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Oladele Olutona]
On: 24 June 2014, At: 21:25
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Obayomi-Davies
a
To cite this article: Godwin Oladele Olutona, Solomon Ayanwuyi Ayano & Oludayo Obayomi-Davies
(2014) Organochlorine pesticide in water and bottom sediment from Aiba Reservoir (Southwestern
Nigeria), Chemistry and Ecology, 30:6, 513-531, DOI: 10.1080/02757540.2013.877002
To link to this article: http://dx.doi.org/10.1080/02757540.2013.877002
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1.
Introduction
The increasing needs of the food production have resulted in overuse of fertilisers and pesticides,
which enter aquatic systems, following aerial application or runoff inputs and reduce quality of
water.[1] As pesticides runoff constitute a significant contribution to aquatic pollution, their use
in agriculture is under constant screening to ensure non-target animals welfare, leading to the
ban and restriction of a large number of products.[2]
In water bodies, many of the persistent organic pollutants such as organochlorine pesticides
(OCPs) and trace metals have been predominantly transported in association with suspended
particulate matter. The suspended particles and the semi-bound pollutants accumulate in the
region of low turbulence, such as groyne fields, harbours and river reservoir.[3] This has resulted
in pollution of bottom sediment.
Within the sediments, usually with anoxic conditions, many contaminants are strongly bound to
the solid phase. Therefore, pore water concentrations, mobility and bioavailability except through
particle ingestion of most pollutants are rather low.[3] However, the possible erosion during
flood events leads to the transfer of contaminated sediments to the oxidised water column, which
generally enhances bioavailability and toxicity of pollutants.[4,5]
Corresponding
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514
Residues of OCPs in sediments and aquatic biota have been an environmental concern since
the 1960s.[6] Owing to their toxicity, persistence, tendency to accumulate in biota, and adverse
impacts on wildlife, the majority of OCP were banned in the US during the 1970s.[7] Yet more
than 20 years later, residue of DDT and other OCP continue to be detected in water sediments
and aquatic biota throughout the world.[8] The mechanism underlying the toxicity of organochlorine involves the induction of enzyme activity through free radicals, ultimately affecting the
immune response, the reproductive and neurological systems, lipid metabolism, and the transport
of vitamins and glucose. In addition, some of these compounds are mutagenic, teratogenic and carcinogenic not only in humans, but also in biotic communities with different levels of sensitivity.[9]
The persistent nature of OCPs in the environment may pose the problem of toxicity to animals
and human through air, water and food intake.[10] Furthermore, because of their chemical stability, long-range atmospheric, lipophilicity and persistence, these chemicals tend to bioaccumulate
and biomagnify in the food chains and persist in the environment for many years, representing
a definite health hazard for both wildlife and human.[11,12] Owing to the hydrophobic nature
of OCPs, these persistent organic pollutant (POP) present in aquatic system have high affinity to
bind to suspended particles and tendency of long-term vertical transport of organic contaminant
from surface waters to the deep sea floor.[13,14] OCPs have the potential to affect development,
reproduction and behaviour of fish and wildlife.[15]
Long-term chronic exposure to OCPs and poly chlorinated biphenyls (PCBs) has been correlated with severe injury to the nervous, endocrine, reproductive and immune systems in birds, fish
and mammals.[16] Ecological effects of OCPs include interference with reproductive success of
organisms high on food chain especially fish eating birds such as osprey, pelicans, falcons and
eagles.[17] DDT has been reported to have esterogenic and enzymes inducing properties.[17]
The adverse effects of DDT demonstrated in experimental animals include infertility,[18] a
decrease in the number of planted ova,[19] intrauterine growth retardation,[20] neurological
developmental disorders [21] and mortality.[22] Isomers of DDT (ortho and para) compete with
estradiol for binding to oestrogen receptors in uterine cytostol therefore causing changes in steroid
metabolism and thereby alter the ability of birds to mobilise calcium to produce strong egg
shell.[23]
Generally, the greatest source of human exposure to OCP is daily intake via food
consumption,[24] in particular, the consumption of sea food from contaminated areas.[25] Moreover, several studies have recently demonstrated a clear correlation between the frequency of fish
consumption and the levels of organochlorine in human tissues, serum and milk.[26,27] Over
90% of the body burden of DDT in the general population is derived from food, particularly fish
and other fatty foods of animal origin.[28] In Nigeria, it has been reported that 116 students of
a school in Doma, Gombe state fell ill and were hospitalised after eating cowpea contaminated
by pesticide.[29] Shaibu [30] reported that two children and 112 people were hospitalised after
eating cowpea treated with pesticide in Cross River state, Nigeria. In 2010, it was reported that
20 fast food outlets were closed in Nigeria because of fatalities traced to pesticide residue in their
products.[31]
Aiba reservoir, the second oldest impoundment of Osun River Basin came into full operation
in 1957 and was created primarily for the provision of portable water with fisheries development as an ancillary benefit to Iwo town and the surrounding communities.[32,33] Recently,
there has been a sharp rise in the development of Iwo as evidenced by the establishment of a
private University and Polytechnic, proliferation of banking industry as well as establishment of
telecommunication industry. This has led to an increase in the population of Iwo. Construction of
residential houses is encroaching into the north-eastern part of the reservoir. Anthropogenic practices in and around the reservoir include intense fishing activity, agricultural practices, washing
of domestic wares and automobiles, bathing and fetching of water for construction and domestic
purposes.[34]
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515
Organochlorine pesticide levels in water, sediment and soil have been studied by various authors.
In Iwo however, no published work has been reported in this regard. Hence, the objective of this
paper is to give a pilot screening of OCP levels in water and sediment of Aiba reservoir and to
provide a preliminary insight into the accumulation pattern based on the matrices considered in
this study.
2.
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516
Figure 1.
spillway area, the lower reaches of the reservoir. In this area, spiritual bath, domestic washing as
well as washing of motor cycle by cyclists are very common features of this area.
Sampling took place in November and December 2012. Samples of bottom sediment for each
four locations were collected in triplicates with grab sampler at a depth of 0 to 10 cm. The samples
collected were stored in clean aluminium foils and preserved in a refrigerator at about 4 C prior
analysis. The samples were air-dried at ambient temperature in an inert surface in a ventilated
cupboard to minimise cross contamination of samples with the atmospheric particulate. Sediment
samples from each location were made into composite representative samples sieved through a
stainless steel 2 mm pore size to get rid of pebbles and large particles.
The water sample was collected in a sterilised 2.5 L Winchester bottles for each of the four
locations. Water collected from each spot was used to rinse the bottles three times before sampling
was done. Alteration of the organics due to microbial activities was prevented by acidification of
the samples to pH 2 by adding concentrated HNO3 immediately after collection.
2.5.
Extraction procedure
Liquid-liquid extraction was used to extract OCP from the water samples. About 500 mL of
the water sample was measured and poured into a 1 L separatory funnel then extracted with
10 mL (three portions) of dichloromethane by shaking vigorously for 30 min for each of the
triplicate extraction. The extracts were then combined, dried with anhydrous sodium sulfate and
concentrated to about 2 mL under a stream of nitrogen gas of 99.99% purity.
The sediment samples were extracted by soxhlet extraction method (USEPA method 3540).
A dried, sieved sediment sample (20 g) was weighed into extraction thimble and placed in a
soxhlet extractor. Extraction was done for about 10 h using triply distilled dichloromethane at
a temperature of about 40 C. The extract was concentrated by distilling off part of the solvent.
The concentrated extract was cooled to room temperature and then concentrated further to about
2 mL under a stream of nitrogen gas of 99.99% purity. The reduced extract was preserved for
chromatographic clean-up prior to GC-ECD analysis.
517
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GC-ECD analysis
Gas chromatography from Institute of Oceanography, Victoria Island Lagos was used in determining the presence and levels of organochlorine in both the surface water and bottom sediment
of Aiba reservoir. The dried eluate above was reconstituted with 1 mL n-hexane and 0.5 mL of
20 ppm of the internal standard. Qualitative and quantitative analysis of the OCPs were carried
out with the aid of HP GC 5890 series 11 coupled with detector (ECD). The levels of OCP were
calculated from the relationship given by Harris (1999) as:
Ax
=F
[x]
As
[s]
where Ax = area of analytical signal; As = area of internal standard signal; F = response factor;
[x] = concentration of analyte and [s] = concentration of internal standard. The GC was under
the following conditions: injector temperature of 250 C; detector temperature, 300 C; (held for
5 min); capillary column, Zebron ZB-1701. 30 m 0.25 mmi.d 0.25 m film thickness; oven
temperature programme, 280 C starting from 50 C for 1 min and continued at 20 C/150 C and
at 5 C/min to 280 C held for 4 min; injected sample volume 1 L; splitless mode; carrier gas N2
at 30 mL/min; and splitless flow rate, 19.6 mL/min. identification of OCP was by comparison of
retention times of the peaks with those of standard OCP compounds.
2.8. Quality control measure
Since no standard pesticide reference materials were available to us during the course of this study,
recovery analysis was performed in order to ascertain the efficiency of the analytical procedures
using standard methods. 500 mL aliquot of ultra-pure water was measured into 1000 mL separatory
funnel and acidified with concentrated HNO3 to pH 2. This was spiked with 10 mL of 1000 ppm
standard mixture consisting 20 different organochlorine pesticides. The mixture was extracted
and clean-up following the procedure outlined above.
Two 20 g portions each of dried sediment samples were pulverised. One portion was spiked with
10 mL of 1000 mg/L standard mixture consisting 20 different organochlorine pesticides, whereas
the other that served as control was left unspiked. The two portions were extracted separately and
taken through the same procedure earlier outlined. Moreover, 10 mL of the standard 1000 mg/L
mixture of the organochlorine in spectra grade n-hexane was put into a clean oven dried sample
bottle and dried at ambient temperature followed by purging with high purity nitrogen gas, whereas
the residue was redissolved in 1 mL n-hexane. To both the spiked and the control standard mixture,
1 L was separately injected into the column of the GC-ECD and analysed sequentially. The
recoveries of the OCPs were determined by comparing the peak areas of the OCPs after spiking
518
with those obtained from the evaporated standard residue. Calculation of the % recoveries was
performed as follows:
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%R =
Statistical analyses
The mean standard deviation for the organochlorine pesticide congeners from duplicate measurements was determined using the Statistical Package for the Social Science (SPSS) software,
15.0 for window evaluation version. Duncans multiple range test [39] was used to determine
significant differences between means. The linear correlation coefficient of the OCP congeners
was determined using the Pearson correlation coefficient.
3.
Results
The reliability and reproducibility of the analytical procedures used based on the recoveries
work of the individual OCP congeners obtained during the spiking experiment gave the values
of 82.54 to 98.35% in water samples and 87.65 to 110.78% in sediment samples with relative
standard deviation of less than 10%. Hence, these values are adjudged reliable and efficient.
The retention time (min) ranges from 6.908 in -BHC to 11.046 in water and 6.965 in -BHC
to 10.687 in sediment, whereas the range of response factors of 0.657 to 1.885 indicated the
separation efficiency of the programmed method for GC-ECD identification and the quantification
of the OCPs was efficient. The LOD values for the OCPs ranged from 0.055 to 2.105 g/L
(Table 1).
The results of the levels of OCPs studied in all the matrices fell into three categories: dichlorodiphenylethanes (pp-DDD, pp-DDE and pp-DDT), cyclodiens (heptachlor,
Response factor, retention time, limit of detection and % recovery for OCPs.
Retention Time
OCP
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519
-BHC
-BHC
BHC
- BHC
Heptachlor
Aldrin
Heptachlor-epoxide
- Chlordane
Endosulfan I
- Chlordane
Dieldrin
pp- DDE
Endrin
Endosulfan II
pp- DDD
Endrin- CHO
Endosulfan III
pp- DDT
Endrin CO
Methoxychlor
% Recovery
Response
factor
Water
Sediment
Water
Sediment
Limit of
Detection (ppb)
1.77 0.01
0.68 0.01
1.16 0.02
1.46 0.02
1.29 0.15
1.34 0.02
1.45 0.01
0.55 0.02
0.56 0.02
0.60 0.01
0.95 0.05
0.89 0.01
1.08 0.02
0.66 0.06
1.88 0.03
1.58 0.01
0.89 0.03
0.95 0.02
1.25 0.02
1.67 0.03
6.91 0.25
7.27 0.12
7.73 0.42
7.89 0.26
8.23 0.34
8.67 0.39
8.95 0.45
9.02 0.15
9.27 0.37
9.52 0.22
9.68 0.17
9.85 0.48
9.91 0.52
10.06 0.44
10.29 0.25
10.40 0.37
10.74 0.51
11.05 0.45
11.33 0.49
11.57 0.53
6.97 0.33
8.18 0.24
8.52 0.45
8.92 0.21
9.04 0.28
9.24 0.18
9.49 0.41
9.65 0.26
9.81 0.29
9.94 0.43
10.06 0.22
10.33 0.35
10.41 0.49
10.59 0.45
10.62 0.52
10.63 0.55
11.09 0.44
11.23 0.57
11.37 0.55
11.48 0.48
84.56 4.58
88.75 6.84
95.06 4.68
90.34 5.75
90.23 5.44
88.52 5.62
91.99 1.45
90.22 4.78
84.23 4.88
92.23 3.75
83.88 4.27
93.55 3.34
82.69 5.25
81.22 3.77
95.82 5.66
92.31 5.80
86.78 4.03
90.32 6.01
84.76 4.67
85.79 5.08
88.91 8.25
95.21 7.70
89.54 5.44
92.38 4.32
89.78 8.77
91.67 4.88
89.43 7.89
93.55 6.88
88.89 3.49
94.15 5.48
89.45 2.38
98.11 4.65
92.34 6.21
86.78 3.99
89.78 2.22
88.89 4.08
89.74 5.12
92.78 4.44
88.65 3.66
90.55 5.64
1.086
0.101
0.095
0.067
1.090
2.105
0.041
0.479
0.076
0.481
0.894
0.182
0.305
0.065
2.001
0.051
0.044
0.055
0.055
0.046
Location
A
B
C
D
-BHC
-BHC
-BHC
ppDDE
ppDDD
ppDDT
Heptachlor
Heptaclor Epox
-Chlordane
0.10 0.14a
ND
0.06 0.08a
0.20 0.28a
0.10 0.15a
0.05 0.08a
0.08 0.11a
0.14 0.20a
ND
ND
ND
ND
0.07 0.10a
ND
0.14 0.20a
0.13 0.19a
ND
ND
0.08 0.11a
0.06 0.09a
ND
ND
0.07 0.10a
0.06 0.09a
0.07 0.09a
ND
0.07 0.09a
0.08 0.12a
0.14 0.20a
0.08 0.12a
0.06 0.09a
0.06 0.08a
ND
ND
0.10 0.15a
0.08 0.12a
ND
ND
0.07 0.10a
0.07 0.09a
Mean with different letter of the alphabet for each column are significantly different (p < 0.05) from each other.
Table 3.
Location
A
B
C
D
Endosulfan I
Endosulfan II
ND
ND
0.08 0.11a
0.07 0.10a
0.46 0.05b
0.06 0.09a
0.13 0.19ab
0.08 0.11a
0.08 0.11a
ND
0.06 0.09a
0.05 0.08a
Endosulfan III
0.38a
0.50
0.27 0.39a
0.07 0.09a
0.08 0.11a
Aldrin
0.17 0.02b
ND
0.08 0.11ab
ND
Endrin
Endrin Aldehyde
ND
ND
0.07 0.10a
0.07 0.09a
0.18 0.26a
ND
0.69 0.09a
0.12 0.17a
Endrin Ketone
Dieldrin
Methoxychlor
0.10
0.09 1.28a
0.08 0.12a
0.08 0.11a
0.09 0.12a
0.18 0.05a
0.12 0.17a
0.07 0.09a
0.06 0.08a
0.14a
ND
0.09 0.12a
0.05 0.07a
Mean with different letter of the alphabet for each column are significantly different (p < 0.05) from each other.
Table 4.
Location
A
B
C
D
-BHC
-BHC
-BHC
ppDDE
ppDDD
ppDDT
Heptachlor
Heptaclor Epox
-Chlordane
0.04 0.00a
0.99 1.24a
0.35 0.01a
0.06 0.07a
0.02 0.00a
0.12 0.02a
0.52 0.03b
0.09 0.11a
ND
0.07 0.11a
ND
0.01 0.01a
0.02 0.00a
0.15 0.10ab
0.28 0.02b
0.03 0.01a
ND
0.40 0.32a
1.14 0.06b
ND
ND
2.04 2.88ab
6.67 0.14b
2.05 2.80ab
0.46 0.02a
1.69 2.39a
ND
ND
0.03 0.00a
0.26 0.16ab
0.36 0.02b
0.05 0.05a
0.06 0.01a
0.47 0.51a
ND
ND
ND
0.19 0.03a
ND
0.38 0.54a
Mean with different letter of the alphabet for each column are significantly different (p < 0.05) from each other.
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520
Table 2.
Location
-Chlordane
Endosulfan I
Endosulfan II
Endosulfan III
Aldrin
Endrin
Endrin Aldehyde
Endrin Ketone
Dieldrin
Methoxychlor
A
B
C
D
0.02 0.00a
0.19 0.00a
1.35 0.02b
0.15 0.22a
0.05 0.01a
0.17 0.01a
ND
0.55 0.77a
1.07 0.01b
ND
ND
ND
ND
ND
ND
ND
0.09 0.00a
0.01 0.01a
ND
0.06 0.09a
ND
0.21 0.04b
0.19 0.01b
0.08 0.11ab
ND
ND
ND
0.03 0.04a
ND
0.43 0.16a
2.78 0.14b
0.46 0.63a
ND
0.09 0.12a
ND
0.38 0.54a
ND
0.32 0.46a
ND
0.51 0.73a
Mean with different letter of the alphabet for each column are significantly different (p < 0.05) from each other.
Table 6.
Medium
-BHC
-BHC
-BHC
-BHC
ppDDE
ppDDD
ppDDT
Heptachlor
Heptaclor Epox
-Chlordane
Water
Sediment
0.09 0.14
0.36 0.63
0.09 0.11
0.19 0.21
Nd
0.02 0.05
0.09 0.12
0.12 0.12
0.04 0.07
0.38 0.51
0.03 0.06
2.69 3.02
0.05 0.08
0.54 1.17
0.09 0.11
0.17 0.16
0.05 0.09
0.13 0.29
0.03 0.06
0.05 0.08
Table 7.
Medium
-Chlordane
Endosulfan I
Endosulfan II
Endosulfan III
Aldrin
Endrin
Endrin Aldehyde
Endrin Ketone
Dieldrin
Methoxychlor
Water
Sediment
0.04 0.07
0.43 0.58
0.19 0.19
0.19 0.37
0.05 0.06
0.27 0.49
0.23 0.28
ND
0.06 0.08
0.04 0.05
0.04 0.06
0.12 0.10
0.09 0.14
0.01 0.02
0.09 0.09
0.92 1.19
0.06 0.08
0.12 0.27
0.11 0.09
0.21 0.40
521
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Table 5.
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522
heptachlor-epox (0.13 0.29), aldrin (0.04 0.05), -Chlordane (0.05 0.08), -Chlordane
(0.43 0.58), endosulfan I (0.19 0.37), endosulfan II (0.27 0.49), endosulfan III (ND),
dieldrin (0.12 0.27), endrin (0.12 0.10), endrin aldehyde (0.01 0.02), endrin ketone
(0.92 1.19), and methoxychlor (0.21 0.40).
WHO [40] recommended the following values (mg/L) for various OCPs compounds in drinking
water 0.02 (lindane), 0.0002(chlordane), 0.006 (endrin), 0.00003(aldrin and dieldrin), 0.001(DDT
and metabolites), and 0.02 (methoxychlor). The values obtained for various OCPs compounds
both in water and sediment in this study were above the stipulated guideline values to chemicals
from agricultural activities to the area of health significance in drinking water by WHO. No
stipulated value for endosulfan and heptachlor by WHO.
4.
Discussion
It was noted that the distribution pattern for the two matrices was not exactly predictable. However,
the mean levels of OCPs in water were generally lower than that of the sediment where similar
findings were reported by Okoya et al.,[41] In water, endosulfan I, II and III, endrin ketone and
endrin aldehyde as well as , and -BHC, heptachlor and methoxychlor were found in significant
concentrations in almost all the sites, indicating their wide use.
The composition of OCPs and its metabolites is a useful tool for better understanding of the origin and transport pathways of these contaminants in the environment.[42] DDT is degraded under
aerobic conditions by micro-organisms to DDE and under anaerobic condition to DDD. DDE
is more stable end-product; resistant to further degradation. DDD is an intermediate metabolite in conversion of DDT to DDE.[42] The result of this study was in agreement of Pandey
et al.,[42] where the percentage distribution of DDD is higher than DDE suggesting fresh input
of DDT rather than historical usage. The concentration of heptachlor both in water and sediment
was higher compared to heptachlor-epoxide. Heptachlor gets mobilised to heptachlor-epoxide in
the aquatic environment.[42] Heptachlor epoxides adsorbed strongly to the soil and very resistant to degradation.[43] The dominance of heptachlor in sediment may be attributed to its slow
degradation due to the low temperature of the bottom sediment.
Residues of BHC isomers in both water and the sediments in significant concentrations
may be attributed to the heavy use of this pesticide both for agricultural and fishing activities
within and around the reservoir. The concentration of the four isomers of BHC reveals a heterogenic nature of distribution. Similarly, the composition of BHC isomers may be relative to
isomerisation of BHC during the process of transport and transformation.[42] It is evident to
assume that vector control programmes are very poor especially in rural area compared to urban
environment.
Agunloye [44] and Tongo [45] studied the occurrence and levels (g/L) of chlorinated hydrocarbons in rivers and lakes in Southern Nigeria and reported the occurrence of lindane (ND - 167),
aldrin (Nd - 190), endosulfan (ND - 750), HCB (ND - 9.2) and heptachlor (ND - 96). Ogunlowo
[46] in his own studies reported the levels of OCPs in nine rivers in Ondo state and obtained a
range of ND - 2150 ng/L for lidane, heptachlor, endrin, aldrin and dieldrin. Nwankwoala and
Osibanjo [47] reported the occurrence of OCPs in surface water in Ibadan the values (ng/L) of
and -BHC (1302), lindane (7297), aldrin (Nd - 19), heptachlor (4202) and total DDT
(Nd-1266). Ogunfowokan et al.,[48] in their studies of OCPs levels in pond water and fish of an
agricultural fish pond in Oke-sun, Osogbo Nigeria reported monthly mean levels (g/L) range
from chlordane (2.65 2.50) in May to pp-DDE (85.12 26.35) in June, the wet season had a
range values between chlordane (12.42 12.75) and o,p -DDD (39.60 36.61); for dry season,
the mean levels ranges between -BHC (0.27 0.90) and dieldrin (17.24 8.71).
Concentrations of organochlorine pesticide residue in water and sediment of some African rivers.
Location/Water Type
pp-DDE
pp-DDD
pp-DDT
Lagos Lagoon
Ero Reservoir
Ero River
Osse River
Owesse River
Apomu River
Ibadan stream
River Ogun
River Imo
Cross River
Awba Dam
Kainji Lake
HartbeepoortReservoir
Voelvlei Reservoir, SA
Mcllwaine Lake
Akure
Ifedore
Idanre
3(Nd-15)
Nd
Nd
Nd
Nd
Nd
83(Nd-344)
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
Nd
100
< 100
100
100
< 100
< 100
100
< 100
< 100
Ogunpa, Ibadan
13(Nd-32)
Nd
0.1(Nd-5.3)
Ona River
7(Nd-14)
Nd
1(Nd-2)
Oniyere
9(Nd-50)
Nd
Nd
Lekki, Lagoon
263(11-555)
Nd
88(Nd-438)
Ebrie Lagoon,CoteDIvorie 7.4(0.1149) 28.1(0.2803) 15.7(0.2354)
Mallwaine, Zimbabwe
Hartbeespoort Dam, SA
10
18
13
Voelvlei Dam, SA
5
2
6
Lake Nakuru, Kenya
10
10
< 10
Numbaya Mungu,Tanzania
1(Nd-1)
1(Nd-3)
3(27)
Pond, Osogbo
Akure
Ifedore
Idanre
-BHC
Water (ng/L)
2500 (Nd-4000)
Nd
Nd
Nd
Nd
Nd
150(1302)
300
-BHC
-BHC
-BHC
Reference
Tongo [45]
Ogunlowo [46]
2.0
2.0
2.0
6.4
4.8
100(7297)
13.3(1.441.9)
0.2(Nd-0.6)
0.3(Nd-1.1)
61(9167)
0.12(Nd-0.24)
Nd
Nd
Nd
Nd
Nd
Nd
0.037
Nd
Nd
Nd
Nd
Nd
0.5(Nd-1.2)
Nd
0.9(Nd-2.0)
0.4(Nd-3.3)
Sunday [54]
Ojo [55]
Marchand and Martins [56]
Mhlanga and Madziva [57]
Grechus et al. [51]
Sediment (ng/g)
0.7(Nd-2)
0.5(Nd-0.9)
0.1(Nd-0.4)
18.6(Nd-116) 1.1(0.14.9)
17.1(1.1997)
76(32146)
16(242)
45
13
w
23.01w
24.59
57.94d
40.06d
Nd
Nd
Nd
4.865.64
Nd
Nd
22.11w
46.31d
Nd
1.23.73
Nd
Author with asterisk reported their result in mg/L and ug/g, w, wet, d, dry.
DDD Total
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Table 8.
Concentrations of organochlorne pesticide residue in water and sediment of some African rivers.
Location/Water Type
Ibadan stream
River Ogun
River Imo
Cross River
Awba Dam
Kainji Lake
Ero Dam
Ero River
Osse River
Owesse River
Apomu River
Akure
Ifedore
Idanre
Ogunpa
Ona River
Oniyere
Lekki Lagoon
Mellwaine
Pond, Osogbo
Akure
Ifedore
Idanre
HCB
Heptachlor
Aldrin
17(Nd-92)
72(4202)
0.28(Nd-0.8)
4(Nd-11.4)
2(Nd-8.6)
0.47(Nd-3.48)
3.3
Nd
5.0
1.6
4.6
Nd
Nd
Nd
20(Nd-40)
40(5.149)
13(Nd-40)
36(Nd-143)
18(1229)
0.55(Nd-3.05)
3.1
Nd
Nd
Nd
3.5
Nd
Nd
Nd
Nd
Nd
Nd
64(Nd-1845)
28.30w
44.69d
Nd
Nd
Nd
Nd
Nd
Nd
56(Nd-3471)
1.0(Nd-12)
28.30w
63.32d
Nd
Nd
Nd-0.02
1.0(Nd-5)
0.8(Nd-2.5)
Heptaclor epoxide
Author with asterisk reported their result in mg/L and ug/g; w, wet season, d, dry season.
Endosulfan
Water (ng/L)
98(Nd-430)
116(Nd-260)
1.3(Nd-41)
20(Nd-80)
20(Nd-30)
Nd
Nd
Nd
Nd
nd
Nd
1.913.12
Nd
0.386.49
Nd
3.426.05
Sediment (ng/g)
Nd
Nd
Nd
30(71155)
23.73w
64.99d
0.191.76
Nd-5.93
86.40127.14
Nd
0.398.29
Endosulfan
Dieldrin
Reference
250(17.8652)
560
740
2150
1120
1380
Nd
0.002
Nd
0.9(Nd-1.8)
0.3(Nd-0.5)
2.0(Nd-6)
4560(1908460)
5.0(Nd-16)
30.63w
69.17d
Nd
Nd-0.11
Nd
Sunday [54]
0.005
0.030
0.0260.034
Nd
0.060.68
0..10.05
0.060.99
Ojo [55]
Mhlanga and Madziva [57]
Oyekunle et al. [49]
Idowu et al. [53]*
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524
Table 9.
Correlation coefficient in water samples for individual OCPs from Aiba Reservoir.
-BHC
-BHC
-BHC
-BHC
Heptachlor
Aldrin
Heptachlor-Epox
-Chlordane
Endo-sulfan I
-Chlodane
Dieldrin
ppDDE
Endrin
Endo-sulfan II
ppDDD
Endrin Aldehyde
Endo-sulfanIII
ppDDT
Endrin Ketone
Methoxychlor
-BHC
-BHC
-BHC
-BHC
Hepta-chlor
Aldrin
Heptachlo Epox
-Chlordane
Endo-sulfan I
-Chlodane
1
0.87
0
0.82
0.02
0.05
0.64
0.71
0.22
0.69
0.26
0.65
0.68
0.79
0.67
0.81
0.14
0.91
0.61
0.29
1
0
0.54
0.76
0.23
0.64
0.69
0.28
0.68
0.79
0.65
0.67
0.33
0.66
0.18
0.49
0.46
0.33
0.29
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0.05
0.31
0.91
0.92
0.16
0.92
0.52
0.92
0.92
0.93
0.92
0.73
0.19
0.95
0.68
0.33
1
0.47
0.18
0.18
0.51
0.18
0.74
0.18
0.18
0.08
0.18
0.19
0.89
0.04
0.12
0.52
1
0.18
0.12
0.75
0.13
0.65
0.17
0.14
0.44
0.16
0.37
0.49
0.31
0.21
0.49
1
0.99
0.09
0.99
0.65
1.00
0.99
0.71
0.99
0.39
0.19
0.76
0.49
0.15
1
0.10
1.00
0.62
0.99
0.99
0.71
0.99
0.42
0.19
0.78
0.49
0.15
1
0.10
0.30
0.09
0.10
0.38
0.09
0.52
0.74
0.31
0.50
0.8
1
0.03
0.99
1.00
0.71
0.99
0.41
0.19
0.77
0.49
0.14
(Continued)
525
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Table 10.
Continued
-BHC
-BHC
-BHC
-BHC
Heptachlor
Aldrin
Heptachlor-Epox
-Chlordane
Endo-sulfan I
-Chlodane
Dieldrin
ppDDE
Endrin
Endo-sulfan II
ppDDD
Endrin Aldehyde
Endo-sulfanIII
ppDDT
Endrin Ketone
Methoxychlor
Dieldrin
ppDDE
Endrin
Endo-sulfan II
ppDDD
Endrin Aldehyde
Endo-sulfan III
ppDDT
Endrin Ketone
Methoxychlor
1
0.64
0.63
0.35
0.64
0.08
0.44
0.36
0.10
0.34
1
0. 99**
0.71
1.00
0.39
0.19
0.76
0.49
0.15
1
0.71
1.00
0.41
0.19
0.77
0.49
0.14
1
0.71
0.91
0.16
0.97
0.75
0.45
1
0.40
0.19
0.77
0.49
0.15
1
0.11
0.89
0.71
0.48
1
0.17
0.16
0.68
1
0.73
0.40
1
0.82
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526
Table 10.
Correlation coefficient in sediment samples for individual OCPs from Aiba Reservoir.
-BHC
-BHC
-BHC
-BHC
-BHC
Hepta-chlor
Aldrin
Hepta chlorEpox
-Chlodane
Endo-sulfan I
-Chlodane
Dieldrin
ppDDE
Endrin
Endo sulfan II
ppDDD
Endrin Aldehyde
Endo sulfanIII
ppDDT
Endrin Ketone
Methoxychlor
1
0.12
0.18
0.53
0.67
0.46
0.9
0.06
0.12
0.71
0.19
0.39
0.60
0.32
0.38
0.23
0
0.22
0.02
0.30
-BHC
1
0.19
0.8
0.79
0.67
0.17
0.9
0.41
0.19
0.07
0.9
0.63
0.49
0.9
0.33
0
0.26
0.9
0.39
-BHC
1
0.15
0.09
0.14
0.04
0.19
0.05
0.54
0.07
0.19
0.23
0.24
0.39
0.06
0
0.9
0.15
0.51
-BHC
1
0.9
0.66
0.28
0.8
0.28
0.19
0.37
0.9
0.74
0.52
0.8
0.27
0
0.23
0.82
0.32
Hepta-chlor
1
0.77
0.45
0.76
0.37
0.37
0.25
0.9
0.8
0.56
0.8
0.39
0
0.17
0.73
0.39
Aldrin
1
0.29
0.62
0.64
0.39
0.35
0.64
0.9
0.59
0.77
0.66
0
0.09
0.65
0.49
Hepta-Chloro Epox
1
0.23
0.04
0.82
0.19
0.13
0.45
0.17
0.09
0.19
0
0.06
0.27
0.18
-Chlodane
1
0.39
0.25
0.12
0.9
0.57
0.44
0.8
0.30
0
0.25
0.9
0.37
Endo-sulfan I
1
0.31
0.22
0.34
0.42
0.24
0.42
0.9
0
0.08
0.40
0.8
-Chlorodane
1
0.09
0.05
0.56
0.33
0.09
0.22
0
0.50
0.26
0.12
(Continued)
527
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Table 11.
Continued
Dieldrin
-BHC
-BHC
-BHC
-BHC
Hepta-chlor
Aldrin
Hepta chlorEpox
-Chlodane
Endo-sulfan I
-Chlodane
Dieldrin
ppDDE
Endrin
Endo sulfan II
ppDDD
Endrin Aldehyde
Endo sulfanIII
ppDDT
Endrin Ketone
Methoxychlor
1
0.34
0.19
0.27
0.09
0.18
0
0.03
0.03
0.11
ppDDE
1
0.68
0.46
0.88
0.30
0
0.25
0.89
0.37
Endrin
1
0.73
0.73
0.48
0
0.13
0.59
0.28
Endo sulfan II
ppDDD
Endrin Aldehyde
Endo sulfanIII
ppDDT
Endrin Ketone
Methoxychlor
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528
Table 11.
1
0.55
0.22
0
0.39
0.47
0.32
1
0.35
0
0.47
0.88
0.52
1
0
0.19
0.31
0.82
1
0
0
0
1
0.22
0.39
1
0.35
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529
Oyekunle et al. [49] studied the levels of organochlorine in pond sediments from a farm settlement in Osogbo Nigeria and reported mean range (g/kg) of 15.45 heptachlor to 45.93 p.p -DDT
in rainy season and 31.88 chlordane to 102.23 p,p -DDE in dry season. Pandey et al.,[26] in their
study of surface sediments of River Yamuna (Delhi, India) reported that total OCPs level ranged
from 157.71 to 307.66 ng/g in June, 195.86577.74 ng/g in August and 306.9844.45 ng/g in
October. Okoya et al.,[25] in their study of OCPs residue in sediments and waters from cocoa
producing area of Ondo state, south-western Nigeria reported mean range of OCPS (g/g)for
sediment as cis-chlordane 0.036.99; -endosulfan 0.036.99; pp-DDE 0.0819.04 and dieldrin
0.017.62.
The organochlorine pesticides residues, their metabolites or conversion from one form to
another are harmful to human and ecologically harmful to aquatic habitats. The toxicity of these
OCPs can result in the death of fish perhaps due to deliberate application or accidental release of
these chemicals to aquatic environment. Contamination of water body and bottom sediment with
these chemicals usually results in bioaccumulation in aquatic habitats.
Comparison with other studies revealed that the concentrations of individual OCPs reported
in this study are consistent with other studies of OCPs reported at the national and international
levels. The values of OCPs observed in this study are comparable to those reported by other
authors. Tables 8 and 9 list different studies together with the individual OCP concentrations
observed in different parts of Africa. Generally, various compartments of the aquatic environment
in Nigeria and other parts of Africa are greatly contaminated by several OCPs. However, the
values recently reported by Okoya et al.,[25] and Idowu et al.,[53] of the cocoa producing area of
Ondo state, Nigeria were exceedingly high compared to this study, which could be attributed to
intensive use of organochlorine pesticides in this area.
Correlation was performed for both water and sediments using bivariate Pearson correlation
coefficient for all pairs of compounds to determine the relationships between individual compounds. Correlation of OCPs in the surface water in Table 10 shows that apart from -BHC
and endosulfan III, which did not significantly correlate with any other compounds, other compounds showed significant positive correlation with at least two other OCPs to a maximum of
nine compounds in -BHC. Table 11 shows the correlation coefficient for bottom sediment where
-chlordane, dieldrin, endosulfan II, pp-DDT, endrin ketone and methoxychlor did not show any
correlation at all; aldrin was negatively correlated with pp-DDD, whereas others showed strong
positive correlation with one another ranging from one to six individuals. The several positive and
significant correlations were an indication that all OCPs were all related derivatives which was
an indication that they were likely to have originated from the same source and similarly affected
by related factors within the same environmental matrix.[26,32]
5.
Conclusion
The preliminary study on the levels of organochlorine pesticide in water and sediments of Aiba
reservoir has been assessed. Three classes of OCPs (chlorinated benzene/cyclohexanes, cyclodienes and dichlorodiphenylethane) were identified and quantified. The study obtained indicated
that both the water and bottom sediments were contaminated with high levels of these chemicals.
The study further indicated that the concentrations of OCPs in water was lower to that of sediments, hence they were hydrophobic and tend to accumulate in the sediments which act as a sink
for these persistent organic pollutants. The levels of OCPs obtained revealed gross anthropogenic
inputs of these chemical species by the farmers, fisher men and domestic sewages. Extensive
research work covering the seasonal evaluation and public enlightenment by the State Government and other appropriate agencies on the adverse health hazards of the use of these chemicals
are highly recommended.
530
Acknowledgement
Downloaded by [Cape Peninsula University of Technology], [Godwin Oladele Olutona] at 21:25 24 June 2014
The authors appreciate the two anonymous reviewers for their objective criticisms which helped to improve the quality
of the manuscript.
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