Tertiary Treatment of Sugar Mill Effluent from Indigenously Developed Cation Exchanger from Agricultural Waste Wheat Straw

Industrial pollution is a global concern due to continue economic growth, green revolution, urbanization, increasing population growth rate are creating enormous stress and threat to the limited fresh water resources.[1] The indiscriminate disposal of liquid waste, solid waste, toxic substances, garbage and other wastes by human community and industries, induce an even greater concern for water resources.[2-3] It is estimated that nearly 70% of our water sources are polluted. The expansion of industry and subsequent increase in the amount of industrial waste has led to considerable environmental problems in all industrialized countries. The indiscriminate disposal of industrial and sewage effluents on agricultural lands is becoming a major source of heavy metal contamination in irrigation soil and in ground water.[4-5] All varieties of cation and anion exchangers nowadays available are imported from other countries. Ion exchange India Limited, which is in collaboration with some other manufacturer in UK, is the major supplier of exchangers. There is hundreds of industries viz. sugar, food, beverages, textiles, dyes and chemicals etc. use these exchangers either at one or the other stage. These can be successfully employed for the removal of heavy metals and these reducing the pollution load of industrial effluents and domestic waste water. India is an agricultural country, so there is a huge quantity of agricultural waste in the form of wheat straw, rice husk; pea nut skin, bagasse, coconut fibre etc. are available. Tens of millions of tons of toxic or otherwise hazards materials enter the environment every year. They cause cancer, delayed nervous damage, mutagenic changes etc. Once the waste water containing toxic substances enter into the environment, it spreads in a very complex way and may be converted into other substances which have different effects.[6] The ion exchanger process is a strong alternative to reduce pollution load in waste water. The conversion of wheat straw into cation exchanger, developed in our laboratory constitutes an indigenous approach for making use of agricultural waste for the production of cation exchanger. Waste water from paper mill, sugar mill, distillery and metal industries has been treated by using cation exchanger from wheat straw before discharging into water bodies or on land. This treated water is used as potential fertilizer for growing various crops. It will reduce the fertilizers cost and thus benefit farmers by decreasing the cost with no adverse side effect on physical, chemical and biological

exchanger and the use of treated water for cultivation of various crops are beneficial as it constitutes a good source of nutrients and has potential to replace chemical fertilizers. Recycling and reuse of industrial waste water after treatment with cation exchanger from wheat straw in agriculture is not only helpful for conserving the water for irrigation, also the plant nutrients. So, it is essential that the implification of the use of treated industrial effluents in the crop field and their effect should be assessed before recommendation for use in irrigation. The treated effluents of various industries did not cause any adverse side effect on physico-chemical and biological properties of soil. If the treated waste water of different industries located in Yamuna Nagar and Jagadhri could successfully use for irrigation then it is possible to prevent Western Yamuna canal pollution and also to augment already scare irrigation water resources. The major limitation is that the technologies include the high cost of resins, the extent of regeneration of resins and the chemical stability of synthetic resins. An estimated cost of sulphonated wheat straw on the basis of the raw materials comes out to be low as compare to synthetic exchanger. Hence it is economically viable alternative to synthetic resins. The treated effluents had a potential to be used as a fertilizer for growing various crops in the field.

Currently India is generating about 18004 mm3 of waste water per day of which 20% is treated in various treatment plants. Sugar industries discharge a large quantity of liquid and solid waste.[7] The side products produced in sugar industries are utilized as raw material in various distilleries. Every litre of alcohol produced about 15 L of waste water named as spent washor distillery effluent are discharged into running water or on land directly. About 10 to 11 billion litre of spent wash is produced annually in India with 329 distilleries which together produced 3.2 billion litre of alcohol per annum. The liquid is dark brown in colour and has unacceptable odour. The high soluble salts contribute for its higher COD (80,000-120,000 mgl-1) and suspended solids, especially organics contributes for higher (30,000-40,000 mgl-1) making it unsuitable on land. The quality of liquid waste generated and the practices followed by the industries are governed by the Central Pollution Control Board in India. Spent wash is a potential fertilizer containing most essential plant nutrients in liquid as no other commercially available fertilizer provides such a complete source of nutrients. Sugarcane (Saccharum officinarum L.) is a globally important cash crop.[8-10] Sugar industries in India, for example, generate about 1 kL of wastewater for one ton of sugar cane months. Sugar mills consume around 2 kL of water and generate about a kL of wastewater of per ton of cane crushed. The effluent is generated from the floor washing wastewater and condensate water, sugarcane juice, syrup, and molasses contained therein.[11] The sugar mill effluent has a BOD of around 1500 mg/L, and it appears clean initially.[12] Sugar mill effluent contains considerable amount of potentially harmful substances including soluble salts and heavy metals such as Fe, Cu, Zn, Mn, Pb. The long-term use of this sugar mill effluent for irrigation must be discouraged, as this improper wastewater usage results in the contamination of soils and crops.[13] The spent wash contains plant nutrients P, K, S in higher concentration. In addition C, N, Fe, Cl and some other elements are also present and hence it can be very well utilized as a source of irrigation on agriculture after subjecting to some pre-treatment. The post anaerobically treated spent wash contains organic intermediates and inorganic salts in significant quantities which are the essential nutrients for plants.[14-15] BOD reduction in anaerobic pond from 1600 mgL-1 to 550 mgL-1 in 7 days, at a loading rate of 0.23 kgha-1day-1, this were followed by an oxidation pond, loaded at 316 kgha-1day-1, which produced an effluent with a BOD ranging from 34 mgL-1 to 180 mgL-1 for a retention time of 13 days. Activated sludge process has not been preferred for sugar mill effluent treatment because of the seasonal nature of the industry. Trickling filtration method is also used by few researchers to treat sugar mill effluent and BOD reduction was 70% to 90%.[16] Use of rotating biological contractor for treating sugar mill effluent with more than 80% COD removal. The maximum COD removal efficiently was found to be 70% with bio-gas yield of 0.65 m3kg-1 COD. Nitrogen content is the digested sludge was found to be 2.32% hence it can be used as fertilizer.[17] Carboxylated chitosan ion exchanger has been synthesized by K. L. Lu et.al, and used for adsorption of lead and copper in the aqueous solution. Cation exchangers can be produced, apart from synthetic materials, from widely different cellulose based substances like rice husk, paper, lignin, wood etc. by sulphonation.[18]

Yamunanagar city and nearby area has been selected for the present study which is comes under the most polluted cities of Haryana. Yamunanagar the district, which forms the eastern boundary with the neighboring Saharanpur district. The northern boundary is also an interstate boundary with the state of Himachal Pradesh to the north. Well known for 3250 small, medium and large scale industries. It has emerged as an important industrial destination in the state. Due to expanding industries, the city kept on extending geographically. The Yamunanagar District lies between 29 09' 50" and 29 50' North Latitude and 76 31' 15" and 77 12' 45" east longitude.

Wheat straw was washed with ethyl alcohol (CH3CH2OH) to remove any alcohol soluble gradient. Cation exchanger from agriculture waste i.e. wheat straw had been prepared by sulphonation with conc.H2SO4 and decomposition and introduction of sulphonic group had been confirmed by various analytical studies. The resin was washed with distilled water (H2O) and then dried in the open air and dried product was graded and screened with the help of mesh sieve of different porosity. The cation exchanger formed was then subjected to various studies viz. ash content, moisture content, carbon, sulphur, density and exchange capacity. The various factors affecting the exchange of S.W.S like effect of particle size, effect of flow on exchange and effect of column size on exchange had been undertaken. Cation exchanger from wheat straw had prepared in large quantity for the treatment of sugar mill effluent. Treatment of Sugarmill Effluent with Newly Formed Cation Exchanger from Wheat Straw Sugarmill effluent was collected from the Sugarmill. Various physico-chemical parameters i.e. pH, methyl orange alkalinity, acidity, free CO2, chloride content, Calcium, Magnesium, Chromium, Copper, Manganese and Zinc were determined by standard methods after dilution (1:100) at 25°C for the assessment of pollution load [APHA 2012]. Chromatographic column (65×250 mm) was packed with S.W.S.H+ (5g) and diluted spent wash (1:100) was passed through the column by controlling the flow rate (9-10 drops/min). The status of the diluted spent wash after passing through column was analyzed by following same parameter. All the chemicals used were of analytical grade. Double distilled water was used for all experimental work. All parameters were done in duplicate. Metals from Plant Samples were extracted using DTPA extraction method. The plant samples were washed with HCl before drying in oven at 65 ± 5 ºC. The various plant samples were dried and weighed. Dry samples were mechanically ground using a sand grass mortar and pestle for digestion. Cr, Cu, Fe, Mn and Zn were analyzed and using Atomic Absorption Spectrophotometer.

Physico-Chemical Studies of Sugar Mill Effluent and its Treatment with S.W.S. The colour of the effluent from sugar mill was blackish grey with unpleasant alcoholic odour of burnt sugar, rich in highly putrescible organics in contrast to clear and odourless nature of well water. The effluent of sugar mill contain considerable amount of suspended and total dissolved solids and in the present study it varied from 1467 mgL-1 to 1652 mgL-1 in case of dissolved solids and 689 mgL-1 to 786 mgL-1 in case of suspended solids in different seasons. It is an important parameter for evaluating the suitability of effluent for irrigation purposes since these solids might clog both the solid pore and components of water distribution system [246]. The pH of the effluent was acidic to neutral 6.5-7.2 whereas well water had a pH nearby area is 7.62-7.9. EC of the effluent ranges from 0.82 dSm-1 in winter to 0.98 dSm-1 in monsoon season against EC 0.27-0.32 dSm-1 for well water. The similar observations were also reported for sugar mill located in Maharashtra [247]. The high value of turbidity in effluent led to very high BOD in different season which ranged from 686-744 mgL-1. Similarly, chemical oxygen demand COD of the effluent was very high in different seasons 11520- 16520 mgL-1, whereas, it will very low 214-276 mgL-1 for well water (Table 1-2). Very high value of BOD and COD for the effluent of sugar industry was also noticed [248]. Chloride content was also high 69-89 mgL-1 as compared to well water. The cationic concentration of Ca2+, Mg2+ was relatively high in the effluent than well water. The cation was higher in summer followed by winter and monsoon season. The similar observation was also reported [249-250]. After tertiary treatment with indigenously prepared cation exchanger S.W.S. the pollution load was reduced. Alkalinity reduced up to 56.6%,

in the sample were reduced to such an extent that it can be successfully used after dilution for irrigation purposes or may be drained into water bodies without causing any harmful effects on soil or in water showing in (Table 3). Analysis of Heavy Metals in the Plants Grown in the Pilot Plot SWS Treated industrial effluent was being used for irrigation of various plants because these effluents contain some nutrients that enhance the growth of crop but these effluents also have some toxic materials. Irrigation of treated sugar mill effluent with S.W.S. after varying dilution had shown very encouraging results on the growth of marigold plants. Concentration of metal in parts of plants ranged from Fe from 26.234 - 38.410 mgkg-1, Mn 7.342-9.646 mgkg-1, Cu: 0.712–1.289 mgkg-1, Cr: 0.138 – 0.245 mgkg-1, Zn 3.434-5.628 mgkg-1 dry basis while in ground water treated soils it ranged from 2.475-5.789 mgkg-1, 1.867-6.384 mgkg-1, 0.7576-1.9870 mgkg-1, 0.0624-0.1864 mgkg-1, 0.5642-1.2960 mgkg-1 and 1.48-3.78 mgkg-1 dry basis. These data denotes that the concentration of all these heavy metals in the plants parts were within the permissible limit similar results were also reported by other workers.[19]

1. Singh A. P. and Ghosh S.K. (1999). Assessment of water quality index for Yamuna, Pollution Research, 18(4), pp. 435-439. 2. Singer S. F. (1970). Global effect of environmental pollution, New York USA, Springer Verlag,. 3. Gangal R. K. and Zutshi K. (1990). Ground water pollution and the effects of rain khetri copper complex, Indian J. of Envir. Health, 32 (40) pp. 339-344. 4. Williams D. E., Vlamis J., Pukite A. H. and Corey J. E. (1980). Trace elements accumulation movement and distribution in soil pacific from massive appreciation of sewage sludge, Soil Science, 12(9), pp. 119-132. 5. Khurana M. P. S., Singh M. and Nayyer V. K. (2004). Assessment of heavy metal contamination in soils and plants irrigated with sewage effluents containing industrial effluents in district Amritsar Punjab, Indian J. Environ. Ecoplant, 8, pp. 167-172. 6. Hussain M. A., Furumai H. and Nakajima F. (2009). Water Science and Technology, 59(2), pp. 303-310. 7. Patil G. D. and Shinde B.N. (1994). Use of sugar industry water in agricultural proc. 7th Joint conv., Sugar technol. assoc. Pune India. 8. Pathak H., Joshi H. C., Chaudhary A., Chaudhary R., Kalra N. and Dwivedi M. K.

9. Joshi H. C., Pathak H., Chaudhary A. and Kalra N. (1996). Distillery effluent as a source of plant nutrients, prospects and problems, Fertilizer News, 41, pp. 41-47. 10. Goyal S.C. and Kapoor K. K. (1995). Effect of distillery waste water application on soil microbiological properties and plant growth, copy right by MKK publication. 11. Hampannavar U. S. and Shivayogimath C. B. (2010). Anaerobic treatment of sugar industry waste water by upflow anaerobic sludge blanket reactor at ambient temperature, International Journal of Environmental Sciences, 1, pp. 631-639. 12. Pande Y. N. (2005). Impact of distillery and sugar mill effluents on hydrobiology of the Paravathi lake. Ecology, Environment and Conservation Paper, 1, pp. 39-42. 13. Fakayode P. K. (2005). Aleteration in physic-chemical characteristics of soil irrigated with sugarmill effluent, Journal of Environmental Biology, 12, pp. 103-109. 14. Tapar N., Shastri S. and Kaul S. N. (2006). Bioresources recovery through waste water management in sugarcane molasses based distillery–A case study. ICSWER proceedings, pp. 91-96. 15. Pushpawali R., Kotteswaran P., Krishanamurhy M. and Parmeswran P. (1995). Impact of application of treated distillery effluent on soil yield and quality of sugarcane, 2nd International conference on contamination in soil in Australia-Pacific region, pp. 47-48. 16. Bhaskaran T. R. and Chakrabarty K.N. (1966). Pilot plant for treatment of sugar cane waste, J. Wat. Poll. Cont. Fed. 38, pp. 1160. 17. Huang J. C. (1983). Growth and activities of fixed films in treating sugar wastes, Proceedings of 38th industrial wastes conference, Purdue University, Indian, 817. 18. Lu K. L., Du Y. L. and Wang C. M. (2009). Synthesis of carboxylated chitosan and its adsorption properties for cadmium(II), lead(II) and copper(II) from aqueous solution, Water Science and Technology, 60(2) pp. 467-474.

Department of Chemistry, OPJS University, Rajgarh Churu Rajasthan, 331303, India