Optik - International Journal for Light and Electron Optics 182 (2019) 1194–1203

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Optik
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Original research article

Energy consumption and photochemical degradation of Imipenem/

T
Cilastatin antibiotic by process of UVC/ Fe2+/ H2O2 through
response surface methodology
⁎ ⁎
Hatam Godinia, Amir Sheikhmohammadib, , Leila Abbaspourc, , Rouhollah Heydarid,
Ghodratollah Shams Khorramabadic, Mahdieh Sardare, Zahra Mahmoudif
a
Department of Environmental Health Engineering, School of Health, Alborz University of Medical Sciences, Karaj, Iran
b
Department of Environmental Health Engineering, School of Health, Khoy University of Medical Sciences, Khoy, Iran
c
Department of Environmental Health Engineering, School of Health, Lorestan University of Medical Sciences, Khorramabad, Iran
d
Razi Herbal Medicines Research Center, Lorestan University of Medical Sciences, Khorramabad, Iran
e
Students Research Office, Department of Environmental Health Engineering, School of Health, Shahid Beheshti University of Medical Sciences,
Tehran, Iran
f
Department of Environmental Health Engineering, Islamic Azad University, Hamedan, Iran

A R T IC LE I N F O ABS TRA CT

Keywords: In the present study, degradation of Imipenem/Cilastatin antibiotic (ICA) from aqueous solution
Optimization was investigated by the integrated advanced oxidation / reduction process (AROP) of UVC/
Energy consumption Fe2+/ H2O2. R software using the response surface methodology was applied to investigate re-
Degradation lationship between the input independent factors (Fe2+, H2O2, time and initial antibiotic con-
Imipenem/Cilastatin
centration) and one dependent output response (removal efficiency). 28 runs per experimental
Advanced oxidation/reduction
design were obtained with generation of a central composite design (CCD). The second-order
model (with p-value, 2.976 e-16; F-statistic, 180.1 on 8 and 19 DF; multiple R-squared, 0.987;
adjusted R-squared, 0.9815 and lack of fit, 0.868 indicated satisfactory adjustment between
model and experimental data for AROP. Based on obtained results, the optimum ranges of
parameters considering both maximum antibiotic removal and minimum energy consumption
were estimated: initial antibiotic concentration, 5–7.5 mg L−1; reaction time, 18.9–33.86 min;
Fe2+, 0.74–1.2 mM and H2O2, 0.28-0.32 mM.

1. Introduction

In the recent years, environmental pollution by pharmaceuticals has become one of the most crucial problems for the global
population. Pharmaceuticals such as antibiotics are widely used to prevent or treat microbial infections [1,2]. They can be found in
the surface water, ground water and possibly end up in drinking water in low concentrations. Improper disposal of unused medicines,
industrial discharges and emissions related to the use of veterinary drugs may also contribute to their occurrence in aquatic en-
vironments. Antibiotics in the environment can affect aqueous ecosystems and human health and cause bacterial resistance [3,4].
These cases can be due to inefficiency removal of conventional wastewater treatment such as filtration and activated sludge (because
of the toxicity of antibiotics for microbes). Therefore, removal of pharmaceuticals by water treatment is an important issue and
researchers have been concentrated study on the alternative degradation processes in order to increase the removal efficiency [5]. In

⁎
Corresponding authors.
E-mail addresses: asheikh1359@gmail.com (A. Sheikhmohammadi), abpu@yahoo.com (L. Abbaspour).

https://doi.org/10.1016/j.ijleo.2019.01.071
Received 15 December 2018; Received in revised form 1 January 2019; Accepted 24 January 2019
0030-4026/ © 2019 Elsevier GmbH. All rights reserved.
H. Godini, et al. Optik - International Journal for Light and Electron Optics 182 (2019) 1194–1203

the recent years, environmental pollution by pharmaceuticals has become one of the most crucial problems for the global population.
Pharmaceuticals such as antibiotics are widely used to prevent or treat microbial infections [6,7]. The advantages of these processes
over the other treatment processes is short reaction times to achieve successful degradation due to rapid degradation kinetics, non-
transferring of target pollutants to the other phase, producing non-toxic products, non-selectively and creating products with high
biodegradability [6,8]. These methods are well developed as a pretreatment option to degrade resistant compounds in the en-
vironment. AROP is the combination of different reductants and oxidants with various activating methods to produce highly reactive
reducing and oxidizing species that have great potential to destruction of pollutants and overcome kinetic limitations [9]. The
simultaneous presence of both reductive and oxidative agents is very important to the complete degradation of resistant compounds
such as antibiotics. AORPS are processes based on the use of the oxidizing hydroxyl radical (%OH), which is a powerful oxidant
(E° = 2.8 V) and eaq− as high intensity reductive specie (E° = - 2.9 V) which react with organic and antibiotic compounds [9–12].
UVC/Fe2+ in presence of H2O2 is an AORP that a reducdant (Fe2+) and an oxidant (H2O2) are in contact with UVC irradiation. The
AORP is included three processes: UVC/H2O2, Fe2+/H2O2 (Fenton) and UVC/Fe2+. The variety range of wavelengths could be used
in the AROP, which it depend on the absorption spectra of the reagent to be activated. UVC at 254 nm (the low-pressure mercury
vapor lamp (UV-L)) is currently used in water and wastewater treatment. UVC/Fe2+ in presence of H2O2 include two processes,
advanced reduction process (ARP) and advanced oxidation process (AOP). In 2013 for the first time, Vellanki et al. introduced UVC/
Fe2+ as an advanced reduction process. UVC/Fe2+ and were applied it in them researches. They expressed the ARP is included
reaction between Fe2+ with UVC. Solutions of ferrous iron can absorb UVC wavelength and UV irradiation promotes formation of
hydrated electrons as Eq. (1) that could cause pollutant degradation [13].
Fe2+ +hv → Fe3+ + e− (1)
%
H2O2 is a commonly used oxidant, which generates very reactive oxidative radical specie of OH in contact with UVC radiation
(Eq. (2)) [14].
H2 O2 +hv → 2HO• (2)
2+
Fenton is the reaction of oxidant such as hydrogen peroxide with Fe . Fenton process is based on electron transfer between
hydrogen peroxide and ferrous ions resulting the generation of hydroxyl radicals (%OH) which in turn could degrade pollutants (Eq.
(3)) [15].
H2 O2 + Fe2 + → Fe3 ++HO• + OH− (3)
Another mechanism for generating hydroxyl radicals is the reduction of ferric to ferrous ions to produce additional hydroxyl
radicals via photolysis (Eq. (4)) [16].

Fe(III) (OH2+)+hv →Fe2+ +HO% (4)

2+
(4) in presence of H2O2 can be an attractive method for two reason, 1- iron is an abundant and non-toxic element 2- H2O2 has
environmentally benign footprint [15,17]. In this study removal of ICA from synthetic wastewater was investigated. Imipenem/
cilastatin is made from combination of Imipenem and Cilastatin which is sold under the brand name Primaxin. ICA is an antibiotic
useful for the treatment of a number of bacterial infections and specifically it is used for pneumonia, sepsis, endocarditis, joint
infections, intra-abdominal infections, and urinary tract infections [18,19]. Common side effects include nausea, diarrhea, diarrhea
and allergic reactions including anaphylaxis. It is on the World Health Organization's List of Essential Medicines. This antibiotic has
been seen at the outlet of the wastewater treatment plants of the pharmaceutical company, which can enter in the water resources
(the structure of this antibiotic is shown in Fig. S1 in the supplementary data). So far, no specific research has been done to reduce
this pollutant in the wastewater. Therefore, for the first time, the present study introduces AROP method for the ICA finishing.

2. Materials and methods

2.1. Experimental procedure and analytical method

AROP was operated in a lab-scale photoreactor at the batch mode. The schematic of the photoreactor is portrayed in Fig. S2 (in
the supplementary data). Photo-reactor applied in this study, comprised a sealed tubular glass (the inner diameter of 3.5 cm and
28 cm in height) for cooling of photochemical chamber. A low-pressure mercury UV light lamp (UV-L) with emission at 254 nm was
placed in the center of the photo-reactor and was protected by a quartz sleeve (2 cm in inner diameter) (as shield of the UV lamp). The
UV lamp was placed at a fixed distance (1 cm) from the quartz sleeve. The UV light intensity was measured by a UVC 512 light meter.
To ensure safe operation and to prevent the entrance of extraneous light, photoreactor was wrapped in an aluminum sheet and
housed in a cabinet. Working volume of photo-reactor was 500 mL. For each test, 500 mL of antibiotic solution with a specific
concentration was injected into the photo-reactor and pH of solution was adjusted to a preset value using sulfuric acid (0.1 N) or
NaOH (0.1). Then, the required amount of FeSO4.7 H2O and H2O2 were added into the reactor. The AROP was initiated by switching
on power supply and irradiation of the UV lamp. The solution was stirred for a predetermined time, and then sample was taken from
the reaction solution and immediately analyzed for the degradation. The samples are filtered through 0.2 μm syringe filters (mdi,
India), then the residual antibiotic concentration was analyzed using a Knauer HPLC (Eclipse Plus C18 column; 3.5 × 4.6 × 100 mm)
and connected to a UV-VIS detector. The mobile phase for Imipenem consisted of 93% water and 7% ethanol; that for Cilastatin was
76% 0.10 M potassium phosphate (pH 2.5) and 24% methanol that applied at a flow rate of 1.0 mL min−1and the analytical

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Table 1
Actual and coded values of independent variables used for experimental design.
Coded level (GFH)

Variable Symbol −1 0 1
Real values

Initial antibiotic concentration (mg L−1) X1 5 12.5 20

Time (min) X2 10 25 40
Fe2+ (mM) X3 0.15 0.67 1.2
H2O2 (mM) X4 0.04 0.18 0.32

wavelength of 300 nm for Imipenem and 220 nm for Cilastatin. The calculation of removal percentage of ICA by AROP and the
related kinetic description were presented in the supplementary data.

2.2. Factorial experimental design and optimization of parameters

The R software was applied for factorial experimental design. RSM is a profitable statistical tool for predicting and modeling the
relations between dependent and independent factors. The variables in this research, were included 4-input independent factors.
Therefore, the levels designed for 4-input independent factors were tabulated in Table 1 [20]. Central composite design (CCD) on R
software was used to generate points (to generate a standard 4-variable full factor design and12 center points), and 28 runs per
experimental design were obtained (Table S1 (in the supplementary data)). To this purpose, data coding was done and experimental
runs were determined. Then CSV (MS-DOS) file was prepared for designed runs. The R software was executed and the CSV (MS-DOS)
file was read back by the software. The coding and edit of CSV (MS-DOS) file was done and coded data were obtained. The coded data
were adapted with three RSM models (including the first order model (FOM), first model with interaction (FMWI) and the second
order model (SOM)), and finally the best model was recorded. The indicator used to select the best model was analysis of variance
(ANOVA) [21]. The model with higher R2 and insignificant lack of fit was selected as appropriate model. Then regression analysis of
the selected model (for coded data) was done and the regression coefficient for each term was determined. Thereafter, regression
analysis for the uncoded data was done. The optimization process was conducted using the independent variables and the regression
coefficients were determined for uncoded data. The regression coefficients were entered in the Solver software and the final equation
for AROP in terms of the uncoded factors was obtained [22].

2.3. Energy consumption

The electric energy per mass removed (EEM) is another controlling parameter that affects the performance of AROP. The EEM value
(in kWh/kg) for each run was calculated as the following formula and was presented in Table 2.

⎛ P× t ⎞
EEM = ⎜ ⎟
⎜ V×log C0
⎝ Ct( ) ⎟
⎠ (5)

where P is the rated power (kW) of the system (UV lamp), V is the volume (m3) of antibiotic treated in time t (h); Ci and Ct are the
initial and final concentrations of antibiotic (mg L−1).The data coding for EEM was done using R software. The coded data were fitted
with three RSM models and the best model was selected according to analysis of variance (model with higher R2 and insignificant
lack of fit). Then the regression coefficients in terms of the uncoded factors were determined and entered in the Solver software and
the final equation for EEM was obtained [23].

Table 2
Kinetic information of the degradation of ICA at different pHS.
Process
R2 Kobs robs Ratio robs
(min−1) (mg L−1.min)

pH = 3 (A) 0.955 0.086 0.43 –

pH = 5 (B) 0.956 0.025 0.125 A/B = 3.44
pH = 7 (C) 0.968 0.004 0.02 A/C = 21.5
pH = 9 (D) 0.960 0.002 0.01 A/D = 43

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Table 3
Kinetic information for the degradation of ICA using different processes.
Process
R2 Kobs robs Ratio robs
(min−1) (mg L−1.min)

UV (A) 0.991 0.003 0.015 (C or D) /A = 9, B/A = 6

UV/Fe2+ (B) 0.972 0.019 0.09 (C or D) / B = 1.5
Fe2+/H2O2(C) 0.994 0.028 0.14
UV/H2O2 (D) 0.991 0.028 0.14

3. Results and discussion

3.1. The kinetic study of the different pHs in the degradation of ICA by only UV and AORP

The conducted different researches on the AOP and ARP have indicated, pH has a noticeable role on the degradation of organic
pollutants. To this purpose the influence of pH (in the over the range from 3.0 to 9) on the degradation of ICA by the direct photolysis
and the AORP was investigated (data are not shown) [24,25]. The results indicated an insignificant effect on the performance of only
UV with altering pH from 3 till 9, whereas increase of pH from 3 to 9 resulted to decrease of AORP performance from 98.5 to 24.6%
(data are not shown).To more understand, relationship between rate constants describing the pseudo first-order kinetic (kobs) and the
pH was investigated and results is tabulated in Table 2.
As Table 2, there was a high degree of fitness (R2 > 0.95) between the experimental results and the pseudo first-order kinetic
equation. It is seen in Table 3, when pH increased from 3 till 9, kobs indicated considerable fall and reached from 0.086 to
0.002 min−1, also robs value changed from 0.43 to 0.01 mg L−1 min [9,26]. The comparison of robs value for the different pHs,
indicated rate of antibiotic degradation in the pH 3.0 was around 3, 21 and 43 times faster than that in the pHs of 5.0, 7.0 and 9.0,
respectively. These results confirm that the altering of pH can synergistically accelerate the generation of ˙OH and eeq- radicals and
thereby enhance the antibiotic degradation rate. Therefore, pH 3.0 selected as proper pH in the follow up experiments.

3.2. Comparison of the different AORP processes performance on the degradation of ICA

The performance of UV only and the different AORP (including UV/Fe2+, UV/H2O2 and Fe2+/H2O2) were evaluated on the
degradation of ICA and results were presented in Fig. S3 (in the supplementary data).The photoreactor operated at initial antibiotic
concentration, 5 mg L−1; reaction time, 40 min; Fe2+, 1.2 mM; H2O2, 0.32 mM and pH, 3.0. As portrayed in Fig. S3 (in the sup-
plementary data), the removal efficiency of the only UV was negligible; so that, 17% of the antibiotic was degraded after 40 min of
the elapsed time. As Fig. S3 (in the supplementary data), the removal efficiencies of antibiotic for UV/Fe2+, UV/H2O2 and Fe2+/H2O2
processes were 57%, 73% and 70%, respectively. These results showed both the oxidation (UV/H2O2 and Fe2+/H2O2) and reduction
(UV/Fe2+) processes can play an important role in ICA degradation. This means that simultaneously generation both of oxidizing
(•OH) and reducing (eaq-) agents can improve degradation efficiency. Table 3 presented information about relationship between
degradation rate constants (kobs) and the different processes. Table 3 depicts a high degree of fitness (R2 > 0.97) between experi-
mental data for the different processes and the pseudo first-order kinetic equation. It is notable that robs value for oxidation process
was about 1.5 times than that in the reduction process. Also robs value was very significant in the AORP than that in the only UV
process. These reconfirm the mentioned results in above. Therefore, the integrated application of AOP (UV/H2O2 and Fe2+/H2O2)
and ARP (UV/Fe2+) processes on the degradation of ICA was further investigated [15,23,27].

3.3. The selection of appropriate equation for the AORP and EEM

Table 4a, bTable 4 (a, b) presented information about design of three models of RSM (including FOM, FMWI and SOM) using
coded data. As Table S2 and Table 4a, b, SOM model with a higher R2, and also an insignificant lack of fit (0.86) indicated superiority
than the rest. Therefore, SOM model was selected as proper model for prediction of AORP. As the analysis of ANOVA (Table 4a, b),
the significant terms for SOM model were included FO (x1, x2, x3, x4), TWI (x1, x2, x3) and PQ (x4). In the other hand terms of x1, x2,

Table 4a
Analysis of variance (ANOVA) for the AORP.
Model formula in RSM DF Sum of squares Mean square F-value Probability (P)

First-order response (x1, x2, x3, x4) 4 2248.48 354.6556 8993.9 < 2.2e-16
Two-way interaction response (x1, x2, x3) 3 112.1 37.36 5.8929 0.005087
Full second order response (x4) 1 26.0 26.03 4.1063 0.056995
Residuals 19 120.5 6.34 – –
Lack of fit 8 29.5 3.69 0.4466 0.868935
Pure error 11 90.9 8.27 – –

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Table 4b
Analysis of variance (ANOVA) for the EEM.
Model formula in RSM DF Sum of squares Mean square F-value Probability (P)

First-order response (x1, x2, x3, x4) 4 785.60 196.400 89.5681 1.788e-12
Two-way interaction response (x1, x2, x3) 3 65.27 21.755 9.9214 0.0003239
Residuals 20 43.85 2.193 – –
Lack of fit 9 10.76 1.196 0.3975 0.9116438
Pure error 11 33.09 3.008 – –

x3, x4, x2:x3 and x4^2 can be entered in the designing of coded data equation for AORP. Also, agreement between R2adj with R2pred (0.98)
approved the presence of these terms in the model (Fig. S4 (a)).The regression analysis of the SOM model was presented in Table 5a.
These coefficients in terms of the coded factors were applied to design the coded data equation for AORP (ϒ AORP). This equation can
be applied for prediction of AORP (using coded data).

ϒ AORP = 41.37417 -20.34139 X1+ 6.11432 X2 + 5.17629 X3 +16.26667 X4-3.78437x1:x2 + 2.24869x2:x3+ 4.13333 X4^2
(6)

As Eq. (10), coded terms of the (x2, x3, x4, x2:x3, x4^2) and (x1, x1:x2) have a synergistic effect and an antagonistic effect on the
AORP. The same procedure as AORP followed to design a proper equation for prediction of EEM value (using coded data). The analysis
of ANOVA to investigate EEM, illustrated SOM and FMWI models with a similar result (insignificant lack of fit (0.911) and R2 (0.951)),
have superiority than the FOM model (Table 4b). As analysis of ANOVA, the significant terms for EEM were included FO (x1, x2, x3, x4)
and TWI (x1, x2, x3). Therefore, coded terms of x1, x2, x3, x4, x1:x2 and x1: x3 were entered in the equation of EEM. Also, agreement
between R2adj with R2pred (0.95) approved the presence of these terms in the model (Fig. S4 (b)).The regression analysis of the sig-
nificant terms was done and the regression coefficients were determined (Table 5b). These coefficients in terms of the coded factors
were applied to design the following equation for EEM (ϒ EEM) [28,29].

ϒ EEM = 16.27724 + 8.76099 X1+4.37432 X2 -4.84808 X3 -3.27852 X4 +2.39495 X1:X2-3.36408 (X1:X3)

(7)

This equation can be applied for prediction of EEM (using coded data). As Eq. (11), terms of the (x1, x2, x1:x2) and (x3, x4, x1:x3)
have a synergistic effect and an antagonistic effect on the EEM. Then analysis of prediction was done for AORP and EEM, and values of
fit, upper and lower were determined for each run (Table 2) [23].

3.4. Optimization process and confirmation

The main purpose of this paper was providing the optimal range of each parameter considering both maximum ICA removal
performance and minimum energy consumption. It should be considered that the best condition for a chemical reaction besides high
antibiotic removal values is in the low energy consumption rate. To this purpose, calculation of regression coefficients using uncoded
data is essential. Therefore, significant parameters (obtained for the coded data) entered in the lm analysis (derivation analysis) on
the R software and regression coefficients determined for the uncoded data. Results of the regression analysis for the uncoded data
are presented in Table 5. Then, these coefficients were entered in the Solver software “Add-ins” in Excel. The optimum condition for
the each reaction involving all the significant terms, were determined using the regression coefficients obtained from R software.
Therefore, the optimum condition for (a high antibiotic removal), (low energy consumption rate) and (maximum antibiotic removal
with minimum energy consumption together) were calculated in the Solver software. Also, equation of the optimization was de-
termined for the AORP and EEM as following [20,23,30]:

ϒAORP = 37.510638 -2.066462 X1 + 0.634950 X2 + 59.659971 X4 -0.033639 X 1: X 2 + 0.288294 X 2: X 3 + 151.513263 X4

^2 (8)

Table 5a
Regression analysis of the AORP with coded and uncoded values of the independent variables.
Coded values Un coded values

Model term Coefficient estimate Std. error t-value p-value Coefficient estimate Std. error t-value p-value

(Intercept) 41.37417 0.72686 56.9219 < 2.2e-16 37.510638 4.631156 8.100 9.62e-08
X1 −20.34139 2.16975 −9.3750 1.473e-08 −2.066462 0.244332 −8.458 4.88e-08
X2 6.11432 1.20520 5.0733 6.752e-05 0.634950 0.139569 4.549 0.000195
X3 5.17629 2.13943 2.4195 0.025740 – – – –
X4 16.26667 0.99529 16.3436 1.206e-12 59.659971 27.362216 2.180 0.041346
X1: X2 −3.78437 0.99529 −3.8023 0.001204 −0.033639 0.008743 −3.847 0.001005
X2: X3 2.24869 1.01016 2.2261 0.038308 0.288294 2.253 0.127987 0.035679
X4^2 4.13333 2.03974 2.0264 0.056995 151.513263 64.199809 2.360 0.028546

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Table 5b
Regression analysis of the EEM with coded and uncoded values of the independent variables.
Coded values Un coded values

Model term Coefficient estimate Std. error t-value p-value Coefficient estimate Std. error t-value p-value

(Intercept) 16.27724 0.42747 38.0783 < 2.2e-16 4.521069 3.047288 1.484 0.152760
X1 8.76099 0.72724 12.0469 1.269e-10 1.241153 0.272313 4.558 0.000171
X2 4.37432 0.70878 6.1716 4.979e-06 – – – –
X3 −4.84808 0.69900 −6.9357 9.822e-07 – – – –
X4 −3.27852 0.58502 −5.6041 1.743e-05 −23.417978 4.130104 −5.670 1.26e-05
X1: X2 2.39495 0.58533 4.0916 0.0005679 0.020196 0.004917 4.107 0.000503
X1: X3 −3.36408 0.94139 −3.5735 0.0019018 −0.862585 0.238573 −3.616 0.001622

ϒ EEM = 4.521069 + 1.241153 X1- 23.417978 X4+ 0.020196 X1:X2 - 0.862585 X1:X3
(9)

The selected values for the each significant parameter were about the stationary points in the original units mentioned in the
summery of R analysis. As the Solver method, the maximum removal performance of ICA was estimated as 100% under selected
conditions (x1, 5 mg L−1; x2, 40 min; x3, 1.2 mM and x4, 0.32 mM). Also the minimum value of EEM was estimated 0.97 kW h/kg by
setting x1, 5 mg L−1; x2, 10 min; x3, 1.2 mM and x4, 0.32 mM. Based on obtained results, the optimum ranges of parameters con-
sidering both maximum antibiotic removal and minimum energy consumption were estimated: x 1, 5 till 7.32; x 2, 18.9 till 33.86; x 3,
0.74 till 1.2 and x 4, 0.28 till 0.32.

3.5. Investigation of interactive effect of variables by contour and perspective plots

The contour and perspective plots were applied to depict the interactive effect of variables on the antibiotic removal performance
and EEM. These plots were prepared by R software and presented in Fig. 1a. Fig. 1aFig. 1 (a) portrayed the interactive effect of initial
antibiotic concentration (5–20) and time (10–40 min) on the performance of AORP. As seen in Fig. 1aFig. 1 (a), for an antibiotic
concentration (5 mg L−1) at the fixed Fe2+ (0.86 mM) and H2O2 (0.22 mM) dosages, increase of time from 10 till 40 resulted to
increase of performance from 57.5 to 75%, while was not observed any significance change on the performance in the higher
concentration (above 5 mg L−1). Also as portrayed in Fig. 1aFig. 1 (a), at the fixed Fe2+ (0.86 mM) and H2O2 (0.22 mM) dosages;
increase of antibiotic concentration from 5 till 20 mg L−1, resulted to decrease of performance from 57.5 to 22% within 10 min. This
decrease in the performance was also observed in the higher times. The results showed that the removal percentage of antibiotic was
influenced by the initial concentration of antibiotic. Decrease of performance with increasing antibiotic concentration (at a fixed
time) can be because of (i) inadequate radicals produced by the reducing and oxidizing reagents (Fe2+ and H2O2) photolysis at higher
concentrations resulting limiting the availability of radicals for the antibiotic degradation and (ii) a long required time to generation
of sufficient reductive and oxidative radicals for antibiotic degradation (specially within higher concentrations) [17,31]. Also di-
minution of degradation efficiency at high concentrations of antibiotic may be related to the use of photo induced agents, before the
oxidation or reduction processes are completed. The conducted study by Ayodele et al. about pillared montmorillonite supported
ferric oxalate as heterogeneous photo-Fenton catalyst for degradation of amoxicillin, showed that the initial concentration of anti-
biotic affect the degradation efficiency. In a high initial concentration of amoxicillin, the degradation efficiency was low, while with
decreasing of initial concentration of amoxicillin antibiotic, the degradation efficiency increased. Because when the initial con-
centration of amoxicillin antibiotic increased, other factors that affect the degradation efficiency did not increase simultaneously.
Consequently, radical %OH was not sufficient to degrade the amoxicillin [32]. Also Fig. 1aFig. 1 (a) portrays the interaction effect
between Fe+ (0.2–1.2 mM) and time (10–40 min). As portrayed in Fig. 1aFig. 1 (a), at the reaction time of 25 min, and also a fixed
initial antibiotic concentration (10.36 mg L−1) and H2O2 (0.22 mM); with an increase in the Fe+ dosage from 0.2 till 1.2 mM, the
AORP effectiveness increased from 46% to 60%. Also at the Fe+ dosage of 0.2 mM, with an increase in the reaction time from 10 till
40 min, the removal performance increased from 42% to 52% (at a fixed initial antibiotic concentration (10.36 mg L−1) and H2O2
(0.22 mM)) [16]. This increase in the performance can be for two reason: 1- perform UV/Fe2+ advanced reduction process that
ferrous iron can absorb UVC wavelength and UV irradiation promotes formation of hydrated electrons as Eq. (1), this could cause
pollutant degradation 2- perform Fenton advanced oxidation process that is based on electron transfer between hydrogen peroxide
and ferrous ions resulting the production of hydroxyl radicals (%OH) which in turn could degrade pollutants (Eq. (3)). Of course, it
must be noted that the formed Fe3+ (in Eqs. (1) and (3)) again enters in a reaction with UV and produces Fe2+ and %OH that resulted
to increase in the removal efficiency (Eq. (4)) [16,33].Yazdanbakhsh et al. expressed there is an optimum concentration for iron ion
in the AOP. They depicted the scavenging effect of overdoses of Fe2+ on %OH radicals. Because in higher dosages of Fe2+, OH radicals
may be scavenged by participating in reaction with Fe2+(Eq. (14)), consequently, the removal performance could decrease [34].

Fe2++•OH →OH−+Fe3+ (10)

Fig. 1bFig. 1 (b) , indicated interaction effect between (initial concentration antibiotic and time at fixed values of Fe2+ and H2O2)
and (initial antibiotic concentration and Fe2+at fixed values of time and H2O2). As portrayed in Fig. 1bFig. 1 (b), at a constant initial

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Fig. 1a. Contour (a) and prespective (b) plots to study the interaction effect between variables in the AORP.

antibiotic concentration (10 mg L−1), with increasing time from 10 till 40 min; EEM increased and reached from 8 to 14%. This
increase became more severe when during a steady period of radiation (25 min), the concentration increased from 5 to 20 mg L−1
(EEM increased from 6 to 22 kW h/kg). This suggests that, according to Eq. (5), increase of the time and initial antibiotic concentration
leads to an increase in energy consumption. Also, according to Fig. 1bFig. 1 (b), it was found that at a constant concentration of
antibiotic, an increase at Fe2+concentration, leads to a decline in energy consumption, while at a constant Fe2+concentration, an
increase at the initial concentration of antibiotic, leads to an increment in energy consumption. This phenomenon can be interpreted
as follows. By increasing the iron dosage (at a constant concentration of antibiotic), the part of the reaction is conducted by the
Fenton process, which does not require the energy of UV; therefore, the amount of energy consumed is decreased. But at a fixed iron
dosage, the cause of increase in the energy consumption is attributed to the part of AORP which is done in the presence of UV light

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Fig. 1b. Contour (a) and prespective (b) plots to study the interaction effect between variables in the EEM.

[9,23].

4. Conclusion

The kinetic studies were done in order to investigation of relationship between robs value and the pH. The comparison of robs value
for the different pHs, indicated rate of antibiotic degradation in the pH 3.0 was around 3, 21 and 43 times faster than that in the pHs
of 5.0, 7.0 and 9.0, respectively. These results confirm that the altering of pH can synergistically accelerate the generation of %OH and
eeq− radicals and thereby enhance the antibiotic degradation rate. Therefore, pH 3.0 selected as proper pH in follow up experiments.
The performance of UV only and different AORP processes including UV/Fe2+, UV/H2O2 and Fe2+/H2O2 were evaluated on the
degradation of ICA. These results showed both the oxidation (UV/H2O2 and Fe2+/H2O2) and reduction (UV/Fe2+) processes can play
an important role in antibiotic degradation. This means that simultaneously generation both of oxidative (•OH) and reductive (eaq−)
agents can improve degradation efficiency. Also, the kinetic studies on different processes indicated that robs value for oxidation
processes was about 1.5 times than that in the reduction process. Consequently, the integrated application of oxidation (UV/H2O2 and
Fe2+/H2O2) and reduction (UV/Fe2+) processes on the degradation of ICA was further investigated. In the present study the R and
solver software were applied as a useful statistical tool to calculate the optimum ranges of parameters considering both maximum

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antibiotic removal and minimum energy consumption. As analysis of ANOVA SOM model was selected as proper model for prediction
and optimization of AORP and EEM. The coded terms including (x2, x3, x4, x2:x3, x4^2) and (x1, x1:x2) were indicated a synergistic
effect and an antagonistic effect on the AORP, respectively. Also, the coded terms including (x1, x2, x1:x2) and (x3, x4, x1:x3) had a
synergistic effect and an antagonistic effect on the EEM, respectively. Therefore, theses terms entered in optimization analysis. As the
Solver method, the maximum removal performance of antibiotic was estimated as 100% under selected conditions (x1, 5 mg L-1; x2,
40 min; x3, 1.2 mM andx4, 0.32 mM). Also the minimum value of EEM estimated 0.97 kW h/kg by setting x1, 5 mg L-1; x2, 10 min; x3,
1.2 mM and x4, 0.32 mM. Based on obtained results, the optimum ranges of parameters considering both maximum antibiotic re-
moval and minimum energy consumption were estimated: x 1, 5–7.32; x 2, 18.9–33.86; x 3, 0.74–1.2and x 4, 0.28-0.32.

Acknowledgement

This study was done in the Lorestan University of Medical Sciences. We appreciate from Lorestan University of Medical Sciences
for their financial support of this study.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the online version, at https://doi.org/10.1016/j.ijleo.2019.01.
071.

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