Talanta 153 (2016) 247–252

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Development of air assisted liquid phase microextraction based on

switchable-hydrophilicity solvent for the determination of palladium
in environmental samples
M. Ezoddin a,n, K. Abdi b,c, N. Lamei c
a
Department of Chemistry, Payame Noor University, P.O. BOX 19395-3697, Tehran, Iran
b
Department of Medicinal Chemistry and Radiopharmacy, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran
c
Drug Design and Development Research Center, Tehran University of Medical Sciences, Tehran, Iran

art ic l e i nf o a b s t r a c t

Article history: A novel switchable-hydrophilicity solvent (SHS) in combination with air-assisted liquid–liquid micro-
Received 15 December 2015 extraction (AALLME) which called AA-SHS-LPME, has been applied for preconcentration of Pd(II). A
Received in revised form water-immiscible solvent, Triethylamine (TEA), was used as a green switchable solvent that switched
3 March 2016
reversibly between one form that was miscible with water to another that formed a biphasic mixture
Accepted 5 March 2016
with water. CO2 was used as a stimulus for triggering the transformation to the water-miscible form and
Available online 7 March 2016
removal of CO2 to achieve the reverse. Separation was carried out by addition of sodium hydroxide,
Keywords: which produced a change on the ionization state of amine. AALLME led to the rapid formation of fine
Switchable-hydrophilicity solvent droplets of the extractant in the aqueous solution, and the contact surface between both immiscible
Air-assisted liquid–liquid microextraction
liquids was significantly enlarged. Detection limit value, preconcentration factor and relative standard
Triethylamine
deviation (RSD, n ¼10) were found 0.07 μg L  1, 64 and 3.5% respectively. The recovery of the analyte in
Pd(II)
Water, road dust and catalytic converter water, road dust and catalytic converter samples was in the range of 98.3–103.2%. The obtained results
samples indicated that the developed method could be an efficient analytical method for the routine analysis in
the environmental field.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction detection, such as solid phase extraction (SPE) [8], liquid–liquid

extraction (LLE) [9], flow injection extraction (FIE) [10], cloud point
Palladium as a metal has important applications in electrical extraction (CPE) [11] and dispersive liquid–liquid microextraction
appliances and chemical catalysts [1]. Some palladium compounds (DLLME) [12]. As a matter of fact, some of these methods have
have been known as potential health risks to humans, causing some shortcomings e.g., like time-consuming, long extraction
asthma, allergy, rhino conjunctivitis and other serious health times, large volumes of extraction solvents and dispersive solvents
problems [2]. The emission levels of toxic gaseous pollutants into and generation of secondary waste which leads to environmental
the environment can diminish with precious metals inside the problems and complex management issues [13]. Utilizing of toxic
converter. They can be deposited on solid air suspended matter, and environmentally damaging solvents is one of the major
road dust, in aquatic environments, soils and sediments when they drawbacks of recent analytical techniques. One of the most im-
disperse into the atmosphere [3]. Owing to the fact that the fine portant advantages of the microextraction methods is the utili-
dispersed particles can cause some diseases such as, asthma, al- zation of green solvents to reduce waste through recycling and
also elimination of toxic solvents using from analytical procedures
lergy and rhino conjunctivitis, the monitoring of Pd(II) in en-
[14–18]. A new generation solvent called switchable hydrophilicity
vironmental and industrial samples has key role of in terms of
solvent(SHS) has received attention as solvent alternatives [19]. A
human health and environmental purposes [4–6]. Due to in-
switchable solvent is a solvent in two forms that can switch re-
sufficient sensitivity of instrumental techniques, determination of
versibly between one form that is miscible with water and another
metal ions at trace levels is limited [7]. To eliminate these lim-
also can form a biphasic mixture with water [19]. Amidines and
itation, different types of preconcentration methods have been
tertiary amines have been determined as switchable solvents
reported for separation and preconcentration of Pd (II) prior to its [20,21] which can be switched between the two forms by the
addition of CO2 and then reverted back to its non-ionic form by
n
Corresponding author. nitrogen, inert gas and or addition of sodium hydroxide [22]. A
E-mail address: [email protected] (M. Ezoddin). chemical reaction of the CO2 and water changes miscibility of

http://dx.doi.org/10.1016/j.talanta.2016.03.018
0039-9140/& 2016 Elsevier B.V. All rights reserved.
248 M. Ezoddin et al. / Talanta 153 (2016) 247–252

amine and generates a water-soluble carbonate salt of the proto- (Kirchlengern, Germany). A 50/60 Hz, 350 W ultrasonic bath with
nated amine [23]. CO2 is used as the trigger for the switching temperature control (BANDELIN SONOREX, Germany) was used.
process because it is inexpensive, non-toxic and easily removed
[20,24–28]. The main advantage of using of SHSs is that allow the 2.3. Synthesis of switchable solvent
extraction of the analytes in a homogeneous phase without dis-
persive solvent [19,20,24,29–34]. These solvents can be considered The switchable solvent was synthesized in an equal volume
as green chemistry. The development of switchable solvents fol- mixture of triethylamine and water. In this approach, 100 mL of
lows on exploiting the wide range of applications such as extrac- TEA were added into a 1 L glass bottle containing 100 mL of Milli-Q
tion, separation and reaction tasks [24–28]. Recently a new version water. A two-phase system was formed after stirring the mixture.
of DLLME namely as air-agitated liquid–liquid microextraction Then, dry ice (10 g) was added gradually on the two phase system
(AALLME) [35] is developed in which fine organic droplets are under vigorous stirring until the solution became cloudy. The dry
formed by repeated pulling in and pushing out of the mixture of ice was added ten times to obtain a single protonated triethyla-
sample solution and extraction solvent into a conical test tube by mine carbonate phase which corresponds to a 1:1 (v:v) water/TEA
using a syringe[36]. Thus, the contact between analyte and the solution. 200 mL of the 1:1 (v:v) water/TEA solution can be easily
extraction solvent as well as turbidity of the solution increases prepared and this volume allows the development of more than
more and more. In this study, a stable homogeneous SHS/water 200 extractions since each one requires only 750 mL of the
mixture was provided by using dry ice as a reagent. AALLME was mixture.
used to accelerate the dispersion of the extraction solvent in the
sample solution. The final separation was achieved using sodium 2.4. Sample preparation
hydroxide (Eq. (1)). To best of our knowledge, there is no report
about the combination of AALLME and SHS-LPME for micro- The water samples containing tap water, waste water, sea water
extraction of palladium ions from environmental samples. and river water samples were filtered through a 0.45 μm mem-
+CO2 brane filter immediately after sampling to remove suspended
NR3 + H2 O ⟹ HNR+3 + HCO−3
⟸ particular matter.
+NaoH
An amount of 0.5 g of homogenized road dust sample (col-
NR3=Triethylamine(TEA) (1) lected from crowded streets of Tehran) was weighed accurately,
transferred into 100 mL beaker and digested with HCl/HNO3 in a
volume ratio of 3:1 by refluxing the mixture for 5 h. The solution
was centrifuged and filtered and at the result, the filtered solution
2. Experimental
was diluted with distilled water up to 25 mL. Finally, 5.0 mL of this
solution was poured into tubes and after adjustment of pH, the
2.1. Reagents and solutions
volume of solution was adjusted to 10 mL.
Portions of 0.01 g of catalytic converter sample were putting
All reagents used were of analytical grade. Aqueous solutions
into 100 mL teflon beaker and digested with 10 mL of HCl/HNO3 in
were prepared in double-distilled deionized water (Milli-Q sys-
a volume ratio of 3:1. The mixture was evaporated near to dryness.
tem, Millipore, USA). Pd(II) stock solution (1000 mg L  1) was
Then 3 mL of concentrated hydrofluoric acid was added and fil-
prepared by dissolution of the proper amount of PdCl2 (Merck,
tered through a filter paper. The filtrated was made up to 100 mL.
Darmstadt, Germany) in 3:1, HCl/HNO3 (v/v) and then diluted with
1 mL of this solution was poured into tubes and after adjustment
double distilled water. Working standard solutions were obtained
of pH, the volume of solution was adjusted to 10 mL.
by appropriate dilution of the stock standard solution. CO2 (Dry
ice) was obtained from Zarin chemical Company (Tehran, Iran).
Triethylamine, HCl, HNO3 and NaOH were purchased from Merck 2.5. Air switchable solvent based microextraction procedure
(Darmstadt, Germany). A solution of 1  10  3 mol L  1 1-(2-Pyr-
idylazo)-2-naphthol(PAN) (Merck, Darmstadt, Germany) was pre- 10 mL of aqueous sample containing Pd (II) and
pared by dissolving an appropriate amount of this reagent in 2  10  5 mol L  1 of PAN were transferred into a 50 mL centrifuge
ethanol. tube. After adjusting pH to 4, 750 mL of protonated triethylamine
carbonate as extraction solvent was added to in the centrifuge
2.2. Instrument tube. Then, 1.0 mL of NaOH solution (20 mol L  1) was injected. The
mixture was rapidly withdrawn and pushed out into the tube (5
The determination of palladium was carried out using a Varian times) using a syringe. At this stage, cloudy solution was formed,
Spectra AA 220 atomic absorption spectrometer (Australia, http:// and the complex was rapidly extracted into the fine droplets of
www.varianinc.com) with a deuterium lamp background correc- triethylamine phase. After centrifugation at 4000 rpm for 3 min,
tion and equipped with a graphite furnace (GTA-110 series). the complete separation of the water and triethylamine phase was
Measurements were accomplished in the integrated absorbance achieved. The triethylamine phase was collected on the surface of
(peak area) mode at 247.6 nm, using a spectral band width of the water phase and diluted with 50 μL of acidified ethanol. Fi-
0.2 nm and lamp current 5 mA. The heating program for palladium nally, 25 μL of the final solution was injected into ETAAS by using
determination was given as follow: the drying temperature was the auto sampler system.
90 °C, hold 10 s; and 120 °C, hold 20 s; the ashing temperature was The preconcentration factor (PF) and relative recovery (RR)
800 °C, hold 8 s; the atomization temperature was 2400 °C, hold were calculated by Eqs. (2) and (3) for evaluation this method.
3 s; the clean temperature was 2600 °C, hold 4 s. Argon 99.995% by Eq. (2).
(from Roham Gas Co., Tehran, Iran) was used as protective and Crec
purge gas. The Measurements of pH values were made with a pH- PF=
Ci (2)
meter(model 692, Herisau, Switzerland) with a glass combined
electrode. where Crec is the concentration of the analyte in the collected
A Universal 320R centrifuge equipped with a swing out rotor triethylamine phase and C0 is the initial concentration of the
(6-place, 5000 rpm, Cat. no. 1628A) was obtained from Hettich analyte within the sample solution.
 M. Ezoddin et al. / Talanta 153 (2016) 247–252 249

RR was calculated by Eq. (3)

Cfound − Creal
RR =
Cadded (3)

where Cfound is the concentration of the analyte after adding a

known amount of standard to the real samples, Creal is the con-
centration of the analyte in the real sample, and Cadded refers to a
standard solution that was spiked in the real sample.

3. Results and discussion

Amines with SHS behavior typically have logarithm of the oc-

tanol/water partition coefficient (log Kow) between 1.2 and 2.5.
Also the strength of their conjugate acids (pKaH) is above 9.5 [24].
TEA can be considered as a non-polar solvent with log Kow of 1.647
Fig. 2. The effect of PAN concentration on the extraction recovery of Pd(II). Con-
and pKaH 10.75. TEA has SHS behavior at a 1:1 volume ratio of ditions: sample volume: 10 mL; pH: 4, 1 mg L  1 of Pd (II) ion, extractant volume:
water to amine. Thus the TEA exhibits switchable miscibility. 750 mL, NaOH volume 1.0 mL (20 mol L  1).
Adding more water to the mixture increases the amount of amine
in the aqueous phase enough to form a monophasic mixture after
addition of CO2 without also resulting in a monophasic mixture
when CO2 is removed. Thus a liquid can be a SHS at one volume
ratio, but not a SHS at another volume ratio [24].

3.1. Effect of pH

pH plays an important role on metal chelate formation and

subsequent extraction. The extraction of Pd (II) from the sample
solution depends on the stability constant of Cd–PAN complex.
Therefore, the effect of pH on the complex formation and the ex-
traction of Pd (II) was studied in the range of 1–7. In acidic med-
ium, a weak complexation and uptake occurs, which can be ex-
plained by competition between metal ions and hydrogen ions for
the binding to ligand. On the other hand by increasing the pH up
to 4, the potential of active sites of ligand for metal ion binding
were increased (Fig. 1). However, increase in pH facilities the
Fig. 3. The effect of the extractant volume on the extraction recovery of Pd(II).
palladium ion to hydrolyze which decreases the extraction re-
Conditions: sample volume: 10 mL; pH: 4, 1 mg L  1 of Pd (II) ion, PAN
covery. Thus a pH value of 4.0 was chosen for further experiments. 2  10  5 mol L  1, NaOH volume 1.0 mL (20 mol L  1).

3.2. Effect of PAN amount

The effect of PAN concentration on extraction of complex is

shown in the concentration range of (0.5–5)  10  5 mol L  1 in
Fig. 2. As it can be seen, the extraction recovery of Pd (II) increased
with the increase of PAN concentration up to 1.5  10  5 mol L  1

Fig. 4. The effect of volume of 20 mol L  1 NaOH on the extraction recovery of Pd

(II). Conditions: sample volume: 10 mL; pH: 4, 1 mg L  1 of Pd (II) ion, PAN
2  10  5 mol L  1, extractant volume: 750 mL.

and then remained constant. Because of some other ions that

could be present in real samples and probably react with PAN,
concentration of 2  10  5 mol L  1 was used in the experiments.

Fig. 1. The effect of pH on the extraction recovery of Pd(II). Conditions: sample

3.3. Effect of extractant volume
volume: 10 mL; 1 mg L  1 of Pd (II) ion, PAN 2  10  5 mol L  1, extractant volume:
750 mL, NaOH volume 1.0 mL (20 mol L  1). The aqueous solubility of TEA can be switched by the addition
250 M. Ezoddin et al. / Talanta 153 (2016) 247–252

Table 1 Table 3
Analytical performance characteristics of AA-SHS- Analytical results for Pd(II) determination in different samples.
LPME method.
sample Add Found (mg L  1) 7SDa Relative recovery
Parameter Analytical feature (mg L  1) (%)a

LOD (mg L  1) 0.07 Tap waterb 0 – –

RSD (%) (n¼ 10, 1 mg L  1) 3.5 2 1.977 0.12 98.3 7 5.8
Correlation coefficient (r2) 0.9943 Waste water 0 – –
Preconcentration factor 64 2 2.067 0.19 103.2 7 6.2
Linear range (mg L  1) 0.16–2.5 Sea waterc 0 – –
Sample volume (mL) 10 2 2.03 70.12 101.6 7 5.9
River waterd 0 0.23 70.02 –
2 2.21 70.16 99.1 77.1
or removal of CO2 concentration in the extraction unit. The solu- Road dust 0 0.187 0.02 (mg g  1) –
2 2.15 70.09 (mg g  1) 98.8 7 4.1
bilization of the TEA can be achieved using dry ice as CO2 as re-
Catalytic converter 0 658.2 744.7 (mg g  1) –
agent and without special device. The effect of the volume of 100 767.29 7 27.6 (mg g  1) 101.2 7 3.5
protonated triethylamine carbonate (P-TEA-C) on the extraction
a
recovery was studied in the volume range of 250–1500 mL by using Mean of three experiments 7 standard deviation.
b
From drinking water system of Tehran.
1 mL of 20 mol L  1 NaOH. As can be shown in Fig. 3, the extraction c
Caspian sea water.
recovery was increased up to 750 mL of PTEA-C. In lower volumes d
Latian river.
of 750 mL, the recovery of the solvent was low while larger vo-
lumes induced an excessive dilution of the analyte. 3.6. Effect of coexisting ions

3.4. Effect of NaOH volume The effects of common coexisting ions on the extraction re-
covery of Pd (II) were studied. An ion was considered to interfere
The removing of CO2 from P-TEA-C causes the two phases in- when its presence produced a variation in the absorbance of the
cluding water and hydrophobic triethylamine phases. In this work, sample of more than 5%. It was found that the tolerable con-
20 mol L  1 NaOH was used to convert the P-TEA-C form of centration ratio of foreign ions to 1 mg L  1 Pd (II) was 5000 for K þ ,
switchable solvent to hydrophobic TEA phase and, at the same Na þ , NO3  , SO42  , and 1000 for Ca2 þ , Mg2 þ , 500 for Co2 þ , Ni2 þ ,
time, extract the complex from water phase to TEA phase. For this Fe2 þ , Zn2 þ , Cd2 þ , Pb2 þ . It demonstrates that the common coex-
evaluation, different volumes of 20 mol L  1 NaOH solution in the isting ions did not have significant effect on the separation of Pd
range of 0.5–3 mL were studied. According to the obtained results (II) and the developed method is fairly free from interferences.
in Fig. 4, the extraction recovery increased up to 1.0 mL of
20 mol L  1 NaOH and then decreased with increasing volume of 3.7. Analytical performance
NaOH. The excess of NaOH, may cause a change of pH sample
solution and broke the complex formed. Also the cloudy state is The performance of proposed method was obtained by several
not well formed. Therefore, the extraction recovery decreases [22]. analytical characteristics such as limit of detection (LOD), pre-
The best result was obtained in 1 mL and was used in all sub- concentration factor (PF) and linearity along with the relative
sequent experiments. standard deviation (RSD) under the optimized conditions (Ta-
ble 1). The calibration curve was exhibited linearity over the range
3.5. Effect of numbers of extraction of 0.16–2.5 μg L  1 with a correlation coefficient (R2) of 0.9968. The
limit of detection, (LOD) based on 3Sb/m (Sb, and m are standard
In the AALLME method, the numbers of extraction was defined deviation of the blank and slope of the calibration equation, re-
as the numbers of the operation that the sample solution and spectively) was 0.07 mg L  1. The relative standard deviation (R.S.
extraction solvent were sucked into a 10-mL glass syringe and D.) for 10 replicate measurements of 1 μg L  1 Pd (II) and also
then injected into the test tube. To increase of extraction recovery, preconcentration factor for 10 mL of the sample solution were 3.5%
the numbers of extraction was examined in the range of 1–12 and 64 respectively.
times. The results exhibited that, by increasing extraction num- The characteristic data of the present method was compared
bers, the extraction recovery was also increased up to 5 times of with other methods. As can be shown from Table 2, high PF, low
extraction and then remained constant. Hence, 5 times of extrac- LOD and RSD are achieved in 3 min and these characteristics are
tion was selected for the further studies. comparable or even better than most of the other methods. This

Table 2
Comparison of the proposed method with other reported procedures.

Methods LOD (mg L  1) PF RSD (%) Volume sample (mL) Total extraction time (min) Ref.

CPE-ICP-OESa 0.3 20.2 3.8 10 25 [39]

DLLME -ETAAS 0.0024 156 4.3 5 45 [38]
SFODME –USD-FAASb 0.6 49.9 2 15 13 [1]
FO-LADS-DLLMEc 0.25 165 o4 10 45 [37]
SPE– FAAS 1.2 75 1.7 75 440 [40]
CPE- ETAAS 0.12 52 3.4 50 10 [41]
SPE– FI-Column-GFAAS 0.28 13.9 3.9 6 43 [42]
AA-SHS-LPME -ETAAS 0.07 64 3.5 10 3 This work

a
Cloud point extraction – inductively coupled plasma-optical emission spectrometry.
b
Solidified floating organic drop microextraction based on ultrasound-dispersion.
c
Fiber optic-linear array detection spectrophotometry and dispersive liquid–liquid microextraction.
 M. Ezoddin et al. / Talanta 153 (2016) 247–252 251

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