MODIFIED--CYCLODEXTRIN FOR THE

PRECONCENTRATION OF SOME TOXIC METAL IONS AND

DITHIOCARBAMATE PESTICIDES
A
Thesis
Presented to the faculty of Physical Sciences of the
Punjabi University, Patiala
In Fulfilment of the Requirement For The
Degree of
DOCTOR OF PHILOSOPHY
IN
CHEMISTRY

Sandeep Jaggi
Department of Chemistry
Punjabi University, Patiala-147002
2014
DEPARTMENT OF CHEMISTRY
PUNJABI UNIVERSITY,

PATIALA-147002

CERTIFICATE
This is to certify that the thesis entitled MODIFIED--CYCLODEXTRIN FOR

THE PRECONCENTRATION OF SOME TOXIC METAL IONS AND

DITHIOCARBAMATE PESTICIDES embodies the work carried out by Sandeep
Jaggi himself under my supervision and that it is worthy of consideration for the award of
Doctor of Philosophy in Chemistry.

Dr. Usha Gupta

Research Supervisor
Assistant Professor
Department of Chemistry,
Punjabi University, Patiala

------ ------- ------Day Month Year

DEPARTMENT OF CHEMISTRY
PUNJABI UNIVERSITY,

PATIALA-147002

DECLARATION
I,

hereby

affirm

that

the

work

presented

in

this

thesis

MODIFIED--

CYCLODEXTRIN FOR THE PRECONCENTRATION OF SOME

TOXIC METAL IONS AND DITHIOCARBAMATE PESTICIDES is
exclusively my own and there are no collaborators. It does not contain any work for which a
degree / diploma has been awarded by any other University/Institution.

Sandeep Jaggi

------- ------- -------Day Month Year

-CountersignedDr. Usha Gupta

Research Supervisor
Assistant Professor
Department of Chemistry,
Punjabi University, Patiala

------ ------- ------Day Month Year

S. No.
CHAPTER-1

CONTENTS

Page No.

INTRODUCTION

1-34

1.1 A Briefing about Cyclodextrins

1.2 Introduction to metals & their Toxicity Profile
1.3 Introduction to dithiocarbamate pesticides
1.4 An Introduction to spectrophotometry
1.5 Introduction to Reagents
CHAPTER-2

LITERATURE REVIEW

35-65

2.1 Review of various preconcentration methods for metal ions

2.2 Various Solid phase extraction sorbents
2.3. Review of various preconcentration methods for DTC pesticides
CHAPTER-3

SYNTHESIS AND CHARACTERIZATION

66-90

OF -CYCLODEXTRIN POLYMER
3.0 Introduction to -Cyclodextrin polymers
3.1 Synthesis of -Cyclodextrin polymers
3.2 Characterization of synthesized polymers
CHAPTER-4

PRECONCENTRATION OF METAL IONS

91-230

USING PAN MODIFIED -CDP

4.0 Introduction
4.1 Preconcentration of Cu(II) using -CDP-PAN polymer
4.2 Preconcentration of Co(II) using -CDP-PAN polymer
4.3 Preconcentration of Ni(II) using -CDP-PAN polymer
4.4 Preconcentration of Fe(III) using -CDP-PAN polymer
4.5 Preconcentration of Pb(II) using -CDP-PAN polymer
4.6 Preconcentration of Cd(II) using -CDP-PAN polymer
4.7 Preconcentration of Hg(II) using -CDP-PAN polymer
4.8 Preconcentration of Zn(II) using -CDP-PAN polymer
4.9 Preconcentration of In(III) using -CDP-PAN polymer
CHAPTER-5 PRECONCENTRATION OF DITHIOCARBAMATE 231-281
PESTICIDE USING PAN MODIFIED -CDP
5.0 Introduction

5.1 Preconcentration of Zineb using -CDP-PAN polymer

5.2 Preconcentration of Ferbam using -CDP-PAN polymer
5.3 Preconcentration of Maneb using -CDP-PAN polymer
References

282-298

Apart from the efforts of oneself, the success of any project depends
largely on the encouragement and guidelines of many others. I take
this opportunity to express my gratitude to the people who have
been instrumental in the successful completion of this project. I
would like to show my greatest appreciation to Dr. Usha Gupta, my
Research Supervisor I cant thank her enough for her tremendous
support and help. I feel motivated and encouraged every time I
attended her meeting. Without her encouragement and guidance
this project would not have been materialized. I am grateful to her
for constant support and help.
I am highly thankful to Prof. Raman K. Verma, Chairperson,
Department of Chemsitry, Punjabi University, Patiala for support
and encouragement during this entire project.
Indebtness is also due to former chairpersons, Prof. Balbir Kaur
and Prof. Baldev Singh for providing necessary research facilities.
I am highly thankful to laboratory and non teaching staff of
Department of Chemistry, PUP for all kind of help.
This thesis is the end of my journey in obtaining my Ph.D. I have
not traveled in a vacuum in this journey. This thesis has been kept
on track and been seen through to completion with the support and
encouragement of numerous people including my well wishers and
dear friends especially Cammy, Aman Sidhu, Aman Samrao, Nishu,

Rajesh, Subhash, Balwinder, Ella and Vikas. At the end of my thesis

I would like to thank all those people who made this thesis possible
and an unforgettable experience for me.

Sandeep Jaggi

With the grace

of Shri Krishna
who is the Lord
of Mighty Lords
whose glory I
shall forever
applaud, master
of this universe,
true bliss,

redeemer, most
compassionate
& most merciful
of all

CHAPTER-1
INTRODUCTION
1.1 Cyclodextrins
1.1.1 History of Cyclodextrins
1.1.1.1 Discovery Period
The first paper was published in 1891 by Villiers that reported the formation of some
unidentified crystalline substance during fermentation of starch [1]. Villiers, the French
author, assumed that this substance is some kind of cellulose and named it cellulosine. An
Australian Microbiologist, Franz Schardinger about 15 years later, whilst studying those
microorganisms which play a role in the deterioration of foods, isolated a microorganism
(named Bacillus macerans) which produced reproducibly two distinct crystalline substances
when cultivated on starch medium [2]. Because most of their properties were similar to the
already known partial degradation products of starch, he named them as -dextrin and dextrin Freudenberg and his co-workers elucidated the cyclic structure of these two dextrins
in the mid 1930s. This period from 1891-1936 is called the discovery stage in the history of
CDs.

1.1.1.2 The exploratory period from 1936-1970

After 1930s, Freudenberg and his co-workers came to the conclusion that the crystalline
Schardinger dextrins are built from maltose units and contain only -(1, 4) glycosidic
linkages [3]. In 1950, -CD was discovered and its structure elucidated.
Freudenberg, Cramer and Plieninger were granted a patent in 1953 [4]. D. French published
the first fundamental review on cyclodextrins 1957 [5].

1.1.1.3 The utilization period: from 1970-onward

The first international symposium on CDs was organized in 1981 [6]. An international CD
symposium has been organised every 2nd year from 1984 onwards. By the end of 2003, the
total numbers of CD related papers/publications were over 26000. P. R. Sundrarajan and V. S.
R. Rao demonstrated by conformation energy map calculations that CDs with less than six
members cannot be formed due to steric considerations [7]. F. V. Lichtenthaler and S. Immel

coined the term cyclodextrin as a generic nomenclature for all the Cyclo-oligosaccharides
depending upon the numbers of glucose units present in a ring [8].
The spectacular development of CD technology relies on a series of reasons such as:
They are natural products, produced form a renewable natural material (starch) by a
relatively simple enzymatic conversion;
They are produced in 1000 tons/yr amounts by environmental technologies;
Their initial high price have dropped to levels where they become acceptable for most
of the industrial purposes;
Through their inclusion complex forming ability, important properties of the
complexed substances can be modified significantly. This unprecedented molecular
encapsulation is utilized in many industrial products, technologies and analytical
methods;
Any of their toxic effects is of secondary character and can be eliminated by selecting
the appropriate CD type, derivative, or mode of application;
CDs can consequently be consumed by humans as ingredients of drugs, foods and
cosmetics.

1.1.2 Structural features of Cyclodextrins (CDs)

Cyclodextrins comprises a family of three well known industrially produced major, several
rare and minor cyclic oligosaccharides. The three major CDs are crystalline, homogeneous,
nonhygroscopic substances, which are torus like macro rings built up from gluocopyranose
units. The -cyclodextrin (Schardingers -dextrin, cyclomaltohexose, cyclohexaglucan,
cyclohexaamylose, -CD, ACD, C6A) consisting six gluocopyranose units, -cyclodextrin
(Schardingers -dextrin, cyclomaltoheptaose, cycloheptaglucan, cycloheptaamylose, -CD,
BCD, C7B) consisting of seven gluocopyranose units and -cyclodextrin (Schardingers dextrin, cyclomaltooctaose, cyclooctaglucan, cyclooctaamylose, -CD, GCD, C8A)
consisting of eight gluocopyranose units.

1.1.3 Shapes and size of Cyclodextrins (CDs)

Cyclodextrins (CDs) have been described as seductive molecules, appealing to investigators
both in pure research and applied technologies. Cyclodextrins have truncated cone or bucket
shaped structure (Fig. 1.1.1). CDs are water soluble, cyclic, non-reducing oligosaccharides
consisting of D-(+)-gluocopyranose units linked through -(1, 4) glycosidic linkages. The
major and most common three cyclodextrins, -cyclodextrin, -cyclodextrin and cyclodextrin consist of six, seven and eight D-(+)-gluocopyranose units, respectively. Native
CDs are crystalline, non-hygroscopic, homogeneous substances that are torus (bucket)

shaped. In Cyclodextrins, the glucose units adopt 4C1 chair conformation and orient
themselves so that the molecule forms a toroidal truncated cone shaped structure. As a
consequence of the 4C1 conformation of the gluocopyranose units, all secondary hydroxyl
groups of gluocopyranose units are situated on one edge of the ring, where as all primary
hydroxyl groups are placed on the other edge. These two edges of the ring are called
secondary and primary face respectively. The ring of gluocopyranose units in CDs is a
conical cylinder which is frequently characterized as a doughnut or wreath shaped truncated
cone. The CD cavity is lined by the hydrogen atoms and glycosidic oxygen bridges. The nonbonding (lone pair of electrons) electron pairs of glycosidic oxygen bridges are directed
towards the inside of the cavity, producing a high electron density and giving it Lewis base
characters [9]. The C-2-hydroxyl group of one gluocopyranose unit can form a hydrogen
bond with C-3-hydroxyl group of the adjacent gluocopyranose units. In the -CD molecule, a
complete secondary belt is formed by these H-bonds; therefore, -CD is a rather rigid
structure. This intramoleculer H-bond formation is cause for the lowest water solubility of CD of all CDs. The H-bond belt is incomplete in -CD molecule, because one
gluocopyranose unit of six is in a distorted position. As a result, instead of the six possible Hbonds, only four can be formed at a time. The -CD is a non-planer, more flexible structure,
that is why, it is more soluble of three CDs. Important physical properties of three major and
most common cyclodextrins have been intensively studied (Table 1.1.1). Cyclodextrins are
not hygroscopic, but form stable hydrates. A quasielectron neutron scattering study on CD.6H2O, -CD.7H2O and -CD.8H2O showed that 2, 6 and 8.8 water molecules are
included in the -CD, -CD and -CD cavity, respectively.

Fig. 1.1.1 Schematic Structure of native -, - and -cyclodextrins

Table 1.1.1 Some chemical and physical properties of three major cyclodextrins
Cyclodextrin Type
Number of glucose

-CD
6

-CD
7

-CD
8

units
Mw(Da)
Solubility in water

972
14.5

1135
1.85

1297
23.2

(g/100 mL, 298K)

[]D at 298 K
Cavity diameter (pm)
Height of torus (pm)
Diameter of outer

150 0.5
470-530
790 10
1460 40

162.5 0.5
600-650
790 10
1540 40

177.4 0.5
750-830
790 10
1750 40

periphery (pm)
Melting point (0C)
Crystal water (wt. %)
Water molecules in

255-260
10.2
6

255-265
13.2-14.5
11

240-245
8.13-17.7
17

Hexagonal

Monoclinic

Quadratic

plates
119
4.23
3.00

parallelograms
117.7
4.39
2.86

prisms
112.6
4.48
2.81

cavity
Crystal Form

C1 -O4-C4 angle( )
O4-O4 distance Ao
O2-O3 distance Ao

Da: Dalton; A0: Angstrom; pm: picometer.

1.1.4 Inclusion complexes of Cyclodextrins (CDs)

The most important, unique and exceptional property of CDs is the formation of inclusion
complexes in solution as well as in crystalline solid form with wide varieties of molecules
depending upon the size of guest molecules. This phenomenon is called molecular
encapsulation. Inclusion complexes are entities comprising two or more molecules; the

host includes a guest molecule, totally or in part, by only physical forces, that is, without
covalent bonding. CDs are typical host molecules and may include a great variety of
molecules having the size of one or two benzene rings, or even compounds, which have a
side chain of comparable size, to form crystalline inclusion complexes.

1.1.4.1 Mechanism of Inclusion complex formation

In an aqueous solution, the slightly apolar cyclodextrin cavity is occupied by water molecules
that are energetically unflavored (polar-apolar interaction). Therefore, water molecules can be
readily substituted by appropriate guest molecules (Fig. 1.1.2) and (Fig. 1.1.3). The
cyclodextrin is the host molecule and part of the driving force of the complex formation
is the substitution of the high enthalpy water molecules by an appropriate guest molecule.
One, two or three CD molecules can trap one or more guest molecules. Most frequently, the
host guest ratio is 1:1. This is the simplest and most frequent case. However, 2:1, 1:2 and 2:2,
or even more complicated associations, and higher-order equilibrium exist. The inclusion
complexes formed can be isolated as stable amorphous or microcrystalline substances. The
association and dissociation of CD-guest complex is governed by a thermodynamic
equilibrium (Eq. 1.1.1), which is characterized by the stability constant, K (Eq. 1.1.2).

The driving force for inclusion complexation is not fully understood. The following factors
have been considered for the formation of an inclusion complex.
Substitution of the energetically unfavored-apolar interactions between the included
water molecules and CD cavity on one hand, and between water molecules and the
guest on the other hand by the more favored apolar-apolar interactions between the
guest and CD cavity and polar-polar interaction between bulk water and the released
cavity-water molecules;
CD-ring strain release on complexation;
Vander walls interactions and

 In the case of some guest, hydrogen bonding between host and guest.
Inclusion complex of Cyclodextrins with different substrates are shown below (Fig. 1.1.4)
and (Fig. 1.1.5).

Fig. 1.1.2 Schematic representation of the formation and dissociation of the

host (cyclodextrin) and guest (resorcinol) inclusion complex. The formed
guest-host inclusion complex can be isolated as a microcrystalline powder.

Fig. 1.1.3 Formation of Host-guest inclusion complex of Cyclodextrin and PAN

also showing primary and secondary faces of Cyclodextrin

Fig. 1.1.4 Inclusion complex of Cyclodextrins with various substrates

Fig. 1.1.5 Inclusion complex of Cyclodextrins with various substrates showing

(1:1) stoichiometry

1.1.5 Synthesis of Cyclodextrins (CDs)

The synthesis of cyclodextrins involves treatment of ordinary starch with easily available
enzymes. In nature, the enzymatic digestion of starch by cyclodextrin glycosyltransferase
(CGTase) produces a mixture of -, - and -cyclodextrins (CDs). Cyclodextrins are obtained
in a large scale by enzymatic degradation induced by bacterial strains such as Bacillus
macerans (Fig. 1.1.6).

Fig. 1.1.6 Schematic representation of synthesis of Cyclodextrins (CDs) based

on enzymatic degradation of starch by CGTase enzyme

1.1.6 Cyclodextrin polymers

Cyclodextrin polymers reserve a special position amongst the derivatives of the cyclodextrins
(CDs). -Cyclodextrin polymers (-CDP) help in biding with the substrates having two or
more guest parts more efficiently [10]. This increased inclusion capacity is observed due to
the co-operativity effect caused by adjacent -CD moieties in polymeric back bone [11-12].
When two or more cyclodextrins are covalently linked they are known as polymers. The
cyclodextrins fixed into polymeric structures behave differently from their monomeric
derivatives. Cyclodextrin polymers can be classified as one of two types; those that are
soluble in water and those that are water insoluble. By varying the reaction conditions, either
water soluble or insoluble polymers can often be obtained. A considerable amount of work
has been done using cyclodextrins to synthesize polyesters, polyurethanes and various other
types of polymeric materials. Much of this work has been completed in the last 10-20 years
with the majority of the work dealing with both native cyclodextrins and their derivatives. A
variety of polymers obtained by more exotic routes than simple polycondensation, radical or
even suspension reactions of functionalities attached to cyclodextrin are known. Girek et al.
[13] suggested two ways in which cyclodextrins can be polymerized, where one is to attach a
cyclodextrin molecule as a pendant group on another polymer chain. Polymers with
cyclodextrin pendants are usually prepared by radical polymerization of the functional
cyclodextrin monomers such as acryloyl cyclodextrin. These monomers are further
copolymerized with other compatible monomers such as acryl amide. The second type of
polymerization is to react cyclodextrin molecules with bifunctional agents. The commonly
used agent is epichlorohydrin, which result in both water soluble and water insoluble
polymers. Other agents such as dihalogenated hydrocarbons and dicarboxylic derivatives are
also used. These nucleophilic substitution reactions with bifunctional agents usually occur
under strong alkaline conditions in order to deprotonate the hydroxyl groups of the
cyclodextrin.

1.1.6.1 Water soluble cyclodextrin polymers

Water soluble polymers have been the subject of many investigations. These polymers have a
wide variety of potential applications such as controlling the release of a soluble substance
across a membrane and partitioning of organic compounds in an aqueous two-phase system.
As with other cyclodextrin-based compounds, the usefulness of these polymers lies mainly in
their ability to form inclusion complexes with lipophilic guests. The polymeric form can

increase the stability constant of the complexes. Renard et al. have investigated the
relationship between preparation conditions and properties of the water soluble cyclodextrin
polymers [14]. The polymers obtained were characterized by physicochemical measurements.
The preparation was achieved by reacting -cyclodextrin with epichlorohydrin in an alkaline
medium by a two-step procedure. Several reaction parameters were considered to develop the
conditions of a reproducible synthesis. For example, the size of the reaction vessel, the speed
of the stirrer and the volume of the reaction mixture were kept constant. These parameters
have a strong influence on the preparation of water soluble -cyclodextrin-epichlorohydrin
polymers. Again, the use of lower mole ratio of epichlorohydrin/-cyclodextrin gave water
soluble polymers even for longer reaction times. It has been observed that at
epichlorohydrin/-cyclodextrin ratios greater than 7, insoluble polymers are usually formed.
Szejtli also gives conditions by which water soluble polymers are obtained namely short
reaction times and lower concentrations of cyclodextrin [15].

1.1.6.2 Water insoluble cyclodextrin polymers

Although water-insoluble polymers have not been extensively investigated, some examples
are known. Insoluble products can often be obtained by increasing the ratio of
cyclodextrin/crosslinking agent in the polymerization process. These types of polymers
usually have a high water sorption capability that tends to make them swell in an aqueous
medium. Polymers that are insoluble can either be crosslinked or linear. One example of this
class of polymer is the polyurethanes. Polyurethane resins containing cyclodextrin units as
specific sorption sites were prepared by crosslinking -cyclodextrin with diisocyanates.

1.1.6.3 Why Cyclodextrins Polymers (CD-Polymers)

CD polymers have several added advantages over other solid supports (Fig 1.1.7). These are
enlisted as:

Environmentally Benign
Thermally stable
Facile one pot synthesis
Stable over a wide range of pH
Applicability in different areas of research
Re-usable

1.1.7 Applications of Cyclodextrins polymers (CDPs)

Polymers of cyclodextrin have very diverse applications, some of which have been
highlighted in the previous sections.
(i)

Sebille et al. reported on the properties of chemically modified cationic cyclodextrin-epichlorohydrin polymer as a chiral support. The polymer was used
in liquid chromatography for enatioselective separations. In food, the

(ii)

epichlorohydrin polymer of cyclodextrin plays a major role [16].

Shaw et al. Used -cyclodextrin-epichlorohydrin polymer to reduce the bitterness
components in grape fruit and navel orange juices in a fluidized bed process.
These polymers were compared with neutral XAD resins used under similar
fluidized bed conditions. It was found that cyclodextrin polymers and XAD resins

(iii)

show effective debittering potential to acceptable levels [17].

Baille et al prepared poly-(-cyclodextrin) (PCD) resins by Crosslinking cyclodextrin with different amounts of epichlorohydrin in which some
cyclodextrin hydroxyl groups were functionalized with alkyl quaternary
ammonium groups. These polymers were used to bind several bile salts from
phosphate buffer solutions. Aminated PCD resins have a higher binding capacity

(iv)

for bile salts [18].

Liu et. al., (2005) Synthesized a novel reagent by reaction of -Cyclodextrin
polymer (-CDP) with 2-DHPH(2,4-dihydroxyacetophenone phenylhydrazone)
and exploited its use in the determination of Cd(II) in different water samples

(v)

[19].
Gao and Zhao synthesized a polymer by the supramolecular reaction of cyclodextrin crosslinking polymer with 1-(2-pyridylazo)-2-naphthol (PAN). The
polymer was used to prepare electrorheological materials of an inclusive complex,

(vi)

named -cyclodextrin-PAN polymer [20].

A porous tubular ceramic membrane impregnated with -cyclodextrin polymer
used to obtain a chiral-selective membrane, was prepared by Krieg et al [21]. This
membrane was evaluated in terms of the effectiveness of impregnation as well as
the ability to separate the enantiomers of the racemic pharmaceutical
chlorthalidone.

1.1.8 Applications of CDs

Cyclodextrins (CDs) have wide range of applicability in different fields. Some of which are
discussed below [22-28].

(a) CDs in Drug Delivery

The following examples illustrate the utility of CD complexation in drugs:
(i)

Garlic oil smells very bad and loses its active ingredients contents rapidly.

(ii)

Cyclodextrin complexation is the ideal solution of the problem.

Cetrizine is a bitter antiallergic drug. Its bitter taste can be masked using -

(iii)

cyclodextrin cetirizine complex.

Ibuprofen in CD complexed form is appropriate for production of a table

(iv)

formulation, which is devoid of bitter taste.

The dextrametamorphan-bromide is a very bitter taste drug used as a peadiatric

(v)
(vi)

drug. Its very bad taste can be reduced by complexation with -CD.
Solubility of Itraconazole can be increased using hydroxypropyl--CD complex.
Effectiveness of herbicides, fungicides and insecticides can be enhanced by

(vii)

complexation with CDs.

The pernitro -CD and its complex with nitramine is an excellent missile
propellent.

(b) In textile industry

The CDs play a significant role in the textile industry. They can be used to remove surfactant
from the washed textile material, textile finishing, bonding the chemical on the fibres in order
to increase wettabiity, include fragrance and removing the insects etc.
(i)

Monochlorotriazinyl group (MCT) is used for textile finishing. This anchor group

(ii)

reacts with the cellulose hydroxyl group, forming permanent covalent bonds.
For inflammatory treatment: the intelligent textiles offer favourable solutions that
remove some of the inconveniencies of the traditional treatments, such as:
sensitivity of the certain patients to the medicine; administration by the mouth;
omission in the case when the children and old people forget to take medicine. A
bandage is able to gradually release the necessary medicine at the inflamed place
avoids the above mentioned difficulties. The structure of such bandage consists of
an absorbing matrix such as cotton cloth, which contains an anti-inflammatory
medicine for example, sodium diclofenac included in the cyclodextrin linked to
the textile material by means of a reticulating agent, viz., dimethyldihydroxy
ethylene urea (DMDHEU). The bandage is executed in two stages: medicine
complexing with cyclodextrin, followed by attaching the complex to cotton using
the reticulating agent. If the textile is impregnated in a vat containing ethanol, the

rate of medicine release increases at the beginning, when the inflammation is

severe. But if the bandage is not treated with ethanol, the initial release of
medicine is slow. At the same time, the increase of medicine release rate is not
proportional to the initial concentration.

(c) Masking unpleasant odour

Complexation ability of -CD can be used to mask unpleasant flavors.
(i)

Chamomile extracts have an antiphlogistic, bacteriostatic and wound healing

effect. These formulations often have an intense and unpleasant odor. This odor is
reduced by complexation with cyclodextrins without affecting the anti-

(ii)

inflammatory activity of chamomile.

Mercapto compounds are used in waving lotions. Due to mercapto compounds, an
extremely unpleasant odor is generated during application. This odor can be

(iii)

eliminated by complexation with cyclodextrins.

Glutathione shows various physiological activities. For example, it inhibits the
melanin pigment formation. Therefore, it is used for skin whitening and skin
improving effects. But glutathione generates an offensive odor upon use in the
cosmetic formulations. However, glutathione complex with cyclodextrin is free of

(iv)

odor but has the same effect on skin as glutathione.

Dihdroxyacetone (DHA) is used as tanning agent. It is not stable in aqueous
solution. It also has an unpleasant odor which is difficult to be masked by using
perfumes. This odor vanishes using CD-complex. The slow release of
dihdroxyacetone (DHA) from the complex results in the more uniform tanning of
the skin.

(d) Solubilization of the guest molecules.

A large number of cosmetic components are nearly insoluble in water. All these chemical
substances are able to form inclusion complexes with CDs. As a result, these complexes
are more soluble compared to pure compounds. The following examples illustrate this
effect.
(i)

Menthol acts as a cooling agent in different cosmetic products. But menthol is

only slightly soluble in water. However, menthol-CD complex is freely soluble in

(ii)

water.
Retinol is used in topical anti-ageing formulations. It reduces wrinkles and
supports the restoration of UV damaged tissues. But, UV-light and atmospheric
oxygen induces the chemical oxidation of retinol. Thus, during oxidation some
peroxidic toxic intermediates are formed. Low solubility of retinol in aqueous

media is also a problem. Retinol forms complex with cyclodextrins that are stable
(iii)

in the presence of light and oxygen without any effect in its activity.
Cyclodextrins are also used to increase the solubility of substances secreted by the
skin. Thus, CDs find their applicability in products for skin cleaning. They are
able to complex and dissolve skin fat. The resulting fat-CD complex can be easily

(iv)

removed from the skin.

Salicylic acid is used for cleaning of the skin. Its action is mainly antibacterial and
keratolytic. The solubility of the acid or its derivatives in aqueous solution is low.
The complex with cyclodextrin is much more soluble and the irritating occurring
with the free acid are prevented due to better homogeneity. Moreover, as a
complex the disinfectant, keratolytic and bacteriostatic activities are also

(v)

enhanced.
Triclosan is used as a topical antiseptic and disinfectant in many personal care and
cosmetic products. But it is insoluble in aqueous solution. However, cyclodextrintriclosan complex is soluble in water giving a clear solution.

(e) Protection of the guest molecules

(i)

Hydroquinone (HQ) is used in skin whitening formulations. In aqueous solution

hydroquinone is stable in limited pH range. Therefore stabilizers are used. But as a
cyclodextrin-hydroquinone complex, the oxidation of hydroquinone is prevented
and has a greater stability. Moreover, the depigmentation property is also

(ii)

enhanced.
Kojic acid (KA) is another substance used as a whitening agent in cosmetic
creams. Its use is limited because it is labile when exposed to light or heat. Due to
decomposition, it turns yellowish brown. But as a CD complex, it has an improved
stability. Also, the skin whitening properties of Kojic acid are enhanced as a

(iii)

cyclodextrin complex.
Peroxyacetic acid (PAA) forms solid complexes with - and -cyclodextrin. These
stable powders are easy to handle and can be used in cosmetic formulations. They
also act as mild oxidants with significant disinfectant properties.

As illustrated by the above examples, a guest complexed with CD can be shielded from the
attack by the reactive species. But if the guest is large size molecule then only a portion of
that molecule will be included with in the CD cavity. Only the portion of the molecule that is
included in the CD cavity would be shielded from chemical attack. This concept can be
utilized in many ways for highly selective synthesis procedures. CDs can also be used as
phase transfer catalyst to transfer reactive components between two immiscible liquids.

Fig. 1.1.7 Schematic diagramme showing applications of CDs in different fields

1.2. Introduction to metal ions

Metals are inorganic substances that occur naturally in geological formations. They are
integral part of our environment. Some metals are essential for our life and are naturally
available in our food and water. Concentrations of metals that are too low may lead to health
problems on the other hand an excess is toxic to plants, animals and human alike.
Metals may be classified into four sub types:
1. Macrominerals are those which are needed in large amounts such as Ca, Mg, Na, K,
Cu, Zn, Fe and S etc.
2. Required Trace minerals include Mn, Cr, Se, B and Mo.
3. Possibly required minerals include Ru, Sn, Au and Ag.
4. Toxic metals are Hg, Pb, As, Sb and U along others.

1.2.1 Exposure to Toxic Metals

Toxic metals are trace elements that form poisonous soluble compounds when considered in
abnormally high toxic doses. Today mankind is exposed to the highest levels in recorded
history of Pb, Hg, Al, Cu, Ni, Sn, Sb, Bi and V. Levels are up to several thousand times
higher than in primitive man. Trace amounts of metals enter our water bodies supplies
naturally as rain percolates through rock, dissolving minute quantities into the water. This
water enters larger water bodies which we use as resource of drinking water and then they
enter our bodies via food, drinking water and air.

1.2.1.1 Modern Diets and Toxic Metals

The danger of toxic metal is greatly aggravated today by the low mineral content of most of
our food supply. An abundance of vital minerals protects our body against toxic metals.
Essentials metals protect body and compete against the toxic metals for absorption and
utilization in enzymes and other tissue structures. However, when food is low in essential
minerals, the body absorbs and makes use of more toxic metals. Causes for low mineral
content of almost all agricultural products are primarily:
Hybrid crops are grown for production or disease resistance, rather than superior nutrition.
Superphosphate fertilizers produce higher yields by stimulating growth, but do not provide all
the trace elements.
Monoculture, the growing of just one crop over and over again on the same land, eventually
depletes the soil. Toxic sprays damage soil microorganisms needed to help the plants to
absorb minerals from soil.

1.2.1.2 Food Sources

Food grown near highways or downwind of the industrial plants may contain Pb [29] and
other toxic amounts of metals. Even organic home gardens may be contaminated if, for
example, old house paint containing Pb leaches Pb into the soil. Sprays and insecticides still
often contain Pb, Hg and other toxic metals. Pesticides used on fruits, vegetables and many
other foods may contain As, Pb, Cu, Hg and other toxic metals.

1.2.1.3 Drinking water

This is the most common source of toxic metals for most people. Al, Cu and many other toxic
chemicals are added to many municipal water supplies. Al allows dirt to settle out of the
water, while Cu kills algae that grows in reservoirs. Wells and even municipal water may also
contain some Pb, As and other undesirable metals. Galvanized and black plastic pipes can be
an important source of Zn and Cd. Lead Soldered pipes and copper pipes may increase these
metals in the drinking water if the water is soft. It is an uncommon problem in hard water
areas. Hydrofluorosilicic acid, the chemical often used to fluoridate drinking water, is a
smokestack waste that contain Pb. Hg, Cd, As, Al, benzene (C 6H6) and radioactive waste
material.

1.2.1.4 Airborne Sources of Toxic Metals

Most toxic metals are effectively absorbed by inhalation. Auto and particularly aircraft
exhaust, industrial smoke and products form incinerators are among the airborne sources of
toxic metals and other chemicals. Hg and coal-fired power plants burnt high in the
atmosphere and aircraft fuel deposits everywhere and affects everyone on earth. Burning coal
can release Hg, Pb and Cd among other metals. Iranian and Venezuelan oil are high in V.
Tetraethyl lead [(C2H5)4Pb] was added to gasoline for many years. Residues are present on
pavement and may settle on buildings, cropland and elsewhere. Today, Mn is added to
gasoline. Incineration of electronic parts, plastics treated fabrics and batteries release all the
toxic metals into the air. The use of scrubbers and newer methods of very high temperature
incineration are much better. Cigarette and tobacco smoke are high in Cd, found in cigarette
paper [30, 31].

1.2.1.5 Medications
Many patented prescriptions and over-the-counter drugs contain toxic metals. Thimerisol, a
mercury containing preservative, is used in some vaccines, including all flu shots. Thiazide

diuretics such as Maxzide, Diazide and many others contain Hg. Antacids such as Gelusil,
Digusil and many others are very high in Al content.

1.2.1.6 Direct Skin Content

Almost all anti-perspirants and many cosmetics contain Al. Dental amalgams contain Hg, Cu
and other metals. Dental bridges and other appliances often contain Ni. Soaps, body lotions
and creams often contain toxic compounds. A few hair dyes contain Pb. Selsun Blue shampoo
contains Se that is quite toxic in high doses. Household lawn and garden chemicals may
contain Pb, As and other compounds. Mercury treated seeds and As treated wood are other
common sources of toxic metals.

1.2.2 Toxic Metals Dangers

Toxicity is described as acute, sub-acute or chronic, according to the level and duration of
exposure. Acute toxicity, which is a measure of the hazard to man and animal following a
single exposure to toxicant, is usually expressed as the dose in milligrams of the chemical per
kilograms of body weight of the test animal. This is referred to as the lethal dose; thus, the
LD50 is the dose which will kill 50% of a given population. Metals are systemic toxins with
specific neurotoxic, nephrotoxic, foetotoxic and teratogenic effects. Breathing heavy metal
particles, even at levels well below those considered non toxic, can have serious health
effects. All aspects of animals and human immune system function are compromised by the
inhalation of metal pollutants. Toxic metals can also increase the acidity of the blood. The
biological half-lives for heavy metals are variably long; the half life for Cd in kidneys is
decades. Most toxic metals are readily transferred across the placenta, found in breast milk,
and are well known to have serious detrimental effects on behaviour, intellect and the
developing nervous systems in children. Heavy metals alter pro-oxidant/antioxidant balance
and bind to free sulfhydryl groups, resulting in inhibition of glutathione metabolism,
numerous enzymes and hormone function. Nutritionally, toxic metals are directly antagonistic
to essential trace elements and compete with nutrient elements for binding sites on transport
and storage proteins, metalloenzymes and receptors. Pb and Hg are well known for their
direct, destructive effects on neuronal functions, while Cd has direct adverse effect on cells in
the arterial wall. Chronic, low level Hg exposure is a problem that goes well beyond the
controversial issue of the dental amalgams. Two primary mechanisms for the toxic effects of
Hg are:

1. Hg is a pro-oxidant which catalyses the production of peroxides and enhances the

subsequent formation of hydroxyl radicals and lipid peroxides.
2. Hg interferes with the bodys capacity to quench highly reactive oxygen species.

Table 1.1.2 Sources, uses and harmful effects of some toxic metals
Sr.
No.
1.

Metal

Sources

Uses

Antimony (Sb)

Antimony
compounds are
used in flame
proofing
compounds,
batteries and as
an alloy for the
leads hardness

2.

Cadmium (Cd)

3.

Cobalt (Co)

Semiconductor
industry in
production of
diodes,
plumbing,
soldering,
antifriction
alloys and
antiprotozoan
drugs
By-product of
Zn, Pb and Cu
extraction,
battery
manufacturing,
volcanoes and
inhaled tobacco
smoke
As a by-product
of Ni and Cu
mining and
refining, central
component of
the vitamin
cobalamin or
vitamin B12

4.

Copper (Cu)

5.

Iron (Fe)

Natural
resources like
forest fires and
volcanoes.
Human activities
like mining and
phosphate
fertilizer
production

Ores such as
hematite,

Accumulation
site
Bone marrow

Harmful effects
on the body
Excess of Sb
leads to
pneumonitis,
fibrosis and
carcinomas

Ni-Cd batteries,
pigments,
stabilizers for
plastics,
electroplated
onto steel, silver
solder

Liver, bones,
testes, kidney
and
cardiovascular
system

Used in making
jet engines,
permanent
magnets,
electroplating
industries,
purification of
histidine-tagged
fusion proteins
In electrical
wiring, electrical
equipment,
alloys, in
insecticides,
fungicides and
herbicides

Lungs

Causes
pneumonitis,
cerebral and
cerebellar
damage, lung
cancer and renal
toxicity
Disease: Itai-Itai
Dilated
cardiomyopathy
and
pneumoconiosis

Cargo ships,
food containers,

Stomach and
small intestine
and liver

Causes hepatic
and renal
damage. Cu
poisoning also
leads to
haemolytic
anaemia and
centrilobular
hepatic necrosis.
Disease: Wilsons
Disease
Vomiting,
gastrointestinal

magnetite and
mining

steel vehicles

6.

Zinc (Zn)

Industrial
activities such as
mining, smelting
and steel
processing

In galvanizing
Fe, alloys,
pigment in
paints, printing
inks.

7.

Mercury (Hg)

Breakdown of
minerals, fossil
fuel combustion,
mining,
smelting, solid
waste
combustion and
fertilizers

In barometers,
manometers,
thermometers,
liquid electrode,
insecticides, rat
poison,
disinfectant,
skin ointment.

8.

Manganese
(Mn)

Mining and
mineral
processing,
municipal waste
water discharge,
sewage sludge,
fossil fuel
combustion and
volcanoes.

In low cost
stainless steel,
disinfectant,
fertilizers and
ceramics.

Muscles and
brain

9.

Nickel (Ni)

Mining and
refining,
stainless steel,
Ni-Cd batteries,
electroplating,
electro refining
and welding.

Coins,
rechargeable
batteries,
stainless steel,
electroplating,
pigments for
paints or
ceramics.

Kidney, liver
and lungs

Brain, pituitary
gland, thyroid
and adrenals

haemorrhage,
metabolic
acidosis, hepatic
cirrhosis
Causes vomiting,
diarrhoea,
anaemia,
neurological
degeneration and
osteoporosis.
Causes
irreversible brain
damage including
cerebral palsy,
mental
retardation,
causes
chromosomal
segregation and
inhibits cell
division in foetus.
Disease: Pink
Disease
Causes multiple
neurological
problems with
symptoms similar
to those of
Parkinsons
disease, facial
muscle spasms
and even
hallucinations.
Disease:
Manganism
Causes allergic
reactions,
encephalopathy,
pulmonary
fibrosis and
reduced sperm
amount. Ni
compounds are
considered as

10.

Lead (Pb)

In ores of Zn,
Ag, Cu,
gasoline, car
engines and car
exhaust

In Pb-acid
batteries,
ceramic glazes,
solders, Pb
crystal
glassware,
ammunition and
bearings.

11.

Vanadium (V)

Minerals such as
patronite,
vanadinite,
carnotite &
bauxite.
Vanadium also
occurs in carbon
containing
deposits such as
crude oil & tar
sands etc.

Used as a steel
additive, in jet
engines and high
speed air
frames, in axles,
gears. Vandium
oxide (V2O5) is
used as a
catalyst in
manufacturing
sulphuric acid &
maleic
anhydride
In bronzing,
hardening and
improving the
sphericity of
shot, wood
preservation, as
pesticides,
pyrotechnics,
semiconductor
devices, LED,
lasers and ICs

12.

Arsenic(As)

Soft tissues,
bone and teeth

human
carcinogen.
Causes
hallucinations
and excitement of
central nervous
system, renal
failure and
chromosomal
aberrations. Pb is
also gametotoxic
and embryotoxic.
Acute effects:
headache, nausea,
vomiting,
insomnia &
irritability.
Chronic effects:
Lung & nasal
cancers

Blood and hair

Hypertension,
hyper
pigmentation,
hypopigmentation,
hyperkeratosis,
periorbital
swelling

1.3 Introduction to Dithiocarbamate Pesticides

The dithiocarbamates form a very important group among fungicides. Most of these are
foliage fungicides, while some are used for soil and seed treatments. Tisdale [32] first
demonstrated the fungicidal possibilities, of the carbonates in 1931 in the laboratories of E.I.
Dupont Company, USA, but the commercial production started about a decade later. The
dithiocarbamates were discovered as a class of chemical compounds early in the history of
organosulphur chemistry e.g., Debus [33] gave the synthesis of dithiocarbamic acids in 1850.
Delepine [34] was one of the pioneers in the field to recognize the metal binding properties of
dithiocarbamates. This property is due to the insolubility of the metal salts, with the exception
of Na and other alkali and alkaline earth metals and to the capacity of the molecules to form
the chelate complexes. It is due to this characteristic that various dithiocarbamates e.g.,
sodium diethyl dithiocarbamate, have been found practical outlet in the field of inorganic
analysis and antioxidants.
Carbamates are the half amides of carbonic acid. Their sulphur analogs, the
dithiocarbamates are the half amides of dithiocarbonic acid. The synthesis and the general
formula of dithiocarbamates are given below:
2NH3 + CO2

H NCOONH
2

The ammonium salt of carbamic acid

2NH3 + CS2 H2NCSSNH4
The ammonium salt of dithiocarbamic acid
The world wide consumption of dithiocarbamates is between 25,000 to 35,000 metric
tonnes per year. Dithiocarbamates are mainly used in agriculture as insecticides, herbicides
and fungicides. In industry, they are used as slimicides in water-cooling systems, in sugar,
pulp, and paper manufacturing, and as vulcanization accelerators and antioxidants in rubber
[35]. Because of their chelating properties, they are also used as scavengers in waste-water
treatment. Dithiocarbamates have been employed extensively as inhibitors in research on

enzymes. Their usefulness is due to their metal binding capacity and their ability to interact
with sulfhydryl-containing compounds. Because of their biological activity they have also
found a more practical application in the field of medicine. They were first used in medicine
in experiments on control of various dermatophytes.
Dithiocarbamates with hydrophilic groups form water-soluble, heavy-metal complexes, while
some of the dithiocarbamate metal complexes used as fungicides are insoluble in water and
soluble in non-polar solvents. Alkylene bisdithiocarbamates (containing two donor CS 2
groups), which form polymeric chelates, are insoluble in both polar and non-polar solvents.
Dithiocarbamates may decompose under certain circumstances into a number of compounds
as ethylenethiourea (ETU), and ethylenediamine (EDA). ETU is fairly stable, has high water
solubility, and is of particular importance because of its specific toxicity.

1.3.1 Toxicity of pesticides

Dithiocarbamates do not belong to systemic fungicides but are protectant fungicide applied
prior to fungus infection. Therefore, they act upon damaging fungi chiefly by surface deposits
[36]. Dithiocarbamates can be absorbed by the organism via the skin, mucous membranes,
respiratory and the gastrointestinal tracts. Whereas dithiocarbamates are absorbed rapidly
from the gastrointestinal tract, metal complexed Alkylene bisdithiocarbamates are absorbed
poorly both from the gastrointestinal tract and through the skin. Dithiocarbamates are known
to have toxicological and mutational effects [37].

1.4 Introduction to spectrophotometry

The spectrophotometry is based on the variation of colour of the system with change in
concentration of coloured species in the solution. The absorbing group in a molecule is called
chromophore. A molecule containing chromophore is called a chromogen. An auxochrome
does not itself absorb radiation, but if present in a molecule, it can enhance the absorption by
a chromophore or shift the wavelength of absorption when attached to a chromophore. The
UV-Vis spectrophotometry is an important tool for identification and estimation of inorganic,
organic and biochemical compounds. The merit of this analytical method is that very small
quantities of substance can be detected and estimated with reasonable accuracy.

1.4.1 Lambert Beers Law

The amount of monochromatic light radiation absorbed by a medium is described by Lambert
Beers Law, according to which, when a beam of monochromatic light radiation is allowed
to pass through a solution, the intensity of the emitted light radiation decreases exponentially
with increase in the thickness of absorbing medium. It could be expressed as follows
-dI/dt = kI
I is the intensity of the incident light radiation of wavelength, t is the thickness of the medium
and k is the constant of proportionality. Upon integrating this equation and putting I = I0 when
t = 0, it becomes
In I0/I = kt
It = I0 e-kt
Beer studied the effect of concentration while Lambert studied the effect of the thickness of
the absorbing medium over the transmission or absorption of light. Thus, Lambert Beer Law
could be represented as:
It = I0. log10. ct
log I0/ It = ct

A = ct
= A/ct
where A is the absorbance, c is the molar concentration i.e., in mol L-1, t is the thickness
of the medium in centimetres and is the molar extinction coefficient or molar absorptivity
in L mol-1 cm-1.
If there is only one absorbing species in the solution, then the quantitative estimation of an
unknown solution involves plotting the absorbance values verses concentration for a set of
standard solutions, keeping the wavelength fixed at a value for which the maximum
absorbance is obtained. After plotting the curve, the concentration of the unknown solution is
determined by measuring the absorbance and referring it to the calibration curve.

1.4.2 Sensitivity of Spectrophotometric methods

Sensitivity refers to the slope of a calibration curve, but is frequently used to mean the least
determinable concentration or amount of the species of interest. The objective numerical
expression of sensitivity of Spectrophotometric methods is the molar absorptivity () at the
wavelength of the maximum absorbance of the coloured species.
= A/ct
(is expressed in the litre mol-1 cm-1).
Savvin suggested the following criteria for describing the sensitivity.
Low sensitivity: < 2 104
Moderate sensitivity: < 2-6 104
High Sensitivity: > 6 104
The sensitivity of the spectrophotometric methods is often expressed in terms of the
expression given by Sandal which represents the number of micrograms of the species
determined per millilitre of a solution having an absorbance of 0.001 for a path length of
1cm. Then sensitivity S according to Sandal is expressed in g/cm2.

1.5 Introduction to reagents

1.5.1 1-(2-pyridylazo)-2-naphthol (PAN)
The most widely used azo dye is [1-(2-pyridylazo)-2-naphthol] (PAN, Fig. ) a heterocyclic
azo dyeforms coloured complexes with most metals. PAN since been developed as a
spectrophotometric reagent with or without extraction. These are red with the alkaline earths,
Al(III), Sc(III), Y(III), Ti(IV), Zn(II), Cd(II), Hg(II), Ga(III), In(III), Tl(III), Pb(II), Bi(III),
Ni(II), Mn(II) and U(IV) etc. With Cu(II), V(IV) and V(V), Fe(II) and Fe(III) and Ru(III),
they are of varying shades from red to violet, whereas with Co(II), Pd(II) and Pt(II) they are
green. The alkali metals, Ge(IV), As Se and Te do not recact. The pH of the solution is of
great importance, and minimum pH for chelation varies from metal to metal. Correct pH
control is of absolute importance in all analytical work with PAN [38]. Many of these
chelates are insoluble in water but can be extracted into various organic solvents as
investigated in detail by Shibita [39], Berger et al. [40] PAN shows both hypsochromic and
bathochromic shifts on protonation and ionization respectively. It is insluble in water, dilute
acids and alkslis, but is soluble in strong acid (pH < 2) to give a yellow-green cation, and in
strong alkalis (pH > 12) to give a red anion as shown below:

PAN acts as tridendate ligand complexing with most metals through the ortho-hydroxyl
group, the azo nitrogen nearest to the phenolic ring and the heterocyclic nitrogen atom, giving
two stable, 5-membered chelate rings [41]. The most common metal-to-ligand ratios
encountered are 1:1 and 1:2 and the structure for these two types of complexes are as shown
below:

Most PAN complexes have absorption maxima lying between 530 and 570 nm, but some
complexes absorb at longer wavelengths, for instance, V(V) (615 nm), Pd(II) (620 and 675
nm) and Rh(III) (598 nm). The spectrophtotmetric application with a wide range of metals
make PAN a useful sensitive and selective reagent. Shibita [42] has reviewed its use for
spectrophtotmetric determination of a number of metals in various samples.

The requirements of a satisfactory analytical method are usually manifold, but certainly
selectivity is counted amongst the most important. Hence there has always been interest in
procedures that can improve the sensitivity and selectivity of the measurement methods
themselves. According to the importance of metals to the aquatic environments, it may be
divided into three groups;
(i)

light metals such as sodium, potassium and calcium which are normally mobile

(ii)

cations in aqueous solution;

transition metals such as zinc, nickel, copper, cobalt and manganese which may be

(iii)

toxic in high concentration and

heavy metals and metalloid such as mercury, lead, cadmium, tin, antimony and
arsenic which are generally not required for metabolic activities and are toxic to
the cell at quite low levels also

Heavy metals though essential for industrial development, have been recognized as major
pollutants. The major source of metallic pollutants in aquatic systems is the discharge of
untreated industrial effluents from various industries such as electroplating, mining
operations, dyeing, battery, tanneries, glass, pharmaceutical and chemical manufacturing.
Metals are released continuously into the environment from the natural and anthropogenic
sources such as industrial effluents, atmospheric emission, fossil fuels, waste water stream
and urban habitation. Heavy metals are non-biodegradable and exist for a long time in the
environment. They have tendency to enter the living tissues. The excessive presence of these
metals in living species results in carcinogenic, mutagenic and other toxic effects on them.
Most of the technologies used for the removal of heavy metals from industrial effluents have
some disadvantages such as high operational and maintenance cost, expensive equipment,
incomplete metal removal, high energy requirement and generation of toxic residual metal

sludge. Analytical chemists continue to search for sample preparation procedures that are
faster, easier, safer and less expensive, to provide accurate and precise data with reasonable
detection limits. The direct determination of trace metal ions from various environmental
matrices is limited and difficult when its concentration is too low to be determined directly
and also interference due to matrix cannot be eliminated. A wide variety of modern
instrumental techniques such as optical, electrochemical, nuclear etc. are extensively
employed for the detection and determination of trace elements. Despite the inherent
selectivity and sensitivity of the analytical techniques such as flame atomic absorption
spectrometry (FAAS), electrothermal atomic absorption spectrometry (ETAAS), inductively
coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma
atomic absorption spectrometry (ICP-AES), inductively coupled plasma mass spectrometry
(ICP-MS) techniques, there is need for the preconcentration and separation of trace metals
prior to their determination, due to their frequent presence at low concentration in various
environmental samples. Preconcentration is a process in which the ratio of the quantity of a
desired trace element to that of the original matrix is increased. Preconcentration improves
the analytical detection limits, increase the sensitivity by several orders of magnitude,
enhances accuracy of the results and facilitate the calibration. Preconcentration and
separation techniques are of great importance:
When concentration of the targeted analyte is extremely low.
When interfering substances exist in the sample.
The techniques generally employed in analytical chemistry are liquid-liquid extraction [4345], co-precipitation [46, 47], cloud point extraction [48, 49], ion-exchange resin [50, 51],
electrothermal deposition [52] and solid phase extraction [53-57]. Electrochemical deposition
used for the preconcentration of different pollutants by applying the laws of electrolysis in
which cationic species are deposited on the electrode surface. The only disadvantage of this
method is that limitation related to the pH control. Co-precipitation is characterized by the
formation of insoluble compounds. The co-precipitation is adopted when direct precipitation
cannot separate the desired metallic species due to its low concentration in solution. The coprecipitation phenomenon can be associated with the metal adsorption on the precipitate
surface or due to metal incorporation onto the precipitate structures. Thus, there is a natural
limitation according to this phenomenon, because the metal used for this purpose cannot be
determined. The separation and preconcentration of metal ions and organic pollutants, after
the formation of sparingly water-soluble complex, based on cloud point extraction have
largely been employed in analytical chemistry. The search for alternatives to traditional

organic solvents in liquid-liquid extraction has fostered the use of more environment friendly
liquids. Liquid-liquid extraction is amongst the most often used method for preconcentration
because of its simplicity, rapidity, ready adaptability and easier recovery of analyte. There
are, however, physical difficulties associated with the use of solvent extraction for enrichment
of large number of samples and/or require vigorous agitation to ensure complete partition of
the analyte between two immiscible phases, and this can be achieved only by the application
of significant human or mechanical effort. In addition, there are increasing environmental and
cost pressures to replace, or at the very least reduce, the volume of solvents employed in
analytical procedures. Solid phase extraction continues to be the leading techniques for the
extraction of pollutants in aquatic systems; recent developments in this field are mainly
related to the use of new sorbents. Solid phase extraction (SPE) has emerged as a powerful
tool for separation/enrichment of inorganics, organics and bio molecules and has almost
replaced liquid-liquid extraction techniques because of associated advantages:

Fast and simple

No solvent loss
Higher preconcentration factor
Hyphenation with different modern analytical techniques
Time and cost savings
No need of toxic, carcinogenic and inflammable organic solvents
No use of surfactants
Rapid phase separation
Stability and re-usability of solid phase.

Different solid sorbents used in the preconcentration of metal ions using solid phase
extraction (SPE) methods have been discussed in Table 2.1.

Table 2.1 Preconcentration of metal ions using different Solid sorbents

Modificatio
n
Mode
Chemically
modified

Adsorbent

Modifier

LOD
(g L-1)

Preconcen
.
Factor
100

Target
Analyte
s
Hg(II)

Oxidized
MWCNTs

S-CS

0.0006

Chemically
modified

Silica gel

2-AT

0.005

29
38
46
133.3

Hg(II)

Chemically
modified

Activated
carbon

EDA

Chemically
modified

Polyurethane
foam

Ros

0.28
0.22
0.09
0.17
N.R.

Chemically
modified

MWCNTs

His

0.04

100-200

Hg(II)

Chemically
modified

Silica
aerogel

AMTT

N.R.

150

Hg(II)

Chemically
modified

AXAD-4

Octa-OMethoxy
Resorcin
[4]

N.R.

105
108
95
112

Ni(II)
Cu(II)
Zn(II)
Cd(II)

Chemically
modified

Fe3O4
NPs

DPC

0.16

100

Hg(II)

Chemically
modified

MWCNTs

EDA

0.3

N.R.

Hg(II)

Physically

Silica gel

HADPD

0.20

200

Mn(II)

100

Cr(III)
Fe(III)
Hg(II)
Pb(II)
Cd(II)
Hg(II)

Eluent

Method
&Mode

Ref.

10 mL of 10M
SPEHCl
CVAAS
Off-line
0.1 mL of 2M
SPEHCl
CVAAS
On-line
3.0 mL of 2%
SPE(w/w) thiourea
ICP& 0.5M HCl
OES
Off-line
0.1M and 2M
SPEHCl
UV-Vis
Off-line
10 mL of 10M
SPEHCl
CVAAS
Off-line
4 mL of 1M
SPEKBr
CVAAS
Off-line
HCl
and
SPEHNO3
UV-Vis,
FAAS,
ICPAES
Off-line
2 mL of 0.5M
SPEHNO3
CVAAS
Off-line
2.5 mL of
SPE0.1M EDTA
FAAS
Off-line
5mL mix. of
SPE-

58

59

60

61

62

63

64

65

66

67

modified

0.15

Chemically
modified

AXAD-1180

TAN

Chemically
modified

AXAD-2

Chemically
modified

MWCNTs

Physically
modified
Physically
modified

Ni(II)
100
50
100
300
300
200
80

Cd(II)
Co(II)
Cu(II)
Mn(II)
Ni(II)
Pb(II)
Co(II)
Mn(II)

PAN

0.3
3.6
0.8
0.1
0.2
1.1
0.82
0.64
(g g-1)
0.058

100

Mn(II)

Naphthalene

QTH

0.001

125

Hg(II)

Activated
carbon

Aliquat336

0.001

1700

Hg(II)

Chemically
modified

Silica gel

DPC

100

Hg(II)

Physically
modified

Sepabeads
SP-207

DDTC

50

Chemically
modified

MWCNTs

Nano
ZrO2

0.18
0.17
0.55
1.67
0.80

Cu(II)
Cd(II)
Pb(II)
Ni(II)
Pb(II)

Physically
modified

TiO2 NPs

DZ

0.38
1.72

N.R.

Cr(III)
Pb(II)

Chemically
modified

MWCNTs

L-Cys

0.28

33

Cd(II)

Physically
modified

Diaion HP2MG

A.
fumigatus

50

Physically
modified

AXAD-4

A.
tumifacien

0.30
0.52
0.41
0.59
0.72
0.32
3.6
3.0
2.8
3.6

Cu(II)
Pb(II)
Zn(II)
Ni(II)
Co(II)
Fe(III)
Fe(II)
Co(II)
Mn(II)
Cr(III)

30

25

5M HNO3:
MeOH
25 mL of 2M
HNO3

FAAS
Off-line
SPEFAAS
Off-line

68

10 mL of 2M
SPEHNO3
ICPAES
Off-line
5 mL of 0.1M
SPEHNO3
FAAS
Off-line
2
mL
of
SPEAcetone
UV-Vis
------SPEXRFS
Off-line
10 mL of PEG
SPEUV-Vis
Off-line
5 mL of 2M
SPEHNO3
in FAAS
Acetone
Off-line

69

5 mL of 1M
HCl

SPEFAAS
Off-line
1.5 mL of
SPE0.25M HCl
ICPAES
Off-line
2 mL of 0.5M SPE-FIHCl
FAAS
On-line
8-10 mL of
SPE1M HCl
FAAS
Off-line

75

10 mL
1/2M HCl

79

of

SPEFAAS
Off-line

70

71
72

73

74

76

77

78

Physically
modified

Silica gel

A. niger

Chemically
modified

AXAD-2

CTA

1.7
5.2
1.6
N.R.

50

Fe(III)
Pb(II)
Ni(II)
Cd(II)
Co(II)
Cu(II)
Fe(III)
Ni(II)
Zn(II)
Fe(III)

10 mL of 1M
HCl

Physically
modified

Analcime
zeolite

L1

0.084

100
150
100
120
200
200
60

Physically
modified

AXAD-7

Xylenol
orange

Chemically
modified

Silica gel

APTES

9
24
6
3
21
6
0.5

50
100
50
100
100
200
5

Physically
modified

AXAD-16

HL

4.59

Chemically
modified

MWCNTs

TAA

Chemically
modified

SiO2 NPs

Chemically
modified

SPEFAAS
Off-line
SPEFAAS
Off-line

80

SPEFAAS
Off-line
SPEFAAS
Off-line

82

10 mL of 1/2
M HCl

25

Cd(II)
Co(II)
Cu(II)
Ni(II)
Zn(II)
Fe(III)
Bi(III)
Pb(II)
Ni(II)
Fe(III)

SPEGFAAS
Off-line
SPEFAAS
Off-line
SPEICPOES
Off-line
SPEUV-Vis
Off-line
SPEICPAES
Off-line
SPEFAAS
Off-line

84

0.32

60

Pb(II)

5 mL of 2M
HCl

DHAQ

0.60

66.7

Cd(II)

6 mL of 1M
HCl

Nanometer
SiO2

SSA

0.09

100

Fe(III)

2
mL
of
0.01M HCl

Adsorption

Cellulose
Nitrate
membrane

Calmagite
Chelates

SWCNTs
disk

--------

150
50
250
250
150
30

Cr(III)
Co(II)
Cu(II)
Fe(III)
Pb(II)
Fe(III)
Cr(III)

2-5 mL of 1M
HNO3

----------

2.5
0.76
0.06
0.33
1.18
2.12
4.08

SPEFAAS
Off-line
2 mL of 1M
SPEHNO3
ICPAES
Off-line

90

Physically
modified

Nanometer
Alumina

CTA

0.14
0.62
0.22
0.54

50
75
100
100

Cd(II)
Cr(VI)
Cu(II)
Fe(III)

10 mL of HCl
or HNO3

10 mL 0.1M
EDTA

5 mL of 2M
HCl
10 mL of 2M
HCl

5 mL of 1M
HNO3

81

83

85

86

87

88

89

91

0.27
0.28
0.53
0.38
0.11
1.70
0.39
0.52
N.R.

75
75
50
100
33.3

33.3

Mn(II)
Ni(II)
Pb(II)
Zn(II)
Cu(II)
Pb(II)
Zn(II)
Cd(II)
Cd(II)

Physically
modified

TiO2 NPs

DDTC

Adsorption

AXAD-4

APDC
chelates

Adsorption

MWCNTs

PAN
chelates

0.43

40

Cd(II)

Chemically
modified

Cross linked
Chitosan

AHBA

0.024
0.058

100

Ni(II)
Pb(II)

5 mL of 1M
HNO3
in
Acetone
10 mL of 2M
HNO3

Chemically
modified

Sub micron
Silica

L-Cys

N.R.

N.R.

Cd(II)
Pb(II)

2 mL of 2M
HNO3

Physically
modified

AXAD-1180

MBT

5.0
0.35

20

Pb(II)
Cd(II)

20 mL of 2M
HNO3

Chemically
modified

AXAD-2

NPTT

60

AXAD-2000

DDTC

Physically
modified

Activated
carbon

APDC

50

Cd(II)
Cu(II)
Ni(II)
Pb(II)
Mn(II)
Fe(III)
Co(II)
Cu(II)
Cd(II)
Zn(II)
Pb(II)
Ni(II)
As(III)

10 mL of 2M
HNO3

Chelate
adsorption

0.22
0.18
0.20
0.16
0.20
0.35
0.25
0.20
0.20
0.15
0.45
0.25
0.05

Adsorption

Cyanopropyl
Modified
Silica
AXAD-2

1,10-Phen
Chelates

0.18
0.073

80
120

Cd(II)
Cu(II)

5-10
1M

Pyrocatechol

0.27
0.59
1.29

44
40
48

Cd(II)
Co(II)
Ni(II)

Chemically
modified

100

1.5 mL
0.1M HCl

of

SPEICPAES
Off-line

92

15 mL of 2M
HNO3

SPEFAAS
Off-line
SPEFAAS
Off-line
SPEFAAS
Off-line
SPEETAAS
Off-line
SPEFAAS
Off-line
SPEICPAES
Off-line

93

1M HNO3 in
acetone

SPEFAAS
Off-line

99

2.0 mL of
0.1M HNO3

SPEGFAAS
Off-line

100

SPEICPOES
Off-line
0.04/0.08 mL
SPEof 0.5M HCl
FAAS
On-line

101

mL of

94

95

96

97

98

102

Embedded

StyreneEGDMA
polymer
AXAD-2

DCQ

2.0
2.0

200
200

Co(II)
Ni(II)

5 mL of 2M
HCl

Tiron

AXAD-2

TSA

200
50
55
150
25
180
65
80
150
180
200

Physically
Modified

Ambersorb563

PAN

Chemically
modified

MWCNTs

PAN

Cu(II)
Cd(II)
Co(II)
Ni(II)
Pb(II)
Zn(II)
Mn(II)
Fe(III)
UO2(II)
Cd(II)
Co(II)
Cu(II)
Fe(III)
Ni(II)
Zn(II)
Cu(II)
Ni(II)
Cd(II)
Pb(II)
Cr(III)
Co(II)
Co(II)

4M HNO3

Chemically
modified

2.0
1.3
5.0
4.0
24.0
0.5
2.5
5.0
1.0
0.48
0.20
4.05
0.98
1.28
3.94
0.67
0.23
0.23
1.4
0.5
0.21
0.55

Adsorption

MWCNTs

APDC
chelates

0.43
0.11
0.46
0.15

N.R.

Co(II)
Ni(II)
Cu(II)
Pb(II)

N.A.

Chemically
modified

AXAD-4

ABA

N.R.

Physically
modified

Silica gel

Salicylaldoxime

Chemically
modified

Silica gel

ATAAQ

1.0
1.5
1.5
2.0
22.5
1.0
2.9
0.95

400
400
150
200
400
66
50
50
40
20

Pb(II)
Cd(II)
Ni(II)
Co(II)
Zn(II)
Cu(II)
Ni(II)
Co(II)
Zn(II)
Pb(II)
Cu(II)
Ni(II)
Co(II)

Chemically
modified

125

300

SPEFAAS
On-line
SPEFAAS
Off-line

103

4-8 mL of 2M
HNO3

SPEFAAS
Off-line

105

10 mL of 1M
HNO3 in
Acetone

SPEFAAS
Off-line

106

3 mL of 0.5M
HNO3

SPEFAAS
Off-line
DMSPE
EDXRF

107

10 mL of 1M
HNO3

SPEFAAS
Off-line

109

A mix.
HClO4
HNO3

Of
+

SPEFAAS
Off-line

110

5 mL of 1%
HNO3

SPEFAAS
Off-line

111

104

108

1.1
Chemically
modified

Cellulose

HQ

Chemically
modified

Silica gel

SPIMP

Physically
modified

Silica gel

HBAHBA

Physically
modified

Activated
carbon

2,4-MBAT

Cd(II)

Chemically
modified

Silica gel

2,4CBABT
PEG

Chemically
modified

MWCNTs

ABTZ

0.79
0.84
2.51
1.61
1.09
2.59
2.44
2.4
2.8
1.6
2.0
2.0
1.4
1.02
4.2
1.54
5.46
2.1
1.62,
2.34
1.63,
2.08
0.66
0.33
1.20
0.3

300
250
300
90
100
250
200
83

Cu(II)
Zn(II)
Fe(III)
Ni(II)
Co(II)
Cd(II)
Pb(II)
Fe(III)
Pb(II)
Cu(II)
Ni(II)
Co(II)
Zn(II)
Cr(III)
Cu(II)
Cd(II)
Zn(II)
Pb(II)
Zn(II)
Cu(II)

10-20 mL of
HCl/
HNO3

SPEFAAS
Off-line

112

6 mL of 4M
HNO3

SPEFAAS
Off-line

113

5 mL of 3N
HNO3

SPEFAAS
Off-line

114

8 mL of 4M
HNO3

SPEFAAS
Off-line

115

3 mL of 1M
HNO3

SPEFAAS
Off-line
SPEICPOES
Off-line
5 mL of 2M
SPEHNO3
in FAAS
EtOH
Off-line
2mL of 1M
SPEH2SO4+
UV-Vis
Acetone
Off-line
(1:2)
2 mL of 1M
SPEHCl
FAAS
Off-line

116

100

Cu(II)
Cd(II)
Mn(II)
Pb(II)

Adsorption

AXAD-7

BPMBDA

0.24

200

Co(II)

Chemically
modified

Silica gel

PEG

0.57

250

Fe(II)

Physically
modified

Naphthalene

TMTA

---------

-CDPU

--------

0.51
0.49
0.17
0.10
1.15

250
250
400
250
250

Co(II)
Ni(II)
Cd(II)
Zn(II)
Pb(II)

Grafting

Fe3O4/SiO2

L2

0.14

87.5

Pb(II)

20

150
170
150
170
66.6

2 mL of 2M
HNO3
3 mL 1M

SPEFAAS
Off-line
SPE-

117

118

119

120

121

122

NPs

0.19
0.12

Cd(II)
Cu(II)

HNO3+ 1 mL
EtOH

FAAS
Off-line
SPEETAAS
Off-line
SPEICPOES
Off-line
SPEFAAS
Off-line
SPEFAAS
On-line

123

SPEFAAS
Off-line
15 mL of
SPE1.5M
Potentio
HNO3
meter
5 mL of 0.1M
SPEHCl in MeOH
FAAS
Off-line

127

SPEFAAS
Off-line
SPEFAAS
Off-line

130

SPEFAAS
Off-line
SPEFAAS
Off-line
SPEFAAS
Off-line

132

Chemically
modified

MWCNTs

5-BrPADAP

0.14

300

Cd(II)

3 mL 0.5 M
HNO3

Chemically
modified

Nanometer
SiO2

ASA

0.49

50

Fe(III)

2mL of 0.01M
HCl

Physically
modified

AXAD-7

EHND

2.82
0.74

200

Ga(III)
In(III)

5 mL of 1M
HNO3

Chemically
modified

Nanometer
Alumina

QAHBA

10

AXAD-4

HMPN

Ag(I)
Pd(II)
Au(III)
Ga(III)
In(III)
Nb(II)
Ga(III)
In(III)

0.6 mL of 1M
HNO3& 3%
(m/v) thiourea

Physically
modified

0.12
0.44
0.27
0.19
0.54
0.18
3.4
0.92

---------

Chelax-100

--------

N.R.

50

Pb(II)

Chemically
modified

SPFGraphene

Porphyrin

600

Co(II)

Adsorption

Graphene

PAN

0.36

200

Co(II)

2 mL of 2M
HNO3

Physically
modified

Al2O3
Coated
Fe3O4
(ACMNPs)
SPFGraphene

DMGSDS

4.6

320

Ni(II)

2 mL of 0.1M
HNO3

Porphyrin

600

Zn(II)

5 mL of 2M
HNO3
10%
V/V MeOH
5 mL of 2M
HCl

Chemically
modified

200

Chemically
modified

TiO2 NPs

Polythiophene

0.4
1.2

100

Cu(II)
Ag(I)

Chemically
modified

Nanoporous
Fructose

DZ

0.025
0.15
0.5
1.2

480

Cd(II)
Cu(II)
Ni(II)
Pb(II)

5 mL of 0.5M
HNO3

2.5 mL of
HNO3 : HCl
[2:1(M)]

124

125

126

128

129

131

133

134

Physically
modified

SDS coated
Al2O3

ITD

Physically
modified

C18 Filled
cartridge

DZ

Chemically
modified

AXAD-4

HBTSC

Chemically
modified

Merrifield
resin

Physically
modified

Activated
carbon

Calix[4]
arene-ovanillin
semicarbazone
NNPP

Chemically
modified

AXAD-16

HMBA

Chemically
modified

Cellulose
fibre

EDTA

Chemically
modified

Ionic liquid
Based
Xerogels

TPTMS

Chemically
modified

Silica
NPs

PAN

Chemically
modified

AC
Anchored
Au NPs
Magnetic
Iron
Oxide
NPs

DHHMB

------------

---------

1.77
1.83
1.93
8.1

444.4

Cu(II)
Ni(II)
Co(II)
Pb(II)

4.5 mL of 2M
HNO3

0.87
0.95
1.03
3.05
6.86

100

Cu(II)
Cd(II)
Pb(II)
La(III)
Ce(III)

10 mL of 2M
HNO3

0.17
0.16
0.11
0.12
0.58
1.08
1.21
0.86
1.72
1.5

550

Cu(II)
Fe(III)
Zn(II)
Pb(II)
Zn(II)
Cu(II)
Ni(II)
Cd(II)
Pb(II)
Pb(II)

3 mL of 4M
HNO3

2.7
2.4
1.7
2.4
2.8
1.5
0.65

150

6 mL of 4M
HNO3

50

Fe(III)
Co(II)
Cu(II)
Ni(II)
Pb(II)
Zn(II)
Co(II)

0.7
1.6
2.2
0.8

165
170
180
200

Cu(II)
Fe(III)
Zn(II)
Pb(II)

10 mL of 4M
HNO3

200

153
133

360
340
300
260
240
200

SPEFAAS
Off-line
SPEFAAS
Off-line
SPEGFAAS
Off-line
SPEUV-Vis
&
ICPAES
Off-line
SPEFAAS
Off-line

135

5 mL of 2M
HCl

SPEFAAS
Off-line

140

10 mL of 1M
HNO3

SPEFAAS
Off-line
SPEFAAS
Off-line

141

SPEUV-Vis
Off-line
SPEFAAS
Off-line
SPEETAAS
Off-line

143

5 mL of 1M
HCl

10 mL 0f
0.01N HNO3 +
3N HCl

7 mL of 5M
HCl

1 mL of 1M
HNO3

136

137

138

139

142

144

145

Chemically
modified

Silica
NPs

RATP

0.36

60

Cu(II)

5 mL of 4M
HCl

SPEUV-Vis
Off-line
SPEFAAS
Off-line
SPEFAAS
Off-line
SPEFAAS
Off-line
SPE-FIICPOES
DCA
Off-line

146

Chemically
modified

AXAD-2

NRS

0.19
0.31

250

Cd(II)
Pb(II)

Chemically
modified

AXAD-1180

PV

0.37
0.20

100

Pb(II)
Fe(III)

8-10 mL of
1M HNO3 in
Acetone
5 mL of 1M
HNO3

Physically
modified

SiO2 NPs

DPC

1.3

20

Cr(III)

0.5 mL of
0.5M HNO3

Adsorption

DCA
modified
Fe3O4 NPs

PAN

Ag
NPs

AC

IPBATP

136
116
120
131
118
150
100
50
100
50
100
50
100
50
50
25

Cd(II)
Co(II)
Cr(III)
Ni(II)
Pb(II)
Zn(II)
Cu(II)
Zn(II)
Co(II)
Cd(II)
Pb(II)

0.3 mL of 0.25
M HCl in
Propanol

Chemically
modified

Chemically
modified

SG

nm
SiO2

p-TSA

Physically
modified

AXAD-4

G. t.
strom.

0.3
0.7
0.5
0.6
0.8
0.2
1. 1.7
5 1.6
1. 1.9
3 1.6
2. 2.5
1
1.
4
2.
5
0.61
0.19
1.59
0.21
2.7

SPEFAAS
Off-line

151

125
250
150
200
50

Cr(III)
Cu(II)
Pb(II)
Zn(II)
U(VI)

4 mL of 0.5M
SPEHCl
ICPAES
Off-line

152

5 mL of 1M
HCl

SPEUV-Vis
Off-line
10 mL of
SPE1.5M
ICPAES
HCl
Off-line
7.5 mL of 2M
SPEHNO3 in
FAAS
Acetone
Off-line

153

Chemically
modified

AXAD-4

ARS

N.R.

10

Rh(III)

----------

AXAD-2000

----------

100

Pb(II)

-----------

SiO2/MnOX
Hybrid
material

----------

0.20

39.4

Cd(II)

1M HNO3

156

5 mL 10mL
of
of
6M
4M
Acetic
acid

SPEFAAS
On-line

147

148

149

150

154

155

Chemically
modified

Silica
gel

Gallic
acid

1.08
1.23
0.87
1.26
21
65

200
200
100
200
90

Pb(II)
Cu(II)
Cd(II)
Ni(II)
Cd(II)
Zn(II)

10 mL of 0.055M HCl

SPEFAAS
Off-line

157

Chemically
modified

Chitosan

APCA

10 mL of 1M
HNO3

158

[{(TESP)
MIm}Cl]

0.48

75

Fe(III)

2 mL of 0.1M
HCl

Peanut
shell

H3PO4

2.3
0.2

40

Pb(II)
Cd(II)

1.5 mL
0.1M HCl

Physically
modified

AXAD-4

AMPDAA

80

AXAD-16

Nitroso
naphthol

1250
833

Cd(II)
Co(II)
Cu(II)
Ni(II)
Zn(II)
Ni(II)
Cu(II)

8 mL of 1M
HCl + 1M
NaCl + 2 mL
of DDI water

Chemically
modified

0.028
0.064
0.042
0.023
0.16
N.R.

SPEFAAS
Off-line
SPEICPAES
Off-line
SPEFAAS
Off-line
SPEFAAS
Off-line

Chemically
modified

Silica gel

Chemically
modified

162

Physically
modified

SDS coated
Al2O3

MBID

N.R.

Cu(II)

Chemically
modified

AXAD-2

05 mL of
0.15M sulfosalicylic acid
NA
mL
3N 15 20
.5N 15 20
1N 15 20

Physically
modified

Naphthalene

Stearic
acid

2.9

84

Pb(II)

Physically
modified

Triton X 100
coated
PVC
-CDP

IYPMI

90

DNAAB

1.25
2.9
1.0
0.024

N.R.

Cu(II)
Fe(III)
Zn(II)
Hg(II)

-CDP

OVFH

0.80

N.R.

Cd(II)

N.Rq

SPEFAAS
Off-line
SPEFAAS
Off-line
SPEUV-Vis
FAAS
ICPAES
Off-line
SPEFAAS
On-line
SPEFAAS
Off-line
SP
UV-Vis
Off-line
SF

Naphthalene

MTOAC

0.42
0.072

300
100

Pb(II)
Cd(II)

5 mL of 2M
HNO3

Sodium

BBHBPDI

2.4

375

Co(II)

4 mL of 5M

Inclusion
Complex
Formation
Inclusion
Complex
Formation
Physically
modified
Impreg-

N.R.

N.R.
91
95
98

87
91
96

Cu(II)
Zn(II)
Cd(II)

of

3 mL of 2M
HCl or HNO3

(250L) 0.25
mL of 1M
HNO3
5 mL of 4M
HNO3
N.Rq

SPEFAAS
Off-line
SPE-

159

160

161

163

164

165

166

167

168

169

170

nated
(Physically
Modified)

Impregnated
(Physically
Modified)

dodecyl
sulfate
(SDS)
coated
alumina
Activated
carbon

DBDP

2.1
2.7
2.6
1.8
1.5
2.5
2.4
1.9
2.1

290

Fe(III)
Pb(II)
Cr(III)
Cu(II)
Cd(II)
Ni(II)
Cu(II)
Zn(II)
Cd(II)

HNO3

FAAS
Off-line

6 mL of 4M
HNO3

SPEFAAS
Off-line

171

Cu(II)
Co(II)
Zn(II)
Ni(II)
Pb(II)
Cu(II)
Fe(III)
Zn(II)

1M HNO3

SPEICPOES
On-line

172

6 mL of 4M
HNO3
in
acetone

SPEFAAS
Off-line

173

5 mL of 2M
HCl

SPEFAAS
Off-line
2 mL of 0.5M
SPE
HCl
ICPOES
Off-line

174

12.5 mL
1M HCl

SPEFAAS
Off-line
SPEFAAS
Off-line

176

8-10 mL of
1M HNO3

SPEFAAS
Off-line

178

2 mL of 0.3M
HCl

SPE
GFAAS
Off-line
SPE
FAAS

179

Chemically
modified

Silica
materials

8-HQ

N.R.

N.R.

Physically
modified

Duolite
XAD-761

BHAPDMPDI

1.8
2.4
1.6

209

Chemically
modified

MWCNTs

DPC

0.05

360

Cd(II)

Chemically
modified

Silica gel

HQANSA

N.R.

Chemically
modified

Groundnut
shell

Tartaric
acid

Impregnation

Triton X-100

HMBTSC

Cu(II)
Zn(II)
Cd(II)
Cr(III)
Ni(II)
Cd(II)
Pb(II)
Cu(II)
Ni(II)
Cu(II)
Zn(II)

Physical
Immobilization

MWCNTs

P.
aeruginosa

-----------

MWCNTs

---------

Chemically
modified

Montmorillonite

3-MTMS

0.85
1.3
2.2
0.92
0.68
0.72
0.64
1.60
g mL-1
3.6
3.2
3.6
0.74
0.24
2.60
0.43
1.18
1.30
0.03
0.01
0.50
N. R.

160

83

50

150

10

Co(II)
Cd(II)
Pb(II)
Mn(II)
Cr(III)
Ni(II)
Cd(II)
Cu(II)
Pb(II)
Pb(II)

of

10 mL of 1M
HNO3

5 mL of 0.5M
HNO3

175

177

180

Off-line
Chemically
modified

Silica gel

1,2DHAQ

Chemically
modified

Silica gel

1,5-DPC

Chemically
modified

AXAD-4

HBAM

Chemically
modified

AXAD-2

DTBA

Chemically
modified

AXAD-4

PTA

Chemically
modified

Silica gel

BTU

Chelate
Adsorption

Dowex
Optipore
SD-2
CPSG

Chelate
Adsorption

AXAD-8

AMOTAC
TA

Chelate
Adsorption

Chromosorb105

PAN

Chemically
modified

0.64
0.47
0.98
0.83
0.75
N.R.

N.R.

0.39
0.49
0.42
0.59
0.71
1.10
0.10
0.34
0.42
0.16
0.52
0.62
0.60
0.65
0.75
0.72
0.84
0.85
2

400
380
380
360
320
320
200
150
130
100
130
190
190
190
180
180
160
160
250

5-Me-TAR

1.03
1.90

50

Cu(II)
Ni(II)

Quercetin

4.18
2.44
15.86
25.00
0.20

200

200

As(V)
Cd(II)
Hg(II)
Pb(II)
Cu(II)

1.74
0.85
0.17

300
250
150

Fe(III)
Zn(II)
Cu(II)

N.R.

Cd(II)
Cu(II)
Ni(II)
Pb(II)
Zn(II)
Pb(II)
Cd(II)
Cu(II)
Zn(II)
Cu(II)
Cr(III)
Ni(II)
Co(II)
Zn(II)
Pb(II)
Cd(II)
Ni(II)
Co(II)
Cu(II)
Zn(II)
Ni(II)
Mn(II)
Cu(II)
Zn(II)
Cd(II)
Cr(III)
Co(II)
U(VI)

10-25 mL of
1.5M HNO3

SPE
ICPOES
Off-line

181

N.R.

SPE
FAAS

182

5 mL of 2M
HCl

SPE
FAAS
Off-line

183

8.0 mL of 2M
HCl& 2 mL
pure water

SPE
FAAS
Off-line

184

5 mL of 3M
HCl

SPE
FAAS
Off-line

185

SPE
UV-Vis
Off-line
5 mL of 1M
SPE
HNO3
FAAS
Off-line
5 mL of 1M
SPE
HCl
ICP-MS
Off-line

186

7.5 mL of 2M
HCl

189

2 mL of 0.1M
HCl

3 mL of 2M
HNO3

SPE
FAAS
Off-line
SPE
MISFAAS

187

188

190

Chemically
modified

0.70

150

Pb(II)

Off-line
2 mL of 0.5M
SPE
HCl
ICPOES
Off-line
5
mL
of
SPE
acidified
FAAS
MeOH
Off-line
3 mL of 3M
SPE
HNO3
in FAAS
methanol
Off-line

191

6 mL of 0.8M
EDTA
in
0.01M NaOH
Soln
8 mL of 0.1M
TU in 2M
H2SO4
6 mL of 4M
HNO3

SPE
FAAS
Off-line

194

SPE
FAAS
Off-line
SPE
FAAS
Off-line

195

SPE
FAAS
On-line
HNO3
SPE
FAAS
Off-line
10 mL of
SPE
0.4M HCl
FAAS
Off-line
2 mL of 3M
SPE
HCl
ICPOES
Off-line

197

10 mL of a
mixture
containing
0.5M Na2S2O3
and KSCN

201

APA

60*

150

Al(III)

Chemically
modified

Nanometer
(TiO2+SiO2)
composite
Nano
graphene

OD

21
12

250

Cr(III)
Cr(VI)

Physically
loaded

Sulfur
NPs

Al2O3

83.3

Chemically
modified

Fe3O4-py
NPs

Cu-BTC

0.30
0.24
0.21
0.63
0.2
1.1

Cd(II)
Cu(II)
Zn(II)
Pb(II)
Cd(II)
Pb(II)

Chemically
modified

-Al2O3

9-AcA

13

200

Au(III)

Physically
modified

Au-NP-AC

BMSAPD

200

Chemically
modified

CMT-PS

PPDOT

2.4
1.7
2.4
2.7
2.8
1.5
0.56

40

Co(II)
Cu(II)
Ni(II)
Fe(II)
Pb(II)
Zn(II)
Cu(II)

Chemically
modified

Cellulose
microfiber

2-AEEDA

0.069

26

Cd(II)

Chemically
modified

PUF

AA

100

--------

Nano
Zirconia

---------

Physically
modified

Organo
Nano clay
Closite 15A

Rhodanine

0.14
0.51
0.14
12
58
24
2
7
36
42.6

Cu(II)
Zn(II)
Mn(II)
Mn(II)
Cu(II)
Cr(III)
Zn(II)
Ni(II)
Co(II)
Au(III)

167

50

70

1 mL of 1M
HNO3

SPE
FAAS
Off-line

192

193

196

198

199

200

Physically
modified

Duolite C20

DAPCH

300

Fe(III)

Chemically
modified

CMT-PS

NAP-dien

1.4

80

Cu(II)

Physically
modified

SDS coated
-alumina

PAR

0.21

50

Cu(II)

Chemically
modified

Vinyl
pyridine

DPC

0.42

245

Pb(II)

------------

Activated
carbon

-----------

80

Chemically
modified

AXAD-4

HQCA

Chemically
modified

AXAD-7

CPDPINP

Chemically
modified

PUF

DTC

Chemically
modified

Silica gel

Curcumin

Chemically
modified

Mesoporous
TiO2

Physically
modified

MicroCrystalline
Triphenyl
methane
RHP

Thiacalix
[4]
Arene
TC
Salicylfluorone

0.17
0.19
1.60
2.60
0.92
1.50
0.14
0.70
0.35
2.92
0.26
0.72
1.6
2.5
2.5
1.4
2.6
0.015
0.015
0.012
0.12
0.15
0.40
0.09
0.23
0.50
0.15
0.013

83-166

Cd(II)
Co(II)
Cu(II)
Ni(II)
Pb(II)
Zn(II)
Cd(II)
Co(II)
Cu(II)
Pb(II)
Mn(II)
Ni(II)
Cu(II)
Ni(II)
Co(II)
Zn(II)
Pb(II)
Fe(II)
Mn(II)
Cu(II)
Cu(II)
Fe(III)
Zn(II)
V(V)
Cu(II)
Pb(II)
Cr(III)
Mo(VI)

0.42

100

Cu(II)

Chelate
formation

NNSA

27.6
23.2
22.3
24.1
24.7
20.2
150

100

75

20

5 mL of 0.5 M
HCl

SPE
FAAS
Off-line
2M HCl
SPE
FAAS
On-line
0.2 mL of 1M
SPE
HNO3
FAAS
Off-line
5 mL of 2M
SPE
HCl
FAAS
Off-line
3 mL of HNO3
SPE
ICPOES
Off-line

202

1M HNO3

SPE
FAAS
On-line

207

6 mL of 4M
HNO3

SPE
FAAS
Off-line

208

SPE
FAAS
Off-line
2 mL of 0.1M
SPE
HCl
ICPOES
Off-line
0.3 mL of 1M
SPE
HNO3
FIICPOES
On-line
6.0 mL of
SPE
Eluent
UV-Vis
Off-line

209

5 mL of 1M
HCl

213

10 mL of 1M
HCl

SPE
FAAS

203

204

205

206

210

211

212

-------------

Amberlyst
36

-------------

0.245

200

Mn(II)

5 mL of 3M
HNO3

-------------

Amberlyst
36

-------------

0.44

200

Co(II)

5 mL of 4M
HNO3

-------------

Amberlyst
36

-------------

0.26

200

Cu(II)

5 mL of 0.4M
KCN Soln.

Chelate
formation

Ambersorb
572

EDTA

3.65
1.42

75
50

Pb(II)
Ni(II)

10 mL
Eluent

Chemically
modified

AXAD-16

HIMB

AXAD-2

DTBA

SPE
FAAS
Off-line

219

AXAD-4

AMPDAA

8 mL of 1M
HCl + 1M
NaCl

SPE
FAAS
Off-line

220

Physically
modified

IL coated
nanometer
TiO2
GO-Silica

TAN

Zn(II)
Mn(II)
Ni(II)
Pb(II)
Cd(II)
Cu(II)
Fe(III)
Co(II)
Cd(II)
Ni(II)
Co(II)
Cu(II)
Zn(II)
Cd(II)
Co(II)
Cu(II)
Ni(II)
Zn(II)
Ni(II)

8mL of 2M
HCl and 2mL
of pure water

Physically
modified

200
250
300
200
150
250
300
250
200
150
130
100
130
80

25 mL of
1.5M
HCl/HNO3

Chemically
modified

1.72
1.30
2.56
2.10
0.44
2.93
2.45
3.23
0.10
0.34
0.42
0.16
0.52
0.028
0.064
0.042
0.023
0.16
0.8

Off-line
SPE
FAAS
Off-line
SPE
FAAS
Off-line
SPE
FAAS
Off-line
SPE
FAAS
Off-line
SPE
FAAS
Off-line

SPE
FAAS
Off-line
0.1 mL of
HF0.5M HNO3
SPME
ICPOES
On-line

221

1mL of 1M
SPE
HNO3
ICPOES
Off-line
0.2mL of 2M
SPE
HNO3 in EtOH FAAS

223

------------

-----------

Chemically
modified

MCM-41

5-Nitro
Fural

Chelate
Adsorption

MMWCNTs

PAN

---------

7.5
0.39
20
23
6.7
28
0.3

10

100

1.0
0.6

390
697

Mn(II)
Co(II)
Ni(II)
Cu(II)
Cd(II)
Pb(II)
U(VI)
Th(IV)
Pb(II)
Mn(II)

of

1 mL of 0.5M
HNO3

214

215

216

217

218

222

224

Chelate
adsorption
------------

SDB
membrane
disks
Silk
fibroin

PSH

100

Cu(II)

-----------

8.0

27.3

Cu(II)

(50/50)
10mL of 1M
HNO3
30 L (=0.03
mL) of 0.5M
HNO3
5mL of DMF

Chelate
adsorption

MWCNTs

PAN

0.010

120

Rh(III)

Physically
modified

Neutral
alumina

DMSO

N.R.

1000

Hg(II)

2 mL of Conc.
HNO3

Chemically
modified

Nanometer
Ceria

Silica-iron
oxide

Silica coated
Magnetic
Fe3O4
NPs
Ultralayered
Co3O4

DZ

18
19
18
14
18
17
16
18
14
14
17
19
19
19
100

175

As(V)
Be(II)
Cd(II)
Co(II)
Cr(III)
Cu(II)
Hg(II)
Mn(II)
Mo(VI)
Ni(II)
Pb(II)
Sb(III)
Se(IV)
V(V)
Cr(III)
Cu(II)
Pb(II)
Zn(II)
Pb(II)

2.5 mL of 2N
HNO3

Physically
modified

0.46**
0.15
0.05
0.12
0.61
0.51
0.10
0.14
0.22
0.14
0.51
0.29
0.24
0.23
35
11
62
8
0.72

20

Cu(II)

5 mL of 1%
(V/V) HNO3

198
205
206
400

Co(II)
Ni(II)
Cu(II)
U(VI)
Th(IV)
La(III)

120 L(=0.12
mL) of 3M
HNO3
15 mL of 1M
(NH4)2CO3

------------

Chemically
modified

Silica

------------

Alumina
NPs

Chemically
modified

MCM resin

-----------

Amidoamide
oxime
-----------

DAPPA

2.5
2.8
2.6
10**
50
89

Off-line
SPE
FAAS
Off-line
SPE
ETAAS
On-line
SPE
FAAS
Off-line
SPE
HGAAS
Or
CVAAS
Off-line
SPE
ICPOES
Off-line

225

226

227

228

229

1 mL of 1.5M MSPE
HNO3
ICPOES
Off-line

230

2 mL of 2M
HNO3

231

SPE
FAAS
Off-line
SPE
FAAS
Off-line
CPE
ETAAS
Off-line
SPE
UV-Vis
Off-line

232

233

234

Chemically
modified

Silica gel

AEPU

0.091#

150

Sc(III)

Chemically
modified

Halloysite
nanotubes

Murexide

0.29

120

Pd(II)

Chemically
modified

Silica gel

MTPB

0.085#

100

Sc(III)

Chemically
modified

MNP

Q-Alizarin

30*

----------

Be(II)

Chemically
modified

SBA-15
Mesoporous
Silica
Magnetic
Fe/Fe2O3
Nanoscavenger

APTES

0.2

44

Cr(VI)

-----------

----------

Chemically
modified

MWCNTs

MnO2

20*
35
25
45
125
4.4*
1.5

Cd(II)
Pb(II)
Ni(II)
Cr(VI)
As(V)
Pb(II)
Cd(II)

Chemically
modified

MWCNTs

Oxidized

0.07*

250

Zn(II)

Chemically
modified

TSK

5-AHQ

50-200

Chemically
modified

Silica gel

SBTD

0.15$
0.009
0.15
0.009
0.12
0.024

5-50

Zr
Hf
Nb
Ta
W
Cr(III)

Chelate
adsorption

Graphene

DTZ

0.61

125

Pb(II)

2 mL of 2M
HNO3

Chemically
modified

AXAD-2

2-MTA

ACMNPs

IDA

300
300
400
150
100
150
----------

Cd(II)
Hg(II)
Ni(II)
Co(II)
Cu(II)
Zn(II)
Pd(II)

10 mL of 1M
HCl

Chemically
modified

0.022
0.028
0.033
0.045
0.041
0.064
47*

--------------

100

1 mL of 0.1M
SPE
HCl
ICPAES
Off-line
2.5 mL of
SPE
0.01M HCl- ICPOES
3% TU Soln.
Off-line
2 mL of 6M
SPE
HCl + 2% TU ICPAES
Soln.
Off-line
3.0 mL of MSPE
0.5M HNO3
UV-Vis
Off-line
-1
0.5 mol mL
SPE
NH3.H2O
FAAS
On-line
200 L(=0.2 MSPE
mL) of 0.5N ETAAS
HNO3
Off-line

235

1.5 mL of
1.5M HNO3

SPE
ETAAS
Off-line
0.5M HNO3
SPE
FAAS
Off-line
20 mL of
SPE
0.5M HNO3
ICP-MS
Off-line

241

10 mL of
0.5M HNO3

SPE
GFAAS
Off-line
SPE
FAAS
Off-line
SPE
FAAS
Off-line

244

MSPE
ETAAS

247

500 L of 1M
HCl

236

237

238

239

240

242

243

245

246

Chemically
modified

Magnetic
Fe3O4
Microsphere
Immobilized
In
KR
SCMNPs

MPTES

Chemically
modified

Attapulgite

ASP

Chemically
modified

Silica gel

Chemically
modified

2.1
1.9
2.5
1.9
1.8
1.7
0.043
0.058
0.085
0.19

46
32
43
44
38
46
96
95
87
200

Ru
Rh
Pd
Pt
Ir
Au
Cr(III)
Cu(II)
Pb(II)
Fe(III)

4.75*

1000

Hg(II)

MWCNTs

MAT
EDAT
DETAT
PP

1.1

200

Pb(II)

--------------

TUSAR

------------

0.15
0.021

60

Pb(II)
Cd(II)

Chemically
modified

MWCNTs

Ga(III) ion
complex
of 8-HQ

3.03

43

Ga(III)

Physically
modified

SNPs

Alumina

83.3

Chemically
modified

AXAD-2

AATP

Chemically
modified

SBA-15
Mesoporous
Silica

DCG

Chemically
modified

AXAD-16

DMABA

0.30
0.24
0.21
0.63
0.10
0.23
0.41
0.13
0.25
0.39
0.58
4.5
0.6
0.2
0.5
1.12
1.38
1.76

Cd(II)
Cu(II)
Zn(II)
Pb(II)
Cd(II)
Hg(II)
Ag(I)
Ni(II)
Co(II)
Cu(II)
Zn(II)
Pb(II)
Cu(II)
Zn(II)
Cd(II)
Zn(II)
Mn(II)
Ni(II)

Immobilization

BMT-II

400
300
200
400
150
100
150
100

300
250
100

0.2M HNO3
with
2.0%
(w/w) thiourea

Off-line
DSPE
FIICPMS
On-line

248

1 mL of 1M MSPE
HNO3
ICPOES
Off-line
2 mL of 0.5M
SPE
HCl
ICPOES
Off-line
2 mL of Conc.
SPE
HNO3
HGAAS
Off-line
10 mL of 3M
SPE
HNO3
FAAS
Off-line
3.0 mL of
SPE
1.5M HNO3
STATFAAS
Off-line
10 mL of
ISPE
Ethanol
& FAAS
acetic
acid Off-line
(9:1, V/V)
3.0 mL of 3M
SPE
HNO3
FAAS
Off-line

249

10 mL of 1M
SPE
HCl/10 mL of ICPAES
0.5M HNO3 Off-line
for Ag(I)

256

25 mL of 3M
HNO3

SPE
FAAS
Off-line

257

25 mL of 12M HCl

SPE
FAAS
Off-line

258

250

251

252

253

254

255

0.67
0.77
2.52
5.92
1.08
10*

250
250
300
450
167
200

Pb(II)
Cd(II)
Cu(II)
Fe(III)
Co(II)
Pb(II)

2.2
2.1
1.7
1.5
2.9
1.5
2.8
2.9
1.0

150

10.0 mL
2M HNO3

100

Co(II)
Ni(II)
Cu(II)
Zn(II)
Pb(II)
Cd(II)
Cr(III)
Fe(III)
Zn(II)

Chemically
modified

Silica coated
Fe3O4 NPs

Zincon

Physically
modified

SDS
Coated
Al2O3

HNMAHN

Chemically
modified

Chitosan
NPs Grafted
with -CD
AXAD-16

----------

MOPPA

4
15

400
333

U(VI)
Th(IV)

0.5M
(NH4)2CO3

Physically
modified

AC

HNBIOH

0.20
1.50

Co(II)
Ni(II)

20 mL of 2M
HNO3

Chemically
modified

Merrifield
resin

Calix[4]
arene
derivatives

5.83
8.48
5.56

117
90
105

Cr(VI)
As(III)
Tl(I)

Chelate
adsorption

RP-C18

QADEAB

0.02

200

Pd(II)

15 mL of 0.1N
H2SO4, 0.5N
HCl and 1N
HNO3/3N HCl
for
Cr(VI),
As(III)
and
Tl(I)
respectively
5 mL of 5M
HCl

Chelate
adsorption

RP-C5

4-BARA

8.5*10-5

50

Au(III)

1.0 mL
EtOH

----------

Nano meter
Sized
TiO2
SiO2
NPs

---------

0.10

30

Sb(III)
Sb(V)

------------------

PAN

0.60

62.20

Sb(III)

4 mL of 2M
HCl

Chemically
modified

Chemically
modified

0.5 mL of 1M
HCl
of

1.0 mL of 1M
EtOH

of

MSPE
GFAAS
Off-line
SPE
FAAS
Off-line

259

SPE
FAAS
Off-line
SPE
UV-Vis
Off-line
SPE
FAAS
Off-line
SPE
GFAAS
Off-line

261

SPE
UV-Vis
Off-line
SPE
UV-Vis
Off-line
SPE
ETAAS
Off-line
SPE
UV-Vis
Off-line

265

260

262

263

264

266

267

268

----------

TiO2 NPs

---------

72

83

As(V)

1.5 mL of
0.7M NaOH

---------

Eggshell
membrane

---------

0.001

33.3

As(V)

5 mL of 2M
HNO3

-----------

S.
cerevisiae

----------

8.7

Sb(III)

Chemically
modified

Nanoporous
Silica stir bar

APTES

1.6
13.8

133
137

Cd(II)
Cu(II)

10 mL of 40
mmol L-1 of
TGA
3 mL of 1M
HClO4

Chemically
modified

MWCNTs

Carboxylic
acid

0.012
0.015

2440
3710

Cd(II)
Pb(II)

3 mL of 1M
HNO3: MeOH
(70:30 v/v)

Chemically
modified

Fe3O4 NPs

DZ

0.12
0.39
0.98
1.20

128

Cd(II)
Zn(II)
Ni(II)
Pb(II)

Chelate
adsorption

Cyclodextrin
cross linked
polymer
-Alumina
nanoparticle
coated with
SDS
MWCNTs

PAR

0.056

25

Cr(III)

7.8 mL of
0.9M Thiourea
in
0.01M
NaOH
Solution
1 mL of 1M
HCl

5-BrPADAP

0.9

25

Mn(II)

PAN

0.02

100

0.1

139

Physically
modified

Chemically
modified
Chemically
modified

Amberlite
XAD-2

DZ

Chemically
modified

Silica
gel

SALD

Physically
modified

Silica
SBA-15

1,3,5TT

1.0
1.5
-----

66
50
------

SPE
GFAAS
Off-line
SPE
HGAFS
Off-line
SPE
ICP-MS
Off-line
SBSE
FAAS
Off-line
PSB-HF
SLPME
DPASV
Off-line
SPE
FAAS
Off-line

269

SPE
GFAAS
Off-line

275

1 mL of 1M
HNO3in EtOH

SPE
FAAS
Off-line

276

Ni(II)

5 mL of 1M
HNO3

277

Zn(II)

0.5M HNO3

SPE
FAAS
Off-line
SPE
FAAS
Off-line
E V SP
15 FS
20
SPE
CVAAS

Cu(II)
Ni(II)
Hg(II)

NA
1.4
1.0

PCA
0.4
0.1
N.R.

270

271

272

273

274

278

279

280

LOD: Limit of detection; S-CS: Schiff base modified chitosan; 2-AT: 2-Aminothiazol;
EDA: Ethylenediamine; DETA: Diethylenetriamine; TETA: Tetraethylenetriamine; Ros:
Rosaniline; His: histidine; AMTT: 4-amino-5-methyl-1,2,4-triazole-3(4H)-thion; DPC: 1,5diphenylcarbazide; NPs: Nanoparticles; NR: Not reported; HADPD: Bis-(2Hydroxyacetophenone)-2,2-Dimethyl-1,3-Propane Diimine; TAN: 1-(2-thiazolylazo)-2naphthol; L: 2-Hydroxy-acetophenone-3-thiosemicarbazone; PAN: 1-(2-pyridylazo)-2naphthol; QTH: Quinoline-8-thiol; Aliquat-336: Tri-octylmethylammonium chloride;
XRFS: X-Ray fluorescence spectrometry; GFAAS: Graphite furnace atomic absorption
spectrometry; CVAAS: Cold vapour atomic absorption spectrometry; DPC:
Diphenylthiocarbazone; PEG: Polyethylene glycol; DDTC: Diethyldithiocarbamate;
MWCNTs: Multiwalled carbon nanotubes; DZ: Dithizone; ETAAS: Electrothermal atomic
absorption spectrometry; CTA: Chromotropic acid; L1: 5-{-(4-Nitrophenylazo)-N-(2, 4dimethoxy-phenyl)}salicylaldimine; APTES: 3-Aminopropyltriethoxy silane; HL: 5hydroxy-4-ethyl-5,6-dipyridin-2-yl-4,5-dihydro-2H-[1,2,4]-triazine-3-thione; TAA: Tris-(2aminoethyl)amine; ICPOES: Inductively coupled plasma optical emission spectrometry;
DHAQ: 1,8-dihydroxyanthraquinone; SSA: 5-sulfosalicylic acid; Calmagite: 3-hydroxy-4[(6-hydroxy-m-tolyl)azo]-naphthalene sulfonic acid; APDC: Ammonium pyrrolidine
dithiocarbamate; AHBA: 4-Amino-3-hydroxybenzoic acid; L-Cys: L-Cysteine; MBT: 2Mercaptobenzothiazole; NPTT: 3-(2-Nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione; 1,10Phen: 1,10-Phenenthroline; DCQ: 5,7-Dichloroquinoline -8-ol; TSA: Thiosalicylic acid;
DMSPE: Dispersive micro solid phase extraction; EDXRF: Energy dispersive X-ray
fluorescence; ABA: O-Aminobenzoic acid; ATAAQ: Aminothioamidoanthraquinone; HQ:
8-Hydroxy quinoline; DHMP: 4,6-Dihydroxy-2-mercapto pyrimidine; SPIMP: 2-[(3Silylpropylimino) methyl]phenol; HBAHBA: 5-[2-Hydroxy benzylideneamino]-2-hydroxy
benzoic acid; 2,4-MBAT: 2-(4-Methoxybenzylideneamino)thiophenol; 2,4-CBABT: 2-(4Chlorobenzylideneamino) benzenethiol; BPMBDA: N,N-Bis(pyridine-2-yl-methyl)benzene1,4-diamine; TMTA: 2,4,6-Trimorpholino-1,3,5-triazin; -CDPU: -Cyclodextrin
polyurethane; L2: 3-(4-methoxybenzylideneamino)-2-thioxothiazolodin-4-one; Py: Pyridine;
Br-PADAP: 2-(5-Bromo-2-pyridylazo)-5-diethylamino phenol; ASA: Acetyl salicylic acid;
EHND:
1-[(1E,9E)-10-(2-hydroxy-1-naphthyl)-4,7-dioxa-2,9-diaza-1,9-decadienyl]-2naphthol; QAHBA: 3-(8-Quinlinylazo)-4-hydroxybenzoic acid; HMPN: 1-{[(6-{[(E)-1-(2hydroxy-1-naphthyl)methylidene]amino}-2-pyridyl)amino]methyl}-2-naphthol;
NRS:
Nitroso-R-Salt; SPF: Organic solution processable functionalized; ACMNPs: Alumina
coated magnetic nanoparticles; DMG: Dimethylglyoxime; SDS: Sodium dodecyl sulfate;
DZ: Dithizone; ITD: Indane-1,2,3-trione-1,2-dioxime; HBTSC: 2-Hydroxybenzaldehydethiosemicarbazone; NNPP: 4-Nitro-2-(2-Nitrophenylazo)phenol; HMBA: 2-Hydroxy-3methoxybenzaldehyde; TPTMS: 3-Thiopropyl-trimethoxy silane; DHHMB: 1-[{6-(-2,4Dihydroxybenzylideneamino)
hexylimino}
methyl]benzene-2,4-diol;
RATP:
Resacetophenone; NRS: Nitroso-R Salt; DPC: Diphenyl carbazone; DCA: Decanoic
acid;IPBATP:
2-(4-Isopropylbenzylideneamino)
thiophenol;
p-TSA:
pToluenesulfonylamide; SG: Silica gel; nm: Nanometer; G. t. strom: Geobacillus
thermoleovorans stromboliensis;APCA: 2-Aminopyridine-3-carboxylic acid; [{(TESP)
MIm} Cl]: N-3-(-3-triethoxysilylpropyl)-3-m3thylimidazolium chloride; NA: Nitric acid;
DDI: Distilled deionized water; AMPDAA: 2-Acetylmercaptophenyldiazoaminobenzene;
MBID: 2-Mercaptobenzimidazole; IYPMI: [(Indolin-3-yl)(phenyl) methyl indoline]; PVC:
Polyvinyl chloride; N.Rq: Not required; DNAAB: 1,3-Di-(4-Nitroamino)benzene; OVFH:
O-Vanillin furfurylhydrazone; SF: Spectrofluorimetry; MTOAC: Methyltrioctylammonium
chloride; BBHBPDI: bis-(5-Bromo-2-hydroxy-benzaldehyde)-2-methyl-1,5-pentane diimine;
DBDP: N,N-Diacetyl-4-bromo-2,6-di(aminomethyl) phenol; BHAPDMPDI: bis-(2hydroxyacetophenone)-2,2-dimethyl-1,3-propanediimine;
HMBTSC:
1-(2-hydroxy-5-

methoxybenzalidene) thiosemicarbazide; 3-MTMS: 3-mercaptopropyltrimethoxysilane; 1,2DHAQ: 1,2-Dihydroxyanthraquinone; 1,5-DPC: 1,5-Dimethyl-1H-pyrazole-3-carbaldehyde;

BMSAPD:
Bis-(4-methoxysalicylaldehyde)-1,2-phenyenediamine;
CMT-PS:
Chloromethylated
polystyrene;
PPDOT:
1-phenyl-1,2-propanedione-2-oxime
thiosemicarbazone;
2-AEEDA:
N,N-bis(2-aminoethyl)ethane-1,2-diamine;
PUF:
Polyurethane
foam;
AA:Acetylacetonate;
NAP-dien:
N,Nbis(naphthylideneimino)diethylenetriamine; (*) LOD is in pg mL-1; OD: Octadecane;
HNMABA: 2-{[1-(2-hydroxynaphthylmethylidene)amino] benzoic acid; GO-Silica:
Graphene oxide silica; HF-SPME: Hollow fibre solid phase microextraction; SDB: Styrene
divinyl benzene; PSH: Pyridoxal salicyloylhydrazone; HGAAS: Hydride generation AAS;
(**) LOQ is in ng mL-1(g L-1); MSPE: Magnetic solid phase extraction; MCM: Merrifield
Chloromethylated resin; DAPPA: (dimethyl amino-phosphonomethyl)-phosphonic acid;
AEPU: 1-(2-aminoethyl)-3-phenylurea; #LOD is in g g-1; MTPB: 4-(2-morinyldiazenyl)-N{3-(trimethylsilyl)propyl}benzamide; MNP: Magnetic nanoparticles; Q-Alizarin:
Quinalizarin; ($) is in pmol kg-1; 5-AHQ: 5-Amino-8-hydroxy quinoline; SBTD: N,N-bis(-methylsalicylidene)-2,2-dimethyl-1,3-propanediimine; 2-MTA: 2-(Methylthio)aniline;
MPTES: -Mercaptopropyltriethoxysilane; FI-ICPMS: Flow injection inductively coupled
plasma mass spectrometry; KR: Knotted reactor; SCMNPs: Silica coated magnetic
nanoparticles; BMT-II: Bismuthiol-II; ASP: Asparagine; MAT: Monoamine-2thiophenecarboxaldehyde; EDAT: ethylenediamine-2-thiophenecarboxaldehyde; DETAT:
diethylenetriamine-2-thiophenecarboxaldehyde; STAT-FAAS: Slotted tube atom trap-FAAS;
TUSAR: Thioureasulfonamide resin; HNMAHN: 1-[6-{-(2-hydroxynaphthalene-1yl)methylenamino}hexylimino]methyl; SNPs: Sulfur nanoparticles; AATP: 2Aminoacetylthiophenol; HIMB: 4-[-{-(2-hydroxyphenyl)imino}methyl]-1,2-benzenediol;
MOPPA:
[2-(1-(Methyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-ylcarbamoyl)-ethyl]phosphonic acid; HNBIOH: (E)-N-(2-hydroxy-5-nitrobenzilidene)isonicotinoylhydrazone;
MCR: Merrifield Chloromethylated resin; TGA: Thioglycollic acid; SBSE: Stir bar sorptive
extraction; PSB-HF-SLPME: Pseudo-stir bar hollow fibre solid/liquid phase micro
extraction; DPASV: Differential pulse anodic stripping voltammetry;

Table 2.2 Preconcentration of metal ions using Cloud point extraction (CPE)
method
Sr.
No.
1.

Chelating
agent
MPBIM

Surfactant

Method

Matrix

TX-114

CPEFAAS

2.

BIYPYBI

TX-114

CPEFAAS

Water
samples,
Blood serum,
urine &
radiology
films
samples
Blood, Lotus
tree, Orange
Juice

LOD
(g/L)
1.47
3.00

1.4
1.9
1.0

PF

Linear
Target
Range
Analyte
40.56 0.007-0.200 Mg(II)
(g mL-1)
Ag(I)

35
30
39

10-250
15-200
10-250

Cu(II)
Ni(II)
Zn(II)

Ref.
281

282

3.

DBDP

TX-114

CPEFAAS

4.

DPTH

TX-114

CPEFAAS

5.

BPDTC

TX-114

6.

5-BrPADAP

TX-114

CPEFAAS
CPEFAAS

7.

----------

TX-114

CPE-FIFAAS

8.

IPMI

TX-114

CPEFAAS

9.

SPAR

TX-100

CPEFAAS

10.

DZ

TX-114

CPEFAAS

11.

DZ

TX-114

CPEFAAS

12.

DMG

TX-114

13.

NTPHPI

TX-114

CPE-UVVis
CPEFAAS

14.

PHCT

SDS

CPE-UVVis

Soil, River
water, Waste
water &
Blood
Water,
environmental &
Food
samples
Real water
samples
Water
samples
Tap & Sea
water
samples
Blood, lotus
tree, liver,
spinach, soil
& orange
juice
Tap, rain &
stream water
samples
Petrochemical
Waste water
Petrochemical
Waste water
Water
samples
Water,
chocolate &
honey
samples
Natural,
waste water
and spiked
human
plasma
samples

2.2

25

15-200
(ng mL-1)
0.04-1.2
0.03-1.6
(g mL-1)

Fe(III)

1.6
1.9

33

Cu(II)
Zn(II)

283

0.95

10.5

10-200
(ng mL-1)

Cd(II)

284

0.5

67

Co(II)

285

2.4
1.7
1.5
0.3

25

2-150
(g L-1)
10-100
(g L-1)

286

63

3-250
(g L-1)

Co(II)
Ni(II)
Cu(II)
Cd(II)

1.6
2.1
1.1
2.8

30

Cu(II)
Ni(II)
Zn(II)
Fe(III)

288

1.64

31

0.01-0.30
0.01-0.30
0.01-0.20
0.01-0.30
(mg L-1)
4-450
(g L-1)

Cu(II)

289

N.R.

N.R.

0.2-2.0
(mg L-1)

Zn(II)
Fe(III)

290

N.R.

0.2-2.0
(mg L-1)

Cu(II)

291

20

Ni(II)

292

1
5
6

70.5
70.65
63.5

10-150
(ng mL-1)
0.007-0.33
(mg L-1)

Ni(II),
Cu(II),
Co(II)

293

2
3

-----

Pb(II)
Cu(II)

294

0.01-090
(g mL-1)

287

15.

STAR

TX-100

16.

ACDTCA

TX-114

17.

CTR

18.

VBB

TX-114
+
CTAB
TX-114

19.

TX-114

20.

HNMAHBA
DTZ

21.

DMIT

TX-114

22.

BTABD

CTAB

CPE
UV-Vis

23.

5-BrPADAP

TX-100

CPE
ICPOES

24.

Sudan II

TX-114/
SDS

CPE
UV-Vis

25.

Ligand
less
Magneson
I

PONPE 7.5

CPE
FAAS
CPE
FAAS

27.

NMIOHCA

TX-114

CPE
FAAS

28.

PAN

TX-114

CPE
ETAAS

29.

TAO

TX-114

CPE
FAAS

30.

ECR

CTAB

CPE
UV-Vis

31.

MOSDA

TX-114

CPE
FAAS

26.

TX-114

TX-114

CPEFAAS
CPE
ETAAS
CPE
UV-Vis

Water & ore

samples
Water
samples
Water
samples

0.75

31

0.04

195

0.035

20

CPE
UV-Vis
CPE
FAAS
CPE
UV-Vis
CPE
FAAS

Beverage
samples
Water
samples
Liver
samples
Natural
Water
samples
Natural
Water
Samples
Urine, lake
water

0.34

36.2

0.59

50

4.6

----

2.85

100

0.6

50

0.72
0.28

----

Different
beverage
samples
Water
samples
Tap water &
food samples

0.085

23

0.5

100

2.5
1.9
2.3

17
18
16

Vegetable,
soil & water
samples
Dust,
drinking &
rain water
samples
Water
samples

0.065

81

10.0

26

------

56
85

Tap & well

water
samples
River water
& Millet

0.05

----

0.47

19

6-2000
(g L-1)
0.04-0.70
(ng mL-1)
0.2-10
(ng mL-1)

Au(III)

295

Bi(III)

296

U(VI)

297

1-30
(g L-1)
4-20.0
(g mL-1)
15-250
(ng mL-1)
0-650
(g L-1)

Cd(II)

298

Cr(III)

299

Cu(II)

300

Pb(II)

301

2.0-240
(ng mL-1)

Pd(II)

302

6-200
2-200
(ng mL-1)
0.285-20
(g L-1)

Ga(III)
In(III)

303

Cu(II)

304

2-100
(g L-1)
20-1500
10-500
10-500
(g L-1)
1.14-4.83
(ng mL-1)

Ni(II)

305

Pb(II)
Fe(III)
Cr(III)

306

Pt(IV)

307

3-200
(g L-1)

Pd(II)

308

0.7-2.6
4.5-8.4
(g L-1)
0.2-20.0

Cd(II)
Pb(II)

309

Al(III)

310

Co(II)

311

0.002-1.2
(g mL-1)

32.

HIQSA

TX-114

CPE
FAAS

33.

MBTHQ

TX-114

CPE
UV-Vis

34.

2-MHQ

TX-114

CPE
FAAS

35.

DDTP

TX-114

CPE
ICP-MS

36.

DZ

TX-114

CPE
UV-Vis

samples
Infant dry
formula
milk, human
and cows
milk, tap,
river, spring
and rain
water
Honey
samples
Med. Plants
& human
blood
River, sea &
enriched
water

Vegetable
samples

1.7
(g)

N.R.

5-150
(g)

Fe(III)

312

3.9
0.19

N.R.

Pb(II)
Cd(II)

313

1.4
(g)

N.R.

5.0-100
0.32-7.5
(ng mL-1)
5-20
(g)

Zn(II)

314

0.004
0.006
0.003
0.006
0.03
0.004
0.02

N.R.

Ag(I)
As(V)
Au(III)
Cd(II)
Cu(II)
Pb(II)
Se(IV)

315

0.2

50

0.1-1
(g L-1)
For Cu(II)
& As(V)
0.01-0.5
(g L-1)
For Ag(I),
Au(III),
Cd(II),
Pb(II) &
Se(IV)
1.0-180

Cd(II)

316

TX-100: Triton X-100; TX-114: Triton X-114; SDS: Sodium dodecyl sulphate; PONPE:
Poly(oxyethylene)nonylphenylether; CTAB: Cetyltrimethyl ammonium bromide; MPBIM:
4-methyl-3-[{1-H-Indol-3-iyl} (phenyl) methyl}]-1-H-Indol; BIYPYBI: 2-[6-{1Hbenzo[d]imidazol-2-yl]-1H-benzo[d]imidazole;
DBDP:
N,N-Diacetyl-4-bromo-2,6di(aminomethyl) phenol; DPTH: 1,5-bis(di-2-pyridylmethylene) thiocarbonohydrazide;
BPDTC:
4-Benzylpiperidinedithiocarbamate;
IPMI:
3-[(Indolin-3-yl)
methyl
phenyl]indoline; SPAR: Sulfapyridylazo resorcinol; DMG: Dimethyl glyoxime; NTPHPI:
N-(2-Thiophenyl)-1-(2-hydroxyphenyl)Imine; PHCT: N1, N2-Diphenylhydrazine-1,2dicrabothioamide; STAR: Sulphathiazolylazo resorcinol; ACDTCA: 2-Amino-cyclopentene1-dithiocarboxylic acid; CTR: Chromotrope-2R; VBB: Victoria Blue B; HNMAHBA: 4-[(1Hydroxynaphthalene-2-yl)-methyleneamino]-2-hydroxy benzoic acid; DTZ/DZ: Dithizone;
DMIT: 4,5-Dimercapto-1,3-dithyol-2-thionate; BTABD: 4-(2-Benzothiazolylazo)-2,2biphenyldiol; Br-PADAP: 2-(5-Bromo-2-pyridylazo)-5-diethylamino phenol; PAN: 1-(2pyridylazo)-2-naphthol; TAO: 4-(5-Bromo-2-thiazolylazo) orcinol; ECR: Eriochrome
cyanine R; MOSDA: 4-Methoxy-2-sulfobenzenediazoaminoazo benzene; HIQSA: 8-

Hydroxy-7-iodo quinoline-5-sulphonic acid; MBTHQ: 7-(6-Methoxy-2-benzothiazolylazo)8-hydroxy quinoline; DDTP: O,O-Diethyl dithiophosphate

Dithiocarbamates have found variety of applications in agriculture as systemic fungicides and

in rubber industry as vulcanization accelerators and antioxidants. DTCs are also used
clinically for the treatment of chronic alcoholism and as anticancer and antitoxic drug agents
[317-20]. DTC complexes are toxic and have mutational effect [321]. Rathore et al. [322]
have studied the mobility of DTC pesticides through soil and this aspect of their behaviors

presents severe

hazards

for

mankind

they

be

as

can

washed in to

drinking water

sources

entering

thus

our

food chains. Hylin et al. developed colorimetric methods for Maneb determination [323].
Turker et al. devised a flame atomic absorption spectrometry method for indirect
determination of Dithiocarbamate pesticides [324]. Crnogorac and Schwack have provided
insight into the various methods for residue analysis of dithiocarbamate fungicides [325].
Waseem et al. have used a flow injection method for the analysis of DTC fungicides with
chemiluminescence detection [326]. A microwave assisted extraction (MAE) method
involving hydrolysis of dithiocarbamates and their analysis in tobacco leaves was developed
by Vryzes et al. [327]. Lo et al. [328] have determined propineb, zineb, maneb and mancozeb
by an HPLC method. Differential pulse polarography (DPP) technique has been employed for
the determination of DTC residues by Schwack et al. [329]. Cesnik et al. [330] have
developed validation for a GC-MS method for the determination of DTCs in foodstuffs.
Crnogorac et al. have presented a method using LC-MS (Liquid chromatography tandem
mass spectrometry) method for the determination of DTC fungicides residues in fruits and
vegetables [331]. Dithiocarbamates can also be determined by other methods such as
iodometry [332], EDTA [333], polarography [334], determination of the pesticides as their
metallic components [335-36], derivative spectrophotometry [337], spectrophotometry [338],
H-Point Standard addition method [339], silica nanoparticles [340], chitin [341], naphthalene
[342], flow injection spectrophotometry [343] have been proposed.

ynthesis and characterization of 1-(2-pyridylazo)-2-naphthol

modified -cyclodextrin polymer

Cyclodextrins (CDs) are water soluble cyclic, non reducing oligosaccharides consisting of D(+)-gluocopyranose units linked through -1,4-glycosidic linkages. The major and most
common three cyclodextrins, -cyclodextrin, -cyclodextrin and -cyclodextrin consists of
six, seven and eight D-(+)-gluocopyranose units, respectively. In CDs every gluocopyranose

unit has three free OH groups, two of which (C-2 and C-3) are secondary and one (C-6) is
primary. As each of these free hydroxyl group can be modified, it makes selective
modification extremely difficult. Cyclodextrins are modified for a wide variety of reasons. In
CD derivative family, CD polymers reserve a special position. In recent years attention has
been expanding from supramolecular chemistry of cyclodextrins to supramolecular chemistry
of cyclodextrins based polymers because more sophisticated structures and advanced
functions have been achieved by the formation of supramolecular cyclodextrin polymers.
Compounds consisting of covalently linked cyclodextrin rings are called cyclodextrin
polymers. The cyclodextrins fixed into polymeric structures behave differently from their
monomeric derivatives. CD polymers not only have the inclusion ability, the controlled
release ability, like their parent CDs, but also have fine mechanical intensity and excellent
stability. Therefore, CD polymers have been studied for a long time and received much
attention in pharmaceutical industry, biomedical areas and environmental chemistry. The first
review of the potential application of cyclodextrin polymers in pharmaceutical industry was
given by Fenivesy [344] and Szeman et al. [345]. Renard et al. proposed that the molecular
weight of the water soluble -cyclodextrin polymer depends on the base concentration and
the reaction time [346]. They proposed that higher base concentration leads to modification
on both the faces of -cyclodextrin, whilst lower base concentration leads to substitution only
on face of cyclodextrin.

Why CD modification is needed?

Cyclodextrins (CDs) are water soluble; therefore they cannot be used as an adsorbent in the
uptake of the metal ions and various organic pollutants. The only possible way is to cross link
the cyclodextrin either by using a suitable cross-linking agent or by covalently binding the
cyclodextrin to the backbone of the existing polymers.

Modification of Cyclodextrins
-Cyclodextrin can be modified by one of the two possible methods:
(i)
(ii)

Direct method
Indirect method.

Direct method involves the direct modification of cyclodextrin using a coupling agent or a
cross-linker that results in the formation of a three dimensional structure (Fig. 3.1.1). The
properties of the cross-linked cyclodextrin are determined by the following factors:

 type of cyclodextrin viz., -, - and -CD,

type of cross-linker and
molar ratio of the cyclodextrin and the cross-linker.
Variation in all these factors leads to the formation of cyclodextrin polymers with different
sorption behaviour, porosity, chemical properties and density.
Indirect method
Indirect method involves the covalent binding of the cyclodextrin molecule to the already
existing polymeric structure alternatively the surface of the fibers can be modified using
cross-linked cyclodextrin polymers and subsequently used for the filtration, delivery or
debittering purposes.
Because of non-toxic, biodegradable and bioabsorbable properties of CDs, cyclodextrins
fixed into polymeric structures have found a range of applications in various fields such as
food industry, pharmaceuticals and in environmental remediation. These applications have
been reviewed as follows:
Liu et. al., (2005) Synthesized a novel reagent by reaction of -Cyclodextrin polymer (CDP) with 2-DHPH(2,4-dihydroxyacetophenone phenylhydrazone) and exploited its use in
the determination of Cd(II) in different water samples [347].
-Cyclodextrin polyurethanes have been exploited for the removal of organic contaminants
by S.D. Mhlanga et. al., (2007) [348].
L. Ding et al., (2010) Studied the -Cyclodextrin-Zn(II) inclusion complex [349].
R. Mirzajani et al., (2013) exploited -Cyclodextrin based polyurethane (-CDPU) polymers
as a solid media for adsorption and determination of Pb(II) ion in dust and water samples
[350].
J. Rima and K. Assaker (2013) Exploited the use of -Cyclodextrin polymer modified with
beet root fibers for the determination of Zn(II), Pb(II) and Cu(II) [351].
Shirasawa et al., (2013) -CD polymer cross-linked with 4,4 -methylenebisphenylene
diisocyante (MPDI) was synthesized and used in the solid phase extraction of patulin from
apple juice [352].
Raoov et al., (2013) -Cyclodextrin ionic liquid (-CDIL) cross-linked with toluene
diisocyante (TDI) was used to adsorb As(V) and phenols [353].
Sikder et al., (2014) presented a novel remediation method for the removal of Cu(II) from
different water samples using -cyclodextrin cross-linked with epichlorohydrin. They found
that the uptake of Cu(II) followed pseudo second order kinetics and justified the Langmuir
adsorption isotherm [354].

Kawano et al., (2014) -CD cross-linked with dibasic acid was synthesized and used as an
adsorbent for the removal of polychlorinated biphenyls (PCBs) from oil samples [355].
Kayaci et al., (2014) carried out a comparative study using electrospun nanofibres modified
with -, - and -cyclodextrin cross-linked with citric acid for the removal of phenanthrene
and concluded that modification of the fibre followed the order: -CDP > -CDP > -CDP
[356].
For exploiting the utility of CD polymers in preconcentration/separation of metal ions,
pristine polymer is modified with a suitable chelating agent. Chelating group can be loaded
into the sorbent by three different means:
i
ii

the synthesis of new sorbents containing chelate group (new sorbents);

the chemical bonding of such groups on existing sorbents (functionalized

iii

sorbents);
the physical binding of the groups on the sorbent by impregnating the solid matrix
with a solution containing the chelating ligand (impregnation, coated or loaded
sorbents).

The latter remains the most simple to be used in practice.

Chapter 3 deals with the synthesis of -Cyclodextrin polymer using 1,4-butanediol diglycidyl
ether as the cross-linker. The synthesized polymer is then further modified using the chelating
reagent, 1-(2-pyridylazo)-2-naphthol (PAN). The chelating reagent was physically loaded on
to -CD polymer (-CDP). The reagent being hydrophobic in nature gets included in the
hydrophobic cavity of the CD polymer resulting in formation of -CDP-PAN inclusion
complex. Inclusion complex is stabilized by the hydrophobic interactions and Vander Waals
interaction. No chemical bond is involved during inclusion complex formation

3.1 Synthesis of -Cyclodextrin Polymer (-CDP) modified 1-(2pyridylazo)-2-naphthol (PAN)

3.1.1 Materials

3.1.1.1 Equipment
A thermostatic shaking water bath (Perfit India Ltd.) was used to carry out all the inclusive
procedures.

3.1.1.2 Reagents
All reagents used were of analytical reagent grade (Sigma Aldrich/Merck). Double distilled
water was used throughout the experiment.
4 10-6 M solution of the PAN reagent was prepared by dissolving an appropriate amount of
PAN (Fluka Chemical Company) in N,N-dimethylformamide (DMF) solvent.
1,4-Butanediol diglycidyl ether was obtained from sigma Aldrich chemical company
(U.S.A.).
-Cyclodextrin was obtained from SD fine chemical India private limited (Mumbai).
Calibrated glass apparatus (Borosil) were used for volumetric purposes. Glass wares were
washed with chromic acid and soaked in 5% nitric acid and rinsed with double distilled water.

3.1.2 Procedure
3.1.2.1 Synthesis of the -Cyclodextrin polymer (-CDP)
-CDP was synthesized by known method [357]. A brief procedure for the synthesis is
described here. 20gm of -CD was dissolved in 50mL of 20% NaOH. To this was added
20mL of 1,4-butanediol diglycidyl ether drop wise. The polymer was formed in 1.5h and
dried at 900C. The polymer was ground, sieved and washed with double distilled water 5-6
times. Then, the polymer was dried again at 900C and kept at room temperature (250C) in a
dessicator.

Fig. 3.1.1 Represents generalized form showing cavity, toroidal form, primary
and secondary faces of -Cyclodextrin (-CD) & -Cyclodextrin polymer (CDP).

Fig. 3.1.2 Schematic representation of the synthesis cyclodextrin polymer

3.1.2.2 Mechanism of the synthesis of -Cyclodextrin polymer (-CDP)

The Synthesis of -Cyclodextrin polymer (-CDP) from -CD (-Cyclodextrin) and cross
linker 1,4-Butanediol diglycidyl ether involves the abstraction of hydrogen ion from free
primary and secondary hydroxyl groups to form oxy anions (I). The resulting oxy anion then
attacks on to the epoxide ring of the cross-linker resulting in the generation of a new oxy
anion (II) which then abstracts the hydrogen ion (H +) from the medium and results in the
formation of (III). This reaction goes on and results in the formation of cross-linked cyclodextrin polymer.

Fig. 3.1.3 Mechanism of the synthesis of -Cyclodextrin polymer (-CDP)

3.1.2.2 Inclusion of the reagent PAN to form PAN modified -CDP polymer
The regent PAN was included into cavity of the -CD polymer following the literature
method [358]. 5.0gm of the synthesized polymer, -CDP was taken in a 250 mL Stoppard
conical flask. To this was added 10mL of 9.5 pH buffer solution and polymer was allowed to
swell for 15 minutes. A fixed volume of 4 10 -6 M solution of the PAN was added to the
treated polymer and made 50 mL with distilled water. It was shaken for two hours. The
colored polymer so obtained was washed with distilled water and dried at 100 0C. The
modified polymer was stored in a dessicator at room temperature for future use.

3.1.3 Structure of the PAN modified -CDP polymer

Fig. 3.1.4 1-(2-pyridylazo)-2-naphthol (PAN) Included in the cavity of Cyclodextrin Polymer (-CDP) to form PAN- -CDP Host-guest inclusion
complex

3.1.4 Characterization of -CDP

The synthesized polymer was subjected to different techniques for characterization purpose
(i)
(ii)
(iii)
(iv)
(v)

FT-IR Analysis,
SEM Analysis,
TGA/DTA Analysis &
XRD Analysis
Elemental Analysis.

3.1.4.1 Fourier Transform Infra-red (FT-IR) Analysis

The reactant -Cyclodextrin (-CD), the synthesized -Cyclodextrin polymer (-CDP) and
PAN modified -CDP (-CDP-PAN) were subjected to IR analysis on a Pro resolution FTIR
system as KBr pellets in the range 4000-400 cm-1region. From FT-IR (KBr) of -CD, -CDP
and -CDP-PAN it can be seen that: for -CD, 3600- 3000 (OH), 2900 (CH); while for CDP a sharp band at 3400 (OH) is obtained which indicates free OH group as shown in the
structure above. A prominent band at 1120 (COC) ether linkage which is present in the
linker and its absence in -CD spectra clearly indicates the polymerization process.

Fig. 3.1.5 FT-IR Spectrum of native -Cyclodextrin

Fig. 3.1.6 FT-IR Spectrum of cross-linked -Cyclodextrin polymer (-CDP)

Fig. 3.1.7 FT-IR spectrum of PAN modified -CD polymer (-CDP-PAN)

3.1.4.2 Scanning Electron Microscope (SEM) Analysis

The synthesized polymers were subjected to SEM analysis to study their morphological
aspects. SEM Scans of the polymers were carried out at Sophisticated Instrumentation centre
(SIC), Punjabi University, Patiala on JEOL (Tokyo, JAPAN) JSM-6510/LV-SEM Instrument.
For the above experiment 1mg. of the sample was mounted on a glass slide and subjected to
scan at an acceleration voltage of 10Kv. The SEM images were taken at five different
magnifications from X200, X1000, X2500, X3000 and X5000. From the SEM micrographs it
is obvious that the structure of -CD is rock like and -CDP is relatively fibrous which shows
that cross-linking has taken place.

Fig. 3.1.8 SEM scan of -CD at X200

Fig. 3.1.9 SEM scan of -CD at X1000

Fig. 3.1.10 SEM Scan of -CD at X2500 Fig. 3.1.11 SEM Scan of -CD at
X3000

Fig. 3.1.12 SEM Scan of -CD at X5000

Fig. 3.1.13 SEM Scan of -CDP at X200 Fig. 3.1.14 SEM Scan of -CDP at
X1000

Fig. 3.1.15 SEM Scan of -CDP at X2500 Fig. 3.1.16 SEM Scan of -CDP at
X3000

Fig 3.1.17 SEM Scan of -CDP at X5000

Fig. 3.1.18 SEM Scan of -CDP-PAN

at X200

Fig. 3.1.19 SEM Scan of -CDP-PAN

at X1000

Fig. 3.1.20 SEM Scan of -CDP-PAN

X2500

Fig. 3.1.21 SEM Scan of -CDP

PAN at X3000

Fig. 3.1.22 SEM Scan of -CDP-PAN at X5000

3.1.4.3 Thermo gravimetric and Differential thermo gravimetric (TGA/DTA)

Analysis
The synthesized polymers were subjected to TGA/DTA analysis on a TA instruments Q-500
to investigate the thermal and stability properties of the polymers. The analysis was carried
out at SMITA Lab, Dept. of Textile Tech., IIT, Delhi. The thermo gravimetric analyses were
carried out in air up to temperature of 600 0C. at a heating rate of 10 0C/min. on a 15-20 mg.
of samples.
The following changes have been observed during:
(i)
(ii)

The weight loss at 100 0C is primarily due to charring of glucose molecules.

The enhanced stability of -CD polymer is attributed to the cross-linked nature.

(iii)

Since it is well known that cross linking leads to thermal stability.

The presence of two exothermic peaks are due to linkage of cross linker

Fig. 3.1.23 TGA/DTA curve of cross-linked -Cyclodextrin polymer (-CDP)

Fig. 3.1.24 TGA/DTA curve of PAN modified -Cyclodextrin polymer (-CDPPAN)

3.1.4.4 XRD Analysis

Further evidence for the formation of the -CD polymer was obtained through the X-ray
powder diffraction (XRD) as demonstrated in the coming slides. The XRD analysis of the
polymers was carried out at XRD analysis centre at IIT Ropar, Ropar (Punjab). From the
XRD scan, it can be observed, the diffraction pattern of -CDP showed several sharp peaks
and is less diffused which corresponds to relatively crystalline nature of -CDP. But XRD
pattern of PAN--CDP is more diffused and peaks are not as sharp as that of parent polymer,
which simply accounts for amorphous nature of PAN modified -CD polymer.

Fig. 3.1.25 XRD Spectra of cross linked -Cyclodextrin polymer (-CDP)

Fig. 3.1.26 XRD spectra of PAN modified cyclodextrin polymer (-CDP-PAN)

3.1.4.5 Elemental analysis

The synthesized polymers were subjected to elemental analysis at Instrumentation Centre
Department of Chemistry, Punjabi University, Patiala on a CHNS Elementar Analysen
Systeme, Vario Micro Cube, Hanau (Frankfurt) Germany Instrument. The experimental
results obtained from elemental analysis of synthesized polymers were found to be same as
that of calculated one.

Fig. 3.1.27 Elemental analysis spectrum of -Cyclodextrin polymer (-CDP)

Fig. 3.1.28 Elemental analysis spectrum of PAN modified -Cyclodextrin

polymer (-CDP-PAN)

Fig. 3.1.29 Elemental analysis spectrum of PAN modified -Cyclodextrin

polymer (-CDP-PAN)

reconcentration and determination of toxic metal ions

using -cyclodextrin polymer modified with PAN {1-(2pyridylazo)-2-naphthol}

Growing industrialization and urbanization has contributed significantly towards the

environmental pollution because of the diversified use of the metals in varied forms. Metals
can be put into category of toxic, persistent and bioaccumulative chemicals that causes health
hazards through environmental and occupational exposures. Assessment of toxic metal ions
in different matrices viz., different water, biological and food samples is of paramount
importance. However, direct determination of toxic metal ions is quite difficult even with
highly

sophisticated

instrumental

techniques

such

as

flame

atomic

absorption

spectrophotometry (FAAS), electrothermal atomic absorption spectrophotometry (ETAAS),

inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively
coupled plasma mass spectrometry (ICP-MS) because of low concentration of analyte ions
and matrix interferences [359-60]. Therefore, suitable preconcentration steps are to be taken
prior to determination using different analytical techniques. Out of the different
preconcentration procedures available, solid phase extraction (SPE) addresses the problem in
a much better way because of its added advantages. Different solid phase extraction materials
including chromosorb-102 [361], modified rice husks [362], Ambersorb-572 [363], AXAD1180 [364], Chromotropic acid functionalized polyurethane foam [365], Merrifield resin
supported chelates [366], polymeric sorbents [367], AXAD-16 [368], pyrollidine
dithiocarbamate (APDC) modified activated carbon [369], chelax-100 [370], SiO2 NPs [371],
egg-shell membrane [372], imminodiacetate resins [373], organonanoclay [374], MIP
modified MWCNTs [375], Au NPs loaded on activated carbon [376], Polystyrene [377],
Cysteine

modified

silica

spheres

[378],

AXAD-2

[379],

sulphur

NPs

[380],

nanopolyacrylonitrile fibre [381], ammonium nanosized titania [382], TiO 2 NPs [383], SDS
coated -alumina nanoparticles [384], Py-MWCNTs [385], HNCATSC modified AXAD-4
[386], Silica gel F254 [387], Mesoporous Silica (SBA-15) [388] etc. have been exploited as
solid phase extractants in the preconcentration of toxic metal ions. The use of chelating
polymers in SPE of metal ions has come out to be the most active area of research in the field
of separation science in recent years [389]. Amongst the chelating agents, 1-(2-pyridylazo)-2naphthol is one of the most commonly used agents. It is a heterocyclic ligand. Analytical
applications of reagent PAN in spectrophotometric determinations of metal ions are well
established [390-92]. PAN is capable of complexing with most of the metal ions through the
heterocyclic nitrogen, azonitrogen nearest to the phenolic ring and o-hydroxyl group of 2naphthol (-naphthol) [393]. The present work deals with the preconcentration of metal ions

using1-(2-pyridylazo)-2-naphthol (PAN) modified -cyclodextrin butanediol diglycidyl ether

polymer as a solid phase extractant.

Scheme 1 Plausible structure of Mn+-PAN--CDP complex

4.1 Preconcentration of Cu(II) using -CDP-PAN polymer

4.1.1 Materials
4.1.1.1 Equipment
A Shimadzu UV-1800 spectrophotometer (Shimadzu Ltd., Japan) equipped with the matched
10-mm quartz cells was used to measure absorbance. All pH measurements were performed
using Digital century pH-meter CP 901 with a combined glass electrode. A thermostatic
shaking water bath (Perfit India Ltd.) was used to carry out all the inclusive procedures.

4.1.1.2 Reagents
All reagents used were of analytical reagent grade unless otherwise specified. Double
distilled water was used throughout the experiment.
Standard Cu(II) solution was prepared by dissolving 0.249gm. of copper sulphate
pentahydrate [CuSO4.5H2O] in 100 mL of distilled water to give std. stock solution.
4 10-6 M solution of the PAN reagent was prepared by dissolving an appropriate amount of
PAN (Fluka Chemical Company) in N,N-dimethylformamide (DMF) solvent.
1,4-Butanediol diglycidyl ether was obtained from sigma Aldrich chemical company
(U.S.A.).
-Cyclodextrin (-CD) was obtained from SD fine chemical India private limited (Mumbai).
Buffer solution used were hydrochloric acid/sodium acetate for pH 2.0-3.5, sodium
acetate/acetic acid for pH 4.0-6.5, ammonia/ammonium chloride for pH 8-11.
Calibrated glass apparatus (Borosil) were used for volumetric purposes. Glass wares were
washed with chromic acid and soaked in 5% nitric acid and rinsed with double distilled water.

4.1.2 Procedure
4.1.2.1 Batch extraction procedure
At room temperature, -CDP-PAN (400 mg.) and 10.0 mL of buffer solution (pH 8.5) were
added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN should swell sufficiently. 150ng. of Cu(II) were
added and made up to 100 mL with double distilled water. After the mixture was shaken in
the thermostatic shaking water bath for 40 min, 5.0 mL of the supernatant solution was
transferred into a 10 mL volumetric flask and the absorbance was measured using standard

spectrophotometric method [394]. Cu(II) retained on -CDP-PAN polymer was eluted using
4.0 mL of 2M HCl.

4.1.3 Optimization of various parameters

4.1.3.1 Effect of pH
The uptake of an analyte on the chelating polymer is dependent on the pH of sample solution
due to the competitive reaction between chelate forming groups and hydrogen ions in the
solutions. 150ng. of Cu(II) were taken and made it 100 mL. To this added 400 mg. of resin
and shook for 40 min. The pH of this solution was adjusted in the range of 3.5 to 10.5 using
different buffer system and then the preconcentration procedure described was applied.
Quantitative uptake ( 95%) was obtained in pH range of 7.5-10.5 0.01(Fig. 4.1.1).

4.1.3.2 Effect of the amount of polymer

The amount of the polymer is another important parameter that affects the uptake of an
analyte. A quantitative retention ( 95%) cannot be achieved when the polymer is less than
the optimum amount. On the other hand, an excess of polymer prevents the quantitative
elution of the retained metal chelate by a small volume of the eluent. In order to optimize the
smallest amount, 100, 200, 300, 400, 500, 600 mg. of the polymer were added to sample
solution containing 150 ng. of Cu(II) and preconcentrated by the general procedure. The
quantitative recoveries were obtained for and above 400 mg. of polymer (Fig. 4.1.2).
Therefore, 400 mg. of the polymer has been used for subsequent studies.

4.1.3.3 Effect of shaking time on % uptake of Cu(II)

Shaking time is an important factor in determining the possibility of application of the CDP-PAN polymer for the % uptake of Cu(II). For studying the effect of shaking time on the
% uptake, 400 mg. of polymer, 150ng. of Cu(II) were taken in 100 mL of solution and shook
for different shaking time (ranging from 10 to 50 minutes) with an interval of 10 minutes at
optimum pH. The results of % uptake of Cu(II) vs. the shaking time show that the percentage
uptake reached maximum (above 95%) at 40 min (Fig. 4.1.3). Therefore, 40 min. was
selected as the optimum shaking time.

4.1.3.4 Effect of sample volume on % uptake of Cu(II)

In order to explore the possibility of enriching low concentration of analytes from large
volume of sample, the effect of sample volume on the retention of Cu(II) was also

investigated. For this purpose 25, 50, 100, 150, 200, 250, 300, 350, 400, 450 and 500 mL of
sample solutions containing a fixed amount of Cu(II), 400 mg. of polymer, optimum pH and
a shaking time of 40 min. Quantitative uptakes ( 95%) were obtained for sample volume of
400 mL (Fig. 4.1.4). But for convenience, 100 mL of sample solution was adopted for the
preconcentration of analyte from sample solutions.

4.1.3.5 Effect of shaking speed (r.p.m.) on % uptake of Cu(II)

The % uptake of Cu(II) increased gradually with a rise in the shaking speed (Fig. 4.1.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Present study suggests that the shaking effect is
high-flying parameter for the maximum % uptake of an analyte ion.

4.1.3.6 Effect of Nature of Eluent on % uptake of Cu(II)

In order to choose the best eluent for the Cu(II) retained on -CDP-PAN polymer, various
eluent were tested. Among the eluents studied, hydrochloric acid (HCl) provided higher
recovery efficiency than the organic solvents.

4.1.3.7 Effect of eluent conc.

The effect of eluent concentration on the recovery of Cu(II) was also examined. Different
concentrations of HCl ranging from (0.5-4M) were tested in order to strip the Cu(II) from
polymer. The recovery of Cu(II) increased, as HCl concentration increased up to 2.0M and it
decreased above this concentration. Therefore an HCl concentration of 2.0 M was selected for
subsequent studies (Fig. 4.1.6).

4.1.3.8 Effect of Eluent volume

In order to choose proper volume of the eluent, the retained complex was stripped with
different volumes (16 mL) of 2.0 M HCl. It is clear that 5 mL would not be suitable because
it gave a smaller preconcentration factor and 3mL was not sufficient for the elution (Fig.
4.1.7). Hence, 4 mL of 2.0 M HCl was chosen for elution of the metal ion complexes. The
preconcentration factor is calculated by the ratio of the highest sample volume (400 mL) and
the lowest eluent volume (4 mL). Thus, the preconcentration factor found was 100.

100
80
60
% Uptake of Cu(II)

40
20
0
3.5 4.5 5.5
6.5 7.5 8.5
9.5 10.5
pH

Fig. 4.1.1 Effect of pH on the % uptake of Cu(II)

100
80
60
% Uptake of Cu(II)

40
20
0
100

200

300

400

500

600

Amount of polymer (mg.)

Fig. 4.1.2 Effect of amount of polymer on the % uptake of Cu(II)

120
100
80
60
% Uptake of Cu(II)

40
20
0
10

20

30

40

50

Shaking Time(min.)

Fig. 4.1.3 Effect of the shaking time on % uptake of Cu(II)

120
100
80
60
% Uptake of Cu(II)

40
20

50
0

40
0

30
0

20
0

10
0

25

Sample Volume(mL)

Fig. 4.1.4 Effect of sample volume on % uptake of Cu(II)

100
80
60
% Uptake of Cu(II)

40
20
0
40

60

80

100

120

140

Shaking Speed (r.p.m.)

Fig. 4.1.5 Effect of shaking speed on % uptake of Cu(II)

100
80
60
% Uptake of Cu(II)

40
20
0
0.5

Eluent Conc. (M)

Fig. 4.1.6 Effect of eluent conc. on % uptake of Cu(II)

120
100
80
60
% Uptake of Cu(II)

40
20
0
1

Eluent Volume (mL)

Fig. 4.1.7 Effect of eluent volume on the % uptake of Cu(II)

4.1.4 Effect of interfering ions

The effect of various foreign ions on the % uptake of a solution containing 150ng. of Cu(II)
was studied. An ion was considered to interfere when its presence produced a variation in the
% uptake of the sample 5%. Among the anions examined CO 32-, SO32-, SO42-, NO3-, IO3-,
NO2- did not interfere at concentrations 1000 times more than those of the analyte (Table
4.1.1). The complexation between Cu(II) and PAN was completely masked by EDTA
(ethylenediamine tetraacetate ion) and cyanate even at lower concentration. Alkali and
alkaline earth metal ions did not interfere.

Table 4.1.1 Tolerance limit of foreign ions in the determination of Cu(II)

Foreign Ion(Anion/Cation)
NO3, SO4, HPO42, SCN,
NO2, PO43, ClO3 , IO3,
Cl, I, Br, CH3COO,
C2O42Na(I), K(I), Mg(II), Ba(II),
Al(III), Rb(I), Cs(I), Ag(I)
Sb(III), Ca(II), Zr(IV),
Ti(IV)
Th(IV), Sn(II), As(III)
a
Fe(III), bNi(II)
c
Zn(II), dPb(II), eFe(II),
e
Mn(II), fHg(II), fCd(II)
EDTA, CN-, F-, S2O32-

Tolerance Limit
[Wforeign ion/WCu(II)]
>2000

1000
500
200
30
10
1

a-masked with 1.0 mL of 5.0% ammonium oxalate; b-masked with 1.0 mL of 2.0%
dimethylglyoxime; c-Masked with 1.0 mL of 10.0% sodium citrate solution; d-masked with
2.0 mL of 1% sodium sulphate; e-masked with 2.0 mL of 3.0% sodium hexametaphosphate
solution; f-masked with mixed masking agent solution of 1.0 mL of 5.0% potassium
pyrophosphate, 1.0 mL of 25.0% citric acid and 1.0 mL of 10.0% thiourea solution.

4.1.5 Validation of the method

The validity of the method was checked by applying it for the determination of Cu(II) in
certified alloy samples, different water and vegetable samples.

4.1.5.1 Determination of copper in standard alloys

The proposed method has been applied for the determination of Cu(II) in Manganin,
Constantan alloys to check the validity of the method. The alloy sample was digested using
the reported method [395]. A 0.1 gm of the standard alloy was completely dissolved in 20 mL
of HCl by heating on a water bath; 2 mL of 30% hydrogen peroxide was added to the
solution. The excess of peroxide was decomposed by heating the solution on a water bath.
The solution was cooled, filtered and diluted to 100 mL with double distilled water. Further
dilutions were made as and when required. An aliquot of this solution was taken and
preconcentration was done by the developed procedure. The good agreement between the
results obtained and the known amount present in the samples indicated the successful
applicability of the developed method (Table 4.1.2).

4.1.5.2 Sample Collection and Conditioning

Water samples were collected from Urban Estate Phase-II of Patiala City. The water samples
were immediately filtered through cellulose membrane filter (0.45 m pore size), and stored
in precleaned polyethylene bottles. After then, pH of the sample was adjusted to 8.5 and the
preconcentration procedure as described above was applied (Table 4.1.3).

4.1.5.3 Determination of Cu(II) in vegetables

The established optimized conditions of extractive preconcentration method were applied to
leafy vegetables, for the determination of Cu(II) content. The leafy vegetables analyzed were
brought from the local market during the month of January. The samples were cleaned and
dried. 10 gm. of leafy vegetable sample was pulverized in a mortar and was transferred into a
precleaned beaker. 50 mL of H2SO4 (3M) was added to the above sample and heated on a hot
plate for about an hour until white fumes ceases to evolve and the residue is completely
evaporated to dryness, then the sample was dissolved in water, filtered and made up to mark
in a standard measuring flask [396] (Table 4.1.4).

Table 4.1.2 Determination of Cu(II) in different alloy samples (n = 3)

Alloy
Sample

Compositi
on
(%)

Prese
nt
(ng.)

Foun
d
(ng.)

%Relati
ve
Error

Mangani

Cu 82; Mn

164

160.8

2.0

15; Ni 3

82

80.2

2.2

41

40.0

2.4

%Recover
y
R.S.
D
98.0
2.2
97.8
1.6
97.6
2.4

Constanta Cu 60; Ni

120

117.7

1.9

150

146.5

2.1

60

58.5

2.5

40

98.1
2.0
97.9
1.8
97.5
1.7

*n is the average of three replicated determinations

Table 4.1.3 Determination of Cu(II) in different water samples (n = 3)

Sample

Spiked
(ng.)

RSD(%)
#
Tap Water

Rose Water

Found
(ng.)

% Relative
Error

% Recovery

0.0

N.D.

-------

-------

45.0

43.5

3.3

96.7 1.6

35.0

33.6

4.0

96.0 2.4

0.0

N.D.

-------

-------

60.0

58.1

3.7

96.8 1.5

65.0

63.7

3.5

96.4 1.5

Mineral Water

0.0

N.D.

-------

-------

55.0

53.4

2.9

96.5 1.5

40.0

38.5

3.8

96.2 1.7

N.D. (not detected)

*n is the average of three replicated determinations
#Tap water samples were collected from Urban Estate Phase-II Patiala

Table 4.1.4 Determination of Cu(II) in different vegetable samples (n = 3)

^Sample

Spiked
(ng.)

RSD(%)
Carrot

Spinach

Cabbage

Found

% Relative

% Recovery

Error

(ng.)

0.0

N.D.

-------

-------

105.0

102.2

2.7

97.3 1.7

90.0

87.4

2.8

97.1 1.2

0.0

N.D.

-------

-------

56.0

54.5

2.7

97.3 1.9

80.0

77.7

2.8

97.1 1.3

0.0

N.D.

-------

-------

85.0

83.2

2.1

97.8 1.8

75.0

73.1

2.5

97.4 1.4

N.D. (not detected)

*n is the average of three replicated determinations
^Samples were collected from vegetable market in Urban Estate Phase-II Patiala

4.1.6 Comparison with other methods

A comparison of the proposed method with other preconcentration methods reported in
literature was carried out. Some parameters obtained were compared to those presented by
other methods described in the literature. As can be seen from the data (Table 4.1.5), the
proposed method developed by using -cyclodextrin polymer modified PAN system has a
relatively high preconcentration factor and a low LOD when compared to other methods.

Table 4.1.5 Comparison of the preconcentration factors of the various solid

supports used for the preconcentration of Cu(II)
Modificatio
n
Mode
Chemically
modified

Polymer

Modifier

Detectio
n
& Mode
FAAS
Off-line

p
H

PF

LO
D

Eluent

Application
s

%
Rec.

Ref.

SD
(mg
)
800

Silica gel

SPIMP

83

1.6

Rice, fish,
biscuit and
vegetables

96.1

379

ICP-AES
Off-line

500

60

0.18

Water and
food
samples

95

397

PAN

FAAS
Off-line

500

50

0.67

Water
and
reference
sediment
material

95100

398

Silica gel

PEG

FAAS
Off-line

350

66.
6

0.66

Sugar and
water
samples

100

399

Silica gel

HBAHB
A

FAAS
Off-line

100

20

4.2

400

DMG

FAAS

300

30

3.5

Mango pulp,
vegetable
and fish
samples
Water and

96.0
99.3

Silica gel

6.0 mL
of
4.0M
HNO3
10.0
mL of
1.0M
HNO3
10.0
mL of
1.0M
HNO3
in
aceton
e
3.0 mL
of
1.0M
HNO3
5.0 mL
of
3.0N
HNO3
10.0

Chemically
modified

XAD-2

NPTAT

Physically
Modified
(Impregnation)

Ambersorb 563

Chemically
modified

Physically
Modified
(Impregnation)
Physically

98.0

401

Modified
(Impregnation)
Chemically
modified

Off-line

Amberlit
e XAD-2

2-MeBTAP

FAAS
On-line

N.R.

30

0.87

Chemically
modified

Amberlit
e XAD1180

PAN

FAAS
Off-line

400

100

0.19

Physically
modified

-CDP

PAN

UV-Vis
Off-line

8.5

400

100

2.43

mL of
0.1M
HCl
200L
of 1M
HCl

20.0
mL of
2.0M
HNO3
4.0 mL
of
2.0M
HCl

standard
reference
materials
Black tea,
rice flour
and ref.
biological
materials
Water and
river
sediment
samples
Water, food
and alloy
samples

93

402

92

403

95

This
work

SD: Sorbent dose(mg); PF: Preconcentration factor; LOD: limit of detection(ng/mL);

PNNPP: 4-Nitro-2-(2-nitro-phenelazo) phenol; BPHA: N-Benzoyl-N-phenyl hydroxyl
amine; HBAHBA: 5[2-hydroxybenzlideneamino]-2-hydroxybenzoic acid; FAAS: Flame
atomic absorption spectrometry; ICP-AES: inductively coupled plasma atomic emission
spectrometry;
NPTAT:3-(2-Nitro-phenyl)-1-H-1,2,4-triazole-5(4H)-thione;
DMG:
Dimethylglyoxime; Me-BTAP: 2-[2-(6-methyl-benzothiazolylazo)]-4-aminophenol; PAN:
1-(2-pyridylazo)-2-naphthol

4.2 Preconcentration of Co(II) using -CDP-PAN polymer

4.2.1 Materials
4.2.1.1 Equipments
Equipments used are same as described in section 4.1.1.1.

4.2.1.2 Reagents
1 10-2M Co(II) solution was prepared by dissolving 0.249gm. Co(NO 3)2. 6H2O of in 100
mL of distilled water to give standard stock solution.
All other reagents used are same as described in section 4.1.1.2.

4.2.2 Procedure
4.2.2.1 Batch Extraction Procedure
At room temperature, -CDP-PAN (300 mg.) and 10.0 mL of buffer solution (pH 8.5) were
added to a 100-mL Stoppard conical flask. The mixture was allowed to stand for about 15
min so that -CDP-PAN polymer could swell sufficiently. 70ng. of Co(II) were added and
made up to 100 mL with double distilled water. After the mixture was shaken in the

thermostatic shaking water bath for 30 min, 5.0 mL of the supernatant solution was
transferred into a 10mL volumetric flask and the absorbance was measured using standard
spectrophotometric method [394]. Co(II) retained on -CDP-PAN polymer was eluted using
4.0mL of 3M HCl.

4.2.3 Optimization of various parameters

4.2.3.1 Effect of pH on % uptake of Co(II)
The uptake of an analyte on the chelating resin is dependent on the pH of sample solution due
to the competitive reaction between chelate forming groups and hydrogen ions in the
solutions. 70ng. of Co(II) were spiked to a 100 mL flask containing 300 mg of resin. The pH
of this solution was adjusted in the range of 3.5 to 10.0 using different buffer system and then
the preconcentration procedure as described was applied. Quantitative uptake ( 95%) was
obtained at pH 7.5-10.0 0.01 (Fig. 4.2.1). Therefore, 8.5 was selected as the working pH.

4.2.3.2 Effect of the amount of polymer on % uptake of Co(II)

The amount of the polymer is another important parameter that affects the uptake of an
analyte. A quantitative uptake ( 95%) cannot be achieved when the polymer is less than the
optimum amount. On the other hand, an excess of polymer prevents the quantitative elution
of the retained metal chelate by a small volume of the eluent. In order to optimize the
smallest amount of polymer 100, 200, 300, 400 and 500 mg. of the polymer were added to
the 100 mL of the sample solution containing 70 ng. of Co(II) and preconcentrated by the
general procedure. The quantitative recoveries were obtained for and above 300 mg. of
polymer (Fig. 4.2.2). Therefore, 300 mg. of the polymer was selected for subsequent
experiments.

4.2.3.3 Effect of shaking time on % uptake of Co(II)

Shaking time is an important factor in determining the possibility of application of the CDP-PAN polymer for the uptake of Co(II). A 300 mg. amount of polymer was shaken with
100 mL of solution containing 70 ng. of Co(II) for different shaking time (ranging from 10 to
50 minutes) with an interval of 10 minutes at optimum pH. The results of % uptake of Co(II)
vs. the shaking time show that the percentage uptake reached maximum ( 95%) at 30 min
(Fig. 4.2.3). Therefore, the shaking time of 30 min. was selected as the uptake equilibrium
time.

4.2.3.4 Effect of the sample volume on % uptake of Co(II)

In order to explore the possibility of enriching low concentration of analytes from large
volume of sample, the effect of sample volume on the uptake of Co(II) was also investigated.
50, 100, 150, 200, 250, 300, 350, 400, 450 mL of sample solutions containing 70 ng. of
Co(II), 300 mg. of polymer at optimum pH and were shaken for 40 min. Quantitative uptakes
( 95%) were obtained for sample volume of 350 mL (Fig. 4.2.4). Therefore, 100 mL of
sample solution was adopted for the preconcentration of analyte from sample solutions.

4.2.3.5 Effect of shaking speed (r.p.m.) on % uptake of Co(II)

The % uptake of Co(II) increased gradually with a rise in the shaking speed (Fig. 4.2.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Therefore, the present study suggests that the
shaking effect is high-flying parameter for the maximum % uptake of an analyte ion.

4.2.3.6 Effect of Nature of Eluent

In order to choose the best eluent for the Co(II) retained on -CDP-PAN polymer, various
eluent were used. Amongst the studied eluents, hydrochloric acid (HCl) provided higher
recovery efficiency than the organic solvents and acids. Therefore, HCl was selected as the
eluent.

4.2.3.7 Effect of eluent concentration

The effect of HCl concentration and volume on elution of Co(II) on -CDP-PAN polymer
was studied by carrying out the elution with (1-5) M HCl. The results indicate that the highest
recoveries for Co(II) were obtained when HCl concentration was 3M or more. Hence 3M was
chosen as eluent for further experimental conditions. The results are presented in (Fig. 4.2.6).

4.2.3.8 Effect of eluent volume

In order to obtain the quantitative recovery of retained Co(II) metal ion on -CDP-PAN
polymer was studied by carrying out the elution with (1-6 mL) of 3M HCl. During these
studies, 100 mL aliquots of the sample solutions containing 70 ng. of Co(II) were used at pH
8.5. Quantitative recovery values were obtained by using 4 mL of eluent. The results are
depicted in (Fig. 4.2.7).

100
80
60
% Uptake of Co(II)

40
20
0
3.5 4.5 5.5
6.5 7.5 8.5
9.5 10
pH

Fig. 4.2.1 Effect of pH on the % uptake of Co(II)

100
80
60
% Uptake of Co(II)

40
20
0
100

200

300

400

500

Amount of polymer(mg)

Fig. 4.2.2 Effect of the amount of polymer on the % uptake of Co(II)

100
80
60
% Uptake of Co(II)

40
20
0
10

20

30

40

50

Shaking time(min.)

Fig. 4.2.3 Effect of the shaking time on the % uptake of Co(II)

120
100
80
60
% Uptake of Co(II)

40
20
0
50 100 150
200 250

300 350 400

450

Sample volume(mL)

Fig. 4.2.4 Effect of the sample volume on the % uptake of Co(II)

100
80
60
% Uptake of Co(II)

40
20
0
40

60

80

100

120

140

Shaking Speed (r.p.m.)

Fig. 4.2.5 Effect of shaking speed on % uptake of Co(II)

100
80
60
% Uptake of Co(II)

40
20
0
1

Eluent Conc. (M)

Fig. 4.2.6 Effect of eluent conc. on % uptake of Co(II)

100
80
60
% Uptake of Co(II)

40
20
0
1

Eluent Volume (mL)

Fig. 4.2.7 Effect of the eluent volume on % uptake of Co(II)

4.2.4 Effect of coexisting ions

The effect of various coexisting ions on the % uptake of a solution containing 70 ng. of
Co(II) was studied. An ion was considered to interfere when its presence produced a variation
in the uptake of the sample 5%. Among the anions examined CO 32-, SO32-, SO42-, NO3-, IO3-,
NO2- did not interfere at concentrations 1000 times more than those of the analyte (Table
4.2.1). The complexation between Co(II) and PAN was completely masked by EDTA
(ethylenediamine tetraacetate ion) and cyanate even at lower concentration. Alkali and
alkaline earth metal ions did not interfere.

Table 4.2.1 Effect of foreign ions in the determination of Co(II)

Ion
NO3, SO4, HPO42, SCN, NO2,
PO43, ClO3 , IO3, Cl, I, Br,
CH3COO, C2O42Na(I), K(I), Mg(II), Ba(II), Al(III),
Rb(I), Cs(I), Ag(I)
Sb(III), Ca(II), Zr(IV), Ti(IV)
Th(IV), Sn(II), As(III)
a
Fe(III), bNi(II)
c
Zn(II), dPb(II), eFe(II), eMn(II),
f
Hg(II), fCd(II)
EDTA, CN-, F-, S2O32-

Tolerance Limit
Wforeign ion/WCo(II)
>1000

1000
1000
100
40
10
1

a-masked with 1.0 mL of 5.0% ammonium oxalate; b-masked with 1.0 mL of 2.0%
dimethylglyoxime; c-Masked with 1.0 mL of 10.0% sodium citrate solution; d-masked with
2.0 mL of 1% sodium sulphate; e-masked with 2.0 mL of 3.0% sodium hexametaphosphate
solution; f-masked with mixed masking agent solution of 1.0 mL of 5.0% potassium
pyrophosphate, 1.0 mL of 25.0% citric acid and 1.0 mL of 10.0% thiourea solution.

4.2.5 Validation of the method

The validation of the developed method was checked by applying it for the determination of
Co(II) in certified alloy samples water, vegetable.

4.2.5.1 Determination of Co(II) in standard alloys

The proposed method has been applied for the determination of Co(II) in alloys to check the
validity of the method (Table 4.2.2). To dissolve the standard reference alloy, modified
literature method was employed. 0.1 gm of the standard alloy was completely dissolved in 20
mL of HCl by heating on a water bath; 2 mL of 30% hydrogen peroxide was added to the
solution. The excess of peroxide was decomposed by heating the solution on a water bath.
The solution was cooled, filtered and diluted to 100 mL with double distilled water. Further
dilutions were made as and when required. An aliquot of this solution was taken and
preconcentration was done by the developed procedure.

4.2.5.2 Sample Collection and Conditioning

Water samples were collected from the Punjabi University, Patiala Campus, Patiala City. The
water samples were immediately filtered through cellulose membrane filter (0.45 m pore
size), and stored in precleaned polyethylene bottles. After then, pH of the sample was

adjusted to 8.5 and the preconcentration procedure as described above was applied (Table
4.2.3).

4.2.5.3 Determination of Co(II) in vegetables

The established optimized conditions of extractive preconcentration method were applied to leafy
vegetables, for the determination of Co(II) content (Table 4.2.4). The leafy vegetables analyzed
were brought from the local market during the month of January. The samples were cleaned and
dried. 10 gm. of leafy vegetable sample was pulverized in a mortar and transferred into a
precleaned beaker. 50 mL of H2SO4 (3M) was added to the above beaker and heated on a hot plate
for about an hour, until white fumes ceases to evolve and the residue is completely evaporated

to dryness. Then the sample was dissolved in water, filtered and made up to mark in a
standard measuring flask.

Table 4.2.2 Determination of Co(II) in certified alloy samples, (for n=3)

Alloy
Sample

Compositio Present Found %Relativ

n
(ng.)
(ng.) e
(%)
Error
Alnico 9
Al 7 Ni 15
35.0
34.0
2.8
Co 35 Cu 4
70.0
68.7
1.8
Ti 5
47.0
45.4
3.4
*n is the average of three replicate determination

%Recovery
R.S.D.(%)
97.11.5
98.11.7
96.61.5

Table 4.2.3 Determination of Co(II) in different water samples (for n=3)

Sample

Spiked
(ng.)

RSD(%)
#
Tap Water

R.O. Water

Found

% Relative

(ng.)

Error

% Recovery

0.0

25.5

-------

-------

50.0

75.5

-1.0

100.0 1.6

45.0

70.5

-1.1

100.0 2.9

0.0

N.D.

-------

-------

60.0

58.5

2.5

97.5 1.7

55.0

53.4

2.9

97.1 2.4

Mineral Water 0.0

N.D.

-------

70.0

68.3

2.4

97.6 1.3

30.0
N.D. (not detected)

29.2

2.7

97.3 2.0

-------

*n is the average of three replicate determination

#

Tap water samples were collected from Punjabi University, Patiala Campus

Table 4.2.4 Determination of Co(II) in leafy vegetable sample (for n=3)

^

Sample

Spiked
(ng.)

RSD(%)
Carrot

Spinach

Found

% Relative

% Recovery

Error

(ng.)

0.0

N.D.

-------

-------

45.0

43.7

2.9

97.1 2.2

75.0

72.9

1.9

97.2 1.9

0.0

N.D.

-------

20.0

19.4

3.0

97.0 2.1

38.9

2.8

97.2 2.2

40.0
N.D. (not detected)

-------

*n is the average of three replicate determination

^Samples were collected from Vegetable market in Urban Estate Phase-II Patiala

4.2.5 Comparison with other methods

A comparison of the proposed method with other preconcentration procedures is presented
(Table 4.2.5). Some parameters obtained were compared to those presented by other methods
described in the literature. As can be seen from the data, the proposed method developed by
using PAN modified -cyclodextrin polymer (-CDP) has a relatively high preconcentration
factor and a low LOD when compared to other methods.

Table 4.2.5 Comparison of the preconcentration factors of the various solid

supports used for the preconcentration of Co(II)
Modification
Mode

Polymer

Modifier

pH/SD

PF

Immobilization
(Physically
modified)
Chemically
modified

Diaion HP2MG

Aspergillus
fumigatus

8/500

50

Silica gel

SPIMP

5/800

Immobilization
(Physically
modified)
Chemically
modified

Silica gel

Salicylaldoxime

Silica gel

Chemically
modified

Cellulose

Aminothioamidoanthr
a
-quinone
8-Hydroxyquinoline

Im-

Amberlite-

PAR

LOD/
RSD(%)

Detection
& Mode

Eluent

Applications

%
Rec.

Ref.

0.72/<7

FAAS
Off-line

10 mL
of 1M
HCl

98

404

83

2.0/2.3

FAAS
Off-line

97.8

397

4.2/800

50

1.5/---

AAS
Off-line

Pharma
samples

93

405

4.5/60

20

0.95/<9

FAAS
Off-line

6.0 mL
of
4.0M
HNO3
20.0
mL of
0.5M
HNO3
5.0 mL
of 1%
HNO3

Water,
tomato
paste, black
tea & dust
Rice, fish,
biscuit
&
vegetables

Different
water
samples

97

406

5.3/500

100

----/3.2

FAAS
Off-line

Water &
Pharma
samples

97.5

407

8.5/----

50

3.3/3.5

FAAS

Buffalo

953

408

20.0
mL of
1.0M
HNO3
20.0

pregnation
(Physically
modified)

XAD-1180

Off-line

mL of
3.0M
HNO3

Chemically
modified

XAD-2

Pyrocatechol

8.0/100

40

0.59/4.7

FAAS
On-Line

100

14.0/3.1

FAAS
On-Line

80 L
0.5M
HCl
1M
HNO3

Chemically
modified

Silica gel

FCPASA

9.0/20

Physically
modified

-CDP

PAN

8.5/400

100

4.2/<2.9

UV-VIS
Off-line

4.0 mL
of
2.0M
HCl

river
sediment
and water
samples
Black tea
& rice flour
Different
water
samples
Water, food
&
alloy
samples

97

409

91

410

95

DM

SD: Sorbent dose; PF: Preconcentration factor; LOD: limit of detection(ng/mL); Rec:
Recovery; FAAS: Flame atomic absorption spectrometry; AAS: atomic absorption
spectrometry; UV-Vis: Ultra violet-visible spectrophotometry; SPIMP: 2-[-(3silylpropylimino) methyl]phenol; TMTA: 2,4,6-trimorpholino-1,3,5-triazin; BPMBDA:
N,N-bis(pyridine-2-yl-methylbenzene-1,4-diamine; 5,7-DCQ: 5,7-dichloroquinone-8-ol;
PAR: 4-(-2-pyridylazo)-resorcinol; FCPASA: 5-formyl-3-(1-carboxyphanylazo) salicylic
acid; PAN: 1-(2-pyridylazo)-2-naphthol; DM: Developed method.

4.2.6. Analytical figure of merits

The spiking method was applied to the real water and vegetable samples and the recoveries
obtained revealed that the proposed method has good accuracy. The analytical procedure was
also validated by determining Co(II) in certified reference alloy material. The results revealed
good agreement between the observed values and the certified values. The limit of detection
(LOD) was calculated as three times the standard deviation (3) of 3 replicate measurements
with the proposed preconcentration procedure. The precision of the method was evaluated as
the RSD, obtained after analyzing a series of three replicates with the preconcentration step;
it is found to be 2.9 for Co(II).

Table 4.2.6 List of various optimized parameters

Parameters

Co(II)

pH

8.5

Shaking Time(min)

30 min.

Temperature(C)

30C

Sample Volume(ml)

100mL

Agitation Speed(r.p.m.)

100 r.p.m.

Adsorbent Dose(mg.)

300mg.

Eluent Used

HCl

Eluent Concentration(M)

3.0M

Eluent Volume(mL)

4 mL

4.3 Preconcentration of Ni(II) using -CDP-PAN polymer

4.3.1 Materials
4.3.1.1 Equipments
Equipments used are same as described in section 4.1.1.1.

4.3.1.2 Reagents
1 10-2M solution of Ni(II) was prepared by dissolving 0.237gm. of nickel chloride
hexahydrate [NiCl2.6H2O] in 100mL of distilled water to give standard stock solution.

4.3.2 Procedure
4.3.2.1 Batch Extraction Procedure
At room temperature, -CDP-PAN (500 mg) and 10.0 mL of buffer solution (pH 9.5) were
added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN could be swollen sufficiently. 100ng. of Ni(II) was
added and made up to 100mL with double distilled water. After the mixture was shaken in the
thermostatic shaking water bath for 40 min, 5.0 mL of the supernatant solution was
transferred into a 10mL volumetric flask and the absorbance was measured using standard
spectrophotometric method [394].

4.3.3 Optimization of various parameters

4.3.3.1 Effect of pH
For solid phase extraction of heavy metal ions on different types of chelating resins, the pH
of the aqueous solution is one of the foremost factors for quantitative recoveries of the
analytes. Therefore, the effect of pH on the uptake of Ni(II) on PAN modified -CD polymer
was studied in the pH range of 4.5-10.5. For this purpose 100 ng. of Ni(II) were spiked to a
100 mL of the model solution and the pH of this solution was adjusted using different buffer
solutions and then the general preconcentration procedure was followed. The results of this
study shows that quantitative uptake (95%) of Ni(II) ions was achieved over pH range of
8.5-10.5 (Fig. 4.3.1). Therefore, for subsequent studies, 9.5 was selected as the working pH.

4.3.3.2 Effect of the amount of polymer

The amount of solid phase extractant material is another imperative factor on the uptake
studies for the quantitative recoveries of metal ions. A quantitative retention ( 95%) cannot
be achieved when the polymer is less than the optimum amount. On the other hand, an excess
amount of polymer prevents the quantitative elution of the retained metal chelate by a small
volume of the eluent. In order to optimize the smallest amount of polymer, 100, 200, 300,
400, 500, 600 and 700 mg. of the polymer were added to a sample containing 100 ng. of
Ni(II) and preconcentrated by the general procedure. The quantitative uptake ( 95%) were
obtained for and above 500 mg of polymer (Fig. 4.3.2). Therefore, 500 mg of the polymer has
been used for subsequent experiments.

4.3.3.3 Effect of shaking time

Effect of shaking time is an important factor in determining the possibility of application of
the -CDP-PAN polymer for the selective uptake of Ni(II). The 500 mg. of the polymer was
shaken with 100 mL of the sample containing 100 ng. of Ni(II) at room temperature for
different shaking times ranging from 20 to 70 min (Fig. 4.3.3) The kinetics of the polymermetal interaction is sufficiently rapid for Ni(II) at optimum pH. The faster uptake of Ni(II) on
-CDP-PAN reflects a good accessibility of the polymers chelating sites to metal ion.
Therefore, the shaking time of 40 min was selected as the optimum uptake equilibrium time.

4.3.3.4 Effect of the sample volume

In order to explore the possibility of enriching low concentration of analytes from large
volume of solution, the effect of sample volume on the retention of Ni(II) ion was also
investigated. For this purpose, 25, 50, 100, 150, 200, 250, 300, 350, 400 and 450 mL of
sample containing 100 ng. of Ni(II) were taken and shook for 40 min.. Quantitative uptake (
95%) was obtained for sample volume of 350 mL (Fig. 4.3.4). But for convenience, 100
mL of sample volume was adopted for the preconcentration purpose.

4.3.3.5 Effect of shaking speed (r.p.m.)

The % uptake of Ni(II) increased gradually with a rise in the shaking speed (Fig. 4.3.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Therefore, the present study suggests that the
shaking effect is high-flying parameter for the maximum % uptake of an analyte ion.

4.3.3.6 Effect of Nature of Eluent

In order to choose the best eluent for the Ni(II) retained on -CDP-PAN polymer, various
eluent were used. Amongst the studied eluents, hydrochloric acid (HCl) provided higher
recovery efficiency than the organic solvents and acids. Therefore, HCl was selected as the
eluent.

4.3.3.7 Effect of the eluent concentration

Various concentrations of hydrochloric acid (HCl) were examined to obtain quantitative
uptake values for Ni(II) from the polymer. The % uptake was not quantitative when the
concentration of HCl was < 2M > used as an eluent. Therefore, 2 M HCl was used for
quantitative recovery of Ni(II) from -CDP-PAN polymer in further studies (Fig. 4.3.6).

4.3.3.8 Effect of the eluent volume

The volume of the eluent (2 M HCl) that could completely strip the retained Ni(II) from the
polymer was also studied for obtaining the maximum preconcentration factor. Thus, some
experiments were carried out in order to choose a proper eluent volume for striping Ni(II)
ions from the polymer (Fig. 4.3.7). The uptake values for Ni(II) ions from the polymer were
quantitative ( 95%) in the eluent volume range of 4-6 mL. Thus, an eluent volume of 5 mL
was selected for further studies. The preconcentration factor comes out to be 70 if the eluent
volume used is 5 mL.

100
80
60
% Uptake of Ni(II)

40
20
0
4.5 5.5
6.5 7.5
8.5 9.5
10.5
pH

Fig. 4.3.1 Effect of pH on % uptake of Ni(II)

100
80
60
% Uptake of Ni(II)

40
20
0
100 200
300 400
500 600
700
Amount of the polymer(mg.)

Fig. 4.3.2 Effect of the amount of polymer on % uptake of Ni(II)

100
80
60
% Uptake of Ni(II)

40
20
0
10

20

30

40

50

60

Shaking Time(min.)

Fig. 4.3.3 Effect of shaking time on % uptake of Ni(II)

120
100
80
60
% Uptake of Ni(II)

40
20
0
25 50 100
150 200 250

300 350 400

450

Sample volume (mL)

Fig. 4.3.4 Effect of the sample volume on % uptake of Ni(II)

100
80
60
% Uptake of Ni(II)

40
20
0
40

60

80

100

120

140

Shaking speed (r.p.m.)

Fig. 4.3.5 Effect of shaking speed (r.p.m.) on % uptake of Ni(II)

100
80
60

% Uptake of Ni(II)

40
20
0

0.5

Eluent Conc. (M)

Fig. 4.3.6 Effect of eluent concentration on % uptake of Ni(II)

100
80
60
% Uptake of Ni(II)

40
20
0
1

Eluent volume (mL)

Fig. 4.3.7 Effect of eluent volume on % uptake of Ni(II)

4.3.4 Effect of coexisting ions

The effect of various coexisting ions on the % uptake of a solution containing 150 ng. of
Ni(II) was studied. An ion was considered to interfere when its presence produced a variation
in the uptake of the sample 5%. Among the anions examined CO 32-, SO32-, SO42-, NO3-, IO3-,
NO2- did not interfere at concentrations 1000 times more than those of the analyte (Table
4.3.1). The complexation between Ni(II) and PAN was completely masked by EDTA
(ethylenediamine tetraacetate ion) and cyanate even at lower concentration. Alkali and
alkaline earth metal ions did not interfere.

Table 4.3.1 Effect of foreign ions in the determination of Ni(II)

Ion
NO3, SO4, HPO42, SCN, NO2,
PO43, ClO3 , IO3, Cl, I, Br,
CH3COO, C2O42Na(I), K(I), Mg(II), Ba(II), Al(III),
Rb(I), Cs(I), Ag(I)
Sb(III), Ca(II), Zr(IV), Ti(IV)
Th(IV), Sn(II), As(III)
a
Fe(III), bCo(II)
c
Zn(II), dPb(II), eFe(II), eMn(II),
f
Hg(II), fCd(II)
EDTA, CN-, F-, S2O32-

Tolerance Limit
Wforeign ion/WNi(II)
>1000

1000
500
100
40
10
1

a-masked with 1.0 mL of 5.0% ammonium oxalate; b-masked with 2.0 mL of 1.0% sodium
thiocyanate; c-Masked with 1.0 mL of 10.0% sodium citrate solution; d-masked with 2.0 mL
of 1% sodium sulphate; e-masked with 2.0 mL of 3.0% sodium hexametaphosphate solution;
f-masked with mixed masking agent solution of 1.0 mL of 5.0% potassium pyrophosphate,
1.0 mL of 25.0% citric acid and 1.0 mL of 10.0% thiourea solution.

4.3.5 Validation of the method

The validity of the developed method was checked by applying it for the determination of
Ni(II) in certified alloy, water and potato chips samples.

4.3.5.1 Determination of Ni(II) in standard alloys

The accuracy of the proposed method was verified by the determination of Ni in standard
reference alloy samples. A 0.1 gm of the standard alloy was completely dissolved in 20mL of
hydrochloric acid by heating on a water bath; 2mL of 30% hydrogen peroxide was added to
the solution. The excess of peroxide was decomposed by heating the solution on a water bath.
The solution was cooled, filtered and diluted to 100 mL with double distilled. Further
dilutions were made as required. An aliquot of this solution was taken and preconcentration
was done by the developed procedure. The good agreement between the results obtained and
the known amount present in the alloy sample indicated the successful applicability of the
developed procedure (Table 4.3.2).

4.3.5.2 Determination of Ni(II) in Water samples

Water samples were collected from Punjabi University, Campus Patiala. The water samples
were immediately filtered through cellulose membrane filter (0.45 m pore size), and stored
in precleaned polyethylene bottles. After then, pH of the sample was adjusted to 9.5 and the
preconcentration procedure as described above was applied. The results of analysis of spiked
water samples are presented in (Table 4.3.3).

4.3.5.3 Determination of Ni(II) in different potato chips sample

Potato chips of the selected brands that were available locally were purchased for further
processing. Wet digestion of the chips was carried out by digesting 0.5 gm of each of the
sample with a mixture of HNO3:H2SO4 (8:4) [411]. This mixture was heated up to 130 C for
1h. After cooling 5mL of distilled water was added to the sample and mixed. The residue was
filtered. The sample was then diluted to 100mL with distilled water. An aliquot of the above
sample was taken and spiked with known amount of the Ni(II) and determined with general
procedure. The results are presented in (Table 4.3.4).

Table 4.3.2 Determination of Ni(II) in certified alloy samples (for n = 3)

Alloy
Sample

Certified
Composition

Present (ng.)
Ni(II)

Found (ng.)
Ni(II)a

% Relative
Error

% Rec.

Constantan

Cu 60, Ni 40

80.0

79.80 0.05

0.25

99.75

40.0

39.81 0.10

0.47

99.52

Ni 60, Cu 33,

100.0
48.0

99.70 0.05
47.76 0.10

0.30
0.50

99.70
99.51

Fe 6.5

32.0

31.85 0.05

0.46

99.53

120.0

119.7 0.07

0.25

99.75

Monel wire

Mean standard deviation

*n is the average of three replicate determinations.

Table 4.3.3 Determination of Ni(II) in different water samples (for n = 3)

Water
Samples
Tap water

Spiked (ng.)
Ni(II)
0.0

Found (ng.)
Ni(II)a
11.6 0.45

% Relative
Error
----

% Recovery

70.0

83.7 0.36

-3.0

103.0

55.5
0.0

68.8 0.21
N.D.

-3.1
-----

103.0
------

60.0

62.1 0.26

-3.5

103.5

50.0
0.0

51.7 0.21
15.7 0.20

-3.4
-----

103.4
-------

60.0

77.3 0.17

-2.7

102.6

70.0
Mean standard deviation

85.7 0.17

-2.0

102.0

Rose water

Bore water

------

*n is the average of three replicate determinations.

Table 4.3.4 Determination of Ni(II) in potato Chips samples (for n = 3)

Sample
*

American
Cream and
Onion Style
*

Classic
Salted

Spiked (ng.)
Ni(II)
75.0

Found (ng.)
Ni(II)a
74.5 0.25

% Relative
Error
0.67

%
Recovery
99.33

80.0

79.4 0.17

0.75

99.25

60.0
35.0

59.5 0.16
34.4 0.21

0.83
1.71

99.16
98.28

40.0

39.5 0.10

1.25

98.75

50.0

49.6 0.15

0.80

99.20

Mean standard deviation

*n is the average of three replicate determination

*

PEPSICO INDIA HOLDINGS PVT. LTD. (Frito-Lay Division), Gurgaon-122002, Haryana

4.3.6 Comparison with other methods

A comparison of the proposed method with other preconcentration procedures is presented

(Table 4.3.5). Some parameters obtained were compared to those presented by other methods
described in the literature. As can be seen from the data, the proposed method developed
using -cyclodextrin polymer modified with PAN, has a relatively high preconcentration
factor and a low LOD when compared to other methods.

Table 4.3.5 Comparison of the described method with some solid phase
extraction methods for Ni(II) determination

Modificatio
n
Mode
Physically
modified

Polymer

Modifie
r

Detectio
n
& Mode
FAAS
Off-line

pH

PF

----

SD
(mg
)
500

Silica gel

2-AT

-----------

CS-107

--------

Chemically
modified

Chitosan

Physically
modified

10

ETAAS
Off-line

/6

300

10

3,4DHBA

FI-ICPAES
Off-line

5.5

----

11.8

0.09

AXAD-2

PV

FAAS
Off-line

3.0

1000

18

--

Chemically
modified

Silica gel

ATAAQ

FAAS
Off-line

60

20

2.9

Physically
modified

AXAD-2

5-P-8HQ

FAAS
Off-line

4.5- 1000
6.0

50

4.0

Chemically
modified

Silica
NPs

PAN

UV-VIS
Off-line

9.2

30

60

0.43

Chemically
modified
Chemically
Modified

TiO2
NTs
Silica gel

8-HQ

FAAS
Off-line
GFAAS
Off-line

8.0

200

66.7

500

----

0.5

Physically
modified

-CDP

9.5

500

70

1.18

3APTES
PAN

UV-Vis
Off-line

LO
D

Eluen
t

Application
s

%
RS
D
3.0

Ref
.

2.3

2M
HCl

---

2.5
mL of
4.5M
HNO3
0.5
mL of
2M
HNO3
7.5
mL of
4M
HCl/
HNO3
5 mL
of 1%
HNO3
20 mL
of 2M
HNO3
5 mL
of 6M
HCl
3 mL
HNO3
5 mL
of 2M
HCl
5 mL
of 2M
HCl

Hydrated
fuel ethanol
samples
Apple
leaves and
sea water
samples
River and
sea water
samples

2.0

413

----

358

Well Water
samples

9.0

414

Different
water
samples
Water
samples

415

5.2

416

Water
samples

4.1

417

Water
samples
Sea Water
Samples

2.6

418

2.0

419

Water,
potato chips
and alloy
samples

<1.0

DM

2-AT: 2-Aminothiazole; CS-107: Chromosorb-107; 3, 4-DHBA: 3, 4-Dihydroxy benzoic

acid; PV: Pyrocatechol Violet; ATAAQ: Aminothioamidoanthraquinone; 5-PHQ: 5Palmitoyl-8-hydroxyquinoline;

8-HQ:

8-Hydroxy

quinoline;

3-APTES:

3-

412

Aminopropyltriethoxy silane; PF: Preconcentration factor; DL: Detection limit (ng/mL or

g/l).

4.3.7 Accuracy of the method

The accuracy of the described preconcentration method was tested in the recovery studies by
adding known amounts of Ni(II) to the water samples and potato chips samples and also by
the analysis of certified alloys containing Ni. The results obtained from the analysis of
different samples are satisfactory. These results confirm the validity of the proposed method.

Table 4.3.7 Various parameters studied for preconcentration of Ni(II) using CDP-PAN modified polymer as the sold phase extractant.
Parameters
pH
Shaking time
Sample volume
Polymer dose
Eluent used
Eluent concentration
Volume of eluent used for elution
Preconcentration factor

Ni(II)
9.5
40 min
100 mL
500 mg
HCl
2M
5 mL
70

4.4. Preconcentration of Fe(III) using -CDP-PAN polymer

4.4.1 Materials

4.4.1.1 Equipments
Equipments are same as discussed in section 4.4.1.1.

4.4.1.2 Reagents
1 10-2M Fe(III) solution was prepared by dissolving 0.270gm of ferric chloride hexahydrate
[FeCl3.6H2O] in 100mL of distilled water to give standard stock solution.

4.4.2 Procedure
4.4.2.1 Batch Extraction Procedure
At room temperature, -CDP-PAN (400mg) and 10.0 mL of buffer solution (pH 5.5) were
added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN could be swollen sufficiently. 55ng. of Fe(III)
were added and made up to 100mL with double distilled water. After the mixture was shaken
in the thermostatic shaking water bath for 45 min, 5.0mL of the supernatant solution was
transferred into a 10mL volumetric flask and the absorbance was measured using standard
spectrophotometric method [394]. Fe(III) retained on -CDP-PAN polymer was eluted using
4mL of 2M HCl.

4.4.3 Optimization of various parameters

4.4.3.1 Effect of pH
The complexation of the metal ion with PAN on the chelating polymer is dependent on the
pH of sample solution due to the competitive reaction between chelate forming groups and
hydrogen ions in the solutions. In order to investigate the effect of pH on % uptake of Fe(III),
55 ng. of Fe(III) were added to a 100 mL of the model solution. The pH of this solution was
adjusted in the range of 3.5 to 10 using different buffer solutions and then the
preconcentration procedure as described was applied. Quantitative uptake ( 95%) was
obtained at pH 5.5 (Fig. 4.4.1). Therefore, 5.5 was chosen as the working pH for the
subsequent studies.

4.4.3.2 Effect of the amount of polymer

The amount of polymer is another important parameter that affects the % uptake of an analyte
ion. A quantitative uptake ( 95%) cannot be achieved when the polymer is less than the
optimum amount. On the other hand, an excess amount of polymer prevents the quantitative

elution of the retained metal chelate by a small volume of the eluent. In order to optimize the
smallest amount of polymer, 100, 200, 300, 400, 500, 600 and 700 mg. were added to the
same volume of the sample containing 55 ng. of Fe(III) and preconcentrated by the general
procedure., Quantitative recoveries were obtained for and above 400 mg of polymer (Fig.
4.4.2). Therefore, 400 mg of the polymer has been used for subsequent studies.

4.4.3.3 Effect of Shaking Time

The shaking time is an important factor in determining the possibility of application of the CDP-PAN polymer for the selective uptake of metal ion. Different shaking time (ranging
from 15 to 75min.) were studied for the % uptake of Fe(III) by -CDP-PAN polymer. The
maximum % uptake was obtained at 45 min (Fig. 4.4.3). Therefore, the shaking time of 45
min. was selected as the uptake equilibrium time.

4.4.3.4 Effect of the sample volume

In order to explore the possibility of enriching low concentration of analytes from large
volume of solution, the effect of sample volume on % uptake of Fe(III) ion was also
investigated. For this purpose, 25, 50, 100, 150, 200, 250, 300, 350, 400 mL of sample
containing 55 ng. were taken. Quantitative uptake ( 95%) was obtained for sample volume
of 300 mL (Fig. 4.4.4). But for convenience, 100 mL of sample volume was adopted for the
preconcentration of analyte ion.

4.4.3.5 Effect of the shaking speed

The % uptake of Fe(III) increased gradually with a rise in the shaking speed. The batch
extraction technique is based on the choice of shaking speed that helps to improve the mass
transfer. Shaking speed here acts as a driving force. The central dogma is that the increasing
driving force could help in mass transfer and facilitate the concentration gradient between the
sample solution and the polymer. Therefore, the present study suggests that the shaking effect
is high-flying parameter for the maximum % uptake of an analyte ion.

4.3.3.6 Effect of Nature of Eluent

In order to choose the best eluent for the Fe(III) retained on -CDP-PAN polymer, various
eluent were used. Amongst the studied eluents, hydrochloric acid (HCl) provided higher
recovery efficiency than the organic solvents and acids. Therefore, HCl was selected as the
eluent.

4.4.3.7 Effect of elution conditions on recovery

Since the adsorption of Ferbam at pH 2.5 is quite low, one can expect that elution will be
favored in the acidic solutions. Thus, the different volumes of HCl at a concentration of 2M
were used for the desorption of retained Fe(III). The experimental results showed that 4 mL
of 2M HCl was sufficient for complete elution of Fe(III) (Fig. 4.4.5 & 4.4.6).

120
100
80
60
% Uptake of Fe(III)

40
20
0
2.5 3.5 4.5
5.5 6.5 7.5
8.5 9.5 10
pH of Sample solution

Fig. 4.4.1 Effect of pH on the % uptake of Fe(III).

120
100
80
60
% Uptake of Fe(III)

40
20
0
100 200
300 400
500 600
700
Amount of polymer(mg.)

Fig. 4.4.2 Effect of the amount of polymer on % uptake of Fe(III)

100
80
60
% Uptake of Fe(III)

40
20
0
15

30

45

60

75

Shaking Time (min.)

Fig. 4.4.3 Effect of the shaking time on the % uptake of Fe(III)

100
80
60
% Uptake of Fe(III)

40
20
0
25 50 100
150 200

250 300 350

400

Sample volume (mL)

Fig. 4.4.4 Effect of the sample volume on the % uptake of Fe(III)

100
80
60
% Uptake of Fe(III)

40
20
0
0.5

1.5

2.5

Eluent Conc. (M)

Fig. 4.4.5 Effect of eluent concentration on the % uptake of Fe(III)

100
80
60
% Uptake of Fe(III)

40
20
0
1

Eluent Volume(mL)

Fig. 4.4.6 Effect of eluent volume on the % uptake of Fe(III)

4.4.4 Effect of foreign ion

Synthetic solutions containing 55 ng. of Fe(III) and various amounts of foreign ions were
prepared and general procedure was followed. The tolerance limit was defined as the amount
of foreign ions causing a change less than 5% in the recovery of Fe(III). (Table 4.4.1), shows
the results. As can be seen a very good selectivity is achieved.

Table 4.4.1 Effect of foreign ions on the determination of Fe(III)

Foreign ions
NO3-, SO42-, HPO42-, SCN-, NO2-, PO43Na+, K+, Mg2+, Ba2+, Al3+, Rb+, Cs+, Ag+
Sb3+, Ca2+, Zr4+, Ti
Th4+, Sn2+, As3+
a
Ni2+, bCu2+, cCo2+
d
Hg2+, dCd2+, ePb2+, fFe2+, gMn2+
EDTA, Br-, F-, CN-, citrate

Tolerance limit[WForeign ion/WFe(III)]

>1500
2000
1500
100
10
1
1

a-masked with 1.0 mL of 2.0% dimethylglyoxime; b-masked with 1.0 mL of 3.0% sodium
thiosulphate; c-masked with 1.0 mL of 10.0% -benzilmonoxime; d-masked with 5.0 mL of
2.0% sodium thioglycollate solution; e-masked with 2.0 mL of 1.0% sodium sulphate

solution; g-masked with 1.0 mL of 2.0% 1,10-phenenthroline; f-masked with 2.0 mL 3.0%
sodium hexametaphosphate solution; g-masked with 1.0 mL of 5% sodium citrate solution.

4.4.5 Validation of the method

The method was applied to the determination of Fe(III) in standard alloy, water and biscuit
samples. The results are given in the Tables 4.4.2, 4.4.3 and 4.4.4 respectively. The accuracy
of the described preconcentration method was tested in the recovery studies by adding known
amounts of Fe(III) to the water sample and biscuit samples. The recovery values obtained
from the spiking study are satisfactory. These results confirm the validity of the proposed
method.

4.4.5.1 Determination of iron in standard alloys

The accuracy of the proposed method was verified by the determination of Fe(III) in standard
reference alloy samples. A 0.1 g of the standard alloy was completely dissolved in 20mL of
hydrochloric acid by heating on a water bath; 2mL of 30% (w/v) hydrogen peroxide was
added to the solution. The excess of peroxide was decomposed by heating the solution on a
water bath. The solution was cooled, filtered and diluted to 100 mL with double distilled.
Further dilutions were made as required. An aliquot of this solution was taken and
preconcentration was done by the developed procedure (Table 4.4.2).

4.4.5.2 Sample Collection and Conditioning

Water samples were collected from the different parts of Patiala City. The water samples were
immediately filtered through cellulose membrane filter (0.45 m pore size), and stored in
precleaned polyethylene bottles. After then, pH of the sample was adjusted to 5.5 and the
preconcentration procedure as described above was applied (Table 4.4.3).

4.4.5.3 Determination of iron in biscuit samples

Biscuit samples were purchased from the local markets nearby Punjabi University, Patiala.
Before starting the analysis, biscuits were ground and dried in an oven at 105 0C for 2h to
remove the moisture content. Biscuit samples were digested following the literature method
[411]. For digestion purpose, accurately weighed 5.0gm. of the sample was placed in a glass
beaker and digested with HNO3:H2SO4 (8:4 V/V). The mixture was heated up to 1300C for 1h.
After cooling the digest 5mL of distilled water was added and filtered with a Whatman Filter
no. 42. After spiking with known concentration of Fe(III), the digested samples were
analyzed using the developed procedure (Table 4.4.4).

Table 4.4.2 Determination of Fe(III) in different alloy samples (mean

standard deviation) (for n = 3)
Alloy sample

Certified
Composition
84 Fe, 15 Mn,
1C

Present Fe(III) Found Fe(III)

(ng.)
(ng.)
Manganese
11.5
11.3 0.12
steel
15.0
14.6 0.10
20.0
19.6 0.15
Stainless
85.6 Fe, 14
25.0
24.5 0.20
steel
Cr, 0.35 C
30.0
29.5 0.10
35.0
34.4 0.19
*n is the average of three replicate determination

% Relative
Error
1.7
2.7
2.0
2.0
1.7
1.7

% Recovery
98.3
97.3
97.8
98.0
98.3
98.2

Table 4.4.3 Determination of Fe(III) in different water samples (mean

standard deviation) (for n = 3)
Sample
Tap Water
(Punjabi
University)

Spiked
(ng.)
0.0
25.0
20.0

Found Fe(III)
(ng.)$
B.D.L.
24.2 0.22
19.4 0.20

% Relative
Error
------3.2
3.0

% Rec.
------96.8
97.0

Tap Water
0.0
B.D.L.
(Urban
36.0
35.4 0.16
Estate
40.0
39.0 0.26
Ph-II)
Bottled
0.0
B.D.L.
mineral
45.0
43.4 0.34
Water
50.0
48.2 0.23
(Bisleri)
B.D.L. (below detection limit)

------1.7
2.5
------3.6
3.6

-----98.3
97.5
-----96.4
96.4

Mean std. deviation

*n is the average of three replicate determinations

Table 4.4.4 Determination of Fe(III) in biscuit samples (mean standard

deviation) (for n = 3)
Biscuit Type

Spiked Fe(III)
(ng.)
*
Krackjack
0.0
(Parle)
45.0
50.0
*
Hide & Seek
0.0
(Parle)
40.0
35.0
B.D.L. (below detection limit)

Found Fe(III)
(ng.)
B.D.L.
44.0 0.13
48.9 0.25
B.D.L.
39.2 0.15
34.3 0.18

% Relative
Error
------2.2
2.2
------2.0
2.0

% Recovery
------97.8
97.8
------98.0
98.0

*n is the average of three replicate determinations

*MKTD BY:
PARLE PRODUCTS PVT. LTD. NORTH LEVEL CROSSING VILE PARLE, EAST
MUMBAI, MH-400057

Table 4.4.5 Comparison of the preconcentration factor of the different

techniques with present method
Modificatio
n
Mode
Physically
modified

Polymer

Modifier

Detectio
n
& Mode
FAAS
Off-line

Diaion
HP-2MG

Aspergillu
s
fumigatus

Chemically
modified

Amberlite
XAD-2

5-PHQ

FAAS
Off-line

Physically
modified

Silica gel

FAAS
Off-line

Physically
modified

Analcime
Zeolite

Aspergillu
s
niger
L

Physically
modified

Amberlite
XAD-16

Inclusion

-CDP

p
H

SD
(mg
)
500

PF

LOD

Eluen
t

Application
s

50

0.32

10 mL
of 1M
HCl

350
0

50

5.5

Water,
tomato
paste, black
tea & dust
Lake water
samples

8.0

200

50

FAAS
Off-line

3.5

100
0

60

HL

FAAS
Off-line

5.0

-----

25

PAN

UV-Vis

5.5

400

75

8.0

20 mL
of 2M
HNO3
1.7 10 mL
of 1M
HCl
0.084 10 mL
of
0.1M
EDTA
4.59 10 mL
of 2M
HCl
1.12 4 mL

Water &
vegetable
samples
Drinking
& river
water
samples
Water &
food
samples
Water &

%
Ref
Rec .
.
~ 99 379

98

416

~ 98

420

~ 99

421

~ 95

422

95

DM

Off-line

of 2M
HCl

food
samples

SSA: 5-sulfosalicylic acid; 5-PHQ: 5-Palnitoyl-8-hydroxy quinoline; SPIMP: 2-[{-(3silylpropylimino)-methyl}phenol] L: 5-[-(4-nitrophenylazo)-N-(2,4-dimethyoxyphenyl)]

salicylaldimine; HL: 5-hydroxy-4-ethyl-5,6-dipyridin-2-yl-4,5-dihydro-2H-[1,2,4] triazine-3thione; PAN: 1-(2-pyridylazo)-2-naphthol; FAAS: Flame atomic absorption spectrometry;
ICP-AES: Inductively coupled plasma atomic emission spectrometry; N.R. not reported;

Table 4.4.6 Optimum experimental conditions for the preconcentration of

Fe(III) using -CDP-PAN as sorbent
Parameters
pH
Shaking Time(min)
Sample Volume(mL)
Polymer Dose(mg.)
Eluent Used
Eluent Concentration(M)
Volume of Eluent(mL)
Preconcentration Factor

Optimum Value
5.5
45min
100mL
400mg.
HCl
2M
4mL
75

4.5 Preconcentration of Pb(II) using -CDP-PAN polymer

4.5.1 Materials
4.5.1.1 Equipments
Equipments are same as described in section 4.1.1.1.

4.5.1.2 Reagents
1 10-2M Pb(II) solution was prepared by dissolving 0.303gm. of lead sulphate (PbSO 4) in
100 mL of distilled water to give standard stock solution.

4.5.2 Procedure
4.5.2.1 Batch Extraction Procedure
At room temperature, -CDP-PAN (400mg) & 10.0 mL of buffer solution (pH 9.0) were
added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN could swell sufficiently. 600 ng. of Pb(II) were
added & made up to 100 mL with double distilled water. After the mixture was shaken in the
thermostatic shaking water bath for 45 min, 5.0 mL of the supernatant solution was

transferred into a 10mL volumetric flask & the absorbance was measured using standard
spectrophotometric method [394]. Pb(II) retained on -CDP-PAN polymer was eluted using 5
mL of 2M HCl as an eluent.

4.5.3 Optimization of various parameters

4.5.3.1 Effect of pH
For solid phase extraction of heavy metal ions on different types of chelating resins, the pH
of the aqueous solution is one of the foremost factors for quantitative recoveries of the
analytes. Therefore, the effect of pH on the uptake of Pb(II) on PAN modified -CDP
polymer was studied in the pH range of 5.0-10.5. For this purpose 600 ng. of Pb(II) were
spiked to a 100 mL of the model solution and the pH of this solution was adjusted using
different buffer solutions and then the general preconcentration procedure was followed. The
correlation between the % uptake of Pb(II) on the polymer and pH is presented in (Fig. 4.5.1).
The results of this study shows that quantitative uptake (95%) of Pb(II) ions was achieved
over pH range of 8.5-9.5. Therefore, for subsequent studies, pH 9.0 was selected as the
working pH.

4.5.3.2 Effect of amount of polymer on % uptake of Pb(II)

The amount of polymer is another important parameter to obtain quantitative uptake. For this
reason the amount of PAN modified -CDP polymer was studied in the range. The uptake of
Pb(II) was examined in relation to the amount of polymer ranging from 100 to 600 mg. It was
found that the recoveries were gradually increased up to 400mg. of polymer beyond which
there was no any increase observed. Therefore, 400mg. of polymer was used for Pb(II) in
subsequent experiments.

4.5.3.3 Effect of shaking time on % uptake of Pb(II)

Kinetics of the metal uptake is an important factor in determining the possibility of
application of the -CDP-PAN polymer for the selective uptake of Pb(II). The 400 mg. of the
polymer was shaken with 100 mL of the solution containing 600 ng. of Pb(II) at room
temperature for different contact times ranging from 15 to 75 min. as shown in (Fig. 4.5.2).
The kinetics of the polymer-metal interaction is sufficiently rapid for Pb(II) at optimum pH.
The faster uptake of Pb(II) on -CDP-PAN reflects a good accessibility of the chelating resin
sites to metal ion. Therefore, the contact time of 45 min. was selected as the uptake
equilibrium time.

4.5.3.4 Effect of sample volume on % uptake of Pb(II)

In order to explore the possibility of enriching low concentration of analytes from large
volume of solution, the effect of sample volume on % uptake of Pb(II) ion was also
investigated. For this purpose, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450 & 500mL of
sample solutions containing same amount of Pb(II) were taken under optimum conditions and
determined experimentally. Quantitative uptake ( 95%) was obtained for sample volume of
400 mL as is seen in (Fig. 4.5.3). But for convenience, 100 mL was adopted as the working
solution for the preconcentration of Pb(II).

4.5.3.5 Effect of shaking speed (r.p.m.) on % uptake of Pb(II)

The % uptake of Pb(II) increased gradually with a rise in the shaking speed (Fig. 4.5.4). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Therefore, the present study suggests that the
shaking effect is high-flying parameter for the maximum % uptake of an analyte ion.

4.5.3.6 Effect of eluent concentration

The effect of eluent concentration on the recovery of Pb(II) was also examined. Different
concentrations of HCl ranging from (0.5-4M) were tested in order to strip Pb(II) from
polymer. The recovery of Pb(II) increased, as HCl concentration increased up to 3M and it
decreased above this concentration. Therefore an HCl concentration of 3M was selected for
subsequent studies (Fig. 4.5.5).

4.5.3.7 Effect of eluent volume

In order to choose proper volume of the eluent, the retained complex was stripped with
different volumes (16 mL) of 3M HCl. Quantitative recoveries were obtained at 5mL of 3M
HCl. Thus, an eluent volume of 5 mL at 3M concentration was selected for further studies.
The preconcentration factor comes out to be 80 if the volume of eluent used is 5 mL (Fig.
4.5.6).

100
80
60
% Uptake of Pb(II)

40
20
0
5 5.5 6
6.5 7.5 8
8.5 9 9.5
10 10.5
pH of sample solution

Fig. 4.5.1 Effect of pH on % uptake of Pb(II)

100
80
60
% Uptake of Pb(II)

40
20
0
15

30

45

60

75

Shaking Time(min.)

Fig. 4.5.2 Effect of shaking time on % uptake of Pb(II)

100
80
60
% Uptake of Pb(II)

40
20

50
0

40
0

30
0

20
0

10
0

25

Sample volume(mL)

Fig. 4.5.3 Effect of the sample volume on % uptake of Pb(II)

100
80
60
% Uptake of Sb(III)

40
20
0
40

60

80

100 120
140

Shaking speed (r.p.m.)

Fig. 4.5.4 Effect of shaking speed on % uptake of Pb(II)

100
80
60
% Uptake of Pb(II)

40
20
0
0.5

Eluent Conc. (M)

Fig. 4.5.5 Effect of eluent Conc. on % uptake of Pb(II)

100
80
60
% Uptake of Pb(II)

40
20
0
1

Elunet Volume(mL)

Fig. 4.5.6 Effect of eluent volume on % uptake of Pb(II)

4.5.4 Matrix Effect

The preconcentration procedure for the trace metals can be strongly affected by other
constituents of the sample. For this reason, the reliability of the proposed method was
examined in the presence of possible interfering ion. Interjecting cations & anions were
added to the model samples. The results are presented in (Table 4.5.1). The results indicate
that most of the alkali and alkaline earth metal cations and anions do not interject in the
analysis of Pb(II) under the reported conditions.

Table 4.5.1 Effect of foreign ions on the determination of 600 ng. of Pb(II)
Foreign ions
NO3-, SO42-, HPO42-, SCN-, NO2-, PO43Na+, K+, Mg2+, Ba2+, Al3+, Rb+, Cs+,
Ag+
Sb3+, Ca2+, Zr4+, Ti
Th4+, Sn2+, As3+
a
Fe3+, bCu2+, cCo2+
d
Hg2+, dCd2+, eFe2+, fMn2+
EDTA, Br-, F-, CN-, citrate

Tolerance limit[WForeign ion/WPb(II)]

>1000
1000
500
200
20
1
1

a-masked with 1.0 mL of 5.0% ammonium oxalate solution; b-masked with 1.0 mL of 3.0%
sodium thiosulphate; c-masked with 1.0 mL of 10.0% -benzilmonoxime; d-masked with 5.0

mL of 2.0% sodium thioglycollate solution; e-masked with 1.0 mL of 2.0% 1,10phenenthroline; f-masked with 2.0 mL 3.0% sodium hexametaphosphate solution; masked
with 1.0 mL of 10.0% sodium citrate solution

4.5.5 Applications of the method

The application of the proposed method for the analysis of real samples was studied by
determining Pb(II) in different water samples and in the biscuit samples like Monaco (Parle)
& Bourbon (Britannia) purchased from local market nearby Punjabi University. These
samples were subjected to digestion, preconcentration & metal ion determination using the
proposed procedure.

4.5.5.1 Sample Collection & Conditioning

Water samples were collected from the different parts of Punjabi University, Patiala. The
water samples were immediately filtered through cellulose membrane filter (0.45 m pore
size), & stored in precleaned polyethylene bottles. After then, pH of the sample was adjusted
to 9.0 & the preconcentration procedure as described above was applied (Table 4.5.2).

4.5.5.2 Determination of Pb(II) in biscuit samples

Biscuit samples were purchased from the local markets nearby Punjabi University, Patiala.
Before starting the analysis, biscuits were ground and dried in an oven at 105 0C for 2h to
remove the moisture content. Biscuit samples were digested following the literature method
[411]. For digestion purpose, accurately weighed 5.0gm. of the sample was placed in a glass
beaker and digested with HNO3:H2SO4(8:4 V/V). The mixture was heated up to 130 0C for 1h.
After cooling the digest 5mL of distilled water was added and filtered with a Whatman Filter
no. 42. After spiking with known concentration of Pb(II), the digested samples were analyzed
using the developed procedure (Table 4.5.3).

Table 4.5.2 Determination of Pb(II) in water samples (n=3)

Water
Samples
Tap water

Rose water

R.O. water

Spiked (ng.)
Pb(II)
0.0

Found (ng.)
Pb(II)
60.5

% Recovery

300.0

361.5

100.3

-0.3

400.0

458.1

99.4

0.6

0.0

N.D.

------

------

350.0

349.2

99.8

0.2

450.0

449.4

99.9

0.1

0.0

N.D.

------

------

280.0

279.8

99.9

0.1

320.0

319.5

99.8

0.2

------

% Relative
Error
------

N.D. not detected; R.O. reverse osmosis

*n is the average of the three replicate experiments

Table 4.5.3 Determination of Pb(II) in biscuit samples (n=3)

Biscuit
Samples
^
Monaco

Spiked (ng.)
Pb(II)
0.0
415.0
450.0
#
Bourbon
0.0
500.0
550.0
N.D. not detected

Found (ng.)
Pb(II)
N.D.
414.0
447.7
N.D.
497.4
546.7

% Recovery
------99.8
99.2
------99.5
99.4

% Relative
Error
------0.2
0.5
-----0.5
0.6

Analyzed Food Products Marketed by:

^

PARLE PRODUCTS PVT. LTD. NORTH LEVEL CROSSING, VILE PARLE EAST,

MUMBAI, MH 400057
#

BRITTANIA INDUSTRIES LTD., 5/1A, HUNGERFORD STREET, KOLKATA

700017. (A WADIA ENTERPRISE)

4.5.5 Accuracy of the method

As no standard reference material for water samples was available in our laboratory, the
accuracy of the described preconcentration/separation procedure was tested in the recovery
studies by adding known amounts of the Pb(II) to the water and food samples of 100 mL. The
results obtained from the analysis of water and food samples are depicted in Tables 4.5.2 and
4.5.3, respectively. The recovery values obtained from the spiked sample analysis were
satisfactory and quantitative. It can be concluded that the described procedure can be
successfully applied to the water and food samples for the preconcentration and
determination of Pb(II).

4.5.5 Comparison of the given method with existing method

A comparison of the proposed method with other SPE methods in terms of preconcentration
factor was evaluated, and the results are summarized in (Table 4.5.4). The SPE method
developed by using -cyclodextrin polymer modified with PAN showed high PF when
compared to other methods reported in literature. These results indicate that the proposed
method is suitable for the determination of Pb(II) in water and food samples.

Table 4.5.4 Comparison with the other off-line solid phase extraction
preconcentration procedures for the determination of Pb (II)
S.
No
.
1.

Modificatio
n
Mode
Physically
modified

Polymer

Modifier

Diaion
HP
2MG

Aspergillus
fumigatus

2.

Chemically
modified

MWCNTs

tris-(2aminoethyl
) amine

3.

Chemically
modified

Amberlite
XAD-2

4.

Physically

Amberlite

5Palmitoyl8-hydroxy
quinoline
2-

Detectio
n
& Mode
FAAS
Off-line

PF

8.0

SD
(mg
)
500

ICP-OES
Off-line

5.0

30

FAAS
Off-line

FAAS

p
H

LOD

Eluen
t

Application
s

Ref
.

50

0.7

10 mL
of 1M
HCl

379

60

32

05 mL
of 2M
HCl

6.0 3500

50

4.2

20 mL
of 2M
HNO3

Water,
tomato
paste, black
tea & dust
Environmental
water
samples
Lake water
samples

9.5

20

5.0

20 mL

Environ-

397

-----

423

416

modified

XAD1180

Mercaptobenzo
Thiazole
NPTT

5.

Chemically
modified

Amberlite
XAD-2

6.

Chemically
modified

Silica gel

7.

Chemically
modified

MWCNTs

8.

Chemically
modified

TiO2 Nano
particles

Dithizone

9.

Chemically
modified

Silica
Nano
particles

RATP

10.

Inclusion
complex

-CDP

PAN

Off-line

of 2M
HNO3

ICP-AES
Off-line

6.0

500

60

0.16

HBAHBA

FAAS
Off-line

4.0

100

20

2.1

Nano-ZrO2

FAAS
Off-line

4.0

200

ICP-AES
or
ETAAS
Off-line
UV-VIS
Off-line

5.0

20

33.
3

8.0

20

60

UV-VIS
Off-line

9.0

500

70

0.80

30

10 mL
of 1M
HNO3
05 mL
of 3N
HNO3

05 mL
of 1M
HCl
1.7
1.5
mL of
0.25M
HCl
0.58
5.0
mL of
0.5M
HCl
0.003
5.0
mL of
2M
HCl

mental
water
samples
Water &
food
samples
Mango pulp,
leafy
vegetables
& fish
samples
Clay & tap
water
samples
Food stuffs,
plants &
water
samples
Natural
water
samples
Water &
food
samples

PF: preconcentration factor; SD(mg): sorbent dose(mg.); LOD: limit of detection (ng.);
RSD: relative standard deviation; NPTT: 3-(2-Nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione;
HBAHBA: 5-[2-hydroxybenzylideneamino]-2-hydroxy benzoic acid; MWCNTs: Multi
walled carbon nanotubes; FAAS: Flame atomic absorption spectrometry; ICP-OES:
Inductively coupled plasma optical emission spectrometry; ICP-AES: Inductively coupled
plasma atomic emission spectrometry; ETAAS: Electrothermal atomic absorption
spectrometry; RATP: Resacetophenone; -CDP: -cyclodextrin polymer; PAN: 1-(2pyridylazo)-2-naphthol.

400

424

425

426

427

DM

Table 4.5.5 Optimum experimental conditions for the preconcentration of Pb(II)

using -CDP-PAN as sorbent
Parameters
pH
Shaking Time(min)
Sample
Volume(mL)
Polymer Dose(mg.)
Eluent Used
Eluent
Concentration(M)
Volume
of
Eluent(mL)
Preconcentration
Factor

Optimum Value
9.0
45min
100mL
400mg.
HCl
3M
5mL
80

4.6 Preconcentration of Cd(II) using -CDP-PAN polymer

4.6.1 Materials
4.6.1.1 Equipments
Equipments are same as described in section 4.1.1.1.

4.6.1.2 Reagents
Cd(II) solution was prepared by dissolving 0.308 gm. of cadmium nitrate tetra hydrate
Cd(NO3)2. 4H2O in 100mL of distilled water to give standard stock solution.

4.6.2 Procedure
4.6.2.1 Batch Extraction Procedure
At room temperature i.e., 300C -CDP-PAN (300mg) & 10.0 mL of buffer solution (pH 9.5)
were added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN could swell sufficiently. 100ng. of Cd(II) was
added & made up to 100mL with double distilled water. After the mixture was shaken in the
thermostatic shaking water bath for 40 min, 5.0 mL of the supernatant solution was
transferred into a 10mL volumetric flask & the absorbance was measured using standard
spectrophotometric method [394]. Cd(II) retained on -CDP-PAN polymer was eluted using
5 mL of 3M HCl.

4.6.3 Optimization of various parameters

4.6.3.1 Effect of pH
For solid phase extraction of heavy metal ions on different types of chelating resins, the pH
of the aqueous solution is one of the foremost factors for quantitative recoveries of the
analytes. Therefore, the effect of pH on the uptake of Cd(II) on PAN modified polymer was
studied in the pH range of 3.5-10.5. For this purpose 100 ng. of Cd(II) were spiked to a 100
mL of the model solution and the pH of this solution was adjusted using different buffer
solutions and then the general preconcentration procedure was followed. The correlation
between the % uptake of Cd(II) on the polymer and pH is presented in (Fig. 4.6.1). The
results of this study shows that quantitative uptake (95%) of Cd(II) ions was achieved over

pH range of 8.5-10.5. Therefore, for subsequent experiments, pH 9.5 was selected as the
working pH.

4.6.3.2 Effect of shaking time

Kinetics of the metal uptake is an important factor in determining the possibility of
application of the -CDP-PAN polymer for the selective uptake of Cd(II). The 300 mg. of the
polymer was shaken with 100 mL of the solution containing 100 ng. of Cd(II) at room
temperature for different contact times ranging from 10 to 60 min as shown in (Fig. 4.6.2).
The kinetics of the polymer-metal interaction is sufficiently rapid for Cd(II) at optimum pH.
The faster uptake of Cd(II) on -CDP-PAN reflects a good accessibility of the chelating resin
sites to metal ion. Therefore, the contact time of 40 min. was selected as the uptake
equilibrium time.

4.6.3.3 Effect of amount of polymer

The amount of solid phase is another important parameter to obtain quantitative recovery. For
this reason the amount of PAN modified -CDP was studied in the range. The uptake of
Cd(II) was examined in relation to the amount of polymer, which was varied from 100 to 500
mg. It was found that the recoveries were gradually increased up to 300 mg. of polymer
beyond which there was no any increase observed. Therefore, 300mg. of polymer was used
for Cd(II) in subsequent experiments. The results are depicted in (Fig. 4.6.3).

4.6.3.4 Effect of sample volume

In order to explore the possibility of enriching low concentration of analytes from large
volume of solution, the effect of sample volume on the retention of Cd(II) ion was also
investigated. For this purpose, 25, 50, 100, 150, 200, 250, 300, 350, 400, 450 & 500 mL of
sample solutions containing a fixed amount of Cd(II) were taken under optimum conditions
and determined experimentally. Quantitative sorption ( 95%) was obtained for sample
volume of 350 mL as is seen in (Fig. 4.6.4). Therefore, 100 mL of sample solution was
adopted for the preconcentration of analyte from sample solutions.

4.6.3.5 Effect of shaking speed

The % uptake of Cd(II) increased gradually with a rise in the shaking speed (Fig. 4.6.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient

between the sample solution and the polymer. Therefore, the present study suggests that the
shaking effect is high-flying parameter for the maximum % uptake of an analyte ion.

4.5.3.6 Effect of elution concentration

In order to obtain the quantitative recovery of retained metal ion on -CDP-PAN, the
different concentrations of HCl (0.5-4M) (Fig. 4.6.6) were examined. Out of these 3M was
selected.

4.5.7 Effect of eluent volume

Different eluent volumes were tested during these studies 100mL aliquots containing 200 ng.
of Cd(II) were used at pH 9.0. Quantitative recoveries were obtained at 4mL. Thus, an eluent
volume of 4 mL at 3M concentration was selected for further studies. The preconcentration
factor comes out to be 87.5 if the volume of eluent used is 4 mL (Fig. 4.6.7).

100
80
60
% Uptake of Cd(II)

40
20
0
3.5 4.5 5.5
6.5 7.5 8.5
9.5 10.5
pH of Sample solution

Fig. 4.6.1 Effect of pH on % uptake of Cd(II)

100
80
60
% Uptake of Cd(II)

40
20
0
10

20

30

40

50

60

Shaking Time(min.)

Fig. 4.6.2 Effect of shaking time on % uptake of Cd(II)

100
80
60
% Uptake of Pb(II)

40
20
0
100

200

300

400

500

Adsorbent dose (mg.)

Fig. 4.6.3 Effect of polymer dose on % uptake of Cd(II)

100
80
60
% Uptake of Cd(II)

40
20
0
25 50 100
150

200250300

350 400450

Sample volume (mL)

Fig. 4.6.4 Effect of sample volume on % uptake of Cd(II)

100
80
60
% Uptake of Pb(II)

40
20
0
40

60

80

100

120

140

Shaking Speed (r.p.m.)

Fig. 4.6.5 Effect of shaking speed on % uptake of Cd(II)

100
80
60
% Uptake of Cd(II)

40
20
0
0.5

Eluent Conc. (M)

Fig. 4.6.6 Effect of eluent conc. on % uptake of Cd(II)

100
80
60
% Uptake of Cd(II)

40
20
0
1

Eluent Volume (mL)

Fig. 4.6.7 Effect of eluent volume on % uptake of Cd(II)

4.6.4. Effect of coexisting ions

The effect of various coexisting ions on the % uptake of a solution containing 200 ng. of
Cd(II) was studied. An ion was considered to interfere when its presence produced a variation
in the absorbance of the sample 5%. Among the anions examined CO 32-, SO32-, SO42-, NO3-,
IO3-, NO2- did not interfere at concentrations 1000 times more than those of the analyte. The
complexation between Cd(II) and PAN was completely masked by EDTA (ethylenediamine
tetraacetate ion) and cyanate even at lower concentration. Alkali and alkaline earth metal ions
did not interfere (Table 4.6.1)

Table 4.6.1 Effect of foreign ions on the determination of Cd(II)

Foreign ions
NO3-, SO42-, HPO42-, SCN-, NO2-, PO43Na+, K+, Mg2+, Ba2+, Al3+, Rb+, Cs+, Ag+
Sb3+, Ca2+, Zr4+, Ti
Th4+, Sn2+, As3+
a
Fe3+, bNi2+, cCu2+, dCo2+
e
Pb2+, fFe2+, gMn2+
EDTA, Br-, F-, CN-, citrate

Tolerance limit[WForeign ion/WCd(II)]

2000
1500
1000
300
10
3
1

a-masked with 1.0 mL of 5.0% ammonium oxalate solution; b-masked with 1.0 mL of 2.0%
dimethylglyoxime; c-masked with 1.0 mL of 3.0% sodium thiosulphate; d-masked with 1.0
mL of 10.0% -benzilmonoxime; e-masked with 2.0 mL of 1.0% sodium sulphate solution; fmasked with 1.0 mL of 2.0% 1,10-phenenthroline; g-masked with 2.0 mL 3.0% sodium
hexametaphosphate solution.

4.6.5 Validation of the method

The validation of the developed method was checked by applying it for the determination of
Cd(II) in water and vegetable samples.

4.6.5.1 Sample Collection and Conditioning

Water samples were collected from the Punjabi University, Patiala Campus, Patiala City. The
water samples were immediately filtered through cellulose membrane filter (0.45 m pore
size), and stored in precleaned polyethylene bottles. After then, pH of the sample was
adjusted to 8.5 and the preconcentration procedure as described above was applied (Table
4.6.2).

4.6.5.2 Determination of Cd(II) in vegetables

The established optimized conditions of extractive preconcentration method were applied to leafy
vegetables, for the determination of Cd(II) content (Table 4.6.3). The leafy vegetables analyzed
were brought from the local market during the month of January. The samples were cleaned and
dried. 10 gm. of leafy vegetable sample was pulverized in a mortar and transferred into a
precleaned beaker. 50 mL of H2SO4 (3M) was added to the above beaker and heated on a hot plate
for about an hour, until white fumes ceases to evolve and the residue is completely evaporated

to dryness. Then the sample was dissolved in water, filtered and made up to mark in a
standard measuring flask.

Table 4.6.2 Determination of Cd(II) in different water samples (n = 3)

Sample
Tap Water
(Punjabi
University)
Bottled
mineral
Water
(Bisleri)

Spiked
(ng.)
0.0
45.0
55.0
0.0
120.0
135.0

Found
(ng.)$
------44.0 1.2
53.4 1.5
------116.8 1.7
130.8 1.4

% Relative
Error
------2.2
2.9
------2.7
3.1

% Rec.
------97.8
97.1
------97.3
96.9

Found R.S.D

Table 4.6.3 Determination of Cd(II) in different vegetable samples (n = 3)

Vegetable
Sample*
Cabbage

Spinach

Spiked
(ng.)
0.0
90.0
95.0
0.0
65.0
75.0

Found
(ng.)$
------87.1 1.0
92.2 1.3
------63.2 2.1
72.5 1.6

% Relative
Error
------3.2
2.9
------2.8
3.3

% Rec.
-----96.8
97.0
-----97.2
96.7

Found R.S.D

*Vegetable samples were collected from market in Urban Estate Ph-II Patiala

4.6.6 Accuracy of the Method

The accuracy of the given method was tested by adding known amount of the analyte to the
different water and vegetable samples. As can be seen from the data presented in Tables 4.6.2
and 4.6.3, the quantitative recoveries are obtained an all of the cases.

4.6.7 Comparison of the developed method

The developed method was compared with the other methods reported in literature for the
preconcentration factor. As can be seen (Table 4.6.4), the developed method for
preconcentration of Cd(II) using -CDP-PAN system is having high preconcentration factor
and lower LOD value.

Table 4.6.4 Comparison of preconcentration factor of different polymer for

Cd(II)
Sr.
No
.

Modification
Mode

Polymer

Modifie
r

LOD
(ng/mL
)

Preconcen. Sorbent
Factor
Dose(mg)

1.

Chemically
modified

XAD-2

5-PHQ

4.2

50

5000

2.

Physically
modified

Sepabeads
SP-207

Na-DDC

0.17

50

600

3.

Chemically
modified

MWCNTs

LCysteine

0.28

33

10

4.

Chemically
modified

DHAQ

0.60

66.4

25

5.

------------

Silica
nanoparticle
s
MWCNTs

--------

0.3

-------

35

6.

Physically
modified

XAD-4

APDC

N.R.

33.3

500

7.

Physically
modified

MWCNTs

PAN

0.43

40

150

8.

Chemically
modified

XAD-2

NPTT

0.22

60

500

9.

Chemically
modified

Silica Gel

PEG

0.33

66.6

350

10.

Chemically
modified

Nanometer
Alumina

CTA

0.14

50

50

11.

Physically
modified

Peanut Shell

H3PO4

0.2

40

-------

12.

Inclusion

-CDP

PAN

0.03

87.5

300

Eluent

20 mL
of 2M
HNO3
5 mL
of 2M
HNO3
2 mL
of
0.5M
HCl
6 mL
of 1M
HCl
2 mL
of 1M
HNO3
15 mL
of 2M
HNO3
5 mL
of 1M
HNO3
10 mL
of 1M
HNO3
3 mL
of 1M
HNO3
2mL of
1M
HNO3
1.5 mL
of
0.1M
HCl
4 mL
of 3M

Method,
Detectio
n
& Mode
SPE
FAAS
Off-line
SPE
FAAS
Off-line
SPE
FAAS
On-line

Ref.

SPE
UV-Vis
Off-line
SPE
ICP-AES
Off-line
SPE
FAAS
Off-line
SPE
FAAS
Off-line
SPE
ICP-AES
Off-line
SPE
FAAS
Off-line
SPE
ICP-AES
Off-line
SPE
FAAS
Off-line

430

SPE
UV-Vis

DM

416

428

429

431

432

433

379

400

434

435

HCl

Off-line

2-MBT: 2-Mercapto benzothiazole; 4-HT: 4-Hydroxy tolune; CTA: Chromotropic acid; 2ATP: 2-Amino thiophenol; PCV: Pyrocatechol violet; PEG: Polyethylene glycol; NPTT: 3(2-Nitrophenyl)-1H-1,2,4-triazole-5(4H)-thione; 5-PHQ: 5-Palmitoyl-8-hydroxy quinoline;
Na-DDC: Sodium diethyl dithiocarbamate; DHAQ: 1,8-Dihydroxy quinoline; APDC:
Ammonium pyrrolidine dithiocarbamate; SDS: Sodium dodecyl sulphate; HBTSC: 2Hydrpxybenzaldehyde thiosemicarbazone; H3PO4: Phosphoric acid; 5-Br-PADAP: 2-(5Bromo-2-pyridylazo)-5-diethylaminophenol; PAN: 1-(2-pyridylazo)-2-naphthol

Table 4.6.5 List of various parameters optimized for the preconcentration of

Cd(II) using -CDP-PAN polymer
Parameter

Optimized Value

pH

9.5

Shaking time (min.)

40 min.

Amount of polymer (mg.)

300 mg.

Sample volume (mL)

100 mL

Shaking speed (r.p.m.)

120 r.p.m.

Eluent Type

HCl

Eluent Concentration (M)

3M

Eluent Volume (mL)

4 mL

4.7 Preconcentration of Hg(II) using -CDP-PAN polymer

4.7.1 Materials
4.7.1.1 Equipments
Equipments are same as described in section 4.1.1.1.

4.7.1.2 Reagents
All reagents used were of analytical reagent grade. Double distilled water was used
throughout the experiment. Hg(II) solution was prepared by dissolving 0.308 gm. of mercuric
sulphate (HgSO4) in 100mL of distilled water to give standard stock solution.

4.7.2 Procedure
4.7.2.1 Batch Extraction Procedure
At room temperature, -CDP-PAN (400mg) & 10.0 mL of buffer solution (pH 9.5) were
added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN can swell sufficiently. 200ng. of Hg(II) was added
& made up to 100mL with double distilled water. After the mixture was shaken in the
thermostatic shaking water bath for 40 min, 5.0 mL of the supernatant solution was
transferred into a 10mL volumetric flask & the absorbance was measured using standard
spectrophotometric method [394]. Hg(II) retained on -CDP-PAN polymer was eluted using
5 mL of 3M HCl.

4.7.3 Optimization of various parameters

4.7.3.1 Effect of pH
The uptake of an analyte on the chelating polymer is dependent on the pH of sample solution
due to the competitive reaction between chelate forming groups and hydrogen ions in the
solutions. An excess of Hg(II) 200ng. were spiked to a 100 mL of the sample solution
containing 400 mg. of polymer and shook for 40 min. The pH of this solution was adjusted in
the range of 7.5 to 10.5 using different buffer system and then the preconcentration procedure
as described was applied. As it can be seen in (Fig. 4.7.1), quantitative uptake ( 95%) was
obtained at pH 9.0-10.0 0.01. Therefore, the working pH was chosen as 9.5 for the
subsequent experiments.

4.7.3.2 Effect of the amount of polymer

The amount of the polymer is another important parameter that affects the uptake of an
analyte. A quantitative retention ( 95%) cannot be achieved when the polymer is less than
the optimum amount. On the other hand, an excess amount of polymer prevents the
quantitative elution of the retained metal chelate by a small volume of the eluent. In order to
optimize the smallest amount, 100, 200, 300, 400, 500, 600 mg. of the polymer were added to
the 100 mL of the sample solution containing 200 ng. of Hg(II) and preconcentrated by the
general procedure. The quantitative recoveries were obtained for and above 400 mg. of
polymer (Fig. 4.7.2). Therefore, 400 mg. of the polymer has been used for subsequent
experiments.

4.7.3.3 Effect of shaking time

Shaking time is an important factor in determining the possibility of application of the CDP-PAN polymer for the uptake of Hg(II). For studying the effect of shaking time on the %
uptake, 400 mg. amount of the polymer was shaken with 100 mL of solution containing 200
ng. of Hg(II) for different shaking time (ranging from 10 to 60 minutes) with an interval of 10
minutes at optimum pH. The results of % uptake of Hg(II) vs. the shaking time show that the
percentage uptake reached maximum (above 95%) at 40 min (Fig. 4.7.3). Therefore, the
shaking time of 40 min. was selected as the adsorption equilibrium time.

4.7.3.4 Effect of the sample volume

In order to explore the possibility of enriching low concentration of analytes from large
volume of sample, the effect of sample volume on the retention of Hg(II) was also
investigated. 50, 100, 150, 200, 250, 300, 350, 400, 450 mL of sample solutions containing a
fixed amount of Hg(II), 400 mg. of polymer at optimum pH and shook for 40 min.
Quantitative uptakes ( 95%) were obtained for sample volume of 350 mL (Fig. 4.7.4).
Therefore, 100 mL of sample solution was adopted for the preconcentration of analyte from
sample solutions. The preconcentration factor is calculated by the ratio of the highest sample
volume (350 mL) and the lowest eluent volume (4 mL). Therefore, the preconcentration
factor was 87.5.

4.7.3.5 Effect of shaking speed

The % uptake of Cu(II) increased gradually with a rise in the shaking speed (Fig. 4.7.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the

mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Present study suggests that the shaking effect is
high-flying parameter for the maximum % uptake of an analyte ion.

4.7.3.6 Effect of nature of eluent

In order to choose the best eluent for the Hg(II) retained on -CDP-PAN polymer, various
eluent were used. Among the eluents studied, the acids provided higher recovery efficiency
than the organic solvents. From the results, it is obvious that higher recovery values were
obtained with Hydrochloric acid (HCl).

4.7.3.7. Effect of eluent conc.

The effect of HCl concentration on elution of Hg(II) retained on -CDP-PAN polymer was
studied by carrying out the elution with (0.5-5)M HCl. The results indicate that the highest
recoveries for Hg(II) were obtained when HCl concentration was 3M or more. Hence 3M was
chosen as eluent for further experimental conditions (Fig. 4.7.6).

4.7.3.8. Effect of eluent volume

In order to obtain the quantitative recovery of Hg(II) retained on -CDP-PAN polymer,
elution was carried out with different volumes ranging from (1-6 mL) of 3M HCl. During
these studies, 100 mL aliquots of the sample solutions containing 200ng. of Hg(II) were used
at pH 9.5. As obvious from the (Fig. 4.7.7), quantitative recovery values were obtained by
using 4mL of eluent.

100
80
60
% Uptake of Hg(II)

40
20
0
7.5

8.5

9.5

10 10.5

pH of sample solution

Fig. 4.7.1 Effect of pH on % uptake of Hg(II)

100
80
60
% Uptake of Hg(II)

40
20
0
100

200

300

400

500

Adsorbent dose (mg.)

Fig. 4.7.2 Effect of polymer dose on % uptake of Hg(II)

100
80
60
% Uptake of Hg(II)

40
20
0
10

20

30

40

50

60

Shaking Time(min.)

Fig. 4.7.3 Effect of shaking time on % uptake of Hg(II)

120
100
80
60
% Uptake of Hg(II)

40
20
0
25 50 100
150

200250 300

350400 450

Sample volume(mL)

Fig. 4.7.4 Effect of sample volume on % uptake of Hg(II)

100
80
60
% Uptake of Hg(II)

40
20
0
40

60

80

100

120

140

Shaking speed (r.p.m.)

Fig. 4.7.5 Effect of shaking speed on % uptake of Hg(II)

100
80
60
% Uptake of Hg(II)

40
20
0
0.5

Eluent Conc.

Fig. 4.7.6 Effect of eluent conc. on % uptake of Hg(II)

100
80
60
% Uptake of Hg(II)

40
20
0
1

Eluent Volume(mL)

Fig. 4.7.7 Effect of eluent volume on % uptake of Hg(II)

4.7.4. Effect of coexisting ions

The effect of various coexisting ions on the % uptake of a solution containing 200ng. of
Hg(II) was studied. An ion was considered to interfere when its presence produced a variation
in the absorbance of the sample 5%. Among the anions examined CO 32-, SO32-, SO42-, NO3-,
IO3-, NO2- did not interfere at concentrations 1000 times more than those of the analyte. The
complexation between Hg(II) and PAN was completely masked by EDTA (ethylenediamine
tetraacetate ion) and cyanate even at lower concentration. Alkali and alkaline earth metal ions
did not interfere (Table 4.7.1)

Table 4.7.1 Effect of foreign ions on a solution containing 200ng. of Hg(II)

Foreign ions
NO3-, SO42-, HPO42-, SCN-, NO2-, PO43Na+, K+, Mg2+, Ba2+, Al3+, Rb+, Cs+,
Ag+
Sb3+, Ca2+, Zr4+, Ti
Th4+, Sn2+, As3+
a
Fe3+, bCu2+, cCo2+
e
Fe2+, fMn2+
EDTA, Br-, F-, CN-, citrate

Tolerance limit[WForeign ion/WHg(II)]

2000
1500
100
200
20
1
1

a-masked with 1.0 mL of 5.0% ammonium oxalate solution; b-masked with 1.0 mL of 2.0%
dimethylglyoxime; c-masked with 1.0 mL of 3.0% sodium thiosulphate; d-masked with 1.0
mL of 10.0% -benzilmonoxime; e-masked with 2.0 mL of 1.0% sodium sulphate solution; fmasked with 1.0 mL of 2.0% 1,10-phenenthroline; g-masked with 2.0 mL 3.0% sodium
hexametaphosphate solution.

4.7.5 Validation of the method

The validation of the developed method was checked by applying it for the determination of
Hg(II) in different water and vegetable samples.

4.7.5.1 Sample Collection and Conditioning

Water samples were collected from the Punjabi University, Patiala Campus, Patiala City. The
water samples were immediately filtered through cellulose membrane filter (0.45 m pore
size), and stored in precleaned polyethylene bottles. After then, pH of the sample was
adjusted to 8.5 and the preconcentration procedure as described above was applied (Table
4.7.2).

4.7.5.2 Determination of Hg(II) in vegetables

The established optimized conditions of extractive preconcentration method were applied to leafy
vegetables, for the determination of Hg(II) content (Table 4.7.3). The leafy vegetables analyzed
were brought from the local market during the month of January. The samples were cleaned and
dried. 10 gm. of leafy vegetable sample was pulverized in a mortar and transferred into a
precleaned beaker. 50 mL of H2SO4 (3M) was added to the above beaker and heated on a hot plate
for about an hour, until white fumes ceases to evolve and the residue is completely evaporated

to dryness. Then the sample was dissolved in water, filtered and made up to mark in a
standard measuring flask.

Table 4.7.2 Determination of Hg(II) in different water samples (n = 3)

Sample
Tap Water
(Punjabi
University)
Bottled
mineral
Water
(Bisleri)

Spiked
(ng.)
0.0
70.0
60.0
0.0
80.0
85.0

Found
(ng.)$

% Relative
Error

% Rec.

------67.6 1.2
57.9 1.3
------77.3 1.1
82.2 1.0

------3.4
3.5
------3.4
3.3

------96.6
96.5
------96.6
96.7

Found R.S.D

Table 4.7.3 Determination of Hg(II) in different vegetable samples (n = 3)

Vegetable
Sample
Cabbage

Spinach

Spiked
(ng.)
0.0
150.0
175.0
0.0
180.0
200.0

Found
(ng.)$
------147.2 1.3
170.4 1.6
------176.0 1.7

% Relative
Error
------1.9
2.6
------2.2

% Rec.
-----98.1
97.4
-----97.8

Found R.S.D

*Vegetable samples were collected from market in Urban Estate Ph-II Patiala

4.7.6 Accuracy of the Method

The accuracy of the given method was tested by adding known amount of the analyte to the
different water and vegetable samples. As can be seen from the data presented in Tables 4.7.2
and 4.7.3, the quantitative recoveries are obtained in all of the cases.

4.7.7 Comparison of the developed method

The developed method was compared with the other methods reported in literature for the
preconcentration factor. As can be seen (Table 4.7.4), the developed method for
preconcentration of Hg(II) using -CDP-PAN system is having high preconcentration factor
and lower LOD value.

Table 4.7.4 Comparison of the procedure developed for the preconcentration of

Hg(II) using -CDP-PAN polymer with other Literature methods
Sr.
No.
1.
2.
3.

Modificatio
n
Mode
Chemically
modified
Chemically
modified
Chemically
modified

Polymer

Modifie
r

PUF

Naphthol
PAR

Off-line

50

200

Off-line

50

50

DPC

Off-line

100

750

Nano
SiO2
Silica gel

Preconcen. Preconcen. Sorbent Eluent Method Ref.

Mode
Factor
Dose(mg)

4.

Chemically
modified

Oxidized
MWCNTs

S-CS

Off-line

100

N.R.

5.

Chemically
modified

Silica

2-AT

On-line

29, 38, 46

100

6.

Chemically
modified

Activated
carbon

EDA

Off-line

133.3

25

7.

Chemically
modified
Chemically
modified

PUF

Ros

Off-line

100

200

SiO2
nanoparticle

PAN

Off-line

50

50

Inclusion

-CDP

PAN

Off-line

87.5

400

8.

9.

0.1M
HNO3
6M
HCl
10 mL
of
PEG
10 mL
of
10M
HCl
0.1
mL of
2M
HCl
3.0
mL of
2%
TU &
0.5M
HCl
2M
HCl
5 mL
of 6M
HCl
4 mL
of 3M
HCl

SPEAAS
SPECVAAS
SPEUV-Vis

436

SPECVAAS

439

SPECVAAS

440

SPEICPOES

441

SPEUV-Vis
SPEUV-Vis

442

SPEUV-Vis

DM

AAS: Atomic absorption spectrometry; CVAAS: Cold vapor atomic absorption spectrometry;
ICP-OES: Inductively coupled plasma optical emission spectrometry; PUF: Polyurethane
foam; PAR: 4-(2-pyridylazo) resorcinol; PEG: Polyethylene glycol; DPC:
Diphenylthiocarbazone; 2-AT: 2-Aminothiazole; EDA: Ethylenediamine; TU: Thiourea;
Ros: Rosaniline; PUF: Polyurethane foam; PAN: 1-(2-pyridylazo)-2-naphthol.

437
438

445

Table 4.7.5 List of various parameters optimized for the preconcentration of

Hg(II) using -CDP-PAN polymer
Parameter

Optimized Value

pH

9.5

Shaking time (min.)

40 min.

Amount of polymer (mg.)

400 mg.

Sample volume (mL)

100 mL

Shaking speed (r.p.m.)

100 r.p.m.

Eluent Type

HCl

Eluent Concentration (M)

3M

Eluent Volume (mL)

4 mL

4.8. Preconcentration of Zn(II) using -CDP-PAN polymer

4.8.1 Materials
4.8.1.1 Equipments

The equipments are same as described in 4.1.1.1.

4.8.1.2 Reagents
Zn(II) solution was prepared by using Zn(SO4).10H2O.

4.8.2 Procedure
4.8.2.1 Batch Extraction Procedure
At room temperature, -CDP-PAN (300mg) & 10.0 mL of buffer solution (pH 9.5) were
added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN can swell sufficiently. 100ng. of Zn(II) was added
& made up to 100mL with double distilled water. After the mixture was shaken in the
thermostatic shaking water bath for 40 min, 5.0 mL of the supernatant solution was
transferred into a 10mL volumetric flask & the absorbance was measured using standard
spectrophotometric method [394]. Zn(II) retained on -CDP-PAN polymer was eluted using 5
mL of 3M HCl.

4.8.3 Optimization of various parameters

4.8.3.1 Effect of pH
The complexation of the metal ion with PAN on the chelating resin is dependent on the pH of
sample solution due to the competitive reaction between chelate forming groups and
hydrogen ions in the solutions. 100 ng. of Zn(II) were spiked to a 100 mL of the model
solution. The pH of this solution was adjusted in the range of 2.5 to 10.5 using different
buffer solutions and then the preconcentration procedure as described was applied.
Quantitative uptake ( 95%) was obtained at pH 9.5 and above (Fig. 4.8.1). Therefore, 9.5
was chosen as the working pH subsequent experiments.

4.8.3.2 Effect of the amount of polymer

The amount of the polymer is another important parameter that affects the uptake. A
quantitative retention ( 95%) cannot be achieved when the polymer is less than the optimum
amount. On the other hand, an excess amount of polymer prevents the quantitative elution of
the retained metal chelate by a small volume of the eluent. In order to optimize the smallest
amount of extractant, 100, 200, 300, 400, 500, 600 and 800 mg. of the polymer were added to
the same volume of the synthetic solution containing 100 ng. of Zn(II) and preconcentrated
by the general procedure. The quantitative recoveries were obtained for and above 500 mg. of

polymer (Fig. 4.8.2). Therefore, 500 mg of the polymer has been used for subsequent
experiments.

4.8.3.3 Effect of shaking time

Shaking time is an important factor in determining the possibility of application of the CDP-PAN polymer for the selective uptake of Zn(II). Different shaking time (ranging from
15 to 75min) were studied for the % uptake of Zn(II) by -CDP-PAN polymer. The results of
% uptake of Zn(II) vs. the shaking time show that the percentage uptake reach maximum
(above 95%) at 45 min (Fig. 4.8.3). Therefore, the shaking time of 45 min. was selected as
the adsorption equilibrium time.

4.8.3.4 Effect of the sample volume

In order to explore the possibility of enriching low concentration of analytes from large
volume of solution, the effect of sample volume on the retention of Zn(II) ion was also
investigated. For this purpose, 25, 50, 100, 150, 200, 250, 300, 350, 400 and 450mL of
sample solutions containing 100 ng. of Zn(II) were taken. Quantitative uptakes ( 95%) were
obtained for sample volume of 350 mL (Fig. 4.8.4). Therefore, 100 mL of sample solution
was adopted for the preconcentration of analyte from sample solutions. The preconcentration
factor was 70 when eluent volume is 5.0 mL.

4.8.3.5 Effect of shaking speed (r.p.m.) on % uptake of Zn(II)

The % uptake of Zn(II) increased gradually with a rise in the shaking speed (Fig. 4.8.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Present study suggests that the shaking effect is
high-flying parameter for the maximum % uptake of an analyte ion.

4.8.3.6 Effect of eluent conc.

Since the adsorption of Zn(II) at pH 2 is quite low, one can expect that elution will be
favored in the acidic solutions. So various concentrations and volumes of HCl were used for
the desorption of retained Zn(II). The experimental results showed that 2M HCl was
sufficient for complete elution of Zn(II) (Fig. 4.8.6).

4.8.3.7 Effect of Eluent volume

In order to choose proper volume of the eluent, the retained complex was stripped with
different volumes (16 mL) of 2.0 M HCl. It was found that quantitative recoveries (95%)
with 5.0 mL of 2M HCl as eluent could be obtained (Fig. 4.8.7). Therefore, for eluting Zn(II)
5.0 mL of 2M HCl was used as eluent.

100
80
60
% Uptake of Zn(II)

40
20
0
2.5 3.5 4.5
6.5 7.5 8.5
9.5 10 10.5
pH

Fig. 4.8.1 Effect of pH on the % uptake of Zn(II)

100
80
60
% Uptake of Zn(II)

40
20
0
100 200
300 400
500 600
700
Amount of polymer (mg.)

Fig. 4.8.2 Effect of the amount of polymer on the % uptake of Zn(II)

100
80
60
(%) Uptake of Zn(II)

40
20
0
15

30

45

60

75

Contact time(min.)

Fig. 4.8.3 Effect of the contact time on the % uptake of Zn(II)

120
100
80
60
% Uptake of Zn(II)

40
20
0
25 50 100
150 200 250

300 350 400

450

Sample Volume (mL)

Fig. 4.8.4 Effect of the sample volume on the % uptake of Zn(II)

100
80
60
% Uptake of Zn(II)

40
20
0
40

60

80

100

120

140

Shaking speed (r.p.m.)

Fig. 4.8.5 Effect of shaking speed on % uptake of Zn(II)

100
80
60
% Uptake of Zn(II)

40
20
0
0.5

Eluent Conc. (M)

Fig. 4.8.6 Effect of eluent concentration on the % uptake of Zn(II)

100
80
60
% Uptake of Zn(II)

40
20
0
1

Eluent volume(mL)

Fig. 4.8.7 Effect of eluent volume on the % uptake of Zn(II)

4.8.4 Effect of foreign ions

Synthetic solutions containing 100ng. of Zn(II) and various amounts of foreign ions were
prepared and general procedure was followed. The tolerance limit was defined as the amount
of foreign ions causing a change less than 5% in the recovery of Zn(II) (Table 4.8.1).

Table 4.8.1 Effect of foreign ions on the determination of 100ng. of Zn(II)

Foreign ions
NO3-, SO42-, HPO42-, SCN-, NO2-, PO43Na+, K+, Mg2+, Ba2+, Al3+, Rb+, Cs+, Ag+
Sb3+, Ca2+, Zr4+, Ti
Th4+, Sn2+, As3+
a
Fe3+,bNi2+, cCu2+, dCo2+
e
Hg2+, eCd2+, fPb2+, gFe2+, hMn2+
EDTA, Br-, F-, CN-, citrate

Tolerance limit[WForeign ion/WZn(II)]

>1000
1000
500
100
10
1
1

a-masked with 1.0 mL of 5.0% ammonium oxalate solution; b-masked with 1.0 mL of 2.0%
dimethylglyoxime; c-masked with 1.0 mL of 3.0% sodium thiosulphate; d-masked with 1.0
mL of 10.0% -benzilmonoxime; e-masked with 5.0 mL of 2.0% sodium thioglycollate
solution; f- masked with 2.0 mL 0f 1.0% sodium sulphate solution; g-masked with 1.0 mL of
2.0% 1,10-phenenthroline; h-masked with 2.0 mL 3.0% sodium hexametaphosphate solution.

4.8.5 Validation of the method

The validation of the developed method was checked by applying it for the determination of
Zn(II) in certified alloy and different water samples.

4.8.5.1 Certified alloy analysis

The accuracy of the proposed method was verified by the determination of Zn(II) in standard
reference alloy samples. The alloy samples were digested following the reported method. A
0.1 g of the standard alloy was completely dissolved in 20mL of hydrochloric acid by heating
on a water bath; 2ml of 30% (w/v) hydrogen peroxide was added to the solution. The excess
of peroxide was decomposed by heating the solution on a water bath. The solution was
cooled, filtered and diluted to 100 ml with double distilled. Further dilutions were made as
required. An aliquot of this solution was taken and preconcentration was done by the
developed procedure (Table 4.8.2).

4.8.5.2 Sample Collection and Conditioning

Water samples were collected from the Punjabi University, Patiala Campus, Patiala City. The
water samples were immediately filtered through cellulose membrane filter (0.45 m pore
size), and stored in precleaned polyethylene bottles. After then, pH of the sample was
adjusted to 8.5 and the preconcentration procedure as described above was applied (Table
4.8.3).

Table 4.8.2 Determination of Zn(II) in certified alloy samples (n=3)

Alloy
Sample
Brass No. 42

Certified
Composition
Cu 58, Pb 2.56,

Present (ng.)
Zn(II)
110.0

Found (ng.)
Zn(II)
109.8

% Relative
Error
0.18

% Recovery

Zn 38.99, Fe

78.0

77.9

0.14

99.85

99.81

Zamak-5

0.09, Sn 0.12
Zn 95, Al 4, Cu

40.0

39.9

0.20

99.80

1, Mg 0.5

45.0

44.8

0.33

99.66

Table 4.8.3 Determination of Zn(II) in different water samples (n=3)

Water

Spiked(ng.)

Found(ng.)

% Relative

% Recovery

Samples
Tap water

Zn(II)
0.0

Zn(II)
25.0

Error
----

------

70.0

94.7

0.4

99.6

55.5
0.0

80.3
N.D.

0.4
-----

99.6
------

50.0

50.5

-1.0

101.0

40.0
0.0

40.6
15.6

-1.5
-----

101.5
-------

60.0

75.4

0.3

99.7

70.0

85.3

0.4

99.6

Rose water

Bore water

N.D. not detected

4.8.6 Accuracy of the method

The method was applied to the determination of Zn(II) in water samples and certified alloy
samples. The accuracy of the described preconcentration method was tested in the recovery
studies by adding known amounts of the metal ion to the water sample and also by analysis of
the certified alloy samples. The results obtained from the analysis of water samples and
certified alloys, are depicted in (Table 4.8.2 and 4.8.3) respectively. The recovery values

obtained from the water and alloy samples were satisfactory. These results confirm the
validity of the proposed method.

4.8.7 Comparison with other methods

The proposed method for the preconcentration and determination of Zn(II) using -CDP-PAN
polymer was compared with the other methods cited in literature (Table 4.8.4). As can be
seen from the comparison table that the developed method has higher preconcentration factor
compared with other methods.

Table 4.8.4 Comparison of preconcentration factors of Zn(II) with other

literature methods
Sr.
No
.
1.

Modification
Mode

Adsorbent

Modifier

Preconcen. Preconcen. Sorbent

Mode
Factor
Dose(mg)

Chemically
modified

Silica gel

SPIMP

Off-line

83

800

2.

Chemically
modified

Nanometer
Sized

CTA

Off-line

100

50

Eluen
t

Metho
d

Ref.

6 mL
of 4M
HNO3
2mL
of 1M

SPEFAAS

398

SPEICP-

446

alumina
Diaion
HP-2MG

A.
Fumigatus

Off-line

50

500

3.

Physically
modified

4.

Chemically
modified

AXAD-4

AMPDAA

Off-line

80

1000

5.

Inclusion

-CDP

PAN

Off-line

70

500

SPIMP:

2-[-(3-Silylpropylimino)methyl]

phenol;

CTA:

Chromotropic

HNO3
810mL
of 1M
HCl
8 mL
of 1M
HCl
5 mL
of 2M
HCl

acid;

AES
SPEFAAS

404

SPEFAAS

447

SPE
FAAS

DM

AMPDAA:

Acetylmercaptophenyldiazoaminobenzene; PAN: 1-(2-pyridylazo)-2-naphthol; -CDP: -Cyclodextrin polymer

4.9 Preconcentration of In(III) using -CDP-PAN polymer

4.9.1 Materials
4.9.1.1 Equipments
Equipments are same as described in section 4.1.1.1.

4.9.1.2 Reagents
In(III) solution was prepared by dissolving 0.308 gm. of Indium sulphate In2(SO4)3 in 100mL
of distilled water to give standard stock solution.

2-

4.9.2 Procedure
4.9.2.1 Batch Extraction Procedure
At room temperature, -CDP-PAN (300mg) & 10.0 mL of buffer solution (pH 6.5) were
added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN could swell sufficiently. 200ng. of In(III) was
added & made up to 100mL with double distilled water. After the mixture was shaken in the
thermostatic shaking water bath for 40 min, 5.0 mL of the supernatant solution was
transferred into a 10mL volumetric flask & the absorbance was measured using standard
spectrophotometric method [394]. In(III) retained on -CDP-PAN polymer was eluted using
5 mL of 3M HCl.

4.9.3 Optimization of various parameters

4.9.3.1 Effect of pH
The sorption of an analyte on the chelating resin is dependent on the pH of sample solution
due to the competitive reaction between chelate forming groups and hydrogen ions in the
solutions. 150ng. of In(III) were spiked to a 100 mL of the sample solution containing 400
mg. of polymer and shook for 40 min. The pH of this solution was adjusted in the range of
3.5 to 8.5 using different buffer system and then the preconcentration procedure as described
was applied. Quantitative uptake ( 95%) was obtained at pH 5.5-7.5 0.01 (Fig. 4.9.1).
Therefore, 6.5 was selected as the working pH for the subsequent experiments.

4.9.3.2. Effect of the amount of polymer

The amount of the polymer is another important parameter that affects the uptake of an
analyte. A quantitative retention ( 95%) cannot be achieved when the polymer is less than
the optimum amount. On the other hand, an excess amount of polymer prevents the
quantitative elution of the retained metal chelate by a small volume of the eluent. In order to
optimize the smallest amount of extractant 100, 200, 300, 400, 500, 600 mg. of the polymer
were added to the 100 mL of the sample solution containing 150 ng. of In(III) and
preconcentrated by the general procedure. The quantitative recoveries were obtained for and
above 300 mg. of polymer (Fig. 4.9.2). Therefore, 300 mg. of the polymer has been used for
subsequent experiments.

4.9.3.3. Effect of shaking time

Shaking time is an important factor in determining the possibility of application of the CDP-PAN polymer for the uptake of In(III). For studying the effect of shaking time on the %
uptake, a 400 mg. of polymer was shaken with 100 mL of solution containing 150 ng. of
In(III) for different shaking time (ranging from 10 to 60 minutes) with an interval of 10
minutes at optimum pH. The results of % uptake of In(III) vs. the shaking time show that the
percentage uptake reached maximum (above 95%) at 40 min (Fig. 4.9.3). Therefore, the
shaking time of 40 min. was selected as uptake equilibrium time.

4.9.3.4 Effect of the sample volume

In order to explore the possibility of enriching low concentration of analytes from large
volume of sample, the effect of sample volume on the retention of In(III) was also
investigated. 50, 100, 150, 200, 250, 300, 350, 400, 450 mL of sample solutions containing a
fixed amount of IN(III), 400 mg. of polymer at optimum pH and shaken for 30 min.
Quantitative uptakes ( 95%) were obtained for sample volume of 300 mL (Fig. 4.9.4).
Therefore, 100 mL of sample solution was adopted for the preconcentration of analyte from
sample solutions. The preconcentration factor is calculated by the ratio of the highest sample
volume (300 mL) and the lowest eluent volume (5 mL). Therefore, the preconcentration
factor was 60.

4.9.3.5 Effect of shaking speed

The % uptake of In(III) increased gradually with a rise in the shaking speed (Fig. 4.9.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Present study suggests that the shaking effect is
high-flying parameter for the maximum % uptake of an analyte ion.

4.9.3.6 Effect of eluent conc.

The effect of HCl concentration and volume on elution of In(III) on -CDP-PAN polymer
was studied by carrying out the elution with (0.5-5) M HCl. The results indicate that the
maximum uptake was obtainable when HCl concentration was 3M or more. Hence 3M was
chosen as eluent for further experimental conditions (Fig. 4.9.6).

4.9.3.7 Effect of eluent volume

In order to obtain the quantitative uptake of retained In(III) metal ion on -CDP-PAN
polymer was studied by carrying out the elution with (1-6 mL) of 4M HCl. During these
studies, 100 mL aliquots of the sample solutions containing 150ng. of In(III) were used at pH
8.5. Quantitative recovery values were obtained using 5mL of eluent (Fig. 4.9.7).

100
80
60
% Uptake of In(III)

40
20
0
3.5 4 4.5
5 5.5 6
6.5 7 7.5
8 8.5
pH of Sample Solution

Fig. 4.9.1 Effect of pH on % uptake of In(III)

100
80
60
% Uptake of In(III)

40
20
0
100

200

300

400

500

Amount of polymer(mg.)

Fig. 4.9.2 Effect of amount of polymer on % uptake of In(III)

120
100
80
60
% Uptake of In(III)

40
20
0
10

20

30

40

50

60

Shaking Time(min.)

Fig. 4.9.3 Effect of shaking time on % uptake of In(III)

100
80
60
% Uptake of In(III)

40
20
0
25 50 100
150 200 250

300 350 400

450

Sample volume (mL)

Fig. 4.9.4 Effect of sample volume on % uptake of In(III)

100
80
60
% Uptake of In(III)

40
20
0
40

60

80

100

120

140

Shaking speed (r.p.m.)

Fig. 4.9.5 Effect of shaking speed on % uptake of In(III)

100
80
60
% Uptake of In(III)

40
20
0
0.5

Eluent Conc. (M)

Fig. 4.9.6 Effect of eluent conc. on % uptake of In(III)

100
80
60
% Uptake of In(III)

40
20
0
1

Eluent Volume(mL)

Fig. 4.9.7 Effect of eluent volume on % uptake of In(III)

4.9.4 Effect of coexisting ions

The effect of various coexisting ions on the % uptake of a solution containing 150ng. of
In(III) was studied. An ion was considered to interfere when its presence produced a variation
in the absorbance of the sample 5%. Amongst the anions examined CO32-, SO32-, SO42-, NO3-,
IO3-, NO2- did not interfere at concentrations 1000 times more than those of the analyte. The
complexation between In(III) and PAN was completely masked by EDTA (ethylenediamine
tetraacetate ion) and cyanate even at lower concentration. Alkali and alkaline earth metal ions
did not interfere (Table 4.9.1).

Table 4.9.1 Effect of foreign ions on a solution containing 150ng. of In(III)

Foreign Ion(Anion/Cation)
NO3, SO4, HPO42, SCN,
NO2, PO43, ClO3 , IO3,
Cl, I, Br, CH3COO,
C2O42Na(I), K(I), Mg(II), Ba(II),
Al(III), Rb(I), Cs(I), Ag(I)
Sb(III), Ca(II), Zr(IV),
Ti(IV)
Th(IV), Sn(II), As(III)
a
Fe(III), bNi(II)
c
Zn(II), dPb(II), eFe(II),
e
Mn(II), fHg(II), fCd(II)
EDTA, CN-, F-, S2O32-

Tolerance Limit
[Wforeign ion/WIn(III)]
>2000

1000
500
200
30
10
1

a-masked with 1.0 mL of 5.0% ammonium oxalate; b-masked with 1.0 mL of 2.0%
dimethylglyoxime; c-Masked with 1.0 mL of 10.0% sodium citrate solution; d-masked with
2.0 mL of 1% sodium sulphate; e-masked with 2.0 mL of 3.0% sodium hexametaphosphate
solution; f-masked with mixed masking agent solution of 1.0 mL of 5.0% potassium
pyrophosphate, 1.0 mL of 25.0% citric acid and 1.0 mL of 10.0% thiourea solution.

4.9.5 Validation of the method

The validation of the developed method was checked by applying it for the determination of
In(III) in water samples.

4.9.5.1 Sample Collection and Conditioning

Water samples were collected from the Punjabi University, Patiala Campus, Patiala City. The
water samples were immediately filtered through cellulose membrane filter (0.45 m pore
size), and stored in precleaned polyethylene bottles. After then, pH of the sample was
adjusted to 6.5 and the preconcentration procedure as described above was applied (Table
4.9.2).

Table 4.9.2 Determination of In(III) in different water samples (n = 3)

Samples

Found
(ng.)$
N.D.

% Recovery

140.0

137.5 2.5

98.2

1.8

150.0
0.0

146.0 1.8
N.D.

97.3
-------

2.7
------

140.0

136.8 1.7

97.7

2.3

150.0
0.0

145.4 2.2
N.D.

96.9
-------

3.1
-------

140.0

137.9 2.1

98.5

1.5

150.0
N.D. not detected

147.9 1.8

98.6

1.4

Tap*
Water

Mineral
water

R.O.
Water

Added
(ng.)
0.0

Obtained R.S.D

4.9.6 Comparison with other methods

-------

% Relative
Error
-------

A comparison of the proposed method with other preconcentration methods reported in

literature was carried out. Some parameters obtained were compared to those presented by
other methods described in the literature. As can be seen from the data (Table 4.9.3), the
proposed method developed by using -cyclodextrin polymer modified PAN system has a
relatively high preconcentration factor and a low LOD when compared to other methods.

Table 4.9.3 Comparison of preconcentration methods of In(III) with the

reported methods

Sr.
No
.
1.

Modificatio
n
Mode
Physically
modified

Polymer

Modifie
r
EHND

Preconcen
.
Mode
Off-line

Preconcen
.
Factor
200

Sorbent
Dose(mg
)
1000

AXAD-7

2.

-------

Chelax-100

-------

Off-line

33

1200

3.

Chemically
modified

Nanometer
Alumina

QAHBA

On-line

10

50

4.

Physically
modified

Naphthalen
e

MCDTCTMAB

Off-line

40

-------

5.

Physically
modified

AXAD-4

HMPN

Off-line

200

1000

6.

Physically
modified

AXAD-2

PAN

Off-line

200

1000

7.

Physically
modified

-CDP

PAN

Off-line

87.5

300

EHND:

Eluent

Metho
d

5 mL of
SPE448
1M
FAAS
HNO3
5 mL of
SPE449
1M
GFAAS
HNO3
0.6 mL
SPE
450
of 1M
ICPHNO3&
OES
3%
(m/v)
thiourea
10 mL
SPE451
of 1m PolaroHCl
graphy
5 mL of
SPE452
0.5M
FAAS
HNO3
5 mL of
SPE
453
0.1M
ETAAS
HCl/2M
HNO3
4mL of
SPE
DM
4M HCl UV-Vis

1-[(1E,9E)-10-(2-hydroxy-1-naphthyl)-4,7-dioxa-2,9-diaza-1,9-decadienyl]-2-

naphthol; QAHBA: 3-(8-Quinlinylazo)-4-hydroxybenzoic acid; HMPN: 1-{[(6-{[(E)-1-(2hydroxy-1-naphthyl)methylidene]amino}-2-pyridyl)amino]methyl}-2-naphthol;

ETAAS:

Electrothermal atomic absorption spectroscopy; PAN: 1-(2-pyridylazo)-2-naphthol; DM:

Developed method

Ref
.

reconcentration and determination of Dithiocarbamate

esticides

(DTCs)

using

1-(2-pyridylazo)-2-naphthol

(PAN) modified -cyclodextrin polymer

Pesticides are efficient tools for preventing crop losses due to plant pests and disease.
Amongst the different classes of pesticides, dithiocarbamates (DTCs) present an important
class of organosulfur pesticides, widely used in agriculture. Dithiocarbamates do not belong

to the systemic fungicide but are protectant fungicide applied prior to fungus infection. They
act upon damaging fungi chiefly by surface deposits [454]. They are characterized by a broad
spectrum of activity against various types of plant pathogens, low acute mammal toxicity, and
low production cost. Furthermore, DTCs are also used clinically for the treatment of chronic
alcoholism and as anticancer and antitoxic drug agents [455-56]. Dithiocarbamates can be
absorbed by the organism via the skin, mucous membranes, respiratory and the
gastrointestinal tracts. Dithiocarbamates are known to have toxicological and mutational
effects. They possess variety of applications in agriculture as fungicides, as well as, in the
rubber industry as vulcanization accelerators and antioxidants. Determination of DTCs is
required for toxicological evaluations since the DTCs and their metabolites differ greatly in
their action mechanism [457].
Maneb [Mn(II) ethylene bis{dithiocarbamate}] is an agricultural dithiocarbamate fungicide
used on a wide variety of plant fungi and diseases. It may be applied to the foliage of plants,
but it is also used for soil or seed treatment. Maneb is used primarily for almonds and stone
fruits (drupes). Zineb [Zn(II) ethylene bis{dithiocarbamate}] is used as a fungicide to prevent
crop damage in the field and to protect harvested crops from deterioration in storage or
transport. Zineb is a foliar fungicide and is used to control late blight of potatoes, early blight
of tomatoes and downy mildew. Ziram [Zn(II) bis{dimethyldithiocarbamate}] is a vegetable
fungicide and is particularly used against anthracnose of tomatoes. Ferbam [Fe(III)
tris{dimethyldithiocarbamate}] is an agricultural dithiocarbamate pesticide and is used as
protective fungicide. The predominant methods for determining DTCs and metabolites are
based on their decomposition to CS2, H2S or amines in an acidic medium, followed mainly by
spectrometry [458] and head space gas chromatography [459] determination. One of the
earliest methods for Zineb determination was based on the colorimetry [460]. Crnogorac have
provided insight into the various methods for the residues analysis of dithiocarbamate
pesticides [461]. HPLC and AAS were used to distinguish Propineb, Zineb, Maneb and
Mancozeb fungicides [462]. GC-MS based method was devised and used for the
determination of DTCs in foodstuffs [463]. Dithiocarbamates can also be determined by
methods, like iodometry [464], polarography [465], biosensors [466], enzyme linked immune
sorbent assay [467], indirect complexometry [468], FTIR spectrometry [469], microwaveassisted extraction [470] and derivative spectrophotometry [471]. Liquid chromatography
(LC) coupled capillary electrophoresis (CE) with UV and /or electrochemical detection are
the techniques most frequently used to discriminate and determine the different DTCs
subclasses [472-75]. -Cyclodextrin (-CD) is a very stable oligosaccharide that is composed

of seven glucose units linked with each other by -(1,4)-glycosidic linkage. It can form
supramolecular complexes with several organic compounds by incorporating them into their
hydrophobic cavities. When two or more -Cyclodextrins are covalently linked with each
other they are known as the polymers. These -cyclodextrin polymers have been used for the
preconcentration of various analytes [476-78]. Here is presented a method that is based on the
preconcentration of dithiocarbamate pesticides such as Ziram, Zineb, Ferbam and Maneb
using 1-(2-Pyridylazo)-2-naphthol (PAN) modified -Cyclodextrin polymers. Metallic part of
the Dithiocarbamate pesticides form chelated complex with the PAN included in the cavity of
-CD polymer. Various analytical parameters such as effect of pH, sorbent dose, shaking
time, sample volume, eluent conc. and eluent volume were optimized using batch extraction
procedure. The effect of the foreign ions (anions, cations and other dithiocarbamate
pesticides) is also studied on individual DTC pesticide. The preconcentration factor has also
been studied for each of the pesticides. The preconcentration factor is determined as the ratio
of the largest sample volume to smallest eluent volume. The developed method is applied for
the preconcentration/determination of pesticides in different water and food samples. The
following reaction between the metallic part of the pesticides and the PAN loaded on to Cyclodextrin polymer forms the basis of the determination of pesticide by above method.

Mn+-[ethylene bis(dithiocarbamate)] + PAN = PAN- Mn+-[ethylene bis(dithiocarbamate)]

(EBDC pesticide)
For Mn+: Zn(II), Mn(II)
EBDC: Ethylene bis (dithiocarbamate) pesticide

(Colored complex)

5.1 Preconcentration of Zineb using -CDP-PAN polymer

The present work describes preconcentration of Zineb using -CDP-PAN polymer

5.1.1 Materials
5.1.1.1 Equipment
A Shimadzu UV-1800 spectrophotometer (Shimadzu Ltd., Japan) equipped with the matched
10-mm quartz cells was used to measure absorbance. All pH measurements were performed
using Digital century pH-meter CP 901 with a combined glass electrode. A thermostatic
shaking water bath (Perfit India Ltd.) was used to carry out all the inclusive procedures.

5.1.1.2. Reagents
All reagents used were of analytical reagent grade. Double distilled water was used
throughout the experiment.
1 10-2M Zineb was prepared as given in literature [459]. Its stock solution was prepared in
dimethyl sulphoxide (DMSO). Further dilutions were made as and when required.
4 10-6M solution of the PAN reagent was prepared by dissolving an appropriate amount of
PAN (Fluka Chemical Company) in N,N-dimethylformamide (DMF) solvent.
1,4-Butanediol diglycidyl ether was obtained from sigma Aldrich chemical company
(U.S.A.).
-Cyclodextrin was obtained from SD fine chemical India private limited (Mumbai).
Buffer solution used were hydrochloric acid/ sodium acetate for pH 2.0-3.5, sodium
acetate/acetic acid for pH 4.0-6.5, ammonia/ammonium chloride for pH 8-11.
Glass wares were washed with chromic acid and soaked in 5% nitric acid and rinsed with
double distilled water.

5.1.2 Procedure
5.1.2.1 Batch Extraction Procedure
At room temperature, -CDP-PAN (500mg) and 10.0 ml of buffer solution (pH 9.5) were
added to a 100-ml Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN could swell sufficiently. 60g of Zineb were added
and made up to 100ml with double distilled water. After the mixture was shaken in the
thermostatic shaking water bath for 45 min, 5.0ml of the supernatant solution was transferred
into a 10ml volumetric flask and the absorbance was measured using standard

spectrophotometric method [394]. Zineb retained on -CDP-PAN polymer was eluted using
5.0 mL of 2M HCl.

5.1.3 Optimization of various parameters

5.1.3.1 Effect of pH on % uptake of Zineb
The uptake of an analyte on a with PAN on the chelating polymer is dependent on the pH of
sample solution due to the competitive reaction between chelate forming groups and
hydrogen ions in the solutions. 60g. of Zineb were added to a 100 mL Stoppard conical
flask. The pH of this solution was adjusted in the range of 2.5 to 10.5 using different buffer
system and then the preconcentration procedure as described was applied. Quantitative
uptake ( 95%) was obtained at pH 9.5 and above (Fig. 5.1.1). Therefore, 9.5 was chosen as
the working pH for the subsequent studies.

5.1.3.2 Effect of the amount of polymer

The amount of the polymer is another important parameter that affects the uptake of an
analyte. A quantitative uptake ( 95%) cannot be achieved when the polymer is less than the
optimum amount. On the other hand, an excess amount of polymer prevents the quantitative
elution of the retained analyte by a small volume of the eluent. In order to optimize the
smallest amount, 100-800 mg. of the polymer were added to the same volume of the sample
containing 60g. of Zineb and preconcentrated by the general procedure. The quantitative
uptake ( 95%) was obtained for and above 500 mg of polymer (Fig. 5.1.2). Therefore, 500
mg of polymer has been used for subsequent studies.

5.1.3.3 Effect of shaking time

Shaking time is an important factor in determining the possibility of application of the CDP-PAN polymer for the selective uptake of an analyte. Different shaking time (ranging
from 15 to 75min) were studied for the % uptake of Zineb by -CDP-PAN polymer. The
percentage uptake reached maximum (above 95%) at 45 min (Fig. 5.1.3). Therefore, the
shaking time of 45 min. was selected as the uptake equilibrium time.

5.1.3.4 Effect of the sample volume on % uptake of Zineb

In order to explore the possibility of enriching low concentration of analytes from large
sample volume, the effect of sample volume on the uptake of Zineb was also investigated.
For this purpose, 25, 50, 100, 150, 200, 250, 300, 350, 400 mL of sample containing 60 g. of

Zineb were taken. Quantitative uptakes ( 95%) were obtained for sample volume of 350
mL (Fig. 5.1.4). But for convenience of handling, 100 mL of sample volume was adopted for
the preconcentration of analyte.

5.1.3.5 Effect of shaking speed (r.p.m.) on % uptake of Zineb

The % uptake of Zineb increased gradually with a rise in the shaking speed (Fig. 5.1.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Therefore, the present study suggests that the
shaking effect is high-flying parameter for the maximum % uptake of an analyte ion.

5.1.3.6 Effect of Nature of Eluent on % uptake of Zineb

In order to choose the best eluent for the Zineb retained on -CDP-PAN polymer, various
eluent were used. Among the eluents studied, the acids provided higher recovery efficiency
than the organic solvents. From the results, it is obvious that higher uptake was obtained with
Hydrochloric acid (HCl).

5.1.3.7 Effect of eluent conc.

Since the uptake of Zineb at pH 2 is quite low, one can expect that elution will be favored
in the acidic medium. Therefore, effect of the eluent concentration on the % uptake of Zineb
was also examined. Different concentrations of HCl ranging from (0.5-4M) were tested in
order to strip the Zineb from polymer. The uptake of Zineb increased, as HCl concentration
increased up to 2.0M and it decreased above this concentration. Therefore an HCl
concentration of 2.0 M was selected for subsequent studies (Fig. 5.1.6).

5.1.3.8 Effect of Eluent volume

In order to choose proper volume of the eluent, the retained complex was stripped with
different volumes (16 mL) of 2.0 M HCl. It is clear that 5 mL would not be suitable because
it gave a smaller preconcentration factor and 3mL was not sufficient for the elution (Fig.
5.1.7). Hence, 5 mL of 2.0 M HCl was chosen for elution of Zineb. The preconcentration
factor is calculated by the ratio of the highest sample volume (350 mL) and the lowest eluent
volume (5 mL). Thus, the preconcentration factor found was 70.

100
80
60
% Uptake of Zineb

40
20
0
2.5 3.5 4.5
6.5 7.5 8.5
9.5 10 10.5
pH

Fig. 5.1.1 Effect of pH on % uptake of Zineb

100
80
60
% Uptake of Zineb

40
20
0
100 200
300 400
500 600
700
Amount of polymer (mg.)

Fig. 5.1.2 Effect of amount of polymer on % uptake of Zineb

100
80
60
%Uptake of Zineb

40
20
0
15

30

45

60

75

Shaking time(min.)

Fig. 5.1.3 Effect of shaking time on % uptake of Zineb

100
80
60
% Uptake of Zineb

40
20
0
25 50 100
150 200 250
300

350 400 450

Sample Volume (mL)

Fig. 5.1.4 Effect of sample volume on % uptake of Zineb

100
80
60
% Uptake of Zineb

40
20
0
40

60

80

100

120

140

Shaking speed (r.p.m.)

Fig. 5.1.5 Effect of shaking speed (r.p.m.) on % uptake of Zineb

100
80
60
% Uptake of Zineb

40
20
0
0.5

Eluent Concentration

Fig. 5.1.6 Effect of eluent concentration on % uptake of Zineb

100
80
60
% Uptake of Zineb

40
20
0
1

Eluent Volume(mL)

Fig. 5.1.7 Effect of eluent volume on the % uptake of Zineb

5.1.4 Effect of Foreign

A sample containing 60g. of Zineb, various foreign ions (both anions and cations) and other
dithiocarbamate pesticides were prepared and general procedure was followed. The tolerance
limit was defined as the amount of foreign ions causing a change less than 5% in the uptake
of Zineb (Table 5.1.1).

Table 5.1.1 Effect of foreign ions on the determination of 60g. of Zineb

Foreign ions
NO3-, SO42-, HPO42-, SCN-, NO2-, PO43Na+, K+, Mg2+, Ba2+, Al3+, Rb+, Cs+, Ag+
Sb3+, Ca2+, Zr4+, Ti
Th4+, Sn2+, As3+
a
Ferbam, bNi2+, cCu2+, dCo2+
e
Hg2+, eCd2+, fPb2+, gFe2+, hManeb
EDTA, Br-, F-, CN-, citrate

Tolerance limit[WForeign ion/WZineb]

>1000
1000
500
200
10
1
1

a-masked with 1.0 mL of 5.0% ammonium oxalate solution; b-masked with 1.0 mL of 2.0%
dimethylglyoxime; c-masked with 1.0 mL of 3.0% sodium thiosulphate; d-masked with 1.0
mL of 10.0% -benzilmonoxime; e-masked with 5.0 mL of 2.0% sodium thioglycollate
solution; f- masked with 2.0 mL 0f 1.0% sodium sulphate solution; g-masked with 1.0 mL of
2.0% 1,10-phenenthroline; h-masked with 2.0 mL 3.0% sodium hexametaphosphate solution.

5.1.5 Validation of the method

The validity of the method was checked by applying it for the determination of Zineb in
water and vegetable samples.

5.1.5.1 Determination of Zineb in water samples

Water samples were collected from Punjabi University, Patiala. The water samples were
immediately filtered through cellulose membrane filter (0.45 m pore size), and stored in
precleaned polyethylene bottles. After that, pH of the sample was adjusted to 9.5 and the
preconcentration procedure as described above was applied (Table 5.1.2).

5.1.5.2 Determination of Zineb in vegetables/crops

The method was applied for the determination of Zineb in crops and vegetable samples. A
known amount of Zineb in dimethyl sulphoxide (DMSO) was crushed with 10 g. of crops and
vegetable samples with the help of a pestle and mortar. The mixture was then stirred with
magnetic stirrer for 1h to provide complete dissolution of Zineb and then filtered to separate
the food residue from the solution containing Zineb. The residue was washed with DMSO to
provide complete extraction of Zineb to the solution. Filtrate and washings were combined
and evaporated to 20.0 mL on a water bath, diluted to 100 mL with DMSO and determined
by the developed method. The results are depicted in (Table 5.1.3).

Table 5.1.2 Determination of Zineb in different spiked water samples (n=3)

Sample
^

0.0

N.D.

% Relative
Error
-------

40.0

39.6

1.0

99.0 1.0

45.0

44.5

1.1

99.0 1.0

Mineral Water 0.0

N.D.

-------

25.0

24.6

1.6

98.4 1.6

20.0

19.6

2.0

98.0 1.3

0.0

N.D

------

-------

30.0

29.5

1.7

98.3 1.2

50.0
N.D. not detected

49.5

1.0

99.1 1.0

Tap Water

Spiked(g.)

Tap Water

Found(g.)

% Recovery
R.S.D.(%)
-------

-------

*n is the average of three replicate determinations

^Tap water samples were collected from Punjabi University, Patiala
#

Bottled Mineral water (Bisleri) locally available in market

Tap water samples collected from Urban Estate Phase-II Patiala

Table 5.1.3 Determination of Zineb in different vegetables/crops (n=3)

^Sample
Wheat

Spiked(g.)

Found(g.)a

% Relative
Error
------

% Recovery
R.S.D.(%)
--------

0.0

N.D.

20.0

19.4

3.0

97.0 2.2

40.0

38.9

2.8

97.2 1.8

0.0

N.D.

--------

15.0

14.6

2.7

97.3 2.0

35.0

34.0

2.8

97.1 2.0

0.0

N.D.

--------

--------

60.0

58.3

2.8

97.2 2.0

65.0
N.D. (not detected)

63.2

2.8

97.2 2.1

Rice

Potato

--------

*n is the average of three replicate determinations

^Samples were collected from local market in vicinity of Punjabi University, Patiala

5.1.6 Accuracy of the method

The accuracy of the described preconcentration method was tested in the recovery studies by
adding known amounts of Zineb to the water and food sample. The results obtained from the
analysis of water and food samples were satisfactory. These results confirm the validity of the
proposed method.

Table 5.1.4 Various parameters studied for the preconcentration of Zineb using
-CDP-PAN polymer as extractant.

Parameters
pH
Volume of buffer(mL)

Studied Range
2.5-10.5

Selected Value
9.5

6-18

10

15-75

45

100-700

500

Sample Volume(mL)

50-450

100

Eluent Concentration(M)

0.5-4

1-6

Shaking Time(min)
Adsorbent Dose

Eluent Volume(mL)
Preconcentration factor

--------

70

5.2. Preconcentration of Ferbam using -CDP-PAN polymer

The present work describes the preconcentration of Ferbam using -CDP-PAN polymer.

5.2.1. Materials
5.2.1.1 Equipments
Equipments are same as described in section 5.1.1.1.

5.2.1.2 Reagents
Ferbam sample was prepared as given in literature [459]. Its stock solution was prepared in
dimethyl sulphoxide (DMSO). Further dilutions were made as and when required.

5.2.2 Procedure
5.2.2.1 Batch Extraction procedure
At room temperature, -CDP-PAN (400mg) and 10.0 ml of buffer solution (pH 5.5) were
added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN could swell sufficiently. 75g of Ferbam were
added and made up to 100ml with double distilled water. After the mixture was shaken in the
thermostatic shaking water bath for 40 min, 5.0ml of the supernatant solution was transferred
into a 10ml volumetric flask and the absorbance was measured using standard
spectrophotometric method [394]. Ferbam retained on -CDP-PAN polymer was eluted using
4.0 mL of 3M HCl.

5.2.3 Optimization of various parameters

5.2.3.1. Effect of pH on % uptake of Ferbam
The uptake of an analyte on the chelating polymer is dependent on the pH of sample solution
due to the competitive reaction between chelate forming groups and hydrogen ions in the
solutions [461]. 75 g of Ferbam were added to a 100 mL Stoppard flask. The pH of this
solution was adjusted in the range of 2.5 to 10.5 using different buffer system and then the
preconcentration procedure as described was applied. Quantitative uptake ( 95%) was
obtained at pH 5.5 (Fig. 5.2.1). Therefore, the working pH was chosen as 5.5 for the
subsequent studies.

5.2.3.2. Effect of the amount of polymer on % uptake of Ferbam

The amount of the polymer is another important parameter that affects the uptake of the
analyte. A quantitative uptake ( 95%) cannot be achieved when the polymer is less than the

optimum amount. On the other hand, an excess amount of polymer prevents the quantitative
elution of the retained analyte chelate by a small volume of the eluent. In order to optimize
the smallest amount, 100, 200, 300, 400, 500 mg. of the polymer were added to the same
volume of the sample solution containing 75 g. of Ferbam and preconcentrated by the
general procedure. The quantitative recoveries were obtained for and above 400 mg of
polymer (Fig. 5.2.2). Therefore, 400 mg of the polymer has been used for subsequent
experiments.

5.2.3.3. Effect of shaking time on % uptake of Ferbam

Shaking time is an important factor in determining the possibility of application of the CDP-PAN polymer for the selective uptake of Ferbam. Different shaking time (ranging from
10 to 50 min.) were studied for the % uptake of Ferbam by -CDP-PAN polymer. The results
of % uptake of Ferbam vs. the shaking time show that the percentage uptake reach maximum
(above 95%) at 40 min (Fig. 5.2.3). Therefore, the shaking time of 40 min. was selected as
the adsorption equilibrium time.

5.2.3.4. Effect of the sample volume on % uptake of Ferbam

In order to explore the possibility of enriching low concentration of analytes from large
volume of solution, the effect of sample volume on the uptake of Ferbam was also
investigated. For this purpose, 25, 50, 100, 150, 200, 250, 300, 350, 400 mL of sample
containing 75 g of Ferbam were taken. Quantitative uptakes ( 95%) were obtained for
sample volume of 300 mL (Fig. 5.2.4). But for convenience, 100 mL of sample volume was
adopted for the preconcentration of analyte.

5.2.3.5 Effect of shaking speed (r.p.m.) on % uptake of Ferbam

The % uptake of Ferbam increased gradually with a rise in the shaking speed (Fig. 5.2.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Therefore, the present study suggests that the
shaking effect is an outstanding parameter for the maximum % uptake of an analyte.

5.2.3.6 Effect of Nature of Eluent on % uptake of Ferbam

In order to choose the best eluent for the Ferbam retained on -CDP-PAN polymer, various
eluent were used. Among the eluents studied, the acids provided higher recovery efficiency
than the organic solvents. Amongst acids studied, HCl provided higher recovery value

5.2.3.7 Effect of eluent concentration on % uptake of Ferbam

The effect of eluent concentration on the uptake of Ferbam was also examined. Different
concentrations of HCl ranging from (0.5-4M) were tested in order to strip the Ferbam from
polymer. The uptake of Ferbam increased, as HCl concentration increased up to 2.0M and it
decreased above this concentration. Therefore an HCl concentration of 2.0 M was selected for
subsequent studies (Fig. 5.2.6).

5.2.3.8 Effect of Eluent volume on % uptake of Ferbam

In order to choose proper volume of the eluent, the retained complex was stripped with
different volumes (16 mL) of 2.0 M HCl. It is clear that 5 mL would not be suitable because
it gave a smaller preconcentration factor and 3mL was not sufficient for the elution (Fig.
5.2.7). Hence, 4 mL of 2.0 M HCl was chosen for elution of the metal ion complexes. The
preconcentration factor is calculated by the ratio of the highest sample volume (300 mL) and
the lowest eluent volume (4 mL). Thus, the preconcentration factor obtained 75.

100
80
60
% Uptake of Ferbam

40
20
0
2.5 3.5 4.5
5.5 6.5 7.5
8.5 9.5 10
pH

Fig. 5.2.1 Effect of pH on % uptake of Ferbam

100
80
60
% Uptake of Ferbam

40
20
0
50

100 200
300 400
500
Amount of polymer (mg.)

Fig. 5.2.2 Effect of amount of polymer on % uptake of Ferbam

100
80
60
% Uptake of Ferbam

40
20
0
10

20

30

40

50

Shaking time (min.)

Fig. 5.2.3 Effect of shaking time on % uptake of Ferbam

100
80
60
% Uptake of Ferbam

40
20
0
25 50 100
150 200 250
300

350 400

Sample Volume (mL)

Fig. 5.2.4 Effect of sample volume on % uptake of Ferbam

100
80
60
% Uptake of Ferbam

40
20
0
40

60

80

100 120
140

Shaking speed (r.p.m.)

Fig. 5.2.5 Effect of shaking speed on % uptake of Ferbam

100
80
60
40

% Uptake of Ferbam

20
0
0.5

1.5

Eluent Conc. (M)

Fig. 5.2.6 Effect of eluent concentration on the % uptake of Ferbam

100
80
60
% Uptake of Ferbam

40
20
0
1

Eluent Volume(mL)

Fig. 5.2.7 Effect of eluent volume on the % uptake of Ferbam

5.2.3 Effect of foreign ions

Synthetic solutions containing 75 g of Ferbam and various types of foreign ions were
prepared and general procedure was followed. The tolerance limit was defined as the amount
of foreign ions causing a change less than 5% in the recovery of Ferbam (Table 5.2.1).

Table 5.2.1 Effect of foreign ions on the determination of 75 g of Ferbam

Foreign ions
Tolerance limit[WForeign ion/WFerbam]
223NO3 , SO4 , HPO4 , SCN , NO2 , PO4
>1500
Na+, K+, Mg2+, Ba2+, Al3+, Rb+, Cs+, Ag+,
1000
Dibam, Nabam, Vapam
Sb3+, Ca2+, Zr4+, Ti
Th4+, Sn2+, As3+
a
Ni2+, bCu2+, cCo2+
d
Hg2+, dCd2+, ePb2+, fFe2+, gManeb, hZineb

800
300
10
1

EDTA, Br-, F-, CN-, citrate

a-masked with 1.0 mL of 2.0% dimethylglyoxime; b-masked with 1.0 mL of 3.0% sodium
thiosulphate; c-masked with 1.0 mL of 10.0% -benzilmonoxime; d-masked with 5.0 mL of
2.0% sodium thioglycollate solution; e- masked with 2.0 mL 0f 1.0% sodium sulphate
solution; f-masked with 1.0 mL of 2.0% 1,10-phenenthroline; g-masked with 2.0 mL 3.0%
sodium hexametaphosphate solution; h-masked with 1.5 mL of 1% sodium thiocyanate.

5.2.4 Validation of the method

The validity of the method was checked by applying it for the determination of Ferbam in
water and vegetable samples.

5.2.4.1 Determination of Ferbam in water samples

Water samples were collected from the different parts of Patiala City. The water samples were
immediately filtered through cellulose membrane filter (0.45 m pore size), and stored in
precleaned polyethylene bottles. After that, pH of the sample was adjusted to 5.5 and the
preconcentration procedure as described above was applied (Table 5.2.2).

5.2.4.2 Determination of Ferbam in vegetables/crops

The method was applied for the determination of Ferbam in crops and vegetable samples. A
known amount of Ferbam in dimethyl sulphoxide (DMSO) was crushed with 10 g. of crops
and vegetable samples with the help of a pestle and mortar. The mixture was then stirred with
magnetic stirrer for 1h to provide complete dissolution of Ferbam and then filtered to separate
the food residue from the solution containing Ferbam. The residue was washed with DMSO
to provide complete extraction of Ferbam to the solution. Filtrate and washings were
combined and evaporated to 20.0 mL on a water bath, diluted to 100 mL with DMSO and
determined by the developed method (Table 5.2.3).

Table 5.2.2 Determination of Ferbam in different water samples (n=3)

Sample

Spiked(g.)

Found(g.)

% Relative

% Recovery

Error

R.S.D.(%)

Tap Water

Tap Water

R. O. Water

0.0

N.D.

-------

15.0

14.7

2.9

97.1 2.1

20.0

19.5

2.5

97.5 1.5

0.0

N.D.

-------

35.0

34.0

1.0

99.0 1.0

40.0

38.7

1.7

98.3 1.2

0.0

N.D

------

-------

55.0

54.6

1.0

99.0 1.0

1.0

99.1 1.0

65.0
64.4
N.D. not detected; R.O. Reverse Osmosis

-------

-------

*n is the average of three replicate determinations

^Tap water was collected from Punjabi University, Patiala
$

Tap water was collected from Urban Estate Phase-II, Patiala

R. O. Water was collected from Department of Chemistry, Punjabi University

Table 5.2.3 Determination of Ferbam in different vegetable samples (n=3)

$

Sample

Spiked(g.)

Found(g.)

% Relative
Error

% Recovery
R.S.D.(%)

Tomato

0.0

N.D.

-------

20.0

19.6

2.0

98.0 1.3

40.0

39.6

1.0

99.0 1.0

0.0

N.D.

-------

50.0

49.5

1.0

99.0 1.0

55.0

54.6

1.0

99.0 1.0

0.0

N.D.

--------

--------

70.0

69.4

1.0

99.1 1.0

75.0
N.D. not detected

74.3

1.0

99.1 1.0

Potato

Cucumber

--------

--------

*n is the average of three replicate determinations

$

Samples were collected from Vegetable market near Urban Estate Phase-II,
Patiala

5.2.6 Accuracy of the method

The accuracy of the described preconcentration method was tested in the recovery studies by
adding known amounts of Ferbam to the water and food sample. The results obtained from

the analysis of water and food samples were satisfactory. These results confirm the validity of
the proposed method.

Table 5.2.4 Various parameters studied for the preconcentration of Ferbam

using -CDP-PAN polymer as solid phase extractant.
Parameters

Studied Range

pH

2.5-10.0

Volume of buffer(mL)

Selected range
5.5

6-18

10

Shaking Time(min)

10-50

40

Adsorbent Dose

50-500

400

Sample Volume(mL)

50-450

100

Eluent Concentration(M)

0.5-3

1-6

-------

75

Eluent Volume(mL)
Preconcentration factor

5.3 Preconcentration of Maneb using -CDP-PAN polymer

The present work describes preconcentration of Maneb using -CDP-PAN polymer.

5.3.1 Materials
5.3.1.1 Equipment
The equipment are same as described in 5.1.1.1.

5.3.2.1 Reagents
Maneb was prepared as given in literature [27]. Its stock solution was prepared in dimethyl
sulphoxide (DMSO). Further dilutions were made as and when required.

5.3.2 Procedure
5.3.2.1 Batch Extraction procedure
At room temperature, -CDP-PAN (500mg) and 10.0 ml of buffer solution (pH 9.5) were
added to a 100 mL Stoppard conical flask. The mixture was allowed to stand for
approximately 15 min so that -CDP-PAN could swell sufficiently. 50g of Maneb were
added and made up to 100 mL with double distilled water. After the mixture was shaken in
the thermostatic shaking water bath for 45 min, 5.0 mL of the supernatant solution was
transferred into a 10ml volumetric flask and the absorbance was measured. Maneb retained
on -CDP-PAN polymer was eluted using 5.0 mL of 2M HCl.

5.3.3 Optimization of various parameters

5.3.3.1 Effect of pH
The uptake of an analyte on the chelating polymer is dependent on the pH of sample solution
due to the competitive reaction between chelate forming groups and hydrogen ions in the
solutions. 50g. of Maneb were added to a 100 mL of the sample, containing 500 mg. of
polymer and shook for 45 min. The pH of this solution was adjusted in the range of 2.5 to
10.5 using different buffer system and then the preconcentration procedure as described was
applied. Quantitative uptake ( 95%) was obtained at pH 9.5-10.5 0.01 (Figure 5.3.1).
Therefore, 9.5 was chosen as the working pH for the subsequent studies.

5.3.3.2 Effect of the amount of polymer on % uptake of Maneb

The amount of the polymer is another important parameter that affects the uptake of an
analyte. A quantitative uptake ( 95%) cannot be achieved when the polymer is less than the
optimum amount. On the other hand, an excess amount of polymer prevents the quantitative
elution of the retained analyte by a small volume of the eluent. In order to optimize the
smallest amount, 100, 200, 300, 400, 500, 600 and 700 mg. of the polymer were added to the
100 mL of the sample solution containing 50 g of Maneb and preconcentrated by the general
procedure. The quantitative recoveries were obtained for and above 500 mg of polymer (Fig.
5.3.2). Therefore, 500 mg of the polymer has been used for subsequent studies.

5.3.3.3 Effect of shaking time on % uptake of Maneb

Shaking time is an important factor in determining the possibility of application of the CDP-PAN polymer for the uptake of Maneb. For studying the effect of shaking time on the %
uptake, 500 mg. amount of polymer was shaken with 100 mL of sample containing 50 g of
Maneb for different shaking time (ranging from 15, 30, 45, 60, 75) min. at optimum pH. The
results of % uptake of Maneb vs. the shaking time show that the percentage uptake reached
maximum (above 95%) at 45 min (Fig. 5.3.3). Therefore, the shaking time of 45 min. was
selected as the adsorption equilibrium time.

5.3.3.4 Effect of the sample volume

In order to explore the possibility of enriching low concentration of analytes from large
volume of solution, the effect of sample volume on the retention of Maneb was also
investigated. For this purpose, 50 g of Maneb were added into 25, 50, 100, 150, 200, 250,
300, 350, 400 mL of sample containing 500 mg. of polymer at optimum pH and shook for 45
min. Quantitative uptakes ( 95%) were obtained for sample volume of 350 mL (Fig. 5.3.4).
But for convenience, 100 mL of sample solution was adopted for the preconcentration of
Maneb.

5.3.3.5 Effect of shaking speed (r.p.m.) on % uptake of Maneb

The % uptake of Maneb increased gradually with a rise in the shaking speed (Fig. 5.3.5). The
batch extraction technique is based on the choice of shaking speed that helps to improve the
mass transfer. Shaking speed here acts as a driving force. The central dogma is that the
increasing driving force could help in mass transfer and facilitate the concentration gradient
between the sample solution and the polymer. Therefore, the present study suggests that the
shaking effect is an outstanding parameter for the maximum % uptake of an analyte.

5.3.3.6 Effect of Nature of Eluent on % uptake of Maneb

In order to choose the best eluent for the Maneb retained on -CDP-PAN polymer, various
eluent were used. Among the eluents studied, the acids provided higher recovery efficiency
than the organic solvents. Amongst acids studied, HCl provided higher recovery value

5.3.3.7 Effect of eluent concentration on % uptake of Maneb

The effect of eluent concentration on the uptake of Maneb was also examined. Different
concentrations of HCl ranging from (0.5-4M) were tested in order to strip the Maneb from
polymer. The uptake of Maneb increased, as HCl concentration increased up to 2.0M and it
decreased above this concentration. Therefore an HCl concentration of 2.0 M was selected for
subsequent studies (Fig. 5.3.6).

5.3.3.8 Effect of Eluent volume on % uptake of Maneb

In order to choose proper volume of the eluent, the retained complex was stripped with
different volumes (16 mL) of 2.0 M HCl. It is clear that 5 mL would not be suitable because
it gave a smaller preconcentration factor and 3mL was not sufficient for the elution (Fig.
5.3.7). Hence, 4 mL of 2.0 M HCl was chosen for elution of the metal ion complexes. The
preconcentration factor is calculated by the ratio of the highest sample volume (350 mL) and
the lowest eluent volume (5 mL). Thus, the preconcentration factor obtainable was 70.

120
100
80
60
% Uptake of Maneb

40
20
0
2.5 3.5 4.5
5.5

6.5 7.5 8.5

9.5 10 10.5

pH

Fig. 5.3.1 Effect of pH on % uptake of Maneb

120
100
80
60
% Uptake of Maneb

40
20
0
100

200

300

400

500

600

700

Amount of polymer (mg.)

Fig. 5.3.2 Effect of amount of polymer on % uptake of Maneb

120
100
80
60
% Uptake of Maneb

40
20
0
15

30

45

60

75

Contact time(min.)

Fig. 5.3.3 Effect of the contact time on % uptake of Maneb

120
100
80
60
% Uptake of Maneb

40
20
0
25 50 100
150 200

250 300 350

400 450

Sample Volume (mL)

Fig. 5.3.4 Effect of the sample volume on % uptake of Maneb

100
80
60
40

% Uptake of Maneb

20
0
40

60

80

100 120
140

Shaking speed (r.p.m.)

Fig. 5.3.5 Effect of shaking speed on % uptake of Maneb

120
100
80
60
% Uptake of Maneb

40
20
0
0.5

Eluent Conc. (M)

Fig. 5.3.6 Effect of eluent concentration on % uptake of Maneb

120
100
80
60
% Uptake of Maneb

40
20
0
1

Eluent Volume(mL)

Fig. 5.3.7 Effect of eluent volume on % uptake of Maneb

5.3.4 Effect of Foreign ion

Samples containing 50 g. of Maneb and various amounts of foreign ions were prepared and
general procedure was followed. The tolerance limit was defined as the amount of foreign
ions causing a change less than 5% in the uptake of Maneb (Table 5.3.1).

Table 5.3.1 Effect of foreign ions on the determination of 50g. of Maneb

Foreign ions
NO3-, SO42-, HPO42-, SCN-, NO2-,
PO43Na+, K+, Mg2+, Ba2+, Al3+, Rb+, Cs+,
Ag+, Dibam, Nabam, Vapam
Sb3+, Ca2+, Zr4+, Ti
Th4+, Sn2+, As3+
a
Ferbam, bNi2+, cCu2+, dCo2+,
e
Hg2+, eCd2+, fPb2+, gFe2+, Zineb,
Ziram
EDTA, Br-, F-, CN-, citrate

Tolerance limit
[WForeign ion/WManeb]
>1000
1000
500
100
10
1
1

a-masked with 1.0 mL of 5.0% ammonium oxalate solution; b-masked with 1.0 mL of 2.0%
dimethylglyoxime; c-masked with 1.0 mL of 3.0% sodium thiosulphate; d-masked with 1.0
mL of 10.0% -benzilmonoxime; e-masked with 5.0 mL of 2.0% sodium thioglycollate
solution; f- masked with 2.0 mL 0f 1.0% sodium sulphate solution; g-masked with 1.0 mL of
2.0% 1,10-phenenthroline; h-masked with 3.0 mL of 1% sodium thiocyanate solution.

5.3.4 Validation of the method

The validity of the method was checked by applying it for the determination of Maneb in
water and vegetable samples.

5.3.4.1 Determination of Maneb in water samples

Water samples were collected from the different parts of Patiala City. The water samples were
immediately filtered through cellulose membrane filter (0.45 m pore size), and stored in
precleaned polyethylene bottles. After that, pH of the sample was adjusted to 5.5 and the
preconcentration procedure as described above was applied (Table 5.3.2).

5.3.4.2 Determination of Maneb in vegetables/crops

The method was applied for the determination of Maneb in crops and vegetable samples. A
known amount of Maneb in dimethyl sulphoxide (DMSO) was crushed with 10 g. of crops
and vegetable samples with the help of a pestle and mortar. The mixture was then stirred with
magnetic stirrer for 1h to provide complete dissolution of Maneb and then filtered to separate
the food residue from the solution containing Maneb. The residue was washed with DMSO to
provide complete extraction of Maneb to the solution. Filtrate and washings were combined
and evaporated to 20.0 mL on a water bath, diluted to 100 mL with DMSO and determined
by the developed method (Table 5.3.3).

Table 5.3.2 Determination of Maneb in different water samples (n=3)

Sample

Spiked(g.)

Found(g.)

% Relative

% Recovery
R.S.D.(%)
-------

0.0

N.D.

Error
-------

15.0

14.7

2.0

98.0 1.4

25.0

24.6

1.6

98.4 0.8

0.0

N.D.

-------

40.0

39.6

1.0

99.0 1.0

30.0

29.5

1.7

98.3 1.2

0.0

N.D

------

40.0

39.5

1.3

99.0 1.0

35.0
N.D. Not detected

34.6

1.1

98.5 0.9

Tap Water

Bore Water

River Water

-------

-------

Table 5.3.3 Determination of Maneb in vegetable samples (n=3)

Sample
Tomato

Potato

Cucumber

Spiked(g.)

Found(g.)

% Relative

% Recovery

0.0

N.D.

Error
-------

20.0

19.6

2.0

98.0 1.3

40.0

39.2

2.0

98.0 1.3

0.0

N.D.

--------

--------

50.0

49.5

1.0

99.0 1.0

45.0

44.4

1.3

98.6 0.8

0.0

N.D.

35.0

34.4

1.7

98.3 1.2

54.4

1.1

98.9 1.0

55.0
N.D. (not detected)

--------

R.S.D.(%)
--------

--------

5.3.6 Accuracy of the method

The accuracy of the described preconcentration method was tested in the recovery studies by
adding known amounts of Maneb to the water and food sample. The results obtained from the
analysis of water and vegetable samples are depicted in table respectively. The recovery
values obtained from the water and vegetable samples were satisfactory. These results
confirm the validity of the proposed method.

Table 5.3.5 Various parameters studied for the preconcentration of Maneb using
-CDP-PAN polymer as solid phase extractant
Parameters
pH
Volume of buffer(mL)

Studied Range
2.5-10.5

Selected Value
9.5

6-18

10

15-75

45

100-700

500

Sample Volume(mL)

50-450

100

Eluent Concentration(M)

0.5-4

1-6

Shaking Time(min)
Adsorbent Dose

Eluent Volume(mL)
Preconcentration factor

Conclusion

--------

70

In conclusion, the present method is an operationally simple and clean procedure for the
determination of dithiocarbamate pesticides (DTCs) in different samples using PAN modified
-cyclodextrin polymer (-CDP). Preparation of the polymer is easy and the method has a
good accuracy, sensitivity and repeatability. The modified polymer has been used in all the
experiments performed for this study. The RSD of the method is 2.0%. The recoveries
obtained were 95% in all the cases. The method has a preconcentration factor of 70 and
above. It possesses some distinct advantages over determination of dithiocarbamates by acid
hydrolysis method which involve formation, extraction and determination of CS 2. The
method also avoids the use of hazardous chemicals such as pyridine etc. used in certain
methods, thus provides a clean, environment friendly methodology for DTCs determination
in different water and food samples.

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1. Sandeep Jaggi, Usha Gupta, Poonam Preet Kaur, Preconcentration of Zn(II) Using CyclodextrinButanediolDiglycidyl Ether Polymer Modified With 1-(2-Pyridylazo)-2Naphthol) (PAN), GU J. Sci., 25(3), 635-643 (2012).
2. Sandeep Jaggi, Usha Gupta, Solid phase extraction and preconcentration of Ni(II)
using 1-(2-pyridylazo)-2-naphthol (PAN) modified -cyclodextrin butanediol
diglycidyl ether polymer as a solid phase extractant, Maced. J. Chem. Chem. Eng.,
32(1), 57-67 (2013).
3. Sandeep Jaggi, Usha Gupta, Inclusion complex based solid phase extraction of
Cu(II) with -Cyclodextrin Polymer, Res. J. Pharm. Biol. Chem. Sci., 5(4), 701-708
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4. Sandeep Jaggi, Usha Gupta, Chelate Modified -CDP As a Green and Economical
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 Participated in National Seminar on Recent Advances in Chemistry and their Impact

on Environment NSRACE-11 held at Department of Chemistry, Punjabi University,
Patiala from February 15-16, 2011.
Presented a poster in 4th National seminar on Chemistry: An Inter Disciplinary
Science NSCIDS-12 held at Department of Chemistry, Punjabi University, Patiala
from February 15-16, 2012.
Presented a poster in 5th National seminar on New Frontiers in Chemistry NFIC2013 held at Department of Chemistry, Punjabi University, Patiala from February 1516, 2013.
Participated in Workshop on Science and Technology 2013, held at Senior
Secondary Model School, Punjabi University, Patiala on 4th and 5th December 2013.
Presented a poster in 6th National Seminar on New Paradigm in Chemical Sciences
NPICS-2014 held at Department of Chemistry, Punjabi University, Patiala on
February 13, 2014.
Presented a poster in National Seminar on Chemistry for a Better Tomorrow: Current
Trends and Challenges held at Department of Chemistry, Mata Gujri College,
Fatehgarh Sahib, on March 8th, 2014.