Journal of Environmental Management 255 (2020) 109872

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Journal of Environmental Management

journal homepage: http://www.elsevier.com/locate/jenvman

Research article

Activated dolomite phosphate rock fertilizers to reduce leaching of

phosphorus and trace metals as compared to superphosphate
Xiaoli Wang a, b, Jibing Xiong a, c, Zhenli He a, *
a
Department of Soil and Water Sciences, Indian River Research and Education Center, Institute of Food and Agricultural Sciences, University of Florida, Fort Pierce, FL,
34945, USA
b
College of Plant Science, Jilin University, Changchun, 130012, China
c
School of Environmental Science & Spatial Informatics, China University of Mining and Technology, Xuzhou, 221116, China

A R T I C L E I N F O A B S T R A C T

Keywords: Use of water-soluble phosphorus (P) fertilizers such as superphosphates (SP) has been increasingly concerned due
Activated slow release fertilizers to the loss of P and trace metals such as cadmium (Cd) into the environment. Activated phosphate rock holds
Trace metals promising as an alternate due to non-destructive and slow release nature. The objective of this study was to assess
Leaching potential
the leaching potential of P and trace metals from newly developed activated dolomite phosphate rock (HA-DPR
Phosphorus
Sandy soils
and SLS-DPR), as compared to water-soluble fertilizers, including superphosphate (SP), diammonium phosphate
(DAP) and original dolomite phosphate rock (DPR). Two representative agricultural soils (Alfisol and Spodosol
soil) were sampled at the 0–20 cm depth from two farms for the column leaching experiments. Seven leachings
were conducted at day 1, 3, 7, 14, 21, 28, and 56, respectively, and a total of 1050 mL of deionized water
(equivalent to half year’s rainfall in the Indian River area) was applied for leaching. Leachates were collected
from each leaching event and analyzed for water-soluble P and metals. Activated DPR application led to an
increase in soil pH by 1.4–1.7 units, whereas SP resulted in a decrease in soil pH by 0.4–1.6 units. P leaching from
activated DPR were 33–61 times less than that from SP or DAP. HA-DPR and SLS-DPR treatments reduced cu­
mulative trace metals in leachate by 1.3–12.3 times for the Alfisol soil, and 1.4 to 8.4 times for the Spodosol soil,
respectively. These results indicate that activated DPR fertilizers are more environmentally friendly than water-
soluble fertilizers.

1. Introduction
Phosphorus is the second most important macronutrient for plant
growth, crop production and human nutrition. Application of P fertil­
izers is vital for sustaining desired crop yield and quality, and phosphate
fertilization has been practiced massively since the end of World War II
(Tilman, 1999). Use of P in agriculture accounts for nearly 90% of the
total world demand; however, world reserve of phosphates is limited
and high-grade phosphate rock is rapidly depleted (Gupta et al., 2014).
The need to feed the world population of 7.2 (now) to 10 billion (2050)
at decreasing reserves of mineable phosphate raises great urgency of
exploiting new P fertilizers (Odongo et al., 2007; Sun et al., 2007; Huang
et al., 2014; Mendes et al., 2014) and improving management of soil P
(Tilman et al., 2002). On the other hand, application of water-soluble P
fertilizers often results in severe environmental problems such as
eutrophication of surface waters due to leaching of P from soil (Litaor
et al., 2003; Torrent et al., 2007; Holman et al., 2010), toxicity of surface
waters (Kier and Kirkland, 2013; Webster et al., 2014), and metallic
contamination of soils (Chen et al., 2006; Heredia and Cirelli, 2007;
Yang et al., 2013).
Phosphate rock (PR) is the major source for producing P fertilizers
(Yang et al., 2013). Properties of phosphate rock vary widely with
sources. High-grade of PR contains 25–37% of P2O5 (Gupta et al., 2014).
Phosphate rock that contains less P2O5 may not be adequate or profit­
able for commercial production of phosphoric acid (Fukuda et al., 2013;
Mihajlovic et al., 2014; Rosolem and Almeida, 2014). Efficient use of the
medium- and low-grade DPR is important to mitigate the problem of
phosphate rock shortage. Accordingly, approaches to increasing P
availability in PR have increasingly been the focus of research efforts in
recent decades, such as incorporation of additives into PR, partial
acidulation of PR, incorporation of PR with water-soluble P fertilizers,
and microbial methods (Odongo et al., 2007). Composting manure or
biological waste with PR has proved to enhance the dissolution of the PR
(Singh and Amberger, 1991). Green waste composting or sulfur addition

* Corresponding author.
E-mail address: zhe@ufl.edu (Z. He).

https://doi.org/10.1016/j.jenvman.2019.109872
Received 25 October 2019; Received in revised form 6 November 2019; Accepted 12 November 2019
Available online 27 November 2019
0301-4797/© 2019 Elsevier Ltd. All rights reserved.
X. Wang et al.
promoted PR solubilization and improved P availability (Bustamante
et al., 2016). Inoculation of phosphate-solubilizing bacteria (PSB) could
improve P transformation and long-term utilization efficiency (Wei
et al., 2017). Also, the efficacy of PR was reported to increase by com­
bined using of organic compost and phosphate solubilizing bacteria
(Yadav et al., 2017). However, most of these studies focused more on the
quality of compost organic fertilizers and were more concerned about
how and what degree did PR improve P availability in the compost
organic fertilizers.
Furthermore, the side effects of most likely releasing of trace metals
from PR accompanied with P dissolution of PR are rarely studied. PR
usually contains three categories of toxic elements, i.e. radiative ele­
ments, trace metals, and rare earth elements, and the former two cate­
gories are the most concerned environmental contaminants (Sadaqah
et al., 2005; Sahu et al., 2014; Siddique et al., 2018). PR is natural
mineral deposits belonging to the species of apatite family, the amounts
of trace metals in PR sources are variable among different sources, and
the sedimentary PR generally encompasses higher toxic elements
(Javied et al., 2009). The reported trace metals in PR include lead (Pb),
arsenic (As), mercury (Hg), cadmium (Cd), antimony (Sb), vanadium
(V), nickel (Ni), and so on. The toxicity of these trace metals depends on
their form and oxidation state. Cd is the most studied toxic metal due to
its high mobility and transfer rate from soil to crops (Roberts, 2014;
Benredjem et al., 2016). Cd concentration in PR in the world tends to be
higher in North Africa with the content up to 60 mg/kg; Pb is higher in
PR of Brazil (44.5 mg/kg), and the highest Zn concentration occurred in
the PR of Tunis (515 mg/kg) (Siddique et al., 2018). Phosphate fertil­
izers produced from phosphate rocks are therefore accompanied with
toxic trace metals, which might result in buildup of different poisonous
metals in soil (Nicholson et al., 2003; Tufail et al., 2006; Yang et al.,
2015). The repeated application of P fertilizers could lead to trace metal
accumulation in the soil over time (Huang et al., 2017), as trace metals
are non-biodegradable (Roberts, 2014; Barkouch et al., 2016).
The phosphate industry in central Florida produces a significant
amount of dolomite phosphate rock (DPR) materials, which are not
adequate for phosphoric acid production due to high dolomite content.
One of the novel technologies developed lately is to activate phosphate
(P) in DPR to convert DPR into highly efficient slow release fertilizers
(Odongo et al., 2007; Sun et al., 2007; Huang et al., 2014; Mendes et al.,
2014). Previous studies indicated that activation of DPR with selected
organic molecules resulted in substantial increases in water-soluble P,
by 10–100 times (He et al., 2017). Moreover, the activated DPR could
continuously supply P to meet the physiological requirement of P by
crops during the growing season according to greenhouse experiments
(Mao et al., 2017). It is hypothesized that during the activation process,
other macroelements and microelements may be also released, as a
result of P release. However, no systematic studies have been conducted
to evaluate environmental impacts of the activated DPR fertilizers with
regards to leaching potential of P and elements, especially potentially
toxic metals, which are concerned due to their potential risks to human
health.
In this study, two pre-screened organic agents were used to activate
and convert DPR into two slow release P fertilizers. Column leaching
experiments were carried out to assess environmental impacts of the
activated DPR fertilizers, as compared with original DPR and water-
soluble fertilizers including SP derived from the same DPR material
and diammonium phosphate (DAP). Two representative agricultural
soils (Alfisol and Spodosol soil) in south Florida were used for testing the
leaching potential of P and metals from the activated DPR fertilizers.
2. Materials and methods
2.1. Activation of DPR
Representative DPR samples of medium- and low-grade were
collected from the mining site in central Florida and ground to <100
2
Journal of Environmental Management 255 (2020) 109872
mesh. Humic acids (HA) and sodium lignosulfonate (SLS) were pur­
chased from Fisher Scientific and used as activating agents. During the
activating process, The DPR powder (<100 mesh) was subjected to re­
action with each of the activating agents at the ratio of 5% by grinding
for 15 min after adding 15% moisture and mixing. The final products
were called activated DPR fertilizers, i.e. HA-DPR and SLS-DPR. Mean­
while, superphosphate (SP) was also prepared from the same DPR ma­
terial acidified using concentrated sulfuric acid following the standard
procedure (Methods of producing phosphatic fertilizers. US2739885 A,
Dana S Lamb, Glen E Cooley, Halfdan Gregersen, Magnus I Gregersen,
Warren Dunham Foster, 1953). The resulted products were air dried and
ground to <1 mm prior to use. The SP fertilizer was used for comparison
with the activated DPR fertilizers.
pH and electrical conductivity (EC) of original DPR, activated DPR
and SP were determined using a pH/EC meter (Accumet AB 200, Fisher
Scientific) at the solid/water ratios of 1:1 and 1:2, respectively. For
measurement of water-soluble P (WSP) in the fertilizers, portions of each
sample (0.50 g each) were weighed into 50-mL centrifuge tubes. After
50 mL deionized water was added to each tube, the suspensions were
oscillated on a shaker at 200 rpm and 25 � 1 � C for 1 h and then
centrifuged at 4000 rpm for 10 min. The supernatant solution was
filtered into a 100-mL plastic bottle through a Whatman no. 42 filter
paper, and the extraction was repeated for additional five times. Con­
centrations of WSP in the filtrate from each extraction were determined
colorimetrically with the molybdenum-blue method (Mao et al., 2017).
The amount of WSP in each fertilizer was calculated as the sum of six
sequential extractions. The measurements of pH, EC, and WSP were
performed in triplicate.
2.2. Collection and preparation of soils
Two representative sandy soils (Spodosol and Alfisol soil) were
collected at the depth of 0–20 cm from the University of Florida-Fort
Pierce farm and McAuthur citrus grove 3 in Fort Pierce, respectively.
The soils were air dried and sieved to <2 mm particle sizes prior to use.
Portions of soil (1.10 kg each) were mixed with each of the following P
fertilizers: DPR, HA-DPR, SLS-DPR, SP, or diammonium phosphate
(DAP) at the rate of 100 mg P/kg soil. A control (without any fertilizer)
was included. Each treatment had three replications. After the soil
moisture was adjusted to 70% field holding capacity, the P-spiked soils
were then incubated at room temperature for 21 days to gain chemical
equilibrium.
At the end of incubation, subsamples of the soils (about 50 g) were
taken, air-dried, and subjected to M3 extraction (Mehlich, 1984). Con­
centrations of P and metals in the M3 extracts were determined using
inductively coupled plasma optical emission spectrometry (ICP-OES,
Ultima, J.Y. Horiba Group, Edison, NJ, USA). The remaining soils were
used for column leaching studies as described in the following section.
2.3. Column leaching
The incubated soils (1.0 kg per column) were weighed and packed
into Plexiglas leaching columns (30.5 cm long, 6.6 cm inner diameter,
with several 5-mm diameter holes) to the bulk density of approximately
1.45 mg/cm3. A circle of Whatman No. 42 filter paper was placed at the
bottom of each column to prevent soil loss and another circle of filter
paper was placed on the surface of soil to mitigate preferential flow.
Prior to leaching, the soil columns were positioned upright in a plastic
pan (3.7 cm height, 14.2 cm inner diameter, each pan for one column)
containing deionized water to moisten the column from the bottom
upward until field-holding capacity was reached. Then the columns
were left upright at room temperature for 3 days to allow the soil to
compact naturally. Any leachate from the columns was collected into the
original pan and all the solution in each pan was collected and analyzed
in the same way as other leachate samples. The amount of P and other
elements lost in the pan was accounted for in the budget.
X. Wang et al. Journal of Environmental Management 255 (2020) 109872

The leaching was conducted at the intervals of 1, 3, 7, 14, 21, 28, and
56 days, respectively. At each leaching event, 150 mL of deionized water
was applied using a peristaltic pump, with a total of 1050 mL, which is
equivalent to the half year’s rainfall in the Indian River area (average of
2015–2016). Leachate solutions were collected from each leaching
event and analyzed for pH, EC, and concentrations of total soluble ele­
ments. pH and EC of leachate were determined immediately after each
leaching event using a pH/EC meter (Accumet AB 200, Fisher Scientific).
Subsamples of the leachate were filtered through a 0.45-μm membrane
filter and then acidified to pH < 2 with concentrated HNO3 prior to
analysis of elemental concentration using the ICP-OES.
After leaching, soil in the columns was taken out, air-dried, mixed
completely, and subjected to M3 extraction (Mehlich, 1984). The con­
centrations of microelements in the extracts were determined using the
ICP-OES. For the analysis of macro- and micro-elements using the
ICP-OES, quality assurance and quality control were followed, with
95–105% recovery of spiked standard for macro-elements and 90–110%
recovery of spiked standard for micro-elements. All the standards were
purchased from SPEXCertiPrep manufactured under UL LSO 9001
Quality System.
2.4. Statistical analysis
Data were expressed as means � SE (n ¼ 3). One-way ANOVA was
performed to determine the treatment effects using the SPSS (SPSS Inc.,
USA, version 17.0). Tukey HSD tests were conducted to make pairwise
comparisons at the 95% confidence level. The differences between the
treatments were considered statistically significant at P < 0.05.
3. Results
indicating that the activated DPR can supply P to crop with a small
quantity but long-lasting, similar to a slow release fertilizer. These
characteristics have important implications for their application in
agriculture in the environmentally sensitive regions such as Florida.
pH and EC of Alfisol and Spodosol soil before and after leaching were
shown in Table 2. SP treatment lowered the pH of both soils by 0.4 and
1.6 units, respectively, while DPR, HA-DPR and SLS-DPR raised pH of
both soils by 1.4–1.7 units. DAP also increased soil pH, but with a much
less extent. After leaching, the pH values of both control and treated soils
with DAP or SP increased, whereas those of Spodosol soil treated with
DPR or activated DPR slightly decreased and those of Alfisol soil with
DPR or activated DPR remained unchanged. Application of DPR or
activated DPR increased the soil pH regardless leaching events. Appli­
cation of SP significantly increased EC, followed by DAP, and the in­
crease was less for soils treated with DPR or activated DPR. The EC of all
soils decreased after leaching and reached a similar level (Table 2).
3.2. Leachate pH and EC
Application of DPR with or without activation resulted in a higher
leachate pH, an increase by 0.8–3.0 units, depending on leaching events
and soil types (Fig. 1), whereas SP application significantly lowered
leachate pH (by 0.6–2.2 units). Application of all P fertilizers increased
the EC of leachate samples, as compared to control, especially for the
soils received SP or DAP (Fig. 1). After the fifth leaching event, leachate
EC values from all the soils with P fertilizer application were similar to
that of control.
3.3. P leaching and retaining characteristics of soils applied with different
P fertilizers

3.1. Chemical properties of fertilizers and soils Leachate P concentration increased in the first four leaching events

pH, EC and WSP of original DPR, and DPR-derived activated and SP Table 2
fertilizers were presented in Table 1. SP had a low pH as it was prepared Chemical properties of control and treated soils before and after leachinga.
from acidification of DPR with concentrated sulfuric acid, whereas Treatments pH EC (μS/cm)
activation with HA or SLS increased the pH of DPR. SP, HA-DPR, and
Before After Before After
SLS-DPR had a higher EC value than the original DPR, indicating leaching leaching leaching leaching
enhanced solubility of DPR by the acidification or activation process.
Alfisol (control) 5.04 � 0.08 5.34 � 0.13 222.5 � 8.9 67.4 � 5.4
The amounts of WSP released from HA-DPR and SLS-DPR were 17.8 and
Alfisol-DAP 5.46 � 0.06 5.59 � 0.03 374.6 � 24.3 59.9 � 4.6
15.4 times larger than that from original DPR, respectively, although Alfisol-SP 4.63 � 0.00 5.26 � 0.10 1022 � 14.8 68.2 � 5.5
they were smaller as compared to SP. These results indicate that acti­ Alfisol-DPR 6.43 � 0.11 6.69 � 0.13 245.5 � 2.1 86.3 � 6.7
vation with HA or SLS enhances the release of WSP from DPR. However, Alfisol-HA-DPR 6.61 � 0.10 6.58 � 0.11 235.2 � 28.1 88.5 � 5.6
the activation efficiency varied between the two activating agents, with Alfisol-SLS-DPR 6.51 � 0.06 6.68 � 0.01 274.7 � 6.9 87.7 � 6.7
Spodosol 5.09 � 0.19 5.23 � 0.22 45.7 � 2.2 23.4 � 4.2
HA being more efficient than SLS. The increase in pH and WSP by (control)
activation could make DPR materials more useful in acidic soil regions Spodosol-DAP 5.39 � 0.19 5.88 � 0.11 312.5 � 15.3 54.3 � 3.2
due to enhanced neutralizing capacity for acidity and increased P Spodosol-SP 3.51 � 0.03 4.68 � 0.09 1071 � 14.8 43.1 � 8.8
availability. Spodosol-DPR 6.47 � 0.13 6.22 � 0.08 75.6 � 2.5 39.6 � 5.1
Spodosol-HA- 6.76 � 0.14 6.07 � 0.18 96.0 � 11.5 52.0 � 4.4
Most of WSP (91.1%) was released from SP in the first extraction, and
DPR
then declined rapidly, whereas only 1.1% of WSP was released from DPR Spodosol-SLS- 6.50 � 0.07 6.08 � 0.01 90.5 � 1.4 56.4 � 0.2
in the initial extraction, but WSP increased in the second and reached a DPR
peak in the third extraction. Total amount of WSP released from the a
Mean � SE (n ¼ 3).
activated DPR was intermediate between DPR and SP (Table 1),

Table 1
Chemical properties of fertilizersa.
Propertiesb pH (H2O) EC (mS/cm) WSP (g/kg)b

Total amount 1st (%) 2nd (%) 3rd (%) 4th (%) 5th (%) 6th (%)

DPR 8.19 � 0.01 0.22 � 0.01 0.51 � 0.05 1.1 11.0 34.2 14.0 16.6 23.2
SP 2.60 � 0.01 21.49 � 0.04 44.76 � 1.08 91.1 4.3 1.9 1.2 0.8 0.6
HA-DPR 9.23 � 0.02 3.51 � 0.12 9.06 � 0.34 69.8 15.8 5.8 4.8 2.5 1.4
SLS-DPR 8.45 � 0.04 3.93 � 0.02 7.84 � 0.15 73.2 14.5 4.5 3.0 2.6 2.3
a
Mean � SE (n ¼ 3).
b
WSP, water soluble P; DPR, dolomite phosphate rock; SP, superphosphate; HA-DPR, humic acid activated DPR; and SLS-DPR, sodium ligninsulfonate activated
DPR.

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X. Wang et al. Journal of Environmental Management 255 (2020) 109872

Control DAP Control DAP DPR

Alfisol DPR SP Spodosol
HA-DPR SLS-DPR SP HA-DPR SLS-DPR
8 8
7 7
6 6
pH

5 5
4 4
3 3
Control DAP
Alfisol
1 3 7 Control
DPR14 21 DAP
28 56
SP
Spodosol
1 3 7 DPR 14 21 SP28 56
HA-DPR SLS-DPR HA-DPR SLS-DPR
3500 3500
EC ( s/cm)

2800 2800
2100 2100
1400 1400
700 700
0 0
1 3 7 14 21 28 56 1 3 7 14 21 28 56

250 400 Control

DAP
200 DPR
SP
150
Soluble P (mg/L)

HA-DPR
200 SLS-DPR
100
50

4 10
3
2 5
1
0 0
1 3 7 14 21 28 56 1 3 7 14 21 28 56

Leaching event (d)

Fig. 1. Variation of pH, EC and soluble P in leachate with leaching events.

and decreased thereafter in Alfisol soil, while it increased in the first two
leaching events and then became steady in Spodosol soil (Fig. 1). SP and
DAP application significantly increased leachate P concentrations,
whereas DPR or activated DPR decreased leachate P concentration in
Alfisol soil, but increased it in Spodosol soil, as compared with control.
As compared to water-soluble fertilizers such as SP and DAP, application
of activated DPRs significantly reduced P leaching, although its leaching
potential was higher than original DPR material (Fig. 1).
Cumulative amount of P recovered in leachate was significantly
greater from water-soluble P fertilizers such as SP and DAP, as compared
to DPR or activated DPRs (Fig. 2). The largest P loss occurred in Alfisol
soil applied with DAP, but in Spodosol soil SP and DAP resulted in
similar P loss. The amounts of cumulative P leached from activated DPR
were 33–61 times less, as compared to SP or DAP. However, activation
with SLS or HA increased cumulative leachate P from both soils by 1–3
times, as compared to original DPR.
M3 extractable P in the soils before and after leaching was also
determined and shown in Fig. 3. The amount of M3 extractable P in
Alfisol soil was obviously higher than that in Spodosol soil. At the same
rate of WSP (100 ppm) added, the amounts of M3 extractable P in the
incubated soils before leaching were similar regardless fertilizer types
(Fig. 3A), with only a slight variability among the different soil and
fertilizer types. The amount of M3 extractable P was highest in SP
treated Alfisol soil; while the SLS-DPR treated Alfisol soil had the lowest
amount of M3 extractable P. However, in Spodosol soil, the highest M3
extractable P occurred in the DAP added soil, and the SLS-DPR treated
Spodosol soil had a relatively higher M3 extractable P. After leaching,
M3 extractable P in the incubated soils generally decreased but more
decrease occurred in the Spodosol than the Alfisol soil (Fig. 3B). Due to
greater leaching potential of SP and DAP (Fig. 2), after leaching M3
extractable P in the SP or DAP treated Spodosol soils was less than that in
the DPR or activated DPR treated soils. However, in Alfisol soil after
leaching the highest M3 extractable P occurred in the SP treatment,
although more P was also recovered in the leachate.

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X. Wang et al. Journal of Environmental Management 255 (2020) 109872

140 from the second leaching event and became steady thereafter.
a
a Cumulative amounts of Zn in leachate were the highest in soils
120 applied with SP regardless of soil type (Fig. 5). However, SP application
Cumulative P in leachate

100 a resulted in a decline in cumulative amount of leachate Cu, as compared

to SLS-DPR for both soils. The formation of complexes between Cu and
80
(mg/column)

b organic materials may explain the high leaching potential of Cu in the

60 soils applied with SLS-DPR fertilizer. As compared with SP, treatment of
HA-DPR or SLS-DPR reduced cumulative Zn in leachate by about 12.3
and 10.6 times for Alfisol soil, and by 1.9 and 2.4 times for Spodosol soil,
4 b respectively. Cumulative amounts of Cd, Co, Cr, Mo, Ni, and Pb in
3 c c leachate were also highest in leachate from the soils applied with SP,
d 1.3–3.6 times higher for Alfisol soil and 1.4–8.4 times higher for Spo­
2 e e d dosol soil, as compared with HA-DPR and SLS-DPR spiked soils (Fig. 5).
1
e Compared to DPR, HA-DPR or SLS-DPR slightly increased the leaching of
0 Ni and Pb in Alfisol soil, and Cd and Mo in Spodosol soil. But the in­
Alfisol Spodosol creases were negligible as compared to those caused by SP treatment.
Control DAP DPR Cumulative trace metals in leachate accounted for <4.0% of M3
SP HA-DPR SLS-DPR extractable trace metals in the activated DPR treated soils except for Cd
(Fig. 6). The percentages of leachate Cd in M3 extractable soil Cd were
Soils
generally higher, as compared to other metals for the same treatments.
Fig. 2. Cumulative P amounts in total leachate. Among the different treatments, SP-amendment persistently resulted in
the highest percentage for the same trace metal except for Cu (Fig. 6).
3.4. Leaching characteristics of trace metals in soils applied with different
P fertilizers 4. Discussion

Of the eight trace metals (Cu, Zn, Pb, Cd, Co, Cr, Mo, and Ni), only Zn 4.1. Activated DPR alleviated the leaching effect of P in sandy soils
was detected in leachate throughout all the leaching events for both soil
types, and Cu was measured in all the leachate samples from Alfisol soils Water-soluble P fertilizers are directly available to plants. Applica­
(Fig. 4). Concentrations of other metals in leachate samples were below tion of WSP fertilizers is vital to sustain desired crop yield. However,
the detection limits, especially after the fourth leaching event. Zinc nutrient utilization efficiency by crops is currently very low, especially
leaching characteristics were different between the Alfisol and Spodosol for P and micronutrients. Fertilizer P that is not taken up by crop plants
soil. Leachate Zn concentrations increased in the first two leaching is subjected to leaching loss (Chen et al., 2006; Yang et al., 2008) or
events, then declined, and became steady after the third leaching event fixation by soil components such as iron/aluminum oxides and clay
in the Alfisol soil except for the SP-spiked samples, in which leachate Zn minerals in acidic soils (G�erard, 2016; Vaneeckhaute et al., 2016). For
increased unexpectedly at the fifth leaching event. In Spodosol soil, instance, WSP leaching loss was as high as 96.6% in Wabasso soil
maximum Zn leaching occurred in the fourth leaching event and then applied with monosodium phosphate (MSP) (Chen et al., 2006). In the
decreased. By comparison, SP and DAP application increased leachate present study, at the same P rate (100 ppm WSP), the leaching loss of
Zn, with the only exception occurring at the fourth leaching event of WSP was 114 � 14.7%, and 63.6 � 1.5%, respectively for SP in the
Spodosol soil, in which the maximum leachate Zn concentration was Spodosol and Alfisol soil. The corresponding values for DAP were 108 �
measured in the DPR-spiked soils. Leachate Cu concentrations increased 9.1% and 82.3 � 9.3%. These results indicate that WSP fertilizers may
in the first three leaching events and reached maximum in the third not be suitable for use in the sand soils due to intensive leaching loss.
leaching event for the DAP- and SP-spiked Alfisol soils. But leachate Cu Soil properties, such as pH, EC, contents of clay, organic matter, and
from Control, DPR-, HA-DPR-, and SLS-spiked Alfisol soils increased Fe/Al oxides, affect P-retaining capacity and subsequent P leaching

240 A 140 100 B a

Mechlich 3 extractable P (mg/kg)
Mehlich 3 extractable P (mg/kg)

a
120 a ab
a
ab
200
Cumulative P contents in

100 a a 80 bc
leachate (mg/column)

160 b b 80bc ab ab
b
c bb 60 c
120 60 a a
40 a
80 d
4 b b
d 20 c
40 3 c c c
d
2 c
e e
0 0 d
1
Alfisol Spodosol Alfisol Spodosol
Control
e Control DAP DPR
0 DAP DPR
SP Alfisol SLS-DPR
HA-DPR SpodosolSP HA-DPR SLS-DPR
Soils Soils
Control DAP DPR
SP HA-DPR SLS-DPR

Soils
Fig. 3. Labile P in the soils before (A) and after leaching (B) based on M3 extraction.

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X. Wang et al. Journal of Environmental Management 255 (2020) 109872

3000 potential (Summers et al., 2000; Elliott et al., 2002; Shuman, 2003; He
Alfisol-Zn
et al., 2005; Yang et al., 2013). Sandy soils contained only a small
2000 amount of clay, organic matter and Fe/Al oxides, and being acidic, and
Zn concentrations ( g/L)

therefore, water soluble fertilizer P are subjected to great P leaching loss,

1000 especially during the rainy season such as June to November in Florida
(Summers et al., 2000; Elliott et al., 2002; Chen et al., 2006).
600 However, the results from the present study clearly showed P fer­
tilizers applied in DPR and activated DPRs tended to stay in soil without
subjecting to leaching loss, as evidenced by < 3.2% of WSP in DPR and
400 activated DPRs being leached, much less than that for SP and DAP. For
most organic or inorganic fertilizers like compost, manures and chemi­
cal fertilizers P leaching loss is often proportional to total WSP in the
200 fertilizers (Kleinman et al., 2002; Kang et al., 2011). However, for DPR
and activated DPRs P leaching loss was significantly lower than that
0 from SP or DAP even at equal amount of WSP applied. This could be
1 3 7 14 21 28 56 attributed to the slow release characteristics of WSP from the activated
DPRs. The release of WSP from activated DPRs is demand-driven, similar
1600 to a slow release fertilizer. The activated DPR fertilizers can be persistent
Spodosol-Zn in the sandy soils without subjecting to significant leaching loss.
concentrations ( g/L)

1200 Furthermore, P leaching is related to soil pH, which was raised by DPR
800 or activated DPR fertilizers, thus reducing P leaching loss. Zhao et al.
(2006) found that pH 6.0 was a turning point, and more P is adsorbed by
400 soils at pH > 6.0, but the amount of adsorbed P tended to decrease at pH
Concentrations

< 6.0. Application of activated DPRs to the sandy soils increased soil pH
150 and thus enhanced the adsorption capacity of soils for P, then indirectly
reduced the leaching loss of P from these soils.
Besides, M3 extractable P serves as an index for estimating potential
100 P availability in soil. Water-soluble P fertilizers are prone to leaching in
(µg/L)

sandy soils. For example, leachate P in the M3 extractable P accounted

for approximately 22% in Alfisol soil (Yang et al., 2013). In the present
Zn

50 study, P recovery in column effluents (100 � leached/M3 extractable P

in soils before leaching) were 55.5% and 66.6%, respectively for DAP
0 treated Alfisol and Spodosol soils, and the corresponding values were
1 3 7 14 21 28 56 33.7% and 78.4%, respectively with SP (Figs. 2 and 3). These results
indicate that P leaching in sandy soils applied with water-soluble P
fertilizers may represent a serious problem of environmental pollution.
1200 As compared to DAP and SP, leaching loss of M3 extractable P in soils
Alfisol-Cu received DPR or activated DPRs was much less (Figs. 2 and 3). M3
extractable P in Alfisol soils spiked with DPR or activated DPR fertilizer
Cu concentrations ( g/L)

(HA-DPR or SLS-DPR) was similar to that treated with water-soluble P

900 fertilizers such as DAP or SP. However, P leaching from DPR or activated
DPR treated soils was significantly lower than that from the SP or DAP
treated soils, with <2.5% of M3 extractable P being leached from the
soils applied with DPR or activated DPR after 7 leaching events. These
600 results imply that activated DPR fertilizers have much smaller leaching
potential as compared to water-soluble fertilizers and therefore, are
useful for the environmentally sensitive areas such as sandy soil region
300 in Florida (Xiong et al., 2002; Chen et al., 2006; Yang et al., 2013). The
amounts of leachate P plus residual M3 extractable P in the leached soils
were comparable with the total amounts of M3 extractable P in the soils
before leaching for control, SP-spiked, and DAP-spiked soils. However,
0 for DPR- and activated DPR-spiked soils, the sum of the leachate P and
1 3 7 14 21 28 56 the residual M3 extractable P was significantly lower than the total M3
extractable P in the soils prior to leaching. These results indicated that
Alfisol the interaction of soil components with water-soluble P was relatively
small in the acidic sandy soils, whereas addition of DPR or activated DPR
Control DAP DPR raised soil pH and subsequently enhanced the formation of Fe and Al
SP HA-DPR SLS-DPR oxides, which can adsorb phosphate, thus resulting in a decrease in M3
extractable P by more than 48% (Fig. 3).

1200 4.2. Activated DPR reduced leaching loss of trace metals in sandy soils

Leaching event (d) In phosphate rocks, radiative elements, trace metals, and rare earth
Fig. 4. Variation of Zn and Cu concentrations in leachate with leaching events.
elements are three kinds of contaminants of concern, of which Pb, Cd
)

and Zn are of special concern, since up to 44.5 mg/kg of Pb, 60 mg/kg of

Cd and 515 mg/kg of Zn were determined in some phosphate rocks

6
X. Wang et al. Journal of Environmental Management 255 (2020) 109872

1.4 0.25
Alfisol Spodosol
a a
1.2
0.20

Cumulative amounts in
leachate (mg/column)
1.0

Cumulative contents in
leachate (mg/column)
0.8 0.15
a
0.6 ab a
0.10 bc
b bc b bc
c
0.4 c b b b
0.05
a
0.2
d c c c b a
c c
0.0 0.00
Cu Zn Cu Zn
Elements
120 160 Elements
Spodosol 160
Alfisol Spodosol
a a
140 a 140
Cumulative contents in
Cumulative amounts in

100

Cumulative contents in
leachate ( g/column)
leachate ( g/column)

leachate ( g/column)
120 120
a a
60 a
60 a aa
40 a a
ab 40
bcc b b a
ab a a
a 40 bb b b
20 bb b bb bb
bbb bb b b b b b c bcb a 20
a b
b b d b b bc cd bcd b bb
d c c bc bc b b b c
a c c bc c bbc bcb b d dc c
20 bc b
0 b c bcb b b 0ccd bcd b bb
Cd Co c
Cr Mo c cbcNi Pb
bc
c bc bc d Cd d c Co c Cr Mo Ni Pb
Control DAP DPR Control DAP DPR
SP 0 HA-DPR SLS-DPR SP HA-DPR SLS-DPR
Cd Co Cr Mo Ni Pb
Control DAP DPR
SP HA-DPR SLS-DPR

Elements
Fig. 5. Cumulative amounts of microelements in leachate.
Percentage of trace metals loss
as in M3 extractable (%)

100 80
Alfisol a Spodosol
80 a
70
b
b Control
DAP
40 DPR
30 SP
cd
c
d
30 HA-DPR
SLS-DPR
20
a 20
a a
a e a a
10 b
b
10 a a
c cbc db c c c a b b
b abbb b
bb
cbb bb ba cc cb ccb c c b b bbb bb bb bb
c cc c
0 0
Cu Zn Cd Cr Ni Pb Cu Zn Cd Cr Ni Pb

Control DAP DPR

SP HA-DPR SLS-DPR

80
Spodosol Elements
70 a
Fig. 6. Percentage of Cumulative amounts of Cu, Zn, Cd, Cr, Ni and Pb in leachate as in M3 Extractable amounts in soil.

(Siddique et al., 2018). The higher contents of trace metals in PR ma­ DPR/activated DPR and DAP treatments were minimal, and soils
terials may result in greater leaching potential of trace metals in soils as received DPR and activated DPR fertilizers actually lowered the con­
compared to chemical fertilizers without trace metals such as DAP. DPR centrations of Cu, Zn in leachate (Fig. 4). Although DPR/activated DPR
fertilizers produced by mixing DPR materials with N-Viro soil were re­ fertilizers added trace metals to soils, but they were not active, being
ported to have higher concentrations of Cu (1–6 times) and Co (1.5–2 locked in the mineral lattice. Moreover, amendment of DPR fertilizers
times) in leachate (Yang et al., 2013). However, in the present study raised soil pH and consequently reduced leaching loss of trace metals
only Spodosol soils amended with DPR or activated DPR resulted in from the amended soils. For the SP amended soils, the added trace
slightly higher concentrations of Ni and Mo, as compared to DAP-treated metals are active and subjected to leaching. In addition, SP amendment
soils. The differences in leachate Cd, Co, Cr and Pb between decreased soil pH and subsequently enhanced the activity and leaching

7
X. Wang et al.
potential of trace metals (He et al., 2005). As a consequence, SP
amendment resulted in the highest amounts of trace metals in leachate
except for Cu and Zn.
For some leaching events, the concentrations of Cd and Pb were up to
46.1 and 156.7 μg/L in leachate from the Alfisol soils and 40.1 and
116.7 μg/L from Spodosol soils amended with activated DPR, which
were higher than the drinking water quality guidance limits ruled by
Florida Department of Environmental Protection (FDEP) (5 and 15 μg/L)
and World Health Organization (WHO) (4.5 and 10 μg/L). Similar Pb
leaching results were observed by Gove et al. (2001) in water from sandy
soils treated with biosolids and Yang et al. (2013) in leachate from sandy
soils spiked with N-vero based DPR fertilizers. The difference in
maximum leachate concentration of Pb might be caused by the differ­
ences in properties between soils and source materials of DPR fertilizers.
For instance, N-vero materials was composed of sewage sludge and fly
ash, both containing variable amounts of trace metals such as Pb.
In the present study, the same amount of DAP or activated DPR
fertilizers was applied to Alfisol or Spodosol soil, but the leaching
characteristics of trace metals from the two soils were different. M3
extractable Cu, Zn, and Cr in Alfisol soil (31.98, 10.38 and 0.22 mg/kg,
respectively) were higher than those in Spodosol soil (1.26, 3.65 and
0.18 mg/kg, respectively), whereas M3 extractable Cd, Ni and Pb in
Alfisol (60.9, 243.4 and 1005 μg/kg, respectively) were lower than those
in Spodosol soil (114.5, 408.5 and 1388 μg/kg, respectively). However,
the maximum concentrations of trace metals in leachate from Alfisol soil
were always higher than those from Spodosol soil for control, or
amended with DAP, DPR, or activated-DPR. Apparently, the retaining
capacity of Spodosol soil for trace metals was larger than Alfisol soil.
However, SP amendment persistently resulted in higher concentrations
of Cd (55.0 and 57.0 μg/L), Ni (172.5 and 221.1 μg/L), Pb (408.5 and
502.8 μg/L) regardless of soil type, as compared to control or other
amendments.
The highest Cu and Zn concentrations occurred in leachate from DAP
(1193 μg/L for Cu) and SP-amended (2881 μg/L for Zn) Alfisol soils, as
compared to 145.6 μg/L of Cu in SLS-DPR treated Spodosol soil and
1456 μg/L of Zn in original DPR treated Spodosol soil. Zinc concentra­
tions in all the leachate samples were below FDEP (5000 μg/L) and WHO
(3000 μg/L) limits, whereas Cu concentrations in leachate from DAP-
amended Alfisol soil were slightly above the FDEP (1000 μg/L) and
WHO (1000 μg/L) limits in the second and third leaching events. HA and
SLS activation resulted in declined Cu and Zn concentrations to below
the FDEP and WHO limits, which were similar to the results of Yang
et al. (2013) who studied the DPR fertilizers produced by mixing DPR
with N-Viro soil. However, Cu and Zn leaching characteristics were
different between Cu and Zn, with higher leaching of Cu, but lower
leaching of Zn from the SLS-DPR amended than the SP-treated soils. On
the other hand, M3 extractable Cu from SLS-DPR amended soils (33.7
and 2.5 g/kg, respectively for Alfisol and Spodosol soil) was higher than
that from SP (32.4 and 1.4 g/kg, respectively for Alfisol and Spodosol
soil), whereas M3 extractable Zn in SLS-DPR amended soils (11.9 and
3.4 g/kg, respectively for Alfisol and Spodosol soil) was lower than the
SP amended soils (13.8 and 4.5 g/kg, respectively for Alfisol and Spo­
dosol soil). Yu et al. (2019) reported similar results that activation of
DPR with organic agents reduced trace metal release from DPR, whereas
the release of Cu increased. This may result in higher Cu leaching from
SLS-DPR amended than the SP amended soils. Moreover, the differences
in physicochemical properties of Cu and Zn, such as ionic radius, elec­
tronegativity, softness and hydrolysis might have resulted in the dif­
ferences in Cu and Zn adsorption by soil components (Wang and Li,
2011). Sodium lignosulphonate is an effective absorbent and has a
greater affinity for Cu than Zn (Ma et al., 2019). Consequently, Cu was
more chelated to SLS and, and leached with SLS, as compared with Zn,
thus leading to higher Cu concentration in leachate.
The changes of physical-chemical properties may have influenced
the mobility of trace metals in the amended soils, as the solubility of
trace metals is sensitive to the changes in pH (Kabata-Pendias, 2001). A
8
Journal of Environmental Management 255 (2020) 109872
decrease in pH after sulfur application was reported to increase the
solubility and uptake of soil Zn and Cd by sunflower and maize (Kayser
et al., 2000). Increased concentrations of soluble salts may displace
weakly sorbed metals and thus increase the concentrations of trace
metals in soil solution. When exposed to high NaCl concentrations, the
leaching of trace metals was enhanced (Norrstro €m and Jacks, 1998;
Ba€ckstro
€m et al., 2004). In the present study, the pH of soils significantly
decreased after SP application (Table 2) and thus increased the solubility
and leaching of trace metals. Meanwhile, the EC of soils obviously
increased after SP treatment (Table 2), which may also enhance the
leaching of trace metals. The relatively small change in soil pH and EC
by DAP application had less effect on trace metal solubility and leaching,
as compared to SP. The changes in soil or leachate pH and EC caused by
HA-DPR or SLS-DPR amendment were similar to that of original DPR.
The increase in pH and EC tended to decrease leaching of metals from
soils. However, HA- or SLS-DPR treatment, to a certain degree, increased
leaching of Zn, Ni and Pb from Alfisol, Cd and Mo from Spodosol, and Cu
from both soils. The organic materials added to soils in the activated
DPR fertilizers might have enhanced solubility and mobility of these
trace metals in soils (Berggren, 1990; Wu et al., 2002; Zhang and Zhang,
2010). Water soluble organic-metal complexes can be formed between
soil organic matter and trace metals (Li and Shuman, 1996). In the
present study, amendment of HA-DPR or SLS-DPR added HA or SLS to
the soils, and therefore slightly promoted leaching of some trace metals
in the soil, due to the formation of metal-activation agent complexes.
5. Conclusions
Activated DPR fertilizers had much smaller leaching potential for P
as compared with water-soluble P fertilizers such as SP, though greater
than original DPR. In addition, the activated DPR fertilizers had a lower
leaching potential for trace metals, including Zn, Cd, Co, Cr, Mo, Ni, and
Pb than the SP made from the same DPR material. These results indicate
that activated DPR fertilizers are more environmentally friendly than
water-soluble fertilizers and suitable for application in those environ­
mentally sensitive regions such as sandy soil areas in Florida.
Acknowledgments
This study was supported by a grant from the Florida Institute of
Phosphate Research (FIPR no. 15-01-208). China Scholarship Council
provided a scholarship to Dr. Xiaoli Wang for one year visiting research
at the University of Florida (CSC NO. 201606175203). The authors
thank the Mosaic Fertilizer Company for assistance with collection of
DPR samples, and Brian M. Cain for his assistance in the determination
of metals in the soil and leachate samples.
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