**2. Materials and methods**

298 International Perspectives on Global Environmental Change

part of Suez Canal from the east and northern side of Manzala Lake from the south. It is considered as the most important vital area along the Mediterranean Sea. Many of the Egyptian coastal zones are subjected to variable significant environmental hazards including, loss of ecosystem quality, coastal erosion, seismic risk and over-exploitation. Moreover, it comprises a lot of land-use changes and modifications to development of future mitigation strategies. High profile example is the region of the eastern Nile Delta coastal ecosystem. It is one of the most beautiful recreation centers along coastal area of the Mediterranean Sea. In addition, it has several natural gas companies, recreational areas and fishing activities. A number of factors acting together on this zone has contributed to environmental and coastline changes. Natural processes and anthropogenic activities have to be considered as the most effective factors at the area of study. The pollution problems in the study sites are chiefly due to high quantity of domestic sewage and the virtually total absence of control on toxic components. Mistakes in their management can have

Contamination by trace metals has not been extensively studied in the Egyptian coastal zones along the Mediterranean Sea which are subjected to intense discharges of pollutants. Therefore, it is important that sediment and water contamination by these pollutants be assessed for better management and protection of these valuable costal ecosystems at El-Gamil beach along the western coast of Port Said on the Mediterranean Sea. Especially, this study area represents a pronounced area for fishing, industrial development, urban

catastrophic consequences for ecosystem integrity and human development.

extensions and more tourism activities along eastern Mediterranean Sea.

Fig. 1. Satellite image shows the location of the study area and the sampling sites

### **2.1 Sampling sites and measurements**

The study area constitutes a small part of the low lands laying west of Port Said City vise El Gamil zone, extending west wards parallel to the Deltaic Coast-Mediterranean Sea. It is boarded by the Suez Canal from the east and by Lake Manzala from the south. It is situated at nearly about 13 kilometers west of Port-Said City and extending between Latitude 31°:10' - 31°:20' N and Longitude 32°:00' - 32°:20' E with about 24 km2 coverage area. Five sites along the El- Gamil beach, including El Gamil airport (Site 1), El Gamil inlet (site 2), El Fardous (Site 3), El Manasra (Site 4) and El Debba (Site 5) were chosen for this study (Fig.1). General features of anthropogenic activities at the study area with emphasis on descriptive features of sampling sites are listed in table (1). Heavy metals (Fe, Mn, Cd, Zn, Cu and Pb) levels were measured in bottom sediment, surface water and bivalve samples collected from each site during December 2005 and August 2006.


Table 1. Locations and descriptive features of sampling sites.

Heavy Metals Contamination of a Mediterranean Coastal Ecosystem, Eastern Nile Delta, Egypt 301

The sediment at the five selected sites showed a highest percentage of very fine and fine sand coupled with low percentage of coarse fraction (Table 2). The maximum percentage of organic matter content was recorded at both sites of El-Gamil inlet and El Fardous with values of 4.13 ± 1.3 % and 4.23 ± 1.77 %, respectively. The high percentage of organic matter in the two mentioned sites can be attributed to the discharge of sewage wastes into the Mediterranean Sea through El Gamil outlet and Ashtoum El Gamil outlet along El Manzala Lake. Furthermore, the untreated domestic sewage discharged into the sea from four touristic villages in this coastal area *vise*: El Gamil, El Abtal, El Maghraby and El Fardous. The calcium carbonate content was very high at El Gamil airport with value of 27. 53 ± 5.10 %, while it was very low (3.03 ± 1.18%) at El Debba. The high values of calcium carbonate content at site (1) can be attributed to the accumulation of tremendous amounts of shell

In the sediment samples, the concentration of heavy metals was higher during winter (Table 3). Even though there was variability among sites, the overall concentration range for a particular metal was relatively narrow, with no values that appeared to be unusual. Generally, in the sediment samples the heavy metals distribution followed the decreasing order of Fe> Mn> Zn> Pb**>** Cu> Cd. Moreover, El Manasra site suistained the heighest values of heavy metal contaminations recorded during the present study. This can be explained by the increasing industrial activities at this site. So, these high contaminants were associated with natural gas companies, pipeline industries and an electric power generating

Table 2. The physical and chemical properties of sediment during summer 2006

fragments blanketing the bottom sediment at El Gamil airport.

station operating at this area.

#### **2.2 Bottom sediment, surface water and bivalve analysis**

A total of 30 sediment samples were collected from the five selected sites along El-Gamil coast during December 2005 and August 2006. The sediment samples were collected by pushing a plastic core (12 cm in diameter) into the bottom sediment to a depth of approximately 5 cm, then put in plastic bags and transferred to the laboratory. Sediments were dried at 100 C° for 24hrs and kept in plastic bags until analysis. A representative 50 gm of sediment sample were repeatedly treated with hydrogen peroxide (30%) for removal of organic matter and loss in weight was determined and the organic matter free samples were treated by using dilute HCl to remove calcium carbonates and loss in weight was determined according to method described by Folk, 1974. The grain size analysis of the examined samples was done according to Friedman and Johnson 1982. Dry sand was fractioned by dry sieving using sieves with openings of 2, 1, 0.5, 0.25, 0.125, 0.063 and 0.032 mm and an electric shaker. The weight percentages of the different size classes were calculated in three replicates per site sampled.

To detect the heavy metal contamination in the sediment samples, an exact weight of dry sample (0.5 gm) of each sediment sample was completely digested for about 2hrs in Teflon vessels using a mixture of HNO3, HCLO4 and HF (3:2:1 v/v 10 ml) (triplicate digestions were made for each sample). The final solution was diluted to 25 ml with distilled deionized water (Oregioni and Astone, 1984).

A total of 30 surface water samples were collected at a depth of 0.5 m from the five selected sites along the El-Gamil coast during December 2005 and August 2006. Water samples were collected in one liter white polyethylene bottles, which were placed in an ice-box following collection, and transferred to the laboratory for storage at 4°C until analysis.

Specimens of the most commercial bivalve *Donax trunculus* were collected from the five sampling sites during December 2005 and August 2006 by obtaining individuals with standard lengths between 1 and 3 cm. Standard length and body weights were recorded for each specimens. Live samples were left in clean water for 30 minutes to purge their guts. Only the soft tissue was kept in plastic bags and frozen until analysis. The soft parts of *Donax trunuculus* were dried at 70°C for 12 hrs before analysis. Exact dry weight of sample (0.5 g) was digested in Teflon vessels with analar nitric acid (HNO3), tightly covered and allowed to predigest overnight at room temperature. Complete digestion and preparation of bivalve sample for trace metal analysis were done according to (UNEP/FAO/IAEA/IOC, 1984).

Total concentrations of Fe, Mn, Zn, Cu, Pb and Cd metals in bottom sediment, surface water and bivale (*D*. *trunculus*) samples were analyzed using an atomic absorption spectrophotometer (AAS) (Perkin Elmer, Waltham, MA, USA, model 1200 A), at the El-Fostat Center, Cairo, Egypt, according to the Standard Method 3110 (APHA 1992). All analyses were carried out in triplicate. For each run, three "blanks" were analyzed using the same procedure to check the purity of reagents and any possible contamination. A similarity test was carried out through cluster analyses from simple Euclidian distance.

### **3. Results and discussion**

A similarity test established that sites 2 and 3 were highly similar, as well as sites 4 and 5, which were equally similar. Site 1 presented a similarity index closer to sites 2 and 3 than to the others. This test verified that El Gamil Beach can be divided into two areas. Sites 1, 2 and 3 represent the first area, and sites 4 and 5, the second.

A total of 30 sediment samples were collected from the five selected sites along El-Gamil coast during December 2005 and August 2006. The sediment samples were collected by pushing a plastic core (12 cm in diameter) into the bottom sediment to a depth of approximately 5 cm, then put in plastic bags and transferred to the laboratory. Sediments were dried at 100 C° for 24hrs and kept in plastic bags until analysis. A representative 50 gm of sediment sample were repeatedly treated with hydrogen peroxide (30%) for removal of organic matter and loss in weight was determined and the organic matter free samples were treated by using dilute HCl to remove calcium carbonates and loss in weight was determined according to method described by Folk, 1974. The grain size analysis of the examined samples was done according to Friedman and Johnson 1982. Dry sand was fractioned by dry sieving using sieves with openings of 2, 1, 0.5, 0.25, 0.125, 0.063 and 0.032 mm and an electric shaker. The weight percentages of the different size classes were

To detect the heavy metal contamination in the sediment samples, an exact weight of dry sample (0.5 gm) of each sediment sample was completely digested for about 2hrs in Teflon vessels using a mixture of HNO3, HCLO4 and HF (3:2:1 v/v 10 ml) (triplicate digestions were made for each sample). The final solution was diluted to 25 ml with distilled de-

A total of 30 surface water samples were collected at a depth of 0.5 m from the five selected sites along the El-Gamil coast during December 2005 and August 2006. Water samples were collected in one liter white polyethylene bottles, which were placed in an ice-box following

Specimens of the most commercial bivalve *Donax trunculus* were collected from the five sampling sites during December 2005 and August 2006 by obtaining individuals with standard lengths between 1 and 3 cm. Standard length and body weights were recorded for each specimens. Live samples were left in clean water for 30 minutes to purge their guts. Only the soft tissue was kept in plastic bags and frozen until analysis. The soft parts of *Donax trunuculus* were dried at 70°C for 12 hrs before analysis. Exact dry weight of sample (0.5 g) was digested in Teflon vessels with analar nitric acid (HNO3), tightly covered and allowed to predigest overnight at room temperature. Complete digestion and preparation of bivalve sample for trace metal analysis were done according to

Total concentrations of Fe, Mn, Zn, Cu, Pb and Cd metals in bottom sediment, surface water and bivale (*D*. *trunculus*) samples were analyzed using an atomic absorption spectrophotometer (AAS) (Perkin Elmer, Waltham, MA, USA, model 1200 A), at the El-Fostat Center, Cairo, Egypt, according to the Standard Method 3110 (APHA 1992). All analyses were carried out in triplicate. For each run, three "blanks" were analyzed using the same procedure to check the purity of reagents and any possible contamination. A similarity

A similarity test established that sites 2 and 3 were highly similar, as well as sites 4 and 5, which were equally similar. Site 1 presented a similarity index closer to sites 2 and 3 than to the others. This test verified that El Gamil Beach can be divided into two areas. Sites 1, 2 and

collection, and transferred to the laboratory for storage at 4°C until analysis.

test was carried out through cluster analyses from simple Euclidian distance.

**2.2 Bottom sediment, surface water and bivalve analysis** 

calculated in three replicates per site sampled.

ionized water (Oregioni and Astone, 1984).

(UNEP/FAO/IAEA/IOC, 1984).

**3. Results and discussion** 

3 represent the first area, and sites 4 and 5, the second.

The sediment at the five selected sites showed a highest percentage of very fine and fine sand coupled with low percentage of coarse fraction (Table 2). The maximum percentage of organic matter content was recorded at both sites of El-Gamil inlet and El Fardous with values of 4.13 ± 1.3 % and 4.23 ± 1.77 %, respectively. The high percentage of organic matter in the two mentioned sites can be attributed to the discharge of sewage wastes into the Mediterranean Sea through El Gamil outlet and Ashtoum El Gamil outlet along El Manzala Lake. Furthermore, the untreated domestic sewage discharged into the sea from four touristic villages in this coastal area *vise*: El Gamil, El Abtal, El Maghraby and El Fardous. The calcium carbonate content was very high at El Gamil airport with value of 27. 53 ± 5.10 %, while it was very low (3.03 ± 1.18%) at El Debba. The high values of calcium carbonate content at site (1) can be attributed to the accumulation of tremendous amounts of shell fragments blanketing the bottom sediment at El Gamil airport.

In the sediment samples, the concentration of heavy metals was higher during winter (Table 3). Even though there was variability among sites, the overall concentration range for a particular metal was relatively narrow, with no values that appeared to be unusual. Generally, in the sediment samples the heavy metals distribution followed the decreasing order of Fe> Mn> Zn> Pb**>** Cu> Cd. Moreover, El Manasra site suistained the heighest values of heavy metal contaminations recorded during the present study. This can be explained by the increasing industrial activities at this site. So, these high contaminants were associated with natural gas companies, pipeline industries and an electric power generating station operating at this area.


Table 2. The physical and chemical properties of sediment during summer 2006

Heavy Metals Contamination of a Mediterranean Coastal Ecosystem, Eastern Nile Delta, Egypt 303

Table 5. Mean concentration of total heavy metals in water samples during winter and

Table 6. Mean concentration of total heavy metals in *Donax trunculus* samples during winter

summer (2005-2006).

and summer (2005-2006).


Table 3. Mean concentration of the total heavy metals in sediment samples during winter and summer (2005-2006)


Table 4. Correlation coefficient matrix between heavy metals, organic matter (O.M.), Calcium carbonate (CaCo3), and grain size in sediment samples during summer 2006


Table 3. Mean concentration of the total heavy metals in sediment samples during winter

Table 4. Correlation coefficient matrix between heavy metals, organic matter (O.M.), Calcium carbonate (CaCo3), and grain size in sediment samples during summer 2006

and summer (2005-2006)

Table 5. Mean concentration of total heavy metals in water samples during winter and summer (2005-2006).


Table 6. Mean concentration of total heavy metals in *Donax trunculus* samples during winter and summer (2005-2006).

Heavy Metals Contamination of a Mediterranean Coastal Ecosystem, Eastern Nile Delta, Egypt 305

Table 7. Concentration factor of metals in the soft tissue of *Donax trunculus* during winter

and summer 2005-2006.

Classification of pollution level of each element according to the American rules for sediment, in conformity to the lowest effect (LEL), heavily polluted category (HPC) and sever effect level (SEL). Judging by the present results, El Gamil beach can be considered a non–metal–polluted area, according to the pollution levels determined by the international rules (Ontario Ministry of the Environment-OME and United States Environmental Protection Agency – EPA).

Correlation coefficient matrix between heavy metals, organic matter, calcium carbonate and grain size of the sediment collected during August 2006 was statistically calculated (Table 4). The correlation coefficient matrix between heavy metal concentrations and physico-chemical characteristics of the sediment samples of El Gamil beach varied between negatively and significantly ones. Strong positive correlations were noticed between Cd and sand (r = 0.995); and Cu and Pb (r = 0.996). While, inverse correlations between Cd and silt (r = -0.904); and sand and silt (r = -0.983) as shown in figures 2, 3, 4, and 5 respectively.

The concentrations of heavy metals were higher in the summer than in the winter in the surface water samples collected during the present study (Table 5). Even though there was variability among sites, the overall concentration range for a particular metal was relatively narrow, with no values that appeared to be unusual. Not surprisingly, Fe concentrations were the highest, ranging from 822.6 ± 14.7 µg g-1 at El Fardous to 896 ± 15 µg g-1 at El Debba. Cd concentrations were the lowest and ranged from 0.8 ± 1.3 µg g-1 at El Gamil inlet to 2.7 ± 0.11 µg g-1 at El Fardous.

The concentrations values of heavy metal (µg g-1 dry wt) in the soft tissue of *Donax trunculus* are shown in table (6). The concentrations of heavy metals were higher in the summer than in the winter in the bivalve samples collected during the present study, and with the decreasing order of Fe> Zn> Pb> Mn> Cu> Cd. Based on the data given in table (6), it seems that the observed variation in metal levels in *Donax trunculus* at different sites can be attributed to two mechanisms. The first is the availability of different metals in different sites, which in its turn depends on the pollution sources that usually vary among different sites. The second is the animal involves different uptake and retention mechanisms which may also vary with physiological and environmental factors (Byran, 1973) or even with the sexual state of the animal (Alexander and Young, 1976). Generally, the values of heavy metals concentration varied with insignificant range in both seasons and among sampling sites due to similar conditions affecting these sites. The highest concentration level of Zn (36.4 ± 3.8 µg g-1) and Cu (4.8 ± 0.3 µg g-1) metals in the analyzed species are less than the maximum permissible levels (MPLs) of 100 µg g-1 and 10 µg g-1 for Zn and Cu, respectively. The (MPLs) of 2 µg g-1, and 5 µg g-1 declared by WHO 1982 and WHO 2006 for Cd and Pb, respectively are much lower than those detected in the soft tissues of D. trunculus with 4.8 ± 0.3 µg g-1 for Cu and 9.2 ± 0.2 µg g-1 for Pb. Donax trunculus inhabiting El Gamil beach along the western coast of Port Said on the Mediterranean Sea are more likely to be toxic for public health.

On the other hand the concentration factor of metals is considered as an indicator of heavy metals accumulation in the tissues of aquatic organisms in relation to their concentration in the ambient water (Sultana and Rao, 1998). The concentration factor values for the studied metals in *Donax trunculus* are delineated in table (7). For *Donax trunculus*, Cd gave the highest accumulation rate in the animal tissue with C.F. values ranging between 833.33 and 592.59 in winter and 2750 and 769.23 in summer. The order of C.F. in the soft tissues of *Donax trunculus* was Cd> Cu> Pb> Zn> Fe> Mn, respectively. This order indicates that *Donax trunculus* can be used as good indicator for the toxic metals as Cd and bio-indicator for essential metals as Cu.


Classification of pollution level of each element according to the American rules for sediment, in conformity to the lowest effect (LEL), heavily polluted category (HPC) and sever effect level (SEL). Judging by the present results, El Gamil beach can be considered a non–metal–polluted area, according to the pollution levels determined by the international rules (Ontario Ministry of the Environment-OME and United States Environmental

Correlation coefficient matrix between heavy metals, organic matter, calcium carbonate and grain size of the sediment collected during August 2006 was statistically calculated (Table 4). The correlation coefficient matrix between heavy metal concentrations and physico-chemical characteristics of the sediment samples of El Gamil beach varied between negatively and significantly ones. Strong positive correlations were noticed between Cd and sand (r = 0.995); and Cu and Pb (r = 0.996). While, inverse correlations between Cd and silt (r = -0.904); and sand and silt (r = -0.983) as shown in figures 2, 3, 4, and 5 respectively. The concentrations of heavy metals were higher in the summer than in the winter in the surface water samples collected during the present study (Table 5). Even though there was variability among sites, the overall concentration range for a particular metal was relatively narrow, with no values that appeared to be unusual. Not surprisingly, Fe concentrations were the highest, ranging from 822.6 ± 14.7 µg g-1 at El Fardous to 896 ± 15 µg g-1 at El Debba. Cd concentrations were the lowest and ranged from 0.8 ± 1.3 µg g-1 at El Gamil inlet

The concentrations values of heavy metal (µg g-1 dry wt) in the soft tissue of *Donax trunculus* are shown in table (6). The concentrations of heavy metals were higher in the summer than in the winter in the bivalve samples collected during the present study, and with the decreasing order of Fe> Zn> Pb> Mn> Cu> Cd. Based on the data given in table (6), it seems that the observed variation in metal levels in *Donax trunculus* at different sites can be attributed to two mechanisms. The first is the availability of different metals in different sites, which in its turn depends on the pollution sources that usually vary among different sites. The second is the animal involves different uptake and retention mechanisms which may also vary with physiological and environmental factors (Byran, 1973) or even with the sexual state of the animal (Alexander and Young, 1976). Generally, the values of heavy metals concentration varied with insignificant range in both seasons and among sampling sites due to similar conditions affecting these sites. The highest concentration level of Zn (36.4 ± 3.8 µg g-1) and Cu (4.8 ± 0.3 µg g-1) metals in the analyzed species are less than the maximum permissible levels (MPLs) of 100 µg g-1 and 10 µg g-1 for Zn and Cu, respectively. The (MPLs) of 2 µg g-1, and 5 µg g-1 declared by WHO 1982 and WHO 2006 for Cd and Pb, respectively are much lower than those detected in the soft tissues of D. trunculus with 4.8 ± 0.3 µg g-1 for Cu and 9.2 ± 0.2 µg g-1 for Pb. Donax trunculus inhabiting El Gamil beach along the western coast of

Port Said on the Mediterranean Sea are more likely to be toxic for public health.

On the other hand the concentration factor of metals is considered as an indicator of heavy metals accumulation in the tissues of aquatic organisms in relation to their concentration in the ambient water (Sultana and Rao, 1998). The concentration factor values for the studied metals in *Donax trunculus* are delineated in table (7). For *Donax trunculus*, Cd gave the highest accumulation rate in the animal tissue with C.F. values ranging between 833.33 and 592.59 in winter and 2750 and 769.23 in summer. The order of C.F. in the soft tissues of *Donax trunculus* was Cd> Cu> Pb> Zn> Fe> Mn, respectively. This order indicates that *Donax trunculus* can be used as good indicator for the toxic metals as Cd and bio-indicator

Protection Agency – EPA).

to 2.7 ± 0.11 µg g-1 at El Fardous.

for essential metals as Cu.

Table 7. Concentration factor of metals in the soft tissue of *Donax trunculus* during winter and summer 2005-2006.

Heavy Metals Contamination of a Mediterranean Coastal Ecosystem, Eastern Nile Delta, Egypt 307

Fig. 4. Correlation between Cd and silt% in sediments

Fig. 5. Correlation between sand% and silt% in sediments

Fig. 2. Correlation between Cd and sand% in sediments

Fig. 3. Correlation between Cu and Pb in sediments

Fig. 4. Correlation between Cd and silt% in sediments

Fig. 2. Correlation between Cd and sand% in sediments

Fig. 3. Correlation between Cu and Pb in sediments

Fig. 5. Correlation between sand% and silt% in sediments

Heavy Metals Contamination of a Mediterranean Coastal Ecosystem, Eastern Nile Delta, Egypt 309

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## **4. Conclusion**

Nearly 40% of industrial development activities are practiced in Egyptian coastal zones, in addition to a number of urban and tourism development activities. Furthermore, coastal zones monopolize the seaports infrastructure, in addition to agricultural and land reclamation sectors, as well as a developed road network capable of accommodating all development aspects. The coastal zones attract increasing numbers of migrating workers from other areas and Governorates. Tourism development represents one of the main activities in Egypt's coastal zones, particularly in terms of beach development regarded as the basis of international tourist attraction.

The quality of marine and coastal environments and their environmental resources along the Nile Delta ecosystem are threatened by a number of hazards related to internal development inside the country whose impacts are carried to coastal zones via the river Nile, agricultural drainage system and air (land sources).

Results of the present study indicate El Gamil beach along the western coast of Port Said City on the Mediterranean Sea is considered a non metal polluted area, suggesting regular monitoring of metals in the sediments, water and marine organisms should be undertaken, due to the rapid growth of area. Different types of pollutants, including agricultural, industrial, organic compounds and domestic discharge were identified by analyzing bottom sediment, surface water and bivalve sampling collected from the study area of heavy metals. Contaminants originating from agricultural and domestic sources were detected along the El Fardous and El Gamil inlets. Industrial pollutants were detected at the El Manasra and El Fardous sites. These contaminants were associated with natural gas companies, pipeline industries and an electric power generating station. The proximity to various anthropogenic sources of pollutants warrants a continue monitoring program in the Egyptian coasts along Mediterranean Sea for inorganic and chemical organic compounds in sediments, water, and biota in order to have an effective coastal management program to protect the ecological integrity of this valuable ecosystem and the health of humans associated with it. The reported results could be considered as documentation of a good understanding to assess the ecosystem status of the concerned sites, and might be useful to researchers interested in the cotastal zones of Mediterranean Sea. Farther environmental studies are required to assess and improve the development planning and economic activities along of study area and its vicinity.
