Topics in Catalysis

https://doi.org/10.1007/s11244-018-1050-y

ORIGINAL PAPER

Decontamination of 1,2-Dichloroethane DNAPL in Contaminated

Groundwater by Polymer-Modified Zero-Valent Iron Nanoparticles
Ndumiso Vukile Mdlovu1 · Kuen‑Song Lin1 · Sat Septian Dwitya1 · Chung‑Yu Chen1 · Chao‑Lung Chiang1

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Remediation of dense non-aqueous phase liquids (DNAPLs) contaminants in groundwater has received considerable atten-
tion in the environmental field. Generally, DNAPLs can flow with groundwater and further infiltrate down to deeper aquitard
zone that is difficult to be removed by pumping. The DNAPLs may also contaminate the soil and groundwater concurrently
in the duration of flowing with groundwater slowly. In this study, remediation of 1,2-dichloroethane (1,2-DCE) in DNAPL
contaminated groundwater was studied by a reductive reaction with polyethylenimine (PEI) surface-modified zero-valent
iron nanoparticles (PEI-nZVI). The prepared PEI-nZVI was injected into upstream wells and reach the plume of DNAPLs
down with the flowing groundwater. Moreover, nZVI was further characterized after field injection and 1-day reaction with
the contaminants to assess its effectiveness for the on-site reduction of 1,2-DCE. After direct injection of PEI-nZVI into the
contaminated plume, the concentrations of 1,2-DCE was significantly reduced. Moreover, the plume was decontaminated to
nontoxic species onto the highly active nZVI. By using resistivity image profiling (RIP), the conductivity data of modified
nZVI solution and sampled groundwater were similar. In addition, RIP can reveal complex subsurface DNAPLs structures
by dense sampling of resistivity variation at shallow depth. Additionally, X-ray absorption near edge structure (XANES) and
extended X-ray absorption fine structure (EXAFS) spectroscopy studies indicated that after the reductive reaction, nZVI and
PEI-nZVI were oxidized to F ­ e3O4. The interatomic distances for the reacted samples were 1.95 Å and 1.93 Å, respectively.
The combined technique of floating surface-modified nZVI and RIP method would be economically and environmentally
attractive.

Extended author information available on the last page of the article

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Vol.:(0123456789)

Graphical Abstract
nZVI aggregates
+ H 2N
Soil surface
Injection
Water table
Fe(0) core PEI shell
Groundwater
flowing
Reduction
reaction
Aquifer
Low permeability layer
Keywords  Zero-valent iron nanoparticles · Polyethylenimine · DNAPLs · Chemical reduction · Injection method ·
Decontamination · Groundwater remediation
1 Introduction
Groundwater, which is one of the most precious natural
resources on Earth, has been widely used for industrial
purposes, agricultural, and human consumption due to its
comparatively good quality when compared to surface water
[1]. However, as the world evolves to industrialization and
urbanization activities, immense exploitation of groundwa-
ter resources has made it vulnerable to many different types
of contaminants [2]. Such activities have led to increased
discharge of a wide range of contaminants in groundwater
and wastewater, which affect the health of millions of people
globally [1–3]. Furthermore, groundwater discharged from
many industrial locations and illegal waste disposal sites has
been reported to be contaminated by chlorinated volatile
organic compounds (CVOCs). These CVOCs such as 1,2-
DCE that have low aqueous solubility and a greater density
than water are called DNAPLs [4–6]. In addition, DNAPLs
include compounds such as chlorinated solvents, coal tar,
polychlorinated biphenyl and chemical intermediates that are
extensively used in industrial and commercial processes [7].
Additionally, when DNAPLs are released into the subsurface
from sources such as leaking underground storage tanks or
pipelines, flow by gravity through the unsaturated zone once
their residual saturation levels are exceeded. The emissions
are at all times combinations of different contaminants and
the concentrations strongly depend on the source where they
are emanated [8, 9]. They will gradually dissolve into flowing
13
Topics in Catalysis
PEI polymer
H 2N
H 2N
PEI–nZVI
In-situ remediation
(1,2–DCE)
(Vinyl
Chloride) (Ethylene)
DNAPL pools
groundwater to major depths below the water table. Because
of their poor solubility and high density, they are quickly
deposited as impermeable layer at the lowermost of an aqui-
fer. The contaminated zones can be a continuous source of
groundwater contamination, triggering serious threats to
human being and ecosystems [10, 11]. The dissolution of
DNAPL results in a contaminated plume of groundwater,
low permeability lenses or layers and then pool [7, 11]. Such
DNAPL pools and residuals become the contaminant sources
and dissolve slowly in the groundwater for a significant long
time, presenting huge challenges to the environment and
human beings [1, 7, 11]. Therefore, in situ remediation tech-
niques for the treatment of DNAPL bring substantial eco-
nomic benefits by allowing soil or groundwater to be treated
without being excavated and transported [12, 13].
Over the past two decades, several field studies have
shown that through the emplacement of permeable reac-
tive barriers (PRB), zero-valent iron nanoparticles (nZVI)
can significantly transform chlorinated contaminants faster
than other in situ technologies [10]. The nZVI is an efficient
reducing agent for DNAPLs reduction via the chemical reac-
tion process [13, 14]. The use of nZVI in the remediation of
hazardous contaminants from groundwater and wastewater
received considerable attention due to its larger surface area
and higher reactivity leading to easier degradation of con-
taminants [15]. The nZVI can easily transfer electrons to the
pollutants then degrade contaminants into non-toxic and less
toxic species all through the degradation processes [16]. The
Topics in Catalysis
tiny size of nZVI makes it more suitable to be injected into
the subsurface forming in situ reactive zones [17]. Moreover,
in recent years, the injection of nZVI to chemically decrease
chlorinated solvents has been proposed as a potentially sim-
ple, economical, and environmentally friendly process to
degrade DNAPLs [18]. Besides, the injection of high reac-
tive nanoparticles into the subsurface is being proposed as
an efficient in situ technology for remediating contaminated
groundwater [19]. The nZVI can be injected into the soil to
degrade chlorinated organic contaminants such as DNAPLs.
The nZVI particles have a strong susceptibility to agglomer-
ate because of their magnetic properties. When these parti-
cles aggregate, the soil acts as a filter and stops them from
penetrating through the soil surface to reach the contami-
nated site [19, 20].
On the contrary, the shortcomings of nZVI such as particle
agglomeration/oxidation, low mobility, and poor stability can
be resolved by modifying the surface of nZVI with PEI, form-
ing PEI-nZVI composite material [21, 22]. Certain polymers,
such as polystyrene sulfonate (PSS), and polyaspartate (PAA),
have been used to modify the surface of nZVI and have been
proved to decrease the aggregation of the nanoparticles [20,
23]. Nevertheless, PEI displays outstanding content of func-
tional groups, high solubility in water, and chemical stability
for a strong attraction with metals. Polyelectrolyte character
and larger macromolecular size of PEI make them very useful
in sequestering metal ions from dilute solutions [24]. Further,
the PEI-nZVI composite can be effectively injected into the
source of contamination through subsoil. In addition, PEI
offers good hydrophilicity, high rate and capacity of adsorp-
tion for contaminants [23–25]. Remediation of contaminated
groundwater ought to be a dynamic process that utilizes
information on the response of the ground-water system to
enhance the efficiency of injection and pumping procedures
[12, 26]. Studies reveal that injection of nZVI at a higher vol-
ume can deliver more nZVI particles at a given distance [26].
Well-controlled laboratory scale studies demonstrated many
insights to better comprehend the central chemistry and mech-
anisms of nZVI. Nevertheless, information obtained from the
field studies is valuable and of paramount importance, with
respect to the application of nZVI.
Equally important, resistively image profiling (RIP) is a
recently developed multi-electrode technology that has been
well utilized in land surveys [27]. This technique was estab-
lished to examine complex subsurface structures, particularly
in areas where conventional direct current (DC) sounding and
other potential methods are inappropriate to use. It is more
suited for areas where sidewise variations of geological struc-
ture have resulted to vertical electrical sounding (VES) unsuit-
able [27–29]. Besides, RIP can show comparatively more lat-
eral and vertical data on sub-water strata than conventional
DC sounding [30]. Through the RIP survey, efficiency can be
enhanced by carrying out measurements at the surface of the
water and thus reducing topographic effect when piloting such
measurements [29, 30].
In Taiwan, remediation of contaminated sites, especially
chlorinated organic compounds is a significant priority in the
environmental field [31]. In Miaoli county of Northern Tai-
wan, the soil and groundwater was contaminated with high
concentrations of DNAPLs released from a petrochemical
plant [32]. Previously there was no remediation conducted
until the Environmental Protection Agency (EPA) of Taiwan
requested the plant to conduct a remediation exercise on the
site a few years ago. Consequently, excavation and exposition
of the contaminated soil and groundwater were performed on
the site.
Therefore, the objectives of this study were to evaluate the
efficiency of nZVI-based treatment process for an aquifer con-
taminated with 1,2-DCE. In addition, the on-site injection of
PEI-nZVI by direct injection method was conducted, followed
by the observation of the reactive lifetime and longevity of
the injected nZVI in the field. Groundwater was then moni-
tored for dissolved/particulate iron species, 1,2-DCE and its
reduction products, site oxidants such as oxygen and other geo-
chemical parameters. The DNAPL contaminants were taken
from the site to the laboratory to test the reactivity of nZVI
collected from the aquifer. Furthermore, X-ray absorption near
edge spectroscopy (XANES) was also used to determine the
corrosion products and the mechanisms of DNAPL reduction
on unmodified nZVI and PEI-nZVI surfaces.
2 Materials and Methods
2.1 Preparation of Nano Zero‑Valent Iron
Nanoparticles
The zero-valent iron nanoparticles were synthesized using a
chemical reduction process that involves the use of sodium
borohydride as a reducing agent for Fe(0) precipitation. The
reaction can be described as:
FeSO4 + R(strong reducing agent) → Fe(0) (nano-mental) + RSO4
(1)
The reaction of a ferrous sulfate aqueous solution with this
strong reducing agent takes place in two steps:
Fe(H2 O)7 2+ + 2e− → Fe(0) ↓ +7H2 O (2)
2BH4 − + 6H2 O → 2B(OH)3 + 2e− + 7H2 (3)
By integrating the two half-reactions, the complete reaction
becomes:
Fe(H2 O)7 2+ + 2BH4 − → Fe(0) ↓ +2B(OH)3 + H2 O + 7H2
(4)
In order to avoid ­H2 hazard while preparing the nano-
particles, the preparation of nZVI was conducted in a high
13

performance hood at 60 fpm (ft/s) of gas emission rate with
a fixed-bed activated carbon absorption column.
Following this method, 15 g of ­FeSO4·7H2O were dis-
solved in 100  mL of 30% ethanol, and 70% deionized
(DI) water. The pH value was adjusted to 6.8 using 3.8 N
­NaOH(aq). After the addition of 2.7 g ­NaBH4 powder, the
mixture was stirred continuously for 1 h then it was sealed
in a Teflon-lined stainless-steel autoclave and maintained at
200 °C for 24 h. The solid product was collected by mag-
netic filtration and washed several times with ethanol. The
resultant nZVI were vacuum-dried overnight. The PEI solu-
tion was prepared by dissolving an appropriate amount of
the polymer into 500 mL DI water followed by sonication
for 2 h. Upon mixing the polymer solution with the resultant
particles, the resulting mixture was sonicated for 1 h and
then dried in an oven at 80 °C for 12 h.
2.2 Characterization of nZVI and PEI‑nZVI
The crystal structure of nZVI was measured by X-ray dif-
fraction (XRD) using monochromatic ­CuKα radiation (MAC
Science, MXP18). The pore volume and specific surface area
of the nZVI were obtained by N ­ 2 adsorption (Micromeritics
ASAP 2010) at 77 K. The morphology and microstructure
of the nZVI were determined by FE-SEM/EDS (Hitachi,
S-4700 Type II) with a resolution of 0.1 nm. In order to
avoid further oxidation, the nZVI samples were prepared by
drying in a small nitrogen-purged hood at room temperature
and then packed into the sample cell directly. XANES spec-
tra were collected at the Wiggler Beamline BL 17C1 at the
National Synchrotron Radiation Research Center (NSRRC)
of Taiwan. The electron storage ring was operated with
1.5 GeV of energy and a current range of 100–200 mA. A
Si (111) DCM was used for providing highly monochroma-
tized photon beams with energies of 5–15 keV and a resolv-
ing power (E/ΔE) of up to 7000. Data were collected in
fluorescence or transmission modes with a Lytle ionization
detector for the K-edge of Fe (7112 eV) at room tempera-
ture [33] XANES spectra were analyzed using the IFEFFIT
package [34].
2.3 Study Area
The potential pollution source in the pilot test site came
from a Taiwan vinyl chloride monomer (VCM), a petro-
chemical plant located in Miaoli county of Northern Tai-
wan. The on-site orthophoto map is shown in Fig. 1a. The
main research area was about (120 m × 60 m) south of the
VCM plant in the groundwater downstream direction. The
primary contaminant inside the plant were TCE, PCE, 1,2-
DCE and other hazard solvents, with 1,2-DCE forming the
major contaminant. Moreover, due to high concentrations
of contaminants on the site, the plant ceased its operation
13
Topics in Catalysis
for many years and was later relocated. The two-dimen-
sional lines are from north to south (wiring points D1, D2,
D18 and D19), covering as much DNAPL contaminated
area as possible were divided into several sampling wells
of A1, A11, A14, A16, and A24 as shown in Fig. 1b.
2.4 Resistively Image Profiling
Resistivity image profiling (RIP) method was developed and
used to investigate complex subsurface structures in areas
where conventional DC sounding and other methods were
unsuitable [29]. Numerous electrodes were inserted into the
surface, along the desired survey line. Two current-injected
electrodes and two potential measuring electrodes were
automatically selected and switched by the control unit of
the resistivity meter. A rough image of a subsurface was
then created from apparent resistivity pseudosection prior
to digital data processing. The resistivity depth profile was
obtained by applying 2D finite-element inversion [26, 32].
The McOhm-21 multi-functional resistivity meter manufac-
tured by OYO Corporation and a pole–pole electrode con-
figuration were used in this field study. Remote current and
potential electrodes were placed at a distance ten times the
expected depth of investigation, away from the survey line.
An electrode cable with electrodes at 1-m intervals and PVC
bottles linked to each electrode to prevent the cable from
sinking were used. Electrodes were kept in good contact
with the groundwater to ensure injection of electric current
into the strata through the groundwater.
2.5 Injection of Fe Nanoparticles and Field
Sampling
Furthermore, to comprehend the size of the contaminated
area and the efficiency of the cleaning operations, fifty-
three pumping and monitoring wells were drilled around
the contaminated site, forty-two wells in factory. The depth
of the wells ranged from 10 to 15 m. The direct injection
technique was used for the in situ applications of the pre-
pared PEI-nZVI particles where the pumpable slurry permit-
ted the injection, dispersed through the aquifer carried by
groundwater flow, and finally reaching the DNAPL pools.
Continuous pumping and treating contaminated groundwater
served as the first step towards the long-term remediation
groundwater. Samples collected from the wells were regu-
larly tested every 3 months to evaluate the efficiencies of
remediation. The liquid samples were filled into the VOC
bottle, dried by a lampshade and then ground in an anaerobic
glove box to facilitate instrumental analysis in the future.
Topics in Catalysis

(b)
(a)

50 (c)
PEI-nZVI
40 Fresh nZVI
30
Zeta potential (mV)

20
10
0
-10
-20
-30
6 7 8 9 10 11 12 13
pH

Fig. 1  a Research site orthophoto map, b line configuration of ground resistivity imaging profile method, and c Zeta potential of nZVI and PEI-
nZVI at different pH values

3 Results and Discussion
3.1 Morphologies, Configurations,
and Physiochemical Properties of nZVI/
PEI‑nZVI
The improved mobility and stability of nZVI and PEI-nZVI
can be characterized further by increasing their surface
potential. The volume of surface potential largely defines the
extent of the electrostatic repulsion between nanoparticles.
In general, the zeta potential is studied to show the surface
potential of the prepared nanoparticles. It have been reported
that a zeta potential of at least ± 30 mV is required to sustain
a metastable suspension [35]. As revealed in Fig. 1c, the
initial pH of fresh nZVI and PEI-nZVI was 7.0 and the zeta
potential of nZVI was 40 mV while as that of PEI-nZVI
was 48 mV. Furthermore, the zeta potential values of both
the fresh nZVI and the PEI-nZVI decreased with increasing
pH values. The fresh nZVI exhibited a negative charge at
pH > 10; on the other hand, PEI-nZVI showed negatively
charged pH ≤ 10.5. Contaminants in groundwater con-
tains predominantly negative surface charges under typical
groundwater environments [35, 36]. Therefore, the positive
charged nZVI will donate electrons to the aquifer materials
causing poor mobility and stability.
Table 1 displays Taiwan groundwater contaminations con-
trol and regulatory standards value for soil and groundwater
pollutants. Furthermore, Fig. 2a indicates the concentration

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 Topics in Catalysis

Table 1  Taiwan EPA groundwater contamination control and regula- 12

tory standards values for soil and groundwater pollutants, respectively 1,2-Dichloroethane (a)
Chlorinated hydrocarbons Monitoring standard value 10 c-1,2-Dichloroethene

Concentration x10-4(μg L–1)

(mg L−1) t-1,2-Dichloroethene
Category ­1a Category ­2b 8 Tetrachloroethene
1,1,2-Trichloroethane
Carbon tetrachloride 0.005 0.050 Trichloroethene
Chlorobenzene 0.100 1.000 6
Vinyl Chloride
Chloroform 0.100 1.000
Chloromethane 0.030 0.300 4
1,4-Dichlorobenzene 0.075 0.750
1,1-Dichloroethane 0.850 8.500 2
1,2-Dichloroethane 0.005 0.050
1,1-Dichloroethylene 0.007 0.070 0
Cis-1,2-Dichloroethylene 0.070 0.700 0 3 6 9 12 15 18 21 24 27 30 33 36 39 42 45 48
Trans-1,2-dichloroethylene 0.100 1.000 Sampling date (months)
2,4,5-Trichlorophenol 0.370 3.700
2,4,6-Trichlorophenol 0.010 0.100
4.0
(b)
Pentachlorophenol 0.008 0.080 A11
3.5
Tetrachlorethylene (tetrachlorethylene) 0.005 0.050 A14

Concentration x10-5(μg L–1)

Trichlorethylene (trichlorethylene) 0.005 0.050 3.0 A16
Vinyl chloride 0.002 0.020
A24
Dichloromethane 0.005 0.050 2.5
1,1,2-Trichloroethane 0.005 0.050
2.0
1,1,1-Trichloroethane 0.200 2.000
1,2-Dichlorobenzene 0.600 6.000 1.5
3,3′-Dichlorobenzidine 0.010 0.100

a
 Tolerable concentrations of groundwater pollutants in drinking water
source protection area
b
 Tolerable concentrations of groundwater pollutants in other area
of seven major DNAPL contaminants found in sampling
well A11. The results shows that the concentrations of seven
major DNAPL contaminants were high. The concentration
of 1,2-DCE (9000 µg L−1) was very high due to the inher-
ently higher concentrations of this DNAPL contaminant at
well A11. On the first feeding, the concentration of DNAPLs
was high because PEI was still on the surface of nZVI. How-
ever, on the second feeding there was a significant decrease
to the concentration of DNAPLs. The concentration decrease
indicated that PEI had fully reached dissolution and the nZVI
suspension solution had gradually dissolved, exposing the
high reactive nZVI to degrade DNAPL contaminants. Addi-
tionally, a significant concentration increase was observed
during month 33 because well A11 was located downstream
where other DNAPL contaminants flow with the groundwater,
resulting in higher concentrations. Moreover, this phenom-
enon was due to contaminants caused by prolonged dissolu-
tion of DNAPL contaminants, which raises the concentration.
Similarly, Fig. 2b reveals a substantial reduction to concen-
tration of DNAPLs after PEI-nZVI injection, indicating that
the high reactive nZVI had an immediate degradation effect.
1.0
0.5
0.0
0 3 6 9 12 15 18 21 24 27 30 33 36 39 42 45
Sampling date (months)
Fig. 2  Concentration profiles of a seven different DNAPLs contami-
nants at sampling well A11. b 1,2-Dichloroethane at different sam-
pling wells of a A1, b A11, c A14, and d A16 over the years
The 1,2-DCE and vinyl chloride concentrations in the wells
were again increased due to the inherently higher concentra-
tions of these two DNAPL contaminants at sampling well
A11. Therefore, through a direct injection of nZVI solution
at an early stage, the DNAPL contaminants were removed.
However, due to limited amount of nZVI solution, DNAPL
contaminants could not be removed completely, and the con-
taminants were re-dissolved to make the concentration of
contaminant high again. Nevertheless, through a long-term
continuous treatment, the contaminants concentration were
effectively reduced.
The FE–SEM analysis of nZVI and PEI-nZVI reacted
with contaminated water samples taken from sampling well
A11 and tested in the laboratory. The nZVI in the absence of
PEI coating (Fig. 3a) exhibited a spherical shape with sizes
of 60–80 nm. In contrast, the PEI-stabilized nZVI (Fig. 3b)

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Topics in Catalysis

311
(a)
440
333
220 400

Intensity (a.u.)
(i)

(ii)

(iii)

20 30 40 50 60 70 80
2θ (degree)

Fe foil (b)
FeO STD

Normalized absorbance (a.u.)

Fe2O3 STD
Fe3O4 STD
nZVI+A11
PEI-nZVI+A11

0.2

0.0
Fig. 3  a and b FE–SEM microphotos of a nZVI and b PEI-nZVI, 7110 7120

reacted with DNAPLs contaminants from sampling well of A11
demonstrated a nearly monodisperse size of 30–60 nm. The
particles were also much smaller. Due to the magnetic prop-
erty of nZVI, most particles formed some aggregates. This
could be because of the nZVI without any surface modifica-
tion by a polymer, which contains smaller surface area that
easily causes particle aggregation. Nevertheless, with the
PEI coating on the surface of nZVI having steric effect, the
particles became evenly dispersed and accordingly rendering
large surface area with highly reactive sites to improve the
removal of more contaminants. The PEI coating on the sur-
face of nZVI particles restrainted the magnetic interactions
between the particles of nZVI.
In addition, the XRD analysis nZVI and PEI-nZVI reacted
with contaminated groundwater samples taken from sam-
pling well A11 is depicted in Fig. 4a. After treatment, the liq-
uid–solid separation by suction filtration was used to collect
the solution. The XRD patterns confirmed the formation of
elemental iron and the phase purity of the nanoparticles. The
peaks assigned to the crystalline structure of Fe(0) (JCPDS
No. 87–0721) were detected in both samples. Consequently,
7100 7110 7120 7130 7140 7150 7160 7170
Photon energy (eV)
Fig. 4  a XRD patterns of (i) ­Fe3O4 (ii) nZVI, (iii) PEI-nZVI after
1  day reaction with DNAPLs contaminated aqueous solutions from
sampling well A11; b Fe K-edge XANES spectra of nZVI and PEI-
nZVI reacted with DNAPLs contaminants from sampling well A11
the surface stabilization process did not display any significant
effect on iron oxidation. Furthermore, regardless of PEI or no
PEI coating, after 1 day reaction with contaminants, the signal
of Fe remained at about 2θ = 45. In order to thoroughly exam-
ine the nature of nZVI products, Fig. 4b shows the XANES
spectra of a Fe atom of nZVI and PEI-nZVI samples reacted
with contaminants from sampling well A11. The XANES
spectra of an Fe atom in reacted nZVI and PEI-nZVI sam-
ples, exhibited as an absorbance feature (Fe = 7115 eV) for the
1s–3d transition. The sharp feature at 7134 eV arose from the
dipole-allowed 1s–4pxy electron transition, showed the pres-
ence of Fe(III) [37, 38]. The strength of the transition was
relative to the population of ­Fe2O3 in the nZVI. In comparison
with iron standards, the XANES spectra of nZVI is similar

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 Topics in Catalysis

Table 2  Fe XANES K-edge Iron compound XANES nZVI nanoparticles were oxidized to forming a thin iron oxide
absorption of nZVI and PEI- absorption layer, hindering more oxidation prior to PEI coating.
nZVI reacted with DNAPLs
from sampling well A11
(eV) Fe K-edge EXAFS spectroscopy can provide the informa-
compared to that of standard Fe(0) foil 7111.99
tion about the atomic arrangement of Fe species in terms
samples
FeO standard 7113.74
of interatomic distance, coordination number, and kind of
Fe3O4 standard 7115.10
neighbors. The results in Fig. 5a, b show the fine-structure
Fe2O3 standard 7117.88
parameters of nZVI and PEI-nZVI after 1 day reaction with
nZVI + A11 7114.84
DNAPL contaminants from sampling well A11. The EXAFS
PEI-nZVI + A11 7117.36
Table 3  Fine-structure parameters of nZVI and PEI-nZVI after 1 day
reaction with DNAPLs contaminants from sampling well A11
to that of ­Fe3O4. The XANES results of reacted species are
First shell CN (± 0.05)a R (± 0.02 Å)b ∆σ2 (Å2)c
itemized in Table 2. It is obvious that after the reaction with
contaminants, nZVI possessed more F ­ e3O4, whereas PEI-nZVI nZVI + A11 Fe–O 4.17 1.95 0.011900
contained more ­Fe2O3. These results are in line with XPS and PEI- Fe–O 3.00 1.93 0.008916
EDS results [4], which indicated that the carbon and oxygen nZVI + A11
content on PEI-nZVI is greater than on the nZVI. Likewise, the a
 Coordination number
b
 Bond distance
c
 Debye–Waller factor
Fe-O (a)

(a)
FT magnitude (a.u.)

FeSO4 Fe3O4
Intensity (a.u.)

FeO

0 2 4 6 8 10
Interatomic distance (Å)
716 714 712 710 708 706 704
Binding energy (eV)
Fe-O (b)
(b)
Fe3O4
FeSO4
FT magnitude (a.u.)

FeO
Intensity (a.u.)

0 2 4 6 8 10 716 714 712 710 708 706 704

Interatomic distance (Å) Binding energy (eV)

Fig. 5  EXAFS Fe K-edge Fourier transformed spectra obtained after Fig. 6  Fine section for Fe 2p3/2 fitting results for 1 day reaction of a
1  day reaction of a nZVI, and b PEI-nZVI with DNAPLs contami- nZVI and b PEI-nZVI with DNAPLs contaminants from sampling
nants from sampling well A11, respectively well A11, respectively

13
Topics in Catalysis
fitting results for the oxygen shell listed in Table 3, suggest-
ing that nZVI and PEI-nZVI have central Fe atoms coordi-
nated primarily by Fe–O. The standard Fe–O interatomic
distances in nZVI and PEI-nZVI were 1.95 Å and 1.93 Å,
with the coordination number of 1.47 and 3.00, respectively.
In both samples, the e Debye–Waller factors (σ2) is < 0.011
(Å2). Therefore, the oxidized permeable layer established
onto the nZVI surface controls mass transfer and subse-
quently the depletion of pollutants by the nZVI core [21,
38]. Through adsorption mechanism, the porous structure
of iron oxides will contribute to the removal of 1,2-DCE.
The higher ligancy in the polymer-coated nZVI is associated
with oxidation number and higher oxygen density [4]. Sub-
sequently, a permeable layer of corrosion products generated
on the reactive sites of the surface of nZVI controls the deg-
radation of contaminants by the nZVI core [21]. The porous
layer on the surface of nZVI breaks it into tiny particles,
making it possible for pollutants to react with the iron core.
(a)
(c)
Fig. 7  a and c ­N2 adsorption/desorption isotherms of nZVI and PEI-
nZVI reaction with DNAPLs contaminants from sampling well A11,
respectively. b and d Pore size distribution curves of nZVI and PEI-
In addition, Fig. 6a, b shows that the main component on the
surfaces of nZVI and PEI-nZVI products after being reacted
with contaminants from sampling well A11 is mainly F ­ e3O4.
The results suggest that surface alteration resulted due to an
increased reduction reaction on the surface of nZVI, where
­Fe3O4 having higher oxidation state substitutes FeO species.
Probably, the suspension of the contaminants on the surface
of PEI-nZVI enhances interaction of nZVI with the pollut-
ants. The nature and the surface of nZVI are the most impor-
tant aspects during the reductive reaction process. The shell
of iron oxides facilitates the reduction reaction via electron
transfer at the surface of iron [38].
Non-specific physical adsorption studies were conducted
for nZVI and PEI-nZVI after 1 day reaction with contami-
nants from sampling well A11 to measure the total surface
area and pore size distribution (Fig. 7a–c). The method of
Barrett, Joyner, and Halenda (BJH) was engaged to exam-
ine the pore size distribution. The distribution showed
(b)
(d)
nZVI, reaction with DNAPLs contaminants from sampling well A11,
respectively
13
 Topics in Catalysis

that the nZVI and PEI-nZVI species are mesoporous. The
adsorption–desorption isotherms display performance of
a Type IV hysteresis isotherm with an H3-like hysteresis
loop. It also shows the existence of mesoporous charac-
teristic capillary condensation of nitrogen, suggesting that
the species were mostly mesoporous. The Type IV hyster-
esis isotherm is believed to portray capillary condensation
principle in that it settles before the saturation pressure is
attained. Adhikari and Lin reported that the mesoporous
capacity is the amount adsorbed at the elevation and the
mesoporous volume is then acquired by assuming the con-
densate density to be that of liquid nitrogen (Fig. 7b–d)
[39, 40].
Resistivity image profiling is a very good technique to
confirm and analyze the exact plume point of DNAPLs. By
using RIP technique, the conductivity data of PEI-nZVI
solution and sampled groundwater were similarly indicat-
ing a lower conductivity of FeO species. As displayed in
Fig. 8a, b, it can be seen that the color changes from deep
red (Fig. 8a) to light orange (Fig. 8b), indicated the success-
ful decontamination of 1,2-DCE contaminants. Evidently,
the data of in situ remediation indicated that concentrations
of 1,2-DCE after using well-injection method was notably
reduced. These results directed that the high resistivity zone
is associated with dense DNAPLs, more especially 1,2-DCE.
The combinative technology of floating PEI-nZVI and RIP
technique would be economically and environmentally
attractive. Figure 9 displays a schematic illustration sum-
marizing the synthesis and application of PEI functionalized
nZVI for in situ remediation of DNAPLs in contaminated
groundwater. The reduction ability of the injected nanopar-
ticles in degrading 1,2-DCE contaminant was effectively

Fig. 8  Resistivity image
Model resistivity with topography
profiling along line 1 a before
PEI-nZVI and b after 1 day 0.0 Iteration 5 RMS error = 3.2 48.0
suspension feedings 0.0 - 16.0 32.0

-5.0 - (a)

-
Elevation (M)

-10.0

-15.0 -
-20.0 -
N
-25.0 - S

-30.0 - Unit Electrode Spacing = 1.00 m

Model resistivity with topography

Iteration 5 RMS error = 3.2 48.0
0.0
0.0 - 16.0 32.0

-5.0 -
(b)
-10.0 -
Elevation (M)

-15.0 -
-20.0 -
-25.0 - N S

-30.0 - Unit Electrode Spacing = 1.00 m

13
Topics in Catalysis
PEI polymer
nZVI aggregates
H 2N
+ H 2N
H 2N
PEI–nZVI
Soil surface
Injection In-situ remediation
Water table
(1,2–DCE)
Fe(0) core PEI
Groundwater
flowing
(Vinyl
Chloride) (Ethylene)
Reduction
reaction
Aquifer
DNAPL pools
Low permeability layer
Fig. 9  Systematic illustration on the synthesis and application of PEI-
nZVI on in situ remediation of 1,2-dichloroethane DNAPL
exploited. The prepared PEI-nZVI particles injected into soil
and it was transported with flowing groundwater to DNA-
PLs site. During the flowing, the coated PEI dissipated with
increasing submerging period in groundwater. Subsequently,
highly reactive nZVI surface flowed with groundwater, while
degrading the 1,2-DCE into low-toxic vinyl chloride and
ethylene.
4 Conclusions
In this work, polymer modified nZVI was seen capable
of remediating 1,2-DCE through direct injection method.
It is apparent that both nZVI and PEI-nZVI demonstrated
extraordinary effects on the degradation of 1,2-DCE contam-
inants. The in situ results indicated that nZVI and PEI-nZVI
successfully removed 1,2-DCE in contaminated groundwa-
ter. Moreover, the injected PEI-nZVI was able to stabilize
and mobilize the nZVI delivery to the DNAPLs plume, thus
enhancing nZVI reactivity and lifespan in contaminated
zone. The efficient reaction and significant degradation of
1,2-DCE indicated that PEI-nZVI remediation technique
is an economically and environmentally friendly method
for in situ remediation and dechlorination of contaminated
groundwater.
Acknowledgements  The financial support of Ministry of Science and
Technology (MOST), Taiwan (MOST 103-2621-M-155-001) is grate-
fully acknowledged. We also thank Prof. Y. W. Yang, Dr. J. F. Lee,
and Dr. Jeng-Lung Chen from Taiwan National Synchrotron Radia-
tion Research Center (NSRRC) for their help in the XANES/EXAFS
experiments or data analyses. We finally thank Prof C.H. Yang from
National Central University (NCU) who helped us with the Resistivity
Image Profiling (RIP) experiments.
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Affiliations
Ndumiso Vukile Mdlovu1 · Kuen‑Song Lin1 · Sat Septian Dwitya1 · Chung‑Yu Chen1 · Chao‑Lung Chiang1
1
* Kuen‑Song Lin
kslin@saturn.yzu.edu.tw
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Department of Chemical Engineering and Materials Science/
Environmental Technology Research Center, Yuan Ze
University, Chung‑Li District, Taoyuan 32003, Taiwan, ROC