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Organochlorine pesticides and PCB residues in sediments
of Alexandria Harbour, Egypt
Abstract
wastewater disposal (both untreated sewage and indus- trial) which are currently
discharged to the harbour and the Mediterranean Sea directly via El-Mex Pump
Sta- tion and through numerous storm and combined sewer outfalls located within
the harbour area. The harbour is also heavily influenced by agricultural run off
from the El-Mahmoudiya and Noubaria canals.
OC pesticides have been used substantially in Egypt for the control of
agricultural pests. Although the usage of PCBs in Egypt is not known, the past
use of these substances in transformers, electrical equipments, ship painting
and other industrial has been common. The objectives of this investigation were to
assess the oc- currence and distribution of persistent OC pesticides and PCB
residues in sediments of Alexandria Harbour and to evaluate their potential
effects on aquatic or- ganisms.
Twenty three sediment samples were collected within
the harbour (Fig. 1) to cover regions affected by intense activities, freshwater
input, wastewater outfalls as well as relatively pristine areas. In
addition, two reference
sediment samples, collected from Stanley Bay and Montazah beach located along the
coast of Alexandria city were analyzed with this sample set.
Surface sediment samples were taken with an Ekman grab sampler. Collected samples
were frozen on dry ice and transferred to the laboratory for processing. Sample
preparation and analysis methods have been described in Wade et al. (1988).
Briefly, about 10 g of freeze-dried sediment was Soxhlet-extracted with
methylene chlo- ride. Concentrated extracts were fractionated with alu-
mina/silica gel (80–100 mesh) column chromatography. Target analytes were eluted
from the column with 50 ml of pentane (aliphatic fraction) and 200 ml
of 1:1 pentane–dichloromethane (aromatic/PCB/pesticide frac- tion). The fractions
were then concentrated to 1 ml using Kuderna–Danish tubes heated in a water bath
at 60 C. The surrogates dibromooctafluorobiphenyl (DBOFB), PCB103, and PCB198 were
added to the samples prior to extraction.
The chlorinated pesticides and PCBs were analyzed by gas chromatography in the
spitless mode using an electron capture detector (ECD). A 30 m 0:32 mm i.d.
fused silica column with DB-5 bonded phase (JW Sci- entific, Inc.) provided
component separations. The chromatographic conditions for the pesticide–PCB
analysis were 100 C for 1 min, then 5 C min 1 to 250
C, hold for 1 min, and then 10 C min 1 to 300 C and
a final hold of 5 min. The internal standard, tetrachloro- m-xylene (TCMX), was
added prior to GC/ECD anal- ysis to monitor the recovery of surrogate. A
standard solution containing only PCBs was used to confirm the identification of
each PCB congener. The QA/QC pro- cedures included analysis of matrix spikes,
duplicates, laboratory blanks and certified reference material (Wade and Cantillo,
1994). For data presentation all concen- trations below the method detection
limits were assigned a value of 0.25 ng/g (dry weight) as the estimated aver- age
detection limit. The instrument was calibrated by injection of the
standards component mixture at five different concentrations, prior to analysis of
the samples.
The following compounds were included in this study:
2,40-DDT (2,40-dichloro-diphenyltrichloroethane), 4,40- DDT and their
degradation products 2,40-DDD (2,40- dichloro-diphenyldichloroethane), 4,40-DDD,
2,40-DDE (2,40-dichlorodiphenyltrichloroethene) and 4,40-DDE, chlordane related
compounds, chlorinated benzenes (CBs), hexachlorocyclohexanes (HCHs), aldrin,
dieldrin, endrin, chloropyrifos, endosulfan, mirex and pentachloro-
anisole. For simplicity, the following nomenclature will be used in this paper:
DDTs for the sum of 2,40- and 4,40- DDT; DDDs for the sum of 2,40- and 4,40-DDD;
DDEs for the sum of 2,40- and 4,40-DDE; total DDTs for the sum of DDTs,
DDDs, and DDEs; total chlordane for the sum of heptachlor and its epoxide, oxy-,
c, and a- chlordane, and cis- and trans-nonachlor; CBs for the sum
Table 1
Concentrations (ng/g, dry wt) of PCBs and chlorinated pesticides in sediments of
Alexandria Harbour, Egypt
Station no.
Sample location PCBsa PDDTsb Chlordanec HCBsd
CHse Aldrin Dieldrin Endrin Chloro-
pyrifos
Mirex Endo- sulfan
1 Arsenal Basin 1211 885 44
2.4 0.8 <dlf <dl <dl 13
0.4 22
2 Arsenal Basin 114 21 8.7
0.5 0.4 <dl <dl <dl 1.5 <dl
2.1
3 Arsenal Basin 280 189 12
1.5 0.8 <dl <dl <dl 7.9 <dl
1.8
4 Boathouse 349 27 9.3
2.9 0.9 <dl 1.4 0.1 1.2
<dl 5.8
5 El-Mahmudiya
Quay
6 El-Mahmudiya
Quay
7 El-Mahmudiya
Quay
8 El-Mahmudiya
Quay
9 Ship Pass (inner harbour)
10 Marine Ship Lift and floating dry dock
11 Ship Pass (outer harbor)
339 58 7.6 <dl 0.3 2.8
0.0 2.1 <dl <dl <dl
Although the observed trends in PCB congeners composition were similar in some of
the samples (e.g. between S-1 and S-3, and between S-5, S-7 and S-10, Fig.
3) the distribution patterns are, in general, different among the sediments of
this study area (Fig. 3), which may indicate different input sources. The usage
of PCB in Egypt is not well established, but the use of PCBs in transformers,
electrical equipment, and other industries is common. The results from this
study suggest that, owing to their persistence, PCBs contamination are widespread
at Alexandria Harbour.
Concentrations of total DDTs varied from <0.25 to
885 ng/g (dry weight) with a median concentration of
87 92 ng/g (Table 1). DDTs (2; 40 þ 4; 40-DDT) and/or their breakdown products
were detected in all of the samples inside the harbour. Samples from
stations 22 and 23, which are located in outside the harbour (Fig.
1), and reference samples contained no detectable
DDTs.
Similar to PCBs, high concentrations of total DDTs were encountered at locations
within the inner harbour and at sites located near ship activities and storm sewer
outfalls (stations 1, 3, 8, 14 and 18; 100–885 ng/g). Other sites with elevated
concentrations of total DDTs (58–66 ng/g) are stations 5, 12, and 13. The
total DDTs con- centrations were in the range from 10 to 40 ng/g (aver- age of 26
7 ng/g) in the remaining samples. The high concentrations of total DDTs and
related compounds in these sediments indicate that DDT usage was heavy and the
harbour has received significant inputs of DDTs.
DDTs undergoes degradation to DDDs and DDEs in natural environment by chemical
and biological pro- cesses (Wedemeyer, 1967; Baxtor, 1990). Fig. 4 shows DDTs
and their metabolites as a percentage of total DDTs at the different
sampling sites. Over 85% of the total DDTs in sediments from stations 1, 3,
and 6 was
present as DDTs and particularly as 2,40-DDT. The dominance of DDTs in the
sediment indicates slow de- gradation of DDTs or recent inputs of fresh DDT
at these locations (Tavares et al., 1999; Yuan et al., 2001). Station 12 also
showed significant concentrations of DDTs (38%).
DDDs and DDEs were predominant in the remaining samples, with DDDs and DDEs
representing over 75% of total DDTs. DDTs were, therefore, not newly re-
leased into those locations and were mainly present as metabolites. DDDs
accounted for the majority of DDT related compounds at these locations (Fig. 4).
The dominance of DDDs over DDEs in these sediments in- dicates reductive
dechlorination of DDTs to DDDs under anaerobic conditions (Wedemeyer, 1967;
Baxtor,
1990). This observation is in agreement with the fact that Alexandria
Harbour is a semi-closed bay with re- stricted water exchange with the open ocean
and the sediments were anoxic.
DDT was widely used in Egypt on a variety of agri- cultural crops and for the
control of disease vectors. The largest agricultural use of DDT has been on
cotton, which accounted for more than 80% of the use before its ban. Although
its usage was banned in 1988, its detec- tion, along with detection of its
breakdown products (i.e., DDEs þ DDDs), in sediments is expected because the
reported environmental half-life of DDTs is esti- mated as 10–20 years
(Woodwell et al., 1971; Sericano et al., 1990).
Sediment concentrations of total chlordane ranged from <0.25 to 44 ng/g (dry
weight) with a median concentration of 6 ng/g (Table 1). a-Chlordane was the major
chlordane isomer in all the samples. This is ex- pected since a-chlordane is one
of the main components of technical grade chlordane (Dearth and Hites, 1991).
Similar to the distribution of DDT and its metabolites,
Baseline / Marine Pollution Bulletin 44 (2002) 1421–1434
1431
Fig. 3. Relative abundance of selected PCB congeners having the highest average
concentrations in representative sediment samples from Alexandria
Harbour.
high concentrations of total chlordane were encountered in the inner harbour area
(Stations 1–8, Fig. 1) with the highest residue concentrations (44 ng/g) found at
station
1 in the Arsenal Basin. These sites in the inner harbour also had the highest
concentrations of total PCBs and total DDTs. In contrast to stations 1–8,
chlordane concentrations at the remaining sites in the outer har- bour area were
low (less than 4 ng/g), indicating that the contamination of sediments in the outer
Alexandria Harbour by chlordane related compounds was minimal. In addition,
chlordanes were not detected at stations 22 and 23 and the reference stations.
The CBs, such as 1,2,4,5-TCB, 1,2,3,4-TCB, and PeCB, may be metabolites of
the commercial pesticide HCB or other CBs, e.g. pentachlorophenol (Wang and
Jones, 1994). The concentrations of these CBs and HCH were either below detection
limits or low (Table 1).
Highest concentrations of chloropyrifos and endo- sulfan II were found in the
inner harbour region. Chloropyrifos (<0.25–51) was detected in 26% of the
samples with highest levels at station 8, while endosulfan II (<0.25–22) was
detected in 44% of the samples with highest concentrations at the Arsenal
basin (station
1). Chloropyrifosis highly toxic to molluscs, fish and
1432 Baseline /
Marine Pollution Bulletin 44 (2002) 1421–1434
detected in 30% of the samples analyzed, dieldrin (<0.25–3.1 ng/g) in 35% samples
and endrin (<0.25–6.7 ng/g) in 39% samples. Other OC pesticides such as mirex and
pentachloroanisole were near or below the method detection limit.
Long et al. (1995) conducted an extensive review of articles that provide both
concentrations of contami- nants in sediment and observed biological effects. They
derived consensus values by considering data from all of the studies reviewed and
ranked from low to high. A
10th and 50th percentile were then determined and were designated effects range
low (ER-L) and effects range median (ER-M). The ER-L and ER-M values for total
Fig. 4. Percentage of total DDTs represented by DDTs and their metabolites DDDs
and DDEs in sediments from Alexandria Harbour.
crustaceans (Briggs, 1992) and it has been reported in Biota samples (Pait
et al., 1992). Endosulfan was reported to be responsible for more fish deaths
in US estuaries and coastal areas between 1980 and 1989 than any currently used
pesticide and was ranked as the most hazardous of the currently used
pesticides considered (Pait et al., 1992).
Aldrin, dieldrin and endrin were found at low con- centrations in several
samples, with highest results found in sediments near El-Mahmoudiya Quay
stations (sta- tions 5, 7 and 8, Table 1). Aldrin (<0.25–4.6 ng/g) was
DDT are 3 and 350 ng/g, for PCBs are 50 and 400 ng/g, and for chlordanes are 0.5
and 6 ng/g, respectively.
Total PCB concentrations in the sediments from nearly all the sites except
for the reference sites and the two sites located in the open ocean were above the
ER-L value and the total PCB concentrations in the samples from five sites
(stations 1, 6, 8, 12, and 14) were above the ER-M value that could elicit toxic
response for most benthic organism. In addition, the DDT concentrations in
samples from all the sites except for the reference sites and sample from the
open ocean (station 22 and 23) were above the ER-L value (Table 1).
Chlordane con- centration exceeded the ER-M at six sites and ER-L at
13 sites. Dieldrin and Endrin concentrations exceeded
Table 2
Comparison of PCB and OC pesticide concentrations (ng/g dry wt) in the sediments
from other locations
Location Year PCBs
Total DDT Chlordane HCHs References
Mediterranean Sea
Northwest Basin 1990 1.4–5.8
1.2–5.8 NA NA Tolosa et al.
(1995)
Open sea 1983 0.8
0.047 NA 0.18a Burns
and Villeneuve (1987)
Coastal
Barcelona Offshore 1990 4.0–64
4.9–79 NA NA Tolosa et al.
(1995) Casco Bay, Maine, USA 1991 0.4–485
<0.2–20 <0.25–4.91 <0.07–0.48a Kennicutt et al. (1994)
Abu-Quir Bay, Egypt 1989–1991 53–231 44–
223 NA 16–82 Abdallah (1992),
Abdallah and
Abbas (1994)
El-Mex Bay, Egypt 1989–1991 68–164
32.3–87 NA 16–53 Abdallah (1992);
Abdallah and
Abbas (1994)
Harbours
Victoria Harbour, Hong Kong 1992 3.2–27 1.4–30
NA n.d.–2.3 Connell et al. (1998) Xiamen Harbour, PRC
1993 0.05–7.2 4.5–311 NA 0.14–
1.12 Hong et al. (1995) Manukkau Harbour, New Zealand
0.5–14.2 1.2–2.3 0.9–5.3 0.1–2.0 Fox et
al. (1988) Alexandria Harbour, Egypt 1998 0.9–1211
<0.25–885 <0.25–44 0.25–6.0 This study
NA: no data available. n.d.: not detected.
a Reported as c-lindane.
Baseline / Marine Pollution Bulletin 44 (2002) 1421–1434
1433
the ER-L at eight and nine sites, respectively. The high concentrations of PCBs,
DDTs, chlordane, dieldrin and endrin in the sediments of Alexandria Harbour,
there- fore, could cause detrimental biological effects for the benthic
organisms (Long and Morgan, 1990).
Compared to concentrations reported in coastal en- vironments from other parts of
the world, PCB con- centrations in surface sediments of Alexandria Harbour were
one to two orders of magnitude higher than most of the riverine/estuaries
systems (Table 2). However, the concentration of total PCBs in the severely
impacted areas from the US and Spain were higher than the Al- exandria
Harbour area. Similarly, concentrations of total DDT were higher than
other harbours and river- ine/estuary systems except in some severely
contami- nated locations, such as in the NW Mediterranean sediments from the Rhone
Prodelta, Spain. (Table 2). Chlordane concentrations were also higher than those
reported from other locations except for the sediments from Washington, DC
area. In comparison, the con- tamination of sediments in the Alexandria
Harbour by PCBs, DDTs and chlordanes appeared to be high on a worldwide basis.
In order to determine the sources of the observed contaminants, intense localized
sampling and analysis of effluents and runoff patterns would be needed. To
determine sediments quality, bioassays of sediments at suspected sites should
be conducted to directly assess the potential for biological impacts.
Acknowledgements
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