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, 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