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HAZMAT-17483; No. of Pages 9 ARTICLE IN PRESS

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Contents lists available at ScienceDirect

Journal of Hazardous Materials

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

Salicylic acid degradation by advanced oxidation processes. Coupling

of solar photoelectro-Fenton and solar heterogeneous photocatalysis
Benjamin Garza-Campos a , Enric Brillas b , Aracely Hernández-Ramírez a ,
Abdellatif El-Ghenymy b , Jorge Luis Guzmán-Mar a , Edgar J. Ruiz-Ruiz a,∗,1
a
Universidad Autónoma de Nuevo León, Facultad de Ciencias Químicas, Av. Pedro de Alba, Ciudad Universitaria, San Nicolás de los Garza, Nuevo León,
Mexico
b
Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i
Franquès 1-11, 08028 Barcelona, Spain

h i g h l i g h t s

• Uniform and mechanical stables TiO2 films on glass spheres were made by sol-gel dip-coating.
• Design and use of 3 L flow reactor for applying SPEF and heterogeneous SPC.
• Synergistic effect on the removal of salicylic acid by coupled SPC with EAOPs.
• Lower energetic cost for salicylic acid mineralization with SPEF-SPC than SPEF.
• Better mineralization current efficiency in all treatments using SPEF-SPC process.

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

Article history: A 3.0 L solar flow plant with a Pt/air-diffusion (anode/cathode) cell, a solar photoreactor and a
Received 14 October 2015 photocatalytic photoreactor filled with TiO2 -coated glass spheres has been utilized to couple solar
Received in revised form 21 January 2016 photoelectro-Fenton (SPEF) and solar heterogeneous photocatalysis (SPC) for treating a 165 mg L−1 sali-
Accepted 21 February 2016
cylic acid solution of pH 3.0. Organics were destroyed by • OH radicals formed on the TiO2 photocatalyst
Available online xxx
and at the Pt anode during water oxidation and in the bulk from Fenton’s reaction between added Fe2+
and cathodically generated H2 O2 , along with the photolytic action of sunlight. Poor salicylic acid removal
Keywords:
and mineralization were attained using SPC, anodic oxidation with electrogenerated H2 O2 (AO-H2 O2 )
Coupled process
Salicylic acid
and coupled AO-H2 O2 -SPC. The electro-Fenton process accelerated the substrate decay, but with low
Solar heterogeneous photocatalysis mineralization by the formation of byproducts that are hardly destroyed by • OH. The mineralization was
Solar photoelectro-Fenton strongly increased by SPEF due to the photolysis of products by sunlight, being enhanced by coupled
Water treatment SPEF-SPC due to the additional oxidation by • OH at the TiO2 surface. The effect of current density on
the performance of both processes was examined. The most potent SPEF-SPC process at 150 mA cm−2
yielded 87% mineralization and 13% current efficiency after consuming 6.0 Ah L−1 . Maleic, fumaric and
oxalic acids detected as final carboxylic acids were completely removed by SPEF and SPEF-SPC.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction such as steroids and hormones, pharmaceuticals, drugs, cosmet-

Over the last two decades, there exists a great scientific and tech-
nological interest for the remediation of waters contaminated with
emerging pollutants to avoid its spreading into the aquatic environ-
ment. This kind of pollutants includes a large variety of compounds
∗ Corresponding author.
E-mail address: edgar.ruizrz@uanl.edu.mx (E.J. Ruiz-Ruiz).
1
URL: http://www.uanl.mx
ics and industrial additives and agents, among others, which are
characterized because they are not yet regulated or under scarce
water-quality regulation and represent potential threats to envi-
ronmental ecosystems and human health and safety [1]. A common
emerging pollutant is salicylic acid (2-hydroxybenzoic acid), largely
employed worldwide in many cosmetic, dermatological, food and
pharmaceutical formulations. It is the main precursor and the major
metabolite of the well-known drug aspirin. Due to its widespread
use, salicylic acid has been detected up to relatively high contents of

http://dx.doi.org/10.1016/j.jhazmat.2016.02.050
0304-3894/© 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: B. Garza-Campos, et al., Salicylic acid degradation by advanced oxidation processes. Coupling of solar
photoelectro-Fenton and solar heterogeneous photocatalysis, J. Hazard. Mater. (2016), http://dx.doi.org/10.1016/j.jhazmat.2016.02.050
G Model
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50 ␮g L−1 in rivers, urban wastewaters and influents and effluents
of wastewater treatment plants of many countries [2–7].
Most of emerging pollutants cannot be completely removed by
microbiological and/or conventional physico-chemical treatments
[1], then being necessary the development of potent oxidation
processes to ensure their total elimination from waters. The use
of advanced oxidation processes (AOPs) has been postulated as
a plausible solution for the remediation of waters contaminated
with organic pollutants [1,8–13]. The effectiveness of AOPs is due
to the in situ production of free radicals, mainly hydroxyl radical
(• OH), which is the second stronger oxidant known after fluo-
rine, with a high standard reduction potential (E0 = 2.80 V/SHE).
The electrophilic character of • OH radical permits its rapid and
non-selective reaction with most electron-rich organic compounds
up to their mineralization. The large variety of AOPs, which
include chemical, photochemical, electrochemical and photoelec-
trochemical methods, offers different ways for • OH production,
thus allowing a better compliance with the specific treatment
requirements [12].
Heterogeneous photocatalysis (PC) has become an important
AOP in the last years because of its ability for the destruction of
low amounts of water-soluble organic pollutants [14–17]. TiO2
nanoparticles, mainly in the anatase phase, are preferred for this
process, although other semiconductor materials like ZnO, WO3 ,
CdS, ZnS, SrTiO3 and SnO2 have also been utilized. Illumination
of a TiO2 surface (band-gap energy of 3.2 eV) by an UV light of
␭ < 380 nm promotes an electron from the filled valence band (e− cb )
to the conduction band and produces a positively charged vacancy
or hole (h+ vb ) by Reaction (1). The holes can react with water or
OH− to give • OH from Reactions (2) and (3), respectively, which is
the responsible of organics degradation. However, the recombina-
tion of the electron/hole pair from Reaction (4) and • OH reduction
with the electron from Reaction (5) are important waste reactions
that cause a large loss in efficiency in PC [16,17].
TiO2 + h → e− cb + h+ vb
h+ vb + H2 O → • OH + H+
h+ vb + OH− → • OH
− +
e cb +h vb → TiO2 + heat
e− cb + • OH → OH−
The main drawback of PC for practical application is the high
electrical cost of the UV lamps utilized. This is solved by means
of the solar PC (SPC) process using the free radiation from sunlight
with ␭ > 300 nm [14,15]. In this AOP, TiO2 nanoparticles are utilized
as a suspended powder, thus possessing a great efficiency for the
photocatalytic degradation of pollutants in waters [9]. However,
this presupposes a serious limitation for large scale application
since separation of the suspended material by filtration is required
after treatment. Another key problem occurs when photocatalysis
is coupled with an electrochemical process, because the electro-
static charge of TiO2 nanoparticles can induce their adherence to
the electrodes and can cause their passivation [18]. These disadvan-
tages can be solved if the TiO2 photocatalyst is immobilized onto a
solid substrate like glass sphere, glass tube, fiberglass, activated car-
bon and silica by sputtering, sol-gel dip-coating or electrophoretic
deposition [15]. Nevertheless, the use of immobilized TiO2 films in
a small surface reduces significantly the photocatalytic efficiency
for organic removal compared with that of TiO2 nanoparticles that
are suspended in all the solution.
Electrochemical AOPs (EAOPs) like anodic oxidation (AO),
electro-Fenton (EF) and photoelectro-Fenton (PEF) have also
received great attention for water remediation [1,10–13]. In
AO, organics are destroyed: (i) by physisorbed hydroxyl radical
Please cite this article in press as: B. Garza-Campos, et al., Salicylic acid degradation by advanced oxidation processes. Coupling of solar
photoelectro-Fenton and solar heterogeneous photocatalysis, J. Hazard. Mater. (2016), http://dx.doi.org/10.1016/j.jhazmat.2016.02.050
(M(• OH)) formed on an active anode with high O2 -overvoltage
evolution (M) such as SnO2 , PbO2 or boron-doped diamond (BDD)
electrode by water oxidation from Reaction (6) or (ii) by super-
oxide radicals produced by the reaction of hydroxyl radicals with
active anodes such as Pt, RuO2 and IrO2 from Reactions (7) and
(8) [13,19–21]. A variant of this method is AO with electrogener-
ated H2 O2 (AO-H2 O2 ) in which this weak oxidant is produced from
the two-electron reduction of O2 gas by Reaction (9), usually at
carbonaceous cathodes like graphite felt [22], carbon felt [23–25],
carbon-polytetrafluoroethylene (PTFE) O2 or air-diffusion [26–28],
activated carbon fiber [29], carbon nanotubes [30] and BDD [31,32].
The EF process enhances the oxidation power of H2 O2 by addition
of Fe2+ ion in catalytic amounts to produce • OH in the bulk from
Fenton’s Reaction (10) with optimum pH near 2.8 [12,33,34]. Reac-
tive oxygen species (ROS) such as H2 O2 and its oxidation product
the hydroperoxyl radical (HO2 • ), M(• OH) and • OH in the bulk can
then attack the organics in EF [12,13,23–25]. The oxidation ability
of EF can be upgraded by irradiating the solution with an UV light or
sunlight by the so-called PEF or solar (PEF) processes, respectively
[28,29,35–39]. The radiation promotes the regeneration of Fe2+
with more • OH production from the photolysis of Fe(OH)2+ species,
predominant at pH 3, by Reaction (11) and the photodecomposi-
tion of generated Fe(III)-carboxylate complexes by Reaction (12)
[28,33].
M + H2 O → M(• OH) + H+ + e− (6)
MOx(• OH) → MOx+1 + H + e + −
(7)
MOx+1 + R → M + RO (8)
+ −
O2(g) + 2 H + 2e → H2 O2 (9)
H2 O2 + Fe2+ + H+ → Fe3+ +H2 O + • OH (10)
Fe(OH) 2+
+ hv → Fe 2+
+ • OH (11)
(1) Fe(OOCR) 2+
+ hv → Fe 2+
+ CO2 + R• (12)
(2) In an undivided cell, the efficiency of EAOPs depends on the
oxidizing ability of M(• OH) species generated at the anode and
(3) the ability of the cathode to produce H2 O2 . It has been found
that the best anode is BDD because of the higher oxidation power
(4) of BDD(• OH) than other physisorbed radicals, whereas O2 or air-
(5) diffusion cathodes allows the accumulation of the greatest amounts
of H2 O2 in solution [12,25,40,41]. In previous work [42], the degra-
dation of 100 mL of 165 mg L−1 salicylic acid solutions was studied
by AO-H2 O2 , EF, PEF and SPEF using an undivided cell with a Pt or
BDD anode and an O2 -diffusion cathode. The most powerful process
was SPEF, which yielded 98% total organic carbon (TOC) removal,
regardless of the anode used, operating at 100 mA with 0.2–1.0 mM
Fe2+ and pH 3.0–4.0 as optimum conditions. More recently, we
introduced the possibility of coupling SPEF with SPC in the treat-
ment of 200 mL of 20 mg L−1 atrazine in 0.05 M Na2 SO4 at pH 3.0
using a BDD/BDD tank reactor with 180 TiO2 -coated glass spheres
[43]. The synergistic effect of both coupled processes was well
proven by adding 0.1 mM Fe2+ and 80% mineralization as maxi-
mal was achieved after 300 min of electrolysis at 100 mA. In view
of these relevant findings, we have built a flow plant of 3.0 L for
the degradation of organics in wastewaters by coupled SPEF-SPC
in order to show the viability of this novel technology at industrial
scale. The flow plant contained a Pt/air-diffusion (anode/cathode)
filter-press cell and two planar solar photoreactors for the sepa-
rated and coupled use of SPEF and SPC, respectively. Pt was chosen
instead of BDD because a similar effectiveness of both anodes was
expected under the potent action of sunlight [42].
This paper presents the results obtained for the degradation
of 3.0 L of a 165 mg L−1 salicylic acid (100 mg L−1 TOC) solution
in sulfate medium of pH 3.0 in the above flow plant. The role of
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the different oxidizing species generated was clarified using sin-
gle processes like SPC, AO-H2 O2 , EF and SPEF and coupled ones
like AO-H2 O2 -SPC and SPEF-SPC. The influence of j on the oxida-
tion ability of SPEF and SPEF-SPC was also examined. The evolution
of the final short-linear aliphatic carboxylic acids was followed by
ion-exclusion HPLC.
2. Experimental
2.1. Chemicals
Analytical grade salicylic acid (>99% purity) was purchased
from Panreac and used without further purification. Standards of
carboxylic acids were supplied by Sigma-Aldrich and Avocado.
Anhydrous sodium sulfate was of analytical grade supplied by VWR
International. Ferrous sulfate heptahydrate (99% purity) was pur-
chased from Jalmek. Analytical grade sulfuric acid from Merck was
used to adjust the initial solution pH to 3.0. Titanium butoxide Ti
(97% purity) and sec-butyl alcohol (99.5% purity) were supplied
by Fluka and Tedia, respectively. Ultrapure water from a Millipore
Milli-Q system (resistivity > 18 M cm) was used to prepare all the
solutions. Other chemicals used were either of HPLC or analytical
grade purchased from Merck, Fluka and Avocado.
2.2. Synthesis and deposition of TiO2 on glass spheres
The TiO2 photocatalyst was synthesized by the sol–gel method
using titanium butoxide as precursor and sec-butyl alcohol as a
solvent [44] and subsequently deposited onto glass spheres by
the dip-coating technique [43]. Briefly, 14.7 mL of precursor were
added to 45 mL of ethanol and the pH was adjusted to 3 by drop
wise addition of glacial acetic acid under stirring. A mixture of
3 mL of water and 40 mL of ethanol was separately prepared and
added drop wise to the above solution. The resulting solution was
stirred for 24 h giving rise to a sol, which was then used to pre-
pare TiO2 coatings on borosilicate glass spheres of 5 mm diameter
purchased from Marienfeld by the dip-coating technique, followed
by calcination at 500 ◦ C during 1 h in a Thermoline 47900 furnace
with a heating rate of 10 ◦ C min−1 . TiO2 deposits were made layer
by layer every 24 h until obtain 10 layers of coated catalyst. The
morphology and composition of TiO2 coatings were analyzed by
scanning electron microscopy (SEM) using a FEI-Nova nano SEM
200 system and X-ray diffraction (XRD) using a Siemens D500 sys-
tem type Bragg–Brentano. It was found that the obtained coating
had a homogeneous morphology and was composed of roughly
spherical TiO2 nanoparticles of about 40 nm of average diameter, a
typical particle size of this material when synthesized by the sol–gel
method. The TiO2 coating onto glass spheres was predominantly
composed of the anatase phase, with higher photocatalytic activity
than the rutile one.
2.3. Photocatalytic and electrolytic systems
Fig. 1 depicts a schematic representation of the flow plant of 3.0 L
designed by us to operate under solar or non-solar conditions by
AOPs like SPC, AO-H2 O2 , AO-H2 O2 -SPC, EF, SPEF and SPEF-SPC. The
solution with 165 mg L−1 salicylic acid and 0.05 M Na2 SO4 as back-
ground electrolyte at pH 3.0 was introduced in the reservoir and
recirculated through the plant with a centrifugal pump at constant
flow of 200 L h−1 controlled by a rotameter. The solution tempera-
ture was maintained at 35 ◦ C with two heat exchangers. The plant
(Fig. 1) had two identical photoreactors, the solar (4) and pho-
tocatalytic (5) photoreactors used for SPEF and SPC, respectively.
They consisted of a polycarbonate box of 24 cm × 24 cm × 2.5 cm
(irradiated volume 600 mL) with a mirror at the bottom and tilted
Please cite this article in press as: B. Garza-Campos, et al., Salicylic acid degradation by advanced oxidation processes. Coupling of solar
photoelectro-Fenton and solar heterogeneous photocatalysis, J. Hazard. Mater. (2016), http://dx.doi.org/10.1016/j.jhazmat.2016.02.050
3
Fig. 1. Experimental setup for the degradation of a salicylic acid solution by
coupled solar photoelectro-Fenton (SPEF) and solar photocatalysis (SPC). (1) One-
compartment filter-press cell with a 20 cm2 Pt anode and a 20 cm2 air-diffusion
cathode, (2) air pump, (3) power supply, (4) solar photoreactor, (5) photocatalytic
photoreactor with TiO2 -coated spheres, (6) reservoir, (7) centrifugal pump, (8)
rotameter and (9) heat exchangers.
41◦ (local latitude) to better collect the sun rays. The photocat-
alytic photoreactor was filled with 200 g of glass spheres covered
with TiO2 , equivalent to 0.25 g TiO2 L−1 . The electrochemical cell
(1) was an undivided filter-press reactor with a 20 cm2 Pt anode
from SEMPSA (Barcelona, Spain) and a 20 cm2 carbon- PTFE gas-
diffusion cathode from E-TEK (Somerset, NJ, USA), which was fed
with atmospheric air from a pump (2) at an overpressure of about
9 kPa to yield H2 O2 by Reaction (7). The separation of both elec-
trodes was 1.2 cm. The experiments were carried out at constant
j using an Agilent 6552A DC power supply (3). The potential dif-
ference of the cell was measured on a Demestres 605 BR digital
multimeter. The flow rate was kept at 200 L h−1 with a flowmeter
(8) and the solution temperature was regulated at 35 ◦ C with two
heat exchangers (9). Samples for analysis were withdrawn from the
solution in the reservoir (6). All the trials were performed in clear
and sunny days of the summer of 2014 in Barcelona, Spain (lati-
tude: 41◦ 21 N, longitude: 2◦ 10 E), with an average UV irradiation
intensity (␭ = 300–400 nm) of 32 W m−2 (about 3.5% of total solar
irradiation), measured with a Kipp & Zonen CUV 5 radiometer. For
the AO-H2 O2 and EF experiments, a black plastic covered the plant
to avoid light irradiation.
A previous electrolysis of a 0.05 M Na2 SO4 solution at pH 3.0 and
100 mA cm−2 was made for 240 min to activate the air-diffusion
cathode. Preliminary tests made under AO-H2 O2 conditions with a
0.1 M Na2 SO4 solution of pH 3.0 showed an accumulation of 23, 37
and 53 mM of H2 O2 after 360 min of electrolysis operating at 50, 100
and 150 mA cm−2 respectively. For the EF and SPEF trials, 0.50 mM
Fe2+ was added to the solution because this concentration yielded
the best performance for these treatments, as reported elsewhere
[43].
2.4. Analytic methods
The solution pH was determined with a Crison 2000 pH-meter.
Prior to analysis, the aliquots withdrawn from the solutions were
filtered with 0.45 ␮m Whatman PTFE filters and those treated by EF
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and SPEF were previously alkalinized to stop the generation of • OH 1.2

a
from Fenton’s Reaction (8). The amount of salicylic acid converted
into CO2 was determined from the decay of the solution TOC, deter- 1.0
mined by injecting 50 ␮L into a Shimadzu VCSH TOC analyzer with
0.8
±1% accuracy.
The removal of salicylic acid was monitored by reversed-phase

0
c/c
0.6
HPLC using a Waters 600 LC fitted with a Spherisorb ODS2 5 ␮m,
150 mm × 4.6 mm (i.d.), column at room temperature, and coupled 0.4
with a Waters 996 photodiode array detector set at ␭ = 303 nm.
Aliquots of 20 ␮L were injected into the liquid chromatograph 0.2
and the mobile phase was a 50:45:5 (v/v/v) methanol/phosphate
buffer (pH 2.5)/propanol mixture at 0.5 mL min−1 . Carboxylic acids 0.0
b
were analyzed by ion-exclusion HPLC upon injection of 20 ␮L
aliquots into the above LC fitted with a Bio-rad Aminex HPX 2.0
87H, 300 mm × 7.8 mm (i.d.), column at 35 ◦ C, with the photo-
diode detector set at ␭ = 210 nm and circulating 4 mM H2 SO4 at 1.5

ln (c / c )
0.6 mL min−1 as mobile phase.

0
1.0

3. Results and discussion

0.5
3.1. Salicylic acid removal by single and coupled AOPs
0.0
0 60 120 180 240 300 360 420
The decay of 165 mg L−1 salicylic acid (100 mg L−1 of TOC) in
3.0 L solutions with 0.05 M Na2 SO4 of pH 3.0 by the different treat- Time / min
ments tested was followed by reversed-phase HPLC, where the
Fig. 2. (a) Normalized salicylic acid concentration decay with time for the degra-
drug displayed a well-defined peak at retention time (tr ) of 2.8 min. dation of 3.0 L of 165 mg L−1 drug solution in 0.05 M Na2 SO4 at pH 3.0 and 35 ◦ C
Previous assays with recirculation of the solution in the darkness using the flow plant of Fig. 1. Method: ( ) SPC, ( ) anodic oxidation with elec-
at 200 L h−1 for 60 min revealed the existence of an insignificant trogenerated H2 O2 (AO-H2 O2 ), ( ) AO-H2 O2 -SPC and ( ) electro-Fenton (EF). A
adsorption of the substrate onto the TiO2 coating or onto the mate- current density of 50 mA cm−2 was applied in the electrochemical methods and
0.50 mM Fe2+ was added to the solution in EF. (b) Pseudo-first-order kinetic analysis
rials of the flow plant. Moreover, the exposition of the solution to
performed for the data of Fig. 2a.
sunlight upon recirculation and covering the photocatalytic pho-
toreactor with a black plastic confirmed the stability of salicylic
1.2
acid concentration, indicating that it was not directly photolyzed a
under the experimental conditions tested. Note that in all the tri-
1.0
als performed by SPC and AO-H2 O2 , alone or coupled, the solutions
remained colorless. For all the treatments made using EF and SPEF 0.8
with 0.50 mM Fe2+ , however, the initial colorless solutions changed
0

to an intense violet color after few minutes of electrolysis, proba-

c/c

0.6
bly by the formation of complexes between the remaining salicylic
acid and Fe(III) generated from Fenton’s Reaction (10) [45]. All the 0.4
violet solutions were completely decolorized again when salicylic
acid disappeared from the solution. 0.2
Comparative experiments of the 165 mg L−1 drug solution were
0.0
made without passing a current through the Pt/air-diffusion cell 0 10 20 30 40 50 60 70
for SPC alone and by applying a j = 50 mA cm−2 to it when EAOPs Time / min
were involved. Fig. 2a depicts a very slow removal of salicylic acid 2.5
by SPC, only being reduced by 14% in 360 min. This is indicative of a b
poor production of oxidizing • OH pre-eminently from Reaction (2)
2.0
induced by sunlight on the surface of the TiO2 -coated glass spheres
filling the photocatalytic photoreactor. In contrast, salicylic acid
1.5
ln (c / c )

was abated much more rapidly by AO-H2 O2 because of the greater

oxidation power of Pt(• OH) formed from Reaction (6), attaining 79%
0

of removal at the end of the electrolysis. For AO-H2 O2 -SPC, the com- 1.0
bined action of hydroxyl radicals produced from Reactions (2) and
(6) caused a quicker substrate reduction up to a final abatement of 0.5
84%.
Fig. 2a also shows a very different behavior when the EF pro- 0.0
cess was tested, since total removal of salicylic acid was achieved in 0 5 10 15 20 25 30
60 min, meaning that it and its Fe(III) complexes react more rapidly Time / min
with the greater amounts of • OH produced in the bulk from Fen-
Fig. 3. (a) Effect of current density on the normalized drug concentration abatement
ton’s Reaction (10) than from Reactions (2) and (6). A slightly higher for the degradation in the solar flow plant of 3.0 L of 165 mg L−1 salicylic acid solution
decay rate can be observed in Fig. 3a when the SPEF and coupled in 0.05 M Na2 SO4 with 0.50 mM Fe2+ at pH 3.0 and 35 ◦ C. Method: SPEF at ( )
SPEF-SPC processes were utilized. This suggests the existence of a 50 mA cm−2 , ( ) 100 mA cm−2 and ( ) 150 mA cm−2 ; SPEF-SPC at ( ) 50 mA cm−2 ,
little participation of Reaction (11) to induce the production of more ( ) 100 mA cm−2 and ( ) 150 mA cm−2 . (b) Kinetic analysis for a pseudo-first-order
• OH under sunlight irradiation and confirms the low • OH genera- reaction of salicylic acid.

Please cite this article in press as: B. Garza-Campos, et al., Salicylic acid degradation by advanced oxidation processes. Coupling of solar
photoelectro-Fenton and solar heterogeneous photocatalysis, J. Hazard. Mater. (2016), http://dx.doi.org/10.1016/j.jhazmat.2016.02.050
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tion from the holes formed at the TiO2 photocatalyst in front of 120
a
the much larger production of such kind of radicals in the electro-
chemical methods, which slightly rise with increasing j explaining 100
the low greater decay rate shown for SPEF and coupled SPEF-SPC
80

-1
in Fig. 3a.

TOC / mg L
The above concentration decays were analyzed by kinetic equa-
60
tions related to simple reaction orders. No good correlations were
obtained for the SPC data, whereas a pseudo-first-order equa- 40
tion was well adjusted to the concentration decays of all the
other treatments involving EAOPs. Figs. 2 b and 3 b present the 20
excellent linear straights found for the latter processes from such
analysis and the corresponding apparent rate constant (k1 ) with 600
its square regression coefficient (R2 ) are summarized in Table 1.
b
As expected, the k1 value grew in the sequence AO-H2 O2 < AO- 50
H2 O2 -SPC  EF ≤ SPEF ∼SPEF-SPC, in agreement with the relative
40
oxidation power of the treatments owe to the action of the dif-

MCE / %
ferent generated hydroxyl radicals, as stated above. This behavior
30
is typical of the degradation of aromatics by EAOPs [12] and can
be accounted for by the quasi-steady concentration attained by 20
Pt(• OH) and/or • OH because they cannot be accumulated since they
are rapidly destroyed having a very short lifetime near 10−8 s [46]. 10
The oxidation ability of the EAOPs relies on the applied j because
this parameter controls the generation of hydroxyl radicals [10,12]. 0
To clarify this dependence in the single and coupled processes 1.2 c
tested for salicylic acid removal, the influence of j between 50 and
1.0

/ kWh g TOC
150 mA cm−2 on its concentration decay was examined by SPEF and
SPEF-SPC. Fig. 3a highlights a similar enhancement of the removal
-1
0.8
rate of the substrate with raising j for both treatments. The time
needed for its total disappearance underwent a gradual reduction 0.6
from 60 to 20 min for raising j values between 50 and 150 mA cm−2 ,
TOC

0.4
EC

regardless of the method used, as expected, the oxidants are pre-

dominantly generated in the SPEF process compared to the SPC one. 0.2
This trend can be associated with the concomitant acceleration of
Reaction (6) yielding greater quantities of Pt(• OH) and of Reaction 0.0
0 60 120 180 240 300 360 420
(9) leading to more H2 O2 concentration, as pointed out above, that
Time / min
upgrades the • OH generation from Fenton’s Reaction (10). Never-
theless, Fig. 3a shows a slightly quicker reaction of salicylic acid Fig. 4. Variation of (a) total organic carbon, (b) mineralization current efficiency and
with• OH originated from the SPC process as j increases, making (c) specific energy consumption per unit TOC mass removed with time for the trials
the coupled SPEF-SPC treatment more powerful than the SPEF one. performed in the same conditions as in Fig. 2. Method: ( ) SPC, ( ) AO-H2 O2 , (
This phenomenon may be ascribed to a faster destruction of more ) AO-H2 O2 -SPC and ( ) EF.

recalcitrant products with the greater amounts of Pt(• OH) and • OH

produced by SPEF, allowing the reaction of higher quantities of • OH
with salicylic acid at the surface of the TiO2 photocatalyst to pro-
duce organic compounds that can be further oxidized mainly by
the hydroxyl radicals generated by SPEF.
Fig. 3b depicts the good linear straights obtained for the con-
centration decays in the SPEF and SPEF-SPC trials assuming a
pseudo-first-order kinetics and their k1 values are collected in
Table 1. These data corroborate the gradual better performance
of SPEF-SPC compared with SPEF when j rose due to the larger
prevalence of • OH originated onto the TiO2 -coated spheres. For
example, the k1 -value varied from 0.074 min−1 at 50 mA cm−2 to
0.113 min−1 at 150 mA cm−2 for SPEF, whereas it increased from
0.076 to 0.149 min−1 under comparable SPEF-SPC conditions. Note
that in such treatments, the k1 -values only grew 1.53 and 1.96 times
while j rose 3 times. This drop in the reactivity of the substrate can
be accounted for by the consumption of the excess of generated
hydroxyl radicals by non-oxidizing waste reactions. These include,
for example, the oxidation of physisorbed Pt(• OH) to O2 by Reac-
tion (13) and the removal of • OH in the bulk with Fe2+ and H2 O2
from Reactions (14) and (15), respectively [10,12,13].
2Pt(• OH) → 2 Pt + O2 + 2 H+ + 2 e−
Fe2+ + • OH → Fe3+ + OH−
H2 O2 + • OH •
→ HO2 + H2 O
3.2. Salicylic acid mineralization by single and coupled AOPs
The mineralization of the 165 mg L−1 drug solution by the sin-
gle and coupled methods tested was monitored from its TOC decay
for 360 min, as presented in Figs. 4 a and 5 a . In all these assays,
the solution pH was not regulated because it remained practically
unchanged during all the treatment time. It should also be note-
worthy that once performed all these trials, they were repeated
again obtaining quite similar TOC decays with a maximum devia-
tion < ±2%. This indicates an excellent stability of the photocatalytic
activity of the TiO2 -coated spheres under sunlight radiation and
confirms their use for long time in the SPC degradation of organics.
Fig. 4a shows that the solution TOC was very slowly removed by
the SPC process, only attaining 9% mineralization at 360 min. This
agrees with the very slow abatement of salicylic acid found for this
AOP (see Fig. 2a), indicating again the low ability of • OH formed
at the TiO2 photocatalyst to attack the oxidation products up to
their conversion to CO2 . Fig. 4a also depicts a gradual TOC decay
with partial mineralization for AO-H2 O2 , AO-H2 O2 -SPC and EF by
applying 50 mA cm−2 . After 360 min of electrolysis, these methods
led to increasing TOC removals of 16%, 24% and 29% (see Table 1),
(13)
then possessing the same relative oxidation power as for salicylic
(14) acid abatement (see Fig. 2a). This allows inferring: (i) the ROS origi-
nated in AO-H2 O2 (mainly Pt(• OH)) caused a very slow destruction
(15) of organics, (ii) the mineralization achieved by the coupled AO-

Please cite this article in press as: B. Garza-Campos, et al., Salicylic acid degradation by advanced oxidation processes. Coupling of solar
photoelectro-Fenton and solar heterogeneous photocatalysis, J. Hazard. Mater. (2016), http://dx.doi.org/10.1016/j.jhazmat.2016.02.050
G Model
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6 B. Garza-Campos et al. / Journal of Hazardous Materials xxx (2016) xxx–xxx

Table 1
Apparent rate constant for salicylic acid decay, along with its square regression coefficient, and percentage of TOC removal, mineralization current efficiency and specific
energy consumption after 360 min of treatment of 3.0 L of a 165 mg L−1 drug solution of pH 3.0 in the flow plant by different single and coupled methods under solar and
non-solar conditions.

Method j (mA cm−2 ) k1 (10−2 min−1 ) R2 % TOC removal at 360 min % MCE at 360 min ECTOC at 360 min (kWh g−1 TOC)

AO-H2 O2 50 0.41 0.995 16 7.3 1.167

AO-H2 O2 -SPC 50 0.49 0.997 24 11 0.751
EFa 50 6.6 0.9990 29 13 0.614
SPEFa 50 7.4 0.994 59 26 0.286
100 10.0 0.992 68 15 0.818
150 11.3 0.993 78 12 1.347
SPEF- 50 7.6 0.998 66 29 0.249
SPCa 100 13.1 0.991 76 17 0.695
150 14.9 0.997 87 13 1.133
a
With 0.50 mM Fe2+ added to the solution.

120 SPEF treatment of the salicylic acid solution at 50 mA cm−2 led to a

a
final TOC reduction of 59%, a value much higher than 27% obtained
100 for EF. This enhancement can be explained by the quick photode-
composition of complexes of Fe(III) with final carboxylic acids upon
80
the potent UV radiation supplied by sunlight [12,28]. The coupling
-1
TOC / mg L

of SPC with SPEF allowed the additional destruction of products

60
by • OH at the surface of the TiO2 photocatalyst that increased TOC
40 decay up to yield 66% mineralization at the end of electrolysis (see
Fig. 5a).
20 The effect of applied j between 50 and 150 mA cm−2 on TOC
abatement in SPEF and SPEF-SPC is shown in Fig. 5a. The increase
0
80 in j caused a faster TOC decay of both processes as a result of
b
70 the enhancement of Reactions (6)–(8) that produced more rapidly
products that can be more rapidly photolyzed by sunlight [28]. A
60 look of Table 1 confirms that the percentage of TOC removal at
50 360 min was 7–9% superior for the coupled SPEF-SPC treatment at
MCE / %

all j values, a value similar to that obtained for SPC. This points to
40
an additive oxidation of organics by the different • OH produced via
30 photolytic and electrochemical ways, as also found when compared
20 AO-H2 O2 and AO-H2 O2 -SPC, as explained above. The greater min-
eralization with 87% TOC removal at a specific charge consumption
10
of 6 Ah L−1 was then obtained for SPEF-SPC operating at the highest
1.40 j of 150 mA cm−2 . It should be noted that the best performance of
c SPEF in the solar flow plant differed significantly from 98% min-
1.2
eralization at 2 Ah L−1 previously reported for the same treatment
of 100 mL of a 164 mg L−1 salicylic acid solution of pH 3.0 using
/ kWh g TOC

1.0
a stirring Pt/O2 -diffusion tank reactor [42]. The loss of oxidation
-1

0.8
power in the solar flow plant can be primordially related to the
0.6 different configuration of both systems like: (i) a major part of the
stirred solution was in contact with the electrodes in the 100 mL
TOC

0.4 cell, whereas only a minor part of the recirculating solution (24 mL)
EC

was comprised between the electrodes in the cell of the 3.0 L flow
0.2
plant, thereby making the action of generated hydroxyl radicals
0.0 more inefficient, and (ii) the sunlight penetrated into all the solu-
0 60 120 180 240 300 360 420
tion in the small tank reactor, but it only acted over the planar solar
Time / min photoreactor of 600 mL in the flow plant, becoming the photolysis
of intermediates much slower and comparatively decelerating the
Fig. 5. (a) Total organic carbon abatement and change of (b) mineralization cur-
rent efficiency and (c) specific energy consumption per unit TOC mass removed mineralization process.
vs. electrolysis time for the experiments made under the same conditions as in
Fig. 3. Method: SPEF at ( ) 50 mA cm−2 , ( ) 100 mA cm−2 and ( ) 150 mA cm−2 ; 3.3. Mineralization current efficiency and specific energy
SPEF-SPC at ( ) 50 mA cm−2 , ( ) 100 mA cm−2 and ( ) 150 mA cm−2 . consumption

H2 O2 -SPC process (24%) was roughly cumulative of the separated
AO-H2 O2 (16%) and SPC (9%) ones, and (iii) the greater amounts of
• OH produced from Fenton’s Reaction (8) in EF (see Fig. 2a) were
unable to mineralize the solution in large extent and yielded a very
slow TOC decay from 120 min of electrolysis (see Fig. 4a), suggesting
the formation of very stable intermediates, like Fe(III)-carboxylate
complexes [12,13,42].
The extra action of sunlight in SPEF strongly accelerated the min-
eralization process compared with EF. As can be seen in Fig. 5a, the
To better analyze the performance of the single and coupled
treatments involving EAOPs, the mineralization current efficiency
(MCE) for each process was estimated from Eq. (16) [47]:
nFV(TOC)exp
MCE (%) = × 100 (16)
4.32 × 107 mIt
where F is the Faraday constant (96,487C mol−1 ), V is the solu-
tion volume (L), (TOC)exp is the amount of TOC removed
(mg L−1 ), 4.32 × 107 is a conversion factor (3600 s h−1 × 12,000 mg

Please cite this article in press as: B. Garza-Campos, et al., Salicylic acid degradation by advanced oxidation processes. Coupling of solar
photoelectro-Fenton and solar heterogeneous photocatalysis, J. Hazard. Mater. (2016), http://dx.doi.org/10.1016/j.jhazmat.2016.02.050
G Model
HAZMAT-17483; No. of Pages 9 ARTICLE IN PRESS
B. Garza-Campos et al. / Journal of Hazardous Materials xxx (2016) xxx–xxx
of C mol−1 ), m is the number of carbon atoms in a salicylic acid
molecule, I is the applied current (A), t is the electrolysis time (h)
and n is the number of electrons consumed in the mineralization of
salicylic acid, which was 28 assuming its total conversion into CO2
as follows:
C7 H6 O3 + 11 H2 O → 7 CO2 + 28 H+ + 28 e−
Figs. 4 b and 5 b depict the current efficiency calculated from
Eq. (16) for the assays shown in Figs. 4 a and 5 a, respectively, and
the values obtained at the end of all these treatments are given
in Table 1. As a general rule, the MCE value always decayed pro-
gressively with prolonging electrolysis as a result of the loss of
organic load by mineralization along with the gradual formation of
more recalcitrant products [10,12]. For example, at 50 mA cm−2 the
current efficiency dropped from 48% to 11% for AO-H2 O2 -SPC (see
Fig. 4b) and from 66% to 29% for SPEF-SPC (see Fig. 5b). From Figs.
4 b and 5 b, one can conclude that the processes become more effi-
cient in the order AO-H2 O2 < AO-H2 O2 -SPC < EF < SPEF < SPEF-SPC,
according to their relative oxidation ability. Moreover, an inspec-
tion of Fig. 5b and Table 1 evidences that increasing j diminished
the current efficiency of SPEF and SPEF-SPC, conversely to the faster
TOC decay observed in Fig. 5a, because of the production of more
amounts of oxidizing hydroxyl radicals. This behavior is typical of
the EAOPs [28,35–38] and can be ascribed to the concomitant larger
enhancement of waste Reactions (11)–(13), decreasing the rela-
tive content of hydroxyl radicals to attack the organics making the
process less efficient. Our results highlight that the most efficient
process was SPEF-SPC when the lowest j tested of 50 mA cm−2 was
applied.
On the other hand, the specific energy consumption per unit
TOC mass removed (ECTOC ) for the same trials was calculated from
Eq. (18) [13,47]:
 
Ecell It
ECTOC kWh g−1 TOC =
V(TOC)exp
where Ecell is the experimental average potential difference of the
electrochemical cell (V) and the other parameters are the same as
defined above.
Figs. 4 c and 5 c evidence that in all cases, ECTOC grew gradu-
ally at longer electrolysis time due to the loss in efficiency of the
processes (see Figs. 4 b and 5 b). According to this, greater spe-
cific energy consumption was found for the treatments with lower
oxidation ability, and consequently, ECTOC rose in the sequence
SPEF-SPC < SPEF < EF < AO-H2 O2 -SPC < AO-H2 O2 . This tendency can
also be deduced from the corresponding ECTOC values after 360 min
of electrolysis at 50 mA cm−2 listed in the last column of Table 1.
Similarly, the rise in j from 50 to 150 mA cm−2 upgraded the ECTOC
value for SPEF and SPEF-SPC also due to the high growth of Ecell ,
as can be seen in Fig. 5b and Table 1. The most inexpensive pro-
cess was then SPEF-SPC at 50 mA cm−2 with 0.249 kWh g−1 TOC
(16.4 kWh m−3 ) at 360 min, which was the most efficient process,
as well.
All these results show the viability of the SPEF-SPC for the reme-
diation of wastewaters polluted with salicylic acid. The use of low
j values enhances the current efficiency and diminishes the energy
consumption, although greater mineralization is achieved as j rises.
3.4. Evolution of final carboxylic acids
The degradation of salicylic acid by hydroxyl radicals in EAOPs
yields hydroxylated derivatives such as 2,3-dihydroxybenzoic,
2,5-dihydroxybenzoic and 2,6-dihydroxybenzoic acids, which sub-
sequently undergo an oxidative cleavage of the benzenic ring to
generate a mixture of short-linear aliphatic carboxylic acids, which
form Fe(III) complexes in EF and SPEF [42]. This was confirmed
from the analysis of the treated solutions by ion-exclusion HPLC
Please cite this article in press as: B. Garza-Campos, et al., Salicylic acid degradation by advanced oxidation processes. Coupling of solar
photoelectro-Fenton and solar heterogeneous photocatalysis, J. Hazard. Mater. (2016), http://dx.doi.org/10.1016/j.jhazmat.2016.02.050
7
100
80
-1
[Oxalic acid] / mg L
60
(17)
40
20
0
0 60 120 180 240 300 360
Time / min
Fig. 6. Time-course of the concentration of oxalic acid detected during the treatment
in the flow plant of 3.0 L of 165 mg L−1 salicylic acid solution in 0.05 M Na2 SO4 with
0.50 mM Fe2+ at pH 3.0 and 35 ◦ C. Method: ( ) AO-H2 O2 at 50 mA cm−2 ; ( ) AO-
H2 O2 -SPC at 50 mA cm−2 ; ( ) EF at 50 mA cm−2 ; SPEF at ( ) 50 mA cm−2 , ( )
100 mA cm−2 and ( ) 150 mA cm−2 ; SPEF-SPC at ( ) 50 mA cm−2 , ( ) 100 mA cm−2
and ( ) 150 mA cm−2 .
to detect and quantify the final carboxylic acids produced. These
chromatograms exhibited well-defined peaks related to oxalic
(tr = 6.5 min), maleic (tr = 7.9 min) and fumaric (tr = 15.1 min) acids.
Apart from these peaks, traces of tartronic, glycolic and glyoxylic
acids were found. Oxalic acid was produced from the degradation
of all the other acids and was the ultimate product because it was
directly oxidized to CO2 [1,12,28,42].
Maximum contents of 3.5 and 7.1 mg L−1 were detected for
(18) maleic and fumaric acids after 30 and 120 min, respectively, of the
EF, SPEF and SPEF-PSC processes, although they were completely
removed at longer time suggesting that their Fe(III) complexes
react rapidly with hydroxyl radicals. It should be mentioned that
in SPEF and SPEF-SPC, maleic and fumaric acids were more rapidly
destroyed with increasing j, as expected from the production of
more hydroxyl radicals, disappearing at times shorter than 90 and
240 min, respectively. In contrast, these acids were much more
poorly accumulated up to 1.45 mg L−1 for AO-H2 O2 and 1.07 mg L−1
for AO-H2 O2 -SPC, remaining as traces at the end of both treatments.
Fig. 6 shows two different behaviors for the evolution of oxalic
acid for in the treatments tested. On one hand, it was slowly
accumulated and destroyed by AO-H2 O2 , AO-H2 O2 -SPC and EF,
attaining 3.3, 2.4 and 19.4 mg L−1 after 360 min of electrolysis. That
means that oxalic acid in AO-H2 O2 and AO-H2 O2 -SPC and Fe(III)-
oxalate complexes in EF were slowly destroyed by Pt(• OH) and/or
• OH at the TiO surface and in the bulk. On the other hand, oxalic
2
acid was largely accumulated up to 71–88 mg L−1 after 60–120 min
of SPEF and SPEF-SPC and disappeared at times <240 min, more
rapidly at greater j values. This can be explained by the quicker
degradation of oxidation products to yield more oxalic acid, produc-
ing greater amounts of Fe(III)-oxalate species that are more quickly
photodecarboxylated by sunlight [28].
The aforementioned findings allow inferring that all detected
acids contribute in small amounts of 0.9, 0.6 and 5.2 mg L−1 TOC
to the 83.5, 75.5 and 71.0 mg L−1 TOC present in the final solutions
of AO-H2 O2 , AO-H2 O2 -SPC and EF, respectively (see Fig. 4a). The
fact that the major components of such treated solutions are unde-
tected products, it can also be deduced for the final solutions of SPEF
and SPEF-PSC, although in these processes the undetected products
are much more difficultly destroyed by hydroxyl radicals and/or
the photolytic action of sunlight than carboxylic acids, because the
latter ones are completely removed from the treated solutions.
G Model
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8 B. Garza-Campos et al. / Journal of Hazardous Materials xxx (2016) xxx–xxx
4. Conclusions
It has been shown that the coupled SPEF-SPC process can be
viable for the decontamination of wastewaters containing salicylic
acid. The study performed in a 3.0 L solar flow plant demonstrates
that SPC with TiO2 photocatalyst, AO-H2 O2 with a Pt/air-diffusion
cell and the coupled AO-H2 O2 -SPC yielded poor substrate removal
and mineralization of a 165 mg L−1 salicylic acid solution of pH 3.0,
indicating a low oxidation power of • OH formed at the TiO2 sur-
face and Pt(• OH) generated at the anode surface. The use of EF
strongly accelerated the salicylic acid decay because of its rapid
reaction with • OH produced from Fenton’s reaction, but with low
mineralization due to the formation of products that are diffi-
cultly destroyed by this radical. These recalcitrant products were
partly degraded under the action of sunlight in SPEF and more
rapidly destroyed by SPEF-SPC thanks to the additional oxidation
by • OH generated by the TiO2 photocatalyst. In both processes,
increasing j enhanced the salicylic acid abatement and mineral-
ization rate, although losing MCE and raising ECTOC . The most
potent treatment was achieved by SPEF-SPC at 150 mA cm−2 giving
87% mineralization, 13% current efficiency and 1.133 kWh g−1 TOC
energy consumption (6.0 Ah L−1 ) after 360 min of electrolysis. Final
carboxylic acids like maleic, fumaric and oxalic were completely
removed under these conditions and the remaining solution con-
tained undetected products that are hardly attacked by • OH and/or
sunlight.
Acknowledgments
The authors thank the financial support from the PAICYT pro-
gram of the Universidad Autónoma de Nuevo León and Conacyt
Project 181057). Financial support from MINECO (Ministerio de
Economía y Competividad, Spain) under project CTQ2013-48897-
C2-1-R, co-financed with FEDER funds, is also acknowledged. B.R.
Garza-Campos acknowledges the granted scholarship awarded by
CONACyT (Consejo Nacional de Ciencia y Tecnología, Mexico).
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Please cite this article in press as: B. Garza-Campos, et al., Salicylic acid degradation by advanced oxidation processes. Coupling of solar
photoelectro-Fenton and solar heterogeneous photocatalysis, J. Hazard. Mater. (2016), http://dx.doi.org/10.1016/j.jhazmat.2016.02.050