Review
PII: S1385-8947(17)31271-8
DOI: http://dx.doi.org/10.1016/j.cej.2017.07.132
Reference: CEJ 17398
Please cite this article as: S. Wacawek, H.V. Lutze, K. Grbel, V.V.T. Padil, M. ernk, Dionysios.D. Dionysiou,
Chemistry of persulfates in water and wastewater treatment: a review, Chemical Engineering Journal (2017), doi:
http://dx.doi.org/10.1016/j.cej.2017.07.132
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Chemistry of persulfates in water and wastewater
treatment: a review
Stanisaw Wacawek 1*, Holger V. Lutze2,3,4, Klaudiusz Grbel5, Vinod V.T. Padil1,
3
IWW Water Centre, Moritzstr. 26, D-45476 Mlheim an der Ruhr, Germany
4
Centre for Water and Environmental Research (ZWU) Universittsstr. 5 D-45141 Essen
5
Institute of Environmental Protection and Engineering, Department of Environmental Microbiology and
6
Environmental Engineering and Science Program, University of Cincinnati, 705 Engineering Research Center,
Abstract
electron transfer are very powerful tools for the treatment of a broad range of impurities,
the reactivity of persulfates is extremely dependent on the related activation techniques and
the composition of the treated water matrix. Direct reactions of peroxydisulfate (PDS) or
1
peroxymonosulfate (PMS) are rather slow and mostly unsuitable for pollutant degradation.
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
radical
1. Introduction
Over the last few decades, ubiquitous contamination with various inorganic and organic
substances has caused serious problems all over 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 pathogens [3]. In many countries with a low human development index (HDI),
particularly in Africa and Asia, surface- and groundwater contamination can be a direct cause
of water scarcity. It is important, therefore, to develop cheap and efficient water and
There are many different water and wastewater decontamination methods, which can be
universally divided into biological [5], physical [6], and chemical methods [7].
2
Oxidants used for environmental purposes can be divided into ones that possess a peroxide
bond and ones that do not. Oxidizing agents such as ozone and hypochlorite have long been
employed for water and wastewater treatment [8,9]. Oxidants possessing the O-O bond
(known as peroxide or the peroxo group), typically form free radicals which in turn may result
in pollutant degradation.
water and wastewater treatment [10-12] (Fig. 1). Many studies have shown that they are
capable of degrading highly toxic and persistent pollutants, e.g. polychlorinated biphenyls
(PCBs) [13,14], and are relatively cheap in comparison to other oxidants [15] (Table 1).
Fig. 1. Annual number of a) publications concerning PDS or PMS and b) citations. Source:
This paper reviews the chemical and physical properties of persulfates in addition to their
determination and activation methods. Moreover, the direct oxidation reactions of persulfates
3
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 electrolysis 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 ammonium PDS can cause residual ammonia and
secondary contamination. 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 oC)
[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 applications. The bond dissociation energy
and bond length of [O3SO-OSO3]2- were respectively determined to be 140 kJ mol-1 and 1.497
[15,16,19].
Table 1
4
ferrate at pH 9
1
PMS is herein considered as the Oxone salt (2KHSO5KHSO4K2SO4);
2
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#.Vu2SzOZxBqF;
[21]
3
[22]
4
Depends on water hardness, transition metal concentration, dissolved organic carbon (DOC)
Peroxymonosulfate (PMS; monopersulfate) has its origin from the Caros acid (H2SO5) also
oxygen closest to the hydrogen atom that carries the active power (Fig. 2b). Since the oxygen
is readily reactive, KHSO5 is usually found in a more stable form of a white triple salt,
the trade-name of Oxone and has a high solubility in water, is safe to handle, hence it has a
good potential applicability [25-27]. In comparison to PDS, PMS has a shorter bond length
(1.46 ), which translates to a higher bond dissociation energy (377 kJ mol-1). In other words,
in theory, PMS requires more energy to produce radicals in the homolytic cleavage of the
peroxide bond.
5
Fig. 2. (a) Sodium PDS and (b) Oxone triple salt molecular structure (*potassium PMS
(KHSO5) - active part of Oxone; bond lengths were taken from [28]).
The cost of Oxone is the highest of all of the conventionally used oxidants in ISCO, although
Persulfates are very stable in the solid state and remain stable for several months in pure
water. One of the advantages of PDS in comparison 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
temperatures (>300 C) it decomposes to SO2 and SO3. PMS is also not stable in water with
6
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
the reduction of PDS anion (Eq. 1) equals to 2.01 V, hence it is higher than that of PMS i.e.
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., photochemical or thermal cleavage of the peroxide bond or chemical reduction.
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 pollutants. 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]. Furthermore, activation of persulfates by
hydroxide ions [44,45] in ozonation [46] or in presence of phenol [47] was described.
7
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+, Co 2+, Ni2+, Cu 2+,
Ru 3+, Ag+), divalent cobalt was determined to be the most efficient 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 long term
application.
A detailed summary of the activation methods of PDS and PMS is presented in Tables 2 and
3, respectively.
8
Table 2
Heat Homolysis of peroxide bond (in presence of chloride / at low temperature increase can effectively cleave O-O [35,36,56]
Homogenous:
One electron transfer Sulfate radical Often requires low pH [48]
Transition metals
Heterogeneous:
trimetallic systems)
9
radical formation
the defective edges and oxygen Reduced mesoporous carbon, carbon nanotubes,
groups (from which the carbonyl group and graphene oxide, displayed great catalytic
Nanocarbons Hydroxyl radical [15,63]
was found as the most active one) of properties, in contrary to nanodiamonds, fullerenes
Radiolysis Reaction with the solvated electron Sulfate radical Electron beam irradiation of aqueous solution [39]
Table 3
10
species
Sulfate radical/ Higher temperatures are required to split the O-O bond, due to
Heat Homolysis of peroxide bond [49]
Hydroxyl radical a higher bond-dissociation energy in comparison to S2O82-
Sulfate radical/
UV radiation Homolysis of peroxide bond Often used =254 nm, Quantum yield 0.52 [49,52]
Hydroxyl radical
Heterogeneous: [60]
One electron transfer Sulfate radical Preparation of catalyst is not economical
Transition metals
One electron transfer from The contaminant degradation rate by an oxidant assisted with
Electrolysis electrochemically/chemically Sulfate radical electrolysis was observed in the following order: PMS > PDS [64]
Nanocarbons One electron transfer Sulfate radical other allotropes of carbon, like: activated carbon (AC), [65]
Sulfate radical/
Organics One electron transfer Polyimide as an electron donor [66]
Hydroxyl radical
11
Formation of an O3SO5 adduct Sulfate radical/
Ozone - [46,52]
that decomposes into radicals Hydroxyl radical
12
The application of PMS and PDS in oxidation treatment belongs to advanced oxidation
AOPs can be either homogeneous or heterogeneous. Whilst homogenous AOPs are the most
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]).
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
significantly 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. They found that PMS was the all-embracing oxidizing agent catalysed by all
ferrous iron-chelates, whereas citrate coupled with ferrous iron was the best chelate/iron
configuration.
On the other hand, heterogeneous processes with material (often in nano-scale) synthesized
beforehand, have drawn much attention recently 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
13
are used for peroxymonosulfate activation). Co 3O4 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] synthesized 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 supports (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
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
Co xFe3-xO4 material and discovered that the iron-cobalt interactions are vital for effective
heterogeneous catalysis of PMS. Lin et al. [82] demonstrated an alternative path to synthesize
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%, displaying its stability and efficient catalytic
activity. In their further study, a nanocomposite was prepared by the carbonization (one-step)
dose, acidic conditions and temperature greatly ameliorated the degradation of caffeine.
14
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
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 minutes. Ding et al. [85] used cobalt and bismuth salts
and sodium hydroxide (as a precipitation agent) to create the Co3O4-Bi2O3 nanocomposite as a
performance towards PMS for the removal of organic contaminants. Moreover, leaching of
cobalt was decreased to 43 g L-1, which is an improvement when compared to that of Co3O4
(158 g L-1) under equivalent testing conditions. Yang et al. [76] claimed that the
heterogeneous oxide CoFe2O4 was capable to steadily catalyse PMS for the abatement of 2,4-
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
secondary contamination. One way to overcome this problem was proposed by Rhadfi et al.
[87], who determined that the partial replacement of cobalt in Co 3O4 with Mn can be a
strategy for decreasing the quantity of the harmful Co element. Mn is more abundant in
nature, more environmentally 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
15
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
simultaneously produced in the activation processes, however SO4- played a more crucial role
(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
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 concerning heterogeneous
compared with the alternative heterogeneous catalytic materials and shown to be superior in
comparison to CuFe2O4, CoFe2O4, CuBi2O4, CuAl2O4, Fe2O3, and MnFe2O4 (whereas the
catalyst order indicates their activity towards PMS). Moreover, it is possible to reuse
CuFe2O4-Fe2O3 catalyst (at least several times) without significant performance loss. In
addition, Zhang et al. [94] observed that the property of nano-Fe3O4 to activated PMS can be
Ghauchs group by working on bi and trimetallic systems has significantly 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 solution to a
minimum and the repeated experiments did not show any efficiency loss [51]. Moreover, their
16
research on the reaction stoichiometric efficiencies (RSE) allows to better understand and
compare the reaction mechanism of different activation methods and its correlation to the
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 environmentally 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 persulfates [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
environmentally friendly catalyst for the efficient activation of PMS that later exhibited
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
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 -
17
sulfur as a metal-free photo-catalyst for PMS (under irradiation with visible light) is efficient,
Considering the fact that large amounts of solid waste that could be used for the activation of
persulfates are produced from various industries, 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 microns 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
detailed study of the activation of oxidants with O-O 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 >
peroxide/AO7 - 10/1). Surprisingly, they also determined that relatively common (in ground,
surface, and wastewaters) anions (i.e. HCO3-, HPO42-, Cl-, and 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
18
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).
Another persulfate activation technique often used in situ is alkaline activation involving an
(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 effectively
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 persulfates. 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.
19
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 degradation of methylbenzene (toluene) from a surfactant flushing
solution. 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]). According to Lin et al. [105], during the
electrolysis, goethite (-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 Wacawek et al. [55]. This study has shown that pseudo first-order reaction rate
constant of lindane removal was (at the optimal conditions) 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).
Recent work reported by Cong et al. [108], focusing on the simultaneous use of PMS and
ozone for degradation of 4-chlorobenzoic acid, indicated that PMS may act in a similar way to
H2O2 in the promotion 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 sulfate and hydroxyl radicals were present in this system, which was confirmed by
20
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, respectively. 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-,
4. Determination methods
Numerous determination methods for PDS and PMS can be found in the literature. These
methods vary in their execution time and sensitivity of detection (see Table 4 and 5).
Tables 4 and 5 present a summary of PDS and PMS determination methods, respectively.
Table 4
Time of
Method Substance used Limit of quantification Reference
measurement
Direct UV-
Spectrophotometry - - [58,109]
absorption
Methylene blue
radiation
N,N-diethyl-p-
Spectrophotometry 10 min 10-5 M [114]
phenylenediamine
21
poly-brilliant
cresyl blue on
carbon nanotube
Electrode (glassy
carbon) with a
nanocomposite
ruthenium oxide
nanoparticles and
thionine
Electrode (glassy
carbon) with a
nanocomposite
ruthenium oxide
nanoparticles and
celestine blue
Prussian blue -
modified
Voltammetry - 5 x 10-5 M [118]
platinum disc
electrode
Mobile phase: 50
rate: 1 mL/min
Table 5
Time of Limit of
Method Substance used Reference
measurement quantification
22
Titration Ce4+/Fe2+ <20 min 10-5 M [110]
N,N-diethyl-p-
Spectrophotometry 10 min 10-5 M [114]
phenylenediamine
anion-exchange column;
flow
Mobile phase:
buffer; flow
nm
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 chromatography and HPLC [119,122,123].
23
5. Persulfate decontamination technologies
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
from the PDS ion [126]. In the Elbs reaction, phenolate anion (or a tautomer) acts as the
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
In Figure 3 the second-order reaction rate constants of persulfate reactions with several
24
Fig. 3. Comparison of the second-order reaction rate constants of persulfates 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];
Further example of PDS oxidation not relying on the radical formation was presented by
Zhang et al. [21]. According to them, PDS weakly interacts with the surface of copper oxide
(under mild conditions) 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
Furthermore, Lei et al. [133] have shown that not only PDS can efficiently 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,
25
they concluded that Cl- anions improved the degradation efficacy of the target pollutants.
Radical quenching experiments and ESR studies revealed that 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
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 hours,
which was possible even after addition of radical scavengers in high concentrations (1.6 M of
methanol).
Electron transfer reactions of oxygen yield reactive oxygen radicals [135]. Also, oxygens
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
shown in Figure 4.
26
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 of
Superoxide disproportion may result in the formation of H2O2 which in turn can react to
with SO4- in reactions 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). Considering 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 10 2 M-1 s-1. However, reactions of SO4- with other
matrix components such as chloride or dissolved organic compounds are likely more
important at that pH-values (for relevant reaction rate constants see Table 6). Studies based on
27
radical scavenging analyses paired with the use of the ESR technique were performed to
Several compounds can be used for scavenging of SO4 and OH. For choosing the correct
scavenging agent, one has to consider reaction kinetics and product formation. It has to be
provided that only reactions under study are relevant and that products which could interfere
TBA (khydroxyl radical = 6.0 10 8 M1 s1, ksulfate radical = 4.0 10 5 M1 s1) and ethanol (khydroxyl
radical = 1.2 10 9 M1 s1, ksulfate radical = 1.6 10 7 M1 s1) are the most often used chemical
probes to evaluate the relative contribution of SO4 and OH because of their different
reaction rate constants [138]. Also with the ESR technique, the radicals can be determined
qualitatively (rough estimation of the intensity of radicals in the spectra). The spin trap
oxidation systems and forms a unique radical adduct that is stable, relative to the radicals of
interest.
Indeed with these techniques, it was shown that in most cases SO4- prevails in acidic media
and OH predominates in alkaline media (e.g. tested at the pH of 5 and 11 by Fang et al.
[139,140] (at the pH of 9 both radicals were in similar quantity [140]). Similar conclusions
were obtained by Liang and Su, [138] by using various probes: TBA, phenol, and
nitrobenzene).
Reactions of SO4- are very different from reactions of OH. SO4- are prone to react by
electron transfer reactions while OH favours H-abstraction and addition reactions. This can
explain that reaction rate 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
28
information see [127] and [141]. For a more detailed explanation of radical identification, e.g.
In persulfate based oxidation processes, pollutants are mainly degraded by reactions of SO4-
which are formed by the different activation 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
3. Formation of by-products
In order to define how fast the reaction proceeds, second order rate 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 SO4- with common anions and
Table 6
Second-order reaction rate constants of hydroxyl and sulfate radicals with common anions
and NOM.
Rate constants
Radical Compound Reference
(M-1 s-1)
29
SO4- Br- 3.5 x 109 [148]
Scavenging is mainly driven by dissolved organic matter (DOM), HCO3- and CO32- and in
some cases nitrite and reduced metal species such as Fe2+. DOM and reduced metal species
mainly consume oxidation capacity because the products formed in these reactions are not
reactive towards pollutants. For the reaction of the sulfate radical and hydroxyl radical with
humic acids the kinetic rate constant was measured to be 6.8 10 3 L mg C-1 s-1 and 1.4 104
L mg C-1 s-1 (mg C = mg carbon), respectively [152]. On the contrary, Luo et al. [32] observed
that the oxidation capacity of the hydroxyl radical and sulfate radical for humic acid
degradation (in the presence of Cl- and Br-) was nearly in the same order. This can be
explained by the below discussed conversion of SO4- into OH in presence of chloride. Hence
in both systems the same oxidant prevails, i.e., the hydroxyl radical. Especially Br- had a
negative impact on the efficiency of these processes, which is in agreement with the research
work of Yang et al. [153] (Although, in several studies a concentration of 1 mM of Br- and/or
Electron transfer reactions of SO4- with phenolic moieties of DOM result in radical cations
which may rearranged in presence of water into carbon centred radicals in analogy to the
reaction of benzenes with SO4 - [154]. Carbon centred radicals react rapidly with oxygen ( 2
109 M-1 s-1 [155]). The ensuing peroxyl radicals eliminate O2- or HO2 or decompose in
30
bimolecular reactions [155]. Both pathways often result in carbonyls [155]. Halide ions also
react with SO4-. The reactivity of bromide towards SO4- is high (k = 3.5 109 M-1 s-1 [148])
and in pure water bromate is formed as a stable product [156], which is undesired due to its
carcinogenic potential (EU and US-EPA drinking water standard 10 g L-1). The presence of
formed in field water matrices [156]. Fang and Shang [157] came to a similar conclusion. Liu
et al. [158] investigated the transformation of Br- in a PMS (activated by cobalt) oxidation
process with the presence of phenol as a model compound imitating NOM. It was determined
that bromide can be efficiently converted to free bromine and bromine radicals. These
reactive species caused bromination of phenol and the formation of brominated disinfection
Brominated disinfection by-products were also degraded by surplus SO4-. Free bromine was
also created when cobalt was not present, indicating that Br- might be directly oxidized 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,
Iodide also reacts fast with SO4-, which may form iodate in analogy 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-
31
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 conventional 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, oxidation 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 - 10 10 M-1 s-1
[149,162]. However, this may be compensated by the small reaction rate of CO3 - with the
Table 7
Reaction rate constants of carbonate radicals with pollutants and matrix components and of
Carbonate radical
32
7 Irgarola 0.73 0.12 107 M-1 s-1 [164]
Sulfate radical
Hydroxyl radical
33
DOC 2.5 104 L mg-1 s-1 [166]
The efficiency of pollutant degradation is depending on the scavenging rate of the water
matrix and the kinetics of the radical reaction with the pollutant. With the kinetics of
scavenger reactions and pollutant reactions at hand one can calculate the apparent degradation
rate (k) in a given water sample according to Katsoyiannis et al. [167]. Figure 5 shows k for
the compounds of Table 7 for reactions of CO3- assuming a water matrix with 1 mg L-1 DOC
and 1 mM HCO3-. k 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-
. Figure 5 also shows k for the same water matrix in SO4- and OH reactions (dashed lines)
for a defined reaction kinetics towards trace compounds (dashed lines in Figure 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 k = 0.25 s-1, in case CO3- reacts with DOC at a rate of 40 L mg-1
s-1. The same k 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 10 9 M-1 s-1 (dashed
lines in Figure 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 10 6 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 pollutant 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
34
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 moieties such as anilines reveal a fast
reactivity towards CO3-. It is conceivable that the degradation of electron rich compounds is
32 (Table 7, phenols and anilines). Most pesticides listed in Table 7, however, reveal reaction
rate constants of < 10 7 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
k / s-1
2.5 -50
15
2
10-14 -100
1.5 1-9 k(SO4 -) = 9 109 M -1 s-1
Fig. 5. Calculated apparent first order kinetics (k) of pollutants degradation by carbonate-,
sulfate- and hydroxyl radicals in presence of 1 mg L-1 DOC and 1 mM HCO3-. Calculations
are based on reaction rate constants shown in Table 7. Circles: k(carbonate radicals)
assuming: k(CO3 -+ DOC) = 40 L mg-1 s-1, squares k(carbonate radicals): assuming k(CO3 -+
35
DOC) = 40 L mg-1 s-1, dashed lines k(sulfate radicals or hydroxyl radicals, as indicated in the
figure) for a given reaction rate constant towards a pollutant, as indicated in the figure.
It was also reported that reactive chlorine species, formed in the reaction of SO4 with Cl,
may also react with other matrix component 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 reduced the abatement efficacy of cyclohexanecarboxylic acid and benzoic
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 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. haloacetic acid and chloroform, only increased a little, but the generation of
slightly decreased. On the contrary, Lu et al. [170] found that after treatment of surface water
36
with 0.1 M PDS for 48 hours, caused increase in concentration of compounds such as:
chloroform, trichloroacetic acid, and dichloroacetic acid by 16%, 37%, and 52%, respectively.
The above results indicate that before the application of persulfates in the field, bench scale
studies should be performed in detail due to the fact that the formation of dangerous by-
To sum up, at typical conditions of drinking water treatment (i.e., pH 6-9) presence of SO4-
scavenged by chloride are largely transformed into OH. Reactive chlorine species are prone
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 selectivity
compared to SO4- and OH, provided that CO3- readily react with such pollutants (k 107 M-1
Although persulfates treatment has many benefits, there are also several downsides that have
to be taken into consideration, i.e. contamination with sulfate salts or even worse newly
created hazardous compounds due to e.g. additional chlorination and/or bromination (as
In addition, many researchers study toxicity in clean systems, although 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 (Wacawek and Kudlek, unpublished data), many new
substances (with a molecular mass larger than 250 g mol-1) were observed after UV/persulfate
treatment that were unnoticed after e.g. UV/hydrogen peroxide treatment. Therefore, during
37
bench-scale testing performed before field application, 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 qinghaiensis sp. Q67 test after the PDS treatment of carbamazepine and
concluded that the acute toxicity has decreased together with the removal of the
pharmaceutical (the inhibitory effect of the solution after treatment decreased to 65% within
60 minutes). 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
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 observations to Temiz et al. [172], concerning toxicity of TX-45 and its oxidation
by-products).
38
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
decontamination of water (subsection 5.5.1) and wastewater (subsection 5.5.2) with the
5.5.1 Water
SO4- are very reactive and able to degrade very persistent organic compounds.
Perfluorooctanoic acid (PFOA) e.g., that is unreactive towards 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 reaction SO4- with perflurocarbonic acid are very
slow (approximately 10 4 M-1 s-1). Since the reaction of SO4- with other matrix components is
oxidation.
SO4- can readily oxidize other organic pollutants such as 2,4-dichlorophenol [75], 2-
chlorobiphenyl [181], aniline [24], bisphenol A [182], calcon [183], Acid Orange 7 [19],
acid [187], C.I. Reactive Black 5 [188], C.I. Basic Red 46 [189], methylene blue [190],
endosulfan [191], antipyrine [192], naproxen [95], chloramphenicol [59], ranitidine [51],
39
Table 8
Possibly SO4- (not Trace quantities of hexachloroethane 7.6 x 10-3 min-1 (activation temperature of
Perchloroethene [144]
identified) as an intermediate. 50 oC)
Possibly SO4- (not Trace quantities of hexachloroethane 4.7 x 10-3 min-1 (activation temperature of
Trichloroethene [144]
identified) as an intermediate. 50 oC)
Possibly SO4- (not Of all the BTEX compounds studied, benzene was 9.5 x 102 day-1 (activation temperature of
Benzene [195]
identified) most resistant to PDS oxidation. 20 oC; Oxidant/BTEX molar ratio 100/1)
BTEXs
Possibly SO4- (not 23.2 x 102 day-1 (activation temperature of
Toluene - [195]
identified) 20 oC; Oxidant/BTEX molar ratio 100/1)
41
Possibly SO4- (not 14.5 x 102 day-1 (activation temperature of
Ethylbenzene - [195]
identified) 20 oC; Oxidant/BTEX molar ratio 100/1)
SO4- (scavenging
Degradation involved one electron transfer, 0.032 h1 (Activation temperature of 50
Diclofenac tests were [197]
o
hydroxylation, decarboxylation. C; Oxidant/Diclofenac molar ratio 10/1)
performed)
Bisoprolol SO4- and OH The formation of hydroxylated products through 8.5 10-2 min-1 (activation temperature of [36]
42
(scavenging tests hydroxylation was proposed. 60 oC; Oxidant/Bisoprolol molar ratio
10-3 sec-1
-
Possibly SO4 Approx. 96.4% of chloride ion was released after
(UV activation parameters: = 254 nm;
Lindane and/or OH (not the treatment, which was consistent with the TOC [107]
10 M = Fe2+; Oxidant/Lindane molar
identified) analysis.
ratio 73/1)
50/1)
Pesticides Triazine
Manoj et al. [198] has determined
pesticides
bimolecular rate constants of the SO4- [32,152,198-
(atrazine, tert- -
Possibly SO4- reaction with triazines in the range of: 200]
butylazine,
and/or OH 4.61073109M1s1, whereas Lutze et
propazine)
al. [152]: 2.23.5 109 M1 s1; Khan et
43
OH, respectively;
0.18 h1
SO4- accepts an electron from the carboxylate
PFOA SO4- and S2O8- (UV activation parameters: = 254 nm; [180]
group in a primary step.
Oxidant/PFOA molar ratio 33/1)
44
Moreover, Neppolian et al. [201] proved that these radicals can also be used for the removal
of inorganic pollutants in water. They investigated 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
(similar 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
Surprisingly, according to Diao et al. [202,203] SO4- coupled with nano zero-valent iron
(supported on bentonite, and used as a radical 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
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 degradation in situ. Recently, Yan et al. [206] combined siderite-catalysed
H2O2 with PDS and effectively used it for the remediation of trichloroethene contamination
from groundwater. It was claimed therein, that in the absence of PDS (only catalysed
peroxide), most of the hydrogen peroxide was reduced within the first hour of the test,
resulting in non-efficient use of OH-radicals. After the addition of PDS, the decomposition
rate of H2O2 was mitigated due to a more sustainable release 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, dichloroacetic 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
46
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
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 simultaneous 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 abatement with and without activation
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 recent
removal with Co2+ catalysed PMS. It was found that DDT was efficiently decomposed within
which enabled calculation of the activation energy (72 kJ mol-1). Several by-products of the
dichlorobenzophenone, 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 intermediates) 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.
47
Several authors examined atrazine degradation with persulfates. 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
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 atrazine in reactions
with OH and SO4- are desethyl-atrazine and desisopropyl atrazine [152,211,212] which are
similarly toxic as the parent compound [213]. The second order rate constant of different
chlorotriazine 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 10 8 M-1 s-1) [152],
Wacawek 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 (-
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 M1 s1).
48
dichlorophenoxyacetic acid by ammonium PDS activated in several ways. 2,4-dichlorophenol
degraded 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 synergistic activation of PDS with heat and ferrous iron to improve the
the optimal degradation conditions (molar ratio between PDS/Fe2+ - 1:2, temp. - 50 C),
minutes, respectively.
As was mentioned in the introduction, the rapid emergence of resistant bacteria worldwide is
probably due to the overuse of medications that can later become a contamination of concern.
Several authors have focussed on the remediation of pharmaceuticals and since persulfates are
one of the newest ISCO reagents used, there are also several new studies describing their
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
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 hours, while full mineralization was achieved after 2 hours.
Also Ayoub and Ghauch [50] applied activated PDS for sulfamethoxazole 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.
49
Chen et al. [197] examined the performance of thermally activated PDS on the degradation of
diclofenac in both water and polluted 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
diclofenac, 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 approach 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 pharmaceuticals in water and sewage water [95].
SO4- treatment also proved to be effective for highly contaminated 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.
50
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 peroxydisulfate is a good
choice for wastewater oxidation below the critical temperature of water. The efficiency of
removal percentages of phenol were good even at 115 C. Nonetheless, it has to be noted that
although this radical initiation 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
wastewater was studied by Babaei and Ghanbari [223] and Kattel et al. [224], respectively. In
both studies, the persulfates proved to be a viable alternative to the conventionally used
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].
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
51
treatment plants (WWTP), was used and achieved a 70% TOC removal. The pretreated
vinasse subjected to a PDS/PMS oxidation process (activated by Fe2+) showed the highest
and 49% TOC removal was achieved for PMS/Fe2+ and PDS/Fe2+, respectively. Also,
Rodrguez-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 observed 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 remediation of organic
contaminants in wastewater according to [27]. They concluded that a CoMn2O4 catalyst was
efficient for the heterogeneous 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 oC)
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)
52
disintegration include the measurement of soluble chemical 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 minutes of
sedimentation and expressed for a known initial sludge concentration. One of the first
references to persulfates being used for sludge disintegration can be found in a study by [230],
who observed that ferrous iron activated PDS has a positive effect on enhancing sludge
dewaterability with an 88.8% capillary suction time (CST) reduction within 1 minute. 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 resistance to filtration (SRF; which is another often used method
for dewaterability 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
mainly be treated by virtue of SO4- descended from the reduction of PDS anions. Also, Zhen
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 temperature is increased to 80 oC
in the presence of PDS, the flocs of waste activated sludge were drastically changed and that
53
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 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 activation of persulfates. However, the temperature threshold sufficient
for PDS to rapidly form radicals (50-90 oC) can be reached using e.g. the heat generated in the
Probably the first reference to the use of PMS for chemical disintegration 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 increase in
the soluble COD value and protein concentration in the supernatant 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
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
Sludge treatment with persulfates can also be focused on anaerobically digested sludge as
reported in a recent study [244] and in a recent article published in Nature: Scientific Reports
54
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 extremely dependent on activation techniques and the
Non-activated persulfates react at rates that are often considered slow, but fast reactions
between the persulfates and free radicals generated 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
chemical methods, allowing to establish SO4 --based oxidation in very different fields such as
reaction. Both of these radical initiation types have benefits and drawbacks, although
especially the high cost, chemical stability (leaching of catalyst constituents), long preparation
time, and chemical stability of heterogeneous catalysts in some cases still largely limits their
55
use in water treatment. In the subsurface the water quality parameters are of great importance.
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 enhance 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
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 conditions 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
In the present review analytical methods for quantification of persulfates 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
Data on decontamination kinetics using activated persulfates show that such reactions are
56
(However, it should be noted, that some compounds might be degraded only by the chemical
reduction). The pseudo-first order kinetic model (experiments conducted with an excess of
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
inorganics and pesticides. However, several disadvantages, i.e. pH changes, salinity of the soil
and creation of hazardous decontamination by-products should be seriously taken into account
Acknowledgements
The work was supported by the project LO1201, the financial support 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,
by the Ministry of Education, Youth and Sports of the Czech Republic under Project No.
LM2015073.
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Chemical and physical properties of persulfates were described in detail
Up-to-date list of persulfates activation and determination methods was created
Direct oxidation, radical oxidation and matrix effects were discussed
Recent developments in the use of persulfates in waters and wastewaters were shown
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