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Department of Earth and Environmental Sciences, Wright State University, Dayton, OH 45435, USA
b
Department of Civil Engineering, Texas A&M University, College Station, TX 77843-3136, USA
Received 19 June 2007; received in revised form 9 October 2007; accepted 11 October 2007
Available online 20 February 2008
Abstract
Transformation of 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) by Fe(II) in 10% cement slurries was characterized using a batch reactor
system. 1,1,2,2-TeCA was completely converted to trichloroethylene (TCE) within 1 h in all experiments, even in controls with cement
that did not include Fe(II). Therefore, complete degradation of 1,1,2,2-TeCA depends on the behavior of TCE. The half-life of TCE was
observed to be 15 d when concentrations of Fe(II) and 1,1,2,2-TeCA were 98 mM and 0.245 mM, respectively. The kinetics of TCE
removal was observed to be dependent on Fe(II) dose, pH and initial substrate concentration. Pseudo-rst-order rate constants linearly
increased with Fe(II) dose up to 198 mM when initial target concentration was 0.245 mM. Pseudo-rst-order kinetics generally described
the degradation reactions of TCE at a specic initial concentration, but a modied LangmuirHinshelwood model was necessary to
describe the degradation kinetics of TCE over a wide range of initial concentrations. A surface reaction of TCE on active solids, which
were formed from Fe(II) and products of cement hydration appears to control observed TCE degradation kinetics.
2007 Elsevier Ltd. All rights reserved.
Keywords: Degradative solidication/stabilization; 1,1,2,2-Tetrachloroethane; Trichloroethylene; Reductive dechlorination; Fe(II); Portland cement
1. Introduction
1,1,2,2-Tetrachloroethane (1,1,2,2-TeCA) has been used
as a solvent for cleaning and degreasing as well as an
intermediate chemical to produce compounds such as tetrachloroethylene (PCE), trichloroethylene (TCE), and 1,2dichloroethylene (1,2-DCE) (Anonymous, 1997). Although
the commercial manufacture of 1,1,2,2-TeCA ceased in the
early 1990s, it is a compound found at contaminated sites
(Registry, 2006). Because 1,1,2,2-TeCA can produce products like vinyl chloride (VC) that is a known human carcinogen, it is important to investigate the reaction mechanism
and rates of its degradation. Iron-based degradative solidication/stabilization (DS/S-Fe(II)) has been developed by
Corresponding author. Tel.: +1 937 775 4225; fax: +1 937 775 3462.
E-mail address: jung.bahngmi@gmail.com (B. Jung).
0045-6535/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2007.10.020
Hwang et al. (Hwang and Batchelor, 2000) as a combination treatment of a chemical process and conventional
solidication/stabilization (s/s). Recent researches have
demonstrated that DS/S-Fe(II) can reductively dechlorinate PCE, TCE, 1,1-dichloroethylene (1,1-DCE), VC,
carbon tetrachloride (CT), chloroform (CF), and polychlorinated biphenyls (PCBs) (Hwang and Batchelor, 2001,
2002; Son, 2002; Hwang et al., 2005). The eectiveness of
DS/S-Fe(II) for degrading these compounds indicates that
it would be applicable to 1,1,2,2-TeCA. In addition, the
complete and rapid removal of 1,1,1-trichloroethane
(1,1,1-TCA) has been reported (Jung and Batchelor,
2004), which means that DS/S-Fe(II) can be extended to
chlorinated ethanes as well chlorinated methanes, chlorinated ethenes and polychlorinated biphenyls. DS/S-Fe(II)
treatment combined with immobilization and the chemical
process could be applied to the sites with waste mixtures
of organic and inorganic contaminants. Furthermore, our
coworkers have tried to identify the active agents in DS/SFe(II) that are responsible for the degradation of chlorinated compounds (Ko and Batchelor, 2007). If the components that contribute to the formation of reductant solid in
DS/S-Fe(II) can be conrmed and synthesized in pure
phases excluding Portland cement, the technique can be
applied to (waste)water treatment to remove the
contaminants.
Previous studies of DS/S-Fe(II) have been based on the
hypothesis that Fe(II) will form reactive solids with cement
components, and these reactive solids are likely to be
similar to Fe(II)Fe(III) (hydro)oxides like green rust.
Recently, our research team provided the results of X-ray
diraction (XRD), scanning electron microscopy (SEM)
and SEM with electron-dispersive spectrometry (SEMEDS) analyses that support this hypothesis (Ko and Batchelor, 2007). In 10% cement slurries with and without Fe(II),
they found solids such as Friedels salt, calcium aluminate
hydrates, and calcium aluminum silicate by XRD analysis.
These solids were observed by SEM images to be
hexagonal plates, which is a characteristic of aluminate
ferrite-monosubstituted (AFm) phases. AFm phases are
structurally similar to layered double hydroxides (LDHs)
(Hewlett, 1998; Kalinichev and Kirkpatrick, 2002). LDHs
are composed of divalent and trivalent cations in the octahedral sheets and an anion in interlayers between the octahedral sheets. Also, addition of Fe(II) into the cement
slurry did not form new solids, which suggests that the
active solids for PCE degradation in DS/S-Fe(II) process
might be AFm with Fe(II) adsorbed onto the surface or
incorporated by isomorphous substitution into their structure (Ko and Batchelor, 2007). The SEM result by Choi
et al., have shown that GR-F (green rust with F-anion)
has the shape of 1 lm hexagonal plates (Choi, 2005).
There are three possible transformation pathways for
1,1,2,2-TeCA: hydrogenolysis, reductive b-elimination,
and dehydrochlorination. Dehydrochlorination is not a
reductive reaction, i.e. it does not involve the transfer of
electrons. 1,1,2,2-TeCA can undergo two major reductive
dechlorination pathways requiring the transfer of two electrons, i.e., hydrogenolysis or reductive b-elimination. The
sequential products of 1,1,2,2-TeCA by hydrogenolysis
are 1,1,2-trichloroethane (1,1,2-TCA), 1,2-dichloroethane
(1,2-DCA), chloroethane (CA), and ethane. cis-Dichloroacetylene (c-DCE) and trans-dichloroacetylene (t-DCE)
can be directly formed from 1,1,2,2-TeCA by reductive belimination or indirectly from an intermediate (TCE) via
hydrogenolysis. If c-DCE undergoes hydrogenolysis, VC
and ethene will be produced, whereas if it undergoes reductive b-elimination, acetylene would be produced which can
be reduced to ethene and ethane.
This study is based on the following hypotheses: (1) the
reducing agent for 1,1,2,2-TeCA (or degradation products)
is a compound produced by reaction of Fe(II) with hydration products of Portland cement to produce reactive solids; and (2) transformations of 1,1,2,2-TeCA and its
degradation products occur on the surfaces of reactive sol-
727
728
dC TCE ;l
k
k
C TCE ;l C TCE ;l
Vg
p
dt
1 H V K s
l
k obs C TCE ;l ;
where CTCE*,l (mM) is the concentration of TCE* in aqueous phase; CTCE*,l0 (mM) is the concentration of TCE* in
aqueous phase at t = 0; H is the dimensionless Henrys
constant; Vg (ml) is the volume of gas phase; Vl (ml) is
the volume of aqueous phase; kobs (d1) is the observed
pseudo-rst-order rate constant; k (d1) is the pseudorst-order rate constant corrected by a partitioning factor;
and p is the dimensionless partitioning factor. The value of
the dimensionless Henrys constant for TCE used was
0.419 (Butler and Hayes, 2000). The values of Vg and Vl
used were 0.3 ml and 23 ml. The solid phase partition coefcient (Ks) was determined as an average of Ks values calculated from controls for three experiments (exp. 1, 2 and 3
in Table 1). The values of the partitioning coecient (Ks)
and partitioning factor (p = 1 + H (Vg/Vl) + Ks) for
TCE* were calculated as 0.031 and 1.04, respectively (see
supplementary material).
A dual-concentration second-order kinetic model
(Eq. (2)) was better tting model to the experiment where
the concentrations of 1,1,2,2-TeCA and Fe(II) were
0.245 mM and 39.2 mM, respectively. This model explicitly
considers the eect of the concentration of reductant on
observed kinetics and is necessary when the concentration
of reductant changes substantially during the reaction. It
expresses the concentration of reductant in terms of its
reductive capacity, which is the amount of target compound that it could reduce at given sucient time. This
729
Table 1
Experimental conditions and pseudo-rst-rate constants of dechlorination of TCE*
Exp.a
1
2
3
4
5
6
7
8
9
10
11
12
C0b (mM)
0.245
0.245
0.245
0.245
0.245
0.245
0.245
0.245
0.01
0.1
1
0.245
Fe(II)c (mM)
39.2
98
196
196
196
196
196
196
196
196
196
196
kobsd (d1)
pH
12.5
12.4
12.0
10.6
11.5
12.1
12.3
13.3
12.0
12.0
12.0
12.0
0.0067(42%)
0.046(20%)
0.088(27%)
0.010(84%)
0.0081(110%)
0.044(16%)
0.019(21%)
0.016(25%)
0.46(34%)
0.18(25%)
0.019(17%)
t1/2 (d)
nf
Products
103
15
8
69
86
16
36
43
2
4
36
24
30
31
20
22
20
23
23
21
22
25
27g
dC TCE ;l
k 2;obs C 0RE pfC 0TCE ;l C TCE ;l gC TCE ;l
dt
730
0.10
0.20
0.08
0.15
kobs (d-1)
0.25
0.10
control, w/ce
Fe(II) 39.2mM
Fe(II) 98mM
Fe(II) 196mM
0.05
0.06
0.04
0.02
0.00
0
20
40
60
80
100
120
140
Time (d)
Fig. 1. Eect of Fe(II) dose on kinetics of degradation of TCE* in 10%
cement slurries. Some error bars are smaller than the symbols. Solid lines
are for the rst-order model, Eq. (1) and dotted line is for the second-order
model, Eq. (2).
0.00
0
50
100
150
200
731
14
11
13
pH
pH
10
9
12
8
pH 10.70
pH 11.80
11
pH 12.24
pH 12.37
pH 13.24
10
0
10
15
20
25
30
10
15
20
25
30
Time (d)
Time (d)
Fig. 3. The pH changes measured during experiments on degradation of 1,1,2,2-TetCA. Lines do not indicate a model t but are used to help guide the
eye.
0.06
0.05
K obs (d-1)
0.04
0.03
0.02
0.01
0.00
-0.01
10
11
12
13
14
pH
Fig. 4. Dependence on pH of pseudo-rst-order rate constants for
reduction of TCE*. Error bars for kobs are 95% condence intervals.
Lines do not indicate a model t but are used to help guide the eye.
732
1.0
C/C0
0.8
0.6
C0 =0.01 mM
C0 =0.1 mM
0.4
C0 =0.245 mM
C0 =1 mM
Control w/ce
0.2
0.0
0
10
15
20
25
30
Time (d)
Fig. 5. Eect of initial target concentration on degradation of TCE*.
Error bars are standard deviations of measured concentrations. Some
error bars are smaller than the symbols. Solid lines show predictions of a
rst-order kinetic model, (exp. 3 and exp. 911).
0.020
0.015
0.010
0.005
0.000
0.0
0.2
0.4
0.6
0.8
1.0
1.2
733
Table 2
Reported degradation products of 1,1,2,2-TeCA
Reductant
Major products
Minor Products
Reference
c-DCE, t-DCE, VC
TCE (19%)
TCE (58%), acetylene (14%)
TCE (84%)
c-DCE (52%), t-DCE (31%)
c-DCE, t-DCE
Ethane
Ethane (61%), ethene (16%)
c-DCE, t-DCE
c-DCE, t-DCE
TCE, acetylene, ethene, ethane
c-DCE, t-DCE, TCE, ethene
c-DCE, t-DCE, 1,1,2-TCA
a
The conversion percentage of 1,1,2,2-TeCA was estimated after 2400 h. The distribution of products in some references was not reported. See the
reference for details.
4. Conclusion
Appendix A. Supplementary material
The accomplishments of this research in degradation
experiment of 1,1,2,2-TeCA by Fe(II) in cement slurries
are that: (1) the eectiveness of DS/S-Fe(II) for degrading
734
rate constants and initial concentration of TCE* are available. Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.chemosphere.
2007.10.020.
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