Environ Monit Assess (2015) 187:4129

DOI 10.1007/s10661-014-4129-3

Vortex-assisted surfactant-enhanced emulsification

microextraction based on solidification of floating organic
drop followed by electrothermal atomic absorption
spectrometry for speciation of antimony (ΙΙΙ, V)
Mohammad Eftekhari & Mahmoud Chamsaz &
Mohammad Hossein Arbab-Zavar & Ali Eftekhari

Received: 5 July 2014 / Accepted: 28 October 2014

# Springer International Publishing Switzerland 2014

Abstract Vortex-assisted surfactant-enhanced emulsifi- Keywords Antimony . Speciation . Graphite furnace

cation microextraction based on solidification of float- atomic absorption spectrometry . Vortex-assisted
ing organic drop (VASEME-SFO) was used for surfactant-enhanced emulsification microextraction .
preconcentration and speciation of antimony (ΙΙΙ, V) Solidification of floating organic drop
followed by electrothermal atomic absorption spectrom-
etry (ETAAS). In this procedure, Triton X-114 was used
as emulsifier and 1-undecanol was used as extraction Introduction
solvent. This method is based on the complexation of
Sb(ΙΙΙ) with dithizone (as complexing agent) at pH 2 and Antimony (Sb) is a cumulative toxic element in the
extraction of the resulting hydrophobic complex into the environment and has serious effects on plants, animals,
extraction solvent (1-undecanol) with vortex-assisted and human health (Hansen and Pergantis 2007; Gebel
liquid phase microextraction, whereas Sb(V) remained 1997). It has extensive applications in pharmaceutical
in solution. Sb(ΙΙΙ) in extraction solvent was directly products, alloys, flame retardants, ceramics, semicon-
analyzed by ETAAS after dilution with ethanol, and ductors, and dyestuffs (Krachler et al. 2001). In the
Sb(V) was calculated by subtracting Sb(ΙΙΙ) from the environment, antimony occurs in two oxidation states
total antimony after reducing Sb(V) to Sb(ΙΙΙ) by L- and may form various inorganic and organic species
cysteine. Under the optimized condition, the calibration having different physicochemical and toxic properties.
curve was linear in the range of 0.4–8 μg L−1 of Sb(ΙΙΙ) Inorganic compounds of antimony are more toxic than
with a correlation coefficient of 0.9995. The detection its organic forms. Toxicity of Sb(III) has shown to be 10
limit based on three times of the standard deviation of times higher than that of Sb(V) (Poon et al. 1998).
the blank (n=8) was 0.09 μg L−1. The validation and the According to the US Environmental Protection Agency,
recovery of the proposed method were performed by the antimony in drinking water should be lower than
analysis of a certified reference material and spike meth- 6 μg L−1. Hence, its determination in environmental
od. The obtained results were in very good agreements samples has received considerable interest.
with certified values. The proposed method was suc- Several atomic spectrometric techniques such as
cessfully applied for the determination of antimony flame and electrothermal atomic absorption spectrome-
species at trace levels in different water samples. try (FAAS and ETAAS) (Jiang et al. 2010; Zih-Perényi
et al. 2008; Rivas et al. 2009), atomic fluorescence
M. Eftekhari (*) : M. Chamsaz : M. H. Arbab-Zavar : spectrometry (AFS) (De Gregori et al. 2005), inductive-
A. Eftekhari
ly coupled plasma atomic emission spectrometry (ICP-
Department of Chemistry, Ferdowsi University of Mashhad,
Mashhad, Iran OES) (Huang et al. 2007), and inductively coupled
e-mail: [email protected] plasma mass spectrometry (ICP-MS) (Morita et al.
4129, Page 2 of 8 Environ Monit Assess (2015) 187:4129

2007) have been used for the determination of antimony Limited Company, Beijing, China) was used as a radi-
species in different samples. Since antimony concentra- ation source. Argon, 99.99 %, was used as the inert gas,
tion in environmental and biological sample is very low, the flow rate being 300 mL min−1 during all the stages,
various separation and preconcentration procedures except atomization when the flow was stopped. The
have been used in combination with the above- instrumental parameters are given in Table 1. The pH
mentioned techniques for accurate, reliable, and sensi- values in the aqueous phase were measured with
tive results (Saracoglu et al. 2003; Ozdemir et al. 2004). Metrohm 827 pH lab (Switzerland) glass-electrode pH
Recently, in the year 2010, Yiantzi et al. introduced a meter. A Vortex Gilson mixer (Villiers Le Bel, France)
new microextraction method termed vortex-assisted liq- was used for thoroughly mixing of the solutions. Phase
uid–liquid microextraction (VALLME), whereby dis- separation was assisted using Centurion Scientific Cen-
persion of low-density extraction solvent into the water trifuge (Model Andreas Hettich D72, Tuttlingen,
is obtained through using vortex mixing, a mild emul- Germany).
sification procedure (Yiantzi et al. 2010). In the
VALLME method, the interface between the extraction
Reagents
solvent and the aqueous solution is enormously enlarged
by forming the fine droplets of extraction solvent. Con-
All reagents were of analytical reagent grade, and de-
sequently, the equilibrium of the extraction was
ionized water was used throughout. Deionized water
achieved in a short time.
(18.1 MΩcm) was obtained from a Barnstead, Nanopure
In the present work, a vortex-assisted surfactant-en-
Diamond purification system. The Sb(III) and Sb(V)
hanced emulsification microextraction based on solidi-
stock standard solutions (1000 mg L−1) were prepared
fication of floating organic drop (VASEME-SFO) was
by dissolving of appropriate amounts of potassium an-
used for speciation of Sb(ΙΙΙ, V). Triton X-114 was used
timony tartrate and potassium hexahydroxyantimonate
as emulsifier to accelerate the emulsification of the
(Fluka, Chemical com., USA) in deionized water, re-
water-immiscible extraction solvent (1-undecanol) in
spectively. Working standard solutions were obtained
the aqueous solution. Dithizone was used as complexing
by appropriate dilutions of the stock standard solutions
agent to form a hydrophobic complex with Sb(ΙΙΙ) at pH
with deionized water. A 10−3 mol L−1 dithizone (Merck,
2, whereas Sb(V) remained in solution. By using the
Darmstadt, Germany) in ethanol was used as the
vortex agitator system, the hydrophobic complex of
complexing agent. 1-Undecanol (Merck, Darmstadt,
Sb(ΙΙΙ)–dithizone extracted into the fine droplets of 1-
Germany) was used as extraction solvent. A
undecanol and quantitatively determined by electrother-
10−3 mol L−1 Triton X-100 (Merck, Darmstadt, Germa-
mal atomic absorption spectrometry. The main parame-
ny) and Triton X-114 (Merck, Darmstadt, Germany)
ters affecting the VASEME-SFO-ETAAS were investi-
was prepared in deionized water and used as emulsifier.
gated in details and optimized. This method was suc-
A solution of 1.5 % (w/v) of L-cysteine (Merck, Darm-
cessfully used for the determination of antimony species
stadt, Germany) was made in deionized water. Diluted
in different water samples.
hydrochloric acid and sodium hydroxide were used to
adjust the pH.
Experimental Table 1 Instrumental parameters and temperature program for
antimony analysis
Instrumentation
Step Temperature/ Ramp Hold Flow rate of argon
°C time/s time/s (mL min−1)
A PerkinElmer HGA 700 model 4100 (Norwalk, CT,
USA), graphite furnace atomic absorption spectrometry Drying 1 130 4 20 300
equipped with deuterium lamp as a background correc- Drying 2 240 25 15 300
tion system was used for the determination of antimony Drying 3 280 20 15 300
in the extraction solvent. Pyrolytically coated graphite Ashing 900 10 15 300
tubes (PerkinElmer, HGA 700) with L’vov platform Atomization 2000 0 3 0
were used. An antimony hollow cathode lamp (Beijing Cleaning 2300 1 3 300
Shuguang-Ming Electronic Lighting Source Instrument
Environ Monit Assess (2015) 187:4129 Page 3 of 8, 4129

Microextraction procedure Results and discussions

Eight milliliters of the sample solution containing an Different parameters such as pH, ligand concentration,
aliquot of Sb(ΙΙΙ) or Sb(V) in the calibration range, 3.2× volume of extraction solvent, ionic strength, and extrac-
10−4 mol L−1 dithizone and 1.25×10−5 mol L−1 Triton tion time which have important effects on the extraction
X-114, was adjusted at pH 2 with diluted hydrochloric efficiency were completely investigated and optimized.
acid and then transferred into a conical bottom glass
centrifuge tube. Then, 65 μL of 1-undecanol was added
and the tube was shaken by a vortex agitator system for Effect of the ETAAS optimization
100 s at 2800 rpm until a cloudy solution (resulting from
the dispersion of the fine droplets of 1-undecanol by the The drying, pyrolysis, and atomization temperature to
vortex system in the aqueous solution) was formed in determine the antimony in the organic phase were opti-
the test tube, and the hydrophobic complex of Sb(ΙΙΙ)– mized and presented in Table 1. The drying step was
dithizone extracted into the fine droplets of 1-undecanol. applied in three steps (to remove 1-undecanol): first, at
To separate the extraction solvent from the aqueous 130 °C; second, at 240 °C; and third, at 280 °C as listed
solution, the mixture was centrifuged at 3600 rpm for in the Table 1. The selection of an appropriate pyrolysis
4 min. The test tube was transferred to a beaker contain- temperature is essential to remove the matrix and
ing ice, and the organic solvent was solidified after preventing the pyrolysis loss of the analytes prior to
10 min (62±2 μL). The solidified organic solvent was atomization. The effect of pyrolysis temperature on the
transferred into a 1.5-mL Eppendorf where it melted absorbance of antimony was investigated in the range of
immediately. After dilution to 150 μL with ethanol 700–1000 °C. Based on the results, the matrix was
(for reducing the viscosity), 20 μL of the organic phase eliminated at a pyrolysis temperature of 900 °C and
was injected into the electrothermal atomizer by an decreased at a higher pyrolysis temperature due to anti-
autosampler to obtain the analytical signal. mony loss. Therefore, 900 °C was selected as the opti-
mum pyrolysis temperature.
The effect of atomization temperature on the signal of
Determination of Sb(ΙІΙ) and Sb(V) antimony was studied at 1800–2200 °C. The results
show that maximum signal was obtained at 2000 °C
(1) Sb(ΙΙІ): According to the microextraction proce- and remained constant up to 2200 °C. Therefore,
dure, 20 μL of the diluted solution was injected 2000 °C was selected as the optimum value.
into the graphite furnace for the determination of
Sb(ІΙІ).
(2) Total Sb: To determine the total Sb in sample Effect of pH
solution, 0.1 % (w/v) of L-cysteine is used as re-
ducing agent at pH 2.5 then the solution was The pH of sample solution is an important parameter
heated in a water bath at 60 °C for 30 min. The affecting the formation of hydrophobic complexes,
total Sb was determined according to the and it has an important effect on the speciation of
microextraction procedure. elements (Chamsaz et al. 2014; Tuzen et al. 2009).
(3) Sb(V): The content of Sb(V) was calculated by the The effects of pH on the absorbance of Sb(ΙΙΙ) and
subtraction of Sb(III) from the total Sb. Sb(V) were studied in the range of 1–9. As can be
seen in Fig. 1, the absorbance of Sb(ΙΙΙ) was reached
to its maximum at pH 2, and decreased gradually at
higher pH values, while there is no extraction of
Preparation of real samples Sb(V) in the pH ranges of 1–9. Based on the results,
the hydrophobic complex of Sb(ΙΙΙ)–dithizone is
Water samples were collected from their local sources stable in acidic conditions and its stability decreases
and filtered through a No. 42 Whatman® paper to re- with increasing pH values. Therefore, pH 2.0 was
move any suspended particles and then analyzed ac- adapted for the selective separation of Sb(III) and
cording to the microextraction procedure. Sb(V).
4129, Page 4 of 8 Environ Monit Assess (2015) 187:4129

Fig. 1 Effect of pH on the absorbance of Sb(ΙΙΙ) and Sb(V). Conditions are 2 μg L−1 Sb(ΙΙΙ)/Sb(V), 3.2×10−4 mol L−1 dithizone, 1.25×
10−5 mol L−1 Triton X-114, 65 μL 1-undecanol, 100-s extraction time, and 4-min centrifugation time

Effect of ligand concentration 70 μL and no significant changes were observed for

higher volumes of extraction solvent. Therefore, 65 μL
Ligand concentration is important to establish the min- of 1-undecanol was selected as the optimum value.
imal reagent concentration leading to a complete com-
plex formation while achieving the highest extraction.
Effect of extraction time
The variation of the absorbance as a function of the
concentration of dithizone in the range of 5.5×10−5–
Extraction time is an important factor influencing the
4.0×10−4 mol L−1 was studied, and the experimental
extraction efficiency for achieving maximum sensitivity
result was demonstrated in Fig. 2. The results show that
of the extraction process. In VASEME, the interface
the absorbance increases from 5.5 × 10 −5 to 2.8 ×
between the extraction solvent and aqueous phase was
10−4 mol L−1 dithizone and then remained constant.
enormously enlarged by forming the cloudy solution.
Therefore, for further studies, a concentration of 3.2×
Consequently, the equilibrium of the extraction was
10−4 mol L−1 dithizone was selected as the optimum
achieved in a short time. In this work, the effect of
value.
extraction time was studied in the range of 30–240 s.
The results show that (data not shown) a 100-s vortex
time is sufficient for the extraction of the analyte. There-
Effect of the volume of the extraction solvent
fore, a 100-s extraction time was selected as the opti-
mum value.
The extraction solvent has an important role to obtain
high recovery and extraction efficiency. For this pur-
pose, the extraction solvent must have low water solu- Effect of surfactant concentration
bility, low volatility, and high hydrophobic nature. 1-
Undecanol is an organic solvent having the advantages In this study, the effect of two non-ionic surfactants,
mentioned above with a melting point near to room Triton X-100 and Triton X-114, as anti-sticking agent
temperature which can be used as an extraction solvent and emulsifier were investigated. In VASEME, the sur-
for SFO (Chamsaz et al. 2013; 2014). Figure 3 shows factant serves as an emulsifier to accelerate the emulsi-
the effect of volume of 1-undecanol on the absorbance fication of the water-immiscible extraction solvent in the
of Sb(III). According to the results, the absorbance aqueous solution under the vortex stream, and hence, its
reaches to its maximum value in the range of 60– correct choice is critical for obtaining satisfactory
Environ Monit Assess (2015) 187:4129 Page 5 of 8, 4129

Fig. 2 Effect of dithizone concentration on the absorbance of Sb(ΙΙΙ). Conditions are 2 μg L−1 Sb(ΙΙΙ), 1.25×10−5 mol L−1 Triton X-114,
65 μL 1-undecanol, 100-s extraction time, and 4-min centrifugation time

extraction efficiency. Also, the surfactants can reduce Therefore, 1.25×10−5 mol L−1 Triton X-114 was select-
the adherence of 1-undecanol to the centrifuge tube, ed as the optimum value.
enabling effective separation of extraction solvent from
the solution (Chamsaz et al. 2013). The effects of two Effect of centrifugation time
non-ionic surfactants were investigated in the concen-
tration range of 2.5×10−6–4.0×10−5 mol L−1. Accord- Centrifugation time is an important parameter that in-
ing to the results (data not shown), Triton X-114 is fluences the separation of extraction solvent from the
superior in the concentration of 1.25×10−5 mol L−1. aqueous phase. A centrifugation time was investigated

Fig. 3 Effect of extraction solvent volume on the absorbance of Sb(ΙΙΙ). Conditions are 2 μg L−1 Sb(ΙΙΙ), 3.2×10−4 mol L−1 dithizone, 1.25×
10−5 mol L−1 Triton X-114, 100-s extraction time, and 4-min centrifugation time
4129, Page 6 of 8 Environ Monit Assess (2015) 187:4129

in the range of 1–10 min at a rate of 3600 rpm. The Table 2 Effect of the interfering ions on the absorbance of
2 μg L−1 Sb(ΙΙΙ)
results show that (data not shown) a 4-min centrifuga-
tion time is adequate to the satisfactory separation of Interfering Added as Concentration Recovery
two immiscible phases. Therefore, a 4-min centrifuga- ions (μg L−1) (%)
tion time at 3600 rpm was selected as the optimum
K+ KNO3 100,000 100.0
value.
Na+ NaNO3 100,000 99.5
Al3+ Al(NO3)3.9H2O 1000 97.1
Effect of ionic strength
Zn2+ Zn(NO3)2 1000 99.0
Addition of salt to the sample may have several Pb2+ Pb(NO3)2 1000 98.0
2+
effects on the extraction efficiency. The increase in Co Co(NO3)2.6H2O 1000 98.3
the extraction efficiency as the result of salting out Fe3+ Fe(SO4)2NH4.H2O 1000 96.3
effect can be explained by the engagement of Mn2+ MnSO4.H2O 1000 99.6
water molecules in the hydration spheres around Ni2+ Ni(NO3)2 500 96.0
the ionic salt and hence in the reduction of the Cd2+ Cd(NO3)2.H2O 250 98.0
2+
water molecules available to dissolve the analytes, Cu Cu(NO3)2.5H2O 250 97.8
so the availability of analyte increases and the Cl− KCl 100,000 97.3
extraction efficiency is improved. On the other NO3− NaNO3 100,000 100.0
hand, increasing the salt concentration may de- SO42− K2SO4 100,000 98.7
crease the dispersion of extraction solvent in the CH3COO− CH3COONa 100,000 96.9
sample solution causing to decrease in extraction
efficiency (Chamsaz et al. 2013). To study the
effect of ionic strength on the absorbance of calculated as the ratio between the volume of the aque-
Sb(III), different experiments were performed by ous phase (8 mL) and the final volume of the extraction
varying the concentration of KNO3 in the range phase (150 μL), was 53. The relative standard deviation
of 0–7 % (w/v). The results show that the absor- (RSD, %) based on six replicate analysis of sample
bance was constant upto 2 % (w/v) KNO3, and it solution containing 2 and 5 μg L−1 of Sb(ΙІΙ) were 5.4
decreased gradually with further increasing of and 4.3 %, respectively. The detection limit (calculated
KNO3 concentration. Therefore, all experiments as the concentration equivalent to three times of the
were performed without the addition of salt. standard deviation of the blank divided into the slope
of the calibration curve after preconcentration) was
Effect of interfering ions 0.09 μg L−1 (n=8).

The effects of different interfering ions on the absor-

bance of Sb(III) were studied. Ions were considered as Analysis of real samples
interfering when their presence caused a variation in the
absorbance of the sample greater than ±5 %. The results The proposed method was used for speciation of anti-
of this investigation are given in Table 2, which clearly mony in different water samples. In order to validate the
indicate that this method has good tolerance to matrix proposed method, recovery experiments were also car-
interference. ried out by spiking the sample with different concentra-
tions of Sb(ΙΙΙ) and Sb(V). The results are given in
Analytical figures of merit Table 3. Also, the accuracy of the proposed method
was successfully performed by the analysis of CRM-
Under the optimum conditions, the calibration curve TMDW (drinking water) certified reference material
was linear in the range of 0.4–8 μg L−1 Sb(ΙІΙ). The with the certified value of 10 μg L−1 antimony. The
calibration equation was determined to be A=0.0203+ observed value of the analysis of CRM was 9.79±
0.0505 C, where A is the analytical signal measured as 0.6 μg L−1 (mean±standard deviation based on three
absorbance and C is the concentration of Sb(ΙΙΙ) in replicate analysis) which shows that the observed value
micrograms per liter. The preconcentration factor, is in very good agreement with certified value.
Environ Monit Assess (2015) 187:4129 Page 7 of 8, 4129

Table 3 Results (mean±standard deviation based on three replicate analyses) for the determination of antimony species in water samples

Samples Added (μg L−1) Founded (μg L−1) Recovery (%)

Sb(ΙΙΙ) Sb(V) Sb(ΙΙΙ) Sb(V) Total Sb Sb(ΙΙΙ) Sb(V) Total Sb

Tap water 0 0 ND ND ND – – –
1 1 0.96±0.02 1.05±0.04 2.01±0.07 96.0 105.0 100.5
2 2 2.15±0.06 1.98±0.07 4.13±0.11 107.5 99.0 103.2
Spring watera 0 0 0.81±0.02 1.01±0.04 1.82±0.06 – – –
2 2 2.68±0.07 2.90±0.06 5.58±0.14 95.4 96.3 95.9
4 4 4.55±0.10 5.10±0.13 9.65±0.31 94.6 101.8 98.3
Mineral water 0 0 ND 0.85±0.02 0.85±0.02 – – –
2 2 2.10±0.05 2.76±0.07 4.86±0.12 105.0 96.8 100.2
4 4 3.93±0.09 4.73±0.10 8.66±0.28 98.2 97.5 97.8

ND not detected
a
Obtained from Nowchah, Mashhad, Iran

Comparison to other methods organic drop (VASEME-SFO) followed by electro-

thermal atomic absorption spectrometry was used
A comparison of the presented method with other for the speciation of Sb(ΙΙΙ, V). The method is
reported preconcentration procedures are given in based on the complexation of Sb(ΙΙΙ) with
Table 4. In comparison with the other reported dithizone at pH 2, while Sb(V) remained in the
methods, the proposed method has the advantages solution. 1-Undecanol was used as extraction sol-
of good linear range, low LOD, and rapidity. vent, and Triton X-114 was used as emulsifier.
Moreover, since this method uses only 65 μL of The hydrophobic complex of Sb(ΙΙΙ)–dithizone
1-undecanol, it is relatively free of organic hazard- was extracted by the assistance of the vortex agi-
ous solvents. Therefore, all these results indicate tator system into the fine droplets of 1-undecanol
that VASEME-SFO is a rapid, environmentally at a short extraction time. The surfactant acceler-
friendly and simple technique that can be used ates the emulsification of the water-immiscible ex-
for the speciation of Sb(ΙΙΙ, V). traction solvent in the aqueous solution under the
vortex stream which can improve the extraction
efficiency. This method is simple, rapid, and rela-
Conclusion tively free of organic hazardous solvent. The pro-
posed method was successfully used for the deter-
Vortex-assisted surfactant enhanced emulsification mination of antimony species in different water
microextraction based on solidification of floating samples.

Table 4 Comparison of the VASEME-SFO-ETAAS with some other recent studies on speciation of antimony

Method Calibration range (μg L−1) LOD (μg L−1) RSD (%) Extraction time (min) References

CPE-FAAS – 1.82 2.6 10 Fan (2005)

SPE-GFAAS – 0.14 6.8 20 Zhang et al. (2007)
CPE-ETV-ICP – 0.09 4.3 – Li et al. (2006)
CPE-GFAAS 0.1–3 0.02 7.8 15 Jiang et al. (2010)
SPE-GFAAS – 0.02 7 >10 Mendil et al. (2013)
VASEME-SFO-ETAAS 0.4–8 0.09 5.4 <2 This work
4129, Page 8 of 8 Environ Monit Assess (2015) 187:4129

References Li, Y., Hu, B., & Jiang, Z. (2006). On-line cloud point
extraction combined with electrothermal vaporization
inductively coupled plasma atomic emission spectrom-
Chamsaz, M., Eftekhari, M., Eftekhari, A., & Yekkebashi, A. etry for the speciation of inorganic antimony in envi-
(2013). 2-Nitroso-1-naphthol as a selective reagent for ronmental and biological samples. Analytica Chimica
preconcentration of cobalt by vortex assisted combined with Acta, 576, 207–214.
solidification of organic droplet and its determination by Mendil, D., Bardak, H., Tuzen, M., & Soylak, M. (2013).
flame atomic absorption spectrometry. Environmental Selec tive speciat ion of inorg ani c antimony on
Monitoring and Assessment, 185, 9067–9075. tetraethylenepentamine bonded silica gel column and its
Chamsaz, M., Eftekhari, M., Tafreshi, S., Yekkebashi, A., & determination by graphite furnace atomic absorption spec-
Eftekhari, A. (2014). Speciation and determination of iron trometry. Talanta, 107, 162–166.
using dispersive liquid–liquid microextraction based on so- Morita, Y., Kobayashi, T., Kuroiwa, T., & Narukawa, T. (2007).
lidification of organic drop followed by flame atomic absorp- Study on simultaneous speciation of arsenic and antimony by
tion spectrometry. International Journal of Environmental HPLC-ICP-MS. Talanta, 73, 81–86.
Analytical Chemistry, 94, 348–355. Ozdemir, N., Soylak, M., Elci, L., & Dogan, M. (2004). Speciation
De Gregori, I., Quiroz, W., Pinochet, H., Pannier, F., & Potin- analysis of inorganic Sb(III) and Sb(V) ions by using mini
Gautier, M. (2005). Simultaneous speciation analysis of column filled with Amberlite XAD-8 resin. Analytica
Sb(III), Sb(V) and (CH3)3SbCl2 by high performance liquid Chimica Acta, 505(1), 37–41.
chromatography–hydride generation–atomic fluorescence Poon, R., Chu, I., Lacavalier, P., Valli, V., Foster, W., Gupta, S., &
spectrometry detection (HPLC–HG–AFS): application to an- Thomas, B. (1998). Effects of antimony on rats following 90-
timony speciation in sea water. Journal of Chromatography day exposure via drinking water. Food and Chemical
A, 1091, 94–101. Toxicology, 36, 21–35.
Fan, Z. (2005). Speciation analysis of antimony (III) and antimony Rivas, R. E., López-García, I., & Hernández-Córdoba, M. (2009).
(V) by flame atomic absorption spectrometry after Speciation of very low amounts of arsenic and antimony in
separation/preconcentration with cloud point extraction. waters using dispersive liquid–liquid microextraction and
Microchimica Acta, 152, 29–33. electrothermal atom ic absorption spectrometry.
Gebel, T. (1997). Arsenic and antimony: comparative approach on Spectrochimica Acta Part B, 64, 329–333.
mechanistic toxicology. Chemico-Biological Interactions, Saracoglu, M., Soylak, M., Dogan, M., & Elci, L. (2003).
107, 131–144. Speciation of antimony using chromosorb 102 resin as a
Hansen, H. R., & Pergantis, S. A. (2007). Identification of Sb (V) retention medium. Analytical Sciences, 19(2), 259–264.
complexes in biological and food matrixes and their stibine Tuzen, M., Citak, D., Mendil, D., & Soylak, M. (2009). Arsenic
formation efficiency during hydride generation with ICP-MS speciation in natural water samples by co-precipitation hy-
detection. Analytical Chemistry, 79, 5304–5311. dride generation atomic absorption spectrometry combina-
Huang, C. Z., Hu, B., & Jiang, Z. C. (2007). Simultaneous speci- tion. Talanta, 78, 52–56.
ation of inorganic arsenic and antimony in natural waters by Yiantzi, E., Psillakis, E., Tyrovola, K., & Kalogerakis, N.
dimercaptosuccinic acid modified mesoporous titanium di- (2010). Vortex-assisted liquid–liquid microextraction of
oxide micro-column on-line separation and inductively octylphenol, nonylphenol and bisphenol-A. Talanta, 80,
coupled plasma optical emission spectrometry determination. 2057–2062.
Spectrochimica Acta Part B, 62, 454–460. Zhang, L., Morita, Y., Sakuragawa, A., & Isozaki, A. (2007).
Jiang, X., Wen, S., & Xiang, G. (2010). Cloud point extraction Inorganic speciation of As (III, V), Se(IV, VI) and Sb(III,
combined with electrothermal atomic absorption spectrome- V) in natural water with GF-AAS using solid phase extrac-
try for the speciation of antimony (III) and antimony (V) in tion technology. Talanta, 72, 723–729.
food packaging materials. Journal of Hazardous Materials, Zih-Perényi, K., Jankovics, P., Sugár, E., & Lásztity, A. (2008).
175, 146–150. Solid phase chelating extraction and separation of inorganic
Krachler, M., Emons, H., & Zheng, J. (2001). Speciation of antimony species in pharmaceutical and water samples for
antimony for the 21st century: promises and pitfalls. Trends graphite furnace atomic absorption spectrometry.
in Analytical Chemistry, 20, 79–90. Spectrochimica Acta Part B, 63, 445–449.