CHAPTER 1 INTRODUCTION Water is elixir of life and one of the most integral components of the environment.

. It is an essential resource for sustaining human, animal and vegetative life. A living cell is mostly water. When earth is viewed from other planet it appears blue which add to its beauty. This bluish beauty is provided by the water present on earth surface which covers nearly two thirds of the earths surface. This water body consist s of both fresh as well as marine water. Fresh water constitutes only 0.5% of the total water on the earth surface. The rest is either in the form of seawater or locked up in icecaps or the soil. Forms of water Water appears in three forms on earth surface i.e. solid, liquid and gas. These three forms keep changing among themselves moving from one form to other and continuously moving around earth surface but still its total quantity on earth surface remains the same. Water is usually encountered in the liquid state, which is its natural state at temperatures between 0 C to 100 C. Seas and oceans account for 97% of all water on Earth but the water present is unfit to drink. Water is also found in the form hot springs examples are (Garampani in Assam and Badrinath in Uttaranchal). Fresh' or drinking water is found as groundwater in underground aquifers, and on the surface in ponds, lakes, and rivers but the quantity is very less. About 2% of the available drinking water is frozen leaving only 1% for drinking purposes. Water stress Recent scenario of world regarding availability of water is that, the consumption of water has doubled every 20 years - more than twice the rate of increase in population. A large amount of water is wasted in agriculture, industry, and urban areas. . A recent estimate gave the total British water extraction as 201 m3 per year or nearly 4 times the domestic consumption and gave a corresponding figure of 712 m3/year for Germany, and 1688 m3/year for the USA. Not only that due to the increase in population there has been a rise in the demand for food, space for housing, consumer products, etc., which has in turn resulted in increased industrialization, urbanization, and demands in agriculture thereby leading to both river and groundwater contamination. There are more than one billion people particularly in North Africa and Western and South Asia, who lack access to a steady supply of clean water.

Access to water and sanitation, so crucial to human well-being and development, has now become a priority for the international community because of which as an immediate action the United Nations has designated 2003 as the International Year of Freshwater. Status of water in India The thirst of water for Indias rapid development is growing day by day. In spite of adequate average rainfall in India, there is large area under the less water conditions/drought prone. There are lots of places, where the quality of groundwater is not good. Another issue lies in interstate distribution of rivers. Water supply of the 90% of Indias territory is served by inter-state rivers. It has created growing number of conflicts across the states and to the whole country on water sharing issues. Indias population is expected to increase from 1.13 Billion in 2005 to 1.66 Billion by 2050. Out of that the urban population is expected to grow from 29.2% of the total population in 2007 to 55.2% by 2050. First and foremost result of the increasing population is the growing demand for more food-grains and allied agricultural produce. It results in expanding area of land under the crops especially high yielding crop varieties. It is estimated that the production of waterintensive crops is expected to grow by 80% between 2000 and 2050. For example Rice, wheat and sugarcane together constitute about 90% of Indias crop production and are the most waterconsuming crops. In addition, states with the highest production of rice and/or wheat are expected to face groundwater depletion of up to 75% by 2050.Industrial water consumption is expected to shoot up its growth between 2000 and 2050. Growth mainly in heavy industries, such as coastal power plants and municipalities has created extreme water scarcity in places like Chennai. Water stress in Varanasi Along with ever-increasing pollution, water shortages are getting noticeably worse. Some sections of the river are already completely dry. Around Varanasi the river once had an average depth of 60 metres (200 ft), but in some places it is now only 10 metres (33 ft). Varanasi, a city of one million people that many pilgrims visit to take a "holy dip" in the Ganges, releases around 200 million litres of untreated human sewage into the river each day, leading to large concentrations of faecal coliform bacteria. Upstream of Varanasi's ghats the river water already contains 120 times as much, 60,000 faecal coliform bacteria per 100 ml.

After the cremation of the deceased at Varanasi's ghats the bones and ashes are thrown into the Ganges. However, in the past thousands of uncremated bodies were thrown into the Ganges during cholera epidemics, spreading the disease. Even today, holy men, pregnant women, people with leprosy/chicken pox, people who had been bitten by snakes, people who had committed suicide, the poor, and children under 5 are not cremated at the ghats but are floated free to decompose in the waters. In addition, those who can not afford the large amount of wood needed to incinerate the entire body, leave behind a lot of half burned body parts. At Varanasi, Ganga recieve32 streams of raw sewage from the city, the concentration of faecal coliforms in the river's waters rises from 60,000 to 1.5 million with observed peak values of 100 million per 100 ml Drinking and bathing in its waters therefore carries a high risk of infection Recycling and reuse This rate of water scarcity can be only reduced by the reduction on the use of fresh water and recycling or treating waste water which is generated in huge amount in the form of domestic waste or industrial wastes etc. Besides being source of irrigation water, these waste waters contain appreciable amounts of plant nutrients. In India, total waste water generated per annum from 200 cities is about 2600 Mm3 (Kaul et al., 1989) and also the use of sewage effluents for irrigating agricultural lands is on the rise especially in the peri-urban area. These waste waters carry appreciable amounts of trace toxic metals and concentrations of trace metals in sewage effluents vary from city to city. This reuse of waste water can provide us with benefits like:

It reduces water wastage by cutting down the amount of freshwater usage in half It can help plant growth in the areas where water deficiency is a common trend Bacteria break down the nutrients in it making it easy for the soil to access thus

improving soil fertility

It can reduce our dependency on groundwater reserves, which is diminishing

everyday

It reduces our energy and effort put in the utilisation of chemical resources for

cultivation and saves money on water bills, well to some extent.

It increases our awareness regarding the proper usage of water

Importance of wastewater contaminants

Contaminants Suspended Solids

Biodegradable Organics

Pathogens Nutrients Refractory Organics Heavy metals Dissolved inorganic solids

Source Environmental significance Domestic use, Industrial effluent, Causes sludge deposits and erosion by infiltration/inflow anaerobic condition in aquatic environment. Domestic wastes and industrial Causes biological degradation, waste which may use up oxygen in receiving water and result in undesirable conditions Domestic waste Transmit communicable diseases Domestic and Industrial waste May cause eutrophication Industrial waste May cause taste and odor problems, may be toxic or carcinogenic. Industrial waste, mining etc. Are toxic, may interfere with effluent reuse Increased above level in water May interfere with effluent reuse supply by domestic and / or industrial use.

Wastewater generation and its treatment in India The major source of organic pollution in fresh water bodies is sewage. In India, all the cities and towns did not have sewage treatment facilities. Untreated or improperly treated human wastes are directly dumped into aquatic resources form where the downstream citys water requirements are drawn, constitute a big public health hazard in terms of their potential for spreading water borne diseases. The total wastewater generated by the 299 class I cities is 16,662 Mld approximately 81% of the water supplied. The state of Maharashtra alone contributes about 23%, while Ganga river basin contributes about 31% of the waste generated. Only 74% of the total wastewater generated is collected. Out of 299 class I cities 160 cities have sewerage coverage for more than 75% of the population and 92 cities have between 50 and 75% of population coverage. On the whole 70% of the population of class I cities are provided with sewerage facility. The type of sewerage system is either open or closed or piped. As per the latest estimate out of 22,900 Mld of wastewater generated, only about 5900 Mld (26%) is treated before letting out, the rest i.e., 17000 Mld is disposed of untreated. Twentyseven cities have only primary treatment facilities and forty-nine have primary and secondary treatment facilities. The level of treatment available in cities with existing treatment plant varies from 2.5% to 89% of the sewage generated.

Wastewater reatment technologies The various treatment technologies adopted in India are UASB (Up Flow anaerobic sludge blanket), ASP (Activated sludge process), RBRC (Rotating Biological Rope Contractor), OP (Oxidation pond), TF (Trickling Filter) and AL (Aerated lagoon). In Varanasi ASP is adopted in all three plants. The various processes involved in these technologies are as follows:1. Primary treatment: The purpose of primary treatment is to remove solid

material from the incoming waste water. Large debris may be removed by screens or may be reduced in size by grinding devices. Inorganic solids are removed in grid channels and much of the organic suspended solids are removed by sedimentation. A typical primary system should remove approximately one half of the suspended solids from the incoming waste water. Operations common to primary treatments are: Screening, Grit removal, Grinding, Skimming, Sedimentation, Septic tank, Imhoff tanks, Flocculation etc 2. Secondary treatment: Secondary treatment involves further treatment of the

effluents coming from the primary sedimentation tank. This is generally accomplished through biological decomposition of organic matter which is carried out either under aerobic or anaerobic conditions. Secondary treatment usually consists of biological conversion of dissolved and colloidal organic into biomass that can subsequently be removed by sedimentation. Operations employed in secondary treatments are: Trickling filters, Activated sludge process, Aerated lagoons and Oxidation ponds. 3. Tertiary treatment: Most often involves further removal of suspended solids and

or the removal of the nutrients. Tertiary treatment is the additional processing of secondary treatment effluents undertaken to further improve their quality. Tertiary treatments refer to methods and processes that remove contaminants from wastewater that are usually taken out by present conventional techniques. Tertiary treatments may be used to further remove almost any undesirable constituents of wastes, suspended solids, BOD, nitrogen and phosphorous.

Operations involved in tertiary treatments are: Oxidation, Adsorption, Ion exchange, Microporus membranes, Reverse osmosis, Chlorination etc. Treatment of wastewater at Varanasi About 80 to 85 per cent of the total pollution of the river at Varanasi is due to disposal of sewage into the river. In the last decade microbial pollution has increased by about 1.5 million during 1991-2001 i.e. from 929,270 to 1,100,748 million. In Varanasi, the coliform bacterial count in the water of Ganges is at least 3,000 times higher than the safe standard set, as has been set by the World Health Organization. Varanasi alone generates 300 MLD of sewage of which only 98 MLD is treated and rest 202 MLD is disposed of untreated. It has up to secondary treatment facilities. Three treatment plants are present in Varanasi. These are BHAGWANPUR sewage treatment plant having a capacity of 10 MLD, DLW sewage treatment plant having a capacity of 8 MLD and DINAPUR sewage treatment plant having a capacity of 80 MLD. In Varanasi there are three treatment plants which undergo a maximum of secondary treatment of waste water. These are based on activated sludge process for treatment of waste water. These are: 1. Bhagwanpur sewage treatment plant treating sewage of 12 MLD per day. 2. Dinapur sewage treatment plant treating sewage of 100 MLD per day. 3. DLW sewage treatment plant treating sewage of 10 MLD per day. The treated water of these sewage plants are either used in irrigation or is discharged directly to Ganga River. The treated waste water of Bhagwanpur sewage treatment plant is used in irrigation purpose as well as surplus water is discharged directly to river Ganga. Varanasi city has the distinction of being the oldest living city of the world. Here the community of human habitation and evolution of culture have been uninterrupted over since the recorded history is available even though the cultural, educational and religious heritage is preserved. Rapid urbanization and industrialization has imposed a serious threat of water pollution in the city. The wastewater of Varanasi contain not only domestic waste rather is also contain discharges from various industries which includes not only organic chemicals but also many harmful and toxic chemicals as well as heavy metals. The treatment plants present in the city are

based on Activated Sludge Process technology which does not meet the criteria of water quality parameters for reuse and safe disposal to the environment (Pierre Cote et al., 1997; Yuansong Wei et al., 2003). Varanasi is suffering from severe water pollution problem. However, no systematic study on the improvement of processing of sewage treatment plant and its eco friendly behavior has been conducted in the city of Varanasi at Bhagwanpur sewage treatment plant. Henceforth, present study aimed to make detailed investigation on the topic, Merits and Demerits of Wastewater Treatment Technologies at Varanasi. Aforesaid aim shall be achieved with the following objectives: 1.) To make general survey Bhagwanpur sewage treatment plant 2.) To study the processing of Wastewater Treatment Plant 3.) To monitor the Physico-Chemical parameters of treated and untreated waste water 4.) To make statistical analysis of observed data to check their significance 5.) To make a suitable recommendations to improve methodologies of the Waste Water Treatment Technologies

CHAPTER 2 REVIEW OF LITERATURE The fresh water that is available for use is 1% or 0.007% of the total water on earth, which is really very little. The search for clean, fresh, and potable water has always been one of mankinds priorities. Due to certain activities of man a large portion of this water is changed into wastewater. Water when changed in its various characteristics gets converted into wastewater. This wastewater is actually consists of 99% of water and rest 1% is such impurities which make the water unsuitable for useful purposes. These impurities if removed in a proper way with proper technologies this water can be used for various useful purposes. When people started releasing the harmful effects of these impurities to humans and other organisms specially aquatic ones then a major concern was given to study of the characteristics which changes water into wastewater ; ways which can be employed in its treatment and the technologies involved in treatment of this wastewater. The works which were undertaken which imparts us with knowledge regarding all the aspects of wastewater and its method for treatment are briefly reviewed. Wastewater: Nemerrow (1978) reported the nature of pollutants converting water into wastewater as well the origins of these pollutants. Fakayode (2005) reported how freshwater is affected by unsafe disposal of waste water into the ambient environment. Kupchella., et.al( 1989) reported ways by which suspended solids affect aquatic lives. De Zuane (1997) reported about the idea of various chemicals which acting as pollutants affecting the quality of drinking water. Jaworski et al.(1992) reported how eutrification of downstream water occurs by the runoff from animal farms containing huge amount of nutrients. There was a further report by Schofield et al., ( 1990) giving how significant increase in ammonia content and biochemical oxygen demand occurs after rain in watershed having seven dairy operations. Hunt et al.(1995) reported how the level of nitrate and phosphate increased in water with high level of animal waste. Sangodoyin,(1995) reported Estuaries and inland water bodies, which are the major sources of drinking water in Nigeria, are often

contaminated by the activities of the adjoining populations and industrial establishments. Sangodoyin (1991) reported how these effluents from industries alter the physical, chemical and biological nature of the receiving water body. Ajayi et.al (1981) reported how increased industrial activities have led to pollution stress on surface waters both from industrial, agricultural and domestic sources. Osibanjo et.al (2011) reported the resultant effect of these effluents on public health and environment. Saad et.al (1984) how population growth has resulted in a tremendous increase in discharge of a wide diversity of pollutants to receiving water bodies of many African countries due to steep increase in urbanization which has caused undesirable effects on the different components of the aquatic environment and on fisheries. Glyn et al (1996) has reported about sources of wastewater from industries. Further reports were made in 1995 that how high levels of pollutants in river water systems causes an increase in biological oxygen demand (BOD), chemical oxygen demand (COD), total dissolved solids (TDS), total suspended solids (TSS), toxic metals such as Cd, Cr, Ni and Pb and fecal coliform and hence make such water unsuitable for drinking, irrigation and aquatic life as well as on sources of industrial wastewaters which have high biochemical oxygen demand (BOD) such as biodegradable wastes from human sewage, pulp and paper industries, slaughter houses, tanneries and chemical industry. Others include those from plating shops and textiles, which may be toxic and require on-site physiochemical pre-treatment before discharge into municipal sewage system by Emongor et.al (2005), Phir et.al (2005), Otokunefor et.al.(2005). Okamura et.al (1994) and Martin et.al (1986) reported that the wastewater generated from many industries may contain a number of heavy metals which have significant toxic effects. Moore (1991) and Murti et.al (1991) reported about why industrial wastes are considered as pollutants. Venkataraman,(1965) reported about the chemistry of synthetic dyes. Nemerow et.al (1958), Walsh et.al(1980) and Anthony (1977) reported that effluents from dye industries are considered as pollutant because of two reasons they impart color to water, which is not acceptable on aesthetic grounds, and they are toxic and adversely affect life. Caturla et.al (1988) and Weiner (2000) reported that phenols are also priority pollutants like metals and dyes. Selassie et.al (1999), Castillo et.al (1999) and Fawell et.al (1988) reported that since phenols impart bad odor and taste to water they are toxic even at low concentration.

De Zuane, (1997) reported about the effluents generated by research laboratories, hospitals, nuclear power plants, and ore processing industries which contains radioactive substances and are harmful because of the radiations generated by them. He further reported about the constituents of wastewater generated by domestic, pharmaceutical and other industries that are rich in synthetic and natural detergents are widely used for cleaning and emulsification purposes. Kupchella et.al.(1989) reported about one class of organic water pollutants of considerable interest that is the family of polychlorinated biphenyls (PCBs) which are made by substituting1 to 10 hydrogen atoms of biphenyl with chlorine atoms. They show high chemical, thermal, and biological stability, as well as low vapor pressure and high dielectric constants. They do not cause a biochemical oxygen demand problem in aquatic ecosystems but are extremely toxic. PCBs are generated in a variety of manufacturing processes, which include the manufacture of brake linings, glass ceramics, grinding wheels, various types of coatings, flame proof paints, varnishes, sealants, electrical equipments, and plastic coatings, etc. Melnikov, (1971) reported about the constituents of rural wastewater which are rich in pesticides. Depending on their function, pesticides are sub classified as insecticides, molluscides, nematicides, rodenticides, avicides, piscides, fungicides, bactericides, slimcides, algicides, and herbicides. Among these, insecticides and fungicides are important pesticides with respect to human exposure in food because they are applied shortly before or even after harvesting. Herbicide production has increased significantly, as chemicals are being increasingly used during the cultivation of land for controlling weeds and now accounts for the majority of agricultural pesticides. Although DDT has been banned, various substitutes such as toxaphene, lindane, parathion, malathion, heptachlor, and endrin can also cause environmental pollution. The problem of pesticide pollution arises not only due to agricultural operations but also from pesticide manufacturing plants. Okamura, et.al (1994), Martin, et.al (1986), Nemerow et.al (1958), Walsh, et.al (1980), Anthony (1977), Selassie et.al (1999), Castillo et.al (1999), Fawell (1988) and Melnikov, (1971) reported about the constituent concentration level and toxic effects of chemical pollutants in wastewater.

The review by Dejoux et.al (1981), Egborge et.al (1999) and Burgis et.al (1987) contains matter on the state of pollution of African inland waters. Calamari (1985) reported about the public debate about environmental effects of effluents discharged into aquatic environments. Ezeronye et.al (1998) reported about the effluent discharge practices in Nigeria and the measures taken by Federal Environmental Protection Agency (FEPA) to check these environmental abuses has had little or no impact on pollution control in the cities of Nigeria. Anetor et al. (2003) discussed about how water pollution has become a global problem. Some reasons are Population explosion, hap hazardous rapid urbanization, industrial and technological expansion, energy utilization and wastes generation from domestic and industrial sources that have rendered many water resources unwholesome and hazardous to man and other living resources. Reviews by Fakayode (2005), Davies et.al (1988), Nubi et.al (2008), Vesiland et.al (1990) and Botkin et.al (1998) contain analysis of the constituents, sources and impact of industrial wastes to aquatic ecosystems of Nigeria. The industrial wastewater includes heavy metals, pesticides, polychlorinated biphenyls (PCBs), dioxins, Polyaromatic hydrocarbons (PAHs), petrochemicals, phenolic compounds and

microorganisms. Nwachukwu et.al (1989) reported about the scenario of water pollution in cities of Nigeria like Kaduna, Lagos and Aba which depend very much on its rivers. He has reported how the rush by African countries to industrialize has resulted in discharge of partially treated or raw wastes into the surrounding bodies of water since the development of treatment facilities are unable to keep pace with the rate at which the wastes are generated by the industries. Kanu et al. (2006) discussed about the seasonal variations in the concentration of effluents in Nigerian water bodies and impact of these effluents to human health due to the bacterial contamination. Kosaric et.al (1992) reported that the constituents of effluents from industries are 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 coloring compounds. FEPA (Federal Environmental Protection Agency). (1991) reported that many small to large cottage industrial establishments in Nigeria that discharge harmful wastewater effluents, the

physicochemical analysis of the effluents indicates that most of these industries conform to the recommended FEPA [25] guidelines, however, exceptions occur in the total dissolved solids (TDS) and Nitrate (NO3-) contents. Agedengbe et.al (2003) analyzed the pH of effluents from food and beverage industries and found that they have abnormally acidic pH which is adversely affecting the humans and the aquatic habitat. Ezenobi et.al (2004) reported about the index of pollution measure in industrial wastewater and according to him an important pollution index of industrial wastewaters is the oxygen function measured in terms of chemical oxygen demand (COD), and biological oxygen demand (BOD), while the nutrient status of wastewater are measured in terms of nitrogen and phosphorus. In addition, other important quality parameters include pH, temperature and total suspended solids. Ogunfowokan et.al (1998) reported that the relative flux in the hydrodynamic conditions and pollution characteristics of wastewater is a function of time. He found that Industrial effluents are characterized by their abnormal turbidity, conductivity, chemical oxygen demand (COD); total suspended solids (TSS) and total hardness. The effluent total hardness concentrations of a chemical-biological treatment plant were found greater than the influents. Adekunle et.al (2008) reported about organic pollution. According to him organic pollution is made worse by land-based sources such as the occasional discharge of raw sewage through storm water outlets, and industrial effluents from refineries, oil terminals, and petrochemical plants. Lateef et.al (2004) reported about the microbiology of pharmaceutical effluent and its public health implications. According to him some of the most representative pharmaceutical and personal care products found in receiving waters include antibiotics, lipid regulators, anti inflammatories, anti epileptics, tranquilizers, and cosmetic ingredients containing oil and grease with very different chemical structures. Belanger et al (2004) conducted a comprehensive study of an AS mixture composed of tetra (C14) and pentadecyl (C15) chain lengths to better understand effects on microbial and macro invertebrate populations and communities. A 56-d exposure of AS was performed at concentrations ranging from 57 to 419 g L-1 (analytically confirmed exposures) and was accompanied by detailed investigations of periphyton community function (autotrophy, heterotrophy, and metabolism of test chemical). Periphyton structure (algal

population and community dynamics based on taxonomic identity), invertebrate structure (benthic abundance, drift), and insect emergence patterns based on taxonomic identity were also studied. A no-observed-effect-concentration (NOEC) of 222 g L-1was concluded for several individual algal and invertebrate species based on univariate statistical analyses. An apparent energetic subsidy from C14-15AS at the highest concentrations of 222 to 419 g L-1 was observed and tied to changes in microbial community processing of AS when added at these high concentrations. A multivariate analysis based on principal response curves (PRC) indicated that communities in streams exposed to 222 to 419 g L-1 were significantly different from the controls leading to an overall conclusion that 106 g L-1 was the ecosystem NOEC. El-Gohary et.al (1987) reported about chemical constituents of industrial wastes from soap industries most of which are very toxic and capable of destroying the microbial habitats in a serious adverse way. For example, characterization of the composite wastewater from both soap and food processing plants indicated that the waste was highly contaminated with organic compounds as indicated by COD and BOD values. Kanu et al (2006) observed an overall seasonal variation of heavy metals such as lead, Zinc and Mn in the rainy season as compared to other metals for dry season. The concentrations of heavy metals were also, generally low in some samples and no similar trends were observed in the control samples. Except for iron and zinc, the concentrations of the other heavy metals were relatively low. Moreover, effluent from the soap manufacturing plant contained significant concentrations of oil and grease amounting to 563 mg L-1. Yusuff et.al (2004) subjected soap manufacturing effluent and the combined wastes discharged from an industrial complex to different treatment processes, namely dissolved air flotation, chemical coagulation sedimentation, and biological treatment via a completely mixed activated sludge process. He found that although coagulation using alum followed by sedimentation removed 52% of COD, residual values did not comply with the regulatory standards. Biological treatment of the composite combined wastewater significantly removed the organic contaminants in wastewater. Average residual BOD, COD, oil and grease values were 30, 92 and 8.3 mg L-1 respectively.

Calamari et.al (1985) observed that effluent from fertilizer plants contain a high concentration of potentially toxic wastes rich in ammonia-nitrogen, urea, nitrate-nitrogen orthophosphate-phosphorus which support the growth of algae, yeast and cyanobacteria. Cellulolytic bacteria such as Klebsiella pneumonia and Enterobacter have been isolated from spent water from the paper and pulp industries. The occurrence of these microbes in the effluents lead to excessive oxygen demand loading and also disturb the ecological equilibrium of the receiving waters with much loss of aquatic life and intense consequences. Ekhaise et.al (2005) reported association of heavy metals with the textile effluents. Kanu et.al (2006) observed wastewater from Brewery Industry originates from liquors pressed from grains and yeast recovery and found that they have the characteristic odor of fermented malt and are slightly acidic. Ekhaise and Anyansi (2005) reported high counts of bacterial population in Ikpoba River in Benin City Nigeria receiving a brewery industrial effluent. Onwuka et al (2004) studied eighty-eight (88) samples of the groundwater near industrial effluent discharges in Enugu in order to evaluate its potability. The parameters of interest are common waste-derivable chemical constituents such as nitrate (NO3-), chloride (Cl-) and sulphate (SO42-), and indicator microorganisms, like Escherichia coli. The study showed that about twenty two percent (22%) of the samples had concentrations of NO3-higher than the WHO permissible level (45mg/L) while eight out of the ten samples analyzed to test the bacteriological quality of the groundwater showed evidence of sewage and industrial effluent contaminations. The identification of E. coli in the water indicates faecal contamination. Improvement in the management of domestic wastes, such as the use of a central sewer, will preserve the aquifer, and consequently improve the quality of the groundwater. Ibekwe et al (2004) analyzed the wastewater in the accumulation pond and final discharge point of Nigerian Bottling Company PLC in Owerri, Nigeria to determine their bacteriological and physico-chemical characteristics. Species of organisms isolated

included Staphylococcus, Bacillus, Lactobacillus, and Streptococcus. Others include Klebsiella, Escherichia, Proteus and Serratia. However, species of Lactobacillus and Proteus were isolated from the final discharge point only. Bacterial count after 72 hours was higher with a maximum count of 6 x 107cfu/ml in the final discharge point. The waste water from both points were clear and had the same residual chlorine (1ppm) and

iron (1ppm) concentration, while the accumulation pond showed more acidity with a pH of 6.61.2. The final discharge contained more dissolved solids (201.8ppm) which was double that of the accumulation pond (102.2ppm). It was also found that dissolved oxygen was slightly higher (6.00.26mg/ml) in the final discharge point than accumulation pond (5.00.33mg/ml). It was found to be within permissible limits as specified by the Federal Ministry of environment in Nigeria by FEPA (Federal Environmental Protection Agency). (1991). The toxicity of benzene, hydroxylbenzene (phenol), chlorobenzene, methylbenzene (toluene) and dimethylbenzene (xylene) to four chemolithotrophic bacteria

(Nitrosomonas, Nitrobacter, Thiobacillus and Leptothrix isolated from the New Calabar River water were investigated by Odokuma and Oliwe (2003). They further reported that wastes containing hydroxyl and chlorosubstituted derivatives of benzene may pose a greater toxicity problem to microbiota than wastes containing methyl-substituted derivatives. The nitrification stage of the nitrogen cycle will also be greatly impaired in the presence of these groups of chemicals in a river. Omoleke (2004) reported that open and indiscriminate dumping of solid wastes in drainages and riverbanks is one of the most critical problems facing the city of Ibadan in the context of improper disposal of domestic wastes, particularly in urban centers of most developing countries. Sewage effluents rich in decomposable organic matter, is the primary cause of organic pollution. Domestic wastes in the country like in many other developing countries may now contain modern environmental health hazardous substances thus posing additional risk to public health were reported in reviews of Nweke et.al (2009), Adefemi et.al (2009) and Sridhar et.al (1981). Nweke et.al (2009) also reported about secondary organic pollution which is defined as the surplus of organic matter, which is the sum of undecomposed organic material introduced into the water body with primary pollution and of the material resulting from an extremely increased bioproductivity within the polluted ecosystem itself. Sridhar et.al (1981) studied about the sanitary excreta disposal system of Nigeria and he found that except for a few regions, in Nigeria urban areas do not have any central sewerage system or sanitary excreta disposal system. The wastewater from most parts of

more than 186 urban centers is carried in open drains into streams and rivers, a characteristic feature of many developing countries.

Davis et.al (1980) reported about the sources of palm oil mill effluent (POME) which is generated from three major sources, namely sterilizer condensate, hydro cyclone waste and separator sludge.. On an average 0.91.5m3 of POME is generated for each ton of crude palm oil produced. Ma (2000) reported that POME is rich in organic carbon with a biochemical oxygen demand (BOD) higher than 20 g/L and nitrogen content around 0.2 g/L as ammonia nitrogen and 0.5 g/L total nitrogen. The PH of the river Yamuna at Agra ranged between7.19 to 8.76 that showed alkaline nature (Sharma, 1999). Sharma and Agarwal (1999) noted the PH ranges of 7.31 to 8.17 from river Yamuna at Kailas Ghat and near Taj Mahal, Agra. The PH in the Ramganga river at Moradabad (UP) fluctuated from 7.35 to 8.76 Sharma and Agarwal (1999) recorded the maximum temperature 29.490C in the river Yamuna at Agra. Archana and Kumar (1999) measured the conductance of Yamuna River at Agra from 179 to 993mScm-1. The higher value of conductivity suggests the presence of ionic species as a pollutant. Dwivedi et. al., (2000) found the turbidity in the range of 73.8 to 145.7 NTU in river Ganga at Varanasi. The total dissolved solids of river Yamuna at Agra ranged from 175 to 1315 mg/L. The total dissolved solids values were found highest in the post monsoon season. It may due to the flow of sediment into the river during monsoon season. Mishra and Tripathi (2001) recorded the recorded the range of DO 3 mg/L to 8.5 mg/L in Ganga river water at Varanasi. Very low DO content showed the presence of high organic matter which leads to the consumption of oxygen during its decomposition by the heterotrophs in Water. Sharma (1999) observed the BOD in Yamuna river water at Agra from 3.60 to 84.0 mg/L that showed significantly higher than the permissible limit and in turn affected the DO values. Sharma and Agarwal (1999) recorded BOD in river Yamuna at Agra from 3.60 to 55 mg/L. BOD in the summer season may be low and the lower value was due to dilution of river water. Dwivedi et.al, (2000) reported the chloride value in the range of 15.2 to 24.4 mg/L in river Ganga at Varanasi. The phosphate content in river Yamuna at Agra ranged from 0.02 to 9.08 mg/L.

Sandeep K. Pandey and Shweta Tiwari (2009) noted the potassium content of Ghazipur city ranges from 4 to 10 ppm.

Wastewater generation and its treatment Mitsch and Gosselink, (1993) reported that nutrient and solids removal in wetlands is facilitated by shallow water (which maximizes the sediment to water interface), high primary productivity, the presence of aerobic sediments and anaerobic sediments, and the accumulation of litter. Gambrell and Patrick, (1978) reported that nitrate and nitrite are removed from the water by plant uptake or Denitrification. Faulkner and Richardson, (1989) further reported that Denitrification brings about a removal of nitrogen from the aqueous system and it is the most important removal pathway for nitrogen in most wetlands. According to Johnston (1991) high nitrogen removal rates have been noted in many wetlands. The reasons to this was further given by Gambrell and Patrick, (1978) that this happens because of the fact that the transformations of nitrogen involve microbial processes so nitrogen removal is enhanced during the growing season when high temperatures stimulate microbial population growth. Richardson (1985) reported that adsorption of phosphorus is the main mechanism for phosphorus removal in wetlands. He further reported that since phosphorus adsorption is enhanced under aerobic conditions, the removal of phosphorus in the anaerobic conditions of wetlands may be less than on dry soil. Kadlec (1985) reported that as phosphorus inputs to a constructed wetland continue over a period of several years, sorption sites in the sediments may become increasingly unavailable and eventually lead to phosphorus release. Gearhart et al. (1989) observed an increase in phosphorus

retention in domestic wastewater treatment wetlands. Hammer (1992) gave a number of strategies which have been adopted at constructed wetland sites to enhance phosphorus sorption. These include distributing the inflow along the length of a pipe to increase the surface area of initial contact between the wastewater and the sediments. It was further reported in the review by James et al. (1992) that adding aluminum to the substrate can also enhance phosphorus removal. It was further supported by Richardson (1985) by the fact that phosphorus adsorption is positively correlated to aluminum content in the substrate. Faulkner and Richardson,

(1989) reported that Periodic draining can allow oxidation and recharge sorption sites for greater phosphorus removal than under permanently reduced conditions.

Gersberg et al. (1989) in his review has thrown light upon the microbial treatment of wetlands in North America. According to his review most related diseases in North America are caused by bacteria and viruses rather than worms and protozoa so the treatment wetlands literature deals primarily with these two groups of organisms. Coliforms are reduced within wetlands for a number of reasons: exposure to sunlight, predation, competition for resources, and toxins. In addition, they may be buried beneath sediment or adsorbed. Instances from his review says that In two cases in which

constructed wetlands were used as tertiary treatment systems for domestic wastewater, bacterial and viral indicators were 90-99% removed. Holmes et al. (1992) reported that milk is the major organic contaminant from the dairy parlor. It has a high 5-day BOD (about 100000 mg BOD 5 l -l) because of its high fat and sugar content. It further receives supports from the report of Midwest Plan Service, (1987) which says that treatment of dairy parlor waste sometimes includes a septic tank/drain field system; however septic tanks are not recommended because of the propensity for the formation of a bacterial slime which can clog soil pores in the drain system. According to McCaskey et al. (1994) currently many swine waste management systems include temporary storage in anaerobic lagoons followed by land spreading. Runoff from the land is potentially detrimental to downstream waters and the odor of surface spread waste is objectionable if not incorporated immediately into the soil. Therefore, new and sustainable waste management strategies are needed. According to the reviews of Mitsch and Cronk, (1992); McCaskey et al., (1994) before construction of an animal wastewater treatment wetland, selection of a suitable site includes consideration of the goals of the wetland, soil type, topography, climate, cost, and potential future changes in farm management. The review of Reed et al., (1988) focuses on The design guidelines provided by the NRCS are based on municipal wastewater treatment wetlands and the experiences of those working with similar systems in the Tennessee Valley Authority. Whereas the review of Krider and Boyd, (1992) focuses on the standards for other waste management structures, such as lagoons.

Further McCaskey et al., (1994) reported that since precipitation exceeds evaporation in areas where treatment wetlands are feasible, it may be desirable to build a detention pond downstream from the wetlands so that if an outflow does occur, the no-discharge requirement can still be met. Reed et al., 1988 reported that both design for construction of wetlands procedures are based on plug flow kinetics. Further The BOD loading rate is conservative compared with the recommendations of Reed et al. (1988), of a BOD loading of 112 kg ha- t day- l (100 lb acre day-l). The residence time depends upon the average temperature and the length of time it takes to degrade the BOD. Hammer, (1992) observed that a surface flow wetland that accommodates varied depths may best promote nitrification and Denitrification. Hammer (1993) further reported on a marsh-pond-marsh system constructed at the Pontotoc Experiment Station in Mississippi to treat swine wastewater. He also reported that subsurface flow systems are susceptible to clogging, therefore they are not recommended for waste with a high concentration of total solids. According to Biddlestone et al., (1991) Sizing of these wastewater treatment beds is based on work by Kickuth in Germany. Several natural and constructed wetlands have been tested for their ability to retain or transform nutrient inputs from municipal wastewater (Odum et.al., 1977; Dierberg and Brezonik, 1983; Kadlec, 1987; Knight et al., 1987; Brodrick et al., 1988; Hammer, 1989). Excellent percent reductions have been noted at constructed wetlands treating swine wastewater in Alabama (McCaskey et al., 1994), North Carolina (Hunt et al. 1994) and Mississippi (Cathcart et al., 1994), perhaps because loading rates have tended to be lower at swine operations than at dairy farms. Lanier et al., (1991) reported about the mechanism of waste treatment on a dairy farm in Sonoma County, California, the waste from the milking parlor, loafing areas, and feeding area are flushed to a settling basin and then to a rotating screen separator. McCaskey et al., (1994) reported that high nutrient reductions have been achieved at the Sand Mountain Agricultural Experiment Station of Auburn University where swine waste is subjected to primary treatment in a two-stage lagoon system that reduces BOD 5 60% before the liquid waste enters the wetlands. In addition, the lagoon effluent is diluted with fresh water at a ratio of 2.7:1 (lagoon effluent: water) to reduce average influent ammonia concentration from 173 to 94 mg l-1.

Reddy and DeBusk, (1987) studied about the nitrogen and phosphate removal of efficiency of wetlands and found that 16-75% of total N removal and 12-73% removal of total P occurs in wastewater treatment wetlands. Jern et.al (2006) reported that direct aerobic treatment of hot wastewater is more difficult since oxygen transfer would be less efficient. Reviews of researchers like Bauer and Fallmann, (1997); Mantzavinos et al., (1997); Otal et al. (1997) and Feigelson et al., (2000) reveal that new developments in the variety of fields to meet the ever-increasing requirements of human beings have also led to the presence of new compounds in the effluent streams of processing plants, which are not readily degraded by the conventional effluent treatment methods.

Wastewater treatment technologies In order to meet the growing demand for potable water and water of good quality for industrial use, it has become necessary to treat wastewaters for renovation, reuse, and pollutant removal before mixing with natural water bodies containing good quality water. The methods that are adopted to treat wastewater for pollution control can be broadly classified in four categories: physicochemical processes, biological processes, nuclear treatment, and acoustical, electrical, and electromagnetic processes. Zouboulis et.al (2002) reported about filtration technology for treatment of wastewater. Sethi and Wiesner. (1995) reported about ultrafiltration and dialysis technologies for treatment of wastewater. Eliassen et.al (1967) reported about ion exchange technology for treatment of wastewater. Evaporation technique reported was by Birchler et.al (1994). Al-Degs et.al (2000) and Nicolet et.al (1999) reported about Adsorption technology for treatment of wastewater. Coagulation technology for treatment of wastewater was reported by Judkins and Hornsby (1978). Foam flotation technique was reported by Ng and Mueller (1975). Photochemical reactions; Activated sludge treatment were reported by Fox and Dulay. (1993); Bromley et.al (2000) respectively. Aerobic and Anaerobic treatment was combinedly reported by Kennedy et.al (1992), Bell et.al (2000) and Dos Santos et.al (2007). Shen and Wang (1994) reported about techniques involving microbial reduction in wastewater. Technique involving bacterial treatment in wastewater was reported by LaPara et.al (2000). Rela et.al (2000) and Basfar et.al (2002) reported about irradiation technique involving nuclear radiations for treatment of

wastewater. Electrodialysis and Electrolysis techniques were respectively reported by Chatchupong et.al (1996) and Szpyrkowicz et.al (1995). Suzuki et.al (2000) and Karapinar (2003) respectively reported about Ultrasonic and Magnetic separation technique for treatment of wastewater. The versatility and wide applicability of adsorption in pollution control has been recognized by Al-Degs et.al (2000), Danis et.al (1998), Quignon et.al (1998), Pirbazari et.al (1991), Carrott et.al (2000), Imamura et.al (2002) and Bansal et.al (2005). Clifford (1999) reported that the by far the largest application of ion exchange to drinking water treatment is in the area of softening, that is, the removal of calcium, magnesium, and other polyvalent cations in exchange for sodium. Besides zeolites, it was shown in 1934 by Adams and Holmes that phenol-formaldehyde resins exhibit cation exchange properties. This led to the development of a different type of resin that is used as adsorbents through a cation or anion exchange mechanism. Further LeVan et.al (1997) explained the characteristics of a Cation Exchange Resins that they generally contain bound sulfonic acid groups or, less commonly, carboxylic, phosphonic, or phosphinic groups. Examples are polystyrene sulfonate, sulfonated phenolic resin, phenolic resin, polystirene phosphonate, and polystirene amidoxime. He also explained the characteristics of an Anion Exchange Resins that they on the other hand generally have quaternary ammonium groups (strongly basic) or other amino groups (weakly basic) and include polystirene-based trimethyl benzyl ammonium, epoxy polyamine, and aminopolystirene. The works of Eliassen et.al (1967) and Yu et.al (2001) further proves that a number of exchange resins have been used quite efficiently for the removal of specific organic compounds. Bansal et.al (1988) reported that Activated carbon83 is the oldest adsorbent known and is usually prepared from source material, such as coal, coconut shells, lignite, and wood, using one of two basic activation methods i.e. Physical activation and Chemical activation. Bansal et.al (1988), Hassler (1963), Carrott et.al (2003) and Phan et.al (2006) reported about Physical activation that it is a process in which the precursor is developed into activated carbons using gases. The precursor is usually subjected to carbonization followed by activation or using either. Carbonization is the first stage where the precursor is pyrolyzed in the temperature range 600900c, in an inert atmosphere

(nitrogen, argon) resulting in the formation of char, which is normally non-porous. The activation is the process in which the material is exposed to oxidizing atmospheres (carbon dioxide, oxygen, or steam) usually in the temperature range 6001200c, which results in the removal of the more disorganized carbon and the formation of a welldeveloped porous structure, leading to high surface area. Carrott et.al (1991) reported the product formed by either of the methods is known as activated carbon and generally has a very porous structure with a large surface area ranging from 500 to 2000 m2 g1. The applicability of activated carbon for water treatment has been demonstrated by Weber et al (1970). In his article, Stenzel (1997) describes adsorption with granular activated carbon to be a proven technology for water purification. Besides these and other workers, Bansal and Goyal (2005) have also discussed activated carbon and its applications in their book. PAC is also used for wastewater treatment due to low capital cost and lesser contact time requirement reported by Najm et.al (1991). Attempts have therefore been made by many research workers in the field of waste management and pollution control to look for alternative adsorbents that are cheaper than activated carbons as reported by Ali et.al (2007). Bailey et.al (1999) presented a nice review of the removal of metals by low-cost adsorbents; similarly, an overview of lowcost adsorbents for heavy metal removal has been presented by Babel and Kurniawan (2003). Heavy metal removal by metabolically inactive non-living biomass of microbial or plant origin has been reviewed by Ahluwalia and Goyal (2007); the application of biosorption using fungi, yeasts, and bacteria for the removal of organic pollutants has been reviewed by Aksu (2005); Crini (2006) reviewed the feasibility of various non-conventional lowcost adsorbents for removal of dyes; chromium removal by various low-cost adsorbents has been discussed by Mohan and Pittman (2006); the possible use of sawdust for removal of various contaminants such as dyes and metals has been discussed by Shukla et.al (2002); the use of polysaccharide-based materials as adsorbents have been reviewed by Crini(2005); and application of chitosan for metal removal has been discussed by Gerente et.al (2007).

Natural coal was studied as an adsorbent for the removal of dyes by Mittal et.al (1993). Coal-based sorbents, namely charfines, lignite coal, and bituminous coal, have been used by Venkata Mohan et.al (1993) who presented results on the adsorption of color removal of the trisazo direct dye C.I. Direct brown 1:1 by adsorption onto these adsorbents. The potential of brown young coals Ilgin and Beysehir lignite to remove copper (Cu2+), lead (Pb2+), and nickel (Ni2+) from aqueous solutions was studied as a function of pH, contact time, metal concentration, and temperature by Pehlivan and Arsalan (2007). In a study of removal and recovery of Cu (II), Cr (III), and Ni (II) from solutions, Chui et.al (1996) utilized crude shrimp chitin packed in small columns. Shrimp shell wastes from Penaeus marginatus were demineralized by dilute HCl in small columns to yield shrimp chitin. 96% of the calcium was efficiently removed by this column method without removal of proteins. Jha et.al (1998) studied chitosan for Cd (II) removal and reported an adsorption capacity of 5.93 mgg1 at a pH range of 4.08.3. It was observed that the presence of ethylene diamine tetra acetic acid (EDTA) significantly decreased the cadmium removal. Biomass of nonliving dried roots of water hyacinth (without any pretreatment) was explored by Low et.al (1995) as an adsorbent for the removal of methylene blue and victoria blue, and the authors found that it possessed good adsorptive capacity128.9 and 145.4mgg1 for methylene blue and victoria blue, respectively. Besides these materials, natural and copper-coated moss and pinus sylvestris bark have been studied by Lee et al.(1995) and Margarida Alves et.al.(1993) respectively, as adsorbents. An adsorbent by a simple amine modification on mycelium from biomass of penicillin fermentation was prepared by Tan and Su (2004). Owing to their low cost, abundance, high sorption properties and potential for ion-exchange, clay materials are a strong candidate as adsorbents as reported by Crini (2006). Pradas et.al (1994) tried heat treatments and acid treatments of natural bentonite for the adsorption of Cd (II) and Zn (II). Results revealed that the adsorption capacity of natural bentonite is improved by heat treatment, while the acid treatment decreased the same. Lee et.al (1997) used organically modified montmorillonite and investigated the removal of three toxic organic phenols (i.e., 2-chlorophenol, 3-cynophenol, and 4-nitrophenol) in

a batch reactor. This modification results in a change in the surface character of montmorillonite from hydrophilic to organophilic. Similar findings were reported by Kim et.al (1996). Wu and coworkers (2001) studied the adsorption of phenol by both inorganic and organic-pillared montmorillonites. The authors suggested that the adsorbing capacity of modified clays depends not only on surface area,but mainly on micropore structure and surface components. The modified organic-pillared

montmorillonites with surfactant were found to improve adsorbing capacity greatly. Ozdemir et.al (2004) investigated modified sepiolite as an adsorbent for a variety of azoreactive dyes and suggested that the adsorption capacities can be improved upon modifying their surfaces with quaternary amines. Clay (montmorillonite) coupled with chitosanthereby forming biopolymer chitosan/montmorillonite nanocompositeswas used by Wang and Wang (2007) to study adsorption characteristic of congo red. The authors suggested that compared with chitosan, the nanocomposite had good flocculation ability in aqueous solution, with comparative low cost and relatively high adsorption capacity in comparison to pure montmorillonite. Crini (2005) has reported use of starch as adsorbents for the removal of pollutants. Daifullah and Girgis (1998) reported for the removal of substituted phenols, who suggested that the adsorption of phenols on these adsorbents was inversely proportional to their solubility. The feasibility of utilizing sunflower stalks, a renewable agricultural waste available at low cost, was explored by Sun and Shi (1998). El-Geundi (1991) studied maize cob, an agricultural waste, without any pretreatment for the removal of two basic dyes (astrazone blue and maxilon red) and two acid dyes (telon blue and erinoyl red). Acemiolu et.al (2003) used organosolvant lignin as sorbent for the removal of copper (II). The removal of the toxic metals Pb (II) and Cd (II)) onto modified lignin from beech and poplar woods by alkali glycerol delignification was studied by Demirbas (2004). Kraft lignin was studied for removal of Cu (II) and Cd (II) by Mohan et al (2006). The efficiency of the coir pith has been investigated by Parab et.al (2006) who studied the adsorption efficiency of the material for the removal of Co (II), Cr (III), and Ni (II) using a batch adsorption technique from synthetic nuclear power plant coolant water. Saw dust, corncob waste, coir pith, and agricultural wastes have been investigated as

adsorbents for metals and dyes by Ajmal et.al (1998) Wu et.al (2001) and Namasivayam et.al (2001) respectively. Corn cob as a low-cost adsorbent has also been used for making microporous activated carbon using zinc chloride by Tsai et.al (1998). Rengaraj et.al (2002) attempted to develop activated carbon from rubber seed coat for the removal of phenols using batch and column operations. They suggested that the adsorbed phenol can be desorbed by sodium hydroxide. Shimada et.al (1999) used newspaper as raw material for the production of activated carbon. The activated carbon so produced possessed good surface area (1000 m2 g1) and the yield was 40%. In view of its high surface area, this product functioned as a good adsorbent, as evidenced by high iodine (1310 mgg1) and methylene blue number (326 mgg1). Sewage sludge with additive coconut husk has been used by Tay et.al (2001) for preparation of activated carbons using ZnCl2 activation. It was suggested that low concentration of ZnCl2 tends to improve microporosity, and 5 M ZnCl2 was found to give the best activated sample with 867.61 m2g1 surface area with 57.99% phenol removal capacity. Advanced oxidation processes are defined as the processes that generate hydroxyl radicals in sufficient quantities to be able to oxidize majority of the complex chemicals present in the effluent water. These processes include cavitation (generated either by means of ultrasonic irradiation or using constrictions such as valves, orifice, venturi, etc.in the hydraulic devices (Adewuyi 2001; Gogate, 2002; Gogate and Pandit, 2001; Gonze et al., 1999; Keil and Swamy, 1999; Pandit and Moholkar, 1996; Moholkar et al., 1999a; Senthilkumar and Pandit, 1999), photocatalytic oxidation (using ultraviolet Radiation near UV light Sun light in the presence of semiconductor catalyst (Bhatkhande et al., 2002; Blake,1997; Herrmann, 1999; Yawalkar et al., 2001) and Fenton chemistry (using reaction between Fe ions and hydrogen peroxide, i.e. Fentons reagent (Venkatadri and Peters, 1993; Bigda, 1995, 1996; Nesheiwat and Swanson, 2000).Hydroxyl radicals are powerful oxidizing reagents with an oxidation potential of 2.33 V and exhibits faster rates of oxidation reactions as compared to that using conventional oxidants like hydrogen peroxide or KMnO4 (Gogate et al.,

2002a).Hydroxyl radicals react with most organic and many inorganic solutes with high rate constants (Glaze et al., 1992; von Sonntag, 1996; Hoigne, 1997).

Chemical oxidation technologies constitute the use of oxidizing agents such as ozone and hydrogen peroxide, but exhibit lower rates of degradation as compared to the processes based on the free radicals (Echigo et al., 1996; Weavers et al., 1998; Freese et al., 1999; Fung et al., 2000a; Zwinter and Krimmel, 2000; Arslan and Balcioglu, 2001a; Gogate et al., 2002a). Free radicals are generated when ozone is used in combination with hydrogen peroxide or action of ozone or hydrogen peroxide is supplemented by other energy dissipating components such as use of UV/sunlight or ultrasound and these hybrid techniques have been found to result in lower treatment times as compared to any of the individual techniques (Weavers et.al., 2000; Fung et al., 2000a; Gogate et al., 2002a). Majority of these oxidation technologies, however, fail to degrade the complex compounds completely, especially in the case of real wastewaters and moreover, cannot be used for processing the large volumes of waste generated with the present level of knowledge about these reactors. This was illustrated in the work of Commenges et al. (2000) where he have shown that cavitation has failed to give substantial degradation in the case of real industrial effluent, whereas similar results have been reported by Beltran et al.(1997) for the case of photocatalytic oxidation being applied to distillery and tomato wastewaters). Hence, these can be used to degrade the complex residue up to a certain level of toxicity beyond which the conventional methods can be successfully used for further degradation (Rachwal et al., 1992; Beltran et al. 1999a,b; Engwall et al., 1999; Kitis et al., 1999; Mastin et al., 2001). There have been a number of illustrations in the literature, dealing with the mechanisms of oxidation of different pollutants using cavitation including some review articles (Adewuyi, 2001; Dewulf et al., 2001; Hoffmann et al., 1996; Hung and Hoffmann, 1999; Weavers et al., 2000; Sivakumar et al., 2002; Shah et al., 1999; Suslick and Hammerton, 1986; Suslick et al., 1990). Suslick, 1990; Lorimer and Mason ;1987; Shah et al., 1999 further reported that Alternate compression and rarefaction cycles of the sound waves results in various phases of cavitation such as generation of the bubble/ cavity, growth phase and finally collapse phase releasing large amount of energy locally. The detailed discussion about the different types of sonochemical reactors has been made earlier by

Pandit and Moholkar, 1996; Shah et al 1999; Thompson and Doraiswamy, 1999; Keil and Swamy, 1999; Gogate et al., 2001a, 2002b. Use of equipments based on multiple frequencies y multiple transducers (device used for converting supplied electrical energy into sound energy and generate ultrasound with frequency in the range of 15kHz10 MHz) has been reported to be more beneficial as compared to the equipments based on a single frequency by Hua et al., 1995a; Thoma et al., 1997; Sivakumar et al., 2002; Gogate et al., 2001a, 2002b. Dahlem et al., 1998, 1999 reported that Ultrasonic horns vibrating in radial directions, which also gives additional advantage of better energy dissipation due to larger irradiating area, is another new development with promising future for medium to large-scale applications, but more work is required in terms of testing these equipments for operation at high frequency and high power dissipation. Higher frequencies of operation are suited for effective destruction of pollutants (until an optimum value and the magnitude of optimum frequency also depend on the type of the effluent and the operating conditions) (Hua and Hoffmann, 1997; Hung and Hoffmann, 1999). It is difficult to operate at higher frequencies greater than 200 kHz (Mason, 1992; Berlan and Mason, 1992) Hung and Hoffmann, 1999 as well as more number of cavitational events (Crum, 1995 reported that continuous operation with high frequencies at larger scale of operation (and hence at higher power dissipation levels), leads to an erosion of the transducer surface (due to lower collapse time of the cavitating bubbles. Mason, 1990 reported that, the power required for the onset of cavitation increases with an increase in the frequency of irradiation and hence the process may become uneconomical at much higher frequencies of irradiation due to the fact that significant quantity of the supplied energy will be used only in the generation of the cavities. Sivakumar et al. (2002) have described a design where 6 transducers in total have been attached on the opposite faces of a rectangular cross-section irradiating 25 and 40 kHz either individually or simultaneously) produces more intense cavitation as indicated by the higher values of the pressure pulse generated at the end of cavitation event for the multiple frequency operation as compared to the single frequency operation and hence results in higher yields of transformation. Moholkar and Warmoeskerken (2000) have also indicated that by adjusting the magnitude of the frequency in the multiple frequency

operation, the collapse of the cavities can be directed at a region away from the surface, so that the erosion of the transducer surface will be less).Also, larger volumes of effluent can be effectively treated due to increased cavitationally active volume for multiple transducers (Sivakumar et al., 2002; Gogate et al., 2002b). Gogate et al., 2001a observed greater energy efficiency for ultrasonic probes with higher irradiating surface, (lower operating intensity of irradiation) which results into uniform dissipation of energy. Aeration and addition of catalyst such as TiO2, NiSO4, CCl4, Fe2/Fe3, CuSO4 and also salts such as NaCl, significantly enhances the extent of degradation (Ingale and Mahajani, 1995; Mason et al., 1996; Seymore and Gupta, 1997; Shirgaonkar and Pandit, 1997; Hung and Hoffmann, 1998; Nagata et.al., 2000; Pandit et al., 2001; Sivakumar et al., 2002; Gogate et al., 2002c).Presence of gases (oxygen, ozone) or gaseous mixtures such as Ar/O3 mixture also increases the efficiency of acoustic cavitation in some cases (Hart and Henglein, 1985; Olson and Barbier, 1994; Entezari et al., 1997; Weavers et al., 1998, 2000). Suslick et al. 1997 and Sivakumar et.al. 2002 reported that rate of the destruction is inversely proportional to the operating temperature, which also affects the vapor pressure of the medium, and hence lowers temperatures (typically of the order of 1015 8C) will be preferred. However Drijvers et al., 1999 reported that if the dominant mechanism of destruction is pyrolysis, e.g. destruction of trichloroethylene this will not be true. The use of sonochemical reactors for the wastewater applications is not new to the researchers and there are many illustrations in the literature (Nagata et al., 1996; Thoma et al., 1998; Petrier et al., 1998; David et al., 1998; Gondrexon et al., 1999; Cyr et al., 1999; Suri et.al., 1999; Colussi et al., 1999; Joseph et al., 2000; Destaillats et al., 2000, 2001; Grieser et al., 2000; Yim et al., 2000; Tauber et al., 2000; Clark et al., 2000; Schramm and Hua, 2001; Teo et al., 2001; Gaddam and Cheung, 2001; Pandit et al., 2001; Yim et al., 2001) where they have been successfully used for the degradation of variety of compounds at different scales of operation. Peters (2001) has studied the sonolytic degradation of 1,2-dichloroethane, prepared in deionized water (model constituent solution) and also in the natural sample (concentration of approx.350 390 mg/L with other VOC amounting to 8085 mg/L), reporting that the destruction was

complete within 120 min for all the components (at conditions of operating frequency of 361 kHz, calorimetric power dissipation of 52 W, volume of effluent as 200 ml, operating pH of 6.28 and temperature of 9 8C) and also for some of the intermediates formed in the destruction process (e.g. trans-1,2-dichloroethane). Commenges et al. (2000) have reported that ultrasonic irradiation failed to induce any decrease in the toxicity and COD for a concentrated sample of the effluent from a paper mill (at operating conditions of operating frequency as 500 kHz, calorimetric power dissipation as 150 kWym3 and operating temperature as 20 8C). This may be possibly attributed to the high concentration of the complex refractory materials. Peters, 2001 reported that the current costs for the cleaning of contaminated ground water using acoustic cavitations are in the order of magnitude, higher than those by an air stripping/active carbon process. Thus, it is important to either find an alternative means for generating cavitation energy efficiently or use acoustic cavitation (generated by ultrasonic irradiation) in combination of other methods such as photocatalytic oxidation (Shirgaonkar and Pandit, 1998; Gogate et al., 2002a), wet air oxidation (Ingale and Mahajani, 1995; Dhale and Mahajani, 1999, 2001) etc. According to Hung and Hoffmann, 1999 it should also be noted that due to higher frequency of operation, higher number of free radicals will indeed be generated, but at the same time lower collapse time of the cavitating bubbles gives lesser contact time for the chemical constituents. As reported by Gogate and Pandit, (2001) one of the alternative techniques for the generation of cavitation is the use of hydraulic devices where cavitation is generated by the passage of the liquid through a constriction such as valve, orifice plate, venturi etc. Orifice plate set-up (Gogate et al., 2001a; Gogate and Pandit, 2001) offers more flexibility in terms of selection of the different orifice plate configurations (differing in number and diameter of holes (Gogate, 2002)) as compared to devices based on the use of throttling valves. There are good reviews available on this subject by Fox and Duley (1993), Legrini et al. (1993), Kamat (1993) and Hoffmann et al. (1995) covering the analysis of the studies prior to 1995 and depicting basics of the processes including the mechanism of oxidation of pollutants in detail. Some of the more recent promising works include Blake (1997),

Herrmann (1999) and Bhatkhande et al. (2002). A major advantage of the photocatalytic oxidation based processes is the possibility to effectively use sunlight or near UV light (Bauer, 1994; Peill and Hoffmann, 1997; Bauer and Fallmann, 1997; Guillard et al., 1999; Dillert et al., 1999; Fallmann et al., 1999; Herrmann et.al., 1999; Vidal et al., 1999; Yawalkar et al., 2001) for irradiation, which should result in considerable economic savings especially for large-scale operations. Various chalcogenides (oxides such as TiO2, ZnO, ZrO2, CeO2 etc.or sulfides such as CdS, ZnS etc.) have been used as photo-catalysts so far in different studies reported in the literature (Davis and Huang, 1990; Richard and Boule, 1994; Choi and Hoffmann, 1997; Chen and Ray, 1998; Chen et al., 1999b; Tanaka et al., 2000; Sakthivel et al., 2000; Andreozzi et al., 2000; Habibi et al., 2001a, b) The surface area and the number of active sites offered by the catalyst (thus nature of catalyst, i.e. crystalline or amorphous is important) for the adsorption of pollutants plays an important role in deciding the overall rates of degradation as usually the adsorption step is the rate controlling (Xu et al., 1999). Degussa P-25 catalyst is the most active form (hybrid mixture of rutile (approx. 70%) and anatase forms) among the various ones available and generally gives better degradation efficiencies, (Sakthivel et al., 2000; Yamazaki et al., 2001). Scouring is another problem associated with films comprising immobilized powders of TiO2 (Bideau et.al., 1995) and reduced catalyst area to volume ratio of the immobilized photocatalyst is likely to cause mass transfer problems. Butterfield et al. (1997) have reported a modified fabrication technique and design of the reactor in order to eliminate scouring. According to Kulkarni, 1998; Andreozzi et al., 2000; Sakthivel et al., 2000; Dijkstra et al., 2001; Gogate et al., 2002a catalyst concentration only till an optimum value should be used since using excess catalyst reduces the amount of photo-energy being transferred in the medium due to opacity offered by the catalyst particles. It should also be noted that the optimum value will strongly be dependent on the type and concentration of the pollutant, as well as the rate of generation of free radicals. Degussa P-25 TiO2 catalyst is the most beneficial (Sakthivel et al., 2000; Yamazaki et.al, 2001). Sensitizers or catalysts, e.g. ferrous ions, silver ions, manganese ions etc. can also be used to improve the treatment efficiency of photocatalytic oxidation process (Sclafani et

al., 1991; Lee et.al., 1993; Feigelson et al., 2000; Chen et al., 1999c; Lu, 1994). This is a major problem associated with the large scale designs (Mukherjee and Ray, 1999). The efficient reactor design must expose highest amount of the activated immobilized catalyst to the illuminated surface and must have a high density of active catalyst in contact with the liquid to be treated inside the reactor. The pioneering work done by a group of Ray is worth to mention in this area (Ray and Beenackers, 1996; Ray, 1997; Ray and Beenackers, 1997; Chen and Ray, 1998; Mukherjee and Ray, 1999; Ray, 1999). Herrmann (1999) have reported that no degradation was observed for real effluent with COD of 800 000 mg/kg and had to be diluted 1000 times after which COD reduction was observed). To give a quantitative idea about the effect, Beltran et.al (1993a) have shown that the destruction of atrazine is 70% for initial concentration of 10 ppm whereas for 100 ppm, only 45% of the initial atrazine is degraded (other reactor operating conditions are kept the same). Herrmann, 1999 reported that at temperatures above 80 8C, the exothermic adsorption of pollutant becomes unfavorable and tends to be the rate limiting step, leading to a decreased activity and hence reduction in the reaction rates. For some of the pollutants, which are weakly acidic, rate of photocatalytic oxidation increases at lower pH due to an increase in the extent of adsorption under acidic conditions (Vohra and Davies, 2000; Tanaka et al., 2000; Andreozzi et.al, 2000). Some of the pollutants, which undergo hydrolysis under alkaline conditions or undergo decomposition over a certain pH range, may show an increase in the rate of photocatalytic oxidation with an increase in the pH (Choi and Hoffmann, 1997; Tanaka and Saha, 1994; Trillas et al., 1996).Fox and Duley (1993) and Davis and Huang (1991) and Matthews and McEvoy (1992b) have reported that pH had marginal effect on the extent of degradation over the range of pH studied in their work. Dijkstra et.al (2001) has shown that there is no appreciable destruction in the absence of oxygen. Chen and Ray (1998) have shown that approximately 70% of the maximum rates of degradation (using pure oxygen) of 4-nitrophenol are observed at partial pressure of 0.2 atm. Thus, air can safely be used at commercial scale operation instead of pure oxygen, which will substantially decrease the operating costs. There have been many illustrations in the literature (Abdullah et al., 1990; Wei et al., 1990; Kormann et al., 1991; Butler and Davies, 1993; Yawalkar et al., 2001) regarding

the effects of various anions and cations. In general it can be said that CO3-, HCO3(they act as radical scavengers and also affect the adsorption process) and Cl- (affect the adsorption step strongly and also absorb UV light partly) ions have strong detrimental effect on the degradation process whereas other anions such as sulfate, phosphate and nitrate affect the degradation efficiency marginally. Yoo et al., 1997; Nagata et al., 2000 reported that real wastewaters may also contain some traces of radical scavengers such as HCO3-, CO32- ions, naturally occurring matter, t-butanol and this significantly affects the rates of advanced oxidation processes. Thus, certain modifications will be required in the overall treatment procedures so as to reduce the inhibiting effects, the effects of the radical scavengers or to bring the level of toxicity below a certain optimum value decided by the reactor operating conditions. According to Bigda, 1996 the oxidation system based on the Fentons reagent (hydrogen peroxide in the presence of a ferrous salt) has been used for the treatment of both organic and inorganic substances under laboratory conditions as well as real effluents from different resources like chemical manufacturers, refinery and fuel terminals, engine and metal cleaning etc. In the literature, three main reactive radical species have been contemplated; two of them involve the presence of hydroxyl radicals (classical Fentons chemistry) in either free or caged form (Walling and Amarnath, 1982) whereas third oxidant has been postulated to be aquo or organocomplexes of the high valence iron, the ferryl ion (Sawyer et al., 1996). The oxidation system can be effectively used for the destruction of toxic wastes and non-biodegradable effluents to render them more suitable for a secondary biological treatment (Chen and Pignatello, 1997).V enkatadri and Peters (1993), Bigda (1995, 1996) and Nesheiwat and Swanson (2000) have written good informative articles on the basics of Fenton chemistry as well as its application to wastewater treatment. The pH of the system has been observed to significantly affect the degradation of pollutants (Sedlak and Andren, 1991; Lin and Lo, 1997; Kang and Hwang, 2000; Nesheiwat and Swanson, 2000; Benitez et al., 2001a).The optimum pH has been observed to be 3 in the majority of the cases (Venkatadri and Peters, 1993; Tang and Huang, 1996; Kwon et al., 1999; Benitez et al., 2001a) and hence is recommended as the operating pH. At operating pH of >4, the decomposition rate decreases because of the

decrease of the free iron species in the solution, probably due to the formation of Fe (II) complexes with the buffer inhibiting the formation of free radicals and also due to the precipitation of ferric oxyhydroxides (Bigda, 1995; Lin and Lo, 1997; Nesheiwat and Swanson, 2000) which inhibit the regeneration of ferrous ions. Also, the oxidation potential of HO radical is known to decrease with an increase in the pH (Kwon et al., 1999). Usually the rate of degradation increases with an increase in the concentration of Ferrous ions (Lin and Lo, 1997; Kwon et al., 1999; Benitez et al., 2001a) though the extent of increase is sometimes observed to be marginal above a certain concentration as reported by Lin et al. (1999) and Kang and Hwang (2000) and Rivas et.al. (2001). Also, an enormous increase in the ferrous ions will lead to an increase in the TDS content of the effluent stream and this is not permitted. Usually it has been observed that the percentage degradation of the pollutant increases with an increase in the dosage of hydrogen peroxide (Lin and Peng, 1995; Lin and Lo, 1997; Kwon et al., 1999; Lin et al., 1999; Kang and Hwang, 2000; Rivas et al., 2001). The residual hydrogen peroxide contributes to COD (Lin and Lo, 1997) and hence excess amount is not recommended. Also, the presence of hydrogen peroxide is harmful to many of the microorganisms (Ito et al., 1998) and will affect the overall degradation efficiency significantly, where Fenton oxidation is used as a pretreatment to biological oxidation. Benitez et al., 2001a have reported that the acetic acid/acetate buffer gives maximum oxidation efficiency whereas least is observed for phosphate and sulfate buffers. According to Nesheiwat and Swanson, 2000 if the reaction temperature is expected to rise beyond 40 8C due to exothermic reactions, cooling is recommended as above 40 8C, efficiency of hydrogen peroxide utilization decreases due to accelerated decomposition of hydrogen peroxide into water and oxygen. Chemical coagulation step is recommended after the Fenton oxidation so as to keep the concentration of the soluble iron within the specified limits (Lin and Lo, 1997). Lin et al. (1999) have also demonstrated the efficacy of chemical coagulation in controlling the concentration of TDS below the specified limits. Fentons reagent has been effectively used for the remediation of dieselcontaminated soils (Watts and Dilly, 1996), removal of color in effluents from dyes industry (Kuo, 1992; Park et al., 1999), destruction of organics such as 2,4,6-

trinitrotoluene (Li et al., 1997a,b), RDX (Hundal et al., 1997), 2,4-dinitrophenol (Wang et al., 1999; Kang et al., 1999b), Chlorobenzene (Watts et al., 1997), tetrachloroethylene (Yoshida et al., 2000), chlorophenols (Barbeni et al., 1987; Watts et al., 1990; Potter and Roth,1993), halomethanes (Tang and Tassos, 1997). A number of devices can be used to transfer the generated ozone into water such as countercurrent bubble column, packed and plate columns, static mixers, jet reactors and agitated vessels (Bowers et al., 1973; Glaze, 1987; Munter et al., 1993; Martin and Galey, 1994). Ozone transfer efficiency should be maximized by increasing the interfacial area of contact (reducing the bubble size by using small size ozone diffusers such as porous disks, porous glass diffusers (Ledakowicz et al. 2001), ceramic membranes (Janknecht et al., 2001; Ciardelli et.al. 2001; Ciardelli and Ranieril, 2001; Picard et al., 2001)) and increasing the contact time between the gas and the effluent (increase the depths in the contactor, optimum being 3.7 to 5.5 m). Martin and Galey (1994) have reported the use of static mixers for the transfer of ozone and showed that the mass transfer coefficient increased with a decreasing water flow rate and increasing gas flow rate. Recently, de Traversay et al. (2001) have studied disinfection of different microorganisms using ozone in the static mixers and reported that ozone transfer efficiency increases with an increase in the pressure drop, decrease in gasyliquid ratio and was independent of the ozone loading. Staehelin and Hoigne (1982) have reported that at high pH values, ozone reacts almost indiscriminately with all organic and inorganic compounds present in the reacting medium. It should also be noted that if the operating pH is above the pK value of the pollutant, i.e. the pollutant is not in molecular state, not much enhancement in the rates of degradation will be observed (Beltran et al., 1992). Increase in the ozone partial pressure increases the extent of degradation (Beltran et al., 1992, 1993a). The best way is to increase and maximize the effective transfer of ozone into the solution (Schulz and Prendiville, 1993). The effect depends on the mechanism of the degradation. If the destruction is by direct attack of ozone on the chemical bonds, not much effect is there (Arslan and Balcioglu, 2000), but if it is through the free radicals, presence of radical scavengers such as

HCO3y ions and humic substances decreases the extent of degradation (Beltran et al., 1994). Due to an increase in the temperature, ozone solubility decreases, thereby reducing the amount of ozone available for the reaction, which may result in decreased degradation (Beltran et al., 1994).However, Meijers et al. (1995) have reported that degradation of diuron increased with an increase in the temperature from 5 to 20 8C. According to Masten and Davies, 1994; Volk et al., 1997; Legube, 1999; Arslan et al., 2000 Catalyst such as BST catalyst TiO2 fixed on alumina beads, Fe (II), Mn (II) can be used to increase the degradation efficiency. Ozonation can be effectively combined with other oxidation techniques such as Ultrasonic irradiation (Weavers et.al. 1998; Kang and Hoffmann, 1998; Kang et al., 1999a), UV irradiation (Beltran, 1997; Rice, 1997; Trapido, et al., 1997; Hautaniemi et al. 1998; Balcioglu and Getoff, 1998), g-irradiation (Gehringer et.al.1997; Balcioglu et al., 2000), Hydrogen peroxide (Ormad et al., 1997; Gehringer et al., 1997; Masten et.al, 1997; Kuo et al., 1997; Beltran et al., 1998; Arslan et al., 1999a; Balcioglu and Arslan., 2001), Fenton oxidation (Bauer and Fallmann, 1997) as well as aerobic digestion (Benitez et al., 1999a,b) Some of the specific examples of ozone use for treatment of wastewaters can be cited as; Textile effluent treatment in terms of color removal (Ruppert et al., 1994) and reduction of TOC and COD to certain limits beyond which biological oxidation can be used (Perkowski et.al, 1996; Rice, 1997), degradation of effluent from dye industry (Law et al., 1996; Liakou et al. 1997; Wu et.al, 1998), conversion of cyanide ions into less toxic cyanate ions (Rice, 1997), degradation of protocatechuic acid (Benitez et al., 1996), chlorinated phenols (Boncz et.al, 1997; Trapido et al., 1997), Chlorobenzenes (Masten et al., 1997), color removal in the effluent from a molasses processing plant (Gehringer et al., 1997), removal of pesticides (Meijers et al., 1995; Reynolds et al., 1989), treatment of wine-distillery (Beltran et.al.1999b; Benitez et al., 1999a) etc. Ozone can also be used for disinfection of water; it is particularly effective against recalcitrant microorganisms. Ayling and Castrantas, 1981 reported that Hydrogen peroxide has been found to be effective in degradation of compounds or treatment of real wastewaters requiring less stringent oxidation conditions but applications to complex mixture of effluents like dyes, textile industry effluent, heteroaromatics etc. need to be explored.

Hydrogen peroxide has been used in the industrial effluent treatment for detoxification of cyanide, nitrite and hypochlorite, for the destruction of phenol aromatics, formaldehyde, removal of sulfite, thiosulfate and sulfide compounds (Bull and Zeff, 1991; Eul et al.,1991).A yling and Castrantas (1981) have presented a good overview for the use of hydrogen peroxide for wastewater treatment applications. Fung et al. (2000a) have shown that the degradation of CI reactive red120 dye was marginal for treatment with hydrogen peroxide alone whereas Arslan and Balcioglu (2001a) have shown that absolutely no degradation was observed for the addition of hydrogen peroxide alone for the dyehouse effluent. Moreover, stability of H2O2 remains a question, as the catalytic decomposition agents present in effluents compete with the pollutants and hence proper injection methods achieving rapid dispersal of hydrogen peroxide, needs to be devised (Ayling and Castrantas, 1981). The rates of formation of hydroxyl radicals are significantly enhanced under the effect of photochemical or ultrasonic irradiation and hence there is significant enhancement in the rates of these types of reactions in the presence of hydrogen peroxide (Eul et al., 1991; Bull and Zeff, 1991; Kim et al., 1997; Ince, 1999). Moreover, the acoustic streaming produced by ultrasound induced cavitation phenomena (Vichare et al., 2001) also helps in decreasing the effect of mass transfer limitations.

CHAPTER 3 DESCRIPTION OF THE SITE UNDER STUDY The work on this plant was started in September, 1986 and it was commissioned in October, 1988 under Ganga Action Plan. There are two streams of 4 mld each and the process consists of screening, primary settling, activated sludge and secondary clarifier. Primary settling activated sludge and secondary clarifier. Primary sludge is pumped to digester where gas is generated and collected in gas holders. Indigenous dual fuel engines have been installed to produce electricity from bio-gas generated. The various design parameters adopted for the design of plant and minimum/maximum actually observed during last three years summarized in Table- 1. The plant receives sewage from two pumping stations within BHU campus and from Assi pumping station. The plan is under operation since March 1989. Removal of B.O.D at different stages is constantly being observed at the laboratory set along with the plant. The quality of treated effluent as required and as actually observed after treatment through his plant is summarized in Table-1 & 2. S.NO Raw Sewage characteristics Design values Minimum-maximum values actually observed during operation & maintenance 7.27 to 7.23 20c to 30c 66 mg/L to 350 mg/L

pH 7.8 Temperature 25c Total suspended 600 mg/L solids 4 BOD 5 days at 20c 300 mg/L 60 mg/L to 240 mg/L 5 Volatile suspended 420 mg/L 36 mg/L to 192 mg/L solids 6 COD 400 mg/L 104 mg/L to 354 mg/L 7 Influent load on plant 8 mld 9.59 mld to 12.72 mld Table-3.1: Layout of treatment efficiency of Bhagwanpur Sewage Treatment Plant Gas produced and electricity generated

1 2 3

Settled sludge from primary clarifier is pumped to digester where anaerobic digestion takes place. Biogas produced under this process contains about 65% of methane and about 26% of

carbon dioxide, hydrogen, nitrogen and oxygen. The combustible constituent in the gas is primarily methane. For an ideal of methane content as 70%, its calorific value is 5800 Kcal/m 3. Indigenous dual fuel engines have been installed for generating electricity using biogas produced from the plant. The composition of gas as analyzed in 1989 is as follows: Methane (CH4) Ethane (C2H6) Carbon dioxide (CO2) Carbon monoxide (CO) Oxygen (O2) Hydrogen (H2) Nitrogen (N2) 65.9% 2.6% 26.4% 1.2% 0.8% 1.5% 1.6%

Caloric value of this gas at 15.6c and 29.32 inches of mercury is 5251.81k.cal/m3 (589.243 BTU/ft3). Three dual engines with alternators as standby have been provided. Alternators are 70 KVA, Amp. 97.4 With P.F. -0.8, volt 415. Model of alternator is CM 225M, whereas engines make is kirloskar Cummins Ltd and Model -DG-495 G. The dual engines run with diesel oil and biogas in the proportion of 35% respectively. The diesel consumption is 1 lit/hour where as biogas consumption is 1.5m3 per hour for one Engine. With the available raw sewage characteristic about 150 to 180 m3 of biogas being produced per day which is generating about 600 KW off electricity per day sufficient run the plant for 5-6 hrs per day. The cost of electricity produced from biogas is Rs.1.25 per KWH including depreciation, where as the electricity charges of U.P State Electricity Board are Rs.2.05 per KWH. Air and oil filters, lubricating oil and coolant of the Engines are changed after every 250 hours run. There exist one old trickling Filter which was earlier constructed by Banaras Hindu University to treat waste water from University hospital and residential quarters. This unit was defunct when works of Ganga Action Plan were taken up at Varanasi. Under this plan the trickling factor unit was completely renovated and made operational. It consists of primary setting, trickling filter and secondary clarifier, each in one number with a capacity of 1.8 MLD. Primary sludge is allowed to remain in sludge chamber for a short period to decompose anaerobically before withdrawing to sludge drying beds. The secondary sludge is recirculated to primary settling tank. The quality of treated effluents meets prescribed standards.

Treated effluents are being used for irrigating 150 acres of land of private farmers besides 20 acres of University agricultural farm and lawns of STP campus. Excess of effluent finds its way to river Ganga through an out fall in a nala joining river. Revenue is being realized from the farmers who irrigating their fields. Digested sludge after drying is converted in manure. It is very good fertilizer for high yield. Its NPK values were realized at Regional Soil Testing Laboratory, Varanasi. These are as follows: Parameter N (nitrogen) P (phosphate) K (potassium) pH Values obtained 0.462% to 0.868% 8.064 to 11.648 kg/ hectare 56.0 to 78.4 kg/ hectare 6.6 to 6.8 Desirable for a good fertilizer. 0.8%

20 kg/ hectare 80 kg/hectare Depends on type of soil (for waste land 6.0) Table 3.2: Nutrient values of water used for irrigation purposes Presence of heavy metals was got examined at Industrial Toxicology Research Centre, Lucknow. Results of the three samples and allowable limit as per as American practice used in Agricultural production is summarized in the table below. This shows that the presence of heavy metals is within safe limit and it can be used safely as manure.

1. 2.

Inlet Collection Chamber Screen Channels

one no. size 1.2M x1.2M Two nos. each to handle 4MLD. Width of screen opening 20mm, openings 12 MS flats in screen 10 mm. thickness of (depth) with Size of each screen channel 2M x 0.5M x 1M 4 nos., non pressure type isolating gates. Two nos. each to handle 4 MLD. Size of grit to be removed 0.15mm Specific gravity of grit 2.65 Allowable overflow rate 1200 m3/m2/day (peak) Size of each grit chamber with depth for grit collection (0.2m) and fee board (0.3m) is 7.15m x 1.2m x 1.3m(depth) Throat width 350mm and capacity of the flume is 4mld (minimum) and 20 mld (maximum). No. of units: Two Surface loading: 24 m3/m2/day (Av.) 60m3/m2/day(peak) Detention time: 1.2 hours at peak flow Diameter : 14.6m & 3.5M(SWD) Weir loading: 87.25m3/m/day (Av) 218.13m3/m/day (peak) No. of units: Two Design flow 4000m3/day for each tank. Assumption is 40% reduction in BOD in primary settling, MLSS 3000 mg/L, F/m ratio 0.36mg/mg per day. Detention time 4hours Size of each tank 15.6m dia and 3.5M SWD Volumetric loading 1.077 kg BOD/m3/day BHP of aerators 30 with efficiency of gear box and motor as 80% No. of units: Two Surface loading 20m3/m2/day (Av.) 50m3/m2/day (peak) Size of each clarifier 16M dia and 3.5M SWD Detention time 3.5hrs (at average flow) 1.4 hrs (at peak flow) Weir loading 79.61m3/m/day (Av.) 199.04 m3/m/day (peak) No. of units: Two. Each 18m dia with liquid depth 8m No. of units: Two. Each 7.5m dia with 4M SWD No. of beds: 9. Size of each bed 28m x 12m Average manure produced per year is about 2500 MT. Primary settling one no. Dia 45 ft. and 8 ft. SWD Trickling filter one no. Dia 75 ft. and filter media depth 5.5 ft. Filter media- stone. Rotating arms two nos. No. a of nozzled in each arm 34 nos. Secondary clarifier one no. Dia 40 ft and 8 ft

3.

Grit Chamber

4. 5.

Parshal flume Primary settling

6.

Aeration Tank

7.

Secondary settling tank

8. 9. 10. 11.

Digesters Gas holders Sludge drying beds Trickling filter

SWD 13. Size of the Pond: 45M x 45M. Depth : 2.0M (approx) 12. Fish Pond Water used in Pond: Treated effluent Main species of fishes: Rohu, Nain, Katla. Table 3.3: Design of Bhagwanpur sewage treatment plant Sl. NO 1 2 3 4 5 6 7 8 9 10 11 12 13 14 INLET CHAMBER BAR SCREEN CHANNEL GRIT SCREEN CHANNEL PARSHALL FLUME PRIMARY SETTLING AERATION TANK SECONDARY SETTLING TANK DIGESTER SLUDGE DRYING BED RECIRCULATION PUMP HOUSE GAS HOLDER ENGINE ROOM GAS BURNER PRIMARY SLUDGE PUMP CUM SUMP HOUSE 15 16 17 18 19 20 21 22 23 FILTER SUMP CUM HOUSE INLET CHAMBER BAR SCREEN CHAMBER GRIT CHAMBER PRIMARY SETTLING TANK BIO FILTER SECONDARY SETTLING TANK RECIRCULATION PUMP HOUSE SLUDGE DRYING BED 1 1 1 2 1 1 1 1 3 3.5 x 3.5 1.70 x 0.9 3.70 x 0.60 x 0.80 4.40 x 1.20 x 1.10 13.720 x 2.44 22.860 x 1.68 12.19 x 2.44 4.90 x 3.5 22.70 x 8.90 1 2 2 1 2 2 2 2 9 1 1 1 1 1 1.20 x 1.20 2.0 x 0.5 x 1.0 7.15 x 1.2 x 1.3 350 MM 14.6 x 3.5 15.6 x 3.5 16.0 x 3.5 18.00 x 9.775 28.0 x 12.0 6.0 x 5.0 7.50 x 4.0 15.5 x 8.55 _ 3.5 x 3.5 Particulars Qty. Size in M

24

GAS BURNER

CHAPTER 4 MATERIALS AND METHODS

Biochemical Oxygen Demand (BOD) The amount of dissolved oxygen needed by aerobic biological organism in a body of water to degrade organic material present in a given water sample at certain temperature over a specific period of time is called Biochemical Oxygen Demand (BOD). BOD in general gives a quantitative index of organic substances which are degraded quickly in a short period of time. The organic pollutants are highly oxygen demanding. Carbon is the most important factor. Oxygen is used for degradation of carbon, which is measured by standard test called BOD 5 days test. The amount of dissolved oxygen required for oxidation over 5 days is measured, and the result is expressed in mg of oxygen per liter. DO is the basis of BOD Test. BOD5 of a water sample is estimated by the difference in the initial Dissolved Oxygen and Dissolved Oxygen after 5 days of incubation period of the sample at 20 0C in the dark condition. The BOD5 value was calculated as follows:
( ) ( )

Here, DO(initial) = Dissolved oxygen of the sample for first BOD bottle, which is not incubated DO(5 dark. Dissolved Oxygen Oxygen saturation or dissolved oxygen (DO) is a relative measure of the amount of oxygen that is dissolved or carried in a given medium.
days incubation)

= Dissolved oxygen of the sample after 5 days incubation in

Estimation of the dissolved oxygen (DO) is a key test in water pollution and waste treatment process control. The solubility of oxygen in water depends upon the partial pressure of oxygen in air, temperature of water and mineral content of water. Azide modification of Wrinklers method is followed to measure the dissolved oxygen. This method for determination of DO depends on the formation of a white precipitate of manganous hydroxide in a glass stoppered bottle completely filled with the water under examination. The oxygen dissolved in water rapidly combined with the manganous hydroxide, forming a mixture of higher oxides (brown color compound), which on acidification in the presence of an iodide, releases iodine in a quantity chemically equivalent to the oxygen content of the water sample. The liberated iodine is then titrated with a standard solution of sodium thiosulphate. The end point is detected using a starch indicator. 2 Mn(OH)2 + O2 = 2 MnO(OH)2 Basic Magnic Oxide MnO(OH)2 + 2 H2SO4 = Mn(SO4)2 +3H2O Mn(SO4)2 + 2 KI = MnSO4 + K2SO4 + I2 2 Na2S2O3 + I2 = Na2S4O6 + 2 NAI The quantity of Iodine liberated during these reactions is equivalent to the quantity of Oxygen present in the sample. The value of Dissolved Oxygen was calculated with the help of the formula:

Here, V and N are Volume and Normality of the titrant respectively. Hardness Hard water is water that has high mineral content. Hardness is generally imparted by the calcium and magnesium ions present in water. Polyvalent ions of some other metals like strontium, iron, aluminium, zinc and manganese etc. are also capable of contributing to the harness. Hardness is generally measured as concentration of only calcium and magnesium. Calcium and magnesium

form a complex of wine red color with Eriochrome Black T at pH of 10+/- 1. The EDTA has stronger affinity towards Ca++ and Mg++ and therefore, by addition of EDTA, the former complex is broken down and a new complex of blue color is formed. Method: 50 ml of sample was taken and 1ml each of buffer solution and sodium sulphide was added to it. Then 4-5 drops of Eriochrome Black T indicator was added which turned the solution to wine red color. This solution was titrated against EDTA solution. Change of wine red color to blue color depicts the end point. ( Alkalinity Alkalinity of water sample measures the ability of a solution to neutralize acids to the equivalence point of carbonate or bicarbonate. The alkalinity is equal to the stoichiometric sum of the bases in solution. It is its quantitative capacity to neutralize a strong acid to a designated pH. The alkalinity is considered as indicator of carbonate, bicarbonate and hydroxide content. It may also include borate, phosphate and silicate etc. It determines the suitability of water for irrigation. In natural water most of the alkalinity is caused due to dissolution of CO2 in water. CO2 + H20 = H2CO3 H2CO3 = H+ +HCO3HCO3 =H+ +CO32Carbonates and bicarbonates thus formed are dissociated and yield OHCO32- +2H2O =H2CO3 +2OHHCO3- +H2O =H2CO3 +OHTotal alkalinity = HCO3- +2CO32- +OH- +H+ Alkalinity also produced by the action of water on CaCO3 CaCO3+ H20 +CO2 = Ca (HCO3)2 Insoluble Soluble
-

Hydroxyl ions present in a sample as a result of dissociation or hydrolysis of solutes are neutralized by titration with standard acid. The alkalinity depends on the end point of pH used. Method: 50 ml of water sample was taken and 2-3 drops of phenolphthalein indicator was added. Pink color appeared. The solution was titrated with 0.02 N H2SO4 acid until the first permanent pink color disappeared which denote phenolphthalein alkalinity. Further, 2-3 drops of methyl orange indicator was added to this solution. It was then titrated against 0.02 N H2SO4 acid. Reappearance of pink color indicates total alkalinity. ( Where, Volume of sample taken = 50 ml Volume of H2SO4 used with phenolphthalein indicator = u ml ( Where, N = Normality of H2SO4. Volume of H2SO4 used with methyl orange indicator =v ml Total Volume of H2SO4 used with both indicator = (u+v) ml. Acidity Acidity of water is its quantitative capacity to neutralize a strong base to a designated pH. Acidity of water is mostly due to presence of strong mineral acids, weak acids (carbonic, acetic acids) and the salts of strong acids and weak bases (e.g. ferrous sulphate, aluminium sulphate etc.). On hydrolysis these salts produce a strong acid and metal hydroxides which are sparingly soluble and produce acidity. FeSO4 +2H2O = Fe (OH)2 +H2SO4 Al2 (SO4)3 +6H2O =2Al(OH)3 +3H2SO4 Hydrogen ions present in the sample as a result of dissociation or hydrolysis of solutes are neutralized by titration with standard alkali. It depends on the end point of pH used. ) )

Requirements: 0.02 N NaOH, phenolphthalein indicator. Method: 50 ml of sample was taken and 2-3 drops of phenolphthalein indicator was added to it and then it was titrated against 0.02 N NaOH. Development of pink color indicated the end point. ( Where, V = Volume of NaOH used (ml) N = Normality of NaOH Total solids (TS) Total solids are the measure of the amount of all kinds of solids (suspended, dissolved, volatile etc.) in water. It is determined as the residue left after evaporation of the unfiltered sample. Requirements: crucible, water bath, oven, desiccators, balance. Method: A clean and dry crucible was taken and was weighed. Then 250-500 ml unfiltered well shaken sample was taken in it. It was then evaporated on water bath. After evaporation it was dried in an oven at 105c for 1h. It was then cooled in desiccators. Then its final weight was taken. ( Where, a = Final weight of crucible (mg/L), b = Initial weight of crucible (mg/L), V = Volume of water sample evaporated (ml) Total dissolved solids (TDS) Total dissolved solids (TDS) denote mainly the various kinds of minerals present in water. It does not contain any gasses or colloids. It is determine as the residue left after evaporation of the filtered sample. Requirements: crucible, water bath, oven, desiccators, balance. Method: ) ( ) )

A clean and dry crucible was taken and was weighed. Then the water sample was filtered using filter paper. Then it was evaporated in the crucible on a water bath. After evaporation it was heated at 180 c for 1h in an oven. It was then cooled in desiccators and the final weight was then taken. ( ) ( )

Where, a = Final weight of crucible (mg/L) b = Initial weight of crucible (mg/L) V = Volume of water sample evaporated (ml) Total suspended solids (TSS) Total suspended solids (TSS) denote the suspended impurities present in water. In most of the cases they are of organic nature and pose severe problems of water pollution. Method: TSS is determined as the difference between total solids and total dissolved solids. TSS (mg/L) = TS TDS Where, TSS = Total suspended solids, TS = Total solids, TDS = Total dissolved solids Phosphate content of water Phosphorous occur in natural water and in waste water almost solely as phosphates. They are classified as orthophosphates, condensed phosphates and organically bound phosphates. These forms of phosphates arise from a variety of sources. Phosphate reacts with molybdate to form phosphomolybdic acid, which on reacting with some reducing agent likes SnCl2 produces a blue color. Requirements: ammonium molybdate, stannous chloride. Method: 20 ml of filtered and cleared solution was taken and 1 ml of ammonium molybdate and 0.4 ml of stannous chloride was added into it. The test tubes were kept for a fixed time

(2.5 min) for blue color to develop. Then OD was taken at 680 nm. Then concentration of PO4 (mg/ml) was computed from standard phosphate graph. ( )

Heavy metal analysis Analysis of heavy metal in water For the analysis of heavy metal, wastewater (Effluent from the treatment plants) was collected inside 250 ml polythene flask. Samples were filtered using whatman membrane filter paper (pore size: 0.45 m), acidified with 3 ml HNO3 (1:1, v/v) per liter and refrigerated in clean, sterile and labeled plastic containers (Ramos et al., 1999). Filtered water samples from all sampling sites were wet digested in HNO3:HClO4 (3:1, v/v) mixtures at 80 0C for 24 h and metal contents were determined using Perkin Elmer 2380 AAS. The concentration of heavy metal in water samples was determined with determined atomic absorption spectrophotometer (Perkin Elmer 2380, USA) fitted with a specific lamp for the particular metal using appropriate drift blanks. Blank and drift standards were run after five determinations to calibrate the instruments.

CHAPTER 5 RESULTS AND DISCUSSION Sampling of untreated sewage and treated wastewater of Bhagwanpur sewage treatment plant was done three times in the months of January, February and March. Water samples were analyzed for the various physico-chemical parameters as well as for the heavy metals and the following results were obtained after the analysis of untreated and treated water samples. 1. Alkalinity

In untreated sewage alkalinity was found to be 402 mg/L. In the second sampling it was found to be 430 mg/L and in the third sampling it was found to be 330 mg/L (Table 5.1). Highest value was obtained in the month of February and minimum value was obtained in March sampling. The reason for the high value in the second sampling can be attributed to the fact that many festivals arrived in the end of February like Shivratri where a large population of pilgrims visit Varanasi to take bath in Ganga which might be responsible for increasing the total Alkalinity of water (Fig. 5.1). In treated secondary effluent alkalinity value was found 372 mg/L in month of January, 360 mg/L in February and 310 mg/L in the month of March. Highest reduction in value was obtained in the second sampling and the minimum reduction in value was obtained in the third sampling. The efficiency of plant in treating of water sample was found to be 7.46%, 16.27% and 6.06% respectively. In totality it was found to be 9.93% effective in treating alkalinity in water sample. (Figure 5.1).

2.

Acidity

In untreated sewage acidity was found to be 37 mg/L. In the second sampling it was found to be 34 mg/L and in the third sampling it was found to be 40 mg/L (Table 5.1). Highest value was obtained in the month of March and the minimum value was obtained in the second sampling. Not much variation was observed in the values of acidity and the slight variation can be attributed to the incoming of acidic substances from the industrial effluents in to river Ganga. (Figure 5.1) In treated secondary effluent acidity value was found to be 21 mg/L. In the second sampling it was found to be 14 mg/L and in the third sampling it was found to be 20 mg/L. Minimum reduction in value was obtained in the first sampling and the reduction value was same for both second and third sampling. The efficiency of plant in treating of water sample was found to be 43.24%, 58.28%, and 50.00% respectively. In totality it was found to be 50.50% effective in treating acidity in water sample.(Figure 5.1) 3. Hardness

In untreated sewage hardness was found to be 420 mg/L. In the second sampling it was found to be 310 mg/L and in the third sampling it was found to be 297 mg/L. (Table 5.1). Highest value was obtained in the month of January and the minimum value was obtained in the third sampling. Not much variation was observed in the value of this parameter and even if some variation was observed it was due to incoming salts of calcium and bicarbonate ions in the form of domestic and industrial sewage. (Figure 5.3) In the treated secondary effluent hardness was found to be 368 mg/L. In the second sampling it was found to be 302 mg/L and in the third sampling it was found to be 290 mg/L. Minimum reduction in value was obtained in the third sampling and the highest reduction in value was obtained in the first sampling. The efficiency of plant in treating of water sample was found to be 12.38%, 02.58% and 02.36% respectively. In totality it was found to be 5.77% effective in treating hardness in water sample.(Figure 5.3)

4.

Dissolved Oxygen (DO)

In the untreated sewage DO was found to be 2 mg/L. In the second sampling it was found to be 0.4 mg/L and in the third sampling it was found to be 0 mg/L. (Table 5.1). Highest value was obtained in the month of February and the minimum value was obtained in the third sampling. Not much variation was observed in this parameter. The low value of DO can be attributed to high organic load in the domestic sewage and industrial effluent and the oxygen present in the water being utilized by the microbes present in the water for the degradation of the biodegradable matter present in the sewage. (Figure 5.2) In the treated effluent DO was found to be 1 mg/L. In the second sampling it was found to be 0.6 mg/L and in the third sampling it was found to be 1 mg/L. In the first sampling DO content of treated water was found to be less than untreated water. The reason for this is that the sample was taken from the extreme edge of the aeration tank which is the only way of increasing the DO content of water sample. When the sample is taken from the place close to aerator the DO content was found to be higher than when taken from the edge of aeration tank. Even if the water sample is withdrawn from the aeration tank and kept for sometime separately then also its DO content gets reduced. The treatment plant was found to be 50.00 % effective in increasing the DO of water samples.(Figure 5.2) 5. Biochemical Oxygen Demand (BOD)

In the untreated sewage BOD value was found to be 100 mg/L and in the third sampling it was found to be 80 mg/L. (Table 5.1). The value was found higher in the month of February than in the month of March. It can be attributed to high pollution load in the effluents coming as sewage water or industrial waste water where the organic load is higher which requires greater amount of oxygen for its degradation. Hence biological oxygen demand is higher. (Figure 5.2) In the treated effluent BOD value was found to be 140mg/L and in the third sampling it was found to be 60 mg/L. The reason for higher BOD of water can be because of the fact that when a power cut occur in the treatment plant they treat only 50% of the water sample and the rest is left as such which gets piled up in each successive day and when water sample was taken from such treated water then its BOD was found to be higher than even the untreated water sample. The efficiency of plant in treatment of this parameter was found to be 25%. (Figure 5.2)

6.

Total solids (TS) and total dissolved solids (TDS) content

In the untreated sewage the value for TS and TDS was found to be 0.78 and 0.52 mg/L respectively. In the second sampling these were found to be 0.4 and 0.58 mg/L and for third sampling these were found to be 0.08 and 0.38 mg/L respectively (Table 5.1). The highest value of TS was obtained in the month of January where as the lowest value was obtained in the third sampling. (Figure 5.3) In case of TDS the highest value was obtained in the month of February and the lowest value was obtained in the third sampling. The reason for this is that end of February is a festive season hence the visit of pilgrims increases at this time. Which causes an increase in the solids content of water since lots of people take bath at this time in Ganga as well as the number of visitors also increases at this time. (Figure 5.4) In the treated effluent the value for TS and TDS was found to be 0.06 and 0.32 mg/L respectively. In the second sampling these were found to be 0.06 and 0.12 mg/L and for third sampling these were found to be 0.04 and 0.34 mg/L respectively. Highest reduction in TS value was observed in the first sampling and for TDS was observed in the second sampling. Minimum reduction in the value of TS and TDS was observed in third sampling. The plant was found to be 36.00% and 54.90% efficient for treating TS and TDS of water sample respectively.(Figure 5.3 and Figure 5.4) 7. Phosphate

The phosphate content in the untreated sewage was found to be 1.00 mg/L and for third sampling it was found to be 0.26 mg/L.(Table 5.1). The value was obtained higher for the month of February in comparison to the March sampling (Figure 5.4). The phosphate content in the treated effluent was found to be 1.12 mg/L and for third sampling it was found to be 0.34 mg/L. The value was obtained higher for second sample in comparison to third sample. (Figure 5.4)

8.

Heavy metals

The untreated sewage of February month sample was assessed for heavy metals. The amounts of heavy metals obtained are Cadmium was found to be 0.045 mg/L while Chromium was found to be 0.252 mg/L. Potassium was found to be 1.113 mg/L while Iron was found to be 0.051 mg/L. No trace of copper and lead was found in the untreated water samples. (Table 5.2) The amounts of heavy metals obtained are: Cadmium was found to be 0.059 mg/L while Chromium was found to be 0.366 mg/L. Potassium was found to be 1.268 mg/L while Iron was found to be 0.037 mg/L. Even traces of lead was found in the treated water sample which amounts to 0.081 mg/L. no traces of copper was found in the treated water samples.(Table 5.2)

500 450 400 Alkalinity (mg/L) 350 Acidity (mg/L) 300 250 200 150 100 50 0 January February March Sampling Duration (Months)

45 40 35

Figure 5.1 Alkalinity and

Untreated Treated

30 25 20 15 10 5 0

Acidity values in treated and untreated water sample from

Untreated Treated

January to March 2012.

January

February Month

March

2.5 2 1.5 1 0.5 0 January February Month March Untreated Treated BOD (mg/L) DO (mg/L)

160 140 120 100 80 60 40 20 0 January February Month March Untreated Treated

Figure 5.2 Dissolved oxygen (DO) and Biochemical oxygen demand (BOD) values in treated and untreated water sample from January to March 2012.

500 450 400 0.9 0.8 0.7 0.6 TS (mg/L) 0.5 0.4 0.3 0.2 0.1 0 January February Month March January February Month March Untreated Treated Untreated Treated

Hardness (mg/L)

350 300 250 200 150 100 50 0

Figure 5.3 Hardness and total solids (TS) values in treated and untreated water sample from January to March 2012.

0.7 0.6 0.5 TDS (mg/L) 0.4 0.3 0.2 0.1 0 January February Month

Untreated Treated

1.15 1.1 Phosphate (mg/L) 1.05 1 0.95 0.9 Untreated Treated

March

January

February Month

March

Figure 5.4 Total dissolved solids (TDS) and Phosphate values in treated and untreated water sample from January to March 2012.

Water Sample Untreated Sewage

Parameters Alkalinity (mg/L) Acidity (mg/L) DO (mg/L) BOD (mg/L) Hardness (mg/L) TS (mg/L) TDS(mg/L) Phosphate (mg/L)

January February 402 430 38 36 2 0.4 140 80 430 310 0.78 0.4 0.52 0.58 1.113 1.11

March 330 40 0 100 300 0.08 0.38 1.128

Treated Secondary Effluent

Alkalinity (mg/L) 372 360 310 Acidity (mg/L) 20 14 20 DO (mg/L) 1 0.6 1 BOD (mg/L) 100 60 70 Hardness (mg/L) 368 302 290 TS (mg/L) 0.06 0.06 0.04 TDS(mg/L) 0.32 0.12 0.34 Phosphate (mg/L) 0.981 1.008 1.013 Table 5.1: Physico chemical parameters analyzed in untreated sewage and treated secondary effluent of bhagwanpur sewage treatment plant Heavy Metal Cadmium Copper Chromium Potassium Iron Lead Untreated Sewage 0.038 0.012 0.203 1.11 0.058 0.037 0.047 0.02 0.249 1.19 0.044 0.043 0.05 0.032 0.303 1.04 0.05 0.038 Treated Secondary Effluent 0.054 0.034 0.325 1.32 0.021 0.002 0.058 0.041 0.347 1.3 0.037 0.125 0.064 0.057 0.426 1.18 0.052 0.118

Table 5.2: Heavy metal analysis in untreated sewage and treated secondary effluent of bhagwanpur sewage treatment plant

Acidity Acidity Pearson Correlation Sig. (2-tailed) Sum of Squares and Cross-products Covariance N Pearson Correlation Sig. (2-tailed) Sum of Squares and Cross-products Covariance N 1 632.000 126.400 6 -.031 .953 -1.200 -.240 6

Correlations BOD DO -.031 .953 -1.200 -.240 6 1 2.353 .471 6 .647 .165 1.040E3 208.000 6 .609 .200 59.667 11.933 6

hardness .288 .580 888.000 177.600 6 * .831 .040 156.533 31.307 6

TS .614 .195 10.320 2.064 6 .655 .158 .673 .135 6

TDS .814 .049

*

Phosphate .954 .003

**

7.440 1.488 6 .216 .681 .121 .024 6

3.482 .696 6 -.114 .830 -.025 -.005 6

BOD

DO

Pearson Correlation Sig. (2-tailed) Sum of Squares and Cross-products Covariance N Pearson Correlation Sig. (2-tailed) Sum of Squares and Cross-products Covariance N Pearson Correlation Sig. (2-tailed) Sum of Squares and Cross-products Covariance N Pearson Correlation Sig. (2-tailed) Sum of Squares and Cross-products Covariance N Pearson Correlation Sig. (2-tailed)

.647 .165 1.040E3 208.000 6 .288 .580 888.000 177.600 6 .614 .195 10.320 2.064 6 * .814 .049 7.440 1.488 6 ** .954 .003

.609 .200 59.667 11.933 6 * .831 .040 156.533 31.307 6 .655 .158 .673 .135 6 .216 .681 .121 .024 6 -.114 .830 -.025 -.005 6

.878 .021

.735 .096 31.433 6.287 6 .754 .084

.561 .247 13.033 2.607 6 .373 .466 16.667 3.333 6 .711 .113

.491 .323 4.552 .910 6 .147 .781 2.617 .523 6 .604 .204 .059 .012 6 .711 .113

4.083E3 816.667 6 * .878 .021 6.887E3 1.377E3 6 .735 .096 31.433 6.287 6 .561 .247 13.033 2.607 6 .491 .323 4.552 .910 6

6886.667 1377.333 6 1

Hardness

1.506E4 3012.267 6 .754 .084 61.867 12.373 6 .373 .466 16.667 3.333 6 .147 .781 2.617 .523 6

61.867 12.373 6 1

TS

.448 .090 6 .711 .113 .173 .035 6 .604 .204 .059 .012 6

.173 .035 6 1

TDS

.132 .026 6 .711 .113 .038 .008 6

.038 .008 6 1

Phosphate

Sum of Squares and 3.482 Cross-products Covariance .696 N 6 *. Correlation is significant at the 0.05 level (2-tailed). **. Correlation is significant at the 0.01 level (2-tailed).

.021 .004 6

Table 5.3: Correlation matrix of physico chemical parameters CHAPTER 6 CONCLUSION AND RECOMMENDATION The parameters for which water quality was tested varied in various ways. High variation was observed in case of total alkalinity. But not much variation was observed in case of acidity and hardness. The DO content was found very low which is because of the high organic load in the water. This was also the reasons for high Biochemical oxygen demand of the water sample. Alkalinity was found to be higher than the permissible limit of 200 mg/L. whereas hardness was found to be in permissible maximum limit of water which is 600 mg/L. In case of total solids the

amount was solely contributed by dissolved solids which were much below the permissible limit of water which is 250 mg/L. The treatment plant was found upto 50% maximum efficiency for treatment of parameters like Acidity, DO and TDS. It was found only 25% efficient in treating BOD of water samples. It was found very less effective in treating parameters like Alkalinity and Hardness of water samples which was even less than 10%. Some recommendations which can be used for improvement of efficiency of treatment are as follows: 1. They always suffer from problems of power cut where they switch to generators

but for this they had to limit the treatment to only one treatment unit which leads to 50% reduction in their capacity for treatment of waste water which leads to overloading and improper treatment efficiency of the plant. So they need to work out on this problem which can be overcome by use of high load efficient generators as well as they can set up a separate power unit for their plant which will solely generate electricity to be used by the plant. 2. Many a times much of the machinery was found in improper working conditions.

Not much attention is given to such issues. Hence the concern towards proper functioning of the machinery should be increased. A proper periodic monitoring should to be done to avoid such problems. 3. They can also include few new techniques in their treatments which are

ecofriendly as well as cost effective which can enhance the efficiency of their treatment of waste water like Photocatalytic oxidation, cavitation as well as ozonation, Fentons method of treatment etc.