Water Air Soil Pollut (2017) 228:339

DOI 10.1007/s11270-017-3532-0

Performance Analysis of Photolytic, Photocatalytic,

and Adsorption Systems in the Degradation of Metronidazole
on the Perspective of Removal Rate and Energy Consumption
Neghi N & Mathava Kumar

Received: 6 January 2017 / Accepted: 6 August 2017

# Springer International Publishing AG 2017

Abstract The efficiency of the following systems: pho- of MNZ via aliphatic carboxylic acid compounds in the
tolysis (UV-C only), photocatalysis with titanium-dioxide photocatalytic system. Overall, the photocatalytic system
(UV-C/TiO2), photocatalysis with granular-activated car- seems to be an energy-efficient treatment option for the
bon (UV-C/GAC), and by adsorption on GAC, was removal of MNZ and similar other micropollutants.
assessed under different initial contaminant concentrations,
i.e., 0.1–100 mg L−1. The experiments were conducted in a Keywords Antibiotics . Oxidative degradation
batch photocatalytic reactor (1.9 L and 32 W UV power). pathway . Metronidazole . Photocatalysis . Wastewater
It was found that UV-C/TiO2 and UV-C/GAC systems treatment . Energy consumption analysis
showed fairly equal removal efficiencies under lower
MNZ concentrations (0.1–5 mg L−1) compared to higher
concentrations at similar catalyst loading of 2.5 g L−1. A
1 Introduction
decline in removal rate (based on first-order reaction) was
observed with respect to increase in initial MNZ concen-
In the recent years, traces of human and animal pharma-
tration in all systems. MNZ removal by adsorption on
ceuticals have been observed in several aqueous systems.
GAC was much lesser compared to UV-C only, UV-C/
Moreover, the effects of pharmaceuticals to various envi-
TiO2, and UV-C/GAC systems. The adsorption data well
ronmental species have been discussed throughout the
correlated with the Freundlich model indicated that the
world. However, pharmaceuticals are one of the inevita-
adsorption was on the heterogeneous surface of the cata-
ble concomitants of everyday activity. Several metric tons
lyst. The effectiveness of the systems were evaluated by
of pharmaceuticals are used annually for controlling dis-
calculating electrical energy consumed per order (EEO).
eases and as feed supplements in poultries, aquaculture
The lowest EEO value was found to be for UV-C/TiO2
farms, animal husbandries, etc. Antibiotics, one of the
(0.03 kWh m−3 order−1) for the degradation of 0.1 mg L−1
major classes of pharmaceuticals, are designed to stop/kill
of MNZ compared to UV-C/GAC (0.06 kWh m−3 or-
the activity of disease-producing microorganisms, i.e.,
der−1), UV-C only (0.15 kWh m−3 order−1), and adsorption
microbial biochemical processes. The release of antibi-
(0.44 kWh m−3 order−1). The total organic carbon and
otics and/or their intermediates in the environment could
nitrogen ion analyses have confirmed the mineralization
produce detrimental effects to non-targeted indigenous
organisms such as cyanobacteria, algae, crustaceans, fish,
N. N : M. Kumar (*) etc. (Guo et al. 2016). The major sources of antibiotic
Environmental and Water Resources Engineering Division, release into various environmental compartments include
Department of Civil Engineering, IIT Madras, Chennai 600036,
India
hospitals, antibiotic formulation/production units, munic-
e-mail: mathav@iitm.ac.in ipal wastewater, households, meat processing units, ma-
e-mail: mathavakumar@gmail.com nure from husbandries, and sewage sludge (Coutu et al.
339 Page 2 of 12
2013; Lien et al. 2016; Perez et al. 2015). In water
systems, antibiotics were detected in the range of nano-
grams per liter to micrograms per liter (Asha and Kumar
2015); however, higher concentration levels in the waste-
waters released from pharmaceutical production and mu-
nicipal wastewater treatment units were reported
(Kimosop et al. 2016). The exposure of indigenous or-
ganisms to antibiotics (especially bacteria) could develop
antibiotic-resistant/antimicrobial-resistant (AMR) genes,
which has the capability to produce detrimental effect to
the humankind (Lupo et al. 2012). Therefore, it is of
utmost concern to stop the entry of antibiotics into the
environment by introducing policy decisions and to de-
sign suitable treatment systems for antibiotics removal.
Metronidazole (C6H9N3O3, MNZ) is one of the pri-
ority antibiotics, which has been used for controlling
infections caused by anaerobic bacteria, protozoa, and
bacteroides (Bendesky et al. 2002). MNZ has a wide-
spread application in human pharmaceuticals and at the
same time, it has been used as an additive in poultry and
fish farms. The cytotoxic intermediates released from
MNZ after ingestion have the potential to damage DNA,
protein, and membrane of the disease-producing organ-
isms. It was reported that MNZ is genotoxic to humans
and it can also produce mutagenic and carcinogenic
effects to the aquatic organisms (Perez et al. 2015).
MNZ is highly soluble in water (~ 10 mg mL−1 at 20 °
C) and can persist in the environment for several days
(Wu and Fassihi 2005). The presence of MNZ in seven
major municipal wastewater treatment plant effluents
(2–40 μg L−1) has been reported (Gros et al. 2010),
which indicates the failure of conventional biological
treatment systems in stopping the entry of MNZ and
similar other micropollutants along with the effluents. In
addition, the exposure of MNZ could lead to AMR
genes. Therefore, it is essential to design a suitable
treatment system to remove micropollutants including
MNZ and to control the propagation of AMR genes.
The advanced oxidation processes (AOPs) such as
ozonation, Fenton, photo-Fenton, photocatalysis, ultra-
sound irradiation, electrochemical, and wet air oxidation
are suitable for the degradation of MNZ (Kanakaraju
et al. 2014); however, photocatalysis employing UV in
the bandwidth of 200 to 280 nm (UV-C/TiO2 and UV-C/
GAC) is found to be very effective in MNZ and AMR
gene (AMRg) removals (Alexander et al. 2016; Guo
et al. 2013; Mckinney and Pruden 2012).
The photocatalytic system employing TiO2 catalyst
has the following advantages: (1) TiO2 is chemically
Water Air Soil Pollut (2017) 228:339
and biologically inert, photoactive, inexpensive, and
non-toxic and (2) the hydroxyl radical (HO·) produced
in the system has strong oxidation potential (+ 2.80 V),
which is non-selective in rapidly oxidizing (rate constants
in the order of 106–1010 M−1 s−1) most organic com-
pounds (Petrovic et al. 2011; Andreozzi et al. 1999).
The mechanism of UV-C/TiO2 in the degradation of
organic micropollutants (R) including MNZ is shown in
Eqs. (1)–(5).
TiO2 þ hv ð254 nmÞ→e−CB þ hþ
VB ð1Þ
H 2 O þ hþ
VB →HO• þ H
þ
ð2Þ
O2 þ e−CB →O−2 • ð3Þ
R þ hþ
VB →R
•
ð4Þ
R þ HO•→R• →CO2 þ H2 O ð5Þ
Where e−CB ; hþ
VB are electrons and holes produced in
the conduction band and valence band of the semiconduc-
tor catalyst (TiO2). The property of semiconductor-free
activated carbons to absorb photons and generate HO·
radicals when exposed to UV irradiation in aqueous me-
dium has been reported (Velasco et al. 2012, 2013;
Velo-Gala et al. 2015). However, the mechanism of radical
generation has not been explored in detail. On the other
hand, the exposure of microorganisms in the UV-C/TiO2
and UV-C/GAC systems could facilitate the dimerization
of thymine (DoT) and the subsequent disruption of DNA
replication process as shown in Eq. (6).
AMRg þ hv ð254 nmÞ→DoT→Cell death ð6Þ
The application of photocatalytic system for
real-time wastewater treatment depends on several fac-
tors including physico-chemical characteristics of the
micropollutant, energy and intensity of UV light, reac-
tion conditions (pH, pollutant concentration, catalyst
dosage, reusability of the catalyst, etc.), and ecotoxicity
of photoproducts formed (if any) in the treated water. In
the past, the efficacy of UV-TiO2 system in the removal
of dyes, phenol, pesticides, solvents, and few pharma-
ceutical compounds (Choquette-Labbe et al. 2014; Mar-
tinez et al. 2011; Pereira et al. 2013; Verma et al. 2013;
Zhu et al. 2012) under different experimental conditions
Water Air Soil Pollut (2017) 228:339
were investigated. But the application of TiO 2
photocatalysis, GAC as a catalyst, and their comparative
evaluation for antibiotics removal was not investigated
in detail. Moreover, photocatalytic degradation antibi-
otics using TiO2 and GAC as catalysts and the perfor-
mance of these systems based on the concept of electri-
cal energy per order (EEO) has not been explored in
detail. Therefore, the present study was focused (i) to
evaluate the performance of photocatalytic system using
TiO2 and GAC (UV-C/TiO2 and UV-C/GAC) as cata-
lysts in the removal of MNZ; (ii) to distinguish the rates
of photolytic, photocatalytic, and adsorption systems
under different initial MNZ concentrations; (iii) to iden-
tify the degradation pathway of MNZ mediated by
hydroxyl radicals; and (iv) to correlate the MNZ remov-
al with energy consumption analysis in terms of EEO.
2 Materials and Methods
2.1 Chemicals
MNZ (99.9% purity) was obtained from Sigma-Aldrich,
India and used as received. Anatase form of TiO2 (size
less than 25 nm) having a surface area of 45–55 m2 g−1
and with a density of 3.9 g mL−1 at 25 °C was purchased
from Sigma-Aldrich, India. Acetonitrile and deionized
water were used for HPLC analysis and they were
procured from Merck, Germany. GAC with particle size
Fig. 1 Schematic of batch
photocatalytic reactor
UV POWER
SUPPLY
DOUBLE WALLED
CYLINDRICAL
GLASS REACTOR
WITH WORKING
VOLUME OF 1.9 L
Page 3 of 12 339
fraction, bulk density, specific surface area (SBET), and
total pore volume (V T ) of 2–5 mm, 0.4 kg m −3,
1010 m2 g−1, and 0.532 cm3 g−1, respectively, was
supplied by S.D. Fine Chemicals Limited, India.
2.2 Photolytic and Photocatalytic Experiments
A double-walled cylindrical reactor with a working vol-
ume of 1.9 L (Fig. 1) was used for the photolytic and
photocatalytic experiments. The UV lamps and probes
(pH, temperature, and oxidation-reduction potential
(ORP)) were inserted into the reactor through the ports in
the lid of the reactor. An electronic overhead stirrer was
mounted centrally and the reactor contents were mixed
continuously at a constant stirring speed. The size of GAC
used in the experiment was of 2–3 mm. The uniform
distribution of the GAC was achieved by the operation of
overhead stirrer at 500 rpm, whereas the uniform distribu-
tion of TiO2 was achieved by operating at 200 rpm. The
light energy was supplied through two UV lamps each of
16 W power (λmax at 254 nm). The reactor was provided
with water circulation arrangement through the double
walls to control the increase in temperature of the reactor
due to the supply of light energy. However, the experi-
ments in this investigation were conducted without circu-
lation of cooling water, i.e., uncontrolled temperature con-
ditions. The experimental conditions of this investigation
are shown in Table 1. Photolytic experiments were con-
ducted at different initial MNZ concentrations, i.e., 0.1, 1,
ELECTRONIC STIRRER
PROBES
CONNECTED TO
pH/ORP/Temp
METER
METRONIDAZOLE AND
TiO2 IN SUSPENSION
339 Page 4 of 12 Water Air Soil Pollut (2017) 228:339

Table 1 Experimental conditions of the study and their outcomes

Expt. MNZ Type of UV TiO2 GAC MNZ MNZ removal

runs concentration system power loading loading removal rate constant (×
(mg L−1) (W) (g/L) (g/L) at 120 min 10−2 min−1)
(%)

E-1 0.1 Photolysis 32 – – 39.2 0.39

E-2 1 32 – – 40.4 0.38
E-3 5 32 – – 38.4 0.33
E-4 15 32 – – 38.9 0.34
E-5 50 32 – – 24.5 0.23
E-6 100 32 – – 20.1 0.17
E-7 0.1 Photocatalysis 32 2.5 – 99.7 4.8
E-8 1 with TiO2 32 2.5 – 98.2 3.2
E-9 5 32 2.5 – 97.1 3.0
E-10 15 32 2.5 – 96.2 2.3
E-11 50 32 2.5 – 79.7 1.4
E-12 100 32 2.5 – 46.8 0.5
E-13 0.1 Photocatalysis 32 – 2.5 96.3 2.5
E-14 1 with GAC 32 – 2.5 94.7 2.3
E-15 5 32 – 2.5 89.7 1.9
E-16 15 32 – 2.5 77.6 1.28
E-17 50 32 – 2.5 72 1.3
E-18 100 32 – 2.5 36.3 0.4
E-19 0.1 Adsorption – – 2.5 23 0.29
E-20 1 – – 2.5 28 0.20
E-21 5 – – 2.5 27.4 0.22
E-22 15 – – 2.5 23.1 0.15
E-23 50 – – 2.5 18.3 0.17
E-24 100 – – 2.5 7 0.007

Note: the experiments were conducted in duplicate and the average values are reported

5, 15, 50, and 100 mg L−1, with continuous supply of
32 W UV power (E-1 to E-6). The experiments were
carried out for 120 min and the samples were collected at
5, 10, 15, 30, 60, and 120 min. The collected samples were
analyzed for pH, temperature, ORP, total organic carbon
(TOC), and MNZ concentration. The experiments were
repeated in the presence of photo catalysts each with the
loading of 2.5 g L−1, i.e., TiO2 (E-7 to E-12) and GAC
(E-13 to E-18) with 32 W UV power. From all experi-
ments, the samples were collected at similar time intervals
and analyzed for various parameters.
2.3 Adsorption Experiments
The adsorption experiments (E-19 to E-24 as shown in
Table 1) were conducted using conical flasks at a
working volume of 250 mL. The experiments were
conducted at room temperature (~ 30 °C) with homog-
enous mixing in an orbital shaker for 120 min. The
aliquots were collected at regular time intervals and
analyzed for MNZ concentration. The outcome of the
adsorption experiments were used to find out the rate of
adsorption and MNZ adsorption capacity of GAC.
2.4 Analytical Methods
The pH, ORP, and temperature of the collected samples
were measured using bench-top meters (Oakton, India).
The total organic carbon remaining in the samples was
analyzed by total organic carbon analyzer equipped with
non-destructive infrared analyzer (Shimadzu, Japan).
The MNZ concentration was measured using
Water Air Soil Pollut (2017) 228:339 Page 5 of 12 339

high-performance liquid chromatography fitted with 3.2 MNZ Adsorption

C 18 220 mm (L) × 4.6 mm (I.D) silica-based
reverse-phase column and a UV-visible detector. The The experimental data corresponding to E-19 to
mobile phase used in the HPLC analysis was acetonitrile E-24 were used to calculate the equilibrium MNZ
and water (60:40), which was pumped at a rate of adsorption concentration on GAC using Eq. (9).
1 mL min−1. Where Ce, V, and W represent equilibrium MNZ
The photocatalytic degradation products of MNZ in concentration at equilibrium time (te), reaction vol-
the samples (E-7 to E-12) were identified using a liquid ume, and weight of GAC. Moreover, the data was
chromatography fitted with ion-trap mass spectrometer used to estimate the maximum MNZ adsorption
(LC-MS) (Thermoscientific, USA) and operated under capacity of GAC using Langmuir (Eq. 10),
positively induced ion scanning-mode. The analyzer Freundlich (Eq. 11), and Sips (Eq. 12) isotherms.
was maintained at an electro spray voltage of +1.5 kV
V
ion source with a capillary temperature of 350 °C. The qe ¼ ðC o −C e Þ ð9Þ
W
samples were injected manually and the obtained spec-
trums were used to identify the degradation products.
The TiO2 and GAC samples (fresh and samples qmL K L C e
collected from the reactor after experimentation) were qe¼ ð10Þ
1 þ K LCe
dried and coated with gold. Subsequently, the surface
morphology of samples was visualized by field emis-
sion scanning electron microscopy (SEM) at an accel- .
1 nL
erating voltage of 30 kV (Genisis 2000, Emcrafts). qe¼ K F C e ð11Þ
Moreover, the elemental composition of the samples
was quantitatively determined using energy dispersive
spectroscopy (EDS, Genesis 2000). qms : K S C m s
e
qe¼ ð12Þ
1 þ K sCe ms

In Eq. (10), qmL is the amount of adsorption

3 Data Interpretation corresponding to the complete monolayer coverage
and KL is the Langmuir isotherm constant. In Eq.
3.1 Rate of MNZ Removal (11), 1/nL and KF are the adsorption intensity and
Freundlich isotherm constant, respectively. In Sips
The photocatalytic removal efficiency of MNZ in the isotherm, qms is maximum adsorption capacity, Ks is
system was calculated as shown in Eq. (7). the sips isotherm constant, and ms is the model
exponent. At lower sorbate concentrations, Eq. (12)
C 0 −C t can reduce to Freundlich isotherm while at higher
η¼  100 ð7Þ
C0 concentrations the sips model can predict the mono-
layer sorption capacity as like the Langmuir iso-
Where C0 and Ct represent the initial MNZ concentra- therm. The rate of adsorption, indicating the resi-
tion and final MNZ concentration at any time (t), respec- dence time of the compound at the solid solution
tively. The relationship between degradation rate and the interface was found out by using kinetic models. In
initial MNZ concentration (C0) in the photocatalytic pro- order to find out the role of GAC on MNZ sorption,
cess can be described by Langmuir-Hinshelwood (L-H) Lagergren’s pseudo-first order (Eq. 13) and
model (Hapeshi et al. 2010; Prados-Joya et al. 2011; pseudo-second order model (Eq. 14) were applied.
Safari et al. 2015; Vishnuganth et al. 2016). The simpli- Moreover, Weber Morris Eq. (15) was used to iden-
fied form of L-H model as shown in Eq. (8) was used to tify the role of intra-particle diffusion in MNZ ad-
find out the rate of MNZ removal (k1). sorption. The rate and order of the adsorption reac-
tion was further validated by Eq. (16) where dC and
Ct CA are the difference and average MNZ concentra-
ln ¼ −k 1 t ð8Þ
C0 tions measured at the successive time intervals. The
339 Page 6 of 12
value of n denotes the order of the reaction
(Table 2).
k1
log ðqe −qt Þ ¼ logqe − t ð13Þ
2:303
t 1 1 an indication of accelerated MNZ degradation by the
¼ þ t ð14Þ
qt K 2 q2e qe
. of fewer quantity of HO· radicals per mole of MNZ at
1 2
qt ¼ K id t þc ð15Þ
 
−dc
log ¼ n logC A þ logk 1 ð16Þ
dt
4 Results and Discussion
4.1 MNZ Removal by Photolysis and Photocatalysis
The outcome of photolysis (E-1 to E-6) and photocatalysis
(E-7 to E-18) experiments are shown in Table 1. A max-
imum of 40.4% MNZ removal was observed in the pho-
tolysis experiments corresponds to E-2 (initial MNZ con-
centration was at 1 mg L−1). A decline in MNZ removal
was observed while increasing the MNZ concentration
beyond 1 mg L−1. The ORP profiles corresponding to
selective photolytic and photocatalytic experiments are
shown in Fig. 2. It can be observed from the figure that
ORP values are significantly higher in photocatalytic sys-
tems (171–323 mV) compared to photolytic systems
(174–241 mV). This could be due to greater quantity of
hydroxyl radicals (HO·) generated in the photocatalytic
system. The MNZ removal efficiencies observed in E-7
and E-8 were 1.5 times higher than that observed in E-2.
As observed in photolytic systems, similar decline in MNZ
removal efficiency was observed beyond 0.1 mg L−1.
However, the lowest MNZ removal observed in the pho-
tocatalytic systems (E-12) was relatively higher than the
maximum MNZ removal observed in photolytic system
(E-2). This could be attributed to MNZ oxidation under
irradiation or hydrolysis in the photolytic system, whereas
MNZ oxidation was mediated by HO· in photocatalytic
system. As a result, higher MNZ removal rates were
observed in photocatalytic system. The pseudo-first-order
Water Air Soil Pollut (2017) 228:339
kinetic model (Eq. 8) has well fitted the experimental data
with high correlation coefficient value (r2 > 0.98). The rate
constant (k1) was determined from the slope of the linear-
ized first-order plot of -ln (C0/C) versus time, and the
values are given in Table 1. The observation of relatively
higher k1 values in E-7 to E-12 compared to E-1 to E-6 is
HO·-mediated oxidation reaction. However, a decline in
k1 value with increase in MNZ concentration can be
noticed in Table 1, which could be due to the availability
higher initial MNZ concentrations. Moreover, the degra-
dation intermediates of MNZ might have accumulated on
the surface of the catalyst causing a negative effect in the
utilization of OH· radicals or positive holes in the valence
band of TiO2 surface (Cai and Hu 2017; Farzadkia et al.
2015). The increase in the value of removal rate constant is
several times higher in both photolytic (2.5 times) and
photocatalytic (9.6 times) systems at lower concentration
(0.1 mg L−1) compared to higher MNZ concentration
(100 mg L−1). A marginal decline in pH was noticed in
the photolytic and photocatalytic systems during the first
20 min of reaction; however, the pH trends of both systems
were found to be similar (Fig. 2). The decline in pH was by
the dissolution of carbon-dioxide (CO2) produced as a
result of partial mineralization, which was evidenced by
the LC-MS analysis. On the other hand, MNZ removal
might not be significant at other pH conditions due to the
nature of MNZ and TiO2 at different solution pHs. The
pHzpc of TiO2 is 6.52 and pKa of MNZ is 2.55. At basic
pH, both TiO2 and MNZ possess negative charge and at
acidic pH both are positively charged. Therefore, at neutral
pH, no repulsive forces might be developed and as a result,
maximum degradation could be achieved (Farzadkia et al.
2015).
The applicability of GAC as a photocatalyst was ex-
amined in E-13 to E-18 and the outcomes are shown in
Table 1. A maximum of 96.3% removal was observed in
E-13, whereas 36.3% was observed at the highest initial
MNZ concentration adopted for UV-C/GAC experi-
ments. Similar ORP and pH trends were observed in
UV-C/GAC system as like UV-C/TiO2 (Fig. 2). The
removal efficiency of GAC photocatalytic system was
146% higher compared to the photolytic system; howev-
er, it was slightly lesser (3.5%) compared to photocata-
lytic system with lowest initial MNZ concentration, i.e.,
E-7. Similar trend was observed under other MNZ con-
centrations, which show that GAC can be used as a
photocatalyst apart from it being used as an adsorbent
Water Air Soil Pollut (2017) 228:339 Page 7 of 12 339

Table 2 Analysis of MNZ adsorption on GAC

Experimental runs Adsorption rate constant, k1 (min−1) based on Outcomes of adsorption isotherm modeling

Eq. (13) Eq. (16) Type of isotherm Parameters

E-19 – 2.09 (1.4) Freundlich KF = 1.145 mg g−1

nL = 0.127
E-20 0.31 1.93 (1.7) r2 = 0.947
E-21 0.05 0.53 (1.3) Langmuir qmL = 3.165 mg g−1
KL = 0.067 L mg−1
E-22 0.009 0.60 (1.2) r2 = 0.904
E-23 0.02 0.59 (1.1) Sips Ks = 2.16 L mg−1
ms = 0.647
E-24 0.06 3.84 (0.7) r2 = 0.962

Note: the values in parenthesis indicate the order of the reaction as calculated from Eq. (16)

(Velasco et al. 2012). The value of k1 was 2.0 min−1 in
E-13 but it was reduced by five times at the highest MNZ
concentration investigated (E-18).
4.2 MNZ Removal by Adsorption
The SEM and EDS analysis confirmed the presence of
MNZ on the surface pores of GAC (Fig. 3). Owing to the
neutrality of MNZ (pKa = 2.5) in the pH range of 6 to 7, the
adsorption could be mainly by physical forces/phenome-
non. Based on the profiles of residual MNZ concentration
in the reaction mixtures, the maximum MNZ adsorption
capacity of GAC were found out and the values are given
in Table 2. A maximum MNZ removal of around 28% was
observed in E-20 and E-21, which was much lesser com-
pared to the MNZ removal observed under photolysis and
photocatalysis systems. The value of MNZ removal rate
constant (k1) in the GAC adsorption was also calculated
using the first-order reaction (Eq. 8). As expected, the k1
values were found to lower compared to the other systems
(E-1 to E-18). In addition, the rate of adsorption was
determined using Eqs. (13)–(16) and it was found that
the first-order equation was found to be suitable compared
to other kinetic models (data not shown). The calculated
adsorption rate constant values based on Eqs. (13) and (16)
and the order of reaction (n) based on Eq. (16) are shown in
Table 2. The value of n indicates that the adsorption
depends on MNZ concentration at lower MNZ

Fig. 2 pH/ORP profiles for UV- 9 350

C only, UV-C/TiO2, and UV-C/
8
GAC experiments for degradation
of 15 mg L−1 of MNZ 7
300

6
250
ORP (mV)

5
pH

4
200
3

2 pH trend - E-4 pH trend - E-10

150
pH trend - E-16 ORP trend - E-4
1
ORP trend - E-10 ORP trend - E-16
0 100
0 20 40 60 80 100 120
Time (min)
339 Page 8 of 12
Fig. 3 SEM images of GAC (a) before adsorption and (b) after adsorption, and EDS images of GAC (c) before adsorption and (d) adsorption
concentration, whereas at the highest MNZ concentration
(adopted in this investigation), the reaction order does not
depend on initial adsorbate concentration.
The Freundlich isotherm was found to be suitable to
represent the MNZ adsorption on GAC. A smaller value
of 1/nL indicates the formation of strong bond between
the adsorbate and adsorbent. The maximum MNZ ad-
sorption capacity of GAC was calculated as
1.145 mg g−1 based on E-19 to E-24. It is envisaged
that the adsorption sites of GAC might be occupied at
much faster rate at higher MNZ concentration (E-24); as
a result, the overall adsorption could not be represented
by the first-order equation. Moreover, the adsorption
might have followed multi-layer rather than monolayer
as expressed by Langmuir’s isotherm at higher concen-
trations. On the other hand, the smaller ms value calcu-
lated based on Sips isotherm indicate that it can
Water Air Soil Pollut (2017) 228:339
converge to Freundlich’s isotherm for the range of
MNZ concentration adopted in this study.
4.3 Comparison of MNZ Removal Based on Energy
Consumption Analysis
The potential of each process, i.e., photolysis (E-1 to E-6),
photocatalysis with TiO2 and GAC (E-7 to E-18), and
adsorption on GAC (E-19 to E-24), in terms of MNZ
removal rates is shown in Fig. 4a. Based on the figure, it
can be concluded that UV-C/TiO2 and UV-C/GAC are
highly efficient processes with greater rate constant values
compared to photolysis (UV-C only) and adsorption on
GAC. Moreover, it can be noticed that the removal rates
were fairly equal for UV-C/TiO2 and UV-C/GAC systems
at higher MNZ concentrations (50 and 100 mg L−1). How-
ever, energy consumption and EEO analysis are better
Water Air Soil Pollut (2017) 228:339 Page 9 of 12 339

Fig. 4 a Removal rates and b

EEO values for various systems
a
0.06
under different initial MNZ

Rate of MNZ removal (min-1)

concentrations 0.05 Photolysis
Photocatalysis with TiO2
0.04 Photocatalysis with GAC
Adsorption
0.03

0.02

0.01

0
0.1 1 5 15 50 100
-1
MNZ concentration (mg L )

b
1.2

Photolysis
1
Photocatalysis with TiO2
EEO (KWh m-3 order-1)

Photocatalysis with GAC

0.8 Adsorption

0.6

0.4

0.2

0
0.1 1 5 15 50 100
MNZ concentration (mg L-1)

suitable in the cost evaluation of different processes. The
EEO of all experimental runs were calculated based on Eq.
(17) and the values were used to identify the effectiveness
of the system (Vishnuganth et al. 2016).
P  t  1000
E EO ¼
C0
V  60  log
Ct
Where P is the power consumed by the system
(expressed in Watt) and V is the volume of the reactor
(i.e., 1.9 L). The term P is the major component, which
accounts for the operational cost of the photolytic and
photocatalytic systems for a given time in the removal of
the target micropollutant, i.e., MNZ. From the EEO values,
it was evident that photocatalytic systems with TiO2 and
GAC were highly energy efficient (0.03 to 0.34 kWh m−3
order−1) compared to photolysis (0.15 to 0.4 kWh m−3
order−1) and adsorption systems (0.44 to 0.99 kWh m−3
order−1) (Fig. 4b). The EEO value was found to be increas-
ing with the increase in MNZ concentrations; however, no
significant difference in EEO value was observed between
0.1 and 15 mg L−1. This shows that photocatalytic system
with TiO2 can be used for the removal of micropollutants
ð17Þ from both industrial wastewater and contaminated surface/
ground waters. However, the effect of other ions and solids
in the removal of micropollutants in photocatalytic system
need to be analyzed.
4.4 MNZ Degradation Pathway
The LC-MS spectrums for the samples (E-10) were
analyzed at 0 and 120 min as shown in Fig. 5a. Based
on LC-MS analysis, a plausible reaction sequence of
MNZ mineralization under TiO2 slurry photocatalytic
system was proposed as shown in Fig. 5b. Previously, it
was reported that the first step in the degradation of
MNZ was mainly by hydroxylation due to HO· radical
 339 Page 10 of 12 Water Air Soil Pollut (2017) 228:339

a b
D:\Raw Data\...\met 0 min_160212230904 3/4/2016 7:53:16 PM met 0 min D:\Raw Data\...\met 120 min_160212230904 3/4/2016 7:55:08 PM met 120 min

met 0 min_160212230904 #98 RT: 0.92 AV: 1 NL: 7.29E6 met 120 min_160212230904 #259 RT: 2.39 AV: 1 NL: 1.45E7
T: FTMS + c ESI Full ms [100.00-2000.00] T: FTMS + c ESI Full ms [100.00-2000.00]
172.0719 116.9856
100 100

95 95

90 90

85 85

80 80

75 75

70 70

65 65

60 60

Relative Abundance
Relative Abundance

55 55

50 50

45 45

40 40

35 35 149.0120
30 30

25 103.9781 25
132.9581
20 20 147.0553
116.9860 103.9779 129.0301 134.9964
15 130.5314 15 113.9765 118.9788
136.0045 155.0294
146.5446 123.0031
10 121.5261 10
153.5254 170.0326 158.0124
105.5129 128.0456 198.0190 164.9845
5 161.0124 175.1193 5
112.9576 191.0455 109.0238 141.9585 174.9914 187.0013 198.9849
0 0
100 110 120 130 140 150 160 170 180 190 200 100 110 120 130 140 150 160 170 180 190 200
m/z m/z

c N Cleavage of the N OH
N -NO3
O ethanol group
+
H3C
N
N H3C OH H3C OH
-
N N
O H (C)
Breaking of
HO
OH HO imidazole moiety -NO3

(A) (B)

O
NH2
O
(D)
OH

CO2
O O
+
Simpler OH
NO3- / NO2- +
aliphatics H2C
+ H2N OH
H2O
(F) (E)
Fig. 5 a LC-MS spectrum of sample collected from E-10 at 0 min, b LC-MS spectrum of sample collected from E-10 at 120 min, and c
proposed metronidazole mineralization pathway in photocatalytic system

produced in the photocatalytic system and subsequent The other major degradation intermediates identified
formation of compound-B (Fig. 5b). Subsequently, the from LC-MS spectrums were found to have m/z values
cleavage of lateral N-ethanol group has resulted in the 116 and 149. The formation of heterocyclic
formation of compound-C as proposed by Perez et al. compound-D (3-carbomoyl prop 2-enoic acid, m/z
(2015). However, both compounds-B and -C 116) was due to the attack by OH· which led to the
(3-(2-hydroxy-ethyl)-2-methyl-3H-imidazol-4-ol and breaking of imidazole moiety and subsequent, release of
2-methyl-3H-imidazol-4-ol, respectively) were not sta- NO3− ion. Further, the removal of lateral groups (i.e., –
ble with time (i.e., no peaks were observed at 120 min). CH = CH–) from compound-D (i.e., compound-E) and
Water Air Soil Pollut (2017) 228:339
the addition of compound-F (2-propen-1-ol, i.e., formed
by addition of OH to the lateral groups) has shown m/z
value of 149. The compound-E is a short-linear aliphatic
carboxylic acid produced by the oxidation of
compound-D. This particular observation correlates
well with the decline in pH of the system toward acidic
range (from pH 8 to pH 5 after 120 min).
The sample collected from E-10 was analyzed for
TOC and the presence of nitrate/nitrite ions using ion
chromatography (Dionex, USA). The results show that
considerable quantity of carbon molecules present in
MNZ was removed from the system as CO2 gas as a
result of photocatalytic oxidation of MNZ. The total
carbon removal in the system was 66.4%, which indi-
cate a partial mineralization of MNZ and formation of
MNZ by-products in the system. On the other hand, ion
chromatography analysis confirmed the formation of
nitrate in the system. Therefore, the effluent from the
photocatalytic system needs to be treated for nitrate or
the stability of nitrate in the same system needs to be
investigated. The experiments and correlations corre-
sponding to the formation of nitrate ion in the system
and the possible theoretical nitrogen release in the sys-
tem are in progress.
5 Microtoxicity Studies
The bioluminescence inhibition assay was conducted
using a marine bacterium Vibrio fischeri to assess the
toxicity of MNZ, TiO2, and the treated samples (after
settling TiO2 catalyst for 6 and 12 h) from selected
experimental runs. The bacterial luminescence readings
were measured using a Microtox model 500 analyzer
(Modern Water Inc., UK) at different exposure time.
The percentage inhibition effect of the samples to the
bacterium is calculated as toxicity units (TU) using
Eq. (18). The 81.9% basic protocol (consisting of four
test dilutions) was carried out to evaluate the ecotoxicity
of the aqueous suspensions. The possible interference of
TiO2 in the luminescence measurements if any were
accounted by measuring the absorbance of the tested
suspension without bacterium addition.
. Alexander, J., Karaolia, P., Fatta-Kassinos, D., & Schwartz, T.
Toxicity unit ðTU50 Þ ¼ 100 EC50 ð18Þ
Accordingly, the toxicity unit of MNZ was found to
be 1.573 after 60-min exposure time, whereas it was
Page 11 of 12 339
2.511 for TiO2 catalyst after 15 min of exposure. The
raw sample from E-10 (0 min), treated sample from
E-10 after 120 min (without settling), and treated
samples from E-10 after 6 and 12 h settling have shown
an inhibition effect of 18.1, 13.8, 11.9, and 9.52%,
respectively, at 15-min exposure time. The difference
in percentage inhibition between 0- and 120-min sam-
ples of E-10 was due to the presence of MNZ metabo-
lites. But the toxic levels of samples are lesser than the
potential toxic limits. However, the long-term persis-
tence of MNZ and their metabolites can lead to bacterial
resistance, which needs further attention.
6 Conclusions
The application of TiO2 and GAC as catalysts in the UV-
C photocatalytic system has been investigated. The
MNZ removal efficiencies in UV-C/TiO2 and UV-C/
GAC systems were fairly equal at lower MNZ concen-
trations (0.1–5 mg L−1). However, decline in MNZ
removal efficiency was observed in both systems be-
yond an initial MNZ concentration of 15 mg L−1. The
MNZ removal was modeled using the first-order rate
equation and the efficiency of various systems were
analyzed by EEO values. The EEO values were in good
correlation with the removal rate constants. The MNZ
mineralization pathway in the photocatalytic system
was proposed based on LC-MS analysis. The release
of ionic compounds of nitrogen and degradation inter-
mediates of MNZ would be of concern in the effluent.
As a whole, it can be concluded that the designed
photocatalytic system is highly efficient in the removal
of micropollutants from industrial wastewater and con-
taminated surface/ground waters.
Acknowledgements The authors acknowledge the financial
support from Centre for Industrial Consultancy and Sponsored
Research (ICSR), IIT Madras to execute this research work (Grant
No: CIE/14-15/832/NFIG/SMAT and CIE/14-15/650/NFSC/
SMAT).
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