sorption and desorption studies of benzimidazole pbsticides on soils

SORPTION AND DESORPTION STUDIES OF
BENZIMIDAZOLE PBSTICIDES ON SOILS
Dr. Naghmana Rashid
Supervisor
Saadia Tazaiyen
Roll No. V 867285
Submitted in partial fulfillment <strong>of</strong> the
requirements for the Master <strong>of</strong>
Philosophy degree in Chemistry with
specialization in Organic Chemistry at
the Faculty <strong>of</strong> Sciences
Allama Iqbal Open University,
Islamabad
August 04,2009

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DEDICATION
Dedicated to
My dear husb<strong>and</strong> <strong>and</strong> sweet sons
Haider, Taimoor
<strong>and</strong> Abdullah
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Title <strong>of</strong> Thesis Sorption <strong>and</strong> De<strong>sorption</strong> Studies <strong>of</strong> Benzimidazole
Pesticides on Soils
Name <strong>of</strong> Student Saadia Tazaiven
Accepted by the Faculty <strong>of</strong> Science Department <strong>of</strong> Chemistry. Allama Iqbal
Open University, in partial fulfillment <strong>of</strong> the requirements for the Master <strong>of</strong>
Philosophy Degree in chemistry with specialization in organic chemistry.
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Institute <strong>of</strong> Avionics & Aeronautics
Air University, lslamabad
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DR. I'J.qGHMANA RASHID
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ABSTRACT
The objective <strong>of</strong> the present study is to investigate the <strong>sorption</strong> <strong>and</strong> transport
behavior <strong>of</strong> <strong>benzimidazole</strong> fungicides <strong>and</strong> their possible environmental impact on soils
<strong>and</strong> ground water. Benzimidazole fungicides studied were 2-(4-fluorophenyl)-111-
<strong>benzimidazole</strong>, N-(111-<strong>benzimidazole</strong>-2-ylmethyl) acetamide <strong>and</strong> methyl 1H-
<strong>benzimidazole</strong>-2-carboxylate (Carbendazim). Carbendazim is commercially used
fungicide whereas 2-(4-fluorophenyl)-1H-<strong>benzimidazole</strong>, N-(1I/-<strong>benzimidazole</strong>-2-
ylmethyl) acetamide was synthesized <strong>benzimidazole</strong>s, exhibiting good fungicidal activity
as compared to commercially used <strong>benzimidazole</strong>s. Soils studied were from agriculture
areas <strong>of</strong> Multan, Tarnol (Islamabad), Murree <strong>and</strong> Ayubia where such types <strong>of</strong> fungicides
are in use.
To better underst<strong>and</strong> the ad<strong>sorption</strong>-de<strong>sorption</strong> phenomena pure soil constituents
silica, alumina, muscovite <strong>and</strong> montmorillonite were also studied.
In all soils <strong>and</strong> minerals ad<strong>sorption</strong>-de<strong>sorption</strong> isotherms were found linear which
show that ad<strong>sorption</strong> is increases with increased concentration. From ad<strong>sorption</strong> <strong>studies</strong> it
is calculated that the <strong>sorption</strong> equilibrium distribution co-efficient K6 is higher for
Carbendazim than 2-(4-fluorophenyl)-lIl-<strong>benzimidazole</strong> <strong>and</strong> N-(1/I-<strong>benzimidazole</strong>-2-
ylmethyl) acetamide indicating higher ad<strong>sorption</strong>.
Effect <strong>of</strong> soil properties on the <strong>sorption</strong> <strong>of</strong> benzimi dazole fungicides was also
evaluated as ad<strong>sorption</strong> is a surface phenomenon <strong>and</strong> it is dependant on soil organic
matter content <strong>and</strong> pH. Ad<strong>sorption</strong> parameters were quite high in forest soil from Ayubia
which has low pH (7.6) <strong>and</strong> higher organic matter content (9.45) than rest <strong>of</strong> the soils so
it exhibited resistance to de<strong>sorption</strong>.
De<strong>sorption</strong> <strong>studies</strong> exhibited that K6 (des) is higher than K6 (aos) for soils <strong>of</strong> Multan,
Tarnol <strong>and</strong> Murree so the potential risk <strong>of</strong> leaching <strong>and</strong> water pollution will be higher in
these soils.

ACKNOWLEDEMENTS
We bow our heads to Allah, The Almighty, Who created man <strong>and</strong> gifted him with
the sense to decipher right from wrong, <strong>and</strong> His blessings on all the Prophets who guided
their followers <strong>and</strong> our Prophet Muhammad S.A.W. who is beacon light for all the
mankind <strong>and</strong> for all the times to come.
I feel gratified <strong>and</strong> privileged in expressing great degree <strong>of</strong> gratitude to my
research supervisor Dr. Naghmana Rashid Associate Pr<strong>of</strong>essor, Deptt. <strong>of</strong> Chemistry,
Faculty <strong>of</strong> Sciences, Allama Iqbal Open University, Islamabad for her excellence advice,
skillful guidance, personal interest <strong>and</strong> valuable suggestions throughout this research
project.
My sincere thanks to Pr<strong>of</strong>. Dr. Mahmood-ul-Hassan Butt Vice Chancellor,
Allama Iqbal Open University, Islamabad <strong>and</strong> Pr<strong>of</strong>. Dr. Muhammad Kaleem Tahir,
Dean Faculty <strong>of</strong> Sciences, Chairman Deptt <strong>of</strong> Chemistry AIOU, Islamabad for providing
necessary research facilities, encouragement <strong>and</strong> moral support.
I would like to thank the thesis committee for their constructive suggestions <strong>and</strong>
scholarly critical review <strong>of</strong> this thesis.
I would like to express my heartfelt appreciation to Dr. Uzma Younas <strong>and</strong>
Dr.Moazzam Hussain Bhatti for their kindness <strong>and</strong> valuable euidance.
behaviour.
Thanks to all the technical <strong>and</strong> supporting staff for their co-operation <strong>and</strong>
I am also grateful to my seniors <strong>and</strong> colleagues Khurram, Shaista, Shakir,
Ashfaq <strong>and</strong> my sweet friend Anila who were always there for me <strong>and</strong> I can never forget
the time that I have spent with them. My special thanks are due to my lab fellows for
their help <strong>and</strong> cooperation during research work.
vl
nlce

I have no words to acknowledge the sacrifice, efforts, support, encouragement,
appreciation <strong>and</strong> lots <strong>of</strong> prayers, <strong>of</strong> my loving parentsn inJaws <strong>and</strong> brothers. I'm also
thankful to my sisters Aliya <strong>and</strong> Sajida for their contribution in compiling my thesis,
their strengthening prayers <strong>and</strong> encouragement, which led me to the completion <strong>of</strong> my
research work.
Finallv" I would like to thank all my well wishers.
vll
Saadia Tazaiyen Abbasi

ABSTRACT
ACKNOWLEDGEMENTS
CONTENTS
LIST OF TABLES
LIST OF FIGURES
CONTENTS
LIST OF ABBREVIATION AND SYMBOLS
CHAPTER
1. INTRODUCTION
1.1 Pesticides
1 . 1 .1 Classification <strong>of</strong> pesticides
1.1.2 Effects <strong>of</strong> pesticide on environment
1.1.3 Pesticides in Pakistan
1.1.3.1 Use <strong>of</strong> pesticides in Pakistan
1.1.3.2 Study <strong>of</strong> pesticides in Pakistan
vl11
Page No.
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.,
1.1.4 Funsicides
1.1.5
1.2 Soils
1.2.1
1.1.4.1 Classification<strong>of</strong>fungicides
Benzimidazole fungicides
Composition <strong>and</strong> structure <strong>of</strong> soils
1.2.I.1 Soil minerals
I.2.1.2 Surface functional groups
1.2.2 Classification <strong>of</strong> soils
1.2.3 Soil sampling
1.2.4 Soils <strong>of</strong> Pakistan
1.3 Ad<strong>sorption</strong>-de<strong>sorption</strong> <strong>studies</strong>
1.3.1 Sorption
1.3.2 Ad<strong>sorption</strong>-de<strong>sorption</strong> models
1.4 Pesticides, Soils <strong>and</strong> soil minerals/clays used in this study
EXPERIMENTAL
2.1 Chemical <strong>and</strong> solvents
2.2 Instruments used
2.3 Soils collection
2.4 Physiochemical properties <strong>of</strong> pesticides
2.4.1 Moisture content
2.4.2 Organic matter content
2.4.3 Soil pH
2.5 Preparation <strong>of</strong> solutions
IX
8
9
l3
I4
15
18
t9
20
24
27
28
29
JZ
36-40
36
36
a-
)t
38
38
38
38
38

3.
2.5.1 Stock solutions
2.5.2 Dilutions
2.6 Ad<strong>sorption</strong> <strong>studies</strong>
2.7 De<strong>sorption</strong> <strong>studies</strong>
RESULTS
3. I Characteristics <strong>of</strong> Pesticides <strong>and</strong> Soil Used In This
Study Ad<strong>sorption</strong>-de<strong>sorption</strong> <strong>studies</strong>
3.2 General Method Used for Ad<strong>sorption</strong>-De<strong>sorption</strong> Studies
3.3 Ad<strong>sorption</strong> <strong>of</strong> carbendazimby alumina
3.4 De<strong>sorption</strong> <strong>of</strong> carbendazim by alumina
3.5 Ad<strong>sorption</strong> <strong>of</strong> carbendazim by silica
3.6 De<strong>sorption</strong> <strong>of</strong> carbendazimby silica
3.7 Ad<strong>sorption</strong> <strong>of</strong> carbendazimby montmorillonite
3.8 De<strong>sorption</strong> <strong>of</strong> carbendazimby montmorillonite
3.9 Ad<strong>sorption</strong> <strong>of</strong> carbendazimby muscovite
3.10 De<strong>sorption</strong> <strong>of</strong> carbendazimby muscovite
3.11 Ad<strong>sorption</strong> <strong>of</strong> carbendazim by soil 1
3. 12 De<strong>sorption</strong> <strong>of</strong> carbendazim by soil I
3. 13 Ad<strong>sorption</strong> <strong>of</strong> carbendazimby soil 2
3.14 De<strong>sorption</strong> <strong>of</strong> carbendazimby soil 2
3. I 5 Ad<strong>sorption</strong> <strong>of</strong> carbendazim by soil 3
3.16 De<strong>sorption</strong> <strong>of</strong> carbendazim by soil 3
3.17 Ad<strong>sorption</strong> <strong>of</strong> carbendazimby soil 4
38
39
39
40
4t-91
4T
42
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

3.1 8 De<strong>sorption</strong> <strong>of</strong> carbendazimby soil 4
3.19 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by alumina
3.20 De<strong>sorption</strong> <strong>of</strong> FBNZ by alumina
3.21 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by silica
3.22 De<strong>sorption</strong> <strong>of</strong> FBNZ by silica
3.23 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by montmorillonite
3.24 De<strong>sorption</strong> <strong>of</strong> FBNZ by montmorillonite
3.25 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by muscovite
3.26 De<strong>sorption</strong> <strong>of</strong> FBNZ by muscovite
3.27 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by soil 1
3.28 De<strong>sorption</strong> <strong>of</strong> FBNZ by soil 1
3.29 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by soil2
3.30 De<strong>sorption</strong> <strong>of</strong> FBNZ by soil2
3.31 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by soil 3
3.32 De<strong>sorption</strong> <strong>of</strong> FBNZ by soil 3
3.33 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by soil 4
3.34 De<strong>sorption</strong> <strong>of</strong> FBNZ by soil 4
3.35 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by alumina
3.36 De<strong>sorption</strong> <strong>of</strong> ABNZ by alumina
3.37 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by silica
3.38 De<strong>sorption</strong> <strong>of</strong> ABNZ by silica
3.39 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by soil I
3.40 De<strong>sorption</strong> <strong>of</strong> ABNZ by soil 1
xl
6l
62
63
64
65
66
67
70
7T
72
73
74
75
76
77
78
79
80
81
84
85
86
87

3.41 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by soil 2
3.42 De<strong>sorption</strong> <strong>of</strong> ABNZ by soil2
3.43 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by soil 3
3.44 De<strong>sorption</strong> <strong>of</strong> ABNZ by soil 3
4. DISCUSSION
f,.
6.
4.1 Biological activity
4.1.1 Antifungal Bioassay
4.2 Ad<strong>sorption</strong> <strong>studies</strong>
4.2.1 Methyl I H- <strong>benzimidazole</strong>-2-carboxylate
(Carbendazim)
4.2.2 2-(4-fl uorophenyl)- 1,F1- <strong>benzimidazole</strong>
(FBNZ)
4.2.3 N-(ll{- benzimidazol -2-ylmethyl)
acetamide (ABNZ)
4.3 De<strong>sorption</strong> <strong>studies</strong>
CONCLUSION
REFERENCES
xll
88
89
90
9l
92-100
92
92
94
95
97
98
99
99-r02
103-107

i.1
1.2
3.1
.).J
3.4
3.5
3.6
Table No.
LIST OF TABLES
Title
The use <strong>and</strong> trade name <strong>of</strong> some <strong>benzimidazole</strong> funeicides.
Soil types <strong>of</strong> Pakistan
Pesticide used in this studv
The relevant physiochemical properties <strong>of</strong> four soil samples
Ad<strong>sorption</strong> <strong>of</strong> carbendazimby AlzOl
De<strong>sorption</strong> <strong>of</strong> carbendazimby AlzOl
a)
b)
De<strong>sorption</strong> <strong>of</strong> carbendazim by AlzOl
De<strong>sorption</strong> <strong>of</strong> carbendazimby AlzOl
Ad<strong>sorption</strong> <strong>of</strong> carbendazim by SiO2
De<strong>sorption</strong> <strong>of</strong> carbendazim by SiO2
a)
b)
De<strong>sorption</strong> <strong>of</strong> carbendazim by SiO2
De<strong>sorption</strong> <strong>of</strong> carbendazim by SiO2
xlll
Page no
l0
26
40
42
46
47
47
48
49
49

an
).1
3.8
3.9
3.10
3.11
3.12
3.13
3.14
3.15
3.t6
Ad<strong>sorption</strong> <strong>of</strong> carbend azim by montmorillonite
De<strong>sorption</strong> <strong>of</strong> carbend azim by montmorillonite
a)
b)
De<strong>sorption</strong> <strong>of</strong> carbenda zim by montmorillonite
De<strong>sorption</strong> <strong>of</strong> carbenda zim by montmorillonite
Ad<strong>sorption</strong> <strong>of</strong> carbend azim by muscovite
De<strong>sorption</strong> <strong>of</strong> carbend azim by muscovite
a)
b)
De<strong>sorption</strong> <strong>of</strong> carbendazim by muscovite
De<strong>sorption</strong> <strong>of</strong> carbendazim by muscovite
Ad<strong>sorption</strong> <strong>of</strong> carbendazim by soil 1
De<strong>sorption</strong> <strong>of</strong> carbendazim by soil 1
a)
b)
De<strong>sorption</strong> <strong>of</strong> carbendazim by soil 1
De<strong>sorption</strong> <strong>of</strong> carbendazim by soil 1
Ad<strong>sorption</strong> <strong>of</strong> carbend azim by
De<strong>sorption</strong> <strong>of</strong> carbend azim by soil2
a)
b)
De<strong>sorption</strong> <strong>of</strong> carbendazimby soil 2
De<strong>sorption</strong> <strong>of</strong> carbendazimby soil 2
Ad<strong>sorption</strong> <strong>of</strong> carbendazim by soil 3
De<strong>sorption</strong> <strong>of</strong> carbendazim by soil 3
a) De<strong>sorption</strong> <strong>of</strong> carbendazim by soil 3
XIV
soil2
50
51
51
52
53
53
54
55
55
56
57
57
58
59

3.17
3.18
3.19
3.20
3.21
3.22
a
J.ZJ ^a
3.24
3.25
3.26
b) De<strong>sorption</strong> <strong>of</strong> carbendazim by soil 3
Ad<strong>sorption</strong> <strong>of</strong> carbendazimby soil 4
De<strong>sorption</strong> <strong>of</strong> carbendazimby soil 4
a)
b)
De<strong>sorption</strong> <strong>of</strong> carbendazimby soil 4
De<strong>sorption</strong> <strong>of</strong> carbendazimby soil 4
Ad<strong>sorption</strong> <strong>of</strong> FBNZ by AlzOr
De<strong>sorption</strong> <strong>of</strong> FBNZ by AlzOr
a)
b)
De<strong>sorption</strong> <strong>of</strong> FBNZ by AlzOr
De<strong>sorption</strong> <strong>of</strong> FBNZ by AlzOr
Ad<strong>sorption</strong> <strong>of</strong> FBNZ by SiOz
De<strong>sorption</strong> <strong>of</strong> FBNZ by SiOz
a)
b)
De<strong>sorption</strong> <strong>of</strong> FBNZ by SiOz
De<strong>sorption</strong> <strong>of</strong> FBNZ by SiOz
Ad<strong>sorption</strong> <strong>of</strong> FBNZ by montmorillonite
De<strong>sorption</strong> <strong>of</strong> FBNZ by montmorillonite
a)
b)
De<strong>sorption</strong> <strong>of</strong> FBNZ by montmorillonite
De<strong>sorption</strong> <strong>of</strong> FBNZ by montmorillonite
Ad<strong>sorption</strong> <strong>of</strong> FBNZ by muscovite
De<strong>sorption</strong> <strong>of</strong> FBNZ by muscovite
59
6l
6l
62
63
63
65
65
67
67

3.27
3.28
3.29
3.30
3.31
aa^
J.J Z
a aa
J.J J
3.34
3.3s
a) De<strong>sorption</strong> <strong>of</strong> FBNZ by muscovite
b) De<strong>sorption</strong> <strong>of</strong> FBNZ by muscovite
Ad<strong>sorption</strong> <strong>of</strong> FBNZ by soil 1
De<strong>sorption</strong> <strong>of</strong> FBNZ by soil 1
a) De<strong>sorption</strong> <strong>of</strong> FBNZ by soil I
b) De<strong>sorption</strong> <strong>of</strong> FBNZ by soil 1
Ad<strong>sorption</strong> <strong>of</strong> FBNZ by soil 2
De<strong>sorption</strong> <strong>of</strong> FBNZ by soil2
a) De<strong>sorption</strong> <strong>of</strong> FBNZby soil2
b) De<strong>sorption</strong> <strong>of</strong> FBNZby soil2
Ad<strong>sorption</strong> <strong>of</strong> FBNZ by soil 3
De<strong>sorption</strong> <strong>of</strong> FBNZ by soil 3
a) De<strong>sorption</strong> <strong>of</strong> FBNZby soll3
b) De<strong>sorption</strong> <strong>of</strong> FBNZ by soil3
Ad<strong>sorption</strong> <strong>of</strong> FBNZ by soil4
De<strong>sorption</strong> <strong>of</strong> FBNZ by soil4
a) De<strong>sorption</strong> <strong>of</strong> FBNZby soII4
b) De<strong>sorption</strong> <strong>of</strong> FBNZby soil4
Ad<strong>sorption</strong> <strong>of</strong> ABNZ by AlzO:
XV1
7I
7l
72
-a
IJ
74
75
75
76
77
77
78
79
79
80

3.36 De<strong>sorption</strong> <strong>of</strong> ABNZ by Al2O3
aa-
).) I
3.3 8
3.39
3.40
3.41
3.42
3.43
3.44
a)
b)
De<strong>sorption</strong> <strong>of</strong> ABNZ by AlzOg
De<strong>sorption</strong> <strong>of</strong> ABNZ by Al2O3
Ad<strong>sorption</strong> <strong>of</strong> ABNZ by SiO2
De<strong>sorption</strong> <strong>of</strong> ABNZ by SiO2
a)
b)
a)
b)
a)
b)
De<strong>sorption</strong> <strong>of</strong> ABNZ by SiOz
De<strong>sorption</strong> <strong>of</strong> ABNZ by SiOz
Ad<strong>sorption</strong> <strong>of</strong> ABNZ by soil 1
De<strong>sorption</strong> <strong>of</strong> ABNZ by soil 1
De<strong>sorption</strong> <strong>of</strong> ABNZ by soil
De<strong>sorption</strong> <strong>of</strong> ABNZ by soil
Ad<strong>sorption</strong> <strong>of</strong> ABNZ by soil2
De<strong>sorption</strong> <strong>of</strong> ABNZ by soil2
De<strong>sorption</strong> <strong>of</strong> ABNZ by soil2
De<strong>sorption</strong> <strong>of</strong> ABNZ by soil2
Ad<strong>sorption</strong> <strong>of</strong> ABNZ by soil3
De<strong>sorption</strong> <strong>of</strong> ABNZ by soil 3
a)
b)
De<strong>sorption</strong> <strong>of</strong> ABNZ by soil3
De<strong>sorption</strong> <strong>of</strong> ABNZ by soil 3
xvll
81
81
84
85
85
86
87
87
88
89
89
90
9I
9I

4.1 Antifungal activity <strong>of</strong> <strong>benzimidazole</strong>s
4.2 Ko values for ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> carbendazim on
minerals/soils
4.3 K6 values for ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ
on minerals <strong>and</strong> soils 98
4.4 Ko values for ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ on
minerals <strong>and</strong> soils. 99
XVIIl
93
96

I
Table No.
Fig. 1.1
Fig.I.2
Fig. 1.3
Fig. 1.4
Fig. i.5
Fig. 1.6
Fig. 1.7
Fig.3.1
Fig.3.2
Fig.3.3
Fig. 3.4
LIST OF FIGURES
Title
Diagrammatic representation <strong>of</strong> muscovite (mica)
Diagrammatic representation <strong>of</strong> montmorillonite
Determining the soil textures with the use <strong>of</strong> a
Soil texture triangle
Map representing 26broad soil types <strong>of</strong> Pakistan
Types <strong>of</strong> <strong>sorption</strong> isotherms
Minerals/clays used in the study
Soils used in the study
Ab<strong>sorption</strong> spectra <strong>of</strong> carbendazimby alumina
(ad<strong>sorption</strong> blank)
Ab<strong>sorption</strong> spectra <strong>of</strong> carbendazim by alumina
(ad<strong>sorption</strong> a)
Ab<strong>sorption</strong> spectra <strong>of</strong> carbendazimby alumina
(ad<strong>sorption</strong> b)
Ab<strong>sorption</strong> <strong>of</strong> carbendazim by alumina
xlx
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25
30
34
35
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44
44

Fig. 3.5
Fig. 3.6
Fig.3,7
Fig. 3.8
Fig. 3.9
Fig. 3.10
Fig. 3.11
Fig.3.12
Fig.3.13
Fig.3.14
Fig.3.15
Fig. 3.16
Fig.3.17
(de<strong>sorption</strong> a)
Ab<strong>sorption</strong> <strong>of</strong> carbendazimby alumina (de<strong>sorption</strong> b)
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by AlzO:
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by SiOz
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by
Montmorillonite
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by
Muscovite
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by soil
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by soil 2
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by soil 3
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by soil4
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZby AlzOz
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZby SiO2
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by
Montmorillonite
Ab<strong>sorption</strong> spectra <strong>of</strong> FBNZ by muscovite
XX
45
45
46
48
50
52
54
56
58
60
62
64
66

Fig.3.18
Fig.3.19
Fig. 3.20
Fig.3.2I
Fig.3.22
Fig.3.23
Fig.3.24
Fig.3.25
Fig.3.26
Fi9.3.27
Fig. 3.28
(ad<strong>sorption</strong> blank)
Ab<strong>sorption</strong> spectra <strong>of</strong> FBNZ by muscovite (ad<strong>sorption</strong> a)
Ab<strong>sorption</strong> spectra <strong>of</strong> FBNZ by muscovite (ad<strong>sorption</strong> a) 68
Ab<strong>sorption</strong> spectra <strong>of</strong> FBNZ by muscovite (de<strong>sorption</strong> a) 69
Ab<strong>sorption</strong> spectra FBNZ by muscovite (de<strong>sorption</strong> b)
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by muscovite 70
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by soil 1
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZby soil2
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by soil 3 76
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZby soll4
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by AlzO: 80
Ab<strong>sorption</strong> spectra <strong>of</strong> ABNZ by silica (ad<strong>sorption</strong> blank) 82
xxi
68
68
72
74
78

Fis.3.29
Fig. 3.30
Fig. 3.31
Fig.3.32
Fig. 3.33
Fig.3.34
Fig. 3.35
Fig. 3.36
Fig. 4.1
Ab<strong>sorption</strong> spectra <strong>of</strong> ABNZ by silica (ad<strong>sorption</strong> a) 82
Ab<strong>sorption</strong> spectra <strong>of</strong> ABNZ by silica (ad<strong>sorption</strong> b) 82
Ab<strong>sorption</strong> spectra <strong>of</strong> ABNZ by silica (de<strong>sorption</strong> a) 83
Ab<strong>sorption</strong> spectra <strong>of</strong> ABNZ by silica (de<strong>sorption</strong> b)
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by SiO2
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by soil 1
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by soil2
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by soil 3
Antifungal activity <strong>of</strong> <strong>benzimidazole</strong>s
KXIl
83
84
86
88
90
94

LIST OF ABBREVIATIONS
ABNZ : N-(111-benzimidazol-2-ylmethyl) acetamide
AEC : anion exchange capacity
ads : adsorbed
add : added
carb
: carbendazim
oC : degree Centigrade
CEC : cation exchange capacity
des : desorbed
DMSO
emp tb
fnd
FBNZ
0D
ha
kg
Ko (uor)
Ko (oes)
= dimethyl sulfoxide
: empty test tube
: find
: 2-(4-fluorophenyl)-1H-<strong>benzimidazole</strong>
: gram
: hectar
- kilogram
: linear equilibrium coefficient for ad<strong>sorption</strong>
: linear equilibrium coefficient for de<strong>sorption</strong>
XXIlI

L
L kg-'
Ir*
M
MBC
ml
mm
mg
ml pg-'
pm
OC
OM
pH
pk.ht
pKa
ppm
PZA
rpm
SOM
litre
litre per kilogram
maximum wavelength
molar
methyl b enzimidazole carbamate
millilitre
millimeter
miligram
milliliter per microgram
micro meter
organic content
organic matter
hydrogen ion concentration
peak height
acid dissociation constant
parts per million
point <strong>of</strong>zero charge
revolution per minute
soil organic matter
xxiv

STB
tb
UV-VIS
: 3-butyl-2, 4-dioxo-s-triazinol, 2-<strong>benzimidazole</strong>
: test tube
ultraviolet <strong>and</strong> visible spectroscopy
XXV

1.1 Pesticide
INTRODUCTION
CHAPTER 1
Pesticide is a substance or a mixture <strong>of</strong> substances used to kill a pest. Pests
(includes insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes <strong>and</strong>
microbes) that compete with humans for food, destroy property, spread or are vector for
disease or cause a nuisance I.
Pesticides have become an integral part <strong>of</strong> the modem agriculture practices. Each
year insects, weeds, bacteria, fungi, virus, parasites, birds <strong>and</strong> rodents consume or destroy
approximately 48 o/o <strong>of</strong> the world's total food production. To control this tremendous loss
<strong>of</strong> production, pesticides are used. Pest controlling practices started a long time ago as the
crude method <strong>of</strong> applying neem oil, olive green etc. These have been transformed into
the extensive use <strong>of</strong> toxic <strong>and</strong> broad spectrum chemical compounds synthesized with the
view to kill the target pest or weeds 2.
Pesticides can save farmers a lot <strong>of</strong> money by preventing crop losses to insects
<strong>and</strong> other pests. Although pesticides can save farmers money, however extensive use <strong>of</strong>
pesticides can have unintended effects on the environment. Unlike heavy metals <strong>and</strong>
other pollutants, pesticides are lethal to the environment even at micro level <strong>of</strong>
concentrations. Pesticides being lipid soluble support the process <strong>of</strong> bioaccumulation,
which intensifies the disastrous nature <strong>of</strong> pesticides. Moreover, their non-degradable
nature adds to further complication in term <strong>of</strong> persistence <strong>of</strong> pesticide in the environment
for decades, leading to their cumulative effect on living organisms 2.

1.1.1 Classification <strong>of</strong> pesticides
A pesticide may be a chemical substance, biological agent (such as virus or
bacteria), antimicrobial, disinfectant or device used against any pest 3. There are multiple
ways <strong>of</strong> classifying pesticides a.
i. Algaecides
An algaecide or algicide is a substance used for killing <strong>and</strong> preventing the growth <strong>of</strong>
algae e.g. copper sulphate.
ii. Bactericide
A bactericide or bacteriocide is a substance that kills bacteria. Bactericides are
disinfectants, antiseptics or antibiotics e.g. Hypochlorite's, chloramines,
dichloroisocyanurate <strong>and</strong> chlorine dioxide etc.
iii. Fungicides
Fungicides are chemical compounds or biological organisms used to kill or inhibit fungi
or fungal spores e.g. Benzimidazoles, organophosphorus <strong>and</strong> morpholine fungicides.
iv. Herbicides
An herbicide is substance used to kill unwanted plants. Selective herbicides kill specific
targets while leaving the desired crop relatively unharmed e.g. Atrazine <strong>and</strong> 2, 4-
dichlorophenoxyacetic acid.
v. Insecticides
An insecticide is a pesticide used against insects. They include ovicides <strong>and</strong> larvicides
used against the eggs <strong>and</strong> lawae <strong>of</strong> insect's respectively e.g. Organophosphate,
organochlorine <strong>and</strong> permethrin.
vi. Miticides
Miticides or acaricides are pesticides that kill mite's e.g. carbamate, formamidine <strong>and</strong>
mite growth regulators.
vii. Molluscicides
Molluscicides, also known as snail baits <strong>and</strong> snail pellets, are pesticides against molluscs
e.g. Metal salts such as iron (lII) phosphate <strong>and</strong> aluminum sulfate.

viii. Rodenticides
Rodenticides are a category <strong>of</strong> pest control chemicals intended to kill rodents, e.g.
coumarins/4-hydroxycoumarins, 1, 3 -ind<strong>and</strong>iones <strong>and</strong> difethialone.
ix. Nematicides
A nematicide is a type <strong>of</strong> chemical pesticide used to kill parasitic nematodes
(roundworms). One common nematicide is obtained from neem tree, Nematophagous
fungi.
x. Avicide
Avicide is any substance (normally, a chemical) which can be used to kill birds.
Commonly used avicides include strychnine, DRC-1339 (3-chloro-4-methylaniline
hydrochloride, starlicide) <strong>and</strong> avitrol (4-aminopyridine).
Defoliants, desiccants, insect growth regulators, plant growth regulators <strong>and</strong>
repellents are also classified as pesticides.
Pesticides can also be classified as synthetic pesticides or biological pesticides,
although the distinctions sometimes blur. According to another classification broad-
spectrum pesticides are those that kill an affay <strong>of</strong> species, while narrow-spectrum or
selective pesticides only kill a small group <strong>of</strong> species 5.
1.1.2 Effects <strong>of</strong> pesticide on environment
With progressive increase in the production <strong>and</strong> application <strong>of</strong> chemicals for
agricultural activities, the contamination <strong>of</strong> soil, ground <strong>and</strong> surface water has become a
problem throughout the world 6-7. Efforts to preserve the environment <strong>and</strong> to reduce the
risk <strong>of</strong> contamination have established the need to underst<strong>and</strong> the behavior <strong>of</strong> pesticides
in the natural environment. Contamination <strong>of</strong> soil <strong>and</strong> ground water with organic
pollutants such as pesticides constitute a threat to the ecosystem <strong>and</strong> human beings 8.
Over 98oh <strong>of</strong> sprayed insecticides <strong>and</strong> 95Yo <strong>of</strong> herbicides reach a destination other
than their target species. Including non target species e.g. air, water, bottom sediments
<strong>and</strong> food e.

The amount <strong>of</strong> pesticide that migrates from the intended application area is
influenced by different properties <strong>of</strong> the pesticide such as its tendency for binding to soil,
its vapor pressure, its water solubility, <strong>and</strong> its resistance to being broken down over time.
Factors in the soil, such as its texture, its ability to retain water, <strong>and</strong> the amount <strong>of</strong>
organic matter contained in it, pH etc. also affect the amount <strong>of</strong> pesticide that will leave
the areae-l'. Onc" contaminated, the ground water may take a long time to clear <strong>and</strong> there
is always the danger <strong>of</strong> bioaccumulation.
Since the use <strong>of</strong> pesticides in agriculture inevitably leads to exposure <strong>of</strong> non-
targeted organisms as a result undesirable effects can appear on whole species,
communities as well as ecosystems. Agricultural <strong>and</strong> outdoor residential use <strong>of</strong> pesticides
is a matter <strong>of</strong> environmental concem because these chemicals are recognized as a source
<strong>of</strong> potential adverse environmental impact (nonpoint <strong>and</strong> point pollution) <strong>and</strong> their
presence in seawater <strong>and</strong> sediments has grown considerablyl2.
Pesticides also reach the aquatic environment through direct run<strong>of</strong>f, leaching <strong>and</strong>
by careless disposal etc. Environmental problem caused by pesticides has induced some
measurements <strong>of</strong> contamination in water, soils <strong>and</strong> atmosphere. These compounds
undergo chemical, photochemical <strong>and</strong> biological transformation leading to new products
that can be more toxic than the parent ones 13.
In addition to ecological impacts in countries <strong>of</strong> application, pesticides that have
been long banned in developed countries (such as DDT, toxaphene, etc.) are consistently
found in remote areas such as the high arctic. Chemicals that are applied in tropical <strong>and</strong>
subtropical countries are transported over long distances by global circulation. The global
situation has deteriorated to the point where many countries are calling for a global
convention on "POPS" (Persistent Organic Pollutants) which are mainly chlorinated
compounds that exhibit high levels <strong>of</strong> toxicity, are persistent, <strong>and</strong> bioaccumulation. The
list is not yet fixed; however, "c<strong>and</strong>idate" substances include several pesticides that are
used extensively in developing countriesla.
Pesticides, like other organic pollutants, are retained by the soil depending on
their physicochemical properties <strong>and</strong> the soil nature <strong>and</strong> compositionl5. Earlier, pesticides

were believed to be immobile in soil environment, but in recent years it has been
established that they are highly mobile <strong>and</strong> contaminate soil, surface water as well as
ground water. The impact <strong>of</strong> pesticides has been observed on the soil itself i.e. soil
fertility including inhibition <strong>of</strong> nitrification with concomitant have reduced uptake <strong>of</strong>
nitrogen by plants. These <strong>studies</strong> also suggest that pesticides adversely affect soil
structure <strong>and</strong> soil microorganism which are responsible for microbial degradation <strong>of</strong> plant
matter <strong>and</strong> some pesticides.
1.1.3 Pesticides in Pakistan
The economy <strong>of</strong> Pakistan is largely based on agriculture. It contributes ab<strong>of</strong>i25Yo
to the national economy. The well being <strong>of</strong> economy largely depends on the production,
processing <strong>and</strong> distribution <strong>of</strong> major products such as cotton, wheat, sugar, milk meat,
edible oil etc.r6
1.1.3.1 Use <strong>of</strong> pesticides in Pakistan
The climate <strong>of</strong> the country ranges from hot, humid with rainfall, to arid spells.
This on one h<strong>and</strong> provides favourable conditions for irrigated agriculture. While on the
other h<strong>and</strong> it also provides an ideal environment for a thriving pest population. Estimates
suggest that around one-third <strong>of</strong> the yield is destroyed by pests or disease in Pakistan. To
overcome this problem, pesticides have developed into a major agricultural product (80%
are used on cotton alone). Introduced in 1954 at the onset <strong>of</strong> the green revolution,
pesticide consumption in Pakistan rose from 3677 metric tonnes in 1981 to 14745 metric
tonnes in 1991. In rupee terms this equalled 4581 million rupees. By 1996 this had gone
up to 43219 metric tonnes. An exhaustive study conducted by the Food <strong>and</strong> Agriculture
Organization (FAO) <strong>of</strong> the United Nations found that pesticide use in Pakistan increased
1,169 percent between 1981 <strong>and</strong> lgggtT. Pesticides used have increased to 129,000 tons
(285, 00 tons active ingredient) in2004t6.
At present 400 products comprising 200 active ingredients are registered. Most <strong>of</strong>
the raw material for the formulation including active ingredients <strong>and</strong> pesticides in
finished form are being imported because local manufacturing <strong>of</strong> pesticides is very

limited in Pakistan. Out <strong>of</strong> total pesticides imported for plant protection 88%;o are
insecticides, IIo herbicides <strong>and</strong> loh fungicidesl8. Agricultural production has greatly
benefited from the use <strong>of</strong> pesticides. The heavy reliance <strong>of</strong> pesticides also generated the
question <strong>of</strong> how to protect the long term quality <strong>of</strong> our soil <strong>and</strong> water resources.
1.1.3.2 Study <strong>of</strong> pesticides in Pakistan
The study <strong>of</strong> the fate <strong>of</strong> pesticides in our own environment is highly significant so
that potential threats can be analyzed <strong>and</strong> necessary steps can be taken for their
abatement. Rural areas are the prime victims <strong>of</strong> pesticide contamination <strong>and</strong> the fact that
conventional water treatments such as chemical oxidation, alkali treatment, aeration,
incineration etc. fail to remove pesticides below allowable limits make rural population
more vulnerable to pesticide contamination. Moreovet, in our country these water
purification systems are not available to most <strong>of</strong> the rural population 2.
Although wide spread usage <strong>of</strong> pesticides had controlled the pest but started
causing environmental problems in the area. In some area <strong>of</strong> Punjab <strong>and</strong> Sindh ground
water was found contaminated due to pesticide, ur. te.
Insecticides residue in ground water samples from Mardan, N.W.F.P were also
reported2O. Stability <strong>of</strong> organophosphate <strong>and</strong> pyrethroid pesticides on wheat in storage
was also studied with reference to temperature <strong>and</strong> moisture2l.
Ad<strong>sorption</strong> <strong>of</strong> pesticides bifenthrien, carbosulfan, )"-cyhalothrin, cypernethrin,
endosulfan, parathion methyl, monocrotophos, <strong>and</strong> 4-nitrophenol by s<strong>and</strong>y, clay loam <strong>and</strong>
s<strong>and</strong>y loam soils with varying organic contents were studied22.
Residues <strong>of</strong> three pesticides popularly used on rice, diazinon (an
organophosphate), lindane (an organochlorine) <strong>and</strong> carbaryl (a carbamate) was detected
in Punjab <strong>and</strong> N.W.F.P. Results obtained indicated that residues <strong>of</strong> all three insecticides
do fall to nesilible levels23.

Sorption behavior <strong>of</strong> non toxic pesticides carbaryl <strong>and</strong> phosalone in soils from
Pakistan gave the <strong>sorption</strong> coefficient K6 value, for carbaryl it ranged from 0.99 to 59.1
L/kg <strong>and</strong> for phosalone it ranged from 15.5 to 1182.2L1kg24.
Heavy use <strong>of</strong> pesticides was observed in Swat valley. Six pesticides are identified
in soil sample from Swat, N.W.F.P these included four banned type dieldrin, DDT,
melathion, lindane <strong>and</strong> two restricted ones ( methyl parathion <strong>and</strong> heptachlor)2s.
Pesticides are prevalent ground water contaminants <strong>and</strong> are significant
components <strong>of</strong> hazardous waste <strong>and</strong> l<strong>and</strong>fills sites26. The production <strong>and</strong> use <strong>of</strong> pesticides
<strong>and</strong> their apparent hazards to human health have prompted investigation concerning their
fate in air, soil, sub surface water <strong>and</strong> treatment facilities.
1.1.4 Fungicides
The type <strong>of</strong> pesticides that are used in this study belongs to the fungicide class.
Fungicides are chemical compounds or biological organism used to kill or inhabit fungi
or fungal spores. Fungi can also cause serious damage in agriculture, resulting in critical
loss <strong>of</strong> yield, quality <strong>and</strong> pr<strong>of</strong>it27.
Fungicides are extensively used in industry <strong>and</strong> agriculture for a number <strong>of</strong>
purposes, including protection <strong>of</strong> seeds <strong>and</strong> grains, germination, protection <strong>of</strong> mature
crops, berries, seedlings, flowers, grasses in the field, in storage, during shipment <strong>and</strong>
protection <strong>of</strong> carpet <strong>and</strong> fabrics in the home.
Fungicides vary enorrnously in their potential for causing adverse effects in
humans. Historically, some <strong>of</strong> the most tragic epidemics <strong>of</strong> pesticide poisoning occurred
because <strong>of</strong> mistaken consumption <strong>of</strong> seed grain treated with organic mercury or
hexachlorobenzene. However, most fungicides currently in use are unlikely to cause
frequent or severe systemic poisonings for several reasons. Apart from systemic
poisonings, fungicides as a class are probably responsible for a disproportionate number
<strong>of</strong> initant injuries to skin <strong>and</strong> mucous membranes, as well as dermal sensitization.

l.l.4.l Classification <strong>of</strong> fungicides
They can be classified according to their chemical composition, application site,
application timing <strong>and</strong> mode <strong>of</strong> action or byproduct behavior. Of these the most
commonly used classifications are according to chemical class <strong>and</strong> application timing on
the crop28.
a) Protectantfungicides
Protectant fungicides are applied to the plant surface before infection occurs.
They remain on the surface <strong>and</strong> kill any fungal spores or bacterial cells that come into
contact with them. Protectant fungicides tend to be broad spectrum <strong>and</strong> be effective
against a wide range <strong>of</strong> fungal diseases.
b) Eradicantfungicides
Eradicant fungicides are applied when an infection has already become visible
<strong>and</strong> for preventing further sporulation <strong>and</strong> spread <strong>of</strong> the disease.
c) Systemic fungicides
Systemic fungicides move inside a plant following ab<strong>sorption</strong> by the plant. With
insecticides <strong>and</strong> most fungicides, this movement is usually upward (through the xylem)
<strong>and</strong> outward. Benzimi dazole compounds belong to this class <strong>of</strong> fungicides.
Systemic fungicides undoubtedly will cover susceptible foliage <strong>and</strong> flower part
more efficiently than protectant fungicides because <strong>of</strong> their ability <strong>of</strong> translocation
through the cuticle <strong>and</strong> across leaves2e.

1.1.5 Benzimid azole Fungicides
The fungicides under study are <strong>benzimidazole</strong> compounds which belong to the
class <strong>of</strong> systemic fungicides. Nearly all <strong>of</strong> the commercially used fungicides are synthetic
in nature. They are heterocyclic aromatic organic compound. These bicyclic compounds
consist <strong>of</strong> fusion <strong>of</strong> benzene <strong>and</strong> imidazole..
lH-<strong>benzimidazole</strong>
Benzimidazoles are prepared from o-phenylenediamine by the action <strong>of</strong>
chlor<strong>of</strong>orm, alcoholic potassium hydroxide <strong>and</strong> formic acid, <strong>and</strong> also by the reduction <strong>of</strong>
o-nitr<strong>of</strong>ormanilide. Less serviceable methods include the interaction <strong>of</strong> o-
phenylenediamine <strong>and</strong> dichloromethylformamidine, or diphenylformamidine, or
formoacetic anhydride, <strong>and</strong> the thermal decarboxylation <strong>of</strong> <strong>benzimidazole</strong>-2-carboxylic
acid. The conversion <strong>of</strong> aliphatic acids to 2-alkylbenzimrdazoles, by heating with o-
phenylenediamine is a general method for preparing solid derivatives30.
The <strong>benzimidazole</strong> compounds have been proved to be the most important group
on fungicides with systemic activity <strong>and</strong> are well known for their pronounced ability to
control a large number <strong>of</strong> fungal diseases. Benomyl, carbendazim, fuberidazole,
thiabendazole, thiophenate <strong>and</strong> thiophenate-methyl are main example <strong>of</strong> their fungicides
class because <strong>of</strong> their svstemic activitv3r.
N
)
N
H

Table 1..1: The use <strong>and</strong> trade name <strong>of</strong> some commercially available <strong>benzimidazole</strong>
fungicides.
Structures <strong>and</strong> Name Trade Name Primary Use
-Y'{".
CARBENDAZIM
I
Lr=C-].IHC.H,
BENOMYL
THIABENDAZOLE
Y vilr
il 'r"r'/
'--,,y' */
FUBERIDAZOLE
,.' \--H\ ,rtO
L \rJl -F .N .)-"*-\,o**,
J= c =ll(cHricN
CYPENDAZOLE
Bavistin. Akozim
Benlate, Tersan
Aliette super, Thiram
Arbotect 20-S
Imazalil
Folcidin
10
Protects orchards, vineyards,
vegetables against many fungal
diseases.
Foliage <strong>and</strong> soil fungicide, effective
against grey mold, apple scab <strong>and</strong>
powdery mildew, also used in seed
dressins.
For the protection <strong>of</strong>apples <strong>and</strong> pears
against fungi.
Effective for seed treatment against
Fusarium,leaf rust, <strong>and</strong> powdery
mildew on barley
activitv as Benomvl.

pesticides can be grouped according to their chemical structures. Pesticides with
similar structure have similar characteristics <strong>and</strong> usually have a similar mode <strong>of</strong> action'
The equitoxcity <strong>of</strong> <strong>benzimidazole</strong> compounds with widely different substituent groups
suggest a common mode <strong>of</strong> action <strong>of</strong> the <strong>benzimidazole</strong> moiety being the active part <strong>of</strong>
the molecule. It is likely that a common mode <strong>of</strong> action for various <strong>benzimidazole</strong>
analogues for fungicidal activity 32.
Benzimidazole nucleus is an important pharmacophore in drug discovery.
Several <strong>of</strong>thous<strong>and</strong>s <strong>of</strong>analogues <strong>of</strong> <strong>benzimidazole</strong> have been synthesized <strong>and</strong> screened
for pharmacological activity. Derivatives <strong>of</strong> <strong>benzimidazole</strong> compounds are known for
their antibacterial, trichomonacidal, anthelmintic, fungicidal, antiviral, antitubercular, anti
allergic, antioxidant, antihistaminic, antimicrobial33'34, antiulcerative, anti-inflammatory,
analgesic, antiHIV-1, antiproliferative, antikinase <strong>and</strong> potential anticancer activities3s.
Benzimidazole fungicides are also called MBC-fungicides because they all
generate MBC (methyl <strong>benzimidazole</strong> carbamate), either as the principal active
ingredient, or as a breakdown compound formed on mixing with water. They have a
common mode <strong>of</strong> action interfering with cell division <strong>and</strong> hyphal growth <strong>of</strong> sensitive
fungi. They are upwardly systemic with a broad range <strong>of</strong> activity against ascomycetes,
fungi imperfecti <strong>and</strong> basidomycetes 36.
In late 1960's they <strong>of</strong>fered systemic, curative fungicidal activity on a number <strong>of</strong>
diseases on fruits <strong>and</strong> vegetables i.e. mold on beans , citrus fruit, berry fruits, grapes, rot
on tomatoes, onions, stone fruits, avocadoes, garlic <strong>and</strong> omamentals, powdery mildew on
cucurbits <strong>and</strong> apples, eyespot on cereals, speckled leaf <strong>and</strong> blot on wheat37.
Resistance to <strong>benzimidazole</strong> fungicide is wide spread among many pathogens i.e.
3 8.
B o tryt i s c ine r e a, Sphaer o the c a ful i gine a, P enc illium di git atum etc
Some important pathogens, such as Pithomyces chartarum, Sclerotinia
sclerotiorum, S.minor <strong>and</strong> Podosphaeria leucotricha are not found resistant yet they are
still effective when applied in mixture <strong>of</strong> protectant fungicides with proper application
rate <strong>and</strong> cultural controls 37'3e.
11

a) Carbendazim
Carbendazim is a systemic <strong>benzimidazole</strong> fungicide <strong>and</strong> it plays a very important
role in plant disease control. Carbendazim is used to control a broad range <strong>of</strong> disease on
arable crops (cereals, oil rapeseed), fruits, vegetables <strong>and</strong> ornamentals 4042.
It is also used in post-harvest food storage, <strong>and</strong> as a seed preplanting treatment
carbendazim works by inhibiting the development <strong>of</strong> fungi by interfering with spindle
formation (cell divisio n) ot'oo .
The fungicide carbendazim is widely used in crop protection. It is also the
principal degradation product <strong>of</strong> benomyl <strong>and</strong> thiophenate methyl for this reason
benomyl <strong>and</strong> thiophenate methyl tolerance is generally expressed as carbendazima5.
During the growing period these agrochemicals are widely applied on various crops like
grapes, pome fruits, stone fruits, lettuce <strong>and</strong> cereal they act systematically. While at post
harvest they are usually applied on bananas, citrus fruits, pomes fruits, mangoes <strong>and</strong>
potatoes to protect them from decay caused by various fungal pathogens a0-46. This
fungicide has been used in the control <strong>of</strong> fungal infections in vineyards <strong>and</strong> is indicated
against Botrytis cinerea, Uncinula necator, Plasmopara viticola <strong>and</strong> other fungi. It can be
used either alone or coupled with other fungicides that exhibit different mechanisms <strong>of</strong>
.. 47 4R
actlon ' -.
b) Benomyl
Benomyl is a systemic <strong>benzimidazole</strong> fungicide that is selectively toxic to
microorganisms <strong>and</strong> to invertebrates. It is used against a wide range <strong>of</strong> fungal disease <strong>of</strong>
field crops, fruits, nuts, ornamentals; mushrooms <strong>and</strong> turfe. It is also useful to control
post harvest rots <strong>and</strong> moldsso. Formulations include wetable powder, dry flowable
powder <strong>and</strong> dispersible granules. Benomyl is strongly bound to soil <strong>and</strong> is highly
persistent sl. It completely degrades to carbendazim within several hours in acidic or
neutral water s2. Benomyl is unstable in water <strong>and</strong> change is completedin24 hours at pH
3 <strong>and</strong> 20oC s3.
t2

The most common degradation product <strong>of</strong> benomyl is carbendazim which is also
fungi toxic. High performance liquid chromatographic method was used to determine
benomyl <strong>and</strong> carbendazim simultaneously by converting benomyl into STB in the
alkaline media while carbendazim remained unaffected sa.
Ad<strong>sorption</strong> <strong>of</strong> <strong>benzimidazole</strong> derivatives on clays, minerals <strong>and</strong> soils are reported.
Ad<strong>sorption</strong> <strong>of</strong> three benzimtdazole derivatives, thia<strong>benzimidazole</strong>, carbendazim <strong>and</strong>
<strong>benzimidazole</strong> showed that increase in the activity <strong>of</strong> suspension resulted in significant
increase in the ad<strong>sorption</strong> <strong>of</strong> fungicide to the clay ss.-Ad<strong>sorption</strong> on three soils also
showed that with increasing acidity increase in ad<strong>sorption</strong> <strong>of</strong> these fungicides to the soil
occurred s6. Adso.ption <strong>of</strong> carbendazim with peat <strong>and</strong> montmorillonite was studied as
function <strong>of</strong> exchangeable cation <strong>and</strong> temperature <strong>and</strong> kinetics showed that ad<strong>sorption</strong>
equilibrium was reached within t hour 57.
1.2 Soils
Soil act as filter <strong>and</strong> buffer but it is recognized that soil is a potential pathway <strong>of</strong>
pesticides transport to contaminate water, air, plant food <strong>and</strong> ultimately to the human via
run<strong>of</strong>f <strong>and</strong> subsurface drainage, interflow <strong>and</strong> leaching, the transfer <strong>of</strong> mineral nutrients
<strong>and</strong> pesticides from soils into the plant <strong>and</strong> animals that constitute the human food chain.
While various physico-chemical processes affect the fate <strong>of</strong> agrochemicals incontact with
soil, the ad<strong>sorption</strong>-de<strong>sorption</strong> is one <strong>of</strong> the most important processes which controls all
other processes such as their movement, persistence, <strong>and</strong> degradation. De<strong>sorption</strong> <strong>of</strong>
chemicals is also critical in determining the availability to the target species, their
behaviour in run<strong>of</strong>f stream <strong>and</strong> in ground water pollution 58-61.
Soils are complex materials, reflecting the variability <strong>of</strong> the present rock material
<strong>and</strong> organic residue from which they are formed. Nevertheless their elemental
composition, particle size <strong>and</strong> mineralogy can be related more or less systematically to
the nature <strong>of</strong> parent material <strong>and</strong> the degree to which this material has been altered by
weathering 62.
1a
IJ

1.2.1 Composition <strong>and</strong> structure <strong>of</strong> soils
Through their surface electrochemical properties, these soil minerals control
ad<strong>sorption</strong>, transformation <strong>and</strong> release behavior <strong>of</strong> chemical constituents (e.g- nutrients
<strong>and</strong> contaminants) to water or soil solution. Soil surface electrochemical properties vary
between soil types <strong>and</strong> depend on factors such as parent material, climate <strong>and</strong> vegetation.
a) Overall makeup <strong>of</strong> soil
ll.
lll.
Inorganic mineral matter defined as soil material made up mostly <strong>of</strong>
oxygen, silicon <strong>and</strong> aluminium. Many other metals in small quantities may
be included.
Organic mineral matter defined as soil material having derived mostly
from plant residue <strong>and</strong> made up mostly <strong>of</strong> carbon, oxygen <strong>and</strong> hydrogen.
Solute refers to the portion <strong>of</strong> soil composed <strong>of</strong> water <strong>and</strong> mostly
dissolved salts (plant nutrients).
iv. Air refers to the gaseous portion <strong>of</strong> soil composed <strong>of</strong> the gases found tn
the atmosphere (oxygen, nitrogen <strong>and</strong> carbon dioxide) but in different
proportion.
Soil is highly complex, highly variable bimolecular sieve with an array <strong>of</strong>
physical <strong>and</strong> chemical properties.
b) Physical properties
i. Macro porosity composed <strong>of</strong> pores with diameter greater than 200 pm.
ii. Micro porosity composed <strong>of</strong> pores with diameter less than 200 pm.
iii. Physical stability refers to bonding strength between soil particles forming
aggregates.
I4

iv. External/intemal surface <strong>and</strong> its geometry defined as magnitude <strong>of</strong> soil
c) Chemical properties
specific in square meters per gram <strong>and</strong> depth or width <strong>of</strong> clay's internal
surface in nanometer's.
i. Permanent charge defined as cat ion exchange capacity, CEC, which is
independent <strong>of</strong> pH.
ii. Variable charge defined as pH-dependant CEC.
iii. Point <strong>of</strong> zero charge, PZA defined as the pH at which the net surface
charge is zero or CEC minus anion exchange capacity, AEC, equal
zero.
iv. Inner sphere/outer sphere surface complexes defined as strong surface
complexes or inner sphere complexes as opposed to weak surface
complexes or outer sphere complexes.
v. Hydrophobic-hydrophilic potential defined as the potential <strong>of</strong> soil to
adsorb water.
vi. pH buffering defined as the potential <strong>of</strong> soil to resist pH changes.
These physiochemical properties play an important role in regulating surface <strong>and</strong>
ground water chemistry 63.
l.2.l.l Soil minerals
a) Inorganic minerals
Inorsanic minerals <strong>of</strong> soil are classified into:
i. Primary minerals
ii. Secondary minerals
15

Generally the size <strong>of</strong> soil mineral varies from clay sized colloids (< 2pm) to gravel (< 2mm) <strong>and</strong>
rocks.
Primary minerals are minerals with chemical composition <strong>and</strong> structure obtained during
the crystallizationprocess <strong>of</strong> molten lava. Primary mineral groups are silica minerals (including
quartz), feldspar, olivines, pyroxene, amphioboles <strong>and</strong> micas based on alrangement <strong>of</strong> connected
silica (SiO+) tetrahedral.
3Sr,1AI
6 (o)
K
6(o)
3SilAl
{o),2(oH)
6Al
4(O),z(OH)
3SrlAl
6(o)
Fig. 1.1: Diagrammatic representation <strong>of</strong> Muscovite (Mica)
Alumino silicates have an inorganic crystalline structure which makes up a large part <strong>of</strong> <
0.2mm soil-sized particle. These minerals known as clay mineral consist <strong>of</strong> Si-O tetrahedra
<strong>and</strong> Al-O octahedra. Substitution <strong>of</strong> aluminum atom for silicon in tetrahedron or substitution
<strong>of</strong> divalent cation (i.e. Mg*2 <strong>and</strong> Fe*2) for aluminum is common occrurence. Substitution <strong>of</strong> a
given coordinating cation by a lower valence in a mineral gives rise to permanent negative
l6

charge or cation exchange capacity CEC location <strong>of</strong> this substitution give rise to clay
minerals with unique physiochemical properties.
4Si
6 (o)
rrarious cations
6(o)
4Si
4(o),2(oH)
6(AI, Fe,IvE)
4(o),2(OH)
4Si
6(O)
Fig. 1.2: Diagrammatic representation <strong>of</strong> Montmorillonite
Whereas secondary minerals are those that have been altered from the original structure
<strong>and</strong> chemical composition by weathering, a process referred to as the geomorphic cycle in clay
fraction <strong>of</strong> soils as sheet silicates. They have numerous structural combinations <strong>of</strong> the tetrahedral
sheets with octahedral coordinated metal cation i.e Kaolonite (1:1), vermiculite (2:1) <strong>and</strong>
smectite (2:l) layer silicates.
t7

) Metal oxides
Metal oxides are present in soil as:
i. Free oxides
ll.
iii.
Clay mineral coatings
Clay edges
Metal oxides exhibit charge due to protonation <strong>and</strong> deprotonation <strong>of</strong> the oxygen
coordinated to metal (F.*', Mn *', Al*3 <strong>and</strong> Si*4; this charge is known as variable charge
or pH dependant charge 6a.
c) Soil organic matter
Soil organic matter (SOM) is made <strong>of</strong> two major groups <strong>of</strong> compounds the non-
nitrogenous compounds which are mainly carbohydrates <strong>and</strong> the nitrogenous compounds
derived from protiens.
As organic matter decomposes the final product humus is produced ,70 to 80% <strong>of</strong>
organic matter, by weight found in most soils consist <strong>of</strong> humic substances.
Humic substances contains a large number <strong>of</strong> identical functional groups with
different pKu values <strong>and</strong> are partitioned into three main fractions based upon their
stability behavior.
l.
ii.
iii.
Humic acid
Fulvic acid
Humin
Humic substance exhibit poly functionality, molecular negative charge,
hydrophobicity <strong>and</strong> structure liability due to intermolecular association. Commonly
humic substance forms a strong complex with clay.
l8

1.2.1.2 Surface functional group
The mineral surface component responsible for ad<strong>sorption</strong> is also called
functional group. In case <strong>of</strong> minerals with permanent charge (e.g. aluminosilicates)
functional group is siloxane or ditrigonal cavity in case <strong>of</strong> clay mineral edges, the surface
functional groups are (OH)- species capable <strong>of</strong> dissociating (H*). There are three such
potential functional groups on clay minerals.
ll.
I ll.
The first group is the -AI-OH (octahedron) or aluminol with pKu around
The second is silanol (-Si-OH) tetrahedron with pKu around 9, the
intermediate -Si-Al-OH2 (OH shared between a tetrahedral sheet <strong>and</strong> an
octahedral sheet) with apparent pKu <strong>of</strong> around 6-7. These functional
groups are distributed on three different clay mineral site types. First site
is planar exposed by siloxane cavities, second is known as edge <strong>and</strong>
represented by aluminol silanol <strong>and</strong> intermediate functional OH groups.
Third site is knows a inter layer <strong>and</strong> is represented by the space between
adiacent siloxane cavities.
1.2.2 Classification <strong>of</strong> soil
Soil textures are classified by the fractions <strong>of</strong>each soil separately (s<strong>and</strong>, silt, <strong>and</strong>
clay) present in a soil. Classifications are typically named for the primary constituent
particle size or a combination <strong>of</strong> the most abundant particle sizes, e.g. "s<strong>and</strong>y clay" or
"silty clay". A fourth term loam, is used to describe a roughly equal concentration <strong>of</strong>
s<strong>and</strong>, silt, clay, <strong>and</strong> lends to the naming <strong>of</strong> even more classifications, e.g. "clay loam" or
"silt loam".
Twelve soil texture classifications are defined by the USDA 67.
ll.
Clay
silt
19

i. S<strong>and</strong>
ii. Loam
iii. Silty clay
iv. S<strong>and</strong>y clay
v. Clay loam
vi. Silt loam
vii. S<strong>and</strong>y Loam
viii. Loamy s<strong>and</strong>
ix. Silty clay loam
x. S<strong>and</strong>y clay loam
Determining the soil textures is <strong>of</strong>ten aided with the use <strong>of</strong> a soil texture triangle.
90
100
\60 50 40
Percent S<strong>and</strong>
Fig. 1.3: Determining the soil textures with the use <strong>of</strong> a soil texture triangle
20

1.2.3 Soil sampling
Soil is a heterogeneous material which is evident from the fact that various types
<strong>of</strong>soil have visual differences in surface appearance <strong>and</strong> in the pr<strong>of</strong>ile 68.
Successful soil testing depends upon the initial soil samples.The importance <strong>of</strong> a
representative soil sample prior to laboratory preparation, extraction, analysis <strong>and</strong>
interpretation <strong>of</strong> results is readily apparent. Obtaining the representative soil sample is the
key to soil sampling program.
a) Time <strong>of</strong> sampling
Fields used for crop production are best sampled at any time after crop harvest
before planting. Fields with non cultivated crops can be sampled during dormant season.
To account for seasonal variation soil samples should be collected at
approximately the same time each year. Soil should be retested as <strong>of</strong>ten as necessary ro
determine the influence <strong>of</strong> crop production <strong>and</strong> cultural practices on soil chemical
properties.
b) Sampling materials
Common tools used to sample soils for routine analysis include: spade, h<strong>and</strong>
probe, h<strong>and</strong> auger, bucket auger, oakfield probe <strong>and</strong> king tube or vehicle mounted
hydraulic probe or auge, 6t.
Sampling equipment should be clean free <strong>of</strong> rust <strong>and</strong> chrome plated, or made <strong>of</strong>
stainless steel, especially for micro nutrient analysis.
c) Sampling procedures
Obtaining the representative soil sample is the key to a soil sampling program.
A representative soil sample gives an average estimate <strong>of</strong> the whole area sampled.
A sub sample <strong>of</strong> soil mixture is removed <strong>and</strong> placed in a soil sample bag, <strong>of</strong>ten
lined with plastic. Individual soil cores from a minimum <strong>of</strong> 20 locations should be mixed
2I

thoroughly in clean plastic containers. This sample commonly referred to as the
composite sample consist <strong>of</strong> a mixture <strong>of</strong> the individual cores.
The altemative to composite sampling is the physical averaging <strong>of</strong> the analytical
results <strong>of</strong> individual soil cores (a costly procedure) to obtain the arithmetic mean.
Composite sampling decreases the cost <strong>of</strong> individual analysis for each soil core <strong>of</strong> the bag
must be properly labeled with_field identification, sampling depth management history
<strong>and</strong> other descriptive characteristics. Moist samples must be air dried before submission
to laboratory to prevent alteration <strong>of</strong> the nutrient concentration by soil microorganism.
Sample contamination from dust <strong>and</strong> foreign materials should be avoided during the air
drying process.
Generally, a 100 acre field comprises <strong>of</strong> the largest area to be sampled as one unit
the number <strong>of</strong> cores to represent an average soil from a field is determined by field
variability not by number <strong>of</strong> acres. The number <strong>of</strong> cores obtained determine the accuracy
<strong>and</strong> precision <strong>of</strong> the analytical result. Crop residues should be removed from the surface
before sampling.
Sampling depth for most soil traditionally has been the tillage depth, which
consists <strong>of</strong> 0-6 inch interval. The top 6 inches is the area that has the majority <strong>of</strong> root
activity <strong>and</strong> pesticide application are restricted to this depth 67.
Uniform field can be sampled in a simple r<strong>and</strong>om, stratified r<strong>and</strong>om or systematic
pattern .The results from these sampling plans, the soil test value, provides an estimate <strong>of</strong>
the entire population <strong>of</strong> possible soil test results. As the number <strong>of</strong> cores increases, the
error or chances <strong>of</strong> obtaining an inaccurate estimate <strong>of</strong> the average soil test value
decreases. A good sampling plan helps to ensure the accuracy <strong>of</strong> the soil test
result.
R<strong>and</strong>om sampling
With a simple r<strong>and</strong>om system each soil core is selected separately, r<strong>and</strong>omly <strong>and</strong>
independently <strong>of</strong> previously drawn units.
22

X
X
X X
X X
XXXX
XX
ii. Stratified r<strong>and</strong>om
X X X
X
A stratified r<strong>and</strong>om sample is taken from a field that has been divided into several
sub units or quadrant from which simple r<strong>and</strong>om cores are obtained. This increases the
precision for the field.
X
KX
X'
X
X
X
X
^a ZJ
X
X
X
X
X
X

111. Systematic sampling
The systematic sample is a further progression in an attempt to ensure
complete field coverage similar to the change from the r<strong>and</strong>om to the stratified
r<strong>and</strong>om cores are taken at regular spaced interval in all directions. The systematic
sampling plan has been widely accepted because it is straight forward <strong>and</strong>
potentially increases the accuracy <strong>of</strong>soil test.
1.2.4 Soils <strong>of</strong> Pakistan
XXIXXX
XXIXXX
X X IX X X
X X IX X X
XXXIXXX
The soils <strong>of</strong> Pakistan are derived from two types <strong>of</strong> parent materials 68
ii.
Alluvium, Loess <strong>and</strong> wind reworked s<strong>and</strong>s. They are <strong>of</strong> mixed
mineralogy.
Residual material obtained from weathering <strong>of</strong> underlying rocks. Most <strong>of</strong>
the rocks are calcareous. In some areas, granites have produced non-
calcareous soil material. Very small quantities <strong>of</strong> salts are released from
most <strong>of</strong> the rocks. The soils are therefore. essentiallv non-saline.
The soils <strong>of</strong> Pakistan have acquired distinct characteristics from the parent
material <strong>and</strong> by their mode <strong>of</strong> formation. The river-laid sediments have developed into
1A

alluvial soils. The desert s<strong>and</strong>s have turned into distinct soils. The hills, mountains <strong>and</strong> the
plateaus have produced Residual Soils with patches <strong>of</strong> alluvial, loess <strong>and</strong> other soils.
Accordingly, the soils <strong>of</strong> Pakistan can be classified into the following six types.
i. Alluvial soils <strong>of</strong> the flood plains.
ii. Alluvial soils <strong>of</strong> the bar upl<strong>and</strong>s.
iii. Soils <strong>of</strong> the Piedmont plains.
iv. Desert soils.
vi.
Soils <strong>of</strong> Potohar plateau.
Soils <strong>of</strong> westem hills based on these broad classes.
't' r
Fig. 1.4: Map represents the 26 broad soil types <strong>of</strong> Pakistan.
25
ti
I
I F
I I
ill I
i
i
i
:
rl
qrn
rffirs
5F
illr
Itlt
I
I
l:llrhd-
I rrrlr*il
{
N
i
i t -rttf r*
j gir,

Table 1.2: Soil types <strong>of</strong> Pakistan (Description <strong>of</strong> figure F.gl.a)
Soil Type Area
(000'ha)
I Loamv <strong>and</strong> s<strong>and</strong>v stratified soils 1.0 0.1
2. Loamy <strong>and</strong> clayey non-calcareous soils 4.6 0.6
J. MOUNTAINS: Loamy shallow soils VALLEYS :
Loamy non-calcareous soils
r 8.6 z.)
4. Loamy s<strong>and</strong>v stratified soils 1.5 0.2
5. Loamy clayey non-calcareous soils 7.7 1.0
6. Loamy non-calcareous soils <strong>of</strong> alluvial/loess plains 18.2 2..)
n
MOUNTAINS: Loamy <strong>and</strong> shallow soils VALLEYS :
Laomy soils
8. MOTINTAINS: Rock out-crops loamy <strong>and</strong> shallow soils
VALLEYS : Loamy soils
t0.2 1.3
17.0 2.1
9. Loamy partly gravelly soils 0.7 0.1
10. MOUNTAINS: Loamy shallow soils <strong>and</strong> rock out-crop
VALLEYS : Loamy soils
l1 MOLINTAINS: Rock out-crop <strong>and</strong> loamy very shallow
soils VALLEYS : Loamy soils
26
2.7 0.3
4r.7 5.2
o/otage

12. MOL|NTAINS:Rock outcrop, some loamy very shallow
soils VALLEYS : Mainlv loamv soils
22.7 2.9
lJ. Laomy s<strong>and</strong>y stratified soils 18.8 2.4
t4. Loamy clayey soils 90.4 tt.4
15. Loamy soils <strong>of</strong> old river terraces 21.9 2.8
t6. Laomy clayey mainly dense saline sodic soils 2.0 0.3
17. Loamy <strong>and</strong> clayey partly slaine sodic soils 52.7 6.6
18. Mainly loamy saline soils 15.3 t.9
t9. Silty <strong>and</strong> calyey saline soils 5.6 0.7
20. Rolling to hilly s<strong>and</strong>y soils 116.9 14.7
21 Mainly loamy partly gravelly soils 46.6 5.8
22. Mainly loamy partly gravelly soils 16.7 2.1
^a z)- MOUNTAINS: Rocky out-crop with patchy soils
VALLEYS : Mainly loamy partly gravelly soils
244.5 30.6
24. Clayey <strong>and</strong> loamy severely slaine sodic soils 2.7 0.3
25. Glaciers <strong>and</strong> snow caps 3.4 0.4
26. Rivers 13.0 r.6
Total 796.1 100.0
27

1.3 Ad<strong>sorption</strong>-de<strong>sorption</strong> <strong>studies</strong>
Soil functions as a chemical <strong>and</strong> biological filter that lessens the environmental
impact <strong>of</strong> organic chemicals soil forms the first line <strong>of</strong> defense against these compounds
into ground water <strong>and</strong> biosphere.A knowledge <strong>of</strong> <strong>sorption</strong> behavior <strong>of</strong> chemical
substances is necessary to underst<strong>and</strong> the consequences that may arise from their
controlled or uncontrolled distribution in the environment.
The ad<strong>sorption</strong> -de<strong>sorption</strong> <strong>of</strong> pesticide interaction <strong>and</strong> the <strong>sorption</strong> phenomena
can influence the translocation volatility, persistence <strong>and</strong> bioactivity <strong>of</strong> pesticide in soil .
Soil curtails mobility <strong>of</strong> organic chemicals by two *uys 6e.
i) Sorption.
ii) Biological <strong>and</strong> chemical degradation.
Although various physiochemical processes affect the fate <strong>of</strong> agrochemicals in
contact with soil, the ad<strong>sorption</strong> with the solid matrix <strong>of</strong> soil is one <strong>of</strong> the most important
phenomenon, which controls other processes such as pesticide transport, persistence
bioavailability <strong>and</strong> degradation.
For predicting the basis <strong>of</strong> the behavior <strong>of</strong> organic pollutant in the soil, <strong>and</strong>
evaluating the risk that a chemical might leach into ground water follows from
underst<strong>and</strong>ing <strong>of</strong>nature <strong>and</strong> extent <strong>of</strong>these ad<strong>sorption</strong> <strong>and</strong> degradation process.
1.3.1 Sorption
In <strong>sorption</strong>, a chemical species may accumulate on a mineral's surface either
through ad<strong>sorption</strong>, hydrophic interaction, <strong>and</strong>l or precipitation.
A mineral <strong>and</strong> organic surface <strong>of</strong> soils (adsorbent) may adsorb organic molecule
(the absorbent) weakly or strongly depending on the strength <strong>of</strong> the adsorbate-adsorbent
interaction. Strong interaction is indicative <strong>of</strong> chemical ad<strong>sorption</strong>, or chemi<strong>sorption</strong>s in
28
for
an

which a covalent or short range electrostatic bond forms between the molecule <strong>and</strong> the
surface.
Weak ad<strong>sorption</strong> on the other h<strong>and</strong> is characteristic <strong>of</strong> physical ad<strong>sorption</strong>
which the bonding interaction is not very energetic (typically 20
Kcal/mole than physical ad<strong>sorption</strong> (< l0 Kcal/mol).
Ad<strong>sorption</strong> & de<strong>sorption</strong> <strong>of</strong> organic molecule in soils is controlled by chemical
properties <strong>of</strong> the molecules <strong>and</strong> the surface properties <strong>of</strong> the particular soil 70.
Organic adsorbate has following relevant properties.
11.
Il1.
lv.
V.
Identity <strong>of</strong> functional group attached to the molecule.
Acidity or basicity <strong>of</strong> the functional groups.
Molecular size <strong>and</strong> shape.
Polarity <strong>and</strong> charge <strong>of</strong> the molecule.
Polarizability <strong>of</strong> the molecule.
These properties determine the water solubility <strong>of</strong> the molecule <strong>and</strong> the tendency
<strong>of</strong> the molecules to adsorb on soil surface. Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> pesticides in soil
influence their bioefficacy <strong>and</strong> persistence. It is also an important factor governing the
migratory behavior <strong>of</strong> pesticides in soil <strong>and</strong> ground water <strong>and</strong> may also influence the
uptake <strong>and</strong> metabolism by plant or microorganisms <strong>and</strong> other organisms present in soil.
29
in
<strong>of</strong>

1.3.2 Ad<strong>sorption</strong>-de<strong>sorption</strong> models
Equilibrium between solution <strong>and</strong> adsorbed or sorbed phases is a condition
commonly used to evaluate ad<strong>sorption</strong> or <strong>sorption</strong> processes in soils or soil-clay
minerals. Equilibrium is defined as the point at which the rate <strong>of</strong> the forward reaction
equals the rate <strong>of</strong> the reverse reaction. Two major techniques commonly used to model
soil ad<strong>sorption</strong> or <strong>sorption</strong> equilibrium processes are the (l) the Freundlich approach <strong>and</strong>
(2) the Langmuir approach. Both involve ad<strong>sorption</strong> <strong>and</strong> <strong>sorption</strong> isotherms. A <strong>sorption</strong>
isotherm describes the relationship between the dissolved concentration <strong>of</strong> a given
species (adsorbate) in units <strong>of</strong> micrograms per liter, milligrams per liter, microequivalents
per liter, or millimoles per liter, <strong>and</strong> the sorbed quantity <strong>of</strong> the same species by the solid
phase in units <strong>of</strong> adsorbate per unit mass <strong>of</strong> adsorbent (solid) at equilibrium under
constant pressure <strong>and</strong> temperature. Sorption isotherms have been classified into four
types, depending on their general shapes.
m
t
b
5
o
t
b
d
m
I
L-Type
Equilibrium Concentration
C-Type
m
t
b
s
o
R
B
E
d
m
I
b
s
o
r
o
e
d
S-Type
Equilibrium Concentration
Equilibrium Concentration Equilibrium Concentration
Fig. 1.5: Types <strong>of</strong> <strong>sorption</strong> isotherms
L-type: describes high affinity ad<strong>sorption</strong> between the adsorbate <strong>and</strong> adsorbent
<strong>and</strong> usually indicate chemi<strong>sorption</strong>s. (e. g. Phosphate-soil interactions)
30

11.
ul.
1V.
S-type: describes adsorbate-adsorbate interactions on the adsorbate, <strong>of</strong>ten referred
to as clustering , <strong>and</strong>/or the interaction <strong>of</strong> the adsorbate with solution lig<strong>and</strong>s.
When lig<strong>and</strong> saturation is reached, ad<strong>sorption</strong> proceeds (e.g. aluminium-fulvic
acid-clay interactions)
C-type: describes interaction between a generally hydrophobic adsorbate with a
hydrophobic adsorbent (e. g. pesticide-organic matter interactions)
H-type: describes strong chemi<strong>sorption</strong>s interactions, which is basically an
extreme case <strong>of</strong> the Ltype isotherms (e.g. phosphate-iron oxide interactions).
As mentioned earlier two major techniques commonly used to model soil
<strong>sorption</strong> equilibrium processes are the (1) the Freundlich approach <strong>and</strong> (2) the Langmuir
approach.
a) Freundlichequilibriumapproach
Soils are multicomponent systems consisting <strong>of</strong> solid, liquid <strong>and</strong> gaseous phases.
These three phases are constantly in a dynamic state, trying to maintain equilibrium. Any
type <strong>of</strong> perturbation in one phase influences the other phases so that a new equilibrium
state is approached. An equilibrium process that has been extensively investigated in soil
systems employing the Freundlich equation involves <strong>sorption</strong>.
-S + l/nC = -SC (t)
where - S denotes a heterogeneous soil mineral surface, C denotes chemicals
substance (e.g. organic contaminant in solution) in equilibrium with -S, l/n is an
empirical linearization constant, <strong>and</strong> -SC denotes the adsorbate-surface complex in
milligrams <strong>of</strong> adsorbate per unit mass <strong>of</strong> soil (e.g. per 100 g <strong>of</strong> soil).
b) Langmuir equilibrium approach
The Langmuir equilibrium approach was developed in 1918 by Langmuir to
describe vapor ad<strong>sorption</strong> on a homogeneous surface. It incorporates several assumptions
31

when employed to model ad<strong>sorption</strong> <strong>of</strong> chemical species-solution suspensions. These
assumptions are that :
i. The number <strong>of</strong> surface ad<strong>sorption</strong> sites are fixed.
ii. Ad<strong>sorption</strong> includes a single monolayer.
iii.Ad<strong>sorption</strong> behavior is independent <strong>of</strong> surface coverage.
iv. All ad<strong>sorption</strong> sites are represented by similar types <strong>of</strong> functional groups.
v. The isotherms displays L-type behavior 7r.
1.4 Pesticides used
In this study commercially used <strong>benzimidazole</strong> derivative methyl IH-
<strong>benzimidazole</strong>-2-carboxylate (Carbendazim) <strong>and</strong> <strong>benzimidazole</strong> derivatives 2-(4-
fluorophenyl)- lH- <strong>benzimidazole</strong> (FBNZ) <strong>and</strong> N-(1I1- <strong>benzimidazole</strong> -2-ylmethyl)
acetamide (ABNZ), synthesized were used.
Table 1.3: Pesticide used in this studv
resticide Structures <strong>and</strong> Chemical Names
arbendazim
FPNZ
ABNZ
\--1
NO
,/\
N O-CH3
m ethyl 1 H-benzim id azole -2-ca(boxvlate
N
\
N
2 -(4 -lluo rop h en yl)-1 H,benzim idazo le
\.. /2
).----*H4e u^
N'r
N-(1 H -benzim idazol-2 -ylm ethyl)acetam ide
JZ

Four field soils were collected from differerrt selected agricultural areas <strong>of</strong> Pakistan.
Mostly agricultural areas <strong>of</strong> NWFP, central <strong>and</strong> southern Punjab districts are focused.
The selection <strong>of</strong> these areas is based on the use <strong>of</strong> <strong>benzimidazole</strong> pesticides. The major
use <strong>of</strong> <strong>benzimidazole</strong> pesticides is against fungal diseases <strong>of</strong> fruits, vegetables <strong>and</strong>
cereals. The areas <strong>of</strong> south Punjab are major wheat growing areas <strong>and</strong> other selected
areas are major fruit growing areas. The soil samples from following areas were
studied:
11.
111.
iv.
Tarnol
Multan
Murree
Ayubia Q{.W.F.P)
The collection <strong>and</strong> processing <strong>of</strong> soil is done by using the st<strong>and</strong>ard methods. Each
soil is characterized by type, pH, moisture <strong>and</strong> organic contents etc.
Besides different soils, following soil minerals/clays
<strong>sorption</strong>/de<strong>sorption</strong> <strong>studies</strong> <strong>of</strong> these pesticides.
11.
iii.
lv.
Silica
Alumina
Montmorillonite
Muscovite
used for
Ad<strong>sorption</strong> experiments with pure soil constituents will provide valuable
knowledge to all <strong>of</strong> the above mentioned points because such experiment will show to
what extent these pesticides are absorbed if there are differences between adsorbent
which could indicate difference between soils with variety <strong>of</strong> composition72.
an
JJ

Ilg; lJ: Mhcnb/drp rEGd ln tbe rtrdy
v

t
i
Trmol
Flg; l.?: So& rrcd
35
l,tnrm Avft

2.1 Chemicals <strong>and</strong> solvents
EXPERIMENTAL
CHAPTER 2
Acetone <strong>and</strong> Methanol used were 99.9 oh pure from Merck, Germany. Sodium
chloride <strong>and</strong> calcium chloride anhydrous powder, extra pure used were products <strong>of</strong>
Scharlau Company, Spain. Benomyl, analytical grade benomyl, 99Yo pure was purchased
from ACCU St<strong>and</strong>ard USA. Carbendazim Analytical st<strong>and</strong>ard was purchased from
ACCU St<strong>and</strong>ard USA. Aluminum Oxide active neutral Brock Mann Grade I, used was
product from BDH Poole, Engl<strong>and</strong> <strong>and</strong> Silica gel 0.2 mm for chromatography was
product <strong>of</strong> Scharlau Company, Spain.
Muscovite, research grade was purchased from Alfa Aesar Company, Germany
<strong>and</strong> Montmorillonite, K-10 obtained from Sigma Aldrich Company, Germany. Pesticides
used in this study are <strong>benzimidazole</strong> derivatives 2-(4-fluorophenyl)-1H- <strong>benzimidazole</strong>
(FBNZ) <strong>and</strong> N-(111- <strong>benzimidazole</strong> -2-ylmethyl) acetamide (ABNZ) were synthesized in
the laboratory.
2.2 Instruments used
Melting points <strong>of</strong> pesticides were determined by melting point apparatus from
Gallen Kamp, Sanyo, UK. Organic matter contents were determined using Vulcan box
furnace. Soil pH was measured using Orion 420 plus, pH meter equipped with glass
electrode. Stuart Orbital shaker was used for agitation. Centrifugation was done in
Hettich Zentrifiigen EBA 20. Ad<strong>sorption</strong> spectra were recorded on UV-Visible
spectrophotometer model U-2800, Hitachi.
2.3 Soil collection
Four soils were collected (0-6 cm) deep from cultivated soil areas <strong>of</strong> Punjab &
N.W.F.P with no recent history <strong>of</strong> pesticides applications.
36

a) soIL I
Twenty sub samples <strong>of</strong> 2-3 kg <strong>of</strong> each were collected from Tarnol, Islamabad in
March 2009. Soil texture was clavey loam. Vesetation <strong>of</strong> the area is wheat.
b) sorl, 2
Twenty sub samples <strong>of</strong> 2 kg each were collected from acre <strong>of</strong> l<strong>and</strong> from chak no
136 W.B Tehsil, Harrapa district Multan, on 25 February 2008. Soil texture was
calcareous s<strong>and</strong>y loam. Vegetation when sampled was cotton <strong>and</strong> wheat.
c) SOIL 3
Fifteen sub samples were collected from Murree region, a boarder <strong>of</strong> Punjab &
N.W.F.P mountain area. It is a mountain soil, red in color locally called as "Ratti Mitti".
Soil texture was clayey loam. Vegetation <strong>of</strong> the area when sampled was apples, apricots
<strong>and</strong> plum. Soil was collected on23 July 2008.
d) sorl, 4
Fourth soil was collected from Ayubia <strong>and</strong> twelve sub samples <strong>of</strong> forest soil were
taken on 5 August 2009. Soil texture is loamy s<strong>and</strong> forest soil. Vegetation <strong>of</strong> the area is
maize, fresh beans <strong>and</strong> cucumbers.
All soil sub samples were collected in polythene bags. Each soil was than mixed
thoroughly, disaggregated first manually <strong>and</strong> than using a mortar <strong>and</strong> pestle. Soils were
than passed through 2 mm sieve <strong>and</strong> mixed manually to achieve homogeneity.
37

2.4 Physiochemical properties <strong>of</strong> pesticides
Samples <strong>of</strong> homogenized soil were used to determine moisture content, organic matter
content <strong>and</strong> pH.
2.4.1 Moisture content
Soils were dried at 105'C until a constant weight was achieved. Moisture contents were
determined by taking the difference in pre <strong>and</strong> post oven weights.
2,4.2 Organic matter content
"Loss on Ignition Methods" was used to determine organic matter contentT3. Same soil
samples moisture contents have been determined were taken <strong>and</strong> heated at 400oC in
fumace for 24 hours to oxidize orqanic matter.
2.4.3 Soil pH
Soil pH <strong>of</strong> all the soils was measured by mixing 1g <strong>of</strong> soil in 10 ml <strong>of</strong> re-distilled <strong>and</strong>
deionized water. After I hour <strong>of</strong> contact time pH <strong>of</strong> the slurry was measured using pH
meter74.
2.5 Preparations <strong>of</strong> solutions
2.5.1 Stock solutions
Solution A: 20 ppm: 20.6 mg <strong>of</strong> ABNZ & FBNZ was dissolved in lL <strong>of</strong> deionized
water separately <strong>and</strong> pH was checked.
Solution B: 10 ppm: 10.3 mg <strong>of</strong> Carbendazim, ABNZ & FBNZ was dissolved in lL
<strong>of</strong> deionized water separately <strong>and</strong> pHwas checkedLT4-7s
38

2.5.2 Dilutions
Eight concentrations <strong>of</strong> Carbendazim (0, 0.25, 0.5, 0.75, I.0,2.5,5.0 <strong>and</strong> 7.5
ppm) due to its limited solubility, <strong>and</strong> nine concentrations <strong>of</strong> FBNZ & ABNZ (0, 0.25,
0.5, 0.75, I.0,2.5,5.0,7.5 <strong>and</strong> 10 ppm) were made in 0.1M sodium chloride.
It was added as background electrolyte in each concentration to simulate ionic
strength similar to that <strong>of</strong> natural soil solution. It was also added as aqueous solvent phase
to improve centrifugation <strong>and</strong> to minimize cation exchange. Dilution <strong>of</strong> the stock solution
was done step wise as follows:
i. 100 ml volumetric flasks were washed, dried <strong>and</strong> labeled.
ii. 10 ml <strong>of</strong> 0.1M NaCl solution was added in each flask.
iii. 0,2.5,5.0,7.5, 10,25 & 50 <strong>and</strong> 75 ml <strong>of</strong> stock solution B was added in flasks
labeled 0, 0.25,0.5, 0.75, I.0,2.5 & 7.5 ppm for each Carbendazim, ABNZ &
FBNZ, respectively .
iv. To prepare 10 ppm solution <strong>of</strong> Carbendazim, ABNZ & FBNZ 50 ml <strong>of</strong> stock
solution A was added in flask labeled 10.
v. Deionized water was added in each flask to achieve the desired concentrations.
2.6 Ad<strong>sorption</strong> <strong>studies</strong>
All experiments were performed under isotherm conditions at 25 + loC. Ad<strong>sorption</strong>
<strong>studies</strong> were conducted as follows:
i. 15 ml Pyrex glass centrifuge tubes with screw cap were weighed.
ii. 0.5 g <strong>of</strong> mineral/soil was added as in each tube.
iii. 10 ml <strong>of</strong> pesticides st<strong>and</strong>ard solution from the volumetric flasks in each tube was
added <strong>and</strong> Sorbent/solution ratio was kept at 1:20.
iv. The tubes were continuously agitated on Shaker at 90 rpm for 24 hours at room
temperature (25 "C) to achieve equilibrium.
v. The ad<strong>sorption</strong> equilibration process was done in duplicate for each concentration
<strong>and</strong> blank sample containing only dissolved fungicides plus 0.1 M NaCl
39

ackground electrolyte without any mineral or soil were prepared <strong>and</strong> treated in
parallel with each set <strong>of</strong> batch experiment to qualifu the losses <strong>and</strong> to account for
possible degradation during ad<strong>sorption</strong> process.
vi. The centrifuge tubes containing equilibrated material were centrifuged at 3000
rpm for 25 minutes atZloC.
vii. Centrifuged tubes were decanted by filtering soil water suspension through 0.2
pm membrane <strong>and</strong> clear aliquots were taken for analysis <strong>of</strong> the pesticides by
visible ad<strong>sorption</strong> spectrophotometry.
viii. Supematant pH was measured in each tube.
2.7 De<strong>sorption</strong> <strong>studies</strong>
De<strong>sorption</strong> was conducted on the same fungicides soil /minerals solutions.
i. After <strong>sorption</strong> experiment the remainder <strong>of</strong> the supernatant was decanted.
ii. The centrifuge tubes plus the contents <strong>of</strong> the tubes were reweighed.
iii. Pesticide was desorbed by adding 9 ml <strong>of</strong> freshly prepared 0.lM CaClz solution
to the soil/minerals remaining in the centrifuge tubes.
iv. The samples were again shaken for 24 hours at25 oC.
v. Tubes were centrifuged for 25 minutes at 3000 rpm.
vi. Part <strong>of</strong> the supernatant was decanted <strong>and</strong> filtered through 0.2 pmmembrane.
vii. Concentration <strong>of</strong> the <strong>benzimidazole</strong> fungicides were measured by ad<strong>sorption</strong>
spectrophotometry <strong>of</strong> the desorbed fungicides.
40

RESULTS
3.1 Characteristics <strong>of</strong> pesticides <strong>and</strong> soils used
CHAPTER 3
In this study commercially used <strong>benzimidazole</strong> derivative methyl lH-
<strong>benzimidazole</strong>-2-carboxylate (Carbendazim) <strong>and</strong> <strong>benzimidazole</strong> derivatives 2-(4-
fluorophenyl)- lH- <strong>benzimidazole</strong> (FBNZ) <strong>and</strong> N-(1.F1- <strong>benzimidazole</strong> -2-ylmethyl)
acetamide (ABNZ), synthesized were used because they showed good antifungal
activity.
Table 3.1: Pesticides used in this study
Pesticide Color &
state
Carbendazinr White
crystalline
FBNZ White
crystalline
A.BNZ Pale white
:rystalline
Structures & chemical names M.P
2 -(4 -lluo ro p h e n yl)-1 H -b e n zim ad a zo le
N-(1H-benzim idazol-2-y lm ethyl)acetam ide
41
250"c
(Dec)
z6t"c
T77"C

Various physical <strong>and</strong> chemical properties <strong>of</strong> the four soils that were used to find out the
<strong>sorption</strong> behaviors <strong>of</strong> the three <strong>benzimidazole</strong> fungicides were determined (table 3.2).
Table 3.2: Relevant physiochemical properties <strong>of</strong> four soils
lharacteristics famol
Soil 1
3.2 General method used for ad<strong>sorption</strong>-de<strong>sorption</strong> <strong>studies</strong>
UV-Visible spectra <strong>of</strong> all the fungicides adsorbed on minerals <strong>and</strong> soils were
recorded at wavelength ranged between 200-300nm. The l. n,* for carbendazim was taken
at 28I.2 nm, FBNZ at 299.2 nm <strong>and</strong> ABNZ at 273 nm as shown in the spectra <strong>of</strong> all the
compounds. Spectra were scanned for a range <strong>of</strong> wavelength (figs 3.1-3.5, 3.I7-3.2I,
3.28-3.32) to ensure that if there is any change in the maximum wavelength (I,*) either
due to degradation <strong>of</strong> pesticides or due to soil-pesticides chemical interaction. The
absorbance <strong>of</strong> solutions recorded at the l.
'-nu*
concentrations <strong>of</strong> the adsorbed fungicides.
was taken as peak height to calculate the
The amount <strong>of</strong> the fungicides adsorbed (pgl g soil or mineral) was obtained
simply by subtracting the value obtained from the blank <strong>and</strong> the fungicide remaining in
the solution after equilibration using the relation:
X:V/m (Ce -CJ
Multan
Soil2
Murree
Soil 3
rH(1:10) 7.9 8.1 8.2 7.6
)rganic matter (oh) 2.29 2.27 2.32 ).45
Soil texture Loamy & clayey Loamy &
s<strong>and</strong>y
regetation when sampled Wheat Wheat,
cotton
42
Ayubia
Soil4
roamy Silt loam
A.pples,
A.pricots,
Peaches.
Maize,
French beans,
Cucumbers.
(2)

Where X: amount adsorbed, V: solution volume, m: grams <strong>of</strong> soil taken, Cs=
equilibrium concentration <strong>of</strong> blank <strong>and</strong> C.: equilibrium concentration <strong>of</strong> treatment
supematant.
The ad<strong>sorption</strong> values found were used to construct following linear type <strong>of</strong> isotherm (C-
tvpe).
X: K61u6ry C. (3)
Where Ko(uor) is linear or <strong>sorption</strong> equilibrium distribution co-efficient in (ml pg-t;. X is
the concentration <strong>of</strong> the pesticide adsorbed in (pg/g soil) <strong>and</strong> C. is the pesticide
concentration (pglml) at the equilibrium concentration.
De<strong>sorption</strong>, expressed as micrograms adsorbed/gram <strong>of</strong> soil/mineral (Wglg soil or
mineral), was obtained from the difference, taken into account the solution remaining in
the soil after the supernatant was poured <strong>of</strong>f. The <strong>sorption</strong> equilibrium distribution co-
efficient Ka(o.s) in (ml pg-'1*as calculated as:
Ko(orr):XIC" (4)
43

o.7
0.6
0.5
o.4
0.3
o.2
0.1
00
o.7
0.6
o.5
o.4
0.3
o.2
o.1
i-.'-.'.,,..,,.:"''"':....:.:..:,]l],;.,..,,.,.-,.'.",','L''.:J1
%o o 350
Fig. 3.1. Ad<strong>sorption</strong> spectra <strong>of</strong> Carbendazim by Almunia (ad<strong>sorption</strong> blank)
%o 300 350
Fig.3.2. Ad<strong>sorption</strong> spectra <strong>of</strong> Carbendazim by Almunia (ad<strong>sorption</strong> a)
o.7
u.o
o.5
o.4
n?
v.z
o.1
%o 300 350
Fig. 3.3. Ad<strong>sorption</strong> spectra <strong>of</strong> Carbendazim by Almunia (ad<strong>sorption</strong> b)

o.3o I
o.25'
o.20 I
I
o.15 i
o.1o I
:
o.ou i\;,,...
1-'
o.oo
'
I
I r r -'f' l nr
2fi 300 350
Fig. 3.4. Ad<strong>sorption</strong> spectra <strong>of</strong> Carbendazim by Almunia (de<strong>sorption</strong> a)
o.so i
o.25 |
I
0.20 i
n 1R
--I
i'
o.ro l"
n\"
0.o5
o.00
l
,. :
I
250
,l 300
Fig. 3.5. Ad<strong>sorption</strong> spectra <strong>of</strong> Carbendazim by Almunia (de<strong>sorption</strong> b)
350
nr
45

3.3 Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Alumina
Table 3.3: Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Alumina
pk.ht carb add ppm add uq/O.5q fnd ppm fnd uq/O.5q ads uq/O.5q ads uo/o % ads
A B C=B*10 p=(g/bt)-A E=D*10 F=C-E G=F*2 H=rrlcrtoo
1 1.7500 0.2500 2.5000 0.1626 1.6264 0.8736 1.7472 34.9442
z 1.7800 0.2500 2.5000 0.1654 1.6543 0.8457 1.6914 33.8290
J 3.5200 0.5000 5.0000 0.3308 3.3083 1.6917 3.3835 33.8346
4 3.5100 0.5000 5.0000 0.3299 3.2989 1.7011 3.4023 34.0226
5.0100 0.7500 7.5000 0.5285 5.2848 2.2152 4.4304 29.5359
b 5.0200 0.7500 7.5000 0.5295 5.2954 2.2046 4.4093 29.3952
6.3800 1.0000 10.0000 0.7641 7.6407 2.3593 4.7186 23.5928
B 5.9700 1.0000 10.0000 0.7150 7.1497 2.8503 5.7006 28.5030
I 15.0500 2.5000 25.0000 1.9364 19.3644 5.6356 11.2712 22.5425
10 15.0900 2.5000 25.0000 1.9416 19.4'159 5.5841 1'1.1683 22.3366
11 29.8900 5.0000 50.0000 3.7883 37.8834 12.1166 24.2332 24.2332
12 29.8000 5.0000 50.0000 3.7769 37.7693 12.2307 24.4613 24.4613
12 41.0100 7.5000 75.0000 5.9596 59.5960 15.4040 30.8080 20.5387
14 40.8800 7.5000 75.0000 5.9407 59,4071 15.5929 31 .1 858 20.7905
o'
B
.$
od
{ ct
di
tr
o
40
30
20
10
0
Fig.3.6
ADSORPTTON & DESORPTTON OF CARBENDAZTM BY At2O3
Equil. conc. ug/ml
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by AlzOs
46
ads
des
o I

3.4 De<strong>sorption</strong> <strong>of</strong> Carbendazim by Alumina
Table 3.4 (a): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Alumina
emo tb tb+min+sol ent sol
c-
A B
(B-A)-.5
carb
ent uq
p=
fndpom*C
Table 3.4 (b): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Alumina
pk ht
oes fnd uo/ml final vol fnd uq
H I J=1 0+C K=l*J
4 I 0.4690 0.0436 10.4580 0.4558
2 0.4580 0.0426 10.5340 0.4484
? 0.7540 0.0709 10.5240 0.7458
4 0.8147 0.0766 10.5140 0.8051
5 1.4850 0.1 566 10.5300 1.6495
6 1.8490 0.1 950 10.5580 2.0593
7 2.1 860 0 2618 10.5200 2.7541
I 1 .9510 0.2337 10.5560 2.4664
I 3.9890 0.5133 10.6780 5.4805
10 3.7780 0.4861 10.5700 5.1 381
11 8.5690 1.0861 10.5420 11.4492
12 8.1 250 1.0298 10.5390 10.8529
1? 11.8560 1.7229 10.5720 18.2147
14 '1 1.'1 150 1.6152 10.5360 17.0182
des des
uo/0.5 uq/q % des
Efnduo-D
F=E*2
Q=
(E/ads/.5)*1 00
1 12.6250 1 3.1 040 0.4580 0.0745 0.3813 0.7627 43.6521
2 12.6430 1 3.1 600 0.5340 0.0883 0.3600 0.7201 42.5720
12.6360 1 3.1 480 0.5240 0.1734 0.5724 1.1449 33.8368
4 12.9810 13.4880 0.5140 0.1696 0.6355 1.2710 37.3570
5 12.3300 12.8450 0.5300 0.2801 1.3694 2.7388 61.8179
o 12.7530 13.2820 0.5580 0.2955 1.7638 3.5275 80.0028
12.5640 13.0740 0.5200 0.3973 2.3568 4.7136 99.8940
8 12.6620 1 3.1 900 0.5560 0.3975 2.0689 4.1378 72.5859
12.3430 12.9320 0.6780 1.3129 4.1676 8.3352 73.9512
10 12.4210 12.9560 0.5700 1.1067 4.0314 8.0628 72.1939
11 12.7320 13.2530 0.5420 2.0533 9.3959 18.7919 77.5460
12 12.3780 12.8430 0.5390 2.0358 8.8171 17.6343 72.0903
13 12.8360 13.3720 0.5720 3.4089 14.8058 29.6117 96.1169
14 12.6520 13.1700 0.5360 3.1842 13.8339 27.6679 88.7194
47

3.5 Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Silica
Table 3.5: Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Silica
40
35
30
ct,
o)
ZJ
.i
q)
oU zo
!t
U,
(!
d15
(E
o
10
5
0
Fig.3.7
ok.ht
carb add
oDm add uq/O.5s fnd ppm
Equil. conc. ug/ml
fnd
uo/0.5o
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by SiO2
ads
uq/0.5q
ads
uo/o % ads
1 1.5200 0.2500 2.5000 0.1514 1.5139 0.9861 1.9721 39.4422
z 1.5300 0.2500 2.5000 0.1524 1.5239 0.9761 1.9522 39.0438
3.2500 0.5000 5.0000 0.3244 3.2435 1.7565 3.5130 35.1297
4 3.2600 0.5000 5.0000 0.3253 3.2535 1.7465 3.4930 34.9301
4.9'100 0.7500 7.5000 0.5376 5.3759 2.1241 4.2482 28.3212
o 4.9500 0.7500 7.5000 0.5420 5.4197 2.0803 4.1606 27.7372
7 6.4600 1.0000 10.0000 0.8055 8.0549 1.9451 3.8903 19.4514
8 6.4700 1.0000 10.0000 0.8067 8.0673 1.9327 3.8653 19.3267
g '15.1500 2.5000 25.0000 1.9819 19.8195 5.1 805 10.361 1 20.7221
10 15.2100 2.5000 25.0000 1.9898 19.8980 5.1020 10.2041 20.4082
11 29.1500 5.0000 50.0000 3.7200 37.2001 12.7999 25.5998 25.5998
12 29.2500 5.0000 50.0000 3.7328 37.3277 12.6723 25.3446 25.3446
13 40.7400 7.5000 75.0000 5.9538 59.5382 15.4618 30.9236 20.6157
14 41 .0100 7.5000 75.0000 5.9933 59.9328 15.0672 30.1 345 20.0896
48
ads
des
o
I

3.6 De<strong>sorption</strong> <strong>of</strong> Carbendazim by Silica
Table 3.6 (a): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Silica
emo tb tb+min+sol ent sol
Table 3.6(b): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Silica
pk ht
des
carb
ent uo
des
uo/0.5
fnd
uo/ml finalvol fnd uq
4 I 0.6780 0.0675 10.8320 0.7315
z 0.5760 0.0574 10.8760 0.6240
J 0.9950 0.0993 10.8940 1 .0818
4 0.9870 0.0985 10.9540 1.0790
6 1.1210 0.1227 10.8920 1.3369
o 1.1120 0.1218 10.8920 1.3261
7 1.7450 0.2176 10.8560 2.3621
I 1 .8910 0.2358 10.8500 2.5583
9 4.1120 0.5379 10.8940 5.8603
10 4.0120 0.5249 10.9200 5.7314
11 8.7560 1.1174 10.8680 12.1440
12 8.4320 1.0761 10.8960 11.7247
13 10.4150 1.5221 10.9160 16.6149
14 10.5690 1.5446 10.8900 16.8204
des
uq/q % des
1 12.9380 13.6040 0.8320 0.1260 0.6055 1.2110 61.4086
z 12.6330 13.3210 0 8760 0.1 335 0.4905 0.9809 50.2479
12.6970 13.3940 0.8940 0.2900 0.7918 1.5836 45.0797
4 12.6410 13.3680 0.9540 0.3104 0.7686 1.5372 44.0089
12.5900 13.2860 0.8920 0.4795 0.8573 1.7146 40.3619
o 12.8520 13.5480 0.8920 0.4834 0.8427 1.6854 40.5079
7 12.7200 13.3980 0.8560 0.6895 1.6726 3.3451 85.9869
8 12.3330 13.0080 0.8500 0.6857 1.8725 3.7451 96.8894
12.5930 13.2900 0.8940 1 .7719 4.0884 8.1 769 78.9193
10 12.5850 13.2950 0.9200 1.8306 3.9008 7.8016 76.4560
11 12.4410 13.1250 0.8680 3.2290 8.9150 17.8300 69.6491
12 12.3330 13.0310 0.8960 3.3446 8.3802 16.7604 66.1 300
13 12.6610 13.3690 0.9160 5.4537 11.1612 22.3224 72.1855
14 12.2390 12.9340 0.8900 5.3340 11.4864 22.9728 76.2342
49

3.7 Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Montmorillonite
Table 3.7: Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Montmorillonite
ok.ht carb add ppm add uq/O.5q fnd oom fnd uq/O.5q ads uq/O.5q ads uq/q % ads
1 2.2150 0.2500 2.5000 0.1 303 1.3029 1.1971 2.3941 47.8824
z 2.2060 0.2500 2.5000 0.1298 1.2976 1.2024 2.4047 48.0941
J 2.3050 0.5000 5.0000 0.1 668 1.6679 3.3321 6.6643 66.6425
4 2.3050 0.5000 5.0000 0.1668 1.6679 3.3321 6.6643 66.6425
5 2.3420 0.7500 7.5000 0.2079 2.0787 5.4213 10.8426 72.2840
2.3420 0.7500 7.5000 0.2079 2.0787 5.4213 10.8426 72.2840
7 2.3700 1.0000 10.0000 0.2292 2.2921 7.7079 15.4159 77.0793
o 2.3700 1.0000 10.0000 0.2292 2.2921 7.7079 15.4159 77.0793
2.4900 2.5000 25.0000 0.3009 3.0087 21.9913 43.9826 87.9652
10 2.4660 2.5000 25.0000 0.2980 2.9797 22.0203 44.0406 88.0812
11 2.7810 5.0000 50.0000 0.3487 3.4867 46.5133 93.0266 93.0266
12 2.7840 5.0000 50.0000 0.3490 3.4905 46.5095 93.0191 93.0191
13 2.8860 7.5000 75.0000 0.3923 3.9233 71.0767 142.1533 94.7689
14 2.6550 7.5000 75.0000 0.3609 3.6093 71.3907 142.7814 95.1 876
o
ct)
o
E o
di
tr
o
160
140
120
100
80
60
40
20
0
46
Equil. conc.ug/ml
Fig.3.8 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by Montmorillonite
s0
ads
des
o I

3.8 De<strong>sorption</strong> <strong>of</strong> Carbendazim by Montmorillonite
Table 3.8 (a): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Montmorillonite
emp tb tb+min+sol ent sol
carb ent
uq
des
uq/0.5
des
uo/o % des
1 12.8130 13.0690 0.0120 0.0016 0.2757 0.55'13 46.0581
z 12.9730 13.2300 0.0140 0.0018 0.3287 0.6574 54.6728
? 12.9720 13.2250 0.0060 0.0010 0.8182 1.6364 49.1093
4 12.9230 13.2190 0.0920 0.0153 0.7370 1.4740 44.2345
5 12.9400 13.2120 0.0440 0.0091 1 .1816 2.3633 43.5920
12.9260 13.2180 0.0840 0.0175 1.2870 2.5740 47.4792
7 12.9620 13.3140 0.2040 0.0468 1.4528 2.9057 37.6972
8 12.6820 12.9890 0.1140 0.0261 1.5961 3.1922 41.4139
a 12.8920 13.2170 0.1 500 0.0451 3.6568 7.3136 33.2569
10 12.6320 12.9620 0.1600 0.0477 3.8540 7.7080 35.0040
11 12.9190 13.2150 0.0920 0.0321 5.2083 10.4165 22.3948
12 12.7010 13.0120 0.1220 0.0426 5.1206 10.2412 22.0195
13 12.9450 13.2140 0.0380 0.0149 5.9072 11.8144 16.6221
14 13.5160 13.8150 0.0980 0.0354 5.7704 11.5409 1 6.1 658
Table 3.8 (b): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Montmorillonite
pk ht
des
fnd
uo/ml finalvol fnd uo
1 0.4700 0.0276 10.0276 0.2772
2 0.5600 0.0329 10.0329 0.3305
3 1.1230 0.0813 10.0813 0.8192
4 1.0320 0.0747 10.0747 0.7523
6 1.3260 0.1177 10.1177 I .1 908
6 1.4510 0.1288 1 0.1 288 1.3045
7 1.5280 0.1478 10.1478 1.4996
B 1.6510 0.1 597 1 0.1 597 1.6222
o 2.9580 0.3574 10.3574 3.7019
10 3.1120 0.3760 '10.3760 3.9017
11 3.9810 0.4991 10.4991 5.2403
12 3.9250 0.4921 10.4921 5.1632
13 4.1250 0.5608 10.5608 5.9221
14 4.0480 0.5503 10.5503 5.8058
51

3.9 Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Muscovite
Table 3.9: Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Muscovite
80
70
60
E)
o)
?so
o(l,
E
o{ ao
at
!, (E
o""
t""
o 20
10
0
pk.ht
carb add
oom
add
uo/0.5q fnd opm
Equil. conc. ug/ml
fnd
uo/0.5o
ads
uo/0.5o
Fig. 3.9 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by muscovite
ads
uo/o
2.0500 0.2500 2.5000 0.1412 1.4118 1.0882 4.3526
2 2.0500 0.2500 2.5000 0.1412 1.4118 1.0882 4.3526
3 5.9500 0.5000 5.0000 0.4685 4.6850 0.3150 1.2598
4 5.9800 0.5000 5.0000 0.4709 4.7087 0.2913 1.1654
6.7700 0.7500 7.5000 0.6501 6.5013 0.9987 3.9949
o 6.8100 0.7500 7.5000 0.6540 6.5397 0.9603 3.8412
7.9200 1.0000 10.0000 0.8131 8.1314 1.8686 7.4743
I 7.9400 1.0000 10.0000 0.8152 8.1520 1.8480 7.3922
I 16.5600 2.5000 25.0000 2.0690 20.6897 4.3103 17.2414
10 16.6500 2.5000 25.0000 2.0802 20.8021 4.1979 16.7916
11 33.1 500 5.0000 50.0000 4.2229 42.2293 7.7707 31.0828
12 33.1 900 5.0000 50.0000 4.2280 42.2803 7.7197 30.8790
13 46.9500 7.5000 75.0000 6.3883 63.8833 11.1167 44.4666
14 46.9100 7.5000 75.0000 6.3829 63.8289 11.1711 44.6843
52
ads
des
o T

3.10 De<strong>sorption</strong> <strong>of</strong> Carbendazim by Muscovite
Table 3.10(a): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Muscovite
emp tb tb+min+sol ent sol
carb ent
Table 3.10(b): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Muscovite
UO
des
uo/0.5
pk ht fnd
des uo/ml finalvol fnd uq
0.4400 0.0303 10.0303 0.3039
2 0.4500 0.0310 10.0310 0.3109
3 0.6900 0.0543 10.0543 0.5463
4 0.6800 0.0535 10.0535 0.5383
1.3500 0.1296 10.1296 1.3132
o '1.2500 0.1200 1 0.1 200 1.2148
7 1.8500 0.1 899 1 0.1 899 1.9355
8 1.8900 0.1 940 1 0.1 940 1.9781
q
3.9900 0.4985 10.4985 5.2335
10 4.0100 0.5010 10.5010 5.2610
11 6.8900 0.8777 10.8777 9.5474
12 6.9100 0.8803 10.8803 9.5774
'13 9.1 900 1.2505 11.2505 14.0682
14 9.1 900 1.2505 11.2505 14.0682
des
uq/q % des
I 12.3230 12.8710 0.5960 0.0841 0.2198 0.4396 20.'1996
2 12.3690 12.9560 0.6740 0.0952 0.2157 0.4314 19.8243
e 12.4470 12.9940 0.5940 0.2783 0.2680 0.5359 85.0797
4 12.3480 12.8750 0.5540 0.2609 0.2774 0.5549 95.2294
12.2990 12.7970 0.4960 0.3225 0.9908 1.9815 99.2028
o 12.2520 12.7290 0.4540 0.2969 0.9179 1.8358 95.5831
12.3730 12.9100 0.5740 0.4667 1.4687 2.9374 78.6006
8 12.3790 12.9340 0.6100 0.4973 1.4808 2.9617 80.1297
o 12.3870 12.8910 0.5080 1.0510 4.1825 8.3650 97.0334
10 12.3730 12.8950 0.5440 1.1316 4.1294 8.2587 98.3673
11 12.3300 12.9190 0.6780 2.8631 6.6843 13.3686 86.0192
12 12.3730 12.8780 0.5100 2.1563 7.4211 14.8422 96.1 31 5
13 '12.3330 12.9290 0.6920 4.4207 9.6474 19.2949 86.7837
14 12.1130 12.6600 0.5940 3.7914 10.2767 20.5535 91.9941
53

3.11 Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil I
Table 3.11: Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil I
ok.ht carb add ppm add uq/O.5q fnd ppm fnd uq/O.5q ads uq/0.5q ads uq/q % ads
1 1.1200 0.2500 2.5000 0.2240 2.2400 0.2600 0.5200 10.4000
z 1 .1 100 0.2500 2.5000 0.2220 2.2200 0.2800 0.5600 11.2000
3.9500 0.5000 5.0000 0.4247 4.2473 0.7527 1.5054 15.0538
4 3.9900 0.5000 5.0000 0.4290 4.2903 0.7097 1.4194 14.1935
5.1200 0.7500 7.5000 0.6667 6.6667 0.8333 1.6667 11.1111
o 5.1 1 00 0.7500 7.5000 0.6654 o.ocJo 0.8464 1.6927 11.2847
6.0100 1.0000 10.0000 0.8735 8.7355 1.2645 2.5291 12.6453
6.0500 1.0000 10.0000 0.8794 8.7936 1.2064 2.4128 12.0640
o 15.8900 2.5000 25.0000 2.0393 20.3927 4.6073 9.2146 18.4292
'10 15.9200 2.5000 25.0000 2.0431 20.4312 4.5688 9.1 376 18.2752
11 28.7900 5.0000 50.0000 3.9886 39.8864 10.1 136 20.2272 20.2272
12 28.8700 5.0000 50.0000 3.9997 39.9972 10.0028 20.0055 20.0055
13 40.4500 7.5000 75.0000 5.8397 58.3975 16.6025 33.2050 22.1367
14 40.4200 7.5000 75.0000 5.8354 58.3542 16.6458 33.2916 22.1944
ED
Et
o
od
tt
(!
ai
tr
o
40
30
25
20
15
10
5
0
Fig.3.10
ADSORPTION & DESORPTION OF CARBENDAZIM BY SOIL 1
Equil. conc. ug/ml
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by soil 1
54
ads
des
o I

3.12 De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil I
Table 3.12(a):De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil I
emp tb tb+soil+sol ent sol
carb
ent uq des uq/O.5 des uo/o % des
1 12.3230 12.7510 0.3560 0.0797 0.1 1 83 0.2365 90.9655
z 12.3690 12.8010 0.3640 0.0808 0.1174 0.2349 B3.B7B3
? 12.4470 12.8810 0.3680 0.1 563 0.1 263 0.2527 33.5717
4 12.3480 12.8110 0.4260 0.1 828 0.1 397 0.2795 39.3788
5 12.4960 12.9890 0.4860 0.3240 0.2211 0.4421 53.0524
o 12.2520 12.7450 0.4860 0.3234 0.2247 0.4494 53.0982
7 12.3730 12.8710 0.4960 0.4333 0.4750 0.9500 75.1242
8 12.3790 12.8790 0.5000 0.4397 0.4525 0.9050 75.0178
a 12.3870 12.9120 0.5500 1.1216 1 .1 685 2.3371 50.7257
10 12.2730 12.7980 0.5500 1.1237 1.1 606 2.3213 50.8073
11 12.3300 12.8950 0.6300 2.5128 1.4694 2.9388 29.0578
12 12.3730 12.9240 0.6020 2.4078 1.6543 3.3086 33.0771
13 12.3330 12.9890 0.8120 4.7419 3.9627 7.9253 47.7359
14 12.1130 12.7840 0.8420 4.9134 3.9452 7.8904 47.4020
Table 3.12(b): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil I
pk ht
des
fnd
uq/ml finalvol fnd uo
1 0.0980 0.0196 10.1020 0.1 980
z 0.0990 0.0198 10.0120 0.1 982
J 0.2560 0.0275 10.2680 0.2826
4 0.2890 0.0311 10.3780 0.3225
5 0.4157 0.0541 10.0700 0.5451
6 0.4125 0.0537 10.2040 0.5481
7 0.6215 0.0903 10.0540 0.9083
B 0.61 15 0.0889 10.0380 0.8922
9 1.7258 0.2215 10.3400 2.2901
10 1.7325 0.2223 10.2740 2.2844
11 2.7950 0.3872 10.2840 3.9822
12 2.8950 0.4011 1 0.1 280 4.0621
IJ 5.8800 0.8489 10.2540 8.7046
14 5.8640 0.8466 10.4640 8.8586
55

3.13 Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil2
Table 3.13: Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 2
40
('r 30
(tt
CD
E' zc
oq,
€ o!t

3.14 De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 2
Table 3.14(a):De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soit 2
emp tb tb+soil+sol ent sol
carb ent
uo
des
uo/.5
Table 3.14@): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 2
pk ht fnd
des uq/ml finalvol fnd uo
I
I 0.2173 0.0183 10.1020 0.1 848
2 0.2276 0.0192 10.0120 0.1 91 B
J 0.3565 0.0312 10.2680 0.3200
4 0 3586 0.0313 10.3780 0.3253
5 0.5247 0.0572 10.0700 0.5760
o 0.5544 0.0604 10.2040 0.6166
I 0.7658 0.0860 10.0540 0.8642
8 0.7590 0.0852 10.0380 0.8551
9 1.1700 0.1 504 10.3400 1.5550
10 1 .1 500 0.1478 10.2740 1.5187
11 2.6800 0.3674 10.2840 3.7786
12 2.6400 0.3619 1 0.1 280 3.6657
13 4.3988 0.6438 10.2540 6.6020
14 4.4126 0.6459 10.4640 6.7583
des
uq/q % des
1 12.8130 13.1140 0.1 020 0.0167 0.1680 0.3360 9.7847
z 12.9730 13.2900 0.1 340 0.0215 0.1702 0.3405 9.5400
J 12.9720 13.3200 0.1960 0.0848 0.2352 0.4703 17.4698
4 12.9230 13.2800 0.2140 0.0930 0.2323 0.4646 17.7170
5 12.9410 13.3200 0.2580 0.1 730 0.4030 0.8060 25.3207
o 12.9260 13.3100 0.2680 0.1 768 0.4399 0.8798 24.3090
7 12.9620 13.4200 0.4160 0.3740 0.4902 0.9804 24.2644
8 12.6820 1 3.1 600 0.4560 0.4089 0.4462 0.8923 21.6054
I 12.8920 13.3900 0.4960 1.0844 0.4705 0.9411 7.5017
10 12.6320 13.1200 0.4760 1.0432 0.4755 0.9510 7.7069
11 12.9190 13.4200 0.5020 2.1755 1.6031 3.2062 12.0297
12 12.7010 13.2200 0.5380 2.3293 1.3364 2.6728 9.9672
13 12.9450 13.5100 0.6300 3.9762 2.6258 5.2515 11.0463
14 12.5160 13.1 100 0.6880 4.3453 2.4130 4.8261 10.1890
57

3.15 Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 3
Table 3.15: Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 3
o)
ct
40
35
30
o
!t
oU ^^
o
t, (!
ci rs
t
o '10
5
0
0
Fig.3.12
carb add
ppm
add
uo/0.5q fnd ppm
246
Equil. conc. ug/ml
fnd
uo/0.5q
ads
uo/0.5o
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by soil 3
ads
uo/o % ads
1 0.2500 2.5000 0.1498 1.4983 1 .0017 2.0034 40.0685
z 0.2500 2.5000 0.1464 1.4640 1.0360 2.0719 41.4384
0.5000 5.0000 0.2749 2.7487 2.2513 4.5026 45.0262
4 0.5000 5.0000 0.2818 2.8185 2.1815 4.3630 43.6300
5 0.7500 7.5000 0.4325 4.3248 3.1752 6.3504 42.3358
o 0.7500 7.5000 0.4358 4.3577 3.1423 6.2847 41.8978
1.0000 10.0000 0.5761 5.7606 4.2394 8.4787 42.3937
B 1.0000 10.0000 0.5794 5.7942 4.2058 8.4116 42.0582
2.5000 25.0000 1.8045 18.0448 6.9552 13.9104 27.8207
10 2.5000 25.0000 1.8096 18.0963 6.9037 13.8073 27.6146
11 5.0000 50.0000 3.9487 39.4874 10.5126 21.0252 21.0252
12 5.0000 50.0000 3.9474 39.4737 10.5263 21.0526 21.0526
13 7.5000 75.0000 5.8324 58.3236 16.6764 33.3527 22.2351
14 7.5000 75.0000 5.8614 58.6142 16.3858 32.7716 21.8478
58
ads
des
o I

3.16 De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 3
Table 3.16(a): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 3
emo tb tb+soil+sol ent sol
carb ent
UO
des
uo/O.5
des
uo/o % des
1 12.6250 13.0100 0.2700 0.0405 0.0509 0.1 01 8 33.9814
2 12.6430 13.0480 0.3100 0.0454 0.0423 0.0847 28.9256
J 12.6360 13.0680 0.3640 0.1 001 0.1 1 01 0.2202 40.0591
4 12.9810 13.4150 0.3680 0.1 037 0.1187 0.2374 42.1210
5 12.3300 12.7650 0.3700 0.1 600 0.2983 0.5966 68.9721
o 12.7530 13.1910 0.3760 0.1 638 0.3117 0.6235 71.5392
12.5640 '13.0150 0.4020 0.2316 0.5064 1.0128 87.9055
8 12.6620 13.1200 0.4160 0.2410 0.4802 0.9604 82.8790
o 12.4340 12.8980 0.4280 0.7723 0.8438 1.6876 46.7617
'10 12.4210 12.8900 0.4380 0.7926 0.8430 1.6859 46.5820
11 12.7320 13.2150 0.4660 1.8401 1.1043 2.2085 27.9652
12 12.3180 12.7990 0.4620 1.8237 1.2179 2.4358 30.8530
13 12.8360 13.3660 0.5600 3.2661 1.5844 3.1 688 27.1659
14 12.6520 1 3.1 990 0.5940 3.4817 1.4012 2.8023 23.9049
Table 3.16(b): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil3
pk ht
des
fnd
uo/ml finalvol fnd uo
1 0.1 056 0.0090 10.1020 0.0914
z 0j024 0.0088 10.0120 0.0877
3 0.2346 0.0205 10.2680 0.2102
4 0.2456 0.0214 10.3780 0.2224
0.4157 0.0455 10.0700 0.4583
o 0.4257 0.0466 10.2040 0.4756
7 0.6562 0.0734 10.0540 0.7380
8 0.6424 0.0719 10.0380 0.7213
o 1.2135 0.1 563 10.3400 1.6161
10 1.2360 0.1 592 10.2740 1.6356
11 2.0889 0.2863 10.2840 2.9444
12 2.1911 0.3003 10.'1280 3.0416
13 3.2564 0.4730 10.2540 4.8505
14 3.2123 0.4666 10.4640 4.8828
59

3.17 Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 4
Table 3.17: Ad<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 4
50
45
40
935
ct,
ui go
(,
E
€zs
o
!t o
d20
u,
(J 1s
'10
5
0
pk.ht
carb add
DDM
add
uq/0.5q fnd ppm
fnd
uq/0.5q
ads
uq/0.5q
ads
uo/o % ads
1 2.1400 0.2500 2.5000 0.'1832 1.8322 0.6678 1.3356 26.7123
2 2j300 0.2500 2.5000 0.1824 1.8236 0.6764 1.3527 27.0548
J 3.9500 0.5000 5.0000 0.3447 3.4468 1.5532 3.1 065 31.0646
4 3.9900 0.5000 5.0000 0.3482 3.4817 1.5183 3.0366 30.3665
5 4.5100 0.7500 7.5000 0.4938 4.9380 2.5620 5.1241 34.1606
b 4.5900 0.7500 7.5000 0.5026 5.0255 2.4745 4.9489 32.9927
5.6600 1.0000 10.0000 0.6331 6.3311 3.6689 7.3378 36.6890
R 5.6800 1.0000 10.0000 0.6353 6.3535 3.6465 7.2931 36.4653
12.5500 2.5000 25.0000 1.6164 1 6.1 643 8.8357 17.6713 35.3426
10 12.4500 2.5000 25.0000 1.6036 16.0355 8.9645 17.9289 35.8578
11 24.3100 5.0000 50.0000 3.3320 33.3196 16.6804 33.3607 33.3607
12 24.2500 5.0000 50.0000 3.3237 33.2374 16.7626 33.5252 33.5252
13 32.2600 7.5000 75.0000 4.6862 46.8623 28.1377 56.2754 37.5169
14 32.2800 7.5000 75.0000 4.6891 46.8913 28.1087 56.2173 37.4782
0
Fig.3.13
Equil. conc. ug/ml
ads
des
Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> carbendazim by soil 4
o T

3.18 De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soit 4
Table 3.18(a):De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 4
emo tb tb+soil+sol ent sol
carb ent
UO
des
uo/0.5
des
uo/q % des
1 12.9380 13.3970 0.4180 0.0766 0.1 099 0.2198 59.9753
z 12.6330 13.0950 0.4240 0.0773 0.1 065 0.2129 58.3781
? 12.6970 13.2100 0.5260 0.1 81 3 0.1 865 0.3730 54.1118
4 12.6410 1 3.1 560 0.5300 0.1 845 0.1791 0.3582 51.4459
5 12.5900 13.1190 0.5580 0.2755 0.4020 0.8040 81.4065
o 12.8520 13.3790 0.5540 0.2784 0.4059 0.81 18 80.7645
7 12.7200 13.2897 0.6394 0.4048 0.5799 1 .1 598 91.5950
R 12.3300 12.8900 0.6200 0.3939 0.6139 1.2278 96.6216
12.9530 13.5550 0.7040 '1 .1380 1.4084 2.8168 87.1 305
10 12.5850 13.1810 0.6920 1.1097 1.4721 2.9441 91.8006
11 12.4410 1 3.1 000 0.8180 2.7255 2.4404 4.8808 73.2426
12 12.3330 12.9870 0.8080 2.6856 2.2618 4.5236 68.0503
13 12.6610 13.3560 0.8900 4.1707 3.9299 7.8599 83.8613
14 12.2390 12.9390 0.9000 4.2202 3.7719 7.5439 80.4397
Table 3.18(b): De<strong>sorption</strong> <strong>of</strong> Carbendazim by Soil 4
pk ht
des
fnd
uo/ml finalvol fnd uo
1 0.2156 0.0185 1 0.1 020 0.1 865
z 0.2144 0.0184 10.0120 0.1 838
J 0.4105 0.0358 10.2680 0.3678
4 0.4016 0.0350 10.3780 0.3636
0.6145 0.0673 10.0700 0.6775
o 0.6125 0.067'1 10.2040 0.6843
7 0.8756 0.0979 10.0540 0.9847
8 0.8976 0.1004 10.0380 1.0078
I 1.9120 0.2463 10.3400 2.5464
10 1.9510 0.2513 10.2740 2.5817
11 3.6650 0.5023 10.2840 5.1 660
12 3.5640 0.4885 1 0.1 280 4.9474
13 5.4384 0.7900 10.2540 8.1 007
14 5.2578 0.7638 10.4640 7.9921
6l

3.19 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Alumina
Table 3.19: Ad<strong>sorption</strong> <strong>of</strong> FBNZ by AlzOs
pk.ht fbnz add ppm add uq/O.5q fnd ppm fnd uo/0.5q ads uq/O.5q ads uq/q % ads
1 3.1187 0.2500 2.5000 0.1306 1.3063 1.1937 2.3873 47.7463
z 2.9628 0.2500 2.5000 0.1241 1.2410 1.2590 2.5179 50.3581
2 5.5462 0.5000 5.0000 0.2876 2.8760 2.1240 4.2480 42.4803
4 5.6000 0.5000 5.0000 0.2904 2.9039 2.0961 4.1922 41.9216
7.8960 0.7500 7.5000 0.4675 4.6746 2.8254 5.6508 37.6723
h 7.8114 0.7500 7.5000 0.4624 4.6245 2.8755 5.7511 38.3404
'13.1078 1.0000 10.0000 0.7856 7.8559 2.1441 4.2882 21.4411
R 12.9847 1.0000 10.0000 0.7782 7.7821 2.2179 4.4357 22.1786
Y 33.4537 2.5000 25.0000 1.9960 19.9597 5.0403 10.0805 20.1611
10 33.3034 2.5000 25.0000 1.9870 19.8700 5.1 300 10.2599 20.5199
11 68.0393 5.0000 50.0000 4.3255 43.2554 6.7446 13.4891 13.4891
12 68.1 1 03 5.0000 50.0000 4.3301 43.3006 6.6994 13.3988 13.3988
13 119.1677 10.0000 100.0000 8.0223 80.2232 19.7768 39.5537 19.7768
14 120.1456 10.0000 100.0000 B.OBB1 80.8815 19.1185 38.2370 19.1 185
45
40
35
ctt
cD 30
q
o^-
od
o^^
Ezu
(U
N
F15
r
ll.
10
5
0
Equi. conc. ug/ml
Fig.3.14 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by Al2O3
62
ads
des
o
I

3.20 De<strong>sorption</strong> <strong>of</strong> FBNZ bY Alumina
Table 3.20 (a): De<strong>sorption</strong> <strong>of</strong> FBNZ by Al2O3
emp tb tb+min+sol ent sol
fbnz
ent uo
des
uq/0.5
des
uo/o % des
1 12.4020 12.7840 0.2640 0.0345 0.1 968 0.3935 16.4842
z 12.4200 12.7870 0.2340 0.0290 0.2027 0.4054 16.1015
12.2820 12.7810 0.4980 0.1432 0.4211 0.8421 19.8241
4 12.2620 12.7530 0.4820 0.1400 0.4304 0.8607 20.5321
12.3820 12.8870 0.5100 0.2384 1.0277 2.0555 36.3742
o 12.2740 12.7720 0.4960 0.2294 1.0536 2.1072 36.6407
7 12.3650 12.8810 0.5320 0.4179 1.4568 2.9135 67.9428
B 12.3430 12.8590 0.5320 0.4140 1.4637 2.9273 65.9947
o 12.3780 12.9160 0.5760 1.1497 2.7702 5.5405 54.9623
10 12.3740 12.9090 0.5700 1.1326 2.6224 5.2449 51.1198
11 12.3560 12.9070 0.6020 2.6040 4.1033 8.2065 60.8382
12 12.1300 12.6810 0.6020 2.6067 3.9100 7.8200 58.3638
13 12.2720 12.8520 0.6600 5.2947 9.9112 19.8225 50.1153
14 12.3090 12.8850 0.6520 5.2735 10.4699 20.9399 54.7634
Table 3.20 (b): De<strong>sorption</strong> <strong>of</strong> FBNZ by AlzOr
pk ht
des
fnd
uo/ml finalvol fnd uq
1 0.5465 0.0229 1 0.1 020 0.2313
2 0.5526 0.0231 10.0120 0.23'18
? 1.0598 0.0550 10.2680 0.5643
4 1.0598 0.0550 10.3780 0.5703
5 2.1238 0.1257 10.0700 1.2661
2.1238 0.1257 10.2040 1.2830
7 3.1112 0.1 865 10.0540 1.8747
B 3.1211 0.1871 10.0380 1.8777
I 6.3540 0.3791 10.3400 3.9199
10 6.1 258 0.3655 10.2740 3.7550
11 10.2589 0.6522 10.2840 6.7072
12 10.1210 0.6434 1 0.1 280 6.5167
13 22.0282 1.4829 10.2540 15.2060
14 22.3491 1.5045 10.4640 15.7434
63

3.21 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Silica
Table 3.21: Ad<strong>sorption</strong> <strong>of</strong> FBNZ by SiO2
ok.ht fbnz add oom add uq/0.5q fnd ppm fnd uq/O.5q ads uq/0.5q ads uq/q % ads
1 3.0858 0.2500 2.5000 0.1 593 1.5932 0.9068 1.8135 36.2701
z 2.9896 0.2500 2.5000 0.1544 1.5436 0.9564 1.9128 38.2569
2 4.4549 0.5000 5.0000 0.2402 2.4016 2.5984 5.1 969 51.9687
4 4.2398 0.5000 5.0000 0.2286 2.2856 2.7144 5.4288 54.2879
6.4186 0.7500 7.5000 0.4114 4.1138 3.3862 6.7724 45.1495
6.3696 0.7500 7.5000 0.4082 4.0824 3.4176 6.8352 45.5683
11.7389 1.0000 10.0000 0.7117 7.1169 2.8831 5.7662 28.8310
12.0442 1.0000 10.0000 0.7302 7.3020 2.6980 5.3960 26.9801
30.7526 2.5000 25.0000 1.8206 18.2064 6.7936 13.5873 27.1745
10 30.2296 2.5000 25.0000 1.7897 17.8967 7.1 033 14.2065 28.4130
11 56.3588 5.0000 50.0000 3.6217 36.2173 13.7827 27.5653 27.5653
12 56.2401 5.0000 50.0000 3.6141 36.1 41 0 13.8590 27.7180 27.7180
13 108.3579 10.0000 100.0000 7.5992 75.9922 24.0078 48.0157 24.0078
14 103.6174 10.0000 100.0000 7.2668 72.6676 27.3324 54.6648 27.3324
ADSORPTTON & DESORPTTON OF FBNZ By SiO2
4
Equil. conc. ug/ml
ads
des
Fig.3.15 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by SiO2
o I

3.22 De<strong>sorption</strong> <strong>of</strong> FBNZ by Silica
Table 3.22 (a\z De<strong>sorption</strong> <strong>of</strong> FBNZ by SiOz
emo tb tb+min+sol ent sol
Table 3.22(b): De<strong>sorption</strong> <strong>of</strong> FBNZ by SiO2
pk ht
des
Fbnz
ent uo
fnd
uq/ml finalvol fnd uq
1 0.9910 0.0512 10.1020 0.5169
2 0.9689 0.0500 10.0120 0.5009
J 1.9983 0.1077 10.2680 1.1061
4 1.8898 0.1 01 9 10.3780 1.0573
5 3.1203 0.2000 10.0700 2.0138
o 3.0580 0.1 960 10.2040 1.9999
7 4.9156 0.2980 10.0540 2.9963
B
I
4.8888
6.7777
0.2964
0.4013
10.0380
10.3400
2.9752
4.1490
10 6.9975 0.4143 10.2740 4.2562
11 12.4518 0.8002 10.2840 8.2290
12 12.4125 0.7977 10.1280 8.0786
13 20.3568 1.4276 10.2540 14.6390
14 19.7799 1.3872 10.4640 14.5154
des
uq/O.5 des uq/q % des
1 12.3300 12.9980 0.8360 0.1332 0.3837 0.7674 16.4842
z 12.4020 13.0790 0.8540 0.1 31 8 0.3690 0.7381 16.1015
2 12.4810 1 3.1 650 0.8680 0.2085 0.8977 1.7953 19.8241
4 12.2820 12.9750 0.8860 0.2025 0.8548 1.7095 20.5321
5 12.2930 '13.0210 0.9560 0.3933 1.6206 3.2411 36.3742
o 12.3280 13.0560 0.9560 0.3903 1.6096 3.2193 36.6407
12.3940 13.07'10 0.8540 0.6078 2.3885 4.7769 67.9428
I 12.3650 13.0420 0.8540 0.6236 2.3516 4.7032 65.9947
o 12.2480 12.8990 0.8020 1.4602 2.6889 5.3777 54.9623
'10 12.3780 13.0950 0.9340 1.6716 2.5847 5.1 693 51.1 1 98
11 12.3870 13.0570 0.8400 3.0423 5.1 868 10.3736 60.8382
12 12.3560 13.0410 0.8700 3.1443 4.9344 9.8687 58.3638
4't 12.2560 12.9490 0.8860 6.7329 7.9061 15.8122 50.1 1 53
14 12.272 12.952 0.86 6.249415 8.266019 16.53204 54.7634
65

3.23 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Montmorillonite
Table 3.23: Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Montmorillonite
200
150
ot
ED
o
06
nnn
ot vv
tt (E
N
z
o
lI-
ok.ht
50
FBNZ
add
DDM
add
uo/0.5o fnd oom
2
fnd
uo/0.5o
aquit. cJrc. r.rglmt
ads
uo/0.5o ads uq/q % ads
I 1.0015 0.2500 2.5000 0.0578 0.5782 1.9218 3.8437 76.8732
z 1.0130 0.2500 2.5000 0.0585 0.5848 1.9152 3.8303 76.6067
1.0426 0.5000 5.0000 0.0687 0.6870 4.3130 8.6259 86.2594
4 1.0385 0.5000 5.0000 0.0684 0.6844 4.3156 8.6312 86.31 17
1.1428 0.7500 7.5000 0.0863 0.8631 6.6369 13.2738 88.4920
1.1528 0.7500 7.5000 0.0871 0.8707 6.6293 13.2587 88.3913
1.2901 1.0000 10.0000 0.1 026 1.0258 8.9742 17.9485 89.7423
8 1.2837 1.0000 10.0000 0.1 026 1.0256 8.9744 17.9489 89.7443
1.3456 2.5000 25.0000 0.1226 1.2261 23.7739 47.5477 95.0955
10 1.3848 2.5000 25.0000 0.1262 1.2618 23.7382 47.4763 94.9526
11 2.1230 5.0000 50.0000 0.1671 1.6715 48.3285 96.6571 96.6571
12 2.3820 5.0000 50.0000 0.1 875 1.8754 48.1246 96.2493 96.2493
13 3.45'10 10.0000 100.0000 0.353'1 3.5310 96.4690 192.9379 96.4690
14 3.5490 10.0000 100.0000 0.3631 3.6313 96.3687 192.7374 96.3687
ads
des
Fig.3.16 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by montmorillonite
66
o I
6

3.24 De<strong>sorption</strong> <strong>of</strong> FBNZ by Montmorillonite
Table 3.24 (a)z De<strong>sorption</strong> <strong>of</strong> FBNZ by Montmorillonite
Table 3.24 @\:
emp tb tb+min+sol ent sol
FBNZ
ent uq
des
uo/0.5
De<strong>sorption</strong> <strong>of</strong> FBNZ by Montmorillonite
des
uo/o % des
4 12.3290 12.6740 0.1 900 0.01 10 0.0080 0.0159 13.7837
2 12.3980 12.7350 0.1740 0.0102 0.0088 0.0177 15.1168
J 12"4470 12.8440 0.2940 0.0202 0.0347 0.0694 50.4922
4 12.3480 12.7450 0.2940 0.0201 0.0356 0.0713 52.0651
12.3740 12.8450 0.4420 0.0381 0.0381 0.0761 44.0931
o 12.2520 12.7250 0.4460 0.0388 0.0387 0.0774 44.4460
12.3730 12.8560 0.4660 0.0478 0.0667 0.1 333 64.9975
8 12.3740 12.8650 0.4820 0.0494 0.0673 0.1 345 65.5749
12.3870 12.8870 0.5000 0.0613 0.0999 0.1 998 81.4784
10 12.2730 12.8190 0.5920 0.0747 0.0856 0.1711 67.8154
11 12.3300 12.8710 0.5820 0.0973 0.1498 0.2995 B9.5931
12 12.3770 12.9150 0.5760 0.1 080 0.1408 0.2815 75.0589
13 12.3330 12.9980 0.8300 0.2931 0.1707 0.3413 48.3320
14 1 2.1 630 12.8120 0.7980 0.2898 0.1 858 0.3716 51.1695
pk ht
des
fnd
uq/ml finalvol fnd uq
1 0.0325 0.0019 1 0.1 020 0.0190
z 0.0329 0.0019 10.0120 0.0190
? 0.0811 0.0053 10.2680 0.0549
4 0.0815 0.0054 10.3780 0.0558
0.1 002 0.0076 10.0700 0.0762
o 0.1 006 0.0076 10.2040 0.0775
7 0.1432 0.0114 10.0540 0.1145
8 0.1455 0.0116 10.0380 0.1167
q
0.1711 0.0156 10.3400 0.1612
10 0.1712 0.0156 10.2740 0.1603
11 0.3051 0.0240 10.2840 0.2470
12 0.3120 0.0246 10.1280 0.2488
13 0.4420 0.04s2 10.2540 0.4637
14 0.4442 0.0455 10.4640 0.4756
67

o.s i
i
v5i
o.7 I
06.i l
ORL
;
04:i
03i l
Ot,i
0.1 i
1.._.
o.o'
0.9
o.8
o.7
0.6
0.5
o.4
o.3
o.2
o.1
o.o
0.9
0.8
o.7
0.6
0.5
o.4
0.3
o.2
o.1
oo
'lnl 350
Fig. 3.17. Ad<strong>sorption</strong> spectra <strong>of</strong> FBNZ by Muscovite (Ad<strong>sorption</strong> blank)
l'{ -
:i ""'':. ' .: :. .,.1
' r i
-.'---f --T--1 nr
%o 300 350
Fig. 3.18. Ad<strong>sorption</strong> spectra <strong>of</strong> FBNZ by Muscovite (Ad<strong>sorption</strong> a)
lil
' I , lr :i:' i:i r:lr::r i I :i::1 :,
60 30
i....,.,,
:-
: . :.
' i i I l'-'-
%o 3m 350
j r 'l- - nr
Fig. 3.19. Ad<strong>sorption</strong> spectra <strong>of</strong> FBNZ by Muscovite (Ad<strong>sorption</strong> b)
68

:
o.45 i
0.4o l
O.35 I
l
0.3o I
:
0.25 I
o.2o l
0.15 I
o.10 ,j
:
lL\
o.o5 :'t,,,.
o.@:\ i
o.lb
0.20
036
o.o
l
06l
oni
o1s i
o,10 :
l)'
o* 1,',t,,.
o.@ |
250
r
I
300
r- -r- I
..,*]
Fig. 3.17. Ad<strong>sorption</strong> spectra <strong>of</strong> FBNZ by Muscovite (de<strong>sorption</strong> a)
'-''' ,.. : I : .-
I r I'l I -r "-''.--r'-l
-
:z5J_s@
Fig. 3.21. Ad<strong>sorption</strong> spectra <strong>of</strong> FBNZ by Muscovite (de<strong>sorption</strong> b)
350
n
69
nr

3.25 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Muscovite
Table 3.25: Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Muscovite
80
70
60
50
E)
$o
a
a80
E
IU
o
EI
,90
T\
z.
fiIn
lL"
ok.ht
FBNZ
add
DOm
add
uq/0.5q fnd ppm
fnd
uq/0.5q
ads
uo/0.5o
ads
uo/o % ads
I I 1.8868 0.2500 2.5000 0.1 089 1.0893 1.4107 2.8214 56.4280
z 2.6381 0.2500 2.5000 0.1523 1.5230 0.9770 1.9539 39.0781
2.6815 0.5000 5.0000 0.1767 1.7670 3.2330 6.4659 64.6594
4 2.6492 0.5000 5.0000 0.1746 1.7459 3.2541 6.5081 65.0811
5 4.1 006 0.7500 7.5000 0.3097 3.0970 4.4030 8.8061 58.7070
4.4272 0.7500 7.5000 0.3344 3.3436 4.1564 8.3127 55.4182
7 6.0331 1.0000 10.0000 0.4797 4.7969 5.2031 10.4061 52.0307
8 5.8391 1.0000 10.0000 0.4665 4.6649 5.3351 10.6701 53.3506
o 13.8008 2.5000 25.0000 1.2575 12.5755 12.4245 24.8491 49.6982
10 15.4883 2.5000 25.0000 1.4113 14.1131 10.8869 21.7738 43.5475
11 34.0750 5.0000 50.0000 2.6828 26.8276 23.1724 46.3448 46.3448
12 34.6436 5.0000 50.0000 2.7275 27.2752 22.7248 45.4495 45.4495
13 54.9270 7.5000 75.0000 4.2151 42.1506 32.8494 65.6989 43.7993
14 51.6294 7.5000 75.0000 3.9620 39.6200 35.3800 70.7600 47.1733
Equillconc. ug/ml
Fig.3.22 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by Muscovite
70
ads
des
e T

3.26 De<strong>sorption</strong> <strong>of</strong> FBNZ by Muscovite
Table 3.26(a)z De<strong>sorption</strong> <strong>of</strong> FBNZ by Muscovite
emo tb tb+min+sol ent sol
Table 3.26(b): De<strong>sorption</strong> <strong>of</strong> FBNZ by Muscovite
pk ht
des
FBNZ
ent uq
des
uq/0.5
fnd
uq/ml finalvol fnd uq
1 0.1072 0.0062 1 0.1 020 0.0625
2 0.1 01 I 0.0059 10.0120 0.0589
3 0.2014 0.0133 10.2680 0.1362
4 0.2013 0.0133 10.3780 0.1377
6 0.2922 0.0221 10.0700 0.2222
o 0.2943 0.0222 10.2040 0.2268
7 0.6232 0.0496 10.0540 0.4982
8 0.6311 0.0504 10.0380 0.5061
o 0.8392 0.0765 10.3400 0.7907
10 0.8451 0.0770 10.2740 0.7912
11 1.2345 0.0972 10.2840 0.9995
12 1.2547 0.0988 10.1280 1.0005
13 2.4122 0.1 851 10.2540 1.8981
14 2.4292 0.1 864 10.4640 1.9506
des
uo/o % des
1 12.8130 13.0690 0.0'120 0.0013 0.0612 0.1224 56.1 953
2 12.9730 13.2300 0.0140 0.0021 0.0568 0.1135 37.2726
3 12.9720 13.2600 0.0760 0.0134 0.1228 0.2456 69.5009
4 12.9230 13.2100 0.0740 0.0129 0.1248 0.2496 71.4689
12.9400 13.2310 0.0820 0.0254 0.1 968 0.3937 63.5616
h 12.9260 13.2180 0.0840 0.0281 0.1 987 0.3975 59.4361
7 12.9620 13.2650 0.1 060 0.0508 0.4473 0.8947 93.2546
8 12.6820 12.9860 0.1 080 0.0504 0.4557 0.91 15 97.6924
o 12.8920 13.2040 0.1240 0.1 559 0.6348 1.2695 50.4755
10 12.6320 12.9620 0.1600 0.2258 0.5654 1.1307 40.0588
11 12.9190 13.2210 0.1 040 0.2790 0.7205 1.4411 26.8578
12 12.7010 13.0100 0.1 1 80 0.3218 0.6786 1.3573 24.8810
IJ 12.9450 13.2230 0.0560 0.2360 1.6621 3.3242 39.4319
14 12.7050 13.0100 01100 0.4358 1.5148 3.0297 38.2339
7T

3.27 Ad<strong>sorption</strong> <strong>of</strong> FBNZ bY Soil l
Table 3.27: Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Soil I
ok.ht fbnz add ppm add uq/O.5q fnd oom fnd uq/O.5q ads ug/O.59 ads uq/q % ads
I 2.5728 0.2500 2.5000 0.1 962 1.9622 0.5378 1.0757 21.5131
z 2.5728 0.2500 2.5000 0.1962 1.9622 0.5378 1.0757 21.5131
? 6.8253 0.5000 5.0000 0.4682 4.6822 0.3178 0.6357 6.3565
4 6.8978 0.5000 5.0000 0.4732 4.7319 0.2681 0.5362 5.3618
5 10.9284 0.7500 7.5000 0.7210 7.2100 0.2900 0.5799 3.8661
o 10.5027 0.7500 7.5000 0.6929 6.9292 0.5708 1.1416 7.6109
I 14.7838 1.0000 10.0000 0.9498 9.4983 0.5017 1.0034 5.0171
I 14.4758 1.0000 10.0000 0.9300 9.3004 0.6996 1.3992 6.9960
o 36.5877 2.5000 25.0000 2.3622 23.6223 1.3777 2.7554 5.5109
10 36.5387 2.5000 25.0000 2.3591 23.5906 1.4094 2.8187 5.6374
11 75.2628 5.0000 50.0000 4.7089 47.0889 2.9111 5.8221 5.8221
12 75.2628 5.0000 50.0000 4.7089 47.0889 2.9111 5.8221 5.8221
13 140.6877 10.0000 100.0000 9.4353 94.3527 5.6473 11.2946 5.6473
14 140.7597 10.0000 100.0000 9.4401 94.4010 5.5990 11.1980 5.5990
40
35
30
Et
ctt
,zJ
o
!,
06 zo
o
t, o
Nrs
z,
o
ll-
'10
5
Equil. conc. ug/ml
Fig.3.23 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by Soil I
72
ads
des
o I

3.28 De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil I
Table 3.28(a): De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil I
emp tb tb+soil+sol ent sol
fbnz
ent uo
Table 3.28(b): De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil I
des
uo/0.5
des
uq/q % des
1 12.3300 12.7510 0.3420 0.0671 0.0159 0.0317 2.9508
z 12.4020 12.7900 0.2760 0.0542 0.0231 0.0462 4.2984
? 12.4810 12.8710 0.2800 0.1 31 1 0.0379 0.0757 11.9168
4 12.2820 12.6810 0.2980 0.1410 0.0369 0.0739 13.7778
12.3940 12.8480 0.4080 0.2942 0.1 51 8 0.3036 52.3481
h 12.3560 12.8370 0.4620 0.3201 0.1 395 0.2791 24.4457
12.2430 12.7510 0.5160 0.4901 0.2213 0.4427 44.1162
8 12.3280 12.8320 0.5080 0.4725 0.1 736 0.3471 24.8081
o 12.2480 12.8900 0.7840 1.8520 0.7613 1.5226 55.2564
10 12.3780 12.9900 0.7240 1.7080 0.8653 1.7305 61.3950
11 12.3870 12.9260 0.5780 2.7217 1.5117 3.0234 51.9293
12 12.3560 12.8900 0.5680 2.6747 1.6011 3.2022 55.0000
13 12.2560 12.6560 0.3000 2.8306 2.8842 5.7684 51.0720
14 12.2720 12.6890 0.3340 3.1 530 2.6694 5.3388 47.6762
pk ht
des
fnd
uq/ml finalvol fnd uo
1 0.1077 0.0082 1 0.1 020 0.0830
2 0.1012 0.0077 10.0120 0.0773
J 0.2399 0.0165 10.2680 0.1 690
4 0.2500 0.0171 10.3780 0.1779
5 0.6713 0.0443 10.0700 0.4460
6 0.6828 0.0450 10.2040 0.4597
7 1.1014 0.0708 10.0540 0.7114
8 1.0017 0.0644 10.0380 0.6460
o 3.9145 0.2527 10.3400 2.6133
10 3.8793 0.2505 10.2740 2.5732
11 6.5795 0.4117 10.2840 4.2334
12 6.7476 0.4222 1 0.1 280 4.2757
13 8.3101 0.5573 10.2540 5.7148
14 8.2967 0.5564 10.4640 5.8224
-a IJ

3.29 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Soil2
Table 3.29: Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Soil2
pk.ht Fbnz add oom add uq/O.5q fnd oom fnd uo/O.5q ads uq/O.5q ads uq/q % ads
1 2.8450 0.2500 2.5000 0.1568 1.5676 0.9324 1.8648 37.2961
2 2.6394 0.2500 2.5000 0.1454 1.4543 1.0457 2.0914 41.8276
7.4861 0.5000 5.0000 0.4269 4.2694 0.7306 1.4612 14.6124
4 7.5034 0.5000 5.0000 0.4279 4.2792 0.7208 1.4415 14.4151
5 9.5114 0.7500 7.5000 0.6901 6.9014 0.5986 1.1972 7.9815
9.5212 0.7500 7.5000 0.6908 6.9085 0.5915 1.1831 7.8871
I 13.2516 1 0000 10.0000 0.8053 8.0526 1.9474 3.8948 19.4740
8 13.4079 1.0000 10.0000 0.8148 8.1476 1.8524 3.7048 18.5242
o 31.4999 2.5000 25.0000 2.0321 20.3207 4.6793 9.3585 18.7171
10 31.3960 2.5000 25.0000 2.0254 20.2537 4.7463 9.4926 18.9852
11 66.0943 5.0000 50.0000 4.2250 42.2505 7.7495 15.4991 15.4991
12 66.0124 5.0000 50.0000 4.2222 42.2221 7.7779 15.5557 15.5557
,.t ? 119.5010 10.0000 100.0000 8.8032 88.0321 11.9679 23.9357 11.9679
14 120.6490 10.0000 100.0000 8.8878 88.8778 11.1222 22.2443 11.1222
ttt
ct
40
35
30
,zc
o
!t
c6zo
,;
!t (E
N15
z
o
ll-
10
5
0
Equil. conc. ug/ml
o
ads
des
Fig. 3.24 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by Soil 2
74
o T

3.30 De<strong>sorption</strong> <strong>of</strong> FBNZ bY Soil2
Table 3.30(a):De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil2
emo tb tb+soil+sol ent sol
Fbnz ent
Table 3.30(b): De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil2
UO
des
uq/0.5
des
uo/o % des
I 12.3300 12.7510 0.3420 0.0536 0.2873 0.5746 30.8148
z 12.4020 12.7900 0.2760 0.0401 0.2851 0.5701 27.2610
3 12.4810 12.8710 0.2800 0.1 1 95 0.3599 0.7198 49.2569
4 12.2820 12.6810 0.2980 0.1275 0.3986 0.7973 55.3096
12.3940 12.8480 0.4080 0.2816 0.4593 0.9186 76.7313
12.3560 12.8370 0.4620 0.3192 0.4627 0.9254 78.2180
7 12.2430 12.7510 0.5160 0.4155 0.9867 1.9734 50.6666
B 12.3280 12.8320 0.5080 0.4139 0.9803 1.9605 52.9184
9 12.2480 12.8900 0.7840 1.5931 1.1462 2.2924 24.4949
10 12.3780 12.9900 0.7240 1.4664 1.2673 2.5347 26.7016
11 12.3870 12.9260 0.5780 2.4421 2.1525 4.3050 27.7757
12 12.3560 12.8900 0.5680 2.3982 2.2028 4.4056 28.3213
13 12.2560 12.6560 0.3000 2.6410 4.2699 8.5398 35.6780
14 12.2720 12.6890 0.3340 2.9685 4.3056 8.61 13 38.7123
pk ht
des
fnd
uq/ml finalvol fnd uq
4 I 0.6125 0.0337 10.1020 0.3409
2 0.5895 0.0325 10.0120 0.3252
3 0.8187 0.0467 10.2680 0.4794
4 0.8890 0.0507 10.3780 0.5262
5 '1.0140 0.0736 10.0700 0.7409
o 1.0560 0.0766 10.2040 0.78'19
7 2.2951 0.1 395 10.0540 1.4022
8 2.2856 0.1 389 10.0380 1.3942
o 4.1067 0.2649 10.3400 2.7393
10 4.1246 0.2661 10.2740 2.7337
11 6.9890 0.4468 10.2840 4.5946
12 7.1026 0.4543 1 0.1 280 4.6010
13 9.1489 0.6740 10.2540 6.9109
14 9.4366 0.6952 10.4640 7.2742
75

3.31 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Soil3
Table 3.31: Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Soil3
pk.ht
Fbnz
add
oom
add
uo/0.5o
fnd
oDm
fnd
uq/0.5o
ads
uq/0.5q ads uq/q % ads
1 1.2100 0.2500 2.5000 0.1 398 1.3978 1.1022 2.2044 44.0889
z 1 .1 000 0.2500 2.5000 0.1344 1.3435 1 .1 565 2.3129 46.2581
J 4.7090 0.5000 5.0000 0.3082 3.0821 1.9179 3.8358 38.3578
4 4.8405 0.5000 5.0000 0.3168 3.1682 1.8318 3.6637 36.6369
8.2975 0.7500 7.5000 0.4672 4.6720 2.8280 5.6560 37.7065
o 8.3675 0.7500 7.5000 0.4751 4.7507 2.7493 5.4987 36.6578
13.5975 1.0000 10.0000 0.6715 6.7148 3.2852 6.5704 32.8519
B '13.6375 1.0000 10.0000 0.6491 6.4910 3.5090 7.0181 35.0904
I 30.6031 2.5000 25.0000 1.986'1 19.8614 5.1 386 10.2772 20.5543
10 30.6453 2.5000 25.0000 1.9889 19.8888 5.1112 10.2224 20.4448
11 63.7089 5.0000 50.0000 4.1504 41.5035 8.4965 16.9930 16.9930
12 63.6987 5.0000 50.0000 4.1497 41.4969 8.5031 17.0062 17.0062
1? 106.7875 10.0000 100.0000 8.3669 83.6689 16.3311 32.6621 16.3311
14 106.6875 10.0000 100.0000 8.3591 83.5906 16.4094 32.B1BB 16.4094
40
35
30
cn
CD
oq)
!t
1ro
o
!t
(!
Nrq
z'-
o
lt '10
5
0
Equil. conc. ug/ml
Fig. 3.25 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by Soil3
76
ads
des
o
I

3.32 De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil3
Table 3.32 (a)z De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil 3
emo tb tb+soil+sol ent sol
Fbnz ent
uo
Table 3.32(b): De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil3
des
uq/.5
des
uo/o % des
1 12.3300 12.6650 0.1 700 0.0238 0.0228 0.0455 2.0643
z 12.4020 12.7120 0.1200 0.0161 0.0287 0.0573 2.4792
? 12.4810 1 3.1 050 0.7480 0.2305 0.4343 0.8685 22.6421
4 12.2820 12.9590 0.8540 0.2706 0.4340 0.8679 23.6897
5 12.3940 12.7990 0.3100 0.1448 0.4801 0.9601 16.9755
o 12.3560 12.7880 0.3640 0.1729 0.4644 0.9288 16.8914
7 12.2430 12.6890 0.3920 0.2632 0.7919 1.5838 24.1045
I 12.3280 12.7890 0.4220 0.2739 0.7320 1.4641 20.8613
o 12.2480 12.7360 0.4760 0.9454 0.9341 1.8682 18.1779
10 12.3780 12.8770 0.4980 0.9905 0.8623 1.7246 16.8711
11 12.3870 12.8900 0.5060 2.1001 1.1686 2.3373 13.7544
12 12.3560 12.8710 0.5300 2.1 993 1.0788 2.1576 12.6870
13 12.2560 12.6810 0.3500 2.9284 2.6152 5.2304 16.0136
14 12.2720 12.7010 0.3580 2.9925 2.6809 5.3619 16.3378
pk ht
des
fnd
uo/ml finalvol fnd uo
1 0.0399 0.0046 10.1020 0.0465
z 0.0366 0.0045 10.0120 0.0448
3 0.9892 0.0647 10.2680 0.6648
4 1.0372 0.0679 10.3780 0.7045
5 1.1021 0.0621 10.0700 0.6249
1.1 001 0.0625 10.2040 0.6373
7 2.1251 0.1 049 10.0540 1.0551
B 2.1055 01002 10.0380 1.0059
o 2.8008 0.1 81 B 10.3400 1.8795
10 2.7787 0.1 803 10.2740 1.8528
11 4.8790 0.3178 10.2840 3.2687
12 4.9684 0.3237 1 0.1 280 3.2781
13 6.9001 0.5406 10.2540 5.5436
14 6.9200 0.5422 10.4640 5.6735
.1.f

3.33 Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Soil4
Table 3.33: Ad<strong>sorption</strong> <strong>of</strong> FBNZ by Soil4
ctl
ct
rt
o
!t
0d
o
E
o
N
z
@
tl.
80
70
60
50
40
30
20
10
0
pk.ht
o2468
Fbnz add
DDM
add
uo/0.5o
fnd
DOm
fnd
uq/0.5o
Equil.conc. ug/ml
Fig.3.26 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ by Soil4
ads
uq/0.5o ads uo/o % ads
I 2.1152 0.2500 2.5000 0.1 576 1.5758 0.9242 1.8485 36.9694
z 2.2051 0.2500 2.5000 0.1643 1.6428 0.8572 1.7144 34.2885
? 4.8112 0.5000 5.0000 0.3056 3.0555 1.9445 3.8890 38.8899
4 4.7812 0.5000 5.0000 0.3036 3.0365 1.9635 3.9271 39.2709
5 7.5622 0.7500 7.5000 0.4828 4.8280 2.6720 5.3441 35.6272
h 7.8774 0.7500 7.5000 0.5029 5.0292 2.4708 4.9416 32.9440
7 11.5808 1.0000 10.0000 0.7429 7.4285 2.5715 5.1429 25.7146
8 10.8706 1.0000 10.0000 0.6973 6.9730 3.0270 6.0540 30.2702
o 24.5788 2.5000 25.0000 1.6026 16.0261 8.9739 17.9479 35.8957
10 24.5532 2.5000 25.0000 1.6009 16.0094 8.9906 17.9812 35.9625
11 44.1200 5.0000 50.0000 2.9047 29.0473 20.9527 41.9054 41.9054
12 44.0952 5.0000 50.0000 2.9031 29.0310 20.9690 41.9381 41.9381
1'4, 74.0285 10.0000 100.0000 6.6111 66.1112 33.8888 67.7777 33.BBB8
14 74.8068 10.0000 100.0000 6.6806 66.8062 33.1938 66.3876 33.1 938
78
ads
des
o
I

3.34 De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil4
Table 3.34(a): De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil4
emo tb tb+soil+sol ent sol
Fbnz ent
Table 3.34(b): De<strong>sorption</strong> <strong>of</strong> FBNZ by Soil4
UO
des
uq/O.5
des
uo/o % des
1 12.3300 12.8200 0.4800 0.0756 0.8544 1.7088 92.4430
2 12.4020 12.9020 0.5000 0.0821 0.7635 1.5269 89.0647
12.4810 13.0100 0.5580 0.1 705 0.9084 1.8168 46.7168
4 12.2820 12.8200 0.5760 0.1749 0.8935 1.7870 45.5035
5 12.3940 12.9510 0.6140 0.2964 1.1178 2.2356 41.8340
6 12.3560 12.9210 0.6300 0.3168 1 .1 166 2.2331 45.1 903
7 12.2430 12.8100 0.6340 0.4710 1.7528 3.5057 68.1650
8 12.3280 12.8990 0.6420 0.4477 1.6271 3.2543 53.7540
9 12.2480 12.8610 0.7260 1.1635 1.8634 3.7268 20.7644
10 12.3780 12.9890 0.7220 1.1 559 2.0072 4.0145 22.3258
11 12.3870 13.3120 1.3500 3.9214 2.1365 4.2730 10.1967
12 12.3560 12.9840 0.7560 2.1947 3.5664 7.1328 17.0079
12.2560 12.9680 0.9240 6.1 087 3.9627 7.9253 11.6931
14 12.2720 12.9650 0.8860 5.9190 4.4486 8.8971 13.4018
pk ht
des
fnd
uq/ml finalvol fnd uq
1 1.2358 0.0921 1 0.1 020 0.9300
2 1.1337 0.0845 10.0120 0.8456
? 1.6545 0.1 051 10.2680 1.0789
4 1.6210 0.1 029 10.3780 1.0684
5 2.1998 0.1404 10.0700 1.4143
6 2.2003 0.1405 10.2040 1.4334
7 3.4482 0.2212 10.0540 2.2238
8 3.2223 0.2067 10.0380 2.0748
4.4896 0.2927 10.3400 3.0269
10 4.7218 0.3079 10.2740 3.1631
11 8.9472 0.5891 10.2840 6.0579
12 8.6400 0.5688 10.1280 5.7611
13 10.9981 0.9822 10.2540 10.0713
14 11.0944 0.9908 10.4640 10.3676
79

3.35 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by Alumina
Table 3.35 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by Alumina
ct
ctt
o
t,
od
c,
!t (!
N
z
o
40
35
30
25
20
15
10
5
0
ok.ht
ABNZ add
DOm
add
uq/0.5o
ADSORPTTON & DESORPTTON OF ABNZ By At2O3
4
Equil. con. ug/ml
Fig.3.27 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by Al2O3
80
fnd
oDm
fnd
uo/0.5o
ads
uo/0.5o ads uq/q % ads
1 1.2341 0.2500 2.5000 0.2340 2.3403 0.1 597 0.3195 6.3890
z 1.2240 0.2500 2.5000 0.2321 2.3210 0.1 790 0.3580 7.1605
? 3.4446 0.5000 5.0000 0.4794 4.7936 0.2064 0.4129 4.1290
4 3.4381 0.5000 5.0000 0.4785 4.7845 0.2155 0.4309 4.3091
5 5.4331 0.7500 7.5000 0.6274 6.2745 1.2255 2.4511 16.3406
o 5.2976 0.7500 7.5000 0.61 18 6.1180 1.3820 2.7640 18.4265
7 7.5654 1.0000 10.0000 0.8281 8.2814 1.7186 3.4373 17.1863
I 7.4516 1.0000 10.0000 0.8157 8.1 570 1.8430 3.6860 18.4298
o 15.1791 2.5000 25.0000 2.2918 22.9182 2.0818 4.1636 8.3272
10 1 5.1 599 2.5000 25.0000 2.2889 22.8892 2.1108 4.2217 8.4434
11 30.4485 5.0000 50.0000 4.6996 46.9961 3.0039 6.0078 6.0078
12 30.3535 5.0000 50.0000 4.6849 46.8494 3.1 506 6.3012 6.3012
13 41.4286 7.5000 75.0000 6.7439 67.4391 7.5609 15.1217 10.0812
14 41.4606 7.5000 75.0000 6.7491 67.4913 7.5087 15.0174 10.01 16
ads
des
o T

3.36 De<strong>sorption</strong> <strong>of</strong> ABNZ by Alumina
Table 3.36 (a): De<strong>sorption</strong> <strong>of</strong> ABNZ by AlzOs
emo tb tb+min+sol
ent
sol
abnz ent
uq
Table 3.36(b): De<strong>sorption</strong> <strong>of</strong> ABNZ by Al2O3
pk ht
des fnd uo/ml finalvol fnd uo
1 0.1257 0.0238 10.1020 0.2408
2 0.1 356 0.0257 10.0120 0.2575
? 0.3569 0.0497 10.2680 0.5100
4 0.3633 0.0506 10.3780 0.5247
5 0.7788 0.0885 10.0700 0.8910
6 0.7542 0.0856 10.2040 0.8734
7 1.0011 0.1 096 10.0540 1.1018
8 1.0024 0.1 097 10.0380 1.1015
o 1.5215 0.2297 10.3400 2.3753
10 1.5142 0.2286 10.2740 2.3489
11 2.9729 0.4589 10.2840 4.7189
12 2.9988 0.4629 10.1280 4.6878
13 4.6125 0.7508 10.2540 7.6991
14 4.6500 0.7569 10.4640 7.9207
81
des
uq/0.5 des uq/q % des
1 12.36 12.771 0.322 0.075357 0.165402 0.330805 70.67649
z 12.467 12.878 0.322 0.074736 0.182769 0.365539 78.74633
12.447 12.866 0.338 0162022 0.34802 0.69604 72.6017
4 12.35 12.765 0.33 0.1 5789 0.36683 0.73366 76.66979
5 12.374 12.845 0.442 0.277331 0.613625 1.22725 97.79739
o 12.254 12.725 0.442 0.270416 0.602965 1.20593 98.55568
7 12.369 12.856 0.474 0.392537 0.709225 1.41845 85.64103
8 12.371 12.865 0.488 0.398063 0.703401 1.406802 86.23263
9 12.41 12.871 0.422 0.967148 1.408149 2.816299 61.44244
10 12.385 12.868 0.466 1.066635 1.282223 2.564447 56.01883
11 12.336 12.882 0.592 2.782169 1.936707 3.873414 41.20995
12 12.272 12.825 0.606 2.839075 1.848707 3.697413 39.46061
13 12.332 12.998 0.832 5.610936 2.088194 4.176387 30.96412
14 12.113 12.799 0.872 5.885241 2.035442 4.070885 30.1 5859

o.7
0.6
NE
0.4
o.3
v-z
0.1
o.o
0.45
0.40
u.53
0.30
0.25
o.20
n 1q
0.10
0.05
0.00
o.45
o.40
0.35
o.30
o.25
o.20
u. t3
0.10
0.o5
o.00
nr
250 300 350
Fig. 3.28. Ad<strong>sorption</strong> spectra <strong>of</strong> ABNZ by Silica (Ad<strong>sorption</strong> blank)
rl
250
l'-Jr--.i- 1'--r"---l
nr
300 350
Fig. 3.29. Ad<strong>sorption</strong> spectra <strong>of</strong> ABNZ by Silica (Ad<strong>sorption</strong> a)
25\J
rrlll
300
l.'::: I nl
350
Fig. 3.30. Ad<strong>sorption</strong> spectra <strong>of</strong> ABNZ by Silica (Ad<strong>sorption</strong> b)
82

0.25
o.20
0.15
0.10
o.o5
o.00
o.45
o.40
0.35
o.30
0.25
o.20
0.15
0.10
0.05
o.00
-o.05
-o.10
-o.15
I
1.,
if*v'*;;-. , -
irrl
250
i\
r\
l\
i\
r\.
I
I
I
I
t.
rll\ ; l-t.1-*,
\\1
_ .- :t-
,lrriT-lnr
3@ 350
Fig. 3.31. Ad<strong>sorption</strong> spectra <strong>of</strong> ABNZ by Silica {de<strong>sorption</strong> a)
26 ri ir llr
2n 300 350
Fig. 3.28. Ad<strong>sorption</strong> spectra <strong>of</strong> ABNZ by Silica (de<strong>sorption</strong> b)
83

3.37 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by Silica
Table 3.37: Ad<strong>sorption</strong> <strong>of</strong> ABNZ by SiO2
70
60
or 5o
ctt
ti
Odo
!t-
06
ti
Ean
(! ""
N
z
@
4zo
10
0
ok.ht
ABNZ add
oom add uq/0.5q fnd ppm
fnd
uo/0.5o
ads
uo/0.5o
ads
uq/o % ads
1 1 .1 300 0.2500 2.5000 0.1 61 8 1.6183 0.8817 1.7635 35.2695
z 1.1370 0.2500 2.5000 0.1628 1.6283 0.8717 1.7434 34.8685
3 1.5933 0.5000 5.0000 0.2157 2.1572 2.8428 5.6855 56.8550
4 1.6114 0.5000 5.0000 0.2182 2.1818 2.8182 5.6365 56.3649
5 2.3305 0.7500 7.5000 0.3413 3.4127 4.0873 8.1746 54.4971
A 2.8254 0.7500 7.5000 0.4137 4.1374 3.3626 6.7251 44.8342
7 4.6043 1.0000 10.0000 0.5040 5.0401 4.9599 9.9199 49.5995
I 4.5890 1.0000 10.0000 0.5023 5.0234 4.9766 9.9531 49.7657
o 9.0670 2.5000 25.0000 1.3690 '13.6898 11.3102 22.6204 45.2407
1n 9.0736 2.5000 25.0000 1.3700 13.6998 11.3002 22.6004 45.2009
11 19.3908 5.0000 50.0000 2.9929 29.9290 20.0710 40.1420 40.1420
12 19.4537 5.0000 50.0000 3.0026 30.0261 19.9739 39.9479 39.9479
13 27.7016 7.5000 75.0000 4.5094 45.0938 29.9062 59.8124 39.8749
14 29.4759 7.5000 75.0000 4.7982 47.9821 27.0179 54.0359 36.0239
Equil. conc. ug/ml
ads
des
Fig. 3.33 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by SiO2
84
o T

3.38 De<strong>sorption</strong> <strong>of</strong> ABNZ by Silica
Table 3.38 (a): De<strong>sorption</strong> <strong>of</strong> ABNZ by SiO2
emp tb tb+min+sol ent sol
Abnz
ent uq
Table 3.38(b): De<strong>sorption</strong> <strong>of</strong> ABNZ by Silica
des
uq/0.5
des
uo/o % des
I 12.3600 13.0150 0.8100 0.1311 0.0767 0.1 533 47.3759
z 12.4670 1 3.1 200 0.8060 0.1312 0.0775 0.1 550 47.6100
a 12.4470 13.1260 0.8580 0.1 851 0.1103 0.2207 51.1453
4 12.3500 13.0250 0.8500 0.1854 0.1145 0.2291 52.5017
5 12.3740 13.1100 0.9720 0.3317 0.2763 0.5525 80.9532
o 12.2540 12.9980 0.9880 0.4088 0.2076 0.4152 50.1754
7 12.3690 13.1 180 0.9980 0.5030 0.4779 0.9557 94.8143
8 12.3710 1 3.1 040 0.9660 0.4853 0.4867 0.9734 96.8891
o 12.4100 13.2010 1.0820 1.4812 1.2064 2.4128 88.1243
10 12.3850 1 3.1 500 1.0300 1.4111 1.2268 2.4535 89.5469
11 12.3360 1 3.1 450 1.1 180 3.3461 2.9539 5.9078 98.6977
12 12.2720 13.0860 1.1280 3.3869 2.7292 5.4583 90.8929
13 12.3320 1 3.1 590 1.1540 5.2038 4.4054 8.8107 97.6932
14 12.1130 12.9490 1.1720 5.6235 4.4221 8.8441 92.1606
pk ht
des fnd uq/ml finalvol fnd uq
1 0.1436 0.020565 10.102 0.207746
2 0.1456 0.020851 10.012 0.208763
3 0.2125 0.028771 10.268 0.295425
4 0.2135 0.028907 10.378 0.299995
E 0.4123 0.060376 10.07 0.607987
o 0.4125 0.060405 10.204 0.616376
7 0.89125 0.09756 10.054 0.980867
8 0.88456 0.09683 10.038 0.971978
o 1.72154 0.259927 10.34 2.687643
10 1.7005 0.25675 10.274 2.63785
11 3.969 0.6126 10.284 6.299982
12 3.9125 0.60388 10.128 6.1 1 6095
13 5.7568 0.937115 10.254 9.609182
14 5.89745 0.960011 10.464 10.04556
85

3.39 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by Soit I
Table 3.39: Ad<strong>sorption</strong> <strong>of</strong> ABNZ by Soil 1
h 5
{
od
$ I
t
40
3o
25
20
'15
10
o
pk.ht
ABNZ
add ppm
add
uo/0.5o fnd opm
ADSORPTION & DESORPTION OF ABNZ BY SOIL 1
Fig.3.34 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by soil I
fnd
uq/0.5q
ads
uo/0.5o ads uq/q % ads
1 2.5959 0.2500 2.5000 0.2312 2.3116 0.1 884 0.3768 7.5362
z 2.6237 0.2500 2.5000 0.2336 2.3363 0.1637 0.3273 6.5467
5 4.2130 0.5000 5.0000 0.4072 4.0715 0.9285 1.8570 18.5695
4 4.2007 0.5000 5.0000 0.4060 4.0596 0.9404 1.8807 18.8073
5 5.9437 0.7500 7.5000 0.5566 5.5662 1.9338 3.8675 25.7834
o 5.9437 0.7500 7.5000 0.5566 5.5663 1.9337 3.8675 25.7830
7 8.6139 1.0000 10.0000 0.7462 7.4624 2.5376 5.0752 25.3762
B 8.4370 1.0000 10.0000 0.7309 7.3091 2.6909 5.3817 26.9087
I 14.8261 2.5000 25.0000 2.0104 20.1 038 4.8962 9.7923 19.5846
10 14.7961 2.5000 25.0000 2.0056 20.0558 4.9442 9.8884 19.7769
11 27.9617 5.0000 50.0000 4.3408 43.4080 6.5920 1 3.1 840 1 3.1 840
12 27.8861 5.0000 50.0000 4.3291 43.2906 6.7094 13.4187 13.4187
13 40.4632 7.5000 75.0000 6.5653 65.6528 9.3472 18.6945 12.4630
14 40.4132 7.5000 75.0000 6.5572 65.5716 9.4284 18.8567 12.5711
86
ads
des
o T

\
3.40 De<strong>sorption</strong> <strong>of</strong> ABNZ by Soil I
Table 3.40(a):De<strong>sorption</strong> <strong>of</strong> ABNZ by Soil 1
emp tb tb+soil+sol ent sol
Table 3.a0@): De<strong>sorption</strong> <strong>of</strong> ABNZ by Soil I
87
Abnz
ent uq
des
uq/0.5
des
uq/q % des
1 12.3600 12.7710 0.3220 0.0744 0.1 956 0.3912 84.6226
2 12.4670 12.8780 0.3220 0.0752 0.2013 0.4027 86.1 71 I
? 12.4470 12.8660 0.3380 0.1376 0.3100 0.6200 76.1429
4 12.3500 12.7650 0.3300 0.1 340 0.3234 0.6468 79.6567
5 12.3740 12.8450 0.4420 0.2460 0.4127 0.8255 74.1486
o 12.2540 12.7250 0.4420 0.2460 0.4129 0.8257 74.1709
7 12.3690 12.8560 0.4740 0.3537 0.5090 1.0180 68.2095
8 12.3710 12.8650 0.4880 0.3567 0.5055 1.0111 69.1 646
o 12.4100 12.8710 0.4220 0.8484 1.2545 2.5089 62.3989
10 12.3850 12.8680 0.4660 0.9346 1.2744 2.5487 63.5413
11 12.3360 12.8820 0.5920 2.5698 2.7715 5.5430 63.8474
12 12.2720 12.8250 0.6060 2.6234 2.6313 5.2626 60.7823
13 12.3320 12.9980 0.8320 5.4623 6.5416 13.0832 99.6392
14 12.1130 12.8120 0.8980 5.8883 6.5261 13.0522 99.5262
pk ht
des
fnd
uq/ml finalvol fnd uo
1 0.3002 0.0267 10.1020 0.2700
2 0.3102 0.0276 10.0120 0.2766
3 0.4511 0.0436 10.2680 0.4476
4 0.4560 0.0441 10.3780 0.4573
5 0.6985 0.0654 10.0700 0.6588
6 0.6895 0.0646 10.2040 0.6589
0.9905 0.0858 10.0540 0.8627
8 0.9915 0.0859 10.0380 0.8622
I 1.4998 0.2034 10.3400 2.1028
10 1.5862 0.2150 10.2740 2.2090
11 3.3456 0.5194 10.2840 5.3412
12 3.3421 0.5188 10.1280 5.2547
13 7.2150 1.1707 10.2540 12.0039
14 7.3120 1.1864 10.4640 12.4144

3.41 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by Soil2
Table 3.41: Ad<strong>sorption</strong> <strong>of</strong> ABNZ by Soil2
ct)
ctt
40
35
30
=^- .zc
o
!t
6. zo
at,
!,
(!
Nrs z- @
10
c
0
pk.ht
ABNZ add
ppm
add
uo/0.5o
fnd
oom
fnd
uq/0.5o
ads
uo/0.5o ads uq/q % ads
1 '1.7358 0.2500 2.5000 0.0921 0.9209 1.5791 3.1582 63.1645
2 1.2045 0.2500 2.5000 0.0639 0.6390 1.8610 3.7220 74.4392
2 3.4204 0.5000 5.0000 0.3338 3.3383 1.6617 3.3234 33.2344
4 3.3293 0.5000 5.0000 0.3249 3.2494 1.7506 3.5013 35.0127
5.5769 0.7500 7.5000 0.6506 6.5061 0.9939 1.9879 13.2527
o 5.6889 0.7500 7.5000 0.6637 6.6367 0.8633 1.7266 11.5105
7 8.4467 1.0000 10.0000 0.8987 8.9869 1.0131 2.0262 1 0.1 308
I 8.3318 1.0000 10.0000 0.8865 8.8647 1 .1 353 2.2705 11.3525
o 14.0068 2.5000 25.0000 2.1679 21.6794 3.3206 6.6412 13.2824
10 14.0268 2.5000 25.0000 2.1710 21.7104 3.2896 6.5793 1 3.1 586
11 27.7618 5.0000 50.0000 4.2897 42.8968 7.1032 14.2064 14.2064
12 27.6709 5.0000 50.0000 4.2756 42.7564 7.2436 14.4873 14.4873
13 39.5480 7.5000 75.0000 6.4168 64.1678 10.8322 21.6643 14.4429
14 40.2104 7.5000 75.0000 6.5243 65.2426 9.7574 19.5148 13.0099
Fig. 3.35 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by soil2
88
ads
des
o
I

3.42 De<strong>sorption</strong> <strong>of</strong> ABNZ by Soil2
Table 3.42(a):De<strong>sorption</strong> <strong>of</strong> ABNZ by Soil2
emp tb tb+soil+sol ent sol
Abnz
ent uq
des
uq/0.5
des
uo/o % des
1 12.2180 12.5450 0.1 540 0.0142 0.0573 0.1146 62.2361
z 12.3530 12.6650 0.1240 0.0079 0.0518 0.1 037 81.1118
J 12.3010 12.6450 0.1 880 0.0628 0.1 490 0.2980 44.6320
4 12.3820 12.7300 0.1 960 0.0637 0.1964 0.3928 60.4490
5 12.2540 12.6030 0.1 980 0.1288 0.4863 0.9726 74.7445
o 12.3710 12.7450 0.2480 0.1 646 0.498,1 0.9962 75.0535
12.3920 12.7780 0.2720 0.2444 0.5955 1 .1910 66.2614
8 12.3010 12.7060 0.3100 0.2748 0.5771 1.1543 65.'1054
o 12.2730 12.7050 0.3640 0.7891 0.8470 1.6939 39.0675
10 12.3070 12.7330 0.3520 0.7642 0.8279 1.6558 38.1 334
11 12.3270 12.7750 0.3960 1.6987 2.2784 4.5568 53.1 1 30
12 12.3520 12.8010 0.3980 1.7017 2.4939 4.9879 58.3290
13 12.3660 12.8350 0.4380 2.8106 3.6782 7.3564 57.3217
14 12.4370 12.8990 0.4240 2.7663 3.8723 7.7447 59.3530
Table 3.42(b): De<strong>sorption</strong> <strong>of</strong> ABNZ by Soil2
pk ht
des
fnd
uo/ml finalvol fnd uq
1 0.1 334 0.0071 1 0.1 020 0.0715
2 0.1125 0.0060 10.0120 0.0598
3 0.2113 0.0206 10.2680 0.2118
4 0.2568 0.0251 10.3780 0.2601
5 0.5236 0.0611 10.0700 0.6151
6 0.5567 0.0649 10.2040 0.6627
7 0.7852 0.0835 10.0540 0.8399
8 0.7977 0.0849 10.0380 0.8520
o 1.0223 0.1582 10.3400 1.6361
10 1.0012 0.1 550 10.2740 1.5921
11 2.5028 0.3867 10.2840 3.9771
12 2.6810 0.4143 1 0.1 280 4.1 956
'13 3.9001 0.6328 10.2540 6.4888
14 3.9101 0.6344 10.4640 6.6386
89

3.43 Ad<strong>sorption</strong> <strong>of</strong> ABNZ by Soil3
Table 3.43: Ad<strong>sorption</strong> <strong>of</strong> ABNZ by Soil3
cn
ctt
f
o
tt
od
o
o
N
z
o
40
35
30
25
20
15
10
5
0
ok.ht
ABNZ add
pDm
add
uq/0.5q
fnd
DOm
4
Equil. conc. ug/ml
fnd
uq/0.5q
Fig.3.36 Ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> ABNZ by soil3
ads
uo/0.5o ads uq/o % ads
1 2.2917 0.2500 2.5000 0.1716 1.7159 0.7841 1.5682 31.3636
2 2.2422 0.2500 2.5000 0.1679 1.6788 0.8212 1.6423 32.8461
3.2405 0.5000 5.0000 0.3530 3.5298 1.4702 2.9404 29.4039
4 3.2279 0.5000 5.0000 0.3516 3.5160 1.4840 2.9680 29.6795
4.1092 0.7500 7.5000 0.5227 5.2272 2.2728 4.5456 30.3041
b 4.0170 0.7500 7.5000 0.5689 5.6888 1.8112 3.6224 24.1492
7.2169 1.0000 10.0000 0.7723 7.7228 2.2772 4.5544 22.7718
8 7.4202 1.0000 10.0000 0.7940 7.9404 2.0596 4.1193 20.5963
I 12.8953 2.5000 25.0000 2.0779 20.7787 4.2213 8.4426 16.8853
10 12.6692 2.5000 25.0000 2.0414 20.4144 4.5856 9.1711 18.3422
11 25.7920 5.0000 50.0000 4.0457 40.4569 9.5431 19.0862 19.0862
12 25.8020 5.0000 50.0000 4.0473 40.4726 9.5274 19.0548 19.0548
13 36.1 91 5 7.5000 75.0000 6.0350 60.3497 14.6503 29.3007 19.5338
14 36.2280 7.5000 75.0000 6.0411 60.4106 14.5894 29.1788 19.4525
t
90
ads
des
O
T

3.44 DesorPtion <strong>of</strong> ABNZ bY Soil 3
Table 3.44(a\: De<strong>sorption</strong> <strong>of</strong> ABNZ by Soil3
emo tb tb+soil+sol ent sol
Abnz
ent uq
Table 3.a4@): De<strong>sorption</strong> <strong>of</strong> ABNZ bY Soil3
des
uo/0.5
des
uo/o % des
1 12.2180 12.6150 0.2940 0.0271 0.0218 0.0437 23.7056
2 12.3530 12.7500 0.2940 0.0188 0.0238 0.0475 37.1804
J 12.3010 12.7080 0.3140 0.1 048 0.0498 0.0997 14.9267
4 12.3820 12.7910 0.3180 0.1033 0.0556 0.1112 17.1084
12.2540 12.6740 0.3400 0.2212 0.0905 0.1 809 13.9042
o 12.3710 12.7860 0.3300 0.2190 0.0851 0.1703 12.8282
7 12.3920 12.8350 0.3860 0.3469 0.1521 0.3042 16.9269
B 12.3010 12.7400 0.3780 0.3351 0.1 373 0.2746 15.4875
9 12.2730 12.7119 0.3778 0.8190 0.3103 0.6205 14.3113
10 12.3070 12.7490 0.3840 0.8337 0.3026 0.6051 13.9361
11 12.3270 12.7810 0.4080 1.7502 0.7036 1.4073 16.4029
12 12.3520 12.7990 0.3940 1.6846 0.7606 1.5213 17.7900
13 12.3660 12.8310 0.4300 2.7592 1.2334 2.4669 19.2220
14 12.4370 12.8990 0.4240 2.7663 1.4440 2.8879 22.1321
pk ht
des
fnd
uq/ml finalvol fnd uq
1 0.0913 0.0048 10.1020 0.0489
2 0.0801 0.0042 10.0120 0.0425
3 0.1 543 0.0151 10.2680 0.1547
4 0.1 569 0.0153 10.3780 0.1 589
5 0.2653 0.0310 10.0700 0.3117
6 0.2555 0.0298 10.2040 0.3041
7 0.4665 0.0496 10.0540 0.4990
8 0.4423 0.0471 10.0380 0.4724
I 0.7056 0.1 092 10.3400 1.1293
10 0.7145 0.1 106 10.2740 1.1362
11 1.5442 0.2386 10.2840 2.4538
12 1.5625 0.2414 1 0.1 280 2.4452
13 2.3998 0.3894 10.2540 3.9926
14 2.4798 0.4024 10.4640 4.2102
9l

4.1 Biological activity
DISCUSSION
CHAPTER 4
The biological activity <strong>of</strong> the synthesized <strong>benzimidazole</strong> derivatives 2-(4-
fluorophenyl)-l/I-<strong>benzimidazole</strong> (FBNZ) <strong>and</strong> N-(111- <strong>benzimidazole</strong> -2-ylmethyl)
acetamide (ABNZ) was determined. The results including this activity are being
discussed.
4.1.1 AntifugalBioassay:
The in vitro antifungal bioassay was carried out by Agar tube dilution protocol. 77
Growth in the compound containing media was determined by measuring linear
growth in millimeter (mm). Concentration <strong>of</strong> each <strong>of</strong> the tested compound was 200pg/ml
in DMSO. The results are reported as o/o inhibition <strong>of</strong> the synthesized compound being
tested. The antifungal bioassay was carried out against six species <strong>of</strong> fungi; Trichophyton
longifusus, C<strong>and</strong>ida albicans, Aspergillus favus, Microsporum canis, Fusarium solani &
C<strong>and</strong>ida Glaberata. The st<strong>and</strong>ard drug used was Miconazole for all the pathogens except
C<strong>and</strong>ida albicans for which Amphotecin-B was taken.
The antifungal activity <strong>of</strong> newly synthesized <strong>benzimidazole</strong> derivatives 2-(4-
fluorophenyl)-1/I-<strong>benzimidazole</strong> (FBNZ) <strong>and</strong> N-(1/I-benzimidazol-2-ylmethyl)
acetamide (ABNZ) <strong>and</strong> commercially used Benomyl was compared.
92

Table 4.1: Antifungal activity <strong>of</strong> <strong>benzimidazole</strong>s
Fungi % Inhibition
Irichpyton Longifusus
l<strong>and</strong>ida Albicans
Benomyl FBNZ A.BNZ
A.spergillus Flavus )0% 35%
Microsporum Canis z0% +0%
usarium Solani J0% 5% +0%
l<strong>and</strong>ida Glabrata
Concentration taken was 200 pg/ml at27 oC <strong>and</strong> incubation time was 7 days.
The results <strong>of</strong> (Table 4.1) showed that compound ABNZ have relatively greater
activity against Microsporum canis & Fusarium solani than the rest <strong>of</strong> the species <strong>and</strong>
compound FBNZ have relatively greater activity against Aspergillus flavus than any other
species.
It was also observed that compounds FBNZ <strong>and</strong> ABNZ antifungal activities are
greater than the commercially used fungicide benomyl. This shows a possibility <strong>of</strong>
replacement <strong>of</strong> benomyl by these compounds.
All the compounds showed zero activity against Trichophyton longifusus,
C<strong>and</strong>ida albicans <strong>and</strong> C<strong>and</strong>ida Glaberata. Compound N-(111- <strong>benzimidazole</strong> -2-
ylmethyl) acetamide (ABNZ) showed in maximum antifungal activity compared to rest
<strong>of</strong> the tested compound.
93

-0
0.r5
o,l
os
--"" c -sQ'
.(c"
ANTIFUNGAL ACTIVITY OF BENZIMIDAZOLES
"."t
"""*
.*f .po"*
a"s
^-t{9
o*""*
-€
^..-

4.2.1 Methyl 1 H- benzim idazole-2-ca rboxylate (Ca rben d azim)
The ad<strong>sorption</strong> isotherms <strong>of</strong> carbendazim on alumina, silica, montmorillonite,
muscovite <strong>and</strong> soils (l-4) respectively (Fig.3.1-Fig.3.8) yielded straight line which
resembles C-type isotherm shape. This type <strong>of</strong> isotherm describes interaction between a
generally hydrophobic adsorbate with a hydrophobic adsorbent (e.g. pesticide-organic
matter interactions) which means that hydrophobic organic contaminant distributes itself
linearly between hydrophobic organic matter adsorbed on an inorganic mineral particle
<strong>and</strong> solutionTl.
Linear or <strong>sorption</strong> equilibrium distribution co-efficient K6, in (ml pg-r) was
calculated by plotting concentration <strong>of</strong> the pesticide adsorbed in (pglg soil or mineral)
against C. the pesticide concentration (pglml) at the equilibrium concentration for all
soils <strong>and</strong> minerals(Table 4.1).For carbendazimit was observed that among minerals the
order <strong>of</strong> K6 ad<strong>sorption</strong> was montmorillonite ) muscovite > silica > alumina which reflects
the fungicide carbendazim may be trapped between the layers <strong>of</strong> montmorillonite clay.
This can be explained by the fact that interlayer spacing is much smaller in muscovite as
compared to montmorillonite.
95

Table: 4,22 Kavalues for ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> carbendazim minerals/soils
CARBENDAZTM
Minerals & soils Ko(uot Ko (oes)
Alzo: 5.22 17.51
SiOz 5.22 15.02
Muscovite 6.94 16.13
Montmorillonite 263.31 21.01
Soil 1 5.81 9.r3
Soil2 3.s9 7.43
Soil 3 4.9r 6.21
Soil4 1 1.6 9.67
Carbendazim is highly adsorbed on forest soil 4 as compared to the other soils.
The different sorptive behaviors exhibited by carbendazim on soils (1-4) are probably
caused by the general physical/chemical properties <strong>of</strong> soil <strong>and</strong> pesticides solution. For
example variation in sorptive behavior was studied with change in pH sa.
Ad<strong>sorption</strong> is surface phenomena <strong>and</strong> is dependant on the surface area <strong>and</strong> the
organic content <strong>of</strong> the sorbent. Forest soil 4 has higher organic content (9.2%) <strong>and</strong> lower
pH (7.6) (Table 3.2) as compared to other soils so its higher ad<strong>sorption</strong> might be due to
the ionized molecules <strong>of</strong> the fungicides is adsorbed by the organic fraction. The increase
in ad<strong>sorption</strong> <strong>of</strong> soil 4 might be dependant on pH. The pH dependant ad<strong>sorption</strong> <strong>of</strong>
<strong>benzimidazole</strong> derivatives may suggest a reaction with clay surface by protonated
molecule. The basicity <strong>of</strong> carbendazim is presented in the following equation
N
)-rt'
NFO
u/
cHr
H
96
N
\)-r.rH
/+ \
NFO
Ho'
cHe
(pK"4.0) (s)

In the presence <strong>of</strong> increased hydrogen ion activity in the clay surfaces,
<strong>benzimidazole</strong> derivatives may be protonated to form a positive charged molecule which
reacts with the clay surface as follows 5a .
Benzimidazole + H*--clay Benzimidazole- H-clav (6)
With increasing acidity <strong>of</strong> soil suspension an increase in the ad<strong>sorption</strong> <strong>of</strong>
fungicide carbendazim to soil 4 occurred. On the other h<strong>and</strong>, organic matter content <strong>of</strong>
soil 4 is also higher than that <strong>of</strong> the other three soils, <strong>and</strong> the ionized molecules could be
adsorbed by the organic fraction <strong>of</strong> the soil. The difference in the amount <strong>of</strong> carbendazim
adsorbed on various soils, as obtained by the ad<strong>sorption</strong> isotherm, may represent actual
variation in the availability <strong>of</strong> this fungicide to the plant50.
4.2.2 2 - (4-fluoro p h eny l) -l H - b enzi m i d azole (FBNZ)
The close similarity <strong>of</strong> the molecular structures <strong>of</strong> all three <strong>benzimidazole</strong> with
each other may be responsible for the values <strong>of</strong> Ka showing the similar behavior in soils
<strong>and</strong> minerals. Other results <strong>of</strong> <strong>sorption</strong> <strong>of</strong> FBNZ a newly synthesized <strong>benzimidazole</strong>
having good fungicidal activity, shows the ad<strong>sorption</strong> isotherms (Figs.3.19-3.26) were
linear also. The amount <strong>of</strong> fungicides adsorbed (%) on were in order, montmorillonite >
muscovite > silica > alumina. FBNZ as calculated in (tables 3.26-3.34) when applied to
the soils <strong>of</strong> varying organic content indicates that the <strong>sorption</strong> is associated with organic
content. The amount <strong>of</strong> fungicides adsorbed (%) was in the order soil 4 > soil3 > soil2 >
soil 1 when calculated (tables 3.26-3.34) again shows the relationship <strong>of</strong> ad<strong>sorption</strong> with
increase in the organic matter contents.
97

Table: 4.3: ko values for ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> <strong>of</strong> FBNZ on minerals <strong>and</strong> soils
FBNZ
Minerals & soils Ko ads K6 des
AlzOg 4.21 13.36
SiOz 6.61 I 1.15
Muscovite 16.01 16.51
Montmorillonite 655.11 7.71
Soil I 1.16 9.28
Soil2 2.61 tt.49
Soil 3 3.5 I 8.69
Soil4 10.49 7.38
4.2,3 N-( 111- benzi m id azol -2 -ylm ethyl)acetamide (ABNZ)
Ad<strong>sorption</strong> <strong>of</strong> ABNZ showed very high value for montmorillonite as compared
to rest <strong>of</strong> the minerals <strong>and</strong> soils (Fig3.27, Figs.3.33-3.36) showing strong ad<strong>sorption</strong> <strong>of</strong>
ABNZ on montmorillonite than muscovite <strong>and</strong> silica. In soils the order <strong>of</strong> ad<strong>sorption</strong> is
same as FBNZ while soils (l-3) show nearly similar values <strong>of</strong> Ko.
98

Table: 4.4: l ABNZ
> FBNZ in soil I from Tarnol, soil 2 from Multan, red soil 3 from Murree. Forest soil 4
from Ayubia has shown the order as carb > FBNZ which clearly indicates that
carbendazim was adsorbed more than other two fungicides <strong>and</strong> fungicide ABNZ was
adsorbed more than FBNZ fungicide. This behavior <strong>of</strong> ad<strong>sorption</strong> might be dependant
upon the size <strong>of</strong> the organic molecule as structural features <strong>of</strong> the adsorbent is one <strong>of</strong> the
main factors for K6 values.
4.3 De<strong>sorption</strong> <strong>studies</strong>
De<strong>sorption</strong> isotherm represents the microgram <strong>of</strong> the fungicide still adsorbed per
gram <strong>of</strong> soil as a function <strong>of</strong> equilibrium concentration after one ad<strong>sorption</strong> cycle.
Ad<strong>sorption</strong> was reversible but the de<strong>sorption</strong> values were constantly higher than those for
ad<strong>sorption</strong>. This is because the higher amount <strong>of</strong> carbendazim, FBNZ <strong>and</strong> ABNZ are not
retained after de<strong>sorption</strong> than that for ad<strong>sorption</strong> at equilibrium concentration. There are
many potential causing this difference, including size <strong>of</strong> the adsorbing -
sorbing organics,
particle size, diffusion effect <strong>and</strong> chemical thermodynamic effects. In addition to the
99

ad<strong>sorption</strong> <strong>of</strong> organics by surface owing to their low pH, the latter also promotes all,
77
cataly zes hydro lysi s reacti on <strong>of</strong> many organi c s
De<strong>sorption</strong> <strong>studies</strong> showed that the Tarnol, soil 1 lost nearly 54.49yo,35.780 ,
68.75% <strong>of</strong> the carbendazim, FBNZ <strong>and</strong> ABNZ. Soil 2 from Multan lost nearly 36.690 ,
43.06% <strong>and</strong> 55.30Yo <strong>of</strong> the carbendazim, FBNZ <strong>and</strong> ABNZ. Red soil 3 from Murree lost
nearly 47.14oA,15.06% <strong>and</strong> 16.95o/o <strong>of</strong> the carbendazim, FBNZ <strong>and</strong> ABNZ. Forest soil 4
lost nearly 75.6304,71.29% carbendazim <strong>and</strong> FBNZ after one de<strong>sorption</strong>.
The percentage <strong>of</strong> de<strong>sorption</strong> as compared to ad<strong>sorption</strong> is quite low found in
soil 4 shows that adsorbed fungicides were retained by the soil particles. The de<strong>sorption</strong>
isotherm <strong>of</strong> all the compounds were linear or <strong>sorption</strong> equilibrium distribution co-
efficient Ka (des), in (ml pg-r) values are constantly higher in soil minerals alumina, silica
<strong>and</strong> muscovite <strong>and</strong> soils (1-3) than those for ad<strong>sorption</strong> (tables 4.I-4.3). This could be
explained by possible hysteresis effect taking place during ad<strong>sorption</strong>, involving various
forces that caused the amount <strong>of</strong> fungicides retained to higher after de<strong>sorption</strong> than after
ad<strong>sorption</strong> at unit equilibrium concentration.
The relative high value <strong>of</strong> Ko (des) compared with Ko (uor) for alumina, silica,
muscovite <strong>and</strong> soils (1-3) shows ad<strong>sorption</strong> was reversible. The Ko (des) were lower in the
montmorillonite <strong>and</strong> soil 4 indicates they are more prone to release the adsorbed
fungicides.
Structure features, hyrophobicity, organic matter content <strong>of</strong> soil pH <strong>and</strong> solubility
are the main factors for K6 values <strong>of</strong> ad<strong>sorption</strong> <strong>and</strong> de<strong>sorption</strong> in all soils being
significantly higher for carbendazimthan other t-wo fungicides.
100

5.1 Conclusions
CONCLUSION
CHAPTER 5
As in above study FBNZ <strong>and</strong> ABNZ antifungal activities are greater than the
commercially used pesticides Benomyl which showed a possibility <strong>of</strong> replacement <strong>of</strong>
pesticide.
In all soils <strong>and</strong> minerals ad<strong>sorption</strong> increased with the increasing concentration <strong>of</strong>
the pesticides <strong>and</strong> no limiting ad<strong>sorption</strong> was observed within the concentration range
studied.
The order <strong>of</strong> carbendazim > ABNZ > FBNZ in all soils <strong>and</strong> minerals indicated
that carbendazim was adsorbed more in all <strong>of</strong> them <strong>and</strong> it is dependent on different
properties <strong>of</strong> the pesticide such as its tendency for binding to soil, its structural features,
hyrophobicity ,its vapor pressure, its water solubility, <strong>and</strong> its resistance to being broken
down over time.
Minerals
Sorption process was reversible in all minerals the de<strong>sorption</strong> values were constantly
higher than those for ad<strong>sorption</strong> in alumina, silica <strong>and</strong> muscovite which clearly indicated
that these minerals are more prone to release the adsorbed fungicides. This is verified by
the K6 values as the relative high value <strong>of</strong> K6 (des) c<strong>of</strong>iip?red with Ko (uor) were for
alumina, silica <strong>and</strong> muscovite except montmorillonite which has highly adsorbed all the
fungicides. While de<strong>sorption</strong> is quite low as compared to ad<strong>sorption</strong> in montmorillonite
which means fungicides are trapped between the layers <strong>of</strong> the mineral. Similarly the Ko
(des) were lower in the montmorillonite showing this mineral more prone to release the
adsorbed fungicides.
101

Soils
Sorption was reversible <strong>and</strong> the order <strong>of</strong> ad<strong>sorption</strong> was soil 4 > soil 3 > soil 2 >
soil l.Highest ad<strong>sorption</strong> on soil 4 is dependent on factors in the soil, such as its texture,
its ability to retain water, <strong>and</strong> the amount <strong>of</strong> organic matter contained in it, its pH etc.
Similarly the de<strong>sorption</strong> values were constantly higher than those for ad<strong>sorption</strong> in rest
<strong>of</strong> the soils this is verified by the K4 values as the relative high value <strong>of</strong> Ko (des) compffed
with Ko 1365; wer€ for these soils which indicated that these soils are more prone to release
the adsorbed fungicides <strong>and</strong> it predicts their mobility <strong>and</strong> leaching potential to the
ground water resulting in bioaccumulation.
Soil 4 having higher organic matter <strong>and</strong> low pH gave low value <strong>of</strong> ad<strong>sorption</strong> as
compared to de<strong>sorption</strong> indicated that it is reluctant to release the fungicide <strong>and</strong> it will
influence the uptake <strong>and</strong> metabolism <strong>of</strong> plant or microorganisms or other bioactivities in
soil.
Data limitations are still the major obstacle towards establishing clear environmental
trends in Pakistan. The environmental regulatory authorities <strong>of</strong> Pakistan can greatly
benefited from these preliminary <strong>studies</strong> to conduct such <strong>studies</strong> on larger scales.
Extensive educational programs are required for capacity building <strong>of</strong> farmers as low
level <strong>of</strong> knowledge <strong>of</strong> farmers requires the need for their proper awareness <strong>and</strong> training
to mitigate health <strong>and</strong> environmental risks associated with the proper selection, usage
<strong>and</strong> h<strong>and</strong>ling <strong>of</strong> pesticides.
This study can set the future course <strong>of</strong> action <strong>of</strong> different <strong>studies</strong> on pesticide in soils
<strong>and</strong> ground water in Pakistan. Results discussed in this part will provide a background to
prioritize pesticides or chemical groups that should be evaluated under various field
conditions with regard to their leaching potential to groundwater in different climates.
r02

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