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Talanta
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A R T I C L E I N F O A BS T RAC T
Keywords: In this paper we present an electrochemical approach to prepare standard solutions of metal ions in a room
Electrochemical dissolution temperature ionic liquid (IL), which can find useful application for analysis in hydrophobic matrices. The
Lead method, developed here for the case of lead ions, is based on the galvanostatic dissolution of a lead anode
Analytical standards dipped directly in a suitable IL, namely tri-hexyl(tetradecyl)phosphonium bis (trifluoromethylsulfonyl) imide
Ionic liquid
([P14,6,6,6]+[NTf2]-). After each oxidation step, the metal dissolution process in the IL solutions was monitored
Olive oil
by cyclic voltammetric measurements at a glassy carbon disk electrode. The results indicated that the peak
current relevant to the reduction of the electro-generated Pb(II) increased linearly while increasing the
oxidation time. By varying the oxidation time from 200 to 6000 s, a set of Pb(II)/[P14,6,6,6]+[NTf2]- solutions at
concentrations ranging between 10 and 300 μg g−1 was prepared. To validate the efficiency of the electro-
chemical procedure to produce metal ion standard solutions, the Pb content was quantified by developing a
microwave digestion procedure specifically suitable for the IL medium, followed by ICP-QMS analysis in the
digested standards. The results indicated a satisfactory agreement between concentrations found by ICP-QMS
and calculated from electrochemical data, with a coulometric efficiency of Pb(II) generation in ionic liquid
≥95.6%. Finally, the applicability of the Pb(II)/IL solutions as standards for analyses in hydrophobic media was
tested by determining, by ICP-QMS, the Pb content in an extra-virgin olive oil spiked with known amounts of a
Pb(II)/IL standard. Satisfactory Pb recoveries, ≥96%, were measured.
⁎
Corresponding author.
E-mail address: toni@unive.it (M.A. Baldo).
http://dx.doi.org/10.1016/j.talanta.2017.05.039
Received 15 March 2017; Received in revised form 9 May 2017; Accepted 12 May 2017
Available online 14 May 2017
0039-9140/ © 2017 Elsevier B.V. All rights reserved.
M.A. Baldo et al. Talanta 172 (2017) 133–138
134
M.A. Baldo et al. Talanta 172 (2017) 133–138
detected, whose peak current increased with increasing the preconcen- at −1.1 V, pulse height 50 mV, scan rate 50 mV s−1. Inset: DPASV recorded for 2.0 mgL−1
Pb(NO3)2 in 0.1 M KNO3 aqueous solution. Preconcentration time 10 s, other stripping
tration time of Pb in the IL medium. Note that the peak potential value conditions as above.
matched with literature data for the anodic stripping peak of lead in
aqueous solutions [8]. Comparison with the anodic stripping signal reoxidation.
recorded for 2.0 mg/L Pb(II) in the same aqueous electrolyte (see the These results indicate that the galvanostatic oxidation of the lead
inset in Fig. 2), further confirmed the attribution of the peak to Pb
135
M.A. Baldo et al. Talanta 172 (2017) 133–138
sacrifice electrode in IL is effective in dissolving controlled amounts of was detected. From ICP-QMS data found for standard deviation of the
Pb(II). The cathodic peak in Fig. 1A can be attributed to the reduction blanks (sb) and the slope of the calibration plot (m), LOD (=3 sb/m)
in [P14,6,6,6]+[NTf2]- of the electro-generated Pb(II), whose concentra- and LOQ (=10 sb/m) values for lead of 0.019 ng g−1 and 0.063 ng g−1,
tion scales with the galvanostatic oxidation time. In particular, by respectively, were obtained.
assuming a 100% efficiency of electro-generation of Pb(II) and by The same digestion procedure, followed by ICP-QMS analysis, was
applying the Faraday law, the amount of Pb(II) in [P14,6,6,6]+[NTf2]- then applied to a set of six samples containing different concentrations
produced for instance by an oxidation step of 200 s is approximately of Pb(II) in [P14,6,6,6]+[NTf2]-, prepared electrochemically as described
10 μg g−1, such a value scaling linearly when increasing the overall above (see Section 3.1). The same procedure was used also to digest
oxidation time. and analyze the lead content in the certified reference standard,
containing 100 ( ± 5) μg g−1 in paraffin oil. Table 2 compares the
3.2. Standardization of lead solutions in [P14,6,6,6]+[NTf2]- experimental lead(II) concentration values (CPb,EC) calculated on the
basis of the experimental charge, Qexp, consumed during the electro-
In order to evaluate the efficiency of the electrochemical dissolution chemical preparation of the Pb(II)/[P14,6,6,6]+[NTf2]- solutions, with the
process of lead to produce standard solutions of the metal ion in ionic relevant Pb content determined on the same samples by ICP-QMS
liquid, the quantification of lead was performed by developing a analysis (CPb,ICP-MS) after MW digestion. From these data, a satisfac-
suitable mineralization procedure based on a MW digestion, followed tory agreement between the two sets of data is observed. These results
by ICP-QMS analysis. This method was applied to the electrochemically indicate that the efficiency of the electrochemical generation of con-
prepared lead solutions in IL, as well as to blank samples and to trolled amounts of Pb(II) in ionic liquid is ≥95.6%.
certified standards in oil. Data reported in the last line of Table 2 confirm also a good
agreement between the lead concentration determined here by ICP-
3.2.1. Mineralization of Pb solutions in IL QMS and the certified values of the reference standard, being the
The mineralization procedures of oily matrices using MW digestion relative error of −4.5%, so validating the reliability of the overall
reported in the literature generally imply the use of mixtures of digestion/analytical procedure here presented. Note that the certified
concentrated HNO3 and H2O2 as reagents, with heating treatment precision given for Pb concentration in the Certipur® standard in
time not exceeding 30 min [34–38]. On the contrary, no specific paraffin oil is 5%.
indication has been reported so far about efficient and safe mineraliza-
tion procedures suitable for ionic liquid media. Thus, in this study a 3.3. Analytical application in olive oil /IL mixtures
microwave digestion program suitable to mineralize and dissolve lead
ions from the organic IL solutions (obtained as above) was developed The real analytical applicability of the Pb(II)/IL solutions prepared
and optimized, using a temperature controlled microwave device. electrochemically, as metal ion standards for quantification procedures
A set of experiments was performed by testing different mixtures of in hydrophobic media, was tested. To this aim, at first the content of Pb
reagents and varying hold times and temperature step gradients in the in a commercial extra-virgin olive oil was determined. The oil sample
digestion program, with the aim to obtain a satisfactory recovery. As was preliminarily mixed with a suitable amount of [P14,6,6,6]+[NTf2]- to
final result of this investigation, Suprapur HNO3 (67–69%) was chosen obtain a 0.5 M IL concentration in the mixture. Afterwards, the Pb
as the most suitable reagent for the MW digestion of the IL. content in the olive oil mixture was quantified by applying the
In order to avoid the risk of explosion due to the presence of the IL, mineralization procedure followed by ICP-QMS analysis, as described
a long and mild heating program was preferred. In brief, the MW above in par. 3.2. By this approach, a Pb(II) concentration value of
digestion program consisted on applying a temperature gradient from 2.66 ± 0.18 ng g−1 in the EV oil sample was determined. It can be noted
room temperature up to 180 °C, formed by a succession of ramps and that in the literature [34–40] average concentrations of lead in EV olive
pauses which are reported in detail in Table 1. The power was fixed at oil range from < 0.8 ng g−1 up to approximately 100 ng g−1 (which is
1500 W. After digestion, each sample was recovered from the Teflon the maximum level for the content of Pb in EV olive oil established by
vessel and diluted ten-times with ultrapure MilliQ water. the European Union Commission in Regulation N°1881/2006 [41]).
The same oil/IL mixture was then spiked with known increasing
3.2.2. Quantification of Lead amounts of the Pb(II)/IL_Std 2 solution (reported above in Table 2),
Preliminarily, the mineralization procedure optimized here was to give added Pb concentrations (CPb,added) listed in Table 3, 2nd
applied in triplicate to the digestion of blank samples, which were column. Total expected Pb concentrations (CPb,expected) together with
composed by: 1) reagent alone (named Reagent Blank: HNO3 67–69%, values determined experimentally by ICP-QMS (CPb,measured) and the
8 mL per sample); 2) ionic liquid + reagent (named IL Blank: 0.5 g relevant recoveries are also collected in Table 3. Data found indicate
RTIL + HNO3 67–69%, 8 mL per sample). ICP-QMS analysis was very satisfactory values for Pb recovery in the spiked samples.
performed on the digested blank samples, and in any case no Pb signal
4. Conclusions
Table 1
Microwave digestion program. This work presents some advances of great practical usefulness for
*
performing accurate analysis of metal ions in hydrophobic samples.
Step Mode Tstart Tend (°C) ΔT (°C) Time ∫ E/t (KW/
(°C) (min) min)
The controlled electrochemical dissolution of lead metal allowed us to
prepare solutions containing known concentrations of Pb(II) in ionic
1 ramp room 50 ~29 7 236 liquid, which can be used as reliable standards for applying direct
temp. quantification procedures in hydrophobic media, such as olive oil.
2 pause 50 50 0 5 177
3 ramp 50 100 50 10 304
The validation of the approach proposed here for generating metal
4 pause 100 100 0 5 316 ion standard solutions was conducted by ICP-QMS analysis and
5 ramp 100 150 50 10 580 required the development of an original microwave procedure for
6 pause 150 150 0 5 676 digesting safely IL samples and oil/IL mixtures.
7 ramp 150 180 30 7 772
In addition to proving the feasibility and reliability of this electro-
8 pause 180 180 0 7 678
9 venting – – – 20 – chemical preparation of Pb(II) /IL standard solutions, on our opinion
this work can open the way to further applications of this approach to
*
Power fixed at 1500 W. the preparation of hydrophobic standards of other metal ions as well as
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M.A. Baldo et al. Talanta 172 (2017) 133–138
Table 2
Experimental Pb(II) concentrations calculated from electrochemical data and determined by ICP-QMS analysis for a set of Pb(II)/[P14,6,6,6]+[NTf2]- standard solutions prepared
electrochemically.
Metal Solution Oxidation time (s) Qexp (C) CPb,ECa (μg g−1) CPb, ICP-QMS
b
(μg g−1) RE%c
a
CPb calculated from the experimental charge Qexp measured from the EC step.
b
CPb determined by ICP-QMS analysis; average values from three replicates, RSD% in parenthesis.
c
Relative percentage error, RE% =(CPb,EC - CPb, ICP-QMS))/ CPb, ICP-QMS ×100.
d
RE% calculated in respect to the reference value (100 μg g−1) of the Certipur® standard.
Table 3
Pb(II) concentrations expected and determined experimentally by ICP-QMS analysis in EV olive oil/IL mixtures spiked with known amounts of a Pb/IL standard solution.
a
Average CPb values from three replicates, RSD% in parenthesis.
b
n.d.=not detected; LOD=0.019 ng g−1 ; LOQ=0.063 ng g−1.
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