Microchemical Journal 147 (2019) 832–837

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Deep eutectic solvent microextraction of lead(II), cobalt(II), nickel(II) and T

manganese(II) ions for the separation and preconcentration in some oil
samples from Turkey prior to their microsampling flame atomic absorption
spectrometric determination
Mustafa Soylak , Meltem Koksal
⁎

Erciyes University, Faculty of Sciences, Department of Chemistry, 38039 Kayseri, Turkey

ARTICLE INFO ABSTRACT

Keywords: A new liquid phase microextraction method based on deep eutectic solvent microextraction was developed for
Edible oil samples separation and preconcentration of lead, cobalt, nickel and manganese from edible oil samples like sunflower oil,
Microextraction baby oil, trout, waste frying oil and syrup-soaked pastry oil. A choline chloride deep eutectic solvent was used for
Trace element microextraction. After extraction, analytical concentrations were determined by flame atomic absorption
Deep eutectic solvent
spectrometry. Effects of analytical parameters such as type and volume of deep eutectic solvent, sample volume,
Flame atomic absorption spectrometry
and temperature on extraction efficiency of lead, cobalt, nickel and manganese were optimized. The recoveries
were generally > 95%. The relative standard deviation (RSD, %, n = 7) of 50 μg/ L of analyte elements was in
the range of 0.9–4.3%. Accuracy of presented microextraction method was checked by addition-recovery studies
to oil samples. The presented deep eutectic solvent microextraction method was finally applied to edible oil
samples and waste oils with different properties for the determination of analyte contents.

1. Introduction classical organic solvents [31–33]. Deep eutectic solvents (DESs) are
typically formed by mixing an appropriate amount of a hydrogen bond
Elements at trace levels have important positive and negative roles acceptor such as choline chloride salt (ChCl, Vitamin B4) with safe
in human life. Some of them such as copper, zinc and manganese are hydrogen bond donors (e.g. urea, glycerol, sugars, carboxylic acids,
necessary for health life [1–3], others like cadmium, lead and arsenic etc.). DESs were prepared from ChCl provide many advantages such as
are non-necessary for our life [4–6]. Their determinations in environ- low price, easy to prepare by simply mixing components, no need to
mental and food samples are given important information about their further purification, most of them are biodegradable, biocompatible
sources and their levels for human [7–10]. Flame atomic absorption and non-toxic when compared to organic solvents and ionic liquids used
spectrometry (FAAS) is one of the popular and main instruments in the in the microextraction methods [34–37].
determinations of metals at trace levels [11–14]. However, thre main Oils are very important food all around world. The human uses oils
disadvantage of FAAS is the high instrumental detection limits [15–18]. in the diet for three purposes, as an energy source, as a structural
In order to solve this problem, analytical chemist are used separation- component and to make powerful biological regulators [38–40]. The
preconcentration methods including solid phase extraction, coprecipi- quality of edible oils is directly related to the level of trace metals
tation, and membrane filtration [19–25]. [41–43]. The levels of metals at trace levels in oil samples are known to
Microextraction procedures are very popular at last decade for the increase the rate of oil oxidation. The presence of metals at trace levels
separation-preconcentration of traces inorganic and organic species due in edible oils may be due to different factors: The metal ions at trace
to their advantages including short extraction times, minimum usage of levels in the oil samples can be incorporated in to the oil from the soil of
organic solvents, high preconcentration factors etc. [26–31]. In the the area or be introduced during the manufacturing of food samples
microextraction studies for trace species, new generation solvents like [44–48].
supramoleculer solvents, switchable solvents and deep eutectic solvents A deep eutectic solvent microextraction procedure for the separa-
that are the member of green chemistry were generally preferred than tion and preconcentration of lead, cobalt, nickel and manganese from

⁎
Corresponding author.
E-mail address: [email protected] (M. Soylak).

https://doi.org/10.1016/j.microc.2019.04.006
Received 16 December 2018; Received in revised form 1 March 2019; Accepted 1 April 2019
Available online 02 April 2019
0026-265X/ © 2019 Elsevier B.V. All rights reserved.
M. Soylak and M. Koksal Microchemical Journal 147 (2019) 832–837

some oil samples has been established in this work. The concentration 2.2. Reagents and solutions
of the analyte elements were determined by using microsampling flame
atomic absorption spectrometric determinations. High purity analytical grade reagents were used. All solutions were
prepared with reverse osmosis purified water (Millipore Milli-Q system
18 MΩ cm−1 resistivity). Stock solutions of the analyte elements were
2. Experimental prepared from their nitrates as 1000 mg L−1, solutions in 0.02 M HNO3.
The working solutions that contain 25 mg L−1 of each analytes were
2.1. Instruments daily prepared by diluting stock solutions.
Except if otherwise stated, analytical-grade lactic acid, oxalic acid,
The instrumental detection system used was a PerkinElmer Model ethyl glycol were obtained from Merck (Darmstadt, Germany). Choline
3110 flame atomic absorption spectrometer (Norwalk, CT, USA) chloride (ChCl) was purchased from Alfa Aesar (Karlsruhe Germany).
equipped with a 10 cm a long slot-burner and hollow cathode lamps of
lead, cobalt, nickel and manganese. The instrument was run under the
conditions suggested by the manufacturer. The samples were injected to 2.3. Preparation of deep eutectic solvents
the FAAS by using micro injection system, which consist of a mini
home-made Teflon funnel with an Eppendorf Pipette [29,32]. The Te- DESs are prepared from available salts and hydrogen bond donors in
flon funnel was connected to the nebulizer of FAAS with capillary laboratory conditions. DESs were prepared by mixing different mole
tubing. The measurements were performed with the continuous as- ratios of ChCl with oxalic acid (1:2 mol), ChCl with ethylene glycol
piration mode of FAAS. A hundred μL of extraction phase was injected (1:2 mol), ChCl with lactic acid (1:2 mol) and ChCl with urea (1:2 mol).
to the micro-injection unit by using Eppendorf pipette and peak heights They were prepared on the water bath by heating choline chlor-
were recorded as signals. ide‑hydrogen bond donors and to 80 °C with constant stirring with
The peak heights were recorded as signals. A Nel pH -900 pH meter magnetic stirrer for 2 min until a homogeneous liquid was formed.
(Ankara, Turkey) with a combined glass electrode was used for the pH
measurements. An RS-VA10 vortex mixer (Phoenix Instrument, 2.4. Microextraction procedure for oil samples
Germany) was used to assist the extraction process. An RH Basic Model
magnetic stirrer (IKA, Germany) was used. A Rotofix 32A Model The presented microextraction procedure was applied to a sun-
(Hettich, Germany) centrifuge was also used. flower oil sample for the optimization of the procedure. 200 μL of

Fig. 1. The schematic diagram of microextraction procedure.

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M. Soylak and M. Koksal Microchemical Journal 147 (2019) 832–837

Table 1 100
Influence of DES type on the recoveries of analytes (N = 3).
Recovery, % 80

Recovery, %
ChCl with oxalic ChCl with ChCl with lactic ChCl with urea 60
acid (1:2 mol) ethylene glycol acid (1:2 mol) (1:2 mol)
(1:2 mol) Co(II)
40 Ni(II)
Pb(II) 100 ± 2 104 ± 8 97 ± 6 97 ± 5
Mn(II)
Co(II) 101 ± 4 96 ± 5 99 ± 2 95 ± 5 20
Ni(II) 94 ± 3 97 ± 4 98 ± 5 98 ± 2 Pb(II)
Mn(II) 99 ± 2 98 ± 6 102 ± 4 96 ± 4
0
100 200 300 400 500
working solution of that contain 25 mg L−1 of Pb(II), Co(II), Ni(II) and DES volume, µL
Mn(II) was introduced to 50 mL centrifuge tube, and followed by se- Fig. 2. The influences of DES volume on the recovery values of the analyte
quentially addition of 20 mL oil sample, and 300 μL of DESs. The elements (N = 3).
sample solution was vortex for 1 min, in result a monophase solution
was achieved. Then, 75 μL of HNO3 was added in the solution and the
100–500 μL of ChCl with urea (1:2 mol). The results are depicted in
obtained solution was placed into a water bath for 30 min at 100 °C.
Fig. 2. The quantitative recoveries of Pb(II), Co(II), Ni(II) and Mn(II)
After this stage, it was wortexed 2 min. Then the prompt phase se-
ions were obtained with 200 μL of ChCl with urea (1:2 mol) and it was
paration was obtained by centrifuging sample mixture at 4000 rpm for
chosen as optimal value for further analysis.
5 min. At this stage, oil and DES rich phase were obtained. The DES was
decanted by the help of micropipette and methanol was added to re-
maining metal enrich DES phase up to final volume 1 mL to decrease 3.3. Effects of volume of nitric acid
the viscosity of DES. Then absorbance values for analyte elements were
measured by using micro-sample injection flame atomic absorption In order to deep eutectic solvent microextraction of analyte ele-
spectrometer (MS-FAAS). The schematic diagram of microextraction ments from oil phase to polar phase, acidic medium was selected by
procedure was given in Fig. 1. using different volume of concentrated nitric acid. Concentrated nitric
acid was added to oil samples at different volumes at the micro-
3. Results and discussions extraction stage. The results were given in Fig. 3. Quantitative re-
coveries were obtained with 75 and 100 μL of concentrated nitric acid.
3.1. Selection of extraction solvent type and volume 75 μL of concentrated nitric acid was selected as an optimal value.

The selection of the type of DES is a critical parameter for the 3.4. Effects of temperature of water bath for the extraction efficiencies
quantitative microextraction of the analytes [49–51]. Four different
DES at different composition given in Table 1 were prepared as an The influences of the temperature of the water bath on the extrac-
extraction solvents for presented work and the procedure given at “the tion efficiency of lead(II), cobalt(II), nickel(II) and manganese(II) for
procedure” section was applied to an oil sample for all DES solutions. As the presented microextraction procedure were also investigated chan-
can be seen in Table 1 in the quantitative recoveries were obtained for ging the temperature of water bath in the range of 20–100 °C. The
Pb(II), Co(II), Ni(II) and Mn(II) ions with four different DES solutions. quantitative recoveries (> 95%) for each analyte elements were ob-
For further works, ChCl with urea DES solution was selected due to its tained at 100 °C of water bath temperature. 100 °C was selected as
easier preparation than other ones. optimal temperature for working temperature for the water bath.
The effects of the different combination on the ChCl with urea so-
lution on the recoveries of the analyte elements were examined under 3.5. Effects of extraction time
optimal working conditions. The results summarized in Table 2. The
quantitative results were obtained for lead(II), cobalt(II), nickel(II) and The effects of the extraction time in the range of 5–45 min at 100 °C
manganese(II) ions with the all working combination of the ChCl and on the water bath were investigated on the recoveries of Pb(II), Co(II),
urea given in Table 2. 1:2 mol Choline chloride with urea combination
were selected for further experiments.
100
3.2. Effect of DES volume
Recovery, %

80
The effects of volume of DES solution (ChCl with urea (1:2 mol)) on
the recoveries of the analyte elements were examined in the range of Co(II)
60
Table 2
Ni(II)
The effects of different combination on the ChCl with urea solution on the re- 40 Mn(II)
coveries of the analyte elements (N = 3).
Pb(II)
Recovery, % 20
ChCl with urea ChCl with urea ChCl with urea 50
75
(1:2 mol) (1:3 mol) (1:4 mol) 100
Pb(II) 97 ± 5 100 ± 4 98 ± 3 Volume of conc. HNO3, µL
Co(II) 95 ± 5 98 ± 5 95 ± 4
Ni(II) 98 ± 2 96 ± 4 101 ± 6
Fig. 3. The influences of volume of HNO3 on the recoveries of analyte elements
Mn(II) 96 ± 4 100 ± 5 94 ± 4
(N = 3).

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Table 3
Analytical characteristics of the presented procedure.
Analyte LODa, μg/L LOQb, μg/L Calibration graph equation R2 Linear range after microextraction, μg/L

c
Pb 2.4 7.9 A = 0.005C - 0.0007 0.997 5–60
Co 4.6 15.2 A = 0.022C - 0.0004 0.986 5–30
Ni 7.5 24.8 A = 0.015C - 0.0030 0.992 10–50
Mn 1.0 3.3 A = 0.072C + 0.0031 0.997 2.5–25

a
LOD: limit of detection.
b
LOQ: limit of quantification.
c
A = the measured absorbance values for FAAS and C = Concentration of analyte element in last phase.

Table 4
Application of the presented microextraction procedure to waste frying sunflower oil and syrup-soaked pastry oil (N = 3).
Waste frying sunflower oil Syrup-soaked pastry oil

Analyte Added Found Recovery, % Added Found Recovery, %

μg/mL μg/mL μg/mL μg/mL

Pb 0 BLQ – 0 BLQ –
1.87 1.92 ± 0.50⁎ 103 1.25 1.24 ± 0.02 99
3.75 3.77 ± 0.10 101 2.56 2.71 ± 0.30 106
Co 0 BLQ – 0 BLQ –
1.87 1.82 ± 0.50 97 1.25 1.24 ± 0.60 99
3.75 3.81 ± 0.10 102 2.56 2.49 ± 0.01 97
Ni 0 BLQ – 0 BLQ –
1.87 1.85 ± 0.05 99 1.25 1.21 ± 0.01 97
3.75 3.69 ± 0.10 98 2.56 2.45 ± 0.10 96
Mn 0 BLQ – 0 2.12 ± 0.10 –
1.87 1.78 ± 0.06 95 1.25 3.45 ± 0.05 96
3.75 3.82 ± 0.05 102 2.56 4.50 ± 0.00 93

BLQ: Below the limit of quantification.

⁎
Mean ± standard deviation.

Table 5
Application of the presented microextraction procedure to baby oil and trout oil (N = 3).
Baby oil Trout oil

Analyte Added Found Recovery, % Added Found Recovery, %

μg/mL μg/mL μg/mL μg/mL

Pb 0 BLQ – 0 BLQ –
0.63 0.65 ± 0.05⁎ 103 0.63 0.63 ± 0.02 100
1.25 1.23 ± 0.10 98 1.25 1.25 ± 0.05 100
Co 0 BLQ – 0 BLQ –
0.63 0.62 ± 0.06 98 0.63 0.64 ± 0.30 102
1.25 1.29 ± 0.20 103 1.25 1.28 ± 0.02 102
Ni 0 BLQ – 0 BLQ –
0.63 0.64 ± 0.05 102 0.63 0.61 ± 0.01 97
1.25 1.21 ± 0.10 97 1.25 1.25 ± 0.30 100
Mn 0 BLQ – 0 0.50 ± 0.01 –
0.63 0.64 ± 0.07 102 0.63 1.13 ± 0.05 100
1.25 1.25 ± 0.05 101 1.25 1.78 ± 0.00 102

BLQ: Below the limit of quantification.

⁎
Mean ± standard deviation.

Table 6
The comparison of the methods for separation and preconcentration of the trace element from oil samples in literature.
Analytes Detection system method Detection limit, μg L−1 Preconcentration Factor Ref

−1
Pb, Cd Electrothermal atomic absorption Deep eutectic liquid organic salt as a new solvent Pb: 8 ng kg , 195 35
spectrometry for liquid-phase microextraction Cd: 0.2 ng kg−1
Fe, Mn, Zn, Cu, Pb, Flame and electrothermal atomic Microwave digestion- direct determination – – 39
Co, Cd, absorption spectrometry
Cd, Pb Electrothermal atomic absorption Micro-solid phase extraction Cd: 0.002 ng/g, – 52
spectrometry Pb: 0.02 ng/g
Pb, Co, Ni, Mn Flame atomic absorption spectrometry Deep eutectic solvent microextraction Pb: 2.4, Co: 4.6, Ni: 100 This
7.5,Mn: 1.0 work

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