Research Article
Effect of mixing on reductive dechlorination of
persistent organic pollutants by Fe/Pd nanoparticles
Abdellatif Moujahid,1 John J. Bang,2 Fei Yan1
1
Department of Chemistry and
Biochemistry, North Carolina Central
University, Durham, North Carolina
2
Department of Environmental, Earth
and Geospatial Sciences, North Carolina
Central University, Durham, North Carolina
Received 26 June 2018; Revised 22 July 2018;
Accepted 24 September 2018
U.S. National Science Foundation, Grant/
Award Number: 1831133 and DMR-
1523617; Department of Education, Grant/
Award Number: P120A150022; North
Carolina Space Grant Consortium
Correspondence to: Fei Yan, Department
of Chemistry and Biochemistry, North
Carolina Central University, Durham, NC.
Email: fyan@nccu.edu
DOI: 10.1002/wer.1018
© 2018 Water Environment Federation
Water Environment Research • 1–10, 2019
• Abstract
Herein, we report the comparison of two different mixing methods for reductive
dechlorination of gamma-­ hexachlorocyclohexane (γ-­ HCH), aldrin, and p, p’-­
dichlorodiphenyl-­trichloroethane (p, p’-­DDT), using iron/palladium (Fe/Pd) bimetal-
lic nanoparticles. A noticeable enhancement of the reaction rate was found when the
reductive dechlorination reaction was carried out in an ultrasound bath as compared
with a platform shaker. These enhancements could be attributed to (a) the continuous
cleaning and chemical activation of the surfaces of nanoscale Fe/Pd bimetallic nano-
particles by the combined chemical and physical effects of acoustic cavitation; and (b)
the accelerated mass transport rates of target POPs to the surfaces of the Fe/Pd nano-
particles. Finally, the degradation intermediates and final products were determined
by gas chromatography/mass spectrometry (GC/MS) analysis and the plausible degra-
dation pathways for γ-­HCH, aldrin, and p, p’-­DDT by Fe/Pd bimetallic nanoparticles
were proposed.   © 2018 Water Environment Federation
• Practitioner points
• Exposure to POPs is a resilient global environmental and health issue.
• Fe/Pd bimetallic nanoparticles demonstrated > 90 % removal of POPs in the first 30
minutes of the reaction via ultrasonic mixing.
• GC-MS analyses provided verification of POPs degradation intermediates and final
products.
• Key words
bimetallic; dechlorination; degradation pathways; persistent organic pollutants;
ultrasound
Introduction
Persistent organic pollutants (POPs) are a group of organic compounds that are
extremely stable and persistent against chemical or biological degradation in the
environment for an extended period of time (Ashraf, 2017; El-­Shahawi, Hamza,
Bashammakh, & Al-­Saggaf, 2010; Katsoyiannis & Samara, 2005; Pawełczyk, 2013).
Several lines of evidence pointed that POPs pose adverse effects on living organ-
isms via endocrine disruption (Basile et al., 2011). They are also characterized by
long-­range transport because they have been detected far from their application
areas through the atmosphere. This is due to the ability of POPs to volatilize from
environmental matrices under ambient conditions, so they travel for a long distance
before their deposition in the environment again (Fiedler, 2003). In recent years,
the demand for effective methods for the complete degradation of POPs in all envi-
ronmental matrices became one of the important research topics, which attracted
enormous research attention around the world. Various methods for reductive dechlo-
rination of p, p’-­dichlorodiphenyl-­trichloroethane (p, p’-­DDT), aldrin, and gamma-­
hexachlorocyclohexane (γ-­HCH) have been developed and evaluated (El-­Temsah,
Sevcu, Bobcikova, Cernik, & Joner, 2016; Erick et al., 2002; Hara, Ito, Suto, Inoue, &
Chida, 2005; Joo & Zhao, 2008; Thangavadivel, Megharaj, Smart, Lesniewski, & Naidu,
2009; Tian, Li, Mu, Li, & Hao, 2009), but most of them suffer some limitations such as
Research Article
long treatment time and high cost, and a majority of the degra-
dation pathways remain unclear. Among which, reductive deg-
radation of POPs by bimetallic nanoparticles has emerged as
one of the most promising techniques that made its way from
the laboratory bench-­scale testing to the field application (Rani,
Shanker, & Jassal, 2017; Yang et al., 2010; Zhang et al., 2018).
The bimetallic nanoparticle-­assisted degradation of POPs has
been found supplementary and complementary to the conven-
tional methods such as high-­temperature incineration, which
results in incomplete degradation of POPs with highly toxic by-­
products that are more harmful than the parent pollutants. The
bimetallic nanoparticle approach offers a more cost-­effective
alternative to bioremediation of POPs, which requires the
growth of special bacteria as well as special environmental con-
ditions for the remediation process to take place; however, the
bioremediation of POPs is still an incomplete process (Varjani,
Gnansounou, & Pandey, 2017). It also provides a superior alter-
native to other remediation techniques such as photochemical
and adsorption (Yamada, Naito, Funakawa, Nakai, & Hosomi,
2008).
Ultrasound is a mechanical wave with periodic vibra-
tions of particles in a continuous, elastic medium at frequen-
cies equal to or greater than 20 kHz. In liquids, its velocity
of about 1000–1,600 m/s translates into the wavelength range
from micrometers to centimeters. The interaction of ultra-
sound with bulk liquid is accompanied by the quite unique
phenomenon of cavitation that leads to an enormous con-
centration and conversion of the diffuse sound energy.
Historically, cavitation has been classified into two types,
noninertial and inertial. Noninertial cavitation bubbles oscil-
late about an equilibrium radius and often persist for many
acoustic cycles. As a result of these oscillations, streaming
of surrounding liquid occurs and mechanical stresses create
mixing of the medium. Inertial cavities are gas bubbles that
grow to near resonance size and may expand to a maximum
before violently collapsing. The temperature and pressure
experienced by the material contained within the imploding
cavities can reach values in excess of 5,000 K and 800 atm.
These extreme conditions may induce a multitude of chemical
Table 1.  Physicochemical properties of representative persistent organic pollutants
COMPOUND CHEMICAL MOLECULAR
NAME STRUCTURE FORMULA
γ-­HCH C6H6Cl6
Aldrin C12H8Cl6
p-­p’-­DDT C14H9Cl5
2 Moujahid et al.
reactions within and surrounding the bubble, including a con-
centration of energy sufficient to generate light, an emission
known as sonoluminescence, and subsequently leading to the
production of reactive oxygen species (Rosenthal, Sostaric, &
Riesz, 2004).
In this study, three representative POPs were chosen based
on their persistency in the environment and their solubility in
water, to evaluate how the difference in those physicochemical
properties affects their degradation efficacy in water and soil,
under similar conditions. As shown in Table 1, γ-­HCH has the
highest water solubility and the lowest n-­octanol-­water parti-
tion coefficient in comparison with aldrin and p, p’-­DDT, which
explains the high persistency and bioaccumulation of aldrin
and p, p’-­DDT over the γ-­HCH in water and soil. Two meth-
ods of mixing namely ultrasound irradiation and mechanical
shaking were selected to examine their effectiveness on the
reductive dechlorination of POPs in the presence of Fe/Pd
bimetallic nanoparticles. We demonstrated the rate of reduc-
tive dechlorination of POPs can be significantly enhanced by
ultrasound bath mixing. The enhancement can be attributed to
the continuous cleaning and activation of the surfaces of Fe/Pd
bimetallic nanoparticles. Moreover, faster mass transport rates
resulting from the hydrodynamic cavitation also contribute to
the enhancement.
Experimental
Chemicals
Lindane (γ-­HCH) and p, p’-­DDT were obtained from Ultra
Scientific, USA. Aldrin, with a purity of 97.9%, was obtained
from Chem Service, Inc. (West Chester, Pennsylvania). All pes-
ticide grade organic solvents such as absolute ethanol, acetone,
dichloromethane, and hexane and other chemicals including
ferrous sulfate FeSO4·7H2O, sodium borohydride NaBH4, and
palladium acetate Pd (COOCH3)2 were purchased from Fisher
Scientific Inc. All solutions were prepared with high purity
deionized water (resistivity ≥18 MΩ·cm) from a Picopure®2
ultrapure water purification system (Hydro, Inc., Durham, NC).
MOLECULAR WATER SOLUBILITY
WEIGHT (MG/L), 25°C LOG KOW
290.83 7.3 3.72
364.92 0.027 6.5
354.49 0.0055 6.91
 Research Article

Synthesis of Fe/Pd bimetallic nanoparticles
The synthesis of Fe/Pd bimetallic nanoparticles was carried out
following a published procedure (Mukherjee, Kumar, Sinha,
Lama, & Saha, 2015) with a slight modification: The synthesis
was conducted under a continuous stream of nitrogen gas to
avoid any oxidation of iron. Specifically, an equal volume of
0.28 M FeSO4 solution and 0.56 M NaBH4 solution was mixed
dropwise under the fume hood at ambient conditions. The as-­
prepared Fe/Pd nanoparticles were washed three times with
water and then three times with ethanol, followed by a cen-
trifugation for 5 min each time at 4,500 rpm. Subsequently, the
washed Fe/Pd nanoparticles were soaked in a 1% (w/w) solu-
tion of palladium acetate in ethanol, centrifuged to separate
the Fe/Pd bimetallic particles from the liquid phase, and then
underwent the last wash cycle with ethanol before the bime-
tallic particles were dried in vacuum oven at 50°C overnight.
Lastly, the Fe/Pd nanoparticles were stored in closed glass vials
and flushed with nitrogen gas and then kept in the freezer until
the use for experiments.
Characterization of Fe/Pd nanoparticles
The morphology of Fe/Pd nanoparticles was examined by
high-­resolution transmission electron microscopy (HR-­TEM,
JEM-­2010F).
Degradation of γ-­HCH, aldrin, and p, p-DDT with Fe/
Pd bimetallic nanoparticles in water
In four 15-­ml amber glass vials lined up with a Teflon cap, a
ratio of 4:1 v/v of water and an acetone solution of γ-­HCH,
aldrin, and p, p΄ DDT were added, each with an initial con-
centration of 10 mg/L, and then the pH of the solution was
adjusted to 2.5 by adding four drops of glacial acetic acid. The
Fe/Pd bimetallic nanoparticles were added to each bottle with a
loading dose of 0.5 g/L.
A batch of vials was mixed with the assistance of an ultra-
sound bath, and another batch was mixed using a platform
shaker for a period of time ranging from 1 to 60 min. A control
sample was prepared under the same conditions without the
bimetallic nanoparticles during the same reaction time frame.
After each reaction time completed, the residual POPs and
its metabolites were extracted with 5 ml of hexane by vortex-­
mixing for 2 min, and then the vial content was set aside for
10 min to allow the water phase and hexane phase to separate.
The organic phase was pipetted to a 1.5-­ml amber GC autosam-
pler vial for further analysis.
nitrogen at a rate of 1.2 ml/min and 15 ml/min, respectively.
The total run time for this method was 10 min. The instru-
ment was first calibrated with five calibration points rang-
ing from 0.04 ppb to 10 ppm with a correlation coefficient
R2 = 0.98.
Analysis of γ-­HCH, aldrin, and p, p’-­DDT by GC/MS
The dechlorination reaction intermediates and by-­products
were analyzed using the Shimadzu GC/MS QP-­ 2010,
equipped with XTI-­5 (5% diphenyl, 95% dimethylpolysilox-
ane) column (30 m, 0.25 mm ID, and 0.25 μm df). Helium
(purity 99.99%) was used as a carrier gas at a constant lin-
ear velocity of 47.2 cm/sec (column flow of 1.69 ml/min).
The initial oven temperature was set at 50°C for 2 min, fol-
lowed by a linear ramp to 180°C at a rate of 25°C/min (held
for 1 min). A final ramp to 250°C was performed at a rate
of 20°C/min with a hold time of 8.30 min. A split–splitless
injector was set at 250°C, and an injection of 1 μl was per-
formed in the splitless mode. The transfer line temperature
was set at 290°C and the source temperature at 220°C. The
mass spectrometer was operated in the electron impact mode
(70 eV).
Results and Discussion
Characterization of Fe/Pd bimetallic nanoparticles
The morphology of Fe/Pd nanoparticles as synthesized was
examined with high-­resolution transmission electron micros-
copy. As demonstrated in Figure 1, the magnetic and electronic
interactions between iron and palladium formed a connected
chain of spherical nanoparticles. The nanosize of the Fe/Pd
bimetallic nanoparticles formed is due to the difference in
molar ratio between iron and borohydride, in which the high

Analysis of γ-­HCH, aldrin, and p, p’-­DDT by GC-­ECD

The POP residuals after the dechlorination reactions were
analyzed by a Thermo Scientific Trace 1300-­ACI 300 Gas
Chromatograph equipped with an electron capture detec-
tor (ECD) and HP-­5 (5% diphenyl, 95% dimethylpolysilox-
ane) column with 0.32 mm thickness, 0.25 μm diameter,
and 30 m length. The oven program was set up at an initial
temperature of 150°C for 0.5 min and then ramped to 260°C
(20°C/min) held for 3 min. The injector temperature and
detector temperature were set at 280°C and 300°C, respec- Figure 1.  A TEM image of Fe/Pd bimetallic nanoparticles with a
tively. The carrier gas was helium and the makeup gas was scale bar of 500 nm.

Water Environment Research • 1–10, 2019 3

Research Article

molarity of borohydride accelerates the reduction rate of iron
which formed more zero-­valent iron nanoparticle nuclei with
high surface area.
Dechlorination of γ-­HCH, aldrin, and p, p’-­DDT
in water
The dechlorination of 10 mg/L POPs (γ-­HCH, aldrin, and p,
p’-­DDT) was conducted under the following conditions : (a)
US only control samples consisting of POP-­ contaminated
water mixed under ultrasound in the absence of Fe/Pd bime-
tallic nanoparticles, (b) Fe/Pd/mixing samples consisting of
POP-­contaminated water in the presence of Fe/Pd bimetallic
nanoparticles (with a loading of 0.5 g/L) mixed by a platform
shaker at 200 rpm, and (c) Fe/Pd/US samples consisting of
POP-­contaminated water in the presence of Fe/Pd bimetal-
lic nanoparticles (with a loading of 0.5 g/L) mixed using an

180
kHz Aldrin (A)
gamma-HCH
150 0 min US only control
DDT
1 min US only control
3 min US only control
5 min US only control
100

50

0
min
–20
4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00

160
150 kHz (B)
10 min US only control
Aldrin 20 min US only control
125 gamma-HCH 30 min US only control
45 min US only control DDT
100 60 min US only control

75
50
25

0
min
–20
4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00

Figure 2.  GC-­ECD profiles of γ-­HCH, aldrin, and p, p’-­DDT control/no Fe/Pd under US ([POP] = 10 mg/L). (a) 0, 1, 3, and 5 min, and (b) 10,
20, 30, 45, and 60 min.

Figure 3.  GC-­ECD profiles of γ-­HCH, aldrin, and p, p’-­DDT Fe/Pd mixing with a platform shaker, treated mixture ([POP] = 10 mg/L, [Fe/
Pd] = 0.5 g/L). (a) 0, 1, 3, and 5 min, and (b) 10, 20, 30, 45, and 60 min.

4 Moujahid et al.
 Research Article

160
150 kHz (A)
Aldrin
0 min Fe/Pd/US gamma-HCH
125 1 min Fe/Pd/US DDT
3 min Fe/Pd/US
5 min Fe/Pd/US
100

75

50

25

0
min
–20
4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00

120
kHz (B)
100 10 min Fe/Pd/US
20 min Fe/Pd/US
80 30 min Fe/Pd/US
45 min Fe/Pd/US
60 60 min Fe/Pd/US
gamma-HCH

40

Aldrin
20

DDT
0
min
–20
4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00

Figure 4.  GC-­ECD profiles of γ-­HCH, aldrin, and p, p’-­DDT Fe/Pd/US-­treated mixture ([POP] = 10 mg/L, [Fe/Pd] = 0.5 g/L). Top: 0, 1, 3, and
5 min, and bottom: 10, 20, 30, 45, and 60 min.

ultrasound bath (FS20H, 70 W, 42 KHz). Figures 2–4 demon-
strate the GC-­ECD profiles of γ-­HCH, aldrin, and p, p’-­DDT
under three aforementioned experimental conditions. A slight
decrease in the concentrations for all three POPs under study
(initial concentration of 10 mg/L each) was found during the
first 5 min of the ultrasonic mixing in the absence of Fe/Pd
bimetallic nanoparticles, the change became negligible from 10
to 60 min (Figure 2), suggesting the ultrasound bath was too
weak to cause any meaningful degradation of γ-­HCH, aldrin,
and p, p’-­DDT. POP-­contaminated water in the presence of Fe/
Pd bimetallic nanoparticles (with a loading of 0.5 g/L) mixed
by a platform shaker led to a slight decrease in the concentra-
tions for all three POPs during the first 5 min of the reaction;
however, aldrin was converted to another highly chlorinated
compound (which was later determined to be endrin) within
1 min of the mixing, and the conversion nearly completed
within 10 min of the reaction. The dechlorination of p, p’-­DDT
proceeded from that point on and did not complete even at
the end of the 60 min’ treatment (Figure 3). Amazingly, the
dechlorination of POP-­contaminated water (10 mg/L each)
in the presence of Fe/Pd bimetallic nanoparticles (with a load-
ing of 0.5 g/L) and mixed using an ultrasound bath accelerated
during the first few minutes of the mixing, and reached ~100%
within 10 min of the reaction (Figure 4).
Figure 5 demonstrates the degradation behavior of γ-­HCH
(10 mg/L). Under control condition (1), there was less than 5%
of γ-­HCH being degraded in the first 20 min of the mixing
and stayed constant after that, the small fluctuations among
different time points were possibly due to the slight variations

Aldrin
γ-HCH 1.1
1.1

0.8
0.8
Control (US only)
C/C0

0.5
Control (US only) Fe/Pd/Mixing
C/C0

0.5
Fe/Pd/Mixing
Fe/Pd/US
Fe/Pd/US 0.2
0.2

–0.1 –0.1
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (min) Time (min)

Figure 5.  Degradation of γ-­ HCH (10 mg/L) with Fe/Pd (loading Figure 6.  Degradation of aldrin (10 mg/L) with Fe/Pd (loading
0.5 g/L, 1 wt.% Pd), pH ≈ 2.5. 0.5 g/L, 1 wt.% Pd), pH ≈ 2.5.

Water Environment Research • 1–10, 2019 5

Research Article

1.1
DDT that in the absence of bimetallic nanoparticles the effect of
ultrasound alone on aldrin degradation could be negligible.
In the presence of bimetallic nanoparticles and by using a
0.8 platform shaker as mixing method (2), the concentration of
aldrin fluctuates as the reaction proceeded due to adsorption
Control (US only) and desorption of aldrin on the surface of Fe/Pd bimetallic
C/C0

0.5
Fe/Pd/Mixing
Fe/Pd/US
0.2
–0.1
0 10 20 30 40 50
Time (min)
Figure 7.  Degradation of p, p’-­DDT (10 mg/L) with Fe/Pd (loading
0.5 g/L, 1 wt.% Pd), pH ≈ 2.5.
of experimental conditions since individual vials were used for
each treatment. In the presence of Fe/Pd bimetallic nanoparti-
cles and by using a platform shaker as the mixing method (2),
the concentration of γ-­HCH remained constant in the first
15 min of the reaction and as the contact time increased the
target compound concentration started to drop slowly and
reached a 30% decrease by the end of the reaction time, which
proves the limitation of platform mixing in helping the deg-
radation process, but the uses of ultrasound bath as a mixing
method the removal rate of γ-­HCH reached approximately 90%
after 10 min and 100% within 30 min of the reaction, this could
be explained by the efficacy of ultrasound waves in increasing
the contact time between the target compound and NPs, which
helped the degradation process.
Figure 6 demonstrates the degradation behavior of aldrin
(10 mg/L). Under control condition (1), less than 10% of
aldrin was degraded after 60 min of the reaction, which proves
nanoparticles, but overall no degradation was observed. The
use of ultrasound bath as a mixing method (3) for the deg-
radation of aldrin in the presence of NPs reached more than
90% in the first 10 min and stayed constant after that as the
reaction proceeds, this could be explained by the efficacy of
60
ultrasound waves in increasing the contact time between the
target compound and NPs which helped dramatically the deg-
radation process.
Figure 7 demonstrates the degradation behavior of p, p’-­
DDT (10 mg/L). It is evident that under control condition (1),
˂10% of p, p’-­DDT was degraded in the first 30 min of the reac-
tion and then it started to fluctuate after that, which may be
due to the experimental conditions since individual vials were
used. In the presence of Fe/Pd bimetallic nanoparticles and by
using a platform shaker for mixing, the concentration of p, p’-­
DDT started fluctuating during the first 30 min of the reac-
tion which is due to its adsorption and desorption by Fe/Pd
nanoparticles, and then the concentration of p, p’-­DDT started
dropping for the remainder of the reaction period until it
reached 30% after 60 min, suggesting the limited effect of plat-
form mixing on the degradation process of p, p’-­DDT. Fe/Pd
bimetallic nanoparticles rapidly degraded p, p’-­DDT with an
ultrasound bath mixing and the process reached 100% removal
after 10 min, and this could be explained by the efficacy of
ultrasound waves in increasing the contact time between the
target compound and NPs which helped dramatically the deg-
radation process.

Figure 8.  Proposed mechanism of reductive dechlorination of POPs (using DDT as an example) with Fe/Pd bimetallic nanoparticles.

6 Moujahid et al.
 Research Article

(x10,000,000)
(x10,000,000)
8.0

7.5 7.0

6.0

5.0

4.0

3.0

2.0
C
5.0 1.0

12.00 12.25 12.50 12.75 13.00

Black: 0 min
B Pink: 15 min
Blue: 30 min
Brown: 45 min
2.5 Green: 60 min
A

0.0
5.0 7.5 10.0 12.5 15.0 17.5

(x10,000)
1.0
167

0.5 A
182
51 77
63 105 128 139
0.0 184
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 300.0 325.0

(x10,000)
1.0
181 Cl Cl

0.5 111
219 B Cl Cl
51 75 146 217 Cl
55 85 121 160
134 202 254
0.0
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 300.0 325.0
(x10,000)
1.0
81 ClCl
Cl
Cl

0.5
67 263
281
C Cl Cl
O

53 113 245
147 209 345
101 173183
139 217 309317
0.0
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.0 250.0 275.0 300.0 325.0 350.0

Figure 9.  Top: degradation final products chromatogram ([POPs] = 100 mg/L, [Fe/Pd] = 0.5 g/L) and bottom: degradation intermediates
mass spectrum ([POPs] = 100 mg/L, [Fe/Pd] = 0.5 g/L), (a) 1,1-­diphenylethane, (b) pentachlorocyclohexene, and (c) endrin.

Proposed mechanism for enhanced reductive
dechlorination of POPs by Fe/Pd bimetallic
nanoparticles by ultrasound irradiation
It was hypothesized that the degradation of POPs by Fe/Pd
bimetallic nanoparticles proceeds via a heterogeneous cata-
lytic reaction which takes place at the surface of both Fe and
Pd metals (Luo, Yang, Wang, & Sun, 2010). The oxidation of
iron occurs first and releases electrons, and then water accepts
those electrons and forms hydrogen gas, which is dissociated
diatomically on the Pd surface forming atomic hydrogen or
metal hydride. Both species are very reactive to carbon–chlo-
rine bond. Subsequently, POPs are adsorbed to the surface of
Fe/Pd nanoparticles where the dechlorination reaction occurs.
The reaction leads to the cleavage of C-­Cl bond, and a chlorine
atom is replaced by a hydrogen atom (Figure 8). The enhance-
ment as a result of ultrasound bath mixing versus mixing by
a platform shaker could be attributed to several factors, these
include the deagglomeration and surface cleaning effects by
ultrasound, as well as accelerated mass transport rate of reac-
tants to the surfaces of the Fe/Pd nanoparticles. It was noticed
that the rate of the degradation during the first 5 min of the
treatment follows the order of p, p’-­DDT > aldrin > γ-­HCH,
suggesting that the solubility of the chosen POPs in water may
play a critical role in the early stage of the dechlorination reac-
tions. In this study, the solubility of three represented POPs
in water is in the order of γ-­HCH > aldrin > p, p’-­DDT. As a
result of the relatively higher solubility in water, there is a less
chance for γ-­HCH molecules to be adsorbed onto the surface
of Fe/Pd nanoparticles than aldrin or p, p’-­DDT.
Identification of degradation intermediates and
final products
A separate study has been conducted using three chosen
POPs, each with an initial concentration of 100 ppm, in order

Water Environment Research • 1–10, 2019 7

Research Article

Figure 10.  (a) γ-­HCH degradation intermediates and final product detected by GC/MS, (b) Aldrin degradation intermediates and final product
detected by GC/MS, and (c) p, p’-­DDT degradation intermediates and final product detected by GC/MS. 1: p, p’-­DDT, 2: p, p’-­DDD, 3: p, p’-­DDE, 4:
p, p’-­DDMS, 5: p, p’-­DDM, 6: DPB, 7: 1-­chloro-­4-­chlorophenylmethyl-­benzene, 8: diphenyl chloromethane, 9: 2-­chloro-­1-­phenylethyl-­benzene,
10: 1,1-­diphenylethane, 11: 1,2-­diphenylethane, 12: p, p’-­dimethyl diphenyl methane, 13: 1-­phenyl-­1-­cyclohexylethane, 14: diphenylmeth-
ane, and 15: cyclohexylmethyl-­benzene.

to better understand the degradation pathways of γ-­HCH,
aldrin, and p, p’-­DDT in the presence of Fe/Pd nanoparti-
cles with an ultrasound bath mixing. The identification of the
degradation intermediates and final product was analyzed
using GC/MS. GC/MS chromatograms and mass spectra of
the final products for the dechlorination of γ-­HCH, aldrin,
and p, p’-­DDT are shown in Figure 9. Three species, namely
1,1-­diphenylethane, endrin, and pentachlorocyclohexene,
were identified as the final products of γ-­HCH, aldrin, and p,
p’-­DDT, respectively, within 60 min of the treatment with a

8 Moujahid et al.

loading dose of 0.5 g/L Fe/Pd bimetallic nanoparticles. Based
on time-­based GC/MS results, we further stipulated the reac-
tion pathways for reductive dechlorination of γ-­HCH, aldrin,
and p, p’-­DDT.
The proposed degradation pathways of γ-­HCH, aldrin,
and p, p’-­DDT by Fe/Pd bimetallic nanoparticles are shown in
Figure 10a–c, respectively. The dechlorination of γ-­HCH by Fe/
Pd bimetallic nanoparticles appears to be a sequential process.
Two intermediates, that is, pentachlorocyclohexene and 2, 3, 4,
5-­tetrachloro-­1,3-­cyclohexadiene, were identified after losing
one and two chloride atoms from γ-­HCH molecules, respec-
tively. Our GC/MS experiments were not able to resolve any
other intermediates and/or end product, probably due to the
extremely fast reduction reaction expedited by the presence of
Fe/Pd bimetallic nanoparticles with the assistance of effective
ultrasonic mixing. According to previous research, the complete
degradation of γ-­HCH generates benzene as the final product
(Nagpal, Bokare, Chikate, Rode, & Paknikar, 2010; Wang, Peng, &
Huang, 2009). The results in Figure 10b indicate that the reduc-
tive dechlorination of aldrin, by Fe/Pd bimetallic nanoparticles
with the assistance of ultrasonic mixing, generates endrin as
aldrin’s degradation intermediate and icosahydro 1,4:5,12:6,11:
7,10-­tetramethanodibenzo (b, h) biphenylene as the final prod-
uct. As shown in Figure 10c, eight chlorinated intermediates as
a result of the degradation of p, p’-­DDT were identified, and
these include p, p’-­DDD, p, p’-­DDE, p, p’-­DDMS, p, p’-­DDM,
DPB, 1-­chloro-­4-­chlorophenylmethyl-­benzene, diphenyl
chloromethane, and 2-­chloro-­1-­phenylethyl-­benzene. The end
product was 1,1-­diphenylethane. Five other nonchlorinated by-­
products were also identified; these include 2-­diphenylethane,
p, p’-­dimethyl diphenyl methane, 1-­phenyl-­1-­cyclohexylethane,
diphenylmethane, and cyclohexylmethyl-­ benzene. Since the
complete dechlorination of DDT occurs within less than
10 min after the ultrasonic mix (as shown in Figure 7), it is
highly likely that the degradation reaction did not follow a step-
wise or sequential dechlorination process as suggested by oth-
ers (Shih, Chen, Chen, Tai, & Tso, 2009).
Conclusions
In summary, Fe/Pd bimetallic nanoparticles demonstrated
high capability (i.e., >90% removal in the first 30 min of the
reaction) in the degradation of POPs in water via ultrasonic
mixing, whereas the mixing by a platform shaker was much
less effective, possibly due to the poor suspension of Fe/Pd
bimetallic nanoparticles in the solution which decreases the
contact time between Fe/Pd and POPs. The results proved
that both ultrasound bath mixing and Fe/Pd play an impor-
tant role in the reductive dechlorination of POPs in water
matrix. Further analyses by GC/MS provided verification of
POP degradation intermediates and final products and helped
us to better understand the underlying reaction mechanisms
of the reductive dechlorination of POPs with Fe/Pd bime-
tallic nanoparticles. We demonstrated ultrasound irradiation
was a much more effective method of mixing compared to
mechanical shaking, during the catalytical dechlorination of
γ-­HCH, aldrin, and DDT. The enhanced rates of reductive
Water Environment Research • 1–10, 2019 9
Research Article
dechlorination of these three POPs by ultrasound irradia-
tion compared to mechanical shaking could be attributed to
adequate mixing of the targeted POP molecules with the Fe/
Pd nanoparticles, which promotes the continuous cleaning
and chemical activation of the surfaces, while minimizing
the uncertainly caused by unintended removal via adsorp-
tion precipitation. Our study may shed new insights into the
effective remediation of water or soils contaminated by a
wide variety of POPs.
Acknowledgments
The authors are grateful for the financial support of this
project by the U.S. National Science Foundation (Award #
1831133 and DMR-­1523617), the Department of Education
(Grant No. P120A150022), and North Carolina Space Grant
Consortium. The authors also thank Dr. Chen Chen for help-
ing with the TEM characterization of the Fe/Pd bimetallic nan-
oparticles. This work was performed in part at the Analytical
Instrumentation Facilities (AIF) at NC State University, which
is supported by the state of North Carolina and the National
Science Foundation (Award ECCS-­1542015). AIF is a member
of RTNN, a site in the National Nanotechnology Coordinated
Infrastructure (NNCI).
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