Development in Analytical Chemistry (DAC) Volume 3, 2016
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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
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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
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