Environ Sci Pollut Res (2017) 24:21128–21137

DOI 10.1007/s11356-017-9696-8

RESEARCH ARTICLE

Leaching of Cu, Cd, Pb, and phosphorus and their availability

in the phosphate-amended contaminated soils under simulated
acid rain
Hongbiao Cui 1,2 & Shiwen Zhang 1 & Ruyan Li 1 & Qitao Yi 1 & Xuebo Zheng 3 &
Youbiao Hu 1 & Jing Zhou 2

Received: 18 October 2016 / Accepted: 4 July 2017 / Published online: 20 July 2017
# Springer-Verlag GmbH Germany 2017

Abstract Phosphate amendments have been used to immobi-
lize heavy metal-contaminated soils. However, phosphate
amendments contain large amounts of phosphorus, which
could leach out to potentially contaminate groundwater and
surface water. A laboratory column leaching experiment was
designed to study the effects of simulated acid rain (SAR) on
the potential release of copper (Cu), lead (Pb), cadmium (Cd),
and phosphorus (P), and their availability after immobilizing
with hydroxyapatite (HAP) and potassium dihydrogen phos-
phate (PDP). The application of HAP and PDP enhanced the
leachate electrical conductivity, total organic carbon, and pH.
Higher P was found in the PDP- (>4.29 mg L−1) and HAP-
treated (>1.69 mg L−1) columns than that in untreated
(<0.2 mg L−1) columns, and they were both over the class V
limit (0.4 mg L−1) mandated by the Chinese National Quality
Standards for Surface Waters (GB 3838-2002). PDP
application decreased the leachate Cu, Pb, and Cd effectively;
however, HAP addition increased leachate Cu and Pb. HAP
and PDP applications decreased the soil CaCl2-extractable
and exchangeable fraction of Cu, Pb, and Cd, and increased
resin P. However, eluviations transformed the heavy metals
from inactive to active fractions and reduced soil labile P.
These findings showed that HAP and PDP had a potential risk
of excessive P-induced eutrophication. Meanwhile, more at-
tention should be paid to the leaching loss of multiple metals
because phosphate amendments might promote the leaching
of some metals while immobilizing others.
Keywords Hydroxyapatite . Potassium dihydrogen
phosphate . Simulated acid rain . Heavy metals . Phosphorus .
Leaching . Chemical speciation

Responsible editor: Philippe Garrigues Introduction

Electronic supplementary material The online version of this article
(doi:10.1007/s11356-017-9696-8) contains supplementary material, Chemical immobilization has been considered as a promising
which is available to authorized users. soil remediation technique compared with conventional tech-
niques, e.g., excavation and off-site disposal (Komárek et al.
* Shiwen Zhang 2013; Valipour et al. 2016). The aim of chemical immobiliza-
mamin1190@126.com tion is not to remove heavy metals but to reduce their mobility
* Jing Zhou and bioavailability by binding toxic heavy metals or changing
zhoujing@issas.ac.cn their chemical speciation in the soil (Komárek et al. 2013).
Numerous studies have noted that phosphate amendments are
1
School of Earth and Environment, Anhui University of Science and effective in immobilizing metals (Pb, Cu, Cd, etc.) in contam-
Technology, Huainan 232001, China
inated soils via conversion of reactive to stable metal species.
2
Key Laboratory of Soil Environment and Pollution Remediation, For instance, hydroxyapatite has been applied extensively to
Institute of Soil Science, Chinese Academy Sciences,
Nanjing 210008, China
remediate soils, sediments, and groundwater (Zhang et al.
3
2010). However, to date, most of the immobilization using
Shandong Industrial Engineering Laboratory of Biogas Production &
Utilization, Qingdao Institute of Bioenergy and Bioprocess
phosphate amendments has focused on the phosphate source
Technology, Chinese Academy of Sciences, 189 Songling Road, and single or multiple metals coexisting in soils and their
Qingdao, Shandong 266101, China immobilization efficiencies (Cao et al. 2013; Chrysochoou
Environ Sci Pollut Res (2017) 24:21128–21137
et al. 2007). For instance, some studies investigated the differ-
ent immobilization efficiencies for Pb, Cu, and Cd by readily
soluble phosphates (phosphoric acid), moderately soluble
phosphates (monocalcium, dicalcium, and tricalcium phos-
phate), and less soluble phosphates (synthetic hydroxyapatite
and phosphate rock) (Chrysochoou et al. 2007; Valipour et al.
2016).
Recently, increasing attention has been paid to the
long-term stability of the initially stabilized metals.
Heavy metal re-mobilization probably happens because
of microbial activity, landfill, weathering, aging, acid de-
position, and temperature fluctuation (Beesley et al. 2009;
Chen et al. 2010a). For example, our previous study
found that apatite (1%, w/w) had a better sustainable ef-
fect on the remediation of heavy metal-contaminated soils
than lime and charcoal in a 3-year field study (Cui et al.
2016). However, the metal immobilization efficiency de-
creased because of aging and acid rain. Unfortunately, the
major heavy metal pollution zone overlaps with the areas
affected by acid rain, particularly in southern China (MLR
and MEP 2014; Zhang et al. 2007). Thus, the mobility
and availability of heavy metals should be carefully eval-
uated during immobilization in an acid precipitation zone.
Phosphate amendments contain large amounts of phospho-
rus (P), and moderately and less soluble phosphate-treated
soils certainly leach less phosphate than readily soluble phos-
phates. For example, the concentration of P in phosphoric
acid-treated Pb-contaminated soils (over 10 mg L−1) was sig-
nificantly higher than that (over 0.6 mg L−1) in 0.5% HAP-
amended soil contaminated by single Cd (Cui et al. 2017;
Yang and Tang 2009). Therefore, it is anticipated that acid rain
will have a strong effect on the mobility and bioavailability of
heavy metals and P in the immobilization of heavy metal-
contaminated soils, depending on the different phosphate
sources.
The overall objective of this research was to investigate the
leaching of heavy metals and P and their availability in a
contaminated soil amended by hydroxyapatite (HAP, less sol-
uble phosphates) and potassium dihydrogen phosphate (PDP,
readily soluble phosphates) under simulated acid rain (SAR),
by determining (1) the characteristics of the effluent, e.g., pH,
electrical conductivity, total organic carbon, P, Cu, Pb, and Cd;
(2) post-leaching changes in soil pH and CaCl2-extractable
heavy metals; and (3) the transformation of the chemical spe-
cies of heavy metals and P.
Table 1 Basic physical and chemical properties of the tested soil
pH SOC A-N S-K O-P
(g kg−1) (mg kg−1) (mg kg−1) (mg kg−1)
5.64 23.7 95.7 42.8 58.5
SOC soil organic carbon, A-N alkali-hydrolyzable N, S-K soil test K, O-P Olsen P, T-P total P, CEC cation exchange capacity
21129
Materials and methods
Soil, PDP, HAP, and SAR
The analyzed soil sample was collected from an abandoned
paddy soil (0–20 cm) contaminated by drainage from slag
disposal sites in Guixi City, Jiangxi province, China, which
is near a large copper smelter. According to USDA soil tax-
onomy (Soil Survey Staff 2010), soil in this region is classified
as ultisols which is primarily derived from Quaternary red
clay. The soil was then air-dried, ground, and sieved through
a 2-mm nylon sieve. Selected soil chemical characteristics are
shown in Table 1.
PDP (analytical reagent) was purchased from
Sinopharm Chemical Reagent Co., Ltd., China. HAP
(purity >96%) was purchased from Nanjing Emperor
Nanomaterial Co. Ltd., China. The specific surface area
(BET) was 44.6 m2 g−1 and the Ca/P molar ratio of
HAP (pH = 7.23) was 1.61. The concentrations of Cu,
Cd, and Pb were 21.6, 0.45, and 8.94 mg kg−1 for HAP,
respectively. Details of the transmission electron micros-
copy (TEM) images and X-ray diffraction (XRD) pat-
terns of hydroxyapatite are given in supporting informa-
tion Figs. S1 and S2.
SAR was designed based on the pH of the local acid rain at
the study site (Cui et al. 2014). The predominant pH value of
SAR was 4.5, and it was prepared using a stock H2SO4–HNO3
at a ratio of 4:1 (v/v).
Soil treatments
HAP and PDP were applied to contaminated soil samples
at a 3:1 molar ratio of P to the sum of Cu, Pb, and Cd
(Cao et al. 2009; Wang et al. 2014). The amount of P
added was much higher than metal P stoichiometry for
M5(PO4)3X (M = Cu, Pb, and Cd; X = F, Cl, OH, and
Br) precipitation. The soil without any P application was
designated as the control (CK). The soil mixtures were
kept at room temperature and at approximately 70% field
moisture capacity. After incubating for 4 weeks, all sam-
ples passed through a 2-mm sieve and were divided into
two subsamples: one subsample was allowed to dry at
room temperature for chemical analysis, and the other
one was used for the leaching experiment.
T-P CEC Cd Cu Pb Zn
(mg kg−1) (mmol kg−1) (mg kg−1) (mg kg−1) (mg kg−1) (mg kg−1)
741 90.4 17.6 2238 1268 159
21130
Leaching experiment
There were three treatments, including no P addition plus
leaching with SAR (pH = 4.5), and PDP- and HAP-treated
soils plus leaching with SAR (pH = 4.5), respectively. PVC
columns (8 cm in diameter and 30 cm in length) were packed
uniformly with 1 kg of soil and repeated three times resulting
in a 20-cm soil core. Each column was filled with a layer of
inert quartz sand and a piece of filter paper (Whatman 1) at
both the top and bottom of the soil column. The column bot-
tom was sealed using a nylon net, placed on a PVC plate with
holes (diameter 2 mm). Prior to the leaching experiment, all
columns were slowly saturated from the bottom with deion-
ized water for 48 h, in order to remove air pockets and main-
tain the chemical equilibrium.
In each column, a peristaltic pump was used to control the
leaching rate at 41 ± 2 mL h−1, which corresponds to a typical
field infiltration velocity of 0.83 cm h−1 (Grolimund et al.
1996). The total amount of added SAR was calculated based
on yearly precipitation (1752 mm) and surface runoff loss
(25%), and the average annual rainfall was set to 6000 mL
(Dai et al. 2013). For each leaching, 500 mL SAR was used
every day (from 8 a.m. to 8 p.m.) to make a total of 12 L,
which corresponds to 2 years of precipitation in this study
area. Leachates were collected daily and then composited in
pairs successively every 2 days to create 12 1-L effluent sam-
ples. After 24 days, the soil from each column was thoroughly
mixed, air-dried, and ground for chemical analysis.
Chemical analysis
The pH and electrical conductivity (EC) were measured using
pH and electrical conductivity meters immediately after sam-
pling (unfiltered). These samples were filtered through a
0.45-μm membrane filter (Whatman 1) and divided into two
aliquots. One aliquot was analyzed for total organic carbon
(TOC) and P. Additionally, 40 mL of the filtered effluent was
acidized with HNO3 to pH <2 and stored at 0–4 °C for the
determination of the Cu, Pb, and Cd contents. The TOC was
determined by a TOC analyzer (Shimadzu TOC-VCSH,
Tokyo, Japan) by acidification/sparging and combustion.
The P was analyzed based on the Murphy and Riley (1962)
method. The concentrations of Cu, Pb, and Cd were analyzed
using a flame or graphite furnace atomic absorption spectro-
photometer (Model Z-2000, Hitachi, Tokyo, Japan).
Soil pH values were analyzed using a pH electrode (E-201-
C, Truelab Instrument, Shanghai, China) at a solid/water ratio
of 1:2.5 (w/v). Soil organic carbon (SOC) and cation exchange
capacity (CEC) were determined based on the methods of
Walkley and Black (1934) and Pansu and Gautheyrou
(2006), respectively. Soil alkali-hydrolyzable N and Olsen P
were measured based on the methods described by Lu (2000)
and Olsen et al. (1954), respectively. Soil test K was
Environ Sci Pollut Res (2017) 24:21128–21137
determined using 1.0 mol L−1 NH4OAc at pH = 7.0 (Pratt
1965). Soil total P was analyzed by the acidic molybdate–
ascorbic acid blue color method (Veldhoven and Mannaerts
1987). Soil total Cu, Pb, Cd, and Zn were determined after
digestion with 5 mL nitric acid (HNO3), 10 mL hydrofluoric
acid (HF), and 5 mL perchloric acid (HClO4) on a hot plate
and analyzed using the flame or graphite furnace atomic ab-
sorption spectrophotometer (Hitachi Model Z-2000, Hitachi).
The CaCl2-extracted heavy metals were analyzed using
0.01 mol L−1 CaCl2 at a 1:5 soil/extractant ratio (Mcbride
et al. 2004). Five chemical species of Cu, Pb, and Cd, which
included exchangeable (EXC), bound to carbonate (CA), Fe–
Mn oxides (Fe–Mn), organic matter (OM), and residual frac-
tion (RES), were determined by the sequential extraction pro-
cedure of Tessier et al. (1979) (see text S1). Soil P species,
including labile resin P, labile inorganic NaHCO 3 –P
(NaHCO3-Pi) and organic NaHCO3–P (NaHCO3-Po), moder-
ately labile inorganic NaOH–P (NaOH-Pi) and organic
NaOH–P (NaOH-Po), stable HCl-P, and residual P, were ana-
lyzed based on the modified method of Tiessen and Moir
(1993) (see text S2).
Data analyses
All results were presented as the mean ± standard error and
were analyzed by one-way analysis of variance (ANOVA)
using SPSS 19.0 (SPSS Inc., Chicago, IL, USA). The multiple
comparisons of the means within the treatments were tested by
the Duncan honestly significant difference test at the 0.05
level.
Results and discussion
TOC, EC, pH, and P in leachate
The dynamics of the selected leachate characteristics across
the different treatments are shown in Fig. 1. The highest ECs
in PDP-4.5 and HAP-4.5 during the collection of the first 1 L
were 3161 and 1391 μS m−1 and decreased to 92.5 and
88.6 μS m−1 until 8 L of effluent was collected, after which
the levels remained within the range of 68.9–78.9 μS m−1
(Fig. 1a). However, EC in the control decreased quickly from
823 to 41 μS m−1 during the collection of the first 3 L and then
ranged from 20.5 to 31 μS m−1. Moreover, EC in leachate
followed the order of PDP-4.5 > HAP-4.5 > CK-4.5. This
result suggested that HAP and PDP promoted the release of
base cations (e.g., K+, Na+, Ca2+, and Mg2+) which might be
caused by the higher dissolution of PDP compared with HAP
(see Fig. 1d).
Similar to EC, the peaks of TOC were found in the initial
effluent and dropped quickly, after which they reached stable
levels of 4.2–17.8 mg L−1; however, they followed the order
Environ Sci Pollut Res (2017) 24:21128–21137 21131

a b
3900 CK-4.5 HAP-4.5 PDP-4.5 1200 CK-4.5 HAP-4.5 PDP-4.5
2600 800
1300 400
900

TOC (mg L )
EC ( S m )

-1
100
-1

600 80

60

300 40

20

0
1L 2L 3L 4L 5L 6L 7L 8L 9 L 10 L 11 L 12 L 1L 2L 3L 4L 5L 6L 7L 8L 9 L 10 L 11 L 12 L

c d
350
CK-4.5 HAP-4.5 PDP-4.5 CK-4.5 HAP-4.5 PDP-4.5
7.5 Class V
300

7.0 250

Phosphate (mg L )

Phosphate (mg L )
-1

-1
0.16

6.5 200 0.12

pH

0.08
150
6.0
0.04

100

1L
2L
3L
4L
5L
6L
7L
8L
9L
10 L
11 L
12 L
5.5
50

5.0
0
1L 2L 3L 4L 5L 6L 7L 8L 9 L 10 L 11 L 12 L 1L 2L 3L 4L 5L 6L 7L 8L 9 L 10 L 11 L 12 L

Fig. 1 Dynamics of effluent electrical conductivity (EC, a), total HAP-4.5 hydroxyapatite (HAP)-treated soil plus SAR (pH 4.5), PDP-4.5
organic carbon (TOC, b), pH (c), and phosphate (d). CK-4.5 potassium dihydrogen phosphate (PDP)-treated soil plus SAR (pH 4.5)
untreated control soil plus simulated acid rain (SAR) (pH 4.5),

of HAP-4.5 > PDP-4.5 > CK-4.5 (Fig. 1b). For instance, the
concentrations of TOC in HAP-4.5 and PDP-4.5 were 844 and
277 mg L−1, which were about 9.5 and 2.6 times higher than
that of the control during the collection of the first 1 L. This
could be attributed to the fact that HAP and PDP compete
strongly for heavy metals from soil organic matters, which
caused the release of TOC. Our results were consistent with
Seaman et al. (2001) and Zhang and Zhang (2010), who found
that HAP and (NH4)3PO4 additions increased soil dissolved
organic carbon.
The pH in the leachate from the control remained within
the range of 5.73 to 6.41 (Fig. 1c). The dissolution of HAP
(Eq. 1) (Ma et al. 1994), however, caused the leachate pH to
increase markedly to 6.67 during the collection of the first 1 L
and then range from 7.0 to 7.31 as the remaining 11 L was
collected. In contrast, PDP decreased the leachate pH to 5.12
initially during the collection of the first 1 L, which was
0.61 unit less than the control. This might reflect the ionization
of H2PO4− from the fast dissolution of PDP, which releases
large amounts of H+ (Eqs. 2 and 3) (Mustafa et al. 2004).
Afterwards, the formation of metal phosphate, Fe–P, Al–P,
and Ca–P increases the soil negative charge, which decreases
H+ by electrostatic attraction. Thus, the leachate pH increased
to 6.47 during the collection of the first 4 L and then
maintained it at 6.55–6.74 as the remaining 8 L was collected.
Ca5 ðPO4 Þ3 ðOH Þ þ 7H þ ¼ 5Ca2þ þ 3H 2 PO4 − þ H 2 O ð1Þ
H 2 PO4 − ↔H þ þ HPO4 2− ð2Þ
HPO4 2− ↔H þ þ PO4 3− ð3Þ
Concentrations of leachate P from the control were lower
than 0.11 mg L−1 during the whole experiment, which was
below the class III limit (0.2 mg L−1) prescribed by the
Chinese National Quality Standards for Surface Waters (GB
3838-2002) (Fig. 1d). The low P in the control might be at-
tributed to the fact that P could react with iron (Fe) and alu-
minum (Al) in acidic soils (ultisols) and form amorphous and
insoluble Al and Fe phosphates (Ling et al. 2007). Large
amounts of P were leached during the collection of the first
5 L (5.04–10.9 mg L−1) from the HAP-4.5 and then gradually
decreased as the remaining 7 L was collected. This revealed
that the dissolution of HAP might be a slow process during the
experiment. Moreover, the least P from HAP-4.5 was
1.69 mg L−1, which was 4.23-fold higher than that of the class
V limit (maximum limit, 0.4 mg L−1). More seriously, P from
PDP-4.5 reached 312 mg L−1 during the collection of the first
1 L, which indicated that PDP dissolved quickly at the
21132 Environ Sci Pollut Res (2017) 24:21128–21137

beginning of the experiment. Afterwards, P was greater than a

10 mg L−1 during the collection of the first 7 L and decreased 400
CK-4.5 HAP-4.5 PDP-4.5

to 4.29–7.68 mg L−1 as the remaining 5 L was collected. This Class V

200
result indicated that PDP induced the highest leaching of P,
which was over 10.7 times higher than that of the class V limit
(GB 3838-2002), and posed a P-induced eutrophication risk.

Cu (mg L )
-1
Our result was consistent with that of Liu and Zhao (2007), 20
who found that the P concentration was 4.68 mg L−1 during
the immobilization of Pb-contaminated acidic soils with sodi-
um phosphate (300 mg L−1 phosphate) at a solution to soil 10
ratio = 2:1. Similarly, Melamed et al. (2003) also noted that
soluble P sources (e.g., H3PO4, KH2PO4) cause a high risk of
enhanced P eutrophication, and it was necessary to evaluate 0
soil P enrichment and leaching when phosphate amendments 1L 2L 3L 4L 5L 6L 7L 8L 9 L 10 L 11 L 12 L

were applied to immobilize heavy metal-contaminated soil.

b
4.8 CK-4.5 HAP-4.5 PDP-4.5
Heavy metal concentrations in the leachate Class V
4.2
3.6
Leaching of Cu, Pb, and Cd from the three soils is shown in
Fig. 2. Effluent Cu from CK-4.5 columns initially decreased
from 145 to 1.8 mg L−1 during the collection of the first 4 L Pb (mg L )
-1 2.0

and then stabilized at 0.38–0.79 mg L−1 during the collection

of the final 8 L (Fig. 2a). PDP addition decreased the Cu
concentration noticeably during the collection of first 1 L 1.0
and then reached the background levels of 0.37–
0.45 mg L−1 after the collection of the last 3 L. However,
the Cu concentration in the HAP-treated columns increased
drastically to 277 mg L−1 during the collection of the first 1 L, 0.0
1L 2L 3L 4L 5L 6L 7L 8L 9 L 10 L 11 L 12 L
which was 1.71 times higher than that of the control.
Afterwards, the Cu concentrations were over the class V limit c
(1 mg L−1) during the collection of the first 8 L. Similar to Cu, 4500 CK-4.5 HAP-4.5 PDP-4.5
3000 Class V
the concentrations of Pb in PDP-4.5 decreased significantly
but were enhanced in HAP-4.5 during the collection of the 1500

first 1 L and then reached background levels of 0.16–

0.27 mg L−1 as the remaining 7 L was collected (Fig. 2b).
Cd ( g L )

400
-1

Furthermore, PDP addition kept Pb within a concentration

of 0.18 to 0.35 mg L−1 during the experiment, indicating a 300

superior fixation capacity for Pb. However, Pb concentrations

were over the class V limit (0.1 mg L−1) for all columns during
200

the whole experiment, which showed a high risk for Pb 100

leaching.
In contrast to Cu and Pb, PDP and HAP both decreased 0
1L 2L 3L 4L 5L 6L 7L 8L 9 L 10 L 11 L 12 L
effluent Cd significantly compared with the control and
followed the order of HAP-4.5 < PDP-4.5 < CK-4.5 (Fig. Fig. 2 Dynamics of effluent Cu (a), Cd (b), and Pb (c). CK-4.5
2c). The highest Cd (3.21 mg L−1) was found in the control, untreated soil plus simulated acid rain (SAR) (pH 4.5), HAP-4.5
hydroxyapatite (HAP)-treated soil plus SAR (pH 4.5), PDP-4.5 po-
which indicated that the majority of Cd in soil was very active tassium dihydrogen phosphate (PDP)-treated soil plus SAR (pH 4.5)
and easily leached. Moreover, Cd was higher than the class V
limit (0.01 mg L−1), which showed a high risk for Cd leaching.
Similar to the performance of PDP in our study, previous compared with those for Cd. It may be due to the fact that
studies also suggested that phosphate amendments could pro- HAP (micro-particles) was dispersed and transformed into
mote the immobilization of heavy metals in soils by the for- large amounts of nano-sized HAP. This was further supported
mation of metal phosphates (Huang et al. 2016; Zhang et al. by the higher turbidity in HAP-4.5 compared with that in the
2010). However, HAP showed different results for Cu and Pb PDP-4.5 and CK-4.5 columns (Fig. S3). Moreover, a high
Environ Sci Pollut Res (2017) 24:21128–21137 21133

concentration of TOC could promote the transport of HAP A

8
based on the results of Wang et al. (2012), and the liberative
a
soluble organic complexes might enhance the mobility and a
b b
leaching potential of heavy metals (Li and Shuman 1997). c c
6
Therefore, high amounts of Cu and Pb adsorbed onto nano-
HAP could migrate into the effluent, resulting in higher Cu

Soil pH
and Pb in HAP-4.5 than that in PDP-4.5 and CK-4.5
4
(Table S1). Nevertheless, Cd in HAP-4.5 was lower than that
in PDP-4.5 and CK-4.5. One possibility could be the higher
sorption maxima (capacity) of HAP for Cu and Pb compared 2
with that for Cd (Chen et al. 2010b). Furthermore, the amount
of Cd adsorbed on HAP was reduced significantly in the pres-
ence of Cu and Pb (Corami et al. 2008), and hence, less Cd 0
was transported into the leachate. However, it failed to explain CK CK-4.5 HAP HAP-4.5 PDP PDP-4.5
why Cd in HAP-4.5 was lower than that in PDP-4.5 and CK-
4.5. Thus, more experiments are required to reveal the reason B
for the discrepant performance: the leaching behavior of Cu, 140 Cu Pb Cd
a a
Cd, and Pb by HAP. 120

Concentrations of metals (mg kg )

-1
100

Soil pH and CaCl2-extractable heavy metals in soil 80 b

affected by SAR 60 b
a
As shown in Fig. 3a, the lowest soil pH was found in the 20

control soil before leaching with SAR. However, HAP and a

PDP additions both increased the soil pH significantly by
1.1 and 0.5 units, respectively. Moreover, there were no sig-
nificant differences of soil pH before and after leaching with
acid rain, which indicated little effect of SAR on soil pH
during the simulated 2-year acid deposition.
As expected, CaCl2-extractable heavy metals in the control
were the highest (Fig. 3b). After leaching with SAR, CaCl2-
extractable Pb was increased, but CaCl2-extractable Cd de-
creased significantly because of the high leaching rate (22%,
Table S1) of Cd. However, Cu, Pb, and Cd concentrations in
the CaCl2 extracts were reduced significantly in the PDP- and
HAP-treated soils and they all followed the order of HAP <
PDP < CK. Compared with the control, CaCl2-extractable Cu,
Pb, and Cd were decreased by 97.8, 99, and 95% in HAP-
treated soils and by 95, 99.4, and 79% in PDP-treated soils.
Eluviations did not enhance CaCl2-extractable Cu and Pb and
only slightly increased CaCl2-extractable Cd in HAP-treated
soil. However, CaCl2-extractable Cu, Pb, and Cd increased
markedly in PDP-4.5 by 5.27, 4.71, and 2.53 times, respec-
tively, compared with those in PDP. Our results were consis-
tent with a previous study which found that HAP and PDP
could decrease CaCl2- and TCLP-extractable heavy metals
effectively (Dong et al. 2016). The immobilization mecha-
nisms for Cu and Cd were surface adsorption and complexa-
tion (Cao et al. 2004; Dong et al. 2016). For Pb, it was attrib-
uted mainly to the precipitation of insoluble Pb phosphates,
e.g., Pb5(PO4)X, where X was Cl, OH, F, or Br, and such
precipitates are the most inert Pb compounds under natural
c
b
d b
d c
d e d d d c
0
CK CK-4.5 HAP HAP-4.5 PDP PDP-4.5
Fig. 3 Soil pH (a) and CaCl2-extractable Cu, Pb, and Cd (b) in
soils before and after leaching with simulated acid rain (SAR). Values
followed by different letters were significantly different at P < 0.05. CK
untreated soil before leaching with SAR, CK-4.5 untreated soil plus SAR
(pH 4.5), HAP hydroxyapatite (HAP)-treated soil before leaching with
SAR, HAP-4.5 HAP-treated soil plus SAR (pH 4.5), PDP potassium
dihydrogen phosphate (PDP)-treated soil before leaching with SAR,
PDP-4.5 PDP-treated soil plus SAR (pH 4.5)
conditions, with a wide pH range (Chen et al. 1997;
Miretzky and Fernandez-Cirelli 2009).
Chemical speciation of Cu, Pb, and Cd in soils affected
by SAR
The total concentrations of Cu, Pb, and Cd and those of the
five chemical species are listed in Table 2. Before leaching
with SAR, Cu (30.3%) and Pb (35%) in the control soil mainly
appeared in the residual fraction; however, Cd (75.4%) was
concentrated in the exchangeable fraction. The main differ-
ence was that exchangeable Cu, Pb, and Cd were decreased
significantly by 89, 95.4, and 48.5%, respectively, in HAP and
by 39.9, 94.9, and 30.5%, respectively, in PDP. HAP and PDP
did not change the residual fractions of Cu and Cd but in-
creased the residual fraction of Pb by 61.7 and 37.8%,
21134 Environ Sci Pollut Res (2017) 24:21128–21137

Table 2 Sequentially extracted Cu, Cd, and Pb fractions in soils before and after leaching with simulated acid rain (SAR)

Treatment Total EXC CA Fe-Mn OM RES

Cu (mg kg−1)
CK 2224 ± 53a 351 ± 24a 401 ± 36b 425 ± 31bc 373 ± 19b 673 ± 50b
CK-4.5 2025 ± 88b 335 ± 16a 417 ± 10ab 448 ± 27bc 272 ± 21c 554 ± 37c
HAP 2238 ± 46a 38.5 ± 1.3e 462 ± 40a 643 ± 48a 426 ± 28a 669 ± 65b
HAP-4.5 1902 ± 57c 88.9 ± 9.1d 324 ± 22d 475 ± 23b 130 ± 17d 883 ± 21a
PDP 2216 ± 70a 211 ± 2.6c 335 ± 32 cd 582 ± 29a 399 ± 17ab 689 ± 52b
PDP-4.5 2173 ± 22a 308 ± 7b 385 ± 21bc 393 ± 27c 403 ± 12ab 651 ± 82bc
Cd (mg kg−1)
CK 17.5 ± 0.6a 13.2 ± 0.67a 0.73 ± 0.03d 0.68 ± 0.06d 0.2 ± 0.02e 2.72 ± 0.31a
CK-4.5 13.7 ± 0.6c 8.81 ± 0.68b 0.79 ± 0.06d 0.98 ± 0.11d 0.61 ± 0.07bc 2.56 ± 0.19a
HAP 17.6 ± 0.3a 6.8 ± 0.66c 3.13 ± 0.27a 4.6 ± 0.43a 0.77 ± 0.08a 2.27 ± 0.27a
HAP-4.5 17.1 ± 0.6ab 7.3 ± 0.23c 2.41 ± 0.13b 4.32 ± 0.03a 0.66 ± 0.06b 2.26 ± 0.35a
PDP 17.7 ± 0.5a 9.17 ± 0.56b 1.75 ± 0.12c 3.41 ± 0.27b 0.54 ± 0.06c 2.8 ± 0.3a
PDP-4.5 16.3 ± 0.3b 9.49 ± 0.37b 1.55 ± 0.17c 2.42 ± 0.19c 0.3 ± 0.02d 2.51 ± 0.41a
Pb (mg kg−1)
CK 1267 ± 46a 439 ± 6a 181 ± 15b 175 ± 13c 36 ± 3.6e 444 ± 39d
CK-4.5 1253 ± 27a 380 ± 33b 264 ± 13a 324 ± 40d 21.5 ± 0.8f 274 ± 15e
HAP 1276 ± 50a 20.3 ± 0.7d 39.2 ± 3.3e 379 ± 5bc 127 ± 10b 718 ± 60a
HAP-4.5 1264 ± 84a 35 ± 2.9d 56.5 ± 2.2d 531 ± 37a 103 ± 9c 525 ± 23c
PDP 1284 ± 52a 22.5 ± 0.2d 25 ± 2.4e 389 ± 28b 218 ± 13a 612 ± 60b
PDP-4.5 1250 ± 44a 143 ± 11c 123 ± 2c 503 ± 42a 62.7 ± 3.1d 422 ± 17d

Mean (n = 3) and standard error followed by different letters indicate significant differences (P < 0.05)
CK untreated soil before leaching with SAR, CK-4.5 untreated soil plus SAR (pH 4.5), HAP hydroxyapatite (HAP)-treated soil before leaching with
SAR, HAP-4.5 HAP-treated soil plus SAR (pH 4.5), PDP potassium dihydrogen phosphate (PDP)-treated soil before leaching with SAR, PDP-4.5 PDP-
treated soil plus SAR (pH 4.5)

respectively. Furthermore, HAP and PDP both increased the
fractions of Cu, Pb, and Cd in Fe–Mn and OM but decreased
the amount of Pb bound to carbonate and increased the Cd
bound to carbonate.
After leaching with SAR, total Cu and Cd were de-
creased slightly because of the leaching loss (Table S1),
and only total Pb was the same before and after SAR
leaching. Similar to the results before leaching with
SAR, the exchangeable fractions of Cu, Pb, and Cd in
HAP-4.5 and PDP-4.5 were less than those in CK-4.5.
Compared to the CK, SAR leaching decreased the ex-
changeable fractions of Cd and Pb in CK-4.5 by 33.3
and 13.4%, respectively. However, the exchangeable frac-
tions of Cu, Pb, and Cd increased in HAP-4.5 and PDP-
4.5 compared with those in HAP and PDP, respectively.
This might explain the increase in CaCl 2 -extractable
heavy metals after leaching with SAR. Furthermore, Cu,
Pb, and Cd bound to organic matter were decreased sig-
nificantly after leaching with SAR in the HAP- and PDP-
treated soils, which might be due to the higher concentra-
tion of TOC in the leachate compared with that in the
control. Overall, eluviations decreased the Cu and Pb in
the residual fraction for all soils except for HAP-4.5, but
no difference in the residual fraction of Cd was found
among all soils. Therefore, we concluded that SAR-
induced metal leaching might originate mainly from the
fractions of exchangeable and those bound to organic
matter.
The exchangeable and carbonate fractions were consid-
ered as weakly bonded metals according to Tessier et al.
(1979). Their sum, corresponding to the total concentra-
tion, has been used to assess the risk related to available
heavy metals (Liu et al. 2009; Tessier et al. 1979) and was
defined as the risk assessment code (RAC). Figure S4
clearly shows that the values of RACCd were the highest,
which were over 46.1% in our previous study (Cui et al.
2016). This may be the reason for the high CaCl2-extract-
able Cd response to the total concentration of Cd, which
indicated that Cd was high-risk and may occur because of
an accidental event in a very short term. Moreover, eluvi-
ations resulted in the increase in RAC values for Cu, Pb,
and Cd in PDP-treated columns; however, only the value
of RACPb was slightly increased after leaching with SAR
in HAP-treated columns. This showed that HAP is more
effective in immobilizing heavy metals than PDP in an
acid precipitation zone.
Environ Sci Pollut Res (2017) 24:21128–21137 21135

Table 3 Sequentially extracted P fractions (mg kg−1) in soils before and after leaching with simulated acid rain (SAR)

Treatment Total P Labile P Moderately labile P Stable P

Resin P NaHCO3-Pi NaHCO3-Po NaOH-Pi NaOH-Po HCl-P Residual P

CK 738 ± 10c 86.7 ± 2.6d 34.5 ± 3.6c 8.64 ± 1.64d 80.9 ± 2.2d 35.6 ± 1.4a 133 ± 19c 358 ± 13c
CK-4.5 734 ± 41c 74.2 ± 4.0d 48.9 ± 4.6d 15.9 ± 1.8 dc 79.5 ± 9.2d 36.3 ± 1.4a 107 ± 5c 378 ± 42c
HAP 2408 ± 60a 358 ± 32c 65 ± 2.9b 17.4 ± 1.5bc 95.3 ± 7.4c 8.7 ± 1.1d 1036 ± 43a 828 ± 76b
HAP-4.5 2379 ± 68a 300 ± 13c 60.2 ± 4.1b 15.7 ± 1.4c 102 ± 6c 5 ± 0.8e 770 ± 44b 1127 ± 72a
PDP 2451 ± 50a 1673 ± 63a 116 ± 9a 20.6 ± 1.3a 141 ± 8a 18.3 ± 1.3b 159 ± 23c 324 ± 46c
PDP-4.5 1984 ± 78b 506 ± 40b 66.9 ± 1.7b 19.0 ± 1.3ab 113.8 ± 3.3b 13.5 ± 1c 147 ± 10c 1199 ± 104a

Mean (n = 3) and standard error followed by different letters indicate significant differences (P < 0.05)
CK untreated soil before leaching with SAR, CK-4.5 untreated soil plus SAR (pH 4.5), HAP hydroxyapatite (HAP)-treated soil before leaching with
SAR, HAP-4.5 HAP-treated soil plus SAR (pH 4.5), PDP potassium dihydrogen phosphate (PDP)-treated soil before leaching with SAR, PDP-4.5 PDP-
treated soil plus SAR (pH 4.5)

Chemical speciation of P in soils affected by SAR
As shown in Table 3, the P fractions were affected mark-
edly by HAP and PDP applications, and the P in the labile
fractions was higher compared with that in the control. As
expected, total P was increased dramatically in HAP- and
PDP-treated soils (by 2.26 and 2.32 times, respectively)
compared with the control. PDP comprises soluble phos-
phates; therefore, total P was decreased significantly by
19.1% in PDP-4.5 compared with that in PDP. However,
no difference was found in total P for HAP-4.5 and CK-
4.5 compared with that before leaching with SAR. The
concentration of resin P in the control was the lowest
(86.7 mg kg−1, 11.7%) among all the soils, which was
consistent with a previous study (Wang et al. 2008),
where the resin P was 13.3% less of the total P in red soil
from Yingtan of Jiangxi China. However, the concentra-
tions of resin P in HAP (14.9%) and PDP (68.3%) were
enhanced significantly (by 3.13 and 18.3 times) and
followed the order of CK < HAP < PDP before and
after leaching with SAR. Similarly, Rivaie et al. (2008)
also found that soil resin P was increased with the appli-
cations of phosphate rock and triple superphosphate.
Moreover, resin P is freely exchangeable P, which can
be used as a good indicator of the short-term P loss po-
tential in soil and causes eutrophication in an aquatic eco-
system ((Li et al. 2016b). Therefore, it is clear that the use
of PDP raises higher risk of P-induced eutrophication
compared with HAP, which was further illustrated by the
high P leaching loss in the PDP-4.5-treated leachate
(Table S1).
According to Negassa and Leinweber (2009), labile inor-
ganic P (NaHCO3-Pi) and moderately labile inorganic P
(NaOH-Pi) are the forms that are likely to be available to
plants. In this study, they were increased significantly after
HAP and PDP applications. These results were similar to
those obtained from previous studies (Liu and Lal 2014;
Malik et al. 2012), where the amounts of NaHCO3-Pi and
NaOH-Pi increased significantly after the application of or-
ganic or inorganic P amendments to the soil. The amounts
of NaHCO3-Pi and NaOH-Pi decreased drastically in PDP-
4.5 (161 mg–kg−1) than those in PDP (257 mg kg−1); howev-
er, they maintained a stable level (160–162 mg kg−1) in HAP-
treated soils before and after leaching with SAR.
Organic P, represented by the amounts of NaHCO3-Po and
NaOH-Po, was decreased after the applications of HAP and
PDP compared with that in the control. Moreover, organic P
(NaHCO3-Po and NaOH-Po) was decreased by 20.7 and
16.5% in HAP- and PDP-treated soils before and after
leaching with SAR, respectively.
Since HCl-extractable P (HCl-P) is an inorganic P associ-
ated with apatite, other Ca–P compounds, or negatively
charged oxide surfaces (Negassa and Leinweber 2009;
Rodrigues et al. 2015). HCl-P was increased drastically after
HAP application. However, no significant differences in HCl-
P were found between CK and PDP. Moreover, the residual P
increased markedly after HAP application. PDP application
did not affect residual P before leaching with SAR but in-
creased dramatically to 1199 mg kg−1 after leaching with
SAR. This indicated that P fractions in control soils mainly
concentrated in residual P before and after leaching with SAR
but concentrated in HCl-P and residual P in HAP-treated soils
before and after leaching with SAR, respectively. For PDP-
treated soils, resin P was predominant before leaching with
SAR, but residual P was predominant after leaching with
SAR.
In general, HAP and PDP applications promoted an in-
crease in soil labile P and stable P but only slightly affected
moderately labile P. The eluviations did not notably disturb
the distribution of P fractions for the untreated soils but re-
duced HCl-P markedly in HAP-treated soils. Moreover, the
eluviations increased residual P significantly and reduced res-
in P drastically in the PDP-treated soils, which had a high risk
of P-induced eutrophication.
21136
Environmental implications
Our results clearly indicated that phosphate amendments could
reduce Cu, Pb, and Cd availability effectively in soils and pro-
mote an increase in soil labile P. This is a good practical approach
for the heavy metal-contaminated soils in southern China (MLR
and MEP 2014), because the soil is largely P-deficient (Li et al.
2016a). Unfortunately, HAP and PDP treatments showed high P
leaching loss at the early stage of the leaching process, especially
the high P (over 4.29 mg L−1) in PDP (readily soluble phos-
phate)-treated soils. Similarly, Yang et al. (2007) noted that P
reached 1–4 mg L−1 in H3PO4-treated soil and mine waste con-
taminated by Pb. Even for the HAP (less soluble phosphate), the
P content was over 1.69 mg L−1 (higher than the class V limit,
0.4 mg L−1) during the leaching process. Moreover, Yang and
Tang (2009) noted that the potential of P enrichment in ground-
water might be reduced in the presence of plant growth.
Unfortunately, only a few plants can grow in the early stage of
remediation. Worse still, the application rates (w/w) reported in
literature range from 1 to 5 (Cui et al. 2013; Dong et al. 2016) and
3% PO43− by weight for remediating soils recommended by US
EPA (2001). Inevitably, such high doses would lead to an en-
hanced risk of eutrophication induced by excessive P loss.
When HAP was transformed from micro-particles to nano-
particles, large amounts of Cu and Pb were leached into the
leachate in HAP-treated soils. This reminds us that it is indis-
pensable to evaluate the transport and fate of nano-materials
before applying them in the natural environment (Wang et al.
2012). Moreover, leaching with SAR transformed heavy
metals from inactive to active fractions; therefore, more atten-
tion should be paid to the long-term stability of immobiliza-
tion. Furthermore, we showed clearly that metal and phos-
phate losses occurred mainly at the early stage of the leaching
process. Accordingly, we propose that the following measures
be applied during practical soil remediation with phosphate
amendments.
First, the application dose of the amendments must be re-
stricted. A preliminary experiment is indispensable to deter-
mine the proper dose that can not only decrease metal bio-
availability effectively but also release the least phosphate into
the soil environment.
Second, some collection channels for surface water should
be built near the soil remediation zone to allow the simple
purification of the wastewater. Such an approach could reduce
the migration of metals and P into rivers, especially at the early
stage of soil remediation.
Third, rapid vegetation restoration is necessary after mixing
soil and phosphate amendments. It is recommended to transplant
remediation plants such as Sedum plumbizincicola, Vetiveria
zizanioides, and Elsholtzia splendens rather than slowly restore
vegetation by direct sowing of plant seeds. This measure could
further decrease water and soil losses and diminish P and heavy
metals in surface- and groundwater.
Environ Sci Pollut Res (2017) 24:21128–21137
Acknowledgments This work was supported by the National Key
Research and Development Program of China (2016YFD030080104
and 2016YFC0201605), the National Natural Science Foundation of
China (41601340), the Natural Science Foundation of Universities of
Anhui Province (KJ2016A191), the National Key Basic Research
Program of China (2013CB934302), the National Key Technology
Research and Development Program of China (2015BAD05B01), and
the Key Laboratory of Soil Environment and Pollution Remediation,
the Institute of Soil Science, Chinese Academy of Sciences. We express
our gratitude to the anonymous reviewers for their constructive comments
and suggestions.
References
Beesley L, Moreno-Jiménez E, Clemente R, Lepp N, Dickinson N (2009)
Mobility of arsenic, cadmium and zinc in a multi-element contam-
inated soil profile assessed by in-situ soil pore water sampling, col-
umn leaching and sequential extraction. Environ Pollut 158:155–
160
Cao X, Ma LQ, Rhue DR, Appel CS (2004) Mechanisms of lead, copper,
and zinc retention by phosphate rock. Environ Pollut 131:435–444
Cao X, Wahbi A, Ma L, Li B, Yang Y (2009) Immobilization of Zn, Cu,
and Pb in contaminated soils using phosphate rock and phosphoric
acid. J Hazard Mater 164:555–564
Cao X, Liang Y, Zhao L, Le H (2013) Mobility of Pb, Cu, and Zn in the
phosphorus-amended contaminated soils under simulated landfill
and rainfall conditions. Environ Sci Pollut Res 20:5913–5921
Chen X, Wright JV, Conca JL, Peurrung LM (1997) Effects of pH on
heavy metal sorption on mineral apatite. Environ Sci Technol 31:
624–631
Chen G, Zeng G, Du C, Huang D, Lin T, Liang W, Shen G (2010a)
Transfer of heavy metals from compost to red soil and ground-
water under simulated rainfall conditions. J Hazard Mater 181:
211–216
Chen SB, Ma YB, Chen L, Xian K (2010b) Adsorption of aqueous Cd2+,
Pb2+, Cu2+ ions by nano-hydroxyapatite: single- and multi-metal
competitive adsorption study. Geochem J 44:233–239
Chrysochoou M, Dermatas D, Grubb DG (2007) Phosphate application to
firing range soils for Pb immobilization: the unclear role of phos-
phate. J Hazard Mater 144:1–14
Corami A, Mignardi S, Ferrini V (2008) Cadmium removal from single-
and multi-metal (Cd + Pb + Zn + Cu) solutions by sorption on
hydroxyapatite. J Colloid Interf Sci 317:402–408
Cui H, Zhou J, Zhao Q, Si Y, Mao J, Fang G, Liang J (2013) Fractions of
Cu, Cd, and enzyme activities in a contaminated soil as affected by
applications of micro-and nanohydroxyapatite. J Soils Sediments
13:742–752
Cui J, Zhou J, Peng Y, He Y, Yang H, Mao J (2014) Atmospheric wet
deposition of nitrogen and sulfur to a typical red soil agroecosystem
in Southeast China during the ten-year monsoon seasons (2003–
2012). Atmos Environ 82:121–129
Cui H, Fan Y, Xu L, Zhou J, Zhou D, Mao J, Fang G, Long C,
Zhu Z (2016) Sustainability of in situ remediation of Cu- and
Cd-contaminated soils with one-time application of amend-
ments in Guixi, China. J Soils Sediments 16:1498–1508
Cui H, Yi Q, Li R, Yang X, Wang X, Wu H, Zhou J (2017) Effects of
hydroxyapatite on leaching of cadmium and phosphorus and their
availability under simulated acid rain. J Environ Chem Eng. doi:10.
1016/j.jece.2017.07.001
Dai Z, Liu X, Wu J, Xu J (2013) Impacts of simulated acid rain on
recalcitrance of two different soils. Environ Sci Pollut Res 20:
4216–4224
Dong A, Ye X, Li H, Zhang Y, Wang G (2016) Micro/nanostructured
hydroxyapatite structurally enhances the immobilization for Cu and
Cd in contaminated soil. J Soils Sediments 16:2030–2040
Environ Sci Pollut Res (2017) 24:21128–21137
Grolimund D, Borkovec M, Barmettler K, Sticher H (1996) Colloid-
facilitated transport of strongly sorbing contaminants in natural po-
rous media: a laboratory column study. Environ Sci Technol 30:
3118–3123
Huang G, Su X, Rizwan MS, Zhu Y, Hu H (2016) Chemical immobili-
zation of Pb, Cu, and Cd by phosphate materials and calcium car-
bonate in contaminated soils. Environ Sci Pollut Res 23:16845–
16856
Komárek M, Vaněk A, Ettler V (2013) Chemical stabilization of metals
and arsenic in contaminated soils using oxides—a review. Environ
Pollut 172:9–22
Li Z, Shuman LM (1997) Mobility of Zn, Cd and Pb in soils as affected
by poultry litter extract—I. Leaching in soil columns. Environ Pollut
95:219–226
Li B, Ge T, Xiao H, Zhu Z, Li Y, Shibistova O, Liu S, Wu J, Inubushi K,
Guggenberger G (2016a) Phosphorus content as a function of soil
aggregate size and paddy cultivation in highly weathered soils.
Environ Sci Pollut Res 23:7494–7503
Li R, Wang JJ, Zhou B, Awasthi MK, Ali A, Zhang Z, Gaston LA, Lahori
AH, Mahar A (2016b) Enhancing phosphate adsorption by Mg/Al
layered double hydroxide functionalized biochar with different Mg/
Al ratios. Sci Total Environ 559:121–129
Ling D, Zhang J, Ouyang Y, Huang Q (2007) Role of simulated acid rain
on cations, phosphorus, and organic matter dynamics in latosol.
Arch Environ Con Tox 52:16–21
Liu R, Lal R (2014) Synthetic apatite nanoparticles as a phosphorus
fertilizer for soybean (Glycine max). Sci Rep 4:5686–5686
Liu R, Zhao D (2007) Reducing leachability and bioaccessibility of lead
in soils using a new class of stabilized iron phosphate nanoparticles.
Water Res 41:2491–2502
Liu JL, Li YL, Zhang B, Cao JL, Cao ZG, Domagalski J (2009)
Ecological risk of heavy metals in sediments of the Luan River
source water. Ecotoxicology 18:748–758
Lu R (2000) Soil agricultural chemical analysis method. China
Agricultural Science and Technology Press, Beijing (in Chinese)
Ma QY, Traina SJ, Logan TJ, Ryan JA (1994) Effects of aqueous Al, Cd,
Cu, Fe (II), Ni, and Zn on Pb immobilization by hydroxyapatite.
Environ Sci Technol 28:1219–1228
Malik MA, Marschner P, Khan KS (2012) Addition of organic and inor-
ganic P sources to soil e effects on P pools and microorganisms. Soil
Biol Biochem 49:106–113
Mcbride MB, Richards BK, Steenhuis T (2004) Bioavailability and crop
uptake of trace elements in soil columns amended with sewage
sludge products. Plant Soil 262:71–84
Melamed R, Cao X, Chen M, Ma LQ (2003) Field assessment of lead
immobilization in a contaminated soil after phosphate application.
Sci Total Environ 305:117–127
Miretzky P, Fernandez-Cirelli A (2009) Phosphates for Pb immobiliza-
tion in soils: a review. Environ Chem Lett 6:121–133
MLR, MEP (2014) The communique of national investigation of soil
contamination. Ministry of Land and Resources of the People’s
Republic of China. Ministry of environmental protection of the
People’s Republic of China, China
Murphy J, Riley JP (1962) A modified single solution method for deter-
mination of phosphate in natural waters. Anal Chim Acta 27:31–36
Mustafa S, Naeem A, Rehana N, Hamid A, Dilara B (2004) Phosphate/
sulphate exchange studies on amberlite IRA-400. Environ Technol
25:1115–1122
Negassa W, Leinweber P (2009) How does the Hedley sequential phos-
phorus fractionation reflect impacts of land use and management on
soil phosphorus: a review. J Plant Nutr Soil Sci 172:305–325
Olsen SR, Cole CV, Watanabe FS, Dean LA (1954) Estimation of avail-
able phosphorus in soils by extraction with sodium bicarbonate.
United States Department of Agriculture, Circular 939. United
States Government Printing Office, Washington
21137
Pansu M, Gautheyrou J (2006) Handbook of soil analysis-mineralogical,
organic and inorganic methods. Springer, Berlin
Pratt PF (1965) Potassium. In: Black CA (ed) Methods of soil analysis.
Part 2. Chemical and microbiological properties. American Society
of Agronomy, Inc., Madison
Rivaie AA, Loganathan P, Graham JD, Tillman RW, Payn TW (2008)
Effect of phosphate rock and triple superphosphate on soil phospho-
rus fractions and their plant-availability and downward movement in
two volcanic ash soils under Pinus radiata plantations in New
Zealand. Nutr Cycl Agroecosys 82:75–88
Rodrigues M, Pavinato PS, Withers PJA, Teles APB, Herrera WFB
(2015) Legacy phosphorus and no tillage agriculture in tropical
oxisols of the Brazilian savanna. Sci Total Environ 542:1050–1061
Seaman JC, Arey JS, Bertsch PM (2001) Immobilization of nickel and
other metals in contaminated sediments by hydroxyapatite addition.
J Environ Qual 30:460–469
Soil Survey Staff (2010) Keys to soil taxonomy, eleventh edn. USDA,
Washington
Tessier A, Campbell PGC, Bisson M (1979) Sequential extraction proce-
dure for the speciation of particulate trace-metals. Anal Chem 51:
844–851
Tiessen H, Moir JO (1993) Characterization of available P by sequential
extraction. In: Carter MR (ed) Soil sampling and methods of analy-
sis, Can J Soil Sci. Lewis Publishers, Boca Raton, pp 75–86
US EPA, Region 10 (2001) Consensus plan for soil and sediment studies:
Coeur d’Alene river soils and 494 sediments bioavailability studies
(URS DCN: 4162500.06161. 05. a. EPA: 16.2), 1–16
Valipour M, Shahbazi K, Khanmirzaei A (2016) Chemical immobiliza-
tion of lead, cadmium, copper and nickel in contaminated soils by
phosphate amendments. Clean - Soil Air Water 44:572–578
Veldhoven PPV, Mannaerts GP (1987) Inorganic and organic phosphate
measurements in the nanomolar range. Anal Biochem 161:45–48
Walkley AE, Black CA (1934) An examination of Degtjareff method for
determining soil organic matter and a proposed modification of the
chromic acid titration method. Soil Sci 37:29–38
Wang X, Jie X, Zhu Y, Hou Y, Zhang T (2008) Relationships between
agronomic and environmental soil test phosphorus in three typical
cultivated soils in China. Pedosphere 18:795–800
Wang D, Bradford SA, Harvey RW, Gao B, Cang L, Zhou D (2012)
Humic acid facilitates the transport of ARS-labeled hydroxyapatite
nanoparticles in iron oxyhydroxide-coated sand. Environ Sci
Technol 46:2738–2745
Wang L, Li Y, Li H, Liao X, Wei B, Ye B, Zhang F, Yang L, Wang W,
Krafft T (2014) Stabilize lead and cadmium in contaminated soils
using hydroxyapatite and potassium chloride. Environ Monit Assess
186:9041-9050
Yang J, Tang X (2009) Leaching characteristics of phosphate-stabilized
lead in contaminated urban soil and mill waste. J Environ Monit
Rest 6:127–134
Yang J, Tang X, Wang Z (2007) Water quality and ecotoxicity as influ-
enced by phosphate and biosolid treatments in lead contaminated
soil and mine waste. J Environ Monit Rest 3:21–33
Zhang M, Zhang H (2010) Co-transport of dissolved organic matter and
heavy metals in soils induced by excessive phosphorus applications.
J Environ Sci 22:598–606
Zhang JE, Ouyang Y, Ling DJ (2007) Impacts of simulated acid rain on
cation leaching from the latosol in south China. Chemosphere 67:
2131–2137
Zhang Z, Li M, Chen W, Zhu S, Liu N, Zhu L (2010) Immobilization of
lead and cadmium from aqueous solution and contaminated sedi-
ment using nano-hydroxyapatite. Environ Pollut 158:514–519