Chemical Engineering Journal 330 (2017) 44–62

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Chemical Engineering Journal

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Review

Chemistry of persulfates in water and wastewater treatment: A review MARK

a,⁎ b,c,d e a
Stanisław Wacławek , Holger V. Lutze , Klaudiusz Grübel , Vinod V.T. Padil ,
Miroslav Černíka, Dionysios.D. Dionysiouf,⁎
a
Centre for Nanomaterials, Advanced Technologies and Innovation, Technical University of Liberec, Studentská 1402/2, 461 17 Liberec 1, Czech Republic
b
University Duisburg-Essen, Faculty of Chemistry, Instrumental Analytical Chemistry, Universitaetsstraβe 5, D-45141 Essen, Germany
c
IWW Water Centre, Moritzstr. 26, D-45476 Mülheim an der Ruhr, Germany
d
Centre for Water and Environmental Research (ZWU) Universitätsstr. 5, D-45141 Essen, Germany
e
Institute of Environmental Protection and Engineering, Department of Environmental Microbiology and Biotechnology, University of Bielsko-Biala, Willowa 2, 43-309
Bielsko-Biała, Poland
f
Environmental Engineering and Science Program, University of Cincinnati, 705 Engineering Research Center, Cincinnati, OH 45221-0012, USA

G RA P H I C A L AB S T R A C T

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

Keywords: Persulfate decontamination technologies either utilizing radical driven processes or direct electron transfer are
Persulfates very powerful tools for the treatment of a broad range of impurities, including halogenated olefins, BTEXs
Peroxydisulfate (benzene, toluene, ethylbenzene and xylenes), perfluorinated chemicals, phenols, pharmaceuticals, inorganics
Peroxymonosulfate and pesticides. Furthermore, the reactivity of persulfates is extremely dependent on the related activation
Remediation
techniques and the composition of the treated water matrix. Direct reactions of peroxydisulfate (PDS) or per-
Oxidation
Sulfate radical
oxymonosulfate (PMS) are rather slow and mostly unsuitable for pollutant degradation. However, PDS or PMS
decompose at elevated temperatures under UV radiation, and radiolysis treatment as well as in presence of
reduced metal ions to form sulfate radicals (SO4%−). (SO4%−)-based oxidation can also form secondary oxidants
for instance carbonate radicals, hydroxyl radicals, superoxide radicals or singlet oxygen which can influence
both transformation efficiency and product formation. The formation of such species is extremely subjected on
the water matrix composition and can hardly be predicted. One important aspect in dealing with PDS or PMS is
their analysis, which is often prone for interference by other matrix components and hampered by the low
stability of PDS and PMS in aqueous systems. Numerous methods for analysis of PDS and PMS are available. The
present work also provides an overview on these methods.

1. Introduction the world [1,2]. One reason is the misuse or overuse of antibiotics e.g.
for agricultural purposes, which enrich the population of multi-resistant
Over the last few decades, ubiquitous contamination with various pathogens [3]. In many countries with a low human development index
inorganic and organic substances has caused serious problems all over (HDI), particularly in Africa and Asia, surface- and groundwater

⁎
Corresponding authors.
E-mail addresses: stanislaw.waclawek@tul.cz (S. Wacławek), dionysios.d.dionysiou@uc.edu (D.D. Dionysiou).

http://dx.doi.org/10.1016/j.cej.2017.07.132
Received 5 June 2017; Received in revised form 18 July 2017; Accepted 19 July 2017
Available online 21 July 2017
1385-8947/ © 2017 Elsevier B.V. All rights reserved.
S. Wacławek et al. Chemical Engineering Journal 330 (2017) 44–62

contamination can be a direct cause of water scarcity. It is important, Table 1

therefore, to develop cheap and efficient water and wastewater treat- Various properties of common oxidants used for in situ remediation.
ment methods [4].
Oxidant OeO bond- Solubility Average Price Price
There are many different water and wastewater decontamination dissociation in water at estimated [USD [USD
methods, which can be universally divided into biological [5], physical energy [kJ 25 °C [g lifetime in kg−1]2 mol−1]
[6], and chemical methods [7]. mol−1] L−1] groundwater4
Oxidants used for environmental purposes can be divided into ones
H2O2 213 soluble hours to days 1.5 0.05
that possess a peroxide bond and ones that do not. Oxidizing agents O3 364 0.1 <1 h 2.3 0.11
such as ozone and hypochlorite have long been employed for water and Potassium – 0.7–33 unstable in 2000 396
wastewater treatment [8,9]. Oxidants possessing the OeO bond (known ferrate water at
as peroxide or the peroxo group), typically form free radicals which in pH ≠ 9
PDS5 926 730 >5 months 0.74 0.18
turn may result in pollutant degradation.
PMS 3776 298 hours to days 2.21 1.36
Peroxydisulfate (PDS) and peroxymonosulfate (PMS) are gaining
increasing attention in water and wastewater treatment [10–12] The remaining data was taken from [16,19].
1
(Fig. 1). Many studies have shown that they are capable of degrading PMS is herein considered as the Oxone® salt (2KHSO5·KHSO4·K2SO4).
2
highly toxic and persistent pollutants, e.g. polychlorinated biphenyls Prices per kg are taken from: [15,20]. http://www.labmanager.com/news/2010/04/
new-battelle-process-slashes-price-of-useful-but-expensive-chemical?fw1pk=2#.
(PCBs) [13,14], and are relatively cheap in comparison to other oxi-
Vu2SzOZxBqF; [21].
dants [15] (Table 1). 3
[22].
This paper reviews the chemical and physical properties of persul- 4
Depends on water hardness, transition metal concentration, dissolved organic carbon
fates in addition to their determination and activation methods. (DOC) concentration, and many other factors.
5
Moreover, the direct oxidation reactions of persulfates as well as oxi- Sodium PDS.
6
[23].
dation with generated radicals are described.

2. Chemical and physical properties of persulfates

Peroxydisulfuric acid (H2S2O8) was first detected by Marcelin

Berthelot (French chemist) in 1878 [16]. It can be formed in the elec-
trolysis process of sulfate salt. The resulting PDS salt is almost non-
hygroscopic and has a good longevity. PDS could be found in the form
of three salts i.e. sodium, potassium and ammonia. Potassium PDS has
very low solubility for in situ remediation, and the application of am-
monium PDS can cause residual ammonia and secondary contamina-
tion. Hence, the sodium PDS salt (Na2S2O8) is the first choice for in situ
chemical oxidation (ISCO) treatment. It has a high solubility of 730 g
kg−1 H2O (at 25 °C) [17,18].
PDS is cheap in comparison to other oxidants used in situ (0.74 USD/
kg), but is still more expensive than hydrogen peroxide for large-scale Fig. 2. (a) Sodium PDS and (b) Oxone triple salt molecular structure (*potassium PMS
applications. The bond dissociation energy and bond length of [O3SO- (KHSO5) - active part of Oxone; bond lengths were taken from [28]).
OSO3]2− were respectively determined to be 140 kJ mol−1 and 1.497 Å
[15,16,19].
potential applicability [25–27]. In comparison to PDS, PMS has a
Peroxymonosulfate (PMS; monopersulfate) has its origin from the
shorter bond length (1.46 Å), which translates to a higher bond dis-
Caro’s acid (H2SO5) also known as persulfuric, peroxymonosulfuric, and
sociation energy (377 kJ mol−1). In other words, in theory, PMS re-
peroxysulfuric acid [24]. It possesses reactive oxygen closest to the
quires more energy to produce radicals in the homolytic cleavage of the
hydrogen atom that carries the active power (Fig. 2b). Since the oxygen
peroxide bond.
is readily reactive, KHSO5 is usually found in a more stable form of a
The cost of Oxone is the highest of all of the conventionally used
white triple salt, 2KHSO5·KHSO4·K2SO4 (potassium hydrogen PMS).
oxidants in ISCO, although it is still much cheaper than ferrates [21].
Commercially, the product goes under the trade-name of Oxone® and
Persulfates are very stable in the solid state and remain stable for
has a high solubility in water, is safe to handle, hence it has a good

Fig. 1. Annual number of a) publications concerning PDS or PMS and b) citations. Source: Web of knowledge (data as of July 2017).

45
S. Wacławek et al.
several months in pure water. One of the advantages of PDS in com-
parison to the other commonly used ISCO reagents (hydrogen peroxide
or ozone) is its much higher stability i.e. smaller transportation issues;
elevated concentrations of PDS can be pumped into the contaminated
area, and it could be moved by the density driven dispersion through
the treated soil [12].
Yen et al. [14] determined that PDS anions can persist in the soil
system for over five months. PMS does not show such a high persistence
as PDS, although when being stored in a dry and cold place, it loses only
around 1% activity/month due to the oxygen and heat release (http://
www2.dupont.com/Oxone/en_US/index.html). Under the influence of
elevated temperatures (>300 °C) it decomposes to SO2 and SO3. PMS is
also not stable in water with higher pH values (at pH 9 the stability
reaches minimum), whereby concentration of its protonated form
(HSO5−) equals the concentration of the unprotonated one (SO52−)
[29]. More described information on the stability of PMS at various pH
values can be found in Bouchard et al. [29].
Peroxydisulfate and peroxymonosulfate are among the strongest
oxidizing agents that are applied in environmental remediation. The
standard oxidation–reduction potential (ORP) for the reduction of PDS
anion (Eq. (1)) equals to 2.01 V, hence it is higher than that of PMS i.e.
1.4 V (Eq. (2)) [30,31].
S2O82 − + 2H+ + 2e− → 2HSO−4 (1)
HSO− + − − They found that PMS was the all-embracing oxidizing agent catalysed
5 + 2H + 2e → HSO4 + H2O (2)
In case persulfates are used for pollutant degradation, the radicals
formed upon cleavage of the peroxide bond are the most important. The
radical formation can be initiated by different means, i.e., photo-
chemical or thermal cleavage of the peroxide bond or chemical re-
duction. PDS typically decays in a radical pathways often resulting in
sulfate radicals. However, PMS may also decompose into sulfate radical
and hydroxyl radical [32].
3. Activation mechanism
The key in PDS and PMS-based oxidation is formation of highly
reactive species, which themselves have a potential to degrade pollu-
tants. This can be achieved mainly by thermal [33–36], photolytic [37],
sonolytic [38], radiolytic activation [39], as well as by the reactions of
PDS and PMS with iron oxide magnetic composites [40,41] including as
well in situ formed iron hydroxides [42] and quinones [43]. Further-
more, activation of persulfates by hydroxide ions [44,45] in ozonation
[46] or in presence of phenol [47] was described. Moreover, sulfate
radicals could be also generated by chemical reduction of PMS and PDS
using low valent transition metals as reductant [48,49] including also
bimetallic or trimetallic iron-based systems as well as iron scrap
[50,51]. Photo and radiodissociation or thermal activation of PMS
precedes the evolution of both SO4%− and %OH [49,52]. The formation
of SO4%− as the main oxidizing species can be performed only via
transition-metal catalysis (although the interchange of radicals in water
solutions can be also notable and will be further discussed in Section
5.3). In the group of the transition element ions (Fe2+, Co2+, Ni2+,
Cu2+, Ru3+, Ag+), divalent cobalt was determined to be the most ef-
ficient catalyst for PMS according to Anipsitakis and Dionysiou [53]
and Fernandez et al. [54]. As for PDS, similarly to the Fenton reaction,
Fe2+ is the most commonly used metal for the homogeneous catalysis.
The type and dose of the transition metal catalysis is of significant
importance, since when it is applied in excess, scavenging of sulfate
radicals may become a problem [55], this problem however can be
solved by adopting the use of solid iron particles where the release of
iron species responsible for PDS activation occurred smoothly without
the risk of sulfate radical quenching as reported by Naim and Ghauch
[51]. Ayoub and Ghauch [50] demonstrated as well that PDS activation
can be better sustained in solution especially while using bimetallic and
trimetallic iron-based systems making the process more efficient toward
46
Chemical Engineering Journal 330 (2017) 44–62
long term application.
A detailed summary of the activation methods of PDS and PMS is
presented in Tables 2 and 3, respectively.
The application of PMS and PDS in oxidation treatment belongs to
advanced oxidation processes (AOPs) because of the free radicals pre-
sence [67].
AOPs can be either homogeneous or heterogeneous. Whilst homo-
genous AOPs are the most efficacious at an acidic pH, heterogeneous
advanced oxidation processes could function in a wide pH spectrum
[68,69]. Despite the fact that heterogeneous AOPs exhibit numerous
benefits in comparison to homogenous ones, the point that the catalyst
creation is not easy nor economical should also be considered [60]
(however there are some exceptions of this rule [51]).
3.1. Homogeneous activation process
In the case of ISCO, activation should be slow to allow the long-term
formation of radicals and the treatment of heterogeneously distributed
contaminants. For homogenous radical based processes, one of the most
common methods is to use chelated transition metals, which sig-
nificantly decreases the metal concentration required for the activation
[70,71]. Rastogi et al. [72] assessed the efficacy of several chelating
agents i.e. ethylenediaminedisuccinate, citrate, and pyrophosphate on
ferrous iron activation of PMS and PDS under neutral pH conditions.
by all ferrous iron-chelates, whereas citrate coupled with ferrous iron
was the best chelate/iron configuration.
3.2. Heterogeneous activation processes with metal catalysts
On the other hand, heterogeneous processes with material (often in
nano-scale) synthesized beforehand, have drawn much attention re-
cently due to their excellent performance. In addition, as mentioned
above, cobalt has been found to be the very best homogenous activator
for PMS. Therefore, heterogeneous catalysts often also contain cobalt
(especially the ones that are used for peroxymonosulfate activation).
Co3O4 was used for instance by Chen et al. [73] and Muhammad et al.
[74] as a catalyst for PMS to degrade Acid Orange 7 (AO7) and phenol,
respectively (see also [75–78]). Interestingly, Zhang et al. [79] syn-
thesized nanoscale Co3O4 and applied it in heterogeneous activation of
PDS. The highest degradation rate of Orange G (as a model compound)
was at pH ∼ 7, where the catalyst dissolution is very low. The authors
also confirmed that the hydroxyl and sulfate radicals were the main
oxidants.
One of the major problems of the activation of persulfates with
Co3O4 is an excessive quantity of cobalt leaching. To improve catalytic
capacity and decrease leaching, cobalt can be attached to several sup-
ports (most often metal oxide) i.e. Al2O3, TiO2, SiO2, MgO or activated
carbon/carbon aerogel or graphene. For example, Yang et al. [78]
confirmed that the TiO2 support increased the content of –OH groups on
the Co/TiO2 catalysts, enhancing the generation of the Co-OH complex,
that is believed to be a crucial stage in heterogeneous activation of PMS
(Eq. (3)).
In another study, Yao et al. [80] used bimetallic oxides CoFe2O4 and
CoFe2O4− on graphene to catalyse PMS and thus abate phenol. Su et al.
[81] successfully synthesized heterogeneous CoxFe3−xO4 material and
discovered that the iron-cobalt interactions are vital for effective het-
erogeneous catalysis of PMS. Lin et al. [82] demonstrated an alternative
path to synthesize a magnetic nano-Co-graphene composite from car-
bonizing of a cobalt-based metal organic frameworks and graphene
oxide, and used it to activate PMS. In order to measure the long-run
catalytic activity, a 50-cycle decolorization of Acid yellow 17 was
performed and the efficacy of degradation remained at 97.6%, dis-
playing its stability and efficient catalytic activity. In their further
study, a nanocomposite was prepared by the carbonization (one-step) of
a Co-based zeolitic imidazolate [83]. Higher cobalt/carbon
 Table 2
PDS activation methods.

Method Mechanism Predominant radical species Comments Reference

S. Wacławek et al.

Heat Homolysis of peroxide bond Sulfate radical/Hydroxyl radical (in Because of the low bond-dissociation energy, often low temperature [35,36,56]
presence of chloride / at elevated increase can effectively cleave OeO bond
pH)
UV radiation Homolysis of peroxide bond Sulfate radical Often used λ = 254 nm, Quantum yield 1.4 (depends on dissolved [57–59]
oxygen concentration)
Homogenous: Transition metals One electron transfer Sulfate radical Often requires low pH [48]
Heterogeneous: Transition metals One electron transfer Sulfate radical Preparation of catalyst is not economical [50,60]
(mono, bi, and trimetallic
systems)
Chelated transition metals One electron transfer Sulfate radical Stabilizes ferrous iron at neutral pH, widely used in situ [61]
Alkaline pH Base-catalysed hydrolysis of PDS to hydroperoxide, which later initiates Sulfate radical/Hydroxyl radical/ Often pH > 11 [44]
radical formation Superoxide radical
Electrolysis Ferrous iron generated in the chemical and electrochemical corrosion of Sulfate radical/Hydroxyl radical Additional Fe3+ reduction on the cathode. Yuan et al. [62] claim that OH [62]
iron radical contribution in this system is more significant
Nanocarbons Peroxide bond of PDS is debilitated on the defective edges and Hydroxyl radical Reduced mesoporous carbon, carbon nanotubes, and graphene oxide, [15,63]
oxygengroups (from which the carbonyl group was found as the most displayed great catalyticproperties, in contrary to nanodiamonds,
active one) of carbocatalysts, than persulfate oxidizes adsorbed water or fullerenes and graphitic carbon nitride
hydroxide ions
Other organics One electron transfer Sulfate radical Low molecular weight, anionic organic compounds [43,47]
Radiolysis Reaction with the solvated electron Sulfate radical Electron beam irradiation of aqueous solution [39]

47
Table 3
PMS activation methods.

Method Mechanism Predominant radical species Comments Reference

Heat Homolysis of peroxide bond Sulfate radical/ Hydroxyl Higher temperatures are required to split the OeO bond, due to a higher bond-dissociation energy in [49]
radical comparison to S2O82−
UV radiation Homolysis of peroxide bond Sulfate radical/ Hydroxyl Often used λ = 254 nm, Quantum yield 0.52 [49,52]
radical
Homogenous: Transition metals One electron transfer Sulfate radical Often requires a low pH to have the metals in a desirable oxidation state [49]
Heterogeneous: Transition One electron transfer Sulfate radical Preparation of catalyst is not economical [60]
metals
Alkaline pH Base-catalysed hydrolysis of PMS to hydrogen Superoxide radical [45]
peroxide
Electrolysis One electron transfer from electrochemically/ Sulfate radical The contaminant degradation rate by an oxidant assisted with electrolysis was observed in the following [64]
chemically produced Fe2+ order: PMS > PDS > H2O2
Nanocarbons One electron transfer Sulfate radical Graphene demonstrated better catalytic performance than few other allotropes of carbon, like: activated [65]
carbon (AC), graphite, graphene oxide, and carbon nanotubes
Organics One electron transfer Sulfate radical/ Hydroxyl Polyimide as an electron donor [66]
radical
Ozone Formation of an – O3SO5− adduct that decomposes Sulfate radical/ Hydroxyl – [46,52]
into radicals radical
Radiolysis Homolysis of peroxide bond Sulfate radical – [49]
Chemical Engineering Journal 330 (2017) 44–62
S. Wacławek et al.
nanocomposite loading, PMS dose, acidic conditions and temperature
greatly ameliorated the degradation of caffeine. Following the change
of the reaction rate after addition of different radical scavengers (i.e.,
methanol (MeOH) and tert-Butyl alcohol (TBA)), it was shown that the
process involves rather sulfate radicals than hydroxyl radicals. Shi et al.
[84] demonstrated Co3O4/expanded graphite, developed in a sol-
vothermal synthesis, as an extremely effective heterogeneous catalyst of
PMS. They concluded that the abatement of Orange II in water is due to
SO4%−, and 100% removal can be reached after 8 min. Ding et al. [85]
used cobalt and bismuth salts and sodium hydroxide (as a precipitation
agent) to create the Co3O4-Bi2O3 nanocomposite as a heterogeneous
catalyst for PMS. The nanocomposite demonstrated substantial catalytic
performance towards PMS for the removal of organic contaminants.
Moreover, leaching of cobalt was decreased to 43 µg L−1, which is an
improvement when compared to that of Co3O4 (158 µg L−1) under
equivalent testing conditions. Yang et al. [76] claimed that the het-
erogeneous oxide CoFe2O4 was capable to steadily catalyse PMS for the
abatement of 2,4-dichlorophenol at pH 7. Furthermore, in this system,
leaching of cobalt was reduced to a very low extent. However, such a
reduction in cobalt leaching requires the pH of the solution to be close
to 7.0, which is problematic in the applicability for treatment of water
or wastewater due to substantial acidification during activation [86].
Hence, it is still an important challenge to develop an efficacious cobalt-
carrying heterogeneous catalyst for PMS without causing a secondary
contamination. One way to overcome this problem was proposed by
Rhadfi et al. [87], who determined that the partial replacement of co-
balt in Co3O4 with Mn can be a strategy for decreasing the quantity of
the harmful Co element. Mn is more abundant in nature, more en-
vironmentally friendly, and is twenty times cheaper than cobalt [88].
Wang et al. [89] provided an example of the PMS catalytic mechanism
using an iron oxide/C core shell magnetic nanosphere supported by
manganese oxide nanoparticle. They found that SO4%− was the primary
radical for phenol degradation. The same authors also attempted to use
3D-hierarchically structured MnO2 to activate PMS [90]. The catalytic
mechanism of PMS activation was determined therein by electron
paramagnetic resonance (EPR (also known as electron spin resonance,
ESR)) spectra and showed that hydroxyl and sulfate radicals are si-
multaneously produced in the activation processes, however SO4%−
played a more crucial role in oxidation of carbolic acid. Similarly, Li
et al. [91] synthesized three trivalent Mn (oxyhydr)oxides, namely
bixbyite, hausmannite and manganite, from which only manganite
showed good catalytic activity for PDS activation. Analogous to Wang
et al. [90], it was also shown that both SO4%− and %OH are present
during the treatment, although the sulfate radicals were selected as the
predominant oxidative species in phenol oxidation.
Similarly to the homogeneous systems, iron-based compounds are
frequently used for persulfate activation due to their lower toxicity
compared to cobalt. Tan et al. [92] reported a nano-Fe3O4 catalyst in
PMS activation process, whose stability decreased significantly from the
first to the third run. In another study, authors of a recent paper con-
cerning heterogeneous catalysis [60], fabricated CuFe2O4-Fe2O3 for the
activation of peroxymonosulfate and subsequent degradation of bi-
sphenol A [93]. The performance of CuFe2O4-Fe2O3 was compared with
the alternative heterogeneous catalytic materials and shown to be su-
perior in comparison to CuFe2O4, CoFe2O4, CuBi2O4, CuAl2O4, Fe2O3,
and MnFe2O4 (whereas the catalyst order indicates their activity to-
wards PMS). Moreover, it is possible to reuse CuFe2O4-Fe2O3 catalyst
(at least several times) without significant performance loss. In addi-
tion, Zhang et al. [94] observed that the property of nano-Fe3O4 to
activated PMS can be recycled by hydroxylamine. Furthermore, the
catalytic ability of Fe3O4 coupled with hydroxylamine soared gradually
in the ten consecutive runs.
Ghauch’s group by working on bi and trimetallic systems has sig-
nificantly contributed to the heterogeneous catalyst in the field of
peroxydisulfate [50]. They have determined inter alia that the iron
scrap of special properties can reduce the release of metal ions in
48
Chemical Engineering Journal 330 (2017) 44–62
solution to a minimum and the repeated experiments did not show any
efficiency loss [51]. Moreover, their research on the reaction stoichio-
metric efficiencies (RSE) allows to better understand and compare the
reaction mechanism of different activation methods and its correlation
to the mineralization extent of the organic contaminant [95].
3.3. Heterogeneous activation with metal-free catalysts
Recently, catalytic materials with no metal content are gaining
popularity due to the many advantages, i.e. lack of secondary pollution,
chemical stability, and that generally they are considered as en-
vironmentally compatible [66]. It was confirmed that the functional
groups of carbonaceous materials that possess oxygen (especially the
carbonyl group) can effectively contribute to the activation of persul-
fates [96]. From the metal-free heterogeneous catalyst, Sun et al. [65]
found that the reduced graphene oxide (rGO) can serve as an effective
heterogeneous catalyst to activate PMS in order to form radicals. Zhang
et al. [97] used granular activated carbon (AC) as a “green” catalytic
material for PMS to degrade Acid Orange 7 in an aqueous solution.
Also, Saputra et al. [98] reported that AC powder can be an en-
vironmentally friendly catalyst for the efficient activation of PMS that
later exhibited excellent potential for phenol degradation mediated by
sulfate radicals.
Lee et al. [63] discovered that carbon nanotubes could catalyse
persulfates to form species that are more reactive. Similarly, Duan et al.
[15] evaluated the ability of various nanocarbons to activate PDS for
degradation of phenolic compounds, dyes, and intermediates formed
during their treatment process. As PDS activators, single wall carbon
nanotubes, rGO, and mesoporous carbon displayed great catalytic
performances, while nanodiamonds, fullerenes, and graphitic carbon
nitride showed lower efficiencies. Furthermore, the carbo-catalysts
manifested much higher activity towards PDS activation in comparison
to the universally applied AC and metal oxides, i.e.: Fe3O4, Co3O4,
MnO2, and CuO.
In a recent study, Andrew Lin and Zhang [99] showed that not only
carbons can act as metal-free peroxymonosulfate activators. They have
demonstrated that the use of orthorhombic α-sulfur as a metal-free
photo-catalyst for PMS (under irradiation with visible light) is efficient,
promising, and friendly for the environment.
Considering the fact that large amounts of solid waste that could be
used for the activation of persulfates are produced from various in-
dustries, there is no need to synthesize expensive catalysis. Fly ashes
derived from coal, biomass or oil combustion are major contributors to
the production of solid waste and could be used to prepare (Co)-based
catalysts for PMS activation [74]. It was found that the fly ash does not
adsorb phenol, however it consists of cobalt oxide, which can be used
for the activation of PMS. In other studies, steel waste powder [100]
and the iron scrap from car rotary disc [51] were applied as activators
for PDS. The iron scrap should be cleaned under dry process where a
layer of 3 µm is removed. This layer contains excellent iron alloys
formed during the friction process between the pad and the disc. This
material is widely available and not expensive.
Electron donor catalysis has various benefits but can also, as was
stated before, become a new source of contamination. In addition, it is
often much less efficient, e.g. only one mole of radical can be obtained
from one mole of oxidant, in contrast to UV or heat activation. A de-
tailed study of the activation of oxidants with OeO bond by UV and
elevated temperature was performed by Yang et al. [19]. They found
that the order for the decontamination efficacy of peroxides activated
by heat is: peroxydisulfate > peroxymonosulfate > hydrogen peroxide
and of UV (254 nm) activated peroxides: peroxydisulfate > hydrogen
peroxide > peroxymonosulfate (conditions: experiments were done in
double distilled water; concentration of AO7 (contaminant of concern)
−20 mg L−1; the molar ratio of hydrogen peroxide/AO7 - 10/1). Sur-
prisingly, they also determined that relatively common (in ground,
surface, and wastewaters) anions (i.e. HCO3−, HPO42−, Cl−, and
S. Wacławek et al. Chemical Engineering Journal 330 (2017) 44–62

CO32−) can initiate formation of more reactive species from PMS. It has
to be mentioned, that the efficiency of the above processes are very
dependent on the water matrix. In natural matrices the presence of
chloride and HCO3−/CO32− can greatly decrease the efficiency of
sulfate radical based processes [101] (however, it depends on the probe
being treated; see below, section Matrix effects).
3.4. Alkaline activation
Another persulfate activation technique often used in situ is alkaline
activation involving an increase in pH (often > 11) by dosing sodium
hydroxide (NaOH) or potassium hydroxide (KOH) solutions [12]. On
the other hand, Cassidy et al. [102] concluded that in situ stabilization
amendments, including fields containing Ca(OH)2 and/or CaO, can ef-
fectively activate PDS by increasing the pH, and in the case of CaO also
the heat upon their reaction with soil water (i.e. additional activation).
Activated PDS decreased concentrations of BTEX compounds and PAHs.
The proposed mechanism of alkaline activation of PDS [44] relies on
the hydrolysis of PDS to hydrogen peroxide anion (HO2−) and
subsequent reduction of PDS by this anion with the production of
sulfate and superoxide radicals (O2%−). Very recently, Qi et al. [45]
proved a similar activation tendency for PMS, which can take place
at high pH with base-catalysed hydrolysis of PMS to hydrogen
peroxide. It was discovered that O2%− was the predominant radical
species in this system, but the role of singlet oxygen was also found to
be significant.
3.5. Electro-activation
Several studies have evaluated the “electro-activation” of persul-
fates. Yuan et al. [62], investigated the activation of PDS using ferrous
iron produced in an electrolytic system. They have determined that PDS
is mainly decomposed by Fe2+ created in two steps – (1) from the
corrosion of Fe0 (chemical and electro-chemical) and (2) from the
cathodic reduction of Fe3+. They also found %OH to be the predominant
radical in their system. Recently, Govindan et al. [64] proved the effi-
cacy of electrochemical activation for persulfates. Electrochemically
activated PMS was the best oxidant (from PDS, PMS and hydrogen
peroxide) for pentachlorophenol decontamination. Long and Zhang
[103] stated that the electro-activation of PDS can be effective for de-
gradation of methylbenzene (toluene) from a surfactant flushing solu-
tion. The results indicated that in the reduction process of ferric iron on
the cathode, there could be produced ferrous iron that could further
activate PDS. This is in agreement with the research work (mentioned
before in this subsection) of Yuan et al. [62]. Also, simultaneous use of
electrolysis and UV process/goethite can enhance the radical formation
from PMS and PDS (Jaafarzadeh et al. [104]; Lin et al. [105]). Ac-
cording to Lin et al. [105], during the electrolysis, goethite (α-FeOOH)
can serve as an additional catalyst for PDS due to continuous generation
of ferrous iron by the reduction and transformation of ferric iron on the
surface of goethite. Whereas Jaafarzadeh et al. [104] concluded that
only with the simultaneous use of electrolysis and UV, PMS (and
electro-generated H2O2) can effectively decolorize acid brown 14.
Moreover, the great efficacy of electro-activation of PDS was shown in
Wacławek et al. [55]. This study has shown that pseudo first-order
reaction rate constant of lindane removal was (at the optimal condi-
tions) 0.04 min−1, which is higher than the one observed by Cao et al.
[106] −0.0083 min−1 (in the PDS/Fe2+ system) but lower than that
presented by Khan et al. [107] −0.124 min−1 (in the PMS/Fe2+/UV
system).
3.6. Other activation methods
Recent work reported by Cong et al. [108], focusing on the si-
multaneous use of PMS and ozone for degradation of 4-chlorobenzoic
acid, indicated that PMS may act in a similar way to H2O2 in the pro-
motion of %OH production in ozonation. This theory was confirmed by
Yang et al. [46], who demonstrated that the reaction between PMS and
ozone is chiefly responsible for promoting ozone disappearance with a
determined second-order rate constant of 2 × 104 M−1 s−1. Both sul-
fate and hydroxyl radicals were present in this system, which was
confirmed by chemical probes and their yields were found to be
0.43 ± 0.1 and 0.45 ± 0.1 per mol of ozone, for SO4%− and %OH, re-
spectively. The first step of the reaction is assigned to formation of an
adduct (–O3SOO– + O3 → –O3SO5−), which can further decompose
into more reactive radicals (SO5%− and O3%−). The following reaction
of SO5%− with ozone is assumed to produce SO4%−, while O3%− can
convert to %OH [8].
4. Determination methods
Numerous determination methods for PDS and PMS can be found in
the literature. These methods vary in their execution time and sensi-
tivity of detection (see Tables 4 and 5).
Tables 4 and 5 present a summary of PDS and PMS determination
methods, respectively.
The first methods used for the determination of PDS and PMS were
most probably iodometric titrations [16]. Their spectrophotometric
alternatives possess much higher sensitivity and do not require as much
reagent and time [111,120]. Determination of persulfates with the use
of dyes has gained popularity lately, although the method has been
known for a long time [115]. Nevertheless, these methods possess very
high sensitivity and short measurement time. More information on the
determination of persulfates with organic dyes can be found in Ding
et al. [124] and Zhang et al. [125]. In addition, the fast and accurate
analysis of both PDS and PMS can be performed with the use of ion

Table 4
PDS determination methods.

Method Substance used Time of measurement Limit of quantification Reference

Spectrophotometry Direct UV-absorption – – [58,109]

Titration Ce4+/Fe2+ <20 min >10−4 M [110]
Spectrophotometry KI/HCO3− 15 min 7 × 10−2 M [111]
Spectrophotometry H2SO4/NH4SCN ∼40 min 2.1 × 10−4 M [112]
Spectrophotometry Methylene blue under microwave radiation 1 min 3 × 10−6 M [113]
Spectrophotometry N,N-diethyl-p-phenylenediamine 10 min 10−5 M [114]
Spectrophotometry Alcian blue 120 min 8.8 × 10−8 M [115]
Amperometry Electrodeposited poly-brilliant cresyl blue on carbon nanotube – 10−5 M [116]
Amperometry Electrode (glassy carbon) with a nanocomposite containing ruthenium oxide nanoparticles – 10−5 M [117]
and thionine
Amperometry Electrode (glassy carbon) with a nanocomposite containing ruthenium oxide nanoparticles – 10−5 M [117]
and celestine blue
Voltammetry Prussian blue - modified platinum disc electrode – 5 × 10−5 M [118]
Ion chromatography Mobile phase: 50 mM KOH; flow rate: 1 mL/min 18 min 5.2 × 10−8 M [119]

49
S. Wacławek et al.
Table 5
PMS determination methods.
Method Substance used
Titration Ce4+/Fe2+
Spectrophotometry KI/HCO3−
Spectrophotometry Co2+/methyl orange
Spectrophotometry N,N-diethyl-p-phenylenediamine
Ion chromatography Stationary phase: Super-Sep anion-exchange column; Mobile phase: 2 mM phthalic acid with
5% (v/v) acetonitrile content, pH 3.0; flow rate 1.5 mL/min; cond. 290 μS/cm
HPLC Stationary phase: Varian Polaris 3 C-18 A column; Mobile phase: methanol/phosphoric acid
buffer; flow rate 1.0 mL/min; UV at 260 nm
chromatography and HPLC [119,122,123].
5. Persulfate decontamination technologies
5.1. Direct oxidation
Although reactions of non-catalysed persulfates occur at rates that
are often slow, several studies reported their direct oxidation processes.
Probably the best known are the Elbs and Boyland-Sims reactions,
which rely on the nucleophilic displacement of peroxide oxygen from
the PDS ion [126]. In the Elbs reaction, phenolate anion (or a tautomer)
acts as the nucleophile, whereas in the Boyland-Sims reaction, the nu-
cleophile is a neutral aromatic amine. In both of these processes, there
is no radical involvement (apart from the side reactions).
In addition, during catalysed persulfate oxidation, persulfates can
react with generated radicals in several ways.
In Fig. 3 the second-order reaction rate constants of persulfate re-
actions with several species in an aqueous phase, can be observed.
Further example of PDS oxidation not relying on the radical for-
mation was presented by Zhang et al. [21]. According to them, PDS
weakly interacts with the surface of copper oxide (under mild condi-
tions) from which it can easily react with the contaminant of concern
(2,4-dichlorophenol). The reaction between PDS and the surface of CuO
was assumed therein to be the rate-limiting step.
Furthermore, Lei et al. [133] have shown that not only PDS can effi-
ciently oxidize target pollutants without the free radicals involvement.
They have discovered that PMS can directly react with cationic pigments
without catalyst and in a broad pH range (2–12). Furthermore, they
concluded that Cl− anions improved the degradation efficacy of the target
pollutants. Radical quenching experiments and ESR studies revealed that
50
Chemical Engineering Journal 330 (2017) 44–62
Time of Limit of quantification Reference
measurement
<20 min 10−5 M [110]
5 min 1.2 × 10−5 M [120]
1 min 5 × 10−7 M [121]
10 min 10−5 M [114]
11 min 4.5 × 10−5 M [122]
– ∼5 × 10−7 M [123]
the degradation of cationic dyes by peroxymonosulfate does not rely on
hydroxyl or sulfate radicals. The proposed mechanism of decolorization
relies on the complex formation between the dyes and PMS followed by
the electron transfer towards the PMS.
In addition, PMS may oxidize As(III) without an external activation
as suggested by Wang et al. [134]. They stated that the PMS can
completely oxidize As(III) to As(V) within 24 h, which was possible
even after addition of radical scavengers in high concentrations (1.6 M
of methanol).
5.2. Basic reactions in water matrices
Electron transfer reactions of oxygen yield reactive oxygen radicals
[135]. Also, oxygen’s role in SO4%− systems was determined to be
significant and was described carefully in a recent paper by Xu et al.
[136] and Ghauch et al. [42]. The step-by-step reduction of an oxygen
molecule to water followed by the formation of radicals during per-
sulfate decomposition is shown in Fig. 4.
Superoxide disproportion may result in the formation of H2O2
which in turn can react to generate %OH (e.g., by chemical reduction).
Furthermore, %OH can also be generated together with SO4%− in re-
actions of PDS or PMS with transition metals [49] or in the photolysis of
PMS [137] and SO4%− can also form %OH in the reaction with OH−
(k = 1.4 × 107 M−1 s−1, Herrmann et al. [57], and reaction 4). Con-
sidering the concentration of OH− at normal conditions of water and
wastewater treatment (e.g., pH 6–8) the observed reaction rate constant
of the reaction of SO4%− with OH− is in the range of 10−1 to
102 M−1 s−1. However, reactions of SO4%− with other matrix compo-
nents such as chloride or dissolved organic compounds are likely more
important at that pH-values (for relevant reaction rate constants see
Fig. 3. Comparison of the second-order reaction rate constants of persul-
fates with aqueous species. Data taken from: Yang et al. [46]; Buxton et al.
[127]; Restelli and Angeletti [128]; Herrmann et al. [57]; Davies et al.
[129]; Roebke et al. [130]; Maruthamuthu and Neta [131]; Gilbert and
Stell [132].
S. Wacławek et al. Chemical Engineering Journal 330 (2017) 44–62

constants of SO4%− with pollutants have a larger spread than %OH,

since most pollutants provide functional groups which can be attacked
by %OH. For more information see [127,141]. For a more detailed ex-
planation of radical identification, e.g. with the use of radical sca-
vengers, see [71,138–140].

5.3. Matrix effects: Scavenging and secondary oxidants

In persulfate based oxidation processes, pollutants are mainly de-

graded by reactions of SO4%− which are formed by the different acti-
vation methods (see above). As in all radical based processes, these
radicals are largely consumed by main constituents of the water matrix.
The reaction of oxidants with water matrix constituents can be divided
into three categories:

1. Scavenging of oxidants
2. Formation of secondary reactive species
3. Formation of by-products
Fig. 4. Black arrows - scheme of oxygen molecule reduction to water; red arrows - radical
formation and behaviour in a persulfate system (dashed arrow - only valid for homolysis
In order to define how fast the reaction proceeds, second order rate
of the PMS peroxide bond). (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
constants and for simplification of the experimental procedure,
“pseudo” first order rate constants are often used.
Table 6 shows second-order reaction rate constants of %OH and
Table 6
Second-order reaction rate constants of hydroxyl and sulfate radicals with common an- SO4%− with common anions and natural organic matter (NOM) present
ions and NOM. in real matrices.
Scavenging is mainly driven by dissolved organic matter (DOM),
Rate constants(M−1 s−1)
Radical Compound Reference
HCO3− and CO32− and in some cases nitrite and reduced metal species
%
OH −
Cl 3.0–4.3 × 10 9
[142,143] such as Fe2+. DOM and reduced metal species mainly consume oxida-
SO4%− Cl− 1.3–6.6 × 108 [144–146] tion capacity because the products formed in these reactions are not
%
OH Br− 1.9 × 109 [147] reactive towards pollutants. For the reaction of the sulfate radical and
SO4%− Br− 3.5 × 109 [148]
%
hydroxyl radical with humic acids the kinetic rate constant was mea-
OH HCO3− n × 107 [149]
SO4%− HCO3− 2.6–9.1 × 106 [109,150]
sured to be 6.8 × 103 L mg C−1 s−1 and 1.4 × 104 L mg C−1 s−1 (mg
%
OH CO32− 4 × 108 [149] C = mg carbon), respectively [152]. On the contrary, Luo et al. [32]
SO4%− CO32− 4.1 × 106 [151] observed that the oxidation capacity of the hydroxyl radical and sulfate
%
OH Humic acid 1.4 × 104* [152] radical for humic acid degradation (in the presence of Cl− and Br−)
SO4%− Humic acid 6.8 × 103* [152]
was nearly in the same order. This can be explained by the below dis-
*(mg of C L−1)−1 s−1. cussed conversion of SO4%− into %OH in presence of chloride. Hence in
both systems the same oxidant prevails, i.e., the hydroxyl radical.
Table 6). Studies based on radical scavenging analyses paired with the Especially Br− had a negative impact on the efficiency of these pro-
use of the ESR technique were performed to identify the dominant ra- cesses, which is in agreement with the research work of Yang et al.
dical species involved in persulfate-based oxidation [56,89,90]. [153] (Although, in several studies a concentration of 1 mM of Br−
Several compounds can be used for scavenging of SO4%− and %OH. and/or Cl− seemed to enhance the removal of some compounds
For choosing the correct scavenging agent, one has to consider reaction [51,59]).
kinetics and product formation. It has to be provided that only reactions Electron transfer reactions of SO4%− with phenolic moieties of DOM
under study are relevant and that products which could interfere the result in radical cations which may rearranged in presence of water into
reactions under study or analytical procedures are not formed. carbon centred radicals in analogy to the reaction of benzenes with
TBA (khydroxyl radical = 6.0 × 108 M−1 s−1, ksulfate radical = 4.0 SO4%− [154]. Carbon centred radicals react rapidly with oxygen
× 105 M−1 s−1) and ethanol (khydroxyl radical = 1.2 × 109 M−1 s−1, (≈2 × 109 M−1 s−1 [155]). The ensuing peroxyl radicals eliminate
ksulfate radical = 1.6 × 107 M−1 s−1) are the most often used chemical O2%− or HO2% or decompose in bimolecular reactions [155]. Both
probes to evaluate the relative contribution of SO4%− and %OH because pathways often result in carbonyls [155]. Halide ions also react with
of their different reaction rate constants [138]. Also with the ESR SO4%−. The reactivity of bromide towards SO4%− is high
technique, the radicals can be determined qualitatively (rough esti- (k = 3.5 × 109 M−1 s−1 [148]) and in pure water bromate is formed as
mation of the intensity of radicals in the spectra). The spin trap com- a stable product [156], which is undesired due to its carcinogenic po-
pound, 5,5- dimethyl-1-pyrroline N-oxide (DMPO) reacts with radical tential (EU and US-EPA drinking water standard 10 µg L−1). The pre-
intermediates in oxidation systems and forms a unique radical adduct sence of organic matter, however, suppresses formation of bromate,
that is stable, relative to the radicals of interest. indicating that no bromate is formed in field water matrices [156]. Fang
Indeed with these techniques, it was shown that in most cases and Shang [157] came to a similar conclusion. Liu et al. [158] in-
SO4%− prevails in acidic media and %OH predominates in alkaline vestigated the transformation of Br− in a PMS (activated by cobalt)
media (e.g. tested at the pH of 5 and 11 by Fang et al. [139,140] (at the oxidation process with the presence of phenol as a model compound
pH of 9 both radicals were in similar quantity [140]). Similar conclu- imitating NOM. It was determined that bromide can be efficiently
sions were obtained by Liang and Su, [138] by using various probes: converted to free bromine and bromine radicals. These reactive species
TBA, phenol, and nitrobenzene). caused bromination of phenol and the formation of brominated disin-
Reactions of SO4%− are very different from reactions of %OH. SO4%− fection products including bromoform and bromoacetic acids and bro-
are prone to react by electron transfer reactions while %OH favours H- mophenols as intermediates. Brominated disinfection by-products were
abstraction and addition reactions. This can explain that reaction rate also degraded by surplus SO4%−. Free bromine was also created when
cobalt was not present, indicating that Br− might be directly oxidized

51
S. Wacławek et al. Chemical Engineering Journal 330 (2017) 44–62

Table 7
Reaction rate constants of carbonate radicals with pollutants and matrix components and of hydroxyl radicals and sulfate radicals with matrix components, apesticides.

Number Reactant Reaction rate constants Reference

Carbonate radical
DOC 40 and 280 L mg−1 s−1 [163,164]
1 Atrazinea 0.37 × 107 M−1 s−1 [164]
2 Fluometurona 0.4 ± 0.3 × 107 M−1 s−1 [164]
3 Atratona 0.43 ± 0.09 × 107 M−1 s−1 [164]
4 Tertbutryna 0.49 ± 0.13 × 107 M−1 s−1 [164]
5 Fenurona 0.54–0.6 × 107 M−1 s−1 [164]
6 Prometryna 0.61 ± 0.12 × 107 M−1 s−1 [164]
7 Irgarola 0.73 ± 0.12 × 107 M−1 s−1 [164]
8 Ametryna 0.74 ± 0.38 × 107 M−1 s−1 [164]
9 Diurona 0.8 ± 0.2 × 107 M−1 s−1 [164]
10 Propanila 1.4 ± 0.7 × 107 M−1 s−1 [164]
11 Monurona 1.5 ± 0.4 × 107 M−1 s−1 [164]
12 Chlorotolurona 1.5–2.2 × 107 M−1 s−1 [164]
13 Isoproturona 2.5–3 × 107 M−1 s−1 [164]
14 4-cyanophenoxide 4.0 ± 1.3 × 107 M−1 s−1 [164]
15 4-nitroaniline 7.7 ± 3.4 × 107 M−1 s−1 [164]
16 Metoxurona 8.1–11 × 107 M−1 s−1 [164]
17 4-carboxyphenoxide 10.4 ± 3.5 × 107 M−1 s−1 [164]
18 vanillinate 11.8 ± 2.7 × 107 M−1 s−1 [164]
19 4-cyanoaniline 18 ± 6 × 107 M−1 s−1 [164]
20 4-aminobenzenesulfonate 24 ± 13 × 107 M−1 s−1 [164]
21 phenoxide 25 ± 5.6 × 107 M−1 s−1 [164]
22 4-chlorophenoxide 35 ± 12 × 107 M−1 s−1 [164]
23 3,4-dichloroaniline 41 ± 9 × 107 M−1 s−1 [164]
24 4-hydroxyphenylacetate 60 ± 20 × 107 M−1 s−1 [164]
25 4-chloroaniline 62 ± 13 × 107 M−1 s−1 [164]
26 4-methylaniline 115 ± 45 × 107 M−1 s−1 [164]
27 4-methylphenoxide 120 ± 25 × 107 M−1 s−1 [164]
28 N,N-dimethylaniline 185 ± 35 × 107 M−1 s−1 [164]
29 N-ethylaniline 220 ± 40 × 107 M−1 s−1 [164]
30 N-methylaniline 255 ± 45 × 107 M−1 s−1 [164]
31 aniline 255 ± 18 – 61 ± 13 × 107 M−1 s−1 [164]
32 4-methoxyphenoxide 310 ± 60 × 107 M−1 s−1 [164]

Sulfate radical
DOC 6.8 × 103 L mg−1 s−1 [152]
HCO3− 9.1 × 106 M−1 s−1 [165]

Hydroxyl radical
DOC 2.5 × 104 L mg−1 s−1 [166]
HCO3− 8.5 × 106 M−1 s−1 [149]

by PMS. In another study these conclusions were confirmed and it was
also found that the brominated intermediates cannot be degraded in the
absence of SO4%− [159]. Similar work was performed by Lu et al.
[160], who determined that reactive bromine species formed in the
reaction with sulfate radicals can react with NOM and might form
brominated products, including brominated disinfection by-products. In
addition, bromoacetic acid and bromoform were formed in the presence
of humic acids.
Iodide also reacts fast with SO4%−, which may form iodate in ana-
logy to bromide.
The products of the reaction of SO4%− with chloride can result in
chlorate formation in an H+ catalysed reaction [101]. However, at
typical conditions of water treatment (pH > 7) no chlorate formation
was observed in UV/S2O82− [101]. The primary step in the reaction of
SO4%− with chloride is an electron transfer yielding chlorine (Cl%)
atoms and sulfate. Cl% forms a H2OCl% complex in water [146,161]. This
complex can deprotonate and the resulting HOCl%− is in equilibrium
with %OH [101,146,161]. At pH 7 and in presence of 1 mM chloride, the
reaction of SO4%− with chloride yields %OH with a nearly 100% yield
[101]. In case of chloride concentrations in the lower mM range most of
SO4%− are scavenged by reactions with chloride resulting in a con-
ventional %OH based AOP [101]. CO32− or HCO3− react fast with Cl%
and dichloride (Cl2%−) and thus, interrupt the %OH forming reactions
[101]. Since typical natural waters contain chloride and HCO3−, the
%
OH yield is likely much below the SO4%− yield [101]. However, oxi-
dation of HCO3− and CO32− gives rise to CO3%−, which also exhibits a
potential to degrade pollutants (depending on their chemical structure
and affinity with carbonate radicals). Table 7 compiles rate constants of
CO3%− with several organic compounds. The reaction rates are in the
range of 106–109 M−1 s−1 and thus, on average slower compared to
SO4%− or %OH, which often react at second order rate constants in the
range of 108–1010 M−1 s−1 [149,162]. However, this may be com-
pensated by the small reaction rate of CO3%− with the scavengers in the
water matrix, as will be explained below.
The efficiency of pollutant degradation is depending on the
scavenging rate of the water matrix and the kinetics of the radical re-
action with the pollutant. With the kinetics of scavenger reactions and
pollutant reactions at hand one can calculate the apparent degradation
rate (ḱ) in a given water sample according to Katsoyiannis et al. [167].
Fig. 5 shows ḱ for the compounds of Table 7 for reactions of CO3%−
assuming a water matrix with 1 mg L–1 DOC and 1 mM HCO3−. ḱ of
CO3%− is shown for the two reaction rate constants with DOC (Table 7).
As will be explained below, HCO3− presumably does not contribute in
scavenging of CO3%−. Fig. 5 also shows ḱ for the same water matrix in
SO4%− and OH% reactions (dashed lines) for a defined reaction kinetics
towards trace compounds (dashed lines in Fig. 5).
The herbicide propanil (compound 10, Table 7) reacts with CO3%−
at a reaction rate constant of 1.4 × 107 M−1 s−1, arriving at
ḱ = 0.25 s−1, in case CO3%− reacts with DOC at a rate of 40 L
mg−1 s−1. The same ḱ is achieved in %OH based processes for pollutants
with a much higher reaction rate constant (k ≥ 9 × 109 M−1 s−1) and
in SO4%− based reactions with k ≥ 1 × 109 M−1 s−1 (dashed lines in

52
S. Wacławek et al.
Fig. 5). This is due to fact, that %OH and SO4%− have a high reactivity
towards DOC (k(SO4%−) = 6.8 × 103 L mg−1 s−1 [152], and k(OH%)
= 2.5 × 104 L mg−1 s−1 [163] and towards HCO3− (k(SO4%−)
= 2.8–9.6 × 106 M−1 s−1 [165], and k(OH%) ≈ 1 × 107 M−1 s−1
[149]. The reaction of CO3%− with organic matter is considerably lower
(see above). Furthermore, HCO3− or CO32− is not important for pol-
lutant degradation, because it presumably yields CO3%−. Hence, the
overall scavenger rate of CO3%− is considerably lower compared to
SO4%−. In case the CO3%− reacts with DOC with a rate constant of
280 L mg−1 s−1 the efficiency of CO3%− for pollutant degradation
drops down and CO3%− has to react with rate constants > 108 M−1 s−1
to yield a faster degradation kinetics compared to %OH. Compound 18
(vanilinate) represents such a compound, assuming that %OH does not
react faster than 9 × 109 M−1 s−1 with vanilinate. In case of SO4%−
which react slower with DOC, CO3%− has to react even faster with
́
pollutants to achieve comparable k. Pollutants with electron rich moi-
eties such as anilines reveal a fast reactivity towards CO3%−. It is
conceivable that the degradation of electron rich compounds is en-
hanced by HCO3−/CO32− in SO4%− or %OH based processes. This ap-
plies for compounds 15 to 32 (Table 7, phenols and anilines). Most
pesticides listed in Table 7, however, reveal reaction rate constants
of < 107 M−1 s−1. Their degradation is probably mitigated in presence
of HCO3−/CO32− in a SO4%− or %OH based process, as observed for
atrazine degradation in river water [101] (cf. further discussion
[101,164]).
It was also reported that reactive chlorine species, formed in the
reaction of SO4%− with Cl–, may also react with other matrix compo-
nent and thus, form chlorinated products [144]. For example, Fang
et al. [140] reported that the total concentration of radicals was greatly
increased in the presence of chloride ion but the degradation efficiency
of PCBs in this system decreased. Yang et al. [153] also investigated the
conversion of %OH and SO4%− to the halogen radicals. Halogens re-
duced the abatement efficacy of cyclohexanecarboxylic acid and ben-
zoic acid (in the presence of seawater), which were chosen as the target
pollutants. It was also concluded therein that the activated PDS was
more affected by Cl− than the activated hydrogen peroxide system
probably due to the fact that Cl− has a higher reactivity with sulfate
radicals than the hydroxyl radicals at pH of 7. Indeed %OH is hardly
effected by Cl− at typical pH values of water treatment (6 −8) since the
reaction of %OH with Cl− has a fast back reaction. The oxidation of Cl−
by %OH is acid catalysed and only becomes important in %OH reactions
at pH < 3 [168]. The degradation efficiency of cyclohexanecarboxylic
acid was not altered by the halogens, probably due to the high
53
Chemical Engineering Journal 330 (2017) 44–62
Fig. 5. Calculated apparent first order kinetics (ḱ) of pollu-
tants degradation by carbonate-, sulfate- and hydroxyl radi-
cals in presence of 1 mg L−1 DOC and 1 mM HCO3−.
Calculations are based on reaction rate constants shown in
Table 7. Circles: ḱ(carbonate radicals) assuming: k
(CO3%− + DOC) = 40 L mg−1 s−1, squares ḱ(carbonate ra-
dicals): assuming k(CO3%− + DOC) = 40 L mg−1 s−1, dashed
lines ḱ(sulfate radicals or hydroxyl radicals, as indicated in the
figure) for a given reaction rate constant towards a pollutant,
as indicated in the figure.
reactivity of alkenes with halogen radicals. This statement was further
confirmed in a study of Liu et al. [169] who found that in the presence
of chloride there could be a different mechanisms of oxidation than that
of the SO4%−, and carbon isotope fractionation of trichloroethene (TCE)
was used to prove this statement.
In another work, Xie et al. [159] focused on the generation of
chlorinated intermediates in a sulfate radical system, and they found
that the formation of carbonaceous disinfection by-products, i.e. ha-
loacetic acid and chloroform, only increased a little, but the generation
of nitrogenous disinfection intermediates, i.e. haloacetonitriles and
trichloronitromethane, slightly decreased. On the contrary, Lu et al.
[170] found that after treatment of surface water with 0.1 μM PDS for
48 h, caused increase in concentration of compounds such as: chloro-
form, trichloroacetic acid, and dichloroacetic acid by 16%, 37%, and
52%, respectively. The above results indicate that before the applica-
tion of persulfates in the field, bench scale studies should be performed
in detail due to the fact that the formation of dangerous by-products
depends highly on the treated water matrix properties.
To sum up, at typical conditions of drinking water treatment (i.e.,
pH 6–9) presence of SO4%− scavenged by chloride are largely trans-
formed into %OH. Reactive chlorine species are prone to be scavenged
by carbonate or bicarbonate, resulting in CO3%−. The fraction of radi-
cals turned into %OH or CO3%− is controlled by kinetics and con-
centration of the corresponding reaction partners (further details on
that reaction system see above and Lutze et al. [101]). CO3%− may
become important for pollutant degradation due to their higher se-
lectivity compared to SO4%− and %OH, provided that CO3%− readily
react with such pollutants (k ≈ 107 M−1 s−1 or faster) (see also Fig. 5
and Table 7).
5.4. Post-treatment toxicity assessment
Although persulfates treatment has many benefits, there are also
several downsides that have to be taken into consideration, i.e. con-
tamination with sulfate salts or even worse newly created hazardous
compounds due to e.g. additional chlorination and/or bromination (as
discussed in Section 5.3).
In addition, many researchers study toxicity in clean systems, al-
though in actual matrix conditions, the background DOC and other
constituents may additionally generate toxicity.
For instance, in our recent study concerning the decontamination of
groundwater polluted with various chlorinated olefins (Wacławek and
Kudlek, unpublished data), many new substances (with a molecular
S. Wacławek et al.
mass > 250 g mol−1) were observed after UV/persulfate treatment
that were unnoticed after e.g. UV/hydrogen peroxide treatment.
Therefore, during bench-scale testing performed before field applica-
tion, toxicity tests (that are relevant to the treated site) should be
performed in order to avoid any environmental side effects.
However, several authors reported that the toxicity of the matrix
after persulfates treatment is significantly lower. One example was
provided by Zhang et al. [171] that evaluated toxicity with Vibrio qin-
ghaiensis sp. Q67 test after the PDS treatment of carbamazepine and
concluded that the acute toxicity has decreased together with the re-
moval of the pharmaceutical (the inhibitory effect of the solution after
treatment decreased to 65% within 60 min). Also Temiz et al. [172]
evaluated the toxicological safety (using two different bioassays) of the
zero-valent iron/PDS oxidation of Triton X-45 (TX-45). Vibrio fischeri
and Pseudokirchneriella subcapitata bioassays were used therein and the
toxicity profiles of the treated matrices significantly decreased from an
original value of 66% relative inhibition to 21% (Vibrio fischeri) and
from 16% relative inhibition to non-toxic values (Pseudokirchneriella
subcapitata). Vibrio fischeri has shown higher sensitivity to TX-45 and its
degradation products than the microalgae Pseudokirchneriella sub-
capitata.
Olmez-Hanci et al. [173] went even further and used three toxicity
tests (Vibrio fischeri, Daphnia magna, and Pseudokirchneriella subcapitata)
and the Yeast Estrogen Screen bioassay to assess the possible estrogenic
and toxic properties of nonionic surfactant octylphenol ethoxylate and
its oxidation products. In the case of Vibrio fischeri and Daphnia magna
tests the inhibitory effect of nonionic surfactant octylphenol ethoxylate
dropped considerably after the application of PMS. However, treatment
with PMS/UV-C generated oxidation products that possessed highly
toxic effect towards Pseudokirchneriella subcapitata (opposite observa-
tions to Temiz et al. [172], concerning toxicity of TX-45 and its oxi-
dation by-products).
5.5. Decontamination of water and wastewater with free radicals generated
in persulfate systems
As shown in Section 3, numerous methods of persulfate activation
can be applied in water and wastewater treatment technology in order
to achieve the expected results. The decontamination of water (Section
5.5.1) and wastewater (Section 5.5.2) with the radicals generated from
persulfates is described in detail below.
5.5.1. Water
SO4%− are very reactive and able to degrade very persistent organic
compounds. Perfluorooctanoic acid (PFOA) e.g., that is unreactive to-
wards %OH, can be degraded in the SO4%− system according to many
[174–179]. Recently, Qian et al. [180] determined the degradation
kinetics of PFOA in a UV/PDS system and proposed its degradation
mechanism, which relies on a sequential loss of CF2 units from it and its
intermediates [179,180]. However, the degradation kinetics of the re-
action SO4%− with perflurocarbonic acid are very slow (approximately
104 M−1 s−1). Since the reaction of SO4%− with other matrix compo-
nents is much faster, a degradation of perfluorinated compounds is not
feasible in SO4%− based oxidation.
SO4%− can readily oxidize other organic pollutants such as 2,4-di-
chlorophenol [75], 2-chlorobiphenyl [181], aniline [24], bisphenol A
[182], calcon [183], Acid Orange 7 [19], hexachlorocyclohexanes
[55,184], Ponceau S [185], 4-fluorophenol [186], pentafluorobenzoic
acid [187], C.I. Reactive Black 5 [188], C.I. Basic Red 46 [189], me-
thylene blue [190], endosulfan [191], antipyrine [192], naproxen [95],
chloramphenicol [59], ranitidine [51], sulfamethoxazole [42,50], bi-
soprolol [36], ibuprofen [35], dimethyl phthalate [193] or di-
methylhydrazine [194] and chlorotriazine pesticides. Table 8 includes
pseudo first-order rate constants of various contaminants with gener-
ated from persulfates radicals.
Moreover, Neppolian et al. [201] proved that these radicals can also
54
Chemical Engineering Journal 330 (2017) 44–62
be used for the removal of inorganic pollutants in water. They in-
vestigated the UV/PDS oxidation of As(III) to the less harmful As(V). It
was established that humic acid had no effect on the reaction rate (si-
milar results to Wang et al. [134], although therein 1.6 M methanol was
used as a scavenger), even at 20 mg L−1. Yet, the continual addition of
nitrogen considerably minimized the rate of the reaction (by 20%),
attributing this to the role of dissolved oxygen in the reaction (at high
concentrations of PDS this phenomenon was not observed, presumably
due to formation of oxygen in the reaction of peroxydisulfate with
SO4%−; [58]).
Surprisingly, according to Diao et al. [202,203] SO4%− coupled
with nano zero-valent iron (supported on bentonite, and used as a ra-
dical initiator), can be effective for the simultaneous abatement of Cr
(VI) and phenol from water. The reaction mechanism according to them
involved the removal of Cr(VI) mainly by reduction with nano zero-
valent iron and phenol removal mainly by the SO4%− generated from
the PDS.
Chlorinated olefins are ubiquitous contaminants, and although they
can be degraded with many biological [204] and less invasive chemical
treatments (i.e.·H2O2) [205], persulfates are often used for their de-
gradation in situ. Recently, Yan et al. [206] combined siderite-catalysed
H2O2 with PDS and effectively used it for the remediation of tri-
chloroethene contamination from groundwater. It was claimed therein,
that in the absence of PDS (only catalysed peroxide), most of the hy-
drogen peroxide was reduced within the first hour of the test, resulting
in non-efficient use of OH-radicals. After the addition of PDS, the de-
composition rate of H2O2 was mitigated due to a more sustainable re-
lease of OH-radicals. Furthermore, the heat given by the decomposition
reaction of H2O2 activated the PDS, and the generated sulfate radicals
were claimed to be the main oxidative species. In addition, di-
chloroacetic acid has been detected as an intermediate. However, it has
to be noted, that it was not explained therein why the %OH formation is
not efficient in the absence and why it is efficient in the presence of
PDS. Xu et al. [207] also studied the abatement of trichloroethene
(TCE) but in a thermally activated peroxydisulfate system. Their results
showed that TCE can be completely removed from the solution within
9 min at 50 °C with an initial trichloroethene concentration of 0.15 mM
and a PDS dose of 0.3 M, as a consequence of the active oxygen species
formation (SO4%−, %OH). Moreover, Zhao et al. [48] studied the si-
multaneous decontamination of 1,4-dioxane, the inherent associate of
TCE (frequently used as a solvent stabilizer for TCE), with heat- and
Fe2+ PDS activation. Analysis of carbon balance revealed that 96% and
93% of the organic carbon was removed after the 1,4-dioxane abate-
ment with and without activation (addition of Fe2+), respectively.
Another commonly found and very toxic group of contaminants is
pesticides, which contribute to nine out of the twelve most hazardous
and assiduous organic compounds defined by the Stockholm
Convention on Persistent Organic Pollutants (POPs) [208]. A very re-
cent study by Qin et al. [209] presented 1,1,1-trichloro-2,2-bis(p-
chlorophenyl) ethane (DDT) removal with Co2+ catalysed PMS. It was
found that DDT was efficiently decomposed within several hours, pro-
portionally to PMS/Co2+ concentrations. The decontamination rates of
DDT were determined with pseudo-first-order reaction rate equations in
several temperatures, which enabled calculation of the activation en-
ergy (72 kJ mol−1). Several by-products of the reaction were de-
termined including: 4-chlorobenzoic acid, benzylalcohol, di-
chlorobenzophenone, and the possible degradation pathway of DDT
was suggested on the foundation of the detected by-products. Zhu et al.
[210] have also followed the DDT degradation (and the reaction in-
termediates) but using PDS (activated by nanoscale zero-valent iron) as
a source of radicals. The degradation pathway was very similar to that
of Qin et al. [209] (in the PMS/cobalt system), although it should be
noted that instead of 4-chlorobenzoic acid, its dechlorinated version has
been found. In addition, ESR results showed simultaneous involvement
of sulfate radicals and hydroxyl radicals in the degradation process.
Several authors examined atrazine degradation with persulfates.
 Table 8
Decontamination of common water pollutants with radicals generated in persulfate systems.

Group of compounds Model contaminant Main oxidative species Comments Pseudo first-order reaction rate constant Reference
S. Wacławek et al.

Chlorinated olefins Perchloroethene Possibly SO4%− (not Trace quantities of hexachloroethane as an intermediate. 7.6 × 10−3 min−1 (activation temperature of 50 °C) [144]
identified)
−3 −1
Trichloroethene Possibly SO4%− (not Trace quantities of hexachloroethane as an intermediate. 4.7 × 10 min (activation temperature of 50 °C) [144]
identified)
−3 −1
cis-dichloroethene Possibly SO4%− (not Isomerization between trans and cis-DCE presumably after 1.6 × 10 min (activation temperature of 50 °C) [144]
identified) formation of a single bonded intermediate.
trans- dichloroethene Possibly SO4%− (not Isomerization between trans and cis-DCE presumably after 3 × 10−3 min−1 (activation temperature of 50 °C) [144]
identified) formation of a single bonded intermediate.

BTEXs Benzene Possibly SO4%− (not Of all the BTEX compounds studied, benzene was most 9.5 × 102 day−1 (activation temperature of 20 °C; Oxidant/BTEX molar [195]
identified) resistant to PDS oxidation. ratio 100/1)
Toluene Possibly SO4%− (not – 23.2 × 102 day−1 (activation temperature of 20 °C; Oxidant/BTEX molar [195]
identified) ratio 100/1)
Ethylbenzene Possibly SO4%− (not – 14.5 × 102 day−1 (activation temperature of 20 °C; Oxidant/BTEX molar [195]
identified) ratio 100/1)
Xylene Possibly SO4%− (not – 21.9 × 102 day−1 (activation temperature of 20 °C; Oxidant/BTEX molar [195]
identified) ratio 100/1)

Phenols Phenol Possibly SO4%− and/or Greater total organic carbon (TOC) removal was observed 0.14–0.16 min−1 (UV activation parameters: λ = 254 nm; Oxidant/ [196]
%
OH (not identified) at elevated pH (11). Phenol molar ratio 168/1)
Bisphenol A SO4%− (scavenging tests Bisphenol A abatement with sulfate radicals was found to 0.025 min−1 (UV activation parameters: λ = 254 nm; 40 W power; [182]
were performed) proceed via one electron transfer reaction mechanism. Io = 1.26 μE s−1; Oxidant/Bisphenol A molar ratio 3/1)

Pharmaceuticals Diclofenac SO4%− (scavenging tests Degradation involved one electron transfer, 0.032 h−1 (Activation temperature of 50 °C; Oxidant/Diclofenac molar [197]
were performed) hydroxylation, decarboxylation. ratio 10/1)
Carbamazepine SO4%− (scavenging tests Electron-transfer between sulfate radicals and 0.087 min−1 (UV activation parameters: λ = 254 nm; 9 W power; [171]

55
were performed) carbamazepine was found to be the major mechanism. Oxidant/Carbamazepine molar ratio 10/1)
Bisoprolol SO4%− and %OH The formation of hydroxylated products through 8.5 × 10−2 min−1 (activation temperature of 60 °C; Oxidant/Bisoprolol [36]
(scavenging tests were hydroxylation was proposed. molar ratio 20/1)
performed)
Chloramphenicol SO4%− and %OH – 29 × 10−2 min−1 (UV activation parameters: λ = 254 nm; Oxidant/ [59]
(scavenging tests were Chloramphenicol molar ratio 80/1)
performed)

Pesticides Lindane Possibly SO4%− and/or Approx. 96.4% of chloride ion was released after the 10−3 sec−1 (UV activation parameters: λ = 254 nm; 10 µM = Fe2+; [107]
%
OH (not identified) treatment, which was consistent with the TOC analysis. Oxidant/Lindane molar ratio 73/1)
Triazine pesticides (atrazine, Possibly SO4%− and/or – 1.7 × 10−3 sec−1 (UV activation parameters: λ = 254 nm; Oxidant/ [32,152,198–200]
%
tert-butylazine, propazine) OH Atrazine molar ratio 50/1) Manoj et al. [198] has determined bimolecular
rate constants of the SO4%− reaction with triazines in the range of:
4.6 × 107–3 × 109 M−1 s−1, whereas Lutze et al. [152]:
2.2–3.5 × 109 M−1 s–1; Khan et al. [199]: 2.59 × 109 M−1 s–1 and
2.25 × 109 M−1 s–1 for the reaction with SO4%− and %OH, respectively;
Endosulfan SO4%− and %OH Degradation of endosulfan was began at the endosulfans 4.14 × 10−4 sec−1 (UV activation parameters: λ = 254 nm; Oxidant/ [191]
(identified) S ] O group. Endosulfan molar ratio 10/1)

Other Methylene blue Possibly SO4%− and/or The first step is an electron transfer from a benzene rings 14.8 × 10−2 min−1 (activation temperature of 60 °C; Oxidant/Methylene [190]
%
OH of MB to SO4%−. After 20 min of reaction, complete blue molar ratio 640/1)
disappearance of all intermediates was noticed.
Acid orange 7 Possibly SO4%− (not Reaction rates differed between UV/PMS and UV/PDS, 0.175 min−1 (UV activation parameters: λ = 254 nm; Oxidant/Acid [19]
identified) possibly due to the production of the hydroxyl radical orange 7 M ratio 10/1)
during the photolysis of PMS and different quantum
yields.
PFOA SO4%− and S2O8%− SO4%− accepts an electron from the carboxylate group in a 0.18 h−1 (UV activation parameters: λ = 254 nm; Oxidant/PFOA molar [180]
primary step. ratio 33/1)
Chemical Engineering Journal 330 (2017) 44–62
S. Wacławek et al.
One group was Luo et al. [32] who tested degradation of atrazine with
three oxidants – H2O2, PMS and PDS (UV activated, 254 nm). The
matrix effects, i.e. water hardness, Cl−, and NOM, were evaluated on
these three AOPs. It was determined that the concentrations of sulfate
radicals and hydroxyl radicals decrease with an increase of carbonate/
bicarbonate concentrations. A detailed description on the reactions of
%
OH and SO4%− with Cl− in presence of HCO3− is described in Section
5.3, see also Lutze et al. [152]. Main transformation products of atra-
zine in reactions with %OH and SO4%− are desethyl-atrazine and desi-
sopropyl atrazine [152,211,212] which are similarly toxic as the parent
compound [213]. The second order rate constant of different chloro-
triazine pesticides with SO4%− was determined to be in the range of
1–5 × 109 M−1 s−1. The primary dealkylation products still react fast
0.8–2 × 109 M−1 s−1. However, in case no alkyl group is attached at
the chlorotriazine ring (i.e., the chlorotriazine diamine) the reaction
becomes very slow for both %OH (k < 107 M−1 s−1) [214] and SO4%−
(k 1.5 × 108 M−1 s−1) [152], hence desethyldesisopropyl atrazine can
be considered to survive oxidative treatment (cf. mechanistic aspects of
chlorotriazine pesticides degradation [152,211,212]. Research work of
Wacławek et al. [184] was one of the first evaluating the degradation
efficiency of hexachlorocyclohexane isomers by PMS. Cao et al. [106]
and Khan et al. [107] provided more detailed study focusing on the
oxidation of one HCH isomer - lindane (γ-hexachlorocyclohexane) by
Fe2+ activated PDS and PMS, respectively. These studies revealed that
oxidation of HCH with activated persulfates is not only beneficial for
the complete removal of the parent compounds but also for obtaining
complete mineralization. Trichlorophenol was the main by-product
detected in all of these studies (although there is no agreement on the
exact isomer generated). In addition, in a further study, Khan et al.
[215] determined the second-order rate constant of lindane with SO4%−
(1.3 × 109 M−1 s−1). Kuśmierek et al. [216] investigated the de-
gradation of 2,4-dichlorophenol and 2,4-dichlorophenoxyacetic acid by
ammonium PDS activated in several ways. 2,4-dichlorophenol de-
graded faster and more efficiently in an alkaline environment
(pH = 9.0), whereas 2,4-dichlorophenoxyacetic degraded faster in an
acidic environment (pH = 3.0). They have also examined the sy-
nergistic activation of PDS with heat and ferrous iron to improve the
oxidation of 2,4-dichlorophenol and 2,4-dichlorophenoxyacetic acid.
They were able to select the optimal degradation conditions (molar
ratio between PDS/Fe2+ - 1:2, temp. - 50 °C), where complete removal
of contaminants was obtained after approximately 45 and 60 min, re-
spectively.
As was mentioned in the introduction, the rapid emergence of re-
sistant bacteria worldwide is probably due to the overuse of medica-
tions that can later become a contamination of concern. Several authors
have focussed on the remediation of pharmaceuticals and since per-
sulfates are one of the newest ISCO reagents used, there are also several
new studies describing their reactivity towards pharmaceutical drugs.
Monteagudo et al. [217] investigated ISCO of a carbamazepine solution
by PDS (at the same time) activated by UV, heat, Fe2+ ions, and H2O2.
Zhang et al. [171] determined the main by-products generated during
the oxidation process, including 10,11-epoxy-carbamazepine, acridine-
9-carbaldehyde, acridine, and other compounds with smaller molecular
weight.
Trimethoprim and sulfamethoxazole in expired sulfamethoxazole
tablets were the subject of research conducted by Liu et al. [218], who
studied their degradation by catalysed PDS treatment. Zero valent-iron
showed much better catalytic properties than alkaline activation, which
was completed after 0.5 h, while full mineralization was achieved after
2 h. Also Ayoub and Ghauch [50] applied activated PDS for sulfa-
methoxazole degradation and determined that the metallic iron-based
particles (heterogeneous systems) are more efficient than conventional
Fe2+ fed systems (homogeneous systems) for the removal of this
pharmaceutical.
Chen et al. [197] examined the performance of thermally activated
PDS on the degradation of diclofenac in both water and polluted
56
Chemical Engineering Journal 330 (2017) 44–62
groundwater. The results implied that the degradation of diclofenac
could be fitted well to a pseudo 1st-order kinetic model, and that the
rate constants were larger at higher temperatures. Activation energy
was also calculated and equalled to 158 kJ mol−1. The presence of a
small dose of chloride (0–10 mM) enhanced the abatement of diclo-
fenac, whereas larger chloride addition (>10 mM) had opposite effect.
HCO3− demonstrated an insignificant effect on diclofenac elimination,
while NOM, e.g., humic acids, slightly inhibited diclofenac removal.
The fast oxidation of diclofenac was further observed in a groundwater
sample from contaminated site. In addition, radical quenching tests
revealed that SO4%− were the leading reactive species for diclofenac
oxidation. Ibuprofen is also considered as an emerging contaminant and
its degradation in the activated PDS system was carried out by Ghauch
et al. [35]. The by-products were not detected throughout the treatment
process. It was concluded that this method could be an adequate ap-
proach for specific treatment of small volumes of hot spot wastewater
containing this contaminant (for example hospital effluents). PDS was
also tested on hospital effluent spiked with naproxen. This study clearly
demonstrated that thermally activated peroxydisulfate is a valid and
efficient method that can be used for the removal of dissolved phar-
maceuticals in water and sewage water [95].
SO4%− treatment also proved to be effective for highly con-
taminated mature landfill leachate. Li et al. [219] used ferrous iron
loaded AC as a heterogeneous PDS catalyst for its pretreatment. The
effects of the iron/PDS dose and initial pH on the abatement of the
organic pollution in the landfill leachate were determined. It was shown
that the chemical oxygen demand (COD) degradation rate exceeded
87.8% when simultaneous conditions were applied i.e. Fe2+ dose of
127 mg L−1, PDS concentration of 0.5 M and initial pH of 3.0.
5.5.2. Wastewater and sludge
Several studies can be found in the literature that describe the use of
persulfates in wastewater treatment technologies. Their use is focused
on exploiting their oxidative potential (removal of contaminants) and
improving the properties of sludge, i.e. dewaterability. Kronholm and
Riekkola [220] tried to answer the question whether potassium per-
oxydisulfate is a good choice for wastewater oxidation below the cri-
tical temperature of water. The efficiency of phenol, 1-naphthol, and
2,3-dichlorophenol oxidation in high-temperature (75–340 °C) pres-
surized (25–45 MPa) wastewater was investigated in an aqueous en-
vironment. The removal percentages of phenol were good even at
115 °C. Nonetheless, it has to be noted that although this radical in-
itiation method is not economically feasible and there were reported
many other methods for treatment of phenolic wastewater [221,222],
the study of Kronholm and Riekkola [220] has shown new alternative
way for wastewater treatment. Recently, the removal of COD from
petrochemical wastewater and from real high-strength industrial was-
tewater was studied by Babaei and Ghanbari [223] and Kattel et al.
[224], respectively. In both studies, the persulfates proved to be a vi-
able alternative to the conventionally used oxidants (i.e., percarbonate,
hydrogen peroxide).
Generally, oxidative wastewater treatment options are considered
as more efficient than the conventional ones; however, one of the
downsides of them is above-mentioned high cost of the chemicals and
energy involved. This drawback could be partially overcome by the
combination of various techniques (e.g. membrane ones), which could
not only reduce the amount of oxidant needed but also improve the
second process, e.g. by decrease membrane fouling [225].
Fagier et al. [226] presented the efficiency of coagulation-floccu-
lation pretreatment coupled with a SO4%− oxidation process in the
removal and mineralization of organic matter of sugarcane vinasse.
Ferric chloride (15 g L−1), a standard coagulation agent in wastewater
treatment plants (WWTP), was used and achieved a 70% TOC removal.
The pretreated vinasse subjected to a PDS/PMS oxidation process (ac-
tivated by Fe2+) showed the highest TOC removal efficiency at pH 7.
Under the selected optimum conditions, approximately 70 and 49%
S. Wacławek et al.
TOC removal was achieved for PMS/Fe2+ and PDS/Fe2+, respectively.
Also, Rodríguez-Chueca et al. [227] investigated winery wastewater
treatment using PMS coupled with a transition metal and UV light. High
COD and TOC removal efficacy (79% and 64%, respectively) was ob-
served under optimal conditions after three hours of treatment.
In another study, wastewater containing cytosine arabinoside (ara-
C) was treated with PDS and H2O2 activated by UV radiation [228]. It
was found that addition of oxidants considerably increased the ara-C
removal effectiveness, and the TOC content in the wastewater declined
with longer oxidation period but the toxicity increased, surprisingly,
mainly in UV/H2O2 system. Shu et al. [229] investigated the UV/PMS
degradation of Acid Blue 113 containing wastewater. They observed
that there was no correlation between initial pH value and dye removal
efficiency but UV light intensity significantly affected the efficiency of
TOC removal.
Heterogeneous activation of PMS could also be used for the re-
mediation of organic contaminants in wastewater according to [27].
They concluded that a CoMn2O4 catalyst was efficient for the hetero-
geneous activation of PMS and environmentally friendly. However, it
showed almost no catalytic activity to PDS and H2O2. They observed
that Rhodamine B degradation in wastewater was enhanced with an
increase in reaction temperature (15–55 °C) and inhibited with an in-
crease in fulvic acid concentration (0–0.08 g L−1).
To date, a very limited number of papers have been published
concerning the use of persulfates for sludge disintegration. There are
many investigations in the matter of sludge disintegration by PDS and
only a few focusing on the disintegration of activated sludge by PMS.
The methods often used for determining the degree of waste activated
sludge (WAS) disintegration include the measurement of soluble che-
mical oxygen demand (SCOD) and the sludge volume index (SVI).
Determining the SCOD can unveil the degree of polymer transfer from
the solid phase to the liquid phase, whereas the SVI is a measurement of
the settleability of the sludge, which can be measured in a 1000 mL
measuring cylinder after 30 min of sedimentation and expressed for a
known initial sludge concentration. One of the first references to per-
sulfates being used for sludge disintegration can be found in a study by
[230], who observed that ferrous iron activated PDS has a positive ef-
fect on enhancing sludge dewaterability with an 88.8% capillary suc-
tion time (CST) reduction within 1 min. The purpose of a CST test is to
characterize the sludge dewaterability rapidly and easily. The time the
filtrate requires to travel a fixed distance in the filter paper is referred to
as the capillary suction time [231]. Similar results to Zhen et al. [232]
were obtained by Shi et al. [233], whereby the highest specific re-
sistance to filtration (SRF; which is another often used method for de-
waterability assessment) and CST reduction efficiencies of 88.5 and
91.5%, respectively, were acquired after PDS/Fe2+ oxidation. Electro-
activated PDS, has also been applied for sludge treatment [234] and it
was concluded that the process can be potentially applied to deal with
wastewater from toluene nitration processes. In addition, it was de-
termined that 2,4-dinitrotoluene in wastewater under electro-activated
PDS oxidation can mainly be treated by virtue of SO4%− descended
from the reduction of PDS anions. Also, Zhen et al. [235] performed
electrolysis/PDS/Fe2+ oxidation to improve sludge dewaterability by
disrupting the protective barrier and cracking the entrapped cells,
which resulted in releasing the water inside extracellular polymeric
substances and cells. Zhen et al. [232] found that a combination of PDS
and thermal processes (at a mild temperature) is efficient in enhancing
the dewaterability of sludge. They concluded that when the tempera-
ture is increased to 80 °C in the presence of PDS, the flocs of waste
activated sludge were drastically changed and that this pretreatment
resulted in the disruption of sludge flocs by degrading extracellular
polymeric substances. These results were confirmed in a recent study
focusing on the disintegration of sludge with heat activated PDS [236].
It was observed that organic matter and polymer transfer from the solid
phase to the liquid phase occurred. An increase in SCOD, (almost a 15-
fold increase over the WAS value) and a decrease in the SVI from
57
Chemical Engineering Journal 330 (2017) 44–62
89.8 cm3 g−1 to 30.6 cm3 g−1 were also observed. A large issue for
introduction of the presented method in WWTP, concerns heat activa-
tion of persulfates. However, the temperature threshold sufficient for
PDS to rapidly form radicals (50–90 °C) can be reached using e.g. the
heat generated in the fermentation process, steam or hot air injection
[237].
Probably the first reference to the use of PMS for chemical disin-
tegration of waste activated sludge was made in our recent papers
[238,239]. Similarly to an earlier study [236], it was concluded that
heat application (50, 70 and 90 °C) for PMS activation causes an in-
crease in the soluble COD value and protein concentration in the su-
pernatant and positively influences the SVI, which decreased from 89.8
to 17.2 mL g−1. Also, Niu et al. [240] and Liu et al. [241] observed
positive effects of WAS oxidation with PMS. Sludge disintegration was
characterised by a change in disintegration degree (DD), sludge particle
size, and the properties of extracellular polymeric substances.
Although thermally activated persulfates are efficacious for the
disintegration and improvement of sludge sedimentation properties
[238], Zhen et al. [242] observed a possible inhibitory effect on
anaerobic digestion. On the contrary, Sun et al. [243] found that PDS
disintegration had a positive influence on the biogas yield. Therefore,
the composition of the sludge and the type of fermentation could be
crucial for assessing the benefits of persulfates for WAS disintegration.
Sludge treatment with persulfates can also be focused on anaero-
bically digested sludge as reported in a recent study [244] and in a
recent article published in Nature: Scientific Reports [245]. In addition
to the enhancement of dewaterability, good efficiency of toluene re-
moval from anaerobically digested sludge could be observed after the
treatment with persulfates catalysed to form radicals with elevated
temperatures from meso- or thermophilic digestion [244].
6. Conclusions
Despite persulfates being efficacious substances for the remediation
of water, wastewater and sludge media, the decay of pollutants is ex-
tremely dependent on activation techniques and the composition of the
treated water matrix.
Non-activated persulfates react at rates that are often considered
slow, but fast reactions between the persulfates and free radicals gen-
erated from them can increase the significance of these processes.
Although non-catalysed persulfate reactions possess advantages, i.e.
lower cost, no secondary contamination due to the catalyst load and
higher stability in the subsurface, drawbacks i.e. often much slower
reaction rates with contaminants and formation of stable disinfection
by-products, which reduce natural attenuation, favour the use of acti-
vated persulfate reactions.
Activation can be achieved by versatile means such as heat, UV
radiation, radiolysis or by chemical methods, allowing to establish
SO4%−-based oxidation in very different fields such as remediation,
wastewater and drinking water treatment.
Chemical activation of persulfates can be considered either a
homogenous or a heterogeneous reaction. Both of these radical initia-
tion types have benefits and drawbacks, although especially the high
cost, chemical stability (leaching of catalyst constituents), long pre-
paration time, and chemical stability of heterogeneous catalysts in some
cases still largely limits their use in water treatment. In the subsurface
the water quality parameters are of great importance. The pH value and
concentrations of halogens/natural organic matter were found to be
especially crucial. In most of the systems pH of ∼ 3 was found to be
beneficial for rapid decontamination (although typically the pH of
natural waters is not that low). However, elevated pH values can en-
hance the reaction rates due to the additional activation (proven for
both persulfates) and the faster reaction of radicals with deprotonated
compounds. Natural organic matter and halogens are of relevance due
to their radical scavenging and them being a precursor to organic dis-
infection by-products. On the contrary, activation can be caused
S. Wacławek et al.
incidentally by specific site conditions (e.g. large transition metal
content or elevated pH).
In the catalysed persulfate systems the SO4%− is often considered to
be the main oxidative species. However, depending on reaction con-
ditions other reactive species such as hydroxyl radical and superoxide
radical were determined by many authors to play an important role,
too. In case SO4%− is converted to other reactive species, sometimes the
unique features of SO4%− cannot be exploited. This is important to
know in case very persistent compounds such as chlorotriazine diamine
or polyfluorinated compounds (e.g. PFOA) have to be degraded, which
are inert towards the conventional degradation methods.
In the present review analytical methods for quantification of per-
sulfates were presented and assessed. Spectrophotometric methods are
among the most commonly used for persulfate determination; however,
it should be noted that the liquid chromatographic methods are among
the most reliable with a low quantification limit.
Data on decontamination kinetics using activated persulfates show
that such reactions are regarded as extremely fast in comparison to
biological or chemical reductive treatment (However, it should be
noted, that some compounds might be degraded only by the chemical
reduction). The pseudo-first order kinetic model (experiments con-
ducted with an excess of oxidant) is mostly used.
Persulfate decontamination technologies either with oxidation via
direct electron transfer or free radical driven processes were found to be
very powerful tools for the remediation of a wide range of con-
taminants, including chlorinated olefins, BTEXs, phenols, pharmaceu-
ticals, inorganics and pesticides. However, several disadvantages, i.e.
pH changes, salinity of the soil and creation of hazardous decontami-
nation by-products should be seriously taken into account before their
application.
Acknowledgements
The work was supported by the project LO1201, the financial sup-
port of the Ministry of Education, Youth and Sports in the framework of
the targeted support of the “National Programme for Sustainability I”
and the OPR & DI project “Centre for Nanomaterials, Advanced
Technologies and Innovation - CZ.1.05/2.1.00/01.0005”. The authors
also acknowledge the assistance provided by the Research
Infrastructure NanoEnviCz, supported by the Ministry of Education,
Youth and Sports of the Czech Republic under Project No. LM2015073.
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