Aginhotri et al.
been made to achieve the degradation of these special organic
pollutants considering the points mentioned above, which led to
the recent development and research on advanced chemical
processes, including reductive dechlorination (Joy et al., 1987; Xu
et al., 2005). A general chemical equation for reductive
dehalogenation follows:
R{XzHz ze{ ?R{HzX{ ð1Þ
Reduction of chlorinated compounds to their hydrocarbon
skeleton effectively detoxifies the compound (Gibb et al., 2004;
Grittini et al., 1995; Tsyganok and Otsuka, 1999). The application
of zerovalent metals (e.g., iron and magnesium) as electron donors
has drawn the attraction of scientists worldwide. Such dechlori-
nation reactions typically are initiated by the ionization of zero-
valent metals, as shown in reactions 2 and 3, with the
corresponding redox potentials.
Mg0 ?Mg2z z2e{ E0 ~{2:2 V ð2Þ
Fe0 ?Fe2z z2e{ E0 ~{0:44 V ð3Þ
In the next step, the electrons derived from the metal are captured
by protons to produce nascent hydrogen. The source of protons
could be acid or water. Simultaneously, the coordinate complex
salts of palladium, such as [PdCl6]22, which is a well-known
hydrogenating catalyst, is reduced to Pd0, which forms deposit
islets on the surface of the corroding metal, such as Mg0 or Fe0.
Atomic hydrogen is presumed to intercalate on the surface of Pd0
(or metals such as nickel, copper, and cobalt) to produce metal
hydride that is highly reactive towards compounds such as
chlorinated pesticides (Cheng et al., 1997).
Based on the above-mentioned literature, the aim of our
investigation was to dechlorinate endosulfan and lindane using the
Mg0/Pd system with the following specific objectives:
(1) To study the effect of H+ ion concentrations and solvent ratio
on the degradation of target compounds,
(2) To study the degradation kinetics of endosulfan and lindane,
and
(3) To identify the intermediates and end-products of the
dechlorination reaction and elucidate the pathways.
Materials and Methodology
Source of Chemicals. The Mg0 granules (approximately 20
mesh), K2PdCl6 [hexachloropalladate (IV) dipotassium], endosul-
fan (6,7,8,9,10,10- hexa chloro- 1,5,5a,6,9,9a- hexahydro–6,9-
methano- 2,4,3- benzodioxathiepine-3-oxide), and lindane (c-
hexachlorocyclohexane) were purchased from Sigma-Aldrich
India Pvt. Ltd Chemical Company (India) and were .98% pure.
Acetone, cyclohexane, hydrochloric acid, and glacial acetic acid
were purchased from Merck Ltd. (Mumbai, India) and were of
analytical grade. No pre-treatment was performed with the
chemicals, and they were used as received. All the glassware
used was of A-grade.
Dechlorination Reaction Protocol. Dechlorination experi-
ments were conducted in a 4-mL reaction volume containing the
reaction phase of water-acetone (1:1, v/v) in the absence and the
presence of hydrochloric acid (0.1 N) or glacial acetic acid. A
stock solution of K2PdCl6 (1 mg/mL) was diluted into deionized
water to attain the required final concentrations (0.1 to 0.5
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mg/mL) in the reaction mixture. An initial concentration of 30 mg/L
(30 ppm) of endosulfan or lindane was added into reaction tubes
from a 1000-mg/L (1000-ppm) stock solution of each pesticide
prepared in acetone. Reactions were initiated by the addition of Mg0
granules (1 to 25 mg/mL). Instantaneous reduction of Pd+4 was
confirmed by the disappearance of a reddish color of the salt,
followed by the formation of palladized magnesium. Table 1 shows
the contents of the reaction mixtures for endosulfan and lindane
dechlorination. All reactions were conducted in quadruplicate under
atmospheric pressure with continuous shaking in a water bath
maintained at 130 rpm at 25uC. No precautions were taken to
exclude oxygen or reduce the redox potential of the reaction phase.
Entire reaction mixtures were sacrificed after 30 minutes of
reaction, extracted twice using cyclohexane (total 5 8 mL), and
0.2- or 1.0-mL volumes of the pooled cyclohexane extracts were
injected for gas chromatographic-electron capture detection (GC-
ECD) analyses.
Optimization of Solvent (Water–Acetone) Ratio for Endo-
sulfan and Lindane Dechlorination. The water–acetone ratio
for the dechlorination of endosulfan was optimized using a
reaction system consisting of K2PdCl6 (0.5 mg/mL) and Mg0
(10 mg/mL), while, in the case of lindane, the water–acetone ratio
was optimized using a reaction system containing K2PdCl6
(0.1 mg/mL) and Mg0 (4 mg/mL). The initial concentration of
both pesticides was 30 mg/L (30 ppm), and no acid was added to
change the pH of the system. In both cases, the water–acetone
ratios were varied from 1:1 to 19:1 (v/v), and a reaction time of
30 minutes was chosen to analyze the extent of disappearance of
each pesticide.
Kinetics of Endosulfan and Lindane Dechlorination Using
Mg0/K2PdCl6 in the Water–Acetone Phase. Kinetic studies
were conducted in the water–acetone (19:1, v/v) phase to
determine the rates and extent of dechlorination of 10-, 30-, and
50-mg/L (10-, 30-, and 50-ppm) initial concentrations of
endosulfan each as a function of (1) varying Mg0 (5, 7.5, and
10 mg/mL) concentrations at a fixed K2PdCl6 concentration
(0.5 mg/mL) and (2) varying K2PdCl6 concentrations (0.3, 0.4,
and 0.5 mg/mL) at a fixed concentration of Mg0 (5 mg/mL) to
establish the order of reaction and rate constant (kobs) values. In
the case of lindane, reactions were conducted at (1) varying
Mg0 (1, 2.5, and 4 mg/mL) concentrations at a fixed K2PdCl6
concentration (0.1 mg/mL) and (2) varying K2PdCl6 concentra-
tions (0.05, 0.075, and 0.10 mg/mL) at a fixed concentration
(4 mg/mL) of Mg0 with 30- and 50-mg/L (30- and 50-ppm) initial
concentrations of lindane. The corresponding control experiments
were conducted to determine the extent of the above-mentioned
pesticides degradation, if any, using K2PdCl6 or Mg0 alone under
the same conditions as the test samples. All reactions were
conducted in quadruplicate under atmospheric pressure with
continuous shaking in a water bath maintained at 130 rpm at 25uC.
No precautions were taken to exclude oxygen or reduce the redox
potential of the reaction phase. Entire reaction mixtures were
sacrificed after 30 minutes of reaction, extracted twice using
cyclohexane (total 8 mL), and a 0.2-mL volume of the pooled
cyclohexane extracts was analyzed for residual pesticides,
intermediates, and end-products using GC-ECD instrumentation.
Gas Chromatographic-Electron Capture Detection Analy-
ses. Extracted samples were analyzed using a gas chromato-
graph equipped with Ni63 electron capture detector (model
no 6890N, Agilent Technologies Inc., India). The column used
2 Cust # 10-11-2163
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Table 1—Dechlorination pattern of endosulfan and lindane (30 mg/L [30 ppm] each) with or without hydrochloric acid
or glacial acetic acid by varying concentrations of Mg0 and K2PdCl6; water: acetone = 1:1 v/v; reaction time =
30 minutes. Values that appear in bold italic font are the optimum values of Mg/Pd doses with % disappearance of ;
endosulfan and lindane.

Mg K2PdCl6 Glacial acetic 0.1 hydrochloric Disappearance

Serial number (mg/mL) (mg/mL) acid (50 mL/mL) acid (50 mL/mL) of pesticides (%)

Endosulfan (30-mg/L [30-ppm]initial concentration)

1 5.0 0.1 * * 30.75
2 5.0 0.1 Added * 27.47
3 5.0 0.1 * Added 31.80
4 10.0 0.2 * * 62.67
5 10.0 0.2 Added * 58.5
6 10.0 0.2 * Added 66.33
7 25.0 0.5 * * 99.51
8 25.0 0.5 Added * 88.6
9 25.0 0.5 * Added 98.68
10 25.0 0.2 * * 44.8
11 25.0 0.2 Added * 58.21
12 25.0 0.2 * Added 79.99
13 10.0 0.5 * * 99.46
14 10.0 0.5 Added * 92.05
15 10.0 0.5 * added 89.95
Lindane (30-mg/L [30-ppm] initial concentration)
1 5.0 0.1 * * 99.0
2 4.0 0.1 * * 99.5
3 2.5 0.1 * * 98.8
4 2.0 0.1 * * 55.0
5 2.0 0.1 Added * 97.0
6 1.0 0.1 * * 36.4
7 5.0 0.075 * * 44.6
8 5.0 0.050 * * 52.4
9 5.0 0.040 * * 55.56
10 5.0 0.020 * * 41.34

* Not added.

was an HP-5 column (320-mm internal diameter, 0.25-mM film
thickness, and 30-m length, Agilent Technologies Inc.). A sample
volume of 0.2 mL was injected to the gas chromatograph using an
auto sampler. Injection was performed in splitless mode, using
nitrogen as a carrier gas (2-mL/min flowrate). The following oven
temperature programming was used: initial oven temperature of
150uC with a hold time of 2 minutes, then ramped to 200uC at
6uC/min with a hold time of 2 minutes, and again ramped to
250uC at 10uC/min with a hold time of 2 minutes. Injector and
detector temperatures were set at 200 and 290uC, respectively.
The residual concentrations of endosulfan and lindane, partially
chlorinated intermediates, and end-products were quantified from
peak areas obtained through automated integration and also by
comparison with known concentrations of pure standard com-
pounds.
Gas Chromatographic–Mass Spectrometric Analyses. Gas
chromatography-mass spectrometry (GC-MS) analyses were
carried out using TRACE GC Ultra (Thermo Scientific, India)
equipped with a mass spectrometer (model DSQII, Thermo
Scientific). The column used for GC-MS analysis was a TR-5
column (0.25-mm internal diameter, 0.25-mM film thickness, and
30-m length, Thermo Scientific). A volume of approximately 1 mL
of samples was injected for analyses. Hydrogen (H2) was used as
carrier gas. The temperature programming used was as follows:
initial oven temperature of 40uC with a hold time of 1 minute,
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ramped to 53uC at 1uC/min with a hold time of 1 minute, again
ramped to 60uC at 10uC/min with a hold time of 1 minute, and
finally ramped to 250uC with a hold time of 1 minute. Injector and
detector temperatures were set at 200 and 300uC, respectively.
The mass spectral data coupled with the systematic reduction in
the retention times of dechlorinated products (resulting from a loss
of chlorine atoms) allowed identification of the intermediates and
end-products with reasonable certainty. The Wiley Registry (8e
Mass Spectral Library) was used to identify the intermediate and
end-products.
Result and Discussion
Hydrogen Ion Concentration Optimization. Table 1 de-
picts the extent of endosulfan and lindane disappearance using
varying Mg0/K2PdCl6 doses in the presence or absence of acid.
As seen in Table 1, Mg0/K2PdCl6 (5/0.1 mg/mL) degraded only
30.75% of the 30-mg/L (30-ppm) initial concentration of
endosulfan within 30 minutes of reaction in the absence of any
acid. Further addition of hydrochloric acid (0.1 N, 50 mL/mL) or
glacial acetic acid (50 mL/mL) did not show any significant
decrease of the 30-mg/L (30-ppm) initial concentration of
endosulfan within 30 minutes (27.47 and 31.80% removal,
respectively). In the case of the 10/0.2-mg/mL dose of Mg0/
K2PdCl6, 62.67, 58.5, and 66.33% removal of endosulfan (30-mg/L
[30-ppm] initial concentration) was observed in the absence of

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Aginhotri et al.
any acid, in the presence of glacial acetic acid (50 mL/mL), and in
the presence of hydrochloric acid (0.1 N, 50 mL/mL), respectively,
within 30 minutes of reaction. A higher dose of Mg0/K2PdCl6
(25/0.5 mg/mL) demonstrated approximately 99% disappearance
of endosulfan (30-mg/L [30-ppm] initial concentration) in the
absence of acid or in the presence of hydrochloric acid (0.1 N,
50 mL/mL), while the addition of glacial acetic acid (50 mL/mL)
resulted in 88% disappearance of endosulfan within 30 minutes of
reaction. Further, endosulfan removal of 99, 92, and 89% was
observed with 10/0.5 mg/mL Mg0/K2PdCl6 dose in the absence of
any acid, in the presence of glacial acetic acid (50 mL/mL), and in
the presence of hydrochloric acid (0.1 N, 50 mL/mL), respectively,
within 30 minutes of reaction. Overall, a 2-fold increase in
endosulfan removal (approximately 30 to 60%) was noticed with
doubling the Mg0/K2PdCl6 dose (5/0.1 to 10/0.2 mg/mL) with or
without acid. A 5-fold increase in Mg0/K2PdCl6 doses (5/0.1 to 25/
0.5 mg/mL) resulted in maximum degradation of endosulfan
(approximately 30 to 99%).
Table 1 also shows the lindane disappearance pattern in the
absence or presence of acid with varying doses of Mg0/K2PdCl6.
All of the tested doses of Mg0/K2PdCl6 (5/0.1, 4/0.1, and
2.5/0.1 mg/mL) degraded approximately 99% of the 30-mg/L
[30-ppm] initial concentration of lindane in the absence of any
acid within 30 minutes of reaction. On reducing the K2PdCl6 dose
(0.1 to 0.075–0.02 mg/mL) with fixed Mg0 (5.0 mg/mL),
endosulfan removal was lowered to approximately 50% in the
absence of any acid within 30 minutes of reaction. In the case of a
Mg0/ K2PdCl6 dose of 2/0.1 mg/mL, the addition of glacial acetic
acid (50 mL/mL) enhanced the lindane degradation to 97%
compared with 36.4% in the absence of acid at same dose of
K2PdCl6 within 30 minutes of reaction time.
Our results are in accordance with earlier reports, where the
extents of dechlorination reaction were found to be significantly
higher, even in the absence of any acid. Gautam and Sumathi
(2007) conducted a study for DDT degradation with a Mg0/Pd+4
bimetallic system in the presence or absence of acid, and their
findings revealed that the introduction of acid can enhance the rate
of reactions by providing extra protons to the reaction mixture and
also reduces metal’s passivation by enhancing the solubility of
metal hydride. Zinovyev et al. (2004) conducted a lindane
degradation study in the presence and absence of acid using a
5% Pd/C system. Their results revealed that 90% removal of
lindane was achieved in 100 minutes of reaction in the presence of
acid (HCl, 1.16 M), while .99% lindane removal was observed
within 50 minutes in the absence of any acid, indicating higher
lindane degradation in the absence of acid. Our study supports the
observation by Zinovyev et al. (2004) and is contrary to Gautam
and Sumathi (2007). The possible reason of lower degradation in
the presence of acid may be the result of excessive hydrogen
generation and fast corrosion of zerovalent metal for both
endosulfan and lindane dechlorination. Based on the results
discussed above, Mg0/K2PdCl6 doses of 10/0.5 and 4/0.1 mg/mL
were chosen as optimum for endosulfan and lindane dechlorina-
tion in the absence of any acid.
Water:Acetone Ratio Optimization. The water:acetone ratio
optimization study was conducted to probe the influence of
acetone as a solubilizing agent on endosulfan and lindane
degradation with the above-mentioned optimized Mg0/K2PdCl6
doses (10/0.5 and 4/0.1 mg/mL, respectively, for endosulfan and
lindane) in the absence of any acid. An approximately 95%
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decrease of the 30-mg/L [30-ppm] initial concentration of
endosulfan was achieved with different water:acetone ratios (1:1
to 19:1, v/v) with a negligible regular decrease in the percent
degradation of endosulfan observed from 99 to 95.8% when the
water:acetone ratio was decreased from 1:1 to 19:1. Further,
maximum endosulfan degradation (99.99%) was achieved at a 2:1
(v/v) water:acetone ratio ,while a 9:1 (v/v) water:acetone ratio
resulted in minimum degradation (95.99%). In the case of lindane,
the water:acetone ratios of 1:1, 2:1, and 4:1 (v/v) degraded
approximately 99.99% of the 30-mg/L [30-ppm] initial concen-
tration of lindane. Only a slight decrease in lindane disappearance
(98 and 97%) was observed with water:acetone ratios of 9:1 and
19:1 (v/v), respectively.
The slight decrease in endosulfan and lindane disappearances
with decreasing acetone content in the reaction mixture may be the
result of an insufficient amount of acetone to dissolve these
pesticides in water. Previous reports also suggest that the suitable
solvent is required to enhance the rate of degradation of chlorinated
pesticides by accelerating the mass transfer. Patel and Sumathi
(2008) used various co-solvents (acetone, methanol, ethanol, 1-
propenol and no solvent) at 1% (v/v) for 10 mg/L pentachlorophe-
nol (PCP) degradation. Maximum removal of PCP was achieved in
the presence of acetone using Mg/Ag and Mg/Pd systems with
1 hour of reaction time. Gautam and Sumathi (2007) observed a
significant decrease in degradation of DDT using Mg/Pd with a
decreasing acetone ratio. These researchers concluded that the use
of acetone as a co-solvent could influence the dechlorination rate of
reaction as it improves the solubility of the pesticides and thus
enhances the rate of mass transfer. Acetone also enhances
nucleophilic substitution by leaving the anionic groups unsolvated.
Thus, our study affirms a previous observation reported by
Gautam and Sumathi (2007). From the environmental and
economical point-of-view, a water:acetone ratio of 19:1 (v/v)
was selected as optimum for a further dechlorination kinetic study
of both compounds.
Kinetics Studies of Endosulfan and Lindane Dechlorination
Using the Mg0/K2PdCl6 System with a Water:Acetone Ratio of
19:1 in the Absence of Acid. Figures 1 and 2 depict time-
course profiles of endosulfan (30- and 50-mg/L [30- and 50-ppm]
initial concentration, respectively) degradation with various
Mg0/K2PdCl6 doses (5/0.3, 5/0.4, 5/0.5, 7.5/0.5 and 10/0.5 mg/mL)
in the absence of any acid and in a 19:1 (v/v) water: acetone reac-
tion mixture.
Figure 1 shows that approximately 96% removal of endosulfan
was achieved within 10 minutes of reaction time with a 5/0.5-
mg/mL Mg0/K2PdCl6 dose. When the Mg0/K2PdCl6 dose was
increased to 7.5/0.5 mg/mL, 66% and approximately 99.99%
removal of the 30-mg/L (30-ppm) initial concentration of
endosulfan was observed within 10 and 30 minutes of reaction
time, respectively. When the Mg0/K2PdCl6 dose was increased
further to 10/0.5 mg/mL, endosulfan degradation reduced to 78
and 88% within 10 and 20 minutes of reaction, respectively.
Approximately 92 and 83% removal of endosulfan (30-mg/L [30-
ppm] initial concentration) was observed at 5/0.4- and 5/0.3-
mg/mL doses of Mg0/ K2PdCl6, respectively, within 15 minutes of
reaction time.
As shown in Figure 2, approximately 97% removal of
endosulfan (50-mg/L [50-ppm] initial concentration) was
achieved within 15 minutes of reaction time, with a 5/0.5-
mg/mL dose of Mg0/K2PdCl6. At a Mg0/K2PdCl6 dose of 7.5/0.5
4 Cust # 10-11-2163
 Aginhotri et al.

Figure 1—Kinetic profiles for endosulfan (initial concentration = 30 mg/L [30 ppm]) dechlorination using various
concentrations of Mg0 and K2PdCl6 (as indicated in the figure) with 19:1 (v/v) water:acetone phases in the absence
of acid.

Figure 2—Kinetic profiles for endosulfan (initial concentration = 50 mg/L [50 ppm]) dechlorination using various
concentrations of Mg0 and K2PdCl6 (as indicated in the figure) with 19:1 (v/v) water:acetone phases in the absence
of acid.
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Aginhotri et al.
Figure 3—Schematic diagram of endosulfan degradation pathway using the Mg0/Pd+4 bimetallic system.
mg/mL, 84% and approximately 94% removal of a 50-mg/L (50-
ppm) initial concentration of endosulfan was observed within 15
and 20 minutes of reaction time, respectively. When the Mg0/
K2PdCl6 dose was increased further to 10/0.5 mg/mL, endosulfan
degradation reduced to 80 and 86% within 15 and 20 minutes of
reaction, respectively. Approximately 89% removal of endosulfan
(50-mg/L [50-ppm] initial concentration) was observed at 5/0.4
mg/mL within 15 minutes of reaction time. The minimum de-
gradation of endosulfan (36%) was observed at a 5/0.3-mg/mL
dose of Mg0/K2PdCl6 within 10 minutes of reaction, which
increased to 88% within 1 hour of reaction time.
The set of data presented in Figures 1 and 2 could be fitted into
exponential curves, thereby suggesting that endosulfan degrada-
tion follows a second-order reaction. The observed rate constant
(kobs’) values for the set of kinetics performed were calculated.
Maximum rate constant values (0.2523 ppm21min21 and
0.334 ppm21min21 for 30- and 50-ppm initial concentrations of
endosulfan, respectively) were achieved with a 5/0.5 mg/mL dose
of Mg0/K2PdCl6. It can be stated clearly that rate constant values
reduce with a change in Mg0/K2PdCl6 concentration from 5/0.5 to
7.5/0.5 mg/mL (0.2523 to 0.1379 ppm21min21 for 30-mg/L [30-
ppm] endosulfan and 0.334 to 0.1528 ppm21min21 for 50-mg/L
[50-ppm] endosulfan concentration). A 5/0.3-mg/mL dose of Mg0/
K2PdCl6 resulted in minimum rate constant values (0.0351 and
0.1135 ppm21min21) for 30- and 50-mg/L (30- and 50-ppm)
endosulfan concentrations, respectively. Further, optimum degra-
dation and rate constant values were achieved at a Mg0/K2PdCl6
dose of 5/0.5 mg/mL.
No partially dechlorinated intermediates/end-products of endo-
sulfan degradation appeared in the GC-ECD profiles. Hence, the
samples were analyzed using GC-MS to identify the intermediates
formed, if any, and end-products of endosulfan degradation. A
dominating peak appeared at retention time of 4.98 minutes.
Based on the molecular ion fragmentation pattern, this peak
eluting at 4.98 minutes was identified as Bicyclo [2,2,1] hepta 2–5
diene, using the Wiley Registry 8e Library. The structure of this
compound was similar to dechlorinated endosulfan, and this might
have formed by the removal of all six chlorine atoms, two carbon
atoms, three oxygen atoms, and one sulfur atom during the
dechlorination reaction. The absence of any other partially
dechlorinated intermediates suggests that the nascent hydrogen
attacks on all six chlorine atoms simultaneously. Based on the
GC-MS analysis, the proposed mechanism of endosulfan degra-
dation by the Mg0/K2PdCl6 system is shown in Figure 3.
Figures 4 and 5 depict the time-course profiles of lindane (30-
and 50-mg/L [30- and 50-ppm] initial concentration, respective-
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ly) degradation with various Mg0/K2PdCl6 doses (4/0.1, 2.5/0.1,
1/0.1, 4/0.075, and 4/0.05 mg/mL) in the absence of any acid
and with the 19:1 (v/v) water:acetone reaction mixture. Figure 4
shows that approximately 99% removal of lindane (30-mg/L [30-
ppm] initial concentration) was achieved within 15 minutes of
reaction time with a 4/0.1-mg/mL Mg0/K2PdCl6 dose. When the
Mg0/K2PdCl6 dose was reduced to 2.5/0.1 mg/mL, 97% removal
of the 30-mg/L (30-ppm) initial concentration of lindane was
observed within 15 minutes of reaction time. When the Mg0/
K2PdCl6 dose was reduced further to 1/0.1 mg/mL, only 17 and
38% removal of lindane was achieved within 15 and 30 minutes
of reaction, respectively. At a 4/0.075-mg/mL dose of Mg0/
K2PdCl6, lindane removal further reduced to 54 and 78% (30-
mg/L [30-ppm] initial concentration) within 15 and 30 minutes
of reaction time, respectively. Approximately 58 and 67%
disappearance of lindane was achieved at a 4/0.05-mg/mL dose
of Mg0/ K2PdCl6 within 15 and 20 minutes of reaction time,
respectively.
As shown in Figure 5, more than 94% lindane (50-mg/L [50-
ppm] initial concentration) disappeared when the reaction was
conducted with a 4/0.1-mg/mL Mg0/K2PdCl6 dose within
15 minutes of reaction time. When the Mg0/K2PdCl6 dose was
reduced to 2.5/0.1-mg/mL, 95.5% removal of the 50-mg/L (50-
ppm) initial concentration of lindane was observed within
30 minutes of reaction time. When the Mg0/K2PdCl6 dose was
reduced further to 1/0.1 mg/mL, only 42 and 62% removal of
lindane was achieved within 15 and 30 minutes of reaction time,
respectively. With a 4/0.075-mg/mL dose of Mg0/ K2PdCl6, <
lindane removal reduced to 66 and 74% (50-mg/L [50-ppm] initial
concentration) within 15 and 30 minutes of reaction time,
respectively. Approximately 56 and 75% disappearance of lindane
was achieved with a 4/0.05-mg/mL dose of Mg0/K2PdCl6 within
15 and 30 minutes of reaction time, respectively.
The set of data presented in Figures 4 and 5 could be fitted into
exponential curves, thereby suggesting that lindane degradation
follows a second-order reaction. The observed rate constant values
reduced from 0.331 to 0.0168 ppm21min21 with a reduced Mg0/
K2PdCl6 dose from 4/0.1 to 1/0.1 mg/mL when the reaction was
conducted with a 30-mg/L (30-ppm) initial concentration of
lindane. Similarly, in the case of 50-mg/L (50-ppm) lindane, rate
constant values decreased quickly. Further, rate constant values
were found to be optimum for a 4/0.1-mg/mL dose of Mg0/
K2PdCl6 (0.3311 and 0.206 ppm21min21, respectively, for 30-
and 50-mg/L [30- and 50-ppm] initial concentrations of lindane).
Similar to the case of endosulfan degradation, no partially
dechlorinated intermediates/end-products of endosulfan degrada-
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 Aginhotri et al.

Figure 4—Kinetic profiles for lindane (initial concentration = 30 mg/L [30 ppm]) dechlorination using various
concentrations of Mg0 and K2PdCl6 (as indicated in the figure) with a 19:1 (v/v) water:acetone phase in the absence
of acid.

Figure 5—Kinetic profiles for lindane (initial concentration = 50 mg/L [50 ppm]) dechlorination using various
concentrations of Mg0 and K2PdCl6 (as indicated in the figure) with a 19:1 (v/v) water:acetone phase in the absence
of acid.
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 Aginhotri et al.
Figure 6—Schematic diagram of the lindane degradation
pathway using the Mg0/Pd + 4 bimetallic system.
tion appeared in the GC-ECD profiles. Hence, the samples were
analyzed using GC-MS to identify the intermediates formed, if
any, and also the end-products of endosulfan degradation. A
dominating peak appeared at a retention time of 3.0 minutes.
Based on the molecular ion fragmentation pattern, this peak
eluting at 3.0 minutes was identified as benzene using the Wiley
Registry 8e Library. The structure of this compound is similar to
dechlorinated lindane, and this might have formed by the removal
of all six chlorine atoms during the dechlorination reaction. The
absence of any other partially dechlorinated intermediates
suggests that produced nascent hydrogen attacks on all six
chlorine atoms simultaneously. Based on the GC-MS analysis, the
proposed mechanism of lindane degradation by the Mg0/K2PdCl6
system is shown in Figure 6.
Similar observations have been reported by various researchers.
Gautam and Sumathi (2007) reported a second-order degradation
reaction of DDT using a Mg/Pd bimetallic system. Patel and
Sumathi (2008) also reported second-order degradation reactions
for the degradation of PCP using Mg/Pd and Mg/Ag systems.
Engelmann et al. (2001) and Gautam and Sumathi (2007)
conducted studies with the Mg0/Pd+4 system using water:acetone
as a solvent medium for DDT degradation and reported the
complete removal of the chlorine atoms in an acidic medium. The
GC-MS analysis revealed that DDT was degraded to its
hydrocarbon backbone, named diphenyl ethane. They suggested
simultaneous removal of chlorine atoms during the dechlorination
process.
Conclusions
The following points have emerged from the present study:
(1) The Mg0/Pd+4 bimetallic system is an efficient system for the
complete dechlorination of endosulfan and lindane solubilized
by the addition of acetone in the aqueous phase.
(2) The addition of acetone in a reaction mixture plays an
important role in the dechlorination reaction by enhancing the
solubility and thereby the mass transfer of target compounds.
(3) The dechlorination reaction proceeds at ambient temperature
and pressure. No precautions are needed to exclude oxygen or
reduce redox potential of the reaction.
(4) The dechlorination reactions of endosulfan and lindane follow
second-order kinetics and the rate of reaction.
= (5) GC-MS analyses revealed that the Mg0/ Pd+4 system is
efficient in complete dechlorination of endosulfan and
lindane, converting them into their hydrocarbon skeletons,
namely Bicyclo [2,2,1] hepta 2–5 diene and benzene,
respectively.
Thus, the Mg0/Pd+4 bimetallic system could be a promising
option for the remediation of chlorinated compounds. There is a
huge potential for the further study and possible application of the
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Water Environment Research waer-83-08-24.3d 13/7/11 11:29:16
Mg0/Pd+4 bimetallic system for the remediation of contaminated
soils, sediments, and groundwater. Further, there is need to study
the reusable capacity of palladium, as it could decrease the cost of
the Mg0/Pd+4 bimetallic process. It is also worthwhile to evaluate
Mg0/Pd+4 reactive system for designing indigenous permeable
barriers or reactors for contaminated water, groundwater, and
wastewater effluent sites.
Credits
The authors sincerely thank the Department of Science and
Technology, Government of India, for providing financial
assistance to conduct the present study. The authors also
acknowledge the Spectroscopy and Analytical Test Facility Lab,
Indian Institute of Science (Bangalore, India), for allowing use
of their GC-MS facility. The authors also thank Asfiya Begum
and K. Johnson of The Energy and Resources Institute,
Bangalore, Karnataka, India, for their assistance and support
during the study.
Submitted for publication November 18, 2010; accepted for
publication February 2, 2011.
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