M. B.

Ibrahim

Bioscience Research Communications Vol. 20, No. 6, December 31, 2008 Printed in Nigeria

0795-8072/2008 $12.00 + 0.00 2008 Klobex Academic Publishers http://www.klobex.org/brc

BRC 2008062/20602

Atomic Absorption Spectrophotometric Determination of Cr(VI) Levels from Tannery Effluents

M. B. Ibrahim
Department of Pure and Industrial Chemistry, Bayero University, P. M. B. 3011, Kano, Nigeria (Received September 8, 2008) ABSTRACT: Effluent samples collected from drainage runways containing discharge from five tanneries located at Challawa Industrial area of Kano state were analysed spectrophotometrically for their Cr(VI) content. The average levels of Cr(VI) at the various sampling points were A(3.00), B (4.00), C(4.83), D(3.00), E(1.00), F(1.33), G(1.50), H(1.33), I(1.83) and J(2.17ppm). Thus, mean chromate content of the effluent is 2.399ppm, with a standard deviation of 1.274645ppm. From the levels of chromate, the results shows high level of chromate in the effluent as it has pass the threshold level of 0.5ppm for effluent discharge. Keywords: Effluent, Chromate, Tannery, Pollution

Introduction
Tanning of hides and skins with a sole aim of changing them to leather have been an important industrial processes since olden days. Pollution has been regarded as an inevitable consequence of such activities for much the same time. Chromium as an environmental pollutant enters into the ecosystem by electroplating, metal finishing, chromate preparation, leather tanning etc. The two form of chromium predominantly present in the environment are Cr(III) and Cr(VI), in which Cr(VI) is soluble, toxic and carcinogenic (Ackerley, et al., 2004). Chromium (III) sulphate salt is used as tanning agent, resulting in severe groundwater contamination around tanneries, which is transformed into Cr (VI) (Thakur, et al., 2001). Large numbers of researchers have engaged themselves in wide ranges of researches in order to bring solution to this and much other environmental pollution. Iwata, et al., 2003 used photoreduction on the surface of titanium oxide (TiO2) films of dilute Cr(VI) solutions at an adjusted pH 2 for a period of 7 days, in which the concentration of Cr(VI) ion was found to decrease from 10ppm to 0.03ppm. The work of Rajmond, 2005; utilised a mixed bed ion exchange column for the simultaneous determination of Cr(III) and Cr(VI) using UV detector at a wave length of 365nm from environmental samples such as rainwater and galvanic sediments. The performance of his method was established from the linearity, limit of detection, limit of quantification and the influence of sample pH.

Email: bashir_mbi@yahoo.com

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Similarly, Jen-Fon, et al., (1993) used a reversed-phase ion pair high-performance liquid chromatographic method for simultaneous determination of Cr(III) and Cr(VI) in aqueous solution. The Cr(III) was first chelated with ethylenedi-aminetetraacetic acid (EDTA) and the resulting Cr(III) EDTA complex was separated with C8 column using an eluent containing acetonitrile and tetrabutylammonium ion. The separated species were then monitored with a UV detector at 242nm. In another work Noroozifar and Khorasani, 2003, developed a procedure that is very specific, selective, simple and inexpensive for the speciation of Cr(VI) and Cr(III) from spiked natural water samples and effluent samples from leather treatment plant. The method is based on the quantitative extraction of chromate and Cr(III) as tetrabutylammonium chromate ion-pair in methyl isobutyl ketone (MIBK), and then back extraction and preconcentration with an acidic diphenylcarbazide (DPC) solution. Whereby the Cr(VI) DPC complex was determined by a spectrophotometer at 548nm. In a summary, industrial waste are the byproducts which result from industrial processing operation. Though industrial wastes include liquids, solids and gases, this work is only concerned with the liquid part, which is commonly known as industrial wastewater, which are either discharged directly into the receiving water (if they meet the necessary standards) or else are discharged into municipal sewers (Uppal, 2005).

Materials and Methods

a. Sampling

Three effluents samples each were collected at ten different points along the drainage runway containing discharge from five different Tanneries situated at Challawa Industrial area of Kano, each sampling point approximately 20meters from the other, by carefully filling a 50cm3 plastic sampling bottles to the very top and stoppered while they were below the water surface. The samples were labeled A1, A2, A3, B1, B2, B3, up to J1, J2 and J3 respectively. b. Sample Pretreatment and Qualitative Analysis

All the samples were centrifuged at 2500rpm for 2min using Hermle z200A labnet centrifuge machine, and the supernatant were used for both the qualitative analysis and the sample digestions. However, were fine particles persists filtration was carried out so as to obtain clear effluent. Qualitative test, with the view to identifying the presence or otherwise of the ion of interest, was conducted on each sample by following the procedure outlined in Vogel, 1996. c. Sample Digestion

A portion (25cm3) of each sample was digested by mixing with 5cm3 mixture of (1:1) conc. H2SO4 and conc. HNO3. The solution was boiled on a hot plate at 120C until dense white fumes of SO3 just appeared. Aliquots of 5cm3 conc. HNO3 were added and the heating was continued until the solution was clear and no brown fumes were observed. 15cm3 of 0.5%v/v HNO3 were added and the solution was boiled to dissolve the soluble salts. After cooling, the solution was transferred into a 50cm3 flask and the volume was made up with 0.5%v/v HNO3 (Arnold, et al., 1985). d. Preparation of Standard Solutions

One thousand parts per million (ppm) of the standard solution was prepared by dissolving 2.828g of anhydrous potassium dichromate (AnalaR Grade) in about 20cm3 distilled deionised water. 1.5cm3 conc. HNO3 was then added and the solution was made up to mark in a 1.0 litre volumetric flask with more water. Using serial dilutions lower concentrations of 2, 4, 6, 8 and 10ppm were prepared from the stock (Arnold, et al., 1985 and Vogel, 1996).

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e. Atomic Absorption Spectrophotometric Measurements

Spectrophotometric measurements were carried out using Alpha 4 Atomic Absorption Spectrophotometer using a chromium hollow-cathode lamp and an air/ acetylene flame with strict adherence to standard calibration guidelines as contained in the operating manual. f. Physical Characterisation of the Effluent

This was done by measuring parameters such as pH, density, viscosity, conductivity and turbidity of the effluent samples. The pH of the samples were measured with Jenway 3320 pH meter after it has been calibrated against acidic buffer of pH 4.01 and a basic buffer of pH 10.01 alternately until the meter reads exactly the same value. The electrode was then rinsed in distilled water and gently blots with a clean cotton wool after which the pH of each samples were read in the same manner (Ibrahim, 2007a). Conductivity values were determined by the use of Jenway 4010 conductivity meter, which was standardized by measuring the conductivity of a 0.01N KCl solution (Jenway 4010 operating manual). Density was determined as per the procedure outlined elsewere (Ibrahim, 2007b), while turbidity and viscosity were determined using Hach turbidometer and Ostwald viscometer respectively (Levitt, 1973).

Results and Discussion

Two measurements often made on water matrices are pH and conductivity. These are usually categorized as physical tests, though they are strongly dependent on the chemical characteristics of the aqueous solution. In the pH range of water hexavalent chromium exist as CrO4 , HCrO4 and Cr2 O7 The tetrahedral, yellow chromate ion CrO4
4 2 2
2

ions. These

form part of many Cr(VI) compounds, which are relatively soluble and thus mobile in the environment. is formed by CrO3 in basic solutions above pH 6 whereas

HCrO and the orange-red dichromate ions Cr2 O72 are in equilibrium between pH 2 and 6. At pH
values below 1 the main specie present is H2CrO4. Thus, the mean value (8.935) of the pH for the various samples indicates that the probable form of the hexavalent chromium in the effluent is CrO4 . Conductivity is a measure of how well a solution conducts electricity. Water with absolutely no impurities (which really does not exist) conducts electricity very poorly. In real life, the impurities in water increase its conductivity. Because of this, if we measure the conductivity of water, we have some estimate of the degree of impurity. The mean value of the conductivity of all the samples analysed (29.69mS) suggest that the effluent contain high level of ionic contaminants. Kinematic viscosity (), simply defined as the ratio of viscosity to density of a sample, provides a good understanding of the behavior of mass transport of a dilute species. Here also from the mean value of the kinematic viscosity (0.0095cm2/s) is indicative that the effluent is highly polluted with unwanted materials. The determination of trace chromium in environmental samples is of great importance due to its toxicity. The two main oxidation states of chromium, Cr(III) and Cr(VI) present in natural waters significantly differ in biological, geo-chemical and toxicological properties(Sule and Ingle, 1996). Cr(III) over a narrow concentration range is considered essential for mammals for the maintenance of glucose, lipid and protein metabolism, whereas Cr(VI) is reported to have a toxic effect in human (Cotton, et al., 1999). The corresponding concentrations presented in Fig. 2 of the mean chromium absorbance per each sample site as presented in Table 1 were obtained by interpolation from the calibration curve shown in Fig.1. The mean value of 2.399ppm as indicated in the result obtained in this work showed that there is a high level of pollution by chromate ion in the effluent as it has exceeded the stipulated level of 0.5ppm (FEEMA, 1986). Though there is significant difference between sampling site C and E, the standard deviation value suggests that there is almost a uniform distribution of the chromate in the effluent. This may be linked to the fact that the samples were collected during the same tanning exercise.
2

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Table 1: Characterisation of the Effluent Sample pH Cond. (mS) 24.0 23.8 24.5 38.4 36.2 31.1 29.9 29.5 29.7 29.8 29.69 4.8800 Density (g/cm3) 0.9961 0.9873 0.9882 0.9902 0.9902 0.9882 0.9873 0.9873 0.9892 0.9882 0.9892 0.0027 Viscosity ( x10-4 kgm-1s-1 ) 11.102 9.641 8.733 9.802 8.775 9.573 9.072 9.240 8.988 9.407 9.4333 0.6891 Turbidity (NTU) 388 295 295 288 64 26 430 200 79 32 209.7 150.8252 Abs

A B C D E F G H I J MEAN STDEV

8.98 10.01 9.59 8.83 8.96 8.13 8.45 8.94 8.92 8.54 8.935 0.5414

0.018 0.024 0.029 0.018 0.006 0.008 0.009 0.008 0.011 0.013 0.014 0.0076

(cm2/s) 0.0111 0.0098 0.0088 0.0099 0.0089 0.0097 0.0092 0.0094 0.0091 0.0095 0.0095 0.0007

0.035 0.03 Absorbance 0.025 0.02 0.015 0.01 0.005 0 0 1 2 3 4 5 6 Concentration/ppm y = 0.006x

Fig. 1: Calibration Curve for Chromium (VI) Ion

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4 Concentration/ppm

0 A B C D E F G H I J Sampling SItes

Fig. 2: Variation of Chromium Concentration with Sampling Site

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Conclusion This work highlighted the need for proper treatment of the effluent analysed as both indicators (Cr(VI) levels and physical parameters) of the effluent are showing high level of pollution.

References
Ackerly, D. F., Gonzalez, C. F., Park, C. H., Balke, I. R., Keyhan, M. and Martin, A. (2004). Chromate reducing properties of soluble flavoprotiens from Pseudomonas patida and Escherichia coli. Appl. Environ. Microbiol. 70, p873-882. Arnold, E. G.; Rhodes, R. T.; Lenore, S. C. and Mary Ann, H. F. (1985): Standard Methods for the Examination of Water and Wastewater, 16th ed., Port City Press, Baltimore, p148, 158. Cotton, F. A., Wilkinson, G., Murillo, C. A., Bochmann, M. (1999) Advanced Inorganic Chemistry 6th ed. Replika Press, Canada, p756. FEEMA (1986): Standard for Effluent Discharge, Environmental Agency of Rio de Janeiro State, Rio de Janeiro, Brazil NT 202. R-10. Ibrahim, M. B. (2007a). Selected Experiments in Physical Chemistry, Publication and Documentation Division, Kano, p21. Ibrahim, M. B. (2007b). Index of Physical Parameters of Coconut (Cocos Nucifera L.) Water from some parts of Lagos State, Nigeria. Best Journal 4(1), p208-211. Iwata, I., Ishikawa, M., Ichino, R. and Okido, M. (2003). Photocatalytic reduction of Cr(VI) on TiO2 film formed by anodizing. Surface and Coatings Tech., Vol. 169-170, p703 706. Jen-Fon, J., Guang-Lien, O., Chi-Shi, C. and Shih-Ming, Y. (1993). Simultaneous Determination of Chromium(III) and Chromium(VI) with Reversed-phase ion-pair high-performance liquid chromatography. Analyst, 118, p12811284. Levitt, B. P. (1973): Findleys Practical Physical Chemistry, 9th revised ed., Longman, London, p93. Noroozifar, M. and Khorasani-Motlagh, M. (2003). Specific Extraction of Chromium as Tetrabutylammonium chromate and Spectrophotometric Determination of Diphenylcarbazide: Speciation of Chromium in Effluent Streams. Anal. Sci., 19(5), p705. Rajmond, M. (2005). Trace Level Determination of Cr(III)/Cr(VI) in Water Samples using Ion Chromatography with UV Detection. J. Liq. Chromat. & Related Tech., 28, p2849-2862. Sule, P. A. and Ingle Jr. J. D. (1996) Effluent Discharge, Anal. Chim. Acta 326, p85. Thakur, I. S., Verna, P. and Upadhyaya, K. C. (2001). Involvement of Plasmid in Degradation of Pentachlorophenol by Pseudomonas sp. From a chemostat. Biochem. Biophys. Res. Comm., 286, p109-113. Uppal, M. M. (2005). Engineering Chemistry (Chemical Technology) Revised by S. C. Bhatia, 7th ed. Khanna Publishers, Delhi, p125. Vogels Qualitative Inorganic Analysis (1996). Revised by G. Svehla, 7th ed., Pearson Education Ltd., India, p139, 237.

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