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Phosphorus Uptake by Upland Rice From Superphosphate Fertilizers

Produced With Sulfuric Acid Treatments of Brazilian Phosphate Rocks

Jos Lavres JRa; Andr Rodrigues Reisb; Thiago Assis Rodrigues Nogueiraa; Cleusa Pereira Cabrala;
Eurpedes Malavoltaa
a
Department of Mineral Nutrition of Plants, Center for Nuclear Energy in Agriculture, University of
Sao Paulo, Piracicaba, Brazil b Department of Environmental Engineer, Waseda University, Tokyo,
Japan
Online publication date: 20 June 2011

To cite this Article Lavres JR, Jos , Reis, Andr Rodrigues , Nogueira, Thiago Assis Rodrigues , Cabral, Cleusa Pereira and

Malavolta, Eurpedes(2011) 'Phosphorus Uptake by Upland Rice From Superphosphate Fertilizers Produced With Sulfuric
Acid Treatments of Brazilian Phosphate Rocks', Communications in Soil Science and Plant Analysis, 42: 12, 1390 1403
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Communications in Soil Science and Plant Analysis, 42:13901403, 2011

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ISSN: 0010-3624 print / 1532-2416 online
DOI: 10.1080/00103624.2011.577859

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Phosphorus Uptake by Upland Rice From

Superphosphate Fertilizers Produced With Sulfuric
Acid Treatments of Brazilian Phosphate Rocks
JOS LAVRES JR,1 ANDR RODRIGUES REIS,2
THIAGO ASSIS RODRIGUES NOGUEIRA,1
CLEUSA PEREIRA CABRAL,1 AND
EURPEDES MALAVOLTA1
1

Department of Mineral Nutrition of Plants, Center for Nuclear Energy in

Agriculture, University of Sao Paulo, Piracicaba, Brazil
2
Department of Environmental Engineer, Waseda University, Tokyo, Japan
Upland rice is an important crop in Brazilian agriculture and phosphorus (P) deficiency
is one of the most yield limiting factors for this crop. A greenhouse experiment was carried out with the objective of evaluating response of upland rice to P rate and sources.
The treatment consisted five P rates: 0, 25, 50, 100, and 200 mg dm3 supplied through
four P sources: Araxa, Catalo, Irece, and Lagamar. The soil used in the experiment
was a Typic Hapludox. Rice grain yield, shoot dry weight, and root dry weight was
significantly increased with increasing resin extractable P in the soil. Maximum shoot
dry weight and grain yield was achieved with resin extractable P of 30 mg P dm3 .
However, root dry weight increased linearly with increasing P concentration in the
range of 4 to 72 mg dm3 . Shoot dry weight, grain yield, and root dry weight increased
significantly in a quadratic fashion with increasing P concentration in the shoot. Rice
yield and P uptake were not affected significantly with P sources. Grain Cd concentration also was significantly affected by P rates but did not exceed the permissible
concentration for human consumption, according to Brazilian food legislation.
Keywords
solubility

Neutral ammonium citrate, legislation, simple superphosphate, water

Introduction
Brazil is the largest producer of upland rice in the world. It is mainly produced in the
central part of Brazil, locally known as the cerrado region. Oxisols and Ultisols are dominating soils in the cerrdao region. Phosphorus (P) deficiency is widely reported for annual
crop production in cerrado soils (Fageria and Baligar 2008). Simple and triple superphosphates are the main sources of P fertilization used by the Brazilian farmers. Simple
superphosphate (SSP) is the product of the following reaction simplified by Sauchelli
(1960): fluorapatite + sulfuric acid (3 [Ca3 (PO4 )2 ] Ca F2 + 7H2 SO4 ) monocalcium
phosphate + gypsum + hydrofluoric acid (3 [Ca (H2 PO4 )2 ] + Ca SO4 + 2HF). However,
Received 11 November 2009; accepted 11 February 2011.
Address correspondence to J. Lavres Jr, Department of Mineral Nutrition of Plant, Center for
Nuclear Energy in Agriculture (CENA), University of Sao Paulo (USP), Av. Centenrio, 303. C.P.
96, CEP 13400-970, Piracicaba, SP, Brazil. E-mail: jlavres@cena.usp.br

1390

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P Uptake by Rice from Brazilian Superphosphates

1391

monocalcium phosphate and gypsum are not the only components of SSP. A list of 16
other products, among them various calcium, iron, and aluminum phosphates is described
in Sauchelli (1960).
Brazilian law requires that simple superphosphate (SSP) should have at least 18%
of neutral ammonium citrate plus water-soluble P2 O5 , and a minimum of 15% of watersoluble phosphorus. However, the minimum P requirements could not been reached when
the apatite due to contents of iron and aluminium sesquioxides (Al2 O3 + Fe2 O3 or R2 O3 )
close or higher than 3%. The SSP used in this study was produced from Brazilian apatite
with the following R2 O3 content: Araxa (2.12%), Catalao (1.48%), Irece (3.09%), and
Lagamar (2.89%). Total acidulation of phosphate rocks treated with sulfuric acid produced
SSP with different concentration of water-soluble phosphorus: Araxa (15.48%), Catalao
(18.94%), Irece (12.33%) and Lagamar (11.11%). In 2004, Brazil produced 5,628,485
metric tons of SSP containing 1,020,731 tons of P2 O5 , making it the main source of phosphorus in the market (ANDA 2006). Brazilian legislation, Agriculture Ministry Normative
Instruction n . 5 of February 23, 2007, regulates the legal specifications of SSP: minimum guarantee of 18% of P2 O5 soluble in neutral ammonium citrate (NAC) plus at least
15% soluble in water. This concentration is obtained by treating concentrated ground
apatite with sulfuric acid. Besides the P2 O5 , there must be minimum levels of calcium (Ca;
10%) and sulfur (S; 8%) in the final product. On the other hand, The Industrial Minerals
Handbook, cited by LapidoLoureiro and Melamed (2006), establishes the specifications
for concentrations of phosphate rocks: P2 O5 up to 42%; iron and aluminum sesquioxides
(R2 O3 ), for example, (Fe2 O3 + Al2 O3 ) <34%; P2 O5 /R2 O3 = 20; Cd <0.8255 ppm. In
the phosphorites (sedimentary origin), due to the partial substitution of calcium by cadmium (Cd), the levels of this element are much higher than in the apatites (igneous origin)
(Alloway and Steinnes 1999).
The R2 O3 level in some Brazilian apatites exceeds the desirable range. The sesquioxides consume part of the acid, giving various iron and aluminum phosphates. In other
words, part of the rock is not completely transformed into monocalcium phosphate, and
as a consequence the legal limit of 15% water-soluble P2 O5 is not attained. Hence, the
question frequently arises that fraction of P2 O5 insoluble in water is available to the plants.
Furthermore, as reported by Prochnow et al. (2006b) research has been conducted on the
agronomic effectiveness of P fertilizers containing lower water solubility, as compared to
those specified by Brazilian legislation. In addition, information provided in the literature
suggests that the level of impurities in P fertilizers would have to be increased above current levels to reduce agronomic effectiveness (Gilkes and LimNunez 1980; Mullins 1988;
Prochnow et al. 2008). Thus, the better use of low-grade phosphatic rocks is possible by
producing agronomically effective P fertilizers varying in water solubility (Mullins and
Evans 1990). These fertilizers will most likely contain high amounts of iron (Fe)-alumium
(Al)-P compounds, and therefore it is important to gain a better understanding of the performance of these new P sources (Prochnow et al. 2006b) and finally, the P availability
from these fertilizers.
The objective of the authors in this study was to determine P availability efficiency of
four superphosphate sources produced from Brazilian phosphate rocks like Araxa, Catalao,
Irece and Lagamar using upland rice as a test crop. Another objective was to determine
translocation of Cd from SSPs to rice grains.

Materials and Methods

A greenhouse experiment was conducted during 19 August 2005 to 11 January 2006 to
evaluate effectiveness of four superphosphates produced from Brazilian phosphate rocks

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1392

J. Lavres Jr et al.

treated with sulfuric acid. The experiment was carried out in a greenhouse. Soil used in
the experiment was a Typic Hapludox. Chemical properties of the 20 cm surface layer soil
used in the experiment were: pH (calcium chloride; CaCl2 ), 4.5; organic matter content,
34 g dm3 ; phosphorus-resin 6 mg dm3 (resin extractable P and colorimetric determination); potassium (K+ ), 1.1 mmolc dm3 (Mehlich-1); calcium (Ca2+ ), 9 mmolc dm3 ;
magnesium (Mg2+ ), 4 mmolc dm3 ; potential acidity (H + Al), 40 mmolc dm3 ; base
sum, 14.2 mmolc dm3 ; cation exchange capacity, 54.2 mmolc dm3 ; and base saturation, 26.2 mmolc dm3 ; sulfur, 7.0 mg dm3 ; B (hot water), 0.22 mg dm3 ; copper (Cu)
(diethylenetriaminepentaacetic acid; DTPA), 0.6 mg dm3 ; Fe (DTPA), 34 mg dm3 ; manganese (Mn) (DTPA), 6.5 mg dm3 ; zinc (Zn) (DTPA), 1.5 mg dm3 ; nickel (Ni) (DTPA),
0.02 mg dm3 ; Cd (DTPA) <0.01 mg dm3 ; chromium (Cr) (DTPA), 0.6 mg dm3 ; and
lead (Pb) (DTPA), 1.26 mg dm3 . Tables 1 and 2 contain the results of superphosphates
analyses and other products that do not satisfy the legal requirement due to the level of
water-soluble P2 O5 is below the minimum. Analysis of Togo SSP from sedimentary rock
was included for comparison.
The experimental design was completely random blocks, with treatments arranged in
a 5 4 factorial fashion, consisting of five rates of P (controlwithout P and 25, 50,
100, and 200 mg of P per dm3 four P sourcesAraxa-SSP, Catalao-SSP, Irece-SSP
and Lagamar-SSP), with four repetitions. Phosphate treatments were applied thirty days
after liming. All treatments received basal fertilizer as nitrogen (N), 50 mg dm3 as urea
and potassium (K), 50 mg dm3 as potassium sulfate (K2 SO4 ). In addition, micronutrients
Table 1
Characteristics of the Brazilian simple superphosphate obtained by total acidulation of
phosphate rock(1)
Characteristics

Araxa-SSP

Catalao-SSP

________________________________

P2 O5 total
P2 O5 water
P2 O5 NAC + H2 O
P2 O5 citric acid
R2 O3 (Al2 O3 + Fe2 O3 )

18.79
15.48
18.35
16.68
2.12

20.90
18.94
20.64
19.67
1.48

Irece-SSP

Lagamar-SSP

% __________________________________
18.07
17.28
12.33
11.11
17.46
17.07
14.40
11.34
3.09
2.89

Notes. Analyzed according Lanarv (1988). NAC = neutral ammonium citrate.

Table 2
Nickel and toxic elements concentrations in Brazilian simple superphosphatea
Superphosphate - rock

Ni

As

___________________________

SSP - Araxa
SSP - Catalao
SSP - Irece
SSP - Lagamar
SSP Togob

16
22
6
9
8

36
38
7
6
10

Cd

Cr

Pb

mg kg1 ____________________________
0.99
10
13
0.99
5
16
1.0
11
4
1.0
11
4
11
35
22

Notes. a Total P2 O5 extractant. Determined by inductively coupled plasma atomic emission

spectroscopy (ICP-AES). Simple superphosphate. b used only to compare.

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P Uptake by Rice from Brazilian Superphosphates

1393

were also applied as boron (B), 1 mg dm3 , as boric acid; Cu, 2 mg dm3 , as sulfate;
Fe, 6 mg dm3 , as Fe-EDTA; Mn, 6 mg dm3 , as sulfate; molybdenum (Mo), 0.1 mg
dm3 , as sodium molybdate; and Zn, 4 mg dm3 , as sulfate. Furthermore, 100 mg dm3 N
and K were applied as topdressing during maximum tillering and panicle formation stages.
The SSP and nutrients were mixed with 3 dm3 of soil, which was then incubated for
45 days with moisture maintained at 50% of the field moisture capacity. At sowing, a soil
sample was taken for chemical analysis and cultivar IAC-202 was planted. After germination, thining was done and five plants were maintained in each pot. The soil moisture
was maintained in the pots at about 50% of the field capacity by weighing. At harvest,
roots, stalks plus leaves and panicles were separated. The plant material was oven-dried
with forced air circulation at 65 C for 72 hours. Dry plant material was ground in a Wiley
mill and the samples were placed in plastic bags. The material was analyzed according to
the methods described by Malavolta, Vitti, and Oliveira (1997).
Soil samples were taken from each pot at harvest and were analyzed according to the
method described by Raij and Quaggio (2001). Cadmium content in the fertilizers was
determined in the same extract obtained for total P determination, by inductively coupled
plasma atomic emission spectroscopy (ICPAES).
The data were submitted to analysis of variance using the statistical program SAS
System for Windows 6.11 (SAS Inst. 1996). Regression analysis was done using the GLM
(General Linear Model) procedure, as described by PimentelGomes and Garcia (2002).
Treatment effects for yield, and for P and Cd accumulation grain, were compared by the
Tukeys test, at 5% significance.

Results
The variance analysis, summarized in Table 3, shows the interaction effects of the sources
and rates only for the total P accumulation by rice plants, shoot dry weight and the
concentration and accumulation of Cd in the rice grains.
Table 3
Analysis of variance, mean and coefficient of variation for variables as related to rates and
sources of P
Source of variation

Grains
____________________________

Sources
Rates
Sources Rates
Mean
CV (%)
Sources
Rates
Sources Rates
Mean
CV (%)

ns

2.60
252.71
1.34ns
10.55
5.6
Total P accumulation
4.73
679.15
3.86
41.29
9.0

Shoot

Roots

Value Fcalculated _____________________________

7.26
1.07ns

84.19
52.34

2.91
2.35ns
8.54
2.99
7.8
10.1
Cd concentration
Cd accumulation
6.49
49.37

1.43
166.87

4.08
9.35
0.16
0.34
31.0
10.3

Notes. ns Not significant. , and is significant at 10%, 5% e 1%, respectively, by the F test.

1394

J. Lavres Jr et al.
YArax = 4.0225 + 0.2837X (R2 = 0.98**)
YCatalo = 7.9975 + 0.2403X (R2 = 0.98**)
70

YIrec = 7.4377 + 0.2919X (R2 = 0.90**)

Resin extractable P (mg dm3)

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60

YLagamar = 7.5175 + 0.2795X (R2 = 0.97**)

50
40
30
20
10
0
0

25

50

100
Rate of P applied (mg dm3)

200

Figure 1. Phosphorus extracted by resin in soil samples (mg dm3 ) as related to P rates (0, 25, 50,
100, and 200 mg dm3 ) of Brazilian simple superphosphates (Araxa, Catalao, Irece, and Lagamar),
before upland rice growth.

Figure 1 shows the soil P analysis (extracted by resin) after the incubation and before
the rice sowing, as related to P rates and sources. There was a linear increase in resinextractable P with increasing P rate from 0 to 200 mg P dm3 as expected. The linear
model (R2 0.90) best explained this relationship, and there were not statistical differences among superphosphates. In other words, available P as measured by a resin test
showed that all superphosphates utilized were an effective P source providing available P
for upland rice.
The range of 41 to 80 mg dm3 , which is considered as a high level by van Raij
et al. (1996), was obtained with a rate of 100 mg dm3 of the phosphates from Irece, and
a P rate of 200 mg dm3 of the phosphates from Araxa, Catalao, and Lagamar rocks. The
anion exchange resin method was shown to be adequate to evaluate P availability for both
upland and flooded rice as recently reported in the literature (Teo, Beyrouty, and Gbur
1995; Francisco et al. 2008).
The phosphorus level in the soil was reflected in the production of dry matter from the
shoot (leaves and stalks), grains with husk, and roots (Figures 2, 3, and 4). Only dry mass
yield of the shoot was affected by SSP sources (Figure 2). On the other hand, there was
no effect of sources on the grain production, and the critical P levels in the soil for 90% of
maximum yield was obtained with 37 mg dm3 of P (Figure 3). There also was no effect of
sources when relating the phosphorus level in the soil with the dry mass yield of the roots
(Figure 4). The P levels in the soil corresponding to the point of maximum dry mass yield
of the shoot were 28, 42, 58, and 50 mg dm3 , respectively, for the Araxa, Catalao, Irece,
and Lagamar sources (Figure 2). In other words, the greatest yield was reached with lower
levels in the soil due to the sources with a higher water-soluble P level. However, the two
other sources (Irece and Lagamar) showed similarly to SSP from Catalao.

P Uptake by Rice from Brazilian Superphosphates

0.1889X)

YArax = 9.4962(1 e

(R2 = 0.86**)

0.1925X)

YCatalo = 9.0342(1 e
YIrec = 9.1599(1 e
12

0.2171X)

(R2 = 0.75**)

(R2 = 0.69**)

0.1471X)

YLagamar = 10.3457(1 e

1395

(R2 = 0.83**)

Shoot dry weight (g per pot)

10
9
8
7
6
5
4

20

40

60

80

Resin extractable P (mg dm3)

Figure 2. Relationship between shoot dry weight (Y) and P extracted by resin in soil samples (X)
collected before upland rice growth.

Yaverage = 12.0204(1 e

0.1598X)

(R2 = 0.87**)

14

Grain yield of milled rice (g per pot)

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11

12

10

20

40

60

80

Resin extractable P (mg dm3)

Figure 3. Relationship between grain yield of milled rice (Y) and P extracted by resin in soil samples
(X) collected before upland rice growth, corresponding to average of the P sources.

1396

J. Lavres Jr et al.
Yaverage = 2.4121 + 0.0209X (R2 = 0.54**)

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Root dry weight (g per pot)

20
40
60
Resin extractable P (mg dm3)

80

Figure 4. Relationship between root dry weight (Y) and P extracted by resin in soil samples (X)
collected before upland rice growth, corresponding to average of the P sources.

Figure 2 shows the difference among sources for all the rates, which is confirmed
by the regression equations. The simple superphosphates produced with rocks from Irece
and Lagamar presented the lowest levels of water-soluble P2 O5 , but with greater effect on
raising the phosphorus in the soil similar to Araxa and Catalao SSP that showed more P2 O5
water-soluble. These results are consistent, and are presented in Tables 3 and 4.
There was no significant effect of sources on the production of roots and grains, but
there was on the dry mass yield of the shoot (Table 3). As can be observed in Table 4, the
differences between sources were the following: Lagamar at a rate of 100 mg dm3 differed
from the same rate of Irece, while Lagamar, at a rate of 200 mg dm3 , led to the production
of more dry matter than did the corresponding rate of Araxa and Catalao. The all simple
superphosphates proved to have the same availability even though two of them (Irece and
Lagamar) did not contain the minimum water-soluble P2 O5 required by the legislation.
In general, P levels increased with the doses of P. However, for the sources of P
there was a statistically significant difference for total P content considering the rate of
50 mg dm3 from the Lagamar source, and for the rate of 100 mg dm3 from the Catalao
source, which did not differ significantly from the Lagamar source (Table 5).
With regard to the nutritional state of the plants, evaluated by calculating the critical
level, which is defined by the P level in the shoot associated with 90% of the maximum
dry mass yield, there was no effect of sources. For this reason, all the data were plotted
as can be seen in Figures 5, 6, and 7. Rice dry mass of shoot, grains, and roots increasing
with the P shoot concentrations reached the highest values of these variables up to about
1.0 g kg1 . The critical level values of P for the dry mass of shoot, grains, and roots were,
respectively, 0.92, 0.87, and 0.95g kg1 which reflect the consistency of the parts sampled
for evaluation the P nutritional status. However, average P content of about 1.6 g kg1 can
be considered as an adequate level in the leaves of rice (Fageria and Barbosa Filho 2007).
Nevertheless, the shoot P concentration can be smaller than those of the new leaves or new
tissues, once inside the plant phosphorus moves readily from older to younger tissue.
Table 6 shows the effect of the various phosphates on the concentration and content
of cadmium in milled grains. The products have different P levels, and for this reason

P Uptake by Rice from Brazilian Superphosphates

1397

Table 4
Dry matter yield of grains, shoot and roots of the upland rice as related to rates and
sources of P
Phosphorus rates

Araxa-SSP

mg dm3

_____________________________

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0
25
50
100
200
CV(%)

6.49cA
9.97bA
12.69aA
11.66aA
11.45aA
5.5

0
25
50
100
200
CV(%)

5.93cA
8.39bA
9.16abA
9.78aA
8.71abB
6.4

0
25
50
100
200
CV(%)

2.61bA
2.88abA
2.74abA
3.32aA
3.24aA
8.9

Catalao-SSP

Irece-SSP

Lagamar-SSP

g pot per pot _______________________________

Grains
6.49cA
6.49cA
6.49cA
10.03bA
10.05aA
10.58bA
12.03aA
12.08aA
12.13aA
11.84aA
12.30aA
12.10aA
11.53aA
12.40aA
11.19abA
5.9
6.2
5.6
Shoot
5.93bA
5.93cA
5.93cA
7.92aA
8.71abA
8.94bA
9.04aA
9.61abA
9.71bA
9.04aAB
8.32bB
9.75bA
9.09aB
9.75aAB
11.33aA
9.7
7.5
7.6
Roots
2.61bA
2.61bA
2.61bA
2.64bA
2.59bA
2.54bA
2.52bA
2.27bA
2.66bA
3.12bA
3.43aA
3.60aA
3.83aA
3.93aA
4.07aA
9.0
9.8
10.4

Notes. Means followed by the same lower case letters on the column and upper case letters on the
row are not different by the Tukeys test (P < 0.05). Control: None P rate (0 mg dm3 ) plus N, K,
Ca, Mg, and micronutrients.

Table 5
Total P accumulation (grains + shoot + roots) on the upland rice as related to rates and
sources of P
Phosphorus rates

Araxa-SSP

mg dm3
0
25
50
100
200
CV (%)

______________________________

7.97dA
30.50cA
41.85bAB
47.80bB
69.77aA
9.8

Catalao-SSP

Irece-SSP

Lagamar-SSP

mg per pot ________________________________

7.97eA
7.97dA
7.97dA
27.07dA
34.97cA
30.45cA
44.07cAB
38.17cB
48.27bA
57.15bA
48.27bB
52.42bAB
80.07aA
70.37aA
72.75aA
6.2
6.7
13.2

Notes. Means followed by the same lower case letters on the column and upper case letters on the
row are not different by the Tukeys test (P < 0.05). Control: None P rate (0 mg dm3) plus N, K,
Ca, Mg, and micronutrients.

1398

J. Lavres Jr et al.

Shoot dry weight (g per pot)

14

(R2 = 0.68**)

12
10
8
6
4
0,0

0,5
1,0
1,5
Shoot P concentration (g kg1)

2,0

Figure 5. Relationships between shoot dry weight (Y) and P shoot concentration (X) in the upland
rice, corresponding to average of the P sources.

Root dry weight (g per pot)

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3.9347X)

Yaverage = 10.0652(1 e

Yaverage = 3.3898(1 e

4.4537X)

(R2 = 0.20*)

1
0,0

0,5
1,0
1,5
Shoot P concentration (g kg1)

2,0

Figure 6. Relationships between grain yield of milled rice (Y) and P shoot concentration (X) in the
upland rice, corresponding to average of the P sources.

different quantities were also used to supply a determined rate of phosphorus. The concentration of Cd in milled grains ranged from 0.12 to 0.18 mg kg1 . All these values are
below the maximum set by the National Sanitary Vigilance Agency (ANVISA), which is
1.0 mg Cd kg1 of dry mass (BRASIL 1965). Since the Cd concentration in the various
products is between 0.99 and 1.00 mg kg1 , no effect of source would be expected. This
result is also probably due to the low Cd translocation in plants and its preferential accumulation in roots (Wu et al. 2007). Besides, in SSPs obtained from Araxa, Catalao, and
Lagamar rocks, the Cd level increased only with the lowest rate of P and remained constant at the others. Nevertheless, only in the case of the Irece-SSP, the concentration and
content of cadmium increased as the phosphate rate up to 0.40 mg kg1 and 0.61 g per
plants, respectively. By all appearances the plant exercises some control on the absorption

P Uptake by Rice from Brazilian Superphosphates

Yaverage = 12.7846(1 e

3.5847X)

1399

(R2 = 0.75**)

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Grain yield of milled rice (g per pot)

14
12
10
8
6
4
0,0

0,5
1,0
1,5
Shoot P concentration (g kg1)

2,0

Figure 7. Relationships between root dry weight (Y) and P shoot concentration (X) in the upland
rice, corresponding to average of the P sources.

or transport of Cd, which regulates the entrance and accumulation in the grain (Iretskaya,
Chien, and Menon 1998; Iretskaya and Chien 1999).

Discussion
Should totally acidulated phosphates always be highly soluble in water? (Prochnow,
Alcarde, and Chien 2004). This question was explored by the authors with the following review (not exhaustive) of the literature. In the case of SSP, the main cause of low
solubility in water is the presence of R2 O3 dissolved preferentially by H2 SO4 in relation
to the apatite (Gilkes and LimNunez 1980; Bolland and Gilkes 1998). As a consequence,
the proportion of the water-soluble fraction is diminished. The SSP prepared experimentally with phosphate rock containing 3%, 4%, and 7% iron oxide presented the following
efficiency in relation to monocalcium phosphate p.a. (MCP): 86%, 80%, and 46%. The
water-soluble P corresponded to 77%, 67%, and 44% of the total (Prochnow et al. 2003).
Recently, Prochnow et al. (2008) verified that at a soil pH of 5.2, the fertilizers (two single
and two triple superphosphates) required 73% to 95% water-soluble P to reach the maximum dry-matter yield of the wheat, while they required 60% to 86% WSP at pH 6.4.
To reach 90% of the maximum yield, all superphosphate fertilizers required <50% WSP.
The authors concluded that these results show that it is not always necessary to have high
water solubility as required by legislation in many countries. Moreover, they suggest that
higher levels of water-insoluble P as compounds of FeAlP can be tolerated in acidulated
P fertilizers when applied to slightly acid soils than when applied to strongly acid soils.
Mullins (1988) showed that SSP with 80% water-soluble P was just as efficient as
MCP in promoting the plant growth. However, the efficiency declined when the ratio
was less than 80%. The results of this and other studies suggest that the current effect
of impurity compounds on the content of water-soluble P is not a problem.
The P fraction of phosphates soluble in neutral ammonium citrate (NAC) with different
levels of R2 O3 was less efficient than those soluble in NAC + H2 O in the direct effect.
However, the residual effect would lead to a higher dry matter yield (Prochnow, van Raij,

1400

J. Lavres Jr et al.

Table 6
Cadmium added by Brazilian simple superphosphate, concentration and accumulationof
Cd in grains of upland rice as related to rates and sources of P
Phosphorus rates

Cadmium added

Cadmium
concetration

Cadmium
accumulation

mg dm3 _____ _____ g dm3 _____ _______ mg kg1 _______ _________ g per pot _________
Araxa-SSP
0
0.000
0.08a
0.12b
25
0.316
0.14a
0.34a
50
0.632
0.12a
0.36a
100
1.264
0.12a
0.33a
200
2.528
0.12a
0.32a
Catalao-SSP
0
0.000
0.08a
0.12b
25
0.294
0.10a
0.25ab
50
0.588
0.12a
0.35a
100
1.176
0.12a
0.34a
200
2.352
0.14a
0.39a
Irece-SSP
0
0.000
0.08b
0.12b
25
0.384
0.14b
0.37ab
50
0.768
0.16b
0.46a
100
1.536
0.18b
0.54a
200
3.022
0.40a
0.61a
Lagamar-SSP
0
0.000
0.08a
0.12b
25
0.357
0.16a
0.40a
50
0.714
0.16a
0.47a
100
1.428
0.18a
0.53a
200
2.856
0.16a
0.40a
CV (%)
7.9
9.1
8.4

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_____

Notes. Means followed by the same lower case letters on the column of each P source are not
different by the Tukeys test (P < 0.05).

and Kiehl 2002). The extraction of the water-soluble P fraction from SSP did not reduce the
P availability as measured by the yield of dry matter and by the accumulation of phosphorus
in the plants (Prochnow, van Raij, and Kiehl 2002), such as observed in this current study.
Malavolta and Alcarde (1986) carried out an extensive review of the Brazilian and
foreign literature reporting experiments with phosphates of different solubilities. The information obtained permitted two conclusions: (i) the sources of P2 O5 soluble in NAC give the
same results as those soluble in water; and (ii) the legislation should remove the minimum
level in water in the case of phosphates obtained by acidulation.
In soils with high capacity of phosphate adsorption, SPPs with lower solubility in
water can give better results than more soluble ones (Prochnow et al. 2006a). Experiments
conducted with non-acidulated phosphates whose P2 O5 is insoluble in water, but soluble in
citrate, also show that this extractor is sufficient to characterize their agricultural value, as
shown by some examples. Magnesium multiphosphate (Fosmag ), in pot soil experiments

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P Uptake by Rice from Brazilian Superphosphates

1401

with corn and soybean plants, showed the same SSP production, although it does not have
P2 O5 water-soluble (IFDC 1989). A similar result was obtained by Ferreira et al. (1989) in
a field experiment with sugarcane. In the studies of Nakayama et al. (1998), thermophosphate insoluble in water but soluble in citrate, produced yields equivalent to 106% and 82%
of those obtained with triple superphosphate (TSP).
The results presented, along with many others, justify the proposal of Alcarde and
Prochnow (2004) of eliminating the requirement for a minimum P water-soluble for
acidulated phosphates sold individually, that is, there should only be a guarantee water-P.
The data of this experiment, which agree with the findings in the published literature,
show that the P fraction of acidulated phosphates that is not soluble in water, but is totally
or partially soluble in neutral ammonium citrate, is promptly available. It thus follows that
there is no justification for setting a minimum P water-soluble in SSPs from the standpoint
of utilization of the phosphorus by the plant. The water-soluble P in these fertilizers appears
as bicalcium phosphate, iron, and aluminum phosphate, which are soluble in NAC and for
this reason, are available (Prochnow, Alcarde, and Chien 2004). It must be remembered,
however, that the solubility evaluated in the laboratory does not necessarily translate into
availability in the field (Malavolta 1998). Moreover, Sikora et al. (1989) noted that, with
the increasing amounts of impurities in the P fertilizers, the AOAC method might become
inadequate to evaluate the P availability to plants, and that a more efficient method should
be developed.
The low Cd level of igneous phosphate rocks, as the case of Brazilian rocks, makes
their concentration low in the phosphates derived from those rocks, as can be noted in this
experiment. Consequently, low transfer to the plant, particularly the edible part such as
rice grains, would be expected. On the other hand, chemical analysis of the SSP produced
from Togo rock (sedimentary rock) shows the highest level of Cd (Table 1) which could
enhance the cadmium concentration or accumulation in the milled rice grains, and finally
would cause negative effects on the grain quality.

Conclusions
Superphosphate fertilizers obtained by total acidulation of phosphate rock, containing
between 17.28% and 20.90% of total P2 O5 , with levels between 17.07 and 20.64% soluble
in NAC + H2 O, and solubility in H2 O of between 11.11% and 18.94%, did not differ significantly in rice production. These results suggest that the fraction between the total level and
that soluble in NAC + H2 O, or in water alone, can be utilized by the plant. Furthermore,
the entrance of Cd via Brazilian superphosphates, and the subsequent transfer to the rice
grains, did not represent a potential risk of contamination of the edible product, so there is
no negative effect on the food chain.

Acknowledgments
This is the last manuscript written by Professor E. Malavolta, who unfortunately passed
away on January 19, 2008. This publication is our tribute to his passion for the Soil
Science and the Mineral Nutrition of Plants. To CNPq for financial support (Ref. Proc.
303184/2006-0). Jos Lavres Jr. and Thiago A. R. Nogueira have FAPESP scholarship
(Ref. Proc. 07/58406-1 and 07/59402-0), respectively. To Galvani Indstria, Comrcio
e Servios Ltda., So Paulo SP. The authors are in debt to Dr. Nand Kumar Fageria
(EMBRAPA/CNPAF) for helpful comments and interesting discussion.

1402

J. Lavres Jr et al.

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