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Room temperature ionic liquids enhanced the speciation of Cr(VI) and Cr(III)
by hollow fiber liquid phase microextraction combined with flame atomic
absorption spectrometry

Article  in  Journal of Hazardous Materials · September 2012

DOI: 10.1016/j.jhazmat.2012.08.061 · Source: PubMed

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 Journal of Hazardous Materials 237–238 (2012) 365–370

Contents lists available at SciVerse ScienceDirect

Journal of Hazardous Materials

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

Room temperature ionic liquids enhanced the speciation of Cr(VI) and Cr(III) by
hollow fiber liquid phase microextraction combined with flame atomic
absorption spectrometry
Chujie Zeng ∗ , Yao Lin, Neng Zhou, Jiaoting Zheng, Wei Zhang
Department of Chemistry and Material, Yulin Normal College, Yulin, Guangxi 537000, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 First reported enhancement effect of

RTILs in HF-LPME for the speciation
of chromium.
 The addition of RTILs led to 3.5 times
improvement of the sensitivity of
Cr(VI).
 The proposed method is a simplicity,
sensitivity, low cost, green method.

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

Article history: A new method for the speciation of Cr(VI) and Cr(III) based on enhancement effect of room tempera-
Received 23 June 2012 ture ionic liquids (RTILs) for hollow fiber liquid phase microextraction (HF-LPME) combined with flame
Received in revised form 17 August 2012 atomic absorption spectrometry (FAAS) was developed. Room temperature ionic liquids (RTILs) and
Accepted 25 August 2012
diethyldithiocarbamate (DDTC) were used enhancement reagents and chelating reagent, respectively.
Available online 4 September 2012
The addition of room temperature ionic liquids led to 3.5 times improvement in the determination of
Cr(VI). In this method, Cr(VI) reacts with DDTC yielding a hydrophobic complex, which is subsequently
Keywords:
extracted into the lumen of hollow fiber, whereas Cr(III) is remained in aqueous solutions. The extrac-
Room temperature ionic liquids
Hollow fiber extraction
tion organic phase was injected into FAAS for the determination of Cr(VI). Total Cr concentration was
Speciation determined after oxidizing Cr(III) to Cr(VI) in the presence of KMnO4 and using the extraction proce-
Chromium dure mentioned above. Cr(III) was calculated by subtracting of Cr(VI) from the total Cr. Under optimized
Flame atomic absorption spectrometry conditions, a detection limit of 0.7 ng mL−1 and an enrichment factor of 175 were achieved. The relative
standard deviation (RSD) was 4.9% for Cr(VI) (40 ng mL−1 , n = 5). The proposed method was successfully
applied to the speciation of chromium in natural water samples with satisfactory results.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction Cr(III). Cr(III) is considered as indispensable for the metabolism

Elemental speciation has been a very important issue because
the toxicological and biological properties of most elements depend
on their chemical forms. The element chromium exists mainly in
two oxidation states in the environment, which are Cr(VI) and
∗ Corresponding author.
E-mail address: cjzeng@126.com (C. Zeng).
of glucose, lipids and proteins in living organisms. Cr(VI) as a
strong oxidizer is highly toxic and can affect lungs, liver and kid-
neys [1]. Total chromium could not provide sufficient information
to understand its toxicity and bioavailability. Thus, accurate and
sensitive methods for the speciation of Cr(VI) and Cr(III) in envi-
ronmental and biological samples are required. Various analytical
techniques such as atomic absorption spectrometry (AAS)[2], spec-
trophotometry [3], inductively coupled plasma-atomic emission
spectrometry (ICP-AES) [4] and inductively coupled plasma mass

0304-3894/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2012.08.061
366 C. Zeng et al. / Journal of Hazardous Materials 237–238 (2012) 365–370
spectrometry (ICP-MS) [5] have been used for the determination of
chromium in various samples.
The concentration of chromium in environmental and biolog-
ical samples is very low. In order to obtain reliable results, an
efficient separation and preconcentration step is usually necessary
prior to analysis. Some techniques have been used for separation
and preconcentration of chromium, such as cloud-point extraction
[6–8], liquid–liquid microextraction [9–12], hollow fiber extraction
[13,14], solid phase microextraction [1,15], flow injection analysis
[16–19] and high-performance liquid chromatography separation
[20,21].
HF-LPME is one of the promising miniaturized preconcentra-
tion techniques and has attracted considerable attention in recent
years [22–26]. HF-LPME owns many advantages over traditional
liquid–liquid extraction, such as low cost, safety, environmental
friendliness and high concentration factors. Recently, HF-LPME
has been extensively applied in organic extraction, metals pre-
concentration and environmental monitoring [27–29]. RTILs have
some unique physicochemical properties such as negligible vapor
pressure, environment-friendly, non-flammability as well as good
extractability for various organic compounds and metal ions [30].
These characteristics make RTILs suitable to be used as the extrac-
tion solvent [31,32]. Recently, RTILs were also used as enhancement
reagents on the chemical vapor generation and cloud point extrac-
tion [33–35]. To the best of our knowledge, RTILs enhanced the
speciation of Cr(III) and Cr(VI) by hollow fiber liquid phase microex-
traction combined with flame atomic absorption spectrometry has
not been reported yet.
The present work was aimed to develop a novel chromium
speciation analytical method with RTILs enhanced HF-LPME com-
bined with FAAS. HF-LPME combined with FAAS determination
Cr(VI) only have an enrichment factor of 50 could be obtained.
The addition of 1-butyl-3-methylimidazolium tetrafluoroborate
([C4 MIM]BF4 ) (RTILs) in the HF-LPME led to 3.5 times improvement
in the determination of Cr(VI), and an enrichment factor of 175
was obtained. The experimental parameters affecting the HF-LPME
efficiency were investigated in detail. The proposed method was
successfully applied to the speciation of chromium in tap water,
river water and industrial waste water samples with satisfactory
results.
2. Experimental
2.1. Instrumentation
A model AA-6601F flame atomic absorption spectrometer
equipped with D2 lamp background correction (Shimadzu Instru-
mental Co., Japan) was used for the determination of chromium.
A hollow cathode lamp of chromium (Ningqiang Source, Hengshui,
China) was used as radiation source at 4.0 mA. The analytical line at
357.9 nm was used in the measurements with 0.4 nm as the spec-
tral bandwidth. A DF-101S constant temperature magnetic stirring
meter (Jintan, Medical Instrument Corporation, Jiangsu, China) was
used to stir the sample solution. 25 ␮L microsyringes (Anting Cor-
poration, Shanghai, China) were used for sampling and flushing the
lumen of hollow fiber.
2.2. Reagent and materials
All chemicals and reagents used in this study were at least
analytical grade, and all dilution was prepared with double dis-
tilled water (DDW). The stock standard solutions of Cr(VI) and
Cr(III) (1 mg mL−1 ) were purchased from the National Center for
Reference Materials (Beijing, China). DDTC was used as the che-
lating reagent for Cr(VI). RTILs of 1-butyl-3-methylimidazolium
hexafluorophosphate ([C4 MIM]PF6 ), 1-octyl-3-methylimida-
zolium hexafluorophosphate ([C8 MIM]PF6 ), 1-hexyl-3-
methylimidazolium hexafluorophosphate ([C6 MIM]PF6 ) and
1-butyl-3-methylimidazolium tetrafluoroborate ([C4 MIM]BF4 )
were purchased from Chengjie Chemistry Corporation (Shanghai,
China). DDTC, KMnO4 , 1-octanol, ethanol, hydrochloric acid (HCl),
nitric acid and sodium hydroxide (NaOH) used in this experiment
were all obtained from Jingmi Chemical Reagent Corporation
(Nanning, China). The polypropylene hollow fiber (320 ␮m i.d.,
50 ␮m wall thickness, and 0.1 ␮m pore size) was purchased from
Kaihong Membrane Corporation (Hangzhou, China). Tap water
was collected in our laboratory. River water was obtained from
Nanliu River (Yulin, China). Industrial waste water was taken from
the sewage system of the industrial zone in Yulin (China). All
the samples except tap water were immediately filtered with a
0.45 ␮m membrane filter, then the samples were stored at 4 ◦ C.
2.3. Extraction procedure
The extraction procedure of HF-LPME was the same as our pre-
vious report [25]. The hollow fiber was cut manually into 15 cm
length. The lumen of the hollow fiber was washed and filled with
1-octanol by the 25 ␮L microsyringe. The two ends of hollow fiber
were sealed by heating ironware and enveloped with a strip of
aluminum foil. Then, the hollow fiber was completely immersed
into the sample solution of 100 mL. RTILs and DDTC were added
to the samples solution of 100 mL before HF-LPME. The concen-
trations of RTILs and DDTC were 0.005% (v/v) and 0.01% (m/v),
respectively. Considering the sampling amount of FAAS, in the same
way, another three hollow fibers were also immersed into the same
sample solution. The extraction was carried out for 15 min under
a magnetic rotation speed of 800 rpm and temperature of 40 ◦ C.
Then, the extracting solution was collected into a 500 ␮L polyeth-
ylene vial. The volume of collected extracting solution was about
35 ␮L. In order to facilitate sampling, 65 ␮L 95% (v/v) alcoholic solu-
tion with 1% (v/v) HNO3 was added to the extractant. The resultant
solutions were siphoned into FAAS for analysis.
2.4. Determination of Cr(VI) and Cr(III)
(1) Cr(VI): After the HF-LPME procedure, the collected analyte was
siphoned into FAAS for determination.
(2) Total Cr: During the determination of total chromium, 5 drops
of KMnO4 (0.02 mol L−1 ) solution and 0.5 mL of concentrated
H2 SO4 were added into 100 mL of the spiked solution Cr(VI)
and Cr(III)[10]. Then, the spiked solution was heated for 15 min
at 45 ◦ C to complete oxidation. After the oxidation, the resulted
solution was submitted to HF-LPME and determined by FAAS.
(3) Cr(III): The content of Cr(III) was calculated by subtraction of
Cr(VI) from the total Cr.
3. Results and discussion
3.1. Effect of DDTC and RTILs
The concentration of DDTC is one of the key factors to the
extraction efficiency and subsequent FAAS determination. DDTC
was used as chelating reagent, which reacts with Cr(VI) yielding a
hydrophobic complex. The effect of the concentration of DDTC on
the absorbance of 140 ng mL−1 Cr(VI) in the absence or presence
of RTILs was studied. As can be seen from Fig. 1., the absorbance
of Cr(VI) increasing with the increasing of the concentration of
DDTC from 0.001% to 0.01% (m/v), then the absorbance of Cr(VI)
leveled off up to the concentration of 0.1% (m/v). Therefore, the
concentration of 0.01% (m/v) for DDTC was selected for the further
experiments. When RTILs were used as enhancement reagents for
 C. Zeng et al. / Journal of Hazardous Materials 237–238 (2012) 365–370
Fig. 1. Effect of concentration of DDTC on the absorbance of Cr(VI) in HF-LPME.
Cr(VI): 140 ng mL−1 ; RTILs: 0.005% (v/v) (with RTILs); stirring rate: 800 rpm; extrac-
tion time:15 min; 0.08 mol L−1 H2 SO4 ; temperature: 40 ◦ C.
HF-LPME of Cr(VI), it can be seen from Fig. 1, the absorbance of
Cr(VI) was improved about 3.5 times in the presence of RTILs com-
pared with in the absence of RTILs. The enhancement mechanism of
the effect of RTILs on the absorbance of Cr(VI) is unknown, which
may be related to the fascinating properties of RTILs. RTILs were
also able to extract the complex by themselves. The combination of
1-octanol and RTILs created a synergetic enhancement effect on the
extraction of the complex. The enhancement mechanism of RTILs
is being researched in our group.
RTILs were used as enhancement reagents for HF-LPME of
Cr(VI). The effects of four RTILs on the extraction efficiency of
Cr(VI) were investigated in detail. As can be seen from Fig. 2,
[C4 MIM]PF6 and [C4 MIM]BF4 gave higher enrichment factors
than [C6 MIM]PF6 and [C8 MIM]PF6 for the analyte. The most
extraction efficiency of Cr(VI) was obtained by [C4 MIM]BF4. Thus,
1-butyl-3-methylimidazolium tetrafluoroborate ([C4 MIM]BF4 )
was selected as enhancement reagent for HF-LPME of Cr(VI) in
the further experiments. The effect of the concentration of RTILs
([C4 MIM]BF4 ) on the extraction efficiency of Cr(VI) was also
studied. The results were shown in Fig. 3. As can be seen from
Fig. 3, the analytical signal of Cr(VI) increasing rapidly with the
increasing of RTILs ([C4 MIM]BF4 ) concentration from 0.0002% (v/v)
to 0.005% (v/v), and then leveled off up to the concentration of
Fig. 2. Effect of type of RTILs on the absorbance of Cr(VI) in HF-LPME. Cr(VI):
40 ng mL−1 ; DDTC: 0.01% (m/v); RTILs: 0.005% (v/v); stirring rate: 800 rpm; extrac-
tion time:15 min; 0.08 mol L−1 H2 SO4 ; temperature: 40 ◦ C.
367
Fig. 3. Effect of concentration of RTILs on the absorbance of Cr(VI) in HF-
LPME. Cr(VI): 40 ng mL−1 ; DDTC: 0.01% (m/v); stirring rate: 800 rpm; extraction
time:15 min; 0.08 mol L−1 H2 SO4 ; temperature: 40 ◦ C.
0.05% (v/v). Therefore, the concentration of 0.005% (v/v) for RTILs
([C4 MIM]BF4 ) was selected for the following experiments.
3.2. Effect of acid concentration
In HF-LPME method, acid concentration plays a unique role
on the complex formation and subsequent extraction. The effect
of acid concentration on the absorbance of Cr(VI) and Cr(III) was
evaluated in the range of 0.02–0.10 mol L−1 sulfuric acid. The
results were shown in Fig. 4. As can be seen from Fig. 4, Cr(VI)
was completely extracted in the range of 0.02–0.10 mol L−1 sul-
furic acid, but Cr(III) was not almost extracted in the range of
0.02–0.10 mol L−1 sulfuric acid. When the concentration of sulfuric
acid was 0.08 mol L−1 , and the absorbance of Cr(VI) was the opti-
mal. Therefore, 0.08 mol L−1 sulfuric acid was selected for further
experiments.
3.3. Effect of extraction time
Extraction time have an important influenced on the extrac-
tion efficiency. Effect of extraction time on the extraction efficiency
of Cr(VI) was evaluated in the range of 5–30 min. As can be seen
from Fig. 5., the absorbance of Cr(VI) increasing with the increas-
ing of extraction time from 5 to 15 min, then the absorbance of
Fig. 4. Effect of the concentration of H2 SO4 on the absorbance of Cr(VI) and Cr(III)
in HF-LPME. Cr(VI) and Cr(III): 40 ng mL−1 ; DDTC: 0.01%(m/v); RTILs: 0.005% (v/v);
stirring rate: 800 rpm; extraction time:15 min; temperature: 40 ◦ C.
368 C. Zeng et al. / Journal of Hazardous Materials 237–238 (2012) 365–370

Fig. 5. Effect of extraction time on the absorbance of Cr(VI) in HF-LPME. Cr(VI): Fig. 7. Effect of temperature on the absorbance of Cr(VI) in HF-LPME. Cr(VI):
40 ng mL−1 ; DDTC: 0.01% (m/v); RTILs: 0.005% (v/v); stirring rate: 800 rpm; 40 ng mL−1 ; DDTC: 0.01% (m/v); RTILs: 0.005% (v/v); extraction time: 15 min;
0.08 mol L−1 H2 SO4 ; temperature: 40 ◦ C. 0.08 mol L−1 H2 SO4 ; stirring rate: 800 rpm.

Table 2
Analytical features of the proposed method compared with other analytical
methods.

Methods LOD (ng mL−1 ) Enrichment factor Reference

CPE 0.08 98 [8]

LLME 1.25 100 [10]
KR(PTFE) 0.8 80 [36]
SPE 45 25 [37]
CPE 0.65 75 [38]
HF-LPME 0.7 175 This work

3.4. Effect of stirring rate

In HF-LPME, magnetic stirring can enhance extraction efficiency

Fig. 6. Effect of stirring rate on the absorbance of Cr(VI) in HF-LPME. Cr(VI):
40 ng mL−1 ; DDTC: 0.01% (m/v); RTILs: 0.005% (v/v); extraction time: 15 min;
0.08 mol L−1 H2 SO4 ; temperature: 40 ◦ C.
Cr(VI) decreasing with the further increasing of extraction time.
The HF-LPME is based on the partitioning of the analyte Cr(VI)-
DDTC between the aqueous phase and 1-octanol. For a long time
extraction, the solvent loss was usually very serious, and chelating
reagent hydrolysis was severity, which would be led to the decrease
of analytical sensitivity, therefore, the extraction time of 15 min
was selected for the subsequent experiments.
and reduce the time to reach dynamic equilibrium. 1-octanol was
used as the acceptor solution which was confined in the lumen of
the hydrophobic hollow fiber membrane, thus it could tolerate rel-
atively high stirring speeds. Effect of stirring rate on absorbance
of Cr(VI) was evaluated in the range of 200–1200 rpm. As can be
seen from Fig. 6., the absorbance of Cr(VI) increasing remarkably
with the increasing of stirring rate from 200 to 800 rpm, then the
absorbance of Cr(VI) decreasing with the further increasing of stir-
ring rate from 800 to 1200 rpm. Because higher stirring rate could
generate excessive air bubbles that adhered to the hollow fiber
surface, which impeded the transfer of analyte and led to possi-
ble experimental failure. On the basis of above considerations, a
stirring rate of 800 rpm was selected in the following experiments.
3.5. Effect of temperature
Temperature is very important to the extraction efficiency of
Cr(VI). Because temperature may be effected on the fascinating

Table 1
Effect of coexisting ions on the extraction and determination of Cr(VI) (40 ng mL−1 ).

Coexisting ions Mass ratioa Recovery (%) Coexisting ions Mass ratioa Recovery (%)
+ 2+
K 10000 101 Zn 200 98
Na+ 10000 94 Cd2+ 100 93
Ca2+ 10000 97 Co2+ 100 102
Mg2+ 10000 92 Hg2+ 100 91
Al3+ 1000 97 Fe3+ 100 90
Ni2+ 500 107 F− 2000 105
Cu2+ 500 103 Cl− 10000 91
Ba2+ 500 98 NO3 − 10000 90
Pb2+ 200 92 SO4 2− 10000 92
a
Coexisting ion/Cr(VI).
 C. Zeng et al. / Journal of Hazardous Materials 237–238 (2012) 365–370 369

Table 3
Determination of Cr(VI) and Cr(III) in environmental water samplesa (mean ± S.D., n = 3).

Samples Added (ng mL−1 ) Found (ng mL−1 ) Recovery (%)

Cr(VI) Cr(III) Cr(VI) Cr(III) Cr(VI) Cr(III)

Tap water 0 0 N.D. N.D. – –

20 20 19.40 ± 0.52 19.10 ± 0.47 97 95
40 40 38.17 ± 0.46 37.13 ± 0.38 95 93

Industrial waste water 0 0 N.D. 13.45 ± 0.32 – –

15 15 14.62 ± 0.29 29.18 ± 0.41 97 105
30 30 28.21 ± 0.53 44.25 ± 0.49 94 103

Nanliu river water 0 0 N.D. N.D. – –

20 20 18.21 ± 0.37 18.52 ± 0.43 91 93
40 40 37.25 ± 0.54 38.28 ± 0.51 93 96

N.D., not detected.

a
The determined value was the mean of three measurements.

properties of RTILs. The effects of temperature on extraction effi- the recoveries of the spiked samples were in the range of 91–105%,
ciency of Cr(VI) were investigated in the range of 20–70 ◦ C. The indicating the good reliability and validity of the proposed method.
results were shown in Fig. 7., it can be seen from Fig. 7, the
absorbance of Cr(VI) increasing with the increasing of tempera-
ture from 20 to 40 ◦ C, then the absorbance of Cr(VI) remarkably 4. Conclusion
decreasing with the further increasing of temperature from 40 to
70 ◦ C. Therefore, a temperature of 40 ◦ C was selected for further A novel method based on enhancement effect of RTILs for HF-
experiments. LPME combined with FAAS for the speciation of Cr(VI) and Cr(III) in
water samples was developed. The addition of RTILs led to 3.5 times
improvement in the HF-LPME of Cr(VI). The developed method
3.6. Interference evaluation showed the merits of high enrichment factor, simplicity, sensitivity,
low cost, good selectivity, environmental friendliness. The method
DDTC was a universal chelating reagent which can complex with has been successfully applied to the speciation of chromium in tap
other metal elements, and interferences may occur due to the com- water, river water and industrial waste water samples.
petition of other metal ions for DDTC. To evaluate the selectivity of
the developed method, potential interferences from coexisting ions
Acknowledgements
were investigated, including Na+ , K+ , Ca2+ , Mg2+ , Zn2+ , Ba2+ , Cu2+ ,
Hg2+ , Pb2+ , Al3+ , Fe3+ , Co2+ , Ni2+ , Cd2+ , F− , Cl− , NO3 − , SO4 2− . A series
The authors gratefully acknowledge the financial support for
of solutions of 40 ng mL−1 Cr(VI) containing the coexisting ions
this project from the National Natural Science Foundation of China
mentioned above at different concentrations were prepared and
(21265024), Key projects of Yulin Normal College (2012YJZD12)
determined by FAAS after HF-LPME, respectively. The results were
and Guangxi Key Technologies R&D Program for Billion Dollar
shown in Table 1, it can be seen from Table 1 that the selectivity of
Industry (NO11107021-1-6).
the developed method was fairly satisfactory.

3.7. Analytical performance and application
Under the optimal experimental conditions, some characteris-
tics of the proposed method such as enrichment factor, linear range,
correlation coefficients, limit of detection (LOD) and repeatability
were evaluated, respectively. The calibration curve was linear in the
range of 3–200 ng mL−1 for Cr(VI) (R2 > 0.998). The limit of detec-
tion (LOD) of 0.7 ng mL−1 was obtained on the basis of 3␴ criterion
for eleven replicated measurements of the blank signal. The rel-
ative standard deviations (RSD) for five replicate determinations
40 ng mL−1 of Cr(VI) was 4.9%. The enrichment factor was defined
as the ratio of the slope of the calibration curves with and with-
out HF-LPME, and an enrichment factor of 175 was achieved. The
figures of merit of the determination of chromium species by devel-
oped method was compared with some of the previously reported
methods. The results were shown in Table 2. It can be seen from
Table 2, the enrichment factor of the proposed method is higher,
its detection limit is lower than most of the other reported methods.
In order to validate the accuracy of the proposed method, cer-
tified reference environmental water sample GSBZ5027-94 with
certified value for Cr(VI) of 99 ± 6 ng mL−1 was analyzed. The deter-
mined value, 97 ± 5 ng mL−1 was in good agreement with the
certified value. The proposed method was applied to the specia-
tion of Cr(VI) and Cr(III) in different environmental water samples,
and the results were given in Table 3. As can be seen from Table 3,
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