Environ Sci Pollut Res (2014) 21:5201–5210
DOI 10.1007/s11356-013-2089-8
RESEARCH ARTICLE
Hydrodechlorination of polychlorinated biphenyls
in contaminated soil from an e-waste recycling area, using
nanoscale zerovalent iron and Pd/Fe bimetallic nanoparticles
Xi Chen & Xiaoyan Yao & Chunna Yu & Xiaomei Su & Chaofeng Shen &
Chen Chen & Ronglang Huang & Xinhua Xu
Received: 18 June 2013 / Accepted: 23 August 2013 / Published online: 5 January 2014
# Springer-Verlag Berlin Heidelberg 2014
Abstract Soil pollution by polychlorinated biphenyls (PCBs)
arising from the crude disposal and recycling of electronic and
electrical waste (e-waste) is a serious issue, and effective reme-
diation technologies are urgently needed. Nanoscale zerovalent
iron (nZVI) and bimetallic systems have been shown to pro-
mote successfully the destruction of halogenated organic com-
pounds. In the present study, nZVI and Pd/Fe bimetallic
nanoparticles synthesized by chemical deposition were used
to remove 2,2′,4,4′,5,5′-hexachlorobiphenyl from deionized
water, and then applied to PCBs contaminated soil collected
from an e-waste recycling area. The results indicated that the
hydrodechlorination of 2,2′,4,4′,5,5′-hexachlorobiphenyl by
nZVI and Pd/Fe bimetallic nanoparticles followed pseudo-
first-order kinetics and Pd loading was beneficial to the
hydrodechlorination process. It was also found that the removal
efficiencies of PCBs from soil achieved using Pd/Fe bimetallic
nanoparticles were higher than that achieved using nZVI and
that PCBs degradation might be affected by the soil properties.
Finally, the potential challenges of nZVI application to in situ
remediation were explored.
Keywords Hydrodechlorination . Polychlorinated
biphenyls . nZVI . Pd/Fe bimetallic nanoparticles . E-waste .
Soil remediation
Responsible editor: Hongwen Sun
X. Chen : X. Yao : X. Su : C. Shen (*) : C. Chen : R. Huang :
X. Xu
Department of Environmental Engineering, Zhejiang University, 866
Yuhangtang Road, Hangzhou, Zhejiang 310058, People’s Republic
of China
e-mail: ysxzt@zju.edu.cn
C. Yu
Center for Biomedicine and Health, Hangzhou Normal University,
Hangzhou 311121, China
Introduction
The crude disposal and recycling of electronic and electrical
waste (e-waste) causes soil pollution with heavy metals and
organic compounds such as dioxins, polychlorinated biphenyls
(PCBs), polycyclic aromatic hydrocarbons, and polybrominated
diphenyl ethers (Tang et al. 2010a; Leung et al. 2011; Luo et al.
2009; Liu et al. 2008). Taizhou city, one of the main e-waste
processing centers in China, has a history of nearly 30 years of e-
waste disassembly (Tang et al. 2010b; Shen et al. 2009a). Our
previous study, using a combination of in vitro bioassays and
chemical analysis, showed that surface soil extracts collected
from this area induced significant aryl hydrocarbon receptor
activities, mainly caused by PCBs (Shen et al. 2008). PCBs
are harming the local residents via inhalation, dermal exposure,
and even oral intake. Once taken into the body, PCBs are
stored in certain tissues, leading to toxic episodes and illness
when the levels reach critical values (Safe 1993; Cogliano
1998). Effective technologies are needed for clean-up of con-
taminated soil in e-waste recycling areas.
The methods used most frequently for remediation of PCB-
contaminated soils and sediments are incineration and disposal
in offsite landfills, but there are now new methods that could be
more sustainable alternatives, including biological treatment
and chemical methods (Gomes et al. 2013). Bioremediation
was demonstrated to be appropriate for the removal of PCBs
from soil over a large contaminated area such as that in
Taizhou city (Shen et al. 2009b; Chen et al. 2010). However,
it is not effective for the removal of highly chlorinated biphe-
nyls, and takes several months to achieve clean-up goals. A
variety of chemical treatments, such as metallic calcium with a
Rh/C catalyst (Mitoma et al. 2009), Fe-based technologies
(O’Carroll et al. 2013), and Pd/C with triethylamine (Kume
et al. 2008), are extremely effective for degradation of PCBs.
Zerovalent iron has been shown to successfully promote the
destruction of many halogenated organic compounds, including
5202
trichloroethylene, chlorobenzenes, chlorophenols, polychlo-
rinated dibenzo-p-dioxins, and PCBs (Chen et al. 2001; Ye
et al. 2011; Marshall et al. 2002; Chuang et al. 1995; Kluyev
et al. 2002; Kim and Carraway 2000). In bimetallic systems (e.g.,
Pd/Fe, Ni/Fe, Pd/Mg, and Ag/Fe), the enhanced corrosion of a
reactive metal is combined with the catalytic hydrogenation
properties of a noble metal to drive the reduction of chlorinated
organic pollutants at the bimetallic interface (Agarwal et al. 2007;
Grittini et al. 1995; Fang and Al-Abed 2008; Hadnagy et al.
2007; Xu and Zhang 2000; Schrick et al. 2002). With the
development of nanotechnology, rapid and complete destruc-
tion of contaminants has been achieved using nanoscale
zerovalent iron (nZVI) and bimetallic nanoparticles with large
specific surface areas and high reactivities (Wang and Zhang
1997; Zhang et al. 1998; Liu and Lowry 2006; Mitoma et al.
2009), and field studies have been performed to assess their
effectiveness in contaminated site remediation (O’Carroll et al.
2013; Cundy et al. 2008).
Previous studies with nZVI and bimetallic systems have
focused on the mechanism, kinetics, and various process
parameters of PCBs hydrodechlorination in solution, but the
removal of PCBs from contaminated soil at ambient temper-
ature still needs to be investigated. In this study, the hydro-
dechlorination kinetics and pathways of 2,2′,4,4′,5,5′-
hexachlorobiphenyl (PCB 153) in deionized water were com-
pared in a series of contact experiments with two types of
reductant: nZVI and Pd/Fe bimetallic nanoparticles. The roles
of the Pd catalyst and adsorption on the nanoparticle surfaces
were investigated. Then different types of contaminated soil
samples collected from the e-waste recycling area in Taizhou
city were treated with the reductants and the removal of PCBs
was investigated. Finally, we explored the potential issues
related to in situ remediation of PCBs contaminated soil.
Materials and methods
Chemicals
Neat PCBs standards were obtained from the J&K Chemical
Co., Ltd. (Beijing, China). Potassium hexachloropalladate
(Pd%=26.2) was purchased from the Aladdin Reagent Co.,
Ltd. (Shanghai, China). A solid-phase extractant (SPE; C18,
6 cm3/500 mg) was purchased from the Waters Technologies
Co., Ltd. (Shanghai, China). Ferrous sulfate (FeSO4; 99.0–
101.0 %), sodium borohydride (NaBH4; ≥96.0 %), florisil
(≥99.5 %), sulfuric acid (95–98 %), methanol (>99.9 %), n-
hexane, and acetone of analytical grade were also used.
Soil samples
Two soil samples were collected from the electronic waste (e-
waste) recycling area in Taizhou. The crude dismantling of
Environ Sci Pollut Res (2014) 21:5201–5210
electrical power devices such as transformers and capacitors is
probably the main source of PCBs (Chen et al. 2010). The two
soil-sampling sites were polluted at almost the same time. The
initial concentrations of PCBs in the two soil samples were
12.90 and 6.57 mg kg−1, respectively. The main physicochem-
ical properties of the two samples are provided in Table 1.
Before testing, the soils were air-dried, passed through a 2-
mm sieve, and stored at 4 °C. The soils were passed through a
0.25-mm sieve before further experiments.
Preparation and characterization of nanoparticles
nZVI and Pd/Fe bimetallic nanoparticles were synthesized
according to the methods described by Zhou et al. (2011).
nZVI was synthesized by adding stoichiometric amounts of
NaBH4 aqueous solution to a 1-L three-necked flask contain-
ing FeSO4·7H2O aqueous solution, with stirring, at 25 °C
under N2 gas. The Pd/Fe bimetallic nanoparticles were then
prepared by adding a K2PdCl6 solution to the synthesized iron
nanoparticles in the aqueous phase. The deposition was 1 mg
of Pd on 1 g of nZVI (0.1 % by weight), based on the Pd mass
balance in the solution.
The morphologies of the nanoparticles were observed by
transmission electron microscopy (TEM; Hitachi H-7650) at
200 kV to determine the size and distribution of the
nanoparticles. The N2 Brunauer–Emmett–Teller (BET) sur-
face areas of the nZVI and Pd/Fe nanoparticles were measured
using a TriStar II 3020 surface area and porosity system. The
crystal structures of the nanoparticles were examined by X-ray
diffraction (XRD; Rigaku D/max-rA powder X-ray diffrac-
tometer). Prior to the measurements, dry nZVI and Pd/Fe
nanoparticles were obtained by washing the wet precipitates
with acetone and drying them at 110 °C for 6 h under a flow of
N2.
Hydrodechlorination of PCB 153 in deionized water
Experimental design
A PCB 153 stock solution (200 mg L−1) was prepared using
acetone as the solvent, and stored in a refrigerator at 4 °C. In
the batch experiments, PCB 153 (0.1 mg) was introduced into
a three-necked flask by adding 0.5 mL of the 200 mg L−1
Table 1 Main physicochemical properties of two soil samples
Soil sample pH SOMa (%) Moisture (%) Texture (%)
Sand Silt Clay
1 6.95 2.34 2.23 59.1 31.7 9.2
2 6.61 5.73 2.31 28.3 47.1 24.6
a
Soil organic matter
Environ Sci Pollut Res (2014) 21:5201–5210
stock solution. The solvent was allowed to evaporate in a
ventilated fume hood and hydrodechlorination of PCB 153
occurred in the three-necked flask containing 50 mL of a
water solution with nZVI or Pd/Fe nanoparticles at 25 °C.
The flasks were wrapped in Al foil to avoid photolysis of PCB
153. The solution in the flask was stirred at 150 rpm with a
mechanical stirrer during the reaction, under a N2 flow to
maintain an anaerobic environment.
Analytical determination
At predetermined time intervals, the solution was centrifuged
at 2000 rpm for 5 min to separate the nanoparticles from the
water. PCB 153 in the water was extracted using SPE C18
columns, and the columns were eluted with 5 mL of n-hexane.
PCB 153 adhered to the flask, and nanoparticles were rinsed
off using 10 mL of n-hexane. The two parts were collected in
20 mL volumetric flask and n-hexane was added to make up
the volume. To understand the adsorption of nanoparticles,
parallel experiments were conducted without rinsing off the
PCB 153 adsorbed on the nanoparticles. Blank samples were
prepared without the addition of nZVI or Pd/Fe nanoparticles.
The concentrations of PCB 153 were measured using a gas
chromatograph (GC) equipped with a 63Ni electron capture
detector (ECD; DB/HP-5 column, Agilent 7890, US). High-
purity (99.99 %) N2 was used as the carrier gas at a flow rate of
60 mL min−1. The heating program for the oven temperature
was as follows: starting temperature 150 °C, held for 1 min;
150–280 °C at 15 °C min−1; 280 °C, held for 8 min. The
injector and the detector were set at 335 °C and 265 °C,
respectively. PCB 153 was quantified using a calibration curve
obtained with standard samples of different concentrations.
The samples were spiked with PCB 209 before extraction,
to determine the recoveries; the recoveries of PCBs were in
the range 78–97 %. In this study, the final concentrations of
PCB 153 were corrected according to the recoveries. Analysis
of the hydrodechlorination products was performed using an
Agilent 7890A GC equipped with an Agilent 5975C mass
spectrometer (MS) and auto sampler. The intermediate prod-
ucts were first qualitatively identified by comparing their
retention times with that of a standard Aroclor 1254 sample,
and then quantified using a calibration curve.
Degradation of PCBs in contaminated soil
Experimental design
Soil samples (3 g) and nanoparticles (1 g) were mixed as a water
slurry (100 mL) in conical flasks to make mixing easier and to
avoid oxidation of the nanoparticles (Varanasi et al. 2007).
Blank samples were prepared, using deionized water, without
nZVI or Pd/Fe bimetallic nanoparticles and all the experiments
were conducted in triplicate. The flasks were placed in a
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constant temperature incubator shaker at 180 rpm and 30 °C.
At selected time intervals, the slurry in the conical flasks was
centrifuged at 2000 rpm for 5 min to separate the soil and
nanoparticles from the water. The concentrations of PCBs in
the water were determined using solid phase extraction with
C18, and the concentrations of PCBs in the mixture (soil and
nanoparticles) were determined using the following method.
Analytical determination
The samples containing soil and nanoparticles were freeze-
dried to avoid volatilization after the reaction. The freeze-
dried samples, together with 30 mL of n -hexane and acetone
(v:v=1:1), were placed in centrifuge tubes and extracted in an
ultrasonic bath for 15 min. The mixture was centrifuged and the
supernatant was collected. The sample was re-extracted twice
with 20 mL of the mixed solvent, as described before. The three
extracts were combined, concentrated to around 1 mL by rotary
evaporation, dissolved in 8 mL of n-hexane, and cleaned up
using a florisil/anhydrous sodium sulfate column. The column
was eluted with 100 mL of n-hexane and the eluant was further
concentrated to 1 mL (He et al. 2009; Shen et al. 2009a).
The concentrations of 50 PCBs congeners with three to
seven chlorine atoms, i.e., PCB 16, 18, 22, 28, 31, 32, 33, 37,
40, 41, 42, 44, 45, 47, 48, 49, 52, 56, 60, 64, 66, 70, 74, 82, 83,
85, 87, 97, 99, 101, 108, 110, 118, 128, 129, 136, 137, 138,
141, 146, 149, 153, 159, 170, 175, 177, 178, 180, 185, 187,
were measured using a GC-μECD. The heating program for
the oven temperature was as follows: starting temperature
150 °C, held for 1 min; 150–175 °C at 10 °C min−1; and
175–250 °C at 1.3 °C min−1. The injector and the detector
temperatures were set at 335 °C and 265 °C, respectively. The
PCBs were quantified using a calibration curve obtained with
standard Aroclor 1254 samples of different concentrations.
Quality control
All procedures were performed under strict quality control to
meet United States Environmental Protection Agency require-
ments. The samples were spiked with PCB 209 before extrac-
tion, to determine the recoveries; the recoveries of PCBs were
in the range 75–105 %. In this study, the final concentrations of
PCBs in the samples were not corrected based on the recover-
ies. The detection limit was in the range 0.009–0.082 μg kg−1
soil.
Results and discussion
Characterization of nanoparticles
TEM images of the synthesized nZVI and Pd/Fe bimetallic
nanoparticles are shown in Fig. 1. Most of the particles were in
5204
Fig. 1 TEM images of a nZVI and b Pd/Fe nanoparticles (Pd loading at
0.1 %)
the size range 1–50 nm. The BET specific surface area of the
nZVI was 10.5 m2 g−1. The XRD patterns of the nZVI and Pd/
Fe nanoparticles are presented in Fig. 2; these patterns show
the crystalline structures of the nanoparticles.
Fig. 2 XRD patterns of nZVI and Pd/Fe nanoparticles
Environ Sci Pollut Res (2014) 21:5201–5210
Fig. 3 Hydrodechlorination of PCB 153 in deionized water by nZVI and
Pd/Fe nanoparticles; T =25 °C, stirring rate=150 rpm, C particles =5 g L−1,
and Pd loading=0.1 %
Hydrodechlorination kinetics of PCB 153
The hydrodechlorination of PCB 153 by nZVI and Pd/Fe bime-
tallic nanoparticles in deionized water at 25 °C in relation to the
reaction time is summarized in Fig. 3. The initial PCB 153
concentration was 2 mg L−1. The amounts of PCB 153 in the
blank samples remained relatively constant over a period of 20 h.
The removal efficiency after 20 h achieved using nZVI was
74.9 % and that using Pd/Fe bimetallic nanoparticles was 93.8 %.
As shown by the data in Table 2, the concentrations of PCB
153 adsorbed on the surfaces of the nanoparticles in the solu-
tion decreased with increasing reaction time. This indicated
that the hydrodechlorination of PCB 153 occurred when it was
adsorbed on the surfaces of the nZVI or Pd/Fe nanoparticles.
Pseudo-first-order kinetics was expected to apply to the
reaction in this study. A linear relationship between ln(C /C 0)
and the reaction time showed that the hydrodechlorination
reaction approximately followed a pseudo-first-order process
for the first 12 h with nZVI and 20 h with Pd/Fe nanoparticles.
With increasing reaction time, the reaction deviated from
pseudo-first-order reaction kinetics, probably as a result of
formation of surface passivation layers or precipitation of
metal hydroxides (e.g., Fe(OH)2 and Fe(OH)3) and metal
carbonates (e.g., FeCO3) on the Fe surface (He et al. 2009).
The pseudo-first-order kinetics plots are shown in Fig. 4. The
Table 2 Concentrations (in milligrams per liter water) of PCB 153
adsorbed on the surface of nanoparticles
Treatment Reaction time (h)
2 4 8 12 20
nZVI 0.364 0.311 0.166 0.054 0.042
Pd/Fe 0.408 0.347 0.258 0.202 0.068
Environ Sci Pollut Res (2014) 21:5201–5210
Fig. 4 Pseudo-first-order plots of hydrodechlorination of PCB 153 in
deionized water using a nZVI and b Pd/Fe nanoparticles
obtained pseudo-first-order rate constants were 0.110 and
0.120 h−1 with the nZVI and Pd/Fe nanoparticles, respectively.
Hydrodechlorination pathways of PCB 153
Biphenyl was identified in a hexane extract of the reaction
mixture by GC/MS and by comparison of the retention time
with that of a standard biphenyl solution. Intermediate hydro-
dechlorination products, i.e., pentachlorobiphenyls, tetrachlo-
robiphenyls, and trichlorobiphenyls, were identified by GC/MS
analysis. PCB 153 was reduced to its lower-substituted counter-
parts, which were subsequently completely hydrodechlorinated
to biphenyl.
Table 3 Analysis of intermediate
products, after 2 h, from PCB 153 Treatment Concentration of PCB congeners (μg L−1 water)
treated with nZVI and Pd/Fe
nanoparticles 101
nZVI 6.768
Pd/Fe 25.91
ND not detected
5205
Table 3 shows the concentrations of the intermediate products
from PCB 153 treated with nZVI and Pd/Fe nanoparticles after
2 h. We found that Pd not only accelerated the hydrodechlo-
rination process but also varied the possible hydrodechlorination
pathways of PCB 153 and its intermediates. PCB 99 and PCB 74
were detected in the presence of Pd/Fe bimetallic nanoparticles
but not in the reaction of nZVI and PCB 153. The possible
hydrodechlorination pathways for PCB 153 in deionized water
in the presence of nZVI and Pd/Fe nanoparticles are shown in
Fig. 5. We inferred that the diversity of hydrodechlorination
pathways might lead to an increase in the removal efficiency of
PCB 153 from deionized water.
Effect of Pd loading on PCBs degradation in contaminated
soil
Degradation of PCBs in soil
The PCBs removal efficiencies increased with increasing
reaction time and were almost constant after 8 days, as shown
in Fig. 6. The PCBs removal efficiencies achieved for the two
soil samples were 81.5 and 53.4 % after 12 days, using the
nanoscale Pd/Fe bimetallic system, compared with 67.4 and
48.3 % using nZVI. These results indicated that the nZVI and
Pd/Fe nanoparticles were effective in removing PCBs in con-
taminated soil from the e-waste recycling area within a short
period of time.
Degradation of PCB 153 in soil
The removal of PCB 153 from the soil was investigated and
compared with hydrodechlorination in deionized water. The
data in Table 4 show that the concentrations of PCB 153 and
PCB 146 (inseparable) in the two soil samples decreased over
time, and the concentrations reached using Pd/Fe nanoparticles
were lower than those achieved using nZVI after 12 days.
These results were in accordance with the hydrodechlorination
of PCB 153 in deionized water.
Degradation of PCBs homologs in soil
The concentrations of trichlorobiphenyl, tetrachlorobiphenyl,
pentachlorobiphenyl, hexachlorobiphenyl, and heptachlo-
robiphenyl in soil after the different treatments for 12 days are
99 74 52 47+48+49 31 28 18
ND ND 2.398 6.277 3.963 4.372 8.395
11.39 1.655 3.044 7.704 2.042 5.538 10.804
5206 Environ Sci Pollut Res (2014) 21:5201–5210

Fig. 5 Proposed
hydrodechlorination pathways for
PCB 153 in deionized water in the
presence of a nZVI and b Pd/Fe
nanoparticles

shown in Table 5. After adding Pd, the removal efficiencies 37.5 to 61.1, 81.9, 82.6, 89.3, and 50.1 %, respectively. The
from soil sample 1 increased from 48.8, 54.6, 52.1, 56.6, and removal efficiencies from soil sample 2 increased from 52.8,
Environ Sci Pollut Res (2014) 21:5201–5210 5207

nZVI and Pd/Fe nanoparticles within 12 days, even though they

were poorly degraded by bioremediation.

Degradation of PCBs homologs in aqueous phase

The concentrations of PCBs in the supernatants after centrifuga-

Fig. 6 Comparison of PCBs removal efficiencies in a soil samples 1 and
b 2, using nZVI and Pd/Fe nanoparticles; T =30 °C, m particles/m soil =1:3,
shaking speed=180 rpm, and Pd loading=0.1 %
37.8, 29.4, 25.0, and 5.9 to 55.7, 47.6, 37.6, 38.8, and 21.6 %,
respectively. These results indicated that Pd loading was bene-
ficial to the degradation of PCBs homologs in contaminated
soil. Highly chlorinated biphenyls were effectively removed by
tion were very low because of their high hydrophobicities. The
residual concentrations of trichlorobiphenyl, tetrachlorobiphenyl,
pentachlorobiphenyl, hexachlorobiphenyl, and heptachlo-
robiphenyl in aqueous phase treated with nZVI and Pd/Fe
nanoparticles after 12 days are presented in Table 6. The results
show that the concentrations of trichlorobiphenyl, tetrachlo-
robiphenyl, and pentachlorobiphenyl in water sample 1 treated
with nZVI were higher than those treated with Pd/Fe nano-
particles and in the blank samples, whereas the concentrations
of hexachlorobiphenyl and heptachlorobiphenyl with nZVI and
Pd/Fe nanoparticles were lower than those in the blank samples.
In water sample 2, the residual concentrations of trichlo-
robiphenyl treated with nZVI were highest, and the residual
concentrations of tetrachlorobiphenyl, pentachlorobiphenyl,
hexachlorobiphenyl, and heptachlorobiphenyl after treatment
with nZVI and Pd/Fe nanoparticles were lower than those in
the blank samples. The increase in low-chlorinated biphenyls
might be caused by the hydrodechlorination of highly chlorinated
biphenyls in the slurry. The residual concentrations of PCBs
homologs treated with Pd/Fe nanoparticles were lower than those
with nZVI, and this also indicated that hydrodechlorination was
promoted by Pd loading.
The removal efficiencies and reaction rates were increased by
adding Pd as a coating on zerovalent Fe. The consumption of
hydrogen ions in the reduction of hexachlorobenzene using
nanoscale Pd/Fe bimetallic particles was more than that using
nZVI (Shih et al. 2009). Grittini et al. (1995) proposed that Pd on
the surface of Fe acts as a collector of hydrogen gas generated by
Fe corrosion, accelerating the hydrodechlorination of PCBs. In
addition to its catalytic effect, Pd can serve as the cathode in a
galvanic cell when used together with Fe, thus contributing to
electron transfer and promoting hydrodechlorination (Zhu and
Lim 2007). Addition of Pd on the nZVI surfaces also promoted

Table 4 Concentrations (in mil-

ligrams per kilogram of soil) of Soil sample Treatment Reaction time (day)
PCB 153+146 in soil samples 1
and 2 with different treatments 0 4 8 12

1 Control 0.106±0.004 0.102±0.003 0.102±0.002 0.102±0.003

nZVI 0.106±0.004 0.054±0.007 0.041±0.002 0.031±0.003
Pd/Fe 0.106±0.004 0.021±0.003 0.016±0.002 0.011±0.002
2 Control 0.053±0.002 0.055±0.004 0.052±0.002 0.054±0.003
nZVI 0.053±0.002 0.035±0.003 0.029±0.006 0.027±0.002
Pd/Fe 0.053±0.002 0.028±0.002 0.023±0.002 0.026±0.002
5208 Environ Sci Pollut Res (2014) 21:5201–5210

Table 5 Concentrations (in mil-

ligrams per kilogram of soil) of Soil sample Treatment Tri- Tetra- Penta- Hexa- Hepta-
PCBs homologs in soil samples 1
and 2 with different treatments 1 Control 3.898±0.129 3.807±0.502 0.795±0.129 0.159±0.027 0.048±0.008
after 12 days nZVI 1.996±0.140 1.728±0.092 0.381±0.054 0.069±0.012 0.030±0.005
Pd/Fe 1.515±0.449 0.688±0.195 0.138±0.045 0.017±0.004 0.024±0.006
2 Control 3.640±0.071 2.075±0.120 0.388±0.013 0.080±0.004 0.051±0.003
nZVI 1.717±0.188 1.290±0.161 0.274±0.009 0.060±0.004 0.048±0.008
Pd/Fe 1.613±0.110 1.087±0.050 0.242±0.026 0.049±0.004 0.040±0.003

the reaction process by decreasing the formation of passivation
layers (Wang and Zhang 1997).
Effect of soil properties on PCBs degradation
A comparison of the degradation of the two soil samples
showed that the PCBs removal efficiencies from soil sample
1 were higher than those from soil sample 2. Table 1 shows the
main physiochemical properties of the two soil samples. The
soil pH influenced the hydrodechlorination, and previous stud-
ies have demonstrated that weakly acidic conditions favor the
removal of PCBs from soil (Wang et al. 2012; He et al. 2009).
Water, as a hydrogen donor, was an important candidate in the
hydrodechlorination process. There was little difference in the
pH and moisture content between the two soil samples.
The grain size distribution could influence PCBs degrada-
tion under the same reaction conditions. The two soil samples
were sandy loam and powder clay, respectively. We supposed
that the lower the content of clay and the higher the content of
sand, the higher the removal efficiency would be, as a result of
less facile desorption of PCBs from clay particles. The degra-
dation of PCBs was also affected by soil organic matter. The
content of organic matter in soil sample 2 was much higher
than that in soil sample 1. Dissolved organic matter (DOM),
released from the soils could retard the hydrodechlorination
in a number of ways (Zhang et al. 2011). The contact and
reaction between PCBs and the nanoparticles was impeded
since DOM molecules on the particle surface can form a mass
transfer and electron transfer barrier. Furthermore, DOM may
compete with PCBs for electron donors in the presence of
nZVI and Pd/Fe nanoparticles.
Pd loading significantly promoted the degradation of PCBs
in soil sample 1, but this promotion was not obvious in soil
sample 2. It was therefore concluded that the catalytic activity
of Pd was also affected by the soil properties. DOM attached to
the surface of the catalyst and consequently reduced the deg-
radation efficiencies of PCBs (Zhang et al. 2011). The soil
properties may therefore be very important when considering
the use of nZVI in PCBs removal from contaminated soil.
Potential challenges of in situ remediation
Although nZVI technology has many advantages such as re-
ducing the overall costs of cleaning up large-scale contaminated
sites and the clean-up time, it is still a challenge to satisfy the
requirements for in situ treatment and disposal of contaminated
soil and groundwater (Karn et al. 2009; Mueller et al. 2012).
Research has shown that nZVI is effective for the in situ
remediation of many subsurface environmental contaminants
(Zhang 2003). However, when exposed to the environment,
nZVI aggregates to some degree, which indicates that surface-
modified nZVIs are needed to improve mobility. High removal
efficiencies of trichloroethene by carboxymethylcellulose-
stabilized Fe/Pd bimetallic nanoparticles and starch-stabilized
Fe/Pd bimetallic nanoparticles have been demonstrated by He
et al. (He et al. 2007; He and Zhao 2005), and enhanced
destruction of chlorinated biphenyls in the subsurface has been
achieved with carboxymethylcellulose-stabilized iron nano-
particles (He et al. 2010).

Table 6 Concentrations (in micrograms per liter of water) of PCBs homologs in water samples 1 and 2 with different treatments after 12 days

Water sample Treatment Tri- Tetra- Penta- Hexa- Hepta-

1 Control 1.480±0.169 1.430±0.144 0.034±0.005 0.054±0.007 0.101±0.001

nZVI 7.210±0.307 3.210±0.078 0.060±0.011 0.039±0.005 0.103±0.006
Pd/Fe 2.900±0.545 0.653±0.164 0.014±0.003 0.033±0.004 0.075±0.001
2 Control 1.150±0.057 0.699±0.270 0.017±0.003 0.039±0.018 0.109±0.011
nZVI 3.350±0.022 0.658±0.314 0.015±0.006 0.008±0.004 0.101±0.007
Pd/Fe 2.000±0.520 0.316±0.216 0.010±0.009 Not detected 0.071±0.003
Environ Sci Pollut Res (2014) 21:5201–5210
When Fe nanoparticles are introduced into PCBs contami-
nated soil for in situ remediation, the secondary environmental
effects and ecotoxicity of nZVI to soil organisms are worth
considering. There are still no definite conclusions with regard
to this question. A previous study showed that nZVI had poten-
tial negative effects on earthworms, but the effects decreased
over time (El-Temsah and Joner 2012). It was found that reduc-
ing conditions and hydrogen created by nZVI stimulated both
sulfate reducers and methanogen populations, and adding nZVI
had no deleterious effect on the total bacterial abundance
(Kirschling et al. 2010). The impact of nZVI on soil microbial
communities was content-dependent (Pawlett et al. 2013).
Further efforts are needed to improve engineering applica-
tions of nZVI technology to in situ remediation and to inves-
tigate whether nZVI is a greater threat to soil organisms
than PCBs are.
Conclusions
Compared with nZVI, Pd/Fe bimetallic nanoparticles gave
more rapid and complete hydrodechlorination of 2,2′,4,4′,5,5′-
hexachlorobiphenyl in deionized water in 20 h at 25 °C. The
hydrodechlorination followed pseudo-first-order kinetics, and
diverse hydrodechlorination pathways were achieved by
contacting the solution with Pd/Fe nanoparticles.
It was found that higher removal efficiencies of PCBs and its
homologs from contaminated soil collected from an e-waste
recycling area were obtained by Pd loading. We inferred that
the degradation of PCBs and the catalytic activity of Pd in
promoting degradation were affected by the soil properties.
The lower the clay content and the higher the sand content, the
higher the removal efficiency. The soil organic matter may retard
the hydrodechlorination process. The degradation of PCBs in
soil sample 1 was strongly promoted by Pd/Fe nanoparticles,
whereas Pd addition had little impact on PCBs degradation in
soil sample 2.
The experimental results suggest that nZVI and bimetallic
nanoparticles effectively removed PCBs from the e-waste
recycling area, especially in the cases of non-biodegradable
highly chlorinated biphenyls. This method provides a basis for
in situ remediation of PCBs contaminated soil. More research
on the transport and toxicities of nZVI and nanoscale bimetal-
lic systems is still needed, to improve engineering applications.
Acknowledgments This work was supported by the Science and Tech-
nology Foundation of Zhejiang Province, China (2009C13003), the
National High Technology Research and Development Program of China
(2012AA06A203), the National Natural Science Foundation of China
(41271334 and 81001475) and the Science and Technology Development
Foundation of Hangzhou (20101131N05).We thank Ms. Lijuan Mao, the
technician of the 985-Institute of Agrobiology and Environmental Sci-
ences of Zhejiang University, for her contributions in determining the
specific surface area of nZVI.
5209
Reference
Agarwal S, Al-Abed SR, Dionysiou DD (2007) Enhanced corrosion-
based Pd/Mg bimetallic systems for dechlorination of PCBs. Envi-
ron Sci Technol 41(10):3722–3727. doi:10.1021/es062886y
Chen JL, Al-Abed SR, Ryan JA, Li Z (2001) Effects of pH on dechlori-
nation of trichloroethylene by zero-valent iron. J Hazard Mater
83(3):243–254. doi: 10.1016/S0304-3894(01)00193-5
Chen YX, Tang XJ, Cheema SA, Liu WL, Shen CF (2010) Beta-
cyclodextrin enhanced phytoremediation of aged PCBs-
contaminated soil from e-waste recycling area. J Environ Monit
12(7):1482–1489. doi: 10.1039/c0em00029a
Chuang FW, Larson RA, Wessman MS (1995) Zero-valent iron-
promoted dechlorination of polychlorinated biphenyls. Environ Sci
Technol 29(9):2460–2463. doi: 10.1021/es00009a044
Cogliano VJ (1998) Assessing the cancer risk from environmental PCBs.
Environ Health Perspect 106(6):317–323
Cundy AB, Hopkinson L, Whitby RLD (2008) Use of iron-based tech-
nologies in contaminated land and groundwater remediation: a
review. Sci Total Environ 400(1–3):42–51. doi: 10.1016/j.scitotenv.
2008.07.002
El-Temsah YS, Joner EJ (2012) Ecotoxicological effects on earthworms
of fresh and aged nano-sized zero-valent iron (nZVI) in soil.
Chemosphere 89(1):76–82. doi:10.1016/j.chemosphere.2012.04.
020
Fa ng Y, A l - A be d SR (2 00 8 ) D e c h l o r i n a t i on k i n e t i c s o f
monochlorobiphenyls by Fe/Pd: effects of solvent, temperature,
and PCB concentration. Appl Catal B: Environ 78(3–4):371–380.
doi:10.1016/j.apcatb.2007.09.009
Gomes HI, Dias-Ferreira C, Ribeiro AB (2013) Overview of in situ and
ex situ remediation technologies for PCB-contaminated soils and
sediments and obstacles for full-scale application. Sci Total Environ
445–446:237–260. doi:10.1016/j.scitotenv.2012.11.098
Grittini C, Malcomson M, Fernando Q, Korte N (1995) Rapid dechlori-
nation of polychlorinated-biphenyls on the surface of a Pd/Fe bime-
tallic system. Environ Sci Technol 29(11):2898–2900. doi: 10.1021/
es00011a029
Hadnagy E, Rauch LM, Gardner KH (2007) Dechlorination of
polychlorinated biphenyls, naphthalenes and dibenzo-p-dioxins by
magnesium/palladium bimetallic particles. J Environ Sci Health Part
A 42(6):685–695. doi: 10.1080/10934520701326222
He F, Zhao D, Paul C (2010) Field assessment of carboxymethyl cellulose
stabilized iron nanoparticles for in situ destruction of chlorinated
solvents in source zones. Water Res 44(7):2360–2370. doi: 10.1016/
j.watres.2009.12.041
He F, Zhao DY (2005) Preparation and characterization of a new class of
starch-stabilized bimetallic nanoparticles for degradation of chlori-
nated hydrocarbons in water. Environ Sci Technol 39(9):3314–
3320. doi: 10.1021/es048743y
He F, Zhao DY, Liu JC, Roberts CB (2007) Stabilization of Fe-Pd
nanoparticles with sodium carboxymethyl cellulose for enhanced
transport and dechlorination of trichloroethylene in soil and ground-
water. Ind Eng Chem Res 46(1):29–34. doi: 10.1021/ie0610896
He N, Li P, Zhou Y, Ren W, Fan S, Verkhozina VA (2009) Catalytic
dechlorination of polychlorinated biphenyls in soil by palladium-
iron bimetallic catalyst. J Hazard Mater 164(1):126–132. doi:10.
1016/j.jhazmat.2008.07.149
Karn B, Kuiken T, Otto M (2009) Nanotechnology and in situ remedia-
tion: a review of the benefits and potential risks. Environ Heal
Perspect 117(12):1823–1831. doi: 10.1289/ehp.0900793
Kim YH, Carraway ER (2000) Dechlorination of pentachlorophenol by
zero valent iron and modified zero valent irons. Environ Health
Perspect 34(10):2014–2017. doi:10.1021/es991129f
Kirschling TL, Gregory KB, Minkley EG, Lowry GV, Tilton RD (2010)
Impact of nanoscale zero valent iron on geochemistry and microbial
5210
populations in trichloroethylene contaminated aquifer materials.
Environ Sci Technol 44(9):3474–3480. doi:10.1021/es903744f
Kluyev N, Cheleptchikov A, Brodsky E, Soyfer V, Zhilnikov V (2002)
Reductive dechlorination of polychlorinated dibenzo-p-dioxins by
zerovalent iron in subcritical water. Chemosphere 46(9–10):1293–
1296. doi:10.1016/s0045-6535(01)00276-4
Kume A, Monguchi Y, Hattori K, Nagase H, Sajiki H (2008) Pd/C-
catalyzed practical degradation of PCBs at room temperature. Appl
Catal B Environ 81(3–4):274–282. doi:10.1016/j.apcatb.2007.12.019
Leung AOW, Zheng J, Yu CK, Liu WK, Wong CKC, Cai Z, Wong MH
(2011) Polybrominated diphenyl ethers and polychlorinated dibenzo-
p-dioxins and dibenzofurans in surface dust at an e-waste processing
site in southeast China. Environ Sci Technol 45(13):5775–5782. doi:
10.1021/es103915w
Liu H, Zhou Q, Wang Y, Zhang Q, Cai Z, Jiang G (2008) E-waste
recycling induced polybrominated diphenyl ethers, polychlorinated
biphenyls, polychlorinated dibenzo-p-dioxins and dibenzo-furans
pollution in the ambient environment. Environ Int 34(1):67–72.
doi:10.1016/j.envint.2007.07.008
Liu YQ, Lowry GV (2006) Effect of particle age (Fe0 content) and
solution pH on NZVI reactivity: H2 evolution and TCE dechlorina-
tion. Environ Int 40(19):6085–6090. doi:10.1021/es060685o
Luo Y, Luo XJ, Lin Z, Chen SJ, Liu J, Mai BX, Yang ZY (2009)
Polybrominated diphenyl ethers in road and farmland soils from an
e-waste recycling region in Southern China: Concentrations, source
profiles, and potential dispersion and deposition. Sci Total Environ
407(3):1105–1113. doi:10.1016/j.scitotenv.2008.10.044
Marshall WD, Kubatova A, Lagadec AJM, Miller DJ, Hawthorne SB
(2002) Zero-valent metal accelerators for the dechlorination of pen-
tachlorophenol (PCP) in subcritical water. Green Chem 4(1):17–23.
doi:10.1039/b108337f
Mitoma Y, Egashira N, Simion C (2009) Highly effective degradation of
polychlorinated biphenyls in soil mediated by a Ca/Rh bicatalytic
system. Chemosphere 74(7):968–973. doi:10.1016/j.chemosphere.
2008.10.034
Mueller N, Braun J, Bruns J, Černík M, Rissing P, Rickerby D, Nowack B
(2012) Application of nanoscale zero valent iron (NZVI) for ground-
water remediation in Europe. Environ Sci Pollut Res 19(2):550–
558. doi:10.1007/s11356-011-0576-3
O’Carroll D, Sleep B, Krol M, Boparai H, Kocur C (2013) Nanoscale
zero valent iron and bimetallic particles for contaminated site reme-
diation. Adv Water Resour 51:104–122. doi:10.1016/j.advwatres.
2012.02.005
Pawlett M, Ritz K, Dorey R, Rocks S, Ramsden J, Harris J (2013) The
impact of zero-valent iron nanoparticles upon soil microbial com-
munities is context dependent. Environ Sci Pollut Res 20(2):1041–
1049. doi:10.1007/s11356-012-1196-2
Safe S (1993) Toxicology, structure-function relationship, and human and
environmental health impacts of polychlorinated biphenyls: prog-
ress and problems. Environ Health Perspect 100:259–268
Schrick B, Blough JL, Jones AD, Mallouk TE (2002) Hydro-
dechlorination of trichloroethylene to hydrocarbons using bimetallic
nickel–iron nanoparticles. Chem Mater 14(12):5140–5147. doi:10.
1021/cm020737i
Shen CF, Chen YX, Huang SB, Wang ZJ, Yu CN, Qiao M, Xu YP, Setty K,
Zhang JY, Zhu YF, Lin Q (2009a) Dioxin-like compounds in agri-
cultural soils near e-waste recycling sites from Taizhou area, China:
chemical and bioanalytical characterization. Environ Int 35(1):50–55.
doi:10.1016/j.envint.2008.07.005
Environ Sci Pollut Res (2014) 21:5201–5210
Shen CF, Huang SB, Wang ZJ, Qiao M, Tang XJ, Yu CN, Shi DZ, Zhu
YF, Shi JY, Chen XC, Setty K, Chen YX (2008) Identification
of Ah receptor agonists in soil of E-waste recycling sites from
Taizhou area in China. Environ Sci Technol 42(1):49–55. doi:10.
1021/es071162z
Shen CF, Tang XJ, Cheema SA, Zhang CK, Khan MI, Liang F, Chen XC,
Zhu YF, Lin Q, Chen YX (2009b) Enhanced phytoremediation
potential of polychlorinated biphenyl contaminated soil from e-
waste recycling area in the presence of randomly methylated-beta-
cyclodextrins. J Hazard Mater 172(2–3):1671–1676. doi:10.1016/j.
jhazmat.2009.08.064
Shih Y, Chen YC, Chen MY, Tai YT, Tso CP (2009) Dechlorination of
hexachlorobenzene by using nanoscale Fe and nanoscale Pd/Fe
bimetallic particles. Colloids Surf A Physicochem Eng Aspects
332(2–3):84–89. doi:10.1016/j.colsurfa.2008.09.031
Tang X, Shen C, Shi D, Cheema SA, Khan MI, Zhang C, Chen Y (2010a)
Heavy metal and persistent organic compound contamination in soil
from Wenling: An emerging e-waste recycling city in Taizhou area,
China. J Hazard Mater 173(1–3):653–660. doi:10.1016/j.jhazmat.
2009.08.134
Tang XJ, Shen CF, Chen L, Xiao X, Wu JY, Khan MI, Dou CM, Chen
YX (2010b) Inorganic and organic pollution in agricultural soil from
an emerging e-waste recycling town in Taizhou area, China. J J Soils
Sediments 10(5):895–906. doi:10.1007/s11368-010-0252-0
Varanasi P, Fullana A, Sidhu S (2007) Remediation of PCB contaminated
soils using iron nano-particles. Chemosphere 66(6):1031–1038. doi:
10.1016/j.chemosphere.2006.07.036
Wang CB, Zhang WX (1997) Synthesizing nanoscale iron particles for
rapid and complete dechlorination of TCE and PCBs. Environ Sci
Technol 31(7):2154–2156. doi:10.1021/es970039c
Wang Y, Zhou D, Wang L, Cang L (2012) Automatic pH control system
enhances the dechlorination of 2,4,4′-trichlorobiphenyl and
extracted PCBs from contaminated soil by nanoscale Fe and Pd/
Fe. Environ Sci Pollut Res 19(2):448–457. doi:10.1007/s11356-
011-0587-0
Xu Y, Zhang WX (2000) Subcolloidal Fe/Ag particles for eeductive
dehalogenation of chlorinated benzenes. Ind Eng Chem Res 39(7):
2238–2244. doi:10.1021/ie9903588
Ye X, Jianguo J, Yong Y, Guolong G (2011) Base-catalyzed destruction
of hexachlorobenzene with zero-valent iron. Chem Eng J 173(2):
415–421. doi:10.1016/j.cej.2011.07.082
Zhang M, He F, Zhao D, Hao X (2011) Degradation of soil-sorbed
trichloroethylene by stabilized zero valent iron nanoparticles: effects
of sorption, surfactants, and natural organic matter. Water Res 45(7):
2401–2414. doi:10.1016/j.watres.2011.01.028
Zhang WX (2003) Nanoscale iron particles for environmental remedia-
tion: an overview. J Nanopart Res 5(3):323–332. doi:10.1023/
a:1025520116015
Zhang WX, Wang CB, Lien HL (1998) Treatment of chlorinated organic
contaminants with nanoscale bimetallic particles. Catal Today 40(4):
387–395. doi:10.1016/S0920-5861(98)00067-4
Zhou H, Han J, Baig SA, Xu X (2011) Dechlorination of 2,4-
dichlorophenoxyacetic acid by sodium carboxymethyl cellulose-
stabilized Pd/Fe nanoparticles. J Hazard Mater 198:7–12. doi:10.
1016/j.jhazmat.2011.10.002
Zhu BW, Lim TT (2007) Catalytic reduction of chlorobenzenes with Pd/
Fe nanoparticles: reactive sites, catalyst stability, particle aging, and
regeneration. Environ Sci Technol 41(21):7523–7529. doi:10.1021/
es0712625