Geoderma 275 (2016) 74–81

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Geoderma

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Release of Pb in soils washed with various extractants

Chunle Chen, Tian Tian, Ming Kuang Wang, Guo Wang ⁎
College of Resource and Environment, Fujian Provincial Key Laboratory of Soil Environmental Health and Regulation, Fujian Agriculture and Forestry University, Fuzhou, Fujian 350002, China

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

Article history: The suitability of an agent for washing heavy metal contaminated soils depends not only on the efficiency of
Received 18 February 2016 heavy metal removal but also on the persistence of the washing effect, especially for agricultural soil. Redistribu-
Received in revised form 12 April 2016 tion of residual heavy metals in washed soil from inert pools to labile pools can reverse the initial washing effect.
Accepted 19 April 2016
In order to study the redistribution of residual Pb in Pb-contaminated soils washed with citric acid (CA), ethyl-
Available online 4 May 2016
enediaminetetraacetic acid (EDTA), FeCl3, and HCl solutions, washed soils were incubated under both flood
Keywords:
and 70% field water capacity (FWC) conditions for 180 days. The Pb availability in CA-, EDTA-, FeCl3-, and HCl-
Soil washing washed soils varied with incubation time. Diethylenetriaminepentaacetic acid (DTPA)-Pb generally increased
Pb-contaminated soil with incubation time, except in CA-washed soil under flood incubation condition. Pb associated with the ex-
Availability changeable/acid extractable fraction (F1) increased, whereas Pb in the easily reducible fraction (F2) decreased
Mobility over time, for all washed soils under flood incubation condition; the changes in the amount of Pb associated
Redistribution with each fraction were much smaller under 70% FWC incubation. The transformation of Pb from F2 to F1 during
flood incubation was largely caused by the mobilization of Fe and Mn oxides. The mobility factors (MF) of Pb for
samples under flood incubation increased with increasing incubation time while those for samples under 70%
FWC incubation changed only slightly, which implies increasing environmental risks of Pb from washed soils
that are flooded. Therefore, the redistribution and potential environmental risks posed by heavy metals in
washed soils, especially in paddy rice soils, should be taken into account when the suitability of a washing
agent is evaluated. In the present study, CA was found to be unsuitable for washing Pb-contaminated agricultural
soil, whereas the FeCl3 solution was the most stable washing agent tested, as it had high removal efficiency and
low release of Pb after washing.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Soil contaminated with Pb, due to activities such as mining and
industrialization, has gained much attention (Arunakumara et al.,
2013; Fang et al., 2014; Li et al., 2014). Pb in soils can enter into livestock
and humans through the food chain (Dong et al., 2011; Nabulo et al.,
2010). Excessive intake of Pb can be damaging to human health
(e.g., affecting nervous, skeletal, and enzymatic systems; Zhang et al.,
2012). Pb affects intelligence and skeletal development of children,
and children younger than 6 years are more sensitive to Pb than older
children (Qin et al., 2010). Therefore, soils contaminated by Pb must
be remediated immediately.
Soil washing can be used to permanently remove toxic metals from
soils (Dermont et al., 2008). Soil washing can remove most of the toxic
Abbreviations: CA, citric acid; DDW, double distilled water; Eh, soil redox potential; F1,
exchangeable and acid extractable fraction; F2, easily reducible fraction; F3, oxidizable
fraction; F4, residual fraction; FWC, field water capacity; P1, 7 days of soil incubation;
P2, 15 days of soil incubation; P3, 30 days of soil incubation; P4, 60 days of soil
incubation; P5, 90 days of soil incubation; P6, 120 days of soil incubation; P7, 150 days
of soil incubation; P8, 180 days of soil incubation.
⁎ Corresponding author.
E-mail address: 1400619353@qq.com (G. Wang).
metals associated with labile fractions and can slightly affect metal
pools in non-labile fractions (Hernandez-Soriano et al., 2011; Wuana
et al., 2010; Ye et al., 2014). It is well known that toxic metals associated
with labile fractions are much more toxic, mobile, and bioavailable to
livestock than metals associated with non-labile fractions (Zhang
et al., 2010). On the other hand, most studies have focused on the re-
moval efficiency and redistribution of heavy metals after washing
(Ash et al., 2015; Finzgar et al., 2014); therefore, the fate of the residual
fraction is still unclear. Re-establishing the equilibrium that is disturbed
during soil washing could initiate the transformation of non-labile
fractions to labile fractions (Udovic and Lestan, 2009). Although it is ob-
vious that residual heavy metals after soil washing may be toxic to the
surrounding environment if they are transformed into mobile and bio-
available fractions, the extent to which this occurs is still not well
known. The transformation of residual heavy metals should be affected
by various abiotic and biotic soil factors (Udovic et al., 2007). Soil pH,
soil redox potential (Eh), and organic matter affect the characteristics
of heavy metals by altering their fractionation, mobility, and metal-
complexes (Kim and Owens, 2009); these alterations may pose ecolog-
ical risks to the surrounding environment. Changes in environmental
conditions could cause heavy metals in less mobile fractions to redis-
tribute to labile fractions (Bourg and Loch, 1995; Jean et al., 2007). It is

http://dx.doi.org/10.1016/j.geoderma.2016.04.015
0016-7061/© 2016 Elsevier B.V. All rights reserved.
 C. Chen et al. / Geoderma 275 (2016) 74–81
important to understand whether residual heavy metals in washed soils
are immobile, stable, or would become mobile if conditions were to
change. Because the ultimate goal of soil washing is re-introducing the
washed soils for agricultural production, the stability of residual heavy
metals in washed soils determine the success (immobile and stable)
or failure (mobile) of a soil washing process.
The objective of this study was to assess the long-term transforma-
tion of Pb in soils washed with various extractants under flood and
70% field water capacity incubation conditions and to evaluate the util-
ity of each soil washing process from the perspective of Pb release for
Pb-contaminated agricultural soils.
2. Materials and methods
2.1. Study area and soil
The study area closes to a former smelter in the town of Meixian,
Youxi County, Fujian Province, China (latitude: 26°15′6″N, longitude:
118°15′20″E; elevation is about 90 m above sea level). It belongs to
the subtropical maritime monsoon climate with annual average tem-
perature and rainfall of 19.6 °C and 1600–1700 mm, respectively. The
mining activity in this area began N30 years ago. The contaminated
soil used in this study was collected from the Ap horizon (0–20 cm) of
an agricultural field, in which rice and vegetables used to be rotationally
cultivated. The soil was classified as sandy loam, mixed, thermic, Typic
Endoaquepts (Soil Survey Staff, 2014). Soil was transported back to
the laboratory to air-dried, ground and passed through 10-mm and
then 2-mm laboratory test sieves, and homogenized. Soil passed
through a 10-mm sieve was used for soil washing and the soil passed
through a 2-mm sieve was used for soil physical and chemical analysis.
Total Pb of this studied soil was 1550.2 mg kg−1.
Soil pH was measured using a pH meter with a complex glass elec-
trode (pHS–3E, Shanghai Precision & Scientific Instrument Co., Ltd,
China) at a soil-to-water ratio of 1:2.5. The cation-exchange capacity
(CEC) was determined by the ammonium acetate (1 mol L−1 NH4OAc,
pH = 7.0) method, and particle size was determined by the sedimenta-
tion method (SSSC, 1999). The organic matter content was determined
by wet oxidation with H2SO4\\K2Cr2O7 (SSSC, 1999). The soil was
digested with HNO3\\HCl\\HClO4\\HF to determine the total Pb con-
centration. Pb concentration in the digested solution was determined
using inductively coupled plasma-mass spectrometry (ICP-Mass,
Nexion 300, Perkin Elmer, NY). A soil sample with a certified concentra-
tion of Pb (GBW07407), provided by the China National Center for
Standard Materials, was used as a reference. The recoveries of Pb from
the reference soils were 95–108%. Soil field water capacity (FWC) was
determined by the laboratory Wilcox method (see Supplementary
method) (Zhu, 1996). Physicochemical characteristics of the contami-
nated soil are shown in Table 1.
2.2. Soil washing
Five hundred grams of air-dried soil was placed in a 2000 mL plastic
bottle and mixed with a 0.1 mol L−1 solution of one of four reagents
(citric acid, Na2EDTA, HCl, or FeCl3) at a soil-solution ratio of 1:2. The
Table 1
Chemical and physical properties of the contaminated soil.
Soil pH OMa CECb (cmol Clay Silt Sand Texture
sample (g kg−1) (+) kg−1)
(%)
MX 6.4 23.5 9.0 12.1 15.1 72.8 SLc
a
Organic matter.
b
Cation-exchange capacity.
c
Sandy loam.
75
bottle was shaken on a back-and-forth shaker (HY-8, Changzhou,
China) for 2 h at 25 ± 2 °C (210 rpm). After shaking, the supernatant
was drained off. This washing process was repeated twice, as previous
studies have indicated that this optimizes washing numbers for Pb
removal (Chen et al., 2015). The washed soil was then rewashed with
double distilled water (DDW) to remove the mobilized metals and
was air-dried. In order to obtain enough washed soil for further use,
washing process with one of the extractant as described above was
repeated for thirty times. The washed soils of the same extractant
were mixed together for incubation. The Pb concentrations in the wash-
ing solutions are presented in Table S1. Washing with citric acid (CA),
EDTA, FeCl3 and HCl removed 9.0, 39.5, 29.7 and 18.6% of total soil Pb,
respectively.
2.3. Incubation
Samples (200 g) of air-dried washed or untreated soils were placed
into individual 250-mL bottles. To stimulate paddy field and dry land
environments, the soil samples were subjected to flood (about 1 cm
water above the soil surface) or to 70% FWC conditions with DDW. To-
tally, there were twenty-four treatments for each washed and untreated
soil under either flood or 70% FWC incubation. Samples were covered
with cling film to decrease water evaporation, and incubated at 25 ±
2 °C. During the incubation period (180 days), DDW was regularly
replenished to the soils to maintain flood or 70% FWC conditions. Soils
were sampled after 7, 15, 30, 60, 90, 120, 150 and 180 days of incuba-
tion, which correspond to period 1 (P1), period 2 (P2), period 3 (P3),
period 4 (P4), period 5 (P5), period 6 (P6), period 7 (P7), and period 8
(P8), respectively. At each sampling time, the soils in three bottles of
each kind of washed soil were taken, air-dried and passed through
2 mm sieve for further analysis. The pH and Eh of the soil solutions
were measured at each sampling time using an automatic ORP depolar-
ization tester (FJA-6, Nanjing, China).
2.4. Determination of available soil Pb
The available Pb in each soil sample was extracted with a
diethylenetriaminepentaacetic acid (DTPA) solution. The extraction
solution contained 0.005 mol L−1 DTPA, 0.01 mol L−1 CaCl2, and
0.1 mol L−1 triethanolamine (TEA) and was adjusted to pH 7.30 ± 0.05.
In a 100 mL polyethylene centrifugation tube, 5.00 g of soil was shaken
with 10 mL of the DTPA extraction solution for 2 h on a horizontal shaker
at approximately 180 rpm. After shaking, samples were centrifuged for
15 min at 3000 rpm (DT5–2, Beijing, China) and filtered through a
0.45 μm Millipore filter. The Pb concentration in the filtrate was deter-
mined using ICP-Mass. Extractions were conducted in triplicate.
2.5. BCR sequential extraction
A three-stage modified BCR sequential extraction procedure (Rauret
et al., 2000) was used to determine the fractionation of Pb, Mn, and Fe in
the soils after incubation for 7, 90, and 180 days. Four operationally
defined fractions were sequentially determined: exchangeable and
acid extractable fraction (F1), easily reducible fraction (F2), oxidizable
fraction (F3), and residual fraction (F4). All data reported were means
of triplicate analyses. A soil sample with certified concentrations of Pb
(GBW080037) was provided by the China National Center for Standard
Materials and was used as a reference. The recoveries of Pb from the ref-
erence soil were 88.3 to 105.6%. Pb in untreated soil was mostly bound-
ed to F2 and F4 (66.8 and 21.8% of total Pb, respectively), with very little
Total Pb
Pb in F1 and F3 (Chen et al., 2015).
(mg kg−1)
1550.2 2.6. Lead mobility in soils
The mobility factor developed by Gusiatin and Klimiuk (2012) was
used to describe the mobility of Pb in incubated soil samples. The Pb
76 C. Chen et al. / Geoderma 275 (2016) 74–81
mobility factor (expressed as MF) was calculated as the proportion of
the Pb contained in all fractions that was recovered from the F1 fraction:
F1
MF ¼ 100%:
F1 þ F2 þ F3 þ F4
2.7. Statistical analysis
The data presented are the mean values of three replicates (n = 3).
Statistical analysis was conducted using SPSS version 16.0 (SPSS Inc.,
Chicago, USA). Mean values were compared by one-way analysis of
variance and Duncan's multiple range test at the 5% level.
3. Results
3.1. Soil Eh and pH
Eh of all soils (untreated soil and soils washed with CA, EDTA, HCl, or
FeCl3) decreased during incubation under both flood and 70% FWC
conditions (Fig. 1 and Table S2). The Eh of soils under flood condition
changed significantly more than those under 70% FWC conditions,
decreasing significantly from 0 days to about 15 days of incubation
(P b 0.05) and remaining relatively stable thereafter (Fig. 1 and
Table S2). After 15 days of incubation, all flood incubation resulted in
Eh values lower than 0 mV (Fig. 1a), whereas the Eh values of soils
Fig. 1. Effect of flood (a, b) and 70% field water capacity (c, d) on soil solution Eh and pH.
under 70% FWC incubation remained N0 mV over the entire 180 days
of incubation (Fig. 1c). Based on the soil redox condition classifications
described by Liu (1985), the redox conditions in untreated, CA- and
HCl-washed soils were strongly reducing (Eh b 100 mV), and the
conditions in EDTA- and FeCl3-washed soils were moderately reducing
(Eh ranged from 200 to − 100 mV) after 15 days of flood incubation.
Under 70% FWC incubation, the soil redox conditions in untreated
and CA-washed soils were weakly reducing (Eh ranged from 400 to
200 mV), and the conditions in EDTA-, FeCl3-, and HCl-washed soils
were moderately reducing after 15 days of incubation.
The pH values of untreated and CA-, EDTA-, FeCl3-, and HCl-washed
soils under flood conditions ranged from 6.14 to 6.67, 4.48 to 6.94, 7.06
to 8.29, 2.84 to 3.62, and 3.48 to 4.48, respectively (Fig. 1b and Table S3).
Washing with HCl, and FeCl3 significantly lowered the soil pH, whereas
washing with EDTA significantly increased pH (Fig. 1b). The pH of un-
treated soil did not vary significantly during incubation. However, the
pH of all washed soils increased during incubation, with that of the
CA-washed soil increasing significantly from 4.6 to 6.8 (P b 0.05). Soil
pHs with incubation under 70% FWC condition changed less than that
of soils incubated under flood condition (Fig. 1d). The pH of FeCl3- and
HCl-washed soils remained almost unchanged during incubation. The
pH of CA-washed soil significantly increased during incubation
(P b 0.05), although the increase under 70% FWC condition was smaller
than that under flood condition (Fig. 1b & d). The pH of soil washed with
HCl, FeCl3, or EDTA did not recover to the level of original soil under
either water condition during 180 days incubation. However, the pH
 C. Chen et al. / Geoderma 275 (2016) 74–81
of the CA-washed soil increased significantly during the first 15 days of
incubation (P b 0.05), indicating that the lowered pH in CA-washed soil
can recover quickly to similar level with the original soil.
3.2. Release of residual Pb in washed soils as a function of incubation time
Available (DTPA-extractable) Pb in soils at different sampling times
was used to measure the release of Pb in the washed soils with various
extractants (Fig. 2 and Table S4). Although the quantity of DTPA-
extractable Pb occasionally decreased, it generally increased with incu-
bation time for all treatments (except for CA-washed soil under flood
incubation; Fig. 2a). After 180 days of incubation (P8) under flood and
70% FWC conditions, the DTPA-extractable Pb increased in comparison
to the washed soils in P1 by 171.5 and 159.4% (EDTA-washed soil),
214.0 and 189.9% (FeCl3-washed soil), and 88.60 and 71.0% (HCl-
washed soil). DTPA-extractable Pb of CA-washed soil under 70% FWC
incubation increased similarly over time and showed large increases
by up to 86.7% from P5 to P8 (Fig. 2b). However, DTPA-extractable Pb
in CA-washed soil under flood incubation significantly decreased by
31.2% from P1 to P2 (P b 0.05) and showed positive and negative fluctu-
ations thereafter; it was, however, always less than DTPA-extractable Pb
at P1 (Fig. 2a).
Although DTPA-extractable Pb in washed soils increased with incu-
bation time, DTPA-extractable Pb in EDTA-, FeCl3-, and HCl-washed
soils was lower than that of original soil (182.1 mg kg−1) during incuba-
tion. In contrast, the DTPA-extractable Pb of CA-washed soil was higher
than that of untreated soil at certain sampling times, especially under
70% FWC incubation (Fig. 2b). It is noteworthy that the DTPA-
extractable Pb in FeCl3-washed soil was generally within the regional
limit (DTPA-Pb ≤ 28.0 mg kg−1) proposed by the General Administration
of Quality and Quarantine of Fujian Province (GAQQF, 2008) after six
months of incubation; the only exceptions were for P7 (29.7 mg kg−1)
and P8 (28.2 mg kg−1), when the DTPA-extractable Pb in these soils
slightly exceeded the regional limit.
3.3. Redistribution of Pb as a function of incubation time
The chemical forms of Pb determined by sequential extraction at
three sampling times, P1, P5 and P8, are presented in Fig. 3. Under
flood conditions, the Pb concentrations associated with F1 increased
significantly (P b 0.05) during incubation, and at P8 were approximately
1.8, 2.6, 1.9 and 2.7 times those at P1 for CA-, EDTA-, FeCl3-, and
HCl-washed soils, respectively. This was consistent with the observed
increase in DTPA-extractable Pb with incubation time in all flooded
Fig. 2. Effect of flood (a) and 70% field water capacity (b) on DTPA-Pb dynamic changes as a function of incubation time. Results are presented as means of three replicates ±SD.
77
soils except for CA-washed soil. In contrast, Pb concentrations in F2 sig-
nificantly decreased in CA- and HCl-washed soils with incubation time
under flood condition (P b 0.05); however, there were no significant dif-
ferences between sampling times in Pb concentrations of F2 in EDTA-
and FeCl3-washed soils (P N 0.05). Pb concentrations in F3 decreased
more obviously over time than Pb concentrations in F2 (Fig. 3). These
results clearly demonstrated that Pb associated with F2 and F3 can
transform into Pb associated with F1 during incubation under flood
conditions.
Under 70% FWC incubation, Pb forms were much more stable than
under flood incubation. No significant changes in Pb fractionation
were observed in EDTA- and FeCl3-washed soils (P N 0.05). The Pb con-
centration of F1 in HCl-washed soil decreased significantly with
prolonged incubation time (P b 0.05). The Pb concentration of F2 in
HCl-washed soil increased during incubation, but these changes were
not statistically significant (P N 0.05). For all soils under 70% FWC incu-
bation, the Pb concentrations associated with F1 and F2 appeared to fol-
low opposite trends (Fig. 3). Pb concentrations associated with F3 in
washed soils always decreased significantly with incubation time
under flood conditions (P b 0.05; Fig. 3). Under 70% FWC incubation,
the Pb concentration of F3 in EDTA-washed soil significantly increased
with incubation time (P b 0.05), whereas the Pb concentration of soils
washed with other extractants did not change significantly over the
course of incubation. Only small changes were observed in Pb concen-
tration of F4 during incubation, indicating that water regime did not sig-
nificantly affect Pb bound to the residual fraction (Fig. 3).
3.4. Redistribution of Fe and Mn as a function of incubation time
As shown in Fig. 4, under flood incubation, Fe and Mn concentrations
of F1 increased greatly over time. At P8, the Fe concentrations of F1 were
about 4.95, 2.21, 7.32, and 13.62 times greater than concentrations at P1
for CA-, EDTA-, FeCl3-, and HCl-washed soils, respectively. Similarly, at
P8, the Mn concentrations of F1 were 1.17, 1.03, 1.33, and 1.26 times
those at P1 for CA-, EDTA-, FeCl3-, and HCl-washed soils, respectively
(Fig. 4a and c). In contrast, Fe concentrations of F2 from CA-, EDTA-,
FeCl3-, and HCl-washed soils were 1.32, 1.92, 1.26, and 1.87 times great-
er at P1 than at P8, respectively, and Mn concentrations were 1.19, 1.15,
1.66, and 1.08 times greater at P1 than P8, respectively (Fig. 4b and d).
Fe and Mn concentrations associated with F1 and F2 changed much
less during 70% FWC incubation than during flood incubation (Fig. 4),
which was primarily due to the relatively high and stable soil Eh
(N0 mV) during 70% FWC incubation.
78 C. Chen et al. / Geoderma 275 (2016) 74–81

Fig. 3. Fractionation of Pb in washed-soils under flood and 70% field water capacity incubation. Results are presented as means of three replicates ±SD. Different superscript letters (a, b, ab
and c) indicate statistically significant differences between incubation periods for a given extractant.

3.5. Mobility changes as a function of incubation time
The time-dependent changes in Pb mobility in washed soils under
flood and 70% FWC incubations are presented in Fig. 5. It was clear
that flood condition resulted in significant increases in mobility, as indi-
cated by the relatively large MF for all treatments under flood condition
(P b 0.05). At P8, MF was 7.86%, 3.49%, 4.38%, and 10.08% larger than at
P1 for CA-, EDTA-, FeCl3-, and HCl-washed soils, respectively. Pb mobil-
ity was highest in CA-washed soil, followed by HCl-washed soil and
then FeCl3-washed soil. The Pb mobility in EDTA-washed soil was the
lowest (Fig. 5).
Generally, the Pb mobility of the washed soils under 70% FWC incu-
bation was much lower than those under flood incubation. Immobiliza-
tion phenomena occurred in EDTA- and HCl-washed soils; the MF values
for these soils significantly decreased over the course of incubation by
0.36 and 1.39%, respectively. MF values significantly increased over the
course of incubation by 1.46 and 1.40% for CA- and FeCl3-washed soils
(Fig. 5), respectively.
4. Discussion
It has been well recognized that soil pH and Eh plays an important
role on availability of heavy metals and moisture management could
significantly influence soil pH and Eh (Li and Xu, 2015; Zheng and
Zhang, 2011). Under flood condition, oxygen will be consumed by
microbial activity accompanying with H+ consumption, resulting in a
decrease in Eh and increase in pH in acid soils (Kashem and Singh,
2001). Therefore, flood incubation could lead to lower Eh for all soils
and higher pH in acid soils in this study compared to their counterpart
under 70% FWC incubation. Additionally, citric acid as a low molecular
organic acid can be easily biodegradable (Evangelou et al., 2006), there-
fore, soil solution pH in CA-washed soil in flood and 70% FWC incubation
could quickly increase.
In most cases, DTPA-extractable Pb increased with time under flood
condition, which is likely due to the mobilization of Fe and Mn oxides
with decreasing Eh. Fe and Mn were released from F2 to F1 under
flood incubation as a function of reductive dissolution (Hindersmann
and Mansfeldt, 2014; Iu et al., 1981; Schulz-Zunkel et al., 2015). Zheng
et al. (2011) reported that soil Fe and Mn oxides play important roles
in the redistribution of solid components of heavy metals. The mobiliza-
tion of Fe and Mn oxides results in the release of heavy metals that
are associated with Fe and Mn oxides (Kashem and Singh, 2001;
Mukwaturi and Lin, 2015). Additionally, the significant increase in Pb
associated with F1 that we observed was consistent with the observed
increase in DTPA-extractable Pb. This implies that the increase in
DTPA-extractable Pb during incubation was initiated by the transforma-
tion of Pb to a more labile fraction in washed soils due to Fe and Mn mo-
bilization. This phenomenon was also observed by Udovic and Lestan
(2009). The increase in DTPA-extractable Pb in CA-washed soil under
flood incubation did not coordinate with changes in F1 concentration
of Pb; the DTPA-extractable Pb in HCl-washed soil under 70% FWC
 C. Chen et al. / Geoderma 275 (2016) 74–81
Fig. 4. Fractionation of Fe in F1 (a) and F2 (b) and Mn in F1 (c) and F2 (d) in washed soils under flood and 70% field water capacity incubation. Results are presented as means of three
replicates ± SD. Different superscript letters (a, b, ab and c) indicate statistically significant differences between incubation periods for a given extractant.
Fig. 5. The changes in Pb mobility factor for washed soils as a function of flood and 70%
field water capacity incubation. Results are presented as means of three replicates ±SD.
Different superscript letters (a, b, and c) indicate statistically significant differences
between incubation periods for a given extractant.
79
incubation was also not coordinated with changes in fraction 1 of Pb.
This can be explained by the fact that DTPA extraction resulted in a
near-neutral pH. This pH was higher than that of the CA-washed soil
and enhanced the formation of heavy metal-hydroxides (Rieuwerts
et al., 1998). In addition, metals were transformed into non-leachable
fractions (i.e., by acetic acid solution) that could be extracted through
the formation of complexes with DTPA (Udovic and Lestan, 2012). The
decrease of DTPA-extractable Pb from P1 to P2 for CA-washed soil
under flood incubation can be attributed to a significant increase in
soil pH from P1 (pH = 5.6) to P2 (pH = 6.5; Naidu et al., 1994;
Paulose et al., 2007). However, in most cases of present study, an
increase in soil pH was not associated with a decrease in DTPA-
extractable Pb. This implies that pH was not the only factor influencing
Pb availability.
Pb release was limited under 70% FWC incubation as there was no
obvious dissolution of Fe and Mn from F2 to F1. The increase in DTPA-
extractable Pb during 70% FWC incubation was likely caused by re-
equilibration among various Pb fractions of the washed soil, resulting
in Pb transformation of non-labile fractions to labile fractions (Udovic
and Lestan, 2009), rather than by Pb release due to the mobilization of
Fe and Mn oxides. As no obvious Fe and Mn oxide mobilization from
F2 to F1 was observed under 70% FWC incubation, the transformation
of Pb from F2 to F1 was not significant and only slight changes in Pb re-
distribution between F1 and F2 were observed. Although the Pb concen-
trations of F3 were also affected by water regime, the relatively low
80 C. Chen et al. / Geoderma 275 (2016) 74–81
amount of Pb in F3 means that it can be ignored in the present study. F4
(the residual fraction) was the most inactive fraction because it was
bound with a crystalline lattice of soil minerals; therefore, water regime
had no effect on F4 (Zheng and Zhang, 2011).
Metal mobility, which determines the potential risks of the metals in
contaminated soils, depends on the forms in which the metals appear
(Gusiatin and Klimiuk, 2012). Under flood incubation, MF values of Pb
in washed soils increased significantly with incubation time, indicating
that Pb was dramatically mobilized. The increase in Pb mobility under
flood incubation was therefore primarily due to the transformation of
F2 to F1 via destabilization, and the increase in MF value over time
was consistent with the increase in F1concentration of Pb over time.
Pb mobility under 70% FWC incubation changed much less than that
under flood incubation. This was due to the relatively low transforma-
tion of Pb from F2 to F1 under 70% FWC conditions. As in flooded soils,
the MF values changed consistently with F1 Pb concentration in soils.
However, the Pb mobility under 70% FWC incubation varied among
different washed soils. Soil properties played important roles in Pb
mobility under 70% FWC incubation; various release mechanisms from
various washed soils resulted in diversity of Pb mobility (Zhang et al.,
2010).
Previous research has confirmed that soil flood condition can result
in decreased availability of some heavy metals in the soil (Li and Xu,
2015; Zhu et al., 2012). There are three main mechanisms for this:
1) flooding increases pH and decreases Eh in the soil, resulting in an
increase of negative charges on the solid surface and therefore greater
adsorption of metal ions (Kashem and Singh, 2001; Sun et al., 2007);
2) decreasing Eh causes more amorphous hydrous oxides to appear,
which favors the adsorption of metal ions (Shuman, 1976); and 3) re-
ducing sulfates to sulfides leads to the formation of metal sulfides
(Kashem and Singh, 2001). Our results demonstrated that the mean
value of DTPA-extractable Pb in CA-washed soils under flood incubation
conditions was much lower than that under 70% FWC incubation condi-
tion, whereas mean value of DTPA-extractable Pb in EDTA- and HCl-
washed soils under flood incubation were only slightly lower than
those under 70% FWC. This suggests that some of the Pb released from
soils was associated with negative charge, amorphous hydrous oxide,
or precipitated as Pb sulfide. However, these processes could not take
place in the low-pH environment created by FeCl3 washing (ranging
from 2.84 to 3.62).
Finally, although DTPA-extractable Pb in washed soils increased
with prolonged flood and 70% FWC incubation in most cases, DTPA-
extractable Pb in EDTA-, FeCl3-, and HCl-washed soils during incubation
was always lower than that of the original and untreated soil. DTPA-
extractable Pb in CA-washed soil was higher than that in untreated
soil. This can be attributed to the formation of Pb-CA complexes that
are re-adsorbed on the soil as described by Bajda (2011). We therefore
determined that CA was not a good washing agent for Pb-contaminated
soil. Of the four agents tested, FeCl3 solution seems to be the most stable
washing agent for Pb-contaminated soil because DTPA-extractable Pb in
FeCl3-washed soil was lower than, or close to the regional limit for agri-
cultural soil (≤28 mg kg−1; GAQQF, 2008) during 180 days of incuba-
tion. However, the suitability of a washing agent for washing heavy
metal contaminated agricultural soil should be fully evaluated based
on its ability to remove heavy metals from the soil, the redistribution
of heavy metals after washing, the damage to soil fertility caused by
washing, and the recovery of soil microorganisms after washing.
5. Conclusions
The Pb availability of CA-, EDTA-, FeCl3-, and HCl-washed soils varied
when the soils were incubated under flood and 70% FWC conditions for
180 days. DTPA-extractable Pb generally increased with incubation for
all washed soils, except CA-washed soil under flood incubation. DTPA-
extractable Pb of EDTA-, FeCl3-, and HCl-washed soils was always
lower than that of untreated soil during incubation. Pb associated with
F1 increased and Pb associated with F2 decreased with incubation
time in all washed soils under flood conditions. No significant transfor-
mation among the various fractions was observed for EDTA- and FeCl3-
washed soils under 70% FWC incubation. However, for HCl-washed soil,
Pb in F1 decreased and Pb in F2 increased with incubation time under
70% FWC condition. Under flood incubation, the transformation of Pb
from F2 to F1 can be primarily attributed to the mobilization of Fe and
Mn, which is caused by a decrease of soil Eh. The mobility of Pb in-
creased with incubation time under flood incubation and was much
higher than that under 70% FWC incubation. It is therefore clear that
the evaluation of the suitability of a washing agent cannot only be
based on the removal efficiency of heavy metals but it must also be
based on the redistribution of the metals after washing of agricultural
soils. In the present study, it was determined that CA is not a good wash-
ing agent for Pb-contaminated soil because CA-washing resulted in the
greatest release of Pb from inert fractions. Among the four agents tested,
FeCl3 solution is the most stable agent for removing Pb from contami-
nated soil because of its high removal efficiency and low release of Pb
after washing.
Acknowledgments
This research was financially supported by the China Environment
Protection Foundation (Project 2007-661).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.geoderma.2016.04.015.
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