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Synthetic hospital wastewater treatment by coupling submerged membrane

bioreactor and electrochemical advanced oxidation process: Kinetic study and
toxicity assessment

Article  in  Chemosphere · November 2017

DOI: 10.1016/j.chemosphere.2017.11.010

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Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Synthetic hospital wastewater treatment by coupling submerged

membrane bioreactor and electrochemical advanced oxidation
process: Kinetic study and toxicity assessment
Yassine Ouarda a, Bhagyashree Tiwari a, Antonin Azaïs a, Marc-Antoine Vaudreuil b,
Sokhna Dieng Ndiaye a, c, Patrick Drogui a, *, Rajeshwhar Dayal Tyagi a, Se

bastien Sauve

b,
Me
lanie Desrosiers , Gerardo Buelna , Rino Dube
c d
d

a
Institut National de La Recherche Scientifique (INRS), 490 rue de La Couronne, Qu
ebec City, QC, G1K 9A9, Canada
b
Universit
e de Montr
eal, 2900 Edouard Montpetit, H3C 3J7, Montr
eal, QC, Canada
c
Centre d’Expertise en analyse environnementale du Qu
ebec, minist
ere du D
eveloppement durable, de L’Environnement, et de La Lutte contre Les
changements climatiques, 2700 rue Einstein, Qu
ebec City, QC GIP 3W8, Canada
d
Centre de Recherche Industrielle du Qu
ebec (CRIQ), 333 Franquet, Qu
ebec City, QC, G1P 4C7, Canada

h i g h l i g h t s

MBR alone shows elimination of biodegradable pollutant only.

EO e MBR coupling does not allow an elimination of all the micropollutants.

MBR followed by EO treatment is efficient on the four selected model contaminants.

MBR e EO coupling generates a non-toxic effluent to Daphnia magna.

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

Article history: In this work, the combination of membrane bioreactor (MBR) and electro-oxidation (EO) process was
Received 17 July 2017 studied for the treatment of a synthetic hospital wastewater fortified with four pharmaceutical pollut-
Received in revised form ants namely carbamazepine (CBZ), ibuprofen (IBU), estradiol (E-E) at a concentration of 10 mg L1 ven-
2 November 2017
lafaxine (VEN) at 0.2 mg L1. Two treatment configurations were studied: EO process as pre-treatment
Accepted 3 November 2017
Available online 4 November 2017
and post-treatment. Wastewater treatment with MBR alone shows high removal percentages of IBU
and E-E (~90%). Unlikely for CBZ and VEN, a low elimination percentage (~10%) was observed. The hy-
Handling Editor: E. Brillas draulic and the solid retention times (HRT and SRT) were 18 h and 140 d respectively, while the biomass
concentration in the MBR was 16.5 g L1. To enhance pharmaceuticals elimination, an EO pretreatment
Keywords: was conducted during 40 min at 2 A. This configuration allowed a 92% removal for VEN, which was far
Hospital wastewaters greater than both treatments alone, with lower than 30% and 50% for MBR and EO, respectively. The
Pharmaceutical pollutants MBR-EO coupling (EO as post-treatment) allows high removal percentages (~97%) of the four pharma-
Electrochemical advanced oxidation process ceutical pollutants after 40 min of treatment at a current intensity of 0.5 A with Nb/BDD as electrodes.
Membrane bioreactor
This configuration appears to be very effective compared to the first configuration (EO-MBR) where EO
Daphnia toxicity test
process is used as a pre-treatment. Toxicity assessment showed that the treated effluent of this
configuration is not toxic to Daphnia magna except at 100% v/v. The MBR-EO coupling appears to be a
promising treatment for contaminated hospital effluents.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction

During the last decades, the production and consumption of

pharmaceuticals has increased significantly, their annual produc-
* Corresponding author. tion now exceeding thousands of tons (Santos et al. (2007); Sim
E-mail address: patrick.drogui@ete.inrs.ca (P. Drogui). et al. (2011)). Pharmaceutical compounds are widely used for

https://doi.org/10.1016/j.chemosphere.2017.11.010
0045-6535/© 2017 Elsevier Ltd. All rights reserved.
 Y. Ouarda et al. / Chemosphere 193 (2018) 160e169
prevention, diagnosis, treatment and mitigation of diseases or to
improve human or animal health. Several studies have reported the
ubiquity of pharmaceuticals in drinking water, surface water and
groundwater with concentrations varying from ng L1 to mg L1 (de
Jesus Gaffney et al. (2016); K'Oreje et al. (2016)). Their presence in
environment has raised concerns about the risks associated with
ecosystems and humans with the exposure to endocrine disruptors
and other pharmaceuticals even at low doses (de Jesus Gaffney et al.
(2016); Zhao et al. (2016)). Indeed, several authors have reported
that the presence of pharmaceutical residues in the environment
can cause ecotoxic effects, bacterial resistance and endocrine dis-
ruptions (Kostich et al. (2014); Yan et al. (2014)). Generally, hospital
wastewaters (HWWs) are directly discharged, without any treat-
ment, into the sewer system to be co-treated with urban waste-
waters (Al Qarni et al. (2016)). Unfortunately, conventional WWTPs
are mostly designed to separate suspended solids and to eliminate
biodegradable organic matter and they are usually not able to
completely eliminate pharmaceuticals, their elimination depend-
ing on their adsorption on biological sludge and biodegradation
(Santos et al. (2007)).
Many authors consider electrochemical advanced oxidation
processes as ones of most effective technologies for an effective
mitigation of no biodegradable pharmaceuticals (Klavarioti et al.
(2009); De Witte et al. (2011); Ganzenko et al. (2014)). Among
these technologies, the anodic electro-oxidation process is able to
eliminate refractory emerging contaminants, such as pharmaceu-
ticals, up to their complete mineralization. Pharmaceuticals
degradation can be done by direct or indirect electrolysis. The direct
electrolysis consists of an exchange of electrons between the pol-
lutants and the surface of the anode without involving other sub-
stances, while during the indirect electrolysis, a mediated oxidation
occurred between the pollutants and active chlorine species (i.e.
HClO, ClO, ClO2), generated in bulk solution (Sires and Brillas
(2012)). The major disadvantage which prevents their large scale
application is their relatively high costs, in particular, those related
to energy consumption during extended processing time to full
mineralization (Oller et al. (2011); Ganzenko et al. (2014)). The
formation of oxidation by-products, such as bromates, chlorates
and disinfection by-products (such as trihalomethanes) is also
considered as a significant drawback of electrochemical advanced
oxidation processes (Dirany et al. (2011); Verlicchi et al. (2015)).
Consequently, the combination of biological processes and elec-
trochemical oxidation technologies appears to be a promising
alternative to reduce the cost and energy consumption of phar-
maceutical degradation while limiting the generation of oxidation
by-products. In fact, several authors have studied the combination
of these processes for the treatment of several recalcitrant com-
pounds and reported a significant improvement on the mitigation
efficiency of the treatment compared to biological treatment alone
(Mascolo et al. (2010); Reungoat et al. (2010); Rosal et al. (2010);
Mansour et al. (2012); Ferrag-Siagh et al. (2013)). Unfortunately,
few studies have focused on the combination of electrochemical
and biological processes for the treatment of hospital effluents
(either in synthetic or in real HWWs) and, in general, experiments
are conducted with pharmaceutical concentrations which are
higher than the measured concentrations in real hospital effluents
(Ganzenko et al. (2014); Yahya et al. (2014)). Ferrag-Siagh et al.
(2013) had studied the combination of electro-Fenton (EF) and
biological process for tetracycline degradation, where EF was used
as a pre-treatment step. A complete removal of tetracycline was
observed after 20 min of treatment at pH 3, a Fe2þ catalyst con-
centration of 0.1 mM and an electrolyte concentration Na2SO4 of
0.05 mol L1. Mansour et al. (2011) had also evaluated the treat-
ment of sulfamethazine-polluted solutions using EF pre-treatment
followed by biological process. Under the optimum conditions
161
(carbon felt cathode and a platinum anode, current intensity: 0.5 A,
temperature: 18  C and treatment time: 30 min), 99.1% of sulfa-
methazine was removed. Finally, a recent study proposed a hybrid
process coupling EF process (0.1 mM Fe2þ and 0.05 M of supporting
electrolyte) and aerobic biological treatment as an efficient treat-
ment of metoprolol (beta-blocker) solutions (0.1 M) (Olvera-Vargas
et al. (2016)). The authors reported an increase of the biodegrad-
ability index (BOD5/COD) from 0.012 to 0.44 and 47% total organic
carbon (TOC) removal after 1 h EF treatment using a BDD anode. An
overall 90% mineralization of metropolol solutions was measured
after a 4-days treatment in the biological reactor. The presented
results are promising, but the need to work with a low pH (<3)
during electro-Fenton represents the main obstacle of this process.
In the framework of this study, the coupling of electro-oxidation
(EO) and the membrane bioreactor (MBR) for the treatment of
hospital wastewaters will be studied. Two scenarios can be
considered, the EO followed by the MBR or the MBR followed by EO.
In fact, the use of EO as a pre-treatment step contributes to increase
the biodegradability of wastewaters (Oller et al. (2011)). On the
other hand, the use of EO as a post treatment (polishing treatment)
helps to eliminate no biodegradable and recalcitrant compounds
(Comninellis et al. (2008)). Consequently, the main purpose of this
study is to evaluate the performances of a combined wastewater
treatment technology, anodic electro-oxidation and MBR, for the
treatment of a synthetic HWW. To the best of our knowledge, only
one publication proposed to use an electrochemical process (i.e. EF
process) either as pre-oxidative treatment or as post-treatment for
removal of pharmaceutical pollutants (i.e. caffeine and 5-
fluorouracil) from industrial pharmaceutical wastewaters in the
presence of a biological process (sequencing batch reactor)
(Ganzenko et al. (2017)). The authors concluded that the choice of
an adequate sequence of such a combined process is significantly
related to biodegradability of pollutants and their reactivity to the
oxidant species. Finally, as the toxicity is an important parameter
which allows to evaluate the treatment performances, ecotoxicity
tests on Daphnia magna have been performed on raw (synthetic)
and treated wastewater for both treatment configurations.
2. Materials and methods
2.1. Selection and characterization of pharmaceuticals
The pharmaceuticals considered in this study belong to different
pharmaceutical groups widely used and reported to occur in
aquatic environment (Lin et al. (2015); Verlicchi et al. (2015)). These
include carbamazepine (CBZ), ibuprofen (IBU), estradiol (E-E) and
venlafaxine (VEN). All the pharmaceutical products were of the
highest purity commercially available, they were purchased from
Sigma-Aldrich Canada Ltd (Oakville, ON, Canada). The characteris-
tics of targeted pharmaceuticals are presented in Table SM-1 in
supporting information. A stock solution of each pharmaceutical
was prepared weekly, from powdered substances in distilled water
at a concentration of 1 mg L1 and then stored in dark at 4  C.
2.2. Preparation of the synthetic hospital effluent
The synthetic HWW was prepared according to Seyhi et al.
(2013). COD, nitrogen and phosphorus were added by glucose,
(NH4)2SO4 and KH2PO4. Nitrogen and phosphorus have been put in
excess into the synthetic effluent so as not to be deficient in
essential nutrients for bacterial activity. The concentrations of
glucose, nitrogen and phosphorus are adjusted in order to maintain
a C:N:P ratio of 100:10:5. The concentrations of pharmaceuticals
were chosen in agreement with those detected in real hospital ef-
fluents (Santos et al. (2013); Yilmaz et al. (2017)).
162 Y. Ouarda et al. / Chemosphere 193 (2018) 160e169
2.3. Experimental units
2.3.1. Membrane bioreactor
The study was performed using a submerged membrane
bioreactor (MBR) with a working volume of 5.0 L in continuous
mode. A hollow fiber ultrafiltration membrane (ZW-1, Zenon
Environmental Inc., Canada) was immersed in the bioreactor (the
membrane characteristics are presented in Table SM-2). MBR
feeding and filtration were carried out by two peristaltic pumps
(Masterflex 7550e00, Cole-Parmer Instrument Co, Canada). The
pump power was adjusted such that the flowrate of permeate was
similar to the feed flowrate 5 mL min1 (14.1  103 LMH). In order
to reduce the membrane clogging, an automatic backwash of the
membrane was carried out for 10 s for each 60 s cycle. The clogging
of the membrane was controlled by monitoring numeric trans-
membrane pressure (TMP) and once the pressure reaches to 40 kPa
the cleaning of the membrane was performed following the pro-
cedure described by Seyhi et al. (2012) consisting in immersion of
the fouled membrane in a solution of 1000 mg L1 of NaClO for 6 h,
followed by cleaning with a solution of 3 g L1 of citric acid for 1 h
and finally a washing with tap water.
2.3.2. Electrochemical oxidation unit
The EO reactor was made of Plexiglas material with dimensions
of 14 cm  5 cm x 10 cm. The total volume was 1000 mL including
the contact reactor and a recirculating tank. The recycling flowrate
was maintained around 200 mL min1 by a peristaltic pump
(Masterflex L/S, Cole-Parmer Co., Montreal, QC, Canada). The cir-
cular mesh anode/cathode electrodes were 12 cm diameter and
0.1 cm thick. The solid surface and the void surface area of the
electrodes were 20.8 and 92.2 cm2, respectively. The distance be-
tween electrodes was maintained at 1 cm and surface/volume ratio
was 28 cm2 L1. The current was provided by a DC power supply
(Sorensen DCS40-75 E, Magna-Power Electronics Inc., Flemington,
New Jersey, USA).
2.4. Experimental procedure
2.4.1. Membrane bioreactor setup
The MBR was initially inoculated with activated sludge obtained
from a municipal wastewater treatment plant (Victoriaville,
Quebec, Canada). The feeding of the bioreactor and filtration were
performed at a constant flowrate of 5 mL min1 (14.1  103 LMH),
corresponding to a hydraulic retention time (HRT) of 18 h and
sludge retention time (SRT) was kept infinite, which represent
approximately 140 d of SRT taking into account sludge sampling for
analyses. During start-up phase, the MBR was fed with the syn-
thetic wastewater without any pharmaceuticals in order to develop
a high concentration of biomass. The initial COD fed to the MBR was
kept high at about 2000 mg L1 to insure quick biomass buildup.
The pH and temperature of the reactor were 7.0 ± 0.5 and
20.0  C ± 1  C, respectively. After 30 d of operation, biomass con-
centration in the MBR reached around 16.5 g L1 VSS and stable
ammonium, phosphate and COD elimination was obtained (see
Figs. SM-1, SM-2 and SM-3). Synthetic influent was then fortified
with 4 pharmaceuticals (CBZ, IBU, E-E and VEN).
The biomass of the bioreactor was acclimated to pharmaceuti-
cals by gradually increasing their concentrations, under identical
operating conditions. The concentration of E-E, IBU, and CBZ in the
influent feed was then gradually increased from 5 to 10 mg L1 and
100e200 ng L1 for VEN. The total COD was adjusted to 1000 mgO2
L1 by a progressive decrease in the concentration of glucose.
2.4.2. Anode selection
In order to select the most efficient electrodes, preliminary tests
were conducted with several anodic materials such as titanium
coated with iridium (IV) oxide (Ti/IrO2), niobium coated with bored
doped diamond (Nb/BDD), titanium coated with platinum (Ti/Pt),
mixed metal oxide (MMO) composed of titanium coated with
iridium oxide and ruthenium oxide (Ti/IrO2/RuO2). For each of
these tests, the cathode was made of titanium (Ti). Experiments
were conducted with different currents (0.5, 1 and 2 A) corre-
sponding to current densities of 24, 48 and 96 mA cm2. A treat-
ment time ranging from 0 to 120 min was selected.
2.4.3. Kinetic experiments
The kinetics of pharmaceutical elimination were realized for the
two configurations with currents of 0.5 and 2 A and a treatment
time ranging between 0 and 120 min with selected anodes. Ex-
periments were duplicated and samples were taken every 20 min.
Concurrently, the hydroxyl radical (
OH) exposure was estimated
from the oxidation of p-chlorobenzoic acid (pCBA). The pCBA is
used as a model
OH probe, it has a very low reactivity with oxidant
species (such as ozone) and reacts quickly with
OH (with
k”OH ¼ 5.0  109 M1s1) (Elovitz and von Gunten (1999)).
2.5. Analytical details
2.5.1. Pharmaceuticals analysis by LC-MS/MS
The pharmaceuticals present in the matrix before and after the
different treatment tests were quantified with a triple quadruple
mass spectrometer (TSQ Quantiva from Thermo Scientific) using
reverse phase C18 column and SPE cartridge (Hypersil Gold C18,
from Thermo Scientific) with an analytical set up that allows on-
line SPE pre-concentration method. Water and methanol are used
both for pre-concentration and elution steps (on charge pump and
analytical pump). Recovery for the four compounds of interest is
above 60%. Limit of detection (LOD) has been estimated using a
signal to noise ratio of three (S/N ¼ 3) and are of the order of low ng
L1.
2.5.2. Hydroxyl radical's measurement
The estimation hydroxyl radical's production was performed
according to the method reported by Azais et al. (2016). Before
electrolysis, pCBA was added to a final concentration of 200 mgL1
and a sample was taken at time zero. This probe compound reacts
specifically with OH radicals (with k”OH ¼ 5.0  109 M1s1).
Therefore, pCBA concentration is followed during the electrolysis.
The degradation of pCBA does not allow to assess the exact quantity
of hydroxyl radicals produced during electrolysis. By contrast, it
gives an idea of the exposure to hydroxyl radicals, expressed in
mol.s, during electrolysis. According to Elovitz and von Gunten
(1999), the exposure to radicals is calculated using the equation
bellow:
(1)
where the time-integrated concentration of OH radical is synony-
mous with the hydroxyl radical exposure.
pCBA analysis was performed using HPLC DIONEX DX-500 de-
vice with a reverse phase C-18 column (BioBasic-18,
250 mm  4.6 mm) with AS50 auto-sampler. An eluent 45% 10 mM
phosphoric acid and 55% Methanol grade HPLC was used. The flow
was fixed at 0.7 mL min1. The PDA-100 detector UV absorbance
was set at 234 nm. Quantification limit (LOQ) of 20 mg L1 was
achieved.
 Y. Ouarda et al. / Chemosphere 193 (2018) 160e169
2.6. Toxicity assessment
Neonate daphnids, i.e. less than 24-h- old raised at the Centre
d’Expertise en Analyse Environnementale du Qu
ebec (CEAEQ) labo-
ratory were used during the toxicity tests. The organisms were
derived from a single clone of Daphnia magna Straus cultured and
maintained in a culture medium (hardness 160e180 mg CaCO3 L1,
dissolved oxygen  80%, pH 7e8, at 20.0 ± 2.0  C with 16- h light
(500e1000 lux) and 8-h dark photoperiod). Neonates were fed
every other day with Pseudokirchneriella subcapitata (20  106 cells
mL1) but they were not fed during the toxicity tests. The alga was
cultured in 965 mL of demineralized water enriched with 5 mL of
each macroelement (NaNO3, CaCl2, MgSO4, K2HPO4, KH2PO4, NaCl)
and 0.5 mL of each microelement (MnCl2, ZnSO4, Co(NO3), MoO3,
CuSO4). Neonates Daphnia magna (<24-h- old) were exposed 48 h,
according to the CEAEQ standardised protocol (CEAEQ (2016)), to
the synthetic hospital wastewater before (n ¼ 2) and after treat-
ment (n ¼ 3) using four different process configurations: MBR, MBR
followed by EO, EO and EO followed by MBR. The dilution factor
recommended for effluent toxicity is between 0.5 and 0.7 (USEPA
(2002)). In this study, we evaluated a wide concentration range
such as 0.2%, 0.4%, 0.8%, 1.6%, 3.1%, 6.3%, 12.5%, 25%, 50%, 75%, 100%.
Briefly, four replicates included five neonates (<24- h-old) were
placed in glass test tubes containing 10 mL of each sample con-
centration (culture medium with effluent) and the control (culture
medium). The dissolved oxygen (DO), conductivity, pH, water
temperature and the hardness of the samples were measured
before and after the toxicity test. If DO concentration in the samples
was less than 80% before exposure, aeration might be used to bring
the DO into equilibrium with air. The measurements of these pa-
rameters are important because the endpoints assessed include the
additive effects of chemical, physical and biological components of
the sample. The neonates were not fed during the test, the exposure
conditions were: 16-h light (500e1000 lux) and 8-h dark photo-
period, 20.0 ± 2.0  C. The toxicity results were accepted if the
control mortality is equal or lower than 5%. The assessment end-
points were mortality and immobilization after 48 h of exposure.
The mortality was evaluated by binocular microscope. The neo-
nates that were able to swim were considered mobile and those
which still moved their antennae but did not swim within 15 s after
a gentle shaking were considered immobile.
3. Results and discussion
3.1. Preliminary tests
The performances of the anodic electro-oxidation process are
greatly affected by the type of anode material and current (García-
Go
mez et al. (2014); Komtchou et al. (2015); Jardak et al. (2016)). In
this study, experiments were conducted to determine the oxidation
behavior of pharmaceuticals using several anode materials (Ti/
PbO2, Nb/BDD, Ti/Pt, Ti/MMO) under specific conditions of current,
recycling flowrate, and initial pharmaceutical concentrations. Pre-
liminary results showed that Nb/BDD and Ti/MMO are more
effective than Ti/PbO2 and Ti/Pt for pharmaceutical oxidation.
The experiments were carried out with two currents, 0.5 and 2
A, for a treatment time of 120 min with both BDD and MMO anodes.
The choice of two different anodes also allows to study the influ-
ence of the anode activity (BDD non-active anode and MMO an
active anode) on the elimination of pollutants and the production
of radicals. After 120 min of treatment, Ti/MMO seems to be very
effective for the degradation of VEN and EE (100% removal), while
the abatement of CBZ and IBU was 92% and 70%, respectively. Nb/
BDD showed very high removal percentages for all pharmaceuticals
163
(CBZ > 97%, IBU > 93%, VEN >90% and IBU > 97%). Therefore, Nb/
BDD and Ti/MMO were chosen for the next step of this study.
3.2. Electrochemical advanced oxidation process as a pre-treatment
First, a kinetic study of the target pollutants degradation was
carried out, by comparing the two selected anodes and two
different currents. Fig. 1 shows the effect of applied current and
anode material on the degradation of selected pharmaceuticals. As
revealed in Fig. 1, current intensity is a significant parameter
affecting pharmaceutical abatement. The highest degradation per-
centages (>93%) were recorded when applying an intensity of 2 A
regardless of the anode material. These results were expected since
a high production of hydroxyl radicals is generally observed with
higher intensities. For all the applied current, the corresponding
concentration decays follow a pseudo-first-order reaction. The
apparent first rate constant (k'app) values increase with the applied
current. These results are in agreement with the results reported by
Ambuludi et al. (2013) during IBU electrolysis using BDD and Pt.
As illustrated in Fig. 1b, BBD is more effective than MMO for IBU
degradation. In fact, within 120 min of electrolysis at an intensity of
2 A, 94% of IBU elimination was achieved with BDD and 80% with
MMO. For both electrodes, the IBU concentration decays followed a
pseudo-first-order kinetic equation and the k'apps were 3.9  104
s1 and 2.2  104 s1 for BDD and MMO respectively. The observed
apparent first order constant was slightly lower than what
Ambuludi et al. (2013) and Skoumal et al. (2009) reported
(respectively 3.12e7.87  104 s1 and 4.86  104 s1) which can
be explained by the fact that in our study, a mixture of pharma-
ceuticals was treated simultaneously in synthetic HWW containing
organic matter, contrary to the reported studies where IBU was the
only pollutant present in aqueous solution. When applying 0.5 A,
70% of IBU was eliminated with BDD whereas only 37% was ach-
ieved with MMO after 120 min of treatment. Ambuludi et al. (2013)
had reported similar results during the electrolysis of IBU con-
firming the efficiency of BDD over Pt on IBU degradation. No sig-
nificant difference was observed between BDD and MMO regarding
CBZ abatement, the only parameter affecting its removal being the
applied current. In fact, more than 96% degradation is observed
with a current of 2 A after 120 min using the two anodes and only
75% is obtained when applying 0.5 A. The k'apps were 5.0  104 s1
and 4.6  104 s1 for BDD and MMO at 2 A respectively, con-
firming an important effect on CBZ elimination compared to anode
material.
Similar results were reported by García-Go
mez et al. (2014)
during the electrochemical oxidation of CBZ (10 mg L1) using
BDD and PbO2 anodes. After 100 min of electrolysis with a current
of 2 A, a high degradation percentage (90%) of CBZ was observed for
both anodes. A lower apparent rate constant was reported by
García-Go
mez et al. (2014) (k'apps 3.5  104 s1) during the elec-
trolysis of CBZ using PbO2 and BDD anodes, however, in this study
10 mg L1 of CBZ was treated compared to 10 mg L1 in our study.
The degradation of E-E and VEN are represented in Fig. 1a and d.
According to the results, VEN abatement is affected by both anode
material and current intensity. The highest elimination percentages
were achieved with high current (2 A). Comparing MMO and BDD
performances, MMO seems to be more effective on VEN molecule,
with a complete removal after 20 min of treatment with a current
of 2 A. In contrast, a treatment time about 120 min using BDD at 2 A
is necessary in order to achieve 90% of VEN elimination, and only
54% abatement was obtained with a current of 0.5 A after 120 min
of treatment with BDD. As shown on Fig. 1a, the complete
destruction of E-E was obtained after 120 min of electrolysis with a
current of 2 A regardless of anode material. A different behavior is
164 Y. Ouarda et al. / Chemosphere 193 (2018) 160e169

Fig. 1. Elimination (%) of pharmaceutical pollutants by EO in synthetic HWW. a: E-E, b: IBU, c: CBZ and d: VEN.

observed when 0.5 A is applied, a better elimination of E-E being
obtained using MMO (90%) as compared to BDD (68%).
The degradation of specific pharmaceuticals is not an indication
that they have been completely mineralized, their oxidation
sometimes leading to the formation of more toxic intermediates, as
it is reported by Donner et al. (2013); Illes et al. (2013); Brezina et al.
(2017) in the case of IBU and CBZ oxidation. The mineralization of
organics was monitored by measuring the dissolved organic carbon
(DOC) abatement of the treated solution during electrolysis,
considering the initial and remaining DOC concentrations. DOC
analysis showed that the anodic oxidation of synthetic HWW using
MMO is not efficient for the mineralization of treated solution (see
Fig. SM-4). Indeed, no DOC removal was observed during the
electrolysis using MMO. However, 67% of DOC removal was ach-
ieved using BBD at 2 A after 120 min of treatment. DOC results
could be explained by the fact that BDD produce a high concen-
tration of hydroxyl radicals compared to MMO. It is believed that, in
our experimental conditions, MMO was not effective to oxidize the
pollutants into CO2 and H2O owing to the fact there was a strong
interaction between MMO and the hydroxyl radical (active elec-
trode) so that this electrode could not easily mineralize the organic
matter. In contrast, with a non-active electrode (such as BDD
anode), weak interactions exist between hydroxyl radical and the
surface, so that the oxidation of organics is mediated by hydroxyl
radical and may results in fully oxidized reaction products
(Comninellis, 1994).
3.3. Hydroxyl radical production
The hydroxyl radical production is an important parameter to
take into consideration when comparing the treatment perfor-
mances using different anode materials. In this study, the evalua-
tion of hydroxyl radical production was done by following pCBA
degradation during EO with the selected anodes (Ti/MMO and
 Y. Ouarda et al. / Chemosphere 193 (2018) 160e169
Fig. 2. Hydroxyl radical exposure ([pCBA] ¼ 200 mg L1) in presence and in absence of
glucose in synthetic HWW.
Nb/BDD).
The results of hydroxyl radical exposition are illustrated in Fig. 2.
In the case of MMO, there was no degradation of pCBA, which
strongly suggests that there was less exposure to hydroxyl radicals
in the vicinity of the MMO surface anode. Unlike MMO, a strong
production of hydroxyl radicals was observed with BDD, with an
exposure to hydroxyl radicals in the order of 4.5  1010 M s after
120 min of treatment.
The main characteristics of BDD are its high reactivity toward
organic oxidation and the effective use of the electrical energy
(Frontistis et al. (2017)). BDD can also generates hydroxyl radicals
weakly adsorbed on the anode which contributes to mineralize
various organic substances. The interaction between BDD and
OH
is considered to be very weak, resulting in a much greater O2
overvoltage than the other conventional anodes and in an
enhancement of organic removal (Panizza and Cerisola (2009)). At
last, several authors reported that BDD is powerful enough to
mineralize organic pollutants and their carboxylic acids generated
from wastewaters and has a much higher oxidizing power than
other common anodes like iridium (IV) oxide (IrO2), platinum and
lead dioxide (PbO2) (Martínez-Huitle et al. (2004); Flox et al. (2005,
2006); Sire
s et al. (2006); Ozcan et al. (2008); Sire
s et al. (2008);
Zhao et al. (2008); Ciríaco et al. (2009); Flox et al. (2009); Hamza
et al. (2009); Zhao et al. (2009)).
Fig. 2 illustrates the hydroxyl radical exposition with and
without organic matter (glucose). According to the results and for
both anodes, the hydroxyl radical exposition was lower in presence
of glucose, suggesting that hydroxyl radicals react with organic
matter and that glucose acts as a radical scavenger. Similar results
were reported by Buffle et al. (2006); Rosenfeldt et al. (2006); Wert
et al. (2007) in terms of hydroxyl radical exposure during phar-
maceutical oxidation using different advanced oxidation processes
such as ozonation, O3/H2O2 and UV/H2O2.
Based on the results of the degradation of pharmaceutical pol-
lutants, mineralization (DOC) and exposure to hydroxyl radicals,
BDD was chosen for this configuration. Treatment time was
maintained at 40 min and a current of 2 A was applied. After EO
pre-treatment, pharmaceuticals’ removal was 50.6 ± 3.9%,
62.5 ± 4.7%, 86.0 ± 4.6% and 66.3 ± 3.6% for VEN, IBU, E-E and CBZ,
respectively.
165
3.4. Coupling of electrochemical advanced oxidation process
followed by membrane bioreactor
The effect of coupling EO and membrane bioreactor was eval-
uated for the pharmaceuticals removal. EO was first assayed up-
stream, as a pre-treatment prior to MBR, using BDD with an
intensity of 2 A for a period of 40 min (Fig. 3). The degradation
percentages recorded with EO alone for the mixture of four
different pharmaceutical pollutants were 50%, 55%, 90% and 66% for
VEN, IBU, E-E and CBZ respectively. Thereafter, the pretreated
effluent was conducted to MBR. A high removal of E-E and IBU more
than 99% was observed in the effluent of the MBR. The removal of
IBU in MBR is reported by several authors as Joss et al. (2006);
Samaras et al. (2013), the main degradation mechanism is found
to be biodegradation (90e100%) while the sorption was less than
5%.
Moreover, this configuration allowed a 92% removal for VEN,
which was far greater than both treatments alone, with lower than
30% and 50% for MBR and EO, respectively (Fig. 3). The high elim-
ination of CBZ <60% was achieved in EO; however, the combination
of both processes shows negative removal of CBZ which decrease
the total removal of CBZ by 20% and a total removal of 42% was
achieved. The negative removal was probably due to CBZ residues
desorption from sludge. Some studies reported a negative removal
of CBZ due to a reconversion of CBZ glucuronides into parent
compounds (Vieno et al. (2007)). However, since this work is con-
ducted using a synthetic wastewater, the probability of presence of
metabolites (glucuronide) and by-products was negligible.
Although MBR shows negative removal, the total removal of CBZ
was greater than that (20% of CBZ removal) reported in the litera-

mez et al. (2016)).
ture using EO as post-treatment (García-Go
These results suggest that the pre-treatment using EO followed
by biological treatment may not be the ideal option for HWW
treatment. This configuration is not always efficient to remove
some recalcitrant pharmaceutical compounds such as CBZ which is
reported to be also persistent during biological processes (Kim et al.
(2014)).
3.5. Electrochemical advanced oxidation process as a post
treatment
The removal of the tested pharmaceuticals was then assayed by
coupling MBR and EO, the latter being installed downstream the
biological reactor. Under the tested conditions, the MBR allowed
the removal of more than 90% of IBU and E-E. Their high sorption
potential on sludge (Log Kow; E-E: 4.01 and IBU: 3.97) has probably
contributed to the observed removal (Tiwari et al. (2017)). On the
other hand, CBZ and VEN were much more recalcitrant to removal
by MBR, with lower than 10%. Their low sorption (Log Kow < 3)
could be behind their recalcitrance. These results are supported by
the finding of Radjenovic et al. (2007). In terms of nutrient removal,
high COD and nitrogen removal rates (>92%) were achieved in the
membrane bioreactor while the orthophosphates are poorly elim-
inated (25e45%) (see Figs. SM-1, SM-2 and SM-3).
The use of EO as a post treatment (polishing treatment)
contributed to the elimination of recalcitrant compounds such as
CBZ and VEN that were barely removed by MBR. As for the first
configuration, a kinetic study using the preselected anodes (MMO
and BDD) was performed with currents of 0.5 and 2 A for 120 min. A
complete removal of E-E, CBZ and VEN was achieved with BDD and
MMO after 40 min of treatment with an intensity of 2 A (Fig. SM-5).
A high removal of IBU (96%) was observed with BDD, but it did not
exceed 24% with MMO under the same conditions. A similar
behavior was observed for the first configuration (EO as a pre-
166 Y. Ouarda et al. / Chemosphere 193 (2018) 160e169

Fig. 3. Pharmaceuticals elimination (%) in the first configuration (EO as a pre-treatment). Nb/BDD as anode, treatment time: 40 min, current intensity: 2 A. a: E-E, b: IBU, c: CBZ and
d: VEN.

treatment), and in agreement with Ambuludi et al. (2013), con-
firming that IBU is better removed by BDD in comparison with
other anodes material. The same results were obtained with other
pharmaceuticals removal with BDD at 0.5 A. A complete removal of
E-E, VEN and CBZ were observed after 40 min, while the removal of
IBU exceeded 92%.
On the other hand, it took 120 min to achieve 44% removal of
IBU and 82% of CBZ using MMO at 0.5 A (Fig. SM-5). Therefore, BDD
was chosen as the preferred anode material for this configuration,
and 0.5 A was considered sufficient as the applied current for
40 min of treatment. The results of pharmaceutical removal for this
configuration are illustrated in Fig. 4.
In order to better understand the difference between BDD and
MMO on pharmaceutical removal, a comparison between those
two anodes was made in terms of hydroxyl radical exposure by
following pCBA degradation (Fig. SM-6). The kinetic of pCBA
degradation was made with an intensity of 0.5 A since with this
intensity a very high removal percentage of pharmaceuticals was
observed. According to Fig. SM-6, the exposition to hydroxyl radi-
cals with BDD was much higher than MMO achieving 5  1011 M.s.
after 60 min of treatment, while it reached only 0.6  1011 M.s.
with MMO. The hydroxyl radical production could explain the high
efficiency of pharmaceutical removal with BDD in comparison with
MMO.
 Y. Ouarda et al. / Chemosphere 193 (2018) 160e169 167

Fig. 4. Elimination (%) of pharmaceutical pollutants in the second configuration (EO as

a post-treatment). Nb/BDD as anode, treatment time: 40 min, current intensity: 0.5 A.

3.6. Toxicity of the synthetic hospital wastewater before and after

treatment

In order to evaluate the toxicity of the synthetic wastewater and

pharmaceutical pollutants before treatment, toxicity tests were
carried out on the synthetic effluent with and without pharma-
ceuticals. The results showed a similar toxicity effect for both ef-
fluents (100% of mortality for 100% v/v), which suggest that
mortality was induced by chemicals other than pharmaceuticals
(see Fig. 5). As reported by Osada et al. (2011), ammonium could be
the reason behind Daphnia magna mortality. No significant toxicity
was measured after the treatment with MBR alone (LC50 > 100% v/
v) has generated the least toxic effluent even with a poor removal of
CBZ and VEN. The absence of toxicity in samples coming from MBR
can be explained by nitrification phenomenon occurring in the
MBR. These results are consisting with those reported by García-
Go
mez et al. (2016) after the application of MBR for CBZ degrada-
tion. According to the authors, the reason of the nontoxic effect on
Daphnia magna and Vibrio fischeri is the elimination of organic
matter and nutrients by MBR. The combination of MBR and EO (EO
as post treatment) has not generated toxic effluents except at 100%
v/v (70 ± 35% of mortality). Several studies reported that secondary
by-products formed during the treatment could be more toxic to-
ward Daphnia magna and Vibrio fischeri, than the parent com- Fig. 5. Toxicity assessment on Daphnia magna for the first (a) and second configuration
(b).
pounds such as CBZ by products (Velegraki et al. (2010); García-
Go
mez et al. (2016)). The toxicity could also be caused by residual
reactive chemical oxidants produced during electrolysis. The sec-
The treatment of synthetic HWW by MBR provided a high
ondary by-products and residual reactive chemical oxidants could
quality effluent in terms of COD, ammonium, and suspended solids
be responsible for the toxicity of the treated effluent. However,
removal and also regarding biodegradable organic compounds
further analyses would be necessary to confirm this hypothesis.
elimination. However, MBR seems not to be very efficient toward
According to the observed toxicity and in terms of pharmaceutical
some recalcitrant pollutants such as CBZ and VEN where the
removal, the second configuration (EO as post-treatment) was
removal does not exceed 20%. On the other hand, it takes more than
chosen as the best configuration for the treatment of HWW.
120 min with an intensity of 2 A to completely eliminate pharma-
ceuticals from synthetic HWW during EO using BDD which is not
4. Conclusions cost effective.
The combination using EO as pre-treatment followed by MBR
From the study, it was concluded that coupled treatment has improved VEN removal. Unlike VEN, CBZ residual concentration
strategy is highly promising in removal of pharmaceuticals from was about 50% of initial concentration. The treatment combining
synthetic wastewater. the MBR followed by EO as polishing treatment using BDD anode,
168 Y. Ouarda et al. / Chemosphere 193 (2018) 160e169
showed a better removal efficiency of the tested pharmaceuticals,
particularly for VEN and CBZ. A very high removal percentage
(>97%) was observed for all pharmaceuticals after 40 min of
treatment with 0.5 A intensity using BDD. The treated effluent of
this configuration is not toxic to Daphnia magna except at 100% (v/
v). Hence, according to the observed toxicity and in terms of
pharmaceutical removal, the second configuration (EO as post-
treatment) was chosen as the best configuration for the treat-
ment of HWW. The high nutrient removal (COD and nitrogen) by
MBR and pharmaceuticals removal by EO, makes the combined
process a suitable technique for the production of high quality ef-
fluents. However, it is of crucial importance to follow the generated
by-product during the degradation of pharmaceuticals. This latter
may be more toxic than the parent compound. This aspect will be
the subject of another ongoing study.
Acknowledgement
Sincere thanks are extended to the National Sciences and En-
gineering Research Council of Canada (STPGP479160-15) and Pre-
mier Tech Aqua for their financial contribution to this study.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.chemosphere.2017.11.010.
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