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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere
a
Institut National de La Recherche Scientifique (INRS), 490 rue de La Couronne, Qu ebec City, QC, G1K 9A9, Canada
b
Universite de Montreal, 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 Quebec (CRIQ), 333 Franquet, Qu ebec City, QC, G1P 4C7, Canada
h i g h l i g h t s
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
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 161
prevention, diagnosis, treatment and mitigation of diseases or to (carbon felt cathode and a platinum anode, current intensity: 0.5 A,
improve human or animal health. Several studies have reported the temperature: 18 C and treatment time: 30 min), 99.1% of sulfa-
ubiquity of pharmaceuticals in drinking water, surface water and methazine was removed. Finally, a recent study proposed a hybrid
groundwater with concentrations varying from ng L1 to mg L1 (de process coupling EF process (0.1 mM Fe2þ and 0.05 M of supporting
Jesus Gaffney et al. (2016); K'Oreje et al. (2016)). Their presence in electrolyte) and aerobic biological treatment as an efficient treat-
environment has raised concerns about the risks associated with ment of metoprolol (beta-blocker) solutions (0.1 M) (Olvera-Vargas
ecosystems and humans with the exposure to endocrine disruptors et al. (2016)). The authors reported an increase of the biodegrad-
and other pharmaceuticals even at low doses (de Jesus Gaffney et al. ability index (BOD5/COD) from 0.012 to 0.44 and 47% total organic
(2016); Zhao et al. (2016)). Indeed, several authors have reported carbon (TOC) removal after 1 h EF treatment using a BDD anode. An
that the presence of pharmaceutical residues in the environment overall 90% mineralization of metropolol solutions was measured
can cause ecotoxic effects, bacterial resistance and endocrine dis- after a 4-days treatment in the biological reactor. The presented
ruptions (Kostich et al. (2014); Yan et al. (2014)). Generally, hospital results are promising, but the need to work with a low pH (<3)
wastewaters (HWWs) are directly discharged, without any treat- during electro-Fenton represents the main obstacle of this process.
ment, into the sewer system to be co-treated with urban waste- In the framework of this study, the coupling of electro-oxidation
waters (Al Qarni et al. (2016)). Unfortunately, conventional WWTPs (EO) and the membrane bioreactor (MBR) for the treatment of
are mostly designed to separate suspended solids and to eliminate hospital wastewaters will be studied. Two scenarios can be
biodegradable organic matter and they are usually not able to considered, the EO followed by the MBR or the MBR followed by EO.
completely eliminate pharmaceuticals, their elimination depend- In fact, the use of EO as a pre-treatment step contributes to increase
ing on their adsorption on biological sludge and biodegradation the biodegradability of wastewaters (Oller et al. (2011)). On the
(Santos et al. (2007)). other hand, the use of EO as a post treatment (polishing treatment)
Many authors consider electrochemical advanced oxidation helps to eliminate no biodegradable and recalcitrant compounds
processes as ones of most effective technologies for an effective (Comninellis et al. (2008)). Consequently, the main purpose of this
mitigation of no biodegradable pharmaceuticals (Klavarioti et al. study is to evaluate the performances of a combined wastewater
(2009); De Witte et al. (2011); Ganzenko et al. (2014)). Among treatment technology, anodic electro-oxidation and MBR, for the
these technologies, the anodic electro-oxidation process is able to treatment of a synthetic HWW. To the best of our knowledge, only
eliminate refractory emerging contaminants, such as pharmaceu- one publication proposed to use an electrochemical process (i.e. EF
ticals, up to their complete mineralization. Pharmaceuticals process) either as pre-oxidative treatment or as post-treatment for
degradation can be done by direct or indirect electrolysis. The direct removal of pharmaceutical pollutants (i.e. caffeine and 5-
electrolysis consists of an exchange of electrons between the pol- fluorouracil) from industrial pharmaceutical wastewaters in the
lutants and the surface of the anode without involving other sub- presence of a biological process (sequencing batch reactor)
stances, while during the indirect electrolysis, a mediated oxidation (Ganzenko et al. (2017)). The authors concluded that the choice of
occurred between the pollutants and active chlorine species (i.e. an adequate sequence of such a combined process is significantly
HClO, ClO, ClO2), generated in bulk solution (Sires and Brillas related to biodegradability of pollutants and their reactivity to the
(2012)). The major disadvantage which prevents their large scale oxidant species. Finally, as the toxicity is an important parameter
application is their relatively high costs, in particular, those related which allows to evaluate the treatment performances, ecotoxicity
to energy consumption during extended processing time to full tests on Daphnia magna have been performed on raw (synthetic)
mineralization (Oller et al. (2011); Ganzenko et al. (2014)). The and treated wastewater for both treatment configurations.
formation of oxidation by-products, such as bromates, chlorates
and disinfection by-products (such as trihalomethanes) is also 2. Materials and methods
considered as a significant drawback of electrochemical advanced
oxidation processes (Dirany et al. (2011); Verlicchi et al. (2015)). 2.1. Selection and characterization of pharmaceuticals
Consequently, the combination of biological processes and elec-
trochemical oxidation technologies appears to be a promising The pharmaceuticals considered in this study belong to different
alternative to reduce the cost and energy consumption of phar- pharmaceutical groups widely used and reported to occur in
maceutical degradation while limiting the generation of oxidation aquatic environment (Lin et al. (2015); Verlicchi et al. (2015)). These
by-products. In fact, several authors have studied the combination include carbamazepine (CBZ), ibuprofen (IBU), estradiol (E-E) and
of these processes for the treatment of several recalcitrant com- venlafaxine (VEN). All the pharmaceutical products were of the
pounds and reported a significant improvement on the mitigation highest purity commercially available, they were purchased from
efficiency of the treatment compared to biological treatment alone Sigma-Aldrich Canada Ltd (Oakville, ON, Canada). The characteris-
(Mascolo et al. (2010); Reungoat et al. (2010); Rosal et al. (2010); tics of targeted pharmaceuticals are presented in Table SM-1 in
Mansour et al. (2012); Ferrag-Siagh et al. (2013)). Unfortunately, supporting information. A stock solution of each pharmaceutical
few studies have focused on the combination of electrochemical was prepared weekly, from powdered substances in distilled water
and biological processes for the treatment of hospital effluents at a concentration of 1 mg L1 and then stored in dark at 4 C.
(either in synthetic or in real HWWs) and, in general, experiments
are conducted with pharmaceutical concentrations which are 2.2. Preparation of the synthetic hospital effluent
higher than the measured concentrations in real hospital effluents
(Ganzenko et al. (2014); Yahya et al. (2014)). Ferrag-Siagh et al. The synthetic HWW was prepared according to Seyhi et al.
(2013) had studied the combination of electro-Fenton (EF) and (2013). COD, nitrogen and phosphorus were added by glucose,
biological process for tetracycline degradation, where EF was used (NH4)2SO4 and KH2PO4. Nitrogen and phosphorus have been put in
as a pre-treatment step. A complete removal of tetracycline was excess into the synthetic effluent so as not to be deficient in
observed after 20 min of treatment at pH 3, a Fe2þ catalyst con- essential nutrients for bacterial activity. The concentrations of
centration of 0.1 mM and an electrolyte concentration Na2SO4 of glucose, nitrogen and phosphorus are adjusted in order to maintain
0.05 mol L1. Mansour et al. (2011) had also evaluated the treat- a C:N:P ratio of 100:10:5. The concentrations of pharmaceuticals
ment of sulfamethazine-polluted solutions using EF pre-treatment were chosen in agreement with those detected in real hospital ef-
followed by biological process. Under the optimum conditions fluents (Santos et al. (2013); Yilmaz et al. (2017)).
162 Y. Ouarda et al. / Chemosphere 193 (2018) 160e169
2.3. Experimental units were conducted with several anodic materials such as titanium
coated with iridium (IV) oxide (Ti/IrO2), niobium coated with bored
2.3.1. Membrane bioreactor doped diamond (Nb/BDD), titanium coated with platinum (Ti/Pt),
The study was performed using a submerged membrane mixed metal oxide (MMO) composed of titanium coated with
bioreactor (MBR) with a working volume of 5.0 L in continuous iridium oxide and ruthenium oxide (Ti/IrO2/RuO2). For each of
mode. A hollow fiber ultrafiltration membrane (ZW-1, Zenon these tests, the cathode was made of titanium (Ti). Experiments
Environmental Inc., Canada) was immersed in the bioreactor (the were conducted with different currents (0.5, 1 and 2 A) corre-
membrane characteristics are presented in Table SM-2). MBR sponding to current densities of 24, 48 and 96 mA cm2. A treat-
feeding and filtration were carried out by two peristaltic pumps ment time ranging from 0 to 120 min was selected.
(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 2.4.3. Kinetic experiments
to reduce the membrane clogging, an automatic backwash of the The kinetics of pharmaceutical elimination were realized for the
membrane was carried out for 10 s for each 60 s cycle. The clogging two configurations with currents of 0.5 and 2 A and a treatment
of the membrane was controlled by monitoring numeric trans- time ranging between 0 and 120 min with selected anodes. Ex-
membrane pressure (TMP) and once the pressure reaches to 40 kPa periments were duplicated and samples were taken every 20 min.
the cleaning of the membrane was performed following the pro- Concurrently, the hydroxyl radical (OH) exposure was estimated
cedure described by Seyhi et al. (2012) consisting in immersion of from the oxidation of p-chlorobenzoic acid (pCBA). The pCBA is
the fouled membrane in a solution of 1000 mg L1 of NaClO for 6 h, used as a model OH probe, it has a very low reactivity with oxidant
followed by cleaning with a solution of 3 g L1 of citric acid for 1 h species (such as ozone) and reacts quickly with OH (with
and finally a washing with tap water. k”OH ¼ 5.0 109 M1s1) (Elovitz and von Gunten (1999)).
2.6. Toxicity assessment (CBZ > 97%, IBU > 93%, VEN >90% and IBU > 97%). Therefore, Nb/
BDD and Ti/MMO were chosen for the next step of this study.
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 3.2. Electrochemical advanced oxidation process as a pre-treatment
derived from a single clone of Daphnia magna Straus cultured and
maintained in a culture medium (hardness 160e180 mg CaCO3 L1, First, a kinetic study of the target pollutants degradation was
dissolved oxygen 80%, pH 7e8, at 20.0 ± 2.0 C with 16- h light carried out, by comparing the two selected anodes and two
(500e1000 lux) and 8-h dark photoperiod). Neonates were fed different currents. Fig. 1 shows the effect of applied current and
every other day with Pseudokirchneriella subcapitata (20 106 cells anode material on the degradation of selected pharmaceuticals. As
mL1) but they were not fed during the toxicity tests. The alga was revealed in Fig. 1, current intensity is a significant parameter
cultured in 965 mL of demineralized water enriched with 5 mL of affecting pharmaceutical abatement. The highest degradation per-
each macroelement (NaNO3, CaCl2, MgSO4, K2HPO4, KH2PO4, NaCl) centages (>93%) were recorded when applying an intensity of 2 A
and 0.5 mL of each microelement (MnCl2, ZnSO4, Co(NO3), MoO3, regardless of the anode material. These results were expected since
CuSO4). Neonates Daphnia magna (<24-h- old) were exposed 48 h, a high production of hydroxyl radicals is generally observed with
according to the CEAEQ standardised protocol (CEAEQ (2016)), to higher intensities. For all the applied current, the corresponding
the synthetic hospital wastewater before (n ¼ 2) and after treat- concentration decays follow a pseudo-first-order reaction. The
ment (n ¼ 3) using four different process configurations: MBR, MBR apparent first rate constant (k'app) values increase with the applied
followed by EO, EO and EO followed by MBR. The dilution factor current. These results are in agreement with the results reported by
recommended for effluent toxicity is between 0.5 and 0.7 (USEPA Ambuludi et al. (2013) during IBU electrolysis using BDD and Pt.
(2002)). In this study, we evaluated a wide concentration range As illustrated in Fig. 1b, BBD is more effective than MMO for IBU
such as 0.2%, 0.4%, 0.8%, 1.6%, 3.1%, 6.3%, 12.5%, 25%, 50%, 75%, 100%. degradation. In fact, within 120 min of electrolysis at an intensity of
Briefly, four replicates included five neonates (<24- h-old) were 2 A, 94% of IBU elimination was achieved with BDD and 80% with
placed in glass test tubes containing 10 mL of each sample con- MMO. For both electrodes, the IBU concentration decays followed a
centration (culture medium with effluent) and the control (culture pseudo-first-order kinetic equation and the k'apps were 3.9 104
medium). The dissolved oxygen (DO), conductivity, pH, water s1 and 2.2 104 s1 for BDD and MMO respectively. The observed
temperature and the hardness of the samples were measured apparent first order constant was slightly lower than what
before and after the toxicity test. If DO concentration in the samples Ambuludi et al. (2013) and Skoumal et al. (2009) reported
was less than 80% before exposure, aeration might be used to bring (respectively 3.12e7.87 104 s1 and 4.86 104 s1) which can
the DO into equilibrium with air. The measurements of these pa- be explained by the fact that in our study, a mixture of pharma-
rameters are important because the endpoints assessed include the ceuticals was treated simultaneously in synthetic HWW containing
additive effects of chemical, physical and biological components of organic matter, contrary to the reported studies where IBU was the
the sample. The neonates were not fed during the test, the exposure only pollutant present in aqueous solution. When applying 0.5 A,
conditions were: 16-h light (500e1000 lux) and 8-h dark photo- 70% of IBU was eliminated with BDD whereas only 37% was ach-
period, 20.0 ± 2.0 C. The toxicity results were accepted if the ieved with MMO after 120 min of treatment. Ambuludi et al. (2013)
control mortality is equal or lower than 5%. The assessment end- had reported similar results during the electrolysis of IBU con-
points were mortality and immobilization after 48 h of exposure. firming the efficiency of BDD over Pt on IBU degradation. No sig-
The mortality was evaluated by binocular microscope. The neo- nificant difference was observed between BDD and MMO regarding
nates that were able to swim were considered mobile and those CBZ abatement, the only parameter affecting its removal being the
which still moved their antennae but did not swim within 15 s after applied current. In fact, more than 96% degradation is observed
a gentle shaking were considered immobile. 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-
3. Results and discussion firming an important effect on CBZ elimination compared to anode
material.
3.1. Preliminary tests Similar results were reported by García-Go mez et al. (2014)
during the electrochemical oxidation of CBZ (10 mg L1) using
The performances of the anodic electro-oxidation process are BDD and PbO2 anodes. After 100 min of electrolysis with a current
greatly affected by the type of anode material and current (García- of 2 A, a high degradation percentage (90%) of CBZ was observed for
Go mez et al. (2014); Komtchou et al. (2015); Jardak et al. (2016)). In both anodes. A lower apparent rate constant was reported by
this study, experiments were conducted to determine the oxidation García-Go mez et al. (2014) (k'apps 3.5 104 s1) during the elec-
behavior of pharmaceuticals using several anode materials (Ti/ trolysis of CBZ using PbO2 and BDD anodes, however, in this study
PbO2, Nb/BDD, Ti/Pt, Ti/MMO) under specific conditions of current, 10 mg L1 of CBZ was treated compared to 10 mg L1 in our study.
recycling flowrate, and initial pharmaceutical concentrations. Pre- The degradation of E-E and VEN are represented in Fig. 1a and d.
liminary results showed that Nb/BDD and Ti/MMO are more According to the results, VEN abatement is affected by both anode
effective than Ti/PbO2 and Ti/Pt for pharmaceutical oxidation. material and current intensity. The highest elimination percentages
The experiments were carried out with two currents, 0.5 and 2 were achieved with high current (2 A). Comparing MMO and BDD
A, for a treatment time of 120 min with both BDD and MMO anodes. performances, MMO seems to be more effective on VEN molecule,
The choice of two different anodes also allows to study the influ- with a complete removal after 20 min of treatment with a current
ence of the anode activity (BDD non-active anode and MMO an of 2 A. In contrast, a treatment time about 120 min using BDD at 2 A
active anode) on the elimination of pollutants and the production is necessary in order to achieve 90% of VEN elimination, and only
of radicals. After 120 min of treatment, Ti/MMO seems to be very 54% abatement was obtained with a current of 0.5 A after 120 min
effective for the degradation of VEN and EE (100% removal), while of treatment with BDD. As shown on Fig. 1a, the complete
the abatement of CBZ and IBU was 92% and 70%, respectively. Nb/ destruction of E-E was obtained after 120 min of electrolysis with a
BDD showed very high removal percentages for all pharmaceuticals 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 our experimental conditions, MMO was not effective to oxidize the
obtained using MMO (90%) as compared to BDD (68%). pollutants into CO2 and H2O owing to the fact there was a strong
The degradation of specific pharmaceuticals is not an indication interaction between MMO and the hydroxyl radical (active elec-
that they have been completely mineralized, their oxidation trode) so that this electrode could not easily mineralize the organic
sometimes leading to the formation of more toxic intermediates, as matter. In contrast, with a non-active electrode (such as BDD
it is reported by Donner et al. (2013); Illes et al. (2013); Brezina et al. anode), weak interactions exist between hydroxyl radical and the
(2017) in the case of IBU and CBZ oxidation. The mineralization of surface, so that the oxidation of organics is mediated by hydroxyl
organics was monitored by measuring the dissolved organic carbon radical and may results in fully oxidized reaction products
(DOC) abatement of the treated solution during electrolysis, (Comninellis, 1994).
considering the initial and remaining DOC concentrations. DOC
analysis showed that the anodic oxidation of synthetic HWW using 3.3. Hydroxyl radical production
MMO is not efficient for the mineralization of treated solution (see
Fig. SM-4). Indeed, no DOC removal was observed during the The hydroxyl radical production is an important parameter to
electrolysis using MMO. However, 67% of DOC removal was ach- take into consideration when comparing the treatment perfor-
ieved using BBD at 2 A after 120 min of treatment. DOC results mances using different anode materials. In this study, the evalua-
could be explained by the fact that BDD produce a high concen- tion of hydroxyl radical production was done by following pCBA
tration of hydroxyl radicals compared to MMO. It is believed that, in degradation during EO with the selected anodes (Ti/MMO and
Y. Ouarda et al. / Chemosphere 193 (2018) 160e169 165
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- In order to better understand the difference between BDD and
firming that IBU is better removed by BDD in comparison with MMO on pharmaceutical removal, a comparison between those
other anodes material. The same results were obtained with other two anodes was made in terms of hydroxyl radical exposure by
pharmaceuticals removal with BDD at 0.5 A. A complete removal of following pCBA degradation (Fig. SM-6). The kinetic of pCBA
E-E, VEN and CBZ were observed after 40 min, while the removal of degradation was made with an intensity of 0.5 A since with this
IBU exceeded 92%. intensity a very high removal percentage of pharmaceuticals was
On the other hand, it took 120 min to achieve 44% removal of observed. According to Fig. SM-6, the exposition to hydroxyl radi-
IBU and 82% of CBZ using MMO at 0.5 A (Fig. SM-5). Therefore, BDD cals with BDD was much higher than MMO achieving 5 1011 M.s.
was chosen as the preferred anode material for this configuration, after 60 min of treatment, while it reached only 0.6 1011 M.s.
and 0.5 A was considered sufficient as the applied current for with MMO. The hydroxyl radical production could explain the high
40 min of treatment. The results of pharmaceutical removal for this efficiency of pharmaceutical removal with BDD in comparison with
configuration are illustrated in Fig. 4. MMO.
Y. Ouarda et al. / Chemosphere 193 (2018) 160e169 167
showed a better removal efficiency of the tested pharmaceuticals, Tetracycline degradation and mineralization by the coupling of an electro-
Fenton pretreatment and a biological process. J. Chem. Technol. Biotechnol.
particularly for VEN and CBZ. A very high removal percentage
88, 1380e1386.
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treatment with 0.5 A intensity using BDD. The treated effluent of incineration of cresols: a comparative study between PbO2 and boron-doped
this configuration is not toxic to Daphnia magna except at 100% (v/ diamond anodes. Chemosphere 74, 1340e1347.
Flox, C., Cabot, P.L., Centellas, F., Garrido, J.A., Rodriguez, R.M., Arias, C., Brillas, E.,
v). Hence, according to the observed toxicity and in terms of 2006. Electrochemical combustion of herbicide mecoprop in aqueous medium
pharmaceutical removal, the second configuration (EO as post- using a flow reactor with a boron-doped diamond anode. Chemosphere 64,
treatment) was chosen as the best configuration for the treat- 892e902.
Flox, C., Garrido, J.A., Rodríguez, R.M., Centellas, F., Cabot, P.-L., Arias, C., Brillas, E.,
ment of HWW. The high nutrient removal (COD and nitrogen) by 2005. Degradation of 4,6-dinitro-o-cresol from water by anodic oxidation with
MBR and pharmaceuticals removal by EO, makes the combined a boron-doped diamond electrode. Electrochim. Acta 50, 3685e3692.
process a suitable technique for the production of high quality ef- Frontistis, Z., Antonopoulou, M., Venieri, D., Konstantinou, I., Mantzavinos, D., 2017.
Boron-doped diamond oxidation of amoxicillin pharmaceutical formulation:
fluents. However, it is of crucial importance to follow the generated statistical evaluation of operating parameters, reaction pathways and antibac-
by-product during the degradation of pharmaceuticals. This latter terial activity. J. Environ. Manage 195, 100e109.
may be more toxic than the parent compound. This aspect will be Ganzenko, O., Huguenot, D., van Hullebusch, E.D., Esposito, G., Oturan, M.A., 2014.
Electrochemical advanced oxidation and biological processes for wastewater
the subject of another ongoing study. treatment: a review of the combined approaches. Environ. Sci. Pollut. Res. Int.
21, 8493e8524.
Acknowledgement Ganzenko, O., Trellu, C., Papirio, S., Oturan, N., Huguenot, D., van Hullebusch, E.D.,
Esposito, G., Oturan, M.A., 2017. Bioelectro-Fenton: evaluation of a combined
biologicaldadvanced oxidation treatment for pharmaceutical wastewater. En-
Sincere thanks are extended to the National Sciences and En- viron. Sci. Pollut. R.
gineering Research Council of Canada (STPGP479160-15) and Pre- García-Go mez, C., Drogui, P., Seyhi, B., Gorta res-Moroyoqui, P., Buelna, G., Estrada-
Alvgarado, M.I., Alvarez, L.H., 2016. Combined membrane bioreactor and elec-
mier Tech Aqua for their financial contribution to this study.
trochemical oxidation using Ti/PbO2 anode for the removal of carbamazepine.
J. Taiwan Inst. Chem. Eng. 64, 211e219.
Appendix A. Supplementary data García-Go mez, C., Drogui, P., Zaviska, F., Seyhi, B., Gorta
res-Moroyoqui, P., Buelna, G.,
Neira-S aenz, C., Estrada-alvarado, M., Ulloa-Mercado, R.G., 2014. Experimental
design methodology applied to electrochemical oxidation of carbamazepine
Supplementary data related to this article can be found at using Ti/PbO2 and Ti/BDD electrodes. J. Electroanal. Chem. 732, 1e10.
https://doi.org/10.1016/j.chemosphere.2017.11.010. Hamza, M., Abdelhedi, R., Brillas, E., Sire s, I., 2009. Comparative electrochemical
degradation of the triphenylmethane dye Methyl Violet with boron-doped
diamond and Pt anodes. J. Electroanal. Chem. 627, 41e50.
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