Journal of Hazardous Materials 300 (2015) 161166

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Journal of Hazardous Materials

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

Role of phosphate and Fe-oxides on the acid-aided extraction

efciency and readsorption of As in eld-aged soil
Jinwoo Im a , Kyung Yang a , Seheum Moon b , Young-Jin Kim b , Kyoungphile Nam a,
a
Department of Civil and Environmental Engineering, College of Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-744, Republic
of Korea
b
Civil Engineering Division, Samsung C&T Corporation, 14, Seocho-daero 74-gil, Seocho-gu, Seoul 137-956, Republic of Korea

h i g h l i g h t s
Combined effect of acid and phosphate on As extraction was investigated in soil.
Phosphate inhibited readsorption of As on Fe-oxides, mainly on amorphous forms.
Optimal ratio of acid and phosphate was 0.2 M HCl/0.1 KH2 PO4 in all soils tested.

a r t i c l e

i n f o

Article history:
Received 18 April 2015
Received in revised form 24 June 2015
Accepted 25 June 2015
Available online 26 June 2015
Keywords:
Arsenic
Phosphate
Iron oxides
Acid extraction
Readsorption

a b s t r a c t
This study was conducted to investigate arsenic (As) readsorption phenomenon in acid-treated soil using
phosphate as a competing ion. Three eld-aged soils (i.e., S1, paddy soil; S2, eld soil; S3, forest soil)
originally contaminated with As ranging from 30 to 59 mg/kg-soil were collected from a former smelter
site. When 0.2 M hydrochloric acid (HCl) alone was used as an extraction solution, As bound to iron
(Fe) oxides was removed but signicant amount of the released As was readsorbed onto residual Feoxides, yielding low As extraction efciency of 1127%. Readsorption of the released As seemed to occur
preferentially on amorphous Fe-oxides. In contrast, As extraction efciency was greatly increased by 0.2 M
HCl solution supplemented with monopotassium phosphate (KH2 PO4 ), which was greatly inuenced by
the molar ratio of acid to phosphate. In addition, by the extraction solution with an optimal ratio of 0.2 M
HCl/0.1 M KH2 PO4 , As extraction efciency differed with soil types, showing 79.6, 44.1, and 61.0% in S1,
S2, and S3, respectively. The reason can be ascribed to the blocking of the available As readsorption sites
by phosphate ions, the sites seemed to mainly reside on the residual amorphous Fe-oxides in soil.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Acid increases the solubility of heavy metals in soil, and thus is
frequently used as an extraction agent from soil [1]. Especially for
oxyanions such as arsenic (As), which are mainly bound to iron (Fe)
oxides in soil, acid liberates bound As into soil solution by dissolving
the oxides [2]. In acidic solution, protonation of the surface of Feoxides (i.e., oxidation process) occurs, which weakens Fe O bond
and consequently dissolves Fe-oxides [3].
Most commonly used effective acids for heavy metals extraction are hydrochloric acid (HCl) and nitric acid (HNO3 ), generating
a strong acidic condition to secure ion exchange and dissolu-

Corresponding author at: Rm. 311, Bd. 35, Department of Civil and Environmental Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-744,
Republic of Korea. Fax: +82 2 873 2684.
E-mail address: kpnam@snu.ac.kr (K. Nam).
http://dx.doi.org/10.1016/j.jhazmat.2015.06.063
0304-3894/ 2015 Elsevier B.V. All rights reserved.

tion of soil mineral components, and thus liberating bound heavy

metals [4]. However, readsorption of released As onto residual Feoxides is likely to happen, which inevitably results in declined As
removal efciency from soil. Sidhu et al. [5] investigated the dissolution of Fe-oxides by HCl. Hydrochloric acid effectively dissolved
most of Fe-oxides tested except for Fe-oxides having high activation energy and closed structure like goethite. Although HCl is
effective in dissolving Fe-oxides, readsorption of the liberated As
has been previously reported [68]. Greubel et al. [6] and Jackson and Miller [7] showed that 0.25 M NH2 OHHCl/0.25 M HCl
solution completely dissolved amorphous Fe-oxides and released
As into solution, but 99.9% of the released As was readsorbed
onto undissolved Fe-oxides like goethite while 100% of extraction efciency of As was obtained in the absence of goethite.
Kim and Baek [8] reported that strong acids like HCl and HNO3
exhibited less than 30% of As removal efciency from soils,
which was lower than when phosphoric acid or oxalic acid was
used.

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J. Im et al. / Journal of Hazardous Materials 300 (2015) 161166

Table 1
Procedures for modied Wenzels sequential extraction for As in soil.
Fraction

Extractant

Extraction condition

Chemical form

0.05 M (NH4 )2 SO4

Non-specically bound

0.05 M (NH4 )H2 PO4

0.2 M NH4 -oxalate buffer; pH 3.25

0.2 M NH4 -oxalate buffer + 0.1 M ascorbic acid; pH 3.25

18 mL HNO3 + 8 mL HF + 2 mL H2 O2 + 2 mL H2 O

1:25 of soil to solution

4-h shaking, 20 C
1:25 of soil to solution
16-h shaking, 20 C
1:25 of soil to solution
4-h shaking in the dark, 20 C
1:25 of soil to solution
30 min in a water basin at 96 3 C in the light
Microwave digestion according to USEPA 3052 method

Phosphate shows similar environmental behaviors to arsenate

(AsO4 3 ), a dominant form of As in oxidized environment [9], and
thus phosphate addition can be an alternative to inhibit readsorption of acid-released As onto soil. Due to its chemical similarity,
PO4 3 and AsO4 3 share the same adsorption sites capable of making inner- and outer-sphere complexation, which makes phosphate
outcompete As for binding on Fe-oxides surface [10]. Manning
and Goldberg [11] reported that the presence of phosphate ions
decreased As adsorption on the goethite surface. Jain and Loeppert
[12] also demonstrated that adsorption of As on ferrihydrite, amorphous Fe-oxide, signicantly decreased by 89% in the presence of
phosphate. The competition between phosphate and As is so effective that phosphate salts are frequently used in extraction methods
for removing strongly or specically adsorbed As [13].
Although separately well known, the combined effect of acid and
phosphate on As extraction, when present phosphate was used to
block readsorption of hydrochloric acid-extracted As on residual
iron oxides, together, has rarely been demonstrated. In this study,
the role of phosphate ions on the extraction efciency of As by
inhibiting readsorption of acid-released As was investigated with
a eld-aged soil. Specically, we studied the mechanisms involved
in the combined action of acid and phosphate on As extraction by
analyzing the chemical forms of As before and after extraction and
the changes in types of iron oxides.
2. Materials and methods
2.1. Soil sampling and characterization
Soil samples were collected from a former Janghang smelter site
located in southwest Korea. The smelter had been operated for over
60 years to rene copper and lead ores and was closed in 1989.
Soils within 1.5 km from the chimney of the smelter were found
to be signicantly contaminated with heavy metals including As,
Pb, and Cd, and especially soil As concentrations, with an average
of 42.7 29.8 mg/kg, exceeded the Korea soil regulatory level (i.e.,
25 mg/kg-soil) [14]. Soil contamination was caused by scattering
ores, rening residues, and chimney dust containing arsenic trioxide (As2 O3 ). The site mainly consists of paddy, elds, and forests,
and the three kinds of soil samples were taken from the surface soil
(030 cm) of each land use. All samples were air-dried and passed
through a 2-mm sieve for further experiments.
Total As concentrations of the eld-collected soil samples S1
(paddy soil), S2 (eld soil), and S3 (forest soil) were determined
by aqua regia digestion method [15]. Soil properties such as soil
texture, soil pH, and Iron (Fe)-oxides content were determined
according to methods of soil analysis [1617]. Soil textures of S1,
S2, and S3 were silt loam, sandy loam, and sand, respectively, and
soil pH (1:5 soil slurry with deionized water) of the soils were
6.1, 6.9, and 7.2, respectively. Iron oxides content was quantitatively determined by dithionite-citrate-bicarbonate (DCB) method
[18]. Briey, 2 g of each soil sample (i.e., S1, S2, and S3 and the
soils treated with either acid or phosphate, or both) and 45 mL of

Specically bound
Amorphous iron-oxide
bound
Crystalline iron-oxide
bound
Residual

buffered citrate-bicarbonate reagent were mixed in a 50 mL conical tube. The tube was immersed in an oil bath maintained at 75 C
with agitation. When the sample reached the temperature of the
bath, the tube was received 1 g of dithionite powder and continuously agitated. After 5 min, another 1 g of dithionite powder was
added and agitation was continued for another 10 min. After nishing digestion, the tube was centrifuged at 16,000 g for 10 min and
the supernatant was ltered through a 0.45-m GHP lter. Iron
concentration in the ltrate was determined with an Inductively
Coupled Plasma Optical Emission Spectrometer (ICP-OES, iCAP
7400 DUO, Thermo Scientic, USA). The presence of Fe-oxides was
also identied by X-ray diffraction (XRD) method. An X-ray powder
diffractometer (D8 ADVANCE with DAVINCI, BRUKER, Germany)
using Cu K radiation was operated at 40 kV and 40 mA and the
scanning range of 2 was between 5 and 90 degree with 0.02 step
sizes.
2.2. Extraction with acid and phosphate
In the presence of 0.2 M HCl (pH 0.8), batch experiments were
conducted with various phosphate concentrations to extract As
from the soil samples S1, S2, and S3. The concentration of HCl was
determined based on the previous study [19] showing that acid
extraction was appreciable in the pH range < 1. Four grams of soil
and 20 mL of 0.2 M HCl amended with KH2 PO4 to give a nal concentration of 0.02, 0.04, 0.1, or 0.2 M were mixed in a 50 mL conical
tube and the mixture was shaken for 4 h at 240 rpm in a reciprocal shaker at room temperature. After shaking, the mixture was
centrifuged at 16,000 g for 10 min and the supernatant was ltered
by a 0.45-m GHP syringe lter and then As in the ltrate was
analyzed by using an ICP-OES. Another set of experiment was performed to determine the behavior of As when extracted with either
acid (0.2 M HCl) or phosphate (0.1 M KH2 PO4 ), or both (0.2 M HCl
amended with KH2 PO4 to give nal concentration of 0.1 M, hereafter expressed as 0.2 M HCl/0.1 M KH2 PO4 ). The pH value of 0.2 M
HCl/0.1 M KH2 PO4 was 1.1.
2.3. Sequential extraction of As
A sequential extraction method proposed by Wenzel et al. [20]
was employed to determine the changes of chemical forms of As
in the soil samples after acid extraction with or without phosphate. For the soils treated with 0.2 M HCl or 0.2 M HCl/0.1 M
KH2 PO4 , rinsing (i.e., 10-min shaking with 1:5 soil to deionized
water) was conducted before sequential extraction. The sequential extraction method differentiates soil As into ve fractions
depending on its chemical form; (i) non-specically bound As (F1,
(NH4 )2 SO4 extractable), (ii) specically bound As (F2, (NH4 )H2 PO4
extractable), (iii) amorphous hydrous iron oxides-bound As (F3,
NH4 -oxlatate extractable), (iv) crystalline hydrous iron oxidesbound As (F4, NH4 -oxalate/ascorbic acid extractable), and (v)
residual As (F5, HNO3 /HF/H2 O2 -extractable). For this study, USEPA
3052 method was employed to determine residual As (F5) [21].

J. Im et al. / Journal of Hazardous Materials 300 (2015) 161166

163

Table 2
Total and sequential extraction data of As concentrations in the soil samples.
Extraction method for As

S1

S2

S3

Total As conc. by aqua regia digestion method (mg/kg)

Total As conc. by Wenzels sequential extraction (mg/kg)
Chemical form of As in soil (%)

59.2
65.6
0.5
12.5
64.5
13
9.5

30.8
36.7
0.9
12.1
36.4
35.4
15.2

53.1
55.9
1.5
13.8
45.6
26.9
12.2

F1a
F2
F3
F4
F5

a
F1: Non-specically bound fraction, F2: Specically bound fraction, F3: Amorphous iron oxide-bound fraction, F4: Crystalline iron oxide-bound fraction, and F5: Residual
fraction.

Statistically signicant difference in As concentration was determined by Students t-test at 5% signicance level with Excel 14.0
(Microsoft Corporation, USA). All experiments were performed in
triplicates.

was 12.5, 12.1, and 13.8% in S1, S2, and S3, respectively. In contrast,
regardless of the As concentrations in the soil samples, As bound to
amorphous and crystalline Fe-oxides (F3 and F4) occupied the highest fractions, yielding 77.5, 71.8, and 72.5%, respectively. Signicant
amounts of Fe-oxides, 8,240, 10,757, and 1,941 mg/kg, respectively,
were identied in the soil samples tested. Adsorption of As in soil
is known to occur mainly on Fe-oxides rather than other soil components such as organic matter [22]. The point of zero charges
of Fe-oxides such as ferrihydrite and goethite are about 7.8 and
9.2, respectively [23], and thus the surfaces are positively charged
under neutral pH conditions, making the soil component a good
sorbent for As oxyanions [11].

3. Results and discussion

3.2. Effect of phosphate on acid extraction of As

3.1. Characterization of soil As

The effect of phosphate concentration on As extraction efciency (i.e., inhibition of As readsorption) was investigated.
Extraction of As by 0.2 M HCl solution amended with KH2 PO4 to
give nal concentration of 0.02, 0.04, 0.1, or 0.2 M was investigated.
As shown in Fig. 1a, extraction of As by 0.2 M HCl was continuously increased until the amended KH2 PO4 concentration reached
0.1 M, but an additional increase was not observed at 0.2 M KH2 PO4
concentration.
For further experiment to determine the combined effect of
acid and phosphate on acid extraction of As, which consequently
inuences on As extraction efciency, 0.2 M HCl solution supplemented with KH2 PO4 to give a nal concentration of 0.1 M (i.e.,
0.2 M HCl/0.1 M KH2 PO4 ) was chosen. Extraction efciencies of As
from the three soil samples were determined with 0.2 M HCl, 0.1 M
KH2 PO4 , and 0.2 M HCl/0.1 M KH2 PO4 . When 0.1 M KH2 PO4 was
used alone, only 12.3, 13.5, and 15.9% of extraction efciencies
were obtained in S1, S2, and S3, respectively (Fig. 1b). The fact that
Fe concentrations in the extracting solution were negligible (i.e.,
less than 1 mg/kg-soil) in all soil samples indicates that dissolu-

2.4. Statistical analysis

Total As of the soil samples S1 (paddy soil), S2 (eld soil),

and S3 (forest soil) were determined by aqua regia digestion
method [15] and the determined concentrations were 59.2, 30.8,
and 53.1 mg/kg, respectively (Table 2). The sequential extraction
method used in this study was the ve-step method proposed
by Wenzel et al. [20] with some modications. The microwaveassisted 5th-step extraction method used in this study, adopted
from USEPA 3052 method [21] provided more harsh extraction
conditions than the original 5th-step extraction condition (i.e.,
HNO3 /H2 O2 extractaction). The extraction efciency with this
modied Wenzels ve-step sequential extraction method was a
little higher, 12% on average, than the concentrations determined
by aqua regia digestion method (Table 2).
Data in Table 2 showing the chemical forms of As demonstrate
that non-specically bound form of As (i.e., sulfate-extractable
form, F1) was very low in all soil samples and phosphateextractable form of As, designated as specically bound form (F2),
100

80

S1
S3

60

S2

40

20

0
0.00

0.2 M HCl-extractable As
0.1 M KH2 PO4 -extractable As
0.2 M HCl/0.1 M KH2 PO 4 -extractable As

(b)
As extraction efficiency (%)

As extraction efficiency (%)

,
4000

100

(a)
80

,
3000

60
2000
,
40
1000
,
20

0
0.05

0.10

0.15

KH2PO4 concentration (M)

0.20

Fe concentration (mg/kg)

Extraction solutions and conditions for each step are described in

detail (Table 1). After each step, the mixture of soil and extraction
solution was centrifuged at 16,000 g for 10 min and the supernatant
was ltered by a 0.45-m GHP lter, and As concentration in the
ltrate was determined by using an ICP-OES.

S1

S2

S3

Soil

Fig. 1. Extraction efciencies of As in the soils tested. (a) Effect of various KH2 PO4 concentrations at 0.2 M HCl and (b) Effect of phosphate on the inhibition of As readsorption
during the extraction by 0.2 M HCl, 0.1 M KH2 PO4 , and 0.2 M HCl/0.1 M KH2 PO4 . Symbols represent Fe concentrations extracted by 0.2 M HCl (open circles), 0.1 M KH2 PO4
(open triangles), and 0.2 M HCl/0.1 M KH2 PO4 (open squares), respectively.

164

J. Im et al. / Journal of Hazardous Materials 300 (2015) 161166

tion of Fe-oxides did not occur by KH2 PO4 and the As extracted
seemed to be SO4 2 - and PO4 3 -exchangeable forms. Actually,
the concentrations of 0.1 M KH2 PO4 -extractable As in Fig. 1b are
consistent with the sums of F1 and F2 fractions in S1, S2, and
S3, respectively (Table 2). Although extraction efciency varied
depending on the soils tested, 0.2 M HCl alone liberated much less
As than 0.2 M HCl/0.1 M KH2 PO4 . The former extracted 27.0, 10.6,
and 19.3% of soil As while the latter could release 79.6, 44.1, and
61.0% from S1, S2, and S3, respectively. Such effectiveness of phosphate ions on enhanced As extraction was previously reported by
many researchers [8,1012,22]. While the extracted As concentrations increased 34 times more, Fe concentrations extracted by
0.2 M HCl and 0.2 M HCl/0.1 M KH2 PO4 were not much different;
2,103.5, 643.4, and 197.1 mg/kg and 2,944.3, 978.7, and 470.4 mg/kg
of Fe were extracted from soil by the two extracted solutions for S1,
S2, and S3, respectively (Fig. 1b). This indicates that similar amount
of Fe-oxides was dissolved and thus corresponding amount of soil
As was assumed to be originally released by 0.2 M HCl and 0.2 M
HCl/0.1 M KH2 PO4 . In the absence of phosphate ions, however, the
released As oxyanions seemed to readsorb to residual Fe-oxides.
This provides another line of evidence showing the blocking effect
of phosphate on the inhibition of As readsorption.

Fig. 2. X-ray diffraction pattern of soil sample S2 showing the presence of crystalline
Fe-oxide (i.e., goethite).

3.3. Effect of Fe-oxides on extraction and readsorption of As

It is worthwhile comparing the As extraction efciencies in
Fig. 1b to the ve-step extraction data presented in Table 2. The
percentages of As extracted by 0.2 M HCl/0.1 M KH2 PO4 (i.e., 79.6,
44.1, and 61.0%) matched well with the sum of F1, F2, and F3 (77.5,
49.4, and 60.9%) in S1, S2, and S3, respectively, suggesting that
SO4 2 - and PO4 3 -exchangeable forms of As and As bound to amorphous Fe-oxides occupied the portions extracted by the combined
action of 0.2 M HCl and 0.1 M KH2 PO4 . In addition, the Fe-oxides
concentrations determined by DBC method [18] before and after
0.2 M HCl extraction (Table 3) are consistent with the previous nding that HCl preferentially dissolves amorphous forms of Fe-oxides
rather than crystalline forms [23]. In soil S1, for instance, total Feoxides concentration decreased from 8,240 mg/kg (original soil) to
5,613 mg/kg after 0.2 M HCl extraction, and thus the proportion of
amorphous Fe-oxides decreased from 40.6 to 29.9%. The same was
true to soil samples S2 and S3. As expected, the presence of 0.1 M
KH2 PO4 did not further decrease the Fe-oxides contents in soil.
Such a huge difference in extraction efciency in Fig. 1 was not
due to pH change during the extraction because the nal pH of
the extraction solutions fell between 1.0 and 1.4. When compared
to the Fe-oxides concentrations in the original soils, signicant
amounts of Fe-oxides were still present in the soil samples after
extraction (Table 3). Such residual Fe-oxides seemed to act as sorbents for readsorption of the liberated As when 0.2 M HCl solution
alone was used. In contrast, when 0.1 M KH2 PO4 was present,
PO4 3 ions outcompeted the extracted As present as AsO4 3 for
adsorption sites on the residual Fe-oxides [12], which probably

resulted in such higher extraction efciencies in Fig. 1. Competition between As oxyanions and phosphate seems to be inuenced
by the molar ratio of As to phosphate. Jain and Loeppert [12]
reported that adsorption of As on Fe-oxides decrease by 89% at
the molar ratio (As to PO4 3 ) of 1:50. Assuming that 100 mg/kg of
As (i.e., 1.3 mmol-As/kg-soil) is present in soil, 0.1 M KH2 PO4 (i.e.,
500 mmol-PO4 3 /kg-soil) seems to be enough to inhibit the readsorption of the acid-released As. In fact, the As concentrations in the
soils tested ranged from 30.8 to 59.2 mg/kg or 36.7 to 65.6 mg/kg
when determined by aqua regia digestion or the sequential extraction method, respectively.
Dissimilar extraction efciencies of As were observed depending on soil types (Fig. 1). Soil sample S1 had higher proportion of
amorphous Fe-oxides than S2 and S3, and the soil exhibited the
highest As extraction efciency by 0.2 M HCl at all KH2 PO4 concentrations tested. The released As was likely to mainly result from
the dissolution of amorphous Fe-oxides. For example, ferrihydrite
is dissolved by acid about 1000 times more and faster than goethite
because of its high solubility product (pKsp 3840 at 25 C) and dissolution rate (1.2 108 mol/m2 .s in ascorbic acid) [23]. Therefore,
it is reasonable to assume that As associated with amorphous Feoxides was more easily released into solution than As bound to
crystalline Fe-oxides. In contrast, soil sample S2 showed the least
As extraction efciency by 0.2 M HCl at all KH2 PO4 concentrations
tested. As shown in Table 3, Fe-oxides content in S2 was the highest, and the proportion of amorphous Fe-oxides was low and that
of crystalline Fe-oxides was high both before and after 0.2 M HCl
extraction. Crystalline Fe-oxides such as goethite, akaganeite, and

Table 3
Iron oxides concentrations determined by DBC method and their crystallinity in the soil samples.
Soil samples

Fe-oxides conc.

(%) estimateda

(mg/kg)

Amorphous Fe-oxides

Crystalline Fe-oxides

Original soil

S1
S2
S3

8,240
10,757
1,941

40.6
15.7
16.3

59.4
84.3
83.7

0.2 M HCl-extracted
soilb

S1
S2
S3

5,613
7,885
1,240

29.9
14.3
13.5

70.1
85.7
86.5

a
b

(Fe conc. in F3 or F4)/(sum of Fe conc. in F3 and F4).

The same soil employed for generating Fig. 1.

J. Im et al. / Journal of Hazardous Materials 300 (2015) 161166

0.2 M HCl/0.1 M KH2 PO4 -extracted soil

0.2 M HCl-extracted soil

Original soil
50

30

25

(c) S3

(b) S2

(a) S1

As concenration (mg/kg)

165

40

20

30

15

25

20

15
20

10
10

10

0
2

Fraction

Fraction

Fraction

Fig. 3. Concentrations of As present as different chemical forms after extraction with 0.2 M HCl, 0.1 M KH2 PO4 , and 0.2 M HCl/0.1 M KH2 PO4 . (a) S1, (b) S2, and (c) S3.

hematite were really identied by XRD analysis in S2 (Fig. 2). This

probably generated the lowest extraction efciency of As in S2.

forms of As were observed in fractions F1 and F5, but they were

negligible and not presented in Fig. 3.
4. Conclusions

3.4. Changes in chemical forms of As

Since Fe-oxides are the major component for As adsorption and
about 71.877.5% of total As was bound to Fe-oxides in the soils
tested, it is meaningful to understand the changes in F3 and F4
fractions after acid and phosphate extraction. In the original soil
sample S1 (Fig. 3a), about 42.8 and 8.6 mg-As/kg-soil were found to
be associated with amorphous and crystalline Fe-oxides (F3 and
F4 fraction), respectively. After 0.2 M HCl extraction, 36.5 mg/kg
of As was found in F3 fraction and As concentration in F4 fraction increased to 13.4 mg/kg. In contrast, when treated with 0.2 M
HCl/0.1 M KH2 PO4 , only 12.8 mg/kg of As remained in amorphous
Fe-oxides in the same soil and little change was observed in F4 fraction. Similar trends, but to different extents, were also observed in
soils S2 and S3 (Fig. 3b and c).
The results in Fig. 3 clearly demonstrate that readsorption of
the acid-released As mainly occurred on amorphous Fe-oxides,
and the presence of phosphate effectively inhibited such readsorption. Previous studies reported that more As is prone to adsorb
to amorphous Fe-oxides than to crystalline Fe-oxides due to the
high surface area and the presence of functional groups of amorphous Fe-oxides [2425]. Since phosphate ions exhibit the similar
binding behavior as As oxyanions, more phosphate ions also had
chances to adsorb to residual amorphous Fe-oxides under excessive phosphate concentrations (i.e., our experimental conditions).
When the As concentration by 0.2 M HCl/0.1 M KH2 PO4 extraction
is compared to that by 0.2 M HCl extraction, the difference represents the extent of inhibition of As readsorption in the presence of
phosphate ion. In all soil samples tested, the difference was higher
in F3 fraction than in F4 fraction. Such blocking effect by phosphate
was higher in soil S1 having more amorphous Fe-oxides than S2
and S3, which is consistent with the data presented in Fig. 1.
The fact that As concentration in F2 fraction greatly decreased in
the soils extracted with 0.2 M HCl/0.1 M KH2 PO4 compared to the
original soils (for instance, from 8.3 to 1.5 mg/kg in S1) suggests
that, apart from blocking effect by phosphate ions, ion exchange
between As oxyanions and phosphate ions occurred probably due
to the excessive phosphate concentration. Changes in chemical

Our data clearly demonstrate that combined action of acid and

phosphate on As extraction is effective to remove Fe-oxides bound
As from soil. An optimal ratio of acid to phosphate was derived:
0.2 M HCl/0.1 M KH2 PO4 showed 79.6, 44.1, and 61.0% of As extraction efciencies in S1 (paddy soil), S2 (eld soil), and S3 (forest soil),
respectively. In addition, the readsorption of the acid-released As
onto Fe-oxides and the inhibition of such As readsorption by phosphate ions were studied, which indicates that overall As extraction
efciency was greatly inuenced by the molar ratio of acid to
phosphate and the amorphous Fe-oxides in soil. Our results would
provide effective design parameters for washing technology in the
remediation of As-contaminated soil.
Acknowledgements
This study received substantial nancial support from the
Geo-Advanced Innovative Action (GAIA) Project of the Korea
Environmental Industry & Technology Institute (KEITI). A partial
nancial support was also provided by Korea Ministry of Environment as Knowledge-based environmental service (Waste to
energy) Human resource development Project.
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