Chemosphere 180 (2017) 117e124

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Chemical oxidation of bis(2-chloroethyl) ether in the Fenton process:

Kinetics, pathways and toxicity assessment
Jiaqi Shi, Tao Long*, Rongrong Ying, Lei Wang, Xin Zhu, Yusuo Lin
State Environmental Protection Key Laboratory of Soil Environmental Management and Pollution Control, Nanjing Institute of Environmental Sciences,
Ministry of Environmental Protection of China, Nanjing, 210042, China

h i g h l i g h t s

Fenton was highly effective to degrade BCEE.

12 chlorinated intermediates and 3 main reaction pathways were proposed.

Dimeric intermediates with potential risks were produced.

TOC concentration and toxicity decreased in the process.

The results were well supported and supplemented by theoretical calculations.

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

Article history: Bis(2-chloroethyl) ether (BCEE) is a common chemical material and a frequently detected contaminant in
Received 3 August 2016 groundwater. It has a strong toxicity and some other chemicals such as poly(vinyl chloride-co-isobutyl
Received in revised form vinyl ether) contain similar chloroaliphatic ether structure. So the effective degradation method and
16 January 2017
transformation pathways for BCEE need to be learned. The present study compared the degradation rate
Accepted 26 March 2017
Available online 30 March 2017
of BCEE by Fenton's reagent and other common oxidation methods, and optimized the reaction condi-
tions. Oxidation intermediates and pathways were also proposed and toxicities of the intermediates
Handling Editor: Min Jang were investigated. Results showed that Fenton was highly effective to degrade BCEE. pH, Fe2þ and H2O2
concentration all affected the oxidation rate, among which Fe2þ was the most significant variable. A total
Keywords: of twelve chlorinated intermediates were detected. Three main reaction pathways involved cleavage of
Fenton the ether bond, hydroxyl substitution for hydrogen, and radical coupling. The pathways could be well
Bis(2-chloroethyl) ether interpreted and supported by theoretical calculations. The reaction mixture showed a decreasing trend in
Oxidation pathway TOC concentration and toxicity until totally harmless to Vibrio fischeri after 15 min, but it was noteworthy
Toxicity change
that toxicities of some dimeric intermediates were stronger than BCEE by calculation.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction
The bis(2-chloroethyl) ether (BCEE) is a commonly used chem-
ical material. It primarily functions as an intermediate for the
manufacture of polyisoprene algicide and diquaternary ammonium
microbicide. It also serves as solvent for fats and esters, constituent
of paints and varnishes, and cleaning fluid for textiles (U.S. EPA,
1989, 1993, 1999). In addition, it is formed as a by-product of in-
dustrial processes such as the manufacture of chloroethanol or
propylene oxide, and the chlorination treatment of waste water
* Corresponding author. 8 Jiangwangmiao street, Nanjing, Jiangsu, China.
E-mail address: longtao@nies.org (T. Long).
(Bednar et al., 1993; Kumar et al., 2014; Pelench, 2008). BCEE is
released into the environment during its production and applica-
tion, and has become one of the most frequently detected chlor-
oaliphatic ether contaminants in the USA and Europe. It occurred in
air, drinking water, groundwater, soil, organisms, sewage sludge
and fertilizers (Cai et al., 2007a, 2007b; Mo et al., 2008; U.S. EPA,
1989, 1993, 1999). High concentration of BCEE was often found in
groundwater near chemical and pesticide production plants. For
example, Huang et al. detected 200 mg L1 BCEE from the groud-
water aquifer underneath a chemical manufacturing plant in
Southeast Texas (Huang et al., 1999). The highest level of BCEE in a
contaminated site in Moss Point, Mississippi was found to be
1700 mg L1 (Mutuc et al., 2008). In the preparation of this work, the
occurence of BCEE was found in groundwater samples taken from

http://dx.doi.org/10.1016/j.chemosphere.2017.03.104
0045-6535/© 2017 Elsevier Ltd. All rights reserved.
118 J. Shi et al. / Chemosphere 180 (2017) 117e124
three chemical plants in China which all had long history of
pesticide production, with the maximum concentration reaching
611 mg L1 (See Text S1 in the supplemental material). BCEE will
cause serious damage to human body through inhalation, dermal
contact or ingestion. It has been labeled as a B2 carcinogen and
priority pollutant by the U.S. Environmental Protection Agency
(EPA) (U.S. EPA, 1989, 1993, 1999). EPA set the ambient water quality
criteria for the protection of human health of BCEE at 0.03 mg L1,
much lower than some common contaminants such as benzene
(0.58 mg L1) and trichloroethylene (0.6 mg L1) due to its high
toxicity (U.S. EPA, 2015). As the reported concentration of BCEE in
contaminated groundwater frequently far exceeded the recom-
mend level, it is of practical significance to seek an effective
remediation method for BCEE in the environment. In addition,
similar chloroaliphatic ether structure could also be seen in some
other chemicals such as poly(vinyl chloride-co-isobutyl vinyl
ether). The exploration on its transformation will supply reference
significance for these chemicals.
Chemical oxidation processes are widely used in groundwater
remediation, which convert hazardous contaminants to non-
hazardous or less toxic compounds that are more stable, less mo-
bile, or inert. The conventional oxidizing agents commonly used
include hydrogen peroxide (H2O2), permanganate, ozone, etc.
Fenton, which plays an important role in advanced oxidation pro-
cesses, has been frequently applied in groundwater remediation. It
uses the high oxidative power of
OH reactive species to degrade
the contaminants (Torrades et al., 2003). Fenton treatment also
exhibits advantages such as relatively low cost, and ease of opera-
tion and maintenance (Swaminathan et al., 2003; Zazo et al., 2005).
In addition, a wide spectrum of contaminants could be removed
with a dramatically deduced toxicity at the end of Fenton process
(Arzate-Salgado et al., 2016; Barhoumi et al., 2016). Studies spe-
cifically aiming at the degradation of BCEE using conventional
oxidizing processes were limited, while the degradation of BCEE in
UV/H2O2 system and surface catalyzed Fenton-like treatment has
been reported (Huang et al., 1999; Li et al., 1995; Mutuc et al., 2008).
Due to the existence of direct photochemical fragmentation
mechanism in the UV/H2O2 process, the transformation process of
BCEE in Fenton process without UV-irradiation has not been fully
understood yet.
Classic Fenton provides practical and theoretical foundation for
various Fenton-like processes. In this study, the effects of initial pH,
ferrous ion (Fe2þ) concentration and H2O2 dosage on BCEE Fenton
oxidation were examined and key variables influencing the
degradation rate were revealed. Then the oxidation pathways of
BCEE were tentatively proposed. Density functional theory (DFT)
was employed to interpret the reaction pathways. Furthermore,
total organic carbon (TOC) and toxicity change of the reaction so-
lution were measured. Toxicity of each intermediate was calculated
as well. This comprehensive work will provide a potential method
to effectively remediate BCEE contamination, and improve the
understanding of the environmental behaviors of chemicals con-
taining chloroaliphatic ether structures.
2. Materials and methods
2.1. Materials and preparation
The BCEE was purchased from J&K Scientific Ltd., with the purity
of 99%. The NaOH, anhydrous NaSO4, NaCl, FeSO4 and 30% H2O2
were received from Sinopharm Chemical Reagent Co., Ltd., among
which anhydrous NaSO4 was baked at 420  C for 4 h before use to
remove water. The 2-chloroethanol were obtained from AccuS-
tandard Inc. Pesticide analysis grade n-hexane, methyl tert-butyl
ether (MTBE), and spectroscopically pure grade concentrated
sulfuric acid were purchased from Merck KGaA (Darmstadt,
Germany).
2.2. Kinetic studies
A set of experiments was performed with the same initial con-
centration of BCEE (5 mg L1), but different Fe2þ (0.2e8 mM) and
H2O2 dosages (1e10 mM). The initial solution pH was adjusted with
H2SO4 or NaOH to a value in the range from 2 to 5. Since the three
variables affected the degradation process synthetically, an
orthogonal test L9(33) was further designed to determine the key
variable influencing the degradation rate.
Each test was conducted in a 250 mL conical flask with stopper,
and had a 200 mL reaction solution. The solution was agitated
moderately with a magnetic stirrer to ensure the homogeneity.
Temperatures were kept at 20  C. Then 5 mL reaction solution was
transfer to 35 mL methanol solution (or Na2S2O3 solution in the
TOC analysis) to quench the reaction at the beginning and at 10s,
30s, 1 min, 2min, 5min, 10min and 15 min, respectively. The ex-
periments were conducted in triplicates and the averaged data was
presented. A control group without oxidizing agent was set to
ensure no loss of BCEE during the experimental period. Quantifi-
cation of BCEE was made using a gas chromatograph/mass spec-
trometer (GC/MS, Agilent 7890A/5975C) with a purge-and-trap
concentrator (Eclipse 4552&4660), and a DB-624 capillary column
(60 m  0.25 mm  1.4 mm, J&W Scientific). Five milliliter of so-
lution entered the purge bottle which was kept at 50  C and the
purging lasted for 11 min. Then desorption was performed at 190  C
for 3 min. Samples were injected in split mode with a split ratio
30:1. The flow rate of the carrier gas (He) was 1.2 mL min1. The
injector temperature was 210  C. The oven temperature was pro-
grammed to increase from 40  C (2 min) to 250  C at 10  C min1,
and held for 5 min. The quadrupole mass spectrometer was oper-
ated in electron ionization (EI) mode. The source temperature and
transfer line temperature were both set at 230  C. Quantitative
determination was made in selective ion monitoring (SIM) mode at
m/z 93, 95, 63 and 65. TOC was measured using an Aurora 1030 W
analyzer (OI Analytical, USA). Using 5 mL water samples, the total
inorganic carbon was removed by the addition of 0.5 mL of 5%
H3PO4 solution for 2 min at 70  C. The TOC in the sample was
oxidized to CO2 by the addition of 1 mL of 10% Na2S2O8 solution for
2 min at 98  C. In both step, the CO2 was purged using high purity
N2 gas for 2 min and measured using a solid-state non-dispersive
infrared (SSNDIR) detector.
2.3. Product analysis
The product analysis was made using the GC/MS after a purge-
and-trap concentrator and liquid-liquid extraction respectively, so
as to capture both volatile and semivolatile products. A different
reactant ratio from the kinetic studies was employed to acquire the
highest product responses. Two groups of batch reactors were
prepared in triplicates. Each reactor had 200 mL of aqueous phase
containing 40 mg BCEE, 0.2 g FeSO4$7H2O and 0.4 mL H2O2. The
reaction was terminated after 1 h, 3 h and 5 h respectively. While
using purge-and-trap concentrator, the solution was injected after
dilution and the measurement conditions were set the same as
those in kinetic studies. When liquid-liquid extraction was taken as
the pretreatment method, some amount of NaCl was added into
each solution before extracting with a solvent containing 95% MTBE
and 5% n-hexane. Organic phase was injected into the GC/MS
(Agilent 7890A/5975C) for analysis after desiccation with anhy-
drous NaSO4. The oxidation products were analyzed using the GC/
MS with a DB-5 capillary column (30 m  0.25 mm  0.25 mm, J&W
Scientific). Samples were injected in splitless mode. The flow rate of
 J. Shi et al. / Chemosphere 180 (2017) 117e124
the carrier gas (He) was 1.0 mL min1. The temperatures of injector,
ionization source and transfer line were 230  C, 230  C and 280  C
respectively. The oven temperature was held at 40  C for 3 min
followed by a ramp of 6  C min1 to a temperature of 200  C fol-
lowed by another ramp of 10  C min1 to a final temperature of
250  C and held for 5 min. The EI source was used and full scan
spectrum (m/z 25e500) was acquired. Controls without oxidizing
agent were also prepared following the same procedures. Chro-
matograms were compared between the experimental group and
the control to detect possible products.
2.4. Calculations for structural properties
The geometries of BCEE and the proposed intermediate prod-
ucts were optimized to ensure that the molecules were at the
minimal potential energy surface. After that the frontier molecular
orbitals (FMOs), frontier electron densities (FEDs) and Wiberg bond
order were computed at the Becke3LeeYangParr (B3LYP)/6-
311G** level (Becke, 1988; Lee et al., 1988) with the Gaussian 09 W
program package (Frisch et al., 2009), and FEDs of the highest
occupied molecular (HOMO) and the lowest unoccupied molecular
orbital (LUMO) were obtained. The values of 2FED2HOMO were
calculated to predict the possible oxidation sites.
2.5. Toxicity test and computation
The toxicity was assessed by Microtox assay with a DeltaTox® II
water toxicity detector (SDIX, USA) in terms of bioluminescence
inhibition of the marine bacteria Vibrio fischeri after 15 min of
exposure time. The acute aquatic toxicities (LC50) to fathead
minnow (96 h) and Daphnia magna (48 h) of BCEE and each
degradation product were predicted by the Consensus method
Fig. 1. The BCEE removal efficiencies at various conditions. (a) BCEE degradation in different oxidation systems. (b) Effect of initial solution pH on BCEE removal (c(Fe2þ) ¼ 0.2 mM,
c(H2O2) ¼ 2 mM). (c) Effect of H2O2 concentration on BCEE removal (pH 3, c(Fe2þ) ¼ 0.2 mM). (d) Effect of Fe2þ concentration on BCEE removal (pH 3, c(H2O2) ¼ 2 mM).
119
using the Toxicity Estimation Software Tool (T.E.S.T., version 4.2)
(U.S. EPA, 2016), which was developed to allow users to estimate
toxicity using a variety of QSAR methodologies and obtained wide
recognition (Lassalle et al., 2014; Liu et al., 2016).
3. Results and discussion
3.1. Comparison with other oxidation processes
An experiment to compare the kinetics of Fenton treatment
with that of conventional chemical oxidation processes (i.e. H2O2,
KMnO4 and Fe2þ activated persulfate) were carried out. The initial
concentrations of oxidants were all set at 5 mg L1. The results
showed that KMnO4, H2O2 and Fe2þ activated persulfate could
remove about 6%, 33% and 42% of BCEE in an hour, respectively.
Fenton process could degrade about 92% of BCEE in 5 min when
using 0.2 mM Fe2þ and 1 mM H2O2 at pH 3 as shown in Fig. 1(a).
Consequently, the hydroxyl radical (
OH) formed from Fenton
process is most effective to degrade BCEE. In the oxidant-free
control experiments, no loss of BCEE was observed, indicating
that the mass loss of BCEE due to volatilization was negligible.
3.2. Effects of initial pH
The effect of pH on the BCEE degradation rate is illustrated in
Fig. 1(b). The initial concentrations of Fe2þ and H2O2 were 0.2 mM
and 2 mM respectively. It can be seen that the reaction was divided
into two stages. The BCEE concentration decreased sharply in the
initial 1e2 min, but after that the reaction rate become much lower.
Each stage followed pseudo-first-order kinetics. For example, the
pseudo-first-order reaction rate constant was 0.0463 s1 and
removal reached about 91.5% in the initial 1 min, while the rate
120 J. Shi et al. / Chemosphere 180 (2017) 117e124
constant was 0.0002 s1 after 2 min and removal was about 94.5%
after 15 min at pH 3. The two-stage reaction was also found in other
studies, and the reason might be that reaction occurred between
Fe2þ and H2O2 in the first stage while the reaction of ferric ion
(Fe3þ) and H2O2 took place in the second stage (de Luna et al., 2013;
Zeng et al., 2015). The degradation had the highest efficiency when
pH was around 3. The reason might be that the (Fe(II) (H2O))2þ
formed when pH was lower, which reacted slowly with H2O2 and
thus produced fewer
OH (Gogate and Pandit, 2004). In addition,
the
OH would be scavenged by Hþ significantly and the reaction
between Fe3þ and H2O2 during the Fenton chain propagation was
inhibited (Wang, 2008). On the other hand, Fe2þ formed Fe3þ at
pH > 4.0, and Fe3þ tended to produce ferric hydroxo complexes or
ferric oxyhydroxides which had low activity (Wang, 2008). Addi-
tionally, the H2O2 was less stable and the production of
OH would
be inhibited at high pH (Masomboon et al., 2009).
3.3. Effects of hydrogen peroxide concentration
H2O2 is the precursor to generate
OH. Usually the degradation
rate of the pollutant increases with H2O2 concentration. But when
excess H2O2 exists in the solution, oxidation reaction will be
inhibited since H2O2 consumes
OH and decomposed to produce
oxygen instead of
OH (Masomboon et al., 2009). In this section of
the work, the initial conditions of 0.2 mM Fe2þ at pH 3 were fixed,
while H2O2 concentrations were varied as 1, 2, 4, 6, 8 and 10 mM.
The results are displayed in Fig. 1(c). The results indicated that
increasing the initial H2O2 concentration from 1 to 6 mM enhanced
BCEE removal. However, when more H2O2 was added, the degra-
dation rate became much lower. The highest initial degradation
rate constant reached 0.0412 s1 and the removal was 95.6% within
15 min at the 6 mM H2O2. The reaction rate constants were all
above 0.0194 s1 and BCEE removal rates were all above 86% when
the initial H2O2 concentration ranged from 1 to 10 mM.
3.4. Effects of ferrous ion concentration
Fe2þ facilitates the oxidation process as it catalyzes the
decomposition of H2O2 to form
OH. However, when the concen-
tration of Fe2þ is in the excess, it can be scavengers of
OH and
attenuate the degradation (Masomboon et al., 2009). The optimal
amount of Fe2þ was explored in this work. The initial conditions
were pH 3 and 2 mM H2O2. The results shown in Fig. 1(d) indicated
that the highest BCEE degradation rate was achieved when Fe2þ
concentration was 2 mM. The initial degradation rate constant
reached 0.1148 s1 and removal rate was 99.9%. The removals of
BCEE were all above 98.5% when Fe2þ concentration was between
0.5 and 1 mM, and it was about 95% when Fe2þ concentration was
0.2 mM.
3.5. Orthogonal test
The orthogonal test results are shown in Table 1. It can be seen
that the concentration of Fe2þ was the primary variable, followed
by pH and H2O2 concentration. The optimal reaction condition
deduced from the orthogonal results was: pH 3, 4 mM of Fe2þ and
6 mM of H2O2.
3.6. Oxidation products and proposed pathways
The intermediates of BCEE were identified by the GC/MS with
different pretreatments. The chromatograms of the reaction solu-
tion sampled at 3 h are shown in Fig. 2(a) and (b). A total of twelve
chlorinated transformation products were detected, in which six
were found via purge and trap. The products obtained via liquid-
liquid extraction were partially overlapped with those via purge-
and-trap, and the overlaps all flowed out their peaks within
20 min. So only the peaks shown after 20 min are displayed in
Fig. 2(b). None of the products were found in the control containing
BCEE alone. Products P2, P3, P4, P11 and P12 had stronger responses
than others, suggesting their possible high concentrations in the
reaction system. All the product mass spectra were displayed in
Fig. S1 in the supplemental material. The products P1, P2 and P4,
which had the chromatographic peaks at 10.573, 11.791 and
14.727 min were determined as 1,2-dichloroethylene, 2-
chloroethanol and 2-chloroethyl acetate respectively by matching
to the NIST MS spectral library. The quality match score were 90%,
94% and 96%. The 2-chloroethanol was also confirmed by compar-
ison with the standard substance. Other structures were deter-
mined by analyzing the fragment peaks in the mass spectra, in
which those of P9P12 were less certain than others. For example,
P3 is supposed to be 2-chloro-1,3-propanediol. The identification
processes are displayed in Eqs. (1)e(5). The isotopic peaks at m/z
79.0/81.0 and 62.0/64.0 with the abundance ratios of 3:1 indicated
the existence of one Cl atom. The fragment ions with m/z 79.0/81.0
were formed by the a- or s-scission from P1, as shown in Eqs. (1)
and (2). Then the ions could be further scissored to form peaks of
m/z 49.0/51.0 or m/z 43.0. The intense peaks at m/z 62.0/64.0 were
formed by the rearrangement process, and a H2O molecule was
eliminated. The ions at m/z 31.0 had the most intense responses. It
came from the a- or s-scission. The symmetrical structure con-
taining two hydroxyls strengthened the responses. The weak peak
at 107.9 might come from the dehydrogenation from the parent
molecule. The proposed fragment ion structures of other products
were also provided in Fig. S1. The reasonable interpretations on the
fragment ion peaks ion provided a high degree of certainty in
structural assignments.
(1)
(2)
(3)
(4)
(5)
The degradation pathways of BCEE were tentatively proposed
according to the structures of the products and shown in Fig. 3.
 J. Shi et al. / Chemosphere 180 (2017) 117e124 121

Table 1 Three distinct pathways might occur simultaneously during the

Factorial level design and results of orthogonal test. oxidation process. Firstly, the CeO bond was cracked and
OH was
Test No. pH Fe2þ con. (mM) H2O2 con. (mM) Degradation ratio added onto the C to form 2-chloroethanol (P2). Similar ether
in 1 min (%) cleavage was also detected in Fenton-like process of MTBE
1 2 1 4 98.24 (Bergendahl and Thies, 2004) and aromatic ethers (Luo et al., 2011;
2 2 2 6 99.42 Methatham et al., 2012). Secondly, the
OH was substituted for
3 2 4 8 99.81 hydrogen to form the hydroxylated BCEE (T1), and then dehydro-
4 3 1 6 99.70
genation or rearrangement reactions occurred, forming P4 and P5
5 3 2 8 99.85
6 3 4 4 99.87 respectively. It has also been reported in other studies that hydroxyl
7 4 1 8 99.29 substitution was the crucial oxidation manner in Fenton process
8 4 2 4 99.84 (Ammar et al., 2015; Barhoumi et al., 2016). Thirdly, coupling of
9 4 4 6 99.89
radicals forms dimeric products, such as P1, P3, P6-P12. Previous
I 99.16 99.08 99.32
II 99.81 99.70 99.67
studies on oxidation degradation of other chemicals such as
III 99.67 99.86 99.65 bisphenol A and halophenols also reported the generation of
R 0.65 0.78 0.35 dimeric products (Molkenthin et al., 2013; Vallejo et al., 2015). But
we did not find any reports on formation of coupling-reaction

Fig. 2. The gas chromatograms of the reaction solution sampled at 3 h. The purge-and-trap pretreatment before analysis produced (a) and liquid-liquid extraction was employed to
produce (b).
122 J. Shi et al. / Chemosphere 180 (2017) 117e124

Fig. 3. Proposed Fenton oxidation pathway scheme of BCEE.

byproducts during oxidation processes of ethers.
Huang et al. (1999) and Li et al. (1995) revealed the mechanisms
of BCEE UV peroxidation, in which
OH was also an important
initiated radical. They found a total of eleven intermediates in
which six are chlorinated. The 2-chloroethanol and 2-chloroethyl
acetate were detected in both their studies and this work. The
chloroethene, 2-chloroethoxy-ethene, enolic tautomer of 2-
chloroethyl acetate, and hydroxylated BCEE were not detected out
in this work although they were also thought to be produced in the
oxidation process. The difference might result from the different
with dense LUMO distribution. Moreover, the atoms with larger
2FED2HOMO values are more easily oxidized (Shi et al., 2015). The
bond with a smaller Wiberg bond order is more easily fractured.
The three-dimensional iso-surfaces of the FMOs (HOMO and
LUMO) at the isovalue of 0.07, the FED (2FED2HOMO and 2FED2LUMO)
values and the Wiberg bond order of BCEE are displayed in Fig. 4. It
could be seen from Fig. 4(a) that 2(20 )C had the larger HOMO dis-
tribution and a higher 2FED2HOMO values than 3(30 )C, meaning that
H connecting 2(20 )C was more apt to be pulled off and replaced by

OH. T1 was generated as a result. The oxygen atom had the largest

reaction condition and spectrum analysis method. Other ten in-
termediates we found in this manuscript were not reported by
previous studies, especially those formed by polymerization. The
application of liquid-liquid extraction in this study could also have
benefitted the detection of more intermediates.
3.7. The oxidation mechanism assisted with DFT calculations
The FMO, FED and bond order calculations could further ratio-
nalize the proposed oxidation products and pathways. According to
the frontier orbital theory proposed by Fukui et al. (1952), the
nucleophilic reaction tends to occur at sites with dense HOMO
distribution, while the electrophilic reaction is apt to occur at sites
2FED2HOMO of all, so an electron was easily lost from it. The CC
bond was thus broken to form R10 although the CC bond is much
stronger than CO and CCl bonds (as indicated in Fig. 4(c)). R11
was formed through similar manner, but its concentration was
much lower because of the smaller 2FED2HOMO value of Cl atom. It
can be seen from Fig. 4(b) that 3(30 )C was much easy to be reduced,
so Cl atom was removed to form P4. The CO bond was easily
scissored while 2(20 )C was being attacked by a
OH for its relatively
weak bond strength, and P2 was produced. Then the formation of
R7 and R8 experienced a similar course as those of R10 and R11. The
CCl bond was also possibly scissored in the oxidation process
owing to its weak bond strength.

Fig. 4. Frontier molecular orbitals, electron densities and Wiberg bond order of BCEE. The hydrogen atoms were not shown for simplicity. (a) The computed 2FED2HOMO and HOMO
isodensity surfaces; (b) The 2FED2LUMO and LUMO isodensity surfaces; (c) The Wiberg bond order of BCEE.
 J. Shi et al. / Chemosphere 180 (2017) 117e124 123

eliminate BCEE in aqueous solution. pH, Fe2þ and H2O2 concen-

tration all affected the oxidation rate, among which Fe2þ concen-
tration was the key influencing factor. A total of twelve chlorinated
intermediates were identified by mass spectrometry analysis, and
the reaction pathways mainly involve cleavage of the ether bond,
hydroxyl substitution for hydrogen, and radical coupling. The
pathways could be well interpreted and supported by theoretical
calculations. The reaction mixture showed a decrease trend in TOC
concentration and toxicity until totally harmless to Vibrio fischeri
after 15 min, in spite that calculated toxicities of some dimeric in-
termediates were stronger than BCEE.

Acknowledgements

The research was supported by National High Technology

Fig. 5. The attenuation of BCEE and TOC during the Fenton process (pH 3, 5 mM BCEE,
4 mM of Fe2þ and 4 mM of H2O2).
Research and Development Program of China (No. 2013AA06A608),
the Natural Science Foundation of Jiangsu Province (Grants No.
BK20160101 and BK20130104), Natural Science Foundation of
China (No. 21607049), and Central Public-interest Scientific Insti-
tution Basal Research Fund (No 20160309). We thank Dr. Erdeng Du
for his valuable comments.

3.8. Mineralization and toxicity of the degradation products Appendix A. Supplementary data

The TOC removal during the oxidation process was measured to Supplementary data related to this article can be found at http://
reflect the mineralization of BCEE (Fig. 5). The results indicate that dx.doi.org/10.1016/j.chemosphere.2017.03.104.
TOC decreases more slowly than BCEE. BCEE was almost completely
decomposed in 1 min at the specified condition that pH 3, 5 mM References
BCEE, 4 mM of Fe2þ and 4 mM of H2O2 while the TOC removal was
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