than 600°C were attained by ap-
plying a minimum MW power of 250 W for 6 min. The high
temperatures reached pointed out the strong ability of GAC to
transform the adsorbed MW power into a rapid temperature
rise, representing the key factor in the regeneration process.
• The correlation between GAC temperatures and their weight
loss percentage provides valuable information to distinguish
among several GACs commercially available. The highest weight
loss percentages obtained in LCGAC (lignite coal GAC) neg-
atively affects its applicability on several successive adsorp-
tion/regeneration cycles.
• A very short MW irradiation time of 3 min allowed the achieve-
ment of temperature needed for PFOS and PFOA thermal des-
orption, resulting in the lowest WL and in the highest RE values
(>90%).
• The enhancement in the RE may not be exclusively attributed
to the complete desorption of PFOA or PFOS, but an increase in
the overall uptake was attributed to the changes in GAC porous
structure (e.g., the development of mesoporosity), as demon-
strated by the variation in pore volume.
• After five successive adsorption/regeneration cycles, the ob-
served values of RE (~65%) jointly with a moderate weight loss
(<7%) demonstrated the potential applicability of MW irradia-
tion for regenerating PFOA- and PFOS-saturated BCGAC.
• Comparing to conventional thermal regeneration, MW irradi-
ation allowed the lowering of treatment time since the tem-
peratures required for PFAS desorption (>600°C) were obtained
within 3 min.
• Negligible amounts of PFOA and PFOS were released from
MW-regenerated GAC. Moreover, considering GAC temperatures
reached during MW regeneration, it could be assumed that
both PFOA and PFOS are thermally degraded without any sig-
nificant formation of related shorter chain compounds.
This study showed for the first time that the regeneration
of PFAS-saturated GACs through MW irradiation is a promising
8
E. Gagliano, P.P. Falciglia, Y. Zaker et al.
technology. Moreover, the obtained findings contributed to in-
crease the knowledge concerning the fate of PFOA and PFOS during
GAC thermal regeneration, which are partially understood. How-
ever, there are still a number of knowledge gaps that need fur-
ther investigation to explore its application such as understand-
ing of the efficiency of MW regeneration in the presence of
co-existing compounds (both organic matter and inorganic com-
pounds), the fate of PFAS molecules during MW regeneration, re-
generation mechanisms, and the experiences with GAC samples
obtained from full-scale filters treating PFAS contaminated waters.
Some of these are currently being investigated in our laboratories
and will be communicated in future publications.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgement
This study was partially funded by the University of Cata-
nia within the “Piano di incentivi per la Ricerca di Ateneo
2020/2022” of the Department of Civil Engineering and Architec-
ture, Project “Materiali e Metodologie chimico-fisiche avanzate per
l’abbattimento di contaminanti Xenobiotici (MaMeX)” and by the
Water Research Foundation (WRF) project 5103. Clemson Univer-
sity thanks WRF for their financial, technical, and administrative
assistance in funding the project through which this information
was discovered. This material does not necessarily reflect the views
and policies of the funders, and any mention of trade names or
commercial products does not constitute the funders’ endorsement
or recommendations thereof.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.watres.2021.117121.
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