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OCPs and PCBs in Seawater from Egyptian Mediterranean Coast of Alexandria M. A. Shreadah1, T. O. Said1,2*, I. M. Othman1, E. I. Fathallah3, M. E. Mahmoud3 National Institute of Oceanography and Fisheries, P.O 4053, Kayet Bay, Alexandria, Egypt.
1
Chemistry Department, Faculty of Science, King Khalid University, KSA.
2
Chemistry Department, Faculty of Science, Alexandria University, Egypt.
3
niof.shreadah@gmail.com; *tareksaideg@yahoo.co.uk; islam_shalaby_2007@yahoo.com; memahmoud10@yahoo.com; Eimanfathallah@yahoo.com
Received 6 May 2014; Accepted 28 May 2014; Published 15 December 2014 © 2014 Science and Engineering Publishing Company Abstract trade since 1988 by the Ministry of Agriculture and Land Reclamation Ministry, Egypt (Morsy 2006). In The residues of 19 EPA‐organochlorine pesticides (OCPs) 1996, a ministerial decree prohibited the import and and polychlorinatedbiphenyl (PCBs) were determined in use of 80 pesticides including aldrin, dieldrin, endrin, water using GC‐ECD and GC‐MS collected from 49 different chlordane, heptachlor, dichloro diphenyl locations along the semi‐closed areas of Egyptian Mediterranean Coast of Alexandria. The pollutants studied trichloroethane (DDT), toxaphene, mirex, lindane, were 7 individual PCBs congeners, HCHs (α,β,γ‐ endosulfan, pentachorophenol and heptachlor epoxide, hexachlorocyclohexane), cyclodienes; TCs (aldrin, endrin, as well as 20 other chlorine containing pesticides and dieldrin) and dichlorodiphenyltrichloroethanes; DDTs (o,p‐ organometallic compounds including tri‐cyclohexyl DDE, p,p‐DDE, o,p‐DDD, p,p‐DDD, o,p‐DDT, p,p‐DDT). tin hydroxide, triphenyl tin hydroxide, triphenyl tin DDTs ranged from <16‐964.68, <16‐767.06, <16‐181.62 and acetate, methoxy ethyl mercury acetate and phenyl 151.86‐839.65 ngL‐1; TCs ranged from <16‐63.48, <16‐126.68, mercury salicylate. Egypt signed the Stockholm <16‐103.81, <16‐90.46 ngL‐1, HCHs ranged from <16, <16‐1.27, Convention on POPs in 2002 and ratified it in 2003. ‐1 <16‐21.24, 43.64‐67.30 ngL for surface water of Abu‐Qir, Nonetheless, many of the pesticides banned or Eastern Harbour, Western Harbour and El‐Max, respectively. withdrawn from markets are still produced in The average concentrations of OCPs and PCBs in bottom developing country markets. Similar to many water at different sites were higher than those of surface countries in the Mediterranean Region, there are no water. 97% and 43% of HCHs and DDTs were recorded at El‐Max Bay, respectively. 29% of TCs was recorded at emission inventories of sources or release of organic Eastern Harbour and 42% of PCBs was recorded at Western and inorganic pollutants in the Egyptian environment, Harbour. PCA was applied for classifying different analytes. or any official data on stockpiles and disposal (Barakat 2004). Keywords Organochlorines; Seawater; Egypt; Mediterranean; Alexandria
Introduction Organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) are two main categories of persistent organic pollutants (POPs) present as contaminants in the environment. They have been used for many years in different industries and agricultural activities. They are strongly associated in aquatic ecosystems due to their hydrophobic properties, and tend to accumulate in water (Binelli et al. 2008). Based on the reports of their harmful effects on wildlife and humans in Egypt, many OCPs were banned or restricted from use or
Although the study of pollutants in the Egyptian Mediterranean Sea has been investigated by numerous workers (Said et al. 1994; Shreadah et al. 2006; El Deeb et al. 2007; Emara et al. 2008; Emara and Shreadah 2009, Berrojalbiz et al. 2011, Shobier et al. 2011; Shreadah et al. 2011; Shreadah et al. 2012; Abdel Ghani et al. 2013). The present paper is considered as one of the most important records to investigate levels and distributions of OCPs in seawater of the Egyptian Mediterranean Sea coast of Alexandria. Materials and Methods A total of 49 samples of seawater were collected from
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Abu‐Qir Bay, Eastern Harbor, Western Harbor, and El‐ Max Bay during 2010 (Table 1 and Fig. 1). Samples were collected using a high quality and Purified PVC Niskin’s bottle. Salinity and pH values were measured during the time of sampling using Hydrolab model (Mutlti Set 430i WTW).
spectrometer, GC‐MS (Thermo Scientific Company ‐ Trace DSQ II MS). OCPs were quantified from individually resolved peak areas with the corresponding peak areas of the external standards (POC mixture provided by IAEA). They include: α, β, and γ‐HCH, aldrin, dieldrin, DDT, and its isomer DDE. For quality control/quality assurance measurements, four analyses were conducted on OCPs reference material SRM‐2974a freeze‐dried Mussel tissue (Mytilus edulis) provided by EIMP‐IAEA. Results showed that the recovery efficiency ranged from 92% to 108% with coefficients of variation of 8–15%. The limit of detection was estimated to be 0.015 ngg‐1 for PCBs and 0.016 ngg‐1 for OCPs based on the minimum quantity of sample required for a discernible peak appeared on the chromatogram. All standards used for calibration are sigma‐Aldriach chemicals with purity > 99%.
FIG. 1. SAMPLING LOCATIONS OF SEAWATER: A) ABU‐QIR BAY; (B) EASTERN HARBOR; (C) WESTERN HARBOR AND (D) EL‐MAX BAY. TABLE 1. LOCATIONS OF THE SAMPLING SITES ALONG THE EGYPTIAN MEDITERRANEAN COAST OF ALEXANDRIA
Results and Discussion The order of decreasing of salinity was: Western Harbor > Eastern Harbor >Abu‐Qir Bay > El‐Max Bay. The order of decreasing of pH was: Abu‐Qir Bay > Western Harbor > Eastern Harbor > El‐Max Bay, while the order of decreasing of (DO) was: Abu‐Qir Bay > Eastern Harbor > Western Harbor > El‐Max Bay. On the other hand, the order of decreasing of OOM was as follow: Eastern Harbor > El‐Max Bay >Western Harbor >Abu‐Qir Bay depending on the heavy load of wastewater discharged into the investigated area (Abdel Ghani et al. 2013).
Dissolved oxygen (DO) was determined using Winkler titration method (Strickland and Parasons 1975). Oxidizable organic matter (OOM) was measured according to FAO (1976). Samples were collected in dark bottles previously washed with detergent, double rinsed with ultra‐pure water (Millipore), rinsed with pesticide grade ethyl alcohol, and dried. The containers were carefully filled to overflowing, without passing air bubbles through the sample and kept in dark at 4ºC. Liquid‐liquid extraction (Guitierrez et al. 2007), followed by gas chromatographic analysis (USEPA 1980) are performed. All samples were analyzed by gas chromatography‐ electron capture detector, GC‐ECD (Chromatograph HP5890 II FID/ECD Series II (5890) USA) and confirmed by gas chromatograph‐mass
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The geographical distribution of OCPs revealed wide variations and cleared out that these contaminants spread in the area of study (Table 2). Fig. 2 cleared out that the highest concentrations for TCs and DDTs were measured at the surface of site 3 of Abu‐Qir Bay located in front of El‐Amia drain (domestic waste source). On the meantime, PCBs showed the highest concentrations at the bottom of site 8 located 3 Km left of Nelson Island in Abu‐Qir Bay. The Highest concentrations of HCHs recorded at the bottom of site 9 in front of the Dry Dock at Abu‐Qir Bay were mainly due to wastewater discharged into the Bay through El‐ Amia Drain, as well as industrial sewages inside the Bay (Shreadah et al. 2012). In the Eastern Harbor, the highest concentrations of TCs were measured at the bottom of site 24 at the Eastern Harbor Boughaz Opening. On the other hand, maximum concentrations of DDTs were measured in the bottom of site 18 adjacent to the
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Egyptian Union for Diving. PCBs exhibited its highest level at the bottom of site 17. The highest concentrations for HCHs were measured at the surface of site 23 located 300 m from Eastern Harbor Boughaz due to the presence of human activities, including fishing, yacht sport and land‐based effluents. Boat building workshops, recreation and sailing boats anchoring inside the Harbor could greatly contribute to the water contamination with PCBs (Shobier et al. 2011). In the Western Harbor, the highest concentrations for HCHs, Cs, and DDTs were measured at site 31 located in front of Coal platform.
sites were higher than those for surface water because these compounds were organic compounds, to a varying degree, resist photolytic, biological and chemical degradation as well as their low water solubility. Their semi‐volatile characteristics enabled them to move long distances before deposition and settling (Van der Veen et al. 2006). Fig. 3 showed that the 97% of HCHs was recorded, at El‐Max Bay, the maximum of 29% of TCs was measured at the Eastern Harbor and the maximum of 42% of PCBs was measured at the Western Harbor. Generally, the maximum of 52% of TP was measured at El‐Max Bay with a minimum of 9% recorded at the Western Harbor. The order of decreasing of HCHs concentrations in water samples was: El‐Max‐Bay > Western Harbor > Abu‐Qir Bay > Eastern Harbor. TCS decreased in the order: Eastern Harbor > El‐Max Bay > Abu‐Qir Bay > Western harbor. DDTs decreased in the order: El‐Max bay >Abu‐Qir Bay > Western Harbor > Eastern Harbor, while PCBs decreased in the order: Western Harbor > Abu‐Qir Bay > El‐Max bay > El‐Max Bay. Significant negative correlation between TP and salinity (r = ‐0.58 at P > 0.001), and (r = ‐0.39 at P > 0.01) for surface and bottom water, respectively. This was due to the fact that pesticides were sparingly soluble in saline waters (Van der Veen et al. 2006). TP, on the other hand, decreased in the order: El‐Max Bay > Western Harbor > Abu‐Qir Bay > Eastern Harbor.
TABLE 2. PHYSICOCHEMICAL PARAMETERS, OCPS AND PCBS CONCENTRATIONS (NG/L) IN SEAWATER FROM THE EGYPTIAN MEDITERRANEAN COAST OF ALEXANDRIA
N.D: below Detection Limit, PCB 28 = 2,4,4‐Trichlorobiphenyl; PCB 52 = 2,2,5,5‐tetrachlorobiphenyl; PCB 101 = 2,2,4,5,5‐ pentachlorobiphenyl; PCB 118 = 2,3,4,4,5‐pentachlorobiphenyl; PCB 138 = 2,2,3,4,4,5‐hexachlorobiphenyl;PCB 153 = 2,2,4,4,5,5‐ hexachlorobiphenyl; PCB 180= 2,2,3,4,4,5,5‐Heptachlorobiphenyl.
In addition, the maximum concentrations of PCBs, were measured at site 34 located at Shipping Control Tower due mainly to exporting/importing activities of raw materials, general goods, fertilizers, cement, wood, grains, coal, oil molasses, in addition to petroleum industry. In El‐Max Bay, maximum concentrations for HCHs were observed at site 41 located about 300 m in front of El‐Nobariya drain. On the other hand TCs and DDTs were measured at site 49. On the meantime,PCBs exhibited their maximum level at site 46 located in front of Polyethylene Factory due to a heavy load of wastewater both directly from industrial outfalls and indirectly from lake Maryut (Emara and Shreadah 2009). The total average concentrations of OCPs and PCBs in bottom water samples at different
A comparative study was carried out between GC‐ ECD and GC‐MS techniques using 25% of all seawater samples selected randomly from different areas. Results of GC‐ECD were qualitatively confirmed by GC‐MS, yet the identification of different detected compounds was more pronounced using GC‐ECD. This was due to the selectivity of ECD detector for chlorinated hydrocarbons (Binelli et al. 2008). Concentrations of HCHs observed in the Eastern Harbor in the present study were generally lower than previously measured (Table 3). In contrast the present concentrations of DDTs were generally higher than those previously recorded as given in Table 3. Aldrin, Dieldrin, Endrin, and DDTs measured in seawater of El‐Max Bay in the present study were slightly higher than previously reported. Concentrations of HCHs, Aldrin, Dieldrin, Endrin, and DDTs in the Egyptian coastal areas along the Mediterranean Sea were lower than concentrations in coastal seawater in Philippines and USA (Table 3). Principle Component Analysis (PCA) indicated that the majority of the variance 85.6% of 12 EPA‐OCPs as
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active variables and 15 sites in Abu‐Qir Bay were explained by four eigenvectors‐principal components. PC1, PC2, PC3, and PC4 explained 36.9%, 29.5%, 9.8% and 9.3% of the total variances, respectively (Table 4). PC1 had a significant correlation with β‐HCH, γ–HCH, p, p‐DDE, p, p‐ DDD, and o, p‐DDT. PC1 had also high loading of p,p‐DDE.
The majority of the variance 88.6% of 7 EPA‐PCBs as active variables and 15 sites was explained by three eigenvectors‐principal components. PC1, PC2, and PC3 explained 40.5%, 25.7%, and 22.4% of the total variances, respectively (Table 4). TABLE 3. CONCENTRATIONS OF PCBS AND ORGANOCHLORINE PESTICIDE
(NGL‐1) COMPARED WITH OTHER AREAS
<DL: below detection limit, *HCHs calculated as lindane, NA: not available, 1) Present study; (2) Morsy and Abdallah (2006); (3) Abd‐ Aballah and Abbas (1994); (4) Abd‐Allah (1992); (5) Tanabe (2000); (6) USEPA (1980).
TABLE 4. ROTATED COMPONENT MATRIX FOR OCPS AND PCBS IN SEAWATER THE EGYPTIAN MEDITERRANEAN COAST OF ALEXANDRIA
FIG. 2 SPATIAL DISTRIBUTIONS OF TOTAL HCHS,TC, AND DDTS (NG L‐1) IN THE SURFACE AND BOTTOM SEAWATER. PC: Principal Component, *significant correlation, Negative values indicate negative correlation.
FIG. 3 PERCENTAGE CONTRIBUTION OF HCHS, CS, DDTS, PCBS, AND TP IN SEAWATER DURING 2010.
The majority of the variance 88.6% of 7 EPA‐PCBs as active variables and 15 sites was explained by three eigenvectors‐principal components. PC1, PC2, and PC3 explained 40.5%, 25.7%, and 22.4% of the total variances, respectively (Table 4).
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PC1 had a significant correlation with PCB 101, and PCB138. Thus, PC1 was a quantitative correlation component and corresponded to the total PCBs concentration. PC1 had high loading of PCB138. In the Eastern Harbor, the majority of the variance 85.6% of 12 EPA‐OCPs as active variables and 13 sites was explained by five eigenvectors‐principal components. PC1, PC2, PC3, PC4, and PC5 explained 30.3%, 16.9%, 13.2% and 12.9%, and 9.9% of the total variances, respectively (Table 4). PC1 had a significant correlation with β‐HCH, Aldrin, p, p‐DDE, and p, p‐ DDT. These compounds gave strong correlation with the total OCPs concentration. Thus PC1 was a quantitative correlation component and corresponded to the total OCPs concentration. PC1 had high loading of p,p‐DDT. The majority of the variance 88.6% of 7
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EPA‐PCBs as active variables and 13 sites was explained by four eigenvectors‐principal components. PC1, PC2, PC3, and PC4 explained 25.7%, 19.7%, 16.2% and 15.9% of the total variances, respectively (Table 4). PC1 had a significant correlation with PCB101, and PCB138.. PC1 had high loading of PCB 138.The majority of the variance 88.6% of 12 EPA‐ OCPs as active variables and 11 sites was explained by five eigenvectors‐principal components. PC1, PC2, PC3, PC4 and PC5 explained 30.0%, 16.1%, 13.9%, 13.0%, and 12.5% of the total variances, respectively (Table 4). PC1 had a significant correlation with β‐ HCH, γ –HCH, Aldrin, and p, p‐DDE. Thus, PC1 was a quantitative correlation component and corresponded to the total OCPs concentration. PC1 had high loading of p,p‐DDE. The majority of the variance 84.5% of 7 EPA‐PCBs as active variables and 11 sites was explained by three eigenvectors‐principal components. PC1, PC2, and PC3 explained 32.8%, 27.9%, and 23.8% of the total variances, respectively (Table 4). PC1 had a significant correlation with PCB 101, PCB 118, and PCB138. These compounds gave strong correlation with the total PCBs concentration. The majority of the variance 91.6% of 12 EPA‐OCPs as active variables and 10 sites was explained by four eigenvectors‐principal components. PC1, PC2, PC3, and PC4 explained 26.2%, 25.7%, 22.3%, and 17.3% of the total variances, respectively (Table 4). PC1 had a significant correlation with α–HCH, β‐HCH, and p, p‐ DDT. These compounds gave strong correlation with the total OCPs concentration. PC1 had high loading of p,p‐DDT. The majority of the variance 85.65% of 7 EPA‐PCBs as active variables and 10 sites was explained by four eigenvectors‐principal components. PC1, PC2, PC3, and PC4 explained 25.6%, 24.6%, 17.9%, and 17.5% of the total variances, respectively (Table 4). PC1 had a significant correlation with PCB 28, and PCB138. PC1 had high loading of PCB138. Conclusions The investigation of water in Abu‐Qir Bay, Eastern Harbor, Western Harbor, and El‐Max Bay revealed that OCPs and PCBs were detected using selected GC‐ ECD technique. The levels were lower than permissible levels recommended by the National Academy of Sciences and National Academy of Engineering, by the Swedish Food Regulation and the US Food and Drug Administration. The baseline data can be used for regular ecological monitoring, considering the industrial and agricultural growth around this important ecosystem. The spatial
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