Determination of selected organochlorine pesticide (OCP)

compounds from the Jukskei River catchment area in

Gauteng, South Africa

Linda L Sibali1*, Jonathan O Okwonkwo2 and Rob I McCrindle3

1
Scientific Services, Rand Water, Vereeniging 1930, South Africa
2
Department of Environmental, Water & Earth Sciences, Tshwane University of Technology, Tshwane 0001, South Africa
3
Department of Chemistry, Faculty of Science, Tshwane University of Technology, Tshwane 0001, South Africa

Abstract

Organochlorine pesticides (OCPs) are continually detected in the environment due to their increasing applications in agri-
culture and industry. The presence of OCPs in the environment is not desirable since they are well known to have negative
impact in humans, animals and birds. Thus, there has been a continual demand to monitor the presence of OCPs within the
environment. Liquid-liquid extraction (LLE) and Soxhlet extraction (SE) methods (using dichloromethane as the extracting
solvent,) were optimised and evaluated for the determination of these compounds in surface water (unfiltered and filtered)
and sediment samples. The crude extracts obtained were subjected to column chromatography for clean-up. Thereafter, 1 µℓ
of the cleaned extracts were injected into the GC equipped with ECD.
Percentage recoveries obtained for OCPs ranged from 98.90±7.32 (2,4’-DDE) - 124.1±8.23 endosulfan II (ENDO II) %
and from 98.99±5.30 (2,4’-DDE) - 121.1±0.38 (4,4’-DDE) % in spiked triply distilled water and sediment samples respec-
tively. The levels of OCPs obtained in unfiltered environmental water samples ranged from 0.631±0.03 (γ-HCH) - 1 540±0.19
ng·mℓ-1 (4,4’-DDT) while levels in filtered water samples ranged from 0.895±0.01 (γ-HCH) - 9 089±0.08 ng·mℓ-1 (HEPTA).
Levels of analysed OCPs obtained in sediments ranged from 0.266±0.01 (δ-HCH) - 22 914±2.85 ng·gdw-1 (2,4’-DDE). Ana-
lytes adsorbed on the sample bottles used for water samples collection gave levels which ranged from 0.01±0.01 - 1.06±0.02
ng·mℓ-1 for OCPs.
The levels obtained from the catchment were significantly higher than the water criteria values recommended by USEPA
and DWAF for the protection of the aquatic environment. Levels obtained were also higher than those of other studies
conducted so far in South African aquatic environments. There is, therefore, a definite pollution of the Jukskei River catch-
ment by the OCPs studied.

Keywords: OCPs, surface water, sediments, liquid-liquid extraction, GC-ECD

Introduction solubility and high lipid solubility. They have been associated
with significant environmental impact in a wide range of spe-
The release of various organic pollutants from different sources cies and at virtually all tropic levels. Many organochlorines have
such as runoff or effluent discharges into the environment is an been implicated in a broad range of adverse human health and
issue of great concern in many countries. The sea, rivers, dams or environmental effects, including impaired reproduction, endo-
lakes have become the immediate environmental reservoirs for crine disruption and immunosuppression. Exposure to orga-
all possible organic pollutants (Chee et al., 1996). These include nochlorines has been correlated with population decline in a
organochlorine pesticides (OCPs) such as lindane, endosulfan number of marine mammals (Tanabe et al., 1994).
(ENDO), dichlorodiphenyltrichloroethane (DDT) and its degra- Due to the toxic effects of organochlorines in aquatic organ-
dation products, DDD and DDE (Tomkins et al., 1992). Some isms, the use and/or sale of most organochlorine pesticides has
OCPs have contributed greatly to the increase in food production been banned or restricted in many developed countries such
and at the same time have improved human and animal health. as United States of America and Sweden since the mid 1970s
However, these successes have been marred by the revelation of (Tanabe et al., 1997). Studies conducted on OCPs in aquatic
their side-effects on non-target species (Barlas, 2002). environments in South Africa (Weaver, 1993; Grobler, 1994;
Some OCPs are highly resistant to degradation by biologi- Naude et al., 1998; London et al., 2000; Fatoki and Awofolu
cal, photochemical or chemical means. They are also liable to 2003; Okonkwo et al., 2007), Europe (Blair et al., 1997 and
bioaccumulation and are prone to long range transport (Tanabe Fernandez-Alba et al., 1998), Asia (Iwata et al., 1994 and Xue
et al., 1994). Many of these compounds have already been listed et al., 2006) and America (Dorothea and Muir, 1991; Guillette
as top-priority pollutants owing to their carcinogenic, hepatoxic et al., 1998) have shown a widespread occurrence of residues
and mutagenic effects (USEPA, 1984 and WHO, 2004). These of these pesticides in environmental aquatic systems, despite
compounds are also typically characterised as having low water the fact that they have been banned for decades. In developing
countries such as South Africa, DDT is still used officially for
malaria vector control in some parts of the country. It is believed
that some group of OCPs may still be in use clandestinely under
* To whom all correspondence should be addressed.
 +2716 430-8419; fax: +2716 455-2055; unknown trade names in agriculture due to their low cost and
e-mail: lsibali@randwater.co.za effectiveness for pest control.

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 Liquid-liquid extraction (LLE) is a common method used 4000C for 3 h before use. All solvents were subjected to distilla-
for the determination of organic compounds in water. The study tion three times before use and were in a range of 99.0 to 99.5%
by Awofolu and Fatoki (2003) has shown this method to be more pure. OCP standards were obtained from Supelco (Supelco,
reliable than solid phase extraction (SPE) cartridges during sam- Belle-fonte, PA, USA). Silica gel, Kieselgel Merck Typ 77754,
ple preparation since the latter method is prone to interferences, 70 to 230 mesh 100 µm was purchased from Sigma-Aldrich,
especially when gas chromatography-electron capture detector South Africa. All the gases used were 99.9% pure obtained
(GC-ECD) is used. SE is also an established technique that has from Afrox, South Africa. Analytical grade sulphuric acid was
been used for the extraction of organic pollutants such as OCPs purchased from Merck.
from marine sediment and soil samples (Snyder et al., 1992). The
use of gas chromatography (GC) with electron capture detector Preparation of stock standard solutions
(ECD) for the detection of OCPs is common because of its high
resolution and good sensitivity in the nanogram range. However, 1000 mg·ℓ-1 of each OCP standard was prepared with hexane in
gas chromatography-mass spectrometry (GC-MS) is also widely a 5 mℓ volumetric flask. Lower working concentrations of OCP
employed for the determination of OCPs in complex matrices standards were prepared from the stock solution. Thereafter,
(Awofolu and Fatoki, 2003). 1.0 µℓ of each was injected into the GC-ECD until the instrument
Studies conducted to date in some South African waters could not show any peaks. Ten injections of the last detected
have shown the presence of OCPs. Grobler (1994) investigated concentration were made and the injection error calculated.
the presence of chlorinated hydrocarbon pesticides and PCB Internal standard method of analysis was chosen because it is
residues in water, fish and sediment from Olifants River. PCBs more accurate and reliable due to the adjusting and correcting
and OCPs investigated were not detected in water and sedi- mechanisms it performs from unavoidable errors that are likely
ments except DDT in fish samples. Naude et al. (1998) stud- to emanate from measurement of syringe volumes of the stand-
ied the comparison of supercritical fluid extraction (SFE) and ards and processed samples.
soxhlet extraction (SE) for the determination of DDT, DDD
and DDE in sediment samples from the Pongolo floodplain in Determination of instrument detection limits (IDLs)
KwaZulu-Natal and the Letaba River in Mpumalanga Prov- and retention times (RT)
ince. London et al. (2000) investigated the quality status of
surface and groundwater in the rural Western Cape for OCPs. The instrument detection limits (IDL) is the lowest detect-
Also in the same year, Meintjies et al. (2000) analysed water able amount of each analyte that the instrument can detect and
samples from the Vaal River in the vicinity of Vereeniging record. The IDL was computed using the method described by
and Vanderbijlpark for organochlorine pesticides using SPE Miller and Miller (1998).
and GC-ECD. Awofolu and Fatoki (2003) determined OCPs in
water and sediment samples respectively in the Eastern Cape. IDL = Yb + 3Sb (1)
Okonkwo et al. (2007) as part of the present study investigated
the extraction efficiency of activated carbon with respect to where:
the occurence of DDT and its metabolites (DDD and DDE) in Yb = blank value
the Jukskei River catchment area. However, in most of these Sb = standard error of the regression line
studies the possible analyte losses through retention on sample
bottles and differences between filtered and unfiltered environ- The noise and thresholds were set during column background
mental water samples were not given adequate attention. Smith run so as to eliminate noise spikes from being registered as
et al. (2001) reported that filtered water samples tend to show peaks. Each standard was injected into the GC to determine its
evidence of lower levels compared to unfiltered water samples. retention time.
It is still impossible to present a complete picture of OCPs dis-
tribution in South Africa waters since their levels within bigger Determination of response factors (Rf )
catchments such as the Jukskei River catchment has not been
adequately reported. Response factor (Rf ) is a ratio of signal-to-sample size used to
The objectives of this study were to use LLE and SE meth- characterise a detector. It can also be explained as the measure
ods with different solvent combinations and varied GC-ECD of the sensitivity and responsiveness of the analytes relative to
conditions for the determination of 13 OCPs in water (filtered the instrument. Rf of the OCP standards relative to the internal
and unfiltered) and sediment samples. In addition, analyte losses standard (IS), pentachloronitrobenzene (PCNB) were carried
through analyte retention on sample bottles and seasonal varia- out by injecting the mixture of OCPs within the concentration
tion at different sampling sites were studied. range 2 to 10 μg· ℓ-1. Ten replicate injections were made. The Rf
was calculated from Eq.(2):
Experimental Peak area of a compound (PAE)
(Rf ) = (2)
Apparatus and reagents Peak area of an internal standard

Thoroughly washed glassware was soaked overnight in dilute Silica gel column chromatography (clean-up)
HNO3 solution and rinsed three times with distilled water and
then with pure acetone. Sample bottles (2.5 ℓ Winchester bot- The chromatographic column (20 cm x 8 mm I.D.) was packed
tles) were used to collect water samples and wide-mouth 500 with 5.0 g of activated silica gel, which was made into slurry
mℓ brown glass Winchester sampling bottles for the collec- with 1.5% (v/m) petroleum ether and then stirred well before use.
tion of sediment samples. All reagents were of analytical and About 1 mℓ of anhydrous sodium sulphate was placed at the top
GC grade (Merck, South Africa). Anhydrous sodium sulphate, of the column to absorb any water in the sample or the solvent.
99.5% pure was deactivated by drying in the muffle furnace at The column was pre-eluted with 15 mℓ of petroleum ether and

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before exposure to sodium sulphate. The reduced 5 mℓ extract Water sampling
from extraction processes was placed in the column and allowed
to sink below the sodium sulphate layer. OCPs extracts were All water samples were collected in triplicate in 2.5 ℓ pre-cleaned
eluted with 2 x 10 mℓ portions of the extracting solvents. The Winchester glass bottles from identified 7 sampling points
eluant was collected, bubbled with nitrogen gas to dryness and within the Jukskei River catchment area. Prior to use, the bottles
reconstituted with 2 mℓ of extracting solvent. Then 1.0 µℓ was were first rinsed with the water samples and then immersed to
injected into the GC. about 5 cm below the surface. 5 mℓ of concentrated sulphuric
acid was added to the water samples for preservation and tightly
Sampling protocol sealed. Samples were then transported in a cooler box with ice
to the laboratory where they were stored in a cold room at 4°C
Description of the study area until they were analysed.

The study area for this research work was the Jukskei River Sediment sampling
catchment area, which is in Gauteng and Northwest Provinces
of South Africa. The Jukskei River catchment was chosen for Sediment samples were collected from about 0 to 5 cm below
this study because it receives effluent from industries and run- the surface from the same locations as water samples using a
off in vast amounts from illegal, unmanaged waste dumps and stainless grab. These samples were placed into pre-cleaned
agricultural practices (DWAF, 2003). The Jukskei River passes wide-mouth 500 mℓ glass bottles and closed immediately after
through the northern part of the densely populated and industr- sampling. The samples were kept cool during transportation in
ialised Witwatersrand complex before flowing into the Croco- a cooler box to the laboratory. At the laboratory they were kept
dile River, as shown in Fig. 1. The Crocodile River drains into frozen at -18°C prior to extraction and analysis.
the Hartbeespoort Dam, which is used for recreational purposes
and as a source of raw water for Magalies Water Board. The Extraction of environmental water and sediment
Jukskei River catchment is largely urbanised and industrialised samples
(DWAF, 2003).
Several extraction methods have been employed in determin-
Sampling sites ing OCPs in water samples. These methods include solid phase
extraction (SPE), liquid-liquid extraction (LLE) (Moeder et al.,
Water and sediment samples were collected from sampling 2000), on-line solid phase extraction (OLSPME) (Brossa et al.,
points during 2005 summer and winter seasons. Sampling 2003) and solid-phase micro-extraction (SPME). SPE is routinely
points were chosen randomly from most accessible sites in the used in many different areas of analytical chemistry. It is used
designated area of study. Six water samples were collected from in the analysis of both polar and non-polar analytes where the
each site (three from the banks and three from the middle except matrix and the analyte of interest are usually dissolved in a liq-
samples S1 and S7 which were taken from the opposite side of uid. It is applied to pesticide analysis in water samples since it is
the banks). The 6 water samples from each point were collected an easy and fast process (Hatrík and Tekel, 1996). The growth of
to make composite samples. Sampling sites which were selected SPE has largely been at the expense of LLE where the perceived
from downstream to upstream for possible sources of pollution advantages of SPE over LLE are that it consumes fewer organic
are as shown in Fig. 1. solvents and that a wider range of extraction mechanisms can be

HARTBEESPOORT N
DAM
1 = Hartbeespoort Dam
1
– S1 (S1BS*1 and S1BS*2),
Crocodile 2 = After Johannesburg
BROEDERSTROO
Water Works– S2 (SB2 and
Hennop Flow of River SM2), 3 = Before Johan-
nesburg Water Works – S3
2 DIEPSLOOT
(SB3 and SM3), 4 = Sand-
NATURE
Jukskei
Crocodile
Little
Johannesburg Water ton /Kyalami – S4 (SB4
Jukskei
3 and SM4), 5 = Marlboro
– S5 (SB5 and SM5), 6 =
MIDRAND Alexander - S6 (SB6 and
4 KEMPTON�
PARK
SM6), 7 = Bruma lake – S7
SANDTON
MODDERFONTEIN
(S7BS*1 and S7BS*2); S =
site; B = bank; S* = side
5
RANDBURG Park and M = middle
ALEXANDRA MODDERFONTEIN
ROODEPOOR DAM
6 Sample Sites
J k k i
EDENVALE

BRUMA Lake
Power Station
7
GERMISTON Sewage Works

Figure 1
Map of South Africa (top left) and sampling sites (bottom right) at the Jukskei River catchment area (DWAF, 2003)

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utilised (Olsen, 1998). However, the study by Tan (1992) and, for 3 to 4 d. These samples were ground and homogenised using
Awofolu and Fatoki (2003) showed that the SPE method is not a clean mortar and pestle and then sieved before subjected to
as reliable as the LLE method. The use of commercial SPE car- further treatment. 10 g of air-dried, sieved and pre-extracted
tridges or disks during sample preparation has also shown to sediment samples were weighed into a pre-extracted What-
give interferences, especially when GC-ECD is used for anal- man extraction thimble in a Soxhlet extraction apparatus using
ysis. In a study, extraneous peaks which appeared in the gas dichloromethane as the extracting solvent. The reduced 5 mℓ
chromatograms were attributed to phthalate esters contained extract was carried through the chromatographic clean-up proc-
in the housing materials of the cartridges used (Awofolu and ess as described above before GC analysis.
Fatoki, 2003). In the case of SPME, the coated fibres employed
can become unstable in complex matrices such as plasma or Quality assurance
urine (Eisert and Levsen, 1996). Analyte recovery with SPME
is between 0.5 to 10% and therefore sensitivity is low. Super- The spiking method with 4 mℓ of (2 to 10 mg·ℓ-1) of OCP stand-
critical fluid extraction (SFE), microwave extraction (ME) and ard mixture and homogenised certified reference material
Soxhlet extraction (SE) are used for the extraction of solid sam- (CRM) as described by Ariese (2001) were used in the quality
ples followed by gas chromatography (GC) or high-performance assurance process for the validation of the analytical methods.
liquid chromatography (Petrovic et al., 2001). The main disad- Several quality assurance measures were also routinely used in
vantages of ME are the use of a single extraction vessel which this study and included running blanks with each sample set and
needs to cool to room temperature which might take some time analysing samples as triplicates. Gas chromatographic condi-
before filtration and this can cause re-adsorption issues (Smith, tions were monitored daily by checking the range of response
2001), and it also requires microwave absorbing solvent. SFE factors of the calibration standards and the recoveries of a test
is described to provide cleaner extracts, less solvent handling, standard that was included in each run.
and equivalent or better recoveries than conventional solvent
extraction technique. Supercritical CO2 has been the most com- Gas chromatography analysis
monly used fluid for SFE because of its low critical constants,
its low toxicity and cost and its ability to extract quantitatively 1 µℓ each of processed sample was injected into the GC (split
a wide range of relatively non-polar organics from a variety of mode – 1 min) for analyses. The injector and detector tempera-
matrices (Rochette et al., 1993). The use of SFE techniques for tures were maintained at 260°C and 300°C respectively. The
the extraction of OCPs from aquatic systems has been widely oven temperature was initially maintained at 100°C, and then
reported in the literature (Snyder et al., 1992 and Barnabas et programmed to increase at 20°C/min to 150°C and ramped to
al., 1994). Despite the fact that SFE of OCPs from aqueous sam- 280°C at 10°C/min. Helium was chosen and used as a carrier gas
ples has shown remarkable advantages over solvent extraction due to the fact that it exhibits a flat Van Dempter profile. The
techniques, there are indications that this technique is not com- make-up gas (nitrogen) was maintained at 28 mℓ·min-1 whilst
pletely successful especially for biotic matrices (Awofolu and carrier gas was kept at the flow rate of 3 mℓ·min-1.
Fatoki, 2003).
Statistical analysis
Unfiltered water
All statistical analyses were carried out using the Statistical
100 mℓ of acidified unfiltered environmental water samples was Package for Social Scientists (SPSS) Software (Version 11.0).
measured into a 500 mℓ separating flask and extracted with 3 x One-Way ANOVA and Pearson’s Correlation Index were used
15 mℓ of dichloromethane (DCM) for OCP analysis. The extract to test for significant differences (95% confidence) and the rela-
was taken through the silica gel column clean-up. The eluates tionship between the results of water and sediments; summer
were concentrated to about 5 mℓ before GC analysis. and winter and among the lower (S1BS1, S1BS2, S2B and S2M),
middle (S3B, S3M, S4B, S4M, S5B and S5M) and upper (S6B,
Filtered water S6M, S7BS1 and S7BS2) streams to identify possible sources of
pollution with respect to OCPs studied.
100 mℓ of acidified filtered water samples from sites S1, S4 and
S7 were subjected to the method used by Koh et al. (2002) and Results and discussions
separated into particulate matter and then dissolved fraction
by using pre-combusted GF/F (0.7 µm nominal) glass-fibre fil- The gas chromatogram of OCPs standard mixture is shown in
ters (Whatman, Maidstone, England) under vacuum and were Fig. 2. Thirteen OCPs were identified and these are fairly well
extracted with DCM. The extraction procedure was carried out resolved. Unidentified peaks can be linked to the 4,4’-DDT tech-
as described earlier. nical grade standard used which is known to contain series of
contaminants.
Extraction test for adsorbed analytes from sampling In the case of the isomers of HCH (α-,γ- and δ), α–HCH eluted
bottle first leading other isomers as tabulated in Table 1. The RT ranged
from 6.12±0.05 (α-HCH, 290.83 g·mol-1) to 14.2±0.23 min (4,4’-
Sample bottles used for collecting water samples from sites S1, DDT, 354.59 g·mol-1). RT reported in the literature for 4,4’-DDT
S4 and S7 were rinsed with 3 x 10 mℓ of extraction solvent. The are 52.42 and 19.91 min (Brossa et al., 2002; Fatoki and Awo-
extracts were taken through the same procedure as described folu, 2003). Analysis time of 21.50 min was also reported for this
above before GC analysis. compound (Awofolu and Fatoki, 2003). Rf range of 0.34±0.05
and 5.59±0.95 was obtained for ENDO II and γ-HCH, respec-
Sediment samples tively. In this case, as in the case of RT, it was also noted that R f
followed no pattern in respect to physicochemical properties of
Sediment samples were thawed and air-dried in a dark cupboard OCPs. However, γ-HCH produced Rf greater than 1.0.

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 Figure 2
Gas chromatogram of OCP
standards, 1 = α –HCH;
2 = γ-HCH; 3 = Pentanitro­
chlorobenzene (IS);
4 = δ-HCH; 5 = Heptachlor; Signal
6 = 2,4’-DDE; 7 = ENDO I;
8 = 4,4’-DDE; 9 = 2,4’-DDD;
10 = Endrin; 11 = ENDO II;
12 = 2,4’-DDT; 13 = 4,4’-DDD
and 14 = 4,4’-DDT

Time (min)

TABLE 1 TABLE 2
Retention times (RT) ± Relative Standard Deviation Instrument detection limits
(RSD) and response factors (Rf ) ± RSD* of OCPs (IDLs) for OCPs
OCPs Retention time (min) Response factor OCPs IDL (ng·ℓ-1)
α-HCH 6.12±0.05 0.67±0.05 α-HCH 15.1
γ-HCH 7.05± 0.08 5.59±0.95 γ-HCH 14.9
δ-HCH 7.56± 0.04 0.62±0.29 δ-HCH 13.9
PCNB 8.06± 0.12 N/A Hepta 10.9
Hepta 8.69± 0.11 0.54±0.05 2,4’-DDE 7.10
2,4’-DDE 10.7±0.97 0.54±0.03 ENDO I 17.2
ENDO I 11.5± 0.34 0.34±0.05 4,4’-DDE 6.90
4,4’-DDE 12.3± 0.31 0.52±0.05 2,4’-DDD 6.00
2,4’-DDD 12.5± 0.43 0.64±0.09 Endrin 12.6
Endrin 12.7± 0.50 0.76± 0.05 ENDO II 15.3
ENDO II 12.9± 0.21 0.12±0.04 2,4’-DDT 5.30
2,4’-DDT 13.4± 0.11 0.46± 0.04 4,4’-DDD 13.0
4,4’-DDD 13.6±0.23 0.68±0.07 4,4’-DDT 16.3
4,4’-DDT 14.2± 0.23 0.31±0.06
*Values are average of twelve injections; RSD = Relative standard (2,4’-DDD) and 69.01%±6.93 (4,4’-DDD). From the results,
deviations; IS = Internal standard; N/A = Not applicable solvent combination of 1:1 DCM/HEX and DCM gave better
recoveries above 70% in all the compounds of interest. Xue et al.
Instrument detection limits (IDLs) (2006) using SPE reported recoveries ranging from 72% (endo-
sulfan sulphate) to 103% (ENDO II). Fatoki and Awofolu (2003)
The IDLs of OCPs are presented in Table 2. The IDL values and Awofolu and Fatoki (2003) using LLE also reported recov-
were calculated from linear regression equation of the calibra- eries from 71.03%±8.15 (dieldrin (C12H8Cl6O)) to 101.25%±2.17
tion curve of the OCPs standards as generated by the Star Chro- (α-BCH).
matograph Work Station Version 6 coupled to the gas chroma- Table 3 (next page) also shows mean percentage recover-
tography and as described by (Miller and Miller, 1998). IDLs of ies of OCPs from spiked sediment samples. Although three
the analysed OCPs ranged from 6.00 (2,4’-DDD) to 17.2 ng·ℓ-1 other evaluated solvents gave good results in most compounds
(ENDO I). Results obtained in the present study are lower than of interest in sediment samples, solvents, hexane, 1:1 DCM/
those reported for the same compounds are (Fatoki and Awofolu, HEX and 1:1 DCM/MET did not recover (2,4’-DDT and 4,4’-
2003; Awofolu and Fatoki, 2003; Basheer et al., 2005). DDT) and (2,4’-DDT). The best recoveries were obtained with
DCM where all analytes were detected. Two analytes (2,4’-
Quality assurance DDT and 4,4’-DDT) were not detected with hexane and 1:1
DCM/HEX. Xue et al. (2006) reported recoveries ranging
Mean percentage recoveries of OCPs in water and from 71% (p,p’-DDT) to 103% (endrin (C12H8OCl6)). Fatoki
sediment samples and Awofolu (2003) and Awofolu and Fatoki (2003) using SE
also reported recoveries ranging from 88.22%±7.85 (endrin)
The mean percent recoveries for triplicate analyses of OCPs to 109.63%±5.10 (β-BCH). The high percentage recoveries
from spiked doubly distilled water and sediment samples are obtained in all the compounds validated the extraction meth-
presented in Table 3. Results from spiked water samples using ods used in the present study.
hexane gave percentage recoveries of 14.50%±0.81 (γ-HCH),
69.05%±3.33 (2,4’-DDE), 45.92%±7.49 (ENDO I), 28.75%±3.28 Background analysis
(endrin) and NR (ENDO I and 2,4’-DDT) all below the accept-
able recovery value of 70%. For solvent 1:1 dichloromethane and Blank samples analysed were found to contain no target ana-
methanol (DCM/MET) recovery, the values below 70% were lytes. Both water and sediment samples did not show any peak
9.950%±0.52 (α-HCH), 12.73%±0.93 (γ-HCH), 67.10%±5.38 that might have had any influence on the results.

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 TABLE 3
Mean percentage recoveries ± RSD* of OCPs in spiked doubly distilled water and sediment samples
(in brackets) using four extracting solvent systems
Comp. HEX 1:1 DCM/HEX 1:1 DCM/MET DCM
α-HCH 106.0±2.49 (110.3±1.96) 111.6±0.39 (108.3±0.05) 9.950±0.52 (98.80±3.89) 119.7±0.34 (113.8±2.12)
γ-HCH 14.50±0.81 (116.7±0.21) 101.6±0.07 (118.7±1.11) 12.73±0.93 (87.70±3.21) 119.0±6.21(122.2±2.40)
δ-HCH 88.82±0.39 (119.3±1.65) 109.7±0.13 (115.6±2.00) 101.9±7.30 (103.1±5.34) 122.3±0.11 (123.2±0.27)
Heptachlor 98.43±4.67 (123.4±2.89) 109.2±0.54 (81.07±2.97) 103.4±5.51 (96.92±0.29) 114.5±5.26 (99.30±2.01)
2,4’-DDE 69.05±3.33 (96.30±0.34) 93.60±4.29 (98.08±6.43) 115.3±0.34 (92.08±6.11) 98.90±7.32 (98.99±5.30)
ENDO I 45.92±7.49 (112.6±0.91) 94.01±6.70 (109.8±2.05) 115.3±0.39 (98.80±0.82) 119.5±0.59 (111.3±0.47)
4,4’-DDE 113.1±2.91 (100.9±0.11) 113.7±0.49 (87.80±5.10) 112.0±0.99 (97.02±0.41) 119.2±0.28 (121.1±0.38)
2,4’-DDD 96.54±0.00 (82.03±0.67) 104.3±0.27 (91.00±1.03) 67.10±5.38 (82.09±1.67) 123.6±0.54 (101.4±0.24)
Endrin 28.75±3.28 (99.8±0.58) 101.4±0.39 (79.10±3.81) 106.7±3.27 (123.9±0.41) 123.7±8.34 (107.9±0.28)
ENDO II NR (72.7±4.89) 109.3±8.41 (79.22±1.34) 119.7±4.28 (81.50±0.07)
2,4’-DDT NR (NR) 90.05±0.60 (NR) 114.3±7.47 (NR)
4,4’-DDD 78.32±0.94 (94.44±0.62) 98.34±5.32 (89.23±2.56) 69.01±6.93 (86.30±0.39) 99.53±0.28 (101.8±0.32)
4,4’-DDT 99.11±0.48 (NR) 120.2±0.01 (NR) 120.1±0.36 (95.05±3.29) 114.3±6.37 (118.9±0.42)
NR = Not recovered

Methods validation Analysis of OCPs during summer and winter season

The results obtained for the analysis of certified reference mate- A typical gas chromatogram obtained from OCP analysis of
rials (CRMs) for OCPs are shown in Table 4. A reference waste- environmental samples is presented in Fig. 3. From the gas chro-
water (NIST QCM–200, North Kingstown, USA) for OCPs was matogram obtained, a fair number of peaks were clearly resolved
analysed to test the accuracy of proposed methods. As can be and the compounds studied could be identified. Un-identified
seen in Table 4, the results were generally in good agreement peaks were also shown from the gas chromatograms and these
with NIST certified values, indicating validity of methods used may be attributed to noise levels during analysis. The results
in this study for analysis of water and sediment samples. (mean levels) obtained from analysed OCP summer water and
sediment samples from the same sites are presented in Tables
TABLE 4 5 and 6; and the levels of OCPs detected in water varied from
Method validation showing true 0.981±0.16 (γ-HCH) to 3 068±0.56 (2,4’-DDE) ng·mℓ-1. The
and recovered values levels of OCPs studied in sediments ranged from 0.226±0.01
OCPs True value Recovered ng·gdw-1 (δ-HCH) to 5963±18.6 ng·gdw-1 (ENDO II).
(ng·mℓ-1) value (ng·mℓ-1) High levels were found at different points without any par-
HEPTA 8.40±0.05 7.20±0.06 ticular pattern. Site S1BS1 from Hartbeespoort Dam showed
high levels of α-HCH, heptachlor, 2,4’-DDD and 4,4’-DDT at
ENDO I 9.00±0.05 8.10±0.04
195.6±1.10 ng mℓ-1, 1 067±9.01 ng·mℓ-1, 117.8±3.02 ng·mℓ-1
4,4’-DDE 0.20±0.05 0.16±0.04
and 1 554±0.38 ng·mℓ-1 respectively. Other high levels of 4,4’-
ENDRIN 1.00±0.05 0.79±0.03 DDE, endrin and ENDO II were recorded from Site S3B at
4,4’-DDD 0.40±0.05 0.33±0.07 96.01±4.01 ng·mℓ-1, 65.87±4.01 ng·mℓ-1 and 629.3±14.1 ng·mℓ-1.
4,4’-DDT 5.00±0.05 4.10±0.06

Analysis of environmental water and

sediment samples

Identification of the OCPs in water and sediment

sample extracts were confirmed by comparing
their RT (time taken for each compound to elute Signal
in a chromatogram) with those of their stand-
ards. Concentrations were calculated using the
following equation: (USEPA, Method 515.3)
(Aa) (Cis)
Ca = (3)
(Ais) (RRF)
where:
Ca = concentration of the analyte (ng·mℓ-1
and ng·gdw-1 for water and sediments Time (min)

respectively)
Cis = concentration of the internal standard Figure 3
Representative gas chromatogram of OCPs environmental samples, 1 =
Aa = peak area of the analyte
α –HCH; 2 = γ-HCH; 3 = Pentanitrochlorobenzene (IS); 4 = δ-HCH; 5 =
Ais = peak area of the internal standard Heptachlor; 6 = 2,4’-DDE; 7 = ENDO I; 8 = 4,4’-DDE; 9 = 2,4’-DDD; 10 =
RRF = relative response factor Endrin; 11 = ENDO II; 12 = 2,4’-DDT; 13 = 4,4’-DDD and 14 = 4,4’-DDT

616 Available on website http://www.wrc.org.za

ISSN 0378-4738 = Water SA Vol. 34 No. 5 October 2008
ISSN 1816-7950 = Water SA (on-line)
 TABLE 5
Mean levels (ng·mℓ-1± RSD*) of OCPs in water samples collected during the summer period
OCPs Sampling sites
S1BS*1 S1BS*2 S2B S2M S3B S3M S4B S4M S5B S5M S6B S6M S7BS*1 S7BS*2
α-HCH 195.6±1.10 26.41±0.23 19.87±1.45 10.77±1.23 63.16±2.02 37.68±0.40 22.09±0.05 5.468±0.11 5.506±0.20 36.99±0.56 16.01±2.62 9.930±1.63 15.26±1.65 6.368±2.04
γ-HCH 3.759±0.20 3.593±0.40 10.29±1.08 2.395±0.34 4.577±0..30 1.733±0.04 1.286±0.06 0.981±0.16 1.316±0.06 4.638±0.45 13.94±2.18 2.754±0.11 2.369±0.05 9.900±1.80
δ-HCH 15.00±2.67 7.312±1.33 104.2±9.03 2.501±0.51 14.90±4.20 13.31±0.32 5.649±1.04 3.619±0.16 17.59±5.01 3.480±0.34 8.623±0.51 182.0±4.06 2.077±3.01 16.42±7.59
HEPTA 1067±9.01 14.14±0.51 43.32±4.04 950.7±16.3 68.05±4.18 639.5±7.16 56.48±9.04 399.9±40.4 13.58±1.88 81.37±1.96 32.50±1.80 421.7±1.03 82.24±3.21 56.62±6.02
2,4’-DDE 169.8±0.06 275.4±2.32 688.3±5.19 22.86±1.04 563.5±0.27 504.4±0.17 265.2±0.30 61.36±0.56 44.49±0.01 1469±0.20 333.9±0.12 3086±0.56 20.59±0.05 222.7±0.08
ENDOI 50.03±6.01 30.67±1.23 55.19±7.04 8.157±0.23 96.76±0.03 34.25±0.03 49.72±0.02 16.77±0.13 21.42±0.61 63.91±0.06 180.5±9.62 34.80±0.93 7.282±0.61 82.65±0.04

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4,4’-DDE 26.47±0.45 64.25±6.02 16.35±1.12 20.04±9.80 96.01±4.01 12.03±2.03 6.752±1.11 3.205±0.32 2.822±0.78 25.16±2.63 43.61±0.01 33.15±0.01 1.320±0..06 2.722±0.34
2,4’-DDD 117.8±3.02 36.05±4.01 41.09±4.23 10.20±0.76 51.00±2.02 4.735±0.45 10.01±1.01 9.474±0.45 38.66±1.90 21.30±2.41 28.35±2.01 21.79±6.04 4.310±0.21 13.75±2.53

Available on website http://www.wrc.org.za

ENDRIN 9.704±1.32 6.939±1.19 6.268±8.04 10.68±0.34 65.87±4.01 9.255±0.07 5.742±0.40 2.805±0.12 10.22±2.04 5.773±0.08 1.955±0.12 8.996±1.45 8.619±0.34 2.008±0.19
ENDOII 153.1±0.04 211.0±8.09 191.3±10.5 121.4±0.01 629.3±14.1 186.6±0.03 25.17±0.13 5.297±0.33 13.98±4.56 36.34±8.01 9.609±1.67 305.6±18.1 3.817±0.31 133.2±15.3
2,4’-DDT 19.50±1.45 53.29±4.01 50.90±16.1 10.44±2.34 180.6±10.2 20.18±9.43 33.31±6.51 5.197±0.42 34.09±2.02 20.10±9.56 250.1.±10.6 73.48±9.01 4.798±0.29 250.3±10.6
4,4’-DDD 36.27±1.01 28.05±2.56 47.19±23.1 25.48±0.34 41.69±1.01 37.16±0.45 4.623±2.76 2.230±0.11 27.05±0.34 59.36±0.01 23.99±9.90 76.00±6.02 8.347±1.65 50.09±2.52

ISSN 0378-4738 = Water SA Vol. 34 No. 5 October 2008

4,4’-DDT 1554±0.38 230.6±10.1 496.0±9.12 126.8±1.03 152.5±3.06 403.5±0.07 74.48±1.20 160.4±10.1 76.00±16.3 80.45±0.32 463.7±18.1 325.2±6.07 54.91±2.34 83.25±8.01
1 = Hartbeespoort Dam – S1 (S1BS*1 and S1BS*2), 2 = Before Johannesburg Water Works– S2 (SB2 and SM2), 3 = After Johannesburg Water Works – S3 (SB3 and SM3), 4 = Sandton /Kyalami – S4 (SB4 and SM4),
5 = Marlboro – S5 (SB5 and SM5), 6 = Alexander - S6 (SB6 and SM6), 7 = Bruma lake – S7 (S7BS*1 and S7BS*2); S = site; B = bank; S* = side and M = middle

TABLE 6
Mean levels (ng·gdw-1± RSD*) of OCPs in sediment samples collected during the summer period
OCPs Sampling sites
S1BS1 S1BS2 S2B S2M S3B S3M S4B S4M S5B S5M S6B S6M S7BS1 S7BS2
α-HCH 445.0±9.01 274.1±6.10 59.60±5.01 38.31±4.10 72.97±3.10 42.20±2.01 24.19±3.10 28.79±1.01 38.49±2.08 53.01±6.02 40.99±.02 37.19±0.02 28.34±3.02 62.37±6.03
γ-HCH 7.800±.1.01 11.00±1.01 1954±18.1 31.99±2.01 10.78±4.01 7.050±1.02 4.250±0.80 1.051±0.10 3.138±0.09 7.344±0.01 4.128±0.01 5.451±0.02 5.452±0.05 3.446±0.08
δ-HCH 122.0±8.02 56.70±3.10 3067±0.22 26.36±1.01 129.1±0.01 41.58±0.02 2.921±0.01 16.05±0.02 0.226±0.01 32.74±0.01 139.8±0.95 21.97±0.03 127.3±0.02 99.99±0.02
HEPTA 2916±0.01 3339±0.01 2237±0.01 3057±0.01 2056±0.10 2033±0.06 1623±0.01 1261±0.02 1063±0.10 1326±0.01 1125±0.04 1247±0.03 250.0±0.05 22.50±0.02
2,4’-DDE 817.0±0.10 369.6±0.10 2119±0.01 3866±0.01 781.2±0.10 739.9±0.06 653.0±0.01 564.6±0.03 770.0±0.10 2411±0.02 2573±0.01 38.64±0.05 1078±0.01 225.1±0.01
ENDO I 488.4±0.01 289.1±5.01 163.0±2.01 154.4±3.01 170.4±8.01 117.0±3.03 97.49±1.02 75.71±2.05 80.97±2.01 50.28±2.02 37.37±1.02 36.55±2.02 44.72±9.00 837.8±8.03
4,4’-DDE 154.9±3.01 83.61±2.10 83.40±4.02 238.1±0.01 115.6±7.10 44.96±6.02 43.78±4.05 21.23±2.02 17.84±1.02 30.21±3.02 11.70±6.01 16.75±2.02 13.72±1.01 49.16±6.01
2,4’-DDD 723.4±6.01 40.74±2.10 68.70±2.01 50.33±1.01 69.07±2.01 56.27±5.02 52.06±5.02 22.41±2.01 11.40±1.02 25.16±1.03 4.622±0.91 9.072±1.02 5.567±0.45 23.55±0.33
ENDRIN 70.90±2.01 40.54±2.10 17.73±1.01 76.17±0.10 71.24±1.10 68.53±4.02 49.42±7.05 22.07±1.01 12.77±1.05 39.11±2.05 21.51±3.10 14.83±1.01 8.940±2.02 6.788±2.16
ENDO II 5963±18.6 782.2±3.10 1490±13.1 703.7±9.01 760.3±11.1 594.7±4.03 50.39±5.02 241.6±2.01 153.9±8.03 201.0±9.04 100.9±6.54 101.5±5.01 119.0±5.01 25.26±2.01
2,4’-DDT 620.1±8.03 215.5±6.01 154.9±7.01 14.99±2.01 142.3±2.01 78.65±3.02 61.66±4.05 75.36±2.02 3.256±2.86 47.27±2.03 38.15±2.02 33.47±8.01 19.23±4.01 45.60±2.03
4,4’-DDD 524.1±6.10 163.9±.01 131.3±0.10 94.78±0.10 102.9±0.01 58.51±0.01 5.677±0.01 33.36±0.06 41.83±0.07 48.03±4.03 32.19±2.05 38.71±3.01 52.71±4.03 32.46±2.01
4,4’-DDT 3279±18.1 2379±6.10 820.8±7.01 1677±4.01 700.5±6.01 959.1±2.01 575.1±6.02 593.8±3.04 568.0±4.01 450.9±3.02 434.8±8.02 419.7±7.01 552.1±7.02 567.5±2.01

617
 TABLE 7

618
Mean levels (ng·mℓ-¹ ± RSD*) of OCPs in water samples collected during the winter period
OCPs Sampling Sites
S1BS*1 S1BS*2 S2B S2M S3B S3M S4 S4M S5B S5M S6 S6M S7BS*1 S7BS*2
α-HCH 71.7±8.05 33.73±6.01 73.21±6.01 28.47±1.56 795.2±5.07 21.69±2.01 22.85±2.01 16.67±3.01 13.05±2.01 61.25±3.02 22.98±4.01 22.15±2.02 17.85±2.01 21.87±4.04
γ-HCH 33.79±5.01 5.045±1.45 159.5±4.86 3.083±0.45 20.73±2.02 3.700±0.12 3.951±0.13 0.631±0.23 1.071±0.02 17.42±2.01 25.90±0.78 11.97±1.01 4.552±0.11 3.477±0.13
δ-HCH 78.62±1.05 34.48±0.01 154.2±1.22 2.061±0.11 42.00±2.03 37.34±0.41 7.000±0.51 5.649±0.12 26.80±1.02 8.428±1.04 51.96±2.01 4.468±0.31 41.67±2.65 34.88±1.69
HEPTA 1285±1.09 245.5±2.10 576.1±5.01 861.8±6.01 804.1±7.50 518.6±4.04 343.0±2.22 509.7±3.02 352.0±1.19 764.6±2.04 424.0±1.11 268.3±2.11 83.80±2.09 79.53±2.07
2, 4’-DDE 392.8±3.09 299.2±2.10 730.5±1.10 928.8±2.01 598.3±1.35 264.1±2.17 582.3±2.54 333.5±0.14 249.6±2.13 175.3±0.01 604.6±3.10 15.18±2.01 373.1±2.09 289.7±5.01
ENDO I 363.9±2.09 242.4±3.12 56.47±1.10 38.25±1.24 293.6±2.29 231.6±1.23 212.2±1.13 21.83±3.01 27.08±2.03 23.32±1.23 48.99±1.01 22.20±2.11 15.74±1.04 15.85±1.03
4, 4’-DDE 140.3±4.12 25.00±2.01 189.8±1.07 179.2±1.66 74.00±3.04 41.62±4.02 7.566±2.65 6.222±0.22 60.01±2.01 27.42±1.01 27.46±2.10 48.19±2.01 4.967±0.11 8.227±1.06
2, 4’-DDD 284.3±2.01 48.32±1.05 68.56±1.80 85.59±0.31 55.60±2.05 19.85±1.01 19.74±1.12 28.32±2.01 38.31±2.01 22.88±1.02 3.453±1.20 2.945±0.01 1.947±0.01 2.529±0.56
ENDRIN 39.31±1.32 5.619±1.08 45.49±1.32 18.64±1.67 50.96±1.03 45.78±1.01 19.00±1.05 9.270±0.23 13.75±1.01 18.28±1.01 5.383±0.42 4.897±0.07 3.226±8.06 6.963±0.93
ENDO II 966.5±1.32 464.5±2.16 241.0±1.32 264.9±1.88 227.6±2.11 210.4±1.13 47.69±1.01 74.88±1.51 52.27±3.04 18.30±1.03 27.32±1.02 7.461±3.22 13.28±1.01 94.85±1.41
2, 4’-DDT 443.6±2.19 84.91±3.03 508.1±2.21 75.98±1.90 310.3±1.34 173.1±1.19 43.01±0.72 59.45±1.01 20.85±1.11 26.57±0.06 8.189±0.08 8.871±0.03 6.956±0.01 19.47±0.65
4, 4’-DDD 306.5±2.04 77.25±1.02 83.90±1.45 23.97±1.70 69.24±1.03 39.46±1.02 5.657±0.16 19.95±0.31 33.51±2.01 31.78±1.06 45.49±1.02 29.34±1.05 17.97±0.41 11.82±0.88
4, 4’-DDT 1453±5.38 1540±2.19 512.4±1.32 145.7±1.68 259.4±3.13 363.2±1.23 200.8±2.06 211.5±2.02 290.2±1.14 214.9±1.67 194.7±1.05 180.4±1.03 198.6±1.01 200.6±1.45

TABLE 8
Mean levels (ng·gdw-1 + RSD) of OCPs in sediment samples collected during the winter period
OCPs Sampling sites
S1BS*1 S1BS*2 S2B S2M S3B S3M S4B S4M S5B S5M S6B S6M S7BS*1 S7BS*2
α-HCH 851.7±2.11 136.3±2.11 673.3±1.18 893.4±2.27 319.2±2.11 281.6±3.04 237.8±1.04 321.2±2.10 164.2±1.23 191.7±1.03 171.3±3.01 64.17±1.01 88.37±1.01 161.5±1.02
γ-HCH 33.57±1.02 274.7±4.03 360.9±2.01 205.0±1.02 23.22±1.01 12.92±1.23 10.12±1.12 47.16±1.39 4.261±0.11 24.38±1.23 60.77±1.01 17.45±1.01 376.1±2.03 481.2±3.13
δ-HCH 6952±5.12 2191±3.45 2650±1.73 12221±3.88 75.49±1.02 100.7±5.01 52.69±2.05 271.6±1.17 1227±7.07 1146±2.76 37.31±1.03 1326±4.32 636.7±2.88 73.31±1.56
HEPTA 4522±4.79 3863±2.11 6643±3.06 7934±3.64 4462±3.01 4832±2.03 4010±2.29 3433±1.48 11141±2.23 6396±1.12 14070±1.68 2708±2.21 4488±1.94 4648±1.48
2,4’-DDE 2521±2.01 11139±3.92 22914±4.85 193.0±1.80 2856±2.33 3712±1.93 2218±1.51 5228±1.24 14016±4.83 7545±2.10 3199±1.99 19630±4.41 104.9±2.03 999.5±1.27
ENDO I 294.5±4.07 157.3±2.01 883.0±1.12 731.9±2.09 486.3±1.15 256.8±0.04 1391±1.13 1451±1.49 250.0±1.06 331.6±2.06 3705±3.35 225.1±1.03 419.6±2.03 348.7±2.05
4,4’-DDE 130.2±1.64 321.0±1.12 130.6±1.04 168.8±2.01 495.5±1.07 91.82±2.01 1133±1.09 1270±1.94 84.06±1.04 127.7±1.12 187.5±1.04 212.0±1.08 80.91±1.02 1143±2.33
2,4’-DDD 462.8±1.16 183.2±1.04 147.2±1.03 84.68±1.02 262.2±1.11 37.28±1.01 10349±2.61 814.4±1.13 130.2±1.01 106.3±1.34 270.6±1.05 140.2±1.05 46.32±1.01 607.5±1.08
ENDRIN 52.96±1.01 142.1±1.05 216.0±2.06 88.84±2.02 342.5±1.07 68.71±1.01 1149±1.14 2363±1.74 55.50±1.01 282.6±2.03 516.4±3.32 56.36±.02 40.76±1.23 983.3±1.58
ENDO II 651.9±1.15 1066±1.40 662.4±1.15 1022±2.08 3242±1.12 1433±1.31 11462±2.38 4580±2.43 1175±1.20 1735±1.51 88.18±1.02 1904±2.12 678.6±2.66 207.0±1.30
2,4’-DDT 83.33±1.03 268.8±1.07 173.3±2.03 86.63±2.02 926.2±1.05 152.4±1.02 1269±1.04 885.2±1.36 94.12±1.04 493.4±1.07 1082.±1.08 466.0±1.09 375.2±2.19 1204±1.49
4,4’-DDD 143.8±1.04 142.8±1.03 162.1±1.01 214.7±1.01 661.3±1.05 342.5±1.06 1252±2.18 903.3±1.66 79.37±2.34 296.1±1.86 102.7±1.01 483.8±2.15 195.2±1.02 289.9±2.03
4,4’-DDT 629.3±1.15 1184±1.03 1715±1.30 1055±2.26 5133±2.02 3164±2.99 13310±2.77 13201±1.23 3016±1.25 2697±1.44 1990.8±1.30 2062±1.34 2315±1.62 407.3±1.12
and
(S7BS2).

ng·gdw-1 (2,4’-DDE).

collected from different parts

respectively, while those of

In the former areas, levels of
sediment, soil and some biota

∑DDT in water, sediments

nant in all the studied areas.
levels of residues were found

DDT and HCH were domi-

areas were substantially high.
levels in the former storage
cultural pesticide use but the
of Tanzania. Generally, low
water, pore water and sedi-
275 to 1 600 ng·ℓ-1 and 5 250
studied were reported and
obtained in this study. Xue et
ies were lower than those
DDT) and those of sediments
7 and 8. The levels of water
The results of analysed
low levels in most sites at
(4,4’-DDD). γ-HCH showed

4.577±0.30 ng·mℓ-1 (S3B),

2.395±0.34 ng·mℓ-1 (S2M),
10.29±1.08 ng·mℓ-1 (S2B),
Site S6M also showed high

ISSN 1816-7950 = Water SA (on-line)

ISSN 0378-4738 = Water SA Vol. 34 No. 5 October 2008
Available on website http://www.wrc.org.za
700 μg·kg−1 and 500 μg·kg-1,
and soil were up to 2 μg·ℓ-1,
in areas associated with agri-
the levels of OCPs in water,
carried out a study to assess
tively. Kishimba et al. (2004)
ervoir. Total levels of OCPs

ment (dry weight), respec-

to 33 400 ng·kg-1 in surface
ranged from 16.7 to 791 ng·ℓ-1,
(γ-HCH) to 22 914±4.85
ranged from 4.261±0.11 to
to 1540.2±0.19 ng·mℓ-1 (4,4’-
varied between 0.631±0.01
period are tabulated in Tables

from Beijing Gaunting res-

surface water and sediments
al. (2006) studied 21 OCPs in
els of OCPs in similar stud-
Some of the reported lev-
collected during the winter
OCPs in water and sediment
9.900±1.80 ng·mℓ-1
2.369±0.05 ng·mℓ-1 (S7BS1)
2.754±0.11 ng·mℓ-1 (S6M),
13.94±2.18 ng·mℓ-1 (S6B),
4.638±0.40 ng·mℓ-1 (S5M),
1.316±0.06 ng·mℓ-1 (S5B),
0.981±0.16 ng·mℓ-1 (S4M),
1.286±0.06 ng·mℓ-1 (S4B),
1.733±0.04 ng·mℓ-1 (S3M),
3.593±0.40 ng·mℓ-1 (S1BS2),
3.759±0.20 ng·mℓ-1 (S1BS1),
and 76.00±6.02 ng·mℓ-1
(δ-HCH), 3 086±0.56 ng·mℓ-1
levels at 182.0±4.06 ng·mℓ-1
∑HCH were up to 0.2 μg·ℓ−1, 132 μg·kg−1 and 60 μg·kg−1, respec- cantly higher values than the upper-stream (237.672 ng·mℓ-1) at
tively. Fatoki and Awofolu (2003) and Awofolu and Fatoki (2003) p ≤ 0.05. Higher levels obtained in the downstream and mid-
studied water and sediment samples from marine and freshwa- stream river might be due to runoff from golf courses and sur-
ter sources in the Eastern Cape Province of South Africa that rounding agricultural fields. Xue et al. (2006) reported that the
receive runoff from agricultural lands and effluents from indus- observed variation in OCP levels in the reservoir (both in water
tries. The levels of OCPs reported ranged from 5.5 (2,4-DDD) to and the sediments) can be expected to be caused by several rea-
450±0.10 ng·ℓ-1 (β-BHC) in water samples and from 0.6 (aldrin sons such as high rates of influx of contaminants into the reser-
and 2,4-DDD) to 184±0.12 ng·g-1 (β-BHC) in sediments for trip- voir through tributary rivers and drainage of contaminated water
licate analyses. Some endocrine disrupting OCPs such as DDT, from the surrounding agricultural fields. The accumulation and
DDE, heptachlor, ENDO and chlordanes were also detected. the inflow from the Crocodile River which joins the catchment
Osuna-Flores and Riva (2002) investigated surface water and downstream might have also contributed to high levels. Lower
sediments from the Bay of Ohuira, Mexico. The highest levels levels in the upper stream compared to other streams are attrib-
were observed for ENDO I (0.0472 to 2.005 µg·g-1) and the low- uted to the absence of agricultural fields in the area.
est range of levels were for DDE with 0.019 to 0.021 µg·g-1 and
were lower than those obtained in this study from environmental Analysis of filtered water samples
water and sediment samples.
Analysis of results of water and sediment samples in this The results of filtered water samples for OCP analyses are
study showed that levels of most OCPs detected were above the represented in Table 9. As can be seen from Table 9, the results
maximum acceptable levels for water, e.g. heptachlor (USEPA, obtained did not show any appreciable differences compared to
1984). These high levels give cause for concern because this the results obtained from unfiltered water samples, although fil-
could expose some of the primary users of water to these pollut- tered water samples have been reported to have slightly lower
ants with potential health effects. Thus the community and the levels (Smith et al., 2001). The higher levels reported for unfil-
environment in the catchment area could be at risk if the trend tered water samples were attributed to the high adsorption affin-
is not monitored. USEPA water quality guidelines to protect ity of OCPs for particulate material in the water samples.
the aquatic ecosystems are 0.00083 ng·mℓ-1 (4,4’DDD), 0.00059
ng·mℓ-1 (4,4’DDE), (4,4’DDT), 0.00021 ng·mℓ-1 (heptachlor), Analysis of OCPs adsorbed on sampling bottle
0.0092 ng·mℓ-1 (α-HCH), 0.0186 ng·mℓ-1 (γ-HCH), and chronic
values are 0.056 ng·mℓ-1 (ENDO I and II) and 0.0023 ng·mℓ-1 Table 10 shows the results obtained from the rinsed sampling bot-
(endrin) (USEPA, 1995). High levels of OCPs obtained in this tles to recover possible analyte losses through analyte retention
study could be because of the runoff from agricultural activities on sample bottles. From Table 10, all compounds studied were
around the catchment, e.g. farms and domestic gardens. detected from the samples. 4,4’-DDT (1.06±0.02 mg·mℓ-1) from
Similarly, the average OCP levels observed in the sediment Site S1BS1 recorded the highest value and ENDOI (0.01±0.01
samples (1 176.12 ng·gdw-1) was significantly higher than that mg·mℓ-1) the lowest detected compound from S4M. The percent-
observed for water samples (142.310 ng·mℓ-1) at p ≤ 0.05. This is age levels of OCPs in environmental water samples (98.90 to
not surprising since sediments are known to act as sinks for pol- 121.10%) were much higher than those recovered on the sampling
lutants in the aquatic environment (Chee et al., 1996). The aver- bottles (0.02 to 5.18%). Therefore, the results show that analytes
age levels were observed to be higher in winter (1 032.37) than studied were capable of adsorbing on the sampling bottle.
in summer (286.06) and this could be attributed to the impact
of precipitation. This difference was observed to be significant Conclusions
(p ≤ 0.05). No significant correlation was, however, observed
between compounds during the two seasons. The conditions of GC-ECD were successfully optimised and the
Comparing the levels of OCPs in the downstream, midstream method developed was applied in the determination of OCPs
and upper-stream river, the average levels in the downstream studied. The analysis times were shortened and peak resolution
(731.210 ng·mℓ-1) and midstream (721.923 ng·mℓ-1) gave signifi- was good in most cases.

TABLE 9
Mean levels (ng·mℓ-1 ± RSD*) of OCPs in filtered water samples
OCPs Sampling sites
S1BS1 S1BS2 S4B S4M S7BS1 S7BS2
α-HCH 189.2±2.10 21.10±0.11 21.09±0.12 5.823±0.21 15.94±0.02 6.149±2.01
γ-HCH 3.345±1.02 2.903±0.15 1.030±0.21 0.895±0.11 2.013±0.01 9.612±0.42
δ-HCH 14.99±1.01 7.349±0.41 5.231±1.01 3.341±0.23 1.989±0.54 16.01±2.10
HEPTA 9089±2.08 26.89±0.19 53.84±0.10 393.4±5.01 81.06±0.51 56.92±0.01
2,4’-DDE 170.1±1.02 2.854±0.91 256.9±0.19 62.01±0.31 19.06±0.31 220.0±2.01
ENDO I 52.94±1.04 34.97±0.22 50.01±1.27 17.04±0.21 7.397±0.19 80.56±2.90
4,4’-DDE 23.96±1.01 33.93±0.12 6.940±1.02 3.012±0.61 1.245±0.71 3.927±0.11
2,4’-DDD 119.0±2.02 36.05±0.11 10.04±0.02 9.344±0.72 4.129±0.52 14.03±0.51
ENDRIN 8.923±1.01 5.934±0.02 5.823±0.01 2.432±0.91 8.465±1.41 2.133±0.17
ENDO II 151.1±3.02 208.0±4.21 23.07±2.02 5.545±0.93 3.423±0.31 131.0±2.13
2,4’-DDT 18.93±2.09 55.93±1.01 36.32±2.01 4.973±0.81 4.534±1.02 248.0±3.90
4,4’-DDD 33.94±1.06 25.93±1.02 5.324±1.01 2.023±0.45 8.213±1.01 51.41±2.10
4,4’-DDT 1559±3.42 243.0±3.01 70.94±2.12 159.4±7.65 53.93±3.06 83.56±2.07

Available on website http://www.wrc.org.za 619

ISSN 0378-4738 = Water SA Vol. 34 No. 5 October 2008
ISSN 1816-7950 = Water SA (on-line)
 TABLE 10
Mean levels (ng·mℓ-1 ± RSD*) of OCPs from rinsed sampling bottle
OCPs Sampling sites
S1BS1 S1BS2 S4B S4M S7BS1 S7BS2
α-HCH 0.03±0.02 0.06±0.01 0.07±0.02 0.02±0.01 0.03±0.02 0.02±0.01
γ-HCH 0.04±0.02 0.05±0.01 0.05±0.01 0.03±0.01 0.02±0.01 0.02±0.02
δ-HCH 0.04±0.01 0.05±0.01 0.02±0.01 0.02±0.01 0.02±0.01 0.03±0.01
HEPTA 0.09±0.01 0.07±0.01 0.09±0.01 0.04±0.01 0.06±0.01 0.05±0.01
2,4’-DDE 0.45±0.02 0.06±0.01 0.08±0.01 0.07±0.01 0.05±0.01 0.04±0.01
ENDO I 0.09±0.01 0.04±0.02 0.02±0.01 0.01±0.01 0.02±0.01 0.03±0.01
4,4’-DDE 1.02±0.02 0.01±0.02 0.08±0.02 0.04±0.01 0.06±0.01 0.04±0.01
2,4’-DDD 1.00±0.02 0.06±0.01 0.09±0.02 0.06±0.02 0.07±0.02 0.05±0.01
ENDRIN 0.07±0.03 0.02±0.02 0.02±0.01 0.03±0.01 0.03±0.01 0.03±0.07
ENDO II 0.03±0.02 0.06±0.02 0.03±0.01 0.02±0.01 0.02±0.01 0.02±0.03
2,4’-DDT 1.01±0.04 0.15±0.01 0.09±0.01 0.02±0.01 0.08±0.02 0.06±0.01
4,4’-DDD 0.09±0.04 0.22±0.02 0.12±0.01 0.03±0.01 0.09±0.01 0.09±0.01
4,4’-DDT 1.06±0.02 0.13±0.01 0.16±0.12 0.05±0.01 0.10±0.06 0.09±0.07

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The authors would like to thank Tshwane University of Tech- FERNANDEZ-ALBA AR, AGUERA A, CONTRERAS M, PNUELA
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