Environmental Technology & Innovation xxx (xxxx) xxx

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Environmental Technology & Innovation

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

p-Nitrophenol degradation by activated persulfate

∗ ∗
Carmen S.D. Rodrigues , Luis M. Madeira
LEPABE - Laboratory for Process Engineering, Environment, Biotechnology and Energy, Faculty of Engineering, University of
Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

article info a b s t r a c t

Article history: The degradation of p-nitrophenol (PNP), which is listed as a priority pollutant by
Received 13 July 2020 the Environmental Protection Agency (EPA), was investigated in this work by the
Received in revised form 13 October 2020 activated persulfate oxidation. Different forms of persulfate activation (namely thermal,
Accepted 19 November 2020
by medium basification and with an iron salt catalyst) were evaluated, apart from
Available online xxxx
founding the best operating conditions for maximizing process performance (assessed in
Keywords: terms of PNP removal and mineralization — evaluated by the overall total organic carbon
Persulfate oxidation (TOC) reduction). For the thermal and alkaline activation of persulfate, the temperature
Sulfate radical was varied in the range of 30 to 90 o C and the pH between 3.0 to 9.0, respectively,
Thermal being found that best performances exist for a reaction temperature of 70 o C while pH
Alkaline and iron activation
above 7.0 is not necessary. In short reaction times (≤10 min) the oxidation of PNP,
p-nitrophenol
mineralization and consumption of persulfate were successfully fitted to a second-order
Intermediate compounds
kinetic model and the apparent activation energies determined. The effect of persulfate
concentration was determined in the range of 0.8 g/L to 9.6 g/L, being noticed that
an increase in its concentration above 6.4 g/L led to worst process performances. An
additional improvement was observed with the presence of iron in solution, indicating
that the metal salt plays an important role in catalyzing the persulfate activation —
again, an optimal iron dose was observed (80 mg/L). The combination of the three
ways to activated the persulfate allowed obtaining the highest PNP (94%) and TOC
(66%) removals, showing that the process is promising in the degradation of PNP and
organics mineralization. Radical scavenging runs allowed concluding that both radicals,
sulfate and hydroxyl, are forming during the oxidation process, however the role of
SO•−
4 predominates. The identification and quantification of reaction intermediates was
also assessed and the contribution of carboxylic acids (oxalic, maleic and pyruvic) in
TOC measured was found to be higher than 95%. Finally, the effect of the matrix was
evaluated, and for this purpose a domestic wastewater was spiked with 500 mg/L of
PNP; it was found that the degradation of the pollutant was almost not affected by the
water matrix.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction

Advanced oxidation processes (AOPs) are promising and efficient technologies that, very often, make use of
environmental-friendly reagents, which has led, in the last decades, to a huge increase in their application to degrade
several compounds and treat complex wastewaters. AOPs are based on the generation of powerful oxidizing agents by
chemical, sonochemical, electrochemical or photochemical reactions (Oturan and Aaron, 2014).

∗ Corresponding authors.
E-mail addresses: [email protected] (C.S.D. Rodrigues), [email protected] (L.M. Madeira).

https://doi.org/10.1016/j.eti.2020.101265
2352-1864/© 2020 Elsevier B.V. All rights reserved.

Please cite this article as: C.S.D. Rodrigues and L.M. Madeira, p-Nitrophenol degradation by activated persulfate. Environmental Technology & Innovation
(2020) 101265, https://doi.org/10.1016/j.eti.2020.101265.
C.S.D. Rodrigues and L.M. Madeira Environmental Technology & Innovation xxx (xxxx) xxx

Abbreviations
AOPs Advanced oxidation processes
COD Chemical oxygen demand
DAD Diode array detector
EtOH Ethanol
EPA Environmental Protection Agency
HPLC – DAD High-performance liquid chromatography with a diode array detector
HQ Hydroquinone
PBQ p-Benzoquinone
PNC p-Nitrocatechol
PNP p-Nitrophenol
PS Persulfate
OP Organic pollutant
TBA Tert-butyl alcohol
TOC Total organic carbon
UVC Ultraviolet C radiation

Commonly, these processes focus in the formation of hydroxyl radical (HO• ) as oxidizing agent. However, in the last
few years some research has been focused on the use of sulfate radical (SO4 •− ) as alternative to the hydroxyl one because
it also has a high redox potential (2.6 V for persulfate (Liang et al., 2007) versus 2.8 V for hydroxyl (Brigda, 1995)),
but a longer lifetime (3-4 × 10−5 and 2 × 10−8 s for persulfate and hydroxyl radicals, respectively) (Devi et al., 2016).
Furthermore, another important advantage associated to the use of persulfate deals with its relatively low cost and high
stability in water, therefore leading to extended reaction times and ultimately to a higher rate of pollutants oxidation
(Gokulakrishnan et al., 2012; Romero et al., 2010).
The sulfate radical can be formed by activation of persulfate through different ways, namely thermal, via basification
of the medium, by using a transition metal like iron, carbon materials or radiation (Anipsitakis and Dionysiou, 2004; Devi
et al., 2016; Gokulakrishnan et al., 2012; Matzek and Carter, 2016). Under temperatures in the range 40–99 ◦ C persulfate
is activated forming the sulfate radical (Eq. (1)) by homolysis of the peroxide bond (Rodriguez et al., 2012; Vicente et al.,
2011; Waldemer et al., 2007). In the activation by employing alkaline conditions the persulfate reacts with HO− and forms
the sulfate radical according to Eq. (2), while the last way for its activation addressed in this work involves an oxidation–
reduction process, in the presence of iron species (Eq. (3)) (Devi et al., 2016; Matzek and Carter, 2016; Waldemer et al.,
2007).

S2 O8 2− + heat → 2SO4 •− (1)

2− − 2− •− + •−
S2 O 8 + HO → SO4 + SO4 + H + O2 (2)
2− 2+ 3+ 2− •−
S2 O 8 + Fe → Fe + SO4 + SO4 (3)
Depending on the pH, the hydroxyl radical may also form according to Eq. (4) and so it can be in solution together with
the sulfate radical; the presence of both species is typically found at pH 7.0–8.5, while above 8.5–9.0 the hydroxyl species
prevail (Bennedsen et al., 2012; Devi et al., 2016; Matzek and Carter, 2016).

SO4 •− + HO− → SO4 2− + HO• (4)

The sulfate radical generated is responsible for degrading the organic pollutants (OP) yielding intermediates that are
subsequently further oxidized, hopefully into innocuous compounds like water and carbon dioxide according to Eqs. (5)
and (6).

OP + SO4 •− → OP′ (5)

′ •−
OP + SO4 → CO2 + H2 O (6)
In the open literature are found some reports wherein the activated persulfate process was applied for studying the
degradation of PNP. In these works the activation occurs by several ways such as with Zn(0) and silica gel (Chen et al.,
2018), microwave (Hu et al., 2019) or UVC (Zarei et al., 2015) radiation, with Fe/Cu bimetallic particles (Ji et al., 2017),
with carbon materials prepared from different biomass sources (Shi et al., 2018), or with sulfur-doped ordered mesoporous
carbons (Liu et al., 2020). In this study it was assessed, for the first time, the combination of thermal and alkaline conditions
with the presence of iron for persulfate activation, as well as the study of the individual processes, for the degradation
of PNP; by combining these persulfate activating techniques, improved performances are expected to be achieved as
compared to state-of-art results. Apart from that, with a detailed parametric study it was intended to found the best
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operating conditions that allow maximizing the PNP removal and the organics mineralization. Moreover, a reaction
mechanism of PNP oxidation by activated persulfate was proposed, the effect of the water matrix analyzed, and the
evaluation of the radical species present and their contribution assessed.
The selection of PNP as a model compound was due to the fact that it is listed as a priority pollutant by EPA (U.S.EPA,
1980), being nonetheless widely used in the petrochemical and chemical industries, namely in the manufacture of
drugs, dyes, explosives and fungicides (ATSDR, 1992; Ji et al., 2017); consequently, PNP is present in many wastewaters.
Inherently, it is necessary and urgent to find efficient technologies to degrade/remove it before discharging the effluents
to reduce the environmental and public health impacts caused by PNP, because it is toxic, carcinogenic and mutanogenic
(Rodrigues et al., 2017).

2. Materials and methods

2.1. Materials

PNP used in this study was purchased from Acros Organics (chemical formula C6 H5 NO4 , molecular weight 155.11 g/mol
and 99% purity), while possible intermediates compounds like p-nitrocatechol (99%), p-benzoquinone (99%), hydroquinone
(99%) and oxalic (99%), maleic (99%) and pyruvic (99%) acids were from Sigma Aldrich. Potassium persulphate (99%) was
obtained from Alfa Aesar. Ferrous sulfate heptahydrate (99%) from Panreac was used as Fe2+ catalyst. The sulfuric acid
(98%) and sodium hydroxide (98%) employed for pH correction were from Normapur and EKA, respectively. Methanol
(98%) from Normapur was employed as mobile phase in the HPLC determinations. The mix of potassium dihydrogen
phosphate (≥98%) and di-potassium hydrogen phosphate (≥98%), used as phosphate buffer, was purchased from VWR
Chemicals. The scavengers ethanol – EtOH – (≥96%) and tert-butyl alcohol – TBA – (99.5%) were from VWR Chemicals
and Sigma-Aldrich, respectively.
All solutions were prepared with distilled water.

2.2. Persulfate’s oxidation procedure

Persulfate’s oxidation experiments were carried out in a batch glass reactor equipped with a water recirculation jacket
connected to a thermostatic bath (Hubber, Polystat CC1) to maintain the temperature constant during the reactions. The
reactor was fed with 200 mL of PNP solution (with a concentration of 500 mg/L; this concentration was selected because
it was usually found in real effluents (Bhatti et al., 2002; Ji et al., 2017) and, after reaching the desired temperature
(varied in the range 30–90 ◦ C), the initial pH was adjusted (range assessed was between 3.0 to 9.0). Then, the desired
amount of potassium persulfate (from 0.8 to 9.6 g/L) was added and the reaction started, i.e. this point was considered
the time zero. In runs where a catalyst was used, immediately before adding the potassium persulfate, the ferrous sulfate
heptahydrate (dose ranged from 40 to 120 mg/L) was also added. During the oxidative process, constant stirring at 200
rpm was performed with a bar and a magnetic plate (model Falc).
Periodically, samples were taken from the reactor and immediately cooled in iced water to slow down the reaction,
once the variations in the PNP and TOC concentration measured immediately and 24 h after collecting the sample that
was kept under refrigeration at 5 ◦ C was less than 1% (data not shown); in this instant, the pH and the concentration
of PNP and total organic carbon (TOC) were immediately measured as detailed below. In some reaction experiments
where the oxidation kinetics was intentionally slowed down to determine reaction intermediates, the concentration of p-
nitrocatechol (PNC), p-benzoquinone (PBQ), hydroquinone (HQ) and oxalic, maleic and pyruvic acids were also determined,
as described in the following section.

2.3. Analytical methods

The determination of PNP concentration and the identification and quantification of the intermediate compounds
forming during the reaction, such as PNC, PBQ and HQ, were performed by high performance liquid chromatography
equipped with a DAD detector (HPLC-DAD, from Hitachi Elite LaChrom). In the determination of these compounds, a
Purospher STAR RP-18 column (5 mm, 250 × 4.0 mm) was used. A volume of 20 µL of the sample was injected, and
the isocratic method was employed, which used an eluent flow rate of 0.75 mL/min (with a composition of 90% of water
and 10% of methanol). The separation of these compounds was done at 35 ◦ C, and the detection was conducted by UV
absorbance at a wavelength of 285 and 270 nm for PNP and the other compounds, respectively.
For measuring the carboxylic acids, namely oxalic, maleic and pyruvic, the same HPLC-DAD apparatus was used, but
working at 25 ◦ C under a flow rate of 0.17 mL/min of 2.5 M H2 SO4 ; in this case, 15 µL of samples were injected. In these
determinations a Rezex ROA-Organic Acid H+ (8%) (250 × 4.6 mm) column was used and the wavelength was 210 nm.
For measuring the TOC, a Shimadzu TOC-L apparatus equipped with auto sampler (Shidmazu ASI-L) was employed.
The TOC was determined by the difference between total carbon and inorganic carbon. In this determination, the carbon
dioxide formed by catalytic oxidation of the organic carbon at 720 ◦ C is quantified in an infrared detector (method 5310D
APHA, 1998).
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The persulfate concentration remaining in solution was determined based on the method reported by other authors
(Liang et al., 2008). In this method, the absorbance at 352 nm resulting from the reaction between persulfate and iodide in
the presence of bicarbonate has been measured in a UV/visible spectrophotometer (model Helios γ , from Thermo Electron
Corporation).
The Chemical oxygen demand (COD) was measured according to method 5220D (APHA, 1998). In this method an
acid digestion, in closed reflux, was performed at 150 ◦ C during 2 h to ensure oxidation of the organic and inorganic
(susceptible to chemical oxidation) compounds by potassium dichromate; then, the absorbance corresponding to the
reduced chromium was measured at 620 nm. For this purpose, a Nanocolor Vario 4 and a Nanocolor 500D (from
Macherey-Nagel) digester and photometer, respectively, were used.
The total nitrogen was evaluated in a TNM-L apparatus from Shimadzu, being that all forms of nitrogen present
in the samples are converted into nitrogen monoxide through oxidative chemiluminescent combustion at 720 ◦ C,
whose concentration was measured in an infrared detector. The nitrite and nitrate species were quantified by molecular
absorbance spectroscopy according with methods 4500B (APHA, 1998) and and D992-71 (ASTM, 1973), respectively; in
both determinations an UV/Vis T60 spectrophotometer (from PG Instruments) was used. For NO2 − quantification it was
measured the absorbance at 537 nm of the purple color developed by reaction between this species and sulfanilamide
under acidic conditions. In NO3 − determination the intensity of the yellow color, which results from the reaction between
the nitrate and brucine, was quantified by the absorbance measurement at 410 nm.
Turbidity was evaluated by method 2130 B (APHA, 1998) using an HI88703 turbidimeter from Hanna Instruments.
The toxicity was evaluated by inhibition of Vibrio fischeri according with the standard DIN/EN/ISO 11348–3 (Standard-
zation, 2005). According with this methodology, the bacteria are put in contact with samples and incubated at 15 ◦ C; after
contact times of 5, 15 and 30 min, the bioluminescence was measured in a Microtox equipment (ModernWater, model
500).
All determination were performed in duplicated and the coefficients of variation were less than 2% for TOC, total
nitrogen and turbidity, 7% for inhibition of Vibrio Fischeri and 5% for the other parameters.

3. Results and discussion

3.1. Thermal activation

The persulfate can been activated by the temperature, as mentioned above, and therefore it is expected that this
variable has an effect in the oxidation processes efficiency, since it benefits the reaction kinetics (because the kinetic
constants increase with temperature). So, firstly, the thermal activation was evaluated in the range of 30–90 ◦ C.
Fig. 1 shows the results obtained, being possible to see that for all temperatures tested, the PNP and TOC removals, as
well as the consumption of persulfate, were faster in the first 15–30 min, while afterwards they continue to proceed slowly
up to 120 min; for higher reaction times these parameters remain nearly constant (Fig. 1 a-c). A similar temporal evolution
was observed for the pH, which considerably decreases in the first 15–30 min, and then the decay was attenuated (Fig. 1
d). The reduction of pH along reaction time is probably due to the formation of intermediate compounds like carboxylic
acids, as well as to the generation of H+ during the persulfate process according to Eq. (2); in fact, the pH decay along
reaction time has also been observed in a blank run (without PNP), which was performed at 70 ◦ C, although this decrease
was not as pronounced as the one obtained in the oxidation of the model compound (see Fig. 1 d). Romero et al. (Romero
et al., 2010) also reported a pH decay during the oxidation of diuron by the activated persulfate process with iron and
attributed this effect to the formation of H+ according to Eqs. 7 and 8. The decrease of pH was also observed by Ghauch
et al. (Ghauch et al., 2012b) during oxidation of methylene blue by thermal activation of persulfate, but any explanation
was pointed out by the authors.

SO4 •− + H2 O ↔ SO4 2− + HO• + H+ (7)

Fe3+ + x H2 O → Fe(OH)x (3−x)+ + x H+ (8)

In short reaction times (≤10 min) the PNP and TOC removals, as well as the consumption of oxidant, increase with the
temperature, and therefore the corresponding apparent second-order kinetic rate constants – kapp (linear fits shown in
Fig. S.1 of the supporting information, with R2 > 0.90) increase up to 90 ◦ C (see Table 1). However, for higher reaction
times the PNP and TOC removals almost did not improve when the reaction temperature was raised from 70 to 90 ◦ C. In
opposition, the consumption of oxidant was increased with the temperature in the whole range tested (Fig. 1). So, one
can conclude that persulfate was activated by temperature, but in what concerns process efficiency, an optimal value of
reaction temperature (70 ◦ C) was achieved. It is reasonable to expect that at 90 ◦ C the concentration of sulfate radicals
increased drastically, but this could easily promote the undesired radical scavenging reaction (Eq. (9) Chen et al., 2019; Li
et al., 2017). In other words, although a high consumption of persulfate occurs at 90 ◦ C, specially at short reaction times
(see Fig. 1c), this does not seem to benefit the process for longer times, once less amount of radicals will be available
to oxidize the PNP and intermediate compounds formed. Therefore, at the end of the reactions the PNP removal and
mineralization reached at 90 ◦ C are nearly identical to those attained at 70 ◦ C (cf. Fig. 1).
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Fig. 1. Evolution of PNP (a) and TOC (b) removals, consumption of persulfate (c) and pH of solution (d) along reaction time for different temperatures
(pHo = 5.0, [S2 O8 2− ] = 1.6 g/L and [PNP] = 500 mg/L or [PNP]blank run = 0 g/L).

Table 1
Apparent second order kinetic rate constants (kapp ) for PNP dye degradation, mineralization and
consumption of the persulfate for each temperature tested (fit for the first 10 min of process time).
Parameter kapp × 103 (L/(mmol min)
T = 30 ◦ C T = 50 ◦ C T = 70 ◦ C T = 90 ◦ C
PNP degradation 4.2 6.5 13.4 15.1
TOC removal 0.2 0.6 0.9 1.3
Consumption of persulfate 12.9 22.0 54.2 93.1

Xu et al. (2016) found, while studying the degradation of naphtenic acids by persulfate oxidation, that their mineral-
ization improved between 40–80 ◦ C, but an increase in the temperature for 97 ◦ C did not benefit the process efficiency.
The authors also report that the decrease in efficiency is due to a higher concentration of radicals generated at 97 ◦ C,
which accelerated the scavenging effect of those radicals.
SO4 •− + SO4 •− → S2 O8 2− (9)
As can be seen in Fig. S2 of the supporting information section, ln(kapp ) shows a good fit with the reverse of the absolute
temperature, with R2 higher than 0.95, showing that the thermal activation of the persulfate is accordance with the
Arrhenius law (Eq. (10)), as well as PNP degradation and organics mineralization. The activation energies found are 21.0,
27.9 and 31.2 kJ/mol for PNP oxidation, organics mineralization and consumption of the oxidant, respectively. The apparent
activation energies reached are similar to those reported by Ma et al. (25.83 kJ/mol) for the degradation of Rhodamine B
using γ -Fe2 O3 /Mn3 O4 nanocomposites for persulfate activation (Ma et al., 2019). However, other authors present much
higher values of activation energies for the degradation of PNP: from aqueous solution by heat and metal ions co-activated
persulfate (127.8 kJ/mol) (Zhang et al., 2015), from soil by thermally activated persulfate (137.29 kJ/mol) (Chen et al.,
2016), and for the activation of persulfate with temperature to generate sulfate radicals (140.26 kJ/mol) (House, 1962).
( )
Ea
− RT
kapp = k0 e (10)
In Eq. (10), ko is the pre-exponential factor, and R the ideal gas constant.
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Fig. 2. Evolution of PNP (a) and TOC (b) removals and pH of the solution (c) along reaction time for runs at different initial pHs with and without
presence of phosphate buffer (T = 70 ◦ C, [S2 O8 2− ] = 1.6 g/L, [PNP] = 500 mg/L and [H2 PO4 − ] = [HPO4 2− ]when used = 50 mmol/L).

3.2. Activation by pH

The activation of persulfate by changing the pH of the medium was also evaluated, and for that the initial pH of the
PNP solution was varied in the range 3.0 to 9.0 at a temperature of 70 ◦ C; the results obtained are depicted in Fig. 2.
Again, in all experiments the PNP removal increases rapidly in the first 15–30 min, coinciding with a fast mineralization
and decrease of pH. Both removals (PNP and TOC) continue to increase, as well as the pH decay, until 120 min. After this
period of reaction, a plateau in the efficiency of the process was again obtained.
The PNP degradation, mineralization and pH decay increase with the initial pH of the solution when this parameter
was changed from 3.0 to 5.0 and up to 7.0; however, an increase of the initial pH to 9.0 did not improve the efficiency
of persulfate’s-based oxidation. So, and to avoid the use of chemicals for further medium basification, one can consider
that best pH is 7.0, under which overall removals of ∼60 and 37% for PNP and TOC, respectively, were reached; in such
experiment, the pH decays down to 4.2.
These results allow concluding that the formation of the sulfate radical occurs according to Eq. (2), due to medium
basification. However, the existence of an optimal pH value around 7 can be explained by the fact that under excessive
basic conditions the sulfate radical reacts with HO− and forms hydroxyl radical (Eq. (4)), which has a shorter lifetime
(Devi et al., 2016; Liu et al., 2018), leading to a decreased efficiency of the process. Moreover, the carbon dioxide formed
through the organics mineralization in alkaline pH forms carbonate that is a well-known radical scavenger, has shown in
Eqs. (11)–(12), generating HCO3 • and CO3 •− that are much less reactive species (Bennedsen et al., 2012; Devi et al., 2016;
Matzek and Carter, 2016).

SO4 •− + HCO3 − → SO4 2− + HCO3 •− (11)

SO4 •− + CO23− → SO4 2− + CO3 •− (12)

The pH of 7.0 was reported by Li et al. (2017) as optimal for oxidation of PNP by persulfate’s reaction activated with
CuFe2 O4 , and the authors attribute this fact to the scavenging reactions under alkaline conditions of: (i) the sulfate radical
itself (Eq. (9)) and, (ii) between the sulfate anion and hydroxyl radicals (both species formed according to Eq. (4)). Other
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authors also report that the efficiency of the persulfate process decay for pH above 7 is due to different undesirable
scavenging reactions namely: (i) between the hydroxyl radical, which is present in solution at pH above 8.5 as mentioned
above, with the sulfate radical (Eq. (13)) (Ghauch et al., 2012a; Gu et al., 2011; Xie et al., 2012), (ii) between the hydroxyl
radical with sulfate anion (Gu et al., 2011; Liang et al., 2007) and, (iii) between the sulfate radical and the bicarbonates
and carbonates (Eqs. (11)–(12)) (Xie et al., 2012).
1
SO4 •− + HO• → HSO4 − + O2 (13)
2
Taking into account that the efficiency of the process did not increased greatly at pH 7–9 comparatively to 5, the latter
was chosen in subsequent experiments because it is the natural pH of the PNP solution; this way one can further reduce
the costs associated with chemicals (namely base) consumption for pH correction.
To assess whether the pH decay over the reaction affects process efficiency, a new run was carried out at pH 5 and
this was kept constant with the addition of phosphate buffer (H2 PO4 − and HPO4 2− with the concentration of 50 mM
of each reagent, as proposed by other authors (Huang et al., 2018; Qi et al., 2014)). As shown in Fig. 2c, the pH change
was insignificant (decreased from 5.0 to 4.9 after 180 min of reaction) compared to that observed in the run without
the addition of phosphate buffer, whose pH at the end of the reaction was 2.7. Although the pH remains nearly constant
along the reaction, a slightly decay in process efficiency was observed, once the removals of PNP and TOC reached in
the run with phosphate buffer were smaller than without the buffer (see Fig. 2a and b). This negative effect was also
reported by other authors (Qi et al., 2014), who noticed a reduction of the apparent first order kinetic constant rate for
abatement of sulfamethoxazole (from 1.06 × 101 to 3.34 × 10−2 min−1 ) and TOC reduction (from 51.1 to 31.2%) without
and with a phosphate buffer, respectively. The same tendency was observed by Ghauch et al. (Ghauch et al., 2012b) who
refers a decay of the apparent first order kinetic constant rate from 9 to 5 min−1 when using a phosphate buffer with
concentration of 48.2 mM in the oxidation of the MB dye. The reduction in process efficiency is explained by the radical
scavenging reaction, thus some sulfate radicals might have reacted with the phosphate added in solution, as reported
by other authors (Ghauch et al., 2012b; Maruthamuthu and Neta, 1978), leading to a reduction of the concentration of
radicals available to oxidize the PNP and the intermediate compounds formed.

3.3. Effect of the persulfate concentration

In AOPs it is crucial to find the best oxidant dose in order to reduce its consumption and thereby reduce the associated
costs. In this sense, experiments were performed where this parameter was varied between 0.8 g/L and 9.6 g/L –
corresponding respectively to 0.10 and 1.21 times the theoretical stoichiometric amount of persulfate required for total
removal of COD (12 gPS/g COD (Silveira et al., 2017)); runs were carried out at 70 ◦ C and initial pH of 5.0. For all
oxidant concentrations evaluated the PNP removal, mineralization, as well as the decreased of pH were again much more
pronounced in the first 15–30 min of reaction, but slowed down up to 120 min and, after this period, all remain nearly
constant (see Fig. 3).
The PNP and TOC removals along reaction time increased with the persulfate concentration up to 6.4 g/L (overall
removals achieved were 80.1% for PNP and 45.6% for TOC at the end of reaction — see Fig. 3a and b); still, this persulfate
concentration showed the highest pH decay (from 5.0 to 1.79 after 180 min — see Fig. 3c), indicating a higher formation
of carboxylic acids. The decays in the process efficiency for the persulfate concentrations of 8.0 and 9.6 g/L, having the
PNP and TOC removals at the end of reaction dropped to 72%–73% and 42%–43%, respectively, are due to the fact that
when having an excess of oxidant in solution it reacts with the sulfate radicals (Eq. (14) (Devi et al., 2016; Matzek and
Carter, 2016)). Therefore, less highly oxidative radicals are available in solution to oxidize the organic compounds (so-
called scavenging process). Previous studies reported the attainment of an optimal persulfate concentration and the same
explanation was presented (Chen et al., 2018; Hori et al., 2005; Li et al., 2017; Olmez-Hanci et al., 2013; Shang et al.,
2019). Moreover, Li et al. (2017), Olmez-Hanci et al. (2013) and Neppolian et al. (2002) report that for the doses above
the optimal (found in each study) occurs the scavenging reaction between the sulfate radical itself (Eq. (9)). Neppolian
et al. (2002) state that, in addition to the reaction between the radicals, also occurs the scavenging of the hydroxyl radical
(generated under alkaline pH according to Eq. (4)) by excess persulfate (Eq. (15)).

S2 O8 2− + SO4 •− → SO4 2− + S2 O8 •− (14)

2− • −
S2 O 8 + 2HO → 2HSO5 (15)

3.4. Iron activation

As occurs in other AOPs, the sulfate radical may be generated through the oxidant activation in the presence of a
transition metal like iron (Eq. (3)). Thus, the persulfate activation by ferrous ion and the effect of the concentration of this
catalyst were evaluated as well.
As can be seen in Fig. 4a and b, for all runs performed a rapid increase in PNP degradation and mineralization were
again observed, but now in shorter times, <15 min. After this reaction time and up to 120 min the efficiency of the
persulfate process slowed down, and afterwards the removals remained nearly constant. Concerning the evolution of pH
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Fig. 3. Evolution of PNP (a) and TOC (b) removals and pH of solution (c) along reaction time for different persulfate concentrations (pHo = 5.0,
T = 70 ◦ C, and [PNP] = 500 mg/L).

during the reaction (see Fig. 4c), a somehow similar temporal profile as compared with the removals of PNP and TOC
was recorded, so that significant decays were observed within 5–15 min (with a slower initial decay for the run with
only 40 mg/L of iron or in the iron-free experiment); such pH decline is related with the use of the iron catalyst, which
accelerates the reaction kinetics and therefore carboxylic acids are formed earlier. Again, there is the clear same pattern
in all 3 figures.
The process benefits with the presence of iron, in addition to thermal and alkaline activation, once PNP and TOC
removals increase (as well as the pH decreases more significantly) in the runs that used iron compared to the iron-
free assay (see Fig. 4). These results lead to conclude that this catalyst activates the persulfate during PNP oxidation, as
previously reported in the oxidation of other organic compounds (Long et al., 2014; Oh et al., 2009; Tan et al., 2012). The
maximum process efficiency was achieved for the dose of 80 mg/L of iron salt (removals of 94% for PNP and 65.7% for
TOC, after 180 min of reaction), which presents the highest decrease in pH (from 5.0 to 1.6 at the end of the reaction),
indicating that the kinetics of the oxidation reactions are faster, generating more carboxylic acids.
The appearance of an optimal dose of iron is explained by the fact that iron in excess reacts with the sulfate radical
according to Eq. (16) (Anipsitakis and Dionysiou, 2004; Devi et al., 2016; Matzek and Carter, 2016; Zhang et al., 2015),
and so the consumed radicals are not available in solution to oxidize either PNP or the intermediate compounds formed.
In other studies, wherein the degradation of different model compounds by activated persulfate has been evaluated, it
is also stressed that the pollutant(s) removals increased with the iron concentration up to a certain value from which it
remained constant or even decreased (Jiang et al., 2013; Liu et al., 2012; Long et al., 2014; Oh et al., 2009; Xu and Li,
2010). These authors present the same explanation previously pointed out for the existence of an optimum catalyst dose.

SO4 •− + Fe2+ → SO4 2− + Fe3+ (16)

3.5. Evaluation of the radical species presence and contribution

Two experiments with two different radical scavengers (TBA and EtOH) were carried out to assess which radical(s),
sulfate and/or hydroxyl, are present and their contribution in the oxidation process. According to Kang et al. (2018),
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C.S.D. Rodrigues and L.M. Madeira Environmental Technology & Innovation xxx (xxxx) xxx

Fig. 4. Evolution of PNP (a) and TOC (b) removals and pH of solution (c) along reaction time for different iron doses (pHo = 5.0, T = 70 ◦ C, [S2 O8 2− ]
= 6.4 g/L and [PNP] = 500 mg/L).

EtOH reacts with both radicals (sulfate and hydroxyl) at a similar reaction rate; in contrast, TBA reacts with the hydroxyl
radical at a higher reaction rate than with sulfate. In all these runs, it was used a 2.4 M concentration of the scavenger
(corresponding to a persulfate:scavenger molar ratio of 1.7, as proposed by other authors (Xian et al., 2020)), and the
operating conditions were the same as set before (T = 70 ◦ C, pH = 5.0, [S2 O8 2− ] = 6.4 g/L and [Fe2+ ] = 80 mg/L).
Fig. 5 shows that with the addition of TBA a small inhibition of both PNP and intermediate compounds oxidation occurs.
In contrast, EtOH had an considerable inhibitory effect on the oxidative process, with a decrease in process efficiency
(assessed at the end of the runs) from 94 to 55% for PNP removal and from 66 to 37% for TOC removal in the absence
and presence of EtOH, respectively. The results obtained lead to conclude that both radicals are formed during persulfate
activation, however, the radical that dominates seems to be the sulfate one, since the efficiency of the process decays
much less markedly in the presence of the scavenger of hydroxyl radical.
The results reached are in line with those reported in other studies, namely those of Liang et al. (2007) who observed
that the reduction of the pseudo-first-order rate constant for the oxidation of TCE was higher when EtOH was present in
solution as compared to the effect of TBA. The same tendency was reported by Xian et al. (2020) who noticed a reduction
of acid orange 7 dye removal from 97.3 to 20.3 and to 76.8% for EtOH and TBA, respectively, whereby the radical that
predominated is the sulfate, but the hydroxyl was also involved. Chen et al. (2018) reported the inhibition of the persulfate
oxidation process in presence of different scavengers, so it was concluded that both radicals contributed to the degradation
of PNP. However, the reduction was more significant when using L-His (universal scavenger of both radicals — HO• and
SO4 •− ) than with TBA and D-Man (scavenger of the hydroxyl radical), which indicated the predominance of SO4 •− in the
persulfate activation process.

3.6. Evaluation of the intermediate compounds formed

In the run whose performance was the best, high degradation of PNP was obtained (94%), but total mineralization
was not reached (∼66%), whereby the intermediate compounds formed and remaining in solution were evaluated.
However, only oxalic acid was found in solution (see Fig. 6a), which has a contribution of over 92% for the TOC measured
experimentally (see Table 2). The reason for that can be related with the fact this compound is difficult to oxidize.
Additionally, the persulfate concentration remaining in solution was evaluated in such experiment as well, being observed
9
C.S.D. Rodrigues and L.M. Madeira Environmental Technology & Innovation xxx (xxxx) xxx

Fig. 5. PNP (a) and TOC (b) removals as a function of reaction time with and without scavengers (pHo = 5.0, T = 70 ◦ C, [S2 O8 2− ] = 6.4 g/L, [Fe2+ ]
= 80 mg/L and [PNP] = 500 mg/L)

Fig. 6. PNP and oxalic acid concentration (a) and persulfate concentration remaining in solution (b) as a function of reaction time for the run under
the best operating conditions (pHo = 5.0, T = 70 ◦ C, [S2 O8 2− ] = 6.4 g/L, [Fe2+ ] = 80 mg/L and [PNP] = 500 mg/L).

a total consumption of the oxidant after 180 min of reaction (see Fig. 6b). So, the efficiency of oxidant used (determined
by the ratio between the TOC converted and the persulfate consumed) was 0.43 molC/mol PS.
With the goal of identifying and quantifying more and different reaction intermediates and oxidation products, a new
experiment was carried out using operating conditions that promote a slow/moderate oxidation rate (T = 30 ◦ C, pH = 5.0,
[S2 O8 2− ] = 0.8 g/L and [Fe2+ ] = 40 mg/L) to slow down the kinetics; still, the reaction time was increased till 240 min.
This slow down of the kinetics was successfully achieved since low PNP (∼27%) and TOC (∼15%) removals were achieved
after 240 min — data reported below, which were quite lower than those obtained in the optimal conditions test (94 and
66% for PNP and TOC removals, respectively, after 180 min), although with a higher efficiency of oxidant used (0.81 vs.
0.43 molC/molPS).
Studies reported in the literature show that oxidation of PNP forms compounds with higher molecular weight like
hydroquinone, p-nitrocatechol or p-benzoquinone, and carboxylic acids as final intermediates before complete oxidation
to CO2 (Chen et al., 2018; Ji et al., 2017; Kavitha and Palanivelu, 2005; Li et al., 2017; Rodrigues et al., 2018). However, the
first intermediates expected to be formed (higher molecular weight compounds) were not detected in our work, probably
because their oxidation by persulfate is very easy and occurs very quickly. Apart from PNP, only maleic, pyruvic and oxalic
acids have been found to be present in solution (see Fig. 7a).
The concentration of carboxylic acids increased up to 30 or 45 min of reaction (Fig. 7a). For the period between 45
and 180 min, the concentration of these compounds decreased, possibly due to their mineralization, and then remained
nearly constant, which coincides with the period when there is almost no oxidant in solution (see Fig. 7b) to generate
sulfate radicals. The concentration of oxalic acid was superior to the two other acids; a possible explanation is that oxalic
acid is formed not only by the degradation of organic compounds with higher molecular weight, but also by the oxidation
of maleic and pyruvic acids themselves, as shown in the proposed mechanism of PNP oxidation (Fig. 8), which takes into
account the results obtained by us and other studies reported in the literature (Chen et al., 2018; Ji et al., 2017; Kavitha
and Palanivelu, 2005; Li et al., 2017; Rodrigues et al., 2018).
Table 2 presents the concentration of each compound identified in terms of carbon and the sum of the identified
compounds, which was compared with the experimentally determined TOC values along reaction time. The carbon mass
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C.S.D. Rodrigues and L.M. Madeira Environmental Technology & Innovation xxx (xxxx) xxx

Table 2
PNP and carboxylic acids concentration in terms of carbon along reaction time, total carbon based on such identified compounds, experimental TOC
and carbon balance.
t (min) PNP Pyruvic Maleic Oxalic Total TOC Carbon
(mgC/L) (mgC/L) (mgC/L) (mgC/L) carbona (mgC/L) balanceb
(mgC/L) (%)
Under the best operating conditions
0 257.6 – – 0.0 257.6 258.4 99.7
5 81.7 – – 42.9 124.5 125.7 99.1
10 66.6 – – 49.6 116.2 116.9 99.4
15 48.9 – – 57.2 106.2 109.0 97.4
30 37.2 – – 61.9 99.1 100.3 98.8
45 27.6 – – 67.6 95.2 96.1 99.1
60 23.0 – – 69.5 92.5 93.4 99.1
90 16.5 – – 69.3 85.8 91.9 93.3
120 15.1 – – 67.2 82.3 88.9 92.5
180 15.1 – – 67.0 82.1 88.6 92.6
Under operating conditions that slow down the kinetics
0 257.5 0.0 0.0 0.0 257.6 258.1 99.8
5 220.3 4.2 2.1 11.2 237.8 247.9 95.9
10 214.3 4.8 3.2 11.9 234.3 246.1 95.2
15 210.5 5.4 3.9 12.9 232.8 241.3 96.5
30 207.3 6.4 4.9 14.5 233.2 236.4 98.6
45 204.4 5.8 4.1 16.3 230.5 235.8 97.8
60 200.5 5.1 3.6 15.5 224.8 232.9 96.6
90 196.8 4.6 3.1 14.7 219.2 227.0 96.5
120 193.0 4.3 2.7 13.8 213.8 222.3 96.2
180 190.9 4.1 2.2 13.5 210.7 218.5 96.4
240 188.4 4.1 2.2 13.4 208.2 218.2 95.4
a
Total carbon assessed from the sum of the identified compounds.
b
Total carbon/TOC × 100.

Fig. 7. PNP and carboxylic acids concentration (a) and persulfate concentration remaining in solution (b) as a function of reaction time for the run
under operating conditions that slow down the kinetic (pHo = 5.0, T = 30 ◦ C, [S2 O8 2− ] = 0.8 g/L, [Fe2+ ] = 40 mg/L and [PNP] = 500 mg/L).

balance allows to conclude that the identified and quantified carboxylic acids in solution represent well the TOC measured,
with a contribution of higher than 95%.

3.7. p-nitrophenol degradation in domestic wastewater matrix

In this study, the effect of the water matrix was also evaluated, with the goal of assessing whether the degradation
of PNP is affected or not in a complex water matrix containing anions such as carbonates, chlorides and nitrates, which
are scavengers of the persulfate radical. For that purpose, a run was carried out using a domestic effluent, collected in a
wastewater treatment plant located in the northern region of Portugal, which was spiked with 500 mg/L of PNP. Table 3
shows the characteristics of the contaminated wastewater; it should be noted that the TOC increased about 1.7 times
as compared with the PNP solution. The degradation of PNP in the wastewater matrix, in the first 90 min of reaction,
proceeded at a lower rate as compared to that obtained in distilled water (see Fig. 9a); this reduction is possibly due to
the degradation of other organic compounds present in the wastewater (competition effect), which leads to a decrease
11
C.S.D. Rodrigues and L.M. Madeira Environmental Technology & Innovation xxx (xxxx) xxx

Fig. 8. Proposed reaction mechanism of PNP degradation by thermal, pH and/or ferrous catalyst activation of persulfate.

Table 3
Characterization of domestic wastewater containing PNP before and after activated persulfate process.
Parameters Before treatment After treatmenta Removal (%)
pH 6.2 7.0 –
Turbidity (NTU) 95 16 83.2
TOC (mgC/L) 425.6 113.5 73.3
COD (mgO2 /L) 1299.4 380.4 70.7
NO2 − (mgN/L) 0.04 0.03 25.0
NO3 − (mgN/L) 0.6 31.8 –
Ntotal (mgN/L) 98.8 96.0 2.9
Inhibition of Vibrio fischeri at 5 min 40 0.0 100
Inhibition of Vibrio fischeri at 15 min 48 0.0 100
Inhibition of Vibrio fischeri at 30 min 57 0.0 100
a
After neutralization.

in the amount of sulfate radicals available to oxidize PNP. However, for higher reaction times, the difference in removals
reached in both matrixes was attenuated, being almost equal at the end of the reaction (Fig. 9a).
The mineralization, as occurs in PNP solution, increased rapidly for short reaction times, increasing very slowly for t >
30 min (see Fig. 9b), being reached a TOC removal of 73.3% after 180 min, which was slightly higher than the one achieved
in the run with PNP only. This improved mineralization can be attributed to the organic matter present in real wastewater,
which might be easier to mineralize by the sulfate radicals than the by-products formed upon PNP degradation.
Characterization of the real wastewater spiked with PNP after 180 min of reaction was performed, being observed
a high reduction of COD and turbidity from 1299.4 to 380.4 mgO2 /L and 95 to 16 NTU (see Table 3), respectively,
corresponding to a reduction of ca. 71 and 83%. Regarding the nitrogen forms, reduction of total nitrogen and nitrite of
about 3% and 25% were respectively observed. The concentration of nitrates increased from 0.6 to 31.8 mgN/L (Table 2),
which is possibly associated with the oxidation of nitrite (released into the solution when PNP was oxidized) to nitrate by
the sulfate and hydroxyl radicals (Eqs. (17) and (18)) (Khan and Adewuyi, 2010). Moreover, a nontoxic wastewater was
12
C.S.D. Rodrigues and L.M. Madeira Environmental Technology & Innovation xxx (xxxx) xxx

Fig. 9. Removals of PNP (a) and TOC (b) as a function of reaction time for PNP solution and domestic effluent spiked with PNP (pHo = 5.0, T = 70 ◦ C,
[S2 O8 2− ] = 6.4 g/L, [Fe2+ ] = 80 mg/L and [PNP] = 500 mg/L).

generated after the activated persulfate process, since the inhibition of Vibrio fischeri was totally eliminated.

NO2 − + SO4 •− → SO4 2− + NO2 (17)

• − +
NO2 + HO → NO3 + H (18)

4. Conclusions

This work focused on the evaluation of the degradation and mineralization of PNP by the sulfate radical generated by
thermal, alkaline conditions or with iron, as well as on finding the best operating condition of each individual process.
The results obtained led to conclude that the three pathways studied activate the persulfate, and of course the overall
process with the conjugation of all these activation procedures is quite effective.
The main process parameters (temperature, initial pH, persulfate concentration and iron dose) affecting the efficiency
of the process were assessed. For short reactions times (<10 min) the PNP and TOC removals, as well as the consumption
of persulfate, increased with the temperature and followed a second-order kinetics (r2 > 0.90); the apparent activation
energies were found to be 21.0, 27.9 and 31.2 kJ/mol, respectively. The addition of a phosphate buffer allowed the pH not
to decay, but it did not benefit the oxidative process, with a decrease in the TOC and PNP removals. When the processes
was carried out under the best operating conditions found (pH = 5.0, T = 70 ◦ C, [S2 O8 2− ] = 6.4 g/L and [Fe2+ ] = 80
mg/L) it was possible to obtain, after 180 min of reaction, a PNP removal of 94% and considerable mineralization (66%).
Thus, it is possible to state that the persulfate oxidation catalyzed with ferrous iron and activated by temperature and pH
is a promising technique for the degradation of p-nitrophenol.
In presence of EtOH and TBA scavengers, the oxidation process efficiency decreased, which suggests that the sulfate
radical predominates in the persulfate activation process (although the hydroxyl radical also plays a role).
A PNP degradation mechanism was proposed and the organic compounds found in solution were mainly carboxylic
acids (short chain compounds), whose contribution for the TOC was higher than 95% along the oxidation process.
The use of an urban wastewater instead of distilled water did not affect the performance of the activated persulfate
oxidation process, allowing to conclude that such water matrix almost did not influence the oxidation of PNP.
Future work should address important issues like the use of heterogeneous processes (to avoid the generation of iron-
containing sludge as occurs in the homogeneous one), the use of statistical tools (e.g. design of experiments) for process
optimization, with reduced experimental effort and a detailed techno-economic analysis.

CRediT authorship contribution statement

Carmen S.D. Rodrigues: Validation, Investigation, Writing original draft, Conceptualization. Luis M. Madeira: Concep-
tualization, Funding acquisition, Resources, Writing - review & editing.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
13
C.S.D. Rodrigues and L.M. Madeira Environmental Technology & Innovation xxx (xxxx) xxx

Acknowledgments

This work was financially supported by: Base Funding - UIDB/00511/2020 of the Laboratory for Process Engineering,
Environment, Biotechnology and Energy – LEPABE - funded by national funds through the FCT/MCTES (PIDDAC). Carmen
S.D. Rodrigues thanks the Portuguese Foundation for Science and Technology (FCT) for the financial support of her work
contract through the Scientific Employment Support Program (Norma Transitória DL 57/2017).

Appendix A. Supplementary data

Supplementary material related to this article can be found online at https://doi.org/10.1016/j.eti.2020.101265.

References

Anipsitakis, G.P., Dionysiou, D.D., 2004. Radical generation by the interaction of transition metals with common oxidants. Environ. Sci. Technol. 38
(13), 3705–3712.
APHA, A., WEF, 1998. StandArd Methods for the Examination of Water and Wastewater. American Public Health Association, American Water Works
Association, Water Pollution Control Federation, Washington DC.
ASTM, 1973. Annual Book of ASTM Standards - Part 23 - Water; Atmospheric Analysis. American Society of Testing and Materials, Philadelphia.
ATSDR, 1992. Toxicological Profile for Nitrophenols: 2-Nitrophenol and 4-Nitrophenol. Public Agency for Toxic Substances and Disease Registry, Health
Service, Atlanta, GA, USA.
Bennedsen, L.R., Muff, J., Søgaard, E.G., 2012. Influence of chloride and carbonates on the reactivity of activated persulfate. Chemosphere 86 (11),
1092–1097.
Bhatti, Z.I., Toda, H., Furukawa, K., 2002. P-nitrophenol degradation by activated sludge attached on nonwovens. Water Res. 36 (5), 1135–1142.
Brigda, R.J., 1995. Consider fenton’s chemistry for wastewater treatment. Chem. Eng. Process. 91, 62–66.
Chen, C., Han, Y., Guo, J., Zhou, L., Lan, Y., 2018. Assessing the role of silica gel in the degradation of p-nitrophenol via zn(0)-activated persulfate. J.
Taiwan Inst. Chem. Eng. 88, 169–176.
Chen, T., Ma, J., Zhang, Q., Xie, Z., Zeng, Y., Li, R., Liu, H., Liu, Y., Lv, W., Liu, G., 2019. Degradation of propranolol by UV-activated persulfate oxidation:
Reaction kinetics, mechanisms, reactive sites, transformation pathways and Gaussian calculation. Sci. Total Environ. 690, 878–890.
Chen, X., Murugananthan, M., Zhang, Y., 2016. Degradation of p-nitrophenol by thermally activated persulfate in soil system. Chem. Eng. J. 283,
1357–1365.
Devi, P., Das, U., Dalai, A.K., 2016. In-situ chemical oxidation: Principle and applications of peroxide and persulfate treatments in wastewater systems.
Sci. Total Environ. 571, 643–657.
Ghauch, A., Tuqan, A.M., Kibbi, N., 2012a. Ibuprofen removal by heated persulfate in aqueous solution: A kinetics study. Chem. Eng. J. 197, 483–492.
Ghauch, A., Tuqan, A.M., Kibbi, N., Geryes, S., 2012b. Methylene blue discoloration by heated persulfate in aqueous solution. Chem. Eng. J. 213,
259–271.
Gokulakrishnan, S., Parakh, P., Prakash, H., 2012. Degradation of malachite green by potassium persulphate, its enhancement by 1, 8-dimethyl-1, 3,
6, 8, 10, 13-hexaazacyclotetradecane nickel(II) perchlorate complex, and removal of antibacterial activity. J. Hard Mater. 213–214, 19–27.
Gu, X., Lu, S., Li, L., Qiu, Z., Sui, Q., Lin, K., Luo, Q., 2011. Oxidation of 1, 1, 1-trichloroethane stimulated by thermally activated persulfate. Ind. Eng.
Chem. Res. 50 (19), 11029–11036.
Hori, H., Yamamoto, A., Hayakawa, E., Taniyasu, S., Yamashita, N., Kutsuna, S., Kiatagawa, H., Arakawa, R., 2005. Efficient decomposition of
environmentally persistent perfluorocarboxylic acids by use of persulfate as a photochemical oxidant. Environ. Sci. Technol. 39 (7), 2383–2388.
House, D.A., 1962. Kinetics and mechanism of oxidations by peroxydisulfate. Chem. Rev. 62 (3), 185–203.
Hu, L., Zhang, G., Wang, Q., Wang, X., Wang, P., 2019. Effect of microwave heating on persulfate activation for rapid degradation and mineralization
of p-nitrophenol. ACS Sustain. Chem. Eng. 7 (13), 11662–11671.
Huang, B.-C., Jiang, J., Huang, G.-X., Yu, H.-Q., 2018. Sludge biochar-based catalysts for improved pollutant degradation by activating peroxymonosulfate.
J. Mater. Chem. A 6 (8978).
Ji, Q., Li, J., Xiong, Z., Lai, B., 2017. Enhanced reactivity of microscale fe/cu bimetallic particles (mfe/cu) with persulfate (PS) for p-nitrophenol (PNP)
removal in aqueous solution. Chemosphere 172, 10–20.
Jiang, X., Wu, Y., Wang, P., Li, H., Dong, W., 2013. Degradation of bisphenol a in aqueous solution by persulfate activated with ferrous ion. Environ.
Sci. Pollut. Res. 20 (7), 4947–4953.
Kang, Y.-G., Vu, H.C., Le, T.T., Chang, Y.-S., 2018. Activation of persulfate by a novel fe(II)-immobilized chitosan/alginate composite for bisphenol a
degradation. Chem. Eng. J. 353, 736–745.
Kavitha, V., Palanivelu, K., 2005. Degradation of nitrophenols by fenton and photo-fenton processes. J. Photochem. Photobiol. A: Chem. 170 (1), 83–95.
Khan, N.E., Adewuyi, Y.G., 2010. Absorption and oxidation of nitric oxide (NO) by aqueous solutions of sodium persulfate in a bubble column reactor.
Ind. Eng. Chem. Res. 49 (18), 8749–8760.
Li, J., Ren, Y., Ji, F., Lai, B., 2017. Heterogeneous catalytic oxidation for the degradation of p-nitrophenol in aqueous solution by persulfate activated
with cufe2o4 magnetic nano-particles. Chem. Eng. J. 324, 63–73.
Liang, C., Huang, C.-F., Mohanty, N., Kurakalva, R.M., 2008. A rapid spectrophotometric determination of persulfate anion in ISCO. Chemosphere 73
(9), 1540–1543.
Liang, C., Wang, Z.-S., Bruell, C.J., 2007. Influence of pH on persulfate oxidation of TCE at ambient temperatures. Chemosphere 66 (1), 106–113.
Liu, S., Lai, C., Li, B., Zhang, C., Zhang, M., Huang, D., Qin, L., Yi, H., Liu, X., Huang, F., Zhou, X., Chen, L., 2020. Role of radical and non-radical pathway
in activating persulfate for degradation of p-nitrophenol by sulfur-doped ordered mesoporous carbon. Chem. Eng. J. 384, 123304.
Liu, L., Lin, S., Zhang, W., Farooq, U., Shen, G., Hu, S., 2018. Kinetic and mechanistic investigations of the degradation of sulfachloropyridazine in
heat-activated persulfate oxidation process. Chem. Eng. J. 346, 515–524.
Liu, C.S., Shih, K., Sun, C.X., Wang, F., 2012. Oxidative degradation of propachlor by ferrous and copper ion activated persulfate. Sci. Total Environ.
416, 507–512.
Long, A., Lei, Y., Zhang, H., 2014. Degradation of toluene by a selective ferrous ion activated persulfate oxidation process. Ind. Eng. Chem. Res. 53
(3), 1033–1039.
Ma, Q., Zhang, X., Guo, R., Zhang, H., Cheng, Q., Xie, M., Cheng, X., 2019. Persulfate activation by magnetic γ -Fe2O3/Mn3o4 nanocomposites for
degradation of organic pollutants. Sep. Purif. Technol. 210, 335–342.
Maruthamuthu, P., Neta, P., 1978. Phosphate radicals, spectra, acid–base equilibriums, and reactions with inorganic compounds. J. Phys. Chem. 82
(6), 710–713.

14
C.S.D. Rodrigues and L.M. Madeira Environmental Technology & Innovation xxx (xxxx) xxx

Matzek, L.W., Carter, K.E., 2016. Activated persulfate for organic chemical degradation: A review. Chemosphere 151, 178–188.
Neppolian, B., Jung, H., Choi, H., Lee, J.H., Kang, J.-W., 2002. Sonolytic degradation of methyl tert-butyl ether: the role of coupled fenton process and
persulphate ion. Water Res. 36 (19), 4699–4708.
Oh, S.-Y., Kim, H.-W., Park, J.-M., Park, H.-S., Yoon, C., 2009. Oxidation of polyvinyl alcohol by persulfate activated with heat, Fe2+, and zero-valent
iron. J. Hard Mater. 168 (1), 346–351.
Olmez-Hanci, T., Arslan-Alaton, I., Genc, B., 2013. Bisphenol a treatment by the hot persulfate process: Oxidation products and acute toxicity. J. Hard
Mater. 263, 283–290.
Oturan, M.A., Aaron, J.-J., 2014. Advanced oxidation processes in water/wastewater treatment: Principles and applications. a review. Crit. Rev. Environ.
Sci. Technol. 44 (23), 2577–2641.
Qi, C., Liu, X., Lin, C., Zhang, X., Ma, J., Tan, H., Ye, W., 2014. Degradation of sulfamethoxazole by microwave-activated persulfate: Kinetics, mechanism
and acute toxicity. Chem. Eng. J. 249, 6–14.
Rodrigues, C.S.D., Borges, R.A.C., Lima, V.N., Madeira, L.M., 2018. P-nitrophenol degradation by fenton’s oxidation in a bubble column reactor. J.
Environ. Manag. 206, 774–785.
Rodrigues, C.S.D., Soares, O.S.G.P., Pinho, M.T., Pereira, M.F.R., Madeira, L.M., 2017. P-nitrophenol degradation by heterogeneous fenton’s oxidation
over activated carbon-based catalysts. Appl. Catal. B 219, 109–122.
Rodriguez, S., Santos, A., Romero, A., Vicente, F., 2012. Kinetic of oxidation and mineralization of priority and emerging pollutants by activated
persulfate. Chem. Eng. J. 213, 225–234.
Romero, A., Santos, A., Vicente, F., González, C., 2010. Diuron abatement using activated persulphate: Effect of pH, fe(II) and oxidant dosage. Chem.
Eng. J. 162 (1), 257–265.
Shang, W., Dong, Z., Li, M., Song, X., Zhang, M., Jiang, C., Feiyun, S., 2019. Degradation of diatrizoate in water by fe(II)-activated persulfate oxidation.
Chem. Eng. J. 361, 1333–1344.
Shi, C., Li, Y., Feng, H., Jia, S., Xue, R., Li, G., Wang, G., 2018. Removal of p-nitrophenol using persulfate activated by biochars prepared from different
biomass materials. Chem. Res. Chin. Univ. 34 (1), 39–43.
Silveira, J.E., Paz, W.S., Garcia-Muñoz, P., Zazo, J.A., Casas, J.A., 2017. UV-LED/ilmenite/persulfate for azo dye mineralization: The role of sulfate in the
catalyst deactivation. Appl. Catal. B 219, 314–321.
Standardzation, I.O.f., 2005. Water quality - determination of the inhibitory effect of water method, samples on the light emission of vibrio fischeri
(luminescent bacteria test) - part 3: Using freeze-dried bacteria.
Tan, C., Gao, N., Chu, W., Li, C., Templeton, M.R., 2012. Degradation of diuron by persulfate activated with ferrous ion. Sep. Purif. Technol. 95, 44–48.
U.S.EPA, 1980. 4-Nitrophenol. H.a.E.E.P.N. 135 (Ed.). Government Printing Office, District of Columbia, U.S.
Vicente, F., Santos, A., Romero, A., Rodriguez, S., 2011. Kinetic study of diuron oxidation and mineralization by persulphate: Effects of temperature,
oxidant concentration and iron dosage method. Chem. Eng. J. 170 (1), 127–135.
Waldemer, R.H., Tratnyek, P.G., Johnson, R.L., Nurmi, J.T., 2007. Oxidation of chlorinated ethenes by heat-activated persulfate: Kinetics and products.
Environ. Sci. Technol. 41 (3), 1010–1015.
Xian, G., Niu, L., Zhang, G., Zhou, N., Long, Z., Zhi, R., 2020. An efficient cuo-γ Fe2O3 composite activates persulfate for organic pollutants removal:
Performance, advantages and mechanism. Chemosphere 242, 125191.
Xie, X., Zhang, Y., Huang, W., Huang, S., 2012. Degradation kinetics and mechanism of aniline by heat-assisted persulfate oxidation. J. Environ. Sci.
24 (5), 821–826.
Xu, X.-R., Li, X.-Z., 2010. Degradation of azo dye orange g in aqueous solutions by persulfate with ferrous ion. Sep. Purif. Technol. 72 (1), 105–111.
Xu, X., Pliego, G., Zazo, J.A., Casas, J.A., Rodriguez, J.J., 2016. Mineralization of naphtenic acids with thermally-activated persulfate: The important role
of oxygen. J. Hard Mater. 318, 355–362.
Zarei, A.R., Rezaeivahidian, H., Soleymani, A.R., 2015. Investigation on removal of p-nitrophenol using a hybridized photo-thermal activated persulfate
process: Central composite design modeling. Process Saf. Environ. Prot. 98, 109–115.
Zhang, M., Chen, X., Zhou, H., Murugananthan, M., Zhang, Y., 2015. Degradation of p-nitrophenol by heat and metal ions co-activated persulfate.
Chem. Eng. J. 264, 39–47.

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