Continental J.

Environmental Sciences 2: 1- 7, 2008

©Wilolud Online Journals, 2008.

SEASONAL VARIATIONS OF ELECTROCHEMICAL PARAMETERS OF SURFACE WATER FROM

LAKE ALAU, MAIDUGURI, NIGERIA

Hati, S. S.1 G. A. Dimari2 B. G. Kolo2 and S. T. Garba2

1
Department of Chemistry, Gombe State University, Gombe, Nigeria, 2Department of Chemistry, University
of Maiduguri, Maiduguri, Nigeria

Abstract
Surface water samples from six (6) sampling stations of Lake Alau were monitored for
seasonal variations of electrochemical parameters, pH, redox potential (Eh) and
electrical conductivity (EC). Sampling stations were located on the basis of outlets to
water treatment plant and irrigation, points of water collections for domestic use by
residents around the Lake Area. Determinations were conducted on-site with Jenway
portable meters. Results of determinations show a general increase in the levels of pH
during the dry season period with an average value of 8.0±0.1, tending towards an
alkaline surface water environment. The general increase in pH level during the dry
season was statistically significant. However, the means of Eh (181.0±11.3 and
209.8±11.5 mV) were recorded for dry and wet seasons respectively. EC on the other
hand was higher in the dry season than the wet season, with mean conductivities of
125.6±10.6 and 169.5±11.0 µS cm-1 respectively. In conclusion, the results of the
electrochemical measurements obtained in this study show that Lake Alau is within the
no problem limits. However further monitoring studies are needed to elucidate the extent
of pollution in terms of toxic heavy metals and certain persistent organic pollutants.

KEYWORDS: water quality, aquatic life, domestic and agricultural wastes

INTRODUCTION
Electrochemical measurement of natural surface water is an important and straightforward way of monitoring
water quality and aquatic life, consequently indicating the level of pollution in such water bodies. Three basic
electrochemical parameters described by Manahan (2005) and Radojevic and Bashkin (2006), and significant
in monitoring both chemical and biological process occurring in surface water are the measure of H+
concentration in water (pH), the measure of oxidizing or reducing properties or power of water, redox
potential (Eh) and, the measure of concentration of ionized substances in water, electrical conductivity (EC).
These parameters, pH, Eh and EC are mainly connected to the quantitative ratio of carbonic acid and its ions
with direct relation to aquatic biota, e.g. fish population, the ability of the aquatic system to supply electrons
to an oxidizing agent and take up electrons form a reducing agent and the approximate measure of the total
concentration of inorganic substances in water.

A number of factors have been attributed to the cause of variations in the electrochemical properties of Lake
surface waters. Major amongst which, is dilution effect following rainfall, leading to an annual seasonal
variation effects (Odo and Ijere, 1997). Others are a wide variety of organic and inorganic pollutants released
into the water from surrounding activities (Manahan, 2005).

Lake Alau receives an average annual inflow of 329,000 m3 of water (Odo and Ijere, 1997). The annual
rainfall in this region ranges from 500mm to 1000mm and relative humidity is about 49%, with evaporation of
2934mm per year and temperature range of 38 to 40oC during the hottest months of March and April. These
factors together with persistent draught, very short rainfall period and desertification had made the water table
very difficult to reach (Idakwo and Abu, 2004). However Lake Alau supplies the municipal water treatment
plant, the major source of drinking water supply to the capital, apart from sporadic water obtained from
boreholes. The Lake supports a significant number of agricultural activities for an estimated population of

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 Hati, S. S et al: Continental J. Environmental Sciences 2: 1- 7, 2008

521492 (Maiduguri), and immediate environs 211204 (Jere) and 156564 (Konduga) (FRN, 2007). They are
about sixteen species of fish in Lake Alau (Bankole and Mbagwu, 2000) and several fresh vegetables farming
(Uwah et al, 2007) all year around the Lake.

In view of the challenges vis-a-viz the immense role of Lake Alau to Borno State and Nigeria, it is important
to carry out pollution monitoring on this natural water, particularly because they are very likely to be polluted
with domestic and agricultural wastes (Nikoladge et al. 1994; Diamant, 1980; Wong, 1979), which are
observed to be the major sources of pollutants in Lake Alau. Thus, this work provides monitoring information
concerning the electrochemical properties of the Lake as an indicator of extent of pollution associated with
domestic and agricultural activities taking place in and around Lake Alau in year 2007.

MATERIALS AND METHODS

Study Area, Sample and Sampling
Lake Alau is located on latitude 11o41′N and longitude 13o16′E on the South Eastern (SE) part of Maiduguri,
capital of Borno State, Nigeria (Google Earth, 2008; Idakwo and Abu, 2004). Surface water of the Lake was
monitored at six sampling stations (Figure 1) for a period of 8 months. This duration was categorized into
two: dry season (February-May) and wet season (July-October) for the year 2007. Sampling stations were
located on the basis outlets to water treatment plant and irrigation, S1, S2 and S5; points of water collections
for domestic use by residents around the Lake Area S3, S4 and S6.

Determination of Electrochemical Parameters

The electrochemical parameters, pH, redox potential (Eh) and conductivity of surface water of Lake Alau
were determined according to standard analytical methods described by Radojevic and Bashkin (2006), in
addition to instructions in the manuals of instruments used. All determinations were conducted on-site with
portable meters at approximately 25oC. Eh and pH were determined using model 3310 pH meter (Jenway Ltd,
Dunmow, UK). The pH meter and electrode was calibrated with buffer solutions of pH 7 and 4 for pH
determinations, while Eh readings were taken on the millivolt (mV) adjustments of the instrument
accordingly. This was standardized using standard redox solution. Conductivity measurements were carried
out using model 4150 conductivity meter (Jenway Ltd, Dunmow, UK). This was calibrated with standard
potassium chloride solution and results presented in µS cm-1. All observations of parameters at each sampling
stations were made in triplicates. Results obtained were statistically analysed for significance in variations
between seasons by t-test and variations between sampling stations by analysis of variance (ANOVA) with
Bonferroni post hoc test using coupled Microsoft Excel+Analyse-it v. 2.10 (Analyse-it®, 2007). Variations
were considered significant at p<0.05.

RESULTS
Figure 2 shows the seasonal variations of pH recorded at the six sampling stations of Lake Alau. There was a
general increase in the levels of pH during the dry season period with an average value of 8.0±0.1, tending
towards an alkaline surface water environment. A record high pH of 8.5±0.08 was observed during the dry
season at S6. On the other hand, observations during wet season show an average pH of 7.3±0.2 tending
towards the neutral point. The highest value observed was at pH 7.5±0.16 recorded at S5. The general
increase in pH level during the dry season was statistically significant and was found to be contributed by
activities in S1, S4 and S6.

2
 S1
S2
S3

S4
S5

S6

©Google Earth Maps (2008)

Figure 1: Lake Alau, Maiduguri-Nigeria showing sampling stations

Contrary to the general increases in pH during the dry season, results of Eh determinations (Figure 2) show a
general decrease in Eh values during the dry season. Of note however is the uniform trend in variations of Eh
between the seasons, along sampling stations, which overall, are not statistically significant. However, the
means of Eh (181.0±11.3 and 209.8±11.5 mV) were recorded for dry and wet seasons respectively. These
observations indicate that surface water from Lake Alau at the time of this study, can be characterized as an
oxidizing environment further depicted (Figure 4) with the Eh-pH plot.

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 Hati, S. S et al: Continental J. Environmental Sciences 2: 1- 7, 2008

Observations in the result of seasonal variations of conductivity determination (Figure 5), shows that
conductivity was higher in the dry season than the wet season, with mean conductivities of 125.6±10.6 and
169.5±11.0 µS cm-1 respectively. This variation was statistically significant and was effectively contributed by
activities in S1, S3 and S6. Remarkable observations were made at S4 and S5 in which a seemingly no
variations in the conductivity was observed indicating usual activities.

DISCUSSION
Many causes of pollution resulting from heavy metals, strong acids, alkalis and organic compounds affect the
environment and humans (Hammer, 1997; O'neil, 1983). An indication of extent of these can be obtained
from monitoring the electrochemical parameters of a natural water body.

Results of this study generally show the influence of dilution upon the electrochemical parameters studied, as
there were increases in pH and conductivity measurements during the wet season. Naturally aquatic biota
shows sensitivity to extremes of pH largely due to osmotic effects (Strickland, 2007). Knowledge of the level
of pH in such natural water provides control and treatment measures in processes involved in water softening,
disinfection and coagulation. Though the highest pH was observed at outlet points to water treatment plant,
yet this level does not pose great demands on pH control during treatment processes. Sulphuric acid produced
from the reaction of pollutant sulfur dioxide which enters natural water as acid rain fall may contribute to the
pH becoming hazardously low a condition that is commonly observed in Lakes of highly industrialized cities
(Uwah et al, 2007). This is hardly the case with Lake Alau situated in an almost no industrial activity region.
Irrigation and intensive agricultural activities have also been known to be responsible for the transport of salts
from irrigated and fertilized land into water bodies, corrosion, leaching and speciation of heavy and toxic
metals in waters have been greatly influenced by the pH (Manahan, 2005). This is likely to be reason of the
significant variations observed in pH values in this study. Since higher agricultural activities takes place
during the wet season.

The EC measure observed in this study, which is simply how easily an electric current runs through water
between two electrodes, shows that factors, such as greater amount of salts, acids and bases are in the water,
which increases conductivity, are within permissible limits. EC is also used to monitor water destined for use
in irrigation, drinking (Carlson and Simpson, 1996; Manahan, 2005) and conductivity is closely related to
salinity, ions that have a major influence on the EC of water are H+, Na+, K+, Ca2+, Mg2+, Cl-, SO42-, and
HCO3- (Radojevic and Bashkin 2006). Therefore EC increases with increase in mineral contents of a water
sample, thus its use in the measure of mineral contents. In general, conductivity is reduced as runoff increases,
and larger lake watersheds have greater conductivity levels than lakes with smaller watersheds (Manahan,
2005). Other factors that are likely to affect the increase in EC are the increase in temperature, which
decreases viscosity and increases dissociation. Thus the unusual observations at S4 and S5 are very likely to
be caused by these factors.

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 Hati, S. S et al: Continental J. Environmental Sciences 2: 1- 7, 2008

The high values of Eh recorded in this study, which indicate high oxidation conditions of Lake Alau, also
indicates favorable condition for aquatic life, since oxygen is the chief chemical species responsible for the
value of Eh in water sample as the increasing content of O2 in water also increases the values of Eh.
(Radojevic and Bashkin, 2006). The Redox couples of molecules in this natural water are also responsible for
these observations. These redox couples do exist in dynamic equilibrium of such natural water (Bartram and
Ballaco, 1996; Comerton, et al, 2006). The nature of Eh values in natural water also affects the speciations of
some heavy (polyvalent) metals such as Mn, Fe, Cr, As, etc. Others are Fe, S and some organic compounds. It
aid to characterize the chemical states of elements (e.g. Fe2+ and Fe3+) in water, and in combination with the
pH controls chemical processes occurring in water and aid in determining the microbiological activity of
waters and consequently, the degree of water self-purification from various organic and inorganic pollutants
((Henry, 1971; Wells, 1977; Sridhar et al, 1981; Radojevic and Bashkin, 2006).

Sewage and fertilizers containing nutrient such as nitrate and phosphorus in excess levels over stimulate the
growth of aquatic plants and algae with resultant consequences to respiratory ability of fish and other
invertebrate residing in the water (Dalzell and Christofi, 1999). These are factors likely to create balance for
aquatic biota in the seemingly less polluted water.

The complex interaction between water and life process is therefore fundamental to our need for suppliers of
potable water (Comerton, et al, 2006). However, Idakwo and Abu (2004), have reported that the fecal
coliform level of 6.0 x 102 to 8.8 x 102/100ml placed Lake Alau water samples in the EEC Grade A2 and
thus, the water was recommended for further treatments before it can be distributed to municipalities for
domestic use. Similarly, Bankole and Mbagwu (2000) expressed positive thriving of fishes and Uwah et al
(2007) of fresh vegetables in and around the Lake.

In conclusion, the results of the electrochemical measurements obtained in this study shows that Lake Alau is
within the no problem limits. However further monitoring studies are needed to elucidate the extent of
pollution in terms of heavy metals and certain persistent organic pollutants.

REFERENCES
Analyse-it® (2007) General and Clinical Laboratory Analyses Software Version 2.10. Analyse-it Software
Ltd. PO Box 77, Leeds, LS12 5XA, England

Bankole, N.O. and Mbagwu, I. G. (2000) Aspects Of The Fishery Of Lake Alau In
Nigeria Afri.J.Trop.Hydrobiol.Fish. Vol. 9 nos. 1 &2, Authors & Abstracts

Battram, J. and Ballaco, R. (1996). Water quality monitoring. A practical guide to the Design of fresh water
quality studies and monitoring programme. Chapman and Hall, London. Pp 23-45

5
 Hati, S. S et al: Continental J. Environmental Sciences 2: 1- 7, 2008

Carlson, R.E. and J. Simpson. (1996). A Coordinator’s Guide to Volunteer Lake Monitoring Methods. North
American Lake Management Society. “A Trophic State Index” http://dipin.kent.edu/tsi.htm. Retrieved
12/3/2008.

Comerton, A. M., Andrews, R. C. and Bagley, D. M. (2006) Impact of Blending Reuse and Lake Water on
Treated Water Quality J Env. Eng. & Sci. (5) 4: 359-363(5)

Dalzell, D.T.B. and Christofi, N. (1999). ATP luminescence used to evaluate the impact Of chemicals and
wastewater to activate sludge. Effluent Eco-Toxicology: An European Perspective. Society of Environmental
toxicology and Chemistry. pp. 14-17 Edinburgh.

Diamant, B.Z. (1980) Environment Health Impacts of water use in Africa. Proc. Water Techn. 13:171-178.

FRN: Federal Republic of Nigeria (2007) Official Gazette. Legal Notice on Publication of the 2006 Census
Report 4 (94) B47-182

Google Earth (2008). Google earth satellite image of Lake Alua, Nigeria. Google Earth 4.3.7204.0836. sever
kh.google.com (Access Date: 12/04/08)

Hammer, J.M. (1977). Water quality and pollution Waste and Water Technology 2nd Edition, John Wiley &
Sons, New York. Pp. 143-168.

Henry, A.S. (1971). "Metal in the Air". The science of environment B (8) pp.18-31.

Idakwo, P. Y. and Abu, G. O. (2004) Distribution and Statistical Analysis of Bacteria in Lake Alau in the Arid
Northern Nigeria J. Appl. Sci. Environ. Mgt. Vol. 8 (1) 5 - 9

Manahan, S. E. (2005) Environmental Chemistry (8th Edn). CRC Press LLC, USA. Pp. 169-180; 687

Nikoladze, G.D., Mints, R. D. and A. Kastalsky, (1994). Water Treatment for Public and Industrial Supply.
Pp. 14-16.

Odo, P. E. and Ijere, J. A. (1997) Quality analysis of water from Alau dam area in the north eastern Nigeria
for irrigation suitability and some related agronomic and environmental implications. Issues in environmental
monitoring in Nigeria. Nig. Geographical Ass. Pp 63-67.

6
 Hati, S. S et al: Continental J. Environmental Sciences 2: 1- 7, 2008

O'niel, P. (1983). Environmental Chemistry, George Alien and Irwin, London. pp.181-184.

Radojevic, M. and Bashkin, V. N. (2006) Practical Environemental Analysis (2nd Edn.) RSC Publishing, UK.
Pp. 147-170

Sridhar, M.K.C.; Oluwande, P.A. and Okubadejo, A.O. (1981). "Health Hazards and Pollution from Open
Drains in a Nigerian city". (A report), Ambio - 10, pp.29-35.

Strickland, R. M. (2007) Salinity. Microsoft® Student 2008 [DVD]. Encarta, Microsoft Corporation.

Uwah, E. I., J. C. Akan, E. A. Moses, J. Abah and V. O. Ogugbuaja (2007). Some anion levels in fresh
vegetables in Maiduguri, Borno State, Nigeria. Agricultural Journal 2(3): 392-396

Wong, M. H. (1979) Agricultural wastes of fresh water supply in Hong Kong Inc. Prog. Water Tech. 6:121-
132.

Received for Publication: 13/06/2008

Accepted for Publication: 15/07/2008

Corresponding Author
Hati, S. S
Department of Chemistry, Gombe State University, Gombe, Nigeria
Email: stevehati@yahoo.com

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Continental J. Environmental Sciences 2: 8 - 11, 2008
©Wilolud Online Journals, 2008.

BACTERIAL EVALUATION OF LOCAL HARD CHEESE (CHUKU) IN KATSINA- NIGERIA.

1
Salihu, M.D., 1Junaidu, A.U. 1Magaji, A.A., 1Gulumbe, M.L., 1Suleiman, A., 2Ahmed, A, and 1Shittu, A.
1
Veterinary Public Health Department, Usmanu Danfodiyo University, Sokoto
2
National Veterinary Research Institute, Vom, Sokoto Research Laboratory.

ABSTRACT
A study was conducted to evaluate bacterial quality of 288 samples of local haed cheese
(Chuku) procured from various retail outlets and markets in katsina town. The samples
were analysed for the presence of bacterial organisms, using the conventional
microbiological techniques for culture and identification. The results revealed the
presence of Escherichia coli, Klebsiella sp., Enterococcus sp., Listeria monocytogenes,
Proteus sp. and Staphylococcus aureus. Other isolates are Bacillus sp., Streptococcus
sp., Yersinia sp and Lactobacillus sp. The isolation of Escherichia coli, Klebsiella sp.,
Enterococcus sp., Listeria monocytogenes, and Staphylococcus aureus from the samples
are indication of poor hygienic conditions encountered during processing, storage and
marketing of the product which is a possible threat to consumer health.

KEY WORDS: Bacteria, Food poisoning, Isolates, Local cheese, Katsina, Milk.

INTRODUCTION
Milk is inherently a very unstable fluid owing to its high moisture content and the suitability of milk as a
growth substance for contaminants is responsible for the ease with which it becomes contaminated with
microorganism (Salihu, et al., 2005). It is therefore, important to convert milk into various products of milk
such as cheese, fermented milk, whey and other stable products of milk. Milk and milk products play vital
roles in human nutrition and also serve as good medium for growth and transmission of many
microorganisms to man. (Gill, et al., 1994).

Wherever, cattle are kept the Fulani men milked the cows and thereafter distribute the milk to the individual
women in the encampment (Fulani farm-stead), the women decide on what will be done with the milk
(Belewu and Aina, 2000). The milk is processed into various products such as cheese, fermented milk etc.
There have been reported cases of out break of food poisoning associated with milk and milk products from
developing and developed countries (Sharp, 1987). Although there are no surveillance activities in Nigeria,
laboratory studies have shown the presence of food borne pathogens and high microbial load in some street
food. (Umoh, et al., 1984; Magaji, et al., 2002: Adetunji, et al., 2003). The local cheese (locally called Chuku)
which is thin white to milky in appearance, slightly hard unripened with little moisture is sold in villages,
markets, and crowded points in and around Katsina. Since the milk products constitute an integral part of the
Nigerian diets (Aduku and Olukosi, 1991), attention should be paid more on the hygienic aspects of the
distribution of such foods. Milk and milk products provide a favourable environment for microbial growth.
Microbes can contaminate milk or milk products via animals themselves, the surrounding atmosphere,
feedstuff, handling, equipment as well as the milker (ILCA, 1988; Belewu and Aina, 2000).

This study was undertaken to evaluate the bacterial organisms associated with local hard cheese (Chuku) so as
to determine their safety for consumption.

MATERIAL AND METHODS

Preparation of local cheese hard (Chuku)
The local hard cheese is prepared in Nigeria by using vegetable rennet. The cheese is made from milk which
is slowly heated in a pot while vegetable rennet extract of Sodom apple (Calotropis procera) which is
commonly found in the tropics and sub-tropics is added. The plant contains calotropin enzyme which curdles
the milk (Aworth, 1990; Kees, 1995; Anon, 1995). The extract is obtained by crushing the leaves and the

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 Salihu, M.D et al: Continental J. Environmental Sciences 2: 8 - 11, 2008

stems of the plant and then rinsed in a calabash with milk. The mixture is strained into warm milk with
constant stirring and heating. Coagulation starts within 15-25 minutes after the addition of coagulant. The
curd is boiled for sometime at least 20 minutes to inactivate the plant enzyme and facilitate whey expulsion
after which the curd is strained through a sieve (usually a small raffia basket which facilitates whey drainage
and gives characteristics shape and size to the cheese) and turned carefully. The fresh cheeses are then spread
on tray or mats or flat wood to dry and become hard in the sun or in the shade.

Collection and processing of samples.

A total of 288 samples used for the study were procured every two weeks and randomly over a period of 24
weeks, from various retail outlets as well as from markets in Katsina metropolis. The procured cheeses were
wrapped in foil papers from the point of collection and transported to the laboratory same day. Care was taken
not to alter the condition of the samples as they are obtained from the sources where consumers purchase them
for direct consumption. The samples were aseptically handled in the laboratory. Samples from each of the
retail outlets were soaked in with distilled water in a beaker and covered with foil paper for 2 to 3 hours to
allowed for the rehydration and softening of the cheese. A loopful each of the softened cheese samples was
then inoculated into peptone water and selenite F broth respectively and incubated at 37OC overnight. A
loopful each from the peptone water was inoculated onto MacConkey agar, Blood agar and Eosin methylene
blue (EMB) agar while a loopful of selenite F broth was inoculated on deoxycholate citrate agar (DCA). The
media were inoculated in duplicate (except the DCA) and incubated aerobically and anaerobically at 37OC for
24-48hrs. Colonies were randomly selected from each medium and restreaked on fresh media plate to obtain
pure culture. Pure cultures of each isolates were stocked in agar slants in MacCarthney bottles. Colonies on
the media were identified based on Bergy’s manual and classification schemes proposed by Cheesbrough,
(2000). The identification was based on morphology and the following characteristics particularly gram stain,
morphology of the cells, motility and anaerobic condition as well as ability to produce catalase enzyme. Other
tests include biochemical coagulase, oxidase, oxidation and fermentation tests, acid/gas production from
sugar, urease test, hydrogen sulphide test, nitrate reduction test, phenylalamine deamination tests and
haemolysis test.

RESULTS
A total of 10 different bacterial organisms that are of public health importance were isolated from the samples
collected. These organisms include Escherichia coli, Klebsiella sp., Enterococcus sp., Listeria
monocytogenes, Proteus sp. and Staphylococcus aureus. Other isolates are Bacillus sp., Streptococcus sp.,
Yersinia sp and Lactobacillus sp.

DISCUSSION
The high level of bacterial isolation in this study is an indication of unsanitary hygienic standard or condition
post processing, storage, handling and retailing of the product. Indicator organisms like Escherichia coli,
Klebsiella sp. and Enterococcus sp. are vital in milk and milk products to evaluate the microbiological safety
and sanitary condition during processing and storage (Belewu and Aina, 2000). The presence of E. coli which
is usually killed at >55oC in 15 minutes in cheese is suggestive of post processing contamination (Adetunji et
al., 2003). The presence of Klebsiella sp in the product could partly be through air (sneezing, coughing,
talking or singing) since the bacteria inhabit the upper respiratory tracts of humans (Belewu and Aina, 2000).
The presence of Escherichia coli and Klebsiella sp. in milk and milk products has been reported in literature
(Aworth and Egounlety, 1985; Joseph and Akinyosoye, 1997; Belewu and Aina, 2000; Adetunji et al., 2003).
The isolation of enterococcus in this study may be attributed to unhygienic handling as man is the reservoir of
this organism.

The isolation of Staphylococcus aureus (coagulase positive) in this study is similar to the findings of
Adesiyun, (1994) and Adetunji (2003). This bacterium is known to cause major food poisoning in both
healthy and immunosuppressed patients (Alonge, 1993). Staphylococcus aureus produces an enterotoxins that
are heat stable and are generally not destroyed during pasteurization or processing (Tatimi, 1981). Listeria
monocytogenes has been incriminated in meningoencephalities, stillbirth and abortion in humans (Adams and
Moss, 1999). Therefore, the isolation of L. monocytogenes in this study is an indication that the organism is an

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 Salihu, M.D et al: Continental J. Environmental Sciences 2: 8 - 11, 2008

important contaminant of milk products; this has a serious public health consequence. Lactobacillus sp is a
lactic acid bacterium that is probably involved fermentation of the products. Proteus sp are usually pathogenic
in cases of wounds, burns, viral infection or similar condition of impaired resistance; their isolation is of
public health significant. This finding is similar to the findings of Belewu and Aina (2000).

The results show high amount of bacteria in the samples and this call for improved storage and retailing of the
product. A high level of sanitary and hygienic condition should be instituted and maintained so as to establish
microbial standards for this product which will go a long way in ensuring safer cheese and other milk
products.

REFERENCES
Adams, M.R. and Moss, R.O. (1999): Food Microbiology. The Royal Society of Chemistry, Thomas
Graham House, Science Park, Cambridge CB 40 WF 3rd edn. 156-218.

Adesiyun, A.A. (1994): Bacteriological quality and associated public health risk of pre-processed bovine milk
in Trinidad. Int. Food Microbiol. 21: 253-261.

Adetunji, V.O., Ikheloa, J.O., adedaji, A.M. and Alonge, D.O. (2003): An evaluation of the bacteria in milk
products sold in Southwestern Nigeria. Nig. Vet. Jour. 24(3):92-96

Aduku, A.O., and Olukosi, J.O. (1991): Animal Products, Processing and Handling in the tropics. Living
Books Series. C.U. Publication, Abuja, Nigeria.

Alonge, D.O.(1993): Food (meat and milk) Hygiene (2nd edn). Farmcoe Publications, Ibadan. 58-63.
Anon (1995): Curd and Whey. Spore. 55:1-4.

Aworth, O.C. and Egounlety (1985): Preservation of West African Soft Cheese by Chemical Treatment. J.
Dairy Res. 52: 189-195.

Aworth, O.C.(1990): Upgarding traditional techniques of food processing and preservation: Cheese making.
West Afr. J. Arch. 20: 232-238.

Belewu, M.A. and Anina, O.S. (2000): Microbial Evaluation of Indigenous Milk Products with Special
Reference to the Bacterial Flora of Some Public Health importance in Nigeria. Afr. J. Clin. Exp. Microbiol.
1(1):13-19.

Cheesbrough, M. (2000): District laboratory practice in tropical countries, Cambridge University Press.

ILCA (International Livestock Centre for Africa) (1988): Rural Dairy Tech. Exp in Ethiopia.

Joseph, J.K and Akinyosoye, F.A. (1997): Comparative studies on red sorghum extracts and other chemical
preservatives for West African soft cheese. Int. Dairy J. 7: 193-198.

Kees, M. (1995): Rural cheese making. Agric and Rural Dev.

Gill, J.P.S., Josh, D.V. and Kwatra, M.S.( 1994): Qualitative bacteriological survey of milk and milk products
with special reference to Staphylococcus aureus. Indian J. Dairy Sci. 47:8.

Magaji, A.A., Salihu, M.D. and Donbou, B.L. (2002): Bacteriological Evaluation of roasted beef “suya” in
Sokoto Metropolis. Proceedings of the 39th annual congress of the Nigeria Veterinary Medical Association,
Sokoto 2002.Pp 131-133.

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 Salihu, M.D et al: Continental J. Environmental Sciences 2: 8 - 11, 2008

Salihu, M.D., Junaidu, A.U., Magaji, A.A., Gulumbe, M.L. and Balogun, S.T.(2005): Determination of
phosphatase enzyme activity in yoghurt sold in Sokoto metropolis. Proceedings of the 42nd congress of
Nigerian Veterinary Medical Association- Maiduguri, 2005. Pp 119-120.

Sharp, J.C.M. (1987): Infections associated with milk and dairy products in Europe and North America 1980-
85. Bull. WHO. 65:397-406.

Tatimi, S.R. (1981): Thermonuclease as an indication of Staphylococcal enterotoxin in food. In: Antinutrients
and Natural Toxicants in Food. Ed. Org. R.C. Food and Nutrition press, Inc. Westport C.T, 53-75.

Umoh, V.J., Dangena, A. and Umoh, J.U (1984): Isolation of Yersnia enterocolitica from milk and milk
products in Zaria, Nigeria. Int. J. Zoon. 11:223-228.

Received for Publication: 13/06/2008

Accepted for Publication: 15/07/2008

Corresponding Author
Salihu, M.D.
Veterinary Public Health Department, Faculty of Veterinary Medicine, Usmanu Danfodiyo University, Sokoto
Email: mdsal70@yahoo.com.

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Continental J. Environmental Sciences 2: 12 - 16, 2008
©Wilolud Online Journals, 2008.

TOXICITY ASSESSMENT OF HEAVY ELEMENTS IN RIVER SEDIMENTS USING ENERGY

DISPERSIVE X-RAY FLUORESCENCE TECHNIQUE

Hankouraou Seydou1, I.O .B. Ewa2

1
Gombe State University, PMB 127, Gombe Department of Physics, 2 Centre for Energy Research and
Training Ahmadu Bello University, Zaria

ABSTRACT
Trace quantities of thirteen elements have been determined from the aquatic sediments,
of the Kubanni River- principal water way at Zaria, Nigeria. Energy Dispersive X-ray
Fluorescence (EDXRF) Technique was used in determining
Si,Ca,K,Ti,V,Fe,Co,Zn,Rb,Sr,Y,Zr and Nb in the sediments. An AXIL computer
programme was used for the spectral analysis. The degree of pollution of the Kubanni
River was ascertain and compared with the literature toxicity data. The Kubanni River
sediments studied showed relatively low state of pollution for the elements determined
and the River could still be used as a principal potable water source for Zaria
inhabitants.

KEYWORDS: EDXRF, toxicity, heavy metals, River sediments, Kubanni

INTRODUCTION
Naturally occurring trace elements are deposited in aquatic environments either in the soluble form and
eventually settle as bottom sediments along the course of the river (Hankouraou, 1998). The presence of these
trace elements in aquatic environments is not without significance: for some of them are known to be very
toxic and act as contaminants in the sediments. Man’s activities have increased the loading of municipal and
industrial contaminants to the nation’s water ways. One of such water ways is the Kubanni River our study
area in Zaria.

This river runs as a major principal drainage artery dissecting Zaria town. The increased loading of river beds
with wastes could result in increased concentration of many heavy metal contaminants in sediments adversely
affecting water quality and even the survival of aquatic organisms. Contaminants in sediments have a wide
range of sources, and could be affected by lotic (running water), lentic (standing water), estuarine or lacustrine
conditions, physical properties of sediments, the chemical state and biological composition of the water
involved (Jenett et al 1980).

Most research in aquatic systems has been concerned with the form of contaminants present, rather than the
amount of potential toxic material bound up in the sediments .The low concentration elements are
undoubtedly the most difficult to study because background levels are always present in the environment
masking their presence, and a small perturbation on an ecosystem could bring about rapid increase in the rates
of synthesis of these heavy metals.

The potential impact of trace elements in sediments is determined here strictly with respect to the Kubanni
River sediments. The detection of such elements requires sensitive and accurate analytical methods. In this
work the Energy Dispersive X-ray Fluorescence (EDXRF) is chosen due to its reliability amongst other
merits. This method of analysis offers an easy and sensitive way of determining any trace element in
sediments. Its advantages include:

i) Simple sample preparation

ii) Non –destructive capability for analysis and
iii) Ability to determine many elements simultaneously.

12
 Hankouraou Seydou and I.O .B. Ewa: Continental J. Environmental Sciences 2: 12 - 16, 2008

EDXRF analysis suffers from certain set backs such as high investment, rigorous radiation protection, matrix
effects, need for well trained personnel; thus limiting its application to few laboratories and research institutes
such as the Centre for Energy Research and Training, Ahmadu Bello University, Zaria, where this work was
carried out.

This paper was a report on the analysis of some trace elements in the Kubanni river sediments by EDXRF
technique.

The method was checked by analyzing United State Geology Survey (USGS) reference materials: USGS-
AGV-1 (Analyzed Andasite) and USGS-G2 (Granite).

EXPERIMENTAL
In order to study the distribution of trace elements along the Kubanni River, 11sediment samples were
collected at different locations (Fadama along Jos Road 5 samples and for Maje Road Bridge, Tudun Wada
Bridge, Kano-Kaduna Bye-Pass Bridge, Zango Bridge, Ahmadu Bello University Dam and Kampangi Hills,
one sample each). The 11 samples were collected in polyethylene containers .The distance between the
sampling points is approximately 3 kilometers.

The sediments were allowed to dry in an oven at 50 o C for three days and were then homogenized, by manual
grinding in agate mortar. The powder obtained after grinding was used for the preparation of pellets used for
the analysis. A Mettler 100 CA digital balance was used for weighing the powdered samples, with only 2.0g
of each sample required for the making of pellets. A cellulose binder polyvinylchloride (PVC) was added to
each 2.0g of the sediments (powder) sample. The mixture was re-homogenized in agate mortar. The samples
were then palletized (using the specac hydraulic press) by applying constantly a pressure of about 11.5 tones
per cm2. Pellets of 20 mm diameter and constant thickness of 5 cm were obtained from the samples.

Two standard reference materials were used for quality control measurements (USGS- AGV-1 and USGS-
G2). Samples and standards were analyzed using the EDXRF facility of the Centre of Energy Research and
Training (CERT), Ahmadu Bello University, Zaria Nigeria. The spectrometer consists of a Si(Li) detector, a
preamplifier, amplifier and 4096 multi-channel analyzer.

X-rays emanating from two sources (109Cd, 55Fe) were used for the excitation of the characteristic K- lines of
the analytes.

The non – linear least square fitting programme developed by IAEA and called AXIL was used for the
determination of line intensities.

RESULTS AND DISCUSSION

Table 1 shows the average concentrations of the elements down-stream Kubanni River (Hankouraou, 1998).

Bowen (1979) had shown that Ca, Co, Fe, K, and Zn are probably essential to all plants. This could be of used
to the seasonal crops grown at the Kubanni River basin. Elements like Si are essential to some groups, not
necessary for all. Rb, K, Sr, and Ca are known to have a very high toxicity, which only arises when a large
proportion of the essential ion has been replaced. Elements like Co are known to be very toxic to seed plants.
Fe, V and Zn are moderately toxic while Ca, K, Rb and Sr are only toxic to very high concentration which was
not the case with regard to Kubanni River. Zn is the element most frequently concerned with plant damage
from industrial emissions, e.g.: on mine wastes, near smelters, sewage sludges, river dredgings, near galvanized
steel buildings and where rubber tyres are burnt (Patterson, 1971). Excess of it inactivates soil enzymes
(Bowen, 1979) and reduces the bacterial population (Griffiths, et al 1975), but does not have marked effects on
the fauna. The Kubanni River level of zinc was found to be in the range 56 ppm to 665 ppm as shown in Table
1, which was less than 900 ppm an upper toxic limit for animals as given by (Jenett et al 1980) but can be
toxic to plants according to Bowen (1979). Most of toxicity problems encountered with zinc are due to
cadmium associated with zinc. As cadmium appears to be highly toxic to aquatic organism in the 0.02- 2.0 ppm

13
 Hankouraou Seydou and I.O .B. Ewa: Continental J. Environmental Sciences 2: 12 - 16, 2008

range, where a dose of 4 ppm in the diets of humans is normally considered to be toxic ( Jenett et al. 1980).
Some specified values have been accepted as the tolerated level in rivers. For example in Missouri the
maximum allowed value as given by Jenett et al. (1980) was 150 ppm, while the Kubanni River mean value of
zinc was obtained to be 149 ppm peaking up with the quoted value.

However, the results of this analysis show that the Kubanni River water might not pose any hazards and are
quite suitable for drinking purposes if well treated.

The quality assurance results (Table2 and 3) shows that the determinations for most of the elements were in
good agreement with the UGSG- AGV-1 SRM and UGSM-G-2 RSM literature values. The values of the
relative errors ranged from 1 to 30% for most of the elements this is within the permissible limits (IAEA,
1988). For Co our results were too far from the recommended values of IAEA. The relative errors were 83%
for USGS – AGV-1 and 133% for USGS-G-2, but they were within the values of the participants (Tran Van et
al, 1989).

Table 1: Average concentrations of the elements detected in Kubanni River sediments. (Values in ppm
otherwise as specified).

Elements Mean value of the elements Toxicity to plants by Bowen

(Values in ppm or as stated) (1979) (in ppm)
±SD
Si% 30.3 (5)
K% 2.0 (0.5)
Ca% 0.4 (0.2)
Ti% 0.5 (0.1)
V 242 (220) 10 -40
Fe% 1.2 (0.1) 10-200
Co <16.4 (5) 0.1 -3
Zn 149 (78) 60 - 400
Rb 118.2(5)
Sr 69.0(8)
Y 51.0 (20)
Zr 884.2 (493)
Nb 33.1(14)

Table 2: Determination of Elemental Content of USGS- AGV-1 SRM (Values in ppm otherwise as specified)
Elements Literature values This work Relative error%
Si% 27.4 25.1 8
K% 2.41 2.50 4
Ca% 3.53 3.71 5
Ti% 0.63 0.68 8
V 121 140 16
Fe% 1.60 1.60 0
Co 15.3 28.0 83
Zn 88.0 <86.7
Rb 67.3 51.1 24
Sr 662 651 2
Y 20.0 15.4 23
Zr 227 227 0
Nb 15.0 <25.5 70

14
 Hankouraou Seydou and I.O .B. Ewa: Continental J. Environmental Sciences 2: 12 - 16, 2008

Table 3: Determination of Elemental Content of USGS G-2 SRM (Values in ppm otherwise as specified)
Elements Literature values This work Relative error%
Si% 32.2 32.0 1
K% 3.71 3.58 4
Ca% 1.40 1.28 9
Ti% 0.28 0.20 29
V 36.0 36.5 1
Fe% 1.60 1.11 31
Co 4.60 <10.7 133
Zn 86.0 86.0 0
Rb 170 170 0
Sr 478 495 4
Y 11.0 12.2 11
Zr 309 309 0
Nb 12.0 12.0 0

CONCLUSION
The application of EDXRF technique in this work has been successful in the determination of elements from
the Kubanni River sediments. Most of the elements identified are heavy metals of environmental concern. The
elements determined were: Si, Ca, K, Ti, V, Fe, Co, Zn, Rb, Sr, Y, Zr and Nb. Only V, Fe, Co and Zn fell
within the plants toxic limits as reported by Bowen (1979).Analysis of various crops during the irrigation
period will give a clear indication of plants that could be affected by the mentioned contaminants. The toxicity
levels of all the elements were found tolerable, showing that the river water can be used for drinking purpose if
well treated.

ACKNOWLEDGEMENT
The Center of Energy Research and Training (CERT) and IAEA are hereby acknowledged for making all the
facilities available and the AXIL programme respectively.

REFERENCES
Bowen, H. J. M (1979) Environmental Chemistry of the elements, Academic Press, London, 213-235.

Griffiths, A. J; Hughes, D. and Thomas O. (1975): Minerals and the environment in: Int. Mining Metallurgy
(Jones M. J. Ed), London, 387.

Hankouraou, S. (1998) Determination of trace elements in the Kubanni River Sediments using Energy
Dispersive X-Ray Fluorescence Technique M .Sc unpublished Thesis.

IAEA(1988): Analytical quality control service programme, LAB/243, IAEA, Vienna

Jenett,J. C; Sten W. E and Bobby G. W (1980): Sediment and Toxicological Aspects of Sedimentary
Contaminants In: Contaminants and Sediment Volume 1 (R. A Baker, Ed) Ann Arbor Science, 429-444.

Patterson, J. B. E (1971): Trace elements in Soils and Crops, Min. of Agric., Fish and Food Technology,
Bulletin 21, 193, H M Stationary Office, London.

Tran Van, L.;Teherani, D. K (1989): Determination of Trace Elements and Heavy Metals in Lake Sediment
by Neutron Activation Analysicls. J. Radioanal. Nucl. Chem., Letters 135/6/ 435-441 Elsevere, Akademiai
Kiado, Budapest

15
 Hankouraou Seydou and I.O .B. Ewa: Continental J. Environmental Sciences 2: 12 - 16, 2008

Received for Publication: 07/09/2008

Accepted for Publication: 15/10/2008

Corresponding Author
Hankouraou Seydou
Gombe State University, PMB 127, Gombe Department of Physics, Gombe State
Email: seydou5k@yahoo.com

16
Continental J. Environmental Sciences 2: 17 - 25, 2008
©Wilolud Online Journals, 2008.

SEASONAL DYNAMICS OF HEAVY METAL POLLUTION OF NIGER DELTA RIVER SEDIMENT

RECEIVING INDUSTRIAL EFFLUENTS

V. C. Eze and G.C. Okpokwasili

Department of Microbiology, University of Port Harcourt, P. M. B. 5323. Port Harcourt, Rivers State, Nigeria.

ABSTRACT
The heavy metal changes of Okpoka-Woji River serving as a sink of effluent of
industries located in its vicinity within the Trans Amadi Industrial area were monitored
over rainy and dry season months in order to follow the seasonal dynamics engendered
by the dumping. Sediment samples from six sampling stations located along the river
were collected for the determination of heavy metals. The mean values for the heavy
metals were as follows: lead ranged from 17 - 67.2 mg/kg and 22.3-67.8 mg/kg; iron
7,995.5 - 17024.2 mg/kg and 6949.3 - 21,403 mg/kg; chromium 0.8-2.3 mg/kg and 16-
3.4 mg/kg; Zinc 3195.1 - 4455.5 mg/kg and 1713.4-3417.3 mg/kg; manganese 22.5 -
100.6 mg/kg and 20.8 - 121.7 mg/kg; nickel 2.4 - 9.2 mg/kg and 2.0-6.9 mg/kg;
vanadium 25.6 - 42.2 mg/kg and 26.1- 50.2 mg/kg; copper 19.5 - 46.9 mg/kg and 36.7 -
67.5 mg/kg; cadmium 0.3 - 1.6 mg/kg and 0.8 - 1.6 mg/kg; barium 21.1 - 77.6 mg/kg
and 22.6 - 34.0 mg/kg respectively for the rainy and dry season months. These results
showed that seasonal changes as well as industrial effluent discharges influenced the
heavy metal values of the river.

KEYWORDS: Seasonal dynamics, heavy metals, pollution, industrial effluents,

sediment.

INTRODUCTION
A pollutant is a substance that occurs in the environment at least in a part as a result of human activities and
which has a deleterious effect on the environment (Moriarty, 1990). Pollutants are now unfortunately part of
our environment as a result of industrial and other sources. There have been substantial increases in the
industrial and agricultural development in the Niger Delta with the attendant population growth. These
activities have resulted in the direct discharge of organic and inorganic substances including crude oil and
refined products through normal operations (effluents), operational failures and sabotage to facilities into the
adjoining water bodies. Other times as these components get into the water body, they finally settle at the
sediment which acts as sinks of contaminants in aquatic systems (Chindah et al., 2004; Muncha et al., 2003).

Sediments are important substrates for heavy metals attachment in any aquatic environment (Horowitz, 1985;
Deely et al., 1992). The degree to which water systems withstand heavy metal pollution is frequently
dependent on the concentration of suspended sediment in the water column. Suspended sediment in the water
particularly clay (< 4 µm) act as sponges adsorbing metals directly from the dissolved settles, the bottom
sediment will build up a record on metal pollution in an area (Cauwet, 1987; Forstner, 1989).

Sediment is composed of a combination of lithogenic, antigenic and biogenic components such as mineral
grains, organic matter, iron and manganese oxides, sulphides and carbonates. Heavy metals may be attached
to any of these phases in proportions, which depend on the physicochemical conditions prevailing in the
sediment and associated water. It has been seen that as the grain size decreases, the concentration of metals
adsorbed onto sediment component increases particularly across the transition zone from silt to clay. The flat
platy structures of clay minerals have high surface areas, surface charges and cation exchange capacities,
which readily attract metals and metals carrying substrates (Forstner and Wittmann, 1981; Horowitz, 1985;
Cauwet, 1980; Deely et al., 1992)

Various heavy metals other than mercury including tin, cobalt, chromium, nickel, cadmium and thallium are
used in metal alloys or as catalysts. Their mining, smelting and ultimate disposal causes heavy metal pollution

17
 V. C. Eze and G.C. Okpokwasili: Continental J. Environmental Sciences 2: 17 - 25, 2008

problems. All these metals are substantially toxic to plants, animal and many microorganisms (Atlas and
Bartha, 1993).

The trace metals that enter the aquatic environment from both natural and anthropogenic sources may be as a
result of direct discharge into both fresh water and marine ecosystem or through indirect routes such as dry
and wet deposition and land runoff. The important natural sources include coastal supply such as rivers,
glaciers wave action and erosion; deep sea supply which included volcanic activities, tectonic activity and
chemical processes in sediment and atmospheric mainly particles and vapours (mercury). The anthropogenic
sources include direct processes such as mining, smelting and refining and indirect processes, which include
electroplating catalysts and petrochemical industry. Other atmospheric sources include fossil fuel burning
(Kiely, 1998).

The aim of this work is therefore to determine the effect of season on the heavy metal of the river receiving
industrial effluents.

MATERIALS AND METHODS

Study area
The Okpoka-Woji River is situated in the coastal environment of the Niger Delta Rivers State, Nigeria. It
arises from the bifurcation to the left of the Okpoka River, which drains into Bonny River. The area has a
mean water depth of 4.8m, which is tidal and gradually transits from fresh to salt water at the head. The
freshwater biotope flows unidirectionally downstream from the Rumuodara swamp forest transversing Port
Harcourt - Aba express road bridge through Rumuogba (Mini-Okoro Police Station) where tidal effects begin,
hence the beginning of the incursion of salt water (Figure 1).

Collection of sediment samples

Sediment samples were collected from the river at the discharge point once in a month from April 2001 -
March 2002. The sediment samples were collected using soil grab and were put in sterile black polyethylene
bags. All the samples were analyzed immediately on reaching the laboratory.

Chemical Reagents
The chemical reagents used in the study were of analytical grade and were products of BDH Chemicals,
Pooles, England; Sigma Chemical Company, St. Louis, Missouri, USA and Hach Company Ltd, Colorado,
USA.

Heavy Metal Analysis

The sediment samples were air dried for 5 days and sieved with a sieve size of 1.70mm. The samples were
digested using the methods adapted from ASTM (2003). This was done by weighing accurately 1g of the
sieved sample, which was placed in the digestion container. Exactly 10ml of water, 5ml, HCL (S. G. I. 19)
and 1ml of HNO3 (S.G.I. 42) were added and swirled gently to mix. The containers were loosely capped and
placed in a rack, which was then put in an autoclave. The samples were autoclaved for 30 minutes at 121o C
and 15 psi. The digestion containers were then removed from the autoclave and allowed to cool at room
temperature. The contents of the digestion containers were quantitatively transferred to a 100ml volumetric
flask and made up to volume with distilled water. The digests were analysed for heavy metals using atomic
absorption spectrophotometer Model 969, Unicam. The statistical methods used were ANOVA and standard
deviation. The determination was done three times.

RESULTS
The seasonal changes in the heavy metal contents of the Okpoka-Woji River sediment are shown in figures 2a
to 4b. The mean values for lead, iron chromium and zinc where shown in Figures 2a - 2d. The mean value
ranges were lead, 17 - 67.2 mg/kg and 22.3 - 67.8 mg/kg; iron, 7,995.5 - 17024.2 mg/kg and 6949.3 - 21,403
mg/kg; chromium, 0.8 -2.3 mg/kg and 1.6 - 3.4 mg/kg; zinc, 3195.1 - 4455.5 mg/kg respectively for rainy and
dry season months. The mean values for lead, iron and chromium were observed to be higher in the dry

18
 V. C. Eze and G.C. Okpokwasili: Continental J. Environmental Sciences 2: 17 - 25, 2008

season month and rainy season month. Statistically the ANOVA P < 0.05 showed that there was significant
difference in the mean values between the dry and rainy season months. The mean value for zinc was higher
in the rainy season months than in dry season months. But statistics showed that there was no significant
difference in the mean values between the rainy and dry season months as P > 0.05.

t
ham Wes Road
E li a E a s t -

a y
ssw
dar
a p re
Ru
mu Ex

Ea
Mg b ue s ilia
st
ru ba
u r t /A We s t
.a r c o
Elelenwo
P o rt H
Ro
ad
Ro a d
ba
O ld A R um uogb a
1
R
oa
d
R u m u o b ia ka n i
Umurou
2
ou d
Trans 3 Woj ur
Um Roa
Amadi
Oginigba -
Road a di
s Am
T ra n tto ir
Aba
Trans Amadi
Industrial Area
4
d C re e
di Roa k
Am a
Tr ans
Okujagu 5

Okwuru Ama 6

Okujagu
Abuloma Road

Fed Coll. Legend

Okpoka River

Scale
0 500m

Expressway
Major Road
Rivers / Creeks
Source: Street Guide of Port Harcourt by SPDC 1986

Fig.1: Map of Woji Creek showing the sampling stations

19
 80.0 25.0
2a Rainy Dry 2b Rainy Dry

70.0

20.0
60.0

50.0

Iron (mg/Kg)x103
15.0
Lead (mg/Kg)

40.0

10.0
30.0

20.0
5.0

10.0

0.0 0.0
Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6 Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6
Stations Stations

4.0
5.0
2c Rainy Dry
2d Rainy Dry
3.5 4.5

4.0
3.0
3.5
Chromium (mg/Kg)

Zinc (mg/Kg) x103

2.5
3.0

2.0 2.5

2.0
1.5

1.5
1.0
1.0

0.5
0.5

0.0 0.0
Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6 Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6
Stations Stations

Fig. 2: Changes in the monthly mean values of lead, iron chromium and
zinc levels of Okpoka-Woji River sediment across the stations.

20
 140 10
3b Rainy Dry
3a Rainy Dry
9
120
8

100 7
Manganese (mg/Kg)

Nickel (mg/Kg)
6
80
5

60 4

3
40

20
1

0
0
Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6
Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6
Stations
Stations
80
60
Rainy Dry
3c Rainy Dry 3d
70

50
60

40
Copper (mg/Kg)
Vanadium (mg/Kg)

50

30 40

30
20

20

10
10

0
0
Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6
Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6
Stations Stations

Fig. 3: Changes in the monthly mean values of manganese, nickel, vanadium

and copper levels of Okpoka-Woji River sediment across the stations.

21
 1.80
4a Rainy Dry
1.60

1.40

1.20
Cadmium (mg/Kg)

1.00

0.80

0.60

0.40

0.20

0.00
Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6
Stations

90
4b Rainy Dry
80

70

60
Barium (mg/Kg)

50

40

30

20

10

0
Stn 1 Stn 2 Stn 3 Stn 4 Stn 5 Stn 6
Stations

Fig. 4: Changes in the monthly mean values of cadmium and barium levels of
Okpoka-Woji River sediment across the stations.
22
 V. C. Eze and G.C. Okpokwasili: Continental J. Environmental Sciences 2: 17 - 25, 2008

Figures 3a - 3d show the mean values for manganese, nickel, vanadium and copper. They had the following
mean values ranges manganese, 22.5 - 100.6 mg/kg and 20.8 -121.7 mg/kg; nickel, 2.4 - 9.2 mg/kg and 2.0 - 6
mg/kg; copper, 19.5 - 46.9 mg/kg and 36.7 - 67 mg/kg respectively for rainy and dry season months. It was
observed that the mean values were higher in the dry season months for manganese, vanadium and
copperwhile the mean values for nickel were higher in the rainy season month than the dry season months. It
was also observed that P < 0.05 showed that there was significant difference in the mean values between the
dry and rainy season months for manganese, nickel and vanadium while P > 0.05 showed no significant
difference in the mean values between the dry and rainy season months for copper.

The mean values for cadmium and barium are shown in Figures 4a - 4b. The mean values ranges were
cadmium, 0.3 - 1.6 mg/kg and 0.8 - 1.6 mg/kg; barium 21.1 - 77.6 mg/kg and 22.6 -34.0 mg/kg respectively
for the rainy and dry season months. It was observed that there was no significant difference in the mean
values between the dry and rainy season months for cadmium and barium as P> 0.05.

DISCUSSION
The accumulation of heavy metals in sediments may become the re-pollution source for an aquatic
environment when environmental changes occur. The levels of the heavy metals observed in the sediments
during the study period were higher than those encountered in the surface water. The trace metal content of
recent sediments depends on the anthropogenic inputs as well as the natural characteristics of the sediments
especially in the grain size (Tkalin et al., 1996; Presley et al., 1992). The domestic and industrial effluents
discharge may be implicated in the high concentration of the heavy metals observed. Okoye et al. (1991)
reported anthropogenic heavy metal environment of Cd, Co, Cu, Fe, Mn, Ni, Pb and Zn in the Lagos Lagoon
and implicated land based urban and industrial wastes. Kakulu and Osibanjo (1988, 1992) revealed elevated
levels of Pb, Cr, V and Zn in Port Harcourt and Warri sediments, which suggest that effluents from petroleum
refineries located in these cities, have contributed significantly to the heavy metal pollution of the respective
aquatic ecosystems.

The high concentrations of these heavy metals call for a serious concern in relation to ecological and human
health. Contaminated sediment can be associated with acute and chromic effects on aquatic life. Sediment also
constitute a major source of persistent bioaccumulative toxic chemicals which may pose threats to ecological
and human health even after contaminants are no longer released from point and non-point sources. Adverse
ecological effects of contaminants in sediment include fin rot skin lesions, increased tumor frequency and
reproductive toxicity in fish, reproductive failure in fish eating, birds and mammals and decreased biodiversity
in aquatic ecosystem. Threat to human health occurs when sediment contaminants bioaccumulate in fish and
shellfish tissues consumed by humans (Armitage, 1997).

The seasonal dependent variation in the sediment of the heavy metals may be associated with seasonal factors
such as nature of the sediment and runoff and water quality (Bryan, 1973; Szefer et al., 1999). It was observed
that zinc, nickel, barium had mean values higher in the rainy season months than the dry season months. The
other metals studied namely lead, iron, chromium, manganese, vanadium, cadmium and copper had mean
values higher in the dry season than in the rainy season months. The means, that there is much concentration
of organic and inorganic nutrients in the sediment in the dry season than rainy season months. It also shows
that the river water is cleaner in the rainy season dilution of industrial wastes as they enter river from rainfall,
soil erosion and runoff.

This was in contrast with the findings of Chindah et al. (2004) and Biney (1997) who reported consistent
higher concentration of zinc and copper in the dry season than in the dry season months while the rest of the
metals higher mean values in the rainy season than dry season months. The mean values for nickel and barium
were in agreement with their findings as the values were higher in the rainy season than dry season months.

Iron is used in steel production and is a byproduct of combustion and such it is expected to be present in large
quantities. However, it is also found in many primary and secondary minerals in a significant weight, so the

23
 V. C. Eze and G.C. Okpokwasili: Continental J. Environmental Sciences 2: 17 - 25, 2008

increases are not necessarily anthropogenic in nature. It is certainly possible that the noted increase explained
as deriving from anthropogenic emissions may to some extent be due to the diagenetic inputs (Varekamp,
1990).

ACKNOWLEDGEMENT
We sincerely thank the management of Quality Control and Testing Laboratories Limited Plot 173
TransAmadi Industrial Layout Port Harcourt Rivers State Nigeria for allowing us the use of their facilities.

REFERENCES
Armitage, T. (1997). Contaminated sediment. In: Proceeding of the U.S. Geological Survey (USGS) Sediment
Workshop February 4-7, U.S. Environmental Protection Agency

ASTM (2003). Standard practices for extraction of trace elements from sediments, Annual book of ASTM
Standards vol. 11.02.

Atlas, R.M. and Bartha, R. (1993). Microbial Ecology Fundamentals and Applications , 3rd edition. The
Benjamin/Cummings Publishing Company Inc. 390 Bridge Parkway, Redwood City, CA94065.

Bryan, G.W. (1973). The occurrence and seasonal variations of trace metals in the scallops Pecten maximus L.
and Chlamys opercalon L., Environmental Pollution; 74: 227- 244.

Cauwet, G. (1987). Influence of Sedimentological Features on the Distribution of Trace Metals in Marine
Sediments Marine Chemistry; 22.221-234

Chindah, A. C., Amabaraye, S. B. Amd Sibeudu, O. C. (2004). Distribution of Hydrocarbons and Heavy
Metals in Sediment and A Crustacean (Shrimps - Penaeus notialis) from the Bonny/New Calabar River
Estuary, AJEAM-RAGEE; 9:1-17.

Deely, J. M. Tunnicliff, J. C., Orange, C. J. and Edgerley, W.H.L. (1992). Heavy Metals in Surface Sediments
of Waiwhetu Stream, Lower Hutt, New Zealand, New Zealand Journal of Marine and Freshwater Research.
26:417-427.

Forstner, U. (1989) Contaminated Sediments: Lectures on Environmental Aspects of Particle Associated

Chemicals in Aquatic Systems, Berlin, Heidelberg, New York Springer-Verlag, pp 157.

Forstner, U., Wittmann, G.T.W. (1981). Metal Pollution in the Aquatic Environment, 2nd Edition, Berlin,
Hedelberg, New York, Spriner-Verlag, pp 486

Horowitz, A.J. (1985). A Primer on Trace Element-sediment. Chemistry, U.S. Geological Survey water
supply paper 2277, pp 6.7

Kakulu, S.E. and Osibanjo O. (1988). Trace Heavy Metal Pollutional Studies in Sediments of the Niger Delta
Area of Nigeria, Journal Chemical Society Nigeria; 13; 9 - 15.

Kakulu, S.E. and Osibanjo O. (1992). Pollution Studies in Nigeria Rivers: trace metal levels of surface waters
in the Niger Delta Area of International Journal of Environmental Studies; 41: 287 - 92.

Kiely, G. (1998). Environmental Engineering, International Edition, Mdiraw-Hill. International Limited,

London, U.K.

Moriarty, F. (1990). Ecotoxicology, A Study of Pollutants in The Ecosystem, 2nd Edition, Academic Press
London.

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 V. C. Eze and G.C. Okpokwasili: Continental J. Environmental Sciences 2: 17 - 25, 2008

Muncha, A. P., Vassconcelos, M. T. S. D. and Bordalo, A. A. (2003). Macrobenthic Community in the

Douuro Estuaryi Relation with Trace Metals and Natural Sediment Characteristics, Environmental Pollution;
121:169-180.

Okoye, S.C.O., Afolabi, O. A. and Ajao, E.A. (1991). Heavy Metals in the Lagos - Lagoon Sediments,
International Journal of Environmental Studies; 37:35-41.

Presley, B.J., Taylor, R.J. and Boothe, P.N. (1992). Trace metal contamination in sediments of the Eastern
Mississippi Bight, Marine Environmental Resources; 33: 267 -82.

Shell Petroleum Development Company (SPDC), (1986). Street Guide of Port Harcourt

Szefer, R., Wolowiez, M., Kusak, A., Desluus-Paoli, M., Garowski, W., Frelek, K. and Belzunce, M.J. (1999).
Distribution of mercury and other trace metals in the cockir Cerastoderma glaucum from the Mediterranean
Lagoon, Etung De Thau. Arch Environmental Contamination Toxicology; 36: 56 – 63.

Tkalin, A.V., Presley, B.J. and Boothe, P.N. (1996). Spatial and temporal variations of trace metals in bottom
sediments of Peter the Great Bay, The Sea of Japan, Environmental Pollution ; 92: 73 – 78.

Varekamp, J.C. (1990). Trace Element Geochemistry and Pollution History of Mudflat and Marsh Sediment
from the Connecticut Coastline, Weslsyen University E& ES Department.

Received for Publication: 04/10/2008

Accepted for Publication: 25/11/2008

Corresponding Author
V.C. Eze
Present address: Department of Microbiology, Michael Okpara University of Agriculture, Umudike, P.M.B.
7267, Umuahia, Abia State, Nigeria.
E-mail: vin13eze@yahoo.com

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