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6/2019 pages 4661-4670 Fresenius Environmental Bulletin

CRITICAL SOLUTION [P] IN DIVERSE CALCAREOUS SOIL


SERIES USING ADSORPTION EQUATIONS
Manzoor Ahmad1, Muhammad Jamal Khan3, Dost Muhammad3, Wajid Ali Shah1, Fahim Ullah Khan4,
Riaz Ahmad Khattak 2, Zafar Hayat Khan5, Amjad Iqbal5, Farooq Shah5,*
1
Department of Agriculture, Bacha Khan University, Charsadda, Khyber Pakhtunkhwa, Pakistan
2
CECOS University of IT & Emerging Sciences, Hayatabad Peshawar, Pakistan
3
Department of Soil and Environmental Sciences, The University of Agriculture, Peshawar, Pakistan
4
Department of Agriculture, Hazara University Mansehra Khyber Pakhthunkhwa Pakistan,
5
Department of Agriculture, Garden Campus, Abdul Wali Khan University Mardan. Pakistan

ABSTRACT nucleic acids, which are the basic component of


gene and chromosomes determining the heredity.
To understand the behaviour of P in calcare- The P supplying capacity of the soils is strong-
ous soils, two diverse lime containing soil series of ly influenced by the extent of adsorption [6] that
Peshawar (19 %) and Guliana (4 %), were selected could provide basis for fertilizer recommendations
for P adsorption capacity. A 50 mL solution con- for different crops [7]. In soils the solid phase of
taining 0, 10, 20, 40, 60, 120, 240 and 360 mg P L-1 adsorbed P is considered to be very complex. Due
(initially applied P, IPA) was applied to 5 g of re- to the process of adsorption and precipitation in
spective air-dried soils taken in triplicates in conical surface soils, all the applied P to the soils is not
flasks and was shaken for 30 h. In strongly calcare- immediately available to plants but subsequently
ous Peshawar soil series, adsorption of P ranged released into soil solution and absorbed by plants.
from 85.7 to 1366 mg kg-1 which was almost dou- Therefore, P use efficiency and its release into soil
ble of the P adsorbed in low lime Guliana soils se- solution are closely associated with the P sorption
ries at the iso-equivalent level of IPA. Both simple (adsorption and desorption) capacity of soils [8].
and modified Langmuir and Freundlich models When phosphate is applied to soil either as solid or
were best fitted (r2 > 0.95 on average) for the P ad- liquid fertilizers it leads to series of chemical reac-
sorption pattern in both soils. However, for main- tions of orthophosphate (H2PO4-, HPO42-), with
taining 0.2 mg P L-1 soil solution, the amount of various soil components [9, 10] and is converted to
P2O5 required was 33.51 kg ha-1 for Peshawar and less soluble phosphates thereby decreasing soil so-
17.47 kg ha-1 for Guliana on the basis of adsorption lution [P]. This phenomenon of conversion of solu-
calculation, which is much lower than the amount ble into less soluble state is termed as P fixation/P
of P fertilizer as determined in series of field exper- retention, and has been reviewed by several authors
iments. To maintain the critical soil solution [P], it [11, 12, 13]. To understand the chemical behaviour
is recommended to add proportionately more P fer- of P, adsorption and desorption reactions are con-
tilizers to highly calcareous soil. sidered as key aspects in soil plant system [10]. The
removal of phosphates ions by soil components
from solution is described as adsorption [14] while
KEYWORDS: desorption describes the reverse process of removal
P adsorption, Calcareous soil series, Critical Soil Solution of bound soil P to the solution [15]. The amount of
[P] P adsorbed is determined largely by the solution P
concentration in a dynamic equilibrium process
[16]. In a calcareous soil P adsorption largely de-
INTRODUCTION pends on the CaCO3 level of soil in addition to soil
pH and other mineralogical factors [9], where [P] is
Phosphorus (P) is an essential macro nutrient pre-dominantly determined by Ca-P compounds
required by plant in relatively larger quantities [17, 18]. This study was undertaken to evaluate the
ranging from 0.2-0.8 % of plant dry matter [1, 2]. It P adsorption and to estimate the amount of fertilizer
is the 2nd growth limiting nutrient after N in most P required to maintain the critical soil solution P in
regions of the world [3]. Plants require adequate diverse calcareous high pH soils.
amount of P for optimum production from the very
early stage of growth [4]. It plays a vital role in
several physiological processes such as photosyn-
thesis, respiration, energy storage and transfer, and
cell enlargement [5]. In addition, it is an important
structural component of many biochemicals i.e.

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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin

RESULTS AND DISCUSSIONS the P adsorbed in Guliana soils series (4 % lime) at


the iso-equivalent level of IPA (0 to 360 mg P L-1).
Phosphorus Adsorption Capacity in Pesha- Such higher adsorption of P in Peshawar soil series
war and Guliana Soil Series. In both the soil se- resulted in comparatively lower EPC than low lime
ries the adsorption of P (x/m) and equilibrium [P] Guliana soil series at each level of IPA (Table 1).
increased with increase in applied P level (IPA) but Similarly, Xad and Kd, which decreased with in-
with different magnitude (Fig 1. and 2). However, P creasing IPA, were comparatively higher in Pesha-
adsorbed expressed, in percent of IPA (Xad), and the war than Guliana soils series.
ratio of x/m to EPC denoted as distribution coeffi- The graphs (Fig. 1 and 2) further revealed that
cient (Kd) decreased with increases in IPA level adsorbed P (x/m) for high lime containing Peshawar
(Table 1). The decreasing order of Xad and Kd val- soil series was higher and had more sharp/steep
ues with increasing level of IPA and or x/m, indi- slope than Guliana soil series. Both the graphs of
cating the affinity of both soils for P, decreased IPA vs x/m (Fig. 1) and EPC vs x/m (Fig. 2) had
with increasing amount of P in the soil solution. higher slope of 3.81 and 6.02 than 1.97 and 2.43
In strongly calcareous Peshawar soil series calculated for Guliana soil which again indicated
containing 19 % lime, adsorption of P ranged from higher affinity of P in the former soils series.
85.7 to 1366 mg kg-1 which was almost double of

1600 Y (Peshawar) = 89.98 + 3.81 X, r2 = 0.97


2
Y (Guliana) = 65.69 + 1.97 X, r = 0.96
1400 Peshawar (19 % CaCO3)

1200
P sorbed (x/m, mg kg )
-1

1000

800
Guliana (4 % CaCO3)
600

400

200

0 100 200 300 400 500 600


-1
Applied P solution concentrations (mg L )
FIGURE 1
Relationship of applied P solution concentrations (IPA) with P adsorption in
Peshawar and Guliana soil series.

1600

1400 Peshawar (19 % CaCO3)

1200
P sorbed (x/m, mg kg )
-1

1000

800
Guliana (4 % CaCO3)

600

400
2
Y (Peshawar) = 153.37 + 6.019 X, r = 0.94
200 2
Y (Guliana) = 183.69 + 2.427 X, r = 0.95

0 100 200 300 400


-1
Equlibrium P Concentrations (mg L )
FIGURE 2
Adsorption isotherms showing relationship of Equilibrium P solution concentrations (EPC)
with incremental P adsorption in Peshawar and Guliana soil series

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TABLE 1
Phosphorus adsorption characteristics in the given soils
Initial P applied (IPA) Equilibrium[P] -----P adsorbed--- Xad Kd EPC/x/m
mg L-1 mg kg-1 mg L-1 mg L-1 mg kg-1 % - -
---------------------------- Peshawar soil series-------------------------------
0 0 0.6 Native Native - - Native
10 100 1.4 8.6 85.7 85.7 59.77 0.017
20 200 4.6 15.4 154.0 77.0 33.48 0.030
40 400 13.9 26.1 261.3 65.3 18.85 0.053
60 600 23.5 36.5 364.7 60.8 15.50 0.065
120 1200 55.3 64.7 646.7 53.9 11.69 0.086
240 2400 131.3 108.7 1086.7 45.3 8.27 0.121
360 3600 223.3 136.7 1366.7 38.0 6.12 0.163
----------------------------- Guliana soil series -------------------------------
0 0 0.6 Native Native - - Native
10 100 4.2 5.8 57.6 57.6 13.59 0.074
20 200 10.2 9.8 98.4 49.2 9.68 0.103
40 400 23.4 16.6 166.1 41.5 7.10 0.141
60 600 37.2 22.8 228.0 38.0 6.13 0.163
120 1200 83.7 36.3 363.3 30.3 4.34 0.230
240 2400 183.9 56.1 561.0 23.4 3.05 0.328
360 3600 287.0 73.0 730.0 20.3 2.54 0.393
Xad = ratio of adsorption expressed as percent with applied P level
Kd = ratio of adsorbed P with equilibrium [P]

The difference in the adsorption capacity, val- [19] and Gunary (1970) [28] reported that curvilin-
ues of Kad and Xad in the high and low lime soil ear relationship was possibly associated to variable
series is evident from data provided in Table 1. Fig. energy of adsorption of P in soils, while slopes of
1 indicates that as IAP increased, P adsorption also the curves represent the P buffering capacity of the
increased. The adsorption at low IAP was higher in soil [29, 30, 19].
magnitude than at higher IAP. The higher lime
Peshawar soil adsorbed much high (two fold) P Langmuir Adsorption Isotherm Equation.
than low lime (Table 1, Fig. 1). The Langmuir adsorption isotherm equation is ex-
It is an established criterion that high Xad and pressed as:
Kd values indicate more efficient removal of P from
the soil solution by soils [19]. The higher Xad and
-------------------- Eq. [1]
Kd for Peshawar soil series indicated its compara-
tively higher affinity and more adsorption of P at whereas, x/m is the amount of P adsorbed (mg
any level of IPA which could be associated to its P kg-1), ‘KL’ is bonding-energy constant, ‘b’ is
higher lime content. In a classical study, Cole et al. Langmuir adsorption maximum (mg P kg-1), EPC is
(1953) [20] reported that upon application to cal- the concentration of P in soil solution at equilibrium
careous soils, P rapidly makes monolayer adsorp- (mg L-1). ‘KLb’ is also known as maximum buffer-
tion on lime (CaCO3) surface and precipitates as di- ing capacity (MBC) of the soil system. The linear
calcium phosphates as its concentrations becomes form of the Eq. [1] is produced below:
high. Griffin and Jurinak (1973) [21] concluded that
the interaction of P with lime surface could be de- )----------- Eq. [2]
scribed as heterogeneous nucleation process. Talor
and Ellis (1978) [22] explained this on the basis of
adsorption initially as two-point attachment of By plotting the EPC/(x/m) against EPC gives
H2PO4- at low equilibrium [P] in comparison to one the linear form where the 1/KLb represents intercept
point-attachment as H2PO4- at high equilibrium [P]. and 1/b slope of the linear scatter graph. Such linear
Some researchers have reported strong associ- plots were developed for both soils which invaria-
ation of P adsorption with soil clay content [23, 24]. bly showed curvilinear shape rather than the
Hussain et al. (2006) [25] reported that organic mat- straight line (Fig. 3 and 4).
ters exert great influence on P adsorption. However, The bonding energy (KL), adsorption maxi-
in the present study the major difference between mum (b) and buffering capacity (KLb) which also
the two soils was lime content that mainly deter- known as maximum buffering capacity [3] were
mined the extent of P adsorption. 1666.7 mg kg-1, 0.016 L mg-1, and 26.31 mg P kg-1
As evident from Fig.1 and Fig.2, the shape of for Peshawar and 1000 mg kg-1, 0.009 L mg-1 and
adsorption isotherm in both the soils was curviline- 9.09 mg P kg-1 for Guliana soil, respectively (Table
ar suggesting similar adsorption mechanism. Javid 2).
1999 [26]; Muljadi et al. (1966) [27]; Hussain 2007

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TABLE 2
Comparative Equilibrium parameters of the Langmuir adsorption isotherm equation
for the given soil series
Parameter Peshawar soil series Guliana soil series
Intercept 0.038 0.11
Slope 0.0006 0.001
r2 0.93 0.98
SE of estimate 0.0148 0.0287
Adsorption maximum (b) mg kg-1 1666.7 1000
Bonding Energy (KL) L mg-1 0.016 0.009
Buffering Capacity (MBC) mg P kg-1 26.31 9.09

0.18
Y (Peshawar) = 0.038 + 0.0006(EPC)
r2 = 0.93
0.16

0.14

0.12
EPC/(x/m)

0.10

0.08

0.06

0.04

0.02

0.00
0 50 100 150 200 250

EPC
FIGURE 3
Langmuir isotherm for Peshawar soil series

0.45

0.40 Y (Guliana) = 0.11 + 0.001(EPC)


2
r = 0.98
0.35

0.30
EPC/(x/m)

0.25

0.20

0.15

0.10

0.05
0 50 100 150 200 250 300

EPC
FIGURE 4
Langmuir isotherm for Guliana soil series.

The P adsorption data fitted to linear form of et al. (1973) [31] were of the opinion that two or
Langmuir Eq. [2] produced curvilinear graph for more population of sites in soils having different
Peshawar [Fig. 3] and Guliana soil series [Fig. 4]. affinity for P might be the reason for the curvature.
The curvilinear behaviour suggested that sites hav- The assumption of constant energy of adsorp-
ing varying bonding energy were available for P tion, adsorption on specific sites and monolayer
adsorption on both soils. It further indicates that adsorption on which the simple Langmuir adsorp-
adsorption capacity of soils decreases with each tion isotherm equation relies [32] was fully (100 %)
additional increment of IPA, whereby a small satisfied in this study as obvious from the curviline-
amount of P is firmly adsorbed and slightly greater ar shape of the relations in both soils. However,
amount of P less firmly and so on. However, Syers regression in both soils were highly significant with

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r2 values of 0.93 and 0.98 in Peshawar and Guliana


soil series, respectively (Fig. 3, Fig. 4 & Table 2) ------- Eq. [4]
and could be successfully used at least for compari-
son of behaviour of P in the two different soils. The The data were plotted (Fig 5) according to the
bonding energy, maximum adsorption and buffer- above linear model which produced linear relation-
ing capacity were higher for high lime Peshawar ships with r2 values of 0.99 in both soils. It suggest-
indicating stronger P adsorption in this soil than ed that like Langmuir model, the Freundlich ad-
low lime Guliana soil series. The higher adsorption sorption isotherm model also fit for the given ad-
maximum and KL values closely determine the sorption study. Values of Log K were 1.819 and
strength of attachment with which P is held by soil 1.394 in Peshawar and Guliana soil series, respec-
particles [33]. The different KL also indicated that tively whereas values of 1/n were 0.56 in Peshawar
sites for P adsorption for both soils were different and 0.59 L kg-1 in Guliana soil series (Table 3,
[34]. Fig.5).
The P adsorbtion data showed perfect fit to
Freundlich adsorption isotherm equation. linear form of the Freundlich equation (Fig.5, Table
The Freundlich equation is expressed by the follow- 3). The Freundlich equation implies that the energy
ing formula for P: of the adsorption on a uniform surface is independ-
ent of surface coverage and that it decreases loga-
------------------ Eq. [3] rithmically as the fraction of the covered surface
increases [32]. The decrease in energy of adsorption
where K and n are empirical constants, x/m is with increase in surface coverage is due to surface
the adsorption and ECP is the equilibrium concen- heterogeneity. It is usually used in the condition
tration of P. The linear model of the equation is: where the Langmuir equation fails [33].

FIGURE 5
Linear Form of Freundlich isotherm for Peshawar and Guliana soil series

TABLE 3
Equilibrium parameters of the Freundlich adsorption isotherm equations for Peshawar and
Guliana soil series
Soil Extent of Slope/Rate of Co-efficient of
Intercept
Series adsorption adsorption regression
1/n
Log K K r2
L mg-1
Peshawar 1.819 66.0 0.5607 0.996
Guliana 1.394 24.8 0.5999 0.999

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Javid (1999) [34] reported that K is the ad- several researches [36, 37, 19].
sorbed P that would sustain a unit P concentrations
in equilibrium solution. The slightly higher 1/n val- Two surface Langmuir adsorption isotherm
ue in Guliana represented more heterogeneity than equation. Because of its deviation from the simple
high lime Peshawar soil series [35]. This employs Langmuir equation and curvilinearity in both the
that lower K in Guliana would have lower P adsorp- soils, multisite and multilayer adsorption as ex-
tion capacity at low P concentration than higher pressed by the following modified Langmuir Model
lime Peshawar soil series. Furthermore, as reported was applied as given by Bohn et al. (1985) [32]:
by Hussain (2007) [19], this only indicates the
amount of P adsorbed at low [P] because large frac-
tion of P is retained through precipitation process ---- Eq. [5]
by soil at higher [P]. The K value for Peshawar soil where the subscripts 1 and 2 refer to regions
series was 66.0 mg P kg-1 which was 2.6 times (or mechanism) 1 and 2, respectively.
higher than 24.8 mg P kg-1 exhibited by low lime The graphs in both soils yielded two straight
Guliana soil series. This suggested that several fold lines for each soil, one at low equilibrium [P] (EPC)
higher P was adsorbed in high lime Peshawar soil and the other at higher EPC (Fig. 6 and Fig. 7). Ta-
series than low lime Guliana. Both the Langmuir ble 4 shows results of relevant parameter for both
and Freundlich adsorption isotherm models sup- soils.
ported that high lime Peshawar soil had higher P Two distinct regions can be seen in Peshawar
affinity and adsorption capacity than low lime Guli- (Fig. 6) and Guliana soil series (Fig. 7) with signifi-
ana soil series. Significant correlation of P adsorp- cant correlation coefficient between EPC and
tion and lime content of soil have been reported by EPC/(x/m).

FIGURE 6
Two surface layer adsorption model of Langmuir adsorption isotherm for P adsorption in Peshawar soil
series having 19 % lime

FIGURE 7
Two surface layer adsorption model of Langmuir adsorption isotherm for P adsorption in Guliana soil
series having 4 % lime.

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TABLE 4
Equilibrium parameters of the two surface Langmuir adsorption isotherm equation for Peshawar and
Guliana soil series
Soil series ------------------ Region I------------- ------------------ Region II-------------
KLb1 KL2
B1 KL1 r2 b2 KLb2 r2
L mg-1 L mg-1
Peshawar soil 357.14 0.192 68.49 0.986 2000 0.009 17.83 0.997
Guliana soil 312.50 0.047 14.81 0.985 1250 0.005 5.86 0.993

TABLE 5
Estimated P fertilizers required for maintaining the desired equilibrium [P] in soil solution (EPS) in the
given soil series based on Langmuir
A B C B/C A*10 -----P Required (x/m+EPS)---
Soil series
EPS KB*EPS 1+K(EPS) x/m EPS P P2O5 P2O5
mg L-1 - - mg L-1 mg kg-1 mg/kg mg/kg kg/ha
Peshawar 0.05 1.33 1.001 1.33 0.5 1.83 4.20 8.39
Guliana 0.05 0.45 1.000 0.45 0.5 0.95 2.19 4.37
Peshawar 0.20 5.33 1.003 5.32 2.0 7.32 16.76 33.51
Guliana 0.20 1.82 1.002 1.81 2.0 3.81 8.74 17.47
Peshawar 0.40 10.67 1.006 10.60 4.0 14.60 33.44 66.87
Guliana 0.40 3.64 1.004 3.62 4.0 7.62 17.46 34.92
Kb and KL values in Peshawar and Guliana soil series are 26.31 and 0.016 and 9.09 and 0.009 L mg-1, respectively.

The region I representing the first straight por- sorption. He concluded this contradictory effect
tion may be associated to P adsorption while at high could be either due to parent material or lack of
EPC precipitation may be responsible for the sec- standard methods. For example, for soils derived
ond straight line in region II [38]. Barrow (1980) from limestone, there was little or no relationship of
[39] also reported that the P is mainly adsorbed on P sorption with total or active lime whereas for soils
lime surface in calcareous soil when EPC is low derived from calcareous Aeolian dust, there was a
while precipitation of P takes place as a Ca-P com- direct relationship between total lime content and P
pound when EPC is higher. Values of adsorption sorption [44]. Pena and Torrent (1990) [45] at-
maximum, bonding energy and maximum buffering tributed this discrepancy to the inability of standard
capacity were calculated in both regions for both methods to measure adequately the reactivity of
soils and were represented as 1 and 2, respectively carbonate towards P sorption.
(Table 4). Adsorption maximum (b2) for both soils
were higher in region II while bonding energy val- Estimated Requirement of P fertilizers in
ues KL1 were higher in region I indicating that op- the two soils. Based on Langmuir adsorption iso-
posite relation existed between the bonding energy therm model, amount of P required to yield critical
and adsorption maximum in region I and II. It ap- solution [P] in both soils were calculated for
peared that bonding energy was more important in maintenance of 0.05, 0.2 and 0.4 mg P L-1 soil solu-
region I while in region II the adsorption affinity tion as shown in Table 5. The data showed that to
was more important as also concluded by [19]. maintain the desired P level in soil solution the high
Such higher b values in region II but higher K val- lime Peshawar soil series required almost double of
ues in region I were also reported by Kumar and P fertilizer than low lime Guliana soil series. For
Singh (1998) [24]. example to maintain 0.2 mg P L-1 in soil solution
Cole et al. (1953) [20] and Holford and Mat- Peshawar soil series needed 33.5 while Guliana
tingly (1976) [40] suggested that at low [P] adsorp- soils needed 17.1 kg P2O5 ha-1.
tion is expected while at higher P the dominant Table 5 shows the amount of P needed to
mechanism is precipitation. Kuo and Lotse (1972) maintain desired soil solution [P]. Roy and DeDatta
[41] suggested that P may replace an adsorbed wa- (1985) [46] and Memon et al. (1991) [47] estimated
ter molecule, bicarbonate or hydroxyl ion when it is 0.2 mg P L-1 soil solution for comparison while
adsorbed by calcite. Akinremi and Cho (1991) [42] Rajan (1973) [48] and Hassan, (1993) [49] used the
described the reaction of P with lime as: (1) adsorp- value of 0.2 and 0.32 mg P L-1 at which most plants
tion of P onto active sites of CaCO3, (2) reaction attain near maximum growth. While the values es-
with exchangeable Ca2+, (3) reaction with Ca2+ re- timated using adsorption data revealed only 17.47
leased by the dissolution of CaCO3. The surface and 33.51 Kg P2O5 ha-1 for Guliana and Peshawar
sorption of phosphate at low concentration can in- soil series for [P] of 0.20 mg L-1. These calculations
clude physical sorption, chemisorption and anion show that addition of 66.87 and 33.92 Kg P2O5 ha-1
exchange [43]. On the other hand, Hussain (2007) would yield critical [P] of 0.40 mg L-1, which are
[19] reported that both total and active CaCO3 highly optimistic and do not conform to yield data.
seemed to be less important factors affecting P ad- The estimated fertilizer quantity for attaining the

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Received: 15.12.2018
Accepted: 08.04.2019

CORRESPONDING AUTHOR

Farooq Shah
Department of Agriculture,
Garden Campus,
Abdul Wali Khan University Mardan
Pakistan

e-mail: farooqshah@awkum.edu.pk

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