A Study of Heavy Metals Pollution in Some Aquatic Organisms... Suez Canal in Port- Said Harbour
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A Study of Heavy Metals Pollution in Some Aquatic Organisms... Suez Canal in Port- Said Harbour
Journal of Applied Sciences Research, 2(10): 657-663, 2006 © 2006, INSInet Publication A Study of Heavy Metals Pollution in Some Aquatic Organisms in Suez Canal in Port- Said Harbour Zienab I. Soliman Agriculture Research Center, Animal Health Research Institute, Dokki, Cairo, Egypt-Port Said Lab.of Food Hygiene. Abstract: The northern Harbor of Port Said at inlet of Suez Canal in the Mediterranean Sea, with its dense ship traffic receives several types of hazardous chemical pollutants affecting dramatically its water. The aims of this study was to determine the current levels of total mercury, cadmium and zinc in edible muscles tissues of different marine organisms caught in Suez Canal to ascertain whether these concentrations exceeded the prescribed legal limits and to identify any potential public health risks that could be associated with dietary intakesof seafood from Suez Canal. Three groupsof aquatic organisms,including fish: mullet (Mugil cephalus) and sardine (Sardine pilshardus), crustacea: crab (Calinictus sapidus) and shrimps (Metapenaeus nonoceras) and Molluscan cephalopods: cuttlefish (Sepia spp.) and squid (Loligo spp.) were analyzed for their content of total mercury, cadmium and zinc. The total mercury concentrations in the edible muscles tissues of fish species were ranged from 0.18 to 1.17 ppm (wet weight) while levels of 0.01 - 0.54 and 0.01 - 0.92 ppm (wet weight) were recorded in edible muscles tissues of crustacean and cephalopods species, respectively. Concentrations exceededthe prescribed legal limitsof Egyptian Organization Standardization and Quality Control (E.O.S.Q.C) and that stipulated by the European Commission (0.5 mg /kg [wet weight]) were observed in 32.50% of fish samples, 2.50% of crustaceans samples and 22.50% of cephalopods samples. Mercury was the only element showing a significant correlation with the size of the specimens’ .The highest mean levels of cadmium were recorded in crab (0.938±0.097, ppm, wet weight) and squid (0.897±0.278,ppm wet weight) in particular and to a lesser extent in cuttlefish and shrimp. No fish samples showed cadmium concentration exceeding the peak permitted values of 0.1 ppm wet wt stipulated by E.O.S.Q. All samples in this study contained zinc within of the general guideline limit for zinc in food of 50 mg/kg. The results were evaluated according to International standards of WHO and FDA. Provisional tolerable weekly intakes or other internationally accepted standards would also be used in this study to assess the relative safety of the Suez Canal fish supply. Key words: INTRODUCTION levels of metals is a concern because chronic exposure to heavy metals can cause health problems. Chronic cadmium exposure has been linked to renal failure, bone fragility and as a cancer–causing agent in humans[1,2,3,4]. Although zinc is an essential nutrient required for proper growth and development, too little zinc can cause problems, but too much zinc is also harmful to human health[5]. Mercury (Hg) is one of the most important pollutants both because of its effect on marine organisms andit is potentially hazardous to humans. Methylmercury, which is formed in aquatic sediments through the bacterial methylation of organic mercury, is toxic chemicals compound of mercury, in fact, nearly all of the mercury in fish muscles occurs as Methylmercury[6]. Methylmercury affects the kidneys and also the central nervous system, particularly during development, as it crosses both the blood –brain barrier and placenta[7]. Suez Canal is artificial waterway of Egypt connecting the Mediterranean Sea with the Gulf of Suez, an arm of the Red Sea, and extending from Port Said to Suez provinces. It is actually, the lonely canal linked between the Mediterranean Sea and the Red Sea. The canal provides a shortcut for ships operating between both European and American ports and ports located in southern Asia, eastern Africa, and Oceania . The northern part of the Suez Canal at Port Said acts as fishing harbor .Fishing is a field of considerable activity and seafood is consumed by a large segment of the population in Port Said. Fish is a commodity of potential public health concern as it can be contaminated with a range of environmentally persistent chemicals, including heavy metals. The consumption of fish containing elevated Corresponding Author: Zienab I. Soliman, Agriculture research center-Animal Health Research Institute, Dokki, Cairo, Egypt-Port Said Lab.of Food Hygiene. E. Mail: [email protected] 657 J. Appli. Sci. Res., 2(10): 657-663, 2006 In light of this concern and the pollution that is the Suez Canal facing, questions have been raised about the safety of eating fish and seafood from the Suez Canal waters. Therefore, the present study was carried out to measures the concentrations of heavy metals (mercury, cadmium and zinc,) in common edible marine tissues of different aquatic species caught in Suez Canal in order to assess the seafood consumption safety. The relationships between size (weight) and metal concentrations in the tissues were investigated. The results were evaluated according to International standards of WHO and FDA to identify any potential public health risks and identify if preventive public health strategies relating to dietary exposure from metal contaminants in seafood are required. Provisional tolerable weekly intakes or other internationally accepted standards would also be used in this study to assess the relative safety of the Suez Canal fish supply. Digestion of samples was carried out according to the methods described by Al-Ghais[8]. Concentrations of cadmium (Cd), zinc (Zn) and Mercury (Hg) were measured with atomic absorption spectrophotometery. The obtained data were statistically analyzed for assessment of variation in metal concentrations among small and large size individuals within each species .The descriptive statistics (mean, maximum, minimum and standard error) were recorded. Weekly intake recommended by the joint Food and Agriculture Organization/World Health Organization were included and discussed in light of present findings. RESULTS AND DISCUSSIONS As shown in Table 2, the total mercury concentrationsin the edible musclestissues offish species were ranged from 0.18 to 1.17 ppm (wet weight) while levels of 0.01 to 0.54 ppm (wet weight) and 0.01 to 0.92 ppm (wet weight) were recorded in edible musclestissues of crustacean and cephalopods species, respectively. Limits of total mercury level have been established in various countries. The FDA has set a maximum total mercury level of 1mg/kg (wet weight) in fish[9]. In Japan, fish containing total mercury concentrations exceeding the Japanese maximum permitted limit of 0.3 mg/kg (wet weight) are considered unsuitable for human consumption[10]. In Europe, the total mercury limit, regulated by European Commission, is 0.5 mg/kg (wet weight), except for some species for which it is 1.0 mg[11]. In Egypt, the total mercury limit, regulated by Egyptian Organization Standardization and Quality Control[12] is 0.5 ppm (wet weight) of fish. On this basis, 32.5% of fish samples, 2.5% of crustaceans samples and 22.5 % of cephalopods samp les had mercury concentrations exceeded the prescribed legal limits of E.O.S.Q.C. and that stipulated by the European Commission (0.5 mg /kg [wet weight]). Total mercury concentrations above the regulatory limits have been observed for certain species occupying high trophic positions[13] and in species that live on or close to sea bed[14]. The high concentration of total mercury recorded in some of examined samples may be attributed to high sources of activities such as loading and unloading operation at Port Said harbor and industrial effluents and MATERIALS AND METHODS Samples of Marine i.e. fish, crustaceans and cephalopods, representing 6 species; consisting commonly consumed species were assembled from the site of harvesting at fishing harbor of the Suez Canal at Port Said. Species targeted for collection and analysis were, fish: mullet (Mugil cephalus) and Sardines (Sardina pilchardus), crustacea: crab (Calinictus sapidus) and shrimps (Metapenaeus nonoceras), and Molluscan cephalopods: cuttlefish (Sepia spp.) and squid (Loligo spp.). The analyses were carried out on 40 individual from each species. An attempt was made to collect consistent size ranges within species. For each species,two subdivisions within which individual samples were collected as a function of their similar size were formed from total number of specimens. Laboratory Analysis: Samples collections were delivered to Laboratory where they were sorted by species, and size. Samples were then sorted into 12 groups, each consisting of 20 individuals. Samples weightranges were recorded in Table (1). Muscles tissues were removed from each group and preserved at –180C until the analysis was carried out. Table 1: Weight ranges (gm) of seafood samples Weight ranges (gm) ----------------------------------------------------Seafood samples Small Large Mullet 100- 120 450-550 Sardine 50-60 80-100 Shrimp 9-12 40-50 Crab 100-120 225-250 Cuttlefish 130-142 330-345 Squid 90-100 120-135 Table 2: Overall percentage of total mercury in seafood samples by groups (n480) Total mercury (ppm) Species -----------------------------Samples exceed group Max Min 0.5ppm: No (%) fish 0.18 1.17 26 (32.50) crustacea 0.01 0.54 2(2.50) cephalopods 0.01 0.92 18(22.50) 658 J. Appli. Sci. Res., 2(10): 657-663, 2006 Table 3: Total mercury concentrations (ppm (wet weight)) with respect to weight for different marine samples (n4 20) Small Large Statistical --------------------------------------------------------------------------------------------------------------------Seafood groups Min Max Mean ±se Min Max Mean ±se Fish Mullet 0.18 0.53 0.334±0.102 0.35 1.17 0.881±0.229 ----------------------------------------------------------------------------------------------------------------------------------------------------------------Sardine 0.20 0.52 0.287±0.910 0.23 0.97 0.568±0.184 ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Crustacean Shrimp 0.01 0.09 0.042±0.230 0.06 0.54 0.256±0.151 ----------------------------------------------------------------------------------------------------------------------------------------------------------------Crab 0.01 0.05 0.028±0.140 0.03 0.25 0.067±0.470 ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Cephalopods Cuttlefish 0.02 0.54 0.036±0.36 0.06 0.72 0.488±0.043 ----------------------------------------------------------------------------------------------------------------------------------------------------------------Squid 0.01 0.51 0.126±0.321 0.02 0.92 0.418±0.321 significant correlation between size of samples and mercury concentrations at p<0.05 and p<0.01 Table 4: Estimated weekly seafood consumptions in a 70 Kg man based on mean and maximum level of mercury found in seafood samples, sufficient to reach the Hg Provisional Tolerable Weekly Intake (PTWI): 5 μg.Kg-1. Estimated weekly seafood intake (kg) ----------------------------------------------------------------Small Large ------------------------------------------------Seafood samples Mean Max Mean Max Mullet 1.05 0.660 0.397 0.299 Sardine 1.22 0.673 0.616 0.361 Shrimp 8.33 3.89 1.37 0.648 Crab 12.5 7 5.22 1.40 Cuttlefish 9.724 0.648 0.717 0.486 Squid 2.78 0.686 0.837 0.380 The joint FAO/WHO Expert Committee on Food Additive has established a provisional tolerable weekly intake (PTWI) of 300 µg of total mercury (for 60 kg person) of which no more than 200 µg should be present as methylmercury[4]. These amount equivalents to 5 µg of total mercury, per kg body weight and 3.3 methylmercury per kg body weight. However, people in different geographical area have different dietary pattern, particularly with regard to seafood consumption. No available data couldbe obtained for consumptions pattern of seafood in Port Said. Therefore, the exposure of the consumer of seafood to mercury has been assessed based on the mean and highest mercury concentration found in these species, which have been compared with Hg PTWI of 5 µg/kg, Table (4). For adult (70 kg body weight), the weakly consumptions of 299-397 gm of large size mullet, or 361- 616 g of large size sardine or 380- 837 gm of large size squid are sufficient to reach the PTWI (5 µg/kg body weight) that may results in a risky daily intake of mercuryif exposure is long term. However, to exceed the PTWI would require consumption of 660 up to 1000 gm or more of small size fish or 686- 2780 gm of small size squid ,according to its mercuryconcentration so there was an adequate margin of safety in consuming small size fish and other seafood samples. On the other hand, all crustaceans’ samples had a mean mercury levels falling within range of 0.01-0.54 ppm (mg/kg). The dietary exposure to mercury would not exceed the PTWI at level up to 648 g for large size shrimp with concentrations of 0.54 ppm. Meanwhile, the risk is greater for women who are pregnant or likely to become pregnant within the followingyear because the effect of methylmercury on the developingnervous system of the fetus[7]. The exceedance of the PTWI is relatively greater for children as their food intake is greater, on a bodyweight basis than that of adult. Mercury has periodically raised concern. Fish consumption is the only significant source of methyl mercury in the public [20]. The earliest clinical signs and symptoms of methylmercury poisoning are diffuse paresthesias in the hands, in feet, and around the mouth. Increased exposure may result in ataxia, constriction of domestic drainage of Port Said city. Moreover, mercury is being used as antifouling agent in marine paints. Thus, ships waiting could add heavy contamination source at Port Said. In this respect, El- Moselhy et al. [15] studied the distribution of mercury in water along the Suez Canal they reported that the worst affected regions in the Suez Canal are Port Said (Hg, 42.77 ng/l). Table (3) provides summary of the mean total mercury concentration found in edible muscle tissues of selected samples with respect to size (weight). Among the examined samples, the highest total mercuryconcentrations were recorded in fish sampleswhile the lowestvalues were found in shrimp and crab. The variation in total mercury concentration among different species could be explained by there different migratory and feeding habits as well as different metabolic and excretion rates, furthermore they hold different position in the marine food. Other author[16,17] reportedsimilar observations.Moreover, the total mercury content of the examined samples increase with increasing size of the specimen, Levels up to 1.17 ppm have been found in large mullet in some samples, which is considerably above the maximum permissible level (0.5 ppm) for edible tissues of fish. Similar finding have shown by other authors for other marine organism (18,19). Older (larger) fish within a species may be more contaminated because they have had more time to ac cu mu la te co nt am in an ts in th ei r bo di es . (Biomagnifications of mercury through the food chain). 659 J. Appli. Sci. Res., 2(10): 657-663, 2006 Table 5: Cadmium concentrations (ppm) wet weight with respect to weight ranges for different marine samples (n4 20). Small Large Statistical ---------------------------------------------------------------------------------------------------------------------Seafood groups Min Max Mean ±se Min Max Mean ±se Fish Mullet 0.01 0.03 0.023±0.010 0.01 0.04 0.030±0.010 ---------------------------------------------------------------------------------------------------------------------------------------------------------------Sardine 0.02 0.04 0.028±0.012 0.03 0.05 0.031±0.014 ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Crustacean Shrimp 0.39 1.51 0.727±0.286 0.43 1.53 0.860±0.308 ---------------------------------------------------------------------------------------------------------------------------------------------------------------Crab 0.31 1.46 0.844±0.289 0.48 1.53 0.938±0.097 ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Cephalopods Cuttlefish 0.27 1.12 0.769±0.256 0.38 1.19 0.865±0.264 ---------------------------------------------------------------------------------------------------------------------------------------------------------------Squid 0.49 1.05 0.755±0.202 0.48 1.17 0.897±0.278 Non significant correlation between size of samples and cadmium concentration. Table 6: Estimated weekly seafood consumption in a 70 Kg man, based on mean and maximum level of cadmium found in seafood samples sufficient to reach the Cd Provisional Tolerable Weekly Intake (PTWI): 7 μg.Kg-1. Estimated weekly seafood intake (kg) ---------------------------------------------------------------Small Large --------------------------------------------------Seafood samples Mean Max Mean Max Mullet 21.30 16.34 16.34 12.25 Sardine 17.50 12.25 15.81 9.80 Shrimp 0.674 0.325 0.570 0.320 Crab 0.522 0.336 0.581 0.320 Cuttlefish 0.637 0.438 0.566 0.412 Squid 0.650 0.467 0.546 0.419 all crustacean and molluscan cephalopods samples analyzed were below that recommended by several agencies and organizations. Crustacean mainly live and feed on sea bottom where deposit accumulate due to runoff from shore. In this respect, Overnell, [26] reported that cadmium levels in edible crab(Cancer pagurus) may be as high as 30–50 ppm. Moreover, Juresa and Blanusa[27] reported that cadmium level were almost 10 times higher in shellfish than in finfish. . The World Health Organization/Food and Agricultural Organization[28] has established a provisional tolerable weekly intake (PTWI) of 490 µg of cadmium for 70 kg person. This amount equivalent to 7 μg Cd per kg body weight/ week. The exposure of the consumer of crustacean and cuttlefish to cadmium has been assessed by the Cd concentrations found in these species, which have been compared with Cd PTWI of 7 µg/kg, Table (6). The weakly consumption of 320-674 gm of shrimp,or 320- 581 g crab, or 412-637 g of cuttlefish may sufficient to reach the PTWI. The data provided in this study not taking other sources of dietary cadmium into account. However apparent exposure may not reflect a consistent weakly intake of this magnitude, as individuals whoconsume crustacean and cephalopods consume them sporadically. On the contrary, the exposure of the consumer of fish to cadmium was low for all fish samples and not considered to be of concern. However, because the bodyhas no mechanism for the excretion of cadmium, cadmiumaccumulatesin tissues; the half-lifeof cadmium in kidney cortex is 10–30 years[29]. Chronic exposure to low-level Cd has been associated with a number of pathologies, such as end-stage renal failure, early onset of diabetic renal complications, osteoporosis, deranged blood pressure regulation, and increased cancer risk[30,31,32]. With regarding to zinc, the present results in Table (7) pointed out that all samples in this studycontained zinc within of the general guideline limit for zinc in food of 50 mg/kg (ppm)[33]. higher concentrations of zinc were seen in cephalopods and crustacean than in the visual field, blurred speech and hearing difficulties. With severe poisoning, patients may develop blindness and general physical and mental debilitation [21]. The lowest mercury levels associated with the onset of clinical sign in adults were reported to be 50 µg/g in hair and 200 µg/L in whole blood this level corresponds to a long-term daily intake of 3 to 7 µg kg of body in form of methylmercury[22]. Level of cadmium in edible tissues of fish and other marine organisms’ samples were recorded in Table (5). The highest mean levels of cadmium were recorded in crab (0.938±0.097, ppm, wet weight) and squid (0.897±0.278, ppm wet weight) in particular and to a lesser extent in shrimp (0.860±0.308, ppm wet weight). Concentrationof cadmium in tissues of mullet and sardine samples were found to be safe for human consumption, there was no fish samples showed cadmiumconcentration exceeding permissible limits stipulated by the European communities[23] of 0.05mg Cd/kg. However, the peak permittedvalues stipulated by E.O.S.Q (12) is 0.1 ppm cd wet weight. The European Community has setting maximum limits (MLs) for Cd in bivalve mollusks at 1 mg/kg wet weight (1 ppm), and Australia, New Zealand, and Hong Kong have a setting (MLs) for Cd in mollusks of 2 ppm[24]. The FDA action level for cadmium in crustacean seafood is 3 ppm and 4 ppm for Molluscan Shellfish[25]. On this basis, the concentrations cadmium in 660 J. Appli. Sci. Res., 2(10): 657-663, 2006 Table 7: Zinc concentrations (ppm) wet weight with respect to weight ranges for different marine samples (n4 20). Small Large Statistical -------------------------------------------------------------------------------------------------------------------Seafood groups Min Max Mean ±se Min Max Mean ±se Fish Mullet 6.45 8.15 7.934±0.763 6.39 9.15 8.397±0.819 ---------------------------------------------------------------------------------------------------------------------------------------------------------------Sardine 6.15 10.30 8.526±0.932 8.15 10.37 8.932±0.614 ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Crustacean Shrimp 12.17 17.05 15.984±1.617 12.80 19.20 17.360±1.052 ---------------------------------------------------------------------------------------------------------------------------------------------------------------Crab 28.48 30.53 29.912±1.617 30.00 33.45 31.012±1.805 ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Cephalopods Cuttlefish 31.35 42.87 36.301±9.172 32.10 45.01 40.237±7.820 ---------------------------------------------------------------------------------------------------------------------------------------------------------------Squid 36.87 43.00 40.451±2.207 37.15 45.17 41.740±2.773 Non significant correlation between size of samples and zinc concentration. Table 8: Estimated daily seafood consumption in a 70 Kg man, based on mean and maximum level of zinc found in seafood samples sufficient to reach the zn Provisional Maximum Tolerable Daily Intakes (PMTDIs): 70 mg/day Estimated daily seafood intake (kg) ---------------------------------------------------------------Small Large -------------------------------------------------Seafood samples Mean Max Mean Max Mullet 8.82 8.59 8.34 7.65 Sardine 8.21 6.80 7.84 6.75 Shrimp 4.38 4.11 4.03 3.65 Crab 2.34 2.29 2.26 2.09 Cuttlefish 1.93 1.63 1.74 1.56 Squid 1.73 1.63 1.68 1.55 Harmful effects generally begin at levels 10-15 times higher than the amount needed for good health. Large doses taken by mouth even for a short time can cause stomach cramps, nausea, and vomiting. Taken longer, it can cause anemia and decrease the levels of good cholesterol[39]. In conclusion, analytical data obtained from this study shows that, in general, total mercury contaminants were higher in fish than crustacean and cephalopods meanwhile, tissues zinc and cadmium showed the opposite. The groups at risk from mercury or other metal poisoning are mostly pregnant women, very young children, and those with weakened immune systems. Moreover, People who eat large quantities of seafood, such as professional fishers and their families should be concerned. However, in general, people should choose smaller fish or other seafood consistent; within a species since theymay have lower contaminant levels also people should eat a diversity of seafood to avoid consuming unhealthy quantities of heavy metals. There is a need to establish the necessary guidelines to the community especially to high-risk groups such as pregnant women and children. fish with values for individual species in general in agreement with literature values[34]. Therefore, the zinc concentrations found in the present study are not of concern. The Joint FAO/WHO Expert Committee on Food Additives[35] established a provisional tolerable weekly intake (PTWI) for zinc of 7000 µg/week / kg .The ProvisionalMaximum Tolerable Daily Intakes (PMTDIs) set by the Joint Expert Committee on Food Additives of the Food and Agriculture Organization of the United Nations and the World Health Organization (JECFA)[36] for zinc is 1.0 mg/kg bodyweight/day (equivalent to 70 mg/day for a 70 kg adult), The dietary intakes of seafood estimated from the present studies to exceed the PMTDIs would require consumption of about 1550 gm or more / day of large size squid (with level of 45.17 ppm wet weight) , below these dietary intakes of any tested seafood samples not represent any known risk to health. Zinc is an essential trace element in our diet that is required for the synthesis of DNA, RNA, and proteinand thus for cell division[37]. 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