Nanotechnology for Environmental Engineering (2021) 6:23

https://doi.org/10.1007/s41204-021-00120-5

ORIGINAL PAPER

Calcite‑based material for desulphation of the 29% in ­P2O5 phosphoric

acid: characterization, modelling and optimization
Abderrahim Najah Elidrissi1 · Abderrahmane Aboulhassane1 · Abdelouahab El Hadrami1 · Mohammed Dahbi1 ·
Khalid Ibno Namr2 · Driss Zakaria1

Received: 30 January 2021 / Accepted: 29 March 2021

© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2021

Abstract
In order to reduce the unwanted effects due to a solid genesis during the phosphoric acid concentration process and for even-
tual valorization on an industrial scale and uses of this material. A natural material, extracted from the soil, in the Doukkala
region of Morocco, is used for 29% ­P2O5 phosphoric acid desulphation with a simple protocol, which can be inserted into the
manufacturing process. The physico-chemical analysis of this material was performed by XRD, FTIR, TGA-DTA, XRF and
SEM–EDX. The XRD shows that the natural material consists mainly of calcite ­(Ca0.97Mg0.03CO3), quartz ­(SiO2) and a low
clay fraction (illite). Different bonds and groups (Si–O–Si (Al), C ­ O32−) were highlighted by FTIR analysis. The TGA-TDA
reveals the decomposition of calcite. XRF and EDX analysis clearly indicate high quantity of calcium and weak amount of
Mg element. They showed that it contains mainly 92wt% of Calcite with very low magnesium content, 7 wt% of quartz and
1 wt% of clay-type illite. The modelling of this protocol, by the methodology of experimental designs with the strategy of
complete factorial designs with three factors [amount of natural material (Q), temperature (T) and time (t)] and two levels,
is statistically validated (R2 = 99.94%) and has shown that temperature and time do not significant effect and the amount of
material has an effect on the reduction of sulphate ions. To avoid an excess of calcium (Ca/SO4 = 1), the optimum quantity
of material is 26.08 g per litre of acid, which reduced the rate of solid formed to 63.64% during concentration of the 29%
acid in P­ 2O5. Such an improvement will undoubtedly have interesting consequences for the improvement of productivity
and the protection of industrial equipment.

Keywords  Phosphoric acid · Calcite · Desulphation · Protocol modelling · Full factorial design

Introduction a level of around 2%, undoubtedly affect the quality of the

On an industrial scale, phosphoric acid is obtained mainly
by wet process following the sulphuric acid attack of phos-
phate rock [1, 2]. Most of the impurities contained either
in the phosphate rock or in the reagents used are present
in the phosphoric acid produced. These impurities have an
impact on the quality of the acid, the equipment and the
cost of production. In particular, sulphate ions, which have
* Driss Zakaria
zakaria.d@ucd.ac.ma
1
Laboratory of Physical Chemistry of Materials (LPCM),
Department of Chemistry, Faculty of Science, Chouaïb
Doukkali University, El Jadida, Morocco
2
Laboratory Geosciences and Technics of Environment
(LGTE), Department of Geology, Faculty of Science,
Chouaïb Doukkali University, El Jadida, Morocco
acid during the concentration step [3]. A solid deposit was
formed upon concentration of phosphoric acid containing
mainly the gypsum and sodium fluosilicate [4], leading to
premature clogging of the production line and consequently
a reduction in production due to washing stops and degrada-
tion of the exchangers.
In recent years, several studies have been performed to
develop a suitable material for purification of phosphoric acid
from sulphate. R. Kijkowska et al. and Aboulhassane et al.
were used C ­ aHPO4.2H2O [5] and B ­ aCO3 [3], respectively. In
our previous work, we used a natural dolomite-based mate-
rial, with the aim of reducing the level of solid formed dur-
ing the phosphoric acid concentration step [6]. Despite the
encouraging results obtained by this material, compare to
those obtained by commercial ­BaCO3 [3], this material has
a high level of magnesium which is an undesirable impurity
because it clearly increases the viscosity of the acid, it forms

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precipitated in the form of (­ MgSiF6,6H2O), it promotes the Natural material

formation of insoluble compounds (­ MgNH4PO4) during the
production of liquid fertilizers or diammonium phosphate
(DAP) [4, 7–9] and sludge in the production circuit [10]. These
sludges exhibit significant losses of ­P2O5 [11, 12]. Our investi-
gation in the field of natural materials using physico-chemical
characterization techniques allowed us to select an optimum
natural calcite-based material with low level of magnesium
to study the disulphation of industrial phosphoric acid 29%
in ­P2O5 and avoid the harmful effects of magnesium. In addi-
tion, the acid attack of calcite is faster compared to dolomite,
which allows control of the foam formed in the reactor and a
reduction in the attack time.
In this work, different techniques were used for the physico-
chemical characterization of the selected natural material such
as: structural XRD, vibrational FTIR, thermal TGA–TDA, ele-
mentary XRF and SEM–EDX. For eventual valorization and
uses of this selected natural material on an industrial scale, a
simple protocol, which can be inserted into the manufacturing
process, was used for disulphation of 29% ­P2O5 phosphoric
acid. In addition to the category of material, several factors
can influence disulphation of phosphoric acid process, such as,
weight ratio of natural material to phosphoric acid, tempera-
ture and reaction time. For modelling the process, design of
experiments (DOE) methodology was used and the optimiza-
tion of the process parameters affecting the pretreatment pro-
cess was carried out by using a two levels full factorial design.
The natural material selected for this work was mined at
shallow depths of the Moroccan soil (Doukkala’s region). It
is a limestone soil with encrustation on the surface (Fig. 1).
This material was used for the desulphation of phosphoric
acid 29% in P­ 2O5, without any specific treatment just a sim-
ple grinding and sieving to less than 150 μm.
Desulphation protocol
The adopted protocol was chosen judiciously in order to
simulate the industrial conditions [4]. The experiment of
desulphation was carried out in a reactor with a mechanical
stirrer. It was furnished with a heating water (jacket) con-
nected to a thermostat. Phosphoric acid was heated to the
desired temperature; then, the natural sediment was added
and the mixture was stirred at the desired time according to
the central composite design matrix. The desulphation is
carried out by precipitation of calcium sulphate according
to the reaction below. After end time stirring, the mixture
is filtered.
( +
2H , SO2−
) ( 2+
+ Ca , CO2−
)
4 3
→ CaSO4 , H2 O + CO2
Instrumentation

Characterization of sediment was carried out by X-ray dif-

Materials and methods
fraction (XRD) on the powder using a Bruker advance D8
Phosphoric acid

Phosphoric acid was produced from Moroccan fluorapatite by

wet process according to the following equation [4, 13]:
( )
Ca10 PO4 6 F2 + 10 H2 SO4 + 10xH2 O
→ 6H3 PO4 + 10CaSO4 , xH2 O ↓ + 2HF ↑

Dependent on the process conditions, such as the tempera-

ture, either calcium sulphate hemihydrates (x = 1/2, HH) or
dehydrate (x = 2, DH or phospho-gypsum) was formed. In the
dihydrate process (DH), the temperature of the reactor was
maintained less than 80 °C. The phosphoric acid obtained con-
tains (between 26 and 29% ­P2O5) with the main impurities
indicated in Table 1.

Fig. 1  Natural material

Table 1  Rate of major Impurities Solid SO42− CaO MgO Fe2O3 Al2O3 SiO2 F− Na2O K 2O
impurities in the phosphoric
acid 27% (ρ = 1.267 g/cm3) wt% 0.05 1.73 0.73 1.62 0.27 0.16 0.42 0.73 0.06 0.06

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Nanotechnology for Environmental Engineering (2021) 6:23 Page 3 of 11  23
eco diffractometer, (50KV-20 mA) equipped with CuKα
radiation source (λ = 1.5418 Å), the diffraction patterns were
collected over a (2θ) angular range of 10°–70°, or 5°–70° for
clay fraction, using a size of 0.06° (2θ) step and a constant
counting time. Fourier transformed infrared spectroscopy
was realized using a spectrometer (Nicolet iS10 Thermo
Fisher spectrometer using FTIR) equipped with Attenu-
ated Total Reflection (ATR) mounting in the wave num-
ber range between 525 and 4000 ­cm−1 with a resolution of
2 ­cm−1 and with 30 scans. Thermogravimetric analysis were
recorded on the Shimadzu DTG-60 h model under static air
with a heating rate of 5 °C/min over a temperature range
of 18–900 °C. X-ray fluorescence (XRF) (Axios, disper-
sion wavelength 3KV, Rh), and scanning electron micros-
copy (Hitachi S-750) operating at 20KV and coupled with
the energy dispersive X-ray (Bruker, XFLASH 6/10). The
residual sulphate was determined by titration with barium
chloride dihydrate (Honeywell Fluka™, ≥ 99%), sulfonazo-3
sodium (Honeywell Fluka™) as an indicator and Acetone
(Sigma-Aldrich, ≥ 99.5%).
Results and discussion
Characterization of the natural sediment
The X-ray diffraction (Fig. 2) shows that the natural sedi-
ment contains mainly calcite with low magnesium content
­(Ca0,97Mg0,03)CO3) and quartz in addition to a low clay
fraction. Following separation by suspension in water, the
rate of the clay fraction is estimated at 1%. The X-ray
diffractograms, on clay fraction (Fig. 3) or on oriented
slides with and without ethylene glycol treatment (Fig. 4),
Fig. 2  X-ray diffractograms
for the natural material and the
standards calcite and silicon
oxide
confirm that it is an illite clay non-swellable with a reticu-
lar distance ­d001 (basal spacing) of around 10 Å.
The infrared spectrum of the natural material (Fig. 5)
shows three absorption bands, at 1426.876 and 710 ­cm−1,
attributed, respectively, to the vibrations of asymmetric
elongation, out-of-plane deformation and in-plane defor-
mation of carbonate groups [14]. The presence of a band
located at 1027 ­cm−1 indicates the existence of silica in
the material [15]. The band observed at 980 ­cm−1 is most
probably related to the presence of the Si–O–Al bond
coming from the clay fraction contained in the material
[16]. Table 2 gives assignment of infrared bands of natural
material.
The TGA–TDA curves of the natural material (Fig. 6)
show overall two mass losses of 4.85% at 110 °C and 34%
between 600 and 850 °C. The first one corresponds to the
departure of water from humidity. The second endothermic
loss is granted to the departure of carbon dioxide follow-
ing the decomposition of calcite [22, 23]. X-ray diffracto-
gram for the residual solid, after calcination of the natural
material at 850 °C (Fig. 7), shows that it is formed mainly
of calcium oxide and silicon oxide.
CaCO3 → CaO + CO2
The chemical composition of the natural material was
determined by X-ray fluorescence. The percentages in the
form of oxides of different elements present in the material
are given in Table 3. It consists mainly of: calcium oxide
(44.4%) and silica (6.7%). Note that, the presence of other
constituents in trace amounts, notably magnesium oxide
with a percentage of less than 1%. The presence of silicon
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Fig. 3  X-ray diffractograms for

pulverulent clay fraction and
standards illite and silicon oxide

Fig. 4  X-ray diffractogram for

clay fraction on oriented slides
with and without ethylene
glycol treatment

and aluminium suggests that the material may contain a
clay fraction, according to the results of the XRD and IR
analysis.
Semi-quantitative analysis, by scanning electron
microscope coupled with energy dispersion spectroscopy
(SEM–EDX) of natural material on a thin slide (Figs. 8, 9
and Table 4), shows the abundance of calcite, in the form of
well-formed crystals, containing only the Ca, C, O, Si and a
very low amount of magnesium.
All the results, obtained by these different characteriza-
tion techniques (XRD, FTIR, TGA-TDA and SEM–EDX),
confirm that the natural material is formed mainly by
calcite, quartz and a small clay fraction of the illite type.
The very low level of magnesium was originally the rea-
son to select this material for use to the desulphation of
phosphoric acid 29% ­P2O5.
Deposit solid characterization
After filtration, the deposit solid formed by precipitation
following the desulphation of phosphoric acid is charac-
terized by XRD. Figure 10 shows that this solid is formed
mainly of hydrated calcium sulphate.

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Nanotechnology for Environmental Engineering (2021) 6:23 Page 5 of 11  23

Fig. 5  FTIR spectra of natural

material

Table 2  Assignment of Infrared Bands of natural material ­ 2SO4 (Y in g/l) in the

was to minimize the residual rate of H
Band frequen- Attribution Band shape References
pretreated phosphoric acid. The amount of phosphoric acid
cies ­(cm−1) to be treated was kept constant at 100 ml for all tests. The
experimental range of variation of these factors (Table 5)
1426 νas ­CO32− Strong/broad [14] was set taking into account the technical and economic
1120 νas Si–O Shoulder [15, 17–21]
aspects of the manufacture of phosphoric acid and the oper-
1085 Shoulder
ating conditions available on the industrial site.
1027 Medium/broad
Two-levels full factorial design methodology sets all
980 νas Si–O-Al Medium/broad [16]
operating conditions for three factors (­ 23 = 8 tests): in total,
912 δ Al–O–H Shoulder [17]
eight experiments were performed out and one in the centre
876 δas ­CO32− Strong/sharp [14]
of the experimental field. The results obtained are summa-
845 δ Si–O–H Shoulder [18]
rized in Table 4. Equation 1 presents the encoded math-
785 νs Si–O–Si Weak [15]
ematical model [25–28]:
710 δs ­CO32− Medium/sharp [14]
580 δ Si–O Weak [18–20] Y = b0 + b1 X1 + b2 X2 + b3 X3 + b12 X1 X2
+ b13 X1 X3 + b23 X2 X3 + b123 X1 X2 X3 + 𝜀, (1)
where Y is the amount of residual sulphate (response to be
Modelling by full factorial design adjusted and optimized). X1, X2 and X3 are factors in codi-
fied units, b0 is the global mean, bi the main and interac-
In order to proceed to the modelization of the desulphation
tion effects and ε is the random error associated with the
process, the two-levels full factorial design has been car-
response. The results in Table 6 are processed by JMP-SAS
ried out [24]. This methodology assumes a linear variation
software to determine the effects bi on the residual quantity
between the response and the different factors, so it uses
of ­H2SO4 (Y g/L) and statistically validate the model. Sta-
less number of tests to determine the main effects of each
tistical analysis by Student’s test with a risk of 5% identifies
factor and their interactions and allows us properly to adjust
the factors having a significant influence on the observed
the average response using a linear model and helps us to
response (Y g/L) [29]. Table  7 summarizes the effects,
avoid alias phenomenon [29]. In this study, three factors
t-ratio and p value of each factor. Based on p values, all
were selected to determine their effects on the desulphation
factors and their interactions have a statistically significant
process, namely the amount of natural material (X1 in g/l),
effect on desulphation (p value < 0.05).
temperature (X2 in °C) and time (X3 in mn). The target goal

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Fig. 6  DTA/TGA analysis of natural sediment

Fig. 7  X-ray diffractogram for

natural material after calcina-
tion at 850 °C

Table 3  Chemical composition, Naturel material Fire loss CaO SiO2 Al2O3 MgO K2O FeO TiO2 Total
determined by X-ray
fluorescence (XRF) analysis wt% 34 44.4 6.7 1.7 0.9 0.2 1.1 0.2 89.2
wt% Normalized 38.12 49.78 7.51 1.91 1.01 0.22 1.23 0.22 100

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Nanotechnology for Environmental Engineering (2021) 6:23 Page 7 of 11  23
Fig. 8  SEM of natural material on a thin slide
The effects of each factor are shown in Fig. 11. Consid-
ering the values of the t-ratio and the graph of the effects
of each factor (Table 7 and Fig. 10), we observed that the
amount of natural matter (X1) has an important effect on the
desulphation process following the decrease in the residual
sulphate rate (Y) when this factor goes from low to high
levels. While temperature (X2) and time (X3) have little
effect on the desulphation process. In fact, the sulphates are
eliminated by precipitation of the calcium sulphate, increase
level of calcium favours the formation of this precipitate.
Temperature will increase the solubility and time will favour
the formation of the precipitate. The effect of these last two
factors is weak because the precipitate formed is stable in
phosphoric acid. The mathematical model is therefore writ-
ten (Eq. 2):
Fig. 9  EDX spectra of natural material on a thin slide (cartography 30 × 60 μm2)
Table 4  Semi-quantitative Element O Ca
analysis by SEM–EDX of
natural material on a thin slide Mass% 56.89 25.25
(cartography 30 × 60μm2)
Atom% 65.19 11.55
Y = 11.487 − 5.849 ∗ X1 + 0.949 ∗ X2
− 1.011 ∗ X3 − 0.459 ∗ X1 ∗ X2
− 0.459 ∗ X1 ∗ X3 − 0.276 ∗ X2 ∗ X3 (2)
Table 8 represents the analysis of variance (ANOVA)
which confirms the statistical validity of the model (Eq. 2)
with a factor R 2 of 99.94%. Indeed, Fig.  12 shows the
graphical fit of the model and confirms the accuracy of the
modelling of the estimated responses (Yest) by the experi-
mental results. Hence, the analysis of the residuals (differ-
ence between Yobs and Yest) shows that the residuals are
distributed randomly around zero without any particular
shape (Fig. 13). To confirm the validation of the modelling,
further testing was conducted in the experimental area and
using untested experiments in the full factorial design matrix
(Table 6). Table 9 shows that the differences between the
experimental results (Yobs) and the estimated results (Yest) are
not significant. Therefore, the desulphation protocol can be
modeled by Eq. 2 to define the optimal operating conditions
for efficient reduction of phosphoric acid sulphates.
For economic reasons, phosphoric acid P ­ 2O5 at 29% can
be pre-treated at its temperature upon arrival in the desul-
phation reactor (75 °C X2 = 1) and for a time that does not
affect the phosphoric acid manufacturing process (90 min
X3 = 1). Hence, the model is written in the following form:
Ytolerated = 11.15 − 6.768 ∗ X1 (3)
With Ytolerated, the maximum residual mass of sulphate
tolerated so as not to have the formation of a solid during
the step of concentrating the phosphoric acid 29% in ­P2O5.
The value of ­Ytolerated was determined by using the solu-
bility product of calcium sulphate in 54% ­P2O5 phosphoric
C Si Mg Al Cu Total
13.16 3.06 0.91 0.72 nd 100.00
20.09 2.00 0.69 0.49 nd 100.00
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Fig. 10  X-ray diffractogram for

deposit solid

Table 5  Experimental variation of each factor Ca2+ = SO2−

[ ] [ ]
54% 4 54%
Factor Amount of natural Temperature Time (mn)
material (g/L) (°C) X3 At the concentration of phosphoric acid 62% of water was
X1 X2 evaporated, from which the volume of phosphoric acid 54%
­P2O5 obtained after concentration of one litre of phosphoric
Level (− 1) 17.6 30 30
acid 29% P ­ 2O5 is V54% = 0.3825 L. Hence, the concentration
Level (+ 1) 37 75 90
of sulphate ions in concentrated acid is as follows:
Ytolerated
SO2−
[ ]
4 54%
= = 0.027 ∗ Ytolerated
2+
(Ks = ­[Ca ]54% ­[SO42−]54% = 0.105)[6]. In this case, the cal- 98 × v54%
cium intake of the natural reagent must be taken into account
This allows you to write:
after desulphation and the molar ratio between the sulphate
and calcium ions in the desulphated acid must be equal to 1: Ks = Ca2+ 54% SO2− = (0.027 ∗ Ytolerated )2
[ ] [ ]
4 54%

n SO2− = n Ca2+ Not reacted 29%

( ) ( ) √
From where: Ytolerated = 0.027s = 12 g∕l.
K
4 Not reacted 29%
In order to avoid the formation of the solid during the con-
Hence, the concentrations of sulphate and calcium ions
centration step, the mass of H
­ 2SO4 in phosphoric acid must be
after phoshoric acid concentration must be equal to:
reduced to 12 g per liter of phosphoric acid 29% as P­ 2O5. For

Table 6  Results of conducted N° Codified values True values Removal ­H2SO4 (g/L)

experiments
X1 X2 X3 Dose (g) T (°C) Time (mn) Obs Pred Res

1  − 1  − 1  − 1 17.6 30 30 16.17 16.18  − 0.01

2 1  − 1  − 1 37 30 30 6.37 6.32 0.05
3  − 1 1  − 1 17.6 75 30 19.6 19.55 0.05
4 1 1  − 1 37 75 30 7.84 7.85  − 0.01
5  − 1  − 1 1 17.6 30 90 15.68 15.63 0.05
6 1  − 1 1 37 30 90 3.92 3.93  − 0.01
7  − 1 1 1 17.6 75 90 17.88 17.89  − 0.01
8 1 1 1 37 75 90 4.41 4.36 0.05
9 0 0 0 27.2 52.5 60 11.27 11.46  − 0.19

Obs.: observed, Pred.: predicted, Res.: residual

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Nanotechnology for Environmental Engineering (2021) 6:23 Page 9 of 11  23

Table 7  Analysis of the effects Term Scaled Plot Estimate Std t Ratio Prob>|t|
of variables
Estimate Error
Interce 11.487222 0.021196 541.95 <0.0001
pt
X1 -5.849375 0.022482 -260.18 <0.0001
X2 0.949375 0.022482 42.23 0.0006
X3 -1.010625 0.022482 -44.95 0.0005
X1*X2 -0.459375 0.022482 -20.43 0.0024
X1*X3 -0.459375 0.022482 -20.43 0.0024
X2*X3 -0.275625 0.022482 -12.26 0.0066

19,6

11,48722
Y

±0,0912

3,92
1

1
-1

-1

-1
0 0 0

X1 X2 X3

Fig. 11  Effects of four factors on the sulphation phosphoric acid 29% ­P2O5

Table 8  Analysis of variance (ANOVA) (natural material) which allowed to remove 83.5% and 53% of
Source DF Sum of squares Mean square F ratio
the solid formed, respectively [3, 6].

Model 6 293.08707 48.8478 12,080.88

Error 2 0.00809 0.0040 Prob > F Conclusion
C. Total 8 293.09516  < 0.0001
The physico-chemical characterization of the natural
material, subject of this work, allowed us to determine its
this purpose, the mass of the reagent is determined on the basis
chemical and phasic composition. The very low level of
of Eq. 3, where the amount of reagent to use is 26.08 g/l. After
magnesium will undoubtedly favour its use for the desul-
concentration of the desulphated acid and the crude phos-
phation of phosphoric acid 29% in P ­ 2O5. The modelling
phoric acid 29%, the total amount of solid formed is 0.92 and
of this process allowed the determination of the optimal
2.53%, respectively. This presents a reduction in the amount
conditions which take into account industrial conditions
of solid formed of at least 63.64%. This result is promising
and which make it possible to remarkably decrease the rate
compared to that of barium carbonate (chemical) and dolomite
of sulphate and consequently to reduce the level of solid
formed during the concentration of phosphoric acid. Such

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 23   Page 10 of 11 Nanotechnology for Environmental Engineering (2021) 6:23

Fig. 12  Adjustment graph

Fig. 13  Residuals graph

Table 9  Additional tests Amount of natural Temperature Time (mn) Observed Estimated Difference
material (g/L) (°C) X3 response (Y) response (Yest)
X1 X2

37 50 60 5.635 5.583 0.052

25 40 70 12.005 12.037 − 0.032
20 60 30 17.15 17.078 0.072

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Nanotechnology for Environmental Engineering (2021) 6:23 Page 11 of 11  23
an improvement will undoubtedly have interesting conse-
quences for the protection of industrial equipment against
fouling. On the other hand, this material is non-hazardous,
inexpensive, abundant and easy to use.
Acknowledgements  "Research carried out within the framework of
the University Center for Research Applied Chemistry and Sustainable
Development CUR-CA2D of Chouaïb Doukkali University."
Declarations  17. Srasra E (1994) Infrared spectroscopy study of tetrahedral and
Conflict of interest  The authors declare that they do not have any con-
flict of interest.
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