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Cloud Point Extraction: A Sustainable Method of Elemental Preconcentration

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Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Review

Cloud point extraction: A sustainable method of elemental

preconcentration and speciation
Pallabi Samaddar, Kamalika Sen *
Department of Chemistry, University of Calcutta, 92 APC Road, Kolkata 700009, India

A R T I C L E I N F O A B S T R A C T

Article history: Trace elements are gaining increasing attention of scientists working in various analytical fields.
Received 1 May 2013 Presence or absence of a trace element in a system seriously modifies its intrinsic behavior. Cloud point
Accepted 19 October 2013 extraction (CPE) is an upcoming technology to preconcentrate and separate many of the trace elements
Available online 27 October 2013
from different chemical and biological systems. The system is sustainable as it involves benign
extractants like surfactants and that too at low concentrations at slightly elevated temperatures to form
Keywords: clouds that separate out from the bulk solution. In addition, the extraction behavior of many elements
Cloud point extraction
depends on its chemical species. Keeping in view the need to summarize the research encompassing this
Trace element
Speciation
technique, many review articles were published which cover a selection of the literature published on
ICP-OES this topic over several time spans. A myriad of various technological developments has been reported by
AAS several workers. These developments have prompted us to revisit the CP technology with a better
understanding of its detection, mechanism and extension to species dependent extraction behavior with
regard to the state of art determination of trace metals in our day to day applications. The present article
summarizes mainly the results of trace metal preconcentration using CP methodology from different
practical samples with an insight to the probable mechanism and speciation involved from 2006
onwards.
ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1210
2. Procedures to detect cloud point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1210
2.1. Particle counting method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1210
2.2. Refractometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1210
2.3. Turbidimetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1210
2.4. Thermo optical method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1210
2.5. Viscometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1211
3. Reagents and methodology for cloud point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1211
4. Mechanistic overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1211
5. Application to natural systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1212
6. Speciation using cloud point extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1212
6.1. Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1212
6.2. Mercury . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1215
6.3. Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1215
6.4. Arsenic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1216
6.5. Antimony . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1216
6.6. Selenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217
6.7. Manganese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217
6.8. Tin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217

* Corresponding author. Tel.: +91 9163295148.

E-mail address: kamalchem.roy@gmail.com (K. Sen).

1226-086X/$ – see front matter ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.10.033
 Author's personal copy

1210 P. Samaddar, K. Sen / Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219

6.9. Thallium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217

7. Future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217
8. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1217
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1218
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1218

1. Introduction particles in a solution at various temperatures, it is expected that at

the temperature where a new phase appears, a sudden change in
The cloud point (CP) of a solution is the temperature at which number of particles would be observed and this temperature
the solution forms two phases. Cloud point preconcentration (CPP), indicates the cloud point for the solution.
based on the clouding phenomena of surfactants has drawn large Imani et al., prepared several solutions of PEG with sulfate salts
attention in separation science. CPP offers many advantages over with varying mass ratios of PEG to salt from 0.8 to 1 and 1–2 [16].
traditional liquid–liquid extraction [1]. The two basic components They used a Spectrex laser particle counter with a laser diode at a
as a prerequisite for CPP are a salt solution and a surfactant wavelength of 670.8 nm. The solution was pumped to a flow cell
solution which separates into immiscible surfactant-rich and and the temperature was measured at the entrance of the cell by a
surfactant-poor phases [2]. In the presence of salt, long-tailed thermocouple. At each temperature, the number of particles was
surfactants self assemble in aqueous solution at a particular measured per cubic centimeter and at the cloud point, a sharp
temperature into long, flexible wormlike micelles, thus rendering change in the number of particles was observed.
the solution viscoelastic [3,4]. An analyte interacting with micellar
systems can therefore be concentrated into the surfactant-rich 2.2. Refractometry
phase in a small volume.
Different elements at low concentrations influence various In designing PEG-salt cloud points, different salt solutions e.g.,
chemical and biological systems and play vital roles in the K3PO4, K2HPO4, Na2HPO4, and Na2CO3 along with PEG solution
determination of their structure and functions [5–11]. Solvent (MW = 10,000) were mixed. A refractometer equipped with a
extraction is a widely used separation tool for rare earth metals digital thermometer was used through which water was circulated
[12]. However, this method has some problems, such as use of toxic using thermostatically controlled bath. The mixtures of solutions
and flammable organic solvents, poor extraction-speed, and low were directly injected into the prism assembly of the instrument
concentration efficiency for solute. Furthermore, due to the using a Hamilton syringe stored at the working temperature to
dilution in the organic phases, the mass action of the extractant avoid evaporation. The refractive index measurements were done
is decreased compared to that potentially present in the pure after the liquid mixtures attained the constant temperature of the
compound. On the other hand, the heterogeneous extraction at refractometer. This procedure was repeated at least three times
cloud point based on surfactants, are simple, rapid and powerful [17].
which extract the solutes existing in the homogeneous or pseudo-
homogeneous aqueous solution into the water-immiscible phase 2.3. Turbidimetry
after the phase separation. Indeed, the extractant is first dispersed
in the aqueous phase by sonication and left to settle at a particular The effect of salt concentration on CP temperatures can be
temperature after reaction with the metal cation to be extracted. studied by the turbidimetry method using a reaction calorimeter.
These methods are more inexpensive, of lower toxicity, and cause The calorimeter is attached with a glass head with turbidity sensor,
negligible environmental pollution than the conventional liquid– temperature sensor and a stirrer along with a temperature control
liquid extraction. Such methodology also provides high precon- and programming device to measure the CP temperature with the
centration factors [13,14]. The system is highly sustainable as it help of the turbidity sensor. The turbidity is measured in % units
involves the use of benign extractants like surfactants and that too (Milli-Q quality distilled water is taking as reference). The second
at low concentrations at slightly elevated temperatures to form method is to study the transmittance of the solution was with
clouds that separate out from the bulk solution. increasing temperature. A slow heating rate of 0.2 8C/min is
maintained in all the measurements to minimize the thermal lag
2. Procedures to detect cloud point between the sample and the solution. The cloud point of each
sample is determined as the average of at least two independent
There are several procedures to detect the cloud point, some of scans. [18].
which are enlisted below
2.4. Thermo optical method
 Light scattering or particle counting method
 Refractometry Thermo optical analysis (TOA) provides a simple and rapid,
 Turbidimetry method to determine cloud point curves of binary polymer/solvent
 Thermo optical method systems. The sample is taken in a pyrex tube which is connected to
 Viscometry a vacuum pump and evacuated. The tube is then collapsed and
sealed by a vacuum when one end is heated by a flame while the
2.1. Particle counting method content of the tube is maintained at sub-ambient temperature by
liquid nitrogen. The cloud point curves are determined at the
The particle counting method for cloud point measurement was saturation vapor pressure of the solvent. A polarizing microscope is
introduced by Eliassi et al. [15]. The basis of this method is the fitted to it through a photodiode and a microprocessor. The
determination of the number of particles in a mixture. When a new heating–cooling stage is designed for observation of the thermal
phase appears in a solution, a large number of small particles are behavior of a sample under the microscope. The temperature
produced and the solution becomes hazy. The particles scatter the program for the given run is entered into the microprocessor. This
light beam passing through it. By measuring the number of program consists of a starting temperature, a heating and cooling
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P. Samaddar, K. Sen / Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219 1211

Table 1
Conditions for cloud point extraction of different metal ions.

M S C T t (min) Y (min) R Reference

Cu Triton X-100 Amino acid 68 8C 10 5 Absolute methanol [21]

Co Triton X-114 PAN 50 8C 10 10 CCl4 [22]
Cd Triton X-114 APDC 45 8C 20 10 Ethanol [23]
Cd Triton X-114 Dithizone 55 8C 20 10 THF [24]
Pb Triton X-114 Dithizone, octanol RT 1 – HNO3 in methanol (1 mol L1) [25]
Cd Triton X-114 Methyl green 50 8C 15 10 HNO3 in methanol (1 mol L1) [26]
Hg Triton X-114 PAN, TAR 50 8C 10 5 Ethanol [27]
Al Triton X-114 Xylidal blue 50 8C 10 – HNO3 in methanol [28]
Hg Triton X-114 Ammonium O,O-diethyldithiophosphate (DDTP) 60 8C 15 5 HCl in methanol [29]
As(III) Triton X-114, SDS Pyronine B 45 8C 20 5 1 M HCl + Antifoam A [30]
Co Triton X-114 4-Benzylpiperidinedithiocarbamate (K-4-BPDC) 60 8C 10 5 HNO3 in ethanol [31]
Cu Triton X-114 N,N0 -bis(2-hydroxy acetophenone)- 35 8C 15 10 HNO3 in methanol [32]
1,2-propanedimine(L)
Zn Triton X-114 2-methyl-8-hydroxyquinoline(quinaldine), PAN 70 8C 20 10 HNO3 in ethanol [33]
Al, Zn Triton X-114 8-HQ 45 8C 10 7 Ethanol [34]
Cd Triton X-114 Iodide, methyl green (MG) 50 8C 15 10 HNO3 in methanol [26]
Pb, Co, Cu Triton X-114 1-Phenylthiosemicarbazide (1-PTSC) 50 8C 20 10 HNO3 in methanol [35]
Fe, Cu Triton X-114 Erichrome cyanine 70 8C 15 – 0.02 M H2SO4 in ethanol [36]
Fe Triton X-114 2-(5-bromo-2-pyridylazo)-5- 50 8C 5 5 Ethanol [37]
diethylaminophenol (5Br-PADAP)
Pb Triton X-114 Brilliant cresyl blue (BCB) 40 8C 30 10 HNO3 in methanol (1 mol L1) [38]
Sn Triton X-100 CTAB,a-polyoxometalate 55 8C 15 15 DMF [39]
Mn Triton X-100 1-phenyl-3-methyl-4-benzoyl-5- 80 8C 25 5 0.1 M HNO3 [40]
pyrazolone (PMBP)
As Triton X-114 Pyronine B, SDS 45 8C 20 5 1.0 mol L1 HNO3 in methanol [30]
Be Triton X-114 Cetyl-pyridinium chloride (CPC) 50 8C 10 10 60:40 methanol–water mixture [41]
containing 0.03 mL HNO3
La, Eu, Lu Triton X-100 Di(2-ethylhexyl)phosphoric acid (HDEHP) 80 8C 60 Water containing Arsenazo-III band [42]
Zr, Hf Triton X-114 Quinalizarine 55 8C 7 7.5 0.1 mol L1 HNO3 [43]
La, Gd, Yb Triton X-100 Calixarenes 73–75 8C 15 – pH 6 acetate buffer [44]
U(VI), Th(IV), Triton X-114 Dibenzoylmethane (DBM) 50 8C 15 5 20:80 Methanol:1 M HNO3 [45]
Zr(IV), Hf(IV)

rate, and an end temperature. Results shown on the microproces- time (t), centrifugation time (Y) and suitable reference (R) for
sor display are connected to the PC for data storage [19]. various CPE have been tabulated in Table 1.

2.5. Viscometry 4. Mechanistic overview

The cloud point separation of a salt – poly(ethylene glycol) –
water system can also be studied using viscometry. The viscometry
measurements are done using a viscometer equipped with a water
bath and a thermostat to control the temperature with accuracy of
0.1 8C. A chronometer measured the time of flow of solutions
through the U-tube of the viscometer. On variation of temperature
and by visual inspection of solutions the cloud points were observed.
The viscometric measurement results were plotted versus temper-
ature. The plots exhibited shallow minima in the viscosity at the
cloud point temperature. The cloud points were determined at the
minimum of the curves obtained on plotting the measured
viscosities versus variation of temperature. The recorded tempera-
ture was the cloud point of the mixture. The viscosity after passing
through a minimum begins to increase and then decrease again, but
more intensively. This phenomenon was explained by the fact that at
higher temperature the molecular motions overcome the molecular
interactions and then, as expected, the viscosity decreases. However,
at the cloud point the number of particles of the new phase suddenly
increases and this causes an increase in the viscosity, which is
dominant over the viscosity decrease because of the temperature
increase [20]. The particle counting method, thermo-optical method
and viscometry were not developed further after 2002, 1991 and
2003 respectively.
3. Reagents and methodology for cloud point
Surfactants are amphiphilic compounds and have high solubi-
lizing effect towards different substrates. This property has been
extensively utilized in the preconcentration of metal ions, for
studying the mobility of drugs in aqueous and lipid media, probing
of biological systems, synthesis of nano-materials etc. These
compounds aggregate to form various assemblies like monolayers,
micelles, reverse micelles or vesicles in aqueous as well as organic
media. Non-ionic surfactants undergo cloud formation on heating,
followed by the formation of two coexisting isotropic phases [46–
49]. Clouding formation has also been observed for concentrated
aqueous salt solutions of certain zwitterionic and ionic surfactants
[50–54]. Clouding behavior, also known as coacervate phase
behavior or lower consolute behavior, is a typical physical change
Metal Surfactant (S) Heat at TºC
(M) + Complexing agent (C) + For time t
Centrifuged for time Y
Cooled in ice-bath

The general method of cloud point extraction is presented Dissolved in reagent R

schematically in Fig. 1 and pictorially in Fig. 2. The details of metal
(M), surfactant (S), chelating agent (C), temperature (T), heating Fig. 1. Schematic diagram of general steps in cloud point extraction.
 Author's personal copy
1212 P. Samaddar, K. Sen / Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219
Fig. 2. Pictorial presentation of cloud point extraction.
in the homogeneous solutions of amphiphilic substances, due to
which the solution separates into a surfactant-rich and a
surfactant-lean phase at a particular temperature. The tempera-
ture, at which this phase separation occurs, is known as the cloud
point (CP) or lower consolute temperature (LCT), an important
character of non-ionic surfactants. Clouding is ascribed to the
efficient dehydration of hydrophilic portion of micelles at higher
temperature condition. The micelles of the surfactant attract each
other and form clusters [55] with the approach of the cloud point
temperature. Recent experimental and theoretical investigations
reveal that the formation of the connected micellar network [56–
58] or the H bonds between water and the surfactant molecules are
responsible for the lower consolute behavior. The value of CP
depends on the structure and concentration of the surfactant and
the presence of additives [59,60]. The clouding may also occur with
the change in pressure [61,62] or due to the presence of certain
additives.
The mechanism by which this separation occurs is attributed to
the rapid increase in the aggregation number of the surfactant’s
micelles, as a result of the increase in temperature, or any other
critical phenomena. Ethylene oxide segments in the micelle repel
each other at low temperatures, when they are hydrated, and
attract each other as the temperature increases due to dehydration.
This effect causes a decrease in the effective area occupied by the
polar group on the micelle surface, increasing the size of the
micelle that can be considered to become infinite at the cloud
point, resulting in the phase separation. In many cases, the addition
of an organic solvent or a salt prior to the extraction step is
necessary to reach efficient extraction. The presence of ethanol
produces an adequate increase on the cloud point temperature of
the system, higher preconcentration factors and a better kinetics of
phase separation. On the other hand, the presence of inorganic
electrolytes decreases the cloud point temperature due to
dehydration of the poly(oxyethylene) chains. Additionally, inor-
ganic salts enhance the hydrophobic interactions among the
surfactant aggregates and the analytes, thus favoring their
extraction from the aqueous to the micellar phase [1].
In order to decrease the viscosity of the surfactant-rich phase
and facilitate its instrumental analysis, it is necessary to find an
optimal diluting agent depending on the surfactant system
employed, the instrumental detection system and the target
analytes [63]. When working with AAS, organic solvents such as
methanol or ethanol containing strong acids are frequently used
for dilution, offering appropriate solution properties for aspiration
and nebulization. In the case of ICP-OES, the enriched surfactant
phase is diluted with concentrated acids. For absorptiometric
measurements, the CPE-extracted phase can be measured without
further treatment, while for flourometric determination with
formic acid, 100% organic solvents, such as acetonitrile, are
employed when injecting the phase into a CE instrument.
5. Application to natural systems
The cloud point technique has used by several researchers to
preconcentrate and analyze different metal ions in a large variety
of samples. Tables 2–5 represent a glimpse of the variety of
samples analyzed for their transition metal, lanthanide, represen-
tative and precious metal content preconcentrated by cloud point
technique.
The extent of different metals studied using cloud point
extractions has been presented in Fig. 3.
6. Speciation using cloud point extraction
6.1. Iron
A simultaneous determination method for traces of Fe(III) and
Fe(II) in water was developed by on-line coupling of spectropho-
tometry with flame atomic absorption spectrometry (FAAS). The
method involves cloud point extraction (CPE) of both species with
ammonium pyrrolidinecarbodithioate (APDC) under standard
conditions, which facilitates the in situ complexation and
extraction of both species. The method is based on a mathematical
modification of the revised ferrozine method which overcomes the
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P. Samaddar, K. Sen / Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219 1213

Table 2
Cloud point preconcentration of transition elements.

Element Reagent Sample type Method of detection

Cu I) O,O-diethyldithiophosphate, Triton Drinking water, blood serum, human FAAS

X-100 [64] hair FAAS
II) N,N0 -bis(2-hydroxyacetophenone)- Water Spectrophotometry
1,2-propanediimine(L) [65] Food and water samples Spectrophotometry
III) Amino acid (Chelating agent), Triton (Certified) defatted milk powder and Atomic absorption spectrometry (AAS)
X-100 [66] tea Spectrophotometry
IV) Triton X-100, Octanol (cloud point Water samples
revulsant and synergic reagent), [67] Synthetic samples
V) Monocarboxylic acids and their
mixtures with amines [68]
VI) N,N0 -
bis(salicylideneaminoethyl)amine
(H2L), Triton X-100 [69]
Zn 2-methyl-8- Medicinal plants, blood samples of liver FAAS
hydroxyquinoline(quinaldine), 1-(2- cancer patients
pyridylazo)-2-naphthol (PAN), Triton
X-114 [70]
Co Polyethyleneglycolmono Drinking water sample Electrothermal atomic absorption
polyethyleneglycolmono p- Tablets of different pharmaceutical spectrometry (ETAAS)
nonylphenylethe [71] containing FAAS
Triton X-100 and sodium dodecyl sulfate Vitamin B12 Laser induced thermal lens
(SDS), pyridylazo compounds [72] Tap, river and sea water spectrometry
1-(2-Pyridylazo)-2-naphthol (PAN),
octylphenoxypolyethoxyethanol (Triton
X-114) [22]
Al and Zn 8-hydroxyquinoline, Triton X-114 [34] Bottled mineral water and foodstuffs Spectrofluorimetry
Cr 1-(2-pyridilazo)-2-naphtol (PAN), Water sample contaminated with Flame atomic absorption spectrometry
Triton X-114 [73] leather effluents Flame atomic absorption spectrometry
Chelating agents, ammonium River water and sea water
pyrrolidinedithiocarbamate for Cr(VI)
and 8-hydroxyquinoline for Cr(III),
Triton X-114 [74]
Cd APDC (0.5%, m/v), TX114 (5%, v/v) [75– Urine sample AAS
79] Soft drinks (TS-FF-AAS)
Pyridyl-azo-naphthol (PAN), Triton X- Rice and water sample Fluorescence spectrometry and TS-FF-
114 [85] Certified reference rice sample and food AAS
Triton X-114, dithizone [86] samples Flame atomic absorption spectrometry
Ion-associated complex in the presence Urine and water sample Thermospray flame quartz furnace
of iodide and methyl green (MG), [36] atomic absorption spectrometry
Ammonium
pyrrolidinedithiocarbamate (APDC)
solution and a Triton X-114 [87]
V 1-(2-pyridylazo)-2-naphthol (PAN) and Water samples, geological samples (FAAS)
hydrogen peroxide in acidic medium,
Triton X-100 [88]
Hg(II) HgI42 reacted with methyl green (MG) Sea food sample ICP-OES
cation, Tap wáter ICP-OES
octylphenoxypolyethoxyethanol Water samples Spectrophotometry
(Triton X-114) [81,89] Natural water and tilapia muscle ICP-MS
Ammonium O,O- samples CVAAS
diethyldithiophosphate (DDTP), Triton Human hair, dogfish liver and dogfish ETAAS
X-114, [90] muscle
Triton X-114, 1-(2-pyridylazo)-2- Hair sample
naphthol (PAN) and 4-(2-thiazolylazo)
resorcinol (TAR) (chelating agent) [27]
1-(2-pyridylazo)-2-naphthol (PAN),
Triton X-114 [82]
Ammonium O,O-
diethyldithiophosphate (DDTP) as the
chelating agent and 0.3% (m/v) Triton
X-114 [83]
2-(5-bromo-2-pyridylazo)-5-
(diethylamino)-phenol (5-Br-PADAP)
polyethyleneglycolmono-p-
nonyphenylether (PONPE 7.5) [84]
Pb(II), Co(II), Cu(II) 1-Phenylthiosemicarbazide (1-PTSC), Tap water, spring water, sea water, FAAS
octylphenoxypolyethoxyethanol canned fish, black tea, green tea, tomato
(Triton X-114) [85] sauce and honey
Cd and Pb Ammonium O,O diethyl Urine sample (GF AAS)
dithiophosphate (DDTP) (chelating
agent), Triton X-114 [86]
Fe and Cu Eriochrome Cyanine R (ECR), Triton X- Bush, branches and leaves; water FAAS
114 [36] samples (mineral and sea water) and
food samples (vegetables, bread and
hazelnut)
Cd, Pb, Cr, Cu, Zn, Ni and Fe Triton X-114, APDC [87] Environmental samples (FAAS) and (ICP-AES)
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1214 P. Samaddar, K. Sen / Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219

Table 2 (Continued )

Element Reagent Sample type Method of detection

Fe(II) 2-(5-bromo-2-pyridylazo)-5- Beer sample Spectrophotometry

diethylaminophenol (5-Br-PADAP) [37]
Mn Laboratory made reagent 4-(5-bromo- Food sample (rice flour, infant formula Flame atomic absorption spectrometry
2_-thiazolylazo)orcinol (Br-TAO) and and corn flour), biological sample (FAAS)
the surfactant Triton X-114 [88] (tomato leaves)
Mn and Fe 1-phenyl-3-methyl-4-benzoyl-5- Water sample Graphite furnace atomic absorption
pyrazolone (PMBP), p- spectrometry
octylpolyethyleneglycolphenylether
(Triton X-100) [89]
Co and Ni 1-(2-pyridylazo)-2-naphthol (PAN), Real and spiked samples Fiber optic-linear array detection
octylphenoxypolyethoxyethanol spectrophotometry
(Triton X-114) [90]
Cu, Ni, Zn and Fe 2-(6-(1H-benzo[d]imidazol-2- Blood, orange juice and lotus tree FAAS
yl)pyridin-2-yl)-1Hbenzo[d]Imidazole samples
(BIYPYBI) (complexing agent), Triton X-
114 [91]

Table 3
Cloud point preconcentration of representative elements.

Element Reagent Sample type Method of detection

As(III) APDC, Triton X-114 [92] Ground water samples (ETAAS)

Pyronine B, sodium dodecyl sulfate Drinking water and tap water samples (HGAAS)
(SDS), polyethylene glycol tert-
octylphenyl ether (Triton X-114) [30]
Sn p-octyl polyethyleneglycolphenyl ether Water sample (GFAAS)
(Triton X-100) and sodium dodecyl
sulfate (SDS) [93]
Sn(II) and Sn(IV) a polyoxometalate (Triton X-100), Various alloy, juice fruit, tape and Flame atomic absorption spectrometry (FAAS)
CTAB [63] waste water samples
Al(III) Xylidyl Blue (XB), Triton X-114, [28] Mineral water Flame atomic absorption spectrometry (FAAS)
Bi Triton X-100, Octanol (revulsant and Water and geological samples Flame atomic absorption spectrometry (FAAS)
synergic reagent) [94]
Pb Triton X-114, octanol (cloud point Tap water, river and lake water FAAS
revulsant and synergic reagent) [25]
Cr(III), Pb(II), Cu(II), Tween 80 [95] Reference material and spiked samples FAAS
Ni(II), Bi(III), and Cd(II)
Be(II) 1,8-dihydroxyanthrone as chelating Water samples. Inductively coupled plasma-atomic emission
agent, Triton X-114 [41] spectrometry (ICP-AES)

interference of Fe(III) on the spectrophotometric determination of
Fe(II); total Fe is determined by flame AAS. The results obtained
reveal that this method is an alternative approach to the speciation
of dissolved iron in natural waters at mg L1 levels, without
interferences. The ferrozine reagent, proposed by Stookey [98],
reacts with Fe(II) to form a stable magenta-colored complex,
absorbing at 562 nm with a molar absorption coefficient close to
30,000 L mol1 cm1 at pH between 4 and 9. As previously
discussed, however, Fe(III) can also react with ferrozine, and
therefore interfere with the determination of Fe(II). Due to the lack
of a highly selective masking agent for Fe(II) or Fe(III) against each
other, a revision of the classic ferrozine method was proposed
which overcomes interference by Fe(III) [99]. In this method a
mixture of dissolved Fe(II) and Fe(III) reacting with the ferrozine
leads to the absorbance A1 where, eFe(II) and eFe(III) are the molar
absorption coefficients,
A1 ¼ eFeðIIÞ l ½FeðIIÞ þ eFeðIIIÞ l½FeðIIIÞ (1)
and [Fe(II)] and [Fe(III)] are the concentrations of the Fe species.
After addition of a reducing agent, application of the additive
property of the Beer–Lambert law should yield the absorbance:
A2 ¼ eFeðIIÞ lð½FeðIIÞ þ ½FeðIIIÞÞ (2)
Solution of the simple linear system of Eqs. (1) and (2) gives

Table 4
Cloud point preconcentration of lanthanides and actinides.

Element Reagent Sample type Method of detection

U(VI)
La(III), Eu(III) and Lu(III)
Zr and Hf
La(III), Gd(III) and Yb(III)
U(VI), Th(IV), Zr(IV), Hf(IV)
Triton X-114, cethyl trimethylammonium bromide (CTAB), Water sample (tap water, UV/vis spectrometer
color reaction of uranium with pyrocatechol violet in the waste water, well water sample)
presence of potassium iodide in hexamethylenetetramine
buffer media [96]
Di(2-ethylhexyl)phosphoric acid and Triton X-100 [42] Synthetic aqueous samples ICP-AES
Quinalizarine (chelating agent), Triton X-114 [43] Water and alloy samples ICP-AES
p-sulfonato thiacalixarene (ST), tetra-sulfonatomethylated Synthetic aqueous samples Spectrophotometry
calix[4]resorcinarene (SR), calix[4]resorcinarene
phosphonic acid (PhR) as chelating agents, Triton X-100
[44]
Dibenzoylmethane(DBM), Triton X-114 [45] Synthetic aqueous samples ICP-AES
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P. Samaddar, K. Sen / Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219
Table 5
Cloud point preconcentration of precious metals.
Element Reagent
Au O,O-diethyldithiophosphate and Triton X-114 [97]
A1 eFeðIIÞ  A2 eFeðIIIÞ
½FeðIIÞ ¼

eFeðIIÞ eFeðIIÞ  eFeðIIIÞ l
A2  A1
½FeðIIIÞ ¼

eFeðIIÞ  eFeðIIIÞ l
A surfactant concentration of 1–1.5 g L1 was found to extract
the complexes of the iron species effectively [100].
Another CPE based separation and spectrophotometric detec-
tion method for iron was proposed by Filik and Giray [37]. In this
method, Fe(II) reacts with 2-(5-bromo-2-pyridylazo)-5-diethyla-
minophenol (5-Br-PADAP) in the presence of EDTA yielding a
hydrophobic complex, which then is extracted into surfactant-rich
phase. Total iron was determined after the reduction of Fe(III) to
Fe(II) by using ascorbic acid as reducing agent. Variable parameters
affecting the CPE efficiency were evaluated and optimized. The
proposed method was applied to the speciation of iron in beer
samples with satisfactory results. CPE was used as a separation and
preconcentration step combined with UV–vis spectrophotometry
for the speciation of iron in beer without sample digestion.
6.2. Mercury
A cloud point extraction methodology was developed for
simultaneous preconcentration of Hg(II), methylmercury (MeHg),
ethylmercury (EtHg), and phenylmercury (PhHg) was developed
using cold vapor atomic fluorescence spectrometry for speciation
analysis of mercury in fish. The four mercury species were taken
into complexes with ammonium pyrrolidine dithiocarbamate
(APDC) in aqueous non-ionic surfactant Triton X-114 medium and
concentrated in the surfactant-rich phase by heating to 40 8C.
Separation of the enriched complexes was achieved on an RP-C18
column with a mixture of methanol, acetonitrile, and water
(65:15:20, v/v) containing 200 mmol L1 acetic acid (pH 3.5) as the
mobile phase. An on-line oxidation of the effluent from HPLC was
done in the presence of K2S2O8 in HCl, prior to optimal cold vapor
generation of mercury species. The variables affecting the
complexation and extraction steps were examined. The precon-
centration of 10 mL of solution with 0.08% w/v Triton X-114 and
0.04% w/v APDC at pH 3.5 gave enrichment factors of 29, 43, 80, and
98 for MeHg, EtHg, PhHg, and Hg(II), respectively. The developed
method was successfully applied to the speciation of mercury in
real fish samples [101].
A dual-cloud point extraction (dCPE) technique was proposed
for the sample pretreatment of capillary electrophoresis (CE)
speciation analysis of mercury. In dCPE, cloud point was carried out
Fig. 3. The percentage use of different metal ions for cloud point extraction.
1215
Sample type Method of detection
Certified reference human hair samples Electrothermal
Vaporization inductively coupled plasma
mass spectrometry
twice in a sample pretreatment. First, four mercury species,
methylmercury (MeHg), ethylmercury (EtHg), phenylmercury
(PhHg), and inorganic mercury (Hg(II)) formed hydrophobic
complexes with 1-(2-pyridylazo)-2-naphthol (PAN). After heating
and centrifuging, the complexes were extracted into the surfac-
tant-rich phase. Instead of the direct injection or analysis, the
surfactant-rich phase containing the four Hg species was treated
with 150 mL 0.1% (m/v) L-cysteine aqueous solution. The four Hg
species were then transferred back into aqueous phase by forming
hydrophilic Hg–L-cysteine complexes. After dCPE, the aqueous
phase containing the complexes was subjected to capillary
electrophoresis (CE). With CE separation and on-line UV detection,
the detection limits were 45.2, 47.5, 4.1, and 10.0 mg L1 (as Hg) for
EtHg, MeHg, PhHg, and Hg(II), respectively. As an analysis method,
the present dCPE–CE with UV detection obtained similar detection
limits as of some CE–inductively coupled plasma mass spectrom-
etry (ICP-MS) hyphenation technique, but with simple instrumen-
tal setup and obviously low costs. Its utilization for Hg speciation
was validated by the analysis of the spiked natural water and
tilapia muscle samples [82].
A sensitive method for speciation analysis of inorganic
mercury (Hg2+) and methyl mercury (MeHg+) was developed by
using high performance liquid chromatography (HPLC) combined
with inductively coupled plasma mass spectrometry (ICP-MS)
after cloud point extraction. The analytes were complexed with
sodium diethyldithiocarbamate (DDTC) and preconcentrated by a
non-ionic surfactant Triton X-114. Mercury species were effec-
tively separated by HPLC in less than 6 min. The enhancement
factors for 25 mL sample solution were 42 and 21, and the limits of
detection were 4 and 10 ng L1 for Hg2+ and MeHg+, respectively
[102].
A nonchromatographic speciation technique for mercury was
developed by sequential cloud point extraction (CPE) combined
with inductively coupled plasma optical emission spectrometry
(ICP-OES). Hg2+ was complexed with I to form HgI42 which
reacted with the methyl green (MG) cation to form hydrophobic
ion-associated complex. The complex was then extracted into the
surfactant-rich phase, which are subsequently separated from
methylmercury (MeHg+) in the initial solution by centrifugation.
The surfactant-rich phase containing Hg(II) was diluted with
0.5 mol L1 HNO3 for ICP-OES determination. The supernatant was
subjected to the similar CPE procedure for the preconcentration of
MeHg+ by the addition of a chelating agent, ammonium pyrrolidine
dithiocarbamate (APDC), in order to form water-insoluble complex
with MeHg+. The mercury species in the micelles was directly
analyzed after disposal as describe above. The developed
technique was applied to the speciation of mercury in real seafood
samples and the recoveries for spiked samples were found to be in
the range of 93.2–108.7%. For validation, a certified reference
material of DORM-2 (dogfish muscle) was analyzed and the
determined values were in good agreement with the certified
values [80].
6.3. Chromium
The potential of polymerized vesicle coacervates made up of (4-
carboxybenzyl)bis[2-(10-undecenoyloxy)ethyl]methylammo-
nium bromide surfactants for the extraction of chromium species
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1216 P. Samaddar, K. Sen / Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219
from natural waters was examined. Linearly linked polymerized
vesicles of (4-carboxybenzyl)bis[2-(10-undecenoyloxy) ethyl]-
methylammonium bromide monomer were prepared by UV
excitation, and several factors affecting their phase behavior were
investigated. Evidently, the permeation of metallic elements
through the polymeric membrane was found to be sensitive to
ionic radius excluding ions larger than the interbilayer space of the
vesicle assembly. To this effect, Cr3+ ions could selectively diffuse
through the polymeric membrane. At the same time, this
minimum positive charge acts synergistically to the low perme-
ability of the bulky CrO42 anions by minimizing electrostatic
attraction with the bulky CH3N+ group. Optimization of vesicle
structure and surface charge were the regulating parameters in
exploiting this unique feature toward the analytical speciation of
Cr in natural waters. Detection limits as low as 0.1 mg L1 were
achieved by preconcentrating only 10 mL of sample volume with
recoveries in the range of 97.0–105.5% [103].
A simple mixed-micelle cloud point extraction procedure was
developed for speciation analysis of chromium in water samples by
electrothermal atomic absorption spectrometry (ET-AAS). A mixed
micelle consisting of sodium dodecyl sulfate (SDS) and Triton X-
114 was used as an extracting agent. Cr(VI) was complexed with
1,5-diphenyl carbazide (DPC) in an HCl medium and it was
concentrated in the surfactant-rich phase after CPE. Total
chromium was subjected to a similar extraction procedure after
oxidation. Then Cr(III) concentration was calculated by subtracting
Cr(VI) from the total chromium. Under optimum conditions, a
detection limit of 1 ng L1 with preconcentration factor of 92 was
achieved. Also the relative standard deviation for five replicate
determinations of 0.1 mg L1 Cr(VI) was 3.5%. The proposed
method was successfully applied to speciation of Cr(III) and Cr(VI)
in environmental water samples [104].
A CPE separation method was coupled with electrothermal
vaporization inductively coupled plasma optical emission spec-
trometry (ETV-ICP-OES) detection was proposed for the determi-
nation of chromium species. Thenoyltrifluoracetone (TTA) was
used both as an extractant for CPE of Cr(III) and a chemical modifier
for ETV-ICP-OES determination. When the system temperature
was higher than the cloud point temperature (CPT) of the selected
surfactant, Triton X-114, the complex of Cr(III) with TTA could
enter the surfactant-rich phase, whereas the Cr(VI) remained in
aqueous solutions. Thus, an in situ separation of Cr(III) and Cr(VI)
could be realized. The concentrated analyte was introduced into
ETV-ICP-OES for determination of Cr(III) after proper disposal.
Cr(VI) is reduced to Cr(III) prior to determining total Cr, and its
assay was based on subtracting of Cr(III) from total chromium. The
proposed method was applied to the speciation of chromium in
different water samples. In order to verify the accuracy of the
method, a certified reference water sample was analyzed, and the
results obtained were in good agreement with certified values
[105].
CPE based speciation of chromium in water samples were
determined by flame atomic absorption spectrometry. Several
chelators have been used for this. Cr(III) reacts with acetylacetone
yielding a hydrophobic complex, which was entrapped in the
Triton X-100 surfactant-rich phase, whereas Cr(VI) remained in
aqueous phase. Thus, separation of Cr(III) and Cr(VI) could be
realized. Total chromium was determined after the reduction of
Cr(VI) to Cr(III) by using ascorbic acid as reducing reagent. Under
the optimal conditions, the detection limit of this method for Cr(III)
was 0.32 ng mL1 with an enrichment factor of 35 [106]. A
preconcentrative separation of Cr(III) species from Cr(VI) by CPE is
also possible using diethyldithiocarbamate (DDTC), bis-[2-Hy-
droxy-1-naphthaldehyde] thiourea, PAN, TAN 8-hydroxyquinoline
or 1-phenyl-3-methyl-4-benzoylpyrazol-5-one (PMBP) as the
chelating agent [73,107–111].
6.4. Arsenic
Reaction of As(V) with molybdate forms a yellow heteropoly
acid complex in sulfuric acid medium. When this solution is taken
in a surfactant medium and heated to 55 8C, analytes are
quantitatively extracted to the non-ionic surfactant-rich phase
(Triton X-114) after centrifugation. To decrease the viscosity of the
extract and to allow its removal methanol was added to the
surfactant-rich phase. 20 mL of this solution with 10 mL of 0.1% m/v
Pd(NO3)2 were injected into the graphite tube and the analyte
determined by electrothermal atomic absorption spectrometry.
Total inorganic As(III,V) was extracted similarly after oxidation of
As(III) to As(V) with KMnO4. As(III) was calculated by difference.
After optimization of the extraction condition and the instrumen-
tal parameters, a detection limit (3sB) of 0.01 mg L1 with
enrichment factor of 52.5 was achieved for only 10 mL of sample.
Relative standard deviations were lower than 5%. The method was
successfully applied to the determination of As(III) and As(V) in tap
water and total arsenic in biological samples (hair and nail) [112].
6.5. Antimony
A simple, sensitive method for the speciation of inorganic
antimony by cloud point extraction combined with electrothermal
atomic absorption spectrometry (ETAAS) was evaluated by Jiang
et al. A hydrophobic complex of antimony(III) was prepared with
ammonium pyrrolidine dithiocarbamate (APDC) at pH 5.0 and
subsequently the hydrophobic complex enters into surfactant-rich
phase, whereas antimony(V) remains in aqueous solutions.
Antimony(III) in surfactant-rich phase was analyzed by ETAAS
after dilution by 0.2 mL nitric acid in methanol (0.1 M), and
antimony(V) was calculated by subtracting antimony(III) from the
total antimony after reducing antimony(V) to antimony(III) by L-
cysteine. The detection limit of the proposed method was
0.02 ng mL1 for antimony(III), and the relative standard deviation
was 7.8%. The proposed method was successfully applied to
speciation of inorganic antimony in the leaching solutions of
different food packaging materials with satisfactory results [113].
A flame atomic absorption spectrometry (FAAS) determination
of antimony species after preconcentration by CPE was developed.
When the temperature was higher than the cloud point extraction
temperature, the complex of antimony(III) with N-benzoyl-N-
phenylhydroxylamine (BPHA) can enter the surfactant-rich phase,
whereas the antimony(V) remains in the aqueous phase. Anti-
mony(III) in surfactant-rich phase was analyzed by FAAS and
antimony(V) was calculated by subtracting of antimony(III) from
the total antimony after reducing antimony(V) to antimony(III) by
L-cysteine. The proposed method was applied to the speciation of
antimony species in artificial seawater and wastewater, and
recoveries in the range of 95.3–106% were obtained by spiking real
samples [114].
Another Sb speciation by on-line cloud point extraction
combined with electrothermal vaporization inductively coupled
plasma atomic emission spectrometry (ETV-ICP-AES) was
reported. The method is based on the complexation of Sb(III)
with pyrrolidine thiocarbamate (PDC) which form an hydrophobic
complex at pH 5.5 and subsequently enter surfactant-rich phase at
pH 5.5, whereas Sb(V) remain in aqueous solutions. The
preconcentration step is mediated by micelles of the non-ionic
surfactant Triton X-114 with ammonium pyrrolidine dithiocarba-
mate (APDC). The micellar system containing the complex was
subjected to FIA and the surfactant-rich phase was retained in a
microcolumn packed with absorbent cotton, at pH 5.5. After the
surfactant-rich phase was eluted with acetonitrile, it was
determined by ETV-ICP-AES. Sb(V) was reduced to Sb(III) by
L-cysteine prior to determination of total Sb, and its assay is based
 Author's personal copy
P. Samaddar, K. Sen / Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219
on subtracting Sb(III) from total antimony. The proposed method
was successfully applied for the speciation of inorganic antimony
in different water samples and urine sample with satisfactory
results [115].
6.6. Selenium
Cloud point extraction method for the separation and precon-
centration of Se(IV) and Se(VI) in environmental water samples as
well as total selenium in animal blood and tissue samples was
developed by Sounderajan and Udas. 3,30 -Diaminobenzidine (DAB)
is a selective and sensitive reagent and is known to form an intense
yellow compound piazselenol with selenium(IV). When a system
consisting of selenium, DAB and surfactant Triton X-114 is warmed
above the cloud point of the surfactant, the DAB–Se(IV) complex gets
extracted into the surfactant-rich phase while the Se(VI) remains in
the aqueous phase. Se(VI) in the sample was reduced to Se(IV) by
microwave heating of solution in 4 mol L1 HCl and total Se was
estimated by carrying out the CPE. The quantification of selenium
was carried out using ETAAS. The detection limit of selenium in
environmental water samples was 0.0025 mg L1 with an enrich-
ment factor of 100. The proposed method was successfully applied to
the determination of selenium(IV), (VI) in environmental water
samples and determination of total selenium in human blood,
animal blood and fish tissue [116].
A fluorometric ligand, 2,3-diaminonaphtalene (DAN) was used
for extraction of trace amounts of organic and inorganic selenium
species prior to their determination by spectrofluorimetry. CPE
parameters affecting complexation and phase separation were
optimized. The limit of detection was calculated by using nine
replicate measurements of 0.020 mg L1 Se solution after com-
plexing with DAN and 10-fold CPE preconcentration was
2.1 mg L1. The suggested method could be used for selenium
species of selenite, selenate, and total organic selenium at mg L1
level [117].
CPE separation followed by electrothermal vaporization induc-
tively coupled plasma mass spectrometry (ETV-ICP-MS) detection
was proposed for the speciation of inorganic selenium in
environmental waters. When the temperature of the system is
higher than the cloud point temperature (CPT) of the selected
surfactant Triton X-114, the complex of Se(IV) with ammonium
pyrrolidine dithiocarbamate (APDC) gets extracted into the
surfactant-rich phase, whereas the Se(VI) remains in aqueous
solutions. Thus, an in situ separation of Se(IV) and Se(VI) could be
realized. The concentrated analyte was introduced into the ETV-
ICP mass spectrometer for determination of Se(IV) after dilution
with 200 mL methanol. Se(VI) was reduced to Se(IV) prior to
determining total selenium, and its assay was based on subtracting
Se(IV) from total selenium. Under the optimized experimental
conditions, the limit of detection (LOD) for Se(IV) was 8.0 ng L1
with an enhancement factor of 39 when 10 mL of sample solution
was preconcentrated to 0.2 mL. The proposed method was applied
to the speciation of inorganic selenium in different environmental
water samples with the recovery for the spiked samples in the
range of 82–102% [118].
6.7. Manganese
The speciation of Mn(II) in tea infusion was studied using CPE.
In tea infusion, the flavonoid bound Mn(II) was extracted at pH 5.0
using 0.2% (v/v) Triton X-100. The remaining free aquated Mn(II)
and weakly complexed Mn(II) in solution were both chelated with
8-hydroxyquinoline (HOx) and CPE preconcentrated with TX-100.
The enriched analyte was determined by flame AAS. The method
was not essentially affected from common ions, and was capable of
Mn speciation in tea infusion by distinguishing free aquated and
1217
weakly complexed (unbound) Mn(II) from flavonoid bound Mn(II)
fractions. This speciation analysis with sequential CPE showed that
about 30% of total manganese in tea leaves was total chelatable Mn
passing into tea infusion, and that about 95% of this chelatable Mn
was in the unbound state, existing primarily as inorganic Mn(II)
species [119].
6.8. Tin
CPE separation and graphite furnace atomic absorption
spectrometry (GFAAS) detection was proposed for the determina-
tion of inorganic tin species. When the system temperature is
higher than the cloud point extraction temperature (CPT) of the
mixed surfactant of p-octyl polyethyleneglycolphenyl ether
(Triton X-100) and sodium dodecyl sulfate (SDS), a PAN complex
of Sn(IV) could be extracted into the surfactant-rich phase,
whereas the Sn(II) remained in the aqueous phase. Thus, an in
situ separation of Sn(IV) and Sn(II) could be achieved. The main
factors affecting the cloud point extraction were investigated
systematically. Under the optimized conditions, the detection limit
for Sn(IV), was found to be 0.51 ng mL1. The proposed method
was applied to the speciation analysis of tin in different water
samples and the recovery of total Sn was in the range of 98.9–
100.7% [93].
6.9. Thallium
Ultra-trace speciation analysis of thallium in environmental
water samples was achieved using CPE and analyzed by
inductively coupled plasma mass spectrometry (ICP-MS). A mixed
micelle consisting of sodium dodecyl sulfate (SDS) and Triton X-
114 was used as a chelating as well as an extracting agent. Tl(III)–
DTPA (diethylenetriaminepentaacetic acid) complex in an HCl
medium could be extracted into a surfactant-rich phase in the
presence of Tl(I). The Tl(I) in the supernatant is subjected to a
similar extraction procedure after bromine oxidation. Ultrasoni-
cally assisted back-extraction is used to extract the Tl(III) species
from the surfactant-rich phase into a small volume of aqueous L-
cysteine. The preconcentration factor and detection limit were 125
and 0.02 pg mL1, respectively. The procedure was validated by
comparing the sum of the concentrations of individual Tl species
with total thallium concentration in certified reference materials
[120].
7. Future perspectives
Keeping in view the large number of CPE procedures for metal
ions and metalloids available, it is noteworthy to have preconcen-
tration techniques for different anionic species as well. The diverse
properties of anionic species both in the direction of its usefulness
and hazard causing effects need the right speciation and
preconcentration technique. CPE being a sustainable method is
worthy of performing such studies. The potential of CPE lies in the
possibility of simultaneous screening for a number of anions in
presence of metal ions in complex matrices. The inclusion of CPE in
advanced analytical chemistry courses could be a potential future
trend owing to the various aspects that may be discussed when a
CPE experiment is demonstrated (green chemistry principles,
elimination of organic solvents and introduction of surfactants in
spectroscopic analysis, trace analysis, the physico-chemical
aspects related to phase separation, etc).
8. Concluding remarks
As a general conclusion regarding the elemental preconcentra-
tion and speciation using cloud point extraction it is imperative
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1218 P. Samaddar, K. Sen / Journal of Industrial and Engineering Chemistry 20 (2014) 1209–1219
that the method is devoid of using toxic solvents. The discussions
demonstrate the potential of this impressive micellar phase
separation technique. Considering the high preconcentration
efficiency, versatility and low cost encountered in CPE, it is
expected that analytical chemistry will flourish to a large extent in
this interesting area, not only in the field of analytical applications
but also with respect to basic development to reach complete
elucidation for phase separation behavior.
Acknowledgments
We gratefully acknowledge University Grants Commission
(UGC, Sanction No. 41-248/2012 (SR)) for funding. One of the
authors, Pallabi Samaddar expresses sincere thanks to the UGC,
India [Memo No. UGC/1228C/Major Research (SC)2012] for
providing necessary fellowship.
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