Journal of Environmental Chemical Engineering 8 (2020) 103849

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Journal of Environmental Chemical Engineering

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

Limitations and prospects of sulfate-radical based advanced oxidation T

processes
Xiaodi Duana,*, Shanshan Yanga,b, Stanisław Wacławekc, Guodong Fangd, Ruiyang Xiaoe,
Dionysios D. Dionysioua,*
a
Environmental Engineering and Science Program, Department of Chemical and Environmental Engineering, 705 Engineering Research Center, University of Cincinnati,
Cincinnati, OH 45221-0012, USA
b
College of Environment and Energy, South China University of Technology, Guangzhou, 510006, China
c
Institute for Nanomaterials, Advanced Technologies and Innovation, Technical University of Liberec, Studentská 1402/2, 461 17 Liberec, Czech Republic
d
Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, 71st East Beijing Road, Nanjing, 210008, China
e
Institute of Environmental Engineering, School of Metallurgy and Environment, Central South University, Changsha, 410083, China

A R T I C LE I N FO A B S T R A C T

Keywords: In recent years, there has been growing interest on the application of advanced oxidation processes (AOPs) based
Advanced oxidation processes on sulfate radical in the elimination of organic contaminants. In such processes, sulfate radical is typically
Sulfate radical generated from the activation of peroxymonosulfate (PMS) or peroxydisulfate (PDS). In this paper, generation of
Wastewater sulfate radical by various methods and mechanism of activation processes for PMS or PDS were discussed.
Groundwater and soil remediation
Moreover, certain applications of sulfate radical-based AOPs in wastewater, groundwater, and soil remediation
were also summarized. More strategies, such as developing stable and highly efficient metal oxide activators,
fabricating efficient carbonaceous-based materials, and combining with other treatment technologies, should be
considered in further applications of sulfate radical-based advanced oxidation processes (SR-AOPs). In addition,
more attention should be paid to elucidate the underlying mechanisms by coupling experimental analysis with
theoretical models. The generation of toxic byproducts, high level of sulfate ion, and complex quenching re-
actions are pointed out as main limitations. Finally, further studies on mechanistic aspects of the chemistry
involved and evaluation of the potential for on-site applications are desired to further explore implementation of
such SR-AOPs.

Speaking of advanced oxidation processes (AOPs), hydroxyl radical
(HO%) is always the keyword, as it possesses high oxidation capability to
decompose a wide variety of contaminants and its generation typically
does not involve hazardous chemicals. However, the non-selectiveness
feature of hydroxyl radical makes it easily scavenged by matrix con-
stituents, such as natural/effluent organic matter (NOM/EfOM) and
common anions. In recent years, there has been a growing interest on
the oxidation of organic contaminants in the aqueous environment by
several other reactive species which are less impacted by NOM or
EfOM, among which is sulfate radical (SR, SO4%). It is a strong single
electron oxidant with high redox potential and selectivity. Compared to
hydroxyl radical, longer half-life makes sulfate radical more readily
diffused and contacted with target pollutants in the complex environ-
mental matrix. Mechanistically, sulfate radical could obtain an electron
from an organic compound to form a radical cation (single electron
transfer), abstract a hydrogen atom from a function group (H-
abstraction), or add to the unsaturated structures forming a radical
adduct (radical addition).
1. Generation of sulfate radical
Common chemicals that can be activated to form sulfate radical are
persulfate, including peroxymonosulfate (SO52−, PMS) and perox-
ydisulfate (S2O82−, PDS, often referred to “persulfate” in commercia-
lized products). The main difference between them is that in the PDS
molecule the peroxide group bridges two sulfur atoms, whereas PMS is
a type of an S-inorganic hydroperoxide. Both oxidants are not very
reactive when non-activated, i.e. when they are not generating radical
species. The primary purpose of the PDS and PMS activation is to break
the (hydro)peroxide (OeO) bond by homolytic or heterolytic cleavage.
The activators could be energy in various forms (e.g. photochemical,
sonochemical, and thermal activation), transition metals (e.g., cobalt,

⁎
Corresponding author.
E-mail addresses: duanxdi@gmail.com (X. Duan), dionysios.d.dionysiou@uc.edu (D.D. Dionysiou).

https://doi.org/10.1016/j.jece.2020.103849
Received 15 January 2020; Received in revised form 9 March 2020; Accepted 10 March 2020
Available online 08 April 2020
2213-3437/ © 2020 Elsevier Ltd. All rights reserved.
X. Duan, et al.
iron, silver, and copper), carbonaceous materials, electrochemical ac-
tivation, alkaline conditions, and several other oxidants (e.g., ozone,
hydrogen peroxide, and calcium peroxide).
Ultraviolet (UV) radiation is a benign and economic method for the
purpose of PDS/PMS activation via cleavage of OeO bond [1]. It has
been demonstrated that PMS can be activated to generate SR by UV
especially in wavelength of 254 nm. Ultrasound with frequencies in the
range 20−1000 kHz produces cavitation phenomena that comprise of
the nucleation, growth, and collapse of bubbles in a liquid. These col-
lapsing bubbles have high temperature (i.e., 5000 K) and high pressure
(i.e., 10 atm) caused by the collapse of cavitation bubbles and can ac-
tivate PDS and PMS to produce free radicals [2]. Heat is an effective
way to activate PDS and PMS [3]. However, the demands of energy
input are high, which makes heat activation inapplicable for the re-
mediation of contaminated water in large scale. Noted that, compared
to the energy-based activation methods, such as UV, ultrasound, heat,
etc., the transition metal activation method is less complex in reactor
equipment and more economical [4].
Transition metal ions can react with PDS or PMS effectively to
generate sulfate radicals [5,6]. Anipsitakis and Dionysiou (2004) [7]
have determined Ag(I) as an optimum homogeneous catalyst for PDS
activation in comparison to other transition metals, and recently the
detailed mechanism of PDS activation by Ag(I) was elaborated by Ike
et al. (2018) [8]; however, there have been more published reports of
PDS and PMS catalysed by iron in its various valence states. Iron overall
was identified as one of the most often used catalytic material for PDS/
PMS activation (especially for PDS, as for PMS divalent cobalt shows
better catalytic properties and is more often applied for its activation
[9,10]). Reasons for the dominance of iron may include the price of
iron, its biocompatibility and its capability for the efficient activation of
PDS. There are several limitations in homogeneous catalytic systems
[11,12]: 1) the recovery of metal ions is very difficult, and more steps
are required for the separation of metal ions; 2) the treatment of was-
tewater with high concentration of organic contaminants will need high
amount of metal ions, leading to high cost and residual metal ions in the
effluent; 3) the catalytic performance is highly dependant on pH be-
cause transition metals form hydrated species in acidic pH and hydro-
xide precipitates in alkaline pH; 4) the existence of organic compounds
can be bonded to the metal ions, which also reduces the generation of
radicals.
To overcome these limitations of homogeneous systems, hetero-
geneous activation has attracted increasing attention. A wide variety of
heterogeneous catalysts have been investigated, such as transition
metal catalysts. For example, nano zero-valent iron (NZVI) can be
successfully applied as a heterogeneous catalyst for the activation of
PDS [13,14] and PMS [15]. The production of SO4%− per mole of PDS
was > 2 times higher when NZVI was used for PDS activation in com-
parison to the ferrous iron activated PDS [13]. The PDS activation
mechanism of zero-valent metal (e.g., Fe0 [16], Zn0 [17], Mn0 [18], and
Al0 [19]) relies on the corrosion effect, irreversibly releasing metal ions
into the effluent. Fe0 has been widely used for PDS or PMS activation
due to its eco-friendliness. However, during the activation process, the
oxidation product of Fe3+ exhibits poor activation ability for PDS or
PMS in the solution phase [20], which limits its further application.
Transition metal oxides such as cobalt oxides, iron oxides and manga-
nese oxides also exhibit good catalytic performance toward PDS or PMS
[21]. Among reported cobalt oxides such as CoO, CoO2, CoO(OH),
Co2O3, and Co3O4, Co3O4 presented excellent activation ability towards
PMS due to the presence of Co(II) and Co(III) in molecule structure
[22]. Besides, the CoO component in Co3O4 is responsible for hetero-
geneous activation of PMS. Meanwhile, Dionysiou’s group firstly in-
vestigated the reason accounting for cobalt leaching in Co3O4 and be-
lieved that the cobalt leaching is ascribed to CoO [23]. For iron oxides,
Fe3+ species cannot produce radicals directly until being reduced to
Fe2+; thus, the generation of Fe2+ is vital for iron oxide-based catalysts.
Encapsulating Fe2O3 with an electron transfer mediator can enhance
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Journal of Environmental Chemical Engineering 8 (2020) 103849
the catalytic performance of Fe2O3. For example, dipicolinic acid,
which contains electron-rich nitrogen and oxygen groups, can be used
as supporting materials and plays the role of an electron shutter to
mediate the electron transfer between Fe3+ and PMS [24]. However,
the application of transition metal-based catalyst still has some lim-
itations such as metal leaching, aggregation phenomena, and corrosion
of catalyst. Developing supported catalyst can be adopted to overcome
the metal leaching and aggregation of transition metal-based catalyst.
Inorganic- and carbon-based supports are the two main kinds of sup-
ports. Recently, metal oxides including MnO2 [25], Mn3O4 [26] and
CuO [27,28] were used as support of iron-based catalysts, which not
only changes the physicochemical properties of the catalyst, but also
induces new functionalities. For example, radical and non-radical
pathways coexist during PMS activation process when Fe3O4 is in-
corporated with CuO [28]. Wu et al. [29] immobilized nanoscale Fe0 on
reduced graphene oxide (rGO) as PDS activator for atrazine degrada-
tion. After three cycles, the degradation efficiency of atrazine decreased
only by less than 15 %. The carbon-based support also attracts attention
as catalyst support. Wang et al. [30] used ordered mesoporous carbon
(OMC) as support to increase the dispersity of cobalt species. The ob-
tained Co-OMC composite exhibited remarkable catalytic ability to-
wards PMS, which was ascribed to the synergistic effect between CoOx
and OMC. In addition, natural minerals can also be used as hetero-
geneous catalyst such as magnetite [31], kaolinite [32], as well as
sulfur-containing minerals [33–35]. Zhou’s group [34] found that PMS
was effectively activated by FeS2 for diethyl phthalate degradation and
sulfides were the dominant electron donor for PMS activation. Natural
negatively charged kaolinite with abundant hydroxyl groups can acti-
vate PMS effectively for the degradation of atrazine, demonstrating the
important role of surface-bonded and structural hydroxyl groups in
activating PMS [32]. Recently, metal-free nanocarbons have stimulated
an immense impetus as heterogeneous catalysts for sulfate radical based
AOPs. Biochar, activated carbon, nanodiamond, carbon nanotube,
graphene and hexagonally ordered mesoporous carbon can be designed
to activate PDS or PMS for contaminant degradation [36]. Graphitiza-
tion degree, heteroatom doping, structural defects, and surface chem-
istry within a porous framework are vital properties for nanocarbons for
superoxide activation. The poor catalytic stability of nanocarbons is the
main drawback for their application in AOPs.
In addition to PDS and PMS, other non-oxidant sulfur source, such
as SO32−, could also be activated to form sulfate radical via S-cycle
processes for oxidation of the contaminants [37]. It needs to be noted
that in most of SR-AOPs, hydroxyl radical is expected to exist and
transformed from/to sulfate radical depending on the matrices (Eq. 1
and 2) [8].
SO4%− + HO− → SO42− + HO% (1) k = 6.5 ± 1.0 × 107 M−1 s−1
SO4%− + H2O → SO42− + HO% + H+ (2) k < 2 × 10−3 s−1
2. Activation mechanism
Although several of mechanisms of conventional activation pro-
cesses for PDS or PMS have been well established in previous studies
[7,20,38], some different results have been reported in recent years
[39–44]. One of the most controversial points is the activation of PDS
by iron (II). It has been reported that the single electron transfer from
Fe(II) to PDS to yield sulfate radical was the main pathway for this
activation system; however, a recent study requested to completely re-
investigate the iron(II) activation of PDS, claiming that Fe(IV) rather
than sulfate radical is the dominant reactive intermediate (under acidic
conditions) [39]. Although additional studies are needed to confirm this
hypothesis, the overwhelming evidence suggests that not only SO4%− is
generated under typical water treatment conditions, but also other re-
active species, including superoxide radical, are produced and
X. Duan, et al.
accounted for pollutant degradation [45,46]. Moreover, non-radical
pathways for PMS or PDS activation have been reported, which in-
cluded singlet oxygen or direct electron transfer between pollutant and
oxidant mediated by carbon materials [47,48]. In addition to the before
mentioned reaction of PDS with ferrous iron [39,40], generation of iron
in high oxidation state was confirmed for PMS reaction with Fe(II)
[41,42] and even in the heterogeneous systems involving PDS [43,44].
In addition, some emerging activators have been developed for PMS
or PDS, and different mechanisms were included in these different ac-
tivation processes. For instance, non-radical pathway has been observed
in the heterogeneous activation of PDS or PMS by carbon materials, and
other reactive species such as singlet oxygen or the direct electron
transfer between PDS or PMS and pollutants were involved in the de-
gradation of target pollutants [49]. However, the mechanism of non-
radical pathway is also not fully understood. Therefore, a fundamental
gap in knowledge in this area should serve as an encouragement for
further research. In general, a deeper understanding is required in the
field of SR-AOPs and some efforts towards this will require a combi-
nation of experimental and theoretical studies including: 1) employing
more novel methods for free radical identification and more effective
methods for the determination of intermediates of pollutant degrada-
tion; 2) combing experimental analysis with theoretical models; and 3)
exercising theoretical calculations improved by the adoption of relative
solutions to the corresponding Density functional theory (DFT) limita-
tions.
3. Application in groundwater and soil remediation
In recent years, AOPs have been attracting increasing attention in
groundwater and soil remediation. Common oxidants being used in-
clude H2O2, PDS and PMS. In general, H2O2-based Fenton or Fenton-
like reactions is applied to generate hydroxyl radical, but the require-
ment of strict acidic conditions and production of iron sludge limits the
application of H2O2 in groundwater and soil remediation. In contrast,
sulfate radical has longer half-life (～10−6 s) than hydroxyl radical (～
10-9 s), which allows the transport of the former further down-gradient
in the subsurface environment. Both the activation of PDS and PMS can
generate sulfate radical, while PDS is chosen as an oxidant for
groundwater or soil remediation because of its lower price, more sta-
bility, and easier transport in the subsurface environment [50]. Thus,
SR-AOPs using PDS as oxidant are highly feasible in in situ chemical
oxidation (ISCO) for soil and groundwater remediation. The addition of
PDS alone was the initial approach of sulfate based AOPs in soil re-
mediation. Transition metals in minerals within the soil can activate
PDS and improve the removal of contaminants. Besides, the activators
of PDS for ISCO could be alkaline conditions, hydrogen peroxide, or
possibly iron (II) [51]; however, their effectiveness in field applications
are highly site-specific [38]. Although some previous studies elucidated
the interaction mechanism of minerals such as Fe/Mn-minerals and
Fe3O4 activated PDS, further studies are needed to examine this process
in situ of realistic soil environment [52,53]. PDS can be dosed to the soil
in direct push injections or through vertical or horizontal recirculation
wells [54]. The dosing methods are usually chosen taking into account
the geological situation at the site. The kinetics and products formed
during the degradation of target pollutants are usually different than in
aqueous solution due to the complex properties of soil. For example, the
mineralization efficiency of pollutants was very low in soil due to the
presence of organic matter, and the potential risk of degradation in-
termediates needs to be evaluated, considering that some intermediates
might be more toxic than their corresponding parent compounds.
Nonetheless, projects focusing on in situ oxidation of persistent or-
ganic contaminants with the use of PDS are being developed. One ex-
ample is the PDS (alkaline activated) treatment that was performed at
the site contaminated with hexachlorocyclohexane isomers - Bailín
[Spain; during the project LIFE DISCOVERED (http://www.
lifediscovered.es/programa-life.html)]. It was found that toxic
3
Journal of Environmental Chemical Engineering 8 (2020) 103849
compounds (i.e., hexachlorocyclohexane, benzene) could be efficiently
removed during the pilot action, and this project was also economically
viable. Complete contaminant oxidation was achieved after 1 month,
whereas the equivalent remediation of the contaminated site by tradi-
tional methods could be degraded ca. in 2–5 years [55].
4. Application in wastewater treatment
SR-AOPs could be applied to eliminate organic contaminants in
wastewater, or to enhance the biological treatment performance by
increasing the biodegradability. The degradation efficiencies of organic
contaminants rely highly on the concentrations of catalysts or intensity
of the energy, dose of oxidants, level of contamination, solution pH and
alkalinity, presence of NOM or EfOM and inorganic ions, as well as
other impurities [56]. For example, degradation rates of SR-AOP at
lower pH values are generally considered to be higher, however, ap-
preciable removal rates were also obtained at neutral and alkaline pH
(which is often associated with interchanging of the radical species)
depending on the contaminant and activation type [57]. Overall, the
decontamination of wastewater using SR-AOPs has been studied in la-
boratories extensively; however, the implementation of such processes
in wastewater treatment plants is not common due to several concerns.
Like other oxidation processes, SR-AOPs may produce toxic by-
products, including transformation products of target contaminants and
the byproducts generated from effluent organic matter. In some cases,
the overall toxicity of the treated matrices may be increased sub-
stantially, indicating that some byproducts generated in SR-AOPs (i.e.,
as in some other AOPs) are more dangerous than the original con-
taminant. Therefore, SR-AOPs are expected to couple with other ad-
vanced treatment processes to reduce the impurities, e.g., combining
membrane technologies with SR-AOPs could improve detoxification
[58], and adding activated carbon as a post-treatment could reduce the
organic byproducts. During the last few years, activated PDS and PMS
were broadly applied in the laboratory for disintegration of waste ac-
tivated sludge [59] and anaerobically digested sludge [60] (both are
undesired products of the biological wastewater treatment). It is well
documented that sulfate radicals can react very fast with the sludge
flocs as well as cell membranes. This leads to the enhancement of de-
waterability and often improvement of other sludge properties. How-
ever, there is a lack of reports regarding the toxicity of such oxidized
sludges.
5. Limitations and strategies of SR-AOPs in application
The increase of publications concerning SR-AOP does not directly
correlate with progress of application of such technologies in practice in
field applications. The largest controversies of SR-AOP could be prob-
ably associated with the formation of different reactive species ac-
counted for pollutant degradation, which was depended on the acti-
vators for persulfate. Developing novel and sensitive analytical
techniques/scavengers to identify and distinguish reactive oxygen
species (ROS) generated in such systems could help in gaining further
knowledge of the mechanisms involved in SR-AOP processes. For ex-
ample, electron paramagnetic resonance (EPR), free radical quenching
and DFT calculations have been developed to identify the free radicals
and subsequently the pathways or intermediates of pollutant degrada-
tion. Although there are already several reports on computational ap-
proaches for prediction of sulfate radical reactivity with different con-
taminants, further mechanistic studies based on ab initio calculations
could help obtain deeper understanding of SR-AOP, since until now (in
AOPs) computational approaches have been mostly limited to hydroxyl
radical [61]. In addition, with the help of Quantitative Structure-Ac-
tivity Relationships (QSARs), the chemical structures of by-products
formed in the SR-AOP [62] can be correlated with their toxicity, which
could help in sustainability assessment of the potential applications of
SR-AOPs in situ treatment.
X. Duan, et al.
One of the major issues associated with SR-AOPs is the generation of
high level of sulfate ion. To protect the aquatic life, sulfate ion is ty-
pically regulated to be less than 500 mg/L [63], which is a challenge to
maintain during the remediation using PDS or PMS for effective re-
moval of contaminants. One approach to overcome this limitation is
integrating SR-AOPs with a cheaper oxidant, e.g., hydrogen peroxide or
ozone, to achieve synergistic oxidation effect, and thus decrease the
PDS dosage and sulfate post-contamination [64]. Compared with PDS,
PMS is easier to be activated in most cases; however, PMS is more ex-
pensive than most of common oxidants [38]. To reduce the dosage of
PMS and minimize the quenching reactions between the radicals, more
efficient and effective activators are required. Nanoscale activators for
sulfate radical generation could be applied. However, how to batch the
production and reduce the cost of nanomaterials in the filed applica-
tions is a problem of concern [65].
To make SR-AOPs promising in the application of environmental
remediation, low-cost, highly efficient, and environmental-friendly
catalysts should be developed. In addition, new equipment should be
explored to increase the transport of oxidants and activators in the
subsurface environment to contact with pollutants in groundwater. To
fill the gaps between the laboratory research and demands for SR-AOPs,
it is necessary to carefully identify the task-specific utilizations with
narrow applicability, and to evaluate the selection of the most pro-
mising SR-AOP for a target application. Investigation on the influence
of pH on PDS/PMS decomposition and SR formation can be considered
as a next important challenge. Further studies on the mechanistic as-
pects and on-site applications are desired.
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
D. D. Dionysiou acknowledges support from the University of
Cincinnati through a UNESCO co-Chair Professor position on “Water
Access and Sustainability” and the Herman Schneider Professorship in
the College of Engineering and Applied Sciences. S. Wacławek also
acknowledges the support of the Ministry of Education, Youth and
Sports in the Czech Republic under the “Inter Excellence – Action
programme” (LTAUSA18078).
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