Journal of Environmental Chemical Engineering 6 (2018) 754–761

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Journal of Environmental Chemical Engineering

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Analysis of metronidazole removal and micro-toxicity in photolytic systems: T

Effects of persulfate dosage, anions and reactor operation-mode
⁎
N. Neghi, Navneeth R. Krishnan, Mathava Kumar
Environmental and Water Resources Engineering Division, Department of Civil Engineering, IIT Madras, Chennai, 600036, India

A R T I C L E I N F O A B S T R A C T

Keywords: The efficiency of persulfate (PS) alone, UV-C activated TiO2 (UV/TiO2), UV-C activated PS (UV/PS) and UV/PS
Antibiotics with TiO2 (UV/PS/TiO2) in the oxidative removal of metronidazole (MNZ) was studied. In addition, applicability
Metronidazole of UV/PS process in batch and continuous photo-reactors (BPR and CPR) was investigated. The performance of
Photo-reactor BPR and CPR was assessed in terms of energy consumed and electrical energy per order (EEO), which indicated that
Energy consumption analysis
both UV/PS and UV/PS/TiO2 systems were energy efficient. On the other hand, MNZ removal kinetics has revealed
Micro-toxicity
a higher MNZ removal rate of 0.232 min−1 in UV/PS/TiO2 system and showed a pseudo-first-order kinetics
(r2 > 0.96). Furthermore, the effect of influent anion concentration (i.e. Cl−, SO42−, NO3− and their combina-
tions) on UV/PS system was examined. The sequence of MNZ removal (from highest to lowest) in the presence of
anions was (SO42− + Cl− + NO3−) > (SO42− + NO3−) > SO42− > (SO42− + Cl−) > Cl− > NO3−. An
oxidative degradation pathway of MNZ in UV/TiO2 system was proposed. The toxicity of treated samples was
evaluated using micro-toxicity assay against V. fischeri. The percentage inhibition of effluent samples to V. fischeri
was within 15%, which denotes the suitability of CPR for real-time application.

1. Introduction whereas it is positively charged at acidic condition and negatively

Emerging contaminants (ECs) such as pharmaceutically active
compounds, personal care products, surfactants and their residues,
plasticizers and industrial additives are used in large quantities in day-
to-day life. These ECs are complex organic molecules having a mole-
cular weight of 100–1000 Da, which can produce detrimental effects to
human and aquatic biota [1]. Antibiotics, one of the major classes of
pharmaceutically active compounds, have secured an inevitable place
in the veterinary and human medications, which can be observed from
their global statistical usage [2]. The frequent use/misuse of antibiotics
in turn accelerates the evolution and spread of antibiotic resistant genes
in microorganisms, which would cause fatal health risks to animals and
human beings [2–4]. After their intended purpose, a large fraction of
these compounds are discharged into the environment either un-
changed or in its metabolized state. As a result, traces of these com-
pounds are observed in all water systems due to incomplete removal by
conventional wastewater treatment methods [5].
Metronidazole (2-methyl-5-nitroimidazole-1-ethanol, MNZ) is one
of the widely used antibiotics for the treatment of anaerobic and pro-
tozoal infections [6]. MNZ is also used in sea food processing units
(prawns, shrimp, etc) [7] and one of the frequently used drugs in US
during pregnancy [8]. MNZ is stable at neutral pH (pKa = 2.55)
charged at basic condition [9]. Moreover, MNZ is non-biodegradable,
highly soluble in water (9.5 g L−1 at 25 °C) and has a tendency to ac-
cumulate in the aquatic environment (log kow ∼ −0.1). As a result,
several researchers reported the presence of MNZ in wastewater and
surface water from one to several ng L−1 (for example, about
3800 ng L−1 of MNZ detected in hospital wastewater, India) [10–13].
However, the removal of MNZ from wastewater and water systems is
gaining paramount importance considering its toxicity, carcinogenicity
[14] and the increasing resistance rate in microorganisms [15–17].
MNZ removal by advanced oxidation processes (AOPs) such as ozona-
tion, heterogeneous photocatalysis, Fenton, photo-Fenton and electro-
Fenton processes have been investigated and their performance was
compared with conventional methods [9,18,19]. Photocatalytic de-
gradation of organic compounds, a most commonly used method in
water/wastewater treatment, was achieved by exciting semiconductors
such as titanium-dioxide (TiO2) in the presence of UV illumination. This
+
generates holes in valence band (hVB ) and electrons in the conduction
−
band (eCB )on the surface of catalyst. The generated holes have the
capability to combine with OH− and H2O, which leads to highly oxi-
dative hydroxyl radicals production (OH%, E0 = +2.80 V). However,
+ −
the recombination of photogenerated hVB and eCB diminishes the overall
rate and efficiency of the photocatalytic process. To avoid the

⁎
Corresponding author.
E-mail address: mathav@iitm.ac.in (M. Kumar).

https://doi.org/10.1016/j.jece.2017.12.072
Received 9 October 2017; Received in revised form 9 December 2017; Accepted 31 December 2017
Available online 02 January 2018
2213-3437/ © 2018 Elsevier Ltd. All rights reserved.
N. Neghi et al.
recombination, oxygen is used as the most common electron acceptor to
react with eCB−
producing superoxide radical(O−2 .) . Alternatively, the
addition of oxidants as electron acceptor could improve the efficiency
of photocatalytic process through increased generation of reactive ra-
dicals and also reduce the recombination [20].
In the recent years, persulfate (PS) addition, as an oxidant, in UV
system has been receiving significant attention. The activation of PS in
any system could be achieved by heat or UV illumination or ferrous ion.
The sulfate radical (SO4− ., E0 = +2.65–3.1 V) [21,22] can be generated
as per the reaction mechanisms shown in Eqs. (1)–(5). The presence of
OH% and SO4− . in the system could result in a higher rate of organic
degradation due to the combined reaction of the radicals. Several in-
vestigations in the past supplemented PS in UV system to understand
the acceleration in organics removal rate of phenolic compounds, dis-
infection by-products, dyes and few pharmaceuticals in water systems
[23–29]. Recently, few investigations tried to explore the effect of PS in
UV/TiO2 system on the degradation of recalcitrant compounds such as
benzotriazole [30] and removal of metals [31]. The advantages of
adding PS in UV/TiO2 system are high stability, non-toxic nature and
low cost of both TiO2 and PS [32,33]. Therefore, the application of PS
in UV/TiO2 system has lot of scope for further research in the removal
of ECs. Moreover, it is expected that UV/TiO2/PS system will be effi-
cient compared to UV/TiO2 system in the mineralization of organic
compounds, owing to the increased radical formation in the system as
shown in Eqs. (6) and (7).
S2 O82 − + h ν → 2SO4·− (1)
SO4·− + OH− → SO42 − + HO· (2)
HO· + HO· → H2O2 (3)
HO· + SO4·− → HSO5− (4)
SO42 − + HO· → SO4·− + OH− (5)
Organics + hν (UV / TiO2) → HO⋅ → CO2 + H2 O + Intermediates (6)
Organics + hν (UV / TiO2/PS ) → HO⋅/SO4.−/ H2 O2
→ CO2 + H2 O + Intermediates (7)
In real-time scenario, the co-existence of cations, anions (i.e. Cl−,
SO42−, NO3−, etc.) and organic pollutants in wastewater are inevitable.
Therefore, understanding the role and effect of anions (individually and
their combination) in the oxidative removal of organic pollutants are
deemed necessary. Additionally, the operating mode (batch or con-
tinuous) and operating conditions (i.e. pH, catalytic dosage and initial
concentration of the target pollutant, etc.) are some of the governing
factors in the scale-up of the laboratory-scale reactors. To the best of
our knowledge, no investigation in the past have compared and ana-
lyzed the organics removal in batch and continuous UV/PS systems.
Therefore, the major aim of this investigation is to (i) optimize the PS
dosage for best possible MNZ removal in the UV/PS system, (ii) explore
the presence of anions (i.e. individual as well as combination of Cl−,
SO42− and NO3− ions) on MNZ removal in UV/PS system, (ii) compare
the performance of UV/PS system with PS alone and UV/PS in the
presence of TiO2 (UV/PS/TiO2) systems based on economic analysis
(i.e. by energy consumed and energy consumed per order), (iv) com-
pare the performance of batch and continuous UV/PS systems and (v)
analyze the toxicity of the treated effluent.
2. Materials and methods
2.1. Chemicals and reagents
MNZ (99.9% purity) was procured from Sigma Aldrich, India and
TiO2 with a mean particle size of 25 nm (98% purity and anatase form)
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Journal of Environmental Chemical Engineering 6 (2018) 754–761
was supplied by Avra Synthesis, India. The oxidant used in the ex-
periments, i.e. potassium persulfate (LR grade), acetonitrile and deio-
nized water (for HPLC analysis) were purchased from Merck, Germany.
The other salts used in the experiments were of greater than 99% purity
and supplied by Ranbaxy fine chemicals, India.
2.2. Reactor set-up
2.2.1. Batch photo-reactor (BPR)
A cylindrical reactor of 1.9 L working volume was fabricated and
used for UV/PS and UV/PS/TiO2 experiments (Fig. 1a). An electronic
overhead stirrer was mounted on the reactor and operated at
200–300 rpm to keep the reactor contents in the homogeneous state.
Two UV lamps (each 16W power and λmax of 254 nm) were installed in
the reactor to supply the UV power. In addition, pH, temperature and
oxidation-reduction potential (ORP) probes were inserted into the re-
actor to measure the variation of parameters during experiments. All
BPR experiments were carried out for 120 min and in ambient condi-
tions.
2.2.2. Continuous photo-reactor (CPR)
The schematic diagram of continuous-mode photo-reactor (CPR)
system is shown in Fig. 1(b). The CPR consists of a feed tank, a UV
reactor tank and an effluent tank of capacities 50 L, 23 L and 50 L, re-
spectively. The inlet and outlet flows of the UV reactor were kept at a
predetermined rate (i.e. fixed hydraulic retention time, HRT) by the
operation of peristaltic pumps (P1 and P2) as shown in Fig. 1(b). The lid
of the UV reactor tank was provided with several ports to accommodate
a maximum of four UV lamps, stirring rod and online monitoring probes
for pH, temperature, oxidation-reduction potential (ORP) and dissolved
oxygen content (DO).
2.3. Experimental procedure
As a precursor, MNZ stock solution was prepared by dissolving
100 mg MNZ in 1 L of distilled water and stored at 4 °C. The entire set of
experiments were conducted either in batch- or continuous-modes. All
the experiments were conducted at an initial MNZ concentration of
10 mg L−1 by diluting the stock solution with distilled water and at
room temperature (32°–33 °C) in uncontrolled temperature and pH
conditions, i.e. without any temperature and pH controls.
2.3.1. Batch-mode experiments using BPR
The BPR experiments were conducted in three phases. In the first
phase, MNZ oxidation by PS (100, 250, 500 and 1000 mg L−1) in the
absence (R-1–R-4) and presence of 32 W UV power (R-5–R-8) was
evaluated under homogeneous mixing condition. Based on the results,
the optimal PS dosage required for MNZ removal was found out. In the
second phase, a pure photocatalytic experiment (R-9) in the presence of
2.5 g L−1 TiO2 was conducted, and another run (R-10) was performed
under optimal PS dosage in the presence of TiO2 (i.e. 32W UV power,
100 mg L−1 PS and 2.5 g L−1 TiO2). In the final phase, the effect of
anions, i.e. NO3−, SO42−, Cl−, individually (R-11–R-13) and their
combination, i.e. NO3−+SO42− at 100:500 mg L−1 (R-14),
SO42− + Cl− at 500:1000 mg L−1 (R-15) and NO3−+SO42− + Cl− at
100:500:1000 mg L−1 (R-16) in UV/PS system was evaluated. The in-
itial concentration of anions was maintained lower than their pre-
scribed levels in the wastewater effluent standards [34]. From all
phases, the samples were collected after 5, 10, 15, 30, 60, 90 and
120 min and the solution pH, ORP, MNZ concentration and quantity of
ion(s) were measured
2.3.2. Continuous-mode experiments using CPR
The CPR experiments were carried out to determine the effects of
UV power and operation-mode on the performance of UV-C/PS system
on MNZ removal. The experiments were conducted at the optimal PS
N. Neghi et al. Journal of Environmental Chemical Engineering 6 (2018) 754–761

Fig. 1. Schematic diagrams of (a) batch photocatalytic re-

actor (BPR) and (b) continuous photocatalytic reactor (CPR).

dosage and at 32W (R-17) and 64W (R-18) UV power. Both experiments the reactor and analyzed for MNZ concentration. The reaction mixture
were conducted by maintaining 60 min HRT and steady-flow condition. pH, ORP, temperature and DO were measured using the online-mon-
At regular intervals, samples were withdrawn from the effluent line of itoring system.

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2.3.3. Micro-toxicity assay Energy used(W) × Reaction time(min)

The micro-toxicity assay was carried out using bioluminescence
freeze dried bacteria Vibrio fischeri (NRRL number B-11177) purchased
from Modern water Inc., UK. The assay was conducted following the
procedures stated in ISO 11348-3:2007 standards [35]. It was adopted
in several investigations due to the high sensitivity of the assay to a
wide range of simple to complex chemicals and its capability to produce
quicker results. Therefore, this assay was followed to test the micro-
toxicity of MNZ and BPR effluent samples containing MNZ, its inter-
mediates as well other anions. The 81.9% basic (consisting of four test
dilutions) and 81.9% screening protocol was carried out to assess the
toxicity of MNZ and the relative toxicity of the effluent samples, re-
spectively. Accordingly, 900 μL of all the samples were equally exposed
in 100 μL of bacterial suspension containing 1 × 106 cells of Vibrio fi-
scheri. The assay was carried out at 15 °C and the bacterial luminescence
reading at different exposure times, i.e. 5, 15, 30 and 60 min, was
measured using Microtox 500 analyzer (Modern water Inc., UK). The
initial intensity of luminescence with that at different exposure times
was used to evaluate the toxicity of the samples. The percentage in-
hibition effect of the samples to the bacterium is calculated as toxicity
units (TU) using Eq. (8). In Eq. (8), EC50 represents 50% inhibition
concentration as percentage. In order to understand the toxicity level of
MNZ, the measured toxicity values of MNZ was compared with the
toxicity of a known standard toxicant ZnSO4 [35], i.e. equivalent-
toxicity approach.
Toxicity unit (TU) = 100/EC50 (8)
2.4. Analytical techniques
MNZ concentration in the sample was analyzed using high perfor-
mance liquid chromatography (Dionex, USA) fitted with C18 silica
based reverse phase column and UV–vis detector. Acetonitrile and
deionized water (Milli-Q) were mixed in the ratio of 60:40 and used as
the mobile phase. The column flow-rate was maintained at 1 mL min−1
and wavelength of the UV detector was set at 254 nm. Under these
conditions, the MNZ peak was observed after a retention time of
2.7 min. The organic carbon constituent in the sample was analyzed
using TOC analyzer (Shimadzu, Japan) equipped with NDIR analyzer.
The photocatalytic degradation products of MNZ in the samples were
identified using a liquid chromatography fitted with ion-trap mass
spectrometer (LC–MS) (Thermoscientific, USA). The reaction mixture
pH, ORP and temperature (in BPR) were measured using a multi-
parameter analyzer (OAKTON, India). In CPR, pH, temperature, ORP
and DO were measured using digital online-monitoring system (Hanna
Equipments Pvt Ltd, India). The anion concentration in the samples was
measured using UV–vis spectroscopy (UV-1800, Shimadzu, Japan).
Energy Consumed =
1000 × 60 (11)
P× t× 1000
EEO = C
V×60 × log C0 (12)
f
Where P is power consumed by the system expressed in Watt and V is
the volume of batch and continuous photo-reactors (i.e. 1.9 L and 23 L,
respectively).
4. Results and discussion
4.1. MNZ removal in BPR
MNZ degradation in the presence of PS (100–1000 mg L−1, R-1–R-
4) is shown in Fig. 2. It can be noticed that the maximum MNZ removal
(i.e. 29.8%) has occurred in R-4 after 120 min. MNZ removal in R-4 was
due to the thermal activation of PS at the experimental temperature
(i.e. 32 °C), which has facilitated homolysis of the peroxide bond and
the subsequent generation of SO4− . in the system [37]. Consequently, the
generated SO4− .might have taken part in the non-selective oxidation of
the MNZ in the system [38]. However, greater MNZ removal efficiency
could not be achieved in PS oxidation system due to the lower reaction
temperature of the BPR, i.e. at 32 °C. On the other hand, the aqueous
solutions were observed to be acidic (pH – 6.18–4.4) at the end of
120 min due to the formation of H2SO4 and the ORP profiles were found
rising with increase in the initial PS dosage (260–571 mV). The initial
concentration of PS addition played a major role in acidifying the re-
action mixture and increasing the ORP of the system.
In UV/PS system, persulfate gets activated in the presence of UV-C
illumination and SO4− .radicals were generated as shown in Eq. (1) and
these radicals lead to a chain of reactions (Eqs. (2)–(5)) resulting in the
generation of OH. and H2O2. As a result, the overall oxidation potential
of the system has increased several folds. Moreover, MNZ has sig-
nificant UV absorption at 254 nm, which is exactly the λmax of the UV-C
lamp used in this investigation [39]. Therefore, MNZ removal in the
UV/PS system was by both photolysis and radical oxidation. This
combined effect has produced almost complete removal 99.9% of MNZ
in R-8 operated with 1000 mg L−1 of PS along with 32W UV illumi-
nation for 120 min (Fig. 2). However, a proportionate increase in SO42−
concentration, from 134.2 mg L−1 to 516.8 mg L−1, was observed in the
treated solutions of the experimental runs (R-5–R-8). As per the reg-
ulatory standards (IS 10500: 2012), the permissible limit of sulfates in
drinking water is 400 mg L−1. Thus, PS dosage up to 100 mg L−1 (R-5)
was found to be reasonable to meet effluent discharge standards
without any further treatment as well as to achieve accelerated MNZ
removal. Under this condition (R-5), 134 mg L−1 of SO42− and
0.083 mg L−1 min−1 of MNZ removal rate was observed (Table 1).
However, decline in pH (4.28-3.11) and increase in ORP (316-723 mV)

3. Data interpretation

The photocatalytic removal efficiency of MNZ in BPR and CPR was

calculated as shown in Eq. (9).

C0 − Cf
η= × 100
C0 (9)

Where C0 and Cf represents initial and final MNZ concentration at

any time (t), respectively. On the other hand, the MNZ removal rate in
different systems was calculated as per Eq. (10).

Removal (%) × concentration(mgL−1)

Removal rate =
Time (min) (10)

The electrical energy consumed and the electrical energy required

to reduce MNZ concentration by one order of magnitude (EEO) was
Fig. 2. MNZ removal in PS oxidation and UV/PS systems in BPR.
calculated by Eqs. (11) and (12), respectively [36].

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N. Neghi et al. Journal of Environmental Chemical Engineering 6 (2018) 754–761

Table 1
Consolidated list of experimental runs.

Run-No Type of system MNZ removal Removal rate Rate constant ‘ka’ Rate constant ‘kb’ Overall pseudo-first EEO (KWh m−3 Energy
(%) at 120 min (mg L−1 min −1) up to 15 min after 15 min order rate constant order−1) consumed
(min−1) (min−1) ‘k’ (min−1) (KWh)

R-1 PS oxidation system 12.63 0.019 0.005 0.0005 0.0007 1328.4 0.084
R-2 23.8 0.02 0.012 0.0007 0.0015 660.8
R-3 13.02 0.01 0.004 0.006 0.0011 1285.8
R-4 29.8 0.025 0.014 0.001 0.0011 507.5
R-5 UV/PS system in BPR 99.1 0.083 0.123 0.028 0.033 38.3 0.148
R-6 97.4 0.081 0.078 0.02 0.022 49.1
R-7 99.8 0.083 0.205 0.025 0.016 29.73
R-8 99.9 0.084 0.227 0.024 0.039 27.6
R-9 UV/TiO2 system in BPR 96 0.08 0.016 0.028 0.026 55.6
R-10 UV/PS/TiO2 system in BPR 98.3* 0.164* 0.232 0.023 0.053* 22.1*
R-11 Effect of individual/ 95.4 0.08 0.179 0.005 0.017 58.3
R-12 combination of anions in 99.9 0.084 0.185 0.034 0.049 24.2
R-13 UV/PS system in BPR 99.8 0.083 0.055 0.052 0.059 28.9
R-14 99.9 0.084 0.197 0.046 0.064 22.5
R-15 99.4 0.082 0.081 0.037 0.044 34.9
R-16 99.7 0.083 0.131 0.011 0.047 58.7
R-17 UV/PS system in CPR 65.9* 0.11* 0.057 0.004 0.013* 83.4* 0.212
R-18 89.5* 0.141* 0.097 0.014 0.033* 39.8*

* +
The values in the parenthesis are at the end of 60 min; MNZ removal per time (after 120 min).

with proportionate increase in initial SO42− concentration was ob-
served with respect to time in R-5 to R-8. It was observed that in R-9
around 96% removal occurred at the end of 120 min rather in R-10,
95.3% MNZ removal was observed within 15 min, which reveals that
improvement in MNZ removal is possible by the combination of TiO2
−
and PS. The addition of oxidant (PS) in UV/TiO2 has scavenged the eCB
(i.e. excited by the irradiation of TiO2) and it has resulted the accu-
+
mulation of highly oxidative hVB in UV/PS/TiO2 system. Additionally,
in UV/TiO2 photocatalysis, OH and O2− .are produced; whereas OH. and
.
On the other hand, the calculation of EEO (Eq. (12)) is useful in esti-
mating the actual efficacy of the system. The calculated EEO values were
38.3 and 22.1 KWh m−3 order−1 for R-5 and R-10, respectively, which
indicate that UV/PS/TiO2 system is comparatively or equally energy
efficient than UV/PS system. However, the comparison of electrical
energy consumed in R-5 and R-10, failed to reflect the efficacy of the
system in MNZ removal because the energy consumed in both the runs
were the same, i.e. 0.148 kWh.

SO4− .and other radicals are generated in UV/PS system (Eqs. (6) and
4.2. Effect of anions in UV/PS systems
(7)). The complete degradation of MNZ in shortest reaction time in UV/
PS/TiO2 system could be attributed to the cumulative effect of both
The effect of anions, i.e. NO3−, SO42−,Cl− and their combination (R-
UV/TiO2 and UV/PS systems.
11 to R-16) during MNZ removal in UV/PS system (at PS dosage of
In all runs, MNZ degradation was found to follow the first-order
100 mg L−1) was investigated in BPR and the results were compared
reaction kinetics and the values are given in Table 1. However, a two-
with R-5 (i.e. UV/PS in the absence of anions). In R-5, 99.1% MNZ re-
phase reaction was observed in UV/PS/TiO2 system (R-10). In Phase-I
moval was observed and the corresponding pseudo-first-order rate con-
(0–15 min) accelerated MNZ degradation was observed; whereas slower
stant was calculated as 0.033 min−1. Although near complete removal of
degradation as well as mineralization of intermediates of MNZ were
MNZ was observed in R-11 to R-16, a noticeable change in the pattern of
achieved in Phase-II (16–60 min). The MNZ removal rate constants
MNZ removal can be seen in Fig. 4. The NO3− present in R-11 under
corresponding to Phase-I and Phase-II were 0.232 min−1 and
highly oxidative condition by UV illumination is expected to change its
0.023 min−1, respectively (Fig. 3). It is inferred that both in UV/PS and
redox state, from NO3− to NO3./NO2. [40,41]. Therefore, there would be
UV/PS/TiO2 systems, MNZ was completely removed but at different
a competition between SO42− (from PS) and NO3− for the utilization of
retention times. However, the energy and material costs need to be
UV energy when both these anions are present in a system. As a result,
evaluated before field-application. It was reported that cost associated
with electrical energy consumption accounts a major portion in the
operational cost of AOPs. The electrical energy consumed in all runs
was calculated as per Eq. (11) and the values are reported in Table 1.

Fig. 3. First-order rate curve for MNZ removal in UV/PS/TiO2 system. Fig. 4. MNZ removal in the presence of co-existing anions in UV/PS system.

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N. Neghi et al. Journal of Environmental Chemical Engineering 6 (2018) 754–761

Fig. 6. Comparison of first-order rate curves of MNZ (at 10 mg L−1) in BPR and CPR.
Fig. 5. MNZ removal at different cycles of CPR.

the MNZ degradation efficiency was decreased by 3.7% in R-11 after rate constant of 0.053 min−1 was obtained in UV/PS/TiO2 after 60 min,
120 min (Table 1).On the other hand, the presence of SO42− (R-12) has whereas it was found to be 0.033 min−1, 0.026 min−1 and
shown a similar MNZ removal as compared to R-5 but at a faster rate of 0.0007 min−1 in UV/PS, UV/TiO2 and PS alone systems at the end of
0.049 min−1 (Table 1). This is due to the fact that SO42−present in the 120 min. As explained earlier, two-phase degradation was observed in
system can participate in the generation of SO4− .as shown in Eq. (5) [42]. all runs and the corresponding rate constants were calculated and
In R-13, the presence of Cl− is expected to produce lesser capable oxi- shown in Table 1. Moreover, the MNZ removal rate constants obtained
dative radicals such as Cl, ClOH% and Cl2% in the presence of OH% and in other AOPs for the degradation of MNZ are compared in Table 2
SO4−% [43], which would lead to the reduction in the availability of [9,18,44]. From Tables 1 and 2, it can be noticed that UV/PS and as-
strong oxidative radicals in the system. As a result, slow and steady sociated systems are highly effective compared to UV/TiO2, UV/H2O2
pattern of MNZ removal was observed as shown in Fig. 5. and UV/H2O2/Fe2+ systems. However, TOC analysis has shown 58%
The combined effects of SO42− + NO3− and SO42− + Cl− on MNZ reduction in the organic carbon in UV/PS systems (theoretically,
removal were evaluated in R-14 and R-15, respectively. At the end of 4.21 mg L−1 of carbon present in 10 mg L−1 of MNZ), which reveal that
15 min, around 96% removal was observed in R-14 whereas only 71% mineralization of MNZ was not complete.
removal was observed in R-15. This could be attributed to the pro-
duction of lesser capable oxidative radicals in R-15 as discussed earlier. 4.5. Mechanism of MNZ degradation
However, the presence of NO3− has not shown any significant effect on
the overall removal of MNZ when the experiment was conducted for The hydroxyl radical mediated oxidative degradation pathway of
longer duration, i.e. 120 min. On the other hand, the presence of MNZ in UV/TiO2 system (R-9) has been proposed based on extensive
SO42− + NO3− + Cl− (R-16) has shown 86% MNZ removal in 15 min. LC–MS analysis. All molecules associated with MNZ appeared with H+
In co-existence of all three ions, the scavenging effects of both Cl− and adduct. The characteristic peak of MNZ (m/z = 171) was not present at
NO3− were defeated by the presence of SO42− ions; as a result, the MNZ the end of 120 min, which indicates that MNZ was broken into some
removal performance was not affected in R-16. intermediates or partially mineralized. At the end of treatment, two
stable intermediates having m/z values 116 and 149 were identified in
the LC–MS spectrums (Fig. 7). The first step in MNZ degradation by
4.3. MNZ removal by UV/PS systems in CPR
hydroxylation was mainly due to HO% in the photocatalytic system
which released nitrogen and led to the formation of compound B.
The CPR experiments were conducted at two different UV-C power
Subsequently, the removal of lateral N-ethanol group has resulted the
levels, i.e. 32W (R-17) and 64W (R-18), but under preset initial MNZ
formation of compound C [18]. Further, the compound C was cleaved
(10 mg L−1) and PS concentrations (100 mg L−1). The HRT in the re-
to compound D (3-carbomoyl prop 2-enoic acid, m/z 116) due to the
actor was kept at 60 min by maintaining the flow rate of the peristaltic
opening of imidazole moiety. The removal of lateral groups
pumps as 383.33 mL min−1. At the end of 60 min, around 66% MNZ
(i.e.−CH = CH−) from compound D led to the formation of compound
removal efficiency was observed in CPR at 32W UV power; whereas, the
E, which was found to be short-linear aliphatic carboxylic acid. The
efficiency was increased to 89.5% when the UV power was 64W.
addition of compounds E and F (2-propen-1-ol) present in the system
Therefore, MNZ removal efficiency can be improved by operating CPR
at 64W UV power or by operating at 32W UV power with longer HRT.
Table 2
Moreover, it is interesting to note that MNZ removal in R-5 and R-17
Comparison of MNZ removal rate constants.
were almost similar but operated at two different modes, i.e. batch and
continuous, respectively. The comparison of MNZ removal efficiency in AOP type Removal (%) Reaction Rate Reference
these two runs reveals that 12 times higher volume can be treated in time (min) constant
(min−1)
CPR in the given time (i.e. 60 min). In addition, it can be noticed in
Fig. 5 that the MNZ removal performance of CPR was unchanged with UV-C/TiO2 99.5 120 0.0233 [10]
no net negative effect even at the end of 5 cycles, i.e. R-17 continued for UV photolysis 12 5 0.023 [32]
5 cycles. These key findings indicate that scale-up of the UV/PS system UV/H2O2 64 5 0.466
can be achieved without any compromise in the performance. H2O2/Fe2+ 76 5 0.066
UV/H2O2/Fe2+ 94 5 0.23
Solar Photo- ∼100 80 0.040 [33]
4.4. MNZ removal kinetics in the considered systems electro Fenton
method
UV/TiO2 96 120 0.026 Present study
The first-order degradation rate curves of MNZ in PS, UV/PS and UV/PS/TiO2 95.3 15 0.232
UV/PS/TiO2 systems are compared in Fig. 6. A maximum MNZ removal

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N. Neghi et al. Journal of Environmental Chemical Engineering 6 (2018) 754–761

Fig. 7. Oxidative degradation pathway of MNZ in UV/TiO2 system.

has shown an m/z value of 149. A similar pathway or a slightly different that MNZ after consumption may transfer to acid and hydroxyl meta-
intermediate formation can be expected in the presence of both hy- bolites. The hydroxyl metabolite, formed by reduction of nitro group
droxyl and sulfate radicals that needs further analysis. from MNZ to a hydroxyl/amine group in the cytoplasm of anaerobes/
protozoa, accounts for 65% activity of the parent drug. This has the
potential to react with DNA and stop the synthesis of nucleic acid in the
4.6. Outcome of micro-toxicity assay
species. On the other hand, the toxicity of effluent samples (at the end
of 120 min) from R-5, R-14 and R-16 was also assessed. The treated
The toxicity of MNZ as well as the final effluent samples was eval-
samples from R-5 (containing 114 mg L−1 of SO42−), R-14 (containing
uated by performing micro-toxicity assay against V.fischeri. The per-
94 mg L−1 of NO3− and 294 mg L−1 of SO42−) and R-16 (containing
centage of V.fischeri inhibited by the samples, i.e. inhibition effect, was
184 mg L−1 of NO3− and 320 mg L−1 of SO42−) have shown an in-
taken as a measure of the quality of sample. A standard test using ZnSO4
hibition effect of 3%, 13% and 15%, respectively after 15 min exposure.
was used to compare (a) the toxicity of MNZ and (b) the treated samples
On the other hand, it is possible to express that 114 mg L−1 of SO42− is
containing MNZ intermediates and other ions. Fig. 8 shows the outcome
equivalent to a toxicity value at 107.8 mg L−1 of MNZ (Fig. 6). Simi-
of micro-toxicity study. It reveals that the initial MNZ concentration
larly, R-14 and R-16 samples have an equivalent toxicity of
(i.e. 10 mg L−1) has no inhibition effect/acute toxicity towards V.fi-
227.1 mg L−1 and 250.9 mg L−1 of MNZ, respectively. Additionally,
scheri. On the other hand, 50% inhibition effect was found at an MNZ
ecological risk of MNZ and similar other compounds in a sample at
concentration of 668.6 mg L−1. Using Eq. (8), the toxicity units (TU) of
different taxon levels can be assessed by fish embryo toxicity test, Ames
ZnSO4 and MNZ were found out as 15.4 and 1.5, respectively. The
fluctuating test for mutagenicity, yeast estrogen screen test, Micro-
corresponding EC50 concentrations were found out as 6.5 mg L-1 and
EROD test, etc. However, the sample equivalent toxicity values were
668.6 mg L-1, respectively (Fig. 8). However, the low TU value ob-
well within the limit but these values give an indication that excessive
served in this study could be attributed to the sensitivity of V.fischeri to
usage of sulfate can produce toxic effect to the environment.
MNZ and the mode of action of MNZ. The factsheet of MNZ indicates

5. Conclusions

MNZ removal in the presence of PS, UV/TiO2, UV/PS, and UV/PS/

TiO2 processes was assessed in batch and continuous photo-reactors. In
batch-mode MNZ experiments, increase in MNZ removal efficiency was
observed with proportionate increase in initial PS dosage. The PS do-
sage for 100 mg L−1 was found to be optimal for removing of 10 mg L−1
of MNZ in batch reactor operated with 32 W UV power. Under the
experimental conditions, MNZ degradation followed the pseudo-first
order degradation kinetics. Around 90% MNZ removal was observed in
CPR, when it was operated with 64W UV power and 100 mg L−1 PS
dosage. Moreover, the effect of Cl−, SO42− and NO3− anions on MNZ
removal was investigated. The presence of SO42− ions promoted the
MNZ removal whereas NO3− and Cl− ion declined the rate of MNZ
removal. The micro-toxicity analysis confirmed that the inhibition ef-
Fig. 8. Outcome of micro-toxicity study.
fects of the treated samples were well below the limits prescribed. The

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N. Neghi et al. Journal of Environmental Chemical Engineering 6 (2018) 754–761

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