Chemosphere 255 (2020) 127005

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

A new approach to removing and recovering phosphorus from

livestock wastewater using dolomite
Zhichao Yin b, c, Qingfeng Chen a, b, *, Changsheng Zhao b, Ying Fu c, Jinye Li b, You Feng b,
Lei Li b
a
College of Geography and Environment, Shandong Normal University, Jinan, 250014, Shandong, China
b
Qilu University of Technology (Shandong Academy of Sciences), Shandong Analysis and Test Center, Key Laboratory for Applied Technology of
Sophisticated Analytical Instrument of Shandong Province, Jinan, 250014, China
c
School of Civil Engineering and Architecture, University of Jinan, Jinan, 250022, China

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

Dolomite can provide calcium and

magnesium sources as cheap ore.

The phosphorus removal rate for
livestock wastewater was 92% under
the optimal conditions.

The cost of dolomite to treat high-
phosphorus wastewater was at least
25.9% lower than the other chemicals
raw material.

Recovered product was mainly the
HAP precursor ACP and 1.67% MAP.

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

Article history: Recovering phosphorus from livestock wastewater could partly mitigate the global phosphorus resource
Received 30 March 2020 crisis. Crystallization is a promising method for removing phosphorus from wastewater, but the costs of
Received in revised form calcium- and magnesium-containing reagents are increasing. Cheap, available, efficient materials are
30 April 2020
required to replace conventional calcium and magnesium reagents. Here, we describe a new approach to
Accepted 6 May 2020
removing and recovering phosphorus from livestock wastewater of a large pig farm, containing a high
Available online 10 May 2020
phosphorus concentration. The effects of the pH, stirring speed, stirring time, and extract dose (con-
Handling Editor: Veeriah (Jega) Jegatheesan taining calcium and magnesium) on phosphorus removal from livestock wastewater were investigated.
The product was characterized by X-ray diffractometry, Fourier-transform infrared spectroscopy, and
Keywords: scanning electron microscopy. Under optimized conditions (pH 9.0, stirring speed 200 r/m, stirring time
Livestock wastewater 600 s, Ca 207.62 mg/L, Mg 122.86 mg/L), 92% of the phosphorus was removed from livestock wastewater.
Phosphorus removal and recovery The product was mainly the hydroxyapatite (Ca5(PO4)3OH) precursor amorphous calcium phosphate but
Dolomite also contained 1.65% (by mass) magnesium ammonium phosphate (MgNH4PO4$6H2O) crystals. The cost
Magnesium ammonium phosphate
of dolomite to treat 1 m3 of high-phosphorus wastewater was 0.20 yuan (45.9%, 25.9%, and 75.9% lower
Hydroxyapatite
than for pure MgCl2, MgSO4, and CaCl2, respectively) in 2019. Using dolomite to provide calcium and
magnesium effectively decreases the crystallization process cost and should encourage the use of
crystallization to remove phosphorus from wastewater.
© 2020 Elsevier Ltd. All rights reserved.

* Corresponding author. Wenhua Donglu 88#, Jinan, Shandong, 250014, China.

E-mail address: chensdcn@163.com (Q. Chen).

https://doi.org/10.1016/j.chemosphere.2020.127005
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
2 Z. Yin et al. / Chemosphere 255 (2020) 127005
1. Introduction
There are limited reserves of phosphate rock, which is a non-
renewable resource. According to data published by the US
Geological Survey in 2017, global phosphate rock reserves are
~300  109 t. Based on current consumption rates, global phosphate
rock reserves will be exhausted in 300 y (Zhang, L. et al., 2017; Hao,
X D. et al., 2010). China is the main consumer of phosphate rock. It is
predicted that China may have a phosphate rock shortage from
2050 and that the phosphate rock resource crisis will become
increasingly severe (Cui, R G. et al., 2019).
Large numbers of livestock are bred in China, and more pigs,
sheep, and small livestock (including poultry) are reared in China
than any other country. The first national census of pollution
sources in China indicated that livestock-breeding (including
poultry-breeding) facilities are the main agricultural non-point-
sources of water pollution in China, contributing 96%, 38%, and
56% of chemical oxygen demand, total nitrogen, and total phos-
phorus emissions, respectively, from agricultural sources (Zhang, Y.
et al., 2016). Large amounts of phosphorus-containing wastewater
are discharged into surface water. This causes eutrophication of
water bodies and serious water pollution problems. Recovering and
reusing phosphorus in wastewater produced in livestock-breeding
facilities could effectively mitigate the phosphorus resource crisis.
Therefore, much research into techniques for removing, recovering,
and reusing phosphorus in wastewater is being performed
(Venkiteshwaran, K. et al., 2018; Wu, Y. et al., 2019).
Crystallization is a promising method for removing phosphorus
from wastewater. Crystallization has several advantages over other
methods, including being quick and efficient, so a great deal of
attention around the world has been paid to crystallization in
recent years (Lin, L. et al., 2019; Zheng, B Y. et al., 2019). The most
common crystallization method involves removing and recovering
phosphorus by causing magnesium ammonium phosphate
(MgNH4PO4$6H2O) and hydroxyapatite (Ca5(PO4)3OH) crystals to
form (Ma, H Y. et al., 2018; Lou, Y Y. et al., 2018). This is achieved
using common sources of calcium and magnesium, typically MgCl2,
Mg2SO4, and CaCl2 (Han, X R. et al., 2017; WuPing and Li, 2017;
Wang, Q Q. et al., 2018; Ren, W C. et al., 2015). These chemicals are
expensive, making removing phosphorus from wastewater by
crystallization expensive as well. A cheap, readily available, efficient
source of calcium and magnesium would effectively decrease the
cost of removing phosphorus from wastewater by crystallization.
This would allow crystallization to be used to remove phosphorus
from wastewater more widely than is currently the case.
Dolomite (CaMg (CO3)2) is a cheap natural mineral found in rich
reserves that are widely distributed (Liu et al., 2003). In this study,
an acidified dolomite solution containing high calcium (Ca2þ) and
magnesium (Mg2þ) ion concentrations was prepared by dissolving
dolomite in dilute hydrochloric acid (HCl). The dolomite solution
was used to remove and recover phosphorus from livestock
wastewater. The effects of the pH, hydrodynamic conditions, and
dolomite solution dose on the phosphorus recovery efficiency were
investigated. The operating parameters were optimized, and the
recovered product was characterized. The results were expected to
support the development of large-scale crystallization facilities for
removing and recovering phosphorus from wastewater.
2. Materials and methods
2.1. Experimental materials
Commercially available dolomite was used. The dolomite con-
tained 30%e31% CaO, 21.5%e22.5% MgO, and small amounts of SiO2,
Al2O3, and Fe2O3 (<1.2%, <0.5%, and <0.1%, respectively). The
dolomite was ground and passed through 20-, 60-, 100-, and 200-
mesh sieves.
Livestock wastewater from a large pig farm in Linyi, Shandong
Province, China was used. Simulated high-phosphorus wastewater
þ
containing 100 mg/L P as PO3 4 and 500 mg/L N as NH4 was pre-
pared by dissolving KH2PO4 and NH4Cl in deionized water. The
nitrogen and phosphorus concentrations used were similar to the
concentrations in the livestock wastewater.
All of the chemicals used (including KH2PO4, NH4Cl, NaOH, HCl,
and H2SO4) were of analytical grade.
2.2. Phosphorus removal and recovery mechanism
The livestock wastewater contained high nitrogen and phos-
phorus concentrations. Phosphorus can be removed from waste-
water and recovered as MAP and HAP crystals by adding Ca2þ and
Mg2þ under controlled conditions. MAP and HAP form through the
reactions shown in Eqs. (1) and (2).
Mg2þ þ NH4þ þ PO3
4 þ 6H2 O/MgNH4 PO4 ,6H2 OY (1)

5Ca2þ þ 3PO3
4 þ OH /Ca5 ðPO4 Þ3 OHY (2)
The solution will become supersaturated with the product if the
ion activity product of a reactant exceeds the solubility product
(Ksp ) of the product. MAP and HAP crystals will precipitate spon-
taneously when the solution becomes supersaturated, allowing
phosphorus to be recovered (Hao, X D. et al., 2010).
2.3. Experimental methods
2.3.1. Preparation of acidified dolomite solution
A 1 g aliquot of dolomite was accurately weighed into a 50 mL
beaker, then 6 mol/L HCl was added. The reaction was allowed to
proceed for some time, then deionized water was added to bring
the volume to 50 mL. The effects of using different reaction tem-
peratures, dolomite mesh sizes, and acidic solution doses on the
Ca2þ and Mg2þ concentrations in the solution (i.e., released from
the dolomite) were evaluated. Changes in the solution pH were also
determined.
2.3.2. Factors affecting the phosphorus removal efficiency
Simulated wastewater (400 mL) was added to a beaker, then an
aliquot of the dolomite solution was added and the pH was adjusted
by adding 1 mol/L or 5 mol/L NaOH. The beaker was placed on a
ZR4-6 six-paddled stirrer (Zhongrun Water Industry Technology
Development Co., Shenzhen, China) and was stirred for a specified
time at a specified speed. After the specified time had passed, the
solution was allowed to stand for 20 min for a precipitate to form.
The mixture was passed through a 0.45 mm membrane filter, then
þ
the concentrations of P as PO3
4 and N as NH4 in the filtered solution
were determined. The solid product collected on the 0.45 mm filter
was dried at 40  C and then analyzed. The effects of using different
pH values, stirring speeds, stirring times, and dolomite solution
doses on the phosphorus removal efficiency were assessed.
2.4. Analytical methods and instruments
The water samples were analyzed following a method published
in “Water and Wastewater Monitoring and Analysis Methods
(Fourth Edition)”. P as PO3
4 was determined by
molybdenumeantimony anti-spectrophotometry. N as NHþ 4 was
determined by adding Nessler’s reagent and then using a 756S/
759S UVevisible spectrophotometer (DorYang, Shanghai, China).
 Z. Yin et al. / Chemosphere 255 (2020) 127005 3

The pH was determined using a PHS-3C pH meter (Leici, Shanghai,

China). Stirring was performed using a ZR4-6 coagulation test
stirrer (ZhongRun, Shenzhen, China). The precipitated product was
characterized by X-ray diffractometry (XRD), Fourier-transform
infrared spectroscopy (FTIR), and scanning electron microscopy
(SEM). The MAP content of the product was determined by per-
forming elemental analysis.

3. Results and discussion

3.1. Factors affecting the release of Ca2þ and Mg2þ

3.1.1. Effect of the reaction temperature

The Ca2þ and Mg2þ concentrations in solution (i.e., released
from the dolomite) over time at temperatures of 20, 30, and 40  C
were determined. The results found at the different reaction tem-
peratures are shown in Fig. 1(a).
The Ca2þ and Mg2þ concentrations initially increased over time,
but after a certain time the Ca2þ and Mg2þ concentrations no longer
changed because equilibrium had been reached, as shown in
Fig. 1(a). The Ca2þ or Mg2þ concentration at equilibrium was the
same at each temperature, but the time required to reach equilib-
rium was different at each temperature. Equilibrium was reached at
~30 min at 40  C, 60 min at 30  C, and 180 min at 20  C. These
results indicated that the time required to reach equilibrium
decreased as the temperature increased. This would have been
because dolomite reacted with the acidic solution to produce CO2.
The solubility of CO2 decreases as the temperature increases, and
CO2 escaping from the solution will have caused the reaction to
proceed, accelerating the acidification reaction. Increasing the
temperature increased the reaction rate and shortened the reaction
time without affecting the Ca2þ and Mg2þ concentrations at equi-
librium. The temperature in the laboratory varied between 20 and
30  C under normal conditions. A dolomite solution with the same
Ca2þ and Mg2þ concentrations could therefore be produced in
180 min at the usual room temperature.

3.1.2. Effect of the dolomite mesh size

The Ca2þ and Mg2þ concentrations in the dolomite solution over
time when 20-, 60-, 100-, and 200-mesh dolomite particles were
used at room temperature were determined, and the results are
shown in Fig. 1(b).
The Ca2þ and Mg2þ concentrations first increased over time,
then remained constant once equilibrium had been reached
(Fig. 1(b)). The time taken for equilibrium to be reached was
different for each dolomite particle size. Equilibrium was reached at
~30 min using 200-mesh dolomite, ~60 min using 100-mesh
dolomite, and 180 min using 20- or 60-mesh dolomite. This
would have been because the specific surface area increases as the
particle size decreases. This means that, at a given dolomite dose,
the smaller the particles the larger the surface area in contact with Fig. 1. Effect of the reaction temperature (a)，different dolomite particle sizes (b) and
different acidic solution doses (c) on the Ca2þ and Mg2þ concentrations in solution (i.e.,
acid and the quicker equilibrium is reached. The Ca2þ and Mg2þ
released from dolomite).
concentrations at equilibrium were higher for the 100-mesh
dolomite than the 20- and 60-mesh dolomite. The Ca2þ and Mg2þ
concentrations were similar for the 200-mesh dolomite and 100- shown in Fig. 1(c).
mesh dolomite, but it was more expensive to prepare 200-mesh At the same temperature and reaction time, increasing the
dolomite than 100-mesh dolomite. Subsequent experiments were acidic extract dose caused the Ca2þ and Mg2þ concentrations to
therefore performed using 100-mesh dolomite. increase and the pH to decrease (Fig. 1(c)). The Ca2þ and Mg2þ
concentrations increased almost linearly and the pH decreased
3.1.3. Effect of the extract dose slowly as the extract dose increased to 3.4 mL. Up to this dose,
The 100-mesh dolomite was reacted with different doses of the excess dolomite was present, and the acid completely reacted with
acidic solution at room temperature for 180 min. The acidic extract the dolomite. Increasing the extract dose to 3.6 mL caused the pH to
doses were 1, 2, 3, 3.2, 3.4, 3.6, 3.8, 4, 5, and 6 mL. The effects of decrease rapidly to pH 2.34 (from pH 4.92 at an extract dose of
using the different acidic extract doses on the release of Ca2þ and 3.4 mL). This indicated that there was an excess of acid when the
Mg2þ and the pH of the extract were assessed, and the results are
4 Z. Yin et al. / Chemosphere 255 (2020) 127005

dose was 3.6 mL, and all of the dolomite reacted. At extract dose
s > 3.6 mL the Ca2þ and Mg2þ concentrations and pH did not change
markedly, indicating that the Ca2þ and Mg2þ in the dolomite had
been completely released. The subsequent reaction was performed
under slightly alkaline conditions, so the optimal extract dose was
determined to be 3.4 mL.

3.2. Phosphorus removal efficiency of the acidified dolomite

solution

A 1 g aliquot of 100-mesh dolomite was added to a beaker, then

3.4 mL of the acidic solution were added and the mixture was
allowed to react at room temperature for 180 min. The solution was
then transferred to a 50 mL volumetric flask and diluted to 50 mL.
The mixture was passed through a filter, and the Ca2þ and Mg2þ
concentrations in the solution, determined by inductively coupled
plasma spectroscopy, were 4360 and 2580 mg/L, respectively.

3.2.1. Effect of the initial pH

Fig. 2. Phosphorus removal efficiencies found at different initial pH values.
The effect of the initial pH on the phosphorus removal efficiency
of the dolomite solution was investigated by performing tests at
initial pH values of 7.5, 8.0, 8.5, 9.0, 9.5, and 10. phosphorus concentration in the untreated water (100 mg/L).
The phosphorus removal rate increased as the pH increased These results indicated that the hydrodynamic conditions affected
(Fig. 2). Increasing the initial pH from 8.5 to 9.0 caused the residual the phosphorus removal efficiency but were not the dominant
phosphorus concentration in the solution to decrease from 28.69 to conditions affecting the phosphorus removal efficiency. Taking
9.35 mg/L and the phosphorus removal rate to increase from 73% to energy consumption and costs into account, the optimal stirring
91%. This indicated that increasing the initial pH from 8.5 to 9.0 speed and stirring time were concluded to be 200 r/min and 600 s,
markedly changed the removal rate. Increasing the initial pH to 9.5
and 10.0 increased the phosphorus removal rate to 97% and 99%,
respectively. The data were subjected to analysis of variance
(ANOVA), performed using SPSS software. The ANOVA indicated
that the residual phosphorus concentrations at initial pH values of
8.5 and 9 were significantly different (a ¼ 0.05). The residual
phosphorus concentrations at initial pH values of 9, 9.5, and 10
were not significantly different. More alkali needed to be added to
change the solution from pH 9.0 to 9.5 and from pH 9.5 to 10.0 than
from pH 8.5 to 9.0. If the initial pH was too high the Ca2þ and Mg2þ
in solution would readily react with OH to form Ca (OH)2 and Mg
(OH)2, which would affect the progress of the desired reactions.
Therefore, the optimal initial solution pH was concluded to be 9.0.

3.2.2. Effects of the hydrodynamic conditions

The effects of different hydrodynamic conditions on the phos-
phorus removal efficiency were investigated by performing tests
using different stirring speeds and stirring times. Each solution had
an initial pH of 9.0.
The phosphorus removal efficiencies found when the dolomite
solution was stirred at different speeds are shown in Fig. 3(a).
Increasing the stirring speed first increased and then decreased the
phosphorus removal rate. The maximum phosphorus removal rate,
93% (which corresponded to a residual phosphorus concentration
of 7.38 mg/L), was found at a stirring speed of 200 r/min. This
indicated that maintaining a stirring speed of 200 r/min benefited
crystal formation. A higher stirring speed would damage the crys-
tals and a lower stirring speed was not conducive to crystal
formation.
The phosphorus removal efficiencies found at different stirring
times are shown in Fig. 3(b). Increasing the stirring time increased
the phosphorus removal rate, but the residual phosphorus con-
centration did not change significantly (a ¼ 0.05; determined by
performing an ANOVA) at stirring times >600 s.
It can be seen from Fig. 3(a) and (b) that the maximum and
minimum residual phosphorus concentrations found using various
optimum stirring speeds and times were 0.82 and 1.99 mg/L, Fig. 3. Effects of different hydrodynamic conditions on the phosphorus removal
respectively. These concentrations were much lower than the efficiency.
 Z. Yin et al. / Chemosphere 255 (2020) 127005 5

respectively.
3.2.3. Effect of the extract dose
The phosphorus removal efficiencies found at extract doses of 4,
8, 12, 16, 20, and 24 mL were determined. The initial conditions
were pH 9.0, stirring speed 200 r/min, and stirring time 600 s.
Increasing the extract dose caused the phosphorus removal rate
to increase and finally reach a plateau (Fig. 4). Increasing the extract
dose from 16 to 20 mL decreased the residual phosphorus con-
centration in the solution from 15.49 to 8.89 mg/L and increased
the phosphorus removal rate from 85% to 92%. Increasing the
extract dose further to 24 mL decreased the residual phosphorus
concentration to 7.67 mg/L and increased the phosphorus removal
rate to 95%. The residual phosphorus concentrations at the extract
doses of 4, 8, 12, 16, and 20 mL were significantly different
(a ¼ 0.05; determined by performing an ANOVA), but the residual
phosphorus concentrations at the extract doses of 20 and 24 mL
were not significantly different. We concluded, taking the removal
rate and cost into account, that the optimal extract dose was 20 mL
(Ca 207.62 mg/L, Mg 122.86 mg/L).
3.3. Characterization of the recovered product
The product obtained under the optimal conditions (pH 9.0,
stirring speed 200 r/min, stirring time 600 s, dolomite solution dose
20 mL) was filtered, dried, and then characterized by XRD, FTIR,
SEM, and energy-dispersive X-ray spectroscopy (EDS). The mass
fraction of MAP in the precipitate was determined by elemental
analysis.
33.3 . The peak was compared with XRD standard card number
71e2089, which indicated that it was a MAP diffraction peak. These
results indicated that the recovered product also contained some
MAP crystals.
3.3.2. FTIR analysis results
The FTIR spectrum of the recovered product (Fig. 5(b)) con-
tained absorption peaks at 563 and 1050 cm1, which were
attributed to PO3
4 . These peaks were broad and strong, indicating
that the recovered sample was mainly phosphate. Absorption peaks
at 1646 and 3400 cm1 were attributed to H2O bending and
stretching vibrations, respectively. This indicated that water of
crystallization was present in the product, meaning that the
recovered product may have contained precursor phases of HAP,
such as ACP and CaHPO4$2H2O. There was a weak absorption peak
at 1431 cm1, which was attributed to NHþ 4 . These results indicated
that the recovered product may have contained some MAP.
3.3.3. SEM and EDS analyses results
It can be seen from the SEM image in Fig. 6(a) that the recovered
product was irregularly shaped, with rough and uneven surfaces
with small particles attached. This indicated that the recovered
product was mainly ACP (Li, Y B. et al., 2007). The EDS spectrum
shown in Fig. 6(b) indicated that the recovered product was rich in
P and Ca, and contained some Mg and O. This indicated that the

3.3.1. XRD analysis results

The XRD spectrum of the recovered product is shown in
Fig. 5(a). A broad peak was found near the diffraction angle 30 .
This peak was consistent with the diffraction peak of amorphous
calcium phosphate (ACP) (Li, Y B. et al., 2007), indicating that the
recovered product was mainly ACP. This would have been because
Ca2þ and PO3 4 in solution could have formed various calcium
phosphate phases such as ACP (Ca3(PO4)2$nH2O), tricalcium phos-
phate (Ca3(PO4)2), and dibasic calcium phosphate dihydrate (CaH-
PO4$2H2O). Once these precursor phases had aged for a certain
period they would have recrystallized and been transformed into
HAP crystals, which are more thermodynamically stable (Kim et al.,
2005). A strong diffraction peak was found at the diffraction angle

Fig. 5. X-ray diffractometry spectrum (a) and Fourier-transform infrared spectrum (b)
Fig. 4. Phosphorus removal efficiencies found at different dolomite solution doses. of the recovered product.
6 Z. Yin et al. / Chemosphere 255 (2020) 127005

Fig. 6. Scanning electron microscopy image (a) and energy-dispersive X-ray spectrum (b) of the recovered product.

product was mainly CaeP compounds but contained some MgeP solution was diluted to 25 mL. The N as NHþ
4 concentration in the
compounds. The XRD, FTIR, SEM, and EDS results indicated that solution was 7.52 mg/L. The mass fraction of MAP was calculated
the recovered product was predominantly the HAP precursor ACP using Eq. (3)
but also contained some MAP.

3.3.4. Analysis of the MAP mass fraction in the recovered product nNHþ N
MMAP
wMAP ¼ 4
 100%; (3)
The MAP mass fraction of the recovered product was deter- mprecipitate
mined by performing elemental analysis. A 200 mg aliquot of the
recovered product was completely dissolved in HCl, then the where wMAP is the mass fraction of MAP, nNH4 þ N is the amount of N
 Z. Yin et al. / Chemosphere 255 (2020) 127005
Table 1
Raw material cost analysis for removing phosphorus from wastewater using calcium and magnesium from different sources.
Wastewater source Agent Dosage (kg/m3) Raw material price (yuan/ton)
Grain fermentation MgCl2 0.42 1000
Wastewater
Sludge dewatering liquid MgCl2 0.40 1000
Brewery wastewater MgCl2 0.37 1000
MgSO4 0.39 700
Sludge water CaCl2 0.98 850
Swine wastewater Dolomite 1.00 200
as NHþ 4 (in mol), MMAP is the molar mass of MAP (245 g/mol), and
mprecipitate is the mass of the recovered product (g).
The N: P: Mg molar ratio for MAP is 1:1:1. According to Eq. (3),
the MAP mass fraction in the recovered product was 1.65%, and the
remaining recovered product was mainly HAP precursors. This was
because HAP has a much lower Ksp (4.7  1055.9) than MAP
(1  1012.6). Given that Ca/Mg ¼ 1 for the reaction, it was easier for
Ca2þ than Mg2þ to react with PO3 4 , meaning calcium phosphate
was preferentially formed and the MAP mass fraction of the
recovered product was lower than the HAP precursor content (Yan
and Shih, 2016). The theoretical calculation results were consistent
with the XRD, FTIR, and SEM-EDS characterization results. We
therefore concluded that the recovered product was mainly HAP
precursors and contained some MAP.
3.4. Analysis of raw material costs
The raw material costs for treating 1 m3 of livestock wastewater
were analyzed. Phosphorus concentrations in different types of
wastewater are different, so the chemical doses were converted to
the equivalents for treating wastewater containing phosphorus at a
concentration of 100 mg/L. The prices of the raw materials were for
industrial-grade chemicals. The raw material cost analysis results
are shown in Table 1.
The dolomite dose was higher than the doses of the other cal-
cium- and magnesium-containing materials, but the cost of dolo-
mite to treat livestock wastewater was only 0.20 yuan/m3 in 2019.
This was 45.9%, 25.9%, and 75.9% lower than the costs of MgCl2,
MgSO4, and CaCl2, respectively, for treating other types of waste-
water (Table 1). The different costs were predominantly caused by
the other chemicals costing several times more than dolomite per
unit mass. Dolomite can therefore be used as a cheap calcium and
magnesium source to effectively decrease the cost of removing and
recovering phosphorus from wastewater through crystallization.
4. Conclusions
(1) The phosphorus removal rate for livestock wastewater was
92% under the optimal conditions (pH 9.0, stirring speed 200
r/min, stirring time 600 s, Ca 207.62 mg/L, Mg 122.86 mg/L).
(2) XRD, FTIR, and SEM characterization and theoretical calcu-
lations indicated that the recovered product was mainly the
HAP precursor ACP. The product also contained small
amounts (mass fraction 1.65%) of MAP crystals.
(3) Phosphorus can be effectively removed and recovered from
livestock wastewater using dolomite as a source of calcium
and magnesium. The cost of dolomite to treat 1 m3 of high-
phosphorus wastewater was 0.20 yuan in 2019, which was
45.9%, 25.9%, and 75.9% lower than the costs of MgCl2,
MgSO4, and CaCl2, respectively, to treat wastewater. Using
dolomite could therefore effectively decrease the cost of
removing phosphorus from wastewater through
7
Treatment price (yuan/m3) P removal efficiency (%) Reference
0.42 92% Han, X R. et al., 2017
0.40 85% Wu, J. et al., 2017
0.37 90% Wang, Q Q. et al., 2018
0.27 90%
0.83 94% Ren, W C. et al., 2015
0.20 92% This study
crystallization. These results may encourage the use of
crystallization to remove phosphorus from wastewater.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Zhichao Yin: Investigation, Formal analysis, Visualization,
Software, Writing - original draft. Qingfeng Chen: Conceptualiza-
tion, Methodology, Validation, Supervision, Resources. Chang-
sheng Zhao: Validation, Formal analysis, Investigation. Ying Fu:
Resources, Writing - review & editing, Data curation. Jinye Li: Re-
sources, Investigation, Formal analysis, Software. You Feng:
Investigation, Formal analysis, Software. Lei Li: Investigation,
Formal analysis, Software.
Acknowledgments
This study was jointly supported by a National Key Research and
Development project (No. 2017YFD0801403), the National Natural
Science Foundation of China (No.41877041), and the Taishan
Scholars Program of Shandong, China (No. tsqn201812086). We
thank Gareth Thomas, PhD, from Liwen Bianji, Edanz Group China
(www.liwenbianji.cn/ac), for editing the English text of a draft of
this manuscript.
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