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Marine Pollution Bulletin

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Photodegradation of diclofenac in seawater by simulated sunlight irradiation: The


comprehensive effect of nitrate, Fe(III) and chloride
N. Zhang a,b,d, J.M. Li b, G.G. Liu a,c,d, X.L. Chen b, K. Jiang a,d,
a
Center for Postdoctoral Studies, Postdoctors of Henan Normal University, Jianshe Road, Xinxiang 453007, PR China
b
Postdoctoral Research Base, Henan Institute of Science and Technology, Key Laboratory for Crops Pest Management of Xinxiang, Xinxiang 453003, PR China
c
Faculty of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006, PR China
d
Henan Key Laboratory for Environmental Pollution Control, Key Laboratory for Yellow River and Huaihe River Water Environment and Pollution Control, Ministry of Education, Jianshe Road,
Xinxiang 453007, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Diclofenac is one of the most frequently detected pharmaceuticals in various aquatic environments. The
Received 22 November 2016 photodegradation of diclofenac in the absence/presence of nitrate, Fe(III) and chloride, especially their interac-
Received in revised form 5 February 2017 tions, were systematically studied. Under the study conditions, photodegradation rate was decreased with in-
Accepted 8 February 2017
creasing nitrate, Fe(III) and chloride concentrations. Nitrate has an synergistic action for Fe(III). Nitrate and
Available online xxxx
chloride have antagonistic effect. An antagonistic action is present between nitrate, Fe(III) and chloride. More-
Keywords:
over, a simple linear model which very well describes the results is given.
Diclofenac 2017 Elsevier Ltd. All rights reserved.
Box-Behnken design
Photodegradation
Simulated sunlight

1. Introduction tissue damage (Mehinto et al., 2010). Therefore, to assess the fate and
risk of diclofenac in aquatic systems would be of value.
In recent years, pharmaceuticals are a novel class of pollutant whose Photodegradation is one of the principle abiotic degradation path-
presence is increasing in the aquatic environment due to an incomplete ways of diclofenac in the aqueous environment, it occurs mainly at the
degradation in the sewage treatment plant (Chong et al., 2017). Phar- water surface, and is affected by various environmental conditions. In
maceutical and Personal Care Products (PPCPs) have been found pollut- natural waters, the main variables in the aquatic environment include
ing a wide range of aquatic environments including groundwater, aqueous dissolved anions, metal ions and dissolved organic matter
surface water and drinking water (Chen et al., 2016; Lin and Li, 2016; (DOMs). Nitrate, Fe(III) and chloride which widely exist in the aquatic
Serra-Roig et al., 2016; Wang and Wang, 2016). Diclofenac (DCF) environment, can produce reactive species that inuence the photo-
(SI.1) is anti-inammatory non-steroidal drug, mostly used as its sodi- chemical degradation of organic pollutants (Yanxia Li et al., 2013). Ni-
um salt in medical care as an antiarthritic, analgesic and antirheumatic. trate, Fe(III) and chloride can inuence photodegradation by acting as
Among the pharmaceuticals, diclofenac is an analgesic with a high rate photosensitizers and/or OH sinks (Koumaki et al., 2015; Poirier-Larabie
of consumption (Zhang et al., 2011). Diclofenac has been detected in et al., 2016). The interaction of various environmental factors could
surface water, groundwater and seawater (He et al., 2016; Sui et al., induce indirect photodegradation of diclofenac and inuence photo-
2015; Wang and Wang, 2016). Nowadays, the harmful effects of DCF chemical fate and persistence in natural waters. Therefore, it is neces-
on different organisms in realistic aquatic environments have been sary to consider the multivariate effects of the main environment
demonstrated (Stlten et al., 2008). For example, diclofenac can cause factors.
renal failure in the Indian vulture and alterations of the gills of rainbow The Box-Behnken statistical experiment design approach (BBD) was
trout. It also can inuence the biochemical functions of sh and lead to reported to be useful of the dependent of a three independent variables
response function (Box and Wilson, 1951; Singh et al., 1995). Response
surface Methodology (RSM) is a collection of statistical and mathemat-
ical techniques that are useful for analyzing and modeling (Raissi,
Corresponding author at: Center for Postdoctoral Studies, Postdoctors of Henan 2009). Pharmaceuticals degradation from aquatic environments can
Normal University, Henan Key Laboratory for Environmental Pollution Control, Key
Laboratory for Yellow River and Huaihe River Water Environment and Pollution Control,
be studied with a minimum number of experiments by using BBD and
Ministry of Education, Jianshe Road, Xinxiang 453007, PR China. the RSM (Catalkaya and Kstwi, 2009; Kummerer, 2001; Stangroom et
E-mail address: 29164616@qq.com (K. Jiang). al., 1998).

http://dx.doi.org/10.1016/j.marpolbul.2017.02.024
0025-326X/ 2017 Elsevier Ltd. All rights reserved.

Please cite this article as: Zhang, N., et al., Photodegradation of diclofenac in seawater by simulated sunlight irradiation: The comprehensive effect
of nitrate, Fe(III) and chl..., Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.024
2 N. Zhang et al. / Marine Pollution Bulletin xxx (2017) xxxxxx

The objectives of this study were to investigate the kinetics of Table 1


diclofenac photodegradation in natural seawater. The aim of the Coded and the levels of variables in Box-Behnken design experimental.

present study was to simulate natural seawater to investigate the Variable Symbol Coded variable level
photodegradation of diclofenac under simulated sunlight, with particu- Low Center High
lar emphasis on the possible interactive impact of those common water 1 0 +1
constituents (nitrate, iron and chloridion). The BoxBehnken statistical
NO3 concentrations (mmol/L) X1 0 0.05 0.1
experiment design and response surface methodology was used in this Fe3+ concentrations (mmol/L) X2 0 0.005 0.01
study to investigate the multivariate effects of the main environment
Cl concentrations (mmol/L) X3 0 0.1 0.2
factors (nitrate, Fe(III) and chloride) on the photodegradation of
diclofenac.

2. Materials and methods 3. Results and discussion

2.1. Chemicals 3.1. Univariate analysis

Diclofenac, 2-[(2,6-dichlorophenyl) amino] benzeneacetic acid, 3.1.1. The effect of NO


3 on photodegradation of DCF

sodium salt (98% purity), was purchased from J&K Chemical Co. Ltd. SI. 3 shows the effect of different concentrations of NO 3 on the

(Beijing, China). NaNO3, NaCl and Fe2(SO4)3 were all obtained from photodegradation of DCF. Linear plots of ln[DCF]/[DCF]0) versus time
Tianjin Guangfu Chemical Reagents Co. Ltd. (Tianjin, China). High per- obtained at NO 3 concentrations of 0.0, 0.01, 0.1 and 1.0 mmol/L, gave

formance liquid chromatography (HPLC) graded methanol was obtain- rate constants of 0.205, 0.191, 0.185 and 0.174 min1, respectively
ed from Suqian Gouda Chemical Reagent Co. Ltd. (Jiangsu, China). All of (Table 2). It can be seen that the addition of NO 3 decreased the

chemicals used were of analytical grade without further purication. photodegradation rate. This result can be explained as competition of
DCF and nitrate ion for the limited number of available photons (SI.
4), leading to a reduction of the degradation rate of DCF with increased
2.2. Photodegradation experiments nitrate ion concentration.

Photolysis experiments were performed on the equipment that had 3.1.2. The effect of Cl on photodegradation of DCF
a 250 mL hollow cylindrical quartz tube photoreactor (SGY-1, Nanjing The effect of different concentrations of Cl on the degradation of
STO Co. Ltd.), as shown in SI. 2. All photodegradation experiments DCF under simulated sunlight is shown in Table 2. The addition of Cl
have been made the same concentration of 0.03 mmol/L of DCF in the was found to inhibit DCF degradation, the degradation rate of DCF re-
quartz tube. A 350 W xenon lamp was put in the double-walled quartz duced with increasing Cl concentration (SI. 5). Chloride ions are likely
cooling jacket and temperature was controlled by the constant-temper- to act as scavengers of hydroxyl radicals (OH) via the mechanism
ature liquid-circulating apparatus. During the whole experiments, the shown in the following reaction equations:
initial concentration of DCF was 0.03 mmol/L and 2 mL reaction liquid

was taken out every 3 min from the quartz tube periodically using a pi- OH Cl Cl OH 1
pette and immediately analyzed by reversed-phase high-performance
liquid chromatography system.
Cl Cl Cl2 2


Cl2 Cl2 2Cl Cl2 3
2.3. Analytical methods

The concentrations of DCF solutions were determined by reversed- Cl Cl Cl2 4


phase high-performance liquid chromatography (HPLC), which
consisted of a Waters 1525 Binary HPLC pumps and Waters 2998 Interestingly, the concentration of Cl was observed to increase with
Photodiode Array detector (Waters, Massachusetts, USA). Analytical irradiation time (Fig. 1), which indicates that Cl is released from DCF
column temperatures were controlled with a Model 1500 Column during degradation. This result is consistent with previous reports by
Heater (Waters, and Product of Singapore). The analytical column was M.J. Galmier (Galmier et al., 2005), P. Calza (Calza et al., 2006) and L.A.
a 150 mm 4.6 mm Waters C18 column, (particle size 5 m). A Waters Prez-Estrada (Prez-Estrada et al., 2005). Due to the release of chloride
guard column (C18, 4.6 20 mm, particle size 5 m) was used to protect during degradation, the addition of Cl inhibits the dechlorination of
the analytical column. The injection volume was 20 L. The mobile phase DCF and therefore inhibits its photodegradation. The overall effect of
was a mixture of 75% HPLC-grade methanol and 25% MilliQ-water Cl on the photodegradation of DCF will therefore depend on the net
(containing 1% Acetic acid) at a constant ow rate of 1.0 mL/min, the contribution of each of these two factors. In this study, Cl was found
detection wavelength was set at 276 nm. to inhibit DCF degradation.

3.1.3. The effect of Fe(III) on photodegradation of DCF


2.4. Experimental design Table 2 shows the effect of different concentrations of Fe3+ on the
photodegradation of DCF. The degradation rate of DCF was found to be
In order to systematically study the effect of all variables on the reduced with increasing Fe3+ concentration (SI. 6). Fe(III)-aquo com-
photodegradation of DCF, we used a BoxBehnken design experimental plexes (Fe3 +, Fe(OH)2 +, Fe(OH)+ 4+
2 , dimer Fe(OH)2 , Fe(OH)
2+
) are
for three variables. A 3-factor Box-Behnken design experimental with 3 known to undergo photolysis through an internal electron transfer
concentration levels and 5 replicates of the center point was used for upon irradiation with wavelengths of 300 nm, yielding Fe(II) and hy-
this multivariate experimental design (Table 1). Nitrate, Fe(III) and droxyl radicals (Stangroom et al., 1998). The addition of Fe3+ is antici-
chloride concentrations were selected as independent variables in pated to yield hydroxyl radicals (Eqs. 58) that can promote the
Box-Behnken design while the calculated photodegradation rate con- photolysis of DCF, and this result runs counter to this hypothesis. The re-
stants were considered as the response functions. sult can be attributed to the strong absorption of Fe3+ in an overlapping

Please cite this article as: Zhang, N., et al., Photodegradation of diclofenac in seawater by simulated sunlight irradiation: The comprehensive effect
of nitrate, Fe(III) and chl..., Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.024
N. Zhang et al. / Marine Pollution Bulletin xxx (2017) xxxxxx 3

Table 2
The pseudo rst order kinetic equations for the photodegradation of DCF at different reaction conditions.

Coexisting substances Concentration (mmolL1) Kinetic equations Half-life (t1/2, min) Regression coefcient Inhibiting ratio (%)

NONE 0.00 LnC/C0 = 0.205t 3.38 0.9996 0.00


NO
3 0.01 LnC/C0 = 0.191t 3.63 0.9982 7.40
0.10 LnC/C0 = 0.185t 3.75 0.9972 10.95
1.00 LnC/C0 = 0.174t 3.98 0.9990 17.75
Cl 0.01 LnC/C0 = 0.185t 3.75 0.9821 10.95
0.10 LnC/C0 = 0.172t 4.03 0.9974 19.23
0.50 LnC/C0 = 0.165t 4.20 0.9994 24.26
1.00 LnC/C0 = 0.153t 4.53 0.9978 34.02
Fe3+ 0.001 LnC/C0 = 0.184t 3.76 0.9998 11.24
0.01 LnC/C0 = 0.178t 3.90 0.9998 15.38
0.1 LnC/C0 = 0.146t 4.75 0.9992 40.53

wavelength range as the absorbance of DCF (SI. 4). The inhibition effect rate (Run 2, 3, 5, 9, 10, 12, 14, 16), the result revealed that an antagonis-
is therefore explained by competitive absorption. tic action was present between NO 3 , Fe
3+
and Cl.
The response surface methodology can provided better understand-
H2 O hv ing of the roles of NO 3 , Fe
3+
and Cl on degradation of DCF for a large
Fe3 FeOH2 Fe2  OH 5
range of concentrations. Fig. 2 shows the effects of NO 3 and Fe
3+

concentration on photodegradation rate constants under simulated


Fe2 O2 Fe3 O2 6 sunlight irradiation. Fig. 3 illustrates the effects of NO
3 and Cl concen-
tration on photodegradation rate constants by simulated sunlight irra-
2O2 2H H2 O2 O2 7 diation. Fig. 4 displayed the effects of Fe3+ and Cl concentration on
photodegradation rate constants by simulated sunlight irradiation. As
can be seen from Figs. 2 and 3, the photodegradation rate constant
Fe2 H2 O2  OH OH 8
was negligible changed when the concentration of Fe3 + or Cl was
xed and changed the concentration of NO 3 , but when the concentra-
tion of NO3 was xed and changed the concentration of Fe
3+
or Cl,
3.2. Multivariate effects of NO
3 , Fe
3+
and Cl the degradation rate constant showed obviously changed. It can be con-
cluded that compared with NO 3 , Fe
3+
and Cl had a more marked in-
The 3-factor BBD and experimental results of the rate constants for uence on DCF photodegradation.
the photodegradation of DCF under different conditions obtained in
the photodegradation runs are shown in Table 3. Comparing the actual 3.3. The response function coefcients and residuals analysis
inhibition rate with the theoretical inhibition rate, it was noted that
when NO 3 and Fe
3+
coexisted in the aquatic environment, the actual Box-Behnken experiment design was used to investigate the effects
inhibition rate of DCF photodegradation was more than the theoretical of three independent variables on dependent variable. In this study,
inhibition rate (Table 3, Run 13 and 15). The results revealed that NO 3 concentrations (X1), Fe
3+
concentrations (X2), and Cl concentra-
NO 3 has an obvious synergistic action for Fe
3+
. As seen from Run 4 tions (X3) were selected as independent variables in Box-Behnken de-
and 7, when NO 3 and Cl
coexisted in the aquatic environment, the ac- sign while the calculated photodegradation rate constants were
tual inhibition rate of DCF photodegradation was less than the theoret- considered as the dependent variable. The low, center and high levels
ical inhibition rate, these experimental results revealed that NO 3 had an of each variable are designated as 1, 0, and + 1, respectively, as
antagonistic action on Cl. Moreover, the actual inhibition rate is similar shown in Table 1. The mathematical relationship between the response
with the theoretical inhibition rate when Fe3+ and Cl coexisted in the function (Y) and the independent variables (X) can be approximated by
aquatic environment (Run 8 and 11). In addition, when NO 3 , Fe
3+
and the second-order polynomial regression model as follows:
Cl were all coexisted in the aquatic environment, the actual inhibition
rate of DCF photodegradation was less than the theoretical inhibition Y b0 b1 X1 b2 X2 b3 X3 b12 X1 X2 b13 X1 X3 b23 X2 X3
b11 X1 2 b22 X2 2 b33 X3 2 9

where Xk are the factors to be studied, with regression coefcients b0


(constant term), b1, b2 and b3 (single factor effects), b11, b22 and b33
(quadratic terms), and b12, b13 and b23 (interaction effects); Y is the re-
sponse function of photodegradation rate constants.
The regression coefcients of the response function were deter-
mined by correlating the experimental data. The relationship between
the response function and independent variables was represented by
the second-order polynomial regression model as follows:

Y 0:200:29X1 6:93X2 0:32X3 2:0 X1 X2 1:21X1 X3


13:40X2 X3 0:60 X1 2 201:30X2 2 0:53X3 2 10

The comparison of the experimental and predicted values of


photodegradation rate constants was shown in Fig. 5. The value of de-
termination coefcient is 0.9773 and the high value of determination
coefcient indicated that only 2.27% of the total variations were not ex-
Fig. 1. Cl and DCF concentration changes during the DCF photodegradation process. plained by the regression model for DCF. In other words, the results

Please cite this article as: Zhang, N., et al., Photodegradation of diclofenac in seawater by simulated sunlight irradiation: The comprehensive effect
of nitrate, Fe(III) and chl..., Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.024
4 N. Zhang et al. / Marine Pollution Bulletin xxx (2017) xxxxxx

Table 3
Results of the 3-factor Box-Behnken design and the value of response function (calculated rate constants k).

Run X1 X2 X3 NO
3 (mmol/L) Fe3+ (mmol/L) Cl (mmol/L) k (min1) Actual inhibition rate (%) Theoretical inhibition rate (%)

1 0 1 1 0.05 0 0 0.1907 6.98 6.98


2 0 0 0 0.05 0.005 0.1 0.1494 27.12 34.54
3 0 0 0 0.05 0.005 0.1 0.1494 27.12 34.54
4 1 1 0 0.1 0 0.1 0.1686 17.76 25.76
5 1 0 1 0.1 0.005 0.2 0.1430 30.24 38.39
6 1 0 1 0 0.005 0 0.1813 11.56 11.56
7 0 1 1 0.05 0 0.2 0.1631 20.44 24.05
8 1 0 1 0 0.005 0.2 0.1475 28.05 28.63
9 0 0 0 0.05 0.005 0.1 0.1487 27.46 34.54
10 0 1 1 0.05 0.01 0.2 0.1420 30.73 37.22
11 1 1 0 0 0.01 0.1 0.1422 30.63 29.17
12 0 0 0 0.05 0.005 0.1 0.1490 27.31 28.30
13 0 1 1 0.05 0.01 0 0.1428 30.34 20.15
14 1 1 0 0.1 0.01 0.1 0.1406 31.41 38.93
15 1 0 1 0.1 0.005 0 0.1527 25.51 21.35
16 0 0 0 0.05 0.005 0.1 0.1503 26.68 38.93
17 1 1 0 0 0 0.1 0.1722 16.00 16.00

indicated good agreement between experimental and predicted values underlying the analyses. Therefore, it conrmed the proposed models
of the photodegradation rate constants. The normal probability plot of are statistically very signicant.
the internally studentized residuals for DCF was shown in Fig. 6. It sug- The analysis of variance (ANOVA) test for response function is listed
gests that there is almost no serious violation of the assumptions in Table 4. This was used to determine the signicance of the effects of
independent variables on the response function (Catalkaya and Kstwi,
2009; Liu and Chiou, 2005). As shown in Table 4, the Model F-value of

Fig. 2. The three-dimensional response surface plots and contour plots of photodegradation Fig. 3. The three-dimensional response surface plots and contour plots of photodegradation
rate constants as the function of NO3 concentration (mmol/L) and Fe
3+
concentration rate constants as the function of NO 3 concentration (mmol/L) and Cl

concentration
(mmol/L), (a) the three-dimensional response surface plots, (b) the contour plots. (mmol/L), (a) the three-dimensional response surface plots, (b) the contour plots.

Please cite this article as: Zhang, N., et al., Photodegradation of diclofenac in seawater by simulated sunlight irradiation: The comprehensive effect
of nitrate, Fe(III) and chl..., Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.024
N. Zhang et al. / Marine Pollution Bulletin xxx (2017) xxxxxx 5

Fig. 6. The normal probability plot of the internally studentized residuals for DCF.

When the P-value was less than the signicance level which was often
0.05 or 0.01, the result was statistically signicant (Liu and Chiou,
2005; Zarei et al., 2010). As shown in Table 4, the P-value of the model
was b 0.0001 which implied that the model was highly signicant. The
Lack of Fit P-value of 0.1652 (N0.05) implied that the Lack of Fit was
not signicant, that is, the quadratic model was statistically signicant
for the response and the model was adequate and valid, and can be
used for further analysis. Moreover, the variables X2, X3, X2X3 and X22
were highly signicant model terms with P-values b 0.01; the variables
X1 and X23 were signicant model terms with P-values b 0.05. These
results demonstrate that compared with NO 3 , Fe
3+
and Cl had more
important effect on the photodegradation of DCF.

3.4. Photodegradation of DCF in natural seawater

The photodegradation rate of DCF in natural seawater is shown in


Fig. 7 and demonstrates that the rate constant of DCF in natural
seawater was slower than in pure water. This difference can be ex-
Fig. 4. The three-dimensional response surface plots and contour plots of plained that numerous species in natural seawater compete with pure
photodegradation rate constants as the function of Fe3+ concentration (mmol/L) and
Cl concentration (mmol/L), (a) the three-dimensional response surface plots, (b) the
water (Peng et al., 2016).
contour plots.
4. Conclusions

390.81 implied that the model was signicant and the adjusted R2 value The BoxBehnken design and response surface methodology were
was 0.9955 which indicated that 99.55% of the total variation was ex- used to generate statistically reliable results for the photodegradation
plained by the model. Moreover, the P-values were used to determine of diclofenac under simulated sunlight. The conclusions are as follows:
the signicance of each of the coefcients, which in turn, are necessary
(1) Degradation pathways proceed via pseudo rst-order kinetics in
to understand the pattern of the interactions between the test variables.
all cases and the photodegradation of diclofenac by simulated
sunlight.

Table 4
Estimated regression coefcients of signicance for the response function Y
(photodegradation rate constants) from the data of BBD experiments.

Source Sum of squares df Mean square F value P-value

Model 0.0023 9 0.0003 390.81 b0.0001


X1 (NO 3 ) 2.02E-05 1 2.02E-05 30.62 0.0009
X2 (Fe3+) 0.0018 1 0.0018 2706.22 b0.0001

X3 (Cl ) 0.0002 1 0.0002 284.30 b0.0001
X1X2(NO 3 -Fe
3+
) 1E-06 1 1E-06 1.52 0.2576
X1X3(NO
3 -Cl ) 5.62E-07 1 5.62E-07 0.85 0.3861
X2X3(Fe3+-Cl) 9.22E-05 1 9.22E-05 139.95 b0.0001
X21(NO3 )
2
2.32E-06 1 2.32E-06 3.53 0.1025
X22 (Fe3+)2 0.0002 1 0.0002 339.11 b0.0001
X23 (Cl)2 5.16E-06 1 5.16E-06 7.84 0.0265
Residual 4.61E-06 7 6.59E-07
Lack of t 3.16E-06 3 1.05E-06 2.90 0.1652
Pure error 1.45E-06 4 3.63E-07
Fig. 5. Comparison of the experimental and predicted values of photodegradation rate
Cor total 0.0023 16
constants k.

Please cite this article as: Zhang, N., et al., Photodegradation of diclofenac in seawater by simulated sunlight irradiation: The comprehensive effect
of nitrate, Fe(III) and chl..., Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.024
6 N. Zhang et al. / Marine Pollution Bulletin xxx (2017) xxxxxx

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Please cite this article as: Zhang, N., et al., Photodegradation of diclofenac in seawater by simulated sunlight irradiation: The comprehensive effect
of nitrate, Fe(III) and chl..., Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.02.024

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