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Chen 2014
Chen 2014
Chen 2014
DOI 10.1007/s11356-013-2089-8
RESEARCH ARTICLE
Received: 18 June 2013 / Accepted: 23 August 2013 / Published online: 5 January 2014
# Springer-Verlag Berlin Heidelberg 2014
trichloroethylene, chlorobenzenes, chlorophenols, polychlo- electrical power devices such as transformers and capacitors is
rinated dibenzo-p-dioxins, and PCBs (Chen et al. 2001; Ye probably the main source of PCBs (Chen et al. 2010). The two
et al. 2011; Marshall et al. 2002; Chuang et al. 1995; Kluyev soil-sampling sites were polluted at almost the same time. The
et al. 2002; Kim and Carraway 2000). In bimetallic systems (e.g., initial concentrations of PCBs in the two soil samples were
Pd/Fe, Ni/Fe, Pd/Mg, and Ag/Fe), the enhanced corrosion of a 12.90 and 6.57 mg kg−1, respectively. The main physicochem-
reactive metal is combined with the catalytic hydrogenation ical properties of the two samples are provided in Table 1.
properties of a noble metal to drive the reduction of chlorinated Before testing, the soils were air-dried, passed through a 2-
organic pollutants at the bimetallic interface (Agarwal et al. 2007; mm sieve, and stored at 4 °C. The soils were passed through a
Grittini et al. 1995; Fang and Al-Abed 2008; Hadnagy et al. 0.25-mm sieve before further experiments.
2007; Xu and Zhang 2000; Schrick et al. 2002). With the
development of nanotechnology, rapid and complete destruc- Preparation and characterization of nanoparticles
tion of contaminants has been achieved using nanoscale
zerovalent iron (nZVI) and bimetallic nanoparticles with large nZVI and Pd/Fe bimetallic nanoparticles were synthesized
specific surface areas and high reactivities (Wang and Zhang according to the methods described by Zhou et al. (2011).
1997; Zhang et al. 1998; Liu and Lowry 2006; Mitoma et al. nZVI was synthesized by adding stoichiometric amounts of
2009), and field studies have been performed to assess their NaBH4 aqueous solution to a 1-L three-necked flask contain-
effectiveness in contaminated site remediation (O’Carroll et al. ing FeSO4·7H2O aqueous solution, with stirring, at 25 °C
2013; Cundy et al. 2008). under N2 gas. The Pd/Fe bimetallic nanoparticles were then
Previous studies with nZVI and bimetallic systems have prepared by adding a K2PdCl6 solution to the synthesized iron
focused on the mechanism, kinetics, and various process nanoparticles in the aqueous phase. The deposition was 1 mg
parameters of PCBs hydrodechlorination in solution, but the of Pd on 1 g of nZVI (0.1 % by weight), based on the Pd mass
removal of PCBs from contaminated soil at ambient temper- balance in the solution.
ature still needs to be investigated. In this study, the hydro- The morphologies of the nanoparticles were observed by
dechlorination kinetics and pathways of 2,2′,4,4′,5,5′- transmission electron microscopy (TEM; Hitachi H-7650) at
hexachlorobiphenyl (PCB 153) in deionized water were com- 200 kV to determine the size and distribution of the
pared in a series of contact experiments with two types of nanoparticles. The N2 Brunauer–Emmett–Teller (BET) sur-
reductant: nZVI and Pd/Fe bimetallic nanoparticles. The roles face areas of the nZVI and Pd/Fe nanoparticles were measured
of the Pd catalyst and adsorption on the nanoparticle surfaces using a TriStar II 3020 surface area and porosity system. The
were investigated. Then different types of contaminated soil crystal structures of the nanoparticles were examined by X-ray
samples collected from the e-waste recycling area in Taizhou diffraction (XRD; Rigaku D/max-rA powder X-ray diffrac-
city were treated with the reductants and the removal of PCBs tometer). Prior to the measurements, dry nZVI and Pd/Fe
was investigated. Finally, we explored the potential issues nanoparticles were obtained by washing the wet precipitates
related to in situ remediation of PCBs contaminated soil. with acetone and drying them at 110 °C for 6 h under a flow of
N2.
Neat PCBs standards were obtained from the J&K Chemical A PCB 153 stock solution (200 mg L−1) was prepared using
Co., Ltd. (Beijing, China). Potassium hexachloropalladate acetone as the solvent, and stored in a refrigerator at 4 °C. In
(Pd%=26.2) was purchased from the Aladdin Reagent Co., the batch experiments, PCB 153 (0.1 mg) was introduced into
Ltd. (Shanghai, China). A solid-phase extractant (SPE; C18, a three-necked flask by adding 0.5 mL of the 200 mg L−1
6 cm3/500 mg) was purchased from the Waters Technologies
Co., Ltd. (Shanghai, China). Ferrous sulfate (FeSO4; 99.0–
Table 1 Main physicochemical properties of two soil samples
101.0 %), sodium borohydride (NaBH4; ≥96.0 %), florisil
(≥99.5 %), sulfuric acid (95–98 %), methanol (>99.9 %), n- Soil sample pH SOMa (%) Moisture (%) Texture (%)
hexane, and acetone of analytical grade were also used.
Sand Silt Clay
Soil samples 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
Two soil samples were collected from the electronic waste (e-
a
waste) recycling area in Taizhou. The crude dismantling of Soil organic matter
Environ Sci Pollut Res (2014) 21:5201–5210 5203
stock solution. The solvent was allowed to evaporate in a constant temperature incubator shaker at 180 rpm and 30 °C.
ventilated fume hood and hydrodechlorination of PCB 153 At selected time intervals, the slurry in the conical flasks was
occurred in the three-necked flask containing 50 mL of a centrifuged at 2000 rpm for 5 min to separate the soil and
water solution with nZVI or Pd/Fe nanoparticles at 25 °C. nanoparticles from the water. The concentrations of PCBs in
The flasks were wrapped in Al foil to avoid photolysis of PCB the water were determined using solid phase extraction with
153. The solution in the flask was stirred at 150 rpm with a C18, and the concentrations of PCBs in the mixture (soil and
mechanical stirrer during the reaction, under a N2 flow to nanoparticles) were determined using the following method.
maintain an anaerobic environment.
Analytical determination
Analytical determination
The samples containing soil and nanoparticles were freeze-
At predetermined time intervals, the solution was centrifuged dried to avoid volatilization after the reaction. The freeze-
at 2000 rpm for 5 min to separate the nanoparticles from the dried samples, together with 30 mL of n -hexane and acetone
water. PCB 153 in the water was extracted using SPE C18 (v:v=1:1), were placed in centrifuge tubes and extracted in an
columns, and the columns were eluted with 5 mL of n-hexane. ultrasonic bath for 15 min. The mixture was centrifuged and the
PCB 153 adhered to the flask, and nanoparticles were rinsed supernatant was collected. The sample was re-extracted twice
off using 10 mL of n-hexane. The two parts were collected in with 20 mL of the mixed solvent, as described before. The three
20 mL volumetric flask and n-hexane was added to make up extracts were combined, concentrated to around 1 mL by rotary
the volume. To understand the adsorption of nanoparticles, evaporation, dissolved in 8 mL of n-hexane, and cleaned up
parallel experiments were conducted without rinsing off the using a florisil/anhydrous sodium sulfate column. The column
PCB 153 adsorbed on the nanoparticles. Blank samples were was eluted with 100 mL of n-hexane and the eluant was further
prepared without the addition of nZVI or Pd/Fe nanoparticles. concentrated to 1 mL (He et al. 2009; Shen et al. 2009a).
The concentrations of PCB 153 were measured using a gas The concentrations of 50 PCBs congeners with three to
chromatograph (GC) equipped with a 63Ni electron capture seven chlorine atoms, i.e., PCB 16, 18, 22, 28, 31, 32, 33, 37,
detector (ECD; DB/HP-5 column, Agilent 7890, US). High- 40, 41, 42, 44, 45, 47, 48, 49, 52, 56, 60, 64, 66, 70, 74, 82, 83,
purity (99.99 %) N2 was used as the carrier gas at a flow rate of 85, 87, 97, 99, 101, 108, 110, 118, 128, 129, 136, 137, 138,
60 mL min−1. The heating program for the oven temperature 141, 146, 149, 153, 159, 170, 175, 177, 178, 180, 185, 187,
was as follows: starting temperature 150 °C, held for 1 min; were measured using a GC-μECD. The heating program for
150–280 °C at 15 °C min−1; 280 °C, held for 8 min. The the oven temperature was as follows: starting temperature
injector and the detector were set at 335 °C and 265 °C, 150 °C, held for 1 min; 150–175 °C at 10 °C min−1; and
respectively. PCB 153 was quantified using a calibration curve 175–250 °C at 1.3 °C min−1. The injector and the detector
obtained with standard samples of different concentrations. temperatures were set at 335 °C and 265 °C, respectively. The
The samples were spiked with PCB 209 before extraction, PCBs were quantified using a calibration curve obtained with
to determine the recoveries; the recoveries of PCBs were in standard Aroclor 1254 samples of different concentrations.
the range 78–97 %. In this study, the final concentrations of
PCB 153 were corrected according to the recoveries. Analysis Quality control
of the hydrodechlorination products was performed using an
Agilent 7890A GC equipped with an Agilent 5975C mass All procedures were performed under strict quality control to
spectrometer (MS) and auto sampler. The intermediate prod- meet United States Environmental Protection Agency require-
ucts were first qualitatively identified by comparing their ments. The samples were spiked with PCB 209 before extrac-
retention times with that of a standard Aroclor 1254 sample, tion, to determine the recoveries; the recoveries of PCBs were
and then quantified using a calibration curve. in the range 75–105 %. In this study, the final concentrations of
PCBs in the samples were not corrected based on the recover-
Degradation of PCBs in contaminated soil ies. The detection limit was in the range 0.009–0.082 μg kg−1
soil.
Experimental design
Soil samples (3 g) and nanoparticles (1 g) were mixed as a water Results and discussion
slurry (100 mL) in conical flasks to make mixing easier and to
avoid oxidation of the nanoparticles (Varanasi et al. 2007). Characterization of nanoparticles
Blank samples were prepared, using deionized water, without
nZVI or Pd/Fe bimetallic nanoparticles and all the experiments TEM images of the synthesized nZVI and Pd/Fe bimetallic
were conducted in triplicate. The flasks were placed in a nanoparticles are shown in Fig. 1. Most of the particles were in
5204 Environ Sci Pollut Res (2014) 21:5201–5210
2 4 8 12 20
Fig. 4 Pseudo-first-order plots of hydrodechlorination of PCB 153 in Degradation of PCB 153 in soil
deionized water using a nZVI and b Pd/Fe nanoparticles
The removal of PCB 153 from the soil was investigated and
obtained pseudo-first-order rate constants were 0.110 and compared with hydrodechlorination in deionized water. The
0.120 h−1 with the nZVI and Pd/Fe nanoparticles, respectively. data in Table 4 show that the concentrations of PCB 153 and
PCB 146 (inseparable) in the two soil samples decreased over
Hydrodechlorination pathways of PCB 153 time, and the concentrations reached using Pd/Fe nanoparticles
were lower than those achieved using nZVI after 12 days.
Biphenyl was identified in a hexane extract of the reaction These results were in accordance with the hydrodechlorination
mixture by GC/MS and by comparison of the retention time of PCB 153 in deionized water.
with that of a standard biphenyl solution. Intermediate hydro-
dechlorination products, i.e., pentachlorobiphenyls, tetrachlo- Degradation of PCBs homologs in soil
robiphenyls, and trichlorobiphenyls, were identified by GC/MS
analysis. PCB 153 was reduced to its lower-substituted counter- The concentrations of trichlorobiphenyl, tetrachlorobiphenyl,
parts, which were subsequently completely hydrodechlorinated pentachlorobiphenyl, hexachlorobiphenyl, and heptachlo-
to biphenyl. robiphenyl in soil after the different treatments for 12 days are
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
the reaction process by decreasing the formation of passivation compete with PCBs for electron donors in the presence of
layers (Wang and Zhang 1997). 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
Effect of soil properties on PCBs degradation sample 2. It was therefore concluded that the catalytic activity
of Pd was also affected by the soil properties. DOM attached to
A comparison of the degradation of the two soil samples the surface of the catalyst and consequently reduced the deg-
showed that the PCBs removal efficiencies from soil sample radation efficiencies of PCBs (Zhang et al. 2011). The soil
1 were higher than those from soil sample 2. Table 1 shows the properties may therefore be very important when considering
main physiochemical properties of the two soil samples. The the use of nZVI in PCBs removal from contaminated soil.
soil pH influenced the hydrodechlorination, and previous stud-
ies have demonstrated that weakly acidic conditions favor the Potential challenges of in situ remediation
removal of PCBs from soil (Wang et al. 2012; He et al. 2009).
Water, as a hydrogen donor, was an important candidate in the Although nZVI technology has many advantages such as re-
hydrodechlorination process. There was little difference in the ducing the overall costs of cleaning up large-scale contaminated
pH and moisture content between the two soil samples. sites and the clean-up time, it is still a challenge to satisfy the
The grain size distribution could influence PCBs degrada- requirements for in situ treatment and disposal of contaminated
tion under the same reaction conditions. The two soil samples soil and groundwater (Karn et al. 2009; Mueller et al. 2012).
were sandy loam and powder clay, respectively. We supposed Research has shown that nZVI is effective for the in situ
that the lower the content of clay and the higher the content of remediation of many subsurface environmental contaminants
sand, the higher the removal efficiency would be, as a result of (Zhang 2003). However, when exposed to the environment,
less facile desorption of PCBs from clay particles. The degra- nZVI aggregates to some degree, which indicates that surface-
dation of PCBs was also affected by soil organic matter. The modified nZVIs are needed to improve mobility. High removal
content of organic matter in soil sample 2 was much higher efficiencies of trichloroethene by carboxymethylcellulose-
than that in soil sample 1. Dissolved organic matter (DOM), stabilized Fe/Pd bimetallic nanoparticles and starch-stabilized
released from the soils could retard the hydrodechlorination Fe/Pd bimetallic nanoparticles have been demonstrated by He
in a number of ways (Zhang et al. 2011). The contact and et al. (He et al. 2007; He and Zhao 2005), and enhanced
reaction between PCBs and the nanoparticles was impeded destruction of chlorinated biphenyls in the subsurface has been
since DOM molecules on the particle surface can form a mass achieved with carboxymethylcellulose-stabilized iron nano-
transfer and electron transfer barrier. Furthermore, DOM may 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
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