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Food Chemistry
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Analytical Methods
a r t i c l e i n f o a b s t r a c t
Article history: A rapid, sensitive, accurate and precise method for the determination of Pb, Cd, As and Cu in seafood and
Received 19 July 2013 sh feed samples by Simultaneous Electrothermal Atomic Absorption Spectrometry was developed in
Received in revised form 12 October 2013 regard to Council Directive 333/2007EC and ISO/IEC 17025 (2005). Different approaches were investi-
Accepted 10 November 2013
gated in order to shorten the analysis time, always taking into account the sensitivity. For method vali-
Available online 20 November 2013
dation, precision (repeatability and reproducibility) and accuracy by addition recovery tests have been
assessed as performance criteria. The expanded uncertainties based on the Eurachem/Citac Guidelines
Keywords:
were calculated. The method was accredited by the Hellenic Accreditation System and it was applied
Seafood
Fish feed
for an 8 years study in seafood (n = 202) and sh feeds (n = 275) from the Greek market. The annual
Eight-year study and seasonal variation of the elemental content and correlation among the elemental content in sh feeds
Heavy metals and metalloids and the respective sh samples were also accomplished.
Uncertainty calculation 2013 Elsevier Ltd. All rights reserved.
Seasonal variation
0308-8146/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodchem.2013.11.045
A.K. Psoma et al. / Food Chemistry 151 (2014) 7278 73
on oxidation with concentrated acids. However, to the best of our The palladium/magnesium modier solution was prepared by
knowledge, no accredited methods have been reported in the liter- appropriate dilution of 10 g/L Pd (Merck) in HNO3 and 1 g/L Mg
ature concerning the simultaneous determination of Cd, Pb, Cu and in 1% (v/v) HNO3 (High Purity Standards, Charleston, SC). The Zr,
As in seafood and sh feed samples. Furthermore, there are few Ir and NH4H2PO4 solutions were prepared by appropriate dilution
studies concerning the seasonal variation of these elements in sea- of 1000 5 lg mL1 ZrOCl22H2O in 0.5% HNO3 (High Purity Stan-
food samples (Ekpo & Ibok, 1999; Mendil et al., 2010; Obasohan & dards), 1000 lg mL1 of Ir in 2% HCl (High-Purity Standards) and
Eguavoen, 2008), but the collected data sets provide conclusions 100 g/L NH4H2PO4 in 0.05% HNO3 (High-Purity Standards) with ul-
only about the correlation between the seasonal variability and tra pure water. Likewise, HNO3 65%, Suprapur (Merck) was used
the elemental annual accumulation. for digestion of the samples.
In this study, a method for the simultaneous determination of Nineteen different seafood species (totally 202 samples) and
Pb, Cd, As and Cu in seafood and sh feed samples by Simultaneous 275 sh feed samples were obtained from local markets in Athens,
Electrothermal Atomic Absorption Spectrometry (SIMAAS) was Greece and different aquaculture farms from Aegean and Ionian
developed in regard to Council Directive 333/2007 EC and ISO/ Sea in Greece (from 2005 to 2013). Samples were milled and
IEC 17025 (2005) was accomplished. For this reason, different ap- homogenised in a food processor as they arrived in the laboratory
proaches, including the single-elemental, the two elemental deter- with a stainless steel cutter to obtain a representative homogenous
mination (PbCd and CuAs) and the simultaneous determination subsample. For sh samples, only the edible muscle was homoge-
of all the four analytes, were investigated in order to shorten the nised whereas, for shrimps, and cephalopods, the whole body was
analysis time. The developed method was accredited by the Hel- homogenised. Finally, only the soft tissue of the mussels was
lenic Accreditation System and it is now available for the ofcial homogenised, after rejection of the shell. The homogenised sam-
control of Pb, Cd, As and Cu in seafood and sh feed samples. Fur- ples were stored at 18 C till analysis.
thermore in this study, an overall seasonal variation of metal accu-
mulation for over 8 years for the sea breams and sea basses 2.3. Analytical procedure
collected from aquaculture centres in Greece and the seasonal var-
iation of the metal content in sh feeds, collected together with the All glassware and polypropylene bottles were cleaned with
sea bass and sea bream samples from the same aquaculture centres acidied ultra pure water. 0.5000 g (wet weight) of the homoge-
during 20052013, was performed. Finally, the metal content of 17 nised seafood or 0.2500 g (wet weight) of the homogenised sh
additional seafood species, purchased from the Greek market in feed samples were weighted into the Teon vessels and 5 mL of
different years was determined for the rst time. Due to the vast 65% HNO3 were added. The samples were digested with the MARS
number of collected data sets, reliable conclusions about the corre- X-Press (CEM Corporation) microwave oven with a preselected
lation between temporal variability and element concentration can programme (rst stage: 1600 W, 2 min ramp time, 165 C, 0 min
be deduced. hold time; second stage: 1600 W, 3 min ramp time, 175 C, 5 min
hold time) and then diluted to a nal volume of 20 mL with ultra-
pure water.
2. Materials and methods
The pyrolysis and atomization temperature curves were ob-
tained by spiking 20 lL of a digested sample solution and 20 lL
2.1. Instrumentation
of the mixed standard solution in order to investigate the electro-
thermal behaviour of those elements. For this purpose, the ele-
A Perkin-Elmer SIMAA-6000 simultaneous multielement atom-
ments were tested separately, in pairs (PbCd and AsCu), or in
ic absorption spectrometer with a longitudinal Zeeman-effect
an all elements mode in the presence of the different chemical
background correction system, equipped with a transversely-
modiers.
heated graphite atomizer (THGA), and an AS-72 autosampler were
Quantication was performed with calibration curves con-
used. Electrodeless discharge lamps (EDL) were used for As
structed from integrated absorbance measurements and prepared
(193.7 nm and slit 0.7 nm), Pb (247.6 nm and slit 0.7 nm), and
by spiking 20 lL of different mixed aqueous or matrix standard
Cd (228.8 nm and slit 0.7 nm) respectively, and a hollow cathode
solutions of Pb, Cd, As and Cu. Standard addition calibration curves
lamp was used for Cu (324.8 nm and slit 0.7 nm) and they were
were also constructed by spiking different standard solutions in
operated according to the conditions recommended by the manu-
both seafood and sh feed samples in order to exploit the possibil-
facturer. Atomic signals were measured in peak area mode. It
ity for matrix interference. The instrumental limits of detection
should be pointed out that the experiments were carried out
(LOD (lg L1)) and of quantication (LOQ) were calculated from
using stabilized temperature platform furnace (STPF) conditions,
the equations LODinst = 3.3 SBL/b and LOQinst = 10 SBL/b, respec-
including Zeeman-effect background correction. The digestions
tively, where SBL was the standard deviation of ten blank determi-
were performed on a MARS X-Press microwave oven (CEM
nations and b the slope of the curve. The LODs of the method were
Corporation).
calculated from the equation LODmeth (ng/g) = LODinstr (ng/
mL) Vdilution (mL) m (g)1. According to Commission Regulation
2.2. Reagents, analytical solutions and samples 333/2007/EC, the LODsmeth and LOQsmeth for Cd and Pb should be
less than one tenth and less than one fth, respectively, of the max-
Ultra pure water (18.2 MX cm at 25 C) from a Millipore Direct- imum level in Regulation (EC) No. 1881/2006.
Q-UV water purier (Millipore) obtained using a Milli-Q system Precision under repeatability and reproducibility conditions
(Millipore). All solutions were prepared with Suprapur grade nitric were also estimated from the calibration curves using sea bass
acid (Merck, Darmstadt, Germany). The argon was of 99.999% and sh feed samples with various concentration-level matrix
purity. spiked solutions. As methods precision performance criteria, the
The mixed standard solution containing 50 lgAs L1, 50 lgCu L1, HORRATr were used, meaning the observed relative standard devi-
50 lgPb L1 and 5 lgCd L1, were daily prepared by appropriate ation (%RSDr) under repeatability conditions divided by the RSDr
dilution of 1000 mg L1 As, Cu, Pb and Cd stock standard solutions value estimated from the Horwitz equation (Thompson, 2000)
and acidied with nitric acid to 1% (v/v). The working solutions using the assumption r = 0.66R, as well as the HORRATR values,
were prepared automatically by the autosampler from the mixed meaning the observed RSDR value under reproducibility divided
standard solution. by the RSDR value calculated from the Horwitz equation. According
74 A.K. Psoma et al. / Food Chemistry 151 (2014) 7278
Table 1
Optimal compromised conditions and the calculated analytical characteristics for all the three different approaches in seafood matrix solutions using Pd as chemical modier.
to Commission Regulation 333/2007/EC, the HORRATr and HOR- modied by Kalantzis, Rousis, Pasias, Thomaidis, and Piperaki
RATR values should be less than two. Furthermore, the accuracy (2012).
of measurements was also assessed through recovery experiments Pyrolysis and atomization curves in both standard and matrix
of the addition of known amounts of the element to sea bass and solutions were established to determine the optimum pyrolysis
sh feed samples. Recovery data are only acceptable when they and atomization temperatures for each modier, used at the opti-
are within 20% of the target value (European Commission Deci- mal mass (Suppl. Fig. 1). When a temperature programme for
sion, 2002; European Commission Directive, 2002; European Com- simultaneous multi-element ETAAS analysis is to be developed,
mission, 2006, 2007, 2008a). compromise furnace temperatures have to be considered related
Internal quality control charts (IQCs) were also constructed in to the group of analytes to be determined. Hence, the compromised
order to monitor whether results are reliable enough to be re- parameters are completely different than individually optimised
leased. The objective of IQCs is the elongation of method valida- single-element conditions. The maximum pyrolysis temperature
tion: continuously checking the accuracy of analytical data (Tpyr) that could be applied is imposed by the most volatile ele-
obtained from day to day in the laboratory. The analytical system ment, which in this case was Cd and the atomization temperature
is under control if no more than 5% of the measured values exceed (Tat) is dictated by the most refractory element, Cu. In this study it
the warning limits and none of them the action or control limits was proved that the most appropriate chemical modier for all ele-
(Taverniers, De Loose, & Van Bockstaele, 2004). ments tested in all possible combinations was 1.25 lg Pd since it
The uncertainty of the method was also calculated based on the provided signicant sensitivity and low background absorption.
Eurachem/Citac Guidelines. For most purposes in analytical chem- The NH4H2PO4 and the permanent chemical modier ZrIr did
istry, an expanded uncertainty U should be used. The expanded not provide signicant sensitivity for the determination of AsCu
uncertainty provides an interval within which the value of the ana- and Cu, respectively. On the contrary, in the presence of PdMg
lyte concentration is believed to lie within a higher level of con- as chemical modier the background absorbance was increased
dence. U is obtained by multiplying uc(y), the combined standard signicantly (Suppl. Fig. 2).
uncertainty, by a coverage factor k. The combined uncertainty Using 1.25 lg Pd as a chemical modier, three different ap-
uc(y) was calculated from the summary squared of several inde- proaches were tested in order to minimise the analyses time and
pendent parameters as: (a) the mass uncertainty; (b) the stock cost: (a) the single element determination; (b) the by pairs ele-
standard solutions; (c) the volume uncertainty; (d) the calibration ment determination (CdPb and CuAs); and (c) the simultaneous
uncertainty; (e) the bias uncertainty; and (f) the random errors determination of all four analytes. Table 1 shows the optimal com-
uncertainty, following the rules of Eurachem/Citac Guidelines. promised conditions and the calculated analytical characteristics
Methods suitable for ofcial control must produce results with for all three different approaches. Among the approaches tested,
standard measurement uncertainties less than the maximum stan- the by pairs element determination proved to be the most appro-
dard measurement uncertainty calculated using the formula below priate for the ofcial determination of Pb, Cd, As and Cu in seafood
(European Commission, 2007): and sh feed samples since it provides low detection limits and
q high calculated sensitivity in short analyses time. The simulta-
Uf LOD=22 aC 2 1 neous determination of all four analytes did not seem to be an
appropriate approach for the ofcial control because it provides
where: high limits of detection due to the fact that the compromised con-
Uf is the maximum standard measurement uncertainty (lg/kg). ditions were signicantly different than the respective conditions
LOD is the limit of detection of the method (lg/kg). in the single element approach and these limits were out of the
C is the concentration of interest (lg/kg). maximum permissible levels. For Pb and Cd in particular, the max-
a is a numeric factor to be used depending on the value of C. imum permissible limits of detection in seafood samples according
Table 2
3. Results and discussion Comparison of the calibration curves obtained by aqueous standard solutions and
seafood matrix matched standard solutions for the simultaneous determination of
3.1. Comparison of single and simultaneous elemental determination CdPb and AsCu. Pd was used as chemical modier.
Table 3 (<30, and <5 lg kg1 for the determination of Pb and Cd in seafood
Comparison of the calculated uncertainties and the maximum standard calculated samples, respectively) and (EC) No. 32/2002 (<500, <50, and
uncertainties obtained by three different concentration levels for the simultaneous
determination of CdPb and AsCu in seafood and sh feed samples.
<400 lg kg1 for the determination of Pb, Cd and As in sh feed
samples, respectively).
Analyte concentration Calculated uncertainty Maximum uncertainty Precision experiments were carried out and the relative stan-
level (ng/g) (ng/g) (ng/g)
dard deviation (%RSD) values achieved from three different con-
Seafood samples centration levels, measured six times under repeatability
Cd (4.5280700) 0.863585 0.9552105
Pb (856706100) 9.568607 18102732
conditions and six times at two different days under reproducibil-
Cu (46010003000) 52108326 74125370 ity conditions, were lower than 10% for all different concentration
As (320130015000) 52143685 591531488 levels and for all analytes. The HORRATr and HORRATR values
Fish feed samples achieved from these different concentration levels, ranged from
Cd (4.5280700) 0.823585 1.052105 0.27 to 0.48 for Cd, 0.19 to 0.50 for Pb, 0.51 to 0.67 for As and
Pb (856706100) 8.347417 23103417 0.30 to 0.54 for Cu. These values were lower than the crucial value
Cu (46010003000) 83128325 89134373
of two, as described by the European Commission Regulation 333/
As (320130015000) 561471280 601541489
2007 for the ofcial control of the levels of lead, cadmium and
other contaminants in foodstuffs. However, this regulation may
be used also when a limited number of fully validated methods
of analysis exist, and a tness-for-purpose approach may be used
to Commission Regulation 333/2007/EC are 30 and 5 lg kg1, to assess the suitability of the method of analysis.
respectively, when the calculated limits were 40 and 3.2 lg kg1, For accuracy estimation additional recovery experiments were
respectively. Furthermore, the limit of detection for the determina- carried out in order to check the trueness of the proposed method.
tion of As was increased at least 100 times compared to the single The (%) calculated recoveries for Cd, Pb, As and Cu, expressed as the
element approach and for about 30 times compared to the by mean value of six different spiked samples for each different con-
pairs approach. On the other hand, the by pairs approach ele- centration level ranged from 86% to 104% for sh feed samples and
mental determination was considered the most appropriate, since 95108% for seafood samples. The recovery data are within 20% of
it provided similar sensitivity compared to the single element the target value (European Commission, 2008a) and for this reason
determination and the limits of detection were less than the max- the developed method was considered as t for purpose.
imum permissible limits of detection in seafood samples according The uncertainty of the method was also calculated based on the
to Commission Regulation 333/2007/EC. By using this approach, Eurachem/Citac Guidelines. In practice, the uncertainty of the re-
the analysis time was reduced signicantly. For example, the anal- sults in this study arose from many possible sources, including ma-
ysis time for the determination of Pb, Cd, As and Cu in 100 samples trix effects and interferences, environmental conditions,
was reduced to about 8 h. uncertainties of masses and volumetric equipment, reference val-
ues, approximations and assumptions incorporated in the mea-
3.2. Method validation surement method and procedure, and random variation. The
combined uncertainty uc(y) was calculated from the summary
Calibration curves for the simultaneous determination of CuAs squared of several independent parameters such as: (a) the mass
and CdPb were constructed using 1.25 lg of Pd for all the differ- uncertainty; (b) the mix stock standard solution; (c) the volume
ent matrices. Curves in the 10.050.0 lg/L for As and Cu 5.00 uncertainty; (d) the calibration uncertainty; (e) the bias uncer-
50.0 lg/L for Pb, and 0.505.00 lg/L for Cd concentration range tainty, as estimated by the addition recovery tests and through
were established using the integrated analyte absorbance versus the comparison of the calculated recoveries and the theoretical
analyte concentration and typical linear correlations of ones provided by the Commission Regulation 333/2007/EC
R2 P 0.998 were obtained. Quantication was also performed with (100 20%), and (f) the precision uncertainty, as estimated by the
matrix-matched calibration curves, constructed from integrated % RSDR values for the three different concentration levels under
absorbance measurements and prepared automatically by the reproducibility conditions. The choice of the factor k is based on
autosampler by spiking 20 lL of a digested sample solution with the level of condence desired. For an approximate level of con-
20 lL of different standard solutions (10.0, 20.0, 40.0 and dence of 95%, k is 2. The calculated expanded uncertainties and
50.0 lg L1 for the simultaneous determination of Cu and As; the respective theoretical one calculated by Eq. (1) are shown in
0.50, 1.00, 2.50 and 5.00 lg L1; and 5.00, 10.0, 25.0 and Table 3. The results show that the method is suitable for the ofcial
50.0 lg L1 for the simultaneous determination of Cd and Pb). Re- control of Cd, Pb, As and Cu in sh and sh feed samples due to the
sults are summarised in Table 2. It was observed that, in the pres- fact that it produced results with standard measurement uncer-
ence of the 1.25 lg of Pd, the slopes of the calibration curves and tainties less than the maximum standard measurement
the matrix matched calibration curves were different for Cd, Pb uncertainty.
and As (Table 2). This means that, for accurate results, calibration
with matrix-matched standards should be applied. 3.3. Determination of Cd, Pb, As and Cu in seafood and sh feed
The instrumental LODs are presented in Table 1. Furthermore, samples
the methods LODs were 0.50, 18, 56 and 11 ng/g for the simulta-
neous determination of CdPb and CuAs in seafood samples, The developed and accredited method was applied for the
respectively, and 1.0, 35, 112, and 22 ng/g for the simultaneous simultaneous determination of Cd and Pb in 19 different seafood
determination of CdPb and CuAs in sh feed samples, respec- species (totally 202 samples) and the results were compared to
tively. Finally, the calculated LOQs were 1.5, 53, 168, and 32 ng/g the European Regulation (EC) No. 1881/2006. Furthermore, the
for the simultaneous determination of CdPb and CuAs in seafood method was also applied for the determination of Cd, Pb, As and
samples and 3.0, 105, 336, and 65 ng/g for the simultaneous deter- Cu in 275 sh feed samples and the results were compared to
mination of CdPb and CuAs in sh feed samples, respectively. the Directive 2002/32/EC. Finally, an overall seasonal variation of
The calculated LODs were lower than the suggested values as pre- metals and metalloid accumulation for over 8 years in the two
sented in Commission Regulation 333/2007/EC and the maximum most produced shes in Greece (sea bream and sea bass) was
permissible levels as presented in Regulations (EC) No. 1881/2006 accomplished for the rst time.
76 A.K. Psoma et al. / Food Chemistry 151 (2014) 7278
Table 4
Cd and Pb content in seventeen different seafood species purchased from the Greek market.
The samples were obtained from local markets in Athens, contrary, the concentrations found for cadmium and lead from
Greece and different aquaculture centres (from 2005 to 2013). Prez Cida, Boia, Pombo, and Rebelo (2001), in the muscle of the
Samples were milled and homogenised in a food processor with Anguilla anguilla, Mullus surmuletus, Trigla lucerna, Mugil cephalus,
a stainless steel cutter to obtain a representative material. Proce- Chelon labrosus, Liza aurata and D. labrax from Portugal were lower
dural blanks were always run and contamination from this step than 0.043, 0.15 respectively.
was never observed. Each sample was digested and measured On the contrary, As and Cu, which are not included in the Euro-
three times. Contents were calculated on a wet weight basis. As pean Commission Regulation 1881/2006, were determined only for
shown in Tables 4 and 5, the contents of Cd, Pb in the muscle tissue the most consumed seafood samples in Greece (sea bream and sea
of the different sh samples (n = 162, from 14 different seafood bass). These sh species showed that As content ranged from
species) ranged from <0.5 lg/kg to 28 lg/kg and <18 lg/kg to 0.038 mg/kg to 3.85 mg/kg, n = 59 and Cu content ranged from
162.6 lg/kg, respectively. As concerns the content levels of Cd 0.17 mg/kg to 1.74 mg/kg, n = 78, respectively (Table 5). Several
and Pb in crustaceans (shrimps), they ranged from <0.5 lg/kg to studies have proven that the greatest part of arsenic is in the or-
165 lg/kg, n = 29 and <18 lg/kg to 89 lg/kg, n = 29, respectively. ganic form (over 68%) (Julshamn et al., 2012; Schaeffer, Soeroes,
Furthermore, bivalve molluscs (mussels) showed the highest con- Ipolyi, Fodor, & Thomaidis, 2005; Shah et al., 2010). Taking into ac-
tent of Cd and Pb among all other seafood species, as expected, count that the greatest portion of As due to dietary exposure (94%
and the values ranged from 0.16 mg/kg to 0.72 mg/kg, n = 4 and of the total As) comes from the seafood group (Ysart et al., 2000)
<18 lg/kg to 88 lg/kg, n = 4, respectively. Finally, in cephalopods and that a provisional tolerable weekly intake (PTWI) for total As
(squids, cuttleshes, octopus) content of Cd and Pb ranged from has not been recommended, a further study for the potential risks
<0.5 lg/kg to 640 lg/kg, n = 7 and <18 lg/kg to 97 lg/kg, n = 7, for human health should be undertaken. However, in a previous
respectively. These values were lower than the crucial values, as study for As speciation in Aegean Sea seafood, no risks associated
described by the European Commission Regulation 1881/2006 set- to As dietary exposure were found (Schaeffer et al., 2005). Never-
ting maximum levels for certain contaminants in foodstuffs. Com- theless, to assess the risk for consumers from copper intake
paring the quality of the consumed seafood species in Greece to through sh consumption, the weekly intake for a 70-kg adult
those in other countries as reported in the literature, it can be pro- was compared with the PTWI (3.5 mg Cu/kg body weight/week)
posed that Greek seafood samples tend to have a lower content of (FAO/WHO, 2004). According to the data available through the
toxic elements. Generally, cadmium and lead levels in analysed sh European programme DAFNE (Data Food Network) based on the
samples, as described in the literature, were found to be similar or average diet per person, the daily average sh consumption in
higher than the maximum permissible limits. For example, Tuzen Greece is equal to 46 g. This means that to overcome the PTWI va-
(2009) found 0.280.87 mg/kg for lead and 0.100.35 mg/kg for lue, a 70-kg adult must consume 570 kg of seafood/week. Compar-
cadmium in ten different seafood species from the Black Sea. Sim- ing the results obtained from the current study to others presented
ilar results were reported from Trkmen et al. (2010) who found in the literature, it can be assumed that the results are in agree-
0.100.47 mg/kg cadmium, 0.190.47 mg/kg for lead in sea bream ment with values reported by many researchers for seafood sam-
(Sparus aurata), European sea bass (Dicentrarchus labrax), and ples (Prez Cida et al., 2001; Trkmen et al., 2008, 2010; Tuzen,
keeled mullet (Liza carinata Valenciennes) from the Mediterranean 2009).
region. High metal concentrations in edible parts of seafood species Similarly, the contents of Cd, Pb and As in sh feed samples
were also reported from Trkmen et al. (2008) (0.020.37 mg/kg were lower than the maximum permissible values, as described
for cadmium and 0.330.86 mg/kg for lead, respectively) from by Directive 2002/32/EC concerning the undesirable substances
Marmara, Aegean and Mediterranean seas in Turkey. On the in animal feeds. More specically, the content of Cd ranged from
A.K. Psoma et al. / Food Chemistry 151 (2014) 7278 77
Table 5
Cd, Pb, As and Cu content in sea bream and sea bass sh samples obtained from Greek aquacultures.
1881/2006 setting maximum levels for certain contaminants in Hanks, A. (2000). Mineral feed contaminants pp. 265269. Oxford, IN: Ofcial
Publication of the Association of Feed Control Ofcials Inc..
foodstuffs. Finally, it was proved that there is no seasonal variation
ISO/IEC 17025. (2005). General requirements for the competence of testing and
of metal content in sea bream and sea bass sh samples and that calibration laboratories.
there is a strong correlation among the sh dietary and the ele- Julshamn, K., Nilsen, B. M., Frantzen, S., Valdersnes, S., Maage, A., Nedreaas, K., et al.
mental accumulation. (2012). Total and inorganic arsenic in sh samples from Norwegian waters.
Food Additives and Contaminants: Part B: Surveillance, 5, 229235.
Kalantzis, V., Rousis, N., Pasias, I., Thomaidis, N., & Piperaki, E. (2012). Evaluation of
Appendix A. Supplementary data different modiers for the determination of arsenic in leachate samples from
sanitary landlls by electrothermal atomic absorption spectrometry. Analytical
Letters, 45, 592602.
Supplementary data associated with this article can be found, Lima, E. C., Krug, F. J., & Jackson, K. W. (1998). Evaluation of tungstenrhodium
in the online version, at http://dx.doi.org/10.1016/j.foodchem. coating on an integrated platform as a permanent chemical modier for
cadmium, lead, and selenium determination by electrothermal atomic
2013.11.045.
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Low, K. H., Zain, S. Md., & Radzi Abas, Mhd. (2012). Evaluation of microwave-
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