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Chemosphere 71 (2008) 294–298

www.elsevier.com/locate/chemosphere

Levels of organochlorine pesticides residues in dairy products

in Kumasi, Ghana
1
Godfred Darko *, Samuel Osafo Acquaah
Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana

Received 15 May 2007; received in revised form 3 September 2007; accepted 5 September 2007
Available online 17 October 2007

Abstract

Determination of six organochlorine pesticides, lindane, aldrin, dieldrin, endosulfan, dichlorodiphenyltrichloroethane (DDT), and
dichlorodiphenyldichloroethylene (DDE), residues were carried out on three dairy products sampled from six communities in the Kum-
asi metropolis in Ghana. Cheese samples were collected from three communities, (Tafo, Asawasi, and Aboabo), yoghurt samples from
K-Poly and Ayeduasi while yoghurt and milk samples were collected from KNUST. Concentrations of DDT and DDE were, respec-
tively, 42.17 ± 6.00 lg kg1 and 31.50 ± 3.44 lg kg1 in cheese sampled from Asawasi. Cheese samples from Tafo had an average
DDT concentration of 298.57 ± 28.02 lg kg1 while DDE concentration was 140.15 ± 56.77 lg kg1. The highest average concentration
of DDT in all the samples was 149.07 lg kg1 detected in cheese samples from Aboabo. Levels of DDT and its metabolite, DDE, in
cheese from all the three sampling sites (Aboabo, Asawasi and Tafo) were well below the levels recommended by World Health Orga-
nisation (WHO). Mean concentration of DDT in fresh milk samples from KNUST was 12.53 ± 1.61 lg kg1. As bioaccumulation of
these residues is likely to pose problems in higher organisms, like human beings, there is the need for effective monitoring of these res-
idues in the environment. This work, thus, seeks to provide information on levels of pesticide residues in dairy products that will assist in
a scientific assessment of the impact of pesticides on public health, agriculture and the environment in Ghana.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Dairy products; Organochlorine pesticides; Gas chromatography; Electron capture detector

1. Introduction widely used in cotton growing areas, on vegetable farms,

Until the early 1980s, many chlorinated insecticides,
mainly; aldrin, dieldrin, DDT, and lindane have been used
in controlling pests of crops, vectors of some diseases and
other aspects of public health in Ghana (UNEP, 2002).
Some of these pesticides are still widely used by farmers
because of their effectiveness and their broad-spectrum
activity (Amoah et al., 2006). Lindane is used on cocoa
plantations, vegetable farms, and for the control of stem
borers in maize. Endosulfan, marketed as thiodan, is
*
Corresponding author. Tel.: +233 24 3239354; fax: +233 51 40808/
60305.
E-mail addresses: godfreddarko@yahoo.com (G. Darko), sosafoac-
quaah@hotmail.com (S.O. Acquaah).
1
Tel.: +233 24 3222276; fax: +233 51 60305.
and on coffee plantations (Ntow et al., 2006). Organochlo-
rine pesticides such as dichlorodiphenyltrichloroethane
(DDT), lindane and endosulfan are also employed to con-
trol ectoparasites of farm animals and pets in Ghana
(Awumbila and Bokuma, 1994).
Most organochlorine insecticides, except lindane, are
very stable solids with limited vapour pressure and very
low water solubility. They are highly lipophilic and resis-
tant to microbial degradation (UNEP, 2001; Kaushik
and Kaushik, 2007). They can, therefore, accumulate in
fatty adipose tissues and in the environment. As these
chemicals are inherently toxic to living organisms, the pres-
ence of their residues in food items is of a major concern to
environmental and consumer groups (Willes et al., 1993).
Acute toxic effects of pesticides on animals and humans
are fairly easily recognized, but the effects that result from

0045-6535/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2007.09.005
 Author's personal copy
G. Darko, S.O. Acquaah / Chemosphere 71 (2008) 294–298
Table 1
Mean recovery (%), relative standard deviation (RSD) (%), limits of detection (LD) (n = 4)
Milk Yoghurt
1
Recovery RSD (%) LD (lg kg ) Recovery
Lindane 66 6 0.08 68
Aldrin 61 5 0.10 72
Endosulfan 72 4 0.15 74
p,p 0 -DDE 82 6 0.10 91
Dieldrin 83 5 0.10 72
p,p 0 -DDT 75 13 0.12 95
long-term exposure to low doses are often difficult to
distinguish. Data on the consumption of individual pesti-
cides in Ghana are very difficult to obtain, because manu-
facturers are reluctant to disclose such information and
there is little governmental control of the use of such
chemicals.
Work already done in some farming communities in the
Ashanti region of Ghana has indicated the presence of
organochlorine pesticide residues in fish (Osafo Acquaah,
1997) vegetables, water, sediments, mother’s milk and
blood samples (Ntow, 2001). Significantly, as high as
30.7 g kg1 hexachlorobenzene and 380.7 g kg1 p,p 0 -
DDE were reported to be present in blood samples of some
farmer in this study. In another study carried out on
the Volta lake, the largest lake in Ghana, lindane and endo-
sulfan were identified in concentrations 60.008 and
0.036 ppb, respectively, in water, and 62.3 and 0.36 ppb,
respectively, in sediments. DDT and dichlorodiphenyldi-
chloroethylene (DDE) were also found in sediment samples
in concentrations 69.0 and 52.3 ppb, respectively, (Ntow,
2001). No data is however available on the levels of these
residues in dairy products which constitute an important
part of meal of many communities in Ghana.
Because of their highly lipophilic nature, organochlorine
pesticides and their residues may easily concentrate in fatty
foods (such as milk products) leading to bioconcentration
and biomagnification through the food chain. There is,
therefore, the need for constant monitoring of levels of
these residues in foodstuffs and the environment in order
to avert any environmental and health disaster. This work,
thus, seeks to provide information on levels of pesticide
residues in dairy products that will assist in a scientific
assessment of the impact of pesticides on public health,
agriculture and the environment in Ghana.
2. Methodology
All chemicals were purchased from BDH and were of
pesticide residue grade. Organochlorine pesticides (lindane,
aldrin, dieldrin, p,p 0 -DDE, p,p 0 -DDT, and endosulfan)
standards were purchased from Ehrenstorfer, GmbH, Ger-
many, in sealed vials. SPE bond elut C–18, 3 cc/500 mg
were purchased from Varian Inc., USA. A Shimadzu GC
– 9A gas chromatograph equipped with a 63Ni electron
capture detector and SPB – 608 (15 m · 0.5 m film) capil-
lary column was used in the analysis.
295
Cheese
1
RSD (%) LD (lg kg ) Recovery RSD (%) LD (lg kg1)
4 0.50 85 4 0.10
2 0.12 73 7 0.20
6 0.23 62 8 0.35
3 0.30 94 6 0.02
2 0.05 71 6 0.40
3 0.04 95 5 0.95
Cheese samples were collected from three communities,
(Tafo, Asawasi, and Aboabo), yoghurt samples from K-
Poly and Ayeduasi while yoghurt and milk samples were
collected from KNUST, all in the Kumasi metropolis.
Sampling was done in two batches of ten samples each
between the period of May–July 2004, for the first batch,
and December 2005–March 2006, for the second batch.
Sampling was carried out weekly.
About 10 ml of fresh yoghurt and of milk were taken
from every drum of processed stuff brought for sale on
the day of sampling. For cheese, two balls were randomly
selected from every 100 balls being offered for sale. Samples
are collected into plain polythene bags, kept frozen in an
ice chest and sent immediately to the laboratory. In the lab-
oratory, each of the products was bulked together, ground
and mixed thoroughly. A total of twenty samples were
taken from each sampling site.
Ten grams of sample (milk or yoghurt) was ground with
anhydrous sodium sulphate to yield a dry free-flowing
powder which was then transferred into a glass extraction
column of length 30 cm and internal diameter 2 cm. The
dry column was then eluted with 80 ml of dichloromethane
with the first 40 ml allowed to stay in contact with the pow-
der for 30 min. Dichloromethane in the eluate was removed
using a rotary evaporator at 35 C under reduced pressure
(US-EPA, 1980).
For cheese, 1 g sample was added to 20 ml methanol,
2 ml of 10% sulphuric acid, and 1 g sodium oxalate to
mix. To this was added 20 ml of ethylether/petroleum ether
(1:1) and then shaken vigorously for 1 min. The mixture
was centrifuged at 1500 rpm for 5 min and the solvent layer
transferred into 1 l separatory funnel. To this, was added
5 ml saturated sodium chloride solution and 2 ml of 10%
sulphuric acid to wash. Aqueous residue in the centrifuge
bottle was re-extracted twice with 10 ml portions of ethyle-
ther/pet ether (1:1). The organic portions were combined
and the aqueous portion discarded. The solvent layer
(extract) was re-washed twice with 20 ml distilled water,
2 ml of 10% sulphuric acid and 5 ml saturated sodium chlo-
ride solution. The extract was allowed to stand for 30 min
and water drained off. The solvent was evaporated on a
rotary evaporator at 40 C. The extract was allowed to cool
and the fat extracted with 10 ml methylene chloride solu-
tion (US-FDA, 2002).
Each of the raw extracts was dissolved in 10 ml hexane
and passed through pre-conditioned octadecyl C18 columns
 Author's personal copy

296 G. Darko, S.O. Acquaah / Chemosphere 71 (2008) 294–298

at a rate of 2 ml min1 to clean up. The column was Table 2

washed with 1 ml, 30% methanol followed by 1 ml distilled Levels of pesticide residues in fresh milk from KNUST
water and was allowed to dry. The sample (analyte) which EMRL/MRL Mean Range SD
was trapped in the column was eluted five times with 0.5 ml (lg kg1) (lg kg1)
aliquots of hexane to recover the pesticide residues. Hexane Lindane 10a <LD <LD <LD
in the sample was then allowed to evaporate off leaving the Aldrin 6b 0.22 <LD– 0.01
0.05
residue alone in the vial. Dried sample was dissolved in Endosulfan 4a 0.60 0.02–0.12 0.03
1 ml portion of hexane, mixed thoroughly with a whirl p,p 0 -DDE – 1.42 0.01–4.62 0.02
mixer and then transferred to autosampler vials ready for Dieldrin 6b 1.32 0.04–4.62 0.20
gas chromatography. p,p 0 -DDT 20b 12.53 0.44– 0.01
The gas chromatographic analysis was performed under 28.62
the following conditions: the detector temperature was n = 20 for each site.
320 C. The injector temperature was 220 C and the col- <LD = below detection.
SD = standard error of mean.
umn temperature was 160 C (isothermal). Carrier gas a
Maximum residue level.
was helium at a flow rate of 30 cm s1. One micro litre b
Extraneous maximum residue level.
(1 l) of sample was injected into the GC.
Recovery analyses were carried out on samples fortified (Gerken et al., 2001). This trend is also reflecting the reduc-
at 1 lg kg1. After extraction and solvent evaporation, the tion and responsible use of organochlorine pesticide in
samples were analysed according to the proposed method. recent times (UNEP, 2002). DDT concentration in milk
The recovery values were calculated from calibration samples was found to be about nine folds that of, its
curves constructed from the concentration and peak area metabolite, DDE. This may suggest recent or continuous
of the chromatograms obtained with standards of the orga- use of DDT on the cattle and/or their feedstuff. Aldrin
nochlorine pesticides (Table 1). Blank analyses were also was detected in 75% of the samples at a mean concentra-
performed in order to check interference from the sample. tion of 0.02 + 0.01 lg kg1 while, its metabolite, dieldrin,
All determinations were done in triplicates. registered an average level of 1.32 ± 0.20 lg kg1 in all
Concentrations of the various residues in each sample the milk samples analysed. This may indicate the metabo-
were calculated in lg kg1 sample and the average concen- lism of original aldrin contaminant into dieldrin. The aver-
tration of each pesticide was compared to the Codex Max- age levels of both aldrin and dieldrin, recorded in milk
imum Residue Limits/Extraneous Maximum Residue were, however, well below their extraneous maximum limit
Limits, MRL/EMRLs, (WHO/FAO, 2006). of 6.00 lg kg1. The average level of 0.06 + 0.03 lg kg1
endosulfan recorded in milk is also lower than the maxi-
3. Results and discussion mum residue level of 4.00 lg kg1 recommended by the
WHO. Lindane was not detected in any of the 20 milk sam-
As shown in Table 2, an average of 12.53 lg kg1 of ples analysed (Table 3).
DDT was recorded for fresh milk sample. This value is Comparatively, yoghurt samples from Ayeduasi regis-
lower than those recorded for fresh milk from some devel- tered the highest average concentration of DDT and
oping countries, for example, Uganda 3.24 mg kg1, Nige- DDE of all yoghurt samples analysed. This was followed
ria 3.83 mg kg1, India 6.55 mg kg1, Kenya 6.99 mg kg1, by samples from K-Poly and then KNUST. Levels of
South Africa 20.10 mg kg1 and Ethiopia 7.75 mg kg1 aldrin and dieldrin also followed a similar trend. DDT
(FAO, 1986). The results are not surprising as all those and DDE were detected in all the yoghurt samples analysed
countries use more chlorinated insecticides than Ghana but were all below the extraneous maximum level of

Table 3
Levels of pesticide residues in yoghurt
EMRL/MRL (lg kg1) Ayeduasi KNUST K-Poly
Mean (lg kg1) Range SD Mean (lg kg1) Range SD Mean (lg kg1) Range SD
a
Lindane 100 <LD <LD <LD 0.03 0.01–0.05 0.01 0.01 <LD–0.01 0.05
Aldrin 150b 0.08 0.03–0.11 0.03 0.03 <LD–0.11 0.04 0.09 0.02–0.15 0.05
Endosulfan 100a 0.05 0.02–0.12 0.04 0.06 <LD–0.34 0.10 0.06 0.01–0.14 0.02
p,p 0 -DDE – 1.60 0.65–2.05 0.60 0.49 0.01–1.55 0.15 0.55 0.02–1.41 0.15
Dieldrin 150b 0.14 <LD–0.34 0.18 0.02 0.01–0.03 0.01 0.02 <LD–0.03 0.01
p,p 0 -DDT 500b 8.96 1.36– 5.67 4.09 0.71– 0.17 7.52 1.30– 2.00
17.50 15.65 19.20
n = 20 for each site.
<LD = below detection.
SD = standard error of mean.
a
Maximum residue level.
b
Extraneous maximum residue level.
 Author's personal copy

G. Darko, S.O. Acquaah / Chemosphere 71 (2008) 294–298 297

Table 4
Levels of pesticide residues (lg kg1) in local cheese
EMRL/MRL (lg kg1) Aboabo Tafo Asawasi
Mean Range SD Mean Range SD Mean Range SD
Lindane 100a <LD <LD <LD 4.41 <LD–4.41 0.01 <LD <LD <LD
Aldrin 150b 2.35 0.26–6.55 0.29 1.54 0.01–5.15 0.26 3.18 0.93–7.88 0.84
Endosulfan 100a 3.31 0.57–9.06 0.18 4.25 0.14–8.21 0.08 2.70 1.29–4.88 1.44
p,p 0 -DDE – 149.07 0.16–485.76 8.51 140.15 13.27–357.45 56.77 31.50 22.00–41.00 3.44
Dieldrin 150b 4.30 0.88–18.60 1.02 15.95 1.41–30.49 0.56 2.01 1.21–3.94 0.12
p,p 0 -DDT 500b 14.02 1.33–38.58 10.59 298.57 1050.71–77.76 28.02 42.17 1.33–119.00 56.00
n = 20 for each site.
<LD = below detection.
SD = standard error of mean.
a
Maximum residue level.
b
Extraneous maximum residue level.

500 lg kg1. The mean concentration of endosulfan
in yoghurt from Ayeduasi (0.05 lg kg1), KNUST
(0.06 lg kg1) and K-Poly (0.06 lg kg1) were almost the
same. Lindane was below detection in all the yoghurt sam-
ples taken from Ayeduasi but was detected in 10% yoghurt
samples from KNUST and 30% of yoghurt samples from
K-Poly. The levels of all the residues detected measured
in yoghurt were below their respective MRL/EMRLs.
Results from the analysis of cheese (Table 4) indicate
DDT level observed in cheese samples from Tafo is seven
fold the levels observed in samples from Asawasi and 21
folds the levels observed in samples from Aboabo. DDE
(a metabolite of DDT) concentrations in cheese samples
from Aboabo and Tafo are rather similar, and almost five
folds the concentration observed in samples from Asawasi.
The ratios of DDE/DDT concentrations in cheese samples
greatly vary by sampling sites: Aboabo: 10.60; Asawasi:
0.75; Tafo: 0.50. Milks used in the production of these local
cheeses are collected from different localities across the
country. The observed trends in the levels of DDT/DDE
by sampling sites could be attributed to differences in the
past and current use of DDT at the different locations
where milk for the production of cheese was collected. It
is likely that DDT is currently used at a larger extent at
the locations where milk was taken to prepare cheese at
Tafo than at the other two communities. It is also likely
that DDT was more extensively used in the past in that
community than in the other two communities. The aver-
age concentrations of DDT and DDE in cheese from all
the three sites were lower than their EMRL of 500 lg kg1.
Lindane concentration was below the detection limit of
0.10 lg kg1 in all cheese from Aboabo. Lindane was
detected in only 2 out of 20 (10%) of the cheese sampled
from Tafo. Levels of lindane, aldrin, endosulfan and diel-
drin were below the recommended limits. Lindane levels
in cheese from both Tafo and Aboabo were below detec-
tion. All the organochlorine residues, except for lindane,
were detected in cheese from Aboabo but at concentrations
lower than the MRL/EMRLs recommended by the World
Health Organization.
These residues might have originated from the feed of
the cattle or from pesticides used as ‘dip’ to control ecto-
parasites on the cattle or from maternal transfer. It is there-
fore recommended that a research conducted into the
fodder and feedstuff feed to these animals. It is essential
to put up mechanisms for monitoring of residues levels in
the ecosystem as well as the food chain. The results from
the study show that residues of organochlorine pesticides
are present in dairy products at concentrations lower than
their maximum residue levels. Although these residues
occurred at very low concentrations in the samples, they
may accumulate to higher levels in human beings who con-
sume these products.
This study has provided the preliminary information on
the concentration of some organochlorine pesticides in
some milk products for the first time in Kumasi, Ghana.
The results will help in a scientific assessment of the impli-
cations of pesticide residues with regards to human risks in
Ghana.
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