HOSTED BY Available online at www.sciencedirect.

com

ScienceDirect
Soils and Foundations xxx (2018) xxx–xxx
www.elsevier.com/locate/sandf

Desorption characteristics of Cr(III), Mn(II), and Ni(II)

in contaminated soil using citric acid and citric
acid-containing wastewater
Tang Qiang a,b,c,⇑,1, Gu Fan d,1, Gao Yufeng b,c, Inui Toru e, Katsumi Takeshi e
a
School of Rail Transportation, Soochow University, Suzhou 215131, China
b
Key Laboratory of Ministry of Education for Geomechanics and Embankment Engineering, Hohai University, Nanjing 210098, China
c
Jiangsu Research Center for Geotechnical Engineering Technology, Hohai University, Nanjing 210098, China
d
Texas A&M Transportation Institute, Texas A&M University System, 3135 TAMU, CE/TTI Bldg. 501A, College Station, TX 77843, USA
e
Graduate School of Global Environmental Studies, Kyoto University, Kyoto 606-8501, Japan

Received 8 September 2016; received in revised form 19 August 2017; accepted 4 October 2017

Abstract

Heavy metal-contaminated soil and wastewater have been attracting an increasing amount of attention due to the potential threat to
the surrounding environment and human health. Thus, in this study, citric acid (CA) and citric acid-containing wastewater (CACW)
were selected for an evaluation of the influence of the contamination level of the soil, the concentration of citric acid, the contact time,
the soil pH, and the ionic interaction on the desorption characteristics of three heavy metals (i.e., Cr(III), Mn(II), and Ni(II)). According
to the experimental results, a high concentration of citric acid, an acidic condition, a low level of contamination, and a lengthy contact
time were found to be beneficial for desorbing the heavy metals from the contaminated soil. Based on the experimental and calculated
results, the H+ ions and organic ligands made substantial contributions to the release and adsorption of the heavy metals. The metal ions
on the low selectivity sorption sites were leached out earlier than those on the high selectivity sorption sites. The removal percentages of
Cr(III), Mn(II), and Ni(II) using CA with a contact time of 6 h were 39.9%, 77.0%, and 62.8%, respectively. By using the CACW as a
desorbent, the removal percentages of Cr(III), Mn(II), and Ni(II) with a contact time of 6 h reached 21.4%, 26.9%, and 63.4%, respec-
tively. This suggests a promising practical application of CACW for removing heavy metals from contaminated soil.
Ó 2018 Production and hosting by Elsevier B.V. on behalf of The Japanese Geotechnical Society. This is an open access article under the CC BY-
NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Desorption; Heavy metal-contaminated soil (Cr(III), Mn(II), and Ni(II)); Citric acid; Citric acid-containing wastewater; Mechanism

1. Introduction
The removal of heavy metals from contaminated soil is
important in terms of protecting human health and the
environment. With the development of industrialization
Peer review under responsibility of The Japanese Geotechnical Society.
⇑ Corresponding author at: School of Rail Transportation, Soochow
University, Suzhou 215131, China.
E-mail address: tangqiang@suda.edu.cn (T. Qiang).
1
These authors contributed equally to this work.
and urbanization, more and more heavy metals are being
discharged into the environment by industrial activities,
which has resulted in serious soil contamination
(Eloussaief and Benzina, 2010; Solgi et al., 2012; Tang
et al., 2015). Unlike organic pollutants that are biodegrad-
able, heavy metal compounds cannot degrade into any
harmless eco-friendly end products (Tang et al., 2010). In
soil, heavy metals can transfer along the filtration or migra-
tion of groundwater and enter the food chain, eventually
threatening human health (Tang et al., 2009, 2012).

https://doi.org/10.1016/j.sandf.2017.12.001
0038-0806/Ó 2018 Production and hosting by Elsevier B.V. on behalf of The Japanese Geotechnical Society.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
2 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx
Traditionally, the main harmful heavy metals to human
health have included lead (Pb), cadmium (Cd), mercury
(Hg), and arsenic (As) (Jarup, 2003). Chromium (Cr(III))
ions are considered to be essential to humans; they not only
participate in the metabolism of the human body, but they
also have a positive effect on curing diabetes. However, Cr
(VI) ions are highly toxic and very mobile; they pose a sig-
nificant threat to human health (Yokel et al., 2006). Tzou
et al. (2002) found that Cr(III) can be oxidized to Cr(VI)
in soils containing Mn(II) oxide. This indicates that Cr
(III) should be removed from the soil to eliminate the
potential threat of the oxidation of Cr(III) to Cr(VI). The
elements manganese (Mn) and nickel (Ni) are two other
trace elements essential to humans. At low concentration
levels, Mn(II) and Ni(II) are crucial to forming several
enzymes in the human body, while at high concentration
levels, Mn(II) and Ni(II) become harmful to humans. Jin
et al. (2016) reported that a high concentration of Mn(II)
caused an outbreak of Parkinson’s disease. Singh and
Prasad (2015) found that Ni(II) at a high concentration
level caused neuron toxicological damage, allergic dermati-
tis, and genotoxicity in humans. Therefore, the World
Health Organization (WHO) and various countries have
limited the upper concentration levels of heavy metals
(e.g., Cr, Mn, and Ni) in drinking water in order to ensure
public health (WHO, 2011; EU, 2013; Japan, 2015; China,
2006; Canada, 2014; U.S., 2001; Australia, 2011).
Since heavy metals can immigrate into the groundwater,
soil contaminated by Cr, Mn, and Ni should be effectively
treated. Several soil remediation approaches have been
applied to contaminated soil, which include chemical treat-
ment, soil washing, the electrokinetic method, the bioreme-
diation and phytoremediation technique, thermal
treatment, etc. (Tang et al., 2016a, 2016b, 2017). Among
them, soil washing is regarded as a cleanup method, and
has already been utilized in field applications to soil reme-
diation projects or case studies all over the world, such as
the Twin Cities Army Ammunition Plant (U.S.), pilot
and demonstration plants for the remediation of urban
contaminated soil (Canada), and mining areas (Korea)
(USEPA, 1996; Mercier et al., 2007; Ko et al., 2006). Soil
washing technology is generally performed as an ex-situ
method, employing acids, bases, chelating agents, surfac-
tants, alcohol, solvents, water, and reducing agents or
other additives as the extracting agent. After chemical
treatment, the washed soil is usually rinsed with water to
remove any residual contaminants and/or residual extract-
ing agents from the soil, and the resulting cleaned soil is
returned to the site (Peters, 1999). The desorption efficiency
of soil washing depends on the type and concentration of
the desorption agents (Torres et al., 2012). According to
Pichtel and Pichtel (1997), HCl with a concentration of
1% only removed 16% of the Cr and 4% of the Pb(II) from
the contaminated soil, while the removal percentage of
heavy metals increased to nearly 100% when the concentra-
tion of HCl was raised to 2–8%. Although strong acids,
such as HCl, H2SO4, and HNO3, can effectively dissolve
Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
the heavy metals in contaminated soil, they damage the
micro-structure of the soil, which thereby harms the soil
revegetation (Peters, 1999; Tampouris et al., 2001). For this
reason, the replacement of strong acids by weak acids
should be taken into consideration for the desorption
agents used in soil washing.
Citric acid is a weak organic acid widely used in the
food, chemical, and metallurgical industries (Chang and
Holtzapple, 2000; Dhillon et al., 2011). The potential use
of citric acid as a desorption agent in soil remediation
has not been clarified, particularly for removing heavy met-
als such as Cr(III), Mn(II), and Ni(II). Meanwhile, a large
amount of citric acid-containing wastewater (CACW) is
produced by industrial activities. Traditionally, CACW is
neutralized by adding a certain amount of calcium sulfate.
This method not only consumes a fairly large amount of
calcium sulfate, but also wastes the discharged citric acid.
From an economic perspective, there is a need to effectively
utilize the CACW.
To address the aforementioned research needs, the aim
of this study is to characterize the desorption behavior of
heavy metals (i.e., Cr(III), Mn(II), and Ni(II)) in contami-
nated soil by taking into account such factors as the con-
tamination level of the soil, the concentration level of the
selected desorption agent, the contact time, the soil pH,
and the ionic interaction. Specifically, citric acid is selected
as a potential low-cost desorption agent for soil remedia-
tion. The evolution of different ions is simulated by the
software Visual MINTEQ for the different desorption con-
ditions. The efficiency of utilizing CACW to remove heavy
metals is also investigated in this study. Based on the above
experimental and calculated results, the adsorption and
desorption behaviors of heavy metals are discussed with
the assistance of XRD, XRF, a N2-BET analysis, and
SEM images.
2. Materials and methods
2.1. Soil and solutions
The soil used in this study is one type of locally available
soil collected from Suzhou, China (31.35°N, 120.58°E). To
eliminate interference from human activities, the soil was
collected from the underground at a depth of 3–4 m. The
soil was oven dried at 105 °C for 24 h, and then pulverized
and stored in plastic bags. Table 1 shows the physical and
chemical properties of the soil. The natural moisture con-
tent of the soil was 23.78%. The swelling index was 2
mL/2g-solid. The pH of the soil was 6.58. Such a slightly
acidic nature might be attributed to the local acid rainfall.
The cation exchange capacity (CEC) was 11.2 cmol+/kg
and the organic matter was 1.35%. Qin et al. (2004) consid-
ered that such low levels of CEC and organic matter would
lead to the easier desorption of metals from the soil. The
grain size distribution curve for the soil is presented in
Fig. 1. The uniformity coefficient and the curvature coeffi-
cient were 96.97 and 0.85, respectively. The specific surface
 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx 3

Table 1
Properties of studied soil.
Property Unit Value Standard
Natural moisture content % 23.78 JIS A 1203
Swelling index mL/2g-solid 2 ASTM D5890-06
Liquid limit % 41.54 JIS A 1205
Plastic limit % 16.57 JIS A 1205
pH 6.58 ASTM D4972-13
EC mS/cm 0.05 JGS 0212
Organic matter % 1.35 ASTM D2974-14
CEC cmol+/kg 11.2 ASTM D7503-10
Grain size distribution JIS A 1204
Sand (0.075–2 mm) % 57.4
Silt (0.005–0.075 mm) % 24.6
Clay (
0.005 mm) % 17.5
Uniformity coefficient 96.97
Curvature coefficient 0.85
N2-BET
Correlation coefficient (R) 0.9999
Specific surface area m2/g 24.49
Average pore Diameter nm 8.23
Total pore volume cm3/g 5.04  102
Mineral composition
Quartz % 35.88
Kaolinite % 39.50
Illite % 12.61
Hematite % 4.91
Calcite % 1.93
Albite % 5.17

100
defined as calcite, which is supported by Bentahar et al.
Cumulative percentage (%)

80 (2016) and Wang et al. (2009). The weak strength of the

60
40
20
Locally available clay
0 Al2O3, and 58.12% SiO2, it was rational to justify the exis-
100 10 1 0.1 0.01
Paticle size (mm)
Fig. 1. Particle size distribution of soil.
area of the soil was 24.49 m2/g, which was much higher
than that of the Heilongjiang soil (i.e., 4.64 m2/g) used by
Qin et al. (2004). According to Bhattacharyya and Gupta
(2011), the higher specific surface area provided more con-
tact opportunities between the heavy metals and the sorp-
tion sites on the soil surface.
Table 2 presents the chemical composition of the soil,
which was determined by X-ray fluorescence (XRF) tests.
The energy dispersive X-ray spectroscopy (EDX) (EDX-
720, Shimadzu, Japan) equipment was used in the XRF
tests with the assistance of a professional testing organiza-
tion. Before the tests, equipment calibration was conducted
to ensure credible XRF results. The X-ray diffraction
(XRD) spectra of the soil are shown in Fig. 2. The charac-
teristic peaks at around 2h = 30°, 39°, and 48° could be
characteristic peaks of calcite indicate its relatively low
content, which was consistent with the 0.91% CaO based
on the XRF analysis shown in Table 2. It should also be
mentioned that both albite and kaolinte exhibited charac-
teristic peaks around 2h = 13°, as shown in Fig. 2.
Together with the composition of 0.44% Na2O, 19.69%
1E-3
tence of albite. Considering several other apparent charac-
teristic peaks of kaolinite (2h = 42° and 46° et al.), the
characteristic peak around 13° should be coincidental for
both albite and kaolinite. Based on the XRD spectra, the
calculated mineral composition is shown in Table 1.
Eight different solutions were used in this study, includ-
ing de-ionized water (DIW), a citric acid solution (CA), a
Cr(III) solution, an Mn(II) solution, an Ni(II) solution, a
citric acid-NaCl solution, a citric acid-CaCl2 solution,
and a citric acid-Na2SO4 solution. The DIW was prepared
from tap water via a water distillation apparatus. To pre-
pare the heavy metal ion solutions, the solids of Cr
(NO2)3 and Ni(NO3)2, and the 50% Mn(NO3)2 solution,
were first dissolved in the DIW, respectively. The solutions
were then diluted into a target concentration of 0.1 mol/L.
The citric acid solid was diluted to different target concen-
trations of 0.1, 0.4, and 0.8 mol/L using the DIW. To pre-
pare the mixed solutions, the solids of NaCl, CaCl2, and
Na2SO4 were dissolved in 0.4 mol/L of the citric acid solu-

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
4 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx

Table 2
Soil compounds detected by XRF-analysis.
Element Unit Concentration Element Unit Concentration
K2O % 1.25 Na2O % 0.44
CaO % 0.91 Rb2O % 0.42
TiO2 % 1.09 SrO % 0.42
V2O5 % 0.18 Y2O3 % 0.26
MnO % 0.17 ZrO2 % 1.50
MgO % 1.09 CdO % ND
Fe2O3 % 4.55 SnO2 % ND
SiO2 % 58.12 PbO % ND
Al2O3 % 19.69

Q: Quartz
Q K: Kaolinite of the citric acid in the CACW was 2–4%. Compared to
I: Illite
pure citric acid, with a concentration of 0.1 M, the pH of
Intensity (CPS)

H: Hematite
C: Calcite the CACW here was slightly higher.
A: Albite

A 2.2. Preparation of contaminated soil

Q Q
A Q
I K(A)
I C HQC K K K K
0 20 40 60
2-Theta ( o )
Fig. 2. XRD spectra of soil.
tion, respectively. The target concentration levels for the
mixing solutions were 2000 mg/L (Na+) and 1000 mg/L
(Ca2+). Table 3 presents the chemical properties of the pre-
pared solutions.
The CACW used in this research was collected from a
citric acid production plant in Jiangsu Province, China,
whose image is shown in Fig. 3 together with that of the
DIW. Since the CACW was collected directly from the
end of the production line without any treatment, it con-
tained large amounts of dissolved organic matter (such as
carbohydrates, fatty acids, proteins, starch, enzymes, and
citric acid), and microorganisms. The selected chemical
and physical properties of the CACW are presented in
Table 4. The pH of the CACW was 4.3. The weight ratio
Q QQ Q
Q The contaminated soil was prepared for the desorption
test. 5 g of pulverized soil were first put into a 50-mL cen-
80 100 trifuge tube. To reach the target contamination levels of Cr
(III), Mn(II), and Ni(II) (i.e., 1 mg/g, 5 mg/g, and10 mg/g),
a certain dose of Cr(III), Mn(II), and Ni(II) solutions and
DIW were injected into the tube to reach a volume of 40
mL. The mixtures were shaken at 250 rpm for 96 h, and
then centrifuged at 3000 rpm for 10 min. The supernatant
was separated in order to measure the concentration of
heavy metals. The actual contamination level of the soil
was calculated by Eq. (1).
Cs  V s
Ca ¼ Ce  ð1Þ
m
where Ca is the actual concentration of Cr(III), Mn(II) or
Ni(II) in the soil (mg/g), Ce is the expectant concentration
of Cr(III), Mn(II) or Ni(II) in the soil (mg/g), Cs is the con-
centration of Cr(III), Mn(II) or Ni(II) in the supernatant
(mg/L), Vs is the volume of supernatant (L), and m is the
weight of the soil (g). All the samples were tested in dupli-
cate and the results were averaged.

Table 3
Measured chemical properties of the solutions.
Liquid Concentration pH EC
mol/L mg/L mS/cm @25 °C
De-ionized water 0 0 6.0 0.01
Cr(III) solution 0.1 5200 2.93 19.89
Mn(II) solution 0.1 5494 2.98 12.15
Ni(II) solution 0.1 5869 4.76 15.42
Citric acid solution 0.1 19,214 2.4 2.71
Citric acid solution 0.4 76,856 2.2 5.91
Citric acid solution 0.8 1,53,712 2.1 7.4
Citric acid-NaCl solution 0.4(2000 mg/L)* 2.1 14.2
Citric acid-CaCl2 solution 0.4(1000 mg/L)* 2.1 10.34
Citric acid-Na2SO4 solution 0.4(2000 mg/L)* 2.3 15.79
*
num1(num2 mg/L): num1 represents the concentration of citric acid solution; num2 represents the concentration of cation.

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx 5

2.3. Desorption experiments

The desorption experiments were conducted according

to the following steps:

 Put 5 g of contaminated soil in a 50-mL centrifuge tube;

 Add 40 mL of 0.4 mol/L CA into the tube;
 Shake the soil mixture at 250 rpm for 6 h;
 Centrifuge at 3000 rpm for 10 min;
 Measure the volume of supernatant and the concentra-
tion of metal ions.

As shown in Table 5, the samples were divided into five

Fig. 3. The comparison between CACW and DIW: (a) CACW; (b) DIW.
groups for evaluating the influence of the factors on the
desorption behavior of the heavy metals. These factors
include the contamination level of the soil, the concentra-
tion of citric acid, the contact time, the soil pH, and the
ionic interaction. For Group 1, the contamination levels
of the soil were expected to be 1 mg/g, 5 mg/g, and 10
mg/g, respectively. For Group 2, the variable was the con-
centration of citric acid. Samples marked number 4 were
blended with 40 mL of 0.1 mol/L CA; those marked num-
ber 5 were blended with 40 mL of 0.4 mol/L CA, and those
marked number 6 were blended with 40 mL of 0.8 mol/L
CA. Group 3 was used to evaluate the effect of the contact
time on the desorption, and thereby, the contact time was
set at 2 h, 6 h, and 12 h, respectively. For Group 4, the
pH of the soil was adjusted to 2.0, 7.0, and 12.0 using
H2SO4 or NaOH, respectively. Group 5 was used to inves-
tigate the influence of the ionic interaction on the desorp-
tion behavior of the heavy metals; NaCl, CaCl2 or
Na2SO4 was added into the tube. All the samples were
tested in duplicate and the results were averaged. The
removal mass and the percentage of heavy metals were cal-
culated by Eqs. (2) and (3).
A ¼ C 0s  V 0s ð2Þ
A
P¼ ð3Þ
m  Ca
where A is the removal mass of the heavy metals (i.e., Cr
(III), Mn(II), and Ni(II)), C0s is the concentration of heavy
metals in the supernatant after desorption (mg/L), V0s is the
volume of the supernatant after desorption (L), and P is
the removal percentage of the heavy metals.

Table 4
Selected chemical and physical properties of the collected CACW. 3. Results and discussion
Items Unit Value Items Unit Value
3.1. Adsorption characteristics of heavy metals
pH 3.8–4.7 Cl mg/L 162–194
EC mS/cm 3.5–4.6 NO 3 mg/L 92–117
Density kg/L 0.95–0.97 SO2 mg/L 389–763 The expected and actual contamination levels of the
4
CA concentration % 2–4 Na+ mg/L 13–32 heavy metals are presented in Table 6. It can be seen that,
TDS ppm 2610–3070 Mg2+ mg/L 234–281 at low contamination levels (e.g., 1 mg/g), the removal
COD mg/L 8–11  104 K+ mg/L 291–337 mass of the heavy metal ions reached the expected values,
TP mg/L 72–93 Ca2+ mg/L 82–127 while at higher contamination levels (e.g., 5 mg/g and 10
F mg/L 354–371
mg/g), the adsorption mass of the three heavy metals

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
6 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx

Table 5
Experiment program with citric acid.
Group Variable Sample Ce Cc T pH Ionic strength
Type Value
Unit mg/g M h mg/L
1 Ce Cr1 & Mn1 & Ni1 1 0.4 6 – – –
Cr2 & Mn2 & Ni2 5 0.4 6 – – –
Cr3 & Mn3 & Ni3 10 0.4 6 – – –
2 Cc Cr4 & Mn4 & Ni4 5 0.1 6 – – –
Cr5 & Mn5 & Ni5 5 0.4 6 – – –
Cr6 & Mn6 & Ni6 5 0.8 6 – – –
3 T Cr7 & Mn7 & Ni7 5 0.4 2 – – –
Cr8 & Mn8 & Ni8 5 0.4 6 – – –
Cr9 & Mn9 & Ni9 5 0.4 12 – – –
4 pH Cr10 & Mn10 & Ni10 5 0.4 6 2 – –
Cr11 & Mn11 & Ni11 5 0.4 6 7 – –
Cr12 & Mn12 & Ni12 5 0.4 6 12 – –
5 Ionic Strength Cr13 & Mn13 & Ni13 5 0.4 6 – NaCl Na: 2000
Cr14 & Mn14 & Ni14 5 0.4 6 – CaCl2 Ca: 1000
Cr15 & Mn15 & Ni15 5 0.4 6 – Na2SO4 Na: 2000
Cr16 & Mn16 & Ni16 5 0.4 6 – – –
NOTE: Ce: expectant initial contamination levels of heavy metal in soil; Cc: concentration of citric acid; T: contact time.

increased with the contamination level, but the adsorption
percentage of the three heavy metals decreased with the
contamination level. It was also found that the actual
adsorption mass of the heavy metals was lower than the
expected value at high contamination levels. To understand
this phenomenon, the microstructure of the soil was firstly
examined by the scanning electron microscopy technique.
As shown in Fig. 4, the main particle size distribution of
the soil was about 10 lm, and the visible inter-particle
pores were around 0.2–0.5 lm, which is much smaller than
those of montmorillonite (Tang et al., 2014). Table 1 shows
that the specific surface area of the soil used in this study
was 24.49 m2/g, which is also much less than that of mont-
morillonite (i.e., 69.87 m2/g). Fig. 2 indicates that the sur-
faces of soil-contained clay minerals, like kaolinite and
illite, have radical groups, AAlOH, ASiOH, and AFeOH.
These groups supply sorption sites for heavy metals
(Madejová et al., 1996). For these reasons, the soil used
in this study had fewer sorption sites, which indicates that
the soil used here had a lower adsorption capacity than
montmorillonite (i.e., 10–20 mg/g) (Fatimah, 2014). The
pH dependence of adsorption was another reason for the
low adsorption percentage. The pH of the aqueous solution
is an important variable which controls the adsorption of
heavy metals at the clay–water interfaces (Farrah and
Pickering, 1977). As shown in Table 3, the heavy metal
solutions were acidic, and a large amount of H+ was
released into the solid–liquid system. The hydroxyl group
(AOH) and the carboxyl group (ACOOH) were the most
common functional groups recognized in the soil at the
adsorption sites. The heavy metal ions can be fixed effectively
on the adsorption sites. This process is described as follows:
SAOH + Mkþ ! SAOM + Hþ
ACOOH + Mkþ !ACOOM + Hþ ð5Þ
where S represents the active surface functional groups,
including the silanol (SiAOA) and aluminol (AlAOA)
sites, and M represents the metal ions. At a low pH level,
the functional groups retain their protons to reduce the
adsorption probability to any positively charged ions
(Demirbasß, 2005). Meanwhile, the released H+ inhibited
the adsorption process. Therefore, the actual adsorption
mass of the heavy metals was lower than the expected value
in a low pH environment.
3.2. Desorption characteristics of heavy metals
3.2.1. Effect of contamination level of soil
Fig. 5 presents the effect of the contamination levels of
soil on the desorption behavior of heavy metals. It was
observed that the desorption masses of Cr(III), Mn(II),
and Ni(II) increased with an increase in the contamination
level. This demonstrates that the citric acid solution is effec-
tive for dissolving heavy metals. As for the removal per-
centage of heavy metals, the three heavy metals exhibited
different trends. For Cr(III) and Mn(II), the removal per-
centages increased when the contamination level increased
from 1 mg/g to 5 mg/g, and then they decreased when the
contamination level reached 10 mg/g. This might be
because of the insufficient amount of organic ligands,
which played a dominant role in the desorption process
(Qin et al., 2004). The sorption sites are divided into two
types, namely, high selectivity sorption sites and low selec-
tivity sorption sites (Gu and Yeung, 2011). At a low con-
tamination level, the metal ions are adsorbed onto the
high selectivity sorption sites. With an increased concentra-
tion level, the metal ions begin to be adsorbed onto the low
ð4Þ selectivity sorption sites. Compared to the high selectivity

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric

Table 6
Expectant and actual concentration of Cr(III), Mn(II) and Ni(II) in soil.
Group No. Expectant Actual Adsorption percentage No. Expectant Actual Adsorption percentage No. Expectant Actual Adsorption percentage
mg/g mg/g mg/g
1 Cr1 1 0.996 99.6% Mn1 1 0.937 93.7% Ni1 1 0.918 91.8%
Cr2 5 3.479 69.6% Mn2 5 2.725 54.5% Ni2 5 3.212 64.2%
Cr3 10 5.599 56.0% Mn3 10 5.412 54.1% Ni3 10 5.004 50.0%
2 Cr4 5 3.440 68.8% Mn4 5 2.864 57.3% Ni4 5 3.21 64.2%
Cr5 5 3.431 68.6% Mn5 5 2.871 57.4% Ni5 5 3.163 63.3%

T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx

Cr6 5 3.462 69.2% Mn6 5 2.859 57.2% Ni6 5 3.211 64.2%
3 Cr7 5 3.457 69.1% Mn7 5 2.893 57.9% Ni7 5 3.278 65.6%
Cr8 5 3.475 69.5% Mn8 5 2.878 57.6% Ni8 5 3.302 66.0%
Cr9 5 3.451 69.0% Mn9 5 2.849 57.0% Ni9 5 3.294 65.9%
4a Cr10 5 1.306 26.1% Mn10 5 1.063 21.3% Ni10 5 1.093 21.9%
Cr11 5 3.386 67.7% Mn11 5 2.796 55.9% Ni11 5 3.155 63.1%
Cr12 5 4.985 99.7% Mn12 5 4.927 98.5% Ni12 5 4.978 99.6%
5 Cr13 5 3.418 68.4% Mn13 5 2.909 58.2% Ni13 5 3.158 63.2%
Cr14 5 3.373 67.5% Mn14 5 2.907 58.1% Ni14 5 3.174 63.5%
Cr15 5 3.431 68.6% Mn15 5 2.913 58.3% Ni15 5 3.173 63.5%
Cr16 5 3.392 67.8% Mn16 5 2.847 56.9% Ni16 5 3.162 63.2%
6b Cr17 0.1 0.099 99.5% Mn17 0.1 0.098 98.4% Ni17 0.1 0.099 99.3%
Cr18 1 0.992 99.2% Mn18 1 0.941 94.1% Ni18 1 0.909 90.9%
Cr19 2 1.969 98.5% Mn19 2 1.861 93.0% Ni19 2 1.649 82.5%
Cr20 5 3.433 68.7% Mn20 5 2.851 57.0% Ni20 5 3.195 63.9%
Cr21 10 5.892 58.9% Mn21 10 5.59 55.9% Ni21 10 5.071 50.7%
7b Cr22 5 3.422 68.4% Mn22 5 2.904 58.1% Ni22 5 3.268 65.4%
Cr23 5 3.457 69.1% Mn23 5 2.877 57.5% Ni23 5 3.174 63.5%
Cr24 5 3.434 68.7% Mn24 5 2.829 56.6% Ni24 5 3.188 63.8%
Cr25 5 3.434 68.7% Mn25 5 2.952 59.0% Ni25 5 3.225 64.5%
Cr26 5 3.426 68.5% Mn26 5 2.947 58.9% Ni26 5 3.245 64.9%
Cr27 5 3.471 69.4% Mn27 5 2.912 58.2% Ni27 5 3.264 65.3%
a
Group at different soil pH.
b
Group using CACW.

7
8 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx
sorption sites, the low selectivity sorption sites have weaker
bonds with the metal ions, which indicates that there is a
tendency for citric acid to leach out metal ions on the
low selectivity sorption sites. Surface cation exchange is
the major source of the low selectivity sorption sites. The
metal ions on the low selectivity sorption sites were leached
out first. The process is described as follows:
XAMþ + 2Hþ ! 2XAHþ + Mþ
where X- is the cation exchange point and M+ represents
the heavy metal ions.
Then, the heavy metal ions on the high selectivity sites
were washed. The adsorption of Cr, Mn, and Ni ions pri-
marily depends on the surface coordination exchange.
The surface hydroxylation sites are mainly from the bond
between the hydrous oxides and the clay minerals. The
reaction of the high selectivity sites is expressed as follows:
SAO A Mþ + Hþ ! SAOH + Mþ
where SAOA represents the bond site of the hydroxyl
hydroxylation of the minerals.
(a) Magnification: 700 times
(b) Magnification: 30000 times
Fig. 4. SEM image of soil.
Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
At a low contamination level, the metal ions on the low
selectivity sorption sites and a portion of the metal ions on
the high selectivity sorption sites were firstly replaced by
H+ and then combined with organic ligands (Naidu and
Harter, 1998; Xu et al., 2009). With an increase in the con-
tamination level, the amount of citric acid was limited and
the amount of metal ions being leached out increased to the
upper limit. This led to the peak removal percentage. For
ð6Þ
Ni(II), the removal percentage decreased from 78.0% to
61.1% when the contamination level increased from 1 mg/
g to 10 mg/g. This could be attributed to the upper limit
of the metal ions being leached out by the citric acid. Thus,
the removal percentage of Ni(II) reached the peak at a low
contamination level.
3.2.2. Effect of concentration of citric acid
Fig. 6 presents the effect of the concentration of citric
acid on the desorption behavior of the three heavy metals.
ð7Þ
As the concentration of citric acid was increased from 0.1
to 0.8 mol/L, the corresponding removal percentage of
Cr(III) increased from 26.9% to 44.4%, the removal per-
centage of Mn(II) increased from 71.6% to 78.7%, and
the removal percentage of Ni(II) increased from 58.1% to
66.4%. The removal mass of the three ions exhibited similar
trends. It was also shown that the rate of the removal per-
centage and the removal mass of the heavy metals
decreased with the increasing concentration of citric acid.
Since citric acid is a weak organic acid, it undergoes acid-
based equilibrium reactions in the aqueous phase, e.g.:
Hn L ¼ Hþ þ Hn1 L ð8Þ
Subsequently,
Hnm Lm ¼ Hþ þ Hnðmþ1Þ Lðmþ1Þ ð9Þ
This fact resulted in the increasing amount of free H+
and organic ligands and was not directly proportional to
the increasing concentration of citric acid. The production
of H+ was dominated in the first step of hydrolysis, while
the second step of hydrolysis only generated a small
amount of H+. A larger amount of free H+ and organic
ligands leads to more collision opportunities between the
cations and the ions, which are effective for desorbing the
heavy metals. This explains why the rate of the removal
percentage and the removal mass of the heavy metals
decreased with the increasing concentration of citric acid.
In the adsorption process, the released H+ inhibited the
adsorption reaction. With the release of H+ and organic
ligands, metal ions were leached out of the sorption sites.
The adsorption reaction was expressed as
SAOM + Hþ ! SAOH + Mkþ ð10Þ
ACOOM + Hþ ! ACOOH + Mkþ ð11Þ
Hnm Lm + Mkþ ! LAM + (n - m)Hþ ð12Þ
The metal ions on the low selectivity sorption sites of the
soil first reacted with the H+ and organic ligands. Subse-
quently, the remaining H+ and organic ligands leached
 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx 9

20 100 removal percentage of the three heavy metal ions increased

Cr(III) removal percentage (%)

Citric acid: 0.4 M
with the contact time. As the contact time increased from 2
Cr(III) removal mass (mg)
Contact time: 6 h
80
15 pH: no adjustment h to 12 h, the removal percentage of Cr(III) increased from
Ionic species: empty
60
30.4% to 46.1%, the removal percentage of Mn(II)
10 Cr3 increased from 68.3% to 79.2%, and the removal percent-
40 age of Ni(II) increased from 59.1% to 65.1%. It is shown
Cr2 in the figure that the removal percentage of the heavy metal
5
Cr1
20 ions reached a relatively high level within the first 2 h. This
Removal mass
Removal percentage indicated that the processes of ion exchange and chelation
0 0
0 2 4 6 8 10 were rapid in this period. Although the metal ions on the
Conmination level of Cr(III) (mg/g) low selectivity sorption sites were leached out within 2 h,
(a) the washing of the rest of the ions on the high selectivity
sorption sites still needed more time. The longer contact
20 100 time provided more collision opportunities for the remain-

Mn(II) removal percentage (%)

Removal mass Removal percentage
ing metal ions with H+ and organic ligands. However, the
Mn(II) removal mass (mg)

Mn3 80
15 release of H+ and organic ligands was limited. With the
Mn2 60
10
40

Cr(III) removal percentage (%)

20 100
Citric acid: 0.4 M Cr(III) in soil: 5 mg/g

Cr(III) removal mass (mg)

5 Contact time: 6 h Contact time: 6 h
Mn1 20
pH: no adjustment pH: no adjustment 80
15
Ionic species: empty Ionic species: empty
0 0 60
0 2 4 6 8 10
10
Contamination level of Mn(II) (mg/g) 40
(b) Cr6
Cr5
5
Cr4 20
20 100 Removal mass
Ni(II) removal percentage (%)

Removal mass Removal percentage Removal percentage

0 0
Ni(II) removal mass (mg)

Ni3 80 0.0 0.2 0.4 0.6 0.8

15
Concentration of citric acid (M)
Ni2 60 (a)
10

Mn(II) removal percentage (%)

40 20 100
Removal mass
Citric acid: 0.4 M
Mn(II) removal mass (mg)

Removal percentage
5 Ni1 Contact time: 6 h 80
20 15
pH: no adjustment
Ionic species: empty Mn5 Mn6
0 0 Mn4 60
0 2 4 6 8 10 10
40
Contamination level of Ni(II) (mg/g) Mn(II) in soil: 5 mg/g
(c) 5 Contact time: 6 h
20
pH: no adjustment
Fig. 5. Desorption behaviors at different contamination level: (a) Cr(III); Ionic species: empty
0 0
(b) Mn(II); (c) Ni(II). 0.0 0.2 0.4 0.6 0.8
Concentration of citric acid (M)

the metal ions from the high selectivity sorption sites of the (b)
soil. The solution with a low pH value reduced the negative 20 100
Ni(II) removal percentage (%)

Removal mass
Ni(II) removal mass (mg)

Removal percentage
charge of the soil surface, which further decreased the affin-
80
ity of the soil to the metal ions. In this case, the metal ions 15
were much more prone to being desorbed (Wu et al., 2003). Ni5 Ni6 60
Ni4
With the development of the reaction, the amount of free 10
H+ and organic ligands decreased, which resulted in the 40
Ni(II) in soil: 5 mg/g
decrease in collision opportunities between the anions 5 Contact time: 6 h
20
and the cations. Eventually, the rate of the removal per- pH: no adjustment
Ionic species: empty
centage of the heavy metals decreased. 0 0
0.0 0.2 0.4 0.6 0.8
Concentration of citric acid (M)
3.2.3. Effect of contact time
Fig. 7 shows the effect of the contact time on the desorp- (c)
tion behavior of the heavy metals. The concentration of Fig. 6. Desorption behaviors at different citric acid concentration: (a) Cr
citric acid is 0.4 mol/L. Both the removal mass and the (III); (b) Mn(II); (c) Ni(II).

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
10 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx

development of the reaction, the amount of released free

Cr(III) removal percentage (%)

20 100
Citric acid: 0.4 M
H+ and organic ligands decreased. Accordingly, the colli-

Cr(III) removal mass (mg)

Cr(III) in soil: 5 mg/g
sion opportunities between the anions and the cations pH: no adjustment 80
15
Ionic species: empty
was reduced, which inhibited the desorption process of 60
the heavy metals. 10
40
Cr9
Cr8
3.2.4. Effect of soil pH 5
Cr7 20
The effect of the soil pH on the desorption characteris- Removal mass
Removal percentage
tics of Cr(III), Mn(II), and Ni(II) are shown in Fig. 8. As 0 0
0 2 4 6 8 10 12 14
the soil pH increased from 2 to 12, the removal mass of
Contact time (h)
Cr(III) increased from 2.04 mg to 8.87 mg, the removal
(a)
mass of Mn(II) increased from 3.36 mg to 12.16 mg, and

Mn(II) removal percentage (%)

the removal mass of Ni(II) increased from 2.62 mg to 20
Removal mass
100

Mn(II) removal mass (mg)

14.88 mg. This indicates that the removal mass of the heavy Removal percentage
80
metals increased with the increase in soil pH. With the 15
increase in the pH value, the soil surfaces were prone to Mn8 Mn9 60
Mn7
adsorb the heavy metals with an increase in the pH value. 10
Thus, more heavy metals were available to be desorbed by 40
Citric acid: 0.4 M
the citric acid agent in the soil with a higher pH value. This 5 Mn(II) in soil: 5 mg/g
20
can be confirmed by the results in Table 6 for which the pH: no adjustment
Ionic species: empty
actual contamination level of the heavy metals increased 0 0
with the increase in the soil pH. Since the amount of citric 0 2 4 6 8 10 12 14
acid was adequate, it was reasonable that the desorption Contact time (h)
amount of heavy metals increased with the increase in soil (b)
pH.

Ni(II) removal percentage (%)

20 100
Removal mass
The removal percentage of three heavy metals showed
Ni(II) removal mass (mg)

Removal percentage
different trends. For Cr(III) and Mn(II), the removal per- 15
80
centage of heavy metals fluctuated with the increase in soil
60
pH. Compared to the increasing trend of the removal mass 10
Ni8 Ni9
of heavy metals, the fluctuating trend of the removal per- Ni7 40
centage revealed that the soil with a low pH value actually Citric acid: 0.4 M
5 Ni(II) in soil: 5 mg/g
favored the desorption of heavy metals (e.g., Cr(III) and pH: no adjustment
20
Mn(II)), even though the desorption amount of heavy met- Ionic species: empty
0 0
als was limited. In the acid environment, more H+ ions 0 2 4 6 8 10 12 14
were released, causing a fiercer competition for sorption Contact time (h)
sites. H+ ions were combined with sorption sites on the soil (c)
surfaces, and hydroxyl groups tended to fix protons, which
led to the increase in desorption (Wang et al., 2009). With Fig. 7. Desorption behaviors at different contact time: (a) Cr(III); (b) Mn
(II); (c) Ni(II).
the increase in pH, the form of the heavy metals changed
to:
ðknÞþ
Mkþ þ nOH ! MðOHÞn ð13Þ the species distribution of Cr(III), Mn(II), and Ni(II) under
variable pH conditions. As seen from Fig. 9(a), Cr(III) did
Heavy metal ions were combined with hydroxyl groups not combine with the organic ligands. The desorption of Cr
on the soil surfaces or transformed into precipitation. (III) was determined by H+ and OH. At a low pH level,
Thus, the desorption process was inhabited in the high the large amount of Cr3+ indicated that H+ ions competed
pH environment. Different from Cr(III) and Mn(II), the with Cr(III) for the sorption sites. However, Mn(II) and Ni
removal percentage of Ni(II) increased with the increase (II) were different from Cr(III). At a low pH level (e.g., pH
in soil pH. < 2), the predominant species of Mn(II) was Mn2+ (98.4%)
The distribution of the ionic species of the three heavy and that of Ni(II) was Ni2+ (95.0%). This implies that Mn
metals in the equilibrium solution at different pH was sim- (II) and Ni(II) were prone to be replaced by H+ from the
ulated by Visual MINTEQ 3.0. According to the chemical sorption sites. With the increase in pH, Mn(II) and Ni(II)
composition of the soil determined by XRF, H+, organic began to react with the organic ligands, and the percentage
ligands (Citrate3), different metal ions (i.e., Na+, Al3+, of Mn-Citrate and Ni-Citrate increased. At a high pH level,
Fe3+, Mg2+, Ca2+, and K+) and pH values (i.e., 0.1 to the concentration of OH increased and the percentage of
13.9) were set into a calculation model to explore the ionic Cr-(OH), Mn-(OH), and Ni-(OH) increased. This implies
interaction under different pH conditions. Fig. 9 showed that the desorption was inhibited.

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx 11

3.2.5. Effect of ionic interaction
The effect of ionic interaction on the desorption behav-
ior of heavy metals is shown in Fig. 10. With the addition
of NaCl, CaCl2, and Na2SO4, the increased removal per-
centage of Cr(III) at different addition rates was in the
order of CaCl2 > Na2SO4 > NaCl. This could be attributed
to: (1) the competition between cations for sorption sites
shown in Eqs. (12) and (13),
(SO)3 AM + Naþ ! SOANa + M3þ
(SO)3 AM + Ca2þ ! SOACaAOS + M3þ
(2) a reduction in the activities of Cr(III) due to the ionic
interaction, and (3) the formation of ionic pairs or chelat-
ing compounds (Yuan et al., 2007). For Mn(II), the
removal percentage slightly decreased due to the addition
20
of Na2SO4, NaCl, and CaCl2. This might be attributed to
the fact that the existence of Na+, Ca2+, Cl, and SO2 4
enhanced the combination of Mn(II) with the sorption
sites. For Ni(II), the removal percentage increased with
the addition of CaCl2, while it decreased with the addition
of Na2SO4 and NaCl. The competition of Ca2+ against Ni
(II) for sorption sites was described in Eq. (13). The com-
bination of Ni(II) with sorption sites was improved by
introducing Na+, Cl, and SO2 4 . The difference among
ð14Þ
the three ions might be because of the different affinities
ð15Þ of functional groups on the soil surface. Additionally, the
presence of salts may compress the electric double layer
surrounding the negatively charged surfaces, which con-
tributes to the different desorption behaviors towards dif-
ferent heavy metals (Xu and Zhao, 2005). However,
Peters (1999) concluded that the chelation process was
insensitive to the ionic strength over the ranges typically
100
encountered in groundwater and that the process was not
Cr(III) removal percentage (%)

Citric acid: 0.4 M affected by the presence of calcium. He (2001) pointed

Cr(III) removal mass (mg)

Cr(III) in soil: 5 mg/g

Contact time: 6 h 80 out that surface precipitation was another direct interac-
15
Ionic species: empty tion through which soil could accommodate metals. The
60 formation of hydrated metal ion precipitation on the soil
10 Cr12
surfaces was influenced by the ions. For Cr(III), the precip-
40
itation was inhibited by the ions, while the ions slightly
Cr11
5
Cr10 20 promoted the precipitation of Mn(II). For Ni(II), Ca2+
Removal mass
Removal percentage
inhibited the precipitation and SO24 promoted the precip-
0 0 itation. The surface complexation and surface precipitation
0 2 4 6 8 10 12 14
pH
mechanisms influenced the desorption at the same time.
(a)
4. Implementation study using CACW
Mn(II) removal percentage (%)

20 100
Removal mass
Mn(II) removal mass (mg)

Removal percentage According to the aforementioned findings, the citric acid

80
15 was effective in removing the heavy metal ions, namely, Cr
Mn12
Mn11 60 (III), Mn(II), and Ni(II) from the contaminated soil. It was
10 inferred that the CACW has the promising potential to
40 remove these heavy metal ions.
Citric acid: 0.4 M
5 Mn10 Mn(II) in soil: 5 mg/g The desorption experiments were conducted according
20
Contact time: 6 h to the following steps:
Ionic species: empty
0 0
0 2 4 6 8 10 12 14  Put 5 g of contaminated soil into a 50-mL centrifuge
pH tube;
(b)  Add 40 mL of CACW into the tube;
20 100
 Shake the soil mixture at 250 rpm for 6 h;
Ni(II) removal percentage (%)

Removal mass  Centrifuge at 3000 rpm for 10 min;

Ni(II) removal mass (mg)

Removal percentage
Ni12 80  Measure the volume of the supernatant and the concen-
15
tration of metal ions.
60
10 Ni11
The samples were separated into Groups 6 and 7, as
40
Citric acid: 0.4 M shown in Table 6. The aim of Group 6 was to investigate
5 Ni(II) in soil: 5 mg/g the effect of the contamination level (e.g., 0.1 mg/g, 1 mg/
Ni10 20
Contact time: 6 h
Ionic species: empty
g, 2 mg/g, 5 mg/g, and 10 mg/g) on the desorption. The
0 0 expected and actual heavy metal concentrations are pre-
0 2 4 6 8 10 12 14
sented in Table 6. The aim of Group 7 as to study the effect
pH
of the contact time (e.g., 2 h, 4 h, 6 h, 8 h, 10 h, and 12 h)
(c) on desorption.
Fig. 8. Desorption behaviors at different soil pH: (a) Cr(III); (b) Mn(II); Fig. 11 presents the effect of the contamination levels of
(c) Ni(II). soil on the heavy metal desorption behavior. With an

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
12 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx

Cr(OH)1+
2
Cr3+ CrOH2+ Cr(OH)3 (aq) Citric acid: 0.4 M Cr(III) in soil: 5 mg/g
Cr(OH)-4 Cr3(OH)5+ Cr2(OH)4+ CrNO32+ Contact time: 6 h pH: no adjustment

Cr(III) removal percentage (%)

100
4 2
15 100
Removal mass

Cr(III) removal mass (mg)

Removal percentage
Ion species percentage (%)

80 12 80

9 Cr14 Cr15 60
60
Cr13 Cr16
6 40
40

3 20
20

0 0
0 NaCl CaCl2 Na2SO4 Empty
0 2 4 6 8 10 12 14
pH Ionic species
(a) (a)
Mn 2+
MnOH +
Mn(OH) 2-
4
MnH-Citrate (aq) Citric acid: 0.4 M Mn(II) in soil: 5 mg/g
MnNO+3 Mn(NO3)2 (aq) Mn-Citrate- Mn 2 (OH)+3 Contact time: 6 h pH: no adjustment
15 100

Mn(II) removal percentage (%)

100 Removal mass

Mn(II) removal mass (mg)

Removal percentage
Ion species percentage (%)

12 Mn13 Mn14
Mn15
Mn16 80
80
9 60
60
6 40
40
3 20
20

0 0
0 NaCl CaCl2 Na2SO4 Empty
0 2 4 6 8 10 12 14
pH Ionic species
(b) (b)
Ni2+ Ni(OH)2 (aq) Ni(OH)-3 NiNO+3 Citric acid: 0.4 M Ni(II) in soil: 5 mg/g
Ni-Citrate- NiH-Citrate (aq) NiH2-Citrate+ Contact time: 6 h pH: no adjustment
15 100

Ni(II) removal percentage (%)

4- 3-
Ni-(Citrate) 2
NiH-(Citrate) 2
Removal mass
Ni(II) removal mass (mg)

100 Removal percentage

Ion species percentage (%)

12 Ni14 80
80 Ni16
Ni13
9 Ni15 60
60
6 40
40
3 20
20
0 0
0 NaCl CaCl2 Na2SO4 Empty
0 2 4 6 8 10 12 14 Ionic species
pH (c)
(c)
Fig. 10. Desorption behaviors at different ionic species: (a) Cr(III); (b) Mn
Fig. 9. Calculation results of species distribution under variable pH (II); (c) Ni(II).
condition: (a) Cr(III); (b) Mn(II); (c) Ni(II).

increase in the contamination level (i.e., from 0.1 mg/g to 60.3% to 58.3%, then increased to 69.4%, and then
10 mg/g), the removal mass of Cr(III) increased from decreased again to 51.0%. The removal percentage (ranged
0.11 mg to 8.44 mg, the removal mass of Mn(II) increased from 20% to 70%) in this study seemed slightly lower than
from 0.14 mg to 7.66 mg, and the removal mass of Ni(II) that in the pilot-scale case studies or field applications,
increased from 0.30 mg to 12.94 mg. However, the removal which had removal percentages between 30% and 80%
percentage of the heavy metals exhibited a different ten- (USEPA, 1996; Mercier et al., 2007; Ko et al., 2006). Such
dency. With an increase in the contamination level, the high removal percentages can be partially attributed to the
removal percentage of Cr(III) decreased from 21.5% to combination of several remediation technologies (e.g.,
16.9%, and then increased to 28.6%. The removal percent- physical separation, chemical extraction or phytoremedia-
age of Mn(II) decreased from 28.6% to 22.2%, then tion) and multiple-time soil washing. Considering that only
increased to 32.0%, and then decreased again to 27.4%. CACW was utilized and that the soil washing process was
Similarly, the removal percentage of Ni(II) decreased from performed once, it is rational to infer that this study

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx 13

15 100 12 100

Cr(III) removal percentage (%)

Cr(III) removal percentage (%)
Removal mass CACW Removal mass

Cr(III) removal mass (mg)

Removal percentage
Cr(III) removal mass (mg)
Cr(III) in soil: 5 mg/g Removal percentage
12 80 80
9

9 Cr21 60 60
6
6 40 40
Cr20 Cr24 Cr25 Cr26 Cr27
Cr22
3 Cr23
3 20 20
Cr18Cr19 CACW
Cr17 Contact time: 6 h
0 0 0 0
0 2 4 6 8 10 0 2 4 6 8 10 12 14
Contamination level of Cr(III) (mg/g) Contact time (h)
(a) (a)
15 100 12 100

Mn(II) removal percentage (%)

Mn(II) removal percentage (%)

Removal mass CACW Removal mass

Mn(II) removal mass (mg)

Mn(II) removal mass (mg)

Removal percentage Mn(II) in soil: 5 mg/g Removal percentage

12 80 80
9

9 Mn21 60 60
6
6 40 Mn23 40
Mn24 Mn27
Mn19 Mn20 3 Mn22 Mn25 Mn26
3 20 20
Mn18 CACW
Mn17 Contact time: 6 h
0 0 0 0
0 2 4 6 8 10 0 2 4 6 8 10 12 14
Contamination level of Mn(II) (mg/g) Contact time (h)
(b) (b)
12 100

Ni(II) removal percentage (%)

15 100
Ni(II) removal percentage (%)

Removal mass
Ni21 Ni23 Ni24 Ni25
Ni(II) removal mass (mg)

Removal percentage
Ni(II) removal mass (mg)

12 80 Ni22 Ni26 80
Ni20
9
Ni27

9 60 60
6
Ni19 40
6 40
3
Ni18 20
3 20
CACW CACW Removal mass
Ni17 Contact time: 6 h Ni(II) in soil: 5 mg/g Removal percentage
0 0 0 0
0 2 4 6 8 10 0 2 4 6 8 10 12 14
Contact time (h)
Contamination level of Ni(II) (mg/g)
(c)
(c)
Fig. 12. Desorption behaviors by contamination level at different contact
Fig. 11. Desorption behaviors by CACW at different contamination level: time: (a) Cr(III); (b) Mn(II); (c) Ni(II).
(a) Cr(III); (b) Mn(II); (c) Ni(II).

selectivity sorption sites, which resulted in a difficult des-

proposes a cost-effective method for the remediation of orption process. At high contamination levels, more metal
heavily polluted areas. ions were on the low selectivity sorption sites and were
With an increasing contamination level, the adsorption more easily leached out. Thus, the removal mass increased
amount also increased. At low contamination levels (i.e., with the contamination level. The different growth rates of
0.1 mg/g and 1 mg/g), the adsorption percentages of Cr the adsorption and desorption amounts led to a fluctuation
(III) were 99.5% and 99.2% respectively, the adsorption in the removal percentage with an increase in the contam-
percentages of Mn(II) were 98.4% and 94.1% respectively, ination level.
and the adsorption percentages of Ni(II) were 99.3% and Fig. 12 presents the effect of the contact time on the des-
90.9%, respectively. At high contamination levels, the orption behavior. The trend of the removal percentage of
adsorption percentage decreased. At the contamination the changing of the three ions was not regular. For Cr
level of 10 mg/g, 58.9% Cr(III), 55.9% Mn(II), and 50.7% (III), the removal percentage reached 17.2% within 2 h,
Ni(II) were adsorbed. Although the amounts of H+ and the maximal percentage was 18.9% at 6 h, and the average
organic ligands were enough to leach the adsorbed metal percentage was 16.9%. For Mn(II), the removal percentage
ions at low contamination levels, the removal percentage reached 16.2% within 2 h, the maximal percentage was
was low. Metal ions had a stronger bond with the high 26.1% at 4 h, and the average percentage was 20.1%. For

Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
14 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx
12
Soil: 5 g DIW
Contact time: 6 h CACW
H2SO4 (0.1 M)
9 mL centrifuge tube. Certain doses of DIW, CACW,
pH
6
3
0
0 2 4 6
Liquid/solid ratio (by mass)
Fig. 13. Soil pH at different liquid/solid ratio.
Ni(II), the removal percentage reached 54.8% within 2 h,
the maximal percentage was 62.8% at 6 h, and the average
percentage was 57.5%. The removal percentage kept chang-
ing from 2 h to 12 h, which could be attributed to the com-
plex composition of CACW (e.g., dissolved organic matter
and microorganisms). Compared to the rapid reaction
between ions, the microorganisms were not able to affect
the desorption behavior in a short period. For this reason,
the contact time should be limited to a short period in
order to avoid the interference of microorganisms.
When leached by CACW, the average removal percent-
age of Cr(III), Mn(II), and Ni(II) was 18.9%, 20.1%, and
57.5%, respectively, which was smaller than that of the soil
leached by CA (Cr(III), 38.5%, Mn(II), 74.5% or Ni(II),
62.2%. For Cr(III), the addition of Na+, Ca2+, Cl, and
SO24 should favor desorption, while the reduction in the
removal percentage was close to 50.9%. This indicated that
Na+, Ca2+, Cl, and SO2 4 were not the predominant factors
affecting the desorption process. It was inferred that there
must be other materials in the CACW causing a large
decrease in the removal percentage. For Mn(II), the reduc-
tion of the removal percentage was about 73.0%. This could
be attributed to the negative influence of Na+, Ca2+, Cl,
SO24 and other materials in the CACW on the desorption.
For Ni(II), the reduction of the removal percentage was only
7.6%. The difference between the three heavy metals could be
due to the different affinities with the sorption sites or
organic ligands. The affinities with the organic ligands were
in the sequence of Ni(II) > Mn(II) > Cr(III).
Considering the CACW as a type of acidic wastewa-
ter, a series of experiments has been conducted to evalu-
Table 7
The desorption behaviors collected from previous researches.
No. Type Concentration
1 HCl 1M
2 EDTA 0.1 M
3 HOAc 0.1 M
4 D-gluconic acid 0.1 M
5 Citric acid 0.4 M
6 CACW 0.1 M
Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
ate the influence of its acidification on the soil
environment. 5 g of pulverized soil was put into a 50
and the 0.1 M H2SO4 solution were added into the tube
to reach the target liquid/solid ratios (e.g., 1:1, 2:1, 3:1,
4:1, 5:1, 6:1, 7:1, and 8:1). The mixtures were shaken
at 250 rpm for 6 h and the pH of each case was mea-
sured, as shown in Fig. 13. Compared with the back-
ground value of the soil pH 6.58, listed in Table 1, the
8 pH under the CACW condition and the H2SO4 condition
decreased to 4.88 and 2.16, respectively. Although H2SO4
has been proved effective for heavy metal removal, it
might result in serious soil acidification (Moutsatsou
et al., 2006). Meanwhile, the nutrient substance in
CACW can be decomposed or adsorbed by plants and
microorganisms, which minimizes the negative impact,
such as eutrophication, on the surrounding environment.
Table 7 shows the removal percentage of the three heavy
metals using different eluent agents. Using 1 M HCl as the
desorbent, the removal percentage of Cr, Mn, and Ni was
high. However, high acidic strength would destroy the soil
structure and dissolve much of the soil solids (Peters, 1999).
Although soil acidity can easily be neutralized by adding
lime, the damaged soil structure would not be repaired with
this approach. Furthermore, compared to CACW as an
industrial waste, HCl and lime as industrial raw materials
are expensive. It is possible that a large amount of lime
would result in an increase in the Ca content in the soil.
Ðolić et al. (2015) used 0.1 M EDTA and 0.1 M HOAc
to wash the contaminated soil. The EDTA and HOAc
agents were effective in removing the heavy metals in a rel-
atively short contact time. However, these two agents are
not eco-friendly products. According to Fischer and Bipp
(2002), the agent of D-gluconic was not effective in remov-
ing the three heavy metals even over a long contact time. In
this study, the CA and CACW were selected as the two des-
orbents. They exhibited a high desorption capacity for the
heavy metals of Cr, Mn, and Ni. Even if the extracted
heavy metals were difficult to recover, these heavy metals
would still not easily be released into the environment to
harm human beings, since they are stabilized as chelate
compounds. Meanwhile, the redundant citric acid is natu-
rally degradable and friendly to microbes and ecosystems.
This demonstrates that CACW shows promise in its appli-
cation for treating contaminated soils.
Contact time Removal percentage References
Cr Mn Ni
24 h 96% 79% 89% Anjos et al., 2014
2h 23.1% 20.2% 20.1% Ðolić et al., 2015
2h 34.0% 36.4% 22.7%
72 h 3.9% – 17.6% Fischer and Bipp, 2002
6h 39.9% 77.0% 62.8% This study
6h 21.4% 26.9% 63.4%
 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx
5. Conclusions
This paper has investigated the desorption behavior of
heavy metals (i.e., Cr(III), Mn(II), and Ni(II)) from contam-
inated soil. CA and CACW were selected as the desorbents.
Several influential factors have been taken into account,
including the contamination level of the soil, the concentra-
tion of citric acid, the contact time, the soil pH, and the ionic
interaction. According to the results, the citric acid solution
was effective in extracting heavy metals from the contami-
nated soil. The removal percentages of Cr(III), Mn(II),
and Ni(II) using CA with a 6-h contact time was 39.9%,
77.0%, and 62.8%, respectively. The optimum conditions
for desorption by CA were recommended as a concentration
of citric acid over 0.4 M, a contact time longer than 6 h, and
a soil mixture pH lower than 7. Heavy metals fixed on the
low selectivity sorption sites were prone to being leached
out due to the weak bonds between them. Thus, H+ and
organic ligands first reacted with the metal ions on the low
selectivity sorption sites, and then reacted with those on
the high selectivity sorption sites. The heavy metal ions
among Cr(III), Mn(II), and Ni(II) exhibited different des-
orption characteristics when the soil pH was varied. The
acidic environment only favored the desorption of Cr(III)
and Mn(II). CACW was proved to be effective in leaching
the heavy metals from the contaminated soil. The removal
percentages of Cr(III), Mn(II), and Ni(II) using CACW with
a 6-h contact time were 21.4%, 26.9%, and 63.4% respec-
tively. In addition, CACW presented less of a negative
impact on the surrounding soil environment because of the
weak acidic nature of CACW, as well as the decomposition
and adsorption by plants and microorganisms.
Acknowledgements
The research presented herein was supported by the
National Nature Science Foundation of China (51708377,
41630633), the Natural Science Foundation of Jiangsu Pro-
vince (BK20170339), a China Postdoctoral Science Foun-
dation funded project (2016M591756), the Natural
Science Fund for Colleges and Universities in Jiangsu Pro-
vince (17KJB560008), Jiangsu Planned Projects for Post-
doctoral Research Funds (1601175C), and a project from
the Jiangsu Provincial Department of Housing and
Urban-Rural Development (2016ZD18). The research
was also supported by the Jiangsu Provincial Transport
Bureau (2016T05), Six Talent Peaks Project in Jiangsu Pro-
vince, China (2015-JNHB-018), and the Bureau of Housing
and Urban-Rural Development of Suzhou.
References
Australia, 2011. Australian Drinking Water Guidelines 6, 2011. <https://
www.clearwater.asn.au/user-data/resource-files/Aust_drinking_water_
guidelines.pdf>.
Anjos, V.E.D., Rohwedder, J.R., Cadore, S., Abate, G., Grassi, M.T.,
2014. Montmorillonite and vermiculite as solid phases for the
preconcentration of trace elements in natural waters: Adsorption and
Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
15
desorption studies of As, Ba, Cu, Cd Co, Cr, Mn, Ni, Pb, Sr, V, and
Zn. Appl. Clay Sci. 99, 289–296.
Bentahar, Y., Hurel, C., Draoui, K., Khairoun, S., Marmier, N., 2016.
Adsorptive properties of Moroccan clays for the removal of arsenic(V)
from aqueous solution. Appl. Clay Sci. 119, 385–392.
Bhattacharyya, K.G., Gupta, S.S., 2011. Removal of Cu(II) by natural
and acid-activated clays: an insight of adsorption isotherm, kinetic and
thermodynamics. Desalination 272, 66–75.
China, 2006. Standards for Drinking Water Quality. <http://www.moh.-
gov.cn/zwgkzt/pgw/201212/33644.shtml>.
Canada, 2014. Guidelines for Canadian Drinking Water Quality. <http://
www.hc-sc.gc.ca/ewh-semt/pubs/water-eau/sum_guide-res_recom/in-
dex-eng.php>.
Chang, V.S., Holtzapple, M.T., 2000. Fundamental factors affecting
biomass enzymatic reactivity. Appl. Biochem. Biotechnol. 84–86, 5–37.
Demirbasß, A., 2005. Adsorption of Cr(III) and Cr(VI) ions from aqueous
solutions on to modified lignin. Energy Sources 27 (15), 1449–1455.
Dhillon, G.S., Brar, S.K., Verma, M., Tyagi, R.D., 2011. Recent advances
in citric acid bio-production and recovery. Food Bioprocess Technol. 4
(4), 505–529.
Ðolić, M.B., Rajaković-Ognjanović, V.N., Marković, J.P., Janković-
Mandić, L.J., Mitrić, M.N., Onjia, A.E., Rajaković, L.V., 2015. The
effect of different extractants on lead desorption from a natural
mineral. Appl. Surf. Sci. 324, 221–231.
EU, 2013. Drinking Water Regulations. <http://ec.europa.eu/environ-
ment/water/water-drink/legislation_en.html>.
Eloussaief, M., Benzina, M., 2010. Efficiency of natural and acid-activated
clays in the removal of Pb(II) from aqueous solutions. J. Hazard.
Mater. 178 (1–3), 753–757.
Fatimah, I., 2014. Preparation of ZrO2/Al2O3-montmorillonite composite
as catalyst for phenol hydroxylation. J. Adv. Res. 5 (6), 663–670.
Farrah, H., Pickeringf, W.F., 1977. The effect of pH on the retention of
Cu, Pb, Zn and Cd by clay–humic acid mixtures. Water Air Soil Pollut.
8 (2), 189–197.
Fischer, K., Bipp, H.P., 2002. Removal of heavy metals from soil
components and soils by natural chelating agents. Part II. Soil
extraction by sugar acids. Water Air Soil Pollut. 138 (1), 271–288.
Gu, Y., Yeung, A.T., 2011. Desorption of cadmium from a natural
Shanghai clay using citric acid industrial wastewater. J. Hazard.
Mater. 191 (1–3), 144–149.
He, H., 2001. Studies on the Interaction of Clay Mineral and Metal Ions.
Petrolic Industrial Press, Beijing (in Chinese).
Jarup, L., 2003. Hazards of heavy metal contamination. Br. Med. Bull. 68
(1), 167–182.
Japan, 2015. Drinking Water Quality Standards. <http://www.mhlw.go.
jp/stf/seisakunitsuite/bunya/topics/bukyoku/kenkou/suido/kijun/ki-
junchi.html>.
Jin, M., Li, W., Spillane, D.E.M., Geraldes, C.F.G.C., Williams, G.R.,
Bligh, S.W.A., 2016. Hydroxy double salts intercalated with Mn(II)
complexes as potential contrast agents. Solid State Sci. 53, 9–16.
Ko, I.W., Lee, C.H., Lee, K.P., Lee, S.W., Kim, K.W., 2006. Remediation
of soil contaminated with arsenic, zinc, and nickel by pilot-scale soil
washing. Environ. Prog. 25 (1), 39–48.
Madejová, J., Bujdák, J., Gates, W.P., Komadel, P., 1996. Preparation
and infrared spectroscopic characterization of reduced-charge mont-
morillonite with various Li contents. Clay Miner. 31 (2), 233–241.
Mercier, G., Blais, J.F., Chartier, M., 2007. Décontamination à l’échelle
pilote de sols pollués en métaux toxiques par des procédés miniers et
lixiviation chimique. J. Environ. Eng. Sci. 6, 53–64.
Moutsatsou, A., Gregou, M., Matsas, D., Protonotarios, V., 2006.
Washing as a remediation technology applicable in soils heavily
polluted by mining–metallurgical activities. Chemosphere 63 (10),
1632–1640.
Naidu, R., Harter, R.D., 1998. Effect of different organic ligands on
cadmium sorption by and extractability from soils. Soil Sci. Soc. Am.
J. 62, 644–650.
Peters, R.W., 1999. Chelant extraction of heavy metals from contaminated
soils. J. Hazard. Mater. 66 (1–2), 151–210.
16 T. Qiang et al. / Soils and Foundations xxx (2018) xxx–xxx
Pichtel, J., Pichtel, T.M., 1997. Comparison of solvents for ex situ removal
of chromium and lead from contaminated soil. Environ. Eng. Sci. 14
(2), 97–104.
Qin, F., Shan, X., Wei, B., 2004. Effects of low-molecular-weight organic
acids and residence time on desorption of Cu, Cd, and Pb from soils.
Chemosphere 57, 253–263.
Singh, A., Prasad, S.M., 2015. A lucrative technique to reduce Ni toxicity
in Raphanus sativus plant by phosphate amendment: special reference
to plant metabolism. Ecotoxicol. Environ. Saf. 119, 81–89.
Solgi, E., Esmaili-Sari, A., Riyahi-Bakhtiari, A., Hadipour, M., 2012. Soil
contamination of metals in the three industrial estates, Arak, Iran.
Bullet. Environ. Contaminat. Toxicol. 88 (4), 634–638.
Tampouris, S., Papassiopi, N., Paspaliaris, I., 2001. Removal of contam-
inant metals from fine grained soils, using agglomeration, chloride
solutions and pile leaching techniques. J. Hazard. Mater. 84 (2–3),
297–319.
Tang, Q., Tang, X.W., Li, Z.Z., Chen, Y.M., Kou, N.Y., Sun, Z.F., 2009.
Adsorption and desorption behaviour of Pb(II) on a natural kaolin:
equilibrium, kinetic and thermodynamic studies. J. Chem. Technol.
Biotechnol. 84, 1371–1380.
Tang, Q., Tang, X.W., Hu, M.M., Li, Z.Z., Chen, Y.M., Lou, P., 2010.
Removal of Cd(II) from aqueous solution with activated Firmiana
Simplex Leaf: behaviors and affecting factors. J. Hazard. Mater. 179,
95–103.
Tang, Q., Tang, X.W., Li, Z.Z., Wang, Y., Hu, M.M., Zhang, X.J., Chen,
Y.M., 2012. Zn(II) removal with activated Firmiana simplex leaf:
kinetics and equilibrium studies. J. Environ. Eng. (ASCE) 138 (2), 190–
199.
Tang, Q., Katsumi, T., Inui, T., Li, Z., 2014. Membrane behavior of
bentonite-amended compacted clay. Soils Found. 54 (3), 329–344.
Tang, Q., Kim, H., Endo, K., Katsumi, T., Inui, T., 2015. Size effect on
lysimeter test evaluating the properties of construction and demolition
waste leachate. Soils Found. 55 (4), 720–736.
Tang, Q., Chu, J.M., Wang, Y., Zhou, T., Liu, Y., 2016a. Characteristics
and factors influencing Pb(II) desorption from a Chinese clay by citric
acid. Sep. Sci. Technol. 51 (17), 2734–2743.
Tang, Q., Liu, Y., Gu, F., Zhou, T., 2016b. Solidification/stabilization of
fly ash from a municipal solid waste incineration facility using
Please cite this article in press as: Qiang, T. et al., Desorption characteristics of Cr(III), Mn(II), and Ni(II) in contaminated soil using citric acid and citric
acid-containing wastewater, Soils Found. (2018), https://doi.org/10.1016/j.sandf.2017.12.001
Portland cement. Adv. Mater. Sci. Eng. 2016, 10. https://doi.org/
10.1155/2016/7101243. Article ID 7101243.
Tang, Q., Zhang, Y., Gao, Y.F., Gu, F., 2017. Use of cement-chelated
solidified MSWI fly ash for pavement material: mechanical and
environmental evaluations. Can. Geotech. J. 54 (11), 1553–1566.
Torres, L.G., Lopez, R.B., Beltran, M., 2012. Removal of As, Cd, Cu, Ni,
Pb, and Zn from a highly contaminated industrial soil using surfactant
enhanced soil washing. Phys. Chem. Earth, Parts A/B/C 37–39, 30–36.
Tzou, Y.M., Loeppert, R.H., Wang, M.K., 2002. Effect of organic
complexing ligands on Cr(III) oxidation by MnOx. Soil Sci. 167 (11),
729–738.
U.S., 2001. National Primary Drinking Water Regulations. <http://water.
epa.gov/drink/contaminants/>.
USEPA, 1996. Engineering Bulletin: Technology Alternatives for the
Remediation of Soils Contaminated with Arsenic, Cadmium, Chro-
mium, Mereury, and Lead. Office of Emergency and Remedial
Response, Cincinnati, OH.
WHO, 2011. Guidelines for drinking-water quality, fourth ed. <http://
www.who.int/water_sanitation_health/publications/2011/dwq_guide-
lines/en/>.
Wu, Z., Gu, Z., Wang, X., Evans, L., Guo, H., 2003. Effects of organic
acids on adsorption of lead onto montmorillonite, goethite and humic
acid. Environ. Pollut. 121 (3), 469–475.
Wang, D., Jiang, X., Rao, W., He, J., 2009. Kinetics of soil cadmium
desorption under simulated acid rain. Ecol. Complexity 6 (4), 432–437.
Xu, C., Xia, B.C., Lin, Y., 2009. Kinetics of heavy metals desorption by
EDTA and citric in contaminated soil and their redistribution of
fractions. J. Soil Water Conserv. 23 (4), 146–151.
Xu, Y., Zhao, D., 2005. Removal of copper from contaminated Soil by use
of poly (amidoamine) dendrimers. Environ. Sci. Technol. 39 (7), 2369–
2375.
Yokel, R.A., Lasley, S.M., Dorman, D.C., 2006. The speciation of metals
in mammals influences their toxicokinetics and toxicodynamics and
therefore human health risk assessment. J. Toxicol. Environ. Health
Part B 9 (1), 63–85.
Yuan, S., Xi, Z., Jiang, Y., Wan, J., Wu, C., Zheng, Z., Lu, X., 2007.
Desorption of copper and cadmium from soils enhanced by organic
acids. Chemosphere 68 (7), 1289–1297.