You are on page 1of 11

Communications in Soil Science and Plant Analysis

ISSN: 0010-3624 (Print) 1532-2416 (Online) Journal homepage: http://www.tandfonline.com/loi/lcss20

Comparison of Kinetic Models for Boron


Adsorption in AlluviumDerived Soils of Punjab,
India
Sanjay Arora & D. S. Chahal
To cite this article: Sanjay Arora & D. S. Chahal (2007) Comparison of Kinetic Models for Boron
Adsorption in AlluviumDerived Soils of Punjab, India, Communications in Soil Science and
Plant Analysis, 38:3-4, 523-532, DOI: 10.1080/00103620601174601
To link to this article: http://dx.doi.org/10.1080/00103620601174601

Published online: 17 Feb 2007.

Submit your article to this journal

Article views: 58

View related articles

Full Terms & Conditions of access and use can be found at


http://www.tandfonline.com/action/journalInformation?journalCode=lcss20
Download by: [Sanjay Arora]

Date: 20 April 2016, At: 22:03

Communications in Soil Science and Plant Analysis, 38: 523532, 2007


Copyright # Taylor & Francis Group, LLC
ISSN 0010-3624 print/1532-2416 online
DOI: 10.1080/00103620601174601

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

Comparison of Kinetic Models for Boron


Adsorption in Alluvium-Derived Soils of
Punjab, India
Sanjay Arora and D. S. Chahal
Department of Soils, Punjab Agricultural University, Ludhiana, India

Abstract: The understanding of the boron (B) adsorption mechanism on soil materials is
vital because plants respond primarily to the B activity in soil solution. Batch studies were
conducted to investigate the adsorption behavior of B in 21 surface soils representing
major soil series of Punjab. The soils varied widely in their properties. Six mathematical
models (viz., zero order, first order, second order, Elovich, power function, and parabolic
diffusion) were used to describe B adsorption. The B adsorption pattern was characterized
by an initial fast reaction followed by a slow process, and it was complete in 24 h of equilibrium. The B equilibrium concentration was negatively correlated with clay content
(r 20.911 ), organic carbon (OC) (20.541 ), and cation exchange capacity (CEC)
(20.540 ) and positively with sand content (r 0.706 ). The Elovich equation was
best to describe the rate of B adsorption followed by the power function.
Keywords: Adsorption, boron, Elovich model, kinetics, power function, Punjab soils

INTRODUCTION
Boron (B) is unique among the essential micronutrients because it is present as
nonionized boric acid, H3BO3, over the pH range suitable for the plant growth.
Boron applied to soils is adsorbed to a variable extent, and equilibrium exists
between B in the solid and liquid phases (Hingston 1964). The availability of
B depends upon sorption processes, which are influenced by various physical
and chemical characteristics of soils (Elrashidi and OConnor 1982).
Received 3 March 2005, Accepted 20 June 2006
Address correspondence to Sanjay Arora, Division of Soil Science and Agricultural
Chemistry, S. K. University of Agricultural Sciences and Technology, Faculty of Agriculture, Main Campus, Chatha 180009, Jammu, India. E-mail: aroraspau@yahoo.co.in
523

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

524

S. Arora and D. S. Chahal

Adsorption of B is an important phenomenon in soils and regulate its supply


from soils for plant growth. A potential source of B in soil solution is that
associated with the solid phase in the adsorbed form. The dissolved B
remains in dynamic equilibrium with sorbed forms and hence cannot be
readily removed through leaching.
The adsorption of B is one of the most important factors determining the
release and fixation of applied B and thus deciding the efficiency of B fertilization. Knowledge of the kinetics of adsorption reaction may be essential for the
sound prediction of nutrient availability to plants. Elrashidi and OConnor
(1982) reported that B sorption reactions were complete in 12 h, whereas
adsorption equilibrium was established in less than 2 h after B was added
(Keren and Gast 1983). Mezuman and Keren (1981) used 24 h whereas
Krishnasamy (1996) reported that adsorption of B was almost complete
after 24 h in all 11 agricultural soils of Tamil Nadu (south India). Boron
adsorption in these soils was best described by parabolic diffusion and Elovichian kinetics. There are a number of studies on the kinetics of potassium (K)
and phosphorus (P) reactions in soils (Sparks 1985), but reported information
on the adsorption kinetics of B in Indian soils is very limited. Therefore,
studies have been conducted to assess the kinetics of B adsorption and
provide information on the behavior of B in alluvium-derived benchmark
soils of Punjab, India. A number of models have been used to describe the
kinetics of the adsorption process of B. The information on B adsorption
kinetics in relation to various factors, which determine B concentration in
soil solution, is limited for major soil series of Punjab. The studies ascertaining the energies of B retention and kinetics of its adsorption will help in
evolving empirical relationships that predict B availability to plants.

MATERIALS AND METHODS


Soils
Twenty-one surface soil samples (0 15 cm) representing major soil series of
Punjab were collected, airdried, and passed through a 2-mm sieve. The homogenized soil samples were then analyzed for selected physical and chemical
properties. Soil pH was measured potentiometrically in a 1:2.5 (w/v) soil/
water ratio using combination electrode (Jackson 1973), and electrical conductivity (EC) was measured through solubridge. Organic carbon (OC) was
estimated by the wet digestion method outlined by Walkley and Black
(1934). Free CaCO3 content was estimated by the rapid titration method
(Richards 1954). Particle-size distribution was measured by the pipette
method after dispersion of the soil particles with sodium hexametaphosphate
(Day 1965). The sand fraction was separated by wet sieving, silt and clay
fractions by sedimentation. Cation exchange capacity (CEC) was determined
by replacing the exchangeable cations with sodium acetate (Chapman 1965).

Boron Adsorption Kinetics

525

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

Kinetics of B Adsorption
Batch equilibration studies were conducted to investigate the adsorption
behavior of B in 21 surface (0 15 cm) soils representing the major soil
series of Punjab. A background electrolyte (20 mL; 0.01 M CaCl2) containing
40 mg ml21 as boric acid (H3BO3) was added to 10 g of soil in 50-mL polypropylene centrifuge tubes in triplicate. The contents were allowed to equilibrate with intermittent shaking at 25 + 18C for different intervals ranging
from 1 to 72 h. At the end of the reaction time, the suspension was centrifuged
and filtered. The B concentration in the equilibrium solution was determined
colorimetrically using Azomethine-H (Wolf 1974). The amount of B adsorbed
was calculated from the difference between the concentrations of the initial
solution and the equilibration solution. The amount of B adsorbed at
various time intervals were fitted to different kinetic models.

Modeling of Rate Kinetics


The kinetic models used to describe B adsorption from 21 soils during 72 h
were tested for goodness of fit by least-squares regression analysis. The
models used are:
i) Zero order: qt qo Kot where Ko is the zero-order rate constant (mg
B kg21 s21).
ii) First order: ln qt ln qo K1t where K1 is the first-order rate constant
(s21).
iii) Parabolic diffusion: qt a Kdt1/2 where Kd is the diffusion rate
constant [(mg B kg21)s21/2].
iv) Elovich: qt qo (1/b) ln (ab) (1/b) ln t, where a is the initial B
adsorption rate [(mg B kg21)h21] and b is B desorption constant [(mg
B kg21)h21].
v) Power function: ln y ln a b ln t, where y is the quantity of B adsorbed/
desorbed at time t and a and b are constants (Dalal 1974).
In all the equations, qo and qt are the amounts of B adsorbed (mg B kg21) at
time zero and t, respectively. To determine the equation that best described the
adsorption of B in soils, a standard error estimate was calculated for each
equation. A relatively high value of the coefficient of determination (R2)
and low standard error estimate (SE) were used as criteria for the best fit
(Chien and Clayton 1980). The SE was calculated as follows:


Sq  q0 2
SE
N  2

0:5

526

S. Arora and D. S. Chahal

where q and q0 are the measured and calculated amounts of B in soil, respectively,
at time t, and N is the number of measurements (Steel and Torrie 1960).
RESULTS AND DISCUSSION

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

Soil Properties
The study included soil representing the major soil series of Punjab, varying
widely in texture (sandy loam to clay loam) with sand content varying from
27.10 to 83.20% and clay content from 8.90 to 33.50%. Soil pH varied
from 6.10 to 9.76, EC from 0.13 to 1.30 dS m21, organic carbon content
from 0.16 to 1.10%, CEC from 4.80 to 12.91 cmol (p ) kg21, and CaCO3
content from 0.00 to 3.40%. Thus, the soil possessed widely varying
physical and chemical properties, which provided sufficient scope for the
study of B adsorption. The details of soil properties for each soil under
study are presented in Table 1.
Kinetics of B Adsorption
In all the soils, the B adsorption was characterized by an initial fast reaction
followed by a slow process. Similar reaction rates of B adsorption have been
reported by Krishnasamy (1996) and Krishnasamy, Jaisankar, and Suresh
(1997) in Tamil Nadu soils from south India. The rapid rate of reaction can
be attributed to a chemical reaction and the slow reaction to diffusion of B
into micropores of inorganic and organic compounds (Krishnasamy 1996).
Soils S19, S9, S10, S8, S3, S18, and S6 soils were the fastest at initial adsorption, and S11, S2, S16, S13, S4, S7, and S20 soils were the slowest.
Adsorption of B was almost complete after 24 h in all the soils, though
complete equilibrium was not attained until 32 h had elapsed. Bingham
et al. (1971) showed that B equilibrium was only attained under conditions
of prolonged reaction periods. The prolonged time requirement is probably
related to diffusion of B from the outer solution into sites that are not
readily accessible for adsorption reactions. Mezuman and Keren (1981)
used 24 h, whereas Elrashidi and OConnor (1982) adopted 12 h of equilibrium time for their experiment on B adsorption by soils.
The concentration of B in the equilibrium solution ranged from 15.4 to
34.0 mg mL21 at the completion of the adsorption reaction (Table 2). The equilibrium concentration of boron for S1, S2, S3, S4, S5, S6, S7, S8, S9, S10, S11,
S12, S13, S14, S15, S16, S17, S18, S19, S20, and S21 soils at 24 h was 26.5,
32.8, 34.4, 23.3, 29.8, 28.0, 23.7, 28.8, 22.2, 21.6, 15.5, 20.4, 30.0, 25.9,
27.2, 31.0, 24.7, 30.6, 29.8, 24.5, 25.5, 21.5, 30.2, 19.3, 33.2, and
24.5 mg mL21, respectively. The finer the texture, the lower was the
concentration of B in the equilibrium solution. Texture and CEC of the soils
influenced the B concentration in the equilibrium solution. The B equilibrium

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

Physical and chemical characteristics of the soils

Soils

pH
(1:2.5)

EC
(dS m21)

Sand
(%)

Clay
(%)

OC
(%)

CaCO3
(%)

CEC
[cmol (p) kg21]

S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21

8.49
8.80
8.40
8.62
8.52
8.79
8.29
8.59
8.48
8.38
8.96
8.41
8.34
8.10
7.84
8.14
9.10
9.76
6.10
8.40
9.50

0.17
0.21
0.26
0.22
0.63
0.28
0.21
0.38
0.35
0.34
0.45
0.23
0.13
0.23
0.18
0.48
0.41
1.30
0.40
0.13
2.82

60.1
76.7
53.4
50.1
41.2
50.2
67.8
27.1
31.1
30.4
69.1
33.6
73.4
34.6
39.1
52.6
54.3
44.9
46.8
83.2
33.6

13.2
14.5
22.2
11.6
12.6
18.9
12.2
24.4
33.5
32.5
9.3
16.9
11.35
16.9
11.7
10.1
16.8
26.8
28.6
8.9
24.2

0.65
0.16
0.53
0.50
0.49
0.55
0.57
0.63
0.72
0.75
0.46
0.57
0.48
1.04
0.61
0.49
0.51
0.45
1.10
0.46
0.18

3.40
1.20
1.53
1.98
0.30
2.28
0.15
0.70
0.00
0.45
0.00
0.23
0.63
0.90
0.00
0.95
1.93
1.73
0.00
0.00
2.60

7.50
5.63
8.93
8.54
7.02
8.50
6.32
10.63
12.39
12.91
7.83
8.06
6.80
9.01
9.54
7.06
9.93
8.72
9.65
4.80
10.83

Boron Adsorption Kinetics

Table 1.

527

528

Table 2.

Concentration of B (mg ml21) in equilibrium solution with respect to reaction timea

Soils

1.0

2.0

4.0

8.0

12.0

16.0

24.0

32.0

48.0

72.0

S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21

34.3
37.5
29.9
36.7
33.9
30.8
36.4
28.8
27.2
27.8
37.8
33.6
37.6
32.2
34.4
37.6
31.2
30.3
25.6
35.8
31.8

32.0
36.1
27.7
34.1
32.4
28.3
34.2
27.0
22.0
25.9
36.0
32.3
36.0
30.9
33.6
35.7
29.9
26.5
24.2
35.0
29.6

30.3
35.4
26.2
33.2
30.9
27.9
32.5
25.0
20.2
24.4
34.8
30.8
34.3
28.6
32.6
34.4
28.7
25.0
22.4
34.6
28.2

28.6
35.1
25.8
32.1
29.4
26.7
30.8
24.6
18.5
23.8
33.6
28.4
33.5
27.9
31.8
32.5
26.5
24.0
20.8
34.2
26.6

27.5
34.9
24.8
31.0
28.9
24.6
29.2
23.2
16.5
22.0
32.7
27.2
32.0
26.6
31.5
31.0
25.9
22.8
20.0
33.9
25.2

27.0
34.5
23.7
30.0
28.6
24.0
28.8
22.4
16.0
21.2
30.8
26.5
31.6
25.6
31.0
30.2
25.4
22.0
19.6
33.5
24.8

26.5
34.4
23.3
29.8
28.0
23.7
28.7
22.2
15.5
20.4
30.0
25.9
31.0
24.7
30.6
29.8
25.5
21.5
19.0
33.2
24.5

26.6
34.2
23.2
29.7
28.0
23.5
28.5
22.0
15.4
20.4
29.4
25.7
31.0
24.5
30.5
29.6
25.2
21.2
19.2
33.2
24.5

26.5
34.2
23.1
29.5
27.9
23.5
28.5
22.0
15.5
20.2
29.4
25.8
31.0
24.6
30.4
29.5
25.3
21.0
19.0
33.0
24.3

26.5
34.1
23.2
29.5
27.8
23.5
28.4
21.7
15.4
20.2
29.2
25.5
30.8
24.4
30.4
29.4
25.2
20.8
19.0
33.0
24.3

Means of three replications.

S. Arora and D. S. Chahal

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

Time (h)

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

Boron Adsorption Kinetics

529

concentration was negatively correlated with clay content (r 20.911 ), OC


(20.541 ), and CEC (20.540 ), and it was positively correlated with sand
content (r 0.706 ), which strengthens these statements. This was also consistent with the previously published literature (Elrashidi and OConnor 1982;
Krishnasamy, Jaisankar, and Suresh 1997), which showed that fine-textured
soils usually had higher B-adsorption capacities than the coarse-textured
soils. Maximum B was adsorbed by S9 soil followed by S19 and S10 soils,
whereas minimum B was adsorbed by the S2 soil. Multiple regression
analyses showed that clay and OC content together accounted for considerable
variation (i.e., 89%) in the adsorption of B on the soils.
Five different kinetic models (viz., zero-order, first-order, Elovich, power
function, and parabolic diffusion) were tested by least-squares regression
analysis for describing B adsorption in soils representing the major soil series
of Punjab. The model that had the highest coefficient of determination (R2) and
the lowest standard error estimate (SE) values was considered to be the best fit.
The first-order kinetic equation could not describe the adsorption of B by soils
because R2 values were very low (0.475 to 0.862) and SE values were large (1.402
to 3.658). Zero-order and second-order equations also did not describe B
adsorption sufficiently in all the soils studied, as is evident by the large SE

Table 3.

Parameters of Elovich kinetic model for boron adsorption

Soils

b
[(mg B kg21)h21]

R2

SE

S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21

0.5348
1.3478
0.6268
0.5971
0.6804
0.5485
0.5216
0.6048
0.4409
0.5265
0.4575
0.4838
0.6126
0.5019
0.9968
0.4850
0.6627
0.4760
0.6202
0.6168
0.5508

0.902
0.909
0.927
0.920
0.927
0.920
0.898
0.917
0.868
0.948
0.965
0.927
0.919
0.954
0.956
0.940
0.892
0.920
0.901
0.921
0.913

0.906
0.346
0.657
0.718
0.604
0.789
0.951
0.732
0.963
0.658
0.609
0.852
0.713
0.645
0.314
0.768
0.775
0.911
0.788
0.701
0.826

S. Arora and D. S. Chahal

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

530

Figure 1. Analysis of kinetic data into Elovichian model for B adsorption in soils.

values of zero-order model (1.576 to 3.884) and small R2 (0.585 to 0.846) and
considerably large SE (1.334 to 2.870) values for the second-order model.
The Elovich equation was best of the various kinetic equations studied to
describe the rate of B adsorption as evidenced by the overall highest values of
coefficient of determination (R2) and lowest values SE (Table 3; Figure 1) over
the entire time range. Such a conformity has also been reported in previous
studies by Krishnasamy, Jaisankar, and Suresh (1997), studying B-adsorption
kinetics in the soils of Tamil Nadu. In the present investigation, the R2 value

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

Boron Adsorption Kinetics

531

was maximum of 0.965 in S11 soil followed by 0.956 in S15; 0.954 in S14;
0.948 in S10; 0.940 in S16; 0.927 in S12, S5, and S3; 0.921 in S20; 0.920
in S4, S6, and S18; 0.919 in S13; 0.917 in S8; 0.909 in S2; 0.902 in S1;
0.901 in S19; 0.898 in S7; 0.892 in S17; and 0.868 in S9 soil.
The power function was nearly as good as the Elovich equation in
describing B adsorption kinetics in all the soils (Table 4). The R2 values
were quite high, ranging from 0.816 in S9 soil to 0.935 in S15 soil, and SE
values were low, between 0.045 and 0.184, with an exception in case of
S16 soil where SE values were quite high (to 0.836), indicating poor fit of
model. The parabolic diffusion kinetic model was also satisfactory in describing the adsorption kinetics of the soil series of Punjab with R2 values between
0.671 and 0.853 and SE values between 0.002 and 0.051 (Table 4).

CONCLUSIONS
The B adsorption data for the present study clearly shows that soils not only
vary in their capacity to retain B but also in the energy with which they
Table 4. Parameters of parabolic diffusion and power function models for boron
adsorption kinetics
Parabolic diffusion

Power function

Soils

R2

SE

R2

SE

S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21

0.686
0.716
0.749
0.733
0.726
0.749
0.682
0.723
0.677
0.792
0.853
0.740
0.716
0.798
0.778
0.759
0.671
0.754
0.685
0.724
0.708

0.023
0.007
0.020
0.018
0.016
0.023
0.002
0.023
0.051
0.024
0.016
0.024
0.017
0.021
0.009
0.020
0.021
0.027
0.027
0.014
0.024

0.856
0.829
0.902
0.846
0.891
0.899
0.840
0.895
0.816
0.934
0.925
0.907
0.855
0.933
0.935
0.877
0.876
0.864
0.886
0.927
0.881

0.116
0.117
0.056
0.154
0.082
0.068
0.165
0.056
0.095
0.045
0.152
0.094
0.179
0.067
0.050
0.184
0.070
0.836
0.047
0.112
0.081

532

S. Arora and D. S. Chahal

absorb it. These two factors affect the ability of a soil to release B and to
maintain supply in the soil solution. The study indicates that the equilibrium
period of 24 h was sufficient to study the B-adsorption characteristics of soils.
Clay and organic matter contents variably affect the adsorption of B in soils.

Downloaded by [Sanjay Arora] at 22:03 20 April 2016

REFERENCES
Bingham, F.T., Page, A.L., Coleman, N.T., and Flach, K. (1971) Boron adsorption
characteristics of selected amorphous soil from Mexico and Hawaii. Soil Science
Society of America Proceedings, 35: 546550.
Chapman, H.D. (1965) Cation exchange capacity. In Methods of Soil Analysis part 2;
Black, C.A., Evans, D.D., White, J.L., Ensminger, I.E. and Clark, F.E. (eds.),
American Society of Agronomy: Madison, WI, 899 900.
Chien, S.H. and 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.
Dalal, R.C. (1974) Desorption of soil phosphate by anion exchange resin. Communications in Soil Science and Plant Analysis, 5: 531 539.
Day, P.R. (1965) Particle fractionation and particle size analysis. In Methods of Soil
Analysis; Part 1 Black, C.A., Evans, D.D., White, J.L., Ensminger, I.E., and
Clark, F.E. (eds.), American Society of Agronomy: Madison, WI, 545 567.
Elrashidi, M.A. and OConnor, G.A. (1982) Boron sorption and desorption in soils. Soil
Science Society of America Journal, 46: 27 31.
Hingston, F.J. (1964) Reaction between boron and clays. Australian Journal of Soil
Research, 2: 83 95.
Jackson, M.L. (1973) Soil Chemical Analysis; Prentice Hall of India: New Delhi, India.
Keren, R. and Gast, R.G. (1983) pH-dependent boron adsorption by montmorillonitic
hydroxy aluminum complexes. Soil Science Society of America Journal, 47:
1116 1121.
Krishnasamy, R. (1996) Kinetics of boron adsorption in soils. Journal of Indian Society
of Soil Science, 44: 783 785.
Krishnasamy, R., Jaisankar, J., and Suresh, M. (1997) Characterization of boron
adsorption in soils of Tamil Nadu. In Boron in Soils and Plants; Bell, R.W. and
Rerkasem, B. (eds.), Kluwer Academic Publishers: Dordrecht, Netherlands,
255 259.
Mezuman, U. and Keren, R. (1981) Boron adsorption by soils using a phenomenological adsorption equation. Soil Science Society of America Journal, 45: 722 726.
Richards, L.A. (1954) Diagnosis and Improvement of Saline and Alkali Soils; U.S.
Government Printing Office: Washington DCUSDA Agric. Handbook No. 60.
Sparks, D.L. (1985) Kinetics of ionic reactions in clay minerals and soils. Advances in
Agronomy, 38: 231 266.
Steel, R.D.G. and Torrie, J.H. (1960) Principles and Procedures of Statistics; McGraw
Hill: New York.
Walkley, A.J. and Black, I.A. (1934) Estimation of soil organic carbon by chromic acid
titration method. Soil Science, 37: 29 38.
Wolf, B. (1974) Improvement in the azomethine H method for the determination of
boron. Communications in Soil Science and Plant Analysis, 5: 39 44.