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Effect of soil properties on

the kinetics of phosphate
release
a b
J. De Smet , J. Vanderdeelen & G. Hofman
a

a
Department Soil Management and Soil Care ,
University of Ghent, Faculty of Agricultural
and Applied Biological Sciences , Coupure
Links 653, Gent, B‐9000, Belgium
b
Department of Applied Analytical and
Physical Chemistry , University of Ghent,
Faculty of Agricultural and Applied Biological
Sciences, Coupure Links 653 , Gent, B‐9000,
Belgium
Published online: 11 Nov 2008.

To cite this article: J. De Smet , J. Vanderdeelen & G. Hofman

(1998) Effect of soil properties on the kinetics of phosphate release,
Communications in Soil Science and Plant Analysis, 29:11-14, 2135-2147, DOI:
10.1080/00103629809370098

To link to this article: http://dx.doi.org/10.1080/00103629809370098

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 COMMUN. SOIL SCI. PLANT ANAL., 29(11-14), 2135-2147 (1998)

EFFECT OF SOIL PROPERTIES ON THE KINETICS OF PHOSPHATE

RELEASE
Downloaded by [Michigan State University] at 12:58 29 December 2014

J. De Smet
Department Soil Management and Soil Care, University of Ghent,
Faculty of Agricultural and Applied Biological Sciences, Coupure Links 653, B-9000 Gent,
Belgium

J. Vanderdeelen
Department of Applied Analytical and Physical Chemistry
University of Ghent, Faculty of Agricultural and Applied Biological Sciences, Coupure
Links 653, B-9000 Gent, Belgium

G. Hofman
Department Soil Management and Soil Care, University of Ghent,
Faculty of Agricultural and Applied Biological Sciences, Coupure Links 653, B-9000 Gent,
Belgium

ABSTRACT

The kinetics of the phosphate release by 35 non-calcareous soil samples were

investigated by consecutive extraction of the soil. The soil samples covered a wide
range of texture, pH and degree of phosphate saturation. For all soils, phosphate
release initially followed first order kinetics. With time, the process became linear to
the logarithm of time. These relationships were used to distinguish between the initial
fast process of phosphate desorption and the much slower diffusion-dissolution
process. The influence of physico-chemical soil properties on the parameters
describing the two processes was investigated using multiple regression analysis. The
total amount of reversibly adsorbed phosphate was highly significant correlated to the
oxalate extractable phosphate of the soil: the former approximated 33 % of the latter.
The rate constant of the initial desorption process was mainly influenced by the pH
of the soil: increasing the pH positively affects the desorption rate. The kinetics of the
final diffusion-dissolution process was most related to the oxalate extractable
phosphorus content of the soil. Under the prevailing experimental conditions, the
reversibly adsorbed phosphate is completely released after eight days only whereas
it will take almost two years to solubilize all the precipitated P. Using the degree of

2135

Copyright © 1998 by Marcel Dekker, Inc. www.dekker.com

 2136 DE SMET, VANDERDEELEN, AND HOFMAN

phosphate saturation (DPS) instead of Pox for estimating the reversibly adsorbed
phosphate results in regression models with about the same determination coefficients.

INTRODUCTION

Since the late sixties, pig breeding has become an important agricultural
activity in the province of West-Flanders, Belgium. As a consequence, large quantities
of pig slurry are annually applied to the cultivated land. The recurrent disequilibrium
between the level of P fertilisation and the P uptake by the crops results in an
Downloaded by [Michigan State University] at 12:58 29 December 2014

accumulation of P in the soil profile. With time, P is transported to deeper soil layers,
in term resulting in elevated P levels in ground and surface waters (Sharpley &
Rekolainen, 1997). From the scope of environmental concerns, the factors affecting
the phosphate release in the soil should receive much attention.
The reaction of ortho-phosphates (PO43") with soil has been studied intensively
(Kuo & Lotse, 1974; Barrow, 1979,1983; Enfield et al, 1981a,b; Van Riemsdijk &
De Haan, 1981; Syers & Curtin, 1988; Van der Zee & Van Riemsdijk, 1991; Morgan,
1997).
Chien & Clayton (1980) found the phosphate sorption as well as the phosphate
release by soils to be linear to In of t. They used a simple modified Elovich equation
to fit the experimental data:

q - (l)*ln(«*P) + (l)*/»r [1]

ß ß

In this equation, q is the amount of phosphate released or sorbed, and a and

ß are constants. However, many authors fail to describe the overall process by a
single mathematical expression. Studying the overall reaction of P sorption by soils,
Van der Zee and Van Riemsdijk (1988, 1991) distinguish between a reversible fast
first-order kinetic adsorption process and a practically irreversible slow diffusion-
precipitation process.
They describe the sorption of P (S) by soil for extended reaction times, i.e.
once the adsorption process has reached equilibrium, by the following equation:

• ^ - a^expi-a^S) [2]
at

with at and ¡^ being constants.

Integration of the previous mathematical expression results in the diffusion-
precipitation process to be linear to the logarithm of time t:

S - à£*ín[a1*a2*t] - constant + à£*lnt tJ

 SOIL PROPERTIES AND PHOSPHATE RELEASE 2137

Both equations [1] and [3] are similar and can be reduced to:

Q - a + b*lnt W

where Q is the amount of phosphate released and a and b being constants.

For a first order kinetics, decrease of the soil P pool which can be desorbed
obeys next equation, in which kd is the rate constant (Van der Zee et al., 1987) :
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ff v
or in the integral form as :

Pt - /> 0 *[«p(-V>] [6]

The P release at time t is :

Q, - PO-P,

Combining both equations [6] and [7] we obtain

Q, - P0*U - e a p ( - V 0 ] [8]

where Po is equivalent to g» which refers to the maximum P amount that can be

released at infinite time.
As stated by Van der Zee et al. (1987), a desorption time of 20 hours in the
presence of an infinite sink is reasonable to assess the amount of reversibly adsorbed
P.
For acidic sandy soils, Van der Zee and Van Riemsdijk (1991) found the
amount of reversibly adsorbed phosphate to be one third of the total sorbed
phosphate. Using this ratio, the P status of the soil was related to the phosphate
concentration in the upper groundwater. Finally, this relationship was used to calculate
the critical P content of the soil above which an environmentally unacceptable
leaching of P takes place.
The objective of this research was to investigate by means of P release and
desorption experiments the ratio reversibly/irreversibly sorbed P as well as the
desorption kinetics for non-calcareous soils with different soil texture in relation to
some physical and chemical soil properties.
 2138 DE SMET, VANDERDEELEN, AND HOFMAN

MATERIALS AND METHODS

In the frame of an inventory of the P status of the arable land in the sandy
loam soil region of West-Flanders, soil samples were taken at 2000 m intervals on a
square grid (De Smet et al, 1996). According to soil taxonomy, the soils in this
region are mainly Typic Eutrochrepts or Typic Haplumbrepts. At each location, the
soil profile was sampled to a depth of 90 cm in layers of 30 cm. In total, 888 soil
samples were taken to the laboratory, air-dried and sieved (<2mm). Soil pH was
measured on a 1:2.5 soil to 1 M KC1 suspension after 10 minutes. Organic carbon
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(OC) content was determined according to Walkley & Black (1934). Particle size
distribution was measured by the pipette method after dispersion of the soil particles
with sodium hexametaphosphate (Day, 1965). Oxalate extractable P, aluminum (Al)
and iron (Fe) were determined after extracting the soil for 2 hours with acid
ammonium oxalate (Schwertmann, 1964). Iron and aluminum in the extract were
measured by atomic absorption spectrophotometry and P as proposed by Scheel
(1936) after oxidation of the oxalate by digestion with sulfuric acid (H2SO4). Finally,
the degree of P saturation (DPS) of the samples was calculated according to Van der
Zee et al. (1990).
For P release and P desorption experiments, in order to cover a wide range in
soil texture, soil pH and DPS, 35 soil samples were selected. These samples covered
a range of soil texture, pH and %OC (Table 1). All samples were free of calcium
carbonate.
P release experiments were conducted by repeated extraction of the soil
samples. One g of soil was gently shaken for 24 hours with 50 ml of a P free 2 mM
KC1 solution. The suspension was centrifuged for 15 minutes (7000 rpm) and the
solution was completely removed for P analysis. To the soil, another 50 ml of 2 mM
KC1 was added and shaken for 24 hours. Again the solution was separated by
centrifugation from the soil for P analysis and a new fresh KC1 solution was added
to the soil. This was repeated 15 times.
P desorption experiments were conducted using the Fe-impregnated filter paper
P extraction method by continuous extraction (Van der Zee et al., 1987; Sharpley,
1993). One g of soil was suspended in 40 ml of a 2 mM KC1 solution in the presence
of 4 loosely added Fe-oxide impregnated filter paper strips (filter paper type
Schleicher & Schuell 589/3). After resp. 4, 8, 22.5, 31 and 55 hours, the strips were
removed and replaced by new ones. The P adsorbed on the filter paper was extracted
by shaking the strips during 4 hours with 40 ml of 0.2 M H2SO4 (Van der Zee et al,
1987).
Concentrations of P in all the solutions were measured colorimetrically
(Murphy & Riley,1962).

RESULTS AND DISCUSSION

Phosphate release experiments

The cumulative quantities of P, Qt, released by repeated extraction in the

absence of an infinite P sink are plotted versus a normal time scale (Figure 1). Five
 Downloaded by [Michigan State University] at 12:58 29 December 2014

1s
S
o.
"8

I1
s
SOIL PROPERTIES AND PHOSPHATE RELEASE
2139
 2140 DE SMET, VANDERDEELEN, AND HOFMAN

16-

¿"44 17
^14- iiiii 31
ooooo 92
• • • • • 165
• • • • • 252
0-12-

¡loi
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T3 '
O) y
m

CO 6-

U 4-
2-

T
T ' i | r i i i |
3.0 3.5 4.0 4.5 5.0 5.5 6.0
ln(t)
Figure 1: Cumulative P release curves (mmol P kg 1 ) by repeated extraction of
the soil samples as a function of t (hours). The initial phosphate
release fits first order kinetics (dashed line).

soil samples are considered, but the remaining samples behave similarly. It is clearly
shown that a non-linear relationship exists at the beginning: the initial process of P
release fits a first order kinetics according to Equation 8.
For each sample, the values ß„ and the rate constant kd were calculated by
means of the LSS method and listed in Table 2.
Using the soil properties presented in Table 1 in a multiple regression analysis
(without DSP), the variable Qa could be best described by the following model:

0.29*pH - 0JO25*Feax - O.O32*i4/M 0-973 [9]

Besides Pm Q„ depends on factors determining the P sorption capacity.

However, the
 SOIL PROPERTIES AND PHOSPHATE RELEASE 2141

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öddddddöddöddo'doöoöödoöödöoöddööciöö
Downloaded by [Michigan State University] at 12:58 29 December 2014

voviviNO \0t>v)QrsciON»Hri'O>'ioooQts0NHr4V)fi»<0fi<n^o^o

[
ddddd dddddSdSdSSSddddddSSddddddddd

ddbdddöcidcSciöbciddddddddddcidcicScidcidcacäd

!
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ta
—

o
82

2
es

H
¿g
 2142 DE SMET, VANDERDEELEN, AND HOFMAN

oxalate extractable P already accounted for 96 % of the variability in reversibly

adsorbed P:

Q„ - 0.29 * P i2 = 0.963 [10]

ox

We obtained approximately the same determination coefficient by substituting

PM by the degree of phosphate saturation (DPS):
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CL = 0.105 * DPS r2 = 0.954 [11]

The calculated rate constants are ten times lower than the ones obtained by Van der
Zee et al. (1987). This is most probably a consequence of the fact that during
extraction without the presence of an infinite sink the P concentration in the solution
gradually rises which prevents further release of P.
In spite of the phenomenon of re-adsorption, from the experiment it is
concluded that this net desorption process also can be described by an overall first
order kinetics equation. However, the overall rate constant k,, is dependent on the
experimental conditions and no definite physical meaning can be attached to it.
As the initial non-linear process can be described by first-order kinetics, at
first, P release most likely is dominated by P desorption. Once the process of P
desorption has diminished, the relation becomes linear and phosphate release will be
governed by the diffusion-dissolution process. Focussing upon this final process,
Equation 4 was used to fit the data (Figure 2). The coefficient of determination (r2)
ranged from 0.993 to 0.999. The standard error of the estimates, expressed as a
percentage of the value b, ranged from 0.4 % to 2.8 %. The constant b for the
different samples is listed in Table 2. The variable Pm accounted for 95 % of the
variation in b, indicating that only the amount of precipitated P was the rate limiting
factor in the process of P dissolution under these specific experimental conditions.

b - 0.16 * /» r2 = 0.947 [12]

The previous equation shows that per unit of lnt, 16 % of Pm is dissolved. As

roughly 70 % of Pm is present as a precipitate (Equation 9), it will take 4.4 units on
the lnt time scale to dissolve all the precipitated P. Under the prevailing experimental
conditions, the process of diffusion-dissolution starts at lnt equal to an average of 5.3.
This brings the estimated time required to release all the P present in the soil sample
to 1.9 years, whereas it takes only 8 days for the total amount of desorbable P to be
solubilised.

Phosphate desorption

The amount of total reversibly adsorbed P, i.e. the amount of P extracted

during a limited time in the presence of an infinite sink, was determined according
 SOIL PROPERTIES AND PHOSPHATE RELEASE 2143

16-1

A¿¿¿¿ 17
60 Í4- ***** 31
3OOOO 92
• •••• 165
«•••• 252

o
£ 10-
Downloaded by [Michigan State University] at 12:58 29 December 2014

£
T3
0J
CO
CO 6 -
CD

fc. 4-

PL O' •

2-

0 f I ( 1 Ï I ( I Í 1 | j I I T I [ I tT t | J ^ ) k t J t T T i )
0 50 100 150 200 250 300 350 400
Time (hours)
Figure 2: Cumulative P release curves (mmol P kg'1) by repeated extraction of
the soil samples as a function of lnt (time in hours). The final
diffusion-dissolution process is linear to lnt (dashed line).

to Equation 8 and listed in Table 2. A fairly good agreement was found between these
values and the amount of desorbable P as determined in Experiment 1 although the
Q„ values as determined out of experiment 1 underestimate the total amount
reversibly adsorbed P (Figure 3).
The results of a multiple regression analysis showed the following model to
be the best estimate for the total desorbable P:

Qm - 0.23*POX + 2.75*OC r2 = 0.957 [13]

Again, the oxalate extractable P of the soil was the most significant variable:

(?. - 0.33 * P r2 = 0.944 [14]

 2144 DE SMET, VANDERDEELEN, AND HOFMAN

16.00

14.00 |Y = 0.87*X - 0.3

/—s. 12.00

's 10.00
CL
O 8.00
E 6.00 •
5
Downloaded by [Michigan State University] at 12:58 29 December 2014

4.00

2.00

0.00
10 12 14 16

1
(mmol P kg' )

Figure 3: The reversibly desorbed P (QTO) determined by repeated extraction

versus the reversibly desorbed P (Q«,¡) determined by the infinite
sink extraction experiment.

Equation 14 indicates that the amount of desorbable P can be estimated as one

third of Pm which is in agreement with the data reported by Van der Zee et al.
(1987).
Substituting POT by DPS results again in about the same determination
coefficient:

= 0.12 * DPS r2 = 0.919 [15]

The rate constant kd of the initial desorption process was significantly correlated to
the pH of the soil:

kd - 0.026 * pH r2 = 0.951 [16]

Since the rate constant kd is positively correlated to the soil pH, an increase
in pH within the studied range (pH 3.75-6.50) in non-calcareous soils, for instance
induced by liming, will accelerate the leaching of P towards ground and surface
waters.
 SOIL PROPERTIES AND PHOSPHATE RELEASE 2145

CONCLUSIONS

Both types of P release experiments on sandy-loam/loam soils confirmed the

results of Van der Zee & Van Riemsdijk (1991) estimating the reversibly adsorbed
P amount as one third of POJt. About the same determination coefficients for the
estimation of Q„ were obtained by substituting P„ by DPS.
The rate of initial P desorption is positively correlated with pH, indicating that
an increase in soil pH until about 6.5 will increase P losses by drainage.
Downloaded by [Michigan State University] at 12:58 29 December 2014

ACKNOWLEDGEMENT

The authors wish to thank the Institute for the Encouragement of Scientific
Research in Industry and Agriculture (IWONL, Brussels) for subsidising this research.
We are also much undebted to the two anonymous reviewers of the first version of
the manuscript for their valuable suggestions and positive criticicsm.

REFERENCES

Barrow, N.J. 1979. The description of desorption of phosphate from soil. Journal of
Soil Science, 30, 259-270.

Barrow, N.J. 1983. A mechanistic model for describing the sorption and desorption
of phosphate by soil. Journal of Soil Science, 34, 733-750.

Chien, S.H. & Clayton, W.R. 1980. Application of Elovich equation to the kinetics
of phosphate release and sorption in soils. Soil Science Society of America
Journal, 44, 265-268.

Day, P.R. 1965. Particle fractionation and particle-size analysis. In: Methods of Soil
Analysis: Part 1, Physical and Mineralogical Properties (eds. Black, C.A. et
al.), pp. 545-567. American Society of Agronomy, Madison, Wisconsin.

De Smet, J., Hofman, G., Vanderdeelen, J., Van Meirvenne, M., Baert, L., 1996.
Phosphate enrichment in the sandy loam soils of West-Flanders, Belgium.
Fertilizer Research, 43, 209-215.

Enfield, C.G., Phan, T., Walters, D.M. & Roscoe Ellis, Jr. 1981a. Kinetic model for
phosphate transport and transformation in calcareous soils: I. Kinetics of
transformation. Soil Science Society of America Journal, 45, 1059-1064.

Enfield, C.G., Phan, T. & Walters, D.M. 1981b. Kinetic model for phosphate
transport and transformation in calcareous soils: II. Laboratory and field
transport. Soil Science Society of America Journal, 45, 1064-1070.

Kuo, S. & Lotse, G.E. 1974. Kinetics of phosphate adsorption and desorption by
hematite and gibbsite. Soil Science, 116, 400-406.
 2146 DE SMET, VANDERDEELEN, AND HOFMAN

Morgan, M.A. 1997. The behaviour of soil and fertilizer phosphorus. In: Phosphorus
loss from soil to water (eds. Tuney, H. et al.) pp. 137-149, CAB International,
Wallingford, United Kingdom.

Murphy, J. & Riley, J.P., 1962. A modified single solution method for the
determination of phosphate in natural waters. Analytica Chirraca Acta, 27, 31-
36.

Scheel, K.C. 1936. Colorimetric determination of phosphoric acid in fertilizers with

Downloaded by [Michigan State University] at 12:58 29 December 2014

the Aulfrich photometer. Zeitschrift für Analytische Chemie, 105, 256-269.

Schwertmann, U. 1964. Differenzierung der Eisenoxide des Bodens durch Extraktion

mit Ammoniumoxalat-Lösung. Zeitschrift Pflanzenernährung, Düngung und
Bodenkunde, 105, 194-202.

Sharpley, A.N. 1993. An innovative approach to estimate bioavailable phosphorus in

agricultural runoff using iron oxide-impregnated paper. Journal of
Environmental Quality, 22, 597-601.

Sharpley, A.N. & Rekolainen, S. 1997. Phosphorus in agricultural and its

environmental implications. In: Phosphorus loss from soil to water (eds.
Tunney, H. et al.) pp. 1-53, CAB International, Wallingford, United Kingdom.

Syers, J.K. & Curtin, D. 1988. Inorganic reactions controlling phosphorus cycling. In:
Phosphorus cycles in terrestrial and aquatic ecosystems (ed. Tiessen, H.) pp.
17-29, UNDP, Saskatchewan Institute of Pedology, Saskatoon, Canada.

Van der Zee, S.E.A.T.M. & Van Riemsdijk, W.H. 1986. Sorption kinetics and
transport of phosphate in sandy soil. Geoderma, 38, 293-309.

Van der Zee, S.E.A.T.M., Fokkink, G.J. & Van Riemsdijk, W.H. 1987. A new
technique for assessment of reversibly adsorbed phosphate. Soil Science
Society of America Journal, 51, 599-604.

Van der Zee, S.E.A.T.M. & Van Riemsdijk, W.H. 1988. Model for long-term
phosphate reaction kinetics in soil. Journal of Environmental Quality, 17, 35-
41.

Van der Zee, S.E.A.T.M., Van Riemsdijk, W.H. & De Haan, F.A.M. 1990. Het
protokol fosfaatverzadigde gronden. Deel I: Toelichting. 69 p.
Landbouwuniversiteit Wageningen, Vakgroep Bodemkunde en Plantevoeding,
The Netherlands.

Van der Zee, S.E.A.T.M. & Van Riemsdijk, W.H. 1991. Model for the reaction
kinetics of phosphate with oxides and soil. In: Interactions at the soil colloid -
 SOIL PROPERTIES AND PHOSPHATE RELEASE 2147

soil solution interface (eds. Bolt, G.H. et al), pp. 205-239, Kluwer Academic
Publishers, Dordrecht, The Netherlands.

Van Riemsdijk, W.H. & De Haan, F.A.M. 1981. Reaction of orthophosphate with a
sandy soil at constant supersaturation. Soil Science Society of America Journal,
45, 261-266.

Van Riemsdijk, W.H., Boumans, L.J.M. & De Haan, F.A.M. 1984. Phosphate
sorption by soils: I. A model for phosphate reaction with metal-oxides in soil.
Downloaded by [Michigan State University] at 12:58 29 December 2014

Soil Science Society of America Journal, 48, 537-541.

Walkley, A. & Black, I.A. 1934. An examination of the Degtjareff method for
determining soil organic matter and a proposed modification of the chromic
acid titration method. Soil Science, 37, 29-38.