G Model
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Y. Wang et al. / Chinese Chemical Letters xxx (2019) xxx–xxx
improve the efficiency of electrochemical oxidation [26,27]. For
example, the Ti/SnO2-Sb/Er-PbO2 electrode demonstrated the
optimal performance for the oxidation of 4-chlorophenol com-
pared to Ti/SnO2-Sb/Ce-PbO2 electrode, Ti/SnO2-Sb/La-PbO2 elec-
trode and Ti/SnO2-Sb/Gd-PbO2 electrode [24]. However, it is
unknow whether the SMX and Ac-SMX can be degraded by Ti/
SnO2-Sb/Er-PbO2 electrode. The electrochemical degradation
mechanism and toxicity variation of SMX and its metabolite have
not been elucidated. Thus, it is necessary to have insights into the
elimination of sulfamethoxazole and its metabolite by electro-
chemical degradation.
In this study, the electrochemical degradation of SMX and Ac-
SMX was investigated by using Ti/SnO2-Sb/Er-PbO2 electrode.
Affecting factors, such as current density, initial solution pH and
inorganic ions, were investigated to analyze the kinetics and
energy consumption of SMX and Ac-SMX. Degradation intermedi-
ates were identified to propose possible electrochemical degrada-
tion pathways of SMX and Ac-SMX in aqueous solution. Total
organic carbon (TOC) and inorganic ions were measured. Toxicities
of SMX, Ac-SMX and their intermediates were predicted using a
quantitative structure-activity relationship (QSAR) model.
Electrochemical degradation experiments were conducted in
an electrolytic cell. The Ti/SnO2-Sb/Er-PbO2 (anode) and stainless
32.6 and 27.4 min, respectively. Compared to the k values (0.05-
0.50 min-1) of SMX degradation at current density of 10-60 mA/
cm2 using Ti/Ru0.3Ti0.7O2 anode, Ti/SnO2-Sb/Er-PbO2 anode
showed higher degradation efficiency [28]. The degradation
efficiencies of SMX and Ac-SMX were accelerated with the
ꢀ
increasing current density, which may be due to the more OH
production at higher current density [29,30]. It also showed that
the removal rates of SMX and Ac-SMX increased slowly when the
current densities were higher than 10 and 14 mA/cm2, respectively,
which may be owing to the lower rising tendency of ꢀOH
production. Thus, 10 and 14 mA/cm2 were chosen as the optimal
current density for the subsequence experiments of SMX and Ac-
SMX to avoid energy waste. The removal rates of SMX and Ac-SMX
under the optimal current density were 99.6% and 88.5% after
20 min and 30 min electrochemical reaction, respectively. These
results illustrate that the Ac-SMX is more difficult to degrade than
SMX. Therefore, investigating the electrochemical degradation
behavior of Ac-SMX is essential to comprehensively analyze the
risks related with SMX in the water bodies.
As shown in Fig. S1 (Supporting information), the effect of
initial pH ranging from 3-11 on the electrochemical degradation
efficiencies of SMX and Ac-SMX was investigated. For SMX, the k
values increased from 0.183 to 0.457 min-1 with the pH decreasing
from 11 to 3, and the corresponding removal rates increased from
97.8% to 99.9%. For Ac-SMX, the k values were 0.074, 0.078, 0.079,
0.087 and 0.094 min-1 at the pH of 11, 9, 7, 5 and 3, respectively. The
corresponding removal rates slightly increased from 88.0% to
94.1%. Obviously, SMX and Ac-SMX were favorable to degrade
under acidic condition. The species and hydration of target
compound molecules are affected by the pH of solution [31].
Based on pKa of SMX (pKa1 = 1.8, pKa2 = 5.8) and Ac-SMX (pKa1 < 2,
pKa2 = 5.1) [7], the molecular forms of SMX and Ac-SMX were
dominant under acidic condition and the negatively charged forms
were dominant under alkaline condition. The mass transfer
coefficient of molecular form was higher than negatively charged
form [32–34]. Thus, mass transfer efficiency under acidic condition
was higher than that under alkaline condition, which resulted in
higher k values at lower pH. In addition, concentration of ꢀOH
decreased at alkaline condition due to its reaction with OHÀ, which
also led to lower degradation efficiency [35,36].
steel
(cathode)
were
with
the
same
dimension
(50 mm  50 mm  1 mm), and the electrode distance was 1 cm.
The life time of this anode was more than 1000 h and the electrode
preparation is described in Supporting information. Initial con-
centrations of SMX (prepared with deionized water) and Ac-SMX
(prepared with 1% acetonitrile cosolvent) were both 10 mg/L.
Volume of electrolyte solution was 120 mL with 20 mmol/L Na2SO4
as supporting electrolyte. Five variables including current densities
(4-18 mA/cm2), initial pH (3-11), Cl- concentrations (1-10 mmol/L),
-
-
HCO3 concentrations (1-10 mmol/L) and NO3 concentrations (1-
10 mmol/L) were investigated during the electrochemical degra-
dation experiments. Degradation rate constants (k), half-lives (t1/2
)
and removal rates are illustrated in Tables S1 and S2 (Supporting
information).
Fig. 1 exhibits the electrochemical degradation efficiencies of
SMX and Ac-SMX under different current density. The k values of
SMX were measured to be 0.058, 0.083, 0.139, 0.268 and 0.299 min-
at the current density of 4, 6, 8, 10 and 12 mA/cm2, and the
Fig. 2 illustrates the electrochemical degradation efficiencies of
1
-
corresponding t1/2 values were 40.4, 28.6, 17.7, 10.4 and 9.2 min,
respectively. The k values of Ac-SMX were 0.030, 0.043, 0.072,
0.073 and 0.090 min-1 at the current density of 10, 12, 14, 16 and
18 mA/cm2, and the corresponding t1/2 values were 77.2, 53.5, 34.0,
SMX and Ac-SMX under different concentrations of HCO3-, NO3
and Cl-. With the concentration of HCO3 increasing from 0 to
-
10 mmol/L, the k values of SMX and Ac-SMX were measured to be
0.244–0.277
and
0.064–0.069 min-1,
respectively.
The
Fig. 1. Effect of applied current density on the electrochemical degradation of SMX and Ac-SMX. Initial concentration: 10 mg/L, Na2SO4: 20 mmol/L, electrode distance: 1 cm,
pH: unadjusted.
Please cite this article in press as: Y. Wang, et al., Insights into the electrochemical degradation of sulfamethoxazole and its metabolite by Ti/