Analytical

Methods
View Article Online

Published on 03 June 2013. Downloaded by Instituto de Invest Marinas on 02/07/2013 07:05:44.

PAPER

Cite this: DOI: 10.1039/c3ay40727f

View Journal

A coprecipitation procedure for the determination of

some metals in food and environmental samples by
ame atomic absorption spectroscopy

Cosxkun Ozdemir,
Sxerife Samac* and xSenol Kartal
A novel, rapid, and simple preconcentration procedure based on the coprecipitation of Cr(III), Cu(II), Fe(III),
Pb(II), Pd(II) and Zn(II) ions with Ni(II)a-benzoin oxime precipitate was developed prior to ame atomic
absorption spectrometric determination. The optimum values of the important analytical parameters
inuencing the quantitative coprecipitation of the analytes were as follows: pH 8.5, amount of abenzoin oxime: 100 mg, amount of Ni(II) as carrier element: 0.25 mg, time duration: 10 min. The eects
of alkali (400015 000 mg L
1) and alkaline earth (10004000 mg L
1) metals on the recovery were also
studied. The alkali metal ions (K+ up to 4000 and Na+ up to 15 000 mg L
1) and alkaline earth metal
ions (Mg2+ up to 1000 and Ca2+ up to 4000 mg L
1) did not show any interference eect on the

Received 2nd May 2013

Accepted 3rd June 2013

recovery of the analytes. Under the optimized conditions, the detection limits (3s, N 10) for the
analytes were in the range of 0.15.3 mg L
1. The accuracy of the presented coprecipitation method was
checked by the analysis of certied reference materials. The method was applied to the determination

DOI: 10.1039/c3ay40727f
www.rsc.org/methods

of the analytes in real samples such as natural water and food samples, and good results were obtained
(relative standard deviation <5%, recovery >95%).

Introduction

Metals are considered very important and highly toxic in various

environmental areas. The input of metals to the environment as
a result of anthropogenic activities is dicult to measure due to
very large natural inputs from erosion or rocks, wind-blown
dust, volcanic activity and forest res.1 Toxic metals can cause
damaging eects even at very low concentrations. They tend to
accumulate in the food chain and in the body, and can be stored
in so (e.g., kidney) and hard tissues (e.g., bone).2 They oen
exist in a positively charged form and can bind onto negatively
charged organic molecules to form complexes. The importance
of metal pollution control has increased signicantly in recent
decades.3
Air, soil, and water pollution are presently contributing to
the presence of harmful elements in the environment.4
Recently, pollution of water and food samples by an appreciable
amount of metals has been considered as the result of human
activities.5 Excessive accumulation of dietary metals in the
human body may cause serious health problems, and there is
growing concern about the eects of dairy food contaminants
on human health. Contamination of food products by metals is
becoming an unavoidable problem nowadays.6
Zinc, copper and iron are essential elements that are
required by a variety of biomolecules to maintain the normal
Department of Chemistry, Faculty of Sciences, Erciyes University, TR-38039, Kayseri,
Turkey. E-mail: sacmaci@erciyes.edu.tr; Fax: +90 352 4374933; Tel: +90 352 4374937

This journal is The Royal Society of Chemistry 2013

structure, function, and proliferation of cells. These metals can

be toxic in excessive amounts, especially in certain genetic
disorders.79 In the environment, lead is known to be toxic to
plants, animals and microorganisms. Plastics, shing tools,
lead crystal glass used in cathode ray tubes, ceramics, solders,
pieces of lead ashing and many other minor products are
materials that contain lead. Lead inuences the nervous
system, slowing down nerval response. Children are exposed to
lead right from their birth, as children in the embryonic stage
receive lead from their mothers through blood.10 Cr(VI)compounds are generally considered to be the most toxic and
carcinogenic. The environmental concerns related to chromium
are focused on applications like tanning, wood preservation,
and the use of pigments and dyes for plastics, paint and
textiles.10,11 Some palladium compounds have been reported as
potential health risks to humans, causing asthma, allergy, rhinoconjunctivitis and other serious health problems.12 The FAO/
WHO has declared that for an average adult (60 kg body weight),
the provisional tolerable daily intakes of Pb, Cu, Fe and Zn are
0.2, 3, 48 and 60 mg, respectively.13 The monitoring and control
of these trace elements in food sources require processing a lot
of samples to accurately characterize their abundance and to
reach reliable conclusions.14
The determination of trace elements and contaminants in
complex matrices, such as food, oen requires extensive sample
preparation and/or extraction regimes prior to instrumental
analysis.5 Therefore, it is of prime importance to determine the
concentration of essential and toxic elements in foods. The

Anal. Methods

View Article Online

Published on 03 June 2013. Downloaded by Instituto de Invest Marinas on 02/07/2013 07:05:44.

Analytical Methods
determination of trace metals in food samples has routinely
been carried out by inductively coupled plasma optical emission spectrometry (ICP-OES),15 inductively coupled plasma
mass spectrometry (ICP-MS),16 graphite furnace atomic
absorption spectrometry (GFAAS),17 and ame atomic absorption spectrometry (FAAS).1820
The preconcentration of traces of metals is oen required
prior to instrumental determination to lower the detection
limits and to improve the precision and accuracy of analytical
results.21 The coprecipitation method is useful for the preconcentration of trace metal ions and is one of the most useful
ways for the preconcentration/separation of trace elements
from the sample matrix.22,23 The coprecipitation method has an
advantage in that many elements other than alkali and alkaline
earth elements are preconcentrated quite eectively under the
same experimental conditions.24,25
In this study, a simple and rapid coprecipitation procedure
using a Ni(II)a-benzoin oxime precipitate was studied to determine Cr(III), Cu(II), Fe(III), Pb(II), Pd(II) and Zn(II) ions in water and
food samples by ame atomic absorption spectrometry (FAAS).
To the best of our knowledge, there is no study on the coprecipitation of the analyte elements by using Ni(II)a-benzoin oxime.
We found that the Ni(II)a-benzoin oxime system has a good
collecting ability for this purpose. Also, the Ni(II)a-benzoin
oxime precipitate is convenient to handle, because it can be
easily dissolved in about 0.5 mL of conc. nitric acid without
heating, which is required for the dissolution of the precipitate.

Experimental

2.1

Instruments

A PerkinElmer model AAnalyst 800 ame atomic absorption

spectrometer (Norwalk, CT, USA) equipped with a deuterium
background correction system and an air-acetylene burner was
used for the determination of all the metal ions. The operating
condition adjustments in the spectrometer were carried out
according to the standard guidelines of the manufacturer. For
measuring pH values in the aqueous phase, a Consort model C533
pH meter combined with a glass-electrode was used and a MLTW54 model centrifuge was used for centrifugation purposes.
2.2

Reagents and standard solutions

All the reagents used were of the highest available purity and of
at least analytical reagent grade (Merck, Darmstadt, Germany).
Deionized ultra pure water was used for the preparation of the
solutions. Standard stock solutions of the analytes, 1000 mg
L
1, were prepared by dissolving appropriate amounts of their
nitrate salts in 2% (w/v) nitric acid. Working standard solutions
were prepared fresh daily by stepwise dilution of the stock
solutions with deionized water. The calibration curve was
established using the standard solutions prepared in 1 mol L
1
HNO3 by dilution of the stock solutions. A 1% (w/v) solution of
a-benzoin oxime was prepared by dissolving 1 g of the reagent
in 100 mL of methanol. The glassware used was cleaned by
soaking overnight in dilute HNO3 (1 : 5) and then rinsed with
deionized water several times.

Anal. Methods

Paper
2.3

Preparation of samples

Ten mL of the certied reference material (SPS-WW2 Batch 108

wastewater sample) was taken and diluted to 25 mL with
deionized water. The pH of this sample solution was adjusted to
8.5 with ammonia/ammonium chloride buer solution. Then
the separation/preconcentration procedure given below was
applied to these sample solutions.
A 1.0 g aliquot from each of the food and the standard
reference material (INCT-TL-1 tea leaves) samples was taken
and treated with 15 mL of concentrated nitric acid and then
heated until a clear solution was obtained. The evaporation
was continued almost to dryness, and to the moist residue was
added 15 mL of nitric acid once more. Again the mixture was
evaporated nearly to dryness and then 3 mL of concentrated
H2O2 was added to it. Aer completing the dissolution process,
the sample solution was ltered through a cellulose lter paper.
The lter paper was washed with 12 mL of 1 mol L
1 HNO3.
The ltrate was diluted to 25 mL with deionized water. These
sample solutions were analyzed by using the proposed procedure. The nal measurement volume of the sample solutions
was 5 mL. A blank digest was prepared in the same way.
The proposed method was applied to various water samples.
First, the pH of the water samples was adjusted to 8.5 and then
the preconcentration procedure was applied. The analyte
concentrations in the nal solution (5 mL) were determined
by FAAS.
2.4

Proposed procedure

The proposed coprecipitation method was tested with model

solutions prior to its application to real samples. 25 mL of the
aqueous sample solution containing individually 20 mg of Cr(III),
Fe(III), Pd(II) and Pb(II), 10 mg of Cu(II) and 2 mg of Zn(II) was
placed into the centrifuge tube. The pH of the solutions was
adjusted to 8.5 with ammonia/ammonium chloride buer
solution (2 mL). Then 0.25 mL of 1000 mg L
1 Ni(II) as a carrier
element and 0.1 mL of 1% (w/v) a-benzoin oxime solution were
added to this solution. Aer the formation of the precipitate,
the solution was centrifuged at 3500 rpm for 10 min. The
supernatant was removed. The precipitate which remained
adhering to the bottom of the tube was dissolved with 500 mL of
concentrated HNO3. Then the nal volume was made up to 5
mL with deionized water. The analytes in the nal solution were
determined by FAAS.

Results and discussion

3.1

Eect of pH

For quantitative coprecipitation eciency of the analyte ions,

the working pH of the media is one of the most important
factors. The inuence of pH on the recovery of the analytes in
the Ni(II)a-benzoin oxime system was studied in the pH range
of 110 by using model solutions containing the analyte ions.
All pH adjustments were made using the following buer
solutions: KCl/HCl solution for pH 12, H3PO4/NaH2PO4 solution for pH 3, CH3COOH/CH3COONa solution for pH 46, and
CH3COONH4 solution for pH 7. An ammonia/ammonium

This journal is The Royal Society of Chemistry 2013

View Article Online

Paper

Analytical Methods

chloride buer solution was used between pH 8 and 10. This

was prepared from 1 mol L
1 solutions of the buer components. Two mL of the buer solution was employed in each
experimental study. The results are shown in Fig. 1. In the pH
range of 810, all the analyte ions were simultaneously and
quantitatively (>95%) recovered. All the further experiments
were performed at pH 8.5.

Published on 03 June 2013. Downloaded by Instituto de Invest Marinas on 02/07/2013 07:05:44.

3.2

Eect of the amount of a-benzoin oxime

The eect of the amount of a-benzoin oxime reagent on the

recovery (%) of the analyte ions was investigated. The results are
given in Fig. 2. When the experiments were performed without
a-benzoin oxime at pH 8.5, the recovery values were not quantitative (#45%) for the studied metal ions. The recovery of the
analyte ions increased with increasing amounts of a-benzoin
oxime. These results show that the a-benzoin oxime reagent is
necessary for the quantitative recoveries of the studied metal
ions. For all the subsequent experiments 100 mL of 1% (w/v)
a-benzoin oxime solution was used (Fig. 3).
3.3

Amount of nickel as carrier element

The inuence of the amount of Ni(II) as carrier element on the

recovery of the analyte ions was also investigated. Without
nickel, the recovery of the analyte ions was below 56%. Quantitative recovery values (>95%) for the analyte ions were
obtained for 0.25 mg of Ni(II). All the further experiments were
performed with 0.25 mL of 1000 mg L
1 Ni(II) solution.

Fig. 1

Fig. 3

3.4

Eect of the amount of Ni(II) on the recoveries of the analyte ions (n 3).

Eects of time duration

The eects of the duration of the coprecipitation procedure on

the recovery of analyte ions were also studied in the time range
of 530 min. Quantitative recoveries for all the analytes were
obtained aer 10 min duration. All the further studies were
performed with 10 min duration time.
3.5

Eect of centrifugation rate and time

One of the most important parameters for coprecipitation

procedures is the centrifugation rate. For this purpose, a series
of experiments was conducted at dierent centrifugation rates
varying from 1000 to 4000 rpm for 10 min. The absorbance
sharply increased up to the centrifugation rate of 2500 rpm
except for Pd, for which a slow increase was observed up to 3000
rpm and then it remained almost constant. A plateau was
observed over the centrifugation rate of 3500 rpm. As the
optimal centrifugation rate, 3500 rpm was selected (Fig. 4).
Another important parameter for coprecipitation procedures
is the centrifugation time. In order to determine the best
centrifugation time, the experiments were performed in the
time range of 530 min under optimized conditions. The results
showed that centrifugation time had a signicant inuence on
the signals of the analytes. The best results were obtained with
10 min centrifugation time. The analyte signals were nearly
constant beyond the centrifugation time of 10 min. The
optimum centrifugation time for this process was chosen as 10
min (Fig. 5).

Eect of pH on the recoveries of the analyte ions (n 3).

Fig. 2 Eect of the amount of a-benzoin oxime on the recoveries of the analyte
ions (n 3).

This journal is The Royal Society of Chemistry 2013

Fig. 4 Eect of the centrifugation rate of on the recoveries of the analyte ions
(n 3).

Anal. Methods

View Article Online

Analytical Methods

Published on 03 June 2013. Downloaded by Instituto de Invest Marinas on 02/07/2013 07:05:44.

3.6

Paper

Sample volume and preconcentration factor

The eect of the sample volume on the recovery of the analyte

ions was investigated with sample volumes in the range of
251000 mL by using the model solutions. The centrifuge tubes
used have a maximum capacity of 50 mL. For sample volumes
larger than 50 mL, we have used the ltration technique.
Quantitative metal recoveries were obtained up to 500 mL of
sample volume, except for Cr(III) and Pd(II). The preconcentration factor was calculated as the ratio of the highest sample
volume (500 mL) to the lowest nal measurement volume
(5 mL) for Fe(III), Pb(II), Cu(II) and Zn(II). As a result, the preconcentration factor was calculated as 100 for these metals,
while it was only 50 for Cr(III) and Pd(II). If we take into
consideration iron alone, it had the highest preconcentration

factor of 200, because it still continued to give quantitative

recoveries at a sample volume of 1000 mL (Fig. 6).
3.7

Alkali and alkaline earth metal ions, and some anions (like Na+,
K+, Ca2+, Mg2+, Cl
, SO42
, H2PO4
) at mg L
1 and higher levels
may have interfering eects on the determination of metal ions
by ame atomic absorption spectrometry. The eects of these
ions on the coprecipitation eciency of Cr(III), Cu(II), Fe(III),
Pb(II), Pd(II) and Zn(II) ions were examined by adding known
concentrations of these ions. Then the coprecipitation procedure was applied individually for all the diverse ions mentioned
above. Tolerable concentrations were found to be 15 000 mg
mL
1 for Na+ ion, 4000 mg mL
1 for K+, Ca2+ and SO42
, 1000 mg
mL
1 for Mg2+, and 500 mg mL
1 for PO43
. The tolerated
amounts of each diverse ion were the concentration values
tested that caused less than 5% absorbance alteration. These
foreign ions did not interfere under the experimental conditions used (Table 1).
3.8

Fig. 5 Eect of the centrifugation time of on the recoveries of the analyte ions
(n 3).

Fig. 6

Eect of the sample volume on the recoveries of the analyte ions (n 3).

Table 1

Eect of foreign ions

Evaluation of method performance

The quantitation of the analytes was performed by using the

external calibration curve method. For each analyte, the calibration curves were prepared from the standard solutions of the
analyte elements. The correlation coecients were at least
0.998.
The limits of detection (LOD) of the proposed method for the
investigated elements were studied under the optimum experimental conditions by applying the proposed procedure for
blank solutions. The detection limits were established by
analyzing 20 blank solutions (3s). The detection limits of Cr(III),
Fe(III), Cu(II), Pb(II), Pd(II) and Zn(II) were found to be 1.1, 0.2, 0.4,
5.3, 3.3, and 0.1 mg L
1, respectively. The relative standard
deviations of the proposed method were <5% for the analyte
ions.
The accuracy of the presented procedure was checked by the
analysis of two certied reference materials (CRM), INCT-TL-1
tea leaves and SPS-WW2 Batch 108 wastewater sample. The
certied and observed values for the certied reference materials are given in Table 2. The results found were in good
agreement with the certied values of CRMs.

The inuence of some ions on the recoveries of analyte ions (n 3)a

Recovery (%)
Ions

Added as

Concentration
(mg L
1)

Na+
K+
Ca2+
Mg2+
SO42

Cl

H2PO4

NaNO3
KNO3
Ca(NO3)2$4H2O
Mg(NO3)2$6H2O
Na2SO4
NaCl
NaH2PO4$2H2O

15 000
4000
4000
1000
4500
12 000
500

Cr(III)

Cu(II)

Fe(III)

Pb(II)

99  1
100  2
100  2
99  1
100  2
98  2
98  1

95  1
96  2
95  2
98  1
100  2
97  2
95  1

95  1
100  1
100  1
99  1
100  1
96  2
98  1

95 
98 
95 
96 
95 
96 
100 

Pd(II)
1
1
1
1
1
1
1

95
95
98
97
97
100
95

1
1
2
1
2
1
1

Zn(II)
96  2
98  2
95  1
96  1
95  1
96  2
100  2

Average  standard deviation.

Anal. Methods

This journal is The Royal Society of Chemistry 2013

View Article Online

Paper
Table 2

Analytical Methods
The results for the standard reference materials (n 3)

Published on 03 June 2013. Downloaded by Instituto de Invest Marinas on 02/07/2013 07:05:44.

INCT-TL-1 tea leaves (mg g
1)

SPS-WW2 Batch 108 waste water (mg L
1)

Analyte

Certied value

Found

RE (%)a

Certied value

Found

RE (%)

Cr(III)
Fe(III)
Cu(II)
Pb(II)
Pd(II)
Zn(II)

1.91  0.22b
432
20.4  1.5
1.78  0.24

34.7  2.7

1.86  0.05
429  2
19.5  0.8
1.70  0.06

33.2  1.3

2.6

0.7

4.4

4.5

4.3

1000
1000
1000
1000

1000

5
5
5
5

984  1
992  2
989  1
991  1

982  6

1.6

0.8

1.1

0.9

1.8

RE%: per cent relative error.

Table 3

Average  standard deviation.

The determination of analyte ions in red mullet, green tea and tap water samples after the application of the presented procedure (N 3)

Tap water (mg L
1)

Sample

Added

Found

Cr

0.1
1.0

0.5
100

1.0
2.0

0.2

1.0

0.5
10
20

0.096 
0.97 
0.37 
0.83 

0.56 
1.49 

0.19 

0.96 
0.28 
0.77 

Fe

Cu

Pb
Pd
Zn

5

0.008a
0.05
0.02
0.05
0.06
0.22

0.04
0.08
0.06
0.11

Red mullet (mg g
1)

Recovery (%)

Found

96
97

96

96

95

96

99

0.05 
0.145 

78 

174 

0.98 
1.9 

0.192 

0.97 
9.7 

19 

1
1
1
2
1
2
3

0.01
0.014
4
6
0.09
0.1
0.043
0.11
0.9
1

Green tea (mg g
1)

Recovery (%)

Found

Recovery (%)

97  2

98  2

98  1
95  1

96  1

97  3

96  2

0.41  0.06

1.35  0.09
178  6

269  5
2.25  0.14
3.09  0.18
4.1  0.13
0.21  0.03
0.39  0.06

0.98  0.07
18.2  2.1

27.7  1.9
37  2

96  2

97  2

95  2
96  1

95  1

98  2

98  3
97  2

Average  standard deviation.

Table 4

Determination of the analytes in some food samples after application of the proposed coprecipitation procedure (n 3, mg g
1)

Sample

Cr(III)

Cu(II)

Fe(III)

Pb(II)

Pd(II)

Zn(II)

Black tea
Carnation
Heath
Green tea
Pomegranate ower
Red mullet
Daisy
Bay leaf
Coee
Corn
Rice
Sesame
Cumin our
Linen
Bean

0.45  0.05a
0.55  0.04
0.33  0.04
0.46  0.08
0.34  0.08
0.06  0.01

0.46  0.01

0.16  0.02

0.92  0.16

1.72  0.16
0.23  0.06
0.19  0.02
2.07  0.11
2.02  0.06

4.02  0.08
0.37  0.06

1.95  0.08
2.53  0.08

0.53  0.06
0.20  0.06
1.81  0.12

152  3
137  6
179  2
173  5
242  4
80  5
249  1
20  1
23  2
14  1
4.6  0.3
19  1
47  2
47  3
201  18

b
0.31  0.01
0.39  0.01
0.17  0.01

0.23  0.04

0.011  0.003
0.38  0.02

14  1
5.3  0.5
3.22  0.65
17  2
14  1
8.8  0.6
21  1
3.04  0.07
0.6  0.1
29  1
29  3
38  4
30  2
40  1
19.7  0.1

Average  standard deviation. b Below detection limit.

This journal is The Royal Society of Chemistry 2013

Anal. Methods

View Article Online

Analytical Methods

Published on 03 June 2013. Downloaded by Instituto de Invest Marinas on 02/07/2013 07:05:44.

Table 5

Paper

Application of the presented procedure for various waters and anode slime samples (n 3)

Sample

Cr(III)

Cu(II)

Fe(III)

Tap water (mg L
1)

Rain water (mg L
1)
Waste water (mg L
1)
Acidic dialysis solution (mg L
1)
Sea water (mg L
1)
Anode slime (mg g
1)

4.7  0.2
0.24  0.09
7.0  1.0
12.3  0.5

5.4  0.3b
0.5  0.1
7.3  0.9
1.2  0.1
7.0  0.8
3610  30

10.8
7.0
12.0
33.3
35.6
2291

 0.5
 0.1
 1.7
 0.6
 1.2
 62

Pb(II)

Pd(II)

Zn(II)

6.7  0.2

2.4  0.4
2.4  0.1
350  40
4.3  0.8
6.6  2.8
95  4

2.0  0.1

22 746  427

Below detection limit. b Average  standard deviation.

Table 6

Comparison of the results of the proposed method with the other published studies

Preconcentration method

Analyte

Technique

LOD (mg L
1)

RSD (%)

PF

Reference

Solvent extraction
Coprecipitation method
SPE
SPE
SPE
SPE
Coprecipitation method

Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn

Pb, Fe, Co, Cr, Zn
Pb, Cu, Cd, Ni
Cr, Cu, Pb
Pb, Cd, Zn
Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn
Cr, Cu, Fe, Pb, Pd, Zn

FAAS
FAAS
FAAS
ICP-OES
FAAS
FAAS
FAAS

0.330.9
0.32.3
0.60.9
4385
0.50.7
0.060.67
0.15.3

<4
<4
0.41.0
3.54.6
<6.3
<1.5
<5

20
150
200
8796
200
100
200 for Fe, 100 for Cu,
Pb, Zn, 50 for Cr, Pd

14
25
26
27
28
29
This work

The recovery studies for the analyte ions were performed for
tap water, red mullet and green tea samples. Known amounts of
the analytes were spiked to the sample solutions in order to
estimate the accuracy of the presented procedure. The results
are given in Table 3. Good agreement was obtained between the
added and found analyte contents using the recommended
procedure.

The proposed method was also free of interference compared to

conventional procedures to determine analyte metal ions. The
presented coprecipitation method can be applied not only to
water but also to food samples. Consequently, the proposed
procedure is fast, precise, reliable and economic.

References
3.9

Applications

Based on the above ndings, the presented procedure was

applied for the determination of analytes in some food samples.
The results are summarized in Table 4. The concentrations
given in Table 4 were calculated on the assumption of 100%
recovery of the analyte ions.
The proposed method was applied to various water samples.
The pH of the samples was adjusted to 8.5. Then the preconcentration procedure was applied to the water samples
under study (Table 5).

Conclusions

The presented procedure using Ni(II)a-benzoin oxime can be

successfully applied for the determination of Cr(III), Cu(II), Fe(III),
Pb(II), Pd(II) and Zn(II) in food samples. The eects of common
matrix ions during FAAS are tolerable. The recoveries of the
analyte ions were greater than 95% at the optimal working
conditions. The coprecipitation method could be performed
within about 30 min. The preconcentration factor was achieved as
200 for Fe(III), 100 for Cu(II), Pb(II), and Zn(II), and 50 for Cr(III) and
Pd(II). The achieved detection limits of the analytes are superior to
some other preconcentration/separation methods (see Table 6).

Anal. Methods

1 http://chem-tox-ecotox.org/wp/wp-content/uploads/2010/01/02Metals-17_01_2010.pdf, on 18 April 2013.

2 K. S. Kostecka, J. Chem. Educ., 2000, 77, 13211323.
3 N. Longas, R. G. Arrona, M. Ostra and E. Millan, At.
Spectrosc., 2009, 30, 47.
4 J. Zukowska and M. Biziuk, J. Food Sci., 2008, 73, 21.
5 M. Zeeb, M. R. Ganjali, P. Norouzi and M. R. Kalaee, Food
Chem. Toxicol., 2011, 49, 1086.
6 G. Xiang, Y. Huang and Y. Luo, Microchim. Acta, 2009, 165, 237.
7 M. das. G. A. Korn, E. S. da. B. Morte, D. C. M. B. dos. Santos,
J. T. Castro, J. T. P. Barbosa, A. P. Teixeira, A. P. Fernandes,
B. Welz, W. P. C. dos. Santos, E. B. G. N. dos. Santos and
M. Korn, Appl. Spectrosc. Rev., 2008, 43, 67.
8 H. S. Ferreira, A. C. N. Santos, L. A. Portugal, A. C. S. Costa,
M. Mir
o and S. L. C. Ferreira, Talanta, 2008, 77, 73.
9 Sx. Samac, Sx. Kartal and M. Samac, Clean: Soil, Air, Water,
2011, 39, 584.
10 http://ec.europa.eu/environment/waste/studies/pdf/heavy_
metalsreport.pdf.
11 Sx. Samac and Sx. Kartal, Int. J. Environ. Anal. Chem., 2011, 91,
448.
12 P. Liang, E. Zhao and F. Li, Talanta, 2009, 77, 1854.
13 O. Acar, Internet Journal of Food Safety, 2011, 13, 45.

This journal is The Royal Society of Chemistry 2013

View Article Online

Published on 03 June 2013. Downloaded by Instituto de Invest Marinas on 02/07/2013 07:05:44.

Paper
14 Sx. Samac and S
x. Kartal, Clean: Soil, Air, Water, 2011, 39, 577.
15 Q. He, X. J. Chang, X. P. Huang and Z. Hu, Microchim. Acta,
2008, 160, 147.
16 D. Hammer, M. Nicolas and D. Andrey, At. Spectrosc., 2005,
26, 203.
17 R. Manjusha, K. Dash and D. Karunasagar, Food Chem.,
2007, 105, 260.
18 L. Liu, L. Ding, M. Qi, X. L. Han and H. Q. Zhang, Spectrosc.
Spectral Anal., 2007, 27, 1436.
19 D. Citak, M. Tuzen and M. Soylak, Food Chem. Toxicol., 2009,
47, 2302.
20 V. A. Lemos, D. G. da Silva, A. L. de Carvalho, D. D. Santana,
G. D. Novaes and A. S. dos Passos, Microchem. J., 2006, 84, 14.

This journal is The Royal Society of Chemistry 2013

Analytical Methods
21 M. Hiraide, H. Hommi and H. Kawaguchi, Anal. Sci., 1991, 7,
169.
22 T. Minami, K. Atsumi and J. Ueda, Anal. Sci., 2003, 19, 313.
23 J. Ueda and C. Mizui, Anal. Sci., 1988, 4, 417.
24 H. Sawatari, E. Fujimori and H. Haraguchi, Anal. Sci., 1995,
11, 369.
25 Sx. Samac and Sx. Kartal, Microchim. Acta, 2010, 170, 75.
26 F. Xie, X. Lin, X. Wu and Z. Xie, Talanta, 2008, 74, 836843.
27 J. S. Suleiman, B. Hu, H. Peng and C. Huang, Talanta, 2009,
77, 15791583.
28 A. Goswami and A. K. Singh, Talanta, 2002, 58, 669678.
29 Sx. Samac, S
x. Kartal, M. Samac and C. Soykan, Bull. Korean
Chem. Soc., 2011, 32, 444450.

Anal. Methods