Environmental Monitoring and Assessment (2006) 117: 271279 DOI: 10.

1007/s10661-006-0989-5

c Springer 2006

LEVELS OF SELECTED METALS IN CANNED FISH CONSUMED IN KINGDOM OF SAUDI ARABIA

WAQAR ASHRAF , ZAKI SEDDIGI, ABDALLAH ABULKIBASH and MAZEN KHALID
King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia ( author for correspondence, e-mail: waqar@kfupm.edu.sa)

(Received 29 March 2005; accepted 1 July 2005)

Abstract. In the present paper, seven heavy metals (Pb, Cd, Ni, Cu, Zn, Cr and Fe) in canned salmon, sardine and tuna sh were determined by using atomic absorption spectroscopy. Cadmium and lead levels were determined by graphite tube AAS whereas Ni, Cu, Cr and Fe were determined by ame AAS. Analytical results were validated by spiking the samples with various concentrations of these metals for recovery. The metal contents, expressed in g/g, wet weight, varied depending upon the specie studied. The levels of Pb ranged from 0.031.20 g-g1 with an average of 0.313 g-g1 for salmon; 0.030.51 g-g1 with an average of 0.233 g-g1 for tuna and 0.131.97 g-g1 with an average of 0.835 g-g1 for sardines. The levels of Cd ranged from 0.020.38 g-g1 with an average of 0.161 g-g1 for salmon; 0.070.64 g-g1 with an average of 0.227 g-g1 for tuna and 0.0100.690 g-g1 with an average of 0.183 g-g1 for sardines. Comparative evaluation of these metals in three varieties of sh showed that average concentration of lead in sardines is about 4 times and Ni about 3 times higher as compared to tuna. Generally, the levels of these metals follow the order sardine > salmon > tuna. The data generated in the present study compared well with the similar studies carried out in different parts of the world. The results indicate that canned sh, in general and tuna in particular, have concentrations within permissible limits of WHO/FAO levels for these heavy metals. Therefore, their contribution to the total body burden of these metals can be considered as negligibly small. Keywords: AAS, canned sh, heavy metals

1. Introduction There has been a growing interest in assessing the levels of trace heavy metals in food. The ingestion of food is an obvious means of exposure to metals, not only because many metals are natural components of foodstuffs but also because of environmental contamination and contamination during food processing/packaging. Concern about quality of food is increasing in several parts of the world (Francesco and Raggi, 2004; Khansari, 2004; Larson, 2002; Onianwa, 2000). Heavy metals are considered to be the most important form of aquatic pollution because of their accumulation by aquatic organisms. Metal pollution in the marine environment is not very visible but its impacts on delicate marine ecosystems and humans are drastic.

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Heavy metal burdens in sh follow a multivariate dependence pattern. Fish accumulates substantial amounts of metals in their tissues especially muscles and thus, represent a major dietary source of these metals for humans (Waqar, 2004; Kalay et al., 1999; Rose, 1999; Tariq et al., 1993). Various shes, as well as marine mammals and sea birds prey on sardines. Eating salmon is known to be a healthy way to get Omega-3 fatty acids into the diet (Steve, 1995). Trace metals are signicant either from the viewpoint of their essentiality or their toxicity (Sharif, 1993; FAO/WHO, 1972; El-Hraiki et al., 1992). Copper and zinc are known to be essential and may enter the food materials during food processing or environmental contamination. Copper is an essential constituent of metalloenzymes and is required in hemoglobin synthesis and in catalysis of metabolic reactions (Aucoin, 1999). However, copper under ionic forms Cu2+ , Cu2 OH+ and CuOH+ is toxic to sh (Moore, 1991). Zinc is present in many enzymes involved in important physiological functions like protein synthesis and constitutes about 33 ppm of adult body weight. Nickel at very trace levels, acts as an activator of some enzyme systems but its toxicity at higher levels is more prominent. It accumulates in lungs and frequently causes bronchial failure. In addition to environmental contamination sources of Ni in foods is from processing activities such as canning and cooking in Ni containing vessels. Based on EPAs oral reference dose of 20 g/kg/day, a provisional maximum tolerable daily intake of Ni of 1.2 mg/person/day can be estimated. Cadmium is widely distributed at low levels in the environment and is, from present knowledge, not an essential element for humans, animals and plants. The WHO/FAO has determined a maximum tolerable weekly intake of 7 g Cd/kg of body weight (US FDA, 1993). Toxicity symptoms induced by cadmium include gastrointestinal disorders, kidney failure and hypertension. Sources of cadmium in foods are environmental and naturally occurring elevated levels of the metal in local soil and water bodies (Enomoto, 1974). Lead is found at high concentration in muscles and organs of sh. It accumulates in the human body where it replaces calcium in bones (DHSS, 1980). Solder used in manufacture of cans has been recognized as source of Pb in canned foodstuff (Shahid, 1987). Iron is vital component of human life and the human body contains 6070 ppm of iron. Most important iron containing complexes in human body are hemoglobin and myoglobin. Chromium is widely distributed in human tissues in extremely low and variable concentrations. Chronic exposure to high Cr levels has been correlated with lung cancer in man and kidney damage in animals (Mertz, 1981). The sheries of gulf are of global as well as regional importance. They comprise an artisanal and industrial sector. Establishment of huge industrial agglomeration around the gulf coast is accompanied by release of high concentration of toxic heavy metals into the marine environment (Price, 1991). Metal contaminations in sea foods has been broadly investigated (Khansari et al., 2004; Liang et al., 1999; Voegborlo et al., 1999). The studies on the transfer of heavy metals through the food chain can provide useful information for the development of surveillance programs aimed at ensuring the safety of the food supply and minimizing human exposure.

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In the present study, we explored the levels of heavy metals Pb, Cd, Cu, Ni, Cr, Fe and Zn in commercial canned sh which is frequently consumed in Saudi Arabia. Keeping in view scarcity of data on this issue, levels of heavy metals were estimated in canned sardine, tuna and salmon sh.

2. Materials and Methods All glassware was cleaned by soaking overnight in 10% nitric acid, followed by rinsing with distilled water. The acids used for wet digestion were of high purity Ultrex (J.T. Baker) grade, while the distilled water was further deionized. The blank values were below the detection limits of the instrument. Metal standard solutions for the atomic absorption analysis were obtained from BDH. Working standards were made from the stock by dilution of the measured aliquots with 1.0 M nitric acid. Spectrophotometric analysis was carried out at most sensitive analytical lines of the metals. Each sample was analyzed in triplicate and the results, which mostly agreed within 1.0%, were averaged. A reagent blank determination was carried out with every batch of 10 samples. Cans of sh (150 g each) were procured from groceries, markets, supermarkets, hypermarkets and main food distribution networks, including most popular markets in areas with high population densities. After opening each can oil/broth was drained off and meat was homogenized thoroughly in a food blender. Samples were then digested without delay. About 5 g of sample were digested in quartz Erlenmeyer ask with 15 ml of suprapure nitric:perchloric:sulphuric acid (25 + 25 + 1 v:v:v) mixture, using a hot plate at 150 C. Further aliquots of nitric acid were added until a complete colorless solution occurred. After evaporation, the residue was dissolved in 10 ml of water with 1 ml of conc. suprapure HCl at 100 C. Finally, the volume was made up to 25 ml with water. Determination of cadmium and lead were performed on stabilized temperature graphite furnace atomic absorption spectrometer. Nickel, copper, zinc, iron and chromium were determined by direct aspiration of the sample solution into the air-acetylene ame. Validity of analytical methodology was checked by spiking the samples with various concentrations of heavy metals for the recovery. The recoveries of the metals were determined by adding increasing amounts of metals to the samples which were then subjected to the digestion procedure. The resulting solutions were analyzed for the metal concentrations. The results are reported in Table I.

3. Results and Discussion The concentrations of Pb, Cd, Ni, Zn, Cu, Cr and Fe in canned sardine, salmon and tuna sh are presented in Table II along with relevant statistical parameters. Fifteen samples for sardines, eleven for salmon and seventeen for tuna, were analyzed to

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TABLE I Recovery of various metals from canned sh samples Metal Pb Concentration added (g-g1 ) 0.20 0.60 1.00 2.00 0.10 0.30 0.50 1.00 2.00 5.00 7.00 0.20 0.60 1.00 0.15 0.30 0.40 0.20 0.40 1.00 5.00 7.50 15.0 Concentration recovered (g-g1 ) 0.18 0.62 1.04 1.96 0.09 0.32 0.52 0.97 1.81 5.52 6.84 0.22 0.58 0.98 0.16 0.32 0.38 0.17 0.38 1.06 5.33 7.78 14.2 % Recovery 90 103 104 98 90 106 104 97 90.5 110 97.7 110 96 98 106 106 95 95 95 106 106 104 94

Cd

Fe

Ni

Cu

Cr

Zn

TABLE II Metal contents (g-g1 ) along with relevant statistical parameters in various varieties of canned sh Salmon Metal Pb Cd Ni Zn Cu Cr Fe Range 0.031.20 0.020.38 0.121.70 5.3119.80 0.633.10 0.110.72 2.809.81 X 0.31 0.16 0.84 12.60 1.75 0.42 6.31 SD 0.11 0.10 0.51 4.65 0.74 0.21 2.38 Range 0.030.51 0.070.64 0.130.81 3.8017.70 0.131.87 0.070.33 1.115.32 Tuna X 0.23 0.22 0.41 10.38 1.02 0.18 2.94 SD 0.24 0.18 0.24 4.68 0.49 0.08 1.37 Range 0.131.97 0.010.69 0.792.13 8.9223.90 0.634.25 0.020.89 2.4212.31 Sardine X 0.84 0.18 1.33 16.15 2.26 0.31 6.80 SD 0.46 0.19 0.43 4.64 1.13 0.24 3.12

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Figure 1. Comparative levels of selected heavy metals in canned sardine, salmon and tuna sh.

assess amounts of these metals. Good recoveries of spiked samples show accuracy of analytical methodology. For sardines (Table II) results indicate that concentrations varied from 0.13 to 1.97 g-g1 with a mean of 0.84 g-g1 for Pb; from 0.01 to 0.69 g-g1 with a mean of 0.18 g-g1 for Cd; from 0.79 to 2.13 g-g1 with a mean of 1.33 gg1 for Ni; from 8.92 to 23.90 g-g1 with a mean of 16.15 g-g1 for Zn; from 0.63 to 4.25 g-g1 with a mean of 2.26 g-g1 for Cu; from 0.02 to 0.89 g-g1 with a mean of 0.31 g-g1 for Cr and from 2.42 to 12.31 g-g1 with a mean of 6.80 g g1 for Fe. Statistical analyses of data by ANOVA showed no signicant differences among all samples. Table II also summarizes levels of heavy metals in canned tuna samples. The results indicate that concentrations of Pb varied from 0.03 to 0.51 g-g1 with an average of 0.23 g-g1 . These levels are lower in magnitude compared to both sardines and salmon. Figure 1 shows the comparative levels of Pb, Cd, Ni and Cr in three varieties of canned sh. It is clear that average concentrations of Pb in sardines is about 4 times higher as compared to tuna. Similarly, levels of Ni are about 3 times higher in sardines as compared to tuna. Similar trend is shown by Cr as well. Average Ni contents in salmon are much lower than in sardines, 0.84 g-g1 as against 1.33 g-g1 . Similar behavior is shown by Zn and Cu. Figure 2 shows comparative levels of Zn, Cu and Fe in sardine, salmon and tuna. It is shown that levels of these metals decrease in the order of sardines>salmon>tuna. A similar study of the cadmium and lead contents in Spanish canned sh showed that sardines and anchovies had the highest levels of Pb (0.132.15 mg/kg) and Cd (0.020.28 mg/kg) (Rafael, 1975). A recent interesting report tells about high levels of toxic metals in farmraised salmon compared to their wild counterparts (News Target, 2005). In a study carried out in US (Dudek, 1989), the levels of Fe and Zn in canned salmon were found to be 6.0 0.9 g-g1 and 11.0 5.8 g-g1 , respectively. They have also reported that Zn and Fe were contributed by the enamel of

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Figure 2. Comparative levels of selected essential metals in canned sardine, salmon and tuna sh.

the cans in which salmon was processed. These values are comparable to our work with levels of Fe and Zn at 6.31 2.38 g-g1 and 12.60 4.65 g-g1 , respectively. The studies carried out in Malaysia showed Pb and Cd in canned sh ranged from 0.400.76 g-g1 and 0.070.14 g-g1 , respectively (Zahari et al., 1987). On the other hand, in Libya, Pb and Cd concentration in canned tuna were found to be 0.28 g-g1 and 0.18 g-g1 (Voegborlo et al., 1999). Our results ranged from 0.030.51 g-g1 for Pb and 0.070.64 g-g1 for Cd, in canned tuna. Cadmium levels lie within safe limits of WHO/FAO (>0.25 ppm) for most samples (FAO/WHO, 1972). Out of total 43 samples analyzed only 5 showed slightly elevated levels of cadmium (>0.25 ppm). Woidich et al., have reported a concentration range of Cd in tuna as 0.050.97 g-g1 ; whereas Muller et al. have reported quite higher levels of Cd in sh, 1040 ppm (Woidich, 1974; Muller, 1973). Levels of Pb and Cd determined in canned sardines from Costa Rica, were 0.130.21 and 0.060.16 mg/kg; whereas in canned tuna the levels of Pb and Cd were 0.290.72 and 0.140.29 mg/kg (Olga Marta et al., 1991). Sardines feed on zooplanktons and phytoplanktons by ller feeding and selective capture of large prey. Their life span is normally 12 to 13 years but some are thought to live 20 to 25 years (Baumgartner, 1992). Moreover, levels of heavy metals in sh depend upon many factors like age, sex, weight, season, place, etc (Kagi and Schaffer, 1998). The concentrations of Pb in our samples agree well with the values reported by other workers (CIFA, 1992). Keeping in view the toxicity of Pb and Cd, the Joint Food and Agriculture Organization/World Health Organization (FAO/WHO) expert committee on food additives have suggested a tolerable intake of 400500 g Cd per week for man; for Pb a weekly intake of 3 mg can be tolerated (FAO/WHO, 1972). The maximum concentration of Pb which is permitted in prepared foods for babies and children is 200 g/kg. Levels of Ni in canned sh from Denmark and Nigeria were 0.20 g/kg and 3.11 g/kg, respectively. Our values compared well with those from Denmark but were signicantly lower than reported from Nigeria. Similar behavior was shown by Zn and Cu (Table III). Levels of Fe showed a wide variation world over, ranging

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TABLE III Comparison of present average values in canned sh with international data Metal Pb Present work range (g-g1 ) 0.230.84 Literature values with relevant location/references (g-g1 ) 0.28 Libya (Voegborlo, 1999), 1.01, 0.40.76 Malaysia (Shahid, 1987) (Zahari, 1987), 0.037 Iran (Khansari, 2004), 0.90 Denmark (Larson, 2002), 1.73 Pakistan (Tariq, 1993), 0.81 Canada (Dick, 1950), 0.0160.049 US (FDA, 2000), 0.130.21 Spain (Olga Marta, 1991) 0.18 Libya (Voegborlo, 1999), 0.022 Iran (Khansari, 2004), 0.28 Denmark (Larson, 2002), 1.03 Pakistan (Tariq, 1993), 0.25 Nigeria (Onianwa, 2000), 0.070.14 Malaysia (Zahari, 1987), (0.0060.088) US (FDA, 2000), (0.060.16) Spain (Olga Marta, 1991) 0.20 Denmark (Larson, 2002), 1.33 Pakistan (Tariq, 1993), 3.11 Nigeria (Onianwa, 2000) 11.0 US (Dudek, 1989), 2.10 Pakistan (Tariq, 1993), 19.9 Nigeria (Onianwa, 2001) 1.10 Pakistan (Tariq, 1993), 2.46 Canada (Dick, 1950), 2.25 Nigeria (Onianwa, 2001) 0.102 Pakistan (Tariq, 1993), 1.14 0.73 US (Aucoin, 1999) 6.0 US (Dudek, 1989), 2.95 Pakistan (Tariq, 1993), 64.1 Canada (Dick, 1950)

Cd

0.160.22

Ni Zn Cu Cr Fe

0.411.33 10.3816.15 1.022.26 0.180.31 2.946.80

from 2.95 to 64.1 g-g1 . Our results also lie within the limits laid down by United States Environmental Protection Agency (US EPA) in sh, i.e., for Cr (8.0 g-g1 ), Cu (120 g-g1 ), Pb (4.0 g-g1 ) and Zn (480 g-g1 ) (Aucoin et al., 1999). Despite the fact that our sh samples does not signicantly contribute to total body burden of Pb, Cd, Ni and Cr, the monitoring of their levels in food is important because various species of sh retain substantial amounts of heavy metals during their life span. Due emphasis need to be given to the study of metal distribution on a temporal basis, so that contributions of man made and natural effects may be assessed. Acknowledgements The authors are grateful to Manager, Central Analytical Labs., KFUPM for his valuable support and guidance throughout this work. Thanks are also due to Mr. Izzat W. Qazi for his help and provision of facility for interlaboratory comparison of data. References
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