Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-021-16154-w

OCCURRENCE, IMPACT AND ELIMINATION OF CONTAMINANTS OF EMERGING CONCERN (CECS) IN

SOIL, WATER AND AIR STREAMS: ADVANCES AND CHALLENGES IN IBERO-AMERICAN
COUNTRIES

Modeling the sulfamethoxazole degradation by active chlorine

in a flow electrochemical reactor
Ricardo E. Palma-Goyes 1 & Fabiola S. Sosa-Rodríguez 2 & Fernando F. Rivera 3 & Jorge Vazquez-Arenas 4

Received: 4 February 2021 / Accepted: 20 August 2021

# The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2021

Abstract
The aim of this study is to propose a continuous physicochemical model accounting for the active chlorine production used to degrade
recalcitrant sulfamethoxazole (SMX) in an electrochemical flow reactor. The computational model describes the fluid mechanics and mass
transfer occurring in the re/actor, along with the electrode kinetics of hydrogen evolution reaction arising on a stainless steel cathode, and
the chloride oxidation on a DSA. Specifically, the anodic contributions assume the heterogeneous nature of the adsorbed chlorine species
formed on this surface, which are a model requirement to correctly define the experimental reactor performance and degradation efficiency
of the contaminant. The experimental validation conducted at different applied current densities, volumetric flows, and chloride concen-
trations is adequately explained by the model, thus evidencing some of the phenomena controlling the electrocatalytic chlorine production
for environmental applications. The best conditions to eliminate the SMX are proposed based on the theoretical analysis of the current
efficiency calculated with the model, and experimentally confirmed. The use of the Ti/RuO2-ZrO2-Sb2O3 anode at the bench scale
improves the SMX removal by using electro-generated chlorine species adsorbed on its surface, which remarkably increases the oxidation
potential of the system along with chlorine desorbed from the electrode. This is a technological innovation concerning other mediated
oxidation methods entirely using oxidants in solution.

Keywords Active chlorine production . Electrochemical flow reactor . Mathematical modeling . CFD . Sulfamethoxazole

Introduction

Water contamination associated with emerging pollutants in-

cluding pharmaceuticals compounds (e.g., antibiotics, ana-
Responsible Editor: Ricardo A. Torres-Palma
bolics, anti-inflammatory) and personal care products (e.g.,
soaps, hair care products, repellents) has attracted a great deal
* Fernando F. Rivera
frivera@cideteq.mx
of attention due to their measured risks concerning human
health at very low concentrations (Verlicchi et al. 2012;
* Jorge Vazquez-Arenas
jorge_gva@hotmail.com
Fatta-Kassinos et al. 2011; Ghoshdastidar et al. 2015).
Antibiotics have been classified as a priority risk group be-
1
Departamento de Química, Universidad del Valle, Santiago de cause of their high toxicity to diverse microbial forms and
CaliCalle 13 # 100-00, CP 760032, Colombia their potential to cause resistance in natural bacterial popula-
2
Research Area of Growth and Environment, Metropolitan tions (Brausch et al. 2012; Wang and Wang 2018). Additional
Autonomous University, Azcapotzalco (UAM-A), Av. San Pablo implications of these compounds involve the disruption of key
180, 02200 Mexico City, Mexico bacterial cycles/processes critical to aquatic ecology (nitrifica-
3
CONACYT - Centro de Investigación y Desarrollo Tecnológico en tion/denitrification), agriculture (soil fertility), and animal pro-
Electroquímica, Parque Tecnológico Querétaro s/n Sanfandila, Pedro duction. They have been reported in a diversity of phases like
Escobedo, 76703 Querétaro, Mexico
hospital wastewater, wastewater treatment plants (WWTP)
4
CONACYT-Departamento de Química, Universidad Autónoma and their biosolids, surface water, groundwater, drinking wa-
Metropolitana-Iztapalapa, Av. San Rafael Atlixco No 186,
09340 Mexico City, Mexico ter, sediments, and soil (Watkinson et al. 2009).

In the last years, the development of treatment
methods has become mandatory for emerging organic
compounds due to environmental regulations and incip-
ient problems detected in human health. Advanced oxi-
dation processes (AOPs) appear to be a promissory so-
lution to eliminate these compounds in various dis-
charges. In this direction, electrochemical oxidation
methods have been widely applied for the destruction
of several contaminants due to their simplicity and ver-
satility to be adapted to numerous operating conditions
in many environmental problems. Overall, this technol-
ogy benefits from the absence of chemical reagents,
mature synthesis of electrodes, facile scale-up, and low
auxiliary engineering requirements, which render its ap-
plication practical for commercial purposes. In this re-
gard, indirect oxidation methods (i.e., mediated electro-
chemical generation) have been preferred over direct
ones exclusively using the electrode surface, mainly ow-
ing to the formation of oxidants with higher oxidation
potential (Palma-Goyes et al. 2015, 2016a, b, 2018a).
In mediated electrochemical processes, the electro-
generation of active chlorine species is one of the most
important oxidants due to the availability of chloride
ions in numerous contaminated discharges. The oxidant
capacity of chlorine species typically rely on the follow-
ing redox couples: Cl2/Cl− E° = 1.36 V vs SHE, HOCl/
Cl− E° = 1.49 V vs SHE and OCl−/Cl− E° = 0.89 V vs
SHE. The oxidant standard potential of these pairs is
not fixed and depends on the anode surface, pH, applied
current density, and chloride concentration (Palma-
Goyes et al. 2018b). Although several TiO2-based di-
mensionally stable anodes (DSA) have been designed
and synthesized (Wang et al. 2007; Zeng et al. 2012;
Ribeiro et al. 2008), Sb2O3-doped Ti/RuO2-ZrO2 has
demonstrated a good performance for active chlorine
electrochemical generation (Palma-Goyes et al. 2015,
2016a, 2018b) due to the combination of two remark-
able phases to perform this reaction, RuO2 and ZrO2. In
addition to the adequate properties of RuO2 (e.g., ad-
sorptive, high positive surface charge, low oxygen/metal
fraction, and binding energy), ZrO 2 increases and
spreads the electroactive species in the TiO 2 matrix;
meanwhile, Sb 2O 3 enhances the service life (Palma-
Goyes et al. 2018b). Along with a deposition method
as Pechini, enabling a low metallic load on Ti, this
formulation can guarantee its successful scale-up at in-
dustrial levels.
One of the most used antibiotics for applications re-
lated to human and veterinarian health is sulfamethoxa-
zole (SMX), which is typically prescribed for a diversity
of pathological illnesses (Dood and Huang 2004). In
connection with this application, some studies have ver-
ified the SMX occurrence in surface and wastewater
Environ Sci Pollut Res
treatment plants, WWTP (Watkinson et al. 2009).
Although many of these contaminated discharges con-
tain chloride ions, there are not enough studies
concerning engineering aspects focused on the macro-
scopic scale for the active chlorine production including
hydrodynamics, applied current density, electrolysis
time, and chloride concentration (Palma-Goyes et al.
2015; Cruz-Díaz et al. 2018), and there are not virtually
mathematical models accounting for pollutant degrada-
tions using this oxidant to our current state of knowl-
edge. Active chlorine species have been described to be
electro-generated on the anode surface (heterogeneous
mechanism based on adsorbed active chlorine), which
differs from the typical homogeneous mechanism rely-
ing only on aqueous redox equilibria departing from
Cl2(aq). Evidence of this behavior arises from the com-
parison of the elimination of Tordon 101 comprised of
a mixture of the herbicides 2,4-D (39.2% w/v) and PCL
(10.2% w/v) using 1 mol L –1 of hypochlorous acid
(soluble chlorine at pH = 5.8), where its elimination
did not exceed 30%, while complete elimination of
PCL and 48% of 2,4-D was achieved in 2 h using
electro-generated active chlorine on a DSA (Elizarragaz
et al. 2019). Likewise, linear sweep voltammograms
conducted on Sb2O3-doped Ti/RuO2-ZrO2 in Na2SO4
and NaCl have revealed an exclusive reduction of active
chlorine species in a backward scan, indicating that ac-
tive chlorine involves an adsorption process to consider
for an appropriate description of this system (Palma-
Goyes et al. 2016b, 2018a). Indeed, the derivation of
a model employing computational fluid dynamics
(CFD) along with mass transfer contributions would
not only reveal the underlying chemical physics of the
system subjected to fundamental laws, but it would also
enable the reactor performance optimization in terms of
input variables as applied current density, volumetric
flow, and chloride concentration, in order to make this
process viable at industrial levels.
Therefore, the present study is devoted to developing a
continuous physicochemical model to comprehensively ac-
count for the SMX elimination via chlorine active species in
a FM01-LC filter press-type electrochemical flow reactor.
This is a well-established experimental configuration in elec-
trochemical processes due to its adequate control in operation-
al parameters and its capacity to attach different reactor com-
ponents (e.g., structured electrodes, net-like spacers, and sep-
arators) (Rivera et al. 2015; Castañeda et al. 2019). The active
chlorine concentration electro-generated on Ti/RuO2-ZrO2-
Sb2O3 anodes is determined at different chloride concentra-
tions (initial pH = 5.8), applied current densities, and volumet-
ric flows to evaluate the model capacities. The model accounts
for the resulting velocity fields calculated by a turbulent flow
model, and subsequently, they were coupled to mass transfer
Environ Sci Pollut Res
equations (i.e., Cl− transference to the anode surface) influenc-
ing the heterogeneous active chlorine mechanism. Then, the
model is predictively used to determine the best conditions to
abate SMX in terms of maximizing the current efficiency and
minimize the electrolysis time, which was experimentally cor-
roborated. The concentration decay of the SMX concentration
during the degradation process was monitored using high-
performance liquid chromatography (HPLC). pH and active
chlorine were determined during the entire electrolysis pro-
cess, to rationalize the physical chemistry of the system at
the different experimental conditions. The effluent herein an-
alyzed was considered a simple matrix of an aqueous solution
with the organic pollutant for a better description with the
model, which itself is already complex to consider additional
degrading compounds. Additionally, it was worthwhile men-
tioning that the production of chlorine active species on the
electrode surface, and their contact with pollutants (e.g., indi-
rect oxidation) is mainly affected by engineering aspects
governed by transport phenomena close to the anode surface,
regardless of the chemical complexity in the matrix effluent.
Material and methods
Chemical reagents
The following analytical reagents were purchased from
Merck: sodium chloride (NaCl, 98%), sulfuric acid (H2SO4,
96% v/v), potassium iodide (KI, 98%), and sodium hydroxide
(NaOH, 98%), ammonium heptamolybdate ((NH4)6 Mo7O24·
4H2O, 98%), RuCl3·H2O (98%), ZrO(NO3)2·H2O (98%),
citric acid (99%), ethylene glycol (99.8%), SbCl3 (98%), and
sulfamethoxazole (99%). The DSA was synthesized using the
Fig. 1 Experimental set-up of the filter-press FM01-LC reactor under recirculation mode
Pechini method on Ti plates, where a Ti/RuO2-ZrO2-Sb2O3
(1:1: 0.004; Ru:Zr:Sb) film was impregnated on this material,
according to ref. Palma-Goyes et al. (2015, 2016a). Note this
anode composition displayed the best performance towards
active chlorine production. Texture and compositional char-
acterizations of these materials can be consulted also in ref.
Palma-Goyes et al. (2015, 2016a).
Macro-electrolysis
A macro-electrolysis test was conducted in the FM01-LC
electrochemical reactor, coupled with a batch recirculation
tank hydraulic configuration (Fig. 1). The concentration of
NaCl in electrolytes ranged from 1 to 20 mol m−3, varying
the current densities (10 to 130 A m−2), and the volumetric
flows (1 to 5 dm3 min−1), while maintaining the temperature at
room conditions (~ 25 °C), according to a design of experi-
ments referred in supporting information S1. Chlorine active
species production electrolysis was performed for 4 h for each
experiment, since similar recalcitrant organic compounds
have been destroyed, and transformed into mineralizable or-
ganic acids at this time (Palma-Goyes et al. 2018a, Elizarragaz
et al. 2019). The electrode assembly consists of a DSA work-
ing electrode and a 316 L stainless steel plate used as cathode
material (both plates have a geometric area of 80 cm2), and an
Ag/AgCl electrode was employed as reference. According to
equilibrium diagrams previously shown in (Palma-Goyes
et al. 2018b, Elizarragaz et al. 2019), the pH of electrolysis
tests was set initially at 5.8 to ensure the HOCl predominance,
thus obtaining the most powerful oxidizing potential of this
system (1.49 V vs. SHE). pH was directly measured using a
portable meter from Hanna Instruments (model 98195). The
aqueous electrolyte was comprised of 79 μM SMX (20 mg

L−1), based on analytical and detection limits for this contam-
inant. The SMX concentration was chosen based on analytical
and detection limits, while the NaCl concentration was varied
between 0.01 and 0.2 M, to avoid exceeding representative
levels of wastewater discharges, but without compromising an
adequate ionic conductivity in the reactor (Palma-Goyes et al.
2016a). Samples for Cl− and SMX analysis were taken in the
recirculation batch tank (which is completely stirred) to avoid
concentration variations that are inherent in the reactor zone.
Production of oxidant species was determined by
iodometry as proposed in ref. (Palma-Goyes et al. 2015): ali-
quots of 600 μL of the sample were placed in a quartz cell
containing 1350 μL of 0.1 mol L−1 KI, and 50 μL of 0.01 mol
L−1 (NH4)6Mo7O24·4H2O with subsequent stirring. The ab-
sorbance at 350 nm was measured after 5 min of reaction.
Single electrochemical experiments were performed for com-
parative purposes using Na2SO4 as a supporting electrolyte, to
rule out the direct oxidation of SMX and another oxidant
formation (i.e H2O2, •OH, 1O2, O2−•) during the electrolysis
(Moreno-Palacios et al. 2019).
The degradation experiments were conducted in an electro-
chemical reactor, and aliquots were sampled and analyzed in
an HPLC (Flexar-DAD, Perkin Elmer) equipped with a
YMC-Pack ODS-AQ (150 x 4.6mm, 5μm) column and a
UV detector (wavelength of 260 nm). The mobile phase was
60:40 (v/v) mixture of water (pH 2.5, H3PO4)/acetonitrile (pH
3) at a flow rate of 0.8 mL min−1. Sodium bisulfite 1 μmolL−1
was used as a quenching agent to reduce chlorine before
analysis.
Model development
Reaction mechanism accounting for the SMX
degradation
The use of computational tools is needed to rationalize and
establish engineering aspects of electrochemical reactors
employed in mediated electrochemical oxidation (e.g., active
chlorine production), since they are subjected to hydrodynam-
ics, mass transport, and potential distribution laws governing
operating conditions and performance. These electrochemical
reactions assume mass conservation to account for the kinetics
of adsorbed species on the electrode surface (i.e., heteroge-
neous formation of HOCl).
A complete mathematical model for chlorine active pro-
duction requires the establishment of the kinetic reaction rates
expressions for the limiting reaction steps and assuming a
mechanism for heterogeneous catalysis as experimentally pro-
posed in (Palma-Goyes et al. 2018a), which is a more realistic
condition at the macroscopic level occurring within the elec-
trochemical reactor:
Environ Sci Pollut Res
MOx þ H2 OðlÞ →MOx ðH2 OÞads ð1Þ
MOx ð•OHÞads →MOx ð•OÞads þ Hþ
ðacÞ þ e
−
ð3Þ
MOx ð•OÞads þ H2 OðlÞ →MOx ð•OOHÞads þ Hþ
ðacÞ þ e
−
ð4Þ
1
MOx ð•OOHÞads →MOx þ O2 þ Hþ
ðacÞ þ e
−
ð5Þ
2
This mechanism relies on that some elementary reactions
are kinetically very fast (Eqs. 2 and 2a), whence they can be
collapsed with other steps. The kinetic and mass balances
equations for all species involved in the reaction mechanism
are simultaneously solved, as established in Table 1.
Additionally, the SMX degradation can arise through its con-
tact with absorbed and aqueous HOCl. In the first instance, the
SMX structure will depend on the solution pH, according to
Fig. 2 (Boreen et al. 2004). In neutral pH, the predominant
form is the deprotonated sulfonamide SMX-B species, while
the protonated sulfonamide species (SMX-A) is only predom-
inant at acidic pH. In the presence of active chlorine species,
the degradation pathway of SMX is complex and different
steps are required to oxidize the pollutant mainly to N-
chloro-p-benzoquinoneimine (NCBQ) and other oxidation
compounds (Dodd and Huang 2004). Under this premise,
99.99% SMX is degraded and around 85% of that yield is to
produce NCBQ (Dodd and Huang 2004). Since the main ox-
idation products were not followed using HPLC mass spec-
troscopy, but using HPLC-DAD, only the main reaction rate
of SMX degradation by the transported aqueous HOCl from
electrode surface was modeled with an apparent rate constant
kapp and where POx indicates the main oxidation product
resulting from SMX elimination (Fig. 3, pathway 1).
Likewise, SMX degradation can be carried out simultaneously
with the direct attack of the adsorbed fraction of HOCl on the
electrode surface, which could possess a stronger oxidant
power in the first instance than the aqueous one (Guzman-
Duque et al. 2014). Hence, this process will be subjected to
mass transport contributions according to Fig. 3 (pathway 2).
Hydrodynamics and mass transport contributions
In this work, hydrodynamics was solved using the coupled
RANS and standard k-ε turbulence model approach, relating
the eddy viscosity and velocity gradients with high numerical
Table 1 Model describing kinetic, mass transport phenomena and material balance equations for the heterogeneous active chlorine mechanism

Mathematical modeling

Electrode kinetics Anode Cathode

 
ð−αÞ F
Environ Sci Pollut Res

Heterogeneous Adsorption HOCl rate:   iH 2 ¼ −i0H 2 exp RT ðηcat Þ

ÞF
iadsHOCl ¼ nFk 0Cl− C 0Cl− ð1−θHOCl −θO2 Þexp ð1−α
RT ðηanode Þ
Desorption HOCl rate:
rdesHOCl ¼ k 0desHOCl Γ max HOCl θHOCl
Oxygen Evolution:  
ÞF
iadsO2 ¼ i0ads exp ð1−α
RT ðηanode þ ΔE Þ ð1−θHOCl −θO2 Þ
rdesO2 ¼ −k des
O2 Γmax;O2 θO2
SMX degradation Degradation at homogeneous phase:
rdeg = −kappCSMXCHOCl
Degradation in electrode surface according to rxn 7:
rhet = −kmθHOClCSMX
Mass balance
Main balance Equilibrium reaction
Fluid phase −v  ∇C i þ ðDiþ DT Þ∇  ∇C i −ri ¼ ∂c ∂t req ¼ k f C HOCl −k b C OCl− C H þ (It is the only reaction at fluid phase)
1
C 0i ¼ C i 1þDa (interfacial concentrations, Da is the first order
Damkhöler number)
0.489 0.33
Sh=0.617Re Sc (mass transport coefficient for electrode kinetics).
DCl− D þ ðz þ −zCl− Þ
D ¼ z þ DNa þ −zN aCl− DCl− (Diffusion
N a Na
coefficient, binary electrolyte)
i ∂θi
Adsorbed species (heterogeneous) Γ i Dθ
Dt −r toti ¼ Γ i ∂t þ v∇  θ i −rtoti ¼ 0
Mass boundary conditions
Mechanism Inlet-outlet-walls Electrode
Heterogeneous Ci =Ci, T (anode)
Di ∇ ·Ci =0 DCl− ∇  C Cl− ¼ iadsHOCl
nFA
(Concentration wall functions reported on15) DHOCl ∇ ·CHOCl −rdesHOCl
DSMX ∇ ·CSMX = −rhet
iH 2
DH þ ∇  C H þ ¼ −nFA
−
C HOCl ¼ 0 COCl ¼ 0 C H þ ¼ 0 (because of cathodic loss and hydrogen generation)
DCl− ∇  C Cl− ¼ −DHOCl ∇  C HOCl (Because of the production of chloride ions after
cathodic loss)
(adsorbed

species,
 at all walls)
∂θi ∂θi
∂x ¼ 0; ∂y ¼ 0
Charge balance (electrolyte solution)
iloc = −κ∇φs
−κ∇2φs =0
Electrochemical charge boundary conditions (galvanostatic mode)
Anode Cathode
ηanode ¼ ðV cell −φa Þ−E aeq −κ∇φc =i  app 
i RT
−κ∇φa =iapp (secondary current φc ¼ ln i0Happ −αF þ E ceq (secondary current distribution)
2
distribution)
Recirculation batch tank Equilibrium and SMX degradation at CSTR
 Environ Sci Pollut Res

accuracy (Leonzio 2018). The complete hydrodynamic turbu-

lence model is described in detail in a previous study conduct-
ed in (Rivera et al. 2017), where a different flow-type FM01-
LC reactor was analyzed. This hydrodynamic numerical solu-
tion is useful to quantify the effect of forced convection in
mass transport. The use of a previous hydrodynamic numeri-
cal solution is preferable to capture the effect of reactor inlet
and outlet, since there are no analytical expressions to deter-
mine the velocity values within the FM01-LC. Likewise, nu-
merical solutions of the fluid motion in 3D are required, due to
the mixing and homogeneous reactions arising in the aqueous
phase for the active chlorine production.
The numerical solution is then coupled to mass balances, in
All symbols and constants (with their respective values) involved in the model are listed in the supplementary material, nomenclature list, and table S4

order to solve the active chlorine species distribution over

time, using Buttler-Volmer kinetic expressions for heteroge-
neous mechanisms. All these equations including the
SMX degradation kinetics are summarized in Table 1.
The model was solved for a 3D subdomain shown in
supplementary material 2.
Here, a Dsmx diffusion coefficient was used as SMX diffu-
Cathode

sion coefficient since there are no data available for this pa-
rameter, thus, it was estimated according to the Wilke-Chang
correlation, as a first approach. The model presented here,
takes into account the homogeneous pollutant degradation in
for t ¼ 0; θi ¼ 0; C HOCl ¼ 0; C Cl− ¼ 50mol m−3 ; C OCl− ¼ 0; −logðC H þ Þ ¼ pH initial ; C SMX ¼ 0:08 mol m−3

the reaction environment by the transport of aqueous desorbed

HOCl from electrode surface to the bulk and in a recirculation
batch tank, and the heterogeneous degradation of SMX by
adsorbed HOCl, providing a more realistic model of the oxi-
dizing effect of active chlorine concentration towards SMX
and other emerging pollutants. Also, hydrodynamic and mass
conservation governing equations were coupled to the mass
balance of a perfect stirred tank, in order to establish a fair
rOCl− ;H þ ¼ −k f C HOCl þ k b C OCl− C H þ

comparison between simulation and experiment. This consists

in coupling the dynamic values of Ci(t) at the outlet of the
rHOCl ¼ k f C HOCl −k b C OCl− C H þ

reactor (which depends on the concentration distribution in-

side the reactor) with the transient changes of Ci,T(t) in the
rdeg = −kappCSMXCHOCl

stirred tank, through a temporal ordinary differential equation,

since Ci,T(t) has no variation with the tank position.

Tertiary current distribution in flow electrochemical

reactor
Anode

This study is intended to calculate the current density values

associated with the theoretical chloride oxidation, in order to
−ri ¼ 0

establish a comparison with the total experimental current

density flowing through the cell. This procedure enables the



estimation of a theoretical current efficiency to evaluate the

dt − V T C iout ðt Þ−C i;T
Mathematical modeling
Table 1 (continued)

performance of the active chlorine production at different op-

Electrode kinetics

erating conditions. The electrochemical production of chlorine

Initial conditions

active species is carried out under galvanostatic mode, indi-

cating the electrolyte potential will be dependent on the elec-
Q


trode kinetics and will rely on the complete coupling between

dC i;T

charge balance and mass transport on the electrode surface.

Environ Sci Pollut Res
Fig. 2 Scheme of equilibrium dissociation for sulfamethoxazole (SMX)
Because of the complexity of the galvanostatic mathematical
model and its intrinsic inconvenience during the numerical
solution, a specialized methodology is proposed to overcome
this concern. This consists of establishing the boundary con-
ditions indicated in Table 1 to describe the secondary potential
distribution in the flow reactor. The calculation enables to
determine the anode electrolyte potential to be used as initial
guessing since a Cauchy-type boundary condition is herein
Fig. 3 Scheme of SMX degradation to degradation products, which
could involve adsorbed (HOCl)ads or soluble chlorine (HOCl)
imposed. Once the secondary current distribution was numer-
ically calculated, (current density distribution is shown in
supplementary material S3), and the anode guess value is cal-
culated, the tertiary distribution case is then solved introduc-
ing the first-order effectiveness factor in the Butler-Volmer
kinetic expressions, to obtain the closure between charge
and mass transfer.
Numerical simulation of transport model
Governing equations comprising the model proposed here
(taking into account the turbulent fluid dynamics, electrolyte
potential distribution, and mass transport of chloride ions) are
discretized and numerically solved employing a finite element
method (FEM) scheme. 3D plots describing concentration
fields are depicted considering the anode perspective
displayed in supplementary material S2b. The FEM was im-
plemented using the COMSOL Multiphysics® 5.2a commer-
cial software. A mesh grid of 578,369 elements was used to
solve the fluid and boundary regions. This mesh grid was
selected from a previous independence grid analysis, as de-
scribed in supplementary material S3. The input parameters to
implement the numerical simulation are detailed in
Supplementary material S4. The FEM scheme employed the

GMRES and MUMPS iterative solvers considering a relative
tolerance between variables of 1 × 10−4 as a criterion of con-
vergence. Computational resources used in these calcu-
lations were similar to those described somewhere else
(Rivera et al. 2017).
Results and discussion
Experimental validation of the CFD approach
The feasibility and robustness of the mathematical model to
account for the analyzed system were contrasted with exper-
imental data collected at different conditions (Fig. 4). As ob-
served in Fig. 4a, the HOCl production at 5 dm3 min−1 and
130 A m−2 is successfully described by the mathematical
model, indicating that the proposed heterogeneous mecha-
nism coupled to transport equations adequately predicts the
experimental active chlorine formation at high current densi-
ties. Electrode kinetics plays an important role in all opera-
tional conditions for HOCl production, as evidenced under the
same conditions at 10 Am−2. There is a low production of
active chlorine species at low current densities, as described
by the mathematical model calculations, regardless of its de-
viations up to 5000 s. Please note that similar kinetic and
transport parameters have been used to simulate both cases,
whence there is a possibility that chloride oxidation kinetics is
altered between 10 and 130 A m−2, which could explain the
model deviations observed in Fig. 4.
Another important engineering criterion to rank the perfor-
mance of an electrochemical process is the current efficiency.
This figure of merit is not calculated directly by the CFD code;
nevertheless, it could be obtained utilizing the following rela-
tionship:
Fig. 4 Experimental validation of calculated HOCl production and current efficiencies at 5 dm3 min−1 and different currents applied indicated inside the
figure. a HOCl concentration. b Current efficiencies
Environ Sci Pollut Res
 
∫A iadsHOCl dA
φcalc ¼ ð6Þ
iapp
Here, the integral term of the relationship represents the
average current density employed to produce the active chlo-
rine species, in comparison to the total current applied which
contains both the Cl− electrochemical oxidation and oxygen
evolution reaction (OER). The experimental current efficiency
involved in the active chlorine production was calculated di-
viding its experimental partial charge for HOCl generation
according to Faraday’s law by the total experimental charge
as follows:
 
zFV r ΔC HOCl
φexp ¼ *100 ð7Þ
iapp t
where z is the number of electrons involved in the electro-
chemical reaction, F is the Faraday constant, Vr is the volume
of the flow reactor, and ΔCHOCl is the concentration measured
by iodometry during the electrolysis time. Figure 4 b shows
that the current efficiency trends at different NaCl concentra-
tions and applied current densities are also adequately simu-
lated at 5 dm3 min−1 by the proposed model, indicating that
the role of electrode kinetics and the fraction of adsorbed
chlorine species play important roles in the overall perfor-
mance of the electrochemical process.
The modeling trends for concentration and efficiency can
be considered satisfactory since the absolute error calculated
between model and experiment were lower than 10% for the
HOCl production, indicating that the mass transport coupled
with electrode kinetics and rate expressions described by re-
actions (1–5) correspond to a realistic description of the phys-
ical chemistry of the active chlorine production arising on a
DSA, as described in Palma-Goyes et al. (2019). In the case of
the current efficiency, an error lower than 10% was also ob-
served, mainly at low current densities.
Environ Sci Pollut Res
As previously mentioned, the discrepancies observed in the
theoretical current efficiency could be attributed to a more
complex kinetic behavior, than the Butler-Volmer-type ex-
pressions proposed in this work, mainly due to the adsorption
of the electroactive species on the anode surface.
Nevertheless, the adequate description of efficiency trends
obtained by our model is so far enough to evaluate the engi-
neering aspects involved in the pollutant removal occurring
within the electrochemical reactor.
Simulation of active chlorine production
Once the mathematical model was validated for HOCl pro-
duction and current efficiency, it is possible to explore the
influence of the different electrolysis conditions involved in
HOCl process performance. Figure 5 a shows typical results
of calculated active chlorine species in the reactor at different
current densities of 10 and 130 A m−2 (sampling time = 600 s),
while maintaining a bulk concentration of 100 mol m−3 NaCl,
and a flow rate of 5 dm3 min−1. These results are part of the
Box–Behnken design (supplementary material S1) carried out
to experimentally analyze this system, and they were obtained
through numerical simulation. As observed, the distribution of
chemical species is strongly affected by the galvanostatic cur-
rent applied on the electrode surface, provoking a strong
Fig. 5 Simulation fields of different variables studied in this work at 100 mol m−3 NaCl, 5 dm3 min−1 applying different current values on galvanostatic
mode. a HOCl concentration. b Local current density. c HOCl adsorbed fractions
difference in the concentration of chemical species produced.
Also, there is a higher production of oxidant species as the
current becomes higher, since the charge transfer is enhanced
in both processes. Since experimental profiles of this param-
eter cannot be collected, it is found that the hydrodynamic
profile influences the paths these species adopt within the
FM01-LC reactor (Rivero et al. 2012), generating strong con-
centration gradients, which on its turn produce differences in
the current density for HOCl production in all reaction zones
(refer to Fig. 5b), and also current efficiency. This effect is
particularly remarked at 130 A m−2, while this effect is atten-
uated when the current density is equal to 10 A m−2. The use
of different hydrodynamics and NaCl concentrations could
favor or hinder these effects in the current distribution.
Likewise, the adsorbed fraction and current efficiency of
HOCl are important variables since they could play important
roles during SMX degradation. Figure 5 c displays the calcu-
lated fraction of this parameter as a function of applied current
density (100 mol m−3 NaCl and 5 dm3 min−1). Similar to the
HOCl production, the adsorbed fraction of HOCl increases as
the current density is augmented. This behavior is not surpris-
ing since the rate of adsorbed species strongly depends on the
electrochemical current density supplied to the reactor (and
consequently on the overpotential obtained on the anode sur-
face). It is clearly a homogeneous distribution along the
 Environ Sci Pollut Res

FM01-LC reactor, which could be attributed to the uniformity

of the activation potential, and the limitations of the adsorbate
formation reaction by the transport of chloride ions. In addi-
tion, the material derivative and the distribution of adsorbed
species do not show a dependence on the reaction rate, and
only the time is involved to calculate the adsorbed fractions of
the different species.

Simulating the effect of NaCl concentration on HOCl

production

The concentration of the supporting electrolyte is also an im-

portant parameter during the electrochemical treatment of wa-
ter, since it affects the ionic conductivity, and consequently
the energy consumption of the process (Palma-Goyes et al.
2010). In several cases, the electrolyte plays an important role
in the process because of the occurrence of parasitic reactions
increasing or diminishing the system efficiency (Guzmán-
Duque et al. 2014). Additionally, it can simultaneously pro-
vide electroactive species as in the present case (i.e., Cl− ions).
Figure 6 a and b describe the effect of NaCl electrolyte con-
centration in the production of active chlorine species as a
function of electrolysis time, considering a constant flow rate
of 5 dm3 min−1, and two different current densities. The HOCl
production at 130 A m−2 considerably varies with the NaCl
concentration, obtaining approximately from 2 to 15 mol m−3
of active chlorine concentration at 9000 s of electrolysis time.
This behavior could be associated with an increment of reac-
tion rate with concentration as occurs in a first-order reaction
type; hence, the NaCl concentration plays an important role in Fig. 6 Production of HOCl species as a function of electrolysis time
the mediated degradation of emerging pollutants using chlo- considering different NaCl concentrations and a flow rate of 5 dm3
rine. The calculated amount of active chlorine species follows min−1 at the recirculation tank. a 130 A m−2. b 10 A m−2
the same trend at 10 A m−2, but it presents a decrease in the
overall production at all computed concentrations. Flow rate effect
Additionally, as observed in Fig. 7, the current efficiency is
considerably affected by the initial chloride concentration at Another critical issue determining the active chlorine forma-
both current densities. Figure 7 a evidences that the current tion in the electrochemical reactor is the recirculation flow
efficiency is lower as the chloride concentration decreases. rate. Figure 8 a depicts the production of HOCl as a function
Particularly, the lowest current efficiency was obtained at of current density and flow rate at 200 mol m−3 NaCl. Indeed,
10 mol m−3 and its decrement is more noticeable as the elec- the flow rate only affects the active chlorine production at 10
trolysis time increases. This effect is attenuated as the A m−2 and long electrolysis times, diminishing the HOCl pro-
concentration increases, presumably due to an enhance- duction. This effect has been reported in other references
ment of the chloride oxidation against the parasitic (Cheng and Kelsall 2007) since the known cathodic loss reac-
OER. On the other hand, the current efficiency in- tion affects the chlorine production at high flow rates (since
creases until close to 90% as the current density is this reaction is limited by mass transfer). This trend is also
decreased (Fig. 7b), improving these parameters as the observed at high electrolysis times when 10 A m−2 is applied.
chloride concentration is escalated. This behavior is pre- As described in the validation tests, the current efficiency
sumably associated with enhancement of the chloride increases with the flow rate at different current densities (Fig.
oxidation against the parasitic OER, the smallest frac- 8b). This is attributed to the hampering of OER reaction at
tion of HOCl adsorbed presented at low current densi- high flow rates since the oxygen generation is not limited by
ties (Fig. 5c), as well as the electrolyte potential obtain- mass transport, likewise the HOCl production, where chloride
ed at this low current density (not shown here). ions depend on the mass transport to the electrode surface.
Environ Sci Pollut Res
Fig. 7 Simulated current efficiencies obtained at different operational
conditions considering a flow rate of 5 dm3 min−1. a Varying NaCl
concentration at 130 A m−2. b Varying NaCl concentration at 10 A m−2
Additionally, the rapid desorption of HOCl could play a mod-
est role in the enhancement of current efficiency. Finally, op-
timal conditions from a current efficiency point of view are
established, to improve the SMX degradation using a physi-
cochemical modeling strategy.
SMX degradation
According to the modeling results and others not shown from
the Box–Behnken design of experiments (refer to supporting
information 1), it is clear that the simulation results at 200 mol
m−3, NaCl, 10 A m−2, and 5 dm3 min−1 were established at the
most efficient conditions to perform the degradation of
0.0790 mol m−3 (20 mg L−1) SMX. Particularly, it favors
the decrease of energy consumption since a low current den-
sity is used. On the other hand, this condition was compared in
the modeling with the optimal condition to degrade complete-
ly the SMX in a minimum time of electrolysis, obtained from
the experimental Box–Behnken design (200 mol m−3 NaCl,
Fig. 8 Flow rate effect on HOCl production. a HOCl production at
different flow rates in recirculation tank and current density applied in a
200 mol m−3 NaCl electrolyte, b Current efficiency at 200 mol m−3
considering different flow rates and current densities applied, shown in
the figure
250 A m−2, and 3.8 dm3 min−1). Under this condition, the
increase in current density enhances the active chlorine pro-
duction for a better attack of SMX.
The pH was monitored to reveal an increase from 5.8 to
around 7.2 (not shown) at the end of both experiments, which
is presumably due to the influence of the following cathodic
reaction, which alkalinizes the solution (Palma-Goyes et al.
2015):
2H 2 OðlÞ þ 2e− →H 2ðgÞ þ 2OH − ð8Þ
This stationary value of pH obtained after an electrolysis t =
500s could be associated with the entrance of chloride oxida-
tion into mass-transport control due to its depletion close to
the anode surface. This indicates that the activation barrier of
reaction (3) has been overcome, whence this contribution pro-
duces H+ which neutralizes the OH− generated on the cathode
side. This process is someway controlled due to the applica-
tion of a low current density in the electrodes.

Fig. 9 Experimental (symbols) 0.0790 mol m−3 (20 mg L−1) SMX normalized degradation obtained at different operational conditions. a 10 A m−2,
200 mol m−3 NaCl, and 5 dm3 min−1. b 250 A m−2, 200 mol m−3 NaCl, and 3.8 dm3 min−1. Simulations are shown as continuous lines
Figure 9 shows the normalized experimental data
(symbols) and the simulation (continuous line) performed
with the model for the SMX elimination in the electrochemi-
cal flow reactor, considering “efficient” (Fig. 9a) and “opti-
mized” (Fig. 9b) conditions. For the current density equals 10
A m−2 (low current density), it is evident that the SMX abate-
ment into most likely NCBQ occurs during the first 2500 s of
electrolysis, and the heterogeneous model is able to describe
this process with good accuracy (relative error lower than
5%). The complete SMX degradation to oxidized products
was carried out during the first 300 s of electrolysis at 250 A
m−2, indicating that the current density is a determining factor
to diminish the electrolysis time for the complete pollutant
removal, but at the cost of rising the energy consumption, as
revealed in the numerical calculations. This last condition is
achieved due to the remarkable rise of the active chlorine
production, and the increase of natural convection (i.e., direct-
ly influencing mass transference and the contact of HOCl with
pollutants) promoted from density changes and gas bubble
interactions, during the parallel formation of oxygen on the
anode (Vogt and Stephan 2015; Angulo et al. 2020; Cheng
and Kelsall 2007). These additional effects were not consid-
ered in our model, explaining the lack of fitting with the ex-
perimental data, within the first electrolysis time.
It is essential to mention that COD and simultaneous HOCl
monitoring was not followed since the removal of the organic
pollutant was the only species of interest to be degraded.
Additionally, several intermediates are required to be identi-
fied since there are no commercial standards and precisely
quantified to propose a multi-component degradation mecha-
nism, which will be the motivation of future studies.
The findings revealed from this comparison enables us to
draw that the active chlorine formation is a heterogeneous
process depending on the anode adsorption of numerous spe-
cies, as previously described in reactions (1–5), and the correct
Environ Sci Pollut Res
closure of the system can only be obtained considering the
convective and mass-transport contributions of chloride ions,
and the chemical reaction arising between SMX and HOCl
(adsorbed and soluble). In the same direction, it was observed
that the system strongly depends on applied current density,
chloride concentration, and flow rate, whence these parame-
ters need to be carefully selected for the particular design of
environmental applications.
Conclusions
A continuous physicochemical model accounting for the ac-
tive chlorine production to degrade recalcitrant sulfamethox-
azole (SMX) in an electrochemical flow reactor was proposed.
The model computationally describes the fluid mechanics and
mass transfer occurring in the reactor, along with the electrode
kinetics of hydrogen evolution reaction arising on a stainless
steel cathode, and the chloride oxidation on a DSA. This mod-
el has some particularities since it is able to describe the effect
of adsorbed chlorine species (HOCl) on the electrode surface
at low and high current densities applied. This is a requirement
to correctly define the experimental reactor performance and
degradation efficiency of the contaminant.
The validation study of HOCl production at different cur-
rent densities applied (galvanostatic mode) and Cl− concentra-
tions, evidenced the feasibility of the formation mechanism
and model proposed to describe the experimental data,
allowing to establish the complex engineering aspects in-
volved during HOCl electrolytic generation. Numerical stud-
ies showed that the current efficiency of HOCl production
increased when 10 A m−2 current densities were employed.
This was attributable to the hindering of parasitic OER reac-
tion at low current densities; in addition, numerical results
evidenced that the activation potential and kinetic current
Environ Sci Pollut Res
density for the formation of active chlorine was uniform since
there were limitations of this reaction by the transport of chlo-
ride ions to the electrode surface.
The best conditions to conduct the SMX degradation were
established from simulation-validation studies, which enabled
to obtain a complete removal of 0.0790 mol m−3 (20 mg L−1)
of the organic pollutant in approximately 1 h. The mathemat-
ical model adequately described the experimental SMX deg-
radation (relative error less than 5%) for the efficient condi-
tion. When the current density is increased, the degradation of
SMX is improved, since the mass transfer could be also im-
proved by the natural convection because of the strong bubble
formation, an effect that is not taken into account in our mod-
el, having a lack of fitting in the first electrolysis times.
Finally, the improvement of the understanding of the phys-
ical chemistry aspects involved in the generation of strong
oxidants (i.e., HOCl) using mathematical modeling and exper-
imental validation will indeed contribute to improve and de-
sign novel processes at the macroscopic scale for the elimina-
tion of recalcitrant organic pollutants (and others like water
disinfection), as sustainable alternatives to traditional chlori-
nation operations. Likewise, it was revealed that the use of the
Ti/RuO2-ZrO2-Sb2O3 anode at the bench scale improved the
SMX removal by using electro-generated chlorine spe-
cies adsorbed on its surface, which remarkably in-
creased the oxidation potential of the system along with
desorbed active chlorine in solution. This is a techno-
logical innovation concerning other mediated oxidation
methods using oxidants in solution.
Supplementary Information The online version contains supplementary
material available at https://doi.org/10.1007/s11356-021-16154-w.
Authors’ contributions REP: Draft writing, data curation, performed the
experiments and methodology.
FSR: Performed the experiments and methodology, project
administration.
FFR: Software, data analysis, conceptualization.
JVA: Data analysis, conceptualization, project administration.
The manuscript was written through the equal contributions of all
authors.
All authors read and approved the final manuscript.
Funding CONACyT “Desarrollo Científico para Atender Problemas
Nacionales” grant no. 5604. Financial support was provided by Ciencia
Básica CONACYT 2018 grant no. A1-S-21608, SECTEI-CDMX-
MEXICO (grant CM 289/2019), SIP-IPN (20200352).
Data availability The datasets used and/or analyzed during the current
study are available from the corresponding author on reasonable request.
All data generated or analyzed during this study are included in this
published article (and its supplementary information files).
Declarations
Ethics approval and consent to participate Not applicable.
Consent for publication Not applicable.
Competing interests The authors declare no competing interests.
References
Angulo A, van der Linde P, Gardeniers H, Modestino M, Fernández-
Rivas D (2020) Influence of bubbles on the energy conversion effi-
ciency of electrochemical reactors. Joule. 4:555–579. https://doi.
org/10.1016/j.joule.2020.01.005
Boreen AL, William A, McNeill K (2004) Photochemical fate of sulfa
drugs in the aquatic environment: sulfa drugs containing five-
membered heterocyclic groups. Environ Sci Technol. 38:3933-
3940. https://doi.org/10.1021/es0353053
Brausch JM, Connors K, Brooks BW, Rand GM (2012) Human pharma-
ceuticals in the aquatic environment: a review of recent toxicological
studies and considerations for toxicity testing. Rev Environ Contam
Toxicol 218:1–99. https://doi.org/10.1007/978-1-4614-3137-4
Castañeda LF, Rivera FF, Pérez T, Nava JL (2019) Mathematical model-
ing and simulation of the reaction environment in electrochemical
reactors. Curr Opin Electrochem 16:75–82. https://doi.org/10.1016/
j.coelec.2019.04.025
Cheng C, Kelsall G (2007) Models of hypochlorite production in electro-
chemical reactors with plate and porous anodes. J Appl Electrochem
37(11):1203–1217. https://doi.org/10.1007/s10800-007-9364-7
Cruz-Díaz MR, Rivero EP, Rodríguez FA, Domínguez-Bautista R (2018)
Experimental study and mathematical modeling of the electrochem-
ical degradation of dyeing wastewaters in presence of chloride ion
with dimensional stable anodes (DSA) of expanded meshes in a
FM01-LC reactor. Electrochim Acta 260:726–737. https://doi.org/
10.1016/j.electacta.2017.12.025
Dodd MC, Huang CH (2004) Transformation of the antibacterial agent
sulfamethoxazole in reactions with chlorine: kinetics, mechanisms,
and pathways. Environ Sci Technol 38:5607–5615. https://doi.org/
10.1021/es035225z
Elizarragaz D, Carrera-Crespo JE, Vazquez-Arenas J, Romero-Ibarra I,
Ruiz-Ruiz EJ, Chairez I (2019) A facile route to synthesize a TiNT-
RuO2 electrocatalyst for electro-generated active chlorine produc-
tion. J Electrochem Soc 166(15):H783–H790. https://doi.org/10.
1149/2.0071915jes
Fatta-Kassinos D, Meric S, Nikolaou A (2011) Pharmaceutical residues
in environmental waters and wastewater: current state of knowledge
and future research. Anal Bioanal Chem 399:251–275. https://doi.
org/10.1007/s00216-010-4300-9
Ghoshdastidar AJ, Fox S, Tong AZ (2015) The presence of the top pre-
scribed pharmaceuticals in treated sewage effluents and receiving
waters in Southwest Nova Scotia, Canada. Environ Sci Pollut Res
22:689–700. https://doi.org/10.1007/s11356-014-3400-z
Guzmán-Duque FL, Palma-Goyes RE, González I, Peñuela G, Torres-
Palma RA (2014) Relationship between anode material, supporting
electrolyte and current density during electrochemical degradation
of organic compounds in water. J Hazard Mater 278:221–226.
https://doi.org/10.1016/j.jhazmat.2014.05.076
Leonzio G (2018) Study of mixing systems and geometric configurations
for anaerobic digesters using CFD analysis. Renew Energy 123:
578–589. https://doi.org/10.1016/j.renene.2018.02.071
Moreno-Palacios AV, Palma- Goyes RE, Vazquez-Arenas J, Torres-
Palma RA (2019) Bench-scale reactor for Cefadroxil oxidation
and elimination of its antibiotic activity using electro-generated ac-
tive chlorine. J Environ Chem Eng 7(3):103173. https://doi.org/10.
1016/j.jece.2019.103173
Palma-Goyes RE, Guzmán-Duque FL, Peñuela G, González I, Nava JL,
Torres-Palma RA (2010) Electrochemical degradation of crystal

violet with BDD electrodes: effect of electrochemical parameters
and identification of organic by-products. Chemosphere 81(1):26–
32. https://doi.org/10.1016/j.chemosphere.2010.07.020
Palma-Goyes RE, Rivera FF, Vazquez-Arenas J (2019) Heterogeneous
model to distinguish the activity of electrogenerated chlorine species
from soluble chlorine in an electrochemical reactor. Ind Eng Chem
Res 58:22399–22407. https://doi.org/10.1021/acs.iecr.9b05185
Palma-Goyes RE, Silva-Agredo J, Vazquez-Arenas J, Romero-Ibarra I,
Torres-Palma RA (2018b) The effect of different operational param-
eters on the electrooxidation of indigo carmine on Ti/IrO2-SnO2-
Sb2O3. J Environ Chem Eng 6(2):3010–3017. https://doi.org/10.
1016/j.jece.2018.04.035
Palma-Goyes RE, Vazquez-Arenas J, Ostos C, Ferraro F, Torres-Palma
RA, González I (2016b) Microstructural and electrochemical anal-
ysis of Sb2O5 doped-Ti/RuO2-ZrO2 to yield active chlorine species
for ciprofloxacin degradation. Electrochim Acta 213:740–751.
https://doi.org/10.1016/j.electacta.2016.07.150
Palma-Goyes RE, Vazquez-Arenas J, Ostos C, Manzo-Robledo A,
Romero-Ibarra I, Calderón JA, González I (2018a) In search of the
active chlorine species on Ti/ZrO2-RuO2-Sb2O3 anodes using
DEMS and XPS. Electrochim Acta 275:265–274. https://doi.org/
10.1016/j.electacta.2018.04.114
Palma-Goyes RE, Vazquez-Arenas J, Ostos C, Torres-Palma RA,
González I (2016a) The effects of ZrO2 on the electrocatalysis to
yield active chlorine species on Sb2O5-doped Ti/RuO2 anodes. J
Electrochem Soc 163:H818–H825. https://doi.org/10.1149/2.
0891609jes
Palma-Goyes RE, Vazquez-Arenas J, Torres-Palma RA, Ostos C, Ferraro
F, González I (2015) The abatement of indigo carmine using active
chlorine electrogenerated on ternary Sb2O5-doped Ti/RuO2-ZrO2
anodes in a filter-press FM01-LC reactor. Electrochim Acta 174:
735–744. https://doi.org/10.1016/j.electacta.2015.06.037
Ribeiro J, Moats MS, De Andrade AR (2008) Morphological and elec-
trochemical investigation of RuO2–Ta2O5 oxide films prepared by
the Pechini–Adams method. J Appl Electrochem 38(6):767–775.
https://doi.org/10.1007/s10800-008-9506-6
Rivera FF, Castañeda L, Hidalgo PE, Orozco G (2017) Study of hydro-
dynamics at AsahiTM prototype electrochemical flow reactor, using
Environ Sci Pollut Res
computational fluid dynamics and experimental characterization
techniques. Electrochim Acta 245:107–117. https://doi.org/10.
1016/j.electacta.2017.05.134
Rivera FF, Ponce de León C, Nava JL, Walsh FC (2015) The filter-press
FM01-LC laboratory flow reactor and its applications. Electrochim
Acta 163:338–354. https://doi.org/10.1016/j.electacta.2015.02.179
Rivero EP, Rivera FF, Cruz-Díaz MR, Mayen E, González I (2012)
Numerical simulation of mass transport in a filter press type electro-
chemical reactor FM01-LC: Comparison of predicted and experi-
mental mass transfer coefficient. Chem Eng Res Des 90(11):1969–
1978. https://doi.org/10.1016/j.cherd.2012.04.010
Verlicchi P, Al Aukidy M, Zambello E (2012) Occurrence of pharma-
ceutical compounds in urban wastewater: removal, mass load and
environmental risk after a secondary treatment-A review. Sci. Total
Environ. 429:123-155. https:// doi.org/10.1016/j.scitotenv.2012.04.
028
Vogt H, Stephan K (2015) Local microprocesses at gas-evolving elec-
trodes and their influence on mass transfer. Electrochim Acta 155:
348–356. https://doi.org/10.1016/j.electacta.2015.01.008
Wang J, Wang S (2018) Microbial degradation of sulfamethoxazole in
the environment. Appl Microbiol Biotechnol 102:3573–3582.
https://doi.org/10.1007/s00253-018-8845-4
Wang X, Tang D, Zhou J (2007) Microstructure, morphology and elec-
trochemical property of RuO270SnO230 mol% and
RuO230SnO270 mol% coatings. J Alloys Compd 430(1-2):60–66.
https://doi.org/10.1016/j.jallcom.2006.04.058
Watkinson AJ, Murby EJ, Kolpin DW, Costanzo SD (2009) The occur-
rence of antibiotics in an urban watershed: From wastewater to
drinking water. Sci Total Environ 407:2711–2723. https://doi.org/
10.1016/j.scitotenv.2008.11.059
Zeng X, Zhang M, Wang X, Chen X, Su X, Tang W (2012) Effects of Sn
content on Ti/RuO2–SnO2–TiO2 anodes used in the generation of
electrolyzed oxidizing water. J Electroanal Chem 677:133–138.
https://doi.org/10.1016/j.jelechem.2012.05.008
Publisher’s note Springer Nature remains neutral with regard to jurisdic-
tional claims in published maps and institutional affiliations.