Spectrochimica Acta Part A 94 (2012) 48–52

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Synergistic enhancement effect of room temperature ionic liquids for cloud point
extraction combined with UV–vis spectrophotometric determination nickel in
environmental samples
Chujie Zeng ∗ , Xili Xu, Neng Zhou, Yao Lin
Department of Chemistry and Material, Yulin Normal College, Yulin, Guangxi 537000, China

a r t i c l e i n f o a b s t r a c t

Article history: A new method based on enhancement effect of room temperature ionic liquids for cloud point extrac-
Received 30 December 2011 tion trace amounts of nickel combined with UV–vis spectrophotometric determination was developed.
Received in revised form 18 February 2012 Room temperature ionic liquids (RTILs) and diethyldithiocarbamate (DDTC) were used enhancement
Accepted 22 March 2012
reagent and chelating reagent, respectively. The addition of room temperature ionic liquids leads to 3.0
times improvement in the determination of nickel. The nonionic surfactant Triton X-100 was used as the
Keywords:
extractant. When the temperature of the system was higher than the cloud point of Triton X-100, Ni-DTC
Room temperature ionic liquids
complex was extracted into Triton X-100 and separation of the analyte from the matrix was achieved.
Cloud point extraction
Diethyldithiocarbamate
Some parameters that influenced cloud point extraction and subsequent determination were evaluated
Nickel in detail, such as the concentrations of RTILs, DDTC and Triton X-100; pH of sample solution, as well as
Spectrophotometer interferences. Under optimized conditions, an enrichment factor of 72 could be obtained, and the detec-
tion limit (LOD) for Ni was 0.5 ng mL−1 . Relative standard deviations for five replicate determinations of
the standard solution containing 50 ng mL−1 Ni was 3.9%. The proposed method was successfully applied
to the determination of nickel in certified reference materials with satisfactory results.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction extraction solvent for separation and preconcentration of various

Nickel has been the subject of many investigations due to it is
essential for living organism but toxic when it is excessive. The con-
centration of nickel in environmental and biological samples is very
low. In order to obtain reliable results, an efficient separation and
preconcentration step is usually necessary prior to analysis. Sev-
eral preconcentration methods including liquid–liquid extraction
(LLE) [1,2], solid phase extraction (SPE) [3–5], cloud point extrac-
tion (CPE) [6,7], liquid phase microextraction (LPME) [8], Hollow
fiber based-liquid phase microextraction [9], ionic liquid extrac-
tion [10] and chemical vapor generation (CVG) [11,12] have been
reported for nickel analysis.
Room temperature ionic liquids (RTILs) are ionic media
resulting from combination of organic cations and various
anions that are liquids at room temperature. RTILs have some
unique physicochemical properties such as negligible vapor pres-
sure, environment-friendly, non-flammability as well as good
extractability for various organic compounds and metal ions [13].
These characteristics make ionic liquids suitable to be used as the
∗ Corresponding author at: Department of Chemistry and Material, Yulin Normal
College, Yulin, Guangxi 537000, China. Tel.: +86 775 2622 315.
E-mail address: cjzeng@126.com (C. Zeng).
organic compounds and metal ions [14–19]. RTILs were also used
as enhancement agent on the chemical vapor generation of Au, Ag
and Cu [20]. Recently, synergetic enhancement effect of ionic liq-
uid and chelating agent on the chemical vapor generation of Fe,
Co and Ni were reported [11,21]. To the best of our knowledge,
synergetic enhancement effect of RTILs for cloud point extraction
trace amounts of nickel combined with UV–vis spectrophotometric
determination has not been reported yet.
The present work was aimed to develop a new nickel analy-
sis method. Synergetic enhancement effect of RTILs for cloud point
extraction combined with UV–vis spectrophotometer were used
for determination nickel. Traditional cloud point extraction com-
bined with UV–vis spectrophotometric determination nickel only
have an enrichment factor of 24 could be obtained. The addition of
1-butyl-3-methylimidazolium hexafluorophosphate ([C4 MIM]PF6 )
(RTILs) leads to 3.0 times improvement in the determination
of nickel. Some parameters that influenced cloud point extrac-
tion and subsequent determination, and interference of coexisting
ions were investigated systematically. The proposed method
possesses the advantages of high enrichment factor, simplicity,
sensitivity, low cost, selectivity and environmental friendship.
This method was successfully applied to determination nickel
in certified reference environmental samples with satisfactory
results.

1386-1425/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2012.03.064
 C. Zeng et al. / Spectrochimica Acta Part A 94 (2012) 48–52 49

2. Experimental

2.1. Apparatus

A model UV-2550 spectrophotometer (Shimadzu Instrumental

Co., Japan) was used for the determination of nickel. A centrifuge
Model 80-2 (Changzhou Guohua Scientific Instrument Corpora-
tion, Jiangsu, China) was used to assist phase separation. A HH-S
thermostated water bath (Jintan, Medical Instrument Corporation,
Jiangsu, China) was used to heat up the sample solution. The pH
values of samples solution were determined by PHS-3C pH meter
(Leici Instruments, Shanghai, China). A 25-␮L microsyringe (Anting
Corporation, Shanghai, China) was used for transferring sample
solution.

2.2. Standard solutions and reagents

The stock standard solutions of Ni(II) (1 mg mL−1 ) were pur-

Fig. 1. Absorption spectra for the determination of Ni with CPE. Ni: 50 ng mL−1 ;
chased from the National Center for Reference Materials (Beijing,
DDTC: 0.02% (m/v); Triton X-100: 0.3% (v/v); RTILs: 0.005% (v/v); pH: 6.0; extraction
China). Working standard solutions were obtained by serial dilu- time: 15 min.
tion of the stock standard solutions. All chemicals used were at
least of analytical-reagent grade and all solutions were prepared
with double distilled water (DDW). Diethyldithiocarbamate (DDTC)
was used as the chelating reagent for nickel. RTIL of 1-butyl-3- ethanol because of the sampling demand of spectrophotometer.
methylimidazolium hexafluorophosphate ([C4 MIM]PF6 ) (Chengjie The resultant sample solution was transported to spectrophotome-
Chemistry Corporation, Shanghai, China) and non-ionic surfactant ter for determination.
Triton X-100 (Sinopharm Chemical Reagent Co., Ltd, Shanghai,
China) were used as cloud point synergic enhancement reagent
and extractant, respectively. DDTC, sodium acetate, acetic acid, 3. Results and discussion
ethanol, methanol, tetrachloromethane (CCl4 ), benzene, acetone,
nitric acid and sodium hydroxide (NaOH) used in this experiment 3.1. Study on the absorption spectra of complex
were all obtained from Jingmi Chemical Reagent Corporation (Nan-
ning, China) UV–vis spectrophotometry was used to accomplish the deter-
mination of nickel. The maximum wavelength of absorption of the
2.3. Sample preparation complex of Ni-DTC should be found out for the quantification anal-
ysis. After CPE, the surfactant-rich phase was diluted with 1.5 mL
The following certified environmental reference materials were ethanol and determined in the range of wavelength from 200 nm
purchased from National Standard Material Research Center (Bei- to 400 nm. The maximum wavelength of absorption of the com-
jing, China), which were employed to validate the accuracy of the plex of Ni-DTC after CPE was found in 285 nm. The concentration
proposed method. GBW(E) 080195 (water sample), GBW 08607 of 4000 ng mL−1 Ni(II) was used for Ni-DTC wavelength scan with-
(water sample) and GSBZ 50009-88 (water sample) were appropri- out CPE. The maximum absorption without CPE was 289 nm. It was
ately diluted with DDW, respectively. Certified reference materials shown in Fig. 1. The blank absorbance of all reagents was used to
of 0.2004 g soil (GBW 07403), 0.2012 g stream sediment (GBW correct in the process of the determination of nickel.
07312) and 0.2025 g stream sediment (GBW 07317) were accu-
rately weighed and dissolved with 10 mL aqua regia in digestion
vessel, respectively. Microwave digestion was chosen for decom-
posing the certified reference environmental samples and the
digestion procedure was based on a reference method [22]. The
residues were transferred into 50 mL centrifuge tubes, appropriate
amounts of DDTC, RTILs and Triton X-100 were added and made up
to the volume with DDW, then adjusting its pH to 6.0 with acetic
acid and NaOH, respectively.

2.4. Cloud point extraction procedure

For CPE preconcentration, 50 mL analytical solution contain-

ing nickel ion and proper amount of chelating agent DDTC were
mixed in 50 mL centrifuge tube. After adjusting the pH 6.0, the
proper amounts of Triton X-100 and RTILs were added into the
centrifuge tube. After shaking the centrifuge tube, the analytical
solution was heated in a thermostated water bath at 75 ◦ C for
15 min. After heated, the resultant solution was subjected to cen-
trifugation at 3500 rpm for 5 min for phase separation, and then
cooled in an ice-water bath for 5 min to increase the viscosity of the
Fig. 2. Effect of concentration of DDTC on the absorbance of Ni in CPE. Ni:
surfactant-rich phase. The water phase was carefully removed with 50 ng mL−1 ; Triton X-100: 0.3% (v/v); RTILs: 0.005% (v/v); pH: 6.0; extraction time:
a syringe, and the surfactant-rich phase was diluted with 1.5 mL 15 min.
50 C. Zeng et al. / Spectrochimica Acta Part A 94 (2012) 48–52
Fig. 3. Effect of concentration of RTILs on the absorbance of Ni in CPE. Ni: 50 ng mL−1 ;
Triton X-100: 0.3% (v/v); DDTC: 0.02% (m/v); pH: 6.0; extraction time: 15 min.
3.2. Effect of RTILs and DDTC
The chelating concentration was very important to the CPE
efficiency and subsequent UV–vis spectrophotometer determina-
tion. The effect of the concentration of DDTC on the absorbance of
50 ng mL−1 Ni(II) in the absence or presence of RTILs was studied.
The results were shown in Fig. 2. It can be seen that the absorbance
of Ni increased with the increase of the concentration of DDTC from
0.001% to 0.02% (m/v). After that, the absorbance of Ni remark-
ably decreased with the increase of the concentration of DDTC from
0.02% to 0.1% (m/v). Therefore, 0.02% (m/v) DDTC was selected for
the following experiments.
RTILs were used as synergistic enhancement reagent for CPE of
Ni. It can be seen from Fig. 2. The absorbance of Ni was improved
about 3.0 times in the presence of RTILs. The efficiency of extraction
of Ni-DTC may be promoted by the role of the RTILs. The effect of the
concentration of RTILs on the absorbance of Ni was also studied. The
results were shown in Fig. 3. It was found that the analytical signal
of Ni increased rapidly with the increasing of RTILs concentration
from 0.001% (v/v) to 0.005% (v/v), and then leveled off up to the
concentration of 0.02% (v/v). Thus, 0.005% (v/v) RTILs was selected
in the following experiments.
Fig. 4. Effect of concentration of Triton X-100 on the absorbance of Ni in CPE. Ni:
50 ng mL−1 ; DDTC: 0.02% (m/v); RTILs: 0.005% (v/v); pH: 6.0; extraction time: 15 min.
Fig. 5. Effect of sample pH on the absorbance of Ni in CPE. Ni: 50 ng mL−1 ; DDTC:
0.02% (m/v); RTILs: 0.005% (v/v); Triton X-100: 0.3% (v/v); pH: 6.0; extraction time:
15 min.
3.3. Effect of Triton X-100 concentration
The amount of the non-ionic surfactant affects not only the
extraction efficiency but also the volume of surfactant-rich phase.
Triton X-100 was used as the extractant in this work. The effect of
concentration of Triton X-100 on the absorbance of Ni was inves-
tigated. As shown in Fig. 4, it was found that the absorbance of
Ni increased with the Triton X-100 concentration increasing from
0.05% to 0.3% (v/v), and then leveled off up to the concentration of
1.0% (v/v). To fulfill the “environmentally benign” extraction, a low
concentration of Triton X-100, 0.3% (v/v), was selected for use in
this experiment.
3.4. Effect of pH
The pH of samples plays an important role on the complex for-
mation and subsequent CPE of the target analyte. In order to obtain
the desired complexing and preconcentration efficiencies, the pH
values were studied in the ranges of 2.0–10.0. The effect of pH on the
extraction efficiency was shown in Fig. 5. The maximum of extrac-
tion efficiency was obtained at pH 6.0. Therefore, pH of 6.0 was
selected in the further experiments.
Fig. 6. Effect of kinds of dilution solvent on the absorbance of Ni in CPE. Ni:
50 ng mL−1 ; DDTC: 0.02% (m/v); RTILs: 0.005% (v/v); Triton X-100: 0.3% (v/v); pH:
6.0; extraction time: 15 min.
 C. Zeng et al. / Spectrochimica Acta Part A 94 (2012) 48–52 51

Table 1 Table 3
Interference from coexisting ions on the extraction and determination of Ni(II) Analytical results for Ni in reference materials (mean ± S.D., n = 3).
(50 ng mL−1 ).
Sample Found value Certified value
Coexisting ions [M]/[Ni(II)] Recovery (%, mean ± S.D., n = 3)
GBW 07403 (soil) 11.7 ± 1.8 (␮g g−1 ) 12.0 ± 2.0 (␮g g−1 )
K+ 100,000 97 ± 1 GBW 07312 (stream sediment) 12.5 ± 1.4 (␮g g−1 ) 12.8 ± 1.3 (␮g g−1 )
Na+ 150,000 95 ± 3 GBW 07317 (stream sediment) 3.6 ± 1.2 (␮g g−1 ) 3.7 ± 1.0 (␮g g−1 )
Mg2+ 1000 93 ± 2 GBW(E) 080195 (water sample) 472 ± 20 (ng mL−1 ) 476 ± 30 (ng mL−1 )
Ca2+ 500 96 ± 2 GBW 08607 (water sample) 510 ± 7 (ng mL−1 ) 515 ± 6 (ng mL−1 )
Zn2+ 200 94 ± 1 GSBZ 50009-88 (water sample) 992 ± 36 (ng mL−1 ) 997 ± 48 (ng mL−1 )
Cu2+ 150 97 ± 2
Hg2+ 100 98 ± 3
Pb2+ 50 96 ± 1
studied interfering ions were found not to effect the determina-
Mn2+ 100 93 ± 1
Fe3+ 150 95 ± 3 tion of Ni when the concentration of interfering ions was less than
Al3+ 100 95 ± 2 50-fold that of Ni. Therefore, the selectivity of this method was
Co2+ 50 92 ± 4 fairly satisfactory.

3.5. Conditions of extraction time and phase separation 3.8. Analytical performance and application

Extraction time is very important to the extraction efficiency.
Effect of extraction time on the extraction efficiency of Ni(II) was
evaluated in the range of 5–30 min. The analytical signal of Ni(II)
increased rapidly with the increasing of extraction time from 5 to
15 min, and then leveled off up to 30 min. Thus the extraction time
of 15 min was chosen as the optimal condition for the proposed
method. To achieve easy phase separation, extraction temperature
and centrifugation rate and time were also optimized. After careful
investigations, a temperature of 75 ◦ C and centrifugation rate of
3500 rpm for 5 min were chosen for use in this work.
3.6. Effect of type of dilution solvent
The demand of sampling volume for the conventional spec-
trophotometer is about 2.0 mL. The developed method synergistic
enhancement effect of RTILs for CPE was a miniaturized extrac-
tion technique. To realize the hyphenation of CPE combined with
UV–vis spectrophotometry, the proper dilution of the surfactant-
rich phase before detection was necessary. The enrichment factor
would be more than 72 (obtained by the proposed method) if
dilution was not adopted. Effect of different dilution solvents on
analytical signal of Ni(II) were also investigated. The results were
shown in Fig. 6. It can be seen that the maximum of extraction
efficiency was obtained by ethanol. Thus, ethanol was selected for
further experiments
3.7. Evaluation of interference
Because DDTC was a universal chelating reagent which can com-
plex with other metal elements, and interferences may occur due
to the competition of other metal ions for DDTC. In this work,
several metal ions were selected for evaluation of the selectivity
of the proposed method. Potential interfering ions were investi-
gated, including Na(I), K(I), Ca(II), Mg(II), Zn(II), Cu(II), Hg(II), Pb(II),
Al(III), Fe(III), Co(II), Mn(II). A series of solutions of 50 ng mL−1 Ni(II)
containing the metal ions mentioned above at different concentra-
tions were prepared and determined by UV–vis spectrophotometry
after CPE, respectively. The results were shown in Table 1. All
Table 2
A comparison of the proposed method with alternative others reported for Ni
determination.
Preconcentration Enrichment LOD Determination Ref.
method factor (ng mL−1 ) method
The figures of merit of the developed CPE–UV–vis spectrophoto-
metric method for the determination of Ni based on the synergetic
enhancement effect of RTILs were evaluated. Under the optimal
experimental conditions, some characteristics of this method such
as enrichment factor, linear range, correlation coefficients, limit of
detection (LOD) and repeatability were investigated, respectively.
The calibration curve was linear in the range of 2–100 ng mL−1 Ni(II)
(R2 > 0.998). Enrichment factor, which was calculated as the ratio of
the slopes for the calibration curves subjected to preconcentration
procedure and direct sampling (without preconcentration), was 72.
The limit of detections of Ni was 0.5 ng mL−1 , which was obtained
on the basis of 3 criterion for eleven replicated measurements of
the blank signal. Relative standard deviations (RSD) for five repli-
cate determinations 50 ng mL−1 of Ni was 3.9%. A comparison of the
proposed method with alternative analytical methodologies for Ni
determination was shown in Table 2. The proposed method offers
a better LOD and a higher enhancement factor.
To validate the potential application of the proposed method, six
certified reference materials (CRMs), GBW(E) 080195 (water sam-
ple), GBW 08607 (water sample), GSBZ 50009-88 (water sample),
GBW 07403 (soil), GBW 07312 (stream sediment) and GBW 07317
(stream sediment) were analyzed for Ni determination. The analyt-
ical results were shown in Table 3. The found values in these CRMs
by the proposed CPE–UV–vis spectrophotometric method based on
the synergetic enhancement effect of RTILs were in good agreement
with the certified values.
4. Conclusion
A new method based on the synergetic enhancement effect of
RTILs for CPE combined with UV–vis spectrophotometry for the
determination of Ni was developed in this work. The addition of
RTILs leads to 3.0 times improvement in the CPE efficiencies of Ni.
To be combined with ordinary UV–vis spectrophotometer, the limit
of detection for Ni was 0.5 ng mL−1 , with sensitivity enhancement
factor of 72. The analytical performance of spectrophotometric
determination was greatly improved, which was comparable with
CPE–flame atomic absorption spectrometry (FAAS). The developed
method offers the merits of high enrichment factor, good accuracy,
simplicity, ease of use, sensitivity, low cost, good selectivity, envi-
ronmental friendship and wide practicability. RTIL-assisted CPE is
a potential method by using UV–vis spectrophotometry in many
cases.

CPE 17 2.7 FAAS [6] Acknowledgments

CPE 39 1.2 FAAS [7]
CPE 58 1.9 FAAS [23] The authors gratefully acknowledge the financial support for
RTIL-CPE 72 0.5 UV–vis This work
this project from Foundation of Doctor of Yulin Normal College
52 C. Zeng et al. / Spectrochimica Acta Part A 94 (2012) 48–52
(G2010004) and Guangxi Key Technologies R&D Program for Billion
Dollar Industry (NO11107021-1-6).
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