Science of the Total Environment 734 (2020) 139435

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Science of the Total Environment

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

Fenton-driven oxidation of contaminant-spent granular activated carbon

(GAC): GAC selection and implications
Klara Rusevova Crincoli a, Patrick K. Jones b, Scott G. Huling b,⁎
a
National Research Council, Robert S. Kerr Environmental Research Center, 919 Kerr Lab Dr., Ada, OK 74820, USA
b
U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, Robert S. Kerr Environmental Research Center, 919 Kerr Lab Dr., Ada,
OK 74820, USA

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

• Treatment of contaminant-spent granu-

lar activated carbon (GAC); chemical
oxidation.
• 31 GACs evaluated in the adsorption ox-
idation treatment process.
• The adsorption oxidation treatment
process is GAC-dependent.
• Success of GAC raw materials was bitu-
minous coal N wood N coconut N peat.
• GAC selection is a key factor in the suc-
cess of adsorption oxidation technology.

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

Article history: Raw materials, activation methods, and post-activation treatment used in manufacturing granular activated car-
Received 15 January 2020 bon (GAC) results in a spectrum of physicochemical characteristics that potentially impact the adsorption oxida-
Received in revised form 27 April 2020 tion treatment process. A comprehensive study is lacking that assesses the effect of GAC characteristics on
Accepted 12 May 2020
adsorption oxidation treatment of contaminant spent-GAC. Consequently, it is inherently assumed the treatment
Available online 15 May 2020
process is GAC-independent. Here, GACs (n = 31) were characterized and used in the hydrogen peroxide
Editor: Ching-Hua Huang (H2O2)-based adsorption oxidation treatment of 2-chlorophenol (2CP)-spent GAC. The GACs exhibited a range
in surface area, pore volume distribution, metals content, surface functionality, and H2O2 reaction. Chloride re-
Keywords: covery, the treatment metric for 2CP oxidation, indicated a wide range in oxidation (0–49.2%) where
Adsorption bituminous- and wood-based GAC performed best. A selected subset of GACs (n = 12), amended with iron,
Oxidation methyl tert-butyl ether (MTBE), and H2O2, exhibited a range in oxidative treatment (1.1–57.9%). Correlations
GAC treatment were established between GAC surface functionality, H2O2 reactivity, adsorption, and MTBE oxidation indicating
GAC characterization multiple parameters play a collective and compounding role. The order of GACs successfully used in the treat-
MTBE
ment process is bituminous-based coal N wood N coconut N peat. Results showed adsorption oxidation treatment
2-chlorophenol
is GAC-dependent, and therefore, GAC selection is a key factor in the success of this technology.
Published by Elsevier B.V.

⁎ Corresponding author.
E-mail addresses: rusevova.klara@epa.gov (K.R. Crincoli), jones.kyle@epa.gov (P.K. Jones), huling.scott@epa.gov (S.G. Huling).

https://doi.org/10.1016/j.scitotenv.2020.139435
0048-9697/Published by Elsevier B.V.
2 K.R. Crincoli et al. / Science of the Total Environment 734 (2020) 139435
1. Introduction
1.1. Adsorption oxidation process description
The oxidative treatment of large volumes of contaminated water is
limited by low aqueous concentrations of target contaminants resulting
in slow and/or inefficient reaction rates (Georgi and Kopinke, 2005). Al-
ternatively, adsorption followed by oxidative treatment
(i.e., “adsorption oxidation”) involves the combined, synergistic use of
two reliable and well-established treatment technologies; contaminant
adsorption onto granular activated carbon (GAC), and subsequent
Fenton-driven oxidation of the sorbed contaminants. During the ad-
sorptive step, environmental contaminants are immobilized and con-
centrated on the GAC; during oxidative treatment, contaminants are
transformed by hydroxyl radicals (•OH) formed through the Fenton
mechanism and are oxidized on or near the GAC surfaces. Mass transfer
of contaminants from the aqueous phase to the GAC in this manner
eliminates the need to carry out chemical oxidation of large volumes
of water; consequently, treatment is directed towards a reduced vol-
ume of water in a GAC slurry involving enhanced rates of reaction and
treatment efficiency. The objectives of the treatment process are to
transform the contaminants into less toxic byproducts, increase the use-
ful life of the GAC, and reduce costs for GAC regeneration and water or
air treatment (Huling et al., 2005).
The raw materials used in GAC production, the activation process,
and post-activation treatment significantly alter GAC physical and
chemical characteristics that potentially impacts the adsorption oxida-
tion treatment process. Studies involving adsorption oxidation treat-
ment of GAC often do not differentiate the GAC type used in the
experiments and therefore, inherently assume the treatment process
is GAC-independent. Further, the adsorption oxidation treatment of
GAC (Huling et al., 2005; Huling et al., 2000a; Kommineni et al., 2003)
potentially involves many key factors in the treatment process including
oxidant type, physical and chemical treatment conditions, oxidant,
method of oxidant activation, contaminant (Huling et al., 2005; Huling
et al., 2000a; Kommineni et al., 2003; Huling and Hwang, 2010;
Anfruns et al., 2013; Kan and Huling, 2009; Huling et al., 2009; Huling
et al., 2012; Kim et al., 2015; De Las Casas et al., 2006; Chiu et al.,
2012; Liu et al., 2018; Toledo et al., 2003; He et al., 2017; Bach and
Semiat, 2011; Liang and Chen, 2010; Huling et al., 2011; Hutson et al.,
2012; Horng and Tseng, 2008). However, the role of GAC type has
never been investigated and a comprehensive study does not exist in-
volving GAC raw materials, their physical and chemical characteristics,
and adsorption oxidation results. Currently, it is unclear whether GAC
behaves similarly, or whether adsorption oxidation treatment is GAC-
dependent.
The purpose of this study was to systematically measure the chem-
ical and physical characteristics of GAC that potentially influence the
treatment process, to assess whether treatment is GAC-dependent,
and if so, to identify top GAC candidates for the adsorption oxidation
treatment process. Here, a range of commercially available GACs (n =
31) consisting of several raw materials (bituminous coal, lignite coal, co-
conut shell, wood, peat) and particle sizes were tested in the adsorption
oxidation treatment of 2-chlorophenol (2CP) using activated hydrogen
peroxide (H2O2). A subset (n = 12) of the original GACs were selected
for further testing of methyl tert-butyl ether (MTBE) adsorption
oxidation.
1.2. Variability in physical and chemical characteristics of GAC
GAC is produced from various raw materials including bituminous
coal, lignite coal, coconut shells, wood, peat, sawdust, and nut shells
(Chiang et al., 2001). The carbon materials are composed of particles
consisting of small, irregularly ordered layer stacks (i.e., graphene layers
that exhibit a preferential orientation parallel to that of the particle sur-
face) (Boehm, 1994). Carbon particles are activated either by high
temperature steam or through a high temperature and/or chemical
treatment process. During thermal activation, the internal porosity in-
creases and begins to separate the layered stacks resulting in high sur-
face area. The internal porosity exhibits a range in pore volume
distribution including micropores (b2 nm in diameter), mesopores
(2–50 nm), and macropores (N50 nm) which impacts molecular size-
dependent diffusional access of the contaminant, H2O2, or other re-
agents used in the adsorption oxidation process.
Carbon activation impacts the formation of functional groups found
at the edges of the GAC's graphene planes. These functional groups can
be categorized based upon their oxygen content and include acidic sur-
face oxide (ASO) functional groups, generally categorized into four
types: carboxyls, lactones, phenols, and carbonyls (Boehm, 1994); ex-
hibit high oxygen content, cation exchange capacity, and are unreactive
with H2O2 (Kinoshita, 1988). ASOs increase the surface polarity of GAC
resulting in a decrease in the carbon surface affinity for some com-
pounds. Basic surface oxide (BSO) functional groups, including
pyrone- and chromene-type structures, exhibit low oxygen content,
anion exchange capacity, and are reactive with H2O2. The distribution
of ASOs and BSOs in GAC influences surface chemistry, contaminant ad-
sorption, and H2O2 reactivity (Morena-Castilla et al., 1995; Zeid et al.,
1995; Choma et al., 1999; Karanfil and Kilduff, 1999).
The metals content, including iron and manganese, can vary signifi-
cantly in the raw materials used to produce GAC. Post-activation acid
washing treatment of the GAC may be carried out to reduce metals,
ash, and other water-soluble metals from leaching out of the GAC
when placed into service. Through these processes, the final GAC prod-
uct exhibits a range in physical and chemical characteristics including
particle size (i.e., mesh size), pH (DeSilva, 2001), metals content, surface
area, pore volume, pore size distribution, and surface functionality. Fur-
ther, the final GAC product exhibits significant variability in adsorptive
properties. For example, five types of physical adsorption curves can
be described that result from variability in the microstructure of the
GAC (Chiang et al., 2001). The pore volume and specific surface area
are still considered the most important factors regarding the adsorption
of volatile organic compounds (VOCs) (Chiang et al., 2001). Overall, it is
likely that these physical and chemical characteristics directly or indi-
rectly impact the adsorption oxidation treatment process. Thus, it is
proposed that a key factor in the success of the adsorption oxidation
treatment technology is functionally dependent on GAC selection.
1.3. Oxidative treatment overview
H2O2-driven processes serve as the basis for different oxidative
treatment applications including the chemical oxidation regeneration
of contaminant-spent GAC (Georgi and Kopinke, 2005; Huling et al.,
2005; Huling et al., 2009; Huling et al., 2007). Oxidative systems based
on iron (Fe)-activated hydrogen peroxide (Fe-AHP) (R1-R3; Table 1)
generate •OH, which are powerful and indiscriminate free radicals that
react with a wide array of environmentally relevant contaminants
(Buxton et al., 1988; Haag and Yao, 1992). Naturally occurring Fe pres-
ent in the GAC matrix, amended Fe present as iron oxides fixed to the
GAC surfaces, and/or soluble or colloidal iron in solution react with
H2O2 in the Fe-AHP mechanism (R4a, R4b; Table 1).
Oxidative transformation of two environmentally relevant and
structurally distinct probe compounds was investigated in this study;
2CP and MTBE. 2CP (R5a; Table 1) and MTBE (R5b; Table 1) react with
•OH at high rates (Buxton et al., 1988; Getoff and Solar, 1986); are rela-
tively hydrophilic, poorly volatile, and exhibit different sorption affini-
ties towards GAC (Supporting Information Table S.1) (US EPA, 2008;
Liu and Chang, 1997).
Inefficiency in the oxidative treatment processes is attributed to two
main mechanisms, radical scavenging and nonproductive reactions
(NPR). The rates of •OH reaction with non-target chemical species
(i.e., scavengers, Si) in the aqueous phase have been determined for
some aqueous systems (Kwan and Volker, 2003; Grebel et al., 2010;
 K.R. Crincoli et al. / Science of the Total Environment 734 (2020) 139435
Table 1
H2O2 activation and related reactions.
H2O2 + Fe2+ → Fe3+ + OH- + •OH k1=76 1/M×s Walling, 1975
H2O2 + Fe3+ → Fe2+ + •O-2 + 2H+
•O-2 + Fe3+ → Fe2+ + O2
H2O2 + ≡Fen-oxide → ≡Fen+1-oxide +
•OH + OH-
H2O2 + ≡Fen+1-oxide → ≡Fen-oxide +
HO2• + H+
10
•OH + 2CP → products k5a = 1.2×10 1/M×s Getoff and
Solar, 1986
•OH + MTBE → products k5b = 1.6×109 1/M×s Buxton et al., R
1988
•OH + Σni=1 [Si] → products
•OH + H2O2 → HO2•- + H2O k7 = 2.7×107 1/M×s Buxton et al., R 7
1988
Mn- and some Fe-oxides
2H2O2 → O2 + 2H2O
C+]OH- + HOOH → C+]OOH- + H2O Kinoshita, 1988
C+]OOH- + H2O2 → C+]OH- + H2O + Kinoshita, 1988
O2
Note: Σni=1 [Si] is the pseudo-first-order rate constant (kS 1/s) for •OH scavenging by all
constituents in solution except the target compound.
Rusevova et al., 2012). These calculations use second-order rate con-
stants (Buxton et al., 1988; Haag and Yao, 1992) and scavenger concen-
trations ([Si]). Si can be naturally occurring (e.g., HCO− 2−
3 , CO3 ), and can
be from anthropogenic sources (e.g. H2O2) (R6-R7; Table 1). •OH scav-
enging by solid surfaces has only recently been measured for some min-
erals (alumina, silica, montmorillonite) (Rusevova Crincoli and Huling,
2020). It is probable that GAC surfaces will also scavenge radicals and
treatment will be GAC-dependent. Therefore, oxidation results may em-
pirically reflect GAC-dependent radical scavenging. Manganese and
some iron oxides are involved in NPR and deplete the source of oxidant
(i.e., H2O2) without formation of •OH. These reactions diminish radical
production and cause treatment inefficiency (R8; Table 1). BSO func-
tional groups (C+]OH−) involving H2O2 disassociation reactions (R9-
R10; Table 1) (Kinoshita, 1988) also cause NPR and contribute to treat-
ment inefficiency.
2. Methods, materials, and analytical
Overall GAC characterization and testing summary: GAC (n = 31) N2
BET surface area, pore volume distribution; average concentration of
metals (Fe, Mn, Cu) and bromide in GAC; 2CP adsorption and oxidation
treatment, H2O2 reaction rate, and Br− residuals; GAC (n = 12) func-
tionality measurements (acidic and basic functional groups), MTBE ad-
sorption and oxidation treatment.
2.1. Analytical methods
The analytical methods used to characterize GAC (surface area and
pore volume, metals and nonmetals content, surface functional groups)
and to measure oxidation performance (i.e., 2CP, MTBE, H2O2, iron, an-
ions [i.e., Cl−, Br−] and pH) are documented in the Supporting Informa-
tion (S.1 Analytical Methods). All analytical measurements included
duplicate analyses.
2.2. GAC samples
Thirty-one (31) commercially available GACs were acquired from
different manufacturers (Table 2). These GACs were manufactured for
water treatment applications, derived from a range of raw materials,
and activated and processed under various conditions. The GACs were
analyzed for physicochemical parameters and used in screening tests
to evaluate their role in the adsorption oxidation treatment process.
Analyses were performed to establish baseline characteristics of each
GAC and to potentially correlate results with adsorption oxidation re-
sults. GAC samples (200 g) were rinsed with deionized water (DIW)
3
to remove fines, dried in an oven (105 °C), and stored in a desiccator
until used. All GAC samples were subjected to a 2CP adsorption oxida-
R1 tion test where 2CP was adsorbed and subsequently oxidized by the ad-
R2 dition of H2O2. A subset (n = 12) of the 31 original GACs used in the 2CP
R3 oxidation tests were selected and used in another adsorption oxidation
R
test where Fe, MTBE, and H2O2 were amended to the GAC to assess
4a
R MTBE adsorption oxidation.
4b
R 2.3. 2CP adsorption oxidation screening test
5a
5b
The 2CP screening test involved the adsorption and oxidation of 2CP
R6 under optimal pH conditions (pH 3.0) (Pignatello et al., 2006). Repre-
sentative GAC samples (1 g) collected using a soil riffle were placed in
a reactor vessel (125 mL Erlenmeyer flask) and amended with an
H2SO4 solution (28.4 mM) to acidify the GAC suspension (pH 3.0;
R8
R9 24 h). The final pH was measured, and the acidic solution was decanted.
R The 2CP stock solution was analyzed (n = 3) and added to the acidified
10 GAC in the flask reactor (40 mL; 5.0–5.8 mM). Flasks were wrapped in
aluminum foil, labeled, para-filmed, and placed on an orbital shaker
(N24 h) to allow 2CP adsorption. The post-sorption 2CP solution was
sampled and analyzed (n = 2) for 2CP and anions (Cl−, Br−). The source
of Cl− could be released from the oxidation of 2CP and/or the GAC
(Huling et al., 2000b); the source of Br− could be released from the ox-
idation of the GAC. The remaining solution was decanted, and oxidation
was accomplished by amending the GAC with H2O2 (50 mL; 20 g/L).
Aqueous samples were collected over time to determine the H2O2 deg-
radation rate (5 ≤ n ≤ 10); and analyzed for [H2O2] (n = 2). After the
H2O2 was fully reacted, the spent H2O2 solution was analyzed for anions
(Cl−, Br−) and the pH was measured. 2CP-free control reactors were
prepared for each GAC type (1 g GAC) and amended with H2O2. These
2CP-free controls were used to quantify Cl− and Br− released from
the oxidation of GAC. Background Cl− measured in the 2CP-free GAC
was used to correct the total Cl− measured in the post-oxidation 2CP-
amended GAC sample. 2CP oxidation evaluation was based on a Cl−
mass balance (1 mol Cl− /mol 2CP) involving the recovery of Cl− re-
leased from the oxidation of 2CP in the GAC suspension relative to the
total amount of Cl− amended to the GAC as 2CP (Eq. 1). Minor amounts
of Cl− were measured in the post-sorption solution phase. Conse-
quently, the post-sorption mass of Cl− amended was adjusted for the
pre-treatment Cl− released during the sorption phase.




MCl−;POST OXID:;2CP−AMENDED ; −; MCl− ;POST OXID:;2CP−FREE ð100Þ
2CP Loss ð%Þ ¼


M Cl− ;PRE OXID:;2CP−AMENDED − MCl− ;POST SORP:;2CP−AMENDED
ð1Þ
where,
MCl-, POST OXID., 2CP-AMENDED = (VH2O2 × [2CP]POST OX × L/
1000 mL × SF)/MW2CP.
MCl-, POST OXID., 2CP-FREE = (VH2O2 × [Cl−] × L/1000 mL)/MW− Cl
MCl-, PRE OXID., 2CP-AMENDED = V2CP × [2CP]INITIAL × MW2CP × SF
MCl-, POST SORP., 2CP-AMENDED = V2CP × [Cl−]POST SORPTION × MW− Cl × SF
VH2O2 = 50 mL
V2CP = 40 mL
[2CP]POST OX = Post oxidation concentration of 2CP (mg/L)
[Cl−] POST SORPTION = Post 2CP sorption [Cl−], before oxidation
(mg/L)
MW2CP = 228.6 (mg 2CP/mmol)
MW− −
Cl = 35.45 (mg Cl /mmol)
SF (stoichiometric factor) = 1 mmol Cl−/1 mmol 2CP
2.4. MTBE oxidation screening test
An MTBE oxidation screening test was conducted on a subset of GAC
samples (n = 12) selected from the original set of GAC samples (n =
31). A ranking method was developed to select GAC samples that exhib-
ited characteristics favorable to adsorption oxidation treatment.
4 K.R. Crincoli et al. / Science of the Total Environment 734 (2020) 139435

Table 2
Granular activated carbon types1, mesh size, raw materials, activation, and general information; , , , peat raw materials.
Manufacturer Mesh Activation
GAC Type Size Method Raw Materials Handling Apparent Density
Calgon Carbon
CGB 8×30 Steam select grades of coal 0.49 g/mL
CGB MOD1 8×30 Steam select grades of coal 0.49 g/mL
CAX 8×30 Steam coconut shell acid washed 0.453 g/mL
BCP MOD12 8×30 Steam bituminous coal 0.366 g/mL
URV-MOD12 8×30 Steam bituminous coal 0.49 g/mL
Filtrasorb 400 12×40 Steam bituminous coal 0.54g/mL, tamped
Filtrasorb 600 12×40 Steam bituminous coal 0.62g/mL, tamped
CarboChem
LQ-900S 8×30 Steam bituminous coal 0.50 g/mL
LQ-1240 12×40 Steam bituminous coal 0.50 g/mL

MeadWestvaco 14×35 Steam wood 0.24-0.30 g/mL

Nuchar WV-BV 20×50 Steam wood 0.26-0.32 g/mL
NucharWV-BV 1500
Bio-Nuchar 120 14×18 Steam wood 0.21-0.28 g/mL
Nuchar RGC 40 12×40 Steam wood 0.23-0.30 g/mL
Norit Americas
C Granular 8×30 Steam + H3PO4 wood 0.23 g/mL
Darco 12×40 12×40 Steam lignite coal HCl washed 0.40 g/mL
HydroDarco 3000 8×30 Steam lignite coal 0.38 g/mL
HydroDarco 4000 10×30 Steam lignite coal 0.38 g/mL
Norit GAC 830 8×30 Steam bituminous coal
Norit GAC 830 Plus 8×40 Steam bituminous coal acid washed 0.51 g/mL
Norit GAC 1240 12×40 Steam bituminous coal 0.5 g/mL
Norit GAC 1240 Plus 12×40 Steam bituminous coal HCl washed 0.5 g/mL
Norit ROX 0.8 Extruded Steam peat HCl washed particle size < 60 mm;
0.2-0.6 g/mL
Waterlink-
Barnebey Sutcliffe
3007 20×50 Steam coconut shell HNO3 washed 3
3034 12×30 Steam coconut shell acid washed 3
4040 12×30 Steam coconut shell acid washed 3
HR5-AW 12×40 Steam coconut shell acid washed 3
206C-AW 12×40 Steam bituminous coal acid washed 0.48 g/mL 3
207A-AW 12×40 Steam bituminous coal acid washed 0.50 g/mL 4
DCL 12×40 Steam wood acid washed 4
HI PUR 8×30 Steam bituminous coal acid washed 0.48 g/mL 4
HI PUR PLUS 8×30 Steam bituminous coal acid washed 0.48 g/mL 4
1
Some GACs have been discontinued by the manufacturer; replaced by other GAC;
2
Specialty carbon;
3
The extent of steam activation and acid/water washing varied between coconut carbons producing a range in ash
content and/or activity;
4
The extent of steam activation, acid washing, and screening varies between coal carbons producing a range in ash
content and/or pore volume distribution.

Parameters included surface area, meso+macro pore volume, [Fe]GAC,
H2O2 half-life, post-sorption and post-oxidation [2CP]. The Cl− released
was used as an indicator of 2CP transformation. The MTBE oxidation test
involved pre-oxidation iron-amendment to the GAC, followed by MTBE
adsorption and oxidation (pH 3.0). The objectives were to assess the ex-
tent to which the naturally occurring iron could be augmented and
immobilized on the GAC, and to quantify the extent of MTBE adsorption
and oxidation. Post-oxidation MTBE residuals on the GAC were ex-
tracted and quantified, and results were used to quantify treatment per-
formance. Pre- and post-oxidation [Fe]GAC and N2 BET surface area were
also measured. This set of treatment objectives was selected to identify
an optimal pool of GACs, widen the range of contaminants tested, im-
prove oxidative treatment via Fe amendment, utilize a method of con-
taminant extraction and analysis for oxidative treatment performance
evaluation, assess Fe retention efficiency, and the overall impact of
treatment on surface area.
Representative GAC samples (5 g) were collected using a soil riffle,
added to the test reactor (250 mL Erlenmeyer flask), and amended
with an Fe solution (15 mL; FeSO4•7H2O; 3.12 g/L as Fe; 55.9 mM).
After sufficient contact time (3 d) the solution was decanted and FeT,
Br−, and Cl− were measured. Fe amendment in GAC using these proce-
dures may result in Fe penetration and immobilization within a short
transport distance into the GAC (Huling et al., 2009). Consequently,
the reactive zone in the GAC where aggressive MTBE oxidation occurs
may be within a narrow interval on the periphery of the GAC particle.
The MTBE solution (0.12 L; 1.83 mg/L) was added to the Fe-amended
GAC (3 d) for the MTBE adsorption step. The post-sorption solution
was sampled, analyzed for MTBE (n = 2), and the pH was adjusted to
3.0 with H2SO4. The H2O2 solution was amended to the Fe- and MTBE-
amended GAC and the reactors were placed on an orbital shaker
(100 rpm) until the H2O2 was fully reacted. The H2O2 dosage was
based on cost for practicality (commercial 50% H2O2 cost ~ $0.34/L; den-
sity of 50% H2O2 = 1.18 g/mL; density of 30% H2O2 = 1.11 g/mL), where
$0.1 H2O2/lb. GAC ($0.22/kg GAC) was applied to the GAC in 3 sequen-
tial treatments using 30% H2O2 (1.91 mL 30% H2O2; 1.11 g/mL; [H2O2]INI-
TIAL = 15.8 g/L). H2O2 re-amendment occurred after the H2O2 was fully
reacted. The GAC suspension was maintained at pH 3.0 during
oxidation.
The post-oxidation solution was sampled and analyzed for MTBE
(n = 2), anions (Cl−, Br−) and the remaining solution was decanted.
Subsamples (n = 2) of the treated GAC were collected and extracted
with methanol (MeOH) (20 mL) and the MeOH extract was analyzed
for MTBE. The remaining wet GAC was weighed, dried, and re-
weighed to determine the moisture content and surface area (n = 2).
Subsamples of the dried GAC were crushed and analyzed for metals
via ICP (n = 3). MTBE adsorption oxidation treatment performance
was determined by percent loss from the initial MTBE immobilized on
the GAC (Eqs. 2–4).



MTBE Loss ð%Þ ¼ MMTBE;INITIAL –MMTBE;FINAL =MMTBE;INITIAL  100 ð2Þ
 K.R. Crincoli et al. / Science of the Total Environment 734 (2020) 139435


MMTBE;INITIAL ¼ ½MTBESTOCK –½MTBEFINAL  VSTOCK

or near the surfaces of the GAC (R1-R4, R5; Table 1). Conversely,
MMTBE;FINAL ¼ ½MTBEEXTRACT  VEXTRACT =1000
where,
MMTBE, INITIAL = pre-oxidation MTBE mass initially immobilized in
GAC (mg).
MMTBE, FINAL = post-oxidation MTBE mass extracted from treated
GAC (mg).
[MTBE]STOCK = MTBE concentration in stock solution amended to
GAC (mg/L).
[MTBE]FINAL = post-sorption MTBE concentration (mg/L).
VSTOCK = volume of stock solution amended to GAC (0.12 L).
[MTBE]EXTRACT = MTBE concentration in MeOH extract solution
amended to GAC (μg/L).
VEXTRACT = volume of MeOH used to extract post-oxidation GAC
(0.02 L).
3. Results and discussion
3.1. GAC characterization
All GACs were activated using steam, and many of the GACs were
acid washed to reduce metals leaching and ash content (Table 2). The
BET surface area of the GAC ranged widely from the 650 m2/g
(HydroDarco 3000 and 4000, lignite-based) to 2200 m2/g (Nuchar
WV-B 1500, wood-based). The average BET surface area for coal (n =
19), wood (n = 6), coconut (n = 5), and peat (n = 1) raw materials
was 990, 1540, 1050, and 980 m2/g, respectively (i.e., as calculated
using values in Table S.2). In general, higher BET surface area of GAC re-
flects a greater potential for interactions with chemicals including con-
taminant adsorption, H2O2 reactivity, and anchoring the iron amended
to the GAC.
Similarly, a broad range in the GAC micropore volume and
meso+macropore volume was measured (Table S.2). For example, the
ratio of micropore volume to the meso+macropore volume ranged
from 0.32 (HydroDarco 4000, lignite coal) to 11.4 (HR5-AW, coconut
shell). The average total pore volume in GAC involving coal (n = 19),
wood (n = 6), coconut (n = 5), and peat based (n = 1) raw materials
was 0.56, 0.91, 0.51, and 0.61 mL/g, respectively. The average ratio of
micropore volume to total pore volume (i.e., total pore volume = sum
of micropore and meso+macropore volume) was greatest for coconut
(0.89, n = 5), followed by coal (0.69, n = 19), peat (0.6, n = 1), and
wood (0.48, n = 6). It is proposed that the ideal GAC used in the adsorp-
tion oxidation process exhibits a balance between micropores and
meso+macropores depending on the molecular size of the contaminant
undergoing adsorption. The surface area generally associated with mi-
cropore volume is ideal for the adsorption of smaller molecules; while
larger pores are needed for larger molecules. A factor of 2.5× the kinetic
diameter of adsorbates is favorable for solute transport to inner pores
(Quinlivan et al., 2005). Given the atomic radii of 2CP and MTBE
(Table S.1), these adsorbates would have access to the surface area
within the micropore volume. Larger pores would also be favorable for
intraparticle transport of Fe ions and H2O2 into the GAC particle and
thus beneficial to the oxidative treatment process.
The concentration of transition metals known to react with H2O2
was variable in the GAC (Table S.3). For example, low concentrations
of Fe (30 mg/kg) and Mn (5 mg/kg) were measured in C Granular, a
steam and phosphoric acid activated wood material; while very high
concentrations of Fe (21,650 mg/kg) and Mn (510 mg/kg) were mea-
sured in LQ-900S, a steam activated bituminous coal. The average [Fe]
GAC in coal (n = 19), coconut (n = 6), wood (n = 5), and peat based
(n = 1) raw materials was 3290, 860, 200, and 144 mg/kg, respectively;
the average [Mn]GAC in coal (n = 19), coconut (n = 6), wood (n = 5),
and peat based (n = 1) raw materials was 54, 20, 6, and 9 mg/kg,
5
ð3Þ respectively. Naturally occurring Fe associated with the GAC can acti-
vate H2O2, forming •OH, which is needed to oxidize contaminants on
ð4Þ lower concentrations of Mn in GAC are favorable to the oxidative treat-
ment process by limiting NPR (R8; Table 1), a well-known source of
treatment inefficiency.
3.2. 2CP oxidation screening
The [2CP]Initial amended to the GAC suspension ranged in concentra-
tion (4970–5770 μM) and the post-sorption [2CP]FINAL was b32 μM in all
samples, resulting in N99% 2CP removal for all GAC (Table S.4). The mass
of 2CP adsorbed to the GAC was used to estimate the initial mass of Cl−
adsorbed. The percentage of Cl− released from the initial Cl− mass
adsorbed was used as an indicator of 2CP transformation, and as a per-
formance metric to assess 2CP oxidation treatment. Fourteen (14) GAC
samples resulted in 0% release of the Cl− from the 2CP; and 8 that re-
sulted in N5% Cl− release. The average percent loss of Cl− from 2CP at-
tributed to oxidative treatment for coal- (n = 19), wood- (n = 6),
coconut shell- (n = 5), and peat-based (n = 1) raw materials was 5.2,
4.6, 0.7, and 0%, respectively. It is noted, however, that transformation
of either the parent chlorinated compound or chlorinated byproducts
may proceed without simultaneous Cl− release. Further, complete Cl−
release does not assure complete mineralization of the parent com-
pound as indicated by intermediates measured in such systems
(Huling et al., 2000a).
The first-order H2O2 degradation rate constants (kH2O2) and H2O2
half-lives were determined using H2O2 concentrations measured during
the 2CP adsorption oxidation treatment (Table S.4). During oxidative
treatment, the H2O2 undergoes intraparticle diffusion-reactive trans-
port into the GAC. H2O2 reactants in the GAC slurry include transition
metals (Fe, Mn, Cu), BSOs, and •OH. Ideally, the longer H2O2 persists
(i.e., lower kH2O2; longer H2O2 half-life), the greater the potential for
intraparticle H2O2 diffusive transport and penetration distance into
the GAC. This allows a larger intraparticle treatment zone critical in ox-
idative treatment of the spent GAC (Kan and Huling, 2009; Huling et al.,
2012).
Post-oxidation solutions were analyzed for Br− in all post-oxidation
solutions and was elevated in several of the GAC slurries (Table S.4). Br−
was measured as a precautionary step to assess whether residuals may
introduce post-treatment disposal issues. Under oxidative conditions,
Br− residuals from the oxidized GAC may potentially form bromate, a
disinfectant byproduct regulated by the US EPA (maximum concentra-
tion limit = 0.01 mg/L). Although post-oxidation solutions were not an-
alyzed for bromate, these data suggest that H2O2 treatment of GAC has
the potential to produce this residual and should be monitored prior
to disposal of the regenerant solution.
Overall, there does not appear to be a correlation between the H2O2
degradation rate and either the GAC BET surface area, the GAC pore vol-
ume, the transition metals concentration of the GAC, or the Cl− released
from 2CP oxidation (Figs. S.1 – S.4). Further, a consistent lack in correla-
tion was observed between Cl− released and [Fe]T, micropore volume,
meso+macropore volume, micropore/meso+macropore volume, sur-
face area, and post-sorption [2CP] (data not shown). The lack of correla-
tion between these parameters and the H2O2 degradation rate and Cl−
release suggests that multiple parameters collectively play a
compounding role in the reaction of H2O2 with GAC, and 2CP oxidation
treatment efficiency. However, empirical observations involving these
treatment metrics and GAC parameters can be used to narrow down
the broad range of commercially available GAC investigated here to
identify good candidates to use in the adsorption oxidation process.
3.3. GAC selection for further testing
GAC parameters and treatment metrics favorable to adsorption oxi-
dation were identified and used in an empirical ranking method. This
6 K.R. Crincoli et al. / Science of the Total Environment 734 (2020) 139435
method was used to identify the top 12 GACs selected for further testing
in the MTBE adsorption oxidation treatment process. The ranking pa-
rameters were BET surface area, meso+macro pore volume, [Fe]GAC,
H2O2 half-life, [2CP]FINAL, and Cl− released. The following criteria were
used in conjunction with the ranking parameters; high surface area
(i.e., reactive surfaces) that favor MTBE adsorption and intraparticle Fe
immobilization; high meso+macro pore volume to accommodate
intraparticle transport of H2O2, Fe, and post-oxidation residuals; high
naturally occurring [Fe]GAC to facilitate Fe activation of H2O2 and •OH
formation; long H2O2 half-lives allowing longer duration for H2O2 diffu-
sive transport and intraparticle penetration distance; lower [2CP]FINAL to
achieve water treatment objectives; and high Cl− released as a general
indicator of overall 2CP oxidation. The top 12 GACs for these ranking pa-
rameters were assigned a value of 1; the ranking parameters were
summed up for an overall ranking (Table S.5). The following 12 GACs
were selected for additional testing where BCP MOD1 and URV MOD1
were ranked the highest (5); the next highest grouping (4) was Nuchar
WV-BV, Nuchar WV-BV 1500, Bionuchar 120, Nuchar RCG 40, and Norit
GAC 1240; followed by the next highest grouping (3) CGB, CGB MOD1,
CAX, C Granular, 207A-AW, and HIPUR. This selection process has limi-
tations, however: CGB was eliminated to broaden the scope of materials
tested; Norit GAC 1240 was selected because it exhibited 4 characteris-
tics favorable for adsorption oxidation yet no Cl− release was measured;
Waterlink-Barneby Sutcliff 3007 exhibited only 2 characteristics favor-
able to adsorption oxidation, including 2.6% Cl− release, but was not se-
lected for further testing.
3.4. MTBE oxidation results
Fe was amended to the GAC in a pre-treatment step to undermine
the role of NPR caused by the naturally occurring BSO and Mn content
of the GAC. Augmenting the naturally occurring Fe enhances the reac-
tion between Fe and H2O2, limits NPR, and helps to limit treatment inef-
ficiency. The amended Fe immobilized in the GAC ([Fe]GAC ~ 900 mg/kg;
n = 12) increased the total [Fe]GAC over background [Fe]GAC (Table S.3)
Fig. 1. MTBE loss in GAC-specific Fe-AHP oxidative treatment system.
by a factor of 1.5–7. In all cases, the total [Fe]GAC measured by ICP anal-
ysis was 2–3 orders of magnitude greater than the [Mn]GAC (Table S.3)
indicating that Fe dominated the reaction with H2O2. The Fe-
amendment pre-treatment method has a potential disadvantage;
while it limits the relative contribution of NPR attributed to Mn and
BSOs, faster H2O2 reaction potentially limits H2O2 diffusive transport
and intraparticle penetration.
The post-sorption aqueous phase concentrations of MTBE (Pre-Ox
[MTBE]AQ) reflect 91% removal of MTBE in CGB MOD 1 and Bio-
Nuchar 120, and 97–99% removal of MTBE in the remaining GACs
(Table S.6). Oxidative losses between the pre- and post-oxidation
[MTBE]GAC indicated 1.1% to 57.9% removal of MTBE (Table S.6; Fig. 1).
The average loss of MTBE attributed to oxidative treatment for coal-
(n = 6), wood- (n = 5), and coconut shell-based (n = 1) raw materials
was 23.4, 12.3, and 1.1%.
The average post-oxidation reduction in BET N2 surface area was
greatest for wood GAC (13.5%), followed by coal GAC (9.9%), and coco-
nut shell GAC (2.8%) (Table S.5). Reduction in surface area could be at-
tributed to blockage of sorption sites or pore throats by the amended
Fe (Huling et al., 2007), or oxidative effects (Huling et al., 2005;
Karanfil and Kilduff, 1999).
3.5. Role of GAC functional groups
The GACs used in the 2CP and MTBE adsorption oxidation tests ex-
hibited a wide range in ASOs and BSOs (Fig. 2). The Norit Americas C
Granular exhibited the highest ASO content, and no BSOs were mea-
sured (i.e., 0.0 μeq/m2). The hydrophilicity, or surface polarity of the
GAC increases with increasing ASOs, resulting in a decrease in contam-
inant adsorption (Quinlivan et al., 2005). This explains why C Granular,
exhibiting the greatest amount of ASOs, exhibited the lowest sorption
capacity of 2CP (i.e., highest [2CP]FINAL) (Table S.4). Similarly, correla-
tions between high ASOs and high [2CP]FINAL are also observed for
CGB MOD1, Nuchar WV-BV, Nuchar WV-BV 1500 and Bio-Nuchar 120.
Given that BSOs were measured in all other GAC samples, measurement
 K.R. Crincoli et al. / Science of the Total Environment 734 (2020) 139435 7

Acidic or Basic Functional Groups (meq/100g)

2000

Acidic Functional Groups GAC Raw Materials

1600 Coal
Basic Functional Groups
Wood
Coconut
1200

800

400

Fig. 2. Acid surface oxide (ASO) and basic surface oxide (BSO) functional groups on specific GACs used in the 2CP adsorption oxidation screening test.

of 100% functionality as ASOs in C Granular was likely attributed to the for adsorption oxidation treatment. Coconut-based GACs are typically
phosphoric acid activation step. Further, C Granular exhibited the characterized as having greater micropore volume than
highest H2O2 half-life (111.8 h; Table S.4) and was attributed to the meso+macropore volume. The ratio of micropore volume and
lack of BSOs and the very low concentrations of Fe and Mn (Table S.3) meso+macropore volume in coconut-based GACs in this study ranged
resulting from phosphoric acid treatment. from 4.2 to 11.4 (Table S.5) indicating predominantly micropore vol-
General correlations can be made between the ASO/BSO ratio and ume. Micropore volume is unlikely to limit the intraparticle transport
H2O2 reaction, and the ASO/BSO ratio and fraction of Cl− released or of 2CP or MTBE due to molecular size (Table S.1; Section 3.1) However,
MTBE removed (Fig. 3). H2O2 reaction is generally correlated to the
BSO content of the GAC (Kinoshita, 1988). Consequently, the extent of 0.6 0.8
2CP oxidative treatment is inversely proportional to the BSO content
and was attributed to NPR. Prior to the oxidation of 2CP in the screening
study, the GAC was acidified (pH 3.0) which reduced the BSO content of 0.7
the GAC by converting some of the BSOs to ASOs (Jones, 2007). The acid- 0.5
ification step limited BSOs and NPR, and increased 2CP oxidative treat-
ment. Similarly, amendment of an acidic Fe solution, and the GAC 0.6
Fraction Cl- released, or MTBE Removed (%)

Fraction Cl- loss from 2CP

acidification step (pH 3.0), were also responsible for suppressing BSO-
related NPR and improving MTBE oxidative treatment. 0.4 Fraction MTBE Loss

kH2O2 (hr-1) 0.5

3.6. Selection of GAC for adsorption oxidation

A wide range of treatment was achieved in 2CP-spent GAC (n = 31; increasing ASOs increasing BSOs

kH2O2 (hr-1)
0.3 0.4
0–49.2% Cl− removal) (Table S.4), and MTBE-spent GAC (n = 12;
1.1–57.9% MTBE removal) (Fig. 1). While the results were variable, in
general, the coal-based raw materials used in GAC manufacturing re-
0.3
sulted in the best 2CP and MTBE oxidative treatment performance,
0.2
followed by wood, coconut, and peat materials. Three GACs produced
by steam activation of bituminous coal (CGB MOD1, BCP MOD1, URV
0.2
MOD1) resulted in the greatest release of Cl− from oxidative treatment
of 2CP (Table S.4) and the greatest removal of MTBE in 3 of the top 4
0.1
GACs tested (Fig. 1). However, it is noted that the lack of 2CP treatment
0.1
was also measured (i.e., 0% removal of Cl−) by all the raw materials used
to make GAC including bituminous and lignite coal, wood, coconut, and
peat (Table S.4). The screening results reported in this study do not nec-
0 0
essarily reflect the level of treatment that could be achieved under opti- 0.0 1.0 2.0 3.0 4.0 5.0 6.0
mized conditions. For example, optimal conditions may involve Fe
amendment conditions (Huling et al., 2007), regeneration temperature ASO/BSO Ratio
(Kan and Huling, 2009), Fe type (Huling and Hwang, 2010), particle size
Fig. 3. General correlation between the ratio of acidic and basic surface oxide (ASO, BSO)
(Huling et al., 2009) and additional applications of H2O2. functional groups in the GAC and (1) the pseudo-first order H2O2 degradation rate
2CP and MTBE removal in the coconut-based GAC was limited sug- constant (kH2O2), and (2) the oxidative treatment of 2CP measured as a percentage of
gesting GACs made from this raw material are generally less favorable Cl− released from 2CP, and percent MTBE removed.
8 K.R. Crincoli et al. / Science of the Total Environment 734 (2020) 139435
accumulation of Fe in the pore throats may limit transport of treatment
chemicals (i.e., H2O2) during oxidation (Huling et al., 2007). The lowest
MTBE removal was measured in CAX, and no Cl− was released in 4 of
the other 5 coconut-based GACs. Conversely, CGB MOD1, a coal-based
GAC exhibiting predominantly micropore volume (Table S.6), as did
the coconut GACs, achieved the greatest treatment for both 2CP
(Table S.5) and MTBE (Fig. 1).
In another study, both H2O2 reaction and MTBE oxidation were in-
versely correlated with GAC particle size and was attributed to shorter
intraparticle diffusion transport distances for both H2O2 and MTBE
(Huling et al., 2009). In the current study, the greatest 2CP oxidation
(i.e., Cl− released) (Table S.4) and MTBE loss (Fig. 1) occurred in GACs
exhibiting the largest particle sizes (8 × 30; avg. particle diam.
1.49 mm) including CGB MOD1, BCP MOD1, URV MOD1, HiPur, and C
Granular; and (14 × 18; avg. particle diam. 1.2 mm) BioNuchar 120.
While it is apparent that GAC particle size plays a key role in oxidative
treatment when utilizing the same type of GAC; when contrasting oxi-
dative treatment results between different GAC types, the effect of par-
ticle size was not found to be a key parameter. Rather, particle size
played a secondary role relative to the collective and compounding ef-
fects of multiple parameters.
Results indicate that chemical oxidation treatment of GAC is func-
tionally dependent on the type of GAC used in the treatment process.
In most studies involving adsorption oxidation treatment of GAC, the
specific type of GAC has not been reported. Consequently, it is difficult
to gather information on the specific characteristics of GAC, compare re-
sults between studies, and to assess which GACs are favorable or unfa-
vorable to chemical oxidative treatment. Two GACs widely used for
adsorption in water treatment processes includes Calgon Carbon
Filtrasorb 400 (F400) and Filtrasorb 600 (F600). These GACs are highly
effective in contaminant adsorption, and in this study achieved the low-
est post-sorption [2CP]FINAL (Table S.4). However, no Cl− was released
during oxidative treatment of the 2CP-spent GAC (Table S.4). It is con-
cluded that contaminant adsorption and contaminant oxidation are
not necessarily complimentary characteristics in the adsorption oxida-
tion treatment process. In trichloroethylene (TCE)-spent F400 GAC re-
generated using ozone and H2O2, or UV-light catalyzed H2O2, the rate
of H2O2 reaction was rapid, and the quantity of oxidants required in
the regeneration process was found to be much more than using homo-
geneous advanced oxidation for TCE destruction (Mourand et al., 1995).
These results are consistent with our study where H2O2 reaction in F400
and F600 was rapid, and 2CP oxidation was limited. Specifically, poor
oxidative treatment in these GACs was attributed to NPR, and rapid
H2O2 reaction led to limited intraparticle penetration of H2O2 into the
GAC.
4. Conclusions
A range of commercially available GACs (n = 31) composed of sev-
eral raw materials (bituminous coal, lignite coal, coconut shell, wood,
peat) and particle sizes were tested in the adsorption oxidation treat-
ment of 2CP. Prior to treatment testing, physical and chemical charac-
teristics of the GAC were measured indicating a wide range in surface
area, pore volume distribution, and transition metals (i.e., Fe and Mn).
Cl− recovery, used as the treatment performance metric for the 2CP ad-
sorption oxidation testing, indicated a wide range of treatment
(0–49.2% loss) where bituminous coal- and wood-based GAC per-
formed best. Subsequently, GAC parameters and treatment metrics fa-
vorable to adsorption oxidation were used in an empirical ranking
method to identify the top 12 GACs selected for further testing involving
MTBE adsorption oxidation. In these experiments, Fe was amended to
the GAC to limit the role of treatment inefficiency caused by NPR. A
wide range in oxidation loss of MTBE in the GAC (1.1–57.9%) was mea-
sured where bituminous coal- and wood-based GAC also performed
best.
An inverse correlation between the ASO content in GAC, and 2CP and
MTBE adsorption was observed (i.e., C Granular, CGB MOD1, Nuchar
WV-BV, Nuchar WV-BV 1500 and Bio-Nuchar 120) and was attributed
to hydrophilicity of the GAC with increasing ASOs. A direct correlation
between H2O2 reaction and the BSO content of the GAC was established.
The NPR between BSOs and H2O2 were responsible for the inverse cor-
relation between BSOs and 2CP and MTBE treatment. These results sug-
gest that multiple GAC-specific parameters played a collective and
compounding role in the treatment process.
Contaminant adsorption oxidation screening results were useful in
identifying top candidate GAC materials to be used in the treatment pro-
cess. The overall order of GAC materials successfully used in the adsorp-
tion oxidation treatment process is bituminous-based coal N wood N
coconut N peat. While the removal of 2CP and MTBE in coal- and
wood-based GACs indicate that these raw materials are most effective,
it is apparent that not all coal- or wood-based GACs are favorable. Con-
sequently, site- and contaminant-specific screening of candidate GAC
materials, using a similar testing approach, would provide a strong
basis for GAC selection. It is concluded that the GAC adsorption oxida-
tion treatment technology is GAC-dependent, and that GAC selection
is an important decision and a key factor in the overall success that
can be achieved.
Notice
The views expressed in this journal article are those of the authors
and do not necessarily represent the views and policies of the U.S. Envi-
ronmental Protection Agency. The U.S. Environmental Protection
Agency, through its Office of Research and Development, funded and
managed the research described here. Any mention of trade names or
commercial products does not constitute endorsement or recommen-
dation for use.
CRediT authorship contribution statement
Klara Rusevova Crincoli:Conceptualization, Methodology, Formal
analysis, Investigation, Resources, Data curation, Writing - review &
editing, Visualization, Supervision, Project administration.Patrick K.
Jones:Conceptualization, Methodology, Formal analysis, Investigation,
Resources, Data curation, Writing - review & editing, Visualization, Su-
pervision, Project administration.Scott G. Huling:Conceptualization,
Methodology, Formal analysis, Investigation, Resources, Data curation,
Writing - review & editing, Visualization, Supervision, Project
administration.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The Authors acknowledge Dr. B. Pivetz (CSS, Buffalo, NY) for scien-
tific support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2020.139435.
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