Microchemical Journal 114 (2014) 106–110

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Microchemical Journal
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Ionic imprinted polymer based solid phase extraction for cadmium and
lead pre-concentration/determination in seafood
M.C. Barciela-Alonso, V. Plata-García, A. Rouco-López, A. Moreda-Piñeiro, P. Bermejo-Barrera ⁎
Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain

a r t i c l e i n f o a b s t r a c t

Article history: A method for trace Cd and Pb determination in fresh fish samples by Electrothermal Atomic Absorption
Received 28 October 2013 Spectrometry (ETAAS) has been developed. A preconcentration step was necessary due to the low levels of
Received in revised form 2 December 2013 these elements in fresh fish samples. Solid phase extraction (SPE) using ionic imprinted polymers (IIPs) as an ad-
Accepted 9 December 2013
sorbent was selected as the preconcentration technique. The IIPs were prepared via precipitation polymerization
Available online 16 December 2013
using 2-(diethylamino) ethyl metacrilate (DEM) as a monomer and 8-hydroxyquinoline as a complexating agent.
Keyword:
The 2,2′-azobisisobutyronitrile (AIBN) and acetonitrile/toluene (3:1) mixture were used as initiator and porogen,
Ionic imprinted polymer respectively. A microwave assisted acid digestion procedure using nitric acid and hydrogen peroxide was applied
Solid phase extraction for sample preparation.
Fish samples The experimental parameters for SPE extraction in column mode, such as pH of the digested sample, sample vol-
Cadmium ume, load rate, and elution rate, have been optimized. The optimum pH for quantitative Cd and Pb retention was
Lead 8.5, and the elution was completed with 2 mL of 2.0 M nitric acid. Cadmium and lead concentrations in the acid
ETAAS extracts were determined by ETAAS using palladium and magnesium nitrates as a chemical modifier. The limits
of detection (LODs) and limits of quantification (LOQs) obtained were 0.15 and 0.52 μg L−1 for Cd determination,
and 0.50 and 1.68 μg L−1 respectively for Pb determination. Taking into account the mass of sample used and the
preconcentration factor (12.5), the LODs obtained were 0.21 and 0.67 ng g−1 for Cd and Pb respectively. These
limits are adequate to determine Cd and Pb at levels lower than the maximum levels allowed in fresh marine
products, by the European Union legislation. The optimized method was applied for Cd and Pb determination
in different seafood samples, such as squid, hake, sardine, horse mackerel, grouper and gilthead bream, and it
was possible to detect both metals in all samples.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction [13–19]. In most of the reported methods, Cd and Pb were determined

Cadmium and lead are toxic elements found in fish samples due to
their presence in the aquatic environment. Consumption of food with
high concentrations of these elements can produce problems for
human health, such as damage to the kidneys and central nervous
system; different legislations establish therefore, maximum levels of
these elements in food to avoid these problems. The European Union
sets maximum levels of Cd and Pb in fresh fish of 0.05 and 0.3 mg kg−1
respectively [1].
Several analytical methods have been used for Cd and Pb determina-
tion in fish and mollusk. These methods include a sample preparation
step usually performed by microwave assisted acid digestion, or the
use of the solid sample using the slurry sample preparation. The determi-
nation can be performed by Flame Atomic Absorption Spectrometry
(FAAS) [2–9], Electrothermal Atomic Absorption Spectrometry (ETAAS)
[10,11], Inductively Coupled Optical Emission Spectrometry (ICP-OES)
[12] or Inductively Coupled Plasma-Mass Spectrometry (ICP-MS)
⁎ Corresponding author. Tel.: +34 881814266; fax: +34 981 547 141.
E-mail address: pilar.bermejo@usc.es (P. Bermejo-Barrera).
in lyophilized fish samples [2,5,13,20], which offer good sensitivity.
However, low sensitivity was obtained when these methods were
applied to determine these elements in fresh fish samples (Cd and Pb
concentrations at ng g−1 levels) [21–23].
In order to improve the sensitivity, several authors include a
preconcentration step prior to analyte determination. Therefore, Citak
et al. [5] performed a coprecipitation step with zirconium(IV) hydroxide
prior to Pb, Co, Cu, Cd, Fe and Ni determination by FAAS. Cloud point ex-
traction was used by Mohamadi et al. [3], and also by Citak and Tuzen
[24], for the determination of Cd and Pb in fish samples. Recently,
Mendil [2] used solid phase extraction (SPE) on modified silica gels
with thiourea for Cd, Cu and Pb determination in food samples by FAAS.
Ionic imprinted polymers (IIPs) have been used in recent years as
adsorbent for solid phase extraction procedures. The most common
applications are for ion preconcentration from environmental samples
such as natural water or seawater. García-Otero et al. [25] used an IIP
for on-line solid phase extraction of nickel and lead from seawater.
Xubiao et al. [26] synthesized an IIP for the removal of Pb(II) ions from
environmental water samples; whereas, Gawin et al. [27] prepared a
Cd(II)-imprinted polymer for its application as a sorbent in SPE before

0026-265X/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.microc.2013.12.008
 M.C. Barciela-Alonso et al. / Microchemical Journal 114 (2014) 106–110
determination of Cd(II) in groundwater and wastewater by FIA-FAAS.
The use of IIPs in SPE offers several advantages: these materials can be
synthesized using inexpensive reagents and present high capacity for
recognizing ions and high selectivity [28].
To the best of our knowledge, there are no applications in the litera-
ture of IIPs as SPE sorbent for Cd and Pb preconcentration from digested
fish samples. Therefore, the objective of this work is to develop a
method using an ionic imprinted polymer as an adsorbent for SPE
when isolating Cd and Pb from digested fresh fish samples. The IIP
used in this work was synthesized in a previous work performed by
our research group [28]. The method developed was applied for Cd and
Pb determination in different fresh seafood products.
2. Experimental
2.1. Instrumentation
An Ethos Plus microwave digester (Milestone, Sorisole, Italy)
equipped with a carousel provided with ten 100-mL high pressure Teflon
vessels with cover, HTC adapter plate and HTC safety springs was used.
The acid microwave digestion was performed operating at a maximum
power of 1000 W. Measurements were performed using a PerkinElmer
Model 1100B atomic absorption spectrometry equipped with an HGA-
700 graphite furnace atomizer and an AS-70 autosampler (PerkinElmer,
Waltham, Massachusetts, USA). A temperature-controllable incubation
camera (Stuart Scientific, Surrey, UK) equipped with a low-profile roller
(Stovall, Greensboro, NC, USA) was used for performing the polymeriza-
tion process. A peristaltic pump (Gilson, Middleton, USA) and polyethyl-
ene tubings of 1.4 mm i.d. were used for SPE. IIPs were packed into 5 mL
syringes (Brand, Wertheim, Germany) between replacement Teflon frits
(Supelco, Bellefonte, PA, USA). Lab Blender Stomacher 400 (Seward Med.
Ltd., London, UK) with Stomacher Closure bags 6041/CLR (Seward) was
used for fish sample homogenization. An ORION 720A plus pH-meter
with a glass-calomel electrode (ORION, Cambridge, UK) was used for
pH measurements.
2.2. Reagents
Cadmium and lead standard solutions (1000 mg L−1) as well as 8-
hydroxyquinoline (8-HQ), used as non-vinylated monomer, were form
Merck (Darmstadt, Germany). Vinylated monomer (2-(diethylamino)
ethyl metacrilate, DEM) and divinylbenzene-80 (DVB), used as cross-
liker, were from Sigma-Aldrich (Steinheim, Switzerland). The latter re-
agent was previously treated for removing the polymerization inhibitor
by passing a few milliliters of the reagent through a mini-column con-
taining around 0.5 g of neutral alumina (Sigma-Aldrich). 2,2′-
Azobisisobutyronitrile (AIBN), used as initiator, was purchased from
Fluka (Buchs, Switzerland). This reagent was purified by crystallization
at − 20 °C after dissolving the reagent in methanol (Merck) at 50–
60 °C. After purification, it was stored at 4 °C. Nitric acid (69% (m/m)),
ammonia 25% (v/v), ammonium chloride, hydrogen peroxide (33%
(v/v)), and analytical grade nickel dichloride (NiCl2·6H2O) were
purchased from Panreac (Barcelona, Spain). HPLC grade acetonitrile and
toluene were obtained from Scharlab (Barcelona, Spain). Palladium ni-
trate 10 g L−1 in HNO3 (15%) (Merck) and magnesium nitrate (Merck)
were used as chemical modifier for Cd and Pb determination by ETAAS.
Ultrapure water of resistivity 18 MΩ cm was obtained from a Milli-Q
purification device (Millipore Co.).
All glassware and plasticware were rigorously cleaned and kept into
10% (v/v) nitric acid for at least 48 h. The material was then rinsed three
times with ultrapure water before used.
2.3. Seafood samples
Seafood samples (gilthead bream, Sparus aurata; horse mackerel,
Trachurus trachurus; sardine, Sardina pilchardus; grouper, Epinephelus
107
marginatus; squid, Loligo vulgaris; and hake, Merluccius merluccius)
were obtained from a local supermarket. Composite samples by pooling
together the soft tissues or flesh of all specimens were prepared by
mechanical blending after removing the bones and entrails. The homog-
enized fish samples were stored at 4 °C until analysis.
2.4. Microwave acid digestion
Portions of 3.0000 g of homogenized fresh fish samples were direct-
ly weighed into digestion vessels and mixed with 2 mL of ultrapure
water, 4 mL of 69% (m/m) HNO3 and 2 mL of 33% (m/m) H2O2. Vessels
were then placed into the microwave oven, where one sample vessel
was temperature and pressure monitored during the operation. The
temperature program used lasted 23.5 min and consisted of four
steps: (1) The temperature was increased from room temperature
(24 °C) to 90 °C in 2.5 min; (2) a temperature ramp of 8.3 °C min−1
was applied up to 140 °C (6.0 min); (3) the temperature was increased
from 140 °C to 200 °C in 5 min; and (4) the temperature was main-
tained at 200 °C during 10 min. After a cooling down stage (venting
time of 40 min), each acid digest was recovered, the digestion vessel
was rinsed with small volumes of ultrapure water, and the washing
water was combined with the acid digest before adjusting to 25 mL
with ultrapure water.
Several blanks were prepared in the same way as the sample but
without the introduction of the sample. The samples analyzed in this
work were digested in triplicate.
2.5. Synthesis of ionic imprinted polymer
The ionic imprinted polymer was synthesized following the method
proposed by Otero-Romaní et al. [28]. Therefore, 0.0668 g of NiCl2·6H2O,
226 μL of DEM and 0.653 g of 8-HQ were mixed in 25 mL of porogen
(3:1 acetonitrile:toluene). This solution was stirred for 5 min and then
filtered. Finally, 1 mL of DVB (cross-linker) and 82.6 mg of AIBN (initia-
tor) were added, the glass tubes purged with nitrogen and immediately
sealed just before thermal induction of precipitation polymerization. The
temperature was ramped from room temperature to 60 °C over 2 h, and
then maintained at 60 °C for a further 24 h under a low stirring rate
(33 rpm). The polymer obtained was then vacuum-filtered, washed
with acetonitrile, and oven-dried overnight at 40 °C. The masses of poly-
mer obtained after polymerization were around 0.624 g and the efficien-
cy of the polymerization process was 62%. The same procedure, except
the presence of NiCl2·6H2O, was applied for preparing non-imprinted
polymers (NIPs).
2.6. Preparation of IIP cartridges
5 mL syringes were filled with 0.20 g of IIP or NIP absorbents. The IIP
or NIP material was between two Teflon frits. The IIP syringes were then
connected to a peristaltic pump via polyethylene tubings, and the
template [nickel(II) ions] was removed from the polymer particles by
extensive washing with 2.0 M nitric acid (5.0 mL aliquots). An efficient
removal of the template from IIP particles was achieved after passing
50 mL of washing solution. This was verified by ETAAS measurements
of nickel in the elution solutions from the cartridges. The NIP was sub-
jected to the same washing pretreatment described above.
2.7. IIP-solid phase extraction procedure
For the SPE procedure, the IIP was first conditioned by passing 25 mL
of buffer solution (NH3/NH4Cl) at pH 8.5 ± 0.5. Afterwards, 25 mL of
digested fish sample adjusted at pH 8.5 was passed through the syringe
at a flow rate of 2.35 mL min− 1. The syringe was then rinsed with
25 mL of Milli-Q® water and the retained ions (Pb and Cd) were subse-
quently eluted with 2 mL of 2 M nitric acid. The whole process was per-
formed using a flow rate of 2.35 mL min−1. Blanks of the procedure
108 M.C. Barciela-Alonso et al. / Microchemical Journal 114 (2014) 106–110

were also obtained by applying the SPE procedure to blank digested 20 Pb Cd

samples. A preconcentration factor of 12.5 was obtained under these
18
operating conditions.

Concentration (µg L-1)

16
14
2.8. ETAAS measurements
12
Measurements were performed by ETAAS, using cadmium and lead 10
hollow cathode lamps, operating at 228.8 and 283.7 nm for Cd and Pb, 8
respectively, as sources of radiation. The spectral bandwidth was 6
0.7 nm for both elements. Pyrolytically coated graphite tubes with 4
L'vov platforms were used for analysis. Integrated absorbances (integra- 2
tion times of 2 and 3 s for Cd and Pb, respectively) were used. The atom-
0
izer temperature programs and the instrumental parameters are listed 7,5 8 8,5 9
in Table 1. Palladium and magnesium nitrates at concentrations of 20 pH
and 15 mg L−1, respectively, were used as a chemical modifier for
both elements. The volume of sample injected into the atomizer was Fig. 1. Influence of pH in the IIP-SPE procedure for Cd and Pb preconcentration in digested
20 μL. fish samples.

3. Results and discussion
3.1. Optimization of Cd and Pb IIP-SPE procedure from fish digests
A set of experiments was performed to select the optimum condi-
tions for the IIP-SPE procedure. Parameters such as pH, load flow rate,
elution flow rate and concentration of HNO3 (used as eluting solvent)
were studied.
3.1.1. pH effect of the sample
Experiments were performed to evaluate the effect of the pH of the
digests in the SPE procedure. Therefore, aliquots (25 mL) of the acid di-
gests from a hake sample were adjusted at different pHs (7.5, 8.0, 8.5
and 9.0) by using a 12.5% (v/v) ammonium hydroxide solution before
SPE (Section 2.5). The SPE procedure was applied in triplicate for each
pH. This study was also performed by using blank digests. Concentration
measured in the blank digest was subtracted from those obtained when
treating samples. Results obtained are shown in Fig. 1. As it can be ob-
served, the highest Cd retention was obtained at pHs 7.5 and 8.0;
while, the retention of Pb increased when increasing the pH, and the
highest retention was obtained at pH 8.5. Compromise pH of 8.0 was
therefore selected to perform the simultaneous Cd and Pb pre-
concentration using IIP-SPE.
3.1.2. Effect of the load and elution flow rates
Experiments were performed to study the influence of the load flow
rate in the Cd and Pb preconcentration from fish digest. Three aliquots of
a pool of digested fish (25 mL) were passed at 0.9, 1.6, 2.4 and
2.9 mL min−1, flow rates controlled by a peristaltic pump. The experi-
ments were also performed using a digest blank. Results obtained
showed that the concentration of Cd decreased when using load flow
rates higher than 2.4 mL min−1; whereas, recovered Pb concentrations
were increased up to a flow rate of 2.4 mL min−1. Taking into account
significant differences were observed for Pb when using all the flow
rates; whereas, recovered cadmium concentrations remained practical-
ly constant until 2.4 mL min−1, and decreased at the highest flow rate
(2.9 mL min−1). An elution flow rate of 2.4 mL min−1 was therefore
selected for the simultaneous Cd and Pb preconcentration from fish
digests.
3.1.3. Effect of nitric acid concentration
The effect of the nitric acid concentration used as an eluting solution
was studied. Experiments were performed passing 25 mL of digest or
blank sample through the IIP-SPE syringe, and elution was studied
with 2 mL of HNO3 at different concentrations (0.5, 1 and 2 M). Elution
with ultrapure water (0 M HNO3) was also tested. Results obtained in
triplicate (Fig. 2) showed that Cd and Pb were retained in the IIP-SPE
when the elution step was performed using water, and the recovered
Cd and Pb concentrations were increased when using HNO3 solutions.
Therefore, 2 M HNO3 was selected as optimum concentration to per-
form elution. This result agreed with those obtained in previous work
[28].
3.2. Analytical characteristics
3.2.1. Calibration
Three different calibration graphs were performed: (1) external
aqueous calibration; (2) external acid calibration (2 M HNO3); and
(3) standard addition calibrations prepared following the IIP-SPE
preconcentration procedure. External calibrations were tested covering
metal concentrations between 0 and 3 μg L−1 for cadmium and between
0 and 30 μg L−1 for lead. Standard addition calibration was performed
12 Cd Pb
Concentration (µg L-1)

these results, and with the purpose of reducing the analysis time, a 10
load flow rate of 2.4 mL min−1 was selected for further experiments.
The effect of the elution flow rate was also studied. The flow rates 8
studied were 0.9, 1.6, 2.4 and 2.9 mL min− 1, and the experiments
6
were also performed in triplicate. The results obtained showed that no
4

Table 1
2
Graphite furnace program for Cd and Pb determination by ETAAS.

Step Temperature Ramp time Hold time Argon flow 0

(°C) (s) (s) (mL min−1) 0 0,5 1 2
Drying 150 15 20 300 [HNO3] mol L-1
Charring 600(Cd)/800(Pb) 10(Cd)/15(Pb) 15(Cd)/10(Pb) 300
Atomization 1800 0 2(Cd)/3(Pb) 0(read)
Fig. 2. Influence of the HNO3 concentration in the IIP-SPE procedure for Cd and Pb
Clean 2200 2 3 300
preconcentration in digested fish samples.
 M.C. Barciela-Alonso et al. / Microchemical Journal 114 (2014) 106–110 109

Table 2

Reference

Present
Slopes and regression coefficients (r) obtained using external aqueous calibration,

work
external acid calibration and standard addition.

[6]

[7]

[8]

[2]

[9]

[5]
Element External aqueous External acid Standard

LODs: 0.085 (Cd); 0.28 (Pb) μg g−1

calibration calibration addition

LODs: 0.24 (Cd); 0.17 (Pb) μg g−1

LODs: 0.30 (Cd); 0.63 (Pb) μg L−1

LODs: 0.16 (Cd); 0.49 (Pb) μg L−1

LODs: 0.27 (Cd); 2.5 (Pb) μg L−1
LODs: 0.5 (Cd); 4.5 (Pb) μg L−1

LODs: 0.35 (Cd); 5 (Pb) μg L−1

Slope r Slope r Slope r

Preconcentration factor/LOD

0.21 (Cd); 0.65 (Pb) ng g−1

Cd 0.0483 0.9988 0.059 0.9970 0.0531 0.9969
Pb 0.0057 0.9999 0.0056 0.9996 0.0068 0.9992

covering Cd concentrations between 0 and 0.24 μg L−1, and Pb concen-

trations within 0–2.4 μg L−1 range. The slopes and the regression coeffi-

12.5 folds
6.6 folds
10 folds

10 folds

75 folds

25 folds
4 folds
cients obtained for both elements using the three different calibration
graphs are listed in Table 2. After statistical comparison of the slopes of
external aqueous calibration, external acid calibration and standard ad-

SPE: 50 mL of sample and eluted with 20 mL 2 M HNO3. Evaporated to dryness

Acid sample digestion with HNO3, H2O2, HCl and HClO4 (final volume 100 mL).

Microwave acid sample digestion (3.0000 g) with HNO3 + H2O2 (final volume
dition graphs by applying the t-test (95% significant level) [29], statisti-

Acid sample digestion ( 1.0000 g) with HNO3 + H2O2 (final volume 50 mL).

Acid sample digestion (1.0000 g) with HNO3 + H2O2 (final volume 50 mL).
cally differences were not detected. Therefore, external acid calibration
was selected to perform the Cd and Pb determination in the acid extracts.

Microwave acid sample digestion (1.0000 g fish) with HNO3 + H2O2

Calcination (2 g of dry fish) followed by dilution with 20 mL HNO3.

Coprecipitation: 50 mL of digested sample and redisolution of the

3.2.2. Sensitivity of the method

SPE: 50 mL of digested sample and elution with 5 mL HNO3.

The limits of detection and quantification were calculated according to

SPE: 300 mL of digested sample and elution with 4 mL.

LOD = (3SD) / m and LOQ = (10SD) / m, where SD is the standard de-

SPE: 25 mL of sample and elution with 2 mL of HNO3.

SPE: 100 mL of sample eluted with 25 mL of HNO3.
viation of eleven measurements of a procedural blank (blank digest
preconcentrated by the IIP-SPE procedure) and m is the slope of the

and the residue diluted with 5 mL 1 M HNO3.

SPE: 20 mL of sample and elution with 3 mL.

acid external calibration graph. The LOD and LOQ obtained were 0.16
and 0.52 μg L−1 for Cd determination, and 0.49 and 1.65 μg L−1 for Pb
determination. Taking into account the mass of fish sample used in the di-
gestion procedure, the preconcentration factor (12.5), the LODs obtained
were 0.21 and 0.65 ng g−1 for Cd and Pb respectively. Therefore, the pro-
posed method presents a high sensitivity for Cd and Pb determination in

(final volume 300 mL).

precipitate with 2 mL.

fresh seafood samples. The LODs obtained are lower than the LODs ob-
Sample treatment

tained by Mendil [2] for Cd (0.24 μg g−1) and Pb (0.17 μg g−1) determi-
nation by FAAS in food samples after preconcentration on modified silica
gels with thiourea, and the LODs reported by Djedjibegovic et al. [16] for

25 mL).
Cd and Pb determination in fish by ICP-MS (3.30 and 2.70 ng g−1 for Cd
and Pb, respectively).

Coprecipitation with zirconium(IV) hydroxide

3.2.3. Repeatability and accuracy
Sorbent: Silica gels modified with thiourea.

The precision of the method was evaluated by studying the repeat-

impregnated Amberlite XAD-1180 resin

ability (within-run precision) and the repeatability of the overall proce- Sorbent: Nanosized sulfur particles
Sorbent: 2-mercaptobenzothiazole

Sorbent: Ionic imprinted polymer

dure (within-bath precision).
Sorbent: Functionalized SBA-15

The within-run precision was calculated by analyzing (eleven times)

Sorbent: Sepabeads SP-207

an acid extract obtained after the preconcentration of a digest fish by the

Preconcentration method

IIP-SPE procedure. The relative standard deviations (RSDs) obtained

were 2% for Cd and Pb.
The within-batch precision was assessed by analyzing six replicates
of a fish digest (application of the IIP-SPE procedure six times) by
ETAAS. The RSDs obtained were 9 and 7% for Cd and Pb, respectively.
SPE
SPE

SPE

SPE

SPE

SPE

We can conclude that the method offers good precision.

Analytical recovery was assessed for two concentration levels, after
spiking different aliquots of a fish digest with 0.12 and 0.2 μg L− 1 of
Cu, Cd, Pb and Zn in water and food samples by FAAS

Cu, Cd, Ni and Pb in water and food samples by FAAS

Comparative studies on Cd and Pb preconcentration.

Cd and with 1.2 and 2.0 μg L− 1 of Pb. Each concentration level was
Cd, Co, Cu, Fe, Ni and Pb in fish samples by FAAS
Cu, Cd, Pb and Zn in dried fish or oyster samples

treated in triplicate by the IIP-SPE procedure, and each extract was an-
alyzed in duplicate by ETAAS. The analytical recoveries obtained were
Cd, Cu and Pb in fish samples by FAAS

103 ± 3% and 99 ± 2%, for spiked cadmium concentration of 0.12

Cd and Pb in fish samples by ETAAS

Table 3
Cd and Pb in water by FAAS

Cd and Pb concentrations in fish samples.

Cd (ng g−1) Pb (ng g−1)

Element and sample

Gilthead bream 4.1 ± 0.5 6.5 ± 0.9

Mackerel 6.4 ± 0.1 19 ± 1
Sardine 1.3 ± 0.1 16 ± 1
Grouper 1.5 ± 0.3 17 ± 1
Table 4

Squid 59 ± 1 10 ± 1
Hake 1.7 ± 0.3 11 ± 1
110 M.C. Barciela-Alonso et al. / Microchemical Journal 114 (2014) 106–110
and 0.2 μg L−1, respectively; and 97 ± 4 and 97 ± 3% for spiked lead
concentration of 1.2 and 2.0 μg L−1, respectively. The method offers
therefore good recovery for both elements at the concentration levels
studied.
4. Application
The developed method was applied for Cd and Pb determination in
fresh seafood samples.
Portions of fresh samples (around 3.0000 g) were digested in tripli-
cate and analyzed using the method described above. Each digest in
was preconcentrated using the IIP-SPE procedure, and Cd and Pb were
then determined in the acid extracts by ETAAS in duplicate. Results ob-
tained are listed in Table 3. Cd and Pb were detected in all the samples
studied, and the obtained concentration ranges were between 1.3 and
59.3 ng g−1 for Cd, and between 6.5 and 19.3 ng g−1 for Pb. The highest
Cd concentration was obtained in the squid sample.
5. Conclusions
A solid phase extraction procedure using an ionic imprinted poly-
mer as an adsorbent for SPE of Cd and Pb from seafood digests was eval-
uated. A preconcentration factor of 12.5 was obtained. The IIP-SPE
procedure combined with ETAAS determination has offered accurate
and precise results. A comparison of the proposed method with other
preconcentration methods is summarized in Table 4. The proposed
solid phase extraction method presents better sensitivity and in some
cases higher preconcentration factor when compared to other methods.
The sensitivity obtained with this procedure allowed the Cd and Pb de-
termination in fresh products, resulting adequate to detect the levels
established by the European Union legislation.
Acknowledgment
The authors wish to thank the Xunta de Galicia (Project number
10PX1B209032PR) for financial support.
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