Separation and Purification Technology 132 (2014) 346–353

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Removal of 2,4-dichlorophenol from contaminated soil

by a heterogeneous ZVI/EDTA/Air Fenton-like system
Haiyan Zhou a,b, Qian Sun a,b, Xun Wang a, Linling Wang a,⇑, Jing Chen a, Jingdong Zhang b, Xiaohua Lu a,b,⇑
a
Environmental Science Research Institute, Huazhong University of Science and Technology, Wuhan 430074, PR China
b
School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The removal of 2,4-dichlorophenol (2,4-DCP) from contaminated soil by an amino carboxylic acid-
Received 8 December 2013 enhanced zero-valent iron/Air (ZVI/Air) Fenton-like system has been performed in this study. The effects
Received in revised form 13 May 2014 of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine-N,N0 -disuccinic acid (EDDS) on the cat-
Accepted 15 May 2014
alytic degradation of 2,4-DCP were primarily studied in the presence of ZVI catalyst and O2 oxidant. The
Available online 2 June 2014
result indicated that the degradation of 2,4-DCP in ZVI/Air system was hindered by EDDS but enhanced
by EDTA. Complete destruction of 2,4-DCP in contaminated soil was achieved in the heterogeneous ZVI/
Keywords:
EDTA/Air (ZEA) Fenton-like system under ambient air and room temperature. ZVI and EDTA were the pre-
Soil remediation
ZVI/EDTA/Air
dominant factors influencing the degradation of 2,4-DCP. The degradation of 2,4-DCP was ascribed to het-
EDDS erogeneous catalytic reaction over the ZVI surface in situ modified by EDTA via the formation of
2,4-Dichlorinphnol monodentate inner-sphere complexes. In this system, two main reactive oxygen species of O 
2 /HO2
Superoxide anion radicals and Fe(IV) were generated, in which O 
2 /HO2 was predominant. The novel ZEA oxidation system provides
a promising eco-friendly alternative for the remediation of contaminated soils.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction in soil is advanced oxidation techniques (AOTs) with Fenton’s

The contamination of soil is becoming a global problem
of increasing concerns. Remediation of soil contaminated by
toxic and carcinogenic chemical compounds known as persistent
organic pollutants (POPs) has been demonstrated as one of the
most difficult challenges. Amongst the group of POPs, 2,4-dichloro-
phenol (2,4-DCP) has been classified as the priority pollutant by US
EPA and European Commission. 2,4-DCP is wildly utilized in many
agricultural and industrial manufactures such as herbicide, fungi-
cide, and wood preservatives. More, chlorophenols (CPs) may
emerge as degradation products from a number of pesticides [1].
Due to their high toxicity and poor biodegradability, contamination
of soil by CPs poses deleterious threats to water resources, public
health and environmental security.
In order to eliminate the risk of CPs contaminated soil, numerous
methods have been developed. One of the techniques used to
remove toxic and biorefractory contaminants of high concentration
⇑ Corresponding authors. Address: Environmental Science Research Institute,
Huazhong University of Science and Technology, Wuhan 430074, PR China (X. Lu).
Tel./fax: +86 27 87792159.
E-mail addresses: wanglinling@mail.hust.edu.cn (L. Wang), hust-esri2009@
hotmail.com (X. Lu).
reagent (Eqs. (1)–(3)) [2,3]. The Fenton reaction has been proved
to be efficient in remediation of organic compounds contaminated
soils [4–6]. However, the pH restriction (pH < 4) hinders the practi-
cal applications of Fenton reaction to natural soil pH which is
approximately neutral or slightly alkaline [7,8].
Fe2þ þ H2 O2 ! Fe3þ þ  OH þ OH ð1Þ
Fe2þ þ  OH ! Fe3þ þ OH ð2Þ
H2 O2 þ  OH ! HO2 þ H2 O ð3Þ
Fe0ðsÞ þ H2 O2 þ 2Hþ ! Fe2þ þ 2H2 O ð4Þ
To overcome this problem, iron-bearing solids [9–11] have been
employed to form heterogeneous Fenton-like reaction with hydro-
gen peroxide (Eq. (4)). Alternatively, chelating agents can be uti-
lized to enhance the efficiency of heterogeneous Fenton’s
reaction under natural soil pH conditions [12–14]. Nevertheless,
when H2O2 encounters iron and manganese oxyhydroxides, or soil
organic matters commonly existing in surface soils, it quickly
decomposes. Therefore, a large amount of H2O2 is required, which
results in the problems of low efficiency and high cost.

http://dx.doi.org/10.1016/j.seppur.2014.05.037
1383-5866/Ó 2014 Elsevier B.V. All rights reserved.
 H. Zhou et al. / Separation and Purification Technology 132 (2014) 346–353
It has been reported that the reaction of zero-valent iron (ZVI)
with dioxygen can generate hydrogen peroxide in situ (Eq. (5)) [15].
Fe0ðsÞ þ O2 þ 2Hþ ! Fe2þ þ H2 O2 ð5Þ
However, the ZVI/Air system also encounters the problem of
iron precipitation under neutral or alkali conditions. Thus, chelat-
ing acids are used to enhance the efficiency of the ZVI/Air system.
It has been revealed that the complexes of EDTA with Fe(II) is able
to break down the O–O bond of molecular oxygen and generate
H2O2 in situ [16,17]. ZVI/EDTA/Air (ZEA) system has been investi-
gated and applied to oxidize various hazardous substances [18,19].
This novel heterogeneous Fenton-like reaction system is
arousing great interests of public and researchers from scientific
institutes; however, almost all the relevant works were carried
out in solution rather than in soil or slurry. Our group has studied
the degradation of DDTs in the soil using the ZVI/EDTA/Air system
[20]. However, the mechanism for the degradation was barely
explored. It has been a controversial issue concerning reactive
oxygen species being hydroxyl radical (OH) or high-valent iron
species (Fe(IV)) in the heterogeneous reaction of ZVI with oxygen
[21,22], while superoxide anion radicals (O 
2 /HO2) was rarely
mentioned, which was also observed in some heterogeneous
Fenton-like systems [23]. Pang et al. [24] have proposed that
peroxyl radical should be taken into account to reasonably explain
the discrepancy between their researches. It has been demon-
strated that O
2 radicals are important active oxidative species in
the degradation of a wide range of organic contaminants, including
chlorinated solvents, pesticides, and dioxins [25,26]. Besides, it can
also reduce 2-CB and Fe(III) to biphenyl and Fe(II) respectively
[27,28]. To provide new insight into the ZVI/EDTA/Air reaction,
such mechanism is necessary to be explored.
As a structural isomer of EDTA, (S,S)-N,N0 -ethylenediamine dis-
uccinic acid (EDDS) has been successfully applied to the remedia-
tion of heavy metals contaminated soils instead of EDTA [29–31].
Recently, Fe(III)–EDDS in H2O2-based homogeneous Fenton-like
system has been employed to degrade bisphenol A in solution,
which offers a new treatment option under higher pH conditions
[32,33].
Herein, The comparison of EDTA and EDDS on the removal of
2,4-DCP from contaminated soil in the ZVI/Air Fenton-like system
is studied firstly to explore the feasibility of EDDS substitution
for EDTA. Based on the comparative result, the effects of variables
such as EDTA, ZVI, soil pH and air aeration in ZVI/EDTA/Air system
were investigated, and the reaction and degradation mechanisms
were clarified as well.
2. Materials and methods
2.1. Materials
2,4-Dichlorophenol (2,4-DCP, 99.9%), 2-monochlorophenol
(99.9%), 4-monochlorophenol (99.9%), phenol (99.9%), catechol
(99.9%) were purchased from Sigma–Aldrich, USA. Iron powder
(325 mesh), H2Na2EDTA (99%) and HNa3EDDS (35%) were obtained
from Sinopharm Chemical Reagent Co. Ltd. Methanol (HPLC grade)
was ordered from Merk, USA. N2 (99.5%) was delivered from
Wuhan oxygen cylinder test factory. De-ionized water was used
to prepare all solutions. All other reagents used were above analyt-
ical grade.
Kaolin clay (chemical purity, Tianjin Kermel Chemical Reagent
Development Center, China) was used as simulated soil. 2,4-DCP
contaminated kaolin clay was prepared by adding 2,4-DCP ethanol
solution into kaolin clay, mixed evenly, vibrated vigorously for 24 h
in 25 °C thermostat water bath, dried in air to evaporate the
methanol thoroughly and grinded to sieve through 100 mesh.
347
2.2. Apparatus
Experiments were performed in a 500 mL Pyrex Jacket Reactor
equipped with a two-stage tail gas absorber. A magnetic stirrer
with a temperature detector was applied to mix the slurry in reac-
tion evenly and keep the slurry temperature constant. Purified air
or nitrogen was supplied through the glass diffuser regulated by a
rotermeter.
2.3. Experimental procedures
A total of 20 g 2,4-DCP contaminated soil, certain iron powder
and 400 mL EDTA solution of certain concentration were added
into the jacket reactor. The reactor was placed on magnetic stirring
apparatus to mix the slurry uniformly, regulated the temperature
at certain degree and then aerated to enable the reaction. At prede-
termined time, 5 mL sample was taken out. At least triplicate runs
were carried out.
The taken-out slurry was separated by centrifugation at
4000 rpm and filtered through 0.45 lm filtration membrane. The
supernatant pH was measured by pH meter and EDTA and 2,4-
DCP were determined by HPLC. The residual 2,4-DCP in solid phase
was extracted by 1 mol/L NaOH solution with the assistance of
ultrasonication (20 kHz) for 30 min. The recovery of 2,4-DCP in
Kaolin was 92.7%. The extraction mixture was then centrifuged,
and the supernatant was regulated to pH 3–4 by using 1 mol/L
sulfuric acid for analysis of 2,4-DCP. Finally 2,4-DCP in the slurry
was quantified.
2.4. Analytical methods
Quantitative analyses of 2,4-DCP, EDTA and EDDS were per-
formed with high performance liquid chromatography (Agilent
1200, HPLC) equipped with an Agilent Eclipse XDB-C18 column
(5 lm, 4.6 mm  150 mm) and a VWD detector at a flow rate of
1.0 mL/min. For 2,4-DCP, mobile phase was a mixture of methanol
and 1% acetic acid aqueous solution (V:V, 65:35) and UV absor-
bance wavelength was 280 nm. For EDTA and EDDS determination,
FeCl3 solution and glacial acetic acid was added to sample to con-
vert EDTA and EDDS to Fe(III) complex. The determination of EDTA
was conducted with mobile phase of 0.03 mol/L acetic acid and
sodium acetate buffer solution (pH = 4) under best UV absorbance
wavelength at 258 nm. The determination of EDDS was conducted
with mobile phase of a mixture of methanol and acetate buffer
(2 mmol/L tetrabutylammonium hydrogen sulfate and 15 mmol/L
sodium acetate) solution (V:V, 20:80) with UV absorbance wave-
length of 236 nm.
Released Cl and low molecular organic acids were detected by
a Dionex ICS-1500 ion chromatography system equipped with CD
25 conductivity detector, IonPac AS 23 analytical column, IonPac
AG 23 guard column, and anion ASRS electrolytic suppressor. Inter-
mediate products were determined by HPLC-MSD. HPLC was Agi-
lent 1100 series and mass spectrometry was carried out using a
XCT ion trap with electrospray ionization source. Attenuated total
reflectance-Fourier transform infrared (ATR-FTIR) analysis was car-
ried out with a VERTEX 70 Micro Fourier Transform Infrared/
Raman spectroscope equipped with a high sensitivity DLATGS
detector and a horizontal ATR-FTIR attachment (Bruker, Germany).
The concentration of total dissolved iron ions was detected by
AA-300 atomic absorbing spectrometer (Perkin Elmer Company,
USA) and dissolved ferrous ion concentration was by 1,10-phe-
nantroline spectrometric method. Dissolve oxygen (DO) was mon-
itored by a dissolved oxygen meter (Shanghai Precision & Scientific
Instrument Co., Ltd., JPB-607A). A pH meter (Sartorius universal
type, PB-10) was utilized to track pH variation.
348 H. Zhou et al. / Separation and Purification Technology 132 (2014) 346–353
3. Results and discussions
3.1. Comparison of 2,4-DCP degradation in systems with different
chelating ligands
Fig. 1a demonstrates the degradation of 2,4-DCP in ZVI/Air,
ZVI/EDTA/Air and ZVI/EDDS/Air systems. In ZVI/Air system, 72%
2,4-DCP could be removed after 3-h reaction, in which 13%
2,4-DCP was removed by volatization. ZVI was quickly oxidized
to ferrous (Fe(II)) and ferric (Fe(III)) irons by O2, which gave rise
to the production of reactive oxygen species (ROS), capable of
decomposing both organic and inorganic contaminants [18,19,34].
Therefore, 2,4-DCP was partly removed in ZVI/Air system.
It is worth noting that ZVI corrosion causes the solution pH to
rise to above 8 in ZVI/Air system. While in ZVI/EDTA/Air and ZVI/
EDDS/Air systems, the pH values were observed to be 5–7 and
5.5–7.5, respectively, without regulating pH. It is believed that
the chelating agents and their degradation products of low molec-
ular weight organic acids play a predominant role in the self-buf-
fering ability [19]. Interestingly, the addition of chelating agents
not only provides the acidic pH buffering ability, but also alters
the degradation rate of 2,4-DCP. When EDTA was introduced into
the ZVI/Air system, the degradation of 2,4-DCP was significantly
promoted. Within 3 h, 98% 2,4-DCP was removal (only including
4% volatile 2,4-DCP). In this system, EDTA could interact with
metal surface to weaken and break the metal oxygen bonds in
the lattice of the surface oxide layer [35], accelerating the reaction
of iron to Fe(II) and Fe(III). The Fe(II) and Fe(III) were then complex
with EDTA to form stable metal-chelate complexes, evidently acti-
vating oxygen to generate H2O2 in situ [19,36]. In contrast, an
inhibitory effect of EDDS ligand on the oxidation reaction was
observed in ZVI/EDDS/Air system, which is consistent with previ-
ous reports in traditional Fenton reaction [37,38].
Further analysis indicated that in ZVI /Air, ZVI/EDTA/Air and
ZVI/EDDS/Air systems, degradation of 2,4-DCP followed the
pseudo-first-order kinetic (R2 > 0.95). The pseudo-first-order rate
constant (kobs) was obtained from the slope of the straight line
for the first-order plot (Table 1). It can be seen that the kobs values
for 2,4-DCP were 1.68, 0.69 and 0.28 h1 in ZVI/EDTA/Air, ZVI/Air
and ZVI/EDDS/Air systems, respectively. It is known that in the
presence of chelating acids, 2,4-DCP and the two chelating acids
are simultaneously degraded, and competitive degradation rela-
tionship forms between target pollutant and chelating agents. In
ZVI/EDTA/Air system, kobs for 2,4-DCP was larger than that for
EDTA (1.02 h1), implying that 2,4-DCP is preferentially oxidized.
While in ZVI/EDDS/Air system, kobs for 2,4-DCP is less than that
for EDDS (0.88 h1), meaning that EDDS is more readily oxidized.
As the result, 2,4-DCP degradation was restrained.
Fig. 1. Performance of different comparison systems: (a) 2,4-DCP decomposition; (b) EDTA decomposition. Initial conditions: iron 12.5 g/L; EDTA(EDDS) 0.4 mmol/L.
Table 1
kobs values in different systems.
System kobs(2,4-DCP) (h1) kobs(EDTA) (h1) kobs(EDDS) (h1)
ZVI/Air 0.69 – –
ZVI/EDTA/Air 1.68 1.02 –
ZVI/EDDS/Air 0.28 – 0.88
Moreover, considering that the different effects of EDTA and
EDDS might also arise from their different coordination modes
with mineral surface, the modified surfaces of ZVI by EDTA and
EDDS were studied with ATR-FTIR spectroscopy. The ATR-FTIR
spectra of ZVI before and after aeration for 1 h were recorded
(Fig. 2a and b). The peaks at 1613 and 1390 cm1 in ZVI/EDTA/
Air system and 1583 and 1393 cm1 in ZVI/EDDS/Air system were
assigned to characteristic asymmetric stretching vibration (vas) and
symmetric stretching vibration (vs) spectral bands of carboxyl
group (–COO). The shifted peaks revealed the direct chemical
bonding between carboxylate groups and ZVI surface.
It has been reported that the coordination modes of carboxylate
and metal could be distinguished by the difference of wavenumber
between the carboxylate stretching bands (Dm = vas(–COO) 
vs(–COO)) [39]. When Dm is larger than 200 cm1, the coordination
between carboxylate and metal is monodentate binding. In the ZVI/
EDTA/Air system, the Dm value of 223 cm1 indicates that EDTA is
surface coordinated with ZVI by monodentate binding, either a
monodentate inner-sphere directly coordinated to surface metal
ions or outer-sphere complexes involving ester linkages through
one carboxylate group of EDTA [23]. Moreover, vas(COO) in the
spectra of ZVI in ZVI/EDTA/Air system shifts up to higher wavenum-
ber in comparison with that of pure EDTA, implying the formation
of a direct bonding between O atom of COO in EDTA and the Fe
atom on ZVI surface, which would shorten the C@O bond and
increase the vas(COO) [40]. Hence, it is concluded that the
adsorption of EDTA onto the surface of ZVI is dominated by the for-
mation of monodentate inner-sphere complexes. The interaction of
EDTA on ZVI surface probably enhances the catalytic activity by
competition of affinity of O2 to ZVI, dissolution of iron from solid
catalysts and enhancement on the redox properties of iron [41].
Consequently, it plays an important role in intensifying the produc-
tion of ROS.
However, in ZVI/EDDS/Air system, the Dm value was 190 cm1,
less than 200 cm1, indicating a different coordination of EDDS
on ZVI surface. Wang et al. [41] have mentioned that on the surface
of FeBiO3, EDTA formed a cave suitable for two H2O2 molecules,
and thus the local concentration of H2O2 was higher than that on
the surface of bare or oxalic acid modified FeBiO3. Therefore, it
accelerated the generation of ROS. The enhancement of EDTA in
 H. Zhou et al. / Separation and Purification Technology 132 (2014) 346–353 349

Fig. 2. ATR-FTIR spectra of (a) pure EDTA, ZVI in ZVI/EDTA/Air system and pure ZVI; (b) pure EDDS, ZVI in ZVI/EDDS/Air system and pure ZVI.

this system could be explained reasonably by the similar state-
ment. However, due to its different coordination from EDTA, EDDS
adsorbed on ZVI surface might fail to form a cave or form a cave of
a different size, which reduces the surface Fe sites available for the
interactions with O2, and leads to lower local concentration of ROS
than that on the bare ZVI surface. Therefore, 2,4-DCP degradation
was decelerated by ZVI/EDDS/Air system.
3.2. Effects of reaction conditions on2,4-DCP degradation in ZVI/EDTA/
Air system
3.2.1. EDTA and ZVI
Both EDTA and ZVI serve as vital agents. Fig. 3a illustrates the
effect of initial EDTA concentration on 2,4-DCP degradation. When
the concentration of EDTA was increased from 0 to 1.2 mmol/L, the
degradation rate constant kobs for 2,4-DCP was significantly
increased from 0.69 to 3.72 h1. While the EDTA concentration
was further improved to be higher than 1.2 mmol/L, kobs decreased
slightly and then approached a constant value. Meanwhile, the
degradation of EDTA occured but it was not so sensitive to EDTA
concentration as that of 2,4-DCP. With 1.2 mmol/L EDTA, 96%
2,4-DCP and 59% EDTA were degraded in 45 min; and prolonging
the reaction time to 6 h, 96% EDTA was removed. In fact, EDTA
remaining in post-reaction solution could be separated for further
reuse in ZEA system. Although EDTA enhances the oxidation abil-
ity, the degradations of both 2,4-DCP and EDTA are hindered by
excessive EDTA. Excessive EDTA not only impedes the formation
of H2O2–FeII/IIIEDTA and O2–FeII/IIIEDTA adducts necessary for
H2O2 production [18,42], but also consumes ROS as an organic
compound competitively.
Fig. 3b shows the effect of ZVI on the degradation of 2,4-DCP
and EDTA. Without ZVI, 2,4-DCP was only volatilized by 27%. As

Fig. 3. Effect of EDTA and ZVI: (a) kobs(2,4-DCP) and kobs(EDTA) as concentration of EDTA changed (initial ZVI 12.5 g/L); (b) kobs(2,4-DCP) and kobs(EDTA) as ZVI increased; (c)
concentrations of total dissolved iron and ferrous ion (left) and molar ratio of EDTA to dissolved iron (right); (d) removal efficiency of 2,4-DCP in different systems (Fe2+ and
Fe3+ 1 mmol/L). Initial conditions: iron 7.5 g/L; EDTA 1.2 mmol/L.
350 H. Zhou et al. / Separation and Purification Technology 132 (2014) 346–353
ZVI dosage increased from 1 to 2.5 g, kobs for 2,4-DCP increased
from 2.15 to 4.01 h1 and kobs for EDTA increased from 0.41 to
0.56 h1. Although more ZVI in the system accelerates the decom-
position of contaminants, simply adding ZVI to the system cannot
intensify the degradation. With increasing the amount of ZVI from
2.5 to 5 g, both kobs(2,4-DCP) and kobs(EDTA) were observed to be
slightly decreased from 4.01 to 3.72 h1 and 0.56 to 0.47 h1,
respectively. Generally, more ZVI means more FeII/IIIEDTA complex
and better regeneration of FeIIEDTA from FeIIIEDTA, which acceler-
ates the production of H2O2. Nevertheless, excessive ZVI would
also consume the generated H2O2 (Eq. (4)), which appears to
overwhelm the benefit of ZVI in H2O2 production (Eq. (5)). There-
fore, balance of the opposite parts of ZVI should be maintained.
Since individually increasing ZVI or EDTA addition amount
restrains the degradation, the coaction of EDTA and ZVI should
be considered. It has been reported that [EDTA]:[FeII/III] molar ratio
above 1:1 inhibited the formation of [FeII(EDTA)(O2)]2+ and
sequential production of H2O2, and consequently decelerated the
degradation rate [43]. Fig. 3c shows the results of [EDTA]:[FeII/III]
molar ratio increased from below 1:1 to above 1:1, as ZVI addition
was altered from 2.5 to 5 g with 1.2 mmol/L EDTA.
Chelating acids could strongly intensify the iron dissolution from
iron-bearing catalysts and promote the Fe3+/Fe2+ recycling. The dis-
solved iron could further propagate homogeneous Fenton reaction
along with generated H2O2. To determine the contribution of
homogeneous Fenton reaction, total dissolved iron and dissociative
ferrous iron (Fe2+) were detected. As shown in Fig. 3c, the concentra-
tion of total dissolved iron increased at the initial 10 min but then
gradually decreased. However, no dissociative ferrous iron was
detected during the whole reaction period. The observed decrease
of total dissolved iron concentration might be primarily caused by
the degradation of EDTA and generation of passive film on ZVI
surface during the reaction. This indicates that the degradation is
not ascribed to homogeneous Fenton reaction. On the other hand,
Fe2+ and Fe3+ were employed to substitute ZVI. It was found that
the 3-h removal efficiency of 2,4-DCP was less than 20% (including
volatile parts) in both Fe2+/EDTA/Air and Fe3+/EDTA/Air system
(Fig. 3d). Accordingly, we deduce that degradation of organic com-
pounds in ZEA system is not attributed to the generated homoge-
neous Fenton reaction, but mainly ascribed to heterogeneous
catalytic reaction over the ZVI surface in situ modified by EDTA.
3.2.2. Aeration
As O2 is indispensable for the oxidation of ZVI to produce reac-
tive oxygen species, aeration is considered to be a critical factor in
the ZEA system. As shown in Fig. 4a, with nitrogen pumped into
the reactor instead of air to create an anoxic system, no obvious
appearance of iron oxides was observed throughout the whole
Fig. 4. Effect of air aeration: (a) trends of kobs(2,4-DCP) and kobs(EDTA) as air aeration changed; (b) concentration of DO. Initial conditions: ZVI 7.5 g/L; EDTA 1.2 mmol/L.
reaction and no more than 20% 2,4-DCP was removed partly via
reductive dehalogenation of ZVI [44–47]. Due to the stable struc-
ture of CPs, the chloride on the aromatic ring is not readily to be
substituted by hydrogen atom generated in the anaerobic system
[48]. When air was pumped into the system at a rate of 1 L/min,
kobs(2,4-DCP) rose to 3.95 h1 rapidly. Nevertheless, kobs(2,4-DCP)
decreased to 2.75 h1 as the aeration rate was improved to 2 L/min.
At the same time, kobs(EDTA) increased to 0.66 h1 at the aeration rate
of 1 L/min, and then stabilized.
During the reaction, dissolved oxygen (DO) variation was mon-
itored. As shown in Fig. 4b, without aeration, DO in solution was
zero. With increasing the aeration rate to 0.5 L/min, DO was almost
zero in the first 2 h and increased rapidly afterword, suggesting that
the deficiency of DO restricted the degradation reaction within the
initial 2 h. When aeration rate was raised to 1 L/min, sufficient DO
was supplied. However, too high aeration might accelerate the for-
mation of hydrated ferric oxide film over the surface of ZVI, imped-
ing the complexing of EDTA with iron and the generation of ROS.
3.2.3. Soil pH
Fig. 5a illustrates the effect of initial pH on the remediation of
2,4-DCP contaminated soil. At initial pH 3.05, 4.91, 7.03 and
10.62, kobs(2,4-DCP) values were 3.30, 3.95, 3.13, 2.70 h1, respec-
tively. In addition, at pH 4.91, which was the original pH of the sys-
tem, more than 96% 2,4-DCP was degraded within 45 min, faster
than the others, which might be contributed by EDTA adsorption
on ZVI. As presented in Fig. 5b, EDTA adsorption increased as pH
increased from 3.05 to 4.91, and then decreased as pH continued
to increase to 10.62. Unlike 2,4-DCP, kobs(EDTA) decreased slightly
as pH increased, because the acidic condition was generally favor-
able for EDTA degradation [49].
Regardless of slight differences in degradation rate constants
under all studied pH conditions, 2,4-DCP were all removed by more
than 98% in 1.5 h. It is inferred that pH in ZEA system is not so
important as that in traditional Fenton or Fenton-like system, but
influence the degradation of contaminants to certain extent by
exerting the effects on surface interaction between EDTA and
ZVI. That means the contaminants could be degraded effectively
equally at acid, neutral and even alkaline conditions, which shows
momentous significance for practical applications.
3.3. Mechanism for 2,4-DCP degradation by ZVI/EDTA/Air system
As mentioned above, the argument concerning reactive oxygen
species has never been stopped in the heterogeneous reaction of
ZVI with oxygen. In order to assess the importance of possible reac-
tive oxygen species being hydroxyl radical (OH), high-valent iron
species (Fe(IV)) or superoxide anion radicals (O2/HO2), several
 H. Zhou et al. / Separation and Purification Technology 132 (2014) 346–353 351

Fig. 5. Effect of pH: (a) trends of kobs(2,4-DCP) and kobs(EDTA) as pH changed; (b) EDTA adsorption rate on ZVI surface. Initial conditions: ZVI 7.5 g/L; EDTA 1.2 mmol/L.

Fig. 6. Linear plot of ln(C/C0) versus time with different probe compounds added (a) for 2,4-DCP; (b) EDTA. Initial conditions: ZVI 7.5 g/L; EDTA 1.2 mmol/L and probe
compounds 2 mmol/L.

compounds were employed based on their different reaction rates

with radical species. Benzoquinone was reported as scavenger for
O2/HO2, while methanol was chosen as a probe for OH and
Fe(IV). Besides, tert-Butyl alcohol (TBA) was chosen specially to
distinguish OH, for it can only be oxidized by OH and other stron-
ger oxidants. Therefore, the addition of these probes would change
the degradation rates of 2,4-DCP and EDTA.
As presented in Fig. 6a, compared with 2,4-DCP degradation
rate of 3.94 h1 in blank system (no scavengers added), addition
of benzoquinone restrained the degradation rate most severely to
2.23 h1, followed by methanol (kobs = 2.64 h1); and TBA had little
impact on the degradation rate (kobs = 3.59 h1), which were in
agreement with their impacts on EDTA degradation (Fig. 6b). The
inhibitory influence in the order of benzoquinone > metha-
nol > TBA suggests that in addition to the participation of OH,
O 
2 /HO2 radical and Fe(IV) were mainly responsible for oxidizing
organic pollutants, of which O 
2 /HO2 radical was the dominant
Fig. 7. Released Cl during reaction. Initial conditions: Kaolin clay 20 g, average 2,4-
reactive oxygen species.
DCP concentration 731 mg/kg, ZVI 7.5 g/L, EDTA 1.2 mmol/L.
On the basis of the information obtained above, a possible reac-
tion mechanism of O2 activation by ZVI in the presence of EDTA
was proposed. Firstly, EDTA is bonded on ZVI surface via monoden- proved that the reaction of O 
2 /HO2 production is superior to the

tate binding, facilitating dissolution and redox recycle of iron. reaction of Fe(IV) production, which might be accounted for by
Then, Fe0(s) is oxidized to „Fe2+ or ferrous ion by O2 to produce the reactants supply to some extent. O2 is adequate during the
H2O2 (Eq. (5)). Herein, „Fe2+ stands for Fe(II) sites on the catalyst reaction by successive aeration, while H2O2 is generated midway
surface, produced from Fe0(s) corrosion, „Fe3+ reduction by Fe0, in a small amount and meanwhile consumed rapidly by other
H2O2 and O 
2 /HO2 (Eqs. (6)–(8)). The further reaction between
reactions (Eqs. (1), (2), (7), (11)–(14)).
„Fe2+ species and H2O2 is responsible for the formation of Fe(IV)
BFe3þ þ Fe0ðsÞ ! BFe2þ ð6Þ
(Eq. (9)), where Fe(IV) represents all forms of this species.
Meanwhile, O2 can compete with H2O2 to react with „Fe2+ species,
leading to the production of O  BFe3þ þ H2 O2 ! BFe2þ þ OH ð7Þ
2 /HO2 (Eqs. (10) and (12)). It is
352 H. Zhou et al. / Separation and Purification Technology 132 (2014) 346–353

Fig. 8. Proposed reaction pathway for the degradation of 2,4-DCP and EDTA.

BFe3þ þ O
2 =HO2 ! BFe
 2þ
þ O2 ðþHþ Þ ð8Þ the aromatic ring ruptured and low molecule weight (LMW)
organic acids such as acetic acid and formic acid are produced. As
BFe2þ þ H2 O2 ! FeðIVÞ ðe:g: FeO2þ Þ þ H2 O ð9Þ an organic compound, EDTA is simultaneously degraded and the
main intermediates are proved to be iminodiacetic acid (IMDA),
oxalic acid, acetic acid and formic acid by IC analysis (Fig. 8), in
BFe2þ þ O2 ! BFe3þ þ O 
2 =HO2 ð10Þ
accordance with previous work [18].

BFe2þ þ O þ
2 =HO2 þ H ! BFe
 3þ
þ H 2 O2 ð11Þ
4. Conclusions
3þ 2þ þ
BFe þ H2 O2 ! BFe þH þ HO2 ð12Þ
We found that the oxidation ability of ZVI/Air system was
2þ þ 3þ greatly enhanced by the addition of EDTA but inhibited by EDDS,
BFe þ H2 O2 þ H ! Fe 
þ OH þ H2 O ð13Þ which was probably resulted from their different degradabilities
for 2,4-DCP and coordination modes with ZVI surface. Accordingly,

OH þ H2 O2 ! HO2 þ H2 O ð14Þ the remediation of 2,4-DCP contaminated soil by the novel hetero-
In response to the generated ROS, both 2,4-DCP and EDTA was geneous ZVI/EDTA/Air Fenton-like system was investigated sys-
oxidized by 96% and 63% within 45 min, respectively. As chloride tematically. The 2,4-DCP degradation was dependent upon the
substituents are responsible for the toxicity of aromatic com- amount of added EDTA and ZVI, supplied O2 and pH. With the sup-
pounds, the dechlorination degree was also measured to estimate plements of 7.5 g/L ZVI, 0.4 mmol/L EDTA and 1 L/min aeration,
the detoxification degree. As shown in Fig. 7, Cl gradually released approximate 800 mg/kg 2,4-DCP in 20 g contaminated soil was
from 2,4-DCP during the reaction, and the dechlorination rate of effectively degraded by 96% within 45 min under ambient atmo-
2,4-DCP almost reached 100%, suggesting that the chlorine on the sphere without pH regulation or H2O2 addition, which is of great
aromatic ring was released and no final chlorinate byproducts significance for practical remediation. Moreover, EDTA was simul-
were generated. The slight decrease of Cl after 45 min might be taneously degraded, exerting little safety threaten towards the
due to the adsorption of iron and iron oxides on the surface. environment. The degradation was mainly ascribed to heteroge-
According to HPLC and HPLC–MS analyses, the detected neous catalytic reaction over the ZVI surface in situ modified by
aromatic intermediates were found to be mono-chlorophenol, cat- EDTA. During the heterogeneous Fenton-like reaction, two main
echol, 2-chlorohydroquinone and hydroxylated product of 2,4-DCP. reactive oxygen species namely O 
2 /HO2 and Fe(IV) were gener-

Considering the experimental results as well as the information
reported in the literatures [50–52], a possible degradation pathway
for 2,4-DCP was proposed in Fig. 8. In this process, some part of
2,4-DCP is dechlorinated to mono-chlorophenols (m/z = 126.5 in
the chromatograph under negative ionization) by ZVI and O 2 . Fang
et al. [28] have found that the degradation of 2-CB by O
2 is a reduc-
tive dechlorination process. The mono-chlorophenols are further
oxidized to corresponding benzenediol (m/z = 108.5). Some other
part of 2,4-DCP is oxidized by ROS, leading to the formation of cer-
tain intermediate products, e.g. hydroxylation product of 2,4-DCP
(m/z = 177), which has also been observed in several researches
[51,52]. They were further transformed to 2-chloro-benzenediol
and 4-chloro-benzenediol (m/z = 144.5). As the reaction proceeds,
ated, in which O 2 /HO 
2 was predominant. The investigation
provides a new insight into the mechanism of ZEA system remedi-
ating organic compounds contaminated soil. The ZEA reaction pro-
vides a promising eco-friendly alternative for the remediation of
contaminated soils.
Acknowledgements
The work was supported by National Natural Science Funds of
China (No. 21077038) and National High Technology Research
and Development (863) Program of China (No. 2012AA06A304)
and Fundamental Research Funds for the Central Universities
(No. 2013QN065). We appreciated the help from Analytical and
 H. Zhou et al. / Separation and Purification Technology 132 (2014) 346–353
Testing Center, Huazhong University of Science and Technology,
China.
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