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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.
Keywords:
Bacteria
Advanced oxidation processes (AOPs)
Biological treatment
Disinfection kinetics
Physicochemical treatment
Micropollutants
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: stefanos.giannakis@ep.ch (S. Giannakis), cesar.pulgarin@ep.
ch (C. Pulgarin).
http://dx.doi.org/10.1016/j.watres.2016.06.066
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
506
Abbreviations list
AOP
AS
CF
CFU
COD
CPD
DBP
DOM
EfOM
Fe/S
HRT
MBBR
MO
MP
MW
OxOM
PhOM
POM
PP
T
ROS
S
SODIS
SRT
SS
SUVA
TOC
TSS
UV
WW
WWTP
507
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
parameters
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
follows:
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.
508
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)).
Parameter
pH
TOC
DOC (0.45 mm)
COD
Alkalinity
TSSa,b
Total Solidsa,b
Total iron
Dissolved iron
UVAT
UVBT
UVCT
Unit
mg/L
mg/L
mg/L
mg CaCO3/L
mg/L
mg/L
mg Fe/L
mg Fe/L
%
%
%
Activated Sludge
Coagulation occulation
7.8e8
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
7.3e7.8
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
6.6e7.4
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
7.3e7.9
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
509
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.
510
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.
511
512
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
513
Table 2
Photochemical characteristics of the various efuents.
Index
PT
AS
MBBR
CF
E2 (254 nm)
E3 (365 nm)
E2:E3
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)
E4:E6
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
280
SUVA (DOC/E2)
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)
0.00250
0.00055
4.697 0.78
0.00130
0.00015
10.472 5.62
0.00055
0.00012
8.750 8.84
0.00275
0.00051
5.413 0.11
514
515