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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
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.
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
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 (%)
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+
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 (%)
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.
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.
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