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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: Determination of metal levels in muscles and livers of twelve fish species from Aegean Sea and Mediter-
Received 24 March 2008 ranean Sea by ICP-AES was made. The levels of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn in muscles of fish were
Received in revised form 24 June 2008 <0.01–0.39, <0.01–0.45, 0.07–1.48, 0.51–7.05, 9.18–136, 0.18–2.78, 0.03–1.72, 0.21–1.28 and 3.51–
Accepted 28 June 2008
53.5 mg kg 1, respectively. Metal levels in muscles were generally lower than those in livers. Metal con-
centrations in the edible parts of fish were assessed for human uses according to provisional tolerable
weekly intake (PTWI) and provisional tolerable daily intake (PTDI). The estimated values of all metals
Keywords:
in muscles of fish in this study were below the established values. Therefore, it can be concluded that
Metals
Fish
these metals in edible parts of the examined species should pose no health problems for consumers.
Aegean Ó 2008 Elsevier Ltd. All rights reserved.
Mediterranean
PTWI
PTDI
1. Introduction tion in key species, because this will give an indication of the tem-
poral and spatial extent of the process, as well as an assessment of
Fish, generally accumulate contaminants from aquatic environ- the potential impact on organism health (Kotze, Preez, & van Vu-
ments, have been largely used in food safety studies. Heavy metals ren, 1999).
discharged into the marine environment can damage both marine Because the metal pollution in aquatic environments can be
species diversity and ecosystems, due to their toxicity and accumu- harmful to human health, it is necessary to understand and control
lative behaviour (Matta, Milad, Manger, & Tosteson, 1999). As the the hazard levels of pollution in seafood. Therefore, this study
spawning and nursery grounds of many marine species, including aimed to determine the levels of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb
the commercially valuable shrimps and fish, are located in estua- and Zn in the muscles and livers of the different species from Ae-
rine and coastal areas, they are directly affected by such influx of gean Sea and Mediterranean Sea, and to assess the public health
chemical contaminants into the marine ecosystem (Gibson, 1994). risks associated with consuming fish harvested from these areas
Low or high trace element unbalances can be considered as risk by estimating daily and weekly intakes and by comparing them
factors for several diseases. Metals, such as iron, copper, zinc and with the PTWI and PTDI recommended by various authorities.
manganese, are essential metals since they play important roles
in biological systems, whereas mercury, lead and cadmium are 2. Materials and methods
toxic, even in trace amounts. The essential metals can also produce
toxic effects at high concentrations. Only a few metals with proven 2.1. Sampling
hazardous nature are to be completely excluded in food for human
consumption. Metal absorption in fish is carried out via two uptake Fish samples were obtained from commercial fishing efforts of
routes: digestive tract (diet exposure) and gill surface (water expo- local fishermen in four different sites in Aegean Sea and Mediterra-
sure) (Ptashynski, Pedlar, Evans, Baron, & Klaverkamp, 2002). Met- nean Sea from November 2004 to July 2005. These sampling sites
als are further transferred via blood to other target organs, such as are Northern Aegean Sea (NAS) and Central Aegean Sea (CAS) in
the liver and kidney. Therefore, we selected muscles as a primary _
Aegean Sea, Antalya Bay (AB) and Iskenderun Bay (IB) in Mediter-
site of metal uptake and liver as tissues specialised in metal storage ranean Sea (Fig. 1). Twelve fish species (124 samples) examined in
and detoxification. Due to the deleterious effects of metals on this study are axillary seabream (Pagellus acarne Risso, 1827), piper
aquatic ecosystems, it is necessary to monitor their bioaccumula- gurnard (Trigla lyra L., 1758), painted comber (Serranus scriba L.,
1758), small-spotted catshark (Scyliorhinus canicula L., 1758), bas-
* Corresponding author. Tel.: +90 326 6141693; fax: +90 326 6141877.
tard grunt (Pomadasys incisus Bowdich, 1825), Atlantic stargazer
E-mail address: mturkmen65@hotmail.com (M. Türkmen). (Uranoscopus scaber L., 1758), thinlip mullet (Liza ramado Risso,
0308-8146/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2008.06.071
234 M. Türkmen et al. / Food Chemistry 113 (2009) 233–237
_
Fig. 1. The sampling locations from Aegean and Mediterranean seas, NAS: North Aegean Sea, CAS: Central Aegean Sea, AB: Antalya Bay, IB: Iskenderun Bay.
1810), European seabass (Dicentrarchus labrax L., 1758), derbio them. Metal analyses were done in the Central of Science Research
(Trachinotus ovatus L., 1758), chub mackerel (Scomber japonicus and Application of Mustafa Kemal University.
Houttuyn, 1782), bluespotted seabream (Pagrus caeruleostictus
Valenciennes, 1830) and yellowmouth barracuda (Sphyraena virid-
ensis Cuvier, 1829). Specimens collected during the sampling peri- 2.3. Statistical analyses
od were frozen in prewashed polyethylene bags and frozen
samples brought to the laboratory in ice chests. Total length and A logarithmic transformation was done on the data to improve
weight of the samples were measured to the nearest millimeter normality. To test the differences between species, one way ANO-
and gram before dissection. Approximately 1 g sample of muscle VA was performed (post-hoc: Tukey). Possibilities less than 0.05
and liver (whole liver for small fish) from each fish were dissected, were considered statistically significant (p < 0.05). All statistical
washed with distilled water, weighed, packed in polyethylene bags calculations were performed with SPSS 13.0 for windows according
and stored at 18 °C until the performance of chemical analysis. to Özdamar (1999).
Table 1
1
Mean metal levels in the muscles of the examined fish species in this study (mg kg wet wt)
Sites Species N Cadmium Cobalt Chromium Copper Iron Manganese Nickel Lead Zinc
ab ab ab b ab ab a ab
NAS P. A. 7 0.05 ± 0.01 0.28 ± 0.06 0.38 ± 0.09 7.05 ± 1.67 37.0 ± 9.06 1.35 ± 0.50 0.75 ± 0.10 0.34 ± 0.14 14.0 ± 3.60a
T. L. 7 0.04 ± 0.01ab 0.12 ± 0.04ab 0.07 ± 0.01a 1.36 ± 0.24ab 35.7 ± 7.95ab 1.93 ± 0.83ab 0.70 ± 0.15a 0.31 ± 0.14ab 4.48 ± 0.85a
S. S. 5 0.06 ± 0.01ab 0.27 ± 0.11ab 1.08 ± 0.36bc 4.88 ± 1.57ab 99.0 ± 30.5ab 2.78 ± 0.32b 0.90 ± 0.37a 0.61 ± 0.13ab 53.5 ± 12.4b
S. J. 8 0.03 ± 0.00ab 0.25 ± 0.09ab 0.15 ± 0.04a 6.22 ± 1.49ab 68.1 ± 20.5ab 1.58 ± 0.69ab 1.00 ± 0.49a 0.54 ± 0.17ab 25.2 ± 8.87a
CAS P. A. 6 0.09 ± 0.03ab 0.02 ± 0.00a 0.22 ± 0.05a 1.63 ± 0.67ab 136 ± 45.3b 0.98 ± 0.28ab 1.72 ± 0.66ab 0.65 ± 0.21ab 6.24 ± 1.11a
T. L. 5 0.05 ± 0.02ab 0.02 ± 0.00a 0.21 ± 0.13a 0.63 ± 0.14a 59.9 ± 13.6ab 0.49 ± 0.09ab 0.51 ± 0.21a 0.14 ± 0.02a 4.47 ± 0.89a
S. J. 4 <0.01 ± 0.00a 0.05 ± 0.01ab 0.18 ± 0.08a 0.51 ± 0.11a 14.8 ± 4.42a 0.18 ± 0.06a 0.12 ± 0.03a 0.21 ± 0.03ab 3.51 ± 0.35a
AB S. C. 4 0.07 ± 0.02ab <0.01 ± 0.00a 0.29 ± 0.08a 0.88 ± 0.23a 34.7 ± 9.32ab 1.04 ± 0.27ab 0.27 ± 0.07a 0.27 ± 0.07ab 10.9 ± 2.93a
P. I. 8 0.39 ± 0.04c 0.45 ± 0.03b 1.48 ± 0.04c 0.34 ± 0.4a 9.18 ± 0.99a 0.69 ± 0.05ab 3.13 ± 0.35b 0.66 ± 0.08ab 8.94 ± 1.47a
U. S. 4 0.08 ± 0.02ab 0.03 ± 0.00a 0.38 ± 0.04ab 0.70 ± 0.17a 31.5 ± 10.0ab 0.80 ± 0.29ab 0.69 ± 0.27a 0.28 ± 0.18ab 8.56 ± 1.27a
S. J. 6 0.08 ± 0.04ab 0.02 ± 0.00a 0.28 ± 0.07a 0.63 ± 0.17a 43.5 ± 20.2ab 0.36 ± 0.05ab 0.84 ± 0.24a 0.25 ± 0.08ab 7.21 ± 0.67a
IB P. A. 5 0.11 ± 0.06abc 0.02 ± 0.00a 0.35 ± 0.18ab 1.27 ± 0.08ab 22.6 ± 1.88a 0.18 ± 0.02a 0.32 ± 0.13a 0.55 ± 0.30ab 6.32 ± 1.02a
T. L. 7 0.13 ± 0.02abc 0.05 ± 0.02ab 0.48 ± 0.10ab 2.48 ± 0.60ab 50.7 ± 19.6ab 1.14 ± 0.15ab 0.45 ± 0.05a 0.42 ± 0.09ab 8.37 ± 1.56a
S. S. 5 0.31 ± 0.15bc 0.37 ± 0.19ab 0.68 ± 0.31ab 1.14 ± 0.29ab 22.6 ± 8.55a 0.61 ± 0.23ab 0.58 ± 0.25a 1.28 ± 0.47b 4.95 ± 0.69a
P. I. 8 0.08 ± 0.02ab 0.02 ± 0.00a 0.15 ± 0.03a 3.97 ± 1.67ab 45.8 ± 12.1ab 0.49 ± 0.20ab 0.51 ± 0.15a 0.52 ± 0.15ab 12.1 ± 3.27a
L. R. 5 0.17 ± 0.7abc 0.08 ± 0.01ab 0.64 ± 0.22ab 1.54 ± 0.33ab 61.6 ± 15.5ab 0.56 ± 0.19ab 0.55 ± 0.05a 0.64 ± 0.21ab 8.04 ± 1.34a
D. L. 8 0.03 ± 0.01ab 0.10 ± 0.03ab 0.27 ± 0.05a 1.06 ± 0.28ab 33.3 ± 10.9ab 0.45 ± 0.04ab 1.02 ± 0.17a 0.48 ± 0.10ab 10.7 ± 1.46a
T. O. 5 0.05 ± 0.01ab 0.03 ± 0.01ab 0.45 ± 0.10ab 0.80 ± 0.18a 9.52 ± 2.20a 0.08 ± 0.03a 0.03 ± 0.01a 0.49 ± 0.11ab 9.27 ± 2.15a
S. J. 5 0.04 ± 0.01ab 0.08 ± 0.03ab 0.48 ± 0.11ab 1.37 ± 0.07ab 33.8 ± 11.6ab 0.47 ± 0.16ab 0.39 ± 0.17a 0.22 ± 0.07ab 8.13 ± 0.67a
P. C. 7 0.21 ± 0.03abc 0.26 ± 0.04ab 0.33 ± 0.08ab 1.18 ± 0.08ab 22.4 ± 7.02a 0.38 ± 0.05ab 0.67 ± 0.12a 0.84 ± 0.29ab 3.80 ± 0.34a
S. V. 5 <0.01 ± 0.00a 0.05 ± 0.02ab 0.35 ± 0.05ab 0.90 ± 0.32a 36.9 ± 11.1ab 0.19 ± 0.06a 0.47 ± 0.14a 0.36 ± 0.06ab 6.90 ± 1.15a
Table 2
1
Mean metal levels in the livers of the examined fish species in this study (mg kg wet wt)
Sites Species N Cadmium Cobalt Chromium Copper Iron Manganese Nickel Lead Zinc
a a a a ab ab a ab
NAS P. A. 7 0.10 ± 0.01 0.42 ± 0.13 0.64 ± 0.21 15.9 ± 2.14 75.3 ± 16.5 4.54 ± 1.63 1.88 ± 0.17 1.23 ± 0.11 17.5 ± 4.98a
T. L. 7 0.11 ± 0.01a 0.28 ± 0.11a 1.90 ± 0.44ab 9.28 ± 1.43a 249 ± 41.8ab 6.12 ± 2.13ab 1.38 ± 0.48a 2.19 ± 0.62ab 51.2±9.89ab
S. S. 5 0.12 ± 0.01a 0.55 ± 0.21a 2.03 ± 0.64abc 15.0 ± 3.71a 168 ± 56.1ab 9.90 ± 2.60b 3.82 ± 1.39a 1.77 ± 0.73ab 93.8 ± 25.2b
S. J. 8 0.33 ± 0.10abc 0.72 ± 0.29a 0.34 ± 0.12a 19.2 ± 5.14a 197 ± 47.2ab 3.65 ± 1.33ab 1.47 ± 0.55a 0.92 ± 0.29ab 35.1 ± 8.76a
CAS P. A. 6 0.60 ± 0.09abc 0.82 ± 0.11a 3.97 ± 0.89c 7.49 ± 1.52a 318 ± 83.9b 8.86 ± 2.79ab 10.2 ± 3.16b 7.15 ± 0.72c 58.6 ± 11.5ab
T. L. 5 0.08 ± 0.03a 0.19 ± 0.03a 1.02 ± 0.17ab 5.25 ± 1.04a 68.7±6.11ab 2.17 ± 0.35ab 4.40 ± 1.11a 0.71 ± 0.28ab 39.1 ± 6.53a
S. J. 4 0.03 ± 0.01a 0.15 ± 0.04a 0.41 ± 0.05a 2.59 ± 0.41a 0.89 ± 0.07a 0.44 ± 0.12a 0.40 ± 0.08a 15.2 ± 0.63a
AB S. C. 4 0.24 ± 0.03ab 0.14 ± 0.02a 0.88 ± 0.11ab 5.10 ± 0.62a 279 ± 55.1ab 2.94 ± 0.36ab 1.64 ± 0.20a 1.10 ± 0.13ab 16.9 ± 2.05a
P. I. 8 0.86 ± 0.07c 0.96 ± 0.09a 2.71 ± 0.19bc 8.62 ± 3.46a 54.2 ± 11.4a 2.25 ± 0.61ab 6.09 ± 1.37ab 1.18 ± 0.09ab 30.3 ± 5.17a
U. S. 4 0.11 ± 0.01a 0.17 ± 0.07a 1.06 ± 0.19ab 19.9 ± 7.76a 153 ± 58.3ab 1.15 ± 0.23ab 1.94 ± 0.35a 0.69 ± 0.29ab 13.3 ± 1.06a
S. J. 6 0.25 ± 0.06ab 0.10 ± 0.02a 0.65 ± 0.09a 1.56 ± 0.36a 94.6 ± 16.0ab 0.80 ± 0.07ab 1.55 ± 0.40a 0.72 ± 0.24ab 17.6 ± 1.81a
IB P. A. 5 0.26 ± 0.10ab 0.14 ± 0.05a 1.04 ± 0.58ab 3.68 ± 1.07a 82.6 ± 28.2ab 0.47 ± 0.07a 1.41 ± 0.59a 2.88 ± 0.68b 23.0 ± 6.68a
T. L. 7 0.71 ± 0.02bc 0.51 ± 0.09a 1.84 ± 0.17ab 9.99 ± 1.36a 176 ± 37.4ab 2.26 ± 0.14ab 1.75 ± 0.23a 2.36 ± 0.39ab 41.9 ± 5.09ab
P. I. 8 0.28 ± 0.07abc 0.13 ± 0.02a 0.56 ± 0.11ab 14.7 ± 3.47a 96.7 ± 16.5ab 0.93 ± 0.18ab 1.07 ± 0.22a 2.05 ± 0.36ab 42.1 ± 10.6ab
L. R. 5 0.56 ± 0.28abc 0.13 ± 0.04a 1.30 ± 0.53ab 3.75 ± 1.30a 188 ± 44.0ab 1.66 ± 0.21ab 1.76 ± 0.25a 1.30 ± 0.26ab 15.9 ± 1.05a
D. L. 8 0.21 ± 0.03ab 0.45 ± 0.14a 0.90 ± 0.27ab 51.1 ± 11.0b 85.7 ± 8.81ab 1.29 ± 0.18ab 3.06 ± 0.49a 1.26 ± 0.12ab 39.5 ± 3.68a
S. J. 5 0.12 ± 0.02a 0.23 ± 0.04a 1.12 ± 0.18ab 3.35 ± 0.32a 270 ± 89.2ab 1.59 ± 0.45ab 1.97 ± 1.02a 0.71 ± 0.09ab 13.2 ± 0.74a
P. C. 7 0.45 ± 0.04abc 0.75 ± 0.09a 0.80 ± 0.10ab 4.40 ± 0.55a 130 ± 22.9ab 1.87 ± 0.23ab 1.22 ± 0.15a 1.45 ± 0.18ab 37.0 ± 4.60a
S. V. 5 0.05 ± 0.01a 0.13 ± 0.05a 0.84 ± 0.08ab 4.49 ± 0.91a 261 ± 45.2ab 2.38 ± 0.42ab 1.79±0.24a 1.34 ± 0.30ab 23.9 ± 3.04a
Cobalt levels were ranged from <0.01 mg kg 1 in S. canicula to (0.73–1.91 mg kg 1) and Türkmen and Ciminli (2007) reported
0.45 mg kg 1 in P .incisus from AB for muscles, and from lower cobalt levels for fish from Mediterranean Sea region
0.10 mg kg 1 in S. japonicus to 0.96 mg kg 1 in P .incisus from AB (<0.001–0.002 mg kg 1 for muscles and livers).
for livers. In the literature, cobalt levels have been reported as Chromium levels in analysed fish ranged from 0.07 mg kg 1 in T
<0.05–0.40 mg kg 1 for muscles of fish from Black Sea coasts (Top- .lyra from NAS to 1.48 mg kg 1 in P. incisus from AB for muscles,
cuoğlu et al., 2002), 0.02–0.67 mg kg 1 for muscles of fish from and from 0.34 mg kg 1 in S. japonicus from NAS to 3.97 mg kg 1
Indian fish markets (Sivaperumal, Sankar, & Nair, 2007), 0.04– in P. acarne from CAS for livers. In the literature, chromium levels
0.41 mg kg 1 for muscles and 0.14–0.51 mg kg 1 for muscles of in fish have been reported in the range of 0.06–0.84 mg kg 1 for
fish from Marmara, Aegean and Mediterranean seas (Türkmen et muscles of fish from the Black Sea coasts (Topcuoğlu et al.,
al., 2008). Our findings were in agreement these literatures. On 2002), 0.10–1.60 mg kg 1 for muscles and 0.20–3.88 mg kg 1 for
the other hand, Türkmen, Türkmen, Tepe, and Akyurt (2005) re- livers of fish from Turkish seas (Tepe et al., 2007), 0.04–
_
ported higher cobalt levels for fish muscles from Iskenderun Bay 1.75 mg kg 1 for muscles and 0.19–2.63 mg kg 1 for livers of fish
236 M. Türkmen et al. / Food Chemistry 113 (2009) 233–237
9534 (1362)
& Lee, 2001), 0.2–1.87 mg kg 1 for muscles of fish from Indian fish
3528 (504)
75.6 (10.8)
221 (31.6)
871 (124)
11.2 (1.6)
67.2 (9.6)
35 (1.75)
140 (20)
markets (Sivaperumal et al., 2007).
Copper concentrations ranged from 0.51 mg kg 1 in S. japonicus
from CAS to 7.05 mg kg 1 in P. acarne from NAS for muscles, and
from 1.56 mg kg 1 in S. japonicus from AB to 51.1 mg kg 1 in D. lab-
4662 (666)
1498 (214)
148 (21.2)
143 (20.4)
2007), 0.7–27 mg kg 1 for muscles and 3.1–323 mg kg 1 for livers
37.8 (5.4)
67.2 (9.6)
4.2 (0.6)
of fish from Lake Budi (Tapia et al., 2006), 0.74–2.24 mg kg 1 for
14 (2)
63 (9)
_
muscles of fish from Iskenderun Bay (Türkmen, Türkmen, Tepe,
Mazlum, & Oymael, 2006), 0.15–5.06 mg kg 1 for muscles and
8624 (1232)
1126 (161)
78.4 (11.2)
89.6 (12.8)
216 (30.9)
89.6(12.8)
23.8 (3.4)
11.2 (1.6)
14.9 mg kg 1 for livers of fish from Marmara, Aegean and Mediter-
77 (11)
ranean seas (Türkmen et al., 2008).
Iron levels ranged from 9.18 mg kg 1 in P. incisus from AB to
136 mg kg 1 in P. acarne from CAS for muscles, and from
6412 (916)
1694 (242)
59.6 and 73.4 mg kg 1 for muscles of fish from Mediterranean
96.6 (13.8)
92.4 (13.2)
556 (79.4)
438 (62.6)
207 (29.6)
54.6 (7.8)
sea (Kalay, Ay, & Canli, 1999), 68.6–163 mg kg 1 for muscles of fish
63 (9)
from Black and Aegean seas (Uluozlu et al., 2007), 30–160 mg kg 1
for muscles of fish from the Black Sea coasts (Topcuoğlu et al.,
2002), 51.4–224 mg kg 1 for livers of fish from Çamlık Lagoon
S. scriba EWI (EDI)
WHO recommends a TDI (tolerable daily intake) of 5 lg/day/kg body weight, i.e. 350 lg/day for a 70-kg person (WHO, 1993).
(Dural et al., 2006), 49.9–889 mg kg 1 for livers of fish from Turk-
13,860 (1980)
7490 (1070)
ish seas (Tepe et al., 2007), 48.1–384 mg kg 1 for livers of fish from
EPA recommends a RfD (reference dose) of 0.14 mg/day/kg body weight, i.e. 9800 lg/day for a 70-kg person (EPA, 2008).
151 (21.6)
683 (97.6)
389 (55.6)
179 (25.6)
43.4 (6.2)
51.8 (7.4)
126 (18)
Tuzla Lagoon, Mediterranean sea region (Dural et al., 2007), 105–
442 mg kg 1 for livers of fish from Marmara, Aegean and Mediter-
The estimated daily and weekly intakes for the economically important fish species consumed by adult people in Turkey
118 (16.9)
29.4 (4.2)
36.4 (5.2)
46.2 (6.6)
53.2 (7.6)
532 (76)
1172 (167)
347 (49.6)
270 (38.6)
58.8 (8.4)
2008).
Nickel levels in fish were found as 0.03 mg kg 1 in T. ovatus
EWI, estimated weekly intake in lg/week/70 kg body weight.
91.0 (13)
189 (27)
_
Iskenderun Bay (Türkmen et al., 2006), 0.02–4.22 mg kg 1 for mus-
cles and 0.40–9.70 mg kg 1 for livers of fish from coastal waters of
Turkish seas (Tepe et al., 2007), 0.02–3.97 mg kg 1 for muscles and
0.13–8.89 mg kg 1 for livers of fish from Marmara, Aegean and
35,000
56,000
70,000
9800h
PTDIc
350f
250
490,000
2450
1750
from CAS for livers. Lead levels in the literature have been reported
in the range of 0.22–0.85 mg kg 1 for muscles of fish from the mid-
PTWI*
3500a
5600a
7000a
980i
25a
7a
–
–
Metal
g
c
i
b
a
f
e
h
Cu
Cd
Co
Zn
Pb
Ni
Fe
Cr