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Water Research 102 (2016) 505e515

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Micropollutant degradation, bacterial inactivation and regrowth risk

in wastewater efuents: Inuence of the secondary (pre)treatment on
the efciency of Advanced Oxidation Processes
Stefanos Giannakis a, *, Margaux Voumard a, Dominique Grandjean b, Anoys Magnet c,
sar Pulgarin a, **
Luiz Felippe De Alencastro b, Ce

SB, ISIC, Group of Advanced Oxidation Processes, Ecole Polytechnique F

erale de Lausanne (EPFL), Station 6, 1015 Lausanne, Switzerland
ENAC, IIE, Central Environmental Laboratory, Ecole Polytechnique F
erale de Lausanne (EPFL), Station 2, 1015 Lausanne, Switzerland
Sanitation Service, City of Lausanne, Rue des terreaux 33, 1002 Lausanne, Switzerland

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 30 April 2016
Received in revised form
29 June 2016
Accepted 30 June 2016
Available online 2 July 2016

In this work, disinfection by 5 Advanced Oxidation Processes was preceded by 3 different secondary
treatment systems present in the wastewater treatment plant of Vidy, Lausanne (Switzerland). 5 AOPs
after two biological treatment methods (conventional activated sludge and moving bed bioreactor) and a
physiochemical process (coagulation-occulation) were tested in laboratory scale. The dependence
among AOPs efciency and secondary (pre)treatment was estimated by following the bacterial concentration i) before secondary treatment, ii) after the different secondary treatment methods and iii)
after the various AOPs. Disinfection and post-treatment bacterial regrowth were the evaluation indicators. The order of efciency was Moving Bed Bioreactor > Activated Sludge > CoagulationFlocculation > Primary Treatment. As far as the different AOPs are concerned, the disinfection kinetics
were: UVC/H2O2 > UVC and solar photo-Fenton > Fenton or solar light. The contextualization and parallel
study of microorganisms with the micropollutants of the efuents revealed that higher exposure times
were necessary for complete degradation compared to microorganisms for the UV-based processes and
inversed for the Fenton-related ones. Nevertheless, in the Fenton-related systems, the nominal 80%
removal of micropollutants deriving from the Swiss legislation, often took place before the elimination of
bacterial regrowth risk.
2016 Elsevier Ltd. All rights reserved.

Advanced oxidation processes (AOPs)
Biological treatment
Disinfection kinetics
Physicochemical treatment

1. Introduction
Throughout the years, urban wastewater treatment plants
(WWTPs) have implemented strategies to eliminate the organic
load, chronologically followed by the inorganic one (phosphorus
and nitrogen), and presently, the current average treatment stops at
the disinfection level. Chlorination was until some time ago the
most common disinfection method. However, its use has been
connected with trihalomethane (THM) production, a harmful
disinfection by-product (DBP) of the reaction with organic matter
(Krasner et al., 2009). Hence, treatment at disinfection and

* Corresponding author.
** Corresponding author.
E-mail addresses: (S. Giannakis), cesar.pulgarin@ep.
ch (C. Pulgarin).
0043-1354/ 2016 Elsevier Ltd. All rights reserved.

decontamination level was turned towards safer greener techniques (Michael et al., 2012).
Lately, ozone and ultraviolet light have been widely employed to
tackle the issue of microorganism elimination in wastewater
(Drinan and Spellman, 2012). UVC alone, combination with H2O2
and/or O3 are some of the most studied and well-understood
Advanced Oxidation Processes (AOPs) for this purpose. The UVCbased processes have a well-established disinfection efciency
when applied in secondary wastewater efuents (Rodrguez-Chueca
et al., 2015), but the main concern of bacterial regrowth is yet to be
resolved. In overall, the AOPs gained supporters during the last two
decades, mainly for their non-selective character against organic
matter and microorganisms (Moncayo-Lasso et al., 2012). However,
despite the interest gain, the limited number of full-scale applications engulfs the danger of over- or mal-dimensioning of such units,
since the pre-treatment process differs from plant to plant.
On the other hand, in less wealthy countries of the developing


S. Giannakis et al. / Water Research 102 (2016) 505e515

Abbreviations list

Advanced Oxidation Process

Activated Sludge
Colony Forming Units,
Chemical Oxygen Demand
Cyclobutane-pyrimidine dimer
Disinfection By-Product
Dissolved Organic Matter
Efuent Organic Matter
Hydraulic Retention Time
Moving Bed BioReactor
Molecular Weight

world, ozone and UV-based techniques are far from applicable.

Instead, the use of solar ponds has been widely applied (Von
Sperling, 2005), as a simple, and quite efcient method of treating
wastewater efuents. As this process has been successfully applied,
enhancing its performance with the photo-Fenton reagents could
signicantly increase the removal of microbial and organic loads
(Moncayo-Lasso et al., 2012). Iron and H2O2 are abundant and
environmentally safe, respectively, and the inactivation potential of
photo-Fenton can improve the efuent quality while reducing the
residence times in such congurations (Von Sperling, 2005) or in
Raceway Pond Reactors (RPRs) (Rivas et al., 2015).
In Switzerland, although special effort has been made to effectively remove micropollutants (Giannakis et al., 2015a; Margot
et al., 2013, Margot et al. 2011), the recommended strategies have
not included the microorganism risk in the design, neither in the
legislation. The upgrade of wastewater treatment plants (WWTPs)
affects the >10.000 inhabitant equivalent, thus leaving a large
number of WWTPs without disinfection units. For instance, the
WWTP of Vidy (Lausanne, Switzerland) in its current reconstruction planning, which focuses on the micropollutant removal after
the secondary treatment of wastewater (WW), involves the use of
activated carbon, ozonation, followed by UVC light, but mostly for
degrading the by-products of the previous two installations.
In this work, we take advantage of the simultaneous presence of
3 parallel secondary treatment systems of wastewater treatment in
the plant of Vidy, in order to study the effect of secondary pretreatment on the efciency of AOPs. More specically, wastewater
from Activated Sludge, Moving Bed Bioreactors and CoagulationFlocculation units (with primary wastewater efuent as control)
has been subjected to various oxidation methods. The UVC alone,
UVC/H2O2, Fenton, solar light and (solar) photo-Fenton processes
(namely UV-based and Fenton-related processes) were tested on
the (immediate) bactericidal removal efciency, as well as the posttreatment regrowth. Finally, to put things into the real wastewater
context, the evolution of 8 micropollutants were monitored, and
insights were given on the comparative order of removal of
micropollutants (MPs) and microorganism (MO) regrowth risks.
2. Materials and methods
2.1. Collection of wastewater samples and treatment plant
For the needs of the microbial testing, 6 sampling campaigns


Oxidizable Organic Matter

Photosensitizable Organic Matter
Particulate Organic Matter
Reactive Oxygen Species
Solar Disinfection
Sludge Retention time
Suspended Solids
Specic UV Absorbance
Total Organic Carbon
Total Suspended Solids
Wastewater Treatment Plant

were performed. During each visit, wastewater from the following

points was collected: i) before secondary treatment (after primary
decantation) (PT), ii) after secondary treatment by activated sludge
and secondary clarication (AS), iii) after secondary treatment by
moving bed bioreactors (MBBR) and iv) after physicochemical
treatment by coagulation-occulation (CF). The aforementioned
points can be found in Fig. 1. Each time, a 5-L grab sample was
collected and transported immediately to the laboratory for treatment. For the micropollutants, the strategy has been analyzed in a
previous work (Giannakis et al., 2015a).
The AS unit has a hydraulic retention time (HRT) of 4 h and
sludge retention time (SRT) of 2 days, approximately, without
nitrication. The MBBR capacity is only 5% compared to the AS unit,
but has a longer retention time and includes a nitrication step.
Finally the CF unit is based on chemical coagulation and occulation process by FeCl3 as coagulant. More details on the different
units can be found in Margot et al. (2013).
2.2. Employed chemicals and reagents
For the experiments of bacterial inactivation H2O2 30%, FeSO4$7H2O and Titanium (IV) oxysulfate was acquired from SigmaAldrich (Switzerland) and NaHSO3 for H2O2 elimination from
Sigma-Aldrich and Acros Organics, respectively. Finally, the plate
count agar (PCA) was purchased from Sigma-Aldrich (Switzerland).
2.3. Experimental set-up: reactors and apparatus
The experiments are divided in two main groups, namely the
UV-based and the Fenton-related ones. For the UV-based experiments, two double-wall, water-jacketed merry-go-round reactors
were used in parallel, for the UVC and UVC/H2O2 experiments,
respectively. The water recirculating in the glass reactors was
controlled at 22  C (for protection of the UVC equipment). UVC light
was provided by 35-W low pressure UVC lamps (Model: UVI 40 4C
P 15/300), with an emission of 350 mW/cm2, acquired from UVTechnik Speziallampen (see Supplementary Fig. S1 for the reactor
scheme). Among the Fenton-related experiments, the solar only
and solar-assisted photo-Fenton process were performed in 100mL Pyrex glass reactors, placed on magnetic stirrers and
constantly agitated by magnetic bars (300 rpm). The Fenton
experiment took place in shaded reactors, in the dark, whereas the
solar and the photo-Fenton experiments took place in a solar
simulator (Atlas, Suntest CPS). This articial solar light source was

S. Giannakis et al. / Water Research 102 (2016) 505e515


Fig. 1. Schematic representation of the WWTP of Vidy, Lausanne (VD, Switzerland) and the sampling points for this research.

set at 900 W/m2 global irradiance (~0.5% UVB, ~5% UVA and ~95%
visible light) and has been analytically presented in previous works
(e.g. Giannakis et al., 2015b). The solar UV intensity and global
irradiance was monitored with a coupled CM3 e CUV3 UV radiometer and pyranometer (Kipp & Zonen, Netherlands).
2.4. Application of AOPs: details and specications
A summary of the conditions is given in Supplementary Table S1,
regarding the experimental times and reagents addition. For each
group of experiments, an analytical presentation follows.
2.4.1. UV-based experiments
For the sole UVC experiments, 300 mL of wastewater were
added in the reactors and exposed to the irradiation. In the case of
UVC/H2O2 experiments, H2O2 was also added from a stock solution
to reach the desired initial H2O2 amount. The pH was monitored
and the samples were immediately analyzed. Samples were also
kept in order to assess bacterial regrowth after the experiments.
2.4.2. Fenton-related experiments
For the solar tests, 100 mL of wastewater were inserted in the
reactors and placed in the Suntest for simulation of solar exposure.
The temperature of the water never exceeded 35  C. The remaining
tests were performed with the addition of Fe2 and H2O2, either in
the dark (Fenton experiments) or under light in similar conditions
(photo-Fenton experiments). In all cases, samples were also kept
for regrowth tests.
2.5. Analytical methods, physicochemical and microbiological
2.5.1. Analytical methods
The micropollutants presence in wastewater was followed by a
UPLC/MS-MS method, used in previous works (De la Cruz et al.,
2013; De la Cruz et al., 2012) and analytically presented in
(Giannakis et al., 2015a). The removal percentage of the 8 micropollutants monitored in this study (Carbamazepine, Diclofenac,
Atenolol, Metoprolol, Venlafaxine, Clarithromycin, Benzotriazole
and Mecoprop) was calculated by weighted arithmetic mean, as

X %

w1 x1 w8 x8
w1 w8

In the graphs, the overall removal X% is given, wi is the micropollutant amount (mol) and xi the removal percentage of each
micropollutant (xi: i 1e8). Finally, we note that the work was
effectuated by the inherent micropollutant content of the collected
wastewater; no spiking took place prior to testing.

2.5.2. Physicochemical parameters

For the pH monitoring throughout the experiments a Mettler
Toledo pH meter was used. A UVevis Lamda 20 spectrophotometer
was used to monitor the evolution of H2O2, followed by the
(modied) DIN method 38 402 H15 and the dissolved iron by the
Ferrozine method (De la Cruz et al., 2012). The principal physicochemical characteristics of the wastewater used in this work are
summarized in Table 1.
2.5.3. Microbiological parameters
The microbial content of wastewater was monitored by cultivation on a non-selective agar (PCA). This medium allows the
enumeration of Escherichia coli, Bacillus subtilis, Listeria monocytogenes, Staphylococcus aureus and other bacteria contained in
water and dairy matrices. The microorganism recovery rate, after
24 h incubation at 35  C, is above 70% for a 1.000e100.000 inoculum (initial population). In such manner, the disinfecting capabilities of the AOPs tested shall not be limited by selectivity on the
medium and our estimation will have the minimum error possible,
given the particularities of the cultivation techniques for inactivation estimation (Michael et al., 2012). The initial CFU/mL in the
working matrices was 6.5  105, 6.5  103, 3.5  103 and 4  105, for
PT, AS, MBBR and CF, respectively. No microorganisms were spiked
in the wastewater samples; the work was realized by the indigenous population. Samples were drawn at the respective points
(~5 mL) and were plated immediately. Appropriate dilutions were
done, to achieve 15e150 colonies per plate. Experiments were done
in duplicates, in the different sample campaigns and at least double
plating was performed, enumerating 3 consecutive dilutions.
Therefore, the average value is presented in all the gures, subjected to <5% (max. 10% in few cases) standard deviation; measurements with higher errors were not considered and error bars
are not shown for clarity.
3. Results
3.1. Micropollutant elimination in the selected wastewater efuents
Fig. 2 summarizes the degradation of the 8 selected organic
micropollutants present in the efuents of the secondary treatment
facilities in the WWTP of Vidy. All the selected AOPs were tested
(UVC, UVC/H2O2, Solar, Fenton, photo-Fenton) against 8 MP in WW
(Carbamazepine, Diclofenac, Atenolol, Metoprolol, Venlafaxine,
Clarithromycin, Benzotriazole, Mecoprop), after treatment by AS,
In a previous study with 6 micropollutants, we have correlated
the degradation of micropollutants with the pretreatment method
and the subsequent AOP (Giannakis et al., 2015a) with an order of
increasing efciency of CF < AS < MBBR, for the pre-treatment


S. Giannakis et al. / Water Research 102 (2016) 505e515

Table 1
Basic physicochemical and optical characteristics of the wastewater used in this study (own measurements and (aMargot et al., 2013, bMargot et al., 2011)).

DOC (0.45 mm)
Total Solidsa,b
Total iron
Dissolved iron


mg CaCO3/L
mg Fe/L
mg Fe/L

Wastewater previously treated with

Primary treatment

Activated Sludge

Moving bed bioreactor

Coagulation occulation

109.1 25.6
89.32 26.42
200 19
282.5 15
35 10.4
59.5 5.4
2.5 0.55
0.25 0.05
37.78 5.78
22.45 3.32
11.42 0.97

28.08 12.62
20.40 1.41
51 10
230 35
12.1 2.8
54.6 4.1
0.95 0.05
0.04 0.002
87.58 4.95
75.77 2.24
65.59 2.34

14.615 7.9
6.39 1.71
20 11
95 10
14.2 1.4
25.5 4.3
1.75 0.15
0.02 0.001
86.10 5.51
74.07 1.57
67.47 3.23

68.47 15.94
29.98 0.88
85 5
240 10
28.5 5.7
58.2 3.3
5.5 1
0.33 0.06
62.22 7.09
44.45 4.09
31.27 6.55

Fig. 2. Micropollutants degradation by AOPs after secondary treatment. a) UV and UV/H2O2 processes. b) Fenton, solar and photo-Fenton process. AS: blue trace, MBBR: red trace,
CF: green trace. Continuous lines and colored symbols show the measured evolution of the experiment, while the dashed lines and open symbols indicate the projection of the
experiment according to the measured rst order degradation rate constant. (For interpretation of the references to colour in this gure legend, the reader is referred to the web
version of this article.)

methods and k UV < k UV=H2 O2 and k (Fenton) < k (solar irradiation) < k
(photo-Fenton), for the AOPs tested. This consistent behavior is also
observed here. Although the list of MPs has widened, including
both photo-sensitive and resistant compounds, the efuents of
MBBR again facilitated the highest MP removal. More specically,
the micropollutant removal efciency dropped as we move from
MBBR to AS and CF, in all types of AOP applied, attributed to the
COD and DOC content of the respective efuents. Furthermore, as
far as the comparison among the tested AOPs is concerned, only a
relative order can be established, as the processes differ signicantly. UVC/H2O2 and its massive HOC production has a profound
effect in MP elimination (2e10 min), whereas UVC alone requires a
mere 35e40 min for total removal of the parent compounds. The
difference among the times in each process is a function of the pretreatment. These processes achieved also a very high degree of
mineralization (Giannakis et al., 2015a), therefore their application
holds high potential.
On the other hand, solar, Fenton and photo-Fenton processes
would require much longer times to fully degrade the MPs. After 1
or 2 h, when our experiments stopped and the apparent rst order
k constant was calculated, a maximum of 50% elimination took
place, in the photo-Fenton reaction after 1 h in MBBR efuents. The
apparent k indicates minimum 2-h exposure to achieve 100%
removal. As at the end of our exposure period more than 75% of the

oxidants was available (data not shown, available in (Giannakis

et al., 2015a), the assumption that the process would continue
uniformly for an additional period holds true. Furthermore, an
interesting observation takes place if the synergy among the constituents of the photo-Fenton reaction is concerned. As it appears,
the photo-Fenton process is more efcient than simply the sum of
its parts. The Synergy (S) is higher in the processes that were
hampered in either way, solar or organic load (see Supplementary
Table S2). The reactivity of the organic pollutants with solar light is
limited and the enhancement of the process with the HO generation could result in efcient removal in relatively reasonable
retention time.
3.2. Microorganism elimination in the different wastewater
efuents, per AOP: inactivation and post-treatment regrowth
3.2.1. UVC and UVC/H2O2 processes
Fig. 3 showcases the bacterial inactivation after the application
of UVC, with or without the addition of H2O2. The efuents of
MBBR, AS, CF and PT were exposed to monochromatic UVC irradiation (Fig. 3a) or UVC and 20 mg/L H2O2. When UVC was applied
alone, two distinct categories of kinetics were observed, in either
MBBR and AS efuents or in CF and PT. In MBBR and AS efuents the
time necessary to completely inactivate bacteria was similar

S. Giannakis et al. / Water Research 102 (2016) 505e515

(<1 min actual difference) while the 4-log reduction in CF and PT

efuents delayed signicantly (10 min). The interpretation lies in
the Achilles heel of UVC applications. The two major drawbacks are
the suspended solids and the organic content in the efuents. The
solids, apart from their physical barrier effect, they effectively
shield microorganisms, and favor aggregation. Hence, as the efciency of the UVC irradiation relies in the transmittance of the
medium, the two efuents with lower SS content and therefore
higher transmittance (UVCT in Table 1) presented the lowest
treatment times.
The combined UVC/H2O2 process builds on the principles of the
UVC disinfection, plus the homolytic disruption of H2O2. The
mechanism of UVC/H2O2 inactivation, is both external and internal.
When H2O2 is added into the bulk, the HOC attacks improve
disinfection in all efuents; till now, there is no microorganism
found with resistance to the oxidation by HOC, contrary to damages by UVC irradiation which is repaired instantly (Sinha and
der, 2002). For the aforementioned reasons, we naturally
observe decrease in all necessary treatment times in Fig. 3b. The
major enhancement observed in the CF and PT efuents lies in the
dependence of the disinfection efciency in the transmission of
UVC light. MBBR and AS efuents contain signicantly low organic
mez et al.,
content, which acts as a HOC scavenger (Ortega-Go
2014), and low SS; the improvement is of some minutes and the
HOC-induced oxidation was proven to affect the overall carbon
content of the matrix (Giannakis et al., 2015a). In CF and PT efuents, since the transmittance levels are lower, the benet of the
oxidative action was higher, with the HOC attacks compensating
the lower inactivation rates demonstrated when UVC alone is
Finally, it should be noted that the wastewater efuents are far
more complex to be dissociated only to solids and organic scavenging, as many actors inuence the degradation efciency. For
instance, phosphorus scavenges the radicals generated (Wu and
Linden, 2010) and UVC is absorbed by nitrates, resulting to nitrite.
Nitrite reacts with hydroxyl radicals, producing nitrite radicals,
which are far less oxidative, but on the other hand are more longliving (Vione et al., 2014). Margot et al (Margot et al., 2011).
measured high values of NO3 ions in MBBR efuents, due to the


nitrication step, and their participation cannot be overlooked.

Finally, another dual mechanism is the scavenging of HOC by carbonates (Carra et al., 2016), or the generation of carbonate radicals
(Wu and Linden, 2010). The high alkalinity measured in AS and CF is
an indication of high (bi)carbonate content, partially explained by
the lower pH values of the MBBR efuents, and the expected
scavenging effect is higher than the benecial impact of the
oxidation by the mildly oxidative carbonate radicals.
The shaded part of Fig. 3 presents the regrowth assays performed for the UV-based processes. When UVC irradiation is
applied, the damage is mainly at the genome level, due to the high
absorption by the thymine and cytosine bases. The result is cyclobutaneepyrimidine dimers (CPDs), 6e4 photoproducts (6e4 PP)
plus their Dewar valence isomers (Douki et al., 2003). Within minutes of UVC exposure, the stress induces responses of chaperones
to repair the DNA damages, but soon this response is surpassed. As
the storage took place in the dark, the presented results are
exclusively an effect of the base or nucleotide excision repair, the
mutagenic repair and other similar mechanisms (Sinha and H
2002). Similarly to UVC disinfection, the regrowth is inuenced by
the dose of UVC received by the microorganisms. Hence, for similar
treatment times, the different efuents result in a regrowth of
increasing rate. After treatment, the microorganisms that are present in the bulk can be categorized in some states, such as healthy
(will grow in WW), injured (which can regrow), apoptotic (which
cannot regrow) and dead ones. The regrowth presented here is the
result of growth or regrowth from the rst two categories. What is
changing for instance in MBBR efuents among 2.5 and 5 min, since
the number of viable counts is the same, is the regrowth potential
and the shift towards the two last states. Finally, the differentiation
among the various statuses of cell conditions is more evident in CF
and PT efuents. These received low UVC doses and the higher nal
populations led to signicant regrowth.
Concerning the UVC/H2O2 inactivation, the baseline damage is
the UVC (common to the previous) adding the oxidative action of
HOC. If the damage was solely attributed to UVC, higher regrowth
would be demonstrated. The CF and PT efuents presented high
regrowth rates, since they received low UVC doses and suffered
from high HOC scavenging. For the AS and MBBR efuents, when

Fig. 3. V-based disinfection and respective regrowth after 24 h. A) UVC irradiation alone. B) UV/H2O2 process (20 ppm initial H2O2 addition). The shaded part and the dashed lines
symbolize the dark storage and regrowth after treatment, for 24 h.


S. Giannakis et al. / Water Research 102 (2016) 505e515

the inactivation process was complete, no detectable regrowth

occurred. The internal and external oxidative stresses posed by
HOC rendered the microorganisms unable to repair their lesions.
Also, compared to the UVC alone, the proportionality of residual
concentration and regrown population was lower, attributed to the
different pathway brought by HOC. Finally, even for the nonfavorable conditions met in CF and PT efuents, looking the
experimental process in retrospect, the regrowth was eliminated
when the treatment was prolonged beyond the necessary time for
total inactivation. Hence in a eld application, increasing the UVC
dose above the threshold for inactivation may ensure limitation of
bacterial regrowth.
3.2.2. Fenton, solar and photo-Fenton processes
Fig. 4 presents the results obtained when the Fenton reaction,
solar light or the (solar-assisted) photo-Fenton reaction were the
inactivation driving forces. Concerning the Fenton reagents
(Fig. 4a), H2O2 causes minor oxidation in outer cell wall layers, but
also diffuses into the cell. The amounts of H2O2 used in this study
are not bactericidal per se, and the modest inactivation achieved
was the result of the external Fenton reaction, by the addition of
Fe2 from our side, resulting to a massive oxidative wave. The
regeneration of ferric iron back to ferrous is very slow and difcult
to recover since the Fe3-dissolved organic matter (DOM) complexes are very stable (Hakala et al., 2009); hence our low inactivation rates. When H2O2 was doubled, the efciency did not
increase importantly. The HOC was partially scavenged by the
organic matter present in the solution. A positive effect though lies
in the complexation of iron by DOM after its conversion to Fe3 and
its reduced precipitation (Hakala et al., 2009). All efuents were in
the near-neutral region, in which the Fe3 aqua-complexes are not
soluble (Ruales-Lonfat et al., 2015). Concerning the precipitated
iron in the form of iron oxides, a small contribution of the heterogeneous Fenton reaction is possible, with the iron oxides acting
as iron source (Ruales-Lonfat et al., 2015), since all efuents contain
iron in lesser or higher amounts (Table 1).
The exposure of the samples to solar only irradiation (Fig. 4b)
caused the bacterial inactivation in a dual manner: UVB is documented to cause similar dimerization to the UVC-inicted one, but
in lower rates (Cadet et al., 2005). UVA on the other hand initiates a
chain of reactions in the bacteria, among which, internal oxidative
(Fenton-like) events are the most crucial (Spuhler et al., 2010;
Imlay, 2003). As it appears, solar light demonstrated aspects
similar to an indirect AOP. The nature of these actions initiated by

UVB and UVA explain the initial lag period (Giannakis et al., 2014)
visible in all graphs of Fig. 4b and the accumulation of this damage
actually resulted to bacterial inactivation. UVB and UVA wavelengths are also subjected to physical blocking and scattering by the
suspended solids, and therefore their efciency was a function of
the turbidity of the samples, as shown in Table 1.
As far as the photo-Fenton process is concerned (Fig. 4c), within
the time-frame studied, the inactivation for any efuent was
dramatically increased. In a recent review, we described the
mechanism of bacterial inactivation in water and wastewater
(Giannakis et al., 2016a,b). Briey, iron can complex with the
organic matter and under light, a ligand-to-metal charge transfer
(LMCT) results to the sacricial oxidation of the organic ligand
(producing organic ligand radicals) and more importantly, the
regeneration of Fe3 to Fe2 (Spuhler et al., 2010). Furthermore, the
simultaneous presence of iron, DOM and solar light initiates
photochemical cycles which can result in the production of ROS,
such as HOC and H2O2 (Canonica, 2007; Ng et al., 2014). This cycle
and its potential implications in wastewater efuents (EfOM) has
been previously analyzed (Giannakis et al., 2015a). Other sources of
ROS are the nitrates and carbonates (Wu and Linden, 2010; Vione
et al., 2014). As a result of the aforementioned actions, signicant
microorganism removal took place in MBBR and AS efuents. In 3 h
the disinfection process was (almost) complete, while even in CF
and PT efuents the removal was important. The combined, multilevel damage inicted by the photo-Fenton process can also be seen
in the synergy calculated for these experiments (see
Supplementary Table S3).
The shaded part of Fig. 4a summarizes the Fenton-related
techniques regrowth. The Fenton process was not efcient in
inactivating the microorganisms present in the efuents. Only 1e2
log units of inactivation represented the highest amount of bacteria
removed from the bulk. Nevertheless, the residual H2O2 and the
iron present in solution (complexed or dissolved) efciently
continued the Fenton process during the dark storage period.
Furthermore, a bacteriostatic behavior is observed in all but the PT
efuents. As discussed before, this is a result of the excess of targets
present in the solution. Also, the nal concentration of bacteria
after 24 h was correlated with the number of leftover microorganisms at the end of the observation period (since the same
action continues for the whole 24 h). This fact is promising, since
this process could be used for suppressing any regrowth risk in
treated wastewater, during storage and before potential reuse.
Solar disinfection and its regrowth was previously studied by

Fig. 4. Fenton-related disinfection and respective regrowth after 24 h. A) Fenton process (2:10 ppm initial Fe2/H2O2 addition). B) bare solar light. C) photo-Fenton process (2:10
10 ppm initial Fe2/H2O2 addition). The shaded part and the dashed lines symbolize the dark storage and regrowth4 after treatment, for 24 h.

S. Giannakis et al. / Water Research 102 (2016) 505e515

our group in synthetic, non-turbid efuents (Giannakis et al.,

2015b), where we correlated the exposure to solar irradiation
with the regrowth, and were able to identify the necessary solar
dose for shifting from (post-irradiation) growth to a deterministic
decay phase. In Fig. 4b, in all efuents, after 5 h of treatment,
regrowth is demonstrated. Only after 6 h of exposure in MBBR efuents a bacteriostatic effect is observed. The main difference in
the present work is the presence of particles in WW which effectively aggregate and shield the microorganisms, thus minimizing
the received solar dose. Furthermore, the action mode of solar
irradiation seems to be heavily inuenced by the UVA irradiation. If
UVB was the main driving force, enhanced regrowth would be
demonstrated. In MBBR efuents, the bacteriostatic/decay phase
observed after the exposure is an indication of the internal oxidative damage occurring in the cell (Imlay, 2003). Finally, the
contribution of the photo-sensitizable organic matter could inuence the inactivation, by the production of HOC and H2O2
(Canonica, 2007); iron is present in the efuents (especially in CF,
Table 1), which in combination with the small H2O2 accumulation
could hamper the regrowth in the dark.
The application of solar photo-Fenton combines the benets
presented in the previous two processes. Firstly, a decay phase is
observed for the end-treatment phase in both AS and MBBR efuents, reaching total elimination during the post-irradiation period.
Most probably, the simultaneous exposure to solar UV and the
Fenton reagents limits the potential of recovery for microorganisms; this effect hinders their growth in the minimal nutritional
contents and the oxidative stress present in the WW efuents
which still contain H2O2 and iron (Giannakis et al., 2015a). The low
organic content is probably the key point in managing to effectively
stop the growth. The PT efuents on the other hand still possess a
great number of healthy cells which continue to thrive. In conclusion, the short times of photo-Fenton by the exposure under light
and the continuous Fenton action have the best overall effect in
inactivation and regrowth inhibition, which makes it a potentially
attractive solution for WW treatment; possibly, if higher Fenton
reagents concentration was added to reduce the observed residence time, the process could be more competitive.
4. Discussion
4.1. The major threat and treatment focus: micropollutants or
The previous chapters have dealt with the isolated problem of
establishing proper disinfection or decontamination in the wastewater efuents. Nevertheless, since the co-existence of MPs and
MOs is the actual situation, in this part we perform a combined
approach and try to assess the treatment strategies for ensuring
both adequate MP removal and MO elimination, while suppressing
post-treatment bacterial regrowth. As thresholds, we have chosen
the 3-log inactivation of microorganisms as minimum removal (3 to
4-log for most reuse purposes; for instance (Liberti et al., 2003))
and the Swiss legislation limits for micropollutants (80% elimination (Giannakis et al., 2015a)).
Fig. 5 (a and b) presents in parallel the disinfection and the
decontamination processes of the UV-based processes. Concerning
the UVC irradiation alone, we have noted the efciency in the
previous chapters, and >99.9% MO removal can be achieved after
5 min of treatment. The immediate MP degradation does not satisfy
the 80% threshold before 30 min of exposure except for the MBBR
efuents. Therefore, one could suggest that MOs are easier to
remove and the design of the process has to be done taking the MPs
as reference. When bacterial regrowth is taken into consideration,
different times are reported to minimize this risk. For MBBR and AS


efuents, 5 and 10 min were necessary, respectively. In our samples,

regrowth suppression was not achieved in CF efuents before
10 min but extrapolating from the MBBR and AS efuents, in 30 min
it is safe to believe that it would be no longer possible to contain
healthy or repairable microorganisms. Even so, 30 min of exposure
is the threshold for MPs removal and therefore, indeed the design
needs to be implemented according to the MPs; their removal
means an already achieved acceptable disinfection level.
For the UV/H2O2 process, the necessary times were decreased.
Only 2.5 and 5 min of treatment were found necessary for MBBR
and AS (and CF) efuents, respectively. The regrowth was
completely suppressed after 2.5, 5 and 10 min for MBBR, AS and CF
as well. Comparing the necessary time for minimum 3-log removal
and regrowth inhibition, we observe that MPs were removed at
least at 85% (up to 99%) for all efuents. This means that if the
design takes place for the minimal MP removal, then efuents that
have been subjected to biological treatment are also microbiologically safe. Only for the physicochemical process a prolongation
would be necessary, and a higher (but not complete) MP removal
was attained. If we take into account the higher oxidative conditions used for MPs removal (25 ppm H2O2 vs. 20 ppm and 5 ppm
Fe2 vs. 2 ppm), the micropollutants should denitely be the primary target. Therefore, for both the UV-based processes, the
reference for micro-contaminant and microbiological safety is the
removal of MPs.
For the Fenton and solar processes presented in Fig. 6a, and 6b
neither MPs nor MOs have been successfully removed; after 6 h,
moderate removal was achieved. In the Fenton process, if the k
constant remains quasi-linear, around 6 h would be necessary for
efcient MP removal, therefore the exposure times would be
similar. After these exposure/treatment times, regrowth should not
be an issue; after 6 h of solar treatment, bacteria in MBBR efuents
demonstrated stationary behavior and when the Fenton process
was used, the presence of the reagents efciently suppressed
On the other hand, the photo-Fenton process shows (Fig. 6c)
promising potential, as the order of magnitude of bacterial decay is
reduced to the hour range. More specically, after 2 h of treatment
the MBBR and AS efuents are almost bacteriologically safe (99 and
97% removal, respectively) and above the 80% threshold for MPs.
Furthermore, after 3 h, apart from the attained disinfection,
regrowth is suppressed for biologically treated efuents and almost
for all efuents decontamination is achieved (~79% for CF). These
results demonstrate that for the Fenton-related processes, a shift in
the importance takes place and bacteriological targets are gaining
importance over the organic contaminant ones. We believe that if
similar oxidative conditions were to be used (higher were used in
MPs experiments), after 2 h, complete disinfection could have been
achieved and the only open question should be regrowth. Nevertheless, the results indicate with a high level of certainty that MOs
inactivation and regrowth could be taken as reference, since >80%
MP removal is estimated to precede the disinfection events.
4.2. Common events and dissimilarities in the treatment of different
targets in secondary efuents
Although we cannot possibly compare the two families of AOPs
applied, i.e. UV-based and Fenton-related ones, a separation can be
made according to the efuents. MBBR efuents always allowed
degradation of the targets faster than AS, CF, and PT, in order of
decreasing efciency. However, an intriguing controversy among
the investigated efuents is the shift in the order of importance,
when the family of AOPs used is modied. When the UV-based
technologies were applied, the MPs were the reference target,
while, in the Fenton-related processes the MOs disinfection and


S. Giannakis et al. / Water Research 102 (2016) 505e515

Fig. 5. . UV-based disinfection and decontamination. A) UVC irradiation alone. B) UVC/H2O2 process. The lines indicate the microorganism inactivation, while the bars the
micropollutant degradation (%). The circles indicate the regrowth suppression points with the respective colors indicating the secondary treatment method, while the horizontal
lines indicate the minimal micropollutant (brown line) and microorganism removal (orange line). (For interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)

Fig. 6. Fenton-related disinfection and respective regrowth after 24 h. A) Fenton process. B) Bare solar light. C) photo-Fenton process. The lines indicate the microorganism
inactivation, while the bars the micropollutant degradation (%). The circles indicate the regrowth suppression points with the respective colors indicating the secondary treatment
method, while the horizontal lines indicate the minimal micropollutant (brown line) and microorganism removal (orange line). (For interpretation of the references to colour in this
gure legend, the reader is referred to the web version of this article.)

their regrowth risk are more important. Even though this difference
is marginal, it contradicts the clear importance of the MPs in the
UV-based processes (and MOs for the Fenton-related) and at this
point we will try to assess the main parameters behind this issue.
1) The nature of the target plays a key role.
The micropollutants are complex, high molecular weight
(HMW) structures with the ones studied here almost all exceeding
the 200 g/mol. Sensitive LC-MS analyses have identied that the
various attacks against the molecules can be either photonic (UVC
induced damage) or ROS-related. These mechanisms can result to
ipso, para, meta attacks, eOH addition, halogen scissions etc. for
UVC light, while ketone formation, decarboxylation, side chain
breakage, protonation, H abstraction (and other) have been found
for the HOC-induced attacks (Zhao et al., 2014). Even a moderate
structural modication, such as short side-chain breakage induced

by e.g. a radical attack, modies the micropollutant signicantly,

and the by-products, even those structurally similar to the parent
compound, are no more considered for the calculation of the
degradation percentage. However, these by-products continue to
get degraded in the bulk, but compared to the carbon content of the
wastewater, their amount is negligible (Giannakis et al., 2015a).
Microorganisms on the other hand, seem to require signicantly
more attacks in order to get inactivated. The inuence of the light or
the radicals in key structures (e.g. lipids in cell membrane) has a
mitigated effect, leaving the microorganism viable. As this damage
progresses, the result could be bacterial death. It is an intriguing
question however, the effect of each process on bacterial viability,
i.e. quantify the UVC photons required to inactivate a microorganism, hinder its regrowth, or the ROS-induced attacks necessary
for membrane rupture etc. For the HOC effect alone and the
necessary amount to inactivate a single E. coli it has been found to
be in the order of 109 (Marug
an et al., 2008).

S. Giannakis et al. / Water Research 102 (2016) 505e515

2) The heterogeneity of targets (number and size) acts in a dual

The amount of each micropollutant in WW efuents is found
most frequently in the ng/L and low mg/L range. If a theoretical sum
of all the contaminants of emerging concern is assumed at mg level,
then in our experiments, a MWy300 g/mol is estimated and
therefore at 300 mL of sample we get around of 1015 pollutant
targets. Similarly, the maximum amount of bacteria encountered
was of 105 CFU/mL, hence ~108 CFU are expected. It becomes clear
that the micropollutants are in order of millions more than the
bacteria. However, the size of a molecule is to nm scale, while
bacteria range around the mm range; hence, the difference is in the
order of thousands. All things considered, although there are far
more MP molecules to degrade, since the HOC radicals are
limited by diffusion, it is probably easier to inict attacks on a big
and rare-to-nd microorganism, rather than reach a small and
abundant pollutant.
Furthermore, the assumptions made in this study have to be reconsidered when experimenting with urban WW. For instance,
bacteria are not the sole microorganism present (especially the
monitored ones), although our medium has optimal recovery for
the spread plate method. Viruses, protozoa and others compete for
the oxidants generated. Also for MPs, we chose a list of contaminants relevant to the research trends, but among the list, there are
contaminants with limited light reactivity (e.g. Atenolol) or high
reaction rate constants with HO (e.g. Diclofenac). As a result, the
percentage of removal is a relative measurement, and in future
studies, the wider the list of contaminants, the better approximation will be achieved.
3) Technical aspects related with the application of AOPs are
This study is a bench-scale simulation of a eld application,
using real WW efuents, but employing a certain reactor geometry.
The experiments were performed under a smaller optical path than
the dimensions of, for instance, a UVC-based plant. This fact explains mainly Fig. 2 and the MP degradation results, where
although a linear change is observed, the difference among the pretreated efuents and the effect on degradation is lower than the
respective one in microorganisms. Another example is the efciency of the UVC process after primary treatment only. Indeed, for
a short exposure time, with a short optical path, the difference is
mitigated, but in a real application, the scale-up problems, the effect of suspended solids, the cleaning of the quartz sleeves due to
particle settling and polymerization would make this application


impossible. As UVC exposure requires low SS and high UVCT waters

(min. 35%), the PT efuents are rejected and the CF ones would be
marginally accepted (see Table 1) to be treated by such a system.
Therefore, although in some cases the results do not justify it
completely, a biological pre-treatment is necessary before AOPs
application for disinfection.
4) Efuent characterization complexity hides the mode of action of
the different AOPs.
Another controversial point comes at the attribution of the effect of AOPs to each efuents, as a direct effect from the physicochemical characteristics presented in Table 1. As found for both
microorganisms and micropollutants, the order of degradation in
all cases is MBBR > AS > CF > PT, for all AOPs used. One could
dissociate the two groups, of MBBR with AS (biologically treated
efuents) and the CF with PT (physicochemical processes). In the
rst group, the efuents present similar light transmittance, and
therefore, their optical-based effects are quite similar. The AS has
higher alkalinity and organics content, so the disinfection is slightly
hindered. In the second group, the efuents present similar SS
content, with the CF efuents having been through a physicochemical removal of smaller (colloidal) particles.
As a result, parameters with profound differences seem to
merely affect the process (e.g. COD), as ultimately, we assess the net
degradation force at each efuent. To better investigate this effect
related with the organic matter, a look into the characterization of
the organics content, which can act either as (photo-) sensitizable
or oxidizable matter, is useful (Giannakis et al., 2015a); to assess
this possibility, a set of photo-activity indices and measurements
were applied to these efuents (see Table 2). The detailed absorption spectra for the four efuents, are given in the supplementary
material (Supplementary Fig. S2).
The specic wavelengths are used for photochemical activity
evaluation purposes. The E2:E3 and the E4:E6 ratios, are measures of
aromaticity, which indirectly imply photo-activity. The MBBR
efuent presented the highest E2:E3 ratio. The E4:E6 indicates
higher colored dissolved organic matter (CDOM) presence; in fact,
higher E4:E6 ratio means low aromaticity (Fu et al., 2016). Since
sometimes the absorbance at 665 nm is zero, the 280 (Helms et al.,
2008) or SUVA (specic UV absorbance) were suggested as
aromaticity indexes. In our case, it corroborates with the rest of the
ndings. Also, the dimensionless slope ratio (SR) (Helms et al.,
2008) increased as we move from PT to MBBR (lowest to highest
ratio) and suggested lower molecular weight fractionated organic
matter present in the efuent (Fu et al., 2016). Ultimately, since
LMW organic matter is proposed to act as photo-sensitizable

Table 2
Photochemical characteristics of the various efuents.





E2 (254 nm)
E3 (365 nm)

0.430 0.16
0.084 0.05
5.432 1.03

0.147 0.04
0.017 0.01
14.545 14.18

0.109 0.04
0.013 0.01
24.386 29.15

0.391 0.22
0.074 0.06
5.935 1.68

E4 (465 nm)
E6 (665 nm)

0.040 0.03
0.021 0.01
1.909 0.13

0.006 0.01
0.004 0.01
0.625 0.88

0.005 0.01
0.004 0.01
0.563 0.8

0.008 0.01
0.004 0.01
0.813 1.15


0.327 0.10
273.15 15.88

0.121 0.03
168.59 3.21

0.091 0.03
70.22 4.66

0.171 0.01
178.32 5.52

Slope 275e295 nm
Slope 350e450 nm
SR (slope ratio)

4.697 0.78

10.472 5.62

8.750 8.84

5.413 0.11


S. Giannakis et al. / Water Research 102 (2016) 505e515

organic matter (PhOM) rather than oxidizable (OxOM) (Giannakis

et al., 2015a; Vione et al., 2014), the possibility to participate in
generating ROS is higher. The generated ROS then participate in the
controversial points 1 and 2, as analyzed before.
With this overview, it is safe to suggest that the physicochemical
parameters followed in the efuents of this work give only a view
on some key factors inuencing the process. This linear behavior is
merely the geometrical sum of the different actors present in WW
water. In each efuent, the presence of secondary parameters,
such as the carbonates, or the organic matter, are vectors which can
act either synergistically or in an antagonistic manner.
5) Differences in the response between the two families of AOPs,
for the different targets.
The UVC and UV/H2O2 processes were found to inactivate microorganisms and degrade pollutants rather efciently in all cases,
whereas the Fenton and solar light (and less the photo-Fenton)
require special conditions (e.g. prolonged exposure) to ensure the
success of the application. Apart from the obvious differences in
kinetics due to massive HOC generation in the UV/H2O2 process
and higher energy in the UVC photons (compared to solar UVB and
UVA ones), there are other biological issues implicated in the
observed change in the reference and the importance attributed to
each target.
When targeting micropollutants, the type and intensity of light
applied, the addition of reagents etc. affect the apparent 1st order
degradation kinetics. However, in microorganisms, when light
based processes are involved, more issues should be considered.
For instance, when UVC light is applied, the absorbance by the
thymine and cytosine bases is much higher than the UVB supplied
by (simulated) solar light (Cadet et al., 2005). As a result, the time
necessary to inactivate microorganisms is in order of minutes,
compared to hours, for UVC and solar light, respectively. On the
contrary, if many hours are required for completing a solar disinfection experiment, given that bacterial (E. coli) cell division takes
place every ~30 min, many generations of microorganisms could be
formed, thus constantly repopulating the sample. In conclusion, the
forces of inactivation and salvation of microorganisms are far from
collinear. This delicate balance, which depends on light irradiance,
solar dose, temperature and more, may contribute signicantly in
the change of order of importance among the chemical and
microbiological contaminants observed in the Fenton related
5. Conclusions
The use of ve AOPs against microorganisms and contaminants
of emerging concern was assessed in this work, focusing in the
differences among the two broad categories tested here, the UVbased and the Fenton-related ones. In combination, three efuents were treated, from which two involved biological treatment
(AS, MBBR) and a physicochemical one (CF), while presenting the
primarily treated as control (PT).
The quality of the efuents inuenced the outcome of the
experiment, for micropollutants and microorganisms, both for
immediate removal or regrowth suppression. In general, the order
of efuent quality was MBBR > AS > CF. The measured physicochemical characteristics of these three efuents inuenced in the
same manner the application of the AOPs. Among the two AOP
groups, the order of efciency for the UV-based processes was
UVC < UVC/H2O2 for both targets, while for the Fenton-related ones
was solar < Fenton < photo-Fenton for micropollutants and
Fenton < solar < photo-Fenton for microorganisms. Even so, high
levels of synergy where observed for the constituents of the photo-

Fenton process and its utilization in neutral pH was encouraged.

The post-treatment events of bacterial regrowth were monitored,
and prolongation of the treatment beyond the required time for
inactivation was the solution for the UV-based processes, while the
Fenton-related ones, as they employ different inactivation mechanisms that can hinder regrowth, need optimization of the Fenton
reagents addition.
Taking into account the levels proposed by the Swiss legislation
for micropollutant removal and the threshold for water reuse of
treated wastewater, if a quaternary treatment unit based on UVC
irradiation (with or without H2O2) was to be considered, the
removal of micropollutants is a better indicator of water quality;
the use of H2O2 reduces signicantly the residence times but increases the operational cost and design implications. In other
contexts than Switzerland, i.e. sunny or developing countries, if the
Fenton-related processes are to be considered, the bacteria were
(marginally) considered to be a better reference for depollution of
wastewater, as for these higher residence times (compared to UV)
the micropollutants demonstrated faster degradation kinetics than
the respective micropollutant ones. The variation appearing among
the two families of AOPs in the secondary efuents are a result i) of
the structural differences among the targets, ii) the degradation/
inactivation pathway, iii) the reactor design specications, iv) the
photochemical characteristics of the efuents and v) the biological
implications of the targets, such as bacterial growth and regrowth
during treatment. As a result, apart from the physicochemical data
which can be easily monitored, photo-chemical indicators, design
implications and a battery of tests (microbiological, analytical)
should be considered, in order to rstly well-characterize the efuents and then rene the treatment strategies applied.
The authors wish to thank the Vidy WWTP administration and
personnel for their assistance during the sampling campaigns,
especially Mr. Guillermo Grunauer and Mr. Yves Duperrex. Also,
Stefanos Giannakis acknowledges the Swiss Agency for Development and Cooperation (SDC) and the Swiss National Foundation for
the Research for Development (r4d) Grant, for the funding through
^te dIvoire
the project Treatment of the hospital wastewaters in Co
and in Colombia by advanced oxidation processes (Project No.
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