POPs in Sediments from the Eastern and Western Egyptian Mediterranean Coast; a Comparative Study

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doi: 10.14355/dac.2016.03.001

POPs in Sediments from the Eastern and Western Egyptian Mediterranean Coast; a Comparative Study Mohamed A.Shreadah1, Tarek O. Said,1,2*, Mohamed A. Mansour1, Fahmy M. El-Sharkawi3, Manal A. Mohamed3 National Institute of Oceanography and Fisheries, Alexandria, Egypt

1

Chemistry Department, College of Science, King Khalid University, Abha, KSA

2

Environmental Health Department, High Institute of Public Health, Alexandria University

3

*tareksaideg@yahoo.co.uk Abstract The residual concentrations of α,β,γ-hexachlorocyclohexane (HCHs), sum of aldrin, endrin and dieldrin (TC), sum of o, p-DDE, p, p-DDE, o, p-DDD, p, p-DDD, o, p-DDT and p, p-DDT (DDTs), total petroleum hydrocarbons (THCs) and sum of 7 individual polychlorinated biphenyl (PCBs) were investigated at different depths collected from 18 stations of sediment samples distributed along the eastern and western coast of the Egyptian Mediterranean Sea. The maximum concentrations of HCHs, TC, DDTs, THCs and PCBs in the Eastern coast of Egypt were 0.19ngg-1 , 0.90 ngg-1, 36.30 ngg-1, 3540 ngg-1 and 136.20 ngg-1, respectively. In the Western coast of Egypt, these concentrations were 0.21 ngg-1, 8.80 ngg-1, 15.90 ngg-1, 9030 ngg-1 and 28.60 ngg1, respectively. Although no significant correlation was observed between total pesticides and total organic carbon (TOC) in sediment samples, there emerges a positive correlation between PCBs and TOC for sediment samples with r = 0.785 and 0.926 at 30 m and 50 m depths, respectively. This is can be attributed to the low solubility of PCBs in water and consequently precipitated reaching bottom waters and contaminated in sediments. The average concentrations of HCHs, TCs, DDTs, TP were much higher in sediment of the western part compared with the eastern one of the Egyptian Mediterranean coast. On contrast, PCBs and TOC% were higher in sediment samples of the eastern part compared to the western one. The present study declared that all recorded concentrations of pesticides and PCBs in the Egyptian Mediterranean coasts were much lower than those reported as permissible levels given by National Academy of Sciences and National Academy of Engineering. Keywords Pesticides; PCBs; THC; Sediments; Mediterranean; Egypt

Introduction The Egyptian marine environment along the Mediterranean Coast has been subjected to a substantial increase since the last decades of pollution due to a great number of industrial, agricultural, commercial and domestic waste effluents and emissions as well as hazardous substances[1-8]. Among these anthropogenic pollutants, major concern has been directed to persistent organic pollutants (POPs) because they are highly resistant to degradation by biological photolytic and/or chemical means [9-10]. These compounds will be present in the environment for a long time, as their break down are very slowly, even if all new sources were eliminated [11]. Organochlorinated pesticides (OCPs) and polychlorinated biphenyls (PCBs) are two main categories of POPs present as contaminants in the environment. OCPs and PCBs compounds were found widespread in the environmental media, such as in air, water, soil, suspended particulate matter (SPM), sediment, atmosphere organisms and other “biota” (living things, e.g. humans and wildlife), and globally distributed including remote areas where they have never been used [12]. POPs are persistent in the environment, and could have a half-life of years or decades in soil/sediment and several days in the atmosphere. Importantly, POPs have the propensity to enter the gas phase under environmental temperatures. Hence, they may volatilize from soils, vegetation and water bodies into the atmosphere because of their resistance to breakdown reactions in air travel long distances before being redeposit. POPs are used to refer to organic compounds whose presence in the environment in very small amounts can cause significant harm to 1


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ecological systems and/or humans. The increasing use and production (sometimes as by-products) of such compounds over the past half century reflects the nature of life in the developed world and increasing industrialization [12]. These organic compounds, particularly those resistant to degradation, become ubiquitous in the environment, with a truly global distribution [13]. This study was aimed to compare the concentration levels of POPs in bottom sediments of the eastern and western sectors of the Egyptian Mediterranean Sea. Our novelty resides in a unified approach that deals with the interpretation of POPs, permissible levels, comparison, and their mobility to improve action classification, scene context categorization, and semantic inferring. We believe that application goals will largely benefit from this perceptual framework. Materials and Methods Sampling Bottom sediment samples were collected using a stainless steel grab sampler from 18 stations distributed along the Eastern and western parts of the Egyptian Mediterranean Sea during 2010 (Figure 1). Sampling was carried out using Salsabeel Research Vessel. Samples were stored in pre-cleaned aluminum containers and frozen in a deep freezer at -200C until analysis. Procedures THC, Organic carbon, and water content were examined according to Strickland and Parsons [14]. The samples were analyzed for organochlorines following the well-established techniques UNEP/IOC/IAEA [15] and IOC [16]. Sediments were freeze-dried, and their dry/wet ratios were determined. Sediments were then sieved through a stainless steel mesh (250µ m). Each sediment sample (30g) was extracted with 250ml of n-hexane for 8 h using a soxhlet, and then re-extracted for 8h into 250 ml of methylene chloride [17]. Then these extracts were combined and concentrated down to ~ 5ml using rotary evaporation at 35ºC followed by concentration with pure N2 gas stream down to a volume of ~ 1ml.

FIGURE 1. SAMPLING STATIONS OF THE STUDY AREA

Sulphur was removed by shaking the extracts with mercury. The final extracted volume (1ml) for each sediment sample was transferred to the top of a column chromatography. This column was prepared by a slurry packing10g of florisil, followed by 10g of alumina and finally 1g of anhydrous sodium sulfate. Elution was performed using 70ml of n-hexane for PCBs fractions, then a 50ml mixture (70% n-hexane and 30% methylene chloride) for Pesticides (HCHs, TC and DDTs) fractions. Finally, eluted samples were concentrated under a gentle stream of purified nitrogen to about 0.3ml, prior to being injected into the GC/ECD (Thermo Scientific Company) equipped with 63 Ni-electron capture detector (ECD). The instrument was operated in split less mode (3µ L split less injection) with the injection port maintained at 290ºC and the detector maintained at 300ºC. A fused- silica capillary column; Thermo TR-35 MS (30 m length, 0.25 mm i.d., 0.25 μm thickness) with 35% phenyl polysilphenylenesiloxane was used for the quantification. The temperature was programmed from 90˚C - 140˚C with rate of 5 ˚C min−1, then held at 140˚C for 1min, and from 140- 250˚C with rate of 3˚C min−1 and was held at 250˚C for 1min, and from 250- 300˚C with rate of 20˚C·min−1 and was held at 300˚C for 1min. The injector and detector temperatures were set at 280˚C and 310˚C, respectively. Three μL of each sample were injected in the split less mode and the purge time was 1min.

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To control the analytical reliability and assure recovery efficiency and accuracy of the results, four analyses were conducted on organochlorine compounds reference material SRM-2974 a freeze-dried muscle tissue (Mytilus edulis) provided by EIMP-IAEA. Results and Discussion TABLE 1. CONCENTRATION OF CHLORINATED PESTICIDES AND PCBS

(ngg-1) MEASURED IN SEDIMENT SAMPLES COLLECTED

AT DIFFERENT DEPTHS FROM EL MAX TO EL SALLOUM OF THE EGYPTIAN MEDITERRANEAN COAST

Depth

Stations

HCHs

TC

DDTs

(m)

El-Saloum

SidiBraani

El-Shallia

Mrsa Matrouh

El-Room

Fokaa

El-Dabaa

Al-Alameen

El-Hammam

SidiKrir

El-Max

PCBs

TP

Total

THCs

TOC

(ngg , dry weight)

(%)

-1

30

ND

ND

3.10

ND

3.1

3.1

90

1.08

50

ND

ND

3.68

ND

3.68

3.68

40

0.69

100

ND

ND

3.35

ND

3.35

3.35

130

0.38

30

ND

ND

6.16

0.60

6.16

6.76

30

0.60

50

ND

ND

2.78

0.26

2.78

3.04

280

0.40

100

ND

ND

14.28

5.42

14.28

19.70

320

0.86

30

0.02

ND

2.34

28.6

2.36

30.96

50

0.84

50

ND

ND

5.99

1.86

5.99

7.85

1260

0.48

100

ND

ND

ND

ND

ND

ND

1330

0.49

30

ND

ND

2.46

2.24

2.46

4.70

1730

0.51

50

ND

ND

ND

ND

ND

ND

1030

0.49

100

ND

ND

ND

ND

ND

ND

290

0.61

30

ND

0.57

4.51

2.36

5.08

7.44

110

0.61

50

ND

ND

2.62

19.4

2.62

22.02

300

0.60

100

ND

ND

ND

ND

ND

ND

1890

0.58

30

ND

8.3

10.3

ND

18.6

18.6

720

0.55

50

0.12

8.80

10.54

ND

19.50

19.47

980

0.57

100

ND

ND

ND

ND

ND

ND

1100

0.45

30

0.02

ND

2.41

1.24

2.43

3.67

1570

0.45

50

0.17

0.36

5.39

7.51

5.92

13.43

120

0.45

100

ND

0.62

4.71

5.37

5.33

10.7

500

0.69

30

ND

ND

ND

ND

ND

ND

640

0.70

50

ND

ND

1.33

ND

1.33

1.33

9030

0.69

100

ND

ND

4.31

0.33

4.31

4.64

ND

0.69

30

ND

ND

2.60

ND

2.6

2.6

640

0.33

50

ND

ND

2.88

ND

2.88

2.88

1360

0.50

100

ND

ND

8.59

ND

8.59

8.59

290

0.69

30

0.21

0.13

4.72

0.99

5.06

6.05

370

0.69

50

0.18

0.13

4.84

18.50

5.15

23.65

110

0.65

100

ND

1.46

9.84

20.05

11.3

31.35

80

0.20

30

ND

ND

2.32

ND

2.32

2.32

370

0.33

50

ND

ND

ND

ND

ND

ND

1700

0.69

100

ND

ND

15.90

7.17

15.85

23.02

4450

0.57

AV

0.12

2.55

5.46

7.62

6.27

10.96

1030

0.579

Maximum

0.21

8.80

15.90

28.6

19.50

31.35

9030

1.080

Minimum

ND

ND

ND

ND

ND

ND

ND

0.200

AV= average, ND: < Detection Limit, HCHs= α–HCH + β-HCH + ɣ-HCH, TCs = Aldrin + Dieldrin + endrin, DDTs = o,p-DDE + p,p-DDE + o,pDDD + p,p-DDD + o,p-DDT + p,p-DDT, TP = Total Pesticides. THCs = total petroleum hydrocarbons in sediment, TOC% = total organic carbon %.

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The laboratory results showed that recovery efficiency ranged from 92% to 108% with coefficients of variation of 8% - 15% for all organochlorine compounds. The detection limit was estimated to be 0.015 ngg−1 for PCBs and 0.016 ngg−1 for pesticides based on the minimum quantity required for a discernible peak appeared on the chromatogram. Table (1) indicated that concentrations of HCHs in sediment samples of the western part ranged from ND to 0.21ngg-1, with an average of 0.12 ngg-1. The descending order of HCHs isomers was: γ-HCH (0.13 ngg-1) > α-HCH (0.04 ngg-1) > β-HCH (ND). Thus, γ-isomer was the most dominant isomer of HCHs. A maximum 0.21ngg-1 of HCHs was measured at Sidi Krir at 30m depth which is mainly due to the electricity station and the Sumed Company. TCs ranged from ND to 8.8 ngg-1; with an average of 2.55 ngg-1. The presence of an average value of 5.42 ngg-1 of Aldrin and 0.13 ngg-1 of Dieldrin declared that concentrations of Aldrin were higher than those of Dieldrin in most of the sediment samples. This may be attributed to the fact that Aldrin is not converted into its epoxide form; Dieldrin in sediment of the area of study [18], in addition to a probable new source of Aldrin. TABLE 2. CORRELATION MATRIX BETWEEN POPs MEASURED IN SEDIMENT SAMPLES COLLECTED AT DIFFERENT DEPTHS FROM EL MAX TO EL SALLOUM OF THE EGYPTIAN MEDITERRANEAN COAST

30m depth Compound

HCHs

TC

DDTs

PCBs

TP

Total

THCs

TOC

HCHs

1.000

TC

-0.116

1.000

DDTs

0.092

0.816

1.000

PCBs

-0.003

-0.143

-0.173

1.000

TP

0.006

0.948

0.959

-0.161

1.000

Total

0.001

0.384

0.370

0.842

0.396

1.000

THCs

-0.091

0.150

-0.170

-0.258

-0.063

-0.274

1.000

TOC

0.135

-0.116

-0.040

0.339

-0.064

0.280

-0.462

1.000

TP

Total

THCs

TOC

50m depth Compound

HCHs

HCHs

1.000

TC

DDTs

PCBs

TC

0.378

1.000

DDTs

0.593

0.768

1.000

PCBs

0.456

-0.175

0.086

1.000

TP

0.534

0.930

0.950

-0.032

1.000

Total

0.692

0.402

0.391

0.809

0.562

1.000

THCs

-0.279

-0.074

-0.286

-0.302

-0.201

-0.369

1.000

TOC

-0.043

0.006

-0.178

0.150

-0.098

0.067

0.383

1.000

TP

Total

THCs

TOC

100m depth Compound

HCHs

HCHs

1

TC

DDTs

PCBs

TC

0.00

1.000

DDTs

0.00

0.214

1.000

PCBs

0.00

0.895

0.565

1.000

TP

0.00

0.288

0.997

0.623

1.000

Total

0.00

0.662

0.654

0.904

0.897

1.000

THCs

0.00

-0.299

0.305

-0.020

0.274

0.140

1.000

TOC

0.00

-0.549

0.220

-0.449

0.174

-0.158

0.051

1.000

The descending order of TCs compounds was: Aldrin (5.42 ng g-1) > Endrin (0.77 ngg-1) > Dieldrin (0.13 ngg-1) revealing that Aldrin was the most dominant isomer of TCs with a maximum of 8.8 ngg-1 measured at 50 m depth of Fokaa area, reflecting a fresh source of Aldrin rather than its epoxide form, Dieldrin. A maximum concentration of DDTs of 15.9 ngg-1 was measured at El-Max sediments especially at 100m depth. This is mainly due to the impacts of different land-based activities such as drainage water from agriculture and/or many other industries.

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DDTs varied from ND to 15.9ngg-1 with an average value of 5.46 ngg-1. The descending order of DDTs isomers was: o, p-DDT (8.65ng g-1) > o, p-DDE (3.76ngg-1) > p, p-DDE (1.92ngg-1) > o, p-DDD; p, p-DDD and p, p-DDT (ND). Thus, o, p-DDT was the most dominant isomer of DDTs. PCBs varied from ND to 28.6ngg-1 with an average of 7.62ngg-1. PCBs was used as insulating fluids and coolants in electrical equipment and machinery. The descending order of PCBs was: PCB138 (9.40ngg-1) > PCB101 (0.95ngg-1) > PCB28 (0.66ngg-1) > PCB153 (0.33ngg-1) > PCB52, PCB118, PCB135 and PCB180 (ND). This order revealed that PCB138 was more frequently detected in sediment samples of El-Shallia at 30 m depth, El-Room at 50 m depth and Sidi Krir at 50 m and 100m depths more than other PCBs. Sum of TP varied from ND to 19.5ngg-1 with an average of 6.27ngg-1. High values of 19.5, 18.6 and 15.9ngg-1 were observed at Fokaa and El-Max, respectively. The order of decreasing concentrations in sediment samples of Western part was: HCHs: Sidi Krir > El-Dabaa > Fokaa > El-Shallia. TCs: Fokaa > Sidi Krir > El-Dabaa > El-Room. DDTs: Sidi Braani > Sidi Krir > El-Max > Fokaa > El-Hammam > El-Dabaa > El- Salloum > El-Shallia > El-Room > AlAlameen > Mrsa Matrouh. PCBS: Sidi Krir > El-Shallia > El-Room > El-Dabaa > El-Max > Sidi Braani > Mrsa Matrouh > Al-Alameen. TP: Fokaa > Sidi Braani > Sidi Krir > El-Max > El-Hammam > El-Dabaa > El-Salloum > ElShallia > El-Room > Al-Alameen > Mrsa Matrouh. The present study cleared out that TP and DDTs were the major pesticides pollutant followed by PCBs, HCHs and finally TCs compounds in sediment samples of the Western area. THCs in sediments ranged from ND to 9030 ngg-1 with an average of 1030 ngg-1 (Table 1). The maximum concentration of THCs (9030ngg-1) was measured at Al-Alameen sediments especially at 50m depth influenced by the agriculture drainage water. A significant correlation was observed between TOC% with PCBs at 30 m and 50 m depths with r = 0.785 and 0.926, respectively. This is due to the low solubility of PCBs in water and consequently it precipitated until it reached to the bottom water and contaminate the bottom sediments leading to an increase in the TOC%. An insignificant correlation was found between TOC% and TP at three different depths (r = -0.023, 0.059 and 0.106 at 30, 50 and 100m depths, respectively) (Table 2). On contrast, a positive correlation between TOC% and THCs at 50 m depth (r = 0.383) and a significant negative correlation at 30m depth (r = -0.462) were found. This is most probably attributed to the ability of petroleum hydrocarbons to be adsorbed onto bottom sediments. The results presented in Table (3) cleared out that HCHs concentration ranges from ND to 0.19ngg-1 with an average concentration of 0.08 ngg-1. The descending order was: γ–HCH (0.07ng g-1) > α –HCH (0.06ng g-1) > β-HCH (ND). Thus, γ-isomer was the most dominant isomer of HCHs in sediment samples of the Eastern part. Table (3) declares that a maximum concentration of α-HCH (0.19 ng g-1) was measured at Damietta at 50m depth, which is affected by the discharge of Food processing and canning company, paper industry, fertilizers industry and textiles manufacturing and/or agricultural effluents. TCs varied from ND to 0.9 ngg-1 with an average of 0.87 ng g-1. The results of the present study declared also that concentrations of Endrin (average: 0.47 ngg-1) were higher than those of Aldrin (average: 0.40 ng g-1) in most of the sediment samples. The descending order was: Endrin (0.47 ngg-1) > Aldrin (0.40ngg-1) > Dieldrin (ND) revealing that Endrin was the most dominant isomer. The maximum value of Endrin (0.9 ngg-1) was measured at Damietta at 50m depth. Moreover, high concentrations of DDTs (36.3ngg-1) were observed, especially at the same location. DDTs concentrations varied from ND to 36.3ngg-1 with an average value of 5.44ngg-1. The descending order was: o,p-DDE (4.99ngg-1) > p,p-DDE (3.16ngg-1) > o,p-DDD; p, p-DDD; o, pDDT and p, p-DDT (ND). Thus, o,p-DDE was the most dominant isomer of DDTs. DDTs in Abu-Qir Bay sediments reflected the use of DDT in Egypt, especially for agricultural purposes. Low concentrations of DDTs in these sediments compared with concentrations worldwide areas indicated that DDT usage was low in Egypt and Abu-Qir Bay received insignificant inputs of DDTs. The major sources for DDTs in the Abu-Qir Bay sediments are resulted mainly from a number of 22 different factories of food processing and canning, paper industry, fertilizer industry, and textile manufacturing [19-24]. The % of DDE and DDD in most stations were higher than DDTs. Tolosa et al. [25] stated that when the means ratios of DDEs/DDTs and DDDs/DDTs are <1, it is probable that the DDT deposits are recent. Since the corresponding ratios for Abu-Qir Bay sediment are <1, we can conclude that the source of DDT deposits in the area of investigation is new. DDTs are therefore newly released into the area and are most probably present as metabolites i.e aged DDTs, which was applied widely in Egypt for agricultural crops and control of disease vectors, especially on cotton. Although its usage according to Barakat et al. [26] was banned in 1988, its detection along with the detection of its breakdown products in sediments

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is expected because the half-life of DDTs is from 10-20 years. Table (3) indicates also that PCBs varied between ND to 136.2 ngg-1 with an average of 35.77 ngg-1. A maximum concentration of PCBs was observed in Abu Qir sediment at 30m depth with136.2 ngg.-1 PCB congeners were in the following descending order: PCB138 (135.52ng g-1) > PCB180 (2.59 ngg-1) > PCB28 (0.80ngg-1) > PCB 52, PCB 101, PCB 118, PCB135and PCB153 (ND). The maximum concentrations of 37.4 ngg-1 and 20.2 ng g-1 were observed at 50m depth in Damietta area and at 30m depth in Abu Qir area, respectively. The order of decreasing concentrations in sediment samples of the Eastern coast of the Egyptian Mediterranean coast was: HCHs: Damietta >Abu Qir > Sahl Altina. TCs: Damietta. DDTs: Damietta > Abu Qir > Rashid > El-Bourllous > El-Bourllous and Damietta > Sahl Altina > Al-Arish. PCBs: Abu Qir > Damietta> Rashid. TP: Damietta > Abu Qir > El-Bourllous > Sahl Altina > Rashid > El Bourlos and Damietta > Al-Arish. The present study indicated that the order of decreasing concentrations was DDTs > HCHs > PCBs > TCs in the Eastern part. High concentrations of THCs of 3540 ngg-1 were observed in Abu-Qir sediments especially at 50m depth as a result of the agriculture drainage water. THCs ranged from 70 to 3540 ngg-1 with an average of 780 ngg-1. A significant positive correlation (r = 0.933) was observed between TOC% and THCs at 30m; while an insignificant positive correlation (r = 0.068) was observed at 50m depth (Table 4). This may be attributed to the ability of hydrocarbons to be adsorbed onto sediments, especially at low depths. A significant positive correlation was observed between TOC% and TP with r = 0.608 at 30 m depth. In general, HCHs, TCs, DDTS, TP were much higher in sediments of the western sector than those measured in the eastern one. On contrast, PCBs and TOC% were higher in sediment of the Eastern sector than those of the Western one (Tables 2, 4). TABLE 3. CONCENTRATION OF CHLORINATED PESTICIDES AND

PCBs (ng g-1) MEASURED IN SEDIMENT SAMPLES COLLECTED

AT DIFFERENT DEPTHS FROM ABU QIR TO AL ARISH OF THE EGYPTIAN MEDITERRANEAN COAST

Station

Abu Qir

Rashid

El-Bourllous

El-Bourlous and Damietta

Damietta

Sahl Altina

Al-Arish

Depth

HCHs

TC

DDTs

PCBs

TP

Total

THC

TOC

(m)

ng g-1

ng g-1

ng g-1

ng g-1

ng g-1

ng g-1

ng g-1

(%)

30

0.03

ND

20.15

136.20

20.20

156.36

790

1.29

50

ND

ND

1.90

ND

1.90

1.90

3540

0.83

100

ND

ND

1.27

0.50

1.27

1.77

860

1.29

30

ND

ND

5.16

0.62

5.16

5.78

950

1.28

50

ND

ND

1.28

ND

1.28

1.28

2540

1.45

100

ND

ND

0.86

ND

0.86

0.86

190

0.86

30

ND

ND

5.24

ND

5.24

5.24

90

0.37

50

ND

ND

3.09

ND

3.09

3.09

350

1.35

100

ND

ND

1.89

ND

1.89

1.89

90

0.81

30

ND

ND

2.30

ND

2.30

2.30

70

0.15

50

ND

ND

ND

ND

ND

ND

1270

0.52

100

ND

ND

2.87

ND

2.87

2.87

1050

0.24

30

ND

ND

1.15

ND

1.15

1.15

260

0.67

50

0.19

0.90

36.30

5.79

37.40

43.16

820

0.67

100

ND

ND

1.49

ND

1.49

1.49

230

0.68

30

ND

ND

3.82

ND

3.82

3.82

110

0.83

50

0.02

ND

1.10

ND

1.12

1.12

70

0.28

100

ND

ND

2.60

ND

2.60

2.60

90

0.68

30

ND

ND

ND

ND

ND

ND

1650

1.80

50

ND

ND

ND

ND

ND

ND

530

1.80

ND

ND

ND

ND

ND

ND

760

0.40

AV

100

0.08

0.87

5.44

35.77

5.51

13.92

780

0.87

Maximum

0.19

0.90

36.30

136.20

37.40

156.36

3540

1.80

Minimum

ND

ND

ND

ND

ND

ND

70

0.15

AV= average, ND: < Detection Limit, HCHs= α–HCH + β-HCH + ŏ-HCH, TCs= Aldrin + Dieldrin + endrin, DDTs = o,p-DDE + p,p-DDE + o,pDDD + p,p-DDD + o,p-DDT + p,p-DDT. TP: Total Pesticides. THCs= total petroleum hydrocarbons in sediment. TOC% = total organic carbon %.

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Development in Analytical Chemistry (DAC) Volume 3, 2016

TABLE 4. CORRELATION MATRIX BETWEEN

www.seipub.org/dac

POPs MEASURED IN SEDIMENT SAMPLES COLLECTED AT DIFFERENT DEPTHS

FROM ABU QIR TO AL ARISH OF THE EGYPTIAN MEDITERRANEAN COAST

30m depth HCHs

TC

DDTs

PCBs

TP

Total

THCs

TOC

HCHs

1.000

TC

0.000

1.000

DDTs

0.957

0.000

1.000

PCBs

1.000

0.000

0.958

1.000

TP

0.957

0.000

1.000

0.958

1.000

Total

0.999

0.000

0.000

0.999

0.967

1.000

THCs

0.170

0.000

0.041

0.171

0.041

0.156

1.000

TOC

0.288

0.000

0.182

0.289

0.183

0.278

0.933

1.000

TP

Total

THCs

TOC

50m depth HCHs

TC

DDTs

PCBs

HCHs

1.000

TC

0.994

1.000

DDTs

0.991

0.997

1.000

PCBs

0.994

1.000

0.997

1.000

TP

0.991

0.997

1.000

0.997

1.000

Total

0.992

0.998

0.998

0.998

1.000

1.000

THCs

-0.214

-0.167

-0.157

-0.167

-0.157

-0.159

1.000

TOC

-0.313

-0.251

-0.244

-0.251

-0.245

-0.246

0.068

1.000

TP

Total

THCs

TOC

100m depth HCHs

TC

DDTs

PCBs

HCHs

1.000

TC

0.000

1.000

DDTs

0.000

0.000

1.000

PCBs

0.000

0.000

-0.133

1.000

TP

0.000

0.000

1.000

-0.133

1.000

Total

0.000

0.000

0.000

0.058

0.982

1.000

THCs

0.000

0.000

-0.047

0.425

-0.047

0.034

1.000

TOC

0.000

0.000

-0.199

0.757

-0.199

-0.055

-0.239

1.000

Except for the north-western basin of the Mediterranean Sea, Tonghui River Beijing China, Danube Delta, Romania, Western Baltic Sea and Barcelona Offshore, Spain concentrations of PCBs measured in the present study were much lower than concentrations observed in Mediterranean Sea sediments and in other coastal sediments from different geographical areas (Table 5).

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Development in Analytical Chemistry (DAC) Volume 3, 2016

TABLE 5. COMPARISON BETWEEN CONCENTRATIONS OF

PCBs AND ORGANOCHLORINE PESTICIDE (ngg-1)

IN SEDIMENTS OF THE PRESENT STUDY AND THAT MEASURED IN A PREVIOUS WORK

Location

HCHs

TCs

DDTs

PCBs

References

Western Mediterranean, Egypt

<DL-0.21

ND-8.8

ND-15.9

ND-28.60

Present study

Eastern Mediterranean, Egypt

<DL-0.190

<DL-0.90

<DL-36.30

<DL-136.20

Present study

El-Max bay, Egypt

<DL-20.78

<DL-2.47

<DL-123.76

<DL-22.02

[10]

Abu-Qir Bay, Egypt

<DL-1.61

<DL-2.80

<DL-15.86

0.83-99.80

[10]

Eastern Harbour, Egypt

<DL-0.93

<DL-13.76

<DL-86.81

<DL-90.25

[10]

Western Harbour, Egypt

<DL-1.57

<DL-5.15

<DL-62.80

<DL-194.24

[10]

Eastern Harbour, Egypt

0.49-23.38

0.38–6.30

1.28-15.74

3.32-48.35

[27]

Abu-Qir Bay, Egypt

<DL-34.5

<DL-28.52

<DL-128

<DL-22.2

[28]

Lake Burullus, Egypt

1.19-134.99

0.65-70.59

1.95-17.39

4.60-143.67

[9]

Eastern Harbour, Egypt

3.8-16.2

NA

0.5-9.6

NA

[29]

Western coast of Alexandria, Egypt

<DL-2.25

0.001–7.23

0.02-3.19

0.79-64.9

[30]

Alexandria Harbour, Egypt

0.25-6

<DL-7.80

<0.25-885

0.9-1210

[26]

Lake Mariut, Egypt

52.8-143b

NA

318-982c

NA

[31]

El-Max bay, Egypt

16-82

0.1-78

32.3-78

68-164a

[32]

Nile Delta, Egypt

NA

0.1–59

NA

NA

[32]

Mediterranean Sea sediments

NA

NA

0.003-75600

0.03-3938

[33]

Haihe River, China

0.997-1620

NA

<DL-155

<DL-253

[10]

Hanoi, Vietnam

0.2-36

NA

4.4-1100

1.3-384

[27]

Lower Mekong River Basin

NA

NA

0.027-52

0.18-310

[28]

Ariake Bay, Japan

0.78-1.5

0.38-0.4

1.0-1.5

NA

[34]

Tonghui River, Beijing, China

0.06-0.38

<DL-0.08

0.11-3.78

0.78-8.47

[35]

Danube Delta, Romania

0.9-6.8

NA

0.9-17

<DL

[36]

Dahan River, Taiwan

<DL-2.5

<DL-5.8

<DL-3.89

NA

[37]

HoChi Minh City´s Canals, Vietnam

NA

NA

1.8-254

<DL-123

[38]

San Francisco Bay, California, USA

NA

NA

11-30212

NA

[39]

Western Baltic Sea

<DL-1.0

NA

<DL-9.0

<DL-11.4

[40]

San Francisco Bay-Delta Estuary

NA

NA

0.1-8.8

NA

[41]

Casco Bay, Maine, USA

<DL-0.48

NA

<0.2-20

0.4-485

[42]

North west Basin, Mediterranean Sea

NA

NA

1.2-5.8

1.4-5.8

[25]

Barcelona Offshore, Spain

NA

NA

4.9-79.0

4.0-64

[25]

Rhone Prodelta, France

38-230

73–704

NA

NA

[25]

Arabian Sea, West Coast of India

0.85-7.87

0.1-0.27

1.5-25.2

NA

[43]

Amur Bay, Russia

0.2-0.8

NA

1.7-16.3

NA

[44]

Conclusion Concentrations of DDTs in the bay sediments of the present study were lower than concentrations previously measured in Mediterranean Sea coastal sediments, but higher than concentrations observed in the Western coast of Alexandria, Egypt, Ariake Bay, Japan, Tonghui River, Beijing, China and Dahan River, Taiwan (Table 4).

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Development in Analytical Chemistry (DAC) Volume 3, 2016

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Concentrations of HCHs measured in the present study were also generally lower than those previously measured worldwide (Table 4). The descending order was: β-HCH (1.45ng g-1) > α-HCH (0.50 ng g-1) > γ-HCH (0.08 ng g-1) with a maximum of 5.80 ngg-1 measured at El-Max area. TCs varied from 0.09 to 8.12ngg-1 with an average of 3.14 ngg-1. The maximum permissible levels of organochlorine pollutants recommended by the National Academy of Sciences and National Academy of Engineering wt).

[45]

–1

–1

are 1000-5000 ngg for PCBs and 100 ngg for cyclodienes (wet –1

–1

–1

The recommended levels by Swedish Food Regulation are 5000ngg for DDTs, 2000ngg for PCBs and 200ngg for –1

HCB [46]. The US Food and Drug Administration (FDA) has ever announced the tolerance limit of 2000 ngg wet wt for total PCBs in fish and shell fish [45]. The present study indicated that all measured concentrations of pesticides and PCBs either in the Egyptian coast along the Mediterranean Sea were much lower than those reported as permissible levels. REFERENCES

[1]

Wahby S. D. and Shreadah M. A. “The effect of sewage discharge on some chemical characteristics of seawater”. VII Journees Etud Pollutions, Lvcerene. CIESM (1984): 81-90.

[2]

Emara H. I., Shreadah M. A., Maoustafa T. H. and El- Deek M. S. “Effects of Sewage and Industrial Wastes on the Chemical Characterstics of the Eastern harbor and El- Max Bay Waters of Alexandria, Egypt”. Science of the Total Environment (1992): 773-784.

[3]

Said, M. A., El-Deek M. S., Mamoud Th. H. and Shreadah M. A. “Effect of pollution on the hydrochemical characteristics of different water types in El-Mex Bay area west of Alexandria, Egypt”. Acta Adriatic 34(1/2) (1994): 9-19.

[4]

Shreadah M. A. and Abdel Ghani S. “Impacts of Land Based Sources on Water Quality of Abu – Qir Drain, Egypt”. Proceeding of 8thInternational Conference on the Mediterranean Coastal Environment. MEDCOAST 07. E. Ozhan (Editor), 13-17 November 2007, Alexandria, Egypt. (2007): 863 – 872.

[5]

El Deeb M. K. Z., Said T. O., El Naggar M. H., and Shreadah M. A. “Distribution and Sources of Apliphatic and Polycyclic Aromatic Hydrocarbons in Surface Sediments, Fish and Bivalves of Abu Qir Bay”. Bulletin Environmental Contamination Toxicology 78(5) (2007): 373 – 379.

[6]

Emara H. I. and Shreadah M. A. “Distribution and Composition of Aliphatic Aromatic Petroleum Hydrocarbons at some Hot Spots of Alexandria Coastal Water, Egypt”. International Workshop on Integrated Coastal Zone Management (IzmirTurkey 20-22 Oct., (2009): 201-217.

[7]

Fathy S. A. H., Abdel Hamid F. A., Shreadah M. A., Mohamed L. A. and El Gazar M. “Application of Principal Component Analysis for Developing Water Quality Index for Selected Coastal Areas of Alexandria Egypt”. Recourses and Environment Journal 2 (6) (2012): 297-305.

[8]

Shreadah M. A., Said T. O., Othman I. M., Fathallah E. M. I. and Mahmoud M. E. “Organochlorines in Seawater from Egyptian Mediterranean Coast of Alexandria”. Development in Analytical Chemistry 1 (2014): 19-24.

[9]

Said T. O., El Moselhy M. K., Rashad M. A. and Shreadah M. A. “Organochlorine Contaminants in Water, Sedi-ment and Fish of Lake Burullus, Egyptian Mediterranean Sea”. Bulletin Environmental Contamination Toxicology 81(2). (2008): 136-146.

[10] Shreadah M. A., Said T. O., Othman I. M., Fathallah E. M. I. and Mahmoud M. E. “Polychlorinated biphenyls and chlorinated pesticides in Sediments along the Semi-closed Areas of Alexandria, Egypt”. Journal of Environmental Protection 3(2) (2012): 141- 149. [11] Chu W., Wong M. and Zhang J. “Accumulation, distribution and transformation of DDT and PCBs by Phragmitesaustralis and Oryza sativa L.: II. Enzyme study”. Environ. Geochem. Health 28(1-2) (2006): 169-81. [12] Koziol S. A. and Pudykiewicz A. J. “Global-scale environmental transport of persistent organic pollutants”. Chemosphere 45 (2001): 1181-1200.

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[13] Warren N., AllanaI. J., Carter J. E., House W. A. and Parker A. “Pesticides and other micro-organic contaminants in freshwater sedimentary environments: A review”. Applied Geochemistry 18 (2003): 159-194. [14] Strickland, J.D.H and Parsons, T.R. “A Practical handbook of seawater analysis; bulletin 167 (second edition); Canada (1972). [15] UNEP/IOC/IAEA. “Sampling of selected marine organisms and sample preparation for the analysis of chlorinated hydrocarbons”. Reference methods for marine pollution studies no. 12, revision 2. Nairobi: United Nations Environment Program 17 (1991). [16] IOC “Chlorinated biphenyls in open ocean waters: sampling, extraction, clean-up and instrumental determination”. Manual and guides no.27. Pairs: Intergovernmental oceanographic commission, UNESCO36 (1993). [17] Villeneuve J. P., Carvalho F. P. and Fowler S. W., Cattini C. “Levels and trends of PCBs, chlorinated pesticides and petroleum hydrocarbons in mussels from the NW Mediterranean Coast: comparison of concentrations in 1973/1974 and 1988/1989”. Sci. Total Environ. 2371(238) (1999): 57–65. [18] CCME (Canadian Council of Ministers of the Environment). “Canadian Water Quality Guidelines”. Prepared by the Task Force on Water Quality Guidelines of the Canadian Council of Ministers of the Environment, Eco-Health Branch, Ottawa, Ontario, Canada (1992). [19] Tayel F. R. and Shreadah M. A. “The distribution of Alkalinity, some major cations and their chlorinity ratios in the seawater of Abu-Qir Bay”. Bull. Fac. Sci. Alex. Univ. 32(A) (1992): 176-194. [20] Shreadah M. A. and Tayel F. R. (1992).Impacts of industrial, sewage and agricultural effluents on Lake Edku and Abu-Qir Bay. Bull. Fac. Sci., Alex. Univ., 32(A), 103-155. [21] Shreadah M. A. and Hassan S. “Distribution and Speciation of Some Heavy Metals in an Industrial Waste Water Discharge Area, Egypt”. Ass. Mod. & Simul. Enterpr. (AMSE), Mod. C., (France) 66 (5) (2005): 31-42. [22] Said T. O., Farag R. S., Younis A. M. and Shreadah M. A. “Organotin Species in Fish and Bivalves samples collected from the Egyptian Mediterranean Coast of Alexandria, Egypt”. Bull. Environ. Contam. Toxicol. 77 (3) (2006): 451-458. [23] Shreadah M. A., Said T. O., Abdel Moniem M. I., Fathallah E. M. I. and Mahmoud M. E. “PAHs in Sediments along the Semi-closed Areas of Alexandria, Egypt”. Journal of Environmental Protection 2(6) (2011): 700- 709. [24] Abdel Salam S., El Zokm G., Shobier A., Othman T. and Shreadah M. A. “Metal Pollution in Surface Sediments of Abu Qir Bay and the Eastern Harbour of Alexandria, Egypt”. Egyptian Journal Aquatic Research 39 (2013): 1-12. [25] Tolosa I., Bayona J. M. and Albaiges J. “Spatial and Temporal Distribution, Fluxes and Budgets of Organochlorinated Compounds in Northwest Mediterranean Sediments”. Environmental Science and Technology 29(10) (1995): 2519-2527. [26] Barakat A. O., Moonkoo K., Yoarong Q. and Wade T. L. “Organochlorine Pesticides and PCB Residues in Sediments of Alexandria Harbour, Egypt”. Marine Pollution Bulletin 44 (12) (2002): 1421-1434. [27] Emara H. I., Said T. O., El Naggar N. A. and Shreadah M. A. “Aliphatic and polycyclic hydrocarbon compounds as chemical markers for pollution sources in relation to physico-chemical characteristics of the Eastern Harbour (Egyptian Mediterranean Sea”. Egyptian Journal Aquatic Research 34(3) (2008): 1- 19. [28] Howell N. L., Suarez M. P., Rifai H. S. and Koenig L. “Concentrations of Polychlorinated Biphenyls (PCBs) in Water, Sediment, and Aquatic Biota in the Houston Ship Channel, Texas”. Chemosphere 70 (4) (2008): 593-606. [29] Morsy H. A. and Abdallah M. A. “Assessment and Distribution of Organic Chlorine Pesticides (HCHs) and (DDTs) in Marine Environment of Eastern Harbour, Alexandria, Egypt”. Egyptian Journal of Aquatic Research 32(2) (2006): 83-94. [30] Said T. O. “Determination of Persistent Organic Pollutants in Sediment and Fish of the Western Coast of Alexandria, Egypt”. Chemistry and Ecology 23(4) (2007): 289-302. [31] Abo-Elamayem M., Saad M. A. and EL-Sebae A. H. “Water Pollution with Organochlorine Pesticides in Egyptian Lakes. Proceedings of the International Egyptian-German Seminar on Environmental Protection from Hazardus of Pesticides, Alexandria”. 24-29 March (1979): 94-108.

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[32] Abd-Allah A. M. and Abbas M. M. “Residue Levels of Organochlorine Pollutants in the Alexandria Region, Egypt”. Toxicology and Environmental Chemistry 41 (3-4) (1994): 239-247. [33] Guitierrez A. G., Garnacho E., Bayona J. M. and Al-baiges J. “Screening Ecological Risk Assessment of Persistent Organic Pollutants in Mediterranean Sea Sediments”. Environment International 33(7) (2007): 867-876. [34] Kim Y. S., Eun H., KataseT. and Fujiwara H. “Vertical Distribution of Persistent Organic Pollutants (POPs) Caused from Organochlorine Pesticides in a Sediment core Taken from Ariake Bay, Japan”. Chemosphere 67(3) (2007): 456-463. [35] Zhang Z., Huang J., Yu G. and Hong H. “Occurrence of PAHs, PCBs and Organochlorine Pesticides in the Tongui River of Beijing, China”. Environment Pollution 130(2) (2004): 249-261. [36] Covaci A., Gheorghe A., Hulea O. and Schepens P. “Levels and Distribution of Organochlorine Pesticides. Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Sediments and Biota from the Danube Delta”. Romania Environmental Pollution 140 (1) (2006): 136-149. [37] Doong R. A., Sun Y. C., Liao P. L., Peng C. K. and Wu S. C. “Distribution and Fate of Organochlorine Pesticides Residues in Sediments from the Selected Rivers in Taiwan”. Chemosphere 48(2) (2002): 237-246. [38] Phuong P. K., Son C. P. N., Sauvain J. J. and Tarradellas J. “Contamination by PCBs, DDTs and Heavy Metals in Sediments of Ho Chi City’s Canals, Viet Nam”. Bulletin of Environmental Contaminants and Toxicology 60(3) (1998): 347-354. [39] Pereira W. E., Domagalski J. L., Hostettler F. D., Brown L. R. and Rapp J. B. “Occurrence and Accumulation of Pesticides and Organic Contaminants in River Sediments, Water and Clam Tissues from the San Joaquin River and Tributaries, California”. Environmental Toxicology and Chemistry 15(2) (1996): 172-180. [40] Dannenberger D. “Chlorinated Micro contaminants in Sur-face Sediments of the Baltic Sea-Investigation in the Belt Sea, the Arkona Sea and the Pomeranian Bight”. Marine Pollution Bulletin 32(11) (1996): 772-781. [41] Periera W. E., Hostettler F. D., Cashman J. R. and Nishioka R. S. “Occurrence and Distribution of Organochlorine Compounds in Sediments and Livers of Striped Bass (Morone Saxatilis) from the San Francisco Bay-Delta Estuary”. Marine Pollution Bulletin 28(7) (1994): 434-441. [42] Kennicutt M. C., Wade T. L., Presley B. J., Requejo A. G., Brooks J. M. and Denoux G. I. “Sediment Contaminants in Casco Bay, Maine: Inventories, Sources and Potential for Biological Impact”. Environmental Science and Technology 28(1) (1994): 115. [43] Sarkar A., Nagarajan R., Chaphadkar S., Pal S. and Singbal Y. S. “Contamination of Organochlorine Pesticides in Sediments from the Arabian Sea along the West Coast of India”. Water Resources 31(2) (1997): 195-200. [44] Vashchenko M. A., SyasinaI. G. and Zhadan P. M. “DDT and Hexachlorocyclohexane in Bottom Sediments and the Liver of Barfin Plaice Pleuronectes Pinnifasciatus from Amur Bay (Peter the Great Bay, the Sea of Japan)”. Russian Journal of Ecology, 36(1) (2005): 57-61. [45] National Academy of Sciences and National Academy of Engineering, Ecol Research Services Environmental. NAS-NAE, Washington, DC, 1972. [46] SFR, Foreign Substances in Food, The National Food Administration SLVFS: 1, Swedish Food Regulation, Uppsala, 1983.

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