Professional Documents
Culture Documents
Review of Sorption-Desorption Kinetics of Phosphorus in A Highly Variable Charge Tropical Soil
Review of Sorption-Desorption Kinetics of Phosphorus in A Highly Variable Charge Tropical Soil
BY
GONI MAKINTA
SPS/20/PSS/00006
COURSE TITLE
ADVANCED SOIL CHEMISTRY
SSC 9302
FEBRUARY, 2022
INTRODUCTION
complexation, adsorption and precipitation that determine its mobility and fate. Those
chemical processes are a complex function of several soil particles including iron and
aluminum oxide forms and content, the amount of silicate clays and calcium carbonate
content (Afif, et al, 1993). The impact of these properties on phosphorus retention and
release depends on soil acidity and alkalinity. Phosphorus is an essential plant nutrients
relatively less available in the soil than nitrogen and potassium (Juo et al., 2007). An
sanitize system water quality. therefore, sorption is one of the key mechanisms that
The recovery of phosphorus by plant from applied fertilizer is limited in acidic and
calcareous soils due to phosphorus fixation. Phosphorus is fixed by high energy sorption
surfaces such as oxides and hydroxides of ion and aluminum resulting in the formation of
insoluble iron and aluminum phosphates by ligand exchange and precipitation reactions.
Similarly, high base status and pH of calcareous soils makes phosphorus sparingly
soluble due to formation of metal complexes such as Ca-P and Mg-P (Marschner, 1995).
In Agricultural soils, large quantities of phosphate applied every year are not utilized due
to strong sorption and fixation processes (Queseda, et al., 2011). Although, other factors
constituents of variable surface charges are considered the most important (Weng et al,
2011). In tropical alfisols, which have undergone high degree of weathering, there are
1
high levels of iron and aluminum oxides and clay minerals of 1:1 type and these
Strong adsorption of inorganic phosphate anions to mineral soils exerts a key control on
the availability of phosphorus to plants and microbes (lioyd et al., 2001). Phosphate
anions at first attach to the highest energy binding sites and then fill lower energy sites
(McGechan and Lewis, 2002). As phosphate anions accumulate at binding sites, the soil
particles surfaces become increasingly negative, decreasing the affinity for P anions as P
Concentrations increase(Barrow, 1978). The affinity for high energy binding sites before
lower energy sites and a decreasing binding strength with increasing concentrations
results in a non linear Isotherm where P mineral is very strong at low concentrations
Sorption of Phosphorus and its availability is influenced by soil solution pH, metal oxides
and carbonates (Harell and Wang, 2006). In a batch experiment, the acidic soil showed
higher sorption and lower availability of sorped p than calcareous soil due to its low pH
and larger concentration of Fe, Al, and Mn oxides which can fix P and reduce its
availability (Greelhoed, et al, 2007). Biochar addition decreased p sorption and increased
available p in the acidic soil attributed to a decrease in point of zero net charge (PZNC),
and increase in the negative charge potential. The soil pH also increase with biochar
addition during incubation which might be due to proton consumption reaction such as
ligand exchange between functional group of biochar and anions of p on aluminol (Al-
2
Perez et al (2014)and Wang et al (2011) considered oxides as components that contribute
cycle related soil fertility problem as well as environmental fate of phosphorus (P)
tropical soils. The effect of these factors on tropical Alfisols were being evaluated by
sorption studies.
adsorption reactions on to active iron and aluminum oxide and allophane microstructure.
Consequently phosphate get adsorbed into the interior of the particle by solid-state
diffusion (Fonds and Weed, 1996), which is often enhanced by rates and frequency of P
fertilizers application. The capacity of the soil to adsorb-desorb P has been expressed by
equations.
The relationship between the labile P sorped to the soil surface can be described by
in the equilibrium solution. The shape of the curve reflects the sorption capacity for
freshly added P, the shape and the placement of the Q/I plot depends on P fertilization
filtration.
3
Barrow, (2015) observed that the concentration of P transported by diffusion is dependent
on the concentration of P in the soil solution (intensity factor), the ability of the soil to
replenish solution P (buttering capacity) and the diffusion coefficient of P in the soil.
Therefore, an increase in buffer capacity affect the ease of P desorption thereby affecting
due to P retention by the highly reactive surfaces of the hydroxides of iron and aluminum
The phosphorus sorption capacity of a soil depends on mineralogy, soil pH, application
of fertilizer P and manure. Soils of tropical alfisols and ultisols are rich in oxides of iron
and aluminum and 1:1 layer kaolinite clays. These soil constituents have high reactive
surfaces with high P retentive capacities. These soils may reduce P availability, due to
three benchmark soil series of India and observed that phosphate sorption was minimum
in pH range of 5.5 – 6.75. The desorption rate as well as quantity desorbed in six
extractions was maximum at pH 5.0 followed by 6.75,4.25 and 8.0 in that order. This
behaviour of P suggested that the amount of tightly held P was greater at low pH
probably due to high concentration of soluble iron and aluminum which react-with
4
A study was conducted on the effect of organic residues addition on P sorption capacity
of an Alfisol. Reddy et al (2005) found that addition of soybean and wheat residues
resulted in net increase in labile inorganic P and organic P including microbial P during
the period of incubation. The addition of the crop residues effectively decreased p
sorption capacity and therefore the standard p requirement of the soil (i.e. the amount of
generally showed that these crop residues have the potential to improve p fertility of the
increased with increase in soil organic matter. However, the bonding energy and
maximum buffering capacity later decreased, probably due to organic ligands competing
for absorption sites leading to P desorption. They concluded that organic matter enhance
p availability by reducing the strength of p adsorption and increase soil buffering capacity
concentration. The best known adsorption equations are Langmuir and Freundlich
equations. Others includes Tomkin equation, Von’t Hoff equation and Brunauer-Emmett-
Teller equation. An advantage of using the Langmuir equation for describing adsorption
is that it defines a limit to adsorption on a given array of sites that meet the Langmuir
model criteria. This apparent limit has been used by many researchers to evaluate the
adsorption capacity of soils for phosphate and various herbicides. Comparing such
5
capacities can only suggest adsorption mechanisms. On the other hand Freundlich
equation has the following limitations; It does not predict a maximum adsorption
capacity; It has little theoretical foundation and constants of the equation have only
systems.
P per gramme at equilibrium (mg g-1), βL(MPAC) is the maximum P adsorption capacity
and n is the parameter reflecting the intensity of sorption. The parameters of the
Another application of P isotherms is the one developed by Yin et al, (1997) under the
stirred flow method. The procedure under the stirred flow is different from the batch
method in that P adsorption and desorption are measured sequentially. Immediately the
adsorption isotherm is calculated by the following equation (Yin et al, 1997) for
adsorption:
6
[ ]
j
Ve
qa ( t )= ∑ C1 ( i )−C 2 ( i ) tj+C1 ( i+ 1 )−C 2 ( i+ 1 ) m
J=1
Where: C1(j) and C2(j) are concentrations of P in the J-th output solution in the absence
and presence of soil C1(i) and C2(i) are the p concentration in the chamber in the presence
and absence of soil respective. Ve is the effective volume of solution in the reactor: m is
the mass of soil sample. The desorbed amount can be determined by the equation.
[∑ C 2 ( i )−C 1 (i ) tjw
]
j
Ve
qd ( t ) = + C2 ( i+1 ) −C1 ( i+1 )
J =1 Ve m
Dual model Langmuir- Freundlich model. The dual model was proposed by Constantino
¿
j
( k i C eq )
C sorb =∑ bi ¿
J=1 1+ ( k i +eq )
The fitting coefficient and the model adequacy were evaluated based on the kinetic
analysis data. The adjustable parameters are b1 ki and n representing the maximum
sorption capacity, the sorbate-sorbent affinity and the site heterogeneity respectively. J
of four Amazonian soils; xanthic ferrosol -1 (FR – 1), Xantic ferrosol -2 (FR – 2; Rhodic
Ferrosol (FR – 3) and Anthrosol (AT) which have varying degrees of crystalline oxide
7
The Langmuir model evaluated the Maximum Phosphorus Adsorption Capacity (MPAC)
Being considered soils with low to medium sorption capacity (Guedes et al, 2016). By
Langmuir model the follow order of P adsorption capacity is as thus: AT < FR -1 < FR –
in stirred flow are shown in Fig. 2. The FR – 3 soil showed higher P adsorption capacity
kg-1 (Table 1). In FR – 2 and FR – 3 most of the P has been adsorbed within the 100
minutes of evaluation (Figure 3B and C), while for FR–1 and AT soil the process
occurred mainly within the first 50 minutes of contact with solution indicating different
levels of affinity and adsorption capacity (Fig. 3A and D). in all the soils, the amount of P
desorped was smaller than that adsorbed and followed the order qmax for adsorption: FR –
1 < AT < FR -2 < FR – 3 (Fig. 2, Table 1). The difference between the adsorbed and
was used considering the two types of negative sites (slow and fast) as described by
dq
=K 1 ( Fqmax −q ) for q < qF
dt
dq
=K 2 [ ( 1−F ) qmax −q ] for q > qF
dt
8
Where dq/dt is the adsorption/desorption rate (mg Kg-1max)-1; K1 is the adsorption
/desorption rate constant for rapid sites (min -1); K2 is adsorption/desorption rate constant
related to the slow site (min-1), F is the fraction of fast site, qmax is the maximum
at the transition from fast to slow sites, obtained for two lines adjusted to q a and dq/dt for
adsorption or q and dq
/dt for desorption, where dF corresponds to the intercept. F is
calculated as ratio qF/qmax, so that if only one site is present, F= 1 and the model
coincides with the pseudo first-order equation for one site (Perez-novo, et al, 2011).
Phosphorus hysteresis index(H) was also calculated according to the principle proposed
by Deng et al (2010), based on the differences between the areas above the isotherms of
adsorption and desorption but using the areas below the isotherms as defined in the
equation below.
H= ( As−AsAd ) ×100
Where As is the area below the adsorption isotherms d for the time variation 0 to t; and
Ad in the area below the desorption isotherm at the same time variation O to t; and Ad in
the area below the desorption isotherm at the same time variation (mg2 Kg-1 L-1).
The high hysteresis index in FR-2 and FR-3and the lowest in AT indicate that AT soil is
more prone to release adsorbed P.The inverse correlation between hysteresis and
P adsorption. Hysteresis is also correlated with clay content (r = 0.75, P < 0.01) which is
associated with the presence of crystalline and poorly crystalline oxides, representing a
factor of greater importance and controlling the P hysteresis in the soils. This probably
occurs because Kaolinite can mix or associate with Fe oxide substantially increasing the
9
soil adsorption capacity (Wei, et al, 2014). Moreover, in mineral structure of goethite, the
adsorption can occur through monodentate and bidentate bonds in the inner sphere
complex (Abdala, et al, 2015), where as in low crystalline oxides as ferrihydrite it can
occur in bidentate and binucleateded inner sphere complex with high binding energy
The effect of hysteresis has been reported in disruption of metals, organic substances and
forces of soil matrix of oxides, clays and organic matter with ions and molecules of the
soil solution (Rampoldi et al, 2014). On the other hand, organic matter may affect
adsorption by limiting the formation of high stability complexes which result in lower
hysteresis as presented by AT, thus accounting for low correlation between hysteresis and
Conclusion
Phosphorus sorption in the soil is an important nutrient cycle related to soil fertility
problem as well as a determinant for environmental fate of P. soil organic and inorganic
phosphorus constitute the quantity and intensity factors which control P availability in the
to adsorption reactions of P onto iron and aluminum oxides and 1:1 Kaolinite clay
prevalent in tropical alfisols. The capacity of the soil to adsorb and desorb P has been
tropical soils which have unique soil properties that encourage P adsorption and retention
10
Fig. 1. Phosphorus sorption isotherms adjusted to the Langmuir model for soils (A) Xanthic Ferralsol-1
(FR-1), (B) Xanthic Ferralsol-2 (FR-2), (C) Rhodic Ferralsol (FR-3) and (D) Hortic Anthrosol (AT).
Source: Guedes e al, (2016)
11
Fig. 2. Accumulated adsorption and desorption in (A) Xanthic Ferralsol-1 (FR-1), (B) Xanthic Ferralsol-2
(FR-2), (C) Rhodic Ferralsol (FR-3) and (D) Hortic Anthrosol (AT).
Source: Guedes e al, (2016)
12
Table 1: Adsorption and desorption kinetic parameters and phosphorus
hysteresis for four highly weathered soils: (A) Xanthic Ferralsol-1 (FR-1),
(B) Xanthic Ferralsol-2 (FR- 2), (C) Rhodic Ferralsol (FR-3) and (D)
Hortic Anthrosol (AT).
Adsorption qF F qmax K1 K2 R12 R22
FR-1 36.87c 0.55a 67.1c 0.034 0.016 0.99 0.99
FR-2 74.78b 0.45c 165.5b 0.018 0.007 0.99 0.97
FR-3 141.06a 0.48b 295.0a 0.011 0.004 0.99 0.97
AT 16.08d 0.33d 49.0d 0.041 0.006 0.99 0.9
Source: Guedes e al, (2016)
13
REFERENCES
Abdala, D.B., Northrup, P.A., Vincentin, F.C., Spark, D.L. (2015). Residence Time and
pH effect on the bonding Configuration of Orthophosphate Surface Complex at
the Goethite/Water Interface as examined by Extended X-ray Absorption Fine
Structure (EXAS) Spectroscopy J. Colloid Interface Sci. 442, 15-21.
Afif, E., Barron, V. Torrent, 1995. Organic Matter Delays but does not prevent phosphate
surption by Cerrado Soil from Bazil. Soil Sci, 159, 207-211.
Almeda, J.A. Torrent, J. Barron, V. (2003).Soil Colour, Phosphorus Pools and Phosphate
adsorption in Latosols developed from basalt in South Brazil R.Bras.Ci. solo. 27,
985-1002.
Almeida, R.F., Sousa, Q., Isabel, D., Martins, F.P., Machado, H.A., Mikhaeel, J.E.R.,
Borges, E.N., Wendling, B. (2014). Cation Availability and Electrochemical
Conditions in Oxisols Modified by Land Use and Management Systems in the
Region of Triangulo Mineiro, Brazil, Afr. J. Agric.Res.9, 1124-1129.
https://dio.org./10/5897/AJAR2014.8482
Azeez, J.O.,Van Averbeke, W. (2011). Effect of Manure Type and Period of Incubation
on Phosphorus-Sorption Indices of a weathered Tropical Soil Sci. Plant Anal. 42,
2200 – 2218.
14
Constantino, L.V., Quirino, J.N., Monteiro,A.M.,Abrea,O.T., Parreira, P., Urbano,A.,
Santos,M.J.(2017).Sorption and Desorption of Silver Ions by Bentonite Clays.
Environ.sci.pollut. R.24.,11349-11359.
Fink, J.R., Inda, A.V., Bavaresco, J.Barron, V., Torrent, J., Bayer, C. (2016a) Adsorption
and desorption of Phosphorous in Subtropical soils as affected by management
system and mineralogy. Soil Till Res. 115: 62-68.
Galunim, E., Ferreti, J., Zapelline,I., Viera, I., Tarley, C.,Abrao, Santos, M.J.
(2014).Cadmium Mobility in Sediments and Soils from a coal mining area on
Tibagi River Mater. 265, 280-287.
Geelhoed, J.S., Hiemstra, T. Van Riemsdijk, W.H. (1997). Phosphate and Sulfate
Absorption on Geothite: Single Amino and Competitive Adsorption, Geochion.
Cosmodion Acta61, 2389 – 2396.
Gracetz, D.A., Nair, V.D. (2009). Phosphorus Sorption Isotherm Determination, InL
Hovar, J.I., Pierzynski, G.M(Eds). Methods of Phosphorus Analysis for Soils, ,
Sediments, Residuals and Waters, Southern Cooperative Series Bulletin No.408.
North Carolina State University, Releigh, N.C.
15
McBridge, M.B. (1994). Environmental Chemistry of Soils, Oxford University Press,
New York, U.S.A.
Morales, M.M. Comerford, N., Guerrini, I.A., Falcao, N.P.S., Leeves, J.B. (2013).
Sorption and Desorption of Phosphate on Biochar and Biochar-Soil Mixture. Soil
Use and Management.
Murphy, J., Riley, J.P., (1962). A Modified Single Solution Method for the
Determination of Phosphate in Natural Waters, Anal Chim Acta. 27, 31-36.
Onishi, B.S.D., Ferreita, C.S.D., Urbano, A., Santos,M.J. (2020). Modified Hydrotalite
for Phosphorus Slow-Release, Kinetic and Sorption-desorption processes in Clay
and Sandy Soils for North of Parana State (Brazil).
Quesada, C.A., Lloyd, J., Anderson, L.O., Fyllas, N.M., Schwarz, M. Czimczik, C.J.
(2011). Soil of Amazoma with Particular Reference to the Rainfor
Sites.Biogeoscience 8, 11415 – 11440.
Rupa, T.P., Tomar, K.P., Srinivasa, C.H. Subba Rao, A. (2001). Kinetics of Phosphate
Sorption-Desorption as influenced by Soil pH and Electrolyte, Agrochimica, A.5,
124 – 133.
Wei, S., Tan,W. Liu, F. Zlao, W., Weng, L. (2014). Surface Properties and Phosphate
adsorption of binary system containing goethite and Kaolinte Geoderma 213, 478
– 484.
Yang, X., Chen, X., Yang, X., (2019). Effect of Organic Matter on Phosphorus
Adsorption and desorption in a Black Soil from Northeast China. Soil Tillage
Res., 187, 85-91
16