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Soil & Tillage Research 156 (2016) 110118

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Soil & Tillage Research


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Phosphorus sorption index in humid tropical soils


Murilo de Campos, Joo Arthur Antonangelo, Lus Reynaldo Ferracci Alleoni*
University of So Paulo, College of Agriculture Luiz de Queiroz, Department of Soil Science, CP 09 Piracicaba, SP 13418-900, Brazil

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 20 January 2015
Received in revised form 28 September 2015
Accepted 29 September 2015
Available online 9 November 2015

The dynamics of phosphorus (P) in soils is strongly inuenced by organic and inorganic solid phases,
biological activity and environmental factors. Highly weathered soils naturally contain low levels of P
available to plants and have high adsorption capacity. The maximum adsorption capacity of P (Smax) has
been widely used to evaluate the adsorption capacity of soil P. The P sorption index (PSI) is also used for
evaluating the P adsorption capacity of soil from a single concentration of P and is an effective alternative
in the estimation of maximum adsorption. We obtained the maximum capacity of P adsorption (Smax) and
the P sorption index (PSI) of 29 Brazilian soils with different chemical, physical and mineralogical
attributes. The use of the PSI to estimate the adsorption of P in a long-term experiment was also
evaluated. For Smax, rates of 10, 25, 50, 100, 200 and 260 mg L1 of P in 24 h of contact were used. For the
PSI, soils were divided into groups because of the variation in their capacity to adsorb P, and each group
received an optimal P rate: 200, 500, 1000, 1500 or 3000 mg L1 of P. The periods of reaction assessed
were 1, 3, 7, 21, 42, and 84 d. Smax was affected by amounts of clay, Fe and Al oxides and organic carbon
(OC), which ranged from 61.7 (Typic Haploxeralf) to 5459.5 mg kg1 (Mollic Fluvaquent). In the PSI, the
average percentage of P adsorbed at the end of the contact period (84 d) ranged from 23% to 49% of P that
was mixed initially and was, on average, four times higher than their values after 1 d of contact. Oxisols,
Alsols and Gleysols had the highest values of PSI. On the other hand, Ultisols and Entisols had the lowest
ones. The PSI behaved similarly to the Smax, and the highest values were found in soils with high contents
of clay, C, crystalline and poorly crystallized Fe and Al oxides. Furthermore, the PSI was higher in the 84th
day, highlighting the inuence of the period of contact on P adsorption.
2015 Elsevier B.V. All rights reserved.

Keywords:
Maximum P adsorption
P sorption index
Humid tropical soils

1. Introduction
The dynamics of phosphorus (P) is controlled by the organic and
the mineralogical constitution of the soil, by the pH and the ionic
strength of the soil solution, as well as by environmental factors
such as moisture content and temperature (Pierzynski et al., 2005).
Highly weathered soils naturally contain low levels of P
available to plants and have a high P adsorption capacity. An
example of these soils are the Oxisols, which cover immense areas
of humid tropical and subtropical regions in Brazil and account for
about 60% of the areas of agricultural importance (Tiessen, 2005;
Soares and Alleoni, 2008). In these soils, due to the advanced
process of weathering, the clay fraction is dominated by 1:1 silicate
minerals, oxides, hydroxides and oxihydroxides of Fe, Al and Mn,
which have a high afnity to adsorb P. This adsorption, at rst, is
rapid, and is followed by a period of specic adsorption (Sposito,
1989).

* Corresponding author.
E-mail address: alleoni@usp.br (L.R.F. Alleoni).
http://dx.doi.org/10.1016/j.still.2015.09.020
0167-1987/ 2015 Elsevier B.V. All rights reserved.

In general, high rates of fertilizers and/or agro-industrial


residues containing P are usually applied to the soil with the
aim of increasing crop production (Townsend and Porder, 2012).
This practice, however, can saturate binding sites in P soil particles
and result in a reduction of the capability of the soil to retain P. In
soils with low P retention potential, there is high likelihood of
release the P into the soil solution, and the element could reach
aquatic environments through runoff or drainage water (Sims
et al., 1998; Allen et al., 2006).
The degree of P saturation is a potential risk indicator of P losses
from non-point sources such as agricultural soils under eld
conditions (Hooda et al., 2000; Casson et al., 2006) and has been
used in many countries. This parameter is calculated from P, Al and
Fe contents extracted with an acidic ammonium oxalate solution
(Pox, Alox and Feox), which will represent the P already sorbed (Pox)
and the most active binding sites (Alox and Feox). It is dened as the
ratio of the amount of P is already sorbed and the sorption capacity
of the soil P (Maguire and Sims, 2002; Hughes et al., 2005). The P
sorption capacity is dened as the sum of P sorption index with Pox
(PSC = PSI + Pox).

M. de Campos et al. / Soil & Tillage Research 156 (2016) 110118

Maximum P adsorption capacity (Smax) is estimated by tting


empirical models, such as the Langmuir isotherm, to data from
laboratory experiment, where soil is equilibrated with solution
containing different amounts of P. However, the traditional
method of calculating Smax requires an extended period, and is
both laborious and expensive for routine use (Bache and
Williams, 1971). Bache and Williams (1971) developed a simple
and alternative way to calculate Smax called the P Sorption Index
(PSI), which is used to evaluate the soil adsorption capacity from
the addition of a single concentration of P. Because it is so
practical, the PSI is often used in environmental studies to
calculate the degree of P saturation (DPS). The DPS is used for
estimating the risk potential of loss of P from the soil and takes
into account the percentage of sites saturated by P in relation to
its adsorption capacity. The PSI is calculated from the addition of
a single rate of P and 18 h of contact being a fast and effective
form to estimate the maximum P adsorption due to the high
correlation with the Smax (Mozaffari and Sims, 1994; Sims, 2009;
Xue et al., 2014).
However, the PSI and the DPS are not widely disseminated in
Brazil. This technique is used mainly in European countries and
USA. To adopt this practice, rstly, there is a need to evaluate
the P sorption capacity using techniques as is used to calculate
DPS. The aim in this study was to obtain the maximum P
adsorption capacity (Smax) and the P sorption index (PSI) of
highly weathered tropical soils from Brazil, and to evaluate the
viability of using the PSI to estimate P adsorption in soils over
the long term. The hypothesis was that the degree of phosphorus
saturation can be calculated for these soils through the
presented methods in order to assess the potential of P releasing
to the environment, taking the water eutrophication by
phosphorus accumulation into account.

111

2. Material and methods


Soil samples were collected from several sites under forestry
(native and planted) in the state of Sao Paulo, Brazil, which had not
been exposed to articial sources of P (Table 1). Soil classes used
were as follows: Oxisols, Ultisols, Alsols, Entisols, Inceptisols,
Histosols and Mollisols (Table 1), making a total of 29 soil samples
(Soil Survey Staff, 1999). Details of the attributes of these soils can
be found in Soares and Alleoni (2008).
Chemical characterization was obtained from air-dried soil
samples and passed through a sieve 2 mm in diameter (10 mesh).
The carbon content (C) was obtained using a modied Walkley
Black method (Nelson and Sommer, 1982). The samples were
passed through a 100 mesh sieve, and the organic carbon content
was measured after oxidation by organic matter in the soil with
potassium dichromate solution, 0.167 mol L1 (K2Cr2O7) in concentrated sulfuric acid.
The clay content was determined following the hydrometer
method (Gee and Or, 2002). A sodium dithionitecitrate
bicarbonate solution (Mehra and Jackson, 1960) was used to
obtain the crystalline oxide contents of Fe and Al, and determination was by atomic absorption spectrophotometry (AAS). Poorly
crystallized forms or amorphous Fe and Al were extracted by
0.1 mol L1 of oxalic acid solution + 0.2 mol L1 ammonium oxalate
at pH 3 (Schoumans, 2009). Iron and aluminum content were
determined by inductively coupled plasma optical emission
spectrometry (ICP-OES).
2.1. Adsorption of P by the soil
2.1.1. P Adsorption capacity (Smax)
The residual phosphorus content (P-rem) was used to obtain
the most appropriate rates of P to add when estimating the

Table 1
Chemical, physical and minerological properties of the soils.
Soils

Geographical coordinates

Clay

Feox

Alox

FeDCB

AlDCB

Qualitative
mineralogy

8
14
8
10
24
50
14
24
14
24
4
4
20
9
19
23
4
22
6
13
8
29
29
33
103
16
12
4
28

181
221
202
201
530
684
716
222
342
470
60
100
247
202
366
246
100
427
80
142
101
345
658
532
476
243
204
40
543

0.3
0.4
0.5
0.6
1.2
2.1
2.7
1.0
0.6
1.3
0.1
0.1
0.8
0.7
1.5
1.3
0.2
2.5
0.2
1.1
0.4
0.8
1.9
6.5
1.4
0.6
1.6
0.2
6.9

0.4
0.7
0.6
0.6
2.0
2.4
2.0
0.9
0.9
2.4
0.1
0.1
0.6
0.4
0.5
0.7
0.2
0.7
0.2
0.3
0.2
1.5
2.2
1.3
9.4
1.1
0.5
0.1
2.0

19.0
13.2
20.8
52.5
85.4
183.1
205.5
18.7
41.6
111.8
3.4
5.2
32.1
8.0
44.2
31.5
8.3
48.8
2.8
6.4
10.7
83.7
190.3
21.1
3.5
18.7
17.0
8.0
106.4

3.6
3.2
4.7
7.4
10.9
8.4
25.4
7.0
8.4
15.3
1.5
1.1
5.5
2.0
1.6
5.5
1.6
5.8
2.3
1.3
1.2
20.7
10.2
40.2
20.4
6.9
1.5
0.9
7.6

Kt, Gt, Hm
Kt, Gt, Hm
Kt, Gt, Hm
Kt, Gb, Gt, Hm
Kt, Gt, Hm
Kt, Gb, Hm
Kt, Gb, Gt, Hm
Kt
Kt, Gb, Gt
Kt, Gb, Gt, Hm
Kt
Kt, Il
Kt, Gt, Hm
Kt, Il
Kt, Il, HIV
Kt, Gt, Hm
Kt, Il
Kt, Gt, Hm
Kt
Il, HIV
Kt, Il
Kt, Gb
Kt, Gb, Hm
Kt, Gt, Hm
Kt
Kt
Kt, Il
Kt, Il, HIV
Kt, Gt, Hm

1

g kg
Arenic Hapludox
Typic Hapludox-1
Typic Hapludox-2
Rhodic Hapludox-1
Rhodic Hapludox-2
Rhodic Eutrudox
Rhodic Acrudox
Xanthic Hapludox-1
Xanthic Hapludox-2
Xanthic Acrudox
Arenic Hapludult-1
Arenic Hapludult-2
Typic Hapludult-1
Typic Hapludult-2
Typic Hapludult-3
Typic Hapludult-4
Rhodic Hapludult-1
Rhodic Hapludult-2
Typic Quartzipsamment
Typic Udorthent
Typic Psammaquent
Typic Rhodudalf
Rhodic Eutrudalf
Typic Fluvaquent
Mollic Fluvaquent
Typic Haplustept
Typic Albaqualf
Typic Haploxeralf
Typic Argiudoll

22 190 S 47 100 W


22 150 S 47490 W
22 190 S 47 100 W
22 010 S 47 530 W
21050 S 47 080 W
22 430 S 47 380 W
21100 S 47480 W
22 150 S 47490 W
21570 S 47 590 W
20 100 S 48 020 W
22 320 S 47 540 W
22 380 S 47 110 W
22 430 S 47 380 W
22 170 S 49 330 W
22 060 S 46 400 W
22 430 S 47 380 W
22 120 S 49 560 W
22 590 S 47 300 W
22 320 S 47 540 W
22 120 S 49 390 W
22 260 S 49 450 W
22 590 S 47 300 W
22 060 S 47 070 W
24 430 S 47 520 W
21100 S 47480 W
22 070 S 47 390 W
22 420 S 47 380 W
22 220 S 46 560 W
22 080 S 47400 W

Kt = Kaolinite; Gt = Goethite; Hm = Hematite; Gb = Gibbsite; Il = Illite e HIV = hydroxy-interlayered vermiculite; Feox e Alox = Fe e Al content extracted by ammonium oxalate;
FeDCB e AlDCB = Fe and Al content extracted by sodium citratebicarbonatedithionite solution.

112

M. de Campos et al. / Soil & Tillage Research 156 (2016) 110118

maximum P adsorption capacity (Smax) (V. Alvarez et al., 2000). The


P content in the equilibrium solution was determined by
colorimetry (Murphy and Riley, 1962).
The Langmuir P adsorption isotherm was tted to the
experimental data for each soil to estimate Smax. To achieve this,
2.0 g of soil were mixed to a 0.01 mol L1 CaCl2 solution amended
with rates of P, derived from a solution of KH2PO4. The P rates (10,
25, 50, 100, 200 and 260 mg L1) were determined in accordance
with the value of the P-rem (Alvarez et al., 2000). Some soil
samples received further rates, since those rst applied were not
sufcient to establish maximum adsorption. Thus, 400, 600 and
800 mg L1 of P were mixed to the soil samples. The samples have
been shaken for 24 h and centrifuged for 15 min at 1844  g. The P
content in the solution was determined by colorimetry (Murphy
and Riley, 1962). The adsorption isotherms were tted according to
the P concentration values as a function of the P adsorbed in nal
equilibrium concentrations in the solution (Olsen and Watanabe,
1957). The Langmuir isotherm is given by equation:
x
K L  ADmax  C e

;
m
1 K L  C e
in which x/m = the amount of P adsorbed to the soil in mg kg1;
KL = the constant related to the energy used in the adsorption of P
to the soil in L mg 1; Smax = the Smax of the soil in mg kg1; and
Ce = the nal concentration of P in the equilibrium solution in
mg L1. For estimation of the constants KL and Smax, the Langmuir
equation was linearized as (Graetz and Nair, 2009):
C
1

1 Smax C e ;
x=m K L  Smax
2.1.2. Phosphorus saturation index (PSI)
The PSI was calculated from a single point isotherm (Bache and
Williams, 1971). For this calculation, 2.5 g of soil, sifted through a
2 mm sieve, were mixed to 25 ml of a solution containing
0.01 mol L1 CaCl2 as supporting electrolyte. Rates of P (KH2PO4)
were calculated from the Smax of previous experiment for every soil
type, since one single concentration would not be effectively with
all the soils over a determined time. Accordingly, the samples were
divided into ve groups, each receiving the optimal concentration
of P in relation to its adsorption capacity. The groups were divided
as follows: IMollic Fluvaquent, Rhodic Acrudox, Xanthic Acrudox
and Rhodic Eutrudox (Very High adsorption capacity with Smax >
2000 mg kg1); IIRhodic Eutrudalf, Typic Argiudoll, Rhodic
Hapludox-2 and Xanthic Hapludox-2 (High adsorption capacity
with Smax between 1000 and 2000 mg kg1); IIITypic Fluvaquent,
Typic Rhodudalf, Xanthic Hapludox-1, Typic Haplustept, Rhodic
Hapludult-2, Rhodic Hapludox-1 and Typic Hapludox-3 (Medium
Adsorption Capacity with Smax between 500 and 1000 mg kg1);
IVTypic Hapludult-4, Arenic Hapludox, Typic Hapludult-3, Typic
Hapludult-3, Typic Hapludox-1 and Typic Albaqualf (Low adsorption capacity with Smax between 200 and 500 mg kg1); and V
Typic Hapludult-2, Typic Quartzipsamment, Typic Udorthent,
Arenic Hapludult-1, Rhodic Hapludult-1, Arenic Hapludult-2, Typic
Psammaquent and Typic Haploxeralf (Very Low adsorption
capacity with Smax < 200 mg kg1).
In order to determine the rates, the values of Smax (mg kg1)
were rst converted to mg L1, which thereby gave the content
level of P in the solution required to attain maximum adsorption in
one day. Freese et al. (1995) and Indiati and Diana (2005) observed
that adsorption in 90 d is approximately three times higher than
that attained in one day. Consequently, the content obtained
(mg L1) in one day was multiplied by 3 to achieve a concentration
of P sufcient to attain P adsorption. Freese et al. (1995, 1992)
suggested that the rates applied should be decreased by

approximately 30% at the end of the contact period, so as to


ensure about 70% of the initial concentration that was mixed still
remained. In this way, the solutions were calculated so that the
equilibrium concentrations at the end of the contact period would
be equivalent to approximately 70% of the amount of P mixed,
which was sufcient to maintain a constant ionic strength in the
solution and induce adsorption.
The P concentrations in solution were assessed at 1, 3, 7, 21,
42 and 84 d. The samples were analyzed in triplicate using a batch
for each reaction period. These were shaken daily for 2 h after the
rst 24 h of agitation, using a horizontal end-over-end agitator.
After each period, samples were centrifuged at 1844  g for 15 min,
and the P content determined by colorimetry (Murphy and Riley,
1962). The adsorbed P was calculated as the difference between the
mixed P and the P that remained in the solution and the PSI was
estimated as:
1

PSImgkg

X
;
logC

in which X = P sorbed (mg kg1) = (PiPf)  (0.025 L)/(0.0025 kg


soil); C = Concentration of P in equilibrium (mg L1); P = initial P in
equilibrium concentration (mg L1) and Pf = nal P in equilibrium
concentration (mg L1).
PSI values and the percentage of adsorbed P were evaluated by
the means comparison test (Tukey test) using SASM AGRI software
(Canteri et al., 2001). Due to the low standard deviation of the
results, we used the Tukey test at 1%. Multivariate analysis was
performed to determine the principal components analyses using
the computer statistical package from Statistica (Statsoft, 2005).
Criteria used to determine the factors followed the Kaiser rule,
which takes into account the eigenvalues 1 or to explain over 85%
of the total variance (Kaiser, 1958). As regards correlations, those
considered were  | 0.70 | (Manly, 1994).
3. Results and discussion
The values of Smax for the soils followed the expectations and
varied mainly as a function of clay content, Fe and Al oxides and C,
which was already expected for tropical soils, in general (Table 2).
In fact, the Alox, which is the amorphous forms of aluminum, also
represents the most reactive aluminum oxide from clay fraction,
responsible for the high phosphorus adsorption. The strong
positive correlations between Smax and Alox as well as the clay
can be observed in Table 3. Due to the wide variations of these
attributes (Table 1), the Smax ranged from 61.7 mg kg1 in the Typic
Haploxeralf to 5459.5 mg kg1 in Mollic Fluvaquent (Table 2).
Mollic Fluvaquent had high contents of C and Alox (Table 1).
Considered as ambivalent, OM is capable of performing a dual role
with regard to the adsorption of P, unfavorable because of the
blocking of adsorption sites (Guppy et al., 2005), and favorable, in
terms of its anionic character, since the sites attract electrostatically cations such as Ca, Fe, and Al and these cations induce P
retention (Sanyal and De Datta, 1991).
The poorly crystallized fraction of Al hydroxides is primarily
responsible for the adsorption of P by having a high specic surface
area and, thus, a high number of active sites (Paulter and Sims,
2000). This fraction inuenced the large adsorption of P in Mollic
Fluvaquent. Some Oxisols such as Rhodic Acrudox and Xanthic
Acrudox had high potential for adsorption (Table 2). The other
Oxisols, as well as the Alsols, also showed an afnity for adsorbing
P (Table 2).
The Oxisols and the Alsols had high levels of FeDCB and AlDCB.
High Smax values are found in these soils due to the intense process
of desilicatization. Because these soils are well-drained and located
in humid tropical regions, they have an accumulation of oxides and

M. de Campos et al. / Soil & Tillage Research 156 (2016) 110118

113

Table 2
Maximum P adsorption capacity (Smax), calculated rates and added to the P sorption index (PSI) for soil groups.
Soil

Smax

Mollic Fluvaquent
Rhodic Acrudox
Xanthic Acrudox
Rhodic Eutrudox
Rhodic Eutrudalf
Typic Argiudoll
Rhodic Hapludox-2
Xanthic Hapludox-2
Typic Fluvaquent
Typic Rhodudalf
Xanthic Hapludox-1
Typic Haplustept
Rhodic Hapludult-2
Rhodic Hapludox-1
Typic Hapludox-3
Typic Hapludult-4
Arenic Hapludox
Typic Hapludult-1
Typic Hapludult-3
Typic Hapludox-1
Typic Albaqualf
Typic Hapludult-2
T. Quartzipsamment
Typic Udorthent
Arenic Hapludult-1
Rhodic Hapludult-1
Arenic Hapludult-2
Typic Psammaquent
Typic Haploxeralf
a
b
c
d

P solution
(90 d)b

mg kg1

P solution
(1 d)a
mg L1

5.459.56
4.487.29
2.909.17
2.717.33
2.129.22
1.462.28
1,757.73
1,354.01
1,042.57
978.90
922.36
892.81
576.62
565.99
538.97
460.49
425.61
303.03
310.93
305.14
285.43
213.57
213.55
180.86
181.62
140.19
121.83
103.31
61.70

545.96
448.73
290.92
271.73
212.92
146.23
175.77
135.40
104.26
97.89
92.24
89.28
57.66
56.60
53.90
46.05
42.56
30.30
31.09
30.51
28.54
21.36
21.35
18.09
18.16
14.02
12.18
10.33
6.17

1.637.87
1.346.19
872.75
815.20
638.77
438.68
527.32
406.20
312.77
293.67
276.71
267.84
172.99
169.80
161.69
138.15
127.68
90.91
93.28
91.54
85.63
64.07
64.06
54.26
54.49
42.06
36.55
30.99
18.51

Calculated ratec

Added
rated

Groups
mg kg1

5.404.96
4.442.42
2.880.08
2.690.16
2.107.93
1.447.66
1,740.15
1,340.47
1,032.14
969.11
913.14
883.88
570.85
560.33
533.58
455.89
421.35
300.00
307.82
302.09
282.57
211.43
211.41
179.05
179.80
138.79
120.61
102.27
61.08

3.000
3.000
3.000
3.000
1.500
1.500
1,500
1,500
1,000
1,000
1,000
1,000
1,000
1,000
1,000
500
500
500
500
500
500
200
200
200
200
200
200
200
200

> 2000
> 2000
>2.000
>2.000
1.0002.000
1.000 - 2000
1,000 - 2000
1,000 - 2000
500 - 1000
500 - 1000
500 - 1000
500 - 1000
500 - 1000
500 - 1000
500 -1,000
200 - 500
200 - 500
200 - 500
200 - 500
200 - 500
200 - 500
< 200
< 200
< 200
< 200
< 200
< 200
< 200
< 200

P Content in the solution required for maximum adsorption in 1 d (mg L1).


P Content in the solution required for maximum adsorption at 90 d (mg L1).
calculated rate to maintain 70% of P in solution.
Rates of P applied in each group.

1:1 silicate mineral predominance, whereby P is preferentially


adsorbed (Mesquita Filho and Torrent, 1993). Pinto et al. (2013)
evaluated the adsorption capacity in the Brazilian Savanna
(Cerrado) Oxisols and found Smax values ranging from 283 to
2635 mg kg1. In the other soils FeDCB had a range from 3.5 in
Arenic Hapludult-1 to 51.3 mg kg1 in Rhodic Hapludult-2 and
1.2 AlDCB in Arenic Hapludult-2 to 41.6 in Typic Fluvaquent.

Table 3
Correlations among soil properties, Smax and PSI (1, 3, 7, 21, 42 and 84 days).
Properties

Correlation coefcients Pearson (r)


Smax

PSI1d

PSI3d

PSI7d

PSI21d

PSI42d

PSI84d

0.75a
0.77b

0.77
0.71

0.76
0.81

0.74
0.78

0.71
0.81

0.76
0.81

0.74
0.79

Clay

0.75
0.86

0.71
0.81

0.79
0.88

0.78
0.80

0.84
0.86

0.82
0.85

0.85
0.87

Feox

0.29
0.53

0.33
0.50

0.38
0.57

0.35
0.53

0.45
0.56

0.44
0.55

0.44
0.53

Alox

0.86
0.96

0.88
0.91

0.85
0.97

0.81
0.91

0.77
0.95

0.81
0.93

0.80
0.95

FeDCB

0.59
0.88

0.52
0.83

0.64
0.91

0.66
0.85

0.69
0.89

0.65
0.90

0.68
0.89

AlDCB

0.61
0.72

0.61
0.66

0.62
0.76

0.60
0.67

0.71
0.73

0.70
0.70

0.71
0.75

a
First line for each soil property represents the correlation coefcients for all
soils.
b
Second line for each soil property represents the correlation coefcients for all
soils except Rhodic Acrudox, Typic Fluvaquent, Mollic Fluvaquent and Typic
Argiudoll, which deviate from the norm (outliers).

The Feox content varied from 0.1 in Arenic Hapludult-1 and


Arenic Hapludult-2 to 6.5 g kg1 in Typic Fluvaquent. With regard
to Alox levels, the variation was 0.1 in Arenic Hapludult-1, Arenic
Hapludult-2 and Typic Haploxeralf to 9.4 g kg1 in Mollic
Fluvaquent, which showed a close correlation between these
levels and the degree of weathering of the soil.
The Ultisols and Entisols presented Smax ranging from 121.8 in
Arenic Hapludult-2 to 576.6 mg kg1 in Rhodic Hapludult-2 and
103.3 in Typic Psammaquent to 213.5 mg kg1 in Typic Quartzipsamment (Table 2), respectively. Guardini et al. (2012) evaluated
the P saturation in Ultisols after application of pig slurry and found
a Smax range of 367426 mg kg1. These values show low
adsorption capacity, primarily represented by the low content of
crystalline and non-crystalline oxides (Table 1). In our study, the P
adsorption capacity in the Typic Haploxeralf and in the Typic
Albaqualf was low, since they are sandy and medium textured soils,
with low concentrations of oxides. The Typic Haplustept and the
Typic Argiudoll presented intermediate Smax values.
In PSI, Mollic Fluvaquent and Rhodic Acrudox belong to the
group I. The rate mixed to these soils (3000 mg L1) was lower than
the rates calculated (5404.96 and 4442.42 mg L1). However, by
using this rate, it was possible to t the four soils into the same
group, and the concentration of P applied was sufcient to
maintain 50% of the P in solution at the end of the contact period.
Likewise, Rhodic Eutrudalf, Typic Fluvaquent, Typic Hapludult2 and Typic Quartzipsamment had a calculated rate slightly higher
than the rate actually mixed but none of them had levels of P in
solution tending to zero.
About 30 to 45% of the P adsorption occurred on the rst day of
contact with the soil in group V (Fig. 1). In soils corresponding to
group III and IV, the adsorption on the rst day represented 2030%
of the total. In groups I and II, the corresponding rst day

114

M. de Campos et al. / Soil & Tillage Research 156 (2016) 110118

adsorption was 3050% of the amount adsorbed after 84 d. These


results are related to P adsorption kinetics, that occur rapidly at
rst, followed by a slower reaction, featuring a specic adsorption
(Barrow and Shaw, 1975; Torrent et al., 1994).
The average percentage of P adsorbed at the end of the contact
period ranged from 23 to 49% of P initially mixed (Fig. 1). In soils
from Groups I and II the decrease of the mixed rates averaged 50%.
As for Groups III, IV and V, the mean decrease was 37, 31 and 23%,

respectively. Freese et al. (1995, 1992) suggested that the mixed


rates should be reduced, on average, about 30% by the end of the
contact period. Our purpose was to mix rates in proportion to the
soils P adsorption capacity, and thus ensure the concentrations
were sufcient to maintain the ionic strength at a constant level
that would favor adsorption over the long term.
In all soils, PSI84d represented, on average, four times the PSI1d,
being 2.28.9 times higher. The PSI84d varied increasingly with the

Fig. 1. Percentage of P adsorbed at rates of 200 (Smax < 200), 500 (Smax 200500), 1000 (Smax 5001,000), 1500 (Smax 10002,000) and 3000 mg L1 (Smax > 2,000) versus
contact time (Tukey test, P < 0.01). The bars represent the mean standard deviation.

M. de Campos et al. / Soil & Tillage Research 156 (2016) 110118

applied rates. The PSI values varied in a similar way to Smax, since
they were affected by the same attributes in the soil.
In Oxisols, the PSI84d ranged from 480 in Typic Hapludox-1 to
4975.8 mg kg1 in Rhodic Acrudox. Together with the Oxisols, the
Entisols, the Alsols, the Typic Argiudoll and the Typic Haplustept
showed the highest values of ISP84d (Fig. 2). The Ultisols and the
Entisols recorded low PSI84d values. Likewise, Typic Haploxeralf
and Typic Albaqualf had low values of PSI84d. The low adsorption
capacity in these soils, as evidenced by Smax, was inuenced,

115

mainly, by the sandy texture and the low levels of oxides and C
(Bolland et al., 2003).
Over the course of the evaluations, the PSI (Fig. 2) did not
always increase. In Typic Psammaquent, Arenic Hapludult-1, and
Arenic Hapludult-2 soils PSI values differed only after 42 d of
contact (p < 0.01). Unlike all other soils, Mollic Fluvaquent, Rhodic
Acrudox, Rhodic Eutrudox, and Typic Hapludult-4 did not differ in
ratings between 42 and 84 d, thus characterizing maximum
adsorption.

Fig. 2. P sorption index (PSI) at rates of 200 (Group V), 500 (group IV), 1000 (Group III), 1500 (Group II) and 3000 mg L1 (Group I) according to contact time (Tukey test;
P < 0.01). The bars represent the mean standard deviation.

116

M. de Campos et al. / Soil & Tillage Research 156 (2016) 110118

6000

PSI84d = 361.81 + 1.14 (Smax)


R2 = 0.90

PSI84d (mg kg-1)

5000

4000

3000

2000

1000

0
0

1000

2000

3000

4000

5000

6000

-1

Smax (mg kg )

95% confidence

Fig. 3. Linear regression between the Smax and the PSI84d in tropical soils.

1,0

Fe ox

0,5

F actor 2 : 2. 65%

AlDCB Clay
CEC
pH
Fe DCB

PSI

C
Alox

0,0

S max

-0,5

-1,0
-1,0

-0,5

0,0
Factor 1 : 97.35%

0,5

1,0

it represented only 3.5% of the total adsorbed content, suggesting


that even over the long-term, the adsorption continues to occur,
making it difcult to reproduce in the laboratory what actually
happens under eld conditions (Maguire et al., 2001).
In general, PSI values at the end of the reaction period were
higher than the values estimated by Smax due to increased contact
time in the PSI. The reaction time of P in soil interferes with the
adsorption, which is an important parameter in the management
of P, whether it is used either as an indicator of environmental
hazards or as available P for cultivated plants. (Fig. 3).
The Smax and PSI parameters were also submitted to principal
component analysis (PCA) that showed what attributes were
responsible for explaining the variations in results in tropical soils.
Fig. 4 shows the projection of variables (a) and cases (b) for all the

1. Arenic Hapludox
2. Ty pic Hapludox
3. Ty pic Hapludox
4. Rhodic Hapludox
5. Rhodic Hapludox
6. Rhodic Eutrudox
7. Rhodic Acrudox
8. Xanthic Hapludox
9. Xanthic Hapludox
10. Xanthic Acrudox
11. Arenic Hapludult
12. Arenic Hapludult
13. Ty pic Hapludult
14. Ty pic Hapludult
15. Ty pic Hapludult
16. Ty pic Hapludult
17. Rhodic Hapludult
18. Rhodic Hapludult
19. Ty pic Quartzipsamm ent
20. Ty pic Udorthent
21. Ty pic Psamm aquent
22. Ty pic Rhodudalf
23. Rhodic Eutrudalf
24. Ty pic Fluvaquent
25. Mollic Fluvaquent
26. Ty pic Haplustept
27. Ty pic Albaqualf
28. Ty pic Haploxeralf
29. Ty pic Argiudoll

Active
Suppl.

1,0
0,8
24
0,6
6
0,4
22 9
F actor 2: 2. 65%

In the Langmuir adsorption model it is assumed that adsorption


occurs at specic sites and takes place in a single layer, reaching the
maximum when it covers the adsorbent surface, and expresses a
nite number of binding sites (Langmuir, 1918). From this, the 84 d
contact period used may not have been sufcient to reach
maximum adsorption, since most of the soils seem to continue
retaining P with the increase of reaction time. Indiati and Diana
(2005) evaluated the retention of P in ten acidic European soils up
to 180 d of reaction and found that, on average, 92% of P was
adsorbed after 90 d of contact; however, adsorption continued
throughout the experiment, even down to a minimum rate (about
2.5%) in some soils during the last days of reaction. Maguire et al.
(2001) evaluated 37 soils from Northern Ireland left 252 d to react
and observed P adsorption continuously. However, in the last 60 d,

0,2

10

5 23

1
131618
27
21
2
28
19
26
17
12
14
20
15 3 8
11

0,0

29

-0,2

25

-0,4
7

-0,6
-0,8

b
-1,0
-3

-2

-1

Factor 1: 97.35%

Fig. 4. Projection of variables (a) and cases (b) subjected to PCA with a number of the soil attributes.

M. de Campos et al. / Soil & Tillage Research 156 (2016) 110118

117

Table 4
Results of principal components analysis.
N

Eigenvalue

% Total variance

Cumulative eigenvalues

Cumulative
%

1
2

1.95
0.05
Eigenvectors
Fator 1
0.70
0.70
Correlations between soil properties

97.35
2.65
Correlations
Fator 2
0.70
-0.70

1.95
2.00

97.35
100.00

Fator 1
0.98
0.98

Fator 2
0.16
-0.16

PSI
Smax

Fator 1
0.37
0.81
0.81
-0.01
0.60
0.73
0.65
0.66

Feox
Alox
Clay
pH
CEC
C
FeDCB
AlDCB
(1)
Correlations |0.70| are signicant (Manly, 1994).

soils studied. Factor 1 (horizontal axis in Fig. 4a) presented the


eigenvalue above as 1, explained 97% of the variations (Table 4) in
results and was inuenced by both the PSI and the Smax. In this case,
the following attributes: Alox, clay and C were the most closely
correlated with these variables ( | 0.70 |). These results were
expected due to the strong relationship between these attributes
and the adsorption of P. The inuence of clay minerals in the
adsorption of P is related to the specic surface area of the
structures (Mesquita Filho and Torrent, 1993). Nwoke et al. (2003)
also found a signicant correlation with Alox, clay, and AlDCB in
highly weathered soils in Northern Nigeria. Fontes and Weed
(1996) used multiple regression equation on Savanna soils in Brazil
and oberved that the contents of Alox, gibbsite, goethite and
hematite accounted for more than 95% of the variation in
maximum P adsorption. In this study, however, levels of Feox
and kaolinite were not included.
Mesquita Filho and Torrent (1993) also used multiple regression
analysis on Brazilian Oxisols samples and observed a good t of the
maximum P adsorption to kaolinite and attributed this result to the
abundance of this mineral in the soils studied, as was the case in
our study. Although they were not signicant in the PCA, the
crystalline structures may inuence the adsorption of P because
they are highly weathered soils, where high levels of crystalline
oxides are observed (Table 2). With regard to C, Eberhardt et al.
(2008) found total C content to be one of the attributes that best
represented adsorption in Oxisols originating from the Brazilian
Savanna. The relation of total C with P adsorption is due to the
increase in C content occuring in function of the clay content and
that clay would be inuencing the adsorption of P (Eberhardt et al.,
2008).
4. Conclusions
1. The PSI behaved similarly to the Smax due to the high correlation
between values of both.
2. In general, the PSI was higher at the end of the contact period,
which emphasizes the inuence of time on the kinetic of P
adsorption.
3. It is necessary to vary the rates of P as a function of the P
adsorption capacity of the soil, but the PSI can be recommended
for long-term adsorption studies in highly weathered tropical
soils because it is practical to determine.
4. The PSI84d and Smax were highly correlated, and clay (high
contents), C and both crystalline and poorly crystallized oxides
of Fe and Al, in general, were the main components related to
the adsorption of P in humid tropical soils.

(1)

Acknowledgment
To CAPES (Brazilian Coordination for the Improving of Higher
Education Personnel) for nancial support of this research.
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