Anal Bioanal Chem (2009) 394:759–782
DOI 10.1007/s00216-009-2660-9
REVIEW
Separation and preconcentration by a cloud point extraction
procedure for determination of metals: an overview
C. Bosch Ojeda & F. Sánchez Rojas
Received: 19 January 2009 / Accepted: 27 January 2009 / Published online: 24 February 2009
# Springer-Verlag 2009
Abstract Recently, cloud point extraction (CPE) has been
an attractive subject as an alternative to liquid–liquid
extraction. The technique is based on the property of most
non-ionic surfactants in aqueous solutions to form micelles
and become turbid when heated to the cloud point
temperature. This review covers a selection of the literature
published on applications of CPE in determination of metal
ions over the period between 2004 and 2008.
Keywords Cloud point extraction . Metal ions .
Preconcentration . Applications . Review
Introduction
Separation and preconcentration based cloud point extrac-
tion (CPE) is an analytical tool that has great potential to be
explored in improving detection limits and other analytical
characteristics over those of diverse methods. CPE as a
preconcentration method has many advantages, such as low
cost, safety, and speed, and is a simple procedure with a
high capacity to concentrate a wide variety of analytes of
widely varying nature with high recoveries and high
concentration factors. CPE also provides results comparable
to those obtained with other separation techniques. Accord-
ingly, any species that interacts with the micellar system,
either directly (generally hydrophobic organic compounds)
or after a prerequisite derivatization reaction (e.g. metal
ions after reaction with a suitable hydrophobic ligand), may
C. B. Ojeda : F. S. Rojas (*)
Department of Analytical Chemistry, Faculty of Sciences,
University of Málaga,
Campus Teatinos,
29071 Málaga, Spain
e-mail: fsanchezr@uma.es
be extracted from the initial solution and may also be
preconcentrated.
CPE consist of three simple steps (Fig. 1): (1) solubili-
zation of the analytes in the micellar aggregates; (2)
clouding; (3) phase separation for analysis. When a
surfactant solution is heated over a critical temperature,
the solution easily separates into two distinct phases: one
contains a surfactant at a concentration below, or equal to, a
critical micelle concentration; the other is a surfactant-rich
phase. The hydrophobic compounds initially present in the
solution and bound to the micelles are extracted to the
surfactant-rich phase. This phenomenon is observed, in
particular, for polyoxyethylene surfactants and can be
attributed to the two ethylene oxide segments in the micelle
that repel each other at low temperature when they are
hydrated and attract each other when the temperature
increases owing to the dehydration.
The theory and relevant applications of this impressive
separation method are discussed in various reviews [1–9].
Two recent and very interesting reviews have been
published covering different aspects of the CPE procedure
and their applications to metal determinations [10, 11].
Applications
Metal analysis by spectroanalytical techniques such as
flame atomic absorption spectrometry (FAAS), graphite
furnace atomic absorption spectrometry (GFAAS), induc-
tively coupled plasma (ICP) optical emission spectrometry
(OES), and ICP mass spectrometry (MS) is well estab-
lished. However, in some situations the sample needs
previous separation and/or preconcentration steps before
analytical measurement. Preconcentration procedures using
several analytical separation techniques have been pro-
760
Fig. 1 Cloud point extraction
(CPE) experimental procedure
Triton X-114
with or without
reagent
T=40oC
T=10oC
Clear
solution
posed. CPE is one of these. CPE has been used for the
extraction and preconcentration of many metal ions. Table 1
summarizes the available literature in the last few years on
applications of CPE in metal analysis, including metal ion,
reagent, micellar system, surfactant-rich-phase diluting
agent, detection limit, preconcentration factor, and matrix
data.
Other comments, in alphabetical order, not included in
Table 1 are as follows.
Aluminium
The synergistic CPE behaviour of Al(III) using 8-quinolinol
derivatives and 3,5-dichlorophenol from a weakly acidic
solution was investigated by Ohashi et al. [110]. The results
clarify the effect of some experimental factors, such as the
heating time and temperature, the pH value, and the
concentrations of reagents and Triton X-100. The method
can be applied to an effective pretreatment for several
analytical techniques, such as atomic absorption spectrom-
etry (AAS), ICP atomic emission spectrometry (AES), and
ICP-MS.
A CPE method based on the complex of Al(III) with 1-
phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and us-
ing Triton X-114 as a surfactant was proposed by Sang et
al. [12]. The surfactant-rich phase can be easily introduced
into the graphite furnace after dilution with 0.1 M HNO3
and aluminium can be directly determined by GFAAS. The
proposed method can be applied to the determination of
trace amounts of aluminium in various real samples.
Antimony
Fan [13] applied CPE as a separation/preconcentration step
for antimony species prior to FAAS determination. In the
system developed, N-benzoyl-N-phenyhydroxylamine
(BPHA) was used as the chelating agent and Triton X-114
as the extracting agent. When the system temperature is
C.B. Ojeda, F.S. Rojas
Aqueous
phase
Phase
separation
1 hr
Cloud Concentrated
solution micellar phase
higher than the CPE temperature, the complex of Sb(III)
with BPHA can enter the surfactant-rich phase, whereas the
Sb(V) remains in the aqueous phase. Sb(III) in the
surfactant-rich phase was analysed by FAAS and the Sb
(V) content was calculated by subtracting the Sb(III)
content from the total antimony content after reduction of
Sb(V) to Sb(III) by l-cysteine.
Li et al. [14] evaluated the feasibility of coupling an on-
line CPE preconcentration with electrothermal vaporization
(ETV) ICP-AES for determination of inorganic antimony
species in environmental and biological samples. In this
work, ammonium pyrrolidine dithiocarbamate (APDC) was
employed not only as a chelating agent in CPE but also a
chemical modifier in ETV-ICP-AES. The advantages of the
proposed method are summarized as follows: (1) simplicity,
selectivity, safety, low cost, and high preconcentration
factor; (2) the Sb(III)–APDC complex can be vaporized
quantitatively from the graphite furnace at a lower
temperature; (3) by combination of on-line CPE with
ETV-ICP-AES, a much lower detection limit could be
achieved.
Hagarová et al. [15] used an optimized CPE procedure
for the selective separation/preconcentration of Sb(III) prior
to its determination by GFAAS. In this procedure, APDC
was used as the chelating agent and Triton X-114 as the
extracting one.
Arsenic
Tang et al. [16] applied CPE as a preconcentration step for
GFAAS determination of As(III). In the system developed,
APDC was used as the chelating agent and Triton X-114 as
the extractant. The proposed method offers many advan-
tages, such as low cost, safety, and a high capacity to
concentrate metal chelate. The method avoided calculating
the As(III) content by difference and realized that the
selective determination of As(III) for the interference of As
(V) was negligible.
Table 1 Cloud point extraction (CPE) applications for individual metal analysis

Ion Reagent Micellar SRP diluting agent Detection system DL PF Matrix Reference
system

Al PMBP Triton X-114 200 µL 0.1 M HNO3 GFAAS 0.09 ng mL−1 37a Biological and water samples [12]
−1 b
Sb BPHA Triton X-114 100 µL methanol FAAS 1.82 ng mL Sb(III) 45 Speciation in artificial [13]
seawater and
wastewater
2.08 ng mL−1 Sb(total)
Sb APDC Triton X-114 100 µL acetonitrile ETV-ICP-AES 0.09 ng mL−1 Sb(III) 872c Speciation in different water [14]
samples and urine
Sb APDC Triton X-114 200 µL 0.2 M HNO3 GFAAS 0.03 ng mL−1 Sb(III) 28b Speciation in natural waters [15]
in methanol
As APDC Triton X-114 100 µL 0.1 M HNO3 GFAAS 0.04 ng mL−1 As(III) 36c Water samples [16]
in methanol
As Molybdate Triton X-114 100 µL methanol GFAAS 0.01 ng mL−1 As(V) 52b Speciation in tap water and total [17]
As in biological
samples (hair and nail)
Be CAS Cetyl pyridinium 300 µL UV/vis 0.05 ng ml-1 25c, 15.6b Water samples [18]
chloride and tetrahydrofuran spectrophotometry
Triton X-114
Be Anthralin Cetyl pyridinium – UV/vis 0.2 ng mL−1 14.2b, 25c Water samples [19]
chloride and spectrophotometry
Triton X-114
Be Anthralin Cetyl pyridinium 400 µL 60:40 methanol/ ICP-AES 0.001 ng mL−1 24.9b; 16.7c Water samples [20]
chloride and water mixture with
Triton X-114 0.03 mL HNO3
Bi Dithizone Triton X-114 50 µL tetrahydrofuran GFAAS 0.02 ng mL−1 196b Tap water and biological sam- [21]
ples (urine and hair)
Bi DDTC Triton X-114 50 µL tetrahydrofuran GFAAS 0.04 ng mL−1 195b Water samples [22]
−1
Bi Bromopyrogallol Triton X-114 300 µL methanol UV/vis 2 ng mL 20c Human urine [23]
red spectrophotometry
Cd DDTC Triton X-114 – GFAAS 2 ng mL−1 51.6c Seawater [24]
−1
Cd DDTP Triton X-114 in 400 µL 5% v/v ethanol FAAS 0.9 ng mL – Mineral water, physiological [25]
the presence of solution containing solution and cigarette
NaCl 0.1 M HNO3 tobacco
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview

Cd PMBP Triton X-100 300 µL methanol with FAAS 0.64 ng mL−1 23a Water samples [26]
0.1 M HNO3
Cd Iodide Triton X-114 At 500 µL with ethanol FAAS 1.0 ng mL−1 55.6c, 14.7b Water samples [27]
−1
Cd APDC Triton X-114 At 600 μL with 10% HNO3 TS-FF-AAS 0.04 ng mL 13b Water and urine [28]
and 20% methanol
Cd – PONPE 7.5 At 2 mL with 3% sodium CV-AAS 0.56 ng mL−1 62b Water samples [29]
tetrahydroborate as reduc-
ing agent and 0.2 M HCl
as carrier solution
Cd PAN Triton X-100 200 µL 2 M HCl GFAAS 5.9 ng L−1 50d Water samples [30]
761
Table 1 (continued)
762

Ion Reagent Micellar SRP diluting agent Detection system DL PF Matrix Reference
system

Cd 5-Br-PADAP Triton X-114 200 µL methanol with GFAAS 0.04 ng mL−1 21a Water samples [31]
0.1 M HNO3
Cd 5-Br-PADAP PONPE 7.5 1.0 mL methanol acidified GFAAS 0.2 ng mL−1 22b Urine samples and a water [32]
with 0.1 M HNO3 standard reference material
Cd APDC Triton X-114 200 µL ethanol WCAAS 5 ng L−1 15c Urine [33]
−1
Cd GBHA Triton X-114/ Ethanol (~0.5 mL) until a GFAAS 7 ng L 22c Water and tobacco [34]
SDS/NaCl final volume of 1 mL
Cd Carboxylic acids OP-10 2 mL distilled water FAAS 2 ng L−1 – Water samples [35]
Ce n-TBHA Triton X-114 At 1.0 mL with 1 M HNO3 ICP-AES 0.4 ng mL−1 13.8b Water samples [36]
Cr N,N′-Bis(α-methyl – – FAAS 0.1 ng mL−1 – Speciation in tap and river [37]
salicylidene) water samples and certified
propane-1, reference material BCR 544
3-diimine
Cr DDTC Triton X-114 50 µL methanol HPLC 3.4 ng mL−1 Cr(III) 65c Cr(III) Speciation in snow water, river [38]
19c Cr(VI) water, seawater, and waste-
water samples
5.2 ng mL−1 Cr(VI)
Cr PMBP – – ICP-AES 0.81 ng mL−1 Cr(III) 20d Speciation in natural water [39]
samples
Cr Br-PF Triton X-100 200 µL methanol solution GFAAS 0.01 ng mL−1 Cr(VI) 50c Water samples [40]
of 1 M HNO3
Cr TTA Triton X-114 100 µL methanol solution ETV-ICP-AES 0.22 ng mL−1 Cr(III) 50c Water samples [41]
of 0.125 M HCl
Cr 1,5- Triton X-114 – FAAS 0.4 ng mL−1 Cr(VI) 27c – [42]
Diphenylcarbazide
Cr APDC Triton X-114 1.0 mL methanol solution GFAAS 2.5 ng L−1 Cr(VI) 30c Speciation in river water [43]
of 0.1 M HNO3
3.7 ng L−1 Cr(total)
Cr Bis(2-hydroxy- Triton X-100 300 µL methanol solution FAAS 0.18 ng mL−1 58c Speciation in tap water and [44]
1-naphthaldehyde) of 0.1 M HNO3 river water
thiourea
Cr PMBP Triton X-114 200 µL 0.1 M HNO3 GFAAS 21 ng L−1 42a Speciation in natural water [45]
−1 a
Cr Acetylacetone Triton X-100 300 µL methanol solution FAAS 0.32 ng mL 35 Water samples [46]
of 0.1 M HNO3
Co PAN Triton X-100 0.5% HNO3/0.1% Pd GFAAS 0.003 ng mL−1 100d Water samples [47]
(NO3)2
Co APDC Triton X-114 200 μL ethanol TS-FF-AAS 2.1 ng mL−1 130b Biological samples [48]
−1 b
Co PAN Triton X-114 20 μL carbon tetrachloride TLS 0.03 ng mL 470 Water samples [49]
Co – PONPE 7.5 75 μL methanol solution of STPF-GFAAS 10 ng L−1 15d Drinking waters [50]
0.8 M HNO3
Cu Dithizone Triton X-114 Tetrahydrofuran UV/vis 4.6 ng mL−1 – Liver samples [51]
spectrophotometry
C.B. Ojeda, F.S. Rojas
Table 1 (continued)

Ion Reagent Micellar SRP diluting agent Detection system DL PF Matrix Reference
system

Cu Me-BTABr Triton X-114 200 μL methanol solution FAAS 1.08 ng mL−1 17b Water samples [52]
of 1.0 M HNO3
Cu NDTT Triton X-114 200 µL methanol solution FAAS 0.22 ng mL−1 22.4c Environmental water samples [53]
of 0.1 M HNO3
Cu Cupron Triton X-114 800 µL methanol solution FAAS 0.04 ng mL−1 88c River water and seawater [54]
of 0.1 M HNO3 samples
Cu HEPTS Triton X-114 2 mL methanol UV/vis 0.1 ng mL−1 – Water and saturated saline [55]
spectrophotometry samples
Cu Me-BDBD Triton X-114 200 μL methanol solution FAAS 1.5 ng mL−1 14b Water samples [56]
of 1.0 M HNO3
Cu 4-BPDC Triton X-114 – UV/vis 1.6 ng mL−1 – Water samples [57]
spectrophotometry
Cu Thiamine Triton X-114 At 2.5 mL with ethanol/ Spectrofluorimetry 0.29 ng mL−1 10c Water samples and parenteral [58]
water (1:1) solutions
Cu Alizarin S Triton X-114 1 mL methanol solution FAAS 1.07 ng mL−1 21b Water samples [59]
of 0.1 M HNO3
Cu PTU Triton X-114 0.5 mL 0.5 M HNO3 FAAS 1.6 ng mL−1 30d Environmental samples [60]
in methanol
Au Without reagent PONPE 7.5 – GFAAS 2.0 ng L−1 200b Water and copper samples [61]
−1
Fe Ferron Triton X-114 0.5 mL 1 M HNO3 FAAS 0.4 ng mL 19.6b Environmental and biological [62]
in methanol samples
Pb – – – GFAAS 0.01 ng mL−1 – Water and salt samples [63]
Pb Dithizone Triton X-114 At 0.5 mL with methanol GFAAS 0.089 ng mL−1 19.1d Water samples [64]
solution of 0.1 M HNO3
Pb 5-Br-PADAP Triton X-114 0.15 mL with methanol GFAAS 0.08 ng mL−1 50a Water samples [65]
solution of 0.1 M HNO3
Pb Without reagent PONPE 7.5 At 400 μL acetonitrile CZE with indirect UV 11.4 ng mL−1 25c Human saliva [66]
at 205 nm
Pb Brilliant cresyl blue Triton X-114 0.5 mL 1 M HNO3 in FAAS 7.5 ng mL−1 25d Sediment and [67]
methanol water samples
Pb PMBP Triton X-114 200 μL methanol FAAS 1.49 ng mL−1 110b Biological and water samples [68]
−1
Mn PAR or PAN OP-7 Distilled water FASS 5.0 ng mL 20c Natural water [69]
Mn PAN Triton X-114 400 μL of a solution of FAAS 0.39 ng mL−1 49.1c Milk and [70]
methanol with 0.1 M water samples
HNO3
Mn PMBP Triton X-100 500 μL of a solution of FAAS 1.45 ng mL−1 20c Natural water samples [71]
methanol with 0.1 M
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview

HNO3
Mn TAR Triton X-114 500 μL methanol in FAAS 0.60 ng mL−1 84b Saline effluents of a petroleum [72]
1% (v/v) HNO3 refinery
Mn Br-TAO Triton X-114 Sulfuric acid as eluent FAAS 0.5 ng mL−1 14b Food samples [73]
−1
Mn PMBP – – GFAAS 0.02 ng mL 31d Speciation of Mn(II) and Mn [74]
(VII) in water samples
Hg Dithizone Triton X-100 – UV/vis spectropho- 14 ng mL−1 6a Natural water samples [75]
tometry at 500 nm
Hg APDC Triton – HPLC coupled on-line 2–9 ng L−1 (as Hg) 29c MeHg Speciation in fish samples [76]
X-114 with CV-AFS
763
Table 1 (continued)
764

Ion Reagent Micellar SRP diluting agent Detection system DL PF Matrix Reference
system

43c EtHg
80c PhHg
98c Hg(II)
−1
Hg – Hydride generation 0.039 ng mL 20d Natural water samples [77]
AAS
Hg Iodide Triton X-114 500 μL ethanol UV/vis spectrophoto 3.0 (UV) 10c Water samples [78]
metry at 300 nm
and CV-AAS
0.1 (CV-AAS) ng mL−1
Hg DDTC Triton X-100 – UV/vis 0.53 ng mL−1 – – [79]
spectrophotometry
Hg DDTP Triton X-114 500 μL solution of CV-AAS 0.4 ng g−1 10b 3 certified reference samples [80]
methanol with of biological origin
0.1 M HNO3
Hg I− and MG for Hg2+ Triton X-114 0.5 mL with 0.5 M HNO3 ICP-AES 56.3 ng L−1 Hg(II) 18.7b Hg(II) Speciation in seafood [81
APDC for MeHg+ 94.6 ng L−1 MeHg 10.3b
MeHg
Hg PAN Triton X-114 150 µL 0.1% l-cysteine CE with UV detection 45.2 ng mL−1 EtHg 17c EtHg 15c Speciation in spiked natural [82]
at 210 nm 47.5 ng mL−1 MeHg MeHg 45c water and tilapia muscle
4.1 ng mL−1 PhHg PhHg 52c samples
10.0 ng mL−1 Hg(II) Hg(II)
(as Hg)
Hg 5-Br-PADAP PONPE 7.5 1.0 mL methanol with GFAAS 0.01 ng mL−1 22b Biological samples and CRM [83]
0.1 M HNO3 QC METAL LL3
Hg DDTC Triton X-114 500 µL methanol HPLC-ICP-MS 13 ng L−1 MeHg 8 ng 18c MeHg Speciation in environmental [84]
L−1 PhHg 6 ng L−1 Hg 46c PhHg water samples and biological
(II) (as Hg) 57c Hg(II) samples of human hair and
ocean fish
Mo 8-HQ Triton X-100 200 µL water ID-ICP-MS 0.8 ng g−1 70c Plants [85]
−1
Mo Bromopyrogallol CTAB 500 µL dimethylformamide UV/vis spectropho- 0.1 ng mL 20c In steels and water samples [86]
red tometry at 576 nm
Ni Br-PADAP Triton X-114 300 μL methanol with 1% FAAS 0.2 ng mL−1 74b Saline effluents from oil [87]
HNO3 refinery samples
Ni PMBP Triton X-100 300 μL methanol with GFAAS 0.12 ng mL−1 27a Water samples [88]
0.1 M HNO3
Pd TMK Triton X-114 At 1.0 mL with methanol UV/vis spectropho- 0.47 ng mL−1 50c Water samples [89]
tometry at 508 nm
Pt 6,5,3(2)-NMIOHCA Triton X-114 600 μL methanol with FASS 0.065 ng mL−1 81b Vegetable, soil and water [90]
0.1 M HNO3 samples
Rh 2-PPC Triton X-114 300 μL methanol with FAAS 0.052 ng mL−1 50c Water samples [91]
0.1 M HNO3
Rh PAN Triton X-114 20 µL carbon tetrachloride TLS 0.06 ng mL−1 450b Water samples [92]
C.B. Ojeda, F.S. Rojas
Table 1 (continued)

Ion Reagent Micellar SRP diluting agent Detection system DL PF Matrix Reference
system

Se APDC Triton X-114 200 µL methanol ETV-ICP-MS 8.0 ng L−1 39a Water samples [93]
−1
Ag BMAA Triton X-114 300 μL methanol with FAAS 0.43 ng mL 50b Water samples [94]
0.1 M HNO3
Ag DDTP Triton X-114 – GFAAS 7.8 ng L−1 35d CRM [95]
Ag TAN and TAR PO-7 At 1 mL with distilled water GFAAS – – Mineral water [96]
Ag MBT Triton X-114 300 μL methanol with FAAS 2.2 ng mL−1 46b Water samples [97]
0.1 M HNO3
Ag Without reagent PONPE 7.5 At 250 µL with methanol/ GFAAS 1.2 ng L−1 60b Water samples [98]
water (3:1) solution
Ag Dithizone Triton X-114 – FAAS 0.7 ng mL−1 38b Water samples [99]
−1
Ag Cu–DDTC Triton X-114 10% HNO3 and 20% TS-FF-AAS 0.2 ng mL 21b Soil, marine sediment, [100]
methanol to 600 µL and ore samples
Tl DTPA Triton X-114 and – ICP-MS 0.02 pg mL−1 125c Speciation in environmental [101]
SDS waters
Sn 8-HQ Triton X-114 100 μL methanol with 1% GFAAS 0.012 ng mL−1 96.2c Water samples [102]
HNO3
Sn PAN Triton X-100/ 200 µL 2.0 M HNO3 GFAAS 0.51 ng mL−1 50c Speciation in water samples [103]
SDS/NaCl
Sn α-Polyoxometalate Triton X-100/ 300 µL dimethylformamide FAAS 12.6 ng mL−1 Sn(IV) 100a Alloy, juice fruit, tape and [104]
CTAB 8.4 ng mL−1 Sn(II) waste water samples
U DMB Triton X-114 At 1 mL with methanol UV/vis spectropho- 11 ng mL−1 62b Water samples [105]
tometry at 400 nm
U Br-PADAP Triton X-114 700 µL ethanol UV/vis spectropho- 0.15 ng mL−1 50.4b Water samples [106]
tometry at 577 nm
U Pyrocatechol violet Triton X-114/ 500 µL dimethylformamide UV/vis spectropho- 0.06 ng mL−1 286b Water samples [107]
with potassium CTAB tometry at 690 nm
iodide
V PAN/H2O2 Triton X-100 300 μL methanol with FAAS 0.6 ng mL−1 79b Water samples [108]
0.1 M HNO3
V Methylene blue Triton X-100 500 μL 2 M HNO3 GFAAS 0.7 ng mL−1 10c Soil samples [109]

AAS atomic absorption spectrometry, AES atomic emission spectrometry, AFS atomic fluorescence spectrometry, APDC ammonium pyrrolidine dithiocarbamate, BMAA bis(2-mercaptoanil)
acetylacetone, 4-BPDC 4-bencylpiperidineditiocarbamate, BPHA N-benzoyl-N-phenyhydroxylamine, 5-Br-PADAP 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol, Br-PF dibromophenylfluor-
one, Br-TAO (5′-bromo-2′-thiazolylazo)orcinol, CAS chrome azurol S, CE capillary electrophoresis, CRM certified reference material, CTAB cetyltrimethylammonium bromide, CV cold vapour,
CZE capillary zone electrophoresis, DDTC diethyldithiocarbamate, DDTP O,O-diethyldithiophosphate, DL detection limit, DMB dibenzoylmethane, DTPA diethylenetriaminepentaacetic acid,
EtHg ethylmercury, ETV electrothermal vaporization, FAAS flame atomic absorption spectrometry, FF flame furnace, GBHA glyoxal bis(2-hydroxyanil), GFAAS graphite furnace atomic absorption
spectrometry, HEPTS 4-ethyl-1-(pyridin-2-yl)thiosemicarbazide, HPLC high-performance liquid chromatography, 8-HQ 8-hydroxyquinoline, ICP inductively coupled plasma, ID isotope dilution,
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview

MBT 2-mercaptobenzothiazole, Me-BDBD 6-[2′-(6′-methyl-benzothiazolylazo)]-1,2-dihydroxy-3,5-benzenedisulfonic acid, Me-BTABr 2-[2′-(6-methyl-benzothiazolylazo)]-4-bromophenol, MeHg

methylmercury, MG methyl green, MS mass spectrometry, NDTT 6-(2-naphthyl)-2,3-dihydro-as-triazine-3-thione, 6,5,3(2)-NMIOHCA 6-nitro-5-methoxy-3-(indoline-2-one) hydrazine
carboxyamide, n-TBHA n-p-tolylbenzohydroxamic acid, PAN 1-(2-pyridylazo)-2-naphthol, PAR 4-(2-pyridylazo)resorcinol, PF preconcentration factor, PhHg phenylmercury, PMBP 1-phenyl-
3-methyl-4-benzoyl-5-pyrazolone, PONPE 7.5 polyethylene glycol mono-p-nonylphenyl ether, 2-PPC 2-propylpiperidine-1-carbothioate, PTU 4-hydroxy-2-mercapto-6-propylpyrimidine, SDS
sodium dodecyl sulfate, SRP surfactant-rich phase, STPF stabilized-temperature platform furnace, TAR 2-(2′-thiazolylazo)resorcinol, TLS thermal lens spectrometry, TMK thio-Michler’s ketone, TS
thermospray, TTA thenoyltrifluoracetone, WCAAS tungsten coil atomic absorption spectrometry
a
Calculated as the ratio of the analytical signal of the preconcentrated sample to that obtained without preconcentration
b
Calculated by dividing the slope of the calibration curve after preconcentration by that obtained without preconcentration
c
Calculated as the ratio of concentration of the analyte in the final surfactant-rich phase to that in the initial solution
d
No definition available
765
766
CPE, using molybdate as a complexing agent and Triton
X-114, was applied for determination of As(III) and As(V)
in tap water and total arsenic in biological samples by
GFAAS in the presence of Pd(NO3)2 as a modifier after
CPE [17]. As(V) with molybdate forms a yellow complex
in sulfuric acid medium. Total inorganic As(III, V) was
extracted similarly after oxidation of As(III) to As(V) with
KMnO4. The As(III) content was calculated by difference.
Beryllium
Beiraghi et al. [18, 19] described two methods for the
preconcentration and determination of beryllium by spec-
trophotometry based on CPE of a complex of beryllium
with chrome azurol S [18] or 1,8-dihydroxyanthrone
(anthralin) [19] in water samples using the mixed micelle
mediated extraction method. A comparison of these
methods with previously reported methods for the precon-
centration and spectrophotometric determination of berylli-
um indicates that these methods are faster and simpler than
the other methods. Later, the same group reported a highly
selective, sensitive, and accurate method based on mixed-
micelle-mediated extraction coupled with ICP-AES for
beryllium determination using anthralin at nanogram per
litre levels in water samples [20].
Bismuth
Shemirani et al. [21] and Moghimi [22] proposed the use of
CPE as an alternative method for the preconcentration of
bismuth as a prior step to its determination by GFAAS; the
aqueous analyte was previously acidified with sulfuric acid
(pH 3.0–3.5). The methods allow the determination of
ultralow levels of bismuth.
CPE followed by spectrophotometric determination of
bismuth was described by Afkhami et al. [23]. The micellar
extract from this procedure was diluted with 0.3 mL of
methanol and transferred into a 0.5-mL quartz cell to
measure its absorbance at 542 nm.
Cadmium
Although higher temperatures are commonly applied to
attain the cloud point, other conditions, such as pressure or
the use of additives (including electrolytes), are possible.
These strategies permit the cloud point to be attained at
room temperature, with inherent advantages for the process.
In this way, Coelho and Arruda [25] investigated a cloud
point separation induced by NaCl for cadmium extraction/
preconcentration. The cadmium determination was carried
out in different samples after complexation with ammonium
O,O-diethyldithiophosphate (DDTP) in an acidic medium
(0.32 M HCl), using Triton X-114 as a non-ionic surfactant
C.B. Ojeda, F.S. Rojas
and the salting-out effect for lowering the cloud point. The
cloud point induced by NaCl, which was formed at room
temperature (25 °C), led to a more versatile routine
procedure with a significant saving of time, which was
successfully applied for cadmium preconcentration before
determination by FAAS.
Liang et al. [26] optimized the use of PMBP in CPE and
assessed its application to the preconcentration of cadmium
prior to FAAS using Triton X-100 as a surfactant. Afkhami
et al. [27] reported the results obtained in a study of the
CPE of cadmium, after the formation of a complex with
iodide using Triton X-114 as a surfactant followed by
analysis by FAAS.
In the investigation presented by Wu et al. [28], the aim
was to further improve the performance of thermospray
flame furnace AAS (TS-FF-AAS) by using CPE as a
preconcentration method for the determination of ultratrace
cadmium. CPE using Triton X-114 and APDC has been
shown to be an efficient yet simple technique for cadmium
preconcentration, and it can be easily coupled to flame
furnace AAS for the highly sensitive determination of
cadmium at ultratrace levels. The surfactant also helps clean
the capillary during the sampling and results in no memory
effect. With the low cost and easily available accessories,
the detectability of a traditional FAAS instrument can be
comparable to that of more sophisticated instruments, such
as GFAAS instruments.
Manzoori et al. [29] developed and optimized a powerful
CPE–cold vapour (CV)–AAS combined method for cad-
mium determination, and it showed excellent and rapid
preconcentration. Cadmium preconcentration was mediated
by polyethylene glycol mono-p-nonylphenyl ether (PONPE
7.5) in the absence of any chelating agent, and later its
determination was performed through CV generation from
the surfactant-rich phase at room temperature using a
continuous flow system coupled to an AAS system.
The work described by Donati et al. [33] is the first
application of a combined CPE and tungsten coil AAS
method. The CPE step reduces the tungsten coil AAS
detection limit to the point where normal urine cadmium
levels may be detected. At the same time, the urine matrix
is reduced and simple background correction techniques
may be employed.
Filik et al. [34] reported the results obtained in a study
of the CPE of cadmium, after the formation of a complex
with glyoxal bis(2-hydroxyanil), and subsequent analysis
by GFAAS using a Triton X-114/SDS mixture as the
surfactant.
Cerium
Shemirani and Yousefi [36] reported the results obtained in
a study of the CPE and preconcentration of Ce(IV), after
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview
the formation of a complex with n-p-tolylbenzohydroxamic
acid, and later analysis by ICP-AES at a wavelength of
318.659 nm, using Triton X-114 as a surfactant. The
method applied significantly widened the ICP application
because it increased the detection power such that cerium
at the microgram per litre level could be accurately
determined.
Chromium
Tang et al. [38] applied CPE as a preconcentration step for
high performance liquid chromatography (HPLC) specia-
tion of chromium. In the system developed, diethyldithio-
carbamate (DDTC) was used as the chelating agent and
Triton X-114 as the extractant. Potential factors affecting
the CPE preconcentration and the subsequent HPLC
separation of the DDTC chelates of Cr(III) and Cr(VI)
were investigated in detail by the authors.
First, Zhu et al. [111] reported a CPE method for the
separation/preconcentration of Cr(III) and Cr(VI) in water
samples after formation of a Cr(III) complex with 8-
hydroxyquinoline (8-HQ). Cr(III) in a surfactant-rich phase
and total chromium were then determined by electrothermal
AAS (ETAAS). Second, the same group realized another
study, the purpose of which was to combine CPE with
ETAAS for the speciation of chromium at trace levels in
cigarettes samples, and to explore the most efficient
extractants for chromium and chromium species [112].
Different extractants were tested for the analytes from the
samples and tetramethylammonium hydroxide was found to
be a very effective extraction reagent for chromium species
in cigarettes and cigarette ash. Later, a method for ETAAS
speciation of chromium in environmental water samples
was proposed by the same authors using CPE with
dibromophenylfluorone (Br-PF) as the chelating agent and
Triton X-100 as the extractant. Under the optimal con-
ditions, the Cr(VI)–Br-PF complex formed was ‘in situ’
entrapped in a surfactant-rich phase at a temperature higher
than the cloud point temperature and separated from Cr(III)
in the aqueous phase [40].
A method combining CPE with ETV-ICP-AES for the
speciation of chromium in environmental water samples
was proposed by Li et al. [41]. Thenoyltrifluoracetone
(TTA) was employed not only as a chelating agent in CPE
but also as a chemical modifier in ETV-ICP-OES. The main
factors affecting CPE and the vaporization behaviour of the
analyte in graphite tubes were investigated in detail. The
advantages of the proposed method are summarized as
follows: (1) the CPE is characterized by simplicity,
selectivity, safety, low cost, and high preconcentration
factor; and it is suitable for the speciation of trace
chromium in environmental water samples; (2) the Cr
(III)–TTA chelate can be vaporized rapidly in the graphite
767
furnace at the low temperature of 1,300 °C, the formation
of refractory carbides of chromium can be effectively
prevented, and the lifetime of the graphite tube prolonged;
(3) by combining CPE with low-temperature ETV-ICP-
OES, one can achieve a much lower detection limit.
Recently, bis(2-hydroxy-1-naphthaldehyde) thiourea, a
novel reagent, was used in a CPE method for the estimation
of chromium species in different environmental samples
[44]. The method was employed for the determination of Cr
(III) in water samples collected from industrial areas, and
this was followed by their determination with FAAS.
Also, the feasibility of chromium speciation in water has
been demonstrated using CPE of Cr(III) with PMBP in the
presence of the surfactant Triton X-114 and sequential
determination by GFAAS [45]. The method is definitely
simple, reproducible, and highly sensitive because of the
distinct and advantageous features of CPE (in situ and
single-step extraction).
Sun and Liang [46] applied CPE as a separation and
preconcentration step combined with FAAS for the speci-
ation of chromium. In the CPE method, Cr(III) reacts with
acetylacetone yielding a hydrophobic complex, which is
entrapped in the Triton X-100 surfactant-rich phase,
whereas Cr(VI) remains 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)
using ascorbic acid as the reducing reagent.
Cobalt
TS-FF-AAS, cobalt derivatization, and CPE were combined
for cobalt determination in foods [48]. Sample preparation
was performed using a procedure based on extraction with
a dilute HCl solution. The procedure is fast and simple and
improves the performance of FAAS for trace analysis. The
implementation of APDC derivatization and CPE steps led
to a gain of about 200-fold in TS-FF-AAS sensitivity, and
these steps were fundamental for cobalt determination in
food samples.
Shemirani and Shokoufi [49] combined thermal lens
spectrometry (TLS), as a highly sensitive method, with
CPE. This combination is favourable because TLS is
suitable for the low volume of sample obtained after CPE
and for organic solvents used to dissolve the remaining
analyte phase (organic solvents enhance the thermal lens
effect in comparison with aqueous media). CPE using 1-(2-
pyridylazo)-2-naphthol (PAN) as a complexing agent and
the non-ionic surfactant Triton X-114 was applied for
separation and preconcentration of cobalt.
A method for cobalt preconcentration by CPE with on-
line phase separation in a polytetrafluoroethylene (PTFE)
knotted reactor (KR) and further determination by GFAAS
was proposed by Gil et al. [50]. This method was associated
768
with GFAAS determination with a stabilized-temperature
platform furnace by mounting the KR in the arm of the
autosampler. One of the most distinct features of this
method is the use of a KR for the on-line retention of the
analyte-entrapped micelles, greatly simplifying the system
design by avoiding the need for a heating device and a
salting-out agent for phase separation. Another important
feature is that all operations for the micelle-mediated
preconcentration are performed in on-line mode.
Copper
Lemos et al. [52] described a CPE for copper by the use of
2-[2′-(6-methyl-benzothiazolylazo)]-4-bromophenol
reagent as a complexing agent prior to FAAS determination
of this metal. The procedure improved significantly the
performance of the FAAS detection. Also, a micelle-
mediated phase separation using Triton X-114 was applied
for preconcentration of copper, by formation of a complex
with 6-(2-naphthyl)-2,3-dihydro-as-triazine-3-thione
reagent, and its analysis by FAAS [53]. This method
permits analysis and quantification of Cu(II) at nanogram
per millilitre levels. In other work, the reagent 1,5-
diphenylbenzoin (Cupron) was used as a complexing agent
and Triton X-114 was added as a surfactant [54]. After
phase separation, dilution of the surfactant-rich phase was
carried out using acidified methanol and the copper content
was subsequently measured by FAAS.
4-Ethyl-1-(pyridin-2-yl)thiosemicarbazide has been used
as a new complexing agent in CPE for preconcentration and
spectrophotometric determination of trace amounts of
copper in saturated saline medium [55].
Azevedo et al. [56] developed a CPE method for copper
using 6-[2′-(6′-methyl-benzothiazolylazo)]-1,2-dihydroxy-
3,5-benzenedisulfonic acid as a complexing agent prior to
FAAS determination. The optimization step of the CPE
system’s variables was performed using a factorial design
and a Doehlert matrix.
Results obtained from application of the CPE-
spectrofluorimetric method for the determination of copper
were reported by Tabrizi [58]. The method is based on
chemical oxidation of thiamine to thiochrome by using Cu
(II), extraction of thiochrome into non-ionic micelles, and
its determination by spectrofluorimetry.
Gold
Manzoori et al. [61] developed and optimized a simple and
powerful combined CPE-GFAAS method for gold determi-
nation which shows rapid preconcentration and excellent
selectivity. Gold preconcentration was mediated by PONPE
7.5 in the absence of any chelating agent, and gold was then
determined by GFAAS. To reduce interferences and
C.B. Ojeda, F.S. Rojas
increase the accuracy, the use of a chemical modifier or a
modifier mixture has become indispensable in GFAAS
measurements. In this study, a palladium modifier was used
in all experiments. The proposed procedure does not need
any chelating agent, heating, long incubation time, or
cooling after centrifugation. Phase separation can be
achieved at room temperature, and the extraction efficiency
is high, resulting in low detection limits and high
enhancement factors.
Lead
Chen et al. [65] reported the results obtained in a study of
the CPE of lead, after the formation of a complex with
2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (5-Br-
PADAP), and later analysis by GFAAS using Triton X-
114 as the surfactant. The surfactant-rich phase can be
easily introduced into the graphite furnace by an
autosampler after dilution with methanol and lead can
be directly detected by GFAAS.
Luconi et al. [66] coupled an enrichment step mediated
by micelles of PONPE 7.5 with capillary zone electropho-
resis (CZE) with indirect UV detection for the separation
and determination of lead in saliva. The results from this
work demonstrated the feasibility of coupling a cloud point
preconcentration step without added chelating reagents with
CZE with indirect detection. Substantial improvements
were attained with this method compared with published
reports for lead determination by capillary electrophoresis
(CE) in terms of simplicity and sensitivity.
PMBP was used as a chelating agent in CPE for the first
time and was applied for the preconcentration of trace
levels of lead as a step prior to its determination by FAAS
[68]. The stability of PMBP and its complex with lead
allow the surfactant-rich phase to be dried after CPE, which
removes the remaining water and leads to a high enhance-
ment factor.
Manganese
The possibility to use 4-(2-pyridylazo)resorcinol and PAN
for Mn(II) concentration by CPE using OP-7 and subse-
quent AAS determination was investigated by Doroschuk et
al. [69]. On the basis of the results obtained, the more
effective manganese extraction should be expected with
PAN owing to its better hydrophobic and amphiphilic
properties compared with those of 4-(2-pyridylazo)resor-
cinol,and the use of the non-ionic surfactant OP-7 for
extraction allows the surplus step of centrifugation of
solutions after phase separation to be avoided. Later, a
similar method for the cloud point preconcentration of
manganese in milk and water samples, using PAN as the
complexing agent and Triton X-114 as the surfactant, was
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview
studied by Rod et al. [70]. Also, Sun et al. [71] optimized
the use of PMBP in CPE preconcentration of Mn(II)
prior to FAAS determination using Triton X-100 as the
surfactant.
Bezerra et al. [72] described the development of a
preconcentration procedure for the determination of man-
ganese in saline effluents of a petroleum refinery by FAAS
based on CPE using 2-(2′-thiazolylazo)resorcinol as the
complexing reagent and Triton X-114 as the surfactant, and
the optimization step was performed using the Doehlert
design, which allowed rapid and efficient optimization of
the chemical and operational variables of the proposed
procedure.
Recently, Azevedo et al. [73] reported the development
of a new on-line CPE system with sequential injection for
FAAS determination of trace manganese in food samples. A
thiazolylazo dye—4-(5′-bromo-2′-thiazolylazo)orcinol—
was prepared for the first time for this application. The
study of variables affecting the on-line system was followed
by application of the procedure in the determination of
manganese in food. No reports on CPE on-line systems
with sequential injection were found in the literature. The
significant features of this method are the simple frequency
and the consumptive index obtained by using the on-line
system, and another interesting feature is the low sample
volume required.
Mercury
Hg(II) is considered a chemical pollutant and although it is
found at low concentration, its toxicity can be dangerous.
On the other hand, CPE has been shown to be an effective
sample pretreatment approach for improving sensitivity and
selectivity prior to flow injection analysis (FIA). In this
way, an automated method for spectrophotometric determi-
nation of Hg(II) in water samples was proposed by Garrido
et al. [75]. With the FIA system developed it was possible
(1) to carry out the pretreatment of the sample on-line to
eliminate Fe(III) interference, (2) to prepare the reagent
(dithizone) on-line by using a solid reagent column, (3) to
preconcentrate the analyte on-line by using a continuous
CPE, and (4) to obtain a spectrophotometric signal of the
analyte for its quantification. The use of Triton X-100 as a
solvent for the preparation of the dithizone reagent was an
important advantage because this surfactant was also used
for cloud point formation. The surfactant-rich phase
containing the complex was collected in a minicolumn
packed with cotton wool; then, a hot water stream was
passed through the column to elute the complex.
A CPE method was developed by Yu [76] for simulta-
neous preconcentration of Hg(II), methylmercury (MeHg),
ethylmercury (EtHg), and phenylmercury (PhHg) prior to
reversed-phase HPLC coupled on-line with CV atomic
769
fluorescence spectrometry (AFS) for speciation analysis of
mercury in fish. The CPE technique described in this work
overcomes several problems and interferences encountered
in the determination of these species by creating stable
micelles and offers a simple, sensitive, and inexpensive
alternative to other preconcentration techniques prior to
HPLC hyphenated with element-specific detectors for
mercury speciation. Baseline separation of the enriched
complexes was achieved on an RP-C18 column with a
mixture of methanol, acetonitrile, and water (65:15:20)
containing 200 mmol L−1 HAc (pH 3.5) as the mobile
phase. An on-line postcolumn oxidation of the effluent
from HPLC, in the presence of K2S2O8 in HCl, was applied
in the system, followed by an optimal CV generation of
mercury species.
CPE with salt-induced phase separation using Triton X-
114 and DDTP was demonstrated for the determination of
mercury in certified reference samples of human hair,
dogfish liver, and dogfish muscle using CV-AAS after the
addition of sodium borohydride as the reducing agent [80].
CV-AAS in association with CPE was shown to be a highly
efficient procedure to determine mercury in biological
samples subjected to microwave-assisted acid digestion
owing to its simplicity, low cost, and sensitivity. The
possibility to analyse samples of very different nature and
the low detection limit obtained owing to the high
efficiency of the preconcentration procedure are valuable
parameters, and they facilitate considerably the difficult
task of determining mercury in biological samples. Phase
separation induced by the addition of Na2SO4 has also
proved to be effective, avoiding possible losses of mercury
due to heating, as is applied in most CPE procedures.
Li and Hu developed [81] a non-chromatographic
speciation technique sequential to CPE for the speciation
of mercury in seafood by ICP-AES. The method involves
the usage of Triton X-114 as the extractant for selective
extraction of a methyl green–Hg(II)–I− associated complex,
which is subsequently separated from MeHg+ in the initial
solution and then determined by ICP-AES. The supernatant
is subjected to a CPE procedure similar to that for the
determination of MeHg+ with the addition of a chelating
agent, APDC, to form a water-insoluble complex with
MeHg+. The APDC complex of MeHg+ was extracted in
the micelles and directly analysed by ICP-AES.
A dual-CPE (dCPE) technique was proposed by Yin [82]
for the sample pretreatment of CE speciation analysis of
mercury. In dCPE, CPE was carried out twice in a sample
pretreatment. First, four mercury species, MeHg, EtHg,
PhHg, and inorganic mercury [Hg(II)], formed hydrophobic
complexes with PAN. After heating and centrifugation, the
complexes were extracted into the Triton X-114 surfactant-
rich phase that formed. Instead of the direct injection or
analysis, the surfactant-rich phase containing the four
770
mercury species was treated with 150 µl 0.1% (m/v) l-
cysteine aqueous solution. The four mercury species were
then transferred back into the aqueous phase by forming
hydrophilic mercury–l-cysteine complexes. After dCPE, the
aqueous phase containing the mercury–l-cysteine com-
plexes was injected into the electrophoretic capillary for
mercury speciation analysis. Because the concentration of
Triton X-114 in the extract after dCPE was only around the
critical micelle concentration, the adsorption of surfactant
on the capillary wall and its possible influence on the
sample injection and separation in traditional CPE were
eliminated. Plus, the hydrophobic interfering species were
removed thoroughly by using dCPE, resulting in significant
improvement in analysis selectivity.
Recently, CPE preconcentration of ultratrace amounts of
mercury species prior to reversed-phase HPLC with ICP-
MS detection was studied by Chen et al. [84]. Mercury
species, including MeHg, EtHg, PhHg, and inorganic
mercury, were transformed into hydrophobic chelates by
reaction with sodium diethyldithiocarbamate, and the
hydrophobic chelates were extracted into a surfactant-rich
phase of Triton X-114. The separation of the concentrated
DDTC chelates of mercury species by reversed-phase
HPLC requires an eluant containing as much as 75%
organic solvent to elute all the DDTC chelates within
15 min. Consequently, special measures such as high
plasma forward power, cooling spray chamber, and
oxygen-containing optional gas flow are required for
stabilization of the ICP discharge when the high-solvent
eluant is introduced directly into the ICP-MS system.
Molybdenum
CPE of molybdenum in plant digests labelled with 98Mo
and quantification by isotope dilution ICP-MS was pro-
posed by Bellato et al. [85]. Recently, Madrakian and
Ghazizadeh [86] proposed a method for preconcentration
and determination of molybdenum by spectrophotometry
based on CPE of the complex of Mo(VI) with bromopyr-
ogallol red in the presence of potassium iodide in pH 1.0
glycine/HCl buffer in surfactant media. This procedure
gives a simple, very sensitive, and low-cost spectrophoto-
metric procedure for determination of molybdenum ion that
can be applied to real samples.
Nickel
Bezerra et al. [87] proposed a preconcentration procedure
for determination of nickel in saline aqueous waste samples
by FAAS. It is based on the CPE of Ni(II) ions as Br-
PADAP complexes using Triton X-114 as the surfactant.
The optimization step was carried out using a four-variable
Doehlert design that enabled rapid and efficient optimiza-
C.B. Ojeda, F.S. Rojas
tion of the chemical and operational variables of the
procedure. This procedure is sufficiently accurate and
precise for determination of nickel in saline effluents from
oil-refinery samples. The detection limit, precision, and
preconcentration factor of the procedure are comparable
with those of other preconcentration systems which use
CPE as a separation technique.
Palladium
Shemirani et al. [89] reported results obtained in a study of
the CPE of palladium, after the formation of a hydrophobic
complex with thio-Michler’s ketone, 4,4′-bis(dimethyla-
mino)thiobenzophenone; the separation occurred efficient-
ly, resulting in a good enrichment factor and low detection
limit.
Platinum
A novel reagent, 6-nitro-5-methoxy-3-(indoline-2-one) hy-
drazine carboxyamide, was synthesized by Rekha et al. [90]
for the determination of platinum in environmental samples
using CPE.
Rhodium
Another novel reagent, 2-propylpiperidine-1-carbothioate,
was synthesized for the CPE of rhodium from various water
samples [91]. The method was based on the complexation
of rhodium with 2-propylpiperidine-1-carbothioate in the
presence of Triton X-114 at pH 8.0 using either HCl or
NaOH.
A new combination method, employing TLS after CPE,
was developed for the preconcentration and determination
of rhodium by Shokoufi and Shemirani [92]. TLS and CPE
methods have good matching conditions for the combina-
tion because TLS is a suitable method for the analysis of
the low-volume samples obtained after CPE. This combi-
nation method exhibits a high enhancement factor as a
result of the preconcentration enhancement factor in CPE
and the enhancement factor of organic solvent effects in
TLS.
Selenium
A method based on CPE separation and ETV-ICP-MS
detection has been proposed for the speciation of inorganic
selenium in environmental waters [93]. APDC was used as
a chelating agent in CPE and a chemical modifier in ETV-
ICP-MS. The Se(IV)–APDC complex can be vaporized
rapidly in the graphite furnace at the low temperature of
1,200 °C, the formation of refractory carbides of selenium
can be effectively prevented, and the lifetime of the
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview
graphite tube can be prolonged. A much lower limit of
detection can be achieved by combining CPE with low-
temperature ETV-ICP-MS.
Silver
A method for the CPE of silver in water samples employing
bis(2-mercaptoanil) acetylacetone as a complexing agent
and Triton X-114 as a surfactant was developed by
Shemirami et al. [94]. The results demonstrate the useful-
ness of the CPE system for the quantitative extraction and
preconcentration of the silver–Schiff’s base complex.
Recently, a CPE method was incorporated into a flow
injection system, coupled with FAAS, for determination of
trace amounts of silver. The analyte in the aqueous solution
was acidified with 0.2 M sulfuric acid and complexed with
dithizone [99]. After the cloud point had been obtained, the
surfactant-rich phase containing the dithizonate complex
was collected in a minicolumn packed with cotton wool.
Then the complex was eluted by passing tetrahydrofuran
through the column and the silver content was determined
by FAAS.
A novel displacement-CPE approach was developed for
the selective determination of trace silver in complicated
matrices by TS-FF-AAS [100]. This method involves two
steps of CPE: firstly, copper ion reacts with DDTC to form
Cu–DDTC before it is extracted; secondly, after the
aqueous phase has been removed, a sample or standard
solution containing silver ion is added and another CPE
procedure is carried out. Because the stability of Ag–DDTC
is greater than that of Cu–DDTC, Ag(I) can displace Cu(II)
from the pre-extracted Cu–DDTC and thus the preconcen-
tration and separation of Ag(I) from the complicated sample
matrix is achieved. Potential interference from coexisting
transition metal ions with lower DDTC complex stability
was largely eliminated as they cannot displace Cu(II) from
the Cu–DDTC complex. The most favourable feature of
this approach is its much higher selectivity over a
conventional CPE procedure.
Thallium
A novel sequential mixed-micelle CPE procedure was
developed for ultratrace speciation analysis of thallium in
environmental water samples by 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.
The Tl(III)–diethylenetriaminepentaacetic acid complex in
an HCl medium is 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. Ultrasonically assisted back-extraction is used to
extract the Tl(III) species from the surfactant-rich phase
771
into a small volume of aqueous l-cysteine [101]. This
procedure utilizes the advantages of mixed micelles,
avoiding the addition of chelating agent as well as external
electrolytes. This has provided good a preconcentration
factor, phase volume ratio, and detection limit.
Tin
Yuan et al. [102] developed a method for the preconcentra-
tion and determination of trace tin by using GFAAS with
CPE. During the procedure, 8-HQ was used as the chelating
reagent. After CPE, tin in samples was separated from the
matrix and preconcentrated with a high enrichment factor.
With use of the matrix modifier (palladium–magnesium
nitrate) and a zirconium-coated graphite tube, this method
was applied to the determination of trace tin in water
samples with satisfactory recoveries.
Zhu et al. [103] combined CPE with GFAAS for the
speciation analysis of inorganic tin in environmental water
samples. PAN, as the chelating agent, and the mixed
surfactant system of Triton X-100/SDS/NaCl as the
extractant were used in CPE. When the system temperature
was higher than the cloud point temperature of the
surfactant mixture, the complex of Sn(IV) with PAN 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 realized.
The CPE behaviour of Sn(II) and Sn(IV) using α-
polyoxometalate and mixed surfactants solution was re-
cently investigated by Gholivand et al. [104]. The mixture
of a nonionic surfactant and a cationic surfactant was
utilized as a suitable micellar medium for preconcentra-
tion and extraction of tin complexes. Sn(II) in the pres-
ence of Sn(IV) was extracted at pH 1.2, whereas pH 3.7
was used for the individual determination of Sn(II) and
Sn(IV) and also for total tin determination under the
same conditions.
Uranium
The possibility of using dibenzoylmethane for U(VI)
concentration by way of micellar extraction at the cloud
point temperature and later direct spectrophotometric
determination was investigated by Shemirani et al. [105].
This method allows the determination of parts per billion
levels of U(VI) by spectrophotometry. The main advantage
of the method is the use of dibenzoylmethane as a chelating
and chromogenic reagent for direct determination of U(VI)
in water samples in almost every laboratory.
Also, U(VI) can be extracted without using organic
solvents by CPE using Triton X-114 as a surfactant [113].
Addition of 8-HQ as a chelating agent to the system leads
to a decrease in the Triton X-114 concentration needed and
772
an increase in the concentration factor, varying from 9 to
100, depending on the Triton X-114 concentration and the
8-HQ to U(VI) molar ratio. The process consists of four
steps: (1) extraction of U(VI) into the micelles of a non-
ionic surfactant as a function of its association constants
with a chelating extractant, 8-HQ; (2) thermoinduced phase
splitting; (3) back-extraction of U(VI) from the surfactant-
rich phase using acidic solution; and (4) a second phase
splitting. The separation can be achieved using an 8-HQ to
U(VI) molar ratio of 10 at pH 4 and U(VI) can be stripped
with a dilute nitric acid solution (pH<1). The concentration
of uranium was determined by ICP-AES using lanthanum
as an internal standard.
Thermoresponsive metal-chelating surfactants permit the
solvent-free CPE of uranyl nitrate and afford a real
molecular economy compared with conventional separation
techniques [114]. In this work, an appropriate amount of
uranyl nitrate was added to 2 mL of a solution of surfactant
(0.04 M), lithium nitrate (4 M), and nitric acid (0.01 M) in
water. After homogenization, the cloud point was measured
and the solution was allowed to stand at 10 °C above the
cloud point temperature in a thermostated bath until phase
separation had been achieved (1–4 h). The surfactant- and
uranium-poor upper diluted phase was separated from the
coacervate (highly viscous) and the concentration of
uranium was measured by X-ray fluorescence spectroscopy.
Using CPE for two metals ions simultaneously
Table 2 summarizes the more important aspects of the
proposed procedures for two metal ions employing CPE.
Tabrizi [115] reported results obtained from applying
CPE for the extraction of aluminium and zinc from waters
and foodstuffs and their determination by spectrofluorim-
etry. Applying the CPE before spectrofluorimetric determi-
nation makes the method more advantageous when
compared with expensive and labour-intensive methods.
The simplicity, high efficiency, and low cost are the other
features of this method.
Li et al. [116] developed a method for simultaneous
speciation of inorganic selenium and antimony in water by
ETV-ICP-MS following selective CPE. The basis of the
method is the use of Triton X-114 for the selective
extraction of DDTC complexes of Sb(III) and Se(IV),
while Sb(V) and Se(VI) did not form DDTC complexes and
were not extracted by Triton X-114 as free species in the
solution. Thus, an in situ separation of Se(IV) and Se(VI),
and Sb(III) and Sb(V) could be realized. Sb(III) and Se(IV)
in the concentrate were determined by ETV-ICP-MS after
proper disposal. The total selenium and total antimony were
determined by the same protocol after Se(VI) and Sb(V)
had been reduced by l-cysteine, and Se(VI) and Sb(V)
concentrations were obtained by subtracting, respectively,
C.B. Ojeda, F.S. Rojas
the contents of Se(IV) and Sb(III) from the total selenium
and the total antimony.
A simultaneous preconcentration procedure using CPE
was proposed by Portugal et al. [119] for the determination
of cadmium and lead, employing fast sequential flame
atomic absorption spectrometry as the analytical technique.
The ligand was 2-(2-thiazolylazo)-p-cresol. The optimiza-
tion step was performed using a factorial design and a
Doehlert matrix. The fast sequential mode is a good
alternative for multielement determination using FAAS.
The limits of quantification obtained with this procedure
allow the determination of cadmium and lead in drinking
water samples.
Very recently, Silva and Roldan [121] developed a new
flow injection separation/preconcentration procedure in
combination with the CPE technique for lead and cadmium
determination by FAAS. Phase separation was performed
by using minicolumns packed with cotton, glass wool, or
TNT compresses, which were tested as filtering material for
effective retention of micellar aggregates. Operations
generally employed in bath CPE such as the heating of
micellar solutions in a thermostatic bath, the use of a
centrifuge and an ice bath, and the dilution of the
surfactant-rich phase were not necessary, so the proposed
procedure improved significantly the performance of bath
CPE methods.
The phase-separation phenomenon of non-ionic surfac-
tants occurring in an aqueous solution was used for the
extraction of cadmium and zinc from water samples [124].
After complexation with 6-(4-nitrophenyl)-2,4-diphenyl-
3,5-diaza-bicyclo[3.1.0]hex-2-ene in an HCl medium (pH
1), the analytes were quantitatively extracted after centrifu-
gation into the phase rich in the non-ionic surfactant.
The application of the CPE technique for CE determi-
nation of metal ions was demonstrated using Cu(II) and Co
(II) as model metal ions [126]. Baseline separation of the
PAN chelates of Cu(II) and Co(II) was realized by CE with
a photodiode-array detector in a 50 cm×75 µm inner
diameter fused-silica capillary at 17 kV. A 50 mM NH4Ac
buffer solution (pH 8.0) containing 0.2 mM PAN in 80%
(v/v) acetonitrile and 20% (v/v) doubly deionized water
was used as the separation medium to avoid the adsorption
of hydrophobic substances and the non-ionic surfactant
Triton X-114 onto the inner surface of the separation capil-
lary, ensuring the separation efficiency and reproducibility.
Safavi et al. [127] reported the results obtained in a study
of the CPE of cobalt and nickel, after the formation of a
complex with 2-amino-cyclopentene-1-dithiocarboxylic ac-
id, and later analysis by spectrophotometry at the wave-
length of maximum absorption of each complex. The
advantage of the method is that traces of nickel and cobalt
can be determine simultaneously without the need for a
chemometric method.
Table 2 CPE applications for two metals simultaneously

Ions Reagent Micellar SRP diluting agent Detection system DL PF Matrix Reference
system

Al 8-HQ Triton X-114 2.5 mL ethanol Spectrofluorimetry 0.79ng mL−1 Al 10c Foodstuffs and waters [115]
Zn at 512 and 500 nm 1.2 ng mL−1 Zn
with excitation
at 375 and 385nm,
respectively
Sb DDTC Triton X-114 100 µL ethanol ETV-ICP-MS 0.03 ng mL−1 50c Speciation in waters [116]
Se Sb 0.05 ng mL−1 Se
Cd DDTP Triton X-114 500 μL methanol with 0.1 M GFAAS 6 ng g−1 Cd 129b Biological samples [117]
Pb HNO3 40 ng g−1 Pb 18b
Cd DDTP Triton X-114 500 μL methanol with 0.1 M GFAAS 2 ng L−1 Cd 16b Urine samples [118]
Pb HNO3 40 ng L−1 Pb 16b
Cd TAC Triton X-114 300 μL methanol with 1% FS-FAAS 0.077 ng mL−1 Cd 22b Drinking waters [119]
Pb HNO3 1.05 ng mL−1 Pb 56b
Cd DDTP Triton X-114 – FAAS – – Natural waters [120]
Pb
Cd TAN Triton X-114 Stream of 3 M HCl FAAS 0.75 ng mL−1 Cd 20.3b Waters [121]
Pb 4.5 ng mL−1 Pb 15.1b
Cd Dithizone Triton X-114 200 µL tetrahydrofuran FAAS 0.31 ng mL−1 Cd 52b Waters [122]
Ni 1.2 ng mL−1 Ni 39b
Cd Schiff base benzylbis Triton X-114 Methanol with 0.1 M HNO3 FAAS 0.08 ng mL−1 Cd 140b Natural waters [123]
Ag (thiosemicarbazone) 0.04 ng mL−1 Ag 60b
Cd NDDBH Triton X-114 500 µL tetrahydrofur an with FAAS 0.33 ng mL−1 Cd 157c Mineral drinking water, [124]
Zn 0.1 M HCl 0.85 ng mL−1 Zn 118c river water, and seawater
Cr 5-Br-PADAP Triton X-114 300 µL HNO3 (1:1) GFAAS 23 ng L−1Cr 26.2b Vegetal samples [125]
Co 12 ng L−1 Co 41.0b
Co PAN Triton X-114 At 400 µL methanol CE 0.12 ng mL−1 Co 15.9c Tap and snow water [126]
Cu 0.26 ng mL−1 Cu 16.3c and flavour wines
Co ACDA Triton X-114 At 1 mL dimethylfor mamide UV/vis spectrophot 7.5 ng mL−1Co – Waters [127]
Ni ometry at 452 and 10 ng mL−1 Ni
534 nm for Co
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview

and Ni
Co PAN Triton X-114 50 µL ethanol (at pH 5) FO-LADS 2 ng mL−1 Co 198b Tap, river, and dispenser [128]
Ni 0.04 ng mL−1 Ni 199b water (for drinking),
saline serum and dextrose
serum (for injection)
and synthetic sample
Co Me-BTABr Triton X-114 200 µL methanol with 1 M FAAS 0.9 ng mL−1 Co 28b Water and CRM, NIST [129]
Ni HNO3 1.1 ng mL−1 Ni 23b 1570a spinach leaves
Cu Pyrogallol Triton X-114 800 μL methanol with 0.1 M FAAS 0.05 ng mL−1 Cu 85c Waters [130]
Pb HNO3 0.4 ng mL−1 Pb 72c
773
Table 2 (continued)
774

Ions Reagent Micellar SRP diluting agent Detection system DL PF Matrix Reference
system

Cu H2mdo Triton X-114 500 μL methanol with 0.1 M FAAS 0.14 ng mL−1 Cu 65a Waters [131]
Ni HNO3 0.2 ng mL−1 Ni 59a
Cu BDAP Triton X-114 200 µL 1:1 methanol with FAAS 0.1 µg g−1 Cu 29b Foods [132]
Ni 1 M HNO3 0.4 µg g−1 Ni 2b
Cu PAN Triton X-114 300 µL ethanol with 1% HNO3 FAAS 0.1 ng mL−1 Cu 36b Foods [133]
Zn 0.15 ng mL−1 Zn 32b
Dy 5-Br-PADAP PONPE 7.5 50 µL acetonitrile CZE-UV at 585 nm 0.20 ng mL−1 Dy 200c Urine [134]
Fe 0.48 ng mL−1 Fe
Au 1,8-Diamino-4,5- Triton X-114 At 5 mL with HNO3 ICP-AES 0.5 ng mL−1 Au 8.6b Mine stones [135]
Pd di-hyroxyanthraqui- (65%, w/w) 0.3 ng mL−1 Pd 20.2b
none
Au Without reagent CTAB/Triton 0.15 mL methanol with 10% ICP-MS 0.12 pg mL−1 Au 125b Environmental samples [136]
Tl X-114 HNO3 0.02 pg mL−1 Tl 110b
Hf Quinalizarine Triton X-114 1.2 mL 1-propanol (30% in ICP-AES 0.31 ng mL−1Hf 35.8b Water and alloy samples [137]
Zr water) with 1 M HNO3 0.26 ng mL−1 Zr 38.9b
Fe PMBP Triton X-100 200 µL 0.1 M HNO3 GFAAS 0.08 ng mL-1 Fe 25a Waters [138]
Mn 0.02 ng mL-1 Mn 31a
Fe 8-Quinolinol Triton X-100 0.5 mL 0.1 M HCl GFAAS – – Fe in riverine water reference [139]
V derivatives
Pd 5-Br-PADAP PONPE 7.5 50 µL acetonitrile CE at 576 nm 0.08 ng mL−1 Pd 250c Spiked water and urine [140]
Pt 0.04 ng mL−1 Pt samples
Sc With and without Triton X-114 UV/vis (672 nm Sc; [141]
Y 8-HQ 655 nm Y)

ACDA 2-amino-cyclopentene-1-dithiocarboxylic acid, BDAP 2-(2′-benzothiazolylazo)-5-(N,N-diethyl)aminophenol, FO-LADS fibre optic–linear array detection spectrophotometry, FS fast
sequential, H2mdo 3-[(8-{[(E)-2-hydroxyimino-1-methylpropylidene]amino}-1-naphthyl)imino]-2-butanone oxime, NDDBH 6-(4-nitrophenyl)-2,4-diphenyl-3,5-diaza-bicyclo[3.1.0]hex-2-ene,
TAC 2-(2-thiazolylazo)-p-cresol
a
Calculated as the ratio of the analytical signal of the preconcentrated sample to that obtained without preconcentration
b
Calculated by dividing the slope of the calibration curve after preconcentration by that obtained without preconcentration
c
Calculated as the ratio of the concentration of the analyte in the final surfactant-rich phase to that in the initial solution
C.B. Ojeda, F.S. Rojas
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview
A combined method including fibre optic–linear array
detection spectrophotometry (FO-LADS) and CPE was
developed using a cylindrical microcell for simultaneous
preconcentration and determination of different species
[128]. The CPE and FO-LADS methods have good
matching conditions for combination because FO-LADS
is suitable as a detection technique for the low volume of
the remaining phase obtained after CPE. This combination
was carried out using 50-µL cylindrical microcells and was
employed for simultaneous preconcentration and determi-
nation of cobalt and nickel. The spectra of cobalt and nickel
complexes were collected by FO-LADS and processed for
normal and first-derivative spectrophotometry.
Lemos et al. [129] developed a CPE method by the use
of 2-[2′-(6-methyl-benzothiazolylazo)]-4-bromophenol
reagent as a complexing agent prior to FAAS determination
of cobalt and nickel.
Shemirani et al. [131] applied CPE as a preconcentration
step for FAAS determination of Cu and Ni by the use of a new
Schiff base, 3-[(8-{[(E)-2-hydroxyimino-1-methylpropyli-
dene]amino}-1-naphthyl)imino]-2-butanone oxime (H2mdo),
as a complexing agent. The results demonstrate the useful-
ness of the CPE system to quantitatively extract and
preconcentrate copper and nickel Schiff base complexes.
Lemos et al. [132] applied a thiazolylazo reagent, 2-(2′-
benzothiazolylazo)-5-(N,N-diethyl)aminophenol in a CPE
procedure for determination of copper and nickel in food
samples. Owing to good analytical characteristics, this CPE
procedure has been demonstrated to be very interesting for
trace copper and nickel analysis.
Ferreira et al. [133] proposed a preconcentration proce-
dure using CPE for determination of copper and zinc in
food samples by fast sequential multielement-FAAS. The
optimization of the preconcentration procedure is per-
formed exploiting the Box–Behnken design that proved to
be efficient for optimization of preconcentration procedures
using CPE for simultaneous determination of copper and
zinc.
The on-line incorporation of CPE and FIA associated
with CE for simultaneously determining dysprosium and
iron at parts per billion levels in urine was presented and
evaluated for the first time by Ortega et al. [134]. A
background electrolyte of 20 mM sodium tetraborate buffer
containing 13% acetonitrile, pH 9.0 was found to be
optimal for the separation of metal chelates. The results
from this work demonstrated for the first time the feasibility
of coupling an on-line cloud point preconcentration step
with CZE. Substantial improvements were attained with
this method compared with published reports. This proce-
dure was found to be easily applicable to the analysis of
human urine, providing a sensitive method for the
determination of dysprosium and other metal ions with
minimal sample handling and high reproducibility.
775
Taking full advantage of the attractiveness of the CPE
approach, Favre-Réguillon et al. [142, 143] investigated the
concept of using this technique for the separation of
lanthanides. The complexation was done with appropriate
chelating agents with the aim of obtaining lipophilic
complexes and the influence of the surfactant nature and
the chelating agent to metal molar ratio on the extraction
efficiency was studied. CPE was used to extract and
separate lanthanum(III) and gadolinium(III) nitrate from
an aqueous solution. The method used is based on the
formation of Ln(III)–8-HQ complexes that are soluble in a
micellar phase of a non-ionic surfactant. The results of this
study demonstrate the usefulness of this type of micelle-
mediated extraction to selectively extract and preconcen-
trate lanthanides. In another study, the same research group
investigated the influence of the pH of the solution, the
structure of the chelating agent, and the chelating agent to
Ln(III) molar ratio on the extraction efficiency and
selectivity [144]. The stripping of the lanthanide ions from
the coacervate phase was also studied. La(III) and Gd(III)
can be separated without using organic solvents by CPE.
The process consists of four steps: (1) extraction of Ln(III)
into the micelles of a non-ionic surfactant as a function of
their association constants with a chelating extractant, 8-
HQ; (2) phase splitting induced by increasing temperature;
(3) back-extraction of Ln(III) from the surfactant-rich phase
using an acidic solution; and (4) a second phase splitting.
The separation can be achieved using an 8-HQ to Ln(III)
molar ratio of 14 at pH 5.5 and Ln(III) can be stripped with
0.01 M nitric acid solution.
Meeravali and Jiang [136] described a fast microwave-
assisted cationic mixed-micelle CPE procedure for the
preconcentration and separation of ultratrace levels of gold
and thallium simultaneously from environmental samples
prior to their determination by ICP-MS. The cationic mixed
micelles (cetyltrimethylammonium bromide/Triton X-114)
were used for selective extraction of anionic species of gold
and thallium in an HCl medium into a small volume of the
surfactant-rich phase, without using any chelating agent.
The high selectivity achieved in the process alleviated the
spectral interferences on gold, and provided interference-
free ultratrace determination, for the first time, in geological
matrices using ICP-MS. The accuracy of the procedure was
verified by analysing certified reference materials such as
NIST 1643c and 1643d (Trace elements in water), 2709
(San Joaquin soil), and 2711 (Montana soil), and NRCC
NASS-5 (ocean seawater).
Using CPE for three metal ions simultaneously
Table 3 summarizes the methods described in the literature
using CPE as a preliminary step for separation and
preconcentration of three metal ions.
776 C.B. Ojeda, F.S. Rojas

Reference
A Box–Behnken design was used for optimizing a

[145]

[146]

[147]

[148]

[149]
procedure for simultaneous preconcentration of cadmium,
copper, and lead ions from mineral water [145]. This
procedure is based on the CPE of these metallic ions into

Water and urine samples

Biological water, natural
water, and wastewater,

Pharmaceutical products
micellar media after complexation. For the first time, the
advantages of simultaneous preconcentration of metallic

soil and blood

ions by CPE and multielemental sequential determination
by TS-FF-AAS were combined to develop a simple, cheap,
fast, and sensitive procedure for determining toxic trace
Waters

Waters
Matrix

metals in waters. The results demonstrated that CPE can be

used as a preconcentration step for metallic ions prior to
their multielemental sequential determination by TS-FF-
59a, 25a, 21a

67a, 65a, 58a

AAS, allowing limits of detection as low as those of

GFAAS for metallic ions. On the other hand, a Box–
20b
PF

Behnken design was successfully applied as a multivariate

8a
–

technique to optimize the extraction conditions of the cad-

5×10–3, 6×10–3, 1×10–3

mium, copper, and lead ions prior to the determination step,

allowing evaluation of interaction effects between opti-
mized variables and economy in terms of time and reagents.
0.025, 0.38, 0.43

0.15, 0.72, 0.03

DL (ng mL−1)

calculated by dividing the slope of the calibration curve after preconcentration by that obtained without preconcentration

A two-step sequential CPE of trace elements from small

2.1, 1.6, 1,9

sample volumes of human serum, animal blood, and food

calculated as the ratio of concentration of the analyte in the final surfactant-rich phase to that in the initial solution
5, 2, 2

diet was proposed by Giné et al. [150] to gain analytical

information in the analysis by ICP-MS. The first CPE was
attained by adding DDTP and Triton X-114 followed by
with individual and PLS
UV/vis spectrophotometry

heating at 40 °C, centrifugation, and cooling to 0 °C. The

resulting surfactant-rich phase was separated to determine
cadmium, lead, and copper by isotope dilution. The pH of
Detection system

the residual surfactant-poor phase solution was adjusted in

calibration
TS-FF-AAS

the range 4–5 before the chelating reagent, 4-(2-pyridylazo)

ICP-MS

resorcinol, and Triton X-114 were added and this was

FAAS

FAAS

followed by the sequence to attain the CPE. Cobalt and

nickel were quantified in the second extracted surfactant-
rich phases by a standard additions method.
of 5 g to decrease viscosity

nebulization for ICP-MS

and facilitate continuous

Mustafina et al. [151] investigated the micelle-mediated

1 M HCl to a total mass
1 mL alcoholic solution

extraction of lanthanide (La3+, Gd3+, and Yb3+) complexes

0.5 mL 1 M HNO3 in
Acidified methanolic
SRP diluting agent

with water-soluble calixarenes using the CPE technique

with 1% HNO3

0.3 mL ethanol

with Triton X-100. Three water-soluble calixarenes, p-

Table 3 CPE applications for three metals simultaneously

sulfonato thiacalixarene, tetrasulfonatomethylated calix[4]

methanol
solution

resorcinarene, and calix[4]resorcinarene phosphonic acid,

able to bind lanthanide ions, were chosen as ligands. As
there is a lack of information about CPE of lanthanide ions
by Triton X-100 without chelating agents, the above-
2-Mercaptobenzothiazole/

mentioned extraction was also examined.

ketone oxime/Triton

Most procedures used for preconcentration and/or

8-HQ/Triton X-114
PAN/Triton X-114

PAN/Triton X-114
Reagent/surfactant

Methyl-2-pyridyl-

determination of lanthanides usually report the results as

Triton X-100

the total content in the sample, since the separation and

PLS partial least squares

analysis of single elements can be very time consuming and

X-114

difficult. The CPE procedure presented by Pérez-Gramatges

and Chatt [152] offers the possibility of simultaneous
determinations of the individual lanthanides. This proce-
Cd, Cu, Zn
Cd, Cu, Pb

Co, Cu, Ni

Co, Ni, Zn

Pd, Pt, Rh

dure was used for the simultaneous extraction of 12

lanthanides, which were determined afterwards by neutron
Ions

activation analysis.
b
a
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview
CPE behaviours of Ln(III) [La(III), Eu(III), and Lu(III)]
with and without di(2-ethylhexyl)phosphoric acid (HDEHP)
using Triton X-100 were investigated by Ohashi et al. [153].
The dependencies of the experimental conditions, such as pH,
the concentration of HDEHP, and ionic strength, were also
investigated. Moreover, the extraction constants of Ln(III)
with HDEHP in the CPE system were obtained.
Recently, new approaches for acceleration of CPE of
rhodium, palladium, and platinum by microwave and
ultrasound irradiation have been investigated by Simitchiev
et al. [149]. Microwave irradiation substantially increased
the procedure efficiency. In contrast, no significant effect
was observed when a micellar solution was treated with
ultrasound energy. The acceleration of complex formation
reactions by reducing agents (KI and SnCl2) has also been
studied. The use of SnCl2 was a prerequisite for quantita-
tive extraction of rhodium. Since the extraction kinetics of
platinum depends on its oxidation state and the presence of
palladium, the addition of SnCl2 equalized the platinum
extraction behaviour. For the first time the whole cloud
point procedure was successively accomplished in a
microwave system. Irradiation for 10 min was sufficient
for gravimetric phase separation and quantitative extraction
of platinum group metals. As a result, the procedure time
was shortened by a factor of 9 in comparison with
conventional hot-plate CPE.
CPE for multielement analysis
A comparative study between CPE and low-temperature
directed crystallization was presented by Giokas et al.
[154]. Trace elements (Cd, Pb, Cr, Cu, Zn, Ni, and Fe) were
preconcentrated by both methods from model and natural
water samples and the results were evaluated with respect
to extraction efficiency, accuracy, precision, sample
throughput, and interferences. FAAS and ICP-AES were
used for the final measurements. Both extraction methods
described in this study offer high extraction efficiency and
high preconcentration factors. However, the detector plays
an important role in their selection, whereas on-line and in
situ applications also determine the method selection. Later,
the same investigation group studied the monitoring of
dissolved metal species in natural waters by FAAS [155];
six metal species were extracted from water samples as
their pyrrolidinedithiocarbamate complexes and were sub-
sequently isolated from the aqueous matrix in the micelles
of a non-ionic surfactant upon increase of the solution
temperature.
The cloud point method was successfully employed for
the preconcentration of heavy metal cations at trace levels
from aqueous samples prior to FAAS; Farajzadeh and
Fallahi reported [156] the results obtained in a study of the
simultaneous CPE of Cu2+, Mn2+, Ni2+, Cd2+, Fe3+, Co2+,
777
Zn2+, Cr3+, and Pb2+ after the formation of a complex with
8-quinolinol, and later analysis by FAAS using Triton X-
114. The detection limits were obtained in the range 0.8–
15 ng mL−1 and improved by 1 or 2 orders of magnitude
with such a simple CPE procedure.
An analytical procedure consisting of separation and
preconcentration using CPE was developed by Bezerra et
al. [157] to allow the simultaneous extraction and determi-
nation of trace amounts of cadmium, chromium, copper,
manganese, nickel, and lead from saline oil-refinery
effluents and digested vegetable samples using ICP-AES.
The procedure was based on CPE of the metals studied as
5-Br-PADAP complexes into micellar media of Triton X-
114. Response surface methodology using Doehlert designs
was applied to optimize the procedure. Principal component
analysis was used to identify similar response surfaces and
to simplify the optimization procedure. Later, the same
group proposed a similar procedure for the determination of
traces of cadmium, cobalt, manganese, and chromium in
petroleum-industry-produced water by ICP-AES [158].
This procedure is based on CPE of these metals, as their
dithizonate complexes, into the surfactant-rich phase of
Triton X-114. Extractions were carried out in solutions with
salinities between 10 and 70‰. Since residual salinity in
the surfactant-rich phase caused differences in its transport
to the plasma, yttrium was used as an internal standard to
correct for this effect. The simultaneous metal extraction
procedure was optimized by response surface methodology
using a Doehlert design and desirability function.
A simultaneous preconcentration using Triton X-114 and
determination of Zn(II), Co(II), Ni(II), and Pb(II) was
described by Dallali et al. [159]. The pH of the sample
solution was adjusted to 9 with buffer solution and the
cations were complexed with 2-guanidinobenzimidazole.
After the phase separation at 40 °C, the surfactant-rich
phase was diluted to 1.5 mL using an ethanolic solution of
HNO3 and the analytes were determined by FAAS.
Meeravali et al. [160] developed a CPE method so that it
could be used for multielement determination in seawater
using GFAAS with iridium as a permanent modifier. The
elements determined were silver, cobalt, chromium, copper,
iron, manganese, nickel, and lead. Triton X-114 and APDC
were used as an extraction medium and a chelating
extractant, respectively.
In another recent study, an on-line CPE system coupled
to a ICP-AES system was designed for simultaneous
extraction, preconcentration, and determination of cadmi-
um, cobalt, chromium, copper, iron, and manganese ions in
water samples [161]. This is based on the complexation of
the metal ions with 1-(2-thenoyl)-3,3,3-trifluoracetone
reagent at pH 6.0 in the presence of Triton X-114. The
micellar solution was heated above 60 °C and loaded
through a column packed with cotton, which acts as a filter
778
to retain the analyte-entrapped surfactant-rich phase. Then
the surfactant-rich phase was eluted using propanol/0.5 M
HNO3 (75:25, v/v) at a flow rate of 3.0 mL min−1 and
directly introduced into the nebulizer of the ICP-AES
system. The new system omitted the process of centrifuga-
tion and cooling in an ice bath and the separation was
performed on a column packed with cotton.
Kilinc et al. [162] reported the synthesis of two chiral bis
(amino alcohol)oxalamides from amino alcohols derived
from natural amino acids, and their application to the
preconcentration of copper, cadmium, cobalt, and nickel by
using a CPE method prior to atomic-absorption determina-
tion. Triton X-114 was found to be the best surfactant.
Another CPE procedure was developed recently for the
determination of trace amounts of Cr(III), Pb(II), Cu(II), Ni
(II), Bi(III), and Cd(II) ions by using FAAS. This method
was based on CPE of analyte metal ions without a ligand
using Tween 80 as the surfactant [163].
Shariati et al. [164] applied CPE as a preconcentration
step for simultaneous extraction and determination of low
concentrations of uranium, thorium, zirconium, and hafni-
um ions in aqueous samples. In the system developed,
dibenzoylmethane was used as a chelating agent and Triton
X-114 as a non-ionic surfactant. The preconcentrated
analytes in the surfactant-rich phase were determined
simultaneously by ICP-AES. This method gives a low limit
of detection as well as good relative standard deviation and
linearity for the analytes.
An extraction procedure based on the cloud point
phenomenon has been developed for simultaneous deter-
mination of cadmium, cobalt, copper, iron, manganese,
nickel, and zinc in liquid samples by ICP-AES [165].
Complexes of metal ions with PAN were extracted from
aqueous solutions into Triton X-114 upon increase of the
solution temperature.
Discussion
On-line CPE
Recently, CPE has become one of the preconcentration
steps of choice to enhance sensitivity for determination of
metal ions. This is mostly due to the enormous potential
benefits and versatility related to this particular process.
Off-line CPE has been applied to extract and preconcen-
trate various metal ions from aqueous solutions. It involves
a series of fussy procedures including incubation, centrifu-
gation, and separation of the surfactant-rich phase from the
bulk aqueous phase and dilution of the surfactant-rich
phase. All these may result in poor reproducibility, a low
preconcentration factor, and a time-consuming procedure.
Most recently, CPE was incorporated on-line into a FIA
C.B. Ojeda, F.S. Rojas
assembly. FIA is a computer-compatible technique and
allows automatic handling of sample and reagent solutions
with strict control of reaction parameters. CPE procedures
offer the possibility for on-line applications through simple
manifolds. The incorporation of CPE into a FIA system is a
very interesting alternative in the field of separation
methods, combining the advantages offered by both
methods.
On-line combination of CPE with FIA has been shown
to be a promising means of analysis because of enhanced
sensitivity and reproducibility, efficient removal of matri-
ces, and high extraction efficiency. In on-line FIA–CPE, the
equilibration and centrifugation procedures are avoided,
making the entire extraction process simpler and the
analysis time shorter. More importantly, the surfactant-rich
phase containing the analytes can be easily removed by on-
line elution rather than by use of a pipette. A larger
preconcentration factor can therefore be achieved by use of
lower concentrations of surfactant. In recent years, on-line
combination of CPE with FIA has attracted much attention.
Fang et al. [166] proposed, for the first time, the on-line
incorporation of CPE and FIA. Ortega et al. [134, 167, 168]
applied this method to determine gadolinium, dysprosium,
and iron in aqueous samples. Also, the on-line incorpora-
tion of CPE and micellar FIA–chemiluminescence was
reported for the first time as a tool for detecting and
quantifying metal species at the nanogram per litre
level by Paleologos et al. [169]. The analytical perfor-
mance of the method was investigated for several metals in
standard solutions and was fully developed for chromium
determination.
CPE has been shown to be an effective sample
pretreatment approach for improving sensitivity and selec-
tivity prior to FIA. Also, the on-line incorporation of CPE
into a FIA system represents an important advantage,
because it avoids all manual operations.
In the on-line mode of CPE, some tedious steps that
could reduce repeatability of the method, such as heating,
centrifugation, cooling in an ice bath, separation of the bulk
aqueous phase from the surfactant-rich phase, and dilution
of the surfactant-rich phase, are omitted. These steps result
in a long extraction time, a small preconcentration factor,
and poor precision. On-line CPE integrates heating of the
sample, trapping of the surfactant-rich phase on a column,
and elution of the entrapped analytes in one step; therefore,
it reduces the analysis time and increases the simplicity,
sensitivity, preconcentration factor, and precision of the
method.
For the determination of trace elements by on-line
combination of CPE with atomic spectrometry, the use of
a salting-out agent to induce cloud point phase separation
on-line may present serious problems because the introduc-
tion of a high concentration of salts is unfavourable for
Separation and preconcentration by a cloud point extraction procedure for determination of metals: an overview
atomic-spectrometric detection. Also, the incorporation of a
heating device within the FIA manifold may complicate the
system design.
Ortega et al. [168] reported an on-line phase-separation
method which included dysprosium preconcentration by
CPE followed by the retention of the micelle-rich phase on
a cotton-filled conical minicolumn and ICP-OES detection.
Similar strategies were employed by Li et al. [14] and Nan
et al. [170].
In the work of Gil et al. [50], for the first time the
coupling of a CPE preconcentration system with the on-line
phase separation by sorption of the micelle-rich phase into
the inner walls of a PTFE KR was performed. In this case,
all the drawbacks were solved by implementing the
proposed on-line phase separation. Cobalt was extracted
by PONPE 7.5 without the use of a complexing reagent; the
cloud point temperature for PONPE 7.5 is around 25 °C,
and the separation was made directly into the PTFE KR.
Speciation
The selective determination of ionic species in aqueous
samples is of critical importance in different areas of
applied analytical chemistry, e.g. in the analysis of a variety
of clinical, horticultural, industrial, and environmental
samples. CPE coupled with atomic spectrometry has been
proved to be a very powerful technique for trace and even
ultratrace element analysis. Furthermore, CPE offers the
possibility for the differential determination of individual
oxidation states of an element by selective preconcentration.
Recently, CPE as a preconcentration step in conjunction
with detection by FIA–spectrofluorimetry, FAAS, ETAAS,
and HPLC for the speciation analysis of chromium [37, 38,
40, 41, 112, 171–174], iron [175, 176], manganese [74],
selenium [93], antimony [14], and tin [103] species was
also reported. Later, the feasibility of chromium speciation
in water was demonstrated using CPE of Cr(III) and
sequential determination by GFAAS [45] and FAAS [46].
The method is definitely simple, reproducible, and highly
sensitive because of the distinct and advantageous features
of CPE (in situ and single-step extraction). Also, CPE using
mixed micelles is a very promising method for the
establishment of new analytical procedures. To carry out
the separation and preconcentration of the tin species in this
way, a mixed-micelle-mediated extraction system was used
by Gholivand et al. [104]. On the other hand, only a few
works have reported on CPE preconcentration of mercury
species. De Wuilloud et al. [177] reported a CPE approach
for preconcentration of trace inorganic mercury in tap water
samples with the chelating reagent 2-(5-bromo-2-pyridy-
lazo)-5-diethylaminophenol and the non-ionic surfactant
PONPE 7.5 prior to flow injection CV generation ICP-
OES, and achieved a detection limit of 4 ng L−1 inorganic
779
mercury. Yu [76] reported the application of CPE as a
preconcentration step prior to HPLC-CV-AFS for the
speciation of mercury. Subsequently, Li and Hu [81]
developed a novel non-chromatographic speciation tech-
nique based on sequential CPE for the speciation of
mercury in seafood by ICP-OES and Yin [82] reported a
dCPE technique for CE speciation of mercury, as described
earlier. Finally, Chem et al. [84] developed a sensitive,
analyst/environment-friendly, and cost-effective method for
the determination of ultratrace mercury species in environ-
mental waters and biological samples by coupling CPE
preconcentration with an HPLC-ICP-MS system.
Heating
Microwaves and ultrasound energy have been used to speed
up some chemical processes. Therefore, it is reasonable to
expect a stimulation of the complex formation and faster
migration of the extractable species into the micelles if CPE
is assisted by microwave or ultrasound irradiation. For the
first time the main steps of a CPE are completed all
together in a microwave system. The replacement of the
conventional hot-plate heating by microwave irradiation
energy increases significantly the CPE procedure efficiency,
while the sonication of micellar solutions does not show
any positive effect [149]. Microwave-assisted CPE with 2-
mercaptobenzothiazole has proved to be an efficient
procedure for separation of platinum group metals from
the sample matrix and can be applied as an independent and
selective method of analysis. The same research group
evaluated the contribution of spectral interferences (poly-
atomic, isobaric, or doubly charged ions) to the rhodium,
palladium, and platinum signals and the feasibility of
mathematical corrections aiming to improve the analytical
performance of ICP-MS for determination of platinum
group metals in road dust. The mathematical approaches
were assessed by calculating the combined uncertainties
corresponding to the corrected signals and the accuracy was
verified by an alternative method based on the previously
developed selective microwave-assisted CPE [178].
Optimization strategy
Method development for CPE requires the optimization of
several experimental parameters, such as pH and the
concentrations of the chelating agent and the surfactant.
Traditional univariate optimization might be a time-
consuming and labour-intensive procedure, requiring sev-
eral experiments to be performed and neglecting possible
interactions between variables. Multivariate optimization
appears to be a more interesting and complete alternative,
allowing maximum information to be obtained owing to the
possibility of evaluating interactions between variables. It
780
also represents a more economical approach, as the number
of experiments can be significantly reduced.
The optimization process can be carried out using
response surface methodology. One of the possibilities is
to use a Box–Behnken design, in which the number of
experiments (N) is defined by the equation N = k2 + k + cp,
where k represents the number of factors (parameters)
involved in the study and cp is the number of replicates of
the central point [118]. The optimization of the experimen-
tal variables (concentration of HCl, chelating reagent, and
Triton X-114) for the CPE will be described using a Box–
Behnken design with three variables. Multivariate method
optimization using factorial and Box–Behnken design has
proved to be an extremely valuable tool, allowing accurate
optimum values of experimental parameters to be deter-
mined as well as the possibility to evaluate the interaction
between variables with a reduced number of experiments.
On the other hand, the Doehlert matrix, commonly
applied, is a second-order design that allows the identifica-
tion of critical points (maximum, minimum, and saddle
points) at each step of the optimization process. The whole
experimental design is assayed with a minimum number of
experiments. For a number factor k with cp repetitions of
the central point, k2 +k+c experiments are required. This
optimization procedure has the following advantages: (1)
valuable information is obtained with a reduced number of
experiments, compared with the classic method of optimi-
zation by one factor at a time; (2) the experimental response
is studied as a function of several variables and therefore
mathematically models this response; (3) it is possible
using this approach to obtain information regarding the
interaction between the factors under study.
In this sense, in another investigation, the optimization
step was performed using a four-variable Doehlert design,
involving the factors centrifugation time of the system after
addition of the surfactant, pH, methanol volume added at
the micellar phase, and buffer concentration. The analytical
response used was absorbance, after volume correction
[87]. The robustness was checked by using saturated
fractional factorial designs, centred on the established
experimental conditions in the optimization step. The
results of these tests demonstrated that the variables
centrifugation time and buffer concentration are robust for
modification by 10% and that pH and methanol volume are
robust for 5%.
Conclusions
CPE offers many advantages over traditional liquid–liquid
extraction. Compared with traditional solvent extraction,
CPE uses water and avoids the use of large amounts of
toxic and flammable organic solvents. In addition, CPE can
C.B. Ojeda, F.S. Rojas
lead to higher recovery efficiency and a large preconcentra-
tion factor because the presence of surfactant can minimize
losses of analytes due to their adsorption onto the container.
CPE has been used for the separation and preconcentration
of metal ions in different samples prior to their determina-
tion by instrumental methods. The recent on-line incorpo-
ration of CPE into a FIA system represents an important
advantage, because it avoids all manual operations.
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