Chemosphere 154 (2016) 276e282

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Potential for leaching of arsenic from excavated rock after different

drying treatments
Jining Li a, Tomoya Kosugi a, Shohei Riya a, Yohey Hashimoto b, Hong Hou c,
Akihiko Terada a, Masaaki Hosomi a, *
a
Department of Chemical Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Naka, Koganei, Tokyo 184-8588, Japan
b
Department of Bioapplications and Systems Engineering (BASE), Tokyo University of Agriculture and Technology, 2-24-16 Naka, Koganei, Tokyo 184-8588,
Japan
c
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Dayangfang 8, Beijing 100012,
PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Considerable total As was water-

leached from an excavated rock.

Air-, 40  C-, and freeze-drying treat- Rock Different drying methods

ments increased the As leaching.

Freeze-drying increased As leaching
by the largest extent.
Excavation

Dissolution of Fe, Al, and dissolved

organic carbon correlated with As
Sequential leaching tests Rapid small-scale column tests
leaching.

Pollution potential indices are pro-
Potential for leaching of arsenic
posed to evaluate the pollution threat
of As.

a r t i c l e i n f o a b s t r a c t

Article history: Leaching of arsenic (As) from excavated rock subjected to different drying methods is compared using
Received 21 January 2016 sequential leaching tests and rapid small-scale column tests combined with a sequential extraction
Received in revised form procedure. Although the total As content in the rock was low (8.81 mg kg1), its resulting concentration
19 March 2016
in the leachate when leached at a liquid-to-solid ratio of 10 L kg1 exceeded the environmental standard
Accepted 28 March 2016
(10 mg L1). As existed mainly in dissolved forms in the leachates. All of the drying procedures applied in
this study increased the leaching of As, with freeze-drying leading to the largest increase. Water
Handling Editor: X. Cao extraction of As using the two tests showed different leaching behaviors as a function of the liquid-to-
solid ratio, and achieved average extractions of up to 35.7% and 25.8% total As, respectively. Dissolu-
Keywords: tion of As from the mineral surfaces and subsequent re-adsorption controlled the short-term release of
Arsenic As; dissolution of Fe, Al, and dissolved organic carbon played important roles in long-term As leaching.
Excavated rock Results of the sequential extraction procedure showed that use of 0.05 M (NH4)2SO4 underestimates the
Leaching readily soluble As. Long-term water extraction removed almost all of the non-specically sorbed As and
Drying
most of the specically sorbed As. The concept of pollution potential indices, which are easily determined
by the sequential leaching test, is proposed in this study and is considered for possible use in assessing
efcacy of treatment of excavated rocks.
2016 Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: hosomimasaaki1130@gmail.com (M. Hosomi).

http://dx.doi.org/10.1016/j.chemosphere.2016.03.129
0045-6535/ 2016 Elsevier Ltd. All rights reserved.
 J. Li et al. / Chemosphere 154 (2016) 276e282
1. Introduction
Arsenic (As), a metalloid belonging to Group 15 of the Periodic
Table, is ubiquitously present in the natural environment at trace
levels (Wilson et al., 2010). According to a report of the World
Health Organization (WHO), As is one of ten chemicals of major
public health concern (WHO, 2012). Long-term As exposure from
food and drinking water can cause cancer and skin lesions, as well
as developmental effects, cardiovascular disease, neurotoxicity, and
diabetes (WHO, 2012). Because of these negative impacts on hu-
man health, the WHO recommended a provisional standard of
10 mg L1 for arsenic in drinking water (WHO, 1994).
Many construction projects require excavation of large quantities
of deep rocks. Although the amounts of As in these rocks are often
very low, the concentrations in their resultant leach solutions can
exceed environmental standards: for example, Tabelin et al. (2014a)
found that the As concentrations in leachates from some excavated
rocks were higher than the Japanese environmental standard
(10 mg L1). This underscores the need to properly dispose of such
rocks. In fact, in Japan, efforts are now directed at the potential risks
of excavated rocks, and the Soil Contamination Countermeasures
Law of Japan (Ministry of the Environment, 2011) was amended to
extend the interpretation to cover these solids. To assess the po-
tential for contamination of As from such rocks and to develop
effective and economically feasible remediation technologies, more
detailed knowledge about As behavior in excavated rocks is required
to better understand its release to the surrounding environment.
To date, the risk of pollutants leaching from a variety of solids
has been determined by laboratory leaching tests, such as batch
and column tests (Grathwohl and Susset, 2009). Batch tests provide
a snapshot of a particular liquid-to-solid (L/S) ratio (Maszkowska
et al., 2013), but do not simulate actual eld conditions because
of friction between the particles during mechanical agitation,
centrifugation, and ltration of the sample prior to analysis. Col-
umn test conditions are more similar to eld conditions and more
representative than batch tests because there is no mechanical
friction, the packed material has self-ltration capacity, and
observation of time-dependent leaching behavior is possible
(Krger et al., 2012). Although some studies have compared batch
and column tests with respect to As release from soils or wastes (Al-
Abed et al., 2008; Kim and Hyun, 2015), no study has quantitatively
compared these techniques for investigating the potential for As
release from excavated rocks.
An appropriate methodology for storage of excavated rocks still
requires development. As it acts on a soil sample, drying treatment
plausibly enables a rock sample to be stored for longer time and
contributes to development of a standardized methodology, which
allows one to compare results for As release from different rocks.
However, drying may change the status and properties of trace el-
ements in the rocks and raises the question of whether As release
from dried samples is representative of eld conditions (Supriatin
et al., 2015). To date, the effect of different drying methods on As
extraction from soils has been studied (Huang et al., 2015), however,
the inuence of drying on As leaching behavior from excavated
rocks is largely unknown. The objectives of this study are, therefore:
(1) to investigate the effects of drying methods on the As leaching
from an excavated rock; (2) to compare the potential for As leaching
under batch and column conditions; and (3) to identify the domi-
nant processes governing As leaching from this excavated rock.
2. Materials and methods
2.1. Sample collection and characterization
The excavated rock used in our study was obtained from Tokyo,
277
Japan, in February 2015. After collection, all samples were placed in
airtight polyethylene bags and transported to the laboratory. The
collected rock was pretreated by four common drying methods: (1)
air-drying at room temperature for 7 days (AD); (2) oven-drying at
40  C for 24 h (40D); (3) freeze-drying at 50  C for 24 h (FD); and
(4) no drying (ND). After being subjected to the selected pretreat-
ment, the samples were gently crushed and sieved through a 2-mm
sieve. A portion of the sample with a particle size of less than 2 mm
was used for the leaching experiments. Further description of
sample characterization is provided in the Supplementary Material.
Selected physicochemical properties are shown in Table S1. The
total As concentration in this rock was 8.81 mg kg1.
2.2. Leaching experiments
2.2.1. Sequential leaching tests
Sequential leaching tests (SLT) are sometimes used to study
long-term leaching of contaminants from solids into water
(Grathwohl and Susset, 2009). In this study, referring to Notica-
tion No. 46 of the Ministry of Environment (Japan), the SLT was
conducted under ambient conditions. A 3-g sample (dry weight
basis; 4.44 g for sample with ND) and 30 mL of deionized water
(18 MU cm) were mixed in a 50-mL centrifuge tube. To determine
an appropriate shaking time, we performed preliminary batch
leaching experiments with different shaking periods (0.5 h, 1 h, 3 h,
6 h, 12 h, and 24 h). The mixture was shaken at a rate of 200 rpm at
room temperature and pressure. The slurry was centrifuged at
about 4700 g for 15 min and the supernatant was ltered through a
0.45-mm membrane lter before analysis. These procedures were
repeated until the As concentration in the leachate was below its
detection limit (0.05 mg L1). The residual sample material was
dried using the methods described above and then digested for As
measurement.
After the 0.45-mm ltration, As in leachates is commonly clas-
sied into dissolved and colloidal fractions (Nystrand et al., 2012).
In our study, part of the 0.45-mm ltered leachate after 24-h
shaking was further ltered using a 0.1-mm lter and the As in
this ltrate was considered to be present in dissolved form. The
difference between the 0.45-mm and 0.1-mm lterable As was
attributed to colloidal form. Fe and Al in the leachates were also
classied by the same method.
2.2.2. Rapid small-scale column tests
Rapid small-scale column tests (RSSCT), which allow break-
through curves as functions of time and volume of permeates to be
generated, were originally developed to simulate the removal of
organic pollutants and natural organic matter by granular activated
carbon (Crittenden et al., 1987, 1991). They are appropriate for use
with the excavated rock in this study because of its high perme-
ability. A series of stand-alone RSSCT columns (internal diameter,
1.7 cm; length, 24 cm) were constructed and an up-ow congu-
ration was employed, which differs from the regular RSSCT test. The
experimental set-up is shown in the Supplementary Material. To
readily compare these As leaching results with those of the SLT, a
3.0-g sample (4.44 g for sample with ND) was packed in each col-
umn. The column was rst slowly saturated with water from bot-
tom to top; water was then continuously supplied at a ow rate of
1.0 mL min1. Fifteen column efuent samples of 30 mL each
(equivalent to 10 L kg1 of L/S) were collected (sample numbers
1e15); thereafter, samples were collected every 50 mL (equivalent
to every 16.7 L kg1) and numbered from 16 onward. Sampling
continued until the As concentration was below its detection limit.
The residual material was dried and digested for As measurement.
278 J. Li et al. / Chemosphere 154 (2016) 276e282

2.2.3. Chemical analysis
pH and Eh of the samples were measured by pH (Navi F-52;
HORIBA, Kyoto, Japan) and oxidationereduction potential meters
(D-53, HORIBA, Kyoto, Japan), respectively. As, Fe, Al, and Mn con-
tents in the leachates were measured by inductively coupled
plasma mass spectrometry (ICPeMS, 7500c, Agilent, Tokyo, Japan),
after appropriate dilution as necessary. Dissolved organic carbon
(DOC) in the leachate was measured using a TOC-VCSH/CSN
analyzer (Shimadzu, Kyoto, Japan).
2.3. Pollution potential indices
release; freeze-drying most enhanced As release (Fig. S1 (b)). After
the second ltration (0.1 mm) step, the As concentrations showed
no obvious decrease in comparison with those of leachates passed
though the 0.45-mm lters (Fig. S2 (a)); however, the Fe and Al
concentrations decreased signicantly (close to zero) after passing
through the 0.1-mm lters (Fig. S2 (b) and (c)). This nding indicates
that most Fe and Al existed in colloidal forms in the leachates, while
As mainly existed in dissolved forms.
3.2. Arsenic leaching in sequential leaching and rapid small-scale
column tests

In this study, we propose the concept of pollution potential
indices (PPI). At a certain L/S value, the ratio of cumulative As to
cumulative volume will reach the environmental standard
(10 mg L1) (see equation (1)). The value of L/S at this time is
considered as the PPI. A higher PPI value indicates a higher pollu-
tion threat. The key point for this method is obtaining the cumu-
lative amount of As released. Two equations were used to t the
cumulative release of As in the SLT and RSSCT with increasing of L/
S: equation (2), based on Cappuyns and Swennen (2008), and
equation (3), described as a two-site rst-order leaching model
according to Kim and Hyun (2015). In the comparison, two L/S data
sets (10e50 and 10e500 L kg1) were tted separately.
1000 CPPI =PPI 10; (1)
Cx k lnx a; (2)
Cx CT 1  f1  expk1 x  f2  exp  k2 x; (3)
The mean As concentrations (the ratio of cumulative As mass to
cumulative leachate volume) during the SLT and RSSCT were
plotted as a function of L/S ratio (Fig. 1). In most cases, the As
concentration dropped sharply at the beginning of the test and then
slowly converged to a stable value; however, As concentrations in
the SLT leachates generated from samples subjected to the 40D, AD,
and ND treatments (Fig. 1 (a)) increased at rst and then gradually
decreased. The cumulative As releases are shown in Table 1. The
percentages of cumulative leached As in the SLT were 1.4 times
higher on average than those of the RSSCT. In addition, compared
with the rock with ND, drying treatments increased the As leaching
and freeze-drying resulted in the largest increase.
For both SLT and RSSCT, the As releases under two L/S ranges
(10e50 and 10e500 L kg1) tted well to equations (2) and (3),
with correlation coefcient (R2) values ranging from 0.935 to 0.999
(Table 2). As shown in Table 2, the PPIs calculated based on equa-
tions (2) and (3) with L/S from 10 to 500 were generally in agree-
ment with the values measured in our experiments, especially for

where x is the L/S ratio (L kg1); Cx is the concentration of As

released at L/S of x (mg kg1); k and a are constants; CT is the total (a) 100
As concentration in the rock (mg kg1); f1 and f2 are the rapid and
40 D AD FD ND
Mean As concentration (g L-1)

slow leaching fractions, respectively, (the sum of f1 and f2 is 1); k1 80

and k2 are the corresponding leaching rate constants. The approx-
imate PPI in equation (1) was solved using the Goal seek function 60 SLT
and equations (2) and (3) were solved using Curve tting and Solver
in Microsoft Excel (2007), respectively.
40

2.4. Sequential extraction procedure 20

The fractionations of As in the rock before and after water

0
extraction (for both SLT and RSSCT) were investigated by a ve-step 0 150 300 450 600 750
sequential extraction procedure (SEP) based on the method L/S (L kg-1)
described by Wenzel et al. (2001). Non-specically sorbed As (F1), (b) 140
specically sorbed As (F2), amorphous oxide-associated As (F3),
120 40 D AD FD ND
Mean As concentration (g L-1)

crystalline oxide-associated As (F4), and residual As were sequen-

tially extracted. The detailed conditions are provided in the Sup- 100
plementary Material.
80
RSSCT
3. Results 60

3.1. Batch leaching experiments with variation of contact time 40

20
Fig. S1 shows the pH and released concentrations of As, Fe, Al,
and DOC in the leachates after different shaking times. All the 0
leachate pH values were alkaline, regardless of the drying method 0 200 400 600 800 1000
and contact time. Irrespective of drying method, the trend of As L/S (L kg-1)
concentrations was consistent: either reaching its highest value or
stabilizing after 6 h. This indicated that 6 h was an appropriate time Fig. 1. Mean As concentrations (ratio of cumulative As mass to cumulative leachate
volume) as a function of L/S ratio during (a) sequential leaching tests (SLT) and (b)
after which to proceed to the next sequential leaching test. rapid small-scale column tests (RSSCT). 40D: oven-drying at 40  C; AD: air-drying at
Compared with that of wet rock without water evaporation, the room temperature; FD: freeze-drying at 50  C; ND: no drying. Experiments used 3 g
dryingerewetting process generally promoted short-term As dried samples (4.44 g for sample with ND).
 J. Li et al. / Chemosphere 154 (2016) 276e282 279

Table 1
Cumulative releases of As in the SLT and RSSCT.
d
Released As Residual As Accountability (%)

mg a % b
mg c
SLT 40D 9.40 35.6 15.3 93.5
AD 9.10 34.4 16.6 97.2
FD 10.9 41.3 13.2 91.2
ND 8.28 31.3 e e
Average 9.42 35.6 15.0 94.0
RSSCT 40D 6.44 24.4 18.0 92.6
AD 6.39 24.2 16.5 86.7
FD 8.35 31.6 16.1 92.4
ND 6.11 23.1 e e
Average 6.82 25.8 16.9 90.6
a
Cumulative mass of As released from 3 g sample (dry weight basis; 4.44 g for sample with ND).
b
Calculated by 100  (cumulative mass of As released from sample/total mass of As in sample).
c
Residual mass of As in the dried residual material.
d
Calculated by 100  [(cumulative mass of released As residual mass of As)/total mass of As]. SLT: sequential leaching tests; RSSCT: rapid small-scale column tests; 40D:
oven-drying at 40  C; AD: air-drying at room temperature; FD: freeze-drying at 50  C; ND: no drying; : not measured.

those of the SLT. When a L/S from 10 to 50 was used, however,
inconsistency existed between the measured PPIs and those
calculated from equation (3); PPIs calculated from equation (2) in
SLT agreed well with the measured PPIs (Table 2).
3.3. Arsenic fractionations
As shown in Table 3, before water extraction, arsenic was pre-
sent mainly in the residual fractions (F5), followed by the specif-
ically sorbed fractions (F2) and the amorphous oxide-associated
fractions (F3), with the other fractions present in minor amounts
(<4.5%). After water extraction, arsenic also mostly existed in the
residual fractions (F5), but in decreased amount; the amounts of
the amorphous oxide-associated fractions (F3), specically sorbed
fractions (F2), and non-specically sorbed fractions (F1) also
decreased, whereas the crystalline oxide-associated fractions (F4)
increased to a certain extent.
4. Discussion
4.1. Comparison of sequential leaching and rapid-small-scale
column tests
Releases of As (L/S from 10 to 150) during the SLTs compared
with those from the RSSCTs are plotted in Fig. 2. Plots below the
diagonal line indicate higher release recorded by the RSSCT than by
the SLT. At an L/S ratio of 10, As release was higher in the RSSCT than
in the SLT, which indicated that As release was underestimated by
the batch test compared with the column test. On the contrary,
when the L/S ratios exceeded 20, the As concentrations from the
SLT were generally higher than those from the RSSCT, resulting in
higher PPI values and greater amounts of total leached As in the SLT.
Fig. 2 also compares the Fe, Al, and DOC concentrations in the
leachates generated by the SLT and RSSCT. The trend of DOC release
was similar to that of As, with higher DOC release in the RSSCT at an
L/S of 10 and then generally higher DOC release in SLT when the L/S
exceeded 10. Such correlations were not observed with the Fe and
Al concentrations: these elements were hardly detected in the
RSSCT leachates. Along with the results in Fig. S1, this trend reveals
that As mobility appears to differ from that of Fe and Al colloids.
As release may crucially depend on the dynamics of the mass-
transfer processes, and equilibrium exists when the mass-transfer
rates between solid and water are equal. At an L/S ratio of 10 in
the RSSCT, the release of As was the highest (Fig. 1 (b)). Equilibria
commonly occur near the beginning of the test because concen-
tration gradients between the solid and aqueous phases at this time
are extremely steep, resulting in high mass-transfer rates. In a dy-
namic column test, water is continuously replaced, which main-
tains the driving force for leaching (Cappuyns and Swennen, 2008);
however, the equilibria are postponed (L/S 20) after the 40D, AD,
and ND treatments in the SLT (Fig. 1 (a)). The equilibria can be
inuenced by the L/S ratio; pH and redox conditions are also very
important (Grathwohl and Susset, 2009). Lower pH and higher Eh
values were obtained in the SLT, compared with those in the RSSCT
(Fig. S3). Although the variations were small, this was consistent
with the later-emerging equilibria under the SLT conditions.
Moreover, agitation of solids in the SLT could mobilize ne particles
created by particle fracturing. This process may promote the release
of elements from the solid materials (Krger et al., 2012); a greater
number of ne particles may also increase contaminant re-

Table 2
Parameters for the tted cumulative release of As and determination of pollution potential indices.

Cx k lnx a; Cx CT 1  f1  expk1 x  f2  exp  k2 x; PPIM

L/S (10e50 L kg1) L/S (10e500 L kg1) L/S (10e50 L kg1) L/S (10e500 L kg1)

k a R2 PPIC k a R2 PPIC f1 k1 k2 R2 PPIC f1 k1 k2 R2 PPIC

SLT 40 D 0.74 1.2 0.9991 297 0.65 0.86 0.9860 278 0.25 0.028 5.6E-07 0.9942 222 0.27 0.021 2.4E-04 0.9932 279 280e290
AD 0.70 1.2 0.9973 272 0.65 1.0 0.9895 264 0.26 0.023 1.0E-14 0.9938 225 0.26 0.019 2.4E-04 0.9949 266 260e270
FD 0.74 0.77 0.9987 358 0.66 0.41 0.9837 342 0.19 0.069 1.5E-03 0.9992 589 0.31 0.028 3.1E-04 0.9841 336 340e350
ND 0.63 1.3 0.9830 208 0.65 1.2 0.9877 228 0.11 0.013 2.2E-03 0.9944 716 0.24 0.015 1.8E-04 0.9976 236 230e240
RSSCT 40 D 0.30 0.067 0.9996 157 0.48 0.53 0.9801 200 0.093 0.17 1.1E-03 0.9989 304 0.17 0.036 3.1E-04 0.9610 192 183e200
AD 0.26 0.095 0.9999 136 0.53 0.87 0.9557 189 0.087 0.16 8.7E-04 0.9992 211 0.14 0.039 4.0E-04 0.9598 178 167e183
FD 0.37 0.46 0.9997 250 0.46 0.21 0.9885 279 0.16 0.20 1.5E-03 0.9992 544 0.25 0.054 3.1E-04 0.9610 271 283e300
ND 0.31 0.30 0.9999 120 0.43 0.68 0.9935 162 0.074 0.081 7.0E-04 0.9999 143 0.14 0.027 2.3E-04 0.9352 142 140e150

PPIC: Calculated PPI; PPIM: Measured PPI.

280 J. Li et al. / Chemosphere 154 (2016) 276e282

Table 3
Fractionations of As before and after water extraction.

Fractions a, mg kg1 (%) b

F1 F2 F3 F4 F5

Before extraction 40D 0.213 (2.41) 2.12 (24.0) 1.17 (13.3) 0.326 (3.70) 4.98 (56.6)
AD 0.228 (2.59) 1.89 (21.4) 1.30 (14.8) 0.395 (4.48) 5.00 (56.8)
FD 0.224 (2.54) 1.89 (21.5) 1.12 (12.7) 0.310 (3.52) 5.27 (59.8)
Average 0.222 0.008 (2.52 0.090) 1.96 0.132 (22.3 1.50) 1.20 0.095 (13.6 1.08) 0.344 0.045 (3.90 0.512) 5.08 0.159 (57.7 1.81)
After SLT 40D 0.000 (0.000) 0.383 (6.62) 0.967 (16.7) 0.555 (9.60) 3.88 (67.1)
AD 0.000 (0.000) 0.427 (6.63) 1.33 (20.7) 0.903 (14.0) 3.77 (58.6)
FD 0.000 (0.000) 0.326 (6.80) 0.865 (18.0) 0.501 (10.4) 3.11 (64.8)
Average 0.000 0.000 (0.000 0.000) 0.379 0.050 (6.69 0.099) 1.06 0.247 (18.5 2.04) 0.653 0.218 (11.4 2.35) 3.59 0.416 (63.5 4.36)
After RSSCT 40D 0.017 (0.27) 0.571 (9.05) 0.875 (13.9) 0.378 (5.98) 4.47 (70.8)
AD 0.011 (0.18) 0.604 (10.0) 0.964 (16.0) 0.473 (7.84) 3.98 (66.0)
FD 0.008 (0.15) 0.443 (8.04) 0.796 (14.5) 0.377 (6.84) 3.88 (70.5)
Average 0.012 0.005 (0.198 0.064) 0.539 0.085 (9.04 0.992) 0.878 0.084 (14.8 1.09) 0.409 0.055 (6.89 0.931) 0.222 0.008 (69.1 2.72)
a
F1: non-specically sorbed As; F2: specically sorbed As; F3: amorphous oxide-associated As; F4: crystalline oxide-associated As; F5: residual As.
b
Values in parentheses: percentage of each fraction (%).

(a) (b) 20
40 D AD FD ND 40 D AD FD ND
100

DOC concentration in SLT (mg L-1)

As concentration in SLT (g L-1)

16

12

10
L/S = 10 8

4
L/S
/S = 10

1 0
1 10 100 0 4 8 12 16 20
As concentration in RSSCT (g L-1) DOC concentration in RSSCT (mg L-1)
(c) (d) 8
4
40 D AD FD ND
40 D AD FD ND
Fe concentration in SLT (mg L-1)

Al concentration in SLT (mg L-1)

2 4

0 0
0 2 4 0 2 4 6 8
Fe concentration in RSSCT (mg L-1) Al concentration in RSSCT (mg L-1)

Fig. 2. Comparison of (a) As (mg L1), (b) DOC (mg L1), (c) Fe (mg L1), and (d) Al (mg L1) in leachates (sample numbers 1e15 with cumulative L/S from 10 to 150) produced in SLT
versus RSSCT.

adsorption because of the increased surface area (Maszkowska leachates were also lower than those of the water extraction
et al., 2013). This re-adsorption probably decreased the As con- leachates (Table S2). This may account for the lower release of As in
centration in the SLT (L/S 10), but the effect may be reversible and F1 extraction because of greater adsorption of As onto clay minerals
adsorbed As would be released again during the later shaking or precipitates (Tabelin et al., 2014a). The Fe and Al concentrations
experiments. in the F2 extraction leachates were also very low (Table S2), which
means that re-adsorption of As probably occurs during this step;
4.2. Potential for As leaching however, it is reported that phosphate and arsenate show similar
environmental behaviors (Smedley and Kinniburgh, 2002). Given
The results revealed that water extraction at an L/S ratio of 10 the fact that phosphate is able to extract not only the easily
released more As than the non-specically sorbed As obtained by adsorbed (outer-sphere complexed) As but also strongly adsorbed
the SEP (Table S2). The Fe and Al concentrations in the leachates of (inner-sphere) As (Cheng et al., 2009), the presence of phosphate
F1 extraction were much lower than those of water extraction potentially competes with arsenate for adsorption sites, leading to
(Table S2), probably because more Fe-/Al-oxyhydroxide precipitate greater As release. This indicates that the use of 0.05 M (NH4)2SO4
was formed during F1 extraction. The pH values of the F1 extraction as the leaching medium in the SEP may result in underestimation of
 J. Li et al. / Chemosphere 154 (2016) 276e282
the readily soluble fraction. After the SLT and RSSCT were
completed, it was found that water extraction could remove almost
all of the non-specically sorbed As and most of the specically
sorbed As (Table 3). These two fractions are suggested as the pri-
mary sources of As release. Furthermore, removing labile species
could disturb the chemical equilibria among different species,
resulting in transformation between different fractions (Wen et al.,
2013). A previous study conrmed that less-crystalline iron oxides
may undergo phase transformations into more crystalline phases
(Cornell and Schwertmann, 2003), which results in the incorpora-
tion of arsenic into the structure of the crystalline product
(Pedersen et al., 2006). This may explain the increase of the crys-
talline oxide-associated As. The total water-extractable As in the
SLT after freeze-drying (41.3%) was slightly higher than the sum of
the rst four fractions in SEP (40.2%), demonstrating that long-term
water extraction can dissolve all or part of the ve As fractions.
It has been reported that As release is controlled by the disso-
lution of Fe or Al oxides (Xu et al., 2011). The relationships between
the mean As and Fe or Al concentrations in the SLT are shown in
Fig. S4. Interestingly, Fe or Al release was delayed compared with As
release at the beginning, which is corroborated by the results in
Fig. S1. This is probably because some dissolved Fe and Al colloids
precipitated at rst and were then re-released to the leachates in
later steps. Correlation plots between As and Fe or Al (Fig. S5)
suggest that the Fe or Al oxides could provide a mechanism for As
leaching. Taking the SEP results into account, it is inferred that As
was rst mainly released from the mineral surfaces, as previously
reported (Wenzel et al., 2001), and then the dissolution of Fe or Al
oxides contributed to the concomitant release of As. DOC plays an
important role in controlling As mobility and the complexation of
As by DOC may increase its leaching from soils (Luo et al., 2008). A
good correlation between the mean As and DOC concentrations in
the RSSCT (Fig. S6) indicates that DOC also controls the As leaching
from this rock.
4.3. Inuence of drying methods on As leaching
Compared with that of wet rock, the higher release of As after
drying (Fig. 1 and Table 1) was in accord with higher release of Fe,
Al, and DOC (Fig. S1). Drying may generate considerable negative
pore water pressures between soil particles and therefore result in
greater generation of colloids (Majdalani et al., 2008; Mohanty
et al., 2015)dthe same effect observed for the rock used in this
study. Drying treatments can also increase DOC concentrations in
soil extractions (Kaiser et al., 2001; Merckx et al., 2001), which is
consistent with our results; however, a larger amount of As was
released after FD treatment, despite smaller Fe, Al, and DOC re-
leases compared with AD and 40D treatments (Fig. S1). Freezing
causes expansion of water to ice in the rock pores, which are similar
to pores in soils; this expansion may break aggregates and form
colloids (Oztas and Fayetorbay, 2003). Moreover, as the ice in the
rock pores sublimates, water movement from nearby pores towards
the freezing fronts lead to new fractures and increases the number
of active fracture sites (Mohanty et al., 2014). The water-extractable
As is mainly associated with surfaces of solid phases, which may
explain the higher As release under these conditions.
The above results demonstrate that the different drying
methods potentially lead to under- or overestimation of As leaching
from an excavated rock. For example, use of fresh samples with no
pretreatment has been previously suggested for determining As
extraction from soils (Sz akova  et al., 2009); however, the As
leaching results from the excavated rock with no pretreatment in
this study resulted in underestimation. Moreover, the As contam-
ination assessment of this rock with respect to pollution level was
easily overestimated if freeze-drying was used, compared with
281
values determined using the other two drying methods.
4.4. Possible application of pollution potential indices in the
disposal of excavated rocks
The leaching of As from excavated rocks can pose a risk to the
environment (Tabelin et al., 2014b). More efcient and safe ways of
managing hazardous excavated rocks are needed. Tatsuhara et al.
(2012) suggested a combined neutralizationeadsorption system
for the disposal of hydrothermally altered excavated rock, which
mainly uses an adsorption layer at the base to immobilize leached
As; however, this approach requires identication of suitable
adsorbent dosages based not only on the adsorption capacity of the
adsorbent, but also on the potential for As leaching. Tabelin et al.
(2013) employed column tests to predict the potential for As
leaching from excavated rocks. Based on this study, the PPI ob-
tained from an SLT may be used to estimate the potential for As
leaching. We consider this method more practical, economical, and
conservative compared with a column test; however, its feasibility
and range of application warrant future investigation.
5. Conclusions
This study investigated the potential for leaching of As from an
excavated rock into water using SLT and RSSCT. The As leaching (L/
S 10) was higher in RSSCT than SLT at the beginning, while the
amount of As leaching in SLT prevailed over that in RSSCT in the
later steps, resulting in higher cumulative As release in the SLT
(average: 35.6%) than in the RSSCT (average: 25.8%). This study also
showed that drying treatments (air-drying, oven-drying, and
freeze-drying) lead to higher As leaching compared with that of
fresh rock; freeze-drying increased As leaching to the greatest
extent. These results underscore the importance of drying treat-
ment selection during the contamination assessment. This study
proposes the concept of PPI to evaluate the pollution threat of As
leaching from excavated rock.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.chemosphere.2016.03.129.
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