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Chemosphere 71 (2008) 726734

www.elsevier.com/locate/chemosphere

Dechlorination of trichloroethylene formed from

1,1,2,2-tetrachloroethane by dehydrochlorination in Portland
cement slurry including Fe(II)
Bahngmi Jung a,*, Bill Batchelor b
a

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

B. Jung, B. Batchelor / Chemosphere 71 (2008) 726734

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

ids. The overall goal of the project that supported this

work is to apply DS/S-Fe(II) to treat chlorinated ethanes.
The objectives of this specic research are to characterize
the transformation kinetics of 1,1,2,2-TeCA in mixtures
of cement and Fe(II) as aected by Fe(II) dose, pH and initial target organic concentration, and to identify chlorinated products that are formed.
2. Materials and methods
2.1. Chemicals
Most of the chemicals used in this study (1,1,2,2-TeCA
(98%), c-DCE (97%), t-DCE (98%), 1,1-DCE (97%), and
VC (200 mg l1 in methanol)) were purchased from
Aldrich, but TCE (>99.5%) was purchased from Fisher Scientic. A gas mixture of 1% CO, CO2, methane, ethane,
ethylene and acetylene in nitrogen were used for analysis
of non-chlorinated products and they were purchased from
Altech Associates, Inc. Stock solutions of chlorinated
organics were prepared daily by diluting them in methanol
(99.8%, HPLC grade, EM). Other chemicals used were ferrous chloride (99+%, tetrahydrate, Sigma), hexane (99.9%,
HPLC grade, EM) and 1,2-dibromopropane (1,2-DBP,
97%, Aldrich Chemical Company, Inc.). Portland cement
(type I, Capitol Cement) that is widely used as a binder
in s/s process was selected in this study. Deaerated deionized water (ddw) was prepared by deoxygenating 18-MX
cm deionized water (Barnstead Nanopure system) with
99.99% nitrogen for 2 h and then purging for 12 h with
mixed gases (5% hydrogen and 95% nitrogen) in an anaerobic chamber (Coy Laboratory Product Inc.). To obtain
the targeted pH, 5 N HCl (37%, Aldrich) and 5 N NaOH
(97%, EM) diluted with ddw was used.
2.2. Experimental procedures
The experimental and analytical procedures reported in
earlier studies were used in this study (Jung and Batchelor,
2004). Experiments were conducted in clear borosilicate
glass vials (24.2 0.1 ml, nominally 20 ml) with triple-seal
closures. These closures consisted of a Teon-lined silicon
septum, lead foil tape (3 M, adhesive backed), and Teon
tape (Norton Performance Plastics Co. nonadhesive,
2 mm thick). All samples were prepared in an anaerobic
glove box. Two types of controls were prepared in duplicate and one control contained water and a target organic
and the other control included cement, water, and the target organic compound. All other experiments were carried
out in triplicate and they included cement, water, ferrous
chloride solution, target organic compound. The mass
ratio of solid to solution was 0.1 in batch experiments.
A kinetic experiment was initiated by adding 10 ll of the
methanolic stock solution of 1,1,2,2-TeCA into the reaction vial, yielding the initial concentration of 0.245 mM.
The Fe(II) dose for experiments with 1,1,2,2-TeCA ranged
from 39.2 mM to 196 mM. The pH of the 10% cement

728

B. Jung, B. Batchelor / Chemosphere 71 (2008) 726734

slurries was reported at approximately 12.5 when the Fe(II)

concentration was 39.2 mM. For experiments to evaluate
pH eects, 5 N HCl or 5 N NaOH were added to the samples to obtain the targeted pH. Three dierent initial target
organic concentrations (0.01 mM, 0.1 mM and 1 mM) were
prepared when it was an experimental factor. After spiking
with the target organics stock solution, the vials were
capped and moved out of glove box and then placed on
a tumbler providing end-over-end rotation at 7 rpm at
room temperature, which ranged from 20 C to 25 C.
2.3. Analytical procedures
Analyses for 1,1,2,2-TeCA and TCE were conducted by
rst separating the aqueous phase by centrifuging the vials
at 2000 rpm (912 g) for 10 min (International equipment
Co. model CS centrifuge). A 50-ll aliquot of supernatant
was rapidly withdrawn and transferred into autosampler
vials containing 1 ml hexane with 2.6 mg l1 1,2-DBP as
an internal standard. Extracted samples were analyzed with
a Hewlett-Packard 6890 GC with a DB-VRX column
(60 m  0.25 mm id, with a lm thickness of 1.4 lm,
J&W scientic) and an electron capture detector (ECD).
The amount of sample injected was 1 ll and the split ratio
was 20:1. The oven temperature program was held at 80 C
for 2 min, ramped at 5 C min1, and held at 130 C for
1 min. The temperature of the injector was 220 C and that
of the detector was 240 C. Nitrogen was used as make up
gas with a ow of 60 ml min1. Chlorinated products (1,1DCE, c-DCE, t-DCE, and VC) were analyzed with a Trace
GC 2000 with a HP-5MS column and a ame ionization
detector (FID). The temperatures of the injector and detector were 200 C. The oven temperature was programmed to
be isothermal at 50 C for 5 min. The column ow rate was
1.5 ml min1 and makeup gas was helium at a ow rate of
40 ml min1. The ignition gases were hydrogen and zero air
and their ows were, respectively, 40 ml min1, and
450 ml min1. A 10-ml sample of supernatant was rapidly
transferred with 10-ml gas tight syringe to a 20-ml amber
vial, following taking 50-ll supernatant sample for analysis
for 1,1,2,2-TeCA and TCE. The vial was tightly capped
and shaken for 30 min at 250 rpm and then allowed to
stand for 5 h at room temperature to equilibrate between
gas and liquid phases. Gas phase samples of 100 ll were
withdrawn from the headspace with a 100-ll gas-tight syringe (Hamilton) and manually introduced into the injection
port. The concentrations of compounds by headspace analysis were quantied by comparing peak areas to standard
calibration curves. Non-chlorinated compounds including
ethane, ethylene and acetylene were analyzed using a
HP6890 GC with a GS-Alumina Column (30 m  0.53 mm
id, J&W Scientic) and a FID. The split/splitless injection
port and detector were both at 150 C and the oven temperature was isothermal at 100 C for 5 min. Nitrogen
was used both as carrier gas and makeup gas. Hydrogen
and zero air were used as ignition gases. The ow rates
of carrier gas and makeup gas were 6.3 and 60 ml min1,

respectively. The same headspace sampling described for

the analysis of chlorinated compounds was applied to
non-chlorinated compounds.
2.4. Kinetic data analysis
In order to nd a better tting kinetic model to the data,
dierent kinetic models with zero order, rst order, second
order, and dual concentration second order rate model
were applied to every experiment and one kinetic model
with lower sum of square errors was selected. Pseudorst-order rate constants represented in this study were
determined by non-linear regression using MATLAB for
windows (version 6.5, The Mathworks, Inc.) and 95% condence intervals of rate constants were obtained. Kinetics
of TCE* degradation could generally be described by a
rst-order model as shown in Eq. (1). Here, the nomenclature TCE* is used to designate trichloroethylene that was
not an original target compound spiked into a reactor but
was produced by degradation of 1,1,2,2-TeCA. Eq. (1) has
been used to obtain pseudo-rst-order rate constants for
PCE, CT, and 1,1,1-TCA in mixtures of cement and Fe(II)
by considering equilibrium partitioning of target organics
into the gas and solid phases (Hwang and Batchelor,
2000; Jung, 2005).


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

B. Jung, B. Batchelor / Chemosphere 71 (2008) 726734

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

Mass ratio of solid to solution was 0.1.

The initial concentration of 1,1,2,2-TeCA that was added to the reactors and assumed to be the initial concentration of TCE*.
c
Source of Fe(II) was FeCl2.
d
kobs is the pseudo-rst-order rate constant for dechlorination of TCE*.
e
Uncertainties represent 95% condence limits expressed in% relative to the estimate for kobs.
f
The number of data points used in the non-linear regression.
g
The number of reactors used.
h
Products analysis was done only for the exp.12. c-DCE, t-DCE, 1,1-DCE and VC were measured at the reaction time of 11 d and TCE* and nonchlorinated compounds (ethane, ethane, and acetylene) were measured at the reaction time of 19 d. The percentage of products to the initial spiked amount
of 1,1,2,2-TeCA are as follows: c-DCE (2.3%), t-DCE (1.3%), 1,1-DCE (0%), VC (0%), ethane (20%), ethene (22%), acetylene(0.9%), and
TCE* (22%).
b

model has been also used to describe results of degradation

of 1,1,1-TCA when Fe(II) concentration was 1.96 mM
(Jung, 2005).


dC TCE ;l
k 2;obs C 0RE  pfC 0TCE ;l  C TCE ;l gC TCE ;l
dt

where C 0RE (mM) is the initial concentration of reductive

capacity of the reductants, k2,obs (d1 mM1) is the pseudo-second-order rate constant. The values of k2,obs and
C 0RE were obtained by conducting non-linear regression
on the TCE* concentration in aqueous phase using
MATLAB.
3. Results and discussion
3.1. Non-reductive reaction of 1,1,2,2-TeCA
Batch kinetic experiments with 1,1,2,2-TeCA were conducted to characterize the eects of Fe(II) dose, pH and initial target organic concentration on degradation kinetics.
1,1,2,2-TeCA was completely and rapidly degraded into
TCE* in the control that contained cement but not as rapidly as in reactors that contained Fe(II). No 1,1,2,2-TeCA
was detected at the rst sample time of 0.2 d in any experiment containing cement. Substantial conversion of 1,1,2,2TeCA (up to 35%) was observed in the control without
cement, which was at approximately pH 8. This behavior
in cement environment of high pH is consistent with other
reports that polychlorinated alkanes undergo dehydrochlorination under neutral or high pH conditions (Vogel et al.,
1987). Therefore, this research focused on the degradation
of 1,1,2,2-TeCA was shifted to investigate the kinetics of
TCE* dechlorination. In other studies, TCE* was also

observed as a major or minor product during abiotic or

biotic transformation of 1,1,2,2-TeCA (Chen et al., 1996;
Butler and Hayes, 2000; Song and Carraway, 2005), but
the formation rate of TCE* was not as fast as the rate
observed in this study. In this work, the rate constant for
dehydrochlorination of 1,1,2,2-TeCA to TCE* was evaluated in two controls. One control contained only water at
pH 8 and had a pseudo-rst-order rate constant of
0.0003(119%) (h1), calculated by Eq. (1), whereas the
rate constant of 1,1,2,2-TeCA by Eq. (2) which showed
better tting was 0.1190(85%) (h1). The other control
contained cement at pH 12.5 and it had a pseudo-rstorder-rate constant of 32.8(5.6%) (h1), calculated by
Eq. (1). Several investigators have evaluated rate constants
for removal of 1,1,2,2-TeCA from solutions without reductants. Butler and Hayes reported an observed rst-order
rate constant (kobs) of 1.11(0.39)  102 (h1) at pH
8.3 (Butler and Hayes, 2000). Song et al. determined
an observed pseudo-rst-order rate constant (kobs) of
1.84(0.42)  102 (h1) at pH 7.28.2 (Song and Carraway, 2005). The observed pseudo-rst-order rate constants of 1,1,2,2-TeCA in cement solution were much
higher than those reported in literature due to the high
pH of 12.5.
Table 1 shows values of pseudo-rst-order rate constants for dechlorination of TCE* cement slurries containing Fe(II).
3.2. Inuence of Fe(II) dose
Fig. 1 shows the loss of TCE* in 10% cement slurries at
three dierent Fe(II) doses (39.2 mM, 98 mM and
196 mM). Although a pH buer was not used, the pH

730

B. Jung, B. Batchelor / Chemosphere 71 (2008) 726734

0.12

0.10

0.20
0.08

0.15

kobs (d-1)

TCE* Concentration (mM)

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).

remained relatively stable due to the buering by hydroxide

ions in the cement solution. At the lowest concentration of
Fe(II) (39.2 mM), the concentration of TCE* decreased
and then remained constant. This indicates that the reductant demand of TCE* exceeded the reductive capacity of
the reductants formed from Fe(II). The dual-concentration
second-order rate model by Eq. (2) was found to provide
the best t to this data (k2,obs = 0.153(55%) (mM1 d1).
Data from experiments conducted at higher concentrations
of Fe(II) was best t by a pseudo-rst-order rate model.
Lines in Fig. 1 are predictions by the best-t models. The
values of sum of square errors and uncertainties for
kinetic data of applied models are presented in the
supplementary material. Pseudo-rst-order rate constants
are shown in Table 1 for all experiments, regardless of
whether that model provided the best t to the data so that
trends in the all of the data could be examined. Fig. 2
shows that a linear relationship describes the eect of
Fe(II) dose on pseudo-rst-order rate constants and linear regression provided the following tting equation:
kobs = 0.0098 + 0.0005  [Fe(II)] (R2 = 0.986). However,
a saturation relationship between pseudo-rst-order rate
constants and Fe(II) dose was observed in previous studies
for degradation of PCE, TCE, and 1,1,1-TCA by mixtures
of cement and Fe(II) (Jung and Batchelor, 2004; Hwang
et al., 2005; Jung, 2005). Therefore, it is expected that the
relationship shown in Fig. 2 would become non-linear as
Fe(II) doses become large.
3.3. Inuence of pH
Prior to batch kinetic experiments, the preliminary tests
were conducted to determine the adequate acid/base solution concentration resulting in a desired pH in a batch reactor. The concentrations of 1.1 N HCl, 0.65 N HCl, 0.22 N
NaOH, and 1.1 N NaOH in a reactor produced approximately pH 10.6, 11.5, 12.3, and 13.2. The eect of pH on

0.00
0

50

100

150

200

Fe(II) dose (mM)

Fig. 2. Dependence of pseudo-rst-order rate constant for TCE* dechlorination on Fe(II) dose. Error bars represent 95% condence intervals for
predicted rate constants. Solid line is tted by linear regression
(kobs = 0.0098 + 0.0005  [Fe(II)], R2 = 0.986).

kinetics of dechlorination TCE* in a mixture solution of

Fe(II) and cement was investigated at ve nominal pH values (pH 10.6, 11.5, 12.1, 12.3 and 13.3). The concentrations
of 1,1,2,2-TeCA and Fe(II) were 0.245 mM and 196 mM,
respectively in these experiments (exp. 48). During the
reaction, the pH was measured for triple reactors with analyzing the concentration of 1,1,2,2-TeCA and TCE* and
the result of pH changes is shown in Fig. 3. In pH eect
experiments, the representative pH was determined as the
average value of measured pH; however, one very low
value was excluded as an outlier. In experiments of pH
10.6 and 11.5, the initial low value appeared to be an error
caused by the incomplete reaction of acids/bases with
cement. At nominal pH 10.6, pH was maintained within
0.2 pH unit after reaction time of 3 d. At nominal pH
11.5, pH was maintained within 0.3 pH unit after a reaction time of 6 d. Experiments at nominal pH of 12.3 and
13.3 showed a constant pH until a reaction time of approximately 10 d. At that time, pH decreased by about 1.5 pH
units and then increased. The experiment at a nominal
pH 12.1 did not include additions of any acid and base
and it showed that pH was maintained at approximately
about 12.1. The pH was decreased to pH 11.1 at a reaction
time of 17 d and then increased. An abrupt decrease of pH
observed during the reaction may convert the chemical
properties of reductant solid therefore aecting the dechlorination rates, even though pH was recovered by Ca(OH)2
produced in cement hydration reactions.
The relationship between kobs and pH is shown in Fig. 4
and it shows that the rate constant of dechlorination of
TCE* reaches a maximum value near pH 12.1. In a mixture
of Fe(II) and cement, similar eects of pH on rate constants have been observed for PCE, CT, CF, and 1,1,1TCA. Maximum rate constants have been reported at pH
12.1 for PCE, pH 12.6 for CT, pH 12.6 for CF, and pH

B. Jung, B. Batchelor / Chemosphere 71 (2008) 726734

12

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.

with various chemical composition due to the isomorphous

replacement of cations and anions in the structure of LDHs
(Taylor, 1997) and the substituted elements will aect the
reactivity of a reductant solid. With pH changes, the concentrations of dissolved species can be changed so that
the composition of AFm phases may be converted, resulting in the changes of reactivity. Also, Ko et al. have investigated the dierence Fe(II)Fe(III)Cl solids (the solids
formed in mixture of FeCl2, FeCl3, and NaCl) formed at
pH 12 and pH 7 by SEM images and EDS spectra (Ko
and Batchelor, 2007). The result showed that the particle
size of the solid formed at pH 12 (0.2 and 0.5 lm) was
much smaller than that formed at pH 7 (45 lm). It can
indicate that pH changes could aect the particle size of
the solid formed in a cement solution and this changes
the reactivity of the solid to reduce the contaminants
because smaller particles would have large specic surface
areas.
3.4. Inuence of initial substrate concentration

12.5 for 1,1,1-TCA, respectively (Hwang and Batchelor,

2000, 2002; Jung and Batchelor, 2004). Lee et al. reported
the pH eect on the dechlorination rate constant for TCE
by sulfate green rust (GRSO4 ) (Lee and Batchelor, 2002).
The rate constant increased with pH increases in the range
from pH 6.8 to pH 10.1. The pH in mixtures of cement and
Fe(II) that are studied here is high relative to the system
investigated by Lee et al. The rate constant in this study
showed that there was an optimum pH for TCE* dechlorination, rather than the linear increase with pH reported by
Lee et al. The actual reductant in this study was hypothesized to be a product of reaction of Fe(II) with cement
hydration products, possibly LDHs. The results by Ko
et al. in our laboratory have documented that AFm phases
formed by the hydration of tricalcium aluminate (C3A) and
tetracalcium aluminoferrite (C4AF) which are major
phases of Portland cement will be responsible to reduce
PCE (Ko and Batchelor, 2007). AFm phases ([Ca2Al(OH)6]+[(Cl)  2H2O]) in a cement system can be formed

The eect of initial 1,1,2,2-TeCA concentration on the

rate of reductive dechlorination of TCE* was investigated
at concentrations of 0.01 mM, 0.1 mM and 1 mM. The
concentration of Fe(II) was 196 mM and pH was approximately 12.1. The initial concentration of TCE* was
assumed to be equal to the initial concentration of
1,1,2,2-TeCA in determining kinetic parameters, which
are shown in Table 1. Fig. 5 shows that a pseudo-rst-order
kinetic model ts well the normalized concentrations of
TCE* (C/C0) at four dierent initial concentrations (exp.
3 and exp. 911).
A plot of logarithm of pseudo-rst-order rate constants
as a function of initial TCE* shows that the rst-order rate
constants change with initial concentration (see supplementary material), which is inconsistent with a rst-order
model. Similar behavior was observed for 1,1,1-TCA degradation (Jung and Batchelor, 2004). This behavior
can be described by a saturation model, such as the

732

B. Jung, B. Batchelor / Chemosphere 71 (2008) 726734

1.2

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).

Initial Degradation Rate for TCE* (r, (mMd-1))

LangmuirHinshelwood (LH) model, which assumes that

all reactants adsorb onto the surface of a solid where the
reaction occurs. This model can be applied by assuming
that the active reductants in mixtures of Fe(II) and cement
are solids and that dechlorination reactions occur on those
solid surfaces. The rate equation for the LH model is
r = (rmaxCTCE*)/(KTCE* + CTCE*). Here, r is the degradation rate for TCE* (mM d1), rmax is the maximum degradation rate (mM d1), and KTCE* is the half-saturation
constant for TCE* (mM). The LH model was applied to
TCE* initial degradation rates by calculating them as the
product of the rate constant (kobs) and the initial TCE*
concentration. Fig. 6 shows the data with a line represent0.025

0.020

0.015

0.010

0.005

0.000
0.0

0.2

0.4

0.6

0.8

1.0

1.2

Initial Conc. of TCE* (mM)

Fig. 6. Dependence of initial degradation rate on initial concentration of
TCE*. Initial degradation rate (r) is a product of pseudo rst-order rate
constant and initial target organic concentration r k obs  C 0TCE . rmax is
the maximum initial degradation rate and KTCE* is the half-saturation
constant for TCE*. The solid line shows the predictions of a saturation
model: r rmax C 0TCE =K TCE C 0TCE , where rmax is 0.022 mMd1 and
KTCE* is 0.026 mM. (exp. 3 and exp. 9-11).

ing predictions by the LH model. Parameters for the model

were determined by non-linear regression to be
rmax = 0.022 (mM d1) and KTCE* = 0.026 (mM).
At very low initial target organic concentrations, the
degradation rate increases proportionally to concentrations, but the rate begins to decrease at higher concentrations, approaching a maximum. How fast this occurs
depends on the value of the half-saturation constant
(KTCE*), which measures the anity between surface sites
and target organics. A lower value of the half-saturation
constant represents a stronger anity for the surface,
which results in the maximum rate being reached at lower
concentrations. The fact that a saturation model described
over a wide range for TCE* (1,1,2,2-TeCA) initial concentration supports the hypothesis that the dechlorination
reaction in mixtures of Fe(II) and cement occurs on the
surface of solid phases that contain a limited number of
active sites.
3.5. Degradation products and reaction pathway
of 1,1,2,2-TeCA
Table 2 summarizes data from the literature for the reaction pathways and products formed during biotic or abiotic
transformation of 1,1,2,2-TeCA. Generally, c-DCE and tDCE were observed as the dominant products during
1,1,2,2-TeCA transformation by metals or bacteria under
methanogenic conditions. Conversion of 1,1,2,2-TeCA to
TCE* by dehydrochlorination was observed to occur to a
greater degree in the presence of FeS and GR than with
other reducing environments. The reduction of 1,1,2,2TeCA by nanosized zero-valent iron or bimetals resulted
in the formation of ethane as a major product, which
was usually reported as a minor product in other studies.
The results by OLoughlin et al. showed that the distribution of degradation products was changed with the addition of trace metals in aqueous suspension of green rust.
In the degradation of 1,1,2,2-TeCA, the major product
was TCE* and it was completely degraded by Fe(II) in
cement slurries under the given conditions. And, 1,1DCE, c-DCE, t-DCE, VC were the only chlorinated products of TCE* degradation that showed identiable peaks
using GC/FID. During TCE* degradation, the concentrations of c-DCE and t-DCE were 2.3% and 1.3% of initially
spiked amount of 1,1,2,2-TeCA, respectively at the reaction time of 11 d (exp. 12, in Table 1). The concentrations
of 1,1-DCE and VC were near zero. Non-chlorinated products (ethane, ethene and acetylene) were measured. The
percentage concentrations of ethane, ethene, and acetylene
to the initial amount of 1,1,2,2-TeCA reported approximately 20%, 22%, and 0.9%, respectively at the reaction
time of 19 d. Total carbon mass recovery (sum of TCE*,
ethane, ethene, and acetylene) was about 65% at the reaction time of 19 d (exp. 12). It is clear that TCE* will not
undergo hydrogenolysis to a substantial extent, because
only traces of intermediate chlorinated products were
found over the reaction time of 11 d, though they were

B. Jung, B. Batchelor / Chemosphere 71 (2008) 726734

733

Table 2
Reported degradation products of 1,1,2,2-TeCA
Reductant

Major products

Minor Products

Reference

Methanogenic bacteria (live)

Reduced smectitea
Iron sulde (FeS)
Green rust
AuGR
Zn(0), Fe(0), Cr(II)
Nanosized iron metal
Nano-sized Pd/Fe

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%)

TCE, 1,1,2-TCA, 1,2-DCA, ethene

Chen et al. (1996)

Cervini-Silva et al. (2001) and Cervini-Silva (2003)
Butler and Hayes (2000)
OLoughlin and Burris (2004)
OLoughlin and Burris (2004)
Arnold et al. (1999) and Arnold et al. (2002)
Song and Carraway (2005))
Lien and Zhang (2005)

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.

not monitored till TCE* was completely degraded. It has

been reported that the major product of PCE and TCE
degradation by Fe(II) in cement slurries is acetylene
(Hwang and Batchelor, 2000; Hwang et al., 2005). Therefore, it can be concluded that degradation of 1,1,2,2-TeCA
in mixtures of cement and Fe(II) occurs in a following process. The rst step is dehydrochlorination to form TCE*
and then conversion of TCE* to chloroacetylene or acetylene by reductive b-elimination. Further conversion to ethene or ethane proceeds.
The pseudo-rst-order rate constant for degradation of
TCE* produced from 1,1,2,2-TeCA was 0.046 (d1), which
is much lower than that (0.47 d1) reported for TCE that
was spiked into mixtures of cement and Fe(II) at comparable concentrations (Hwang et al., 2005). Since chloroacetylene has not been measured, it is not easy to estimate the
eect of chloroacetylene on the disappearance of TCE*.
However, the following assumption can be suggested to
explain lower reactivity of TCE* than TCE. If the solid
formed in this system spiked with 1,1,2,2-TeCA does not
provide sucient electrons to reduce from TCE* to acetylene, an intermediate chloroactylene formed from TCE*
by reductive b-elimination can be accumulated and chloroacetylene sorbed onto the reactive sites might be competitive with TCE*, so that dechlorination rates of TCE* can
be decreased. Here, the assumption that the reaction from
chloroacetylene to acetylene may be a limiting step was
excluded with a literature data that chloroacetylene rapidly
transformed to VC and acetylene by Zn(0) (Arnold and
Roberts, 1998). Also, the lower rate constant of TCE*
could be due to H+ produced during the dehydrochlorination reaction that produces TCE*, which was mentioned in
an earlier study (Jung and Batchelor, 2007). The H+ being
produced could change the surface properties of the active
reductants over the reaction or form a dierent chemical
composition of the solid at the initial step. As the result
of that, active sites can be converted into nonactive sites,
resulting in decrease of reaction rates.

1,1,2,2-TeCA, TCE* was proven; (2) the eects of factors

that aect reduction kinetics were characterized; (3) understanding of the reaction mechanism of 1,1,2,2-TeCA and
TCE* in DS/S-Fe(II) system was improved through identication the degradation products. Half-lives of TCE* (TCE
produced by dehydrochlorination of 1,1,2,2-TetCA) in
Fe(II)/Cement systems were calculated in the range from
2 d to 103 d. The pseudo-rst-order rate model, which
described dechlorination of many chlorinated ethenes, presented well the dechlorination of 1,1,2,2-TeCA. But dualconcentration second-order rate model was a better t to
the data when reductant capacity is limited to reduce a target compound. A linear relationship was shown to describe
the relationship between the pseudo-rst-order rate constant (kobs) for TCE* disappearance and Fe(II) dose up
to a dose of 196 mM. However, it is expected that saturation behavior will be observed at higher Fe(II) dose. The
optimum pH was observed at pH 12.1 for Fe(II) doses of
196 mM. Degradation rates for TCE* showed saturation
relationship with initial target organic concentration of a
range between 0.01 mM and 1 mM. These saturation
behaviors were properly described by a modied
LangmuirHinshelwood kinetic model. This supports the
working hypothesis of this research that reductive dechlorination of chlorinated compounds occurs on the surface
of active solids formed in mixtures of Fe(II) and cement.
In DS/S-Fe(II) process, 1,1,2,2-TeCA dechlorination will
favor reductive b-elimination than hydrogenolysis and it
has an environmental benet because toxic and recalcitrant
VC is not accumulated.
Acknowledgements
This project has been funded primarily with funds from
the State of Texas as part of the program of the Texas Hazardous Waste Research Center. The contents do not necessarily reect the views and policies of the sponsor nor does
the mention of trade names or commercial products constitute endorsement or recommendation for use.

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

The results for calculation of partition coecient (Ks)

and partitioning factor (p), and the relationship between

734

B. Jung, B. Batchelor / Chemosphere 71 (2008) 726734

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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