Water Air Soil Pollut (2017) 228: 425
https://doi.org/10.1007/s11270-017-3611-2
Degradation of Recalcitrant Safranin T Through
an Electrochemical Process and Three Photochemical
Advanced Oxidation Technologies
Carlos F. Granda-Ramírez & Gina M. Hincapié-Mejía &
Efraím A. Serna-Galvis & Ricardo A. Torres-Palma
Received: 29 June 2017 / Accepted: 12 October 2017 / Published online: 24 October 2017
# Springer International Publishing AG 2017
Abstract This work studies the degradation of safranin T
(SF, a recalcitrant pollutant) by an electrochemical process
and three photochemical advanced oxidation technologies
(TiO2 photocatalysis, UV/H2O2, and photo-Fenton). The
degradation routes of each process were elucidated initial-
ly. Based on the mineralization extent, improvement of the
treated solutions’ biodegradability, and energy consump-
tion, the most suitable process was identified. Interesting-
ly, in the electrochemical system, safranin T was efficient-
ly eliminated through electrogenerated HOCl. In contrast,
the popular photo-Fenton process was unable to degrade
SF. Moreover, the pollutant was refractory to highly ener-
getic UV254 irradiation. Meanwhile, the UV/H2O2 and
TiO2 photocatalysis processes removed SF slowly. Inter-
estingly, the electrochemical system produced biodegrad-
able solutions. Furthermore, the electrical energy
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s11270-017-3611-2) contains
supplementary material, which is available to authorized users.
C. F. Granda-Ramírez : G. M. Hincapié-Mejía
Grupo de Investigación Ambiente, Hábitat y Sostenibilidad,
Facultad de Arquitectura e Ingeniería, Institución Universitaria
Colegio Mayor de Antioquia (IUCMA), Carrera 78 No. 65-46,
Medellín, Colombia
E. A. Serna-Galvis (*) : R. A. Torres-Palma (*)
Grupo de Investigación en Remediación Ambiental y Biocatálisis
(GIRAB), Instituto de Química, Facultad de Ciencias Exactas y
Naturales, Universidad de Antioquia UdeA, Calle 70 No. 52-21,
Medellín, Colombia
e-mail: efrain.serna@udea.edu.co
e-mail: easg19@gmail.come-mail: ricardo.torres@udea.edu.co
consumption (EC) for the 100% removal of SF showed
that the electrochemical process only spent 0.04 and
0.06% of the EC needed by TiO2 photocatalysis and
UV/H2O2, respectively. Therefore, the fast SF degrada-
tion, the high biodegradability intensification, and the very
low energy consumption evidenced the relative advan-
tages of the electrochemical process for the remediation
of water containing safranin T. Finally, to obtain a deeper
understanding of SF degradation by the electrochemical
system, an analysis of structural transformations was
made. It was found that the electrogenerated HOCl initial-
ly attacked the central azine and the aromatic amines on
SF. Subsequently, aliphatic compounds were formed,
which due to their biodegradable character could be
completely eliminated by a conventional biological sys-
tem or discharged into natural media.
Keywords Pollutant degradation . Water treatment .
Processes comparison . Biodegradability intensification
1 Introduction
In cell staining processes (used to differentiate Gram-
positive and Gram-negative microorganisms), wastewa-
ters are produced with a high concentration of dyes
(Gerardi 2002). These compounds are noxious and car-
cinogenic and induce strong negative environmental
effects (Hayat et al. 2011). Such dyes have low biode-
gradability and they are recalcitrant to conventional
biological treatments (Shariati et al. 2011). One of the
most widely used azine-type dyes is safranin T (SF, also
425 Page 2 of 12
named safranin O or basic red 2). Indeed, SF is among
the oldest synthetic dyes. Moreover, SF is highly per-
sistent in water and toxic to aquatic organisms (Santa
Cruz Biotechnology Inc. 2012). Due to its extensive
application in microbiological analysis (Gram stain),
safranin T is constantly released in effluents of the food
industry (Gupta et al. 2006). Therefore, to minimize the
environmental impact of such effluents, SF degradation
is an indispensable step before final discharge.
The problems associated with SF in natural waters
have attracted the attention of the scientific commu-
nity. In fact, previous papers have evaluated the re-
moval of safranin T in water using adsorbent materials
(e.g., activated carbon, magnetic nanoparticles)
(Gupta et al. 2006; Shariati et al. 2011). However,
these systems only transfer the pollutant from the
liquid to a solid phase, requiring further treatment of
such solid wastes. Ultrafiltration has efficiently re-
moved SF, but this technique is very expensive
(Zaghbani et al. 2008).
On the other hand, advanced oxidation processes
(AOPs) have been shown as effective options for
treating water polluted with refractory substances (De
la Cruz et al. 2012; Lopez-Alvarez et al. 2012; Villegas-
Guzman et al. 2015). AOPs are based on the production
and use of hydroxyl radical (•OH). This specie is able to
degrade many classes of organic compounds. UV/H2O2,
photo-Fenton, and TiO2 photocatalysis are the most
commonly applied AOPs for water treatment (Wang
and XU 2012). Of these processes, only photocatalytic
(including photolytic) processes have been tested for SF
degradation (Abdullah et al. 2007; Ahmed and Huang
2012; El-Kemary et al. 2011; Gupta et al. 2007; Hayat
et al. 2011; Mahajan et al. 2016; Pouretedal et al. 2009).
Such works are mainly focused on the study of param-
eter effects (e.g., pH, catalyst dose or morphology, dye
concentration).
As an alternative to advanced oxidation processes,
electrochemical treatments can be exploited for the
elimination of organic pollutants in water (Comninellis
and Chen 2010; Palma-Goyes et al. 2014). In electro-
chemical processes, it is possible to degrade pollutants
by direct interaction on the surface of the electrodes or
by reaction with species electrogenerated from ions in
the electrolytic medium (Panizza and Cerisola 2009).
Indeed, dimensionally stable anodes (such as Ti/IrO2)
used in electrochemical treatments are recognized for
their high ability to produce oxidizing agents from the
medium, which can efficiently remove organic
Water Air Soil Pollut (2017) 228: 425
compounds in water (Giraldo et al. 2015; Panizza and
Cerisola 2009).
Therefore, electrochemical methods and AOPs are
suitable options for degrading recalcitrant pollutants
from water. Hence, this work compares the application
of three photochemical AOPs (UV/H2O2, photo-Fenton,
and TiO2 photocatalysis) and an electrochemical treat-
ment (using a Ti/IrO2 anode) for degradation of SF in
water. Initially, the main degradation routes involved in
the pollutant removal were established. Then, the min-
eralization ability, the biodegradability achievement,
and the energy consumption of the four processes were
determined. This evidenced some advantages of the
electrochemical technology over the AOPs. Conse-
quently, in order to better understand the electrochemi-
cal degradation of the pollutant, a study on the structural
transformations of safranin T was carried out.
2 Materials and Methods
2.1 Reagents
SF was provided by Carlo Erba. Hydrogen peroxide was
purchased from Sigma Aldrich. Hydrochloric acid from
J.T Baker was used. Sodium hydroxide was purchased
from Macron Fine Chemicals. Sodium sulfate, sodium
chloride, ferrous sulfate, acetonitrile, sulfuric acid, and
potassium iodide were provided by Merck. Ammonium
heptamolybdate and sodium bisulfite were purchased
from Panreac. Titanium dioxide was supplied by
Evonik. Potassium dichromate was purchased from
R.A Chemicals. All chemicals were used as received.
2.2 Reaction Systems
2.2.1 Reaction System Used in the Photochemical
Processes
The UV/H2O2, photo-Fenton, and TiO2 photocatalytic
processes were carried out in a homemade aluminum
reflective reactor. For UV/H2O2, five 15-W Lumex
lamps (with emission maximum at 254 nm) were used,
whereas for the other two processes, five 15-W LuxTech
lamps (with emission maximum at 365 nm) were used.
Beakers containing 150 mL of SF solution at constant
stirring were placed in the reactor.
Water Air Soil Pollut (2017) 228: 425
2.2.2 Electrochemical Reactor
Electrochemical experiments were carried out in an
electrolytic cell containing 150 mL of safranin T solu-
tion under constant stirring conditions and at 40 mA of
applied current (current density 5.0 mA cm−2). ATi/IrO2
electrode with a working surface area of 8 cm2 was used
as the anode. The cathode was a titanium plate of
12.5 cm2. NaCl or Na2SO4 was used as the supporting
electrolyte. The experimental conditions were selected
based on our previous successful works using this elec-
trochemical system (Serna-Galvis et al. 2017a, b).
2.2.3 Experimental Conditions
The sample solutions were prepared using distilled wa-
ter. The SF was used at concentrations of 20 mg L−1
(57 μmol L−1). The initial pH for the UV/H2O2, TiO2
photocatalysis, and electrochemical processes was
6.8 ± 0.1 (the natural pH of SF solution). In the photo-
Fenton process, 1000 μmol L −1 of H 2 O 2 and
90 μmol L−1 Fe (II) were used and the initial pH was
close to 3.0, taking into account that such experimental
conditions have shown to be adequate for the elimina-
tion of organic pollutants (Serna-Galvis et al. 2016a, b).
In UV/H2O2, 1000 μmol L−1 of hydrogen peroxide was
also employed. For TiO2 photocatalysis, 1.0 g L−1 of the
catalyst was used considering that such concentration is
typical for pollutant degradation (Palma-Goyes et al.
2014). The lamps were turned on after the adsorption
equilibrium was achieved (30 min under constant stir-
ring, see: Fig. SM1 in Supporting Information). Before
analyzing the treated solutions, the catalyst was re-
moved using a cellulose mesh of 0.45 μm. In the elec-
trochemical system, 0.05 mol L−1 of supporting electro-
lyte was used.
2.3 Analytical Procedures
Quantitative analysis of safranin T was carried out by
absorbance measurement at 520 nm using a Lab Scient
(UV-1100) spectrophotometer (for the band of maxi-
mum absorption of SF, see: Fig. SM2 in the Supporting
Information). Oxidants generated or consumed during
the different processes were determined by iodometry,
as reported by Serna-Galvis et al. (2016a, b).
The degree of pollutant mineralization during the
different treatments was determined by measuring the
Page 3 of 12 425
total organic carbon (TOC) according to the Standard
Method 5310 B.
Chemical oxygen demand (COD) was performed
according to the Standard Method 5220 D. Biochemical
oxygen demand at 5 days (BOD5) was carried out
according to the Standard Method 4500-OG. Before
the COD and BOD5 analyses, the residual hydrogen
peroxide or chlorine species were eliminated using so-
dium bisulfite (0.1 M).
To evaluate the direct electrochemical oxidation of
SF on the anode surface, linear voltammetry experi-
ments were performed using an Autolab PGSTAT30
in a conventional three-electrode cell: Ti/IrO2 anode
as working electrode, Ag/AgCl (3 M KCI) as the
reference electrode, and titanium plate as cathode.
The measurements were conducted at a sweep rate of
20 mV s−1.
3 Results and Discussion
3.1 Degradation of Safranin T by the Photochemical
Advanced Oxidation Processes
3.1.1 UV/H2O2 Process
Initially, the individual action of UV254 and H2O2 on
safranin T was tested. UV254 is recognized for its high
capability to induce transformation of organic com-
pounds (Challis et al. 2014; Fatta-kassinos et al. 2011),
while H2O2 acts as an oxidative agent (E° = 1.776 V),
which is able to degrade many substances (Petri et al.
2011). Nevertheless, when SF was submitted to irradia-
tion with UV254 light, there was no degradation, even
after 60 min of treatment (Fig. 1a). In addition, under the
experimental conditions, safranin T was not eliminated
by hydrogen peroxide action. In fact, the H2O2 concen-
tration remained unchanged after 60 min of contact with
the dye (Fig. 1b). The resistance of SF to removal by
UV254 or H2O2 evidences the strong recalcitrant char-
acter of this substance.
Interestingly, the combination of UV-C and hydrogen
peroxide (UV/H2O2) degraded ~ 40% of SF after 60 min
of treatment. It is reported that UV254 induces the ho-
molytic cleavage of H2O2 (Eq. 1). Indeed, the hydrogen
peroxide concentration decreased from 1000 to
615 μmol L−1 after 60 min of treatment (Fig. 1b),
indicating the formation of •OH. Hydroxyl radical is
considered the most powerful oxidizing agent in
425 Page 4 of 12 Water Air Soil Pollut (2017) 228: 425
1.2
A UV254nm
superoxide anion radicals, which evolve in various steps
1.0 toward hydroxyl radicals (Eq. 6) (Chen et al. 2005).
H2O2

0.8 TiO2 þ hν ðλ< 387 nmÞ →TiO2 ðe− −hþ Þ ð3Þ

UV254nm / H2O2
C/Co

0.6
hþ þ H2 O → Hþ þ •OH ð4Þ
0.4
hþ þ −
OH →•OH ð5Þ
0.2

0.0
e− þ O2 → •O2 − →→ •OH ð6Þ
0 10 20 30 40 50 60
Time (min) The application of TiO2 photocatalysis to eliminate
1200 safranin T is shown in Fig. 2. As seen, this process
B degrades ~ 50% of the pollutant after 90 min of treat-
1000 ment. During the photocatalysis with TiO2, in addition
H2O2 concentration (μmol L-1)

to hydroxyl radical attacks, the organic compounds (P)

800
can be degraded by UV-A photolysis (Eq. 7) or by direct
600
oxidation at the photogenerated holes (Eq. 8). There-
fore, the participation of these degradation routes was
400 H2O2 alone evaluated.
UV254 / H2O2

200
P þ hν → transformation products ð7Þ

0 hþ þ P → Pox ð8Þ
0 10 20 30 40 50 60
Time (min)

Fig. 1 a Degradation of safranin T (SF) by UV/H2O2 process. b
Evolution of hydrogen peroxide. Experimental conditions: [SF],
20 mg L−1 (57 μmol L−1); [H2O2], 1000 μmol L−1; and light
potency, 75 W
aqueous phase (E° = 2.8 V) (Palma-Goyes et al. 2014).
Hence, the removal of safranin T in the UV/H2O2 sys-
tem can be attributed to the attack of •OH (Eq. 2).
H2 O2 þ hvðλ ≤ 290 nmÞ →2•OH
SF þ •OH → degradation products
3.1.2 Heterogeneous Photocatalytic Degradation of SF
When light with wavelength ≤ 387 nm acts on the TiO2,
the promotion of an electron from the valence band to
the conduction band occurs, thereby forming an
electron-hole pair (Eq. 3). Photogenerated holes have a
high redox potential (E° = 2.7 V) and, therefore, are able
to oxidize water and hydroxide anion generating hy-
droxyl radicals (Eqs. 4 and 5) (Ohtani 2014). The excit-
ed electrons can react with dissolved oxygen to produce
To determine the contribution of the photolytic route,
a solution of safranin T was irradiated with UV-A light
in the absence of TiO2. Under such conditions, dye
degradation was not observed after 90 min of irradiation
(Fig. 2). The photons of UV-A light used in this process
are less energetic than those of UV-C in the UV/H2O2
system. Furthermore, the SF presents low absorption in
the range 300–400 nm and the lamp mainly emits at
365 nm (Fig. SM2). This explains the absence of SF
ð1Þ
degradation under UV-A action.
Meanwhile, to establish the participation of holes and
hydroxyl radicals, an experiment using acetonitrile as
ð2Þ
reaction medium was performed and compared with SF
degradation in distilled water (Fig. 2). When acetonitrile
is the solvent, hydroxyl radicals are not formed
(Villegas-Guzman et al. 2015). Additionally, a total
inhibition of degradation indicates that the attack of
•OH is the main route, whereas noninhibition of pollut-
ant elimination indicates the predominance of hole ac-
tion. In this case, it was found that safranin T is degraded
in the acetonitrile medium. Nevertheless, the removal
percentage (20%) is lower than for the treatment carried
out in water (50%). Hence, this result (a partial inhibi-
tion of dye removal) suggests that both hydroxyl
Water Air Soil Pollut (2017) 228: 425 Page 5 of 12 425
1.2 1.2
UV365 A
1.0 1.0

ACN
0.8 0.8
C/Co

C/Co
0.6 0.6
Fenton
DW
Photo-Fenton
0.4 0.4

0.2 0.2

0.0 0.0
0 20 40 60 80 100 0 20 40 60 80 100 120
Time (min) Time (min)
Fig. 2 Degradation of SF by TiO2 photocatalysis. Experimental 1.4
conditions: [SF], 20 mg L−1 (57 μmol L−1); [TiO2], 1.0 g L−1; and B
SF
light potency, 75 W 1.2 Fe(II)
SF-Fe(II)
1.0
radicals and photogenerated holes at the TiO2 surface

Absorbance (A.U.)
participate in the SF degradation by the photocatalytic 0.8

process.
0.6

0.4
3.1.3 Homogeneous Photocatalytic Degradation
0.2

Fenton and photo-Fenton are among the advanced oxi- 0.0

dation processes with the largest applicability level. In
recent years, these systems have been successfully used
at both lab and pilot scales to treat diverse types of
wastewater (Babuponnusami and Muthukumar 2014;
Lopez-Alvarez et al. 2012; Pignatello et al. 2006). The
Fenton and photo-Fenton processes are characterized by
the removal of high percentages of pollutants in short
treatment periods (Pignatello et al. 2006). Therefore,
safranin T was treated by these two processes. Surpris-
ingly, either Fenton or photo-Fenton was not able to
degrade the SF dye, even after 120 min of treatment
(Fig. 3a). Moreover, the H2O2 concentration remained
unchanged during the application of the processes (Fig.
SM3).
To establish the reason for the failure of the pro-
cesses to induce SF degradation, the interaction be-
tween iron (II) and the dye was studied. Figure 3b
presents the UV-Vis spectra for safranin T and Fe(II)
individually and for the SF-Fe (II) mixture. From Fig.
3b, it can be observed that the spectrum of the mixture
is different to the individual components. The intense
absorption between 310 and 400 nm for the SF-Fe(II)
solution (region where SF or Fe(II) has low absor-
bance) suggests that iron is complexed by the pollut-
ant. The strong affinity of ferrous ions to aromatic
200 300 400 500 600
Wavelength (nm)
Fig. 3 a Treatment of SF by Fenton and photo-Fenton processes.
b UV-Vis spectra of SF, Fe (II), and SF-Fe (II) mixture. Experi-
mental conditions: [SF], 20 mg L−1 (57 μmol L−1); [Fe (II)],
90 μmol L−1; [H2O2], 1000 μmol L−1; and light potency, 75 W
nitrogen-containing structures (as in safranin T) is
well known (Bruijnincx et al. 2008; Janiak 2000;
Olguín and Brooker 2011; Santoro et al. 2015), be-
cause heterocycles having two or more nitrogen atoms
(as the central ring of SF) present a high capacity to
coordinate metals (such as iron) to form metal-ligand-
metal links (Inoue and Kubo 1976), leading to a com-
plex stoichiometry of Fe(II):SF 2:1. This may explain
why the Fenton reaction does not occur even when the
iron concentration (90 μmol L−1) is higher than safra-
nin T (57 μmol L−1). Thus, the interaction between
ferrous ions and dye inhibits the first step in the Fenton
and photo-Fenton processes (Eq. 9). Consequently,
the hydroxyl radical is not produced and the pollutant
remains in solution even after long periods of appli-
cation of the processes.
−
Fe2þ þ H2 O2 → Fe3þ þ •OH þ OH ð9Þ
425 Page 6 of 12
3.1.4 Electrochemical Degradation of Safranin T
Electrochemical systems using a Ti/IrO2 anode in the
presence of chloride anion are an efficient form of
technology for the elimination of refractory pollutants
in water (Giraldo et al. 2015; Panizza and Cerisola 2009;
Sirés and Brillas 2012). Therefore, the treatment of SF
dye by this process was evaluated. Figure 4a shows that
more than 85% of the initial pollutant concentration was
removed at 60 min of electrolysis (SF was 100% de-
graded after 120 min). In this electrochemical system,
the dye can be removed through direct degradation on
the anode surface (Eq. 10) or by reaction with
electrogenerated active chlorine species (Cl2, HOCl,
OCl−), which come from the oxidation of the chloride
anion (Eqs. 11–14) (Panizza and Cerisola 2009; Sirés
and Brillas 2012).
Ti=IrO2 þ SF → oxidation products þ ne− ð10Þ
2Cl− → Cl2 þ 2e− ð11Þ
Cl2 þ H2 O → HOCl þ HCl ð12Þ
HOCl þ H2 O → OCl− þ H3 Oþ pKa : 7:5 ð13Þ
HOCl; OCl− ; Cl2 þ SF → degradation products ð14Þ
To determine the participation of the direct route,
experiments using a sulfate anion as the supporting
electrolyte were performed. This is because, under the
tested conditions, oxidizing agents from such anions are
not produced (BK/Na2SO4 in Fig. 4b) (Giraldo et al.
2015). Electrochemical measurements of linear volt-
ammetry were carried out with and without SF in the
presence of sodium sulfate (Fig. SM4). Such analyses
showed a peak around 1.0 V (before water oxidation/
1.12 V/), which is associated to direct oxidation of SF on
the Ti/IrO2 anode surface. Additionally, in the Ti/IrO2-
Na2SO4 electrochemical system, only 10% of the initial
safranin T concentration is removed after 60 min of
treatment (Fig. 4a). This indicates that the contribution
of pollutant degradation on the anode surface is low.
The accumulation of electrogenerated chlorine spe-
cies in both the absence and presence of SF was
assessed. In the presence of safranin T (with SF, in
Fig. 4b), the accumulation of oxidants is much lower
than in its absence (BK/NaCl in Fig. 4b), which suggests
Water Air Soil Pollut (2017) 228: 425
the oxidation of the dye by the chlorine species. Addi-
tionally, during the experiments, the pH remained in the
range 6.8–7.1. At these pH values, hypochlorous acid
(HOCl) is the major chlorine specie in solution
(Deborde and von Gunten 2008). Therefore, HOCl is
the main agent responsible for the safranin degradation
in the Ti/IrO2-NaCl system.
It can be noted that the electrogenerated hypochlorous
acid is an interesting alternative to hydroxyl radical or
holes photogenerated to fastly degrade the recalcitrant
safranin T.
3.2 Comparison of the UV/H2O2, TiO2 Photocatalysis,
and Electrochemical Processes
3.2.1 Mineralization Evolution
In addition to the evaluation of concentration decreasing,
the transformation of the initial pollutant into carbon
dioxide, water, and inorganic ions (mineralization)
should be tested. Therefore, the ability to achieve the
mineralization of safranin T (measured as TOC evolu-
tion) was compared. The TOC removal was determined
at different treatment times (which were normalized with
respect to the period necessary to remove 100% of the
SF). The time necessary to remove 100% of safranin T
(τ = 1), twice this time (τ = 2), and half (τ = 0.5) of this
time were considered. As seen in Fig. 5, significant
differences can be noted. The degree of mineralization
followed the order: TiO2 photocatalysis > UV/H2O2
system > electrochemical process.
The extent of mineralization in the three degrading
processes is determined by both the degradation route
and the chemical reactivity of SF and the by-products
toward the eliminating agents (e.g., UV light, hydroxyl
radical, or hypochlorous acid) (Serna-Galvis et al.
2016a, b).
When safranin T was completely degraded by TiO2
photocatalysis (τ = 1), ~ 90% of the initial organic
carbon in the solution was also eliminated. At τ = 0.5
(which is 5 h of treatment), the photocatalytic system
eliminated more than 70% of TOC. In addition to the
high mineralization, at τ = 1, the UV-Vis spectrum is
strongly changed, with the main absorptions occurring
at wavelengths lower than 220 nm (Fig. SM5). This last
fact suggests the transformation of the dye and its initial
by-products into highly oxidized compounds such as
carboxylic acids. During TiO2 photocatalysis of dyes
structurally related to SF (e.g., methylene blue), such
Water Air Soil Pollut (2017) 228: 425
1.2
A reaction pathway of hydroxyl radical with aromatic
1.0
0.8
C/Co
0.6
0.4
0.2
0.0
0 10
B Fig. 5.
Electrogenerated oxidizing species ( mol L-1)
120
100
80
60
40
20
0 toward oxidized forms (e.g., alcohol, aldehyde, or car-
0 10
Fig. 4 a Evolution of SF during the electrochemical treatment
using sodium chloride or sodium sulfate as supporting electrolyte.
b Electrogenerated species evolution, blank: distilled water plus
NaCl (or Na2SO4) in the absence of SF. Experimental conditions:
[SF] 20 mg L−1 (57 μmol L−1); [NaCl]: [Na2SO4], 0.05 mol L−1;
Ti/IrO2 anode—Ti cathode; and applied current, 40 mA
transformations are typical (Houas et al. 2001; Rauf and
Ashraf 2009). Furthermore, as presented in
Section 3.1.2, the hole significantly participates in this
degrading process, and carboxylic-type compounds can
be easily converted into carbon dioxide through the
photo-Kolbe reaction (Eq. 15) (Villegas-Guzman et al.
2015).
hþ þ RCOOH → R• þ Hþ þ CO2
UV/H2O2 has a moderate mineralization. After 100%
of safranin degradation (τ = 1), ~ 30% of TOC was
removed (Fig. 5), and a decrease in pH from 6.9 to 4.4
was found. As observed for the TiO2 photocatalysis, the
production of carboxylic-type substances may occur.
The •OH can initially react with the benzene rings of
safranin, inducing oxidations (which is the main
Page 7 of 12 425
compounds (Pignatello et al. 2006)). The successive
Na2SO4
attacks of •OH on the rings of safranin T could induce
their opening, thereby producing carboxylic-type struc-
tures. The hydroxyl radical is able to mineralize these
last compounds through hydrogen abstraction (Eq. 16)
(Oturan et al. 2008).
NaCl
During TiO 2 photocatalysis, both photo-Kolbe
(Eq.15) and hydrogen abstraction pathways can partic-
ipate in mineralization (Eq. 16), while in UV/H2O2, only
the latter pathway is plausible. Hence, the mineralization
20 30 40 50 60 level in the UV/H2O2 system is lower than in TiO2
Time (min)
photocatalysis, which is consistent with the results in
R‐COOH þ •OH → R• þ H2 O þ CO2 ð16Þ
In the electrochemical system, despite a fast elimina-
BK/NaCl
with SF
tion of the dye, ~ 70% of the initial TOC remained in
BK/Na2SO4
solution, even at τ = 2. This indicates that the
electrogenerated HOCl was able to transform SF. Nev-
ertheless, the by-products are not susceptible to miner-
alization via HOCl. Unlike the hydroxyl radical or
photogenerated hole, hypochlorous acid is less reactive
20 30 40 50 60
boxylic functional groups) (Deborde and von Gunten
Time (min)
2008). Moreover, dimensionally stable anodes such as
Ti/IrO2 have a low ability to degrade highly oxidized
substances (Feng and Li 2003). This explains the small
mineralizing power of the electrochemical treatment.
3.2.2 Biodegradability Evolution
Taking into account that the UV/H2O2 and electrochem-
ical processes presented moderate and low degrees of
mineralization, respectively, the accumulation of trans-
formation products that are more dangerous than the
parent compound is possible. Consequently, the harm-
fulness associated with the resultant solutions must be
assessed. Therefore, the biodegradability of the treated
ð15Þ solutions was determined to assess the accumulation of
hazardous by-products.
Figure 5 also presents the evolution of biodegradabil-
ity (measured as the BOD5/COD ratio) of the safranin T
solutions treated by UV/H2O2 and Ti/IrO2-NaCl. As can
be seen, the biodegradability of the pollutant solution
increased with the application of both processes. How-
ever, the electrochemical treatment achieved higher
values of BOD5/COD than UV/H2O2 as the treatment
425 Page 8 of 12 Water Air Soil Pollut (2017) 228: 425

Fig. 5 Comparative evolution of 1.2 1.4

mineralization and Electrochemical process
UV254 / H2O2
biodegradability during the 1.2
1.0 TiO2-Photocatalysis
processes. Experimental
conditions: as described in 1.0
Figs. 1, 2, and 4 0.8

BOD5 /COD
TOC/TOCo
0.8
0.6
0.6

0.4
0.4

0.2
0.2

0.0 0.0
0.0 0.5 1.0 1.5 2.0

τ (normalized time)

time increased. In fact, the electrochemical system in-
creased biodegradability from 0.1 to 0.55 when safranin
was 100% degraded (τ = 1), whereas for the photochem-
ical process, the ratio only changed from 0.1 to 0.28.
Wastewater is considered as biodegradable when the
BOD5/COD ratio is higher than 0.40 (Torres et al.
2003). Hence, the results indicate that the electrochem-
ically generated by-products are more susceptible to
biodegradation than the SF, and therefore, they could
be eliminated by a conventional biological process or
discharged in natural media.
3.2.3 Comparison of Energy Consumption
The electrical energy consumption (EC) required to
fully degrade safranin T was estimated for each process
using Eq. 17, where P is the input potency in watts, t is
the time in hours, and V is the treated volume in liters.
Thus, EC has the units kilowatt hour per liter.
EC ¼ ðP  t Þ=V
Interestingly, the electrical energy consumption fol-
lows the order: electrochemical treatment <<< UV/
H2O2 < TiO2 photocatalysis (Table 1). Indeed, TiO2
photocatalysis and UV/H2O2, respectively, consume
2500 and 1650 times the electrical energy used by the
electrochemical system.
Although the TiO2 photocatalysis showed the highest
mineralization, it requires long periods of treatment
(10 h), which means a high EC. Even if solar light is
used, this photocatalytic process is strongly dependent
on mass transfer and the reaction kinetic is slow (Gar
Alalm et al. 2015). Furthermore, the catalyst must be
separated from the solution after the treatment. These
aspects highlight the limitations of TiO2 photocatalysis
for practical applications in SF elimination. As shown
above, the UV/H2O2 degrades the pollutant. However, it
has a moderated mineralization level, the resultant solu-
tion is not biodegradable, and the process shows high
electrical energy consumption. In contrast, the electro-
chemical treatment presented the lowest EC value, and
transformed the recalcitrant safranin T into biodegrad-
able products, which demonstrates its potential utility in
real applications.
3.3 Proposal of the SF Structural Transformations
During the Electrochemical Treatment
Due to the advantages of the electrochemical treatment
in comparison with the other tested processes, a deeper
understanding of the safranin T degradation during the
process is needed. Thus, the structural transformations
ð17Þ
induced on safranin by the electrochemical process were
proposed based on UV-Vis spectrum changes.
Table 1 Energy electrical energy consumption (EC) by processes
required to degrade 100% of safranin T
Process TiO2 UV/ Electrochemistry
photocatalysis H2O2
Energy 5.0 3.3 0.002
consumption
(kWh L−1)
Water Air Soil Pollut (2017) 228: 425 Page 9 of 12 425
HOCl
The initial spectrum of SF presents two characteristic
absorptions: one in the visible region centered at 520 nm
and other in the UV region around 274 nm. The evolu-
H3C CH3
N
tion of UV-Vis spectra for safranin during the electro-
chemical treatment was followed (Fig. SM6A). As seen,
the main bands decreased as the electrolysis time in- H2N N
+
NH2

creased. In fact, after 120 min, both bands disappeared

and the treated solution became colorless. Additionally, HOCl HOCl

the final spectrum had a strong UV absorption at wave-

lengths below 200 nm.
The absorption of safranin T in the visible region is
attributed to the azine central structure, whereas the Attacks of the
electrogenerated
band observed in the UV region is assigned to aromatic hypochlorous acid
rings (Ahmed and Huang 2012). Therefore, the gradual
decreasing of the intensity for these absorptions and
their subsequent disappearance suggests that the pollut- Rupture of central azine
H3C CH3
ant is degraded by the initial attacks of electrogenerated N

HOCl on both the aromatic rings and azine.

It is recognized that the chlorine species have high H
N N
+
N
H

reactivity toward reduced moieties (e.g., amines or Cl Cl

azines) (Deborde and von Gunten 2008; Sandler and Chlorination of amines
Karo 1986). Indeed, the attack on azine may occur at
double bonds, leading to the rupture of the central ring
of safranin T (Sandler and Karo 1986). Meanwhile, the
reaction of aromatic amines (aniline-type, as in safranin Combined
action of
T) with chlorine species initially generates an N- HOCl
chloroaniline intermediate, which can evolve to a chlo- +
rinated ring after rearrangement (i.e., the aromatic ring is
Ti/IrO2 anode
modified in the process) (Deborde and von Gunten
2008; Haberfield and Paul 1965). Highly oxidized aliphatic
The further action of the electrochemical system by compounds

direct and mediated routes can lead to the transformation
of the primary by-products (Rajkumar and Palanivelu
2003). In fact, the decrease in COD with the treatment
time (Fig. SM6B) indicates that the initial pollutant is
converted into by-products that are more oxidized than
the parent compound. Moreover, the final spectrum with
predominant absorptions below 200 nm suggests the
formation and accumulation of aliphatic substances.
Therefore, the structural transformations of SF by the
electrochemical system can be described as an initial
attack of electrogenerated hypochlorous acid that mod-
ifies the central azine and aromatic amines followed by
the action of the anode and HOCl. This, over long elec-
trolysis times, leads to highly oxidized aliphatic com-
pounds of a biodegradable nature (Fig. 6). At this point,
it is important to remark that safranin T transformation
schema is global and this is suggested considering the
available information from the general analysis
Fig. 6 Scheme of structural transformations of SF by electro-
chemical process
developed here. However, a complete pollutant degrada-
tion mechanism can be proposed using GC-MS or
HPLC-MS techniques to establish the chemical structures
of by-products and validate the transformation schema.
4 Conclusions
The results presented in this work demonstrate the rela-
tive advantages of the electrochemical process using Ti/
IrO2 anodes to eliminate the safranin T cell staining dye
in water. The pollutant degradation by the highly popular
photo-Fenton process was inhibited by a complexation
of iron (II) with SF. On the other hand, the UV/H2O2 and
TiO2 photocatalysis were able to degrade SF. However,
425 Page 10 of 12
the kinetic of dye removal by these treatments was slow.
The TiO2 photocatalytic process, which is recognized for
its high mineralizing ability, needed 10 h to remove ~
90% of TOC. The UV/H2O2 process only mineralized
30% after 6.5 h of process application. In contrast, the
electrochemical system was able to rapidly degrade saf-
ranin T (2 h of electrolysis). At 100% of SF degradation,
20% of TOC was removed. Additionally, the resultant
solution from the electrochemical process was biode-
gradable. On the other hand, UV/H2O2 was not able to
generate biocompatible solutions. Furthermore, the com-
parison of energy consumption showed that TiO2
photocatalysis and UV/H2O2 spent, respectively, 2500
and 1650 times the electrical energy required by the
electrochemical system. This highlights the relatively
high economic viability of the electrochemical process
over the most traditional AOPs for the removal of the
recalcitrant safranin T from water. Additionally, the anal-
ysis of pollutant transformations by the electrochemical
system showed that this process modified the recalcitrant
structure of SF toward highly oxidized aliphatic com-
pounds of biocompatible nature. This evidences the
comparative benefits of the electrochemical process ap-
plication in decreasing the negative environmental im-
pact of this recalcitrant cell staining dye.
Acknowledgments The authors thank Stephanía Lopera,
Estefanía Salazar, and Margee Perea for their research assistance.
E. Serna-Galvis thanks Colciencias for his Ph.D. scholarship
(Convocatoria 647 de 2014).
Funding Information The authors thank IUCMA and
Colciencias for the financial support through the projects:
“Tratamiento de residuos orgánicos vía Procesos Avanzados de
Oxidación (PAOs) del Laboratorio de Ambiental de la Institución
Universitaria Colegio Mayor de Antioquia (IUCMA)” and
“Desarrollo y evaluación de un sistema electroquímico asistido
con luz solar para la eliminación de contaminantes emergentes en
agua (No. 111565842980), respectively.
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