Talanta 172 (2017) 133–138

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

Electrochemical preparation of standard solutions of Pb(II) ions in ionic MARK

liquid for analysis of hydrophobic samples: The olive oil case
⁎
M. Antonietta Baldoa, , Angela M. Stortinia, Ligia M. Morettoa, Michael Ongaroa,d,
Marco Romanb,c, Paolo Ugoa
a
Department of Molecular Science and Nanosystems, Ca’ Foscari University of Venice, Via Torino 155, I-30172 Venezia Mestre, Italy
b
Department of Environmental Sciences, Informatics and Statistics, Ca’ Foscari University of Venice, Via Torino 155, I-30172 Venezia Mestre, Italy
c
ECSIN-European Center for the Sustainable Impact of Nanotechnology, ECAMRICERT SRL, Viale Porta Adige 45, I-45100 Rovigo, Italy
d
Merck S.p.A., Via XI Febbraio 99, 20090 Vimodrone, MI, Italy

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.

1. Introduction rather than because of real lack of inorganic contamination in this

Toxic metal ions represent a hazardous category of food and
environmental contaminants which can cause serious problems to
human health and environmental safety [1–4]. In the last decades, this
risk has pushed the impressive development of reliable and sensitive
analytical methods and devices, suitable to detect trace and ultratrace
concentration levels of metals ions and their complex species in
aqueous matrixes and/or in water soluble samples [3–9]. A completely
different situation is observed for lipophilic samples insoluble or
unmixable with water, for which the majority of analytical assessments
has been focused almost exclusively on the determination of organic
analytes, while neglecting inorganic pollutants. The scarcity of studies
in this direction seems related more to the complexity and difficulties
encountered in developing analytical procedures suitable to extract and
quantify accurately the inorganic analytes in hydrophobic media,
kind of samples.
Among the others, a problem still unsolved in this field is the lack of
standard solutions suitable to calibrate and evaluate the accuracy of the
analytical procedures. Very often, aqueous standards are added at the
end of complex and time-consuming pretreatment procedures used to
bring metal ions to an aqueous environment suitable for the applica-
tion of standard quantification methods [10–13]. However, this “a
posteriori” methodology does not allow to evaluate the recovery of the
method, i.e. verifying whether there can be loss of, or contamination
with the analyte, during the extraction/change of medium procedure.
A standard solution suitable for direct use in hydrophobic samples
should be mixable/soluble in the raw sample, and it should contain an
accurately known concentration of the analyte. However, it is not easy
to prepare standards with such features for the case of solutions of
metal ions in a hydrophobic medium. We faced this problem recently,

⁎
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.
while investigating the development of an analytical approach able to
determine the concentration of metal ions in edible oils, in particular in
olive oil; as a consequence, in the present work we are proposing a
possible solution to this issue.
In recent studies [14–16], it has been demonstrated that it is
possible to perform electrochemical measurements in olive oil after
proper mixing with a suitable room temperature ionic liquid (IL),
namely tri-hexyl(tetradecyl)phosphonium bis (trifluoromethylsulfonyl)
imide ([P14,6,6,6]+[NTf2]-). This IL is highly hydrophobic and mixes well
in certain ratios with the oil, allowing to lower the electrical resistivity
of the solution and furnishing the required ions which act as supporting
electrolyte [14–16]. ILs are salts composed by a large organic cation
and a relatively small anion, which are finding application both in
synthetic and analytical chemistry as “green” and not hazardous aprotic
media [17–21]. Among other uses, ILs can be employed in electro-
analytical chemistry to stabilize electrogenerated reactive species or
water insoluble redox probes while operating over a wide accessible
potential window [18,19,22,23]. Moreover, the availability of ILs with
different hydrophilicity/hydropobicity and viscosity allows one to
optimize the mixing with other liquids as well as to modulate the mass
transport behavior of electroactive analytes to the solution/electrode
interface [15,24–28].
Some decades ago, the problem of preparing anhydrous standard
ionic solutions in aprotic organic solvents such as acetonitrile, DMSO,
DMF, propylencarbonate etc., was faced by developing relatively easy
electrochemical preparation methods [29,30]. It was demonstrated
that, by oxidizing a metal anode under controlled anhydrous conditions
in the aprotic medium, it was possible to generate metal ion solutions
whose concentration could be controlled coulometrically [29,30]. The
method showed to be feasible also for preparing with accuracy
solutions of anhydrous HClO4 obtained by the electrochemical oxida-
tion of hydrogen gas in pre-dried aprotic solvents, which were
successfully used as standards to define an absolute pH scale from
proton basicity in aprotic solvents [31,32].
In the present work we revisited this electrochemical approach,
adapting and optimizing the anodic dissolution of a lead anode directly
in the IL, to prepare standard solutions of Pb(II) in [P14,6,6,6]+[NTf2].
The development of such preparation procedure required the develop-
ment of a reliable validation method. To this aim, we present here for
the first time a microwave digestion procedure suitable for mineralizing
the complex organic matrix of the IL medium and dissolving heavy
metal species, prior to spectroscopic analysis. Concentrations of Pb(II)
were then determined in the digested standards by Inductively Coupled
Plasma-Quadrupole Mass Spectrometry (ICP-QMS). Finally, the ap-
plicability of the method to real matrices was tested by performing ICP-
QMS quantification of Pb(II) concentrations in olive oil spiked with
known amounts of a Pb(II)/IL standard.
2. Experimental
2.1. Reagents and samples
The IL [P14,6,6,6]+[NTf2]- (assay ≥95.0%) and KNO3 (analytical-
reagent grade) were purchased from Sigma-Aldrich (Milan, Italy).
HNO3 (67–69%, Romil® Suprapur) was obtained from Delchimica
(Napoli, Italy). All chemicals were used as supplied by the manufac-
turer. According to the technical sheet, the water content of
[P14,6,6,6]+[NTf2]- was lower than 1000 ppm.
An extra-virgin (EV) olive oil sample was purchased from a local
supermarket and it was stored at room temperature under dark in an
amber bottle, until use.
For producing lead solutions in pure IL, a bar of Pb (0.5×0.2×1.5 cm)
was used. To test its purity, a fragment of 1.777 g of this bar was dissolved
in Suprapur HNO3 and then diluted with MilliQ water. The voltammetric
measurements performed on this Pb test solution did not show any other
stripping peak apart a well-defined peak at −0.420 ± 0.005 V vs Ag,
134
Talanta 172 (2017) 133–138
relevant to Pb.
When required, pure nitrogen (≥99.9%) supplied from SIAD
(Bergamo, Italy) was used to remove oxygen from the solution.
To validate the data obtained from ICP-QMS measurements, the
multielemental reference standard Certipur® Merck (Milan, Italy), 100
( ± 5) μg g−1 in paraffin oil, was employed.
2.2. Instrumentation and procedures
2.2.1. Electrochemical measurements
Electrochemical experiments were carried out at room temperature
(21 ± 1 °C) by using electrochemical CHI660 (CH Instruments, USA)
workstation controlled via PC. The preparation of the Pb(II) solutions
in IL were performed directly in a 2 mL glass vial, assembled in an
undivided three-electrode cell configuration with the Pb bar employed
as working electrode, a Pt wire (0.4 cm diameter) as counter electrode
and an Ag wire (1 cm long and 1 mm diameter) as pseudo-reference.
Note that the half-wave potential (E1/2) of the ferrocene/ferricinium
(Fc/Fc+) couple taken as internal redox standard [31], recorded vs the
Ag pseudo-reference in the [P14,6,6,6]+[NTf2]- medium, resulted:
+0.195 ( ± 0.005) V [15].
For cyclic voltammetric (CV) and differential pulse anodic stripping
voltammetric (DP-ASV) investigations, a polytetrafluoroethylene-
shrouded glassy carbon (GC) disk, 3 mm diameter, from Tokai
Carbon Japan, grade GC-20S, was employed as working electrode. In
these experiments, the reference electrode was a saturated Ag/AgCl
electrode (AMEL, Milan, Italy). Prior to its use, the GC electrode was
polished to a mirror finish with graded alumina powder (0.3 and
0.05 µm).
2.2.2. Preparation of lead solutions in IL
Solutions containing different concentrations of Pb(II) in
[P14,6,6,6]+[NTf2]- were prepared by galvanostatic dissolution of the
Pb bar in 2 mL volume samples of IL, equilibrated at room temperature
(i.e., 21 ± 1 °C) and kept under stirring at 150 rpm, by setting the
applied constant current at 1×10−4 A for different oxidation time (tox).
Before application of the electrochemical procedure, the medium was
purged with N2 for a long time (about 45 min), in order to remove
effectively oxygen from the ionic liquid.
2.2.3. Preparation of the olive oil/IL mixtures
The olive oil/[P14,6,6,6]+[NTf2]- mixtures were prepared by mixing
accurately weighted amounts of the two liquids inside the 2 mL glass
vial. On the basis of previous findings [15,16], the suitable proportion
of IL and olive oil was 50/50 (% w/w), which corresponds to a
concentration of 0.5 M IL in the mixture. To allow fast homogenisation
between olive oil and RTIL, the solutions were mixed by an Advanced
Vortex Mixer (Velp Scientifica, Italy) for 3 min, and then left equili-
brating for about 5 min prior to measurements. By this way, a visibly
clear homogeneous solution, with absence of clouds, was obtained. A
similar procedure was employed to homogenise the olive oil/IL mixture
after it was spiked with amounts of standard Pb solutions in IL.
2.2.4. Microwave (MW) digestion of ionic liquid and olive oil samples
All materials used for samples treatment were cleaned preliminarily
with Contrad 2000 detergent (Z.E.U.S., Bolzano) and HNO3
(Romil®Suprapur) and then accurately rinsed with MilliQ (Merck
Millipore, Milano) purified water.
For validation of Pb concentrations, 0.5 g of each sample (weighted
with precision of ± 0.1 mg) was diluted with 8 mL Suprapur HNO3
(67–69%) and transferred inside a Teflon vessel (100 mL), held in a 10
place high pressure carousel (Milestone® HPR-1000/10 S High
Pressure). Sample preparation and dilution were performed under
hood, in controlled atmosphere. The digestion was then carried out by
a microwave unit Ethos1-Milestone® (Bergamo, Italy). Between sam-
ples digestion batches, each Teflon vessel was cleaned with 10 mL
M.A. Baldo et al. Talanta 172 (2017) 133–138

HNO3, applying a MW temperature controlled program which con-

sisted in a 20 min ramp from room temperature to 160 °C, followed by
a pause at the final temperature for 10 min.

2.2.5. ICP measurements

After MW digestion of the samples, the lead content in the solutions
investigated was quantified using an Inductively Coupled Plasma-
Quadrupole Mass Spectrometer (ICP-QMS-Agilent 7500 I, Santa
Clara, United States). The plasma conditions were: RF Power
1500 W, carrier Ar flow rate 1.2 L min−1, torch horizontal alignment
0.6 mm, torch vertical alignment −0.4 mm, sampling depth 8 mm,
instrument sampler cone in Nickel. Sample introduction during
analyses was carried out by an autosampler Cetac ASX-500. Each
value obtained was the average of seven readings per sample (with
RSD < 3%) and concentration data were obtained after subtraction of
the blank value. The limit of detection (LOD) was calculated on the
basis of LOD=3 sb/m, where sb is the standard deviation of the blank
and m is the slope of the calibration plot (sensitivity). Analogously, the
limit of quantification (LOQ) was calculated as LOQ=10 sb/m. For
obtaining the calibration plot, standard solutions at Pb(II) concentra-
tion ranging from 0.02 up to 20 ng g−1 were prepared from the multi-
elemental standard ICUS 1675, 10 mg/mL in HNO3 5% (ULTRA
Scientific Italia S.r.l., Bologna, Italy) with lead at the certified concen-
tration. A spike of Tl (50 ppb) was added in each vessel to assess the
recovery; values ranging between 94–97% were found.

3. Results and discussion

3.1. Electrochemical oxidation of lead in ionic liquid

The electrochemical dissolution of lead was performed galvanosta-

tically using a lead bar as working anode dipped in [P14,6,6,6]+[NTf2]-,
by imposing an anodic constant current, IA=1×10−4 A. The potential of Fig. 1. (a) Cyclic voltammograms recorded at a GC disk electrode, 3 mm diameter, in the
the working electrode was monitored vs the Ag pseudo-reference and it N2-purged [P14,6,6,6]+[NTf2]- medium after a sequence of galvanostatic Pb dissolution
ranged between 2 and 3 V even for electrolysis time as long as 30 min. steps, using a lead anode. CVs after the first ( ), second ( ), third ( ), fourth
During the galvanostatic step, at the Pt cathode a small evolution of ( ) oxidation step, with time interval of 200 s each; scan rate 50 mV s−1. (b) Ip,c vs
bubbles was observed. Considering the value of the potential recorded oxidation time plot.
during the electrolysis as well as the fact that the IL medium was used
as received and not dried before use, the main cathodic process can be
ascribed to hydrogen evolution from the presence of trace water in the
ionic liquid [17,19,20,23,33]. However, concomitant reduction of other
species cannot be excluded.
In a set of experiments, the above anodic constant current was
applied for a time interval of 200 s, repeating the process 4 times. After
each oxidation step, a cyclic voltammogram was recorded in the same
solution using a GC working electrode between 0.0 V, as starting
potential, and −2.0 V vs Ag. As shown in Fig. 1A, in the forward scan
a cathodic peak at about −1.00 ± 0.01 V was detected, whose peak
current (Ip,c) increased linearly with the oxidation time used to prepare
the relevant sample (see Fig. 1B). In the backward scan, no reoxidation
peak was detected in the potential window explored.
For IL samples prepared by using a Pb dissolution time of 300 s,
DP-ASV measurements using a GCE were also performed. To this aim,
a medium transfer procedure was used. At first, a deposition potential
(Edep) of −2.0 V vs Ag was applied in the ionic liquid solution. After
careful rinsing with water, the GCE was transferred into an aqueous Fig. 2. Differential pulse anodic stripping voltammograms recorded at a GC disk
electrolyte (0.1 M KNO3), where a DPV anodic stripping scan was electrode, 3 mm diameter, after increasing preconcentration time in a Pb(II)/IL sample
performed from −1.1 to 0.2 V vs Ag/AgCl. Typical anodic stripping prepared by the galvanostatic procedure, and then transferring the working electrode in a
DPVs recorded using preconcentration times ranging from 30 to 120 s 0.1 M KNO3 aqueous solution. Applied preconcentration time in the IL solution of 30
are shown in Fig. 2. In both cases a stripping peak at −0.420 V was ( ), 60 ( ) and 120 s ( ), at Edep=−2.0 V vs Ag/AgCl. DPASV initial potential

detected, whose peak current increased with increasing the preconcen-
tration time of Pb in the IL medium. Note that the peak potential value
matched with literature data for the anodic stripping peak of lead in
aqueous solutions [8]. Comparison with the anodic stripping signal
recorded for 2.0 mg/L Pb(II) in the same aqueous electrolyte (see the
inset in Fig. 2), further confirmed the attribution of the peak to Pb
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
conditions as above.
reoxidation.
These results indicate that the galvanostatic oxidation of the lead

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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

136
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

Pb(II)/IL _Std 1 200 1.93×10−2 9.70 9.63 (2.3) 0.73

Pb(II)/IL_Std 2 400 3.86×10−2 19.1 18.8 (1.4) 1.6
Pb(II)/IL _Std 3 1000 9.67×10−2 48.5 47.3 (2.8) 2.5
Pb(II)/IL _Std 4 2000 1.93×10−1 96.8 92.7 (2.5) 4.4
Pb(II)/IL _Std 5 4000 3.91×10−1 196.4 193.5 (3.7) 1.5
Pb(II)/IL _Std 6 6000 5.93×10−1 296.8 302.7 (8.1) −1.9
Certipur® Merck, 100 ( ± 5) μg g−1 – 95.5 (0.71) −4.5d

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.

Sample CPb, CPb,expected CPb,measureda Recovery %

added (ng g−1) (ng g−1)
(ng g−1)

IL Blank – – n.d. ( < LOD)b –

Unspiked oil/0.5 M IL – – 2.66 (6.8) –
Oil/0.5 M IL + spike 1 6.48 9.14 8.91 (6.7) 97.5
Oil/0.5 M IL + spike 2 12.5 15.2 14.7 (5.3) 96.7
Oil/0.5 M IL + spike 3 28.3 31.0 30.4 (2.3) 98.1

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.

to direct analysis of the heavy metal content in a variety of lipophilic
samples which can include mineral oils and gasoline, fatty foods as
milk, butter and other biological matrices.
Acknowledgments
This work was partially supported by MIUR, (Rome), project PRIN
2010AXENJ8. We also thank Dr. Giulio Cozzi from CNR-IDPA
(Institute for the Dinamics of Environmental Processes, via Torino
155, Venezia Mestre, Italy) for useful discussions and suggestions.
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