Study of Pollution in Mediterranean Sea El-Gamal, Yousry & Bayoumi, Mohamed Engineering & Technology Collage, Arab Academy for Science & Technology, Alexandria- Egypt. Abstract This study represents the early outcomings of a research maritime trip in the Mediterranean sea. This trip was conducted by the training vessel of the Arab Academy for Science & Technology in June 1996 starting from Alexandria port. The vessel course passed Lattaquie port in Syria and the port of Napoli in Italy and terminated at Alexandria. A specially designed log was used to sample 1012 surface samples during this trip. These samples are prepared to be analyzed for three objectives; Pollution by hydrocarbons, heavy metals pollution and radioactive survey. The actual work represents the outcomings of the hydrocarbons pollution state along this trip. 1. Introduction Pollutant substances entering the marine environment have increased due to the rapid growth of technology and population activities. Generally, the sources of solid wastes introduced to the sea are mainly coming from garbage, wreckage and by-products of solid wastes. Radioactive wastes are coming from nuclear power plants used in power generation and military activities. Heat pollution is resulting from heat exchanges and from cooling system wastes. Sewage is resulting from sanitary drainage which contains the human and the animal wastes. Chemical wastes are resulting from noxious chemicals of industrial activities. Oil wastes are resulting from noxious, industrial and domestic wastes on land and also from shipping activities in the sea. Most of the mentioned pollutants are mainly coming from industrial and domestic activities by man on the land whichfinallyfindtheir way to the sea. The main source of marine pollution is coming from shipping transportation and associated activities such as operational discharges, bunkering, docking and ship accidents... etc. Oil is considered as the most serious type of pollution, this is because oil is very widely used in most industrial, urban and domestic activities on the land and in the sea. So, the possibility that oil would spill in the sea is more than any other type of pollutant. The degree of risk by oil is not always proportional to the volume or the quantity of spilled oil, but it depends on some factors such as: wind, tide,
206 Water Pollution temperature and others environmental conditions. It also depends on the properties of oil such as; its toxicity, solubility, density, volatility, biodegradability, etc. Oil has destroying effects to the marine biota and the biological life. It has toxicity effects on some sea's animals and aquatic plants and consequently destroy the natural resources in the sea. However, the biological and medical effects of oil pollution on the marine life and the man is beyond the scope of this work. Oil pollution destroys commercial fisheries, beaches and affects tourism activities. In Egypt, it was noticed in the last years that the sea catch in Egyptian coast in Mediterranean sea is decreased. Also it can be observed that the water color was changed. Many studies were carried out to examine this pollution problem and specially oil pollution [1, 2, 3]. The actual study was planed to measure the extent of pollution in some areas in the Mediterranean sea to be able to estimate the situation in the Egyptian ports and coasts. 2. The Study A trip was conducted by the training vessel of the Arab Academy for Science & Technology in June 1996 starting from Alexandria port. The vessel started navigation June 14. 1996 from Alexandria and reached Lattaquie port in Syria in June 17. After two days of stay the vessel took new heading to Napoli in Italy. Berth at Napoli port was done in June 22. The back home leg started in June 26 to reach the Alexandria sheltered area in June 30. The details of the trip are represented on Figure (1). A specially designed log was used to sample 1012 surface samples during this trip. These samples are prepared to be analyzed for three objectives; pollution by hydrocarbons, heavy metals pollution and radioactive survey. The actual work represents the outcomings of the hydrocarbons pollution state along this trip. Gas Chromatography (GC) evolved as an accepted oil fingerprinting technique during the 1970s. The initial use involved packed column technology and the use of both a Flame lonization Detector (FID) tofingerprintthe normal alkane distributions and a Flame Photometric Detector (FPD) tofingerprintthe sulfur distributions. The development of capillary columns for gas chromatography provided an increase in resolution of the separated eluants and substantially an increase in the ability to use only the FID fingerprint to distinguish oils of similar types. It should be pointed out, that gas chromatography is a science of separating compounds in their vapor phase on liquid column coating. The FID is simply a detector to monitor the separation of the oil components. This method uses a gas chromatographic capillary column for the separation of petroleum hydrocarbons and detection of these compounds using a flame ionization detector (FID). The separation of the hydrocarbons is based on the
Water Pollution 207 partitioning of molecular species between an inert carrier gas (helium) and the stationary liquid phase coating the interior walls of the capillary column. This process essentially separates the injected petroleum oil hydrocarbon mixture in the approximate order of their boiling points. The separated components, as they elute off the column, are detected by a flame ionization detector. The distribution of hydrocarbons is recorded (plotted) as they elute from the column as a series of peaks or verticals. The relative retention times of the separated compounds forms the characteristic chromatogram for that particular oil. Samples were prepared for analysis by extracting all of the dissolved and dispersed oil in the sample container from the water and the other substrates present by high grade cyclohexane solvent from the surface layer. The oil-cyclohexane solution (unknown concentration) was concentrated and then placed in for analysis by (GC/FID) in order to obtain a suitable gas chromatogram The operation of the gas chromatography is under computer control. The operating program is TURBOCHROM v4, a userfriendlysystem, developed by PERKIN ELMER corporation. The experimental conditions are given in table below. L Initial Oven Temperature 2. Initial Hold Time 3. Filial Oven Temperature 4. Final Hold Time 5, Equilibration Time 6. Oven Program Rate 7. Column Head Pressure 8. Injector Port Temperature 9. Detector Manifold Temperature 10. Carrier Gas Make Up Flow 11. Hydrogen Gas Flow 12. Air Flow 3. Results & Discussion 40 degrees C 4 minutes 350 degrees C 60 minutes 3 minutes 8 degrees C/min. 15psig 250 degrees C 300 degrees C 30 ml/min. 30 ml/min. 300 ml/min. The results are presented as a function between the detected component "Response"; Rinmv against the retention time RT in min. This response is proportional to the electric conductivity of the detected component concentration. The retention time is the residence time of such component in the column of analysis. The heavier components have larger retention time and vice versa.
208 Water Pollution The samples were analyzed by the above mentioned method and technique. Only 535 samples were considered for analysis. A blank sample analysis was carried out. This represents the analysis of the solvent of extraction which is the cyclohexano figure(2-a). The fingerprints of this solvent will appear in all analysis as a band of long verticals which appear between nearly 2 and 3 min. of retention time. A back ground sample was taken as an "open sea water" sample, this gives a clear bleeding curve as shown in figure (2-b). The open sea samples were taken as a mixture of the samples from number 218 to 399. Those samples come from a sea area facing the Greece and Italian coasts at approximately from 5 to 40 miles from the shore. Such area observed by eye was supposed to be probably clean. The experimental analysis for this sample exhibited no oil pollution in this area up to the sensitivity of the analyzer. Fifteen mixes were prepared to group the selected 535 samples. Many other samples were excluded as supposed to have clean open sea conditions. The samples were taken always from the starboard side at the prow of the vessel. This position was selected to be far from any pollution which may probably attributed to the vessel itself. Samples from 1 to 5: Those samples were taken at the berth of the vessel in Alexandria port as shown in figure (3). The results of the analysis of those samples are represented on figure (4-a). It showed verticals from the beginning to the end of heating range the analyzing column. Those verticals extend from 0-3 5 mm. retention time. This means that those samples contain nearly all oil components; light and heavy. In other words, this area is highly and continuously polluted by oil. Sample from 5 to 9: Those samples were taken along the course from berth to the outlet of the sheltered area of the port of Alexandria. The results of their analysis are given on figure (4 -b). It can be easily noticed that this area is highly polluted by oil. Only heavier oil components are represented. This means that the polluted oil in this area is left for longer time enough to evaporate the lighter components. Samples from 10 to 15: Those represent the mix of samples taken in the territorial waters of Egypt along the distance from Alexandria to territorial. Those samples represents the average of the Egyptian territorial waters. The results are represented on figure (4-c). It can be seen that some heavy components but at lower concentration are still existed. Samples from 16 to 75: Those samples were taken on crossing the territorial waters of Israel, Lebanon and Syria. The water appearance in this segment of the voyage justifies the equal mixing from all those sample in one mix The results of this mix is presented on figure (5-a). Very low level of oil pollution was detected. This minimal pollution lies in the range of heavy components; which may be a spill rejected from a very long time.
Water Pollution 209 Samples form 179 to 193: From those samples, equal quantities are taken to give an average mix for the Syrian territorial water. The results given on figure (5-b) show a lone vertical for a medium density oil component. Samples from 194 to 197: Those samples which were equally mixed in one mix give the results given on figure (5-c). The medium and heavy components appear at low concentrations. Samples from 198 to 206: Those samples are taken on entering the sheltered area of Lattaquie port to the berth location figure (6). The whole band of oil pollution is remarked from this mix analysis as given on figure (7-a). The concentration of this pollution is small with respect to that observed on leaving Alexandria port. This concentration could be regarded as to be relatively high when taking into consideration the actual observed very low maritime traffic compared to Alexandria port. Samples from 207 to 217: Those samples were taken on leaving Lattaquie port to near the Cyprus island. Results are given on figure (7-b) show heavy components. This is probably logic due to the heavy traffic in this comer of Mediterranean sea. Samples from 214 to 217: Those are samples near Cyprus island. The results on figure (7-c) show nearly the same components of the previous mix Samples from 218 to 399: Those sample are regarded as open sea samples. Traces of pollution are remarked for the samples from 218 to 224 as shown on figure (8-a). The rest of samples showed nearly no oil pollution as given on figure (8-b), (8-c) and (9-a). Samples from 430 to 434: Those are the samples taken on approaching Capry of Italy. Heavy components are remarked from the result of the mix as given on figure (9-b). This could be logic because this area leads to the anchorage area for the port of Napoli. Samples from 438 to 447: Those samples were taken in the anchorage area facing the port of Napoli. The results of mix given on figure (9-c) and (10-a) show that this anchorage area is polluted. The existence of the light components proves that the crossing vessels do no take the required measures to avoid spilling oil at sea in the vicinity of the port of Napoli figure (11). The observation by eye proved a high level of oil pollution. For this reason the samples from 459 to 463 were analyzed separately. Those samples show, as given on figure (12), a pollution of all oil components. Samples from 464 to 489: Those samples were taken on leaving the port of Napoli. Figure (13-a), (13-b) and (13-c) show a decrease of the oil pollution on leaving the port of Napoli. Sample from 490 to 500: Those samples were taken at open sea during the home back leg to Alexandria. The analysis of this mix showed clean sea water as given on figure (14-a). Samples from 501 to 510: Those samples were taken on entering the Egyptian territorial water from the west. It can be seen from figure (14-b) that the oil pollution began to appear.
270 Water Pollution Samples from 511 to 520: Those samples were taken on navigating parallel to the Egyptian coast from the west at an average distance of 10 miles. As shown from figure (14-c) the oil pollution still exists. Samples from 520 to 535: Those sample were taken on approaching the sheltered area of Alexandria port from the west. Figure (15-a) shows that the pollution increases. This pollution probably comes from many inshore and offshore petroleum industries recently located at the north coast of Egypt. 4. Conclusions: 1. The oil pollution in the Mediterranean sea was found in the water area of the ports and in territorial water in spite of all the international water convictions. 2. Concerning the Egyptian territorial waters, the oil pollution exists at high concentration. It can be shown that the eastern part of the territorial waters of Egyptian north coasts are more polluted than the western part of the territorial waters of the Egyptian north coasts. A revision for pollution prevention measures must be done for all inshore and offshore companies related to those areas. Acknowledgment Thanks to Captain Hosam Taha and Chemist Mohamed Yousef for their great help. Reference 1. Pollution Status of Abu-Kir Bay, Final Report of the Academy of Science and Technology- Mediterranean Branch- Alexandria 1984. 2. Osman El-Rayis, Massoud Saad and Fatma El-Nady. Level and Changes in Storage of Some Trace metals in Alexandria Eastern Harbour. Pro. 5th Int. Conf; "Environmental Protection is a Must" Alexandria, Egypt. 25-27 April 1995. 3. A. El-Demerdash and A.M. Fakhry. Species Diversity in the habitat types of the delatic Mediterranean Coastal region of Egypt. Pro. 5th Int. Conf; "Environmental Protection is a Must", Mansoura University, Egypt. 25-27 April 1995.
Water Pollution 211 '?$ W. ~5
I Hi! RT R i JJJj IS 20 25 30 35 60 ti RT 15 70 75 30 2i «0 <5 RT figure 3 figure 4
Water Pollution ;-#: ft en
214 Water Pollution r 3'i
Water Pollution T~ H :.5' I - Z?«3
Water Pollution 50 K H
Water Pollution 277 3 I W V - 5
Pollution