International Journal of Scientific Research in Environmental Sciences (IJSRES), 1(9), pp. 240-249, 2013 Available online at http://www.ijsrpub.

com/ijsres ISSN: 2322-4983; 2013 IJSRPUB http://dx.doi.org/10.12983/ijsres-2013-p240-249

Full Length Research Paper Physicochemical and Microbial Composition of Wastewater Samples Collected from a Petrochemical Company in Southern Nigeria
Beckley Ikhajiagbe1*, Osazuwa Omoregbe2, Anita Adigwe2
1 2

Dept. of Plant Biol. and Biotechnology, University of Benin, Benin City, Nigeria Dept. Science Laboratory Technology, University of Benin, Benin City, Nigeria *Corresponding author: Dr. B. Ikhajiagbe, ikhaj@yahoo.com
Received 26 July 2013; Accepted 22 August 2013

Abstract. The present study investigated the physicochemical and microbial composition of wastewater samples collected from a petrochemical company in Ekpan, Delta State, Nigeria. The aim was to investigate whether these effluent discharges met international standards for safe limits. Waste water samples were collected within the month of April, 2012, from three points, including petrochemical channel (PC), outfall channel (OC) and saver pit (SP). The control was raw water (tap water) for general use in the company. Results showed that following statutory provisions of Nigerian Federal Environmental Protection Agency in 1991 and the Canadian Council of Ministers of the Environment in 1995, waste water samples collected did not pose any environmental risk even when let into open waters. Fungi species identified in the water samples were Aspergillus niger, Fusarium solani, Penicillium sp., and Trichoderma sp. Bacteria species included; Micrococus varians, Bacillus subtilis, Pseudomonas putida, Proteus vulgaris and Bacilus pumilis. Key words: heavy metals, microbiological, petrochemical, physiochemical, waste water

1. INTRODUCTION The demand for petroleum as a source of energy and as a primary raw material for chemical industries in recent years has resulted in an increase in world production (Gutnick and Rosenberg, 1977). This dramatic increase in production, refining and distribution of crude oil has brought with it an ever increasing problem of environmental pollution (Atlas and Bartha, 1992). The fate of petroleum hydrocarbons in the environment is largely controlled by abiotic factors which influence rates of microbial growth and enzymatic activities that determine the rates of petroleum hydrocarbon utilization (Leahy and Colwell, 1990). The persistence of petroleum pollution depends on the quantity and quality of hydrocarbon mixture and on the properties of the affected ecosystem depending on the conditions available. This is even more of a concern when waste water from petrochemical industries is released into the environment without credence to its physicochemical composition. The worst hit is water quality. Water quality expresses the suitability of water for various uses or processes. Water quality is currently been compromised by a wide range of natural and human influences. This therefore leaves behind traces of scarcity of clean water. This scarcity of clean water and pollution of fresh water has led to a situation where most of the urban dwellers in developing countries and three quarters of their rural dwelling

population no longer have access to reasonably safe water supplies (Lloyd and Helmer, 1992). Water and wastewater assessment is very crucial to safeguard public health and the environment (Okoh et al., 2005; 2007). However, water quality data on fresh and portable waters in most of Africa and other developing countries are still sparse and uncoordinated. Therefore, monitoring these parameters is important for safety assessment of the environment and human public health in particular. Most of the accessed water is at the mercy of indiscriminate disposal of toxic waste. Even some of the waste water that has been properly channeled into most water ways may not have been declared clean. More so, certain physicochemical parameters of waste water need to meet with standards before declared fit for onward disposal into water bodies. Comparisons of some of these statutory limits show some level of discrepancies. For example, comparing heavy metal limits using the Canadian Council of Ministers of the Environment and Nigerian Federal Environmental Protection benchmarks (FEPA, 1991; CCME, 1995) show disparities in acceptable limits. Incidentally these two benchmarks are commonly used by water analytical laboratories within and around the study area. This therefore forms the basis for the present study. Waste water streams from a petrochemical company like a refinery can contain a number of chemicals which originate from crude oil, including petroleum hydrocarbons, heavy metals, phenolic

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compounds, sulfides and ammonia. The study area, as a refinery, was commissioned in Nigeria in 1978. It was built to process 100,000 barrels of crude per day and this was later debottlenecked in 1987 to 125,000 barrels per day. The petrochemical plants commissioned in March 1988 are made up of a 35,000MT/year polypropylene and 18,000MT/year carbon production facilities. Industrial wastewaters entering a water body represent a heavy source of environmental pollution in Nigerian rivers. It affects both the water quality as well as the microbial and aquatic flora. With competing demands on limited water resources, awareness of the issues involved in water pollution, has led to considerable public debate about the environmental effects of industrial effluents discharged into aquatic environments. Moneim et al. (2010) investigated the chemical and physical properties of the wastewater from bakers yeast industry from the Sudanese fermentation industry (SFI). The study showed that all wastewater samples contained higher amounts of micro-elements and lower amounts of macro-elements. Although screening benchmarks were not a basis for adjudging the safety of the waste water, the wastewater was found to be rich in minerals and nutrients, for this reason it is useful to use it in agriculture, irrigation and energy purposes after being treated. Lokhande et al. (2011) studied the physico-chemical parameters of industrial waste water effluents collected from Taloja industrial belt of Mumbai. The study revealed that engineering, paper mill, fine chemical, dyes, paint, pharmaceutical, petrochemical and textile industries were some of the major industries responsible for polluting the surrounding aquatic environment. It was observed that pH values of effluent samples collected from paint, pharmaceutical and dyes industries were slightly above and below the limit of 6.5 to 8.5 by ISI and WHO. The researchers observed that these industrial effluents had resulted in pollution of nearby Kasardi River thereby affecting the growth of vegetation and aquatic life. In 2008, Israel and coworkers investigated the physicochemical properties of effluents and soil samples where sediments from the treated effluents were dumped. They compared these parameters with established international standard (FEPA). Low concentrations of iron, zinc, copper, cadmium, lead, nickel and cobalt was also observed. Some heavy metals were not detected at all in some of the effluent samples analyzed. Apart from temperature and total dissolved solid TDS, all the other parameters were below FEPA effluent limitations in Nigeria. The present study however aims to investigate the physiochemical properties of effluent discharges from a petrochemical company in Ekpan, Delta State, Nigeria with a view to

determining whether they meet international standards for safe limits. The refinery was designed to process Escravos Light Crude (Chevron) and Ughelli Quality Control Crude (UQCC), which is also known as Shell Crude into, finished Petroleum products while the petrochemical plants convert the otherwise low utility refining by-products namely propylene and decant oil to produce value-added polypropylene and carbon black products. The main objective of the company is to efficiently and profitably process crude oil into petroleum products, manufacture and market petrochemical products through effective resource utilization, while exploiting new business opportunities. The companys production processes can be classified into broad categories namely the primary and secondary processes. The primary processes use distillation principles to separate crude into intermediate and some finished products while the secondary processes use catalyst to convert the intermediates to higher quality finished and value added petrochemical products. All these production processes eventually affect the quality of waste water generated from the company. However, this water is subjected to a number of treatment platforms before final discharge into the environment. The first stage of the treatment process is the API separator, which is named after the American Institute of Petroleum. As its name suggests, the separator physically separates the free oil and solids from the water. Gravity allows any oil in the water to rise to the surface of the separator and any solid particles to sink to the bottom. A continually moving scraper system pushes oil to one end and the solids to the other. Both are removed and the recovered oil is sent back to the Refinery for reprocessing. In the second stage, small suspended oil particles are removed in the Dissolved Air Flotation unit. A polyelectrolyte chemical is added to the waste water to help bind the small oil droplets into larger ones, which will float. Air is also injected to lift the amassed particles to the surface where they can be skimmed off. Both the API separator and the Dissolved Air Flotation Unit are covered processes, which prevents oil from evaporating and being released into the atmosphere. In this way, the refinery has greatly reduced its emissions of volatile organic compounds. The third treatment step is the removal of dissolved organic contaminants and nutrients in the Activated Sludge Units (ASUs). In this process, naturally occurring microorganisms feed on the dissolved organics in the waste water, and convert them to water, carbon dioxide and nitrogen gas, which can be safely released into the atmosphere. In the final stage,

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waste water enters the clarifying tanks, where the microorganisms settle to the bottom while the treated waste water flows away. An optional treatment step is to conduct further settling in the polishing ponds, or the water can be pumped back to the Activated Sludge Unit for retreatment. Once water is cleaned to the appropriate standard it is discharged directly to the Sepia Depression Ocean Outfall Line (SDOOL). The study therefore aims to reveal if there is any impending adverse impact on the physico-chemical characteristics of the receiving watershed as a result of the discharge of treated effluents from the wastewater treatment plant. 2. MATERIALS AND METHODS 2.1. Sample Collection Wastewater samples were collected from three points in the Environmental Unit of the Petrochemical

Company. These points included the petrochemical channel (PC), which usually contained treated petrochemical wastes that come directly from the petrochemical waste treatment plant. The other points were the outfall channel (OC) and the saver pit (SP). The OC contains general wastes from the refinery plants. The SP is the point where the entire wastes in the company go directly before subsequent treatment prior to discharge into the environment. Wastewater samples were collected in sterile plastic bottles and kept in an ice park, before taking directly into the laboratory for physicochemical and microbial analyses. The control was raw water (tap water) for general use in the company. Sample collection was done once in the month of April, 2012.

Fig. 1: Map showing study area (Uzoekwe and Oghosanine, 2011)

2.2. Water Analyses 2.2.1. Microbiological Analysis Potato dextrose agar (PDA) and nutrient agar (NA) were used during the course of this study. The medium used was sterilized by autoclaving at 15psi (1210C) for 15minutes. Chloramphenicol and fulscin at 0.02g per 200ml of medium was introduced at pouring to inhibit the growth of bacteria and fungi. Inoculation and transfer of culture were carried out on sterile inoculating bench CRC model HSB 60*180, after wiping with methylated spirit. Nine (9) ml of distilled water was pipette into six McCarthy bottles prepared in duplicate and labelled 101 to 106 for serial dilution preparation and were labeled accordingly. The bottles were sterilized in an autocalved at 1210C

for 15 minutes. McCarthy bottles also labeled accordingly represented the stock solution. From the stock bottles, with a sterile pipette 1ml each was transferred from the stock bottle into the bottle labeled 101 to 106 for Serial dilution preparation for each of the samples collected. 0.1ml aliquots from the 106 tubes were aseptically inoculated onto already prepared plates of nutrient agar and potato dextrose agar using the spread plate method of inoculation. The nutrient agar (for bacteria) were incubated at 37oC for 24 hours while the potato dextrose agar plates (for fungi) were incubated at ambient laboratory temperature (282oC) for 72 hours. After the incubation period, plates with distinct colonies were counted and recorded as cfu/g. The bacterial isolates were identified and characterized using cultural, morphological and standard

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biochemical tests as described by Cheesebrough (2003). The fungal isolates were identified based on their colour of aerial hyphae and substrate mycelium, arrangement of hyphae, and conidial arrangement. 2.2.2. Physicochemical Analysis This was determined using pH meter 3015, Jenway, U. K. Ten mls of the sample was placed in a beaker; it was allowed to stand for 30 minutes. A buffer solution was used to zero the pH meter. Then the electrode of the pH meter was inserted into the sample and the pH readings were taken. 2.2.3. Electrical Conductivity (EC) EC is the measure of the ability of an aqueous solution to convey an electric current. This ability depends upon the presence of ions, their total concentration, mobility, valence and temperature. EC was determined by conductivity meter following the procedure of Richard (1954). 2.2.3. Sodium, potassium, calcium and magnesium determination Absorption Spectrophotometric (Chem. Tech. Analytical) using standard methods established by APHA (1985) for metals determination. Exactly 2.5 ml of concentrated HNO3 (Analar grade) was added to 25 ml of water sample in a clean Teflon beaker. The mixture was heated on a hot plate to concentrate the sample to about 10 ml. Heating of the sample continued with periodical addition of 1 ml portion of concentrated HNO3 until a clear solution was obtained. The clear solution was then allowed to cool after which it was transferred into 25 ml standard flask and made up to the mark with distilled water. Blank samples were prepared for background correction using the method as described. The analytical procedure described was quality controlled. Quality assurance study was carried out in terms of recoveries of metals from a spiked sample in order to ascertain the efficiency of the analytical procedures. This was done by spiking water with known amount of standard of the metals and recovered as described by AOAC (1990). 2.2.4. Determination of Chemical Oxygen Demand (COD) 10ml of the sample were taken in a100 ml bottle then 5 ml of conc. H2SO4 was added and about 1g of copper sulphate (CuSO4) also added. Then 3 ml of prepared 40N KMnO4 solution was added and immersed the bottle in boiling water for 30min while

keeping the surface of the boiling water at the higher level than the surface of the sample. Then 3 ml prepared 40N sodium oxalate (Na2C2O4) was added and immediately titrated with 40N potassium permanganate (KMnO4) until violet colour appeared then repeated for the blank separately under same condition using 10 ml of distilled water instead of 10 ml of sample. Then,

where: A = ml of KMnO4 used for sample; B = ml of KMnO4 used for blank. 1/40 = Molarity of KMnO4; 8000 = milliequivalent weight of oxygen 1000 ml/l. 2.2.5. Determination Demand (BOD) of Biochemical Oxygen

Two 100 ml bottles was obtained with lid and cleaned well. 25 ml sample was taken in each bottle and 75 ml of distilled was added to the two bottles. Then the two bottles closed well .One bottle was kept in the incubator at (20-22)C for 5 days. Then 10 ml of manganese sulphate solution and 2 ml of alkali- iodide solution were added to the other bottle well below the surface of the liquid by using a syring. Then the bottle closed and mixed by inverting the bottle several times. When the precipitate settles leaving a clear supernatant above the precipitate shaked again slowly by inverting the bottle, and when the setting has produced at least 50 ml supernatant 8 ml of con. H2SO4 were added. Then the bottle was closed and mixed by gentle inversion until dissolution was completed. Then 100 ml of the sample was titrated with 0.05M Na2S2O3 solution until a pale yellow solution is reached. Then 2 ml of freshly prepared starch solution was added and titration was continued until a blue colour appeared. The procedure was then repeated using 100 ml distilled water (blank). Then, repeated for incubated sample after 5 days. The BOD was calculated as follows: BOD as mgO2/L = 16(V1 - V2) where: V1 = ml of Na2S2O3 used for the sample before incubation; V2 = ml of Na2S2O3used for the sample after incubation. 2.2.6. Determination of Suspended Solids (NonFilterable Solids) Cleaned crucible with filter paper was ignited to constant weight in an oven (W1). Then 25 ml sample was taken and filtered through the crucible. Then the crucible was dried in a constant temperature oven maintained at 103C for 24 hours. Then cooled and weight (W2). The suspended solids were then calculated as follows:

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3. RESULTS where: W1 = Weight of empty crucible plus filter paper; W2 = Weight of the crucible and filter paper after drying; V = Volume of the sample. 2.2.7. Determination of Total Dissolved Solids Total dissolved solids were determined by evaporating the waste samples to dryness. In this method 50 ml of sample were transferred to a weighed evaporating dish, and evaporated to dryness by heating for 1-2 hours at 180C to a constant weight. Total dissolved solids were calculated as follows: Results from the present study are present on the Tables 1 4. The pH of waste water collected from petrochemical channel (PC) was 5.2 as against 8.2 in waste water collected from saver pit (SP). Electric conductivity ranged from 70.8 /cm 250.0/cm, the lowest value being recorded in raw water (control) whereas, and the highest value was recorded in the saver. Salinity content of waste water was 0.08g/l in the outfall channel, 0.042 g/l in the PC and 0.927 g/l in the SP, compared to 0.032 g/l in the control. Turbidity was undetected in both raw water (control) and PC, where as turbidity in the SP was 10.2 NTU. Total dissolved solids (TDS) was 1.2mg/l in the PS and 22.9 mg/l in the SP, compared to 1.5 mg/l in the raw water (control). Chemical oxygen demand (COD) ranged from 28.8mg/l to 181.6mg/l, the highest being recorded in the SP. Magnesium in waste water was 0.16mg/l in the PC, 0.24mg/l in the outfall channel (OC), and 3.44mg/l in the raw water control. Obviously physiochemical parameters listed on Table 1 were higher in the SP than from any other source of the waste water in the present study. Table 2 presents the heavy metal composition of the wastewater collected in the study area, Nigeria. Fe content in wastewater was 0.18 mg/l in the petrochemical channel, 0.16 mg/l in the outfall channel and 0.10mg/l in raw water (control). Fe in waste water collected from the saver pit was highest (1.6 mg/l). The range of values obtained for manganese in the waste water was 0.04mg/l to 0.07mg/l. In the PC channel, waste water contained 0.09mg/l of Zn, compared to 0.21mg/l obtained from the SP. Chromium, Nickel, Lead and Vanadium where undetected, with the sensitivity of the spectrophotometer being 0.001mg/l. The Total Hydrocarbon Content THC ranged from 0.03mg/l to 5.3 mg/l, the highest THC resulting from the saver pit. Hazard quotients (HQ) helps researchers to compare contaminant levels with toxicity or bench mark levels in other to establish ecological toxicity when HQ is greater than one (HQ>1). HQ was less than one (HQ < 1) in all contaminants assayed for waste water collected from all the channels; indicating that no toxicity was due to contaminant concentration in the waste water samples. Common bacterial isolates from the waste water were Pseudomonas putida, Bacillus substillis, Micrococcus varians and Micrococcus varians (Table 4). Bacteria counts in the petrochemical channel was 2.7 x 105 cfu/g, 2.6 x 105 cfu/g in the outfall channel, 3.2 x105cfu/g in the saver pit, compared to 2.1 x 105cfu/g in the raw water (control). Fungal isolates included Penicillium species, Aspergillus niger, Aspergillus flavus and Rhizopus sp, among which

2.2.8. Determination of Turbidity The turbidity was determined photoelectrically using photometer 7000. The turbidity of waste water depends on the quantity of solid matters present in the suspension state. Turbidity is a measure of lightemitting properties of waste water, and turbidity test is used to indicate the quality of waste discharges with respect to colloidal matter. The turbidity depends up on the strength of waste water. The stronger or more concentrated the waste, the higher is it is turbidity. 2.2.9. Extraction of Micronutrients in Soils by Hydrochloric Acid Method Ten (10) l of water was weighed into a 250 ml plastic bottle. 100 ml of 0.1 m HCI was added, stoppered, and then shaken for 30 minutes. And then Fe, Cu, Mn, Zn, Cd, Cr, Pb, Ni, and V were determined in the water by Atomic Absorption Spectrometry (APHA, 1985). 2.2.10. Computation of Hazard Quotient (HQ) HQ expresses the possibility of the contaminant being an ecological risk or a contaminant of potential ecological concern (COPEC). The hazards Quotient is expressed by the following equation:

When HQ > 1: Harmful effects are likely due to contaminant in question; When HQ = 1: Contaminant alone is not likely to cause ecological risk; When HQ < 1: Harmful effects are not likely.

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Penicillium, Aspergillus niger and Aspergillus flavus were hydrocarbon degraders (Table 4). Hydrocarbon degrading fungal count was 1.1 x 105 cfu/g in the petrochemical chemical, compared to 1.5 x105 cfu/g of total fungal count. Hydrocarbon degrading fungi count was 0.4 x 105 cfu/g in waste water collected from saver pit, compared to 1.1 x 105 cfu/g of total fungi count. 4. DISCUSSION Wastewaters are generated by many industries as a consequence of their operation and processing. Depending on the industry and their water use, the wastewaters contain suspended solids, both degradable and nonbiodegradable organics; oils and greases; heavy metal ions; dissolved inorganics; acids, bases and colouring compounds Industrial effluent characteristics provide basic information about the integrity of the aquatic habitat within such rivers and streams into which they are discharged. Most of these effluents pose inestimable harm to which the microbial entity is the most adversely affected. The present study provides information on physicochemical [parameters of waste water collected from a petrochemical industry in the Niger Delta. The pH values observed for all the samples collected in the petrochemical industry were 5.2, 5.3 and 8.2. These values were either below or above statutory limits provided by FEPA (1991). The control was however safe. However values obtained for both TSS and TDS were within statutory limits (FEPA, 1991). TSS in the control was 1.5 mg/l, whereas in both the petrochemical channel and saver pi, TSS was 28.8 and 181.6 mg/l. Solids suspended in water may consist of inorganic or organic particles. Inorganic solids such as clay, silt and other soil constituents are common in running surface water as rivers and streams. Organic material such as plant fibers and biological solids as algal cells and bacteria are also common constituents of surface waters. Because of the filtering capacity of the soil, and because of stagnation as in wells, suspended material is a rare constituent of groundwater. Ordinarily, sanitary sewage usually contains large quantities of suspended solids that are mostly organic in nature. This may also account for highest TSS value in the saver pit. The odour of water samples vollected from the saver pit was offensive. An explanation would be that because suspended organic solids degrade biologically, it may result in objectionable by-products of foul odours. Presence of dissolved solids alone gives taste. However a concentration greater than 500 - 1000 mg/l of

dissolved salts may give rise to bitter taste and laxative effect. Results of the present study presented TSS of lower values of < 200 mg/l. Turbidity was undetected in water samples collected from both control and petrochemical channels; but 3.9 and 10 Nephelometric turbidity units (NTU) in samples obtained from outfall channel and saver pit respectively. Turbidity is the property of absorption of light or its scattering by suspended material in water. Both absorption and scattering are influenced by size and surface characteristics of the suspended material. Turbidity may not be caused by transparent suspended solids. Colloidal material of clay, silt, rock fragments and metal oxides from the soil, vegetable fibres and microorganisms cause turbidity. Also soaps, detergents and emulsifying agents produce stable colloids that result in turbidity. The higher NTU value obtained in the saver pit might be accounted for especially being the receiver end of some of these other waste water channels in the experimental area studied. Although turbidity measurements are not commonly run on wastewater, discharges of wastewater may increase the turbidity of natural bodies of water. The colloidal material associated with turbidity provides adsorption site for chemicals, that may be harmful or cause undesirable tastes and odours and shield pathogenic biological organisms from disinfection. Water samples collected from all collection points in this study were coloured apart from the raw water control. Pure water as rain water is colourless. But water is a universal solvent and is often coloured by many substances. Running water carries suspended solids which cause apparent colour. Water whose colour is due to suspended matter is said to have apparent colour. Apparent colour fades out when suspended solids settle. Colour contributed by dissolved solids is known as true colour which remains permanently. The colour of the samples from the saver pit was grey. The researcher however observed that when samples collected from saver pit was kept in a conical flask and left for about 3 months, there was a clear supernatant, and a grey sediment that settled at the bottom of the flask. Previous studies have shown that this grey colour eventually deepens with time, depending on the concentration of organic matter. Colour is a visible pollutant. Coloured water is not aesthetically acceptable for domestic as well as industrial use. Highly coloured water may not be accepted for laundering, dyeing, papermaking, beverage manufacturing, dairy production, food processing, textile and plastic production.

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Table 1: Physiochemical parameters of waste water collected from different sources in a petrochemical industry in southern Nigeria pH EC Sal. Col. Turb. TSS TDS COD HCO3 Na K Ca Code (S/cm) (g/l) (Pt.Co) (NTU) Units

Mg (mg/l) Nil 0.16 0.24 3.44 0.06

Cl

NH4N

NO2

NO3

SO4

TH A B C D

6-9 *5.2 *5.3 *8.2 6.9

Nil 93.5 177.9 2050 70.8

Nil 0.042 0.080 0.927 0.032

Nil ND 2.5 21.7 ND

Nil ND 3.9 10.2 ND

30.0 1.2 5.8 22.9 1.5

2000.0 46.8 88.9 1020 35.2

40.0 28.8 *178.4 *181.6 28.8

Nil 36.6 42.7 500.2 67.1

Nil 10.60 28.68 49.80 3.02

Nil 0.08 0.13 0.87 0.02

Nil 1.42 2.74 10.62 0.49

600.0 44.31 106.4 124.1 44.32

5.0 0.10 1.41 0.17 0.13

Nil 0.032 0.055 1.24 0.045

Nil 0.03 1.48 2.46 0.49

20.0 0.04 3.91 4.92 1.70

50.0 10.27 48.90 *53.64 9.46

*above statutory limits provided by FEPA (1991) Threshold by FEPA (1991)= TH; Petrochem. Channel= A; Outfall channel= B; Saver pit= C; Raw water (Control)= D

Table 2: Heavy metal composition of waste water collected from different sources in a petrochemical industry in southern Nigeria
Sources of waste water Fe Mn Zn Cu Cr Cd mg/l BDL 0.01 0.02 0.01 Ni Pb V THC

Petrochem. Channel Outfall channel Saver pit Raw water (Control)

0.18 0.16 1.60 0.10

0.04 0.04 0.07 0.08

0.09 0.05 0.21 0.07

0.02 0.05 0.08 0.04

BDL BDL BDL BDL

BDL BDL BDL BDL

BDL BDL BDL BDL

BDL BDL BDL BDL

0.03 0.05 5.30 0.04

BDL beyond detectable limit (<0.0001 mg/l).

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Table 3: Hazard quotients for heavy metal composition of waste water collected from different sources in a petrochemical industry in southern Nigeria
Sources of waste water Fe Mn Zn Cu Cr Cd Ni Pb V

a. Threshold by CCME (1995) Petrochem. Channel (x 10-3) Outfall channel (x 10-3) Saver pit (x 10-3) Raw water (Control) (x 10-3) b. Threshold by FEPA (1991) Petrochem. Channel Outfall channel Saver pit Raw water (Control)

300.00 0.600 0.530 5.330 0.330 20.00 0.009 0.008 0.080 0.005

80.00 0.50 0.50 0.88 1.00 Nil Nil Nil Nil Nil

30.00 3.00 1.67 7.00 2.33 1.00 0.09 0.05 0.21 0.07

2-4.00 22.50 12.50 20.00 10.00 1.50 0.013 0.033 0.053 0.027

2-20.00 <1.00 0.50 1.00 0.50 Nil Nil Nil Nil Nil

0.017 <1.00 <1.00 <1.00 <1.00 1.00 <10-3 0.01 0.02 0.01

25-150.00 <1.00 <1.00 <1.00 <1.00 1.00 <10-3 <10-3 <10-3 <10-3

1-7.00 <1.00 <1.00 <1.00 <1.00 0.50 <10-3 <10-3 <10-3 <10-3

19.00 <1.00 <1.00 <1.00 <1.00 Nil Nil Nil Nil Nil

Nil not available for determination

Table 4: Microbial composition of waste water collected from different sources in a petrochemical industry in southern Nigeria
*Micrococus varians *Bacillus subtilis *Pseudomonas putida Proteus vulgaris Bacilus pumilis Total Bacterial Count (x 105cfu/g) Total Hyd. Deg. Bact. (x 105cfu/g) Percentage Hyd. Deg. Bact. (%) *Aspergillus niger *Fusarium solani *Penicillium sp. Trichoderma sp. Total fungi count (x 105cfu/g) Total hyd. Deg. Fungi (x 105cfu/g) Percentage Hyd. Deg. Fungi (%) Petrochem. Channel Outfall channel Bacteria species + + + + + + 2.7 1.3 48.1 + + + + 1.5 1.1 73.3 2.6 1.2 46.2 Fungi species + + + 2.1 1.4 66.7
+present, -absent

Saver pit + + 3.2 1.1 40.0 + + 3.8 0.4 13.3

Raw water (Control) + + + 2.1 1.1 52.4 + + 2.4 0.8 33.3

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Concentration of HCO3 in water samples ranged from 36.6 500.2 mg/l. Alkalinity is the ability of water to neutralize acids. HCO3 is quite common in atmosphere and soil contribute to alkalinity. This compound results from the dissolution of mineral substances in the soil and atmosphere. Phosphates from detergents and fertilizers and insecticides of agricultural land may also cause alkalinity. Fungi species identified were Aspergillus niger, Fusarium solani, Penicillium sp., and Trichoderma sp. bacteria species included Micrococus varians, Bacillus subtilis, B. pumilis, Pseudomonas putida, and Proteus vulgaris. These were among the bacteria species isolated by Ali and Naseem (2012) in a pharmaceutical industry. 5. CONCLUSION The study showed that following statutory provisions of FEPA (1991) and CCME (1995), water samples collected could not pose any environmental risk even when let into open waters. Although adjudged ecologically safe, the saver pit was observed to contain more toxicants than other effluent discharge points because, from the experience gathered in the study, all waste water collected in the petrochemical industry end up in the saver pit. The researcher however observed that the waste from the saver pit undergoes further treatment before discharge into open waters. This is further to ascertain the quality of waste water discharged into the environment REFERENCES Ali A, Naseem F (2012). Frequency distribution of bacteria isolated from different industrial effluents. Daffodil International University Journal of Science and Technology, 7 (1): 28 33. AOAC (1990). Methods of Analysis. Association of Official Analytical Chemists, Washington D. C. 326p. APHA (1985). Standard method for the examination of water and waste water. American Public Health Association, Washington DC. 256p Atlas RM, Bartha R (1992). Hydrocarbon biodegradation and oil spill bioremediation. Advanced Microbial and Ecology, 12: 287-338. Canadian Council of Ministers of the Environment (CCME). (1995). Protocol for the Derivation of Canadian Sediment Quality Guidelines for the Protection of Aquatic Life. Report CCME EPC98E. Prepared by the Task Group on Water Quality Guidelines, Winnipeg, Manitoba. 38p.

Cheesebrough M (1998). District Laboratory Practice in Tropical Countries, Part II (Microbiology). Cambridgeshire Tropical Health Technology, Cambridge, UK. 326pp. Federal Environmental Protection Agency (FEPA) (1991). National Guidelines and Standards for Waste Management in Oil and Gas Industry in Nigeria. FEPA Nigeria). Official Gazette, Nigeria, 1991. Gutnick DL, Rosenberg E (1977). Oil tankers and Pollution: A Microbiological approach. Annual Review of Microbiology, 341: 379-396. Israel AU, Obot IB, Umoren SA, Mkpenie V, Ebong GA (2008). Effluents and Solid Waste Analysis in a Petrochemical Company- A Case Study of Eleme Petrochemical Company Ltd, Port Harcourt, Nigeria. E-Journal of Chemistry, 5(1): 74-80 Leahy JG, Colwell RR (1990). Microbial degradation of hydrocarbons in the environment. Microbiology Review, 54: 305-315. Lloyd B, Helmer R (1992). Surveillance of Drinking Water Quality in Rural Area. Longman Scientific and Technical Publication, New York. 108pp. Lokhande RS, Singare PU, Pimple DS (2011). Study on Physico-Chemical Parameters of Waste Water Effluents from Taloja Industrial Area of Mumbai, India. International Journal of Ecosystem, 1(1): 1-9 Moneim A, Sulieman EH, Yousif AWM, Mustafa AM (2010) Chemical, Physicochemical and physical properties of wastewater from the Sudanese fermentation industry ((SFI). Fourteenth International Water Technology Conference, IWTC, 2010, Cairo, Egypt. Okoh AI, Barkare MK, Okoh OO, Odjadjare E (2005). The cultural microbial and chemical qualities of some waters used for drinking and domestic purpose in a typical rural setting of Southern Nigeria. Journal of Applied Science, 5(6): 1041- 1048. Okoh AI, Odjadjare EE, Igbinosa EO, Osode AN (2007). Wastewater treatment plants as a source of microbial pathogens in the receiving watershed. African Journal of Biotechnology, 6(25): 2932-2944 Richard LA (1954). Diagnoses and improvement of saline and alkali soils. Agriculture Hand Book 60: USDA, USA. Uzoekwe SA, Oghosanine FA (2011).The effect of refinery and petrochemical effluent on water quality of Ubeji Creek Warri, Southern Nigeria. Ethiopian Journal of Environmental Studies and Management Vol. 4 No.2.

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Dr. B. Ikhajiagbe, Environment Mgt Consultant and Lecturer at the Dept of Plant Biology and Biotechnology, University of Benin, Benin City, Nigeria. His area of specialty is Ecophysiology and Bioremediation Technology. He is a member of the Nigeria Environmental Society.

Mr. Osazuwa Omoregbee, He is a research graduate of the Dept. of Science Laboratory Technology, University of Benin, Benin City. He is a researcher and support staff of the Dept. of Science Laboratory Technology, University of Benin, Benin City.

Adigwe Chukwuelofuna Anita, She is from Ibusa in Delta State, born to the Christain family of Mr and Mrs R.E Adigwe on 15th of April 1991. She was a student of University of Benin. Faculty of life Sciences, Dept of Science Lab Tech Class of 2012. She also is a safety supervisor certified by the Nigerian Institute of Safety Professionals (NISP) in Warri, Delta State, Nigeria.

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