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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin
1200
P sorbed (x/m, mg kg )
-1
1000
800
Guliana (4 % CaCO3)
600
400
200
1600
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
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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin
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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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin
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
0.30
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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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin
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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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin
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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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin
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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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin
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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin
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© by PSP Volume 28 – No. 6/2019 pages 4661-4670 Fresenius Environmental Bulletin
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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