MDMW Apatite Rockphosphate04

Solubilization of Tunisian Phosphate with Microorganisms
Solubilization of Tunisian Phosphate with

Microorganisms: Physicochemical Investigation of the
Process
D. Bojinova*, R. Ivanova and R. Velkova
University of Chemical Technology and Metallurgy,
8 Kliment Ohridski Blvd., 1756 Sofia, Bulgaria.
E-mail: [email protected]
ABSTRACT: A good future strategy should consider the biological processing approach, which could be
economically feasible not only for high quality phosphate raw minerals, but also for low-quality highly impure
phosphates. This study presents the results from physicochemical investigations of the products of bioorganomineral fertilizers. These samples were synthesized after dissolution of Tunisian PHOSPHORITE (TP)
with microbial suspension, obtained by cultivation of Aspergillus niger fungi. On the basis of the results of X-ray
analysis and IR-spectroscopy, compared with chemical analyses have been proved that a decomposition of the
phosphorite was performed. The creation of some new chemical phases, such as CaHPO 4.2H2O, CaH2P2O7 and
Ca3H2(P2O7)2 were established. The data of chemical and physicochemical analyses give us a sufficient
assumption to propose a probable chemistry of the process of dissolution of TP and obtaining of new bioorganomineral fertilizers.
1. INTRODUCTION
Investigations connected with creating of new
nontraditional technologies for obtaining of
effective phosphoric fertilizers are very actual in
fertilizers production. A good future strategy
should consider the biotechnological methods,
which could be a promising alternative for
natural phosphate processing. Rock phosphate
may be acidified and efficiently processed by
bringing the ore into contact with microorganisms, or their fermentation products (organic
acids) under appropriate conditions (Sperber,
1958; Agnihorti, 1970; Cerezine, et al., 1988;
Narsian, et al., 1993). There are hypotheses in the
literature concerning the chemistry and the
mechanism of inorganic phosphates solubilization, but these processes are not clearly
identified (Halder, et al., 1990; Goldstein, 1995).
Some authors (Azea, et al., 1988; Bojinova et al.,
2004) established low values of phosphates
solubilization with organic acids compared with
the extent of solubilization with cultural liquid
containing the same organic acids. Illmer and
Schinner (1992), assume the formation of
inorganic and organic phosphates and secondary
dissolution of P-containing organic complexes.
This conclusion was made on the basis of the not

lineal correlation between pH values and the
quantity of dissolved phosphate, which was
obtained.
The aim of this study was to establish the
results from physicochemical investigations
made on bio-organomineral fertilizers, obtained
through dissolution of Tunisian Phosphorite (TP)
with microbial suspension of Aspergillus niger.
On the basis of chemical and physicochemical
analyses a probable chemistry of the processes of
solubilization of TP was presented.
2. MATERIALS AND METHODS
Bio-organomineral fertilizers were obtained
through solubilization of TP and an additive of Pcontaining waste (PW) with microbial suspension
of Aspergillus niger fungi. The cultural liquid
contains citric acid with concentration 21.2 g/l.
For this purpose the Optimal Composite Design
with full factorial analysis was used. The
obtained samples were with different chemical
content, especially with different content of
water-soluble and utilizable phosphorus. The
availability of phosphorus for plants was
estimated by its solubility in 2% citric acid
4
(P2O5c.s.), neutral ammonium citrate solution
(P2O5a.s.) and 2% formic acid (P2O5f.s.). The
analysis of P2O5 was made spectrophotometrically based on the produced with
vanadomolybdate yellow complex.
Physicochemical examinations have been
carried out using X-ray Diffraction (XRD) and
infrared spectrometry (IRS). X-ray analysis was
performed with powder samples using
diffractometer DRON UM-1, CuK, rate 10.min-1
for the range from 5 to 400. IRS utilized infrared
spectrophotometer M-80, using cuvettes of KBr
at wavelengths in the range 4000-500 cm-1.
Mineral Processing Technology (MPT 2007)
2.01; 1.95 and 1.83. There are some patterns,

which can be connected with CaSO 4 at d ():
3.81; 3.47; 2.82; 2.21 and 1.87. By comparing Xray diffraction patterns of the initial materials
with those of some products, obtained (Figure 2)
it was established that a decomposition of the
phosphorite crystal structure took place. The
establishment for this conclusion is the fact that
new lines appear at d (): 5.50; 5.09;3.80; 3.65;
3.44; 2.96; 2.88; 2.77 and at d: 4.44; 3.80; 3.34;
3.19. 2.87; 2.68; 2.20; 2.05; 1.83 which can be
connected with a creation of pyrophosphates,
such as CaH2P2O7 and Ca3H2(P2O7)2.H2O.
3. RESULTS AND DISCUSSION

The characteristic diffraction patterns of the TP
and an additive of PW were presented on Figure
1.
Figure 2: XRD patterns of products of bioorganomineral fertilizer, obtained at different

conditions (Table 1): sample no. 1 (position 1);
sample no. 2 (position 2); sample no.3
(position 3)
Figure 1: XRD patterns of TP (position 1) and

PW (position 2)
The basic diffraction maxima for carbonate

fluorapatite can be seen clearly at d (): 3.43;
3.15; 3.07; 2.78; 2.68; 2.62; 2.28; 2.22; 1.91;
1.85; 1.82; 1.77; 1.74; 1.72 and 1.62 (position 1).
X-ray diffractogram for PW (position 2) shows
the characteristic diffraction patterns for CaHPO 4
at d (): 3.35; 2.95; 2.71 and CaHPO 4.2H2O at d
(): 4.25; 3.07; 3.04; 2.64; 2.46; 2.30; 2.25; 2.18;
Some of the characteristic patterns for

Ca5F(PO4)3 at d = 3.44; 3.07; 2.78; 2.68; 2.62 ,
respectively for CaHPO4.2H2O at d = 3.07; 2.95;
2.62; 2.25 1.83 indicated higher intensity
(Figure 2). This fact could be explained with an
overlapping of these maximum points with those
of the new chemical phases, latterly mentioned.
The comparison of the data from the chemical
analyses, established in Table 1and the data from
X-ray phase analysis confirm the fact of the
formation of new chemical phases in the products
of bio-organomineral fertilizers. The values of
5
from X-ray analyses connected with a generation
of acidic pyrophosphates. Comparing the results
from X-ray analyses and those of IRS confirms
this conclusion.
Solubilization of Tunisian Phosphate with Microorganisms
the assimilable P2O5 in the case of formic and

citric acid, more slightly solubility in ammonium
citrate solution and the extent of P2O5
solubilization, respectively, confirms the results
Table 1: Chemical composition of the obtained bio-organomineral fertilizers
P2O5
total
1
2
3
%, w/w
18.9
17.6
28.9
citric soluble
water soluble
formic soluble
%, w/w
10.2
8.3
12.2
%, w/w
2.3
1.5
1.6
%, w/w
10.7
10.0
16.3
, %
54.0
47.2
42.2
As seen from Figure 3 (position 1) an

intensive absorption bands observed in the range
575-605 cm-1 and 1042 cm-1, which are typical
for PO43- group (P-O bond), at 1430-1470 cm-1
and 870 cm-1 typical for C-O bond.
Figure 3: IR-spectra of the initial TP (position 1)

and products of bi-organomineral fertilizers,
obtained at different conditions (Table 1): sample
no. 1 (position 1); sample no. 2 (position 2);
sample no. 3 (position 3)
The IR-spectra of the products of fertilizers,

obtained (Figure3, position 2, 3, 4) showed that
, %
12.2
8.5
5.5
, %
56.6
56.8
56.4
ammonium
citrate
soluble
%, w/w , %
8.4
44.4
5.0
28.4
8.8
30.4
deformation oscillations corresponding to the

vibrations of asymmetric and symmetric
extension of the P-O bond at wave numbers 575
605-1 strongly decreased their intensity , but those
of 1042 cm-1 was disappeared. The other spectral
bands corresponding to the C-O bond vibration,
like the characteristic doublet at 1430-1470 cm -1
were strongly decreased and in the area of 870
cm-1, disappears completely. The new bands of
wave number 920, 1100, 1120, 1645, 1727, 2926
cm-1 can be explained with the presence of an
asymmetric and symmetric oscillation of the PO-P bond, typical for CaH2P2O7 (Figure 3,
position 2, 3, 4). The new doublet, which could
be seen at 1030-1100 cm-1 and 1200 cm-1 together
with some ionization minimum partly coincides
also with these of CaH2P2O7 can be connected
with the availability of the acid pyrophosphate
Ca3H2(P2O7)2.H2O. The absorption bond observed
in the range of 3394-3407 cm-1 is typical for the
free water.
On the basis of the experimental results and
the analysis of the system CaO-P2O5-H2O it could
be concluded that under action of the citric acid a
chemical decomposition of TP was observed
concerning the equations (1-3).
2Ca5F(PO4)3 + 14HX = 3Ca(H2PO4)2 + 7CaX2 + 2HF
(1)
2Ca5F(PO4)3 + 4HX = 3CaHPO4 + 2CaX2 + HF
(2)
2Ca5F(PO4)3 + 10HX = 5CaX2 + 3H3PO4 + HF
(3)
The available CaCO3 in the phosphate reacts

with the citric acid following reaction 4.
CaCO3 + 2C6H8O7 = Ca3(C6H5O7)2 + 3CO2 + 3H2O
(4)
6
The obtained phosphoric acid (equation 3)
could be react with CaCO3 and Ca5F(PO4)
according reaction 5 and 6.
H3PO4 + CaCO3 = CaHPO4 + H2O + CO2
(5)
Ca5F(PO4) + 7H3PO4 = 5Ca(H2PO4)2 + HF
(6)
It is possible the formation of CaHPO4.2H2O

also as a result of hydrolysis of the initially
obtained Ca(H2PO4)2 (equation 7).
Ca(H2PO4)2 + xH2O = CaHPO4 + H3PO4 + (x + 1) H2O
(7)
The obtained H3PO4 reacts with the

phosphate additionally and dissolves new
quantities of P2O5 in the solution and another part
of it is converted intro pyrophosphoric acid
(equation 8).
2 H3PO4 = H4P2O7 + H2O
(8)
The presence of pyrophosphate is probably

due to the following reaction:
2CaHPO4 + H4P2O7 = 2CaH2P2O7 + H2O
(9)
3CaH2P2O7 + 4H2O = Ca3H2(P2O7)2.4H2O + H4P2O7
(10)
2CaH2P2O7 + 3H2O = Ca2P2O7.3H2O + H4P2O7
(11)
CONCLUSIONS
Physicochemical examinations showed that the
bio-organomineral fertilizers contain utilizable
P2O5 in the forms slow soluble for plants. The
basic new chemical phases, which were proved
are CaH2P2O7 and Ca3H2(P2O7)2.H2O together
with CaHPO4.2H2O. This new products could be
considered as an alternative to the traditional Pcontaining fertilizers.
REFERENCES
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Mineral Processing Technology (MPT 2007)

[1] Agnihorti, V.P., Solubilization of insoluble
phosphates by some soil fungi isolated from
nursery seed beds. Can. J. Microbiol., 16, 877880 (1970).
[2] Asea, P.E.A. Kucey, R.M.N., and Stewart,
J.W.B., Inorganic phosphate solubilization by
two Penicillium species in solution culture and
soil. Soil Biol. Biochem., 20, 459-464 (1988).
[3] Bojinova, D., Ivanova, R. and Velkova, R.,
Method for obtaining of organomineral fertilizers
in disintegrator. J. of the Balkan Tribological
Association, 10, 383-393 (2004).
[4] Cerezine, P.C., Nahas, E. and Banzatto, D.A.,
Soluble phosphate accumulation by Asp. Niger
from fluorapatitr. Appl. Microbio. Biotechnol.
29, 501-505 (1988).
[5] Goldstein,
A.H.,
Recent
progress
in
understanding the molecular genetics and
biochemistry of calcium phosphate solubilization
by gram negative bacteria. Biol. Agric. Hortic.,
12, 185-193 (1995).
[6] Halder, A.K., Mushra, A.K., Bhatacharyya, P.
and Chakrabarty, P.K., Solubilization of rock
phosphate by Rhizobium and Bradyrhizobium.
J.Gen. Appl. Microbiol., 36. 81-92 (1995).
[7] Illmer, P. and Schinner, F., Solubilization of
inorganic phosphates by microorganisms isolated
from forest soil. Soil Biol. Biochem., 24, 389395 (1992).
[8] Narsian, V., Thakkar, J. and Patel, H.H.,
Solubilization of natural rock phosphates and
pure insoluble inorganic phosphates by
Aspergillus niger. Indian J. Exp. Biol., 31, 347349 (1993).
[9] Sperber, J.I., Solubilization of apatite by soil
microorganisms producing organic acids.
Austral. J. Agric., 9, 482-487 (1958).

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Solubilization of Tunisian Phosphate with Microorganisms

Solubilization of Tunisian Phosphate with

This conclusion was made on the basis of the not

Mineral Processing Technology (MPT 2007)

2.01; 1.95 and 1.83. There are some patterns,

3. RESULTS AND DISCUSSION

Figure 2: XRD patterns of products of bioorganomineral fertilizer, obtained at different

Figure 1: XRD patterns of TP (position 1) and

The basic diffraction maxima for carbonate

Some of the characteristic patterns for

Solubilization of Tunisian Phosphate with Microorganisms

the assimilable P2O5 in the case of formic and

Table 1: Chemical composition of the obtained bio-organomineral fertilizers

As seen from Figure 3 (position 1) an

Figure 3: IR-spectra of the initial TP (position 1)

The IR-spectra of the products of fertilizers,

deformation oscillations corresponding to the

2Ca5F(PO4)3 + 4HX = 3CaHPO4 + 2CaX2 + HF

2Ca5F(PO4)3 + 10HX = 5CaX2 + 3H3PO4 + HF

The available CaCO3 in the phosphate reacts

Ca5F(PO4) + 7H3PO4 = 5Ca(H2PO4)2 + HF

It is possible the formation of CaHPO4.2H2O

The obtained H3PO4 reacts with the

The presence of pyrophosphate is probably

3CaH2P2O7 + 4H2O = Ca3H2(P2O7)2.4H2O + H4P2O7

2CaH2P2O7 + 3H2O = Ca2P2O7.3H2O + H4P2O7

Mineral Processing Technology (MPT 2007)

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