Remediation of cadmium-contaminated paddy soils by washing

with calcium chloride: Verication of on-site washing

Tomoyuki Makino
a,
*
, Takashi Kamiya
b
, Hiroyuki Takano
b
, Tadashi Itou
c
,
Naoki Sekiya
c
, Kouta Sasaki
b
, Yuji Maejima
a
, Kazuo Sugahara
a
a
National Institute for Agro-Environmental Sciences, 3-1-3, Kannondai, Tsukuba, Ibaraki 305-8604, Japan
b
Taiheiyo Cement Corp., 2-4-2 Osaku, Sakura, Chiba 285-8655, Japan
c
Nagano Agricultural Research Center, 429 Ogawara, Suzaka, Nagano, 382-0072, Japan
Received 3 April 2006; received in revised form 15 August 2006; accepted 16 August 2006
In situ soil washing in a paddy eld using an on-site wastewater treatment system resulted
in an effective decrease of Cd in soil and rice grains without affecting rice yield.
Abstract
We developed a new, three-step soil-wash method to remediate Cd-contaminated paddy elds. The method comprises (1) chemically washing
the eld soil with a CaCl
2
solution; (2) washing the treated soil with water to eliminate residual Cd and CaCl
2
; and (3) on-site treatment of
wastewater using a portable wastewater treatment system. Cd concentrations in the treated water were below Japans environmental quality stan-
dard (0.01 mg Cd L
1
), and the removal of Cd from the exchangeable fraction was 55% and from the acid-soluble fraction 15%. While soil
fertility properties were affected by the soil washing, adverse effects were not crucial and could be corrected. The washing had no affect on
rice growth, and reduced the average Cd concentration in rice grains by about two-thirds compared to a control plot. These results conrmed
the effectiveness of the soil-wash method in remediating Cd-contaminated paddy elds.
2006 Elsevier Ltd. All rights reserved.
Keywords: Soil washing; On site; Paddy soil; Rice; Cadmium
1. Introduction
The soil in many Japanese paddy elds has been affected
by Cd derived from old mines and rening plants. Excessive
intake of Cd into the human body is detrimental to human
health, causing serious illnesses such as itai-itai disease. To en-
sure the safety of foods, the concentrations of Cd in staple
crops should be below a standard value; this applies particu-
larly to rice because 34e50% of the Cd intake by Japanese
people has derived from rice (Kawada and Suzuki, 1998).
Current Japanese regulations designated certain paddy
elds, which have produced rice grains containing more than
1 mg kg
1
of Cd, as contaminated paddy elds. There has
been an effort to remediate these paddy elds by applying
soil dressing; however, this remedy is increasingly difcult
owing to the high cost and the difculty of obtaining uncon-
taminated dressing materials. Furthermore, the Codex Alimen-
tarius Commission of the United Nations Food and
Agriculture Organization (FAO) and the World Health Organi-
zation (WHO) recently proposed a new international standard
for Cd concentrations in polished rice, 0.4 mg Cd kg
1
(Codex
Alimentarius Commission (Codex), 2005). Therefore, de-
velopment of remediation methods for Cd-contaminated soil
has become an urgent task to ensure food safety.
Various in situ and ex situ remediation methods have
been employed for restoration of soils contaminated with
heavy metals. Soil-wash methods are particularly efcacious
in removing heavy metals from soils (Vangronsveld and
* Corresponding author. Tel.: 81 29 838 8314; fax: 81 29 838 8199.
E-mail address: michiai@affrc.go.jp (T. Makino).
0269-7491/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2006.08.037
Environmental Pollution 147 (2007) 112e119
www.elsevier.com/locate/envpol
Cunningham, 1998; Calmano et al., 2001; Mulligan et al.,
2001). Soil washing is, however, conventionally performed
ex situ in treatment plants that employ extracting reagents to
displace metals from soil into aqueous solution (Elliott and
Herzig, 1999). Few studies of on-site soil washing in paddy
elds have been conducted, even though on-site soil washing
could be suitable for paddy elds, which usually have an im-
pervious layer that keeps the wash solution in the surface layer.
Ogawa et al. (1985) used HCl to wash soil in a batch exper-
iment and conducted pot tests to clarify the resulting decreases
in Cd concentrations in unpolished rice. Although Nakashima
and Ono (1979) and Takijima et al. (1973) conducted wash
tests on actual paddy elds using EDTA and HCl, respectively,
and conrmed the effects, they did not study the treatment of
wastewater. In situ soil washing using an on-site wastewater
treatment system has not been applied before to Cd-contami-
nated paddy elds.
Another approach to soil washing uses size-selection pro-
cesses to separate smaller, more contaminated soil particles
from larger, cleaner soil particles. Several processes can be
used for the separations, including hydrocyclone processes,
uidized bed separation, and otation (Klima and Kim,
1997). However, this method is impractical for paddy elds,
because the separated smaller particles, namely, the clay and
silt fractions, are essential to maintain a favorable soil environ-
ment for crops in agricultural land.
For application of the soil-wash method to paddy elds, we
previously set up four points to guide the development of po-
tential on-site remedial technologies for Cd-contaminated
paddy soils (Makino et al., 2006):
1. Identication of wash chemicals with minimal environ-
mental impact on the paddy eld and its surrounding envi-
ronment, but with high Cd-removal efciency.
2. Development of a cost-effective and environmentally
sound soil-wash and on-site wastewater-treatment system
that puries the heavy metal-contaminated wastewater
generated by the washing process.
3. Preservation of soil fertility and plant growth after the
wash treatment.
4. Conrmation of the sustainability of the wash effect.
As chemicals for soil washing, strong metal chelating, neu-
tral salts and strong acid agents have been used (Davis, 2000).
In particular, ethylenediaminetetraacetic acid (EDTA) was able
to efciently remove Cd from contaminated soils (Nakashima
and Ono, 1979; Abumaizar and Smith, 1999). EDTA, however,
has the disadvantage that it remains in the environment for
quite some time due to its low biodegradability (Tandy et al.,
2004). Because EDTA has a high environmental burden,
some researchers have used biodegradable agent (Elliott and
Herzig, 1999; Mulligan et al., 1999; Hong et al., 2002; Tandy
et al., 2004). Though biodegradable agents are favorable wash-
ing chemicals from the viewpoint of environmental impact, the
costs of these chemicals are relatively high for washing of
paddy soils. Thus, we have already addressed the rst point, se-
lecting CaCl
2
as one of the promising soil-wash chemicals to
remediate Cd-contaminated soil in paddy elds. We have
also determined the optimum conditions for on-site soil wash-
ing by CaCl
2
at a paddy eld in Nagano prefecture, based on
laboratory results previously reported (Makino et al., 2006).
The objectives of this study were to develop a new on-site
soil-wash system to remediate Cd-contaminated soil and to
verify the practical effectiveness of the wash system by an
on-site trial.
2. Materials and methods
2.1. Experimental site
2.1.1. Description of the experimental site
Fig. 1 is a schematic representation of the on-site soil-wash experiment
conducted in a paddy eld in Nagano prefecture. Old mines around the exper-
imental area are thought to be the source of the Cd contamination in the paddy
eld soil. Below a 17-cm-thick Ap horizon lies an impermeable hardpan about
2 cm thick. Because of the hardpan, which is characteristic of most paddy
elds in Japan, the water requirement of the paddy eld is low, about
1 cm day
1
.
Cd concentrations in agricultural water used in the soil-wash experiment
were below 0.3 mg L
1
, the detection limit of inductively coupled plasma
optical emission spectrometry (ICP-OES) (VISTA-PRO, Varian Inc., USA).
2.1.2. Soil
The relevant chemical properties of soil samples collected from the Ap ho-
rizon at the experimental site were summarized in a previous report (Makino
et al., 2006; this soil was named Nagano soil). The soil is classied as a Flu-
vaquent (U.S. Department of Agriculture (USDA), 1998). X-ray diffraction
analysis identied kaolinite, mica, and chlorite in the soil. The total Cd con-
centration of the soil is 0.710 mg kg
1
, substantially higher than the mean
values in uncontaminated soils, which average 0.33 mg kg
1
in Japan (Yama-
saki et al., 2001) and 0.155 mg kg
1
in the United States (Holmgren et al.,
1993).
2.2. Newly developed portable system for
on-site wastewater treatment
2.2.1. Performance evaluation of chelating resin
We used a portable treatment system with a chelating resin to remove
heavy metals in the wastewater generated by the washing process. We selected
a porous chelating resin made from epoxy resin and iminopropionyl-group
chemicals, which function as carrier and selective adsorbent for heavy metals,
respectively (AClean Z, Asahi Glass Engineering Co. Ltd., Japan). We tested
the efcacy of the chelating resin by an acceleration experiment as follows.
We placed 10 g of Nagano soil in a 50-mL polypropylene (PP) tube and
added 15 mL of 0.1 mol L
1
CaCl
2
. The PP tube was shaken, side-to-side, for
1 h at 25

C and centrifuged for 10 min at 3000 rpm (1900 g). The
supernatant was ltered through a disposable membrane lter, pore size
0.2 mm(Millex, Millipore Corp., USA), with a 10-mLdisposable plastic syringe
(SS-10ESZ, Terumo Corp., Japan). Concentrations of Ca, Mg, K, Na, Cd, Co,
Cu, Mn, Ni, and Zn in the ltrates were analyzed by ICP-OES, after 50 mL of
13.4 mol L
1
concentrated nitric acid was added to 4.95 mL of the ltrates.
An articial wastewater, in which concentrations of heavy metals and
other cations were 10 times to those in the above-mentioned ltrate (concen-
tration factor 10), was made using special-grade, CaCl
2
, MgCl
2
$ 6H
2
O,
KCl, NaCl, CdCl
2
$ 2.5H
2
O, CoCl
2
$ 6H
2
O, CuCl
2
$ 2H
2
O, MnCl
2
$ 4H
2
O,
NiCl
2
$ 6H
2
O and ZnCl
2
.
A peristaltic pump delivered 1200 mL of the articial wastewater to
20 cm
3
of the chelating resin in a plastic column at a uid velocity of
200 mL h
1
. Efuent water from the column was sampled in increments of
50 mL and the 5 mL of the each increment was ltered by the membrane lter.
Concentrations of Cd and other heavy metals in the ltrates were measured by
ICP-OES as aforementioned.
113 T. Makino et al. / Environmental Pollution 147 (2007) 112e119
2.2.2. Basic conguration and schematic diagram of the portable
wastewater treatment system
The portable wastewater-treatment system set up at the experimental site
(Fig. 1) comprised a cyclone (diameter 100 mm), pH adjustment tank
(600 950 mm), reservoir tank (450 800 mm), compression lters (diame-
ter 300 650 mm), and 45 L of chelating resin in a plastic column (diameter
300 800 mm). The height and total weight were 2300 mm and 600 kg, re-
spectively (Fig. 2). The cyclone was used to remove sand in the wastewater.
The pH regulator increased the wastewater pH to 7e8 by adding NaOH solu-
tion. The compression lters removed most suspended solids from the waste-
water. The system composted of cyclone, compression lter, chelating resin.
2.3. On-site soil washing
The on-site soil-wash procedure comprised three steps: chemical washing,
water washing, and on-site treatment of wastewater generated in the wash pro-
cesses. A part of the paddy eld was bounded with 60-cm-high plastic boards,
which were partially buried on edge in the paddy eld so that the upper two-
thirds of each board remained above the ground surface (Fig. 1). This boundary
provided containment for additional water and chemicals in the paddy eld.
Soil washing was conducted in the bounded area, which encompassed 116 m
2
.
2.3.1. Chemical washing
Food-grade CaCl
2
(437 kg) was applied to the bounded experimental eld,
followed by 11.6 kL of agricultural water, creating a soil-solution ratio and
a CaCl
2
concentration of 1:1.5 and 0.1 mol L
1
, respectively. These were
the optimal values for soil washing in this paddy, as demonstrated previously
(Makino et al., 2006). Following the water addition, the initial water level of
the experimental eld was 32 cm above the subsurface impervious layer, pro-
viding total 29.74 kL of water in the led.
The soil solution was mixed by a 13-metric-hp cultivator (Kubota Corp.
B7000, Japan) for 1 h until it turned into slurry; the slurry was allowed to
rest for 1 h and then mixed again for 1 h. After the second mixing, the slurry
was allowed to rest again for 2 h, and then the supernatant of the slurry was
drained off as wastewater.
The experimental eld was then lled with agricultural water until the water
level reached the initial point followingthe reapplicationof CaCl
2
(147 kg) to the
eld. The resulting concentration of CaCl
2
in the paddy eld was 0.1 mol L
1
.
The slurry was then mixed, allowed to rest, and drained as described above.
25 m
Roadway
Generator
Analysis
shed
Portable wastewater
Treatment system
Water intake
chamber
Unwashed control
area
Washed
experimental
area (116 m
2
)
A
c
c
e
s
s
r
o
a
d
Irrigation
canal
Water
inlet
4
0

m
N
S
W
E
Fig. 1. Schematic representation of an on-site soil washing experiment conducted at a paddy eld in Nagano prefecture.
Water sampling Water sampling
Drainage
Chelating
resin
column
Compression
filter B
Compression
filter A
Pump
Control panel
Reservoir
tank
pH adjustment
tank
Cyclone
Stirrer
Alkali
storage
tank
1
8
5
0

m
m
Waste
water
2400 mm
Fig. 2. Schematic of portable wastewater treatment system.
114 T. Makino et al. / Environmental Pollution 147 (2007) 112e119
Concentrations of various ions in the wastewater of the rst chemical wash
were determined as follows: Na, K, Ca, and Mg in the extraction with CaCl
2
solutions were analyzed by ICP-OES, while NH
4
in those solutions was mea-
sured by steam-distillation methods. Anions (Cl

, NO
3

, PO
4
3
, SO
4
2
) were
measured using an ion chromatography equipped with an anion exchange col-
umn (CS-12A, Dionex Corp., USA), auto suppressor, electric conductivity and
UV detector. (DX-320, Dionex Corp.). Dissolved organic carbon (DOC) in the
ltrates extracted by chloride (Cl) salt solution was measured with a TOC an-
alyzer (TOC-5000, Shimadzu Corp., Japan). The ion, DOC, and pH data sets
were used to estimate the Cd speciation in the wastewater using the chemical
speciation software Visual MINTEQ (Gustafsson, 2004).
2.3.2. Water washing
The paddy eld was lled with agricultural water until the water level
reached the initial point. To eliminate residual Cd and Cl, the soil solution
was mixed for 1 h until it turned into slurry, allowed to rest for 2e5 h and
then the supernatant of the slurry was drained off as wastewater. This proce-
dure was repeated eight times, until the residual Cl concentration was reduced
to lower than the target value for rice growth (400 mg L
1
). The amounts of
the water application in the each water-washing process were summarized
in Table 1. The supernatant Cl concentration was measured by a Cl meter
(IM-40S, DKK-TOA Corp., Japan).
2.3.3. On-site treatment of wastewater
The wastewater produced by chemical and water washing was pumped
into the on-site wastewater treatment system at a ow rate of 1.3 kL h
1
.
The system removed Cd from the wastewater as described in Section 2.2.2,
and then discharged the treated water to a canal. The chelating resin in the
treatment system was changed every washing operations. The wastewater
was sampled before and after the treatment system (Fig. 2). The concentrations
of Cd and Cl were determined by ICP-OES and ion chromatography, respec-
tively, in the wastewater and the treated water.
2.4. Verication of the wash effect
2.4.1. Changes of Cd concentration in washed soil
The washed experimental area was divided into four plots for a wet rice
culture experiment (Fig. 1). Two soil samples were collected from the Ap ho-
rizon in each plot, before and after the washing. Soil samples were also col-
lected from four control plots located in the unwashed experimental area.
All samples were air dried at 25

C and a relative humidity of approximately
60% for a week, and were then passed through a 2-mm mesh sieve before anal-
ysis, except samples for EC analysis and the Cd extraction analysis using am-
monium nitrate (NH
4
NO
3
) solution; these fresh samples were sieved through
a 2-mm mesh but were not air dried.
Four grams of soil from each sample was placed in a 50-mL PP tube, and
20 mL of 0.1 mol L
1
or 0.01 mol L
1
HCl solution, or 40 mL of 1 mol L
1
NH
4
NO
3
solution, was added. The extracts of the soil-solution mixtures
were sampled and ltrated as described in Section 2.2.1. Cd in the ltrates
was analyzed by ICP-OES. The concentrations of soil Cd measured by
0.1 mol L
1
, 0.01 mol L
1
HCl and 1 mol L
1
NH
4
NO
3
solution were dened
as that of acid soluble, weakly soluble and exchangeable fraction, respectively.
The total soil Cd was analyzed by the digestion method with a mixture nitric
and perchloric acids on a hot plate (Makino et al., 2006).
2.4.2. Changes in soil fertility properties with the wash treatment
Air-dried soils described in Section 2.4.1 were analyzed for soil fertility
properties. Total carbon, pH, and nitrogen were measured by the methods
described previously (Makino et al., 2006). Soil EC was analyzed by the elec-
trode method (Mettler, MC126, USA) with a soil:water ratio of 1:5. Exchange-
able cations and available phosphate were analyzed according to Thomas
(1982) and Truog (1930), respectively. Available nitrogen was measured by
phosphate-buffer extraction method (Matsumoto et al., 2000).
2.4.3. Paddy rice cultivation experiment
Two rice cultivars, Akitakomachi and Milyang 23, were transplanted
on 20 June 2003, and harvested on 25 October 2003, in the experimental and con-
trol plots described in Section 2.4.1. Akitakomachi is one of the popular rice in
the region. However, Milyang 23 has a high capacity for adsorbing Cd (Mura-
kami et al., 2004). We used a split-plot design, with the wash treatment area com-
prising the main plots and cultivars as the subplots with a single replicate. Base
fertilizer containing 150, 250, and 50 kg ha
1
of N, P
2
O
5
, and K
2
O, respectively,
was applied to all plots. Magnesium sulfate and magnesium carbonate fertilizer
containing 250 and 150 kg ha
1
of Mg, respectively, were also applied to the
washed plot to balance the magnesium loss caused by soil washing.
Mature rice was harvested by hand, taking two 1.65-m
2
quadrilaterals in
each subplot. Air-dried shoot material and brown rice yield were measured,
and the brown rice yield was converted to ordinary water concentration
(150 g kg
1
dry weight). A part of the shoot material and of the brown rice
was ground in a stainless steel vibration sample mill (TI-100, Heiko Seisa-
kusho, Ltd., Japan), and 1 g of each ground sample was digested with concen-
trated HNO
3
followed by HClO
4
(Benton, 2001). Cd concentration in the
digested solution was determined by ICP-OES.
3. Results and discussion
3.1. Performance evaluation of the chelating resin
Fig. 3 shows the efciency of the chelating resin in remov-
ing Cd from the articial wastewater. While Wasay et al.
Table 1
Changes of chloride concentration in wastewater during soil-wash operations
No. of washings (n) Chloride concentration (mg L
1
) Measured value
b
(MV) Water application (kL)
Calculated value
a
(CV)
Chemical washing 1 7770 11.6
2 7250
c
7250 11.0
Water washing 1 4990 4300 9.3
2 4020 3040 5.8
3 2140 1340 13.9
4 1180 790 13.3
5 927 775 6.4
6 728 420 6.4
7 558 420 7.0
8 438 390 6.4
a
Calculated on the basis of the amount of water applied.
b
Measured by Cl meter.
c
CV
(0)
that is equivalent to the measured value at second chemical washing.
115 T. Makino et al. / Environmental Pollution 147 (2007) 112e119
(1999) and Bassi et al. (1999) used granular activated carbon
(GAC) and chitosan akes, respectively, in laboratory experi-
ments to remove heavy metals from leachates of soils contam-
inated with metals, we used chelating resin owing to its high
capacity to adsorb heavy metals.
The Cd concentration in efuent water was lower than the
target wastewater quality standard (Japans environmental
quality standard: 0.01 mg Cd L
1
) (Fig. 3), indicating that
the chelating resin was successfully adsorbing most of the Cd
in the water. However, the Cd concentration began to increase
when the BVexceeded 40, indicating breakthrough. Therefore,
the maximum treatment or breakthrough capacity of the chelat-
ing resin was 40 BV. Because the treatment system contained
45 L of the chelating resin, we determined that the chelating
resin needed to be changed within 18 kL of wastewater treat-
ment, on the basis of the following equation:
MTC BCCRVCF 1
where MTC is the maximum throughput of chelating resin in
the treatment system (L); BC is the breakthrough capacity of
the chelating resin ( 40); CRV is the chelating resin volume
in the treatment system ( 45 L); CF is the concentration fac-
tor of the articial wastewater ( 10).
3.2. On-site soil washing
3.2.1. Removal of Cd from the wastewater by
the treatment system
Fig. 4 shows the prole of Cd concentration in the pre-
treated and treated wastewaters generated during the chemical
washes and the water wash. The Cd concentration in the
treated wastewater of the rst chemical wash was below Ja-
pans environmental quality standard (0.01 mg Cd L
1
), dem-
onstrating that the treatment system could treat the wastewater
in situ. However, the Cd concentration in the treated wastewa-
ter of the second chemical wash exceeded that of the rst
chemical wash. We believe that this occurred because the che-
lating resin surface was covered with suspended solids gener-
ated at pH adjustment tank, reducing the resins adsorptive
capacity. Although two compression lters were used to re-
move suspended solids (Fig. 2), some suspended solids passed
through the lters. The suspended solid removal phase of the
treatment system needs improvement.
The Cd concentration of pre-treatment wastewater in the
rst chemical wash was 0.069 mg L
1
(Fig. 4), while that of
the laboratory experiment was 0.133 mg L
1
, as described
previously (Makino et al., 2006). This decrease of Cd concen-
tration in the on-site test compared to the laboratory test could
be ascribed to the low efciency of soil-solution mixing, as
discussed in the next section.
3.2.2. Dilution prole of Cl concentration during
water washing
Table 1 shows the Cl concentrations in the pretreatment
wastewater: both calculated values (CV), as determined from
the amount of water applied, and measured values (MV), as
analyzed by the Cl meter during soil-wash operations. The
CV were calculated by using the following equation:
CV
n
CV
n1
TAWAW
n
=TAW 2
where CV
(n)
is the calculated Cl concentration at (n) water
washing times (mg L
1
); TAW is the total amount of water
in the experimental eld (29.74 kL); AW
(n)
is the amount of
water applied at (n) water washing times (kL).
MV values were lower than CV values during water wash-
ing operations (Table 1), although we previously found a good
agreement between CV and MV in a laboratory experiment
(Makino et al., 2006). The agreement in the laboratory exper-
iment meant that little Cl was adsorbed onto the Nagano soil;
that the dilution rate of Cl was equivalent to the rate of water
application if the soil-solution mixture was fully mixed; and
0.20
0.15
0.10
0.05
0.00
C
d

c
o
n
c
e
n
t
r
a
t
i
o
n

i
n

e
f
f
l
u
e
n
t

(
m
g

L
-
1
)
Breakthrough
Capacity (40)
Target wastewater quality standard
Bet volume
(BV; Influent volume of artifical wastewater/Chelating resin volume)
0 10 20 30 40 50 60
Fig. 3. Relationship between Cd load in articial wastewater and Cd concen-
tration in efuent treated with the chelating resin. Target wastewater quality
standard is equivalent to Japans environmental quality standard (0.01 mg
Cd L
1
).
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
C
o
n
c
e
n
t
r
a
t
i
o
n

o
f

C
d

(
m
g

L
-
1
)
Pretreatment wastewater
#1 #2 #1 #2 #3 #4 #5 #6 #7 #8
Chemical wash
frequency
Water-wash frequency
Treated wastewater
Fig. 4. Proles of Cd concentration in the pretreatment and treated wastewater
generated during the on-site soil-wash process.
116 T. Makino et al. / Environmental Pollution 147 (2007) 112e119
thus that Cl concentrations in the wastewater during water
washing operations can be used to estimate the degree of in
situ soil-solution mixing. Therefore, the discrepancy between
MVand CV in Table 1 indicates low efciency of soil-solution
mixing in situ compared with that in the laboratory experi-
ment. Because the cultivator in the paddy eld did not mix
the soil solution thoroughly enough, the structure of soil clods
was maintained and the diffusion of Ca and Cl ions into the
clods was likely a rate-controlling factor for the ion exchange
of Cd
2
adsorbed on to the soil by Ca
2
, decreasing the ef-
cacy of soil-solution mixing.
3.2.3. Chemical speciation of Cd in the wastewater
Cadmium has a good capacity to form complexes with var-
ious anions, such as Cl

, SO
4
2
, CO
3
2
, PO
4
3
, organic acids,
and fulvic acid (Traina, 1999). Because paddy soils receive
a wide variety of anions from different sources, including irri-
gation water, fertilizer, and soil amendments, the Cd extracted
from soil adsorption sites may easily form complexes with ex-
isting anions during the extraction process. To evaluate the
kinds of Cd complexes that formed during the rst chemi-
cal-wash process, we calculated the chemical species of Cd
that would be present in the extracts, using Visual MINTEQ
software (Gustafsson, 2004). The CdeCl complexes such as
CdCl

and CdCl
2
(aq) exceeded 75% of the total dissolved
Cd at 0.1 mol L
1
CaCl
2
(Fig. 5). Doner (1978) reported
that Cd is leached more rapidly in the presence of Cl

than
in the presence of ClO
4

. Sakurai and Huang (1996) showed

that the Cd desorption rate from montmorillonite-sorbed Cd
extracted by KCl solution is greater than that extracted by
KNO
3
solution. Smolders and McLaughlin (1996) suggested
that high concentrations of Cl

might increase plant uptake

of Cd either by enhancing mass transport of Cd or by enhanc-
ing uptake of the CdeCl

complex by plant roots. Accord-

ingly, the formation of stable CdeCl complexes could
promote Cd desorption from soils and inhibit resorption of
extracted Cd onto adsorption sites on the surface of the soil
particles.
3.3. Verication of the wash effect
3.3.1. Changes of Cd concentration in washed soil
The soil Cd concentrations extracted with three chemicals
and digested with acids are summarized in Table 2. There
was no signicant difference in soil Cd concentration between
the unwashed plot and the washed plot before the wash treat-
ment. All of the Cd concentrations were signicantly lower in
the washed plot than in the unwashed plot after the wash treat-
ment. In particular, the exchangeable Cd concentration in the
washed plot extracted with 1 mol L
1
NH
4
NO
3
decreased dra-
matically to 45% of that in the unwashed plot. This decrease
can be attributed to the Cd-extraction function of CaCl
2
, pri-
marily by ion exchange between Ca
2
supplied by CaCl
2
and Cd
2
adsorbed on soil (Makino et al., 2003).
The concentration of acid-soluble Cd in washed soils ex-
tracted with 0.01 and 0.1 mol L
1
HCl decreased signicantly
to 66% and 85%, respectively, of those in unwashed soils. The
total Cd concentration in washed soils digested with nitric
acid/perchloric acid also decreased to 83% of that in unwashed
soils. The formation of CdeCl complexes during the chemical
wash process may enhance the extraction of the acid-soluble
fractions, as described in Section 3.2.1.
3.3.2. Changes in soil fertility properties in washed soil
Table 3 summarizes the changes in soil fertility properties
with soil washing. Exchangeable Mg and K decreased owing
to soil washing; Mg, in particular, decreased to 25%, while ex-
changeable Ca increased. The Mg decit was corrected by the
application of Mg fertilizer to the washed plot, restoring the
Mg concentration in soil during the growth period to approx-
imately 70% of the value in the unwashed plot (data not
shown). Although EC increased, it did not reach a level that
would affect growth. Total carbon and total nitrogen concen-
trations and available nitrogen decreased slightly after
washing.
Cd
2+
, CdCl
+
, CdCl
2
(aq), Other species
Fig. 5. Percent distribution of Cd species in wastewater generated at the rst
chemical wash.
Table 2
Effects of washing treatment on the concentrations of various chemical forms
of Cd in soils
Sampling plot Soil Cd (mg kg
1
dry soil)
Exchangeable Weakly acid
soluble
Acid soluble Total
Before washing
Unwashed
a
0.021 0.05 0.67 0.71
Washed
b
0.020 0.27 0.68 0.71
After washing
Unwashed 0.022 0.26 0.67 0.71
Washed 0.010** 0.17** 0.57*** 0.59***
Signicant at the **0.01 and ***0.001 probability levels.
a
Washed without CaCl
2
.
b
Washed with CaCl
2
.
117 T. Makino et al. / Environmental Pollution 147 (2007) 112e119
As a result, although changes in some soil fertility proper-
ties were observed, they can be corrected, and we determined
that this soil-wash method did not have crucial adverse effects
on soil fertility.
3.3.3. Paddy rice cultivation
For Akitakomachi, no signicant difference was observed in
yields of shoot and brown rice grains between the washed and
unwashed plots (Table 4). Although Milyang 23 was almost
sterile owing to damage from cold summer weather, its shoot
yield was also similar among the plots. These results indicate
that the washing method did not affect the growth and yield
of paddy rice.
On the other hand, the shoot Cd concentration decreased
considerably with the soil-wash treatment in both plots. Cd
concentrations in rice also decreased from 0.44 and
0.13 mg kg
1
in the unwashed plot to 0.25 and 0.083 mg kg
1
for Milyang 23 and Akitakomachi, respectively. This reduc-
tion rate of plant Cd is higher than that of soil Cd estimated
by the total and acid-soluble form (Table 1), while the reduc-
tion rates of plant Cd and exchangeable soil Cd were about the
same. Cd
2
is the phytoavailable form of Cd (Wolt, 1994),
and could be equilibrated with exchangeable Cd (Kabata-
Pendias, 2000). Therefore, the removal of exchangeable Cd
by CaCl
2
washing enhanced the reduction of Cd uptake by
rice plants.
4. Conclusion
We developed a new on-site soil-wash process for Cd-con-
taminated paddy elds, comprising chemical washing fol-
lowed by water washing and on-site treatment to remove Cd
in the wastewater generated during the chemical and water
washes. The soil-wash experiment revealed the effectiveness
of in situ soil Cd removal, especially exchangeable fraction,
with on-site wastewater treatment. The washing had no effect
on rice yield, although it changed soil fertility properties, and
the Cd concentrations in soil and brown rice were lower in the
washed plot than in the unwashed plot, conrming the wash
effects. This is the rst experiment to verify the efcacy of
soil washing with a portable, on-site wastewater treatment sys-
tem to remediate Cd-contaminated paddy elds. We need,
however, to conrm the stability of the washing effects, as
a re-equilibration of exchangeable Cd possibly occurs, which
means that over time its concentration will increase again.
Acknowledgments
The authors gratefully acknowledge the useful suggestions
given during this work by Drs. H. Imai, M. Saito and S. Ono,
National Institute for Agro-Environmental Sciences. Thanks
are also due to Ms. J. Hino, Ms. G. Bao, Ms. F. Ochida, Ms.
M. Yasuda, Ms. T. Ishijima, and Ms. M. Asakawa for their as-
sistance in the experiments. This work was supported in part by
a Grant-in-Aid (Hazardous Chemicals) from the Ministry of
Agriculture, Forestry, and Fisheries of Japan (HC-04-1140-1).
References
Abumaizar, R.J., Smith, E.H., 1999. Heavy metal contaminants removal by
soil washing. Journal of Hazardous Materials 70, 71e86.
Bassi, R., Prasher, S.O., Simpson, B.K., 1999. Remediation of metal-contam-
inated leachate using chitosan akes. Environmental Technology 20,
1177e1182.
Benton, J.J., 2001. Plant analysis. In: Benton, J.J. (Ed.), Laboratory Guide for
Conducting Soil Tests and Plant Analysis. CRC Press, New York, pp.
191e245.
Calmano, W., Mangold, S., Stichnothe, H., Thoming, J., 2001. Clean-Up and
assessment of metal contaminated soils. In: Stegmann, R., Brunner, G.,
Calmano, W., Matz, G. (Eds.), Treatment of Contaminated Soil. Springer,
Berlin, pp. 471e490.
Codex Alimentarius Commission (Codex), 2005. Report of the 37th session
of the Codex Committee on Food Additives and Contaminants. Alinorm
05/28/12, 1e189.
Davis, A.P., 2000. Chemical and engineering aspects of heavy metal-contam-
inated soils. Revista Internacional de Contaminacion Ambiental 16,
169e174.
Doner, H.E., 1978. Chloride as a factor in mobilities of Ni(II), Cu(II), and
Cd(II) in soil. Soil Science Society of America Journal 42, 82e885.
Elliott, H.A., Herzig, L.M., 1999. Oxalate extraction of Pb and Zn from
polluted soils: solubility limitations. Journal of Soil Contamination 8,
105e116.
Gustafsson, J.P., 2004. Visual MINTEQ, version 2.30. Department of Land and
Water Resources Engineering. KTH, Stockholm.
Holmgren, G.G., Meyer, M.W., Chaney, R.L., Daniels, R.B., 1993. Cadmium,
lead, zinc, copper and nickel in agricultural soils of the United States of
America. Journal of Environmental Quality 22, 335e348.
Table 4
Effects of the washing treatment on yields and Cd concentration of two rice
varieties
Rice variety Plot Yield (kg ha
1
) Cd concentration (mg kg
1
)
Shoot Brown rice Shoot Brown rice
Akitakomachi Unwashed 1025 385 1.118 0.250
Washed 999 394 0.235** 0.083*
Milyang 23 Unwashed 622 NY
a
1.281 0.438
Washed 641 NY 0.421* 0.126**
Signicant at the *0.05 and **0.01 probability levels.
a
No yield (rendered sterile by cold summer weather).
Table 3
Comparisons of selected soil properties before and after washing treatment
Sampling plot
a
Before
washing
After
washing
pH(H
2
O) 5.88 5.75
pH(KCl) 4.69 5.22**
Electric conductivity (mS cm
1
) 0.04 0.36***
Total carbon (g kg
1
) 2.64 2.21*
Total nitrogen (g kg
1
) 0.23 0.20
Cation-exchange capacity 7.51 7.12
Exchangeable cations Ca
2+
(cmol
c
kg
1
) 3.45 7.78***
Exchangeable cations Mg
2+
(cmol
c
kg
1
) 2.01 0.52***
Exchangeable cations K
+
(cmol
c
kg
1
) 0.46 0.27**
Available phosphorus (mg P kg
1
) 123 216**
Available nitrogen (mg Nkg
1
) 156 124*
Signicant at the *0.05, **0.01 and ***0.001 probability levels.
a
Soils were sample from washed plots.
118 T. Makino et al. / Environmental Pollution 147 (2007) 112e119
Hong, K.J., Tokunaga, S., Kajiuchi, T., 2002. Evaluation of remediation pro-
cess with plant-derived biosurfactant for recovery of heavy metals from
contaminated soils. Chemosphere 49, 379e387.
Kabata-Pendias, A., 2000. Soils and soil processes. In: Kabata-Pendias, A.
(Ed.), Trace Elements in Soils and Plants, third ed. CRC Press, New
York, pp. 27e48.
Kawada, T., Suzuki, S., 1998. A review on the cadmium content of rice, daily
cadmium intake, and accumulation in the kidneys. Journal of Occupational
Health 40, 264e269.
Klima, M.S., Kim, B.H., 1997. Multi-stage wide-angle hydrocyclone circuits
for removing ne, high density particles from a low density soil matrix.
Journal of Environmental Science and Health, Part AdEnvironmental Sci-
ence and Engineering and Toxic and Hazardous Substance Control 32,
715e733.
Makino, T., Sugahara, K., Sakurai, Y., Takano, H., Kamiya, T., Sasaki, K.,
Itou, T., Sekiya, N., 2003. Remediation of cadmium contaminated paddy
soils by washing chemicals (1st Report). Feasibility of Chemical Washing
and Selection of Washing Chemicals. Promising Agriculture Practices and
Technologies for Reducing Heavy Metal Contamination in Relevant Staple
Crops, Abstract of the 23rd NIAES Symposium, 78e79.
Makino, T., Sugahara, K., Sakurai, Y., Takano, H., Kamiya, T., Sasaki, K.,
Itou, T., Sekiya, N., 2006. Restoration of cadmium contamination in paddy
soils by washing with chemicals: Selection of washing chemicals. Environ-
mental Pollution 144, 2e10.
Matsumoto, S., Ae, N., Yamagata, M., 2000. The status and origin of available
nitrogen in soils. Soil Science and Plant Nutrition 46, 139e149.
Mulligan, C.N., Yong, R.N., Gibbs, B.F., 1999. Removal of heavy metals from
contaminated soil and sediments using the biosurfactant surfactin. Journal
of Soil Contamination 8, 231e254.
Mulligan, C.N., Yong, R.N., Gibbs, B.F., 2001. Remediation technologies for
metal-contaminated soil and groundwater: an evaluation. Engineering
Geology 60, 193e207.
Murakami, H., Ae, N., Sugiyama, M., Ishikawa, S., 2004. Phytoremediation of
cadmium-contaminated paddy elds by a rice cultivar with high cadmium-
accumulation properties. NIAES Annual Report 2004, 5e6.
Nakashima, S., Ono, S., 1979. Counter plants of paddy soils contaminated by
cadmium and other heavy metals in Tsushima Island. Bulletin of Nagasaki
Agricultural Experimental Station 7, 337e385 (in Japanese).
Ogawa, B., Taguchi, K., Uemura, R., 1985. Studies on the mitigation of dam-
age for crop by heavy metals in soils. Bulletin of Akita Agricultural Exper-
imental Station 35, 1e64 (in Japanese).
Sakurai, K., Huang, P.M., 1996. Inuence of potassium chloride on desorption
of cadmium sorbed on hydroxyaluminosilicate-montmorillonite complex.
Soil Science and Plant Nutrition 42, 475e481.
Smolders, E., McLaughlin, M.J., 1996. Chloride increases cadmium uptake in
Swiss chard in a resin-buffered nutrient solution. Soil Science Society of
America Journal 60, 1443e1447.
Takijima, Y., Katsumi, F., Koizumi, S., 1973. Cadmium contamination of soils
and rice plants caused by zinc mining, V. Removal of soil cadmium by
a HCl-leaching method for the control of high Cd rice. Soil Science and
Plant Nutrition 19, 245e254.
Tandy, S., Bossart, K., Mueller, R., Ritschel, J., Hauser, L., Schulin, R.,
Nowack, B., 2004. Extraction of heavy metals from soils using biodegrad-
able chelating agents. Environmental Science and Technology 38, 937e944.
Thomas, G.W., 1982. Exchangeable cations. In: Page, A.L., Miller, R.H.,
Keeney, D.R. (Eds.), Methods of Soil Analysis, Part 2, Chemical and Mi-
crobiological Properties, second ed. Soil Science Society of America,
Madison, pp. 739e768.
Traina, S.J., 1999. The environmental chemistry of cadmium. In:
McLaughlin, M.J., Singh, B.R. (Eds.), Cadmium in Soils and Plants.
Kluwer Academic Publishers, Dordrecht, pp. 11e37.
Truog, E., 1930. Determination of the readily available phosphorus of soils.
J. Am Soc. Agronomy 22, 874e882.
U.S. Department of Agriculture (USDA), Natural Resources Conservation Ser-
vice, 1998. Keys to Soil Taxonomy, eighth ed. Washington, D.C.
Vangronsveld, J., Cunningham, S.D., 1998. Introduction to the concepts. In:
Vangronsveld, J., Cunningham, S.D. (Eds.), Metal-Contaminated Soils.
Springer, Berlin, pp. 1e15.
Wasay, S.A., Barrington, S., Tokunaga, S., 1999. Efciency of GAC for treat-
ment of leachate from soil washing process. Water, Air and Soil Pollution
116, 449e460.
Wolt, J.D., 1994. Trace elements in soil solution. In: Wolt, J.D. (Ed.), Soil
Solution Chemistry. Wiley and Sons, New York, pp. 246e274.
Yamasaki, S., Takeda, A., Nanzyo, M., Taniyama, I., Nakai, M., 2001. Back-
ground levels of trace and ultra-trace elements in soils of Japan. Soil
Science and Plant Nutrition 47, 755e776.
119 T. Makino et al. / Environmental Pollution 147 (2007) 112e119