Journal of Hazardous Materials 262 (2013) 464471

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Journal of Hazardous Materials

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

Chelant extraction of heavy metals from contaminated soils using

new selective EDTA derivatives
Tao Zhang a , Jun-Min Liu b , Xiong-Fei Huang a , Bing Xia a , Cheng-Yong Su b , Guo-Fan Luo a ,
Yao-Wei Xu b , Ying-Xin Wu a , Zong-Wan Mao c , Rong-Liang Qiu a,d,
a

School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou 510275, PR China
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and
Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, PR China
c
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275,
PR China
d
Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Guangzhou 510275, PR China
b

h i g h l i g h t s
Two EDTA derivatives were synthesized to enhance the selectivity of chelators.
PDTA had the highest stability constants for Cu2+ and Ni2+ .
PDTA had the highest overall selectivity for trace metals over major cations.

a r t i c l e

i n f o

Article history:
Received 13 April 2013
Received in revised form 30 July 2013
Accepted 26 August 2013
Available online 1 September 2013
Keywords:
EDTA derivatives
Potentiometric titration
Cu(II)
Selectivity
Extraction

a b s t r a c t
Soil washing is one of the few permanent treatment alternatives for removing metal contaminants.
Ethylenediaminetetraacetic acid (EDTA) and its salts can substantially increase heavy metal removal
from contaminated soils and have been extensively studied for soil washing. However, EDTA has a poor
utilization ratio due to its low selectivity resulting from the competition between soil major cations and
trace metal ions for chelation. The present study evaluated the potential for soil washing using EDTA and
three of its derivatives: CDTA (trans-1,2-cyclohexanediaminetetraacetic acid), BDTA (benzyldiaminetetraacetic acid), and PDTA (phenyldiaminetetraacetic acid), which contain a cylcohexane ring, a benzyl
group, and a phenyl group, respectively. Titration results showed that PDTA had the highest stability
constants for Cu2+ and Ni2+ and the highest overall selectivity for trace metals over major cations. Equilibrium batch experiments were conducted to evaluate the efcacy of the EDTA derivatives at extracting
Cu2+ , Zn2+ , Ni2+ , Pb2+ , Ca2+ , and Fe3+ from a contaminated soil. At pH 7.0, PDTA extracted 1.5 times more
Cu2+ than did EDTA, but only 75% as much Ca2+ . Although CDTA was a strong chelator of heavy metal ions,
its overall selectivity was lower and comparable to that of EDTA. BDTA was the least effective extractant
because its stability constants with heavy metals were low. PDTA is potentially a practical washing agent
for soils contaminated with trace metals
2013 Elsevier B.V. All rights reserved.

1. Introduction
Heavy metal contamination of soils, resulting from rapid industrialization, increased urbanization, modern agricultural practices,
and inappropriate waste disposal methods, has become a serious
problem worldwide [13]. The available remediation technologies
for heavy metal-contaminated soils are mainly divided into two

Corresponding author at: School of Environmental Science and Engineering, Sun

Yat-sen University, Guangzhou 510275, PR China. Tel.: +86 20 84113454;
fax: +86 20 84113616.
E-mail address: eesqrl@mail.sysu.edu.cn (R.-L. Qiu).
0304-3894/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2013.08.069

groups: namely immobilization, such as in situ chemical xation,

and separation, such as soil washing. Chelant-enhanced soil washing is a technology that is potentially useful for the economically
feasible remediation of contaminated soils [48].
The chelating agent ethylenediaminetetraacetic acid (EDTA) and
its salts have been extensively studied for their potential use in soil
washing [912]. They have been reported to appreciably increase
the dissolution and mobilization of cationic heavy metals [13,14].
EDTA has low biodegradability in soil and a high efciency of
metal extraction through the formation of thermodynamically stable and soluble metalEDTA complexes [15,16]. In addition, recent
advances in recovery and recycling techniques of used EDTA have
enhanced its appeal [17].

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465

Table 1
Soil properties.
Soil

pH

OM (%)

CEC (cmol kg1 )

Sand (%)

Silt (%)

Clay (%)

Cu (mg kg1 )

Ni (mg kg1 )

Pb (mg kg1 )

Zn (mg kg1 )

GD

7.3

5.1

9.5

61

31

10

1388

26

507

236

A majority of the literature focused on demonstrating the remediation capabilities of EDTA has found that extraction of heavy
metals was faster and more complete with increased quantities
of added EDTA. Competition between the major cations of the soil
(e.g., Ca2+ , Mg2+ , and Fe3+ ) and minor cations for chelation by EDTA
may be one of the factors affecting the efciency of trace metal
extraction [1823]. As illustrated in previous studies [24,25], when
Ca solubility in calcareous soils is raised, the effectiveness of EDTA
extraction is diminished signicantly, increasing the cost of remediation. For non-calcareous soils, Fe and Al dissolution may be more
crucial, in view of their high tendency for complexation (i.e., large
stability constants). Excessive addition of chelating agent can cause
extensive dissolution of soil minerals and organic matter, leading
to alteration of soil physical and chemical properties and even disintegration of soil structure, which could render the soil unt for
future use for vegetation or construction. Therefore, there has been
a growing need to develop highly selective chelating agents for the
extraction of heavy metal ions from polluted soils.
In previous studies, EDTA has been modied to improve its
selectivity in chelating target metal ions [2628]. Highly selective
EDTA derivatives have a wide range of application in the elds
of analytical chemistry, biology and medicine, as well as in many
industrial processes. In this study, two new EDTA derivatives were
designed and synthesized with the goal of enhancing its selectivity
as a chelating agent. These EDTA derivatives contain a phenyl or
benzyl group directly bonded to the nitrogens of the ethylenediamino group, and thus potentially are more sterically constrained
than the parent compound. The objective of this study was to characterize these EDTA derivatives in aqueous solution and assess their
potential as selective washing agents. Batch experiments were conducted to determine their efcacy in the simultaneous extraction
of trace metal ions and major cations from contaminated soils and
to investigate the extraction mechanisms.
2. Materials and methods
2.1. Soil Characteristics
Soil samples were collected from 0.7 to 1.7 m below the ground
surface at a demolished industrial site in South China, air-dried at
room temperature (2030 C), and passed through a 2 mm sieve.
The soil properties in Table 1 were the average of three replicates.
Various soil physical and geochemical characterization tests
were carried out. The physical and chemical characteristics of the
soil are shown in Table 1. The metal concentrations in soil were
determined by acid digestion with HFHClO4 HNO3 and inductively coupled plasma optical emission spectrometry (ICP-OES)
measurement (5300DV, Perkin Elmer). Soil pH was determined
using a 1:5 soil-to-water ratio and pH meter. The CEC of the sample

was determined by the ammonium acetate/sodium acetate method

[29]. Organic matter content was determined by heating the dried
samples at 350 C for 5 h [30]. The particle size distribution was
established by mechanical sieving, followed by the hydrometer
method [31].
2.2. Synthesis of EDTA derivatives
Phenyldiaminetetraacetic acid (PDTA) was synthesized as illustrated in Fig. 1 according to a previously published procedure
[32]. A solution of 1,2-diaminobenzene (1.1 g, 10 mmol), ethyl bromoacetate (6.7 mL, 60 mmol), sodium iodide (1.3 g, 8.5 mmol), and
diisopropylethylamine (8.3 mL 50 mmol) in 10 mL acetonitrile was
reuxed under nitrogen for 7 h, then cooled and poured into 50 mL
water. The resulting mixture was extracted with dichloromethane
(3 40 mL). The extract was dried and was concentrated to give
brown oil, which was puried by ash chromatography using
petroleum ether/ethylacetate (10:1, v/v) as eluant. The product
obtained was 2.1 g (45%) of a white solid (A) (Fig. 1); a mixture
of ethanol, complex A, and NaOH (14.0 M) were reuxed at 78 C
for 24 h. The solution was cooled to room temperature, ethanol was
evaporated, and the residue was washed with 6.0 M HCl solution
and dried under high vacuum to give a white solid (B) (Fig. 1).
Benzyldiaminetetraacetic acid (BDTA) was synthesized as illustrated in Fig. 2. To a mixture of 1,2-bis(bromomethyl)benzene
(1.0 mmol) in 5.0 mL dry CH3 CN was added diethyliminodiacetate
(2.0 mmol) and anhydrous K2 CO3 (10 mmol). The resulting reaction mixture was stirred at room temperature for 5 h, then the
solids were ltered off and solvent was removed under vacuum.
The residue was again dissolved in ethyl acetate and washed with
water and saturated NaOH solution, which was puried by ash
chromatography using petroleum ether/ethylacetate (10:1, v/v) as
eluant. Light yellowish oil (A) (Fig. 2) was obtained by evaporation
of the organic phase. Then the residue was dissolved in the solution of KOH. The mixture was stirred at room temperature for 24 h,
and then resulting mixture was poured into ice water, after which
it was acidied with concentrated HCl (pH 1) to obtain a white
solid (B) (Fig. 2).
2.3. Potentiometric titration
An automatic titrator (Metrohm 702GPD Titrino) coupled to a
Metrohm electrode was used and calibrated according to the Gran
method [33,34]. The electrode system was calibrated with buffers
and checked by titration of HClO4 with NaOH solution(0.01 M).
The thermostated cell contained 25 mL of 1.0 mM species (free ligand/metal ligand complex) in aqueous solution with ionic strength
maintained at 0.10 M by potassium nitrate. All titrations were carried out on the aqueous solutions under nitrogen at 298 0.1 K, and

Fig. 1. Synthesis of PDTA.

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T. Zhang et al. / Journal of Hazardous Materials 262 (2013) 464471

Fig. 2. Synthesis of BDTA.

initiated by adding xed volumes of 0.10 M standard NaOH in small

increments to the titrated solution. Triplicate measurements were
performed, for which the experimental error was below 1%. The
titration data were tted from the raw data with the Hyperquad
2000 program to calculate the log and the pKa values of species
[3538].
2.4. Batch experiments
In the batch experiments, contaminated soil was mixed with a
measured volume of chelating agent solution in 50-mL polyethylene tubes. To probe the inuence of EDTA derivative concentration
on metal mobility in the washed soil, every 1.000 g of soil was mixed
with 20 mL chelating agent solution of different concentrations
(0.005 M, 0.01 M, 0.02 M, 0.05 M and 0.1 M) in tubes. The tubes were
agitated using a thermostatic shaker at 180 rpm at room temperature (25 2 C) for a given time. The suspensions were centrifuged
at 5000 rpm for 10 min and the supernatants were then ltered
through a 0.45 m membrane. All solutions were stored in amber
vials at 4 C prior to analysis.
Another two sets of batch equilibrium experiments were conducted to study the inuence of solution pH and liquid-to-soil ratio
on metal extraction by the EDTA derivatives. An initial chelator
concentration of 0.02 M was used in both sets. In the rst set, the
liquid-to-soil ratio was 20:1 (i.e., 20 mL g1 soil) while the solution
pH were adjusted using NaOH or HNO3 to pH values of 3.0, 4.0, 5.0,
6.0, 7.0, 8.0, 9.0, 10.0, 11.0, and 12.0. In the second set, the solution pH was kept at pH 6.0 while ve liquid-to-soil ratios of 2.5:1
(2.5 mL g1 ), 5:1 (5 mL g1 ), 10:1 (10 mL g1 ), 20:1 (20 mL g1 ), and
40:1 (40 mL g1 ) were studied. These ratios were achieved using a
constant solution soil mass of 1.0 g.

pKa values with the protonation constants of EDTA (2.67, 6.16, and
10.26) is acceptable.
The pKa1 value reects the acidity of the carboxyl groups, and
the pKa2 and pKa3 values characterize the basicity of the amino
nitrogens. The pKa2 and pKa3 values of CDTA and BDTA were similar
to those of EDTA. The pKa3 value of CDTA was higher as a result of
the electron-donating effect of the cyclohexane ring attached to the
amino nitrogens.
The obtained pKa1 value of PDTA (2.79 0.01), corresponding
to the protonation of carboxyl groups, was lower than that of
EDTA (3.05 0.02). The lower pKa1 value of PDTA indicates that the
acidity of the carboxyl groups was increased due to the electronwithdrawing effect of the aromatic group.
Similarly, PDTA had lower pKa2 and pKa3 values in comparison
with EDTA, indicating that the basicity of the nitrogen atoms is
signicantly lower for PDTA relative to EDTA [39]. This may be
attributed to the lower electronic density of the nitrogens in the
former due to the presence of a phenyl group, since the electronwithdrawing effect is increased when an aromatic group is directly
bonded to nitrogens of an ethylenediamino group [32].
In total, three deprotonation events were observed for the
free ligands PDTA and BDTA (Fig. 3 and Table 2). At pH < 4.0, the

2.5. Analytical methods

The 1 H NMR spectra of EDTA derivatives was obtained by
Mercury-Plus 300 1 H Nuclear Magnetic Resonance (VARIAN, USA).
We determined the molecular weight of PDTA and BDTA as 339 and
364, respectively, with electro spray ionization mass spectroscopy
(negative ion mode). The heavy metals of concern (Cu, Ni, Zn and Pb)
and soil component elements (Ca and Fe) were measured by inductively coupled plasma optical emission spectrometry (ICP-OES).
3. Results and discussion
3.1. Acidbase properties of EDTA derivatives
The protonation constants of PDTA and BDTA in water were
determined with a view to assessing their acidbase properties,
since these properties control what species exist in solution at
various pH values. Both PDTA and BDTA have six potential sites
that can bind with a proton, including the two nitrogens of the
ethylenediamino groups and the four carboxyl groups. However,
only three deprotonation events were observed by potentiometry
(Table 2). For comparison, Table 2 also includes the literature values and determined values for EDTA. The agreement of the obtained

Fig. 3. Distribution plots of species of the free ligands PDTA (1.0 mM) and BDTA
(1.0 mM).

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467

Table 2
Deprotonation constants (pKa ) of EDTA, CDTA, PDTA, and BDTA.
Equilibrium

H3 Y /H2 Y (pKa1 )
H2 Y2 /HY3 (pKa2 )
HY3 /Y4 (pKa3 )
a
b

EDTAa

CDTAa

EDTAb

PDTAb

BDTAb

2.67
6.16
10.26

3.53
6.15
12.40

3.05 0.02
6.42 0.02
10.50 0.03

2.79 0.01
3.70 0.02
5.95 0.03

3.56 0.03
8.31 0.05
10.00 0.06

Literature values.
Determined values.

percentage of species H3 Y /H2 Y2 was higher for BDTA than for

PDTA, which is consistent with the pKa2 values of BDTA and PDTA.
Similarly the percentage of BDTA existing as the species HY3 (i.e.,
with one nitrogen deprotonated) at pH < 5.0 was approximately
zero, in accordance with the high pKa3 values of BDTA.
3.2. Selectivity of EDTA derivatives
The metalligand (ML) complexation equilibrium constant, KML ,
expresses the ligands afnity toward the target metal (reaction (I)).

Table 3
Equilibrium constants (log KML ) of EDTA and derivatives in aqueous solution.
Metals

EDTAa

CDTAa

PDTAb

Pb(II)
Cu(II)
Cd(II)
Zn(II)
Ni(II)
Hg(II)
Ca(II)
Mg(II)

17.88
18.70
16.36
16.44
18.52
21.50
10.61
8.83

20.24
21.92
19.84
19.35
20.20
24.79
13.15
11.07

20.30
24.84
18.18
17.99
23.28
19.73
11.25
10.41

a
b

M2+ + H2 Y

2 KML

2H+ + MY2

0.05
0.07
0.03
0.09
0.05
0.09
0.05
0.08

Literature values.
Determined values.

(I)

The equilibrium constants of PDTA and BDTA complexes with a

range of metals were determined by pH potentiometric titration,
with the calculated results for the [MPDTA] complex summarized in Table 3. The [MBDTA] complex, however, did not exist
in distribution plots of species, except for CdBDTA(OH), which
demonstrated that MBDTA was not thermodynamically stable
(Table 4). We deduced that the structure of BDTA allowed it to form

a seven-membered ring complex with most metal ions, but not a

stable chelate compound with a ve-membered or six-membered
ring.
Table 3 also shows that PDTA has higher selective capability
for Cu2+ and Ni2+ , relative to Cd2+ , Zn2+ , Ca2+ , and Mg2+ , than do
the conventional chelators EDTA and CDTA. The differences in the
log KML values for Cu2+ and Ni2+ complexes with PDTA, CDTA, and

Fig. 4. Extraction efciency of different concentrations of chelating agents (liquid/solid = 20; contact time, 24 h; temperature, 25 C).

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T. Zhang et al. / Journal of Hazardous Materials 262 (2013) 464471

Table 4
Equilibrium constants of MBDTA in aqueous solution at 298 0.1 K.
Species

Table 5
pKtarget and SR values of EDTA and EDTA derivatives.

Equilibrium constants

CdL
CdL(OH)
CaL(OH)

log

log KML

7.41 0.08
4.67 0.07
0.35 0.02

3.57

0.30
1.28
2.27
1.89
0.90

MgL(OH)
ZnL(OH)
NiL(OH)
PbL(OH)
HgL(OH)
CuL(OH)

0.05
0.04
0.04
0.02
0.05

pKPb + pKCu + pKCd + pKZn + pKNi + pKHg

6

pKambient =

pKCa + pKMg
2

pKtarget

SR

EDTA
CDTA
PDTA

18.23
21.06
20.72

1.88
1.74
2.11

The selectivity of chelating agents toward heavy metals can be

quantitatively computed on the basis of the selectivity ratio (SR),
which is dened as:

SR =

EDTA are related to the steric constraints created by the benzene

ring in PDTA and the cyclohexane ring in CDTA [40] that are not
present in EDTA. Because the radii of Ni2+ and Cu2+ are similar,
PDTA does not exhibit good selectivity between the two [41].
In evaluating EDTA derivatives, we determined the equilibrium
constants (log KML ) of PDTA for complexation with six divalent target metals, including Pb, Cu, Cd, Zn, Ni, and Hg [42], and with two
ambient divalent cations, Ca and Mg.
pKtarget =

Chelating agents

pKtarget
pKambient

(3)

According to formula (3), a strong chelator will have large

pKtarget (>12) and pKambient values, whereas a strong and selective chelator toward heavy metals will have a large pKtarget and
a relatively small pKambient , and thus a large SR value (>2) [42].
The pKtarget and SR were calculated and summarized in Table 5,
which may serve to guide in the selection of chelators that are both
effective and selective toward the six target metals. The results
demonstrated that CDTA and PDTA were strong chelators, each
having as large a pKtarget (>12) as EDTA. More interestingly, PDTA,
compared with EDTA and CDTA, had a larger SR value (>2), showing
that it has a higher selectivity toward heavy metals.

(1)
3.3. Comparison of heavy metal removal with different chelators
(2)

3.3.1. Inuence of concentration

EDTA and its derivatives in a range of concentrations were used
to extract the heavy metals Cu, Ni, Pb, and Zn from a contaminated

Fig. 5. Extraction efciency using chelator solutions with different liquid/soil ratios (contact time, 24 h; temperature, 25 C).

T. Zhang et al. / Journal of Hazardous Materials 262 (2013) 464471

469

Fig. 6. Inuence of pH on extraction of metals using chelators (initial concentration, 0.02 M; liquid/solid = 20; contact time, 24 h; temperature, 25 C).

soil. The extent of removal of the four metals increased with

increasing concentration of the chelators from 0.005 to 0.10 M, but
the rate of increase for most metalchelator combinations was less
steep above a chelator concentration of 0.02 M (Fig. 4). At a chelator concentration of 0.02 M, the extraction of Cu was 62% by PDTA,
59% by CDTA, 48% by EDTA, and 8.6% by BDTA, while at the highest chelator concentration (0.10 M), these values increased to only
73%, 65%, 60%, and 10%, respectively. Over the entire concentration range, addition of PDTA caused the extraction increase slightly
compared with EDTA due to the low concentration of Ni in the soil,
from 4.4% to 15% by PDTA and from 2.2% to 11% by EDTA, respectively. Pb extraction by PDTA increased from 2.0% to 10%, while the
corresponding Pb values for EDTA were much higher, increasing
from 8.1% to 21%. Zn showed a trend similar to that of Pb, with
extraction values reaching 13% for PDTA and 28% for EDTA at the
highest chelator concentration. In light of these results, a chelator
concentration of 0.02 M was selected for further studies.
As the chelator concentration was increased, only a small fraction of the added chelator was incorporated into metalchelant
complexes, while the excess remained in the free form or was complexed with other cations (Ca, Mg, Fe, Al, etc.) [43]. Similarly, when
EDTA is used for soil washing, not all EDTA added to soil binds
the target metals, because other ions in the soil such as Ca and
Fe also interact with EDTA due to their high concentrations and
the relatively high stability of their complexes [44]. Above 0.02 M,
PDTA was the most efcient of the tested chelators at extracting Cu
from soil. This result can be attributed not only to stronger chelation of Cu by PDTA compared to the other chelators, but also to
the weaker chelation between PDTA and other soil cations (Ca, Fe,
etc.) and heavy metals, as evidenced by the pKML constants of their
complexes (Table 3). In fact, PDTA had the second lowest Pb and

Zn extraction efciencies, only slightly higher than those of BDTA,

which is unable to form a stable chelate compound with a ve- or
six-membered ring.
3.3.2. Inuence of liquid-to-soil ratio
At a constant chelator concentration of 0.4 mmol g1 soil, the
extraction efciency of the target metals was measured as the
liquid-to-soil ratio increased from 2.5:1 to 40:1. For EDTA and
CDTA, increasing the liquid-to-soil ratio over this range generally
increased the efciency of extraction of Cu (from 21% to 54% by
EDTA and from 24% to 61% by CDTA), Ni (from 0 to 12% by EDTA
and from 0% to 10% by CDTA), Pb (from 8% to 18% by EDTA and from

Fig. 7. Distribution plots of species of 1.0 mM Cu:PDTA as a function of pH at 0.10 M

KNO3 and (298 0.1) K.

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T. Zhang et al. / Journal of Hazardous Materials 262 (2013) 464471

Fig. 8. Solubilization of Ca and Fe by EDTA and EDTA derivatives (a: initial concentration, 0.02 M; liquid/solid = 20; contact time, 24 h; temperature, 25 C. b: initial pH of 6.0;
liquid/solid = 20; contact time, 24 h; temperature, 25 C).

6% to 17% by CDTA), and Zn (from 8% to 17% by EDTA and from 6% to

24% by CDTA), respectively (Fig. 5). However, for PDTA and BDTA,
extraction of the four metals was found to be independent of the
liquid-to-soil ratio.
The extraction efciency, as determined by the mole ratio of
extracted potentially toxic trace metals to chelant inputs [45],
increased with increasing liquid-to-soil ratio because a larger
amount of organic matter could be dissolved from a greater mass of
soil [8,43]. In addition, Cu has a high afnity toward organic matter, and the hydrophobic aromatic groups present in PDTA may
have facilitated soil organic matter dissolution, making Cu quickly
extractable and independent of the liquid:soil ratio.
3.3.3. Inuence of solution pH
As shown in Fig. 6, extraction efciency was highest at pH 3.0,
and generally decreased as solution pH was increased from pH 3.0
to pH 12.0. At pH 12.0, 24% of Cu was removed by PDTA but almost
none was removed by EDTA and BDTA.
The important mobilization processes of heavy metals in soil
include: (1) acidication, (2) competitive adsorption of other metal
ions or anions, (3) reductive and non-reductive dissolution of the
solid phase, and (4) complexation of metal ions by ligands [46].
Metals bound to soil hydrous oxides can often be retrieved simply
by lowering pH because protons can promote oxide dissolution.
Hydrogen ions are also weak competitive cations which can replace
the adsorbed heavy metals via a cation exchange mechanism, and
as the H+ ion concentration increases, the particle surface generally
becomes increasingly protonated and acquires a positive charge,
thus promoting desorption of metals [13]. Therefore this is why
heavy metal extraction is higher at lower values of solution pH.
In addition, the pH-potentiometric titration results showed that
the equilibrium species of Cu at a 1:1 metal:PDTA ratio are primarily ML, ML(OH), and ML(OH)2 (Fig. 7). The concentration of free
Cu2+ was very low in aqueous solution, and Cu is almost completely
complexed above pH 3.5. As pH is increased, one water molecule
is deprotonated but remains in the inner coordination sphere of
the complexed Cu2+ , forming a stable chelate compound, which
explains why even at a solution pH of 12.0, 24% of Cu was removed
by PDTA. In practice, however, the pH is normally controlled within
the range of 5.09.0 in order to eliminate adverse changes in the
soils chemical and physical structure brought about by too acidic or
alkaline a solution [14]. As pH increased from 5.0 to 9.0, the extraction efciency of Cu by PDTA decreased from 72% to 56%, but the
decrease was from 52% to 35% for EDTA. Thus, at constant pH, PDTA
is more efcient at extracting Cu from soil than is EDTA.

3.3.4. Solubilization of major soil mineral elements

The solubilization of soil mineral elements (i.e., Ca, and Fe) by
EDTA and its derivatives was also measured (Fig. 8). EDTA solubilized a large amount of Ca from the soil, with values that decreased
from 13 400 mg kg1 to 4510 mg kg1 as pH rose from pH 4.5 to pH
9.0, while the amount of Ca solubilized by PDTA was considerably
lower (10 500 mg kg1 to 2900 mg kg1 over the same pH range).
Similarly, at pH 6.0 and a chelator concentration of 0.05 M, EDTA
solubilized more Fe than did PDTA, with values of 227 mg kg1 and
102 mg kg1 , respectively.
Some researchers have found that co-dissolution of soil Ca is
an important factor that can result in a low degree of heavy metal
complexation by EDTA [20,21]. Another study showed that Ca2+ is
the main competitive cation, because CaCO3 is strongly dissolved
in the EDTA leaching solution under acidic conditions [20,25]; thus,
concentrations of Ca2+ in the leaching solution are very high compared to those of the target heavy metals. However, at pH 7.0, PDTA
solubilized 25% less Ca and extracted 54% more Cu from the contaminated soil than did EDTA (Figs. 6 and 8). These results can
be partly attributed to the low metal selectivity of EDTA, causing potential chelation of all of the exchangeable cations present
in the soil [18], and partly to the selective complexing ability of
PDTA for Cu. Thus, the minerals present in soil may not interfere
with PDTA extraction of Cu, conrming the potential applicability of PDTA for remediation of heavy metal-contaminated soil
containing high concentrations of mineral elements such as Ca
and Fe.
4. Conclusions
Two new EDTA derivatives, BTDA and PDTA, were synthesized
and their metalligand complexation equilibrium constants and
selective capabilities in aqueous media were investigated, along
with those of EDTA and CDTA. Titration results showed that PDTA
had the highest stability constants for Cu and Ni and the highest
overall selectivity for trace metals over major cations. Equilibrium
batch experiments were conducted to evaluate the efcacy of the
EDTA derivatives at extracting Cu, Zn, Ni, Pb, Ca, and Fe from a contaminated soil. At pH 7.0, PDTA extracted 1.5 times more Cu than
did EDTA, but only 75% as much Ca. Although CDTA was a strong
chelator of heavy metals, its overall selectivity was lower and comparable to that of EDTA. BDTA was the least effective extractant
because its stability constants with heavy metals were low. PDTA
is potentially a practical washing agent for soils contaminated with
trace metals, especially Cu.

T. Zhang et al. / Journal of Hazardous Materials 262 (2013) 464471

Acknowledgements
The project was supported by National Natural Science Foundation (No. 41171374), National Funds for Distinguished Young
Scientists of China (No. 41225004), Guangdong Province Higher
Vocational Colleges & Schools Pearl River Scholar Funded Scheme,
the Ministry of Environmental Protection of China (No. 201109020)
and the Research Fund Program of Guangdong Provincial Key
Laboratory of Environmental Pollution Control and Remediation
Technology (No. 2011K0007).
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