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International Journal of Agriculture, Environment & Biotechnology

Citation: IJAEB: 6(3): 355-361 September 2013


DOI Number 10.5958/j.2230-732X.6.3.003 2013 New Delhi Publishers. All rights reserved

Environment

Heavy Metals Concentration at Different Tannery Wastewater Canal of Chittagong City in Bangladesh
S. Islam, F. Islam*1, M.A. Bakar, S. Das and H.R. Bhuiyan
Bangladesh Council of Scientific and Industrial Research (BCSIR) Laboratories, Chittagong, Bangladesh

*Email: faridacct@yahoo.com Paper No. 123


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Received: April 17, 2013 Accepted: July 12, 2013

Published: September 01 , 2013

Abstract Industrialization and urbanization grow up the development of any country. Chittagong, the second largest city of Bangladesh, is suffering a great deal for water pollution problem. Various types of compound contaminated with heavy metals or heavy metals compound are conventionally used in different industry. Wastage from the industries is finally discharged into different surface water body without treatment creating pollution. Our investigation was carried out to evaluate the status of heavy metal in the different canal of Chittagong City. Concentration of Cu, Mn, Zn, Pb, Ni, Co, Ag Fe, Cd, Al and Ag were determined by Atomic Absorption Spectrophotometer (AAS). In all canals Pb contents were higher than the standard limit of Environment Conservation Rules 1997. Pb concentration of Hamzerbagh canal was the highest (8.03 mg/ml) of all and second highest was Mirzapol canal i.e. 7.777 mg/l. Cr content that found to very much higher in the two canals near from Kulgoan (Tannery Bottal) area were 23.73 mg/ L and 10.45 mg/L. Fe concentration of sample, collected from Muradpur canal, Hamzerbag canal and Mirzarpol canal found higher than the standard limit were 7.95, 4.94 and 4.41 respectively. High concentration of Pb, Cr and Fe were found also higher than the standard limit indicating imperiled state of canal water of Chittagong City.

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Highlights The samples were collected from nine tannery canals


Twelve heavy metals were determined from tannery wastewater Chromium, Lead and Iron was the highest concentration than other heavy metals

Keywords: Wastes, heavy metals,waste water and Atomic Absorption Spectrophotometer (AAS).

Introduction The water is another name of life. It is one of the most important natural resources. This natural resource is being contaminated every day by various anthropogenic activities such as rapid growth of populations, urbanization and industrialization that ultimately make the environment polluted. Recently, sewage waters have been used for

irrigation purposes (Vasseur et al., 2000). There are greater concerns about heavy metal contamination (Gardiner et al., 1995; Logan and Chaney, 1983) in the receiving water system and land. The occurrence of toxic heavy metals in the soil is an anthropogenic origin. Heavy metals from the point of origin and other sources can be transported to distant environments (Andersen et al., 1998). High levels

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of heavy metals can damage soil fertility and may affect productivity (Chang et al., 1992; Hooda and Alloway, 1994). Heavy metals in the environment may also change plant diversity and affect aquatic life. Chittagong city is positioned on bank of the river of Karnaphully and the city is surrounded by rich natural resources like green hilly territory and the Bay of the Bengal on the west. Chittagong is heart of all commercial and business activities in Bangladesh as prime seaport situated here. After independence Chittagong city has developed up here many large, medium and small-scale industries. Industrial effluents in the costal water of Chittagong region are very high as most of the industry lacking waste water treatment plant. As a result, all of the waste of Chittagong City Corporation directly or indirectly discharged into different canals and finally finds its way into the river Karnaphully through these canals, thus polluting only surface water resource, is a great concern. Water channels are used for dumping wastes that ultimately end up in the Bay of Bengal. Every sector like industry, agriculture, mining, energy, transportation, construction and consumers generate wastes. Industrial wastes are usually generated from different industrial processes. The tannery effluents are ranked as the highest pollutants (Shen, 1999). In developing countries, many industrial units are operating in a small and medium scale. These industrial units can generate a considerable pollution load by discharging untreated effluents directly into the environment due to the poor enforcement of law. According to a recent estimate, about 60,000 tons of raw hides and skins are processed in these tanneries every year, which release nearly 95,000 L of untreated effluents into the open environment daily, resulting into a dead river, named Buriganga (Rusal et al., 2006). Tanneries are one of the most prominent sources of chromium pollution to the aquatic environment. If not adequately treated, wastewater from tanneries contaminates surface water and sediments to an unacceptable level, as shown by numerous studies from Poland (Wardas et al., 1996 and Molik et al., 2004), Ireland (Walsh and Ohalloran, 1996), India (Khwaja et al., 2001) and many other countries. The tanning process is carried out with the use of chromium tanning agents, principally basic chromium sulphates. As a result of proteolysis and condensation processes in water solution, these salts form a mixture of hydroxo- and aquacomplexes. The presence of sulphate radicals, showing also complexing properties, increases the stability of collagen and tannin fixations. The reaction
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of cationic complexes of chromium (III) with ionized carboxyl groups (COO-) of asparganine and glutamine acid radicals is central for the tanning process. These reactions lead to the crosslinking (coordination bonds) of collagen fibres, giving the leather its durable finish and stability (Lasek, 1978; Michalec, 1996). Chromium from tanneries is thus discharged principally as Cr (III) bound to organic and inorganic ligands (Logan and Chaney, 1983). At neutral or slightly basic pH, chromium is relatively immobile in tannery sludge (Chuan and Liu, 1996).The characteristics of tannery wastewater vary widely depending on the nature of the adoptedtanning process, the amount of water used, the process of hide preservation, the hide processing capacity, and the in-plant measures followed to reduce pollution. Treatment of this wastewater by conventional biological methods is often inadequate to remove pollutants completely, especially ammonia and tannins, the latter being characterized by low biodegradability, which is common in poly-phenolic compounds. Meanwhile, the biological treatment of wastewaters containing resistant and toxic compounds requires a long duration of time (Szpyrkowicz et al., 2005). Tanneries discharge pre-treated or raw wastewater into the local sewers or directly into streams. Chromium compounds introduced into the river are temporarily accumulated in bottom sediments. It appears that even nominally dissolved Cr (III) is largely associated with the colloidal phase (Dominik et al., 2003; Bobrowski et al., 2004) forming polynuclear hydroxide complexes which acquire a higher molecular weight during transport (Pereira et al., 2005) and can be incorporated into sediments due to colloid aggregation followed by sedimentation. The affinity of Cr (III ) for the particulate phase obviously decreases its bioavailability to phytoplankton, but its high concentrations in sediments might have detrimental effects for benthic organisms and ultimately for the higher level of aquatic food chain. In the case of the tannery wastewaters having a good conductivity and a high concentration of chloride ions, electrochemical methods have been reported to be effective as a final polishing step because organic pollutants, ammonium, and sulfide ions are oxidized by a direct anodic process and indirect electrolysis via the electro-generation of active chlorine. The effectiveness of the electrochemical oxidation strongly depends on the experimental conditions and, above all, on the nature of the electrode materials. Up to now, several anodes, such as Ti-Pt, Ti-Ir, Ti-Pt-Ir, Ti-Ta, and Ti alloys, as well as graphite electrodes, have been tested for the electrochemical oxidation of tannery wastewater (Panizza and Cerisola, 2004). Furthermore, the electro-coagulation technique was
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Heavy Metals Concentration at Different Tannery Wastewater Canal of Chittagong City in Bangladesh

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observed to be more effective for the removal of chemical COD than the conventional coagulation and sedimentation process. Soluble metal electrodes like Al and Fe were found to be very effective compared to insoluble electrodes. Al and Fe ions support to coagulation of colloidal particles (Murugananthan et al., 2004). It has been reported that the EF oxidation process (pH 3-4) is able to reduce total organic carbon content by mineralization of organic compounds (Schrank et al., 2004; Schrank et al., 2005). However, the process requires acid consumption to decrease pH and might make the system invulnerable to corrosion. For these reasons, if the intended removal rate is sufficient, it seems that it would be more convenient to perform the process at the pH of raw wastewater near neutral pH level. In this case research, the pH of wastewater taken from an outlet of an equalization basin in a common treatment plant of the Organized Tannery Industrial Region located in the Tuzla District in Istanbul was 7.4. There are considerable dissimilarities in the concentration range of pollutants in tannery wastewaters given by different authors (Ates et al., 1997; Balasubramian et al., 1999; Dhungana et al., 2009; Krishanamoorthi et al., 2009; Nourisepehr et al., 2005), but all of the authors observed that the tannery industry causes horrendous environmental pollution and high environmental impact of tannery effluents makes its treatment an essential fact, mainly due to its volume, nature and concentration of pollutants such as tanning agents (chromium and tannin), color, organic matter and others (Mohanta et al., 2010). Excessive release of heavy metals into the environment due to industrialization and urbanization has posed a great problem worldwide. Unlike organic pollutants, the majority of which are susceptible to biological degradation, heavy metal ions do not degrade into harmless end products (Gupta et al., 2001). The presence of heavy metal ions is a major concern due to their toxicity to many life forms. Heavy metal contamination exists in aqueous wastes of many industries, such as metal plating, mining operations, tanneries, chloralkali, radiator manufacturing, smelting, alloy industries and storage batteries industries, etc. (Kadirvelu et al., 2001). Chromium in trace concentration is an essential element in the diet, because it regulates the glucose metabolism in the human body. Excess amounts of chromium uptake are very dangerous due to its carcinogenic effect. Chromium in soils affects plant growth (Shanker et al., 2003), it is non-

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essential for microorganisms and other life forms and when in excess amounts it exerts toxic effect on them after cellular uptake. Cr (VI) is more toxic than Cr (III). Leather and chromium plating industries are the major causes for environmental influx of chromium (Baker et al., 1994; Safe et al., 1997). The movement of chromium and its bioavailability poses a potential threat to the environment. In recent years, cyanobacteria were used as bioadsorbent for the removal of certain heavy metals from heavy metal polluted water (Jones et al., 1986). However, most of the conventional methods generate secondary effluent impacts on the recipient environment; mainly microbial bioadsorbent methods are economically not feasible. In this context, the phytoremediation technology is an emerging technology, which is considered for the removal of chromium in contaminated systems because of its cost effectiveness, aesthetic advantages and long-term applicability. The aim of the present research work was to test the applicability of plant material for the removal of Cr (VI) in the industrial wastewater. As a result, a number of research work carried out around the world regarding the treatment of tannery effluents using different technology. Several studies have been carried out for the treatment of industrial effluents through coagulation and flocculation process (Stephenson and Duff, 1996).Treatment processes for heavy metal removal from wastewater include precipitation, membrane filtration, ion exchange, adsorption, and co-precipitation/ adsorption. Studies on the treatment of effluent bearing heavy metal have revealed adsorption to be a highly effective technique for the removal of heavy metal from waste stream and activated carbon has been widely used as an adsorbent (Chand et al., 1994).There is an increasing society concern with regard to the importance of the preservation of our environment and the corresponding legislation which regulates effluents discharges. So, any contaminating substance which, though having been processed is not of free disposition represents a mortgage for the industry. So, the treatment of tannery effluents is a matter of great concern in the country having leather tanning industry. But in Bangladesh, most of the work regarding tannery effluents is related to their characterization and impact assessment [Das et al., 2006; Mohanta et al., 2010). Hence, proper treatment of tannery wastewater is essential before releasing into the recipient environment. Our objective of this research is to find out the pollution level of different canal (Locally called Khal) of Chittagong City by tannery Industry.

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Materials and Methods For the determination of heavy metals, the samples of water were collected from nine sites of tannery industry area of Chittagong city of Bangladesh and marked as 01-09. The water samples were collected in plastic bottles and acidified immediately with 2 mL of HNO3 per litre of water and preserved in refrigerator at 4C for laboratory analysis. 100 ml of each sample was taken to 250 ml beaker and added 5 ml of concentrated nitric acid .Then evaporated the sample to near dryness on a hot plate. Then cooled the sample and added another 5 ml concentrated nitric acid. Samples were returned to hot plate and continued heating, adding additional acid as necessary until digestion was completed. This digestion decomposed organics. Then washed down the beaker walls with deionised water and filtered the sample into a 100 ml volumetric flask to remove silicate and other insoluble materials. Then each sample was made up to the mark with deionised water. These solutions were used for the determination of Cu, Mn, Zn, Pb, Ni, Cr, Fe, Co, Cd, Al, Ag and As. The standard solution of the elements Cu, Mn, Zn, Pb, Ni, Cr, Fe, Co, Cd, Al, Ag and As were prepared by pouring the required amount of the solution from the stock solution, manufactured by Fisher Scientific Company, USA. Every metal standard solution was prepared for calibration the instrument for each element being determined on the same day as the analyses were performed due to possible deterioration of standard with time. Working standards were commonly prepared from stock solution at 1000 mg/L level

using micropipettes. These solutions were prepared from their pure metal turnings and pure compound using nitric acid. Working standard and blanks were acidified to the same extent as samples. The atomic absorption instrument was set up and flame condition and absorbance were optimized for the analyte. Then blank, standards and samples were aspirated into the flame of AAS (Model- iCE 3000, Thermo Scientific). Only arsenic was estimated by hydride vapour generation technique. The analytical procedures were also calibrated against the above standard reference materials. The average recovery ranged between 94 to 107%. Results and Discussion Chromium is the most important metal in tannery waste. The highest concentration of chromium was found in the waste water of Baluchora canal is 23.73 mg/l and second lowest concentration was found in Baluchora west canal is 10.44 mg/l as shown in Table 1. The range of chromium is 0.01(Baluchora canal) to 23.73 mg/l (Baluchora east canal). The permissible limit of west water of tannery is 2 mg/l (The Environment Conservation Rules, 1997). But all the canals except Baluchora canal and Baluchora west canal chromium concentration were lower than permissible limit. The second dominant element was Pb. The highest concentration of lead was found in Hamgerbag canal (8.03 mg/l) and second highest concentration was 7.78 mg/l (Mirzapol canal). The range of the Pb concentration was 0.64 (Baluchora canal) to 8.03 mg/l. Fe is the abundant in all areas but in tannery it is not true. The range of Fe was

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Table 1: Heavy metals concentration at different tannery canal in Chittagong city of Bangladesh Sl. No. Sample ID Baluchora Parameter canal 01 (mg/L) 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. Cu Mn Zn Pb Ni Cr Fe Co Cd Al Ag As 0.079 0.062 0.698 0.643 0.004 23.73 1.827 0.01 0.011 0.135 0.038 0.028 Baluchora west canal 02 (mg/L) 0.196 0.101 0.197 0.841 0.013 10.446 1.632 0.035 0.013 0.025 0.012 0.026 Baluchora east canal 03 (mg/L) 0.049 0.54 0.064 0.94 0.014 0.01 1.938 0.013 0.006 0.013 0.008 0.01 Majargate canal 04 (mg/L) 0.176 0.052 0.322 1.136 0.021 0.205 1.27 0.011 0.013 0.03 0.073 0.022 Majargate west canal 05 (mg/L) 0.088 0.082 0.099 2.529 0.015 0.096 1.226 0.022 0.014 0.051 0.007 0.021 Majargate east canal 06 (mg/L) 0.078 0.053 0.142 3.822 0.017 0.063 0.848 0.01 0.133 0.016 0.009 0.015 Muradpur Canal 07 (mg/L) 0.072 0.378 0.171 6.433 0.007 0.02 7.95 0.016 0.009 0.905 0.011 0.01 Hamzerbag Mirzapol Canal 08 Canal 09) (mg/L) (mg/L) 0.024 0.378 0.352 8.028 0.022 0.216 4.942 0.014 0.008 0.102 0.01 0.022 0.078 0.278 0.153 7.777 0.009 0.022 4.411 0.004 0.012 0.981 0.01 0.021

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7.95 to 0.85 mg/l. The highest concentration of Fe was found in Muradpur canal (7.95 mg/l) and lowest concentration was found in Majargate (0.85 mg/l). The highest concentration of Al, Zn, Mn were more or less similar as 0.98 (Mirzapol canal), 0.70 (Baluchora canal), 0.54 (Baluchora east canal) mg/l respectively. The range of Cu was 0.2 to 0.18 mg/l. But highest concentration of Cu was found in Baluchora west canal (0.2 mg/l) and lowest concentration was found in Hamzerbag canal (0.02 mg/l). The highest concentration of Cd was found in majargate east canal (0.13 mg/l) and range from 0.13 mg/ l to 0.008 mg/l (Hamgerbag canal). The range of silver in tannery waste water was 0.07 to 0.007 mg/l. The lowest value (0.007 mg/l) was ten times lower that of higher value of silver (0.07 mg/l). The highest concentration of Co was found in Baluchora west canal (0.035 mg/l) and lowest in Mirzapol canal (0.004 mg/l). The Ni is a micronutrient for plant and animal but its concentration in waste tannery water harmful for organism. In our examined tannery waste water Ni concentration varies from 0.02 mg/l to 0.004 mg/l. The least concentration among the heavy metal was As. The range of As from 0.03 to 0.01 mg/l. In descending order of the above heavy metal was Cr>Pb>Fe> Al>Zn>Mn>Cu>Cd>Ag>Co>As>Ni. Conclusion Having a large number of heavy and small industries at Chittagong city in Bangladesh. It is in an advantageous position for getting a start in developing countries. The tannery sector is economically important and that is contribution to the GDP in a poor country like Bangladesh is not negligible. Mismanagement, inferior technologies, lack of facilities for treating industrial wastes, wrong approach towards industrialization aggravating environmental problems in the country day by day. The public demand for color-free waste discharge in receiving waters has made decolorization of a variety of industrial wastes a top priority. Unfortunately, with the complicated color-causing compounds, the decolorization of the effluent is a difficult and challenging task. From the present investigation it was revealed that chromium contains the highest amount i.e. 23.73 and 10.446 mg/l of two canals such as (Baluchora canal and Baluchora west canal) and as well as lead is the second highest amount i.e. 8.028 and 7.777 mg/l of others two canal (Hamzerbag Canal and Mirzapol Canal) in the tannery industries of Chittagong city in Bangladesh.

The main human activities that increase chromium (VI) concentrations are chemical, leather and textile manufacturing, electro painting and other chromium (VI) applications in the industry. These applications will mainly increase concentrations of chromium in water. Most of the chromium in air will eventually settle and end up in waters or soils. Chromium (III) is an essential element for organisms that can disrupt the sugar metabolism and cause heart conditions, when the daily dose is too low. Chromium (VI) is mainly toxic to organisms. It can alter genetic materials and cause cancer. Other health problems that are caused by chromium (VI) are: Skin rashes, Upset stomachs and ulcers, Respiratory problems, weakened immune systems, Kidney and liver damage, Alteration of genetic material, Lung cancer and Death. On the other hand, Lead can cause several unwanted effects, such as: Disruption of the biosynthesis of haemoglobin and anaemia, A rise in blood pressure, Kidney damage, Miscarriages and subtle abortions, Disruption of nervous systems, Brain damage, Declined fertility of men through sperm damage, Diminished learning abilities of children, Behavioural disruptions of children, such as aggression, impulsive behavior and hyperactivity. Bangladesh is a developing country. The main role plays to develop the industrial sector as like as tannery industries. But, there are no strong rules to protect the environment. The value of heavy metals exceeds the ECR-1997. It is the great harmful for our environment and healthy life because the wastewater goes to the river through canal and next to the Bay of Bengal. We can collect the various types of fishes from the river and Ocean. By the life cycle, we consume it and next it gives the wide range of diseases. So, it is the great concern for us and the government cans proper action to protect the environment and living beings as soon as possible. Acknowledgment The research was supported by Bangladesh Council of Scientific and Industrial Research (BCSIR) References
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