Chemical Engineering Journal 290 (2016) 12–20

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Chemical Engineering Journal

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

Removal of emerging contaminants from a primary effluent of municipal

wastewater by means of sequential biological degradation-solar
photocatalytic oxidation processes
O. Gimeno ⇑, J.F. García-Araya, F.J. Beltrán, F.J. Rivas, A. Espejo
Departamento de Ingeniería Química y Química Física, Universidad de Extremadura, Avenida de Elvas S/N, 06071 Badajoz, Spain

h i g h l i g h t s

Sequential biodegradation-solar AOPs have been applied to remove ECs from MWWTP.

Biological oxidation only removes caffeine and acetaminophen from wastewater.

Ozonation system led to removal of ECs in less than 45 min.

Solar photocatalytic ozonation with TiO2 showed the highest TOC removal rate.

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

Article history: Treatment of primary wastewater effluent containing a mixture of nine pharmaceuticals model
Received 4 September 2015 compounds (acetaminophen ACM, antipyrine ANT, caffeine CAF, ketorolac KET, metoprolol MET,
Received in revised form 18 December 2015 sulfamethoxazole SFX, carbamazepine CARB, hydrochlorothiazide HCT and diclofenac DIC) has been
Accepted 12 January 2016
carried out by means of aerobic biodegradation followed by different advanced oxidation processes
Available online 19 January 2016
(solar heterogeneous photocatalysis with TiO2, solar photo-Fenton and ozonation). Only ACM and CAF
were completely removed from municipal wastewater in aerobic biological experiments. Apparently,
Keyword:
the bacteriostatic nature of SFX could lead to some extent to bacterial growth inhibition.
Solar photocatalysis
Titanium dioxide
Photocatalytic ozonation allows for a higher degradation rate than simple photocatalytic oxidation in
Ozonation the presence of oxygen. Under the conditions investigated, emerging compounds (ECs) degradation
Pharmaceuticals compounds (sum of concentrations) in the photocatalytic ozonation was in the range 80–100% depending on the sys-
Domestic wastewater tem. Application of solar light (SL) Fe(III) photocatalytic ozonation, SL/O3/Fe (III) (180 min) and ozonation
(45 min) systems reduced the concentrations of the studied emerging contaminants below their
detection limit (2 lg L1). Nevertheless, photocatalytic ozonation led to 41.3% mineralization compared
to 34% achieved by single ozonation. Toxicity analyses by Daphnia magna showed no effluent toxicity
after the application of the three tertiary treatments.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction remaining in solution after the secondary treatment has taken

A number of physical, biological, and chemical processes are
used in wastewater treatment to deal with a variety of contami-
nants. However, some micropollutants found in wastewater, such
as the catalogued as emerging contaminants, are recalcitrant to
some extent to conventional applied wastewater treatment pro-
cesses. Thus, although biological oxidation is likely one of the most
advantageous technologies to deal with wastewater remediation,
some biorefractory compounds are not effectively removed [1–3],
⇑ Corresponding author. Tel.: +34 924289300; fax: +34 924289385.
E-mail address: ogimeno@unex.es (O. Gimeno).
place. Alternative available technologies to deal with this kind of
contaminants include the use of the so-called advanced oxidation
processes (AOPs).
AOPs are based on the chemistry of hydroxyl radicals (
OH),
which are non-selective reactive species, able to oxidize pollutants
into harmless end-products, yielding CO2 and inorganic ions [4–5].
The main drawback of these technologies relies on the economy of
the process. Hence, operating costs associated to the use of AOPs
are much higher than those considered in conventional biological
treatments.
Accordingly, suitable application of AOPs should not consider,
whenever possible, the replacement of the more economic biological

http://dx.doi.org/10.1016/j.cej.2016.01.022
1385-8947/Ó 2016 Elsevier B.V. All rights reserved.
 O. Gimeno et al. / Chemical Engineering Journal 290 (2016) 12–20
processes [6], but the proper combination of both systems. AOPs can
be used as pre- and/or post-treatment of biological systems. In the
former case, AOPs aim at improving biological treatability of
wastewaters, thus favouring their processing by means of common
microorganisms [7]. In the latter situation, the oxidation step is
directed towards the removal of those contaminants not completely
degraded during the biological treatment [8].
In order to ensure the economic optimization of the combined
process, it is necessary to limit the intensity and/or duration of
the advanced treatment. In this sense, in recent years the attention
of research has been focused on AOPs that can be driven by solar
light as photo-Fenton and heterogeneous photocatalysis [9–11].
These technologies, a type of green oxidation systems, have also
been recognized as energy saving and environmentally friendly
processes. Green oxidation is an important challenge since this
technology can effectively reduce the use of energy and consum-
ables [12]. Solar radiation is an incessant source of energy in many
regions, as a consequence, wastewater treatments developed
under the idea of using solar radiation constitute an interesting
research field from the economic point of view. The application
of solar-enhanced AOPs in water/wastewater treatment is a rela-
tively new area of research. The number of studies on the simulta-
neous removal of chemical pollutants and pathogens by solar AOPs
is scarce [13].
Thus, in this study three different oxidation technologies have
been tested in the degradation of some pharmaceutical compounds
not eliminated in a previous biological oxidation step. The systems
investigated were solar heterogeneous photocatalysis with TiO2,
solar photo Fenton (using Fe (III) and magnetite as aqueous iron
source) and single ozonation.
Among light-based systems, heterogeneous photocatalysis with
titanium dioxide as semiconductor is one of the promising AOPs
using minimum energy input costs. Due to photochemical stability,
low toxicity and low cost, powdered titanium dioxide has been
efficiently used to eliminate a large variety of organic pollutants
present in water [14]. Among the drawbacks, the difficult separa-
tion of fine particles of TiO2 from the aqueous matrix and the
wastage of radiation after electron–hole recombination can be
listed.
Additionally, ozonation is a well-established and widely used
technology. Ozone has already been applied at full-scale, but this
process is an energy intensive treatment, characterized by high
operating costs, mainly associated to ozone generation. In any case,
comparison to solar AOPs efficiency is of interest.
Pharmaceuticals are usually non-volatile and often charged
molecules, and many of them pass through treatment plants that
are traditionally designed to get rid of more common pollutants
[2–3]. They have been lurking in the environment since they have
been in use, but it is only in the recent decades that analytical
methods have advanced enough to detect them at the low
levels–less than 1 lg/litre–found in very complex matrixes includ-
ing liquid and solid states, in wastewater, and in surface and
ground waters. Although these levels are becoming easier to quan-
tify, the potential risk they pose is a more complex issue. Nowa-
days it is known that active pharmaceutical ingredients (APIs)
and their biotransformation products are present in a range of
habitats. Some of these compounds can bioaccumulate involving
significant, but largely unstudied, consequences for individuals,
populations and ecosystems [15]. Known environmental effects
of some ECs include the reduction of macroinvertebrate diversity
in rivers, behavioural changes in mosquito fish and reproductive
disruption in fish, etc. [16].
The pharmaceuticals most frequently found in water treatment
effluents are: antibiotics, steroids, antidepressants, analgesics, anti-
inflammatories, antipyretics, beta-blockers, lipid-lowering drugs,
tranquilizers, and stimulants [17]. Different water treatments and
13
their effect on pharmaceutical compounds are described in the
literature, focused on: adsorption/bioadsorption on activated car-
bon, ozonation, photooxidation, radiolysis and electrooxidation
[17]. The simultaneous application of heterogeneous photocatalysis
and ozonation has also great potential in pharmaceuticals
abatement [18]. Various light sources have been employed in pho-
tocatalytic ozonation. Mercury lamp is one the most widely imple-
mented technologies. Cooled xenon and black-light lampshave also
been used. The replacement of UV lamps accounts for a relatively
big part of the operation cost. Thus, the combination of solar light
and ozone could be the ultimate objective from a practical point
of view [18]. As far as the Authors knowledge is concerned, there
are no publications in the specialised literature simultaneously
dealing with biological treatment, solar photocatalytic ozonation,
emerging contaminants, primary municipal wastewater effluent,
magnetite and in situ generation of hydrogen peroxide for photo-
Fenton processes.
Therefore, in this work, experiments of sequential aerobic
biodegradation–AOPs have been conducted by using primary
wastewater effluent containing a mixture of nine pharmaceutical
model compounds. The ECs added to the domestic wastewater
were acetaminophen (ACM, analgesic and antipyretic); antipyrine
(ANT, analgesic and antipyretic); caffeine (CAF, stimulant drug);
ketorolac (KET, nonsteroidal anti-inflammatory drug); metoprolol
(MET, b1 receptor blocker); sulfamethoxazole (SFX, antibiotic);
carbamazepine (CARB, anticonvulsant); hydrochlorothiazide
(HCT, thiazide diuretic) and diclofenac (DIC, nonsteroidal anti-
inflammatory drug). Concentration of pharmaceutical compounds,
mineralization levels (as total organic carbon, TOC) and chemical
oxygen demand (COD) were monitored to assess the extent of
the oxidation. Also, the concentration of some intermediates and
toxicity were measured.
2. Materials and methods
2.1. Primary wastewater effluent and chemicals
The Municipal Wastewater Treatment Plant (MWWTP) of
Badajoz (Spain) has the following consecutive stages: physical
pre-treatment, primary sedimentation units, aerobic biological
process and secondary sedimentation units (water line). At this
point, treated municipal wastewater is discharged into Guadiana
River. Anaerobic digestion is only used for sludge treatment. Pri-
mary effluent samples from the Rincón de Caya (Badajoz) MWWTP
were collected and spiked with the nine selected pharmaceuticals
with a concentration of 200 lg L1 each. This concentration was
higher than real levels found in some urban wastewater [19–20],
but it allows for accurate and fast quantitative chemical analysis
with available analytical equipments (see below). Nevertheless,
sources concentration levels of pharmaceuticals (measured in
raw municipal wastewater), up to 140 lg L1 have been reported
in the literature [3,21–22]. The physical–chemical characterization
of the wastewater used in this work was given in a previous article
[23]. Pharmaceuticals and Fe(ClO4)3.xH2O were purchased from
Sigma-Aldrich (Spain), Fe3O4 from Bendix (Spain) and TiO2
AeroxideÒP25, from Evonik Industries AG, (Germany). All reagents
were used as received. Other chemicals were at least reagent grade
and also used as received.
The emerging contaminants used in this study were chosen
from different pharmaceutical compound families (analgesic,
beta-blockers, antiepileptic, antibiotic, etc) and their presence in
different natural waters bodies has been reported (rivers, lakes,
etc., [24–25]).
Conventional activated sludge was used as biomass for aerobic
biological experiments and collected from the secondary aeration
14 O. Gimeno et al. / Chemical Engineering Journal 290 (2016) 12–20
basin of Badajoz MWWTP. This aeration tank was operated at a
food to microbial (F/M) ratio of 0.5, hydraulic retention time of
7 h and a Mixed Liquor Volatile Suspended Solids concentration
(MLVSS) of 1.5 g L1.
2.2. Experimental setup
2.2.1. Biological treatment
The aerobic method has been used to reproduce the activated
sludge system operating in the Municipal Wastewater Treatment
Plant of Badajoz. Biological oxidation experiments in aerobic con-
ditions were carried out batch mode in a rectangular 30-L glass
tank provided with several air diffusers and mechanical stirring.
Biodegradation of the ECs studied was carried out by duplicate at
atmospheric pressure in 30 L of primary wastewater effluent. Air
fed in a continuous regime through a glass diffuser allowed for a
dissolved oxygen concentration in wastewater of roughly 3.0 mg
O2 L1. Hydraulic retention time (HRT) of biological experiments
was 7 h and sludge age of biomass utilized was between 5 and 6
days. The biological reactor was kept at room temperature
(20 ± 1 °C), dissolved oxygen level was maintained in the range
2–4 mg L1, MLVSS/MLSS was approximately 0.80.
During experiments, samples were regularly (hourly) with-
drawn to follow different parameters like pharmaceuticals concen-
tration, total organic carbon (TOC), chemical oxygen demand
(COD) and aromatic and unsaturated organic content (Abs254).
Mixed liquor samples were tested for Mixed Liquor Volatile Sus-
pended Solids (MLVSS) concentrations as well as the Sludge Vol-
ume Index (SVI). Also, carboxylic acids and ecotoxicity to
Daphnia magna were measured at the beginning and the end of
the assay. Prior to the analysis, centrifugation (5415D Eppendorf
Centrifuge, Hamburg, Germany) and subsequent filtration through
0.45 lm filter (Millex HV Millipore, Madrid, Spain) of samples were
carried for solid removal.
2.2.2. Advanced oxidation processes
Experiments were carried out in duplicate in semi batch mode in
a 5 L (1.8 L of irradiated volume) compound parabolic collector
(CPC) solar photo-reactor developed by Ecosystem-Environmental
Services S.A. (Barcelona, Spain) (see Fig. 1). This reactor provided a
Fig. 1. Advanced oxidation treatment setup with solar radiation. 1: air compressor; 2: ozone generator; 3: ozone analyser (inlet stream); 4: mass flow controller; 5: CPC
reactor; 6: UV radiometer; 7: ozone analyser (outlet stream); 8. ozone destructor; gas-liquid separator; 10: pump; 11: sample point.
0.25 m2 reflection surface made of electropolished aluminum
320 G following an involute around four parallel borosilicate glass
tubes so that the concentration factor is near 1 and the radiation
acceptance semi-angle is 90°. Aqueous solution and the required
catalysts and reagents (i.e., iron oxides, TiO2) were loaded into a
tank and were continuously pumped through the tubes by a
centrifugal pump at a flow rate of 10 L min1. When heterogeneous
catalytic reactions were carried out, spiked wastewater with cata-
lyst was recirculated under dark conditions during 30 min to test
pharmaceutical adsorption onto solids. Instantaneous global UV
(direct plus diffuse) was measured with an UV radiometer
ACADUS85-PLS (Ecosystem-Environmental Services S.A., Barcelona,
Spain). In order to achieve the highest possible incident radiation
flux, experiments were started at midday and the photoreactor
was placed on a fixed platform inclined 45° with respect to the hori-
zon, which is approximately similar to the latitude of the local place.
The accumulated UV-A energy (kJ L1) incident on the reactor at a
given time (QUVA,n) was calculated using the following Eq. (1), [11]:
UV Gn Ai;T
Q UVAn ¼ Q UVAn1 þ Dtn ð1Þ
1000V
Dtn ¼ tn  tn1
where tn is the time corresponding to n water sample (seconds),
UVG,n the average solar ultraviolet radiation measured during the
period Dtn (Wm2), V the total reactor volume and Ai,T is the illumi-
nated area of collectors (m2). With the use of this parameter, the
effect of radiation flux, reactor geometry and solar radiation spec-
trum on the performance of the system can be accounted for.
Ozonation experiments were carried out with an ozone-oxygen
gas flowrate of 0.58 L min1 (ozone concentration in the gas phase
13 mg L1). Ozone was produced from pure oxygen by using a San-
der Ozone Generator. Ozone gas concentration at the inlet and out-
let was monitored through a GM-6000-RTI and GM-6000-PRO
ozone analyzers, respectively (Anseros).
Catalyzed reactions with 2.8 mg L1 Fe(III) or 150 mg L1 Fe3O4
were carried out under acidic conditions (pH 3) to avoid the forma-
tion of iron hydroxide precipitates [26]. Catalyzed reactions with
250 mg L1 TiO2Aeroxide P25 were carried out at natural pH.
 O. Gimeno et al. / Chemical Engineering Journal 290 (2016) 12–20
During each experiment, samples were withdrawn from the
reactor to analyse the concentration of pharmaceuticals, TOC,
COD, hydrogen peroxide, dissolved ozone, Abs254, carboxylic
acids, and D. magna ecotoxicity.
2.3. Analytical methods
Prior to analysis, the solid was removed from samples by filtra-
tion through a Millex-HV filter (Millipore, 0.22 lm). Micro pollu-
tants concentration in the aqueous phase was analysed by high
performance liquid chromatography (HPLC) using a LaChrom Elite
equipment (Hitachi, Spain) provided with a Phenomenex (Spain)
Synergi Hydro-RP column (250  4.60 mm, particle size 4 lm,
80 Å), a L-2450 DA detector and an EZ Chrom software for data
treatment. A binary mixture of acetonitrile (A) and acidified water
with 0.1% formic acid (B) was used as the mobile phase. A linear
gradient of 40 min from 10% to 100% of A with a flow rate of
0.2 mL min1 mobile phase gradient program was used. The injec-
tion volume was 99 lL. Detection and quantification limits for
accurate measurements of concentrations were about 2 lg L1
and 5 lg L1, respectively. Analysis of standard solutions was
repeated to establish the precision of the method that resulted to
be ±2%, while accuracy was 1.3%.
TOC was determined by a TOC-VCSH Shimadzu Analyser (VWR,
Spain). COD was measured following the standard dichromate
reflux method in a Dr. Lange spectrophotometer [27]. Hydrogen
peroxide concentration was determined by the method proposed
by Maschelein [28], based on cobalt (II) and bicarbonate oxidation
through hydrogen peroxide and the formation of a complex with
maximum absorbance at 260, 440 and 635 nm. Determination of
hydrogen peroxide was measured at 260 nm. Dissolved ozone con-
centration in aqueous solutions was analysed by the indigo
method [29]. Ozone in the gas phase was monitored by means of
an AnserosOzomat ozone analyser. Also, the generation of car-
boxylic acids was monitored by ion chromatography using a
Metrohm 881 Compact IC pro equipped with a Metrosep A Supp
7 column (150  4.0 mm, particle size 5 mm) (Metrohm, Herisau,
Switzerland). The injection volume was 20 mL. The program used
for anionic analysis comprised a 15 min isocratic step with
0.6 mM Na2CO3, followed by a 9-min gradient program to reach
a 90/10 (v/v) of a mixture of 0.6 mM Na2CO3 and 35.6 mM Na2CO3,
respectively, and finally, another 26 min gradient program to end
with a 60/40 (v/v) mixture of 0.6 mM Na2CO3 and 35.6 mM
Na2CO3, respectively. The mobile phase flow rate was
0.7 mL min1. pH was tested with a Crison GLP-21+ pH meter.
Finally, acute toxicity Daphnia tests were conducted following
the commercial kit DAPHTOXKIT FTM test (Creasel BVBA; Deinze,
Belgium) using water flea D. magna according with conditions
prescribed by OECD Guideline 202 [30].
3. Results and discussion
3.1. Aerobic biological oxidation. Activated sludge system
In order to ascertain the biodegradability of the ECs under
study, prior to chemical oxidation, a series of aerobic biodegrada-
tion experiments were carried out by varying the initial amount
of biomass (measured as Mixed Liquor Volatile Suspended Solids,
MLVSS) and various hydraulic retention times (HRTs). A control
experiment (without emerging pollutants) was also conducted to
assess the effect of ECs on the activated sludge.
3.1.1. Influence of initial biomass concentration
Initially, a series of batch experiments were performed with a
biomass concentration ranged between 1000 mg L1 and
15
2000 mg L1 measured as MLVSS (see Table 1). To reproduce the
aerobic biological oxidation process taking place in Badajoz
Wastewater Treatment Plant, runs were conducted for a period of
7 h (HRT of Badajoz MWWTP). Fig. 2 shows the evolution of the nor-
malised remaining concentration of COD versus time corresponding
to experiments completed with different initial biomass concentra-
tions and the control experiment. As it can be inferred from this
figure, the activity of the tested sludge is almost the same for the
three experiments and it is lower than the control reaction. Hence,
after 7 h of biological oxidation just 50% of COD (average value) elim-
ination was achieved in experiments conducted in the presence of
emerging contaminants compared to 82% of COD removal
experienced in the control biodegradation test. Accordingly, the
impact of ECs occurrence on COD removal is considerable. This fact
evidences some kind of disturbance to microorganisms present on
the activated sludge. Hence, Collado et al. [31] found that the
bacteriostatic nature of sulfamethoxazole can cause a shift of the
microbial composition. SFX (at a concentration of 50 lg L1) altered
the distribution of bacteria within the community and substantially
decreased microbial diversity during the exposure period [31].
Taking into account that in this study, SFX initial concentration
was 200 lg L1, the observed DQO inhibition is likely due to the
presence of this antibiotic. Furthermore, this inhibitory effect of
SFX has also been reported by other authors [32–34].
The evolution of other parameters like total carbon (TC) and
total organic carbon (TOC) followed a similar trend. The initial
and final values of additional measured parameters like the sludge
volume index (SVI) are also presented in Table 1. Activated sludge
settling capability is a critical factor in wastewater treatment
plants. An efficient and rapid separation between treated wastew-
ater and biomass in the secondary settler unit is always required.
Table 1 shows the sludge volumetric index parameter correspond-
ing to the biodegradation experiments. As seen from Table 1, SVI
factor did not show a general trend regardless of the initial biomass
concentration. Under the batch conditions applied in this study, it
is not expected to observe any effect on SVI values by the only
presence of ECs. SVI factor usually increases due to the increasing
abundance of filamentous bacteria in the medium.
Regarding ECs biodegradation, with the exception of CAF, ACM
and MET, the rest of pharmaceuticals compounds were hardly
removed from the urban wastewater after the aerobic biological
oxidation took place (see Figure S1 in supplementary section).
The concentrations of ACM and CAF partially decreased at the
beginning of the process leading to 61% and 57% removal values
(see Figure S1 of supplementary section), respectively, after 2 h
in the presence of 1510 mg MLVSS L1. High conversion values
for ACM and CAF have also been reported by other authors in aer-
obic biodegradation processes [35–37]. ANT, KET, CARB, HCT and
DIC were the pharmaceuticals showing the lower removal efficien-
cies (below 4%), when treated with activated sludge.
ECs removal in the activated sludge process is mainly attributed
to two mechanisms: sorption onto biological flocs and biodegrada-
tion. The elimination of ACM and CAF under these conditions is
predominantly endorsed to biotic transformation processes
[38–41]. In the case of the beta blocker, literature reports that
MET is not removed efficiently by conventional wastewater treat-
ments [3,42–44]. In this research, a 42% MET conversion was
attained in 7 h of biological degradation after an initial induction
period of 4 h (see Figure S1, supplementary section). Similar results
were found in the experiments carried out with a different initial
concentration of microorganisms (930 and 1970 mg MLVSS L1)
(results not shown).
3.1.2. Influence of hydraulic retention time
Finally, a series of experiments was conducted at different
hydraulic retention times from 7 to 24 h and approximately
16 O. Gimeno et al. / Chemical Engineering Journal 290 (2016) 12–20

Table 1
Initial conditions and conversion (in parenthesis) of some parameters in experiments of domestic wastewater biodegradation in the presence of pharmaceutical compounds.

Run (h) MLVSSo (mg L1) CODo (mg L1) COTo (mg L1) SVIo, mLgSSV1 SVIf, mLgSSV1 lmax h1  103
7 1970 ± 57 195 (44 ± 7%) 43 (41 ± 5%) 41 ± 7 30 ± 5 5.7 ± 0.8
7 1510 ± 77 229 (51 ± 3%) 45 (47 ± 6%) 33 ± 2 30 ± 6 6.4 ± 0.9
7 930 ± 21 196 (55 ± 9%) 75 (45 ± 7%) 65 ± 8 95 ± 1 6.8 ± 1.7
7* 1140 ± 42 229 (82 ± 6%) 80 (69 ± 3%) 189 ± 25 150 ± 2 4.3 ± 0.5
12 1000 ± 35 273 (64 ± 8%) 73 (47 ± 7%) 24 ± 1 38 ± 4 7.4 ± 1.2
24 990 ± 38 296 (66 ± 7%) 78 (53 ± 9%) 32 ± 6 45 ± 7 6.3 ± 0.8

Error calculated from repeated experiments and analysis by triplicate of each sample after determination of 95% confidence interval based on standard deviation.
*
Control run.

defined in Eq. (3) and YSSV/COD is the heterotrophic yield coefficient,

described in Eq. (4), which relates substrate (COD) consumption
and increase of biomass during the exponential growth phase.

COD
l ¼ lmax ð3Þ
K S þ COD

MLVSS  MLVSSo
Y MLVSS=COD ¼ ð4Þ
CODo  COD
In Monod Eq. (3), lmax denotes the maximum specific growth
rate and Ks is the saturation constant. Now assuming that the term
mMLVSS is negligible (in the exponential growth phase of biologi-
cal batch experiments, almost all substrate consumption goes to
formation of new biomass), the heterotrophic yield coefficient
remains constant during the exponential growth and the value of
Ks is often rather small [46], after integration Eq. (2) gives:
Fig. 2. Aerobic biological degradation of domestic wastewater doped with ECs.  
Evolution of the normalised remaining chemical oxygen demand (COD) with time. W  Y MLVSS=COD COD
Influence of initial biomass concentration. Conditions: T = 293 K, pH = 8; DO:
ln ¼ lmax t ð5Þ
MLVSSo
3 mg L1, CODo = 212 mgO2 L1 (average value). MLVSSo (mg L1): r 1140 (control
experiment in absence of pharmaceuticals), j 1970, N 1510, d 930.
where the parameter W is defined as follows:

W ¼ MLVSSo þ Y MLVSS=COD CODo ð6Þ

1000 mg L1 of initial biomass concentration. As expected, the
increase of HRT in biological oxidation leads to a higher COD and
TOC conversion (see Table 1). Nevertheless, in both cases, removals
were lower than those achieved in the control experiment (7 h
period).
Regarding to ECs degradation, after 12 and 24 h, ACM and CAF
were completely removed from wastewater (results not shown),
respectively. In the case of MET, an improvement of its biological
degradation when increasing the reaction period from 7 to 12
and 24 h was experienced, achieving 83% and 88% elimination val-
ues, respectively. The rest of ECs studied kept their recalcitrant nat-
ure to conventional biodegradation as they were not eliminated
from wastewater after 24 h of biological treatment.
From Eq. (5), a plot of the left term vs. time should lead to a
straight line of slope lmax. Table 1 displays the results of the linear
regression applied to the experiments presented in the previous
section. A reasonably consistency of the value lmax was attained
in experiments carried out under similar conditions of temperature
and pH. Nevertheless, these values were lower than those achieved
in the control experiment. As stated previously, the presence of SFX
can cause some bacterial growth inhibition. This hypothesis was
corroborated by MLVSS analysis (after 7 h period) obtaining an
increase in microorganism concentration of 40, 71 and 30 mg
MVLSS L1 in experiments conducted with an initial concentration
of 1970, 1510 and 930 mg MLVSS L1, respectively. In the control
experiment the bacterial growth after 7 h was 500 mg MVLSS L1.

3.2. Biodegradation kinetic model 3.3. Solar AOPS after biodegradation

Substrate depletion in an aerobic biological oxidation process is
due to two possible pathways, on one hand, the organic matter
may be the carbon supply of the biomass to produce new cells
and, on the other hand, the substrate may provide the energy nec-
essary to preserve cell activity. Thus, the following equation was
proposed to describe the kinetics of substrate removal [45]:
dCOD 1 with TiO2, solar photo-Fenton (with Fe (III) and magnetite) and
r S ¼  ¼ lMLVSS þ mMLVSS
dt Y MLVSS=COD
In Eq. (2), rS is the substrate removal rate (in this case COD),
t stands for reaction time, MLVSS is the biomass concentration
expressed as the amount of volatile suspended solids, m the main-
tenance energy coefficient, l the specific growth of biomass
As stated previously, conventional biological oxidation is not
able to completely degrade some emerging contaminants. Conse-
quently, different advanced oxidation processes were applied as
tertiary treatments for their elimination from domestic wastewa-
ter. Thus, in a second series of experiments, biologically treated
wastewater (7 h HRT) was subsequently exposed to different AOPs.
Applied technologies were: solar heterogeneous photocatalysis
ð2Þ ozonation.
Experiments were carried out at the normal pH of the sec-
ondary municipal wastewater effluent (pH = 7). Nevertheless, since
at the natural pH of wastewater, iron hydroxide precipitates are
formed [26], solar photofenton reactions with 2.8 mg L1 Fe3+ or
150 mg L1 Fe3O4 were carried out at pH 3.
 O. Gimeno et al. / Chemical Engineering Journal 290 (2016) 12–20
Fig. 3. AOPs removal of ECs after biological oxidation. Evolution of normalized TOC.
Experimental conditions: T = 293 K, pH = 7, CO3inlet = 13 mg L1, Qg = 35 L h1,
CTiO2 = 250 mg L1. Symbols: r SL/O2/TiO2, j SL/O3/TiO2, N O3.
3.3.1. Solar heterogeneous photocatalysis with TiO2
Elimination of the seven pharmaceuticals remaining in the
municipal WWTP secondary biological effluent by solar photo-
catalysis with titanium dioxide was first investigated. For this pur-
pose, a titanium dioxide concentration of 250 mg L1 was used. ECs
adsorption onto TiO2 particles surface was negligible (results not
shown).
Fig. 3 shows the evolution of the normalised remaining concen-
tration of TOC against time corresponding to photocatalytic oxida-
tion (SL/TiO2/O2) and photocatalytic ozonation (SL/TiO2/O3)
systems. Additionally, Table 2 displays the percentage of elimina-
tion of pharmaceuticals from water (sum of concentrations) and
other measured parameters such as COD and absorbance at
254 nm. The absorbance at 254 nm (UV254) has been reported to
be a qualitative indicator of aromatic and unsaturated compounds
present in wastewater [47]. By only considering the system SL/O2/
TiO2 (QUV = 38.23 kJ L1), the percentage of pharmaceuticals degra-
dation is lower if compared to photocatalytic ozonation, with some
emerging contaminants such as metoprolol (3.81%) and antipyrine
(6.52%) being hardly degraded (see Table 3). Thus, from Table 2 it
can be seen that under the experimental conditions applied in this
work, photocatalytic ozonation allows for a higher degradation
rate than simple photocatalytic oxidation in the presence of oxy-
gen. ECs degradation (sum of concentrations) in the photocatalytic
ozonation (QUV = 30 kJ L1) was >80% although they were not com-
pletely removed from wastewater.
In the photocatalytic ozonation process, ozone can enhance the
removal rate by preventing the recombination of photo generated
electron-holes. Additional hydroxyl radicals can also be generated
by reaction between ozone and electrons in the conduction band of
the semiconductor. When oxygen is used as electron acceptor, the
Table 2
Conversion values of some parameters in experiments corresponding to AOPs of biologically treated wastewater in the presence of pharmaceutical compounds. Initial conditions:
RECs = 1.3 mg L1, TOC = 26 mg L1, COD = 53 mg L1. Initial UV254 is given in parentheses.
System pH RECs (mg L1)
SL/TiO2/O2 7 34 ± 5
SL/TiO2/O3 7 80 ± 15
SL/Fe3O4/O2 3 51 ± 9
SL/Fe3O4/O3 3 74 ± 11
SL/Fe(III)/O2 3 60 ± 16
SL/Fe(III)/O3 3 100 ± 0
O3 7 100±0
Error calculated from repeated experiments and analysis by triplicate of each sample after determination of 95% confidence interval based on standard deviation.
17
less reactive superoxide ion radical is formed. The presence of
ozone gives rise to two routes of hydroxyl radicals generation. Sto-
ichiometrically, ozone consumes one electron, while oxygen reacts
with three electrons [48]. Ozone is a better electron acceptor than
oxygen. Accordingly, the SL/TiO2/O3 system showed an enhanced
TOC-removal rate (see Fig. 3). Similar results were found by
Márquez et al. [49] that applied different solar oxidation methods
to remove pharmaceuticals in secondary effluents. Results revealed
that solar photocatalytic ozonation is a promising oxidation
method leading to 95% removal of ECs and 40% mineralization.
3.3.2. Solar photo-Fenton
Solar photo-Fenton, using Fe(III) (homogeneous catalysis) and
magnetite particles (heterogeneous catalysis), was also tested as
a tertiary treatment for remediation of biologically treated
wastewater containing seven emerging contaminants. In this work,
Fe3O4 has been used as a source of aqueous iron. In a previous
work, Rodríguez et al. [26] reported that the presence of oxalic acid
and pH as low as 3 favoured the leaching of iron from the iron oxi-
des (especially from magnetite). Also, it is well known that pH in
the interval 2.5–3 is the optimal to complete Fenton trials.
Degradation of remaining ECs with solar photo-Fenton at pH 3
was carried out with no addition of hydrogen peroxide to the reac-
tion media. Ozonation of pharmaceutical compounds with aro-
matic ring and/or unsaturated carbon bonds in their molecules
leads to in situ generation of hydrogen peroxide. The process is
the result of ozone cycloaddition reaction to double carbon bonds
(Criegge Mechanism, [50]) and aromatic ring electrophilic substi-
tution reaction followed by ring opening, (ozone direct reactions).
This fact has been demonstrated in previous studies [51–52].
Moreover, dissolved organic matter (mainly humic substances,
HS) absorbs solar energy mostly between 300 and 500 nm. Absorp-
tion of irradiation in this region can generate excited triplet states
that initiate a number of photochemical processes, producing per-
oxy and hydroxyl radicals as well as hydrated electrons, hydrogen
peroxide, singlet oxygen and superoxide radical [53]. Taking into
account that the superoxide ion radical is in equilibrium with the
hydroperoxide radical:
pK¼4:8
HO
2 ƒƒƒƒƒ
ƒƒƒƒƒ
ƒ!


ƒ O2 þ H þ ð7Þ
At pH < 4.8, HO2

prevails in water and its recombination reac-
tion generates hydrogen peroxide with a rate constant of
8.3  105 M1 s1 [54]. Once hydrogen peroxide is formed a Fenton
process develops because of the presence of iron in solution.
In this work, the hydrogen peroxide concentration generated in
the four systems applied was experimentally detected reaching a
maximum value of 1.9  105 M (after 240 min of reaction),
4.6  105 M (after 90 min of reaction), 9.5  106 M (after
300 min) and 9.1  105 M for SL/O3/Fe (III), SL/O2/Fe (III), SL/O2/
Fe3O4 and SL/O3/Fe3O4, respectively.
The efficiency of the AOP systems investigated is illustrated in
Fig. 4. This plot shows the dimensionless remaining concentration
TOC (mg L1) COD (mg L1) UV254 elimination
7 ± 0.5 9 ± 0.5 (0.301)86 ± 13
41 ± 9 59 ± 15 (0.302)84 ± 14
7±2 12 ± 3.5 (0.211)8 ± 0.5
19 ± 5 30 ± 8 (0.206)21 ± 5
8 ± 1.5 26 ± 2 (0.239) 20 ± 3
26 ± 8 38 ± 6 (0.251)79 ± 14
35 ± 5.5 58 ± 6 (0.231)72 ± 10
18 O. Gimeno et al. / Chemical Engineering Journal 290 (2016) 12–20

Table 3
Initial concentrations (lg L1) and conversion (%) of micropollutants after 300 min of advanced oxidation processes applied (ozonation not included).

ANT CARB DIC HCTZ KET MET SFX

SL/TiO2/O2 193 198 194 200 200 114 190
7 ± 0.3% 27 ± 5% 49 ± 12% 61 ± 11% 53 ± 8% 4 ± 0.8% 21 ± 4%
SL/TiO2/O3 191 198 194 200 200 114 180
81 ± 11% 77 ± 8% 86 ± 15% 80 ± 9% 86 ± 17% 62 ± 12% 84 ± 14%
SL/Fe3O4/O2 191 200 186 200 200 114 192
18 ± 3% 30 ± 10% 49 ± 5% 86 ± 5% 98 ± 11% 25 ± 3% 39 ± 2%
SL/Fe3O4/O3 191 198 194 200 200 115 180
87 ± 15% 82 ± 12% 54 ± 3% 96 ± 8% 100 ± 1% 66 ± 5% 81 ± 11%
SL/Fe(III)/O2 191 198 194 200 200 114 180
37 ± 7% 41 ± 8% 41 ± 7% 86 ± 10% 91 ± 9% 63 ± 4% 55 ± 4%
SL/Fe(III)/O3* 195 198 194 200 200 114 180
100 ± 1% 100 ± 1% 100 ± 1% 100 ± 1% 100 ± 1% 100 ± 1% 100 ± 1%

Error calculated from repeated experiments and analysis by triplicate of each sample after determination of 95% confidence interval based on standard deviation.
*
After 180 min of illumination.

Fig. 4. AOPs removal of ECs after biological oxidation. Evolution of the dimension-
less remaining concentration of the sum of the seven micropollutants detected.
Experimental conditions: T = 293 K, pH = 7, C O3 inlet = 13 mg L1, Qg = 35 L h1,
C Fe3 O4 = 150 mg L1, CFe(III) = 2.8 mg L1. Symbols: r SL/O2/Fe3O4, j SL/O3/Fe3O4,
N SL/O2/Fe(III), d SL/O3/Fe(III).
of the sum of the seven pharmaceuticals detected versus time for a
period of five hours after the biological treatment took place. From
this figure, it can be inferred that after 180 min of illumination
time (21.24 kJ L1), application of the SL/O3/Fe (III) system leads
to 100% removal of emerging compounds (also see Table 3). The
illumination time necessary for solar photo-Fenton to degrade over
50% of the emerging compounds was 300, 120, 180, 60 min and the
accumulated energy was 47.9, 13.4, 13.5 and 6.6 kJ L1 for SL/O2/
Fe3O4, SL/O3/Fe3O4, SL/O2/Fe(III) and SL/O3/Fe (III), respectively.
Moreover, as it can be seen from Table 2, mineralization was lower
than 30% in all cases. For the systems in the absence of ozone, the
degree of mineralization was even lower (<10%in ozone free pro-
cesses). Low TOC removal efficiencies were also reported by other
authors by solar photo-Fenton in MWWTP effluents [19,55].
3.3.3. Ozonation treatment
Finally, municipal secondary effluents were treated by conven-
tional ozonation without carbonate stripping or pH modification.
After a treatment time of 45 min and an ozone concentration of
13 mg L1 all the pharmaceuticals were removed from municipal
wastewater. Other authors reported similar results, i.e: [11,56].
Molecular ozone degradesorganic contaminants by direct and
indirect reactions trough free radicals that came from O3 decompo-
sition. Thus, ECs under study would be degraded by a combination
of these reactions, depending on water composition, pH and ozone
dose. The time required for ozone to degrade ANT, CARB, DIC,
HCTZ, KET, MET and SFX under the detection limit was 20, 10,
30, 15, 5 and 45 min, respectively.
Also, the evolution of normalized TOC with time is displayed in
Fig. 3. According to this figure and by comparing the results
obtained in the solar photocatalysis with TiO2, the following con-
siderations can be inferred. By only considering the process in
the absence of ozone (SL/O2/TiO2), the presence of titania powder
involves a negative effect on TOC degradation profiles if compared
to ozone based processes. Bubbling of ozone into reaction media
significantly enhances TOC depletion rate, especially when com-
bined with solar radiation and titanium dioxide (Fig. 3). The
remaining TOC in wastewater effluent is formed by intermediates
as no complete mineralisation was attained. Thus, some of the
main intermediates detected along the reaction period that accu-
mulates in the effluent were: propionic, formic, dichloroacetic, suc-
cinic and oxalic acids, for O3, SL/O3/TiO2 and SL/O2/TiO2 systems,
respectively. Nevertheless, toxicity analyses performed showed
no inhibition of D. magna immobilization tests.
Moreover, a significant decrease of COD was experienced in O3
and SL/O3/TiO2 systems (see Table 2). Hence, a 59.3% (SL/O3/TiO2)
and 57.5% (O3) COD conversions were attained compared to values
below 39% for the rest of systems used (see Table 2).
4. Conclusions
From the previous study, the following conclusions can be
gained:

Aerobic biological experiments allows for a complete reduction
of ACM and CAF content of domestic wastewater effluent.

The efficiency of the different ozone-based processes tested
shows the following trend in terms of pharmaceuticals
elimination:
SL/Fe3O4/O3 < SL/TiO2/O3 < SL/Fe (III)/O3 < O3

Solar photocatalytic ozonation with titania significantly favours
COD and TOC elimination of domestic wastewater effluent.

In ozone iron photocatalytic experiments, Fenton processes
develop without the need of supplying hydrogen peroxide. This
oxidant is generated through ozone-ECs direct reactions.
Acknowledgements
The authors thank Spanish DGICYT and Feder funds for the
economic support through project CTQ2009/13459/C05/05. Also,
A. Espejo thanks Junta de Extremadura for her FPI grant.
 O. Gimeno et al. / Chemical Engineering Journal 290 (2016) 12–20
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2016.01.022.
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